Fungicide agent and preparation method of active substance
Abstract
A fungicidal composition containing as an active ingredient a compound of the general formula I or II GLf N 2 Q··/ R/ %N fi3 aj to (II) where the general symbols have the meanings given below, or their acid addition salts or their complex compounds with a metal. A method of preparing the active ingredients is further described.

Term
No projected expiry on record.
- Priority
- Filed
- Granted
- Today
10 claims: 2 independent, 8 dependent
- 1PREDMET 1. Fungicidní prostředek, vyznačený tím, že obsahuje jako účinnou látku sloučeninu obecného vzorce I nebo II Go f (II) kde znamená Qi, Q2 a Q3 na sobě nezávisle atom vodíku nebo methylovou skupinu, Ri alkylovou skupinu s 2 až 18 atomy uhlíku, cykloalkylovou skupinu s 3 až 6 atomy uhlíku, naftylovou skupinu nebo skupinu obecného vzorce VYNÁLEZU kde znamená Ri‘ alkylovou skupinu s 6 až 18 atomy uhlíku, cykloalkylovou skupinu s 3 až 6 atomy uhlíku, naftylovou skupinu nebo kde znamená Rl a Rs na sobě nezávisle atom vodíku, atom halogenu, methoxyskupinu, trifluormethoxyskupinu, thiomethylovou skupinu vzorce SCH3, skupinu vzorce —SO2CH3, fenylovou skupinu, fenylovou skupinu substituovanou atomem halogenu a/nebo alkylovou skupinou s 1 až 4'atomy uhlíku a/nebo trifluormethylovou skupinou, fenoxyskupinu, fenoxyskupinu substituovanou atomem halogenu a/nebo alkylovou skupinou s 1 až 4 atomy uhlíku a/nebo trifluormethylovou 127 128 skupinou, trifluormethylovou skupinu, alkylovou skupinu s 1 až 4 atomy uhlíku nebo cyklohexylovou skupinu, za podmínky, že v případě sloučeniny obecného vzorce II, nemohou symboly Ri a Rs znamenat zároveň atom vodíku, Rž a R3 na sobě nezávisle alkylovou skupinu s 1 až 6 atomy uhlíku, cykloalkylovou skupinu s 3 až 6 atomy uhlíku, skupinu obecného vzorce OR6 nebo obecného vzorce kde znamená R6 atom vodíku nebo alkylovou skupinu s 1 až 4 atomy uhlíku, za podmínky, že R2 a R3 neznamenají oba vždy hydroxylovu skupinu a R2 a R3 mohou vytvářet 1,2-glykolový, 1,3-glykolový nebo 1,4-glykolový můstek nebo 1,4-nenasycený glykolový můstek substituovaný až 4 alkylovými skupinami R7 až R10, které mají celkem až 4 atomy uhlíku nebo její adiční sůl s kyselinou nebo její komplexní sloučeninu s kovem.
- 2Fungicidní prostředek podle bodu 1, vyznačený tím, že obsahuje jako účinnou látku sloučeninu obecného vzorce I, kde Ql, Q2, Ri, R2, R3, R6, R7 — R10 mají v bodu 1 uvedený význam a kde Ri a Rs znamenají na sobě nezávisle atom vodíku, atom halogenu, methoxyskupinu, trifluormethoxyskupinu, thiomethylovou skupinu vzorce SCH3, skupinu vzorce — SO2CH3, fenylovou skupinu, fenylovou skupinu substituovanou atomem halogenu a/nebo alkylovou skupinou s 1 až 4 atomy uhlíku a/nebo trifluormethylovou skupinou, fenoxyskupinu, fenoxyskupinu substituovanou atomem halogenu a/ /nebo alkylovou skupinou s 1 až 4 atomy uhlíku a/nebo trifluormethylovou skupinou, trifluormethylovou skupinu, alkylovou skupinu s 1 až 4 atomy uhlíku nebo cyklohexylovou skupinu nebo její adiční sůl s kyselinou nebo její komplexní sloučeninu s kovem.
- 3Fungicidní prostředek podle bodu 2, vyznačený tím, že jako účinnou látku obsahuje (Ι,Γ-bif enyI-4-yl) dimethyl (1H-1,2,4-triazol-l-ylmethyl Jsilan.
- 4Fungicidní prostředek podle bodu 2, vyznačený tím, že jako účinnou látku obsahuje bis- (4-chlorf enyl Jmethyl (1H-1,2,4-triazol-l-ylmethyl jsilan.
- 5Fungicidní prostředek podle bodu 2, vyznačený tím, že jako účinnou látku obsahuje [bis (4-fluorfenyl) ]methyl(lH-l,2,4-triazol-l-ylmethyl) silan.
- 6Fungicidní prostředek podle bodu 2, vyznačený tím, že jako účinnou látku obsahuje 4-fluorfenyl (methyl jfenyl (1H-1,2,4-triazol-l-ylmethyl jsilan.
- 7Fungicidní prostředek podle bodu 1, vyznačený tím, že obsahuje jako 1 účinnou látku sloučeninu obecného vzorce II, kde Qi, Q2, Qs, Ri‘, R2, R3, Ri, Rs, Re, R7 — R10 mají význam uvedený v bodu 1 nebo její adiční sůl s kyselinou nebo její komplexní sloučeninu s kovem.
- 8Fungicidní prostředek podle bodu 7, vyznačený tím, že jako účinnou látku obsahuje (2,4-dichlorfenyl J dimethyl (lH-imidazol-l-ylmethyl jsilan.
- 9Způsob přípravy účinné látky podle bodu 2, obecného vzorce I, kde jednotlivé symboly mají v bodu 2 uvedený význam, vyznačený tím, že se nechá reagovat meziprodukt ze souboru zahrnujícího sloučeniny vzorce CI3S1CH2CI, Rs I C12SÍCH2C1 a R2 I Cl—Si—CH2CI I R3 kde R2 a R3 mají shora uvedený význam, ve vhodném rozpouštědle se sloučeninou obecného vzorce RlM kde 129 130 R2 Ri má shora uvedený význam a M znamená atom sodíku nebo atom lithia nebo MgX, kde X je atom chloru, bromu nebo jodu, při teplotě —80 °C až 40 °C za vzniku chlormethylsilanu, který se nechá reagovat s 1,2,4-triazolem, jeho 3-methylderivátem nebo 3,5-dimethylderivátem nebo s jeho solí s alkalickým kovem, v polárním aprotickém rozpouštědle, v etherech nebo ketonech při teplotě 0 až 150 °C.
- 10Způsob přípravy účinné látky podle bodu 7 obecného vzorce II, kde jednotlivé symboly mají v bodu 7 uvedený význam, vyznačený tím, že se nechá reagovat meziprodukt volený ze souboru zahrnujícího sloučeninu vzorce CbSiCHzCl, R3 i CI2SÍCH2CI a Cl—Si—CH2CI I r 3 kde R2 a R3 mají shora uvedený význam ve vhodném rozpouštědle se sloučeninou obecného vzorce RiM kde Ri má shora uvedený význam a M znamená atom sodíku nebo atom lithia nebo MgX, kde X je atom chloru, bromu nebo jodu, při teplotě —80 °C až 40 °C za vzniku chlormethylsilanu, který se nechá reagovat s imidazolem, jeho 2-methylderivátem, 2,4-dimethylderivátem, 4,5-dimethylderivátem a 2,4,5-trimethylderivátem nebo s jeho solemi s alkalickým kovem v polárním aprotickém rozpouštědle, v etherech nebo ketonech při teplotě 0 °C až 150 °C. Severografia, n. p., závod 7, Most Cena 2,40 Kčs
Independent claims10
3,018 paragraphs in 153 sections, as filed
The invention relates to fungicidal compositions which are particularly suitable for the treatment of live plants which contain, as active ingredient, silylmethyltriazoles and imidazoles as such, for example dimethyl (phenyl) (1H-1,2,4-triazole-1-methyljsilane and (1,1'-). biphenyl-4-yl) dimethyl (1H-1H-indazol-1-ylmethyl) silane.
U.S. Pat. No. 3,692,798 protects compounds of the formula
CH
CH, and its use as fungicides.
Silyl ethers of the formula -N are also known
OSLRi I <sup>3</sup> R 1 -CH 2 CH-CH-CH 2 CH 2 wherein
R1, R2 and R3 are lower alkyl or phenyl and have antimicrobial activity.
European Patent Publication No. 29 993 protects compounds of the general formula
<img file="CS238626B2_D0001.tif" />
where it means
R is C 1 -C 4 alkyl;
Y and Z are hydrogen or a group of formula
Where S1R2R3R3 denotes
Ar is a substituted phenyl group,
X is CH or N and R is alkyl;
these compounds are said to be useful as agricultural fungicides.
NSR 3,000,140 discloses silyl ethers of the general formula: sulfur<sub>3</sub>
Ar-O-CH-CH-C (CH 2 -)
AND
N where where means
R 1, R 2 and R 3 are alkyl, haloalkyl, alkenyl, alkynyl or substituted phenyl. These compounds are considered agricultural fungicides.
U.S. Patent Nos. 3,256,308 and 3,337,598 protect compounds of the formula <sup>RÍ</sup>,
<img file="CS238626B2_D0002.tif" />
Ar is a substituted phenyl group,
X is CH or N;
R is phenyl or lower alkyl. These compounds are said to be useful as agricultural fungicides.
U.S. Pat. No. 4,248,992 discloses a class of organosilicon compounds having at least one monovalent guanidine group of the formula
NR2
Z —N = where
NR2
R 1 is methyl, ethyl, vinyl or phenyl. They are said to be effective against fungi.
Belgian Patent No. 785,127 discloses quaternary ammonium salts of the formula wherein
R represents a hydrogen atom or a monovalent hydrocarbon group.
121
122
Compound% Disease Control
<td colspan="2">rice</td>
<td>[4- (4-Chlorophenoxy) phenyl] dimethyl (1H-imidazol-1-ylmethyl) silane</td><td> 100</td>
<td>Butyl (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 90</td>
<td>(1,1'-Biphenyl-4-yl) butyl (1H-imidazol-1-ylmethyl) methylsilane</td><td> 90</td>
<td>Butyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) methylsilane</td><td> 100</td>
<td>(1,1'-Biphenyl-2-yl) dimethyl (1H-imidazol-1-ylmethyl) silane</td><td> 90</td>
<td>(Ι, Γ-Biphenyl-3-yl) dimethyl (1H-imidazol-1-ylmethyl) silane</td><td> 80</td>
<td>[bis (2-Chlorophenyl)] (1H-imidazol-1-ylmethyl) methylsilane</td><td> 90</td>
<td>Dimethyl (1H-imidazol-1-ylmethyl) - (4-methylsulfonylphenyl) silane</td><td> 100</td>
<td>[bis (4-Bromophenyl)] (1 H -imidazol-1-ylmethyl) methylsilane</td><td rowspan="2"> 80</td>
<td rowspan="2">bis (4-fluorophenyl) hydroxy (1 H -dazol-1-ylmethyl) silane</td>
<td rowspan="2"> 60</td>
<td rowspan="3">Dimethyl [1H-imidazol-1-ylmethyl] J (4-trifluoromethoxyphenyl) - silane</td>
<td></td>
<td> 90</td>
<td>(4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl)</td><td></td>
<td>silane</td><td> 90</td>
<td>Dimethyl (1H-hidazol-1-ylmethyl) octadecylsilane</td><td> 80</td>
<td>Oxybis [bis (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 50</td>
<td>(4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td>
<td>(Ι, Γ-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 complex with copper chloride</td><td> 100</td>
<td>Methyl [bis (4-methylphenyl)] (1H-1,2,4-triazol-1-ylmethyl)</td><td></td>
<td>silane</td><td> 80</td>
<td>Example 78</td><td></td>
The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). These suspensions are sprayed on the tomato seedlings to the point where they start to run off. The next day, the plants are inoculated with a spore suspension of Phytophthora infestans causing tomato mold and incubated in a moisture-saturated chamber at 20 ° C for 24 hours and then left in the growth chamber for a further 7 days before assessing the degree of infestation. The percentage of infestation is shown in the following table. Treated plants show no or little attack, while untreated plants show attack on each leaf.
Table XXX
Compound% Reduction of Tomato Mold [Bis (2-Fluorophenyl)] methylfH-1,2,4-triazol-1-ylmethyl) silane: 1 Complex with Copper Chloride (4-Bromophenyl) (1H-imidazole-1) -ylmethyl] dimethylsilane 30 (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 50 (1H-Imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane 80
Dimethyl (1H-imidazol-1-ylmethyl) (3-trifluoromethylphenyl) silane 70 (2,6-Dimelhoxyphenyl) (dimethyl) (1H-imidazol-1-ylmethyl) silane 50 [bis (2-Chlorophenyl)] (1H- imidazol-1-ylmethyl jmethylsilane 60
Dimethyl (4-phenoxyphenyl) [1H-1,2,4-triazol-1-ylmethyl] silane 50 [4- (4-Chlorophenoxy) phenyl] dimethyl (1H-1,2,4-triazol-1-yl) ylmethyl jsilane 50 (1,1'-Biphenyl-2-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl jsilane 50 (1,1'-Biphenyl-4-yl) dimethyl (1H- 1,2,4-triazol-1-ylmethyl) silane, 4-dodecylbenzenesulfophonic acid salt 60
119
120
Compound% reduction of bacterial blotch of rice sheath
23862B
Compound% Reducing Rice Disease
Methyl [bis (4-methyl} phenyl] (1H-1,2,4-triazol-1-ylmethyl) silane 30
Example 77
The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters).
<td colspan="2">holůj. These suspensions are sprayed onto the rice seedlings until they begin to run down. The next day, the plants are inoculated with a rice disease spore suspension of Pyricularia oryzae and incubated in a humidified chamber at 28 ° C for 24 hours and then left in the growth chamber for a further 7 days before assessing the degree of infestation. The percentage of infestation is shown in the following table. Treated plants do not show infestation or are infested slightly, untreated show infestation on each leaf.</td>
<td>Table XXIX</td><td></td>
<td>Compound</td><td>% disease reduction rice</td>
<td>Dimethyl (1-naphthalenyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 70</td>
<td>bis (4-Chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td>
<td>[4- (Dimethylethylphenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td>
<td>(4-Chlorophenyl) methylphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90 1</td>
<td>bis (4-Fluorophenyl) (methyl) (1H-1,2,4-trlazol-1-ylmethyl) silane</td><td> 100</td>
<td>Butyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td>
<td>(2-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>(1,1'-Biphenyl-4-yl) butyl (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>Butyl (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
Dibutylphenyl] (1H-1,2,4-triazol-1-ylmethyl) silane 80 bis (1,1'-Biphenyl-4-yl) (methyl j (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1,1'-Biphenyl-2-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 90
2-Chlorophenyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane 100
4-Bromophenyl (methylphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 80 [bis (2-Chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 90
Dimethyl (4-methylsulfonylphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 70 [bis (4-bromophenyl)] methyl
-1,2,4-triazol-1-ylmethyl jsilane 90 (1,1'-Biphenyl-4-yl) dimetbyl (1H-1,2,4-triazol-1-ylmethyl jsilane, 4-dodecylbenzenesulfonic acid salt 80 (1)) 1,1'-Biphenyl-4-yl] dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane: 1 complex with copper (I) chloride 100 (1,1'-Biphenyl-4-yl) dimethyl (1H- 1,2,4-triazol-1-ylmethyl jsilane: 1 complex with zinc chloride 100 [bis (2-fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane,
1: 1 complex with cuprous chloride 90 [bis (2-Fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethylsilane): 1 complex with cuprous chloride 100 (1H-Imidazol-1-ylmethyl) Dimethyl 4-phenoxyphenylsilane 70 [4- (1,1-Dimethylethylphenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 80 (4-Fluorophenyl) (1H-imidazol-1-ylmethyl) (phenyl) silane
100
117
118
238G2B
<td>Compound</td><td>% reduction of bacterial spots of rice sheath</td><td>Compound</td><td>% reduction of bacterial spots of rice sheath</td>
<td>Butyl (methyl) phenyl (1H-1,2,4-</td><td></td><td>(4-Fluorophenyl) (1H-imidazole-1-</td><td></td>
<td>(triazol-1-ylmethyl) silane (1,1'-Biphenyl-4-yl) butyl (methyl-</td><td> 90</td><td>-ylmethyl) methyl (phenyl) silane (1 H-Imidazol-1-ylmethyl) [2-</td><td> 90</td>
<td>thyl) (1H-1,2,4-triazol-1-ylinethyl) silane Butyl (4-Fluorophenyl) methyl (1H-</td><td> 80</td><td>methoxyphenyl) dimethylsilane [4- (4-Chlorophenoxy) phenyl] dimethyl (1H-imidazol-1-ylmethyl) -</td><td> 90</td>
<td>-1,2,4-triazol-1-ylmethyl) silane bis [Ι, Γ-Biphenyl-4-yl] (methyl) -</td><td> 80</td><td>thyl) silane Butyl [1H-imidazol-1-ylmethyl] -</td><td> 70</td>
<td>[1H-1,2,4-triazol-1-ylmethyl) silane [bis [4-Methoxyphenyl]] methyl-</td><td> 90</td><td>methyl (phenyl) silo an (1,1'-Biphenyl-4-yl) butyl [1H-imidazol-1-ylmethyl] methyl-</td><td> 80</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) - silane</td><td> 80</td><td>silane Butyl (4-fluorophenyl) [1H-imida-</td><td> 90</td>
<td>2-Chlorophenylphenyl) phenyl (1H- (1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td><td>zol-1-ylmethyl) methylsilane (1,1'-Biphenyl-2-yl) dimethyl-</td><td> 80</td>
<td>4-Bromophenyl (methyl) phenyl (1H-1,2,4-trlazol-1-ylmethyl) silane</td><td> 90</td><td>[1H-imidazol-1-ylmethyl] silane (1,1'-Biphenyl-3-yl) dimethyl (1H-</td><td> 90</td>
<td>[bis [2-Chlorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 60</td><td>-imidazol-1-ylmethylsilane [bis (2-Chlorophenyl)] [1H-imida-</td><td> 90</td>
<td>(Ι, Γ-Biphenyl-4-yl) dimethyl- (1H-1,2,4-triazxl-1-ylmethyl) silane, 1: 1 chloride complex</td><td></td><td>zol-1-ylmethyl) methylsilane (1,1'-Biphenyl-4-yl) dimethyl [1H-</td><td> 40</td>
<td>copper (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane,</td><td> 90</td><td>(imidazol-1-ylmethyl) silane, 1: 1 complex with copper (I) chloride [2-Chlorophenyl] [dimethyl] (1H-</td><td> 50</td>
<td>1: 1 complex with zinc chloride</td><td> 90</td><td>imidazol-1-ylmethyl) silane bis [4-fluorophenyl] hydroxy [1H-</td><td> 90</td>
<td>2-Chlorophenyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl)</td><td></td><td>imidazol-1-ylmethyl) silane</td><td> 90</td>
<td>thyl) silane [bis (2-Fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 complex with copper-</td><td> 70</td><td>[3-Chlorophenyl) dimethyl (1 H -imidazol-1-ylmethyl) silane [4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) -</td><td> 90</td>
<td>ným (1H-Imidazol-1-ylmethyl) dimime</td><td> 90</td><td>thyl) silane (3,5-Dichlorophenyl) dimethyl (III-)</td><td> 90</td>
<td>thyl (4-phenoxyphenyl) silane bis (4-Fluorophenyl) (1H-imidazole)</td><td> 70</td><td>imidazol-1-ylmethyl) silane Dimethyl [1H-imidazol-1-yl-</td><td> 90</td>
<td>(1-ylmethyl) methylsilane (1H-Imidazol-1-ylmethyl) dimethyl (2-trifluoromethylphenyl) -</td><td> 90</td><td>methyl) octadecylsilane (4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) -</td><td> 100</td>
<td>silane Butyl (2,4-dichlorophenyl) [1H-imidazol-1-ylmethyl) methyl-</td><td> 80</td><td>thyl) silane (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane,</td><td> 90</td>
<td>silane</td><td> 90</td><td>2: 1 complex with chloride: copper-</td><td></td>
<td>bis [2,4-Dichlorophenyl) [1H-imidazol-1-ylmethyl) methylsilane</td><td> 80</td><td>natým</td><td> 80</td>
115
118
Compound% reduction of peach brown rot. The percentage of infestation (percent inhibition of colony growth on treated peaches compared to colonies on untreated peaches) is shown in the following table.
Table XVII
Compound% Brown Rot Control (Dimethylphenyl (1,2,4-triazol-1-ylmethyl) silane 89 (Butyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 95 (1,1'-Bif) enyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100
Butyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 98
Dimethyl (4-methoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 97 (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis ( 4-Chlorophenyl] (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 95 (1,1'-Biphenyl-4-yl) dimethyl (4H-1,2,4-triazole -4- Sulfate 96 bis (4-Fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100
Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 98 (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) ) Silane 70 (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90
Butyl (4-Fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100
Dibutyl (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 81 (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 83
Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 45 (1H-Imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane 80 (2,4-Dichlorophenyl) dimethyl (1H-imidazol-1) -ylmethyl jsilane 100
Diphenyl (1H-imidazol-1-ylmethyl) methylsilane 76 (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl jsilane) 45 (4-Fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl jsilane 65
Example 76
The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). The suspensions are then sprayed onto the rice seedlings to the point where they begin to run down. The next day, the plants are inoculated with a mixture of pulp and mycelium of Rhizoctonia solani, causing bacterial staining of the rice sheath, and incubating in the growth chamber for 7 days. Plant infestation is evaluated. The percentage of infestation is in the <following table. Treated plants show slight infestation while untreated plants are heavily infested.
Table XXVIII
Compound% Reducing Bacterial Spots of Rice (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 40 (3,4-Dichlorophenyl) dimethyl (1H-1, 2,4-triazol-1-ylmethyl jsilane 80 bis (4-fluorophenyl) (methyl j (1H-1,2,4-triazol-1-ylmethyl) jsilane 80 (4- (1,1-Dimethylethyl) phenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 90
Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 50 (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1) -ylmethyl jsilane 90 (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 80
113
114
Table XXVI
Compound% rust reduction on beans
Compound% Suppression of Yellow Spots of Groundnuts (1,1'-Biphenyl-4-yl) Hydroxy (Methyl) (1H-1,2,4-Triazol-1-ylmethylsilane) 100 (1,1'-Biphenyl-4-yl) (4-Fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100
Dimethyl (4-trifluoromethoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 50 (4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-1,2, 4-Triazol-1-ylmethyl) silane 100 (1,1'-Biphenyl-4-yl) dimethyl (5-methyl-1H-1,2,4-triazol-1-ylmethyl) silane 100 (1H-Biphenyl-4) -yl 1-Dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1,1'-Biphenyl-4-yl) dimethyl] (1H-1,2,4-triazol-1-ylmethyl) silane, 2: 1 copper chloride complex 100
AND<sub>b</sub> phytotoxic browning
B compound used at 400 ppm BB compound used at 20 ppm
Example 74
The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 80 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). These suspensions are sprayed onto the seedlings of God in amounts that are just starting to run down. The next day the plants are inoculated with a spore suspension of the fungus Uromyces phaseoli causing rust to the god and incubated in a humidified chamber at 20 ° C for 24 hours and then left in the greenhouse for a further 7 days. The degree of infestation is assessed. The percentage of infestation is shown in the following table. Treated plants show little or no attack on rust, while untreated plants are covered with rust. Some treated plants exhibit phytotoxicity in the form of reduced growth, in addition to reducing infestation.
(2,4-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane 83 (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 30G<sup>AND</sup> bis (4-Chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100G (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1) -ylmethyl) silane 98<sup>b</sup> (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane i00<sup>(B)</sup> bis (4-Fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane gs<sup>(B)</sup> (1,1'-Biphenyl-4-yl) diinethyl (1H-imidazol-1-ylmethyl) silane 100
AND<sub>C</sub> reducing growth
B compound used at a concentration of 16 ppm Example 75
The active compounds according to the invention are dissolved in acetone corresponding to 5% of the final volume and then suspended at a concentration of 100 ppm in purified water containing the surfactant TREM 014 (polyhydric alcohol esters) in an amount of 700 ppm. The preserved halved peaches are soaked in this suspension for three minutes and then placed in a sterile dry air package. After drying, the halved peaches are inoculated with two pieces of Monilinia fructicola mycelium causing brown stone decay and incubated in sterile containers for 5 days. Then the radius of colonies on each peach is measured. Colonies on treated peaches do not show growth or show only graying a few millimeters in diameter, while untreated peaches cover the entire surface
111
112
Compound% suppression of yellow spots of peanut leaves
<td>Compound</td><td>° / o suppression of yellow spots of leaves peanuts</td>
<td>(4-Fluorophenyl) - (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 100</td>
<td>(2-Chlorophenyl) (11-1-imidazol-1-ylmethyl) dimethylsilane</td><td> 80</td>
<td>(1,1'-Biphenyl-4-yl) butyl (ΙΗ-imidazol-1-ylmethyl) methylsilane</td><td> 90</td>
<td>bis (1,1'-Biphenyl-4-yl) (β-imidazol-1-ylmethyl) methylsilane</td><td> 60</td>
<td>(1,1'-Biphenyl-4-yl) (β-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 80</td>
<td>(1,1'-Biphenyl-2-yl) dimethyl (β-imidazol-1-ylmethyl) silane</td><td> 30</td>
<td>(1,1'-Biphenyl-3-yl) dimethyl (ΙΗ-imidazol-1-ylmethyl) silane</td><td> 80</td>
<td>(2-Chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 100</td>
<td>(4-Bromophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 90</td>
<td>(bis (2-Chlorophenyl)] (β-imidazol-1-ylmethyl) methylsilane</td><td> 100</td>
<td>[bis (4-Bromophenyl)] (6-imidazol-1-ylmethyl) methylsilane</td><td> 50</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (ΙΗ-imidazol-1-ylmethyl) silane, 1: 1 copper chloride complex</td><td> 100</td>
<td>(2-Chlorophenyl (4-chlorophenyl) (β-imidazol-1-ylmethyl) methylsilane</td><td> 80</td>
<td>bis (4-Chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>Methyldiphenyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane .100 (4-Chlorophenyl} dimethyl (1H-1,2,4-triazole) 1-ylmethyl) silane 90
Dimethyl (1-naphthalenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90 (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (4-Fluorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane 50 bis (4-Chlorophenyl) hydroxy (ΙΗ-imidazol-1-ylmethyl) silane 50 (1,1'-Biphenyl-4-yl) (4-Fluorophenyl) (ΙΗ-imidazol-1-ylmethyl) methylsilane 100
Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethoxyphenyl) silane 90 (4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 90 bis (4 -Chlorophenyl) hydroxy (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (4-Fluorophenyl) hydroxy (1H-1,2,4-triazol-1-ylmethyl) silane 100 tris (4 -Fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90 bis (4-Chlorophenyl) hydroxy (4H-1,2,4-triazol-1-ylmethyl) silane 100
Oxybis [bis (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) (1,1'-Biphenyl-4-yl) methyl (2-propoxy) (1H-1,2, 4-triazol-1-ylmethyl) silane
100
3 β β 2 Η
103
110
<td>Compound</td><td>% yellow suppression spots of leaves peanuts</td><td>Compound</td><td>% yellow suppression spots of leaves peanuts</td>
<td>(2-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) - Sílán</td><td> 30</td><td>(1,1'-Biphenyl-4-yl) dimethyl- (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 complex with sulfate</td><td></td>
<td>(1,1'-Biphenyl-4-yl) butyl (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td><td>manganese 2-Chlorophenyl (4-chlorophenyl) methyl- (1H-1,2,4-triazol-1-)</td><td> 100</td>
<td>bis (1,1'-Biphenyl-4-yl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) - silane</td><td> 80</td><td>-ylmethyl) silane [bis (2-Fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) -</td><td> 90</td>
<td>[1,1'-Biphenyl-4-yl) methyl-</td><td></td><td>silane, 1: 1 copper chloride complex</td><td> 100</td>
<td>(phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td><td>[bis (2-Fluorophenyl)] methyl-</td><td></td>
<td>[bis (4-Methoxyphenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) silane, 2: 1 chloride complex copper</td><td> 100</td>
<td>silane (1,1'-Biphenyl-2-yl) dimethyl- (1H-1,2,4-triazol-1-ylmethyl) -</td><td> 30</td><td>(1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane</td><td> 100</td>
<td>silane (1,1'-Biphenyl-3-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) -</td><td> 100</td><td>(2,4-Dichlorophenyl) dimethyl- (1 H -imidazol-1-ylmethyl) - silane</td><td> 100</td>
<td>silane 2-Chlorophenylmethyl] phenyl-</td><td> 90</td><td>Diphenyl (1H-imidazol-1-ylmethyl) methylsilane</td><td> 50</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) - silane</td><td> 100</td><td>bis (4-Fluorophenyl) -</td><td></td>
<td>4-BiOmenyl (methylphenyl)</td><td></td><td>(1 H -imidazol-1-ylmethyl) - methylsilane</td><td> 100</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) - silane</td><td> 100</td><td>Dimethyl (4-fluorophenyl) -</td><td></td>
<td>[bis (2-chlorophenyl)] methyl-</td><td></td><td>(1 H -imidazol-1-ylmethyl) - silane</td><td>60B<sup>AND</sup></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) - silane</td><td> 100</td><td>Dimethyl (1H-imidazole-1-</td><td></td>
<td>[bis (4-Bromophenyl)] methyl</td><td></td><td>(methylmethyl) (4-trifluoromethylphenyl) silane</td><td> 36<sup>(B)</sup></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td><td>Dimethyl [1H-imidazole-1-</td><td></td>
<td>(1,1'-Biphenyl-4-yl) dimethyl-</td><td></td><td>ylmethyl) (3-trifluoromethylphenyl) silane</td><td> 50</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) silane, 4-dodecylbenzenesulfonic acid salt</td><td> 100</td><td>Butyl (2,4-dichlorophenyl) [1H-imidazol-1-ylmethyl) -</td><td></td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 copper chloride complex</td><td> 100</td><td>methylsilane bis (2,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane</td><td> 100 90</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) - silane, 1: 1 chloride complex</td><td></td><td>(2,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 100</td>
<td>zinc</td><td> 100</td><td>(4-Chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 100</td>
107
108
Compound% Reduction of Southern Corn Leaf Bacteria
Dimethyl (4-methoxyphenyl) (1H-1,2,4-triazol; -1-ylmethyl silane 90 (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) yl) Silane 90 bis (4-Chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 80 bis (4-Chlorophenyl) hydroxy (1H-1,2,4-triazol-1-yl) 90-bis (4-fluorophenyl) hydroxy (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (4-chlorophenyl) hydroxy (4H-1,2,4-triazole-) 1-ylmethyl) silane 80
Oxybis [(4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 97 (1,1'-Biphenyl-4-yl) methyl (2-propoxy) (1H-1,2, 4-Triazol-1-ylmethyl) silane 90 (1,1'-Biphenyl-4-yl) (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 80
Dimethyl (4-trifluoromethoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 80 (4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazole) 1-ylmethyl) silane 70 (1,1'-Biphenyl-4-yl) dimethyl (5-methyl-1H-1,2,4-triazol-1-ylmethyl) silane 80 (1,1'-Biphenyl- 4-yl-dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 complex with copper (I) chloride 80 ti in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). These suspensions are sprayed onto the groundnut seedlings so that they begin to run down. The following day, the plants are inoculated with a spore suspension of Cercospora arachidicola, causing yellow spots of the leaves of the pseudocarpus and incubated in a chamber saturated with moisture; at; at a temperature of 27 ° C for 24 hours and then left in the growth chamber for a further 14 days and then assessed for degree of infestation. The results are shown in the following table. Treated plants show little or no staining, while untreated plants have numerous stains. In some treated plants, phytotoxicity is observed as burning.
