DE1940370A1 - New Dicarboximides - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKUSEN-Beyenrak P »tent-AbteUunx Fy / MH

-7, Aug. 1369

New dicarboximides

The invention relates to new N- (aroxy- or haloalkoxycarbonyl) -dicarboximides and a method for their production.

It has been found that the carboximide derivatives mentioned can be used obtained when cyanic acid esters of the general formula

R-O-CsN

in which R is a haloalkyl radical or an optionally substituted aromatic radical, which can also be linked to heterocyclic radicals can means

with dicarboxylic anhydrides of the general formula

ii 0

Le A 12 407 - 1 -

1098087 220?

in the *>

R and / or R hydrogen, halogen, nitro, alkoxy ^

Denote alkyl or aryl radicals;

1 2
R and R also together with the neighboring ones

C atoms can stand together for a ring system that is aromatic or can be cycloaliphatic, carry further substituents or condensed with further ring systems can be and optionally also contains heteroatoms;

X equals hydrogen or both X ge

mean a bond together,

at temperatures between about 0 ° and 250 ° G, optionally in a diluent and optionally in the presence of a catalyst. .

Especially about 50 and 150 ⁰ C is preferably between 20 and 200 ° C, is employed.

Haloalkyl radicals R are, for example, hydrocarbon radicals with up to 12 carbon atoms, which are preferably in the ß-position Carry chlorine, bromine, fluorine or iodine atoms.

Aromatic hydrocarbon radicals come as aromatic radicals R with up to 20 carbon atoms (preferably with up to 14 carbon atoms), in particular with 6 or ~ ίΰ carbon atoms in the ring system into consideration. The aromatic radicals R can have, for example, as substituents: Alkyl, alkylamino, dialkylamino, alkoxy radicals with up to 12 carbon atoms (preferably with up to 6 carbon atoms), furthermore lower acylamino and acyloxy groups, also aryl and aroxy groups with up to 10 carbon atoms (but preferably phenyl, phenoxy), the same

Le A 12 4-07 . - 2 -

109808/2207

Nitro, halogen, carbonyl, carboxyl, carbon ester, amide, sulfonyl, sulfonester, amide, acyl, cyano, flhodanide, Alkyl mercapto, aryl mercapto or acyl mercapto groups.

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

The cyanic acid esters used as starting compounds are known (Chem. Ber. 22a 3 ° ¹² ( ¹ 96 ⁴ )) The following cyanic acid esters can, for example, be used in the reaction:

Phenyl cyanate, mono- and polyalkylphenyl cyanates such as 3-methyl-, 4-isododecyl-, 4-cyclohexyl-, 2-tert-butyl-, 3-trifluoromethyl-, 2,4-dimethyl-, 3,5-biinethyl-, 2 , 6-diethyl-, α-allyl-2-biethoxyphenyl cyanate; Arylphenyl cyanates such as cyanatodiphenyl; Dialkylaminophenyl cyanates 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 _T , 2,4-dichloro, 2,6-dichloro, 3-bromine, 4-fluorine, 4-iodine, 2-chloro 6-methyl-phenylcyanate; Cyanatophenylcarboxylic acids, esters and amides such as ethyl 2-cyanato-benzoate, morpholide 2-cyanatobenzoic acid and diethylamide; Cyanatophenylsulfonic acid, esters, and amides, such as 4-cyanatobenzenesulfonic acid esters; Alkoxyphenyl cyanates such as 2-methoxy, 3-methoxy, ^ -isopropoxyphenyl cyanate; Phenoxyphenylcyanates such as 4-cyanatodiphenyl ether; Acyloxyphenyl cyanates such as 3-acetoxyphenyl cyanate; Acylphenyl cyanates such as 4-acetyl phenyl cyanate; 4-methylmercapto-phenylcyanate and ^ -NN-dimethylcarbamylphenylcyanate; as well as cC- and ß-naphthyl cyanate and quinoline cyanates such as 5-cyanatoquinoline and the cyanic acid esters, for example of the following alcohols:

Le A 12 407 - 3 -

1 0 9 8 0 8/2 2 G 7

■■■ "■" .- ■ -.- ■ Tr

β, β, β-tricbloroethyl alcohol, β, β, β-trifluoroethyl alcohol, β, β, β-tribromoethyl alcohol, β, β-diohloroethyl alcohol,

Aliphatic radicals R or R can be lower alkyl radicals or Be alkylene radicals; as aryl radicals are preferably phenyl

Λ 2

remnants into consideration. If R and R together with the neighboring carbon atoms form an aromatic ring system, which also has further Carry substitutes, condensed with other ring systems and can contain heteroatoms, for example systems such as benzene, naphthalene, phenanthrene, Anthracene, pyridine, quinoline, carbazole rings. If the ring systems are cycloaliphatic, the ent-P Talking fully or partially hydrogenated rings, but also cyclopentane or heptane rings. The anhydrides The following dicarboxylic acids can, for example, be used in the reaction:

Maleic acid; 2-methyl maleic acid; Succinic acid; 2-methylsuccinic acid; 2,3-dimethyl succinic acid; Phenylsuccinic acid; Methoxysuccinic acid; Chlorosuccinic acid; Nitro succinic acid; Phthalic acid; Methylphthalic acid; Mono-, Di-, tri-, tetra-chloro (bromo-, fluoro) -phthalic acid; Nitrophthalic acid ; Tetrahydrophthalic acids, hexahydrophthalic acid; Cyclopentane-o-dicarboxylic acid; Naphthalene dicarboxylic acid (1,2) or - (2,3); Anthracene-dicarboxylic acid-Ci ^) or - (2,3); "Phenantbrendicarboxylic acid; Cbinoline-o-dicarboxylic acids; Carbazole-o-dicarboxylic acids; Tetra (or Deka) hydroquinolino dicarboxylic acids.

