DE1768678C3 - Process for the preparation of new imfnocarbonic acid ester derivatives - Google Patents

Description

N-acyl-iminocarbonic acid ester halides are not known. A reaction of cyanic acid esters with acyl halides is also not described. Only with a benzoyl chloride SbCl complex can be UnterRl ^r <gschlußaus2 moles of cyanate ester and 1 mole of said complex pyrylium salts prepared (Chemische Berichte, 100, 3739 [1967]).

Surprisingly, a process for the preparation of new iminocarbonic acid ester derivatives has now been found found, which consists in the fact that one cyanic acid ester of the general formula

R (OCNj _n

(D

40

in which R is a haloalkyl radical or an optionally substituted aromatic radical, which can also be linked to heterocyclic radicals and contain bridging members, and η stands for I or 2, with acyl halides of the general formula

R ¹ COX (II)

in which R ^{1 stands} for optionally substituted aliphatic. cycloaliphatic, aromatic or heterocyclic radicals and X is halogen, is reacted at temperatures from about -20 to about 250 ° C., preferably from -10 to 200 ° C., optionally in an inert diluent.

Haloalkylresic R are /. B. Hydrocarbon radicals with up to 12 carbon atoms, which are preferably in the // position of chlorine. Carry bromine, fluorine or iodine atoms.

Aromatic residues R are aromatic hydrocarbon residues with up to 20 carbon atoms in the ring system into consideration. The aromatic For example, radicals K can be substituted as substituents : Alkyl-. Aryl, alkylamino. Dialkylamino, acylamino. Nitro. Halogen, alkoxy, aroxy, acyloxy, carbonyl, carboxyl, carbon ester, amide. Sulfonyl, Sullon ester. -amid-, acyl-, cyano-, rhodanide-, alkylmerkaplo-. 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.

As bridge members, for example, alkylene groups with 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), furthermore oxygen, sulfur, SO ₂ and carbonate may be mentioned.

The cyanic acid esters used as starting compounds are known. It can be used for the inventive method, for. B. used the following cyanic acid esters will:

Phenylcyanate, mono- and polyalkylphenylcyanals such as 3-methyl-, 4-isododecyl-, 4-cyclohexyl-, 2-tert-butyl-, 3-trifluoromethyl-, 2,4-dimethyl-, 3,5-dimethyl- ^ o -äthyl- ^ AIlyl-I-methoxyphenylcyanatiArylphenylcyanate such as 4-cyanatodiphenyl; Dialkyl aminophenyl cyanates such as 4-dimethylamino, 4-dimethylamino-3-methylphenyl cyanate; Acylaminophenyl cyanates such as acetylaminophenyl cyanate; Nitiuphenyl cyanates such as 4-nitro-. 3-nitro-, 4-nitro-3-methyl. 3-nitro-6-meih>l-phenylcyanate; Halogenphenylcyanaie such as 2-chloro, 3-chloro, 4-chloro, 2,4-dichloro. 2,6-dichloro-, 3-bromo-. 4-fluoro, 4-iodine, 2-chloro-6-methylphenylcyanai: Cyanatophenylcarboxylic acid. -ester. -amides such as ethyl 2-cyanato-benzoate. 2-Cyanatobenzoic acid morpholide and diethylamide: C \ anatophenylsulfonic acid, esters, amides such as ethyl 4-cyanatobenzenesulfonate; Alkoxyphenyl cyanates such as 2-methoxy-. 3-methoxy-, 4-isopropoxy-phenyl cyanate: phenoxyphenyl cyanates such as 4-cyanatodiphenyl ether; Acyloxyphenyl cyanates such as 3-acetoxyphenyl cyanate: acylphenyl cyanate such as 4-acetylphenyl cyanate: 4-methylmercaptophenyl cyanate and 3-NN-dimethylcarbamylphenyl cyanate; as well as u- and // - naphthyl cyanate and quinoline cyanates such as 5-cyanatoquinoline. also bisfunctional cyanates such as 1,3- or 1,4-dicyanatobenzene, 1,3-. 1.4-, 1.5-. 2,5-dicyanatonaphthalene, 4,4'-dicyanato-diphemyl-methane. -ethane (II): -ethane (1.2): -propane (2.2); 4,4'-dicyanalodiphenyl: 4,4'-dicyanatodiphenyl sulfone. -sulfide. -ether and the cyanic acid esters, for example, of the following alcohols: />'./>Vi-Tribromälhylalkohol, //./i-Dichloräthylalkohol. H (CF ₂ -CF ₂ I ₅ CH ₂ OH.