Table XXV
Compound% Suppression of Yellow Spots of Groundnut Leaves (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl silane, 2: 1 copper chloride complex 80
Example 73 Bis (4-Fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100
Dimethyl [4-fluorophenyl] (1H-1,2,4-triazol-1-ylmethyl) silane 50 [4- (1,1-Dimethylphenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silan 35
Dimethyl (1H-1,2,4-triazol-lylmethyl) (2-trifluoromethylphenylsilane 25 ')
Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (2,4-Dichlorophenyl) (methyl j (1H-1,2,4- triazol-1-ylmethyl] silane 100 (2,4-Dichlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100 (4-Chlorophenyl) methyl (phenyl) (1H- 1,2,4-Triazol-1-ylmethyl) silane 100 (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100
The active compounds according to the invention are dissolved
105
106
<td>Compound</td><td>% reduction of southern corn leaf blotch</td><td>Compound</td><td>% reduction of southern corn leaf blotch</td>
<td>4-Bromophenyl (methyl) phenyl-</td><td></td><td>bis (4-fluorophenyl) (1H-</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>-imidazol-1-ylmethyl) -</td><td></td>
<td>silane</td><td> 80</td><td>methylsilane</td><td> 60</td>
<td>[bis (2-Chlorophenyl)] methyl-</td><td></td><td>[4- (1,1-Dimethylethyl) phenyl]</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>(ΙΗ-Imidazol-1-ylmethyl) -</td><td></td>
<td>silane</td><td> 60</td><td>dimethylsilane</td><td> 70</td>
<td>Cyclohexyl (dimethyl) -</td><td></td><td>(1 H-Imidazol-1-ylmethyl) -</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl)</td><td></td><td>dimethyl (2-trifluoromethyl-</td><td></td>
<td>silane</td><td> 50</td><td>phenyl jsilane</td><td> 90</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl</td><td></td><td>Butyl (2,4-dichlorophenyl) -</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>(ΙΗ-Imidazol-1-ylmethyl) -</td><td></td>
<td>silane, 4-dodecylbenzenesulfonic acid salt</td><td> 100</td><td>methylsilane</td><td> 80</td>
<td></td><td></td><td>bis (2,4-Dichlorophenyl)</td><td></td>
<td>(1,1'-Biphenyl-4-yl) dimethyl</td><td></td><td>(1 H -imidazol-1-ylmethyl) -</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>methylsilane</td><td> 80</td>
<td>silane, 1: 1 copper chloride complex</td><td> 100</td><td>(4-Fluorophenyl) -</td><td></td>
<td>(1,1'-Biphenyl-4-yl) dimethyl</td><td></td><td>(1 H -imidazol-1-ylmethyl) -</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>methyl [phenyl] silane</td><td> 80</td>
<td>silane, 1: 1 chloride complex zinc</td><td> 90</td><td>(2,6-Dimethoxyphenyl) (dimethyl) (1H-imidazole-1-</td><td></td>
<td>(1,1'-Biphenyl-4-yl) dimethyl</td><td></td><td>ylmethyl jsilan</td><td> 50</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) - sllan, 1: 1 complex with sulfate</td><td></td><td>Dibutyl (1H-imidazole-1-</td><td></td>
<td>manganese</td><td> 100</td><td>-ylmethyl is methylsilane</td><td> 90</td>
<td>2-Chlorophenyl (4-chlorophenyl) -</td><td></td><td>(1,1'-Biphenyl-4-yl) -</td><td></td>
<td>methyl (1H-1,2,4-triazole-1-</td><td></td><td>[1H-imidazol-1-ylmethyl] -</td><td></td>
<td>-ylmethyl) silane</td><td> 60</td><td>methyl (phenyl) silane</td><td> 80</td>
<td>(Ι, Γ-Biphenyl-4-yl) dimethyl-</td><td></td><td>(1,1'-Biphenyl-3-yl) dimethyl-</td><td></td>
<td>(1 H -imidazol-1-ylmethyl) -</td><td></td><td>(1 H -imidazol-1-ylmethyl) -</td><td></td>
<td>silane</td><td> 90</td><td>silane</td><td> 90</td>
<td>Butyl (4-chlorophenyl) -</td><td></td><td>[bis (2-Chlorophenyl)]</td><td></td>
<td>(1H-imidazol-1-ylmethyl) -</td><td></td><td>(ΙΗ-Imidazol-1-ylmethyl) -</td><td></td>
<td>silane</td><td> 50</td><td>methylsilane</td><td> 90</td>
<td>(3,4-Dichlorophenyl-</td><td></td><td>Cyclohexyl (dimethyl)</td><td></td>
<td>(1H-imidazol-1-ylmethyl) -</td><td></td><td>(ΙΗ-Imidazol-1-ylmethyl) -</td><td></td>
<td>silane</td><td> 70</td><td>silane</td><td> 50</td>
<td>(2,4-Dichlorophenyl) dimethyl-</td><td></td><td>(4-Bromophenyl) dimethyl-</td><td></td>
<td>(ΙΗ-Imidazol-1-ylmethyl) -</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>silane</td><td> 70</td><td>silane</td><td> 90</td>
<td>bis (4-Chlorophenyl-</td><td></td><td>((1,1'-Biphenyl-4-yl) dimethyl-</td><td></td>
<td>(ΙΗ-Imidazol-1-ylmethyl) -</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>methylsilane</td><td> 60</td><td>silane</td><td> 90</td>
<td>(ΙΗ-Imidazol-1-ylmethyl) -</td><td></td><td>(3,4-Dichlorophenyl) dimethyl-</td><td></td>
<td>triphenylsilane</td><td> 50</td><td>(1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td>
Diphenyl (1H-imidazol-1-ylmethyl) methylsilane
103
104
Compound% reduction of apple scab
Compound% Reduction of Southern Corn Leaf Bacteria
Dimethyl (octadecyl) (1H, 1,2,4-triazol-1-ylmethyl) silane 60
AND<sub>G</sub> reducing growth
(B)<sub>C</sub> chlorose
C compound used at 400 ppm D<sub>b</sub> Brown
Example 72
The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). These suspensions are sprayed onto the maize seedlings to the point where they begin to run down. The next day, the plants are inoculated with a spore suspension of Helminthosporium maydis, causing bacterial blotch of southern maize leaves, and incubated in a moisture-saturated chamber at 20 ° C for 24 hours and then left in the growth chamber for a further 7 days to assess the extent of infestation. The percentage of infestation is shown in the following table. Treated plants show little or no attack, while untreated plants have numerous spots. Some plants exhibit phytotoxicity as a reduction in growth, along with a reduction in infestation.
Table XXIV
Compound% Reduction of Southern Corn Leaf Bacteria
Methyl-diphenyl (1H-1,2,4-triazol-1-ylmethyl) silane 80 (1,1'-Biphenyl-4-yl) dimethyl (4H-1,2,4-triazol-4-ylmethyl) silane 100 bis (4-Fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100
Dimethyl (4-fluorophenyl) [1H-1,2,4-triazol-1-ylmethyl) silane 90
Dimethyl (4-methylthiophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 80
Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (4-trifluoromethylphenyl) silane 50 [4- (1,1-Dimethyl) phenyl] dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 60 (2-Methoxyphenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane
Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (2,4-Dichlorophenyl) (methyl) (1H-1,2,4-triazol-1) -ylmethylsilane 80 (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90 (4-fluorophenyl) methyl (phenyl j (1H-1,2,4) -triazol-1-ylmethyl) silane 90 (2-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 [4- (4-Chlorophenoxy) phenyl] dimethyl (1H-l, 2,4-Triazol-1-ylmethyl Silane 50 (3,5-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 40 f 1,1'-Biphenyl-4-yl-butyl (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 50 (Ι, Γ-Biphenyl-4-yl) methyl (phenyl) (1H) -1,2,4-triazol-1-ylmethylsilane 90 [bls (4-Methoxyphenyl) methyl] (1H-1,2,4-triazol-1-ylmethyl) silane 90 (1,1'-Biphenyl-2-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 90 (Ι, Γ-Biphenyl-3-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100
2-Chlorophenyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane 100
101
102
238826
<td>Compound</td><td>% of apple scab</td><td>Compound</td><td>% of apple scab</td>
<td>[bis (4-Bromophenyl)] (1H- -imidazol-1-ylmethyl) -</td><td></td><td>Dimethyl (1H-imidazol-1-ylmethyl) octadecylsilane</td><td> 80</td>
<td>methylsilane (1,1'-Biphenyl-4-yl) -dimethyl (1H-imidazol-1-ylmethyl) -</td><td> 50</td><td>bis (4-Chlorophenyl) hydroxy (1H-1,2,4-triazol-1-ylmethyl) - silane</td><td> 100</td>
<td>silane, 1: 1 copper chloride complex</td><td> 100</td><td>bis (4-Fluorophenyl) (hydroxy-</td><td></td>
<td>(2-Chlorophenyl) [4-chlorophenyl] -</td><td></td><td>[1H-1,2,4-triazol-1-ylmethyl] - silane</td><td> 100</td>
<td>(1 H -imidazol-1-ylmethyl) methylsilane</td><td> 80</td><td>tris (4-Fluorophenyl) - (1 H-</td><td></td>
<td>(1H-Imidazol-7-ylmethyl) -</td><td></td><td>-1,2,4-triazol-1-ylmethyl- silane</td><td> 60</td>
<td>phenyl [bis (2-propoxy)] silane (2-Chlorophenyl) (dimethyl) (1H-imidazol-1-ylmethyl) -</td><td> 70</td><td>bis (4-Chlorophenyl) hydroxy (4H-1,2,4-triazol-4-ylmethyl) silane</td><td> 100</td>
<td>silane Dimethyl (4-methylphenyl) (1H-1,2,4-triazol-1-ylmethyl) -</td><td> 60</td><td>Oxybis [bis (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) - silan]</td><td> 100</td>
<td>silane (4-Bromophenyl) dimethyl (1H1,2,4-triazol-1-ylmethyl) -</td><td>50G<sup>AND</sup></td><td>(1,1'-Biphenyl-4-ylmethyl- (2-propoxy) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>silane (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) -</td><td>90G</td><td>(1,1'-Biphenyl-4-yl) hydroxy (methyl (1H-1,2,4-triazol-1-ylmethyl) silane)</td><td> 100</td>
Silane 100 (1,1'-Biphenyl-4-yl) (4-fluorophenyl) -
<td>(4-Chloro-phenyl) -dimethyl-1-</td><td colspan="3">methyl (1H-1,2,4-triazole-1-</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>-ylmethyl jsilan</td><td> 100</td>
<td>silane</td><td> 100</td><td>Dimethyl (4-trifluoromethoxy-</td><td></td>
<td>Butyl (4-chlorophenyl) methyl</td><td></td><td>phenyl) (1H-1,2,4-triazole-1-</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>-ylmethyl jsilan</td><td> 90</td>
<td>silane</td><td>100G</td><td>(4'-Bromo-1,1-biphenyl-4-yl) -</td><td></td>
<td>Dimethyl (1-naphthalenyl) -</td><td></td><td>dimethyl (1H-1,2,4-triazole-1-</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>-ylmethyl jsilan</td><td> 100</td>
<td>silane</td><td> 50</td><td>(1,1'-Biphenyl-4-yl) dimethyl-</td><td></td>
<td>(3-Chloro-phenyl) dimethyl-</td><td></td><td>(5-methyl-1H-1,2,4-triazole-</td><td></td>
<td>(1H-imidazol-1-ylmethyl) -</td><td></td><td>-1-ylmethyl jsilane</td><td> 100</td>
<td>silane</td><td> 60</td><td>(1,1'-Biphenyl-4-yl) dimethyl-</td><td></td>
<td>(1,1'-Biphenyl-4-yl) (4-fluoro-</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>phenyl] (1H-imidazole-1-</td><td></td><td>silane, 1: 1 chloride complex</td><td></td>
<td>- ylmethyl) methylsilane</td><td> 50</td><td>copper</td><td> 100</td>
<td>Dimethyl (1H-imidazole-1-</td><td></td><td>(1,1'-Biphenyl-4-yl) dimethyl-</td><td></td>
<td>- ylmethyl (4-trifluoromethoxy)</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>phenylj silane</td><td> 50</td><td>silane, 2: 1 chloride complex</td><td></td>
<td>(4'-Bromo-1,1'-biphenyl-4-yl) -</td><td></td><td>copper</td><td> 100</td>
<td>dimethyl (1H-imidazole-1-</td><td></td><td>(3-Chlorophenyl) di-ethyl-</td><td></td>
<td>-ylmethyl jsilan</td><td> 50</td><td>(1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 60</td>
<td>(3,5-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane</td><td> 50</td><td></td><td></td>
100
<td>Compound</td><td>% of apple scab</td><td>Compound</td><td>% of apple scab</td>
<td>2-Chlorophenyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td><td>(4-Fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 100</td>
<td>2-Chlorophenyl (dimethyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 60</td><td>(ΙΗ-Imidazol-1-ylmethyl) - (2-methoxyphenyl) - dimethylsilane</td><td> 60</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) -</td><td></td><td>(2-Chlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane</td><td> 90</td>
<td>silane Butyl (4-chlorophenyl) -</td><td> 80</td><td>Butyl (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 80</td>
<td>(ΙΗ-Imidazol-1-ylmethyl) - methylsilane</td><td> 90</td><td>1,1'-Biphenyl-4-yl) butyl-</td><td></td>
<td>(1 H -imidazol-1-ylmethyl) -</td><td></td><td>(1H-imidazol-1-ylmethyl) methylsilane</td><td> 100</td>
<td>dimethyl (1-naphthalenyl) silane</td><td> 40</td><td>Butyl (4-fluorophenyl) -</td><td></td>
<td>(3,4-Dichlorophenyl)</td><td></td><td>(1H-imidazol-1-ylmethyl) methylsilane</td><td> 80</td>
<td>(1 H -imidazol-1-ylmethyl) dimethylsilane</td><td> 80</td><td>Dibutyl (1H-imidazole-1-</td><td></td>
<td>(1H-imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane</td><td> 100</td><td>-ylmethyl) methylsilane bis (1,1'-Biphenyl-4-yl) (1H-imidazol-1-ylmethyl) -</td><td> 30</td>
<td>(2,4-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane</td><td> 100</td><td>methylsilane (1H-Imidazol-1-ylmethyl) [bis (4-methoxyphenyl)] -</td><td> 50</td>
<td>Diphenyl (1H-imidazol-1-ylmethyl) methylsilane</td><td> 50</td><td>methylsilane (1,1 * -Biphenyl-2-yl) -dimethyl · ·</td><td> 50</td>
<td>bi9 (4-Fluorophenyl) -</td><td></td><td>(1H-imidazol-1-ylmethyl) silane</td><td> 90</td>
<td>(1H-imidazol-1-ylmethyl) methylsilane</td><td> 100</td><td>(1,1'-Biphenyl-3-yl) dimethyl-</td><td></td>
<td>Dimethyl (1H-imidazole-1-</td><td></td><td>(1H-imidazol-1-ylmethyl) silane</td><td> 90</td>
<td>ylmethyl) (4-trifluoromethylphenyl) silane</td><td> 60<sup>C</sup></td><td>(2-Chlorophenyl) (1H-irnidazole-</td><td></td>
<td>[4- (1,1'-Dimethylethyl) phenyl] -</td><td></td><td>(1-ylmethyl) methyl (phenyl) silane</td><td> 100</td>
<td>(1 H -imidazol-1-ylmethyl) dimethylsilane</td><td> 50</td><td>(4-Bromophenyl) (1H-imidazole-</td><td></td>
<td>Butyl (2,4-dichlorophenyl) -</td><td></td><td>-1-ylmethyl jmethyl (phenyl) silane</td><td> 30</td>
<td>(1 H -imidazol-1-ylmethyl) methylsilane</td><td>100B</td><td>[bis (2-Chlorophenyl)] (1H-</td><td></td>
<td>bis (2,4-Dichlorophenyl)</td><td></td><td>-imidazol-1-ylmethyl-methylsilane</td><td> 60</td>
<td>(1 H -imidazol-1-ylmethyl) methylsilane</td><td> 40</td><td>Dimethyl (1H-imidazole-1-</td><td></td>
<td>(2,4-Dichlorophenyl)</td><td></td><td>ylmethyl) (4-methylsulfonylphenyl) silane</td><td> 80</td>
<td>(1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 80</td><td>Cyclohexyl (dimethyl (1H-</td><td></td>
<td>(4-Chlorophenyl) -</td><td></td><td>imidazol-1-ylmethylsilane</td><td>100B</td>
(ΙΗ-imidazol-1-ylmethyl) methyl (phenyl) silane 100
Compound% reduction of apple scab
Compound% apple scab reduction (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (4-Chlorophenyl) (methyl) (1H-1,2,4-triazole- 1-ylmethylsilane 100
Methylphenyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1,1'-Biphenyl-4-yl) dimethyl (4H-1,2,4-triazol-4-ylmethyl) silane 80 bis (4-Fluorophenyl) (methyl 1 (1H-1,2,4-triazol-1-ylmethyl) silane 100
Dimethyl (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 80C<sup>(B)</sup>
Dimethyl<sup>1</sup> (4-methylthiophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 60
Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (2-trifluoromethylphenyl) silane 65G<sup>AC</sup> (2-Methoxyphenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 80
Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100G bis (2,4-Dichlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) ) Silane 100 (2,4-Dichlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100G (4-Chlorophenyl) methyl [phenyl] (1H-1,2,4) -triazol-1-ylmethyl) silane 100 (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100
Butyl (methylphenyl (1H-1,2,4-triazol-1-ylmethyl) silane 80)
Dodecyl (dimethyl) (1H-1,2,4-triazol-1-ylmethyl) silane 40B<sup>cn</sup> (2-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 [4- (4-Chlorophenoxyphenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1, T-Biphenyl-4-yl) butyl (methyl 1 (1H-1,2,4-triazol-1-ylmethyl) silane 80
Butyl (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1,1'-Biphenyl-4-yl) methyl (phenyl) (1H-1,2,4- triazol-1-ylmethyl jsilane 100 (1,1'-Biphenyl-2-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 60 (1,1'-Biphenyl-3-yl) dlmethyl (1H-1,2,4-triazol-1-ylmethyl) silane 50
2-Chlorophenyl (methylphenyl (1H-1,2,4-triazol-1-ylmethyl) silane 90
4-Bromophenyl (methylphenyl) - (1H-1,2,4-triazol-1-ylmethyl) silane 100 [bis (2-Chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) Silane 40 [bis (4-Bromophenyl) methyl] (1H-1,2,4-triazol-1-ylmethyl) silane 80 (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazole) -1-ylmethyl) silane, 4-dodecylbenzenesulfonic acid salt 100 (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 copper chloride complex 100 (Ι, Γ-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 complex with zinc chloride 100 (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 complex with manganese sulfate 100
<img file="CS238626B2_D0003.tif" />
Compound% Barley Powdery Mildew Restriction
Example 70
The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the total volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). These suspensions are sprayed onto the barley seedlings to the point where they begin to run down. The following day, the plants are inoculated with a spore suspension of Erysiphe graminis causing mildew of barley and incubated in a growth chamber for 7 days. The attack rate is then assessed. The percentage of infection limits is shown in the following table. Treated plants show little or no attack by powdery mildew, while untreated plants are powdery mildew
<td colspan="2">you.</td>
<td>Compound</td><td>barley mildew reduction</td>
<td>Dodecyl (dimethyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100<sup>AND</sup></td>
<td>Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane</td><td> 100</td>
<td>(3,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane</td><td> 80</td>
<td>Dimethyl (1H-imidazol-1'-ylmethyl) J (4-methoxyphenyl) silane</td><td> 100</td>
<td>(2,4-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane</td><td> 100</td>
<td>bis (4-Chlorophenyl) J (1H-imidazol-1-ylmethyl) methylsilane</td><td> 100</td>
<td>Diphenyl (1H-imidazol-1-ylmethyl) methylsilane</td><td> 100</td>
<td>Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethylphenylsilane)</td><td> 100</td>
<td>Dodecyl (dimethyl) (1H-imidazol-1-ylmethyl) silane</td><td> 100'</td>
<td>Butyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td>
<td>(3,4-Dichlorophenyl) dimethyl (1H-1,2,4-trlazol-1-ylmethyl) silane</td><td> 100</td>
Dimethyl (4-methoxyphenyl) -1H-1,2,4-triazol-1-ylmethylsilane 100 (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (4 (Chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1H-1,2,4-Triazol-1-ylmethyl) triphenylsilane 100
Methyldiphenyl (1H-1,2,4-triazol-1-ylmethyl) silane 100
Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (2-trifluoromethylphenyl) silane 100
A compound used at a concentration of 200 ppm Example 71
The active compounds according to the invention are dissolved in acetone corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing the day, inoculated with a spore suspension of TREM 014 (polyhydric alcohol esters). apple seedlings. The next day, the plants are inoculated with a spore suspension of the fungus Venturia inaequalis, which causes scab of apples, and incubated in a saturated humidity chamber at 20 ° C for 24 hours, and then left in a growth chamber for 10-12 days. The degree of infestation is assessed and is shown in the following table. Treated plants show less scab compared to untreated plants that are covered with speckles. Phytotoxicity manifested by reduced growth is observed in some plants along with a reduction in scab infestation.
Compound% apple scab reduction (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 80
Dimethyl (4-phenoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100
Dimethyl (4-methoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane
100
<td>Compound</td><td>% reduction of cucumber powdery mildew</td><td>Compound</td><td>% reduction of cucumber powdery mildew</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl-</td><td></td><td>bis (4-fluorophenyl) hydroxy-</td><td></td>
<td>(1H-imidazol-1-ylmethyl) -</td><td></td><td>(1 H -1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>silane, 1: 1 chloride complex</td><td></td><td>silane</td><td>100H</td>
<td>copper</td><td> 100</td><td>tris (4-Chlorophenyl)</td><td></td>
<td>(2-Chlorophenyl) (4-chlorophenyl) -</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>(1 H -imidazol-1-ylmethyl) -</td><td></td><td>silane</td><td> 100</td>
<td>methylsilane</td><td> 100</td><td>bis (4-Chlorophenyl) hydroxy-</td><td></td>
<td>(2-Chlorophenyl) (dimethyl) -</td><td></td><td>(4H-1,2,4-Triazol-1-ylmethyl) -</td><td></td>
<td>(ΙΗ-Imidazol-1-ylmethyl) -</td><td></td><td>silane</td><td> 100</td>
<td>silane</td><td>G0</td><td>Oxybis [bis (4-fluorophenyl) -</td><td></td>
<td>(Dimethyl) phenyl (1,2,4-</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>(triazol-1-ylmethyl) silane</td><td> 100</td><td>silan]</td><td> 100</td>
<td>Ethyldimethyl (1H-1,2,4-</td><td></td><td>(1,1-Biphenyl-4-yl) methyl-</td><td></td>
<td>(triazol-1-ylmethyl) silane</td><td> 100</td><td>(2-propoxy (1H-1,2,4-triazole- . 1-ylmethyl) silane</td><td> 100</td>
<td>Butyldimethyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td><td>(1,1'-Biphenyl-4-yl) hydroxymethyl) (1H-1,2,4-triazol-1-yl)</td><td></td>
<td>Dimethyl (4-methylphenyl) -</td><td></td><td>ylmethyl) silane</td><td> 100</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) silane</td><td>100G '</td><td>(1,1'-Biphenyl-4-yl) (4- -fluorophenyl) methyl (1H-</td><td></td>
<td>[4-Bromophenyl] dimethyl-</td><td></td><td>1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>silane</td><td> 100</td>
<td>silane</td><td>100G</td><td>Dimethyl (4-trifluoromethoxy-</td><td></td>
<td>tris (4-Chlorophenyl) (1 H-</td><td></td><td>phenyl) (1H-1,2,4-triazole-1-</td><td></td>
<td>imidazol-1-ylmethyl) silane</td><td> 100</td><td>-ylmethyl) silane</td><td>100G</td>
<td>tris (4-Fluorophenyl) (1H-</td><td></td><td>(4'-Bromo-1,1'-biphenyl-4-yl) -</td><td></td>
<td>imidazol-1-ylmethyl] silane</td><td> 100</td><td>dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>bis (4-Fluorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane</td><td> 100</td><td>(1,1'-Biphenyl-4-yl) dimethyl (5-methyl-1H-1,2,4-triazole-</td><td></td>
<td>bis (4-Chlorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane</td><td> 100</td><td>-1-ylmethyl Jsilane</td><td> 100</td>
<td></td><td></td><td>(1,1'-Biphenyl-4-yl) dimethyl-</td><td></td>
<td>(3-Chlorophenyl) dimethyl (1 H-</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>imidazol-1-ylmethyl) silane</td><td> 80</td><td>silane, l: copper (II) chloride complex</td><td> 100</td>
<td>(1,1'-Biphenyl-4-yl) (4-fluorophenyl) (1H-imidazole-1-</td><td></td><td>(1,1-Biphenyl-4-yl) dimethyl-</td><td></td>
<td>-ylmethyl] methylsilane</td><td> 100</td><td>(1H-1,2,4-triazol-1-ylmethyl) silane, 2: 1 chloride complex</td><td></td>
<td>Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethoxy-</td><td></td><td>copper</td><td> 100</td>
<td>phenyl) silane</td><td>100G</td><td>(4-Fluorophenyl) methyl (2-propoxy) (1H-1,2,4-triazole-</td><td></td>
<td>(4'-Bromo-1,1'-biphenyl-4-yl) -</td><td></td><td>-1-ylmethyl (silane</td><td> 100</td>
<td>dimethyl (1H-imidazol-1-ylmethyl) silane</td><td> 100</td><td>(1,1'-Dimethyl-1-ethoxy) [bis (4-fluorophenyl)] (1H-1,2,4-</td><td></td>
<td>(3,5-Dichlorophenyl) dimethyl (β-imidazol-1-ylmethyl) -</td><td></td><td>triazol-1-ylmethyl) silane</td><td> 100</td>
<td>silane</td><td>100G</td><td>AND<sub>G</sub> reducing growth B, t hormonal action</td><td></td>
100H bis (4-Chlorophenyl) hydroxy (1H-1,2,4-triazo; 11-ylmethyl) silane
<td>Compound</td><td>% reduction of cucumber powdery mildew</td><td>Compound</td><td>% reduction of cucumber powdery mildew</td>
<td>bis (4-Chlorophenyl) - (1H-imidazol-1-ylmethyl) -</td><td></td><td>Dodecyl (dimethyl) (1H-imidazol-1-ylmethyl) -</td><td></td>
<td>methylsilane (1H-Imidazol-1-ylmethyl) -</td><td> 100</td><td>silane (2-Chlorophenyl) (1H-imidazole-</td><td> 55</td>
<td>triphenylsilane Diphenyl (1H-imidazole-1-</td><td> 100</td><td>(1-ylmethyl) dimethylsilane [4- (4-Chlorophenoxy) phenyl] -</td><td> 100</td>
<td>-ylmethyl) -methylsilane bis (4-Fluorophenyl) -1H-imidazol-1-ylmethyl) -</td><td> 100</td><td>dimethyl (1H-imidazol-1-ylmethyl) silane Butyl (1H-imidazol-1-ylmethyl) -</td><td> 100</td>
<td>methylsilane Dimethyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) -</td><td> 100</td><td>methyl (phenyl) silane (1,1'-Biphenyl-4-yl) butyl- (1H-imidazol-1-ylmethyl) -</td><td> 100</td>
<td>Sílán Dimethyl (1H-imidazol-1-ylmethyl) (4-methylthiophenyl) -</td><td>100G</td><td>methylsilane Butyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) methyl</td><td> 100</td>
<td>silane Dimethyl (1H-imidazole-1-</td><td> 100</td><td>silane Dibutyl (1H-imidazole-1-</td><td> 100</td>
<td>(methylmethyl) (4-trifluoromethylphenyl) silane Dimethyl (1H-imidazole-1-</td><td> 100</td><td>-ylmethyl) methylsilane 1,1'-Biphenyl-4-yl) (1H- (imidazol-1-ylmethyl) methyl-</td><td> 100</td>
<td>-ylmethyl) (3-trifluoromethylphenylsilane) [4- (1,1-Dimethyl-ethyl) -</td><td> 80</td><td>(phenyl) silane 1,1-Dimethylethoxy) (1H-imidazol-1-ylmethyl) methyl-</td><td> 100</td>
<td>phenyl] (1H-imidazol-1-ylmethyl) dimethylsilane (ΙΗ-Imidazol-1-ylmethyl) -</td><td> 80</td><td>(phenyl) silane (ΙΗ-Imidazol-1-ylmethyl) methyl (phenyl) (2-propoxy) -</td><td> 100</td>
<td>dimethyl (2-trifluoromethylphenyl) silane Butyl (2,4-dichlorophenyl) -</td><td>100G</td><td>silane (ΙΗ-Imidazol-1-ylmethyl) [bis (4-methoxyphenyl)] -</td><td> 90</td>
<td>(1H-imidazol-1-ylmethyl) methylsilane bis (2,4-Dichlorophenyl)</td><td>100G</td><td>methylsilane (1,1'-Biphenyl-2-yl) dimethyl (1H-imidazol-4-ylmethyl) -</td><td> 50</td>
<td>(1H-imidazol-1-ylmethyl) methylsilane (2,4-Dichlorophenyl) - [1H-</td><td> 100</td><td>silane (2-Chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) -</td><td> 50</td>
<td>imidazol-1-ylmethyl) methyl (phenyl) silane (4-Chlorophenyl) (1H-imidazole-</td><td> 100</td><td>silane (4-Bromophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) -</td><td> 1.00</td>
<td>(1-ylmethyl) methyl (phenyl) silane (4-Fluorophenyl) (1H-imidazole-</td><td> 100</td><td>silane [bis (2-Chlorophenyl)] (1H-imidazol-1-ylmethyl) methyl-</td><td> 100</td>
<td>(1-ylmethyl) methyl (phenyl) silane</td><td> 100</td><td>silane Cyclohexyl (dimethyl (1H-</td><td> 100</td>
<td>(ΙΗ-Imidazol-1-ylmethyl) (2-methoxyphenyl) dimethyl-</td><td></td><td>imidazol-1-ylmethyl) silane</td><td>100G</td>
<td>silane</td><td>100G</td><td>[bis (4-Bromophenyl)] (1H-imidazol-1-ylmethyl) methyl-</td><td></td>
<td>(2,3-Dimethoxyphenyl) (1H-imidazol-1-ylmethyl) dimethylsilane</td><td> 100</td><td>silane</td><td> 100</td>
<td>Compound</td><td>% reduction of cucumber powdery mildew</td><td>Compound</td><td>% reduction of cucumber powdery mildew</td>
<td>(1,1'-Biphenyl-4-yl) methyl-</td><td></td><td>Phenyl [bis (2-propoxy)] -</td><td></td>
<td>(phenyl) 1H-1,2,4-triazole-1-</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>-ylmethyl) silane</td><td> 100</td><td>silane</td><td> 100</td>
<td>(1,1-Dimethylethoxy) methyl-</td><td></td><td>[bis (2-Fluorophenyl)] methyl-</td><td></td>
<td>(phenyl) 1H-1,2,4-triazole-1-</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>-ylmethyl) silane</td><td> 100</td><td>silane, 1: 1 copper chloride complex</td><td> 100</td>
<td>Methyl (phenyl) (2-propoxy) -</td><td></td><td></td><td></td>
<td>(1H-1,2,4-triazolylmethyl) -</td><td></td><td>[bis (2-Fluorophenyl)] methyl-</td><td></td>
<td>silane</td><td> 100</td><td>(1H-1,2,4-triazol-1-ylmethyl) silane, 2: 1 chloride complex</td><td></td>
<td>1,1'-Biphenyl-2-yl) dimethyl-</td><td></td><td>copper</td><td> 100</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td><td>Dimethyl (1H-imidazol-1-ylmethyl) phenylsilane</td><td> 100</td>
<td>2-Chlorophenyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>Ethyl (1H-imidazol-1-ylmethyl) -</td><td></td>
<td>silane</td><td> 100</td><td>diinethylsilane</td><td> 100</td>
<td>4-Bromophenyl (methyl) phenyl-</td><td></td><td>Butyl (1H-imidazol-1-ylmethyl) -</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>dimethylsilane</td><td> 100</td>
<td>silane</td><td> 100</td><td>(ΙΗ-Imidazol-1-ylmethyl) dimethyl (4-methylphenyl) -</td><td></td>
<td>[bis (2-Chloro-phenyl)] -ethyl (1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>silane</td><td>100G<sup>AND</sup></td>
<td>silane</td><td> 100</td><td>(4-Bromophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane</td><td> 100</td>
<td>Cyclohexyl (dimethyl) (1H, 1,2,4-triazol-1-ylmethyl) -</td><td></td><td>(1,1'-Biphenyl-4-yl) dimethyl-</td><td></td>
<td>silane</td><td>100G</td><td>(1H-imidazol-1-ylmethyl) silane</td><td> 100</td>
<td>(bis (4-Bromophenyl) methyl) (1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>(4-Chlorophenyl) (1H-imidazole-</td><td></td>
<td>silane</td><td>80G</td><td>(1-ylmethyl) dimethylsilane</td><td> 100</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl-</td><td></td><td>Butyl (4-chlorophenyl) (1H-</td><td></td>
<td>(1 H -1,2,4-triazol-1-ylmethyl) -</td><td></td><td>imidazol-1-ylmethyl) methyl-</td><td></td>
<td>silane, salt (4-dodecylbenzene-</td><td></td><td>silane</td><td>100G '</td>
<td>sulfonic acids</td><td> 100</td><td>(ΙΗ-Imidazol-1-ylmethyl) -</td><td></td>
<td>(1,1'-Biphenyl-4-yl) dimethyl-</td><td></td><td>Dimethyl 1 (1-naphthalenyl) -</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>silane</td><td> 100</td>
<td>silane, 1: 1 copper chloride complex</td><td> 100</td><td>(3,4-Dichlorophenyl) -1H-imidazol-1-ylmethyl) -</td><td></td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>dimethylsilane</td><td> 100</td>
<td>silane, 1: 1 chloride complex</td><td></td><td>(1H-Imidazol-1-ylmethyl-</td><td></td>
<td>zinc</td><td> 80</td><td>dimethyl (4-phenoxyphenyl) silane</td><td> 100</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl- (1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>Dimethyl (1H-imidazole) -1-</td><td></td>
<td>silane, 1: 1 complex with sulfate</td><td></td><td>-ylmethyl) (4-methoxyphenyl) -</td><td></td>
<td>manganese</td><td> 90</td><td>silane</td><td> 100</td>
<td>2-Chlorophenyl (4-chlorophenyl) -</td><td></td><td>(2,4-Dichlorophenyl) dimethyl-</td><td></td>
<td>methyl (1H-1,2,4-triazole-1-</td><td></td><td>(1H-imidazol-1-ylmethyl) -</td><td rowspan="2">100H<sup>(B)</sup></td>
<td>-vlmethvllsilan</td><td> 100</td><td>silane</td>
<td>Compound</td><td>% reduction of cucumber powdery mildew</td><td>Compound</td><td>% reduction of cucumber powdery mildew</td>
<td>(4-Chlorophenyl) dimethyl-</td><td></td><td>-1-ylmethyl) (2-trifluoro-</td><td rowspan="2"> 100</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>methylphenyl) silane</td>
<td>Sílán</td><td> 100</td><td>(2-Methoxyphenyl (dimethyl) -</td><td></td>
<td>Butyl (4-chlorophenyl) methyl-</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td rowspan="2">100G</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>silane</td>
<td>silane</td><td>100G</td><td>Butyl [2,4-dichlorophenyl) methyl-</td><td></td>
<td>Dimethyl (1-naphthalenes 1) -</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td rowspan="2">100G</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>silane</td>
<td>silane</td><td> 100</td><td>bis (2,4-Dichlorophenyl) (methyl) -</td><td></td>
<td>(3,4-Dichlorophenyl) dimethyl-</td><td></td><td>(1H-1,2,4-Triazol-1-ylmethyl) -</td><td rowspan="2">100G</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>silane</td>
<td>silane</td><td> 100</td><td>(2,4-Dichlorophenyl) methyl-</td><td></td>
<td>Dimethyl (4-phenoxyphenyl) -</td><td></td><td>(phenyl) (1H-1,2,4-trlazole-1-</td><td rowspan="2">100G</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>-ylmethyl) silane</td>
<td>silane</td><td> 70</td><td>(4-Chlorophenyl) methyl (phenyl) -</td><td></td>
<td>Dimethyl (4-methoxyphenyl) -</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td rowspan="2">100G</td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>silane</td>
<td>silane</td><td> 100</td><td>(4-Fluorophenyl) methyl (phenyl) -</td><td></td>
<td>(2,4-Dichlorophenyl) dimethyl-</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>silane</td><td> 100</td>
<td>silane</td><td>100H<sup>(B)</sup></td><td>Butyl (methyl) phenyl (1H-</td><td></td>
<td>bis (4-Chlorophenyl) (methyl) -</td><td></td><td>1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>silane</td><td> 100</td>
<td>silane</td><td> 100</td><td>(2,3-Dimethoxyphenyl) dimethyl-</td><td></td>
<td>(1H-1,2,4-Triazol-1-ylinethyl) -</td><td></td><td>(1H-1,2,4-triazol-1-ylmethyl) -</td><td></td>
<td>triphenylsilane</td><td> 100</td><td>silane</td><td>100G</td>
<td>Methyldiphenyl (1H-1,2,4-</td><td></td><td>(2,6-Dimethoxyphenyl) dimethyl-</td><td></td>
<td>(triazol-1-ylmethyl) silane</td><td>100G</td><td>(1H-1,2,4-triazol-1-ylmethyl) - silane</td><td>100G</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (4H-1,2,4-triazol-4-ylmethyl) -</td><td></td><td>Dodecyl (dimethyl) (1H-</td><td></td>
<td>silane</td><td> 90</td><td>1,2,4-triazol-1-ylmethyl) silane</td><td> 60<sup>C</sup></td>
<td>bis (4-Fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>(2-Chlorophenyl) dimethyl (1 H-</td><td></td>
<td>silane</td><td>100G</td><td>1,2,4-triazol-1-ylmethyl) silane</td><td>100G</td>
<td>Dimethyl (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>(4- (4-Chlorophenoxy) phenyl J -</td><td></td>
<td>silane</td><td>100G</td><td>dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 80</td>
<td>Dimethyl (4-methylthiophenyl) (1H-1,2,4-triazol-1-ylmethyl) -</td><td></td><td>(1,1'-Biphenyl-4-yl) butyl 1-methyl) -</td><td></td>
<td>silane</td><td> 100</td><td>(1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (4-trifluoro-</td><td></td><td>Butyl (4-fluorophenyl) methyl-</td><td></td>
<td>methylphenyl) silane</td><td>100G</td><td>(1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (3-trifluoro-</td><td></td><td>bis (1,1'-Biphenyl-4-yl) (methyl) -</td><td></td>
<td>methylphenyl) silane</td><td> 100</td><td>(1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
Dimethyl (1H-1,2,4-triazole238626)
Compound% rust reduction on wheat
<td>Compound</td><td>% rust reduction on wheat</td>
<td>bis (4-Fluorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane</td><td> 100</td>
<td>bis (4-Chlorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane</td><td> 80</td>
<td>(3-Chlorophenyl) dimethyl (1H- imidazol-1-ylmethyl jsilane</td><td> 80</td>
<td>(1,1'-Biphenyl-4-yl) (4-fluorophenyl) (1H-imidazol-1-ylmethyl) - methylsilane</td><td> 80</td>
<td>Dimethyl (1H-imidazol-1-ylmethyl) - (4-trifluoromethoxyphenyl) silane</td><td> 100</td>
<td>(4'-Bromo-1,1'-biphenyl-4-yl) -dimethyl (1H-imidazol-1-ylmethyl) silane</td><td> 100</td>
<td>bis (4-Chlorophenyl) hydroxy (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td>
<td>bis (4-fluorophenyl) hydroxy (1H- -1,2,4-triazol-1-ylmethyl jsilane</td><td> 90</td>
<td>tris (4-Chlorophenyl (1H-1,2,4-triazol-1-ylmethyl) silane)</td><td> 40</td>
<td>tris (4-Fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td>
<td>bis (4-Chlorophenyl) hydroxy (4H-1,2,4-triazol-4-ylmethyl) silane</td><td> 90</td>
<td>Oxybis [bis (4-fluorophenyl) (111-1,2,4-triazol-1-ylmethyl) silane]</td><td> 100</td>
<td>(1,1'-Biphenyl-4-yl) methyl (2-propoxy) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>(1,1'-Biphenyl-4-yl) hydroxy (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td>
<td>(1,1'-Biphenyl-4-yl) (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>Dimethyl (4-trifluoromethoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>(4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazolylmethylmethyl) silane</td><td> 100</td>
(1,1'-Biphenyl-4-yl) dimethyl (5-methyl-1H-1,2,4-triazol-1-ylmethyl) silane
100 ALIGN! (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane: 1 complex with copper (I) chloride 100 (1,1'-Biphenyl-4-yl) dimethyl (1H-1) 1, 2,4-triazol-1-ylmethyl jsilane: 1 complex with copper (I) chloride 100 <sup>AND</sup> The compound was used at a concentration of 200 ppm Example 69
The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). These suspensions are sprayed to run down onto the cucumber seedlings. The next day, the plants are inoculated with a spore suspension of Erysiphe cichoracearum causing powdery mildew and incubating in a growth chamber for 7 days. The degree of attack is then evaluated. The percentage of infestation is shown in the following table. Treated plants show little or no attack, unlike untreated plants that are covered with powdery mildew. Phytotoxicity as a growth restriction or a detrimental effect on growth is observed on some plants along with a reduction in powdery mildew.
