DE1912225A1 - D hydro-thiadiazine derivs as plant protect - ion agents - Google Patents

Abstract

Dihydro-thiodiazine derivs. as plant protection agents. New compounds of formula (I):- (in which R = Halogenated alkyl residue or a subst. aromatic residue, which may also be joined to another heterocyclic group and R' = H or a substd. aliphatic, alicyclic, aromatic or heterocyclic group, and n = 1 or 0), are prepared by reacting an iminocarbonic acid ester derivative with the formula: R-O-CCl=N-CO-Cl (in which R has the same connotation as in I) pref. in a diluting solvent, with a compound of formula: R'-(O)n-CS-NH2 (in which R' and n are as in I (above)).

Description

New dihydro-thiadiazine derivatives The invention relates to new ones 2-Ar (alk) oxy-6-aryl- (or.

alkyl, aroxy, alkoxy) -1, 4-dShydro-f.3.5-thiadiazinone (4) and a Process for their manufacture.

It has now been found that new dihydro-thia-diazine derivatives are obtained if iminocarbonic acid ester 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 linked to heterocyclic radicals, with compounds of the general formula in which R1 represents hydrogen, an optionally substituted aliphatic, cycloaliphatic, aromatic or heterocyclolic radical and n represents O or 1, optionally reacted in the presence of a diluent. Temperatures from 0 ° to 2,000, preferably 200 to 15,000, are used.

The new compounds obtained according to the invention have the general formula in which R, R1 and n have the meaning given above.

Haloalkyl radicals R are e.g. hydrocarbon radicals with up to 12 Carbon atoms, preferably in the ß-position chlorine, bromine, fluorine or iodine atoms wear.

aromatic hydrocarbon radicals come as aromatic radicals R with up to 20 carbon atoms (preferably with up to 14 carbon atoms), Especially with 10 carbon atoms in the ring system, the aromatic ones Rests R can, for example, carry alkyl, alkylamino, dialkylamino, Alkoxy radicals with up to 12 carbon atoms (preferably with up to 6 carbon atoms), further lower acylamino and acyloxy groups, distant aryl and aroxy groups with up to 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.

Furthermore, the aromatic radicals R with 5- or 6-membered ring systems, which can also contain heteroatoms such as N, O or S, be connected.

The components of the used for the inventive method Formula 1 are known and based on our own older proposals (see P 16.6810d.6) can be prepared from phosgene and cyanic acid esters.

The following cyanic acid esters are preferably used for this: 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-methoxyphenyl cyanate; Arylphenyl cyanates such as cyanatodiphenyl; Dialkylaminophenylcyanates such as 4-dimethylamino, 4-dimethylamino-3-methylphenyl cyanate; Acylaminophenyl cyanates such as acetylaminophenyl cyanate; Nitrophenyl cyanates such as 4-nitro, 3-nitro, 4-nitro-3-methyl, 3-nitro-6-methyl-phenyl cyanate; Halophenyl cyanates such as 2-chloro, 3-chloro, 4-chloro, 2,4-dichloro, 2,6-dichloro, 3-bromo, 4-fluoro, 4-iodo, 2-chloro-6-methyl-phenyl cyanate; Cyanatophenylcarboxylic acid, esters, amides such as ethyl 2-cyanato-benzoate, morpholide 2-cyanatobenzoic acid and -di-ethylamide; Cyanatophenylsulphonic acid, -ester, -amides such as 4-cyanatobenzosulphonic acid ethyl ester; 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-acetylphenyl cyanate; 4-methylmercapto-phenylcyanate and 7, N-dimethylcarbamylphenylcyanate; and - and ß-naphthyl 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) 5 CH20H.

Aliphatic radicals R 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 bonds, and cycloaliphatic Residues with 5, 6, 7, 8, 10 or 12 carbon atoms in the ring system, which optionally can also be substituted by, for example, aryl (up to C20 in the longitudinal system), Aroxy (up to C10 in the ring system), alkoxy (C1-C6), nitro, halogen (fluorine, chlorine, Bromine, iodine), acyl (C1-C6, phenyl), alkyl mercapto- (C1-C6), aryl mercapto- (phenyl), Cyano, Rhodanó, carbon ester (C1-C12, aryl to C20 in the ring system), carbonamide, Dialkylamino (C1-C8) or acylamino (C1-6, phenyl) radicals.

For aromatic radicals R1, the same definition as above for the corresponding radicals R given apply.

Compounds of the general formula which are used for the process according to the invention If n = 1, thiocarbamic acid esters come into consideration, which are preferably obtained by reacting cyanic acid esters with H2S according to the following equation: (see Chem. Ber. 97, 3022 (1964)).

Specifically, all of the above list of cyanic acid esters can be used Compounds derived from H2S addition can be used in the reaction. For the case n = 0, thiocarboxamides, which are adequately defined, come into consideration are, which is why only a few characteristic representatives are listed here as examples be: thioacetic acid amide, thiopropio acid amide, thiostearic acid amide, phenylthioacetic acid amide, Thioacrylamide, Thiobenzamide, p- (m-, o -) - ethyl-thiobenzamide, p- (m-, o -) - nitrothiobenzamide, p- (m-, o -) - Halogen (chlorine, bromine, fluorine, iodine) thiobenzamide, thionaphthoic acid amide (1) or - (2).

