DE1768678B2 - - 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-SbCls complex can including 2 moles of cyanate and 1 mole of the said complex to prepare pyrylium salts (Chemical Reports, 100, 3739 [1967]).

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

R (OCN) ,,

(D

40

in which R is a haloalkyl radical or an optionally substituted aromatic radical, which is also with heterocyclic residues be connected and bridges may contain, and π is I or 2, with acyl halides of the general formula

R ¹ COX (II)

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

Haloalkyl radicals R are, for. B. hydrocarbon radicals with up to 12 carbon atoms, which are preferably in / f-position chlorine, bromine, fluorine or iodine atoms wear.

Aromatic hydrocarbon radicals with up to 20 carbon atoms come as aromatic radicals R in the ring system into consideration. The aromatic radicals R can have, for example, as substituents: Alkyl, aryl, alkylamino, dialkyiamino. Acylamino, nitro, halogen, alkoxy. Aroxy, acyluxy, Carbonyl, carboxyl, carbon ester, amide, sulfonyl, sulfonic ester. -amid-. Acyl, cyano, rhodanide, alkyl mercapto, Arylmercapto or Acylmerkaplo groups. Furthermore, the aromatic radicals R can have 5- or 6-membered ring systems which also contain heteroatoms as N, O or S can reveal.

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 for the invention Method z. B. the following cyanic acid esters are used:

Phenyl cyanate, mono- and polyalkylphenyl cyanates such as 3-methyl-, 4-isododecyl-, ^ cyclohexyl-, 2-tert-butyl-, 3-trifluoromethyl-, 2,4-dimethyl-, 3,5-dimethyl- ^ o- ethyl- ^ AUyW-methoxyphenylcyanatiArylphenylcyanate such as 4-cyanatodiphenyl; Dialkyl aminophenyl cyanates such as 4-dimethylamino, 4-dimethylamino-3-methylphenyl cyanate; Acylaminophenyl cyanates such as acetylaminophenyl cyanate; Nitropheuylcyanate such as 4-nitro-, 3-nitro-, 4-nitro-3-methyl, 3-nitro-6-methyl-phenylcyanate; Halotiene phenyl cyanates such as 2-chloro, 3-chloro, 4-chloro, "2,4-dichloro, 2,6-dichloro, 3-bromo, 4-fluoro, 4-iodo, 2-chloro -6-methylphenylcyanate; cyanatophenylcarboxylic acid, esters, amides, such as ethyl 2-cyanato-benzoate, 2-cyanatobenzoic acid norpholide and di-ethylamide; cyanatophenylsulfonic acid, esters, amides such as 4-cyanatobenzenesulfonate such as ethyl 2-cyanatobenzenesulfonate; , 3-methoxy-, 4-isopropoxyphenyl cyanate; phenoxyphenyl cyanates such as 4-cyanatodiphenyl acid; acyloxyphenyl cyanates such as 3-acetoxyphenylcyanal; acylphenyl cyanate such as 4-acetyIphenyl cyanate; and N-methyl-phenyl-cyanate, and Nyanatyl-cyanatyl and 3-methyl-cyanatyl-α, dimethyl-phenyl-α, Nyanatodiphenyl-phenyl-3-phenyl-phenyl-phenyl-3-phenyl-cyanate and 4-cyanatodiphenyl cyanate / i-Naphlhyl 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 and 4,4'- Dicyanato-diphenyl-methane, -ethane (lj); -athine (1.2): -propane (2.2); 4,4'-dicyanatodiphenyl: 4,4-dicyanatodiphenylsulfone, -sulfide, -ether and the cyanic acid esters, for example e of the following alcohols: /i./^/i-tribromoethyl alcohol, / ί, / ί-dichloroethyl alcohol, 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, 10 or 12 carbon atoms in the ring system, which can optionally also be substituted by, for example, aryl (up to C ₂₀ in the ring system), aroxy (up to C ₁₀ in the ring system), alkoxy (C _{, -C 6} ), nitro-halogen (fluorine, chlorine, bromine , Iodine), acyl (C, _{-C 1} , phenyl), alkyl mercapto (C, -C ₆ ), aryl mercapto (phenyl), cyano, rhodano, carbon ester (C, -C ₁₂ aryl to C ₂₀ im ring system), carbonamides dialkyl amino- (Q-C ₈₎ or acylamino (C, _ _6, phenyl) radicals.