Table XXI
Compound% Cucumber powdery mildew (Dimethyl) phenyl (1,2,4-triazol-1-ylmethyl) silane
Ethyldimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100
OF
Butyldimethyl (1H-1,2,4triazol-1-ylmethyl) silane 100
Dimethyl (4-methylphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100G<sup>AND</sup> (4-Bromophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100G (1,1'-Biphenyl-4-yl) -dimethyl (1H-1,2,4-triazol-1- ylmethyl jsilan
100
<td>Compound</td><td>% rust reduction per pedestrian-<sup>1</sup> nici</td><td>Compound</td><td>% rust reduction on wheat</td>
<td>bis (1,1'-Biphenyl-4-yl (methyl) -</td><td></td><td>bis (4-Fluorophenyl) (1H-imidazole-</td><td></td>
<td>(1 H -1,2,4-triazol-1-ylmethyl) -</td><td></td><td>-1-ylmethyl jmethylsilane</td><td> 100</td>
<td>silane</td><td> 80</td><td>Dimethyl (4-fluorophenyl) (1H-</td><td></td>
<td>(1,1'-Biphenyl-4-yl) methyl (phe-</td><td></td><td>imidazol-1-ylmethylsilane</td><td> 80</td>
<td>nyl] (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td><td>Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethylphenyl) -</td><td></td>
<td>(1,1'-Biphenyl-3-yl) dimethyl (1H-</td><td></td><td>silane</td><td> 100'</td>
<td>-1,2,4-triazol-1-ylmethyl jsilane 2-Chlorophenyl (methyl) phenyl (1H-</td><td> 80</td><td>Butyl (2,4-dichlorophenyl) (1H-imidazol-1-ylmethyl) methyl</td><td></td>
<td>-1,2,4-triazol-1-ylmethyl jsilane</td><td> 80</td><td>hind</td><td> 100</td>
<td>[bis (2-Chlorophenyl)] methyl (1H-</td><td></td><td>bis (2,4-Dichlorophenyl) (1H-imi)</td><td></td>
<td>-1,2,4-triazol-1-ylmethyl jsilane</td><td> 100</td><td>dazol-1-ylmethyl) methylsilane</td><td> 100</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-</td><td></td><td>2,4-Dichlorophenyl (1H-imidazole-</td><td></td>
<td>-1,2,4-triazol-1-ylmethyl jsilane,</td><td></td><td>-1-ylmethyl) methyl (phenyl) -</td><td></td>
<td>4-dodecylbenzenesulfonic acid</td><td> 100</td><td>silane</td><td> 90</td>
<td></td><td></td><td>4-Chlorophenyl (1H-imidazol-1-yl)</td><td></td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-</td><td></td><td>methyl j methyl (phenyl 1 j silane)</td><td> 100</td>
<td>-1,2,4-triazol-1-ylmethyl jsilane, 1: 1 complex with zinc chloride</td><td></td><td>Dodecyl (dimethyl j (1H-imida-)</td><td></td>
<td>nečnatým</td><td> 100</td><td>zol-1-ylmethyl jsilane</td><td> 80<sup>Λ</sup></td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-</td><td></td><td>(4- (4-Chlorophenoxyphenyl) dimime-</td><td></td>
<td>-1,2,4-triazol-1-ylmethyl jsilane,</td><td></td><td>thyl (1H-imidazol-1-ylmethyl) -</td><td></td>
<td>1: 1 complex with manganese sulphate</td><td> 90</td><td>silane</td><td> 90</td>
<td></td><td></td><td>Butyl (1H-imidazol-1-ylme-</td><td></td>
<td>2-Chlorophenyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl)</td><td></td><td>thyl j methyl (phenyl j silane)</td><td> 90</td>
<td>thyl jsilan</td><td> 100</td><td>(1,1'-Biphenyl-4-yl) butyl (1H-imidazol-1-ylmethyl) methyl-</td><td></td>
<td>(bis (2-Fluorophenyl)] methyl (1H-</td><td></td><td>silane</td><td> 100</td>
<td>-1,2,4-triazol-1-ylmethylsilane, 1: 1 complex with copper-</td><td></td><td>(1,1'-Biphenyl-4-yl) (1H-imido-</td><td></td>
<td>ným</td><td> 90</td><td>zol-1-ylmethyl) methyl (phenyl) silane</td><td> 100</td>
<td>[bis (2-Fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane,</td><td></td><td>(1,1'-Biphenyl-3-yl) dimethyl (1H-</td><td></td>
<td>2: 1 copper chloride complex</td><td> 100</td><td>imidazol-1-ylmethyl jsilane</td><td> 90</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-</td><td></td><td>(4-Bromophenyl) (1H-imidazole- -1-ylmethyl) methyl (phenyl)</td><td></td>
<td>-imidazol-1-ylmethyl jsilane</td><td> 100</td><td>hind</td><td> 90</td>
<td>(4-Chlorophenyl) (1H-imidazole-1-</td><td></td><td>(1,1'-Biphenyl-4-yl) dimethyl (1H-</td><td></td>
<td>(methylmethyl) dimethylsilane</td><td> 50</td><td>-imidazol-1-ylmethyl jsilane, 1: 1 complex with copper (I) chloride</td><td> 100</td>
<td>Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane</td><td> 90</td><td>(2-Chlorophenyl) (4-chlorophenyl) -</td><td></td>
<td></td><td></td><td>(1H-imidazol-1-ylmethyl) methyl-</td><td></td>
<td>(1H-Imidazol-1-ylmethyl) di-</td><td></td><td>thylsilane</td><td> 100</td>
<td>methyl (4-phenoxyphenyl) silane</td><td> 60</td><td>(2-Chlorophenyl) (dimethyl) (1 H-</td><td></td>
<td>Dimethyl (1H-imidazol-1-ylmethyl) (4-methoxyphenyl) silane</td><td> 60</td><td>imidazol-1-ylmethyl jsilane</td><td> 80</td>
<td></td><td></td><td>Iris (4-Fluorophenyl) (1H-imida-</td><td></td>
<td>(2,4-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane</td><td> 90</td><td>zol-1-ylmethyl jsilane</td><td> 80</td>
238628 cyano (3-phenoxyphenyl) methyl 4-chloro-alpha- (1-methylethyl) benzeneacetate (fenvalerate (3-phenoxyphenylmethyl) + (- cis, trans -3- (2,2-dichloroethenyl) -2,2- dimethylcyclopropanecarbosylate (permethrin dimethyl N, N '- [thiobis-] (N-methylimino) carbonyloxy-bis (ethanimidothioate) (thiodicarboxylic phosphorothiolothionic acid, O-ethyl-O- [4- (methylthio) phenyl] -Sn-propyl ester (sulprofos) alpha-cyano-3-phenoxybuzyl-3- (2,2-dichlorvinyl) -2,2-dimethylcyclopropanecarboxylate (cypermethrin) cyano ( 3-Phenoxyphenyl methyl-4- (difluoromethoxy) -alpha- (methylthyl) benzene acetate ("Payoff")
0,0-Diethyl-O- (3,5,6-trichloro-2-pyridyl) phosphorothioate (chlorpyrifos)
O, O-dimethyl-S - [(4-oxo-1,2,3-benzotriazin-3-] 4H (-yl) methyl] phosphorothioate (azinphos-methyl)
5,6-Dimethyl-2-dimethylamino-4-pyrimidyldimethylcarbamate ('pirimor')
S- (N-formyl-N-methylcarbamoylmethyl) -Ο, Ο-dimethylphosphorothioate (formothion)
S-2- (ethylthioethyl) -, Ο-dimethylphosphorothioate (demeton-S-methyl) alpha-cyano-3-phenoxybenzyl cis-3- (2,2-dibromvinyl) -2,2-dimethylcyclopropanecarboxylate (deltamethrin) ) N- (2-chloro-4-trifluoromethylphenyl) alanine ('Mavrik') methyl cyano- (3-phenoxyphenyl) methyl ester.
Example 68
The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant compound TERM 014 (polyhydric alcohol esters). These suspensions are sprayed onto wheat seedlings. The next day, the plants are inoculated with a spore suspension of Puccinia recondita var. tritics that cause wheat rust and are incubated in a room with saturated humidity at 20 ° C for 24 hours and then left in the growth chamber for a further 7 days, and then the disease is evaluated. The percentage of disease reduction is shown in the following table. Treated plants have few "sores" or are free of sores, untreated plants have numerous rust sores on the leaves.
Table XX
Compound% rust reduction on wheat (Dimethyl) phenyl (1,2,4-triazol-1-ylmethyl) silane 90
(4-Bromophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane (4-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane (1,1 ') -Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane
Butyl (4-chlorophenyl) methyl (111-1,2,4-triazol-1-ylmethyl) silane (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane (2,4 -Dichlorophenyl dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane bis (4-Chlorophenyl) (methyl j (1H-1,2,4-triazol-1-ylmethyl) silane
Dimethyl (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane (4- (1,1-Dimethylethyl) phenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane
Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane bis (2,4-Dichlorophenyl) (methyl) (1H-1,2,4-triazol-1- ylmethylsilane (2,4-Dichlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1) -ylmethyl jsilane (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane
Dodecyl-dimethyl) (1H-1,2,4-triazol-1-ylmethyl) silane [4- (4-Chlorophenoxy) phenyl] -dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane (3,5- Dichlorophenyl dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane (1,1'-Biphenyl-4-yl) butyl (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane rust reduction on wheat
100
100
100
80<sup>AND</sup>
100
100
100
100
100<sup>AND</sup> racearum; Erysiphe graminis; Venturia inaequalis; Helminthosporium maydis; Cercospora arachidicola; Uromyces phaseoli; and Monilinia fructicola; Rhizoctonia solani; Pyricularia oryzae; They are also suitable for the treatment of seed diseases, for example caused by Pythium aphanadermatum.
The disease is generally treated by applying an effective amount of the active ingredient either before or after infection to parts of the plant to be protected, such as roots, stems, leaves, fruits, seeds, tubers, or to the environment (soil or sand) where The active substances can also be applied to the seeds from which the protected plant will grow.
The doses of active substance used are influenced by numerous factors such as environmental conditions and are to be determined on a case-by-case basis. The leaves are generally protected by treatment with a dose of 1 to 500 ppm of active ingredient. Plants growing in soil can be protected from disease by treatment with 0.1 to 20 kg / ha. Seeds and seedlings are generally protected by treating the seeds with an active ingredient in an amount of 0.06 to 3 g per kg / seed.
The active compounds according to the invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides or other biologically active substances in order to achieve the desired results in the shortest possible time, with minimal effort and minimum active substance consumption. The amount of these biologically active substances for each part by weight of the composition according to the invention is 0.05 to 25 parts by weight. Suitable active ingredients of this type are well known to those skilled in the art. Some are also mentioned:
Fungicides:
manganese (nianeb) 1,4-dichloro-2,5-dimethoxybenzene (chloroneb) methyl-1- (butylcarbamoyl) -butylcarbamate (1-) butylcarbamate (2-benzimidazolecarbamate) (tetramethylthium amide sulfide (thiuram) n-dodecylguanidinedine acetate (dodine) ethylenebisdithiocarbamate (nianeb) 1,4-dichloro-2,5-dimethoxybenzene (chloroneb) )
2-Cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil)
N-Trichloromethylthiotetrahydrophthalimide (captanj
N-Trichloromethylthiophthalimide (folpet J dimethyl-4,4'- (of enylene) bis (3-thioallophthalate) (thiophane methyl)
2- (thiazol-4-yl) benzimidazole (thiabendazole iodine (O-ethylphosphonate) aluminum ("Aliette") tetrachlorophthalonitrile (chlorothalonil) 2,6-dichloro-4-nitroaniline (dichlorane)
(Metalaxyl) cis-N- [, (1,1,2,2-tetrachloroethyl) thio] cyclohex-4-ene-1,2-dicarbioximide N- (2,6-dimethylphenyl) -N- (methoxyacetyl) alanine methyl ester (captafol)
3- (3,5-dichlorophenyl) -N- (1-methylethyl) -2,4-dioxo-1-imidazolidinecarboxamide (iprodione)
3- (3,5-dichlorophenyl) -5-ethenyl-5-methyl-2,4-oxazolidinedione (vinclozolin) kasugamycin
O-ethyl-S, S-diphenylphosphorothioate (edifsnphos)
Bactericides:
tribasic copper sulphate streptomycin sulphate oxytetracycline
Acaricides:
seneciic acid, 2-sec-butyl-4,6-dinitrophenol ester (binapacryl)
6-Methyl-1,3-dithiolo [2,3-B] quinolin-2-one (oxythioquinox)
2,2,2-trichloro-1,1-bis (4-chlorophenyl) ethanol (dicofol) bis (pentachloro-2,4-cyclopentadiene-1-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin i hexakis (2-methyl-2) -phenylpropyl) distannoxane (fenbutinoxide)
Nematocides:
2- (diethoxyphosphinylimino) -1,3-dithietane (fosthietane)
S-methyl-1- (dimethylcarbamoyl) -N- (methylcarbamoyloxythiophimidimidate (oxamyl)
S-methyl-1-carbamoyl-N- (methylcarbamoyloxy) thioformimidate
N-isopropylphosphoramic acid, O-ethyl-O'- [4- (methylthio) -m-tolyl] diester (phenamiphos)
Insecticides:
3-Hydroxy-N-methyl-crotonamide (dimethylphosphate) (monocrotophos) methylcarbamic acid ester, 2,3-dihydro-2,2-dlmethyl-7-benzofuranol ester (carbofuran)
O- [2,4,5-trichloro-alpha- (chloromethyl) benzyl] phosphoric acid,
O ', O'-dimethylester (tetrachlorvlnfos)
2-mercaptosuccinic acid, diethyl ester, thionophosphoric acid S-ester, malathion phosphorothioic acid dimethyl ester, Ο, Ο-dimethyl, (methylparathion) methylcarbamic acid β-nitrophenyl ester, alpha-naphthol (carbaryl) methyl ester [(methylamino) carbonyl] ester ] oxyjethanimidothioate (methomyl)
N '- (4-chloro-i-tolyl) -N, N-dimethylformamidine (chlorodimeform)
O, O-diethyl-O- (2-isopropyl-4-methyl-6-pyrimidyl) phosphorothioate (diazinoj octachlorkamfen (toxapen)
O-ethyl-Op-nitrophenylphosphonothioate (EPN J
78
The components are mixed, coarsely ground in a hammer mill and then in an air mill until substantially all particles have a diameter below 10 microns. The product is mixed again and filled into containers.
Example 60
Wettable powder (1,1'-biphenyl-4-yl) dimethyl (1 H -imidazol-1-ylmethyl) silane 40% dioctyl sodium sulfosuccinate 1.5% sodium lignin sulfonate 3.0% low viscosity methylcellulose 1.5% attapulgite 54.0%
The ingredients are mixed thoroughly, passed through an air mill to a particle size below 15 microns, mixed again and sieved through a 0.3 mm sieve and then packed.
All the active compounds according to the invention can be formulated in the same manner.
Example 61
(1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane concentrate 30% mixture of oil-soluble sulfonates and polyoxyethylene ethers 4% xylene 66%
The ingredients are mixed and mixed under gentle heating to accelerate dissolution. A fine sieve is used when filling into packages to ensure the absence of any undissolved material.
Example 62
Emulsifiable concentrate (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethylsilane) 20% chlorobenzene 74% sorbitan monostearate and polyoxyethylene condensates 6%
The ingredients are mixed and mixed to form a solution that can be emulsified in water for use.
Example 63
Aqueous suspension of (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 25% hydrated attapulgite 3% crude calcium lignin sulphonate 10% sodium dihydrogen phosphate 0.5% / water 61.5%
The components are ground together in a ball mill or roller mill until the particle diameter is below 10 microns.
Example 64
Highly concentrated (1,1'-biphenyl-4-yl) dimethylf-1H-imidazol-1-ylmethylsilane 98.5% silica airgel 0.5% synthetic amorphous fine silica 1.0%
The components are mixed and ground in a hammer mill to form a highly concentrated concentrate with particle sizes of substantially 0.3 mm. This material can then be processed in various ways.
Example 65
Granule wettable powder of Example 60 15% gypsum 69% potassium sulfate 16%
The ingredients are mixed in a rotary mixer and sprayed with water to effect granulation. When most of the particles reach the desired size - diameter 1.0 to 0.42 mm - the granules are removed, dried and sorted. Larger sized particles are crushed and also used if they are of the desired size. The granules contain the active ingredient.
Example 66
Powder highly concentrated concentrate according to example 64 25.4% pyrophyllite powder 74.6%
The ingredients are mixed thoroughly and packaged for use.
Example 67
Emulsifiable concentrate
4-chloromethyl (methyl) phenyl (1H-imidazol-1-ylmethyl) silane 20% chlorobenzene 74% sorbitan monostearate and polyioixyethylene condensates 6%
The ingredients are mixed and mixed to form a solution that can be emulsified in water for use.
The active compounds according to the invention are useful for combating plant diseases. They are effective against a wide variety of plant diseases, in particular leaf disease of ornamental plants, vegetables, cereals and fruit plants such as Puccinia recondita, Erysiphe cicho238626
Example 51
Emulsifiable dimethyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane concentrate 20% chlorobenzene 74% sorbitan monostearate and polyoxyethylene condensates 6%
The ingredients are mixed and mixed to form a solution that can be emulsified in water for use.
Example 52
Emulsifiable dimethyl (4-methylphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane concentrate 30% oil soluble sulfonates and polyoxyethylene ethers 4% xylene 66%
The ingredients are mixed and mixed with gentle heating to accelerate dissolution. A fine filter is used for packaging to ensure the absence of any undissolved substance in the product.
Example 53
Granule wettable powder of Example 46 15% gypsum 69% potassium sulfate 16%
The ingredients are mixed in a rotary mixer and sprayed with water to achieve granulation. When most of the material reaches the desired size range, 1.0 to 0.42 mm, the granules are removed, dried and sieved. The larger size material is crushed to provide additional material of appropriate size. These granules contain the active ingredient.
Example 54
Emulsifiable (2,4-dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 30% mixture of oil-soluble sulfonates and polyoxyethylene ethers 4% xylene 66%
The ingredients are mixed and mixed under gentle heating to accelerate dissolution. A fine sieve is used when filling into the packaging so that the product does not contain any undissolved material.
Example 55
Emulsifiable concentrate of butyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 30% oil-soluble sulfonates and polyoxyethylene ethers 4% / xylene 66%
The ingredients are mixed and mixed under gentle heating to accelerate dissolution. A fine sieve is used when filling into packages to ensure the absence of any undissolved material.
Example 56
Emulsifiable concentrate
<td>bis (4-chlorophenyl) methyl (1H-1,2,4-</td><td></td><td></td>
<td>-triazoil-1-ylmethyl jsilane</td><td> 39</td><td> %</td>
<td>a mixture of oil - soluble sulfonates and</td><td></td><td></td>
<td>polyoxyethylene ethers</td><td> 4</td><td> %</td>
<td>xylene</td><td> 66</td><td> %</td>
<td>The ingredients are mixed and mixed after</td><td colspan="2">mild-</td>
heating to accelerate dissolution. A fine sieve is used when filling into packages to ensure the absence of any undissolved material.
Example 57
Emulsifiable concentrate of bis (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 20% chlorobenzene 74% sorbitan monostearate and polyoxyethylene condensates 6%
The ingredients are mixed and mixed to form a solution that can be emulsified in water in use.
Example 58
Emulsifiable concentrate
4-Fluorophenyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane 39% oil-soluble sulfonates and polyoxyethylene ethers 4% xylene 66%
The ingredients are mixed and mixed with gentle heating to accelerate dissolution. A fine sieve is used when filling into packages to ensure the absence of any undissolved material.
Example 59
Wettable powder of (1,1'-biphenyl-4-yl) dimethyl (1 H -imidazol-1-ylmethyl) silane 59% sodium alkyluaphthalenesulfoinate 2% low viscous methylcellulose 2% diatomaceous earth 46 ° / q vu are mixed and sieved through a sieve with mesh diameter All active ingredients according to the invention are processed into a wettable powder in the same way.
Example 47
Wettable powder of (4-bromophenyl) dirnyl-1H-1,2,4-triazole Depending on the intended use and physical properties of the active ingredient, the composition may contain higher or lower amounts, and a higher ratio of active ingredient to surfactant is sometimes desirable and achievable. by introducing a surfactant into the composition of the invention or while mixing in a tank.
Typical solid diluents are described by Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Edition, Dorland Books, Caldwell, New Jersey. Higher absorbency solvents are preferred for wettable powders and denser. Typical liquid solvents and diluents are described in Marsden's "Solvent Guide", 2nd Edition, Intersicience, New York, 1950. Solubility below 0.1% is preferred for suspension concentrates; the solution concentrates are preferably resistant to phase separation at 0 ° C. McCutcheon Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, New Jersey; and Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publishing Co., Inc. , New York, 1964, lists surfactants and recommended uses. All formulations may contain minor amounts of additives to reduce foaming, cake formation, corrosion, microbial growth and the like.
Methods for making such compositions are generally known. Solutions are prepared by simply mixing the ingredients. The fine solid compositions are prepared by mixing and generally crushing, for example in a hammer mill or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets can be prepared by spraying the active ingredient on a preformed granulate carrier or by agglomeration techniques. See JE Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp. 147 et seq., And "Perry's Chemical Engineer's Handbook," 4th Edition, McGraw-Hill, New York 1963, pp. 8-59.
Example 46
Wettable powder (1,1-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 40% dioctyl sodium sulfosuccinate 1.5% sodium lignosulfonate 3% low viscosity methylcellulose 1.5% attapulgite 54 %
The ingredients are mixed thoroughly, passed through an air mill until a mean particle size of less than 15 microns is formed, zno-1-ylmethyljsilane 20% sodium alkylnaphthalene sulfonate 2% low viscous methylcellulose 2% diatomaceous earth 76%
The ingredients are mixed, coarsely ground in a hammer mill, and then ground in an air mill until the particle size is below 10 microns. The product is mixed again and packaged.
Example 48
Highly concentrated (4-chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 98.5% silica airgel 0.5% synthetic amorphous fine silica 1.0%
The ingredients are mixed and ground in a hammer mill until a highly concentrated concentrate is passed through a 0.3 mm sieve. This concentrate can then be processed in various ways.
Example 49
Powder, highly concentrated concentrate according to example 48 25.4% pyroyl yl, powder 74.6%
The ingredients are mixed thoroughly and packaged for use.
Example 50
Aqueous suspension of (Ι, Γ-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 50.0% polyacrylic acid thickener 0.3% dodecylphenylethylene glycol ether 0.5% disodium phosphate 1.0% mono-sodium phosphate 0.5% polyvinyl alcohol 1.0% pentachlorophenyl 0.4% water 46.3 <sup>ιθ</sup>/ ο
The components are ground together in a sand mill up to a particle size of substantially below 5 microns.
