JPS58144393A - Bactericidal 1,2,4-triazole and imidazole derivatives - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention relates to zolylmethyl) II azoles and imidazoles, such as dimethyl(phenyl)rlH-1,
2,4-)riazol-1-ylmethyl)7rane and (
1,1'-biphenyl-4-yl)dimethyl(IH-imidazol-1-ylmethyl)silane, and the use of these novel compounds in the control of fungal diseases, especially of live plants. . U.S. Patent No. 3.69 Z798 discloses that in the formula Rt , R
1 and R8 can be lower alkyl and phenyl. These compounds are said to be useful as antimicrobial agents. European Patent No. 29,993 discloses that R is C, -C4 alkyl, and Y and Z can be H or SiR, R, R, T, which ζ
and R+, Rt and R9 are alkyl, haloalkyl,
Discloses compounds of which can be alkenyl, alkynyl or substituted phenyl. The compounds are taught to be useful as agricultural fungicides. U.S. Patent No. 256,308 and 3,337;
No. 598 discloses compounds of the formula where at hamethyl, ethyl, vinyl, mata can be phenyl. Their use for controlling fungi has also been taught. Belgian Patent No. 785.127 discloses quaternary ammonium salts, such as CH,
syCH. and their use as fungicides. Research Disclosure (1'tsearch
Disclosure) No. 17,652 has the formula %formula%) in which A" can be substituted phenyl, XH
Discloses silyl ethers which can be CH or N, and R can be alkyl. The compounds are taught to be useful as agricultural fungicides. West German Patent 1) R3,000,140 describes the formula % where Ar#-1, can be substituted phenyl, can be X#'iCH or N, and R is phenyl discloses a silyl ether of which can be lower alkyl or lower alkyl. These compounds are taught to be useful as agricultural fungicides. U.S. Pat. No. 4,248,992 discloses that at least one monovalent guanidine group represented by the general formula R is a hydrocarbon atom or a monovalent hydrocarbon group.
Discloses a class of compounds having organosilicon compounds in their molecules. The guanidine-containing organosilicon compounds are described as useful as antimicrobial agents for molded plastics and rubbers, particularly silicone rubbers.・Baet Socialist Republic Federal Patent No. 346,306 has the formula % formula % where R3 and Rffi are an alkyl group, and n is 0 to
3, and At is an optionally substituted pyrazole, imidazole, or penzimitazole;
discloses silylethylazoles of Sakai. USSR Patent No. 271,552 discloses silylethylazoles of the formula % where R, , R, , n and Ax are exactly as described above. The present invention relates to silylmethyl)+1 azoles of the formula I and silylmethylimidazoles of the formula (I) and agriculturally useful compositions of these compounds. Q. In the formula, Q+, Qt and C3 are independently H or CHs, 1 n is l, R1 is Ca Cps argyl, Cs Ca cycloargyl, naphthyl, R( is Cs Cps alkyl, C, -C. cycloalkyl, naphthyl or 4Its, and R7 and R8 are independently C, -C, alkyl, C, -C
, cycloalkyl, OR6 or, R4 and R6 are independently -H; halogen; 0CH8;
0CFI; 8CHs; 80tCHs: phenyl; phenyl substituted with halogen and/or C, -C4 alkyl and/or -CF3; phenoxy; halogen and/or C, -C4 alkyl and/or
Phenoxy substituted with O or 10F; CFa; C
I 04 alkyl;
, and R8 cannot both be OH, and R1 and R1 together can be 1,2- or 1,3- or 1,4-glycol bridges or up to 4 with a total of up to 4 carbon atoms. can be a 1,4 unsaturated glycol bridge substituted with an argyl group R2R1 (l). H or CH, n is 1, R6 and R) are C*-C+ s alkyl, cl-
C6 cycloalkyl, naphthyl or R2H. and R and R8 are independently C+ Co alkyl, C, -
C, cycloargyl, 0Raitake, R4 and R6 are independently -HH/・rogen; OCHm;
0CFs; scHm; 5OtCHs; phenyl; halogen and/or Cl-04 alkyl and/
or 10F, substituted with 9 phenyl: phenoxy;
or phenoxyny CFm substituted with 10 FA;C
+ c4 alkyl; or cyclohexyl, and R1 is H or C+ C4 alkyl, with the proviso that R
Both 2 and R3 cannot be tiOH and R1 and R8 together can be 1,2- or 1,3- or 1,4-glycol bridges or up to 4 carbon atoms with a total of up to 4 carbon atoms. Alkyl group R7-R,. Diseases of fungi, especially those of living species, consisting of applying an effective brush of a compound of , which can be a 1,4-unsaturated glycol bridge substituted with , to the place to be protected. Concerning how to suppress. When R, t or R5 is OH, formula ■ and formula ■ are
It should be understood to include dioxolane. The present invention also relates to salts of the compounds of formulas (1) and (2) with protonic acids and complexes with gold S ions. Due to their high activity and/or suitably easy synthesis, preferred compounds are those in the general range where Ql=Qt=ii. More preferred compounds because of their higher activity and/or because they are preferably easier to synthesize are the preferred range of compounds where R4R@R8 is c, -c4 alkyl. The highest activity and/or the most suitable synthesis @ where R4 is R+'! or BE, and R4 is H, F, CI, Br4, or phenyl, and R is H, FSClt, or BE, and K. and R3 is C,-C4 alkyl. Particularly preferred compounds, due to their excellent activity and/or because they are most preferably easy to synthesize, have the following formula 1:
It is a compound of: 1dimethyl)phenyl(IH-1,2,4-)riazol-1-ylmethyl)silane, dimethyl(4-methylphenyl1(IH-1,2゜4-
triazol-1-ylmethyl)7rane, C4-bromophenyl)dimethyl (IH-1,2゜4-triazol-1
-ylmethylisilane, (1*1'-viazniru4-
yl)dimethyl(IH-1,2,4-)lyazol-1-
ylmethyl)silaneC4-chlorophenyl)dimethyl(IH-1,2゜4-
triazol-1-ylmethyl)silane, (2,4-dichlorophenyl)dimethyl(IH-1,2,4-)riazol-1-ylmethyl)silane, butylC4-chlorophenyl)methyl rlH~1.2.
4-) Riazol-1-ylmethyl)silane, bis(4-chlorophenyl)methyl(IH-1゜2.4
-17azol-1-ylmethyl)7rane, methyl(diphenyl)(IH-1,2,4-triazol-1-ylmethyl)silane, [bis(4-fluorophenyl)]methyl(IH-1,2,4- triazol-1-ylmethyl)
Silane, C4-fluorophenyl)dimethyl (IH-1
゜2.4-)riasol-1-ylmethyl)silane, butyl゛(2,4-dichlorophenyl)methyl cIH-1,
2,4-triazol-1-ylmethyl)silane, [bis(2,4-dichlorophenyl)]methyl(1)(
-1,2,4-)riazol-1-ylmethyl)silane 2,4-dichlorophenyl(methyl)phenylMH-1
,2,4-)riazol-1-ylmethyl)silane 4-chlorophenylfmethyl)phenyl(I H-1,
2,4-)riazol-1-ylmethyl)puran, 4-fluorophenyl(methyl)phenyl (IH-11
2,4-triazol-ylmethyl)silane, butylCmethyl)phenyl(IH-1,2,4-triazol-1-
ylmethyl)silane, butylC4-fluorophenyl)
Methyl (I H-1,2,4-)riazol-1-ylmethyl)7, [bisN,1'-biphenyl-4-yl)]dimethyl I
H-1,2,4-)riazol-1-ylmethyl)silane, (1,1'-biphenyl-4-yl)butyl(methyl)
(IH-1,2,4-triazol-1-ylmethyl)silane, and rl,1'-biphenyl-4-yl)methyl(phenyll (IH-1,2,4-triazol-1-ylmethyl)7ran Particularly preferred compounds, methods, and compositions of formula ■ are:
R1s A compound in which at least one group of R or R8 is other than lower alkyl (C, -C,) or phenyl. In particular, the compound of the following formula (1) is particularly preferred because it has excellent activity and /f or is most preferably synthesized: (1,1'-biphenyl-4-yl)dimethyl (IH-imidazole) 1-ylmethyl)7
Ran, (2,4-dichlorophenyl)dimethyl (I H
-imidazol-1-ylmethyl)silane, 7'thyl(2
,4-dichlorophenyl)(IH-imidazol-1-ylmethyl)methylsilane, [bis(4-fluorophenyl)](]IH-imidazol-l-ylmethylmethylsilane, "bis(2,4-dichlorophenyll](lH-
imidazol-l-ylmethyl)methylsilane, C2,4
-dichlorophenyl1l)(-imidazol-1-ylmethyl)methyl(phenyl)silane, (4-chlorophenyl1(IH-imidazol-l-ylmethyl)methyl(phenyl)silane, (4-fluorophenyl)(IH-imidazol-l-ylmethyl) MethylC phenyl) 7rane, (1,1'-biphenyl-4-yl)butyl CIH-
imidazol-l-ylmethyl)methylsilane, (1,1
'-biphenyl-4-yl) (IH-imidazole l-
ylmethyl)methyl(phenyl)silane, [bisC], 1-biphenyl-4-yl)](]1H-
imidazol-1-ylmethylmethyl 7ran, butyl

[4
-chlorophenyl)(IH-imidazol-1-ylmethyl)methylsilane, C4-chlorophenyl)dimethyl(IH-imidazol-1-ylmethyl)silane, dimethylC4-fluorophenyl1(IH-imidazol-1-ylmethyl)silane, and butylC4-fluorophenyl 1 (1H-imi4r sol-1-ylmethyl)
Me Chirsilla y6 Q1 and Ql both and book, H or both CH. When , the process for preparing triazole derivatives of formula I usually produces a mixture of two triazole isomers: 1 The t* group of the triazole is H, and the # substituent AtCH of the other , then the n-form of 3f11 may be present: Formula IC Formula IE This mixture mainly contains the n-form of formula IA or formula IC. However, the isomers of formula IS, ID and IE have substantial bactericidal activity and separation of the isomers is unnecessary. For the imidazole derivative of formula 11, Q, and Q,
Isomers are produced when & are the same: Q. Formula TIA Formula 11B The isomer of formula [A generally predominates. I tried my best,
The isomer of formula B is also toxic to humans and separation of the isomer is unnecessary. In the following description, R1 is understood to represent both R and R(, as all semantic powers of R) are included in the definition of ERI. Furthermore, the word 'azole' may be substituted as appropriate. In order to mean 1,2,4-triazole and imidazole, Q, , Qt and Ql can be 8 or CH. or cQs is used to refer to both triazole and imidazole ring systems.Synthesis The compounds of the present invention are composed of chloromethylsilane and 1.2.
4-) Can be prepared from 17um salts of lyazole or imidazole or their methylated congeners: Q. Azole salts of lithium and potassium can also be used. Bromomethyl 7-lane, code methylsilane, or arylsulfonyloxymethyl 7-lane can be used in place of chloromethylsilane. You should use the reagent of Emomol Dragon except when R, = ORII.
(see below), azole salts are often used in a 5 to 1 O 3 stoichiometric excess. Additionally, 1@214-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, bare 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, dimethylsulfophosphate, or acetonitrile; ethers, such as tetrahydrofuran or 1,2-dimethoxyethane, and ketones, such as 2-butanone. The reaction temperature varies between 0°C and 200°C, preferably between 25°C and 100°C. 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 at approximately 2 molar concentrations in dimethylformamide at 80-90°C in approximately 2 hours.
1,2,4-triazole and potassium carbonate give approximately 1% conversion in 2-butanone.
At molar concentrations it takes 8 to 12 hours at reflux temperature. Generally, reaction times of 1 to 24 hours are required. Progress of the reaction was confirmed by finalizing an aliquot for nmr analysis, with a singlet of starting material 5iCH, CI around 2.9, and product 5i
It can be traced by measuring the strength of the -line of CHIN (around 3.8 for compounds of formula (1) and around 3.7 for compounds of formula). Regarding the triazole derivatives of formula I, the tH-1,2,4-)riazol-1-ylmethyl compound prepared above has a minor amount of isomeric 4H-1°2.4-)riazol-
4-yl compound. The ratio of isomers varies with the meaning of R and the historical conditions, and the ratio of 1-# substitution to 4-substitution is often observed to be about 10:l. Monomethyltriazole and dimethyltriazole produce similar 4H-! as small amounts of products. ! Styloid CH. give. When a substituted (unsubstituted zolylmethyl) IJ azole is available, metalation-methylation provides an alternative method of synthesis of methylated analogues.
This is possible only when and Q, are not 1lffl-. 2?1 isomers occur: Formula [8 The product of formula 11A generally accounts for the major proportion. If desired, the S-form can be separated by standard techniques, such as crystallization, distillation, or chromatography. Triazole or imidazole R3=OR6
For the case of chloroychloromethyl)7, the chlorine can be substituted 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: 1 See! Suitable solvents and reaction conditions are -1- as outlined on the previous page for azole substitutions. The temperature of the alcohol cis is not critical and when R,=C,-C4 alkyl warming to 50-1001:) can be used to complete the retention. However, for R, = H, hydrolysis is often carried out near room temperature to form disiloxane, desiring that silanol-disiloxane equilibrium is possible whenever Rg = H. It is possible to minimize: Q. The position of equilibrium and the rate at which it is established varies with the meaning of R5 and R1, the solvent, the volume, and the presence or absence of an acidic or basic catalyst. In the second method, silicon-oxygen bonds are formed,
The azole substitution then occurs as previously described: The reaction of the chloro7rane with Re O) (1) can be carried out in almost any non-hydrogylic solvent, ether,
For example, diethyl ether, 1,2-dimethoxyethane, and tetrahydrofuran or the dipolar aprotic solvents, 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 vary between θ°C and ]00C, and R@OH is often used in excess of the amount of brass. The combination of 2 equivalents of RaOH, 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 gives dioxygenated silanes: 1 R, -5i-CH2Cl --> If diol is used in place of 2 molecules of Ra OH, 1 glycol derivatives are similarly obtained. It's generated. Another method for the synthesis of alkoxyCchloromethyl)silanes consists of selectively replacing one alkoxy group of the dialkoxysilane with an organometallic reagent; the conditions for this replacement are explained in the next section. However, the organometallic should be added to the dialkoxysilane. The necessary lolomethylsilane starting material is made from commercially available chloro(chloromethyl)dimethylsilane, chloromethylCdichloro)methylsilane, or chloromethyltrichlorosilane: CH, CI R, - 8%-CH,CI A or CI, SiCH,CI The 8l-Cl bond in these compounds can be reacted with lithium, organosodium or Grignard reagents according to literature procedures to release alkyl and/or aryl groups. form and leave the C-Cl bond intact. 2 or 3
For silanes containing Ss C1 bonds, stepwise substitution is possible and provides considerable flexibility as to the meaning of R, -R,. 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,
-80°C depending on how it was produced and the solvent
Varies between 40°C. For example, when an aryllithium reagent is prepared from an arylbromide using butyllithium in tetrahydrofuran, the mixture is approximately =4
It should be kept below 0°C to avoid side reactions including the formation of bromobutane. However, when the organometallic solution is stable at higher temperatures, the reaction can be carried out at -20°C to 25°C in the absence of competing reactions of Ct (, CI groups). The reaction is rapid at all temperatures. , and a slightly shorter time, e.g. 30-60 minutes, is required to combine the reaction components and complete the reaction. The reaction of CISICH31tCHICI with a Grignard reagent is described by C, Eaborn and J, C, Jeff
ey. J, Chem, Soc, 1954. 4266 and CIs i (CH3)ICH,CI
CIs i (
A recent review of the synthesis of aryl IJ methylsilanes from CHs'm, Habic-h and F.
FJffenberger. 5ynthesis, 1979. 841. 1 new alkyl group + 7) CI, Si
The introduction into rcH*1c'HwcI is V, P, K
uznetsova and l (, M. 31897 p), and one aryl group can be introduced equally well and selectively. In both cases, organometallic reagents are used to optimize bird collection. should be added to the dichloro7 run at low temperature and with good mixing. The reaction of CI a8s CHt c + with Grignard reagent is described in A, A, Zhdanov, V, 1
．． Pakhomov, and V. Bazhanova, Zh, Qbshch, Kh
Jm, 1973°. Addition of organometallic reagents to trichlorosilane is recommended even when introducing three identical groups. Because (1'1ls
This is because addition of icH1cI to organometallic reagents is usually unsuccessful. A single aryl group can also be introduced: l Cl5SiCH1C1+ ArLi −+Ar-8i
A useful modification of the literature procedure, applicable when CHlClCI R or R is an aryl group, was developed in this work. Mido and a chlorosilane such as CISi (CH,3tCH,CI) are sweetened in an inert solvent such as tetrahydrofuran and at -80°C.
We have discovered that it is possible to treat with butyllithium at ~-40<0>C. The bromine-lithium exchange proceeds selectively and the resulting aryl lithium is ICH reacting with S+-C1 as it forms. CH. Ar-8i-CH, C1 CH. This reaction is effective for aryl-substituted chlorosilanes such as C.I.S.
i (CHnl (CeHs ICHtCl ) proceeds equally well and can be used to introduce two aryl groups into cl, sth C) 1m) CH,CI . With further stretching, aryl and n-butyl groups can be introduced in one step: CHs Ar -8t cu, Ct n-C,) (. When other alkyllithium RLi is used for n-butyllithium, Ar (CHs 181(R)CH
, a general route to CI is obtained. In the examples below, temperatures are reported in degrees Celsius. The abbreviations for nuclear magnetic resonance (nmr) spectra are as follows: diS--duplex, d = diacid, t = triplet, q = quartet, m = multiplet. The peak position is downfield from the internal tetramethylsilane.
Reported as ppm. Infrared rir) peak position is
It is expressed in reciprocal centimeters (cm-"). Hexanes means isomer mixtures with a boiling point of 68-69°C, and ether means diethyl ether. m, p melting point, bp boiling point, mo and mw respectively mean the molecular weight. Example 1 (1,1'-biphenyl-4-yl) (chloromethyl)
Preparation of dimethyl 7rane 9.9f (0,0
A solution of 42 mol) of 4-bromobiphenyl was cooled to -78°C under nitrogen atmosphere and stirred while a solution of 26.5 mol of 1.6 mol of n-butyllithium in hexane was cooled to -78°C and stirred.
sIj (0,042 mol) was added over 15 minutes. A viscous slurry formed and 35-tetrahydrofuran was added to facilitate stirring. With continuous cooling, 5
．． 9M (6,7F, 0.046 mol) of chloro(chloromethyl)dimethylsilane was added over 10 minutes to form a clear solution which was brought to room temperature t/Cmm. 300d
of ether was added, the precipitated lithium chloride was removed by heating, and the p-liquid was evaporated, leaving 13.2 f of semi-solid. Redissolve in ether, filter and evaporate the ν liquid,
11.0fl100% coarse! The title compound of 1) was obtained as a colorless solid, melting point 30-40°C. This is suitable for further reactions. A trace amount of impurities was removed at 30℃/ (1,1
Removal by sublimation at tm left the title compound unsublimated with recovery of 83q6: m, p, 37-40
°;1r(NujolR11585,1240,]11
0.830.810.750.690cm'; n
mr (CDC1110, 4 (6H. S), 2.9 (28, 31, 7, 3-7°7 (9H, m
). Example 2 (Preparation of 4-bromophenyl 1(chloromethyl)dimethyl
f (0,050 mol) of 1,4-dibromobenzene and 1.29 (0,050 gram atoms) of magnesium turnings in 75 m ether (). P, Schiemenz, Org, Syn, ,
Cn11. Vol. 5, 496 (1973). The resulting mixture was cooled in water under a nitrogen atmosphere while 10 d(7):f--(7)6
．． A solution of 6 m (7°2 t, o, os. mol) of chloro(Fe+methyl)dimethylsilane was added dropwise. The reaction mixture was then stirred overnight at room temperature, quenched with a phased aqueous ammonium chloride solution, and filtered. The ether phase of the filtrate was washed with prine, dried over magnesium sulfate, and evaporated to leave 9.8 f of oil. , to give 3.8fr29t) of the title compound as a colorless liquid: bp 97″ (1m); ir
(Pure) 2950.1575.1475.1370.1
250.1065.10 ] 0,840,805.7
20rM':nmr (CDCIj)0.4 (6HS
s l, 2.9 (2H. S), 7.3-7.7 (4H, m). Example 3 Preparation of orchid 75-9.6fr0.050 in tetrahydrofuran
mol) of 4-bromochlorobenzene and 6.6 *
(7.2t, 0.050 mol) of chloro(chloromethyl)dimethylsilane 111! While stirring under a nitrogen atmosphere at r-78 DEG C., 1.6 mol of n-butyllithium (0,050 mol) in hexane was added dropwise. When the resulting clear solution is warmed to room temperature, no further lithium chloride precipitates f! The filtrate was evaporated to leave 10.6f of a pale yellow liquid, which was distilled to give 6.0f (55% 1 of the title compound as a colorless liquid. :bp54-58C(0,
05 throat 1; ir (pure) 2910.1560.1470
．． 1370.1250, 1080.1010, 840.
