CS238626B2 - Fungicidal composition and method of preparation of the active ingredient - Google Patents

Abstract

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

Description

The invention relates to fungicidal compositions, particularly suitable for the treatment of living plants, which contain as active ingredient silylmethyltriazoles and imidazoles as such, for example dimethyl(phenyl) (1H-1,2,4-triazole-1-methyl)silane and (1,1'-biphenyl-4-yl)dimethyl(1H-1-imidazol-1-yl-methyl)silane.

U.S. Patent No. 3,692,798 protects compounds of the general formula

CH

CH, and its uses as fungicides.

Silyl ethers of the general formula ~N are also known.

OSLRi I ³ ^r-CHjCH-CH-CfCH^ where

R 1 , R 2 and R 3 represent a lower alkyl group or a phenyl group and which have antimicrobial activity.

European Patent No. 29,993 protects compounds of the general formula

where means

R is an alkyl group with 1 to 4 carbon atoms and

Y and Z are hydrogen or a group of the general formula

SÍR1R2R3 where means

Ar substituted phenyl group,

X is a group of formula CH or a nitrogen atom and R is an alkyl group;

These compounds are reported to be useful as agricultural fungicides.

German Patent No. 3,000,140 describes silyl ethers of the general formula ₃

Ar-O~CH-CH-C(CH^

AND

N where where means

R1, R2 and R3 represent an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group or a substituted phenyl group. These compounds are considered agricultural fungicides.

U.S. Patent Nos. 3,256,308 and 3,337,598 protect compounds of the general formula ^R1 ,

Ar substituted phenyl group,

X a group of formula CH or a nitrogen atom and

R is a phenyl group or a lower alkyl group. These compounds are said to be useful as agricultural fungicides.

U.S. Patent No. 4,248,992 describes a class of organosilicon compounds having at least one monovalent guanidine group in the molecule of the general formula

NR2

Z —N= where

NR2

R1 represents a methyl, ethyl, vinyl or phenyl group. They are said to be effective against fungi.

Belgian patent number 785 127 describes quaternary ammonium salts of the formula where

R represents a hydrogen atom or a monovalent hydrocarbon group.

121

122

Compound % disease reduction

rice [ 4-(4-Chlorophenoxy]phenyl]dimethyl (1H-imidazol-1-ylmethyl 100 Butyl (1H-imidazol-1-ylmethyl J methyl (phenyl J silane 90 (1,1'-Biphenyl-4-yl j butyl (1H-imidazol-1-ylmethyl j methylsilane 90 Butyl (4-fluorophenyl J (1H-iniidazol-1-ylmethyl Jmethylsilane 100 (1,1'-Blfenyl-2-yl dimethyl (1H-imidazol-1-ylmethyl 90 (Ι,Γ-Bifenyl-3-yl jdimethyl (1H-imidazol-1-ylmethyl} silane 80 [bis(2-Chlorophenyl}](1H-imidazol-1-ylmethyl jmethylsilane 90 Dimethyl (1H-imidazol-1-ylmethyl j (4-methylsulfonylphenyl) silane 100 [bis(4-Bromoenyl) | (1H-iiuidazol-1-ylmethyl jmethylsilane 80 bis (4-Eumorphenyl} hydroxy (111-hmdazol-1-ylmethyl islate 60 Dimethyl [1H-imidazol-1-ylmethyl J (4-trifluoromethoxyphenyl J - silane 90 (4'-Bromo-1,1'-biphenyl-4-yl J dimethyl (1H-imidazol-1-ylmethyl J - silane 90 Dimethyl (1H-nidazol-1-ylmethyljoctadecylsilane 80 Oxybis [ bis (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl Jsilane 50 (4'-Bromo-1,1'-biphenyl-4-yl jdimethyl (1H-1,2,4-triazol-1-ylmethyl Jsilane 90 (Ι,Γ-Biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-ylmethyl silane, 1 : 1 complex with copper(II) chloride 100 Methyl[bis(4-methylphenylj ](1H-1,2,4-triazol-1-ylmethyl J - silane 80 Example 78

The active ingredients of the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TRÉM 014 (esters of polyhydric alcohols). These suspensions are sprayed onto tomato seedlings until they start to run off. The following day, the plants are inoculated with a suspension of spores of Phytophthora infestans, the cause of tomato blight, and incubated in a humidity chamber at 20°C for 24 hours and then left in the growth chamber for a further 7 days and then the degree of infestation is assessed. The percentage reduction in infestation is given in the following table. Treated plants show no infestation or only a slight infestation, while untreated plants show infestation on every leaf.

Table XXX

Compound % tomato blight control [bis (2-Fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl)silane, : 1 complex with copper chloride 40 (4-Bromophenyl) (1H-imidazol-1-ylmethyl)dimethylsilane 30 (1,1'-Biphenyl-4-yl)dimethyl (1H-imidazol-1-ylmethyl)silane 50 (1H-Imidazol-1-ylmethyl)dimethyl (4-phenoxyphenyl)silane 80

Dimethyl (1H-imidazol-1-ylmethyl j (3-trifluoromethylphenyl)silane 70 (2,6-Dimethylhydroxyphenyl) (dimethyl) (1H-imidazol-1-ylmethyl)silane 50 [bis(2-Chlorophenyl) ] (1H-imidazol-1-ylmethyl jmethylsilane 60

Dimethyl (4-phenoxyphenyl) [1H-1,2,4-triazol-1-ylmethyl]silane 50 [4-(4-Chlorophenoxy)phenyl]dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane 50 (1,1'-Bifenyl-4-yl j dimethyl(1H-1,2,4-triazol-1-ylmethyl) silane, salt of 4-dodecylbenzenesulfonic acid 60

119

120

Compound % reduction of bacterial leaf spot of rice

23862B

Compound % rice disease reduction

Methyl [bis(4-methyl}phenyl](1H-1,2,4-triazol-1-ylmethyl)silane 30

Example 77

The active ingredients of the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TRÉM 014 (esters of polyhydric alcohols)

bare. These suspensions are sprayed on rice seedlings until they start to drip. The next day, the plants are inoculated with a suspension of Pyricularia oryzae spores, which cause rice blight, and incubated in a humidity chamber at 28°C for 24 hours, then left in a growth chamber for another 7 days, and then the degree of infestation is assessed. The percentage reduction in infestation is shown in the following table. Treated plants show no infestation or are slightly affected, untreated plants show infestation on every leaf. Table XXIX Compound % disease reduction rice Dimethyl (1-naphthalenyl)(1H-1,2,4-triazol-1-ylmethyl)silane 70 bis (4-Chlorophenyl)methyl 1H-1,2,4-triazol-1-ylmethyl isolate 90 [ 4-(Dimethylethyl j phenyl] dimethyl (1H-1,2,4-triazol-1-ylmethyl 90 (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90 1 bis (4-Fluorophenyl j (methyl) (1H-1,2,4-trazol-1-ylmethyl islate 100 Butyl (methyl Jphenyl (1H-1,2,4-triazol-1-ylmethyl Jsilane 90 (2-Chlorophenyl J dimethyl 1H-1,2,4-triazol-1-ylmethyl isolate 100 (1,1'-Bifenyl-4-yl J butyl (methyl) (1H-1,2,4-triazol-1-ylmethyl islate 100 Butyl (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl 100

Dibutylf methyl] (lH-l,2,4-triazol-l-ylmethyl Jsilane 80 bis (l,l'-Biphenyl-4-yl j (methyl j(lH-l,2,4-triazol-l-ylmethyl j)silane 100 (l,l'-Biphenyl-2-yljdimethyl(lH-l,2,4-triazol-l-ylmethyl)silane 90

2-Chlorophenyl (methyl j phenyl(1H-1,2,4-triazol-1-ylmethyl) silane 100

4-Bromophenyl (methyl j phenyl (1H-1,2,4-triazol-l-ylmethyl islan 80 [ bis (2-Chlorophenyl jjmethyl (1H-1,2,4-triazol-l-ylmethyl islan 90

Dimethyl (4-methylsulfonylphenyl)j (1H-1,2,4-triazol-1-ylmethyl islan 70 [ bis (4-Bromophenyl) j methyl (111 ·

-1,2,4-triazol-1-ylmethyl silane 90 (1,1'-Biphenyl-4-yl dimethyl (1H-1,2,4-triazol-1-ylmethyl silane, salt of 4-dodecylbenzenesulfonic acid 80 (1,1'-Biphenyl-4-yl dimethyl (1H-1,2,4-triazol-1-ylmethyl silane, : 1 complex with copper chloride 100 (1,1'-Biphenyl-4-yl dimethyl (1H-1,2,4-triazol-1-ylmethyl silane, : 1 complex with zinc chloride 100 [ bis (2-Fluorphenyl j ] methyl (1H-1,2,4-triazol-1-ylmethyl j silane,

1: 1 complex with copper chloride 90 [ bis (2-Fluorph enyl j ] methyl (1H-1,2,4-triazol-l-ylmethyl j silane, : 1 complex with copper chloride 100 (1H-Imidazol-l-ylmethyl j dimethylphen 4-phenoxyphenyl j silane 70 [ 4-(1,1-Dimethylethyl Jphenyl ] (1H-imidazol-1-ylmethyl j dimethylsilane 80 (4-Fluorophenyl) (1H-imidazol-lylmethyl) (phenyl) silane

100

117

118

238G2B

Compound % reduction in bacterial leaf spot of rice Compound % reduction in bacterial leaf spot of rice Butyl (methyl)phenyl(1H-1,2,4- (4-Fluorophenyl) (1H-imidazole-1- -triazol-1-ylmethyl) silane (1,1'-Biphenyl-4-yl)butyl (me- 90 -ylmethyl) methyl (phenyl) silane (1H-Imidazol-1-ylmethyl) [2- 90 thyl) (1H-1,2,4-triazol-1-ylylethyl) silane Butyl (4-Fluorophenyl Jmethyl (1H- 80 methoxyphenyl) dimethylsilane [ 4-(4-Chlorophenoxy)phenyl]dimethyl (1H-imidazol-1-ylmethyl- 90 -1,2,4-triazol-1-ylmethyl)silane bis [Ι,Γ-Biphenyl-4-yl] (methyl)- 80 thyl) silane Butyl [1H-imidazol-1-ylmethyl)- 70 [1H-1,2,4-triazol-1-ylmethyl) silane [ bis [4-Metho <yf enyl) ] methyl- 90 methyl (phenyl) sil an (1,1'-Biphenyl-4-yl)butyl [1H-imidazol-1-ylmethyl]methyl- 80 (1H-1,2,4-triazol-1-ylmethyl) - silane 80 silane Butyl (4-fluorophenyl) [1H-imida- 90 2-Chlorophenylmethyl)phenyl(1H- -1,2,4-triazol-1-ylmethyl) silane 90 zol-1-ylmethyl) methylsilane (1,1'-Bifenyl-2-yl)dimethyl- 80 4-Bromophenyl(methyl)phenyl(1H-1,2,4-trazol-1-ylmethyl)silane 90 [1H-imidazol-1-ylmethyl)silane (1,1'-Bifenyl-3-yl)dimethyl (1H- 90 [bis[2-Chlorophenyl)]methyl(1H-1,2,4-triazol-1-ylmethyl)silane 60 -imidazol-1-ylmethyl Jsilane [bis(2 Chlorophenyl)][IH-imida- 90 (Ι,Γ-Bifenyl-4-yl)dimethyl- (1H-1,2,4-triazxl-1-ylmethyl) silane, 1 : 1 complex with chloride zol-1-ylmethyl) methylsilane (1,1'-Biphenyl-4-yl)dimethyl [1H- 40 copper (1,1'-Biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane, 90 -imidazol-1-ylmethyl)silane, 1:1 complex with copper chloride [ 2-Chlorophenyl) [ dimethyl) (1H- 50 1:1 complex with zinc chloride 90 -imidazol-1-ylmethyl) silane bis [ 4-Fluorophenyl) hydroxy [ 1H- 90 2-Chlorophenyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl- -imidazol-1-ylmethyl) silane 90 thyl) silane [ bis (2-Fluorphenyl) ] methyl (1H-1,2,4-triazol-1-ylmethyl)silane, 1 : 1 complex with copper chloride- 70 [3-Chlorophenyl)dimethyl (1H-imildazol-1-ylmethyl)Silan [ 4'-Bromo-1,1'-biphenyl-4-yl)dimethyl (1H-imidazol-1-ylmethyl- 90 by him (1H-Imidazol-1-ylmethyl) dime- 90 thyl) silane (3,5-Dichlorophenyl)dimethyl (lyl- 90 thyl (4-phenox.yf enyl} silane bis (4-Fluorophenyl) (1H-imidazoi- 70 -imidazol-1-ylmethyl) silane Dimethyl [1H-imidazol-1-yl- 90 -1-ylmethyl) methylsilane (1H-Imidazol-1-ylmethyl] dimethyl (2-trifluoromethylphenyl)- 90 methyl) octadecylsilane (4'-Bromo-1,1'-biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-ylmethyl- 100 silane Butyl (2,4-dichlorophenyl) [1H-imidazol-1-ylmethyl) methyl- 80 thyl) silane (1,1'-Biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane, 90 silane 90 2 : 1 complex with chloride: copper- bis[2,4-Dichlorophenyl)[1H-imidazol-1-ylmethyl)methylsilane 80 first 80

115

118

Compound % control of peach brown rot. The percentage control of infestation (percent inhibition of colony growth on treated peaches compared to colonies on untreated peaches) is shown in the following table.

Table XVII

Compound % Brown Rot Reduction (Dimethyl)phenyl (1,2,4-triazol-1-ylmethyl)silane 89 (Butyl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane 95 (1,1'-Biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane 100

Butyl (4-chlorophenyl)methyl (1H-1,2,4-triazol-1-ylmethyl)silane 98

Dimethyl (4-methoxyphenyl) (1H-1,2,4-triazol-l-ylmethyl) silane 97 (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-l-ylmethyl) silane 100 bis (4-Chlorophenyl ] (methyl) (1H-1,2,4-triazol-l-ylmethyl) silane 95 (1,1'-Biphenyl-4-yl) dimethyl (4H-1,2,4-triazol-4-ylmethyl) silane 96 bis (4-Fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100

Butyl (2,4-dichlorophenyl jmethyl(1H-1,2,4-triazol-l-ylmethyl) silane 98 (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-l-ylmethyl) silane 70 (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-l-ylmethyl) silane 90

Butyl (4-Fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl isolate 100

Dibutyl (methyl) (1H-1,2,4-triazol-1-ylmethyl islan 81 (1,1'-Biphenyl-4-yl j dimethyl (1H-imidazol-1-ylmethyl islan 83

Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl jmethylsilane 45 (1H-Imidazol-1-ylmethyl jdimethyl (4-phenoxyphenyl)silane 80 (2,4-Dichlorophenyl)dimethyl (1H-imidazol-1-ylmethyl)silane 100

Diphenyl (1H-imidazol-1-ylmethyl jmethylsilane 76 (4-Chlorophenyl) (1H-imidazol-1ylmethyl)methyl (phenyl silane 45 (4-Fluorophenyl j (1H-imidazol-1ylmethyl) methyl (phenyl silane 65

Example 76

The active ingredients of the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TRÉM 014 (esters of polyhydric alcohols). The suspensions are then sprayed onto rice seedlings until they start to run off. The following day, the plants are inoculated with a mixture of the pulp and mycelia of Rhizoctonia solani, which causes bacterial leaf spot of rice, and incubated in a growth chamber for 7 days. The infestation of the plants is assessed. The percentage reduction in infestation is shown in the following table. The treated plants show a slight infestation, while the untreated ones are heavily infested.

Table XXVIII

Compound % reduction of bacterial leaf spot of rice (l,l'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl silane 40 (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl silane 80 bis (4-Fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl silane 80 (4- (1,1-Dimethylethyl) phenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl silane 90

Butyl (2,4-dichlorophenyl)methyl 1(1H-1,2,4-triazol-l-ylmethyl) silane 50 (4-Chlorophenyl) methyl (phenyl j (1H-1,2,4-triazol-l-ylmethyl) silane 90 (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-l-ylmethyl) silane 80

113

114

Table XXVI

Compound % rust reduction on beans

Compound % control of yellow leaf spot in peanuts (1,1'-Biphenyl-4-yl) hydroxy(methyl) (1H-1,2,4-triazol-1-ylmethyl)silane 100 (1,1'-Biphenyl-4-yl) (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl)silane 100

Dimethyl (4-trifluoromethoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 50 (4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1,Γ-Biphenyl-4-yl) dimethyl(5-methyl-lH-l,2,4-triazol-l-ylmethyl) silane 100 (l,r-Biphenyl-4-yl Jdimethyl(lH-l,2,4-triazol-l-ylmethyl )silane 100 (l,l'-Bipheny]-4-yl)dimethyl](lH-l,2,4-triazol-l-ylmethyl)silane, 2:1 complex with chloride copper 100

A _b phytotoxic browning

B compound used at a concentration of 400 ppm BB compound used at a concentration of 20 ppm

Example 74

The active ingredients of the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 80 ppm in purified water containing 250 ppm of the surfactant TRÉM 014 (esters of polyhydric alcohols). These suspensions are sprayed onto the seedlings of the gourd in an amount that just starts to run off. The following day, the plants are inoculated with a suspension of spores of the fungus Uromyces phaseoli, which causes gourd rust, and incubated in a humidity chamber at 20°C for 24 hours and then left in a greenhouse for a further 7 days. The degree of infestation is assessed. The percentage reduction in infestation is given in the following table. Treated plants show little or no rust infestation, while untreated plants are covered with rust. In addition to the reduction in infestation, some of the treated plants show phytotoxicity in the form of reduced growth.

(2,4-Dichlorophenyl J dimethyl(1H-imidazol-1-ylmethyl)silane 83 (1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)j silane 100 (2,4-Dichlorophenyl Jdimethyl(1H-1,2,4-triazol-1-ylmethyl)silane 30G ^A bis (4-Chlorophenyl) (methyl)(1H-1,2,4-triazol-1-ylmethyl) silane 100G (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 98 ^b (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane i00 ^B bis (4-Fluorophenyl) (methyl)(1H-1,2,4-triazol-1-ylmethyl)silane gs ^B (1,1'-Biphenyl-4-yl)diinethyl(1H-imidazol-1-ylmethyl)silane 100

A _c reduction in growth

B compound used at a concentration of 16 ppm Example 75

The active ingredients of the invention are dissolved in acetone in an amount corresponding to 5% of the final volume and then suspended at a concentration of 100 ppm in purified water containing the surfactant TRÉM 014 (esters of polyhydric alcohols) in an amount of 700 ppm. The preserved peach halves are soaked in this suspension for three minutes and then placed in a sterile package with dry air. After drying, the peach halves are inoculated with two pieces of Monilinia fructicola mycelium, which causes brown rot of stone fruits, and incubated in sterile packages for 5 days. The radius of the colonies on each peach is then measured. The colonies on the treated peaches do not show growth or only show a graying with a diameter of a few millimeters, while in the untreated peaches they cover the entire surface

111

112

Compound % suppression of yellow leaf spot in groundnut

Compound °/o yellow leaf spot suppression of groundnut (4-Fluorophenyl)-(1H-imidazol-1-ylmethyl jmethyl (phenyl)silane 100 (2-Chlorophenyl)(11-1-imidazol-lylmethyl)dimethyl silane 80 (1,1'Biphenyl-4-yl)butyl(ΙΗ-imidazol-1-ylmethyl)methylsilane 90 bis(1,1'-Biphenyl-4-yl)(ΙΗ-imidazol-1-ylmethyl)methylsilane 60 (1,1'-Blphenyl-4-yl)(ΙΗ-imidazol-1-ylmethyl) methyl (phenyl) silane 80 (1,1'-Bifenyl-2-yl)dimethyl(ΙΗ-imidazol-1-ylmethyl)silane 30 (1,1'-Biphenyl-3-yl)dimethyl(ΙΗ-imidazol-1-ylmethyl)silane 80 (2-Chlorophenyl) (1H-imidazol-1-ylmethyl) Jmethyl (phenyl)silane 100 (4-Bromophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 90 (bis(2-Chlorophenyl)](ΙΗ-imidazol-1-ylmethyl)methylsilane 100 [bis(4-Bromophenyl)](ΙΗ-imidazol-1-ylmethyl)methylsilane 50 (l,l‘-Biphenyl-4-yl)dimethyl(ΙΗ-imidazol-1-ylmethyl)silane, 1:1 complex with copper(II) chloride 100 (2-Chlorophenyl (4-chlorophenyl) (ΙΗ-imidazol-1-ylmethyl)methylsilane 80 bis (4-Chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100 Methyldiphenyl (1H-1,2,4-triazol-1-ylmethyl) silane 100

(1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane 100 (4-Chlorophenyl}dimethyl 1(1H-1,2,4-triazol-1-ylmethyl)silane 90

Dimethyl (1-naphthalenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90 (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (4-Fluorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane 50 bis (4-Chlorophenyl) hydroxy(ΙΗ-imidazol-1-ylmethyl) silane 50 (1,1'-Biphenyl-4-yl) (4-fluorophenyl)(ΙΗ-imidazol-1-ylmethyl) methylsilane 100

Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethoxyphenyl) silane 90 (4'-Bromo-1,1'-biphenyl-4-y])dimethyl (1H-imidazol-1-ylmethyl) silane 90 bis (4-Chlorophenyl) hydroxy(1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (4-Fluorophenyl) hydroxy(1H-1,2,4-triazol-1-ylmethyl) silane 100 tris (4-Fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl)silane 90 bis (4-Chlorophenyl) hydroxy(4H-1,2,4-triazol-1-ylmethyl) silane 100

Oxybis [ bis (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) (1,1'-Biphenyl-4-yl)methyl(2-propoxy) (1H-1,2,4-triazol-1-ylmethyl) silane

100

3 β β 2 H

103

110

Compound % suppression of yellow leaf spot in groundnut Compound % suppression of yellow leaf spot in groundnut (2-Chlorophenyl 1)dimethyl(1H-1,2,4-triazol-1-ylmethyl)- strong 30 (1,1'-Biphenyl-4-yl)dimethyl- (1H-1,2,4-triazol-1-ylmethyl) silane, 1:1 complex with sulfate (1,1'-Biphenyl-4-yl)butyl (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100 manganese 2-Chlorophenyl (4-chlorophenyl) methyl-(1H-1,2,4-triazol-1- 100 bis (1,1'-Biphenyl-4-yl) (methyl) (1H-1,2,4-triazol-1-ylmethyl)- silane 80 -ylmethyl) silane [bis(2-Fluorophenyl)]methyl(1H-1,2,4-triazol-1-ylmethyl]- 90 [1,1'-Bifenyl-4-yl)methyl- silane, 1:1 complex with copper chloride 100 (phenyl)(1H-1,2,4-triazol-1-ylmethyl)silane 100 [ bis (2-Fluoropheny 1) ] methyl- [ bis (4-Methoxyphen 1) J methyl (1H-1,2,4-triazol-1-ylmethyl)- (1H-1,2,4-triazol-1-ylmethyl)silane, 2:1 complex with copper(II) chloride 100 silane (1,1'-Biphenyl-2-yl)dimethyl- (1H-1,2,4-triazol-1-ylmethyl)- 30 (1,1'-Biphenyl-4-yl)dimethyl(1H-imidazol-1-ylmethyl)silane 100 silane (1,1'-Biphenyl-3-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)- 100 (2,4-Dichlorophenyl)dimethyl- (1H-imidazol-1-ylmethyl) - silane 100 silane 2-Chlorophenyl methyl ]phenyl- 90 Diphenyl (1H-imidazol-1-ylmethyl) methylsilane 50 (1H-1,2,4-triazol-1-ylmethyl)- silane 100 bis (4-Fluorphenyl]- 4-BiOmlenyl (methyl j phenyl- (1H-imidazol-1-ylmethyl) - methyl silane 100 (1H-1,2,4-triazol-1-ylmethyl]- silane 100 Dimethyl (4-fluorophenyl) - [ bis (2-Clylorphenyl) ] methyl- (1H-imidazol-1-ylmethyl) - silane 60B ^A (1H-1,2,4-triazol-1-ylmethyl)- silane 100 Dimethyl (1H-imidazol-1- [bis(4-Bromophenyl]]methyl- ‘ -ylmethyl) (4-trifluoromethylphenyl) silane 36 ^B (1H-1,2,4-triazol-1-ylmethyl)silane 100 Dimethyl [1H-imidazol-1- (1,1'-Biphenyl-4-yl)dimethyl- ylmethyl) (3-trifluoromethylphenyl) silane 50 (1H-1,2,4-triazol-1-ylmethyl )silane, 4-dodecylbenzenesulfonic acid salt 100 Butyl (2,4-dichlorophenyl) [1H-imidazol-1-ylmethyl)- (1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane, 1:1 complex with copper chloride 100 methyl silane bis(2,4-Dichlorophenyl)(1H-imidazol-1-ylmethyl)methylsilane 100 90 (1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl) - silane, 1:1 complex with chloride (2,4-Dichlorophenyl)(1H-imidazol-1-ylmethyl)methyl (phenyl)silane 100 zinc 100 (4-Chlorophenyl)(1H-imidazol-1-ylmethyl)methyl(phenyl)silane 100

107

108

Compound % control of bacterial leaf spot in southern corn

Dimethyl (4-methoxyphenyl) (1H-1,2,4-triazol;-l-ylmethyl silane 90 (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-yhneth,yl) silane 90 bis (4-Chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl)r silane 80 bis (4-Chlorophenyl) enyl jhydroxy{1H-1,2,4-triazol-1-ylmethyl j silane 90 · bis (4-Fluorophenyl) hydroxy(1H^1,2,4-triazol-1-ylmethyl) silane 100 bis (4-Chlorophenyl) hydroxy(4H-1,2,4-triazol-1-ylmethyl) silane 80

Oxybis[ (4-fluorophenyl )(lHt-l,2,4-triazol-l-ylmethyl) silane 97 (l,l'-Biphenyl-4-yl)methyl(2-propoxy) (lH-l,2,4-triazol-l-ylmethyl)silane 90 (l,l'-Biphenyl-4-yl)( 4-fluorophenyl Jmethyl (lH-l,2,4-triazol-l-ylmethyl) Silane 80

Dimethyl (4-trifluoromethoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl)silane 80 (4'-Bromo-1,1'-biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane 70 (1,1'-Biphenyl-4-yl)dimethyl(5-methyl-1H-1,2,4-triazol-1-ylmethyl)silane 80 (1,1*-Biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane, 1:1 complex with copper chloride 80 in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TRÉM 014 (polyhydric alcohol esters). These suspensions are sprayed on the seedlings peanuts so that they start to drip. The next day, the plants are inoculated with a suspension of Cercospora arachidicola spores, which cause yellow leaf spot on peanuts, and incubated in a humidity chamber at 27°C for 24 hours and then left in a growth chamber for a further 14 days and then the degree of infestation is assessed. The results are in the following table. Treated plants show little or no infestation, while untreated plants have numerous spots. Phytotoxicity such as scorching is observed in some treated plants.