<td>Ri *</td><td>Re</td><td>Qi</td><td>Q2</td><td> 03</td>
<td>phenyl</td><td>—CH2CH = CHCH2—</td><td>H</td><td>H</td><td>H</td>
<td>phenyl</td><td>- C (CH 3) 2 CH = CHC (CH<sub>3</sub>) 2— CHs CHs II</td><td>H</td><td>H</td><td>H</td>
<td>phenyl</td><td>1 1 —CHCH2CH2CH—</td><td>H</td><td>H</td><td>H</td>
<td>phenyl</td><td>- C (CH 3) 2 CH 2 CH 2 C (CH 3) 2 -</td><td>H</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>—CH2CH = CHCH2— CH3 CH3 I 1</td><td>H</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>1 1 —CH2C = CCH<sub>2</sub>—</td><td>H</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>—CH2 — CH — CHCH2—</td><td>H</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>—CH2CH2CH2CH2— n-ClHg 1</td><td>H</td><td>H</td><td>H</td>
<td>4-Phenoxyphenyl</td><td>1 —CH2CH2CH2CH— CH3 CH3 i 1</td><td>CH5</td><td>H</td><td>H</td>
<td>3-trifluoromethylphenyl</td><td>1 1 —CHCH = CHCH— CH3 CH3 i 1</td><td>H</td><td>CH3</td><td>CH3</td>
<td>2-methoxyphenyl</td><td>1 1 —CFIsCH - CHCH2—</td><td>CHs</td><td>CH3</td><td>CH3</td>
Resources
Useful compositions containing the active compounds of the invention can be prepared by conventional methods. These are powders, granules, pellets, solutions, emulsion wettable powders, emulsifiable concentrates and the like. Many of the active compounds according to the invention can be used directly. Highly concentrated formulations are used primarily as intermediates for the preparation of other formulations. The compositions generally contain from 1 to 99% by weight of the active compound (s) and from about 0.1 to 20% of surfactant (s) and / or from 5 to 99% of a solid or liquid inert diluent or solid or liquid inert diluents. Especially they are. the individual components are included in the following approximate amounts:
<td></td><td>Active substance</td><td>Diluent (s) weight</td><td>Surfactant (s) %</td>
<td>Wettable powders</td><td> 20 — 90</td><td> 0 — 74</td><td> 1 — 10</td>
<td>Oil suspensions, emulsions, solutions (including emulsifiable concentrate)</td><td> 5 — 50</td><td> 40 — 95</td><td> 0 — 15</td>
<td>Aqueous suspensions</td><td> 10 — 50</td><td> 40 — 84</td><td> 1 — 20</td>
<td>Pills</td><td> 1 — 25</td><td> 70 — 99</td><td> 0—5</td>
<td>Granules and pellets</td><td> 1-95</td><td> 5 — 99</td><td> 0 — 15</td>
<td>Highly concentrated agents</td><td> 90 — 99</td><td> 0 — 10</td><td> 0—2</td>
Ri '
Re
Qi Qž Q3
11-C3H7
<td>phenyl</td><td>—CH2CH—</td><td>H</td><td>H</td><td>H</td>
<td>phenyl</td><td>- C (CH3)<sub>2</sub>C (CH3) 2--</td><td>H</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>—CH2CH2— C2H5</td><td>H</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>| —CH2CH— CH3 CH3 I 1</td><td>H</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>1 1 —CH - CH—</td><td>H</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>- CH2CH2— CH3</td><td>H</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>| —CHzCH— C2H5 1</td><td>H</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>1 —CHžCH—</td><td>H</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>—CICH3) 2C (CH3) 2— CHs</td><td>H</td><td>H</td><td>H</td>
<td>3-trifluoromethylphenyl</td><td>| —CHCH2C (CH3) 2— 11-C4H9</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>2-methoxyphenyl</td><td>| —CH2CH—</td><td>CH3</td><td>H</td><td>H</td>
<td>2,3-dimethylphenyl</td><td>—CH2CH2— C2H5 |</td><td>H</td><td>CHs</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>1 —CH2CH— 11-C3H7 AND</td><td>H</td><td>H</td><td>H</td>
<td>2,4-dlchlorophenyl</td><td>1 —CH2CH— CH3 CH3</td><td>H</td><td>H</td><td>H</td>
<td>2-methoxy-5-fluorophenyl</td><td>| | - ~ CHC (CH3) 2CH—</td><td>CH3</td><td>H</td><td>H</td>
<td>2,6-dimethoxyphenyl</td><td>—CH2CH2— CH3 CH3 i 1</td><td>H</td><td>H</td><td>H</td>
<td>3,4-dichlorophenyl</td><td>1 1 —CHCH2CH— CH3 CHs II</td><td>CHs</td><td>CH3</td><td>CH<sub>3</sub></td>
<td>3,5-dichlorophenyl</td><td>i 1 —CH --- CH—</td><td>CH3</td><td>CH3</td><td>CHs</td>
<td>C2H5</td><td>- CH<sub>2</sub>CH = CHCH2— CH<sub>3</sub> CH3 i 1</td><td>H</td><td>CH3</td><td>CH3</td>
<td>n-CisHsz</td><td>1 1 —CHCH2CH2CH—</td><td>H</td><td>CH3</td><td>CH3</td>
Table XVIII
<img file="CS238626B2_D0004.tif" />
<td>Rl *</td><td>Re</td><td>Qi</td><td>Q2</td><td>Q3</td>
<td>C2H5</td><td>t-C 6 H 9</td><td>H</td><td>H</td><td>H</td>
<td>11-C4H9</td><td>C2H5</td><td>H</td><td>H</td><td>H</td>
<td>11-C18H37</td><td>CH3</td><td>H</td><td>H</td><td>H</td>
<td>cyclohexyl</td><td>11-C3H7</td><td>H</td><td>H</td><td>H</td>
<td>1-Naphthyl</td><td>I-C4H9</td><td>H</td><td>H</td><td>H</td>
<td>phenyl</td><td>CH3</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>n-C3r7 <sup>:</sup></td><td>CH3</td><td>H</td><td>H</td>
<td>phenyl</td><td>1-C3H7</td><td>H</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>t-C 4 H 9</td><td>H</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>C2H5</td><td>H</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>n-C4H9</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>4-fluorophenyl</td><td>CH3</td><td>CH3</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>C2H5</td><td>H</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>C2H5</td><td>H</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>1-C3H7</td><td>H</td><td>H</td><td>H</td>
<td>3-trifluoromethylphenyl</td><td>S-C4H9</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>2-methoxyphenyl</td><td>11-C3H7</td><td>CH3</td><td>H</td><td>H</td>
<td>2,3-dimethylphenyl</td><td>1-C4H9</td><td>H</td><td>H</td><td>H</td>
<td>2,4-dichlorophenyl</td><td>CH3</td><td>H</td><td>H</td><td>H</td>
<td>2,4-dichlorophenyl</td><td>C2H5</td><td>H</td><td>H</td><td>H</td>
<td colspan="2">2-methoxy-5-fluorophenyl 1-C 3 H 7</td><td>H</td><td>H</td><td>H</td>
<td>2,6-dimethoxyphenyl</td><td>CH3</td><td>H</td><td>H</td><td>H</td>
<td>3,4-dichlorophenyl</td><td>C2H5</td><td>H</td><td>H</td><td>H</td>
<td>3,5-dichlorophenyl</td><td>n-C4H9</td><td>H</td><td>H</td><td>H</td>
<td></td><td>Table XIX</td><td></td><td></td><td></td>
<td> 0 0</td><td>> A</td><td></td><td></td><td></td>
<td colspan="2">d ^ are, K Ί</td><td></td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td>
<td>Ri *</td><td>Re</td><td>Qi</td><td>Q2</td><td>Q3</td>
<td>C2H5</td><td>—CH2CH2—</td><td>H</td><td>H</td><td>H</td>
<td>11-C4H9</td><td>CH3 1 —CH2CH—</td><td>CH3</td><td>H</td><td>H</td>
<td>n-CwH37</td><td>—CH2CH2CH2—</td><td>H</td><td>CH3</td><td>CH3</td>
<td>cyclohexyl</td><td>C2H5 1 —CH2CH—</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>1-Naphthyl</td><td>—-CH2CH2—-</td><td>CH3</td><td>H</td><td>H</td>
<td>phenyl</td><td>—CH2CH2—</td><td>H</td><td>H</td><td>H</td>
<td>phenyl</td><td>C2H5 1 —CH2CH—</td><td>H</td><td>H</td><td>H</td>
R1 * R2 R6
<td>3-trifluoromethylphenyl 2-methoxyphenyl 2-chlorophenyl 3-trifluoromethylphenyl 2-fluoro-4-chlorophenyl 2,3-dimethylphenyl 2,6-dimethoxyphenyl 3,4- dichlorophenyl 4-fluorophenyl</td><td>3-Trifluoromethylphenyl 2-methoxyphenyl 4-fluorophenyl 4-t-butylphenyl 4-bromophenyl 4-methylthiophenyl 4-methoxyphenyl 4-methylphenyl 4-fluorophenyl</td><td>I-C4H9 H H n-CiHg 1-C3H7 C2H5 H i-ClHg Mp 114-116 ° C</td>
<td></td><td>Table</td><td>XVII</td>
[ / ]
STEED<sub>fe</sub> 4
<td>Rl *</td><td>R2;</td><td></td><td>Qi</td><td>Qž</td><td>Q3</td>
<td>C2H5</td><td>ch<sub>3</sub></td><td>CH3</td><td>CH3</td><td>CHs</td><td>CHs</td>
<td>cyclohexyl</td><td>CH3</td><td>1-C3H7</td><td>H</td><td>CHs</td><td>CHs</td>
<td>n-Cl<sub>8</sub>Hs7</td><td>n-C 6 H 13</td><td>t-C 1 H 8</td><td>CHs</td><td>H</td><td>H</td>
<td>1-Naphthyl</td><td>CHs</td><td>I-C3H7</td><td>CH3</td><td>H</td><td>H</td>
<td>phenyl</td><td>ch<sub>3</sub></td><td>t-C 1 H 8</td><td>H</td><td>CHs</td><td>H</td>
<td>phenyl</td><td>ch<sub>3</sub></td><td>t-C 6 H 8</td><td>H</td><td>H</td><td>CHs</td>
<td>phenyl</td><td>CH3</td><td>t-C 6 H 8</td><td>CHs</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>ch<sub>3</sub></td><td>S-C4H9</td><td>H</td><td>CHs</td><td>CH3</td>
<td>phenyl</td><td>CH3</td><td>I-C3H7</td><td>CH3</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>11-C1H9</td><td>t-C 1 H 8</td><td>ch<sub>3</sub></td><td>CH3</td><td>CH3</td>
<td>4-phenylphenyl</td><td>CHs</td><td>t-C 1 H 8</td><td>CH3</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>ch<sub>3</sub></td><td>t-C 1 H 8</td><td>CHs</td><td>CH3</td><td>CHs</td>
<td>4-chlorophenyl</td><td>CHs</td><td>t-C 4 H 8</td><td>CHs</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>CH<sub>3</sub></td><td>t C4H9</td><td>H</td><td>CHs</td><td>CHs</td>
<td>4-fluorophenyl</td><td>CHs</td><td>t-C 1 H 8</td><td>H</td><td>CH3</td><td>H</td>
<td>4-fluorophenyl</td><td>CHs</td><td>t-C 4 H 8</td><td>H</td><td>H</td><td>CHs</td>
<td>phenyl</td><td>phenyl</td><td>C2H5</td><td>CH3</td><td>CHs</td><td>CHs</td>
<td>phenyl</td><td>phenyl</td><td>nC<sub>3</sub>H7</td><td>CHs</td><td>CHs</td><td>CH3</td>
<td>4-fluorophenyl</td><td>phenyl</td><td>I-C3H7</td><td>H</td><td>CH3</td><td>CHs</td>
<td>4-fluorophenyl</td><td>phenyl</td><td>t-C 6 H 8</td><td>CH3</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>phenyl</td><td>I-C3H7</td><td>CH3</td><td>H</td><td>H</td>
<td>2,4-dichlorophenyl</td><td>phenyl</td><td>H</td><td>CH3</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>t-C 4 H 8</td><td>CH3</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>t-C 1 H 8</td><td>H</td><td>CHs</td><td>CH3</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>t-C 4 H 9</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>2-methoxyphenyl</td><td>2-methoxyphenyl</td><td>C2H5</td><td>CHs</td><td>H</td><td>H</td>
<td>3-methylphenyl</td><td>3-methylphenyl</td><td>I-C4H9</td><td>CHs</td><td>H</td><td>H</td>
Example 45
NMR (CDCl3)
Preparation of (1H-imidazol-1-ylmethyl) phenylbis (2-propoxy) silane 1H-imidazol-1-ylmethyl (phenylbis) 2-propoxysilane can be prepared by the method of Example 26 using chloromethyl (phenyl) bis (2-propoxy) silane:
1.2 (12 H, d, J = <sub>6</sub>),
3.6 (2H, s),
4.2 (2H, septet, J = 6),
6.8-7.6 (8H, m).
Similarly, compounds of Table XVIII and XIX can be prepared.
n "<sup>22</sup> 1,4971;
Table XVI or<sub>6</sub>
Ri '
C2H5 t-C4H9
11-C 4 H 9 n-C 12 H 25
11-C18H37 cyclopropyl cyclohexyl
1- Naphthyl
2-naphthyl phenyl phenyl phenyl phenyl phenyl
4-phenylphenyl
4-phenylphenyl
4-phenylphenyl
4-phenylphenyl
4-chlorophenyl
4-chlorophenyl
4-chlorophenyl
4-fluorophenyl
4-fluorophenyl
4-Phenoxyphenyl
4-t-butylphenyl
3-Trifluoromethylphenyl 2-methylthiophenyl 2,4-dichlorophenyl 2,4-dichlorophenyl 2,4-dichlorophenyl
2,4- dichlorophenyl
2,3-dimethylphenyl
2-methyl-5-fluorophenyl 2,6-dimethoxyphenyl
3-Methyl-4-chlorophenyl
3,5-dichlorophenyl 11-C 12 H 25 n-C 16 H 37
1-naphthyl phenyl
4-fluorophenyl 4-chlorophenyl 4-phenylphenyl 4-phenylphenyl 4-t-butylphenyl
3-fluorophenyl
2-Methoxyphenyl 2-chlorophenyl
2,4- dichlorophenyl
3,5-dichlorophenyl
4-fluorophenyl 4-fluorophenyl 4-chlorophenyl 4-chlorophenyl 4-phenylphenyl 2,4-dichlorophenyl
<td>R2</td><td>Rs</td>
<td>CH3</td><td>CH3</td>
<td>CH3</td><td>t-C 6 H 8</td>
<td>CH3</td><td>C2H5</td>
<td>C2H5</td><td>CH3</td>
<td>n-C6H13</td><td>CH3</td>
<td>CH3</td><td>S-C4H9</td>
<td>CH3</td><td>CH3</td>
<td>I-C3H7</td><td>1-C3H7</td>
<td>cyclobutyl</td><td>n-C3H7</td>
<td>CH3</td><td>H</td>
<td>CH3</td><td>CH3</td>
<td>CH3</td><td>C2H5</td>
<td>CH3</td><td>I-C3H7 n<sub>D</sub><sup>20</sup> 1,5 3 5 2</td>
<td>t-C 1 H 8</td><td>H</td>
<td>11-C4H9</td><td>CH3</td>
<td>t-C 4 H 9</td><td>H</td>
<td>CH3</td><td>C2H5</td>
<td>CH3</td><td>n-C4H9</td>
<td>n-Cl9</td><td>n-C4Hg</td>
<td>CH3</td><td>CH3</td>
<td>CH3</td><td>C2H5</td>
<td>n-CsHt3</td><td>n-C3H7</td>
<td>CH3</td><td>C2H5</td>
<td>cyclohexyl</td><td>I-C4H9</td>
<td>n-C3H7</td><td>S-C4H9</td>
<td>I-C4H9</td><td>H</td>
<td>cyclopentyl</td><td>C2H5</td>
<td>CH3</td><td>CH3</td>
<td>ch<sub>3</sub></td><td>C2H5</td>
<td>CH3</td><td>t-C 4 H 8</td>
<td>11-C4H9</td><td>C2H5</td>
<td>cyclopropyl</td><td>I-C3H7</td>
<td>S-C1H9</td><td>11-C3H7</td>
<td>1,1-dimethylpropyl</td><td>H</td>
<td>C2H5</td><td>CH3</td>
<td>n-CsHu</td><td>C2H5</td>
<td>2,4-dichlorophenyl</td><td>I-C4H9</td>
<td>phenyl</td><td>CH3</td>
<td>phenyl</td><td>C2H5</td>
<td>phenyl</td><td>I-C4H9</td>
<td>phenyl</td><td>CH3</td>
<td>phenyl</td><td>11-C3H7</td>
<td>phenyl</td><td>C2H5</td>
<td>phenyl</td><td>S-C4H9</td>
<td>phenyl</td><td>s-CdHg</td>
<td>phenyl</td><td>C2H5</td>
<td>phenyl</td><td>H</td>
<td>phenyl</td><td>CH3</td>
<td>phenyl</td><td>1-C3H7</td>
<td>phenyl</td><td>11-C3H7</td>
<td>4-fluorophenyl</td><td>I-C4H9</td>
<td>4-fluorophenyl</td><td>C2H5</td>
<td>4-chlorophenyl</td><td>CH3</td>
<td>4-chlorophenyl</td><td>C2H5</td>
<td>4-phenylphenyl</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>C2H5</td>
ir (Nujol<sup>TO</sup>), 1590, 1515, 1250, 1110, 840, 820,
750, 695, 650 cm '<sup>1</sup>;
By the method of Example 42, any compound of Table XIV, XV, XVI, XVII, XVIII or XIX can be converted to metal complexes or salts.
Example 43
Preparation of (1,1'-biphenyl-4-yl) (1H-imidazol-1-ylmethyl) (methoxy jmethylsilane)
A mixture of (1,1'-biphenyl-4-yl) chloro (chloromethyl) methylsilane and two equivalents of the imidazole sodium salt in dimethylformamide is maintained at 80-90 ° C for two hours. 10 equivalents of methanol are then added and the mixture is maintained at 70<sup>C</sup>C for one hour, cooled, diluted with water and extracted rapidly with ether. The ether solution was washed with water and brine, dried over magnesium sulfate and evaporated to give (1,1'-biphenyl-4-yl) (1H-imidazol-1-ylmethyl) (methoxy) methylsilane.
Related compounds can be obtained in the same manner using the appropriate chlorosilane and alcohol; for R 5 in the meaning of the hydroxyl group, water is used instead of the alcohol and the hydrolysis is carried out at 20 to 25 ° C instead of at 70 ° C.
Example 44
Preparation of 1,1- (dimethylethoxy) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane
A mixture of 3.6 g (0.015 mol) of chloromethyl- (1,1-dimethylethylixes) methyl (phenyl) silane and 1.3 g (0.015 mol) of imidazole sodium in 10 ml of dimethylformamide is stirred at 50 DEG C. for three hours. , allowed to stand at room temperature for 72 hours, poured into water and extracted with ether. The ether extracts were washed three times with water and once with brine, dried over magnesium sulfate and evaporated to give 3.8 g of an oil. The impurities were removed by distillation in a collar flask at 90 ° C (air bath) and at 6.66 Pa to give 2.9 g (71%) of 1,1- (dimethylethoxy) - (1H-imidazol-1-ylmethyl) methyl (phenyl jsilane) in the form of a pale yellow oil:
n<sub>D</sub><sup>20</sup> 1,5291;
ir (neat) 3105, 3070, 3045, 2970, 1590, 1500,
1425, 1360, 1250, 1235, 1185, 1110, 1055,
1020, 900, 805, 740, 700, 660 cm-<sup>1</sup>;
NMR (CDCl3)
0.6 (3 H, s),
1.3 (9H, s)
3.6 (2 H, s),
6.8 (1 H, s),
7.0 (1 H, s) and
7.3-7.7 (6H, m).
The compounds shown in Table XVI and XVII can be prepared by the method of Examples 43 and 44.
Example 44a
Preparation of [bis (4-chlorophenyl)] hydroxy (1H-imidazol-1-ylmethyl) silane
A mixture of 5.5 g (15.3 mmol) of chloromethyl [bis (4-chlorophenyl)] (2-propoxy jsilane) and 1.5 g (17.0 mmol) of imidazole sodium in dimethylformamide is maintained at 80-90 ° C. for two hours, cooled, diluted with ethyl acetate, washed three times with water and once with brine, dried over magnesium sulphate and evaporated to give a viscous oil. Trituration with ether gave 1.0 g (19%) of the title compound. as a colorless solid, m.p. 131-133 ° S;
NMR (CD3SOCD3)
4.1 (2 H, s),
6.8 (1 H, s),
6.9 (1 H, s),
7.4 (4H, d).
7.6 (5 H, d).
<td>Ri *</td><td>Rž</td><td>R3</td>
<td>2-Naphthyl</td><td>4-methylthiophenyl</td><td>4-methylthiophenyl</td>
<td>4-chlorophenyl</td><td>2-methoxyphenyl</td><td>2-methoxyphenyl</td>
<td>4-chlorophenyl</td><td>3-chlorophenyl</td><td>3-chlorophenyl</td>
<td>phenyl</td><td>2-chlorophenyl</td><td>4-fluorophenyl</td>
<td>phenyl</td><td>4-chlorophenyl</td><td>4-phenylphenyl</td>
<td>1-Naphthyl</td><td>4-bromophenyl</td><td>3-methylphenyl</td>
<td>4-Phenoxyphenyl</td><td>3,5-dimethylphenyl</td><td>3,4-dichlorophenyl</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>4-fluorophenyl mp 85-88 ° C</td>
<td>4-phenylphenyl</td><td>4-fluorophenyl</td><td>methylphenyl n<sub>n</sub><sup>22</sup> 1,6181</td>
<td rowspan="3">Ri '</td><td rowspan="3">T abu 1 ka<sup>R</sup>2. r <sup>1</sup>R<sub>1</sub> -Si-C 1 R2</td><td colspan="4">XV;</td>
<td colspan="3"></td><td rowspan="2">Qj</td>
<td>GL · /</td><td colspan="2">Ql () 2</td>
<td>C2H5</td><td>CH3</td><td>C-H3</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>n-CwH37</td><td>CH3</td><td>CH3</td><td>H</td><td>CPI3</td><td>CHs</td>
<td>cyclohexyl</td><td>CH3</td><td>ch<sub>3</sub></td><td>H</td><td>CH3</td><td>CHs</td>
<td>1-Naphthyl</td><td>CH3</td><td>CH3</td><td>CH3</td><td>H</td><td>H</td>
<td>phenyl</td><td>CH5</td><td>CH3</td><td>H</td><td>CH3</td><td>H</td>
<td>phenyl</td><td>CH3</td><td>CH3</td><td>H</td><td>H</td><td>CH3</td>
<td>4-phenylphenyl</td><td>CH3</td><td>ch<sub>3</sub></td><td>CH3</td><td>H</td><td>H</td>
<td>4- (4-fluorophenyl) phenyl</td><td>CH3</td><td>CH3</td><td>CH3</td><td>H</td><td>H</td>
<td>4-Phenoxyphenyl</td><td>CH3</td><td>ch<sub>3</sub></td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>3-trifluoromethylphenyl</td><td>CH3</td><td>CH3</td><td>H</td><td>CH3</td><td>CH3</td>
<td>2-methoxyphenyl</td><td>CH3</td><td>CH3</td><td>CHs</td><td>H</td><td>H</td>
<td>2,4-dichlorophenyl</td><td>CH3</td><td>CH3</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>2-chloro-4-phenylphenyl</td><td>CH3</td><td>CHs</td><td>H</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>n-CdHg</td><td>CH3</td><td>CH3</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>11-C4H9</td><td>ch<sub>3</sub></td><td>H</td><td>CH3</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>n-C6H13</td><td>CH3</td><td>CH3</td><td>H</td><td>H</td>
<td>4- (4-chlorophenoxy) phenyl</td><td>cyclohexyl</td><td>CH3</td><td>CH3</td><td>H</td><td>H</td>
<td>phenyl</td><td>phenyl</td><td>ch<sub>3</sub></td><td>CH3</td><td>CHs</td><td>CH3</td>
<td>4-fluorophenyl</td><td>phenyl</td><td>CH3</td><td>CH3</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>phenyl</td><td>ch<sub>3</sub></td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>4-chlorophenyl</td><td>phenyl</td><td>ch<sub>3</sub></td><td>H</td><td>CH3</td><td>CHs</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>ch<sub>3</sub></td><td>CH3</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>CH3</td><td>H</td><td>CH3</td><td>CH3</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>CH3</td><td>CH3</td><td>CH3</td><td>CHs</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>CH3</td><td>CH3</td><td>H</td><td>H</td>
<td>2-chlorophenyl</td><td>4-chlorophenyl</td><td>ch<sub>3</sub></td><td>CH3</td><td>CH<sub>3</sub></td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td colspan="2">2,4-dichlorophenyl CH3</td><td>CH3</td><td>H</td><td>H</td>
<td>n-C18H37</td><td>n-C6H13</td><td>11-C6H13</td><td>H</td><td>CH3</td><td>C.H3</td>
<td>1-naphthyl</td><td>n-CdHg</td><td>n-ClHg</td><td>CH</td><td>CHs</td><td>CHs</td>
<td>phenyl</td><td>phenyl</td><td>phenyl</td><td>CH3</td><td>H</td><td>H</td>
<td>phenyl</td><td>phenyl</td><td>phenyl</td><td>CH3</td><td>H</td><td>CH3</td>
<td>phenyl</td><td>phenyl</td><td>phenyl</td><td>CH3</td><td>CH3</td><td>H</td>
Example 42
Preparation of a 1: 1 (1,1'-biphenyl-4-yl) -dimethyl (1H-imidazol-1-ylmethyl) silane-copper (II) chloride complex
A mixture of 0.50 g (0.0017 mol) of (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane and 0.22 g (0.0017 mol) of cuprous chloride in ml of tetrahydrofuran was added. reflux under nitrogen for 15 minutes and the resulting dark green solution was evaporated to give a 1: 1 (Ι, Γ-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane / chloride complex copper (I) as a dark green solid, m.p. 72 DEG-80 DEG C. (dec.);
Ri '
R2
Rs
I-C3H7
11-C4H9 n-C10H11 n-C12H25
11-C14H29
11-C18H37 cyclopropyl cyclopentyl cyclohexyl
1-Naphthyl
1- Naphthyl
2-naphthyl phenyl phenyl phenyl phenyl
4-phenylphenyl
4-phenylphenyl
4-broniphenyl
4-chlorophenyl
4-fluorophenyl
4-Phenoxyphenyl
4-i-Propylphenyl
4-t-butylphenyl
3-phenylphenyl
3-trifluoromethylphenyl
3-chlorophenyl
2-methoxyphenyl
2-thiomethylphenyl
2-phenylphenyl
2,4-dichlorophenyl
2,4- dichlorophenyl
2,3-dimethylphenyl
2-methyl-5-fluorophenyl
2,5-dimethoxyphenyl
2,6-dimethylphenyl
3,4- dichlorophenyl
3,5-dichlorophenyl
3,5-dichlorophenyl
3-Methyl-4-chlorophenyl
4-fluorophenyl
4-chlorophenyl
4-bromophenyl
4-Phenylphenyl 4-t-butylphenyl 4-thiomethylphenyl 4-phenoxyphenyl
4-Trifluoromethoxyphenyl 4-methylsulfonylphenyl 4-cyclohexylphenyl 4- (4-fluorophenyl) phenyl
3-Trifluoromethylphenyl 2-chlorophenyl 2-methoxyphenyl
2,4-dichlorophenyl 2-chloro-4-phenylphenyl
2-fluoro-4-phenylphenyl
3,5-dichlorophenyl
2,5-dimethoxyphenyl
2,6-dimethoxyphenyl
4-fluorophenyl 4-chlorophenyl 4-bromophenyl 4-phenylphenyl 4-methoxyphenyl
3-Trifluoromethylphenyl cyclohexyl
11-C4H9 cyclopropyl
11-C3H7
I-C3H7
3-methylbutyl
N-C6H43 cyclopentyl cyclohexyl n-C1Hg t-C1Hg
11-C5H11
11-C3H7
11-C4H9
1,1-dimethylpropyl
11-C6H13
CžHs
11-C4H9 i-CsH?
11-C4H9
11-C1H9
C 1 -C 4 H 9 cyclopropyl
I-C4H9
1-C4H9
S-C 4 H 9 n-C 5 H 11 t-C 1 H 8 cyclobutyl
I-CjHg
II-C4H9 cyclopropyl
11-C 3 H 7 cyclopentyl
4-methylpentyl
1-methylbutyl
II-C5H11 n-C6Hc cyclohexyl cyclopropyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl
4-fluorophenyl
4-chlorophenyl
4-bromophenyl
4-phenylphenyl
4-methoxyphenyl
3-trifluoromethylphenyl
<td>CH3</td>
<td>CH3 n<sub>D</sub><sup>22</sup> 1,4710</td>
<td>CH3</td>
<td>CHs</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CHj</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CHs</td>
<td>CHó</td>
<td>CHs n<sub>at</sub><sup>22</sup> 1,5 4 49</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CHs n<sub>D</sub><sup>22</sup> 1,5880</td>
<td>CHó</td>
<td>CH<sub>3</sub> n<sub>D</sub><sup>21</sup> 1,5415</td>
<td>CH3 n<sub>D</sub><sup>22</sup> 1,5161</td>
<td>CHj</td>
<td>CHj</td>
<td>CH3</td>
<td>CHj</td>
<td>CHj</td>
<td>CH3</td>
<td>CHj</td>
<td>CH3</td>
<td>CHj</td>
<td>CH3 n<sub>D</sub><sup>21</sup> 1,5588</td>
<td>CH3</td>
<td>CHj</td>
<td>CH3</td>
<td>CH3</td>
<td>CHj</td>
<td>CHj</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3 n<sub>D</sub><sup>19</sup> 1,5810</td>
<td>CH3 n<sub>D</sub><sup>21</sup> 1,6000</td>
<td>CH3 n<sub>D</sub><sup>22</sup> 1,6115</td>
<td>CH3 n<sub>D</sub><sup>21</sup> 1,6378</td>
<td>CHs</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CHs n<sub>D</sub><sup>22</sup> 1,6058</td>
<td>CH3</td>
<td>CHs n<sub>D</sub><sup>22</sup> 1,6150</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3</td>
<td>CH3 n<sub>D</sub><sup>22</sup> 1,5569</td>
<td>CH3 n<sub>n</sub> 1,5820</td>
<td>CHs n<sub>D</sub><sup>21</sup> 1,6305</td>
<td>CH 3 mp 44-53 ° C</td>
<td>CH3 n<sub>D</sub><sup>21</sup> 1,5947</td>
<td>CH3</td>
R2
R3
Ri '_
2-chlorophenyl
2-methoxyphenyl
2,4- dichlorophenyl
3,5-dichlorophenyl
2-chlorophenyl
2-chlorophenyl 4-phenylphenyl 4-phenylphenyl 4-phenylphenyl 4-fluorophenyl 4-chlorophenyl
1-naphthyl 4-phenoxyphenyl C2H5
1-C 3 H 7 n-C 4 H 9 η-ϋβ-7 n-C 14 H 29 n-C 16 H 37 cyclopropyl cyclohexyl
1- Naphthyl
2-naphthyl phenyl
4-phenylphenyl
4-phenylphenyl
4-phenylphenyl
4-phenylphenyl
4-chlorophenyl
4-fluorophenyl
4-Phenoxyphenyl
4- (4-chlorophenoxy) phenyl
4-t-butylphenyl
3-methoxyphenyl
3-Trifluoromethylphenyl 2-thiomethylphenyl
2-phenylphenyl
2,4- dichlorophenyl
2,6-dimethylphenyl
3,5-dichlorophenyl
3-Methyl-4-chlorophenyl 2-methyl-5-fluorophenyl C2H5 cyclohexyl n-C18H37 n-C1H9 n-C12H25
I-Naphthyl cyclopropyl n-C4H9 n-C4Hg n-C3H7
C 1 -C 4 H 9 cyclopentyl
II-C14H29
11-C4H9 phenyl
4-chlorophenyl
4-fluorophenyl
4-phenylphenyl
2,4-dichlorophenyl phenyl phenyl phenyl phenyl
2-chlorophenyl
2-methoxyphenyl
2,4- dichlorophenyl
3,5-dichlorophenyl 4-chlorophenyl 4-fluorophenyl 4-chlorophenyl
4-fluorophenyl 2,4-dichlorophenyl 2,4-dichlorophenyl
2,4- dichlorophenyl
2,6-dimethoxyphenyl
3,4-dichlorophenyl C2H5
1-C 3 H 7 n-C 6 H 8
C 2 H 5 cyclopropyl n-C 6 H 13
C 2 H 5 n-C 3 H 7 n-C 6 H 8 n-C 4 H 9 cyclopropyl
C 2 H 5 n-C 4 H 9 n-C 6 H 13 cyclohexyl
11-C4I-19
11-C3H7
11-C4H9
11-C4H9
5- C4H9
C2H5
S-C4H9
1-C3H7 cyclohexyl n-CdHg t-CdHg cyclopentyl
S-C 1 H 9 n-C 1 H 8 phenyl phenyl phenyl
4-chlorophenyl
4-chlorophenyl
4-fluorophenyl phenyl phenyl phenyl phenyl phenyl phenyl
4-chlorophenyl
4-fluorophenyl phenyl
4-chlorophenyl
4-fluorophenyl
4-phenylphenyl
2,4-dichlorophenyl 4-fluorophenyl 4-chlorophenyl 4-phenylphenyl 2,4-dichlorophenyl
CH3 n<sub>D</sub><sup>20</sup> 1,5 9 9 9
CHs
CH3 n<sub>D</sub><sup>22</sup> 1,6019
CH3
CH3 n<sub>D</sub><sup>20</sup> 1,6044
CH<sub>3</sub> ch<sub>3</sub>
CH3 ch<sub>3</sub> gh<sub>3</sub>
CH3
CH3
CH3
C2H5
1-C 3 H 7 n-C 4 H 8 cyclopentyl
1-methylbutyl n-C 6 H 13 S-C 4 H 9
II-C 3 H 7 n-C 1 H 8 cyclobutyl n-C 6 H 13
C2H5 n-C4H9 n-C6H13 cyclohexyl n-C1Hg n-C3H7 cyclohexyl n-C1Hg
1- CiHg t-CiHg
S-C4H9
3-methylbutyl cyclohexyl n-C1Hg t-QHg cyclopentyl
S-C4U9-C1H9 phenyl phenyl phenyl
4-chlorophenyl 4-chlorophenyl 4-fluorophenyl 4-t-butylphenyl 4-phenylphenyl
2,4- dichlorophenyl
3-Trifluoromethylphenyl
3,5-dichlorophenyl
2,6-dimethoxyphenyl
2-fluorophenyl
4-phenylphenyl phenyl mp 175-178 ° C
4-chlorophenyl
4-fluorophenyl
4-phenylphenyl
2,4-dichlorophenyl
4-fluorophenyl
4-chlorophenyl
4-phenylphenyl
2,4-dichlorophenyl
Table XIV
<img file="CS238626B2_D0005.tif" />
<td>Ri '</td><td>R2</td><td>R3</td>
<td>ch<sub>3</sub></td><td>CH3</td><td>CH3 n<sub>D</sub><sup>22</sup> 1,4805</td>
<td>C2H5</td><td>CH3</td><td>CH3 n<sub>D</sub><sup>22</sup> 1,4848</td>
<td>1-C3H7</td><td>CH3</td><td>CHs</td>
<td>11-C4H9</td><td>. CH3</td><td>CH3 n<sub>D</sub><sup>19</sup> 1,4811</td>
<td>t-C 1 H 8</td><td>CH3</td><td>CHs</td>
<td>11-C12H25</td><td>CH3</td><td>CH3 n<sub>D</sub>25 1,4585</td>
<td>11-C14H29</td><td>CH3</td><td>CHs</td>
<td>11-C18 H57</td><td>CHs</td><td>CH3 n<sub>D</sub><sup>21</sup> 1,4639</td>
<td>cyclopropyl</td><td>CH3</td><td>CH3</td>
<td>cyclobutyl</td><td>ch<sub>3</sub></td><td>CH3</td>
<td>cyclopentyl</td><td>CHs</td><td>CH3</td>
<td>cyclohexyl</td><td>CHs</td><td>CH3 n<sub>D</sub><sup>22</sup> 1,4999</td>
<td>1-Naphthyl</td><td>CH3</td><td>CH<sub>3</sub> n<sub>D</sub><sup>23</sup> 1,6188</td>
<td>2-Naphthyl</td><td>CH5</td><td>CH3</td>
<td>phenyl</td><td>CH3</td><td>CH 2 t 120-125 ° C</td>
<td>4-bromophenyl</td><td>CHs</td><td>CHs n<sub>D</sub><sup>2</sup>« 1,5741</td>
<td>4-fluorophenyl</td><td>ch<sub>3</sub></td><td>CHs n<sub>D</sub><sup>23</sup> 1,5314</td>
<td>4-methoxyphenyl</td><td>CHs</td><td>CH3 n<sub>D</sub><sup>25</sup> 1,5485</td>
<td>4-Phenoxyphenyl</td><td>CH3</td><td>CH3 n<sub>D</sub><sup>22</sup> 1,5833</td>
<td>4- (4-chlorophenoxy) phenyl</td><td>CHs</td><td>CH3 n<sub>D</sub><sup>22</sup> 1,5564</td>
<td>4- (Fluorophenoxy) phenyl</td><td>CH3</td><td>CH3</td>
<td colspan="2">4- [4-Trifluoromethylphenoxy) 1-enyl CH3</td><td>CH3</td>
<td>4- (4-methylphenoxy) phenyl</td><td>CHs</td><td>CH3</td>
<td>4-thiomethylphenyl</td><td>CH3</td><td>CHs n<sub>D</sub><sup>23</sup> 1,5855</td>
<td>4-methylsulfonylphenyl</td><td>CH3</td><td>CH3 η<sub>η</sub><sup>21</sup> 1,5552</td>
<td>4 trifluoromethylphenyl</td><td>CH3</td><td>CH3 n<sub>at</sub><sup>22</sup> 1,4867</td>
<td>4-methylphenyl</td><td>CH3</td><td>CHs n<sub>D</sub><sup>21</sup> 1,5482</td>
<td>4-i-Propylphenyl</td><td>CHs</td><td>CH3</td>
<td>4-t-butylphenyl</td><td>CH3</td><td>CHs n<sub>D</sub><sup>23</sup> 1,5229</td>
<td>4-cyclohexylphenyl</td><td>CH3</td><td>CHs n<sub>n</sub><sup>22</sup> 1,5085</td>
<td>4-Trifluoromethoxyphenyl</td><td>CH3</td><td>CHs lip<sup>22</sup> 1,4888</td>
<td>4- (4-chlorophenyl) phenyl</td><td>CH3</td><td>CH3</td>
<td>4- [4-methylphenyl) phenyl</td><td>CHs</td><td>CH3</td>
<td>4- (4-Trifluoromethylphenyl) phenyl</td><td>CHs</td><td>CH3</td>
<td>4- (4-fluorophenyl) phenyl</td><td>CH3</td><td>CH3</td>
<td>4- (4-bromophenyl) phenyl</td><td>CH3</td><td>CH3 n<sub>D</sub><sup>22</sup> 1,5745</td>
<td>3-phenylphenyl</td><td>CHs</td><td>Cf13 n<sub>D</sub><sup>21</sup> 1,6002</td>
<td>3-trifluoromethylphenyl</td><td>CH3</td><td>CH3 n<sub>D</sub><sup>20</sup> 1,4927</td>
<td>3-chlorophenyl</td><td>CHs</td><td>CH3 n<sub>D</sub><sup>22</sup> 1,5560</td>
<td>2-Trifluoromethylphenyl</td><td>CH3</td><td>CH3 n<sub>D</sub><sup>23</sup> 1,5056</td>
<td>2-phenylphenyl</td><td>CH3</td><td>CH3 n<sub>D</sub><sup>22</sup> 1,5996</td>
<td>2-chlorophenyl</td><td>CH3</td><td>CHs n<sub>D</sub><sup>22</sup> 1,5382</td>
<td>2-methoxyphenyl</td><td>CH3</td><td>CH3 n<sub>D</sub><sup>22</sup> 1,5344</td>
<td>2,3-dimethylphenyl</td><td>CH3</td><td>CH3</td>
<td>2,3-dimethoxyphenyl</td><td>CH3</td><td>CH3 n<sub>D</sub><sup>22</sup> 1,5350</td>
<td>2,4-difluorophenyl</td><td>CH3</td><td>CH3</td>
<td>2-fluoro-4-chlorophenyl</td><td>CH3</td><td>CH3</td>
<td>2-chloro-4-fluorophenyl</td><td>CHs</td><td>CH3</td>
<td>2-chloro-4-phenylphenyl</td><td>CH3</td><td>ch<sub>3</sub></td>
<td>2-fluoro-4-phenylphenyl</td><td>CH3</td><td>CH3</td>
<td>2-methyl-5-chlorophenyl</td><td>CH3</td><td>CH3</td>
<td>2,6-dimethoxyphenyl</td><td>CH3</td><td>CHs n<sub>D</sub><sup>23</sup> 1,5348</td>
<td>2,6-dimethylphenyl</td><td>CH3</td><td>CHs</td>
<td>3,4-dichlorophenyl</td><td>CH3</td><td>CH3 n<sub>D</sub><sup>23</sup> 1,5673</td>
<td>3-methyl-4-fluorophenyl</td><td>CH3</td><td>CHs</td>
<td>3,5-dichlorophenyl</td><td>CHs</td><td>CH3 n<sub>D</sub><sup>22</sup> 1,5461</td>
<td>C2H5</td><td>C2H5</td><td>ch<sub>3</sub></td>
6.6 (1H, broad sj,
6.9 (1H, broad s),
7.1 (1H, broad s),
7.3 (4 H, s).