805.790. 740cm-”; nmr (C
L) CI 10.4 (6H, sl, 2.9 (2B, s
l, 7.1-7.6 (4H,q l. The in situ aryllithium formation described in this example is also useful in preparing the product of Example 1. When carried out at 0.5-0.7 mol in bromobiphenyl and keeping the temperature between -65 and -55°C upon addition of butyllithium, little or no solid precipitates (7). Example 4 Preparation] 17.0 f (0
, 075 mol) of 2,4-dichloropromobenzene 10.8+j (11,8f, 0.082 mol l of chloromethyl)dimethyl 7 was cooled to -70°C in a nitrogen atmosphere. And in the meantime, 1 in xane
．． 491Ij (0,07
9 mol) was added dropwise at a rate that kept the mixture below -70C. The resulting cloudy reaction mixture was warmed to room temperature and
Pour into hexanes of o-, FA, and evaporate to give 20
．． 59 grams of yellow liquid remained. When distilled, 12.6f (
The title compound of 664) was obtained as a colorless liquid: b
p83゜(0,02w1; nID'1.5522;
ir (pure) 1565.1455.1360.12
55.1120.1100, 1040.825m-1;
nmr (CDCI,)0.5 (6[-T, s
), 3.1 (2H. S), 7-0-7.5 r3H, ml. Example 5 Preparation of methylsilane 25.0f (0,1
A solution of 81 mol) of 1,3-dimethoxybenzene is mixed at room temperature under an atmosphere of 9 atoms while a solution of 1.6 mol of n-butyllithium (125 aj
0,200 mol) was added dropwise over 305+ hours. The resulting mixture was clarified for 1.5 hours, resulting in a yellow-brown solution, which was cooled to 5°C] 7. Stir, during which time 27 m12
9.4 f x 0.205 mol) of chloro(chloromethyl)
Dimethylsilane was added dropwise over 15 minutes. The resulting white solution 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 and distilled with magnesium sulfate to give 37. or (84% 1 of the title compound was obtained as a colorless liquid &: bp 98-1 ] 0'(0,1
? II) ; nmr (CDCI, l 0.4 (6
-H,s I,3.1(2H,Sl,3.7(6H,s
1,6,3(2H,dl,7.1(IH,m).) The compounds in Table 1 can be prepared using the procedures of Examples 1-5 by changing the Grignard reagent. Closely related procedures are also known from the literature,
For example, the use of arylmagnesium chloride
(', Eaborn and J, C, Jeffrey
, J. Chem, Soc, 1954°4266
It is described in. For compounds where R1 is phenyl Sakai with a 2-halo substituent, a modification to the in situ procedure of Example 4 is C, Eaborn. K, L, Jaura, and R, M, Wa
I ton, J. Chem. Sac, 1964.1198, a special magnesium iodide method. 6 υ (・
Lo Lo Ri “ −
Het size ~ 8P+
F+ Imp-1++ F+C,c,:
R: Q lo α, Q, j: l
Ce, lo-x
:oeeee to -η
G force −−〇 −〇night heya l; luxury + + ) (＼ 11 ) l to ) II-1 N -totoya-he 7 Alt to food base to 8 - year old It )l tose H++
Dormitory HII II Hh
tl J h )I S
? h mouth) luxury to he
Musu ka wo Toro l r ＼
N ---- also L gourd ・-)1111
11111111 cqh dimension dimension dimension dimension
Dimensions So Dimensions Dimensions To Dimensions
I'm n
1) 啼-Fi
■
σ=ρ −Q 0 Years 6 Total 11 Sheets t 11 ) 4 Also 11
)! @t'= II 8 years old
Ku He To Night H Sa7, 11110 Now IIr\Isoisokuchi +l @ Hp 1 @ a
l l −k １嬶 FltXt′−
To X 1 mouth M+-1 extra day+
lr:>olh1%htzr, r H night sound seven! De − beak? 1 year old mouth 1 mouth + J-ko, 1-day x sunny\mouth! t. To) () (Toro 10-1 (outside 1 grass W ° to non °pe + wa + age) °fu year
SA L Ill 礒 D + l 1
Distance 1＼ 9 9 o'clock h outside
S Q size ＼ ME1 ・ --1111
--1- Guri Cli N% Hi: % t%I
to N(Ttsu Ou Oτ Example 6 Preparation of 0 methyl) methyl 7 Run The title compound was prepared using (butyl)chloro() instead of chloro(chloromethyl)dimethylsilane by the procedure of Example 1
It can be produced using chloromethyl) methyl 7rane. Related compounds were selected from the hand MK of Examples 1 to 5, including the corresponding organolithium or Grignard sample and CI (R*)8i.
(CHll) It can be produced using CHlC1. The necessary lolomethylsilane starting materials are:)j, MgCI
or R4L i and CI, S i (CH,)CHl
Examples 14 and 15 from CI and literature procedures such as V, P. Kuznetsova and R.M., 5oknlov
askaya. Zh, Obihch, Khim, 1969.
Created in accordance with 1997. Alternatively, both biphenyl and butyl groups can be introduced simultaneously as follows. 150-z3.3r (0.10 mol) of 4-bromobiphenyl and 12.7m (16.4f, 0.10 mol) in dry chitrahydrofuran
A solution of chloromethyl(dichloro)methylsilane of
5 m (0.2 mol) were added at such a rate that the mixture was kept below 160C. The resulting dilute slurry was warmed to room temperature, treated carefully with 101 Ij of ethyl acetate, and poured into 300 m of water. The organic layer was separated, the aqueous phase was washed with another 100-hexane group, the combined organic phases were washed three times with water and once with brine, dried over (fl magnesium and evaporated to 33.9 f of viscous oil remained. Distillation gave the title compound of 9.5 F (31 omitted): bpl 35-158° (0,1 m+); n"
1.5743: ir (pure) 3060.301
5.2960,2920°2870.1600.148
5.1390゜】380.1250.11″'20,1
075.1005.875.810,800,760°700cm-'; nmr (CDCIg): 0.
4 (3H, S), 0.6-1.8 (9H, m), 2
．． 9 (2B, S) and 7.0-7.7 (9
H, m). i1! Example 7 14.4f(0) in 159m(7) tetrahydrofuran
,075 mol) t7) A solution of 4-7" lomochlorobenzene and 9.511j (12,3f, 0.075 mol) of chloromethyl(dichloro)methylsilane [--
Cool in a 60 cK nitrogen atmosphere, stir, and ＼
9411 of 1.6 mol of butyllithium in xane
7 (0.15 mol) was added dropwise at such a rate that the mixture was maintained at -65 to -55°C. The resulting slurry was warmed to room temperature and a solution was obtained which was diluted with hexane until no more lithium danide precipitated. Filtered, evaporated Part F, dissolved the residue in hexanes, refiltered and evaporated leaving 19.82 pale orange liquid. Distillation yields -1.8F (12%) chloromethyl(dibutyl)methylsilane, bp 45°C (0.05m)
was obtained, and then 6.8f (35%) of the title compound was obtained as a colorless liquid.
5m) ;n-' 1.5246 + r r (pure) 2925.1580°1380.1260.10Q
O,] 015.820°740cm-'; nmr
(CDCI, l) 0.4 (3H,S), 0.6-
1.5 (9H, m), 2.9 (2H, 8), 7.0-
7.4 (4H,Q). Example 8 Preparation of chloromethyl(2,4-dichlorophenyl)methyl(phenyl)silane.
, 06 mol) (7) 2.4-Schiff" lomobenzene and 12.3f (0,060 mol) of chloro(chloromethyl)methyl(phenyl)silane (prepared as in Example 14) in a nitrogen atmosphere. 381a/(0,060 mol) of 1.6 mol n-butyllithium in hexane was added dropwise at a rate that kept the mixture below 155° C. The resulting red color The solution was warmed to room temperature, treated with 5 d of ethyl acetate to quench the unreacted organolithium reagent, and poured into 170 d of water. The organic layer was separated and the aqueous phase was washed with 50 d of hexanes. , and washed the combined Ariiso phase three times with water and once with prine,
Drying over magnesium sulfate and evaporation left a bright yellow oil of 19.Of. When distilled, 8.6F (45
1. The title compound was obtained as a colorless liquid.1.
125-130@(0.05m)! nfi1.59?
8 wealth ir (pure) 3080.3060°2960,
2930% 1570. 1540.1460%14
30.1365.1!60.1120,1100°10
40.820,745,735,705su-IInmr
(CDCIg)0.8C3H,a), 14(2B%g
')-7,2-7,9(8H,rn). Example 8A (1,1'-biphenyl-4-yl)(chloromethyl)methyl(2-propoxy)silane 1-0.0132.8 moles) and 4-in 30-mol of dry tetrahydrofuran
A solution of 161 J bromofluorobenzene (3Z 8 mmol) was cooled to -60 °C under nitrogen and 1.6 mol n-butyllithium 2O, sm (azs
(mmol) was added at a rate to keep the mixture below 50 ml and then stirred. After stirring for an additional 30 minutes at -706, the solution was allowed to warm to room temperature and processed as in Example 8. The obtained crude product was 130-150@
(0.2 m) to remove unreacted starting materials,
The title compound remained as an oil. ? L'1.51 old n
mr(CDCIg)fO,7(3B,11.3.1(
2H. g), 7.1 (L#, t), 7.1-7.8 (11H,
m). Example 9 19.11 in 200 ml dry tetrahydrofuran
A solution of i' (0,10 mol) of 4-chlorobromobenzene is cooled to -60° C. in a nitrogen atmosphere and stirred while a solution of L6 mol of 4-chlorobromobenzene in hexane is added to
d (0.10 mol) was added dropwise at such a rate that the mixture was kept below 155°C. Stirring and cooling were continued while 6.3 m (&210.05 moles) of chloromethyl(dichloro)methyl 7 ran was added dropwise at a rate that kept the mixture below 150°C. The resulting orange solution is warmed to room temperature and worked up as in Example 8 to give 1
6.52 pale yellow oil was obtained. original tube fKu5relr
ohr) distillation is carried out at 0.05 m and an air bath temperature of 130-150°C, 9. ! The title compound of M'(609G) was obtained as a colorless liquid: n"1.591
3; ir (pure) 3080.3040.3020.29
60.2930.1580, 1490.1380.12
60.1085.1015.805.790,775.
740cm-'; nrr+ r (C1)C1g)
0.7 (3HxS), 3.1 (2HxS
), 7.2-7.7 (RH, m); e, , H,, a
Analysis and calculation values for t, lsi (mw 315.70): C, 53, 26: H, 4, 15; C 1, 33,
69 actual measurement value: C, 53, 4; ) (, 4, 4; C
1,34,253,5; 4.4; 34
．． 1° Example 10 Preparation of (chloromethyl)bis(4-fluorophenyl)methylsilane 35f(0,2
A solution of 1.6 mol of n-butyllithium 126117 in hexane was cooled to -60°C under a nitrogen atmosphere and stirred.
(0.20 mol) was added dropwise at a rate that kept the mixture below 155C. Continue stirring and cooling, during which time 12.
8m (16.4f, 0.10 mol) of chloromethyl(dichloro)methylsilane was added dropwise at a rate that kept the mixture below 150C. The resulting solution was warmed to room temperature and worked up as in Example 8 to give a bright yellow liquid at 26.4F. When distilled, 20.6F<734)
The title compound was obtained as a colorless liquid: bpl
07-127QIO, 1m);n”1.5481;
nmr (CDCI, ): 0.7 (3H, s), 3
．． 2 (2H,8), 7.1 +4H,t, J=9)
and 7.6(4) (, d of d, J=6 and 9),. When this reaction was repeated using chloromethyl(jethoxy)methyl 7 run instead of dichlorosilane, the title compound was obtained with 58% retention after distillation: bp 115-
138'(0,2m);n''Example 11 Chloromethyl I 2-chlorophenyl)+4-10lophenyl)methyl 7ranno Preparation 75-6.35IjT in dry tetrahydrofuran
A solution of 8.2 f, 0.05 mol) of chloromethyl(dichloro)methylsilane and 8.1 f, 0.05 mol) of 2-fo-mochlorobenzene was dissolved in N! (
7) Cool to 60C and stir while stirring - 33 d of 1.6 mol of n-butyllithium in xane
0.05 mol) was added at a rate that kept the mixture below 155°C. While continuing cooling and stirring, the temperature was increased to 8.1f (
0.05 mol) of 4-bromochlorobenzene was added as a solid, followed by another 31 m portion of the 1.6 mol n-butyllithium solution described above at a rate that kept the mixture below 155°C. The resulting dilute slurry was warmed to room temperature, treated carefully with 17-ethyl acetate, and worked up as in Example 8 to give a bright yellow chain of 15.0f (37%). : bp150-165°(0
,78):n"1.5916: ir (pure>30
60,3020,2960.2920.2870.15
80.1560.1490.1420.1380.12
55.1125.1115.1085.1035.10
15.805.750m”;nmr(CDCI, l
)0.8 + 3H,,s l,3.3(2H,S),
7.2-7.7 (8H, m). Like
- Seal P So C Houki = 弗 误7 - Takui I く１ 外礒 碌 鵵子也也 1111 も 11 夜 +1 ) 1 ) 1 \)
-I It )l to Hero
If) I l-1) (111111 -
He he he he he he he sang groan call sun nE year old X's eV)
6 5 礒 + 1 H 礒 11 礒 1 0U 口 φ の = p ＼ ＼ 口 tlj＼ 礒 7年 口 口 r＼ 礒 IR Example 1 (1,1'-biphenyl-1-yl )C chloromethyl)
Preparation of diethylsilane The compound can be prepared simply according to Example 10, using chlorochloromethyldiethylsilane in place of chlorochloromethyldimethylsilane. The procedures of Examples 1 to 5 were repeated using a suitable organolithium and Grignard reagent and CI (R1) S l (R1) CH4'
By applying CI K, 51 compounds can be produced. If necessary, rolochloromethyldialkylsilane can be added to CI,
5iC) From I, CI, when R, = H, 2 equivalents of R
, MgC1 or l, made using Li (for example,
A, A, Zhrlannv, ν, 1. Pakh
omov, and T, Bazhanova, Z
-h-, 0bshch, KAJm, , 1 j7.
3° 1280), or when R2 is not equal to R3, use one element of the art l(, MgC1 or it, Li and then one element of Rs M g CI or R3L
Example 13 using i 12.6 mg (18,
A solution of 4F, 0.10 mol) C chloromethyl) trichlorosilane was stirred under nitrogen and cooled in water, while a solution of 1.85% in cyclohexane-x-f Lua 0:30 was stirred under nitrogen and cooled in water.
162 m (0.30 mol) of phenyllithium were added dropwise to the mixture at a rate that remained below 150 mol. The resulting slurry was stirred overnight at room temperature and treated with 10% ethyl acetate to quench residual phenyllithium, washed with ice and brine, and dried over magnesium sulfate.

[7
Upon evaporation, 33 tons of viscous solid remained. 3o resistant
When recrystallized from cyclo-\xane, ts, 5t15
The title compound of 11) was obtained as a gray solid: m, p
, 112-115°C; i r (pJu jnl”)
1420.1110.735, 730.705.695
cj” l nncr (CDCL@) 3.5 (2H
*a), 7. o-7,8 (15 Be m )@Example 13.4
1.6M duck-butyl in hexane and cooled to
Lithium gQIILt (0,128 mol) was added to the mixture.
The addition was stirred at a rate that maintained the temperature below 50°. Obtained
Stir for another 10 minutes at -60° to -700°.
, then chloromethyltrichloro in tetrahydrofuran
Solution f3 of 5.2 mJ (0,041 mol) of rosilane
Added dropwise over 0 minutes. Stir the resulting solution f-To'' to 11' in the dark and bring it to violet temperature.
Warm and quench with saturated aqueous ammonium chloride
Extracted with chill. Wash the proboscis with brine.
Clean, dry over magnesium sulphate and evaporate to a viscous oil.
remained. Chromatograph this on silica glu
Elute with hexane). Compound 9 of the title as a non-battery that solidifies when left standing, I
II (53 arrogance) is obtained. Melting point 89-93@. nmr (CDCI, )14 (2B, #), 7.5
(12H.!Load 1). Example 11 of the surface compound! - Follow method 13A”c
cl, 5iCH, CL os i -CI M Konno WI
'Produced by 1:1° conversion. 21 ″e″(', )ゝ″ ~ 1 1
1 - ~ V size - gold +1 Pehe Higashi Sakimoto \ ζ year old hH II, +1 + to HII N r'X - size Example 14 Manufacture of 200117! of ether in 12.7 m1 (16,4
f, 0.10 mol) glue cIeff methyl C dichloro)
A solution of methylsilane was cooled to -70°C under zero nitrogen,
Now mix e, 30nia 0'r--chill-cycloheki
55m of S mole phenyl lithium, glue in Sun! 0.
A mixture of 10 mol) and 55 w/m of ether
Dripping at a rate that maintains the temperature below -70C (7t, occurs)
Warm the slurry to room temperature, then let it stand overnight (
~is. Filtration [~, when the filtrate is evaporated, 20.49 gold
Colored oil-75: Obtained, when distilled, +4.6P
171 width) was obtained as a colorless liquid.
p71-74°(0,6w);n”1.5337;ir
(Cotton swab > 3oso, 3060.2980.2Q30,
1590.1430.1260.1120.82θ, 7
90,740,700C11-'Rei nmr (CDC1,
) 0.8C3B, 71), 3.1 (2H. #), 7°3-7.6 (3H, m), 7.6-7.8 (
2B, habit). Example 14A Magnesium 111J shavings (tur
n-4Bgs)7. OEl (0,288'tl)
The suspension was stirred under -pg while 200 rnl of ether
4-10 mofluorobenzene in 50. ! ,! i'
(0,287 mol) of bath liquid is kept at gentle reflux
It was added dropwise in a flashlight. After 2 hours the mixture was heated to reflux.
Glue p-promethyltrichloride in ice-cooled 7 and ether 20 ν
+1 solution of rolosilane tzo shoulder t (0,096 mol)
．． ];, below. The resulting mixture was incubated for 4 hours.
After cooling in water, add isopropylene in ether 20ν.
Treat with 7.5 red solution, stir for 5 minutes, and p
passed. Evaporate the p-liquid and leave a viscous oil, which is
A slurry was obtained by stirring with xane. Overexposure under nitrogen
The evaporation of p-liquid leaves all the mobile oil residue.
This was distilled to give the title compound 17.6N (61%)
t- got it. Boiling point 10G-140° (0,1m)s n
mr(CDClBmC2B,a), 7.1C4H,t
),'I,? (4//I d of d). Example 15 Title compound 1 equimole gold violet 4-bromo piphenyl, chloro
lomethyldichloro(methyl)silane, and n-butyl
Lithium! ! Follow the procedure of Example 3. Can be manufactured. Compounds of Table V @-4 following the procedure of Fruitful Examples 14 and 15
r# Can be left behind. Iso Isao-tw
wwww+QCQeaNNaszOH Example 16 Preparation of run 100-1.6y (1,3f. 0.040 mol) of methanol in ether and 3.0m12.2
stir a solution of triethylamine (f, 0.022 mol)
Mix, while IQsd 4.1f (0,0
20 mol) of chloro(chloromethyl)methyl(phenyl)
) A solution of silane was added dropwise. The resulting slurry was heated continuously for 2 hours.
Rinse, cool, solution in water, 0.1N HCl, saturated N
af (washed with CO1 aqueous solution, water, and brine, sulfur
After drying with magnesium acid and evaporating, 3.2 tons of pale yellow
A colored liquid remained. When distilled, 1.7F (Table 421)
The title compound was obtained as a colorless liquid: bp46-49
°(0,05m); n” 1.5207; nmr
(CDCI, ); 0.5 (3H, s), 3.0 (2
H,S), 3.5 (3H.S) and 7.3-7.8 (5H,m). Example] 7 15.4F (0,075 mol) of chloro(chloromethyl
) Methyl(phenyl)silane, 14mrlllf, 0.
15 mol) of t-butanol, 11.1j (8,3f,
0.082F) triethylamine and 0.5F (0
,008 mol) of 60- in dimethylformamide.
