CS238626B2 - Fungicide agent and preparation method of active substance - Google Patents

Abstract

A fungicidal composition containing the active ingredient the compound of formula I or II GLf N 2 Q ·· / R /% N fi3 aj to (II) where the general symbols have the meaning given below, or their acid addition salts or their salts metal complex compounds. Next, a process for preparing the active compounds is described substances.

Description

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

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

CH

CH, and its use as fungicides.

Silyl ethers of the formula -N are also known

OSLRi I ³ ^ r-CHjCH-CH-wherein CfCH

R1, R2 and R3 are lower alkyl or phenyl and have antimicrobial activity.

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

where it means

R is C 1 -C 4 alkyl;

Y and Z are hydrogen or a group of formula

Where S1R2R3R3 denotes

Ar is a substituted phenyl group,

X is CH or N and R is alkyl;

these compounds are said to be useful as agricultural fungicides.

NSR 3,000,140 discloses silyl ethers of formula ( ₃₎

Ar-O-CH-CH-C (CH 2 -)

AND

N where where means

R 1, R 2 and R 3 are alkyl, haloalkyl, alkenyl, alkynyl or substituted phenyl. These compounds are considered agricultural fungicides.

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

Ar is a substituted phenyl group,

X is CH or N;

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

U.S. Pat. No. 4,248,992 discloses a class of organosilicon compounds having at least one monovalent guanidine group of the formula

NR2

Z —N = where

NR2

R 1 is methyl, ethyl, vinyl or phenyl. They are said to be effective against fungi.

Belgian Patent No. 785,127 discloses quaternary ammonium salts of the formula wherein

R represents a hydrogen atom or a monovalent hydrocarbon group.

121

122

Compound% Disease Control

rice [4- (4-Chlorophenoxy) phenyl] dimethyl (1H-imidazol-1-ylmethyl) silane 100 ALIGN! Butyl (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 90 (1,1'-Biphenyl-4-yl) butyl (1H-imidazol-1-ylmethyl) methylsilane 90 Butyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 100 ALIGN! (1,1'-Biphenyl-2-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 90 (Ι, Γ-Biphenyl-3-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 80 [bis (2-Chlorophenyl)] (1H-imidazol-1-ylmethyl) methylsilane 90 Dimethyl (1H-imidazol-1-ylmethyl) - (4-methylsulfonylphenyl) silane 100 ALIGN! [bis (4-Bromophenyl)] (1 H -imidazol-1-ylmethyl) methylsilane 80 bis (4-fluorophenyl) hydroxy (1 H -dazol-1-ylmethyl) silane 60 Dimethyl [1H-imidazol-1-ylmethyl] J (4-trifluoromethoxyphenyl) - silane 90 (4‘-Bromo-1,1‘-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 90 Dimethyl (1H-hidazol-1-ylmethyl) octadecylsilane 80 Oxybis [bis (4-fluorophenyl) (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 90 (Ι, Γ-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 complex with copper chloride 100 ALIGN! Methyl [bis (4-methylphenyl)] (1H-1,2,4-triazol-1-ylmethyl) silane 80 Example 78

The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). These suspensions are sprayed on the tomato seedlings to the point where they begin to run down. The next day, the plants are inoculated with a spore suspension of Phytophthora infestans causing tomato mold and incubated in a moisture-saturated chamber at 20 ° C for 24 hours and then left in the growth chamber for a further 7 days before assessing the degree of infestation. The percentage of infestation is shown in the following table. Treated plants show no or little attack, while untreated plants show attack on each leaf.

Table XXX

Compound% Reduction of Tomato Mold [Bis (2-Fluorophenyl)] methylfH-1,2,4-triazol-1-ylmethyl) silane: 1 Complex with Copper Chloride (4-Bromophenyl) (1H-imidazole-1) -ylmethyl] dimethylsilane 30 (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 50 (1H-Imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane 80

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

Dimethyl (4-phenoxyphenyl) [1H-1,2,4-triazol-1-ylmethyl] silane 50 [4- (4-Chlorophenoxy) phenyl] dimethyl (1H-1,2,4-triazol-1-yl) ylmethyl jsilan 50 (1,1'-Biphenyl-2-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl jsilan 50 (1,1'-Biphenyl-4-yl) dimethyl (1H- 1,2,4-triazol-1-ylmethyl) silane, 4-dodecylbenzenesulfophonic acid salt 60

119

120

Compound% reduction of bacterial blotch of rice sheath

23862B

Compound% Reducing Rice Disease

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

Example 77

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

holůj. These suspensions are sprayed onto the rice seedlings until they begin to run down. The next day, the plants are inoculated with a rice disease spore suspension of Pyricularia oryzae and incubated in a moisture-saturated chamber at 28 ° C for 24 hours and then left in the growth chamber for a further 7 days before assessing the degree of infestation. The percentage of infestation is shown in the following table. Treated plants do not show infestation or are infested slightly, untreated show infestation on each leaf. 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) silane 90 [4- (Dimethylethylphenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 90 (4-Chlorophenyl) methylphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90 1 bis (4-Fluorophenyl) (methyl) (1H-1,2,4-trlazol-1-ylmethyl) silane 100 ALIGN! Butyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) silane 90 (2-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! (1,1'-Biphenyl-4-yl) butyl (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! Butyl (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN!

Dibutylphenyl] (1H-1,2,4-triazol-1-ylmethyl) silane 80 bis (1,1'-Biphenyl-4-yl) (methyl j (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1,1'-Biphenyl-2-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 90

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

4-Bromophenyl (methylphenyl (1H-1,2,4-triazol-1-ylmethyl) silane 80 [bis (2-Chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 90

Dimethyl (4-methylsulfonylphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 70 [bis (4-bromophenyl)] methyl

-1,2,4-triazol-1-ylmethyl jsilane 90 (1,1'-Biphenyl-4-yl) dimetbyl (1H-1,2,4-triazol-1-ylmethyl jsilane, 4-dodecylbenzenesulfonic acid salt 80 (1)) 1,1'-Biphenyl-4-yl] dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane: 1 complex with copper (I) chloride 100 (1,1'-Biphenyl-4-yl) dimethyl (1H- 1,2,4-triazol-1-ylmethyl jsilane: 1 complex with zinc chloride 100 [bis (2-fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane,

1: 1 complex with cuprous chloride 90 [bis (2-Fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethylsilane): 1 complex with cuprous chloride 100 (1H-Imidazol-1-ylmethyl) Dimethyl 4-phenoxyphenylsilane 70 [4- (1,1-Dimethylethylphenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 80 (4-Fluorophenyl) (1H-imidazol-1-ylmethyl) (phenyl) silane

100 ALIGN!

117

118

238G2B

Compound % reduction of bacterial spots of rice sheath Compound % reduction of bacterial spots of rice sheath Butyl (methyl) phenyl (1H-1,2,4- (4-Fluorophenyl) (1H-imidazole-1- (triazol-1-ylmethyl) silane (1,1'-Biphenyl-4-yl) butyl (methyl- 90 -ylmethyl) methyl (phenyl) silane (1 H-Imidazol-1-ylmethyl) [2- 90 thyl) (1H-1,2,4-triazol-1-ylinethyl) silane Butyl (4-Fluorophenyl) methyl (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-Methoxyphenyl]] methyl- 90 methyl (phenyl) silo 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-Chlorophenylphenyl) phenyl (1H- (1,2,4-triazol-1-ylmethyl) silane 90 zol-1-ylmethyl) methylsilane (1,1'-Biphenyl-2-yl) dimethyl- 80 4-Bromophenyl (methyl) phenyl (1H-1,2,4-trlazol-1-ylmethyl) silane 90 [1H-imidazol-1-ylmethyl] silane (1,1'-Biphenyl-3-yl) dimethyl (1H- 90 [bis [2-Chlorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane 60 -imidazol-1-ylmethylsilane [bis (2-Chlorophenyl)] [1H-imida- 90 (Ι, Γ-Biphenyl-4-yl) dimethyl- (1H-1,2,4-triazxl-1-ylmethyl) silane, 1: 1 chloride complex 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 (I) 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-Fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 complex with copper- 70 [3-Chlorophenyl) dimethyl (1 H -imidazol-1-ylmethyl) silane [4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) - 90 ným (1H-Imidazol-1-ylmethyl) dimime 90 thyl) silane (3,5-Dichlorophenyl) dimethyl (III-) 90 thyl (4-phenoxyphenyl) silane bis (4-Fluorophenyl) (1H-imidazole) 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 ALIGN! 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 natým 80

115

118

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

Table XVII

Compound% Brown Rot Control (Dimethylphenyl (1,2,4-triazol-1-ylmethyl) silane 89 (Butyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 95 (1,1'-Bif) enyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100

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

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

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

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

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

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

Diphenyl (1H-imidazol-1-ylmethyl) methylsilane 76 (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl jsilane) 45 (4-Fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl jsilane 65

Example 76

The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). The suspensions are then sprayed onto the rice seedlings to the point where they begin to run down. The next day, the plants are inoculated with a mixture of pulp and mycelium of Rhizoctonia solani, causing bacterial staining of the rice sheath, and incubating in a growth chamber for 7 days. Plant infestation is evaluated. The percentage of infestation is in the <following table. Treated plants show slight infestation while untreated plants are heavily infested.

Table XXVIII

Compound% Reducing Bacterial Spots of Rice (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 40 (3,4-Dichlorophenyl) dimethyl (1H-1, 2,4-triazol-1-ylmethyl jsilane 80 bis (4-fluorophenyl) (methyl j (1H-1,2,4-triazol-1-ylmethyl) jsilane 80 (4- (1,1-Dimethylethyl) phenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 90

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

113

114

Table XXVI

Compound% rust reduction on beans

Compound% Suppression of Yellow Spots of Groundnuts (1,1'-Biphenyl-4-yl) Hydroxy (Methyl) (1H-1,2,4-Triazol-1-ylmethylsilane) 100 (1,1'-Biphenyl-4-yl) (4-Fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100

Dimethyl (4-trifluoromethoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 50 (4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-1,2, 4-Triazol-1-ylmethyl) silane 100 (1,1'-Biphenyl-4-yl) dimethyl (5-methyl-1H-1,2,4-triazol-1-ylmethyl) silane 100 (1H-Biphenyl-4) -yl 1-Dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 (1,1'-Biphenyl-4-yl) dimethyl] (1H-1,2,4-triazol-1-ylmethyl) silane, 2: 1 copper chloride complex 100

A _b phytotoxic browning

B compound used at 400 ppm BB compound used at 20 ppm

Example 74

The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 80 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). These suspensions are sprayed onto the seedlings of God in amounts that are just starting to run down. The next day, the plants are inoculated with a spore suspension of the fungus Uromyces phaseoli causing rust to the god and incubated in a humidified chamber at 20 ° C for 24 hours and then kept in the greenhouse for a further 7 days. The degree of infestation is assessed. The percentage of infestation is shown in the following table. Treated plants show little or no attack on rust, while untreated plants are covered with rust. Some treated plants exhibit phytotoxicity in the form of reduced growth, in addition to reducing infestation.

(2,4-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane 83 (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 30G ^A bis (4-Chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) 100G silane (4-Chlorophenyl) methyl (phenyl) (lH-l, 2,4-triazol-l-ylmethyl) silane 98 ^b (4-Fluorophenyl) methyl (phenyl) (lH-l, 2,4 triazol-l-ylmethyl) silane I00 ^B bis (4-fluorophenyl) (methyl) (lH-l, 2,4-triazol-l-ylmethyl) silane gs ^B (l, biphenyl-4-yl) Dimethyl (1H-imidazol-1-ylmethyl) silane 100

A _c reduce growth

B compound used at a concentration of 16 ppm Example 75

The active compounds according to 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 TREM 014 (polyhydric alcohol esters) in an amount of 700 ppm. The preserved halved peaches are soaked in this suspension for three minutes and then placed in a sterile dry air package. After drying, the halved peaches are inoculated with two pieces of Monilinia fructicola mycelium causing brown stone rot and incubated in sterile containers for 5 days. Then the radius of colonies on each peach is measured. Colonies on treated peaches do not show growth or show only graying a few millimeters in diameter, while untreated peaches cover the entire surface

111

112

Compound% suppression of yellow spots of peanut leaves

Compound ° / o suppression of yellow spots of leaves peanuts (4-Fluorophenyl) - (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 100 ALIGN! (2-Chlorophenyl) (11-1-imidazol-1-ylmethyl) dimethylsilane 80 (1,1'-Biphenyl-4-yl) butyl (ΙΗ-imidazol-1-ylmethyl) methylsilane 90 bis (1,1'-Biphenyl-4-yl) (β-imidazol-1-ylmethyl) methylsilane 60 (1,1‘-Biphenyl-4-yl) (ΙΗ-imidazol-1-ylmethyl) methyl (phenyl) silane 80 (1,1'-Biphenyl-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) methyl (phenyl) silane 100 ALIGN! (4-Bromophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 90 (bis (2-Chlorophenyl)] (β-imidazol-1-ylmethyl) methylsilane 100 ALIGN! [bis (4-Bromophenyl)] (6-imidazol-1-ylmethyl) methylsilane 50 (1,1‘-Biphenyl-4-yl) dimethyl (ΙΗ-imidazol-1-ylmethyl) silane, 1: 1 copper chloride complex 100 ALIGN! (2-Chlorophenyl (4-chlorophenyl) (β-imidazol-1-ylmethyl) methylsilane 80 bis (4-Chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! Methyldiphenyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN!

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

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

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

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

100 ALIGN!

3 β β 2 Η

103

110

Compound % yellow suppression spots of leaves peanuts Compound % yellow suppression spots of leaves peanuts (2-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) - Sílán 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 ALIGN! manganese 2-Chlorophenyl (4-chlorophenyl) methyl- (1H-1,2,4-triazol-1-) 100 ALIGN! 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'-Biphenyl-4-yl) methyl- silane, 1: 1 copper chloride complex 100 ALIGN! (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! [bis (2-Fluorophenyl)] methyl- [bis (4-Methoxyphenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) - (1H-1,2,4-triazol-1-ylmethyl) silane, 2: 1 chloride complex copper 100 ALIGN! 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 ALIGN! silane (1,1'-Biphenyl-3-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) - 100 ALIGN! (2,4-Dichlorophenyl) dimethyl- (1 H -imidazol-1-ylmethyl) - silane 100 ALIGN! silane 2-Chlorophenylmethyl] phenyl- 90 Diphenyl (1H-imidazol-1-ylmethyl) methylsilane 50 (1H-1,2,4-triazol-1-ylmethyl) - silane 100 ALIGN! bis (4-Fluorophenyl) - 4-BiOmLenyl (methylphenyl- (1 H -imidazol-1-ylmethyl) - methylsilane 100 ALIGN! (1H-1,2,4-triazol-1-ylmethyl) - silane 100 ALIGN! Dimethyl (4-fluorophenyl) - [bis (2-chlorophenyl)] methyl- (1 H -imidazol-1-ylmethyl) - silane 60B ^A (1H-1,2,4-triazol-1-ylmethyl) - silane 100 ALIGN! Dimethyl (1H-imidazole-1- [bis (4-Bromophenyl)] methyl- (methylmethyl) (4-trifluoromethylphenyl) silane 36 ^B (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! Dimethyl [1H-imidazole-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 ALIGN! Butyl (2,4-dichlorophenyl) [1H-imidazol-1-ylmethyl) - (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 copper chloride complex 100 ALIGN! methylsilane bis (2,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 100 ALIGN! 90 (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) - silane, 1: 1 chloride complex (2,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 100 ALIGN! zinc 100 ALIGN! (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 100 ALIGN!

107

108

Compound% Reduction of Southern Corn Leaf Bacteria

Dimethyl (4-methoxyphenyl) (1H-1,2,4-triazol; -1-ylmethyl silane 90 (2,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) yl) Silane 90 bis (4-Chlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 80 bis (4-Chlorophenyl) hydroxy (1H-1,2,4-triazol-1-yl) 90-bis (4-fluorophenyl) hydroxy (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (4-chlorophenyl) hydroxy (4H-1,2,4-triazole-) 1-ylmethyl) silane 80

Oxybis [(4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 97 (1,1'-Biphenyl-4-yl) methyl (2-propoxy) (1H-1,2, 4-Triazol-1-ylmethyl) silane 90 (1,1'-Biphenyl-4-yl) (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 80

Dimethyl (4-trifluoromethoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 80 (4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazole) 1-ylmethyl) silane 70 (1,1'-Biphenyl-4-yl) dimethyl (5-methyl-1H-1,2,4-triazol-1-ylmethyl) silane 80 (1,1'-Biphenyl- 4-yl-dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, 1: 1 complex with copper (I) chloride 80 ti in acetone corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 (polyhydric alcohol esters), these suspensions are sprayed onto the peanut seedlings to start to run off, and the next day, the plants are inoculated with a spore suspension of Cercospora arachidicola causing yellow spots of the peanut leaves and incubated in a saturated chamber at a temperature of 27 ° C for 24 hours and then left in the growth chamber for a further 14 days and then evaluated for the degree of infestation. The treated plants show little or no stains, while the untreated plants have numerous stains. In some treated plants, phytotoxicity is observed as burning.

