DD271905A5 - METHOD FOR PRODUCING NEW THIENYL-AZOLYLMETHYL-SILANES - Google Patents

Abstract

A process for the preparation of novel Thienylazolyl-methylsilane of the general formula I, wherein X is a nitrogen atom or a CH group, Y is a hydrogen or halogen atom and R is a straight-chain or branched alkyl radical having 1 to 6 carbon atoms, an unsubstituted, on or repeatedly substituted by halogen phenyl or thienyl, a Biphenylyl- or naphthyl radical, which is carried out by reacting a substituted chloro-methyl-chloromethylsilane with a thiophene salt and the resulting compound with an alkali metal salt of imidazole or triazole react. By adding acid, the plant-physiologically acceptable acid addition salts can be prepared. The novel compounds and their acid addition salts are useful as fungicides. Formula I

Description

2 71 9 0S

Process for the preparation of novel thienyl-azolylmethyi-ailane Field of the invention

The invention relates to a process for the preparation of novel thienyl-azolylmethylsilane, which are useful as fungicides.

Characteristic of the known state of the art

U.S. Patent 3,697,798 discloses alkyl, alkylphenyl or phenyl-3-silylmethylimidazoles having antimycotic properties. US Pat. No. 4,510,136 describes alkyl-, alkylphenyl- or phenyleilylalkyltriazoles whose phenyl radicals can be frequently substituted with fungicidal properties. EP-A 148.026 discloses fungicidal silylmethylimidazoles and -triazoles which contain unsaturated alkyl groups. The construction principle of thienyl-azolylmethyl-3ilan compounds, however, is nowhere mentioned.

Object of the invention

Unexpectedly, thienyl-azolylmethyl-silanes have now been found which are distinguished by a strong fungicidal action. These connections are new.

The present invention therefore provides a process for the preparation of novel thienyl-azolylmethyl-silanes of the general formula I of the formula sheet in which X is a nitrogen atom or a CH group, Y is a hydrogen or halogen atom and R is a straight-chain or branched alkyl radical having 1 to 6 C atoms, an unsubstituted, mono- or polysubstituted by halogen phenyl or thienyl radical, a biphenylyl or naphthyl radical, which is characterized in that

a) a compound of the general formula II of the formula sheet,

in which R has the abovementioned meaning, with a compound of. general formula HI of the formula sheet in which Y has the abovementioned meaning and M is Li, Na or MgBr, allowed to react and

«U

b) the reaction product of general formula IV of the formula sheet formed with an alkali metal salt of iridazole or trlazole with elimination of the corresponding Alkalichloridä to oiner compound of general formula I.

The thienyl-azolylmethyl-silanes according to the invention have excellent fungicidal properties and thus represent an enrichment of the art.

In formula I, R represents a straight-chain or branched one; Alkyl radical having 1 to 6 carbon atoms, an unsubstituted or mono- or polysubstituted by Hslogen substituted phenyl or thienyl radical or a Biphenylyl- or Naphthylrest, wherein the biphenylyl and the halogen-substituted phenyl radical are preferred;

X represents a nitrogen atom or a CH group, preferably a nitrogen atom, and Y represents a hydrogen or halogen atom, preferably a hydrogen atom.

The thienyl radical may be bonded to the silicon in a 2- or 3-membered form, where it may optionally be substituted by halogen. Halogen is fluorine, chlorine or bromine. The thienyl radical in the 2-position is preferably bonded to the silicon.

The term alkyl, depending on the number of carbon atoms given, is understood to mean, for example, one of the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. and their isomers, such as, for example, isobutyl, tert , Butyl, sec. Butyl, isopentyl, etc.

Of the new compounds, acid addition salts can also be prepared. Suitable acid addition salts are all plant-physiologically acceptable salts of inorganic or organic acids, for example hydrochlorides, nitrates and oxalates. Likewise, the new compounds may be present as metal complexes.

Explanation of the essence of the invention

The starting compound of general formula H in which R represents a methyl group is a commercial product. If R is other radicals, these can be obtained by reaction of chloromethyl-dichloro-methylsilane, likewise a commercial product, according to D. Häbich, F.Effenberger, Synthesis, 1P79, 841-871 and C.Eabom, J.C. Jeffrey, J. former Soc. 4266 - 4268, 1954, wherein the resulting compounds of general formula H, without having to be isolated, can be used in reaction step a).