The mixture was negative boiled at 8 Qtl' for 2 hours. resulting slurry
Cool, pour into 200-mL water, and extract with ether.
I put it out. The ether extract was washed three times with water and then diluted with 0.
1 of IN (C1 * solution, saturated Na 14 CO * water solution
Wash with solution and brine and dry with magnesium sulfate.
, evaporates leaving behind a pale orange oil of 14.
+e, m distillation yields the title compound of 11.9r (651)
obtained h9f677$-82"(a2sm+1ts"
15010tD ir (pure) 3080, 3060, 2990.2940
゜1600.1435.1395,1370,1!80
゜1245.1195.1125,1060,1030
゜815.790,740.725.705.650♂
蓼nmr(CDCI,)sO,5(3H,a),1
．． 3 (9H.s), ze (2H9a”) and 7.3-7.8C5H
, vn). Example 17A 4-20 Mobife in Tetrahydrofuran 300 ze
The bath solution of Nil 713Ii (0,315 mol) was diluted with tetrahydride.
Magnesium 7°64f in LoFlan 100d! (0,
315 mol) to maintain a gentle reflux in the stirred suspension.
It was added dropwise at a rate of Electrolyte the resulting clear solution.
Stir with an anchor for 1 hour, then cool in water, and add
Dorofuran 100fLt
) A solution of methylsilane 4QRt (α315 mol) was quickly added.
I cried out. The resulting solution was stirred at room temperature for 20 hours and then
Treated with Sopro Gunol 50W11 and cooled again in water.
did. Then triethylamine in tetrahydrofuran
A solution of 48% (0,344 mol) from mixture 925@
The force was reduced to zero at a low holding speed. Stir for 90 minutes at room temperature
and a slurry was obtained. evaporate the P solution, then
Tritucation with San and filtration with Kawaji to remove remaining residue.
Minsalt modified salt was removed. Title by evaporation of hexane solution
Compound 9211 (96%) was obtained as a pale yellow oil;
This solidified when left to stand. Melting point, 35-38"l
smv(CDCL@)0.5C3H,s), L2(6#
, d), 3.0 (2#, s). 42 (IH, Septet (mouth ptgg)), 7.3-7.
8 (911, ml. Example 17B Magnesium 2&!I (α95
5 mol) and iodine 5 osy. 4-Glomofluoro tetrapensene 1 in ether 800+J
Hold a solution of 67.9 C & 954 mol) at gentle reflux.
The mixture was stirred while adding at a rate of After another 2 hours at reflux, f
14 in water and chloromethyl in ether.
A solution of 40d (0.31 mol) of trichlorosilane
The mixture was stirred dropwise over a period of minutes. can get
The mixture was stirred at room temperature for 1 hour, cooled in water, and
Treated with Low Deluxe Nord 241, j! Stir for 10 minutes and set aside.
and filtered. Concentrate solution F to obtain a sticky solid tIi-, and add hexane.
. Filter the resulting slurry and evaporate the hexane solution
There was some oil left over. Analyzes using external methods show that unreacted chloro
showed the presence of silane. So I poured 30-liters of oil onto it.
#4% in hexane containing reel and the solution in water.
Cool and dilute triethylamine 4 wJ (a3
0 mol) solution. The resulting slurry at room temperature
Stir for 3 hours. - filtration and evaporation of the f-liquid leaving an oil. By distillation
The title compound L8J' (43 pieces) was obtained as a colorless liquid.
Electrical boiling point 120-140 @ (0,1W) 8%”L5
1!11eS Korede (CDCI,)1.2C*H,d),
s, *ctH, a), tt (tHti ensemble), 7.1 (
4HIt), Fu, Fu (d of 4H, d). EXAMPLE IS Preparation of Orchid 1 & 2 Red (112 g, 0.2 g in dry ether)
10 moles) Nori I! Protyl(V-ethoxy)methylsila
The solution of water is stirred vigorously under N, cooled, and then
Between 70 and 130 cyclohexane-18 mol in ether
A mixture of 56a/(alO mol) of phenyllithium
was added at a rate that maintained the temperature below -50°C. The resulting sura
Warm the lily to room temperature and carefully add 1OIIj of ethyl acetate.
Washed with water and prine, and treated with magnesium isoate.
After drying and evaporation, 16.8 f of golden liquid remains.
Ta. When distilled, the surface compound of 9.5F (44%) becomes colorless.
Obtained as a liquid: bpso-84° (0,1m)
; n” 1.5144 ; nmr (CDCjl
) 0.5 k (3H, 8), 1.2 (3H, t, J=7), 3.
0 (2H, S), 3.8 (21 (% q %J palm 7
), 7.2-7.8 (5H, m). Compounds of Table V were prepared using the procedures of Examples 16-18.
can. X Dimension T Dimension C ~ ~
~ ~ ~ ~ To 0 years old 1 Perrault〇0 e He Pe He He He Be Be Be
He he year old 1 1 111811111 CQ ee-to moan size size size
size = = ni
Flash Example 19 2.62 (0,0
10 mol) of (1,1'-biphenyl-4-yl)chloro
lomethyldimethylsilane and 1.1f (0,012
mole) (7) 1 , 2 , 4- ) Q7 Sol Natori
Wet the mixture of salts at 80-90℃ for 2 hours and cool it.
diluted with water and extracted with ether. Wash the nityl solution with water and brine for 1y, then dilute with magnesium nitrate.
After drying with
, p, 79-86°C were obtained. 2511/hexa
Recrystallize from a mixture of salts and ethyl acetate.
And 1. If (38%) entitlement was obtained: m
, r), '12-93'': 1r(NujnlR)1
255.1130, ]000.825.760.695
Qll'; nmr (CDCIq) 0.4 (6
H, S), 3.9 (2H, S), 7.2-7.7 (
9H, m), 7.8 (IH, s), 7.9 (] HX
S ) :CBH+*N1Si(N15i(,43)
Analysis: 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゜1.2.4-) Riazole and Na
All equimolar mixtures with thorium methoxide were preformed.
Can be used in place of triazole sodium salt
can. These reagents must be combined before addition of plan.
Be careful not to use an umbrella. Because Chrollo
Methyl heptans are sodium methoxide and dimethylform.
Reacts very violently in Muamide, producing undesired
It is abundant because it produces things. Example 20 +1.1'-biphenyl-4-yl)dimethyl(4H-
1,2,4-triazol-4-ylmethyl)silane
Sodium methoxide as in Example 14
Once crystallized using 1,2,4-) lyazole,
1, 1'-(biphenyl-4-yl)dimethyl (
IH-1,2,4-trisol-1-ylmethyl)sila
The sample at 5F of the engine was subjected to high pressure. Thornfish (Wat)
ers Prep PAK-500 silica gel car
tridge, flow rate of 250 d/min). , WES et
Elution with 50:50 chill-hexane is unpalatable.
<IH impurities are removed, then pure IH
-1,2゜4-triazol-1-ylmethyl compound, ■
, 0°99-10071: was obtained. Ethyl acetate
Continuing the elution with acetonitrile 80:20
, the titleable appendage of the purse was obtained as a colorless solid: m,
p, 130-1337:;nmr(CDck,)
(1,4(6H,s), 3.7(2H,s), 7.2
-7.7 (9H, m), 7.9 (2H, S);
C+yH+*N5Sf(m w 293.43) I
/C Tweet (D Microanalysis: Calculated value: C, 69, 58; H
, 6,53; N, 14.32 Actual value: C, 69,0;
H, 6,7; N, 13.969.3;
fi, 7; 14.2° Example? ] azo-]-ylmethyl) 7-run In25- dimethyl
9.0-(9,2F, 0.05
0 mol) of chloromethyldimethylphenyl 7rane and
5.4M (0,060 mol) of 1.2.4-) riazo
Stir the sodium salt mixture and heat to 90-95°C for 2 hours.
7. Dilute with water and extract with ether.
Ta. Wash the ether solution with water and brine L, sulfuric acid mug
When dried with nesium and evaporated, 8.1 f (75 excellent)
A light brown oil, n” 1.5350, remains, which is nm
Contains the title compound and a small amount of impurity as determined by r.
. A more pure sample was obtained by distillation: bp
99'(0,02m);n"1.5403 ;℃ nmr (CDCI, ) 0°4(6H,!I),3
．． 8 (2H.S), 7.2-7.7 (5B%m), 7.7 (IH,
S), 7.8 (18% S); CuHnN*Si(m
Analysis of W217.34): Calculated value C, 60, 78; H, 6, 96: N, 19.
33; Actual value C, 60, 7: H,? ,0;
N, 16.9; C, 60,2; H, 7,0:
N, 16.8I. Example 22 2.22 (0,010
mol) of chloromethyl(4-chlorophenyl)dimethyl
t of 7 runs and 1.1 f (0,012 mol), 2
．． 4-1 lyazole sodium salt mixture at 80-90%
C., diluted with water and extracted with ether. Aete
Wash the solution with water and prine, then with magnesium oxalate.
When purified and evaporated, 2.1? (83%) of the title compound
Obtained as a yellow liquid: n"1.5428; ir
(Pure) 1555.1470.1245.1130.
1o80.1010.835.805.795.735
cm';nmr (CDC1g) 0.4 (6H,S
), 3.8 (2H. S), 7.4 (4B, wide S), 7.8 (IH, s)
, 7.9 (IH%S). Example 23 Preparation of 5,1f (1011j) in dry dimethylformamide
0,020 mol) of chloromethyl C2,4-dichlorophene
phenyl)dimethylsilane and 2. ov (0,022 mo
mixture of 1,2,4-triazole sodium salts of
was stirred at 80-90°C for 2 hours. resulting slurry
was cooled, diluted with water and washed with ether. ether
Wash the extract once with several portions of water and prine
death,? Dry with magnesium acid and evaporate to 4.6F
The title compound (81) remained as a pale yellow liquid: n
"1.5580; Lr (Pure 11550,14
85, 1440.1345.1260.1240.11
30゜1085.1025.1005.835Qll
, nmr (CDCI, )0.5 + 6HSS)
, 4.1 (2HXs), 7.2-7.5 (3H, m
), 7.8 white H,! >, 7.9(1)1%S). Example 24 Preparation 6.3II (0
,020 mol) of chlorotetramethylbis(4-chlorophenylene)
) Methylsilane and! 0.9 (0,021!mol)
A mixture of l*4@4-triazole sodium salt of
Stir at 80°C for 4 hours. Cool the resulting slurry,
Dilute with water, wash with ether, fc, and extract the ether extract.
with several parts water. Purify 11g1fk with prine-6'ttiV magnesium
After drying and evaporation, a yellow oil of L4jl was obtained.
0 ball Th height*t 120~I S 0℃ (air bath) 7
When carried out at 0.05 m, 4.0I (s8Is
) The title compound was obtained as a pale colored oil.%%1.5
9661smr (CDC1B) a7 (3Hy a ),
41(28g m)-7,2-7,5(8H,m),7
．． 8 (IH,a), 7.9 (lB,a), similar experiments
Upon evaporation of the ether extract, a sticky solid was obtained.
and triturated with hexane to give the title compound as a colorless solid.
Obtained by doing. Melting point 76-80@. Example 25 Preparation of 2.4-triazol-1-ylmethyl)silane 4.2f(0,015
(mol) of (chloromethyl)bis(4-fluorophenyl)
) Methylsilane! 1.4 f (0,015 mol)
1.2.5-) A mixture of lyazole sodium salts,
Stir at 80°C for 2 hours. Cool the resulting slurry,
When diluted with water and worked up as in Example 24, 4
．． A light yellow electric oil of Of was obtained. Impurities are removed by distillation
When removed at 120-125C (0.05m),
2.3f (49th) of the title compound leaves a yellow oil fp
+, n 13f 1.5538; ir (pure) 3065.3030.29
6G, 2925.15・90.1500.1270.1
235.1165.1110.1010.830.79
QeWI-1; nmr ((:'1)CI,):
0.7 (38%g), 4.2 (2R,s), 7.1
(4H*t, J, -91°7.5C4H, dj=@
and 9), 7.8 (lH, brutal) and? −9(lHe
s)e Sample Q produced in the same manner - Hexane at 120℃
A colorless solid 1 was obtained by crystallization from . Melting point 52-53°C. Examples 19 and 21 to 250 moves Jl [as appropriate
By applying methylsilane, Q, =Q, =H
Compounds shown in Table 1 can be produced. t'-(Q to
Engineering He ■ Tori
Request Q ・+ C-
j-el: to C to 0 ■ C■
Shun pus ψ to ■ ro's
of ~ of t lotto ■
The list of
■■ Vl 0 call ro he ψ
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1) - Possible Example 26 The procedure of Example 25 for the production of chloromethyl
-fluorophenyl)]methylsilane and 3,5-di
Applicable to methyl-1,2,4-) lyazole sodium salt
The title compound is then prepared. 3-methyl instead of 3.5-dimethyltriazole salt
-1,2,4-) By using a salt of lyazole
, related compounds can be produced. Example 27 40-5.99 (0,0
20 mol) of (t, 1'-biphenyl-4-yl)
Dimethyl (IH-1,2,4-triazol-1-ylme)
A solution of silane (chill) was cooled to -40°C under N,
Meanwhile, 1.6 moles of n-butyllithium in hexane
12.1 J (0,020 mol) was added dropwise. resulting yellow color
The solution was stirred for an additional 15 min at -40°C, then 1.9 m
(4,2F, 0.030 mol) treated with methyl iodide
and warmed to room temperature. The resulting solution was diluted with water and extracted with hexanes. Wash the bound extract with water and prine and add magnesium chloride.
After drying and evaporation, a 5.7f solid was obtained, which
11F dry column chromatography on silica gel (vinegar
Purification by elution with ethyl acetate) gave the crude product of 11f.
was gotten. Then 12ml of 3:l hexanes-
Recrystallization from ethyl acetate yields o,97r (t6%).
The title compound was obtained as a gray solid: m, p, 95-
98°; ir (Nu jo IR) 1590.1
270.1250.1180.1120°830.76
5.700ts” ; nmr (CIJCII
)0.5 (61(,s), 2.2(3H% s)
3.7 (28°S), 7.2-7.7 (98%m
), 7.8 (IH, S). Although the structure shown is preferred for steric reasons, the triazole method
The position of the methyl group at the end has not been determined, but the product is (
tu1'-biphenyl-4-yl)dimethyl(5-methy
(IH-1,2,4-)riazol-1-ylmethyl)
It can be a silane. Using the Example 26 and 270 procedures, the compounds of Table VII
Can manufacture things. n ~ to to to to to a little captive moan
G Size Example 28 5.0f (0,01
7 mol) of (1,1'-biphenyl-4-yl)dimethy
(IH-1,2,4-)riazol-1-ylmethyl)
Silane and 1.7 f (0,017 mol) cuprous chloride
The mixture was refluxed under N for 30 min, and then
Evaporating the resulting deep green solution gives the title compound a dark green tinge.
Obtained as a brown solid: m, p, 85-90°: i
r (Nujol)3110.1590.1280,
1250,1120.1010.990.840.82
5.760.700ffi". <l*1'-bisnyl-4-yl)dimethyl (IH-1
,2,4-)riazol-4-ylmethyl)silane
A metal complex was similarly prepared: 1:] complex of cuprous chloride steel.
Body: m, p, 83-87℃, 2 with chlorinated steel:
1 complex: m, p, 85-92 °C, 1 with zinc chloride
=l complex: n”1.5737, 1 with manganese sulfate
:l complex: m, p, 244-250°C (decomposition). Example 29 Preparation of salt 10- in dichloromethane. Of (0,0034
mole) of (1,1,'-biphenyl-4-yl)dimethy
(tH-t, 2.4-)riazol-1-ylmethyl)
Seven runs of the solution were diluted with 1.0 ml of dichloromethane.
1F (0,0034 mol) of 4-dodecylbenzenesulfate
Combined with a solution of fonic acid. Live f! When the water evaporates,
The title salt was obtained as a viscous yellow oil: n”i-5
645; r r (pure) 3110, 3050.30
20.2960.2920.2850.2570.19
20.1600.1545.1485.1455.14
05.1250.1225.1165.1120.10
30.1010.990.845.825, 755, 7
35,700. 670, 635cWv'nExample 30 Production of 2:1 complex of orchid and chlorinated steel 39sl Tet
1.0f (0,0032 mol) of [
Bis(4-fluorophenyl)]methyl (IH-1,2
, 4-1 riasol-1-ylmethyl)silane and 0.2F
(0,0016 mol) of cupric chloride in a mixture of N,
Reflux for 30 minutes, then evaporate.
The compound remained as a patina glass: m, p, unclear
;1, (NujoIR) 15801, 49o, 123Q
, '1160, ]110.830.785cW
I-'. A 1:1 complex with dichloride was similarly prepared to give a dark green color.
Russ was obtained: m, p, unclear; i "as per
. By applying the procedure of Examples 26-28, Table ■,
Which of the compounds ■, kl, IX, ■ and X1ll?
The salts or gold complexes can also be changed. Example 31 2.4-)Reazol-1-ylmethyl)Cmeth,4-di
(1,1'-biphenyl-4 in methylformamide)
-yl)chlorochloromethylmethylsilane and 2.1 of the art
．． 2.4-) Sodium lyazole at 80-90℃
Add 2 hours to the session. Then add 10 parts methanol
, the mixture was kept at 70°C for 1 hour, cooled and diluted with water.
Then, quickly extract it with ether. This ether solution
Washed with water and brine, dried with magnesium dibasic acid, and evaporated.
When emitted, the title compound remains. Use appropriate rolosilane and alcohol L, R@=OH
For, use water instead of alcohol and add
If water splitting is carried out at 20-25°C instead of 70°C,
Related compounds can be made in the same way. Example 32) Preparation of silane 3.6f (0,015
mol) of chloromethyl (],]1-dimethylethoxymethane
Chill(phenyl)silane and 1.3 f (0,015 mo
1.2.4-) of 1.2.4-) Mixing with lyazole sodium salt
The material was stirred at 80° C. for 2 hours, cooled and poured onto water. The resulting mixture is extracted with water and the ether extract is mixed with water.
Washed with ink, dried with sulfur-magnesium, and evaporated.
, 2.79 of Yellow Denyu remained. Chromatog with siliga gel
Raffy with 50:50 ethyl acetate-hexane.
Upon elution, 1.5f (36%) of the title compound appeared as a pale yellow electron.
Obtained as oil: '"D"1.5134;
t r (pure) 3120.3070.3045.29
75.2925.1500゜1425.1380,】3
65.1270.1255.1240.1190.11
40.1115.1050.1020, ]010.83
0.810.790.740.700.68051-”
; nmr (CDCI, ): 0.6 (3H.S), 1.3 (9B% sl, 3.9 (2H,S)
, 7.3-7.7 (5H, rr), 7.9 (IH, s
) and (j8.o (I H,s ). Example 32A Preparation of Silane
fluorophenyl)3C2-propoxy)silane lO,o
130.6 mmol) and 1,2°4-triazolna
A mixture of 11.9 (3α6 mmol) thorium salt was added to the nitrogen thread.
The mixture was stirred at 80-90° for 2 hours. In Example 32
A waxy solid is obtained by treatment such as lr.
l! 1 Wash with ether-hexane to obtain the title compound.
10II (:110%) remained. from chlorobutane
A pure sample was obtained by recrystallization: melting point 130-13
1@1Bmr(CDCL@)41(27f,a),
5.8 (IB*Broad B), 7.1 (4B, tl, 7
．． 7 (4Hed's d)% 7.8 (1#, j),
&0(1)J, 8). Example 32E The method of Example 32A was applied to chloromethyl [bis(4-chloro
It was applied to phenyl)-(2-propoxy)silane. place
The oil is obtained by distilling the oil, which is then decanted.
And residual oil f9! 1 hexane-ethyl acetate
The product was recrystallized to obtain a lH glumellar prismatic solid. Melting point 1
3G-131” 寥nmrccD(:L@3 4
1 (2B, a), 6.3 (IB, broad
a), 'I-4 (4He d), 7.6 (4H,
d), 7.8 CIH, a), 8-0 (IHes). The mother liquor was chromatographed on silica gel and then
Extract with xane 1 and then 9! IN chloromethane-acetate
The 4H isomer was obtained as a solid by elution with mp 9
g-103° Reference%mf (CDCJI) L7 (1#*:
'Load' s t 2 (2H*a).r,5csH,a),r,5czH,a).Example sgc (l,1-biphenyl-4-yl)methyl(2-deropo
xy)(IH-112,4-triazol-1-ylme
chill)-silane 10I (8,9 mol), concentrated hydrochloric acid 31
t, a mixture of water IQy and tetrahydrofuran IQs'
was stirred overnight at room temperature. Dilute the resulting solution with ether
Wash with saturated aqueous sodium bicarbonate solution and prine.