Table XXV

Compound % control of yellow leaf spot in groundnut (l,l'-Biphenyl-4-yl) dimethyl(lH-l,2,4-triazol-l-ylmethyl silane, 2:1 complex with copper chloride 80

Example 73 bis (4-Fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl] silane 100

Dimethyl [ 4-fluorophenyl j (1H-1,2,4-triazol-1-ylmethyl) silane 50 [ 4-(1,1-Dimethyl jphenyl] dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 35

Dimethyl (1H-1,2,4-triazol-lylmethyl) (2-trifluoromethylphenyljsilane 25"

Butyl (2,4-dichlorophenyl ] methyl(1H-1,2,4-triazol-l-yl.methyl)silane. 100 bis (2,4-Dichlorophenyl j (methyl j (1H-1,2,4-triazol-1-ylmethyl) ] silane 100 (2,4-Dichlorophenyl)methyl(phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100 (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-l-ylmethyl) silane 100 (4-Fluorophenyl j methyl (phenyl) (1H-1,2,4-triazol-l-ylmethyl) silane 100

The active ingredients according to the invention are dissolved in

105

106

Compound % reduction in bacterial leaf spot of southern corn Compound % reduction in bacterial leaf spot of southern corn 4-Bromophenyl (methyl)phenyl- bis (4-Fluorophenyl) (1H- (1H-1,2,4-triazol-1-ylmethyl)- -imidazol-1-ylmethyl) - silane 80 methylsilane 60 [ bis (2-Chlorophenyl)] methyl- [ 4-(1,1-Dimethylethyl)phenyl] (1H-1,2,4-triazol-1-ylmethyl) - (ΙΗ-imidazol-1-ylmethyl j- silane 60 dimethylsilane 70 Cyclohexyl (dimethyl) - (IH-Imidazol-1-ylmethyl) - (1H-1,2,4-triazol-1-ylmethylj dimethyl (2-trifluoromethyl- silane 50 phenyl ysilane 90 (1,1'-Biphenyl-4-yl)dimethyl Butyl (2,4-dichlorophenyl) - (1H-1,2,4-triazol-1-ylmethylj- (ΙΗ-imidazol-l-ylmethyl] - silane, salt of 4-dodecylbenzenesulfonic acid 100 methylsilane 80 bis (2,4-Dichlorophenyl) - (1,1'-Biphenyl-4-yl)dimethyl (1H-imidazol-1-ylmethyl)- (1H-1,2,4-triazol-1-ylmethylj - methylsilane 80 silane, 1:1 complex with copper(II) chloride 100 (4-Fluorophenyl)- (1,1'-Biphenyl-4-yl)dimethyl (1H-imidazol-1-ylmethyl)- (1H-1,2,4-triazol-1-ylmethyl)- methyl [phenyl silane 80 silane, 1:1 complex with chloride zinc 90 (2,6-Dimethoxyphenyl j (dimethyl) (1H-imidazole-1- (1,1'-B ifenyl-4-yl)dimethyl ylmethyl silane 50 (1H-1,2,4-triazol-1-ylmethylj- sllan, 1:1 complex with sulfate Dibutyl (1H-imidazol-1- manganese team 100 -ylmethyl j methylsilane 90 2-Chlorophenyl (4-Chlorophenyl) - (l,l‘-Biphenyl-4-yl)- methyl (1H-1,2,4-triazol-1- [ 1H-imidazol-1-y Imethyl j - -ylmethyl)silane 60 methyl (phenyl silane 80 (Ι,Γ-Bifenyl-4-ylj dimethyl- (1,1'-Biphenyl-3-yl)dimethyl- (IH-imidazol-1-ylmethyl) - (1H-imidazol-1-ylmethyl)- silane 90 silane 90 Butyl (4-chlorophenyl) - [ bis (2-Chlorophenyl) ] - (1H-imidazol-1-ylmethyl)- (ΙΗ-imidazol-1-ylmethyl) - silane 50 methylsilane 90 (3,4-Dichlorophenyl- Cyclohexyl (dimethyl j- (1H-imidazol-1-ylethyl) - (ΙΗ-imidazol-1-ylmethyl) - silane 70 silane 50 (2,4-Dichlorophenyl)dimethyl- (4-Bromophenyl)dimethyl- (ΙΗ-imidazol-1-ylmethyl) - (1H-1,2,4-triazol-1-ylmethyl j - silane 70 silane 90 bis (4-Chlorophenyl- ((1,1'-Biphenyl-4-yl)dimethyl- (ΙΗ-imidazol-1-ylmethyl) - (1H-1,2,4-triazol-1-ylmethyl) - methylsilane 60 silane 90 (ΙΗ-imidazol-1-ylmethyl) - (3,4-Dichlorophenyl j dimethyl- triphenylsilane 50 (1H-1,2,4-triazol-1-ylmethyl)silane 90

Diphenyl (1H-imidazol-1-ylmethylj methylsilane

103

104

Compound % reduction of apple scab

Compound % control of bacterial leaf spot in southern corn

Dimethyl (octadecyl) (1H1,2,4-triazol-1-ylmethyl) silane 60

And _g growth reduction

B _c chlorosis

C compound used at a concentration of 400 ppm D _b brown

Example 72

The active ingredients of the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TRÉM 014 (esters of polyhydric alcohols). These suspensions are sprayed onto corn seedlings until they start to run off. The following day, the plants are inoculated with a suspension of Helminthosporium maydis spores, which cause bacterial leaf spot of southern corn, and incubated in a humidity chamber at 20°C for 24 hours and then left in the growth chamber for a further 7 days and the extent of infestation is assessed. The percentage reduction in infestation is given in the following table. Treated plants show little or no infestation, while untreated plants have numerous spots. In some plants, phytotoxicity is manifested in the form of reduced growth, along with the reduction in infestation.

Table XXIV

Compound % control of bacterial leaf spot in southern corn

Methyldiphenyl (1H-1,2,4-triazol-1-ylmethyl) silane 80 (1,1'-Bifenyl-4-yl j dimethyl (4H-1,2,4-triazol-4-ylmethyl) silane 100 bis (4-Fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl)silane 100

Dimethyl (4-fluorophenyl)[1H-1,2,4-triazol-1-ylmethyl)silane 90

Dimethyl (4-methylthiophenyl) (1H-1,2,4-triazol-1-ylmethyl j silane 80

Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (4-trifluoromethylphenyl) silane 50

Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-l-ylmethyl) silane 100 bis (2,4-Dichlorophenyl j (methyl) (1H-1,2,4-triazol-l-ylmethyl j silane 80 (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90 (4-Fluor enyl) methyl (phenyl j (1H-1,2,4-triazol-l-ylmethyl) silane 90 (2-Chlorophenyl j dimethyl(1H-1,2,4-triazol-1-ylmethyl) J silane 100 [ 4-(4-Chlorophenoxy) phenyl ] dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 50 (3,5-Dichlorophenyljdimethyl(lH-l,2,4-triazol-l-ylmethyl) silane 40 f 1,l'-Bif phenyl-4-yl J butyl(methyl) (lH-l,2,4-triazol-l-ylmethyl) silane 50 (Ι,Γ-Bif phenyl-4-yl) methyl(phenyl) (lH-l,2,4-triazol-l-ylmethyl) silane 90 [bls(4-Methoxyphenylj jmethyl(1H-1,2,4-triazol-l-ylmethyl) J silane 90 (1,1'-Biphenyl-2-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl) silane 90 (Ι,Γ-Biphenyl-3-yl j dimethyl(1H-1,2,4-triazol-1-ylmethyl) j silane 100

2-Chlorophenyl (methyl]phenyl(1H-1,2,4-triazol-1-ylmethyl)silane 100

101

102

238826

Compound % reduction in apple scab Compound % reduction in apple scab [ bis (4-Bromophenylj ] (1H- -imidazol-1-ylmethyl) - Dimethyl (1H-imidazol-1-ylmethyl) joctadecylsilane 80 methyl silane (1,1'-Biphenyl-4-yl)-dimethyl(1H-imidazol-1-ylmethyl)- 50 bis (4-Chlorophenyl j hydroxy(1H-1,2,4-triazol-1-ylmethyl)- silane 100 silane, 1:1 complex with copper chloride 100 bis( 4-Fluorphenyl (hydroxy- (2-Chlorophenyl] [ 4-Chlorophenylj - [ 1H-1,2,4-triazol-1-ylmethyl j - silane 100 (1H-imidazol-1-ylmethyl)methylsilane 80 tris (4-Fluorphenyl) - (1H- (1H-Imidazol-7-ylmethyl)- -1,2,4-triazol-1-ylmethylj- silane 60 phenyl [ bis (2-propoxy) ] silane (2-Chlorophenyl(dimethyl)(1H-imidazol-1-ylmethyl)- 70 bis (4-Chlorophenyl)hydroxy(4H-1,2,4-triazol-4-ylmethyl) silane 100 silane Dimethyl(4-methylphenyl) (1H-1,2,4-triazol-1-ylmethyl) - 60 Oxybis[bis(4-fluorophenyl)(1H-1,2,4-triazol-1-ylmethyl)- silane] 100 silane (4-Bromophenyl j dimethyl (1H1,2,4-triazol-1 -ylmethyl J - 50G ^A (1,1'-Biphenyl-4-ylmethyl- (2-propoxy J (1H-1,2,4-triazol-1-ylmethyl isolate 100 silane (1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)- 90G (1,1'-Bifenyl-4-yl j hydroxy(methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100

silane 100 (1,1'-Biphenyl-4-yl) (4-fluorophenyl)-

(4-Chlorophenyl)dimethyl 1- methyl (1H-1,2,4-triazol-1- (1H-1,2,4 triazol-1-ylmethyl) - -ylmethyl silane 100 silane 100 Dimethyl (4-trifluoromethoxy- Butyl (4-chlorophenyl Jmethyl- phenyl) (1H-1,2,4-triazol-1- (1H-1,2,4-triazol-1-ylmethyl]- -ylmethyl silane 90 silane 100G (4'-Bromo-1,1-biphenyl-4-yl j - Dimethyl (l-naphthalenyl) - dimethyl (1H-1,2,4-triazole-1- (1H-1,2,4-triazol-1-ylmethyl) - -ylmethyl silane 100 silane 50 (1,1'-Bifenyl-4-yl j dimethyl- (3-Chlorophenyl)dimethyl- (5-methyl-1H-1,2,4-triazole- (1H-imidazol-1-ylmethyl)- -1-ylmethyl silane 100 silane 60 (1,1'-Biphenyl-4-yl jdimethyl- (1,1'-Biphenyl-4-yl)(4-fluoro- (1H-1,2,4-triazol-1-ylmethylj- phenyl] (IH-imidazol-1- silane, 1:1 complex with chloride - ylmethyl) methylsilane 50 cupric 100 Dimethyl (IH-imidazol-1- (1,1'-Bifenyl-4-yl)dimethyl- - ylmethyl j (4-trifluoroformethoxy- (1H-1,2,4-triazol-1-ylmethyl j - phenyl silane 50 silane, 2:1 complex with chloride (4'-Bromo-1,1'-biphenyl-4-yl j - cupric 100 dimethyl (1H-imidazol-1- (3-Chlorophenyl idinethyl- -ylmethyl silane 50 (1H-1,2,4-triazol-1-ylmethyl j silane 60 (3,5-Dichlorophenyl)dimethyl(1H-imidazol-1-ylmethyl)silane 50

100

Compound % reduction in apple scab Compound % reduction in apple scab 2-Chlorophenyl (4-chlorophenyl)methyl (1H-1,2,4-triazol-1-ylmethyl 90 (4-Fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 100 2-Chlorophenyl (dimethyl) (1H-1,2,4-triazol-1-ylmethyl) silane 60 (ΙΗ-Imidazol-l-ylmethyl j - (2-methoxyphenylj- dimethyl silane 60 (1,1'-Biphenyl-4-yl)dimethyl(1H-imidazol-1-ylmethyl) (2-Chlorophenyl j (1H-imidazol-1-ylmethyl j dimethylsilane 90 silane Butyl (4-chlorophenyl)- 80 Butyl (1H-imidazol-1-ylmethyl) methyl (phenyl j silane 80 (ΙΗ-imidazol-1-ylmethylj - methyl silane 90 1,1'-Biphenyl-4-yl)butyl- (1H-imidazol-1-ylmethyl)- (1H-imidazol-1-ylmethyl j methylsilane 100 dimethyl (1-naphthalenyl) silane 40 Butyl (4-fluorophenyl)- (3,4-Dichlorophenyl j- (1H-imidazol-1-ylmethyl j methylsilane 80 (1H-imidazol-1-ylmethyl)dimethylsilane 80 Dibutyl (1H-imidazol-1- (1H-imidazol-1-ylmethyl] dimethyl (4-phenoxyphenyl) silane 100 -ylmethyl) methylsilane bis(1,Γ-Bifenyl-4-yl)(1H-imidazol-1-ylmethyl)- 30 (2,4-Dichlorophenyl)dimethyl(1H-imidazol-1-ylmethyl)silane 100 methyl silane (1H-Imidazol-1-ylmethyl) [ bis (4-methoxyphenyl j j - 50 Diphenyl (1H-imidazol-1-ylmethylj methylsilane 50 methyl silane (1,1*-Bifenyl-2-yl j -dimethyl·· 50 bi9(4-Fluorophenyl)- (1H-imidazol-1-ylmethyl) silane 90 (1H-imidazol-1-ylmethylj methylsilane 100 (1,1'-Bifenyl-3-yl)dimethyl- Dimethyl (1H-imidazol-1- (1H-imidazol-1-ylmethyl j silane 90 ylmethyl) (4-trifluoromethylphenyl isolate 60 ^cents (2-Chlorophenyl) (1H-irnidazole- [ 4-(1,1'-Dimethylethyl jphenyl] - -1-ylmethyl) methyl (phenyl) silane 100 (1H-imidazol-1-ylmethyl)dimethylsilane 50 (4-Bromophenyl) (IH-imidazole- Butyl (2,4-dichlorophenyl) - -1-ylmethyl jmethyl (phenyl) silane 30 (1H-imidazol-1-ylmethyl)methylsilane 100B [bis(2-Chlorophenyl)](1H- bis (2,4-Dichlorophenyl) - -imidazol-1-ylmethyl j methylsilane 60 (1H-imidazol-1-ylmethyl)methylsilane 40 Dimethyl (1H-imidazol-1- (2,4-Dichlorophenyl)- ylmethyl) (4-methylsulfonylphenyl islan 80 (1H-imidazol-1-ylmethyl) methyl (phenyl islan 80 Cyclohexyl (dimethyl (1H- (4-Chlorophenyl)- -imidazol-1-ylmethyl j silane 100B

(ΙΗ-imidazol-1-ylmethyl) methyl (phenyl isolate 100

Compound % reduction of apple scab

Compound % reduction of apple scab (2,4-Dichlorophenyl) dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane 100 bis (4-Chlorophenyl) (methyl)(1H-1,2,4-triazol-1-ylmethyl j silane 100

Methylphenyl(1H-1,2,4-triazol-1-ylmethyl) silane 100 (1,1'-Biphenyl-4-yl j dimethyl (4H-1,2,4-triazol-4-ylmethyl) j silane 80 bis (4-Fluorophenyl) (methyl j (1H-1,2,4-triazol-1-ylmethyl) silane 100

Dimethyl (4-fluorophenylj(1H-1,2,4-triazol-1-ylmethyl)silane 80C ^B

Dimethyl ¹ (4-methylthiophenyl )(1H-1,2,4-triazol-1-ylmethyl j silane 60

Dimethyl (1H-1,2,4-triazol-1-ylmethyl] (2-trifluoromethylphenyl) silane 65G ^AC (2-Methoxyphenyl jdlmethyl (1H-1,2,4-triazol-1-ylmethyl) silane 80

Butyl (2,4-dichlorophenyl jmethyl(lH-1,2,4-triazol-l-ylmethyl)j silane 100G (4-Chlorophenyl j methyl [phenyl) (1H-1,2,4-triazol-l-ylmethyl) silane 100 (4-Fluorophenyl j methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100

Butyl (methyl jphenyl(1H-1,2,4-triazol-1-ylmethyl) silane 80

Dodecyl (dimethyl) (1H-1,2,4-triazol-1-ylmethyl) silane 40B ^cn (2-Chlorophenyl)dimethyl(1H-1,2,4-triazol-1-ylmethyl) silane 100 T-Biphenyl-4-yl (butyl) methyl (1H-1,2,4-triazol-1-ylmethyl)silane 80

Butyl (4-fluorophenyl J methyl(1H-1,2,4-triazol-1-ylmethyl)silane 100 (1,1'-Biphenyl-4-yl)methyl(phenyl) (1H-1,2,4-triazol-1-ylmethyl)silane 100 (1,1'-Biphenyl-2-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane 60 (1,1'-Biphenyl-3-yl)dlmethyl(1H-1,2,4-triazol-1-ylmethyl)silane 50

2-Chlorophenyl (methyl jphenyl(1H-1,2,4-triazol-1-ylmethyl) silane 90

4-Bromophenyl (methyl)phenyl- (1H-1,2,4-triazol-1-ylmethyl)silane 100 [bis (2-Chlorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane 40 [bis (4-Bromophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane 80 (1,1 ‘-Biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane, 4-dodecylbenzenesulfonic acid salt 100 (1,1 ‘-Biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane, 1:1 complex with copper chloride 100 (Ι,Γ-Biphenyl-4-yl) dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane, 1:1 complex with zinc chloride 100 (1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane, 1:1 complex with manganese sulfate 100

Compound % barley powdery mildew control

Example 70

The active ingredients of the invention are dissolved in acetone in an amount corresponding to 6% of the total volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TRÉM 014 (esters of polyhydric alcohols). These suspensions are sprayed onto barley seedlings until they start to run off. The following day, the plants are inoculated with a suspension of spores of the fungus Erysiphe graminis, which causes powdery mildew of barley, and incubated in a growth chamber for 7 days. The degree of infestation is then assessed. The percentage of infestation reduction is given in the following table. Treated plants show little or no powdery mildew infestation, while untreated plants are covered with powdery mildew.

you. Compound % reduction in barley powdery mildew Dodecyl (dimethyl) (1H-1,2,4-triazol-1-ylmethyl j silane ^100A Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 100 (3,4-Dichlorophenyl)(1H-imidazol-1-ylmethyl)dimethylsilane 80 Dimethyl (1H-iniidazol-1'-ylmethyl J (4-methoxyphenyl J silane 100 (2,4-Dichlorophenyl J dimethyl (1H-imidazol-1-ylmethyl) J silane 100 bis (4-Chlorophenyl J (1H-imidazol-1-ylmethyl J methylsilane 100 Diphenyl (1H-imidazol-1-ylmethyl)-methylsilane 100 Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethylphenyljsilane 100 Dodecyl (dimethyl) (1H-imidazol-1-ylmethyl isolate 100' Butyl (4-chlorophenyljmethyl(1H-1,2,4-triazol-1-ylmethyl) silane 90 (3,4-Dichlorophenyl)dimethyl(1H-1,2,4-trazol-1-ylmethyl)silane 100

Dimethyl (4-methoxyphenyl J (1H-1,2,4-triazol-1-ylmethyl)silane 100 (2,4-Dichlorophenyl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane 100 bis(4-Chlorophenyl) (methyl)(1H-1,2,4-triazol-1-ylmethyl)silane 100 (1H-1,2,4-Triazol-1-ylmethyl j triphenylsilane 100

Methyldiphenyl(1H-1,2,4-triazol-1-yhnethyl)silane 100

Dimethyl (1H-1,2,4-tri.zol-1-ylmethyl) (2-trifluoromethylphenyl)-silane 100

A compound used at a concentration of 200 ppm Example 71

The eye-catching substances according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 100 ppm of the active ingredient. On the same day, the plants are inoculated with a suspension of TRÉM 014 spores (esters of polyhydric alcohols). These suspensions are sprayed onto apple seedlings until initial runoff. The following day, the plants are inoculated with a suspension of spores of the fungus Venturia inaequalis, which causes apple scab, and incubated in a chamber with saturated humidity at 20 °C for 24 hours and then left for 10 to 12 days in a growth chamber. The degree of infestation is assessed and is shown in the following table. Treated plants show less scab compared to untreated plants, which are covered with spots. Phytotoxicity, manifested by a reduction in growth, is observed in some plants simultaneously with a reduction in scab infestation.

Compound % reduction of apple scab (3,4-Dichlorophenyl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane 80

Dimethyl (4-phenoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl j silane 100

Dimethyl (4-methoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl j silane

100

Compound % reduction in powdery mildew of cucumbers Compound % reduction in powdery mildew of cucumbers (1,1'-Biphenyl-4-yl)dimethyl- bis (4-Fluorphenyl)hydroxy- (1H-imidazol-1-ylmethyl)- (1H-1,2,4-triazol-1-ylmethyl)- silane, 1:1 complex with chloride silane 100H copper 100 tris (4-Chlorophenyl)- (2-Chlorophenyl) (4-Chlorophenyl) - (1H-1,2,4-triazol-1-ylmethyl) - (1H-imidazol-1-ylmethyl)- silane 100 methylsilane 100 bis (4-Chlorophenyl) hydroxy- (2-Chlorophenyl) (dimethyl)- (4H-1,2,4-triazol-1-ylmethyl)- (ΙΗ-imidazol-1-ylmethyl) - silane 100 silane G0 Oxybis[ bis(4-fluorenyl)- (Dimethyl Jphenyl (1,2,4- (1H-1,2,4-triazol-1-ylmethyl) - -triazol-1-ylmethyl)silane 100 silane] 100 Ethyldimethyl (1H-1,2,4- (1,1-Biphenyl-4-yl)methyl- -triazol-1-ylmethyl)silane 100 (2-propoxy(1H-1,2,4-triazole- . -1-ylmethyl) silane 100 Butyldimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1,1'-Biphenyl-4-yl Jhydroxymethyl) (1H-1,2,4-triazol-1- Dimethyl (4-methylphenyl) - ylmethyl)silane 100 (1H-1,2,4-triazol-1-ylmethyl)silane 100G' (1,1'-Biphenyl-4-yl)(4- -fluorenyl) methyl (1H- [ 4-Bromophenyl)dimethyl- 1,2,4-triazol-1-ylmethyl)- (1H-1,2,4-triazol-1-ylmethyl) - silane 100 silane 100G Dimethyl (4-trifluoromethoxy- tris (4-Chlorophenyl) (1H- phenyl) (1H-1,2,4-triazol-1- -imidazol-1-ylmethyl) silane 100 -ylmethyl)silane 100G tris í 4-Fluorphenyl) (1H- (4'-Bromo-1,1'-biphenyl-4-yl) - -imidazol-1-ylmethyl ]silane 100 dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (4-Fluorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane 100 (1,1'-Biphenyl-4-yl)dimethyl(5-methyl-1H-1,2,4-triazol- bis (4-Chlorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane 100 -1-ylmethyl Jsilane 100 (1,1'-Biphenyl-4-yl)dimethyl- (3-Chlorophenyl)dimethyl (1H- (1H-1,2,4-triazol-1-ylmethyl) - -imidazol-1-ylmethyl) silane 80 silane,l:l complex with copper chloride 100 (1,1'-Biphenyl-4-yl) (4-fluorophenyl) (1H-imidazol-1- (1,1-Bifenyl-4-yl)dimethyl- -ylmethyl ] methylsilane 100 (1H-1,2,4-triazol-1-ylmethyl) silane, 2:1 complex with chloride Dimethyl (1H-imidazol-1-ylmethyl (4-trifluoromethoxy- cupric 100 phenyl)silane 100G (4-Fluorophenyl)methyl (2-propoxy) (1H-1,2,4-triazol- (4'-Bromo-1,1'-biphenyl-4-yl) - -1-ylmethyl (silane 100 dimethyl (1H-imidazol-1-ylmethyl) silane 100 (1,1'-Dimethyl-1-ethoxy)[bis(4-fluorophenyl)](1H-1,2,4- (3,5-Dichlorophenyl)dimethyl(ΙΗ-imidazol-l-ylmethyl) - triazol-1-ylmethyl)silane 100 silane 100G A _G growth reduction B,t hormonal action

100H bis(4-Chlorophenyl)hydroxy(1H-1,2,4-triazo;1-1-ylmethyl)silane

Compound % reduction in powdery mildew of cucumbers Compound % reduction in powdery mildew of cucumbers bis(4-Chlorophenyl)-(1H-imidazol-1-ylmethyl)- Dodecyl (dimethyl) (1H-imidazol-1-ylmethyl) - methyl silane (1H-Imidazol-1-ylxenethyl) - 100 silane (2-Chlorophenyl) (1H-imidazole- 55 triphenylsilane Diphenyl (1H-imidazole-1- 100 -1-ylmethyl) dimethyl silane [ 4-(4-Chlorophenoxy)phenyl] - 100 -ylmethyl)-methylsilane bis(4-Fluorophenyl))1H-imidazol-1-ylmethyl)- 100 dimethyl (1H-imidazol-1-ylmethyl) silane Butyl (1H-imidazol-1-ylmethyl)- 100 methyl silane Dimethyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl)- 100 methyl (phenyl) silane (1,1'-Biphenyl-4-yl)butyl- (1H-imidazol-1-ylmethyl) - 100 strong Dimethyl (1H-imidazol-1-ylmethyl) (4-methylthiophene 1) - 100G methyl silane Butyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) methyl- 100 silane Dimethyl (1H-imidazole-1- 100 silane Dibutyl (1H-imidazole-1- 100 -ylmethyl) (4-trifluoromethylphenyl) silane Dimethyl (1H-imidazole-1- 100 -ylmethyl) methylsilane 1,1'-Biphenyl-4-yl)(1H- -imidazol-1-ylmethyl) methyl- 100 -ylmethyl) (3-trifluoromethylphenylsilane [ 4-(1,1-Dimethylethyl)- 80 (phenyl)silane 1,1-Dimethylethoxy) (1H-imidazol-1-ylmethyl Jmethylyl- 100 phenyl] (1H-imidazol-1-ylmethyl)dimethylsilane (ΙΗ-Imidazol-l-ylmethyl] - 80 (phenyl)silane (ΙΗ-Imidazol-l-ylmethyl) methyl (phenyl) (2-propoxy) - 100 dimethyl (2-trifluoromethylphenyl) silane Butyl (2,4-dichlorophenyl) - 100G silane (ΙΗ-Imidazol-1-ylmethyl) [bis (4-methoxyphenyl) ] - 90 (1H-imidazol-1-ylmethyl)methylsilane bis (2,4-Dichlorophenyl)- 100G methyl silane (1,1'-Biphenyl-2-yl Jdimethyl(1H-imidazol-1 -ylmethyl) - 50 (1H-imidazol-1-ylmethyl)methylsilane (2,4-Dichlorophenyl) - [1H- 100 silane (2-Chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) - 50 -imidazol-1-ylmethyl) methyl(phenyl) silane (4-Chlorophenyl) (1H-imidazole- 100 silane (4-Bromophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) - 1.00 -1-ylmethyl) methyl (phenyl) silane (4-Fluorophenyl) (1H-imidazole- 100 silane [ bis (2-Chlorophenyl) ] (1H-imidazol-1-ylmethyl jmethyl- 100 -1-ylmethyl) methyl (phenyl) silane 100 silane Cyclohexyl (dimethyl (1H- 100 (ΙΗ-Imidazol-1-ylmethyl)(2-methoxyphenyl)dimethyl- -imidazol-1-ylmethyl) silane 100G silane 100G [ bis (4-Bromophenyl) ] (1H-imidazol-1-ylmethyl) methyl- (2,3-Dimethoxyphenyl)(1H-imidazol-1-ylmethyl)dimethylsilane 100 silane 100

Compound % reduction in powdery mildew of cucumbers Compound % reduction in powdery mildew of cucumbers (1,1'-Bifenyl-4-yl)methyl- Phenyl [ bis (2-propoxy) ] - (phenyl)1H-1,2,4-triazol-1- (1H-1,2,4-triazol-1-ylmethyl) - -ylmethyl)silane 100 silane 100 (1,1-Dimethylethoxy)methyl- [ bis (2-Fluorophenyl) ] methyl- (phenyl ] 1H-1,2,4-triazol-1- (1H-1,2,4-triazol-1-ylmethyl) - -ylmethyl)silane 100 silane, 1:1 complex with copper(II) chloride 100 Methyl (phenyl) (2-propoxy) - (1H-1,2,4-triazol-1-ylmethyl)- [ bis (2-Fluorophenyl) ) methyl- silane 100 (1H-1,2,4-triazol-1-ylmethyl)silane, 2:1 complex with chloride 1,Γ-Bif eny-2-yl)dimethyl- cupric 100 (1H-1,2,4-triazol-1-ylmethyl)silane 90 Dimethyl (1H-imidazol-1-ylmethyl jphenylsilane 100 2-Chlorophenyl (methyl)phenyl(1H-1,2,4-triazol-1-ylmethyl)- Ethyl (1H-imidazol-1-ylmethyl)- silane 100 diethylsilane 100 4-Bromophenyl (methyl)phenyl- Butyl (1H-imidazol-1-ylmethyl)- (1H-1,2,4-triazol-1-ylmethyl) - dimethylsilane 100 silane 100 (ΙΗ-Imidazol-1-ylmethyl) dimethyl (4-methylphenyl)- [bis(2-Chlorophenyl)j inethyl(1H-1,2,4-triazol-1-ylmethyl)- silane 100G ^A silane 100 (4-Bromophenyl)(1H-imidazol-1-ylmethyl)dimethylsilane 100 Cyclohexyl (dimethyl) (1H1,2,4-triazol-1-ylmethyl) - (1,1'-Biphenyl-4-yl)dimethyl- silane 100G (1H-imidazol-1-ylmethyl)silane 100 (bis(4-Bromophenyl) Jmethyl(1H-1,2,4-triazol-1-ylmethyl)- (4-Chlorophenyl) (1H-imidazole- silane 80G -1-ylmethyl)dimethylsilane 100 (1,1'-Biphenyl-4-yl)dimethyl- Butyl (4-chlorophenyl) (1H- (1H-1,2,4-triazol-1-ylmethyl)- imidazol-1-ylmethyl) methyl- silane, salt (4-dodecylbenzene- silane 100G' sulfonic acids 100 (ΙΗ-Imidazol-1-ylmethyl) - (1,1'-Biphenyl-4-yl dimethyl- dime t hy 1 (1-naphthalenyl) - (1H-1,2,4-triazol-1-ylmethyl)- silane 100 silane, 1:1 complex with copper(II) chloride 100 (3,4-Dichlorophenyl)-1H-imidazol-1-ylmethyl)- (1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)- dimethylsilane 100 silane, 1:1 complex with chloride (lH-Imidazol-l-ylmethyl- zinc 80 dimethyl (4-phenoxyphenyl) silane 100 (1,1'-Bifenyl-4-yl)dimethyl- (1H-1,2,4-triazol-1-ylmethyl)- Dimethyl (1H-imidazole) -1- silane, 1:1 complex with sulfate -ylmethyl) (4-methoxyphenyl) - manganese team 90 silane 100 2-Chlorophenyl (4-chlorophenyl) - (2,4-Dichlorophenyl)dimethyl- methyl (1H-1,2,4-triazol-1- (1H-imidazol-1-ylmethyl}- 100H ^B -vlmethvllsilan 100 silane