The conversion of the compound of general formula II of the formula sheet with a reactive thiophene of formula III is carried out, optionally without having isolated separately the compound of general formula II, in the presence of a solvent or diluent at low temperatures of about -80 to 0 ⁰ C. , Especially at temperatures from -75 to -60 ⁰ C. The compounds of general formula IV formed are partially new.

Suitable diluents are, for example, organic solvents such as pentane, hexane, benzene, toluene, xylene, diethyl ether, diisopropyl ether, Pet ^ oiether, tetrahydrofuran and combinations of these diluents, with diethyl ether and / or tetrahydrofuran are preferred.

To remove the resulting inorganic salt, the reaction product is worked up by conventional extraction methods, wherein about the reaction mixture is added to water and the organic phase extracted several times with water. The organic phase is dried and the solvent removed. The residue can be purified by distillation or column chromatography.

The reaction of the compounds of general formula IV with an alkali metal salt of imidazole or triazole is also usually carried out in the presence of a solvent or diluent at temperatures between about 0 to 200 ⁰ C, preferably between 20 and 100 ⁰ C. As a solvent or diluent are polar , organic solvents such. For example, methanol, ethanol, tetrahydrofuran, dimethylformamide or dimethyl sulfoxide, with dimethylformamide being particularly preferred.

The workup is carried out by conventional Exf.raktionsmethoden by about the reaction mixture oin organic, immiscible with water, solvent such. For example, ethyl acetate, dichloromethane, diethyl ether and water and the organic phase is washed with water. After removal of the solvent, the further purification of the organic phase can be carried out, for example, by column chromatography.

The preparation of the acid addition salts, which may optionally also constitute a purification step, can be carried out by dissolving the base of a compound of general formula I in a solvent such as acetone, ethyl acetate or diisopropyl ether and precipitating the acid addition salts by acid addition. The purification can be carried out expediently by recrystallization.

In all reactions, the starting material is usually employed in a stoichiometric ratio. An excess of one or the other may be quite advantageous in individual cases.

embodiments

Example 1;

(l _t l'-biphenyl-4-ylX2-thienyl) methyl (l, 2,4-triazol-l-ylmethyl,) silane

Preparation of the starting substances:

37.7 g bromobiphenyl (0.16 mol) were cooled in 400 ml of tetrahydrofuran at -75 ⁰ C. At this temperature, 100 ml of a 1.6 molar butyllithium solution in hexane (0.16 mol) was added dropwise. The resulting milky suspension of Biphenyüithium was added dropwise at -70 ⁰ C to a solution of 25.6 g dichloro-methylchloromethyl-silane (0.16 mol) in 100 ml of diethyl ether. The resulting reaction product (!, L'-biphenyl-A-yD-chloro-methyl-chloromethyl-silane was, without isolating it, used in reaction step a).

13.4 g of thiophene (0.16 mol) were added in 100 ml of diethyl ether at room temperature with 100 ml of a 1.6 molar butyllithium solution in hexane (0.16 mol) and heated to reflux for about 15 minutes. The suspension thus obtained was used as such in reaction step a).

a) (1,1'-biphenyl-4-ylX2-thienyl) methyl-chloromethyl-silane

The solution of (ljl'-BiphenyM-yOchlor-methyl-chloromethyl-silane, which was obtained by the above procedure, was cooled to -70 ⁰ C and dropwise added to the suspension of 2-ThienyHithiums obtained as described above. After the reaction had ended, the mixture was allowed to warm to room temperature and water was added, the organic phase was washed with water, dried and evaporated, and the residue was purified by column chromatography to give 22.5 g (43% of theory) of a colorless oil.

IH-NMR: 0.7 (s, 3H); 3.2 (s, 2H); 7.2 (m, lH); 7.3-7.4 (m, 4H), 7.5-7.7 (m, 7H).

b) (l, l ^{l-biphenyl-4-yl)} (2-thienyl) methyl (l, 2,4-triazol-l-ylmethyl) silane

271 9 0s

22.5 g (l, l ^l -biphenyl-4-> lx2-thienyl) meth>l-chlormet; -.-Yl 3ilan (0.07 mol) were dissolved in 100 ml of dimethylformamide, and 7.6 g of Natrlumsalzea of the triazole (0.083 mol) stirred for 3 days at room temperature. After completion of the reaction, 200 ml of water were added and extracted several times with ethyl acetate. The organic phase was washed with water, dried and evaporated. The residue was purified by column chromatography

 There was obtained 14.7 g (58% of theory) of a light yellow oil.

