DE2220102A1 - N-acyl-carboxylic acid imino ethers - plant protection agents - Google Patents

Abstract

Title cpds of formula R1R2CH-C(OR)=N-(CO)n-A' (I) (where R is haloalkyl or an opt. subst. aromatic residue which can also be linked with heterocyclic residues or contain bridge members; R1 and R2 are unsatd; electron withdrawing, residues, and can also be joined to form a 5- or 6-membered ring; n is 1 or 2; and A' is R3, OR3 or CHR1R2, R3 being an opt. subst. aliphatic, aromatic, or heterocyclic residue), are prepd by reacting cpds: Hal-C(OR)=N-(CO)nA (where Hal is halogen and A is -(O)R3 or halogen) with CH-acidic cpds. R1-C2H-R2 at -50 degrees to 120 degrees C in the presence of base.

Description

New N-acylcarboxylic acid imino ethers The invention relates to new ones N-acylcarboxylic acid iminoethers and a process for their preparation.

It has been found that new N-acyl-imino ethers are obtained if compounds of the general formula are used in which R stands for a haloalkyl radical or an optionally substituted aromatic radical, which can also be connected to heterocyclic radicals or contain bridge members, Hal stands for halogen, A stands for R3, Ohr3 and Hal and n stands for 1 or 2, where R3 is an optionally substituted one aliphatic, cycloaliphatic, aromatic or heterocyclic radical means, with CH-acidic compounds of the general formula R¹ -CH2 -R² (II) where R1 and R2 are unsaturated, electron-withdrawing groups and where R1 and R2 are optionally also part of a five- or six-membered ring system can be, at temperatures between -50 and 1200C, preferably in the presence of a base, in a molar ratio of halogen atom to CH-acidic compound 1: # 1. You can work in a diluent. It is preferred to work at -20 to 500C.

Examples of unsaturated, electron-withdrawing radicals are named: -CN, -CHO, -Co-R4, -CooR4, -CO-NH2, -CONHR4, -CON (R4) 2, -SOR4, SO2R4, in which R4 is an optionally substituted aliphatic radical (with up to 20, preferably 6 carbon atoms) or an optionally substituted aromatic (preferably Phenyl) should mean radical. The following are preferably mentioned as substituents on the radical R4: Alkyl (C1-6), aryl (phenyl, naphthyl), halogen (fluorine, chlorine, bromine), nitro, alkoxy (C.1-4), aroxy (phenoxy, naphthoxy), alkyl mercapto (C1 4), aryl mercapto (phenyl, Naphthyl mercapto), dialkylamino (each C1-4), cyano.

The new compounds have the general formula in which R, R1, R2 and n have the meanings given above and A 'stands for R3, OR3 and CHR¹ R² and R1, R2, R3 have the meanings given above for these radicals.

The implementation is explained using the following equations as an example: + NC-CH2-CN + base n NC-CH-CN 2) 0 + 2Base tS -Oc = Nc-cl + 2 NC-CH2 HClt Cl- = 9 ~~~~~~~~~ Ü'Ä-C = N-6-CH (CN) 2 NC-CH-CN Haloalkyl radicals R are, for example, aliphatic hydrocarbon radicals with up to 12 carbon atoms, which preferably have chlorine, bromine, fluorine or iodine atoms in the β-position.

Aromatic hydrocarbon radicals come as aromatic radicals R with up to 20 carbon atoms in the ring system (preferably phenyl, naphthyl) into consideration. The aromatic radicals R and R1 can also be substituted and as For example, carry substituents: Alkyl with preferably 1 to 18 carbon atoms, aryl (preferably phenyl, naphthyl), alkylamino (preferably C1.6 Dialkylamino (preferably C1-6), acylamino (preferably C16, benzyol), nitro, Halogen alkoxy (preferably C1 6) aroxy (preferably phenoxy and naphthoxy), Acyloxy (C1,6, benzoyl), carbonyl, carbon esters (preferably alkyl C1-12 and phenyl), Carbonamide, sulfonyl, sulfonic esters (preferably alkyl C1-6 and phenyl), sulfonamide, Acyl (preferably C112 alkyl and benzoyl), cyano, rhodanide, alkyl mercapto (preferably C1, 6) aryl mercapto (preferably phenyl) or acyl mercapto (preferably alkyl C16 and phenyl) groups. Furthermore, the aromatic radicals R can be 5- or 6-membered Ring system, which can also contain heteroatoms such as N, 0 or S, be connected.

