JPS6253515B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention describes the use of silylmethyltriazoles, such as dimethyl(phenyl)(1H-1.2.4-triazol-1-ylmethyl)silanes, and these new compounds to treat fungal diseases.
diseases), especially in the control of living plant diseases. More specifically, the present invention is based on the following formula-1 where Q ₁ and Q ₂ are independently H; R ₁ is C ₂ -C ₁₈ alkyl, C ₆ cycloalkyl, naphthyl or

[Formula]; R ₂ and R ₃ are independently C ₁ -C ₆ alkyl, OR ₆ or

[Formula]; R ₄ and R ₅ are independently H, halogen, -OCH ₃ , -
_OCF3 , _-SCH3 , _-SO2CH3 , phenyl, halogen-substituted phenyl, phenoxy, halogen-substituted phenoxy, _-CF3 , _C1 - _C4 alkyl, or _cyclohexyl ; _R6 is H or _C1 - _C4 alkyl; with the proviso that both _R2 and _R3 cannot be OH at the same time, salts and metal complexes thereof, as well as their preparation and use. U.S. Patent No. 3,692,798 describes the formula Discloses compounds of the formula wherein R ₁ , R ₂ and R ₃ can be lower alkyl and phenyl. These compounds are said to be useful as antimicrobial agents. European Patent No. 29993 describes the formula where R is _C1 - _C4 alkyl, and Y and Z can be H _{or SiR1R2R3 ,}
Disclosed are compounds where R ₁ , R ₂ and R ₃ can be alkyl, haloalkyl, alkenyl, alkynyl or substituted phenyl. The compounds are taught to be useful as agricultural fungicides. U.S. Patent Nos. 3,256,308 and 3,337,598 are
formula Discloses compounds of the formula wherein R ₁ can be methyl, ethyl, vinyl, or phenyl. Their use for controlling fungi has also been taught. Belgian patent No. 785127 discloses quaternary ammonium salts, e.g. and their use as fungicides. Research Disclosure
Disclosure) No. 17652 is a formula Discloses silyl ethers of the formula wherein Ar can be substituted phenyl, X can be CH or N, and R can be alkyl. The compounds are taught to be useful as agricultural fungicides. West German patent DE3000140 is based on the formula Discloses silyl ethers of the formula wherein Ar can be substituted phenyl, X can be CH or N, and R can be phenyl or lower alkyl. These compounds are taught to be useful as agricultural fungicides. U.S. Patent No. 4,248,992 describes the general formula In the formula, R is a hydrocarbon atom or a monovalent hydrocarbon group, and at least one of the monovalent guanidine groups represented by
Discloses a class of organosilicon compounds having in one molecule. The guanidine-containing organosilicon compounds are described as useful as antimicrobial agents for molded plastics and rubbers, particularly silicone rubbers. USSR Patent No. 346306 has the formula (R ₁ ) _o (R ₂ O) _3-o SiCH ₂ Az where R ₁ and R ₂ are alkyl groups and n is 0.
~3 and Az is an optionally substituted ring of pyrazole, imidazole, or benzimidazole. USSR Patent No. 271552 describes the formula (R ₁ ) _o (R ₂ O) _3-o SiCH ₂ CH ₂ Az where R ₁ , R ₂ , n and Az are as described above. Certain silylethylazoles are disclosed. The present invention also relates to the silylmethyltriazoles of the formula-1 and agriculturally useful compositions thereof. In the following, for reference, the silylmethyltriazoles of the following formula include the formula-1. may be explained. Furthermore, in order to facilitate understanding, silylmethylimidazoles of the following formula may also be mentioned for reference. where _Q1 , _Q2 and _Q3 are independently H or _CH3 , n is 1, and _R1 is _C2 - _C18 alkyl, _C3 - _C6 cycloalkyl, naphthyl or

[Formula], and R ₁ ′ is C ₆ -C ₁₈ alkyl, C ₃ -C ₆ cycloalkyl, naphthyl or

[Formula], R ₂ and R ₃ are independently C ₁ -C ₆ alkyl, C ₃ -C ₆
Cycloalkyl, OR ₆ or

[Formula], R ₄ and R ₅ are independently -H; halogen; -
_OCH3 ; _-OCF3 ; _-SCH3 ; _-SO2CH3 ;phenyl; phenyl substituted with halogen and/or _{C1- C4} alkyl and _/ or _-CF3 ; phenoxy; halogen and/or _C1- phenoxy substituted with _C4 alkyl and/or _-CF3 ; _-CF3 ; _C1 - _C4 alkyl; or cyclohexyl, provided that both _R4 and _R5 are simultaneously H for compounds of formula cannot, and R ₆ is H or C ₁ -C ₄ alkyl, with the proviso that
Both R ₂ and R ₃ cannot be OH, and R ₂ and R ₃ together are 1.2- or 1.3
- or 1,4-glycol crosslinking or a total of 4
up to 4 alkyl groups having up to 4 carbon atoms
can be a 1,4 unsaturated glycol bridge substituted with _R7 - _R10 ,

[expression] or

[expression] or

[expression] or

[Formula] The present invention also provides protection against fungi by applying an effective amount of at least one compound selected from the formula-1 compound, salts thereof, and metal complexes to a place to be protected. Concerning ways to control diseases of plants, especially fungal diseases of living plants. When R ₂ or R ₃ is OH, the formula and formula are dioxolane, or should be understood to include. The present invention also relates to a complex of the compound of formula-1 and a salt of a protonic acid and a metal ion. Preferred compounds, because of their high activity and/or suitably easy synthesis, are those in the general range where Q ₁ =Q ₂ =H. Compounds that are more preferred because they are more active and/or easier to synthesize are those in which R ₁ is

[Formula], and R ₂ is C ₁ -C ₄ alkyl or

A preferred range of compounds are: and R ₃ is C ₁ -C ₄ alkyl. The most preferred compounds, because they are most active and/or most preferably easy to synthesize, are those where R ₁ is

[Formula], where R ₄ is in the para position of R ₁ and R ₄ is H, F, Cl, Br or phenyl;
and R ₅ is H, F, Cl or Br, and R ₂ is

or C ₁ -C ₄ alkyl, and R ₃ is C ₁ -C ₄ alkyl. Particularly preferred compounds, because of their excellent activity and/or because they are most preferably easy to synthesize, are compounds of the following formula: (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-ylmethyl)silane, (2,4-dichlorophenyl)dimethyl (1H
-1,2,4-triazol-1-ylmethyl)silane, butyl(4-chlorophenyl)methyl(1H-
1,2,4-triazol-1-ylmethyl)silane, bis(4-chlorophenyl)methyl(1H-
1,2,4-triazol-1-ylmethyl)silane, methyl(diphenyl)(1H-1,2,4-triazol-1-ylmethyl)silane, [bis(4-
fluorophenyl)]methyl (1H-1,2,4-
triazol-1-ylmethyl)silane, (4-fluorophenyl)dimethyl(1H-
1,2,4-triazol-1-ylmethyl)silane, butyl(2,4-dichlorophenyl)methyl(1H-1,2,4-triazol-1-ylmethyl)silane, [bis(2,4-dichloro phenyl)] methyl (1H-1,2,4-triazol-1-ylmethyl)silane, 2,4-dichlorophenyl(methyl)phenyl (1H-1,2,4-triazol-1-ylmethyl)silane, 4-chlorophenyl(methyl)phenyl (1H
-1,2,4-triazol-1-ylmethyl)silane, 4-fluorophenyl(methyl)phenyl(1H-1,2,4-triazol-ylmethyl)silane, butyl(methyl)phenyl(1H-1,2・4
-triazol-1-ylmethyl)silane, butyl(4-fluorophenyl)methyl(1H
-1,2,4-triazol-1-ylmethyl)silane, [bis(1,1'-biphenyl-4-yl)]methyl(1H-1,2,4-triazol-1-ylmethyl)silane, (1・1'-biphenyl-4-yl)butyl(methyl)(1H-1,2,4-triazol-1-ylmethyl)silane, and (1,1'-biphenyl-4-yl)methyl(phenyl)(1H -1,2,4-triazol-1-ylmethyl)silane. Q ₁ and Q ₂ are both H or both CH ₃
When

[expression] and When one triazole substituent is H and the other substituent is _CH3 , three isomers can exist:

[expression] and

[expression] and This mixture mainly contains isomers of formula A or formula C. However, the isomers of formulas B, D and E also have fungicidal activity and separation of the isomers is unnecessary. In addition, in the above formula A,
The definitions of Q ₁ , Q ₂ , R ₁ , R ₂ and R ₃ are as follows from the above formula-1
The specification of the present invention is defined as follows. For imidazole derivatives of formula, when Q ₂ and Q ₃ are not identical, isomers are produced:

[expression] and Isomers of formula A generally predominate. However, the isomer of formula B is also toxic to the fungus;
and separation of isomers is unnecessary. In the following explanation, all meanings of R ₁ ′ are defined as R ₁
R ₁ is understood to represent both R ₁ and R ₁ ′. Additionally, the term "azole" is used to mean suitably substituted 1,2,4-triazoles and imidazoles:

[expression] and

In the formula, Q ₁ , Q ₂ and Q ₃ can be H or CH ₃ . When writing a structural formula, the structure of the parts

where X is N or CQ ₃ is used to refer to both triazole and imidazole ring systems. Synthesis The compounds of the formula including the compound of formula-1 of the present invention, as well as the compounds of the formula, are prepared from chloromethylsilane and the sodium salt of 1,2,4-triazole or imidazole or methylated homologs thereof. can: Azole salts of lithium and potassium can also be used. Bromomethylsilane, iodomethylsilane, or arylsulfonyloxymethylsilane can be used in place of chloromethylsilane. Approximately equimolar amounts of reagents are used (except when R ₃ =OR ₆ , see below), and the azole salt is often used in a 5-10% excess of the theoretical amount.
Additionally, 1,2,4-triazole or imidazole themselves can be used when adding acid acceptors. Suitable acceptors are azoles in excess, alkali metal alkoxides such as sodium methoxide or potassium tert-butoxide, inorganic bases such as potassium carbonate or sodium hydride, and tertiary amines such as triethylamine. When the acid acceptor is a good nucleophile, such as sodium methoxide, excess amounts should be avoided to prevent undesirable side reactions. Examples of suitable solvents are polar aprotic solvents such as dimethylformamide, dimethylsulfoxide or acetonitrile; ethers such as tetrahydrofuran or 1,2-dimethoxyethane, and ketones such as 2-butanone. The reaction temperature is 0°C to 200°C, preferably 25°C
It can vary between ℃ and 100℃. Although the reaction can be carried out under elevated pressure, it is generally preferred to carry out the reaction under atmospheric pressure. The optimum temperature and reaction time will vary with the concentration and selection of reaction components, especially the choice of solvent. For example, 1,2,4-triazole and sodium methoxide were dissolved in dimethylformamide at a concentration of approximately 2 molar in approximately 2 hours.
Gives excellent conversion at 90°C, but 1.
2,4-triazole and potassium carbonate are 2-
It takes 8 to 12 hours at reflux temperature at a concentration of approximately 1 molar in butanone. Generally, reaction times of 1 to 24 hours are required. The progress of the reaction was completed with an aliquot for nmr analysis, starting material around 2.9
It can be traced by measuring the intensities of the SiCH ₂ Cl singlet and the product SiCH ₂ N singlet (around 3.8 for compounds of formula and around 3.7 for compounds of formula). Regarding triazole derivatives of the formula, 1H-1.2.4-triazole-1 prepared as above
-ylmethyl compound has a small amount of isomer 4H-1.
2,4-triazol-4-yl compound, accompanied by. The ratio of isomers varies with the meaning of R and the reaction conditions, with the ratio of 1-substituted to 4-substituted approximately
A ratio of 10:1 is often observed. Monomethyltriazole and dimethyltriazole contain similar 4H-isomers as minor products,