Example 2; (DimethylX2-thienyl) (l, 3-imidazol-l-yl) 3ilan

a) (dimethylX2-t-enyl) chloromethyl-3-silane

3.4 g of thiophene (0.04 mol) were refluxed in 100 ml of diethyl ether with 25 ml of a 1.6 molar butyllithium solution in hexane (0.04 mol). The reaction solution was then cooled to -70 ⁰ C and a solution of 5.6 g of chloromethyl-dimethyl-chlorosilane (0.04 mol) in 50 ml of diethyl ether was added dropwise. The mixture was then allowed to warm to room temperature, the organic phase extracted twice with water and dried over sodium sulfate. The solvent was inoculated abged and the residue subjected to vacuum distillation (b.p. 72-73 ⁰ C, 5 Torr)

 4.4 g of a colorless oil (58% of theory) were obtained.

b) (dimethylX2-thienylXl, 3-imidazol-1-yl) silane

2.2 g of dimethyl (2-thienyl) chloromethyl-sian (0.011 mol) were dissolved in 5 ml of dimethylformamide and stirred with 1.0 g (0.011 mol) of the Na salt of imidazole for 3 days at room temperature. Then water was added and extracted several times with ethyl acetate.

The organic phase was washed with water, dried over sodium sulfate and evaporated, the residue purified by column chromatography

 0.8 g (31% of theory) of a brown oil was obtained.

Using the above procedure, the compounds 3 to 18 listed in Table were prepared using appropriate starting materials.

The thienyl radical in compounds 3 to 15 is bonded in the 2-position to the silicon, in the compounds Id, 17 and 18 in the 3-position.

No.

salt

3 methyl N H Oil hydrochloride 4 methyl N H 5 M-thyl N 5-Chloro oil 6 n-butyl N H oil 7 phenyl N H oil hydrochloride 8th phenyl N H Nitrate ' 9 phenyl N H 10 4-fluorophenyl N H oil 11 Is 2,4-dichlorophenyl N H oil 12 3,5-dichlorophenyl N H oil 13 naphthyl N H oil 14 2-thienyl N H oil 15 5-chloro-2-thi3nyl N 5-Chloro oil nitrate 16 I, r-biphenyl-4-yl N H 17 4-fluorophenyl N H oil nitrate 18 4-fluorophenyl N H

Physical data of the new connections

Compound 1 0.8 (3.3H) /4.2 (s, 2H) /7.? - 7.6 (m, 1H) /7.7 (d, 1H, thiophene) / 7.8 (s, 1H); 7.9 (3, 1H) triazole

Compound 2 0.4 (s, 6H) / 3.8 (3.2H) /6.7 (s, 1H); 7.0 (s, 1H); 7.2 (s, 1H) imidazole / 7.2-7.3 (m, 2H); 7.6 (m, lH) thiophene

Compound 3 0.4 (s, 6H) /3.8 (s, 2H) /7.2 (m, 1H); 7.3 (d, 1H) j7.6 (d, 1H) thiophene / 7.8 (s, 1H); 7.9 (s, 1H) triazole

Compound 4 0.4 (3.6H) /4.2 (s, 2H) /7.1 (m _f lH); 7.25 (m, lH); 7.6 (m, lH) thiophene / 8.2 (s, lH) jlO.5 (s broad , IH) triazole

Compound 5 0.4 (s, 6H) /3.9 (s, 2H) /6.9 (d, 1H); 7.0 (d, 1H) thiophene / 7.8 (s, 1H); 7.9 (s, 1H) triazole

Compound 6 0.4 (3.3H) /0.8-0.9 (m _l 5H) /1.2-1.3 (m, 4H) /3.9 (d, 2H) /7.1-7.2 (m _> 2H); 7.6 (d, lH) thiophene /7.7(s,lH);7.8(s,lH) triazole

Compound 7 0.8 (S, 3H); 4.2 (s, 2H); 7.3-7.6 (m, 7H); 7.7 (d, lH); 7.8 (s, lH) 7.9 (s, lH) triazole

Compound 8 0.8 (s, 3H); 4.4 (s, 2H); 6.9-7.7 (m, 7H); 7.7 (d, lH); 8.3 (s, lH); 9.0 (s.lH); triazole

Compound 9 0.8 (s, 3H); 4.6 (m, 2H); 7.2 (m, lH); 7.3-7.4 (m, 4H); 7.5 (m, 2H); 7.6 (d, lH); (S, lH); 10.3 (s, lH) triazole

