Insecticide
Abstract
This record has no abstract on file.
Term
Term ended
Expired 3 February 2001, 25.6 years ago.
- Priority
- Filed
- Granted
- Expired
- Today
2 claims: 2 independent, 0 dependent
- 1Pateno disclaimer Zastrzeżenie patenoowe An insecticide containing the active substance and diluents and / or surfactants, characterized in that as active substance it contains at least one new heterocyclic compound of formula 1 in which n is 0 or 1, 12 3 4 Środek owadobójczy, zawierający substancję czynną oraz rozcieńczalniki i/lub środki powierzchniowo-czynne, znamienny tym, że jako substancję czynną zawiera co najmniej jeden nowy związek heterocykliczny o wzorze 1, w którym n oznacza 0 lub 1, 12 3 4 R , R , R i R niezależnie od siebie oznaczają atom wodoru lub grupę metylową, R oznacza atom wodoru ].ub grupę metylową^ χ oznacza atom siarki, tlenu, grupę o wzorze -^-R^ lub -CH przy czym R^ oznacza atom wodoru, grupę alki^wą o 1 - 3 atomach oęgla, grupę allilową, grupę acetylową, grupę metylosulfonylową, grupę dwumetyloaminokarbonylową, grupę fenoksykarbonyIową, grupę benzoilową ewentualnie podstawioną chlorem, grupę etcrsyrarbcnylową, grupę benzylową ewentualnie podstawioną chlorem, grupę O-etylo-S-n-propylotiolofosfonową, albo grupę -CH?-W lub -CO-W, w których to grupach W oznacza 5-6-czoonową grupę heterocykliczną, zawierającą jeden lub dwa heteroaoorny, takie jak tlen, siarka lub azot, przy czym co najmniej jeden z nich stanowi atom azotu, ewentualnie podstawioną chlorem lub grupą metylową, Y oznacza atom azotu albo grupę o wzorze = C-R^,, w którym R^ °znacza atom wodoru, chlorowca, grupę alkiCraarCtyyoową o 1 - 3 atomach węgla, grupę benzoilową ewentualnie podstawioną grupą metylową, grupę etorsykarbonllooą, fenylosuioonylową, fenoksykarbonyIową, fenylo^io lub fenylosufonι^/Όο^ι nokarbo ny lows, a Z oznacza 5-6-członową grupę heterocykliczną, zawiera jącą 1-3 heteroaoomy, takie jak tlen, siarka lub azot, przy czym co najmniej jeden z nich stanowi atom azotu, ewentualnie podstawioną co najmniej jednym podstawnikiem, takim jak atom fluoru, chloru, bromu, grupa trifluoΓimelyCowa, me149 199 R, R, R and R are each independently a hydrogen atom or a methyl group, R is a hydrogen atom]b groupsę methyl ^ χ is the colostrum atomkand, oxygen, grupę with the formula - ^ - R ^ or -CH wherein R^ is a hydrogen atom, grupę alcove 1 - 3 atomich oęgla, gallyl group, acetyl group, methylsulfonyl group, dimethylaminocarbonyl group, phenoxycarbonyl group, benzoyl group optionally substituted with chlorine, etcrirburcnyl group, benzyl group optionally substituted with chlorine, O-ethyl-Sn-propylthiolophosphonic group, or -CH- -W or W, in which groups W is a 5-6-membered heterocyclic group containing one or two heterooornes, such as oxygen, sulfur or nitrogen, at least one of which is nitrogen, optionally substituted with chlorine or lubgruPa methyl, Y is nitrogen or Grupę with formula = C-R ^, in which R ^ °fromona hydrogen atom, a halogen atom, a 1 -C 3 carbon atom, a benzoyl group optionally substituted with a methyl group, an etoricarbonyl group, a phenylsioonyl group, a phenoxycarbonyl group, a phenyl group or a phenyl sulfonium group;membered heterocyclic group containing 1-3 heteroaooms, such as oxygen, sulfur or nitrogen, at least one of which is a nitrogen atom, optionally substituted with at least one substituent, such as fluorine, chlorine, bromine, trifluoΓimelyCowa group, me149 199 1 Rear, ethyl, cyano, methoxy, methylthio, trifluoroethoxy, wherein when R, R, R 2 and R 5 are hydrogen at the same time, X is -NH and Y is »ÓH, then Z is not a pyridyl group. 1 7 tyłowa, etylowa, cyjanowa, metoksylowa, metylotio, trifluoroetoksylowa, przy czym gdy R , R , R^ i.R^ oznaczają jednocześnie atomy wodoru, X oznacza -NH, a Y oznacza »ÓH, wtedy Z nie oznacza grupy pirydylowej. R4 R3 R4 R3 FROM Z R2 R2 R1 R1 N - NO2 N — NO2 PATTERN Ib WZOR Ib h2n h2n Z - CH — M Z — CH—M MODEL 8 WZÓR 8 HN HN C — NH — NO2 // C—NH —NO2 // PATTERN 9 WZOR 9 -CHNO2 [2S> = CHNO2 CHNO2 [2S>=CHNO2 CH2 CH2 Cl cl MODEL 15 WZOR 15 WZÓR 19 Walkthrough level 19 PATTERN 11 WZOR 11 149 199 149 199 WZOR 22 Walkthrough level 22 MODEL 28 —CH3 c2h5 WZOR 28 —CH3 c2h5 WZOR 31 Walkthrough level 31 Γ )=N— NO2 Γ) = N— NO2 0Η2WZOR 33 0Η2Walkthrough level 33 H H PATTERN 36 WZOR 36 About cX N O cX N CH2N ', NH CH2N„,NH O2N sWZOR 37 O2N sWZOR 37 149 199 149 199 Cl cl I-1 I-1 CH2N NH o2n conhso2— CH2N NH2n conhso2— PATTERN 36 WZOR 36 ABOUT2 NssN c3h7what2 OCH2NysN c3h7co no2 WZOR 41 Walkthrough level 41 Cl cl WZOR 45 Walkthrough level 45 WZOR 46 Walkthrough level 46 OrCH2Y_CH2Yo;OrCH2Y_CH2Yo;N-N02 N—Ń02 WZÓR 39 Walkthrough level 39 N-x nx H3C - (/ "V H3C-(/”V = Ν / Ν=/ WZÓR 47 Walkthrough level 47 Cl cl N-N NN WZOR 48 — CH2N —C3H7-i Walkthrough level 48 - CH2N —C3H7-and II II CI Ν —NO2 CI Ν —NO2 HtC h3c HtC h3c WZÓR 49 Walkthrough level 49 WZOR 40 Walkthrough level 40 WZOR 43 Walkthrough level 43 WZOR 44 Walkthrough level 44 WZÓR 50 Walkthrough level 50 N-NO2 N—NO2 WZOR 51 Walkthrough level 51 H H WZÓR 54 Walkthrough level 54 WZÓR 58 WZOR 59 Walkthrough level 58 TEMPLATE 59 WZÓR 52 Walkthrough level 52 R4 R3 H \ / R2HYb ^ 5 ch2n ^ n _ R Y - N02 R4 R3 H \ / R2HYb^ 5 ch2—n^n _ R Y — N02 PATTERN 60 PATTERN 61 WZOR 60 WZÓR 61 WZOR 55 Walkthrough level 55 CH, CH, H \ I H ~Y ch-no2 H \ IH ~ Y ch-no2 WZOR 53 Walkthrough level 53 -ch2-n analysis2-n WZÓR 56 Walkthrough level 56 WZÓR 57 Walkthrough level 57 OH OH I c —chcci3 I want to3 WZÓR 62 Walkthrough level 62 C-COH ^ HCHg MODEL 63 C-COH^HCHg WZÓR 63 Cl cl 149 199 149 199 -N '^ = CHNO2 \/ -N‘ ^=CHNO2 \/ WZOR 66 Walkthrough level 66 C-CONCCO - (/ \) C-CONCCO—(/ \) MODEL 6 5 WZÓR 6 5 9-CH-T- 9-T-CH-
- 22ΉβΓ5 . 1 WZÓR 70 y=CHNO'2 o 2ΉβΓ5. 1 MODEL 70 y = CHNO'2 sts about o II s - ch3 II 3 about II s — ch3 II 3 o WZÓR 68 Walkthrough level 68 -COLOVER 67 -COOWZÓR 67 H^OC2C5 ^ H OC2C5 P ^ pc3h7 P ^sc3h7 WZÓR 69 «^rn Walkthrough level 69 «^ -N -N CHy = CCNO2 s Her 2 1 CHy = CCNO2 s her 2 1 WZÓR 72 Ri R3 H \ / H Walkthrough level 72 ri R3 H \ / H S N S—N SNS-N WZÓR 78 WZÓR 79 „ n l-K Walkthrough level 78 Walkthrough level 79 " n lK H ^ | \S 5 Z— CC2-ΝγΝ~ R5 H^ |\S 5 Z— CC2-ΝγΝ~ R5 Y-NO2 Y-NO2 WZÓR 84 Walkthrough level 84 H3C H3C PicturedR 76 WZĆR 77 WZOR 76 WZĆR 77 CCNO2 MODEL 88 CCNO2 WZÓR 88 CH2—X / _ \ / N = < CH2—X/ _\ / N=< WZÓR 89 / T 5 -OHJ WZÓR 89 /T 5 -OHJ Cl cl WZÓR 86 WZÓR 85 Walkthrough level 86 Walkthrough level 85 H3C H3C WZÓR 82 Walkthrough level 82 WZÓR 81 Walkthrough level 81 Ch ch N- N N-N WZÓR 87 Walkthrough level 87 CC2 CC2 I-N ^s^chno2 IN ^ chno2 WZÓR 83 r~ Walkthrough level 83 Γ >=N— N Γ> =N- N NO2 Ch2“\j? ' NO2 ch2“\j? ' WZÓR 91 Walkthrough level 91 WZÓR 90 Walkthrough level 90 149 199 149 199 Η2Ν - (CH ^ —NH2CH2· Η2Ν —(CH^—NH2-CH2· H3C C 2—ch2nhch2ch2sh + C12€=CH — N02 (CH3S)2C = chno2 oCHNO2 H3CC 2 — ch2NHCH2ch2sh + C12€ = CH - N02 (CH3S)2C = chno2 oCHNO2 DIAGRAM 1 SCHEMAT 1 CH-N CH-N CH_// _ // CH SCHEMAT 2 ξβ-ΟΗ,ΝΗΟΗ^Η + CI3C —CHCl—NO2 Cl —=J> —CH2NH_ +->N — NHC^^ SCHEME 2 ξβ-ΟΗ, ΝΗΟΗ ^ Η + CI3C —CHCl — NO2 Cl - = J> —CH2NH_ + -> N - NHC ^^ NH 'NH2 NH 'NH2 Cl cl Och2- Oh2- Cl cl DIAGRAM 3 SCHEMAT 3 DIAGRAM 4, ζ-ξε = NH SCHEMAT 4 ,ζ-ξε =NH HNO3 HNO3 CH CH C) = N ~ NO2 N 1 .fi in \ - chno2 H C)=N~ NO2 N 1 .fi w \ — chno2 H -ch2ci analysis2these CH— Cl = CHN0about CH— Cl = CHN0o Z <from Zc, Z—<z Zc, DIAGRAM 5 SCHEMAT 5 DIAGRAM 6 SCHEMAT 6 R R AND I Z — CHR ^ R3 H \ / R3 hYZr1 Z—CHR^ R3 H \ / R3 hYZr1 - Ν ^ χΝΗ - Ν^χΝΗ -CHNO2 CHNO2 R ^ R3 H \ / R3 JC)n R^ R3 H \/ R3 JC)n Z — CH- Nx> N Z—CH- Nx>N DIAGRAM 7 SCHEMAT 7 AND I CH = N ^ OH CH = N ^OH R R AND I Z - CHand r3 H \ / R2 Z — CH ra r3 H \ / R2 ZZ '- N ^^ zNH ZZ’ — N^^zNH T T N - NO2 N — NO2 R ^ R3H X /2 R^ R3H X/2 R1 R1 Z-CH-Ννγ> Ν Z-CH-Ννγ>Ν NH-N02 NH—N02 DIAGRAM 8 SCHEMAT 8
Independent claims2
294 paragraphs in 1 section, as filed
<td rowspan="2">POLAND REPUBLIC CHINA</td><td>PATENT DESCRIPTION</td><td> 149199</td>
<td rowspan="3">Additional patent to patent No. ---</td><td rowspan="4">KTTE1IM isίlll</td>
<td></td>
<td></td>
<td></td><td>reported: <sup>86 02 03</sup> /?· <sup>257774</sup></td>
<td></td><td>Priority; 85 10 03 Japan</td><td>Int. Cl.<sup>4</sup> A01N 43/50</td>
<td></td><td></td><td>AOlS 43/34</td>
<td>OFFICE PATENT</td><td>The application was announced: 88 02 04</td><td>A01N 43/76. A01N 43/78 A01N 43/86</td>
<td>PRL</td><td>Patent description 'published: 90 04 30</td><td></td>
Creator of the invention Patent holder: Nihon Tokushu Noyaku Seizo KK ·, Tokyo / Japan /
INSECTICIDE
The subject of the invention is an insecticide containing new heterocyclic compounds as active substance. It is known that certain nitromethylene derivatives have an insecticidal effect, e.g. known from REN OE-OS No. 2514402 1-benzyl-2-nitromety1enotetrahydropyrimidine, and some triazolithry derivatives have anti-tumor activity against gastrointestinal cancer / see Japanese Laid-out No. 196877 / 1964 /. In addition, in Can. J.Chem., Vol. 39, p. 1787-1796 describes 1-benzyl-nitroeminoimiazolidine. It has now been found that certain new heterocyclic compounds have excellent insecticidal activity.