The heterocyclic radicals R and R1 are preferably 5-, 6- or 7-membered ring systems with one or more heteroatoms white 0, N or 5 im Ring system into consideration.

If R and R1 together stand for a ring system that also contains further heteroatoms may contain, so is in particular 5-, 6- or 7-ring systems such as piperidine, Morpholine, pyrrolidine, decahydroquinoline, tetrahydroisoquinoline, dodecahydrocarbazole, Benztriazole, imidazole or even hexamethyleneimine thought.

Aliphatic radicals R³ are preferably straight-chain or branched, saturated or unsaturated hydrocarbon radicals with up to 25 carbon atoms, which can contain up to 2 double or one triple bond, and cycloaliphatic Radicals with 5, 6, 7, 8, 10 or 12 carbon atoms in the ring system, which can optionally also be substituted by, for example, aryl (bis to C20 in the ring system), aroxym (up to C10 in the ring system), alkoxy (C1-C6), nitro, Halogen (fluorine, chlorine, bromine, iodine), acyl (C1-C6, phenyl), alkylmercapto (C1-C6), Aryl mercapto (phenyl), cyano, rhodano, carbon ester (C1-C12, aryl to C20 in the ring system), Carbonamide 'dialkylamino (C1-C8) or acylamino (C1-6' phenyl) radicals.

The aromatic radicals R3 can have the same meaning for have the abovementioned radicals R indicated.

The heterocyclic radicals R3 are preferably 5-, 6- or 7-membered ones Ring systems with one or more heteroatoms such as 0, N or S in the ring system into consideration.

The starting compounds used for the process according to the invention of the formula I are known (see Angewandte Chemie 81, 623 (1969)) and from cyanic acid esters and phosgene or carboxylic acid halides or carbonic acid ester halides or oxalic acid halide derivatives manufacturable.

For example, the following cyanic acid esters can be used for this purpose: Phenyl cyanate, mono- and polyalkylphenyl cyanates such as 3-methyl-, 4-isododecyl-, 4-cyclohexyl-, 2-tert-butyl-, 3-trifluoromethyl-, 2,4-dimethyl- 3, 5-dimethyl-, 2,6-diethyl-, 4-allyl-2-methoxyphenylcyanate; Arylphenyl cyanates such as cyanatodiphenyl; Dialkylaminophenylcyanates such as 4-dimethylamino, 4-dimethylamino-3-methylphenyl cyanate; Acylaminophenyl cyanates how Acetylaminophenyl cyanate; Nitrophenyl cyanates such as 4-nitro-, 3-nitro-, 4-nitro-3-methyl, 3-nitro-6-methyl-phenylcyanate; Halophenyl cyanates such as 2-chloro, 3-chloro, 4-chloro, 2,4-dichloro, 2,6-dichloro, 5-bromo, 4-fluoro, 4-iodo, 2-chloro-6-methyl-phenyl cyanate; Cyanatopehylcarbonsäure-, -esters, -amides such as 2-cyanatobenzoic acid ethyl ester, 2-cyanatobenzoic acid morpholide and diethylamide; Cyanatophenylsulfonic acid, esters and amides such as ethyl 4-cyanatobenzenesulfonate; Alkoxyphenyl cyanates such as 2-methoxy, 3-methoxy, 4-isopropoxyphenyl cyanate; Phenoxyphenyl cyanate such as 4-cyanatodiphenyl ether; Acyloxyphenyl cyanates such as 3-acetoxyphenyl cyanate; Acyl phenyl cyanates such as 4-acetyl plenyl cyanate; 4-methyl mercaptophenyl cyanate and 3-N, N-dimethylcarbamylphenyl cyanate; as well as cY- and β-naphthyl cyanate and quinoline cyanates such as 5-cyanatoquinoline, furthermore bisfunctional cyanates such as 1,3- or 1,4-dicyanatobenzene, 1,3-, 1,4-, 1,5-, 2,5-dicyanatonaphthalene, 4,4-dicyanato-diphenyl-methane, -ethane (1, 1); -ethane (1,2); propane (2.2); 4,4'-dicyanatodiphenyl; 4,4'-Dicyanatodiphenylsulfon, -sulfid, -ether and the cyanic acid esters for example the following alcohols: ß, 13, ß-trichloroethyl alcohol, ß, ß, ß-trifluoroethyl alcohol, ß, ß, ß-tribromoethyl alcohol, ß, ß-dichloroethyl alcohol, H (CF2-CF2) 5CH20H.

