Fungicidal 1,2,4-triazole and imidazole derivatives.
13 claims: 7 independent, 6 dependent
- 1Ενωσις τοϋ τύπου Μ·(° Η 2)π\ Α a R. ΛΑ- 2 I t Μ* είς τόν οποίον τά καί Q 2 είναι κεχωρισμένως Η ή CH^* τό η είναι 1 ’ τό R^ είναι αλκύλιον Cg-G^g, κυκλοαλκύλιον G^-Cg ναφθύλιον, ή R, „ 4 3 ένθα τά R^ καί R^ είναι κεχωρισμένως -Η· άλογόνον* -OCH^· -OCF^· -SCH^* -SOgCH^* φαινύλιον* φαινύλιον ύποκατεστημένον δι’αλογόνου ή/ καί άλκυλίου G^-G^ ή/καί -GP^* φαινοξυ όμάς’ φαινοξυ όμάς υποκατεστημένη δι’άλογόνου ή/καί άλκυλίου C^-G^ ή/καί -CF^* -ΟΡ^’άλκύλίον* ή κυκλοεξύλιον* τά Rg καί R^ είναι κεχωρισμένως άλκύλιον G^-Cg, κυκλοαλκύλιον C^-Cg, ORg, ή „ τ »4, 5 ένθα τό Rg είναι Η ή άλκύλιον C^-C^» I ύπό τόν ορον δτι άμφότερα τά Rg καί R^ δύνανται νά μήν είναι ΟΗ'καί τά Rg καί R^ όμοϋ δύνανται νά είναι γέφυρα 1,2- ή 1,3- ή 1,4-γλυκόλης ή γέφυρα 1,4 άκορέοτου γλυκόλης,υποκατεστημένης δι’εως τεσσάρων άλκυλομάδων R^-R^ έχουσών συνολικώς έως τέσσαρα ατομα ανθρακος. f 7 -R 10 Η 7 -Η,ο ?7 . Ηιθ R7 _ Rio ή R:R, ίγ-ΚΐΟ Ηγ6 ό R7-R1ο ο καί αλατα αύτής μετά πρώτονιακων οξέων καί σύμπλοκα ιόντων. έ'’μείάλλικώ , ν^ 1 , Β«ύλ ι'1~
- 2Η ενωσις τής ’Αξιώσεως 1, ήτις είναι τό (1 ,1/^διφ\ινΌ? δ ι μεθυλο (1 Η-1,2,4-τρ ιαζολ-1 -υλομεθυλο)-σιλάυιον, ·*? * ·.? -132— ϊ··ν;’Α ·'·. ’·
- 33, *Η ένωσις τής άξιώσεως 1,ήτις είναι τό δις(4-χλωροφαινυλο) μεθυλο(ΐΗ-ΐ,2,4-τριαζολ-1-υλομεθυλο)σιλάνιον. :I
- 4'Η ένωσις τής Άξιώσεως 1 ,ητις είναι τό /δις(4-φθοροφαίνυλοΥ7μεθυλο(ΐΗ-1,2,4-τριαζολ-1-υλομεθυλο)σιλάνιον. ί
- 55» ‘Η ςνωσις τής Άξιώσεως 1, ήτις είναι τό 4-φθοροφαινυλο(μεθυλο)φαινυλο(ΐΗ-1,2,4-τριαζολ-1-υλομεθυλο)σιλάνιον. ί
- 6“Ενωσις τού τόπου q tj * ’ιΐ Bj-s'(CH 2 ) n ] II είς τόν οποΓον τά , Q 2 Ηα ζ είναι κεχωρισμένως Η ή CH^* I τό η ενναι 1 * τό R' είναι άλκόλιον Cg-G^θ, κυκλοαλκύλιον, G^-Cg, ναφθόλιον ή 4 5 ( i ένθα τά R. καί R,. είναι κεχωρισμένως -Η* άλογόνον* -OCH * -OCF,* 4 3 3 3 -SCH^* -SOgCH^* φαινύλιον* φαινύλιον ύποκατεστημένον δι’άλογόνου ή/ καί αλκυλίου C^-C^ ή/καί -GF^* φαινοξυ όμάς* φαινοξυ όμάς ύποκατεστη-'I μένη δι’άλογόνου ή/καί άλκυλίου G.-G. ή/καί -GF ’ -CF * άλκύλιόν 1 4 3 3 σ ΐ“°4* κυκλοεξύλιον* ύπό τόν δρον δτι δι’ένώσεις τού Τόπου II άμφό- ; ‘ τέρα τά R^ καί R^ δύνανται νά μήν είναι ταύτοχρόνως Η* καί τά R~ καί R, είναι κεχωρισμένως άλκόλιον G^-Gg,κυκλοαλκύλιον C^-Cg, °Ra, ή Μ, R. R c Ά 5 ένθα τό Rg είΰαι Η ή άλκόλιον 0^0^, ύπό τόν δρον oy αμ§6 καί R^ δύνανται νά μήν είναι ΟΗ* καί τά R καί R_ —133— ναι γέφυρα 1,2- ή 1,3- ή 1,4-γλυκόλης,ή γέφυρα 1,4 άκορέστου γλυκό- j' :;λης υποκατεστημένης δι,’εως τεσσάρων άλκυλομάδων % θ εχουσών συνολικές έως τέσσαρα άτομα άνθρακος: ?7“ Κ 10 θ η 1 ~ Κ 1 ο καί , άλ,ατα ταύτης ;μέ άξέα καί ,,σόμπλο^α μετά μετάλλων.7. Η ενωσις τής Αξιώσεως β,ητις είναι τό (2,4-διχλωροφαινυλο) διμεθυλο(1Η-ίμνδαζολ-1-υλομεθυλο)σιλάνιον. 8» Σύνθεσις διά καταπολέμησιν μυκητιάσεων,συνισταμένη ούσιφδώς έξ αποτελεσματικής ποσότητος ενώσεως τίνος τής ’Αξιώσεως 1 έως τής ’Αξιώσεως 7 καί τούλάχιστον ένός έκ τών επομένων:έπιφανειακώς 'δρώσης ούσίας, στερεού ή υγρού αδρανούς μέσου άραιώσεως. j 9. Μέθοδος διά καταπολέμησιν μυκητιάσεως,ήτις περιλαμβάνει ίέφαρμογήν,εις τήν θέσιν η οποία πρόκειται νά προστατευθή,αποτελεσματικής ποσότητος ένώσεως τίνος τής ’Αξιώσεως 1 έωςτής ’Αξιώσεως 5. 10. Μέθοδος διά καταπολέμησιν μυκητιάσεως,ήτις περιλαμβάνει: έφαρμογήν είς τήν θέσιν ή οποία πρόκειται νά προστατευθή,αποτελεσματικής ποσότητος ένώσεως τίνος τού τόπου: είς τόν οποίον τά % , $2 κ{χ ί είναι κεχωρισμένως Η ή Οϊ%* τό η είναι 1’ τό R' είναι άλκύλιον C 2“^18* κυκ λοαλκύλιον G^-Gg, ναφθύλιον ή λατεσττίένθα τά R^ καί R^ είναι κεχωρισμένως -Η* άλογόνον* —SCH^’ -SOgCH^* φαινύλιον* φαινύλιον υποκατεστημένο καί άλκυλίου G^-G^ ή/καί -03%’ φαινοξυ όμάς* φαινο -134μένη δι’άλογόνου ή/καί άλκυλίου G^-C^ ή/καύ -GF^‘ -CF^’ άλκυλίον θ1~^4* κυκλοεξυλιον* καί τά Rg καί R^ είναι κεχωρισμένως άλκύλιον C^-Gg, κυκλοαλκύλιον C^-Cg, ORg, ή ένθα τό Rg είναι Η ή άλκύλιον C^-G^, ύπό τόν δρον δτι άμφότερα τά Rg καί R^ δόνανται νά μήν είναι ΟΗ’ καί τά Rg καί R^ όμού δύνανται νά είναι γέφυρα 1,2- ή ί,3- ή 1,4-γλυκόλης ή γέφυρα 1,4 άπορέστου γλυκόλης υποκατεστημένης δι’έως τεσσάρων άλκυλομάδων R^-R^q έχουσών συνολικώς έως τέσσαρα άτομα άνθρακος. ?7“ β 10 rn ,7-Rio
- 77“ a 10
- 811. Μέθοδος διά παρασκευήν ένώσεως τού τύπου I:Ιι Rg-STCCHg^N Q, είς τόν όποιον τά καί Qg είναι κεχωρισμένως Η ή CH^‘ τό η είναι 1 * ! τό R.J είναι άλκύλιον O 2 “ G 18* Μυκ λοαλκυλίον CyCg, ναφθύλιον, ή -135τά Rg καί R^ όμοϋ δύνανται νά είναι γέφυρα 1,2- ή 1,3- ή 1,4-γλυκόλης ή γέφυρα 1,4 άκορέστου γλυκόλης ύποκατεστημένης δι’έως τεσσάρων άλκυλομάδων R^-R^q έχουσών συνολικώς έως τέσσαρα ατομα άνθρακος. X 1 X. . Ο * kJ η \ η k ζ° ήτις (μέθοδος) περιλαμβάνει άντίδρασιν ΐ)ένδιαμέσου τίνος ένώσεως έκλεγομένης έκ τής όμάδος ?3 Cl 3 S:CHgCl, ClgSiCHgCx καί ?2 Cl-ST-CH-Cl ι £ ,, ,, είς κατάλληλον διαλύτην, μετά R^M, ένθα τό Μ είναι Να,ΙΛ ή Μ^Χ,ένθα τό X είναι Br, Cl , I, είς θερμοκρασίαν άπό -80°0 έως 40°θ,σχήματιζομένου χλωρομεθυλοσιλανίου τίνος* καί 2) άντίδρασιν τοϋ χλωρομεθυλοσιλανίου μετά 1,2,4-τριαζόλης, τοϋ 3-μεθυλο ή τοϋ 3,5-διμεθυλό παραγώγου του,ή τοϋ μετά μετάλλου άλκάλεως αλάτων των,είς πολικούς μή πρωτονιακούς διαλύτας, αιθέρας ή κετόνας είς 0° έως 150°C.
- 912. Μέθοδος διά παρασκευήν ένώσεως τοϋ τύπου I, ώς καθωρίσθη είς τήν ’Αξίωσιν 1,ήτις περιλαμβάνει 1) άντίδρασιν C1 Ri-i όι R J-CHgCl καί R.-Si-CHoCl Ji μετά RgOH είς κατάλληλον διαλύτην,μετά καταλλήλου βάσεως,είς θερμοκρασίαν θ-100°0, σχηματιζομένου άλκοξυ ή διαλκοξυ χλωρομεθυλοσιλανίου* καί 2) άντίδρασιν τών χλωρομεθυλοσιλανίων μετά 1,2,4-τριαζόλης, τοϋ 3-μεθυλο ή τοϋ 3,5-διμεθυλο παραγώγου της ή τοϋ μετά μετάλλου άλκάλεως αλάτων των, είς πολικούς μή πρωτονιακούς διαλύτας,αιθέρας ή κετόνας, είς 0° έως 15θ°θ· '
- 1013. Μέθοδος διά παρασκευήν ένώσεως τοϋ τόπου II , :R M.HW. rf-. X II -136είς τόν όποιον τά , Q 2 καί είναι κεχωρισμένως Η ή CH^* τό η είναι 1 ’ τό R.j' είναι άλκύλιον Ο^-Ο^θ, κυκλοαλκύλιον C^-Cg, ναφθύλιον, ή γ Α ένθα τά R^ καί R^ είναι κεχωρισμένως -Η* άλογόνον* -OOH^’ -OCF^* -SCH^· -SOgCH^’ φαινύλιον* φΟΐνύλιον ΰποκατεστημένον δι’άλογόνου ή/ καί άλκυλίου C^-C^ ή/καί -CF^* φαινοξυ όμάς’ φαινοξυ όμάς υποκατεστη-^ ‘. μένη δι'αλογόνου ή/καί άλκυλίου C^-C^ ή/καί -CF^* -CF^* άλκύλιον C^-C^* ή κυκλοεξύλιον* ύπό τόν δρον δτι δι'ενώσεις τοϋ Τύπου II, άμφότερα τά R^ καί R^ δύνανται νά μήν είναι'ταύτοχρόνως Η* καί τά Rg καί R^ είναι κεχωρισμένως άλκύλιον Ο^-Ο^,κυκλοαλκύλιον G^-Cg, , °Rg, ή Rc ένθα τό Rg είναι Η ή άλκύλιον C^-C^, ύπό τόν δρον δτι άμφότερα τά R 2 καί R^ δύνανται νά μήν είναι 0Η* καί τά R 2 καί R^ όμοϋ δύνανται νά είναι γέφυρα 1,2- ή 1,3- ή 1,4-γλυκόλης ή γέφυρα 1,4 άκορέστόυ γλυκόλης ύποκατεστημένης δι’εως τεσσάρων άλκυλομάδων R^-R^q έχουσαν συνολικές έως τέσσαρα άτομα άνθρακος ! R 7 -Rf Ο ?7“ β 10 p7 -R 1 Ο - 0-« γ·,.;·//.·'· :.7 ή';:· ήτις (μέθοδος) περιλαμβάνει άντίδρασιν 1) ενδιαμέσου τίνος ένώσεως εκλεγομένης έκ τής όμάδος ί·:':. ,·,. ?3 ?2 Cl^SiCHgCl , C1 2 S:CH 2 C1 καί Cl-Si-CH 2 ‘f' ~ '· ®3 ' είς τινα κατάλληλον διαλύτην μετά R^M ένθα τό ένθα τό X είναι Br, Gl_, I, είς θερμοκρασίαν ά ·ί ·?-·Χ·: 137 ματιξομένου χλωρομεθυλοσιλανίου τίνος’ καί 2) αντίδρασήν του χλωρομεθυλοσιλανίου μετά ίμιδαζόλης, τοΰ 2-μεθυλο, 2,4-διμεθυλο, 4,5διμεθυλο, καί 2,4,5-τριμεθυλο παραγώγου της, ήστοΰ μετά μετάλλου άλκάλεως, αλάτων των, είς πολικούς μή πρωτονιακούς διαλύτας,αιθέρας ή κετονας, ενς u εως 150 C. i
- 1114. Μέθοδος διά παρασκευήν ενώσεως τοΰ Τύπου II ώς καθωρίσθη είς τήν ’Αξίωσιν 6, ήτις περιλαμβάνει α) αντίδρασιν Ci . R, I I R.-S CH_Ct καί R.-S -CH-Cl i 1 | 2 1,2 Ct , Cl μετά RgOH είς κατάλληλον διαλύτην, μετά καταλλήλου βάσεως, είς θερμοκρασίαν άπδ 0° έως 100°C, σχηματιζομένου άλκοζυ ή διαλκοξυ χλωρομεθυλοσιλανίου* καί 2) αντίδρασιν τοΰ χλωρομεθυλοσιλανίου μετά ίμιδαζόλης, τοΰ 2-μεθυλο, 2,4-διμεθυλο, 4,5-διμεθυλο καί 2,4,5-τριμεθυλο παραγώγου της, ή τοΰ μετά μετάλλου άλκάλεως αλάτων των, είς πολικούς μή πρωτονιακούς διαλύτας, αιθέρας ή κετδνας, είς 0° έως 150°C.
- 1215. '’Η ένωσις τής άξιώσεως 1 ή οποία είναι τδ δις (4-φθαροφαιϊυλα) ύδροζυ {1Η-1,2,4-τριαζολ-1 -υλομεθυλο)σιλάνιον.
- 1316. ’Η ένωσις τής άζιώσεως ί ή οποία είναι τδ όζυ δις /5ις(4-φθοροφαινυλο) 1Η-1,2,4-τριζολ-1 -υλομεθυλο)σιλάνιον.
Independent claims13
2,556 paragraphs in 104 sections, as filed
CELLULAR PRODUCTS 1,2,4- (
TRIAZOAE AND IMIDAZOL!
Excerpt from the 'Invention'
I.
Silicylmethyl 1,2,4-triazole and imidazole have a wide range of fungicidal activity.
i
Historical 'Overview' The present invention relates to pyrithylmethyl triazole in
and imidazole such as, for example, dimethyl (phenylXH-1,2,4 triazol-1-ylmethyl) silane and (1,1<sup>G.</sup>-diphenyl-4-yl) dimethyl (1Himidazol-1-ylmethyl) silane and the use of these novel compounds in the fight against fungi, particularly living plant diseases.
U.S. Patent No. 3,692,798 does not explicitly state compounds at the site!
R, e<sub>2</sub>- |: ch<sub>2</sub>/ ^ T <sup>R</sup>,)) Any one of R, R, R and R may be lower alkyl and phenyl. It is stated that the compounds allowed are useful as i
antimicrobial agents.
European Patent No. 29,993 discloses compounds of the type
Cr w <sub>t</sub> I T in which R may be C, -C alkyl. and Y and Z 14 may be H or STR ^ H ^ R ^, where R ^, R<sub>2</sub> and R ^ δόΧΧΧ )ά είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι άλ είναι είναι άλ είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι than ή ύ είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι είναι. It is indicated that the compounds are useful as / fungi-Z 'fungicides.
4No numbers. U.S. Patents 3,256,308 and 3,337,598 disclose site compounds
THE<sup>1</sup>- hey - Cr which Rj can be methanol, ethyl, vinyl or phenol.
I.
It is also indicated or used for fighting myths.
I.
No. 7885.127 Belgian Patent discloses quaternary ammonium salts, such as:
CH ^ (♦) (CH ^ O) S; CH<sub>2</sub>GH<sub>2</sub>NnC<sub>1 g</sub>H<sub>3?</sub>
CH,. <sup>5</sup> and their use as fungicides.
'177652 'Research Disclosure Reveals OSylR locus
Ar-CH<sub>2</sub>-CH-CH-G (GH<sub>5</sub>)<sub>5</sub> a
in which Ar may be a substituted phenyl, X may be CH or N and R may be alkyl. It is shown that the compounds are useful as agricultural fungicides.
U.S. Patent No. 3,000,140 discloses silicon ether at:
OSfRj
Ar-O-CH-CH-C (CH,),
-k <sup>3 3</sup> Ar which can be a substituted phenol, X * /)!
may be CH or N and S may be phenyl and / or lower alkyl. It is indicated that the compounds are permitted! as agricultural fungicides.
<img file="GR76497B_D0001.tif" />
-sNo. U.S. Patent No. 248,992 discloses a class of organosilicone compounds having at least one monovalent guanidine group represented by the general formula.
<img file="GR76497B_D0002.tif" />
in which R is a hydrocarbon atom or a monovalent hydrocarbon group. Do they contain guanidine compounds containing organosilicon, are antifungal agents described useful? molded plastics and tires, especially silicone tires.
USSR Patent Nos. 346 * 306, discloses the formula (R)<sub>1</sub>)<sub>n</sub>(R.<sub>2</sub>O)<sub>5</sub>_<sub>n</sub>STCH<sub>2</sub>Axes in which R1 and Rg are alkyl groups, n is Oj-3, and Az is a pyrazole, imidazole or benzimidazole ring, heretically substituted.
No. 272,552 USSR Patent discloses (N, E)<sub>n</sub>(H<sub>2</sub>°)<sub>3</sub>_nS! 0H<sub>2</sub>CH<sub>2</sub>A.<sub>I.</sub> where R ^, Rg, and Az are as described in the preceding reference.
i
Summary of the Invention The present invention relates to Formula I and Formula II and to agricultural compositions of these compounds.
<img file="GR76497B_D0003.tif" />
-6 to Qp Q<sub>2</sub> and is separately H or CH ^ * n is 1 * R<sub>1</sub> is alkyl Cg-C ^, cycloalkyl C ^ -Cg, naphthyl or R 'is alkyl Cg- ^ g, cycloalkyl C ^ -Cg <sup>cycloalk</sup>^<sup>li</sup>'9<sup>n</sup>, <sup>to</sup>Ψ!
pylon, or I here
<img file="GR76497B_D0004.tif" />
R and R are separately -H * halogen * -OCH ^ * -OCF ^ '-SCH ^ * -SOgCH ^ phenyl * halogen-substituted phenyl and / or CpC ^ and / and -CF ^ * phenoxy both a phenoxy group substituted by halogen and / or alkyl C ^ -C ^, and / or -CF ^ '"alkyl ^ -C ^'> 1 t VV | cyclohexyl * provided that, for the compounds of Site II, both R R and R ^ cannot be simultaneously R 'and Rg and R είναι are separately alkyl CpCg, cycloalkyl C ^-Cg, OR<sub>6</sub>, the <sup>THE</sup>4 <sup>l</sup>5 wherein Rg is H or CpCp alkyl, provided that both Rg and R ^ may not be OH and Rg and R ^, however, may be 1,2- or 1,3- or 1-bridge; 4- glycol or 1,4 unsaturated 'I glycol bridge' substituted by up to four R ^-R ^ q alkyl groups having a total of up to four carbon atoms j
5 »0”? The present invention is also referred to in the method of & quot;
! Λέ fungal infections, especially live plant fungi,
<img file="GR76497B_D0005.tif" />
shall apply, at the location or site to be protected, an effective amount of compounds of Site I or Sites II
Q.
Ba-SHCa,) ^
<img file="GR76497B_D0006.tif" />
Q, k<sub>2</sub>-s: (op<sub>2</sub>)<sub>the</sub>/ ^> i
II where Qp Qg and are respectively H or CH ^ * n is 1 * R, j and are alkyl θ2 ~ θ8 ' <sup>cc</sup>λ ·<sup>oa</sup>C1 -Cg alkyl, naphthyl, or
<img file="GR76497B_D0007.tif" />
R<sub>c</sub><sup>k</sup>4 5 where R ^ and R ^ are separately -H * halogen * -OCH ^ * -OCF ^ *
-SCHj * -SOgCH ^ * phenyl Halogen and / or alkyl substituted phenol 0.-C. and / or -CF 'phenoxy group' phenoxy group 'substituted14 3; 01 * 2; Halogen and / or alkyl C ^ -C ^ or / and -CF ^ '/ alkyl C ^ -C ^' or cyclohexyl *!
Rg and R2 are separately C1 -C6 alkyl, C1 -C8 cycloalkyl. ORg, or
<img file="GR76497B_D0008.tif" />
Rr '4 5 wherein Rg is H or alkyl C ^ -C ^ under the assumption that both R ^ and R ^ cannot be 00' and R '<sub>2</sub> and R ^ can be 1,2- or 1,3- or 1,4-glycyl bridge or 1,4-unsaturated glycol bridge substituted by four R R-R ^ q alkyl groups having a total of up to foursomes carbon <sup>R</sup>7”<sup>R</sup>10 p7 ~<sup>R</sup>10 f7 “<sup>ft</sup>10 Or "a
R <7 ”Rl
<img file="GR76497B_D0009.tif" />
Whenever you type or <sub>t</sub><5 is OH, it is understood that Formula II comprises disiloxane:
Rc
IL-Si-C1
CHr
Q,
Q.
-SI?<sup>THE</sup>2
<img file="GR76497B_D0010.tif" />
The present invention also relates to salts of the compounds of Site I and type II with protic acids and salts with metal ions.
Preferred for their great ease and / or ease of synthesis, they are compounds of general limits, where
Q, = Q<sub>2</sub> = H. '
Preferably for the greater of the surfaces and / or the most satisfactory of the easy compositions, they are compounds of the preferred range
L- I come here
I • and R ^ and R 'are
R.
<img file="GR76497B_D0011.tif" />
R<sub>c</sub> R ^ is an alcohol or even R ^ is an elk<sup>K</sup>4 <sup>d</sup>5 lion C.-C .. i
4
I.
It is preferred for the maximum amount of acne and / or longer! "Easy to synthesize, are compounds of the preferred limits, where Rj and R | is R ^;
<img file="GR76497B_D0012.tif" />
* 5 where R is R or R ', and R ^ is H, P, Cl, Br or phenyl, and is H, R, Cl or Br * and R<sub>2</sub> is
.......... 'Ί- “4
<img file="GR76497B_D0013.tif" />
<sup>The</sup>,-=4·
<img file="GR76497B_D0014.tif" />
-9 Especially preferred for the excellent performance and / or the most satisfactory of ease of synthesis, are the following compounds;
(Dimethyl) -phenyl (1H-1,2,4-triazol-1-ylmethyl) silane * Dimethyl (4-methylphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane * ( 4-Bromophenyl) dimethyl (1 EL.1,2,4-triazol-1-ylmethyl) silanone '(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) ) silan '(4-chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane *
I.
I (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 (Biphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane * / ”bis (4-fluorophenyl27methyl (1H-1,2,4-triazol-1-ylmethyl) silane '(4-Fluorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane *
Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane * (2,4-Dichlorophenyl27methyl (1H-1,2,4-triazol-1-ylmethyl) sila-.
<sup>1</sup> yes'
2,4-Dichlorophenyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane
4-chlorophyll (methyl) phenyl (1H-1, 2,4-triazol-1-ylmethyl) silane ion. 4-Fluorophenyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane * Butyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane:
Butyl (4-fluorophenyl) methyl (1H-J, 2,4-triazol-1-ylmethyl) silane '/' bis (1,1)<sup>G.</sup>-Diphenyl-4-yl27methyl (1H-1,2,4-triazol-1-ylmethyl) silane * (1,1'-Biphenyl-4-yl) butyl (methyl) - (1H-1,2,4-silanone) and
<img file="GR76497B_D0015.tif" />
(1,1'-Biphenyl-4-yl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane.
Particularly preferred compounds, methods and compositions of Formula II are compounds having at least one group i.
iq, Rg or is other than lower alkyl (C1 -C2) i) phenyl. In particular, the following compounds of Formula II are particularly preferred for their excellent performance and / or greater ease of synthesis:
(1,1'-Diphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silaneCV * (2,4-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane *
Butyl (2,4-dichlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane / ”bis (4-Fluorophenyl) 7 (1H-imidazol-1-ylmethyl) methylsilane * /“ bis (2,4-Dichloro) 1H-imidazol-1-ylmethyl) methylsilane * (2,4-Dichlorophenyl) (1H-1didazol-1-ylmethyl) methyl (phenyl) silanone * (4-Chlorophenyl) (1H-imidylmethyl) ) silanone * (4-Fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silanone * (1,1'-Biphenyl-4-yl) butyl (1H-imidazol-1-ylmethyl) methylsilon * (1,1'-Biphenyl-4-yl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silanone '/ bis (1,1-Biphenyl-4-yl27)<sup>2</sup>-imd'azol-1-ylmethyl) methylsilane '
Butyl (4-chlorophenyl) (1X-imidazol-1-ylmethyl) methylsilane; 7 '' (4-Chlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane *
Dimethyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) silane * and 7; '.
Butyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) silane.
Where and Mrs. Q<sub>2</sub> is either H or both OH, or the process for the preparation of the triazole derivatives of Formula I will usually produce a mixture of the two isomeric triazoles.
Qt
<img file="GR76497B_D0016.tif" />
<sup>hot</sup> u <sup>2</sup> or A<sub>2</sub>
R,
Type N.
R2-S1-OH2-N
<img file="GR76497B_D0017.tif" />
Place IB
<img file="GR76497B_D0018.tif" />
<img file="GR76497B_D0019.tif" />
-II<sup>n</sup>When a triazole substituent is H and the other is
CH ^, three isomers are possible:
CH,
GHx
R1, -ET-CH.
a,
R<sub>2</sub>-S7-CH<sub>2</sub>- ^^ And
R.
CEL
Site ID and R-2 “0 * - 0¾ j<sup>-</sup>®. r<sub>3</sub>
Place IE
Place m
The mixture will contain, to a lesser extent, the isomers of Site 1A or Site I; however, the isomers of Site IB, ID and IL also acquire fungicidal pathways and are not required to be separated,
For the imidazole derivatives of Type II, isomers were produced when Q2 <sup>Ms</sup>^ are not alike:
??
R «'- Si-CH<sub>2</sub>-N
<img file="GR76497B_D0020.tif" />
Type IIA
I.
Site IIA isomers will generally prevail, although Site IIB isomers also possess fungal toxicants and no separation of the isomers is required.
Detailed Description of the Invention
In the following discussion, R ^ is understood as representing both RJ and R ^, since the questions R 'are included in the definition of R ^. The azole derivative will be used with reference to suitably substituted 1,2,4-triazoles and imidazoles.
Qi Qa xi therein <& | and Qg and may be OH or Harmonic formulas, the part of the pension
<img file="GR76497B_D0021.tif" />
and
Q,
<img file="GR76497B_D0022.tif" />
-iA
If X is N or C1, both triazole and imidazole finger systems will be used to indicate.
··
Composition!
Compounds of the present invention may be prepared from chloromethylsilanes and sodium salt, 1,2,4-triazole or imidazole or methylated homologs of:
r, -s? -ch<sub>2</sub>oi ♦ » <sup>iii</sup>g ~ ™<sup>2</sup>Az
Qc 'may also be used with lithium and potassium azoles. Instead of chloromethylsilanes, they can be used
I bromomethylsilane, iodomethylsilane or arylsulfonyloxymethylsilane. Generally, equimolar amounts of tween reagents are used (except where R ^<sup>=</sup>* g) below) of the azole salt usually obtained in excess of 5-10% of the theoretical * In addition, if an acid acceptor is added, this 1,2,4-triazole or imidazole per se may be used. , include excess azole, alkali metal alkoxides, such as sodium methoxide or potassium tert-butoxide, inorganic bases such as potassium carbonate, or sodium hydrogen and tertiary amines such as triethylamine. "When the acid acceptor is a good nucleophile, such as sodium methoside, it should be avoided as much as possible to prevent unwanted secondary reactions. Suitable solvent to say
V j. They include polar non-protonated solvents, such as dimethylformamide, dimethylsulfoxide or acetonitrile ether, such as radion or 1,2-dimethoxyethane and ketone, such as 2-butyl. the reaction temperature can vary between 0 ° and a value between 25 ° and 100 ° C; Reaction may;
<img file="GR76497B_D0023.tif" />
-13 high pressure but generally preferable to atmospheric pressure. The optimized temperature and reaction time will vary with the concentration and selection of the reagents, particularly with choice of 2: sodium, at approximately 2 molar concentrations of dimethylformamide, provides good conversion at about 2 hours at 80-90 ° C, while 1,2,4-triazole and potassium carbonate at approximately 1 molar concentration of 2-butanone, it requires 8-12 hours of reflux. And imidazole reactions? it is generally faster. Reaction times are generally required from 1 to 24 hours. The reaction course can be monitored by sample processing by NHR analysis followed by the single (spectral line) intensities of the single starting point of 2 SJ solid material. lines) of the SiCHgN product, which is close to 3.8 by compounds of Formula I and 3.7 by compounds of Formula II.
Relative to the triazole derivatives of Formula I, or 1H-1,2,4-triazol-1-ylmethyl compound, as prepared above, is accompanied by a small amount of 4H-1,2,4-triazol-4-ylmethyl isomer. j<sup>2</sup> / ^ ir
R.-SJ-CHoN · <sup>1</sup> A <sup>2</sup>\ ^ * 3 'The ratio of isomers varies with the value of R and t!
Under reaction conditions, with a 1-substituted to 4-substituted, a ratio of approximately 10: 1 is sometimes observed. The only dimethyl triazoles provide, as secondary products, similar I4H-CH isomers:
??
R, -S »-CH<sub>O</sub>N i
<img file="GR76497B_D0024.tif" />
Rg or R ^ J-CHjB i<sub>3</sub>
0X_
-14I When either unsubstituted silylmethyltriazole or methylation by transfer (I4ETALATI0N) is provided, alternative substitution of the methylated bonds
R, -j: -OH<sub>2</sub>0
R,
1. C<sub>4</sub>H<sub>9</sub>Li
2. GH ^ I
R.-et-OHON,
L.
CH,
With respect to the imidazole derivatives of Site II, isomers are only possible when Qg <sup>Ms</sup>^ are alike. There are two isomers:
CH,
B.
Ri-et-OHNN
V and
R <
Rj-Si-CHglT jr
«,
Place IIB
Place IIIA
The product of Site IIA would generally be preferable. If desired, the isomers can be separated by standard techniques such as crystallization, distillation or chromatography.
For the case where you have the product triazole or imidazole R ^ <sup>t <</sup>* Chlorine chloro (chloromethyl) silane chlorine is replaced in one of six ways. In one method, at least equivalent doses of sodium azole can be used. Intermediates are formed containing highly reactive silicone-azole bonds, and reaction with water or alcohol provides the desired oxygenated compounds:
<img file="GR76497B_D0025.tif" />
··/':<sup>:</sup> '
<img file="GR76497B_D0026.tif" />
·. '<sup>7</sup> / SB
-15Suitable to dissolve and reaction conditions are as set out in general lines on pages 11,12 and 13 for azole shifts. Alcohol temperature is not critical, and temperature is set to 50 ° C. Ensuring complete reaction when Rg-alkyl C1-6 O. However, for Rg = H, II hydrolysis is carried out near the warm room temperature, to limit at least formation
disiloxane, recognized as the flanol-disiloxane equilibrium
I is possible at any time R ^ = H:
<img file="GR76497B_D0027.tif" />
- <sup>THE</sup>2h <sub>c</sub> f ♦ H.<sub>2</sub>0
<img file="GR76497B_D0028.tif" />
* The position of equilibrium and the rate at which it is achieved will vary with the values of R and Rg, solvent, temperature and the presence or absence of acid or basic catalyst.
R.-SJ-CHgCl
In the second method, the silicone-oxygen bond is formed first, followed by the azol substitution, as described above:
? W · 1C '. T, et al. R.-Si-CHJS |
- ». H, -S, -CH<sub>2</sub>a »1, <sup>0R</sup>6 <sup>6 Q</sup>2 <sup>1</sup> The reaction of chlorosilane with RgOH can be carried out in virtually any nonhydroxyl solvent, of ethers such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuronium diphthalimonium, or diphthydromuran
<img file="GR76497B_D0029.tif" />
-16 the reaction temperature may vary from 0 ° to 1 ° C, and or
R.0H is sometimes obtained in excess of the theoretical combination of C equivalents of RgOH 1.1 equivalents of triethylamine and 0.1 equivalents of imidazole in dimethylformamide at 80 ° C for two hours, widely applied. Extending these methods to (chloromethyl) dichlorosilane, provide di-oxygenated silanes:
C1 r, -s: -ch<sub>o</sub>I 2
ORz / 6 L
r.-s: -ch<sub>?</sub>n 9 is,
Glycol derivatives are similarly formed, using diol of tin instead of two RgOH molecules.
Alternative substitution with alkoxy (chloromethyl) silanes involves selective replacement of an alkoxy group of dialkoxysilane with an organometallic reagent:
Λ (r<sub>6</sub>o)<sub>2</sub>s: -ch<sub>2</sub>oi <sup>R</sup>iV
R ^ i or R Na * 2
R.-S * -CH_C1 I i
ORg
The conditions for such substitution are as described in the following paragraph, after the addition of diacoxylalanine should be added after the addition of the metal or metallic compound.
',. i
The required chloromethylsilane starting materials are prepared from six commercially available chloro (chloromethyl) dimethylsilane, chloromethyl (dichloro) methylsilane, or chloromethyltrichlorosilane. ip, ci-s; -ch „ci, i 2 CH,
The SI-C1 bonds to these compounds are either lithium, organo sodium, or GRIGNARD reagents!
ch<sub>5</sub> gi-s; -gh<sub>o</sub>ci
I 2 Cl or Cl ^ SiCHgCl? 2 '
R. -s; -ch<sub>o</sub>qi
I 2
<img file="GR76497B_D0030.tif" />
<-,
-17 alkyl and / or aryl according to a bibliographic procedure, after intact C-C1 bond. For silanes containing two or three ST-C1 bonds, stepwise replacements are possible, with a yield of remarkable flexibility at the values of R ^ -. How many?