[expression] or give. When unsubstituted silylmethyltriazoles are available, metalation-methylation provides an alternative method for the synthesis of methylated congeners: Regarding imidazole derivatives of formula, isomers are possible only when Q ₂ and Q ₃ are not identical. Two isomers occur:

[expression] and

[Formula] The product of formula A generally accounts for the major proportion.
If necessary, isomers can be isolated using standard techniques, e.g.
Can be separated by crystallization, distillation, or chromatography. R ₃ in triazole or imidazole
For the case of =OR ₆ , chloro(chloromethyl)
Chlorine in the silane can be replaced in one of two ways. In one method, at least 2 equivalents of the sodium salt of the azole can be used. An intermediate containing a highly reactive silicon-azole bond is formed, and reaction with water or alcohol gives the desired oxygenated compound: Suitable solvents and reaction conditions are the same as outlined on the previous page for azole substitutions. The temperature of alcohol cis is not critical and R ₆
When = _C1 - _C4 alkyl, warming to 50-100C can be used to complete the preservation. but,
For R ₆ =H, hydrolysis is best carried out near room temperature to minimize disiloxane formation, recognizing that silanol-disiloxane equilibrium is possible whenever R ₆ =H. be able to: The position of equilibrium and the speed at which it is established is
The meaning of R ₁ and R ₂ varies with solvent, temperature, and the presence or absence of acidic or basic catalysts. In the second method, silicon-oxygen bonds are first formed and then azole substitution occurs as described above: The reaction of chlorosilane with R ₆ OH can be carried out in almost any non-hydroxyl solvent. Ethers, such as diethyl ether, 1,2-
Dimethoxyethane and tetrahydrofuran or dipolar aprotic solvents such as dimethylformamide and acetonitrile are preferred.
Although an acid acceptor is not necessary, it is preferred to add a tertiary amine, such as triethylamine or pyridine. The reaction temperature can be varied between 0<0>C and 100<0>C, and R ₆ OH is often used in excess of the stoichiometric amount. The combination of 2 equivalents of R ₆ OH, 1.1 equivalents of triethylamine, and 0.1 equivalents of imidazole in dimethylformamide for 2 hours at 80° C. could be widely used. Extending these methods to (chloromethyl)dichlorosilane yields dioxygenated silanes: When a diol is used in place of two molecules of R ₆ OH, a glycol derivative is similarly produced. Another method for the synthesis of alkoxy(chloromethyl)silanes consists of selectively replacing one alkoxy group of the dialkoxysilane with an organometallic reagent: The conditions for this replacement will be explained in the next section. However, the organometallic should be added to the dialkoxysilane. The required chloromethylsilane starting materials include commercially available chloro(chloromethyl)dimethylsilane, chloromethyl(dichloro)methylsilane,
Or made from chloromethyltrichlorosilane: The Si-Cl bonds in these compounds are reacted with organolithium, organosodium or Grignard reagents according to literature procedures to generate alkyl and/or aryl groups, leaving the C-Cl bonds intact. For silanes containing two or three Si-Cl bonds, stepwise substitution is possible and provides considerable flexibility as to the meaning of _R1 - _R3 . Bromosilanes, iodosilanes, or alkoxysilanes can be used in place of chlorosilanes in these reactions. Examples of preferred solvents for these reactions are ethers such as tetrahydrofuran, 1,2-dimethoxyethane,
and diethyl ether, or hydrocarbons such as hexane and toluene. The preferred temperature depends on the nature of the organometallic reagent, the method by which it was produced,
and varies between -80°C and 40°C depending on the solvent. For example, when an aryllithium reagent is prepared from an arylbromide using butyllithium in tetrahydrofuran, the mixture is approximately −40
It should be kept below 0°C to avoid side reactions including the formation of bromobutane. However, when the organometallic solution is stable at temperatures higher than this, the reaction is
It can be carried out at -20<0>C to 25<0>C in the absence of competitive reactions of _CH2Cl groups. The reaction is rapid at all temperatures and only a short time, eg 30-60 minutes, is required to bring the reaction components together and complete the reaction. The reaction of ClSi(CH ₃ ) ₂ CH ₂ Cl with Grignard reagent is described by C. Eaborn and JC Jeffrey, J. Chem.
Soc. 1954 , 4266, and ClSi
A recent overview of the synthesis of aryltrimethylsilanes from ClSi( _CH3 ) ₃ , including experimental procedures useful for the reaction of ( _CH3 ) _{2CH2Cl ,} is given by D. Habich and F. Effenberger, Synthesis, 1979 , 841. One new alkyl group Cl ₂ Si
The introduction of (CH ₃ ) into CH ₂ Cl was described by VPKuznetsova and RMSokolovaskaya, Zh.Obshch.Khim.
1969 , 1977; Chem.Abstr., 72 , 31897p, and one aryl group can be introduced selectively as well: In both cases, the organometallic reagent should be added to the dichlorosilane at low temperature and with good mixing for best yields. The reaction between Cl ₃ SiCH ₂ Cl and Grignard reagent is
AAZhdanov, VIPakhomov, and T.
Bazhanova, Zh.Obshch.Khim., 1973 , 1280;
Chem.Abstr., 79 , 66452m.
Addition of organometallic reagent to trichlorosilane
recommended even when introducing two identical groups. This is because the addition of Cl ₃ SiCH ₂ Cl to organometallic reagents is usually unsuccessful. Single aryl groups can also be introduced: A useful modification of the literature procedure, applicable when R ₁ or R ₁ ' is an aryl group, was developed in this work. Instead of forming an organolithium reagent and then combining it with a chlorosilane, an aryl bromide and a chlorosilane such as ClSi
It has been discovered that ( _CH3 ) _2CH2Cl can be combined in an inert solvent such as tetrahydrofuran and treated _with butyllithium at -80<0>C to -40<0>C. Bromine-lithium exchange proceeds selectively,
The resulting aryllithium then reacts with Si-Cl as it forms: This reaction works with aryl-substituted chlorosilanes such as
It proceeds equally well with ClSi(CH ₃ )(C ₆ H ₅ )CH ₂ Cl and can be used to introduce two aryl groups into Cl ₂ Si(CH ₃ )CH ₂ Cl. With further stretching, aryl and n-butyl groups can be introduced in one step: When another alkyllithium RLi is used in place of n-butyllithium, Ar(CH ₃ )Si(R)
A general route to CH ₂ Cl is obtained. In the examples below, temperatures are reported in degrees Celsius. The abbreviations for nuclear magnetic resonance (nmr) spectra are: s=-doublet, d=doublet, t=
Triplet, q = quartet, m = multiplet. Peak positions are reported as ppm downfield from internal tetramethylsilane. Infrared (IR) peak positions are expressed in reciprocal centimeters (cm ^-1 ). By hexanes is meant a mixture of isomers with a boiling point of 68-69°C, and by ether is meant diethyl ether. mp is melting point, bp is boiling point,
and mw respectively mean molecular weight. Example 1 Preparation of (1,1'-biphenyl-4-yl)(chloromethyl)dimethylsilane 9.9 g in 50 ml of dry tetrahydrofuran
(0.042 mol) of 4-bromobiphenyl was cooled to -78°C under a nitrogen atmosphere and stirred while 26.5 ml (0.042 mol) of 1.6 mol n-butyllithium in hexane was added over 15 minutes. added. A viscous slurry formed and 35 ml of tetrahydrofuran was added to facilitate stirring. With continuous cooling, 5.9 ml (6.7 g, 0.046 mol) of chloro(chloromethyl)dimethylsilane was added over 10 minutes and a clear solution formed which was allowed to warm to room temperature. 300 ml of ether was added, the precipitated lithium chloride was removed by filtration, and the liquid was evaporated, leaving 13.2 g of semi-solid. Redissolving in ether, filtering, and evaporating the liquid yielded 11.0 g (100
% crude) The title compound is a colorless solid, melting point 30−40
℃, was obtained. This is suitable for further reactions. Removal of trace impurities by sublimation at 30°C/0.1mm left the title compound unsublimated with 83% recovery: mp37−40°; ir (Nujol ^R )
1585, 1240, 1110, 830, 810, 750, ^{690cm -1} ;
nmr (CDCl ₃ ) 0.4 (6H, s), 2.9 (2H, s),
7.3−7.7 (9H, m). Example 2 Production of (4-bromophenyl)(chloromethyl)dimethylsilane 4-bromophenylmagnesium bromide,
GP from 11.8 g (0.050 mol) of 1,4-dibromobenzene and 1.2 g (0.050 gram atom) of magnesium turnings in 75 ml of ether.
Schiemenz, Org.Syn., Coll.Vol. 5 , 496
(1973). The resulting mixture was cooled in ice under a nitrogen atmosphere while a solution of 6.6 ml (7.2 g, 0.050 mol) of chloro(chloromethyl)dimethylsilane in 10 ml of ether was added dropwise. The reaction mixture was then stirred at room temperature overnight, quenched with saturated aqueous ammonium chloride, and filtered. The liquid ether phase was washed with brine, dried over magnesium sulfate and evaporated leaving 9.8 g of oil.
Distillation gave 3.8 g (29%) of the title compound as a colorless liquid: bp 97° (1 mm); ir (pure) 2950, 1575, 1475, 1370, 1250, 1065;
1010, 840, 805, 720cm ^-1 ; nmr ( _CDCl3 ) 0.4
(6H, s), 2.9 (2H, s), 7.3−7.7 (4H, m). Example 3 Preparation of chloromethyl(4-chlorophenyl)dimethylsilane 9.6 g (0.050 mol) of 4-bromochlorobenzene in 75 ml of tetrahydrofuran and 6.6 ml
(7.2g, 0.050mol) of chloro(chloromethyl)
A solution of dimethylsilane was stirred at −78 °C under a nitrogen atmosphere while 1.6 moles of n in hexane
-31 ml (0.050 mol) of butyllithium were added dropwise. The resulting clear solution was warmed to room temperature, diluted until no more lithium chloride precipitated, and filtered. Evaporation of the liquid left 10.6 g of pale yellow liquid, which was distilled to yield 6.0 g (55%) of the title compound as a colorless liquid: bp54-
58℃ (0.05mm); IR (pure) 2910, 1560, 1470,
1370, 1250, 1080, 1010, 840, 805, 790, 740cm
^-1 ; nmr (CDCl ₃ ) 0.4 (6H, s), 2.9 (2H,
s), 7.1−7.6 (4H, q). The in situ aryllithium production described in this example is also useful in making the product of Example 1. This reaction was carried out in 4-bromobiphenyl.
When carried out at 0.5-0.7 mol and the temperature is kept between -65 and -55°C during the addition of butyllithium, little or no solids precipitate. Example 4 Preparation of chloromethyl(2,4-dichlorophenyl)dimethylsilane 17.0 g in 100 ml dry tetrahydrofuran
A solution of (0.075 mol) of 2,4-dichlorobromobenzene and 10.8 ml (11.8 g, 0.082 mol) of chloro(chloromethyl)dimethylsilane was cooled to −70° C. in a nitrogen atmosphere while 1.6
49 ml (0.079 mol) of mole n-butyllithium
was added dropwise at a rate that kept the mixture below -70°C. Warm the resulting simmering reaction mixture to room temperature,
Pour into 400ml of hexanes, filter and evaporate leaving 20.5g of yellow liquid. When distilled,
12.6 g (66%) of the title compound was obtained as a colorless liquid: bp 83° (0.02 mm); n ²⁴ _D 1.5522; ir
(Pure) 1565, 1455, 1360, 1255, 1120, 1100,
1040, 825cm ^-1 ; nmr (CDCl ₃ ) 0.5 (6H, s),
3.1 (2H, s), 7.0−7.5 (3H, m). Example 5 Chloromethyl (2,6-dimethoxyphenyl)
Preparation of dimethylsilane 25.0 g (0.181
A solution of 1,3-dimethoxybenzene (mol) of
ml (0.200 mol) was added dropwise over 30 minutes.
The resulting mixture was refluxed for 1.5 hours, yielding a yellow and colored solution, which was cooled to 5°C and stirred while
27 ml (29.4 g, 0.205 mol) of chloro(chloromethyl)dimethylsilane was added dropwise over 15 minutes.
The resulting white suspension was warmed to room temperature, stirred for 1 hour, diluted with ethyl acetate, poured into water and extracted with ether. The organic phase was washed with brine, dried over magnesium sulfate, and distilled to yield 37.0 g (84
%) of the title compound was obtained as a colorless liquid:
bp98−110゜(0.1mm); nmr( _CDCl3 )0.4
(6H, s), 3.1 (2H, s), 3.7 (6H, s), 6.3
(2H, d), 7.1 (1H, m). By varying the organolithium or Grignard reagent, the procedures of Examples 1-5 can be used to prepare the compounds in the table. Closely related procedures are also known from the literature, for example the use of arylmagnesium chlorides is described by C. Eaborn and J.
C. Jeffrey. J. Chem. Soc., 1954 , 4266. For compounds where R ₁ is a phenyl ring with a 2-halo substituent, a modification to the in situ procedure of Example 4 is described by C. Eaborn, KLJaura and
DRM Walton, J.Chem.Soc., 1964 , 1198, a special arylmagnesium iodide method.