Possible carboxylic acid halides are: The fluorides, chlorides, Bromides or iodides, for example the following carboxylic acids: Acetic acid, Chloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid, tribromoacetic acid, Fluoroacetic acid, trifluoroacetic acid, methoxyacetic acid, phenoxyacetic acid, methyl-phenoxyacetic acid , Chlorophenoxyacetic acids, phenylacetic acid, nitroacetic acid, cyanoacetic acid, methylmercaptoacetic acid, Acetylpropionic acid, propionic acid, butyric acid, isobutyric acid, stearic acid, palmitic acid, Oleic acid, cinnamic acid, benzoic acid, methylbenzoic acid, chlorobenzoic acid, di- (tri-, Tetra-, penta) chlorobenzoic acid, dimethylaminobenzoic acid, nitrobenzoic acid, di- (Tri) -nitobenzoic acid, methoxybenzoic acid, phenoxybenzoic acid, acetylbenzoic acid, Cyanobenzoic acid, methyl mercaptobenzoic acid, naphthoic acid (1) or (2), pyridine carboxylic acid (Nicotinic acid, isonicotinic acid), quinoline carboxylic acid, benzimidazole carboxylic acid, Benztriazolecarboxylic acid, benzthiazolecarboxylic acid, dichloroquinoxylincarboxylic acid and others

Possible carbonic ester halides are: The fluorides, chlorides, Bromide or iodide, for example the following carbonic acid ester: carbonic acid methyl ester, ethyl ester, chloroethyl ester, dichloroethyl ester, trichloroethyl ester, bromoethyl ester, -tribromoethyl ester, -fluoroethyl ester, -trifluoroethyl ester, -methoxy-ethyl ester, -phenoxyethyl ester, -o, m, p-methylphenoxyethyl ester, -o, m, -o, m, p-chlorophenoxyethyl ester, Phenyl ethyl ester, -nitroethyl ester, -cyanethyl ester, -methylmetkaptoäthylester, -acetylpropylester, -propylester, butylester, -isobutylester, -stearylester, -palmitylester, -oleyl ester, -cinnamylester, -phenylester, -methylphenylester, -chlorphenylester, -di (tri, tetra, penta-) chlorophenyl ester, dimethylaminophenyl ester, nitrophenyl ester, di (tri) nitrophenyl ester, -methoxyphenylester, -phenoxyphenylester, -acetylphenylester, -cyanophenylester, methyl mercaptophenyl ester, cd (13) naphthyl ester, pyridyl ester, quinoyl ester, -benzimidazolyester, -benztriazolylester, -benzthiazolylester.

Oxalic acid ester halides and oxalic acid thioester halides which are to be considered and oxalic acid amide halides are only mentioned as a selection: The fluorides, Chlorides, bromides or iodides, for example the following oxalic acid half-esters, half-thioesters and half-amides: methyl esters, ethyl esters, n-iso-propyl esters, n-iso-tert-butyl esters, Benzyl esters, phenyl esters, naphthyl esters, alkyl (C1-C6) phenyl esters, halophenyl esters, Nitrophenyl ester, alkoxyphenyl ester; those corresponding to the O-esters mentioned Thioester; each mono- or di-methylamide, ethylamide, allylamide, n-iso-propylamide, n-iso-tert-butylamide, benzylamide, phenylamide, naphthylamide, alkyl (C1 -C6) -phenylamide, Halophenylamide, nitrophenylamide, alkoxyphenylamide, also methyl-phenylamide (N-methylanilide) Methyl-benzylamide, morpholide, pyrrolidide, piperazide and others

Suitable CH-acidic compounds are those compounds the unsaturated electron-attracting one on the carbon atom carrying the acidic hydrogen atom 2 Carry radicals R1 and R2, both of which can also be components of a ring system.

