DE1912227A1 - Urea n-thiocarbonic acid amides as plant pro- - tection agents - Google Patents

Abstract

Urea N-thiocarbonic acid amides as plant protection agents. Compounds of the formula R-(O-CCl=N-CO-NH-CS-NR1R2)n are prepared by condensing R (0-CCl=N-CO-Cl)n with H2N-CS-NR1R2 (in a thinner at 0-120 degrees C) where R is haloalkyl or (subs.) aromatic or aromatic/heterocyclic, R1 and R2 are H, aliphatic, aromatic or together they form an N-heterocyclic and n= 1 or 2.

Description

New urea derivatives The invention relates to new N- (roxy-chloro-methylene-) - urea-N'-thiocarboxamides and a method for their production.

It has been found that new N- (aroxy-chloro-methylene) -urea-N'-thiocarboxamides are obtained when iminocarbonate derivatives of the general formula are obtained in which R stands for a haloalkyl radical or an optionally substituted aromatic radical, which can also be connected to heterocyclic radicals and contain bridge members, and n is 1 or 2, with thioureas of the general formula in which R1 and R2 each represent an optionally substituted aliphatic, cycloaliphatic or aromatic radical or hydrogen and in which R¹ and R² can also be part of a ring system together with the nitrogen atom, which can also contain further heteroatoms, preferably in a diluent with the exclusion of Rasser implements.

In general, temperatures between about 0 ° and 120 ° C. are used. The novel compounds obtainable according to the invention have the general formula in which X, R1, R2 and n have the meaning given above.

Haloalkyl radicals R are, for example, alkylene hydrogen octets with up to 12 Carbon atoms, which are preferably chlorine, bromine, fluorine or iodine atoms in the ß-position wear.

Aromatic hydrocarbon radicals come as aromatic radicals K with up to 20 carbon atoms (preferably with up to 14 carbon atoms), in particular with 1G carbon atoms in the ring system. The aromatic vest X can carry as substituents, for example: alkyl, alkylamino, dialkylamino, @lkoxy radicals with up to 12 carbon atoms (preferably with up to 6 carbon atoms), furthermore lower @ rylamino and acyloxy groups, also aryl and aroxy groups with up to u 10 carbon atoms (but preferably phenyl, phenoxy), also nitro, Halogen, carbonyl, carboxyl, carbon ester, amide, sulfonyl, sulfonic ester, amide, Acyl, cyano, rhodanide, alkyl mercapto, aryl mercapto or acyl mercapto groups. Further the aromatic radicals R can be 5- or 6-membered Ring systems, which can also contain heteroatoms such as N, O or S, connected be. As bridge members, for example, alkylene groups with 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), Farner Sanersotff, sulfur, SO2 and carbonate called.

The components of the Formula 1 are known and based on our own older proposals (see P 16.68108.6) can be prepared from phosgene and cyanic acid esters.

The following cyanic acid esters are used with preference; Phenylcyanut, Mono- and polyalkylphen; lcyanate mie @@@ etayl-, 4-isododecyl-, 4-cyclohexyl-, 2-tert-butyl-, 3-trifluoromethyl, 2,4-dimethyl, 3,5-dimethyl, 2,6-diethyl, 4-allyl-2-methoxyphenyl cyanate; Arylphenyl cyanates such as cyanatoquiphenyl; Dialkylaminophenylcyanates such as 4-dimetoylamino, 4-limetaylamino-3-methylphenyloyanate; Acylaminophenyl cyanates such as acetylaminophenyl cyanate; Nitrophenyl cyanates such as 4-nitro, 3-nitro, 4-nitro-3-methyl, 3-nitro-6-methyl-phenyl cyanate; Halegenylcyanate such as 2-chloro, 5-chloro, 4-chloro, 2,4-Lich @@@ -, 2,6-dichloro, 3-bromo-, 4-fluoro-, 4- @ od-, 2-chloro-6-met @@ - phenyloyanate; Cyanatophenyl carbonate, esters, amides such as ethyl 2-cyanatobenzoate, @ -cyanatobenzoic acid morpholide and diethylamide; Cyan; tophenylsulfonic acid, - @@@@, amides such as 4-cyanatotenzenesulfonabureethyl ester; Alkoxyphenylcyanates such as @ methoxy-, 3-methoxy-, 4-isopropoxyphenylcy @@@@ Phenoxyphenylcyanate such as 4-cyanatodiphenyl ether; Acyloxyphenyl cyanates such as 3-acetoxyphenyl cyanate; Acyl phenyl cyanates such as 4-acetylphenyl cyanate; 4-methylmercapto-phenylcyanate @@@ 3-N, N-dimethylcarbamylphenylcyanate; as well as α- and ß-naphth @@ .- cyanate and quinoline cyanates such as 5-cyanatoquinoline and the cyanic acid esters, for example, of the following alcohols: ß, ß, ß-trichloroethyl alcohol, ß, ß, ß-trifluoroethyl alcohol, ß, ß, ß-tribromoethyl alcohol, ß, ß-dichloroethyl alcohol, H (CF2-CF2) 5CH2OH.

