DE3303741A1 - Process for the preparation of heterocyclic compounds - Google Patents

Abstract

The invention relates to a process for the preparation of imidazole or 1,2,4-triazole derivatives of the formula <IMAGE> in which Y represents N or CH, and R1, R2 and R3 are as defined in the description. The compounds of the formula I have a biocidal action.

Description

Process for the production of heterocyclic

bonds The invention relates to a process for the preparation of heterocyclic compounds of the formula in Y is CH or N; R1 for phenyl; a phenyl radical substituted by 1 to 2 halogen atoms, the phenyl or nitro group; a C1-C10-alkyl radical, the carbon chain of which can also be interrupted by oxygen or sulfur; an alkenyl radical with up to 10 carbon atoms; a C1-C10-alkyl radical substituted by one or two phenyl radicals (which can optionally be substituted by halogen, methyl or nitro groups); or a possibly

C3-C7-cycloalkyl radical substituted by C1-C4-alkyl, C2-C4-alkenyl, benzyl or phenyl; R2 stands for hydrogen or C1-C4-alkyl or phenyl; R3 stands for C1-C4-alkyl, phenyl or benzyl or a phenyl radical substituted by a methylenedioxy group or a phenyl radical which is optionally mixed with halogen, nitro, trifluoromethyl, C1-C4-alkyl, C1-C8-alkoxy or a similarly benzyl radical substituted in the nucleus; NR2R3 also for a heterocyclic radical of the formula in which X 0, CH2 'CH-CH2C6H5 and R4 and R5, which can be identical or different, denote hydrogen or Cl-C4-alkyl.

The compounds of formula I can be used as racemates, in shape of the individual antipodal or diastereomeric pairs of antipodes, as free compounds or copper complexes are present.

The compounds of the formula I are new insofar as they do not correspond to the following formula Y: CH or N; R1: phenyl; a phenyl radical substituted by 1 to 2 halogen atoms, the phenyl or nitro group; a C1-C10-alkyl radical; an alkenyl radical with up to 10 carbon atoms; a C1-C10-alkyl radical substituted by one or two phenyl radicals (which can optionally be substituted by halogen or nitro groups); or a C3-C7-cycloalkyl radical optionally substituted by C1-C4-alkyl, C2-C4-alkenyl, benzyl or phenyl; R2 is hydrogen or C1-C4-alkyl; R3: C1-C4-alkyl, phenyl or a phenyl radical which is optionally mixed with one or three substituents by halogen, nitro, trifluoromethyl, C1-C4-alkyl or -alkoxy.

The aliphatic hydrocarbon groups can be straight-chain or be branched.

It has been found that the compounds of the formula I can, surprisingly, be obtained according to the following reaction scheme (R1, R2, R3 and Y have the meanings given above): The new process is therefore characterized in that carbonyldiimidazole or carbonylditriazole (III) is reacted with an aldehyde of the formula Iv and the compound of the formula V obtained is reacted with the amine of the formula VI, in which R2 and R3 have the above meaning .

The compounds of the formula I contain at least one center of asymmetry.

They can be converted into the enantiomers or, if appropriate, in the customary manner separated into diastereomeric pairs of antinodes.

The reaction of III with IV is expediently carried out in an inert solvent, e.g. toluene, benzene, acetonitrile, dioxane, tetrahydrofuran, methylene chloride, chloroform, or solvent mixture at temperatures between room temperature and the boiling point of the reaction mixture. Preferably a few minutes to several hours Heated to reflux. After the mixture has cooled down, generally at around 0-100C, the amine VI is added. The conversion to the end product takes place at temperatures between 0 and 100 ° C.

In the case of particularly easily reacting amine components, several hours are sufficient Stand at a low temperature, while in other cases it is advantageous to Shortening the reaction time to heat. Unless the reaction product is sufficient is sparingly soluble, the solvent can be distilled off and the residue through Recrystallize or, if appropriate, by column chromatography or other customary methods Cleaning methods are cleaned.

The compounds of the formula I can also be prepared by processes known per se be won.

1. Put a compound of the formula in which R1, R2 and R3 have the above meanings and Z stands for chlorine or bromine, with an imidazole or triazole salt of the formula wherein Me stands for an equivalent of a metal cation, in a dry organic solvent.

Acetone, acetonitrile, tetrahydrofuran, for example, can be used as solvents or serve toluene; acetonitrile is preferably used. The reaction temperature can be between about OOC and about 1200C. Because the reaction speed is strong Depending on the temperature, it is advisable to heat during the reaction. After the reactants have been brought together, the resulting organic separates Salt off. It is separated off after the reaction and the solvent is evaporated off. That remaining reaction product of the formula I is then if desired e.g. purified by recrystallization, distillation or column chromatography. Aldehyde present in the organic solution of the reaction product can be extracted by shaking with aqueous sodium bisulphite solution, acidic organic components can through Shake out with sodium bicarbonate before removing the organic solvent evaporates.