【table】

【table】

[Table] Example 6 Preparation of (1,1'-biphenyl-4-yl)butyl(chloromethyl)methylsilane The title compound was prepared by replacing chloro(chloromethyl)dimethylsilane with (butyl)silane according to the procedure of Example 1. It can be produced using chloro(chloromethyl)methylsilane. Related compounds were prepared using appropriate organolithium or Grignard reagents and Cl
It can be produced using (R ₂ )Si(CH ₃ )CH ₂ Cl.
The required chloromethylsilane starting material is R ₂ MgCl
or from _R2Li and _Cl2Si ( _CH3 ) _CH2Cl Example 14
and 15 and procedures in the literature e.g. VP
Kuznetsova and RMSokolovaskaya, Zh.
Created according to Obshch.khim., 1969 , 1997. Alternatively, both biphenyl and butyl groups are
You can install them at the same time as follows: 23.3 g (0.10 mol) of 4 in 150 ml dry tetrahydrofuran
- bromobiphenyl and 12.7 ml (16.4 g, 0.10
A solution of chloromethyl(dichloro)methylsilane (1.6 mol) in hexane is cooled to −70° C. in a nitrogen atmosphere and stirred while stirring.
125 ml (0.2 mol) of butyllithium was added at a rate such that the mixture was kept below -60°C.
The resulting dilute slurry was warmed to room temperature, treated carefully with 10 ml of ethyl acetate, and poured into 300 ml of water. The organic layer was separated, the aqueous phase was washed with another 100 ml of hexanes, the combined organic phases were washed three times with water, once with brine, dried over magnesium sulfate,
Upon evaporation, 33.9 g of viscous oil remained. Distillation gave 9.5 g (31%) of the title compound:
bp135−158゜(0.1mm); n ²² _D 1.5743; ir (pure)
3060, 3015, 2960, 2920, 2870, 1600, 1485,
1390, 1380, 1250, 1120, 1075, 1005, 875,
810, 800, 760, 700cm ^-1 ; nmr ( _CDCl3 ): 0.4
(3H, s), 0.6-1.8 (9H, m), 2.9 (2H, s)
and 7.0−7.7 (9H, m). Example 7 Preparation of butyl(chloromethyl)(4-chlorophenyl)methylsilane 14.4 g (0.075 g) in 150 ml of tetrahydrofuran
mol) of 4-bromochlorobenzene and 9.5 ml
A solution of (12.3 g, 0.075 mol) chloromethyl(dichloro)methylsilane was cooled to −60° C. in a nitrogen atmosphere and stirred while 94 ml (0.15 mol) of 1.6 mol n-butyllithium in hexane was added to
The mixture was added dropwise at a rate that maintained the temperature between -65 and -55°C. The resulting slurry was warmed to room temperature and a solution was obtained which was diluted with hexane until no more lithium chloride precipitated. After filtering, evaporating the liquid and dissolving the residue in hexanes, refiltering and evaporating, 19.8 g of pale orange liquid remained. When distilled, first 1.8g (12%) of chloromethyl(dibutyl)methylsilane, bp45℃
(0.05 mm) was obtained, followed by 6.8 g (35%) of the title compound as a colorless liquid: bp 90°C.
(0.05mm); n ²¹ _D 1.5246; ir (pure) 2925, 1580,
1380, 1260, 1090, 1015, 820, 740cm ^-1 ; nmr
( _CDCl3 ) 0.4 (3H, s), 0.6−1.5 (9H, m),
2.9 (2H, s), 7.0−7.4 (4H, q). Example 8 Preparation of chloromethyl(2,4-dichlorophenyl)methyl(phenyl)silane 13.6 g in 85 ml dry tetrahydrofuran
(0.06 mol) of 2,4-dibromobenzene and
12.3g (0.060mol) chloro(chloromethyl)
A solution of methyl(phenyl)silane (prepared as in Example 14) was cooled to −60° C. in a nitrogen atmosphere while 38 ml (0.060 mol) of 1.6 mol n-butyllithium in hexane was added to the mixture to −60° C. 55
The dropwise addition was carried out at a rate that maintained the temperature below °C. The resulting red solution was warmed to room temperature, treated with 5 ml of ethyl acetate to quench unreacted organolithium reagent, and poured into 170 ml of water. The organic layer was separated, the aqueous phase was washed with 50 ml of hexanes, and the combined organic phases were washed three times with water and once with brine, dried over magnesium sulfate, and evaporated to give 19.0 g of a bright yellow color. Oil remained. Distillation gave 8.6 g (45%) of the title compound as a colorless liquid: bp125−130
° (0.05mm); n ²¹ _D 1.5978; ir (pure) 3080,
3060, 2960, 2930, 1570, 1540, 1460, 1430,
1365, 1260, 1120, 1100, 1040, 820, 745,
735, 705cm ^-1 ; nmr (CDCl ₃ ) 0.8 (3H, s), 3.4
(2H, s), 7.2−7.9 (8H, m). Example 9 Chloromethyl [bis(4-chlorophenyl)]
Preparation of methylsilane 19.1 g in 200 ml dry tetrahydrofuran
A solution of (0.10 mol) of 4-chlorobromobenzene was cooled to -60°C in a nitrogen atmosphere and stirred, while 63 ml (0.10 mol) of 1.6 mol of n-butyllithium in hexane was added until the mixture was below -55°C. was added at such a rate that it was maintained at . Continue stirring and cooling while adding 6.3 ml (8.2 g, 0.05 mol) of chloromethyl(dichloro)methylsilane until the mixture reaches -50
The dropwise addition was carried out at a rate that maintained the temperature below °C. The resulting orange solution was warmed to room temperature and worked up as in Example 8 to give 16.5 g of a pale yellow oil. Ball tube (Kugelrohr) distillation with 0.05mm and
When performed at an air bath temperature of 130-150°C, 9.5 g
(60%) of the title compound was obtained as a colorless liquid: ^n24D _1.5913 ; ir (pure) 3080, 3040, 3020,
2960, 2930, 1580, 1490, 1380, 1260, 1085,
1015, 805, 790, 775, 740cm ^-1 ; nmr ( _CDCl3 )
0.7 (3H, s), 3.1 (2H, s), 7.2−7.7 (8H,
m); Analysis of C ₁₄ H ₁₃ Cl ₃ Si (mw315.70): Calculated value: C, 53.26; H, 4.15; Cl, 33.69 Actual value: C, 53.4; H, 4.4; Cl, 34.2 53.5; 4.4 ;34.1. Example 10 Preparation of (chloromethyl)bis(4-fluorophenyl)methylsilane 35g in 300ml dry tetrahydrofuran
(0.20 mol) of 4-fluorobromobenzene was cooled to -60°C in a nitrogen atmosphere and stirred, while 126 ml (0.20 mol) of 1.6 mol of n-butyllithium in hexane was added to the solution until the mixture was at -55°C. Dropwise at a rate maintained below. Stirring and cooling were continued while 12.6 ml (16.4 g, 0.10 mol) of chloromethyl(dichloro)methylsilane was added dropwise at a rate that maintained the mixture below -50°C. The resulting solution was warmed to room temperature and worked up as in Example 8 to yield 26.4 g of a bright yellow liquid.
Distillation gave 20.6 g (73%) of the title compound as a colorless liquid: bp 107−127° (0.1
mm); ^n22D _1.5481 ; nmr ( _CDCl3 ): 0.7 (3H,
s), 3.2 (2H, s), 7.1 (4H, t, J=9) and 7.6 (4H, d of d, J=6 and 9). When this reaction was repeated using chloromethyl(diethoxy)methylsilane in place of dichlorosilane, the title compound was obtained in 58% yield after distillation: bp 115-138° (0.2 mm); n ²¹ _D 1.5464; nmr ,
As above. A sample similar to the title compound was crystallized from ether-hexane at -78°C to give a colorless solid. Melting point 39-40°. Example 11 Preparation of chloromethyl(2-chlorophenyl)(4-chlorophenyl)methylsilane 6.3 ml (8.2
A solution of chloromethyl(dichloro)methylsilane (g, 0.05 mol) and 8.1 g (0.05 mol) of 2-bromochlorobenzene was cooled to -60 °C under _N2 and stirred while 1.6 mol of n in hexane -31 ml (0.05 mol) of butyllithium were added at a rate that kept the mixture below -55°C. While continuing to cool and stir, add 8.1 g (0.05 mol) of 4
-Bromochlorobenzene was added as a solid, then another 31 ml portion of the 1.6 molar n-butyllithium solution described above was added at a rate that kept the mixture below -55°C. The resulting dilute slurry was warmed to room temperature, treated carefully with 10 ml of ethyl acetate, and worked up as in Example 8 to yield 15.0 g (37%).
A bright yellow liquid was obtained: bp 150-165° (0.7 mm); n ²⁰ _D 1.5916; ir (pure) 3060, 3020,
2960, 2920, 2870, 1580, 1560, 1490, 1420,
1380, 1255, 1125, 1115, 1085, 1035, 1015,
805, 750cm ^-1 ; nmr (CDCl ₃ ) 0.8 (3H, s), 3.3
(2H, s), 7.2−7.7 (8H, m). _Cl2Si ( _CH3 ) following the procedure of Examples 6-11
By stepwise substitution of the Si-Cl bond in CH ₂ Cl, the compounds in the table are obtained.