Example 39
Preparation of (2,4-dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane
A mixture of 5.1 g (0.020 mol) of chloromethyl- (2,4-dichlorophenyl) dimethylsilane and 2.0 g (0.022 mol) of imidazole sodium in 10 ml of dry dimethylformamide was stirred at 80-90 ° C for two hours and worked up. according to the procedure of Example 18 to give 3.9 g (69%) of (2,4-dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane as a brown oil:
n<sub>D</sub><sup>23</sup> 1,5637;
ir (neat) 1560, 1500, 1450, 1355, 1250, 1105,
1095, 1075, 1025, 840, 780, 735 cm @ -1;
NMR (CDCl3)
0.4 (6H, s);
3.9 (2 H, s),
6.7 (1H, broad s),
7.0 (1H, broad sj,
7.2-7.5 (4H, m).
Example 40
Preparation of diphenyl (1H-imidazol-1-ylmethyl) methylsilane
A mixture of 4.9 g (0.020 mol) of chloromethyl (diphenyl) methylsilane and 2.0 g (0.022 mol) of imidazole sodium salt in 10 ml of anhydrous dimethylformamide was stirred at 80 DEG C. for 3.5 hours and worked up as in Example 18. Distillation in a collar flask at 125 ° C and at 6.66 Pa removed the volatile impurities to give 2.9 g (52% of theory) diphenyl (1H-imidazole-1). -ylmethyl) methylsilane as an oil;
n<sub>D</sub><sup>22</sup> 1,5995;
ir (neat) 3375, 3250, 1500, 1430, 1255, 1230,
1110, 1075, 1025, 810, 790, 735, 700, 660 cm<sup>1</sup>;
NMR (CDCl3)
0.6 (3 H, s),
3.9 (2H, s,
6.6 (1H, broad s),
6.9 (1H, broad sj,
7.2-7.5 (11H, m).
The compounds of Table XIV were prepared from the appropriate chloromethylsilanes by the method of Examples 37-40.
Example 41
Preparation of (1,1'-Biphenyl-4-yl) dimethyl [2-methyl-1H-imidazol-1-ylmethyl) silane (1,1'-Biphenyl-4-yl) dimethyl (2-methyl-1H-imidazole- 1-ylmethyljsilane was prepared as described in Example 37 using (1,1'-biphenyl-4-yl) chloro methyldimethylsilane and 2-methylimidazole sodium salt.
Related compounds can be prepared in the same manner using salts of 2,4-dimethylimidazole, 4,5-dimethylimidazole and 2,4,5-trimethylimidazole.
The method of Example 41 can be used to prepare the compounds listed in Table XV.
Rl
Re
Qi
Q2 phenyl phenyl
4-phenylphenyl
4-phenylphenyl
4-fluorophenyl
4-chlorophenyl
4-Phenoxyphenyl
3-trifluoromethylphenyl
2-methoxyphenyl
CHo CH3
II —CHCH2CH2CH — H — C (CH3) 2CH2CH2C (CH3) 2 - η —CH<sub>2</sub>CH = CHCH 2 - h
CHo CH3,
II —CH2C = CCH2— h —CH2CH = CHCH2 h —CH2CH2CH2CH2 — H n-CáHg
I - CH 2 CH 2 CH 2 CH - CH 3
CHo CHó
II —CHCH = CHCH — H
CH3 CHo
II —CH2CH - CHCH2— Η
H
H
H
H
H
H
CH3
CH3
H
Example 37
Preparation of (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane
A mixture of 2.6 g (0.010 mol) of (1,1'-biphenyl-4-yl) chloromethyldimethylsilane and 1.1 g (0.012 mol) of imidazole sodium salt in 5 ml of dimethylformamide is maintained at 80-90 ° C for two hours, cooled The ether solution was washed with water and brine, dried over magnesium sulphate and evaporated to give 2.0 g of a viscous, pale-yellow oil. Trituration of a small sample with hexanes gave a solid. The mass of the crude product is then taken up in a hot mixture of 20 ml of hexanes and 3 ml of ethyl acetate, the solution is cooled slowly and seed crystals are added as soon as haze is observed. The resulting crystals were collected and dried, yielding 0.84 g (29% of theory) of (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylinethyl) silane as colorless flakes:
mp 51-53 ° C;
(Nujor) 1235, 1215, 1105, 1065, 900, 830, 785, 750, 730, 685 cm -1;
NMR (CDCl3)
0.4 (6H, s);
3.7 (2 H, s),
6.7 (1H, broad s),
7.0 (1H, broad s),
7.1 - 7.8 (10H, m);
Analysis for C 18 H 20 N 2 Si (molecular weight: 292.45) calculated:
C 73.92 H 6.89 N 9.58 found:
C 73.40 H 7.00 N 9.40
C 73.70 H 7.00 N 9.40
Example 38
Preparation of (4-chlorophenyl) dimethyl (1H, imidazol-1-ylmethyl) silane
A mixture of 2.2 g (0.010 mol) of chloromethyl (4-chlorophenyl) dimethylsilane and 1.1 g (0.012 mol) of imidazole sodium in 5 ml of dimethylformamide was stirred at 80-90 ° C for two hours, cooled, diluted with water The ether solution was washed with water and brine, dried over magnesium sulfate and evaporated to give 2.0 g (81%) of (4-chlorophenyl) dimethyl (1H, imidazol-1-ylmethyl) silane in m.p. form of yellow liquid:
n<sub>D</sub>2 1,5 1.5472, ir (net) 1560, 1495, 1480, 1375, 1250, 1105, 1080, 905, 830, 810, 740 cm '<sup>1</sup>;
NMR (CDCl3)
0.3 (6H, s); 3.6 (2H, s);
<td>Ri</td><td>Re</td><td>Qi</td><td>Qž</td>
<td>phenyl</td><td>-C (CH 3) 2 C (CH 3) 2 -</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>—CH2CH2— C2H5 AND</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>1 —CH2CH— CH3 CH3 I 1</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>1 1 —CH CH</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>—CH2CH2— CH3 AND</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>1 —CH2CH— C2H5</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>—CH2CH—</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>—C (CH3) 2C (CH3) 2— CH3</td><td>H</td><td>H</td>
<td>3-trifluoromethylphenyl</td><td>1 —CHCH2C (CH3) 2— nC-1H</td><td>CH3</td><td>CH3</td>
<td>2-ethoxyphenyl</td><td>| —CH2CH—</td><td>H</td><td>ch<sub>3</sub></td>
<td>2,3-dimethylphenyl</td><td>—CH2CH2— C2H5</td><td>CH3</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>| —CH2CH— n-C3H7</td><td>H</td><td>H</td>
<td>2,4-dichlorophenyl</td><td>| —CH2CH— CH3 CH3 1</td><td>H</td><td>H</td>
<td>2-methoxy-5-fluorophenyl</td><td>—CHC (CH3) 2CH—</td><td>H</td><td>H</td>
<td>2,6-dimethoxyphenyl</td><td>—CH2CH2— CH3 CH3 1</td><td>H</td><td>H</td>
<td>3,4-dichlorophenyl</td><td>—CHCH2CH— CH3 CH3 1 1</td><td>H</td><td>H</td>
<td>3,5-dichlorophenyl</td><td>1 1 —CH CH—</td><td>H</td><td>H</td>
<td>C2H5</td><td>—CH<sub>2</sub>CH = CHCH2— ch<sub>3</sub> ch<sub>3</sub></td><td>CH3</td><td>CH3</td>
<td>n-C 16 H 37</td><td>| | —CHCH2CH2CH—</td><td>H</td><td>CH3</td>
<td>phenyl</td><td>—CH2CH = CHCH2—</td><td>H</td><td>H</td>
<td>phenyl</td><td>-C (CH 3) 2 CH = CHC (CH 3) 2 -</td><td>H</td><td>H</td>
Table XII
<img file="CS238626B2_D0006.tif" />
©»2
<td>Rl</td><td>Rs</td><td>Qi</td><td>Q2</td>
<td>C2H5</td><td>t-C 4 H 9</td><td>H</td><td>H</td>
<td>11-C4H9</td><td>C2H5</td><td>H</td><td>H</td>
<td>11-C18H37</td><td>CHs</td><td>H</td><td>H</td>
<td>cyclobexyl</td><td>n-C3H7</td><td>H</td><td>H</td>
<td>1-Naphthyl</td><td>1-C4H9</td><td>H</td><td>H</td>
<td>phenyl</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>11-C3H7</td><td>H</td><td>CH3</td>
<td>phenyl</td><td>I-C3H7</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>t-C 4 H 9</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>C2H5</td><td>CH3</td><td>CH3</td>
<td>4-phenylphenyl</td><td>n-C4Hy</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>CH<sub>3</sub></td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>C2H5</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>C2H5</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>1-C3H7</td><td>H</td><td>H</td>
<td>3-trifluoromethylphenyl</td><td>S-C4H9</td><td>CH3</td><td>CH3</td>
<td>2-methoxyphenyl</td><td>n-CsH7</td><td>H</td><td>ch<sub>3</sub></td>
<td>2,3-dimethylphenyl</td><td>1-C4H9</td><td>CH3</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>CHs</td><td>H</td><td>H</td>
<td>2,4-dichlorophenyl</td><td>C2H5</td><td>H</td><td>H</td>
<td>2-methoxy-5-fluorophenyl</td><td>1-C3H7</td><td>H</td><td>H</td>
<td>2,6-dimethoxyphenyl</td><td>CH3</td><td>H</td><td>H</td>
<td>3,4-dichlorophenyl</td><td>C2H5</td><td>H</td><td>H</td>
<td>3,5-dichlorophenyl</td><td>n-C4H9</td><td>H</td><td>H</td>
Table XIII
<img file="CS238626B2_D0007.tif" />
Rl
Q2
<td>C2H5</td><td>—CH2CH2—</td><td>CH3</td><td>CH3</td>
<td>n-C4H9</td><td>CH3 1 —CH2CH—</td><td>H</td><td>ch<sub>3</sub></td>
<td>n-C 18 H 37</td><td>—CH2CH2CH2—</td><td>H</td><td>H</td>
<td>cyclohexyl</td><td>C2H5 1 —CH2CH—</td><td>H</td><td>CH3</td>
<td>1-Naphthyl</td><td>—CH2CH2—</td><td>CH3</td><td>H</td>
<td>phenyl</td><td>—CH2CH2—</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>C2H5 1 —CH2CH—</td><td>H</td><td>H</td>
<td>phenyl</td><td>n-C3H7 1 —QH2CH—</td><td>H</td><td>H</td>
<td>Ri</td><td>Re</td>
<td></td><td>C2H5</td>
<td>2,4-dichlorophenyl</td><td>| —CH2CH— n-C3H7</td>
<td>2,4-dichlorophenyl</td><td>| —CH2CH— CH3 CH3</td>
<td>2-methoxy-5-fluorophenyl</td><td>1 —CHC (CH3) 2CH—</td>
<td>2,6-dimethoxyphenyl</td><td>—CH2CH2— CH3 CH3</td>
<td>3,4-dichlorophenyl</td><td>| | —CHCH2CH— CH3 CH3</td>
<td>3,5-dichlorophenyl</td><td>—CH — CH—</td>
<td>C2H5</td><td>—CH2CH = CHCH2— CH3 CH3</td>
<td>n-C1-4H37</td><td>| | —CHCH2CH2CH—</td>
<td>phenyl phenyl</td><td>—CH<sub>2</sub>CH = CHCH2— —C (CH3) 2CH = CHC (CH3) 2— CH3 CH3</td>
<td>phenyl</td><td>1 —CHCH2CH2CH— at 57 to 60 ° C (19,99 Pa)</td>
<td>phenyl 4-phenylphenyl</td><td>—C (CH3) 2CH2CH2C (CH3) 2— —CH2CH = CHCH2— CH3 CH3</td>
<td>4-phenylphenyl</td><td>| | —CH<sub>2</sub>C == CCH<sub>2</sub>—</td>
<td>4-fluorophenyl 4-chlorophenyl</td><td>—CH2 — CH = CHCH2— —CH2CH2CH2CH2— 11-C4H9 AND</td>
<td>4-Phenoxyphenyl</td><td>1 —CH2CH2CH2CH— CH3 CH3 I 1</td>
<td>3-Trifluoromethylphenyl</td><td>1 1 —CHCH = CHCH— CH3 CH3</td>
<td>2-methoxyphenyl</td><td>| | —CH2CH — CHCH2</td>
Ri
C2H5 n-C6Hg
11-C18H37 cycloliexyl
1-naphthyl phenyl phenyl
phenyl phenyl
4-phenylphenyl
4-phenylphenyl
4-phenylphenyl
AND
4-fluorophenyl
4-fluorophenyl
4-chlorophenyl
4-chlorophenyl
3-Trifluoromethyl-phenyl
2-methoxyphenyl 2,3-dimethylphenyl
Table XI
O
R ^ are -CH ^Ct
Re —CH2CH2—
CH3
I —CH2CH —— CH2CH2CH2—
C2H5
I —CH2CH— —CH2CH2— —CH2CH2—
C2H5
I-CH 2 CH-n-C 3 H 7
I - CH 2 CH - C (CH 3) 2 C (CH<sub>3</sub>Mp 142-162 ° C. (13.33 Pa) —CH2CH2—
C2H5
I —CH2CH—
CH3 CH3
II —CH — CH — CH2CH2—
CH3
I —CH2CH—
C2H5
I —CH2CH— —C (CH3) 2C (CH3) 2—
CH3
I - CHCH2C (CH3) 2-n-C4H9
I —CH2CH— —CH2CH2—
Example 35
Preparation of chloromethyl (phenyl) bis (2-propoxy) silane
A solution of 2.0 g (0.009 mol) of chloromethyl (dichloro) phenylsilane and 5 ml of 2-propanol in 15 ml of dimethylformamide was stirred under a nitrogen atmosphere while 2.5 ml (1.9 g, 0.018 mol) of triethylamine was added dropwise. The resulting suspension was heated to 80 ° C and held at this temperature for two hours, cooled, diluted with water and extracted with ether. The ether extracts were washed with water and brine, dried over magnesium sulfate and evaporated to give 2.2 g of a liquid. Column chromatography on silica gel, eluting with petroleum ether gave 1.4 g (58% of theory) of chloromethyl (phenyl) bis (2-propoxy) silane as a colorless liquid: n<sub>D</sub>22 1,4741;
NMR (CDCl3)
1.2 (12H, d, J = 6),
3.0 (2H, s);
4.3 (2H, septet, J = 6),
7.3 to 7.8 (5H, m).
The compounds listed in Tables X and XI were prepared by the method of Examples 33-35.
Example 36
Preparation of phenylbis (2-propoxy) (1H-1,2,4-triazol-1-ylmethyl) silane
Phenylbis (2-propoxy) (1H-1,2,4-triazol-1-ylmethyl) silane can be prepared by the method of Example 32 from chloromethyl (phenyl) bis (2-propoxy) silane:
NMR (CDCl3)
1.1 (12H, d, J-1),
4.0 (2H, s);
4.3 (2H, septet, J-6),
7.2 to 8.0 (7H, m).
Similarly, the compounds listed in Tables XII and XIII were prepared.
Table X
ORe
AND
R1-Si-CH2Cl
AND
ORe
<td>Ri</td><td>Re</td>
<td>C2H5</td><td>t-C 4 H 9</td>
<td>n-C4H9</td><td>C2H5</td>
<td>n-C 18 H 37</td><td>CH3</td>
<td>cyclohexyl</td><td>n-C3H7</td>
<td>1-Naphthyl</td><td>1-C4H9</td>
<td>phenyl</td><td>CH3</td>
<td>phenyl</td><td>n-C3H7</td>
<td>phenyl</td><td>t-C 4 H 9</td>
<td>4-phenylphenyl</td><td>C2H5</td>
<td>4-phenylphenyl</td><td>11-C4H9</td>
<td>4-fluorophenyl</td><td>CH3</td>
<td>4-fluorophenyl</td><td>C2H5</td>
<td>4-Chlorophenyl</td><td>C2H3</td>
<td>4-chlorophenyl</td><td>1-C3H7</td>
<td>3-trifluoromethylphenyl</td><td>S-C4H9</td>
<td>2-methoxyphenyl</td><td>IVC3H7</td>
<td>2,3-dimethylphenyl</td><td>I-C4H9</td>
<td>2,4-dlchlorophenyl</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>C2H5</td>
<td>2-methoxy-5-fluorophenyl</td><td>I-C3H7</td>
<td>2,6-dimethoxyphenyl</td><td>CH3</td>
<td>3,4-dichlorophenyl</td><td>C2H5</td>
<td>3,5-dichlorophenyl</td><td>n-C4Hg</td>
n<sub>D</sub>22 1,4962;
Table IX 'a,
<td>Ri</td><td>R2</td><td>Re</td><td>Qt</td><td>Q2</td>
<td>C2H5</td><td>CH3</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>cyclohexyl</td><td>CH3</td><td>I-C3H7</td><td>H</td><td>CH3</td>
<td>n-C 18 H 37</td><td>η-0βΗΐ3</td><td>t-C 4 H 9</td><td>CH3</td><td>CH3</td>
<td>1-Naphthyl</td><td>CH3</td><td>I-C3H7</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>CH3</td><td>I-C4H9</td><td>H</td><td>CH3</td>
<td>phenyl</td><td>CH3</td><td>t-C 4 H 9</td><td>CH3</td><td>H</td>
<td>phenyl</td><td>CH3</td><td>t-C 4 H 9</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>CH3</td><td>S-C4H9</td><td>H</td><td>CH3</td>
<td>phenyl</td><td>CH3</td><td>I-C4H9</td><td>H</td><td>CH3</td>
<td>4-phenylphenyl</td><td>11-C4H9</td><td>t-C 4 H 9</td><td>H</td><td>CH3</td>
<td>4-phenylphenyl</td><td>CH3</td><td>t-C 4 H 9</td><td>H</td><td>CH3</td>
<td>4-phenylphenyl</td><td>CH3</td><td>t-C 4 H 9</td><td>CHs</td><td>CH3</td>
<td>4-chlorophenyl</td><td>CH3</td><td>t-C 4 H 9</td><td>H</td><td>CHs</td>
<td>4-chlorophenyl</td><td>CH3</td><td>t-C 4 H 9</td><td>CH3</td><td>CHs</td>
<td>4-fluorophenyl</td><td>CH3</td><td>t-C 4 H 9</td><td>H</td><td>CH3</td>
<td>4-fluorophenyl</td><td>CH3</td><td>t-C 4 H 9</td><td>CHs</td><td>CH3</td>
<td>phenyl</td><td>phenyl</td><td>C2H5</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>phenyl</td><td>n-C3H7</td><td>CH3</td><td>CH3</td>
<td>4-fluorophenyl</td><td>phenyl</td><td>I-C3H7</td><td>H</td><td>CH3</td>
<td>4-fluorophenyl</td><td>phenyl</td><td>t-C 4 H 9</td><td>CH3</td><td>CH3</td>
<td>4-chlorophenyl</td><td>phenyl</td><td>I-C3H7</td><td>H</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>phenyl</td><td>H</td><td>CH3</td><td>CH3</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>t-C 4 H 9</td><td>H</td><td>CH3</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>t-C 4 H 9</td><td>CH3</td><td>H</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>t-C 4 H 9</td><td>CHs</td><td>CH3</td>
<td>2-methoxyphenyl</td><td>2-methoxyphenyl</td><td>C2H5</td><td>CH3</td><td>CH3</td>
<td>3-methylphenyl</td><td>3-methylphenyl</td><td>1-C4H9</td><td>H</td><td>CHs</td>
Example 33 Example 34
Preparation of chloromethyl (dichloro) phenylsilane
A solution of 25.1 mL (36.8 g, 0.200 mol) of chloromethyltrichlorosilane in 400 mL of dry tetrahydrofuran was cooled to -78 ° C under a nitrogen atmosphere and stirred vigorously with vigorous dropwise addition over a period of 48.0 mL (0.100 mol). 2.1 molar phenyllithium. Stir for an additional 30 minutes at -78 ° C, then allow the solution to warm to room temperature and evaporate to 200 mL. Ether (500 ml) was added, the lithium chloride was removed by filtration and the filtrate was evaporated to give 25.0 g of liquid. Distillation yielded 6.5 g (29%) of chloromethyl (dichloro) phenylsilane as a colorless liquid;
boiling point 62-82 ° C (19,99 Pa); NMR (CDCl 3) δ: -
3.3 (s, 2) and
7.1 to 7.9 (m, 5).
Preparation of chloromethyl (diethoxy) phenylsilane
A solution of 1.0 g (0.0044 mol) of chloromethyl (dichlorophenylsilane) in 8 ml of absolute ethanol is cooled to 0 ° C at room temperature.<sup>1</sup>of triethylamine while slowly adding 0.61 mL (0.445 g, 0.0044 mol) to give a suspension which is slowly warmed to room temperature. Ether (50 ml) was added, the precipitated triethylamine / hydrochloride was removed by filtration and the filtrate was evaporated to give the product as a residue which was filtered through a short silica gel column (95% petroleum ether: ethyl acetate) to give 0.80 g. (73% of theory) chloromethyl (diethoxy) phenylsilane as colorless<sup>1</sup> oils:
NMR (CDCl3)
1.25 (t, 6, J = 6 Hz), 3.0 (s, 2),
3.9 (q, 4, J = 6 Hz);
7.2 to 7.9 (m, 5).
238826
Ri Ra Re
<td>4-chlorophenyl</td><td>CH3</td><td>C2H5</td>
<td>4-fluorophenyl</td><td>n-C6H13</td><td>n-C3H7</td>
<td>4-fluorophenyl</td><td>CH3</td><td>C2H5</td>
<td>4-Phenoxyphenyl</td><td>cyclohexyl</td><td>1-C4H9</td>
<td>4-t-butylphenyl</td><td>n-Cl7</td><td>S-C4H9</td>
<td>3-trifluoromethylphenyl</td><td>t-C4H0</td><td>H</td>
<td>2-methylthiophenyl</td><td>cyclopentyl</td><td>C2H5</td>
<td>2,4-dichlorophenyl</td><td>CH3</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>CH3</td><td>C2H5</td>
<td>2,4-dichlorophenyl</td><td>CH3</td><td>t-C 4 H 9</td>
<td>2,4-dichlorophenyl</td><td>nC ^Hg</td><td>C2H5</td>
<td>2,3-dimethylphenyl</td><td>cyclopropyl</td><td>1-C3H7</td>
<td>2-methyl-5-fluorophenyl</td><td>S-C4H9</td><td>n-C3H7</td>
<td>2,6-dimethoxyphenyl</td><td>1,1-dimethylpropyl</td><td>H</td>
<td>3-methyl-4-chlorophenyl</td><td>C2H5</td><td>CH3</td>
<td>3,5-dichlorophenyl</td><td>n-CsHil</td><td>C2H5</td>
<td>11-C12H25</td><td>2,4-dichlorophenyl</td><td>I-C4H9</td>
<td>n-C 18 H 37</td><td>phenyl</td><td>CH3</td>
<td>1-Naphthyl</td><td>phenyl</td><td>C2H5</td>
<td>phenyl</td><td>phenyl</td><td>t-C 4 H 9</td>
<td>4-fluorophenyl</td><td>phenyl</td><td>CH3</td>
<td>4-chlorophenyl</td><td>phenyl</td><td>n-C3H7</td>
<td>4-phenylphenyl</td><td>phenyl</td><td>C2H5</td>
<td>4-phenylphenyl</td><td>phenyl</td><td>S-C4H9</td>
<td>4-t-butylphenyl</td><td>phenyl</td><td>S-C4H9</td>
<td>3-fluorophenyl</td><td>phenyl</td><td>C2H5</td>
<td>2-methoxyphenyl</td><td>phenyl</td><td>H</td>
<td>2-chlorophenyl</td><td>phenyl</td><td>CHs</td>
<td>2,4-dichlorophenyl</td><td>phenyl</td><td>1-C3H7</td>
<td>3,5-dichlorophenyl</td><td>phenyl</td><td>n-CsH7</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>t-C 1 H 8</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>C2H5</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>CH3</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>C2H5</td>
<td>4-phenylphenyl</td><td>4-phenylphenyl</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>2,4-dichlorophenyl</td><td>C2H5</td>
<td>3-trifluoromethylphenyl</td><td>3-trifluoromethylphenyl</td><td>I-C4H9</td>
<td>2-methoxyphenyl</td><td>2-methoxyphenyl</td><td>H</td>
<td>2-chlorophenyl</td><td>4-fluorophenyl</td><td>H</td>
<td>3-trifluoromethylphenyl</td><td>4-t-butylphenyl</td><td>n-C4H9</td>
<td>2-fluoro-4-chlorophenyl</td><td>4-bromophenyl</td><td>1-C3H7</td>
<td>2,3-dimethylphenyl</td><td>4-methylthiophenyl</td><td>. C2H5</td>
<td>2,6-dimethoxyphenyl</td><td>4-methoxyphenyl</td><td>H</td>
<td>3,4-dichlorophenyl</td><td>4-methylphenyl</td><td>1-C4H9</td>
sodium bicarbonate, water, brine, dried (MgSO 4) and evaporated to give 2.3 g of a viscous oil. Chromatography on silica gel, eluting with hexane and then ether gave 1.1 g (42%) of the title compound as a viscous oil which solidified on standing.
Melting point: 97-99 ° C;
NMR (CDCl3)
0.5 (3H, s);
3.9 (2 H, s),
5.2 (1H, broad sj,
7.3 to 7.8 (9H, m),
7.9 (1 H, s),
8.0 (1H, sj.
The compounds of Tables VIII and IX can be prepared by the methods of Examples 31-32c.
Example 32d
Preparation of oxybis [bis (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane]
A solution of 11.0 g (33.7 mmol of chloromethyl [bis (4-fluorophenyl)] - (2-propoxy) silane and 10 ml of 49% aqueous hydrofluoric acid in ethanol is refluxed for two hours under nitrogen, cooled. The organic layer was washed with water and brine, dried over magnesium sulfate and evaporated to give 9.7 g (100%) of chloromethyl (fluoro) [bis (4-fluorophenyl)] silane in in the form of mobile oil:
n<sub>D</sub><sup>22</sup> 1,5387;
NMR (CDCl3)
3.2 (2H, d,
7.2 (4H, ie,
7.8 (4H, d from d).
A mixture of 4.5 g (16 mmol of fluorosilane prepared as above) and 1.6 g (18 mmol of 1,2,4-triazole as the sodium salt in dimethylformamide) was stirred at 80-90 ° C for two hours. The resulting suspension was diluted with ether, washed three times with water and once with brine, dried (MgSO4) and evaporated to give a viscous oil. in the form of a colorless solid:
mp 165-168 ° C;
NMR (CDCl3)
4.1 (2 H, s),
7.0 (4 H, t),
7.4 (4H, d from DJ),
7.8 (1 H, s),
7.9 (1 H, s).
Table VIII
Ri R6 R6
<td>C2H5</td><td>CH3</td><td>CH3</td>
<td>t-C 4 H 9</td><td>CH3</td><td>t-C 6 H 8</td>
<td>n-Cl9</td><td>CHs</td><td>C2H5</td>
<td>h-Cl2H25</td><td>C2H5</td><td>CH3</td>
<td>11-C18H37</td><td>n-C6H13</td><td>CH3</td>
<td>cyclopropyl</td><td>CH3</td><td>S-C4H9</td>
<td>cyclohexyl</td><td>CH3</td><td>CH3</td>
<td>1-naphthyl</td><td>I-C3H7</td><td>1-C3H7</td>
<td>2-Naphthyl</td><td>cyclobutyl</td><td>n-C3H7</td>
<td>phenyl</td><td>CH3</td><td>H</td>
<td>phenyl</td><td>CH3</td><td>CH5</td>
<td>phenyl</td><td>CH3</td><td>C2H5</td>
<td>phenyl</td><td>CH3</td><td>1-C3H7 n<sub>D</sub><sup>20</sup> 1,5 3 67</td>
<td>phenyl</td><td>I-C4H9</td><td>H</td>
<td>4-phenylphenyl</td><td>n-C4H9</td><td>CH3</td>
<td>4-phenylphenyl</td><td>I-C4H9</td><td>H</td>
<td>4-phenylphenyl</td><td>CH3</td><td>C2H5</td>
<td>4-phenylphenyl</td><td>CH3</td><td>n-CaHg</td>
<td>4-chlorophenyl</td><td>II-C4H9</td><td>n-C4H9</td>
<td>4-chlorophenyl</td><td>CH?</td><td>CH?</td>
yielding (Γ, Γ-biphenyl-4-yl) (1H-1,2,4-triazol-1-ylmethyl) methoxy / methylsilane.