The agent according to the invention contains as active substance new heterocyclic compounds of formula 1 in which n is 0 or 1, R ^, R<sup>2</sup>, R<sup>P</sup> and R 4 are independently of each other a hydrogen atom or a methyl group, R is a hydrogen atom or a methyl group, X is a sulfur atom, an oxygen group, the formula -NR or -C 4, wherein R is a hydrogen atom, an alkyl group of 1-3 carbon atoms, allitic, acetyl, methylsulforyl, dimethylaminocarbonyl, phenoxycarbonyl, benzoyl optionally substituted with chlorine, ethoxycarbonyl group, benzyl group optionally substituted with chlorine, O-ethyl-Sn-propylthioOoOero group or a group of formula -C ^ -W or -CO-W, in which groups W is a 5-6 membered heterocyclic group containing one or two heteroatoms, such as oxygen, sulfur or nitrogen, at least one of them is a nitrogen atom,
149 199 optionally substituted with chlorine or a methyl group, Y is a nitrogen atom or a group of formula = CR CR, in which is hydrogen, halogen, <sup>g</sup>ru<sup>p</sup>ę a] .ki<sup>about</sup>okrbbonyoow<sup>and</sup> with 1-3 carbon atoms, a benzoyl group optionally substituted with a methyl group, ethoxycarbonyl, phenylsioonyl, phenoxycarbonyl, phenylthio or phenylsioorylaminocarbonyl group, and Z is a 5-6 membered heterocyclic group containing 1-3 heteroaooms, such as oxygen, sulfur or nitrogen, at least one of them is a nitrogen atom, optionally substituted with at least one substituent, such as fluorine, chlorine, bromine, trffluoromethyl, methyl, ethyl, cyano, methoxy, methylthio,
2 3 4 trfflbobeebokyybowa, where when R, R, R<sup>and * 3</sup> and R<sup>4</sup> are both hydrogen atoms,
X is -NH and Y is = in, then <sup>FROM</sup> does not mean <sup>g</sup>ru<sup>p</sup>pyridyl y.
A method for preparing compounds having formula 1a wherein n, R1, R5, R5, R5, R, R5
7 and Z are as defined above, X is sulfur, oxygen or a group of formula -NR,
5 wherein R is as defined above for R, with the exception of acyl groups, including Gru
2 sulphonic and phosphonic dusts, consists in the fact that a / 2 compounds in which n, R, R,
4 1 *
R, R, R, X and Z have the above meanings, are reacted with compounds of formula 3 in which R * is a lower alkyl or benzyl group, or two R 'can form a ring with two sulfur atoms<sup>ki</sup>, with ^ p<sup>and</sup> bound and R ^ is above <sup>after</sup>da<sup>n</sup>e <sup>know</sup>the compound, optionally in the presence of an inert solvent, or b / compounds of formula 2 is reacted with compounds of formula 4 in which Hal is a halogen atom and R "is a hydrogen atom, a halogen atom or a lower alkyl group, optionally in the presence of an inert solvent and in the presence of acid acceptors, the compounds are reacted with compounds of formula 5 in which Hal and R "have the meanings given above, optionally in the presence of an inert solvent and in the presence of acid acceptors.
The method for producing compounds having formula 1b in which n, r1, R ^, r \ r \ Rf χ1 and Z are as defined above is that d / compounds of formula 2 as defined above are reacted with nitroguanidine of formula 9 , optionally in the presence of an inert solvent.
2 3 4
A method for preparing compounds having formula 1c wherein n, R, R, R<sup>3</sup>, r4, X, R and Z have the meaning given above, it is ty that e / compounds of the formula 6 in which n,
3 4
R, R, R, R, X, R and Z have the meanings given above, are reacted with fuming nitric acid, optionally in the presence of an inert solvent.
The method of producing compounds of formula 1 consists in the fact that f / compounds of formula 7, 12 3 4 in which n, R, R, R, R, X and Y have the above meanings, are reacted with compounds of formula Θ, in wherein R and Z are as defined above, M is a halogen atom or a group with -OSOpT in which T is a lower alkyl group, a phenyl or folio group, optionally in the presence of an inert solvent and in the presence of acid acceptors. Speech, heterocyclic compounds have strong insecticidal properties.
It has been surprisingly found that the new compounds exhibit higher and more excellent insecticidal activity than the known compounds mentioned in the prior art. In addition, the new heterocyclic compounds also exhibit significant insecticidal activity against harmful insects, especially sucking insects, which are represented by Hemópter's insects, such as grasshoppers and jumble jolts, which have become resistant to the action of phosphomides and organic carbonates such as use. If in the process a / will be used as starting substances e.g. N- / 1-methyl-4pi-azoliboraethyl / tΓOmeyltbodamine and 1-nitro-2,2-bs / methylthio / ethylene, the reaction is illustrated in Scheme 1.
149 199
If, in process b / as starting substances, e.g. 2- / 2-methyl-5-pyrazinylmethylamino / ethanethiol and 2,2-dichloronitroethane are used, the course of the reaction is illustrated in Scheme 2. If in process c /, e.g. 2- / 2-chloro-5-thiazolioraethylaiino / ethanethiol and 1,2,2,2-tetrachloro-1-nitroethane, the course of the reaction is illustrated in scheme 3
If, for example, N- / 2-chloro-5-pyridylmethyl / trimethyldimine and nitroguanidine is used in the d / process as starting materials, then the reaction is illustrated in Scheme 4. If in the e / process, e.g. 1- / 2- chlorine / -5-pyridyl binets loZ - ^^ - miJ ^ noiMidazololina and fuming nitric acid, the reaction is illustrated in scheme 5. If in the process f / as starting substances, e.g. 2-nitromethylene thiazolidine and 2-chlorine / -5-pyridylethyl chloride, the course of the reaction is illustrated in scheme 6. The compounds of formula 1 also include tautomers, as shown for the case when X is NH and Y is CH, in scheme 7, and for the case where X is NH and Y is N, in Scheme 8.
In addition, the compound of formula 1 also includes the E, Z isomers. The compounds of formula 1 may also exist in the form of salts. Examples of salts are inorganic acid salts, sulfonate salts, organic acid salts and metal salts. The new compounds have strong insecticidal activity, so they are the active substance of insecticides.
They can be used to combat and eradicate a wide range of pests, including sucking insects, biting insects and other plant parasites, stored grain pests and health / health hazards.
Examples of pests are: Cooeopterous insects: Call / s / bruchus chinensis, Sitophilus zeamais, Triboliura castaneus, E? Ilachna vigitoctomaculata, Agriotes fus cicoHis, An.o mai a rufocuprea, Lep tino tar sa decemlineata, Diabrotochoruspp, Monus oryzophilus and Lyctus bruneus.
Lepidopterous insects: Lymmnnria dispar, Malocosoma neustria, Pieris rapae, Methodoptera litura, Mammetra brassicae, Chilo suppressalis, Pyrausta nubileMa, Ephestia cautella, Adorophyes orana, Carpocapsa p / raonoela, Agrotis fucosa, Gaaieria meellaislella, Placaenella,
Hen ^ terous insects: NephoOetiix cinotioeps, Ni ^ pa ^ a ^ lugens, Pseudococcit cometocki, Unaspis yanonensis, Myzus persicae, Aphto pomi, Aphis gossypii, Riopałoslphum pseudobrassicas, Stephanntis nashi, Nazara spurl.
Orthopterous insects: Blatella germanica, Periplaneta americana, Cr ^ y-otalpa africana and Locusta migratoria migΓat / rlodes.
Insects IsopteΓ / us: Deucotermes speratus i Copt / teΓmes formosanus.
Dipterous insects: Musca domistica, Aedes aegypti, Hleniia platura, Gulex pipens, Anopheles sloeosisi Culez trimaonOorhynchus.
In the veterinary field, the new compounds are effective against various animal external parasites such as insects and worms.
Examples of animal parasites are the following insects:
Gastrophilus spp., Stomorys spp., Trichodectes spp., Rh / dlui epp. and Ctenocephalides canto. The active compounds are converted into known preparations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, me / zOzoles, natural and synthetic substances of iipΓego / iaae active compound, small capsules in polymeric substances, com
149 199 coating positions for use on seeds and preparations used with the incinerator, such as smoke removal cartridges, cans and spirals, as well as ultra-low volume preparations of cold fog and warm fog.
These preparations are prepared by known methods, e.g. by mixing active substances with fillers, i.e. liquid, liquefied gas or solid diluents or carriers, optionally with the addition of surfactants, i.e. emulsifying agents and / or dispersing agents and / or forming agents. foam.
When water is used as the filler, organic solvents can also be added as additional solvents.
As liquid solvents, diluents or carriers, mainly aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. mineral oil fractions, alcohols such as butanol or glycol, their ethers and esters, ketoo such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone or highly polar solvents such as dimethylfungamide and dimethyl sulfoxide as well as water. . '
Liquefied gaseous diluents or carriers are liquids which are gaseous under normal pressure and temperature conditions, e.g. aerosol propellants such as halogenated hydrocarbons and. butane, propane, nitrogen and carbon dioxide. As solid carriers, ground natural minerals such as kaolin, clays, talc, chalk, quaternary, attapulgite, and admironite are used. or diatomaceous earth and ground synthetic minerals such as highly dispersed silicic acid, alumina and silicates. As solid carriers for granules, crushed and fractionated natural rocks such as calcite, marble, pumice, sepioliti dolomite, as well as synthetic granules from inorganic and organic substances and granules from organic substances such as sawdust, coconut shells can be used, corn cobs and tobacco stalks. As emulsifying and / or foam forming agents, nonionic and anionic emulsifiers such as polyoxyethyl and fatty acid esters, polyoxyethylene and fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonary, alkyl sulfate, aryl sulfonate as well as albumin hydrolysis products can be used. Dispersants include, for example, lignosirΓNew waste liquors and methylcellulose.
Adhesives such as carboxymethyl cellulose and natural and artificial polymers in the form of powders, granules or lotions, such as acacia, polyviro alcohol and polyvinyl acetate can be used in the formulations. It is possible to use dyes such as inorganic pigments, e.g. iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizayne dyes, nitrogen dyes or metal phthalocyanide dyes and traces of nutrients such as salts of iron, magnesium, boron, copper, cobalt, molybdenum and zinc. The formulations usually contain 0.1 95% by weight, preferably 0.5 - 90% by weight, of the active substance.
The compounds of formula I may exist in commercial preparations and in use forms prepared from these preparations, as mixtures with other active compounds, such as insecticides, baits, sterilizing agents, acaricides, nicietiobcyclic, fungicidal, growth regulating substances or herbicides.
Insecticides include e.g. phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenyl urines, substances produced by microorganisms. New relationships
149 199 may also be present as mixtures with synergistic agents. These are compounds that increase the action of active compounds, but they do not have to be active themselves. The content of the active compound in the forms to be used prepared from commercial preparations depends on many factors. The active compound concentration in the dosage form is 0.000000199.9% by weight, preferably 0.0001 '- 1% by weight.
The agents are used in a known manner, appropriate to the form used. When active compounds are used against hygiene pests and stored products, they are distinguished by excellent debris action on wood and clay and good stability on alkalis and calcareous substrates. The following examples illustrate how to prepare the active ingredient of an agent of the invention.