The following groups come, for example, as radicals R1 and R2 Consideration: -CN, -CO-alkyl (C1-C12) e.g. -COCH3, -CO-stearyl, -COC6H5, N02-C6H4-CO-, CH30-C6H4-CO-, CH3-C6H4-CO, -COOCH3? -COOCH3, -COOC2H5, -COO-iso C3H7, -COOC6H5, -CONHC6H5 '-CONH-C6H5-Cl, -ClNH-C6H4-CH3 -CO-NH-C6H3- (CH3 2 CONH-C6H4-OCH3, -SOCH3, SOC6H5 '-S02CH3, -S02-C2H5, -CHO, -CO-N (CH3) Exemplary starting compounds are: malonitrile, dimethyl malonate, diethyl malonate, ethyl acetoacetate, Phenyl acetoacetate, acetoacetic anilide, -2-chloroanilide, -2 toluidide, -2,4-xylidide, -2-anisidide, -3-chloranilide, -4-chloranilide, stearyl acetic ester, acetoacetic acid-4-chloro-2,5-dimethoxyanilide, Ethyl benzoyl acetate, ethyl 3-nitrobenzoyl acetic acid, ethyl 4-nitrobenzoyl acetic acid ester, 4-methoxy-benzoxyl acetic acid ethyl ester, acetylacetone, benzoylacetone, dibenzoylmethane, Cyclo-hexanedione- (1,3), bis- (methylsulfono) -methane, bis- (phenylsulfono) -methane, Cyanoacetone.

The diluents used are those which are not compatible with the halogen compounds of formula I react, for example chlorinated hydrocarbons such as methylene chloride, Carbon tetrachloride, chlorobenzene; nitrated hydrocarbons such as nitrobenzene; Hydrocarbons such as light petrol, ligroin, benzene, toluene; ethers such as diethyl ether, Dioxane.

The following can be used as the base: -Alkali and alkaline earth hydroxides, carbonates, hydrides (such as LiOH, NaOH, KOCH; Ca (OH) 2, Li2C03, Na2C03, K2C03, Ca03, NaHC03, KHC03, NaH, LiH, KH etc.) but also tertiary amines such as pyridine, trimethylamine, Triethylamine, methyl-dicyclohexylamine, methyldiisopropylamine and others

and alkali metals such as Na, K or alcoholates such as e.g.

NaOCH3, NaOC2H5.

The reaction is generally carried out in such a way that the components lets act on each other in a diluent. An excess of CH-acidic Connection can sometimes be beneficial. Instead of using a CH-acidic connection plus a base, a salt of a CH-acidic compound can also be used. The end products If necessary, inorganic substances which have precipitated out are cleaned by washing with water or amine salts, and sets them, if they occur in the form of salts, if necessary free by acidification.

The compounds obtainable according to the invention are new and show Effectiveness as a plant protection agent.

The temperature data in the following examples relate to ° C.

Example: 4.6 g of sodium are dissolved in 200 ml of methanol, then 13.2 g (0.1 mol) of malodinitrile, dissolved in 40 ml of methanol, are added at -100 to 00C. When the addition is complete, the solvent is stripped off and the residue is washed with ether and vacuumed dry.

The sodium salt of malodinitrile prepared in this way is suspended in 200 ml of benzene, a solution of 10.9 g (0.05 mol) of N-chlorocarbonyliminocarbonic acid phenyl ester chloride in 100 ml of benzene is added dropwise at 8-10000, the mixture is stirred for 30 minutes at room temperature and the solution is concentrated in vacuo to dry one. The residue (24 g) is taken up in water, the aqueous solution is covered with a layer of ether and neutralized with dilute hydrochloric acid. 4 g of the compound fall from the ether phase from F: Zers. from 2500. Another 9 g are obtained after concentrating the ethereal solution. Total crude yield 13 g (= 94% of theory) Analysis: C14H7N5O2 (molar weight 277) CHNO molar weight.