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

Possible acyl halides are:

The fluorides, chlorides, bromides or iodides, at spicil wise the following carboxylic acids:

acetic acid, chloroacetic acid, dichloroacetic acid, trichk.ressigsäure, bromoacetic acid, tribromoacetic acidc

FUioracetic acid, trifluoroacetic acid, methoxyacetic acid, Phenoxyacetic acid, methyl-phenoxyacetic acids, Chlorophenoxyacetic acids, phenylacetic acid. Nitroacetic acid, cyanoacetic acid, methylmereaptoacetic acid, Acetylpropionic acid, propionic acid, butyric acid, isobutyric acid, stearic acid, palritic 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, methoxybenzoic acid, Phenoxybenzoic acid, acetyl benzoic acid, cyanobenzoic acid. Methyl mercaptobenzoic acid, naphthoic acid (l) or (2), pyridine carboxylic acid (nicotinic acid, isonicotinic acid), quinoline carboxylic acid, benzimidazole carboxylic acid, Benzotriazole carboxylic acid, benzothiazole carboxylic 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; nitrided Carbons hydrogen such as nitrobenzene; Hydrocarbons such as light gasoline, 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

- C = N-CO-CCl ₃

The method can for example. e done as follows will:

The components are, if appropriate in a diluent, preferably in a molar ratio of about 1: optionally heated to temperatures up to 25O ⁿ C combined with each other and 1. 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 easily be controlled in the IR spectrum (strong bands at 5.75 and 5.95 to 6.00 μ).

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

R-IO-C = N-CO-R ¹

(III)

(R. R ¹ , X and π have the meaning given above) They show effectiveness as crop protection agents.

example 1

29.4 g (0.2 mol) of dichloroacetyl 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 (116 ° C.) and, after cooling, a small amount of precipitated by filtration Crystals (0.9 g) removed. After distilling off the Solvent i, V. 50 g (= 94% of theory) remain of crude

O Cl

- C = N-C-CH

Cl Cl

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.

^{| C} boiling point: 9970.2 Torr (after standing for several days, the distilled product crystallizes).

Analysis: C ₉ H ₆ Cl ₃ O ₂ N (266.5).

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 strong 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 refluxed for 7 hours in 100 ml of dry toluene. The toluene is then removed in a water jet vacuum (at a maximum of 80 ^c ). 31 g (= 79% of theory) raw

Cl

0-C = NC-CH ₃

are preserved in this way.

Bp .: 7170.15 Torr or 63 / 0.09 Torr (product solidified when standing).

Analysis: C ₉ H ^ ClNO 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) / ^, // - 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 (= 87% of theory) of crude are obtained

CI

Cl

Cl ₃ 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

3, C! 66.1, N 4.35, 09.95%; ^ Bp, 10 8 ° C / O, 4 torr; Crude yield: 80% of the theoretical

1.2, Cl 65.5, N 4.6 O 9.9% ^I0 'V ^a « ^s M / W trichloroethylcyanal and monochloro

acetyl chloride:
IR spectrum: characteristic bands at 5.75
and 5.95 µ. Cl °

Example 4 _IS Cl ₃ C-CH ₂ -OC = NC-CH ₂ Cl

Analogously to Example 3, 16.9 g (0.1 mol) are obtained, boiling point: 97 ° C./0.3 Torr; Gross yield: 78% of the

u-naphthyl cyanate and 14.7 g (0.1 mol) dichloroacetyl rie.