These chlorosilanes can be substituted with bromosilanes, psodosilanes or alkoxysilanes. Preferred dissolved in these reactions include ether such as tetrahydrofuran
V. <sup>1</sup>
1,2-dimethoxyethane and diethyl ether, or hydrocarbons such as hexane and toluene. The preferred temperature will vary between
-80 ° C and 40 ° C, depending on the phase of the metallic metal;
for example, when aryl lithium reagents are produced in tetrahydrofuran from aryl bromides using butyl lithium, the mixture should be maintained at approximately 40 ° C.
Avoiding secondary reactions involves the bromobutane produced. However, if the metal-metal solution is stable at higher temperatures, the reactions may be carried out.
The concentration was -20 ° C to 25 ° C, with no competitive reaction of the jCH ^ Cl group. The reaction is rapid at all temperatures and to ensure complete reaction only a short period of time is needed, for example 30 to 60 minutes, after the coupling of the reagents. i
ΊΨί...
CIS * reactions (CH ^ CH ^ Cl with GRIGNARk reagents are described by C. EAB0RN and JC JEFFREY, J.CHEM.S0C. 1954, 4266 * and recent review on the synthesis of aryltrimethylsilanes in CH V by ClSi). contains experimental procedure useful by reaction of CIS "(CH ^ Cl ^ Cl, is that of D. HABICR ^ Si) fL EFFENBERGER, SYNTHESIS, 1 979, 841. 'Optical introduction of mids / reverses. Ή / lob within ClgSi (CH JCHgCl is described by VF EUJNETSOVA / <;).
L ***
-18AND RM SOKOLOVASKAYA, MR. OBSHCH.KHIM. 1969, 1 STVCHEM ^ ABSTR. '72, 31,897 P and also may be selectively inserted into an aryl mass:
Cl ^ Sj-CHgCl + ArLt -Cl-SI-Cl ^ l
Ar »>
In both cases, the organometallic reagents should be added with dichlorosilane at a low temperature after good mixing, for optimal yields.
Reactions of Cl ^ SICHgCl with GRIGNARD reagents are described by AA ZHDANOV. VI PAKHOMOV, AND T. BAZHANOVA, ZH.OBSHSH.
KHIM, 1.973, 1280 * CHSM.ABSTR. 79, 66452 m. Ή Adding Organic Metals ~ ——————<sub>(</sub> Some trichlorosilane reagents are still constituted, and when three similar groups are to be introduced, adding Cl2 SICH2 Cl to an organometallic reagent is usually not successful. Also only one ariloma can be inserted:
CljSJCHgOl ♦ ArLi - »Ar- ^ I-CHgCl
Cl
Useful modification of bibliographic procedures, applicable whenever R ^ or R 'is aryl has been developed for this work. Instead of preparing an organolithium reagent and having it combined with chlorosilane, it was found that aryl bromide and chlorosilane such as C1 SJ (CH ^ JgCHgOl) can be combined with such inorganic acids butyl lithium. Bromine-lithium exchange selectively and the resulting aryl lithium react nC.H-LJ - 4 9
-0<sub>4</sub>H<sub>9</sub>Br
-L * C1 after the SI-C1 bond as OHj is formed
ArBr + C1-S! -CH<sub>O</sub>C1 i *
CH, ch<sub>5</sub>
Ar-S; -CH<sub>2</sub>C1 ch<sub>5</sub>
ArU
<img file="GR76497B_D0031.tif" />
-19 This reaction is equally well applied to aryl-substituted chloro silanes such as C1SI (CH ^) (CgH ^ JCHgCl, and may be used to insert two aryl groups within GlgS * (CH ^).<sub>2</sub>C1. By extension, the aryl and even-butyl group can be introduced in one step.
GH ^
Ar-Si-GH<sub>2</sub>G1 £ - ° 4<sup>THE</sup>9 ®3 ci<sub>2</sub>s: -ch<sub>2</sub>ci
ArBr
2n — GH<sub>q</sub>L * 4 9 «
Substitution of RLT alkyl lithium esters by n-butyl lithium provides a general route to Ar (CH ^) S '(RjGHgCl.
In the following examples the temperatures are reported as degrees Celsius. Abbreviations for Nuclear Magnetic Resonance (NMR) spectra are δ-simple (spectral line), d = double, triple C | - quadruple, m<sup>=</sup> multiple * peak positions are denoted as parts per million eq of tetramethylsilane internal threshold. the infrared (IR) peak positions are provided in reverse centimeters (cm 1). Hexanes are denatured in the mixture of isomers at 68-69 ° C, and ether is denatured in diethyl ether.
<img file="GR76497B_D0032.tif" />
-20Example_1
Friday 0_ (1<sub>£</sub>1'-Biphenyl-4-yl) (chloromethyl) dimethylsilane
9.9 g solution. (0.042 mol) 4-Bromodiphenyl in mL of dry tetrahydrofuran, cooled to -78 ° C under nitrogen and stirred, while added dropwise at 15 minutes, 26.5 mL. (0.042 mol) 1.6 mM cantbutyl lithium solution in hexane. Concentrated slurry was formed and, to facilitate stirring, 35 ml of tetrahydrofuran was added. After continuous cooling, 5.9 ml (6.7 mol) of dimethylsilane chloro (chloromethyl), yielding a clear solution, was allowed to stand for 10 minutes, which was allowed to warm to room temperature at 300 ° C. . ether, filtration to remove and precipitate lithium chloride and filtration of the evaporated filtrate, leaving (as a residue) 13.2 g of semisolid. (1 00% crude product) of the title compound as a colorless solid, mp 30-40 ° C, suitable for further reaction. Traces of impurities found or impossible to remove <sup>1</sup> Brush with 30 0 / 0.1 mm of stainless steel head blend, 83%. m.p. 37-4 ° C. IR spectrum Spectrum (NUJ0L<sup>R</sup>) 1585,1240,1110, 830,810, 750, 690 cm. ”<sup>1</sup>/ N1® (CDCl) 0.4 (6X, S), 2.9 (2H, S), 7.3-7.7 ($ H, m).
Example 2
Preparation of (4-bromophenyl) _ (chloromethyl) dimethylsilane
Prepared 4-bromo-phenylmagnesium-bromide ex 11.8; gr. (0.050 mol) of 1,4-dibromobenzene and 1.2 g. (0.050 mole) magnesium jets in 75 ml ether according to OR PSHIEMENZ, 0RG> SYN. COLL Vol. 5, 496 (1973). The resulting mixture was cooled in ice under nitrogen, while adding dropwise to 6.6 ml of lysate. (7.2 g of 0.050 mol) (chloroform)) with a;
-21methylsilane in 10 mL of ether. After the reaction mixture was allowed to stir overnight at room temperature, quenched (or reacted) carefully with saturated aqueous ammonium chloride solution and filtered. The ether phase of the filtrate was washed with brine, dried over magnesium sulfate! and subjected to scrubbing, remaining 9.8 g. Submitted with distillation, it yielded 3.8 grams. (29%) of the title compound as a colorless liquid. bp 97 ° (1 mm) * IR spectrum (inaudible): 2950,1575,1475,
Spectrum
1370, 1250, 1065, 1010, 840, 805, 72D cm. / NMR (ODCl ^) 0.4 (6H, S)
2.9 (2H, S), 7.3-7.7 (4H, m).
Example 3
Preparation of dimethylsilane chloromethyl (4-chlorophenyl) dimethylsilane
9.6 g solution. (0.050 g) of 4-bromochlorobenzene and 6.6 ml. (7.2 g, 0.050 mol) of chloro (chloromethyl) dimethylsilyl in 75 ml of tetrahydrofuran, stirred at -78 ° C under nitrogen, while 31 ml (0.050 mol) was added dropwise. you know The resulting clear solution was allowed to warm to room temperature, diluted with ether until no other lithium chloride precipitated, and? Filtrate. Evaporate the filtrate to leave (as a residue) 10.6 g. of light yellow liquid, which was subjected to distillation, yielding 6.0 g. (55%) of the title compound as colorless: b.p. 54-58 ° C (0.05 mm) * IR spectrum (endless): 2910, 1560, 1470, 1370, 1250, 1080, 1010, 840, 805, 790, 740 cm. "<sup>1</sup> . NMR (<2DCl): 0.4 (6H, S); 2.9 (2H, S) * 7.1-7.6 (4H, <p.
The in situ production of aryl lithium, described in this example, is also useful for the production of the pyrophosphate of Example 1. If the reaction was diazed at / 6.5-0 /, 7 molar solution of 4-bromodiphenyl or Temperature maintained at -22 ° C to -55 ° C upon the addition of butyrolithium, C-precipitated with little or no solid.
Example 4 i
Preparation of Chloromethyl (2,4-dichlorophenyl) dimethylsilane
I.
17.0 g solution. (0.075 mol) 2,4-dichlorobromobenzene and 10.8 mL (11.8 g.0,082 mol) chloro (chloromethyl) dimethylsilane in 100 mL dry tetrahydrofuran were cooled to -70 ° C and cooled to -70 ° C. drip 49 ml. (0.079 mol) of 1.6 mM n-butyl lithium solution in hexane, at a speed which kept the mixture below -70 G. The resulting cloudy reaction mixture was allowed to warm to: room temperature, 400 ° C. filtered i
and subjected to evaporation, remaining 20.5 g of yellow: liquid. Submitted by distillation, it yielded 12.6 g. (66%) of the title compound as a colorless liquid, b.p. 83 ° C (0.02 mm) 1.5522 *
IR spectrum (endless) 1565, 1455, 1360, 1255, 1120, 1100, 1040,825 cm;<sup>1 </sup>NMR (CDCl): 0.5 (6H, S); 3.1 (2H, S) * 7.0-7.5 (3H, m).
Example 5
Preparation of Chloromethyl (2<sub>L.</sub>β-diethoxy (polyethyl) dimethylsilane
A solution of 25.0 g (0.181 mol) of 1,3-dimethoxybenzene
250 mm. tetrahydrofuran was lowered to room temperature;
of nitrogen, while a 30-minute time interval (0,200 mol) of 1.6 molar solution of n-butyl lithium hexane was added dropwise. The resulting mixture was heated at reflux for 1.5 h to give an orange solution which was cooled to 5 ° C and stirred, while added dropwise over a period of 15 minutes, 27 ml. (29.4 g of 0.205 mol) chloro (chloromethyl) dimethylsilane. The resulting white suspension was allowed to warm to room temperature, stirred for 1 hour, diluted; - / <sup>:</sup>: :\·
<img file="GR76497B_D0033.tif" />
-23 g of ethyl acetate, poured into water and extracted with ether. The organic layers were washed with brine, dried over magnesium sulfate and distilled, yielding 37.0 g (84%) of the title compound as a colorless liquid: b.p. 98-11 ° C (Q, 1 mm). NMR spectrum (CDCl): 0.4 (6H, 3) * 3.1 (2H, S) * 3.7 (6H, S) * 6.3 (2H, J) * 7, 1 (1H, m) .
Preparations of the compounds of Table I may be used by the procedures of Examples 1-5, by substitution of the organolithic compound or the GRIGNARD reagent. In the literature, very related procedures are known, for example, e.g. G. EABOEN AND JG JEFFREY
J.CHEH.300. 1954, 4266. For compounds such as: 2-halogen substituted phenyl ring, alternative to i.
An example procedure of Example 4 is the specific method of arylmagnesium iodide by G. EABORN, KL JAURA and DRM WALTON J.GHEM.30G. 1964, 1198!
TABLE I
7¾ xs; -ch<sub>2</sub>ci
CH<sub>5</sub>
X = H<sub>1</sub> or R * ° 2®5
- 4 9
B-OiA-s cyclopropyl cyclopentyl cyclohexyl
1- naphthylone
2-naphthyl phenyl 4-fluorophenyl 4-methoxyphenyl
bp 127-128 ° C bp 172 ° C<sup>5</sup> 1.4510 wt<sup>2</sup> 1.4556
bp 120-130 ° (10mm) b.p.112 / ^ 0.08 mm)
<img file="GR76497B_D0034.tif" />
Hslf .;), 05 <sup>:</sup>* L ·
-24 TABLE I (continued)
X = R<sub>1</sub> or Rf
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-iso-propylphenol
4-tert-butylphenyl
4-Methylsulfonylphenyl 4-cyclethoxyylphenyl
4-trifluoromethoxyphenyl
4- (4-chlorophenyl) phenyl
4- (4-bromophenyl) phenyl
4- (4-methylphenyl) phenol
4- (4-Trifluoromethylphenyl) phenyl
4- (4-fluorophenyl) phenyl
3-phenylphenyl
3-trifluoromethylphenyl
3-chlorophenyl
2-trifluoromethylphenyl
2-phenylphenyl yl
2-chlorophenol
2-methoxyphenol
2.3-dimethylphenyl
2.3-dimethoxyphenyl
2.4-difluorophenyl
2-fluoro-4-chlorophenyl
2-chloro-4-phenylphenyl
2-fluoro-4-phenylphenol
2-methyl-5-chlorophenyl
2,6-dimethylphenyl
3.4-Dichlorophenyl
3-methyl-4-fluorophenyl
3.5-dichlorophenyl
bp 122 ° (0.03 mm);<sup>2</sup> 1.5773
bp 92-93 ° (0.05 mm .;) 1.4 ° C (5 ° C)
bp 96 ° (7mm)
1.5056 m.p. 64-68 ° C<sup>1</sup> 1.5424
bp 55-57 ° (0.15 mm) or 1.5862
bp 59-62 ° (0.3 mm) b.p. 73 ° (0.15 mm);<sup>3</sup> 1.4826
1.5772
bp 78-80 ° (0.3 mm);<sup>1</sup> 1.5164
1.5254 j
<img file="GR76497B_D0035.tif" />
- ” ·:·
4·?
-25Example 6
Preparation (1<sub>L.</sub>1 The title compound can be prepared by the procedure of Example 1, substituted chloro (chloromethyl) dimethyl (dimethyl) dimethylsilyl (chloromethyl) dimethylsilyl (methyl) dimethyl (dimethyl) dimethylsilyl (dimethyl) dimethylsilyl th. i
By the procedures of Examples 1-5, related compounds can be prepared, using an appropriate organolithium or reagent GRIGNARD and CliRgJSiiCH ^ JCHgCl; procedures such as VP KUZNETSOVA and R. M. SOKOLOVASKAWA, Z. 0BSH05.KHII4 1969,1997.
Alternatively, both diphenyl and butyl groups may be injected simultaneously as follows: Solution 23.3 g (0.10 mol) of 4-bromodiphenyl and 12.7 ml (16.4 g.0.0 mol). ) methylsilane (dichloro) methylsilane in 150 ml of tetrahydrofuran dry, cooled to -70 ° C and bubbled, while addition, 125 ml (0.20 mol) of 1.6 mole of solvent was added. , at a speed maintained by the mixture ♦ - | below -60 C. The resulting slurry was allowed to warm to room temperature, carefully treated with 10 ml of ethyl acetate, and poured into 300 ml of water. The organic layer was separated by 100 ° C. mm. The hexanes and the combined organic phases were washed three times with water and once with brine, dried over magnesium sulfate, and subjected to evaporation, a residual 33.9 g of yellow. Submissions distilled gave 9 5 grams.
X grams thick - - · · ', / · \ ·
About 7-26 (31%) of the compound title: b.p. 135-158 ° C (0.1 mm);<sup>22</sup> 1,5743 * IS spectrum (unbroken): 3060, 3015,2960, 2920, 2870, Ί600,,
1485, 1390, 1380, 1250, 1120, 1075, 1005, 875,810,800,760,700 cm.<sup>1</sup>. NMR (CDCl): 0.4 (3H, S); 0.6-1.8 (9H, m); 2.9 (2H, 3); and 7.0-7.7 (9H, m) .
Example 7
Preparation of Butyl (chloromethyl) (4-chlorophenyl) methylsilane Solution 14.4 g (0.075 g) of 4-bromochlorobenzoyl and
9.5 ml. (12.3 g, 0.075 mol) methyl chloro (dichloro) methyl-. of silane in 150 ml of tetrahydrofuran, cooled to -60 ° C under nitrogen; and stirred, while 94 ml (0.15 g) of 1.6 mM n-butyl lithium solution of hexanes were added dropwise, which maintained the mixture between -65 and -55 ° C. The suspension was allowed to warm to room temperature, yielding a solution which was diluted with hexanes until another lithium chloride precipitated. Filtration, evaporate the filtrate<sup>;</sup>Residual dissolution in hexanes, reflux and evaporation yielded 19.8 g. pale orange liquor. 'Submerged distillate, give 1.8 g (12%) of chloromethyl (dibutyl) methylsilane b. 45 ° C (0.05 mm) followed by 6.8 g (35%) of the compound -> -, ligation compound as a colorless liquid: b.p. 90 ° C (0.05 mm) * n ^<sup>1</sup> 1,5246*
IR spectrum (endless): 2925, 1580, 1380, 1260, 1090, 1015, 820,740 cm.<sup>1</sup>.
BMR spectrum (ODO1): 0.4 (3H, S) * 0.6-1.5 (9H, m) * 2.9 (2H, S) '7.0-7.4 (42, ^) ,
Example 8 <sup>of</sup> methyl (2,4-dichlorophenyl) methyl (phenyl) silane chloride.
13.6 g solution. (0.060 mol) 2,4-dichlorobenz (moiepezole) and 12.3 g (0.060 mol) chloro (chloromethyl (phenyl) -l ·,
-27silane (prepared as in Example 14) in 85 ml. tetrahydrofuran dried, cooled to -60 ° C under nitrogen and stirred, while 38 ml (0.060 mol) of 1.6 molar solution of either, -butyl lithium hexane, at speed, or at a speed, were added dropwise.
kept the mixture below -55 ° C. It was precipitated by a red solution!
To warm to room temperature, treatment was performed with 5 ml of ethyl acetate to suppress any unreacted organolithium reagent and poured into 170 ml. The organic layer was separated, or the aqueous phase was washed with 50 ml. hexanes and the combined organic phases were washed three times with water and once with brine, dried over
<sub>t</sub><sup>1</sup> magnesium sulfate and evaporated, leaving one remaining 19.0 g of yellow oil. 'Submersion yielded 8.6 g. (45) of the title compound as a colorless liquid: b.p. 125-13Q ° C (0.05 mm). 1.5978 * IR spectrum (unbroken): 3080,3060,2960,2930,<sup>D</sup> 1 1570,1540,1640,1430,1365,1260,1120,1100,1040,820,475,735,705 cm.<sup>1</sup>. RL spectrum (CDC1<sub>5</sub>): 0.8 (3H, S) * 3.4 (2H, S) * 7.2-7.9 (8H, m). Example 9
Preparation of Chloromethyl / bis (4-chlorophenyl) 7methylsilane
19.1 g solution. (0.10 mol) of 4-chlorobromobenzene in 200 ml of tetrahydrofuran dry, cooled to -60 ° C under nitrogen
I stirred and 63 ml were added dropwise. (0.10 mol) 1.6 Molar N-Butyl Lithium Solution You are hexane;
cast, which kept the mixture below -55 ° C.
the saline was continued, while 6.3 ml of saline was added. (8.2 g)
0.05 mM) chloromethyl (dichloro) methylsilane at a rate which kept the mixture below -50 ° C.<sup>G.</sup>what solution was allowed to warm to 0 ° C / room temperature? & lt; L 'worked as in Example 8, supplying 16.5 g of citrus /!
-28 ° C oil. 'Distillation KUGELR0HR at 0.05 mmHg and air bath temperature 13 ° C-15 ° C, yielded 9.5 g (60%) of the title compound -.
as colorless liquid: 1,5913 * O spectrum (endless) 380, 3040, 3020,
2960, 2930, 1580, 1490, 1380, 1260, 1085, 1015, 805, 790, 775,740;<sup>1</sup>./®® (CDCl<sub>5</sub>0.7 (3H, S), 3.1 (2H, S), 7.2-7.7 (8H, m); Analysis for G ^ H ^ Cl ^ SI (w / o 315.70)
Calculated: G 53.26 * H, 4.15 * 01, 33.69
Found:
53.4
53.5
4,4
4,4
34,2
34,1
Example 10
Preparation of (Chloromethyl) bis- or thioacinyl) methylsilane
35 g solution. (0.20 mol) 4-fluorobromobenzene in 300 ml. of dry tetrahydrofuran was cooled to -60 ° C under nitrogen and stirred, 126 ml (0.20 mol) was added dropwise.
1.6 mM n-butyl lithium solution in hexane, at a rate which maintained the mixture below -55 ° C. Unfolding and cooling were continued until 12.6 ml (16.4 g 0.10) was added dropwise. m) of chloromethyl (dichloro) methylsilane, at a rate which maintained the mixture below 50 ° C. of yellow liquid. Submission distillation yielded 20.6 g. (73%) of the title compound as a colorless liquid: b.p. 107-127 ° C (0.1 mm) * 1,5481 Spectrum ®® (CDClj): 0.7 (3H, S), 3.2 (2H, S), 7.1 (4H, s, J = 9) and 7.6 (4H, J of d, J = 6 and 9). I!
Repeating this reaction using chloromethyl (diethoxy) methylsilane instead of dichlorosilane yielded the title compound with a yield of 58%, after submission by distillation, v: b.p. 115-138 ° C (0.2 mm) Ex 1.5464 * NjffiR spectrum as; . ··. ·. · '♦ - r * ·,
<img file="GR76497B_D0036.tif" />
-29Check ^ ba_1Ί
Chlorobutyl (2-chlorophenyl) (4-chlorophenyl) methylanilane
A solution of 6.3 mL (8.2 g, 5.05 mol) (methylsilyl dichloro) methylsilane and 8.1 g. (0.05 mol) 2-Bromochlorobenzene in 75 ml. dry tetrahydrofuran, cooled to -60 ° C
EL and unbuttoned, with 31 ml (0.05 mM) \ 1.6 mole of n-butyl lithium-hexane solution at a speed which maintained below -55 ° C. By continuous cooling and stirring, i
8.1 g were added. (0.05 mol) 4-Bromochlorobenzene, as a solid and then a further 31 ml of 1.6 mM n-butyl lithium solution, at a speed which maintained the mixture below -55 ° C. The resulting slurry was allowed to warm to room temperature carefully, treated with 1Q ml.
ethyl acetate and treated to Example 8, yielding
15.0 g of yellow oil clarifier. 'Distillate', provided 5.9 g (37%) of the compound title: b.p. 15O-165 ° C (0.7 mm) * 1.5916 * Spectrum<sup>u</sup>
LH / (endless) 3060, 3020, 2960, 2920, 2870, 1580, 1560, 1490, 1420,
1380,1255, 1125, 1115, 1085, 1035, 1015, 805, 750 cm. ”<sup>1</sup>.
NMR spectrum (CDCl _): 0.8 (3H, S), 3.3 (2H, 3), 7.2-7.7 (8H, m).<sub>:</sub>
The compounds of Table II are prepared by the partial antisense state of the Si-Cl bonds of C1<sub>2</sub>S? (CH ^ CHgCl, according to the procedure shown in Examples 6-11.
' -,.
GENERAL II
<img file="GR76497B_D0037.tif" />
-301
TABLE_II (continued)
X = R<sub>p</sub> R '; -<sup>G</sup>, o<sup>H</sup>2 ° C - 37 ° C cyclopropyl cyclohexyl
1- naphthylone
2- naphthyl phenyl phenyl phenyl
4-phenylphenyl 4-bromophenyl 4-fluorophenyl 4-phenoxyphenyl 4-tert-butylphenyl
3-trifluoromethylphenol 3-chlorophenyl 2-thiomethylphenyl 2-phenylphenyl
2,4-dichlorophenyl
2.4-dichlorophenyl 2,3-dimethylphenol
2-methyl-5-fluorophenyl
2.5-dimethoxyphenyl
2.6-Dimethylphenyl 315-dichlorophenyl 3,5-dichlorophenyl
3-methyl-4-chlorophenyl phenyl
4-fluorophenyl 4-chlorophenyl 4-β-bromophenyl 4-phenylphenyl 4-tert-butylphenyltoy 4-thiomethylphenyl 4-phenoxyphenyl
4-trifluoromethoxyphyl nylon * 2 cyclopropyl
3-methylbutyl
2-°6<sup>THE</sup>13 L cyclohexyl
£ £ ° · ° 4<sup>THE</sup>9
2-Vn £ “<sup>i</sup>3<sup>X</sup>7 n-0.X<sub>the</sub> bp 82-90 ° (C. Eichlst)
1,1-dimethylpropylene θ2<sup>THE</sup>5 !
is-0, H „
--- 3 7 £-°4<sup>THE</sup>9 £ £ Wood ° 4<sup>THE</sup>9 cyclopentylion * * ° 5<sup>THE</sup>11 cyclobutyl S22-<sup>i</sup>4<sup>X</sup>9 £-°4<sup>THE</sup>9 cyclopropyl n-C1 H1 cyclopentyl
bp 90-92 (0.1 mm)
bp 109-112 ° C (0.1 mm)
4-methylpentyl
1-methylbutyl 4 ° C<sup>THE</sup>9 cyclohexyl cyclopropyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl
bp 104-410 ° (0.2mm) nj 1.5624 bp 140-148 ° (0.1 mm) bp 144-155 ° (0.1 mm)
<img file="GR76497B_D0038.tif" />
-31*=<sup>R</sup>1· <sup>R</sup>i
4-Methylsulfonylphenol 4-cyclohexylphenyl 4- (4-fluorophenyl) phenol
3- (trifluoromethylphenol 2-chloro <rhynyl 2-methoxyphenyl
2-chloro-4-phenylphenyl
2-fluoro-4-phenylphenyl
3.5-dichlorophenyl
2.5-dimethoxyphenyl
2.6-dimethoxyphenol
4- bromophenyl
4-phenylphenyl 4-methoxyphenol
3-trifluoromethylphenol 2-methoxyphenol 2-chlorophenol
2.4-dichlorophenol
3.5-dichlorophenol 2-chlorophenyl yl
4- phenylphenyl alloy 4-phenylphenyl yl4-phenylphenyl 4-fluorophenyl 4-chlorophenol 1-naphthyl
4-phenoxyphenyl phenyl phenyl phenyl phenyl phenyl phenylbenz.132-133 ° (0.1 mm) phenyl phenyl phenyl phenyl
I phenyl phenyl
4-bromophenol b.p. 160-170 ° C (0.1mm) 4-phenylphenol a, m.115-117 ° 4-methoxyphenyl bp 166-171 ° (0.1mm),
3-trifluoromethylphenyl
2-methoxyphenyl
2-chlorophenol b.p. 135-140 ° (0.1mm)
2.4-dichlorophenol 1,5956
3.5-dichlorophenol (
4- fluorophenyl
4-chlorophenyl;
4-fluorophenol
2.4-dichlorophenyl
I.
2.4-dichlorophenol
2.4-dichlorophenol
2.6-dimethoxyphenol i
3.4-dichlorophenol.
Example 1 ^ 2
Preparation of (1.1<sup>G.</sup>-Diphenyl-1-yl) (chloromethyl) diethylsilane; The title compound can be prepared by itself! for. ! I. Process of Example 1, Using Chloro-Chloromethyl-P;<sup>? </sup>diethylsilane instead of chloro-chloromethyl-dimethylsulfate; Analogous compounds may be prepared by the application of "X" ... / ...
procedures of Examples 1-5 with the appropriate lithium or \ ______ of the L-32 GRIGNARD reagent and Cl (R)<sub>2</sub>Si (R ^ JCHgCl. The required chlorochloromethyl dialkylsilanes are prepared from Cl2 SO2 Cl2 using two RgMjGl or R equivalents<sub>2</sub>L * whenever R<sub>2</sub>= R ^ <sup>Well</sup>"A.A. ZHDANOV, VI PAKHOMOV, AND T. BAZHANOVA, ZH. OBSHGH.KHIM, 1973, 1280) or using an R equivalent<sub>2</sub>I4 <jCl or R<sub>2</sub>Ii? and thereafter one equivalent of R ^ MjGl or R ^ L · *, where R<sub>2</sub> is not equal to R ^.
i
Example £ 5
Preparation of (Chlorom, ethyl) triphenylsilane
Solution 12.6 ml. (18.4 gm.0,10 mol) (trichlorosilane chloromethyl) in 150 mL of dry ether, nitrogen free
Ice was cooled and 162 ml was added dropwise. (0.30 | mol) 1.85 molar solution of phenyl lithium in cyclohexane: ether 70:30, at a rate which kept the mixture below 15 ° C.
It was slurried overnight under temperature. In the room, the treatment was carefully treated with 10 ml.
of ethyl acetate to suppress any residual phenyl lithium, washed with water and brine, dried over i
magnesium sulfate and evaporated, remaining 33 g; of a sticky solid. Recrystallization from 30 ml of cyclohexane provided 15.8 g (51%) of the title compound as an off-white solid: m.p. 112-115 ° C * IR spectrum (UUJ0Ii<sup>R</sup>): 1420,1110,735,730,705,695 cm.<sup>1</sup> i
- ·. . i
NMR (CDCl2): 3.5 (2H, S), 7.0-7.8 (15H, m).
The compounds of Table III are prepared by gradual substitution of the Cl-StCHgCl SI-G1 bonds, according to the procedure of Examples 12-13.
TABLE III
<img file="GR76497B_D0039.tif" />
<img file="GR76497B_D0040.tif" />
<td>X = R<sub>1</sub>, B *</td><td> *2</td><td></td>
<td> °2<sup>THE</sup>5</td><td> *2*5</td><td> °2<sup>THE</sup>5</td>
<td> £22<sup>G</sup>3<sup>E</sup>7</td><td>222z<sup>G</sup>3<sup>H</sup>7</td><td>iso-C ^ Hg</td>
<td> 2-<sup>i</sup>4<sup>THE</sup>9</td><td> 2-<sup>G</sup>4<sup>H</sup>9</td><td> 2-°4<sup>THE</sup>9</td>
<td> 2-<sup>G</sup>8<sup>H</sup>17</td><td><sup>G</sup>2<sup>H</sup>5</td><td>cyclopentylion</td>
<td> £“<sup>G</sup>14<sup>H</sup>29</td><td>cyclopropol</td><td>1-methylbutyl</td>
<td>H ~<sup>G</sup>18^37</td><td> -<sup>p</sup>6<sup>THE</sup>13</td><td> 2-°6<sup>the</sup>13</td>
<td>cyclopropol</td><td> °2<sup>THE</sup>5</td><td> £-°4<sup>THE</sup>9</td>
<td>cyclohexyl</td><td> 2-<sup>p</sup>3<sup>THE</sup>7</td><td>nC ^</td>
<td>1-naphthylone</td><td> 2-<sup>G</sup>4<sup>H</sup>9</td><td>nC.H<sub>rt </sub>— 4 9</td>
<td>2-naphthylone</td><td> 2~<sup>G</sup>4<sup>H</sup>9</td><td>cyclobutanol</td>
<td>phenol</td><td>cyclopropol</td><td> 2-°6<sup>the</sup>,3</td>
<td>4-phenylphenyl</td><td>nC.H<sub>Q </sub>- 4 9</td><td>B-<sup>G</sup>4<sup>H</sup>9 ’</td>
<td>4-phenylphenyl</td><td> 2-<sup>C</sup>6<sup>H</sup>13</td><td>no<sub>6</sub>a,<sub>3</sub></td>
<td>4-phenylphenyl</td><td>cyclohexyl</td><td>cyclohexyl</td>
<td>4-chlorophenyl</td><td>nC<sub>4</sub>Hg</td><td>n-CLH<sub>Q</sub> - 4 9</td>
<td>4-fluorophenol</td><td>£ - ° L.</td><td></td>
<td>4-phenoxyphenol</td><td> 2-<sup>G</sup>4<sup>H</sup>9</td><td>cyclohexyl</td>
<td>4- (4-chlorophenoxy) phenyl</td><td> 2-<sup>p</sup>4<sup>THE</sup>9</td><td> 2“<sup>g</sup>4<sup>H</sup>9 '</td>
<td>4-tert-butylphenyl</td><td>S-<sup>G</sup>4<sup>H</sup>9</td><td>i2 £ "<sup>G</sup>4<sup>H</sup>9</td>
<td>3-methoxyphenol</td><td>c<sub>2</sub>h<sub>5</sub></td><td>tm-G ^ Hg</td>
<td>3-trifluoromethylphenol</td><td>s-<sup>g</sup>4h<sub>9</sub></td><td> -**<sup>G</sup>4<sup>H</sup>9</td>
<td>2-thiomethylphenol</td><td>iso-C ^ H ^</td><td>3-methylbutyl</td>
<td>2-phenylphenyl</td><td>cyclohexyl</td><td>cyclohexyl</td>
<td>2,4-dichlorophenyl</td><td> 2-<sup>g</sup>4<sup>H</sup>9</td><td>nC.H<sub>Q </sub>- 4 9</td>
<td>2,6-dimethylphenol</td><td>X ££ Σ · ° 4<sup>THE</sup>9</td><td>MS · - ° 4<sup>THE</sup>9</td>
<td>3,5-dichloromethane</td><td>cyclopentylion</td><td>cyclopentylion</td>
<td>3-methyl-4-chlorophenylene</td><td> £-<sup>G</sup>4<sup>H</sup>9</td><td>2-h</td>
<td> °2<sup>THE</sup>5</td><td>phenol</td><td>phenol</td>
<td>cyclohexyl</td><td>phenol</td><td>phenol '</td>
<td> 2-<sup>The</sup>1^37</td><td>phenol</td><td>phenol</td>
<td> 2-<sup>The</sup>L.</td><td>4-chlorophenol</td><td>4-chlorophenol</td>
<td> 2-°12»2<sub>5</sub></td><td>4-chlorophenol</td><td>4-chlorophenol</td>
<td>1-naphthol</td><td>4-fluorophenol</td><td>4-fluorophenol</td>
<td>cyclopropol</td><td>phenol</td><td>4-tert-butylphenylion</td>
<td> 2-°4<sup>THE</sup>9</td><td>phenol</td><td>4-phenylphenol / nolion</td>
<td>In £ X · ”<sup>p</sup>4<sup>THE</sup>9</td><td>phenol</td><td>2,4-6 dichloromethane</td>
<td> 2-°4<sup>THE</sup>9</td><td>phenol</td><td>3-Trifluoromethylphenol I.</td>
<td>iso-C.H.<sub>the </sub>----4 9</td><td>phenol</td><td>3,5-dichlorophyll 1 n material</td>
-34IHNAS III (continued)
<td>X = R<sub>1</sub> , R {</td><td> *2</td><td></td>
<td>cyclopentylion</td><td>phenyl</td><td>2,6-dimethoxyphenyl</td>
<td> £<sup>C</sup>14<sup>THE</sup>29</td><td>4-chlorophenyl</td><td>2-fluorophenyl</td>
<td>4 °<sup>THE</sup>9</td><td>4-fluorophenyl</td><td>4-phenylophen yl</td>
<td>4-chlorophenyl</td><td>4-chlorophen yl</td><td>4-chlorophenyl</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td>4-fluorophenyl</td>
<td>4-phenylphenyl</td><td>4-Phenylphenyl methyl</td><td>4-phenylphenyl</td>
<td>2,4-dichlorophen yl</td><td>2,4-dichlorophenyl</td><td>2,4-dichlorophenylion</td>
<td>phenyl</td><td>4-fluorophenyl</td><td>4-fluorophenyl</td>
<td>phenyl</td><td>4-chlorophen yl</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-dichlorophenylirn</td>
<td>2-naphthylone</td><td>4-methylthiophenyl</td><td>4-methylthiophenyl</td>
<td>4-chlorophenylion</td><td>2-methoxyphenyl</td><td>2-Methoxyphenyl:</td>
<td>4-chlorophenyl</td><td>3-chlorophenylion</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-naphthylone</td><td>3-bromophenyl</td><td>3-methylphenyl</td>
<td>4-phenoxyphenyl</td><td>3,5-dimethylphenyl</td><td>3,4-dichlorophenyl</td>
Example 14 \ I
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, cooled to -70 ° C in nitrogen and vigorously stirred, while 0 mL of mixture was added dropwise. , 10 mol) 1.8 mM phenyl lithium solution in ether: cyclohexane 3 g: 7 g and 55 ml ether, at a rate which kept the mixture below -70 ° C. The resulting suspension was cooled and warmed to 0 ° C. then allowed to remain for the whole i
Overnight, filtration and evaporation of the filtrate left 20.4 g.
of golden oil, which was subjected to distillation, yielding 14.6 g. (71) of the title compound as a colorless liquid: / bp 71 (0.6 mm) * n;<sup>3</sup> 1,5337 * IR (unbroken) 3080,3060,2980,2930,155 <sup>the</sup> Spectrum . T / '- λ g
1260,1120,820,790,740,700 cm.<sup>1</sup>/ ®® (CDCl_) 0.8 (3H 3), 6 ^ 1 ^ (& gt;
<img file="GR76497B_D0041.tif" />
-74 ° C;<sub>r</sub>U30,
2P, 'S); A ·' ·:
-357.3-7.6 (3H, m), 76.-7.8 (2H, m).