Table XXV

Compound% Suppression of Yellow Spots of Groundnut Leaves (1,1‘-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl silane, 2: 1 copper chloride complex 80

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

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

Dimethyl (1H-1,2,4-triazol-lylmethyl) (2-trifluoromethylphenylsilane 25 ')

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

The active compounds according to the invention are dissolved

105

106

Compound % reduction of southern corn leaf blotch Compound % reduction of southern corn leaf blotch 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) - silane 60 dimethylsilane 70 Cyclohexyl (dimethyl) - (1 H-Imidazol-1-ylmethyl) - (1H-1,2,4-triazol-1-ylmethyl) dimethyl (2-trifluoromethyl- silane 50 phenyl jsilane 90 (1,1'-Biphenyl-4-yl) dimethyl Butyl (2,4-dichlorophenyl) - (1H-1,2,4-triazol-1-ylmethyl) - (ΙΗ-Imidazol-1-ylmethyl) - silane, 4-dodecylbenzenesulfonic acid salt 100 ALIGN! methylsilane 80 bis (2,4-Dichlorophenyl) (1,1'-Biphenyl-4-yl) dimethyl (1 H -imidazol-1-ylmethyl) - (1H-1,2,4-triazol-1-ylmethyl) - methylsilane 80 silane, 1: 1 copper chloride complex 100 ALIGN! (4-Fluorophenyl) - (1,1'-Biphenyl-4-yl) dimethyl (1 H -imidazol-1-ylmethyl) - (1H-1,2,4-triazol-1-ylmethyl) - methyl [phenyl] silane 80 silane, 1: 1 chloride complex zinc 90 (2,6-Dimethoxyphenyl) (dimethyl) (1H-imidazole-1- (1,1'-Biphenyl-4-yl) dimethyl ylmethyl jsilan 50 (1H-1,2,4-triazol-1-ylmethyl) - sllan, 1: 1 complex with sulfate Dibutyl (1H-imidazole-1- manganese 100 ALIGN! -ylmethyl is methylsilane 90 2-Chlorophenyl (4-chlorophenyl) - (1,1'-Biphenyl-4-yl) - methyl (1H-1,2,4-triazole-1- [1H-imidazol-1-ylmethyl] - -ylmethyl) silane 60 methyl (phenyl) silane 80 (Ι, Γ-Biphenyl-4-yl) dimethyl- (1,1'-Biphenyl-3-yl) dimethyl- (1 H -imidazol-1-ylmethyl) - (1 H -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) (1H-imidazol-1-ylmethyl) - (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) - 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) dimethyl- triphenylsilane 50 (1H-1,2,4-triazol-1-ylmethyl) silane 90

Diphenyl (1H-imidazol-1-ylmethyl) methylsilane

103

104

Compound% reduction of apple scab

Compound% Reduction of Southern Corn Leaf Bacteria

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

And _g reduce growth

B _c chlorose

C compound used at 400 ppm D _b brown

Example 72

The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). These suspensions are sprayed onto the maize seedlings to the point where they begin to run down. The next day, the plants are inoculated with a spore suspension of Helminthosporium maydis, causing bacterial blotting of southern corn leaves, and incubated in a moisture-saturated chamber at 20 ° C for 24 hours and then left in the growth chamber for a further 7 days to assess the extent of infestation. The percentage of infestation is shown in the following table. Treated plants show little or no attack, while untreated plants have numerous spots. Some plants exhibit phytotoxicity as a reduction in growth, along with a reduction in infestation.

Table XXIV

Compound% Reduction of Southern Corn Leaf Bacteria

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

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

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

Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (4-trifluoromethylphenyl) silane 50 [4- (1,1-Dimethyl) phenyl] dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 60 (2-Methoxyphenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane

Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 bis (2,4-Dichlorophenyl) (methyl) (1H-1,2,4-triazol-1) -ylmethylsilane 80 (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90 (4-fluorophenyl) methyl (phenyl j (1H-1,2,4) -triazol-1-ylmethyl) silane 90 (2-Chlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 [4- (4-Chlorophenoxy) phenyl] dimethyl (1H-l, 2,4-triazol-1-ylmethyl jsilane 50 (3,5-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 40 f 1,1'-Biphenyl-4-yl J butyl (methyl ) (1H-1,2,4-Triazol-1-ylmethyl) silane 50 (Ι, Γ-Biphenyl-4-yl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90 [ bls (4-Methoxyphenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 90 (1,1'-Biphenyl-2-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) ) Silane 90 (Ι, Γ-Biphenyl-3-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100

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

101

102

238826

Compound % of apple scab Compound % of apple scab [bis (4-Bromophenyl)] (1H- -imidazol-1-ylmethyl) - Dimethyl (1H-imidazol-1-ylmethyl) octadecylsilane 80 methylsilane (1,1'-Biphenyl-4-yl) -dimethyl (1H-imidazol-1-ylmethyl) - 50 bis (4-Chlorophenyl) hydroxy (1H-1,2,4-triazol-1-ylmethyl) - silane 100 ALIGN! silane, 1: 1 copper chloride complex 100 ALIGN! bis (4-Fluorophenyl) (hydroxy- (2-Chlorophenyl) [4-chlorophenyl] - [1H-1,2,4-triazol-1-ylmethyl] - silane 100 ALIGN! (1 H -imidazol-1-ylmethyl) methylsilane 80 tris (4-Fluorophenyl) - (1 H- (1H-Imidazol-7-ylmethyl) - -1,2,4-triazol-1-ylmethyl- 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 ALIGN! silane Dimethyl (4-methylphenyl) (1H-1,2,4-triazol-1-ylmethyl) - 60 Oxybis [bis (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) - silan] 100 ALIGN! silane (4-Bromophenyl) dimethyl (1H1,2,4-triazol-1-ylmethyl) - 50G ^A (1,1'-Biphenyl-4-ylmethyl- (2-propoxy) (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! silane (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) - 90G (1,1'-Biphenyl-4-yl) hydroxy (methyl (1H-1,2,4-triazol-1-ylmethyl) silane) 100 ALIGN!

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

(4-Chloro-phenyl) -dimethyl-1- methyl (1H-1,2,4-triazole-1- (1H-1,2,4-triazol-1-ylmethyl) - -ylmethyl jsilan 100 ALIGN! silane 100 ALIGN! Dimethyl (4-trifluoromethoxy- Butyl (4-chlorophenyl) methyl phenyl) (1H-1,2,4-triazole-1- (1H-1,2,4-triazol-1-ylmethyl) - -ylmethyl jsilan 90 silane 100G (4‘-Bromo-1,1-biphenyl-4-yl) - Dimethyl (1-naphthalenyl) - dimethyl (1H-1,2,4-triazole-1- (1H-1,2,4-triazol-1-ylmethyl) - -ylmethyl jsilan 100 ALIGN! silane 50 (1,1'-Biphenyl-4-yl) dimethyl- (3-Chloro-phenyl) dimethyl- (5-methyl-1H-1,2,4-triazole- (1H-imidazol-1-ylmethyl) - -1-ylmethyl jsilane 100 ALIGN! silane 60 (1,1'-Biphenyl-4-yl) dimethyl- (1,1'-Biphenyl-4-yl) (4-fluoro- (1H-1,2,4-triazol-1-ylmethyl) - phenyl] (1H-imidazole-1- silane, 1: 1 chloride complex - ylmethyl) methylsilane 50 copper 100 ALIGN! Dimethyl (1H-imidazole-1- (1,1'-Biphenyl-4-yl) dimethyl- - ylmethyl (4-trifluoromethoxy) (1H-1,2,4-triazol-1-ylmethyl) - phenylj silane 50 silane, 2: 1 chloride complex (4‘-Bromo-1,1‘-biphenyl-4-yl) - copper 100 ALIGN! dimethyl (1H-imidazole-1- (3-Chlorophenyl) di-ethyl- -ylmethyl jsilan 50 (1H-1,2,4-triazol-1-ylmethyl) silane 60 (3,5-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane 50

100 ALIGN!

Compound % of apple scab Compound % of apple scab 2-Chlorophenyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 90 (4-Fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 100 ALIGN! 2-Chlorophenyl (dimethyl) (1H-1,2,4-triazol-1-ylmethyl) silane 60 (ΙΗ-Imidazol-1-ylmethyl) - (2-methoxyphenyl) - dimethylsilane 60 (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) - (2-Chlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 90 silane Butyl (4-chlorophenyl) - 80 Butyl (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 80 (ΙΗ-Imidazol-1-ylmethyl) - methylsilane 90 1,1'-Biphenyl-4-yl) butyl- (1 H -imidazol-1-ylmethyl) - (1H-imidazol-1-ylmethyl) methylsilane 100 ALIGN! dimethyl (1-naphthalenyl) silane 40 Butyl (4-fluorophenyl) - (3,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 80 (1 H -imidazol-1-ylmethyl) dimethylsilane 80 Dibutyl (1H-imidazole-1- (1H-imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane 100 ALIGN! -ylmethyl) methylsilane bis (1,1'-Biphenyl-4-yl) (1H-imidazol-1-ylmethyl) - 30 (2,4-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane 100 ALIGN! methylsilane (1H-Imidazol-1-ylmethyl) [bis (4-methoxyphenyl)] - 50 Diphenyl (1H-imidazol-1-ylmethyl) methylsilane 50 methylsilane (1,1 * -Biphenyl-2-yl) -dimethyl · · 50 bi9 (4-Fluorophenyl) - (1H-imidazol-1-ylmethyl) silane 90 (1H-imidazol-1-ylmethyl) methylsilane 100 ALIGN! (1,1'-Biphenyl-3-yl) dimethyl- Dimethyl (1H-imidazole-1- (1H-imidazol-1-ylmethyl) silane 90 ylmethyl) (4-trifluoromethylphenyl) silane 60 ^c (2-Chlorophenyl) (1H-irnidazole- [4- (1,1'-Dimethylethyl) phenyl] - (1-ylmethyl) methyl (phenyl) silane 100 ALIGN! (1 H -imidazol-1-ylmethyl) dimethylsilane 50 (4-Bromophenyl) (1H-imidazole- Butyl (2,4-dichlorophenyl) - -1-ylmethyl jmethyl (phenyl) silane 30 (1 H -imidazol-1-ylmethyl) methylsilane 100B [bis (2-Chlorophenyl)] (1H- bis (2,4-Dichlorophenyl) -imidazol-1-ylmethyl-methylsilane 60 (1 H -imidazol-1-ylmethyl) methylsilane 40 Dimethyl (1H-imidazole-1- (2,4-Dichlorophenyl) ylmethyl) (4-methylsulfonylphenyl) silane 80 (1H-imidazol-1-ylmethyl) methyl (phenyl) silane 80 Cyclohexyl (dimethyl (1H- (4-Chlorophenyl) - imidazol-1-ylmethylsilane 100B

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

Compound% reduction of apple scab

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

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

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

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

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

Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100G bis (2,4-Dichlorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) ) Silane 100 (2,4-Dichlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100G (4-Chlorophenyl) methyl [phenyl] (1H-1,2,4) -triazol-1-ylmethyl) silane 100 (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100

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

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

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

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

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

Compound% Barley Powdery Mildew Restriction

Example 70

The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the total volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). These suspensions are sprayed onto the barley seedlings to the point where they begin to run down. The next day, the plants are inoculated with a spore suspension of Erysiphe graminis causing barley powdery mildew and incubated in a growth chamber for 7 days. The attack rate is then assessed. The percentage of infection limits is shown in the following table. Treated plants show little or no attack by powdery mildew, while untreated plants are powdery mildew

you. Compound barley mildew reduction Dodecyl (dimethyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100 ^A Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 100 ALIGN! (3,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 80 Dimethyl (1H-imidazol-1'-ylmethyl) J (4-methoxyphenyl) silane 100 ALIGN! (2,4-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane 100 ALIGN! bis (4-Chlorophenyl) J (1H-imidazol-1-ylmethyl) methylsilane 100 ALIGN! Diphenyl (1H-imidazol-1-ylmethyl) methylsilane 100 ALIGN! Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethylphenylsilane) 100 ALIGN! Dodecyl (dimethyl) (1H-imidazol-1-ylmethyl) silane 100 ' Butyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 90 (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-trlazol-1-ylmethyl) silane 100 ALIGN!

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

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

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

A compound used at a concentration of 200 ppm Example 71

The active compounds according to the invention are dissolved in acetone corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing the day, inoculated with a spore suspension of TREM 014 (polyhydric alcohol esters). The following day, plants are inoculated with a spore suspension of Venturia inaequalis, which causes apple scab, and is incubated in a humidified chamber at 20 ° C for 24 hours and then left for 10 to 12 days in a growth chamber. The treated plants show less scab compared to untreated plants which are covered with speckles, and the phytotoxicity associated with reduced growth is observed in some plants at the same time as the scab attack.

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) silane 100

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

100 ALIGN!

Compound % reduction of cucumber powdery mildew Compound % reduction of cucumber powdery mildew (1,1'-Biphenyl-4-yl) dimethyl- bis (4-fluorophenyl) hydroxy- (1H-imidazol-1-ylmethyl) - (1 H -1,2,4-triazol-1-ylmethyl) - silane, 1: 1 chloride complex silane 100H copper 100 ALIGN! tris (4-Chlorophenyl) (2-Chlorophenyl) (4-chlorophenyl) - (1H-1,2,4-triazol-1-ylmethyl) - (1 H -imidazol-1-ylmethyl) - silane 100 ALIGN! methylsilane 100 ALIGN! bis (4-Chlorophenyl) hydroxy- (2-Chlorophenyl) (dimethyl) - (4H-1,2,4-Triazol-1-ylmethyl) - (ΙΗ-Imidazol-1-ylmethyl) - silane 100 ALIGN! silane G0 Oxybis [bis (4-fluorophenyl) - (Dimethyl) phenyl (1,2,4- (1H-1,2,4-triazol-1-ylmethyl) - (triazol-1-ylmethyl) silane 100 ALIGN! silan] 100 ALIGN! Ethyldimethyl (1H-1,2,4- (1,1-Biphenyl-4-yl) methyl- (triazol-1-ylmethyl) silane 100 ALIGN! (2-propoxy (1H-1,2,4-triazole- . 1-ylmethyl) silane 100 ALIGN! Butyldimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! (1,1‘-Biphenyl-4-yl) hydroxymethyl) (1H-1,2,4-triazol-1- Dimethyl (4-methylphenyl) - ylmethyl) silane 100 ALIGN! (1H-1,2,4-triazol-1-ylmethyl) silane 100G ' (1,1‘-Biphenyl-4-yl) (4- -fluorophenyl) methyl (1H- [4-Bromophenyl] dimethyl- 1,2,4-triazol-1-ylmethyl) - (1H-1,2,4-triazol-1-ylmethyl) - silane 100 ALIGN! silane 100G Dimethyl (4-trifluoromethoxy- tris (4-Chlorophenyl) (1 H- phenyl) (1H-1,2,4-triazole-1- imidazol-1-ylmethyl) silane 100 ALIGN! -ylmethyl) silane 100G tris (4-Fluorophenyl) (1H- (4‘-Bromo-1,1‘-biphenyl-4-yl) - imidazol-1-ylmethyl] silane 100 ALIGN! dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! bis (4-Fluorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane 100 ALIGN! (1,1'-Biphenyl-4-yl) dimethyl (5-methyl-1H-1,2,4-triazole- bis (4-Chlorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane 100 ALIGN! -1-ylmethyl Jsilane 100 ALIGN! (1,1'-Biphenyl-4-yl) dimethyl- (3-Chlorophenyl) dimethyl (1 H- (1H-1,2,4-triazol-1-ylmethyl) - imidazol-1-ylmethyl) silane 80 silane, l: copper (II) chloride complex 100 ALIGN! (1,1'-Biphenyl-4-yl) (4-fluorophenyl) (1H-imidazole-1- (1,1-Biphenyl-4-yl) dimethyl- -ylmethyl] methylsilane 100 ALIGN! (1H-1,2,4-triazol-1-ylmethyl) silane, 2: 1 chloride complex Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethoxy- copper 100 ALIGN! phenyl) silane 100G (4-Fluorophenyl) methyl (2-propoxy) (1H-1,2,4-triazole- (4‘-Bromo-1,1‘-biphenyl-4-yl) - -1-ylmethyl (silane 100 ALIGN! dimethyl (1H-imidazol-1-ylmethyl) silane 100 ALIGN! (1,1‘-Dimethyl-1-ethoxy) [bis (4-fluorophenyl)] (1H-1,2,4- (3,5-Dichlorophenyl) dimethyl (β-imidazol-1-ylmethyl) - triazol-1-ylmethyl) silane 100 ALIGN! silane 100G A _G decrease B growth, t hormonal action

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

Compound % reduction of cucumber powdery mildew Compound % reduction of cucumber powdery mildew bis (4-Chlorophenyl) - (1H-imidazol-1-ylmethyl) - Dodecyl (dimethyl) (1H-imidazol-1-ylmethyl) - methylsilane (1H-Imidazol-1-ylmethyl) - 100 ALIGN! silane (2-Chlorophenyl) (1H-imidazole- 55 triphenylsilane Diphenyl (1H-imidazole-1- 100 ALIGN! (1-ylmethyl) dimethylsilane [4- (4-Chlorophenoxy) phenyl] - 100 ALIGN! -ylmethyl) -methylsilane bis (4-Fluorophenyl) -1H-imidazol-1-ylmethyl) - 100 ALIGN! dimethyl (1H-imidazol-1-ylmethyl) silane Butyl (1H-imidazol-1-ylmethyl) - 100 ALIGN! methylsilane Dimethyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) - 100 ALIGN! methyl (phenyl) silane (1,1'-Biphenyl-4-yl) butyl- (1H-imidazol-1-ylmethyl) - 100 ALIGN! Sílán Dimethyl (1H-imidazol-1-ylmethyl) (4-methylthiophenyl) - 100G methylsilane Butyl (4-fluorophenyl) (1H-imidazol-1-ylmethyl) methyl 100 ALIGN! silane Dimethyl (1H-imidazole-1- 100 ALIGN! silane Dibutyl (1H-imidazole-1- 100 ALIGN! (methylmethyl) (4-trifluoromethylphenyl) silane Dimethyl (1H-imidazole-1- 100 ALIGN! -ylmethyl) methylsilane 1,1'-Biphenyl-4-yl) (1H- (imidazol-1-ylmethyl) methyl- 100 ALIGN! -ylmethyl) (3-trifluoromethylphenylsilane) [4- (1,1-Dimethyl-ethyl) - 80 (phenyl) silane 1,1-Dimethylethoxy) (1H-imidazol-1-ylmethyl) methyl- 100 ALIGN! phenyl] (1H-imidazol-1-ylmethyl) dimethylsilane (ΙΗ-Imidazol-1-ylmethyl) - 80 (phenyl) silane (ΙΗ-Imidazol-1-ylmethyl) methyl (phenyl) (2-propoxy) - 100 ALIGN! 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 methylsilane (1,1'-Biphenyl-2-yl) dimethyl (1H-imidazol-4-ylmethyl) - 50 (1H-imidazol-1-ylmethyl) methylsilane (2,4-Dichlorophenyl) - [1H- 100 ALIGN! silane (2-Chlorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) - 50 imidazol-1-ylmethyl) methyl (phenyl) silane (4-Chlorophenyl) (1H-imidazole- 100 ALIGN! silane (4-Bromophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl) - 1.00 (1-ylmethyl) methyl (phenyl) silane (4-Fluorophenyl) (1H-imidazole- 100 ALIGN! silane [bis (2-Chlorophenyl)] (1H-imidazol-1-ylmethyl) methyl- 100 ALIGN! (1-ylmethyl) methyl (phenyl) silane 100 ALIGN! silane Cyclohexyl (dimethyl (1H- 100 ALIGN! (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 ALIGN! silane 100 ALIGN!