Chloride in boiling benzene 29.0 g (= 91% of the theo- (8) from 4-methylphenylcyanate and dichloroacetyl-

rie) raw jo chloride:

ei ο I Il

I Il H ₃

y O— C = NC-CHCU ₂₅

Bp: 130 to 134 ° C / 1.3 to 1.5 torr; Crude yield: as an undistillable oil. 72% of theory.

(9) from / ^, / I-trichloroethyl cyanate and acetyl chloride: Analysis of the crude substance: C ₁₃ H ₈ Cl ₃ NO ₂ (316.5). 30th

Calculated: 9

C 49.4, H 2.54, Cl 33.7, N 4.42, 0 10.1%; _r , _{r rH n} _p_ _N _ _ro __ _rH

found: Cl ₃ C-CH ₂ Ό CM CU CH ₃

C 49.7, H 2.8, Cl 32.7, N 5.0. O 9.7%. _{χ S (Jp} . _{5Q bjs 5TC / O2 Torr}

IR spectrum: characteristic bands at 5.75
and 5.95 µ. B is ρ ie 1 10

. ... 34.8 g (0.2 mol) of trichloroethyl cyanate and 15.8 g

Example ^ ^ _{22 Mo} ^ A _Cet y | _c hk> chloride were without solvents

combined at 30 ° C and then 2 hours on

Analogously to Example 1, 30.6 g (0.2 mol) of boiled reflux are obtained. Towards the end the temperature was up

p-chlorophenyl cyanate and 29.4 g (0.2 MoT) dichloro 100 ° C. The excess acetyl chloride was removed

acetyl chloride distilled in 100 ml of toluene 58 g of crude, 29.0 g (= 90% of theory) of the same

45 Product obtained as in Example 9. identification

Cl O Cl by comparison of IR spectra.

, ^ ~ \ I Il /

Cl-f 1 ^ 0-C = N-C-CH

Example 11

Cl 50 Analogously to Example 10 is obtained by converting

ftft / K trichloroethyl cyanate and propionyl chloride without in the form of an ice oil that slowly crystallizes. Solvent that

M.p .: 47 ° C (from petroleum ether).

Cl O

Analysis: C ₉ H ₅ Cl ₄ NO ₂ (301). 55 I Il

Calculated: _g Cl ₃ C-CH ₂ -OC = NC-CH ₂ -CH ₃

C 36.0, H 1.66, Cl 47.1, N 4.65, O 10.65%; IR spectrum: strong bands at 5.75 and 5.95 a.

found:

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

⁶⁰ Example 12

IR spectrum: strong bands at 5.75 and 5.95 μ.

17.5 g (0.1 mol) ftft / I-trichloroethyl cyanate and 15.5 g (0.11 moles) of benzoyl chloride are solvent-free

Examples 6 to 9 slowly together to reflux temperature

65 (19O ° C) heated and 10 minutes at this temperature

The same procedures were kept. After cooling, 4 g of trimerized fall and in each case by comparison of IR spectra or / and / ^, / i-trichloroethyl cyanate (= tri - (/ i, /), / f-trichloroethyl) elementary analysis identified: cyanate) and are removed by suction.

and as indefinable decomposition residue? u- (6) and phenylcyunate and trichlonicetyl chloride: | V remains (18 g). I ar

Bp .: 107 to 109 ^[1 C / 0.9 Torr or 96 to IOOC / 0.4 Cl O

to 0.7 Torr,, _. I Il

5 <f XOC = NC-CCI ₃

Analysis: C ₅ H ₁ CI ₀ NO, (322). \ = /

Hey:
id:

■) - ■ ti

The excess Benzoylehlorid i. V. distilled off that

Cl
CUC-CH, -O — C = N-CO-

bJ-sibt back.

IR spectrum: strong bands at 5.75 μ and 6.00 u.

Example 13

35 g (0.2 mol / trichloroethyl cyanate, 18.7 ml (0.2 mol)

Propionyl bromide and 70 ml of benzene is heated for 1 hour at 70 'C ^1. After the benzene has been stripped off, the remaining oil is distilled in a high vacuum. This gives 33.7 g (= 63% of theory) of the

20 Cl ₃ C-CH ₂ -OC = N-CO-CH ₂ -CH ₃

Br
from bp 88 to 92 "C / 0.35 torr.