Cleaned, dried over magnesium and evaporated.
A viscous oil of zsy remained. Chromatograph with silica glu
and eluted with hexane, followed by ether.
The title compound was then obtained as a viscous oil, which was released.
It solidified when left to stand. Melting point, 97-99"t
(CDCIB) as (3H, s). 19(1!ff,#), &x(tH*puse)@#)
%7.3-7.8(sB,s), 7.9(tH,a)
. &0(IBe')e Table ■ and hawk compounds use the method of Example 8l-31G
It can be manufactured by Example 32 Describes the production of disiloxane from DIIC
. Example ssD Chloromethyl [bis(4-fluorophenyl)] (]2
-Propoxysilane 11. Og (3 & 7 mmol) and
4911 aqueous hydrofluoric acid 1G in ethanol solution
2 hours under nitrogen! Take 1flL and cool. Partitioned between water and ether. Organic water and prine
washed with water, dried over magnesium sulfate, and evaporated.
In total, 9.7j+(10(1) of chloromethyl (fluoro)
) [Bis(4-fluorophenyl)]silane is a persistent oil.
The meeting that remained as (mobile oil)*” L5
! 1871 nmr (CDCI,) r19 (2E
ed),? 4 (4H, t), 7.8 (4H, d of d). The film prepared as above in dimethylformamide
fluorosilane 4.5116t mol) and 1,2.4-
Triazole sodium salt L69 (18t!j mol)
The mixture was stirred at 80-90' for 2 hours. Surah obtained
Dilute the lee with ether, three times with water, and then with prine.
Washed once, dried over magnesium sulfate, and evaporated
It left a viscous oil. 111 ether-hexane
Reachesition and Lllll! 3'll) title
Disiloxane was obtained as a colorless solid. Melting point 11i5
-1118 @1ssr(ni'jJcj@)41(2
Hes), 7.0 (4B, t), 7.4C4H, d of d
). r, sc *H, s), y, s(xH, a). , ki − he he he he he he
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- Example 33 25.1 m (3
6,8F, 0.200 mol) of chloromethyltrichloro
The solution of silane was cooled to -78°C under nitrogen and vigorously
Stir, while 2 of 48.01/(0,100 mol)
．． Add 1 mole of phenyllithium for 1 hour.
I put it down. After stirring for an additional 30 minutes at -78°C
, the solution was warmed to room temperature and evaporated to about 200-
. After addition of ether of 5QQid, the salt precipitated by filtration
After removing the lithium chloride and evaporating the filtrate, 25. Of
Liquid remained. Upon distillation, the title compound of 6.5F (291) is obtained as a colorless
Obtained as a liquid: bp 62-82° (0,15 m)
; nmr (CDCIs): δ3.3 (s, 2) and
and 7.1-7.9 (m, 5). Example 34 Preparation of chloromethyl(jetoxy)phenylsilane 1.0f (0,0044
Dissolution of molar)nochloromethyl(dichloro)phenylsilane
The solution was cooled to 0°C and stirred with nitrogen, during which time the solution was heated to 0°C.
61m (0,445fX0.0044mol) of triethyl
Slowly add the rumamine until a slurry is obtained, which is then
It was warmed up. Add 50% of ether and precipitate by heating.
Remove triethylamine/hydrogen chloride and evaporate the filtrate.
A residue is then obtained, which can be removed using a short silica gel plug.
Use 95% petroleum as an eluent.
ether: ethyl acetate) and 0.8Of (73 tatami) surface
The compound was obtained as a colorless oil: nmr (C1) C1
I: 1.25 (electric, 6, J=6Hz),
3.0 (s, 2), 3.9 (q, 4, J=6Hz
) and 7.2-7.9 (m, 5). Example 35 Preparation of silane 15-2.0f (0,00
9 mol) of chloromethyl(dichloro)phenylsilane
Add a solution of 2-propanol and 5-propanol to N.
! Mix, while 2.1j (1.9f% 0.018 mol)
of triethylamine was added dropwise. The resulting slurry
℃ for 2 hours, cooled, diluted with water and extracted with ether.
I put it out. Wash the ether extract with water and prine, add sulfuric acid
When dried with magnesium and evaporated, a 2.2F liquid is obtained.
T left. Perform silica gel column chromatography
, when eluted with petroleum ether, 1.4F (58'll &
) was obtained as a colorless liquid: n","
1.4741; nmr (CDCIB) 1.2
(12Hsd, J=6), 3.0 (2H, S), 4.
3 (2H. 5eptet%J=6), 7.3-7.8 (5B,
m). Using the procedures of Examples 33-35, the compounds of Tables X and ■
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Example 36 Phenylbis(2-propoxy) (IH-1,2゜4-
Production example 32 of triazol-1-ylmethyl)silane
The procedure for chloromethyl(phenyl)bis(2-propoxy)
c) Create a compound in the table by applying it to silane.
Can: nv1.4962: nmr (CDCI,
) 1.1 (12H, d. J=6), 4.0 (2B, 8), 4.3 (2H. 5eptetSJ=6), 7.2-8.0 (7H, m
l. Compounds in Tables
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Example 37 Preparation 5Id 2.6ft0.01 in dimethylformamide
0 mol) of (1,1'-biphenyl-4-yl)chloro
Methyldimethylsilane and 1.1f (0,012 mol)
Compound with imidazole sodium salt at 80-90℃
Warm for 2 hours, cool, dilute with water and extract with ether.
Next. Wash this ether solution with water and prine, and
When dried with magnesium and evaporated, it becomes a viscous pale 2°Of
Yellow electric oil remained. When a small amount of sample is crushed with xane, the solid is
Obtained. The crude product was then converted into 20117 xanes.
and 311j with ethyl acetate, and this solution
Cool the liquid slowly, and when the crystals are observed,
added. When the resulting crystals are collected and dried, 0°54r
Colorless flakes of the compound (291) were obtained:
m, p, 51-53'; 1r (NujolR)
1235.1215.11o5.1o65.900.
830.785.750,730,685cm'
: nmr rcDci, ) 0.4 (6HSs)
, 3.7 (2Hls) 6.7 (I H% wide S
), 7.0 (161 wide 8), 7.1-7.8 (1
0H, m );C+gHeoN*Sj (mw 29
Analysis of 2.45): ! Calculated value C, 73,92; H, 6,89; N, 9.
58; Actual value C, 73,4; H, 7,0;
N, 9.4; 73.7; 7.0; 9.4
゜Example 38 2.2f (0,010
chloromethyl(4-chlorophenyl)dimethyl (mol)
Silane and 1.1f (0,012 mol) imidazolna
Stir the mixture with thorium salt at 80-90℃ for 2 hours.
, cooled, diluted with water and extracted with ether. This a
The solution was washed with water and prine, and then washed with magnesium sulfate.
Drying and evaporation yielded 2.0f (81%) of the title compound.
was obtained as a yellow liquid: n” 1.5472:i
r (pure) 1560, 1495.1480.1375
．． 1250.1105.1080.905.830.8
]0.740aR':nmr (CDC1,)0.3
(6H, s), 3.6 (2B. S), 6.6 (IH, wide S), 6.9 (IH, wide
S), 7.1(If(, wide 8), 7.3(4)(
, s). Example 39 5.1f(0,
020 mol) of chloromethyl (2,4-dichlorophenylene)
2) dimethylsilane; Of (0,022 mol)
mixture with imidazole sodium salt at 80-90℃
Stir for 2 hours and finish as in Example 18.
, 3.9y (cs9%) of the title compound as a kaden oil.
Obtained: n “D” l-5637; ir (pure)
1560.1500.1450.1355.1250.
1105.1095.1075.1025.840.7
80.735 m'; nm r (CDCIs) O-
4 (6H%!!), 3.9 (2H-3), 6.7
(IH, wide S), 7.0 (IH. wide 3), 7.2-7.5 (4H, m). Example 40 4.9f (10117) in dry dimethylformamide (
0,020 mol) of chloromethylCdiphenyl)methyl
Silane and 2.0f (0,022 mol) imidazolna
Stir the mixture with thorium salt at 80°C for 3.5 hours,
When finished as in Example 18, a yellow light of 4.8 f.
Oil was obtained. Original tube distillation: 125 tl: 10.05 ■
2.9f (5210
The title compound was obtained as an oil: n"1.5995
; if (pure) 3375, 3250.1500.1
430.1255.1230.1110.1075.1
025.810.790.735.700.660cm
” ; nmr (CDC11) 0.6 (3H,S)
, 3.9 (2H,s), 6.6 (In2 wide range)
, 6.9 (IH, wide S), 7.2-7.5 (11
H, m). The procedures of Examples 37-40 were followed as appropriate for colomethylsila/s.
Compounds of Table XIV by applying to ? : Can be manufactured
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611 year old lie, ・home 11 1 1 1 ・ groan 1 year old +1 tX, - size Example 41 (1,l'-biphenyl-4-yl ) dimethyl (2-meth)
Chil-IH-imidazol-l-ylmethylated Example 37
(1,1'-biphenyl-4-yl)chloromethyl
Sodium dimethylsilane and 2-methylimidazole
By applying K to the salt, a surface compound is prepared. In this way, 2,4-dimethylimidazole, 4.5
-dimethylimidazole and 2,4,5-trimethyl
Related compounds can be prepared by using imidazole salts.
Can be built. Using the procedure of Example 41, the compounds of Table Xv can be prepared.
Ru. Ro he 0 Roto
t'11 tX ce a ce ce ro
0.5Of(0,00
17 mol) of (1,1'-biphenyl-4-yl)dime
Chil(IH-imidazol-1-ylmethyl)silane and 0
．． A mixture of 22F (0,0017 mol) under N
After centrifugation for 15 minutes, the resulting dark green solution was evaporated and
A solid of the title complex with 8P peak p was obtained: m, p, 7
2-80'(decomposition); i r (Nujol") 159
0.1515.1250.1110.840,820.
750,15.65051''-1゜By applying the procedure of Example 24, Tables X1■, XV
, XVI, XVI,
It can be converted into a reed complex or salt. Example 43 Preparation of orchid (1,1'-biphenyl-4 in dimethylformamide)
-yl)chloro(chloromethyl)methylsilane and 2 equivalents
of imidazole sodium salt at 80-90%
Warm to ℃ for 2 hours. Next, add 10 equivalents of methanol.
Then, this mixture was kept at 70 CIC for 1 hour and cooled (7,
Diluted with ice and rapidly extracted with ether. this ether
Wash the solution with water and brine and dry with magnesium chloride.
and evaporates to leave the title compound. Unfortunately, using Roronran and alcohol, Rs = OH
Therefore, use water instead of alcohol and add
Water splitting at 20~ instead of 70C? When carried out with 5C,
Related compounds can be made in a lW1-like manner. Preparation of Example 44 3,6t (0,01
5 mol) of chloromethyl (1,1-dimethylethoxy)
Methyl(phenyl)silane and 1,3f (0,915 mol
) with 1 part of imidazole sodium at 50°C.
It’s time! Mix, let stand at room temperature for 72 hours, pour into water,
Extracted with ether. This ether extract was mixed with water for 3 (ψ
, washed once with brine, dried with magnesium nitrate,
After evaporation, 3.89 g of oil remained. Vaporize impurities
Removed by tube at 90°C (air bath) 10.05 m5
Then, the table-compound of 2.9F (section 71) is the light back oil and
= n ”v L 5291; effect (pure
)3105.3070.3045.2Q70.1590
゜1500, 1425, 1360, 1250, 1235
．． 1185.1110.1055.1020.900.
805.740,700,660cm': nm
r' (CDCI, ): 0.6 (3H,s),
1.3 (9H, s), 3.6 (2H, S), 6.
8(IH,s), 7.0(11(,8) and 7.3-
7.7 (6H, m). Using hand III of Examples 43 and 44, ζTable XVI
and X■ compounds can be prepared. Example 44A L Chloromethyl [bis(4-k) in dimethylformamide
lorophenyl)3Ct-propoxy)silane 5I9(
IL3 Denrimol) and imidasil sodium salt 1.5
jl (17 mmol mixture heated to 80-90° for 2 hours)
Warm, cool, dilute with ethyl vinegar, rinse with water 3 times and rinse with water.
Wash once in the inn. Dry over magnesium sulphate and evaporate to a viscous oil.
remained. When triturated with ether, the title
Compound 10119%) was obtained as a solid.
-Melting point, 131-133” fkaiso de (CD, 5OC
D,) Table 1 (2#, jL6.8 (1 horn, s
L 6.9 (IBss), 7
．． 4 (411°d), 7.6 (sH,d 1°4NCQC4NC'QNaaxc-a Implementation fl145 Production of bis(2-propoxy) 7 run The procedure of Example 26 was repeated for chloromethyl(phenyl)bis(2
- When applied to (propoxy)silane, the title compound
Able to manufacture products: n” 1.4971 enmr (CD
CIs) 1.2 (12H, dSJ=6), 3.6 (
2H, 8), 4.2 (2H, 5ppt, J=61
．． 6.8-7.6 (8H, m). Compounds flff1 in Tables XvI and X■ can be prepared like
. /'' (- Iso 11 groan n
Useful formulations of compounds within the scope of this invention can be formulated in a conventional manner.
Can be prepared. For example, compounds can be found in dust, granules, pellets.
liquids, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates.
It can be blended as a thick liquid. Many of these are directly applicable. Sprayable formulations are suitable
Increase with proper medium, several liters to several hundred liters/hectare
Can be used with a spray volume of High strength compositions
It is mainly used as an intermediate for blending. Distribution
The compound broadly contains about 0.1 to 991 Kt% of active ingredient;
(approximately 0.1-20% by weight of surfactant and lbl
about 5 to 9 liters or at least 1 bottle of liquid inert diluent
It can also contain ash. More specifically, those formulations are
, these components are contained in approximate ratios as shown in Table 3.
Will. Weight moisture ratio III powder 20-90 0-74
(including 1-10 thick liquid) Aqueous $18 liquid 10-50 40-84 1
-20 dust 1-25 70-99
0-5 grains and pellets 1-95 5-99
0-15 High strength composition 90-99 0-1
0 0-2 lower level than these higher level
The active ingredient is the intended use and physical properties of the compound.
Of course, it can exist depending on. surfactant
A high ratio of agent to active ingredient is sometimes desirable and formulation
Achieved by mixing into a substance or by mixing in a tank
. Some typical solid diluents, Waxkins. pt al. , @)landbnok nf
In5ecticideIJust Diluents
and Carriers”, 2nd Ed., Dor
land Books, Caldwplj, New
Jersey. More absorbent dilution
The agent is preferred for wet powders, and the denser ones are for dust
preferred. Typical liquid diluents and solutions *1-1, M
arsten, ``5olvpnts Guide,
”2ndEd+, Infer 5science,
New York, 1950. 0
．． A solubility of 1% or higher is preferred for suspension concentrates;
Thick materials are preferably stable against phase separation at 0°C.
Ru. @McCutchp-on'sl)eterge
nts and EmulsifiersAnnua
I”, Me Publishing Carp. Ridgpwood, New Jersey, Nara
and 5iselyand Wood, -Encycle
npedia of E3urfnceActive
Chemical Publish
ingCn, Inc, New York, 1
9 6 4 Surfactants (3) and recommended uses
is listed. All formulations can be foamed, caked,
Add small amounts of additives to inhibit corrosion and microbial growth.
Incurred by inclusion. Methods of making such compositions are well known. The solution is prepared by simply mixing the ingredients. slight
Fine solid compositions can be compounded, usually by hammering.
By grinding as in a mill or fluid energy electric
Create and create. ! ! ! ! Sawa liquid is l! by two wet rings!
1IIl (e.g., Litter, U.S. Pat.
No. 60,084 #fi). Granules and pellets are
By spraying the chemical substance onto the preformed granules,
The liquid is formed by any one of a number of agglomeration techniques.
can be done. J. h:, Browning, -Ag
Chemical gngineering, Dec
ember 4. 1 967, pp. t47 ff. and “Pe
rry'sChemical Engineer's
Handbook”, 4th edition, McGraw-H
I, New York, 196B. pp, 5-59ff #Sho. Example 46 Wet f14 powder azol-l-ylmethyl)silane 40 11g
Dioctyl sodium sulfosuccinate
1.51g lignin sulfone agent
Thorium 3g6 low viscosity methylcellulose
1.5-cho tapalgite
54 #I Mix these ingredients well and add air
passed through a mill to an average particle size of less than 15 microns;
Remix and sieve through □ American Standard 50 sieve (0.3ms opening)
After that, wrap it. All compounds of the invention can be formulated in the same manner. Example 47 Wettable powder-1-ylmethyl)silane
Sodium lennaphthalene sulfonate 2-low
Viscosity methyl cellulose
± 76 regret these ingredients
Blend, roughly hammer mill, then 9-kiss-y-g
Essentially all active particles with a diameter of 10 electrons or less
Generate children. This product is reformulated and then packaged.
. Example 48 High strength concentrate C4-/lorophenyl)dimethyl-1-ylmethyl)silane 9B, Sf4silane
Rika airgel O, S* synthesis
Amorphous moldy silica 1.011 these
The ingredients are blended and crushed in a hammer electric kettle to essentially
All are passed through US standard 450 sieve (0.3tm opening)
Produces a high strength concentrate that passes through. This material is then
It can be blended using the rice method. Example 49 High strength-thickness from Dust Example 48 25.411 Pa
Irophyllite, powder? 4.691 this
Mix the ingredients thoroughly and package for use. Example 50 Aqueous suspension azol-1-ylmethyl)silane 50.99 g
Lyacrylic acid thickener 0.3 width dodeci
7EL polyethylene glycol ether 0.591
Disodium phosphate 1.01 phosphorus
Acid-sodium 0.5° polyvinylvinyl
Nil alcohol i,o saka pentaku
Lorophenyl 0.4191 water
46.3 visit
These ingredients are blended together in a sand mill to substantially
All produce particles with a size of less than 5 tons. Example 61 Rough 20gI
Iria benzene 749! hmm
Rubitan monostearate and its polyoxyethylene condensate 6-These
The components of are combined and stirred to form a solution. This solution
can be emulsified in water for application. Example 52 1-ylmethyl)silane 30 oil-soluble
Blend of sulfonate and polyoxyethylene ether 4g! Kishi
Ren 6691G this
Combine the ingredients and stir while gently heating.
Accelerates dissolution. Fine-sieve filter for packaging work
Including, non-example 53 heterogeneous in the product I of granular example 46! #Il powder 15 excellent
Setsufou 69 acid potassium
Rium 16 these
The ingredients are blended in a rotating tdp machine and granulated by spraying with water.
conduct. Most of the materials are 1.0~α42■ (US standard 41
When the desired range (8-4o sieve) is reached, remove the granules.
Drain, dry, and sieve. Large materials are crushed
to create the desired range of additional material. These granules are active
Contains ingredients. Example 54 1-ylmethyl) Sila 7 304 oil-soluble
Blend of sulfonate and polyoxyethylene ether
6611 these
Combine the ingredients and stir with gentle heating until dissolved.
Accelerate the solution. Include fine sieve filters in packaging operations.
ensure that no foreign, undissolved substances are present in the product
Let's do it. Example 55 -1-ylmethylsilane 309I oil soluble
4111I xylene blend of polyoxyethylene ether and sulfonate
60qk Combine these components.
Combine and stir while gently heating to accelerate dissolution.
Ru. Including fine sieve filters in packaging operations
to ensure that foreign, undissolved substances are not included in the product.
K. Example 56 Bis(4-/lorophenyl)methyl(IH-1,2,4-triazol-1-ylmethyl)silane 3096 oil soluble
Blend of sulfonate and polyoxyethylene ether 4qb
Len 66m these
Combine the ingredients and dissolve by stirring with gentle heating.
accelerate. A fine sieve filter is used in packaging operations.
to ensure that foreign, undissolved substances are not encased in the product.
I'll do my best. Example 57 Bis(4-fluorophenyl)methyl(1) 1-1 ,2 ,4-)riazol-1-ylme
chill) silane 2o chlorobenzene
74 tin rubitan monostear
and its polyoxyethylene condensate
The components of are combined and stirred to form a solution. This solution
Can be emulsified in water for application. Example 5B Sol-1-ylmethyl)silane
66III these
Combine the ingredients and stir while gently heating to dissolve.
Accelerate the solution. Fine sieve filter for packaging work
If foreign, undissolved substances are present in the product, including
K to make sure it doesn't happen. Example 59 Wettable powder ylmethyl)silane 504 alkyl
Lunafta V Sodium Sulfonate 29G Low
Viscosity of methyl cellulose
± 46 悌These ingredients
blended, roughly hammer milled, then air milled.
essentially all are active below the diameter IQt Chron.