Example 1 Compound No. 1 of formula 10. A mixture of 4.3 g N- / 2-chloro-5-pyridylmethyl / -3-teinopropannkiol, 3.3 g 1-nitro-2,2-bis / methylthio / ethylene and 40 g ml of ethanol is kept under reflux for 10 hours under a stream of nitrogen. After the reaction is completed, about 2/3 of the ethanol is distilled off under reduced pressure. A little ether is added to the reaction mixture to excipient triests. The crystals are filtered off, washed with a mixture of ethanol and ether to give 1.3 g of the desired compound 3- (2-chloro-5-pyridylmethyl) -2-thread - methylene-tetthyrido-2H-1J-Uzyri in the form of yellow crystals with a melting point of 164 - 166 ° C.
Example II Compound No. 2 with the formula 11. 2.9 g of 2-nitromethylene thiazolddyra is dissolved in 30 ml of dry acetonitrile and 0.9 g of 60% sodium hydride is added at room temperature and under a nitrogen stream. The reaction mixture is stirred at room temperature until no more hydrogen is released. Then, a solution of 3.2 g of 2-chloride-5-pyricylmethyl chloride in 5 ml of dry acetonitrile is added at room temperature, and the resulting mixture is stirred at room temperature for 1 day.
Then acetonitrile is distilled off under reduced pressure and dichloromethane is added to the residue. The mixture is washed with water and dichloromethane is distilled off from the dichloroethane layer. The residual oil is purified by silica gel column chromatography, to give 1.6 g of 3- / 2-chloro-5-pyridylkeeiyroO-2-nitrkmeeylene thiazolidine, mp 177-179 ° C.
Example III. Compound No. 3 of formula 12. A mixture of 1.8 g of N - ^ - pyridylmethyl amide / -3-aeopinoproteinyl, 1.7 g of 1-nitro-2,2-bis / mitrlotio / ethylene and 40 ml of ethanol is refluxed under reflux condenser and stream of nitrogen for 5 hours. After the reaction is completed, about 2/3 of the ethanol volume is distilled off under reduced pressure. A little ether is added to the reaction mixture to precipitate the crystal. The crystals are filtered off and washed with a mixture of ethanol and ether to give 1.2 g of 3- (3-pyridylkeyl) / -2-nitkeeetrlenktettahydτo-2H-1,3-thiazine, m.p. 147-146 ° C.
Example IV Compound No. 4 of formula 13. 2.9 g of 2-nitroethylene thiazolidyrine is suspended in 30 ml of dry acetonitrile and 0.9 g of 60% sodium hydride is added in a stream of nitrogen. The mixture is stirred at room temperature until hydrogen evolution ceases, then a solution of 3.2 g of 3-picolyl chloride in 5 ml of dry acetonitrile is added and the mixture is stirred at room temperature for 3 hours.
is distilled off under reduced pressure, and dichloromethane is added to the residue, and the ottoman mixture is washed with water. Then dichloromethane is distilled off from the organic layer. The residual oil product is purified by column chromatography to give 0.5 g of 3- (3-pyri-methyl) -2-nitroithenylenectiazolyrin, mp 96-100 ° C.
149 199
Example 5 Compound No. 5 of formula 14. A mixture of 16.8 g N- (1-methyl-4-pyrazolylmethyl) -trimethylene diaryl, 16.5 g 1-nitro-2,2-bis / methylthio / ethylene and 200 ml ethanol under reflux until cessation of methylmercaptan evolution ceases. The mixture is cooled and the precipitated crystals are filtered off. After washing with methanol, 16.6 g of 1- (1-methyl-4-pyrazolylethyl) / 2- (nitlomlttlθ / l / tβtaahydlopitomidine) are obtained in the form of pale yellow crystals, mp 186 19 ° C ... ...
'Example 6 .. Compound No. 6 with formula 15. Mixture 15.5 g N- / 3-O-tyloyl-5-isazylxazllilyl / ethylodimιint, 16.5 g 1 - / ^ γο-2,2-bis / methylthio / ethylene and 200 ml of ethanol is boiled under reflux until cessation of oetylerkaptan ceases, · after about 3 hours. The reaction mixture is cooled to room temperature, crystallizing the product. The crystals are filtered off and washed with ethanol to give 12.5 g of 1- (3-methyl-5-isoxazllyl-ethyl / 2- / nitromet<sup>s</sup>leno / imidazo] .idyn<sup>s</sup> in <sup>p</sup>ostaci. <sup>zł</sup>łtyc<sup>hk</sup>r<sup>s</sup>szta<sup>L</sup>that have a melting point <sup>168</sup> - <sup>170</sup>°<sup>C</sup>.
Example VII. Compound No. 7 of formula 16. 12.9 g of 2-nitlmoltylenololidazolidine is dissolved in 60 ml of dry dimethyl namidium and a little bit of 4.4 g of 60% sodium hydride is added in a stream of nitrogen at room temperature. The mixture is stirred from the temperature after<sup>k</sup>about her <sup>d</sup>at 3 ° C within three hours to produce salt,<sup>d</sup>this relationship<sup>k</sup>at ioi<sup>d</sup>new azolidt. Then 11.8-5-oxaiolylethyl chloride at room temperature is added and the mixture is stirred at room temperature for 24 hours. The reaction mixture is carefully poured into 150 ml of ice water and extracted twice with dichloromethane.
From the organic layers, dichloromethane is distilled off to give 12 g of 1- (5-oxo-oxazole: Loose or lower) and 61 ^ 0 / - 01: azolddir in the form of brown crystals mp 156-158 ° C.
Example VIII. Compound No. 8 of formula 17. 18.5 g N- (2-methyl-5-thiazolylethyl) / trimethyl / nodtomine is dissolved in 100 ml acetonitrile and 16.5 g 1-nitro2,2-bis / methylthio / ethylene is added . The mixture is refluxed for 6 hours with stirring and then cooled to room temperature. The obtained crystals are filtered off and washed with meta / l.o., to obtain 10.2 g of 1- (2-methyl-5-thiazolylmethyl) - 2 - / ythromethyl / o / tetra] rt drop-iryo and dyne at the top temperature. 204-207 ° C.
Example IX. Compound No. 9 of Formula 1Q. A mixture of 9.5 g of 2-fluoro-5-pyridylethyl bromide, 6.5 g of 2- (nitroimino / imidazolidine), 7.6 g of carbonate and 100 ml of acetonitrile is refluxed for 2 hours with stirring. After the reaction is completed, the mixture is cooled to room temperature and 100 ml of 'water' added. The crystals obtained are filtered off and washed with ether, affording 6.0 g light iabarvil / 1- 1- (2-cyclo-5-pyrido) n-ethyl / -2- / nitroimide / noidididolddirdt, mp 121-124 ° C.
Example X. Compound No. 10 of formula 19. A solution consisting of 10 g N- / 2-III-5-pyridylethyl / trimethyltyldiamint, 9.7 g nitroguanidry and 80 ol water heated <sup>s</sup>ut <sup>in 80</sup>°<sup>C in</sup> c<sup>and</sup>Ag<sup>k 3</sup> g ^ z ^ Mixtures<sup>ę</sup> the reaction is cooled <sup>d</sup>o-teoperate and extracted twice with 50 ml of dichloromethane. Dichloromethane is distilled off from the extracts, and the smelly residue is purified by silica gel column chromatography, obtaining 6.1 g of almost colorless 1- / 2-chloro-5-five-idyllicolyl / -2 - // itroimino / tetahyy dropirindine with melting point 113 - 117 ° C.
Example XI. a / Production of compound 20. Solution 18.6 g N- / 2-chloro-5-pyrid<sup>d</sup>tlooethyl / ettlnodiaoint in 200 ml toluene is stirred at room temperature
149 199 and 10.6 g cyan bromide are added in portions, after which the mixture is stirred again.
The desired 1- / 2-chloro-5-pii precipitates from the mixture<sup>,</sup>ydylmethyl / -2-iminoimidazolidine as the hydrobromide salt. The product is filtered off and washed with ether. The melting point is 202 - 205 ° C.
b / Preparation of compound No. 11 of formula 21. The hydrobromide produced in a. in 5.8 g is added to 30 ml of 98% sulfuric acid at 0 ° C, then 2 ml of fuming acid is added dropwise at 0 ° with stirring. and stirring the resulting mixture for 2 hours at 0 ° G. The reaction mixture is poured into 100 g ice water and extracted with dichloromethane. After distilling off the dichloromethane extract under reduced pressure, pale yellow crystals are obtained, which are washed with ether. 1.5 g are obtained
1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazoline, m.p. 136 139 ° C.
Example XII. Compound No. 12 of formula 22. To a solution of 2.4 g 2,2,2-trifluoroethanol in 30 mL toluene, 0.48 g sodium hydride is added and the resulting mixture is stirred until the evolution of hydrogen ceases. To the obtained 2,2,2-trifluoroethanol sodium salt, 5.1 g of 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine, obtained as described in Example 3, and a catalytic amount of 4-dimethylaminopyridine are added. The mixture is heated at 80 ° C for 10 hours with stirring. After cooling the reaction mixture, crystals precipitate, which, after filtration, are washed with water with ether and purified by silica gel column chromatography. 1.5 g 1- / ~ 2- /
2,2,2-trifluoroethoxy / -5-pyridylmethyl_7-2- / nitroimino / imidazolidine, m.p. 109-112 ° C.
Example XIII. Compound No. 13 of formula 23. A mixture of 15.2 g N- / 5-pyrimidinylmethyl / ethylenediamine, 14.9 g 1-nitro-2,2-bis / methylthio / ethylene and 100 g ethanol is refluxed. reflux (about 3 hours) until cessation of methylmercaptan secretion. The reaction mixture is cooled to room temperature and the crystals obtained are filtered off. The crystals are washed with ethanol and dried to give 12<sub>t</sub>7g 1/5-piryraic Nylonyl / -2- / nitrome thylene / imidazoline in the form of pale yellow crystals. This product decomposes at 236 ° C.
Example XIV. Compound No. 14 of formula 24. 12.9 g of 2-nitromethyleneimidazolidine is dissolved in 100 ml of dry dimethylformamide and added at room temperature
4.4 g of 60% sodium hydride in oil. The mixture is stirred at room temperature until hydrogen evolution ceases. Then 14.3 g of α-methyl-5-pyrazinylmethyl chloride is added at room temperature and the mixture is stirred at 40 ° C for 8 hours. After cooling to room temperature, the reaction mixture is added to 200 ml of water and extracted with dichloromethane. After distilling off the dichloromethane from the organic layer under reduced pressure, 5.4 g of 1- (2-methyl-5-pyrazinylethyl) / -2- (n-tromethylene) imidazolidine are obtained in the form of yellow crystals, m.p. 163-166 ° C.
Example XV Compound No. 15 of formula 25 · A mixture of 2 g 2-amino-1- (2-chloro-5-pyridylmethylamino / propane, 1.6 g 1-nitro-2,2-bis / methylthio / ethylene and 20 ml methanol under reflux for 5 hours, stirring.
After standing at room temperature, a crystalline product precipitates, which is suction filtered, washed with methanol and dried under reduced pressure. 1.9 g of 1- (2-chloro-5-pyridylmethyl) -4-methyl-2- (nitromethylene) imidazolidine are obtained in the form of light yellow crystals, m.p. 170-174 ° C.
Example XVI. Compound No. 16 of formula 26. A mixture of 2.6 g N- / 3-methyl-58
149 199 isoxazolylmethyl / -N- / 1-methyl-4-pyrazolylmethyl / trimethylenediamine, 1.6 g of 1-nitro-2,2bis / methylthio / ethylene- and 10 ml-ethanol are kept under cool 15 hours feedback, stirring. After completion of the reaction, ethanol is removed by vacuum distillation. The smo residue is purified by silica gel chromatography. 0.7 & 1- / 3-methyl-5- is obtained.<sup>,,</sup>iaoxazolylmethyl / -3- / 1-ethyll4-pyrazolyl-Otytyl / -2- / ni20-tethylene / letropyropyrimidine in the form of a viscous oil, n ^ 1.5670.