Compound % reduction of cucumber powdery mildew Compound % reduction of cucumber powdery mildew (1,1'-Biphenyl-4-yl) methyl- Phenyl [bis (2-propoxy)] - (phenyl) 1H-1,2,4-triazole-1- (1H-1,2,4-triazol-1-ylmethyl) - -ylmethyl) silane 100 ALIGN! silane 100 ALIGN! (1,1-Dimethylethoxy) methyl- [bis (2-Fluorophenyl)] methyl- (phenyl) 1H-1,2,4-triazole-1- (1H-1,2,4-triazol-1-ylmethyl) - -ylmethyl) silane 100 ALIGN! silane, 1: 1 copper chloride complex 100 ALIGN! Methyl (phenyl) (2-propoxy) - (1H-1,2,4-triazol-1-ylmethyl) - [bis (2-Fluorophenyl)] methyl- silane 100 ALIGN! (1H-1,2,4-triazol-1-ylmethyl) silane, 2: 1 complex with chloride 1,1'-Biphenyl-2-yl) dimethyl- copper 100 ALIGN! (1H-1,2,4-triazol-1-ylmethyl) silane 90 Dimethyl (1H-imidazol-1-ylmethyl) phenylsilane 100 ALIGN! 2-Chlorophenyl (methyl) phenyl (1H-1,2,4-triazol-1-ylmethyl) - Ethyl (1H-imidazol-1-ylmethyl) - silane 100 ALIGN! diinethylsilane 100 ALIGN! 4-Bromophenyl (methyl) phenyl- Butyl (1H-imidazol-1-ylmethyl) - (1H-1,2,4-triazol-1-ylmethyl) - dimethylsilane 100 ALIGN! silane 100 ALIGN! (ΙΗ-Imidazol-1-ylmethyl) dimethyl (4-methylphenyl) - [bis (2-Chloro-phenyl)] -ethyl (1H-1,2,4-triazol-1-ylmethyl) - silane 100G ^A silane 100 ALIGN! (4-Bromophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 100 ALIGN! Cyclohexyl (dimethyl) (1H, 1,2,4-triazol-1-ylmethyl) - (1,1'-Biphenyl-4-yl) dimethyl- silane 100G (1H-imidazol-1-ylmethyl) silane 100 ALIGN! (bis (4-Bromophenyl) Jmethyl (1H-1,2,4-triazol-1-ylmethyl) - (4-Chlorophenyl) (1H-imidazole- silane 80G (1-ylmethyl) dimethylsilane 100 ALIGN! (1,1'-Biphenyl-4-yl) dimethyl- Butyl (4-chlorophenyl) (1H- (1 H -1,2,4-triazol-1-ylmethyl) - imidazol-1-ylmethyl) methyl- silane, salt (4-dodecylbenzene- silane 100G ' sulfonic acids 100 ALIGN! (ΙΗ-Imidazol-1-ylmethyl) - (1,1'-Biphenyl-4-yl) dimethyl- Dimethyl 1 (1-naphthalenyl) - (1H-1,2,4-triazol-1-ylmethyl) - silane 100 ALIGN! silane, 1: 1 copper chloride complex 100 ALIGN! (3,4-Dichlorophenyl) -1H-imidazol-1-ylmethyl) - (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) - dimethylsilane 100 ALIGN! silane, 1: 1 chloride complex (1H-Imidazol-1-ylmethyl- zinc 80 dimethyl (4-phenoxyphenyl) silane 100 ALIGN! (1,1'-Biphenyl-4-yl) dimethyl- (1H-1,2,4-triazol-1-ylmethyl) - Dimethyl (1H-imidazole) -1- silane, 1: 1 complex with sulfate -ylmethyl) (4-methoxyphenyl) - manganese 90 silane 100 ALIGN! 2-Chlorophenyl (4-chlorophenyl) - (2,4-Dichlorophenyl) dimethyl- methyl (1H-1,2,4-triazole-1- (1H-imidazol-1-ylmethyl) - 100H ^B -vlmethvllsilan 100 ALIGN! silane

Compound % reduction of cucumber powdery mildew Compound % reduction of cucumber powdery mildew (4-Chlorophenyl) dimethyl- -1-ylmethyl) (2-trifluoro- 100 ALIGN! (1H-1,2,4-triazol-1-ylmethyl) - methylphenyl) silane Sílán 100 ALIGN! (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-naphthalenes 1) - (1H-1,2,4-triazol-1-ylmethyl) - 100G (1H-1,2,4-triazol-1-ylmethyl) - silane silane 100 ALIGN! 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 ALIGN! (2,4-Dichlorophenyl) methyl- Dimethyl (4-phenoxyphenyl) - (phenyl) (1H-1,2,4-trlazole-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 ALIGN! (4-Fluorophenyl) methyl (phenyl) - (2,4-Dichlorophenyl) dimethyl- (1H-1,2,4-triazol-1-ylmethyl) - (1H-1,2,4-triazol-1-ylmethyl) - silane 100 ALIGN! 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 ALIGN! silane 100 ALIGN! (2,3-Dimethoxyphenyl) dimethyl- (1H-1,2,4-Triazol-1-ylinethyl) - (1H-1,2,4-triazol-1-ylmethyl) - triphenylsilane 100 ALIGN! silane 100G Methyldiphenyl (1H-1,2,4- (2,6-Dimethoxyphenyl) 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 ^c bis (4-Fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) - (2-Chlorophenyl) dimethyl (1 H- 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'-Biphenyl-4-yl) butyl 1-methyl) - silane 100 ALIGN! (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (4-trifluoro- Butyl (4-fluorophenyl) methyl- methylphenyl) silane 100G (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! Dimethyl (1H-1,2,4-triazol-1-ylmethyl) (3-trifluoro- bis (1,1'-Biphenyl-4-yl) (methyl) - methylphenyl) silane 100 ALIGN! (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN!

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

Compound% rust reduction on wheat

Compound % rust reduction on wheat bis (4-Fluorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane 100 ALIGN! bis (4-Chlorophenyl) hydroxy (1H-imidazol-1-ylmethyl) silane 80 (3-Chlorophenyl) dimethyl (1H- imidazol-1-ylmethyl jsilane 80 (1,1'-Biphenyl-4-yl) (4-fluorophenyl) (1H-imidazol-1-ylmethyl) - methylsilane 80 Dimethyl (1H-imidazol-1-ylmethyl) - (4-trifluoromethoxyphenyl) silane 100 ALIGN! (4‘-Bromo-1,1‘-biphenyl-4-yl) -dimethyl (1H-imidazol-1-ylmethyl) silane 100 ALIGN! bis (4-Chlorophenyl) hydroxy (1H-1,2,4-triazol-1-ylmethyl) silane 90 bis (4-fluorophenyl) hydroxy (1H- -1,2,4-triazol-1-ylmethyl jsilane 90 tris (4-Chlorophenyl (1H-1,2,4-triazol-1-ylmethyl) silane) 40 tris (4-Fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90 bis (4-Chlorophenyl) hydroxy (4H-1,2,4-triazol-4-ylmethyl) silane 90 Oxybis [bis (4-fluorophenyl) (111-1,2,4-triazol-1-ylmethyl) silane] 100 ALIGN! (1,1'-Biphenyl-4-yl) methyl (2-propoxy) (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! (1,1'-Biphenyl-4-yl) hydroxy (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane 90 (1,1'-Biphenyl-4-yl) (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! Dimethyl (4-trifluoromethoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! (4‘-Bromo-1,1‘-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN!

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

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

The active compounds according to the invention are dissolved in acetone in an amount corresponding to 6% of the final volume and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of TREM 014 surfactant (polyhydric alcohol esters). These suspensions are sprayed to run down onto the cucumber seedlings. The next day, the plants are inoculated with a spore suspension of Erysiphe cichoracearum causing powdery mildew and incubating in a growth chamber for 7 days. The degree of attack is then evaluated. The percentage of infestation is shown in the following table. Treated plants show little or no attack, unlike untreated plants that are covered with powdery mildew. Phytotoxicity as a growth restriction or a detrimental effect on growth is observed on some plants along with a reduction in powdery mildew.

Table XXI

Compound% Cucumber powdery mildew (Dimethyl) phenyl (1,2,4-triazol-1-ylmethyl) silane

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

OF

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

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

100 ALIGN!

Compound % Reduction rust on ^one nition PSE- Compound % rust reduction on wheat bis (1,1 ‘- Biphenyl-4-yl (methyl) - bis (4-Fluorophenyl) (1H-imidazole- (1 H -1,2,4-triazol-1-ylmethyl) - -1-ylmethyl jmethylsilane 100 ALIGN! silane 80 Dimethyl (4-fluorophenyl) (1H- (1,1'-Biphenyl-4-yl) methyl (phe- imidazol-1-ylmethylsilane 80 nyl] (1H-1,2,4-triazol-1-ylmethyl) silane 100 ALIGN! Dimethyl (1H-imidazol-1-ylmethyl) (4-trifluoromethylphenyl) - (1,1'-Biphenyl-3-yl) dimethyl (1H- silane 100 ' -1,2,4-triazol-1-ylmethyl jsilane 2-Chlorophenyl (methyl) phenyl (1H- 80 Butyl (2,4-dichlorophenyl) (1H-imidazol-1-ylmethyl) methyl -1,2,4-triazol-1-ylmethyl jsilane 80 hind 100 ALIGN! [bis (2-Chlorophenyl)] methyl (1H- bis (2,4-Dichlorophenyl) (1H-imi) -1,2,4-triazol-1-ylmethyl jsilane 100 ALIGN! dazol-1-ylmethyl) methylsilane 100 ALIGN! (1,1'-Biphenyl-4-yl) dimethyl (1H- 2,4-Dichlorophenyl (1H-imidazole- -1,2,4-triazol-1-ylmethyl jsilane, -1-ylmethyl) methyl (phenyl) - 4-dodecylbenzenesulfonic acid 100 ALIGN! silane 90 4-Chlorophenyl (1H-imidazol-1-yl) (1,1‘-Biphenyl-4-yl) dimethyl (1H- methyl j methyl (phenyl 1 j silane) 100 ALIGN! -1,2,4-triazol-1-ylmethyl jsilane, 1: 1 complex with zinc chloride Dodecyl (dimethyl j (1H-imida-) nečnatým 100 ALIGN! zol-1-ylmethyl jsilane 80 ^Λ (1,1'-Biphenyl-4-yl) dimethyl (1H- (4- (4-Chlorophenoxyphenyl) dimime- -1,2,4-triazol-1-ylmethyl jsilane, thyl (1H-imidazol-1-ylmethyl) - 1: 1 complex with manganese sulphate 90 silane 90 Butyl (1H-imidazol-1-ylme- 2-Chlorophenyl (4-chlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) thyl j methyl (phenyl j silane) 90 thyl jsilan 100 ALIGN! (1,1'-Biphenyl-4-yl) butyl (1H-imidazol-1-ylmethyl) methyl- (bis (2-Fluorophenyl)] methyl (1H- silane 100 ALIGN! -1,2,4-triazol-1-ylmethylsilane, 1: 1 complex with copper- (1,1'-Biphenyl-4-yl) (1H-imido- ným 90 zol-1-ylmethyl) methyl (phenyl) silane 100 ALIGN! [bis (2-Fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane, (1,1'-Biphenyl-3-yl) dimethyl (1H- 2: 1 copper chloride complex 100 ALIGN! imidazol-1-ylmethyl jsilane 90 (1,1'-Biphenyl-4-yl) dimethyl (1H- (4-Bromophenyl) (1H-imidazole- -1-ylmethyl) methyl (phenyl) -imidazol-1-ylmethyl jsilane 100 ALIGN! hind 90 (4-Chlorophenyl) (1H-imidazole-1- (1,1'-Biphenyl-4-yl) dimethyl (1H- (methylmethyl) dimethylsilane 50 -imidazol-1-ylmethyl jsilane, 1: 1 complex with copper (I) chloride 100 ALIGN! Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane 90 (2-Chlorophenyl) (4-chlorophenyl) - (1H-imidazol-1-ylmethyl) methyl- (1H-Imidazol-1-ylmethyl) di- thylsilane 100 ALIGN! methyl (4-phenoxyphenyl) silane 60 (2-Chlorophenyl) (dimethyl) (1 H- Dimethyl (1H-imidazol-1-ylmethyl) (4-methoxyphenyl) silane 60 imidazol-1-ylmethyl jsilane 80 Iris (4-Fluorophenyl) (1H-imida- (2,4-Dichlorophenyl) dimethyl (1H-imidazol-1-ylmethyl) silane 90 zol-1-ylmethyl jsilane 80

238628 cyano (3-phenoxyphenyl) methyl-4-chloro-alpha- (1-methylethyl) benzeneacetate (fenvalerate (3-phenoxyphenylmethyl) + (-cis, trans-3- (2,2-dichloroethenyl) -2,2 -dimethylcyclopropanecarbosylate (permethrin dimethyl dimethyl N, N '- [thiobis-] (N-methylimino) carbonyloxy-bis (ethanimidothioate (thiodicarboxylic phosphorothiolothionic acid), O-ethyl-O- [4- (methylthio) phenyl] -Sn-propyl ester (sulprofos) alpha-Cyano-3-phenoxybuzyl-3- (2,2-dichlorvinyl) -2,2-dimethylcyclopropanecarboxylate (cypermethrin) cyano- (3-phenoxyphenyl) methyl 4- (difluoromethoxy) -alpha- (methylthyl) benzene acetate ("Payoff")

0,0-Diethyl-O- (3,5,6-trichloro-2-pyridyl) phosphorothioate (chlorpyrifos)

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

5,6-Dimethyl-2-dimethylamino-4-pyrimidyldimethylcarbamate ('pirimor')

S- (N-formyl-N-methylcarbamoylmethyl) -Ο, Ο-dimethylphosphorothioate (formothion)

S-2- (ethylthioethyl) -, Ο-dimethylphosphorothioate (demeton-S-methyl) alpha-cyano-3-phenoxybenzyl cis-3- (2,2-dibromvinyl) -2,2-dimethylcyclopropanecarboxylate (deltamethrin) ) N- (2-chloro-4-trifluoromethylphenyl) alanine ('Mavrik') methyl cyano- (3-phenoxyphenyl) methyl ester.

Example 68

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

Table XX

Compound% rust reduction on wheat (Dimethyl) phenyl (1,2,4-triazol-1-ylmethyl) silane 90

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

Butyl (4-chlorophenyl) methyl (111-1,2,4-triazol-1-ylmethyl) silane (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane (2,4 -Dichlorophenyl dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane bis (4-Chlorophenyl) (methyl j (1H-1,2,4-triazol-1-ylmethyl) silane

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

Butyl (2,4-dichlorophenyl) methyl (1H-1,2,4-triazol-1-ylmethyl) silane bis (2,4-Dichlorophenyl) (methyl) (1H-1,2,4-triazol-1- ylmethylsilane (2,4-Dichlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane (4-Chlorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1) -ylmethyl jsilane (4-Fluorophenyl) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane

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

100 ALIGN!

100 ALIGN!

100 ALIGN!

80 ^A

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

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

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

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

Fungicides:

manganese (nianeb) 1,4-dichloro-2,5-dimethoxybenzene (chloroneb) methyl-1- (butylcarbamoyl) -butylcarbamate (1- (butylcarbamoyl) -butyl) benzamazole-carbamate (thiuram) n-dodecylguanidinedine acetate (dodine) ethylenebisdithiocarbamate (nianeb) )

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

N-Trichloromethylthiotetrahydrophthalimide (captanj

N-Trichloromethylthiophthalimide (Folpet J dimethyl-4,4‘- (o-phenylene) bis (3-thioallophthalmate))

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

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

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

3- (3,5-dichlorophenyl) -5-ethenyl-5-methyl-2,4-oxazolidinedione (vinclozolin) kasugamycin

O-ethyl-S, S-diphenylphosphorothioate (edifsnphos)

Bactericides:

tribasic copper sulphate streptomycin sulphate oxytetracycline

Acaricides:

seneciic acid, 2-sec-butyl-4,6-dinitrophenol ester (binapacryl)

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

2,2,2-trichloro-1,1-bis (4-chlorophenyl) ethanol (dicofol) bis (pentachloro-2,4-cyclopentadiene-1-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin i hexakis (2-methyl-2) -phenylpropyl) distannoxane (fenbutinoxide)

Nematocides:

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

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

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

N-isopropylphosphoramic acid, O-ethyl-O- [4- (methylthio) -m-tolyl] diester (phenamiphos)

Insecticides:

3-Hydroxy-N-methyl-crotonamide (dimethylphosphate) (monocrotophos) methylcarbamic acid ester, 2,3-dihydro-2,2-dlmethyl-7-benzofuranol ester (carbofuran)

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

O ‘, O‘-dimethyl ester (tetrachlorvlnfos)

2-mercapto succinic acid, diethyl ester, thionophosphoric acid S-ester, malathion phosphorothioic acid dimethyl ester, Ο, Ο-dimethyl, (methylparathion) methylcarbamic acid β-nitrophenyl ester, alpha-naphthol (carbaryl) methyl ester [(methylamino) carbonyl] ester ] oxyjethanimidothioate (methomyl)

N - (4-chloro-1-tolyl) -N, N-dimethylformamidine (chlordimeform)

O, O-diethyl-O- (2-isopropyl-4-methyl-6-pyrimidyl) phosphorothioate (diazinoj octachlorkamfen (toxapen)

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

78

The components are mixed, coarsely ground in a hammer mill and then in an air mill until substantially all particles have a diameter below 10 microns. The product is mixed again and filled into containers.

Example 60

Wettable powder (1,1‘-biphenyl-4-yl) dimethyl (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 mixed thoroughly, passed through an air mill to a particle size below 15 microns, mixed again and sieved through a 0.3 mm sieve and then packed.

All the active compounds according to the invention can be formulated in the same manner.

Example 61

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

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

Example 62

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

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

Example 63

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

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

Example 64

Highly concentrated (1,1'-biphenyl-4-yl) dimethylf-1H-imidazol-1-ylmethylsilane 98.5% silica airgel 0.5% synthetic amorphous fine silica 1.0%

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

Example 65

Granule wettable powder of Example 60 15% gypsum 69% potassium sulfate 16%

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

Example 66

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

The ingredients are mixed thoroughly and packaged for use.