Example J 5
Preparation of (1.1 <sup>G.</sup>-Diphenyl-4-yl) chloro (chloromethyl) methylsilane; The title compound may be prepared by reaction of equimolar amounts of 4-bromodiphenyl, 3-methyl dichloride (methyl) silyl chloride.
Compounds of Table IV can be prepared using the procedures of Examples 14 and 15.
TABLE IV xs: -ch<sub>o</sub>ci t
Cl
XR<sub>1</sub>, R ' <sup>C</sup>2<sup>H</sup>5 t-p<sub>4</sub>THE<sub>9</sub> £-°4<sup>H</sup>9 £ - ° iA5 £ ° 1 £ p57 cyclopropyl cyclohexyl
1-naphthol
2-naphthol phenyl
4-phenylphenol 4-phenylphenol 4-chlorophenyl 4-chlorophenyl 4-fluorophenyl 4-phenoxyphenyl
4-tert. -b out of 4-trifluoromethoxyphenyl 4- (4-fluorophenyl) phenyl
3-trifluoromethylphenyl
<img file="GR76497B_D0042.tif" />
-36 TABLE IV (continued)
X = R<sub>p</sub> R {
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-O<sub>12</sub>THE<sub>25</sub>
2- ° IL7 1-naphthyl phenol
4- fluorophenyl
4-chlorophenyl 4-phenylphenyl 4-tert-butylphenyl
3-fluorophenyl 2-methoxyphenyl
2-chlorophenyl
2.4-dichlorophenyl
3.5-dichlorophenyl
4- fluorophenyl
4-chlorophenyl 4-phenylphenyl v
2,4-dichlorophenyl methyl
3-trifluoromethylphenyl 2-methoxyphenyl
2- chlorophenyl yl
3-trifluoromethylphenyl 2-fluoro-4-chlorophenyl
2.3-dimethylphenyl
2.6-dimethoxyphenyl
3.4-Dichlorophenyl cyclopentyl <sup>GH</sup>3 nC.H<sub>Q</sub>
- 4 9
CH, cyclopropyl
1,1-dimethylpropylene.
£‘<sup>C</sup>5<sup>H</sup>ii
2,4-dichlorophenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl
4-fluorophenyl
4-chlorophenol
4-phenylphenyl
2,4-dichlorophenyl
3-trifluoromethylphenyl 2-methoxyphenyl
4- fluorophenyl
4-tert-butylphenyl 4-bromophenyl 4-methylthiophenyl i
4-Methoxyphenyl 4-methylphenyl
<img file="GR76497B_D0043.tif" />
Example 16 Non-ethyl (ethyl) ethyl (gynyl) silyl
-37Solution 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. ether was quenched while a solution of 4.1 g (0.020 g) was added dropwise<sub>;</sub> mp) chloro (chloromethyl) methyl (phenyl) silane in 10 mL ether. The resulting suspension was heated to reflux for 2 hours, cooled with water, washed with 0.1N aqueous HCl solution, saturated aqueous NaHCO3, with water and brine, dried overnight. 3.2 grams. Distillation provided 1.7 g (42%) of a compound title as a colorless liquid: b.p. 46-49 ° C (0.05 mm) n<sup>2</sup> 1.5207 * NIF spectrum (GDCl j: 0.5 (3H, S) * 3.0 (2H, S) * 3.5 (3H, S) * and 7.3<sub>;</sub>-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 mm. (1], 1 g.0.15 mol) tert-butanol, 11.5 ml. (8.3 g.0.082 g) triethylamine and 0.5 g g. (0.008 mol) Imidazole in 60 ml of dimethylformamide was stirred at 80 ° C for 2 h. The resulting slurry was cooled, poured into 200 ml. The ether extracts were washed three times with water and then with 0.1 N aqueous HCl solution, saturated aqueous solution of CaHCl2 and brine, dried overnight, and dried overnight. gr. oily-orange oil. Submerged distillation provided 11.9 g. (65%) of the compound title: b.p. 78-82 ° C (0.2 mL);<sup>1</sup> 1,5010 * IR spectrum (endless): 3080 ^ 30 ^ 0.2990, 2940.1600.1435, 1395, 1370, 1260, 1245,1195,1125,1060,103
725, 705, 650 cm.<sup>1</sup>. HMR (CDClj) / 0.5 (3H, S) * 1A (2H, S) and 7.3-7.8 (5H, m). '/> // //
<img file="GR76497B_D0044.tif" />
<img file="GR76497B_D0045.tif" />
I.
-38Example ^ y ^ ha_1_8
Preparation of chloromethyl (ethoxy) methyl (phenyl) silane; 18.2 ml solution. (18.2 g, 0.10 mol) of chloromethyl (diethoxy) methylsilane in 200 ml of dry ether, was strongly stirred under Ng and ground, with 56 ml (0.10 mol) of 1.8 mol. cyclohexane: ether 70: 3, the Q 'j casting which kept the mixture below 50-C.
The verb was allowed to warm to room temperature, treated carefully with 10 ml of ethyl acetate, washed with water and brine, dried over magnesium sulfate and dried overnight. golden yellow liquidSubmit distilled, provided 9.5 g. ($ 44), a liquid-free compound header: b.p. 80-84 ° C (0.1 mm) * 1.5144 * NMR spectrum (ODCl2): 0.5 (3H, 3); 1.2 (3H, I, J = 7) * 3.0 (2H) , S) * 3.8 (2H, <j, J = 7) * 7.2-7.8 (5H, m).
Compounds of Table V can be prepared using the procedure of Examples 16-18.
TABLE VR<sub>o</sub> ΐ2 x-sr-cH.ci 1 2 OR.
<td>X = R<sub>1</sub>, Rf</td><td>-B</td><td colspan="2">L.</td>
<td>h</td><td>oh<sub>5</sub></td><td colspan="2">CEL</td>
<td>I £ ilA ”° 4<sup>H</sup>9</td><td></td><td>ts. — C</td><td>L.</td>
<td> 2-°4<sup>THE</sup>9</td><td>i</td><td colspan="2"> °2<sup>THE</sup>5</td>
<td> £“<sup>p</sup>ΐ2<sup>THE</sup>25</td><td><sup>C</sup>2<sup>H</sup>5</td><td colspan="2"></td>
<td> £^18^37</td><td> £-°6<sup>H</sup>13</td><td colspan="2"></td>
<td>cyclopropyl</td><td>CB ^</td><td colspan="2">S ”<sup>C</sup>4<sup>H</sup>9</td>
<td>cyclohexylion</td><td>CH ^</td><td>OH, / W</td><td></td>
<td>1-naphthylone</td><td>iso-0 ^ Hg</td><td>equals / c ^ H</td><td> 7</td>
<td>2-naphthylone</td><td>cyclobutyl</td><td> £/3<sup>3</sup>^</td><td></td>
<td>phenyl</td><td></td><td>HZ '</td><td></td>
-39 TABLE V (continued)
<td>X = R<sub>p</sub> R (</td><td> ^2</td><td></td>
<td>phenolithin</td><td>CH, 3</td><td>ioo-C_H „--3 7</td>
<td>phenyl</td><td>t.-C ^ Eth</td><td>H</td>
<td>4-phenylphenyl</td><td>£ - ° L.</td><td>CH, 3</td>
<td>4-phenylphenyl</td><td>£ · · -<sup>p</sup>5<sup>THE</sup>9</td><td>H</td>
<td>4-phenylphenyl</td><td>Oh,</td><td> °2<sup>H</sup>5</td>
<td>4-phenylphenyl</td><td>CH, 3</td><td> £-°4<sup>H</sup>9</td>
<td>4-chlorophenyl</td><td> 3-°4<sup>X</sup>9</td><td> 2-<sup>G</sup>4<sup>H</sup>9</td>
<td>4-chlorophenyl</td><td>ch<sub>5</sub></td><td>CH, 3</td>
<td>4-chlorophenyl</td><td>ch<sub>3</sub></td><td>c<sub>9</sub>h<sub>k </sub>λ 3</td>
<td>4-fluorophenyl</td><td>S ”<sup>g</sup>6<sup>h</sup>13</td><td>nC ^ H?</td>
<td>4-fluorophenyl</td><td>ch<sub>5</sub></td><td><sup>G</sup>2<sup>H</sup>5</td>
<td>4-phenoxyphenyl</td><td>cyclohexyl</td><td>Equal-ΰ<sub>4</sub><sup>THE</sup>9</td>
<td>4-tert -butylphenyl</td><td>nC<sub>5</sub><sup>H</sup>?</td><td>S-<sup>g</sup>4<sup>H</sup>9</td>
<td>3-trifluoromethylphenyl</td><td>SWISS · -<sup>p</sup>4<sup>THE</sup>9</td><td>THE</td>
<td>2-methylthiophenyl</td><td>cyclopentylion</td><td><sup>i</sup>2ΐ5</td>
<td>2,4-dichlorophenyl</td><td>ch<sub>5</sub></td><td>0P<sub>3</sub></td>
<td>2,4-dichlorophenyl</td><td>gh<sub>3</sub></td><td><sup>THE</sup>2=5</td>
<td>2,4-dichlorophenyl</td><td>CH ^</td><td>m-C ^</td>
<td>2,4-dichlorophenyl</td><td>nC<sub>4</sub>H<sub>9</sub></td><td>The<sub>2</sub>X</td>
<td>2,3-dimethylphenyl</td><td>cyclopropyl</td><td>iso-C ^ Hg</td>
<td>2-methyl-5-fluorophenyl</td><td> £“<sup>G</sup>a<sup>H</sup>q</td><td></td>
cp.722.6-dimethoxyphenyl. 3-Methyl-4-chlorophenol 3,5-dichlorophenol
1,1-dimethylpropylyl H CH2 <sup>Pi</sup>2<sup>THE</sup>5 n-O,
IP IP ° 12<sup>THE</sup>25 <sup>i</sup>2<sup>THE</sup>5
2,4-dichlorophenyl tert-C2 Hg
<td>B ”<sup>p</sup>ΐ ^ 37</td><td>phenyl</td><td>ch<sub>3</sub></td>
<td>1-naphthol</td><td>phenyl</td><td><sup>G</sup>2<sup>H</sup>5</td>
<td>phenyl</td><td>phenyl</td><td>tert;<sup>G</sup>4^<</td>
<td>4-fluorophenyl</td><td>phenyl</td><td> %”</td>
<td>4-chlorophenyl</td><td>phenyl</td><td>n-CJL</td>
<td>4-phenylphenyl</td><td>phenyl</td><td><sup>p</sup>2H5</td>
<td>4-Phenylphenyl methyl</td><td>phenyl</td><td>s-<sup>g</sup>A <a</td>
<td>4-tert-butylphenyl</td><td>phenyl</td><td>i-<sup>G</sup>4% J</td>
<td>3-fluorophane</td><td>phenyl</td><td><sup>i</sup>2<sup>THE</sup>^ iii</td>
<td>2-methoxyphenyl</td><td>phenyl</td><td>H p /</td>
<td>2-chlorophenyl</td><td>phenyl</td><td></td>
V A. ΐ ··· L · ~. · '.
-40 TABLE V (continued)
<td>X = R<sub>p</sub> R (</td><td> »2</td><td> «6</td>
<td>2,4-dichlorophenyl</td><td>phenyl</td><td>iso-C ^ Hg</td>
<td>3,5-dichlorophenyl</td><td>phenyl</td><td>n-0<sub>L.</sub></td>
<td>4-fluorophenylene</td><td>4-fluorophenylene</td><td>tm-O ^ Hg</td>
<td>4-fluorophenyl</td><td>4-fluorophenyl</td><td> °2<sup>THE</sup>5</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>CH_ 3</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td> °2<sup>THE</sup>5</td>
<td>4-phenylphenyl</td><td>4-phenylphenyl</td><td>CH, 3</td>
<td>2,4-dichlorophenyl</td><td>2,4-dichlorophenyl</td><td>G<sub>2</sub>H5</td>
<td>3-trifluoromethylphenyl</td><td>3-trifluoromethylphenyl</td><td> £22-<sup>p</sup>4<sup>THE</sup>9</td>
<td>2-methoxyphenylone</td><td>2-methoxyphenyl</td><td>THE</td>
<td>2-chlorophenyl</td><td>4-fluorophenyl</td><td>THE</td>
<td>3-trifluoromethylphenyl</td><td colspan="2">4-tert-butylphenyl n-O2 H2 O</td>
<td>2-fluoro-4-chlorophenyl</td><td>4-bromophenyl</td><td>iso-C ^ Hg</td>
<td>2,3-dimethylphenyl</td><td>4-methylthiophenyl</td><td>The<sub>2</sub>the<sub>5</sub></td>
<td>2,6-dimethoxyphenyl</td><td>4-methoxyphenyl</td><td>THE</td>
<td>3,4-dichlorophenyl methyl</td><td>4-methylphenyl</td><td>iso-G.H.<sub>the </sub>--4 9</td>
Example 19
Preparation of (1,1-Diphenyl-4-yl) dimethyl (1H)<sub>x</sub> 1 , 2<sub>A</sub>4 of az-ol-1-ylmethyl) silane
Size 2.6 g (0.010 mol)<sup>G.</sup>-diphenyl-4-yl) chloromethyldimethylsilane and 1.1 g (0.012 mol) of sodium 1,2,4-triazyl in 5 ml of dimethylformamide, heated at 80 ° C for 2 hours, 2 ° C, 2 ° C; The ether solution was washed with water and brine, dried over magnesium sulfate and evaporated to a residue of 2.3 g. colorless solid, f. 79-S6 ° C. Recrystallize from a mixture of 25 ml of hexanes and 2 ml of ethyl acetate of the title compound: m.p. 92-93 ° C IR 1000, 825, 760,695 cm. ”<sup>1</sup>. NMR spectrum (CDGl2):
7.2-7.7 (9H, m) * 7.8 (1H, S); 7.9 (1H, 3) *
<img file="GR76497B_D0046.tif" />
-41'Analysis for C ^ H ^ N ^ ST (N / A 293.43):
Calculated: C 69.58 * H, 6.53 * N, 14.32 *
Found: 70.0 6.6 13.9
69.8 6.7 13.8 'Equivalent molar mixture of 1,2,4-triazole and one may be used instead of the preformed sodium salt of triazole <sup>n</sup> Sodium oxide. Note that the reagents are properly fed<sup>!</sup>as combined prior to the addition of silane, as the anhydrous chloromethylsilanes very vigorously with sodium methoxide in dimethylformamide, yielding undesirable products.
Badassi_20
I | Insulation |<sub>±</sub>1<sup>G.</sup>-Diphenyl-4-yl) dimethyl (4H-1,2,4-triazol-4-yl) |
Sample 5 g once crystallized 1.1<sup>G.</sup>- (Diphenyl ~ 4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, prepared as in Example 14 using sodium methoxide (1,2,4-triazole) under high pressure liquid chromatography / cartridges (silica gel) of WATERS PREP PAK-500, flow rate 250 ml per minute_7 · Elution with ethyl acetate: 50:50 hexane eliminated at first a small amount of impurities and then cleaned 1 , 4-triazol-1-ylmethyl, ref. 99-100 ° C. Continuation of elution with ethyl acetate: 80: 20 acetonitrile provided a small amount of the title compound as a colorless solid: mp 133-113 ° C * NMR spectrum (CDC1<sub>5</sub>): 0.4 (6H, S) * 3.7 (2H, S) * 7.2-7.7 (9H, m) * 7.9 (2H, S). Microanalysis for C ^ H ^ N ^ S * (N / A 293.43) Calculated: C 69.58 * H 6.53 * Found:<sup>So n</sup>* <sup>L r,</sup>‘
14,32
13,9
14,2
69,0’
63,3*
6,7'
6,7*
<img file="GR76497B_D0047.tif" />
Example 21 Preparation of 2-nyl) (II H-1,2,4-triazole-1-yl) silanomium • {:
L.
!
'·/
-42Mix 9.0 ml. (9.2 g of 0.050 mol) chloromethyl dimethylphenylsilane and 5.5 g. (0.060 mol) of sodium salt
1,2,4-triazole in 25 ml of dimethylformamide, stirred and heated at 9 ° -95 ° C for 2 hours, cooled, diluted with water, and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulfate and evaporated, remaining 8.1 g. (75%) oily-brown oil, 1.5550, containing the title compound and all the impurities, as detected by NMR spectrum. (Clearest sample was obtained by distillation: bp 99 ° C (0.02 mm) x ° 1,5403 * NKR spectrum (CDC1): 0.4 (6H, S) * 3.8 (2H, S) * 7.27.7 (5H, m) * 7.7 (1H, S) '7.8 (1H, S).
<td colspan="2" rowspan="2">Analysis by Tune Calculated: C 60.78; H,</td><td colspan="2">(nw.217.34)</td>
<td> 6.96*</td><td>N, 19.33</td>
<td>Found:</td><td> 60.7*</td><td> 7,0*</td><td> 16.9*</td>
<td></td><td> 60.2*</td><td> 7,0*</td><td> 16.8.</td>
Example 22
Preparation of 0_ (4-Chlorophenyl) 'dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane
A mixture of 2.2 g. (0.010 mol) chloromethyl (4-chlorophenyl)
Of dimethylsilane and 1.1 g. (0.012 moles) of sodium salt 1,
2,4-triazole in 5 ml dimethylformamide, heated to 80-90 ° C
After 2 hours, it was diluted with water and extracted with ether. The ethereal solution was washed with water and brine, dried over magnesium sulfate and evaporated, leaving 2.1 g (83%) of the precipitate.<sup>c</sup> · 21 compound scissors as a yellow liquid: the * 1,5428 * IR spectrum (extreme): 1555 1470,1245,1130,1080,1010, 835,805,795,735 cm.<sup>1</sup>. i
HMR spectrum (CDCl2): 0.4 (6H, S) * 3.8 (2H, S); 7.4 (4H, S stream) * 7.8 (1H, S) * 7.9 (1H, S). L j H
Example 23 Il \
Preparation of (2,4-Dichlorophenyl) dimethyl (1H-1 j 2 L 4-trifluoro-1-yl)
<img file="GR76497B_D0048.tif" />
-43yl) silane
A mixture of 5.1 g. (0.020 mole) of chloromethyl (2,4-dichlorophenyl) dimethylsilane and 2.0 g. (0.022 mol) of 1,2,4-triazole sodium salt in 10 ml dry dimethylformamide, stirred at 80-90 ° C for 2 h. The resulting suspension was cooled, diluted with water and washed with ether. The ether extracts were washed several times with water and once with brine, dried over magnesium sulfate, and evaporated, remaining 4.6 g (81%) of 1.5 g of IR buffer: extreme): 1550, 1485, 1440, 1345, 1260, 1240, 113, 1085, 1025, 1005,835 cm.<sup>1</sup>
NMR spectrum (CDC1<sub>5</sub>): 0.5 (6H> S); 4.1 (2H, S); 7.2-7.5 (3H, m); 7.8 (1H,
3) '7.9 (1H, 3).
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 methylsilane chloromethyl bis (4-chloroph-L; nyl) and 2.0 g. (0.022 mol) of sodium salt
1,2,4-triazole in 10 mL of dry dimethylformamide, stirred at 80 ° C for 4 h. The resulting slurry was cooled, diluted with water and washed with ether. The ether extracts were washed several times with water and once with brine, dried over magnesium sulfate, and evaporated to a residue of 5.4 g.<sup>; </sup>Distillation of KUGE1R0HR at 120-150 ° C (air bath) / 0.05 mm yielded 4.0 g. (58%) of the compound title as pale yellow; X single oil: 1.5966; RMR spectrum (CDCl,): O, 7 (3H S); 4.1 (2H, S);
7.2-7.5 (8H, m); 7.8 (1H, S); 7.9 (1H, S).
Example 25
Preparation of bis (4-fluorophenyl) methyl (1H-1, 2,4-tert) silane
<img file="GR76497B_D0049.tif" />
-44Mix 4.2 gr. (0.015 mol) (chloromethyl) bis (4-fluorophenyl) methylsilane and 1.4 g (0.015 mol) of 1,2,4-triazdal sodium salt in 8 ml of dimethylformamide, stirred at 80 ° C. The resulting slurry was cooled, diluted with water, and treated to Example 24, yielding 4.0 g. ocher-yellow oil. The impurities were removed by distillation of EUGEIROHR at 120-125 ° C (0.05 mmol), with a residual 2.3 g. (49%) of the title compound as a yellow oil: ru 1,5538 IR spectrum (endless): 3065.3030, <sup>u</sup> Spectrum
2960,2925, 1590,1500,1270,1235,1165,1110,1010,830,790 cm. / NMR (CDCl ^) s O, 7 (3H, S), 4.2 (2H, S), 7.1 (4H, i, J = 9), 7.5 (4H, cl of J, J = 6 and 9), 7 , 8 (1H, S) and 7.9 (1H, S).
i
By applying the procedures of Examples 19 and 21) -25 with suitable chloromethylsilanes, the compounds of Table VI can be prepared which Q ^ = Qg = H.
TABLE_WIN
R.-ST-GH.N 5 ° 2<sup>THE</sup>5 L-C ^ Hγγ £θ44<sup>THE</sup>9 tf-0<sub>4</sub>THE<sub>9</sub>
-°12<sup>X</sup>25 £<sup>C</sup>14<sup>H</sup>29
-<sup>C</sup>18 Cyclopropyl cyclobutyl cyclopentyl cyclohexyl
1- naphthylone
2- naphthyl on<sub>5</sub>
OH + on<sub>3</sub>
CH, ox<sub>3</sub> ^3
CH, on<sub>3</sub>
CHL
Ohj
CH,
OH,
CH,
0^
CH,
CH,
CH,
1.4713
1.4687 n £<sup>3</sup> 1.4626
<img file="GR76497B_D0050.tif" />
-45IIIX VI (continued)
4-bromophenyl
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-methylsulfonylphenyl 4-isopropylphenyl 4-tert-butylphenyl cyclohexyl
4-trifluoromethoxyphenyl
4- (4-chlorophenyl) phenyl
4- (4-bromophenyl) phenyl
4- (4-methylphenyl) phenyl
4- (4-Trifluoromethylphenyl) phenyl
4- (4-fluorophenyl) phenyl
3-phenylphenyl
3-trifluoromethylphenyl; 3-chlorophenyl vinyl
2-trifluoromethylphenyl
2-phenylphenyl
2-chlorophenyl
2-methoxyphenyl
2.3-dimethylphenyl
2.3-dimethoxyphenyl
2.4-difluorophenylone
2-fluoro-4-chlorophenyl 2-chloro-4-fluorophenyl 2-chloro-4-phenylphenyl 2-fluoro-4-phenylphenyl
<td></td><td colspan="3"> ^3</td>
<td><sup>CH</sup>3</td><td> 01¾</td><td> „20 %</td><td> 1.5647</td>
<td>CH, 3</td><td></td><td rowspan="2">bp ' 26<sup>n</sup>D</td><td>108 ° (0.2 mm)</td>
<td>CH, 5</td><td>CH, 3</td><td>1 .5401 i</td>
<td>CH K</td><td> 0¾</td><td></td><td> 1.5754</td>
<td>CH, 3</td><td>CH, 3</td><td>“D<sup>2</sup></td><td>1.5703 I.</td>
<td> (3¾</td><td>ch<sub>3</sub></td><td></td><td></td>
<td>CH,</td><td>CH,</td><td></td><td></td>
<td> 3</td><td> 3</td><td></td><td></td>
<td>oh<sub>3</sub></td><td> 01¾</td><td rowspan="2"> ”?2</td><td></td>
<td> (3¾</td><td> (3¾</td><td> 1.5790</td>
<td> 01¾</td><td> (3¾</td><td></td><td> 1.4909</td>
<td>ch<sub>5</sub></td><td>ch<sub>3</sub></td><td>"S '</td><td> 1.5350</td>
<td>CH<sub>5</sub></td><td>OH, 3</td><td> $</td><td> 1.5538</td>
<td>CH,</td><td>OH,</td><td></td><td></td>
<td>3 CH<sub>5</sub></td><td>3 C ^</td><td></td><td> 1.5125</td>
<td>CH<sub>3</sub></td><td> (3¾</td><td></td><td> 1.5235</td>
<td>gh<sub>3</sub></td><td>CH, 3</td><td> „22</td><td> 1.4768</td>
<td> (3¾</td><td>GB?</td><td rowspan="2"> „22</td><td></td>
<td>OH, 3</td><td> 01¾</td><td> 1.5802</td>
<td>OH,</td><td></td><td></td><td></td>
<td>OH,</td><td>OH,</td><td></td><td></td>
<td>(3¾ OH,</td><td>(3¾ OH, 3</td><td> „21</td><td> 1.5939</td>
<td>CH, 3</td><td> 01¾</td><td>g °</td><td> 1.4845</td>
<td>0¾ CH, 3</td><td> (3¾ 01¾</td><td>m.p. 23 V.</td><td> , 37-43° 1.4964</td>
<td>CH, 3</td><td> 01¾</td><td> „22 <sup>n</sup>D</td><td> 1.5900</td>
<td>OH, 3</td><td> 01¾</td><td>n<sup>22</sup></td><td> 1.5442</td>
<td>OH,</td><td>C ^</td><td></td><td> 1.5216</td>
<td>OH,</td><td> 01¾</td><td rowspan="2"> „22</td><td></td>
<td> (3¾</td><td> (3¾</td><td> 1.5322</td>
<td> 0¾</td><td>OH, 3</td><td></td><td></td>
<td><sup>GH</sup>3</td><td> 0.1¾</td><td></td><td></td>
<td></td><td>ca ^</td><td></td><td></td>
<td> 01¾</td><td> (3¾</td><td></td><td></td>
<td>CH, 3</td><td> (3¾</td><td></td><td></td>
<img file="GR76497B_D0051.tif" />
-46—
TABLE VI (continued)
-i
2-methyl-5-chlorophenyl 2,6-dimethoxyphenol
2, β-dimethylphenyl
3.4-Dichlorophenyl
3-methyl-4-fluorophenyl
3.5-dichlorophenyl ° 2<sup>X</sup>5 iso-O ^ n-0.X<sub>a </sub>- 4 9 n-0 n-0 n-0 n-0 n-0
CHCH,
CH, gh<sub>5</sub>
CH<sub>5</sub>
CH<sub>3</sub>
OH
Ox ^ ch<sub>5</sub>
OH,
CH,
CH, m.p. 63-69 ° CH ^
V.