. Example XVII. Compound hr 17 · of formula 27. 6.6 g of finely powdered 1-nitro-2,2-bis-Ethylthio / ethylene is thoroughly mixed with 7.5 g of 2- (2-chloro-5-pyridylmethylamino / ethanol). The mixture is heated by s<sup>11</sup>0-<sup>12</sup>0 ° C in constant water <sup>thirty m</sup>-<sup>n</sup>at<sup>t</sup> ] .ub <sup>down</sup> ronant cessation of methylreaptaptan secretion. The oil obtained is cooled to room temperature and purified by silica gel column chromatography. 1.7 g of 3- / 2-chloro-5-pyridylmolyl / -2- / nitro-methylene / oxazllidine are obtained with a melting point.<sup>123</sup> - <sup>124</sup>°<sup>C</sup>.
Example XIII. Compound No. 18 of Formula 28. 2.6 g potassium hydroxide is dissolved in 20 mL anhydrous ethanol. 3.7 g of 2- (2-methyl-5-pirc) binoculars are added to the solution under nitrogen. Winter rosette<sup>ę</sup>bl.a. <sup>d</sup>at ° C <sup>and</sup> at 0 - 10 ° G, 3.0 g of 2.2-0ichloro-1-nitroethylene are added dropwise, followed by mixing the resulting meazan<sup>and</sup>n<sup>ę</sup> in <sup>10</sup>° C within <sup>1 g</sup>odziny. Ethanol is removed after<sup>p</sup>by means of artificial distillation, chloroform is added to the residue and the chloroform layer is transferred with 1% sodium hydroxide solution and water. The chlorormorm vapor is treated in a known manner, and 2.0 g of pale yellow 3- / 2-raethyl-5-pyrazinyl-chlorantol-2- / nitromelylene-l-thiazolidine crystals are obtained, mp 147-150 ° G.
Example XIX. Compound No. 19 of formula 29. A mixture of 4.7 g of N- / 1,2,5-thiadiazol-3-ylntyltythylenediamine, 3.4 g of nitroguanidine and 20 ml of water is stirred at 50-60 ° C:<sup>1</sup> hours, <sup>and</sup> then in <sup>7</sup>° Administrative of the week <sup>20</sup> minutes. kept ozi solution<sup>EB</sup>and a p<sup>and</sup>ę <sup>p</sup>owoli <sup>d</sup>about <sup>5</sup>°<sup>G</sup>, and precipitates on<sup>and</sup>property Crystals of the link<sup>ut</sup>, <sup>p</sup>rzem<sup>s</sup>wa water<sup>and</sup> 1. methanol and dried. 2.9 g of 1- / 1,2,5-thiadiazol-3-ylethyl / -2- (nitromino / imrdazolidine) are obtained, mp 162-165 ° G.
Example XX. Compound No. 20 of formula 30. A mixture of 2.9 g of 2-nitroiminothiazolidine, 2.9 g of anhydrous potassium carbonate, 3.2 g of 2-chloro-1-5-methylene chloride and 50 ml of acetonitrile are refluxed. within 5 hours, stirring vigorously. After completion of the reaction, most of the acetonitrile is distilled off and water is added to the residue. The resulting solid product is filtered off and recrystallized from ethanol to give 3.8 g of 3- (2-chloro-5-pyridylmethyl) -2- (nitrommino) tarotin, mp 137-138 ° G.
EXAMPLE XXI Compound No. 21 of formula 31. To a mixture of 1.3 g of finely powdered 2-nitroiminoiiazolidine and 30 ϋ dry acetonitrile is added portionwise 0.4 g of sodium hydride / 600% in oil / at room temperature and stirring until no more hydrogen is produced. Then a solution of 1.7 g of 2-chloro-5-thiazorilimethyl chloride in 10 ϋ acetonitrile and the resulting mixture of the mixture is added dropwise at room temperature for 3 hours at room temperature, then poured into ice water. The organic matter is extracted with dichloromethane, the chlorolimethane extracts are washed with 1% sodium hydroxide solution and water. The precipitated product after evaporation of dichloromethane is fused with ether and dried. 1.4 g of 1- (2-Chl-5-thiazolylmethyl) -2- (nitroiminl / imidazolidine) are obtained, mp 147-150 ° G.
Example XXII. Compound No. 22 with formula 32. The method is described in the example
149 199
VII, from 2.3 g nitro / tetrahydro-2H-1,3-thiazine-2-ylidene / ethyl acetate and 1.6 g of 2-chloro-5-pyridylmethyl chloride is obtained as a gummy substance. This product is triturated with ethanol, the insoluble material is washed with hexane and purified on a silica gel column. 0.2 g / ethyl 3- (2-chloro-5-pyridylmethyl) tetrahydro-2H-1,3-thiazole-2-ylene-7-ethyl acetate are obtained, mp 180-184 ° C.
Example d. HIII. Compound No. 23 of formula 33.5.8 g 2-imino-3- (4-pyridylmethyl) thiazolddyra is added to 20 ml concentrated sulfuric acid in -. 50 ° C.
Then 6 ml of fuming nitric acid is added to the solution at the same temperature<sup>g</sup>o. Mixtures<sup>ę</sup> reaction<sup>and</sup> mixed in coagulum <sup>30</sup> minutes in <sup>0</sup> - 5°<sup>C</sup> and - pours on <sup>p</sup>about<sup>k</sup>ru.szon<sup>s </sup>ice. Extraction with dichilormethane twice and treatment in the usual way gives 1.4 g of 2-nitroimint-3- / 4-pyridylmethylt / thiazolddyra with a melting point of 151-152 ° C.
Example XXII. Compound No. 24 of formula 34. A mixture of 2.7 g 3- (2-^^^ - 5-pyridyloraethyl-22 / nitroethylene / thiazolidine, 3.5 g of methylvinyl tone and 30 ml of chloroform misz sd.ę<sup>p</sup>slaughter <sup>2 d</sup>than in 4<sup>0</sup>°<sup>C</sup>under nitrogen. Nast<sup>Ep</sup>does not add 3.5 <sup>g</sup> methyl vinyl ketone and mix for another 2 days at the same temperature. The volatile material is removed under reduced pressure and the residue is purified by silica gel column chromatography. 0.1 g of 3- (2-chloro-5-pyridylmethyl) -2- (1-eitro-4-oxopentylidene) / thiazolddyra is obtained, m.p. 75-80 ° C.
Example XIV. Compound No. 25 of formula 35. 2.5 g of 1- (2-CHOΓO-5-pirddy-emeeyl / -2- / nitremethylene / emidazoldidine) is dissolved in 40 ml of dry dichloromethane and 10 ml of vocdy are added. A solution of 1.6 g bromine in 10 ml dichloromethane is added to the mixture over 10 minutes at 0-5 ° C with good stirring. The reaction mixture is stirred for 10 minutes at 0-5 ° G, the crystallized product is filtered off, washed with cold water and a small amount of dichloromethane and dried. 2.5 g of 1- (2-chloro-5-pyridylmethylt / -2 / bromonitiomethylene / imidaztlidine) are obtained, m.p. 110-115 ° C (decomposed).
Example XJXTI. Compound No. 26 of formula 36. 3.1 g of phenyl chloroformate is added to a solution of 1.6 g of 1-methylimidazole in 50 ml of dichloromethane at a temperature of less than 0 ° C and the mixture at this temperature within 30 minutes. , 5 g
1- / 2-chloro-5-pyridylmtoyl / - / 2nnrteotθtyletoemidazolddyJιy and stir for 24 hours at room temperature. The mixture is then washed with water, 1% saline acid and 1% sodium hydroxide solution. Removal by distillation of dichloromethane gives 3.2 g of vitreous nitro 1 // 2-chloro-5-prridylmeromer 0 // 3-phenylcabtonytemidazolidyπ-2-obvious_<sub><</sub>7 phenyl. This compound is dissolved in 20 ml of dimethyloeramide, 1.7 g of sodium carbonate are added to the solution, and the resulting mixture of mashine for 3 days at room temperature. Water is then added and the organic layer is extracted with dichloromethane. The extract is washed with 1% sodium hydroxide solution and water. The dichloromethane is evaporated and the residue is purified on a silica gel chroeatogaphase column.
0.2 g of nitro ~ "1- (2-chloro-5-pyriethylmethyl / emidazolidin-2-yidteπo) is obtained.<sub>-</sub>Phenyl 7acetate with a 'melting point' <sup>224</sup> - 2<sup>28</sup>° C. <sup>/</sup>with timetable.
Example XXII. Compound No. 27 of formula 37. 0.2 g of 60% sodium hydride in oil is added to a solution of 1.3 g of 1- (2-chloro-5-pyridylmethyl) -2-ni'-methylene imidazolidine in 15 ml of dry dimethyltrofloemaeide and mixed. at room temperature to stop the evolution of hydrogen. Then 0.9 g of 4-chlorobenzene sulfite chloride are added dropwise to the solution at 0 ° C. with stirring for 1 hour at room temperature and poured into ice water. The separated crystals are filtered off and recrystallized from ethyl acetate. 1.3 g of 1- (2-chloro-5-pyridylmethyl) -2-chloro-4-chlorophenyl-7-imidazolidyrine are obtained. <sup>t</sup>opeiteia<sup>59</sup> - <sup>161</sup>° C.
149 199
Example XXIII. Compound No. 28 of formula 38. A solution of 0.9 g of benzenesulfonylisocyanate in 10 ml of dry dichloromethane is added dropwise to a solution of 1.3 g of 1- (2-chloro-5-pyridylmethyl) -2-riitrorTiethylenininiidazolidine in 25 ml of dry dichloromethane at room temperature · The solution is stirred is stirred at the same temperature for 2 hours and the dichloromethane evaporated under reduced pressure to about half volume. The crystallized product is filtered off and washed with ether. 1 g of 2 - / "1- (2-chloro-5-pyridylmethyl) imidazolidin-2-ylidene_7-2-nitooacetmmide N-benzenesulfonyl is obtained at a temperature of<sup>p</sup>not suitable 95 - 1 ° 0 ° C. .
Example XXIX. Compound No. 29 of formula 39. A mixture of 2.2 g of 2-nitro-methyl-1/3-pyridylethyl / -idazolidine, 1.6 g of 2-chloro-5-chloromethylpyridine, 1.4 g of anhydrous potassium carbonate in 3 ° ml of acetonitrile reflux for 16 hours with stirring. The acetonitrile is removed under reduced pressure, dichloromethane is added to the residue, washed with water and 1% sodium hydroxide solution. Dichloromethane is removed under reduced pressure, and the residue is purified on a silica gel chroiatric column. 2.1 g of 1- (2-chloro-5-propyl-Syloxy) are obtained<sup>s</sup>lo / -2-nitro ^ ino-1-Zlpyrpy ^ lmmethyl / L-dimidazoline at a temperature of<sup>p</sup>pressure<sup>and</sup> 1<sup>43</sup>-<sup>144</sup>° C.
Example XXX. Compound No. 3 ° with a formula of 4 °. 0.4 g of 60% sodium hydride in oil is added portionwise to a solution of 2.6 g of 1- (2-chloro-O-5-pyridylethyl) -2-nitroamidamidoline in 20 ml of dry dimethylformamide. The mixture is stirred at room temperature until no more hydrogen is removed. A solution of 1.5 g of isopropyl bromide in 5 ml of dry dimethylformamide and a meal is added dropwise to the mixture at room temperature over 3 hours at room temperature. The mixture is then poured into ice water and the precipitated crystals are filtered off. After recrystallization from ethanol, 1.5 g of 1- (2-chloro-5-pyrid-1-methyl) --- isophenyl-2-nitroimiazolidyrine is obtained, mp 138-142 ° G.
Example XXXI. Compound No. 31 is used in 41. A mixture of 2.7 g 3- (2-chloro-5-pyridylmethyl) -2-nitromethylene-thiazoldidine and 8 ϋ butyric anhydride is stirred for<sup>8 g</sup>about<sup>d</sup>from: LN in <sup>60</sup>°<sup>G</sup> in the atmosphere<sup>f</sup>nitrogen era. Then volatile substances are removed under a pressure of 1.333 hPa, maintaining the bath temperature below 60 ° C. The residue is dissolved in dichloromethane and washed with 1% sodium hydroxide solution. The dichloromethane layer is purified on a silica gel column. 0.15 g of 1- (1-) - 2-chloro-5-DirsdylmneySo / thiazolidsη-2-s1idene 7-1-nitro-4-pannonone 20 * is obtained in the form of a viscous oil, 1.6342. The following compounds of formula 1 are also obtained by the method described in the above examples:
a / compound No. 32 of compound 42, in which Z represents a group of compound 44, n is zero and Y is nitrogen; melting temperature 143 - 145 ° C;
b / Compound No. 33 on Figure 42, in which Z is a group of formula 50, n is zero, and Y is C-GOCHOCH; = 1.6358;
c / compound No. 34 of formula 42, wherein Z is a group of formula 44, n is 1 and Y is C-COOC ^ H ^;
j - 1.5978;
d / compound No. 35 of formula 51, n ^ = 1.5995;
e / compound No. 336 of formula 53, melting point 137-14 (^ 0;
f / compound No. 37 of formula 87, melting point 140 - 14 ° Gc decomposition /.