Example 67

Emulsifiable concentrate

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

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

The active compounds according to the invention are useful for combating plant diseases. They are effective against a wide variety of plant diseases, in particular leaf disease of ornamental plants, vegetables, cereals and fruit plants such as Puccinia recondita, Erysiphe cicho238626

Example 51

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

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

Example 52

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

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

Example 53

Granule wettable powder of Example 46 15% gypsum 69% potassium sulfate 16%

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

Example 54

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

The ingredients are mixed and mixed under gentle heating to accelerate dissolution. A fine sieve is used when filling into the packaging so that the product does not contain any undissolved material.

Example 55

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

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

Example 56

Emulsifiable concentrate

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

heating to accelerate dissolution. A fine sieve is used when filling into packages to ensure the absence of any undissolved material.

Example 57

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

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

Example 58

Emulsifiable concentrate

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

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

Example 59

Wettable powder of (1,1'-biphenyl-4-yl) dimethyl (1 H -imidazol-1-ylmethyl) silane 59% sodium alkyluaphthalenesulfoinate 2% low viscous methylcellulose 2% diatomaceous earth 46 ° / q vu mixed and sieved through a sieve with mesh All active ingredients according to the invention are processed into a wettable powder in the same way.

Example 47

Wettable powder of (4-bromophenyl) dirnyl-1H-1,2,4-triazole Depending on the intended use and physical properties of the active ingredient, the composition may contain higher or lower amounts, and a higher ratio of active ingredient to surfactant is sometimes desirable and achievable. by introducing a surfactant into the composition of the invention or while mixing in a tank.

Typical solid diluents are described by Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Edition, Dorland Books, Caldwell, New Jersey. Typical liquid solvents and diluents are described in Marsden &quot; Solvent Guide &quot;, 2nd Edition, Intersicience, New York, 1950. Solubility below 0.1% is preferred for suspension concentrates; resistant to phase separation at 0 [deg.] C. &quot; McCutcheor &apos; s Detergents and Emulsifiers Annual &quot; Compounds], Chemical Publishing Co., Inc., New York, 1964, contains 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 simply mixing the ingredients. The fine solid compositions are prepared by mixing and generally crushing, for example in a hammer mill or fluid energy mill. Suspensions are prepared by wet grinding (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets can be prepared by spraying the active ingredient on a preformed granulate carrier or by agglomeration techniques. See JE Browning, "Agglomeration", Chemical Engineering, 4.12.1967, p. 147 et seq., And "Perry's Chemical Engineer's Handbook," 4th Edition, McGraw-Hill, New York, 1963, pp. 8-59.

Example 46

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

The ingredients are mixed thoroughly, passed through an air mill until a median particle size of less than 15 microns is formed, zno-1-ylmethyljsilane 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 until the particle size is below 10 microns. The product is mixed again and packaged.

Example 48

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

The ingredients are mixed and ground in a hammer mill until a highly concentrated concentrate is passed through a 0.3 mm sieve. This concentrate can then be processed in various ways.

Example 49

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

The ingredients are mixed thoroughly and packaged for use.

Example 50

Aqueous suspension of (Ι, Γ-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 50.0% polyacrylic acid thickener 0.3% dodecylphenylethylene glycol ether 0.5% disodium phosphate 1,0% ^{mono-sodium phosphate} 0,5 ° / o polyvinyl alcohol 1,0% pentachlorophenyl 0,4% water 46,3 ^ιθ / ο

The components are ground together in a sand mill up to a particle size of substantially below 5 microns.

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

Resources

Useful compositions containing the active compounds of the invention can be prepared by conventional methods. These are powders, granules, pellets, solutions, emulsion wettable powders, emulsifiable concentrates and the like. Many of the active compounds according to the invention can be used directly. Highly concentrated formulations are used primarily as intermediates for the preparation of other formulations. The compositions generally contain from 1 to 99% by weight of the active compound (s) and from about 0.1 to 20% of surfactant (s) and / or from 5 to 99% of a solid or liquid inert diluent or solid or liquid inert diluents. Especially they are. the individual components are included in the following approximate amounts:

Active substance Diluent (s) 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 Pills 1 - 25 70 - 99 0—5 Granules and pellets 1-95 5 - 99 0 - 15 Highly concentrated agents 90 - 99 0 - 10 0—2

Ri ‘

Re

Qi Qž Q3

11-C3H7

phenyl —CH2CH— H H H phenyl - C (CH 3) ₂ C (CH 3) 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 AND H H H 2,4-dlchlorophenyl 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 = CHCH ₂ - CH ₃ CH 3 i H CH3 CH3 n-CisHsz 1 1 —CHCH2CH2CH— H CH3 CH3

Table XVIII

Rl * Re Qi Q2 Q3 C2H5 t-C 6 H 9 H H H 11-C4H9 C2H5 H H H 11-C18H37 CH3 H H H cyclohexyl 11-C3H7 H H H 1-Naphthyl I-C4H9 H H H phenyl CH3 CH3 CH3 CH3 phenyl n-C3ří7 ^: CH3 H H phenyl 1-C3H7 H CH3 CH3 phenyl t-C 4 H 9 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-C 3 H 7 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 ^ are, 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-methoxyphenyl 4-methylphenyl 4-fluorophenyl I-C4H9 H H n-CiHg 1-C3H7 C2H5 H i-ClHg Mp 114-116 ° C Table XVII

[/]

ÓR _fe 4

Rl * R2; Qi Qž Q3 C2H5 ch ₃ CH3 CH3 CHs CHs cyclohexyl CH3 1-C3H7 H CHs CHs n-C ₈ HS7 n-C 6 H 13 t-C 1 H 8 CHs H H 1-Naphthyl CHs I-C3H7 CH3 H H phenyl ch ₃ t-C 1 H 8 H CHs H phenyl ch ₃ t-C 6 H 8 H H CHs phenyl CH3 t-C 6 H 8 CHs CH3 CH3 phenyl ch ₃ S-C4H9 H CHs CH3 phenyl CH3 I-C3H7 CH3 H H 4-phenylphenyl 11-C1H9 t-C 1 H 8 ch ₃ CH3 CH3 4-phenylphenyl CHs t-C 1 H 8 CH3 H H 4-phenylphenyl ch ₃ t-C 1 H 8 CHs CH3 CHs 4-chlorophenyl CHs t-C 4 H 8 CHs H H 4-chlorophenyl CH ₃ t C4H9 H CHs CHs 4-fluorophenyl CHs t-C 1 H 8 H CH3 H 4-fluorophenyl CHs t-C 4 H 8 H H CHs phenyl phenyl C2H5 CH3 CHs CHs phenyl phenyl nC ₃ H7 CHs CHs CH3 4-fluorophenyl phenyl I-C3H7 H CH3 CHs 4-fluorophenyl phenyl t-C 6 H 8 CH3 H H 4-chlorophenyl phenyl I-C3H7 CH3 H H 2,4-dichlorophenyl phenyl H CH3 H H 4-fluorophenyl 4-fluorophenyl t-C 4 H 8 CH3 H H 4-fluorophenyl 4-fluorophenyl t-C 1 H 8 H CHs CH3 4-fluorophenyl 4-fluorophenyl t-C 4 H 9 CH3 CH3 CH3 2-methoxyphenyl 2-methoxyphenyl C2H5 CHs H H 3-methylphenyl 3-methylphenyl I-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 by 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, compounds of Table XVIII and XIX can be prepared.

n ^'22 1.4971;

Table XVI _OR6

Ri ‘

C2H5 t-C4H9

11-C 4 H 9 n-C 12 H 25

11-C18H37 cyclopropyl cyclohexyl

1- Naphthyl

2-naphthyl phenyl phenyl phenyl phenyl phenyl

4-phenylphenyl

4-phenylphenyl

4-phenylphenyl

4-phenylphenyl

4-chlorophenyl

4-chlorophenyl

4-chlorophenyl

4-fluorophenyl

4-fluorophenyl

4-Phenoxyphenyl

4-t-butylphenyl

3-Trifluoromethylphenyl 2-methylthiophenyl 2,4-dichlorophenyl 2,4-dichlorophenyl 2,4-dichlorophenyl

2,4- dichlorophenyl

2,3-dimethylphenyl

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

3-Methyl-4-chlorophenyl

3,5-dichlorophenyl 11-C 12 H 25 n-C 16 H 37

1-naphthyl phenyl

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

3-fluorophenyl

2-Methoxyphenyl 2-chlorophenyl

2,4- dichlorophenyl

3,5-dichlorophenyl

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

R2 Rs CH3 CH3 CH3 t-C 6 H 8 CH3 C2H5 C2H5 CH3 n-C6H13 CH3 CH3 S-C4H9 CH3 CH3 I-C3H7 1-C3H7 cyclobutyl n-C3H7 CH3 H CH3 CH3 CH3 C2H5 CH3 1- _C 3 H 7 n _D ²⁰ 1.5 3 5 2 t-C 1 H 8 H 11-C4H9 CH3 t-C 4 H 9 H CH3 C2H5 CH3 n-C4H9 n-Cl9 n-C4Hg CH3 CH3 CH3 C2H5 n-CsHt3 n-C3H7 CH3 C2H5 cyclohexyl I-C4H9 n-C3H7 S-C4H9 I-C4H9 H cyclopentyl C2H5 CH3 CH3 ch ₃ C2H5 CH3 t-C 4 H 8 11-C4H9 C2H5 cyclopropyl I-C3H7 S-C1H9 11-C3H7 1,1-dimethylpropyl H C2H5 CH3 n-CsHu C2H5 2,4-dichlorophenyl I-C4H9 phenyl CH3 phenyl C2H5 phenyl I-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 I-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 to metal complexes or salts.

Example 43

Preparation of (1,1'-biphenyl-4-yl) (1H-imidazol-1-ylmethyl) (methoxy jmethylsilane)

A mixture of (1,1'-biphenyl-4-yl) chloro (chloromethyl) methylsilane and two equivalents of the imidazole sodium salt in dimethylformamide is maintained at 80-90 ° C for two hours. Then, 10 equivalents of methanol are added and the mixture is maintained at 70 ^° C for one hour, cooled, diluted with water and extracted rapidly with ether. The ether solution was washed with water and brine, dried over magnesium sulfate and evaporated to give (1,1'-biphenyl-4-yl) (1H-imidazol-1-ylmethyl) (methoxy) methylsilane.

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

Example 44

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

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

n _D ²⁰ 1.5291;

ir (neat) 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 (3 H, s),

1.3 (9H, s)

3.6 (2 H, s),

6.8 (1 H, s),

7.0 (1 H, s) and

7.3-7.7 (6H, m).

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

Example 44a

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

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

NMR (CD3SOCD3)

4.1 (2 H, s),

6.8 (1 H, s),

6.9 (1 H, s),

7.4 (4H, d).

7.6 (5 H, d).

Ri * Rž 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 mp 85-88 ° C 4-phenylphenyl 4-fluorophenyl methylphenyl _nn ²² 1.6181

Ri ‘ TABLE ^R 2 R ¹ R ₁ -Si-C 1 R 2 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-C6H13 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-C18H37 n-C6H13 11-C6H13 H CH3 C.H3 1-naphthyl n-CdHg n-ClHg 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 a 1: 1 (1,1'-biphenyl-4-yl) -dimethyl (1H-imidazol-1-ylmethyl) silane-copper (II) chloride complex

A mixture of 0.50 g (0.0017 mol) of (1,1'-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane and 0.22 g (0.0017 mol) of cuprous chloride in ml of tetrahydrofuran was added. reflux under nitrogen for 15 minutes and the resulting dark green solution was evaporated to give a 1: 1 (Ι, Γ-biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane / chloride complex copper (I) as a dark green solid, m.p. 72 DEG-80 DEG C. (dec.);

Ri ‘

R2

Rs

I-C3H7

11-C4H9 n-C10H11 n-C12H25

11-C14H29

11-C18H37 cyclopropyl cyclopentyl cyclohexyl

1-Naphthyl

1- Naphthyl

2-naphthyl phenyl phenyl phenyl phenyl

4-phenylphenyl

4-phenylphenyl

4-broniphenyl

4-chlorophenyl

4-fluorophenyl

4-Phenoxyphenyl

4-i-Propylphenyl

4-t-butylphenyl

3-phenylphenyl

3-trifluoromethylphenyl

3-chlorophenyl

2-methoxyphenyl

2-thiomethylphenyl

2-phenylphenyl

2,4-dichlorophenyl

2,4- dichlorophenyl

2,3-dimethylphenyl

2-methyl-5-fluorophenyl

2,5-dimethoxyphenyl

2,6-dimethylphenyl

3,4- dichlorophenyl

3,5-dichlorophenyl

3,5-dichlorophenyl

3-Methyl-4-chlorophenyl

4-fluorophenyl

4-chlorophenyl

4-bromophenyl

4-Phenylphenyl 4-t-butylphenyl 4-thiomethylphenyl 4-phenoxyphenyl

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

3-Trifluoromethylphenyl 2-chlorophenyl 2-methoxyphenyl

2,4-dichlorophenyl 2-chloro-4-phenylphenyl

2-fluoro-4-phenylphenyl

3,5-dichlorophenyl

2,5-dimethoxyphenyl

2,6-dimethoxyphenyl

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

3-Trifluoromethylphenyl cyclohexyl

11-C4H9 cyclopropyl

11-C3H7

I-C3H7

3-methylbutyl

N 1 -C 6 H 43 cyclopentyl cyclohexyl n-C 1 H 8 t-C 1 H 8

11-C5H11

11-C3H7

11-C4H9

1,1-dimethylpropyl

11-C6H13

CžHs

11-C4H9 i-CsH?

11-C4H9

11-C1H9

C 1 -C 4 H 9 cyclopropyl

I-C4H9

1-C4H9

S-C 4 H 9 n-C 5 H 11 t-C 1 H 8 cyclobutyl

I-CjHg

II-C4H9 cyclopropyl

11-C 3 H 7 cyclopentyl

4-methylpentyl

1-methylbutyl

II-C5H11 n-C6Hg cyclohexyl cyclopropyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl

4-fluorophenyl

4-chlorophenyl

4-bromophenyl

4-phenylphenyl

4-methoxyphenyl

3-trifluoromethylphenyl

CH3 CH 3 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 CH 3 n _D ²² 1.5880 CHó CH ₃ n _D ²¹ 1.5415 CH 3 n _D ²² 1.5161 CHj CHj CH3 CHj CHj CH3 CHj CH3 CHj CH 3 n _D ²¹ 1.5588 CH3 CHj CH3 CH3 CHj CHj CH3 CH3 CH3 CH 3 n _D ¹⁹ 1.5810 CH 3 n _D ²¹ 1.6000 CH 3 n _D ²² 1.6115 CH 3 n _D ²¹ 1.6378 CHs CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH n _D ²² 1.6058 CH3 CH n _D ²² 1.6150 CH3 CH3 CH3 CH3 CH3 CH 3 n _D ²² 1.5569 CH3 _nn 1.5820 CH 2 n _D ²¹ 1.6305 CH 3 mp 44-53 ° C CH 3 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

1-C 3 H 7 n-C 4 H 9 η-ϋβ-7 n-C 14 H 29 n-C 16 H 37 cyclopropyl cyclohexyl

1- Naphthyl

2-naphthyl phenyl

4-phenylphenyl

4-phenylphenyl

4-phenylphenyl

4-phenylphenyl

4-chlorophenyl

4-fluorophenyl

4-Phenoxyphenyl

4- (4-chlorophenoxy) phenyl

4-t-butylphenyl

3-methoxyphenyl

3-Trifluoromethylphenyl 2-thiomethylphenyl

2-phenylphenyl

2,4- dichlorophenyl

2,6-dimethylphenyl

3,5-dichlorophenyl

3-Methyl-4-chlorophenyl 2-methyl-5-fluorophenyl C2H5 cyclohexyl n-C18H37 n-C1H9 n-C12H25