Ber .: 60.6 Vo 2.5% 25.3% 11.5% 277 Found: 61.1% 2.9% 25.2% 11.4 , 270 Note: The malodinitrile salt can also be mixed with Na in toluene can be obtained.

Example 2: 26.7 g (0.1 mol) of N-propionyl-iminocarbonic acid (ß-ß-ß-trichloroethyl ester) chloride are added dropwise to 23.7 g (0.1 mol) of p-nitrobenzoyl acetic acid ethyl ester, initially charged in 20 ml of pyridine, and the mixture is left a few Stand at room temperature for hours. After diluting with plenty of ether, suction, soak and dry the product. The residue (28.5 g) is stirred with dilute HCl, filtered off with suction and washed. After drying, 16 g of the 1 mol of pyridine crystallizing compound remain: F: 164-1650 (from acetone) C17H17Cl3N207. C5H5N (molar weight 546.5) CH C1 NO Calc .: 48.3% 4.0% 19.4% 7.8% 20.6% Found: 48.4% 4.0% 19.5% 7.8% 20.6% In a procedure analogous to Example 1 and 2, the following were obtained: Reaction F: 0C temperature ° C decomp> 255 ° 5 to 10 ° O reaction F: 0C 4) -C = N-CII \ = / CH F: 278-790 / \ 5 F: 278-79 CN CN 5) C13C-CH2-0-C = N-C0-C2H5 CN CH CN -10 to 0 ° F: 224 ° 0 II 6) oC = N-8-C2H5 CH -10 to 0 ° F: 1820 (dec.) CH CN CONH2 C1 7) o O-C = N-CO-CH2-0 4 C1 o F: 136-1370 NC-CH-COOC2H5 i 8) Cl3C-CH2-0-C = N- 0 to 50 F: 200 - 2020 1 5 0 to 5 F: 200 - 202 NC-CH-C0NH2 NDÖ 9) Cl3C-CH2-0-C1 = N-C0-C2H5 N0 F: 164-1660 NC-CH-COOC2H5 N C1 10) e 0-1C-N-CO-CH2-O t -C1 0 to 50 F: 205-2060 NC-CH-CONH2.

Reaction F: ° C temperature ° C 0 to 10 ° F: 192 ° 25 to 45 ° F: 158 - 60 °

Claims (3)

-Patent claims (1) New compounds of the formula in which R stands for a haloalkyl radical or an optionally substituted aromatic radical, which can also be linked to heterocyclic radicals or contain bridge members, R1 and R2 stand for unsaturated, electron-withdrawing radicals, where R1 and R2 optionally also together form part of a five- or six-membered ring system may be, n denotes the numbers 1 or 2 and A 'denotes R3, -oR3 and -CHR1R2, where R1 and R2 have the meaning given above and R3 denotes an optionally substituted aliphatic, aromatic, cycloaliphatic or heterocyclic radical. 2. A process for the preparation of new iminocarboxylic acid ° deritates, characterized in that compounds of the general formula are used in which R stands for a haloalkyl radical or an optionally substituted aromatic radical, which can also be connected to heterocyclic radicals or contain bridging members, Hal stands for halogen, A stands for R3, OR3 and Hal and n stands for 1 or 2, where R3 is an optionally substituted aliphatic , cycloaliphatic, aromatic or heterocyclic radical, with CH-acidic compounds of the general formula 1 2 R1 -CH2R2 in which R1 and R2 are unsaturated, electron-withdrawing radicals and in which R1 and R2 can optionally also be part of a five or six ring system, at temperatures between -500 and 1200C, in the presence of a base, in the molar ratio of halogen atom to CH-acidic compound at 1 to = 1. 3. The method according to claim 2, characterized in that one is in the presence of a diluent works.