1.5404
1,5602 cyclohexyl CH, n-σ<sub>4</sub>THE<sub>i</sub> CH / n ^<sup>2</sup> 1.4672
<td> 10<sup>THE</sup>21</td><td>cyclopropyl</td><td>CH, 3</td>
<td> 12<sup>THE</sup>25</td><td>n-O ^ Xr</td><td>Ci / i</td>
<td> 14<sup>THE</sup>29</td><td>L-C Η Hγ</td><td>CH, 5</td>
<td> 18<sup>THE</sup>37</td><td>3-methyl- pylon</td><td>CH ^ I.</td>
cyclopropyl cyclopentyl cyclohexyl 1-naphthol
1- naphthol
2- Naphthalene vinyl vinyl vinyl 1,1 vinyl
4-phenylphenyl
4-phenylphenyl
4-bromophenyl
4-chlorophenyl
4-fluorophenyl
4-phenoxyphenyl
4-iso-propylphenyl
4-tert -butylphenyl
3-phenylphenyl
3-trifluoromethylphenyl
3-chlorophenyl
<td> -<sup>a</sup>6<sup>X</sup>13</td><td>0X<sub>5</sub></td>
<td>cyclopentolone</td><td>OH ^</td>
<td>cyclohexyl</td><td>Oh,</td>
<td>nC .H<sub>rt</sub></td><td>0H_</td>
<td> - 4 9</td><td> 3</td>
<td>2 £ iT.-C<sub>4</sub>H<sub>g</sub></td><td>CH, 5</td>
<td>nC<sub>c</sub>H ..</td><td>CH,</td>
<td> - 5 11</td><td> 3</td>
<td>nC ^</td><td></td>
<td> 2-¾</td><td>Oh,</td>
<td colspan="2">, dimethylpropyl CH,</td>
<td>N ° 6<sup>THE</sup>13</td><td>OB,</td>
<td> 0^</td><td>0X<sub>5</sub></td>
<td>nC.H<sub>n</sub></td><td>Oh,</td>
<td> -49</td><td> 3</td>
<td>1C-c ^ Hg</td><td> %</td>
<td>nC, H<sub>n</sub></td><td>CH,</td>
<td> - 4 9</td><td> 3</td>
<td>nC, H<sub>n</sub></td><td>OH,</td>
<td> - 4 9</td><td> 3</td>
<td>In £ ah-<sup>p</sup>4<sup>THE</sup>9</td><td>CH, 3</td>
<td>cyclopropyl</td><td>OH ^</td>
<td>Equal-0, H.<sub>the</sub></td><td>CH,</td>
<td></td><td> 3</td>
<td>iso-C, H - 4 9</td><td><sup>CH</sup>3</td>
<td> 5-¾</td><td> 0¾</td>
<td> 2¾,</td><td> 0¾</td>
£ 1.5297 h<sup>2</sup> 1.5838 %<sup>1</sup> £ 1,5344<sup>2</sup> 1.5120
<img file="GR76497B_D0052.tif" />
-47 TABLE VI (continued)
<td>h</td><td>L.</td><td> «3</td>
<td>2-methoxyphenyl</td><td>£££ Ξ ·<sup>a</sup>4<sup>THE</sup>9</td><td>Oh,</td>
<td>2-thiomethylphenyl</td><td>cyclobutyl</td><td>CHj</td>
<td>2-phenylphenyl</td><td>equal, H.<sub>a </sub>- 4 y</td><td>CH,</td>
<td>2,4-dichlorophenyl</td><td>H-<sup>G</sup>4<sup>H</sup>9</td><td>CH<sub>3</sub> 1.5411</td>
<td>2,4-dichlorophenyl</td><td>cyclopropyl</td><td><sup>GH</sup>3</td>
<td>2,3-dimethylphenyl</td><td>THE"<sup>p</sup>3<sup>THE</sup>7</td><td>GH<sub>3</sub></td>
<td>2-methyl-5-fluorophenyl</td><td>cyclopentylion</td><td>cn<sub>5</sub></td>
<td>2,5-dimethoxyphenyl</td><td>4-with pouches</td><td>CH</td>
<td>2,6-dimethylphenol</td><td colspan="2">1-methylbutyl CH_</td>
<td>3,4-dichlorophen yl</td><td> 2-<sup>p</sup>5<sup>X</sup>ii</td><td>ch<sub>5</sub></td>
<td>3,5-dichlorophenyl</td><td>b-<sup>p</sup>4<sup>THE</sup>9</td><td>CH, 3</td>
<td>3,5-dichlorophenyl</td><td>cyclohexyl</td><td>ch<sub>5</sub></td>
<td>3-methyl-4-chlorophenol</td><td>cyclopropyl</td><td>ch<sub>5</sub></td>
<td>phenyl</td><td>phenyl</td><td>CH<sub>5</sub> n ^<sup>2</sup> 1.5852</td>
<td>4-fluorophenyl</td><td>phenyl</td><td>CH<sub>5</sub> r ^ ° 1.5718</td>
<td>4-chlorophenyl</td><td>phenyl</td><td>GH<sub>3</sub> q22 1.5926</td>
<td>4-bromophenyl</td><td>phenyl</td><td>CH ^ »22! .5076</td>
<td>4-phenylphenol</td><td>phenyl</td><td>CH ^ n ^<sup>1</sup> 1.6328</td>
<td>4-tert-butylphenyl</td><td>phenyl</td><td>CH,</td>
<td>4-thiomethylphenyl</td><td>phenylcone</td><td></td>
<td>4-phenoxyphenyl</td><td>phenyl</td><td>ch<sub>3</sub></td>
<td>4-trifluoromethoxyphenyl</td><td>phenyl</td><td> %</td>
<td>4-methylsulfonylphenol</td><td>phenyl</td><td><sup>CH</sup>3</td>
<td>4-cyclohexylphenyl</td><td>phenyl</td><td>CH,</td>
<td>4- (4-fluorophenyl) phenyl</td><td>phenyl</td><td><sup>GH</sup>3</td>
<td>3-trifluoromethylphenyl</td><td>phenyl</td><td>ch<sub>5</sub></td>
<td>2-chlorophenyl</td><td>phenyl</td><td>CH, m.p. 1.5742</td>
<td>2-methoxyphenyl</td><td>phenyl</td><td></td>
<td>2,4-dichlorophenyl</td><td>phenyl</td><td>CH ^ nJ<sup>5</sup> 1.5941</td>
<td>2-chloro-4-phenyl ylophen yl</td><td>phenyl</td><td><sup>GH</sup>3</td>
<td>2-fluoro-4-phen ylphenol</td><td>phenyl</td><td>CH, / -x</td>
<td>3,5-dichlorophenyl</td><td>phenyl</td><td>* 5 / I</td>
<td>2,5-dimethoxyphenyl</td><td>phenyl</td><td><sup>CH</sup>3 / x, '·</td>
<td>2,6-dimethoxyphenyl</td><td>phenyl</td><td>CH, / - ..cP?: 3/91</td>
<td colspan="2">4-bromophenyl 4-bromophenyl yl</td><td>CH<sub>3</sub> / 15I1.6H5</td>
-48 TABLE VI (continued)
<td>i!</td><td> ®2</td><td></td><td></td>
<td>4-phenylphenyl</td><td>4-phenylphenyl</td><td>CH, m.p. ? 91</td><td> 42-46°</td>
<td>4-methoxyphenyl</td><td>4-methoxyphenyl</td><td>CH<sub>5</sub> ng<sup>1</sup></td><td> 1.5890</td>
<td>3-trifluoromethylphenyl</td><td>3-trifluoromethylphen-</td><td>• CH,</td><td></td>
<td></td><td>nylon</td><td> 9</td><td></td>
<td>2-chlorophenyl</td><td>2-chlorophenyl</td><td> ®3 4' ’</td><td> .5965</td>
<td>2-methoxyphenyl</td><td>2-methoxyphenyl</td><td>CH</td><td></td>
<td>2,4-dichlorophenyl</td><td>2,4-dichlorophenyl</td><td>CH- ng<sup>2</sup> 1</td><td> .6009</td>
<td>3 ”, 5-dichlorophenyl</td><td>3 "5-dichlorophenyl</td><td>ch.</td><td></td>
<td>2-chlorophenyl</td><td>4-chlorophenyl</td><td>2 20 CH<sub>3</sub> n £ ° 1</td><td> .5918</td>
<td>2-chlorophenyl</td><td>4-fluorophene yl</td><td>ch<sub>3</sub></td><td></td>
<td>4-phenylphenyl</td><td>4-chlorophenyl</td><td>ch<sub>3</sub></td><td></td>
<td>4-phenylphenyl</td><td>4-fluorophenyl yl</td><td>CH<sub>3</sub></td><td></td>
<td>4-phenylphenyl</td><td>2,4-dichlorophenyl</td><td>ch<sub>3</sub></td><td></td>
<td>4-fluorophenyl</td><td>2,4-dichlorophenyl</td><td></td><td></td>
<td>4-chlorophenyl</td><td>2,4-dichlorophenyl</td><td>CH,</td><td></td>
<td>1-naphthylone</td><td>2,6-dimethoxyphenyl</td><td>ch<sub>3</sub></td><td></td>
<td>4-phenoxyphenyl</td><td>3,4-dichlorophenyl yl</td><td>CH<sub>3</sub></td><td></td>
<td> °2<sup>THE</sup>5</td><td><sup>G</sup>2<sup>H</sup>5</td><td>c<sub>2</sub>H<sub>5</sub></td><td></td>
<td> £22^5¾</td><td></td><td>Equal- Xx</td><td></td>
<td></td><td> £-=4<sup>THE</sup>9</td><td> ?<sup>G</sup>4<sup>H</sup>9</td><td></td>
<td> 2“<sup>G</sup>8<sup>H</sup>17</td><td>L.</td><td colspan="2">cyclopentylion</td>
<td>£ r ° i4<sup>H</sup>29</td><td>cyclopropyl</td><td colspan="2">1-methylbutyl</td>
<td> -^18^37</td><td> 2-<sup>p</sup>6<sup>X</sup>13</td><td> 2-<sup>C</sup>6<sup>h</sup>,<sub>3</sub></td><td></td>
<td>cyclopropyl</td><td></td><td>Ϊ '° 4<sup>THE</sup>9</td><td></td>
<td>cyclohexyl</td><td>nC, H „ - 5 /</td><td>n-CjH?</td><td></td>
<td>1-naphthylone</td><td> £-°4<sup>THE</sup>9</td><td> 2-°4<sup>H</sup>9</td><td></td>
<td>2-naphthylone</td><td> £-°4<sup>THE</sup>9</td><td colspan="2">cyclobutanol</td>
<td>phenyl</td><td>cyclopropyl</td><td> £-°6<sup>H</sup>13</td><td></td>
<td>4-phenylphenyl</td><td>g<sub>2</sub>h<sub>5</sub></td><td> °2<sup>H</sup>5</td><td></td>
<td>4-phenylphenyl</td><td> 2-<sup>G</sup>4<sup>H</sup>9</td><td> £-<sup>C</sup>4<sup>H</sup>9</td><td></td>
<td>4-phenylphenol</td><td> £-<sup>G</sup>6<sup>H</sup>13</td><td> 2-°6<sup>H</sup>13</td><td></td>
<td>4-phenylphenyl</td><td>cyclohexyl</td><td colspan="2">cyclohexyl</td>
<td>4-chlorophenyl</td><td>S- ° 4<sup>H</sup>9</td><td> 2-°4<sup>H</sup>9</td><td></td>
<td>4-fluorophenylene</td><td>£ - ° L.</td><td>nG ^</td><td></td>
<td>4-phenoxyphenyl</td><td>S- ° 4<sup>H</sup>9</td><td>cyclohexyl /</td><td>> V -i- .V '·</td>
<td>4- (4-chlorophenoxy) phenyl</td><td> 2-°4<sup>THE</sup>9</td><td> 2-<sup>C</sup>4<sup>H</sup>9 /</td><td></td>
-49 TABLE VI (continued)
4-tert-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 g<sub>2</sub>h<sub>5</sub> cyclohexyl
X-<sup>p</sup>4<sup>THE</sup>9 nG<sub>12</sub>THE<sub>25</sub>
1-naphthyl cyclopropyl<sup>G</sup>4<sup>H</sup>9 £ ££ Σ · ·<sup>p</sup>4<sup>THE</sup>9 n-σ ^
2½
Gr<sub>4</sub><sup>THE</sup>9 °2<sup>THE</sup>5
S-<sup>C</sup>4<sup>H</sup>9 i £ 2 ”<sup>G</sup>5<sup>H</sup>7 cyclohexyl + - ° 4<sup>THE</sup>9 tm-σ4<sup>THE</sup>cyclopentylion £ -<sup>p</sup>4<sup>THE</sup>9
X.<sup>THE</sup>9 phenyl phenyl phenyl
4-chlorophenyl
4-chlorophenyl
4-fluorophenyl phenyl phenyl phenyl phenyl i
Soc<sub>4</sub><sup>THE</sup>9
O ££ OL<sup>a</sup>4<sup>THE</sup>9
5<sup>-G</sup>4<sup>H</sup>9
3- methylbutyl cyclohexyl;<sup>p</sup>4<sup>THE</sup>9 t-C2H6 cyclopentylion
5-°4<sup>THE</sup>9 iso-G, H.<sub>a </sub>phenyl phenyl <sup>1</sup> phenyl
4-chlorophenyl 4-chlorophenyl 4-fluorophenyl 4-tert-butylphenyl 4-phenylphenyl
2,4-dichlorophenyl 3-trifluoromethylphenyl
<td>iso-G.H.<sub>the </sub>--- 4 9</td><td>phenyl</td><td colspan="2">3,5-dichlorophenyl</td>
<td>cyclopentylion</td><td>phenyl</td><td colspan="2">2,6-dimethoxyphenyl</td>
<td> £~<sup>G</sup>14<sup>H</sup>29</td><td>4-chlorophenyl</td><td>2-fluorophenyl</td><td></td>
<td> £“°4<sup>THE</sup>9</td><td>4-fluorophenyl</td><td>4-phenylphenyl</td><td></td>
<td>phenyl</td><td>phenyl</td><td colspan="2">phenyl mp.118-121 °</td>
<td>4-chlorophenyl</td><td>4-chlorophenyl</td><td>4-chlorophenyl</td><td></td>
<td>4-fluorophenylcone</td><td>4-fluorophenyl</td><td>4-fluorophenyl</td><td></td>
<td>4-phenylphenyl</td><td>4-phenylphenyl</td><td>4-phenylphenyl</td><td></td>
<td>2,4-dichlorophenyl</td><td>2,4-dichlorophenyl</td><td colspan="2">2,4-dichlorophenyl</td>
<td>phenyl</td><td>4-fluorophenylene</td><td>4-fluorophenyl</td><td></td>
<td>phenyl</td><td>4-chlorophenyl yl</td><td>4-chlorophenyl</td><td></td>
<td>phenyl</td><td>4-phenylphenyl</td><td>4-phenylphenyl</td><td></td>
<td>phenyl</td><td>2,4-dichlorophenyl</td><td colspan="2">2,4-dichlorophenyl</td>
<td>2-naphthylone</td><td>4-methylthiophenyl</td><td>4-methylthiophenol</td><td></td>
<td>4-chlorophenyl</td><td>2-methoxyphenyl</td><td>2-methoxyphenyl</td><td></td>
<td>4-chlorophenyl</td><td>3-chlorophenyl methyl</td><td>3-chlorophyll n.v.</td><td> /</td>
<td>phenyl</td><td>2-chlorophenyl</td><td>4-fluorophen / Han</td><td></td>
-L
<td> -1-</td><td>TABLE VI (continued)</td><td>h</td>
<td>phenyl</td><td>4-chlorophenyl</td><td>4-phenylphenyl</td>
<td>1-naphthylone</td><td>4-bromophenyl</td><td>3-methylphenyl</td>
<td>4-phenoxyphenyl</td><td>3,5-dimethoxyphenyl</td><td>3,4-dichlorophenyl</td>
<td>Example_26</td><td></td><td></td>
Preparation of (3,5-Dimethyl-1H-1 <sub>></sub>2<sub>></sub>4-tert-benzol-or-ylmethyl) - / ~ bis- (4-fluorophenyl) 7-ethylsilane * The title compound is prepared by applying the procedure of Example 25 with an equimolar amount of 4-methylphenyl ) 7methylsilane and 3,5-dimethyl-1,2,4-triazole and sodium salt. i
By substituting the salt of 3,5-dimethyl triazole with 3-methyl-, 2,4-triazole salts, related compounds can be prepared.
Example 27
Preparation of (1, 1) <sup>G.</sup>-Diphenyl-4-yl) dimethyl (3-methyl-1H-1L, 2<sub>L.</sub>4-triazolylmethyl) silane
5.9 g solution. (0.020 mol) (ΐ, 1'-diphenyl-4-yl) dimethyl (1H-1, 2,4-triazol-1-ylmethyl) silane in 40 ml dry tetrahydrofuran, cooled to -40 ° C under nitrogen and eluted, while 12.5 ml (0.020 mol) of 1.6 mM n-butyl lithium solution of hexane was added dropwise. The yellow solution was stirred for 15 minutes at -40 ° C, treated with 1.9 g. (4.2 ppm, 0.030 mol) of methyl iodide and allowed to warm to room temperature. The solution was diluted with water and extracted with hexane. Washing of Organic Extracts-
<img file="GR76497B_D0053.tif" />
and brine, drying over magnesium sulfate and submitting six (s) • <sup>9</sup> i <sup>;</sup> They gave 5.7 gm. solid, which was purified by tomography<sup>9</sup> r *. · Pillar column on silica gel (elution with ethyl acetate / zaptoicides)
-511.1 g of primary product. Recrystallize from 12 ml. (mixture) of hexanes: 3: 1 ethyl acetate, afforded 0.97 g (16%) of the title compound as an off-white solid: mp 95-98 ° C * IR spectrum (NUJ0L<sup>R</sup>): 1590, 1270, 1250, 1180, 1120, 830, 765, 700 cm.<sup>-1</sup> KMR mass (CDCl)) 0.5 (6H, S), 2.2 (3H, S), 3.7 (2H, S), 7.2-7.7 (9H, m), 7.8 (1H, S).
Although said structure is preferred for stereochemical reasons, the position of the methyl group on the triazole ring has not been demonstrated and it is possible that the product is (ΐ, 1'-biphy; nyl-4-yl) -dimethyl (5-yl) -dimethyl-5-yl-dimethyl). -1X-1,2,4-triazol-1-ylmethyl) silane.
The procedures of Examples 26 and 27 may be used to prepare the compounds of Table II.
I.
TABLE VII. i
R, r
R.-S: -CH<sub>O</sub>H. I.<sup>1 1 2</sup> n ° 2<sup>B.</sup>5 C1 - =, 8 ^ 7 cyclohexyl
1- naphthyl phenyl phenyl
4-phenylphenyl 4- (4-fluorophenyl) phenyl 0 '4-phenoxyphenyl
3-trifluoromethylphenyl
2-methoxyphenyl
2.4- dichlorophenyl 2-chloro-4-phenylphenyl phenyl
4-phenylphenyl
2.4-dichlorophenyl '3
Q,
<td></td><td> *3</td><td> 5.</td><td> «2</td>
<td>CR-</td><td>A</td><td>CH, 3</td><td>A.</td>
<td> ®%</td><td>CH, 3</td><td>H</td><td> 01%</td>
<td>CH, 3</td><td>CI%</td><td>CH, 3</td><td>OH,</td>
<td>OE%</td><td>C5</td><td>CH, 3</td><td>CH, 3</td>
<td> 01%</td><td>A.</td><td>H</td><td> 01%</td>
<td>CH, 3</td><td>Ohj</td><td>CH, 3</td><td>H</td>
<td>CH, 3</td><td>CH, 3</td><td>C5%</td><td>ch<sub>3</sub></td>
<td> 0^</td><td>CH, 3</td><td> ®3</td><td>0H<sub>3</sub></td>
<td>GHj</td><td> <2%</td><td> ®3</td><td>CH, 3</td>
<td> ™3</td><td> ®3</td><td> ®3</td><td>CI%</td>
<td>CH, 3</td><td>CI%</td><td>OH, 3</td><td>CH, 3</td>
<td>CH, 3</td><td>What%</td><td>ch<sub>5</sub></td><td rowspan="2">A.</td>
<td>CH, 3</td><td>CH,</td><td>ch<sub>3</sub></td>
<td>£ · ° L £ - ° 4<sup>H</sup>9</td><td>CH, A.</td><td>h /</td><td></td>
<td> 2-°6<sup>H</sup>13</td><td> %</td><td></td><td>~ \ oiL</td>
-52PITAX _VII (continued)
<td></td><td>h</td><td colspan="2">V.</td><td>h T</td>
<td colspan="2">4- (4-chlorophenoxy) phenyl cyclohexyl</td><td>CH<sub>3</sub></td><td>CH,</td><td>CH<sub>3</sub></td>
<td>phenyl</td><td>phenyl</td><td>CH, j</td><td>THE</td><td>CH<sub>3</sub></td>
<td>4-fluorophenylene</td><td>phenyl</td><td> 0¾</td><td>CH 3</td><td>CH<sub>3</sub></td>
<td>4-fluorophenyl</td><td>phenyl</td><td>CH,</td><td>THE</td><td>CH, 3</td>
<td>4-chlorophenol</td><td>phenyl</td><td>CH, 3</td><td>THE</td><td>ch<sub>3</sub></td>
<td>4-fluorophenol</td><td>4-fluorophenyl</td><td>CH,</td><td>THE</td><td>WHICH</td>
<td>4-fluorophenol</td><td>4-fluorophenol</td><td>CH, 3</td><td></td><td>H .</td>
<td>4-chlorophenol</td><td>4-chlorophenol</td><td>ch<sub>5</sub></td><td>THE</td><td> ^3</td>
<td>4-chlorophenyl</td><td>4-chlorophenol</td><td>CHj</td><td>gh<sub>3</sub></td><td> %</td>
<td>2-chlorophenyl methyl</td><td>4-chlorophenyl</td><td>CH,</td><td>THE</td><td>ch<sub>3</sub></td>
<td>2,4-dichlorophenol</td><td>2,4-dichlorophenol</td><td>CH,</td><td>CH,</td><td> ^3</td>
<td> 2“°1 ^37</td><td> 2“<sup>C</sup>6<sup>H</sup>1 <sub>5</sub></td><td> £-=6=13</td><td>sk ^</td><td>CH, 3</td>
<td>1-naphthylone</td><td> 2-<sup>C</sup>4<sup>H</sup>9</td><td> 2-=4=9</td><td>THE</td><td>CH, 3</td>
<td>phenyl</td><td>phenyl</td><td>phenyl</td><td>THE</td><td> ?<sup>H</sup>3</td>
<td>phenyl</td><td>phenyl</td><td>phenyl</td><td></td><td>H</td>
<td>phenyl</td><td>phenyl</td><td>phenyl</td><td>CH<sub>3</sub></td><td>ch<sub>3</sub></td>
Example 28
Preparation of the compound of compound (1<sub>r</sub>1'-Diphenyl yl-4-yl) dimethyl (1H)<sub>±</sub>1 , 2, 4-triazol-1-yl} methyl) silyl and * 1: 1 copper hypochlorite
A mixture of 5.0 g. (0.017 mol) (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane and 1.7 g (0.017 g - - / mol) of copper chloride hypochlorite in 170 ml of STH were heated to reflux at Ng for 30 minutes, and stirred in deep green.
solution was evaporated, leaving a head / unit residue as a dark greenish-brown solid: m.p. 85-90 ° C.
IR spectrum (NUJ0L<sup>R</sup>): 3110, 1590,1280, 1250, 1120, 1010,990,840,825,760,
700 from.<sup>1</sup>.
f<sup>a</sup> / I '. '' '' '' ''
The following metal complexes were prepared of the following (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazM-4-ylmethyl) cis-metal complexes. / 'T. ·'? ·? /?
lanyard: / / 1 \
-531: 1 Copper Chloride Complex: m.p. 83-87 ° C 2: 1 Complex with copper chloride: m.p. 85-92 ° C
1: 1 Complex with zinc chloride: eth 1.5737
1: 1 Complex with manganese sulfate: m.p. 244-250 (with dec.). Example 29
Preparation of To-S-Dodecyl Enzenesulfonate Salt (1, 1<sup>G.</sup>- Double ->
nyl-phenyl) dimethyl (1H-1,2,4-tetrazol-1-ylmethyl2-silane)
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 was then combined of a solution of 1.1 g. (0.0034 mol) 4-D-decylbenzenesulfonic acid with 10 ml of dichloromethane. The solution was evaporated, remaining in a titrated salt (31 ° C to 45 ° C). 3050, 3020, 2960,2920, 2850,2570,1920,1600,1545, 1485,1455,1405,1250,1225, 11 65,1120, Ϊ030,1010,990,845,825,755; 735, 700,670,635 cm. "<sup>1</sup>.
<img file="GR76497B_D0054.tif" />
1_,2<sub>L.</sub>4-Triazol-1-ylmethyl) silane and 2: 1 copper chloride
A mixture of 1.0 g (0.032 mol) / 'bis (4-fluorophenyl) 7methyl (1H-1,2,4-triazol-1-ylmethyl) silane and 0.2 g. (0.0016 lines-
<img file="GR76497B_D0055.tif" />
• n. *
X. "h
-54For applying the procedures of Examples 26-28, any of the compounds of Tables VI, VII, VIII, IX, XII and XIH may be converted to metal complexes.
Example_31_
Preparation of (1 (methoxy) methylsilane
Mixture (1.1<sup>g</sup>-diphenyl-4-yl) chloro-chloromethyl-methylsilane and two equivalents of 1,2,4-triazole sodium salt in dimethylformamide, heated at 8 ° -9 ° C for 2 hours. C for 1 hour, cooled, diluted with water and extracted rapidly with ether. Rinse of ethereal solution with water and brine, dry with magnesium sulfate and evaporate, provide (as a residue) a residue.
<img file="GR76497B_D0056.tif" />
by using the appropriate chlorosilane and alcohol *
<img file="GR76497B_D0057.tif" />
at 20-25 ° C instead of 70 ° C.
Example 32
Preparation of ^ (1, 1-Dimethylethoxy) methyl (phenyl) (1H-1,2,4-triazol1)<sub>></sub>2) silane<sup>i</sup>u
3.6 g mixture. (0.015 mol) chloromethyl (1,1-dimethylethoxy) methyl (phenyl) silane and 1.3 g. (0.015 mol) sodium salt of 1,2,4-triazole in 8 mL of dimethylformamide, stirred at 80 ° C for 2 hours, cooled and poured into water. water
<img file="GR76497B_D0058.tif" />
-55 ($ 36) of a compound title as a pale yellow oil; 1115,1050,1020,1010,830,810,790,740, 700,680 cm.<sup>1</sup>. NMR spectrum (CDCl2): 0.6 (3H, S), 1.3 (9H, S), 3.9 (2H, S), 7.3-7.7 (5H, m), 7.9 (1H, S) and 8, 0 (12, S). ,
The compounds of Table VIII and IX which can be prepared using the procedures of Examples 31 and 32.
TABLE_VIII
R «
I.
R ^ Si-GHgN
OR.
N = 2¾
1 ° C-4 °<sup>THE</sup>9
2-°4<sup>THE</sup>9 £-°12<sup>THE</sup>25 C 1 - 37 3 cyclopropyl cyclohexyl
1- naphthylone
2- naphthol phenyl phenyl phenyl phenyl phenyl phenyl
4-phenylphenyl 4-phenylphenyl 4-phenylphenyl 4-phenylphenyl 4-chlorophenyl 4-chlorophenyl, 4-chlorophenyl 4-fluorophenyl h
<sup>0E</sup>3
CH, ®3 <sup>C</sup>2<sup>H</sup>5 £<sup>p</sup>6<sup>THE</sup>13 GH,
OH, iso-G ^H ^ cyclobutyl ch<sub>3</sub>
Oh, <sup>0H</sup>3
CH, tt.-p<sub>4</sub><sup>THE</sup>θ £ - ° 4<sup>THE</sup>9
W £ · - °<sub>4</sub><sup>THE</sup>9
GH<sub>3</sub>
GH<sub>3</sub> £-°4<sup>E.</sup>9 oob<sub>3</sub> £-<sup>a</sup>6<sup>THE</sup>,<sub>3</sub>
£ 11 · - = 4<sup>THE</sup>9 °2<sup>the</sup>5
Oh,
CH,
5-°4<sup>THE</sup>9
CH<sub>5</sub>
£ 2<sup>p</sup>3<sup>THE</sup>7 nG ^
THE
OH, = 2 g iso-O ^ H 1 H
CH,
O.<sub>2</sub>the<sub>5</sub> „20 <sup>n</sup>D
- A1.5367
<img file="GR76497B_D0059.tif" />
-56Ip IP
4-Fluorophenyl 4-phenoxyphenyl 4-tert-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
-°12<sup>X</sup>25 “°18^37
1- naphthylphenyl
4- fluorophenyl
4-chlorophenyl 4-phenylphenyl <sub>j</sub>4-phenylphenyl
4-tert-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
3-trifluoromethylphenyl 2-methoxyphenyl
2-chlorophenyl
<img file="GR76497B_D0060.tif" />
-571
3-Trifluoromethylphenyl 2-fluoro-4-chlorophenyl
2.3-dimethylphenyl
2,6-dimethoxyphenyl
3.4-Dichlorophenyl
PICTURE_WEB (continued)
D.
4-tert-butylphenylion
4-bromophenyl 4-methylthiophenyl 4-methoxyphenyl 4-methylphenyl
D.
H-4<sup>THE</sup>9
2222g;
Equal-C H.<sub>the </sub>----4 9
O IX
JIHAS
<td>X</td><td>R.-St- <1 1<sup>0R</sup>6</td><td>A,</td><td><sup>Q</sup>2 <sup>1</sup></td><td></td><td></td>
<td> *1</td><td><sup>R</sup>2</td><td></td><td><sup>R</sup>6</td><td><sup>Q</sup>1</td><td></td>
<td></td><td></td><td></td><td> ····</td><td></td><td></td>
<td>c<sub>2</sub>h<sub>5</sub></td><td>CH, 3</td><td></td><td>CH ^</td><td>CH<sub>5</sub></td><td>A.</td>
<td>cyclohexyl</td><td>CH ^</td><td></td><td>iso-C ^ Hg</td><td>THE</td><td>CH<sub>3</sub></td>
<td> £**<sup>p</sup>i</td><td> 2-°6<sup>h</sup>1<sub>3</sub></td><td></td><td>t-C ^ Hg</td><td>C ^</td><td>ch4 3</td>
<td>1-naphthylone</td><td>OH,</td><td></td><td> 2222^¾</td><td>OH,</td><td>CH * 3</td>
<td>phenyl</td><td>CH, 5</td><td></td><td>tm-C ^</td><td>H</td><td><sup>gh</sup>3</td>
<td>phenyl</td><td>OH,</td><td></td><td> 2222-<sup>G</sup>4<sup>H</sup>9</td><td><A.</td><td>H</td>
<td>phenyl</td><td>CH, 3</td><td></td><td>C £ 2Xl- ° 4<sup>THE</sup>9</td><td>CH, 3</td><td>CH * 3</td>
<td>phenyl</td><td>CH ^</td><td></td><td>SC.H<sub>q </sub>- 4 9</td><td>H</td><td>- a</td>
<td>phenyl</td><td>CH ^</td><td></td><td>iso-O ^ H- 4 y</td><td>H</td><td>A.</td>
<td>4-phenylphenyl</td><td> 2-°4<sup>H</sup>9</td><td></td><td> 2£22<sup>, -G</sup>4<sup>H</sup>9</td><td>H</td><td>OH,</td>
<td>4-phenylphenyl</td><td>CH ^</td><td></td><td>2 £ 22j. "<sup>g</sup>4<sup>H</sup>9</td><td>X</td><td>A.</td>
<td>4-phenylphenyl</td><td>C ^</td><td></td><td>t-C ^ Hg</td><td>A.</td><td>CH ^</td>
<td>4-chlorophenyl</td><td>CH</td><td></td><td>£ £ 2λ ° ° 4<sup>THE</sup>9</td><td>H</td><td>A.</td>
<td>4-chlorophenyl methyl</td><td>OH,</td><td></td><td> 2£22-<sup>g</sup>4<sup>H</sup>9</td><td>OH,</td><td>CH<sub>3</sub></td>
<td>4-fluorophenyl</td><td>CH, 3</td><td></td><td> 2222±-<sup>g</sup>4<sup>H</sup>9</td><td>H</td><td>A.</td>
<td>4-fluorophenyl</td><td>OH,</td><td></td><td>2 £ 22x-<sup>G</sup>4<sup>H</sup>9</td><td>OH,</td><td>ch<sub>3</sub></td>
<td>phenyl</td><td>phenyl</td><td></td><td>C ^</td><td>CH ^</td><td>A.</td>
<td>phenyl</td><td>phenyl</td><td></td><td> 2-<sup>G</sup>3<sup>H</sup>7</td><td>ch<sub>3</sub></td><td>Ohi</td>
<td>4-fluorophenyl</td><td>phenyl</td><td></td><td>is-O ^ H;</td><td>H</td><td>CH *</td>
<td>4-fluorophenyl</td><td>phenyl</td><td></td><td> 2222--¾^</td><td>CH</td><td>oh '</td>
<td>4-chlorophenyl</td><td>phenyl</td><td></td><td>equal</td><td>H</td><td>A.</td>
THE
4-fluorophenyl 4-fluorophenyl 4-fluorophenyl
2-methoxyphenyl
3-methylphenyl
C £ E-<sup>The</sup>4<sup>THE</sup>9
C £ 22 ° -4 °<sup>THE</sup>9
I2 · · -<sup>p</sup>4<sup>X</sup>9
<img file="GR76497B_D0061.tif" />
OH / Ca2 +;
4-fluorophenyl 4-fluorophenyl 4-fluorophenyl 2® methoxyphenyl 3-methylphenyl c<sub>2</sub>h<sub>5</sub> iso-C.H.<sub>the </sub>--4 9
-58Example_33
Preparation of phenylalanine chloromethyl (dichloro)
Solution 25.1 ml. (36.8 g, 0,200 mol) chloromethyltrichlorosilane in 400 ml of tetrahydrofuran in 400 ml. tetrahydrofuran, cooled to -78 ° C under nitrogen and stirred vigorously, while slowly instilled, over an hour, 48.0
I mm. (0,100mol) 2.1 Molecular Phenyl Lithium Solution.
After stirring for 30 minutes at -78 ° C, the virus solution was allowed to incubate at room temperature.
to warm to room temperature and evaporated to about 200 ml. Addition of 500 ml of ether, filtration to remove precipitated lithium chloride and evaporation of the filtrate, providing 25.0 g. g.62-82 ° C (0.15 mm); NMR (CDCl2) δ: 3.3 (S,
2) and 7.1-7.9 (m, 5).
Example 34
Preparation of Chloromethyl (diethoxy) <ylenylsilane
1.0 g solution. (0.0044 mol) chloromethyl (dichloro) phenylsilane in 8 ml of absolute ethanol, cooled to 0 ° C under nitrogen and stirred, while 0.61 ml (0.445 g, 0.44 mmol) was slowly added. Leave to warm to room temperature. Add 50 ml of ether, filtration to remove precipitated triethylamine chloride and filter the filtrate; They afforded a residue which was filtered through a short column of silica gel (95% petroleum ether: ethyl acetate as eluent) to give 0.80 g. (73%) of the title compound as colorless
HMR (CDClC) spectrum: 1.25 (-t, 6, J = 6Hx), 3.0 (S, 2), 3.6H2) and 72-7.9 (m, 5).
<img file="GR76497B_D0062.tif" />
-595 '£ ^ exp | Aca_35
Preparation of Chlorobutyl (phenyl) bis (2-propoxy) silane
2.0 g solution. (0.009 mol) of chloromethyl (dichloro) phenylsilane and 5 ml of 2-propanol in 15 ml of dimethylformamide was stirred at Ng while 2.5 ml (1.9 g of 0.018 mol) was added dropwise. The resulting slurry was heated to 80 ° C for 2 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 a residue of 2.2 g. liquid. Silica gel column chromatography eluting with petroleum ether provided 1.4 g (58%) of the title compound as a colorless liquid: 1.4741; NMR (CDCl2): 1.2 (12H, c, J = 6 ), 3.0 (2H, S), 4.3 (2H, permissible, J = 6), 7.3-7.8 (5H, m)
The compounds of Tables X and XI may be prepared using the procedures of Examples 33-35.
<td rowspan="2"></td><td colspan="3">FIX</td>
<td>ORg r.4: -ch<sub>o</sub>ci x</td><td colspan="2"></td>
<td>The<sub>2</sub>the<sub>5</sub></td><td></td><td>tf-0<sub>4</sub>THE<sub>i</sub></td><td></td>
<td> -<sup>THE</sup>L.</td><td></td><td> °2<sup>THE</sup>5</td><td></td>
<td> £-°13<sup>THE</sup>37</td><td></td><td>oh<sub>3</sub></td><td></td>
<td>cyclohexyl</td><td></td><td>n-0 ^ 7</td><td></td>
<td>1-naphthylone I.</td><td></td><td>is-0 H</td><td></td>
<td>phenyl</td><td></td><td>oh<sub>5</sub></td><td></td>
<td>phenyl</td><td></td><td>n-C_H „ - 5 l</td><td></td>
<td>phenyl</td><td></td><td>£ £ · -<sup>p</sup>4<sup>THE</sup>9</td><td></td>
<td>4-phenylphenyl</td><td></td><td><sup>C</sup>2<sup>H</sup>5</td><td></td>
<td>4-phenylphenyl</td><td></td><td> -<sup>n</sup>-°4<sup>H</sup>9 z:</td><td> -1 - · -</td>
<td>4-fluorophenyl</td><td></td><td><sup>ch</sup>3 f '</td><td></td>
<td>4-fluorophenyl</td><td></td><td>c<sub>2</sub>h<sub>5</sub></td><td></td>
<td>4-chlorophenyl</td><td></td><td>c<sub>2</sub>h<sub>5</sub> /</td><td> •</td>
<td>4-chlorophenyl</td><td></td><td></td><td></td>
-60PMX (continued) «1
3-Trifluoromethylphenyl 2-methoxyphenyl
2.3-dimethylphenyl
2.4-dichlorophenyl
2.4-dichlorophenyl 2-methoxy-5-fluorophenyl
2,6-dimethoxyphenyl
3.4-Dichlorophenyl
3.5-dichlorophenyl
R,
S-<sup>G</sup>4<sup>H</sup>9 L 2-4 °<sup>THE</sup>9 oh<sub>5</sub><sup>p</sup>2<sup>THE</sup>5 is-0<sub>5</sub>THE<sub>?</sub> %
<sup>C</sup>2<sup>S</sup>5 £-°4<sup>THE</sup>9
TABLE XI
Ah <sub>X.</sub>0 ^ -Sf-C ^ Cl
R, o<sub>2</sub>the<sub>5</sub> £-<sup>C</sup>4<sup>H</sup>9 C1-37 ^ cyclohexyl
1-naphthyl phenyl
Uv phenyl phenyl <sup>g</sup>·<sup>;</sup> ·. L / .'_ '' phenyl
4-phenylphenyl
4-phenylphenol
4-phenylphenyl 4-fluorophenyl
-CH CH on<sub>5</sub> • -Ox<sub>2</sub>OH-0H<sub>2</sub>GH<sub>2</sub>CH<sub>2</sub>?2<sup>THE</sup>5
-GH<sub>2</sub>GH-CH<sub>2</sub>0H<sub>2</sub>-CH<sub>2</sub>CH<sub>2</sub>c<sub>2</sub>h<sub>5</sub>
-CHgCEn — O ^ Hg
-CHgGH-CHgCH.g (ch<sub>3</sub>)<sub>2</sub>c (ch)<sub>2</sub>bp 142-146 '
<img file="GR76497B_D0063.tif" />
TABLE XI (continued)
4-fluorophenyl
4-chlorophenyl
4-chlorophenyl
3-trifluoromethylphenyl
2-methoxyphenyl
2.3-dimethylphenyl
2.4-dichlorophenyl
2.4-dichlorophenyl
2-methoxy-5-fluorophenyl 2,6-dimethoxyphenyl
3.4-Dichlorophenyl
3.5 - dichloromethane ° 2 °<sup>THE <</sup>5
2<sup>> _O</sup>1 e; 37 phenyl phenyl phenyl phenyl
4-phenylphenyl
4-phenylphenyl 4-fluorophenyl 4-chlorophenyl
4-phenoxyphenyl
3-trifluoromethylphenyl <sup>R</sup>6 —-CH, i 3
-GH CH? 2<sup>H</sup>5
-CHgCH-CiCH ^ JgCiCH ^ gCH<sub>5</sub>
-chch<sub>2</sub>c (ch<sub>3</sub>)<sub>2</sub> nC ^ Hg
-ch<sub>2</sub>ch-ch<sub>2</sub>ch<sub>2</sub>?2<sup>H</sup>5
-CH<sub>2</sub>CHn-C, H - i3 i
-CHgCHCH, CH, »3 i3
-CHCiCH ^ gCH-ch<sub>2</sub>ch<sub>2</sub>on,
CH,
-chch<sub>2</sub>ch?<sup>h</sup>3 0 i ·
-CH — CH-GH<sub>2</sub>CH = CHCH<sub>2</sub>CH, CH, <5 4 3
-CHCH<sub>2</sub>CH<sub>2</sub>CH-CH<sub>2</sub>CH = GHCH<sub>2</sub>-C (CH<sub>3</sub>)<sub>2</sub>CfH = CHC (CH ^)<sub>2</sub>^ i ft ft <sub>o</sub> i
-CHCH-CELCH- bp 57-60 ° (0.15, <sup>d</sup> * mm)
-C (ch<sub>3</sub>)<sub>2</sub>ch<sub>2</sub>ch<sub>2</sub>c (ch<sub>3</sub>)<sub>2</sub>-CH<sub>2</sub>CH = CHCH<sub>2</sub>-CHgC: -CHg-CHsCHCHg-CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>£-?<sub>4</sub>H<sub>9 </sub>-CH „CH, CH<sub>0</sub>CHCH | <sup>z</sup> cS<sub>3 </sub>-0HCH = CH0Hft
<img file="GR76497B_D0064.tif" />
-62Table XI (continued)
2-methoxyphenyl "6" OS, CH "3,3
-CH<sub>2</sub>CH — CHCHg
Example 56
Preparation of 50% ethylbis (2-propoxy) (1H-1,2,4-triazol-1-ylmethyl) silane - - - - - | * The title compound can be prepared by applying the procedure of Example 32 in the form of chloromethyl (phenyl) bis (2-propoxy) silanes:<sup>2</sup> 1.4962 * NMR spectrum (CDGl2): 1.1 (l2H ^ d, J = 6):
4.0 (2H, S); 4.3 (2H, test, or J = 6); 7.2-8.0 (7H, m);
The compounds of Tables XII and XIII can be avoided. '.