The compounds described in the following tables are also obtained by the method described in the above examples.
149 199
Table 1 Compounds of formula 54
<td>Relationship 1 No. 1 1</td><td>rn</td><td>i Connection position 1 ring pyridine 1</td><td>ί <sup>Q</sup>2 <sup>j</sup> 1 1 1 1</td><td>Temppratura m.p. ° C</td><td>Ί</td>
<td></td><td></td><td></td><td></td><td></td><td></td>
<td> 38 ! 1</td><td> 2</td><td><sup>1</sup> . <sup>3</sup>- 1</td><td>1 1 1 'J. 1 1 AND</td><td>90 - 94 / distribution /</td><td></td>
<td> 39 !</td><td> 2</td><td> 1 4- |</td><td>1 l '1</td><td> 154 - 157</td><td></td>
<td>40 units</td><td> 3</td><td>and 4-</td><td> 1 _ 1</td><td> 163 - 165</td><td></td>
<td>41 - I |</td><td> 2</td><td><sup>1</sup> 5- 1</td><td>! 2-CH<sub>3</sub> !</td><td> 157· - 650</td><td></td>
<td> 42 1</td><td> 3</td><td> ! 5-</td><td>1 2-CH3 j</td><td> 155,5 - 15^3,5</td><td></td>
<td> 43 |</td><td> 2</td><td> 1 5- |</td><td>1 - and<sub>l</sub> 2-CF<sub>3</sub><sup>1</sup> 1 3 1</td><td> 134 - 146</td><td></td>
<td>44 units 1 ----------------- '</td><td> 2</td><td> 1 1 5- 1</td><td>1 3-Br j -L__ ____J</td><td> 1 98 - 201</td><td></td>
Table 2
Compounds of formula 55
<td rowspan="2"></td><td rowspan="2">and Relationship and<sup>No.</sup> and 1 1</td><td rowspan="2"><sup>Q</sup>2</td><td rowspan="2">T 1 1 1 1 1 1 1 1</td><td colspan="2"> -----------<sub>r</sub>Positions j ring-1 piry-1</td><td colspan="2" rowspan="2">R<sup>1</sup>! r2 1 1 1 1 1</td><td rowspan="2">'T Ί 1 1 1 1 1 1</td><td rowspan="2">R<sup>3</sup></td><td rowspan="2">Τ ' 1 AND 1 1 1 1 1 1</td><td rowspan="2">TT 1 1 1 1 1</td><td rowspan="2">n</td><td rowspan="2">ii AND 1 1 1 1</td><td rowspan="2"></td><td rowspan="2">r - - - * 1 1 y 1 1 1 1 1</td><td rowspan="2">-T</td>
<td>dyniowe- §</td><td> 1 1 1</td>
<td></td><td> - -<sup>1</sup>—</td><td> 2</td><td>Ί<sup>-</sup> 1</td><td> 3</td><td>T 1</td><td colspan="2">_4_L-5_</td><td>T 1 4 ..</td><td> 6</td><td>1 J ..</td><td>and 1</td><td> 8</td><td>1 c</td><td></td><td> 1 10</td><td></td>
<td></td><td> 45 (</td><td></td><td> 1 1 1</td><td> 4-</td><td> 1 1 1</td><td>H</td><td><sup>CH3</sup></td><td> 1 1 1</td><td> -</td><td> 1 1 1</td><td>j _ j</td><td> 0</td><td>j 1H</td><td></td><td>1 j CH</td><td></td>
<td></td><td> 46 1</td><td> -</td><td> 1 1</td><td> 3-</td><td> 1 1 1</td><td></td><td>CH3</td><td> 1 1 |</td><td> -</td><td>l 1 AND</td><td> 1 |</td><td> 0</td><td>and H. AND</td><td></td><td><sup>1</sup> CH 1</td><td></td>
<td></td><td>47 units</td><td> -</td><td> 1 1</td><td> 4-</td><td> 1 1</td><td>H</td><td>H</td><td> 1 1</td><td><sup>CH3</sup></td><td> 1 1</td><td>CH<sub>3</sub>j</td><td> 1</td><td>1H</td><td></td><td>j CH</td><td></td>
<td></td><td>48 units</td><td> -</td><td> 1 1</td><td> 3-</td><td> 1 1</td><td>H</td><td>H</td><td> 1 1</td><td></td><td> 1 1</td><td></td><td> 0</td><td>their</td><td></td><td>THEIR |</td><td></td>
<td></td><td>49 units</td><td>2-C1</td><td> 1 1 1</td><td> 5-</td><td> 1 1</td><td>H</td><td>H</td><td> 1 1</td><td> -</td><td> 1 1 1</td><td> “ 1</td><td> 0</td><td>Their?</td><td></td><td>J CH</td><td></td>
<td></td><td> 50 1</td><td> -</td><td> 1 1</td><td> 3-</td><td> 1 1</td><td>H</td><td>H</td><td> 1 1</td><td> -</td><td> 1 1</td><td> 1</td><td> 0</td><td>1 7 and reference</td><td> 56</td><td>1 CH</td><td></td>
<td></td><td> 51 '</td><td> -</td><td> 1 1 |</td><td> 4-</td><td>1 1 l</td><td>H</td><td>H</td><td> 1 1 1</td><td> -</td><td> 1 1 1</td><td> 1 ” 1</td><td> 0</td><td>1 j pattern</td><td> 57</td><td>j CH</td><td></td>
<td></td><td> 52 1</td><td>2-C1</td><td> 1 1</td><td> 5-</td><td>1 l</td><td>H</td><td>H</td><td> 1 1</td><td> -</td><td> 1 1</td><td>_ AND</td><td> 0</td><td>j pattern</td><td> 58</td><td>j CH</td><td></td>
<td></td><td>53 and</td><td>2-C1</td><td> 1 1 |</td><td> 5-</td><td> 1 1 |</td><td>H</td><td>H</td><td> 1 1 |</td><td> -</td><td> 1 1 |</td><td> 1 |</td><td> 0</td><td>j pattern</td><td> 57</td><td><sup>1</sup> CH l</td><td></td>
<td></td><td> 54 ;</td><td>2-C1</td><td> 1 1</td><td>E_</td><td> 1 1</td><td>H</td><td>H</td><td> 1 1</td><td> -</td><td> 1 1</td><td> _ 1</td><td> 0</td><td>[pattern</td><td> 56</td><td>1 CH</td><td></td>
<td></td><td>55 and</td><td>2-C1</td><td> 1 1</td><td> 5-</td><td>1 1 AND</td><td>H</td><td>H</td><td>1 1 AND</td><td> -</td><td>1 1 AND</td><td>f AND</td><td> 0</td><td>j pattern 1</td><td> 60</td><td><sup>1</sup> CH |</td><td></td>
<td></td><td> 56</td><td>2-C1</td><td> 1 1</td><td> 5-</td><td> 1 1</td><td>H</td><td>H</td><td> 1 1</td><td> -</td><td> 1 1</td><td></td><td> 0</td><td>j pattern</td><td> 61</td><td>J CH</td><td></td>
<td></td><td> 57 <sup>1</sup></td><td>2-C1</td><td> 1 1</td><td> 5-</td><td> 1 1</td><td>H</td><td>H</td><td> 1 1</td><td> -</td><td> 1 1</td><td> 1</td><td> 0</td><td> 1</td><td></td><td>j model 62 AND</td><td></td>
<td></td><td>56 units</td><td>2-C1</td><td> 1 1 1</td><td>c J</td><td> 1 1</td><td>H</td><td>H</td><td>AND 1</td><td> -</td><td> 1 1</td><td> ” 1</td><td> 0</td><td>jk</td><td></td><td>j C-CCC h?</td><td></td>
<td></td><td>59 units</td><td>2-C1</td><td> 1 1</td><td> 5-</td><td> 1 1</td><td>H</td><td>H</td><td> 1 1</td><td> -</td><td> 1 1</td><td> 1</td><td> 0</td><td>| h</td><td></td><td>and formula 63</td><td></td>
<td></td><td> 60 <sup>1</sup></td><td>2-C1</td><td> 1 1 1</td><td> 5-</td><td> 1 1 1</td><td>H</td><td>H</td><td> 1 1 1</td><td> -</td><td> 1 1 1</td><td> 1 1</td><td> 0</td><td>jh</td><td></td><td>J C-C00CoH</td><td></td>
<td></td><td>61 j AND</td><td>2-C1</td><td> 1 1 1</td><td></td><td> 1 1 1</td><td>H</td><td>H</td><td> 1 1 |</td><td> -</td><td> 1 1 |</td><td>_ AND |</td><td> 0</td><td>1 u 1</td><td></td><td>j model 65 l</td><td></td>
<td></td><td>62 j</td><td>2-C1</td><td> 1 1</td><td>E</td><td> 1 1</td><td>H</td><td>H</td><td> 1 1 1</td><td> -</td><td>1 1 AND</td><td> 1 1</td><td> 0</td><td><sup>ICH3</sup></td><td></td><td rowspan="2"><sup>1</sup> C-CCCJH1 3 7 2<sup>] N</sup></td><td></td>
<td></td><td> 63 1</td><td>2 -Cl</td><td> 1 1</td><td> 5-</td><td> 1 1</td><td>H</td><td>H</td><td> 1 1</td><td> -</td><td> 1 1</td><td> _ 1</td><td> 0</td><td>JCH<sub>2</sub>CH</td><td>= CH</td><td></td>
<td></td><td> 1</td><td></td><td> 1</td><td></td><td> 1</td><td></td><td></td><td> 1</td><td></td><td> 1</td><td> 1</td><td></td><td> 1</td><td></td><td></td><td></td>
Melting point c<sub>n</sub>
184 - 187 177 - 180 190 - 191 107 - 110 128 - 130
175 - 178
176 - 180
152 - 153
156 - 160
Πρθ1,6495
154 - 156 n | ° 1.6480
135 - 140
102 - 105
213 - 215
169 - 171
- 94 / distribution //
100 - 105 <sup>n</sup>^°1<sup>,</sup>5854 continuation of the table on page 12
149 199
Table 2 cont
<td colspan="6">! and! 2<sup>!</sup> 3 '</td><td> 4 <sup>!</sup></td><td colspan="2"> 5 <sup>!</sup></td><td> 6</td><td colspan="2"><sup>!</sup> 7</td><td>and 8</td><td> . —------</td><td>Ί ------ 1 10</td><td> ! 11</td><td>r -----</td>
<td></td><td>T</td><td></td><td> 1</td><td></td><td> 1</td><td></td><td></td><td>and</td><td></td><td>r</td><td></td><td> |</td><td>AND</td><td></td><td>AND</td><td></td>
<td> ! 64</td><td>AND AND</td><td>2-C1</td><td>1 and |</td><td> 5-</td><td> 1 |</td><td>H <sup>!</sup> |</td><td>H</td><td> 1 1 |</td><td> -</td><td>1 1 AND</td><td> -</td><td>! about</td><td>! formula 64</td><td>ί N.</td><td> ' 126 -</td><td>128 J.</td>
<td> ! &</td><td> 1 1 1</td><td>2-C1</td><td> 1 1</td><td> 5·</td><td> 1 1</td><td>h!</td><td>H</td><td> 1 1</td><td> -</td><td> 1 1</td><td> -</td><td>! about</td><td>! model 57</td><td> ! /</td><td> ! 146 -</td><td>148 and</td>
<td>and 66</td><td>1 and</td><td>2-C1</td><td>1 t 1</td><td> 5-</td><td> 1 1 |</td><td>H <sup>!</sup>AND</td><td>H</td><td> 1 1 |</td><td> -</td><td> 1 1 |</td><td> -</td><td>! about</td><td>and pattern 60</td><td>ΐ /</td><td>J 128 -</td><td> 131 [</td>
<td> ! 67</td><td> 1 1</td><td>2-C1</td><td> 1 1</td><td> 5-</td><td> 1 1</td><td>hj</td><td>H</td><td> 1 1</td><td> -</td><td> 1 1</td><td> -</td><td> 1 °</td><td>1 goch<sub>3</sub></td><td> ! /</td><td>and 144.5</td><td> -146 !</td>
<td> ! 68</td><td> 1</td><td>2-C1</td><td> 1 1</td><td> 5-</td><td> 1 1</td><td>H and AND</td><td>H</td><td> 1 1 |</td><td> -</td><td> 1 1 1</td><td> -</td><td><sup>1</sup> about 1</td><td>and formula 66</td><td>! N</td><td> ; 118 -</td><td>122 J.</td>
<td>J 69</td><td> 1 1 1</td><td>2-C1</td><td> 1 1</td><td>c_</td><td> 1 1</td><td>h!</td><td>h '</td><td> 1 1</td><td> -</td><td> 1 1</td><td> -</td><td> ! °</td><td>] C00C<sub>2</sub>huh</td><td>! N</td><td> ! 125 -</td><td> 126 !</td>