[Table] Enil

[Table] Enil

[Table] Enil Lolofue
Example 12 Preparation of (1,1′-biphenyl-1-yl)(chloromethyl)diethylsilane The title compound was prepared using the procedure of Example 1 using chlorochloromethyldiethylsilane in place of chlorochloromethyldimethylsilane. can be manufactured. Similar compounds can be prepared by applying the procedures of Examples 1-5 to the appropriate organolithium, Grignard reagent, and Cl( _R2 )Si( _R3 ) _CH2Cl .
the necessary chlorochloromethyldialkylsilane,
From Cl ₃ SiCH ₂ Cl, when R ₂ = R ₃ , 2 equivalents of
made using R ₂ MgCl or R ₂ Li (e.g.
AAZhdanov, VIPakhomov, and T.
Bazhanova, Zh. Obshch. Khim., 1973 , 1280), or when R ₂ is not equal to R ₃ , use 1 equivalent of R ₂ MgCl or R ₂ Li and then 1 equivalent of
Produced using R ₃ MgCl or R ₃ Li. Example 13 Preparation of (chloromethyl)triphenylsilane 12.6 ml (18.4 g, 0.10 g in 150 ml dry ether)
A solution of (chloromethyl)trichlorosilane (1.85 mol) in 70:30 cyclohexane-ether was stirred under nitrogen and cooled in ice while 162 ml (0.30 mol) of 1.85 mol phenyllithium in 70:30 cyclohexane-ether was added to the mixture until 15 mol) of (chloromethyl)trichlorosilane was stirred under nitrogen and cooled in ice. The dropwise addition was carried out at a rate that maintained the temperature below °C. The resulting slurry was stirred overnight at room temperature, carefully treated with 10 ml of ethyl acetate to quench the remaining phenyllithium, washed with water and brine, dried over magnesium sulfate, and evaporated to give 33 g of a viscous solid. remained. Recrystallization from 30 ml of cyclohexane gave 15.8 g (51%) of the title compound as a gray solid: mp 112-115°C; ir (Nujol ^R )
1420, 1110, 735, 730, 705, 695 cm ^-1 ; nmr
( _CDCl3 ) 3.5 (2H, s), 7.0-7.8 (15H, m). Compounds in the table were prepared according to the method of Examples 12-13.
It was produced by stepwise substitution of Si-Cl bonds in Cl ₃ SiCH ₂ Cl.

【table】

[Table] Enil Enil

[Table] Lofenyl Lofenyl 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 heated under nitrogen to - Cool to 70 °C, stir vigorously, 1.8 in 30:70 ether-cyclohexane
55 ml (0.10 mol) of mole phenyllithium and 55
ml of ether was added dropwise at a rate that kept the mixture below -70°C. The resulting slurry was stirred, warmed to room temperature, and then allowed to stand overnight.
Filtration and evaporation of the liquid gave 20.4 g of a golden oil, which was distilled to give 14.6 g (71%) of the title compound as a colorless liquid: bp 71-74° (0.6 mm). ;n ²³ _D 1.5337; ir (pure) 3080, 3060,
2980, 2930, 1590, 1430, 1260, 1120, 820,
790, 740, 700 cm ^-1 ; nmr (CDCl ₃ ) 0.8 (3H,
s), 3.1 (2H, s), 7.3−7.6 (3H, m), 7.6−
7.8 (2H, m). Example 15 Preparation of (1,1′-biphenyl)-4-yl)chloro(chloromethyl)methylsilane The title compound was mixed with equimolar amounts of 4-bromobiphenyl, chloromethyldichloro(methyl)silane, and n-butyllithium. It can be manufactured according to the procedure of Example 3. Following the procedures of Examples 14 and 15, the compounds listed in the table can be prepared.

【table】

[Table] Example 16 Chloromethyl (methoxy) methyl (phenyl)
Preparation of Silane A solution of 1.6 ml (1.3 g, 0.040 mol) methanol and 3.0 ml (2.2 g, 0.022 mol) triethylamine in 100 ml ether is stirred while 4.1 g (0.020 mol) chloride in 10 ml ether is stirred. A solution of (chloromethyl)methyl(phenyl)silane was added dropwise. The resulting slurry was refluxed for 2 hours, cooled, and diluted with water, 0.1N aqueous HCl, saturated
Wash with _NaHCO3 aqueous solution, water, and brine;
After drying with magnesium sulfate and evaporating, 3.2 g
A pale yellow liquid remained. When distilled, 1.7g
(42%) of the title compound was obtained as a colorless liquid: bp 46-49° (0.05 mm); ^n22D _1.5207 ; nmr
(CDCl ₃ ); 0.5 (3H, s), 3.0 (2H, s), 3.5
(3H, s) and 7.3−7.8 (5H, m). Example 17 Preparation of chloromethyl(1,1-dimethylethoxy)methyl(phenyl)silane 15.4 g (0.075 mol) of chloro(chloromethyl)methyl(phenyl)silane, 14 ml (11.1 g,
0.15 mol) t-butanol, 11.5 ml (8.3 g,
0.082 g) of triethylamine and 0.5 g (0.008
mol) in 60 ml of dimethylformamide was stirred at 80° C. for 2 hours. The resulting slurry was cooled, poured into 200ml of water, and extracted with ether. The ether extract was washed three times with water, then with 0.1 N aqueous HCl, saturated _aqueous NaHCO and brine, dried over magnesium sulfate,
Evaporation left 14.0 g of pale orange oil. Distillation gave 11.9 g (65%) of the title compound: bp78-82° (0.2 mm); ^n21D _1.5010 ; ir
(Pure) 3080, 3060, 2990, 2940, 1600, 1435,
1395, 1370, 1260, 1245, 1195, 1125, 1060,
1030, 815, 790, 740, 725, 705, 650cm ^-1 ; nmr
(CDCl ₃ ): 0.5 (3H, s), 1.3 (9H, s), 2.9
(2H, s) and 7.3−7.8 (5H, m). Example 18 Chloromethyl(ethoxy)methyl(phenyl)
Preparation of silane 18.2 ml (18.2 g, 0.10 g in 200 ml dry ether)
A solution of chloromethyl(diethoxy)methylsilane (mol) in 70:30 cyclohexane-ether was stirred vigorously under _N2 and cooled.
56ml (0.10mol) of 1.8mol phenyllithium
was added at a rate that kept the mixture below -50°C. The resulting slurry was warmed to room temperature, treated carefully with 10 ml of ethyl acetate, washed with water and brine, dried over magnesium sulfate, and evaporated.
16.8g of completely yellow liquid remained. When distilled,
9.5 g (44%) of the title compound was obtained as a colorless liquid: bp 80-84° (0.1 mm); n ²⁰ _D 1.5144;
nmr (CDCl ₃ ) 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 procedures of Examples 16-18 can be used to prepare the compounds in the table.