> <sup>n</sup> g <sup>1</sup> in the same way. j
TABLE XII
R, -SI-CH<sub>O</sub>N, <sup>1</sup> » <sup>2</sup>
0R<sub>r</sub> i! <sup>G</sup>2<sup>H</sup>5
2”<sup>G</sup>4®9
-“<sup>G</sup>18<sup>H</sup>37 cyclohexyl
1-naphthyl phenol phenol phenol phenol phenol
4-phenylphenyl 4-phenylphenol 4-fluorophenol 4-fluorophenyl 4-chlorophenyl 4-chlorophenol 3-trifluoromethylphenyl
R,
£ 2 £ · -<sup>p</sup>4<sup>X</sup>9 °2<sup>THE</sup>5
0H<sub>3</sub> n-0 ^ £ 22-<sup>p</sup>4<sup>THE</sup>9 <sup>0H</sup>3 n-O ^ H ^ ^ σο-C Ο Hγ
4 ° C-4<sup>X</sup>9 °2<sup>THE</sup>5
X-<sup>p</sup>4<sup>THE</sup>9 <3H_ ° 2<sup>THE</sup>5 iso-C ^γH? ° 4<sup>THE</sup>9
<img file="GR76497B_D0065.tif" />
-63 TABLE XII (continued)
<td> .1</td><td><sup>R</sup>6</td><td>2l</td><td> -<sup>2</sup> I.</td>
<td>2-methoxyphenyl</td><td>n-σ ^</td><td>X</td><td>ch, 3</td>
<td>2,3-dimethylphenol</td><td>££ S.<sup>p</sup>4<sup>THE</sup>9</td><td>CH, 3</td><td>CH, 3</td>
<td>2,4-dichlorophenyl</td><td>GH, r</td><td>X</td><td>h;</td>
<td>2,4-dichlorophenyl</td><td><sup>C</sup>2<sup>H</sup>5</td><td>H</td><td>H</td>
<td>2-methoxy-5-fluorophenyl</td><td> £££-^5¾</td><td>H</td><td>H</td>
<td>2,6-dimethoxyphenyl</td><td>GH ^</td><td>H</td><td><sup>H</sup></td>
<td>3,4-dichlorophenyl</td><td><sup>G</sup>2<sup>H</sup>5</td><td>H</td><td>H</td>
<td>3,5-dichlorophenyl</td><td>H-<sup>C</sup>4<sup>H</sup>9</td><td>H</td><td>X</td>
TABLE XIII <sup>R</sup>6 <sup>Q</sup>1 <sup>Q</sup>2 18 ^ 7 cyclohexyl 1-naphthyl phenol phenyl phenyl phenyl phenyl
4-phenylphenyl
4-laminated material
4-phenylphenyl 4-fluorophenyl
4-fluorophenyl
-ch<sub>2</sub>gh<sub>2</sub>CH<sub>3</sub>
-GELGH-ch; gh<sub>9</sub>ch<sub>9</sub>C<sub>2</sub>fi<sub>5</sub>
-CHgCH-gh<sub>2</sub>ch<sub>2</sub>-CH<sub>2</sub>CH<sub>2</sub>?2<sup>H</sup>5
-CH<sub>2</sub>CHnCl
-GHgGH-CH<sub>2</sub>CH<sub>2</sub>-CHgCH-CH — CH-
<img file="GR76497B_D0066.tif" />
-gh<sub>2</sub>gh<sub>2</sub>-GHgCH — 64—
TABLE XIII (continued)
R. R.<sub>6</sub>
-s<sub>2</sub>THE<sub>5 </sub>-CH<sub>2</sub>CH-C (CH<sub>5</sub>)<sub>2</sub>C (CH<sub>3</sub>)<sub>2 </sub>CH,
I>
3-trifluoromethylphenyl-CHCH<sub>9</sub>C (CH,)<sub>9</sub>- n = 3 g of 4 c4-chlorophenyl 4-chlorophenyl
2-methoxyphenyl
2.3-dimethylphenyl
2.4-dichlorophenyl
2,4-dichlorophenyl
2- ii<sup>X</sup>9
-CHgCH-ch<sub>2</sub>ch<sub>2</sub>3
-CH<sub>2</sub>CH-OH, CH®J, CH,
2-Methoxy-5-fluorophenyl-CHC (CH2)
2,6-dimethoxyphenyl
3,4-dichlorophenyl
3,5-dichlorophenyl c<sub>2</sub>h<sub>5</sub>
-CH<sub>2</sub>CH<sub>2</sub>CH, CH,. 3 i 3
-CHCHgCH-CH — CH-ch<sub>2</sub>ch = chch<sub>2</sub>
2°18<sup>THE</sup>37 phenyl phenyl phenyl phenyl 4-phenylphenyl
4-phenylphenyl 4-fluorophenyl 4-chlorophenyl
CH ^
-CHCH<sub>2</sub>CH<sub>2</sub>CH-CH<sub>2</sub>CH = CHCH<sub>2</sub>-C (CH<sub>3</sub>)<sub>2</sub>CH = CHC (CH<sub>3</sub>)<sub>2</sub>CH<sub>3</sub>
-CHCHgCHgCH—
-0 (0 ^ JgCHgOHgGCCHjJg. -CH<sub>2</sub>CH = CHCH<sub>2</sub>CH,
CH,
CH,, 3 = CCH,
-CH<sub>2</sub>2-CH<sub>2</sub>-CH = CHCH<sub>2</sub>-CH<sub>2</sub>GH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>-<sup>_G</sup>4<sup>H</sup>9
-CH CH CH<sub>2</sub>CHCH, CH, I J 3
3-trifluoromethylphenyl-CHCH = CHCHCH, CH, • 5 m 3
2-methoxyphenyl-CHgCH-CHCHg4-phenoxyphenyl
<img file="GR76497B_D0067.tif" />
-65Example 37 i
Preparation of (1.1<sup>g</sup>-Diphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane
A mixture of 2.6 g. (0.010 mol) (1,1 '-diphenyl-4-yl) chloromethyldimethylsilane and 1.1 g. (0.012 mol) of imidazole sodium salt in 5 ml of dimethylformamide was heated to 80-90 ° C for 2 h, cooled, diluted with water and extracted with ether, ether, ether on magnesium sulfate and evaporated, remaining 2.0 g. viscous ocher-yellow oil. Micro-sample friction treatment by j
hexanes, yielded solid. Most of the primary product was taken with a warm mixture of 20 ml of hexanes and 3 ml of ethyl acetate, the solution was slowly bubbled, and when turbidity was observed, inoculum crystals were added. The precipitated crystals were collected and dried, yielding 0.84 g. (29%) of the compound title as colorless (flakes) m.p. 51-53 ° C; 1 H spectrum (NUJOL<sup>R</sup>): 1235, 1215,1105, 1065, 900,830,785, 750, 730,685 cm ”<sup>1</sup>
I.
NMR (0DCl): 0.4 (6H, S), 3.7 (2H, S), 6.7 (1H, S); L y (1H, broad S), 7.1-7j8 (10H, m);
Analysis by tin <sup>G</sup>13 ^ 2O<sup>N</sup>2<sup>S</sup>* (w / o 292.45); Calculated: G 73.92 H 6.89 N 9.58
Found: 73.4 7.0 9.4 '
73,7 7,0 9,4
Example 2®
Preparation of (4-chlorophenyl) dimethyl (X-R)<sup>1</sup> dazol-1-ylmethyl) silane
2.2 g of aqueous solution. (0.010 moles) of dimethylsilane chloromethyl (4-x-Rophenyl) dimethylsilane and 1.1 g. (0.012 mol) of imidazole sodium salt in 5 mL of dimethylformamide, stirred at 80-90 g / L, cooled, diluted with water and extracted with water / extract. water and brine, dried over magnesium sulfate /?
V · -V
-66All evaporated, remaining 2.0 g. (81%) of compound head in yellow liquid: 1,5472 * IR spectrum (end)
1560, 1495, 1480, 1375, 1250, 1105, 1080, 905, 830, 810, 740 cm.<sup>1</sup>.
Spectrum (CDC1): 0.3 (6H, S), 3.6 (2H, S), 6.6 (1H, S range), 6.9<sup>THE</sup>, < <
range S), 7.1 (1H, range S), 7.3 (4H, S).
Example 39
Preparation of (2,4-Dichloroenyl) dimethyl (1H-imidazol-1-ylmethyl) silane
A mixture of 5.1 grams (0.020 mol) of dimethylsilane chloromethyl (2,4-dichlorophenyl) and 2.0 grams. (0.022 mol) sodium imidazole salt in 10 mL of dry dimethylformamide, stirred at 8090 ° C for 2 h and treated to Example 1d, to yield.
3.9 g (69%) of the title compound as brown oil: n<sup>r</sup> 1,5637
IR spectrum (endless): 1560,1500,1450,1355,1250,1105,1095,1075,1025.
840, 780, 735 cm.<sup>1</sup>. ’
NMR spectrum (CDCl): 0.4 (6H, S), 3.9 (2H, S), 6.7 (1H, S range), 7.0 (1H, broad S), 7.2-7.5 (4H, m).
Example 40 i
Preparation of diphenyl (1H-imidazol-1-ylmethyl) methylsilane
Size 4.9 g (0.020 mol) of methylsilane chloromethyl (biphenyl) and 2.0 g. (0.022 mol) imidazole sodium salt in 10 ml dry dimethylformamide, reduced to 80 ° C in 3.5<sup>; X.</sup> C?
hour and treated to Example 18, yielding 4.8 g.
Filter by distillation KUGEIR0HR at 125 ° C / 0, Q5 mm. remove volatile impurities, remaining 2.9 g. (% 2%) of.<sup>:</sup> a compound title as an oil: n<sup>2</sup> 1,5995 * IR spectrum (aka-tov)
3375,3250,1500,1430,1255,1230,1110,1075,1025,810,790,735,700,660cm.<sup>1</sup>. NMR (CDCl3): 0.6 (3D, 3), 3.9 (2H, S) 1
6.9 (1H, range S), 7.2-7.5 (1H, m). //
-67For applying the procedures of Examples 37-40, suitable chloromethylsilanes are prepared to prepare the compounds thereof
Table XIV,
<td>PIN 2</td><td>XIV</td>
<td colspan="2"><sup>R</sup>2</td>
<td>1 r; -sj-</td><td></td>
<td> • 1</td><td><sup>2</sup> \</td>
<td colspan="2">j</td>
<td><sup>R</sup>,'</td><td> *2</td>
<td> ——</td><td></td>
<td>CH_ J</td><td>CH ^</td>
<td><sup>i</sup>2<sup>THE</sup>5</td><td>CH, 5</td>
<td>i.22 “C<sub>3</sub>B</td><td>A.</td>
<td>κ a v.-CH<sub>n</sub></td><td>CH,</td>
<td> 4 9</td><td> 3</td>
<td>t ° A</td><td></td>
<td> -<sup>-C</sup>12<sup>H</sup>25</td><td>A.</td>
<td> 2-°14<sup>H</sup>29</td><td>CH ^</td>
<td>2- ° i Father</td><td>ch<sub>5</sub></td>
<td>cyclopropyl</td><td>ch<sub>3</sub></td>
<td>cyclobutyl</td><td>ch<sub>3</sub></td>
<td>cyclopentylion</td><td>CHj</td>
<td>cyclohexyl</td><td>ch<sub>3</sub></td>
<td>1-naphthol</td><td>CH<sub>5</sub></td>
<td>2-naphthylone</td><td>ch<sub>5</sub></td>
<td>phenyl</td><td> 01¾</td>
<td>4-bromophenyl</td><td> (31¾</td>
<td>4-fluorophenyl</td><td>A.</td>
<td>4-methoxyphenyl</td><td> 01¾</td>
<td>4-phenoxyphenyl</td><td>CH, 3</td>
<td>4- (4-chlorophenoxy) phenyl</td><td>gh<sub>3</sub></td>
<td>4- (4-fluorophenoxy) phenyl</td><td>CH<sub>3</sub></td>
<td>4- (4-trifluoromethylphenoxy) ph</td><td>ethylene 01¾</td>
<td>4- (4-methylphenoxy) phenyl</td><td>OH</td>
<td>4-thiomethylphen yl</td><td>A.</td>
<td>4-methylsulfonylphenyl</td><td>. OH,</td>
h
CH, ¢ 31¾
CH
Ohj
CH<sub>3</sub> oh<sub>3</sub> ¢2¾ (31¾ <sup>CH</sup>3 gh<sub>3</sub>
01¾
CH,
CH,
CH,
CH,
CH,
01¾ (31¾
01¾ n £<sup>2</sup> 1.4805 n £<sup>2</sup> 1.4848 nJ<sup>9</sup> 1.4811 tx> 1 .4585 n £<sup>1</sup> 1.4639 n £<sup>2</sup> 1.4999 njp 1.6188
bp 120-125 ° (0.05 mm) 1.5741
4<sup>5</sup> 1.5314 n £<sup>5</sup> 1,5485 ppm d <sup>1</sup>·5833 '
<img file="GR76497B_D0068.tif" />
/ <sub>5</sub> Bj / TO;
-68—
TABLE XIV (continued)
<td>-i</td><td> *2</td><td colspan="3"></td>
<td>4-trifluoromethylphenyl</td><td>CH- 3</td><td>CH,</td><td>* D 1</td><td> .4867</td>
<td>4-methylphenyl</td><td>ch<sub>5</sub></td><td>CH_ 3</td><td> 4<sup>1 1</sup></td><td> .5482</td>
<td>4-iso-propylphenyl</td><td>CH,</td><td>CH, 3</td><td rowspan="2">23 V.</td><td></td>
<td>4-tert-butylphenol</td><td>CH_ 3</td><td>CH,</td><td> 1 .5229</td>
<td>4-cyclohexylphenyl</td><td>CH,</td><td>CH,</td><td> „22 <sup>n</sup>D</td><td> 1.5085</td>
<td>4-trifluoromethoxyphenol</td><td>az?</td><td>CH,</td><td>“22 “D</td><td> 1.4888</td>
<td>4- (4-chlorophenyl) phenol</td><td></td><td></td><td></td><td></td>
<td>4- (4-methylphenyl) phenyl</td><td>CH- 5</td><td>CH,</td><td></td><td></td>
<td>4- (4-trifluoromethylphenyl) phenyl</td><td>CH_ 3</td><td>CH,</td><td></td><td></td>
<td>4- (4-fluorophenyl) phenyl</td><td>CH,</td><td>CH, 5</td><td rowspan="2">22 “D.</td><td></td>
<td>4- (4-bromophenyl) phenyl</td><td>ch,</td><td>CH,</td><td> 1.5745</td>
<td>3-phenylphenyl</td><td>CH,</td><td>CH,</td><td>“21 “D</td><td> 1.6002</td>
<td>3-trifluoromethylphenyl</td><td>CH,</td><td>CH,</td><td> „20 <sup>n</sup>D</td><td> 1.4927</td>
<td>3-chlorophenyl</td><td>CH,</td><td>CH,</td><td></td><td> 1.5560</td>
<td>2-trifluoromethylphenyl</td><td>CH- 3</td><td>CH,</td><td> 4<sup>3</sup></td><td> 1.5056</td>
<td>2-phenylphenyl</td><td>ch<sub>3</sub></td><td>GH_ 2</td><td> „22 <sup>n</sup>D</td><td> 1.5996</td>
<td>2-chlorophenyl</td><td>CH,</td><td>CH,</td><td> „22</td><td> 1.5382</td>
<td>2-methoxyphenyl</td><td>CH,</td><td>CH,</td><td> „22 <sup>n</sup>D</td><td> 1.5344</td>
<td>2,3-dimethylphenyl</td><td> <*3</td><td>CH,</td><td rowspan="2"> 4<sup>2</sup></td><td></td>
<td>2,3-dimethoxyphenyl</td><td>ch<sub>3</sub></td><td>CH,</td><td> 1.5350</td>
<td>2,4-difluorophenyl</td><td>CH,</td><td>CH,</td><td></td><td></td>
<td>2-fluoro-4-chlorophenyl</td><td>ch,</td><td>CH-</td><td></td><td></td>
<td>2-chloro-4-fluorophenyl</td><td>CH</td><td>CH,</td><td></td><td></td>
<td>2-chloro-4-phenylphenyl</td><td>ch<sub>3</sub></td><td>CH,</td><td></td><td></td>
<td>2-fluoro-4-phenylphenyl</td><td>CH,</td><td>CH,</td><td></td><td></td>
<td>2-methyl-5-chlorophenyl</td><td>CH </td><td>CH,</td><td rowspan="2"></td><td></td>
<td>2,6-dimethoxyphenyl</td><td>ch<sub>3</sub></td><td>CH,</td><td></td>
<td>2,6-dimethylphenyl</td><td>CH,</td><td>CH,</td><td rowspan="3"></td><td></td>
<td>3,4-dichlorophenyl</td><td>CH,</td><td>CH,</td><td>H.567Z</td>
<td>3-methyl-4-fluorophenyl</td><td>CH,</td><td>CH,</td><td>z</td>
<td>3 "5-dichlorophenyl</td><td></td><td>CH,</td><td> 2 2</td><td><sup>Mr</sup>U $ (6</td>
<td><sup>p</sup>2<sup>THE</sup>5</td><td> 0-¾ 2 5</td><td>CH,</td><td></td><td></td>
; 4...
1 'W.
-69 TABLE XIV (continued)
<td></td><td></td><td></td>
<td>ia-O ^ H?</td><td>cyclohexyl</td><td>CH ^</td>
<td></td><td>n-C ^Hθ</td><td>CH ^</td>
<td> 2^21</td><td>cyclopropyl</td><td>CH<sub>5</sub></td>
<td>nC,</td><td>nC, H</td><td>CH,</td>
<td> 2 12 25</td><td> - 3 7</td><td> 3</td>
<td> 2-<sup>C</sup>i4<sup>H</sup>29</td><td> £22“^3^7</td><td>ch<sub>3</sub></td>
<td> 2“°18^37</td><td>3-methylbutylene</td><td>CH, 3</td>
<td>cyclopropyl</td><td> 2-<sup>c</sup>6<sup>a</sup>i3</td><td>CH ^</td>
<td>cyclopentylion</td><td>cyclopentylion</td><td>CEL ^</td>
<td>cyclohexyl</td><td>cyclohexyl</td><td>C ^</td>
<td>1-naphthylone</td><td> 2-°4<sup>THE</sup>9</td><td>Cl · ^</td>
<td>1-naphthylone</td><td> ££££·“ °4<sup>THE</sup>9</td><td>CE ^</td>
<td>2-naphthylone</td><td> 2-°5<sup>THE</sup>11</td><td>CH, 3</td>
<td>phenyl</td><td> 2-0^</td><td>ch<sub>5</sub></td>
<td>phenyl</td><td> 2-<sup>p</sup>4<sup>THE</sup>9</td><td>C ^</td>
<td>phenyl 1, 1 </td><td>-dimethylpropylene</td><td>CH, 9</td>
<td>phenyl</td><td> 2-<sup>p</sup>6<sup>X</sup>13</td><td>ch<sub>5</sub></td>
<td>4-phenylphenyl</td><td> °2<sup>THE</sup>5</td><td>CH- 9</td>
<td>4-phenylphenyl</td><td> 2-<sup>p</sup>4<sup>THE</sup>9</td><td></td>
<td>4-bromophenyl</td><td>iso-C, H --- 3 L</td><td>CH<sub>5</sub></td>
<td>4-chlorophenyl</td><td> £-<sup>G</sup>4<sup>H</sup>9</td><td>c ^</td>
<td>4-fluorophenyl</td><td> 2-°4<sup>THE</sup>9</td><td>es ^</td>
<td>4-phenoxyphenyl</td><td> ££££·-°4<sup>THE</sup>9</td><td>ch<sub>5</sub></td>
<td>4-S-propylophen yl</td><td>cyclopropyl</td><td>CHj</td>
<td>4-tert-butylphenyl</td><td>iso-CH - 4 9</td><td>CH ^</td>
<td>3-phenylphenyl</td><td>iso-C.H_ ---- 4 9</td><td>CHj</td>
<td colspan="2">3-trifluoromethylphenyl c -C</td><td>ch<sub>3</sub></td>
<td>3-chlorophenyl</td><td> 2~°5<sup>THE</sup>11</td><td></td>
<td>2-methoxyphenol</td><td> ££££·“°4<sup>THE</sup>9</td><td>C ^</td>
<td>2-thiomethylphenyl</td><td>cyclobutanol</td><td>ch<sub>3</sub></td>
<td>2-phenylphenyl</td><td>iso-OH<sub>0 </sub>--4 9</td><td>C®<sub>3</sub></td>
<td>2,4-dichlorophenyl</td><td> 2“<sup>a</sup>4<sup>THE</sup>9</td><td>c ^</td>
<td>2,4-dichlorophenyl</td><td>cyclopropyl</td><td>CSj</td>
<td>2,3-dimethylphenyl</td><td></td><td>CH, 3</td>
2-methyl-5-fluorophenyl
2.5-dimethoxyphenol
2.6-Dimethylphenyl 3 or 4-diethyl; orophenyl
1.47W ng 1.5449 <sup>u</sup> i
Dp 1.5880
1¾<sup>1</sup> 1.5415 n22 1.5161 cyclopentyl CH 4-methylbutyl CEL, 1-methylbutyl CH_, 2-<sup>p</sup>5<sup>THE</sup>11
<img file="GR76497B_D0069.tif" />
-70Chapter Xiv (continued)
<td>X</td><td>V.</td><td>E P</td><td></td><td></td>
<td>3,5-Cichlorophen yl</td><td> 2-<sup>c</sup>A.</td><td>defeat</td><td></td><td></td>
<td>3 "5-dichlorophenyl</td><td>cyclohexyl</td><td>ciu r</td><td></td><td></td>
<td>3-methyl-4-chlorophenyl</td><td>cyclocyclone</td><td>CLL, P</td><td rowspan="2">1st 4 '</td><td rowspan="2"> 1.5310</td>
<td>4-fs-orphaniline</td><td>phenylion</td><td>CH, 'P.</td>
<td>4-chlorophenyl</td><td>phenylion</td><td>Oh, P</td><td> 21</td><td> 1.5000</td>
<td>4-β romophenyl yl</td><td>phenylion</td><td>Oh, P</td><td>the<sup>22</sup>D</td><td> 1.5115</td>
<td>4-phenylphenyl</td><td>phenylion</td><td>CH „ r</td><td> „21 <sup>n</sup>D</td><td> 1.6373</td>
<td>4-tert-bp hydrophilic material</td><td>phenylion</td><td>The/</td><td></td><td></td>
<td>4-thiomethylphen yl</td><td>phenylion</td><td>oh.</td><td></td><td></td>
<td>4-phenoxy yarn;</td><td>phenylion</td><td>CH ..</td><td></td><td></td>
4-methylsulfonylphenyl phenyl
4-cyclohexylphenyl phenyl
4- (4-fluorophenyl) phenyl phenyl
3-Trifluoromethylphenyl phenyl onc
2-chlorophenyl phenyl
2-methoxyphenyl. phenylion
2,4 ~ dichloromethane phenyl vinyl
2-chloro-4-phenylphenylphenyl
2-fluorine-4-phenyl phenyl ylophen
3 "5-dichlorophenyl phenyl
2.5-dimethoxyphenyl phenyl
2.6-Dimethylphenylphenyl
CH „
P
3¾
OHOH, <sub>The:</sub>/ on<sub>3</sub><sup>ΰΰΐ</sup>Mr ch<sub>3</sub>
Ci /
CH,
1.6058
2?
ng 1.5150
<td>4-fluorophenyl</td><td>4-fluorophenyl chloride</td><td>Ja.</td><td><sup>r</sup>TD</td><td colspan="2"> 1.5559</td>
<td>4-chlorofluidyl nylon</td><td>4 x xenophenylone</td><td>The/</td><td>1)</td><td colspan="2"> 1.5820 !</td>
<td>4-bromophyne;</td><td>4-bromophenyl</td><td><sup>0P</sup>3</td><td> 21 <sup>a</sup>o</td><td colspan="2"> 1.5305</td>
<td>4-phenylphenyl</td><td>4-phenylphenyl ion</td><td>OIL</td><td rowspan="2">m.p. 21<sup>k</sup>d</td><td colspan="2"> 44-53°</td>
<td>4-methylphenyl</td><td>4-methoxyphenyl</td><td>ch<sub>5</sub></td><td colspan="2"> '1.5947 1</td>
<td>3-tris-oromed-ylphenyl</td><td>3-trifluorophenylphenyl</td><td>oh /</td><td></td><td></td><td>I. k! l i</td>
<td>2-chlorophenyl</td><td>2-chlorophenyl</td><td><sup>CIi</sup>3</td><td>20 D</td><td> /.39:</td><td>jpf <sup>1</sup></td>
<td>2-methoxylated nylon</td><td>2-methoxyphenyl</td><td>CH, r</td><td></td><td></td><td> 1 !</td>
<td>2.4; -d; 10 o'clock</td><td>2,4-chloroform material</td><td>CH_ j></td><td>22- W</td><td>1 .CO</td><td> 9</td>
<td>3.3-5-chloramphenicol, eth</td><td>p, 5-dichlorophenyl</td><td>ex ... y</td><td></td><td></td><td></td>
<td>2-chlorophenyl</td><td>4-chloroform yl</td><td>3H_. P</td><td> /5</td><td>1.5bs</td><td>1 d</td>
-71PIN_X (continued)
IX IX
<td>* i</td><td colspan="3"> ^2</td>
<td>2-chlorophenyl</td><td>4-fluorophenol</td><td>CH, 3</td><td></td>
<td>4-phenylphenyl</td><td>4-chlorophenyl</td><td>ch<sub>5</sub></td><td></td>
<td>4-phenylphenyl</td><td>4-fluorophenyl</td><td>CH, 3</td><td></td>
<td>4-phenylphenyl</td><td>2,4-dichlorophenyl</td><td>CH, 3</td><td></td>
<td>4-fluorophenyl</td><td>2,4-dichlorophen yl</td><td>CH, 5</td><td>I. I.</td>
<td>4-chlorophenyl</td><td>2,4-dichlorophenyl</td><td>ch<sub>5</sub></td><td></td>
<td>1-naphthylone</td><td>2,6-dimethoxyphenol</td><td>CH<sub>5</sub></td><td></td>
<td>4-phenoxyphenyl</td><td>3,4-dichlorophenol</td><td>ch<sub>5</sub></td><td></td>
<td></td><td> °2<sup>THE</sup>5</td><td>c<sub>2</sub>h<sub>5</sub></td><td>I.</td>
<td>iso-C ^ Hg</td><td>Iso-O ^ Hg</td><td>iso-C ^ Hg</td><td>I.</td>
<td>xC ^ Hg</td><td> *-<sup>C</sup>4<sup>H</sup>9</td><td>* L.<sup>THE</sup>9</td><td></td>
<td> -~<sup>C</sup>8<sup>H</sup>17</td><td><sup>C</sup>2<sup>H</sup>5</td><td colspan="2">cyclopentylion '</td>
<td>i-<sup>t_C</sup>l4<sup>H</sup>29</td><td>cyclopropyl</td><td colspan="2">1-methylbutylene</td>
<td> -~<sup>G</sup>18<sup>H</sup>37</td><td> -<sup>-C</sup>6<sup>H</sup>1<sub>5</sub></td><td> £“<sup>C</sup>6<sup>h</sup>13</td><td></td>
<td>cyclopropyl</td><td><sup>C</sup>2<sup>H</sup>5</td><td>S-<sup>G</sup>4<sup>H</sup>9</td><td></td>
<td>cyclohexyl</td><td>hc<sub>3</sub>e<sub>?</sub></td><td>m-C Ο Hγ</td><td></td>
<td>1-naphthylone</td><td></td><td>x-<sup>C</sup>4<sup>H</sup>9</td><td></td>
<td>2-naphthol</td><td>k-<sup>C</sup>4H<sub>9</sub></td><td colspan="2">cyclobutyl '</td>
<td>phenyl</td><td>cyclopropyl</td><td>xC<sub>6</sub>H<sub>n</sub></td><td></td>
<td>4-phenylphenyl</td><td>c<sub>2</sub>h<sub>5</sub></td><td>c<sub>2</sub>h<sub>5</sub></td><td>I. i</td>
<td>4-phenyphenol phenol</td><td>D "<sup>p</sup>4<sup>THE</sup>9</td><td> *-<sup>C</sup>4<sup>H</sup>9</td><td> .</td>
<td>4-phenylphenyl</td><td> -<sup>C</sup>6<sup>H</sup>13</td><td> -~<sup>G</sup>6<sup>H</sup>13</td><td></td>
<td>4-phenylphenyl</td><td>cyclohexyl</td><td colspan="2">cyclohexyl I</td>
<td>4-chlorophenyl</td><td>k-<sup>C</sup>4<sup>H</sup>9</td><td> -“<sup>G</sup>4^9</td><td></td>
<td>4-fluorophenyl</td><td>K-<sup>The</sup>5H<sub>c</sub></td><td>mr.H.</td><td></td>
<td>4-phenoxyphenyl</td><td>mr.H.</td><td colspan="2">cyclohexyl</td>
<td colspan="2">4- (4-chlorophenoxy / phenyl n-C.Hg</td><td>2i-<sup>i</sup>4<sup>THE</sup>9</td><td>I.</td>
<td>4-tert-butylphenol</td><td>S ”<sup>C</sup>4<sup>H</sup>9</td><td>k2-<sup>C</sup>4<sup>H</sup>9</td><td>I.</td>
<td>3-methoxyphenyl</td><td><sup>C</sup>2<sup>H</sup>5</td><td>tm-C ^ Hg</td><td>I.</td>
<td>3-trifluoromethylphenyl</td><td>S-<sup>C</sup>4<sup>H</sup>9</td><td>S-Vg</td><td></td>
<td>2-thiomethylphenyl</td><td>iso-C ^ Hg</td><td colspan="2">3-methylbutyl</td>
<td>2-phenylphenol</td><td>cyclohexyl</td><td colspan="2">cyclohexyl</td>
<td>2,4-dichlorophenyl</td><td>XC<sub>4</sub>Hg</td><td> *-<sup>G</sup>4<sup>H</sup>9</td><td></td>
<td>2,6-dimethylphenyl</td><td>XDD · -<sup>THE</sup>4<sup>THE</sup>9</td><td></td><td></td>
<td>3,5-dichlorophenyl</td><td>cyclopentylion</td><td>cyclogentyl</td><td>, ov!</td>
<td>3-methyl-4-chlorophenol</td><td> £-<sup>C</sup>4<sup>H</sup>9</td><td> -~<sup>c</sup>4%</td><td> -</td>
<td>2-methyl-5-fluorophenyl</td><td>XC ^ Hg</td><td>—- “C4<sup>THE</sup>9</td><td></td>
TABLE XIV (continued)
<td><sup>b</sup>i</td><td> *2</td><td> *3 ,</td>
<td></td><td><sup>GSG</sup></td><td></td>
<td> °2<sup>THE</sup>5</td><td>phenyl</td><td>phenyl</td>
<td>cyclohexyl</td><td>phenyl</td><td>phenyl</td>
<td> -“°18<sup>THE</sup>37</td><td>phenyl</td><td>phenyl</td>
<td> £-<sup>C</sup>4<sup>H</sup>9</td><td>4-chlorophenyl</td><td>4-chlorophenyl</td>
<td> -°12<sup>THE</sup>25</td><td>4-chlorophenyl</td><td>4-chlorophenyl</td>
<td>1-naphthylone</td><td>4-fluorophenyl</td><td>4-fluorophenyl</td>
<td>cyclopropyl</td><td>phenyl</td><td>4-tert -butylphenyl</td>
<td> 2-°4<sup>THE</sup>9</td><td>phenyl</td><td>4-phenylphenyl</td>
<td>· ”<sup>p</sup>4<sup>THE</sup>9</td><td>phenyl</td><td>2,4-dichlorophenyl</td>
<td>nC ^</td><td>phenyl</td><td>3-trifluoromethylphenyl</td>
<td>iso-0.H ---- 4 g</td><td>phenyl</td><td>3,5-dichlorophenyl</td>
<td>cyclopentylion</td><td>phenyl</td><td>2,6-dimethoxyphenyl</td>
<td> -°14<sup>THE</sup>29</td><td>4-chlorophenyl</td><td>2-fluorophenyl!</td>
<td> 2-<sup>C</sup>4<sup>H</sup>9</td><td>4-fluorophenyl</td><td>4-phenylphenyl</td>
<td>phenyl</td><td>phenyl</td><td>phenyl mp.175-178 °</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>4-dichlorophenyl</td><td colspan="2">2,4-dichlorophenyl 2,4-dichlorophenyl</td>
<td>phenyl</td><td>4-fluorophenyl</td><td>4-fluorophenyl> I.</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-naphthylone</td><td colspan="2">4-methylthiophenyl 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 is</td>
<td>phenyl</td><td>2-chlorophenylone</td><td>4-fluorophenyl:</td>
<td>phenyl</td><td>4-chlorophenyl</td><td>4-phenylphenyl</td>
<td>1-naphthylone</td><td>4-bromophenyl</td><td>3-methylphenyl</td>
<td>4-phenoxyphenyl</td><td>3,5-dimethylphenyl</td><td>> 3,4-dichlorophenyl. ./<1</td>
Example 41
Preparation of (1,1'-Diphenyl-4-yl) dimethyl (2-methyl-1H-Ampadazol-1-ylmethyl) silane
The title compound is prepared by applying the procedure of Example 37 (1,1'-biphenyl).
<img file="GR76497B_D0070.tif" />
hourly ^
-73w of lodimethylsilane and 2-methylimidazole sodium salt. ·<sub>(</sub>.
Conjugates can thus be prepared using 2,4-dimethylimidazole, 4,5-dimethyl- salts. ..
imidazole and 2,4,5-trimethylimidazole. !
G The process of Example 41 may be used to prepare the compounds of Table XV
<img file="GR76497B_D0071.tif" />
-<sup>-0</sup>18 Cyclohexyl
1-naphthyl phenyl phenyl
4-phenylphenyl
4- (4-fluorophenyl) phenyl
4-phenoxyphenyl
CH ^ on<sub>3</sub><sup>oh</sup>3
0H<sub>3</sub>
CH<sub>5</sub>
CH ^
CHj
OU
3-trifluoromethylphenyl CH,
CH, ch:
2-Methoxyphenyl 2,4-dichlorophenol 2-chloro-4-phenylphenyl OH-phenyl
4-phenylphenyl
US<sub>6</sub>xx<sub>Ϊ5</sub> ®3 ®3
OK,
OH,
OH,
OH,
CH_
OH,
CH,
OH,
CH,
OH,
2l
OH,
H
H
CH ^
H
H ch<sub>3</sub> ^3
CH,
H%
CH,
H
OH,
H
CH „£ -C<sub>4</sub><sup>h</sup>9 *-<sup>p</sup>4<sup>THE</sup>9
2,4-dichlorophenyl 4- (4-chlorophenoxy) phenyl cyclohexyl CH ^ CH ^
CH ^
CH,
CH,, H OH, H H H
CH,
CH,
THE
C ^
Oh,
THE
CH,
THE
Yeah, yeah<sub>5</sub>
CH ^
THE
THE
CH<sub>5</sub>
THE
THE
CH,
CH,
THE
THE<sub>; </sub>CH, H I phenyl 4-fluorophenyl 4-fluorophenyl 4-chlorophenyl 4-fluorophenyl 4-fluorophenyl 4-chlorophenyl 4-chlorophenyl phenyl phenyl phenyl phenyl
4-chlorophenyl
<img file="GR76497B_D0072.tif" />
? ’ ' · · ,··>'·; ·
-74PIN3 XV (continued)
<td></td><td></td><td> ^2</td><td>2i</td><td></td><td> %</td>
<td>2-chlorophenyl</td><td>4-chlorophenyl yl</td><td>CH</td><td></td><td> %</td><td><sup>CH</sup>5</td>
<td>2,4-dichlorophenyl</td><td colspan="2">2,4-dichlorophenyl CH_</td><td>OB,</td><td>THE</td><td>THE</td>
<td>X-ray p37</td><td> 2-<sup>c</sup>6<sup>h</sup>i<sub>3</sub></td><td colspan="2"><sub>£</sub>-c<sub>6</sub>h<sub>13</sub> the</td><td><sup>0H</sup>3</td><td> %</td>
<td>1-naphthylone</td><td>E-Vs</td><td> 2-<sup>ΰ</sup>4<sup>THE</sup>9</td><td>GH</td><td></td><td>CR, j</td>
<td>phenyl</td><td>phenyl</td><td colspan="2">phenyl CH,</td><td>THE</td><td>THE</td>
<td>phenyl</td><td>phenyl</td><td>II</td><td>CH,</td><td>THE</td><td>oh<sub>5</sub></td>
<td>phenyl</td><td>phenyl</td><td>Pi</td><td> “3</td><td></td><td>THE</td>
Example 42
Preparation of the compound of (1,1'-Biphenyl-4-yl) -dimethyl (1-imidazol-1-ylmethyl) .silane and 1: 1 Copperchloride
0.50 g mixture. (0.0017 mol) (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane and 0.22 g (0.0017 moles) of copper chloroform hypochlorite in 15 ml. tetrahydrofuran was heated to reflux under Ng for 15 minutes, and the resulting deep green solution was evaporated, leaving the compound compound as a dark green solid (mp: 72-80 ° C).