2. Put a compound of the formula (where R2, R3 and Y have the above meanings) in a dry organic solvent with an aldehyde of the formula R10CHO (1v), the reaction being catalyzed if desired by adding organic bases (such as pyridine, triethylamine) or mixtures of such bases.

Solvents such as toluene, benzene, acetone, acetonitrile, Tetrahydrofuran can be used; toluene is preferred. The reaction temperature lies between the ambient temperature and the boiling temperature of the reaction mixture, generally between 200C and 1500C. The implementation is expediently carried out at the Boiling temperature. The friction product obtained after the solvent has been distilled off is cleaned if desired as described in procedure 1.).

Solvent mixtures can also be used instead of individual solvents will.

Racemates can then, if desired, be converted into the optical antipodes be separated. Provided the compounds obtained have two asymmetric carbon atoms have, because of their different solubility, they can be converted into the diastereomers Antipode pairs are separated.

If desired, the compounds of the formula I are reacted with copper salt solutions in copper complexes (molar ratio azole / copper equal to 2: 1) convicted.

The starting materials are obtained by customary processes.

The compounds of formula I are suitable. e.g. as active ingredients in biocidal agents, especially in agents for controlling phytopathogenic fungi.

Mildew and rust fungi are particularly noteworthy.

In addition to the free active ingredients, complex compounds are also used for this application of compounds of the formula T with copper ions.

The new compounds respectively. their complex compounds in the usual way with auxiliaries and / or carriers processed into common forms of pesticides, e.g. into solutions, Solution or emulsion concentrates, suspension powders, dusts, emulsions.

If necessary, the concentrates are diluted with water before use, so that spray liquors with an active ingredient content between about 0.005 and 1 percent by weight can be obtained. When used as a low-volume or ultra-low-volume formulation the active ingredient content can also be considerably higher (up to 20 or 50 percent by weight). The application can be done by foliar or soil treatment.

Examples of formulations according to the invention: 1. Suspension powder 20 parts by weight of 1- {2, 2-Dimethvl-1- (2, 6-dimethylmorpholino-carbonyloxy ) -l-pentyl3 -1,2,4-triazole 20 parts by weight kaolin 5 parts by weight sodium sulfate 2 parts by weight Chalk 9 parts by weight of calcium lignosulfonate (dispersant) 1 part by weight Diisobutylnaphthalene sodium sulfonate (wetting agent) 43 parts by weight of silica chalk Die Ingredients are ground up and the agent is suitable for use in as much water suspended so that the active ingredient concentration is about 0.005 to 0.5 percent by weight.

2. Emulsion concentrate 15 parts by weight of 1- [2,2-dimethyl-1- (2,6-dimethylmorpholino-carbonyloxy-1-pentyl] -imidazole 10 parts by weight of dodecylbenzenesulfonic acid triethylamine salt and 75 parts by weight of dimethylformamide The strong action of the compounds according to the invention is evident from the following test results emerged.

The effect against powdery mildew on barley was investigated.

The evaluation was made with grades 1 - 3 (leaf effect).

It means: 1: Infestation 0 - 10% 2: Infestation 11 - 40% 3: Infestation 41 - 100% Example application evaluation concentration note Tab. I, No. 5 10 ppm 1 Tab. II, No. 1 20 ppm 1 Tab . II, No. 2 20 pps 1 Tab. III, No. 1 20 ppm 1 Tab. III, No. 2 20 ppm 1 Tab. IV, No. 1 20 ppa 1 The following examples are intended to explain the invention in more detail: Example 1 N- (4-chlorophenyl) -O- [1- (1-imidazolyl) -2,2-dimethyll-pentyl-carbamate 5.7 g of 2,2-dimethylpentanal are in 50 ml of abs. Dissolved toluene and added 8.1 g of N, N'-carbonyldiimidazole and heated the solution under reflux for half an hour. It is then cooled to 0 ° C. and a suspension of 6.4 g of 4-chloroaniline in 10 ml of toluene at the same temperature is added. After 14 hours, 1 g of a substance which melts at 315 ° C. is filtered off. After a further 48 hours at + 50 ° C., 11.0 g of the desired substance have precipitated in crystalline form (yield 66% of theory). After recrystallization from methanol / water 4: 1, colorless crystals with a melting point of 1760c are obtained.