I-Naphthyl cyclopropyl n-C4H9 n-C4Hg n-C3H7

C 1 -C 4 H 9 cyclopentyl

II-C14H29

11-C4H9 phenyl

4-chlorophenyl

4-fluorophenyl

4-phenylphenyl

2,4-dichlorophenyl phenyl phenyl phenyl phenyl

2-chlorophenyl

2-methoxyphenyl

2,4- dichlorophenyl

3,5-dichlorophenyl 4-chlorophenyl 4-fluorophenyl 4-chlorophenyl

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

2,4- dichlorophenyl

2,6-dimethoxyphenyl

3,4-dichlorophenyl C2H5

1-C 3 H 7 n-C 6 H 8

C 2 H 5 cyclopropyl n-C 6 H 13

C 2 H 5 n-C 3 H 7 n-C 6 H 8 n-C 4 H 9 cyclopropyl

C 2 H 5 n-C 4 H 9 n-C 6 H 13 cyclohexyl

11-C4I-19

11-C3H7

11-C4H9

11-C4H9

5- C4H9

C2H5

S-C4H9

1-C3H7 cyclohexyl n-CdHg t-CdHg cyclopentyl

S-C 1 H 9 n-C 1 H 8 phenyl phenyl phenyl

4-chlorophenyl

4-chlorophenyl

4-fluorophenyl phenyl phenyl phenyl phenyl phenyl phenyl

4-chlorophenyl

4-fluorophenyl phenyl

4-chlorophenyl

4-fluorophenyl

4-phenylphenyl

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

CH3 n _D ²⁰ 1.5 9 9 9

CHs

CH 3 n _D ²² 1.6019

CH3

CH 3 n _D ²⁰ 1.6044

CH ₃ CH ₃

CH 3 ch ₃ gh ₃

CH3

CH3

CH3

C2H5

1-C 3 H 7 n-C 4 H 8 cyclopentyl

1-methylbutyl n-C 6 H 13 S-C 4 H 9

II-C 3 H 7 n-C 1 H 8 cyclobutyl n-C 6 H 13

C2H5 n-C4H9 n-C6H13 cyclohexyl n-C1Hg n-C3H7 cyclohexyl n-C1Hg

1- CiHg t-CiHg

S-C4H9

3-methylbutyl cyclohexyl n-C1Hg t-QHg cyclopentyl

S-C4U9-C1H9 phenyl phenyl phenyl

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

2,4- dichlorophenyl

3-Trifluoromethylphenyl

3,5-dichlorophenyl

2,6-dimethoxyphenyl

2-fluorophenyl

4-phenylphenyl phenyl, mp 175-178 ° C

4-chlorophenyl

4-fluorophenyl

4-phenylphenyl

2,4-dichlorophenyl

4-fluorophenyl

4-chlorophenyl

4-phenylphenyl

2,4-dichlorophenyl

Table XIV

Ri ‘ R2 R3 ch ₃ CH3 CH 3 n _D ²² 1.4805 C2H5 CH3 CH 3 n _D ²² 1.4848 1-C3H7 CH3 CHs 11-C4H9 . CH3 CH 3 n _D ¹⁹ 1.4811 t-C 1 H 8 CH3 CHs 11-C12H25 CH3 CH 3 n _D 25 1.4885 11-C14H29 CH3 CHs 11-C18 H57 CHs CH 3 n _D ²¹ 1.4639 cyclopropyl CH3 CH3 cyclobutyl ch ₃ CH3 cyclopentyl CHs CH3 cyclohexyl CHs CH 3 n _D ²² 1.4999 1-Naphthyl CH3 CH ₃ n _D ²³ 1.6188 2-Naphthyl CH5 CH3 phenyl CH3 CH 2 C 120-125 ° C 4-bromophenyl CHs CH n ² _D «1.5741 4-fluorophenyl ch ₃ CH 3 n _D ²³ 1.5314 4-methoxyphenyl CHs CH 3 n _D ²⁵ 1.5485 4-Phenoxyphenyl CH3 CH 3 n _D ²² 1.5833 4- (4-chlorophenoxy) phenyl CHs CH 3 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 CH 3 n _D ²³ 1.5855 4-methylsulfonylphenyl CH3 CH3 η _η ²¹ 1.5552 4 trifluoromethylphenyl CH3 CH 3 n _u ²² 1.4867 4-methylphenyl CH3 CH 3 n _D ²¹ 1.5482 4-i-Propylphenyl CHs CH3 4-t-butylphenyl CH3 CH 3 n _D ²³ 1.5229 4-cyclohexylphenyl CH3 CH 2 n _n ²² 1.5085 4-Trifluoromethoxyphenyl CH3 CHs lip ²² 1.4888 4- (4-chlorophenyl) phenyl CH3 CH3 4- [4-methylphenyl) phenyl CHs CH3 4- (4-Trifluoromethylphenyl) phenyl CHs CH3 4- (4-fluorophenyl) phenyl CH3 CH3 4- (4-bromophenyl) phenyl CH3 CH 3 n _D ²² 1.5745 3-phenylphenyl CHs CF3 n _D ²¹ 1.6002 3-trifluoromethylphenyl CH3 CH 3 n _D ²⁰ 1.4927 3-chlorophenyl CHs CH 3 n _D ²² 1.5560 2-Trifluoromethylphenyl CH3 CH3 n _D ²³ 1.5056 2-phenylphenyl CH3 CH 3 n _D ²² 1.5996 2-chlorophenyl CH3 CH 3 n _D ²² 1.5382 2-methoxyphenyl CH3 CH 3 n _D ²² 1.5344 2,3-dimethylphenyl CH3 CH3 2,3-dimethoxyphenyl CH3 CH 3 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 CH 3 n _D ²³ 1.5348 2,6-dimethylphenyl CH3 CHs 3,4-dichlorophenyl CH3 CH 3 n _D ²³ 1.5673 3-methyl-4-fluorophenyl CH3 CHs 3,5-dichlorophenyl CHs CH 3 n _D ²² 1.5461 C2H5 C2H5 ch ₃

6.6 (1H, broad sj,

6.9 (1H, broad s),

7.1 (1H, broad s),

7.3 (4 H, s).

Example 39

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

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

n _D ²³ 1.5637;

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

1095, 1075, 1025, 840, 780, 735 cm @ -1;

NMR (CDCl3)

0.4 (6H, s);

3.9 (2 H, s),

6.7 (1H, broad s),

7.0 (1H, broad sj,

7.2-7.5 (4H, m).

Example 40

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

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

n _D ²² 1.5995;

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

1110, 1075, 1025, 810, 790, 735, 700, 660 cm ^-1 ;

NMR (CDCl3)

0.6 (3 H, s),

3.9 (2H, s,

6.6 (1H, broad s),

6.9 (1H, broad s j,

7.2-7.5 (11H, m).

The compounds of Table XIV were prepared from the appropriate chloromethylsilanes by the method of Examples 37-40.

Example 41

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

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

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

Rl

Re

Qi

Q2 phenyl phenyl

4-phenylphenyl

4-phenylphenyl

4-fluorophenyl

4-chlorophenyl

4-Phenoxyphenyl

3-trifluoromethylphenyl

2-methoxyphenyl

CHo CH3

II -CHCH2CH2CH- H -C (CH3) 2CH2CHzC (CH3) 2 _-CH2 CH η = CHCH 2 H

CHo CH3,

I - CH 2 C = CCH 2 - h - CH 2 CH = CHCH 2 h - CH 2 CH 2 CH 2 CH 2 - H n-C 6 H 8

I - CH 2 CH 2 CH 2 CH - CH 3

CHo CHó

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-4-yl) chloromethyldimethylsilane and 1.1 g (0.012 mol) of imidazole sodium salt in 5 ml of dimethylformamide is maintained at 80-90 ° C for two hours, cooled The ether solution was washed with water and brine, dried over magnesium sulphate and evaporated to give 2.0 g of a viscous, pale-yellow oil. The crude product is then taken up in a hot mixture of 20 ml of hexanes and 3 ml of ethyl acetate, the solution is cooled slowly and seed crystals are added as soon as the cloudiness is observed, and the resulting crystals are collected and dried to give 0.84 g (29%). (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylinethyl) silane in the form of colorless flakes:

mp 51-53 ° C;

(Nujor) 1235, 1215, 1105, 1065, 900, 830, 785, 750, 730, 685 cm -1;

NMR (CDCl3)

0.4 (6H, s);

3.7 (2 H, s),

6.7 (1H, broad s),

7.0 (1H, broad s),

7.1 - 7.8 (10H, m);

Analysis for C18H20N2Si (MW: 292.45) calculated:

C 73.92 H 6.89 N 9.58 found:

C 73.40 H 7.00 N 9.40

C 73.70 H 7.00 N 9.40

Example 38

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

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

n _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 (CH 3) 2 C (CH 3) 2 - H H 4-phenylphenyl —CH2CH2— C2H5 AND H H 4-phenylphenyl 1 —CH2CH— CH3 CH3 I 1 H H 4-phenylphenyl 1 1 —CH CH H H 4-fluorophenyl —CH2CH2— CH3 AND 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-1H CH3 CH3 2-ethoxyphenyl | —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 = CHCH ₂ - ch ₃ ch ₃ CH3 CH3 n-C 16 H 37 | | —CHCH2CH2CH— H CH3 phenyl —CH2CH = CHCH2— H H phenyl -C (CH 3) 2 CH = CHC (CH 3) 2 - H H

Table XII

© »2

Rl Rs Qi Q2 C2H5 t-C 4 H 9 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-C 4 H 9 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-C 18 H 37 —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-C1-4H37 | | —CHCH2CH2CH— phenyl phenyl —CH ₂ CH = CHCH ₂ - —C (CH 3) 2 CH = CHC (CH 3) 2 - CH 3 CH 3 phenyl 1 —CHCH2CH2CH— mp 57-60 ° 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-C6Hg

11-C18H37 cycloliexyl

1-naphthyl phenyl phenyl

phenyl phenyl

4-phenylphenyl

4-phenylphenyl

4-phenylphenyl

AND

4-fluorophenyl

4-fluorophenyl

4-chlorophenyl

4-chlorophenyl

3-Trifluoromethyl-phenyl

2-methoxyphenyl 2,3-dimethylphenyl

Table XI

O

R ^ are -CH ^Ct

Re —CH2CH2—

CH3

I —CH2CH —— CH2CH2CH2—

C2H5

I —CH2CH— —CH2CH2— —CH2CH2—

C2H5

I-CH 2 CH-n-C 3 H 7

M.p. 142-162 ° C; - CH 2 CH - C (CH ₃ ) 2 C (CH ₃ ) 2? (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 a nitrogen atmosphere while 2.5 ml (1.9 g, 0.018 mol) of triethylamine was added dropwise. The resulting suspension was heated to 80 ° C and held at this temperature for two hours, cooled, diluted with water and extracted with ether. The ether extracts were washed with water and brine, dried over magnesium sulfate and evaporated to give 2.2 g of a liquid. Column chromatography on silica gel, eluting with petroleum ether, gave 1.4 g (58% of theory) of chloromethyl (phenyl) bis (2-propoxy) silane as a colorless liquid: n _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).

Compounds listed in Tables X and XI were prepared by the method of Examples 33-35.

Example 36

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

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

NMR (CDCl3)

1.1 (12H, d, J-1),

4.0 (2H, s);

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

7.2 to 8.0 (7H, m).

Similarly, the compounds listed in Tables XII and XIII were prepared.

Table X

ORe

AND

R1-Si-CH2Cl

AND

ORe

Ri Re C2H5 t-C 4 H 9 n-C4H9 C2H5 n-C 18 H 37 CH3 cyclohexyl n-C3H7 1-Naphthyl 1-C4H9 phenyl CH3 phenyl n-C3H7 phenyl t-C 4 H 9 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 I-C4H9 2,4-dlchlorophenyl CH3 2,4-dichlorophenyl C2H5 2-methoxy-5-fluorophenyl I-C3H7 2,6-dimethoxyphenyl CH3 3,4-dichlorophenyl C2H5 3,5-dichlorophenyl n-C4Hg

n _D 22 1.4962;

Table IX 'a,

Ri R2 Re Qt Q2 C2H5 CH3 CH3 CH3 CH3 cyclohexyl CH3 I-C3H7 H CH3 n-C 18 H 37 η-0βΗΐ3 t-C 4 H 9 CH3 CH3 1-Naphthyl CH3 I-C3H7 CH3 CH3 phenyl CH3 I-C4H9 H CH3 phenyl CH3 t-C 4 H 9 CH3 H phenyl CH3 t-C 4 H 9 CH3 CH3 phenyl CH3 S-C4H9 H CH3 phenyl CH3 I-C4H9 H CH3 4-phenylphenyl 11-C4H9 t-C 4 H 9 H CH3 4-phenylphenyl CH3 t-C 4 H 9 H CH3 4-phenylphenyl CH3 t-C 4 H 9 CHs CH3 4-chlorophenyl CH3 t-C 4 H 9 H CHs 4-chlorophenyl CH3 t-C 4 H 9 CH3 CHs 4-fluorophenyl CH3 t-C 4 H 9 H CH3 4-fluorophenyl CH3 t-C 4 H 9 CHs CH3 phenyl phenyl C2H5 CH3 CH3 phenyl phenyl n-C3H7 CH3 CH3 4-fluorophenyl phenyl I-C3H7 H CH3 4-fluorophenyl phenyl t-C 4 H 9 CH3 CH3 4-chlorophenyl phenyl I-C3H7 H CH3 2,4-dichlorophenyl phenyl H CH3 CH3 4-fluorophenyl 4-fluorophenyl t-C 4 H 9 H CH3 4-fluorophenyl 4-fluorophenyl t-C 4 H 9 CH3 H 4-fluorophenyl 4-fluorophenyl t-C 4 H 9 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 was cooled to -78 ° C under a nitrogen atmosphere and stirred vigorously with slow dropwise addition over a period of 48.0 mL (0.100 mol). 2.1 molar phenyllithium. Stir for an additional 30 minutes at -78 ° C, then allow the solution to warm to room temperature and evaporate to 200 mL. Ether (500 ml) was added, the lithium chloride was removed by filtration and the filtrate was evaporated to give 25.0 g of liquid. Distillation gave 6.5 g (29%) of chloromethyl (dichloro) phenylsilane as a colorless liquid;

boiling point 62-82 ° C (19,99 Pa); NMR (CDCl 3) δ: -

3.3 (s, 2) and

7.1 to 7.9 (m, 5).

Preparation of chloromethyl (diethoxy) phenylsilane

A solution of 1.0 g (0.0044 mole) of chloromethyl (dichlorophenylsilane) in 8 mL of absolute ethanol was cooled to 0 ° C in at least ¹ N of nitrogen and stirred while slowly adding 0.61 mL (0.445 g, 0.0044 mole). of triethylamine to give a suspension which is slowly warmed to room temperature, 50 ml of ether are added, the precipitated triethylamine / hydrochloride is removed by filtration, and the filtrate is evaporated to give a residue which is filtered through a short silica gel column ( eluačního agent employs 95% petroleum ether: ethyl acetate) to give 0.80 g (73%) of chloromethyl (diethoxy) phenylsilane as a colorless oil ^1:

NMR (CDCl3)

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

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

7.2 to 7.9 (m, 5).

238826

Ri Ra Re

4-chlorophenyl CH3 C2H5 4-fluorophenyl n-C6H13 n-C3H7 4-fluorophenyl CH3 C2H5 4-Phenoxyphenyl cyclohexyl 1-C4H9 4-t-butylphenyl n-Cl7 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-C 4 H 9 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 I-C4H9 n-C 18 H 37 phenyl CH3 1-Naphthyl phenyl C2H5 phenyl phenyl t-C 4 H 9 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-C 1 H 8 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 I-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 (MgSO 4) and evaporated to give 2.3 g of a viscous oil. Chromatography on silica gel, eluting with hexane and then ether gave 1.1 g (42%) of the title compound as a viscous oil which solidified on standing.

Melting point: 97-99 ° C;

NMR (CDCl3)

0.5 (3H, s);

3.9 (2 H, s),

5.2 (1H, broad sj,

7.3 to 7.8 (9H, m),

7.9 (1 H, s),

8.0 (1H, sj.

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

Example 32d

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

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

n _D ²² 1.5387;

NMR (CDCl3)

3.2 (2H, d,

7.2 (4H, ie,

7.8 (4H, d from d).

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

mp 165-168 ° C;

NMR (CDCl3)

4.1 (2 H, s),

7.0 (4 H, t),

7.4 (4H, d from DJ),

7.8 (1 H, s),

7.9 (1 H, s).

Table VIII

Ri R6 R6

C2H5 CH3 CH3 t-C 4 H 9 CH3 t-C 6 H 8 n-Cl9 CHs C2H5 h-Cl2H25 C2H5 CH3 11-C18H37 n-C6H13 CH3 cyclopropyl CH3 S-C4H9 cyclohexyl CH3 CH3 1-naphthyl I-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 I-C4H9 H 4-phenylphenyl n-C4H9 CH3 4-phenylphenyl I-C4H9 H 4-phenylphenyl CH3 C2H5 4-phenylphenyl CH3 n-CaHg 4-chlorophenyl II-C4H9 n-C4H9 4-chlorophenyl CH? CH?

yielding (Γ, Γ-biphenyl-4-yl) (1H-1,2,4-triazol-1-ylmethyl) methoxy / methylsilane.

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

for the R-hydroxyl group, water is used instead of alcohol and the hydrolysis is carried out at 20-25 ° C instead of at 70 ° C.

Example 32

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

A mixture of 3.6 g (0.015 mol) of chloromethyl (1,1-dimethylethoxy) methyl (phenyl jsilane) and 1.3 g (0.015 mol) of 1,2,4-triazole sodium salt in 8 ml of dimethylformamide was stirred at 80 ° C for The mixture was extracted with ether and the ether extracts were washed with water and brine, dried (MgSO 4) and evaporated to give 2.7 g of a yellow oil. 50:50 ethyl acetate-hexanes gave 1.5 g (36%) of (1,1-dimethylethoxy) methyl (phenyl) (1H-1,2,4-triazol-1-ylmethyl) silane as a slightly yellow oil:

m ?! 1.5134;

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

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

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

700, 680 ^cm-1;

NMR (CDCl 3)

0.0 (3H, sj,

1.3 (9H, s)

3.9 (2 H, s),

7.3 - 7.7 (5H, ia,

7.9 (1H, sj a)

8.0 (1H, sj.

The compounds listed in Tables VIII and IX, wherein

Q 1 = q ₂ = H can be prepared similarly as described in Examples 31 and 32.

Example 32a

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

A mixture of 10.0 g (30.6 mmol of chloromethylphis (4-fluorophenyl)] (2-propoxy) silane and 3.1 g (30.6 mmol of 1,2,4-triazole as the sodium salt in dimethylformamide) was stirred at 80 DEG-90 DEG C. under nitrogen for two hours, working up as in Example 32 to give 3.0 g (30%) of the title compound, recrystallization from chlorobutane to give the pure compound, mp 130 DEG-131 DEG C .;

NMR (CDCl 3)

4.1 (2H, s).

5.8 (1H, broad s),

7.1 (4H, t).

7.7 (4H, d from d),

7.8 (1H, s,

8.0 (1 H, s).

Example 32b

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

Proceed as described in Example 32a using chloromethyl [bis (4-chlorophenyl)] (2-propoxy) silane to give an oil which was triturated with hexanes, then the hexane layer was decanted and the residual oil was recrystallized from system 9. : 1 hexanes-ethyl acetate to give the 1H isomer as a solid.

Mp 130-131 ° C;

NMR (CDCl 3)

4.1 (2H, s,

6.3 (1H, broad sj,

7.4 (4H, DJ)

7.6 (4H, dj)

7.8 (1 H, s),

8.0 (1H, sj.

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

NMR (CDCl 3)

1.7 (1H, broad s),

4.2 (2 H, s),

7.8 (8H, s,

7.8 (2H, sj.

Example 32c

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

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

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-C 18 H 37 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 1: 1 (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane / cuprous chloride complex.

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

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

990, 840, 825, 760, 700 cm ¹ .

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

: 1 complex with cuprous chloride, m.p. 83-87 ° C; 1 complex with cuprous chloride, m.p. 85-92 ° C;

1: 1 complex with zinc chloride: n _D ²¹ 1.5737,: 1 complex with manganese sulfate, m.p. 244-250 ° C with decomposition.

Example 29

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

A solution of 1.0 g (0.0034 mol) of (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane in 10 ml of dichloromethane is combined with solution 1, 1 g (0.0034 mol) of 4-dodecylbenzenesulfonic acid in 10 ml of dichloromethane. The resulting solution was evaporated to give (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 4-dodecylbenzenesulfonate salt as a viscous yellow oil:

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

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

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

1010, 990, 735, 700, 670, 635 cm ^-1 .