The method according to the invention is illustrated by way of example using the following reaction equation: The reaction is generally carried out by combining the two components in an inert diluent and, if appropriate, heating them together. Working up is carried out by known methods (concentration, suction, crystallization). The temperature range for the reaction is from 0.degree. C. to 2000, preferably between 200 and 1500.

The components are preferably used in a molar ratio of about 1: 1.

Is diluents are preferably ethers, such as diethyl ether, Dioxane, ketones such as acetone, nitriles such as acetonitrile, esters such as ethyl acetate and optionally halogenated or nitrated hydrocarbons such as benzene, toluene, light petrol, Petroleum ether, nitrobenzene, chlorobenzene, ethylene chloride, chloroform or carbon tetrachloride used.

The compounds according to the invention are new and are effective as crop protection agents, Example 1: 11.6 g (0.05 mol) of N-chlorocarbonyl-iminocarbonic acid (4-methyl phenyl ester) chloride are added to a mixture of 8.4 g (0, 05 mol) of 4-methylphenyl thiocarbamic acid and 100 ml of benzene were added. The mixture is heated to the boil until no more HCl escapes. When the cooled benzene solution is concentrated to about half the volume, 3-7 g of the fall and are obtained by suction. All of the benzene is drawn off from the filtrate. There remain 12.8 g of oily residue, from which, after stirring with ether, a further 4.9 g and, after further addition of ether, another 1.1 g of the same product are obtained. Mp of all portions: 181-182 ° C. Overall yield: 3.7 g + 4.9 g + 1.1 g = 9.7 g (= 60% of theory).

Analysis: C17H14N2O3S (326) CHNQS Calculated: 62.5%; 4.3; 8.6 atv; 14.7%; 9.8%; Found: 62.4%; 4.5%; $ 8.8%; 14.8%; 9.6% Example 2: In a procedure analogous to Example 1, 54.8 g (0.2 mol) of N-chlorocarbonyl-iminocarbonic acid (4-tert-butylphenyl ester) chloride and 33.4 g (0.2 mol ) Thiocarbamic acid 4-methylphenyl ester in 100 ml of benzene after 45 minutes refluxing a total of 47.0 g (= 64% of theory) of the Mp: 124-125 ° (from ethanol) Analysis: C20H20O3S (368) CCHN0S Calculated: 65.2%; 5.43%; 7.6%; 13.6%; 8.7% Found: 64.7%; 5.6%; 7.8%; 13.2%; 8.5% Example 3: When 11.6 g (0.05 mol) of N-chlorocarbonyliminocarbonic acid (4-methylphenyl ester) chloride and 6.85 g (0.05 mol) of thiobenzamide are combined at room temperature, the temperature rises at 27 °. The products first go into solution with the development of HCL, then the reaction product begins to fill out. After refluxing for half an hour, cooling and filtering off the precipitated product, 14 g (= 94% of the Tneorie) des of m.p. 177-1780C.

Analysis: C16H12N2O2S (296) Calculated: 64.9%; 4.05%; 9.45%; 10.8%; 10.8% Found: 65.0%; 4.1%; 9.6%; 10.9%; 10.6% Example 4: Analogous to Example 1, but with ether instead of benzene as the solvent, the N-chlorocarbonyl-imino-carbonic acid (4-methylphenyl ester) chloride and thiocarbamic acid 3-chlorophenyl ester give the mp: 199-201 ° C Analysis: C16H11ClN2O3S (346) CH Cl NOS Calculated: 55.5%; 3.18%; 10.2%; 8.1%; 13.9%; 9.25% Found: 55.6%; 3.4%; 10.1%; 8.3%; 13.9%; 9.2% Example 5: Analogously to Example 1, N-chlorocarbonyl-iminocarbonic acid - (-4-tert-butylphenyl ester) chloride and thiocarbamic acid 3-chlorophenyl ester give the of m.p. 162-1630 (Z.) Yield: 69% Analysis: C19H17ClN2O3S (388.5) Calculated: 58.8; 4.4%; 9.15; 7.2%; 12.3; 8.25% Found: 58.6%; 4.6%; 9.05%; 7.2%; 12.3%; 7.8% 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 nil carbon tetrachloride at Pa temperature. After the solution has cooled to 0 ° C., 60 g of 4-methylphenyl cyanate are 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 phenylcyant are formed, precipitate and are removed by suction. The remaining carbon tetrachloride is distilled off in a water jet vacuum and the clear, liquid residue 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 / 0.18 torr.

IR spectrum: strong bands at 5.65 µ 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 represents a haloalkyl radical or an optionally substituted aromatic radical, which can also be linked to heterocyclic radicals, and R1 represents hydrogen, an optionally substituted aliphatic, cycloaliphatic, aromatic or heterocyclic radical, and n can be the numbers 0 and 1 . 2) Process for the preparation of new dihydrothiadiazine 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 with compounds of the general formula in which H1 is hydrogen, an optionally substituted aliphatic, cycloaliphatic, aromatic or heterocyclic radical, and n can be the numbers 0 and 1, optionally reacted in the presence of an inert diluent. 3) Method according to claim 2, characterized in that in Temperature range from about 0 to 200 ° C works.