<td> ! 70</td><td> 1 1</td><td>2-C1</td><td>1 AND AND</td><td></td><td> 1 1</td><td>H!</td><td>H</td><td> 1 1</td><td> -</td><td>1 1 AND</td><td> -</td><td>! about t</td><td>and formula 67 |</td><td><sup>!</sup> /</td><td> [ 135 -</td><td>140 J</td>
<td> ! 71</td><td>1 1 l</td><td>2-Cl</td><td> 1 1 1</td><td> 5-</td><td> 1 1</td><td>H!</td><td>H</td><td> 1 1</td><td> -</td><td> 1 1</td><td> -</td><td> ! <sup>0</sup></td><td>J pattern 68</td><td>ΐ N.</td><td>! 19i -</td><td> 192 !</td>
<td>! 72 ΐ 73</td><td> 1 1 1 1 1</td><td>2-Cl 2-C1</td><td> 1 1 1 1 1</td><td> 5- 5-</td><td>1 1 1 1 AND</td><td>H! 1 H!</td><td>H H</td><td> 1 1 1 1 1</td><td> -</td><td> 1 1 1 1 1</td><td> -</td><td>1 st 1 and 0</td><td>Ί CON / CH ^ / ą J model 69</td><td><sup>!</sup> / ! /</td><td><sup>1</sup> 186 <sup></sup>! N201 • <sup>n</sup>D <sup>1</sup> '</td><td>188 J. 5615</td>
<td>L ___-</td><td> 1</td><td></td><td> 1</td><td></td><td> 1</td><td> 1</td><td></td><td> 1</td><td></td><td></td><td></td><td>-U -</td><td> .—1__ _ _ ___</td><td> 1</td><td></td><td>___J</td>
Table 3 Compounds of formula 70
<td></td><td></td><td> 1</td><td></td><td>"Ί<sup>-</sup> 1</td><td>Connection position</td><td> 1 |</td><td></td><td>1 ' 1 t</td><td></td><td>-1 ------ 1 l</td><td>[Temppeatura!</td>
<td></td><td>Relationship</td><td> 1 1</td><td>Het</td><td> 1</td><td>joining the group</td><td> 1</td><td rowspan="2"><sup>Q</sup>2</td><td> 1</td><td>R</td><td>1 m</td><td>1 melting and</td>
<td></td><td>No.</td><td> 1 |</td><td></td><td>1 l</td><td>heterocyclic</td><td> 1 1</td><td> 1 1</td><td></td><td> 1 1</td><td><sup>and</sup> ° C. <sup>!</sup></td>
<td></td><td></td><td> 1</td><td></td><td> 1</td><td>football</td><td> 1</td><td></td><td> 1</td><td></td><td> 1</td><td></td>
<td></td><td> 74</td><td> 1 1 1 1</td><td> 0</td><td> 1 1 1</td><td> 2</td><td> 1 1 1</td><td> -</td><td> 1 1 1</td><td>H</td><td>ΐ ! 3</td><td> 1 1 ,'194-196 !</td>
<td></td><td> 75</td><td> 1 1</td><td>S</td><td> 1 1</td><td> 2</td><td> 1 1</td><td> -</td><td> 1 1 (</td><td>H</td><td> ! 3</td><td><sup>!</sup> 189 - 190 {</td>
<td></td><td> 76</td><td> 1 1 |</td><td>s</td><td>AND 1 1</td><td> 3</td><td> 1 1 1</td><td> -</td><td> 1 1</td><td>H</td><td> [ 3</td><td> ! 196 - 198 !</td>
<td></td><td> 77</td><td> 1 1</td><td> /</td><td> 1 1</td><td> 2</td><td> 1 1</td><td>1-H</td><td> 1 1</td><td>H</td><td> ! 2</td><td> ! 201 - 205 !</td>
<td></td><td> 78</td><td> 1 1 |</td><td> /</td><td> 1 1 |</td><td> 2</td><td>1 1 l</td><td>1-H</td><td> 1 1 1</td><td>H</td><td> ! 3</td><td> ] 183 - 185 !</td>
<td></td><td> 79</td><td> 1 1</td><td> /</td><td> 1 1</td><td> 2</td><td> 1 1</td><td>1-CH</td><td> 1 1</td><td>H</td><td> ! 3</td><td>! 207 - 213! AND</td>
<td></td><td> 80</td><td> 1 1 |</td><td> 0</td><td> 1 1 1</td><td> 2</td><td>1 1 AND</td><td>5-CH</td><td> 1 1 1</td><td>H</td><td>J 2</td><td> 1 151 - 152 ;</td>
<td></td><td> 81</td><td> 1 1</td><td> 0</td><td> 1 1</td><td> 2</td><td> 1 1</td><td>5-d</td><td> 1 1</td><td>H</td><td>and 2</td><td> ! 130 - 131 !</td>
<td></td><td> 82</td><td> 1 1</td><td>S</td><td> 1 1</td><td> 2</td><td> 1 1</td><td>5-Br</td><td>f 1 |</td><td>H</td><td> '[ 3</td><td>J 184-186;</td>
<td></td><td> 83</td><td> 1 1 1</td><td> 0</td><td> 1 1</td><td> 2</td><td> 1 1</td><td>5-C /</td><td> 1 1</td><td>H</td><td> 1 2</td><td> '212-215 !</td>
<td></td><td> 84</td><td> 1 1</td><td> 0</td><td> 1 1</td><td> 2</td><td> 1 1</td><td>model 85</td><td>1 1 AND</td><td>H</td><td><sup>!</sup> 2 AND</td><td> ' 127 <sup>-</sup> 129 units</td>
<td></td><td> 85</td><td> 1 1 1</td><td>s</td><td> 1 1 1</td><td> 2</td><td> 1 1</td><td>4-CH3</td><td> 1 1</td><td rowspan="2"><sup>CH</sup>3</td><td> ! 2</td><td> ' 170-171,5 '</td>
<td></td><td></td><td> 1</td><td></td><td> 1</td><td></td><td> 1</td><td></td><td> 1</td><td> 1</td><td>II</td>
149 199
Table 4
A compound of formula 71
<td>Compound No.</td><td> —<sub>r</sub>_AND AND AND AND</td><td>Het</td><td> ---<sub>r</sub>- 1 1 1 1 1</td><td>Attachment position of the heterocyclic group</td><td> —1— 1 1 1 1 1</td><td>Q</td><td> 2</td><td> Γ 'and 1 1 1 1</td><td></td><td>"Γ1 1 1 1 1</td><td>Temppratura m.p. ° C</td>
<td></td><td></td><td></td><td></td><td></td><td> 1</td><td></td><td></td><td> 1</td><td></td><td> 1</td><td></td>
<td> 86</td><td>AND AND AND</td><td> 0</td><td> 1 1 1</td><td> 3 ·</td><td> 1 1 1</td><td>5-CH3</td><td></td><td> 1 1 1</td><td> 3</td><td>L 1 1</td><td> 186 - 188</td>
<td> 87</td><td> 1 1 |</td><td> 0</td><td> 1 1 |</td><td> 5</td><td> 1 1 1</td><td>3-CH3</td><td></td><td>1 1 AND</td><td> 3</td><td> 1 1</td><td> 200 - 201</td>
<td> 88</td><td> 1 1</td><td> 0</td><td> 1 1</td><td> 5</td><td> 1 1</td><td>3-GP</td><td></td><td> 1 1</td><td> 3</td><td> 1 1</td><td> 177 -190</td>
<td> 89</td><td>1 1 AND</td><td>N</td><td> 1 1</td><td> 5</td><td> 1 1</td><td>1-H.</td><td></td><td> 1 1</td><td> 2</td><td> 1 1</td><td> 190 - 193</td>
<td> 90</td><td> 1 1</td><td>N</td><td> 1 1</td><td> 4</td><td> 1 1</td><td>1-H</td><td></td><td> 1 1 1</td><td> 2</td><td>and 1</td><td> 196 - 198</td>
<td> 91</td><td> 1 1</td><td>N</td><td> 1 1</td><td> 4</td><td> 1 1</td><td>1-H</td><td></td><td> 1 1</td><td> 3</td><td> 1 1</td><td> 222 - 225</td>
<td> 92</td><td> 1 1</td><td>N</td><td> 1 1 1</td><td> 3</td><td> 1 1 1</td><td>their<sub>3</sub></td><td></td><td>1 1 AND</td><td> 2</td><td>1 1 l</td><td> 212 - 215</td>
<td> 93</td><td> 1 1</td><td>N</td><td> 1 1</td><td> 4</td><td> 1 1</td><td>and-CH</td><td></td><td> 1 1</td><td> 2</td><td> 1 1</td><td> 179 - 180</td>
<td> 94</td><td>1 1 l</td><td>N</td><td> 1 1 1</td><td> 4</td><td>1 1 AND</td><td>1-C<sub>2</sub><sup>h</sup>5</td><td></td><td> 1 1 |</td><td> 3</td><td> 1 1 |</td><td> 145 - 148</td>
<td> 95</td><td> 1 1</td><td>N</td><td> 1 1</td><td> 5</td><td> 1 1</td><td>1-H, 3</td><td> -<sup>C</sup>*<sup>3</sup></td><td> 1</td><td> 2</td><td> 1 1</td><td> 183 - 185</td>
<td> 96</td><td> 1 1 1</td><td>N</td><td> 1 1 1</td><td> 3</td><td> 1 1 1</td><td>their<sub>3</sub>,</td><td>5-C1</td><td>1 1 AND</td><td> 2</td><td> 1 1</td><td> 195 - 198</td>
<td> 97</td><td> 1 1</td><td>N</td><td> 1 1</td><td> 3</td><td> 1 1</td><td>1-s<sub>3</sub>,</td><td>5-C1</td><td> 1 1</td><td> 3</td><td> 1 1</td><td> 222 - 224</td>
<td> 98</td><td>1 1 1 J_ -</td><td>N</td><td>1 1 1 _ _Ł</td><td> 4</td><td> 1 1 1 --1</td><td> 1,3,5-</td><td>H</td><td>1 1 1 __L- -</td><td> 3</td><td> 1 1 1 -</td><td> 192 - 194</td>
Table 5
Compounds of formula 72
<td></td><td rowspan="2">Relationship</td><td>Ί AND</td><td></td><td> 1 1</td><td>Connection position</td><td> 1 1</td><td></td><td> 1 1</td><td></td><td>AND AND</td><td>Temp eratura</td><td></td>
<td></td><td>AND 1</td><td>Het</td><td> 1 1</td><td>of the heterocyclic group</td><td> 1 ’ 1</td><td>q<sub>2</sub></td><td> 1 1</td><td>p</td><td>and AND</td><td>m.p.</td><td></td>
<td></td><td>No.</td><td> 1 1 1</td><td></td><td> 1 1 1</td><td>cyclical</td><td> 1 1 1</td><td></td><td> 1 1 1</td><td></td><td>1 r 1</td><td>° C.</td><td></td>
<td></td><td rowspan="2"> 1</td><td>and</td><td rowspan="2"> 2</td><td> r ~ 1</td><td rowspan="2"> 3</td><td> ~1 1</td><td rowspan="2"> 4</td><td> 1</td><td rowspan="2"> 5</td><td>r 1</td><td rowspan="2"> 6</td><td></td>
<td></td><td></td><td>- ł_ - -</td><td></td><td></td><td></td><td></td>
<td></td><td> 99</td><td> 1 1 1</td><td> 0</td><td> 1 1 1</td><td> 5</td><td> 1 1 1</td><td>4-CH3</td><td> 1 1 1</td><td> 2</td><td>AND 1 1</td><td> 200 - 202</td><td></td>
<td></td><td> 100</td><td> 1 1 |</td><td> 0</td><td> 1 1 |</td><td> 5</td><td> 1 1 1</td><td rowspan="2">4-CH3</td><td> 1 1</td><td> 3</td><td> 1 1</td><td> 221 - 224</td><td></td>
<td></td><td> 101</td><td> 1 1</td><td>s</td><td> 1 1</td><td> 4</td><td> 1 1</td><td> 1 1</td><td> 2</td><td> 1 1</td><td> 21 3-21 6</td><td></td>
<td></td><td> 102</td><td> 1 1 |</td><td>s</td><td>l 1 f</td><td> 4</td><td>1 1 AND</td><td> -</td><td> 1 1</td><td> 3</td><td> 1 1</td><td> 181 - 183</td><td></td>
<td></td><td> 103</td><td> 1 1</td><td>s</td><td> 1 1</td><td> 5</td><td> 1 1 1</td><td> -</td><td> 1 1</td><td> 2</td><td> 1 1</td><td> 169 - 174</td><td></td>
<td></td><td> 104</td><td> 1 1</td><td>s</td><td> 1 1</td><td> 4</td><td> 1 1</td><td>2-CH3</td><td> 1 1</td><td> 2</td><td> ] 1</td><td> 170 - 172</td><td></td>
<td></td><td> 105</td><td> 1 1</td><td>s</td><td> 1 1</td><td> 4</td><td> 1 1</td><td>2-CH3</td><td> 1 1</td><td> 3</td><td> 1 1</td><td> 203 - 206</td><td></td>
<td></td><td> 106</td><td> 1 1</td><td>. s</td><td> 1 1</td><td> 5</td><td> 1 1</td><td rowspan="2">2-CH3 2-C1</td><td> 1 1</td><td> 2</td><td> 1 1</td><td> 162 - 166</td><td></td>