Compound % reduction in powdery mildew of cucumbers Compound % reduction in powdery mildew of cucumbers (4-Chlorophenyl)dimethyl- -1-ylmethyl) (2-trifluoro- 100 (1H-1,2,4-triazol-1-ylmethyl) - methylphenyl)silane silane 100 (2-Methoxyphenyl (dimethyl)- Butyl (4-chlorophenyl)methyl- (1H-1,2,4-triazol-1-ylmethyl) - 100G (1H-1,2,4-triazol-1-ylmethyl) - silane silane 100G Butyl [2,4-dichlorophenyl)methyl- Dimethyl (1-naphthalene 1) - (1H-1,2,4-triazol-1-ylmethyl) - 100G (1H-1,2,4-triazol-1-ylmethyl) - silane silane 100 bis (2,4-Dichlorophenyl) (methyl) - (3,4-Dichlorophenyl)dimethyl- (1H-1,2,4-triazol-1-ylmethyl) - 100G (1H-1,2,4-triazol-1-ylmethyl)- silane silane 100 (2,4-Dichlorophenyl)methyl- Dimethyl (4-phenoxyphenyl) - (phenyl) (1H-1,2,4-triazol-1- 100G (1H-1,2,4-triazol-1-ylmethyl) - -ylmethyl)silane silane 70 (4-Chlorophenyl)methyl (phenyl)- Dimethyl (4-methoxyphenyl) - (1H-1,2,4-triazol-1-ylmethyl) - 100G (1H-1,2,4-triazol-1-ylmethyl) - silane silane 100 (4-Fluorophenyl) methyl (phenyl) - (2,4-Dichlorophenyl)dimethyl- (1H-1,2,4-triazol-1-ylmethyl)- (1H-1,2,4-triazol-1-ylmethyl) - silane 100 silane 100H ^B Butyl (methyl)phenyl (1H- bis (4-Chlorophenyl) (methyl)- 1,2,4-triazol-1-ylmethyl)- (1H-1,2,4-triazol-1-ylmethyl) - silane 100 silane 100 (2,3-Dimethoxyphenyl)dimethyl- (1H-1,2,4-Triazol-1-ylylethyl) - (1H-1,2,4-triazol-1-ylmethyl) - triphenylsilane 100 silane 100G Methyldiphenyl (1H-1,2,4- (2,6-Dimethbxyf enyl) dimethyl- -triazol-1-ylmethyl )silane 100G (1H-1,2,4-triazol-1-ylmethyl)- silane 100G (1,1'-Biphenyl-4-yl)dimethyl(4H-1,2,4-triazol-4-ylmethyl) - Dodecyl (dimethyl) (1H- silane 90 1,2,4-triazol-1-ylmethyl) silane 60 ^cents bis (4-Fluorophenyl) (methyl)(1H-1,2,4-triazol-1-ylmethyl) - (2-Chlorophenyl)dimethyl (1H- silane 100G 1,2,4-Triazol-1-ylmethyl)silane 100G Dimethyl (4-fluorophenyl)(1H-1,2,4-triazol-1-ylmethyl) - (4-(4-Chlorophenoxy)phenyl J - silane 100G dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 80 Dimethyl (4-methylthiophenyl) (1H-1,2,4-triazol-1-ylmethyl) - (1,1'-Bifenyl-4-yl)buty 1-meth hy 1) - silane 100 (1H-1,2,4-triazol-1-ylmethyl)silane 100 Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (4-trifluoro- Butyl (4-fluorenyl) methyl- methylphenyl)silane 100G (1H-1,2,4-triazol-1-ylmethyl)silane 100 Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (3-trifluoro- bis(1,1'-Blfenyl-4-yl)(methyl)- methylphenyl)silane 100 (1H-1,2,4-triazol-1-ylmethyl)silane 100

Dimethyl (1H-1,2,4-triazole238626

Compound % rust control on wheat

Compound % reduction in wheat rust bis (4-Fluorophenyl j hydroxy (1H-imidazol-1-ylmethyl isolate 100 bis(4-Chlorophenyl]hydroxy(1H-imidazol-1-ylmethyl)Silan 80 (3-Chlorophenyl)dimethyl (1H- -imidazol-1-ylmethyl isolate 80 (1,1'-Bifenyl-4-yl) (4-fluorophenyl) (1H-imidazol-1-ylmethyl) - methyl silane 80 Dimethyl (1H-imidazol-1-ylmethyl j (4-trifluoromethoxyphenyl) isolate 100 (4'-Bromo-1,1'-biphenyl-4-yl)-dimethyl (1H-imidazol-1-ylmethyl 100 bis (4-Chlorophenyl) hydroxy(1H-1,2,4-triazol-1-ylmethyl isolate 90 bis (4-Fluorophenyl) hydroxy (1H- -1,2,4-triazol-1-ylmethyl isolate 90 tris (4-Chlorophenyl (1H-1,2,4-triazol-1-ylmethyl islan 40 tris (4-Fluorophenyl j (1H-1,2,4-triazol-1-ylmethyl 90 bis (4-Chlorophenyl) hydroxy (4H-1,2,4-triazol-4-ylmethyl 90 Oxybis [ bis (4-fluorophenyl j (111-1,2,4-triazol-1-ylmethyl isolate] 100 (1,1'-Biphenyl-4-yl} methyl (2-propoxyj (1H-1,2,4-triazol-1-ylmethyl 100 (1,1'-Biphenyl-4-yl)hydroxy (methyl) (1H-1,2,4-triazol-1-ylmethyl islate 90 (1,1'-Biphenyl-4-yl) (4-fluorophenyl) methyl (1H-1,2,4-triazol-lylmethyl 100 Dimethyl (4-trifluoromethoxyphenyl j (1H-1,2,4-triazol-1-ylmethyl 100 (4'-Bromo-1,1'-biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-yl)methyl 100

(1,1'-Biphenyl-4-yl) dimethyl (5-methyl-1H-1,2,4-triazol-1-ylmethyl) silane

100 (l,l'-Biphenyl-4-yl)dimethyl(lH-1,2,4-triazol-l-ylmethyl jsilane, : 1 complex with copper chloride 100 (l,l'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-l-ylmethyl jsilane, : 1 complex with copper chloride 100 ^A Compound used at a concentration of 200 ppm Example 69

The active ingredients of the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TRÉM 014 (esters of polyhydric alcohols). These suspensions are sprayed onto cucumber seedlings so that they just run off. The following day, the plants are inoculated with a suspension of spores of the fungus Erysiphe cichoracearum, which causes powdery mildew, and incubated in a growth chamber for 7 days. The degree of infestation is then assessed. The percentage reduction in infestation is given in the following table. Treated plants show little or no infestation, in contrast to untreated plants, which are covered with powdery mildew. Phytotoxicity, as growth restriction or adverse growth effects, is observed on some plants together with powdery mildew reduction.

Table XXI

Compound % Cucumber Powdery Mildew Control (Dimethyl)phenyl(1,2,4triazol-1-ylmethyl)silane 100

Ethyldimethyl(1H-1,2,4triazol-1-ylmethyl) silane 100

FROM

Butyldimethyl (1H-1,2,4triazol-1-ylmethyl) silane 100

Dimethyl (4-methylphenyl j(1H-1,2,4-triazol-1-ylmethyl)silane 100G ^A (4-Bromophenyl)dimethyl (1H1,2,4-triazol-1-ylmethyl)silane 100G (1,1'-Biphenyl-4-yl)-dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane

100

Compound % reduction of rust on wheat ¹ Compound % reduction in wheat rust bis(1,1'-Bifenyl-4-yl(methyl)- bis (4-Fluorophenyl) (1H-imidazole- (1H-1,2,4-triazol-1-ylmethyl) - -1-ylmethyl jmethylsilane 100 silane 80 Dimethyl (4-fluorophenyl j (1H- (1,1'-Bifenyl-4-yl) methyl (f e- -imidazol-1-ylmethyl j silane 80 nyl (1H-1,2,4-triazol-1-ylmethyl isolate 100 Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethylphenyl j - (1,1'-Bifenyl-3-yl)dimethyl (1H- silane 100' -1,2,4-triazol-1-ylmethyl isolate 2-Chlorophenyl (methyl)phenyl (ηH- 80 Butyl (2,4-dichlorophenyl) (1H-imidazol-1-ylmethyl j methylsi- -1,2,4-triazol-1-ylmethyl isolate 80 lan 100 [ bis (2-Chlorophenyl j ] methyl (1H- bis (2,4-Dichlorophenyl j (1H-imi- -1,2,4-triazol-1-ylmethyl isolate 100 dazol-1-ylmethyl) methylsilane 100 (1,1'-Bifenyl-4-yl jdimethyl (1H- 2,4-Dichlorophenyl (1H-iniidazole- -1,2,4-triazol-1-ylmethyl isolate, -1-ylmethyl) methyl (phenyl j - 4-dodecylbenzenesulfonic acid 100 silane 90 4-Chlorophenyl (1H-imidazol-1-yl- (1,1'-Bifenyl-4-yl jdimethyl (1H- methyl j methyl (pheny 1 j silane 100 -1,2,4-triazol-1-ylmethyl silane, 1 : 1 complex with zinc chloride- Dodecyl (dimethyl j (1H-imida- unknown 100 zol-1-ylmethyl silane 80 ^Λ (1,1'-Biphenyl-4-yl j dimethyl (1H- (4-(4-Chlorophenoxyphenyl] dime- -1,2,4-triazol-1-ylmethyl isolate, thyl (1H-imidazol-1-ylmethyl)- 1:1 complex with manganese sulfate 90 silane 90 Butyl (1H-imidazol-1-ylme- 2-Chlorophenyl (4-chlorophenyl)methyl (1H-1,2,4-triazol-1-ylmethyl- ethyl j methyl (phenyl j silane 90 thyl jsilan 100 (1,1'-Biphenyl-4-yl j butyl (1H-imidazol-1-ylmethyl)methyl- (bis(2-Fluorophenyl)]methyl(1H- silane 100 -1,2,4-triazol-1-ylmethyl j silane, 1:1 complex with copper chloride- (1,1'-Biphenyl-4-yl) (1H-imida- new 90 zol-1-ylmethyl) methyl (phenyl) silane 100 [ bis (2-Fluorophenyl) j methyl (1H-1,2,4-triazol-1-ylmethyl isolate, (1,1'-Bifenyl-3-yl jdimethyl (1H- 2 : 1 complex with copper chloride 100 -imidazol-1-ylmethyl silane 90 (1,1'-Biphenyl-4-yl jdimethyl (1H- (4-Bromophenyl) (1H-imidazol- -1-ylmethyl)methyl (phenyl is- -Imidazol-1-ylmethyl silane 100 lan 90 (4-Chlorophenyl) (1H-imildazol-1- (1,1'-Bifenyl-4-yl)dimethyl (1H - -ylmethyl)dimethylsilane 50 -imidazol-1-ylmethyl silane, 1 : 1 complex with copper (II) chloride 100 Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl jmethylsilane 90 (2-Chlorophenyl) (4-Chlorophenyl j - (1H-imidazol-1-ylmethyl) me- (1H-Imidazol-1-ylmethyldi- thylsilane 100 methyl (4-phenoxyphenyl isolate 60 (2-Chlorophenyl) (dimethyl) (1H- Dimethyl (1H-imidazol-1-yhnethyl) (4-methoxyphenyl islan 60 -imidazol-1-ylmethyl silane 80 Iris (4-Fluorophenyl] (1H-imida- (2,4-Dichlorophenyl)dimethyl (1H'imidazol-1-ylmethyl isolate 90 zol-1-ylmethyl silane 80

238628 cyano (3-phenoxyphenyl )methyl-4-chloro-alpha- (l-methylethyl jbenzeneacetate (fenvaleratej (3-phenoxyphenylmethyl-j + (-cis,trans-3-(2,2-dichloroethenyl j -2,2-dimethylcyclopropanecarbosylate) (permethrinj dimethyl-N,N'- [ thiobis- ] (N-methylimino)carbonyloxy-bis (ethanimidothioate (thiodicarfaj phosphorothiothionic acid, O-ethyl-O-[4-(methylthio)phenyl ]-S-n-propyl ester (sulprofos) alpha-cyano-3-phenoxybeuzyl-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (cypermethrin) cyano-(3-phenoxyphenyl methyl-4-(difluoromethoxy)-alpha-(methyl benzeneacetate ("Payoff")

0,0-diethyl-0-(3,5,6-trichloro-2-pyridyl jphosphothioate (chlorpyrifos)

O,O-dimethyl-S-[(4-oxo-1,2,3-benzotriazin-3-]4H(-yl)methyl]phosphordithioate (azinphos-methyl

5,6-dimethyl]-2-dimethylamino-4-pyrimidyldimethylcarbamate ("pirimor" j

S-(N-formyl-N-methylcarbamoylmethyl)-Ο,Ο-dimethyl phosphordithioate (formothione)

S-2-(ethylthioethyl)-Ο,Ο-dimethylphosphorothioate (demeton-S-methyl) alpha-cyano-3-phenoxybenzyl-cis-3-(2,2-dibromovinyl]-2,2-dimethylcyclopropanecarboxylate (deltamethrin) cyano-(3-phenoxyphenyl j methyl ester N-(2-chloro-4-trifluoromethylphenyl)alanine ("Mavrik")}.

Example 68

The active ingredients of the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surface-active compound TERM 014 (esters of polyhydric alcohols). These suspensions are sprayed onto wheat seedlings. The following day, the plants are inoculated with a suspension of Puccinia recondita var. tritici spores, which cause wheat rust, and incubated in a room saturated with humidity at 20 ° C for 24 hours and then left in a growth chamber for a further 7 days and then the disease is evaluated. The percentage reduction of the disease is in the following table. Treated plants have few "sores" or are free of sores, untreated plants have numerous rust sores on the leaves.

Table XX

Compound % wheat rust control (Dimethyl)phenyl (1,2,4-triazol-1-ylmethyl jsilane 90

Compound (4-Bromophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl)isolan (4-Chlorophenyl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)isolan

Butyl (4-chlorophenyl) methyl (111-1,2,4-triazol-l-ylmethyl islan (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-l-ylmethyl islan (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-l-ylmethyl) islan bis (4-Chlorophenyl) (1H-1,2,4-triazol-1-ylmethyl isolate

Dimethyl (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl silane (4-(1,1-Dimethylethyl)phenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl

Butyl (2,4-dichlorophenyl) methyl(1H-1,2,4-triazol-l-ylmethyl j silane bis (2,4-Dichlorophenyl) (methyl) (1H-1,2,4-triazol-l-ylmethyl j silane (2,4-Dichlorophenylj methyl (phenyl j (1H-1,2,4-triazol-l-ylmethyl) silane (4-Chlorophenyl) (1H-1,2,4-triazol-1-ylmethyl)silane

Dodecyl dimethyl) (1H-1,2,4-triazol-1-ylmethyl silane [4-(4-Chlorophenoxy)phenyl] -dimethyl (1H-1,2,4-triazol-1-ylmethyl silane (3,5-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl silane (1,1'-Biphenyl-4-yl) butyl (methyl) (1H-1,2,4-triazol-1-ylmethyl silane % reduction of rust on wheat

100

100

100

80 ^A

100

100

100

100

100 ^A racearum, Erysiphe graminis, Venturia inaequalis, Helminthosporium maydis, Cercospora arachidicola, Uromyces phaseoli and Monilinia fructicola, Rhizoctonia solani, Pyricularia oryzae, Phytophthora infestans and other Phytophthora species. They are also suitable for the treatment of seed diseases, for example caused by Pythium aphanadermatum.

The disease is usually treated by applying an effective amount of the active ingredient either before or after infection to the parts of the plants to be protected, such as roots, stems, leaves, fruits, seeds, tubers, or to the environment (soil or sand) where the protected plant grows. The active ingredients can also be applied to the seeds from which the protected plant will grow.

The doses of active ingredient used are influenced by numerous factors such as environmental conditions and should be determined for each individual case. Leaves are generally protected by treatment with a dose of 1 to 500 ppm of active ingredient. Plants growing in the soil can be protected from the disease by treatment with 0.1 to 20 kg/ha. Seeds and seedlings are generally protected by treatment of the seeds with an active ingredient in an amount of 0.06 to 3 g per kg/seed.

The active ingredients of the invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides or other biologically active ingredients to achieve the desired results in the shortest possible time, with minimal effort and with minimal consumption of active ingredients. The amount of these biologically active ingredients per part by weight of the composition of the invention is 0.05 to 25 parts by weight. Suitable active ingredients of this type are well known to those skilled in the art. Some are listed below:

Fungicides:

methyl 2-benzimidazole carbamate (carbendazlm) tetramethylthium ramdlsulfide (thiuram) n-dodecylguanidine diacetate (dodine ] manganese ethylene bisdithiocarbamate (nianeb) 1,4-dichloro-2,5-dimethoxybenzene (chloroneb ] methyl 1-(butylcarbamoyl )-2-benzimidazole carbamate (ienomyl)

2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil)

N-trichloromethylthiotetrahydrophthalimide (captanj

N-trichloromethylthiophthalimide (folpet J dimethyl-4,4'-(o-phenylene)bis(3-thioallophanatj(thiophanatemethyl)

2-(thiazol-4-yl jbenzimidazole (thiabendazole j tris (O-ethylphosphonate) aluminum ("Aliette") tetrachlorophthalonitrile (chlorothalonil) 2,6-dichloro-4-nitroaniline (dichlorane)

N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl ester (metalaxyljcis-N-[,(1,1,2,2-tetrachloroethyl)thio]cyclohex-4-ene-1,2-dicarboximide (captafol)

3-(3,5-dichlorophenyl)-N-(1-methylethyl j -2,4-dioxo-1-imidazolidinecarboxamide (iprodione)

3-(3,5-dichlorophenyl]-5-ethenyl-5-methyl-2,4-oxazolidindione (vinclozolin, kasugamycin

O-ethyl-S,S-diphenyl phosphorodithioate (edifsnphos)

Bactericides:

tribasic copper sulfate streptomycin sulfate oxytetracycline

Acaricides:

Senecioic acid, ester with 2-sec.butyl-4,6dinitrophenol (binapacrylj

6-methyl-1,3-dithiolo[2,3-B]quinolin-2-one (oxythioquinox)

2,2,2-trichloro-l,l-bis (4-chlorophenyl J ethanol (dicofol) bis (pentachloro-2,4-cyclopentadien-1-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin j hexakis (2-methyl-2-phenylpropyl) distannoxan (phenbutynoxide)

Nematocides:

2-(diethoxyphosphinylimino)-1,3-dithietane (phosthietane)

S-methyl-1-(dimethylcarbamoyl)-N-(methylcarbamoyloxythiophorimidate (oxamyl

S-methyl-1-carbamoyl-N-(methylcarbamoyloxy) thiophorimidate

N-Isopropylphosphoramic acid, O-ethyl-O'-[4-(methylthio)-m-tolyl] diester (fenamiphos)

Insecticides:

3-hydroxy-N-methylcrotonamide (dimethyl phosphate) ester (monocrotophos) methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol (carbofuran)

O-[2,4,5-trichloro-alpha-(chloromethyl)benzyl]phosphoric acid,

O',O'-dimethyl ester (tetrachlorovlnphos)

2-Mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, Ο,Ο-dimethyl, O-p-nitrophenyl ester (methylparathion) methylcarbamic acid, ester with alpha-naphthol (carbaryl) methyl) [ (methylamino j carbonyl] oxyjethanimidothioate (methomyl)

N'-(4-chloro-i-tolyl)-N,N-dimethylformamidine (chlorodimeform)

O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidylphosphorothioate (diazinoi octachlorocamphene (toxapene)

O-ethyl-O-p-nitrophenylphosphonothioate (EPN J

78

The ingredients are mixed, coarsely ground in a hammer mill and then in an air mill until essentially all particles are below 10 micrometers in diameter. The product is mixed again and filled into containers.

Example 60

Wettable powder (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 40% dioctyl sodium sulfosuccinate 1.5% sodium lignin sulfonate 3.0% low viscosity methylcellulose 1.5% attapulgite 54.0%

The ingredients are thoroughly mixed, passed through an air mill until the particle size is below 15 micrometers, mixed again and sieved through a sieve with a mesh diameter of 0.3 mm, and then packaged.

All active ingredients of the invention can be formulated in the same way.

Example 61

Emulsifiable concentrate (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl)silane 30% mixture of oil-soluble sulfonates and polyoxyethylene ethers 4% xylene 66%

The ingredients are mixed and stirred with gentle heating to accelerate dissolution. A fine sieve is used when filling into containers to ensure the absence of any undissolved material.

Example 62

Emulsifiable concentrate (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl)silane 20% chlorobenzene 74% condensates of sorbitan monostearate and polyoxyethylene 6%

The ingredients are mixed and stirred to form a solution that can be emulsified in water for use.

Example 63

Aqueous suspension of (1,1'-biphenyl-4-yl)dimethyl (1H-imidazol-1-ylmethyl)silane 25% hydrated attapulgite 3% crude calcium lignin sulfonate 10% sodium dihydrogen phosphate 0.5% water 61.5%

The ingredients are ground together in a ball mill or roller mill until the particle diameter is below 10 micrometers.

Example 64

Highly concentrated concentrate (1,1'-biphenyl-4-yl dimethylf lH-imidazol-1-ylmethyl Jsilane 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

The ingredients are mixed and ground in a hammer mill to produce a highly concentrated concentrate with particle sizes of substantially 0.3 mm. This material can then be processed in various ways.

Example 65

Granules wettable powder according to example 60 15% gypsum 69% potassium sulfate 16%

The ingredients are mixed in a rotary mixer and sprayed with water to effect granulation. When most of the particles reach the desired size — 1.0 to 0.42 mm in diameter — the granules are removed, dried, and sorted. Larger particles are crushed and also used if they are of the desired size. The granules contain the active ingredient.

Example 66

Powder highly concentrated concentrate according to example 64 25.4% powdered pyrophyllite 74.6%

The ingredients are mixed thoroughly and packaged for use.

Example 67

Emulsifiable concentrate

4-chloromethyl (methyl)phenyl (1H-imidazol-1-ylmethyl)silane 20% chlorobenzene 74% sorbitan monostearate and polyoxyethylene condensates 6%

The ingredients are mixed and stirred to form a solution that can be emulsified in water for use.

The active ingredients of the invention are useful for controlling plant diseases. They are effective against a wide variety of plant diseases, especially against leaf diseases of ornamental plants, vegetables, cereals and fruit plants, such as Puccinia recondita, Erysiphe cicho238626

Example 51

Emulsifiable concentrate dimethyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl)silane 20% chlorobenzene 74% condensates of sorbitan monostearate and polyoxyethylene 6%

The ingredients are mixed and blended to form a solution which can be emulsified in water for use.

Example 52

Emulsifiable concentrate dimethyl (4-methylphenyl j (1H-1,2,4-triazol-1-ylmethyl]silane 30% mixture of oil-soluble sulfonates and polyoxyethylene ethers 4% xylene 66%

The ingredients are mixed and stirred with gentle heating to accelerate dissolution. A fine filter is used during packaging to ensure the absence of any undissolved matter in the product.

Example 53

Granular wettable powder according to Example 46 15% gypsum 69% potassium sulfate 16%

The ingredients are mixed in a rotary mixer and sprayed with water to achieve granulation. When most of the material reaches the desired size range, 1.0 to 0.42 mm, the granules are removed, dried and screened. The larger sized material is crushed to obtain additional material of the appropriate size. These granules contain the active ingredient.

Example 54

Emulsifiable concentrate (2,4-dichlorophenyl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane 30% mixture of oil-soluble sulfonates and polyoxyethylene ethers 4% xylene 66%

The ingredients are mixed and stirred with gentle heating to accelerate dissolution. A fine sieve is used when filling into the container to ensure that the product does not contain any undissolved matter.

Example 55

Emulsifiable concentrate butyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl jsilane 30% mixture of oil-soluble sulfonates and polyoxyethylene ethers 4% xylene 66%

The ingredients are mixed and stirred with gentle heating to accelerate dissolution. A fine sieve is used when filling into containers to ensure the absence of any undissolved material.

Example 56

Emulsifiable concentrate

bis(4-chlorophenyl)methyl (1H-1,2,4- -triazoyl-1-ylmethyl silane 39 % a mixture of oil-soluble sulfonates and polyoxyethylene ethers 4 % xylene 66 % The ingredients are mixed and blended for mild-

heating to accelerate dissolution. When filling into containers, a fine sieve is used to ensure the absence of any undissolved material.

Example 57

Emulsifiable concentrate bis (4-fluorophenyl] methyl (1H-1,2,4-triazol-1-ylmethyl]silane 20% chlorobenzene 74% condensates of sorbitan monostearate and polyoxyethylene 6%

The ingredients are mixed and blended to form a solution that can be emulsified in water when used.

Example 58

Emulsifiable concentrate

4-fluorophenyl (methyl)phenyl (1H-1,2,4-triazol-1-ylmethyl)silane 39% mixture of oil-soluble sulfonates and polyoxyethylene ethers 4% xylene 66%

The ingredients are mixed and stirred with gentle heating to accelerate dissolution. A fine sieve is used when filling into containers to ensure the absence of any undissolved material.

Example 59

The wettable powder (1,1'-biphenyl-4-yl) dimethyl (11-imidazol-1-ylmethyl jsilane 59% sodium alkyl phthalene sulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46% is mixed and sieved through a sieve with a mesh diameter of 0.3 mm and then packaged. All active ingredients according to the invention are processed into a wettable powder in the same way.

Example 47

Wettable powder (4-bromophenyl] dimethyl-1H-1,2,4-triazole Depending on the intended use and the physical properties of the active substance, the composition may contain a higher or lower amount. A higher ratio of active substance to surfactant is sometimes desirable and is achieved by incorporating the surfactant into the composition according to the invention or by tank mixing.

Typical solid diluents are described by Watkins et al. in Handbook of Insecticide Dust Diluents and Carriers, 2nd ed., Dorland Books, Caldwell, New Jersey. Diluents with higher absorptive capacity are preferred for wettable powders and denser ones for powders. Typical liquid solvents and diluents are described in Marsden's "Solvent Guide," 2nd ed., Interscience, New York, 1950. Solubility below 0.1% is preferred for suspension concentrates; solution concentrates are preferably resistant to phase separation at 0°C. McCutcheor's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, New Jersey, and Sisely and Wood's "Encyclopedia of Surface Active Agents" Surfactants], Chemical Publishing Co., Inc., New York, 1964, contains a list of surfactants and recommended uses. All compositions may contain minor amounts of additives to reduce foaming, caking, corrosion, microbial growth, and similar effects.

Methods of making such compositions are generally known. Solutions are prepared by simple mixing of the ingredients. Fine solid compositions are prepared by mixing and usually grinding, for example in a hammer mill or in a fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent No. 3,060,084). Granules and pellets can be prepared by spraying the active ingredient onto a preformed granular carrier or by the agglomeration technique. See J. E. Browning, "Agglomeration," Chemical Engineering, December 4, 1967, pp. 147 et seq., and Perry's Chemical Engineer's Handbook, 4th ed., McGraw-Hill, New York, 1963, pp. 8-59.

Example 46

Wettable powder (1,1-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl silane 40% dioctyl sodium sulfosuccinate 1.5% sodium lignosulfonate 3% low viscosity methylcellulose 1.5% attapulgite 54%

The ingredients are thoroughly mixed, passed through an air mill until an average particle size of less than 15 microns is formed, zno-1-ylmethylsilane 20% sodium alkylnaphthalene sulfonate 2% low-viscosity methylcellulose 2% diatomaceous earth 76%

The ingredients are mixed, coarsely ground in a hammer mill, and then ground in an air mill to a particle size below 10 microns. The product is mixed again and packaged.

Example 48

Highly concentrated concentrate (4-chlorophenyl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

The ingredients are mixed and ground in a hammer mill until a highly concentrated concentrate is obtained, passing through a 0.3 mm mesh screen. This concentrate can then be processed in various ways.

Example 49

Powder highly concentrated concentrate according to example 48 25.4% pyrophylllt, powder 74.6%

The ingredients are mixed thoroughly and packaged for use.

Example 50

Aqueous suspension of (Ι,Γ-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane 50.0% thickener based on polyacrylic acid 0.3% dodecylphenyl ethylene glycol ether 0.5% disodium phosphate 1.0% monosodium phosphate 0.5% polyvinyl alcohol 1.0% pentachlorophenyl 0.4% water 46.3 ^ηθ /ο

The ingredients are ground together in a sand mill to a particle size substantially below 5 micrometers.