[Table] Nil

[Table] Phenyl

[Table] Phenyl Example 19 Preparation of (1,1'-biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane 2.6 g (0.010
A mixture of (1,1'-biphenyl-4-yl)chloromethyldimethylsilane (1,1'-biphenyl-4-yl) and 1,1 g (0,012 mole) of 1,2,4-triazole sodium salt was heated to 80-90°C for 2 hours, Cooled, diluted with water and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulfate, and evaporated to give 2.3 g of a colorless solid, mp79−
86℃ was obtained. When recrystallized from a mixture of 25 ml hexanes and 2 ml ethyl acetate, 1.1 g
(38%) of the title compound was obtained: mp92−93
゜;ir (Nujol ^R ) 1255, 1130, 1000, 825, 760,
695cm ^-1 ; nmr (CDCl ₃ ) 0.4 (6H, s), 3.9
(2H, s), 7.2-7.7 (9H, m), 7.8 (1H, s),
7.9 (1H, s); Analysis of C ₁₇ H ₁₉ N ₃ Si (mw293.43): Calculated value C, 69.58; H, 6.53; N, 14.32; Actual value C, 70.0; H, 6.6; N, 13.9 ; 69.8; 6.7; 13.8. An equimolar mixture of 1,2,4-triazole and sodium methoxide can be used in place of the preformed triazole sodium salt. It should be noted that these reagents must be combined before adding the silane. This is because chloromethylsilanes react very violently in dimethylformamide with sodium methoxide, producing undesirable products. Example 20 Isolation of (1,1'-biphenyl-4-yl)dimethyl(4H-1,2,4-triazol-4-ylmethyl)silane Sodium methoxide-1,2, as in Example 14 1,1'-(biphenyl-4-yl)dimethyl (1H-1,2,4-triazole-
A 5 g sample of 1-ylmethyl)silane was subjected to high pressure liquid chromatography (Waters Prep PAK-500).
Silica gel cartridge, flow rate 250ml/min)
It was attached to. Elution with ethyl acetate-hexane 50:50 first removes some small amounts of impurities and then gives the pure 1H-1.2.4-triazol-1-ylmethyl compound, mp 99-100°C.
was gotten. Ethyl acetate-acetonitrile 80:20
Continued elution with gave a small amount of the title compound as a colorless solid: mp 130−133°C; nmr
(CDCl ₃ ) 0.4 (6H, s), 3.7 (2H, s), 7.2−
7.7 (9H, m), 7.9 (2H, s); C ₁₇ H ₁₉ N ₃ Si
Microanalysis for (mw293.43): Calculated: C, 69.58; H, 6.53; N, 14.32 Observed: C, 69.0; H, 6.7; N, 13.9 69.3; 6.7; 14.2. Example 21 Preparation of dimethyl(phenyl)(1H-1.2.4-triazol-1-ylmethyl)silane 9.0 ml (9.2
g, 0.050 mol) of chloromethyldimethylphenylsilane and 5.5 g (0.060 mol) of 1.2.4
- The mixture of triazole sodium salts was stirred and warmed to 90-95°C for 2 hours, cooled, diluted with water and extracted with ether. The ether solution was washed with water and brine, dried over magnesium sulphate and evaporated to give 8.1 g (75%) of a pale and colored oil, ^n22D _.
1.5350, remained, which contained the title compound and small amounts of impurities as judged by nmr. A purer sample was obtained by distillation: bp99° (0.02
mm); n ²⁰ _D 1.5403; nmr (CDCl ₃ ) 0.4 (6H,
s), 3.8 (2H, s), 7.2-7.7 (5H, m), 7.7
(1H, s), 7.8 (1H, s); C ₁₁ H ₁₅ N ₃ Si
Analysis of (mw217.34): Calculated value C, 60.78; H, 6.96; N, 19.33; Actual value C, 60.7; H, 7.0; N, 16.9; C, 60.2; H, 7.0; N, 16.8. Example 22 (4-chlorophenyl)dimethyl (1H-1.
Preparation of 2,4-triazol-1-ylmethyl)silane 2.2 g (0.010
mol) of chloromethyl(4-chlorophenyl)dimethylsilane and 1.1 g (0.012 mol) of 1.
80% of the mixture of 2,4-triazole sodium salts
Warmed to ~90°C, diluted with water and extracted with ether. The ether solution was washed with water and brine, washed with magnesium sulfate, and evaporated to yield 2.1 g (83
%) of the title compound was obtained as a yellow liquid: n ²¹ _D
1.5428; ir (pure) 1555, 1470, 1245, 1130,
1080, 1010, 835, 805, 795, 735 cm ^-1 ; nmr
(CDCl ₃ ) 0.4 (6H, s), 3.8 (2H, s), 7.4
(4H, wide s), 7.8 (1H, s), 7.9 (1H,
s). Example 23 (2,4-dichlorophenyl)dimethyl (1H-
Preparation of 1,2,4-triazol-1-ylmethyl)silane 5.1 g in 10 ml dry dimethylformamide
A mixture of (0.020 mol) chloromethyl(2,4-dichlorophenyl)dimethylsilane and 2.0 g (0.022 mol) 1,2,4-triazole sodium salt was stirred at 80-90°C for 2 hours. The resulting slurry was cooled, diluted with water, and washed with ether. The ether extract was washed once with several portions of water and brine, dried over magnesium sulfate, and evaporated to leave 4.6 g (81%) of the title compound as a pale yellow liquid: n ²³ _D 1.5580; ir (pure) 1550, 1485, 1440, 1345, 1260, 1240,
1130, 1085, 1025, 1005, 835 cm ^-1 ; nmr
(CDCl ₃ ) 0.5 (6H, s), 4.1 (2H, s), 7.2−
7.5 (3H, m), 7.8 (1H, s), 7.9 (1H, s). Example 24 Bis(4-chlorophenyl)methyl (1H-
Preparation of 1,2,4-triazol-1-ylmethyl)silane 6.3 g in 10 ml dry dimethylformamide
(0.020 mol) of chloromethylbis(4-chlorophenyl)methylsilane and 2.0 g (0.022 mol)
A mixture of 1,2,4-triazole sodium salt was stirred at 80°C for 4 hours. The resulting slurry was cooled, diluted with water, and washed with ether. The ether extract was washed with several portions of water, once with brine, dried over magnesium sulfate, and evaporated to give 5.4 g of a yellow oil. bulb and tube distillation
Performed at 120-150<0>C (air bath)/0.05 mm yielded 4.0 g (58%) of the title compound as a pale yellow oil: ^n26D _1.5966 ; nmr ( _CDCl3 ) 0.7.
(3H, s), 4.1 (2H, s), 7.2−7.5 (8H, m),
7.8 (1H, s), 7.9 (1H, s). In a similar experiment, evaporation of the ether extract gave a gummy solid, which was triturated with hexane to give the title compound as a colorless solid. Melting point 76-80°. Example 25 Bis(4-fluorophenyl)methyl (1H-
Preparation of 1,2,4-triazol-1-ylmethyl)silane 4.2 g (0.015
(mol) of (chloromethyl)bis(4-fluorophenyl)methylsilane and 1.4 g (0.015 mol)
A mixture of 1,2,5-triazole sodium salt was stirred at 80°C for 2 hours. The resulting slurry was cooled, diluted with water, and worked up as in Example 24 to yield 4.0 g of a pale yellow oil. Impurities were removed by bulb-tube distillation at 120-125° C. (0.05 mm), leaving 2.3 g (49%) of the title compound as a yellow oil: n ²¹ _D 1.5538; ir (pure) 3065;
3030, 2960, 2925, 1590, 1500, 1270, 1235,
1165, 1110, 1010, 830, 790cm ^-1 ; nmr
(CDCl ₃ ): 0.7 (3H, s), 4.2 (2H, s), 7.1
(4H, t, J=9), 7.5 (4H, d of d, J=6 and 9), 7.8 (1H, s) and 7.9 (1H, s).
A similarly prepared sample was crystallized from hexane at -20°C to give a colorless solid. Melting point 52-53℃. By applying the procedure of Examples 19 and 21-25 with appropriate chloromethylsilane, Q ₁ =Q ₁ =H
Compounds in the table can be produced.

【table】

【table】

【table】

【table】

【table】

[Table] Example 26 Production of (3,5-dimethyl-1H-1,2,4-triazol-1-ylmethyl)[bis(4-fluorophenyl)]methylsilane The procedure of Example 25 was repeated in equimolar amounts. The title compound is prepared by application to chloromethyl[bis(4-fluorophenyl)]methylsilane and 3,5-dimethyl-1,2,4-triazole sodium salt. 3 instead of 3,5-dimethyltriazole salt
- By using salts of methyl-1,2,4-triazole, related compounds can be prepared. Example 27 (1,1'-biphenyl-4-yl)dimethyl(3-methyl-1H-1,2,4-triazol-
Preparation of 1-ylmethyl)silane 5.9 g in 40 ml dry tetrahydrofuran
(0.020 mol) of (1,1'-biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-
1-ylmethyl)silane under _N2
Cool to 40 °C while 1.6 mol n in hexane
-12.5 ml (0.020 mol) of butyllithium were added dropwise. The resulting yellow solution was stirred at −40° C. for an additional 15 minutes, treated with 1.9 ml (4.2 g, 0.030 mol) of methyl iodide, and warmed to room temperature. The resulting solution was diluted with water and extracted with hexanes. The organic extract was washed with water and brine, dried over magnesium sulfate, and evaporated to give 5.7 g of a solid, which was purified by dry column chromatography on silica gel (elution with ethyl acetate) to give 1.1 g. A crude product was obtained. Recrystallization from 12 ml of 3:1 hexanes-ethyl acetate yielded 0.97 g (16
%) of the title compound was obtained as a gray solid:
mp95−98゜; ir (Nujol ^R ) 1590, 1270, 1250,
1180, 1120, 830, 765, 700cm ^-1 ; nmr
(CDCl ₃ ) 0.5 (6H, s), 2.2 (3H, s) 3.7
(2H, s), 7.2-7.7 (9H, m), 7.8 (1H, s). Although the structure shown is preferred for steric reasons, the position of the methyl group on the triazole ring is not proven, but the product is (1·1′-biphenyl-4-yl)
It can be dimethyl(5-methyl-1H-1.2.4-triazol-1-ylmethyl)silane. The procedures of Examples 26 and 27 can be used to prepare the compounds in the table.