<td></td><td> 107</td><td> 1 1 1</td><td>s</td><td> 1 1 1</td><td> 4</td><td>1 1 AND</td><td> 1 1 |</td><td> 2</td><td>f 1 AND</td><td> 162 - 165</td><td></td>
<td></td><td> 108</td><td> 1 1</td><td>s</td><td> 1 1</td><td> 4</td><td> 1 1</td><td>2-C1</td><td> 1 1</td><td> 3</td><td>AND 1</td><td> 190 - 194</td><td></td>
<td></td><td> 109</td><td> 1 1 |</td><td>s</td><td> 1 1 |</td><td>R</td><td> 1 1 )</td><td> 2-01</td><td>1 L |</td><td> 2</td><td> 1 1 1</td><td> 191 - 192</td><td></td>
<td></td><td> 110</td><td> 1 1</td><td>s</td><td> 1 1</td><td> 5</td><td> 1 1</td><td>2-C1</td><td>and 1</td><td> 3</td><td> 1 1</td><td> 203 - 205</td><td></td>
<td></td><td> 1 1 1</td><td> 1 1 |</td><td>s</td><td> 1 1 1</td><td> 5</td><td>1 1 AND</td><td>2,4-Cl</td><td>1 1 f</td><td> 2</td><td> 1 1</td><td> 179 - 181</td><td></td>
<td></td><td> 1 1 2</td><td> 1 1</td><td>N</td><td> 1 1</td><td> 2</td><td> 1</td><td>1-H</td><td> 1 1</td><td> 2</td><td> 1 1</td><td> 239 - 240</td><td></td>
<td></td><td> 113</td><td> 1 1 1 1</td><td>N</td><td> 1 1 1 1</td><td> 4</td><td> 1 1 1 1</td><td>1-H</td><td>1 1 t 1</td><td> 3</td><td> 1 1 1 1</td><td> 169 - 173</td><td></td>
<td></td><td></td><td> 1</td><td></td><td> 1</td><td></td><td> 1</td><td>series</td><td>1 further</td><td colspan="3">1 table on page 14</td><td> .1</td>
149 199
Table 5 cont
<td></td><td> 1</td><td>AND l -</td><td> 2</td><td> 1 1</td><td> 3</td><td> 1 1</td><td> 4</td><td>AND 1</td><td> 5</td><td>r</td><td> 6</td><td></td><td>—1 AND</td>
<td></td><td> 114</td><td>n 1 1</td><td>N</td><td> Γ 1 1 |</td><td> 2</td><td> 1 1 1</td><td>1 CH?</td><td>and 1 1</td><td> 2</td><td> 1 1 1</td><td> 246 -</td><td> 252</td><td></td>
<td></td><td> 115</td><td> 1 1</td><td>S</td><td> 1 1</td><td> 5</td><td> 1 1</td><td rowspan="2">2-SCH ^</td><td> 1 1</td><td> 2</td><td> 1 1</td><td> 150 -</td><td> 153</td><td></td>
<td></td><td></td><td> 1</td><td></td><td>____L __</td><td></td><td> ___1---</td><td>1 _at---</td><td></td><td>-at-</td><td></td><td></td><td></td>
Table 6
Compounds of formula 73
<td></td><td>Relationship No.</td><td>1 1 1 1 1 1 t</td><td>from</td><td></td><td> --<sub>r</sub>- - 1 1 and 1 1 1</td><td>R</td><td> _<sub>T</sub>------------ 1 1 them AND 1 1</td><td>--- ---- 1 1 1 1 1 1 u.</td><td>Temperature m.p. ° C</td><td>j</td>
<td>Γ</td><td> 116</td><td>Γ 1 1 |</td><td>pattern</td><td> 74</td><td> 1 1 1</td><td>H</td><td>and ! <sup>2</sup></td><td> 1 1 1</td><td> 206 - 210</td><td></td>
<td></td><td> 117</td><td> 1 1</td><td>pattern</td><td> 75</td><td> 1 1</td><td>H</td><td> 1 2</td><td>1 1 AND</td><td> 265 - 267</td><td></td>
<td></td><td> 118</td><td>1 1 AND</td><td>pattern</td><td> 76</td><td>AND 1 1</td><td>H</td><td> ! 2</td><td>1 AND</td><td> 221 - 225</td><td></td>
<td></td><td> 119</td><td> ) 1</td><td>pattern</td><td> 77</td><td> 1 1</td><td>H</td><td> ! 2</td><td> 1 1</td><td> 178 - 180</td><td></td>
<td></td><td> 120</td><td> 1 1</td><td>pattern</td><td> 78</td><td>1 1 AND</td><td>H</td><td> ! 2</td><td> 1 1</td><td> 188 - 190</td><td></td>
<td></td><td> 121</td><td> 1 1</td><td>pattern</td><td> 79</td><td> 1 1</td><td>H</td><td> ! 3</td><td> 1 1</td><td> 207 - 210</td><td></td>
<td></td><td> 1 22</td><td> 1 1</td><td>pattern</td><td> 80</td><td> 1 1 1</td><td>H</td><td><sup>1</sup> 2 AND</td><td>and 1 1</td><td> 21 2 - 21 5</td><td></td>
<td></td><td> 1 23</td><td> 1 1 1</td><td>pattern</td><td> 81</td><td> 1 1</td><td>H</td><td>and 2</td><td> 1 1</td><td> 185 - 187</td><td></td>
<td></td><td> 124</td><td> 1 1</td><td>pattern</td><td> 82</td><td> 1 1</td><td>H</td><td>and 2 1</td><td>1 1 AND</td><td> 216 - 217</td><td></td>
<td></td><td> 125</td><td> 1 1 |</td><td>pattern</td><td> 47</td><td> 1 1</td><td>H</td><td> ! 2</td><td> 1 1</td><td> 188 - 189</td><td></td>
<td></td><td> 126</td><td> 1 1</td><td>pattern</td><td> 52</td><td> 1 1</td><td>H</td><td> ! 2</td><td> 1 1</td><td> 259 - 260</td><td></td>
<td></td><td> 127</td><td>1 1 l</td><td>pattern</td><td> 52</td><td> 1 1 1</td><td>analysis<sub>3</sub></td><td>ί 2</td><td> 1 1</td><td> 173 - 174</td><td></td>
<td></td><td> 128</td><td> 1 1</td><td>pattern</td><td> 83</td><td> 1 1</td><td>H</td><td>and 2</td><td> 1 1</td><td> 216 - 218</td><td></td>
<td></td><td> 129</td><td> 1 1</td><td>pattern</td><td> 48</td><td> 1 1 1</td><td>H</td><td>AND ! 2</td><td> 1 1</td><td> 172 - 175</td><td></td>
<td>l_</td><td></td><td> —±</td><td></td><td></td><td>_ _L</td><td></td><td> 1</td><td> .. 1 .</td><td></td><td></td>
Table 7
Compounds of formula 84
<td></td><td>Relationship No.</td><td>1 1 1 1 1 AND</td><td></td><td>FROM</td><td> 1 1 1 1 1 1</td><td>R<sup>3</sup></td><td> 1 1 1 1 1 1</td><td> 1 1 1</td><td>m</td><td>Ί 1 1 1 1 1</td><td colspan="2"> .. 7 1 1 1</td><td>Y</td><td> — <sub>T</sub>__ 1 1 1 1 1</td><td>Tempero-] top round</td>
<td></td><td></td><td> 1 . -1 -</td><td></td><td></td><td> 1 - 4--</td><td></td><td> 1 1</td><td> 1 1</td><td></td><td> 1 1</td><td></td><td> 1 1</td><td></td><td> 1 1</td><td>° C <sup>!</sup></td>
<td></td><td> 1</td><td> 1 1</td><td></td><td> 2</td><td>T 1</td><td> 3</td><td>Γ 1</td><td> -4.-1..</td><td> 5</td><td> 1 - -1 .</td><td></td><td> 6 <sup>1</sup></td><td> 7</td><td> 1 _ 1</td><td> 8 !</td>
<td>Γ</td><td></td><td>AND</td><td></td><td></td><td> 1</td><td></td><td> 1</td><td>and</td><td></td><td> 1</td><td></td><td> 1</td><td></td><td> 1</td><td> --- -----!</td>
<td></td><td> 130</td><td>and 1</td><td>pattern</td><td> 44</td><td> 1 1</td><td> -</td><td> 1 1</td><td> _ 1</td><td> 0</td><td> 1 1</td><td>H</td><td> 1 1</td><td>N</td><td>AND AND</td><td>149-150 and</td>
<td></td><td> 131</td><td> 1 1</td><td>pattern</td><td> 45</td><td> 1 1</td><td>H</td><td> 1 1 1</td><td>H! |</td><td> 1</td><td> 1 1 |</td><td>H</td><td> 1 1 |</td><td>N</td><td>AND AND AND</td><td> 123-128 !</td>
<td></td><td> 132</td><td> 1 1</td><td>pattern</td><td> 86</td><td> 1 1</td><td> -</td><td> 1 1</td><td> ” 1</td><td> 0</td><td> 1 1</td><td>H</td><td> 1 1</td><td>N</td><td>AND AND</td><td>141 - 1-45 j</td>
<td></td><td> 133</td><td> 1 1</td><td>pattern</td><td> 46</td><td>1 1 AND</td><td> -</td><td>1 1 AND</td><td> 1 |</td><td> 0</td><td> 1 1 1</td><td>H</td><td> 1 1 |</td><td>N</td><td>AND AND |</td><td> 181 - 183 !</td>
<td></td><td> 134</td><td> 1 1</td><td>pattern</td><td> 49</td><td> 1 |</td><td> -</td><td>1 l</td><td> “ 1</td><td> 0</td><td> 1 1</td><td>H</td><td> 1 1</td><td>N</td><td>AND AND</td><td> 142 - 144 !</td>
<td>L</td><td> _______</td><td>. L_</td><td></td><td></td><td></td><td></td><td>- J.</td><td>t</td><td></td><td> 1</td><td></td><td> 1</td><td></td><td>AND</td><td></td>
continuation of the table on page 15
149 199
Table 7 cont
<td></td><td> 1</td><td> —,—</td><td> 2</td><td> —<sub>r</sub>-AND</td><td> 3</td><td>-Γ-</td><td> 4</td><td>"Τ- ι</td><td> 5</td><td>-Γ 1</td><td> 6</td><td colspan="2"> ! 7</td><td>- - η ----</td><td> 8</td><td>'' Ί 1</td>
<td></td><td> 135</td><td> 1 1 1</td><td>formula 48</td><td>AND 1 1</td><td> -</td><td> 1 1 1</td><td> -</td><td> 1 1 1</td><td> 0</td><td> 1 1 1</td><td>H</td><td></td><td>N</td><td> [21 6</td><td> - 219</td><td></td>
<td></td><td> 136 137</td><td>1 and 1 1</td><td>2 pattern 43 formula 44</td><td>AND 1 AND</td><td>CH3</td><td>1 AND AND 1</td><td><sup>CH3</sup></td><td> 1 1 1 1 1</td><td> 1 0</td><td> ! 1 1 1 1</td><td>H pattern</td><td> 61</td><td>CH CH.</td><td>'210 'twenty. and<sup>n</sup>X> 1</td><td> - 213 ,5 980</td><td></td>
<td></td><td> 138</td><td>1 AND</td><td>formula 44</td><td> 1 1</td><td> -</td><td> 1 1</td><td> -</td><td> 1 1</td><td> 0</td><td> 1 1</td><td>H</td><td></td><td>O-COOO</td><td>C J<sup>0 53</sup></td><td> -155</td><td></td>
<td></td><td> 139</td><td>1 AND</td><td>formula 44</td><td>1 AND 1</td><td> -</td><td> 1 1</td><td> -</td><td> 1 1 1</td><td>about</td><td>1 1 AND</td><td>COCH3</td><td></td><td>N</td><td> [134</td><td> - 136</td><td></td>
<td></td><td> 140</td><td>AND 1 AND ___ l-</td><td>formula 44</td><td>1 1 1 --AT--</td><td> -</td><td>1 1 1 -at-</td><td> -</td><td>1 1 1 -k-</td><td>about</td><td>1 1 1 --J-</td><td>pattern</td><td> 68</td><td>N</td><td>, '156 AND</td><td> - 158</td><td> --AND</td>
The following examples illustrate the biological effect of the agent according to the invention. The comparative compounds used were:
Comparative compound A-1 of formula 88, described in DOS No. 2514402. Comparative compound A-2 of formula 89, described in Japanese Laid-open No. 196-77 / 1984. Comparative compound A-3 of formula 90, described in the above-mentioned opium. Comparative compound A-4 of formula 91, described in Can. J.Chem., Vol. 38, pp. 1787-1796.