Related compounds can be prepared in the same manner using the appropriate chlorosilane and alcohol;
for the R-hydroxyl group, water is used instead of alcohol and the hydrolysis is carried out at 20-25 ° C instead of at 70 ° C.
Example 32
Preparation of (1,1-dimethylethoxy) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane
A mixture of 3.6 g (0.015 mol) of chloromethyl (1,1-dimethylethoxy) methyl (phenyl jsilane) and 1.3 g (0.015 mol) of 1,2,4-triazole sodium salt in 8 ml of dimethylformamide was stirred at 80 ° C for The mixture was extracted with ether and the ether extracts were washed with water and brine, dried (MgSO4) and evaporated to give 2.7 g of a yellow oil. Chromatography on silica gel, eluting with 50:50 ethyl acetate-hexanes, afforded 1.5 g (36%) of (1,1-dimethylethoxy) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane in in the form of a slightly yellow oil:
m ?! 1.5134;
ir (neat) 3120, 3070, 3045, 2975, 2925, 1500,
1425, 1380, 1365, 1270, 1240, 1190, 1140,
1115, 1050, 1020, 1010, 830, 810, 790, 740,
700, 680 cm-<sup>1</sup>;
NMR (CDCl 3)
0.0 (3H, sj,
1.3 (9H, s)
3.9 (2 H, s),
7.3 - 7.7 (5H, ia,
7.9 (1H, sj a)
8.0 (1H, sj.
The compounds listed in Tables VIII and IX, wherein
Ql = q<sub>2</sub> = H can be prepared similarly as described in Examples 31 and 32.
Example 32a
Preparation of bis (4-fluorophenyl) hydroxy (1H-1,2,4-triazol-1-ylmethyl) silane
A mixture of 10.0 g (30.6 mmol of chloromethylphis (4-fluorophenyl)] (2-propoxy) silane and 3.1 g (30.6 mmol of 1,2,4-triazole as the sodium salt in dimethylformamide) was stirred at 80 DEG-90 DEG C. under nitrogen for two hours, working up as in Example 32 to give 3.0 g (30%) of the title compound, recrystallization from chlorobutane to give the pure compound, mp 130 DEG-131 DEG C .;
NMR (CDCl 3)
4.1 (2H, s).
5.8 (1H, broad s),
7.1 (4H, t).
7.7 (4H, d from d),
7.8 (1H, s,
8.0 (1 H, s).
Example 32b
Preparation of bis (4-chlorophenyl) hydroxy (1H-1,2,4-triazol-1-ylmethyl jsilane) and bis (4-chlorophenyl) hydroxy (4H-1,2,4-triazol-4-ylmethyl jsilane)
Proceed as described in Example 32a using chloromethyl [bis (4-chlorophenyl)] (2-propoxy) silane to give an oil which is triturated with hexanes, then the hexane layer is decanted and the residual oil is recrystallized from system 9. : 1 hexanes-ethyl acetate to give the 1H isomer as a solid.
Mp 130-131 ° C;
NMR (CDCl 3)
4.1 (2H, s,
6.3 (1H, broad sj,
7.4 (4H, DJ)
7.6 (4H, dj)
7.8 (1 H, s),
8.0 (1H, sj.
Chromatography of the mother liquors on silica gel, eluting first with hexane and then with 9: 1 dichloromethane-acetone gave the 4H isomer as a solid: mp 98-103 ° C;
NMR (CDCl 3)
1.7 (1H, broad s),
4.2 (2 H, s),
7.8 (8H, s,
7.8 (2H, sj.
Example 32c
Preparation of (1,1'-biphenyl-4-yl) hydroxy (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane
A mixture of 3.0 g (8.9 mmol) of (Ι, Γ-biphenyl-4-yl) methyl (2-propoxy) (1H-1,2,4-triazol-1-ylmethyl) -silane, 3 ml of concentrated hydrochloric acid, 10 ml of water and 10 ml of tetrahydrofuran was stirred at room temperature overnight. The resulting solution was diluted with ether, washed with a saturated aqueous solution.
<td>Rl</td><td>R2</td><td>R3</td><td>Qi</td><td>Q2</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>CH3</td><td>H</td><td>CH3</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>CH3 -</td><td>CH3</td><td>H</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>CH3</td><td>H</td><td>CH3</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>CHs</td><td>CH3</td><td>CHs</td>
<td>2-chlorophenyl</td><td>4-chlorophenyl</td><td>ch<sub>3</sub></td><td>H</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>2,4-dichlorophenyl</td><td>CH3</td><td>CH3</td><td>CHs</td>
<td>n-C 18 H 37</td><td>n-CeHis</td><td>n-CsHi3</td><td>CH3</td><td>CH3</td>
<td>1-Naphthyl</td><td>n-C4H9</td><td>n-CiHg</td><td>H</td><td>CH3</td>
<td>phenyl</td><td>phenyl</td><td>phenyl</td><td>H</td><td>CH3</td>
<td>phenyl</td><td>phenyl</td><td>phenyl</td><td>CH3</td><td>H</td>
<td>phenyl</td><td>phenyl</td><td>phenyl</td><td>CH3</td><td>CH3</td>
Example 28 n<sub>D</sub><sup>20</sup> 1,5645;
Preparation of a 1: 1 (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane / copper (II) chloride complex.
A mixture of 5.0 g (0.017 mol) of (Ι, Γ-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) -silane and 1.7 g (0.017 mol) of copper (I) chloride in 170 ml of tetrahydrofuran was refluxed under nitrogen for 30 minutes and the resulting deep green solution was evaporated to give a 1: 1 (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,2) complex. 4-triazol-1-ylmethylsilane and cuprous chloride as a pale green-brown solid, mp 85-90 ° C;
ir (Nujol<sup>R</sup>) 3110, 1590, 1280, 1250, 1120, 1010,
990, 840, 825, 760, 700 cm '<sup>1</sup>.
Similarly, the following (Ι, Γ-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-4-ylmethyl) silane complexes were prepared:
: 1 complex with cuprous chloride, m.p. 83-87 ° C; 1 complex with cuprous chloride, m.p. 85-92 ° C;
1: 1 complex with zinc chloride: n<sub>D</sub><sup>21</sup> M.p. 244-250 ° C with decomposition.
Example 29
Preparation of (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) -silane 4-dodecylbenzenesulfonate salt
A solution of 1.0 g (0.0034 mol) of (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane in 10 ml of dichloromethane is combined with solution 1, 1 g (0.0034 mol) of 4-dodecylbenzenesulfonic acid in 10 ml of dichloromethane. The resulting solution was evaporated to give (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 4-dodecylbenzenesulfonate salt as a viscous yellow oil:
ir (neat) 3110, 3050, 3020, 2960, 2920, 2850,
2570, 1920, 1600, 1545, 1485, 1455, 1405,
1250, 1225, 1165, 1120, 1030, 845, 825, 755,
1010, 990, 735, 700, 670, 635 cm '<sup>1</sup>.
Example 30
Preparation of 2: 1 (bis (4-fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) -silane-copper (II) chloride complex
A mixture of 1.0 g (0.0032 mol) of [bis (4-fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane and 0.2 g (0.0016 mol) of chloride of copper (II) in 30 mL of tetrahydrofuran was heated at reflux under nitrogen for 30 min and evaporated to give a 2: 1 [bis (4-fluorophenyl)] methyl (1H-1,2,4-triazole-1-) complex. ylmethyl Jsilane and cupric chloride in the form of blue-green glass: there is no significant melting point;
ir (Nujol<sup>R</sup>) 1580, 1490, 1230, 1160, 1110, 830,
785 cm<sup>1</sup>.
Similarly, a 1: 1 complex with copper (I) chloride was prepared as a dark green glass without significant melting point; ir as above.
Using the methods described in Examples 26 to 28, any compound of Table VI, VII, VIII, IX, XII and XIII is converted to salts or metal complexes.
Example 31
Preparation of (1,1'-biphenyl-4-yl) (1H-1,2,4-triazol-1-ylmethylmethoxy) methylsilane
A mixture of (1,1'-biphenyl-4-yl) chlorochloromethylmethylsilane and two equivalents of 1,2,4-triazole salt in dimethylformamide is maintained at 80-90 ° C for two hours, then 10 equivalents of methanol are added and the mixture is maintained at 70 ° C for 1 hour, cooled, diluted with water and extracted rapidly with ether, washed with water and brine, dried (MgSO 4) and evaporated to give a white solid.
Example 26
Preparation of (3,5-Dimethyl-1H-1,2,4-triazol-1-ylmethyl) [bis (4-fluorophenyl)] methylsilane (3,5-Dimethyl-1H-1,2,4-triazole- 1-ylmethyl) [bis (4-fluorophenyl)] methylsilane was prepared as described in Example 25 using equimolar amounts of chloromethyl [bis- (4-fluorophenyl)] methylsilane and 3,5-dimethyl-1,2-sodium salt. Of 4-trlazole.
Related compounds were prepared using 3-methyl-1,2,4-triazole instead of 3,5-dimethyltriazole salt.
Example 27
Preparation of (1,1'-biphenyl-4-yl) dimethyl (3-methyl-1H-1,2,4-triazol-1-ylmethyl) silane
A solution of 5.9 g (0.020 mol) of (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane in 40 mL of dry tetrahydrofuran was cooled to -40 ° C. 12.5 ml (0.020 mol) of a 1.6 molar solution of n-butyllithium in hexane was added dropwise while stirring, and the resulting yellow solution was stirred for a further 15 minutes at -40 [deg.] C. 1.9 ml (4.2 g, 0.030 mol) of methyl iodide were allowed to warm to room temperature. The resulting solution was diluted with water and extracted with hexanes. The organic extracts were washed with water and brine, dried over magnesium sulfate and evaporated to give 5.7 g of a solid which was purified by silica gel column chromatography (ethyl acetate solution) to give 1.1 g of crude product. Recrystallization from 12 mL of 3: 1 hexanes-ethyl acetate gave 0.97 g (16 (% of theory)) (1,1'-biphenyl-1H-1,2,4-triazol-1-ylmethyl) [bis (4 -fluorophenyl) methylsilane as a white solid:
mp 95-98 ° C;
ir (Nujol<sup>R</sup>j 1590, 1270, 1250, 1180, 1120, 830
765.700 cm '*
NMR (CDCl3)
0.5 (6H, sj,
2.2 (3H, s)
3.7 (2H, s,
7.2 - 7.7 (9H, m),
7.8 (1H, ss.
Although preferred for spherical reasons, the position of the methyl group on the triazole ring has not been demonstrated and it is possible that the product is (1,1'-biphenyl-4-yl) dimethyl (5-methyl-1H-1,2,4- triazol-1-ylmethyl jsilane.
The methods described in Examples 26 and 27 can be used to prepare the compounds listed in Table VII.
Table VII
<img file="CS238626B2_D0008.tif" />
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<td>n-C 16 H 37</td><td>CH3</td><td>CH3</td><td>H</td><td>CHs</td>
<td>cyclohexyl</td><td>CH3</td><td>CHs</td><td>CH3</td><td>CH3</td>
<td>1-Naphthyl</td><td>ch<sub>3</sub></td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>CH3</td><td>CH3</td><td>H</td><td>CH3</td>
<td>phenyl</td><td>CH3</td><td>CH3</td><td>CH3</td><td>H</td>
<td>4-phenylphenyl</td><td>CH3</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>4- (4-fluorophenyl) phenyl</td><td>ch<sub>3</sub></td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>4-Phenoxyphenyl</td><td>ch<sub>3</sub></td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>3-trifluoromethylphenyl</td><td>ch<sub>3</sub></td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>2-methoxyphenyl</td><td>CH3</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>ch<sub>3</sub></td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>2-chloro-4-phenylphenyl</td><td>CH3</td><td>CHs</td><td>CH3</td><td>CH3</td>
<td>phenyl</td><td>n-CiHg</td><td>CH3</td><td>CH3</td><td>CH3</td>
<td>4-phenylphenyl</td><td>n-CaHg</td><td>CH3</td><td>H</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>n-C 6 H 13</td><td>CH3</td><td>CHs</td><td>CH3</td>
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<td>4-chlorophenyl</td><td>phenyl</td><td>CH3</td><td>H</td><td>CH3</td>
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4.1 (2H, s);
7.2 - 7.5 (3H, m)
7.8 (1 H, s),
7.9 (1 H, s).
Example 24
Preparation of bis (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane
A mixture of 6.3 g (0.020 mol) of clilormethyl-bis (4-chlorophenyl) methylsilane and 2.0 g (0.022 mol) of 1,2,4-triazole sodium salt in 10 ml of dry dimethylformamide is stirred at 80 ° C for 4 hours. The resulting suspension was cooled, diluted with water and washed with ether. The ether extracts were washed with several portions of water and one portion of brine, dried over magnesium sulfate and evaporated to give 5.4 g of a yellow oil: by distillation in a flask at 120 to 150 ° C (air bath) and at 6, 66 Pa, 4.0 g (58% of theory) of bis (4-chloromethyl-methyl (1H-1,2,4-triazol-1-ylmethyl) -silane) are obtained in the form of a slightly yellow oil: n<sub>D</sub><sup>26</sup> 1,5966;
NMR (CDCl3)
0.7 (3H, s);
4.1 (2H, s).
7.2 - 7.5 (8H, ia,
7.8 (1 H, s),
7.9 (1 H, s).
In a similar preparation, evaporation of the ether extracts gave a gummy solid which was triturated with hexanes to give the title compound as a colorless solid, mp 76-80 ° C.
Example 25
Preparation of bis (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane
A mixture of 4.2 g (0.015 mol) of (chloromethyl) bis (4-fluorophenyl) methylsilane and 1.4 g (0.015 mol) of 1,2,4-triazole sodium salt in 8 ml of dimethylformamide was stirred at 80 ° C for two hours. The resulting suspension was cooled, diluted with water and treated as described in Example 24 to give 4.0 g of a slightly yellow colored oil. The impurities were removed by distillation in a collar flask at 120-125 ° C and 6.66 Pa to give 2.3 g (49%) of bis (4-fluorophenyl) methyl (1H-1,2,4-triazole-). 1-ylmethyl) silane in the form of a yellow oil:
n<sub>D</sub><sup>21</sup> 1,5538;
ir (pure 3065, 3030, 2960, 2925, 1590, 1500,
1270, 1235, 1165, 1110, 1010, 830, 790 cm @ -1; NMR (CDCl3)
0.7 (3H, s,
4.2 (2H, s);
7.1 (4H, t, J = 9).
7.5 (4H, d from d, J = 6 and 9),
7.8 (1H, sj a)
7.9 (1 H, s).
A similarly prepared sample after recrystallization from hexane at-120 ° C gave a colorless solid, mp 52-53 ° C. According to Examples 19 and 21 to 25, from the appropriate chloromethylsilanes, compounds of Table VI are prepared wherein Q 1 = Q 2 = H.
g sample of single recrystallized 1 ', 1'- (biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-ylmethyl) silane, prepared as described in Example 14, using sodium methoxide-1,2,4-triazole is subjected to high pressure liquid ehromatography (sillkagel Water Prep PAK-500, flow rate 250 ml / min.). -triazol-1-ylmethyl compound, m.p. 99-100 ° C. Continued elution with 80:20 ethyl acetate-acetonitrile gave a small amount of 1,1'-biphenyl-4-yl (dimethyl-4H-1,2,4-triazol-4-yl) methylsilane as a colorless solid mp 130-133 ° C; NMR (CDCl 3)
0.4 (6H, s);
3.7 (2 H, s),
7.2 - 7.7 (9H, m),
7.9 (2H, sj.
Microanalysis for C17H19N3Si (MW 293.43) calculated:
C 69.58, H 6.53 N 14.32 found:
C 69.00 H 6.70 N 13.90
C 69.30 H 6.70 N 14.2
Example 21
Preparation of dimethyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane
A mixture of 9.0 ml (9.2 g, 0.050 mol) of chloromethyldimethylphenylsilane and 5.5 g (0.060 mol) of 1,2,4-triazole sodium salt in 25 ml of dimethylformamide is stirred and maintained at 90-95 ° C for for two hours, cooled, diluted with water and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulfate and evaporated to give 8.1 g (75% of theory) of a slightly brown oil.<sub>D</sub><sup>22</sup> 1.5350, containing dimethyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane and less impurity as determined by NMR.
boiling point 99 ° C at 2.66 Pa;
n<sub>D</sub><sup>20</sup> 1,5403;
NMR (CDCl3)
0.4 (6H, s);
3.8 (2H, s,
7.2 - 7.7 (5H, m),
7.7 (1H, s,
7.8 (1 H, s);
Analysis for C 11 H 15 N 3 Si (MW 217.34) calculated:
No 60.78 H 6.96 N 19.33 found:
C 60.70 H 7.00 N 16.90
C 60.20 H 7.00 N 16.80
Example 22
Preparation of (4-chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane
A mixture of 2.2 g (0.010 mol) of chloromethyl (4-chloromethyl) dimethylsilane and 1.1 g (0.012 mol) of 1,2,4-triazole sodium salt in 5 ml of dimethylformamide is kept at 80-90 ° C for two hours, The ether solution was washed with water and brine, dried (MgSO4) and evaporated to give 2.1 g (83%) of (4-chlorophenyl) dimethyl (1H-1,2,4-triazole). 1-ylmethyl Jsilane in the form of a yellow liquid:
n<sub>D</sub><sup>21</sup> 1,5428;
ir (net) 1555, 1470, 1245, 1130, 1080, 1010,
835, 805, 795, 735 cm-1<sup>1</sup>;
NMR (CDCl3)
0.4 (6H, s);
3.8 (2 H, s),
7.4 (4H, broad s),
7.8 (1H, ss.
Example 23
Preparation of (2,4-dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane
A mixture of 5.1 g (0.020 mol of chloromethyl (2,4-dichlorophenyl) dimethylsilane) and 2.0 g (0.022 mol) of 1,2,4-triazole sodium salt in 10 ml of dry dimethylformamide is stirred at 80-90 ° C for two hours. The resulting suspension was cooled, diluted with water and washed with ether. The ether extracts were washed with several portions of water and one portion of brine, dried (MgSO4) and evaporated to give 4.6 g (81%) of (2,4-dichlorophenyl) dimethyl (1H, 1,2,4-triazole). -1-ylmethyljsilane in the form of a pale yellow liquid:
n<sub>D</sub><sup>23</sup> 1,5580;
ir (neat) 1550, 1485, 1440, 1345, 1260, 1240,
1130, 1085, 1025, 1005, 835 cm @ -1;
NMR (CDCl3)
0.5 (6H, s);
X = R 1, R 1, R 2 R 5
<td>2,4-dichlorophenyl</td><td>n-C4H9</td><td>C2H5</td>
<td>2,3-dimethylphenyl</td><td>cyclopropyl</td><td>I-C3H7</td>
<td>2-methyl-5-fluorophenyl</td><td>S-C4H9</td><td>n-C3H7</td>
<td>2,6-dimethoxyphenyl</td><td>1,1-dimethylpropyl</td><td>H</td>
<td>3-methyl-4-chlorophenyl</td><td>C2H5</td><td>CH3</td>
<td>3,5-dichlorophenyl</td><td>n-CsHii</td><td>C2H5</td>
<td>n-C 12 H 25</td><td>2,4-dichlorophenyl</td><td>I-C4H9</td>
<td>n-CwH37</td><td>phenyl</td><td>CH3</td>
<td>1-Naphthyl</td><td>phenyl</td><td>C2H5</td>
<td>phenyl</td><td>phenyl</td><td>t-C 4 H 9</td>
<td>4-fluorophenyl</td><td>phenyl</td><td>CH3</td>
<td>4-chlorophenyl</td><td>phenyl</td><td>n-C3H7</td>
<td>4-phenylphenyl</td><td>phenyl</td><td>C2H5</td>
<td>4-phenylphenyl</td><td>phenyl</td><td>S-C4H9</td>
<td>4-t-butylphenyl</td><td>phenyl</td><td>S-C4H9</td>
<td>3-fluorophenyl</td><td>phenyl</td><td>C2H5</td>
<td>2-methoxyphenyl</td><td>phenyl</td><td>H</td>
<td>2-chlorophenyl</td><td>phenyl</td><td>CPI3</td>
<td>2,4-dichlorophenyl</td><td>phenyl</td><td>I-C3H7</td>
<td>3,5-dichlorophenyl</td><td>phenyl</td><td>n-C3H7</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>t-C 4 H 9</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>C2H5</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>ch<sub>3</sub></td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>C2H5</td>
<td>4-phenylphenyl</td><td>4-phenylphenyl</td><td>ch<sub>3</sub></td>
<td>2,4-dichlorophenyl</td><td>2,4-dichlorophenyl</td><td>C2H5</td>
<td>3-trifluoromethylphenyl</td><td>3-trifluoromethylphenyl</td><td>I-C4H9</td>
<td>2-methoxyphenyl</td><td>2-methoxyphenyl</td><td>H</td>
<td>2-chlorophenyl</td><td>4-fluorophenyl</td><td>H</td>
<td>3-trifluoromethylphenyl</td><td>4-t-butylphenyl</td><td>n-CdH9</td>
<td>2-fluoro-4-chlorophenyl</td><td>4-bromophenyl</td><td>I-C3H7</td>
<td>2,3-dimethylphenyl</td><td>4-methylthiophenyl</td><td>C2H5</td>
<td>2,6-dimethoxyphenyl</td><td>4-methoxyphenyl</td><td>H</td>
<td>3,4-dichlorophenyl</td><td>4-methylphenyl</td><td>1-C4H9</td>
<td>4-fluorophenyl</td><td>methyl</td><td>1-C3H7 η '2θ 1.4827</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>i-CgHt 110-111<sup>0</sup> (13.33 Pa)</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>1-C3H7 n<sub>D</sub>22 1,5650</td>
Example 19
Preparation of (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane
A mixture of 2.6 g (0.010 mol) of (1,1'-biphenyl-4-yl) chloromethyldimethylsilane and 1.1 g (0.012 mol) of 1,2,4-triazole sodium salt in 5 ml of dimethylformamide is maintained at a temperature of 80- 90 ° C for two hours, cooled, diluted with water and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulfate and evaporated to give 2.3 g of a colorless solid, mp 79-86 ° C. Recrystallization from a mixture of 25 ml of hexanes and 2 ml of ethyl acetate gave 1.1 g (38% of theory) of (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, m.p. mp 92-93 ° C;
ir (Nujol<sup>R</sup>) 1255, 1130, 1000, 825, 760, 695 cm "<sup>1</sup>;
7.2 - 7.7 (9H, m),
7.8 (1 H, s),
7.9 (1 H, s);
Analysis for C17H19N3SI (MW 293.43) calculated:
C 69.58 H 6.53 N 14.32 found:
C 70.0 H 6.6 N 13.9 C 69.8 H 6.7 N 13.8
An equimolar mixture of 1,2,4-triazole and sodium methoxide may be used in place of the previously prepared sodium triazole salt. These reactants must be mixed prior to the addition of the silane, as chloromethylsilane reacts very intensively with sodium methoxide in dimethylformamide to give undesired products.
NMR (CDCl3)
0.4 (6H, s), 3.9 (2H, s),
Example 20
Preparation of (1,1'-biphenyl-4-yl) dimethyl (4H-1)<sub>?</sub>2,4-triazol-4-ylmethyl) silane is therefore dissolved in hexanes containing 30 ml of isopropanol and the solution is cooled rapidly in ice and treated with a solution of 42 ml (0.30 mol) of triethylamine in hexanes. The resulting suspension was stirred at room temperature for three hours and filtered and the filtrate was evaporated to give an oil. Distillation gave 44.8 g (43% of theory) of the title compound as a colorless liquid, bp 120-140 [deg.] C .; n<sub>D</sub><sup>22</sup> 1,5211;
NMR (CDCl3)
1.2 (6H, d),
3.2 (2H, s).
4.1 (1 H, septet),
7.1 (4H, t).
7.7 (4H, d from d).
Example 18
Preparation of chloromethyl (ethoxy) methyl (phenyl) silane
A solution of 18.2 mL (18.2 g, 0.10 mol) of chloromethyl (diethoxy) methylsilane in 200 mL of dry ether was stirred vigorously under nitrogen and cooled while adding 56 mL (0.10 mol) of 1.8 of a 70: 30 cyclohexane-ether solution at a rate such that the temperature of the mixture is below -50 ° C. The resulting suspension was allowed to warm to room temperature, treated cautiously with 10 mL of ethyl acetate, washed with water and brine, dried over magnesium sulfate and evaporated to give 16.8 g of a golden yellow oil. Distillation gave 9.5 g (44% of theory) of chloromethyl (ethoxy) methyl] phenyl silane as a colorless liquid, b.p. 80 DEG-84 DEG C. at 1 mm Hg;
n<sub>D</sub><sup>20</sup> 1,5144;
NMR (CDCl3)
0.5 (3H, s), 1.2 (3H, t, J = 7),
3.0 (2H, s);
3.8 (2H, q, J = 7);
7.2-7.8 (5H, m).
The compounds of Table V can be prepared using the method described in Examples 16-18.
Table V
R2
AND
X — Si — CH2GI
AND
ORe
X = R 1, R 1, R 2 Re
<td>C2H5</td><td>CH3</td><td>CH3</td>
<td>t-ClHs</td><td>CHs</td><td>t-C 4 H 9</td>
<td>11-C4H9</td><td>CH3</td><td>C2H5</td>
<td>n-C 12 H 25</td><td>C2II5</td><td>GH-3</td>
<td>11-C18H37</td><td>n-CeHis</td><td>CH3</td>
<td>cyclopropyl</td><td>CHí</td><td>S-C4H9</td>
<td>cyclohexyl</td><td>GHs</td><td>CHs</td>
<td>1-Naphthyl</td><td>I-C3H7</td><td>I-C3H7</td>
<td>2-Naphthyl</td><td>cyclobutyl</td><td>n-C? H?</td>
<td>phenyl</td><td>CHs</td><td>H</td>
<td>phenyl</td><td>CH3</td><td>I-C3H71. v. 72 to 76 ° C (13, 33 Pa)</td>
<td>phenyl</td><td>t-CiHa</td><td>H</td>
<td>4-phenylphenyl</td><td>11-C 1 H 5</td><td>CH3</td>
<td>4-phenylphenyl</td><td>t-CdHg</td><td>H</td>
<td>4-phenylphenyl</td><td>CH3</td><td>G2H5</td>
<td>4-phenylphenyl</td><td>CH3</td><td>11-C4H9</td>
<td>4-chlorophenyl</td><td>11-G4H9</td><td>11-G4H9</td>
<td>4-chlorophenyl</td><td>CH3</td><td>CHs</td>
<td>4-chlorophenyl</td><td>CH3</td><td>C2H5</td>
<td>4-fluorophenyl</td><td>n-C 6 H 13</td><td>n-G 3 H 7</td>
<td>4-fluorophenyl</td><td>CH3</td><td>C2H5</td>
<td>4-Phenoxyphenyl</td><td>cyclohexyl</td><td>I-G4H9</td>
<td>4-t-butylphenyl</td><td>n-C3H7</td><td>S-C4H9</td>
<td>3-trifluoromethylphenyl</td><td>t-C 6 H 8</td><td>H</td>
<td>2-methylthiophenyl</td><td>cyclopentyl</td><td>G2H5</td>
<td>2,4-dichlorophenyl</td><td>CH3</td><td>CH3</td>
<td>2,4-dichlorophenyl</td><td>GH3</td><td>C2H5</td>
<td>2,4-dichlorophenyl</td><td>CH3</td><td>I-C4H9</td>
Example 16
Preparation of chloromethyl (methoxy) methyl (phenyl) silane
A solution of 1.6 mL (1.3 g, 0.040 mol) of methanol and 3.0 mL (2.2 g, 0.022 mol) of triethylamine in 100 mL of ether was stirred while adding a solution of 4.1 g (0.020 mol) of chlorine ( chloromethyl) methyl (phenyl jsilane) in 10 ml of ether dropwise. The resulting suspension was maintained at reflux for two hours, cooled, washed with water, 0.1 N aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution and brine, dried over magnesium sulfate and evaporated to give 3.2 g. g of a slightly yellow liquid. Distillation gave 1.7 g (42%) of chloromethyl (methoxy) methyl (phenyl jsilane) as a colorless liquid:
boiling point 46-49 [deg.] C at 6.66 Pa; n<sub>D</sub><sup>22</sup> 1,5207;
NMR (CDCl3)
0.5 (3H, s);
3.0 (2H, s,
3.5 (3H, s);
7.3-7.8 (5H, m).
Example 17
Preparation of chloromethyl (1,1-dimethylethoxy) methyl (phenyl) silane
A mixture of 15.4 g (0.075 mol) of chloro (chloromethyl) methyl (phenyl) silane, 14 ml (11.1 g, 0.15 mol) of tert-butanol, 11.5 ml (8.3 g, 0.082 mol) of triethylamine and 0.5 g (0.008 mol) of imidazole in 60 ml of dimethylformamide was stirred at 80 ° C for two hours. The resulting suspension was cooled, poured into 200 ml of water and extracted with ether. The ether extracts were washed with water three times, then washed with 0.1 N aqueous hydrochloric acid, saturated aqueous sodium bicarbonate and brine, dried over magnesium sulfate and evaporated to give 14.0 g of a slightly orange oil. Distillation gave 11.9 g (65% of theory) of chloromethyl (1,1-dimethylethoxy) methyl (phenyl) silane, bp 78-82 [deg.] C at 26.66 Pa;
n<sub>D</sub><sup>21</sup> 1,5010;
ir (neat) 3080, 3060, 2990, 2940, 1600, 1435,
1395, 1370, 1260, 1245, 1195, 1125, 1060,
1030, 815, 790, 740, 725, 705, 650 cm '<sup>1</sup>; NMR (CDCl3)
0.3 (3 H, s),
1.3 (9H, s).
2.9 (2H, s);
7.3 - 7.8 (3H, m).
Example 17a
Preparation of (1,1'-biphenyl-4-yl) chloromethyl (methyl (2-propoxy) silane)
A solution of 73.3 g (0.315 mol) of 4-bromobiphenyl in 300 ml of tetrahydrofuran is added dropwise to a stirred suspension of 7.64 g (0.315 mol) of magnesium in 100 ml of tetrahydrofuran at such a rate that the temperature is maintained at moderate reflux. The resulting clear solution was stirred at room temperature for one hour and then cooled in ice and a solution of 40 mL (0.315 mol) of chloromethyl (dichloro-methylsilane in 100 mL of tetrahydrofuran) was quickly added. The resulting solution was stirred at room temperature for 20 hours, treated with 50 ml of isopropanol and cooled again in ice. A solution of 48 ml (0.344 mol) of triethylamine in tetrahydrofuran is then added at a rate such that the temperature of the mixture is kept below 25 DEG C. A suspension is obtained by stirring at room temperature for 90 minutes, filtered, evaporated, triturated with hexanes and filtered. removes amine hydrochloride residues. Evaporation of the hexane solutions gave 92 g (96% of theory) of the title compound as a pale yellow oil which solidified on standing, mp 35-38 ° C;
NMR (CDCl3)
0.5 (3H, s);
1.2 (6H, d),
3.0 (2H, s);
4.2 (1 H, septet),
7.3-7.8 (9H, m).