【table】

[Table] Example 28 Preparation of a 1:1 complex of (1,1'-biphenyl-4-yl)dimethyl (1H-1,2,4-triazol-1-ylmethyl)silane and cuprous chloride 170 ml 5.0 g (0.017
A mixture of (1,1'-biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane and 1.7 g (0.017 mole) of cuprous chloride was heated with _N2 reflux for 30 minutes and evaporate the resulting deep green solution to give the title compound as a dark greenish and colored solid: mp85-
90°; ir (Nujol ^R ) 3110, 1590, 1280, 1250,
1120, 1010, 990, 840, 825, 760, ^{700cm -1} . The following metal complexes of (1,1'-bisnyl-4-yl)dimethyl(1H-1,2,4-triazol-4-ylmethyl)silane were prepared simultaneously: 1:1 complex with cupric chloride : mp83-87℃, 2:1 complex with cupric chloride: mp85-92℃, 1:1 complex with zinc chloride: ^n21D _1.5737 , 1:1 complex with manganous sulfate: mp244-
250℃ (decomposition). Example 29 Preparation of 4-dodecylbenzenesulfonate salt of (1,1'biphenyl)-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane 1.0 g (0.0034 A solution of 1.1 g (0.0034 mol) of (1,1'-biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane in 10 ml of dichloromethane was prepared by adding 1.1 g (0.0034 mol) of 4- Combined with a solution of dodecylbenzenesulfonic acid. Evaporation of the resulting solution gave the title salt as a viscous yellow oil:
n ²⁰ _D 1.5645; ir (pure) 3110, 3050, 3020,
2960, 2920, 2850, 2570, 1920, 1600, 1545,
1485, 1455, 1405, 1250, 1225, 1165, 1120,
1030, 1010, 990, 845, 825, 755, 735, 700,
670, 635 cm ^-1 . Example 30 [Bis(4-fluorophenyl)]methyl (1H
-1,2,4-triazol-1-ylmethyl)
Preparation of a 2:1 complex of silane and cupric chloride 1.0 g (0.0032
A mixture of [bis(4-fluorophenyl)]methyl(1H-1.2.4-triazol-1-ylmethyl)silane (mol) and 0.2 g (0.0016 mole) of cupric chloride was heated under _N2 . Reflux for 30 min and evaporation left the title compound as a patina glass: mp unclear; ir (Nujol ^R ) 1580,
1490, 1230, 1160, 1110, 830, ^{785cm -1} . A 1:1 complex with cuprous chloride was similarly prepared,
A dark green glass was obtained: mp unclear; ir as above. By applying the procedures of Examples 26-28, any of the compounds in Tables XII and XII can be converted into salts or metal complexes. Example 31 (1.1'-biphenyl-4-yl) (1H-1.
Preparation of 2,4-triazol-1-ylmethyl)(methoxy)methylsilane (1,1'-biphenyl-4-yl)chlorochloromethylmethylsilane and 2 equivalents of 1,2,4-triazole sodium salt in dimethylformamide and heated to 80-90°C for 2 hours. Then 10 equivalents of methanol are added and the mixture is kept at 70° C. for 1 hour, cooled, diluted with water and rapidly extracted with ether. This ethereal solution was washed with water and brine, dried over magnesium sulfate, and evaporated.
The title compound remains. Using appropriate chlorosilane and alcohol,
For R ₆ = OH, use water instead of alcohol and perform hydrolysis at 20-25 °C instead of 70 °C.
Related compounds can be made using the same method. Example 32 Preparation of (1,1-dimethylethoxy)methyl(phenyl)(1H-1,2,4-triazol-1-ylmethyl)silane 3.6 g (0.015
A mixture of chloromethyl(1,1-dimethylethoxy)methyl(phenyl)silane (mol) and 1.3 g (0.015 mol) of 1,2,4-triazole sodium salt was stirred at 80°C for 2 hours, cooled, and poured over water. poured into. The resulting mixture was extracted with water, and the ethereal extracts were washed with water and brine, dried over magnesium sulfate, and evaporated to leave 2.7 g of a yellow oil. Perform chromatography on silica gel,
When eluted with 50:50 ethyl acetate-hexanes,
1.5 g (36%) of the title compound was obtained as a pale yellow oil: ^n21D _1.5134 ; ir (pure) 3120, 3070,
3045, 2975, 2925, 1500, 1425, 1380, 1365,
1270, 1255, 1240, 1190, 1140, 1115, 1050,
1020, 1010, 830, 810, 790, 740, 700, 680cm
^-1 ; nmr (CDCl ₃ ): 0.6 (3H, s), 1.3 (9H,
s), 3.9 (2H, s), 7.3-7.7 (5H, m), 7.9
(1H, s) and 8.0 (1H, s). Using the procedure of Examples 31 and 32, Q ₁ =Q ₂ =
Compounds of table H and can be prepared.

【table】

【table】

【table】

【table】

[Table] Example 33 Preparation of chloromethyl(dichloro)phenylsilane 25.1 ml in 400 ml dry tetrahydrofuran
A solution of (36.8 g, 0.200 mol) chloromethyltrichlorosilane was cooled to -78°C under nitrogen and stirred vigorously while 48.0 ml (0.100 mol) of 2.1
mol of phenyllithium was slowly added dropwise over 1 hour. After stirring for an additional 30 min at −78°C, the solution was warmed to room temperature and evaporated to approximately 200
ml. After addition of 500 ml of ether, the precipitated lithium chloride was removed and the liquid was evaporated, leaving 25.0 g of liquid. When distilled, 6.5g
(29%) of the title compound was obtained as a colorless liquid: bp62-82° (0.15 mm); nmr ( _CDCl3 ): δ
3.3 (s, 2) and 7.1-7.9 (m, 5). Example 34 Preparation of chloromethyl(diethoxy)phenylsilane A solution of 1.0 g (0.0044 mol) of chloromethyl(dichloro)phenylsilane in 8 ml of absolute ethanol was cooled to 0° C. under nitrogen, stirred,
During that time, 0.61 ml (0.445 g, 0.0044 mol) of triethylamine was slowly added, resulting in a slurry that was warmed to room temperature. Add 50ml of ether;
After removing the precipitated triethylamine/hydrogen chloride and evaporating the liquid, a residue is obtained which is passed through a short column of silica gel (95% petroleum ether: ethyl acetate as eluent). 0.80 g (73%) of the title compound was obtained as a colorless oil: nmr ( _CDCl3 ): 1.25 (t, 6,
J = 6Hz), 3.0 (s, 2), 3.9 (q, 4, J = 6
Hz) and 7.2−7.9 (m, 5). Example 35 Preparation of chloromethyl(phenyl)bis(2-propoxy)silane 2.0 g (0.009
A solution of chloromethyl(dichloro)phenylsilane (mol) and 5 ml of 2-propanol was stirred under N ₂ while 2.5 ml (1.9 g, 0.018 mol) of triethylamine was added dropwise. The resulting slurry was warmed to 80° C. for 2 hours, cooled, diluted with water, and extracted with ether. The ether extract was washed with water and brine, dried over magnesium sulfate,
After evaporation, 2.2 g of liquid remained. Column chromatography on silica gel and elution with petroleum ether gave 1.4 g (58%) of the title compound as a colorless liquid: n ²² _D 1.4741; nmr
(CDCl ₃ ) 1.2 (12H, d, J=6), 3.0 (2H,
s), 4.3 (2H, septet, J=6), 7.3−7.8
(5H, m). Using the procedures of Examples 33-35, the compounds of Tables and XI can be prepared.

【table】

【table】

【table】

[Table] Example 36 Phenylbis(2-propoxy) (1H-1・
Preparation of 2,4-triazol-1-ylmethyl)silane By applying the procedure of Example 32 to chloromethyl(phenyl)bis(2-propoxy)silane, the title compound can be made: n ²² _D
1.4962; nmr (CDCl ₃ ) 1.1 (12H, d, J=
6), 4.0 (2H, s), 4.3 (2H, septet, J=
6), 7.2−8.0 (7H, m). Compounds of Table XII and can be made similarly.

【table】

【table】

【table】

【table】

TABLE FORMULATIONS Useful formulations of compounds within the scope of this invention can be prepared by conventional methods. For example, the compounds can be formulated as dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, and the like. Many of these are directly applicable. Sprayable formulations can be bulked up with suitable media and used at spray volumes of a few liters to a few hundred liters/ha.
High strength compositions are primarily used as intermediates for further compounding. The formulation is widely used in approx.
0.1-99% by weight of active ingredient and (a) about 0.1-20% by weight;
of a surfactant and (b) about 5-99% by weight of at least one solid or liquid inert diluent. More specifically, the formulations will contain these components in approximate proportions as shown in Table 3.