Ri* Re Qi Q2 03 phenyl —CH2CH=CHCH2— H H H phenyl —C(CH 3 ) 2 CH=CHC(CH ₃ ) 2 — CH s CH s II H H H phenyl 1 1 —CHCH2CH2CH— H H H phenyl — C(CH3)2CH2CH2C(CH3)2— H H H 4-phenylphenyl —CH2CH=CHCH2— CH3 CH3 I 1 H H H 4-phenylphenyl 1 1 —CH2C=CCH ₂ — H H H 4-fluorophenyl —CH2—CH—CHCH2— H H H 4-chlorophenyl —CH2CH2CH2CH2— n-CíHg 1 H H H 4-phenoxyphenyl 1 —CH2CH2CH2CH— CH3 CH3 and 1 CH5 H H 3-trifluoromethylphenyl 1 1 —CHCH=CHCH— CH3 CH3 and 1 H CH3 CH3 2-methoxyphenyl 1 1 —CFIsCH--CHCH2— CHs CH3 CH3

Resources

The compositions containing the active ingredients according to the invention which can be used can be prepared in conventional ways. They are powders, granules, pellets, solutions, emulsions, wettable powders, emulsifiable concentrates and similar compositions. Many of the active ingredients according to the invention can be used directly. Sprayable compositions can be prepared in a suitable medium and used in amounts of up to several hundred liters per hectare. Highly concentrated compositions are used primarily as intermediates for the preparation of other compositions. The compositions generally contain 1 to 99% by weight of the active ingredient or ingredients and approximately 0.1 to 20% of the surfactant or surfactants and/or approximately 5 to 99% of a solid or liquid inert diluent or solid or liquid inert diluents. In particular, the individual components are contained in the following approximate amounts:

Active ingredient Thinner or thinners by weight Surfactant(s) % Wettable powders 20 — 90 0 — 74 1 — 10 Oil suspensions, emulsions, solutions (including emulsifiable concentrate) 5 — 50 40 — 95 0 — 15 Aqueous suspensions 10 — 50 40 — 84 1 — 20 Powder 1 — 25 70 — 99 0—5 Granules and pellets 1-95 5 — 99 0 — 15 Highly concentrated products 90 — 99 0 — 10 0—2

Ri'

Re

Qi Qž Q3

11-C3H7

phenyl —CH2CH— H H H phenyl — C(CH3) ₂ C(CH3)2-- H H H 4-phenylphenyl —CH2CH2— C2H5 H H H 4-phenylphenyl | —CH2CH— CH3 CH3 I 1 H H H 4-phenylphenyl 1 1 —CH--CH— H H H 4-fluorophenyl — CH2CH2— CH3 H H H 4-fluorophenyl | —CHzCH— C2H5 1 H H H 4-chlorophenyl 1 —CHžCH— H H H 4-chlorophenyl —CICH3)2C(CH3)2— CHs H H H 3-trifluoromethylphenyl | —CHCH2C(CH3)2— 11-C4H9 CH3 CH3 CH3 2-methoxyphenyl | —CH2CH— CH3 H H 2,3-dimethylphenyl —CH2CH2— C2H5 | H CHs CH3 2,4-dichlorophenyl 1 —CH2CH— 11-C3H7 I H H H 2,4-dichlorophenyl 1 —CH2CH— CH3 CH3 H H H 2-methoxy-5-fluorophenyl | | -~CHC(CH3)2CH— CH3 H H 2,6-dimethoxyphenyl —CH2CH2— CH3 CH3 i 1 H H H 3,4-dichlorophenyl 1 1 —CHCH2CH— CH3 CHs I I CHs CH3 CH ₃ 3,5-dichlorophenyl i 1 —CH---CH— CH3 CH3 CHs C2H5 — CH ₂ CH=CHCH2— CH ₃ CH3 i 1 H CH3 CH3 n-CisHsz 1 1 —CHCH2CH2CH— H CH3 CH3

Table XVIII

Rl* Re Qi Q2 Q3 C2H5 t-CáH9 H H H 11-C4H9 C2H5 H H H 11-C18H37 CH3 H H H cyclohexyl 11-C3H7 H H H 1-naphthyl Í-C4H9 H H H phenyl CH3 CH3 CH3 CH3 phenyl n-C3ří7 ^: CH3 H H phenyl 1-C3H7 H CH3 CH3 phenyl t-C4H9 H H H 4-phenylphenyl C2H5 H H H 4-phenylphenyl n-C4H9 CH3 CH3 CH3 4-fluorophenyl CH3 CH3 H H 4-fluorophenyl C2H5 H H H 4-chlorophenyl C2H5 H H H 4-chlorophenyl 1-C3H7 H H H 3-trifluoromethylphenyl S-C4H9 CH3 CH3 CH3 2-methoxyphenyl 11-C3H7 CH3 H H 2,3-dimethylphenyl 1-C4H9 H H H 2,4-dichlorophenyl CH3 H H H 2,4-dichlorophenyl C2H5 H H H 2-Methoxy-5-fluorophenyl 1-C3H7 H H H 2,6-dimethoxyphenyl CH3 H H H 3,4-dichlorophenyl C2H5 H H H 3,5-dichlorophenyl n-C4H9 H H H Table XIX 0 0 > A d ^sú-ch,K Ί Ri* Re Qi Q2 Q3

C2H5 —CH2CH2— H H H 11-C4H9 CH3 1 —CH2CH— CH3 H H n-CwH37 —CH2CH2CH2— H CH3 CH3 cyclohexyl C2H5 1 —CH2CH— CH3 CH3 CH3 1-naphthyl —-CH2CH2—- CH3 H H phenyl —CH2CH2— H H H phenyl C2H5 1 —CH2CH— H H H

R1* R2 R6

3-trifluoromethylphenyl 2-Methoxyphenyl 2- chlorophenyl 3-trifluoromethylphenyl 2-fluoro-4-chlorophenyl 2.3-dimethylphenyl 2,6-dimethoxyphenyl 3.4-dichlorophenyl 4-fluorophenyl 3-trifluoromethylphenyl 2-methoxyphenyl 4-fluorophenyl 4-t-butylphenyl 4-bromophenyl 4-methylthiophenyl 4-MethyOxyphenyl 4-methylphenyl 4-fluorophenyl 1-C4H9 H H n-CiHg 1-C3H7 C2H5 H i-ClHg H m.p. 114 -- 116 °C Table XVII

[ / ]

OR _fe 4

Rl* <;R2 Qi Qž Q3 C2H5 ch ₃ CH3 CH3 CHs CHs cyclohexyl CH3 1-C3H7 H CHs CHs n-Cl ₈ Hs7 n-CeHi3 t-CiHg CHs H H 1-naphthyl CHs Í-C3H7 CH3 H H phenyl ch ₃ t-CiHa H CHs H phenyl ch ₃ t-CáHg H H CHs phenyl CH3 t-CáHg CHs CH3 CH3 phenyl ch ₃ S-C4H9 H CHs CH3 phenyl CH3 Í-C3H7 CH3 H H 4-phenylphenyl 11-C1H9 t-CiHg ch ₃ CH3 CH3 4-phenylphenyl CHs t-CíHg CH3 H H 4-phenylphenyl ch ₃ t-CiHg CHs CH3 CHs 4-chlorophenyl CHs t-C4Hg CHs H H 4-chlorophenyl CH ₃ t C4H9 H CHs CHs 4-fluorophenyl CHs t-CiHg H CH3 H 4-fluorophenyl CHs t-C4Hg H H CHs phenyl phenyl C2H5 CH3 CHs CHs phenyl phenyl nC ₃ H7 CHs CHs CH3 4-fluorophenyl phenyl Í-C3H7 H CH3 CHs 4-fluorophenyl phenyl t-CáHg CH3 H H 4-chlorophenyl phenyl Í-C3H7 CH3 H H 2,4-dichlorophenyl phenyl H CH3 H H 4-fluorophenyl 4-fluorophenyl t-C4Hg CH3 H H 4-fluorophenyl 4-fluorophenyl t-CiHg H CHs CH3 4-fluorophenyl 4-fluorophenyl t-C4H9 CH3 CH3 CH3 2-methoxyphenyl 2-methoxyphenyl C2H5 CHs H H 3-methylphenyl 3-methylphenyl Í-C4H9 CHs H H

Example 45

NMR (CDCl3)

Preparation of (1H-imidazol-1-ylmethyl)phenylbis(2-propoxy)silane 1H-imidazol-1-ylmethyl(phenylbis)2-propoxysilane can be prepared according to the method of Example 26 using chloromethyl(phenyl)bis(2-propoxy)silane:

1.2 (12H, d, J = ₆ ),

3.6 {2H, s),

4.2 (2H, septet, J = 6),

6.8 - 7.6 (8H, m).

Similarly, the compounds of Tables XVIII and XIX can be prepared.

n n ²² 1.4971;

Table XVI or ₆

Ri'

C2H5 t-C4H9

11-C4H9 n-Ci2H25

11-C18H37 cyclopropyl cyclohexyl

1- naphthyl

2- naphthyl phenyl phenyl phenyl phenyl phenyl

4-phenylphenyl

4-phenylphenyl

4-phenylphenyl

4-phenylphenyl

4-chlorophenyl

4-chlorophenyl

4-chlorophenyl

4-fluorophenyl

4-fluorophenyl

4-phenoxyphenyl

4-t-butylphenyl

3-trifluoromethylphenyl 2-methylthiophenyl 2,4-dichlorophenyl 2,4-dichlorophenyl 2,4-dichlorophenyl

2.4- dichlorophenyl

2,3-dimethylphenyl

2- methyl-5-fluorophenyl 2,6-dimethoxyphenyl

3-methyl-4-chlorophenyl

3.5-dichlorophenyl 11-C12H25 n-CieH37

1- Naphthyl phenyl

4-fluorophenyl 4-chlorophenyl 4-phenylphenyl 4-phenylphenyl 4-t-butylphenyl

3-fluorophenyl

2- methoxyphenyl 2-chlorophenyl

2.4- dichlorophenyl

3.5- dichlorophenyl

4-fluorophenyl 4-fluorophenyl 4-chlorophenyl 4-chlorophenyl 4-phenylphenyl 2,4-dichlorophenyl

R2 Rs. CH3 CH3 CH3 t-CáHg CH3 C2H5 C2H5 CH3 n-C6Hi3 CH3 CH3 S-C4H9 CH3 CH3 Í-C3H7 1-C3H7 cyclobutyl n-C3H7 CH3 H CH3 CH3 CH3 C2H5 CH3 I-C3H7 n _D ²⁰ 1.5 3 5 2 t-CíHg H 11-C4H9 CH3 t-C4H9 H CH3 C2H5 CH3 n-C4H9 n-CíH9 n-C4Hg CH3 CH3 CH3 C2H5 n-CsHt3 n-C3H7 CH3 C2H5 cyclohexyl Í-C4H9 n-C3H7 S-C4H9 Í-C4H9 H cyclopentyl C2H5 CH3 CH3 ch ₃ C2H5 CH3 t-C4Hg 11-C4H9 C2H5 cyclopropyl Í-C3H7 S-C1H9 11-C3H7 1,1-dimethylpropyl H C2H5 CH3 n-CsHu C2H5 2,4-dichlorophenyl Í-C4H9 phenyl CH3 phenyl C2H5 phenyl Í-C4H9 phenyl CH3 phenyl 11-C3H7 phenyl C2H5 phenyl S-C4H9 phenyl s-CdHg phenyl C2H5 phenyl H phenyl CH3 phenyl 1-C3H7 phenyl 11-C3H7 4-fluorophenyl Í-C4H9 4-fluorophenyl C2H5 4-chlorophenyl CH3 4-chlorophenyl C2H5 4-phenylphenyl CH3 2,4-dichlorophenyl C2H5

ir (Nujol ^K ), 1590, 1515, 1250, 1110, 840, 820,

750, 695, 650 cm ¹ ;

By the method of Example 42, any compound of Table XIV, XV, XVI, XVII, XVIII or XIX can be converted into metal complexes or salts.

Example 43

Preparation of (1,1'-biphenyl-4-yl) (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 maintained at 80-90°C for two hours. Ten equivalents of methanol are then added and the mixture is maintained at 70 ^° C for one hour, cooled, diluted with water and rapidly extracted with ether. The ether solution is washed with water and brine, dried over magnesium sulphate and evaporated to give (1,1'-biphenyl-4-yl)(1H-imidazol-1-ylmethyl)(methoxy)methylsilane.

Related compounds can be obtained in the same manner using a suitable chlorosilane and an alcohol; for R 5 as a hydroxyl group, water is used instead of alcohol and the hydrolysis is carried out at 20-25°C instead of 70°C.

Example 44

Preparation of 1,1-(dimethylethoxy)(1H-imidazol-1-ylmethyl)methyl(phenyl)silane

A mixture of 3.6 g (0.015 mol) of chloromethyl-(1,1-dimethylethoxy)methyl(phenyl)silane and 1.3 g (0.015 mol) of sodium imidazole in 10 ml of dimethylformamide was stirred at 50 degrees Celsius for three hours, allowed to stand at room temperature for 72 hours, poured into water and extracted with ether. The ether extracts were washed three times with water and once with brine, dried over magnesium sulfate and evaporated to give 3.8 g of an oil. The impurities were removed by distillation in a neck flask at 90 °C (air bath) and 6.66 Pa to give 2.9 g (71%) of 1,1-(dimethylethoxy) (1H-imidazol-1-ylmethyl)methyl (phenyl)silane as a pale yellow oil:

_nD20 ^1.5291 ;

ir (pure) 3105, 3070, 3045, 2970, 1590, 1500,

1425, 1360, 1250, 1235, 1185, 1110, 1055,

1020, 900, 805, 740, 700, 660 cm- ¹ ;

NMR (CDCl3)

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).

The compounds listed in Tables XVI and XVII can be prepared by the method of Examples 43 and 44.

Example 44a

Preparation of [bis(4-chlorophenyl)]hydroxy(1H-imidazol-1-ylmethyl)silane

A mixture of 5.5 g (15.3 mmol) of chloromethyl[bis(4-chlorophenyl)] (2-propoxy)silane and 1.5 g (17.0 mmol) of sodium imidazole in dimethylformamide was maintained at 80-90 °C for two hours, cooled, diluted with ethyl acetate, washed three times with water and once with brine, dried over magnesium sulfate and evaporated to give a viscous oil. Trituration with ether gave 1.0 g (19% of theory) of the compound prepared as a colorless solid with a melting point of 131-133 °C;

NMR (CD3SOCD3)

4.1 (2H, s),

6.8 (1H, s),

6.9 (1H, s),

7.4 (4H, d),

7.6 (5H, d).

Ri* Rye R3 2-naphthyl 4-methylthiophenyl 4-methylthiophenyl 4-chlorophenyl 2-methoxyphenyl 2-methoxyphenyl 4-chlorophenyl 3-chlorophenyl 3-chlorophenyl phenyl 2-chlorophenyl 4-fluorophenyl phenyl 4-chlorophenyl 4-phenylphenyl 1-naphthyl 4-bromophenyl 3-methylphenyl 4-phenoxyphenyl 3,5-dimethylphenyl 3,4-dichlorophenyl 4-fluorophenyl 4-fluorophenyl 4-fluorophenyl, m.p. 85 — 88 C 4-phenylphenyl 4-fluorophenyl methylphenyl n _n ²² 1.6181

Ri' Table 1 ^R 2. r ¹ R ₁ -SÍ-C 1 R2 XV ; Qj GL·/ Ql ()2 C2H5 CH3 C-H3 CH3 CH3 CH3 n-CwH37 CH3 CH3 H CPI3 CHs cyclohexyl CH3 ch ₃ H CH3 CHs 1-naphthyl CH3 CH3 CH3 H H phenyl CH5 CH3 H CH3 H phenyl CH3 CH3 H H CH3 4-phenylphenyl CH3 ch ₃ CH3 H H 4-(4-fluorophenyl)phenyl CH3 CH3 CH3 H H 4-phenoxyphenyl CH3 ch ₃ CH3 CH3 CH3 3-trifluoromethylphenyl CH3 CH3 H CH3 CH3 2-methoxyphenyl CH3 CH3 CHs H H 2,4-dichlorophenyl CH3 CH3 CH3 CH3 CH3 2-chloro-4-phenylphenyl CH3 CHs H CH3 CH3 phenyl n-CdHg CH3 CH3 H H 4-phenylphenyl 11-C4H9 ch ₃ H CH3 CH3 2,4-dichlorophenyl n-C6Hi3 CH3 CH3 H H 4-(4-chlorophenoxy)phenyl cyclohexyl CH3 CH3 H H phenyl phenyl ch ₃ CH3 CHs CH3 4-fluorophenyl phenyl CH3 CH3 H H 4-fluorophenyl phenyl ch ₃ CH3 CH3 CH3 4-chlorophenyl phenyl ch ₃ H CH3 CHs 4-fluorophenyl 4-fluorophenyl ch ₃ CH3 H H 4-fluorophenyl 4-fluorophenyl CH3 H CH3 CH3 4-chlorophenyl 4-chlorophenyl CH3 CH3 CH3 CHs 4-chlorophenyl 4-chlorophenyl CH3 CH3 H H 2-chlorophenyl 4-chlorophenyl ch ₃ CH3 CH ₃ CH3 2,4-dichlorophenyl 2,4-dichlorophenyl CH3 CH3 H H n-Cl8H37 n-C6Hi3 11-C6H13 H CH3 C.H3 1 -naphthyl n-CdHg n-CíHg CH CHs CHs phenyl phenyl phenyl CH3 H H phenyl phenyl phenyl CH3 H CH3 phenyl phenyl phenyl CH3 CH3 H

Example 42

Preparation of 1 : 1 complex of (1,1'-biphenyl-4-yl)-dimethyl(1H-imidazol-1-ylmethyl)silane and copper chloride

A mixture of 0.50 g (0.0017 mol) of (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl)silane and 0.22 g (0.0017 mol) of copper (I) chloride in ml of tetrahydrofuran is refluxed under nitrogen for 15 minutes and the resulting dark green solution is evaporated to give a 1 : 1 complex of (Ι,Γ-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl)silane and copper (I) chloride as a dark green solid with a melting point of 72 to 80 degrees Celsius (with decomposition);

Ri'

R2

Rs.

I-C3H7

11-C4H9 n-CioH2 n-Ci2H25

11-C14H29

11-C18H37 cyclopropyl cyclopentyl cyclohexyl

1-naphthyl

1- naphthyl

2- naphthyl phenyl phenyl phenyl phenyl

4-phenylphenyl

4-phenylphenyl

4-bromophenyl

4-chlorophenyl

4-fluorophenyl

4-phenoxyphenyl

4-i-propylphenyl

4-t-butylphenyl

3-phenylphenyl

3-trifluoromethylphenyl

3-chlorophenyl

2-methoxyphenyl

2-thiomethylphenyl

2-phenylphenyl

2,4-dichlorophenyl

2.4- dichlorophenyl

2,3-dimethylphenyl

2-methyl-5-fluorophenyl

2,5-dimethoxyphenyl

2,6-dimethylphenyl

3,4-dichlorophenyl

3.5- dichlorophenyl

3,5-dichlorophenyl

3-methyl-4-chlorophenyl

4-fluorophenyl

4-chlorophenyl

4-bromophenyl

4-phenylphenyl 4-t-butylphenyl 4-thiomethylphenyl 4-phenoxyphenyl

4-trifluoromethoxyphenyl 4-methylsulfonylphenyl 4-cyclohexylphenyl 4-(4-fluorophenyl)phenyl

3-trifluoromethylphenyl 2-chlorophenyl 2-methoxyphenyl

2.4-dichlorophenyl 2-chloro-4-phenylphenyl

2-fluoro-4-phenylphenyl

3.5- dichlorophenyl

2,5-dimethoxyphenyl

2,6-dimethoxyphenyl

4-fluorophenyl 4-chlorophenyl 4-bromophenyl 4-phenylphenyl 4-methoxyphenyl

3- trifluoromethylphenyl cyclohexyl

11-C4H9 cyclopropyl

11-C3H7

I-C3H7

3-methylbutyl

J1-C6H43 cyclopentyl cyclohexyl n-CiHg t-CtHg

11-C5H11

11-C3H7

11-C4H9

1,1-dimethylpropyl

11-C6H13

CzHs

11-C4H9 i-CsH?

11-C4H9

11-C1H9

I-C4H9 cyclopropyl

I-C4H9

1-C4H9

S-C4H9 n-C5Hii t-CiHg cyclobutyl

I- CjHg

II- C4H9 cyclopropyl

11-C3H7 cyclopentyl

4-methylpentyl

I-methylbutyl

II- C5H11 n-CáHg cyclohexyl cyclopropyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl

4-fluorophenyl

4-chlorophenyl

4-bromophenyl

4-phenylphenyl

4-methoxyphenyl

3-trifluoromethylphenyl

CH3 CH3 n _D ²² 1.4710 CH3 CHs CH3 CH3 CH3 CHj CH3 CH3 CH3 CHs CHó CHs n _u ²² 1.5 4 49 CH3 CH3 CH3 CHs n _D ²² 1.5880 CHó CH ₃ n _D ²¹ 1.5415 CH3 n _D ²² 1.5161 CHj CHj CH3 CHj CHj CH3 CHj CH3 CHj CH3 n _D ²¹ 1.5588 CH3 CHj CH3 CH3 CHj CHj CH3 CH3 CH3 CH3 n _D ¹⁹ 1.5810 CH3 n _D ²¹ 1.6000 CH3 n _D ²² 1.6115 CH3 n _D ²¹ 1.6378 CHs CH3 CH3 CH3 CH3 CH3 CH3 CH3 CHs n _D ²² 1.6058 CH3 CHs n _D ²² 1.6150 CH3 CH3 CH3 CH3 CH3 CH3 n _D ²² 1.5569 CH3 n _n 1.5820 CHs n _D ²¹ 1.6305 CH3 mp 44 — 53 °C CH3 n _D ²¹ 1.5947 CH3

R2

R3

Ri' _

2-chlorophenyl

2-methoxyphenyl

2.4- dichlorophenyl

3.5- dichlorophenyl

2-chlorophenyl

2-chlorophenyl 4-phenylphenyl 4-phenylphenyl 4-phenylphenyl 4-fluorophenyl 4-chlorophenyl

1-naphthyl 4-phenoxyphenyl C2H5

Í-C3H7 n-C4H9 η-ϋβΗΐ7 n-Ci4H29 n-CieH37 cyclopropyl cyclohexyl

1- naphthyl

2- naphthyl phenyl

4-phenylphenyl

4-phenylphenyl

4-phenylphenyl

4-phenylphenyl

4-chlorophenyl

4-fluorophenyl

4-phenoxyphenyl

4-(4-chlorophenoxy)phenyl

4-t-butylphenyl

3- methoxyphenyl

3-trifluoromethylphenyl 2-thiomethylphenyl

2-phenylphenyl

2.4- dichlorophenyl

2,6-dimethylphenyl

3.5- dichlorophenyl

3-methyl-4-chlorophenyl 2-methyl-5-fluorophenyl C2H5 cyclohexyl n-Ci8H37 n-CiH9 n-Ci2H25

I- naphthyl cyclopropyl n-C4H9 t-C4Hg n-C3H7

Í-C4H9 cyclopentyl

II- C14H29

11-C4H9 phenyl

4-chlorophenyl

4-fluorophenyl

4-phenylphenyl

2,4-dichlorophenyl phenyl phenyl phenyl phenyl

2-chlorophenyl

2-methoxyphenyl

2.4- dichlorophenyl

3.5-dichlorophenyl 4-chlorophenyl 4-fluorophenyl 4-chlorophenyl

4-fluorophenyl 2,4-dichlorophenyl 2,4-dichlorophenyl

2.4- dichlorophenyl

2,6-dimethoxyphenyl

3.4- dichlorophenyl C2H5

Í-C3H7 n-CáHg

C2H5 cyclopropyl n-CeHi3

C2H5 n-C3H7 n-CαHg n-C4H9 cyclopropyl

C2H5 n-C4H9 n-C6Hi3 cyclohexyl

11-C4I-I9

11-C3H7

11-C4H9

11-C4H9

5- C4H9

C2H5

S-C4H9

1-C3H7 cyclohexyl n-CdHg t-CdHg cyclopentyl

S-C1H9 n-CdHg phenyl phenyl phenyl

4-chlorophenyl

4-chlorophenyl

4-fluorophenyl phenyl phenyl phenyl phenyl phenyl

4-chlorophenyl

4-fluorophenyl phenyl

4-chlorophenyl

4-fluorophenyl

4-phenylphenyl

2.4-dichlorophenyl 4-fluorophenyl 4-chlorophenyl 4-phenylphenyl 2,4-dichlorophenyl

CH3 n _D ²⁰ 1.5 9 9 9

CHs

CH3 n _D ²² 1.6019

CH3

CH3 n _D ²⁰ 1.6044

CH ₃ ch ₃

CH3 ch ₃ gh ₃

CH3

CH3

CH3

C2H5

1-C3H7 n-C4Hg cyclopentyl

I-methylbutyl n-CeHi3 S-C4H9

II- C3H7 n-CiHg cyclobutyl n-C6Hi3

C2H5 n-C4H9 n-C6Hi3 cyclohexyl n-CiHg n-C3H7 cyclohexyl n-CiHg

1- CiHg t-CiHg

S-C4H9

3- methylbutyl cyclohexyl n-CiHg t-QHg cyclopentyl

S-C4U9 I-C1H9 phenyl phenyl phenyl

4-chlorophenyl 4-chlorophenyl 4-fluorophenyl 4-t-butylphenyl 4-phenylphenyl

2.4- dichlorophenyl

3-trifluoromethylphenyl

3.5- dichlorophenyl

2,6-dimethoxyphenyl

2-fluorophenyl

4- phenylphenyl phenyl m.p. 175 -- 178 °C

4-chlorophenyl

4-fluorophenyl

4-phenylphenyl

2,4-dichlorophenyl

4-fluorophenyl

4-chlorophenyl

4-phenylphenyl

2,4-dichlorophenyl

Table XIV

Ri' R2 R3 ch ₃ CH3 CH3 n _D ²² 1.4805 C2H5 CH3 CH3 n _D ²² 1.4848 1-C3H7 CH3 CHs 11-C4H9 . CH3 CH3 n _D ¹⁹ 1.4811 t-CiHg CH3 CHs 11-C12H25 CH3 CH3 n _D 25 1.4585 11-C14H29 CH3 CHs 11-C18H57 CHs CH3 n _D ²¹ 1.4639 cyclopropyl CH3 CH3 cyclobutyl ch ₃ CH3 cyclopentyl CHs CH3 cyclohexyl CHs CH3 n _D ²² 1.4999 1-naphthyl CH3 CH ₃ n _D ²³ 1.6188 2-naphthyl CH5 CH3 phenyl CH3 CHs b. v. 120 to 125 °C 4-bromophenyl CHs CHs n _D ² « 1.5741 4-fluorophenyl ch ₃ CHs n _D ²³ 1.5314 4-methoxyphenyl CHs CH3 n _D ²⁵ 1.5485 4-phenoxyphenyl CH3 CH3 n _D ²² 1.5833 4-(4-chlorophenoxy)phenyl CHs CH3 n _D ²² 1.5564 4-(fluorophenoxy)phenyl CH3 CH3 4-[4-trifluoromethylphenoxy)1'enyl CH3 CH3 4-(4-methylphenoxy}phenyl CHs CH3 4-thiomethylphenyl CH3 CHs n _D ²³ 1.5855 4-methylsulfonylphenyl CH3 CH3 η _η ²¹ 1.5552 4 trifluoromethylphenyl CH3 CH3 n _u ²² 1.4867 4-methylphenyl CH3 CHs n _D ²¹ 1.5482 4-i-propylphenyl CHs CH3 4-t-butylphenyl CH3 CHs n _D ²³ 1.5229 4-cyclohexylphenyl CH3 CHs n _n ²² 1.5085 4-trifluoromethoxyphenyl CH3 CHs June ²² 1.4888 4-(4-chlorophenyl)phenyl CH3 CH3 4- [ 4-methylphenyl)phenyl CHs CH3 4-(4-trifluoromethylphenyl J phenyl CHs CH3 4-(4-fluorophenyl)phenyl CH3 CH3 4-(4-bromophenyl)phenyl CH3 CH3 n _D ²² 1.5745 3-phenylphenyl CHs CfÍ3 n _D ²¹ 1.6002 3-trifluoromethylphenyl CH3 CH3 n _D ²⁰ 1.4927 3-chlorophenyl CHs CH3 n _D ²² 1.5560 2-trifluoromethylphenyl CH3 CH3 n _D ²³ 1.5056 2-phenylphenyl CH3 CH3 n _D ²² 1.5996 2-chlorophenyl CH3 CHs n _D ²² 1.5382 2-methoxyphenyl CH3 CH3 n _D ²² 1.5344 2,3-dimethylphenyl CH3 CH3 2,3-dimethoxyphenyl CH3 CH3 n _D ²² 1.5350 2,4-difluorophenyl CH3 CH3 2-fluoro-4-chlorophenyl CH3 CH3 2-chloro-4-fluorophenyl CHs CH3 2-chloro-4-phenylphenyl CH3 ch ₃ 2-fluoro-4-phenylphenyl CH3 CH3 2-methyl-5-chlorophenyl CH3 CH3 2,6-dimethoxyphenyl CH3 CHs n _D ²³ 1.5348 2,6-dimethylphenyl CH3 CHs 3,4-dichlorophenyl CH3 CH3 n _D ²³ 1.5673 3-methyl-4-fluorophenyl CH3 CHs 3,5-dichlorophenyl CHs CH3 n _D ²² 1.5461 C2H5 C2H5 ch ₃

6.6 (1H, wide sj,

6.9 (1H, wide s),

7.1 (1H, wide s),

7.3 (4H, s).

Example 39

Preparation of (2,4-dichlorophenyl)dimethyl(1H-imidazol-1-ylmethyl)silane

A mixture of 5.1 g (0.020 mol) of chloromethyl-(2,4-dichlorophenyl)dimethylsilane and 2.0 g (0.022 mol) of sodium imidazole in 10 ml of dry dimethylformamide was stirred at 80-90 °C for two hours and worked up as in Example 18 to give 3.9 g (69%) of (2,4-dichlorophenyl)dimethyl(1H-imidazol-1-ylmethyl)silane as a brown oil:

_nD ²³ 1.5637;

ir (clean) 1560, 1500, 1450, 1355, 1250, 1105,

1095, 1075, 1025, 840, 780, 735 cm-*;

NMR (CDCl3)

0.4 (6H, s],

3.9 (2H, s),

6.7 (1H, wide s),

7.0 (1H, wide sj,

7.2 - 7.5 (4H, m).