Aliphatic radicals R ¹ are 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, IC or 12 carbon atoms in the Rip ' isysiem, which can optionally also be substituted by, for example, aryl (up to C;! ₀ in the ring system). Aroxj- (up to C ₁₀ in the ring system). Alkoxy (C ₁ -C "). Nitro. Halogen (fluorine. Chlorine, bromine.. Iodine). Acyl- (C _{1 -C 1} , phenyl). Alkyl mercapto i | C, -C ₆ ). Aryl mcrcapto (phenyl). Cyano. Rhodano, carbon ester (C ₁ - C ₁ , aryl to C ₂₁ , in Ringsyslern). Carbonamides Dialkylamino (C ₁ -C ₈ ) or acylamino (C ₁ ,,. Phenyl) · radicals.

For aromatic properties R ¹ , the same definition as above for the corresponding radicals R should apply. Suitable heterocyclic radicals R ¹ are preferably 5-, 6- or 7-membered ring systems with one or more heteroatoms such as O, N or S in the Ritig system.

Possible acyl halides are:

The fluoride. Chlorides, bromides or iodides for example the following carboxylic acids:

Acetic acid, chloroacetic acid, dichloroacetic acid. Chloroacetic acid. Bromoacetic acid. Tribromoacetic acid

piuoroacetic acid, trifluoroacetic acid, methoxyacetic acid, Phenoxyacetic acid, methyl-phenoxyacetic acid, chlorophenoxyacetic acid, phenylacetic acid, nitroacetic acid, Cyanoacetic acid, methylmereaptoacetic acid, acetylpropionic acid, Propionic acid, butyric acid, isobutyric acid, stearic acid, palmitic acid, oleic acid, Cinnamic acid, benzoic acid, methylbenzoic acid, chlorobenzoic acid, Di- (Tn-, tetra-, penta-) - chlorobenzoic acid, Dimethylaminobenzoic acid, nitrobenzoic acid, di- (tri) -nitrobenzoic acid, melhoxybenzoic acid, Phenoxybenzoic acid, acetylbenzoic acid, cyanobenzoic acid, methyl mercaptobenzoic acid, naphthoic acid (l) or (2), pyridine carboxylic acid (nicotinic acid, isonicotinic acid), quinoline carboxylic acid, benzimidazole carboxylic acid, Benzotriazolecarboxylic acid, benzothiazolecarboxylic acid, dichloroquinoxaline carboxylic acid and others.

The diluents used are those which do not react with acid halides, for example chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride, chlorobenzene; nitrated * o Hydrocarbons such as nitrobenzene; Hydrocarbons like petrol, ligroin. Benzene. Toluene: ether like diethyl ether.

The method according to the invention is explained using the following reaction equation as an example:

> —OCN + CI - CO - CCl,

Cl

^ "V-O-C = N-CO-CCI.,

The procedure can be carried out, for example, as follows:

The components are combined, if appropriate in a diluent, preferably in a molar ratio of about 1: 1 and, if appropriate, heated together to temperatures of up to 250.degree. The reaction temperature depends largely on the reactivity of the acid halide. The end products are isolated by known methods (distillation, crystallization), if appropriate after removal of the solvent. A number of the compounds III according to the invention cannot be distilled without decomposition. However, the raw products are pure enough for further reactions. The formation of the desired products can be easily monitored in the IR spectrum (strong bands at 5.75 and 5.95 to 6.00 ).

The compounds according to the invention are new and have the general formula

R -

R ¹

ner crystals (0.9 g) removed. After distilling off the Solvent i. V. 50 g (= 94% of theory) remain raw

O Cl

Il /

O-C = N-C-CH

ι \

ei a

During the distillation only one fraction passes over, i.e. that is, the crude product is sufficiently pure for others Implementations. The yield of distilled product is only 38 g (= 72%), because the substance is partially decomposed at the distillation temperature.

Bp .: 9970.2 Torr (crystallized after standing for several days the distilled product).

Analysis: CqH _n Cl ₃

Calculated:

C 40.5, H 2.23, Cl 39.9, O 12.0, N 5.25%.

Molecular weight 266.5;

found:

C 40.8. H 2.4, Cl 39.8, 0 12.0. N 5.3%.

Molecular weight 267; 269.

The IR spectrum shows the characteristic siarkcn bands at 5.75 μ and 5.95 μ.

Example 2

23.8 g (0.2 mol) of phenyl cyanate and 15.8 g (0.2 mol) of acetyl chloride are added to 100 ml of dry toluene Boiled under reflux for 7 hours. The toluene is then removed in a water jet vacuum (max. 80). 31 g (= 79% of theory) raw

Cl

1 1

55

(R. R'.X and / 1 have the meaning given above). You / own effectiveness as a pesticide

Example I.