Table of Contents Of course, lower or higher levels of active ingredient can be present depending on the intended use and physical properties of the compound. A high ratio of surfactant to active ingredient is sometimes desirable and achieved by incorporation into the formulation or by bath mixing. Some typical solid diluents are Watkins,
et al., “Handbook of Insecticide Dust
Diluents and Carriers”, 2nd Ed., Dorland
Books, Caldwell, New Jersey. More absorbent diluents are preferred for wet powders;
And denser ones are preferable to dust. Typical liquid diluents and solvents include Marsden,
“Solvents Guide,” 2nd Ed., Inter science,
New York, 1950. A solubility of 0.1% or less is preferred for suspension concentrates and solution concentrates are preferably stable to phase separation at 0°C.
Emulsifiers Annual”, MC Publishing Corp.,
Ridgewood, New Jersey, and Sisely and
Wood. “Encyclopedia of Surfae Active
Chemical Publishing Co., Inc.
New York, 1964 describes surfactants and recommended uses. All formulations may contain small amounts of additives to inhibit foaming, caking, corrosion, and microbial growth. Methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Finely divided solid compositions are created by blending, usually by grinding, such as in a hammer mill or fluid energy mill. Suspensions are prepared by wet milling (e.g.
Litter, U.S. Pat. No. 3,060,084). Granules and pellets can be made by spraying the active agent onto preformed granules or by any one of a number of agglomeration techniques. JE
Browning, “Agglomeration”, Chemical
Engineering, December 4, 1967, pp.147ff. and “Perry’s Chemical Engineer’s
Handbook”, 4th edition., McGraw-Hill, New
See York, 1963, pp. 8-59ff. Formulation example 1 Wettable powder (1,1-biphenyl-4-yl)dimethyl (1H
-1,2,4-triazol-1-ylmethyl)silane 40% Dioctyl sodium sulfosuccinate 1.5% Sodium lignin sulfonate 3% Low viscosity methyl cellulose 1.5% Attapulgite 54% These ingredients were mixed well and passed through an air mill. , reformulated to an average particle size of less than 15 microns,
After sieving through a US Standard 50 sieve (0.3 mm opening), package. All compounds of the invention can be formulated in the same manner. Formulation example 2 Wettable powder (4-bromophenyl) dimethyl (1H-1.2.
4-Triazol-1-ylmethyl)silane 20% Sodium alkylenenaphthalene sulfonate 2% Low viscosity methylcellulose 2% Diatomaceous earth 76% These ingredients were blended, coarsely hammer milled, then air milled to give essentially all Produces active particles less than 10 microns in diameter. After the product is reformulated, it is packaged. Formulation example 3 High strength concentrate (4-chlorophenyl) dimethyl (1H-1・2・
4-Triazol-1-ylmethyl)silane 98.5% Silica airgel 0.5% Synthetic amorphous finely divided silica 1.0% These ingredients were blended and ground in a hammer mill to ensure that essentially all of the components passed through a US Standard No. 50 sieve ( produces a high strength concentrate that passes through a 0.3 mm aperture). This material can then be formulated in a variety of ways. Formulation Example 4 Dust High Strength Concentrate from Formulation Example 3 25.4% Pyrophyllite, Powder 74.6% These ingredients are blended well and packaged for use. Formulation example 5 Aqueous suspension (1,1'-biphenyl-4-yl)dimethyl (1H
-1,2,4-triazol-1-ylmethyl)silane 50.0% Polyacrylic acid thickener 0.3% Dodecyl phenyl polyethylene glycol ether 0.5% Disodium phosphate 1.0% Monosodium phosphate 0.5% Polyvinyl alcohol 1.0% Pentachlorophyll Enyl 0.4% Water 46.3% These ingredients are blended together in a sand mill to produce particles that are substantially all less than 5 microns in size. Formulation example 6 Emulsifiable concentrate Dimethyl(phenyl)(1H-1.2.4-triazol-1-ylmethyl)silane 20% Chlorobenzene 74% Sorbitan monostearate and its polyoxyethylene condensate 6% These ingredients Combine and stir to form a solution. This solution can be emulsified in water for application. Formulation example 7 Emulsifiable concentrate dimethyl (4-methylphenyl) (1H-1・2・
4-Triazol-1-ylmethyl)silane 30% Blend of oil-soluble sulfonate and polyoxyethylene ether 4% Xylene 66% Combine these ingredients and stir with gentle warming to accelerate dissolution. A fine sieve filter is included in the packaging operation to ensure that no extraneous undissolved material is present in the product. Formulation Example 8 Granules Wettable powder of Example 46 15% Setsukou 69% Potassium sulfate 16% These ingredients are blended in a rotary mixer and granulated by spraying with water. Most of the material is 1.0~0.42
When the desired range of mm (US Standard No. 18-40 sieve) is reached, the granules are removed, dried and sieved. Larger materials are ground to create the desired range of additional material. These granules contain the active ingredient. Formulation example 9 Emulsifiable concentrate (2,4-dichlorophenyl)dimethyl (1H-
1,2,4-triazol-1-ylmethyl)silane 30% Blend of oil-soluble sulfonate and polyoxyethylene ether 4% Xylene 66% These ingredients are combined and stirred with gentle heating to accelerate dissolution. do. Fine sieve filters are included in the packaging operation to ensure that extraneous, undissolved materials are not included in the product. Formulation example 10 Emulsifiable concentrate butyl (4-chlorophenyl) methyl (1H-
1,2,4-triazol-1-ylmethylsilane
30% oil-soluble sulfonate and polyoxyethylene ether blend 4% xylene 60% Combine these components and stir with gentle warming to accelerate the solution. Fine sieve filters are included in the packaging operation to ensure that extraneous, undissolved materials are not included in the product. Formulation example 11 Emulsifiable concentrate bis(4-chlorophenyl)methyl (1H-1.
2,4-triazol-1-ylmethyl)silane
30% oil-soluble sulfonate and polyoxyethylene ether blend 4% xylene 66% These ingredients are combined and stirred with gentle warming to accelerate dissolution. Fine sieve filters can be wrapped in the packaging operation to prevent extraneous, undissolved materials from becoming encased in the product. Formulation example 12 Bis(4-fluorophenyl)methyl (1H-
1,2,4-triazol-1-ylmethyl)silane 20% Chlorobenzene 74% Sorbitan monostearate and its polyoxyethylene condensate 6% These components are combined and stirred to form a solution. This solution can be emulsified with water for application. Formulation example 13 Emulsifiable concentrate 4-fluorophenyl(methyl)phenyl (1H
-1,2,4-triazol-1-ylmethyl)silane 30% Blend of oil-soluble sulfonate and polyoxyethylene ether 4% Xylene 66% These ingredients are combined and stirred with gentle heating to accelerate dissolution. do. Fine sieve filters are included in the packaging operation to ensure that extraneous, undissolved materials are not included in the product. Practicality The compounds of the present invention are useful as agents for controlling plant diseases. They are foliar pathogens of a wide spectrum of plants, especially ornamental plants, vegetables, cereals and fruit crops, e.g.
Pucciniarecondita, Erysiphe cichoracearum,
Erysiphe graminis, Venturia inaequalis,
Helminthosporium maydis, Cercospora
arachidicola Uromyces phaseoli and Monilinia
fructicola, Rhizoctonia solani, Pyricularia
oryzae, Phytophthora infestans and other
Effective against Phytophthora species. Also, they are pathogens of species, for example, Pythium
Suppress aphanadermatum. Disease control is usually achieved by applying an effective amount of a compound to the part of the plant to be protected, such as roots, stems, leaves, fruits, seeds, tubers or bulbs, or to the medium in which the plant to be protected is growing (soil or sand). ), applied before or after infection. Also,
The compounds can be applied to the plants to be protected and to the seeds to be grown. The application rate of these compounds can be influenced by many environmental factors and should be determined under actual conditions of use. Leaves can usually be protected when treated at proportions of active ingredient from less than 1 ppm up to 500 ppm. Plants grown in soil treated with concentrations of 0.1 to about 20 Kg/ha can be protected from disease.
Seeds and seedlings usually contain 0.06 to about 3 kg/kg of seeds.
Protection can be achieved by treating at a ratio of The compounds of the present invention can be used as fungicides, bactericides,
It can be mixed with acaricides, nematicides, insecticides, or other biologically active compounds to achieve the desired results with minimal consumption of time, effort, and materials. The amount of these biologically active substances added per part by weight of the composition of the invention can vary between 0.05 and 25 parts by weight. Suitable substances of this type are well known. Some are listed below. Fungicides Methyl 2-benzimidazole carbamate (carbendazim) Tetramethylthiuram disulfide (thiram) t-Dodecylguanidine acetate (dodine) Manganese ethylene bisdithiocarbamate (maneb) 1,4-dichloro-1,5-dimethoxybenzene (chloroneb) ) Methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate (benomyl) 2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil) N-(trichloromethylthio)tetrahydrophthalimide (captan) N-(trichloromethylthio) ) Phthalimide (folpet) Dimethyl 4,4'-(o-phenylene)bis(3
-Thioallophanate) (throphanate-
methyl) 2-(thiazol-4-yl)benzimidazole (thiabendazole) Aluminum tris(O-ethylphosphonate (“Aliette”)) Tetrachloroisophthalonitrile (chlorothalonil) 2,6-dichloro-4-nitroaniline (dichloran) N -(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl ester (metelaxyl) cis-N-[(1,1,2,2-tetrachloroethyl)thio]cyclohex-4-ene-1. 2-
Dicarbioximide (captafol) 3-(3,5-dichlorophenyl)-N-(1 methylethyl)-2,4-dioxo-1-imidazolidinecarboxamide (iprodione) 3-(3,5-dichloro phenyl)-5-ethenyl-5-methyl-2,4-oxazolidinedione (vinclozolin) Kasugamycin O-ethyl-S.S-diphenylphosphorodithioate (edifenphos) Bactericide Tribasic copper sulfate Streptomycin sulfate Oxygen Tetracycline acaricide Senecionic acid, ester with 2-sec-butyl-4,6-dinitrophenol (binapacryl) 6-methyl-1,3-dithiolo[4,5-B]
Quinoxalin-2-one (oxythioquinox) 2,2,2-trichloro-1,1-bis(4-
chlorophenyl) ethanol (dicofol) bis(pentachloro-2,4-cyclopentadien-1-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin) hexakis(2-methyl-2-phenylpropyl) distannoxane (fenbutin oxide) Nematode agent 2-(diethoxyphosphinylimino)-1/3
-fosthietan S-methyl 1-(dimethylcarbamoyl)-N-
(Methylcarbamoyloxy)-thioformimidate (oxamyl) S-Methyl 1-carbamoyl-N-(methylcarbamoyloxy)thioformimidate N-isopropylphosphoramidic acid, O-ethyl-O'[4-(methylthio )-m-tolyl]diester (fenamiphos) Insecticide 3-hydroxy-N-methylcrotonamide (dimethyl phosphate) ester (monocrotophos) Methylcarbamic acid, 2,3-dihydro-2.
2-dimethyl-7-benzofuran (carbofuran) O-[2,4,5-trichloro-α-(chloromethyl)benzyl]phosphoric acid, O', O'-dimethyl ester (tetrachlorvinphos) 2-mercaptosuccinic acid, diethyl ester,
S-ester with thionolinic acid, dimethyl ester (malathion) Phosphorothioic acid, O.O-dimethyl, O-p
-Nitrophenyl ester (methyl parathion) Methylcarbamic acid, ester with α-naphthol (carbaryl) Methyl N-[[(methylamino)carbonyl]oxy]ethanimidothioate (methomyl) N'-(4-chloro-o -tolyl)-N・N-dimethylformamidine (chlordimeform) O・O-diethyl-O-(2-isopropyl-
4-Methyl-6-pyrimidyl) phosphorothioate (diazinon) Octachlorocamphene (toxaphene) O-ethyl O-p-nitrophenylphenyl phosphonothioate (EPN) Cyano-(3-phenoxyphenyl) methyl 4
-chloro-α-(1-methylethyl)benzene acetate (fenvalerate) (3-phenoxyphenyl)methyl (±)-cis, trans-3-(2,2-dichloroethenyl)-2,2-dimethylcyclo Propanecarboxylate (permethrin) Dimethyl N・N'-[thiobis[(N-methylimino)carbonyloxy]]bis[ethanimidothioate] (thiodicarb) Phosphorothiorothionate, O-ethyl-O-
[4-(Methylthio)phenyl]-S-n-propyl ester (sulprofos) α-cyano-3-phenoxybenzyl 3-
(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (cypermethrin) cyano(3-phenoxyphenyl)methyl 4-
(difluoromethoxy)-α-(methylethyl)benzene acetate (“Payoff”) O・O-diethyl-O-(3,5,6-trichloro-2-pyridyl)phosphorothioate (chlorpyrifos) O・O-dimethyl-S −[(4-oxo-1・
2,3-benzotriazin-3-(4H)-yl)
Methyl phosphorodithioate (azinphosmethyl) 5,6-dimethyl-2-dimethylamino-4-
Pyrimidinyl dimethyl carbamate (“Pirimor”) S-(N-formyl-N-methylcarbamoylmethyl)-O.O-dimethylphosphorodithioate (formothion) S-2-(Ethylthioethyl)-O.O-dimethyl Phosfluorothioate (demeton-S-
methyl) α-cyano-3-phenoxybenzylcis-3
-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (deltamethrin) N-(2-chloro-4-trifluoromethylphenyl)alanine (“Mavrik”) The invention will be further explained. Test Example 1 A compound of the present invention was added to 6% of the final volume in acetone.
and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM014 (a polyhydric alcohol ester).
These suspensions were sprayed onto rice seedlings to the extent that they dripped. The next day, the plants were infected with Puccinia recondita var., the pathogen of wheat leaf rust.
tritici spore suspension and cultured for 24 hours in a saturated humidity chamber at 20° C. and then for a further 7 days in a growth chamber, and then the disease was graded. The table below shows the percentage of disease control. The treated plants had few or no rust warts, whereas the untreated plants had many warts on each leaf.

【table】

【table】

[Table] Test Example 2 The compound of the present invention was added to 6% of the final volume in acetone.
and then suspended at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM014 (a polyhydric alcohol ester).
These suspensions were sprayed onto cucumber seedlings to the point of dripping. The next day, the plants were inoculated with a spore suspension of the cucumber powdery mildew pathogen Erysiphe cichoracearum and incubated in a growth chamber for 7 days. The disease grade was then determined. The percentage of disease control is shown in the table below. The treated plants have little or no powdery mildew, in contrast to untreated plants which are covered with powdery mildew. Phytotoxicity in the form of reduced growth or hormonal effects was observed in some plants in connection with disease control.