Example 40

Preparation of diphenyl(1H-imidazol-1-ylmethyl)methylsilane

A mixture of 4.9 g (0.020 mol) of chloromethyl(diphenyl)methylsilane and 2.0 g (0.022 mol) of imidazole sodium salt in 10 ml of anhydrous dimethylformamide was stirred at 80°C for 3.5 hours and worked up as in Example 18 to give 4.8 g of a yellow oil. Distillation in a neck flask at 125°C and 6.66 Pa removed the volatile impurities and gave 2.9 g (52% of theory) of diphenyl(1H-imidazol-1-ylmethyl)methylsilane as an oil;

_nD ²² 1.5995;

ir (pure) 3375, 3250, 1500, 1430, 1255, 1230,

1110, 1075, 1025, 810, 790, 735, 700, 660 cnr ¹ ;

NMR (CDCl3)

0.6 (3H, s),

3.9 (2H, sj,

6.6 (1H, wide s),

6.9 (1H, wide with j,

7.2 - 7.5 (11H, m).

The compounds of Table XIV are prepared from suitable chloromethylsilanes by the method of Examples 37 to 40.

Example 41

Preparation of (1,1'-biphenyl-4-yl)dimethyl[2-methyl-1H-imidazol-1-ylmethyl)silane (1,1'-Biphenyl-4-yl)dimethyl[2-methyl-1H-imidazol-1-ylmethyl]silane was prepared as described in Example 37 using (1,1'-biphenyl-4-yl)chloromethyldimethylsilane and 2-methylimidazole sodium salt.

Related compounds can be prepared in the same manner using salts of 2,4-dimethylimidazole, 4,5-dimethylimidazole and 2,4,5-trimethylimidazole.

The method of Example 41 can be used to prepare the compounds listed in Table XV.

Rl

Re

Qi

Q2 phenyl phenyl

4-phenylphenyl

4-phenylphenyl

4-fluorophenyl

4-chlorophenyl

4-phenoxyphenyl

3-trifluoromethylphenyl

2-methoxyphenyl

CHo CH3

II —CHCH2CH2CH— H —C(CH3)2CH2CHzC(CH3)2— η —CH ₂ CH=CHCH2— h

CHo CH3 ,

I I —CH2C=CCH2— h —CH2CH=CHCH2 h —CH2CH2CH2CH2— H n-CáHg

I —CH2CH2CH2CH— CH3

CHo CHo

I I —CHCH=CHCH— H

CH3 CHo

I I —CH2CH--CHCH2— Η

H

H

H

H

H

H

CH3

CH3

H

Example 37

Preparation of (1,1'-biphenyl-4-yl)dimethyl (1H-imidazol-1-ylmethyl)silane

A mixture of 2.6 g (0.010 mol) of (1,1'-biphenyl-4yl)chloromethyldimethylsilane and 1.1 g (0.012 mol) of sodium imidazole in 5 ml of dimethylformamide was maintained at 80-90 °C for two hours, cooled, diluted with water and extracted with ether. The ethereal solution was washed with water and brine, dried over magnesium sulfate and evaporated to give 2.0 g of a viscous, pale yellow oil. Trituration of a small sample with hexanes gave a solid. The crude product mass was then taken up in a hot mixture of 20 ml of hexanes and 3 ml of ethyl acetate, the solution was slowly cooled and seed crystals were added as soon as turbidity was observed. The resulting crystals were collected and dried to give 0.84 g (29% of theory) (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylethyl)silane in the form of colourless flakes:

melting point 51 to 53°C;

(Nujor) 1235, 1215, 1105, 1065, 900, 830, 785, 750, 730, 685 cnrl;

NMR (CDCl3)

0.4 (6H, s),

3.7 (2H, s),

6.7 (1H, wide s),

7.0 (1H, wide s),

7.1-7.8 (10H, m);

analysis for C18H20N2Si (molecular weight: 292.45) calculated:

C 73.92 H 6.89 N 9.58 found:

C 73.40 H 7.00 N 9.40

C 73.70 H 7.00 N 9.40

Example 38

Preparation of (4-chlorophenyl)dimethyl (1H,imidazol-1-ylmethyl)silane

A mixture of 2.2 g (0.010 mol) of chloromethyl(4-chlorophenyl)dimethylsilane and 1.1 g (0.012 mol) of sodium imidazole in 5 ml of dimethylformamide was stirred at 80-90 °C for two hours, cooled, diluted with water and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulphate and evaporated to give 2.0 g (81% of theory) of (4-chlorophenyl)dimethyl(1H,imidazol-1-ylmethyl)silane as a yellow liquid:

n _D 2« 1.5472, ir (neat) 1560, 1495, 1480, 1375, 1250, 1105, 1080, 905, 830, 810, 740 cm'¹;

NMR (CDCl3)

0.3 (6H, s), 3.6 (2H, s),

Ri Re Qi Qž phenyl -C(CH3)2C(CH3)2— H H 4-phenylphenyl —CH2CH2— C2H5 I H H 4-phenylphenyl 1 —CH2CH— CH3 CH3 I 1 H H 4-phenylphenyl 1 1 —CH CH H H 4-fluorophenyl —CH2CH2— CH3 I H H 4-fluorophenyl 1 —CH2CH— C2H5 H H 4-chlorophenyl —CH2CH— H H 4-chlorophenyl —C(CH3]2C(CH3)2— CH3 H H 3-trifluoromethylphenyl 1 —CHCH2C(CH3]2— n-C-iHg CH3 CH3 2-inethoxyphenyl | —CH2CH— H ch ₃ 2,3-dimethylphenyl —CH2CH2— C2H5 CH3 CH3 2,4-dichlorophenyl | —CH2CH— n-C3H7 H H 2,4-dichlorophenyl | —CH2CH— CH3 CH3 1 | H H 2-methoxy-5-fluorophenyl —CHC(CH3)2CH— H H 2,6-dimethoxyphenyl —CH2CH2— CH3 CH3 1 | H H 3,4-dichlorophenyl —CHCH2CH— CH3 CH3 1 1 H H 3,5-dichlorophenyl 1 1 —CH CH— H H C2H5 —CH ₂ CH=CHCH2— ch ₃ ch ₃ CH3 CH3 n-CieH37 | | —CHCH2CH2CH— H CH3 phenyl —CH2CH=CHCH2— H H phenyl -C(CH3)2CH=CHC(CH3)2- H H

Table XII

©»2

Rl Rs. Qi Q2 C2H5 t-C4H9 H H 11-C4H9 C2H5 H H 11-C18H37 CHs H H cyclobexyl n-C3H7 H H 1-naphthyl 1-C4H9 H H phenyl CH3 CH3 CH3 phenyl 11-C3H7 H CH3 phenyl I-C3H7 CH3 CH3 phenyl t-C4H9 H H 4-phenylphenyl C2H5 CH3 CH3 4-phenylphenyl n-C4Hy H H 4-fluorophenyl CH ₃ H H 4-fluorophenyl C2H5 H H 4-chlorophenyl C2H5 H H 4-chlorophenyl 1-C3H7 H H 3-trifluoromethylphenyl S-C4H9 CH3 CH3 2-methoxyphenyl n-CsH7 H ch ₃ 2,3-dimethylphenyl 1-C4H9 CH3 CH3 2,4-dichlorophenyl CHs H H 2,4-dichlorophenyl C2H5 H H 2-methoxy-5-fluorophenyl 1-C3H7 H H 2,6-dimethoxyphenyl CH3 H H 3,4-dichlorophenyl C2H5 H H 3,5-dichlorophenyl n-C4H9 H H

Table XIII

Rl

Q2

C2H5 —CH2CH2— CH3 CH3 n-C4H9 CH3 1 —CH2CH— H ch ₃ n-Ci8H37 —CH2CH2CH2— H H cyclohexyl C2H5 1 —CH2CH— H CH3 1-naphthyl —CH2CH2— CH3 H phenyl —CH2CH2— CH3 CH3 phenyl C2H5 1 —CH2CH— H H phenyl n-C3H7 1 —QH2CH— H H

Ri Re C2H5 2,4-dichlorophenyl | —CH2CH— n-C3H7 2,4-dichlorophenyl | —CH2CH— CH3 CH3 2-methoxy-5-fluorophenyl 1 | —CHC(CH3)2CH— 2,6-dimethoxyphenyl —CH2CH2— CH3 CH3 3,4-dichlorophenyl | | —CHCH2CH— CH3 CH3 3,5-dichlorophenyl —CH—CH— C2H5 —CH2CH=CHCH2— CH3 CH3 n-Ci.BH37 | | —CHCH2CH2CH— phenyl phenyl —CH ₂ CH=CHCH2— —C(CH3)2CH=CHC(CH3)2— CH3 CH3 phenyl 1 | —CHCH2CH2CH— mp 57 to 60 °C (19.99 Pa) phenyl 4-phenylphenyl —C(CH3)2CH2CH2C(CH3)2— —CH2CH=CHCH2— CH3 CH3 4-phenylphenyl | | —CH ₂ C==CCH ₂ — 4-fluorophenyl 4-chlorophenyl —CH2—CH=CHCH2— —CH2CH2CH2CH2— 11-C4H9 AND 4-phenoxyphenyl 1 —CH2CH2CH2CH— CH3 CH3 I 1 3-trifluoromethylphenyl 1 1 —CHCH=CHCH— CH3 CH3 2-methoxyphenyl | | —CH2CH—CHCH2

Ri

C2H5 n-CáHg

11-C18H37 cyclohexyl

1- naphthyl phenyl phenyl y

phenyl phenyl

4-phenylphenyl

4-phenylphenyl

4-phenylphenyl

AND

4-fluorophenyl

4-fluorophenyl

4-chlorophenyl

4-chlorophenyl

3-trifluoromethylphenyl

2- methoxyphenyl 2,3-dimethylphenyl

Table XI

O

R^Sú-CH^Ct

Re —CH2CH2—

CH3

I —CH2CH——CH2CH2CH2—

C2H5

I —CH2CH— —CH2CH2— —CH2CH2—

C2H5

I —CH2CH— n-C3H7

I —CH 2 CH— —C(CH 3 ) 2 C(CH ₃ ) 2 — mp 142 to 162 °C. (13.33 Pa) —CH2CH2—

C2H5

I —CH2CH—

CH3 CH3

I I —CH—CH —CH2CH2—

CH3

I —CH2CH—

C2H5

I —CH2CH— —C(CH3)2C(CH3)2—

CH3

I —CHCH2C(CH3)2— n-C4H9

I —CH2CH— —CH2CH2—

Example 35

Preparation of chloromethyl{phenyl)bis(2-propoxy)silane

A solution of 2.0 g (0.009 mol) of chloromethyl(dichloro)phenylsilane and 5 ml of 2-propanol in 15 ml of dimethylformamide was stirred under nitrogen while 2.5 ml (1.9 g, 0.018 mol) of triethylamine was added dropwise. The resulting suspension was heated to 80 °C and maintained at this temperature for two hours, cooled, diluted with water and extracted with ether. The ether extracts were washed with water and brine, dried over magnesium sulfate and evaporated to give 2.2 g of a liquid. Column chromatography on silica gel, eluting with petroleum ether, gave 1.4 g (58% of theory) of chloromethyl(phenyl]bis(2-propoxy)silane as a colorless liquid: n _D 22 1.4741;

NMR (CDCl3)

1.2 (12H, d, J = 6),

3.0 (2H, s),

4.3 (2H, septet, J = 6),

7.3 to 7.8 (5H, m).

The compounds listed in Tables X and XI were prepared according to the method of Examples 33 to 35.

Example 36

Preparation of phenylbis(2-propoxy)(1H-1,2,4-triazol-1-ylmethyl)silane

Phenylbis(2-propoxy)(1H-1,2,4-triazol-1-ylmethyl)silane can be prepared by the method of Example 32 from chloromethyl(phenyl)bis(2-propoxy)silane:

NMR (CDCl3)

1.1 (12H, d, J — 6),

4.0 (2H, s),

4.3 (2H, septet, J — 6),

7.2 to 8.0 (7H, m).

The compounds listed in Tables XII and XIII are prepared similarly.

Table X

ORe

AND

R1—Si—CH2Cl

AND

ORe

Ri Re C2H5 t-C4H9 n-C4H9 C2H5 n-Ci8H37 CH3 cyclohexyl n-C3H7 1-naphthyl 1-C4H9 phenyl CH3 phenyl n-C3H7 phenyl t-C4H9 4-phenylphenyl C2H5 4-phenylphenyl 11-C4H9 4-fluorophenyl CH3 4-fluorophenyl C2H5 4-chlorophenyl C2H3 4-chlorophenyl 1-C3H7 3-trifluoromethylphenyl S-C4H9 2-methoxyphenyl IVC3H7 2,3-dimethylphenyl Í-C4H9 2,4-dichlorophenyl CH3 2,4-dichlorophenyl C2H5 2-methoxy-5-fluorophenyl Í-C3H7 2,6-dimethoxyphenyl CH3 3,4-dichlorophenyl C2H5 3,5-dichlorophenyl n-C4Hg

_nD 22 1.4962;

Table IX 'a,

Ri R2 Re Qt Q2 C2H5 CH3 CH3 CH3 CH3 cyclohexyl CH3 Í-C3H7 H CH3 n-Ci8H37 η-0βΗΐ3 t-C4H9 CH3 CH3 1-naphthyl CH3 Í-C3H7 CH3 CH3 phenyl CH3 Í-C4H9 H CH3 phenyl CH3 t-C4H9 CH3 H phenyl CH3 t-C4H9 CH3 CH3 phenyl CH3 S-C4H9 H CH3 phenyl CH3 Í-C4H9 H CH3 4-phenylphenyl 11-C4H9 t-C4H9 H CH3 4-phenylphenyl CH3 t-C4H9 H CH3 4-phenylphenyl CH3 t-C4H9 CHs CH3 4-chlorophenyl CH3 t-C4H9 H CHs 4-chlorophenyl CH3 t-C4H9 CH3 CHs 4-fluorophenyl CH3 t-C4H9 H CH3 4-fluorophenyl CH3 t-C4H9 CHs CH3 phenyl phenyl C2H5 CH3 CH3 phenyl phenyl n-C3H7 CH3 CH3 4-fluorophenyl phenyl Í-C3H7 H CH3 4-fluorophenyl phenyl t-C4H9 CH3 CH3 4-chlorophenyl phenyl Í-C3H7 H CH3 2,4-dichlorophenyl phenyl H CH3 CH3 4-fluorophenyl 4-fluorophenyl t-C4H9 H CH3 4-fluorophenyl 4-fluorophenyl t-C4H9 CH3 H 4-fluorophenyl 4-fluorophenyl t-C4H9 CHs CH3 2-methoxyphenyl 2-methoxyphenyl C2H5 CH3 CH3 3-methylphenyl 3-methylphenyl 1-C4H9 H CHs

Example 33 Example 34

Preparation of chloromethyl (dichloro)phenylsilane

A solution of 25.1 ml (36.8 g, 0.200 mol) of chloromethyltrichlorosilane in 400 ml of dry tetrahydrofuran is cooled to -78 °C under nitrogen and stirred vigorously while 48.0 ml (0.100 mol) of 2.1 molar phenyllithium is slowly added dropwise over one hour. Stirring is continued for a further 30 minutes at -78 °C, then the solution is allowed to warm to room temperature and evaporated to 200 ml. 500 ml of ether are added, the lithium chloride is removed by filtration and the filtrate is evaporated to give 25.0 g of liquid. Distillation gives 6.5 g (29% of theory) of chloromethyl (dichloro)phenylsilane as a colourless liquid;

boiling point is 62 to 82°C (19.99 Pa); NMR (CDCb) δ:'

3.3 (s, 2) and

7.1 to 7.9 (m, 5).

Preparation of chloromethyl(diethoxy)phenylsilane

A solution of 1.0 g (0.0044 mol) of chloromethyl(dichloro)phenylsilane in 8 ml of absolute ethanol was cooled to 0 °C under ^a nitrogen atmosphere and stirred while slowly adding 0.61 ml (0.445 g, 0.0044 mol) of triethylamine to give a suspension which was slowly warmed to room temperature. 50 ml of ether was added, the precipitated triethylamine/hydrochloride was removed by filtration and the filtrate was evaporated to give the product as a residue which was filtered through a short silica gel column (95% petroleum ether:ethyl acetate as eluent) to give 0.80 g (73% of theory) of chloromethyl(diethoxy)phenylsilane as a ^colourless oil:

NMR (CDCl3)

1.25 (t, 6, J = 6Hz), 3.0 (s, 2),

3.9 (q, 4, J = 6Hz) and

7.2 to 7.9 (m, 5).

238826

Ri Ra Re

4-chlorophenyl CH3 C2H5 4-fluorophenyl n-C6Hi3 n-C3H7 4-fluorophenyl CH3 C2H5 4-phenoxyphenyl cyclohexyl 1-C4H9 4-t-butylphenyl n-CíH7 S-C4H9 3-trifluoromethylphenyl t-C4H0 H 2-methylthiophenyl cyclopentyl C2H5 2,4-dichlorophenyl CH3 CH3 2,4-dichlorophenyl CH3 C2H5 2,4-dichlorophenyl CH3 t-C4H9 2,4-dichlorophenyl n-C^Hg C2H5 2,3-dimethylphenyl cyclopropyl 1-C3H7 2-methyl-5-fluorophenyl S-C4H9 n-C3H7 2,6-dimethoxyphenyl 1,1-dimethylpropyl H 3-methyl-4-chlorophenyl C2H5 CH3 3,5-dichlorophenyl n-CsHil C2H5 11-C12H25 2,4-dichlorophenyl Í-C4H9 n-Ci8H37 phenyl CH3 1-naphthyl phenyl C2H5 phenyl phenyl t-C4H9 4-fluorophenyl phenyl CH3 4-chlorophenyl phenyl n-C3H7 4-phenylphenyl phenyl C2H5 4-phenylphenyl phenyl S-C4H9 4-t-butylphenyl phenyl S-C4H9 3-fluorophenyl phenyl C2H5 2-methoxyphenyl phenyl H 2-chlorophenyl phenyl CHs 2,4-dichlorophenyl phenyl 1-C3H7 3,5-dichlorophenyl phenyl n-CsH7 4-fluorophenyl 4-fluorophenyl t-CiHa 4-fluorophenyl 4-fluorophenyl C2H5 4-chlorophenyl 4-chlorophenyl CH3 4-chlorophenyl 4-chlorophenyl C2H5 4-phenylphenyl 4-phenylphenyl CH3 2,4-dichlorophenyl 2,4-dichlorophenyl C2H5 3-trifluoromethylphenyl 3-trifluoromethylphenyl Í-C4H9 2-methoxyphenyl 2-methoxyphenyl H 2-chlorophenyl 4-fluorophenyl H 3-trifluoromethylphenyl 4-t-butylphenyl n-C4H9 2-fluoro-4-chlorophenyl 4-bromophenyl 1-C3H7 2,3-dimethylphenyl 4-methylthiophenyl . C2H5 2,6-dimethoxyphenyl 4-methoxyphenyl H 3,4-dichlorophenyl 4-methylphenyl 1-C4H9

sodium bicarbonate, water, brine, dried over magnesium sulfate and evaporated to give 2.3 g of a viscous oil. Chromatography on silica gel, eluting with hexane and then ether, gave 1.1 g (42% of theory) of the title compound as a viscous oil which solidified on standing.

The melting point is 97 to 99°C;

NMR (CDCl 3 )

0.5 (3H, s),

3.9 (2H, s),

5.2 (1H, wide sj,

7.3 to 7.8 (9H, m),

7.9 (1H, s),

8.0 (1H, s.j.)

The compounds of Tables VIII and IX can be prepared by the methods of Examples 31 to 32c.

Example 32d

Preparation of oxybis[bis(4-fluorophenyl)[(1H-1,2,4-triazol-1-ylmethyl]silane]

A solution of 11.0 g (33.7 mmol) of chloromethyl[bis(4-fluorophenyl) ] (2-propoxy) silane and 10 ml of 49% aqueous hydrofluoric acid in ethanol was refluxed for two hours under nitrogen, cooled and partitioned between water and ether. The organic layer was washed with water and brine, dried over magnesium sulfate and evaporated to give 9.7 g (100% of theory) of chloromethyl(fluoro) [bis(4-fluorophenyl)] silane as a mobile oil:

_nD ²² 1.5387;

NMR (CDCl 3 )

3.2 (2H, dj,

7.2 (4H, i.e.,

7.8 (4H, d from dj.

A mixture of 4.5 g (16 mmol) of fluorosilane, prepared as above, and 1.6 g (18 mmol) of 1,2,4-triazole in the form of the sodium salt in dimethylformamide was stirred at 80-90 °C for two hours. The resulting suspension was diluted with ether, washed three times with water and once with brine, dried over magnesium sulfate and evaporated to give a viscous oil. Trituration with a 1:1 ether-hexane system gave 1.1 g (23% of theory) of the prepared disiloxane as a colorless solid:

the melting point is 165 to 168°C;

NMR (CDCl3)

4.1 (2H, s),

7.0 (4H, t),

7.4 (4H, d from dj,

7.8 (1H, s),

7.9 (1H, s).

Table VIII

Ri R6

C2H5 CH3 CH3 t-C4H9 CH3 t-CáHg n-CíH9 CHs C2H5 h-Cl2H25 C2H5 CH3 11-C18H37 n-C6Hi3 CH3 cyclopropyl CH3 S-C4H9 cyclohexyl CH3 CH3 1 -naphthyl Í-C3H7 1-C3H7 2-naphthyl cyclobutyl n-C3H7 phenyl CH3 H phenyl CH3 CH5 phenyl CH3 C2H5 phenyl CH3 1-C3H7 n _D ²⁰ 1.5 3 67 phenyl Í-C4H9 H 4-phenylphenyl n-C4H9 CH3 4-phenylphenyl Í-C4H9 H 4-phenylphenyl CH3 C2H5 4-phenylphenyl CH3 n-CáHg 4-chlorophenyl II-C4H9 n-C4H9 4-chlorophenyl CH? CH?

gives (Ι,Γ-biphenyl-4-yl)(1H-1,2,4-triazol-lylmethyl)methoxy/methylsilane.

Related compounds can be prepared in the same manner using the appropriate chlorosilane and alcohol;

for Re — hydroxyl group, water is used instead of alcohol and hydrolysis is carried out at 20 to 25 °C instead of 70 °C.

Example 32

Preparation of (1,1-dimethylethoxy)methyl(phenyl)(1H-1,2,4-triazol-1-ylmethyl)silane

A mixture of 3.6 g (0.015 mol) of chloromethyl(1,1-dimethylethoxy)methyl(phenyl)silane and 1.3 g (0.015 mol) of 1,2,4-triazole sodium salt in 8 ml of dimethylformamide was stirred at 80 °C for two hours, cooled and poured into water. The resulting mixture was extracted with ether and the ether extracts were washed with water and brine, dried over magnesium sulfate and evaporated to give 2.7 g of a yellow oil. Chromatography on silica gel, eluting with 50 : 50 ethyl acetate — hexanes, gave 1.5 g (36% of theory) of (1,1-dimethylethoxy)methyl(phenyl) (1H-1,2,4-triazol-1-ylmethyl)silane as a pale yellow oil:

m?! 1.5134;

ir (pure) 3120, 3070, 3045, 2975, 2925,1500,

1425, 1380, 1365, 1270, 1240, 1190, 1140,

1115, 1050, 1020, 1010, 830, 810, 790, 740,

700, 680 cm ^-1 ;

NMR (CDCl3)

0.0 (3H, sj,

1.3 (9H, s),

3.9 (2H, s),

7.3 - 7.7 (5H, among others,

7.9 (1H, sj and

8.0 (1H, s.j.)

Compounds listed in Tables VIII and IX, where

Q1 = _q2 = H can be prepared similarly as described in Examples 31 and 32.

Example 32a

Preparation of bis(4-fluorophenyl)hydroxy(1H-1,2,4-triazol-1-ylmethyl)silane

A mixture of 10.0 g (30.6 mmol) of chloromethyl bis(4-fluorophenyl) (2-propoxysilane) and 3.1 g (30.6 mmol) of 1,2,4-triazole in the form of the sodium salt in dimethylformamide is stirred at 80-90°C under nitrogen for two hours. Working up as described in Example 32 yields 3.0 g (30% of theory) of the desired compound. Recrystallization from chlorobutane yields a purer compound. Melting point is 130-131°C;

NMR (CDCl3)

4.1 (2H, s),

5.8 (1H, wide s),

7.1 (4H, t),

7.7 (4H, d from d),

7.8 (1H, sj,

8.0 (1H, s).

Example 32b

Preparation of bis (4-chlorophenyl) hydroxy (1H-1,2,4-triazol-1-ylmethyl silane and bis (4-chlorophenyl) hydroxy (4H-1,2,4-triazol-4-ylmethyl silane

The procedure described in Example 32a was followed using chloromethyl[bis(4-chlorophenyl)] (2-propoxy)silane. Workup gave an oil which was stirred with hexanes. The hexane layer was then decanted and the remaining oil was recrystallized from 9:1 hexanes-ethyl acetate to give the 1H isomer as a solid.

The melting point is 130 to 131°C;

NMR (CDCl3)

4.1 (2H, sj,

6.3 (1H, wide sj,

7.4 (4H, dj,

7.6 (4H, dj,

7.8 (1H, s),

8.0 (1H, s.j.)

Chromatography of the mother liquors on silica gel, eluting first with hexane and then with a 9:1 dichloromethane-acetone system, gives the 4H isomer as a solid: melting point 98-103 °C;

NMR (CDCl3)

1.7 (1H, wide s),

4.2 (2H, s),

7.8 (8H, sj,

7.8 (2H, s.j.)

Example 32c

Preparation of (1,1'-biphenyl-4-yl)hydroxy(methyl) (1H-1,2,4-triazol-1-ylmethyl)silane

A mixture of 3.0 g (8.9 mmol) of (Ι,Γ-biphenyl-4-yl)methyl (2-propoxy) (1H-1,2,4-triazol-1-ylmethyl)silane, 3 ml of concentrated hydrochloric acid, 10 ml of water and 10 ml of tetrahydrofuran was stirred at room temperature overnight. The resulting solution was diluted with ether, washed with saturated aqueous

Rl R2 R3 Qi Q2 4-fluorophenyl 4-fluorophenyl CH3 H CH3 4-fluorophenyl 4-fluorophenyl CH3 - CH3 H 4-chlorophenyl 4-chlorophenyl CH3 H CH3 4-chlorophenyl 4-chlorophenyl CHs CH3 CHs 2-chlorophenyl 4-chlorophenyl ch ₃ H CH3 2,4-dichlorophenyl 2,4-dichlorophenyl CH3 CH3 CHs n-Ci8H37 n-CeHis n-CsHi3 CH3 CH3 1-naphthyl n-C4H9 n-CiHg H CH3 phenyl phenyl phenyl H CH3 phenyl phenyl phenyl CH3 H phenyl phenyl phenyl CH3 CH3

Example 28 n _D ²⁰ 1.5645;

Preparation of a 1:1 complex of (1,1'-biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane and copper chloride.

A mixture of 5.0 g (0.017 mol) of (Ι,Γ-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane and 1.7 g (0.017 mol) of copper (I) chloride in 170 ml of tetrahydrofuran is refluxed under nitrogen for 30 minutes and the resulting deep green solution is evaporated to give a 1 : 1 complex of (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane and copper (I) chloride as a dark greenish brown solid; melting point 85 to 90 °C;

ir (Nujol ^R ) 3110, 1590, 1280, 1250, 1120, 1010,

990, 840, 825, 760, 700 cm" ¹ .

Similarly, the following complexes of (Ι,Γ-biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-4-ylmethyl)silane are prepared:

:1 complex with copper chloride with a melting point of 83 to 87 °C, :1 complex with copper chloride with a melting point of 85 to 92 °C,

1:1 complex with zinc chloride: n _D ²¹ 1.5737, : 1 complex with manganese sulfate with a melting point of 244 to 250 °C with decomposition.

Example 29

Preparation of 4-dodecylbenzenesulfonate salt of (1,1'-biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)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 is combined with a solution of 1.1 g (0.0034 mol) of 4-dodecylbenzenesulfonic acid in 10 ml of dichloromethane. The resulting solution is evaporated to give the 4-dodecylbenzenesulfonate salt of (1,1'-biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane as a viscous yellow oil:

ir (clean) 3110, 3050, 3020, 2960, 2920, 2850,

2570, 1920, 1600, 1545, 1485, 1455, 1405,

1250, 1225, 1165, 1120, 1030, 845, 825, 755,

1010, 990, 735, 700, 670, 635 cm" ¹ .

Example 30

Preparation of 2:1 complex of (bis(4-fluorophenyl)]methyl(1H-1,2,4-triazol-1-ylmethyl)silane and copper chloride

A mixture of 1.0 g (0.0032 mol) [bis(4-fluorophenyl)]methyl(1H-1,2,4-triazol-1-ylmethyl)silane and 0.2 g (0.0016 mol) copper (II) chloride in 30 ml tetrahydrofuran was heated under reflux under nitrogen for 30 min and evaporated to give a 2:1 complex of [bis(4-fluorophenyl)]methyl(1H-1,2,4-triazol-1-ylmethyl)silane and copper (II) chloride as a blue-green glass: no distinct melting point;

ir (Nujol ^R ) 1580, 1490, 1230, 1160, 1110, 830,

785 cm ¹ .

Similarly, a 1:1 complex with copper chloride is prepared in the form of a dark green glass without a significant melting point; ir as above.