The diluents used are those which do not react with acid anhydrides, for example chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride, chlorobenzene; nitrated hydrocarbons such as nitrobenzene;

Le A 12 4Ό7

1 0 9 8 0 £ / 2 2 0 7

SAD ORlQlNAL

Hydrocarbons such as petrol, ligroin, benzene, toluene, Ether like diet nylon ether.

The method of the invention is exemplified by the following Reaction equation explained:

ο Il h H, C_ CHj II
c _v O -4 \ V OCN

The catalysts used are preferably tertiary amines such as pyridines, quinolines, N-methylpiperidine, N, N-dimethylaniline, Ν, Ν-dietbylaniline, Ν, Ν-dimethylbenzylamine, trimethylamine, Triethylamine, methyldiisopropylamine.

The method can be carried out, for example, as follows will:

The components are, if necessary in a diluent, preferably combined in a molar ratio of about 1: 1 and, optionally after the addition of a catalyst, optionally heated together to temperatures of up to 250 ° C. The reaction temperature largely depends on the reactivity of the acid anhydride or the cyanate ester. The end products are isolated by known methods (distillation, crystallization), if appropriate after stripping of the solvent.

The new compounds correspond to the general formula

Le A 12 407

vf \ /.

N-C-OR

0 - 5 -

109808/2207

wherein R, R ¹ , R ² and X have the meaning given above.

They can be used to manufacture plant protection products, but can also be used directly as such.

example 1

29.6 g (0.2 mol) of phthalic anhydride and 32.5 g (0.22 mol) 2,4-Dimethylphenylcyanate are heated together to 180 ° C, then added 0.5 ml of triethylamine. There is a exothermic reaction which causes the temperature to rise to 230 ° C. After 15 minutes of roasting at the same temperature is cooled, mixed with a little alcohol and the excreted

sucked off. Yield: 48 g (= 81 % of theory); Fp: 1 4 ⁰ C (from Essigester).

Analysis: C ₁₇ H ₁₃ NO ₄ (295)

CHN 0

Calculated: 69.2 % \ 4.4 % 4.7 % 21.7 % Found: 68.9 % 4.5 % 4.7 # 21.7 %

Example 2

29.6 g (0.2 mol) of phthalic anhydride, 32.5 g (0.22 mol) of 2,4-dimethylphenyl cyanate and 1 ml of xylenol are placed together in 50 ml of xylene. At 130 ⁰ C 1 ml of triethylamine is

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10980 8/220 7

added and refluxed for one hour. After cooling down and suction gives 32 g of the same product as in Example 1 (identical IR spectra, no mixed melting point depression).

Examples 3-5

Analogous to example .1 and 2 are obtained from phthalic anhydride and .

3) ß.ßjß-Trichloräthylcyanat das

O
-CO-CH ₂ -CCl,

of m.p. 138-139 ° C.

Analysis: C ^ lL-Cl ^ NCv (322.5)

^{M to} "■ * ■ MoI-

_C H Cl N 0 weight

Calculated: 41.0 % 1.9 % 33.0 % 1.3% 19.8 % 322.5 Found: 41.2% 2.2 % £ 32.6 4.5 % 19.8 # 325

4) 4-Methylphenylcyanat das

from pp. 152 - 154 ⁰ C.

Le A 12 407 - 7 -

109808/220?

Analogue IR spectrum as the compound from Example 1.

5) pbenyl cyanate that

Il

6)

of m.p. 147-149 ° C.

IF, spectrum such as VerLinduriuen from examples

1 - 4-

ι C

⁰ V ϊ

CH,

7)

ir

fi-b .-- J / ν

3)

egg

Le A 12

1098 06/2207

ORIGINAL

Br ο

Compounds 6-12 also show analogous IR spectra like the compounds "from Examples 1 to 4 · '

Le A 12

109808/2 20

Claims (2)

19-0370 10 claims 1) Compounds of the general formula N-C-OR -. Il in the , R is a haloalkyl radical or a optionally substituted aromatic Radical, which can also be connected to heterocyclic radicals, means 1 2 R and / or R hydrogen, halogen, nitro, alkoxy ^ Mean alkyl or aryl radicals, 12 ' R and R also together with the neighboring ones C atoms can stand together for a ring system that is aromatic or can be cycloaliphatic, carry further substituents or condensed with further ring systems can be and given- W if also contains heteroatoms, X is hydrogen or both X together mean a bond. Le A 12 407 - 10 - 109808/2207 2) Process for the preparation of N- (aroxy or haloalkoxycarbonyl) -dicarboximides, characterized in that cyanic acid esters of the general formula ', -' R-O-CsN ■ "... ■■■■ · ■ • in the R is a haloene alkyl radical or a optionally substituted aromatic radical, which also has heterocyclic radicals can be connected, means with dicarboxylic anhydrides of the general formula 0 2 * C ' IO Xv v w X ti 0 in the / or R ² Mean alkyl or aryl radicals, '· ■ 2
R and / or R hydrogen, halogen, nitro, alkoxy ·; 12th
R and R also together with the neighboring ones C atoms can stand together for a ring system that is aromatic or can be cycloaliphatic, carry further substituents or can be condensed with further ring systems and optionally also contains heteroatoms, X is hydrogen or both Xs together mean a bond, Le A 12 407 - 11 - 109808/2207 at temperatures between about 0 ° and 25O ⁰ C, optionally in a diluent and if appropriate in the presence of a catalyst, are reacted. Le A- 12 407 - 12 - 109808/2207 ORIGINAL INSPECTED