Produces paddy. After the product is reformulated, it is packaged. Example 60 Wettable powder ylmethyl)silane 40% sulfonate
Dioctyl sodium succinate
1,5 oz Sodium lignin sulfonate
3mm low grade methyl cell fourth
1.51 Attapulgiyaite 54
Mix these ingredients well, pass through an air mill, and flatten.
Generates average particles with an average particle size of 15ε or less, and external compounding
and passed through a US Standard layer 50 sieve (0.3 mm opening).
After sieving, it is packaged. All compounds of the invention can be formulated in the same manner. Example 61 (1,1'-biphenyl-4-yl)dimethyl(IH-ikidacyl-1-ylmethyl)silane 30Is oil soluble
Blend of sulfonate and polyoxyethylene ether)” 41g
xylene 66
Combine the ingredients and stir while gently heating to dissolve.
Accelerate the solution. Wrapping fine sieve filter into packaging operation
to ensure that no foreign, undissolved substances are present in the product.
I'll do it. Example 62 ylmethyl)silane 2ochlorochloro
Benzene ゛74% Sorbitan
Monostearate and its polyoxyethylene condensate 6%
The components of are combined and stirred to form a solution. This solution
can be emulsified in water for application. Example 63 Aqueous suspension (lel'-biphenyl-4-yl) dimethyl(IH-imidazol-l-ylmethyl)silane 25-hydrated atta
Pulgite 3 Sac crude lignins
Calcium sulfonate 10 11 Dihydrogen phosphate
um 0.5 slow water
61.5 these ingredients
Grind together in a ball mill or roller kill to harden.
The particles should be smaller than 10 microns. Example 64 High strength concentrate (Ilmethyl) 7 runs 98.5 vomit
Kae aerogel 0.51G synthesis
Amorphous fine silica 1. OIG these
The ingredients of
All were passed through a US standard 450 sieve (0.3 m opening).
Produces a high strength concentrate that passes through. This substance is then used in various
It can be blended using the following method. Example 65 Wettable powder of granules Example 60 15 Chisetsuko
C 69% potassium sulfate
16 ingredients
Blend in a rotating electric mixer, spray with water, and granulate. Most of the materials are 1.0 to 0.42■ (US standard ji18
~40 sieves), remove the granules.
Take out, dry and sieve. Crush large materials
, to produce the desired range of additional materials. These particles are active
Contains sexual components. ,' Example 66 High Strength Concentrate from Dust Example 64 Zat*Pyro
Phyllite, Powder 74.611 These ingredients are blended well and packaged for use. Example 67 Emulsifiable concentrate 4-chlorophenyl(methyl)phenyl(18-imidazol-l-ylmethyl)silane
Benzene 74 Sorbitanmo
Nostearate and its oxyethylene condensate 6Is
The components are combined and stirred to form a solution. This melt
The liquid can be milked in water for application. Practicality The compounds of the present invention are useful as agents for suppressing plant diseases.
It is for use. They cover a wide spectrum of species, especially
foliar pathogens of ornamental plants, vegetables, cereals and fruit crops
, for example, Pucc-i-1isrecond a,
gde clchoracearum. Eryslpbe gram Inis, Venturi
a 1naequa-lis, He1minthosp
orium mayd! -8, Cp-r, co-Hato
Mitsufusenra 1nfestsl and other Phyto
It is effective against phthora species. Also, they are diseases of seeds.
A bulk substance, for example, Pyt: jurn aph! na-d
Suppress ermJl tum. Disease control is usually done by adding effective food compounds to the plants that are to be preserved.
parts of things, such as roots, stems, leaves, fruits, young, tubers, etc.
or a medium in which the scales or the torage to be preserved grow c.
± The sand can be applied before or after infection.
will be accomplished. Additionally, the application rate of these compounds is
can be influenced by many factors, such as busyness, and
It should be determined based on actual usage conditions. The leaves are usually
, source of active ingredients from less than x ppm up to 500 ppm
Can be protected when processed at high temperatures. 0.
In soil treated with concentrations of 1 to about 20 Kt/ha.
Growing vegetative, can protect against diseases. seeds and seedlings
are usually treated at a rate of 0.06 to about 31 per seed.
It can be protected. The compounds of the present invention can be used as fungicides, bactericides, acaricides, etc.
, nematicides, insecticides, or other biologically active agents.
Mix with metallurgical materials to minimize time, effort and material consumption
to achieve the desired results. 1 weight of the composition of the invention
qFi of these biologically active substances per unit,
It can vary between 0.05 and 25 coulometric parts. child
Suitable materials of the species are well known. some,
Described below. Rodenticide methyl 2-benzimidazole carbamate (carb
andamim) Tetramethylthiuramzosulfide (thi de(!I
I) 5-dodecyldaaniynoacetate 1dedin*
) manganese ethylene bisdithiocal 14fi-)(m
aneh) 1,4-dichloro-1,5-P) metomecype/zen(a
hle de ASSS) Methyl l-(butylcarbamoyl)-2-penzimine
Zolkarha fi-) (&#%omyj)2-cyano
-N-ethyl cal/4 moyl-! -Methoxyi Kennoase
Egmozanil N-(trichloromethane)
aaptan
) N-(trichloromethylthio)phthalimide (folp
at) trimethyl4,4'-(e-phenylene)bis(3-thi)
(thiophanate-me)
thyl)2-(thiazol-4-yl)benzimidazo
Al(thiabmndagolm) Aluminum tris(0-ethylphosphonate ("A
11stta') Tetrachloroiso7talonitrile (chlorothα
-1onil) 2,6-zochloro-4-nitroaniline (dieh-1
era calculation) N-(R,8-dimethylphenyl)-N-(methoxya
cetyl) alanine methyl ester (ynatalazy
l ) Cus N-[(l*t, g, 2-tetrachloroethyl)
thiokocyclohekiku 4-ethy-t, g-dicarpioki
aaptafol 8-(3,5-dichloro)
lophenyl) -N-(t-methylethyl)-g,i-
Dioxo-1-imidazolidine carboxyamide (1p
rodion#)3-(3,5-dichlorophenyl)-
5-ethynyl-5-methyl-2,4-oxasilyt,p
yyoy (v<scjogo[%) Kasugamycin〇-ethyl8. S-Zophenylphosphorodithioate
(edifylhag) tribasic sulfate steel sulfate stregtomy 7-oxytetracycline acaricide senecioic acid, it-##e-butyl-4,6-cinit
Esters with lophenol (binapaeryl)
6-Methyl-1,3-dithiolo(4,5-83quinoxa)
Lin-2-oy (otxythioqsinaz)
2,! , 2-) pomegranate 1,1-bis(4-chloroph)
henyl)ethanol (dicofol)bis(-4)
tachloro-2,4-cyclopentadixy-x-yl) (
d(s%*ehl or) tricyclohexyl tin
Droxide (cyhe-zat (s) hexakis(!-methyl-2-phenylglobil) diss
Tannostin oxide (fmnbstin oxide)
Granule insecticide 2-[shedoxyphosphinyl imino)-1゜3-diti
eta y (10st &(#tam) S-1 chill 1-(t
/Methylcarbamoyl)-N-(Methylcarbamoyl)
xy)-thioformimidate (u*amyl) S-methyl l-carbamoyl-N-(methylcarbamoy
ruoxy)thioformidate N-isozolobylphos
Foraozonic acid, 〇-ethyl〇'[4-(methylthio)
)-m-tolyl] diester (fgnamsAs5) Insecticide 3-hydro-N-methylcrotonate (dimethyl
phosphate) ester (monoeroto-pho)
a) Methylcarboxylic acid, 2,3-dihydro-2゜2-zo
Methyl-7-penzofuranol (aarbe-fs de α
duck) Q-[2,4,5-)chlorolo α-(chloromethyl)
Pe/solcholic acid, 0',0'-tumethylester A/
(tatraehlorvinphoa) 2-merca
S with ctosuccinic acid, soethyl ester, thionolinic acid
-Ester, trimethylester (malathion)
) Phosphorothioic acid, 0.0-dimethyl, 0-13-dito
methyl parathi
on) Esthetic treatment with methyl carbanoic acid and α-naphthol
(6αrbαdeyj) Methyl N-[[(methylamino)carvinyl]+#V”
Jxri/imidothioate (mmthomyl)N'
-(4-chloro-o-tolyl)-/V, #-sol f
k * A/ A 7mi Ny (aklerdinuf
orm) OoO-diethyl-〇-(!-isoglobil-
4-Methyl-6-bilielectrosol) phosphorothioate
(d(6g inn%) octachlorocaftene (tetaaphena)〇
-Ethyl 0-p-nitrozeerphenylphosphonotio
ate (IIPN) cyano(3-phenokycuphenyl)methyl 4-chloro-
α-(l-methylethyl)benzene acetate Cfa*
valerata) (3-phenokycuphenyl)methyl(±)-cis,tra
ence-8-<2.2-dichloroethynyl)-$1. ! −
Zomethylcycloglononanxylate (p# de
sgthrin) diethyl N, Nl-[thiobis[(N-methylimino)
Bis[ethane]
] (thiodicarb) phosphorothiolothione
Acid, 〇-ethyl〇-[4-(methylthio)phenyl)
-8-s-globyl ester (asLprofoa)
α-Sitaano-3-phenoxybencyl s (g, 2-
dichlorovinyl)-2,2-dimethylschiff o yo
717 force A/ &*shiv-) (eyperme
trrts) cyano(3-phenoxyphenyl)methyl
to 4-(difluorometho)-α-(methylethyl)
yce/a*f-) ("Payoff')0.0-
diethyl-〇-(3,5,11-trichloro-2-pyri
phosphorothiony) (aAj-orpy decifo
a) O,O-dimethyl-8-((4-oxo-1゜2.3-
benzotriazin-5-(4H)-yl)methyl]phos
Phrodithioate (αzinphoa-matk111
) 5.6-dimethyl-2-diethylamino-4-pyrimidi
Nilzomethylcarpamate ('Pirimor') S-
<N-yF, lumi-N-methylcarbamoylmethyl)
-0,0-N methyl phosphorodithiony) (for
motion) S-*-(ethylthioethyl)-0,0-somethylphos
(dematon-8-met)
hyL) α-cyano-3-phenocypendirux-3-(12
,2-'/bromovinyl)-g,g-zomethylcyclolog
(deltamet-rude)
5s) N-(2-chloro-4-trifluoromethylphenyl)
7 Raniy ('Mavrik') according to the following example.
The present invention will now be further explained. Example 68 Compounds of the invention were added to a final volume equal to 691 in acetate/
250 ppm* surfactant MT
Contains ItEMO14 (multi-flfi alcohol ester)
In purified water with a concentration of 100 ppH &! l
I! Cloudy nine. these! Dripping the slurry onto wheat seedlings
I sprayed it until it dripped. The next day, the plants were covered with wheat leaves.
Pxeeiniarmcondit containing pathogens of mildew
inoculate with a tar, tritiai,
24 hours in a saturated humidity chamber at 20°C, then a growth chamber.
The virus was incubated for an additional 7 days and then graded as disease t'4. The table below shows the percentage of disease control. Treated plants may have only a few rust warts or
The untreated plants had a large number on each section.
He had a wart. Table 1 Triazol-1-ylmethyl) 7ran 90 lumethyl
) Silane 80 ru 1-il
Methyl)silane 100Methyl)silane
100-ylmethyl)silane
801-ylmethyl)cran
60(!,4-dichlorotetraphenyl)dimethyl(Iff-1,!,4-)lyazol-! -ylmethyl
) Silane 90bis(4-chlorophene)
(1#-1,2,4-)lyazol-1ylmethyl)silane 90 methyl
(4-fluorophenyl) (IH-1,1!, 4-triazol-1-ylmethyl)
Silane 100[:4-(1,1-dime
ethyl) phenyl] dimethyl (1/f-1, 2, 4
hmm
80A l-l-ylmethyl)silane
100azol-1-ylmethyl)silane
100 triazol-1-ylmethyl)sila7 10
0 sol-1-ylmethyl) 7 run 90 dodecy
(dimethyl)(1#-1,11,4-triazole-1
-ylmethyl) Silane 10G, 4 [Reef
-(4-chlorophenoxy)phenyl]dimethyl(1#-1,2,4-triazol-1-ylmethyl)silane 9゜l-y
methyl)silane 8゜-triazole
-1-ylmethyl)silane
90viaj (1,1'-biphenyl-
4-yl)(methyl)(x/f-t,!,4-)lyazo
(l-1-ylmethyl)silane 80(1,1'
-biphenyl-4-yl)methyl(phenyl)-(1#
-1,1 4-triazol-1-ylmethyl)silane 100(1,
1'-biphenyl-3-yl)dimethyl (1#-1,2
,4-triazol-1-ylmethyl)silane 802-chloro
Lophenyl(methyl)phenyl(1#-i, 2,4-triazol-1-ylmethyl)silane 801-i
(Methyl) Sila 7 10G Ru l-ilme
silane, 4-dodecrupenzenosulfonate to. g-ria Lophenyl (4-chlorophenyl) methyl-(x#-x, 2.4-triazol-1-ylmethyl) 7 run 100 with steel
l:1 complex 2:l complex with steel
body 100 runs
5゜Luciran
90 silane
6°) Silane 9
゜Luciran 100kura
8゜dimethyl (l
H-Imisol-Ik15-(4-T+)Fluoromethylphenyl)
Silane 1ooAru) Silane
100 dodecyl (dimethyl) (1l
i-i2dacyl-l-ylmethyl)sila/
80A-1-ylmethyl)silane 90but
Chil(lH-imidazol-ylmethyl)-methyl(phenyl)7 90(phenyl)
silane 10G(i t 1'
-Piphenyl-4-yl)CIH-imidazol-1-y
methyl)methyl(phenyl)silane 1
00(i*1'-piphenyl-3-yl)dimethyl
(IB-imidazol-1-ylmethyl)silane 9°(4-
bromophenyl)(l#-tri-piphenyl-4-yl)dimethyl(IH-imidazol-1-ylmethyl)silane, 1=l complex 100(2-
Chlorophenyl)(4-chlorophenyl)(IH-imidacyl-l-ylmethyl)methylsilane 1(). (2-chlorophenyl)(dimethyl)CIH-dimethyl-1-ylmethyl)silane
8゜bis(4-chlorophene)
hydroxy(IH-1,2,4-)lyazol-1-ylmethyl
) Silane 9゜bis(4-fluoro
phenyl)hydroxy(1-1,2,4-)lyazo
(1-ylmethyl)silane 9°
Lis(4-chlorophenyl)CIH-1,2,4-tri
azol-1-ylmethyl)silane
40 Tris(4-fluorophenyl)(IH-
1,2,4-)riazol-1-ylmethyl)silane
90 bis(4-chlorophenylene)
) hydroxy(4B-1,2,4-triazole-4
-ylmethyl)silane 90oxy
Bis[bis[4-fluorophenyl](IH-1,2,
4-) Riazol-1-ylmethyl)silane]
100(i*1'-piphenyl-4-yl)methane
Chil (2-propoxy) (17/-1,2-4-thoria
sol-1-ylmethyl)silane
100 (1,1'-piphenyl-
4-yl)hydroxy(methyl)-(IH-1,2,4
-triazol-1-ylmethyl)silane
　　　　　　　　　　　　　　　　　　　　　　　　　
90(1,1'-piphenyl-4-yl)(4-flu
orophenyl)-methyl(xH-1* 2 e 4-
) lyazol-1-ylmethyl)silane
100 dimethyl (4-trifluoromethoxy)
Cyphenyl)-(IH-1,2,4-)lyazole-1
-ylmethyl)silane 100 (4'-promo
l,1'-biphenyl-4-yl)dimethyl-(lB-
1,2,4-Driazol-l-ylmethyl)silane
　　　　　　　　　　　　　　　　　　　　　　　　　
100(1,1'-piphenyl-4-yl)dime
thyl (5-methyl-1H-t I 214-triazo
(l-1-ylmethyl)silane 100(1,t'-pif
phenyl-4-yl)dimethyl(IB-1,2,4-)ly
Azol-1-ylmethylsilane, 11 with cupric chloride
1 complex 100 (1,1'-pi
phenyl-4-yl)dimethyl(1#-1,2,4-)
Riazol-1-ylmethyl)silane, 1π-cured Kuruma Ni Steel and
2 1 complex of 100 tris (
4-fluorophenyl) (1#-imidazole-1-y)
methyl)silane
80 bis (4-fluor
(lophenyl) hydroxy CIH-imidazol-1-y
methyl)silane 100
Bis(4-chlorophenyl)hydroxy(IH-imida)
sol-1-ylmethyl)silane
80(3-chlorophenyl)dimethyl(
tH-imidazol-1-ylmethyl)silane
　　　　　　　　　　　　　　　　　　　　　　　　　
80 dimethyl (if-iden mesol-1-izo
(1-ylmethyl)methylsilane 80 (1-yl)methylsilane
methyl)silane 100A compound is 20
It was applied at a concentration of 0 ppm. Practical Example 69 The compound of the present invention was added to m and n volumes equal to 81 in acetone.
Dissolve 1 then 250 pp bait surfactant rn
Contains Ehio 14 (polyhydric alcohol ester)
fII1111 suspended in water at a density of 100 pνm.
Good. These suspensions were applied to seedlings of medium-sized cucumbers.
Chiru right 1fK erupted. The next day, 11 on the plant? Euri's
Powdery mildew [11 E digi iphm ai6 0-r
inoculated with aeaar sulcus spore suspension and grown for 7 days.