IR spectrum (NOJOL;<sup>11</sup>159 ° C, 1515,125 ° C, 111 ° C, 84 ° C, 82 ° C, 75 ° C, 695.65 ° C.<sup>1</sup>
By applying the procedure of Example 24, any of the compounds of Tables XIV, XV, XVI, XVII, XVIII or XIX can be converted into metal complexes or salts. '
Example 45 i!
Preparation of (1,1'-Biphenyl-4-yl5 (1H-imidazol-1-ylmethyl) (methoxy) methylsilane
A mixture of (1,1'-biphenyl-4-yl) chloro (chloromethyl) methylsilane and two equivalents of imidazole sodium salt in dimethylformamide is heated at 8Q-90 ° C for 2 hours. Then add ten equiv of methanol and keep the mixture at 70 ° C in water, cool the jar with water and extract rapidly with ether. In aqueous solution with water and brine, dry overnight.
-75 magnesium and evaporated shotgun, provides the title compound.
Related compounds can be prepared in this manner, using appropriate chlorosilane and alcohol * for Rg = OH, water is used, alcohol is removed, and hydrolysis is carried out at 2 ° C-25 ° C instead of 70 ° C.
Example 44
Preparation of 1, 1 - (Dimethylethoxy) (1H-imidazol-1-ylmethyl} .methyl (phenyl) silane _____________________________________________________ i.
3.6 g mixture. (0.015 mol) chloromethyl (1,1-dimethyl- - ethoxy) methyl (phenyl) silane and 1.3 g. (0.015 mol) imidazole sodium salt in 10 ml dimethylformamide, stirred at 50 ° C for 3 h, allowed to stand at room temperature for 72 h, poured into water and extracted with water. of water and once with brine, dried over magnesium sulfate and evaporated to a residue of 3.8 g of oil. © Impurities were removed by distillation. .
KUGELR0HR at 90 ° C (air bath -) / 0.05 mm, 2.9 mm <sup>: ; ;</sup>.
gr. (71) of the title compound as a pale yellow oil: or 1, 5291; IR spectrum (unbroken): 3105, 3 ° 7 °, 3045, 2970, 1590, 1500, 1425,
1360, 1250, 1235, 1185, 1110, 1055, 1020, 900,805, 740,700,660 cm.<sup>1</sup>.
NMR (CDOI): 0.6 (3H, S), 1.3 (9H, S), 3.6 (2H, S), 6.8 (1H, S),
7.0 (1H, S), and 7.3 7.7 (6H, m). j
The compounds of Tables XVI and XVII can be prepared by the procedures of Examples 43 and 44.! m
<img file="GR76497B_D0073.tif" />
<td>* i</td><td> *2</td><td colspan="2"> ?6 \</td>
<td><sup>C</sup>2<sup>H</sup>5</td><td>CH, 5</td><td>si ^</td><td></td>
<td>t £ it<sub>L.</sub>-THE<sub>4</sub><sup>THE</sup>9</td><td>Ohj</td><td>£ £ ·<sup>a</sup>4<sup>THE</sup>9</td><td></td>
<td> £-<sup>g</sup>4<sup>H</sup>9</td><td><sup>0H</sup>2l</td><td><sup>G</sup>2^5</td><td> ! . · . ·;</td>
<td> -<sup>-G</sup>12<sup>H</sup>25</td><td> °2<sup>THE</sup>5</td><td>GH, 3</td><td></td>
<td>n-CigH<sub>57</sub></td><td> 2-°6<sup>the</sup>13</td><td>GH, 3</td><td></td>
<td>cyclopropol</td><td>off,</td><td>S- ° 4<sup>H</sup>9</td><td></td>
<td>cyclohexyl</td><td><sup>0H</sup>3</td><td>OH, 5</td><td></td>
<td>1-naphthol</td><td>Uo-G ^</td><td>is-0<sub>3</sub>Hg</td><td></td>
<td>2-naphthylone</td><td>cyclobutanol</td><td>nO ^</td><td></td>
<td>phenol</td><td>CH</td><td>THE</td><td>·</td>
<td>phenol</td><td></td><td>GH, 5</td><td></td>
<td>phenol</td><td><sup>CH</sup>3</td><td colspan="2">C ^ L ·<sup>2 5</sup> _____</td>
<td>phenol</td><td>CH ^</td><td>lOO-Gyt-,</td><td> 1.5352</td>
<td>phenol</td><td>£ 2X · -<sup>p</sup>4<sup>THE</sup>9</td><td>THE</td><td> - </td>
<td>4-phenylphenol n</td><td>X-<sup>p</sup>4<sup>THE</sup>9</td><td>CH ^</td><td></td>
<td>4-phenylphenyl</td><td>£ XIX "<sup>p</sup>4<sup>THE</sup>9</td><td>THE</td><td></td>
<td>4-phenylphenyl</td><td> %</td><td><sup>i</sup>2<sup>X</sup>5</td><td> '</td>
<td>4-phenylphenyl</td><td>GHj</td><td> 2-°4<sup>THE</sup>9</td><td></td>
<td>4-chlorophenolone</td><td> 2-°4<sup>X</sup>9</td><td> £~<sup>p</sup>4<sup>THE</sup>9</td><td></td>
<td>4-chlorophenyl</td><td></td><td>GH, 5</td><td></td>
<td>4-chlorophenyl</td><td></td><td><sup>G</sup>2<sup>H</sup>5</td><td></td>
<td>4-fluorophenyl</td><td>h<sub>6</sub>THE<sub>13</sub></td><td>nG ^</td><td><sup>r</sup>-<sup>:</sup>' :</td>
<td>4-fluorophenyl</td><td> %</td><td> °2<sup>THE</sup>5</td><td></td>
<td>4-phenoxyphenyl</td><td>cyclohexyl</td><td> £££-<sup>G</sup>4<sup>H</sup>9</td><td> ' </td>
<td>4-tert-butylphenyl</td><td>n-0 ^ 7</td><td></td><td> 7 7/-</td>
<td>3-trifluoromethylphenyl</td><td>£ £-<sup>p</sup>4<sup>THE</sup>9</td><td>THE</td><td> /.?/ </td>
<td>2-methylthiophenolone</td><td>cyclopentylion</td><td>The<sub>2</sub>the<sub>5</sub></td><td></td>
<td>2,4-dichlorophenyl methyl</td><td>OB,</td><td>gh<sub>3</sub></td><td> ' 7</td>
<td>2,4-dichlorophenol</td><td></td><td> *2*5</td><td></td>
<td>2,4-dichlorophenyl</td><td>Oh,</td><td>W £ · - °<sub>4</sub><sup>THE</sup>9</td><td></td>
<td>2,4-dichlorophenol</td><td> 5-°4<sup>THE</sup>9</td><td rowspan="2"><sup>G</sup>2<sup>H</sup>5 ioo-C ^</td><td></td>
<td>2,3-dimethylphenol</td><td>cyclopropol</td><td></td>
<td>2-methyl-5-fluorophenyl</td><td>i-<sup>p</sup>4<sup>THE</sup>9</td><td>nG H.</td><td></td>
<td>2,6-dimethoxyphenyl</td><td colspan="2">1,1-dimethylpropolone H ''</td><td></td>
<td>3-methyl-4-chlorophenyl</td><td> 5¾</td><td></td><td>i: * r · \ C ~ · \ ** '· - ..</td>
<td>3,5-dichlorophenyl</td><td> 2-°5<sup>THE</sup>I1</td><td>iii</td><td> <’7-</td>
<td>THE"<sup>p</sup>ΐ2<sup>THE</sup>25</td><td colspan="2">2,4-dichlorophenol tert, -C ^B</td><td> 9 7-/ <sup>;</sup>7\ 7 7 ·/ /7 ,.</td>
S XVI (oneksia)
<td>i</td><td>PI.</td><td>THE- * 5:</td>
<td rowspan="2">- t '. · <</td><td>. IV V '. 1;</td><td>CX ..</td>
<td></td><td>j</td>
<td>1-neophyl, onc</td><td>fa 1 Vil.VuQV</td><td> 2-5</td>
<td>phenyl</td><td>be happy</td><td>li, i '';</td>
<td>4-fluoro;</td><td>phenyl</td><td>'' A.</td>
<td>4-ml; > d</td><td>ni nylon</td><td>tt: - yy,</td>
<td>4-phenylphenyl; be</td><td>• Nanyl t</td><td>lm</td>
<td>4-phenylphenyl</td><td>Ci., I nylon</td><td> -49</td>
<td>4-tert *; 3-butyl nylon</td><td>phenyl</td><td>i-al i</td>
<td>3-fluorophenyl</td><td>phenyl</td><td>C<sub>£</sub>II<sub>5</sub> :</td>
<td>2-methoxyptinyl</td><td>phenyl</td><td>THE ;</td>
<td>i-chlorophenyl</td><td>phenyl</td><td></td>
<td>2,4-3 mm wide</td><td>phenyl</td><td>100-, XXx</td>
<td>3, n-L-x; .-.; Rophenylion</td><td>phenyl</td><td></td>
<td>4-f <i> ser ;;</td><td>4-fluorophenyl</td><td>third-O, H-</td>
<td>4-fluorophenyl;</td><td>4-fluorophenyl</td><td>lol</td>
<td>4-chloride;</td><td>4-chlorophenyl amine</td><td></td>
<td>4-chlorophenyl</td><td>4-x chloroenyl</td><td>'-A.D: C. J</td>
<td>4-phenylphenyl.</td><td>4-phenylphenyl</td><td></td>
<td>2,4-dichlorophenyl</td><td>2,4-dichlorophenyl</td><td></td>
<td>3-trifluoromethylphenyl</td><td colspan="2">3-trifluoromethylphenyl i</td>
<td>2-methoxyphenyl</td><td>2-methoxyphenyl</td><td>X</td>
<td>2-chlorophenyl</td><td>4-fluorophenyl</td><td>Pi <sup>:</sup></td>
<td>3-trifluoromethylphenyl</td><td colspan="2">4-tert-butylphenyl ———— - e- V</td>
<td>2, -fluoro-4-chlorophenyl</td><td>4-Bromophenyl</td><td>i · o-m, II</td>
<td>2,3-dimethylphenyl</td><td>4-Ethylthiophenyl vinyl</td><td>l<sup>I:</sup>5</td>
<td>2, S-dimethoxyphenyl</td><td>4- {Nylon Nylon</td><td>X</td>
<td>3,4-dichlorophenyl</td><td>4 ~ methylphenyl</td><td> £22-¾¾</td>
<img file="GR76497B_D0074.tif" />
nylon a <'. i nylon
-78 TABLE XVII (continued)
<td></td><td> %</td><td></td><td>2i</td><td> ?2</td><td> :-2</td>
<td>phenyl</td><td>° s</td><td>£££ Ξ ·<sup>p</sup>4<sup>THE</sup>9</td><td>THE</td><td>H</td><td>C ^</td>
<td>phenyl</td><td>ch<sub>3</sub></td><td>§ ££ Sl- ° 4<sup>THE</sup>9</td><td>CH, 3</td><td>CH, 3</td><td>GH<sub>3</sub></td>
<td>phenyl</td><td>GH ^</td><td> £-<sup>p</sup>4<sup>THE</sup>9</td><td>THE</td><td>CH, 3</td><td></td>
<td>phenyl</td><td>CH,</td><td>iso-C.H.<sub>the </sub>--4 9</td><td>CH, 3</td><td>H</td><td>The</td>
<td>4-phenylphenyl</td><td> -<sup>the</sup>- ° L</td><td>t-C.H.<sub>the</sub></td><td>CH, 3</td><td>ch<sub>3</sub></td><td>^ oh<sub>3</sub></td>
<td>4-phenylphenyl 4-phenylphenyl</td><td>CH, CH,</td><td>··· - 4 y t-C ^ t-C H</td><td>CH ^ CH, 3</td><td>H<sup>GH</sup>3</td><td>H : ch,</td>
<td>4-chlorophenyl</td><td>CH ^</td><td>t-CH-,</td><td>CH, 3</td><td>H</td><td>The</td>
<td>4-chlorophenol</td><td>C ^</td><td>t-G H.</td><td>THE</td><td>ch<sub>3</sub></td><td>CH, 3</td>
<td>4-fluorophenyl</td><td></td><td>T.-G H.</td><td>THE</td><td></td><td rowspan="2">H ch<sub>3</sub></td>
<td>4-fluorophenyl</td><td>OB,</td><td>* C. tf-0H</td><td>THE</td><td>H</td>
<td>phenyl</td><td>phenyl</td><td> °2<sup>THE</sup>5</td><td>oh<sub>3</sub></td><td>CH ^</td><td>CH, 3</td>
<td>phenyl</td><td>phenyl</td><td rowspan="3">- "θ3 ^ 7 £ 22 ^ 3 ^ 7 t-C ^ iso-O ^ Hg</td><td></td><td>CH, 3</td><td>OH,</td>
<td>4-fluorophenyl</td><td>phenyl</td><td>THE</td><td>C ^</td><td>CH, 3</td>
<td>4-fluorophenyl 4-chlorophenyl methyl</td><td>phenyl phenyl</td><td>CH, 3 CH ^</td><td>H H</td><td>H H</td>
<td>2,4-dichlorophenyl</td><td>phenyl</td><td>THE</td><td>CH,</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>4-fluorophenol</td><td rowspan="2">tse-0<sub>4</sub>Ho £ £ Sl '^ 4®9</td><td>CH, 3</td><td>H</td><td>H</td>
<td>4-fluorophenol</td><td>4-fluorophenyl</td><td>THE</td><td>CEL</td><td>CH, 3</td>
<td>4-fluorophenyl</td><td colspan="2">4-Fluorophenyl tert-O2 H2 O</td><td>CH ^</td><td>CH,</td><td></td>
<td>2-methoxyphenyl</td><td colspan="2">2-methoxyphenyl CgH2 +</td><td>CH ^</td><td>H</td><td>H</td>
<td>3-methylphenyl</td><td colspan="2">3-methylphenyl iso-O ^H Η</td><td>CH ^</td><td>X</td><td>H 1</td>
Example 45
Preparation of (1H-imidazol-1-ylmethyl) phenyldis (2-propoxy) silane The title compound can be prepared by applying the procedure of Example 26 (chloro). phenyl) bis (2-propoxy silane: 1,4971 * HMR (CDCl2): 1.2 (l2H, olp = 6);
3.6 (2H, S) * 4.2 (2H, permissible, J = 6) * 6.8-7.6 (8H, m).
The compounds of Tables XVIII and XIX may be exemplified in the same way.
TABLE XVIII OR, r {-s; -gh<sub>2</sub>n ^
OR,
<img file="GR76497B_D0075.tif" />
<td>what <*</td><td>'PI'</td><td></td><td></td>
<td><sup>L.</sup>Ί</td><td> 6</td><td>Ί</td><td>X</td>
<td> **—</td><td></td><td></td><td> *-··<·</td>
<td>dx</td><td>C / i</td><td>• i</td><td> 11 ,</td>
<td>* - * J</td><td></td><td></td><td></td>
<td></td><td></td><td></td><td>LL</td>
<td>XX</td><td><sup>c</sup>~5</td><td></td><td>Phi</td>
<td>circulate Yulion</td><td>CL</td><td>Pi</td><td>Pi</td>
<td>1-neophyl. u</td><td> 222¾¾</td><td>Pi</td><td>Ii</td>
<td>phenyl</td><td>ex</td><td>M., ></td><td>XL</td>
phenol in vitro, ex ex
etc.
,THE
THE
H
THE
<td>c-. vinyl</td><td></td><td>Pi</td><td>SI</td><td></td>
<td>4-phen ylphenyl</td><td> /¾</td><td>i</td><td> 11</td><td>II</td>
<td>4-phenylphenyl nylon</td><td> 2-¾¾</td><td>x</td><td>fr: e '3</td><td>CIX</td>
<td>4-fluorophenyl</td><td>GX ''</td><td>X</td><td>SI</td><td>Ii</td>
<td>4-fluorophane material</td><td>X '</td><td>Pi</td><td>II</td><td>Si</td>
<td>4-chlorophenyl</td><td> /¾</td><td>THE</td><td>II</td><td>SI</td>
<td>4-stroke c</td><td>iso-hydroxy.</td><td>THE</td><td>THE</td><td>Uh</td>
<td>3-trifluoromethylphenyl</td><td></td><td>XL.</td><td>CX x</td><td>e.g. V- ~</td>
<td>2-i: holo-c: vinyl</td><td>XX</td><td></td><td> C. A.</td><td> 11</td>
<td></td><td>-? Ύ</td><td> ></td><td></td><td></td>
<td>2, 2- <i> thiophenyl vinyl</td><td> 222¾¾</td><td>II</td><td>• i</td><td>iii</td>
<td>2, dichlorophenyl</td><td>ex</td><td>II</td><td>II</td><td> |</td>
<td>2, L-chlorophyllin</td><td>XX</td><td>Pi</td><td>i r</td><td>Pi</td>
<td>2-; x 0 ol-l-; -fluorophenyl</td><td>x—. ^ 77</td><td>Pi</td><td>Pi</td><td> 3</td>
<td>2, xy-xyzyl vinyl</td><td>; -r; - -</td><td>II</td><td>THE</td><td>M.</td>
<td>3,4-41-chlorophenyl</td><td> /¾</td><td>II</td><td>THE</td><td>II</td>
<td>>, 5-0ix; xJi of vinyl</td><td> 2¾¾</td><td>Pi</td><td>SI</td><td> 11</td>
Table XIX
<img file="GR76497B_D0076.tif" />
1 ^ ϋ D '<sup>ΰ</sup>kx7: 'yl · yl · yl; 1 -y- · yl yl'. ' foil nylon ly
<img file="GR76497B_D0077.tif" />
-80—
TABLE XIX (continued)
<td></td><td></td><td> %</td><td> %</td><td> %</td>
<td></td><td> ?2<sup>THE</sup>5</td><td></td><td></td><td></td>
<td>4-phenylphenyl</td><td rowspan="2">-CHgCH- CH, CH, , 3.3 -CH —- CH-</td><td>H</td><td>H</td><td>H</td>
<td>4-phenylphenyl</td><td>H</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td rowspan="2">-ch<sub>2</sub>ch<sub>2</sub>- CH<sub>3</sub>-CHgCH- ? 2<sup>H</sup>5</td><td>H</td><td>H</td><td>H</td>
<td>4-fluorophenyl</td><td>H</td><td>H</td><td>H</td>
<td>4-chlorophenyl</td><td>-CH<sub>2</sub>CH-</td><td>H</td><td>H</td><td>X</td>
<td>4-chlorophenyl</td><td>-cCch ^ cCch ^ - CH,</td><td>H</td><td>H</td><td> : <sup>H</sup></td>
<td colspan="2">3-trifluoromethylphenylcone -CBCH<sub>2</sub>C (CH<sub>3</sub>)<sub>2</sub> -<sup>-</sup>?4<sup>THE</sup>9</td><td>C ^</td><td>C ^</td><td>A.</td>
<td>2-methoxyphenyl</td><td>-CHgCH-</td><td>CH,</td><td>H</td><td>H</td>
<td>2,3-dimethylphenylene</td><td>-ch<sub>2</sub>ch<sub>2</sub>- c<sub>2</sub>h<sub>5</sub></td><td>✓ H</td><td>CH,</td><td>; CH, I.</td>
<td>2,4-dichlorophenyl</td><td>-CHgCH-</td><td>H</td><td>H</td><td>H</td>
2> 4-dichlorophenyl
2-methoxy-5-fluorophenyl 2,6-dimethoxyphenyl
3,4-dichlorophenyl
- 73 7 -ch<sub>2</sub>chCH, OH, 3a 3
-CH0 (GH ^)<sub>2</sub>CH-CH<sub>2</sub>CH<sub>2</sub>A 'A.
-0HGH<sub>2</sub>CHCH, H hn n
<img file="GR76497B_D0078.tif" />
<img file="GR76497B_D0079.tif" />
3,5-dichlorophenyl
-CH — CH-ch<sub>2</sub>gh = ghgh<sub>2</sub>nG H - 18 37 phenyl phenyl
CH<sub>3</sub>
-CHCH<sub>2</sub>GH<sub>2</sub>CH-CH<sub>2</sub>CH = CHGH<sub>2</sub>CH<sub>5</sub> CH<sub>3</sub> Ci ^
H CH, CH,
3 phenyl 4-phenylphenyl phenyl
-G (GH<sub>3</sub>)<sub>2</sub>CH = CHG (GH ^)<sub>2</sub>AA
-GHCH<sub>2</sub>GH<sub>2</sub>GH-g (ch<sub>5</sub>)<sub>2</sub>ch<sub>2</sub>gh<sub>2</sub>c (ch<sub>3</sub>)<sub>2</sub>-CH<sub>2</sub>CH = CHCH<sub>2</sub>-
<img file="GR76497B_D0080.tif" />
h'-Z'-V; \
H
-81 TABLE XIX (continued) <sup>E.</sup>6
Q,
<img file="GR76497B_D0081.tif" />
4-phenylphenyl 4-fluorophenyl 4-chlorophenyl
4-phenoxyphenyl
CH, GH, «3» 3 _CH<sub>2</sub>G = cch<sub>2 </sub>-CH<sub>2</sub>-CH = CHGH<sub>2</sub>-CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>-CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>GHch<sub>5</sub> H, H
CH,
3-trifluoromethylphenyl — GGH = GHGHCH, GH, 3 g
2-methoxyphenyl-CHgCH-CHGHgCH ^
<img file="GR76497B_D0082.tif" />
0¾
<img file="GR76497B_D0083.tif" />
Configurations j
Useful formulations of compounds which are within the scope of the present invention can be prepared in standard ways. They include powders, granules, pellets, solutions, emulsions, powders, emulsifiable concentrates; and the like. Many of these can be applied directly. Sprayable configurations can be diluted appropriately and used with small pint spray volumes up to several hundred gallons per acre. High-content compositions
I> <sup>1</sup> active ingredient are primarily used as intermediates for further formulations. The formulations generally contain about 1% to 99% by weight of the active ingredient (s) and at least one of: (a) about 0.1% to 20% of surfactant (s) and (b) about 5% to 99% solid or liquid inert diluent (s). More specifically, they will contain
<img file="GR76497B_D0084.tif" />
-82, 'One Hundred Hundred Cavalry Weights
Active means (s) Surface diluent active substance (s)
<td>Wet powders</td><td> 20-90</td><td> 0-74</td><td> 1-10</td>
<td>Oily suspensions</td><td></td><td></td><td></td>
<td>Emulsions, Solutions</td><td></td><td></td><td></td>
<td>(including Ga-</td><td></td><td></td><td></td>
<td>emulsifiable</td><td></td><td>L.<sup>v</sup>:</td><td></td>
<td>Concentrates)</td><td> 5-50</td><td> 40-95</td><td> 0-15</td>
<td>Water suspensions</td><td> 10-50</td><td> 40-84</td><td> 1-20</td>
<td>Powders</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>Great Compositions-</td><td></td><td></td><td></td>
<td>(you are very active)</td><td></td><td></td><td></td>
<td>component)</td><td> 90-99</td><td> 0-10</td><td> 0-2</td>
Of course, smaller or larger active ingredient levels may be present, depending on their intended use and the physical properties of the compound. tank.
Typical solid diluents are described in WATKINS et al. HANDBOOK OF INSECTICIDE DUST DILUENTS AND CARRIERS 2ND ED, DORLAND BOOKS, CALDWELL, NEW JERSEY. Most diluent absorbent media are preferred for thinner powders and the thicker (impregnable) powders. Typically, diluent liquids are dissolved. written by MARSDEN SOLVENTS GUIDE 2ND ED., INTERSCIENCE,
NEW YORK, I95O. For suspension concentrations it is preferred to have a solubility below 0.1%; the solution concentrations are preferably constant over phase separation at 0 ° C <0c0 CUTCHEON'S DETER EMULSIFIERS ANNUAL MO PUBLISHING CORP. RIDGEWOOD, NEW JZ ^ SE and SISELY AND WOOD, ENCYCLOPEDIA OF SURFACE / CTIVE CHEMICAL PUBLISHING CO., INC. NEW YORK, 1964, catalog
GENTS AND '
I, apparently AGENTS;
<img file="GR76497B_D0085.tif" />
-83Substances and recommended uses. "The formulations are intended to contain a small amount of additives, to reduce the foaming of welding, oxidation, microbial annealing, etc.
The methods of preparing such compositions are well known. Solutions are prepared by simply mixing the ingredients.
Pulp solid compositions are prepared by admixture and usually by other means, such as hammer or fluid energy alone (FLUID ENERGY MILL). Suspensions are prepared by grinding mud / see for example 3; 060,084 U.S. Patent (disclaimer) LITTLSR 7; Granules and pellets are vibrated to prepare /<sup>on</sup> spraying the active! Material / Preformed Granular Carriers or by Techniques of Technical Coagulation. No JE BROWNING AGGLOMERATION ”CHEMICAL ENGINEERING, Dec 4, 1967, p. FF.
Example 46
Powdered Powder (1,1-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 40% sodium dioctyl sulfosuccinate 1.5% sodium lignosulphonate 3% methylcellulose 1.5% micellar 54%
The ingredients are thoroughly mixed, passed through a breeze, to produce particles of average size less than 15 microns, re-mixed and, before packaging, pass through a Sieves Sieve US No 50 (0.3 mm aperture).
<img file="GR76497B_D0086.tif" />
They will love you;
The compounds of the invention may be formulated in this manner.
-84I
Example 47
Wet Powder (4-Bromophyl Nyl) Dimethyl (1H-1, 2,4-triazol-1-ylmethyl) silicon methylcellulose low viscosity earth alkylonaphthalenesulfonate
20%
2%
2%
76% of you are a mill mill
The ingredients are mixed, grind hammered and then ground in an air mill to produce the active ingredient substantially below 10 microns in diameter.
The product is pre-packaged.
Example 48
Condensate Concentrate (s) (4-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 98.5% 0.5% silicon dioxide silicon aerosol 1.0%
I.
I.
The ingredients are mixed and milled with a hammer to produce a high concentration of concentrate (active constituent), passing substantially across the US series sieve. No 50 (aperture of 0.3 mm) This material can be educated in a variety of ways.
Example 49
Powder i
High concentrate (active ingredient) of Example 48. 25.4% pyrophyllite, powdered 74.6%
The ingredients are thoroughly mixed and packaged for use.
Example 5c 'Aqueous' Suspension (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1; ylmethylsilane
<img file="GR76497B_D0087.tif" />
-85 polyacrylic acid, gelling agent 0.3% ether dodecylphenyl polyethylene glycol 0.5% disodium phosphate 1.0% monosodium phosphate 0.5% polyvinyl alcohol 1.0% pentachlorophenyl 0.4% water 46%
The components are assembled in a sand grinder, producing substantially substantially less than 5 microns in size. Example 51 Emulsion particulate matter in a concentrate
Dimethyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 20% chlorobenzene 74% sorbitan monostearate and 6% polyoxyethylene concentrates
The constituents are combined and stirred, producing a solution which can be emulsified with water for application. Example 52
Emulsifiable Concentrate
30% Dimethyl (4-methylphenyl) (1H-1,2,4-triazol-1ylmethyl) silane
Mixture of oil-soluble 4% xylene sulfonates and polyoxyethylene ethers 66%
I.
The ingredients are combined and stirred under gentle heating, to ensure dissolution. During the packaging process a thin screen filter is included, ensuring the product is free of any foreign insoluble material.
Example 53
Granules
Wetting powder of Example 46 potassium sulfate gypsum
The ingredients are mixed
<img file="GR76497B_D0088.tif" />
-86 of these are sprayed with water, fiber granulation achieved. “When the largest-. The bulk of the material has assumed the desired size (I) of 0.42 mm. (US Series Sieve # 18 to 40), the granules are withdrawn, dried, and spun. The larger material is crushed to produce a desired area of material size. The granules taate contain (6 $) of active
<td colspan="2">component.</td>
<td>Example 54 Emulsifiable Concentrate</td><td>I. i</td>
<td>(2,4-Dichlorophenyl) dimethyl (ΐΉ-1,2,4-triazol-1ylmethyl) silanone</td><td> 30$</td>
<td>Mix of oil-soluble esters of sulfonates and polyoxyethylene ethers</td><td> 4$</td>
<td>xylene</td><td> 66$</td>
<td>The ingredients are combined and stirred</td><td>mild heat,</td>
<td colspan="2">to accelerate dissolution. During the packaging work</td>
<td>Thin screen filter is included, fiber secure in the absence of any foreign insoluble material;</td><td>do you have the product or</td>
<td>Example 55</td><td></td>
<td>Emulsifiable Concentrate Buccaryl-xorophenyl7-methoxy-T7-7-triaxox-1-ylmethyl) silane</td><td> 30$</td>
<td>Mix of oil-soluble esters of sulfonates and polyoxyethylene ethers</td><td> 4$</td>
<td>xylene</td><td> 66$</td>
t;
The ingredients are combined and stirred under gentle heating, to accelerate dissolution. The packaging work involves a thin screen filter, or the absence of any foreign insoluble Example 56
Emulsifiable concentrate of bis (4-Chlorophenyl) methyl (1H-1,2,4-ylmethyl) silane
Oil-soluble mixture of polyoxyethylene sulfonate intermediates
<img file="GR76497B_D0089.tif" />
-87xylol &&
The ingredients are combined and stirred gently,
to accelerate dissolution. The packaging work involves a thin screen filter, securing the product or the absence of any foreign insoluble material.
'' i
I.
Example 57
Emulsifiable bis (4-fluorophenyl) methyl (ΐH-1,2,4-triazol-1ylmethyl) silane 20% chlorobenzene 74% sorbitan monostearate and 6-polyoxyethylene concentrates
L.
The ingredients are combined and stirred to produce a solution which can be emulsified with water for application.
Example 58
Emulsifiable concentrate!
4-Fluorophenyl (methyl) phenyl (1H-1,2,4-triazol-1ylmethyl) silane 30 g
Mixture of oil-soluble sulfonates and polyoxyethylene ethers' $ 4 <sup>5</sup> xylene 66 $
The ingredients are combined and stirred under gentle heating to accelerate the dissolution.
a thin-film screen is obtained, securing the product or not *, as in any foreign insoluble material.
Example 59 - Cement Powder (1.1<sup>G.</sup>-Diphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) acetyl naphthalenesulfonate sodium methylcellulose low viscosity hammer diatomaceous earth and then grind mills
<td> 50$</td><td></td>
<td>$ 2 / - x</td><td></td>
<td>2t »</td><td></td>
<td>J $:<sub>;</sub>·</td><td>/ B.</td>
<td></td><td></td>
<td>I you j</td><td>most of the time</td>
<td></td><td> \<sup>?</sup>-ΐ!</td>
<td>mimat M.</td><td>viruses act.</td>
-88 component substantially less than 10 microns in diameter. The product is pre-packaged.
Leave blank_60
Liquid powder (1,1-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) diacetyl sulfosuccinate sodium lignosulfonate sodium methylcellulose low viscosity
4h%
1,5%
3%
1,5%
54%
The ingredients are thoroughly mixed, passed through an air mill, to produce particles of average size smaller than 15 microns, then mixed and, prior to packaging, passed through a US Sieve series. No. 50 (0.3 mm aperture) "It is possible for the compounds of the invention to be formulated in this manner.
I.
Example 61
Emulsifiable 30% silicon (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane concentrate
Mixture of oil-soluble esters of sulfonates and 4% polyoxyethylene ethers:
xylene 66%
The components are combined and stirred, under gentle heating, to accelerate dissolution. A thin screen filter is employed in the packaging process, the product is secured in the product or in the absence of any foreign insoluble material.
Example 62
Emulsifiable, Concentrated α (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1ylmethyl) chlorobenzene sorbitan monostearate and polyoxyethane concentrates
<img file="GR76497B_D0090.tif" />
-89The components are combined and stirred to produce a solution which can be emulsified with water for application.
Example_63
Aqueous 'Suspension (1,1' -Diphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane hydrogen atapulgite primary calcium lignosulfonate sodium dihydrogen phosphate
25%
3%
10%
0.5%
61.5%. A roller
The constituents are assembled in a ball mill until the solid particles are reduced to less than 10 microns in diameter.
Example 64
High Content Concentrate (an Active Ingredient) (1,1<sup>G.</sup>-Diphenyl-4-yl) dimethyl (1H-imdazol-1-ylmethyl) silane 93.5% 0.5% silicon aerosol aerosol 1.0% synthetic amorphous silicon dioxide 1.0%
The ingredients are mixed and milled through a high-concentrated hammer mill (active ingredient), passing through substantially all-in-line US No. 5c sieve (0.3 mm aperture). This material can be shaped in a variety of ways.
Example 65
Granules
Wetting powder of Example 60 Potassium sulphate gypsum
The components are mixed by rotating them with water sprayed, the granulation being achieved. Part of the material has the desired 1.0 to 0.42 mm. (Sieves I1PA # 18 to 40)
<img file="GR76497B_D0091.tif" />
and so on
': 0: -' -, Big Air
The largest material is crushed to produce a desired range (size) of complementary material. These granules contain (6%) of the active ingredient.
Example_66
High concentrate powder (active ingredient) of Example 64 25.4%;
pyrophyllite, powdered 74.6%,
The ingredients are mixed, carefully and packaged for use. i
Example_67
Emulsifiable Concentrate
4-chlorophenyl (methyl) phenyl (1H-imidazol-1-ylmethyl) silane 20% chlorobenzene 74% sorbitan monostearate and 6% polyoxyethylene concentrates
The components are combined by stirring to produce a solution which can be emulsified with water for application.
USER j
The compounds of the present invention are useful in controlling plant disease agents. They are effective in combating a wide range of plant diseases, particularly fungal pathogens (organisms) in ornamental crops, vegetables, wild, cereals and fruits, such as PUCCINIA RECOHDITA, ERYSIPHE GRAYORIPE ARAOHIDIGOLA, UROKYOES PHASBOLI κ <
ERUGTIGOLA, RHIZOCTONIA SOLANI, TPYZAE, P]
INESSTANS AND OTHER PHYTOPHTHORA SPECIES Pathogenic grains, such as PYTHIUM_APHANADEi 'The fight against the disease usually occurs in the
IHA
<img file="GR76497B_D0092.tif" />
Jun.
by applying an ineffective amount of the compound, either before or after infection, to the part of the plant to be protected, such as root, stems, foliage, fruit, seeds. tubers or bulbs, or the media (soil or sand) that grow the plants that are to be protected. The compounds can also be applied to the granule from which the plants to be protected are to be grown.