Compound 10 0.8 (3.3 ^ / 4.2 (3.241 / 7.0-7.1 (01.2 ^ 57.4-7.6 (01.2 ^ phenyl protons / 7.2-7.3 (m,) H); 7.3 (d, lH) 57.7 (i.e. , lH) thiophane / 7.8 (3, lH)} 7.9 (s, lH) tria ^ ol

Compound 11 0.8 ( ₃ , 3H), 4.3 (m,? H) /7.2-7.3 (m, 3H) /7.3 (2d, 2H) /7.7 (d, 1H) /7.8 (3,2H) 7riazole

Compound 12 0.8 (3,3H) /4.2 (s, 2H) /7.2-7.3 (m, 2H) /7.3 (m, lH) /7.4 (d _f lH) /7.45 (d, lH) /7.7 (d, lH) / 7.8 (s, lH); 7.9 (s, lH) triazole

Compound 13 0.8 (S, 3H); 4.2 (s, 2H); 7.1-8.0 (m, 12H)

Compound 14 0.8 (s, 3H) /4.2 (s, 2H) /7.2 (m, 2H); 7.4 (d, 2H); 7.7 (d, 2H) thiophene / 7.8 (s, 1H) j7.9 (3, 1H) triazole

Compound 15 0.8 (s, 3H) /4.2 (s, 2H) /7.0 (m, 2H) 57.1 (m, 2H) thiophene / 7.9 (d broad, 2H) triazole

Compound 16 0.8 (s, 3H); 4.6 (3, 2H); 7.3-7.4 (m, 4H); 7.4-7.6 (m, 6H); 7.9-8.0 (m, 2H); 8.4 (s, lH); 8.9 (s.lH); triazole

Compound 17 0.8 (s, 3H); 4.3 (d, 2H); 7.1-7.3 (m, 3H); 7.5-7.6 (m, 4H); 7.9 (m, lH); 8.0 (m, lH) triazole

Compound 18 mp. 141 - 150 ⁰ C

Example 19; wettable powder

20% active ingredient of compound 16

50% kaolin

20% Wessalon "SV"

10% Arkopon Tf *

The active ingredient was intimately mixed in a mixer with the additives and then ground through rollers and mills, whereby a wettable powder of excellent wettability was obtained, which can be diluted with water to give suspensions of any desired concentration.

Example 20: Emulsifiable concentrate

10% active ingredient of compound 1

25% 4-butyrolactone

55% xylene

10% Atlox 3335-B

From these concentrates, emulsions of any desired concentration can be prepared with water.

Example A In vitro tests

Cooled culture media were inoculated with an aqueous suspension of Hyphenteiien and / or Konidiosporen the respective test fungi. Filter plates (diameter: 5 mm) were soaked in aqueous 0.001% 0.2% dispersions of active ingredient formulations and placed on the inoculated nutrient media.

The minimum inhibitory concentration (MIC) was used for the assessment. That is the concentration of the active ingredient in the dispersion that completely inhibits the growth of the fungus.

As standards, A: propicinazole (1- (2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl) -1H-l, 2 _f 4-triazole) and B: thiabendazole ( 2- (4-thiazolyl) benzimidazole).

Results:

test fungus

Cercospora

beticola Cochliobolus

sativus phaeosphaeria

nodorum Vonturia inaequalis

fertile soil

Potato and carrot extract, agar biomalt and agar

Yeast extract, glucose and agar peptone, biomalt and agar

MHK (in ppm a.i.) Verbin was standing was standing Verbin 10 ard A ard B Training 1 10 5 50 100 25 50 10 5 10 2.5

Example B

Protective effect of the compound against powdery mildew (Erysiphe cichoracearum) on cucumbers

Ten day old cucumber plants were sprayed with an aqueous dilution of the formulated active ingredient.

After the spraying liquid had dried, the plants were inoculated with conidiospores of infested cucumber plants. The treated plants then remained in the greenhouse under given conditions

 14 days after the artificial infection, the infection with Erysiphe cichoracearum was evaluated.

For example, compounds 1 and 10 of an active substance concentration of 10 ppm were able to completely prevent the onset of the disease.

Example C

Protective effect of the compounds on cereal powdery mildew (Erysiphe graminia) on wheat and barley

Geraten- and wheat plants in the early 2-Blattstadlum were sprayed with an aqueous dilution of the formulated drug to drip point. After the spraying liquid had dried, the plants were inoculated with conidiospores of infested plants. The treated plants then remained in the greenhouse under given conditions.