29.4 g (0.2 mol) of dichloroacelyl chloride are placed in 100 ml of toluene and at room temperature 23.8 g (0.2 mol) of phenyl cyanate were slowly added. After the violent reaction has subsided, will still Boiled under reflux for 1 hour (16 ° C.) and after cooling a small amount of precipitated O by filtration - C --- N - C - CH.,

are preserved in this way.

Bp .: 7Γ / 0.Ι5 Torr or 6370.09 Torr (product solidified when standing).

Analysis: CJI _n CINO ₂ (197.5).

Calculated:

C 54.7. H 4.07. Cl 18.0. N 7.1. 0 16.2%:

found:

C 55.4, H 4.2. Cl 17.0. N 7.1. O 16.2%.

IR spectrum: characteristic strong bands at 5.75 and 5.95 μ.

Example 3

A mixture of 52.5 g (0.3 mol) /i./i./i--trichloroethyl cyanate. 47.9 g (0.33 mol) of dichloroacetyl chloride and 150 ml of carbon tetrachloride is 3 hours on Refluxed. After the solvent has been stripped off, 84 g (= S7% of theory) of crude are obtained

Cl

Cl

CI., C ~ - CH ₂ -OC = NC-CH

Cl

during their distillation, 63 g (= 75% of the raw material) of pure product pass over and the remainder decomposes

1

and remains as undistillable decomposition residue (18g).

Bp .: 107 to 109 ° C / 0.9 Torr or 96 to 100 "C / 0.4 up to 0.7 Torr.

Analysis: C ₅ H ₃ CI ₆ NO ₂ (322).

Calculated:

C 18.6, H 0.93, Cl 66.1, N 4.35, O 9.95%; found:

C 19.4, H 1.2, Cl 65.5, N 4.6, O 9.9%.

IR spectrum: characteristic bands at 5.75 and 5.95 μ.

IO

Example 4 "5

Analogously to Example 3, 16.9 g (0.1 mol) of u-naphthyl cyanate and 14.7 g (0.1 mol) of dichloroacetyl chloride are obtained 29.0 g (= 91% of theory) of crude in boiling benzene

678

(6) from phenylcyiimite and trichloroacety | chl «» ric |: Cl O

/ ~ Vo-c = N-c-cci ₃

Bp x 108 ° C / 0.4 torr; Crude yield: 80% of the theoretical

^ne (7) from //, / ^ - tricbloroethyl cyanate and monochloroacetylchloride:

Cl ₃ C-CH ₂ -OC = NC-CH ₂ CI boiling point: 97 "C / 0.3 Torr; crude yield: 78% of the theory

^nC (8) from 4-methylphenylcyanate and dichloroacetyl chloride:

Vc. ABC

Cl O

I Il

^s O-C = NC-CHCU H ₃ C

// v

. ₀ _C = N- ^

as undisclosed oil.

Analysis of the crude substance: C ₁₃ H ₈ Cl ₃ NO ₂ (316.5).

Calculated:

C 49.4, H 2.54, Cl 33.7, N 4.42, O 10.1%:

found:

C 49.7. H 2.8, Cl 32.7, N 5.0, O 9.7%.

IR spectrum: characteristic bands at 5.75 and 5.95 a .

35

Example 5

Analogously to Example 1, 30.6 g (0.2 mol) of p-chlorophenyl cyanate and 29.4 g (0.2 mol) of dichloroacetyl chloride are obtained in 100 ml of toluene 58 g of crude

40

45

Cl- / X-O-C = N-C-CH

in the form of an oil that slowly crystallizes. M.p .: 47 C (from petroleum ether).

Analysis: C ₉ H ₅ Cl ₄ NO ₂ (301).

Calculated:

C 36.0. H 1.66, Cl 47.1, N 4.65, 0 10.65%; found:

C 36.4, H 2.0. Cl 45.8, N 4.6, O 10.8%.

IR spectrum: strong bands at 5.75 and 5.95 μ.

Example c6 to 9

65

The same procedures were used to obtain 'and in each case by comparing IR spectra and / or Elemental analysis identified:

Bp: 130 to 134 C / 1.3 to 1.5 torr; Crude yield:

72% de · theory.

(9) from / i, /;, / i-trichloroethyl cyanate and allyl chloride

Cl
CI ₃ C-CH ₂ -OC = N-CO-CH ₃

Bp: 50 to 52'-C/0.2 Torr.