Analysis: Ber. C 60.80% H 6.56% N 12.52% found C 60.87% H 6.42% N 12.53, 'Example 2 N- (4-chlorophenyl) -O- [1- (1 , 2,4-triazol-1-yl) -2,2-dimethyl-1-pentyl] carbamate 5.7 g of 2,2-dimethylpentanal are in 30 ml of abs. Dissolved toluene and added 8.2 g of N, N'-carbonylditriazole and heated this mixture under reflux for 30 minutes, then cooled to -5.degree. A suspension of 6.4 g of 4-chloroaniline in 20 ml of abs is added to this solution. Toluene added. After 4 hours at + 5 ° C., 1.2 g of triazole have precipitated and are filtered off.

The mixture is left to stand for a further 12 hours at room temperature and then heated for one hour at 50 ° C.

It is then extracted with water, and the toluene phase is dried (MgSO4) and the toluene is distilled off.

After adding a mixture of toluene and gasoline, the Residue crystalline.

Yield: 11.3 g (67% of theory); Mp 140-141 ° C.

Analysis: boron .: C 57.06% H 6.24% N 16.64, found: C 57.32% H 6.20% N 16.77, 'Example 3 1- [2,2-dimethyl- 1- (2,6-dimethyl-morpholino-carbonyloxy) -1-pentyl] -imidazole 5.7 g of dimethylpentanal are in 30 ml of abs. Dissolved toluene and added 8.1 g of carbonyldiimidazole, the mixture is refluxed for 30 minutes.

After cooling to -5 ° C., 5.75 g of 2,6-dimethylmorpholine are added in 20 ml Section. Toluene added. The mixture is 4 hours at + 50C and 15 hours at 200C ditched. The solvent is evaporated and the residue in toluene / acetone Dissolved 1: 4 and passed through a column filled with silica gel. The desired Fraction is identified by DC.

Rf value 0.46 (Merck prefabricated plates 60 F - 254, spraying with Dragendorffs reagent).

There are 11.3 g (68.5% of theory) of a slightly yellowish viscous get oeles.

Analysis: Calculated: C 63.16% H 8.98% N 13.00% Found: C 62.86, H 9.06 , N 12.94% The compounds of the tables below are obtained accordingly.

Table I compounds of the formula Example YR Fp (0c1 L VJ 1 CH <C1 155-136 cl 2 CH C1 171 1 3 CH {> 3 135-136 4 CH mw 145-146 CF3 5 CH <98 C. 6 cH MwoH3 146-147 7 CH C6H5 149-150 8 N C6H5 125-126 9 N MM) \ cH3 138-139 Example YR Fp (0c] LV 10 N ~ Br 152-153 11 N yÄ C1 158-159 C1 12 N oC2H5 137-138 13 CH to Br 175-176 14 CH t 127-128 15 CH n -C4H9 61-62 16 CH <On-C6H13 17 N 4¼. 0-CH2CH (CH3) 2 18 CH 0-C (CH3) 3 19 N <0-n-C8H17 20 N <° -C6H13 21 N 4 CH3 138-139 22 2J.Br 152-153 Example YR 23 CH tovCH (CH3) 2 168 24 N 9 CH) 130 25 N <CF3 165-166 26 CH ~ 9 2H5 156-157 27 CH M3 165 28 N + 105 29 N 113-114 1 30 N to1 116-118 31 CH ½; 0CH3 177 32 CH); OH3CH3 160-161 v ; 5H 33 N O 114 34 N -CH2-C6H5 oil 35 CH -CH2-C6H5 92 Table II Compounds of Formula Example YX R4 R5 Rf value * 1 CH 0 HH 0.43 (toluene / acetone 2: 8) 2 CH CH HH 0.45 (toluene / acetone 2: 8) * Determination of the Rf values: Merck prefabricated plates, silica gel 60 F - 254; Spraying with Dragendorff's reagent.