Cultured in a long room. The disease grade was then determined. disease
The suppression percentage of Qi is shown in the table below. Nine processed plants make udon noodles
1 powdery mildew in contrast to untreated plants covered with mildew
Even the slightest bit of illness or stammering
stomach. Phytotoxicity in the form of reduced growth or hormonal effects is
Some of the plants are associated with disease control. f! Shigeichi'
ZoG ethyl V methyl ([f-t,
Snow, 4-triazol-1-ylmethyl)silane to. Tutylmethyl (t H-t -t @ 4-triazole
-1ylmethyl)cran 100lmethyl)sila
y 10 oGA (4-10 mo
phenyl)dimethyl(i ff-1,1,4-)riazol-1-ylmethyl)cla
y 1ooG lunyl-ylmethy
100 methyl) silane
100-ylmethyl)sila/100G dimethyl(l-naphthalenyl)(IH-1,!, 4-triazol-1-ylmethyl)Vu)ltG. (!1,4-t/chlorophenyl)dimethyl (t#-i
o! , 4-triazol-1-ylmethyl)silane 10G-yl
methyl)silane 70-ylmethyl)
Silane to. l-ylmethyl)7 run 100#B-i
methyl) silane 100 (1//
-1,1,4-)riazol-1-ylmethyl)triphe
Nilkuran lOOon
100G (1, 1'-
biphenyl-4-yl)dimethyl(4H-1,2,4-
triazol-4-ylmethyl)silane 90-1-y
methyl)silane 100G methyl(4
-fluorophenyl) (1#-1,2,4-triazol-1-ylmethyl)silane tooGzome
Chil(IH-1,!,4-)lyazol-1-ylmethyl14-)lyfluoromethylphenyl)-clan 100G dimethyl
Chill (x H-to! @ 4-Driazol-1
-ylmethyl)(3-trifluorotetramethylphenyl)-7rane 100zomethy
(lH-t,g,a-triazol-1-ylmethyl)
(!-)Lifluoromethylphenyl)-Sila/
100(2-methoxyphenyl)dimethyl(If-1,!,4-)riazol-1-ylmethyl)sil
Ran 100G Tsuchiru (11,4-
(1#-1,!,4-)ria
Sol-1-ylmethyl) Clan 100G Bis
(2,4-Zokukudaphenyl) (!,4-dichlorophenyl)methyl(phenyl)-(lH-t,z,a- triazol-1-ylmethyl)silane 100G(4
-chlorophenyl)methyl(phenyl)(iH-t*z -4-triazol-1-y
methyl) sila7 100G (4-fluorophore)
phenyl)methyl (phenylll//-1,!, 4-)riazol-1-ylmethyl)7ran Zo. Butyl (methyl) phenyl (lH-X, 2,4-triazol-1-ylmethyl) 7 runs 100 (!, 3
- phenylmethyl (1#-1,1!, 4-triazol-1-ylmethyl) in dimeth
) Silane 1ooG(2,6-dimethoxy
Cyphenyl)zomeddecyl(dimethyl)(tH-t,2(2-chlorophenyl)dimethyl(l-methyl)silane 1ooG[4-
(4-chlorophenol)phenyl]dimethyl-(1#-1,2,4-triazol-1-ylmethyl)cla7
80(1,1'-biphenyl-4-yl)
triazol-1-ylmethyl)silane 1OO1-y
methyl) silane 10 (1 azole) 1
-ylmethyl)silane lOOran
Bo. 1-ylmethyl)silane 1004-bro
Mophenyl(methyl)phenyl(x#-t,!,4-)reasol-1-ylmethyl)silane 100[bis
(8-Kurota phenyl)] mel (17f-1,!,
4-)Ryazol-1-ylmethyl)7ran
1G.O cyclohedral (dimethyl) (1#- x * z * 4- triazol-1-ylmethyl)
Silane hooG [Bis(4-
bromophenyl)]dimethylIf-t,t,4-)riazol-1-ylmethyl
) Silane 80G (1,1'-Bife
nyl-4-yl)dimethyl(tH-i,g,4-tria
Sol-1-ylmethyl)silane, 4-dodecylbenzenesulfone 11 salt 100 (1,1'-biphenyl-4-yl)dimethyl (l/7
- l* s @ 4-triazol-1-ylmethyl)
Silane, chloride-filled l:1 complex with steel 100 (1,
1'-biphenyl-4-yl)dimethyl (lH-t,z
, 4-triazol-1-ylmethyl)silane, 1=1 complex with subchloride@(I) 80(
tri'-biphenyl-4-yl)dimethyl(if-
1,2,4-)liazol-l-ylmethyl)silane, a
l:l complex with SS-manfy 90 thoria
sol-1-ylmethyl)silane 100 phenyl
s(!!-proxy)]()1#-1.!, 4-rear
Sol-1 ÷ylmethyl) Clan 100 [Bis(
1:1 complex with dimethyl 1//-1,14-) reazol steel 100[bis(
2-fluorothenyl)]dimethyllff-t, 5e4-triazoldimethyl(lH
-imidazol-l-ylmethyl)-phenylsilane 100ethyl(
1/f-idenmesol-1-ylmethyl)-dimethylsila
y to. Butyl (lH-Idendacyl!-ylmethyl)-dimethylchloride 100 y
lo oGA(4
-bromophenyl)(IH-imidazol-l-ylmethyl)dimethylsilane 100(1,
l-biphenyl-4-yl)dimethyl (lH-imidazol-l-ylmethyl)cry to. (4-chlorophenyl)(1//-imidazol-1-y
dimethylsilane 100 (lH
-imidazol-1-ylmethyl)dimethyl-(1-naph
Tarenil) Clan
l 0O(3,4-dichlorophenyl)(1
H-Ikidacyl-l-ylmethyl) dimethylsila 7 100 (
lH-idenmesol-l-ylmethyl)dimethyl-(4-
phenoxyphenyl)silane
100 dimethyl(IH-imidazol-1-ylmethyl)-(4-methoxytzenyl)silane
1OO(2,4-dichloroph)
phenyl)zomethisilane 100(xH-
IZdacyl-1-ylmethyl)trizenylsilane
100 diphenyl (IH-iden mesol)
-1-ylmethyl)-methylsilane 100 lucrane
100 rufenyl) sira
80[4-1,1-dimethyl ether
(chill) phemethyl) dimethylsilane 80 phenylene
) Silane 100G methylsilane
100 phenyl
Ran Zo. enyl) silane 10G (fe
silane 100(2,3-dichlorosilane)
lorophenyl)(lH-Mesol-l-ylmethyl)dimethylsilane lOOdodecyl
(dimethyl)(IH-imidacyl-1-ylmethyl)cran 55(2-
Chlorophenyl)(IH-imidazol-1-ylmethyl)dimethylcran 100(4-
(4-chlorophenol)phenyl]dimethyl-(lH-ikendacyl-1-ylmethyl)silane 100butyl(
tH-ifdasyl-l-ylmethyl)-methyl(phenyl)silane 100 (1,
1'-Piphenyl-4-yl)butyl (xH-imidazo
1-ylmethyl)methylsilane 100butyl
(4-Fluorophenyl)(I H-imidazol-l-ylmethyl)methylcran 100 diptych
(lH-imidacyl-1-ylmethyl)-methylsilane 100 methyl
(phenyl)cran 100 (1,1-di
Methyl ethoxy) (1#) silane 9゜thi
Run ls. methyl)silane SOenyl
) Silane 100enyl) Silane
100 [bis(8-chloro
phenyl)〕(〕lHlmidazol-1-ylmethylmethylcran!OOcyclo
Hechusil (dimethyl (lH-i is dasyl-1-ylmethyl) silane 100G
(4-10mophenyl)](lH-itdacyl-1-ylmethylmethylsilane 1OO(l,
1-Piphenyl-4-yl)zomethylCIH-inmesol-1-ylmethyl)silane, 1 with cuprous chloride! 1 complex 100(2-
Chlorophenyl)(4-chlorophenyl)(lH-iomesol-1-ylmethyl)methylsilane 100(2-
Chlorophenyl)(dimethyl)(IB-imidazol-1-ylmethyl)silane
80 bis(4-chlorophene)
100H bis(
4-Fluorophenyl)hyP lotris(4-fluorophenyl)(IB-1e2*4-triazol-1-ylmethyl
) Silane 100 bis(4-chloro
lophenyl)hydroxy(4H-1,294-triazol-4-ylmethyl)silane 100oxy
Bis[bis(4-fluorophenyl)(i#-1w2,4-triazol-1-ylmethyl)silane] 100(1,
1-piphenyl-4-yl)methyl(2-propoxy)(x#-1゜2.4-triazol-1-ylmethyl 100l)sil
Ran(1,1-piphenyl-4-yl)hydroxy(methyl)-CIB-1,2m4-triazo
(l-1-ylmethyl) 1007 ran(1,1'-piphenyl-4-yl)(4-fluorophenyl)
phenyl)-methyl(I H-1,2,4-triazol-1-ylmethyl)silane 100 tons
(4-trifluoromethoxyphenyl)-(1#-1$2*4-1-riazole-1
-ylmethyl)silane 100G(4'-promo 1,
1'-piphenyl-4-yl)dimethyl-(i H-t
l 2 e4-triazol-1-ylmethyl) silane 100 (1,
l-piphenyl-4-yl)dimethyl(5-methyl-I H-1*2*4-tria
sol-1-ylmethyl) silane 100-ru
1-ylmethyl) silane, ttiR form with Go chloride io. c t , t'-biphenyl-4-yl)tumethyl (
1#-1,2,4-) riazol-1-ylmethylsilane, 2*1 complex with disteel chloride io. (4-Fluorophenyl)methyl(2-deropoxy)IH-1,2,4-)lyazol-1-ylmethyl)silane 1o. (l,1-dimethylethoxy)[bis(4-fluorophenyl)(IH-1*2.4-tria
sol-1-ylmethyl)-silane io. Tris(4-chlorophenyl)CsH-'iz-mesol-1-ylmethyl)silane
io. Tris(4-fluorophenyl)(I B-imidazol-1-ylmethyl) silane io. Bis(4-fluorophenyl)hydroxy(lB-imidazol-1-ylmethyl)silane 100bis(
4-chlorophenyl)hydroxy(IB-imidazol-1-ylmethyl)silane 100(3-
chlorophenyl)tumethyl(I H-inmesol-1-ylmethyl) silane 80(1,
1'-Piphenyl-4-yl) (4-fluorophenyl)-C111-i-benzene mesol-
1-ylmethyl)methylsilane 100V
thyl(IB-inmesol-1-ylmethyl)(4-)lifluoro,methoxyphenyl)
Silane 100G (4'-promo 1,
1'-biphenyl-4-yl)dimethyl-CIM-imie
dazol-1-ylmethyl)silane 100thyl)
Silane 100GAG = Growth
Hypoallergenicity and BH = hormonal effect. Example 70 The compound Ta1J of the present invention was applied in a calm manner to six strict volumes.
1 bath in setone then 250 ppm surfactant
THEMO14 (ester of polyhydric alcohol)
The suspension was suspended in pure water at a strength of 1100 pp. these
Spray the suspension onto the barley seedlings until it drips.
The first day after the repair, the barley powder pathogen E was detected.
Inoculated with spore suspension of ryaiphttgraminim
and then cultured in a growth chamber for 7 days. Then sick
The grade was determined. The disease suppression rate is shown in the table below. processed
The plants were compared to untreated plants covered with powdery mildew.
It had little or no powdery mildew. Table 3 (t#-i,g,4-triazol-1-ylmethyl)crane 901-i
100-ylmethyl)silane 100-ylmethyl
)silane 1001-ylmethyl)silane
Ran 100 bis(4-chlorophenyl
)(methyl)(IH-1,!!,4-)reasol-1-
ylmethyl)silane 100 (1#-
1,1! , 4-)liazol-1-ylmethyl)toritsue
Nylsilane 10G methylphenyl (1#-t, g,
a- triazol-1-ylmethyl)silane 100zomethy
(IH-1,1,4-dryallomethylphenyl)silane lOObutyl
(4-chlorophenyl)(IH-IZdacyl-1-ylmethyl)methylsilane 100(3,4
-dichlorophenyl) (IH -idendacyl-1-ylmethyl)ymethylsilane 80 silane
io. (1!,4-dichlorophenyl)dimethyl(1/7-y
midazol-1-ylmethyl)silane
100 bis(4-chlorotetraphenyl)(lH-ran 100 Zof
enyl(lH-imidazol-l-ylmethyl)-methylsilane 100 rufe
silane 100 dodecyl (di)silane
methyl)(IH-imidazol-1-ylmethyl)silane xooAA conversion
The compound was applied at 1 l 100 pp S degree. Actually! a Gaff 1 A compound of the invention was added in acetone in an amount equal to the final volume of 6-
then 250 pf JtNk of surfactant T
Contains HEMO14 (ester of polyhydric alcohol)
Suspended at 10099% in purified water. these
The F! ! Spray the slurry onto the limp seedlings with a dripping bottle.
did. The next day, the plant 7-1F) Rot @ @ Vant
Inoculated with spore suspension of tyia 1naeqsalia.
, in a saturated humidity chamber at 20℃! Incubate for 4 hours, then in the growth room
SaraKIG-1! I was arrested for days. Next, the grade of the disease
Determine and record nine sickles as shown in the table below. The treated plants
, compared to untreated plants covered with rot lesions.
It had fewer rot lesions. Expressed as a decrease in growth
The phytotoxicity of some species of dandelion is related to disease control.
114 cases were observed. Table 4 7-run 5oGA lume
Chill) Silane 9oG Ru! −il
methyl)silane 1GG(4-chlorophenylene)
)dimethyl(I H-x,z,a-triazol-1-ylmethyl)silane 100butyl
(4-ri4ophenyl)methyl(1#-111,4-)riazol-1-ylmethyl)silane 100G
Chil(1-su7talenyl)(iH -1,!, 4-triazol-1-ylmethyl)cran 5O(3,
4-dichlorophenyl)dimethyl(IH-1,2,4-)riazol-1-ylmethyl)silane 80zomethy
(4-phenoxyphenyl) (x#-i*2e4-triazol-1-ylmethyl)silane io. Dimethyl(4-methoxyphenyl) (1#-1,2,4-triazol-1-ylmethyl)silane 100(2,
4-dichlorophenyl)dimethyl(lH-L I 214-triazol-1-ylmethy
) silane 100 bis(4-chloroph)
phenyl)(methyl)(1#-1,2,4-triazole-
1-ylmethyl)7 run 10G methyl
Zophenyl (1//-1,2,4-triazol-1-y
methyl) sila y io. (1,1'-biphenyl-4-yl)dimethyl(4H-
1,2*4-triazol-1-ylmethyl)silane 80-ilme
methyl)silane 5oCBV methyl(4-
methylthiophenyl) (1/f-1,1!, 4-・triazol-1-ylmethyl
601-ylmethyl)silane
Ran 80 (1!,4-dichlorophene
silane) methyl(l-ylmethyl)silane
100 l-ylmethyl)silane to. hmm
100n
80 Butyl (4-chloro
phenyl) (IH lumether) V methylsilane 15° methyl (lH-imidazol-l-ylmethyl) methylsilane 100 butyl
(4-fluoromethyl) (tH-imidazole-1-
ylmethyl) methylsilane 80 sq.
(lB-Idenmezol-1-ylmethyl)methylsilane 30bis(
i, i'-biphenyl-4-yl) (1/'/-imida
Sol-1-ylmethyl)methylsilane
50CIH-imidazol-1-ylmethyl
) [bis(4-methoxyphenyl)]methylcran 50 (1,
1'-biphenyl-2-yl)dimethyl (lH-imida
Sol-1-ylmethyl)silane 90(1,
1'-biphenyl-3-yl)dimethyl(x/f-imy
Dazolu-l-ylmethyl)silane
90(2-chlorophenyl)(IH-imidacyl-1-ylmethyl)methyl(phenyl)silane 100(4-butyl)silane
romophenyl) (1//-imidacyl-1-ylmethyl
) Methyl(phenyl)silane 30 silane
60 Silane riazol-1-ylmethyl] Silane υ (I
Orchid 50AG = raw
Length reduction BC,=whitening C compound was applied at a concentration of 400 pp groove. DB = Burn Example 7! Compounds of the invention were added to acetone with a key equal to 6 of the final volume.
then tsopp* surfactant THEM
Purified products containing O14 (ester of polyhydric alcohol)
Full13 was placed in water at an angle of LOOpptn. this
Suspend several corn seedlings until pressure drips.
Sprayed. The next day, pickles itsuden tou v:o:yshi(
go%thaws earn) leaf insect disease yAi11
I1mLts axis of m
Grafted with spore S suspension and cultured in a saturated humidity room at 20℃ for 24 hours.
1. Next, keep it in the growth chamber for another 7 days to prevent illness etc.
The class was decided. Disease suppression rate f is shown in F. processed
[#lJ#iIf the lesion is slightly or completely
Although it did not make a lot of noise, each untreated plant had a large number of 1/4 VC.
It was found in lesion '1. Phytotoxicity expressed as reduced growth
, some of the plants were detected in relation to the disease control.
. Table 5 (4-f romophenyl) dimethyl (1/-1,2,4-triazol-1-ylmethyl) 7 runs) 90 (
1,1'-biphenyl-4-yl)dimethyl(1#-1o2.4-)lyazol-1-ylme
Chill) Silane @0(s, 4-s//ro
lophenyl) dimethyl (1#-1,2,4-triazole
-1-ylmethyl)silane 90
Tsumethyl (4-methoxyphenyl) (ls -112@
4-)Reazol-1-ylmethyl)silane
90(2,4-dichlorophenyl)di
Methyl()H-i*R*4-)Reazol-1
-ylmethyl) 7rane 90bis
(4-chlorophenyl) (male) (1#-1m!-4
-) lyazol-1-ylmethyl)silane
80 methylphenyl (1#-16!, 4-)
azol-1-ylmethyl)7 run 80(1,1
'-Piphenyl-4-yl)dimethyl(4//-1,2
,4-)riazol-4-ylmethyl)silane
100 bis(4-furusuriphenyl)(methyl)
(177-1,1,4-triazol-1-ylmethyl)
Silane 100 dimethyl (4-ph)
fluorophenyl) (I M -1,2,4-triazole
-1-ylmethyl) 7 runs
90zomethyl(4-methylthiophenyl) (1#-1,11,4-)riazol-1-ylmethyl)
Silane 80tIlfk (1M-
1,1,4-)riasol-1-4-methyl)(4-tri
Fluo! (romethylphenyl)sila
50 (4-(1,1-1'methyl ether)
thyl)phenyl]dimethyl(1#-1,1,4-tria
sol-1-ylmethyl)silane 60(!-meth)
xyphenyl)dimethyl(l#-1,1,4-)lyazo
(ru-1-ylmethyl) 7 runs
70tutyl(1!,4-8/chlorophenyl)methyl
(1#-1,114-triazol-71-ylmethyl)
Silane 100C (1,4-8/chrome)
Tetraphenyl)(methyl)(sn-t * * I 4-
) lyazol-1-ylmethyl)silane
80(4-chlorophenyl)methyl(phenyl)(1
#-1-jl*4-triazol-1-ylmethyl〉Sila
90(4-fluorophenyl)methane
Chil(phenyl)(1#-1,f!,4-)reasol-
1-ylmethyl)silane 90(2-
lorophenyl) dimethyl (IB'-1-2@4”) rear
sol-1-ylmethyl)7ran
100 [4-(4-ri-tetralophenoxy)phenyl]
Zomethyl-(111-L, 2,4-triazol-1-y
(3,5-dichlorophene) 7ran 60 (3,5-dichlorophene)
dimethyl(1#-1,2,4-)lyazol-1-
ylmethyl) 7 runs 40(1
@1'-piphenyl-4-yl)butyl(methyl)-(
1#-1,2,4-triazol-1-ylmethyl)sila
50 (1@1/-biphenyl-4-yl
) Methyl(phenyl)-(1#-1,2,4-triazo
(l-1-ylmethyl) 7rane 90 [bis(4
-methoxyphenyl)]methyl (1//-1,2,4-
) lyazol-1-ylmethyl)silane
90(1,lξbiphenyl-!-yl)dimethy
(1#-1,1,4-triazol-1-ylmethyl)
Silane 9゜(1,1ξbiphenyl-
3-yl)dimethyl(1#-1,1,4-triazol-
1-ylmethyl)silane 1002-ri
Talophenyl (methyl) phenyl (17/-1, ffi
, 4-triazol-1-ylmethyl)silane
1004-Bromophenyl(methyl)phene
nyl(111-i l 2-4- ) lyazol-1-y
methyl)silane 8゜(r-methyl)silane
<*-chlorophenyl))/f-r(1 horn-1,2,
4-)Reazol-1-ylmethyl)silane
60cyclohexyl(dimethyl)(1#- 1,1!,4-)riazol-1-ylmethyl)silane
5゜(let'-'Feni
(4-yl)dimethyl(1)/-1,1! , 4-) Li
Azol-1-ylmethyl) 7rane, 4-dodecylbenze
sulfonate 10G (1,1
biphenyl-4-yl)dimethyl(1//-1,2,4
-) lyazol-1-ylmethyl)silane, di-steel chloride and
No l:1 hectic Zo. (1,1ξbiphenyl-4-yl)dimethyl (1#-1
,2,4-)riazol-1-ylmethyl)silay, chloride
1:1 complex with zinc (layer)
90(111'-biphenyl-4-yl)dimethyl(I
H-1*s+*4-) lyazol-1-ylmethyl)7
l:l complex with sulfuric acid and manganese
1002-chlorophenyl (4-chlorophenyl
) Methyl(1#-1,2,4-)riazol-1-yl
methyl)silane 60(141'-biphenylene)
dimethyl (IH-4-yl)
Methyl) 7 runs 90 buti
(4-chlorophenyl) (1//-iomesol-1-
ylmethyl) methyl 7rane
50 (sen-dichlorophenyl) (1
//-Iken mesol-1-ylmethyl) dimethyl 7rane
7゜(2@4
-8/chlorophenyl) dimethyl (IH-ii mesol)
l-ylmethyl) 7 runs
7゜bis(4-chlorophenyl) (1//
-Mesol-l-ylmethyl)methylsilane
　　　　　　　　　　　　　　　　　　　　　　　　　
6゜(lB-if mesol-1-ylmethyl)trif
phenylsilane 5゜diphenyl
(lH-imidacyl-1-ylmethyl)methylsilane
60 bis(4-fluorophenyl) (
1#-imidablue 1-ylmethyl)methyl 7ran
60C4-(
1,1'-Nmethylethyl)phenyl)(1#-imida
Nor-1-ylmethyl)dimethylsilane
70(lH-iomesolyl-l-ylmethyl)dime
Thyl(2-)lifluoromethylphenyl)silane
90 Butyl (2,4-dichloro
phenyl) (111-imidazol-1-ylmethyl)methyl72
80 bis (2,4-bis
lorophenyl) (IH-imidazol-1-ylmethyl)
Methylsilane 80 (
4-fluorophenyl)(1//-imidacyl-l-y)
methyl)methyl(phenyl)silane
8゜(2,6-zomethokitaphenyl)(E)
(17/-inmesol-1-ylmethyl)sila
5°VR chill <1i
t-Inmesol-1-(methyl)methylsilane
9゜(1,1'-N phenyl-4-yl
) (1) l-imidazol-l-ylmethyl)methyl
phenyl) 7 8゜(1,1'-bifu
phenyl-3-yl)ymethyl(lH-inmesol-1-
ylmethyl) 72° 9°
(bis(!-chlorophenyl)]□(lH-inmesol
-1-ylmethyl)methyl 7rane 90 silane 70 silane
80 Example 73 The compound of the present invention was added to acetone in an amount equal to 6 g of the final volume.
Then 250 ppm surfactant dissolved in THE
Purification containing MO14 (ester of polyhydric alcohol)
The suspension was suspended in water at a concentration of 1100 pp. These concerns
Spray the slurry onto the peanut seedlings until it drips.