Example 30

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

A mixture of 1.0 g (0.0032 mol) of [bis (4-fluorophenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl) silane and 0.2 g (0.0016 mol) of chloride of copper (II) in 30 mL of tetrahydrofuran was heated at reflux under nitrogen for 30 min and evaporated to give a 2: 1 [bis (4-fluorophenyl)] methyl (1H-1,2,4-triazole-1-) complex. ylmethyl Jsilane and cuprous chloride in the form of blue-green glass: there is no significant melting point;

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

785 cm ¹ .

Similarly, a 1: 1 complex with copper (I) chloride was prepared as a dark green glass without significant melting point; ir as above.

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

Example 31

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

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

Example 26

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

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

Example 27

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

A solution of 5.9 g (0.020 mol) of (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane in 40 mL of dry tetrahydrofuran was cooled to -40 ° C. 12.5 ml (0.020 mol) of a 1.6 molar solution of n-butyllithium in hexane was added dropwise while stirring, and the resulting yellow solution was stirred for a further 15 minutes at -40 [deg.] C. 1.9 ml (4.2 g, 0.030 moles) of methyl iodide were allowed to warm to room temperature, the solution was diluted with water and extracted with hexanes, and the organic extracts were washed with water and brine, dried (MgSO4) and evaporated to give 50 mg. 5.7 g of solid are obtained, which is purified by dry column chromatography on silica gel (ethyl acetate solution) to give 1.1 g of crude product, and recrystallization from 12 ml of hexanes-ethyl acetate 3: 1 yields 0.97 g. (16 (% of theory) (1,1'-biphenyl-1H-1,2,4-triazol-1-ylmethyl) [bis (4-fluorophenyl)] thylsilane as a white solid:

mp 95-98 ° C;

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

765.700 cm '*

NMR (CDCl3)

0.5 (6H, sj,

2.2 (3H, s)

3.7 (2H, s,

7.2 - 7.7 (9H, m),

7.8 (1H, ss.

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

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

Table VII

Ri R2 R3 Qi Q2 C2H5 ch ₃ CH3 CH3 CH3 n-C 16 H 37 CH3 CH3 H CHs cyclohexyl CH3 CHs CH3 CH3 1-Naphthyl ch ₃ CH3 CH3 CH3 phenyl CH3 CH3 H CH3 phenyl CH3 CH3 CH3 H 4-phenylphenyl CH3 CH3 CH3 CH3 4- (4-fluorophenyl) phenyl ch ₃ CH3 CH3 CH3 4-Phenoxyphenyl ch ₃ CH3 CH3 CH3 3-trifluoromethylphenyl ch ₃ CH3 CH3 CH3 2-methoxyphenyl CH3 CH3 CH3 CH3 2,4-dichlorophenyl ch ₃ CH3 CH3 CH3 2-chloro-4-phenylphenyl CH3 CHs CH3 CH3 phenyl n-CiHg CH3 CH3 CH3 4-phenylphenyl n-CaHg CH3 H CH3 2,4-dichlorophenyl n-C 6 H 13 CH3 CHs CH3 4- (4-chlorophenoxy) phenyl cyclohexyl CH3 CHs CH3 phenyl phenyl CHs H CH3 4-fluorophenyl phenyl CHs CH3 CH3 4-fluorophenyl phenyl CH3 H CH3 4-chlorophenyl phenyl CH3 H CH3

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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 clilormethyl-bis (4-chlorophenyl) methylsilane and 2.0 g (0.022 mol) of 1,2,4-triazole sodium salt in 10 ml of dry dimethylformamide is stirred at 80 ° C for 4 hours. The resulting suspension was cooled, diluted with water and washed with ether. The ether extracts were washed with several portions of water and one portion of brine, dried over magnesium sulfate and evaporated to give 5.4 g of a yellow oil: by distillation in a flask at 120 to 150 ° C (air bath) and at 6, 4.0 g (58% of theory) of bis (4-chloromethyl-methyl (1H-1,2,4-triazol-1-ylmethyl) -silane) are obtained in the form of a slightly yellow oil: n _D ²⁶ 1.5966;

NMR (CDCl3)

0.7 (3H, s);

4.1 (2H, s).

7.2 - 7.5 (8H, ia,

7.8 (1 H, s),

7.9 (1 H, s).

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

Example 25

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

A mixture of 4.2 g (0.015 mol) of (chloromethyl) bis (4-fluorophenyl) methylsilane and 1.4 g (0.015 mol) of 1,2,4-triazole sodium salt in 8 ml of dimethylformamide was stirred at 80 ° C for two hours. The resulting suspension was cooled, diluted with water and treated as described in Example 24 to give 4.0 g of a slightly yellow colored oil. The impurities were removed by distillation in a 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:

n _D ²¹ 1.5538;

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

1270, 1235, 1165, 1110, 1010, 830, 790 cm @ -1; NMR (CDCl3)

0.7 (3H, s,

4.2 (2H, s);

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

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

7.8 (1H, sj a)

7.9 (1 H, s).

A similarly prepared sample after recrystallization from hexane at-120 ° C gave a colorless solid, mp 52-53 ° C. According to Examples 19 and 21 to 25, from the appropriate chloromethylsilanes, compounds of Table VI are prepared wherein Q 1 = Q 2 = H.

g sample of single recrystallized 1 ', 1'- (biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-ylmethyl) silane, prepared as described in Example 14, using sodium methoxide-1,2,4-triazole is subjected to high pressure liquid ehromatography (sillkagel Water Prep PAK-500, flow rate 250 ml / min.). -triazol-1-ylmethyl compound, m.p. 99-100 [deg.] C. Continued elution with 80:20 ethyl acetate-acetonitrile gave a small amount of 1,1'-biphenyl-4-yl (dimethyl J-4H-1,2). 4-triazol-4-yl (methyl jsilane as a colorless solid, m.p. 130-133 ° C; NMR (CDCl 3))

0.4 (6H, s);

3.7 (2 H, s),

7.2 - 7.7 (9H, m),

7.9 (2H, sj.

Microanalysis for C17H19N3Si (MW 293.43) calculated:

C 69.58, H 6.53 N 14.32 found:

C 69.00 H 6.70 N 13.90

C 69.30 H 6.70 N 14.2

Example 21

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

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

boiling point 99 ° C at 2.66 Pa;

n _D ²⁰ 1.5403;

NMR (CDCl3)

0.4 (6H, s);

3.8 (2H, s,

7.2 - 7.7 (5H, m),

7.7 (1H, s,

7.8 (1 H, s);

Analysis for C 11 H 15 N 3 Si (MW 217.34) calculated:

No 60.78 H 6.96 N 19.33 found:

C 60.70 H 7.00 N 16.90

C 60.20 H 7.00 N 16.80

Example 22

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

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

n _D ²¹ 1.5428;

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

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

NMR (CDCl3)

0.4 (6H, s);

3.8 (2 H, s),

7.4 (4H, broad s),

7.8 (1H, ss.

Example 23

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

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

n _D ²³ 1.5580;

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

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

NMR (CDCl3)

0.5 (6H, s);

X = R 1, R 1 -R 2 R 5

2,4-dichlorophenyl n-C4H9 C2H5 2,3-dimethylphenyl cyclopropyl I-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-C 12 H 25 2,4-dichlorophenyl I-C4H9 n-CwH37 phenyl CH3 1-Naphthyl phenyl C2H5 phenyl phenyl t-C 4 H 9 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 I-C3H7 3,5-dichlorophenyl phenyl n-C3H7 4-fluorophenyl 4-fluorophenyl t-C 4 H 9 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 I-C4H9 2-methoxyphenyl 2-methoxyphenyl H 2-chlorophenyl 4-fluorophenyl H 3-trifluoromethylphenyl 4-t-butylphenyl n-CdH9 2-fluoro-4-chlorophenyl 4-bromophenyl I-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- _C 3 H 7 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 mole) of (1,1'-biphenyl-4-yl) chloromethyldimethylsilane and 1.1 g (0.012 mole) of 1,2,4-triazole sodium salt in 5 ml of dimethylformamide is maintained at a temperature of 80-50 ° C. 90 ° C for two hours, cooled, diluted with water and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulfate and evaporated to give 2.3 g of a colorless solid, mp 79-86 ° C. Recrystallization from a mixture of 25 ml of hexanes and 2 ml of ethyl acetate gave 1.1 g (38% of theory) of (1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane, m.p. mp 92-93 ° C;

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

7.2 - 7.7 (9H, m),

7.8 (1 H, s),

7.9 (1 H, s);

Analysis for C17H19N3SI (MW 293.43) calculated:

C 69.58 H 6.53 N 14.32 found:

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

An equimolar mixture of 1,2,4-triazole and sodium methoxide may be used in place of the previously prepared sodium triazole salt. These reactants must be mixed prior to the addition of the silane, as chloromethylsilane reacts very intensively with sodium methoxide in dimethylformamide to give undesired products.

NMR (CDCl3)

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

Example 20

Preparation of (l ' -biphenyl-4-yl) dimethyl _(4H-l? 2,4-triazol-4-ylmethyl) silane rope, so the oil was dissolved in hexanes containing 30 ml of isopropanol and the solution is chilled in ice and Treat with 42 ml (0.30 mol) of triethylamine in hexanes. The resulting suspension was stirred at room temperature for three hours and filtered and the filtrate was evaporated to give an oil. Distillation gave 44.8 g (43% of theory) of the title compound as a colorless liquid, bp 120-140 [deg.] C; n _D ²² 1.5211;

NMR (CDCl3)

1.2 (6H, d),

3.2 (2H, s).

4.1 (1 H, septet),

7.1 (4H, t).

7.7 (4H, d from d).

Example 18

Preparation of chloromethyl (ethoxy) methyl (phenyl) silane

A solution of 18.2 mL (18.2 g, 0.10 mol) of chloromethyl (diethoxy) methylsilane in 200 mL of dry ether was stirred vigorously under nitrogen and cooled while adding 56 mL (0.10 mol) of 1.8 of a 70: 30 cyclohexane-ether solution at a rate such that the temperature of the mixture is below -50 ° C. The resulting suspension was allowed to warm to room temperature, treated cautiously with 10 mL of ethyl acetate, washed with water and brine, dried over magnesium sulfate and evaporated to give 16.8 g of a golden yellow oil. Distillation gave 9.5 g (44% of theory) of chloromethyl (ethoxy) methyl] phenyl silane as a colorless liquid, b.p. 80 DEG-84 DEG C. at 1 mm Hg;

n _D ²⁰ 1.5144;

NMR (CDCl3)

0.5 (3H, s), 1.2 (3H, t, J = 7),

3.0 (2H, s);

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

7.2-7.8 (5H, m).

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

Table V

R2

AND

X — Si — CH2GI

AND

ORe

X = R 1, R 1 -R 2 Re

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Example 16

Preparation of chloromethyl (methoxy) methyl (phenyl) silane

A solution of 1.6 mL (1.3 g, 0.040 mol) of methanol and 3.0 mL (2.2 g, 0.022 mol) of triethylamine in 100 mL of ether was stirred while adding a solution of 4.1 g (0.020 mol) of chlorine ( chloromethyl) methyl (phenyl jsilane in 10 ml of ether dropwise) The resulting suspension was maintained at reflux for two hours, cooled, washed with water, 0.1 N aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution and brine, dried with magnesium sulfate and evaporated to give 3.2 g of a slightly yellow liquid to give 1.7 g (42%) of chloromethyl (methoxy) methyl (phenyl jsilane) as a colorless liquid:

boiling point 46-49 [deg.] C at 6.66 Pa; n _D ²² 1.5207;

NMR (CDCl3)

0.5 (3H, s);

3.0 (2H, s,

3.5 (3H, s);

7.3-7.8 (5H, m).

Example 17

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

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

n _D ²¹ 1.5010;

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

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

1030, 815, 790, 740, 725, 705, 650 cm ^-1 ; NMR (CDCl3)

0.3 (3 H, s),

1.3 (9H, s).

2.9 (2H, s);

7.3 - 7.8 (3H, m).

Example 17a

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

A solution of 73.3 g (0.315 mol) of 4-bromobiphenyl in 300 ml of tetrahydrofuran is added dropwise to a stirred suspension of 7.64 g (0.315 mol) of magnesium in 100 ml of tetrahydrofuran at such a rate that the temperature is maintained at moderate reflux. The resulting clear solution was stirred at room temperature for one hour and then cooled in ice, and a solution of 40 ml (0.315 mol) of chloromethyl (dichloro-methylsilane in 100 ml of tetrahydrofuran) was quickly added and the solution was stirred at room temperature for 20 hours. The reaction mixture was treated with 50 ml of isopropanol and cooled again in ice, and a solution of 48 ml (0.344 mol) of triethylamine in tetrahydrofuran was added at such a rate that the temperature of the mixture was kept below 25 DEG C. Stirring at room temperature for 90 minutes gave a suspension. Filtration, evaporation of the filtrate, trituration with hexanes and a second filtration remove the amine hydrochloride residues, and evaporation of the hexane solutions afforded 92 g (96%) of the title compound as a pale yellow oil which solidified on standing.

NMR (CDCl3)

0.5 (3H, s);

1.2 (6H, d),

3.0 (2H, s);

4.2 (1 H, septet),

7.3-7.8 (9H, m).

Example 17b

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

A mixture of magnesium (23.2 g, 0.955 mol) and iodine (50 mg) in ether (200 ml) was stirred while adding a solution of 4-bromofluorobenzene (167 g, 0.954 mol) in ether (600 ml) at such a rate as to maintain the reflux temperature. It is then kept at reflux for a further 2 hours, the solution is cooled in ice and stirred with the dropwise addition of a solution of 40 ml (0.32 mol) of chloromethyltrichlorosilane in ether over 40 minutes. The resulting mixture was stirred at room temperature for 17 hours, cooled in ice, treated with 24 ml of isopropanol, stirred for an additional 10 minutes, and filtered. The filtrate was concentrated to a gummy solid, hexanes were added and the resulting suspension was filtered and the hexane filtrate was evaporated to give an oil. NMR analysis showed the presence of unreacted chlorine238626

Table IV

R2

X - Si - CH: Cl

X = Ri, Ri *

C2H5 t-CaHg

11-C 4 H 9 n-C 12 H 25

11-C18H37 cyclopropyl cyclohexyl

1- Naphthyl

2-naphthyl phenyl

4-phenylphenyl

4-phenylphenyl

4-chlorophenyl

4-chlorophenyl

4-fluorophenyl

4-Phenoxyphenyl

4-t-butylphenyl

4-trifluoromethoxyphenyl

4- (4-fluorophenyl) phenyl

3-Trifluoromethylphenyl

2-thiomethylphenyl

2,4-dichlorophenyl

2,4- dichlorophenyl

2-chloro-4-phenylphenyl

2,3-dimethylphenyl

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

3-Methyl-4-chlorophenyl

3,5-dichlorophenyl n-C 12 H 25 n-C 16 H 37

1-naphthyl phenyl

4-fluorophenyl

4-chlorophenyl 4-phenylphenyl 4-t-butylphenyl

3-fluorophenyl

2-methoxyphenyl

2-chlorophenyl

2,4- dichlorophenyl

3,5-dichlorophenyl

4-fluorophenyl 4-chlorophenyl 4-phenylphenyl

2,4-dichlorophenyl

3-Trifluoromethylphenyl 2-methoxyphenyl

2-chlorophenyl

3-trifluoromethylphenyl 2-fluoro-4-chlorophenyl

2,3-dimethylphenyl

2,6-dimethoxyphenyl

3,4- dichlorophenyl

4-chlorophenyl

Cl

R2

CHs

CH3

CH3

C2H5 n-C6H13

CH3

CH3

1-C 3 H 7 cyclobutyl 1-C 1 H p n-C 1 H 8 n-C 6 H 13 n-C 4 H 9

CH 3 n-C 6 H 13 cyclohexyl n-C 3 H 7

CHs

CH 3 t-C 1 H 9 cyclopentyl

CH3 n-CiHa

CHs cyclopropyl

S-C4H9

1,1-dimethylpropyl

C2H5 n-CsHi

2.4-Dichlorophenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl

4-fluorophenyl

4-chlorophenyl

4-phenylphenyl

2,4- dichlorophenyl

3-Trifluoromethylphenyl

2-methoxyphenyl

4-fluorophenyl

4-t-butylphenyl

4-bromophenyl

4-methylthiophenyl

4-methoxyphenyl

4-methylphenyl

4-chlorophenyl, mp 110-130 ° C (13.33 Pa)

X = Ri, Ri ‘

R2

R3 phenyl

1-Naphthyl

4-Phenoxyphenyl

4-fluorophenyl

4-chlorophenyl

4-bromophenyl

3,5-dimethylphenyl

4-fluorophenyl

4-phenylphenyl

3-methylphenyl

3,4-dichlorophenyl

4-fluorophenyl, mp 57-60 ° C

Example 14

Preparation of chloro (chloromethyl) methyl (phenyl) silane

A solution of 12.7 mL (16.4 g, 0.10 mol) of chloromethyl (dichloro-methylsilane in 200 mL of ether) was cooled to -70 ° C under a nitrogen atmosphere and stirred vigorously with the addition of 55 mL (0.10 moles). )

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

boiling point 71-74 [deg.] C under 1 mm Hg; n _D ²³ 1.5337;

ir (neat) 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 jmethylsilane) (1,1'-Biphenyl-4-yl) chloro (chloromethyl j methylsilane) can be prepared by reacting an equimolar amount of 4-bromobiphenyl, chloromethyldichloro (methyl) silane and n. -butyllithium as described in Example 3.

Example 14a

Preparation of chloro [bis (4-fluorophenyl) Jinethylsilane

A suspension of 7.0 g (0.288 mol) of magnesium turnings in 50 ml of ether was stirred under a stream of nitrogen while dropwise addition of the solution.

50.2 g (0.287 mol) of 4-bromofluorobenzene in 200 ml of ether at such a rate that the temperature was maintained at reflux. After an additional two hours of 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 in a stream of nitrogen and evaporation afforded a mobile oil which was distilled to give a crude oil

17.6 g (61%) of the title compound, b.p. 100-140 ° C (13.32 Pa);

NMR (CDCl3)

3.3 (2H, sj)

7.1 (4H, t);

7.7 (4H, d from d).