Using the methods described in Examples 26 to 28, any compound of Tables VI, VII, VIII, IX, XII and XIII is converted into salts or complexes with metals.

Example 31

Preparation of (1,1'-biphenyl-4-yl) (1H-1,2,4-triazol-1-ylmethylmethoxy) methylsilane

A mixture of (1,1'-biphenyl-4-yl)chlorochloromethylmethylsilane and two equivalents of the 1,2,4-triazole salt in dimethylformamide is maintained at 80-90°C for two hours. 10 equivalents of methanol are then added and the mixture is maintained at 70°C for one hour, cooled, diluted with water and rapidly extracted with ether. The ether solution is washed with water and brine, dried over magnesium sulphate and evaporated to give

Example 26

Preparation of (3,5-dimethyl-1H-1,2,4-triazol-1-ylmethyl) [bis(4-fluorophenyl)] methylsilane (3,5-Dimethyl-1H-1,2,4-triazol-1-ylmethyl)[bis(4-fluorophenyl)] methylsilane was prepared as described in Example 25 using equimolar amounts of chloromethyl[bis-(4-fluorophenyl)] methylsilane and sodium salt of 3,5-dimethyl-1,2,4-triazol.

Related compounds are prepared using 3-methyl-1,2,4-triazole instead of the 3,5-dimethyltriazole salt.

Example 27

Preparation of (1,1'-biphenyl-4-yl)dimethyl (3-methyl-1H-1,2,4-triazol-1-ylmethyl)silane

A solution of 5.9 g (0.020 mol) of (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane in 40 ml of dry tetrahydrofuran was cooled to -40 °C under nitrogen and stirred while 12.5 ml (0.020 mol) of a 1.6 molar solution of n-butyllithium in hexane was added dropwise. The resulting yellow solution was stirred for a further 15 min at -40 °C, treated with 1.9 ml (4.2 g, 0.030 mol) of methyl iodide and allowed to warm to room temperature. The resulting solution was diluted with water and extracted with hexanes. The organic extracts were washed with water and brine, dried over magnesium sulfate and evaporated to give 5.7 g of a solid which was purified by chromatography on a silica gel column. by dry column chromatography on silica gel (ethyl acetate solution) to give 1.1 g of crude product. Recrystallization from 12 ml of hexanes-ethyl acetate 3:1 then gave 0.97 g (16% of theory) of [1,1'-biphenyl-1H-1,2,4-triazol-1-ylmethyl][bis(4-fluorophenyl)]methylsilane as a white solid:

the melting point is 95 to 98°C;

ir (Nujol ^R j 1590, 1270, 1250, 1180, 1120, 830,

765, 700 cm'*

NMR (CDCl3)

0.5 (6H, sj,

2.2 (3H, s),

3.7 (2H, sj,

7.2 - 7.7 (9H, m),

7.8 (1H, sj.

Although the above structure is advantageous for spherical reasons, the position of the methyl group on the triazole ring has not been proven and it is possible that the product is (1,1'-biphenyl-4-yl)dimethyl (5-methyl-1H-1,2,4-triazol-1-ylmethyl)silane.

The methods described in Examples 26 and 27 can be used to prepare the compounds listed in Table VII.

Table VII

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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 chloromethyl-bis(4-chlorophenyl)methylsilane and 2.0 g (0.022 mol) of sodium salt of 1,2,4-triazole in 10 ml of dry dimethylformamide was stirred at 80°C for 4 hours. The resulting suspension was cooled, diluted with water and washed with ether. The ether extracts were washed with several portions of water and one portion of brine, dried over magnesium sulfate and evaporated to give 5.4 g of a yellow oil: distillation in a neck flask at 120-150 °C (air bath) and 6.66 Pa gave 4.0 g (58% of theory) of bis(4-chloromethyl)methyl (1H-1,2,4-triazol-1-ylmethyl)silane as a pale yellow oil: n _D ²⁶ 1.5966;

NMR (CDCl3)

0.7 (3H, s),

4.1 (2H, s),

7.2 — 7.5 (8H, among others,

7.8 (1H, s),

7.9 (1H, s).

In a similar preparation, evaporation of the ether extracts afforded a rubbery solid which was triturated with hexanes to give the title compound as a colorless solid, mp 76-80 °C.

Example 25

Preparation of bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane

A mixture of 4.2 g (0.015 mol) of (chloromethyl)bis(4-fluorophenyl)methylsilane and 1.4 g (0.015 mol) of 1,2,4-triazole sodium salt in 8 ml of dimethylformamide was stirred at 80 °C for two hours. The resulting suspension was cooled, diluted with water and worked up as described in Example 24 to give 4.0 g of a pale yellow oil. The impurities were removed by distillation in a neck flask at 120-125 °C and 6.66 Pa to give 2.3 g (49% of bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane as a yellow oil:

_nD21 ^1.5538 ;

ir (net 3065, 3030, 2960, 2925, 1590, 1500,

1270, 1235, 1165, 1110, 1010, 830, 790 cm!; NMR (CdClb)

0.7 (3H, sj,

4.2 (2H, s),

7.1 (4H, t, J = 9),

7.5 (4H, d from d, J = 6 and 9),

7.8 (1H, sj and

7.9 (1H, s).

A similarly prepared sample, after recrystallization from hexane at -120°C, gives a colorless solid with a melting point of 52-53°C. According to Examples 19 and 21-25, the compounds of Table VI are prepared from suitable chloromethylsilanes, where Qi = Q2 = H.

A 1 g sample of once recrystallized 1',1'-(biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-4-ylmethyl)silane, prepared as described in Example 14 using sodium methoxide-1,2,4-triazole, was subjected to high-pressure liquid chromatography (sillkagel Water Prep PAK-500, flow rate 250 milliliters per minute). Elution with the ethyl acetate-hexane system in a ratio of 50:50 removes the first small amount of impurities and then yields the pure 1H-1,2,4-triazol-1-ylmethyl compound with a melting point of 99 to 100 °C. Continued elution with the ethyl acetate-acetonitrile system in a ratio of 80:20 yields a small amount of 1,1'-biphenyl-4-yl(dimethyl)-4H-1,2,4-triazol-4-yl(methyl)silane in the form of a colorless solid. melting point 130-133 °C; NMR (CDCl 2 )

0.4 (6H, s),

3.7 (2H, s),

7.2 - 7.7 (9H, m),

7.9 (2H, s.j.)

Microanalysis for C17H19N3Si (molecular weight 293.43) calculated:

C 69.58, H 6.53 N 14.32 found:

C 69.00 H 6.70 N 13.90

C 69.30 H 6.70 N 14.2

Example 21

Preparation of dimethyl (phenyl) (1H-1,2,4-triazol·-1-ylmethyl jsilane

A mixture of 9.0 ml (9.2 g, 0.050 mol) of chloromethyldimethylphenylsilane and 5.5 g (0.060 mol) of 1,2,4-triazole sodium salt in 25 ml of dimethylformamide was stirred and maintained at 90-95 °C for two hours, cooled, diluted with water and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulfate and evaporated to give 8.1 g (75% of theory) of a pale brown oil, n _D ²² 1.5350, containing dimethyl (phenyl) (1H-1,2,4-triazol-1-yl-methyl)silane and minor impurities as determined by NMR. A purer sample was obtained by distillation:

boiling point 99 °C at a pressure of 2.66 Pa;

_nD20 ^1.5403 ;

NMR (CDCl 3 )

0.4 (6H, s),

3.8 (2H, sj,

7.2 - 7.7 (5H, m),

7.7 (1H, sj,

7.8 (1H, s);

analysis for C11H1.5N3Si (molecular weight 217.34) calculated:

L 60.78 H 6.96 N 19.33 found:

C 60.70 H 7.00 N 16.90

C 60.20 H 7.00 N 16.80

Example 22

Preparation of (4-chlorophenyl)dimethyl{1H-1,2,4-triazol-1-ylmethyl)silane

A mixture of 2.2 g (0.010 mol) of chloromethyl(4-chloromethyl)dimethylsilane and 1.1 g (0.012 mol) of sodium salt of 1,2,4-triazole in 5 ml of dimethylformamide was maintained at 80-90 °C for two hours, diluted with water and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulfate and evaporated to give 2.1 g (83% of theory) of (4-chlorophenyl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane as a yellow liquid:

_nD21 ^1.5428 ;

ir (pure) 1555, 1470, 1245, 1130, 1080, 1010,

835, 805, 795, 735 cm ^-1 ;

NMR (CDCl3)

0.4 (6H, s),

3.8 (2H, s),

7.4 (4H, wide s),

7.8 (1H, sj.

Example 23

Preparation of (2,4-dichlorophenyl)dimethyl {1H-1,2,4-triazol-1-ylmethyl}silane

A mixture of 5.1 g (0.020 mol) of chloromethyl(2,4-dichlorophenyl)dimethylsilane and 2.0 g (0.022 mol) of 1,2,4-triazole sodium salt in 10 ml of dry dimethylformamide was stirred at 80-90 °C for two hours. The resulting suspension was cooled, diluted with water and washed with ether. The ether extracts were washed with several portions of water and one portion of brine, dried over magnesium sulphate and evaporated to give 4.6 g (81% of theory) of (2,4-dichlorophenyl)dimethyl(1H,1,2,4-triazol-1-ylmethyl)silane as a pale yellow liquid:

_nD ²³ 1.5580;

ir (clean) 1550, 1485, 1440, 1345, 1260, 1240,

1130, 1085, 1025, 1005, 835 cm -1 ;

NMR (CDCl3)

0.5 (6H, s),

X = Ri, Ri' R2 Rs

2,4-dichlorophenyl n-C4H9 C2H5 2,3-dimethylphenyl cyclopropyl Í-C3H7 2-methyl-5-fluorophenyl S-C4H9 n-C3H7 2,6-dimethoxyphenyl 1,1-dimethylpropyl H 3-methyl-4-chlorophenyl C2H5 CH3 3,5-dichlorophenyl n-CsHii C2H5 n-Ci2H25 2,4-dichlorophenyl Í-C4H9 n-CwH37 phenyl CH3 1-naphthyl phenyl C2H5 phenyl phenyl t-C4H9 4-fluorophenyl phenyl CH3 4-chlorophenyl phenyl n-C3H7 4-phenylphenyl phenyl C2H5 4-phenylphenyl phenyl S-C4H9 4-t-butylphenyl phenyl S-C4H9 3-fluorophenyl phenyl C2H5 2-methoxyphenyl phenyl H 2-chlorophenyl phenyl CPI3 2,4-dichlorophenyl phenyl Í-C3H7 3,5-dichlorophenyl phenyl n-C3H7 4-fluorophenyl 4-fluorophenyl t-C4H9 4-fluorophenyl 4-fluorophenyl C2H5 4-chlorophenyl 4-chlorophenyl ch ₃ 4-chlorophenyl 4-chlorophenyl C2H5 4-phenylphenyl 4-phenylphenyl ch ₃ 2,4-dichlorophenyl 2,4-dichlorophenyl C2H5 3-trifluoromethylphenyl 3-trifluoromethylphenyl Í-C4H9 2-methoxyphenyl 2-methoxyphenyl H 2-chlorophenyl 4-fluorophenyl H 3-trifluoromethylphenyl 4-t-butylphenyl n-CdH9 2-fluoro-4-chlorophenyl 4-bromophenyl Í-C3H7 2,3-dimethylphenyl 4-methylthiophenyl C2H5 2,6-dimethoxyphenyl 4-methoxyphenyl H 3,4-dichlorophenyl 4-methylphenyl 1-C4H9 4-fluorophenyl methyl 1-C3H7 η„2θ 1.4827 4-fluorophenyl 4-fluorophenyl i-CaHg tv 110 to 111 ⁰ (13.33 Pa) 4-chlorophenyl 4-chlorophenyl 1-C3H7 n _D 22 1.5650

Example 19

Preparation of (1,1'-biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane

A mixture of 2.6 g (0.010 mol) of (1,1'-biphenyl-4-yl)chloromethyldimethylsilane and 1.1 g (0.012 mol) of 1,2,4-triazole sodium salt in 5 ml of dimethylformamide was maintained at 80-90 °C for two hours, cooled, diluted with water and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulphate and evaporated to give 2.3 g of a colourless solid, m.p. 79-86 °C. Recrystallization from 25 ml of hexanes and 2 ml of ethyl acetate gave 1.1 g (38% of theory) of (1,1'-biphenyl-4yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane, m.p. 92-93 °C;

ir (Nujol ^R ) 1255, 1130, 1000, 825, 760, 695 cm"¹;

7.2 - 7.7 (9H, m),

7.8 (1H, s),

7.9 (1H, s);

analysis for C17H19N3SI (molecular weight 293.43) calculated:

C 69.58 H 6.53 N 14.32 found:

C 70.0 H 6.6 N 13.9 C 69.8 H 6.7 N 13.8

An equimolar mixture of 1,2,4-triazole and sodium methoxide can be used instead of the pre-prepared sodium triazole salt. These reactants must be mixed before adding the silane, as chloromethylsilane reacts very vigorously with sodium methoxide in dimethylformamide to form unwanted products.

NMR (CDCl3)

0.4 (6H, s), 3.9 (2H, s),

Example 20

Preparation of (1,1'-biphenyl-4-yl)dimethyl(4H-1 _? 2,4-triazol-4-ylmethyl)silane lan, therefore the oil is dissolved in hexanes containing 30 ml of isopropanol and the solution is rapidly cooled in ice and treated with a solution of 42 ml (0.30 mol) of 'triethylamine in hexanes. The resulting suspension is stirred at room temperature for three hours and filtered and the filtrate is evaporated to give an oil. Distillation gives 44.8 g (43% of theory) of the prepared compound as a colorless liquid with a boiling point of 120-140 ° C (13.32 Pa); n _D ²² 1.5211;

NMR (CDCl)

1.2 (6H, d),

3.2 (2H, s),

4.1 (1H, septet),

7.1 (4H, t),

7.7 (4H, d from d).

Example 18

Preparation of chloromethyl (ethoxy)methyl (phenyl)silane

A solution of 18.2 ml (18.2 g, 0.10 mol) of chloromethyl (diethoxy)methylsilane in 200 ml of dry ether is stirred vigorously under a nitrogen atmosphere and with cooling, while adding 56 ml (0.10 mol) of a 1.8 molar solution of phenylthio in the cyclohexane-ether system in a ratio of 70:30 at such a rate as to keep the temperature of the mixture below -50 °C. The resulting suspension is allowed to warm to room temperature, treated carefully with 10 ml of ethyl acetate, washed with water and brine, dried with magnesium sulfate and evaporated, thereby obtaining 16.8 g of a golden yellow oil. Distillation yields 9.5 g (44% of theory) of chloromethyl (ethoxymethylphenyl)silane in the form of a colorless liquid with a boiling point of 80 to 84 °C at a pressure of 13.33 Pa;

_nD20 ^1.5144 ;

NMR (CÎCks)

0.5 ('3H, s), 1.2 (3H, t, J = 7),

3.0 (2H, s),

3.8 (2H, q, J = 7),

7.2-7.8 (5H, m).

The compounds of Table V can be prepared using the method described in Examples 16 to 18.

Table V

R2

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X = Ri, Ri' R2 Re

C2H5 CH3 CH3 t-ClHs CHs t-C4H9 11-C4H9 CH3 C2H5 n-Ci2H25 C2II5 GH-3 11-C18H37 n-CeHis CH3 cyclopropyl CHí S-C4H9 cyclohexyl GHs CHs 1-naphthyl Í-C3H7 Í-C3H7 2-naphthyl cyclobutyl n-CjH? phenyl CHs H phenyl CH3 Í-C3H71. at. 72 to 76 °C (13.33 Pa) phenyl t-CíHa H 4-phenylphenyl 11-CiHs CH3 4-phenylphenyl t-CdHg H 4-phenylphenyl CH3 G2H5 4-phenylphenyl CH3 11-C4H9 4-chlorophenyl 11-G4H9 11-G4H9 4-chlorophenyl CH3 CHs 4-chlorophenyl CH3 C2H5 4-fluorophenyl n-CeHi3 n--G3H7 4-fluorophenyl CH3 C2H5 4-phenoxyphenyl cyclohexyl Í-G4H9 4-t-butylphenyl n-C3H7 S-C4H9 3-trifluoromethylphenyl t-CáHg H 2-methylthiophenyl cyclopentyl G2H5 2,4-dichlorophenyl CH3 CH3 2,4-dichlorophenyl GH3 C2H5 2,4-dichlorophenyl CH3 Í-C4H9

Example 16

Preparation of chloromethyl (methoxy) methyl (phenyl) silane

A solution of 1.6 ml (1.3 g, 0.040 mol) of methanol and 3.0 ml (2.2 g, 0.022 mol) of triethylamine in 100 ml of ether was stirred while a solution of 4.1 g (0.020 mol) of chloro(chloromethyl)methyl (phenyl)silane in 10 ml of ether was added dropwise. The resulting suspension was refluxed for two hours, cooled, washed with water, 0.1 N aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution and brine, dried over magnesium sulfate and evaporated to give 3.2 g of a pale yellow liquid. Distillation gave 1.7 g (42%) of chloromethyl(methoxy)methyl (phenyl)silane as a colourless liquid:

boiling point is 46 to 49 °C at a pressure of 6.66 Pa; n _D ²² 1.5207;

NMR (CDCl 3 )

0.5 (3H, s),

3.0 (2H, sj,

3.5 (3H, s) and

7.3 - 7.8 (5H, m).

Example 17

Preparation of chloromethyl (1,1-dimethylethoxy)methyl (phenyl)silane

A mixture of 15.4 g (0.075 mol) of chloro(chloromethyl)methyl(phenyl)silane, 14 ml (11.1 g, 0.15 mol) of tert-butanol, 11.5 ml (8.3 g, 0.082 mol) of triethylamine and 0.5 g (0.008 mol) of imidazole in 60 ml of dimethylformamide was stirred at 80 °C for two hours. The resulting suspension was cooled, poured into 200 ml of water and extracted with ether. The ether extracts were washed with water three times, then washed with 0.1 N aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution and brine, dried over magnesium sulphate and evaporated to give 14.0 g of a pale orange oil. Distillation yields 11.9 g (65% of theory) of chloromethyl (1,1-dimethylethoxy) methyl (phenyl)silane with a boiling point of 78 to 82 °C at a pressure of 26.66 Pa;

_nD ²¹ 1.5010;

ir (pure) 3080, 3060, 2990, 2940, 1600, 1435,

1395, 1370, 1260, 1245, 1195, 1125, 1060,

1030, 815, 790, 740, 725, 705, 650 cm"¹; NMR (CDCb)

0.3 (3H, s),

1.3 (9H, s).

2.9 (2H, s) and

7.3-7.8 (3H, m).

Example 17a

Preparation of (1,1'-biphenyl-4-yl)chloromethyl (methyl (2-propoxy)silane)

A solution of 73.3 g (0.315 mol) of 4-bromobiphenyl in 300 ml of tetrahydrofuran is added dropwise to a stirred suspension of 7.64 g (0.315 mol) of magnesium in 100 ml of tetrahydrofuran at such a rate as to maintain the temperature at a gentle reflux. The resulting clear solution is stirred at room temperature for one hour and then cooled in ice and a solution of 40 ml (0.315 mol] chloromethyl (dichloro)methylsilane in 100 ml tetrahydrofuran is quickly added. The resulting solution is stirred at room temperature for 20 hours, treated with 50 ml isopropanol and cooled again in ice. Then a solution of 48 ml (0.344 mol] triethylamine in tetrahydrofuran is added at such a rate that the temperature of the mixture is maintained below 25 °C. Stirring at room temperature for 90 minutes gives a suspension. Residues of amine hydrochloride are removed by filtration, evaporation of the filtrate, trituration with hexanes and a second filtration. Evaporation of the hexane solutions gives 92 g (96% of theory) of the compound prepared in the form of a pale yellow oil, which solidifies on standing. Melting point is 35-38 °C;

NMR (CDCl3)

0.5 (3H, s),

1.2 (6H, d),

3.0 (2H, s),

4.2 (1H, septet],

7.3 — 7.8 (9H, m).

Example 17b

Preparation of chloromethyl [bis(4-fluorophenyl)] (2-propoxy) silane

A mixture of 23.2 g (0.955 mol) of magnesium and 50 mg of iodine in 200 ml of ether is stirred while adding a solution of 167 g (0.954 mol) of 4-bromofluorobenzene in 600 ml of ether at such a rate as to maintain the temperature at gentle reflux. It is then maintained at reflux for a further two hours, the solution is cooled in ice and stirred while a solution of 40 ml (0.32 mol) of chloromethyltrichlorosilane in ether is added dropwise over a period of 40 minutes. The resulting mixture is stirred at room temperature for 17 hours, cooled in ice, treated with 24 ml of isopropanol, stirred for a further 10 minutes and filtered. The filtrate was concentrated to a gummy solid, hexanes were added, the resulting suspension was filtered, and the hexane filtrate was evaporated to give an oil. NMR analysis showed the presence of unreacted chlorosi238626

Table IV

R2

X—Si—CH:C1

X = Ri, Ri*

C2H5 t-CáHg

11-C4H9 n-Ci2H25

11-C18H37 cyclopropyl cyclohexyl

1- naphthyl

2- naphthyl phenyl

4-phenylphenyl

4-phenylphenyl

4-chlorophenyl

4-chlorophenyl

4-fluorophenyl

4-phenoxyphenyl

4-t-butylphenyl

4-trifluoromethoxyphenyl

4-(4-fluorophenyl)phenyl

3-trifluoromethylphenyl

2-thiomethylphenyl

2,4-dichlorophenyl

2.4- dichlorophenyl

2-chloro-4-phenylphenyl

2,3-dimethylphenyl

2- methyl-5-fluorophenyl 2,6-dimethoxyphenyl

3-methyl-4-chlorophenyl

3.5-dichlorophenyl n-Ci2H25 n-CieH37

1- Naphthyl phenyl

4-fluorophenyl

4-chlorophenyl 4-phenylphenyl 4-t-butylphenyl

3-fluorophenyl

2- methoxyphenyl

2-chlorophenyl

2.4- dichlorophenyl

3.5- dichlorophenyl

4-fluorophenyl 4-chlorophenyl 4-phenylphenyl

2,4-dichlorophenyl

3-trifluoromethylphenyl 2-methoxyphenyl

2-chlorophenyl

3-trifluoromethylphenyl 2-fluoro-4-chlorophenyl

2,3-dimethylphenyl

2,6-dimethoxyphenyl

3,4-dichlorophenyl

4-chlorophenyl

Cl

R2

CHs

CH3

CH3

C2H5 n-C6Hi3

CH3

CH3

Í-C3H7 cyclobutyl t-C1Hp n-C1Hg n-C6Hi3 n-C4H9

CH3 n-C6Hi3 cyclohexyl n-C3H7

CHs

CH3 t-CiH9 cyclopentyl

CHs n-CiHa

CHs cyclopropyl

S-C4H9

1,1-dimethylpropyl

C2H5 n-CsHii

2.4- dichlorophenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl

4-fluorophenyl

4-chlorophenyl

4-phenylphenyl

2.4- dichlorophenyl

3-trifluoromethylphenyl

2-methoxyphenyl

4-fluorophenyl

4-t-butylphenyl

4-bromophenyl

4-methylthiophenyl

4-methoxyphenyl

4-methylphenyl

4-chlorophenyl b.p. 110 to 130°C (13.33 Pa)

X = Ri, Ri'

R2

R3 phenyl

1-naphthyl

4-phenoxyphenyl

4-fluorophenyl

4-chlorophenyl

4-bromophenyl

3,5-dimethylphenyl

4-fluorophenyl

4-phenylphenyl

3-methylphenyl

3,4-dichlorophenyl

4-fluorophenyl m.p. 57 to 60 °C

Example 14

Preparation of chloro(chloromethyl)methyl(phenyl)silane

A solution of 12.7 ml (16.4 g, 0.10 mol) of chloromethyl (dichloro)methylsilane in 200 ml of ether is cooled to -70 °C under a nitrogen atmosphere and stirred vigorously while a mixture of 55 ml (0.10 mol) of

A 1.8 molar solution of phenyllithium in ether-cyclohexane (30:70) and 55 ml of ether are added dropwise at a rate such that the temperature of the mixture is maintained below -70 °C. The resulting suspension is stirred and warmed to room temperature and then left to stand overnight. Filtration and evaporation of the filtrate give 20.4 g of a golden oil, which is distilled to give 14.6 g (71%) of chloro(chloromethyl)methyl(phenyl)silane as a colorless liquid:

boiling point is 71 to 74 °C at a pressure of 79.98 Pa; n _D ²³ 1.5337;

ir (pure) 3080, 3060, 2980, 2930, 1590, 1430,

1260, 1120, 820, 790, 740, 700 cm'¹;

NMR (CDCl3)

0.8 (3H, s),

3.1 (2H, s),

7.3 — 7.6 (3H, m),

7.6-7.8 (2H, m).

Example 15

Preparation of (1,1'-biphenyl-4-yl] chloro (chloromethyl) methylsilane (1,1'-Biphenyl-4-yl] chloro (chloromethyl) methylsilane can be prepared by reacting equimolar amounts of 4-bromobiphenyl, chloromethyldichloro (methyl) silane and n-butyllithium as described in Example 3.

Example 14a

Preparation of chloro[bis(4-fluorophenyl)]inethylsilane

A suspension of 7.0 g (0.288 mol) of magnesium turnings in 50 ml of ether is stirred under a stream of nitrogen while a solution of

50.2 g (0.287 mol) of 4-bromofluorobenzene in 200 ml of ether at a rate to maintain the temperature at reflux. After a further two hours at reflux, the mixture was rapidly cooled in ice and a solution of 12.0 ml (0.096 mol) of chloromethyltrichlorosilane in 30 ml of ether was added dropwise. The resulting mixture was heated at reflux for 4 hours, rapidly cooled in ice, treated with a solution of 7.5 ml of isopropanol in 20 ml of ether, stirred for 5 minutes and filtered. The filtrate was evaporated to give an oil which was stirred in hexanes to form a suspension. Filtration under a stream of nitrogen and evaporation gave a mobile oil which was distilled to give

17.6 g (61%) of the compound being prepared with a boiling point of 100 to 140 °C (13.32 Pa);

NMR (CDCl3)

3.3 (2H, sj,

7.1 (4H, t),

7.7 (4H, d from d).

Example 15

Preparation of (1,1'-biphenyl)chloro(chloromethyl)methylsilane (1,1'-Biphenyl-4-yl)chloro(chloromethyl)methylsilane can be prepared by reacting equimolar amounts of 4-bromobiphenyl, chloromethyldichloro(methyl)silane and n-butyllithium as described in Example 3.

The compounds of Table V can be prepared as described in Examples 14, 14a and 15.

CbSiCHzCl

The compounds listed in Table III are prepared by successively replacing the silicon-chlorine bond in the compound of formula by the method described in Examples 12 to 13a.

Table III

Rz

AND

X—Si—CH2Cl

I : aotA»....

R3

X = Rj, Ri' R2 R3

C2H5 C2H5 C2H5 1-C3H7 Í-C3H7 1-C3H7 n-CíHg n-C4H9 n-C4H9 U-CbHi7 C2H5 cyclopentyl n-Ci4H29 cyclopropyl 1-methylbutyl n-CieH37 n-CeHu n-C6Hi3 cyclopropyl C2H5 S-C4H9 cyclohexyl 11-C3H7 n-C3H7 1-naphthyl 11-C4H9 11-C4H9 2-naphthyl n-C4H9 cyclobutyl phenyl cyclopropyl n-C6Hi3 4-phenylphenyl n-C4H9 n-C4H9 4-phenylphenyl 11-C6H13 n-C6Hi3 4-phenylphenyl cyclohexyl cyclohexyl 4-chlorophenyl 11-C4H9 11-C4H9 4-fluorophenyl U-C3H7 n-C3H7 4-phenoxyphenyl 11-C4H9 cyclohexyl 4-(4-chlorophenoxy)phenyl n-C4H9 n-C<H9 4-t-butylphenyl S-C4H9 1-C4H9 3-methoxyphenyl C2H5 t-CéHg 3-trifluoromethylphenyl S-C4H9 S-C4H9 2-thiomethylphenyl 1-C3H7 3-methylbutyl 2-phenylphenyl cyclohexyl cyclohexyl 2,4-dichlorophenyl n-CdHg n-C4H9 2,6-dimethylphenyl Í-C4H9 t-CdHg 3,5-dichlorophenyl cyclopentyl cyclopentyl 3-methyl-4-chlorophenyl S-C4H9 S-C4H9 C2H5 phenyl phenyl cyclohexyl phenyl phenyl n-Ci8H37 phenyl phenyl tl-C4H9 4-chlorophenyl 4-chlorophenyl n-Ci2H25 4-chlorophenyl 4-chlorophenyl 1-naphthyl 4-fluorophenyl 4-fluorophenyl cyclopropyl phenyl 4-t-butylphenyl 11-C4H9 phenyl 4-phenylphenyl t-CdHg phenyl 2,4-dichlorophenyl 11-C3H7 phenyl 3-trifluoromethylphenyl Í-C4H9 phenyl 3,5-dichlorophenyl cyclopentyl phenyl 2,6-dimethoxyphenyl n-CidH29 4-chlorophenyl 2-fluorophenyl n-CdHg 4-fluorophenyl 4-phenylphenyl 4-chlorophenyl 4-chlorophenyl 4-chlorophenyl 4-fluorophenyl 4-fluorophenyl 4-fluorophenyl 4-phenylphenyl 4-phenylphenyl 4-phenylphenyl 2,4-dichlorophenyl 2,4-dichlorophenyl 2,4-dichlorophenyl phenyl 4-fluorophenyl 4-fluorophenyl phenyl 4-chlorophenyl 4-chlorophenyl phenyl 4-phenylphenyl 4-phenylphenyl phenyl 2,4-dichlorophenyl 2,4-dichlorophenyl 2-naphthyl 4-methylthiophenyl 4-methylthiophenyl 4-chlorophenyl 2-methoxyphenyl 2-methoxyphenyl 4-chlorophenyl 3-chlorophenyl 3-chlorophenyl phenyl 2-chlorophenyl 4-fluorophenyl

X = Ri, Ri'

R2

4-fluorophenyl

4-chlorophenyl

4-fluorophenyl

2,4-dichlorophenyl

2,4-dichlorophenyl

2.4-dichlorophenyl 2,6-dimethoxyphenyl

3.4-dichlorophenyl 4-methylphenyl

2-chlorophenyl

4-phenylphenyl 4-phenylphenyl 4-phenylphenyl 4-fluorophenyl 4-chlorophenyl

1-naphthyl 4-phenoxyphenyl 4-methylphenyl

Example 12

Preparation of (1,1'-biphenyl-1-yl) (chloromethyl)diethylsilane (Ι,Γ-Biphenyl-1-yl) (chloromethyl)diethylsilane can be prepared by the method of Example 1 using chlorochloromethyldiethylsilane instead of chlorochloromethyldimethylsilane.