Example 17b
Preparation of chloromethyl [bis (4-fluorophenyl)] (2-propoxy) silane
A mixture of magnesium (23.2 g, 0.955 mol) and iodine (50 mg) in ether (200 ml) was stirred while adding a solution of 4-bromofluorobenzene (167 g, 0.954 mol) in ether (600 ml) at such a rate as to maintain the reflux temperature. It is then kept at reflux for a further 2 hours, the solution is cooled in ice and stirred with the dropwise addition of a solution of 40 ml (0.32 mol) of chloromethyltrichlorosilane in ether over 40 minutes. The resulting mixture was stirred at room temperature for 17 hours, cooled in ice, treated with 24 ml of isopropanol, stirred for an additional 10 minutes, and filtered. The filtrate was concentrated to a gummy solid, hexanes were added and the resulting suspension was filtered and the hexane filtrate was evaporated to give an oil. NMR analysis shows the presence of unreacted chlorine238626
Table IV
R2
X - Si - CH: Cl
X = Ri, Ri *
C2H5 t-CaHg
11-C 4 H 9 n-C 12 H 25
11-C18H37 cyclopropyl cyclohexyl
1- Naphthyl
2-naphthyl phenyl
4-phenylphenyl
4-phenylphenyl
4-chlorophenyl
4-chlorophenyl
4-fluorophenyl
4-Phenoxyphenyl
4-t-butylphenyl
4-trifluoromethoxyphenyl
4- (4-fluorophenyl) phenyl
3-Trifluoromethylphenyl
2-thiomethylphenyl
2,4-dichlorophenyl
2,4- dichlorophenyl
2-chloro-4-phenylphenyl
2,3-dimethylphenyl
2-methyl-5-fluorophenyl 2,6-dimethoxyphenyl
3-Methyl-4-chlorophenyl
3,5-dichlorophenyl n-C 12 H 25 n-C 16 H 37
1-naphthyl phenyl
4-fluorophenyl
4-chlorophenyl 4-phenylphenyl 4-t-butylphenyl
3-fluorophenyl
2-methoxyphenyl
2-chlorophenyl
2,4- dichlorophenyl
3,5-dichlorophenyl
4-fluorophenyl 4-chlorophenyl 4-phenylphenyl
2,4-dichlorophenyl
3-Trifluoromethylphenyl 2-methoxyphenyl
2-chlorophenyl
3-trifluoromethylphenyl 2-fluoro-4-chlorophenyl
2,3-dimethylphenyl
2,6-dimethoxyphenyl
3,4- dichlorophenyl
4-chlorophenyl
Cl
R2
CHs
CH3
CH3
C2H5 n-C6H13
CH3
CH3
1-C 3 H 7 cyclobutyl 1-C 1 H p n-C 1 H 8 n-C 6 H 13 n-C 4 H 9
CH 3 n-C 6 H 13 cyclohexyl n-C 3 H 7
CHs
CH 3 t-C 1 H 9 cyclopentyl
CH3 n-CiHa
CHs cyclopropyl
S-C4H9
1,1-dimethylpropyl
C2H5 n-CsHi
2.4-Dichlorophenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl
4-fluorophenyl
4-chlorophenyl
4-phenylphenyl
2,4- dichlorophenyl
3-Trifluoromethylphenyl
2-methoxyphenyl
4-fluorophenyl
4-t-butylphenyl
4-bromophenyl
4-methylthiophenyl
4-methoxyphenyl
4-methylphenyl
4-chlorophenyl at 110-130 ° C (13.33 Pa)
X = Ri, Ri '
R2
R3 phenyl
1-Naphthyl
4-Phenoxyphenyl
4-fluorophenyl
4-chlorophenyl
4-bromophenyl
3,5-dimethylphenyl
4-fluorophenyl
4-phenylphenyl
3-methylphenyl
3,4-dichlorophenyl
4-fluorophenyl mp 57-60 ° C
Example 14
Preparation of chloro (chloromethyl) methyl (phenyl) silane
A solution of 12.7 mL (16.4 g, 0.10 mol) of chloromethyl (dichloro-methylsilane in 200 mL of ether) was cooled to -70 ° C under a nitrogen atmosphere and stirred vigorously with the addition of 55 mL (0.10 moles). )
A 1.8 molar solution of phenyllithium in ether-cyclohexane (30:70) and 55 ml of ether was added dropwise at such a rate that the temperature of the mixture was kept below -70 ° C. The resulting suspension was stirred and warmed to room temperature and then allowed to stand overnight. Filtration and evaporation of the filtrate gave 20.4 g of a golden oil which was distilled to give 14.6 g (71%) of chloro (chloromethyl) methyl (phenyl) silane as a colorless liquid:
boiling point 71-74 [deg.] C under 1 mm Hg; n<sub>D</sub><sup>23</sup> 1,5337;
ir (neat) 3080, 3060, 2980, 2930, 1590, 1430,
1260, 1120, 820, 790, 740, 700 cm-1<sup>1</sup>;
NMR (CDCl3)
0.8 (3H, s);
3.1 (2H, s);
7.3 - 7.6 (3H, m),
7.6 - 7.8 (2H, m).
Example 15
Preparation of (1,1'-biphenyl-4-yl) chloro (chloromethyl jmethylsilane) (1,1'-Biphenyl-4-yl) chloro (chloromethyl j methylsilane) can be prepared by reacting an equimolar amount of 4-bromobiphenyl, chloromethyldichloro (methyl) silane and n. -butyllithium as described in Example 3.
Example 14a
Preparation of chloro [bis (4-fluorophenyl) Jinethylsilane
A suspension of 7.0 g (0.288 mol) of magnesium turnings in 50 ml of ether was stirred under a stream of nitrogen while dropwise addition of the solution.
50.2 g (0.287 mol) of 4-bromofluorobenzene in 200 ml of ether at such a rate that the temperature was maintained at reflux. After an additional two hours at reflux, the mixture was cooled rapidly in ice and a solution of 12.0 ml (0.096 mol) of chloromethyltrichlorosilane in 30 ml of ether was added dropwise. The resulting mixture was heated at reflux for 4 hours, cooled rapidly in ice, treated with a solution of 7.5 ml of isopropanol in 20 ml of ether, stirred for 5 minutes and filtered. The filtrate was evaporated to give an oil which was stirred in hexanes to form a suspension. Filtration in a stream of nitrogen and evaporation gave a mobile oil which was distilled to yield
17.6 g (61%) of the title compound, b.p. 100-140 ° C (13.32 Pa);
NMR (CDCl3)
3.3 (2H, sj)
7.1 (4H, t);
7.7 (4H, d from d).
Example 15
Preparation of (1,1'-biphenyl) chloro (chloromethyl jmethylsilane (1,1'-Biphenyl-4-yl) chloro (chloromethyl) methylsilane can be prepared by reacting an equimolar amount of 4-bromobiphenyl, chloromethyldichloro (methyl) silane and n-butyllithium as described in Example 3.
The compounds of Table V can be prepared as described in Examples 14, 14a and 15.
CbSiCH2Cl
The compounds listed in Table III were prepared by successively replacing the silicon-chlorine bond in a compound of the formula as described in Examples 12 to 13a.
Table III
Rz
AND
X - Si - CH 2 Cl
I: aotA »....
R3
X = R 1, R 1, R 2 R 3
<td>C2H5</td><td>C2H5</td><td>C2H5</td>
<td>1-C3H7</td><td>I-C3H7</td><td>1-C3H7</td>
<td>n-ClHg</td><td>n-C4H9</td><td>n-C4H9</td>
<td>U-CbH17</td><td>C2H5</td><td>cyclopentyl</td>
<td>n-C 14 H 29</td><td>cyclopropyl</td><td>1-methylbutyl</td>
<td>n-C 16 H 37</td><td>n-CeHu</td><td>n-C6H13</td>
<td>cyclopropyl</td><td>C2H5</td><td>S-C4H9</td>
<td>cyclohexyl</td><td>11-C3H7</td><td>n-C3H7</td>
<td>1-Naphthyl</td><td>11-C4H9</td><td>11-C4H9</td>
<td>2-Naphthyl</td><td>n-C4H9</td><td>cyclobutyl</td>
<td>phenyl</td><td>cyclopropyl</td><td>n-C6H13</td>
<td>4-phenylphenyl</td><td>n-C4H9</td><td>n-C4H9</td>
<td>4-phenylphenyl</td><td>11-C6H13</td><td>n-C6H13</td>
<td>4-phenylphenyl</td><td>cyclohexyl</td><td>cyclohexyl</td>
<td>4-chlorophenyl</td><td>11-C4H9</td><td>11-C4H9</td>
<td>4-fluorophenyl</td><td>U-C3H7</td><td>n-C3H7</td>
<td>4-Phenoxyphenyl</td><td>11-C4H9</td><td>cyclohexyl</td>
<td>4- (4-chlorophenoxy) phenyl</td><td>n-C4H9</td><td>nC & lt; H9</td>
<td>4-t-butylphenyl</td><td>S-C4H9</td><td>1-C4H9</td>
<td>3-methoxyphenyl</td><td>C2H5</td><td>t-C 6 H 8</td>
<td>3-trifluoromethylphenyl</td><td>S-C4H9</td><td>S-C4H9</td>
<td>2-thiomethylphenyl</td><td>1-C3H7</td><td>3-methylbutyl</td>
<td>2-phenylphenyl</td><td>cyclohexyl</td><td>cyclohexyl</td>
<td>2,4-dichlorophenyl</td><td>n-CdHg</td><td>n-C4H9</td>
<td>2,6-dimethylphenyl</td><td>I-C4H9</td><td>t-CdHg</td>
<td>3,5-dichlorophenyl</td><td>cyclopentyl</td><td>cyclopentyl</td>
<td>3-methyl-4-chlorophenyl</td><td>S-C4H9</td><td>S-C4H9</td>
<td>C2H5</td><td>phenyl</td><td>phenyl</td>
<td>cyclohexyl</td><td>phenyl</td><td>phenyl</td>
<td>n-C 18 H 37</td><td>phenyl</td><td>phenyl</td>
<td>tl-C4H9</td><td>4-chlorophenyl</td><td>4-chlorophenyl</td>
<td>n-C 12 H 25</td><td>4-chlorophenyl</td><td>4-chlorophenyl</td>
<td>1-Naphthyl</td><td>4-fluorophenyl</td><td>4-fluorophenyl</td>
<td>cyclopropyl</td><td>phenyl</td><td>4-t-butylphenyl</td>
<td>11-C4H9</td><td>phenyl</td><td>4-phenylphenyl</td>
<td>t-CdHg</td><td>phenyl</td><td>2,4-dichlorophenyl</td>
<td>11-C3H7</td><td>phenyl</td><td>3-trifluoromethylphenyl</td>
<td>I-C4H9</td><td>phenyl</td><td>3,5-dichlorophenyl</td>
<td>cyclopentyl</td><td>phenyl</td><td>2,6-dimethoxyphenyl</td>
<td>n-CidH29</td><td>4-chlorophenyl</td><td>2-fluorophenyl</td>
<td>n-CdHg</td><td>4-fluorophenyl</td><td>4-phenylphenyl</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>4-chlorophenyl</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>4-fluorophenyl</td>
<td>4-phenylphenyl</td><td>4-Phenylphenyl</td><td>4-phenylphenyl</td>
<td>2,4-dichlorophenyl</td><td>2,4-dichlorophenyl</td><td>2,4-dichlorophenyl</td>
<td>phenyl</td><td>4-fluorophenyl</td><td>4-fluorophenyl</td>
<td>phenyl</td><td>4-chlorophenyl</td><td>4-chlorophenyl</td>
<td>phenyl</td><td>4-phenylphenyl</td><td>4-phenylphenyl</td>
<td>phenyl</td><td>2,4-dichlorophenyl</td><td>2,4-dichlorophenyl</td>
<td>2-Naphthyl</td><td>4-methylthiophenyl</td><td>4-methylthiophenyl</td>
<td>4-chlorophenyl</td><td>2-methoxyphenyl</td><td>2-methoxyphenyl</td>
<td>4-chlorophenyl</td><td>3-chlorophenyl</td><td>3-chlorophenyl</td>
<td>phenyl</td><td>2-chlorophenyl</td><td>4-fluorophenyl</td>
X = Ri, Ri '
R2
4-fluorophenyl
4-chlorophenyl
4-fluorophenyl
2,4-dichlorophenyl
2,4-dichlorophenyl
2,4-dichlorophenyl 2,6-dimethoxyphenyl
3,4-dichlorophenyl 4-methylphenyl
2-chlorophenyl
4-phenylphenyl 4-phenylphenyl 4-phenylphenyl 4-fluorophenyl 4-chlorophenyl
1-naphthyl 4-phenoxyphenyl 4-methylphenyl
Example 12
Preparation of (1,1'-biphenyl-1-yl) (chloromethyl) diethylsilane (Ι, Γ-Biphenyl-1-yl) (chloromethyl) diethylsilane can be prepared by the method of Example 1 using chlorochloromethyldiethylsilane instead of chlorochloromethyldimethylsilane.
Similar compounds can be prepared by the method of Examples 1-5 from suitable organolithium or Grignard compounds and compounds of formula
Cl (R 2) Si (R 3) CH 2 Cl
The desired chlorochloromethyl dialkylsilanes are prepared from a compound of formula
ml of ethyl acetate to remove any residual phenyllithium, washed with water and brine, dried over magnesium sulfate and evaporated to give 33 g of a sticky solid. Recrystallization from 30 ml of cyclohexane gave 15.8 g (51% of theory) of chloromethyltriphenylsilane as a white solid:
mp 112-115 ° C;
ir (Nujol<sup>R</sup>) 1420, 1110, 735, 730, 705, 695 centimeters to <sup>-1</sup>;
NMR (CDCl3)
3.5 (2H, s);
7.0 - 7.8 (15H m).
Cl3SiCH2Cl
Example 13a using two equivalents of compound of formula
R 2 MgCl or R 2 L 1 if R 2 is the same as R 3 (see, for example, AA Ždanov, VI Pachomov and T. Bazanova, Žur. Obščej. Chim., 1973, p. 1280), or using one equivalent of a compound of formula
R 2 MgCl or R 2 L 1 and then one equivalent of a compound of formula
R3MgCl or R3L1 when R2 and R3 do not have the same meaning.
Example 13
Preparation of (chloromethyl) triphenylsilane
A solution of 12.6 mL (18.4 g, 0.10 mol) of (chloromethyl jtrichlorosilane) in 150 mL of dry ether was stirred under nitrogen and cooled with ice while adding 162 mL (0.30 mol) of 1.85 molar phenyllithium solution. in a 70: 30 cyclohexane-ether system dropwise at a rate such that the temperature of the mixture was maintained below 15 [deg.] C. The resulting suspension was stirred overnight at room temperature, carefully treated with 10 ml.
Preparation of chloromethyl [tris (4-chlorophenyl)] silane
A solution of 24.5 g (0.128 mol) of 4-bromochlorobenzene in dry tetrahydrofuran was cooled to -60 ° C under a stream of nitrogen and 80 ml (0.128 mol) was added with stirring.
Of a 1.6 molar solution of n-butyllithium in hexane at a rate such that the temperature of the mixture was maintained below -50 ° C. The resulting solution was stirred for an additional 10 minutes at -60 to -70 ° C and then a solution of 5.2 ml (0.041 mol) of chloromethyltrichlorosilane in tetrahydrofuran was added dropwise over 30 minutes. The resulting solution was stirred at RT. at -70 ° C for one hour, allowed to warm to room temperature, quenched with saturated aqueous ammonium chloride, and extracted with ether. The ether solution was washed with brine, dried over magnesium sulfate and evaporated to give a viscous oil which was chromatographed on silica gel (hexane elution) to give
9.1 g (53% of theory) of the title compound as a colorless oil which solidifies on standing:
mp 89-93 ° C;
NMR (CDCl3)
3.4 (2H, s,
7.5 (12H, broad ref.
Table II
CH3
AND
X - Si - CH 2 Cl
AND
R2
X = R1, R1 *
C2H5
I-C3H7
II-C 4 H 9 n-C 10 H 11 n-C 18 H 17 cyclopropyl cyclohexyl
1- Naphthyl
2-naphthyl phenyl phenyl phenyl
4-phenylphenyl
4-bromophenyl
4-fluorophenyl
4-Phenoxyphenyl
4-t-butylphenyl
3-Trifluoromethylphenyl 3-chlorophenyl 2-thiomethylphenyl 2-phenylphenyl 2,4-dichlorophenyl
2,4- dichlorophenyl
2,3-dimethylphenyl
2-methyl-5-fluorophenyl
2,5-dimethoxyphenyl
2,6-dimethylphenyl
3,5-dichlorophenyl
3,5-Diclorophenyl
3-Methyl-4-chlorophenylphenyl
4-fluorophenyl
4-chlorophenyl
4-bromophenyl
4-phenylphenyl
4-t-butylphenyl
4-thiomethylphenyl
4-Phenoxyphenyl
4-Trifluoromethoxyphenyl 4-methylsulfonylphenyl 4-cyclohexylphenyl 4- (4-fluorophenyl) phenyl
3-Trifluoromethylphenyl 2-chlorophenyl 2-methoxyphenyl 2-chloro-4-phenylphenyl
2-fluoro-4-phenylphenyl
3,5-dichlorophenyl
2,5-dimethoxyphenyl
2,6-dimethoxyphenyl
4-bromophenyl
4-phenylphenyl
4-methoxyphenyl
3-Trifluoromethylphenyl 2-methoxyphenyl 2-chlorophenyl
2,4- dichlorophenyl
3,5-dichlorophenyl
R2
C 2 H 5 cyclohexyl n-C 4 H 8 cyclopropyl
3-Methylbutyl n-CsH13 cyclohexyl t-C1Ho n-CsHu n-C3H7 n-ChHg
1,1-dimethylpropyl
C2H5
1-C 3 H 7 n-C 1 H 8 t-C 4 H 9 cyclopentyl
S-C 4 H 9 n-C 5 H 11 cyclobutyl
1- C 4 H 9 n-C 6 H 8 cyclopropyl
II-C3H7 cyclopentyl
4-methylpentyl
1-methylbutyl n-C4Hg cyclohexyl cyclopropyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl
4-bromophenyl
4-phenylphenyl
3-methoxyphenyl
3-Trifluoromethylphenyl
4-methoxyphenyl
2-chlorophenyl
2,4- dichlorophenyl
3,5-dichlorophenyl
tv 45 ° C
tv 82 to 90 ° C (13.33 Pa)
tv 90-92 ° C (13.33 Pa)
tv 109 to 112 C (13.33 Pa)
mp 104-110 ° C (26.66 Pa) n<sub>D</sub><sup>22</sup> 1,5624
tv 140 to 148 ° C (13.33 Pa) tv 145 to 155 ° C (13.33 Pa) tv 173 to 178 ° C (13.33 Pa)
tv 132-135 ° C (13.33 Pa)
tv 160-170 ° C (13.33 Pa)
mp 115-117 ° C
tv 166-171 ° C (13.33 Pa)
mp 135-140 ° C (13.33 Pa) n<sub>0</sub>2l 1,5956
NMR (CDCl3)
0.7 (3H, s);
3.1 (2H, s).
7.2-7.7 (8H, m);
Analysis for C14H13Cl3Si (molecular weight 315, 70) calculated:
C 53.26 H 4.15 Cl 33.69 found:
C 53.4 H 4.4 Cl 34.2
C 53.5 H 4.4 Cl 34.1
Example 10
Preparation of (chloromethyl) bis (4-fluorophenyl) methylsilane
A solution of 35 g (0.20 mol) of 5-fluorobromobenzene in 300 ml of dry tetrahydrofuran was cooled to -60 ° C under nitrogen and stirred while adding 126 ml (0.20 mol) of a 1.6 molar solution of n-butyllithium in hexane dropwise and at a rate to maintain the temperature of the mixture below -55 ° C. Stirring and cooling was continued with the dropwise addition of 12.6 ml (16.4 g, 0.10 mol) of chloromethyl (dichloro) methylsilane at a rate to maintain the temperature of the mixture below -50 ° C. The resulting solution was allowed to warm to room temperature and treated as described in Example 8 to give 26.4 g of a clear yellow liquid. Distillation gave 20.6 g (73%) of (chloromethyl) bis (4-fluorophenyl) methylsilane as a colorless liquid;
bp 107-127 ° C (at 13.33
Bye);
n<sub>D</sub><sup>22</sup> 1,5481;
NMR (CDCl3)
0.7 (3H, s);
3.2 (2H, s).
7.1 (4H, t, J = 9)
7.6 (4H, d, z, D1) = 6 and 9).
Repeating the procedure using chloromethyl (diethoxy) methylsilane instead of dichlorosilane gave (chloromethyl) bis (4-fluorophenyl) methylsilane in a yield of 58% of theory after distillation:
NMR (CDCl3) see above.
A similar sample of the title compound after recrystallization from ether-hexane at -78 ° C gave a colorless solid, mp 39-40 ° C.
Example 11
Preparation of chloromethyl (2-chlorophenyl) (4-chlorophenyl) methylsilane
A solution of 6.3 ml (8.2 g, 0.05 mol) chloromethyl (dichloro) methylsilane and 8.1 g (0.05 mol)
2-Bromo-chlorobenzene in 75 mL of dry tetrahydrofuran was cooled to -60 ° C under a nitrogen atmosphere and stirred while 31 mL (0.05 mol) of a 1.6 molar solution of n-butyllithium in hexane was added at such a rate that the temperature of the mixture maintained below -55 ° C. Stirring and cooling was continued with the addition of 8.1 g (0.05 mol) of 4-bromochlorobenzene as a solid followed by addition of an additional 31 mL portion of 1.6 molar n-butyllithium solution at such a rate that the temperature of the mixture was kept below. —55 ° C. The resulting slurry was allowed to warm to room temperature, treated cautiously with 10 mL of ethyl acetate and then treated as described in Example 8 to give 15.0 g of a clear yellow oil. Distillation yielded 5.9 g (37%) of chloromethyl (2-chlorophenyl) (4-chlorophenyl) methylsilane: bp 150-165 [deg.] C at 10 mmHg;<sub>D</sub><sup>20</sup> 1,5916;
ir (neat) 3060, 3020, 2960, 2870, 1580, 1560,
1490, 1420, 1380, 1255, 1125, 1115, 1085,
1035, 1015, 805, 750 cm-<sup>1</sup>;
NMR (CDCl3)
0.8 (3H, s);
3.3 (2 H, s),
7.2-7.7 (8H, m).
The compounds of Table II are prepared by successively replacing the silicon and chlorine bonds of the compound of formula
Cl 2 Si (CH<sub>3</sub>CH 2 Cl 2 as described in Examples 6-11.
boiling point 115-138 ° C at 25.66 Pa; n<sub>D</sub><sup>21</sup> 1,5464;
238826 residue in hexanes, re-filtered and evaporated to give 19.8 g of a slightly orange liquid. By distillation, first 1.8 g (12%) of chloromethyl (-dibutyl) methylsilane having a boiling point of 45 DEG C. at a pressure of 6.66 Pa were obtained, followed by 6.8 g (35%) of butyl (chloromethyl) (4-chlorophenyl) methylsilane. in the form of a colorless liquid:
boiling point 90 ° C at 6.66 Pa; n<sub>D</sub><sup>21</sup> 1,5246;
ir (neat) 2925, 1580, 1260, 1090, 1015, 820,
740 cm '<sup>1</sup>;
NMR (CDCl 3)
0.4 (3H, sj,
0.6-1.5 (9H, m),
2.9 (2 H, s),
7.0-7.4 (4H, qj).
Example 8
Preparation of chloromethyl (2,4-dichlorophenyl) methyl (phenyl jsilane)
A solution of 13.6 g (0.060 mol) of 2,4-dichlorobromobenzene and 12.3 g (0.060 mol) of chloro (chloromethyl) methyl (phenyl) silane, prepared as described in Example 14, in 85 ml of dry tetrahydrofuran is rapidly cooled to room temperature. -60 ° C under a nitrogen atmosphere and stirred while adding 38 mL (0.060 mol) of a 1.6 molar solution of n-butyllithium in hexane dropwise at such a rate that the temperature of the mixture was maintained below -55 ° C. The resulting red solution was allowed to warm to room temperature, treated with 5 mL of ethyl acetate to remove any unreacted excess organolithium reagent and poured into 170 mL of water.
The organic layer was separated, the aqueous phase was washed with 50 ml of hexane, and the combined organic phases were washed three times with water, once with brine, dried over magnesium sulfate and evaporated to give 19.0 g of a bright yellow oil. Distillation gave 8.6 g (45% of theory) of chloromethyl (2,4-dichlorophenyl) methyl (phenyl) silane as a colorless liquid: boiling point 125-130 [deg.] C at 6.66 Pa;<sub>D</sub><sup>21</sup> 1,5978;
ir (neat) 3080, 3060, 2960, 2930, 1570, 1540,
1460, 1430, 1365, 1260, 1120, 1100, 1040,
820, 745, 735, 705 cm-<sup>1</sup>;
NMR (CDCl3)
0.8 (3H, s);
3.4 (2H, s);
7.2 - 7.9 (8H, m).
Example 8a
Preparation of (Ι, Γ-biphenyl-4-yl) chloromethyl (4-fluorophenyl) methylsilane
A solution of 10.0 g (32.8 mmol) of (1,1'-biphenyl-4-yl) (chloromethyl) methyl (2-propoxy) silane and 3.6 ml (32.8 mmol) of 4-bromofluorobenzene in 30 mL of dry tetrahydrofuran was cooled to -60 ° C under a stream of nitrogen and stirred with the addition of 20.5 mL (32.8 mmol)
Of a 1.6 molar solution of n-butyllithium in hexane at a rate such that the temperature of the mixture was maintained below 50 ° C. Stir at -70 degrees Celsius for an additional 30 minutes, allow the solution to warm to room temperature and work up as described in Example 8. The resulting crude product is distilled at a temperature of 130-150 ° C removal of unreacted starting materials to give the title compound as an oil:
n<sub>D</sub><sup>23</sup> 1,5128;
NMR (CDCl 3)
0.7 (3H, s);
3.1. (2H, S).
7.1 (2 H, t),
7.2 - 7.8 (11H, inter alia.
Example 9
Preparation of chloromethyl [bis (4-chlorophenyl)] methylsilane
A solution of 4-chlorobromobenzene (19.1 g, 0.10 mol) in dry tetrahydrofuran (200 ml) was rapidly cooled to -60 ° C under a nitrogen atmosphere and stirred with the addition of 63 ml (0.10 mol) of a 1.6 molar solution. n-butyllithium in hexane was added dropwise at a rate such that the temperature of the mixture was maintained below -55 ° C. Stirring and cooling was continued with the addition of 6.3 ml (8.2 g, 0.05 mol) of chloromethyl (dichloro-methylsilane) dropwise and at a rate such that the temperature of the mixture was kept below -50 ° C. The resulting orange solution was allowed to warm to room temperature and treated as in Example 8 to give 16.5 g of a slightly yellow oil. Distillation in a flask at 6.66 Pa and at an air bath temperature of 130-150 ° C afforded 9.5 g (60% of theory) of chloromethyl [bis (4-chlorophenyl) methylsilane as a colorless liquid:
n<sub>D</sub><sup>24</sup> 1,5913;
ir (neat) 3080, 3040, 3020, 2960, 2930, 1580,
1490, 1380, 1260, 1085, 1015, 805, 790, 775,
740 cm<sup>-1</sup>;
X = Ri or Ri '
4- (4-Methylphenyl) phenyl 4- (4-trifluoromethylphenyl) phenyl 4- (4-fluorophenyl) phenyl
3-phenylphenyl
3-Trifluoromethylphenyl 3-chlorophenyl
2-trifluoromethylphenyl 2-phenylphenyl 2-chlorophenyl 2-methoxyphenyl
2,3-dimethylphenyl
2,3-dimethoxyphenyl
2,4-difluorophenyl
2-fluoro-4-chlorophenyl
2-chloro-4-phenylphenyl
2-fluoro-4-phenylphenyl
2-methyl-5-chlorophenyl
2,6-dimethylphenyl
3,4-dichlorophenyl t.
3-methyl-4-fluorophenyl
3,5-dichlorophenyl t.
Example 6
Preparation of (1,1'-Biphenyl-4-yl) butyl (chloromethyl) methylsilane (1,1'-Biphenyl-4-yl) butyl (chloromethyl) methylsilane can be prepared as described in Example 1 using (butyl jchlor (chloromethyl) methylsilane) instead of chloro (chloromethyl) dimethylsilane.
Related compounds can be prepared by the method of Examples 1-5 using suitable organolithium compounds or Grignard reagents and suitable compounds of formula
Cl (R 2) Si (CH 3) CH 2 Cl
The necessary chloromethylsilane starting materials are prepared from a compound of formula
R2MgCl or R2L1 and from CbSi (CH5) CH2Cl as described in Examples 14 and 15 and, for example, VP Kuznetsov and RM Sololovaska in the journal Zur. Obščej. Chim., 1969, p. 1997.
Alternatively, both biphenyl and butyl groups can be simultaneously introduced as follows:
A solution of 23.3 g (0.10 mol) of 4-bromobiphenyl and 12.7 ml (16.4 g, 0.10 mol) of chloromethyl (dichloro-methylsilane) in 150 ml of dry tetrahydrofuran is rapidly cooled to -70 ° under nitrogen. C. and stirred while adding 125 mL (0.20 mole) of a 1.6 molar solution of n-butyllithium in hexane at such a rate that the temperature of the mixture was kept below -60 [deg.] C. The resulting slurry was allowed to warm to room temperature. The reaction mixture was treated with 10 ml of ethyl acetate and poured into 300 ml of water. The organic layer was separated, the aqueous phase was washed further<sub>D</sub><sup>20</sup> 1,5862
t 59 to 62 ° C (39,99 Pa) t 73 ° C (19,99 Pa) n<sub>D</sub><sup>23</sup> 1,4826 n<sub>D</sub><sup>20</sup> 1,5772
mp 78-80 ° C (39,99 Pa) n<sub>D</sub><sup>21</sup> 1,5164 n<sub>D</sub><sup>22</sup> 1,5254
98 ° C (79.98 Pa)
v. 94-95 [deg.] C. (100 mm Hg) with 100 ml of hexane and the combined organic phases were washed three times with water, once with brine, dried (MgSO4) and evaporated to give 33.9 g of a viscous yellow oil. Distillation yielded 9.5 g (31% of theory) of (1,1'-biphenyl-4-yl) butyl (chloromethyl) methylsilane.
Boiling point 133-158 ° C at 13.33
Bye;
n<sub>D</sub><sup>22</sup> 1,5743;
ir (neat) 3060, 3015, 2960, 2920, 2870, 1600,
1485, 1390, 1380, 1250, 1120, 1075, 1005,
875, 800, 760, 700 cm-<sup>1</sup>;
1 H NMR (CDCl 3)
0.4 (3 H, s),
0.6 - 1.8 (9H, ia,
2.9 (2H, s) a
7.0 - 7.7 (9H, m).
Example 7
Preparation of butyl (chloromethyl) (4-chlorophenyl) methylsilane
A solution of 14.4 g (0.075 mol) of 4-bromochlorobenzene and 9.5 ml (12.3 g, 0.075 mol) of chloromethyl-dichloro-methylsilane in 150 ml of tetrahydrofuran was cooled to -60 ° C under nitrogen and stirred with the addition of 94 ° C. ml (0.15 mol) of a 1.6 molar n-butyllithium solution in hexane dropwise at a rate such that the temperature of the mixture was maintained at -65 to -55 ° C. The resulting suspension was allowed to warm to room temperature to give a solution which was diluted with hexane until no more lithium chloride precipitated. Filtration, evaporation of the filtrate, dissolution
2β
NMR (CDCl3)
0.5 (6Η, s),
3.1 (2H, s);
7.0 - 7.5 (3H, m).
Example 5
Preparation of chloromethyl (2,6-dimethoxyphenyl) dimethylsilane
A solution of 1,3-dimethoxybenzene (25.0 g, 0.181 mol) in tetrahydrofuran (200 ml) was stirred at room temperature under a nitrogen atmosphere while adding 125 ml (0.200 mol) of a 1.6 molar solution of n-butyllithium in hexane dropwise over the course of 30 minutes. The resulting mixture was heated to reflux for 1.5 hours to give an orange-brown solution, which was cooled to 5 ° C and stirred with the addition of 27 mL (29.4 g, 0.205 mol) of chloro (chloromethyl) dimethylsilane. dropwise over 15 minutes. The resulting white suspension was allowed to warm to room temperature, stirred for one hour, diluted with ethyl acetate, poured into water and extracted with ether. The organic layers were washed with brine, dried over magnesium sulfate and distilled to give 37.0 g (84%) of chloromethyl (2,6-dimethoxyphenyl) dimethylsilane as a colorless liquid:
boiling point 98-110 ° C at 1 mm Hg; NMR (CDCl3)
0.4 (6H, s);
3.1 (2H, s).
3.7 (6 H, s),
6.3 (2 H, d),
7.1 (1 H, m).
Using various organolithium compounds or Grignard reagents, the compounds of Table I can be prepared by the method of Examples 1-3. Soc., 1954, p. 4266. For compounds wherein R 1 is a phenyl ring with a substituent at the 2-position, an alternative to the in situ method of Example 4 is the special arylmagnesium iodide procedure described by C. Eaborn, KL Jaura and DRM Walton, J. Chem. Soc., 1964, 1198,
X = Ri or Ri '
C2H5 n-CdHg n-C12H5
11-C18H37 cyclopropyl cyclopentyl cyclohexyl
1- Naphthyl
2-naphthyl phenyl
4-fluorophenyl
4-methoxyphenyl
4-Phenoxyphenyl
4- (4-chlorophenoxy) phenyl
4- (4-fluorophenoxy) phenyl
4- (4-Trifluoromethylphenoxy) phenyl
4- (4-methylphenoxy) phenyl
4-thiomethylphenyl
4-trifluoromethylphenyl
4-methylphenyl
4-i-Propylphenyl
4-t-butylphenyl
4-methylsulfonylphenyl
4-cyclohexylphenyl
4-trifluoromethoxyphenyl
4- (4-chlorophenyl) phenyl
4- (4-Bromophenyl) phenyl
Table I
CHs
AND
X - Si - CH 2 Cl
AND
CHs
t 127 to 128 ° C t 172 ° C n<sub>D</sub><sup>23</sup> 1,4510 n<sub>D</sub><sup>22</sup> 1,4556
tv 120-130 ° C (1333 Pa) tv 112 ° C (10.66 Pa)
tv 85 to 86 ° C (399.9 Pa) tv 59 to 60 ° C (13.33 Pa) tv 80 ° C (6.66 Pa) tv 122 ° C (3.99 Pa) n<sub>D</sub><sup>22</sup> 1,5773
mp 92-93 ° C (6.66 Pa) n<sub>D</sub><sup>23</sup> 1,4686
tt 96 ° C (933.1 Pa) n<sub>D</sub><sup>23</sup> 1,5056
mp 64-68 ° C n<sub>D</sub><sup>21</sup> 1,5424
55-57 ° C (19,99 Pa) is not agitation. While cooling, 5.9 ml (6.7 µg, 0.046 mol) of chloro (chloromethyl) dimethylsilane are added over 10 minutes to give a clear solution which is allowed to warm to room temperature. the precipitated lithium chloride and the filtrate were evaporated to yield
13.2 g semi-solid. Redissolved in ether, filtered and evaporated to afford 11.0 g (100% crude) of Ι, Γ-biphenyl-4-yl (chloromethyl) dimethylsilane as a colorless solid, m.p. Traces of impurities can be removed by sublimation at 30 ° C at 13.33 Pa to give 1,1'-biphenol-4-yl (chloromethyldimethylsilane unsublimed in 83% yield, m.p. Mp 37-40 ° C;
ir (Nujol<sup>R</sup>1585, 1240, 1110, 830, 810, 750, 690 cm<sup>-1</sup>;
NMR (CDCl3)
0.4 (6H, s,
2.9 (2 H, s),
7.3-7.7 (9H, m).