Application analogs for these compounds can be affected by many environmental factors and should be fluorescent under the actual conditions of use. million of active ingredient. Trees grown in treated soil at concentrations from 0.1 to about 20 mg / ha. can protect against disease. Grains and saplings can be protected normally when the grain is treated in an analogy of from 0.06 to about 3 grams per kilogram of grain.
The compounds of the present invention may be used with fungicides, bactericides, acaricides, filamentous pesticides, insecticides, or other biologically active compounds, for the purpose of achieving such desirable results. The amounts of these biologically active materials present in each weight portion of the composition of the present invention may vary from 0.05 to 25 parts by weight. · Other agents of this type are well known in this regard. Some are listed below:
Fungicides:
2-methyl benzimidazolecarbamate (carbentazim)
<img file="GR76497B_D0093.tif" />
Nidi-92-tetramethylthiouramide-disulfide (thiuram) n-dodecylguanidine acetate (dodin) ethylenediodysthiocarbamate magnesium (manneb)
1.4-dichloro-2,5-dimethoxybenzene (chloroneb)
Methyl 1- (butylcarbamoyl) -2-benzimidazolcarbamate (benenyl),
2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil), N-trichloromethylthiotetrahydrofalimide (captan), N-trichloromethylthiophthalimide (flop)>
4,4'- (o -phenylene) bis (3-thiophenylphenone) dimethyl (n -methylphenyl), '
2- (thiazol-4-yl) benzimidazole (thiabendazole), tris (O-ethylphosphonate) aluminum. (ALIETIE), tetrachloroisophthalonitrile (chlorothalonil),
2,6-dichloro-4-nitroaniline (dichloran), N- (2,6-dimethylphenyl ') - N- (methoxyacetyl) alanine methyl ester; (metallaxol), i
CIS-N- / (1,1,2,2-tetrachloroethyl) thio7cyclohex-4-ene-1,2-dicarboxiimide (captapol),
carboxamide of 3- (3,5-dichlorophenyl) ~ R ~ (1-methylethyl) -2,4-dioxo-1-imidazolidine (iprondione) i
3- (3 '5-dichlorophenyl) -5-ethenyl-5-methyl-2,4-oxazolidinodione (vincrosoline), I cassugamycin, |
5.5- diphenylphosphorodithioic acid 0-ethanol (opposite) j
Bactericides
Tribasic copper sulphate i streptomycin sulfate / λ J
<img file="GR76497B_D0094.tif" />
-93 (binapacryl)? -Methyl-1, -butylphenyl-3-β__7<sup>and</sup>'<sup>nonol</sup>'<sup>n</sup>·<sup>2</sup><sup><</sup>5<sup>d1</sup> (oxythioquinox)> 2,2,2-trichloro-1,1-bis (4-chlorophenyl) ethanol (dicofol), bis (pentachloro-2,4-cyclopentadien-1-ol) (dienechloro), tricyclohexyl hydroxide ), six (2-methyl-2-phenylpropyl) dicetroxane (fentanyl oxide)
Non-herbicides
2 - ^ * "two € Xu-i · ° x,<sup>u</sup><p<sup>oh</sup>nuomluno7- 1,3-dithiethane (fosthiethane),
1- (dimethylcarbamoyl) -N- (methylcarbamoyloxy) thioformimidate, S-mes';
oxyl,
S-methyl 1-carbamoyl-N- (methylcarbamoyloxy) thioformimidate,
0-a-ethyl-0 '- /' 4-thiomethyl) -] t-tolyl ~ 7-thiopyridine N-1-thiopropylphosphoric acid (Fenamic) 3-hydroxy (N-dimethro-dimethyro) Bentomicides (dimethylphosphate) ester ), methylcarbamidic acid ester with 2,3-dihydro-2,2-dimethyl-1,7-benzofuranol (carbofuran)
O, O'-dimethylester 0- / 2,4,5-trichloro-α- (chloromethyl) -benzyl7-phosphoric acid (tetrachlorinated),
S-ester of 2-mercaptoelectric acid diethyl ester with dimethyl thionophosphoric acid (malathion)
O, O-dimethyl-O - N - nitrophenylester phosphorothioic acid (methyl-parathion), methylcarbamidic acid ester with α-naphthol (carbaryl), <sup>:</sup>
H - / (methylamino) carbonyl ethoxy ethanimidothioate methanol (bromyl)
N '- (4-chloro-o-tolyl) -N, N-dimethylformamidine (buffer), ** /: LYXV th- (2-isopropyl-4-methyl-6-pyrimidyl) phosphorothiol ( XV ~ B-diethyl virus v ';'
-94 (diazinon);
Phenylphosphonothioate C-ethyl<sub>T.</sub> O-p-nitrophenyl (EPN),
4-Chloro-α- (ΐ-methylethyl) benzeneacetic acid (3-phenoxyphenyl) methyl (fenvalerate), L
(4 ·) -CIS. » TRAIL3-3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylate (3-phenoxyphenyl) methyl (permethrin),
N, N '- /' thiodis 7 (N-methylimino) carbonyloxy-bis / ethanimidothioate dimethyl (thionic acid)
0-ethyl-0- / 4- (methylthio) phenyl7-3-n-propylester phosphorothiolothionic acid (sulfur),
Α-cyano3-phenoxybenzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropylcarboxylate (cypermethrin),
4- (difluoromethoxy) -α- (methylethyl) benzeneacetic acid (3-phenoxyphenyl) methyl (PAYOFF),
O, O-diethyl (3,5,6-trichloro-2-pyridyl) phosphorothioate (chloropyrifox)
5-, (4-oxo-1,2,3-benzotriazine-3- (4H) -yl-) methyl7-phosphorodithioate (O-dimethyl) (azine-methyl),
5- (N-Formyl-N-methylcarbamoylmethyl) - 0-O-dimethyl (3-methyl) -phosphorodithium carbamate 5,6-dimethyl-2-dimethylamino-4-pyrimidinyl dimethyl (”PIRII40R) phosphorodithioate O, O-dimethyl (demetone-Semethyl),
CIS-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate, acyano-3-phenoxybenzyl (deltamethrin) cyano (3-phenoxyphenyl) methyl ester N- (2-chloroaline) MA.
The present invention is illustrated by way of Examples.
<img file="GR76497B_D0095.tif" />
-95 Example 68 The compounds of the present invention were dissolved in acetone, an amount equal to 6% of the final volume, and then suspended / concentrated to 100 ppm in purified water containing about 250 ppm of water (about 4 ppm). . The suspensions were then sprinkled, to the point of discharge, on wheat seedlings. The following day, the plants were inoculated with a suspension of PUOQIHIA PBGOKDITA parasiticus spores, a causative agent of the rusting of the wheat leaf, and left for 24 hours in a saturated chamber of 20 ° C. the estimates of the disease. The percentage of disease control is shown in the following table. The treated plants had little or no rust blisters, whereas the untreated plants had many rust blisters on each
I leaf.
TABLE 1
2®_Y_h_<sup>p</sup>E (dimethyl) phenyl (1,2,4-triazol-1-ylmethyl) silanone, (4-Boomophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silanone (1,1 ' -Diphenyl-4-yl) dimethyl) (1H-2,4-triazol-1-ylmethyl) silane (4-chlorophenyl> dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane
Butyl (4-chlorophenyl) methyl (1H-1, 2,4-triazol-1ylmethyl) silanone (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1ylmethyl) silanone (2 , 4-Dichlorophenyl) dimethyl (1H-1, 2,4-triazol-1ylmethyl) silane bis (4-chlorophenyl) (methyl) (1H ~ 1,2,4-triazol-1% Anti Wheat Rust
-------80
<img file="GR76497B_D0096.tif" />
-96 TABLE 1 (continued)
High Yield Methyl Silane% Anti-rusting Wheat __, _____
Dimethyl (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silicon 100 / 4- (ΐ, 1-dimethylethyl) phenyl7dimethyl (1H-1,2,4-triazol-1-ylmethyl) silicone ~
Butyl (2,4-dichlorophenyl) methyl (ΐ2-1,2,4-triazol1-ylmethyl) silane
Bis (2,4-Dichlorophenyl) (methyl) (1H-) 2,4-triazol-1-ylmethyl) silanone (2,4-Dichlorophenyl) methyl (phenyl) (1H-1,2,4-trihoacyclobenz) nin °<sup>THE</sup>^<sup>no</sup>m) (1H-1,2,4-triazolorphenyl) methyl (phenyl) (1H-1,2,4-triazol1-ylmethyl) silane
Dodecyl (dimethyl) (1H-1,2,4-triazol-1-ylmethyl) silane / "4- (4-chlorophenoxy) phenyl7dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane" ( 3,5-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane (1,1'-Diphenyl-4-yl) butyl (methyl) (1H-1,2,4-triazole) -1-ylmethyl) silane;
twice (1.1 <sup>G.</sup>-Diphenyl-4-yl) (methyl) (1H-1, 2,4-triazol1-ylmethyl) silanone (1,1 '-Diphenyl-4-yl) methyl (phenyl ((1X-1, 2,4-triazole)) -1-ylmethyl) silane (1,1 <sup>G.</sup>-Diphenyl-3-yl) dimethyl (1H-1,2,4-triazol-1ylmethyl) silane
2-Chlorophenyl (methyl) phenyl (1H-1,2,4-triazol-1 ylmethyl) silanose (2-chlorophenyl) 7methyl (1H-1,2,4-triazol) 1-methyl) silane ~ (1,1 <sup>G.</sup>-Diphenyl-4-yl) dimethyl (1H-1, 2,4-triazol-1 ylmethyl) silane, 4-dodecylbenzenesulfonic acid salt (1,1) <sup>G.</sup>-Diphenyl-4-yl) dimethyl (1H -), 2,4-triazol-1-methyl) silane, complexed with 1: 1 mild round chloride (II)
80'
100
100
100
100
100<sup>A</sup>
100
100
<img file="GR76497B_D0097.tif" />
(1,1 <sup>G.</sup>-Diphthyl-4-yl) dimethyl (1H-1, 2,4-triazol-1ylmethyl) silane, complex with manganese sulfate: 1
-97Table 1 (cont.)% Of the fight against the wheat germ in Scotland
2-Chlorophenyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane / bis (2-fluorophenyl) 7-methyl (1H-1,2,4-triazol-1-ylmethyl) silicon, hypochlorite 1: 1/1 * bis (2-fluorophenyl) 7-methyl (1H-1, 2,4-triazol-1 fluomethyl) silane, 2: 1 copper chloride complex (1.1 '-Diphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl'Silan (4-chlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane
Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane (1H-imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane
Dimethyl (1H-imid, dazol-1-ylmethyl) (4-methoxyphenyl) silanone (2,4-Dichlorophenyl) dimethyl (1H-Imidazol-1-ylmethyl) silanone bis (4-fluorophenyl) (1H-imidyl) ) methylsilane
Dimethyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) silane
Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethylphenyl) silane
Butyl (2,4-dichlorophenyl) (1H-imidazol-1-ylmethyl) methylsilicone bis (2,4-D-dichlorophenyl) (, 1H-imidazol-1-ylmethyl) methylsilane
2,4-Dichlorophenyl (1H- (midazol-1-ylmethyl) methyl (phenyl) silane
4-Chlorophenyl (1H-imidazol-1-ylmethyl) methyl (phenyl) silane
Dodecyl (dimethyl) (1H-imidazol-1-ylmethyl) silane / 4- (4-x lorofluoromethoxy) phenyl7dimethyl (1H-imidazol-1ylmethyl) silane ~
Butyl (1H-imidazol-1-ylmethyl) methyl (phenyl) silica
100
100
100
100
<img file="GR76497B_D0098.tif" />
i - ^ * 1> /
-98Table_1_ (Continued) fight against the “rusting” € 22_ — € 22 ___<sub>;</sub>____ (1,1 '-Diphenyl-4-yl) butyl (1H-imidazol-1-ylmethyl) methylsilane 100;
(1,1 '-Diphenyl-4-yl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 100, (1,1' -Diphenyl-3-yl) dimethyl (1H-imidazol-1-ylmethyl) 9H (4-Bromoethynyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silanone 90 (1,1'-Diphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) dimethyl silane 1: 1 100 (2-Chlorophenyl) (4-chlorophenyl (1H-imidazol-1ylmethyl) methylsilane 100 (2-chlorophenyl) (dimethyl) (1H-imidazol-1-ylmethyl) silane 80
A = “Compound was applied at a concentration of 200 PPM.
Example 69 Compounds of the present invention were dissolved in acetone, an amount equal to 6% of the final solvent, and then suspended in acetone.
concentration of 100 PPM in purified water containing 250 ';
PPM of TREM 014 surfactant (polyhydric esters)
W in alcohol). The suspensions were then sprinkled, to the point of discharge, on sycamore (cucumber) seedlings. The following day, the plants were inoculated with a spore suspension of the fungus ERYSIPHE CI0H0RACEARUM, a causative agent of the powdery mildew, and lost to a growth chamber. The following chart shows one hundred percent of the disease. The treated plants had little or no oyster, as opposed to what to look for! non<sup>1</sup> * / V ___ treated plants, which were covered with oleaginous shoots. On some plants, I do not combine with / after.
-99 of the disease, phytotoxicity in the form of growth restriction or hormonal effects was observed.
Table 2
As a% control of Siky (cucumber) (Dimethyl) phenyl (ΐ, 2.4 triazol-1-ylmethyl) silicon powder
Ethylenedimethyl (ΐH-2, 2,4-triazol-1-ylmethyl) silane
Butyldimethyl (1H-1,2,4-triazol-1-ylmethyl) silane
Dimethyl (4-methylphenyl) (1H-1,2,4-triazol1-ylmethyl) silane (4-Bromophenyl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silane (1,1'-Diphenyl-4) -yl) dimethyl (1X-S, 2,4-triazol1-ylmethyl) silane (4-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1 ylmethyl) silane
Butyl (4-chloroenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane
Dimethyl (1-naphthalenyl) (1H-1,2,4-triazol-1 ylmethyl) silane (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silane
Dimethyl (4-phenoxyphenyl) (1R-1,2,4-triazol1-ylmethyl) silane
Dimethyl (4-Methoxyphenyl) (1H-1,2,4-triazol-1ylmethyl) silanone (2,4-Dichlorophenyl) dimethyl (1H-1, 2,4-triazol1-ylmethyl) silane bis (4-Chloro) ethyl) (methyl) (1H-1,2,4-triazol1-ylmethyl) silanone (1H-1, 2,4-Triazol-1-ylmethyl) triphenylsilane
Cetyldiphenyl (1H-1,2,4-triazol-1-ylmethyl) silanone (1,1'-biphenyl-4-yl) dimethyl (4H-1,2,4-triazol4-ylmethyl) silane bis (4-fluorophenyl) (methyl) (1H-1,2,4-triazol-1ylmethyl) silane
100
100
100
1000<sup>;</sup>
1OO<sup>G</sup>
100
100
100G
100
100
100
100H
<img file="GR76497B_D0099.tif" />
.- / ¾ j .L ... ·
-100Table 2 (continued)
E____s_
Dimethyl (4-fluorophenyl) (1H-1,2,4-triazol-1ylmethyl) silane
Dimethyl (4-methylthiophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane
Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (4-trifluoromethylphenyl) silane
Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (3-trifluoromethylphenyl) silane
Dimethyl (1H-1, 2,4-triazol-1-ylmethyl) (2-trifluoromethylphenyl) silanone (2-Methoxyphenyl) dimethyl (1H-1,2,4-triazol-1ylmethyl) silane
Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silanone bis (2,4-dichloro-phenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) ) silane (2,4 * Dichlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silanone (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane (4-Fluorophenyl) methyl (phenyl (1H-1,2,4-triazol-1-ylmethyl) silane
Butyl (methyl) phenyl (1H-1, 2,4-triazol-1-ylmethyl) silanone (2,3-Dimethoxyphenyl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silicone (2,6) -Dimethoxyphenyl) dimethyl (1H-1, 2,4-triazol1-ylmethyl) silane
Dodecyl (dimethyl) (1X-1,2,4-triazol-1-ylmethyl) silane
2-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane / 4- (4-Chlorophenoxy) phenyl7dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane (1,1 ' -Diphenyl-4-yl) butyl (methyl) (1H-1,2,4triazol-1-ylmethyl) silicone% control of Erisibus powdery mildew (cucumber)
1000
100
1000
100
100
100G
1000
1000
1000
1000
100
100
1000
1000 ,0
<img file="GR76497B_D0100.tif" />
-101Table 2 (continued)
<td>Union</td><td>$ control of Eriksib powders of Sikyos (cucumber) _ ___</td>
<td>Butyl (4-fluorophenyl) methyl (1H-1,2,4 triazazol-1-ylmethyl) silane</td><td> 100</td>
<td>billion (1.1<sup>G.</sup>-Diphenyl-4-yl) (methyl) (1H-1,2,4 triazazol-1-ylmethyl) silane</td><td>i 100</td>
<td>(1,1'-Diphenyl-4-yl) methyl (phenyl) (1H1, 2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>(1H-Dimethylethoxy) methyl (phenyl) (1H-1,2, 4-triazol-1-ylmethyl) silane</td><td>I. 100</td>
<td>Ethyl (phenyl) (2-propoxy) (1H-1,2,4-triazol1-ylmethyl) silane</td><td>I. i 100</td>
<td>(1,1'-Diphenyl-2-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 90</td>
<td>2-Chloro-phenyl (methyl) phenyl (1H-1,2,4 triazazol-1-ylmethyl) silane</td><td> 100</td>
<td>4-Bromophenyl (methyl) phenyl (1H-1,2,4 triazol-1-ylmethyl) silane</td><td> 100</td>
<td>/ bis (2-Chlorophenyl) 7methyl (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 100</td>
<td>Cyclohexyl (dimethyl) (1H-1, 2,4-triazol-1-ylmethyl) silane</td><td>100G</td>
<td>/ bis (4-bromophenyl) 7methyl (1H-1,2,4-triazolT-ylmethyl) silane</td><td> 800 1</td>
<td>(1,1'-Diphenyl-4-yl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silane, 4-dodecylbenzenesulfonic acid salt.</td><td> 100 ' !</td>
<td>(1,1'-Diphenyl-4-yl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silane, complexed with 1: 1 copper hypochlorite</td><td> 100</td>
<td>(1,1'-Diphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1ylmethyl) silane, complexed with 1: 1 zinc chloride</td><td> ,<sup>80</sup></td>
<td> (1,1<sup>G.</sup>-Diphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1- ylmethyl) slanane, complex with manganese sulphate 1: 1</td><td>/ 3 ° /, J</td>
<td>2-Chlorophenyl (4-chlorophenyl) methyl (1H-1,2,4 triazazol-1-ylmethyl) silane></td><td>'; 10 <P</td>
<td>Bisyl (2-propoxy27 (1H-1, 2,4-triazol-1-yl = methyl) silane ~ /</td><td>rlo</td>
-102Table 2 (continued)% control of _Z c____> -P. ~ .tr \ ___ Erysibus the Sikyus (^ Cucumber)
<img file="GR76497B_D0101.tif" />
bis (2-fluorophenyl) 7methyl (1H-1,2,4-triazol-1-ylmethyl) silane, complexed with 1: 1 / 'bis (2-fluorophenyl) 7methyl (1H-1,2,4-) copper chloride triazol-1-ylmethyl) silane, complex with 2: 1 copper chloride
Dimethyl (1H-imidazol-1-ylmethyl) phenylsilanone
Aethyl (1H-imidazol-1-ylmethyl) dimethylsilane
Butyl (1H-imidazol-1-ylmethyl) dimethylsilane (1H-1-imidazol-1-ylmethyl) dimethyl (4-methylphenyl) silanone (4-Bromophenyl) (1H-1h dimazol-1-yl) methylsilane
(1,1'-Diphenyl-4-yl) dimethyl (1H-L-dazol-1-ylmethyl) silanone (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) dimethylbutyl (4-chlorophenyl) -imidazol-1-ylmethyl) methylsilane (1H-imidazol-1-ylmethyl) dimethyl (1-naphthalinyl) silanone (3,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) 1-dimethyl-1-dimethyl ylmethyl) dimethyl (4-phenoxyphenyl) silane
Dimethyl (1H-imidazol-1-ylmethyl) (4-methoxyphenyl) silane (2,4-Dichlorophenyl) dimethyl (1H-L, dazol-1-ylmethyl) silane bis (4-chlorophenyl) (1H-yl) 1-ylmethyl) methylsilane (1H-imidazol-1-ylmethyl) triphenylsilane
Biphenyl (1X-imidazol-1-ylmethyl) methylsilane / bis (4-fluorophenyl) (1H-im, dazol-1-ylmethyl) methyl- / silane /
Dimethyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) - / silane L-100
100
100
100
100
1000<sup>A</sup>
100
100
100
1000
100
100
100
100
I.
<img file="GR76497B_D0102.tif" />
-103Table 2 (cont.) $ Emerald pest control. Sibi's cucumber (cucumber)<sub>;</sub> “Union
Dimethyl (1H-L midazol-1-ylmethyl) (4-methylthiophenyl) silicone
Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethylphenyl) silane
Dimethyl (1H-imidazol-1-ylmethyl) (3-trifluoromethylphenyl) silane
2<sup>_</sup>4- (1, 1-Dimethylethyl) phenyl7 (1H-imidaz, ol-1 ylmethyl) dimethylsilane (1H-imidazol-1-ylmethyl) dimethyl (2-trifluoromethylphenyl) silane
Butyl (2,4-dichlorophenyl) (1H-imidazol-1-ylmethyl) methylsilicone bis (2,4-dichlorophenyl) (1H-imidazol-1-ylmethyl) -. methylsilane (2,4-Dichlorophen yl) (1H-L midazol-1-ylmethyl) methyl. (phenyl) silanone (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) -methyl (phenyl) silanone (4-fluoro-ethyl) (1H-imidazol-1-ylmethyl) methyl (phenyl).
(1H-imidazol-1-ylmethyl) (2-methoxyphenyl) dimethylsilane (2,3-Dimethoxyphenyl) (1H-imidazol-1-ylmethyl) dimethylsilane
Dodecyl (dimethyl) (1H-L midazol-1-ylmethyl) silanone (2-Chlorophenyl) (1H-L midazol-1-ylmethyl) dimethylsilane / ”4- (4-chlorophenoxy) phenyl7 dimethyl-dimethyl-dimethyl) silicone
Butyl (1H-imidazol-1-ylmethyl) methyl (phenyl) silanone (1.T-Biphenyl-4-yl) butyl (1H-imidazol-1-ylmethyl Amethylsilane)
Butyl (4-fluorophenyl) (1H-L midazol-1-ylmethyl) with thylosilane
Dibutyl (1H-imidazol-1-ylmethyl) methylsilicone (1,1-Biphenyl-4-yl) (1H-imidazol-1-ylmethyl) (phenyl) silane
<img file="GR76497B_D0103.tif" />
100
100
100G
100G100
100
100
100
1000
100
100
100
100 ~ ~ · · · · · ·. -n '
A '; c. / ·· '·
-114;
Table_2 (continued)% control of Erisibia powders
Compound of Siky (cucumber) (1,1-Dimethylethoxy) (1H-imidazol-1-ylmethyl) methyl (phenyl) silanone 100 (1H-imidazol-1-ylmethyl) methyl (phenyl) (2-propyl) (2-propyl) -imidazol-1-ylmethyl) / "bis (4-methoxyphenyl) 7-methylsilane" 50 (1,1'-Diphenyl-2-yl) dimethyl (1X-imidazol-1-ylmethyl) silane 50 (2-Chlorophenyl) -1-ylmethyl) methyl (phenyl) silanone 100 (4-Bromophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silanone 100
-chlorophenyl27 (1H-imidazol-1-ylmethyl) methylsilane ”100
Cyclohexyl (dimethyl) (1H-imidazol-1-ylmethyl) silane 100G '/ ~ bis (4-bromophenyl) 7- (1H-imidazol-1-ylmethyl) methylsilane' 100 (1,1'-biphenyl-4-yl) ) dimethyl (ΐH-imidazol-1-ylmethyl) silane, copper hypochlorite blocker <sup>1</sup>
1: 1; 100 (2-chlorophenyl) (4-chlorophenyl) (1H-imidazol-1ylmethyl) methylsilane 100 (2-chlorophenyl) (dimethyl) (1H-imidazol-1-ylmethyl) silane 80
Ab <sup>=</sup> growth restriction; and
Bg - Harmonic acting
Example 70 Compounds of the present invention were dissolved in acetone, in an amount equal to 6% of the final volume, and then suspended in a concentration of 100 PPM in purified water containing 25 ppm of surface: · Suspensions were then boiled to the point of exhaustion / in barley barley. The following day, the plants were inoculated / with transient - * 'spores of the fungus ERYSIPHE GRAKINI3, a topological agent; of kV
-105 ounces of barley oysters, and lost to 7 days growth chamber. Then he made estimates of the disease. * Percentage of disease control is shown in the following table. The treated plants had little or no powdery mildew, in contrast to the untreated plants that were covered with powdery mildew.
ILINAX 3 “Union
Butyl (4-chlorophenyl) methyl (1H-1,2,4 triazol-1-ylmethyl) silane (3,4-Dichlorophenyl) dimethyl (1H-1,2,4 triazol-1-ylmethyl) silane
Dimethyl (4-Methoxyphenyl) (1H-1,2,4-triazol-4-ylmethyl) silanone (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silanone% Powders Control oyster mill<sup>K</sup>_____: _____
100
100
I.
100 cis (4-chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silanone 100 (1H-1,2,4-triazol-1-ylmethyl) triphenylsilane 100
Methylldiphenyl (1H-2,4-triazol-1-ylmethyl} silane 100
Dimethyl- (1H-1,2,4-triazol-1-ylmethyl) (2-trifluoromethylphenyl) silicone 100
Dodecyl (dimethyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100<sup>J</sup>
Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 100 (3,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 80
Dimethyl (1H-imidazol-1-ylmethyl) (4-methoxyphenyl) silanone 100 (2.4-Dichlorophenyl) dimethyl (1H-L midazol-1-ylmethyl) silage 100.
bis (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane ic
Biphenyl (1H-imidazol-1-ylmethyl) methylsilane
Dimethyl (1H-L-midazol-1-ylmethyl) (4-trifluoromethyl-phenyl) silane
<img file="GR76497B_D0104.tif" />
-106Table_3 (continued) ———— | % control of Erisibia powders: Union <________: _______.
Dodecyl (dimethyl) (1H-imidazol-1-ylmethyl).
silicone 100 *
A- “The compound was applied at a concentration of 200 PPM.
2 Compounds of the present invention were dissolved in acetone in an amount equal to 6% of the final volume, and then suspended in a concentration of 100 ppm in purified water containing 250 ppm of water. / These suspensions were sprayed, to the point of discharge, on apple seedlings. The following day, the plants were inoculated with a spore suspension of the fungus VENTURIA INAEQUALIS, a causative agent of the apple foliage, and were left in a saturated moisture chamber for 2 hours at 20 ° C for 24 hours. They then made assessments of the disease and recorded it
I will show you the following table. Treated plants had fewer fescue oil changes when treated with untreated plants, which were covered * *<sup>1</sup> by fusion cyclic changes. In some plants, in combination with the control of the disease, phytotoxicity was observed as a growth restriction.
Table 4
Notice
Dimethyl (4-methylphenyl) (1H-1, 2,4-triazol-2-ylmethyl) silane (4-Bromophenyl) oxy (1H-1, 2,4-triazol-1-ylmethyl) silane (1,1'-Diphenyl-4-yl) dimethyl (1H-1, 2,4-triazol-1-ylmethyl) silane (4-Chlorophenyl) dimethyl (1H-1, 2,4-triazol-1-ylmethyl) silane % control of Mila's fuselage
<img file="GR76497B_D0105.tif" />
—107—
Table_4_ (continued)
Compound% combustion of its fuselic acid
Miley
Butyl (4'-chlorophenyl) methyl (1H-1,2,4-triazolylmethyl) silanone 1000
Dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 50 (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 80
Dimethyl (4-phenoxyphyl) ((1H-1,2,4-triazol-1ylmethyl) silane 100
Dimethyl (4-methoxyphenyl) (1H-1,2,4-triazol-1ylmethyl) silane 100 L (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-!
ylmethyl) silane 100 <sup>!</sup> bis (4-chlorophenyl) (methyl) (1H -), 2,4-triazol-1ylmethyl) silane 100
Methylldiphenyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1,1C-Biphenyl-4-yl) dimethyl (4H-1,2,4-triazol-1-ylmethyl) silicone 80 J bis (4-fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100 •. i
Dimethyl (4-fluorophenyl (1H-1,2,4-triazol-L-ylmethyl) silyl 80i
I.
I.
Dimethyl (4-methylthiophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 60i
Dimethyl (1H-1,2,4-triazol-1-ylmethyl) - (2-trifluoro-A 0 methylphenyl) silane 65Cr j (2-Methoxyphenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl);
silane) 80
Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1 ylmethyl) silane (1H-1,2,4-triazol-1-ylmethyl) silanone (1H-1,2,4-triazol-1 ylmethyl) 2,4-Dichlorophenyl) methyl (phenyl (1H-1,2,4-triazol1-ylmethyl) silane (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazolyl-methyl) silicon (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1 ylmethyl) silane
<img file="GR76497B_D0106.tif" />
-108Illax 4 (cont'd) control no
E oh_s_ £ _s
Butyl (methyl) phenyl (1E-1,2,4-triazol-1ylmethyl) silicone silicone
Quercetin of Nododecyl (dimethyl) (1H-1, 2,4-triazol-1-ylmethyl) silane 40 '(2-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 ^<sup>_</sup>4- (4-Chlorophenoxy) phenyl7dimethyl (1H-1, 2,4tr iszol-1-ylmethyl) silyl 100 (1,1'-biphenyl-4-yl) butyl (methyl) (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,?, 4-triazol-1) 100 (1,1'-Biphenyl-2-yl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silanone 100 (1,1'-Diphenyl-3-yl) dimethyl (1X-1) , 2,4-triazol1-ylmethyl) silane 50
2- Chlorophenyl (methyl) phenyl (1H-1,2,4-triazol1-ylmethyl) silane 90
4-Bromophenyl (methyl) phenyl (1H-1,2,4-triazol1-ylmethyl) silane 100 / 'bis (2-chlorophenyl27methyl (1B-1,2,4-triazol-1ylmethyl) silane' 40 / ~ bis 4-Bromophenyl) 7-methyl (1H-1,2,4-triazol-1-ylmethyl) silane ~ 80 (1,1'-Diphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, salt 4-dodecylbenzenesulfonic acid 100 (1,1 '-Diphenyl-4-yl) dimethyl (1H-1,2)<sub>?</sub>4-triazol1-ylmethyl) silane, 1: 1 100 (1,1 '-Diphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1ylmethyl) silane complex with copper chloride hypochlorite / / (1) 1QO (1,1 '-Diphenyl-4-yl) dimethyl (-H-1,2,4-triazol-1ylmethyl) silanone (ΐΐ) 1: 1 yl, complexed with 1: 1 y manganese sulfate
100
-109Table_4 (continued)% of its fusible oil control
________ _____ Ileas
2-Chlorophenyl (4-chlorophenyl) methyl (1H-1,2,4 triazol-1-ylmethyl) silane 90
2-Chlorophenyl (dimethyl) z 1 H-1, 2,4-triazol-1-ylmethyl) silane 60 (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 80
Butyl (4-chlorophenyl) (1H-L midazol-1-ylmethyl) methylsilane 90 (1H-imidazol-1-ylmethyl) dimethyl (1-naphthalinyl) silanone 40 (3,4-Dichlorophenyl) (1H-imidazol) ylmethyl) dimethylsilane 80 (1H-imdazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silanone 100 (3.4-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane
Bisphenyl (1H-imidazol-1-ylmethyl) methylsilane 50 bis (4-fluorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 100
Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethylphenyl) silane / ~ 4- (1,1-Dimethylethyl) phenyl7 (1H-imidazol-1-ylmethyl) dimethylsilane
Butyl (2,4-dichlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane bis (2,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane (2,4-Dichlorophenyl) -1-ylmethyl) methyl (phenyl) silanone) (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenylphylanyl) (4-fluorophenyl) (1H-imidazol-1-ylmethyl) H-imidazol-1-ylmethyl) (2-methoxyphenyl) dimethylsilane I (2-chlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilyl;
100B
100
<img file="GR76497B_D0107.tif" />
-110 Table_4 (continued)% Combat
Milk fuselage compound
Butyl (1H-Imidazol-1-ylmethyl) methyl (phenyl) silane 80 (1,1'-Biphenyl-4-yl) butyl (1H-imidazol-1-ylmethyl) methylsilane 100>
Butyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 80
Dibutyl (1H-imidazol-1-ylmethyl) methylsilane 30 bis (1,1 '-Biphenyl-4-yl) (1H-imidazol-1-ylmethyl) methylsilane 50 (1H-imidazol-1-ylmethyl) 4-methoxyphenyl) 7-methylsilane 50 '(1,1 <sup>G.</sup>-Diphenyl-2-yl) dimethyl (1H-imidazole-1-ylmethyl) silane 90 (1,1'-Biphenyl-3-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 90 (2-chloroethyl) -imy, dazol-1-ylmethyl) methyl (phenyl) silanone 100 (4-Bromophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 30 / bis (2-chlorophenyl27 (1H-yl) ylmethyl) methylsilane '60
Dimethyl (1H-imidazl-1-ylmethyl) (4-methylsulfonylphenyl) silane 80
Cyclohexyl (dimethyl) (1H-imidazol-1-ylmethyl) silavuov 100B
2 "bis (4-bromophenyl) _7 (1H-imidazol-1-ylmethyl) methylsilane" 50 (1,1'-Biphenyl-4-yl) dimethyl (| H -imidazol-1-ylmethyl) silicon, sublocal post hypochloro 1: 1. 100 (2-chlorophenyl) (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane (1H-imidazol-1-ylmethyl) phenyl / bis (2-propoxy) 7-silan (2-chloro) diethyl) (1H-L-diazol-1-ylmethyl) silane
<img file="GR76497B_D0108.tif" />
D.<sub>&</sub> - restriction of displacement B.<sub>b</sub>= chlorosis
The compound was applied at a concentration of 400 ppm aft's / 'XX-XV-X' .'jsK · '
OS! .
-111 Example 72 'Compounds of the present invention were dissolved in acetone, an amount equal to 6% of the final volume, and then suspended in conc. 100 PPM in purified water containing 250 ppm of TH: The suspensions were then sprinkled, to the point of discharge, on maize seedlings. The following day the plants were inoculated with a HBU-IIKTHOSPORIUI spore suspension; NSAIDs were the causative agent of the southern maize leaf (southern flounder), and were lost to a saturated humidity chamber at 20 ° C for 24 hours and had a growth chamber of 7 days. The percentage of disease control is shown in the following table. The treated plants had little or no alterations, while the untreated plants had many leaf lesions on each leaf.