Similar compounds can be prepared by the method of Examples 1 to 5 from suitable organolithium or Grignard compounds and a compound of the general formula

Cl(R2)Si(R3)CH2Cl

The desired chlorochloromethyldialkylsilanes are prepared from a compound of the formula

b.p. 118-122°C (13.33 Pa) ml of ethyl acetate to remove any remaining phenyllithium, washed with water and brine, dried over magnesium sulfate and evaporated to give 33 g of a sticky solid. Recrystallization from 30 ml of cyclohexane gave 15.8 g (51% of theory) of (chloromethyl)triphenylsilane as a white solid:

the melting point is 112 to 115°C;

ir (Nujol ^R ) 1420, 1110, 735, 730, 705, 695 centimeters per ^-1 ;

NMR (CDCl3)

3.5 (2H, s),

7.0 — 7.8 (15H m).

CI3SÍCH2CI

Example 13a using two equivalents of the compound of the general formula

RzMgCl or R2L1 if R2 is the same as R3 (see for example A. A. Zhdanov, V. I. Pakhomov and T. Bažanova, Zhur. Obshchej. Chim., 1973, p. 1280), or by using one equivalent of a compound of the general formula

R2MgCl or R2L1 and then one equivalent of a compound of the general formula

R3MgCl or R3L1 in the case where R2 and R3 do not have the same meaning.

Example 13

Preparation of (chloromethyl)triphenylsilane

A solution of 12.6 ml (18.4 g, 0.10 mol) of (chloromethyl)trichlorosilane in 150 ml of dry ether is stirred under nitrogen and cooled with ice while 162 ml (0.30 mol) of a 1.85 molar solution of phenyllithium in cyclohexane-ether in a ratio of 70:30 is added dropwise at such a rate that the temperature of the mixture is maintained below 15 °C. The resulting suspension is stirred overnight at room temperature, carefully worked up 10

Preparation of chloromethyl [tris(4-chlorophenyl j]silane

A solution of 24.5 g (0.128 mol) of 4-bromochlorobenzene in dry tetrahydrofuran is cooled to -60 °C in a stream of nitrogen and 80 ml (0.128 mol) of

of a 1.6 molar solution of n-butyllithium in hexane at a rate to maintain the temperature of the mixture below -50°C. The resulting solution was stirred for a further 10 minutes at -60 to -70°C and then a solution of 5.2 ml (0.041 mol) of chloromethyltrichlorosilane in tetrahydrofuran was added dropwise over 30 minutes. The resulting solution was stirred at -70°C for one hour, allowed to warm to room temperature, quenched rapidly with saturated aqueous ammonium chloride and extracted with ether. The ethereal solution was washed with brine, dried over magnesium sulphate and evaporated to give a viscous oil which was chromatographed on silica gel (hexane elution to give

9.1 g (53% of theory) of the compound prepared in the form of a colorless oil which solidifies on standing:

the melting point is 89 to 93°C;

NMR (CDCl3)

3.4 (2H, sj,

7.5 (12H, wide sj.

Table II

CH3

AND

X—Si—CH2Cl

AND

R2

X = R1, R1*

C2H5

I- C3H7

II- C4H9 n-CtoHii n-Ci8Hj7 cyclopropyl cyclohexyl

1- naphthyl

2- naphthyl phenyl phenyl phenyl

4-phenylphenyl

4-bromophenyl

4-fluorophenyl

4-phenoxyphenyl

4-t-butylphenyl

3-trifluoromethylphenyl 3-chlorophenyl 2-thiomethylphenyl 2-phenylphenyl 2,4-dichlorophenyl

2.4- dichlorophenyl

2,3-dimethylphenyl

2-methyl-5-fluorophenyl

2,5-dimethoxyphenyl

2,6-dimethylphenyl

3.5- dichlorophenyl

3,5-dichlorophenyl

3- methyl-4-chlorophenylphenyl

4-fluorophenyl

4-chlorophenyl

4-bromophenyl

4-phenylphenyl

4-t-butylphenyl

4-thiomethylphenyl

4-phenoxyphenyl

4-trifluoromethoxyphenyl 4-methylsulfonylphenyl 4-cyclohexylphenyl 4-(4-fluorophenyl)phenyl

3-trifluoromethylphenyl 2-chlorophenyl 2-methoxyphenyl 2-chloro-4-phenylphenyl

2-fluoro-4-phenylphenyl

3.5- dichlorophenyl

2,5-dimethoxyphenyl

2,6-dimethoxyphenyl

4-bromophenyl

4-phenylphenyl

4-methoxyphenyl

3-trifluoromethylphenyl 2-methoxyphenyl 2-chlorophenyl

2.4- dichlorophenyl

3.5- dichlorophenyl

R2

C2H5 cyclohexyl n-C4Hg cyclopropyl

3- methylbutyl n-CsHi3 cyclohexyl t-CíHo n-CsHu n-C3H7 n-ChHg

1,1-dimethylpropyl

C2H5

1-C3H7 n-CiHg t-C4H9 cyclopentyl

S-C4H9 n-CsHu cyclobutyl

I- C4H9 n-CaHg cyclopropyl

II- C3H7 cyclopentyl

4-methylpentyl

1- methylbutyl n-C4Hg cyclohexyl cyclopropyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl

4-bromophenyl

4-phenylphenyl

3-methoxyphenyl

3-trifluoromethylphenyl

4- methoxyphenyl

2-chlorophenyl

2.4- dichlorophenyl

3.5- dichlorophenyl

b.t. 45 °C (6.66 Pa)

t. v. 82 to 90°C (13.33 Pa)

b.p. 90 to 92 °C (13.33 Pa)

b.p. 109 to 112 C (13.33 Pa)

tv 104 to 110 °C (26.66 Pa) n _D ²² 1.5624

bp 140 to 148 °C (13.33 Pa) bp 145 to 155 °C (13.33 Pa) bp 173 to 178 °C (13.33 Pa)

b.p. 132 to 135 °C (13.33 Pa)

b.p. 160 to 170 °C (13.33 Pa)

mp 115 to 117 °C

mp 166 to 171 °C (13.33 Pa)

tv 135 to 140°C (13.33 Pa) n ₀ 2l 1.5956

NMR (CDCl 3 )

0.7 (3H, s),

3.1 (2H, s),

7.2 - 7.7 (8H, m);

analysis for C14H13Cl3Si (molecular weight 315.70) calculated:

C 53.26 H 4.15 Cl 33.69 found:

C 53.4 H 4.4 Cl 34.2

C 53.5 H 4.4 Cl 34.1

Example 10

Preparation of (chloromethyl)bis(4-fluorophenyl)methylsilane

A solution of 35 g (0.20 mol) of 5-fluorobromobenzene in 300 ml of dry tetrahydrofuran was cooled to -60 °C under nitrogen and stirred while 126 ml (0.20 mol) of a 1.6 molar solution of n-butyllithium in hexane was added dropwise at a rate to maintain the temperature of the mixture below -55 °C. Stirring and cooling were continued while 12.6 ml (16.4 g, 0.10 mol) of chloromethyl (dichloro) methylsilane was added dropwise at a rate to maintain the temperature of the mixture below -50 °C. The resulting solution was allowed to warm to room temperature and worked up as described in Example 8 to give 26.4 g of a clear yellow liquid. Distillation yields 20.6 g (73% of theory) of (chloromethyl)bis(4-fluorophenyl)methylsilane in the form of a colorless liquid;

boiling point 107 to 127 °C (at a pressure of 13.33

Pa);

_nD ²² 1.5481;

NMR (CDCl3)

0.7 (3H, s),

3.2 (2H, s),

7.1 (4H, t, J = 9) and

7.6 (4H, d, z, D, ) = 6a 9).

Repeating the procedure using chloromethyl (diethoxy) methylsilane instead of dichlorosilane gives (chloromethyl) bis (4-fluorophenyl) methylsilane in a yield of 58% of theory after distillation:

NMR (CDCl3) see above values.

A similar sample of the prepared compound, after recrystallization from the ether-hexane system at a temperature of -78 °C, yields a colorless solid with a melting point of 39-40 °C.

Example 11

Preparation of chloromethyl(2-chlorophenyl) (4-chlorophenyl) methylsilane

A solution of 6.3 mL (8.2 g, 0.05 mol) of chloromethyl (dichloro) methylsilane and 8.1 g (0.05 mol) of

of 2-bromochlorobenzene in 75 ml of dry tetrahydrofuran was cooled to -60 °C under nitrogen and stirred while adding 31 ml (0.05 mol) of a 1.6 molar solution of n-butyllithium in hexane at a rate to maintain the temperature of the mixture below -55 °C. Stirring and cooling were continued while adding 8.1 g (0.05 mol) of 4-bromochlorobenzene as a solid and then adding another 31 ml portion of a 1.6 molar solution of n-butyllithium at a rate to maintain the temperature of the mixture below -55 °C. The resulting thin suspension was allowed to warm to room temperature, treated cautiously with 10 ml of ethyl acetate and then worked up as described in Example 8 to give 15.0 g of a clear yellow oil. Distillation gave 5.9 g (37%] of chloromethyl (2-chlorophenyl) (4-chlorophenyl) methylsilane: boiling point 150 to 165 °C at a pressure of 93.31 Pa; n _D ²⁰ 1.5916;

ir (pure) 3060, 3020, 2960, 2870, 1580, 1560,

1490, 1420, 1380, 1255, 1125, 1115, 1085,

1035, 1015, 805, 750 cm ^-1 ;

NMR (CDCl3)

0.8 (3H, s),

3.3 (2H, s),

7.2 - 7.7 (8H, m).

The compounds of Table II are prepared by successively replacing the silicon and chlorine bonds of a compound of the formula

Cl2Si(CH ₃ )CH2Cl by the method described in examples 6 to 11.

boiling point 115 to 138 °C at a pressure of 25.66 Pa; n _D ²¹ 1.5464;

238826 residue in hexanes, re-filtration and evaporation yield 19.8 g of a pale orange liquid. Distillation yields first 1.8 g (12%) of chloromethyl(-dibutyl)methylsilane with a boiling point of 45 °C at a pressure of 6.66 Pa, after which 6.8 g (35%) of butyl(chloromethyl)(4-chlorophenyl)methylsilane is obtained as a colorless liquid:

boiling point 90 °C at a pressure of 6.66 Pa; n _D ²¹ 1.5246;

ir (pure) 2925, 1580, 1260, 1090, 1015, 820,

740 cm ^-1 ;

NMR (CDCl3)

0.4 (3H, sj,

0.6 — 1.5 (9H, m),

2.9 (2H, s),

7.0-7.4 (4H, q.s.)

Example 8

Preparation of chloromethyl (2,4-dichlorophenyl)methyl (phenyl)silane

A solution of 13.6 g (0.060 mol) of 2,4-dichlorobromobenzene and 12.3 g (0.060 mol) of chloro(chloromethyl) methyl(phenyl) silane, prepared as described in Example 14, in 85 ml of dry tetrahydrofuran was rapidly cooled to -60 °C under nitrogen and stirred while 38 ml (0.060 mol) of a 1.6 molar solution of n-butyllithium in hexane was added dropwise at a rate to maintain the temperature of the mixture below -55 °C. The resulting red solution was allowed to warm to room temperature, treated with 5 ml of ethyl acetate to remove any unreacted excess organolithium reagent, and poured into 170 ml of water.

The organic layer is separated, the aqueous phase is washed with 50 ml of hexane, and the combined organic phases are washed three times with water, once with brine, dried over magnesium sulfate and evaporated to give 19.0 g of a bright yellow oil. Distillation gives 8.6 g (45% of theory) of chloromethyl (2,4-dichlorophenyl)methyl (phenyl)silane as a colorless liquid: boiling point 125-130 °C at 6.66 Pa; n _D ²¹ 1.5978;

ir (pure) 3080, 3060, 2960, 2930, 1570, 1540,

1460, 1430, 1365, 1260, 1120, 1100, 1040,

820, 745, 735, 705 cm ^-1 ;

NMR (CDCl)

0.8 (3H, s),

3.4 (2H, s),

7.2-7.9 (8H, m).

Example 8a

Preparation of (Ι,Γ-biphenyl-4-yl)chloromethyl (4-fluorophenyl)methylsilane

A solution of 10.0 g (32.8 mmol) of (1,1'-biphenyl-4-yl) (chloromethyl) methyl (2-propoxy) silane and 3.6 ml (32.8 mmol) of 4-bromofluorobenzene in 30 ml of dry tetrahydrofuran is cooled to -60 °C in a stream of nitrogen and stirred while adding 20.5 ml (32.8 mmol) of

of a 1.6 molar solution of n-butyllithium in hexane at a rate to maintain the temperature of the mixture below 50 °C. Stir at -70 degrees Celsius for a further 30 minutes, allow the solution to warm to room temperature and work up as described in Example 8. The resulting crude product is distilled at 130 to 150 °C (26.64 Pa) to remove unreacted starting materials, thereby obtaining the compound being prepared as an oil:

_nD ²³ 1.5128;

NMR (CDCl3)

0.7 (3H, S),

3.1 (2H, S),

7.1 (2H, t),

7.2 — 7.8 (11H, among others)

Example 9

Preparation of chloromethyl [bis(4-chlorophenyl)]methylsilane

A solution of 19.1 g (0.10 mol) of 4-chlorobromobenzene in 200 ml of dry tetrahydrofuran is rapidly cooled to -60 °C under a nitrogen atmosphere and stirred while 63 ml (0.10 mol) of a 1.6 molar solution of n-butyllithium in hexane is added dropwise at a rate to maintain the temperature of the mixture below -55 °C. Stirring and cooling are continued while adding 6.3 ml (8.2 grams, 0.05 mole) of chloromethyl (dichloro)methylsilane dropwise at a rate to maintain the temperature of the mixture below -50°C. The resulting orange solution is allowed to warm to room temperature and is worked up as in Example 8 to give 16.5 g of a pale yellow oil. Distillation in a neck flask at a pressure of 6.66 Pa and an air bath temperature of 130 to 150°C yields 9.5 g (60% of theory) of chloromethyl [bis (4-chlorophenyl)] methylsilane as a colorless liquid:

_nD ²⁴ 1.5913;

ir (pure) 3080, 3040, 3020, 2960, 2930, 1580,

1490, 1380, 1260, 1085, 1015, 805, 790, 775,

740 cm ^-1 ;

X = Ri or Ri'

4-(4-methylphenyl)phenyl 4-(4-trifluoromethylphenyl)phenyl 4-(4-fluorophenyl)phenyl

3-phenylphenyl

3-trifluoromethylphenyl 3-chlorophenyl

2-trifluoromethylphenyl 2-phenylphenyl 2-chlorophenyl 2-methoxyphenyl

2,3-dimethylphenyl

2,3-dimethoxyphenyl

2,4-difluorophenyl

2-fluoro-4-chlorophenyl

2-chloro-4-phenylphenyl

2-fluoro-4-phenylphenyl

2-methyl-5-chlorophenyl

2,6-dimethylphenyl

3.4- dichlorophenyl t.

3-methyl-4-fluorophenyl

3.5- dichlorophenyl t.

Example 6

Preparation of (1,1'-biphenyl-4-yl)butyl (chloromethyl)methylsilane (1,1'-Biphenyl-4-yl)butyl (chloromethyl)methylsilane can be prepared by the method described in Example 1 using (butyl)chloro(chloromethyl)methylsilane instead of chloro(chloromethyl)dimethylsilane.

Related compounds can be prepared by the method of Examples 1 to 5, using appropriate organolithium compounds or Grignard reagents and appropriate compounds of the general formula

Cl(R2)Si(CH3)CH2Cl

The necessary chloromethylsilane starting materials are prepared from a compound of the general formula

R2MgCl or R2L1 and from CbSi(CH5)CH2Cl by the method described in examples 14 and 15 and, for example, by V. P. Kuznětsova and R. M. Sololovaska in the journal Žur. Obščej. Chim., year 1969, p. 1997.

Or, both the biphenyl and butyl groups can be introduced simultaneously in this way:

A solution of 23.3 g (0.10 mol) of 4-bromobiphenyl and 12.7 ml (16.4 g, 0.10 mol) of chloromethyl(dichloro)methylsilane in 150 ml of dry tetrahydrofuran is rapidly cooled to -70 °C under a nitrogen atmosphere and stirred while adding 125 ml (0.20 mol) of a 1.6 molar solution of n-butyllithium in hexane at such a rate as to maintain the temperature of the mixture below -60 °C. The resulting thin suspension is allowed to warm to room temperature, carefully treated with 10 ml of ethyl acetate and poured into 300 ml of water. The organic layer is separated, the aqueous phase is washed with _D ²⁰ 1.5862

tv 59 to 62 °C (39.99 Pa) tv 73 °C (19.99 Pa] n _D ²³ 1.4826 n _D ²⁰ 1.5772

tv 78 to 80 °C (39.99 Pa) n _D ²¹ 1.5164 n _D ²² 1.5254

at 98 °C (79.98 Pa)

at 94 to 95 °C (33.32 Pa) with 100 ml of hexane and the combined organic phases are washed three times with water, once with brine, dried over magnesium sulfate and evaporated to give 33.9 g of a viscous yellow oil. Distillation yields 9.5 g (31% of theory) of (1,1'-biphenyl-4-yl)butyl(chloromethyl)methylsilane.

The boiling point is 133 to 158 °C at a pressure of 13.33

Pa;

_nD ²² 1.5743;

ir (clean) 3060, 3015, 2960, 2920, 2870, 1600,

1485, 1390, 1380, 1250, 1120, 1075, 1005,

875, 800, 760, 700 cm ^-1 ;

' NMR (CDCl 3 )

0.4 (3H, s),

0.6 — 1.8 (9H, etc.)

2.9η (2H, s) and

7.0 - 7.7 (9H, m).

Example 7

Preparation of butyl (chloromethyl) (4-chlorophenyl)methylsilane

A solution of 14.4 g (0.075 mol) of 4-bromochlorobenzene and 9.5 ml (12.3 g, 0.075 mol) of chloromethyldichloromethylsilane in 150 ml of tetrahydrofuran was cooled to -60 °C under nitrogen and stirred while 94 ml (0.15 mol) of a 1.6 molar n-butyllithium solution in hexane was added dropwise at a rate to maintain the temperature of the mixture at -65 to -55 °C. The resulting suspension was allowed to warm to room temperature to give a solution which was diluted with hexane until no more lithium chloride precipitated. By filtration, evaporation of the filtrate, dissolution

2β

NMR (CDCl3)

0.5 (6H, s],

3.1 (2H, s),

7.0-7.5 (3H, m).

Example 5

Preparation of chloromethyl (2,6-dimethoxyphenyl)dimethylsilane

A solution of 25.0 g (0.181 mol) of 1,3-dimethoxybenzene in 200 ml of tetrahydrofuran was stirred at room temperature under nitrogen while 125 ml (0.200 mol) of a 1.6 molar solution of n-butyllithium in hexane was added dropwise over 30 minutes. The resulting mixture was refluxed for 1.5 hours to give an orange-brown solution, which was cooled to 5 °C and stirred while 27 ml (29.4 g, 0.205 mol) of chloro(chloromethyl)dimethylsilane was added dropwise over 15 minutes. The resulting white suspension was allowed to warm to room temperature, stirred for one hour, diluted with ethyl acetate, poured into water and extracted with ether. The organic layers were washed with brine, dried over magnesium sulfate, and distilled to yield 37.0 g (84% of theory) of chloromethyl (2,6-dimethoxyphenyl)dimethylsilane as a colorless liquid:

boiling point 98 to 110 °C at a pressure of 13.33 Pa; NMR (CdClb)

0.4 (6H, s),

3.1 (2H, s),

3.7 (6H, s),

6.3 (2H, d),

7.1 (1H, m).

Using various organolithium compounds or Grignard reagents, the compounds of Table I can be prepared by the method of Examples 1 to 3. Very similar procedures are also known from the literature, for example the use of arylmagnesium chlorides is known according to C. Eaborn and J. C. Jeffrey, J. Chem. Soc., 1954, p. 4266. For compounds where R1 is a phenyl ring with a substituent in position 2, an alternative method to the in situ method of Example 4 is the special arylmagnesium iodide procedure described by C. Eaborn, K. L. Jaura and D. R. M. Walton, J. Chem. Soc., 1964, p. 1198,

X = Ri or Ri'

C2H5 n-CdHg n-Ci2Hz5

11-C18H37 cyclopropyl cyclopentyl cyclohexyl

1- naphthyl

2- naphthyl phenyl

4-fluorophenyl

4-methoxyphenyl

4-phenoxyphenyl

4-(4-chlorophenoxy)phenyl

4-(4-fluorophenoxy)phenyl

4-(4-trifluoromethylphenoxy)phenyl

4-(4-methylphenoxy)phenyl

4-thiomethylphenyl

4-trifluoromethylphenyl

4-methylphenyl

4-i-propylphenyl

4-t-butylphenyl

4-methylsulfonylphenyl

4-cyclohexylphenyl

4-trifluoromethoxyphenyl

4-(4-chlorophenyl)phenyl

4-(4-bromophenyl)phenyl

Table I

CHs

AND

X—Si—CH2Cl

AND

CHs

tv 127 to 128 °C tv 172 °C n _D ²³ 1.4510 n _D ²² 1.4556

bp 120 to 130°C (1333 Pa) bp 112°C (10.66 Pa)

tv 85 to 86 °C (399.9 Pa) tv 59 to 60 °C (13.33 Pa) tv 80 °C (6.66 Pa) tv 122 °C (3.99 Pa) n _D ²² 1.5773

tv 92 to 93°C (6.66 Pa) n _D ²³ 1.4686

tv 96°C (933.1 Pa) n _D ²³ 1.5056

mp 64 to 68 °C n _D ²¹ 1.5424

b.p. 55-57°C (19.99 Pa) no stirring. With continued cooling, 5.9 ml (6.7 µg, 0.046 mol) of chloro(chloromethyl)dimethylsilane is added over 10 minutes to give a clear solution which is allowed to warm to room temperature. 300 ml of ether is added, the precipitated lithium chloride is removed by filtration and the filtrate is evaporated to give

13.2 g of semi-solid. Redissolve in ether, filter, and evaporate the filtrate to give 11.0 g (100% crude) Ι,Γ-biphenyl-4-yl(chloromethyl)dimethylsilane as a colorless solid, mp 30-40 °C, suitable for further reaction. Traces of impurities can be removed by sublimation at 30 °C under 13.33 Pa to give 1,1'-biphenol-4-yl(chloromethyl)dimethylsilane unsublimed in 83% yield, mp 37-40 °C;

ir (Nujol ^R ) 1585, 1240, 1110, 830, 810, 750, 690 cm ^-1 ;

NMR (CDCl3)

0.4 (6H, sj,

2.9 (2H, s),

7.3 - 7.7 (9H, m).

Example 2

Preparation of (4-bromophenyl](chloromethyl)dimethylsilane

4-Bromophenylmagnesium bromide is prepared from 11.8 g (0.050 mol) of 1,4-dibromobenzene and

1.2 g (0.050 gatom) of magnesium turnings in 75 ml of ether according to G. P. Schiemenz, Org. Syn., Coll. Vol. 5, p. 496: (.1973), The resulting mixture is cooled rapidly in a 1' copper under a nitrogen atmosphere while adding dropwise a solution

6.6 ml (7.2 g, 0.050 mol) of chloro(chloromethyl)dimethylsilane in 10 ml of ether. The reaction mixture was then stirred overnight at room temperature, carefully quenched with saturated aqueous ammonium chloride solution, and filtered. The ether phase of the filtrate was washed with brine, dried over magnesium sulfate, and evaporated to give 9.8 g of an oil. Distillation gave 3.8 g (29%) of (4-bromophenyl)(chloromethyl)dimethylsilane as a colorless liquid:

boiling point 97 °C (133.3 Pa), ir (pure) 2950, 1575, 1475, 1370, 1250,. 1065, 1010, 840, 805, 720 cm ¹ ;

NMR (CDCl3)

0.4 (6H, sj,

2.9 (2H,s),

7.3-7.7 (4H, m).

Example 3

Preparation of chloromethyl (4-chlorophenyl)dimethylsilane

A solution of 9.6 g (0.050 mol) of 4-bromochlorobenzene and 6.6 ml (7.2 g, 0.050 mol) of chloro(chloromethyl)dimethylsilane in 75 ml of tetrahydrofuran is stirred at -78 °C under nitrogen while 31 ml (0.050 mol) of 1.6 molar n-butyllithium in hexane is added dropwise. The resulting clear solution is allowed to warm to room temperature, diluted with ether until no more lithium chloride precipitates, and filtered. Evaporation of the filtrate yields 10.6^ g of a pale yellow liquid, which on distillation yields 6.0 g (55% yield) of chloromethyl(4-chlorophenyl)dimethylsilane as a colorless liquid:

boiling point 54 to 55 °C at a pressure of 66.6 Pa;

ir (pure) 2910) 1560, 1470, 1370, 1250, 1080,

1010; 840, 805, 790, 740 cm ¹ ;

NMR (CDCl3)

0.4 (6H, s),

2.9 (2H, s),

7.1-7.6 (4H, q).

The in situ preparation of aryllithium described in this example is also suitable for the preparation of the product of Example 1. If the reaction is carried out with 0.5 to 0.7 molar amounts of 4-bromobiphenyl and at a temperature maintained at -65 to -55°C during the addition of butyllithium, no precipitate is formed or only a slight solid precipitate is formed. Example 4

Preparation of chloromethyl (2,4-dichlorophenyl) dimethylsilane

A solution of 17.0 g (0.075 mol) of 2,4-diclilorbromobenzene and 10.8 ml (11.8 g, 0.082 mol) of chloro(chloromethyl)dimethylsilane in 100 ml of dry tetrahydrofuran is rapidly cooled to -70 °C under a nitrogen atmosphere and stirred while adding 49 ml (0.079 mol)

A 1.6 molar solution of n-butyllithium in hexane was added dropwise at a rate such that the temperature of the mixture was maintained below -70 °C. The resulting cloudy reaction mixture was allowed to warm to room temperature, poured into 400 ml of hexane, filtered and evaporated to give

20.5 g of yellow liquid. Distillation yields

12.6 g (66% of theory) of chloromethyl(,2,4-dichlorophenyl)dimethylsilane in the form of a colorless liquid:

boiling point 83 °C at a pressure of 2.66 Pa; n _D 24 1.5522;

ir (clean) 1565, 1455, 1360, 1255, 1100, 1040,

825 ^cm2 ;

3 8 6.2 Ο

CH3 CH3

I I

Cl·—Si—CH2Cl + ArLi--->C1—Si—CH2Cl

AND

Ar

In both cases, the organometallic reagent should be added to the dichlorosilane at room temperature with good stirring to achieve the best yields.

Reaction of a compound of the formula

CI3SÍCH2CI with Grignard reagents was described by A. A. Zhdanov, V. I. Pakhomov and T. Bažanova in the journal Žur. Obščej. Chimii, 1973, p. 1280, Chem. Abstr. 79, 66452 m. The addition of organometallic reagents to trichlorosilane is also recommended when three identical groups are to be introduced, since the addition of a compound of the formula

CI3СИCH2CI into the organometallic reagent prepared

the pitchfork is not successful. It can also be introduced single aryl group: Cl

CI3SICH2CI + ArLi---► Ar—Si—CH2CI

Cl

A useful modification of the prior art methods applicable when R1 or R1' represents an aryl group is described herein. Instead of pre-forming an organolithium reagent and then mixing it with a chlorosilane, it has been found that an aryl bromide and a chlorosilane such as a compound of the formula

ClSi(CH3)2CH2Cl can be mixed in an inert solvent such as tetrahydrofuran and treated at -80 to -40 °C with butyllithium. The bromine-lithium exchange occurs selectively and the resulting aryllithium reacts with the silicon-chlorine bond as soon as the bond is formed:

CH3 | n-CáHaLi

ArBr + Cl—Si—CH2Cl---.

| —CaHgBr

CH3

CH, ³

ArLi + Ct-Si.-CH.Ct I ^í ch ₅

CH3

AND

----► Ar—Si—CH2CI —faces I

CH3

This reaction proceeds equally well for aryl-substituted chlorosilanes such as the compound of the formula

ClSi(CH3)(C6Hg)CH2Cl and can be used to introduce two aryl groups into a compound of the formula

Cl2Si(CH3)CH2Cl

In addition, an aryl and n-butyl group can be introduced in one step.