Example 2
Preparation of (4-bromophenyl) (chloromethyl) dimethylsilane
4-Bromophenyl magnesium bromide was prepared from 11.8 g (0.050 mol) of 1,4-dibromobenzene and
1.2 g (0.050 gatoms) of magnesium shavings in 75 ml of ether according to GP Schiemenz, Org. Syn., Coll. Vol. 5, p. 496: (1973). The resulting mixture was rapidly cooled in ice under nitrogen atmosphere while dropwise addition of the solution.
6.6 ml (7.2 g, 0.050 mol) of chloro (chloromethyl) dimethylsilane in 10 ml of ether are then stirred overnight at room temperature, carefully quenched with saturated aqueous ammonium chloride solution and filtered. brine, dried (MgSO4) and evaporated to give 9.8 g of an oil, distilling to give 3.8 g (29%) of (4-bromophenyl) (chloromethyl dimethylsilane) as a colorless liquid:
boiling point 97 ° C (133.3 Pa), ir (neat) 2950, 1575, 1475, 1370, 1250 ,. 1065, 1010, 840, 805, 720cm<sup>1</sup>;
NMR (CDCl3)
0.4 (6H, s,
2.9 (2 H, s),
7.3-7.7 (4H, m).
Example 3
Preparation of chloromethyl (4-chlorophenyl) dimethylsilane
A solution of 9.6 g (0.050 mol) of 4-bromochlorobenzene and 6.6 ml (7.2 g, 0.050 mol) of chloro (chloromethyl) dimethylsilane in 75 ml of tetrahydrofuran was stirred at -78 ° C under nitrogen with the addition of 31 ml ( The resulting clear solution was allowed to warm to room temperature, diluted with ether until no more lithium chloride precipitated and was filtered. Evaporation of the filtrate gave 10.6 g of a pale yellow liquid which, by distillation, yielded 6.0 g (55% yield) of chloromethyl (4-chlorophenyl) dimethylsilane as a colorless liquid:
bp 54-55 ° C at 1 mm Hg;
ir (neat) 2910) 1560, 1470, 1370, 1250, 1080,
1010; 840, 805, 790, 740 cm<sup>1</sup>;
NMR (CDCl3)
0.4 (6H, s);
2.9 (2 H, s),
7.1 - 7.6 (4H, q).
The in situ aryllithium preparation described in this example is also suitable for the preparation of the product of Example 1. When the reaction is carried out with 0.5 to 0.7 molar amounts of 4-bromobiphenyl and> maintained at -65 to -55 ° C during addition of butyllithl, no precipitate forms or only slightly solid precipitates. Example 4
Preparation of chloromethyl (2,4-dichlorophenyl) dimethylsilane
A solution of 17.0 g (0.075 mol) of 2,4-diclilorbromobenzene and 10.8 ml (11.8 g, 0.082 mol) of chloro (chloromethyl) dimethylsilane in 100 ml of dry tetrahydrofuran is rapidly cooled to -70 ° C under a nitrogen atmosphere and stirred with the addition of 49 ml (0.079 mol)
A 1.6 molar solution of n-butyllithium in hexane dropwise at a rate such that the temperature of the mixture was maintained below -70 ° C. The resulting cloudy reaction mixture was allowed to warm to room temperature, poured into 400 mL hexane, filtered and evaporated to give
20.5 g of yellow liquid. Distillation was obtained
12.6 g (66% of theory) of chloromethyl (1,2,4-dichlorophenyl) dimethylsilane as a colorless liquid:
bp 83 [deg.] C at 2.65 Pa; n<sub>D</sub>24 1,5522;
ir (neat) 1565, 1455, 1360, 1255, 1100, 1040,
825 cm "<sup>1</sup>;
3 8 6.2 Ο
CHs CH3
II
CL · —Si — CH2Cl + ArLi ---> C1 — Si — CH2Cl
AND
Ar
In both cases, the organometallic reagent should be added to the dichlorosilane at a temperature with good mixing to achieve the best yields.
Reaction of compound of formula
C 13 SiCH 2 Cl with Grignard reagents was described by AA Zdanov, VI Pakhomov and T. Bazanov in the journal Zur. Obščej. Chimii, 1973, 1280, Chem. Abstr. 79, 66452 m. The addition of organometallic reagents to trichlorosilane is also recommended when three identical groups are to be introduced, as the addition of a compound of formula
Cl3SiCH2Cl to organometallic reagent
<td colspan="2">saw was not successful. It can also be introduced</td>
<td>single aryl group:</td><td>Cl</td>
Cl 3 SiCH 2 Cl + ArLi --- Ar-Si-CH 2 Cl
Cl
A useful modification of methods known in the art useful when R 1 or R 1 'is an aryl group is described herein. Instead of the previously prepared organolithium reagent and its subsequent mixing with chlorosilane, it was found that aryl bromide and chlorosilane such as a compound of formula
ClSi (CH 3) 2 CH 2 Cl can be mixed in an inert solvent such as tetrahydrofuran and can be treated at -80 to -40 ° C with butyllithium. The bromine-lithium exchange is selective and the aryllithium formed reacts with the silicon-chlorine bond as soon as the bond is formed:
CH3 | n-CaHaLi
ArBr + Cl-Si-CH 2 Cl ---.
| —CaHgBr
CH3
CH, <sup>3</sup>
ArLi + Ct-Si.-CH.Ct <sup>and</sup> ch<sub>5</sub>
CH3
AND
---- ► Ar — Si — CH2Cl — face I
CH3
This reaction proceeds as well for aryl substituted chlorosilanes such as a compound of formula
ClSi (CH3) (C6Hg) CH2Cl and can be used to introduce two aryl groups into a compound of formula
Cl 2 Si (CH 3) CH 2 Cl
In addition, aryl and n-butyl groups can be introduced in one step.
CH3 CH3 | 2n-C4H9Li |
ArBr + Cl 2 S 1 - CH 2 Cl ----> Ar - Si - CH 2 Cl
In-C4H9
Replacing n-butyllithium with another alkyl lithium compound of formula RLi provides a general process for preparing compounds of formula
Ar (CH 3) Si (R) CH 2 Cl
In the following examples, temperatures are given in degrees Celsius. Abbreviations have the following meanings:
NMR = nuclear magnetic resonance, s = singlet, d-doublet, t = triplet, q = quartet, m-multiplet;
the peak position is reported as parts per million with respect to internal tetramethylsilane. The position of the infrared (IR) peak is given in reciprocal centimeters (cm -1)<sup>1</sup>). By hexanes is meant a mixture of isomers having a boiling point of 68-69 ° C and ether means diethyl ether.
Example 1
Preparation of (1,1'-biphenyl-4-yl) (chloromethyl) dimethylsilane
A solution of 9.9 g (0.042 mol) of 4-bromobiphenyl in 50 ml of tetrahydrofuran was cooled to -78 ° C under nitrogen and stirred with dropwise addition of 26.5 ml (0.042 mol) of 1.6 molar n-butyllithium in hexane. within 15 minutes. A thick suspension is formed and tetrahydrofuran (35 ml) is added to facilitate 236262 a
IR-SC-CH3C1-
Cl ·
Glycol derivatives are similarly formed using diol instead of two molecules of a compound of formula ReOH.
Alternative synthesis of alkoxy (chloromethyl) silanes involves the selective replacement of one alkoxy group of dialkoxysilane with an organometallic reagent:
R2 | RiMgX (ReO6Si-CH2Cl2->)
RiL1 or RiNa
R2
AND
--- ►R1 - -
AND
ORe
The conditions of this reaction are further described under the additional condition that the organometallic compound is to be added to the dialkoxysilane.
The desired chloromethylsilane as starting material is prepared from commercially available chlorine (chloromethyl j dimethylsilane, chloromethyl (dichloro-methylsilane) or chloromethyltrichloromethylsilane
CH3
AND
Cl — Si — CH2Cl,
I ch<sub>3</sub>
CH3
AND
Cl — Si — CH2Cl,
AND
Cl or
R2
AND
CbSiCH 2 Cl -> R 1 -Si-CH 2 Cl
AND
R3
The silicon and chlorine bonds in these compounds react with organolithium, organosodium, or Grignard reagents to introduce alkyl and / or aryl groups in a manner known in the literature, while the carbon and chlorine bond remains intact. For silanes containing two or three silicon bonds
<img file="CS238626B2_D0011.tif" />
and chlorine, successive substitutions are possible, giving great possibilities for the meanings of R1 to R<sub>3</sub>. Bromosilanes, iodosilanes or alkoxysilanes may be used in place of chlorosilanes in these reactions. Preferred solvents for these reactions are ethers such as tetrahydrofuran, 1,2-dimethoxyethane and diethyl ether or hydrocarbons such as hexane and toluene. Temperatures of -80 to +40 ° C are preferred depending on the nature of the organometallic reagent as prepared and the solvent used. For example, when the aryl lithium reagents are prepared in tetrahydrofuran from aryl bromides using butyllithium, the mixture should be maintained at a temperature of about -40 ° C to avoid side reactions involving the formation of bromobutane. If the organometallic solution is stable at higher temperatures, the reaction can be carried out at a temperature of -20 ° C to +25 degrees Celsius without a competitive reaction on the CH 2 Cl 2 group. The reaction is rapid at all temperatures and only a short time is required, for example 30 to 60 minutes after mixing the reagents to ensure complete reaction.
Reaction of compound
ClSiCH5-CH2Cl2 with Grignard reagents are described by C. Eaborn and JC Jeffrey in J. Chem. Soc., 1954, p. 4266; recent description of the preparation of aryltrimethylsilanes from a compound of formula
ClSi (CH<sub>3</sub>j<sub>3</sub> and experimental conditions for the reactions of the compound of formula
ClSi (CH<sub>3</sub>12CH 2 Cl are described by D. Habich and F. Effenberger in Synthesis 1979, p. 841. Selective introduction of a new alkyl group into a compound of formula
Cl2Si (CH3) CH2Cl was described by VP Kuznetsov and RM Solokovaskaya in the journal Zur. Obščej. Chim., 1969, 1977; Chem. Abstr. 72, 31897 pa and one aryl group can be selectively introduced according to the equation:
23882B
Ri-SL-CH.Ct & lt; + & gt ;. <sup>1</sup> ii
Cl
0-4
VrN 2A / a <I
O,
R <
0-4
R,
0-,
<img file="CS238626B2_D0012.tif" />
GL.
OR, <3-,
Suitable solvents and reaction conditions are as described above for the azoles. The temperature of the alcoholysis is not critical and can be carried out by heating to 50 to 100 ° C to achieve complete reaction in cases where R 6 is C 1 -C 4 alkyl. However, in the case where R 5 is a hydrogen atom, hydrolysis preferably proceeds at a temperature close to room temperature to minimize disiloxane formation, since the silanol-disiloxane equilibrium is always possible when R 6 is a hydrogen atom
Q ,.
Rr Sů ~ <sup>7</sup> and
OH <sup>CH</sup>AND
<img file="CS238626B2_D0013.tif" />
The equilibrium and rate at which the equilibrium is adjusted depends on the importance of R1 and R2, the solvent selected, the temperature and the possible presence of acidic or basic catalysts.
In the second process, a silicon-oxygen bond is formed first, and then the azole is prepared as described above:
R,
Rx-Si-CH3CiQ-1
RrSi-CH<sub>?</sub>N <sup>1</sup> 1 R, i<sup>£</sup>
STEED,
OR, a,
The reaction of chlorosilane with a compound of formula ReOH can be carried out in almost any non-hydroxyl solvent with ethers such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran or in dipolar aprotic solvents such as dimethylformamide, with acetonitrile being preferred. Although it is not necessary to use an acid acceptor, it is preferable to add a tertiary amine such as triethylamine or pyridine. The reaction temperature may be 0 to 100 ° C and the compound of formula R 6 OH is often used in excess of the theoretical amount. Generally, 2 equivalents of the compound of formula R60H are used,
1.1 equivalents of triethylamine and 0.1 equivalents of imidazole in dimethylformamide at 80 DEG C. for two hours.
Using the following methods for (chloromethyl iodochlorosilanes) a strong one containing two oxygen atoms is obtained:
which has a singlet close to 2.9 and singlets of the product
The S1CH2N derivative at the 4-position of the substituted 10: 1 derivative.
which is close to 3.8 for compounds of formula I and close to 3.7 for compounds of formula II.
With respect to the triazole derivatives of the formula I, the 1H-1,2,4-triazol-1-ylmethyl compound prepared as described above is accompanied by a smaller amount of the isomeric 4H-1,2,4-triazol-4-ylmethyl compound of the formula or
R, - 1
<img file="CS238626B2_D0014.tif" />
The ratio of isomers varies with the meaning of R and depending on the reaction conditions, roughly the ratio at the 1-position is substituted.
<sup>R</sup>ro N
1 »CjfHg LL
2-CH<sub>O</sub>J ll
RvSL-CH. <sup>1</sup> 1 t
R, r = N, J
CH <
In the case of imidazole derivatives of the general formula II, isomers are possible only if Q2 and Q3 do not have the same meaning. Two isomers are obtained:
CH »
R, -Si-cHjM formula IIA '
<img file="CS238626B2_D0015.tif" />
In general, the product of formula IIA predominates. Optionally, the isomers can be separated by standard methods such as crystallization, distillation or chromatography.
In the case where R5 is OR6 in the triazole or imidazole product, chlorine in chlorine (chloromethylsilane) can be replaced by one of two methods, in which at least two equivalents of the azole sodium salt can be used. azole bond and reaction with water or alcohol yields the desired oxygen-containing compound:
Formula IIB
23862-6
<td rowspan="2"></td><td colspan="2">„Wc. > = n</td>
<td> 1</td><td><sup>2</sup> > = A a,</td>
<td>of formula IIB</td><td></td><td></td>
<td>Isomers prevail,</td><td colspan="2">of formula IIA as a rule, however, isomers of formula</td>
where
HN. J> -N
Q 1, Q 2 and, Q 1 represent a hydrogen atom or a methyl group. When writing structural formulas take a structural share
Gkj
IIB also have fungicidal activity and isomer separation is not necessary.
In addition, the symbol Ri 'is also meant to mean that all the meanings of Ri' are included in the definition of Ri. The term "azole" continues to be used for suitably substituted 1,2,4-triazoles and imidazoles
<img file="CS238626B2_D0016.tif" />
<img file="CS238626B2_D0017.tif" />
where
X represents a nitrogen atom or CQ 3 group used to designate both the triazole and imidazole ring systems.
The active compounds of the formula I and II according to the invention can be prepared from the chloromethylsilanes and the 1,2,4-triazole or imidazole sodium salt or from their methyl-homologues:
<img file="CS238626B2_D0018.tif" />
<img file="CS238626B2_D0019.tif" />
Lithium and potassium azole salts may also be used. Instead of chloromethylsilanes, bromomethylsilanes, iodomethylsilanes or arylsulfonyloxymethylsilanes may be used. Approximately equimolar amounts of reagents are used (except when R5 is OR6, as described below), and the azole salts are often used in 5-10% excess above the theoretical amount. In addition, when an acid acceptor is added, 1,2,4-triazole or imidazole may be used as such. Suitable acid acceptors include excess azole, alkali metal alkoxides such as sodium methoxide or potassium tert-butoxide, inorganic bases such as potassium carbonate or hydride. sodium, and tertiary amines such as triethylamine. If the acid acceptor is well nucleophilic, such as sodium methoxide, excess use thereof should be avoided to avoid side reactions. Suitable solvents include polar aprotic solvents such as dimethylformaroid, dimethylsulfoxide or acetonitrile; ethers such as tetrahydrofuran or 1,2-dimethoxyethane; and ketones such as 2-butanone. The reaction temperature may be 0 to 200 ° C, preferably 25 to 100 ° C. The reaction may be carried out at elevated pressure, but it is generally preferred to work at atmospheric pressure. The optimum temperature and reaction time varies depending on the concentration and choice of the reactants, and particularly depending on the choice of solvent. For example, 1,2,4-triazole and sodium methoxide at about 2 molar concentration in dimethylformamide provide good conversion in about two hours at 80 to 90 ° C, whereas 1,2,4-triazole and potassium carbonate at about 1 molar concentration in butanone requiring reaction for 8-12 hours at reflux temperature. Imidazole reactions are generally faster. Generally, a reaction time of 1 to 24 hours is required. The progress of the reaction can be monitored by nuclear magnetic resonance analysis and by assessing the intensities of the starting material
SÍCH2CI
Butyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane;
Butyl (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane;
[bis (1,1'-Bisphenyl-4-yl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane;
(Ι, Γ-Biphenyl-4-yl) butyl (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane; and (1,1'-Biphenyl-4-yl) methyl (phenyl) ( 1H-1,2,4-triazol-1-ylmethylsilane).
Particularly preferred are compounds of formula II wherein R 1, R 2 or R 3 do not represent a C 1 -C 4 alkyl group or a phenyl group. The following compounds of formula II are preferred for their excellent activity and / or easiest process of preparation:
(1,1'-Biphenyl-4-yl) dimethyl (1'-imidazol-1-ylmethyl) silane;
(2,4-Dichlorophenyl) dimethyl (1H-Imidazol-1-ylmethyl) silane;
Butyl (2,4-dlchlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane;
[bis (4-Fluorophenyl)] (1H-imidazol-1-ylmethyl) methylsilane;
[bis (2,4-Dichlorophenyl)] (1H-imidazol-1-ylmethyl) methylsilane;
(2,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane;
(4-Chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane;
(4-Fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane;
(1,1'-Biphenyl-4-yl) butyl (1H-imidazol-1-ylmethyl) methylsilane;
(1,1'-Biphenyl-4-yl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane;
[bis (1,1-Biphenyl-4-yl)] (1H-imidazol-1-ylmethyl) methylsilane; · '' ''
Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane;
(4-Chlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane;
Dimethyl (4-fluorophenyl) (1H-imidazol-ylmethyl) silane;
Butyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) methylsilane.
When Q1 and Q2 are each hydrogen or methyl, a mixture of two isomers is generally obtained in the preparation of the triazole derivatives of formula (I):
Formula IB
R,
If the triazole substituent is a hydrogen atom and the other a methyl group, three isomers may be obtained:
/> M
R.-Are-CHrN J formula IC a
CH, formula ID a
of formula IE rSt-CH “Ν '
I z. \ I
R,
CH.
\ *
R<sub>r</sub>Sc-CH<sub>r</sub>N ^
R <
> ó t
R,
The mixture mainly comprises isomers of formula IA or formula IC; however, the isomers of formula IB, ID and IE also have fungicidal activity and separation of isomers is not necessary.
In the case of imidazole derivatives of the general formula (II), isomers are obtained when Qz and Q3 do not have the same meaning:
R ^ · CH /
Ø, <sup>N</sup>
Λ
R.-S1-CH, N1 = <sup>R</sup>sa)
Pl · formula IA formula IIA
R,
Rf Si CH<sub>3</sub><sup>R</sup>L <sup>1</sup>
R f Sl,
CH<sub>OF</sub>
ΊΓ
N
0-,
<img file="CS238626B2_D0020.tif" />
<img file="CS238626B2_D0021.tif" />
<img file="CS238626B2_D0022.tif" />
The invention also relates to salts of compounds of the formulas I and II with protic acids and their metal ion complexes.
The compounds of the formulas I and II are preferred for their activity and / or preferably for easy preparation
Q 1 = Q 2 = - = hydrogen
They are more preferred for their activity: and / or for a preferably easy method of preparing a compound wherein
R 1 and R 1 'are a group of the formula
<img file="CS238626B2_D0023.tif" />
R2 is alkyl having 1; up to 4 carbon atoms or a group of formula
<img file="CS238626B2_D0024.tif" />
R 5 is C 1 -C 4 alkyl.
Most preferred for their highest activity and / or for the easiest method of preparation are the compounds of formulas I and II wherein
R 1 and R 1 'are of the general formula
<img file="CS238626B2_D0025.tif" />
where it means
R 1 is para to R 1 or R 1 'and is hydrogen, fluoro, chloro or bromo, or phenyl; and
R 5 is hydrogen, fluorine, chlorine or bromine; and
R2 is a group of formula
R 1 or C 1 -C 4 alkyl and
R 5 is C 1 -C 4 alkyl.
The following compounds of the general formula I are particularly preferred for their excellent activity and / or for the easiest process of preparation:
(Dimethyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane;
Dimethyl (4-methylphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane;
(4-Bromophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane;
(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane;
(4-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethylsilane);
(2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane;
Butyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane;
bis (4-Chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane;
Methyl (diphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane;
(bis (4-Fluorophenyl)) methyl (1H-1,2,4-trlazol-1-ylmethyl) silane;
(4-Fluorophenyl) dimethyl (1H-1,2,4-triazol-L-ylmethyl) silane;
Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-4-ylmethyl) silane;
[bis (2,4-Dichlorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane;
2,4-Dichlorophenyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane;
4-Chlorophenyl (methyl J phenyl (1H-1,2,4-triazol-1-ylmethyl) silane;
4-Fluorophenyl (methyl J phenyl (1H-1,2,4-triazol-1-ylmethyl) silane;
or η
Οχ ζΟ of a gene and / or C 1 -C 4 alkyl and / or trifluoromethyl, trifluoromethyl, C 1 -C 4 alkyl or cyclohexyl group,
R 2 and R 3 independently of one another are C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, OR 6 or R 6
<img file="CS238626B2_D0026.tif" />
OxzO
R,
<img file="CS238626B2_D0027.tif" />
R<sub>F</sub>
The invention also relates to a method for combating fungal diseases of living plants by treating them with an effective amount of a compound of formula I or II
Kl / rzN Rj-SICHA-J
Q aj
R1 '/ ττΝ R<sub>OF</sub>-SLCH ^ <sup>r</sup>a and a;
where it means
R 6 is hydrogen or C 1 -C 4 alkyl, provided that R 2 and R 3 are not both hydroxyl and R 2 and R 5 may together form a 1,2-glycol, 1,3-glycol or 1,4-glycol bridge; , 4-unsaturated glycol bridge substituted with up to 4 R7-R10 alkyl groups having up to 4 carbon atoms in total
Rf R<sub>10</sub>
<img file="CS238626B2_D0028.tif" />
or where it is
Q1, Q2 and Q3 independently of one another are hydrogen or methyl,
R 1 and R 1 'are C 2 -C 18 alkyl, C 3 -C 6 cycloalkyl, naphthyl or formula
Rf R «
<img file="CS238626B2_D0029.tif" />
or
RfR where is
Rd and R5 are independently hydrogen, halogen, methoxy, trifluoromethoxy, thiomethyl —SCH3, —SO2CH3, phenyl, phenyl substituted with halogen and / or C1 -C4 alkyl and / or trifluoromethyl a phenoxy group optionally substituted by a halogen atom
When R2 or R3 is a hydroxyl group, formula I and II include a disiloxane of formula
These guanidine-containing organosilicon compounds are effective as antifungal agents for molded plastics and rubbers, especially for<sup>1</sup> silicone rubbers.
Soviet Patent No. 346,306 protects the methyl methyl azoles of the general formula
<img file="CS238626B2_D0030.tif" />
(Rl)<sub>n</sub> (R2O) <sub>3</sub>- “SiCH2Az where they mean
R1 and R2 are each alkyl, zero to 3 and
The az pyrazole, imidazole or benzimidazole ring, optionally substituted.
Soviet Patent Specification No. 271'552 protects silylethylazoles of general formula (R1)<sub>n</sub>(R2O)<sub>3</sub>.<sub>n</sub>SiCH2CH2Az where
R 1, R 2, and Az are always as defined in Soviet Patent No. 346,306, supra.
The present invention provides a fungicidal composition, characterized in that it contains a compound of the formula I or II as active ingredient.
<img file="CS238626B2_D0031.tif" />
where it means
R1 and R5 independently of one another are hydrogen, halogen, methoxy, trifluoromethoxy, thiomethyl SCH3, -SO2CH3, phenyl, phenyl substituted by halogen and / or C1-C4 alkyl and / or trifluoromethyl , phenoxy, phenoxy substituted with halogen and / or C 1 -C 4 alkyl and / or trifluoromethyl, trifluoromethyl, (C až-C) alkyl or cyclohexyl, provided that in the case of the compound of formula (II), R Ri and R5 cannot both be hydrogen,
R 2 and R 3 are each independently C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, OR 6 OR
<img file="CS238626B2_D0032.tif" />
where it means
R 6 is hydrogen or C 1 -C 4 alkyl, provided that R 2 and R 3 are not both hydroxyl and R a and R 3 can each form a 1,2-glycol, 1,3-glycol or 1,4-glycol bridge; or 1,4-unsaturated glycol bridge substituted with up to 4 alkyl groups R? to R10 having a total of up to 4 carbon atoms where is
Q1, Q2 and Q3 independently of one another are hydrogen or methyl,
R 1 is C 2 -C 18 alkyl, C 3 -C 6 cycloalkyl, naphthyl or o- or
<img file="CS238626B2_D0033.tif" />
<img file="CS238626B2_D0034.tif" />
Rf R
R 1 'is C 6 -C 18 alkyl, C 3 -C 6 cycloalkyl, naphthyl or formula
Compound of 5 species
Phytophthora restricted in vitro
123
Compound% Reduction of Tomato Mold (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane,
1: 1 copper (I) chloride complex 100 (Ι, Γ-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane,
1: 1 complex with zinc chloride 90 (4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-yl-30-methylsilane (Ι, Γ-Biphenyl- 4-yl dimethyl (5-methyl-1H-1,2,4-triazol-1-ylmethyl) silane 80 (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-yl) ylmethyl jsilan,
1: 1 complex with copper chloride 90
Example 79
The active compounds according to the invention are introduced into standard V-8 agar at 45 [deg.] C. in an amount of 200 ppm. The conditioned agar is then dispersed in Petri dishes and allowed to solidify. Agar cultures of approximately 4 mm area are introduced into the culture medium<sup>2</sup> 5 Phytophthora species: Phytophthora cinamomi, P. cactorum, P. infestans, P. palmivora and P. parasitica var. nicotianae and incubated at 22 ° C for 6 days. Colonies with a radial increase of not more than 1 mm are considered to be inhibited by the active ingredient according to the invention as compared to colonies with a radial increase of more than 15 mm growing on the untreated medium. The number of Phytophthora limited by certain active substances according to the invention is shown in the following table.
Table XXXI
Compound of 5 species
In vitro restricted phytophthora (Butyl j dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 1 (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 2 (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 3 (1H-imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane 4- (2,4-Dichlorophenyl) dimethyl (1H-iroidazole) 1-ylmethyl jsilane 5
124
Diphenyl (1H-imidazol-1-ylmethyl) methylsilane 2 (4-Fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl jsilane 2)
Example 80
The active compounds according to the invention are introduced into a suitable composition and used to coat cotton seeds in an amount of 2 g / kg of seeds. After<sup>!</sup> perfect bedding, the seeds are allowed to air dry at room temperature. Cotton seeds are then sown in soil treated with Pythium aphanadermatum, sand, corn flour in sufficient quantity to destroy most seeds. The seeds in this soil are kept at room temperature for one week and then the degree of infestation is evaluated. The percentage of infestation is shown in the following table. Most or all of the treated seeds germinate and good seedlings are obtained, while untreated seeds do not germinate or produce weak and slow seedlings.
Table XXXII
Compound% cotton burn restriction
Ethyldimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 48 (Ι, Γ-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 12 (4-Chloro) enyl j dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 53 '
Dimethyl (4-phenoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 18<sup>Λ</sup> (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 18 (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 18<sup>Λ</sup> (3,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 15<sup>Λ</sup><sup>AND</sup>active ingredient used in an amount of 0.5 g / kg seed
Example 81
The active compounds according to the invention are formulated in suitable formulations and are then used to coat corn grains in an amount of 2 g / kg of grains. After thoroughly covering the grains
125
126
Compound% restriction
The pythia on corn is allowed to air dry at room temperature. The seeds are then sown in soil treated with a mixture of Pythium aphanadermatum, sand, and corn flour in an amount sufficient to destroy most of the neoclass.
<td colspan="2">of rubbed grains. It is kept at 9 ° C for two weeks and then at 21 ° C for another week. After this time, the assault is evaluated. The percentage of infection limits is shown in the following table. Most or all of the treated grains sprout and grow healthy seedlings, while untreated grains either do not come at all or produce seedlings or slowed seedlings.</td>
<td>Table XXXIII</td><td></td>
<td>Compound</td><td>% reduced Pythia to maize</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane</td><td> 32</td>
<td>(4-Chlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane</td><td> 25</td>
<td>(1 H -imidazol-1-ylmethyl) dimethyl (1-naphthalenyl) silane</td><td> 27</td>
<td>(3,4-Dichlorophenyl) (1H-imidazol-1-ylinethyl) dimethylsilane</td><td> 30</td>
(1H-imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane 5
Dimethyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) silane 15
Ethyldimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 13 (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 30 (4- Chlorophenyl j dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 8
Dimethyl (1-naphthalenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 30 (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 43
Ethyl (1H-imidazol-1-ylmethyl) dimethylsilane 70 (ΙΗ-Imidazol-1-ylmethyl) dimethyl (4-methylphenyl) silane 30
Contents153
34 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34
41 members in 20 offices
Priority claims20
| Document | Office | Kind | Date |
|---|---|---|---|
| 27698681 | United States of America | A | |
| 27698681 | United States of America | A | |
| 27698781 | United States of America | A | |
| 27698781 | United States of America | A | |
| 34926182 | United States of America | A | |
| 34926182 | United States of America | A | |
| 37712182 | United States of America | A | |
| 37712182 | United States of America | A | |
| 37712282 | United States of America | A | |
| 37712282 | United States of America | A | |
| 81276986 | – | – | – |
| 81276987 | – | – | – |
| 82349261 | – | – | – |
| 82377121 | – | – | – |
| 82377122 | – | – | – |
| US19810276986 | – | – | – |
| US19810276987 | – | – | – |
| US19820349261 | – | – | – |
| US19820377121 | – | – | – |
| US19820377122 | – | – | – |
Members41
| Document | Office | Kind | |
|---|---|---|---|
| IL66114A0 | Israel | A0 | |
| IL66114D0 | Israel | D0 | |
| DK282782A | Denmark | A | |
| EP0068813A2 | European Patent Office (EPO) | A2 | |
| AU8509982A | Australia | A | |
| JPS584791A | Japan | A | |
| EP0068813A3 | European Patent Office (EPO) | A3 | |
| BR8203631A | Brazil | A | |
| ES8307829A1 | Spain | A1 | |
| JPS58144393A | Japan | A | |
| PL237088A1 | Poland | A1 | |
| KR840000570A | Republic of Korea | A | |
| ZA824460B | South Africa | B | |
| ES8404367A1 | Spain | A1 | |
| ES8404368A1 | Spain | A1 | |
| ES8404369A1 | Spain | A1 | |
| GR76497B | Greece | B | |
| CA1176258A | Canada | A | |
| US4496551A | United States of America | A | |
| NZ201061A | New Zealand | A | |
| PH18112A | Philippines | A | |
| PH18132A | Philippines | A | |
| US4510136A | United States of America | A | |
| PL133929B1 | Poland | B1 | |
| EP0068813B1 | European Patent Office (EPO) | B1 | |
| AT15804T | Austria | T | |
| ATE15804T1 | Austria | T1 | |
| DE3266532D1 | Germany | D1 | |
| CS238626B2This record | Czechoslovakia (until 1993) | B2 | |
| HU189152B | Hungary | B | |
| AU553808B2 | Australia | B2 | |
| SU1324573A3 | Soviet Union (until 1991) | A3 | |
| JPS6253515B2 | Japan | B2 | |
| IL66114A | Israel | A | |
| KR880002604B1 | Republic of Korea | B1 | |
| DK126490A | Denmark | A | |
| DK126490D0 | Denmark | D0 | |
| DK126790A | Denmark | A | |
| DK126790D0 | Denmark | D0 | |
| DK160364B | Denmark | B | |
| DK160364C | Denmark | C |
Numbers
- Publication, DOCDB
- 238626
- Publication, EPODOC
- CS238626
- Application
- 824735
- Application, DOCDB
- 473582
- Application, EPODOC
- CS19820004735
Titles
- English
- Fungicidal composition and method of preparation. active ingredients
Classification
- IPC, 1
- A01N55 00