Table 5% control of the red<sub>u</sub> leaf (Compound) leaf Compound of Southern Corn (4-Bromophenyl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silanone 90 (1,1 '-Diphenyl-4-yl) dimethyl (1H) 1,2,4-Triazol-1-ylmethyl) silane (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane
Dimethyl (4-Methoxyphenyl) (1H-1,2,4-triazol1-ylmethyl) silanone (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silanone bis (4-chloroenyl) ) (methyl) (1H-1,2,4-triazol1-ylmethyl) silane
Methyldiphenyl (1H-1, 2,4-triazol-1-ylmethyl) silane '
<img file="GR76497B_D0109.tif" />
<img file="GR76497B_D0110.tif" />
<img file="GR76497B_D0111.tif" />
-112 Table 5 (cont'd) "Eighty percent of the fatty acids of the southern maize leaf ___ (1,1'-Biphenyl-4-yl) dimethyl (4H-1,2,4 triazol-4)" bis (4-fluorophenyl) (methyl) (1H-1,2,4 triazazol-1-ylmethyl) silane-ylmethyl) silane
Dimethyl (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane
Dimethyl (4-methylthiophenyl) (1H-1,2,4 triazol-1-ylmethyl) silane
Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (4trifluoromethylphenyl) silane
C4- (1,1-Dimethylethyl) phenyl7 dimethyl (PHH-2,4-triazol-1-ylmethyl) silicon (2-Methoxyphenyl) dimethyl (1H-1, 2,4-triazol1-ylmethyl) silane
Butyl (2,4-dichloroenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane bis (2,4-dichlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silicon (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4 triazol-1-ylmethyl) silanone (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4 triazol-1-ylmethyl) silane (2-Chlorophenyl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silane
Z4 - (4-chlorophenoxy) phenyl7dimethyl (1X1,2,4-triazol-1-ylmethyl) silane
100
100 .80
100 (3,5-Dichlorophenyl) dimethyl (1H-1,2,4-dimethyl) (1,1'-biphenyl-4-yl) butyl (1H-1,2,4tr) jazol-1-ylmethyl) silane (1,1'-Diphenyl-4-yl) methyl (phenyl) (1H-1,2,4 triazol-1-ylmethyl) silane / bis (4-Methoxyphenyl27methyl (1H-1,2) , 4-Triazol-1-ylmethyl) silanone (1,1 '-Diphenyl-2-yl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silane (1,1' -Diphenyl-3-yl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silane
100
<img file="GR76497B_D0112.tif" />
-113Table 5 (continued)
<td>“Emotion</td><td>% control of the fern on the leaf of South Maize</td>
<td>2-chlorophenyl (methyl) phenyl (1H-1,2,4-tria-</td><td></td>
<td>zol-1-ylmethyl) silane</td><td> 100</td>
<td>4-Bromophenyl (methyl) phenyl (1H-1,2,4-tria)</td><td></td>
<td>zol-1-ylmethyl) silane</td><td> 80 )</td>
<td>Diss (2-chlorophenyl) 7-methyl (1H-1,2,4-tria)</td><td></td>
<td>zol-1-ylmethyl) silane</td><td> 60 !</td>
<td>Cyclohexyl (dimethyl) z 1 H-1,2,4-triazol-1-yl-</td><td></td>
<td>methyl) silane</td><td><sup>50</sup></td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-tria)</td><td></td>
<td>zol-1-ylmethyl) silane, 4-dodecylbenzo salt</td><td></td>
<td>lsulfonic acid</td><td> 100</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-tria)</td><td></td>
<td>zol-1-ylmethyl) silane, a block after sub-</td><td></td>
<td>1: 1 copper chloride</td><td> 100</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-tria)</td><td><sup>1</sup></td>
<td>zol-1-ylmethyl) silane, complex with chloro-</td><td></td>
<td>zinc (II) 141</td><td> 90</td>
<td>(1'-Diphenyl-4-yl) dimethyl (1H-1,2,4-tria)</td><td></td>
<td>zol-1-ylmethyl) silane, complex with sulfur-</td><td> !</td>
<td>of 1: 1 manganese</td><td>100 I.</td>
<td>2-Chlorophenyl (4-chlorophenyl) methyl (1H-1,2,</td><td></td>
<td>4-triazol-1-ylmethyl) silane</td><td> 60</td>
<td>(1,1'-Diphenyl-4-yl) omethyl (1H-imidazol-1-</td><td></td>
<td>ylmethyl) silane</td><td> 90</td>
<td>Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl-</td><td></td>
<td>methylsilane)</td><td> 50</td>
<td>(3,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl)</td><td></td>
<td>dimethylsilane</td><td> 7°</td>
<td>(2,4-Dichlorophenyl) dimethyl (1H-imidazol-1-</td><td></td>
<td>ylmethyl) silane</td><td> 70</td>
<td>bis (4-chlorophenyl) (1H-imidazol-1-ylmethyl) -</td><td></td>
<td>methylsilane</td><td> 60</td>
(1H-imidazol-1-ylmethyl) triphenylsilane
Biphenyl (1H-imidazol-1-ylmethyl) methylsilicone bis (4-fluorophenyl) (1X-imidazol-1-ylmethyl) methylsilane
Z ~ 4- (1,1-Dimethylethyl) phenyl / (1H-imidazol-1ylmethyl) dimethylsilane ”
<img file="GR76497B_D0113.tif" />
-114Table_5 (continued)% control of oil on the leaf
G-P * I · L Z _ <sup>1</sup>
<td>“South West</td><td>Maize</td>
<td>(1H-Imidazol-1-ylmethyl) dimethyl (2-trifluoromethylphenyl) silane</td><td> 90 .</td>
<td>Butyl (2,4-dichlorophenyl) (1H-imidazol1-ylmethyl) methylsilane</td><td> 80</td>
<td>bis (2,4-dichlorophenyl) (1H-imidazol-1ylmethyl) methylsilane</td><td> 80</td>
<td>(4-fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 80</td>
<td>(2,6-Dimethoxyphenyl) (dimethyl) (1H-imidazol-1-ylmethyl) silane</td><td><sup>50</sup></td>
<td>Dibutyl (1H-imidazol-1-ylmethyl) methylsilane</td><td> 90</td>
<td>1,1'-Biphenyl-4-yl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 80</td>
<td> (1,1 <sup>G.</sup>-Diphenyl-3-yl) dimethyl (1H-imidazol-1ylmethyl) silane</td><td>90 L</td>
<td>bis (2-chlorophenyl27 (1H-imidazol-1-ylmethyl) methylsilane ~</td><td>9h</td>
<td>Hyclohexyl (dimethyl) (1H-imidazol-1-ylmethyl) silane</td><td> 50</td>
<td>Example 73</td><td></td>
<td>Compounds of the present invention have been diluted</td><td>you acetone, you who;</td>
Equal to 6% final solution, and the suspension was suspended in a concentration of 100 ppm in purified water containing 250 ppm of: surface active substance TREM 014 (polyhydric alcohol esters). effluent, on peanut seedlings. The following day, the plants were inoculated with a suspension of CERP300PROPAL_ALEA0HB0000A spores, a 24-hour-old morning-blooming spider, and a 27-day-old seaweed. growth rates were based on estimates of the disease
SSI.
next Table. The treated plants had a few or no leaf spots, whereas the non-treated plants had a lot of leaf spots. For some plants treated, in combination with the control of the disease, phytotoxicity was expressed as burning.
Table 6% Early Stain Control <sup>p</sup>Sheet of Leaf Species of bis (4-chlorophenyl) (methyl) (1H-1,2,4-tria-).
zol-1-ylmethyl) silanone-100
Methylldiphenyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1,1 '-Diphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane (4- chlorophenyl) dimethyl (1H-1,2,4-triazol-1ylmethyl) silane
Dimethyl (1-Naphthalenyl) (1H-1, 2,4-triazol-1-ylmethyl) silanone (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silanone bis (4-fluoroenoyl) ) (methyl) (1H-1,2,4-triazol1-ylmethyl) silane
Dimethyl (4-fluorophenyl) (1H-1, 2,4-triazol-1ylmethyl) silanone / 4- (1H-1-dimethylethyl) phenyl7dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane
Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (2-trifluoromethylphenyl) silicone
Butyl (2,4-dichloroenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silicone bis (2,4-dichloroenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silanone (2,4-Dichlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) phenyl (1H-1,2,4 triazol-1-ylmethyl) silanone (4-chlorophenyl) methyl (phenyl) silane (4-fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane
100
100
100
25<sup>1</sup>
100
100
100
<img file="GR76497B_D0114.tif" />
·<«.·
-116Table 6 (continued)
Okay
2- (Chlorophenyl) dimethyl (1H-1,2,4-trnazol1-ylmethyl) silanone (1,1'-Diphenyl-4-yl) butyl (methyl) (1H-
1,2,4-triazol-1-ylmethyl) silane bis (1H, 1'-biphenyl-4-yl) methyl (1H-1,2,4 triazol-1-ylmethyl) silane (1, 1<sup>G.</sup>-Diphenyl-4-yl) methyl (phenyl) (1H1,2,4-triazol-1-ylmethyl) silane / bis (4-Methoxyphenyl) 7methyl (1H-1,2,4triazol-1-ylmethyl) silane (1,1'-Diphenyl-2-yl) dimethyl (1H-1,2,4 triazol-1-ylmethyl) silanone (1,1 '-Diphenyl-3-yl) dimethyl (1H-1,2,4 triazol) 1-ylmethyl) silane
2-chlorophenyl (methyl) phenyl1 H-1,2,4 triazol-1-ylmethyl) silane
4-Bromophenyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane / bis (2-chlorophenyl) 7-methyl (1H-1,4,4-azazol-1-ylmethyl) silane / 'bis - (4-Bromophenyl27methyl (1H-1,2,4triazol-1-ylmethyl) silane (1,1'-Diphenyl-4-yl) dimethyl silane -H-1,2,4triazol-1-ylmethyl) silane , 4-dodecylbenzenesulfonic acid salt (1,1'-Biphenyl-4-yl) dimethyl (1H-1, 2,4tr azazl-1-ylmethyl) silane, 1: 1 (1,1'-Biphenyl-4-yl) dimethyl (1H-12,4 triazol-1-ylmethyl) silane complex with copper hypochloride, 1: 1 (1, zinc chloride complex) (1, 1 '-Diphenyl-4-yl) dimethyl (1H-2,4,4-azazol-1-ylmethyl) silane, complexed with 1: 1 manganese sulfate
2-Chlorophenyl (4-chlorophenyl) methyl (1H1,2,4-triazol-1-ylmethyl) silane / bis (2-fluorophenyl27methyl (1H-1,2,4-triazol-1-ylmethyl) silane Copper Chloride 1: 1: 1 'Combating Early Spotting on Peanut Leaf'
100
100
100
100
100
100
100
100
100
100
100
<img file="GR76497B_D0115.tif" />
CL · “1) Il
-117 Table 6 (cont.)% Of the Early Spotting of Peanut Spotted Peanut ___________: ______ / "bis (2-fluorophenyl) 7methyl (ΐH-1,2,4trazazol-1-ylmethyl) silanil" 2: 1 100 (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol1-ylmethyl) silicon 100 (2, A-DichlorophenylimethylethylH-imidazolyl-ylmethyl) copper copper chloride
Biphenyl (1X-imidazol-1-ylmethyl) methyl-50 silane bis (4-fluorophenyl) (1X-imidazol-1-ylmethyl) methylsilane 100
Dimethyl (4-fluorophenyl) (ΐH-imidazol-1-ylmethyl) silane ~ 60B
36 ° Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoro-methylphenyl) silane:
Dimethyl (1H-imidazol-1-ylmethyl) (3-trifluoromethylphenyl) silicone 50
Butyl (2,4-dichlorophenyl) (1H-imidazol-1ylmethyl) methylsilane 90 (2,4-dichlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 90 (2,4-Dichlorophenyl) ylmethyl) methyl (phenyl) silanone 100 (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silanone 100 (4-fluorophenyl) (1H-imidazol-1-ylmethyl) 100 (2-chlorophenyl) (1H- (m, dazol-1-ylmethyl) dimer!
thylosilane 80 (1,1 '-Diphenyl-4-yl) butyl (1H-imidazol-1ylmethyl) methylsilane 90 billion (ΐ, 1 <sup>G.</sup>-Diphenyl-4-yl) (1H-imid, dazol-1-ylmethyl) methylsilane (1,1 '-Diphenyl-4-yl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane (1,1') -Diphenyl-2-yl) dimethyl (1H-imidazol-1-ylmethyl) silanone (1,1) <sup>G.</sup>-Diphenyl-3-yl) dimethyl (1H-imidazol-1ylmethyl) silane
<img file="GR76497B_D0116.tif" />
—118—
Table__6 (continued) <sup>W</sup>Anti-Spotting Sheet (2-Chlorophenyl) (1H-L midazol-1-ylmethyl) methyl (phenyl) methyl (phenyl) silane 100% (4-bromophenyl) (1-bromophenyl) ) 9-methyl (phenyl) silane 9'-bis (2-chlorophenyl) Y7 (1H-L midazol-1-ylmethyl) methyl silane 100;
/ ”Bis (4-bromophenyl27 (1H-imidazol-1-ylmethyl) methylsilicane 5H (1,1'-Diphenyl-4-yl) dimethyl (1H-imidazol1-ylmethyl) silicone: 1 1 · 100:
(2-chlorophenyl) (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 80
Ath - phytotoxic burning
B = compound applied at a concentration of 40 µg PPM.
i
Example 74 Compounds of the present invention were dissolved in acetone, an amount equal to 6% of the final volume, and suspended in 1%.
concentration of 80 PPM in purified water containing 250 PPM of surfactant THEM 014 (polyhydric alcohol esters;
<img file="GR76497B_D0117.tif" />
fungal spore verb, gROMYCES PHASE0LI, causative agent-
<img file="GR76497B_D0118.tif" />
In the treatment, in combination with the fight against disease, phytotoxicity in the form of growth restriction was observed.
Table_7% Fighting Her?
<td><sup>u</sup>Notice</td><td>of Fassiolou</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4 triazol-1-ylmethyl) silane</td><td> 100</td>
<td>(2,4-Dichlorophenyl) dimethyl (1H-1,2,4-</td><td><sub>L.</sub> A</td>
<td>triazol-1-ylmethyl) silane</td><td>30G<sup>a</sup></td>
<td>bis (4-chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td>100G-</td>
<td>(4-chlorophenyl) methyl (phenyl) (1H-1,2,4 triazol-1-ylmethyl) silane</td><td>98B</td>
<td>(4-fluorophenyl) methyl (phenyl) (1H-1,2,4 triazol-1-ylmethyl) silane</td><td> 100®</td>
<td>bis (4-fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td> 96<sup>s</sup></td>
<td>(1,1'-Diphenyl-4-yl) dimethyl (1H-imidazol1-ylmethyl) silane</td><td> 100</td>
<td>(2,4-Dichlorophenyl) dimethyl (1H-imi, dazol1-ylmethyl) silane</td><td> 83</td>
<td>Aq = growth restriction</td><td></td>
B = compound was applied at a concentration of 16 PPM
Example 75 Compounds of the present invention were dissolved in acetone, in an amount equal to 5% of the final volume, and suspended in a concentration of 100 PPM in purified water containing about 700 PPM of surfactant. The suspension was immersed in three minutes of iconic canned peach halves and then placed in sterile, dry air containers. Upon drying, the peaches halves were inoculated with two pieces of MONILINIA PRUOTlboLA MY0EUUM, the causative agent of grayish brown rash.<sup>Managing</sup> Car- / · / \ - i · ^ \ say, and they lost to sterile container containers. At that time, on each peach was removed)
-120aktines of the developed colonies .'Epi of submitted not treated peaches were grown colonies or grown only oligo millimeters in diameter, while ekeinai al grow for untreated treated peaches covered the range entire surface of rodakinou.'I percent control of disease (on one hundred percent inhibition of colony growth on weed-treated peaches, as applied to those colonies untreated peaches) are expressed in the Table below.
Table 8 c <sup>g</sup> (Dimethyl) Phenyl (1,2,4-Triazol-1-ylmethyl) Silane% Combat Gray Separation (Butyl) Dimethyl (1H-1,2,4-Triazol-1-ylmethyl) Silane 95 (1 , 1'-Diphenyl-4-yl) dimethyl (1H-1,2,4 triazol-1-ylmethyl) silane 100
Butyl (4-chlorophenyl) methyl (1H-1,2,4 triazol-1-ylmethyl) silane
Dimethyl (4-Methoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane (4-chlorophenyl) (methyl) (1H-1,2,4 triazol-1-ylmethyl) silanone (1,1'-Biphenyl-4-yl) dimethyl (4H-1,2,4 triazol-4-ylmethyl) silane (4-fluorophenyl) ) methyl (1H-1,2,4-triazol-1-ylmethyl) silane
Butyl (2,4-dichloroenyl) methyl (1H-1,2,4 triazol-1-ylmethyl / silane (4-chlorophenyl) methyl (phenyl) (.1 H-1, 2,4-triazol-1-ylmethyl) silane (4-fluorophenyl) methyl (phenyl) (1H-1,2,4 triazol-1-ylmethyl) silane
Butyl (4-fluorophenyl) methyl (1H-1, 2,4 triazol-1-ylmethyl) silane
100
100
<img file="GR76497B_D0119.tif" />
-121Table_8_ (continued)% Fight against it
<td>Union</td><td>Feeding Sepsis</td>
<td>Dibutyl (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane</td><td><sup>81</sup></td>
<td>(1,1'-Diphenyl-4-yl) dimethyl (1H-imidazol-1 ylmethyl) silane</td><td>83 I.</td>
<td>Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane</td><td> 45</td>
<td>(1H-L midazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane</td><td> 80</td>
<td>(2,4-dichlorophenyl) dimethyl (1H-imidazol-1 ylmethyl) silane</td><td> 100</td>
<td colspan="2">Biphenyl (1H-imidazol-1-ylmethyl) methylsilane 76</td>
<td>(4-chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 45</td>
<td>(4-fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane</td><td> 65</td>
<td>Example 76</td><td></td>
Imbrosions of the present invention were dissolved in acetone, in an amount equal to 6% of the final volume, and then suspended in a concentration of 100 PPM in purified water containing 250 PPM of superficial superficial. This suspension was lifted to the point of no more!
rice paddies. The following day, the plants were inoculated with a mixture of bran and mycelium (cultivated) RHIZ0CT0NIA 30LANI, the causative agent of the rice leaf oil, and were left alone for 7 days. Vita made disease estimates. * Percentage of disease control is highlighted in the following Table. The treated plants had a small amount of silt in contrast to the untreated plants which were covered by a silty silt (
<img file="GR76497B_D0120.tif" />
-122Table 9
2® (1,1<sup>g</sup>-Diphenyl-4-yl) dimethyl (1H-1,2,4 triazol-1-ylmethyl) silanone (3,4-Dichlorophenyl) omethyl (1H-1,2,4 triazol-1-ylmethyl) silane
6is (4-Dorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silanone / "4- (1,1-dimethylethyl) phenyl7dimethylT1H-1,2,4-triazol-1-ylmethylsilane"
Butyl (2,4-dichlorophenyl) methyl (1H1,2,4-triazol-1-ylmethyl) silane (4-chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane (4-fluorophenyl) ) methyl (phenyl) (1H-1,2,4 triazol-ylmethyl) silane
Butyl (methyl) phenyl (1H-I, 2,4-triazol1-ylmethyl) silane (1,1)<sup>G.</sup>-biphenyl-4-yl) butyl (methyl (1H-1, 2,4-triazol-1-ylmethyl) silane
Butyl (4-fluorophenyl) methyl (1H-1,2,4 triazol-1-ylmethyl) silane.
bis (1H, 1-diphenyl-4-yl) (methyl) (1H-1,2,4triazol-1-ylmethyl) silan / bis (4-methoxyphenyl) 7methyl (1H-1,2,4triazol-1-ylmethyl) ) silicone
2-Chlorophenyl (methyl) phenyl (1H-1,2,4 triazazol-1-ylmethyl) silanone
4-Bromophenyl (methyl) phenyl (1H-1,2,4 triazol-1-ylmethyl) silane / bis (2-chlorophenylth27methyl (1H-1,2,4 triazol-1-ylmethyl) silane (1,1'- Biphenyl-4-yl) dimethyl (1H-1,2,4tr yazfl-1-ylmethyl) silane, complexed with 1: 1 (1,1 '-Diphenyl-4-yl) imethyl (1H-2,4-yl) 2,4-triazole -1-ylmethyl) silane, complex with zinc chloride (II) 1: 1 $ Combat, Elysium to Rice
I
<sup>5</sup>° ,
I ΐ
}
I.
<sup>80</sup> ;
ΐ
<img file="GR76497B_D0121.tif" />
-123Table 9_. (<sup>incl</sup> n X <sup>e</sup> %) fight against Erysibus in Eloise on rice rice ______
2-Chlorophenyl (4-chlorophenyl) methyl (1X-1,2,4 triazol-1-ylmethyl) silane 7H-bis (2-fluorophenyl) 7-methyl (1H-1,2,2-triazolT-ylmethylmilonyl silicon 1: 1 90 (1H-imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silanone 70 bis (4-fluorophenyl) (1H-imidazol-1-ylmethyl) methylsilon 9H (1H-ylmethyl) 2-trifluoromethylphenyl) silane
Butyl (2,4-dichlorophenyl) (1H-imi, dazol-1-ylmethyl) methylsilane .. <sub>guy</sub> , .
^ canada<sup>20</sup>^<sup>01 nylon</sup>'imidazol-1-ylmethyl) 4-fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silanone (1H-imidazol-1-ylmethyl) (2-methoxyphenyl)
<img file="GR76497B_D0122.tif" />
Butyl (1H-imidazol-1-ylmethyl) methyl (phenyl) silane. 80 (1,1'-Diphenyl-4-yl) butyl (1H-imidazol-1-ylmethyl) methylsilane 90
Butyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 80 (1,1 '-Diphenyl-2-yl) dimethyl (1H-imidazol-1-ylmethyl) silane / 90 (1,1'-Diu) 3-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 90 bis (2-chlorophenyl27 (1H-imidazol-1-ylmethyl) methylsilane 40 (1,1'-biphenyl-4-yl) dimethyl 1-ylmethyl) silane, copper hypochlorite sublot
1: 1 (2-Chlorophenyl) (dimethyl) (1H-imidazol-1-ylmethyl) silane Example 77 The compounds of the present invention were dissolved
<img file="GR76497B_D0123.tif" />
-124 equal to 6% of the final call, and then suspended
VI concentration of 100 PPM in purified water containing 250 PPM of surface active substance TEEM 014 (polyhydric esters
I n!
alcohol). The suspensions were then sprinkled to the point of discharge on the seedling seedlings. The following day the plants were inoculated with a spore suspension of PYEICUBARIA 0RYZAB, a causative agent of horoscope burning, and lost to a saturated moisture chamber at 28 ° C for 24 hours and 24h after 24 hours. The percent control of the disease is shown in the following table. The treated plants had no or no lesions, whereas the untreated plants had many lesions on each leaf.
Table 10
Okay
Dimethyl (1-naphthalenyl) (1H-1,2,4-triazol-1-ylmethyl) bis (4-chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silicon bis (4- fluorophenyl) (methyl) (1H-1,2,4 triazol-1-ylmethyl) silane
C4- (1,1-dimethylethyl) phenyl / dimethyl (1H-1,2,4-triazol-1- (4H-1,2,4-triazol-1-ylmethyl) silanone (4 - $. Orophenyl) methyl (phenyl) ylmethyl) silane
Butyl (methyl) phenyl (1H-1,2,4-triazol-1ylmethyl) silane
C 2-chlorophenyl) dimethyl (1H-1, 2,4-triazol-1-ylmethyl) silane, (1,1'-Biphenyl-4-yl) butyl (methyl) z1H1, 2,4-triazol-1-ylmethyl) silicone
Butyl (4-fluorophenyl) methyl (1H-1,2,4 triazazol-1-ylmethyl) silane
Dibutyl (methyl) (1H-1,2,4-triazol-1-ylmethyl) silicone% Combating the burning of the abyss
100
<img file="GR76497B_D0124.tif" />
-125 Table_10 (cont'd) '' Hypoxyl bis (1H-1'-biphenyl-5-yl) (methyl) (1H-1,2,4 triazol-1-ylmethanesulfonyl (1,1) <sup>G.</sup>-Diphenyl-2-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane% to control rice burning
100
2-Chlorophenyl (methyl) phenyl (1H-1, 2,4-triazol-1-ylmethyl) silane 100
4-Bromophenyl (methyl) phenyl (1H ~ 1,2,4-triazol-1-ylmethyl) silane 80
(2-Chlorophenyl27methyl (1X-1,2,4-triazazol-ylmethyl) silicon ”
Dimethyl (4-methylsulfonylphenyl) (1H-1,2,4 triazol-1-ylmethyl) silane 70
Dissimilar (4-bromophenyl) 7methyl (1H-1,2,4-triazolT-ylmethyl) silane "90 (1, 1<sup>G.</sup>-Diphenyl-4-yl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silane 80-4-dodecylbenzenesulfonic acid salt (1,1 <sup>G.</sup>-Diphenyl - <} - yl) dimethyl (1H-1,2-4-triazol1-ylmethyl) silane, complexed with 1: 1 100 copper hypochlorite (1.1 <sup>G.</sup>-Diphenyl-4-yl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silane, complexed with 1: 1 zinc chloride (II) 1: 1/100 bis (2-fluorophenyl) 7methyl (1H-1,2, 4-triazolT-ylmethyl) silane, 1: 90 'copper / 2-bis (2-fluorophenyl) 7methyl (1H-1,2,4-triazol-1-ylmethyl) silane complex, complex with 1: 100 copper / hypochlorite (1H-imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane 70
C4- (1,1-Dimethylethyl) phenyl7 (1H-imidazol-1ylmethyl) dimethylsilane ”. 80
<img file="GR76497B_D0125.tif" />
(4-fluorophenyl) (1H-L midazol-1-ylmethyl) methyl (phenyl) silane
C4- (4-chlorophenoxy) phenyl7 dimethyl (1H-imidazolT-ylmethyl) silane ~. ·
Butyl (1H-imidazol-1-ylmethyl) methyl (phenyl) silane
<img file="GR76497B_D0126.tif" />
—126—
Table 10 (cont.)% Of combustion of rice burns
9 (1,1'-Diphenyl-4-yl) butyl (1H-imidazol-1ylmethyl) 9-methylsilane
Butyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 100 (1.1<sup>G.</sup>-Diphenyl-2-yl) dimethyl (1H-imidazol-1-yl) methyl) silicone 90 (1,1 '-Diphenyl-3-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 80 /' bis (2-chlorophyll) (ΐH-imidazol-1-ylmethylmethylsilane "90
Dimethyl (1H-imidazol-1-ylmethyl) (4-methylsulfonylphenyl) silicone 100 g (.4-Bromophenyl) 7 (1H-imidazol-1-ylmethyl) methylsilane 80
Example 78
Compounds of the present invention were dissolved in acetone in an amount equal to 6% of the final solution and then suspended in a concentration of 100 PPM in purified water containing 250 ppm of surfactant. They were then sprinkled to the point of extraction on tomato seedlings. The following day, the plants were inoculated with a suspension of spores PHYTOPHTHORA IKPESTAN3, a topological agent of tomato latex, and were left in a chamber for 24 hours at 0 ° C and 20 ° C. disease. * Its 100 percent combat. The disease is shown in the following table. The invasive: treated plants had no or no other virus; the untreated plants had many other / invasive plants, each leaf.
<img file="GR76497B_D0127.tif" />
<sub>c</sub>...........
-127Table 11% Combat Observation
<td>Dimethyl (4-phenoxyphenyl) (1H_1,2,4-triazol-1-ylmethyl) silicon</td><td> 50</td><td></td>
<td>/ ~ 4- (4-Chlorophenose) phenyl7dimethyl (PHT, 2,4-triazol-1-ylmethyl) silane</td><td> 50</td><td>- L.</td>
<td>(L, 1'-Biphenyl-2-yl) dimethyl (1H-1,2,4 triazol-1-ylmethyl) silane</td><td> 50</td><td></td>
<td>(1,1'-Biphenyl-4-yl) imethyl methyl -H-1,2,4 triazol-1-ylmethyl) silane, 4-dodecylbenzenesulfonic acid salt</td><td> 60</td><td> -</td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4 triazafl-1-ylmethyl) silane, complexed with 1: 1 copper hypochlorite</td><td> 100</td><td></td>
<td>(1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4triazol-1-ylmethyl) silane, complexed with zinc chloride (1) 1: 1</td><td> 90</td><td></td>
<td>Bis (2-fluorophenyl27methyl (1H-1,2,4 triazafl-1-ylmethyl) silane, complexed with 2: 1 copper hypochlorite</td><td> 40</td><td>i. i, ', -.' · ·</td>
<td>(4-Bromophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane</td><td> 30</td><td></td>
<td>(1,1'-Diphenyl-4-yl) dimethyl (L-imidazol1-ylmethyl) silane</td><td> 50</td><td>· -7/7 ; : xx</td>
<td>(1H-imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silicone</td><td> 80</td><td></td>
<td>Dimethyl (1H-imidazol-1-ylmethyl) (3-trifluoromethylphenyl) silane</td><td><sup>70</sup></td><td>! ·. - '. x3 ····: \ ·' : iSiW .c ·: ·· · · - ····</td>
<td>(2,6-dimethoxyphenyl) (dimethyl) (1H-imidazol1-ylmethyl) silane</td><td> 50</td><td>•, j γ γ; / / · ·: /.<sup>1</sup> 7: * Xx; / // 77-7-</td>
<td>/ "Bis (2-chlorophenyl270H-imidazol-1-ylmethyl) methylsilane"</td><td> 60</td><td> ·*- <sup>1</sup> '' '· ·:' · .Y ' !</td>
<td>Example 79</td><td></td><td></td>
Compounds of the present invention were incorporated into a V-δ power standard at 45 ° C at a concentration of 200.0 PPM. The immobilized media were dispensed into PETRI plates and allowed to solidify. Plugs were mounted on the media about 7 // 2 3 / mm in <5 agar cultures PHYT0PHTH0RA: PHW0pHi5 ///; / <: 7 '? · ·.'; '.
-128CIHNAMOMI, P. CACTORUM, P. INFB3TAN3, P. PALMIVORA, and P. PARAgITICA paras. They are inhibited by union, interfered with a colony whose radial growth was tested 15 mm or more when grown on unmodified media. The following table lists the number of species of PHYTQPHTHORA dissolved in certain compounds of the present invention.
Table 12
The 5 types
PHYTQPHTHORA stained in vitro '_____ i
"Butyl" Dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane (3,4-dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) ) (1,1'-Biphenyl-A-ylidimethylethylHH-imidazol-ylmethyl) silanone (1H-imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane (2,4-dichloromethyl) i midazed ol-1-methyl) silane
Biphenyl (1H-imidazol-1-ylmethyl) methylsilane (4-fluoroalkyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane
Example 80 Compounds of the present invention were incorporated into a specific formulation and used to overlay cotton seeds at a ratio of 2 g / kg. seeds. After careful coating, the seeds were allowed to air dry at room temperature. Then the cotton seeds I sowed in a fungus-modified Fungus AHIANADERI4AroMvas and only maize, are you proportionally sufficient to kill the part with?
-129 of untreated seed treatment. Seeds were kept at room temperature for 1 week, after which estimates of disease were made. most or all of the seeds from the treatments were seeded and produced seedlings, in contrast to the untreated seeds that either did not germinate or did not germinate.
Table $ 15 Fight it
See PYTHIUM on Cotton
Ethyldimethyl (1H-1,2,4-triazol-1-ylmethyl) silanone 48 (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol1-ylmethyl) silane '12 (4- chlorophenyl) dimethyl (1H-1,2,4-triazol-1 -.
(methyl) silane 53
Dimethyl (4-phenoxyphenyl) (1H-1,2,4-triazol-1-.
ylmethyl) silane 18<sup>A</sup>
(1,1'-Diphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 18 (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) dimethyl.
losilane 18<sup>A</sup> (3,4-Dichlorophenyl) (LX-imidazol-I-ylmethyl) di-.
methylsilane 15<sup>A</sup>
A = 0.5 g / kg seed control. |
Example 81 Compounds of the present invention were incorporated into a specific formulation and used to coat maize seeds at a rate of 2 g / kg of seeds, after careful processing. room. Then the seeds sown / Within x $> µm modified with PYTHIUM / p
1 '' · «» e3.
-130 maize and maize flour, with a ratio sufficient to kill most of the untreated seeds. The seeds were maintained at 49 ° F for 2 weeks and then at 70 ° C; After one more week, estimates of the disease were made. The one hundred percent control of the disease is shown in the following table. Most or all of the seeds from the treatments also sprouted and produced seedlings, in contrast to untreated seeds that either did not germinate or produce rotten or weak seedlings.
Table 14
Ethyldimethyl z1 H-1,2,4-triazol-1-ylmethyl) silanone (1,1'-Biphenyl-4-yl) dimethyl (1H-1, 2,4 triazol-1-ylmethyl) silanone% Control of PYTHIUM on ' Abbacitus (4-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 8
Dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 3H (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 43
Ethyl (1H-imidazol-1-ylmethyl) dimethylsilane 7H (1H-1 imidazol-1-ylmethyl) dimethyl (4-methylphenyl) silanone 30 (1,1'-Biphenyl-4-yl) dimethyl (1H-dimethyl) silane 32 (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 25 (1H-imidazol-1-ylmethyl) dimethyl (1-naphthalinyl) silanone 27 (3,4-Dichloromethyl) 1-ylmethyl) dimethylsilane (1H-imidazol-1-ylmethyl) dimethyl. (4-phenoxy-phenyl) silane. . . ·
Dimethyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) silane
<img file="GR76497B_D0128.tif" />
-131-
Contents104
128 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 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51 Sheet 52 Sheet 53 Sheet 54 Sheet 55 Sheet 56 Sheet 57 Sheet 58 Sheet 59 Sheet 60 Sheet 61 Sheet 62 Sheet 63 Sheet 64 Sheet 65 Sheet 66 Sheet 67 Sheet 68 Sheet 69 Sheet 70 Sheet 71 Sheet 72 Sheet 73 Sheet 74 Sheet 75 Sheet 76 Sheet 77 Sheet 78 Sheet 79 Sheet 80 Sheet 81 Sheet 82 Sheet 83 Sheet 84 Sheet 85 Sheet 86 Sheet 87 Sheet 88 Sheet 89 Sheet 90 Sheet 91 Sheet 92 Sheet 93 Sheet 94 Sheet 95 Sheet 96 Sheet 97 Sheet 98 Sheet 99 Sheet 100 Sheet 101 Sheet 102 Sheet 103 Sheet 104 Sheet 105 Sheet 106 Sheet 107 Sheet 108 Sheet 109 Sheet 110 Sheet 111 Sheet 112 Sheet 113 Sheet 114 Sheet 115 Sheet 116 Sheet 117 Sheet 118 Sheet 119 Sheet 120 Sheet 121 Sheet 122 Sheet 123 Sheet 124 Sheet 125 Sheet 126 Sheet 127 Sheet 128
41 members in 20 offices
Priority claims24
| 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 | |
| 34926282 | United States of America | A | |
| 34926282 | 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 | |
| 267986 | – | – | – |
| 267987 | – | – | – |
| 349261 | – | – | – |
| 349262 | – | – | – |
| 377121 | – | – | – |
| 377122 | – | – | – |
| US19810276986 | – | – | – |
| US19810276987 | – | – | – |
| US19820349261 | – | – | – |
| US19820349262 | – | – | – |
| 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 | |
| GR76497BThis record | 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 | |
| CS238626B2 | 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
- 76497
- Publication, EPODOC
- GR76497
- Application
- 68538
- Application, DOCDB
- 820168538
- Application, EPODOC
- GR19820168538
Classification
- CPC, 5
- C07F7/0812
- C07F7/08
- A01N55/00
- C07F7/0838
- C07F7/1804
- IPC, 3
- C07F7 08
- A01N55 00
- C07F7 18