Analysis: C _n H ₇ BrCl ₃ NO ₂ (311.4).

Calculated:

C 23.0, H 2.3, Br 25.7. Cl 34.0. N 4.5. 0 10.3%: found: C 23.0, H 2.7, Br 25.8, Cl 33.9. N 4.6, 0 10.6%. This gives 21 g (= 45% of theory) pure

Cl O

<r ^ 0-C = NC-CH ₂ Cl

of bp 103X70.3 torr.

Analysis: CqH ₇ CI ₂ NO ₂ (232).

Calculated: C 46.6. H 3.0. Cl 30.6, N 6.0. O 13.8%: found:

C 47.0, H 3.2. Cl 29.7, N 6.2, O 14.1%.

Example 15

23.95 g (0.1 mol) of 2,4-dichlorophenoxyacetic acid chloride and 11.9 g (0.1 mol) phenyl cyanate are mixed in 100 ml toluene at ~ 120 ° C. for 30 minutes heated. Almost the entire contents of the flask solidify on cooling. After moving the contents of the flask with Ligroin, take up in ether, filter and concentrate, you get 30.2 g (= 84% of theory)

-O — C = N- C - CH, -

Example 14

35

23.8 g (0.2 mol) of phenyl cyanate are placed in KX) ml of toluene and at 10 to 15 C 22.6 g (0.2 mol) Chloroacetyl chloride was added dropwise. Any resulting cloudiness disappears again. After 3 hours there will be little (0.5 g) triphenyl cyanurate eliminated by suction, the toluene drawn off from the filtrate and the remaining oil distilled.

(16)

M Γ / -U Γ \ #

-QC = NC from Kp. 100 to 10! ¹ X.

Analysis: C ₁₅ H ₁₀ CI ₃ NO ₃ (358.5).

Calculated:

C 50.3. H 2.8. Cl 29.7. N 3.9, O 13.4%: found:

C 50.9, H 3.2. Cl 28.9. N 3.9, O 14.0%.

Example 16 to 28

Analogously to Examples 1 to 15, cyanic acid esters and acid chlorides were sometimes obtained from the ic th:

Mp. 113 to I'4 C

O - C = Ν - C-CH ₂ - O - \ V ~ ^C1

Mp 126-128 ° C

(18)

COOCH ₃

Cl O

I Il

QC = NC-CH ₂ -O-

Mp 70-72 ° C

(19)

f XOC = NC-CH ₂ -OC ₂ H

Kp. _O6 116 to Π r C 409524 /

Cl O

(ο

Cl- / VO C = NC-CH ₂ -O- / V-Cl

CH ₃

Cl O

-Ο-C = N-C-CH ₂ - Ο- / ~ \ ~ Cl

CH ₃

Cl O

Cl

Cl

(23) H ₃ C

Cl O

Cl O

<ζ JO- C = -Ν— C— <

Cl O

/ V-O-C = N-C-

Cl 0

S-, \ W

H ₃ C- /> - Ο— C = NC--

Cl

Cl

Cl O

Cl ₃ C-CH, -Ο — C = NCC - <f ')

Cl / ~ ^%; -y- Ο —C = Ν — C-CCl.,

COOCH ₃ °

10

M.p. 91 to 93 ° C

M.p. 86 to 88 ° C

Κρ. _{() 1} 5 156 to

Mp. 95 to 97 C Kp. ,, ₅ 186 to Fp. 74 to 76 C

Mp 68 to 69 C.

Bp ₀₄ 160 to mp 56-58 C.

4119

Claims (1)

I 768 Claim: Process for the production of new iminocarbonic acid ester derivatives, characterized, that one cyanate of the general formula R (OCN) _n in which R is a halogenalkyl radical or an optionally substituted aromatic radical, the can also be connected to heterocyclic radicals and contain bridges, means and η stands for 1 or 2, with acyl halides of the 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.