Example HH. Study of Nephooettix ciencticeps resistant to organophosphorus agents. The test compound is prepared as follows:
Solvent: 3 parts by weight of xylene
Emmugator: 1 part by weight of ether and ethoxylated ether. In order to form a suitable preparation, 1 part by weight of the active substance is mixed with the abovementioned amount of solvent containing the abovementioned amount of ernuua ^ tc ^ra. The mixture is diluted with water to the specified concentration.
The following test method shall be used: Rice plants approximately 10 cm high, planted in 12 cm pots, are sprayed with 10 ml per pot of the aqueous solution of each active substance in the specified concentration prepared as described above. After drying the preparation, a wire mesh with a diameter of 7 cm and a height of 14 cm is applied to each pot, after which 30 perfect female / imago / Nephotettix cinoticeps female insects are shown under each mesh, showing resistance to phosphorous agents. The pots are placed in a constant-temperature chamber and two days later the number of dead insects is checked by calculating the killing rate.
The obtained results showed that the new active substances reach 100% killing at 8 ppm of the active substance. For comparison, the comparative compounds show:
A-1 - 65% killing at 40 ppm active substance
A-2 - 40% killing at 200 ppm active substance and 0% at 40 ppm active substance
A-3 - 0% at 200 ppm active substance
A-4 - 30% at 200 ppm active substance.
Example ΙΧΧΙΙΙ. Tests against jumping insects were carried out as follows: The preparation is prepared as described in the example ΙΧΧΙΙ it is diluted with water to a certain concentration of the active substance and sprayed with rice plants about 10 cm high, growing in pots with a diameter of 12 cm, in the amount of 10 ml of the preparation for flowerpot. After drying the preparation, a wire mesh with a diameter of 7 cm and a height of 14 cm is applied to each pot. 30 pieces of Imil Nilaparveta lugens Stal, which are resistant to organophosphorus agents, are introduced under the mesh. The pots are placed in a chamber at
149 At 200 ° C and two days later, the number of dead insects is checked and the killing rate is calculated.
In a manner analogous to that described above, the killing rate for Sogatella furcifera Horvath and resistant to organophosphorus compounds Laodelpha striatellus Fallen is determined. It was found that the new active substances 100% 'killing at 40 ppm of the active substance against jumping insects.
In contrast, comparative compounds show: A-1 at 40 ppm 50% killing against N.lugens, 40% against S.furcifera and L.striatellus, A-2 at 200 ppm 30% killing against N.lugens, 20% against L.striatellus and 50% against S.furcifera, at 40 ppm. 0% against all jumping insects, A-3 at 200 ppm 0% against all jumping insects,
A-4 at 200 ppm 100% against N.lugens, 0% against L.striatellus and S.furcifera.
Example<sup>K</sup>ad XXXIV. Test against Mzus persicae (peach-potato aphids), showing resistance to organophosphorus compounds and carbamates carried out as follows: grown, resistant to organophosphorus compounds and carbamates, peach-potato aphids inoculated on seedlings of idols / black elongated balkans 20 cm high / about 20 cm high / growing in unglazed pots with a diameter of 15 cm, in an amount of about 200 aphids per seedling. After a day, the plants were sprayed with a sprayer, a part-water preparation containing the active substance in a certain concentration, prepared as described in Example 22. The pots were put back into the greenhouse at 28 ° C. Killing coefficient was calculated 24 hours after spraying. The test was repeated twice for each compound. It was found that the new active substances show 100% killing at 200 ppm of active substance. In contrast, comparative compounds show: A-1 80% killing at 1000 ppm active substance ·, 30% at 200 ppm, A-3 60% at 1000 ppm, 0% at 200 ppm, A-4 60% at 1000 ppm, 0% at 200 ppm active substance.
83 members in 25 offices
Priority claims6
| Document | Office | Kind | Date |
|---|---|---|---|
| 1862785 | Japan | A | |
| 1862885 | Japan | A | |
| 2368385 | Japan | A | |
| 10685385 | Japan | A | |
| 10685485 | Japan | A | |
| 21908285 | Japan | A |
Members83
| Document | Office | Kind | |
|---|---|---|---|
| DK51986D0 | Denmark | D0 | |
| GR860308B | Greece | B | |
| DK51986A | Denmark | A | |
| AU5286686A | Australia | A | |
| JPS61178981A | Japan | A | |
| JPS61178982A | Japan | A | |
| JPS61183271A | Japan | A | |
| EP0192060A1 | European Patent Office (EPO) | A1 | |
| KR860006454A | Republic of Korea | A | |
| ZA86763B | South Africa | B | |
| BR8600428A | Brazil | A | |
| JPS61267561A | Japan | A | |
| JPS61267575A | Japan | A | |
| DD242742A5 | German Democratic Republic (until 1990) | A5 | |
| JPS6281382A | Japan | A | |
| HUT41954A | Hungary | A | |
| CS75486A2 | Czechoslovakia (until 1993) | A2 | |
| ES8800951A1 | Spain | A1 | |
| PL257774A1 | Poland | A1 | |
| ES8801799A1 | Spain | A1 | |
| ES8801800A1 | Spain | A1 | |
| ES8801801A1 | Spain | A1 | |
| CS255867B2 | Czechoslovakia (until 1993) | B2 | |
| US4742060A | United States of America | A | |
| JPS63156786A | Japan | A | |
| BR8706927A | Brazil | A | |
| BR8706927A | Brazil | A | |
| EP0277317A1 | European Patent Office (EPO) | A1 | |
| KR880007492A | Republic of Korea | A | |
| NZ215008A | New Zealand | A | |
| HUT47085A | Hungary | A | |
| TR23196A | Türkiye | A | |
| AU584388B2 | Australia | B2 | |
| US4845106A | United States of America | A | |
| IL77750A | Israel | A | |
| US4880933A | United States of America | A | |
| HU895815D0 | Hungary | D0 | |
| PL149199B1This record | Poland | B1 | |
| HU200651B | Hungary | B | |
| HU200753B | Hungary | B | |
| CA1276018C | Canada | C | |
| US5001138A | United States of America | A | |
| HU202365B | Hungary | B | |
| EP0277317B1 | European Patent Office (EPO) | B1 | |
| DE3769122D1 | Germany | D1 | |
| EP0192060B1 | European Patent Office (EPO) | B1 | |
| AT67493T | Austria | T | |
| ATE67493T1 | Austria | T1 | |
| DE3681465D1 | Germany | D1 | |
| IL84843A | Israel | A | |
| DK104292A | Denmark | A | |
| DK104292D0 | Denmark | D0 | |
| JPH0514716B2 | Japan | B2 | |
| US5204360A | United States of America | A | |
| CA1320202C | Canada | C | |
| KR930006348B1 | Republic of Korea | B1 | |
| JPH066585B2 | Japan | B2 | |
| US5298507A | United States of America | A | |
| JPH0629258B2 | Japan | B2 | |
| HK34294A | Hong Kong, China | A | |
| SG138493G | Singapore | G | |
| JPH0649699B2 | Japan | B2 | |
| EG18157A | Egypt | A | |
| JPH07613B2 | Japan | B2 | |
| JPH0730070B2 | Japan | B2 | |
| US5428032A | United States of America | A | |
| JPH0784461B2 | Japan | B2 | |
| US5461167A | United States of America | A | |
| KR960003320B1 | Republic of Korea | B1 | |
| US5580889A | United States of America | A | |
| PH30435A | Philippines | A | |
| NL971014I1 | Netherlands (Kingdom of the) | I1 | |
| NL971014I2 | Netherlands (Kingdom of the) | I2 | |
| US5001138B1 | United States of America | B1 | |
| US5750704A | United States of America | A | |
| DK172809B1 | Denmark | B1 | |
| DK172805B1 | Denmark | B1 | |
| US6022967A | United States of America | A | |
| US6297374B1 | United States of America | B1 | |
| PH11997055815B1 | Philippines | B1 | |
| PH11997055817B1 | Philippines | B1 | |
| PH11997055816B1 | Philippines | B1 | |
| PH11997055821B1 | Philippines | B1 |
Numbers
- Application
- 257774
Titles
- English
- INSECTICIDE
Classification
- CPC, 44
- C07D239/06
- C07D401/00
- A01N43/40
- A01N43/50
- A01N43/54
- A01N43/56
- A01N43/58
- A01N43/60
- A01N43/653
- A01N43/74
- A01N43/80
- A01N43/82
- A01N43/86
- A01N47/02
- A01N47/16
- A01N47/22
- A01N47/38
- A01N51/00
- A01N57/32
- C07D207/20
- C07D207/22
- C07D211/70
- C07D211/72
- C07D233/20
- C07D233/52
- C07D239/18
- C07D263/10
- C07D263/28
- C07D265/08
- C07D277/10
- C07D277/18
- C07D279/06
- C07D401/06
- C07D401/14
- C07D403/06
- C07D405/06
- C07D405/14
- C07D409/06
- C07D409/14
- C07D413/06
- C07D413/14
- C07D417/06
- C07D417/14
- C07F9/65583
- IPC, 60
- A01N43 78
- A01N
- A01N33 18
- A01N43 00
- A01N43 40
- A01N43 50
- A01N43 54
- A01N43 56
- A01N43 58
- A01N43 60
- A01N43 647
- A01N43 653
- A01N43 66
- A01N43 72
- A01N43 74
- A01N43 76
- A01N43 80
- A01N43 82
- A01N43 84
- A01N43 86
- A01N43 88
- A01N47 02
- A01N47 16
- A01N47 22
- A01N47 38
- A01N51 00
- A01N57 32
- C07D
- C07D207 20
- C07D207 22
- C07D211 70
- C07D211 72
- C07D213 00
- C07D213 61
- C07D233 20
- C07D233 52
- C07D239 06
- C07D239 18
- C07D263 10
- C07D263 28
- C07D265 08
- C07D277 00
- C07D277 10
- C07D277 18
- C07D279 00
- C07D279 06
- C07D401 06
- C07D401 14
- C07D403 06
- C07D403 14
- C07D405 06
- C07D405 14
- C07D409 06
- C07D409 14
- C07D413 06
- C07D413 14
- C07D417 06
- C07D417 14
- C07D419 06
- C07F9 6558