Table III Compounds of Formula Example y Rf value solvent Example Y NR e5 mix rru 1 N - N 0 0.47 0 toluene / (M.p. 1120C) acetone 8: 2 3 CH3 Yes 2 CH -N 0 0.37 toluene / ¼ acetone 7: 3 CH3 CH3 3 N -N (cH 0.58 toluene / CH32 acetone 7: 3 CH 3 2 4 CH -N (CH 0.46 toluene / Acetone 7: 3 CH32 5 CH -N (nC) 0.52 toluene / (M.p. 870C) acetone 9/1 ¼C6Hs 6 N -N C6H5 0.60 0 toluene / \ CH3 (m.p. 159 C) acetone 7: 3 3 Example Y NR 2R3 Rf value * solution middle- mixture 7 CH C6H5 0.381080C) -NCgH, N¼cH3 (mp toluene / 3 9 valley 8 N -N (CH3) CH (CH) C2H5 O (1030C acetoin 9: 1 9 CH -NtCH3) -CH (CH3) C2H5 0 (01O70C) toluene / 9: 1 10 N -N (CH3) -n-C4H9 0.68 toluene / acetone 7: 3 11 CH -N (CH) -n-CH, 0.47 O) toluene / (M.p. 85 c) acetone 7: 3 12 N -N (CH3) -nC O56116o toluene / <Mp c) acetone 7: 3 13 CH -N (CH3) -nC 0.40 toluene / to 1270c) acetone 7: 3 14 CH-NH-n-C4Hg m.p. 114 ° C 15 N -NH-n-C4Hg m.p. 1030C * Macherey-Nagel Polygram SIL G / W 254 precast plates sprayed with Dragendorff's reagent, Table IV, compounds of the formula At solution play Y Rw NR2R3 Rf value * mix L / mix 1 CH C6H5 -N 0 0.43 toluene / \ H acetone 1: 1 CH3 3 2 CH C6H5 -N (CH kC6Hs 0.36 toluene / Acetone 7: 3 3 N C6H5 N (C6H5) 2 0.67 toluene / Acetone 7: 3 4 CH C6H U -N (c6H5) 2 0.42 tolutene / 5 CH4-C1-C6H5 -N (CH3) 2 0.30 acetone (Fp 161ort 6 N C6H5 -N (CH3) 2 0.34 toluene / acetone (Fp 140 C) 7 CH C 6 H 5 U -N (CH 3) 2 mp 1540C 8 CH4-CH3-C6H4-N (CH3) 2 mp 1480C 9 CH 2,4-C12-C6H3 -N (CH) 2 0,33 toluene / 23 32 acetone 3: 7 10 N 2,4-C12-C6H3 -N (CH3) 2 0,37 toluene / Acetone 7: 3 * Macherey-Nagel Polygram SIL G / tJV 254 prefabricated panels; Spraying with Dragendorff's reagent. Solution At- YR "NR3R3 Rf value * medium- game or F. mix 11 N n -C 4 Hg -NH 4 -C 1 m.p. 115 ° C 12 N n-C4 - NH - (- OCH3 mp 84-85 & 13 CH n -C 4 H 9 -NH OCH 3 m.p. 105-106 ° C Prefabricated panels Macherey-Nagel Polygram SIL G / UV 254; Spraying with Draqendorff's Reaqenz.

Table V Compounds of Formula At- Y R1 MR R 3 Fp [0c) game 1 CH4-C1-C6H4-N (CH3) 2 99 2 N4-C1-C6H4 -N (CH3) 2 139 3 NC (CH3) 3 o OC2H5 140-141 4 NC (CH3) 3 -NH 9 1 154-155 5 CH C (CH) 3 -NH to C1 158 6 CH C (CH3) 3 1 -NH o OC2H5 162-163 7 NC (CH3)) '-NH 4 0> 168 J- 2 8 NC (CH3) 3 1); cl 131 9 NC (CH3) 3; -NH 123 H3 10 NC (CH3) 3 N (CH3) C6H5 δ1 At- game y R1 NR2R3 Fp [c) 11 N -C (CH3) 2 -NH - (o) C1 146-147 CH2-SCH3 12 * N -C (CH3) 2 -NH - (03- C1 164 CH (CH3) -0C2H5 13 * N -C (CH3) 2 -NH-C1 153 cH (CH3) -oc2H5 14 ** CH -C (CH3) 2 NHQCl 153 CH (CH3) -OC2H5 NNC (CH3) 3 -N-CH2C6H5 101 16 NC (CH3) 3 -NH 4 148 17 N c (cH3) 3 -NM-F 128-129 18 NC (CH3) 3 -NHO) -cl 197 19 NC (CH3) 3 -NH <C1 105-106. F. * 12 and 13 are each one of the diastereomeric antipodal pairs.

