DE2023077A1 - N-carboxy-imide cpds - with plant protection activity - Google Patents

Abstract

Title cpds. of formula:- (I) (where R1 and R2 are H, halogen NO2, alkoxy, alkyl, or aryl or R1 and R2 together with the adjacent C-atoms stand for a ring system which can be aromatic or cycloaliphatic, can carry further substitis. or can be fused with further ring systems and opt. also contains hetero atoms; R3 is an opt. substd. aromatic residue which can also contain bridge members; and each X is H or two X's together form a bond), which are plant-protection agents, are prepd. by reacting R3(OCN)2 with 2 mol. of corresp. anhydride at 0-250 degrees C.

Description

New dicarboxylic acid imides from bifunctional cyanates and dicarboxylic acid anhydrides (1st addition to patent ............ (P 19 40 370.4)) Subject matter of the main patent .......... (P 19 40 370.4) are new N- (aroxy- or haloalkoxycarbonyl-) dicarboximides and a method for their production.

They were obtained by cyanic acid esters of the general formula ROC # N in which R denotes a haloalkyl radical or an optionally substituted aromatic radical, which can also be linked to heterocyclic radicals, with dicarboxylic anhydrides of the general formula in which R1 and / or R2 are hydrogen, halogen, nitro, alkoxy, alkyl or aryl radicals; A 1 and R 2 together with the adjacent carbon atoms can also stand together for a ring system which can be aromatic or cycloaliphatic, carry further substituents or can be fused with further ring systems and optionally also contains heteroatoms; X is hydrogen or both X are together a bond, at temperatures between about 00 to 2500C, if appropriate in a diluent and if appropriate in the presence of a catalyst. It is preferred to work between 20 to 2000C, in particular 50 to 1500C.

In pursuance of the inventive concept underlying the main patent, it has now been found that bifunctional dicarboximide derivatives are obtained if bifunctional cyanic acid esters of the general formula R3 (0CN) 2 in R3 signify an optionally substituted aromatic radical which can also contain bridge members, with dicarboxylic acid anhydrides the general formula in which R1, R2 and X have the meaning given above for the main patent, in a molar ratio of 1: 2 at 0 to 2500C.

It is preferred to work at 20 to 2000C, in particular 50 to 1500C. In general, in the presence of a diluent and optionally under Worked addition of a catalyst.

Aromatic hydrocarbon radicals come as aromatic radicals R3 with up to 20 carbon atoms (preferably with up to 14 carbon atoms, in particular with 6 or 10 carbon atoms) in the ring system. The aromatic leftovers R3 can have as substituents, for example: alkyl, alkylamino, dialkylamino, Alkoxy radicals with up to 12 carbon atoms (preferably with up to 6 carbon atoms), furthermore lower acylamino and acyloxy groups, furthermore aryl and aroxy groups with up to 10 carbon atoms (but preferably phenyl, phenoxy), the same Nitro, halogen, carbonyl, carboxyl, carbon ester (preferably up to C6), amide, Sulphonyl, sulphonic ester (preferably up to c6-), amide, acyl (aliphati.sche up to C6 - CO, benzoyl), cyano, rhodanide, alkyl mercapto (preferably C1 4), aryl mercapto (preferably phenyl) or acyl mercapto groups (aliphatic to C6-CO, benzoyl).

Furthermore, the aromatic radicals R3 with 5- or 6-membered ring systems, which can also contain heteroatoms such as N, O or S, be connected.

The following can function as bridge members in R3: straight-chain or optionally branched alkylene (preferably C1 6) and cycloalkylene (preferably cyclohexylene, cyclophentylene) or Oxygen, sulfur, lower alkyl.

The bifunctional cyanic acid esters used as starting compounds are known (Chem. Ber. 97, 3012 (1964)).

Examples of bifunctional cyanic acid are: 1,3- or 1,4-dicyanatobenzene, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6-, 2,7-dicyanatonaphthalene, 1,4-, 1,5-dicyanatoanthraquinone, bis (4-cyanatophenyl) methane; -ethane- (1.1), -ethane- (1,2), -propane- (2,2), -cyclohexane (1, l), 4,4'-dicyanatodiphenyl ether, sulfide, -sulfoxyds -sulfon, 4,4'-dicyanatobenzophenone, 4,4'-dicyanato-diphenyl-methylamine, 2,2'-Dicyanatobisnaphthyl- (l, l) of polyesters or polyethers with terminal ends bifunctional cyanic acid esters derived from aromatic OH groups.

Aliphatic radicals R1 and R2 can be lower alkyl radicals or alkylene radicals be; phenyl radicals are preferably used as aryl radicals. Form R1 and R2 together with the neighboring carbon atoms an aromatic ring system, which also has other Carry substituents, be fused with other ring systems and heteroatoms can contain, for example, systems such as benzene, naphthalene, Phenanthrene, anthracene, pyridine, quinoline, carbazole rings.