ftliphatic radicals R¹ and RS 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 Residues with 5, 6, 7, d, 10 or 12 sole atoms in the ring system, which optionally can also be substituted by, for example, hryl- (up to C20 in the ring system), Aroxy (up to C10 in the ring system), alkoxy (C1-C6), nitro, halogen (fluorine, chlorine, Bromine, iodine), acyl (C1-C6, Phnyl), alkyl mercapto- (C1-C6), aryl mercapto- (phenyl), cyano, Rhodano, carbon ester (C1-C12, aryl to C20 in the ring system), carbonamide, lialkylamino (C1- '' 8) or acrylamino (C1-6, phenyl) radicals.

The same definition as above should be used for aromatic radicals R¹ and R² for the corresponding radicals R given apply.

R1 and k2 stand together for a ring system that also contains further heteroatoms can deflate, in particular on 5-, 6- or 7-ring systems, such as piperidine, Morpholine, pyrrolidine, decahydroquinoline, tetrahydroisoquinoline, dodecahydrocarbazole, Benztriazole, imidazole or also rexamethyleneimine, thought.

Compounds used for the process according to the invention For formula II such thioureas come into consideration, which at least one free Own NH2 group.

Here are just a few typical representatives, for example: Thichurea, N-methylthiourea, N-ethylthiourea, N-isopropylthiourea, N-tert-butyl thiourea, N-allylthioburea, N-stearylthiourea, N, N-dimethylthiourea, N, N-diethylthiourea, N, N-diallylthiourea, N-methyl-N-stearylthiourea, N-benzylthiourea, N, N-dibenzylthiourea, N-methyl-N-benzylthiourea, N-aminothiocarbonylmorpholine, N-aminothiocarbonylpiperidine, N-aminothiocarbonylpyrrolidine, N-aminothiocarbonyltetrahydroisoquinoline, N-amino-thio-carbonyldekahydroquinoline, N-methyl-N-phenylthiourea, N-phenylthiourea, N, N-diphenylthiourea, N- (p (m, o) tolylthiourea, N-p (m, o) nitrophenylthiourea, N-p (m, o) chlorophenylthiourea, N-p (m, o) methoxyphenylthiourea, N-p (m, o) -dimethylaminophenylthiourea, N-p (m, o) cyanophenylthiourea, N-p (m, o) acetylphenylthiourea, N-Di (tri, tetra, Penta) chlorophenylthiourea, N-cyclohexylthiourea.

The method according to the invention is illustrated by way of example using the following implementation: The reaction is carried out by combining the two components, preferably in an inert organic solvent. In general, the components are combined at room temperature and, depending on the basicity of the thiourea, the reaction mixture may have to be heated. The temperature limits are generally between about OOC and 120 ° C. The reaction product, which generally precipitates out during the reaction, is usually isolated by suction (if appropriate after concentration). The substances must be protected from moisture.

Ittfier are preferably used as solvents, such as i) ethyl ether, Dioxane, ketones such as acetone, nitriles such as Acetontril, esters such as ethyl acetate, and optionally halogenated or nitrated hydrocarbons, such as benzene, toluene, xlevene, petroleum ether, nitrobenzene, chlorobenzene, methylene chloride, chloroform or carbon tetrachloride is used.

The compounds are new and show effectiveness in pesticides.