** Mixture of the diastereomeric pairs of antipodes

Claims (11)

Claims 1. Compounds of the formula in which Y is CH or N; R1 for phenyl; a phenyl radical substituted by 1 to 2 halogen atoms, the phenyl or nitro group; a C1-C10-alkyl radical, the carbon chain of which can also be interrupted by oxygen or sulfur; an alkenyl radical with up to 10 carbon atoms; a Cl-ClO-alkyl radical substituted by one or two phenyl radicals (which may optionally be substituted by halogen, methyl or nitro groups); or a C3-C7-cycloalkyl radical optionally substituted by C1-C4-alkyl, C2-C4-alkenyl, benzyl or phenyl; R2 represents hydrogen or C1-C4-alkyl or phenyl; R3 stands for C1-C4-alkyl phenyl or benzyl or a phenyl radical substituted by a methylenedioxy group or a phenyl radical which is optionally mixedly substituted by halogen, nitro, trifluoromethyl, C1-C4Alkyl, Cl-C8-alkoxy or a phenyl radical which is also substituted in the nucleus Benzyl radical; NR2R3 also stands for a heterocyclic radical of the formula where X 0, CH2, CH-CH2C6H5 unH L4 and R5, which can be the same or different, denote hydrogen or C1-C4-alkyl, as racemates, as individual enantiomers or optionally diastereomeric pairs of antipodes, as free compounds or as copper complexes. 2. Compounds of the formula I in which the group NR3R is the remainder of the formula where X is 0, CH2 or CH-CH2C6H5, R4 and R5, which can be identical or different, are hydrogen or C1-C4-alkyl. 3. Pest control agents, characterized by a content on a compound according to claim 1 or 2. 4. Use of compounds according to claim 1 or 2 in pest control. 5. Use of compounds according to Claim 1 or 2 in combating phytopathogenic fungi. 6. Process for the preparation of compounds of the formula in which Y is CH or N; R1 for phenyl; a phenyl radical substituted by 1 to 2 halogen atoms, the phenyl or nitro group; a C1-C10-alkyl radical, the carbon chain of which can also be interrupted by oxygen or sulfur; an alkenyl radical with up to 10 carbon atoms; a C1-C10-alkyl radical substituted by one or two phenyl radicals (which can optionally be substituted by halogen, methyl or nitro groups); or a C3-C7-cycloalkyl radical optionally substituted by C1-C4-alkyl, C2-C4-alkenyl, benzyl or phenyl; R2 stands for hydrogen or C1-C4-alkyl or phenyl; R3 stands for C1-C4-alkyl, phenyl or benzyl or a phenyl radical substituted by a methylenedioxy group or a phenyl radical which is optionally mixed with halogen, nitro, trifluoromethyl, C1-C4-alkyl, C1-C8-alkoxy or a similarly benzyl radical substituted in the nucleus; NR2R3 also stands for a heterocyclic radical of the formula wherein X o, C2 or CH-CH2C6H5 and R4 and R5, which can be the same or different, denote hydrogen or C1-C4-alkyl, as racemates, as individual enantiomers or diastereomeric pairs of antipodes, as free compounds or as copper complexes, characterized in that one carbonyldiimidazole or carbonylditriazole of the formula in which Y has the above meaning, with an aldehyde of the formula R1CHO (IV), in which R1 has the above meaning, to give a compound of the formula converts and this compound with an amine of the formula where R2 and R3 have the above meaning, cause them to react and, if desired (according to their structure), separate the products obtained into the enantiomers or diastereomeric pairs of antipodes and / or convert them into copper complexes. 7. Compounds of the formula I, with the exception of the compounds of the formula A in which Y is CH or N; R1 phenyl; a phenyl radical substituted by 1 to 2 halogen atoms, the phenyl or nitro group; a C1-C10-alkyl radical; an alkenyl radical with up to 10 carbon atoms; a C1-C10-alkyl radical substituted by one or two phenyl radicals (which can optionally be substituted by halogen or nitro groups); or a C3-C7-cycloalkyl radical which is optionally substituted by C1-C4-alkyl, C2-C4-alkenyl, benzyl or phenyl; R2 is hydrogen or C1-C4-alkyl; C1-C4-alkyl, phenyl or a phenyl radical which is optionally mixed substituted by halogen, nitro, trifluoromethyl, C1-C4-alkyl or -alkoxy. 8. Compounds of the formula I in which R2 is phenyl and R1, R3 and Y have the above meaning. 9. Compounds of the formula I in which R1 is one by oxygen or Means sulfur-interrupted alkyl radical with up to 10 carbon atoms. 10. Compounds of the formula I in which R3 is one through a methylenedioxy group substituted phenyl radical or an optionally one to three times in the core Halogen, nitro, trifluoromethyl, C1-C4-alkyl, C1-C8-alkoxy (mixed if necessary) or benzyl radical substituted in the nucleus by methylenedioxy. 11. Process for the preparation of nice compounds of the formula I, in which the radicals are as defined above, characterized in that a) a compound of the formula wherein Z is chlorine or bromine, with an imidazole or triazole salt of the formula wherein Me is an equivalent of a cation or b) a connection of the formula with an aldehyde of the formula R1 - CHO (IV).