The next day, the plants were cleaned of early spot pathogenic horns on peanuts.
C6τcos - 24 hours at 27°C in a room with normal humidity
Cultivate. It is then incubated for an additional 14 days in the growth chamber and the disease grade determined.
Decided. The results are shown in the table below.The treated plants did not suffer from spot disease.
Little or no, but still unpunished.
The plants had numerous spot diseases. expressed as a burn
Phytotoxicity has been shown in some of Danga in relation to disease control.
It was celebrated as a sacrifice. 1 Bis(4-chlorophenyl)(methyl)(t#-x*2
e4-)Reazol-1-ylmethyl)silane 10G methyl
Diphenyl(t#-to2*a-'triazol-1-ylmethyl)cran
10
0H,t'-biphenyl-4-yl)dimethyl(t#-t,!s4-triazol-1-ylmethyl)silane 100(4-
ri-prophenyl)dimethyl(1 #-1-2*4-)lyazo-1-ylmethyl)silane 90 dimethyl
(l-naphthalenyl)(IH-1,g,4-)reasol-1-ylmethyl)7ran 90(2,
4-dichlorophenyl)dimethyl (1#-1,2,4-
) lyazol-l-ylmethyl)silane
100 bis(4-fluorophenyl)(methyl)+
1H-1,! , 4-1-lyazol-1-ylmethyl)
Run io. Dimethyl (4-fluorophene-) (1#-1,2,
4-triazol-1-ylmethyl)cran
50(4-(1,1-8/methylethyl
) phenyl]dimethyl(1#-1,2,4-)reasol
-1-ylmethyl)silane 35 dimethyl(1
#-11! , 4-triazol-1-ylmethyl)(2-
1 trifluoromenalphenyl)-7 run 2
5B Butyl(2,4-1'chlorophenyl)methyl(1
#-1,2,4-)riazol-1-ylmethyl)silane
10G bis(2,4-t, P chlorophyll
phenyl) (methyl) (1#-1,1,4-)reasol
-1-ylmethyl)7 run 100 (2,
4-s/chlorophenyl)methyl(phenyl)-(1/
/-x,g,4-)riazol-1-ylmethyl)silane
100(4-40lophenyl)methyl(phenyl
il#-1,3,4-triazol-1-ylmethyl) 7 runs 100 (4-
fluorophenyl)methyl(phenyl) (1#-1, meaning
, 4-triazol-1-ylmethyl)7ran
10G(!-cudylophenyl)dimethyl(lH-1
,2,4-)riazol-1-ylmethyl)silane
30H,1'-biphenyl-
4-yl)butyl(methyl)-(1//-1,2,4-
) lyazol-1-ylmethyl)silane 100bis
(l B 1'-biphenyl-4-yl)(methyl)(
1)/-1,2,4-triazol-1-ylmethyl)
Ran 80 (1,1'-biphenyl-4-y
) Methyl(phenyl)-(1//-1,2,4-tri
Azol-1-ylmethyl)silane 100 [bis(4
-Methomethyl phenyl
lyazol-1-ylmethyl)silane
30(1,1'-biphenyl-2-yl)tumethyl(
1#-1,2,4-)riazol-1-ylmethyl)sila
100 (1,1'-biphenyl-3
-yl)dimethyl(1//-1,2,4-)reasol-
1-ylmethyl)7ran 902-k
Lorophenyl(/+ru)phenyl(1//-11!14
-) lyazol-1-ylmethyl)cran
No. 100-Bromophenyl(methyl)phenyl
(1#-1,214-triazol-1-ylmethyl)sil
La / 100 [bis(2-chloro
phenyl)]methyl (t#-t, 2.4-triazole-
1-ylmethyl) 7 runs 100 [
Bis(4-bromophenyl)]methyl (1#-1,2,
4-triazol-1-ylmethyl)silane
100(tex'-biphenyl-4-yl)di
Methyl (t/7-i, ge4-) lyazol-1-ylme
Chill) 7ran, 4-dodecylbenzenesulfonate
10G(tex'-biphenyl
-4-yl)dimethyl(L#-1,2,4-triazole
-1-ylmethyl) silane, 1:1 integration with KAKADAI-Hagane
100 (1,l 7 k.
dimethyl(l,#-t,2.4-yl)dimethyl(l,#-t,2.4-yl)
azol-1-ylmethyl) 7 run, with enriched zinc (zen)
l: l integrated 10G (ti
t'biphenyl-4-yl)dimethyl (1#-11!,
4-) lyazol-i-ylmethyl)7 run*m #! 4
-1:1 #1 body with manganese
10O1! -/Rolophenyl (4-/Rolophenyl)methane
Chil(1#-1,214-)riazol-1-ylmethyl
) 7 runs 9G [bis(2-fluorophenyl
)] Methyl (1#-L, S2.4-triazol-l-
ylmethyl) V run, l:l integral with chloride A-steel
10G [Bis(2-fluoro
phenyl)]methyl(x#-t,!,4-)reasol-
1-ylmethyl)silane, 2:1f with cupric chloride! i
m body 100 (1+1'
-biphenyl-4-yl)dimethyl(IH-imidazole
-1-ylmethyl)silane
100(2,4-dichlorophenyl)dimethyl(iB-
imidazol-1-ylmethyl)7ran
100 diphenyl (IB-imidazole
-1-ylmethyl)methylsilane 5
0bis(4-fluoro7enyl)(1#-imidablue
1-ylmethyl 1-methylsilane
100 dimethyl (4-fluorophenylate)
)(IR-imidazol-1-ylmethyl)silane
　　　　　　　　　　　　　　　　　　　　　　　　　
60 BA dimethyl (IB-imidazol-1-yl
methyl)-(4-)lifluoromethylphenyl)cyano
36B dimethyl (IH-i)
midacyl-1-ylmethyl)-(1-)lifluoromethyl
Luphenyl) 7 runs 50f
f−k<264-dichlorophenyl)(lB-imidazo
1-ylmethyl)methyl 7rane
LQQ bis(2,4-dichlorophenyl)(I
H-4i mesol-1-(lumether)methylsilane
g. (2,4-dichlorophenyl)(IH-imidazol-1
-ylmethyl)methyl(phenyl>Vran 100(4
-chlorophenyl><xtt-imidazol-1-ilme
methyl) methyl (phenyl) 7/
io. (4-fluorophenyl) (1//-iden meso A/-1
-4szlthyl)methyl(phenyl)sila5/
100 (spirit-chloropheny
(1H-idenmesol-1-ylmethyl)dimethyl 7
80(i*tL biphenyl-4-yl)bu
methyl(IH-2mesol-1-ylmethyl)methylsila
90 screws (tet' screws)
phenyl-4-yl) (lH-iden mesol-1-yl
methyl) methyl 7ran 60
(1@1'-biphenyl-4-yl) (IB-iden meso
1-ylmethyl)methyl(phenyl)cran
80 (l・1'-biphenyl-2-yl
) f/methyl(IH-imidazol-1-ylmethyl)k
Run 30 (lφlξbi
phenyl-3-yl)dimethyl(lH-imidablue 1
-ylmethyl)silane 8
0 (!-ri-a-rophenyl) (1#-is-mesol-1-i
methyl)methyl(phenyl) 7rane
io. (4-bromophenyl)(1#-imidazolyl-1-y
lumedel) methyl (phenyl) 7ran
90 [bis(2-chlorophenyl)](]
17/-Imimezo A/-1-ylmethylmethylsilane
Zo. [Bis(4-bromophenyl))1#-IZ mesol-1
-ylmethyl)methylsilane
5O(111'-biphenyl-4-y
) Dimethyl (lH-idenmesol-1-ylmethyl)
Orchid pot 1:1111114 1o with IKI copper chloride. (2-chlorophenyl)(4-chloro7methyl)methyl
Silane 8° Tris (4-fluoro
7A) (IB methyl)silane
9゜bis(4-ri-tetradiphenyl)hydroxy(4
B-1, 2! , 4-) lyazol-4-ylmethyl)
Ran 100 Oxybis [Bis(4-
Fluoro7(1-ylmethyl)silane
93B'4-triazol-1-ylmethyl)silane
100 (1*
1'-biphenyl-4-yl)hydrone
100
(1@1'-biphenyl-4-yl)(4-fluoro
7A)-methyl(IH-1t2t4-triazole
-1-ylmethyl)silane
10G dimethyl (4-trifluoromethoxyphenyl)
-(IB-1,2,4-)lyazol-1-ylmethyl
) Silane g. (4'-bromo1,1'-biphenyl-4-yl)di
Methyl-(lH-112, 4-triazol-1-yl
methyl)silane
1G(1(l,1-biphenyl-
4-yl)dimethyl(5-methyl-I H-1t 2
*4 “Triazol-1-ylmethyl)silane 1
GG(1,1'-biphenyl-4-yl)8/methyl(
IB-19214-) riazol-1-ylmethyl)
Ran, 111 complex with steel chloride
100(i11′-′phenyl-4-yl)dimethy
(IH-1@2*4-triazol-1-ylmethyl
) Silane, 211 complex with steel chloride
Zo. Bis(4-fluorophenyl)hydroxy(IB-IZ
mesol-1-ylmethyl)silane
50bis(4-ri-tetraphenyl)hydroxy
Shishiran 5゜zo
(1-ylmethyl)methylsilane (100 phenyl)
Silane 9゜L-1-ylmethylate
) Silane 90B' IIoptsm concentration
Compound AB was applied at a phytotoxic burn. B Compound 1f'14009ν was applied at the bait concentration. Example 74 A compound of the present invention was acetated with 6% Vc% of the final volume.
250 ppm surfactant TEE dissolved in
Purification containing MO14 (ester of polyhydric alcohol)
The suspension was suspended in water at a concentration of 80 ppm. This @turbid liquid
On the 6th day after spraying the bean seedlings until drippings,
Uromycma phaago, a fungus that causes rust on beans
Inoculated with Li spore suspension and kept at 20°C in a saturated humidity room.
The cells were incubated for 24 hours, then incubated in a greenhouse for 7 days, and then incubated in a greenhouse for 7 days.
The disease grade was then determined. Disease inhibitory groups are shown in the table below.
show. The treated plants will not get rusty warts or will have more rust.
In contrast, untreated plants have no rust disease.
It was covered with wood. 4* Nasal toxicity in the form of reduced growth
Some of the examiners' records have been observed in relation to diseased controls.
Ta. Table 7 (1,t'-biphenyl-4-yl(ymethyl(1#-
1,2,4-triazol-1-ylmethyl)7 run
io. (2,4-s/chlorophenyl)dimethylbis(4-k)
lorophenyl)(methyl)(1/7-1.2.4-)ly
azol-1-ylmethyl)72
100G(4-chlorophenyl)methyl(phenyl)(
t#-1,2,4-triazol-1-ylmethyl)sila
5sfl (4-fluorophenyl)
Methyl(phenyl)(l#-x*z,t-)reasol-
1-ylmethyl)silane 10(1bis(4
-fluorophenyl)(methyl](i#-toget-
) lyazol-1-ylmethyl)silane
98B(1・l'-biphenyl-4-yl)dime
Chil (l//-ifsol-1-ylmethyl) 7 runs
100[,4-/chlorophyll
(phenyl) dimethyl (lH-i-denmezol-1-ylmethyl) 7 runs
83AG=reduced growth
. B Compound WFiI@jl was applied at a conventional concentration. Example 7!1 Compounds of the invention were added to acetate with a key equal to Is% of the final moth volume.
KR and then TOOνpts surface activity 1fj
Contains TREM014 (ester of polyhydric alcohol)
100FW in purified water? lf's nematode made me sad
. Soak half of the canned peaches in this suspension for 3 minutes, then
The mixture was placed in a sterilized container and air-dried. dry and mourning
Then half of the peaches were treated with MoxiL, a traditional brown rot pathogen.
i舊IA fdehat+t4eela! 1 L island ioi piece
The cells were inoculated and cultured in an sterilized container for 6 days. That darkness,
The half-vkt of Ronnie's growth was measured for each stage. process
The pronye on the peach that has been exposed will not grow or the radius number t
Grows only 17 meters, but grows on untreated peach
The colony covered the whole area. sick
Inhibition i1+1 rate (compared to the growth of colonies on peach plants
(percentage inhibition of colony growth on treated peaches)
Shown in the table. ” (1 triazol-1-ylmethyl)plan 89 (2
) Nlfk<1#-1,2,4-triazole-1-
ylmethyl)silane 95(tet'-zephenyl-
4-yl)dimethyl(1#-1,2,4-)reasol-
1-ylmethyl)silane 1001 thyl
(4-chlorophenyl)methyl(s#-1,1,4-)riazol-1-ylmethyl)k
Ran @8 dimethyl (4-meth)
diphenyl<IH-1-2*4-triazol-1-yl
methyl) cran 97(2
, 4-1/chlorophenyl)dimethyl(1#-1,2,
4-triazol-1-ylmethyl)cran
100bis(4-ri-tetraphenyl)(methyl
) (1#-1,!64-triazol-1-ylmethyl)
72 no 954111'-Bife
nyl-4-yl)dimethyl(4#-x,,4-triazo
(4-ylmethyl) 7rane 96 bis(
4-fluorophenyl)(methyl)(1#-1,1,4
-) lyazol-1-ylmethyl)7 run
10@butyl (!e4-/chlorophenyl) meso
# (l II -1* 11 @ 4-triazole-
1-ylmethyl)7ran 98(4-
Chlorophenyl)methyl(phenyl)(1#-1,2,
4-)Reazol-1-ylmethyl)silane
Di0(4-fluorophenyl)methyl(7enyl
) (1#-1,2,4-triazol-1-ylmethyl)
Silane SO gtyl (4-fluorophe
lfk(1#-1,2,4-triazol-1-y)
methyl) clan Io. Tubutyl (methyl) (i#-t,g,4-tIj 7
Sol-1-ylmethyl)one9y l1l(i, i'
-biphenyl-4-yl)dimethyl(xH-imidazole
-1-ylmethyl)7 runs
83 Tutyl (4-chlorophenyl) (17/-iden)
Mesol-1-ylmethyl)methylcran
45 (lH-imidazole
-1-ylmethyl)dimethyl(4-phenok7enyl
) Silane 80
(t, 4-5) l lorophenyl pr, y mail (l
H-idenmesol-1-ylmethyl)silane
io. V-phenyl (1//-idenmethol-1-ylmethyl)methane
Circran 76 (4-chlorophenylene)
)(1/1'-imidazol-1-ylmethyl)methyl
(phenyl)silane 45
(4-fluorophenyl)(1#-imidazole-1-y
methyl)methyl(phenyl) 7rane
65v#, Example 76 Uninvented compound 1 of t-11 is equal to the final volume of 64bv
Dissolve VC in acetone and then add 250 ppm to the interface.
Sex-saving agent THEMo 14 (Ester of polyhydric alcohol
) at a concentration of 100pp to purified Kusuiko containing! cloudy
did. Spray this s droplet onto the rice seedlings until it drips.
-I did. The next day, the plants were washed with Rhig
Mixture of 1 thread of ootonia moLani and bran
41 species were cultivated in a growth chamber for τ times, and then the disease
I have decided on @. The disease O suppression rate is shown in the table below. process
The planted plant #'i had almost no leaf sheath disease, but this
It was covered with F1 leaf sheath disease.
. Table 9 L-ylmethyl)7 run 40(8,
4-dichlorophenyl)dimethyl(1//-1,2,4
-) lyazol-1-ylmethyl)silane
80 bis(4-fluorophenyl)(methyl)
(t # -1-2* 4-)
Chill) 7 runs 80 (4-(1,
1-dimethylethyl)phenyl]V methyl (1#-1,
1,4-)riazol-1-ylmethyl)silane
90 ts+-s/dichlorophenylmethyl(1
#-1,1,4-)ryanol-1-ylmethyl)silane
50(4-chlorophenyl)butyl
(phenyl)(1#-1,2,4-)lyazol-1-y
(4-fluoromethyl) 7rane 90 (4-fluoromethyl)
lophenyl)methyl(phenyl)C1jl-i n-1
,4-triazol-1-ylmethyl)silane
80 Butyl(methyl)phenyl(1//-t.2.4-)riazol-1-ylmethyl)silane
90 (lki′-bipheni
(4-yl)butyl(methyl)(1#-1,2,4-
) lyazol-1-ylmethyl) 7 runs 8゜b
thyl(4-fluorophenyl)methyl (t#-1ez,
+-)Reazol-1-ylmethyl)silane
80 bis(x,t'-biphenyl-4-y
)(methyl)(1#-1,2,4-)reasol-1-
ylmethyl)silane 90 [bis(4-meth)silane
xyphenyl)]methyl (1#-1,2,4-) lyazo
(l-1-ylmethyl) 7 runs 80
2-Rolophenyl(methyl)phenyl (1//-1
12,4-triazol-1-ylmethyl) 7 runs
904-Bromophenyl(methyl)phenyl
phenyl(1)/-1,2,4-triazol-1-yl
methyl)silane 90 [bis(2
-chlorophenyl)]methyl (1//-1,2,4-t)
lyazol-1-ylmethyl)silane
601t*t'-biphenyl-4-yl)$/Methi
(1//-1,214-)riazol-1-ylmethyl
) Silane, 1:11ffl with Koka Daiichi
90 (1・l'-piphenyl-4-
yl) dimethyl(17/-1,214-triazol-1
-ylmethyl) 7 run "-lat complex with chlorinated steel*
5O2-/iff
phenyl (4-chlorophenyl) methino... (five! no 1
*2-4-1'riazol-1-ylmethyl)silane
70 [bis(2-fluorophenyl)]#
-ol(1#-1@2.4-)reazol-1-ylmethyl
) Silane, 1:1 #jil with chlorinated steel
90 (1n-imidazole-1-i
dimethyl)dimethyl(4-)diphenyl)silane
70 screws (4-
Fluorophenyl) (17-fluorophenyl)
Chill) Menarsilane
90 (tH-ynitol mesol-1-ylmethyl) (
trimethyl (2-tricleolmerlefuer) 7u7
80 butyl (2,4-1/chloro
(l-imidablue 1-ylmethyl)
Methylsilane SObis
(2,4-dichlorophenyl)(IU-imidazol-1
--f-methyl)methylsilane
8G (4-fluorophenyl) (1#-
imidablue 1-ylmethyl)methyl(phenyl)7
90 (lH-iden meso
1-ylmethyl)(2-/)”?diphenyl)dime
chill 7 run
90 (4-(4-chloropheno
xy)phenyl]zomethyl(1#-1mi〆sol-l-i
methyl) 7 runs 70 punals (
IH-imimesol l-ilmenal
silane 80(tit'-biphenyl-
4-yl)butyl(IH-idenmesol-1-ylmethyA)
) Methylsilane 9
0-butyl (4-fluorophenyl) (1#-imidazole
-1-ylmethyl)methylsilane
80 (1ex'-biphenyl-2-yl)
Dimethyl(IH-it/sol-1-ylmesal)silane
9゜(”1.1ξbi
phenyl-3-yl)dimethyl(IH-imidazole)
-ylmethyl)silane 9
0 [bis(2-chlorophenyl)J(1#-imimesol
-1-ylmethyl)methylsilane
40 (t*1'-biphenyl-4-yl)
Dimethyl(17-imimesol-1-ylmethyl)sila
50 (2-chlorophene), 1:1 complex with quaternary steel
(I If-imidablue-1-ylmethyl)silane
90 bis(4-fluoro)
lophenyl) human tetraxy(if-iki mezo-ru 1-
ylmethyl)silane 90
(3-chlorophenyl)dimethyl CIB-ikenmezole
-1-ylmethyl)silane
90 (4'-pro
Mo1.1'-biphenyl-4-yl)dimethyl-CI
E-imidacyl-l-ylmethyl)silane
90(3,5-8/ria-rophenyl)dimethyl CI
B-Idenmezol-1-ylmethyl)silane
90 dimethyl (lH-imidazo
(1-ylmethyl)-octadecylsilane
100 (4-promo 1,1'-biphenyl-4-yl
) dimethyl-(IB-1,2,4-driazole-l-
ylmethyl) sila 7
90(1,1'-biphenyl-4-yl)dime
Chil(1#-1114-)lyazol-1-ylmethyl)silane, 211 complex with ferric chloride
80 methyl [bis(4-meth)
tylphenyl)] (I H-t t 214- ) rear
sol-1-ylmethyl)silane
30 Example 77 The compound of the present invention was treated with acetate with a filter equal to 6 of the final volume.