Example 1: 7.6 g (0.1 mol) of thiourea are dissolved in 25G ml of anhydrous acetone and at 25 ° 23.2 g (0.1 mol) added dropwise with external cooling. After 30 minutes of stirring, the precipitated sucked off, washed with acetone and dried in a desiccator. Yield: 21.1 g (= 77% of theory) decomp. points: 1580 Analysis: C10H10ClN3O2S (271.5) CHNOS Calculated: 44.3%; 3.69%; 15.5%; 11.8%; 11.8%; Found: 44.4%; 4.1; 15.4%; 12.3%; 11.5% Example 2: 15.2 g (0.1 mol) of phenylthiourea and 23.2 g (C, 1 mol) of N-chlorocarbonyl-iminocarbonic acid (4-methylphenyl ester) chloride are dissolved in 150 ml of dry toluene heated to boiling temperature. At 850 HCl begins to develop. After boiling for 10 minutes, the mixture is cooled. The unusual one is filtered off with suction, washed cold with toluene and dried.

Yield: 23.6 g of yellow Tulver (= 68% of theory).

Dec. point: 207 - 208 ° C Analysis: C16H14ClN3O2S (347.5) C H Cl N 0 Calculated: 55.3%; 4.02%; 10.2%; 12.1%; 9.2%; 9.2%; Found: 55.0%; 4.2%; 10.1%; 12.0 %; 9.5%; 9.3%.

Example 3: 15.2 g (0.1 mol) phenylthiourea is added in 10C ml p.a.

@ceton submitted. 23.2 g (0.1 mol) of N-chlorocarbonyl-iminocarbonic acid (4-methylphenil ester) chloride are added to this solution added dropwise at 50-100. The same product as in Example 2 turns out white. (Identical IR spectra, no mixed melting point depression).

Rus yield: 31.2 g (= 90% of theory) decomp. Ic. @ 206 - 208 ° C.

Example 4: Analogously to Example 3, 9 g (0.1 mol) of methylthiourea and 23.2 g (0.1 mol) of N-chlorocarbonyl-iminocarbonic acid (4-methylphenyl ester) chloride in 150 ml of acetone (pa) are obtained at room temperature 25.4 g (= 89 of theory) des from decomp. Pt: 170 ° C Analysis: C11H12ClN3O2S (285.5) CH Cl N O S Calculated: 46.0%; 4.2%; 12.5%; 14.7%; 11.2%; 11.2%; Found: 46.0%; 4.4%; 12.0%; 14.5%; 11.6%; 11.5% The preparation of the starting compounds (I) is illustrated by the following example: 45 g of phosgene (0.45 mol) are introduced and dissolved in 250 ml of carbon tetrachloride at room temperature. After cooling the solution to 0 ° C., 60 g of 4-methylphenyl cyanate were added dropwise. Little white substance has precipitated, which dissolves again when warmed to room temperature. When the reaction has ended, 100 ml of carbon tetrachloride are distilled off.

8.5 g of tris-4-methyl-phenylcyanurate, obtained as a by-product by trimerization of the phenylcyanates are formed, precipitate and are removed by suction. The remaining carbon tetrachloride is distilled off in a water jet vacuum and the clear, liquid Rückstana degassed at 800 C / 0.3-0.5 torr. The one left behind The residue is distilled.

The distilled one is obtained with a yield of 68% with a boiling point of 81 ° -82 ° C / 0.IQ torr.

IR spectrum: strong bonds at 5.65 and 5.95 µ.

Also the others necessary to carry out the procedure Starting compounds can be obtained in an analogous manner.

Claims (3)

Patent claims: 1) Compounds of the general formula in which R stands for a haloalkyl radical or an optionally substituted aromatic radical, which can also be connected to heterocyclic radicals and contain bridge members, and R1 or R2 stands for hydrogen, optionally substituted aliphatic, cycloaliphatic or aromatic radicals, and in which R1 and R2 together with the nitrogen atom can be part of a ring system which can also contain further heteroatoms and n is 1 or 2. 2) Process for the preparation of new urea derivatives, characterized in that one iminocarbonic acid ester derivatives of the general formula in which R stands for a haloalkyl radical or an optionally substituted aromatic radical, which can also be connected to heterocyclic radicals and contain bridge members, and n is 1 or 2, with thioureas of the general formula in which R1 and R2 denote hydrogen, optionally substituted aliphatic, cycloaliphatic or aromatic radicals, and in which R1 and R2 together with the nitrogen atom can be part of a ring system which can also contain further heteroatoms, preferably in a diluent, with the exclusion of water implements. 3) Method according to claim 2, characterized in that in Temperature range from about 0 to 12000 works.