Example 10

34.8 g (0.2 mol) of trichloroethyl cyanate and 15. <Sg (0.22 mol) acetyl chloride were combined without solvent at 30 "C and then on for 2 hours Refluxed. Towards the end the temperature was 100'C. The excess acetyl chloride was distilled off, 29.0 g (= 90% of theory) of the same product as in Example 9 were obtained. identification by comparison of IR spectra.

Example 11

Analogously to Example 10, conversion of ^, //. / I-Trichlorätliylcyanat and propionyl chloride is obtained without Solvent that

Cl O

I Il

Cl ₃ C-CH ₂ -O — C = NC ~ -CH ₂ --CH., IR spectrum: strong bands at 5.75 and 5.95 ·, ..

Example 12

17.5 g (0, l-MoOftftp Trichloräthylcyanatund 15.5 g (0.11 mol) of benzoyl chloride are heated together without solvent slowly to reflux temperature (190 ⁰ C) and held for 10 minutes at this temperature. After cooling, 4 g fall trimerized

/ Μ, / ί-trichloroethyl cyanate (= tri - (/ yf, / mrichloroethyl) cvanate) and are eliminated by suction.

⁷ , _W Hd i V This gives 21 g (= 45% of theory) pure

The excess benzoyl chloride,. V.

distillicrt, that

Π C-CH ₇ -OC = N-CO- / ^{Cl3C 2} ^

from bp. 1O3-C / O.3 Torr.

Example

after removing the benzene

: r _chn ; Z _{0 0} ", _y . C 46.6, H 3.0, Cl 30.6, N 6.0, O 13.8%. ÄsZ, Cl 29.7, N 6.2, O 14.1%.

Example 15 ^ -Dichlorphenoxyacetic acid chloro-

Br

you get 30.2 g (= 84% of theory)

^25th

from bp. 88 1 * 92 ^ / 0.35 Torr. Analysis: C ₆ H ₇ BrCl ₃ NO ₂ (311.4).

Calculated: _{rn4 () N} 4 5. 0 10.3%:

C 23.0, H 2.3. Br 25.7, Cl 34.0. N

found: " _{g N46} 0 10.6%.

C 23.0. H 2.7. Br 25.8, Cl 33.9. N 4. ^ ^ C ₁₅ H ₁₀ Cl ₃ NO ₃ (358.5).

Examples 35 fjSw Cl 29.7. N 3.9. O 13.4%:

" ³ · ² · ^{cl 28} · ⁹ · ^{N 3} · ⁹ ·

-. - mo ,, jpsc ^

Toluene presented and ^ e; H) J »^^^ _Trü . Chloracetyl chloride added _hours is little

B bis _P , e. 16 to

1 to 15 were made from the each

remaining oil is distilled.

Cl

(16)

Cl

_ / Vo-c = i m.p. 1.3bi _S H4 C

Cl

(17)

(18)

(19)

COOCH ₃

Cl O

Cl

wr = N-C-CH, -O

σ ο

/ -VOC = NC-CH ₂ -OC ₂ H ₅

Fp 70 to 72 ^r C 116 to

Cl O

Cl- / "XOC = NC-CH ₂ -O- / X-Cl

Cl O

Ο-C = N-C-CH, -O

Cl O

. I Il

^ v-O-C = N-C

Cl

Cl

Cl 0

H ₃ C- <f VOC = NC- /

Cl O

. I Il

V-O-C = N-C-

Cl O

A-O-C = N-C-A

Cl

Cl O

Q-C = N-C

Cl

Cl Cl O

I Il

Cl ₃ C-CH ₂ -Ο —C = NCC- <Cl

- Ο -C = NC-CCl _{3 COOCH 3} °

10

M.p. 91 to 93 C.

M.p. 86 to 88 C.

Kp. ,, ₁₅ 156 to 159 (

M.p. 95 to 97 ° C

Kp. _Os 186 to 191 (

M.p. 74 to 76 C.

M.p. 68 to 69 C.

Kp. _O4 160 to

M.p. 56 to 58 C.

Claims (1)

Claim: Process for the production of new iminocarbonic acid ester derivatives, characterized in that cyanic acid esters of the general formula R (OCN) ₁ , in which R is a haloalkyl radical or an optionally substituted aromatic radical, which can also be linked to heterocyclic radicals and may contain bridging members, and η i is 1 or 2, with acyl halides of general formula R ¹ COX in which R ^{1 represents} optionally substituted aliphatic, cycloaliphatic, aromatic or heterocyclic radicals and X represents halogen, at temperatures from about -20 to about 250 ° C., optionally in an inert diluent.