If the ring systems are cycloaliphatic, then the corresponding fully or partially hydrogenated rings, but also cyclopentane or heptane rings. The anhydrides of the following dicarboxylic acids can, for example, be used in the reaction will: Maleic acid; 2-methyl maleic acid; Succinic acid; 2-methylsuccinic acid; 2,3-dimethylsuccinic acid; Phenylsuccinic acid; Methoxysuccinic acid; Chlorosuccinic acid; Nitro succinic acid; Phthalic acid; Methylphthalic acid; Mono-, di-, tri-, tetra-chlorine (bromine, fluoro) phthalic acid; Nitrophthalic acid; Tetrahydrophthalic acid; Hexahydrophthalic acid; Cyclopentane-o-dicarboxylic acid; Naphthalene dicarboxylic acid - (1,2) or - (2,3); Anthracene dicarboxylic acid (1,2) or - (2,3); Phenanthrene dicarboxylic acid; Quinoline-o-dicarboxylic acids; Carbazole-o-dicarboxylic acids; Tetra (or Deka) hydroquinoline o-dicarboxylic acids.

The diluents used are those that do not contain acid anhydrides react, for example chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride, Chlorobenzene; nitrated hydrocarbons such as nitrobenzene; Hydrocarbons like Light petrol, ligroin, benzene, toluene, ethers such as diethyl ether.

The process according to the invention is explained to us on the basis of the following exemplary reactions: The catalysts used are preferably tertiary amines, such as pyridines, quinolines, N-methylpiperidine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethylbenzylamine, trimethylamine, triethylamine, and ethyldiisopropylamine.

The method can be carried out, for example, as follows: The Components are, optionally in a diluent, preferably in the given molar ratios and, if necessary after addition of catalyst, optionally heated together to temperatures up to 250 ° C. The reaction temperature depends largely on the reactivity of the acid anhydride or the cyanate ester away.

The end products are isolated by known methods (suction , Crystallization), optionally after removing the solvent.

The new compounds correspond to the general formula: in which R1, R2, R3 and X have the meaning given above.

The new compounds are effective as pesticides.

In the following examples, the temperature data relate to OC Example 1: 29.6 g (0.2 mol) of phthalic anhydride and 16.0 g (0.1 mol) of 1,4-dicyanatobenzene are refluxed in 100 ml of xylene for 15 hours. The unusual one is sucked off.

Q .: Dec. from 3250 (from DMF) Both starting compounds can be re-isolated from the mother liquor. Yield based on conversion: 56 °, ó Analysis: C24H12N208 (molar weight 456) CHNO calc .: 63.0% 2.6% 6.2% 28.1% found: 62.4% 2.8% 6, 4% 28.1% Example 2: Analogously to Example 1, one obtains from and phthalic anhydride that Softening from 1850 analysis: C39H30N208 (molar weight 622) CHNO calc .: 75.2% 4.85% 4.5 ° / 0 15.4% found: 74.4% 5.4% 4.5% 15, 8% Further examples: The following was produced analogously to Example 1 and identified by comparison of IR spectra: Q .:> 3000 Q .:> 3000

Claims (5)

Claims: 1. Compounds of the general formula in which R1 and / or R2 are hydrogen, halogen, nitro, alkoxy, alkyl or aryl radicals; R1 and R2 together with the adjacent carbon atoms can also stand together for a ring system which can be aromatic or cycloaliphatic, carry further substituents or can be fused with further ring systems and optionally also contains heteroatoms; R³ denotes an optionally substituted aromatic radical which can also contain bridge members and X is hydrogen or both Xs together denote a bond. 2. Process for the preparation of dicarboximides by reacting cyanic acid esters with dicarboxylic acid anhydrides according to the main patent .. (P 19 40 370.4), characterized in that bifunctional cyanic acid esters of the general formula R3 (0CN) 2 in R3 is an optionally substituted aromatic radical which may also contain bridge members, with dicarboxylic acid anhydrides of the general formula in the R1 and / or R2 denote hydrogen, halogen, nitro, alkoxy, alkyl or aryl radicals, R1 and R2 together with the adjacent carbon atoms can also stand together for a ring system which can be aromatic or cycloaliphatic and carry further substituents or can be condensed with further ring systems and optionally also contains heteroatoms and X is hydrogen or both Xs together represent a bond, in a molar ratio of 1: 2 at 0 to 2500C. 3. The method according to claim 2, characterized in that at 50 to 1500C works. 4. Process according to Claims 2 and 3, characterized in that one works in the presence of a diluent, 5. The method according to claims 2, 3 and 4, characterized in that one works with the addition of a catalyst.