8 to 10 days after the artificial infection, the infection was evaluated with Erysiphe graminis.

In this case, for example, the compounds 1 and 10 in a drug concentration of 10 to 30 ppm completely prevent the onset of the disease.

Example D

Protective effect of compounds against wheat brown rust (Puccinla recond'ta) on wheat

Wheat plants in the early 2-leaf stage were sprayed to drip point with an aqueous dilution of the formulated active toffee. After the spray liquid has dried, inoculation was carried out with uredospore obtained from infected plants. Subsequently, the test plants were incubated for 24 hours at 20 ⁰ C and about 95% humidity in a climate chamber. Until the complete onset of disease on the control plants, the test plants were under given conditions in the greenhouse.

In this test, for example, compounds 1 and 10 in a concentration of 50 ppm completely prevented the infestation of the test plants.

Example E

Protective effect of the compounds against oat crown rust (Puccinia coronata) on oats

Oat plants in the early 2-leaf stage were sprayed with an aqueous dilution of the formulated drug to drip wet. After the spraying liquid had dried on, the inoculation was carried out with uredospore obtained from infected plants. Subsequently, the test plants were incubated for 24 hours at 20 ⁰ C and about 95% humidity in a climate chamber

 Until the complete onset of disease on the control plants, the test plants were under given conditions in the greenhouse.

In this test, for example, compounds 1 and 10 in a concentration of 50 ppm sufficiently prevented the infestation of the plants.

Example F

Protective effect of the compounds against wheat leaf drought (Phaeosphaeria nodorum) on wheat

Wheat plants in the early 2-leaf stage were sprayed to drip point with an aqueous dilution of the formulated active ingredient. After the spray liquid has dried on, it was inoculated with an aqueous suspension of Pyknidiospores of Phaeosphaeria nodorum.

Subsequently, the test plants were incubated for 36 to 40 hours at 20 ⁰ C and about 95% humidity in a cold room.

Until the complete onset of disease on the control plants, the test plants were under given conditions in the greenhouse.

In this test, for example, compounds 1 and 10 at a concentration of 200 ppm prevented a. i. completely or in sufficient measure an infestation of the plants.

271 9 OS

Example G

Protective effect of the compounds against downy mildew (Plasmopara viticola) on wine

2 months old grape seedlings were sprayed to drip point with an aqueous dilution of the formulated drug. After the spray liquid had dried on, it was inoculated with an aqueous suspension of Sporanqiosporene Plasmopara viticola. Subsequently, the test plants were incubated for 24 hours at 20 ⁰ C and about 95% humidity in a climate chamber

 Until the complete onset of disease on the control plants, the test plants were under given conditions in the greenhouse.

In this test, for example, Compound 1 prevented a concentration of 200 ppm a. i. completely an infestation of the test plants.

317889-4

formula sheet

CH.

CH-

Cl -Si-CH ₂ Cl

Si

CH ₂ Cl

Claims (5)

claims 1. A process for preparing thienylazolylmethyl-silanes of the general formula I of the formula sheet 3 in which X is a nitrogen atom or a CH group, Y is a hydrogen atom or a halogen atom and R is a straight-chain or branched alkyl radical having 1 to 6 C atoms, an unsubstituted, one or more times halogen-substituted phenyl odor Thienylrest, a BiphenylyJ- or naphthyl radical, characterized in that a) a compound of general formula II of the formula sheet in which R has the meaning given above with a compound of general formula III of the formula sheet in which Y has the abovementioned meaning and M is Li, Na or MgBr, reacting and b) the formed reaction product of the general formula IV of the formula sheet with a sodium salt of imidazole or triazole with elimination of NaCl to a compound of general formula I um & etzt. 2. The method according to claim 1, characterized in that one converts the compounds of general formula I by adding an acid optionally in a solvent in the plant-physiologically acceptable acid addition salts. 3. The method according to claim 1, characterized in that one uses a compound of general formula II in which R is a l, l'-biphenyl-4-yl radical and the sodium salt of triazole. 4. The method according to claim 1, characterized in that a compound of the general formula II in the R is a 4-fluorophenyl radical and the sodium salt of triazole used. 5. The method according to claim 1, characterized ^ ^ that one prepares the compound of the general formula II of the formula sheet, in which R has the abovementioned meaning, d'mrch reaction of chloromethyl-dichloro-methylsilane with RLi or RMgBr and without isolating them in the reaction step a) is used. OZ 855 / DDR / V
05 1988