CH3 CHs | 2n-C4H9Li |

ArBr + Cl2S1—CH2Cl----> Ar—Si—CH2Cl

In-C4H9

Replacing n-butyllithium with another alkyllithium compound of formula RLi gives a general method for preparing compounds of formula

Ar(CH3)Si(R)CH2Cl

In the following examples, temperatures are given in degrees Celsius. The abbreviations have the following meanings:

NMR = nuclear magnetic resonance, s = singlet, d — doublet, t = triplet, q = quartet, m — multiplet;

Peak positions are reported in parts per million relative to internal tetramethylsilane. Infrared (IR) peak positions are reported in reciprocal centimeters ( ^cm'1 ). Hexanes are a mixture of isomers with a boiling point of 68-69°C and ether is diethyl ether.

Example 1

Preparation of (1,1'-biphenyl-4-yl)(chloromethyl)dimethylsilane

A solution of 9.9 g (0.042 mol) of 4-bromobiphenyl in 50 ml of tetrahydrofuran is cooled to -78 °C under nitrogen and stirred while 26.5 ml (0.042 mol) of 1.6 molar n-butyllithium in hexane is added dropwise over 15 minutes. A thick suspension is formed and 35 ml of tetrahydrofuran is added to the mixture.

I ^rSC-CH^Ct->

Cl·

Glycol derivatives are formed similarly using a diol in place of two molecules of a compound of the general formula ReOH.

An alternative synthesis of alkoxy(chloromethyl)silanes involves the selective replacement of one alkoxy group of a dialkoxysilane with an organometallic reagent:

R2 | RiMgX (ReOjžSi—CH2CI--->

RiLl or RiNa

R2

AND

---►Rl—- Shi— CH2CI

AND

ORe

The conditions of this reaction are described below with the additional condition that the organometallic compound is to be added to the dialkoxysilane.

The desired chloromethylsilane, as a starting material, is prepared from commercially available chloro(chloromethyl)dimethylsilane, from chloromethyl(dichloro)methylsilane or from chloromethyltrichloromethylsilane.

CH3

AND

Cl—Si—CH2Cl,

I ch ₃

CH3

AND

Cl—Si—CH2Cl,

AND

Cl or

R2

AND

CbSiCH2Cl--->Ri—Si—CH2CI

AND

R3

The silicon-chlorine bonds in these compounds react with organolithium, organosodium or Grignard reagents to introduce alkyl and/or aryl groups in a manner known from the literature, while the carbon-chlorine bond remains intact. For silanes containing two or three silicon bonds,

ku and chlorine, a gradual replacement is possible, thus giving a wide range of possibilities for the meanings of the symbols R 1 to R ₃ . Bromosilanes, iodosilanes or alkoxysilanes can be used in place of chlorosilanes in these reactions. Preferred solvents for these reactions include ethers such as tetrahydrofuran, 1,2-dimethoxyethane and diethyl ether or hydrocarbons such as hexane and toluene. Temperatures of -80 to +40°C are preferred, depending on the nature of the organometallic reagent, how it was prepared and the solvent used. For example, if aryllithium reagents are prepared in tetrahydrofuran from aryl bromides using butyllithium, the mixture should be maintained at a temperature of about -40°C to avoid side reactions involving the formation of bromobutane. If the organometallic solution is stable at higher temperatures, the reaction can be carried out at a temperature of -20°C to +25 degrees Celsius without competing reaction on the CH 2 Cl group. The reaction is rapid at all temperatures and only a short period of time, e.g. 30 to 60 minutes after mixing the reactants, is required to ensure complete reaction.

Compound reaction

ClSijCHsjžCHsCl with Grignard reagents are described by C. Eaborn and J. C. Jeffrey in the journal j. Chem. Soc., 1954, p. 4266; the most recent description of the preparation of aryltrimethylsilanes from the compound of the formula

ClSi(CH ₃ j ₃ and experimental conditions for the reactions of the compound of the formula

ClSi(CH ₃ )2CH2Cl are described by D. Habich and F. Effenberger in the publication Synthes 1979, p. 841. Selective introduction of a new alkyl group into a compound of the formula

Cl2Si(CH3)CH2Cl was described by V. P. Kuznetsova and R. M. Solokovaskaya in the journal Zh. Obshchej. Chim., 1969, p. 1977; Chem. Abstr. 72, 31897 p and one aryl group can be selectively introduced according to the equation:

23882B

Ri-SL-CH.Ct + ¹ ii

Cl

0-4

VrN 2A/a< I

O,

R<

0-4

R,

0-,

GL.

OR, <3-,

Suitable solvents and reaction conditions are the same as those mentioned above for azoles. The temperature of the alcoholysis is not critical and can be carried out by heating to 50 to 100°C to achieve complete reaction in cases where R6 is an alkyl group with 1 to 4 carbon atoms. However, in the case where R6 is hydrogen, the hydrolysis is best carried out at a temperature close to room temperature to minimize the formation of disiloxane, since silanol-disiloxane equilibrium is possible whenever R6 is hydrogen.

Q,.

Rr So~ ⁷ i

OH ^CH A

The equilibrium and the rate at which equilibrium is established depend on the values of R1 and R2, the solvent chosen, the temperature and the possible presence of acidic or basic catalysts.

In the second method, a silicon-oxygen bond is first formed, after which the azole is prepared as described above:

R,

Rx-SÍ-CHjCiQ-l

RrSi-CH _? N ¹ 1 R, í ^£

STEED,

OR, and,

The reaction of the chlorosilane with the compound of the general formula ReOH can be carried out in almost any non-hydroxyl ether solvent such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran or in dipolar aprotic solvents such as dimethylformamide, with acetonitrile being preferred. Although it is not necessary to use an acid acceptor, it is advantageous to add a tertiary amine such as triethylamine or pyridine. The reaction temperature can be 0 to 100 °C and the compound of the general formula R6OH is often used in excess with respect to the theoretical amount. Generally, 2 equivalents of the compound of the general formula R6OH are used,

1.1 equivalents of triethylamine and 0.1 equivalents of imidazole in dimethylformamide at 80°C, allowing the reaction to proceed for two hours.

Using these methods for (chloromethyl)dichlorosilanes, silanes containing two oxygen atoms are obtained:

which has a singlet close to 2.9 and a singlet product

S1CH2N of the derivative to the 4-substituted derivative 10 : 1. Monomethyltriazoles and dimethyltriazoles give similar 4H-isomers as the products formed in smaller amounts:

which is close to 3.8 for compounds of general formula I and close to 3.7 for compounds of general formula II.

With regard to the triazole derivatives of general formula I, the 1H-1,2,4-triazol-1-ylmethyl compound, prepared as described above, is accompanied by a minor amount of the isomeric 4H-1,2,4-triazol-4-ylmethyl compound of general formula or

R,- 1

The ratio of isomers varies with the value of R and the reaction conditions, roughly the ratio at position 1 is substituted. When using unsubstituted silylmethyltriazole, metalation — methylation provides methylated homologues:

^R ro N

1» CjfHg LL

2-CH _ó J ll

RvSL-CH. ¹ 1 t

R, r=N \J

CH<

In the case of imidazole derivatives of the general formula II, isomers are only possible if Q2 and Q3 do not have the same meaning. Two isomers are obtained:

CH»

R,- sí-cHjM formula IIA '

Generally, the product of formula IIA predominates. Optionally, the isomers can be separated by standard methods such as crystallization, distillation or chromatography.

For the case where Rs represents a group of the general formula OR6 in the triazole or imidazole product, the chlorine in the chloro(chloromethyl)silane can be replaced in one of two ways; in one method at least two equivalents of the azole sodium salt can be used. An intermediate containing a very reactive silicon-azole bond is formed and reaction with water or an alcohol gives the desired oxygen-containing compound:

formula IIB

23862-6

„ w.c . >=n 1 ² >=N and, formula IIB Isomers prevail, general formula IIA usually but isomers of general formula

where

HN. J >-N

Q1, Q2 and Qj represent a hydrogen atom or a methyl group. When writing structural formulas, the structural moiety

Gkj

IIB also have fungicidal activity and separation of isomers is therefore not necessary.

The symbol Ri is still used to refer to the symbol Ri', since all meanings of the symbol Ri' are included in the definition of the symbol Ri. The term "azole" is still used for suitably substituted 1,2,4-triazoles and imidazoles.

where

X represents a nitrogen atom or a CQ3 group is used to denote both a triazole and an imidazole ring system.

The active ingredients of the general formula I and II according to the invention can be prepared from chloromethylsilanes and 1,2,4-triazole or imidazole sodium salts or from their methylated homologues:

Lithium and potassium azole salts may also be used. Instead of chloromethylsilanes, bromomethylsilanes, iodomethylsilanes or arylsulfonyloxymethylsilanes may be used. Approximately equimolar amounts of the reactants are used (except when Rs is OR6 as will be discussed below), with the azole salt often being used in a 5 to 10% excess over the theoretical amount. In addition, when an acid acceptor is added, 1,2,4-triazole or imidazole per se may be used. Suitable acid acceptors include excess azole, alkali metal alkoxides such as sodium methoxide or potassium tert-butoxide, inorganic bases such as potassium carbonate or sodium hydride, and tertiary amines such as triethylamine. If the acid acceptor is highly nucleophilic, such as sodium methoxide, its use in excess should be avoided to avoid side reactions. Suitable solvents include polar aprotic solvents such as dimethylformamide, dimethylsulfoxide or acetonitrile; ethers such as tetrahydrofuran or 1,2-dimethoxyethane; and ketones such as 2-butanone. The reaction temperature may be 0 to 200°C, preferably 25 to 100°C. The reaction may be carried out under elevated pressure, but it is generally preferred to operate at atmospheric pressure. The optimum temperature and reaction time vary depending on the concentration and choice of reactants and in particular on the choice of solvent. For example, 1,2,4-triazole and sodium methoxide at about 2 molar concentration in dimethylformamide give good conversion in about two hours at 80 to 90 °C, while 1,2,4-triazole and potassium carbonate at about 1 molar concentration in butanone require reaction for 8 to 12 hours at reflux temperature. Imidazole reactions are generally faster. Generally, a reaction time of 1 to 24 hours is required. The progress of the reaction can be monitored by nuclear magnetic resonance analysis and by assessing the intensities of the starting material.

SÍCH2CI

Butyl (methyl)phenyl (1H-1,2,4-triazol-1-ylmethyl isolate;

Butyl (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl)silane;

[ bis (1,1'-Bisphenyl-4-yl)] methyl (1H-1,2,4-triazol-1-ylmethyl isolate;

(Ι,Γ-Biphenyl-4-yl)butyl (methyl) (1H-1,2,4-triazol-1-ylmethyl silane; and (1,1'-Biphenyl-4-yl)methyl(phenyl)(1H-1,2,4-triazol-1-ylmethyl silane).

Compounds of formula II are particularly preferred, wherein R1, R2 or R3 are not C1-4 alkyl or phenyl. The following compounds of formula II are preferred due to their excellent efficacy and/or the easiest preparation method:

(1,1'-Biphenyl-4-yl)dimethyl (1PI-imidazol-1-ylmethyl Jsilane;

(2,4-Dichlorophenyl)dimethyl (1H-Imidazol-1-ylmethyl Jsilane;

Butyl (2,4-dichlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane;

[ bis (4-Fluorophenyl) ] (1H-imidazole-1-yhnethyljmethylsilane;

[bis(2,4-Dichlorophenyl)](1H-imidazol-1-ylmethyl)methylsilane;

(2,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl)methyl(phenyl)isolate;

(4-Chlorophenyl)(1H-imidazol-1-ylmethyl)methyl (phenyl)silane;

(4-Fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl isolate;

(1,1'-Biphenyl-4-yl)butyl (1H-imidazol-1-ylmethyl)methylsilane;

(1,1'-Biphenyl-4-yl) (1H-imidazol-1-ylmethyl) methyl (phenyl isolate;

[bis(1,1-Biphenyl-4-yl)] (1H-imidazol-1-ylmethyl)methylsilane; ·''''

Butyl (4-chlorophenyl)(1H-imidazol-1-ylmethyljmethylsilane;

(4-Chlorophenyl)dimethyl (1H-imidazol-1-ylmethyl isolate;

Dimethyl (4-fluorophenyl) (1H-imidazohl-ylmethylsilane; a

Butyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl)methylsilane.

If Q1 and Q2 each represent a hydrogen atom or a methyl group, the preparation of triazole derivatives of general formula I usually results in a mixture of two isomers:

formula IB

R,

If the triazole substituent is a hydrogen atom and the other is a methyl group, three isomers can be obtained:

/>M

R.-Sú-CHrN J formula IC and

CH, formula ID and

IE formula rSt-CH “Ν'

I from. \ i

R,

CH.

\ *

R _r Sc-CH _r N^

R<

>oh t

R,

The mixture mainly contains isomers of formula IA or formula IC; however, isomers of formula IB, ID and IE also have fungicidal activity and separation of the isomers is not necessary.

In the case of imidazole derivatives of general formula II, isomers are obtained if the symbols Q2 and Q3 do not have the same meaning:

R^· CH/

R, ^N

Λ

R.-Sl-CH,N 1 í \= ^R sa)

Pl· formula IA formula IIA

R,

Rf Si CH ₃ ^R L ¹

R f Sl,

CH _Z

ΊΓ

N

0-,

The invention also relates to salts of compounds of general formula I and II with protic acids and their complexes with metal ions.

For their effectiveness and/or preferably easy preparation, compounds of general formula I and II are preferred, where means

Qi=Q2=-=hydrogen atom

They are more preferred for their effectiveness: and/or for the advantageously easy method of preparing the compound, where

Ri and Ri' denote a group of the formula

R2 represents an alkyl group with 1 to 4 carbon atoms or a group of the formula

R 5 is an alkyl group having 1 to 4 carbon atoms.

The most preferred compounds for their highest efficiency and/or for the easiest method of preparation are the compounds of general formula I and II, where means

Ri and Ri' a group of the general formula

where means

Ri is a group in the para position to the Ri or Ri' group and represents a hydrogen atom, a fluorine, chlorine or bromine atom or a phenyl group and

Rs is a hydrogen atom, a fluorine, chlorine or bromine atom and

R2 group of general formula

Rj or an alkyl group with 1 to 4 carbon atoms and

R 5 is an alkyl group having 1 to 4 carbon atoms.

The following compounds of general formula I are particularly preferred due to their outstanding efficacy and/or the easiest method of preparation:

(Dimethyl Jphenyl(1H-1,2,4-triazol-1-ylmethyl Jsilane;

Dimethyl (4-methyl lf enyl) (1H-1,2,4-triazol-1-ylmethyl J silane;

(4-Bromophenyl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane;

(1,1'-Biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-yl-methyl)silane;

(4-Chlorophenyl)dimethyl (1H-1,2,4-triazol-lylmethyl)silane;

(2,4-Dichlorophenyl J dimethyl (1,H-1,2,4-triazol-1-ylmethyl) J silane;

Butyl (4-chlorophenyl)methyl(;1H-1,2,4-triazol-1-ylmethyl)silane;

bis(4-Chlorophenyl Jmethyl (1H-1,2,4-triazol-1-ylmethyl) silane;

Methyl (diphenyl) (1H-1,2,4-triazol-1-ylmethyl)silane;

(bis (4-Fluorophenyl) Jmethyl (1H-1,2,4-trazol-1-ylmethyl) Jsilane;

(4-Fluorophenyl)dimethyl (1H-1,2,4-triazol-L-ylmethyl Jsilane;

Butyl (2,4-dichlorophenyl Jmethyl (1H-1,2,4-triazoMylmethyl Jsilane;

[ bis (2,4-Dichlorophenyl J ] methyl (1H-1,2,4-triazol-1-ylmethyl J silane;

2,4-Dichlorophenyl (methyl)phenyl (1H-1,2,4-triazol-1-ylmethyl) silane;

4-Chlorophenyl (methyl J phenyl (1H-1,2,4-triazol-1-ylmethyl J silane;

4-Fluorophenyl (methyl J phenyl (1H-1,2,4-triazol-1-ylmethyl J silane;

or η

Οχ ζΟ gene and/or an alkyl group with 1 to 4 carbon atoms and/or a trifluoromethyl group, a trifluoromethyl group, an alkyl group with 1 to 4 carbon atoms or a cyclohexyl group,

R2 and R3 independently represent an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, a group of the general formula OR6 or of the general formula

OxzO

R,

R _f

The invention also relates to a method of controlling fungal diseases of living plants by treating them with an effective amount of a compound of general formula I or II.

Kl /rzN Rj-SÍCHA-J

Q a-j

R1 '/ττΝ R _Ž -SLCH^ ^r í a, a;

where means

R6 is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, provided that R2 and R3 do not both represent a hydroxyl group and R2 and R5 can together form a 1,2-glycol, 1,3-glycol or 1,4-glycol bridge or a 1,4-unsaturated glycol bridge substituted with up to 4 alkyl groups R7 — R10 having a total of up to 4 carbon atoms

Rf R ₁₀

or where does it mean

Q1, Q2 and Q3 independently represent a hydrogen atom or a methyl group,

Ri and Ri' represent an alkyl group with 2 to 18 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, a naphthyl group or a group of the formula

Rf R«

or

RfR, where means

Rd and Rs independently represent a hydrogen atom, a halogen atom, a methoxy group, a trifluoromethoxy group, a thiomethyl group of the formula —SCH3, a group of the formula —SO2CH3, a phenyl group, a phenyl group substituted with a halogen atom and/or an alkyl group with 1 to 4 carbon atoms and/or a trifluoromethyl group, a phenoxy group optionally substituted with a halo atom or

When R2 or R3 represents a hydroxyl group, the general formulae I and II include a disiloxane of the general formula

These guanidine group-containing organosilicon compounds are effective as antifungal agents for molded plastics and rubbers, especially ^silicone rubbers.

Soviet patent number 346,306 protects sihylmethylazoles of the general formula

(Rl ) _n (R2O) ₃ -„SiCH2Az where they mean

R1 and R2 are always an alkyl group, n zero to 3 and

Az is a pyrazole, imidazole or benzimidazole ring, optionally substituted.

Soviet patent number 271'552 protects silylethylazoles of the general formula (Rl) _n (R2O) ₃ . _n SiCH2CH2Az where

Ri, Rz, n and Az always have the meaning as in Soviet Patent Specification No. 346,306, cited above.

The subject of the present invention is a fungicidal composition, characterized in that it contains a compound of the general formula I or II as an active ingredient.

where means

R1 and R5 independently of each other are a hydrogen atom, a halogen atom, a methoxy group, a trifluoromethoxy group, a thiomethyl group of the formula SCH3, a group of the formula —SO2CH3, a phenyl group, a phenyl group substituted by a halogen atom and/or an alkyl group with 1 to 4 carbon atoms and/or a trifluoromethyl group, a phenoxy group, a phenoxy group substituted by a halogen atom and/or an alkyl group with 1 to 4 carbon atoms and/or a trifluoromethyl group, a trifluoromethyl group, an alkyl group with 1 to 4 carbon atoms or a cyclohexyl group, provided that in the case of a compound of general formula II the symbols Ri and R5 cannot simultaneously represent a hydrogen atom,

R2 and R3 independently represent an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, a group of the general formula ORe or of the general formula

where means

Re is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, provided that R2 and R3 do not both always represent a hydroxyl group and Ra and R3 may form a 1,2-glycol, 1,3-glycol or 1,4-glycol bridge or a 1,4-unsaturated glycol bridge substituted with up to 4 alkyl groups R1 to R10 having a total of up to 4 carbon atoms where

Q1, Q2 and Q3 independently represent a hydrogen atom or a methyl group,

R1 is an alkyl group with 2 to 18 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, a naphthyl group or an o- or

R-f R

R1' is an alkyl group of 6 to 18 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, a naphthyl group or a group of the formula

Compound 5 species

Phytophthora restricted in vitro

123

Compound % tomato mildew control (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl silane,

1:1 complex with copper chloride 100 (Ι,Γ-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane,

1:1 complex with zinc chloride 90 (4'-Bromo-1,1'-biphenyl-4-yldimethyl(1H-1,2,4-triazol-1-yl-30 methyl ysilane) (1H-1,2,4-triazol-1-ylmethyl isolate,

1:1 complex with copper chloride 90

Example 79

The active ingredients of the invention are added to standard V-8 agar at 45°C in an amount of 200 ppm. The treated agar is then spread in Petri dishes and allowed to solidify. Agar cultures of approximately 4 mm2 ^of 5 Phytophthora species are added to the nutrient medium: Phytophthora cinnamomi, P. cactorum, P. infestans, P. palmivora and P. parasitica var. nicotianae and incubated at 22°C for 6 days. Colonies whose radial growth is not more than 1 mm are considered to be inhibited by the active ingredient of the invention compared to colonies with a radial growth of more than 15 mm growing on untreated medium. The number of Phytophthora restricted by certain active ingredients of the invention is given in the following table.

Table XXXI

Compound 5 species

Phytophthora restricted in vitro (Butyl j dimethyl (1H-1,2,4-triazol-l-ylmethyl silane 1 (3,4-Dichlorophenyl j dimethyl (1H-1,2,4-triazol-l-ylmethyl) silane 2 (1,l'-Biphenyl-4-yl jdimethyl (1H-imidazol-l-ylmethyl 1) dimethyl silane) (4-phenoxyphenyl isolate 4 (2,4-Dichlorophenyl jdimethyl (1H-iroidazol-1-ylmethyl islate 5

124

Diphenyl (1H-imidazol-1-ylmethyl jmethylsilane 2 (4-Fluorophenyl j (1H-imidazol-1-ylmethyl jmethyl (phenyl isilane 2

Example 80

The active ingredients of the invention are incorporated into a suitable composition and used to coat cotton seeds at a rate of 2 g/kg of seeds. ^After complete coating, the seeds are allowed to air dry at room temperature. The cotton seeds are then sown in soil treated with the fungus Pythium aphanadermatum, sand, and cornmeal in sufficient quantities to kill most of the seeds. The seeds are kept in this soil at room temperature for one week and then the degree of infestation is assessed. The percentage reduction in infestation is shown in the following table. Most or all of the treated seeds germinate and produce good seedlings, whereas untreated seeds do not germinate or produce weak and stunted seedlings.

Table XXXII

Compound % cotton blight reduction

Ethyldimethyl (1H-1,2,4-triazol-1-ylmethyl islan 48 (Ι,Γ-Bifenyl-4-yl j dimethyl (1H-1,2,4-triazol-1-ylmethyl islan) 12 (4-Chlorophenyl j dimethyl (1H-1,2,4-triazol-1-ylmethyl islan 53'

Dimethyl (4-phenoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl jsilane 18 ^Λ (1,1'-Biphenyl-4-yl) dimethyl(1H-imidazol-1-ylmethyl jsilane 18 (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 18 ^Λ (3,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 15 ^{Λ And} the active substance used in the amount of 0.5 g/kg of seeds

Example 81

The active ingredients according to the invention are processed into suitable compositions and then used to coat corn grains in an amount of 2 g/kg of grains. After thorough coating, the grains

125

126

Compound % restriction

Pythia on corn is allowed to air dry at room temperature. The seeds are then sown in soil treated with a mixture of the fungus Pythium aphanadermatum, sand, and cornmeal in sufficient quantity to kill most of the untreated

of the treated grains. It is kept at 9°C for two weeks and then at 21°C for another week. After this time, the infestation is assessed. The percentage of infestation reduction is given in the following table. Most or all of the treated grains will germinate and grow healthy seedlings, while the untreated grains will either not germinate at all or will produce seedlings or stunted seedlings. Table XXXIII Compound % limited Pythia to corn (1,Γ-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl j silane 32 (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 25 (1H-imidazol-1-ylmethyl) dimethyl (1-naphthalenyl isolate 27 (3,4-Dichlorophenyl j (1H-imidazol-1-ylylethyl)dimethylsilane 30

(1H-imidazol-1-ylmethyl j dimethyl (4-phenoxyphenyl isolate 5

Dimethyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl isolate 15

Ethyldimethyl(1H-1,2,4-triazol-1-ylmethyl)silane 13 (1,1'-Biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane 30 (4-Chlorophenyl j dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane 8

Dimethyl (1-naphthalenyl] (1H-1,2,4-triazol-l-ylmethyl islan 30 (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-l-ylmethyl islan 43

Ethyl (1H-imidazol-l-ylmethyl j dimethylsilane 70 (ΙΗ-Imidazol-1-ylmethyl j dimethyl (4-methylphenyl silane 30

Claims (10)

SUBJECT 1. A fungicidal composition comprising as active ingredient a compound of the formula I or II Go <f (II) where means Q1, Q2 and Q3 independently of one another are hydrogen or methyl, R 1 is C 2 -C 18 alkyl, C 3 -C 6 cycloalkyl, naphthyl or formula Of the invention C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, naphthyl or where R1 and R5 independently of one another are hydrogen, halogen, methoxy, trifluoromethoxy, thiomethyl SCH3, -SO2CH3, phenyl, phenyl substituted by halogen and / or C1-C4alkyl and / or trifluoromethyl a phenoxy group, a phenoxy group substituted with a halogen atom and / or a C 1 -C 4 alkyl group and / or a trifluoromethyl group 127 128, trifluoromethyl, C1-C4alkyl or cyclohexyl, provided that in the case of the compound of formula (II), R @ 1 and R @ 5 cannot both be hydrogen, R 2 and R 3 independently of one another are C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, OR 6 or wherein R 6 is hydrogen or C 1 -C 4 alkyl, provided that R 2 and R 3 are not both hydroxyl and R 2 and R 3 may each form a 1,2-glycol, 1,3-glycol or A 1,4-glycol bridge or a 1,4-unsaturated glycol bridge substituted with up to 4 alkyl groups R7 to R10 having up to 4 carbon atoms in total or an acid addition salt thereof or a metal complex thereof. 2. A fungicidal composition as claimed in claim 1, wherein the active ingredient comprises a compound of formula (I), wherein Q1, Q2, R1, R2, R3, R6, R7-R10 are as defined above and wherein R1 and R5 are independently of one another hydrogen, halogen, methoxy, trifluoromethoxy, thiomethyl SCH3, -SO2CH3, phenyl, phenyl substituted by halogen and / or C1-C4 alkyl and / or trifluoromethyl, phenoxy, phenoxy substituted with halogen and / or C 1 -C 4 alkyl and / or trifluoromethyl, trifluoromethyl, C 1 -C 4 alkyl or cyclohexyl, or an acid addition salt thereof or a metal complex thereof. 3. A fungicidal composition as claimed in claim 2, characterized in that (Ι, Γ-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane is the active ingredient. 4. A fungicidal composition according to claim 2, wherein the active ingredient is bis- (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane. 5. A fungicidal composition according to claim 2, wherein the active ingredient is [bis (4-fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane. 6. A fungicidal composition according to claim 2, wherein the active ingredient is 4-fluorophenyl (methylphenyl (1H-1,2,4-triazol-1-ylmethyl) silane. 7th fungicidal composition according to claim 1, characterized in that it contains as active ingredient ^one compound of formula II wherein Qi, Q 2, Q, R ', R2, R3, Ri, Rs, Re, R7 - R10 are as defined in point 1 or an acid addition salt thereof or a metal complex thereof. 8. A fungicidal composition according to claim 7, wherein the active ingredient is (2,4-dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane. 9. A process for the preparation of an active compound as claimed in claim 2, wherein each of the symbols is as defined in claim 2, characterized in that an intermediate of the formula (I) is reacted. CI3S1CH2CI, Rs AND C12SiCH2Cl a R2 AND Cl-Si-CH 2 Cl AND R3 where R2 and R3 are as defined above, in a suitable solvent with a compound of formula Rl where 129 130 R2 R1 is as defined above and M is sodium or lithium or MgX, wherein X is chlorine, bromine or iodine at -80 ° C to 40 ° C to give chloromethylsilane which is reacted with 1,2,4 triazole, its 3-methyl derivative, or 3,5-dimethyl derivative or an alkali metal salt thereof, in a polar aprotic solvent, in ethers or ketones at a temperature of 0 to 150 ° C. 10. A process for the preparation of an active compound according to the general formula II, wherein the individual symbols are as defined in the general formula 7, characterized in that an intermediate selected from the group consisting of a compound of the formula I is reacted. CbSiCHzCl, R3 i Cl 2 S 2 CH 2 Cl 2 a Cl-Si-CH 2 Cl I r ₃ where R2 and R3 are as defined above in a suitable solvent with a compound of formula RiM where R1 is as defined above and M is sodium or lithium or MgX, wherein X is a chlorine, bromine or iodine atom at a temperature of -80 ° C to 40 ° C to form chloromethylsilane which is reacted with imidazole, its 2- a methyl derivative, a 2,4-dimethyl derivative, a 4,5-dimethyl derivative, and a 2,4,5-trimethyl derivative or its alkali metal salts in a polar aprotic solvent, ethers or ketones at a temperature of 0 ° C to 150 ° C. Severography, n. P., Plant 7, Most Price 2,40 Kčs