Example 15

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

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

CbSiCH2Cl

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

Table III

Rz

AND

X - Si - CH 2 Cl

I: aotA »....

R3

X = R1, R1-R2 R3

C2H5 C2H5 C2H5 1-C3H7 I-C3H7 1-C3H7 n-ClHg n-C4H9 n-C4H9 U-CbH17 C2H5 cyclopentyl n-C 14 H 29 cyclopropyl 1-methylbutyl n-C 16 H 37 n-CeHu n-C6H13 cyclopropyl C2H5 S-C4H9 cyclohexyl 11-C3H7 n-C3H7 1-Naphthyl 11-C4H9 11-C4H9 2-Naphthyl n-C4H9 cyclobutyl phenyl cyclopropyl n-C6H13 4-phenylphenyl n-C4H9 n-C4H9 4-phenylphenyl 11-C6H13 n-C6H13 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-C 6 H 8 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 I-C4H9 t-CdHg 3,5-dichlorophenyl cyclopentyl cyclopentyl 3-methyl-4-chlorophenyl S-C4H9 S-C4H9 C2H5 phenyl phenyl cyclohexyl phenyl phenyl n-C 18 H 37 phenyl phenyl tl-C4H9 4-chlorophenyl 4-chlorophenyl n-C 12 H 25 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 I-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 1-5 from suitable organolithium or Grignard compounds and compounds of formula

Cl (R 2) Si (R 3) CH 2 Cl

The desired chlorochloromethyl dialkylsilanes are prepared from a compound of formula

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

mp 112-115 ° C;

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

NMR (CDCl3)

3.5 (2H, s);

7.0 - 7.8 (15H m).

Cl3SiCH2Cl

Example 13a using two equivalents of compound of formula

R 2 MgCl or R 2 L 1 if R 2 is the same as R 3 (see, for example, A. A. Zdanov, V. I. Pachomov and T. Bazanova, Zur. Obs. Chim., 1973, p. 1280), or using one equivalent of a compound of the formula

R 2 MgCl or R 2 L 1 and then one equivalent of a compound of formula

R3MgCl or R3L1 when R2 and R3 do not have the same meaning.

Example 13

Preparation of (chloromethyl) triphenylsilane

A solution of 12.6 mL (18.4 g, 0.10 mol) of (chloromethyl jtrichlorosilane) in 150 mL of dry ether was stirred under nitrogen and cooled with ice while adding 162 mL (0.30 mol) of 1.85 molar phenyllithium solution. in a 70: 30 cyclohexane-ether system dropwise at a rate such that the temperature of the mixture was maintained below 15 [deg.] C. The resulting suspension was stirred overnight at room temperature, carefully treated with 10 ml.

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

A solution of 24.5 g (0.128 mol) of 4-bromochlorobenzene in dry tetrahydrofuran was cooled to -60 ° C under a stream of nitrogen and 80 ml (0.128 mol) was added with stirring.

Of a 1.6 molar solution of n-butyllithium in hexane at a rate such that the temperature of the mixture was maintained below -50 ° C. The resulting solution was stirred for an additional 10 minutes at -60 to -70 ° C and then a solution of 5.2 ml (0.041 mol) of chloromethyltrichlorosilane in tetrahydrofuran was added dropwise over 30 minutes. The resulting solution was stirred at RT. at -70 ° C for one hour, allowed to warm to room temperature, quenched with saturated aqueous ammonium chloride, and extracted with ether. The ether solution was washed with brine, dried (MgSO4) and evaporated to give a viscous oil which was chromatographed on silica gel (hexane elution) to give

9.1 g (53% of theory) of the title compound as a colorless oil which solidifies on standing:

mp 89-93 ° C;

NMR (CDCl3)

3.4 (2H, s,

7.5 (12H, broad ref.

Table II

CH3

AND

X - Si - CH 2 Cl

AND

R2

X = R1, R1 *

C2H5

I-C3H7

II-C 4 H 9 n-C 10 H 11 n-C 18 H 17 cyclopropyl cyclohexyl

1- Naphthyl

2-naphthyl phenyl phenyl phenyl

4-phenylphenyl

4-bromophenyl

4-fluorophenyl

4-Phenoxyphenyl

4-t-butylphenyl

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

2,4- dichlorophenyl

2,3-dimethylphenyl

2-methyl-5-fluorophenyl

2,5-dimethoxyphenyl

2,6-dimethylphenyl

3,5-dichlorophenyl

3,5-Diclorophenyl

3-Methyl-4-chlorophenylphenyl

4-fluorophenyl

4-chlorophenyl

4-bromophenyl

4-phenylphenyl

4-t-butylphenyl

4-thiomethylphenyl

4-Phenoxyphenyl

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

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

2-fluoro-4-phenylphenyl

3,5-dichlorophenyl

2,5-dimethoxyphenyl

2,6-dimethoxyphenyl

4-bromophenyl

4-phenylphenyl

4-methoxyphenyl

3-Trifluoromethylphenyl 2-methoxyphenyl 2-chlorophenyl

2,4- dichlorophenyl

3,5-dichlorophenyl

R2

C 2 H 5 cyclohexyl n-C 4 H 8 cyclopropyl

3-Methylbutyl n-CsH13 cyclohexyl t-C1Ho n-CsHu n-C3H7 n-ChHg

1,1-dimethylpropyl

C2H5

1-C 3 H 7 n-C 1 H 8 t-C 4 H 9 cyclopentyl

S-C 4 H 9 n-C 5 H 11 cyclobutyl

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

m.p. 45 ° C (6.66 Pa)

mp 82-90 ° C (13.33 Pa)

mp 90-92 ° C (13.33 Pa)

m.p. 109-112 C (13.33 Pa)

mp 104-110 ° C (26.66 Pa) n _D ²² 1.5624

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

mp 132-135 ° C (13.33 Pa)

mp 160-170 ° C (13.33 Pa)

mp 115-117 ° C

mp 166-171 ° C (13.33 Pa)

mp 135-140 ° C (13.33 Pa) n ₀ 21 1.5956

NMR (CDCl3)

0.7 (3H, s);

3.1 (2H, s).

7.2-7.7 (8H, m);

Analysis for C14H13Cl3Si (molecular weight 315, 70) calculated:

C 53.26 H 4.15 Cl 33.69 found:

C 53.4 H 4.4 Cl 34.2

C 53.5 H 4.4 Cl 34.1

Example 10

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

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

bp 107-127 ° C (at 13.33

Bye);

n _D ²² 1.5481;

NMR (CDCl3)

0.7 (3H, s);

3.2 (2H, s).

7.1 (4H, t, J = 9)

7.6 (4H, d, z, D1) = 6 and 9).

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

NMR (CDCl3) see above.

A similar sample of the title compound after recrystallization from ether-hexane at -78 ° C gave a colorless solid, mp 39-40 ° C.

Example 11

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

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

2-Bromo-chlorobenzene in 75 mL of dry tetrahydrofuran was cooled to -60 ° C under a nitrogen atmosphere and stirred while adding 31 mL (0.05 mol) of a 1.6 molar solution of n-butyllithium in hexane at such a rate that the temperature of the mixture The temperature was maintained below -55 [deg.] C. Stirring and cooling was continued with the addition of 8.1 g (0.05 mol) of 4-bromochlorobenzene as a solid followed by an additional 31 ml portion of a 1.6 molar n-butyllithium solution at such a rate The resulting slurry was allowed to warm to room temperature, treated cautiously with 10 mL of ethyl acetate, and then treated as described in Example 8 to give 15.0 g of a clear yellow oil. afforded 5.9 g (37% j chloromethyl (2-chlorophenyl j (4-chlorophenyl jmethylsilanu: bp 150-165 ° C at 93.31 Pa, n _D ²⁰ 1.5916;

ir (neat) 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 (2 H, s),

7.2-7.7 (8H, m).

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

Cl ₂ Si (CH ₃ ) CH ₂ Cl ₂ as described in Examples 6-11.

boiling point 115-138 ° C at 25.66 Pa; n _D ²¹ 1.5464;

238826 residue in hexanes, re-filtered and evaporated to give 19.8 g of a slightly orange liquid. By distillation, first 1.8 g (12%) of chloromethyl (-dibutyl) methylsilane having a boiling point of 45 DEG C. at a pressure of 6.66 Pa were obtained, followed by 6.8 g (35%) of butyl (chloromethyl) (4-chlorophenyl) methylsilane. in the form of a colorless liquid:

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

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

740 cm ^-1 ;

NMR (CDCl 3)

0.4 (3H, sj,

0.6-1.5 (9H, m),

2.9 (2 H, s),

7.0-7.4 (4H, qj).

Example 8

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

A solution of 13.6 g (0.060 mol) of 2,4-dichlorobromobenzene and 12.3 g (0.060 mol) of chloro (chloromethyl) methyl (phenyl) silane, prepared as described in Example 14, in 85 ml of dry tetrahydrofuran is rapidly cooled to room temperature. -60 ° C under a nitrogen atmosphere and stirred while adding 38 mL (0.060 mol) of a 1.6 molar solution of n-butyllithium in hexane dropwise at a rate such that the temperature of the mixture was maintained below -55 ° C. Warm to room temperature, treat with 5 mL of ethyl acetate to remove any unreacted excess organolithium reagent and pour into 170 mL of water.

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

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

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

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

NMR (CDCl3)

0.8 (3H, s);

3.4 (2H, s);

7.2 - 7.9 (8H, m).

Example 8a

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

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

Of a 1.6 molar solution of n-butyllithium in hexane at a rate such that the temperature of the mixture was maintained below 50 ° C. Stir at -70 degrees Celsius for an additional 30 minutes, allow the solution to warm to room temperature and work up as described in Example 8. The resulting crude product is distilled at a temperature of 130-150 ° C removal of unreacted starting materials to give the title compound as an oil:

n _D ²³ 1.5128;

NMR (CDCl 3)

0.7 (3H, s);

3.1. (2H, S).

7.1 (2 H, t),

7.2 - 7.8 (11H, inter alia.

Example 9

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

A solution of 4-chlorobromobenzene (19.1 g, 0.10 mol) in dry tetrahydrofuran (200 ml) was rapidly cooled to -60 ° C under a nitrogen atmosphere and stirred with the addition of 63 ml (0.10 mol) of a 1.6 molar solution. n-butyllithium in hexane was added dropwise at a rate such that the temperature of the mixture was maintained below -55 ° C. Stirring and cooling was continued with the addition of 6.3 ml (8.2 grams, 0.05 mol) of chloromethyl (dichloro-methylsilane) dropwise and at a rate such that the temperature of the mixture was kept below -50 ° C. The resulting orange solution was allowed to warm. to room temperature and worked up as in Example 8 to give 16.5 g of a pale yellow oil. % of theory) chloromethyl [bis (4-chlorophenyl)] methylsilane as a colorless liquid:

n _D ²⁴ 1.5913;

ir (neat) 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 as described in Example 1 using (butyl jchlor (chloromethyl) methylsilane) instead of chloro (chloromethyl) dimethylsilane.

Related compounds can be prepared by the method of Examples 1-5 using suitable organolithium compounds or Grignard reagents and suitable compounds of formula

Cl (R 2) Si (CH 3) CH 2 Cl

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

R2MgCl or R2L1 and from CbSi (CH5) CH2Cl as described in Examples 14 and 15 and, for example, by V. P. Kuznetsova and R. M. Sololovaska in the journal Zur. Obščej. Chim., 1969, p. 1997.

Alternatively, both biphenyl and butyl groups can be simultaneously introduced as follows:

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

t 59 to 62 ° C (39,99 Pa) t 73 ° C (19,99 Pa) n _D ²³ 1,4826 n _D ²⁰ 1,5772

t 78-80 ° C (39.99 Pa) n _D ²¹ 1.5164 n _D ²² 1.5254

98 ° C (79.98 Pa)

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

Boiling point 133-158 ° C at 13.33

Bye;

n _D ²² 1.5743;

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

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

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

1 H NMR (CDCl 3)

0.4 (3 H, s),

0.6 - 1.8 (9H, ia,

2.9 (2H, s) a

7.0 - 7.7 (9H, m).

Example 7

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

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

2β

NMR (CDCl3)

0.5 (6Η, s),

3.1 (2H, s);

7.0 - 7.5 (3H, m).

Example 5

Preparation of chloromethyl (2,6-dimethoxyphenyl) dimethylsilane

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

boiling point 98-110 ° C at 1 mm Hg; NMR (CDCl3)

0.4 (6H, s);

3.1 (2H, s).

3.7 (6 H, s),

6.3 (2 H, d),

7.1 (1 H, m).

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

X = Ri or Ri ‘

C2H5 n-CdHg n-C12H5

11-C18H37 cyclopropyl cyclopentyl cyclohexyl

1- Naphthyl

2-naphthyl phenyl

4-fluorophenyl

4-methoxyphenyl

4-Phenoxyphenyl

4- (4-chlorophenoxy) phenyl

4- (4-fluorophenoxy) phenyl

4- (4-Trifluoromethylphenoxy) phenyl

4- (4-methylphenoxy) phenyl

4-thiomethylphenyl

4-trifluoromethylphenyl

4-methylphenyl

4-i-Propylphenyl

4-t-butylphenyl

4-methylsulfonylphenyl

4-cyclohexylphenyl

4-trifluoromethoxyphenyl

4- (4-chlorophenyl) phenyl

4- (4-Bromophenyl) phenyl

Table I

CHs

AND

X - Si - CH 2 Cl

AND

CHs

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

120-130 ° C (1333 Pa) melting point 112 ° C (10.66 Pa)

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

mp 92-93 ° C (6.66 Pa) n _D ²³ 1.4686

tt 96 ° C (933.1 Pa) n _D ²³ 1.5056

mp 64-68 ° C n _D ²¹ 1.5424

mp 55-57 ° C (19,99 Pa) is not agitation. With continued cooling, 5.9 ml (6.7 µg, 0.046 mol) of chloro (chloromethyl) dimethylsilane was added over 10 minutes to give a clear solution which was allowed to warm to room temperature. the precipitated lithium chloride and the filtrate were evaporated to yield

13.2 g semi-solid. Redissolved in ether, filtered and evaporated to afford 11.0 g (100% crude) of Ι, Γ-biphenyl-4-yl (chloromethyl) dimethylsilane as a colorless solid, m.p. Traces of impurities can be removed by sublimation at 30 ° C at 13.33 Pa to give 1,1'-biphenol-4-yl (chloromethyldimethylsilane unsublimed in 83% yield, m.p. Mp 37-40 ° C;

ir (Nujol ^R ) 1585, 1240, 1110, 830, 810, 750, 690 cm &^lt; ^{-1 &gt};;

NMR (CDCl3)

0.4 (6H, s,

2.9 (2 H, s),

7.3-7.7 (9H, m).

Example 2

Preparation of (4-bromophenyl) (chloromethyl) dimethylsilane

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

1.2 g (0.050 gatoms) of magnesium shavings in 75 ml of ether according to G. P. Schiemenz, Org. Syn., Coll. Vol. 5, p. 496: (1973). The resulting mixture was rapidly cooled in ice under nitrogen atmosphere while dropwise addition of the solution.

6.6 ml (7.2 g, 0.050 mol) of chloro (chloromethyl) dimethylsilane in 10 ml of ether are then stirred overnight at room temperature, carefully quenched with saturated aqueous ammonium chloride solution and filtered. brine, dried over magnesium sulphate and evaporated to give 9.8 g of an oil, distilling to give 3.8 g (29%) of (4-bromophenyl) (chloromethyl dimethylsilane) as a colorless liquid:

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

NMR (CDCl3)

0.4 (6H, s,

2.9 (2 H, s),

7.3-7.7 (4H, m).

Example 3

Preparation of chloromethyl (4-chlorophenyl) dimethylsilane

A solution of 9.6 g (0.050 mol) of 4-bromochlorobenzene and 6.6 ml (7.2 g, 0.050 mol) of chloro (chloromethyl) dimethylsilane in 75 ml of tetrahydrofuran is stirred at -78 ° C in nitrogen with the addition of 31 ml ( The resulting clear solution was allowed to warm to room temperature, diluted with ether until no more lithium chloride precipitated and was filtered, and the filtrate was evaporated to give 10.6 g of light light (0.050 mol). a yellow liquid which, by distillation, yielded 6.0 g (55% yield) of chloromethyl (4-chlorophenyl) dimethylsilane as a colorless liquid:

bp 54-55 ° C at 1 mm Hg;

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

1010; 840, 805, 790, 740 cm ^-1;

NMR (CDCl3)

0.4 (6H, s);

2.9 (2 H, s),

7.1 - 7.6 (4H, q).

The in situ aryllithium preparation described in this example is also suitable for the preparation of the product of Example 1. When the reaction is carried out with 0.5 to 0.7 molar amounts of 4-bromobiphenyl and> maintained at -65 to -55 ° C during addition of butyllithl, no precipitate forms or only slightly solid precipitates. Example 4

Preparation of chloromethyl (2,4-dichlorophenyl) dimethylsilane

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

A 1.6 molar solution of n-butyllithium in hexane 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 hexane, filtered and evaporated to give

20.5 g of yellow liquid. Distillation was obtained

12.6 g (66% of theory) of chloromethyl (1,2,4-dichlorophenyl) dimethylsilane as a colorless liquid:

bp 83 [deg.] C at 2.65 Pa; n _D 24 1.5522;

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

825 cm ^-1 ;

3 8 6.2

CHs 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 a temperature with good stirring to achieve the best yields.