【table】

【table】

[Table]

【table】

[Table] Test Example 3 A compound of the invention is dissolved in acetone in an amount equal to 6% of the final volume and then at a concentration of 100 ppm in pure water containing 250 ppm of the surfactant TREM014 (ester of polyhydric alcohol). Suspended.
These suspensions were sprayed dripping onto barley seedlings. The next day, the plants were inoculated with a spore suspension of the powdery mildew pathogen of barley, Erysiphe graminis, and then incubated in a growth chamber for 7 days.
The disease grade was then determined. The disease suppression rate is shown in the table below. The treated plants had little or no powdery mildew compared to untreated plants covered with powdery mildew.

[Table] Triphenylsilane

[Table] Test Example 4 A compound of the invention is dissolved in acetone in an amount equal to 6% of the final volume and then at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM014 (ester of polyhydric alcohol). Suspended. These suspensions were sprayed onto apple seedlings until dripping. The next day, the plants were inoculated with a spore suspension of the apple rot pathogen Venturia inaequalis and incubated in a saturated room at 20°C for 24 hours and then in a growth room for an additional 10-12 days. The disease grade was then also determined and recorded as shown in the table below. The treated plants had fewer rot lesions compared to untreated plants which were covered with rot lesions. Phytotoxicity, expressed as a reduction in growth, was observed in some of the plants in relation to diseased controls.

【table】

【table】

【table】

[Table] Test Example 5 A compound of the invention is dissolved in acetone in an amount equal to 6% of the final volume and then at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM014 (ester of polyhydric alcohol). Suspended. These suspensions were sprayed onto corn seedlings until dripping. The next day, the plants were inoculated with a spore suspension of Helminthosporium maydis, a foliar pathogen of southern corn, incubated in a saturated chamber at 20°C for 24 hours, and then incubated in a growth chamber for an additional 7 days. , determined the grade of the disease. The disease suppression rate is shown in the table below. Treated plants had few or no lesions, while untreated plants had numerous lesions on each leaf. Phytotoxicity, expressed as a reduction in growth, was observed in some of the plants in relation to the disease control.

[Table] Silane

【table】

[Table] Test Example 6 A compound of the invention is dissolved in acetone in an amount equal to 6% of the final volume and then at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM014 (ester of polyhydric alcohol). Suspended. These suspensions were sprayed onto peanut seedlings until dripping. The next day, plant the early spot pathogen Cercospora on peanuts.
arachidicola spore suspension, incubated for 24 hours at 27°C in a room with saturated humidity, and then cultured for an additional 14 days in a growth chamber to determine the disease grade. The results are shown in the table below. The treated plants had little or no leaf spot, whereas the untreated plants had a lot of leaf spot. Phytotoxicity expressed as burns was observed on some of the plants in relation to disease controls.

【table】

【table】

Table Example 74 A compound of the invention is dissolved in acetone in an amount equal to 6% of the final volume and then dissolved in purified water containing 250 ppm of the surfactant TREM014 (ester of polyhydric alcohol) at a concentration of 80 ppm. Suspended. This suspension was sprayed onto bean seedlings until drippings. The next day, remove the plants from the bean rust fungus.
It was inoculated with a spore suspension of Uromyces phaseoli and cultured for 24 hours at 20° C. in a saturated humidity chamber, and then for 7 days in a greenhouse. The disease grade was then determined. The disease suppression rate is shown in the table below. The treated plants had few or no rust warts, whereas the untreated plants were covered with rust warts. Phytotoxicity in the form of reduced growth was observed in some of the plants in relation to disease controls.

[Table]

Table Test Example 8 A compound of the invention was dissolved in acetone in an amount equal to 5% of the final volume and then dissolved in purified water containing 700 ppm of the surfactant TREM014 (ester of polyhydric alcohol) at a concentration of 100 ppm. Suspended. Canned peach halves were soaked in this suspension for 3 minutes and then placed in a sterile container to air dry. When dry, half of the peaches were inoculated with two pieces of the stone fruit and color rot pathogen Monilinia fructicola mycelium and incubated in sterile containers for 5 days. At that time, the radius of colony growth was measured for each peach. Colonies on treated peaches either did not grow or only grew within a radius of a few millimeters;
Colonies grown on untreated peaches covered the entire surface of the peaches. The disease inhibition rate (percentage inhibition of colony growth on treated peaches compared to colony growth on untreated peaches) is shown in the table below.

[Table] Silane

[Table] Test Example 9 A compound of the invention is dissolved in acetone in an amount equal to 6% of the final volume and then at a concentration of 100 ppm in purified water containing 250 ppm of the surfactant TREM014 (ester of polyhydric alcohol). Suspended. This suspension was sprayed onto rice seedlings until drippings. The next day, the plants were inoculated with a mixture of rice bran and mycelium of Rhizocotonia solani, a leaf beetle pathogen of rice, and cultured in a growth chamber for 7 days. The disease grade was then determined. The disease suppression rate is shown in the table below. The treated plants had almost no sheath disease, whereas the untreated plants were covered with sheath disease.

【table】

Table: Test Example 10 A compound of the invention is dissolved in acetone in an amount equal to 6% of the final volume and then dissolved in purified water containing 250 ppm of the surfactant TREM014 (ester of polyhydric alcohol) at a concentration of 100 ppm. Suspended. These suspensions were sprayed onto rice seedlings until dripping. The next day, the plants were inoculated with a spore suspension of Pyricularia oryzae, the pathogen of rice leaf blight, and cultured for 24 hours at 28°C in a room with saturated humidity, and then for an additional 7 days in a growth room. The disease grade was then determined. The disease suppression rate is shown in the table below. Treated plants had few or no lesions, whereas untreated plants had numerous lesions on each leaf.

[Table] Silane

【table】

[Table] Compound inhibition%

Claims (1)

[Claims] 1 formula where Q ₁ and Q ₂ are independently H; R ₁ is C ₂ -C ₁₈ alkyl, C ₆ cycloalkyl, naphthyl or [Formula]; R ₂ and R ₃ are independently C ₁ -C ₆ alkyl, OR ₆ or [Formula]; R ₄ and R ₅ are independently H, halogen, -OCH ₃ , -
_OCF3 , _-SCH3 , _-SO2CH3 , phenyl, halogen-substituted phenyl, phenoxy, halogen-substituted phenoxy, _-CF3 , _C1 - _C4 alkyl, or _cyclohexyl ; _R6 is H or _C1 - _C4 alkyl; provided that both _R2 and _R3 cannot be OH at the same time; salts thereof and metal complexes. 2. The compound according to claim 1, which is (1,1'-biphenyl-4-yl)dimethyl(1H-1,2,4-triazol-1-ylmethyl)silane. 3 Bis(4-chlorophenyl)methyl(1H-
1. The compound according to claim 1, which is 1,2,4-triazol-1-ylmethyl)silane. 4. The compound according to claim 1, which is [bis(4-fluorophenyl)]methyl(1H-1.2.4-triazol-1-ylmethyl)silane. 5. The compound according to claim 1, which is 4-fluorophenyl(methyl)phenyl(1H-1.2.4-triazol-1-ylmethyl)silane. 6 formula where Q ₁ and Q ₂ are independently H; R ₁ is C ₂ -C ₁₈ alkyl, C ₆ cycloalkyl, naphthyl or [Formula]; R ₂ and R ₃ are independently C ₁ -C ₆ alkyl, OR ₆ or [Formula]; R ₄ and R ₅ are independently H, halogen, -OCH ₃ , -
_OCF3 , _-SCH3 , _-SO2CH3 , phenyl, halogen-substituted phenyl, phenoxy, halogen-substituted phenoxy, _-CF3 , _C1 - _C4 alkyl, or _cyclohexyl ; _R6 is H or C ₁ - C ₄ alkyl; provided that both R ₂ and R ₃ cannot be OH at the same time; at least one compound selected from compounds, salts thereof, and metal complexes as an active ingredient. An agent for suppressing diseases caused by fungi. 7. The agent according to claim 6 in the form of a composition comprising the active ingredient and at least one of a surfactant and a solid or liquid inert diluent. 8 formula where Q ₁ and Q ₂ are independently H; R ₁ is C ₂ -C ₁₈ alkyl, C ₆ cycloalkyl, naphthyl or [Formula]; R ₂ and R ₃ are independently C ₁ -C ₆ alkyl, OR ₆ or [Formula]; R ₄ and R ₅ are independently H, halogen, -OCH ₃ , -
_OCF3 , _-SCH3 , _-SO2CH3 , phenyl, halogen-substituted phenyl, phenoxy, halogen-substituted phenoxy, _-CF3 , _C1 - _C4 alkyl, or _cyclohexyl ; _R6 is H or C ₁ -C ₄ alkyl; provided that both R ₂ and R ₃ cannot be OH at the same time; A method of controlling dental disease, which consists in applying it where it is needed. 9 formula where Q ₁ and Q ₂ are independently H; R ₁ is C ₂ -C ₁₈ alkyl, C ₆ cycloalkyl, naphthyl or [Formula]; R ₂ and R ₃ are independently C ₁ -C ₆ alkyl, OR ₆ or [Formula]; R ₄ and R ₅ are independently H, halogen, -OCH ₃ , -
_OCF3 , _-SCH3 , _-SO2CH3 , phenyl, halogen-substituted phenyl, phenoxy, halogen-substituted phenoxy, _-CF3 , _C1 - _C4 alkyl, or _cyclohexyl ; _R6 is H or C ₁ -C ₄ alkyl; provided that both R ₂ and R ₃ cannot be OH at the same time; (1) Cl ₃ SiCH ₂ Cl,
An intermediate selected from the group of [formula] and [formula] is prepared in a suitable solvent with R ₁ M (wherein M is Na, Li) or M ₈ X (wherein X is Br,
Cl, I) to form chloromethylsilane, and (2) react the chloromethylsilane with 1,2,4-triazole, its 3-methyl or 3,5-dimethyl derivative, or their A process comprising reacting an alkali metal salt in a polar aprotic solvent, an ether or a ketone at 0°C to 150°C. 10 [Formula] and [Formula] are reacted with R ₆ OH in a suitable solvent in the presence of a suitable base to form an alkoxy or dialkoxychloromethylsilane,
And (2) this chloromethylsilane is 1,2,4-
Claim 1, wherein the triazole, its 3-methyl or 3,5-dimethyl derivative, or an alkali metal salt thereof is reacted in a polar aprotic solvent, ether or ketone at 0°C to 150°C. Method for producing a compound of formula-1.