Then 260pp of surfactant THE
MO14 (ester of polyhydric alcohol) t-gold layer essence
It was suspended in the prepared water at a concentration of 100 pptn. Jinre et al.
A suspension of rice seedlings (VC) was sprayed until they dripped.
Pyie irises of blight disease 1aria orν 廖α-
Soak the moth larvae suspension in a room with saturated humidity at 1~8℃.
Stay! Incubate for 4 hours, then grow and store indoors for another 7 days.
After six years of fighting, I added an opportunity to the sick class. The disease suppression rate is shown in the table below. Treated m1ti lesions
have little or no
Processing FIIL111IFI Each collection can contain a large number of lesions.
Ta. Table 10 Dimethyl (1-su7talenyl) (1#-t-z e
4-) rifsol-1-ylmethyl)silane
10bis(4-chlorophenyl)
()? ) (l#-t, !, 4-) lyazol-1-i
methyl) 79n SO bis(4
-fluorophenyl)(methyl)(1//-t, g, 4
-) lyazol-1-ylmethyl)silane
100[4-(1φl-dimethylethyl
, u) tIlfk(I H-1,2,4-) Reazol
-1-ylmethyl)silane 1IO(4-/Rolo
Tzenyl)methyl(phenyl)(1#-1,2,4-t
lyazol-1-ylmethyl)silane 1
00butyl(methyl)phenyl(t#-i.2.4-)reasol-1-ylmethyl)7ran
static 0 (2-chlorophenyl)
Dimethyl (lH-1*1*4-triazol-1-ylme
Chill J shoes y 100 (t
it/-biphenyl-4-yl)butyl(methyl)(1
#-1,2,4-)riazol-1-ylmethyl)cran
100 butyl(4-fluorophenyl)methyl
(IH-1,1!, 4-triazol-1-ylmethyl)
7 run 100zo″butyl (methyl
) (1#-1,g,4-triazol-1-ylmethyl)
Cran 80 bis(1,11-biphenyl-4-y)
)(methyl)(1#-1,!64-)reasol-1-
ylmethyl) cran io. (1411-biphenyl-!-yl)dimethyl 4k
# -l* 2 * 4-triazol-1-ylmethyl
) Silane 908-chlorophenyl (
methyl)phenyl(1#-1,2,4-)reasol-1
-ylmethyl)7ran 1004-
Bromophenyl(methyl)phenyl (1#-1,t,4
-) lyazol-1-ylmethyl)cran
80 [bis(i!-riaa phenyl)]methyl
(1#-1-2,4-triazol-l-ylmethyl)
Ran 90 dimethyl (4-methyl
sulfonylphenyl) (1#-1, $1.4-) riazo
(l-1-ylmethyl)72n 10 [
Bis(4-10mophenyl)]methyl(1// ”'
L I 2@4- ) lyazol-1-ylmethyl)7
Tsun 5O(x, t'-biphenylene
(l-4-yl) dimethyl (1//-1@!, 4-)ria
sol-1-ylmethyl) 7ran, dodenrupenyansul
Hon imaginary 80 (111'
e)s-nyl-a-yl)N1thyl(1#-
1,1! , 4-) lyazol-1-ylmethyl)cran,
Chloride man - L with steel: 1 unity
ZoG(set'-biphenyl-4-yl)dimethyl (
1#-1,g14-)riazol-1-ylmethyl)sila
1:1 complex with zinc chloride (pongee)
to. [Cs(3-fluorophenyl)]methyl (17/-1
,1,4-triazol-1-ylmethyl)chloride
No. 6 tits with steel
SO[bis(!-Truo a722)]methyl(1#-
1,2,4-triazol-1-ylmethyl)7ran, salt
With Ka Daini Steel! ;1 complex
to. (IH-idenmesol-1-ylmethyl)dimethyl(4-
(phenoxytzenyl) silane
70[4-(1,1-t/methylethyl
phenyl] (IH-imidablue 1-ylmethyl)
Dimethylsilane 80 (4-fluoro
(lophenyl) (IH-ikenmesyl=1-ylmethyl)
Methyl(phenyl)silane
IQO(4-(4-/rolophenoxy)phenyl)zome
Chil(IH-idenmesol-1=ylmethyl)silane
100 butyl (lH-iden mesoru 1
-ylmethyl)methyl(phenyl)silane 9
0(1,1'-biphenyl-4-yl)butyl(1H-
Idenmezol-1-ylmethyl) methyl 7ran
Butyl (4-fluorophenyl)
) (1#-Izu mesol-1-ylmethyl) methylsilane
100 (1,
1-biphenyl-2-yl)dimethyl(lH-if/sol-1-ylmethyl)silane
s. H*l'-biphenyl-3-yl)dimethyl(IH-i
den mesol 1-, ylmethyl) cran
80 [bis(11-chlorophenyl)]
(1#-idenmezol-1-ylmethyl)methylsilane
90 dimethyl
CIH-Mesol-1-ylmethyl) (4-methyls)
sulfonylphenyl)silane
100 [bis(4-butamophenyl)3(tH-iden
Mesol-1-ylmethyl)methylsilane
80 bis(4-fluorophenyl
) H'roxy (IB-cymimesol-1-ylmethyl)
Silane 60 dimethyl (l
B-idenmezol-1-ylmethyl) (4-trifluoro)
Cemethoxyfluor) silane
90 (4'-fomomo-*l'-biphenyl-4-yl
) trimethyl-(iB-idenmezol-1-ylmethyl)
Silane 90 dimethyl (if-iden meso
-1-ylmethyl)-octadecylsilane
80 Oxybis[bis(4-fluorophenyl)(t
#-t*gw4-)lyazol-1-ylmethyl)sila
) 5O (4-promo 1.1-bifu
phenyl-4-yl)dimethyl-(IB-1,2,4-t)
lyazol-1-ylmethyl)silane
90(
l* i'-biphenyl-4-yl) 1-rich 1-complex with Tsume
100 Example 78 A compound of the present invention was added to acetone in an amount equal to 6 parts of the final volume.
1 then 26 Oppflk surfactant dissolved in TE
Essence containing EMO14 (ester of polyhydric alpour)
R was added to the prepared water at a concentration of 1009 jlfi. this
Sprinkle the suspension on the tomato seedlings until it drips.
Ta. The next day, the plants were infected with the pathogen of late-stage tomato blight.
Spores of Phytophtko de αtfLfaatasa
Inoculated as a suspension and incubated at 20°C for 24 hours in a room with saturated humidity.
The cells were cultured for an hour and then further cultured in a growth chamber for 7 days. The disease grade was then determined. The disease suppression rate is shown in the table below.
As shown, the treated Kyushu* has lesions as low as VL4 or r.
I don't have it at all, and for this fL * Other documents for processing are on each page.
There were many lesions on the upper part of the body. Table 11 Dimethyl(4-phenoxyphenyl) (x#-t,i,4-)reasol-1-bermethyl)7
Ran 50 (4-(4-chloro
phenoxy1 phenyl)S/methy#(1#-1,2,4
-) lyazol-1-ylmethyl)7ran 50
(t*t'-biphenyl-en-yl)dimethyl(1#-
1,1! Φ4-triazol-1-ylmethyl)silane
50 (111'-♂ phenyl-4-i
) trimethyl(1#-t*1e4-triazol-1-4
methyl) 7ran, 4-dobuclebenzene sulfonate
60 (1,1ξpiphenyl-4
-yl)dimethyl(lt)-1,2,4-triazole-
1-ylmethyl)silane, 1:lfi form with Kadai-ichi
Zo. (1,1ξbiphenyl-4-yl)dimethyl (x#-t
, gs4-)riazol-1-ylmethyl)7ran, chloride
1:1 complex with zinc(1)
9゜[bis(g-fluorophenyl)]methyl (1)
7-1.2.4-triazol-1-ylmethyl)silane
, 2:1i body with Kanka Souji Steel
4゜(4-noroheptaphenyl)(1//-4t meso
(1-ylmethyl)dimethylsilane 3°(1,1
'-biphenyl-4-yl)dimethyl(17/-imida
Sol-1-ylmethyl)7ran
SO(t it-imidazol-1-ylmethyl)
Dimethyl(4-phenoxyphenyl)silane
80 dimethyl (IB-
idenmesol-1-ylmethyl) (a −) +7 y
(ruo-tetramethylphenyl)silane
7゜silane
50 [bis(2-chlorophenyl)] (]IH-
Iken mesol-1-ylmethylmethylsilane
　　　　　　　　　　　　　　　　　　　　　　　　　
60 (4'-promo 1,1'-biphenyl-4-yl
) dimethyl-(1#-1,2,4-)lyazole-1-
ylmethyl)silane 30(1,1'-biphenyl
-4-yl)dimethyl(5-methyl-tB-t*2.t
-triazol-1-ylmethyl)silane 80
(1,1-biphenyl-4-yl)dimethyexample 7s The compound of the present invention was added to agar of standard strength Y-8 at 45°C.
The amended medium was then mixed at a concentration of 20 αOpν pigeons.
Distributed into bird dishes and allowed to solidify. Five types of Pkytophthora species Phytop
from an agar culture of hthora%1cottana-
Place approximately 4 Mayuzumi plugs (Cp1%Ly) on the medium.
, and cultured at 22°C for 6 days. The growth in the middle diameter direction is I.
Colonies with a code of W or higher will grow on unamended medium.
When the growth in the medium diameter direction is larger than IS, the colony
Comparatively, it was thought that the compound 'tlK was more inhibited. Main departure
phy-1 inhibited by certain compounds 'IIK
The number of y1μm seeds is listed in the table below. ! 5! 11! (Dityl) dimethyl (1#-1,2,4-triazole-
1-ylmethyl)silane 1(3*4-t/chlorophyll
phenyl)dimethyl(1#-1,214-triazol-1
-ylmethyl)7 run 2(1
,1'-biphenyl-4-yl)dimethyl(l)I-y
midazol-l-ylmethyl)cran
3(111-y(/sol-1-ylmethyl)
Dimethyl (4-phenoxyphenyl) 7 runs
4 (2,4-y chlorophyll
phenyl)dimethyl(lH-2mesol-l-ylmethyl
) Silane 5Jif
enyl<IM-imimyl-1-ylmethyl)methyl7
Ran 8 (4-fluorophenyl) (
1#-Cimimesol-1-ylmethyl)methyl(phenyl
) 7 runs! Example 80 A compound of the present invention was incorporated into an undisclosed blended proboscis and
f! to liquid seed the offspring at a ratio of lf/~Neko. Katsutomo,
After completely drying, the seeds were crushed at room temperature for 9 minutes. dim
So, Maki-no-ken-t, IM7'yt4+-ina virgin pigeon seeds
Most of the molecules: Dochu round pipe that has been corrected at the same rate as the VC of Rsu
My friend, I kept Ako at room temperature for 1 week. 4I on that 41! The grade of 4 ki was determined. Disease control rate
is shown to F. Most or all of the treated seeds
It germinated and produced a healthy seedling, but it died due to burrs.
The seeds either do not germinate or die and produce weak seedlings.
accomplished. Ethyldimethyl (t#-1m!!, 4-triazol-1
-ylmethyl)silane 48(1,1'-biphenylene
(17/-11!*4-)ria
Sol-1-ylmethyl)silane 12(
4-chloro7enyl)dimethyl(17/-1,2,4-
Triazol-1-ylmethyl) 7rane 53AV Methyl
(4-phenoxyphenyl) (17(-1,2,4-)ly!sol-1-ylmethyl
) Silane 18A (1,1'-'F
phenyl-4-yl)dimethyl(lH-cimimesol-1-
ylmethyl)silane 18
(4-chlorophenylil#-idenmesol-1-ylmethyl)dimetersicune 18A (3,
4-dichlorophenyl) (17/-4i mesol-1-
ylmethyl) dimethyl 7,
1! SAA αsr/Danko Saki's seeds 11 cups
Suppression fruit 1M9181 book@Akira's training vlJ is beautiful in unpublished handout, Tomo
Coat Rokoshi seeds at a ratio of tt/Kl1 seed 4 r
c () For K-d. Then steel pythists
espka-nadg fee le atsL, sand JP1 biko
In the mixed bamboo shoots of Corn f-le, most of the tree-treated seeds tfj are used.
V in sufficient proportion. 0 seeds in the amended soil were 497 (9.4℃)
tc! 1st place to hold the week? 0″F (21C) Ic Sara
The disease was then graded. disease
The suppression of Qi is shown to Shimo Ni. Most of the processed miko
All of them sprouted successfully and produced healthy seedlings, but compared to this
Untreated toothpicks may not germinate or may wither or wither.
Seedlings were produced. Table 14 Ethyldimethyl(1#-1,2,4-triazol-1-ylmethyl)silane 13(ll
l'-biphenyl-4-yl)dimethyl(177-1-
2*4-)Reazol-1-ylmethyl)silane
30(4-/lorophenyl)tumethyl(I

Claims (1)

[Claims] 1. In the formula, Ql and Q t id are independently H or CH,
nVil, R6 is C, Cl1l alkyl, C, -C, cycloalkyl, naphthyl or;
, c, -c, cycloalkyl, OR6
or, R4 and R3 are independently -H; halogen: OCHm;
OCF@: SCH, knee 80. C'H*: Phenyl: substituted with halogen and/or rac, -C4 alkyl and/or -CFs Saleta phenyl: phenyl: halogen and/or C, -C4 alkyl and/
Fhenogishi replaced with F3:-CF, :C
, -C, alkyl; or cyclohegycyl, R6 is H or C, -C4 argyl, with the proviso that R1
and R3 cannot both be FiOH, and R1 and R, together with t, 2-'d or 1,3- or 1,4-glycol bridges or have a total of up to 4 carbon atoms. Up to 4 alkyl groups R9-R,. Compounds, salts thereof, and battle complexes thereof, which are 1,4 uninitiated glycol bridges substituted with . 2, (1,1'-biphenyl-4-yl)dimethyl (l
H-1,2,4-trisol 1-i1,. 2. The compound according to claim 1, which is methyl)silane. 3. The compound according to claim 1 which is his(4-chlorophenyl 1 methyl C] 7 run. 4. [bis(4-fluorophenyl)] dimethyl IH-
The compound according to claim 1Jii, which is 1,2,4-)riazol-1-ylmethyl)silane. 5.4-Fluorophenyl(methyl)phenyl (IH-
1,2,4-triazol-1-ylmethyl)silane. 6. In the formula, Q+, Q, and Q, t- are independently H or CH,
, n is 1, R; is C, -CII alkyl, C, -C, cycloalkyl, naphthyl or, R1 and R3 are independently C, -CII alkyl, C -
C, cycloalkyl, OR, or, R4 and R3 are independently -H: halogen; -OCH,;
-0CFS; -8CHs; -80,CH,; phenyl: substituted with halogen and "t'+hc, -C4 alkyl and/or -CF, saletaphenyl: phenoxy; halo/r'7o and/or C, - Phenoxyni CFs substituted with C, alkyl and/or -CF, l: C+ c, alkyl; and R6 is H or C,-C4 alkyl, with the proviso that R,
and R, cannot both be OH, and R
, and R3 together with 1,2- or 1,3- or 1
．． Rw Rto R? can be a 4-glycol bridge or a 1,4-imminated glycol bridge substituted with up to 4 alkyl groups R7-R,n having a total of up to 4 carbon atoms. Compounds of RI6, their salts and Kintung complexes. 7. (2,4--)chlorophenyl)dimethyl rl
A compound according to claim 6 which is H-(migsol-1-ylmethyl)silane, 8. An effective amount of the compound according to any one of claims ml-7, a surfactant, and a solid. or at least one liquid inert diluent. 9. A method for suppressing fungal diseases, which comprises applying an effective amount of the compound according to any one of Items 1 to 5 to the area to be protected. 10. Effective Amount Formula Where Qs, Q, and Qsij are independent KH or CH,l, where n is 1, and RtsuC! C+ s 7 Le* Le, C@ Q @
cycloalkyl, naphthyl or R, and Rll are independently Cl Cs alkyl, Cl
1-C0/chloroalkyl, OR*1& is, R4 and R9 are independently -H; halogen; 0CHa:
0CFa; 8CHa-SO*CHm: phenyl; halogen and /i*uc, -C4 alkyl and/
saletaphenyl substituted with f or -CF; phenoxy; phenoxy substituted with halogen and/or C, -C4 alkyl and/or -CF; -CF, :C, -
C4 alkyl; or cyclohexyl, R6 is Hl or C,-C4 alkyl, with the proviso that R1
and R1's double sword cannot be OH, and R
, and R1 together are 1,2- or 1,3- or 1
, 4-glycol bridge or a 1,4-unsaturated glycol bridge substituted with a 4-alkyl group R1-R, having a total of up to 4 carbon atoms. consisting of applying it where it should be;
How to control fungal diseases. 11, where Q and Q are independently H or FiCH, n is 1, R8 is ctell alkyl, Cs-C6 cycloalkyl, naphthyl or R, and Rll are independently C, -C, alkyl, C3-
C, cycloalkyl, OR6 or, R4 and R11 are independently -H: halogen: 0CHa
: 0CF3 : 5CHs : 5oICHI
I; phenyl; halogen and U/4ft- are c+ C
phenyl substituted with 4 alkyl and/or -CF; phenoxy; , R, means C, -C4 alkyl, where R9
and R1 cannot both be OH, and R
, and R3 together with 1,2- or 1,3- or 1
,4-glycol bridge or a 1,4-unsaturated glycol bridge substituted with up to 4 argyl groups R1RI11 having a total of up to 4 carbon atoms. 'l,,5iC
Hyrl. 3. In a suitable solvent, the intermediate selected from R, MC in the formula M
is Na, Li) or MgX (wherein X is Br
, CI, j) to produce chloromethyl 7 run, and 2) react this chloromethylsilane with 1.2
．． ．． 4-triazole, its 3-methyl or 3,5-
dimethyl derivatives or their alkali metal salts in a polar aprotic solvent, ether or ketone at θ°C ~ 1
A method consisting of reacting at 50°C. CI ■ 12, 1) R, -8iCH11 and CI R. R,-S 1-CH,CI is reacted with RaoH in a suitable solvent in the presence of a suitable base to form an alkoxy-bridged dialkoxychloromethylsilane, and 21 this chloromethylsilane is 1,2,4-triazole, its 3-methyl or 3,5-dimethyl derivative, or its alkali gold Mtfi, in a polar aprotic solvent, ether or ketone at θ°C ~]50c. A method for producing a compound of formula (1) as described in section No. 1. 13, where Ql, Qt and Qll are independently H or CH, nll1t, Rr is Cs C111 alkyl, C, -C, cycloalkyl, naphthyl or, R1 and R8 are independently KC, -C, C111 alkyl,
cycloalkyl, ORs or, R4 and R6 are independently -H; halogen; 0CHa:
0CFs: SCH@: SOICHm:
Phenyl; halogen oj U / t k f'i C
Saletaphenyl substituted with +-C4 alkyl and/or -CF3; phenoxy: halogen and/or C, -
phenoxy substituted with C4 alkyl and/or -CF; -CF, ;C, -04 alkyl; or cyclohexyl, with the proviso that for compounds of formula ■ both R4 and R3 cannot be simultaneously KH and R. is H or C, -C, argyl, where R3
and R1 cannot both be OH, and R
, and R8 are together 1,2- or 1,3- or 1
, 4-glycol bridge or up to 4 alkyl groups R with a total of up to 4 element atoms? can be a 1,4 unsaturated glycol bridge substituted with Ran, R? In preparing the compound of RI6 . CI, 1) at -80°C to 40°C to produce chloromethyl/rane, and 2) react this chloromethylsilane with imidazole, its methyl, 2,4
-dimethyl, 4,5-dimethyl, and 2,4.5-to-11 methyl derivatives, or alkali gold ll7A thereof
A process consisting of reacting the salt with a polar aprotic solvent, an ether or a ketone at 0°C to 150°C. 14, 1) Reacting R, -8iCH2C1 and C1-S1-CHICI with R@OR in a suitable solvent in the presence of a suitable base to produce an alkoxy or dialkoxy7chloromethylsilane, And 2.1 This chloromethylsilane is imidazole, its methyl, 2,
4-Methyl, 4.5-methyl and 214.5-)1 methyl derivatives or alkali metal salts thereof are reacted with a polar aprotic solvent, ether or ketone at 0°C to 150°C. A method for producing a compound of the formula described.