Reaction of compound of formula

C 13 SiCH 2 Cl with Grignard reagents was described by A. A. Zdanov, V. I. Pakhomov and T. Bazanov in the journal Zur. Obščej. Chimii, 1973, 1280, Chem. Abstr. 79, 66452 m. The addition of organometallic reagents to trichlorosilane is also recommended when three identical groups are to be introduced, as the addition of a compound of formula

Cl3SiCH2Cl to organometallic reagent

saw was not successful. It can also be introduced single aryl group: Cl

Cl 3 SiCH 2 Cl + ArLi --- Ar-Si-CH 2 Cl

Cl

A useful modification of methods known in the art useful when R 1 or R 1 is an aryl group is described herein. Instead of the previously prepared organolithium reagent and its subsequent mixing with chlorosilane, it has been found that aryl bromide and chlorosilane such as a compound of formula

ClSi (CH 3) 2 CH 2 Cl can be mixed in an inert solvent such as tetrahydrofuran and can be treated at -80 to -40 ° C with butyllithium. The bromine-lithium exchange is selective and the aryllithium formed reacts with the silicon-chlorine bond as soon as the bond is formed:

CH3 | n-CaHaLi

ArBr + Cl-Si-CH 2 Cl ---.

| —CaHgBr

CH3

CH, ³

ArLi + CT-Si. CH.Ct _I-5 ^I CH

CH3

AND

---- ► Ar — Si — CH2Cl — face I

CH3

This reaction proceeds as well for aryl substituted chlorosilanes such as a compound of formula

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

Cl 2 Si (CH 3) CH 2 Cl

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

CH3 CH3 | 2n-C4H9Li |

ArBr + Cl 2 S 1 - CH 2 Cl ----> Ar - Si - CH 2 Cl

In-C4H9

Substitution of n-butyllithium with another alkyl lithium compound of formula RLi provides a general process for preparing compounds of formula

Ar (CH 3) Si (R) CH 2 Cl

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

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

the peak position is reported as parts per million with respect to internal tetramethylsilane. The position of the infrared (IR) peak is reported in reciprocal centimeters (cm ^-1 ). By hexanes is meant a mixture of isomers having a boiling point of 68-69 ° C and ether means diethyl ether.

Example 1

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

A solution of 9.9 g (0.042 mol) of 4-bromobiphenyl in 50 ml of tetrahydrofuran was cooled to -78 ° C under nitrogen and stirred with the dropwise addition of 26.5 ml (0.042 mol) of 1.6 molar n-butyllithium in hexane. within 15 minutes. A thick suspension is formed and tetrahydrofuran (35 ml) is added to facilitate 236262 a

IR-SC-CH3C1->

Cl ·

Glycol derivatives are similarly formed using a diol instead of two molecules of a compound of formula ReOH.

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

R2 | RiMgX (ReO6Si-CH2Cl2->)

RiL1 or RiNa

R2

AND

--- ►R1 - -

AND

ORe

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

The desired chloromethylsilane as starting material is prepared from commercially available chlorine (chloromethyl j dimethylsilane, chloromethyl (dichloro-methylsilane) or chloromethyltrichloromethylsilane

CH3

AND

Cl — Si — CH2Cl,

I ch ₃

CH3

AND

Cl — Si — CH2Cl,

AND

Cl or

R2

AND

CbSiCH 2 Cl -> R 1 -Si-CH 2 Cl

AND

R3

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

to chlorine and can be gradual replacement, thereby a possibility for meaning of the symbols R to R _3rd Bromsilanes, iodosilanes or alkoxysilanes may be used in place of chlorosilanes in these reactions. Preferred solvents for these reactions are ethers such as tetrahydrofuran, 1,2-dimethoxyethane and diethyl ether or hydrocarbons such as hexane and toluene. Temperatures of -80 to +40 ° C are preferred depending on the nature of the organometallic reagent as prepared and the solvent used. For example, when 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 a competitive reaction on the CH 2 Cl 2 group. The reaction is rapid at all temperatures and only a short time is required, for example 30 to 60 minutes after mixing the reagents to ensure complete reaction.

Reaction of compound

ClSiCH5-CH2Cl2 with Grignard reagents are described by C. Eaborn and J. C. Jeffrey in J. Chem. Soc., 1954, p. 4266; recent description of the preparation of aryltrimethylsilanes from a compound of formula

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

ClSi (CH ₃ ) ₂ CH ₂ Cl is described by D. Habich and F. Effenberger in Synthesis 1979, p. 841. Selective introduction of a new alkyl group into a compound of formula

Cl2Si (CH3) CH2Cl was described by V. P. Kuznetsova and R. M. Solokovaskaja in the journal Zur. Obščej. Chim., 1969, 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 as described above for the azoles. The temperature of the alcoholysis is not critical and can be carried out by heating at 50 to 100 ° C to achieve complete reaction in cases where R 6 is C 1 -C 4 alkyl. However, in the case where R 5 is a hydrogen atom, hydrolysis preferably proceeds at a temperature close to room temperature to minimize disiloxane formation, since the silanol-disiloxane equilibrium is always possible when R 6 is a hydrogen atom

Q ,.

Rr Su ~ ⁷ i

OH ^CH A

The equilibrium and rate at which the equilibrium is adjusted depends on the importance of R1 and R2, the solvent selected, the temperature and the possible presence of acidic or basic catalysts.

In the second process, the silicon-oxygen bond is first formed, and the azole is prepared as described above:

R,

Rx-Si-CH3CiQ-1

RrSi-CH _? N ¹ 1 R, I ^£

STEED,

OR, a,

The reaction of chlorosilane with a compound of formula ReOH can be carried out in almost any non-hydroxyl solvent with ethers such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran or in dipolar aprotic solvents such as dimethylformamide, with acetonitrile being preferred. Although it is not necessary to use an acid acceptor, it is preferable to add a tertiary amine such as triethylamine or pyridine. The reaction temperature may be 0 to 100 ° C and the compound of formula R 6 OH is often used in excess of the theoretical amount. Generally, 2 equivalents of the compound of formula R60H are used,

1.1 equivalents of triethylamine and 0.1 equivalents of imidazole in dimethylformamide at 80 DEG C. for two hours.

Using the following methods for (chloromethyl iodochlorosilanes) a strong one containing two oxygen atoms is obtained:

which has a singlet close to 2.9 and singlets of the product

The S1CH2N derivative k at the 4-position of the substituted 10: 1 derivative. The monomethyltriazoles and dimethyltriazoles provide similar 4H-isomers as the products formed in smaller amounts:

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

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

R, - 1

The ratio of isomers varies with the meaning of R and depending on the reaction conditions, roughly the ratio at position 1 is substituted. Using unsubstituted silylmethyltriazole metalation - methylation yields methylated homologs:

^R ro N

1 »CjfHg LL

2-CH ₆ J 11

RvSL-CH. ¹ 1 t

R, r = N, J

CH <

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

CH »

R, - s-cHjM formula IIA '

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

In the case where R5 is OR6 in the triazole or imidazole product, chlorine in chlorine (chloromethylsilane) can be replaced by one of two methods, in which at least two equivalents of the azole sodium salt can be used. azole bond and reaction with water or alcohol yields the desired oxygen-containing compound:

Formula IIB

23862-6

'W.c. > = n 1 ² > = a a, of formula IIB Isomers prevail, of formula IIA as a rule, however, isomers of formula

where

HN. J> -N

Q 1, Q 2 and, Q 1 represent a hydrogen atom or a methyl group. When writing structural formulas take a structural share

Gkj

IIB also have fungicidal activity and isomer separation is not necessary.

Ri also means Ri ‘since all meanings of Ri‘ are included in the definition of Ri. The term "azole" continues to be used for suitably substituted 1,2,4-triazoles and imidazoles

where

X represents a nitrogen atom or CQ 3 group used to designate both the triazole and imidazole ring systems.

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

Lithium and potassium azole salts may also be used. Instead of chloromethylsilanes, bromomethylsilanes, iodomethylsilanes or arylsulfonyloxymethylsilanes may be used. Approximately equimolar amounts of reagents are used (except when R 5 is OR 6 as described below), the azole salt being often used in a 5 to 10% excess above the theoretical amount. In addition, when an acid acceptor is added, 1,2,4-triazole or imidazole may be used as such. Suitable acid acceptors include excess azole, alkali metal alkoxides such as sodium methoxide or potassium tert-butoxide, inorganic bases such as potassium carbonate or hydride. sodium, and tertiary amines such as triethylamine. If the acid acceptor is well nucleophilic, such as sodium methoxide, excess use thereof should be avoided to avoid side reactions. Suitable solvents include polar aprotic solvents such as dimethylformaroid, dimethylsulfoxide or acetonitrile; ethers such as tetrahydrofuran or 1,2-dimethoxyethane; and ketones such as 2-butanone. The reaction temperature may be 0 to 200 ° C, preferably 25 to 100 ° C. The reaction may be carried out at elevated pressure, but it is generally preferred to work at atmospheric pressure. The optimum temperature and reaction time varies depending on the concentration and choice of the reactants, and particularly depending on the choice of solvent. For example, 1,2,4-triazole and sodium methoxide at about 2 molar concentration in dimethylformamide provide good conversion in about two hours at 80-90 ° C, whereas 1,2,4-triazole and potassium carbonate at about 1 molar concentration in dimethylformamide butanone requiring reaction for 8-12 hours at reflux temperature. Imidazole reactions are generally faster. Generally, a reaction time of 1 to 24 hours is required. The progress of the reaction can be monitored by nuclear magnetic resonance analysis and by assessing the intensities of the starting material

SÍCH2CI

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

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

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

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

Particularly preferred are compounds of formula (II) wherein R 1, R 2 or R 3 are not C 1 -C 4 alkyl or phenyl. The following compounds of formula II are preferred for their excellent activity and / or easiest process of preparation:

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

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

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

[bis (4-Fluorophenyl)] (1H-imidazol-1-ylmethyl) methylsilane;

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

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

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

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

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

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

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

Butyl (4-chlorophenyl) (1H-imidazol-1-ylmethyl) methylsilane;

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

Dimethyl (4-fluorophenyl) (1H-imidazol-ylmethyl) silane;

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

When Q1 and Q2 are each hydrogen or methyl, a mixture of two isomers is generally obtained in the preparation of the triazole derivatives of formula (I):

Formula IB

R,

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

/> M

R.-Are-CHrN J formula IC a

CH, formula ID a

of formula IE rSt-CH “Ν '

I z. \ I

R,

CH.

\ *

Sc _r R _r CH N?

R <

> ó t

R,

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

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

R ^ · CH /

Ø, ^N

Λ

R.-S1-CH, N 1 = ^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 the compounds of the formulas I and II with protic acids and their metal ion complexes.

For their activity and / or preferably an easy preparation process, the compounds of the formulas I and II are preferred

Q 1 = Q 2 = - = hydrogen

They are more preferred for their activity: and / or for a preferably easy method of preparing a compound wherein

R 1 and R 1 are a group of formula

R2 is alkyl having 1; up to 4 carbon atoms or a group of formula

R 5 is C 1 -C 4 alkyl.

Most preferred for their highest activity and / or for the easiest method of preparation are the compounds of formulas I and II wherein

R 1 and R 1 ‘a group of formula

where it means

R 1 is para to R 1 or R 1 and is hydrogen, fluoro, chloro or bromo, or phenyl; and

R 5 is hydrogen, fluorine, chlorine or bromine; and

R2 is a group of formula

R 1 or C 1 -C 4 alkyl and

R 5 is C 1 -C 4 alkyl.

The following compounds of the general formula I are particularly preferred for their excellent activity and / or for the easiest process of preparation:

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

Dimethyl (4-methylphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane;

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

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

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

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

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

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

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

(bis (4-Fluorophenyl)) methyl (1H-1,2,4-trlazol-1-ylmethyl) silane;

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

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

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

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

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

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

or η

A aχ ζΟ gene and / or C 1 -C 4 alkyl and / or trifluoromethyl, trifluoromethyl, C 1 -C 4 alkyl or cyclohexyl group,

R 2 and R 3 independently of one another are C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, OR 6 or R 6

OxzO

R,

R _f

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

Kl / rzN Rj-SICHA-J

Q a-j

R 1 '/ R ττΝ -SLCH _F ^ ^r I A, and;

where it means

R 6 is hydrogen or C 1 -C 4 alkyl, provided that R 2 and R 3 are not both hydroxyl, and R 2 and R 5 may together form a 1,2-glycol, 1,3-glycol or 1,4-glycol bridge; , 4-unsaturated glycol bridge substituted with up to 4 R7-R10 alkyl groups having up to 4 carbon atoms in total

Rf R ₁₀

or where it is

Q1, Q2 and Q3 independently of one another are hydrogen or methyl,

R 1 and R 1 are C 2 -C 18 alkyl, C 3 -C 6 cycloalkyl, naphthyl or formula

Rf R «

or

RfR where is

Rd and R5 are independently hydrogen, halogen, methoxy, trifluoromethoxy, thiomethyl —SCH3, —SO2CH3, phenyl, phenyl substituted with halogen and / or C1 -C4 alkyl and / or trifluoromethyl a phenoxy group optionally substituted by a halogen atom

When R2 or R3 is a hydroxyl group, formula I and II include a disiloxane of formula

The guanidino group-containing, organosilicon compounds are active as antifungal agents for molded plastics and rubbers, especially silicone rubbers ^1.

Soviet Patent No. 346,306 protects the methyl methyl azoles of the general formula

(R 1) _n (R 20) ₃ - "SiCH 2 Az 2 where they denote

R1 and R2 are each alkyl, zero to 3 and

The az pyrazole, imidazole or benzimidazole ring, optionally substituted.

Soviet Patent Specification No. 271'552 protects the silylethylazoles of formula (R1) _n (R2O) ₃ . _n SiCH ₂ CH ₂ Az where

R 1, R 2, n and Az are each as defined in Soviet Patent Specification No. 346,306, supra.

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

where it means

R1 and R5 independently of one another are hydrogen, halogen, methoxy, trifluoromethoxy, thiomethyl SCH3, -SO2CH3, phenyl, phenyl substituted by halogen and / or C1-C4 alkyl and / or trifluoromethyl , phenoxy, phenoxy substituted with halogen and / or C 1 -C 4 alkyl and / or trifluoromethyl, trifluoromethyl, C 1 -C 4 alkyl or cyclohexyl, provided that in the case of a compound of the formula: II, R1 and R5 cannot both be hydrogen,

R 2 and R 3 are each independently C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, OR 6 OR

where it means

R 6 is hydrogen or C 1 -C 4 alkyl, provided that R 2 and R 3 are not both hydroxyl, and R a and R 3 may form a 1,2-glycol, 1,3-glycol or 1,4-glycol bridge; or 1,4-unsaturated glycol bridge substituted with up to 4 alkyl groups R? to R10 having a total of up to 4 carbon atoms where is

Q1, Q2 and Q3 independently of one another are hydrogen or methyl,

R 1 is C 2 -C 18 alkyl, C 3 -C 6 cycloalkyl, naphthyl or o- or

R-f R

C 1 -C 6 alkyl or C 1 -C 3 cycloalkyl, naphthyl or formula

Compound of 5 species

Phytophthora restricted in vitro

123

Compound% Tomato Mold Control (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane,

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

1: 1 complex with zinc chloride 90 (4'-Bromo-1,1'-biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-yl-30-methylsilane) (Ι, B-Biphenyl- 4-yl dimethyl (5-methyl-1H-1,2,4-triazol-1-ylmethyl) silane 80 (1,1'-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-yl) ylmethyl jsilan,

1: 1 complex with copper chloride 90

Example 79

The active compounds according to the invention are introduced into standard V-8 agar at 45 DEG C. in an amount of 200 ppm. The conditioned agar is then dispersed in Petri dishes and allowed to solidify. Agar cultures with an area of approximately 4 mm ^{2 of} 5 Phytophthora species: Phytophthora cinamomi, P. cactorum, P. infestans, P. palmivora and P. parasitica var. nicotianae and incubated at 22 ° C for 6 days. Colonies with a radial increase of not more than 1 mm are considered to be inhibited by the active ingredient according to the invention as compared to colonies with a radial increase of more than 15 mm growing on the untreated medium. The number of Phytophthora limited by certain active substances according to the invention is shown in the following table.

Table XXXI

Compound of 5 species

In vitro restricted phytophthora (Butyl j dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 1 (3,4-Dichlorophenyl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 2 (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 3 (1H-imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane 4- (2,4-Dichlorophenyl) dimethyl (1H-iroidazole) 1-ylmethyl jsilane 5

124

Diphenyl (1H-imidazol-1-ylmethyl) methylsilane 2 (4-Fluorophenyl) (1H-imidazol-1-ylmethyl) methyl (phenyl jsilane 2)

Example 80

The active compounds according to the invention are introduced into a suitable composition and used to coat cotton seeds in an amount of 2 g / kg of seeds. Po ^! perfect bedding, the seeds are allowed to air dry at room temperature. Cotton seeds are then sown in soil treated with Pythium aphanadermatum, sand, corn flour in sufficient quantity to destroy most seeds. The seeds in this soil are kept at room temperature for one week and then the degree of infestation is evaluated. The percentage of infestation is shown in the following table. Most or all of the treated seeds germinate and good seedlings are obtained, while untreated seeds do not germinate or produce weak and inhibited seedlings.

Table XXXII

Compound% cotton burn restriction

Ethyldimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 48 (Ι, Γ-Biphenyl-4-yl) dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 12 (4-Chloro) enyl j dimethyl (1H-1,2,4-triazol-1-ylmethyl) silane 53 '

Dimethyl (4-phenoxyphenyl) (1H-1,2,4-triazol-1-ylmethyl) silane 18 ^Λ (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 18 (4-Chlorophenyl) ) (1H-imidazol-1-ylmethyl) dimethylsilane 18 ^Λ (3,4-Dichlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 15 ^{Λ A} active ingredient used in 0,5 g / kg seeds

Example 81

The active compounds according to the invention are formulated in suitable formulations and then used to coat 2 g / kg of corn grains. After thoroughly covering the grains

125

126

Compound% restriction

The pythia on corn is allowed to air dry at room temperature. The seeds are then sown in soil treated with a mixture of Pythium aphanadermatum, sand and corn flour in an amount sufficient to destroy most of the seeds.

of rubbed grains. It is kept at 9 ° C for two weeks and then at 21 ° C for another week. After this time, the assault is evaluated. The percentage of infection limits is shown in the following table. Most or all of the treated grains sprout and grow healthy seedlings, while untreated grains either do not come at all or produce seedlings or slowed seedlings. Table XXXIII Compound % reduced Pythia to maize (1,1'-Biphenyl-4-yl) dimethyl (1H-imidazol-1-ylmethyl) silane 32 (4-Chlorophenyl) (1H-imidazol-1-ylmethyl) dimethylsilane 25 (1 H -imidazol-1-ylmethyl) dimethyl (1-naphthalenyl) silane 27 Mar: (3,4-Dichlorophenyl) (1H-imidazol-1-ylinethyl) dimethylsilane 30

(1H-imidazol-1-ylmethyl) dimethyl (4-phenoxyphenyl) silane 5

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

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

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

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

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