DE1817541C3 - Process for the preparation of new iminocarbonic acid ester derivatives - Google Patents

Description

O - C = N- CO - CO - YRV _n IR (OCN) ₁ ,

in the io in the R and η have the meaning given above,

R stands for a haloalkyl radical or for one of the ¹ ^ compounds of the general formula

optionally substituted aromatic radical, O O

which may contain bridges, stands, and - || ||

R ¹ for an optionally substituted ali- Ri γ c - C - X

phatic or aromatic radical, and ^15. , _ ,, ,,. ",. . , _n j ^

Y for oxygen, sulfur or the group NR * ^{m of the} * \ ^Y ™ ^{d X} <* ^{ie the} meaning given above

where R * is hydrogen, an aliphatic Jg ** · at temperatures from about -20 to about

see aromatic or heterocyclic 150 ° C, optionally with merten Verdunmings-

Remainder means and together with nitrogen ^mi "^el; ^umF * zt." .. ""., ~

and Ri and optionally further ^a ° haloalkyl radicals R are ζ B. Hydrocarbon

Heteroatoms a heterocyclic ring system ^res . ^{te with} ^ ™ ^U carbon atoms, the preferred

can form and ^{wise in} 0 ^position 8 chlorine, bromine, fluorine or iodine

X for halogen and carry atoms.

η stands for 1 to 3 aromatic radicals R are aromatic

'* 5 hydrocarbon residues with up to 20 carbon

characterized in that atoms in the ring system are considered. The aromatic

Cyanic acid esters of the general formula R radicals can be used as substituents, for example

RiOCN) wear: alkyl, aryl, alkylamino, dialkylamino,

Acylamino, nitro, halogen, alkoxy, aroxy,

in which R and η have the meaning given above 30 acyloxy, carbonyl, carboxyl, carbon ester, amide,

have, with compounds of the formula sulfonyl, sulfonic ester, amide, acyl, cyano, rho

Q Q danid, alkyl mercapto, aryl mercapto or acyl

Il μ merkapto groups. Furthermore, the aromatic

πι γ rr ν radicals R with 5- or 6-membered ring systems, the

^R - * - <- - <- - ^x 35 can also contain heteroatoms such as N, O or S,

in which R ¹ , Y and X are linked as defined above.

have, at temperatures from about -20 to about.

150 ⁰ C, if appropriate in an inert dilution groups having 1 to 6 carbon atoms (preferably

medium, implements. 1 to 3 carbon atoms), furthermore oxygen, sulfur

40 fei, called SO ₂ and carbonate.

The cyanic acid esters used as starting compounds are known. It can for the invention Method z. B. the following cyanic acid ester a-N-acyl-iminocarbonic acid ester halide are not to be set:

known. Also a conversion of cyanic acid esters 45 phenyl cyanate, mono- and polyalkylphenyl cyanates

with acyl halides is not described. Only like 3-methyl-, 4-isododecyl-, 4-cyclohexyl-, 2-tert-

With a benzoyl chloride SbCl ₅ complex, butyl, 3-trinomethyl, 2,4-dimethyl, 3,5-dimethyl

with ring closure from 2 moles of cyanate and 1 mole of ethyl, 2,6-ethyl, 4-allyl-2-methoxyphenyl cyanate; Aryl

of the complex mentioned pyrilium salts produce phenylcyanates such as 4-cyanatodiphenyl; Dialkyl amino

(Chemical Reports, 100, 3739 [1967]). 50 phenylcyanates such as 4-dimethylamino-, 4-dimethyl-

Surprisingly, a process for amino-3-methylphenylcyanate has now been used; Acylaminophenylcy-

Production of new iminocarbonate derivatives of the anate such as acetylaminophenyl cyanate; Nitrophenyl

general formula cyanate such as 4-nitro-, 3-nitro-, 4-nitro-3-methyl,

_x . S-nitro-G-methyl-phenyl cyanate; Halophenylcyc-

l \ 55 anates such as 2-chloro, 3-chloro, 4-chloro, 2,4-dichloro,

¹ _ J 2,6-dichloro, 3-bromine, 4-fluorine, 4-iodine, 2-chlorine

C = N CO CO YRVn I 6-methylphenyl cyanate; Cyanatophenylcarboxylic acid,

esters, amides such as ethyl 2-cyanato-benzoate, 2-CyanatobenzoesäuΓemoφholid and diethylamide;

R for a haloalkyl radical or for a 60 cyanatophenylsulfonic acid, ester, amide such as 4-Cy-

optionally substituted aromatic radical, ethyl anatobenzenesulfonate; Alkoxyphenyl-cy-

the bridge members may contain, stands, and anates such as 2-methoxy, 3-methoxy, 4-isopropoxy

R ^{1 represents} an optionally substituted aliphatic phenyl cyanate; Phenoxyphenyl cyanates such as 4-cyanato-

or aromatic radical, and diphenyl ether; Acyloxyphenyl cyanates such as 3-acetoxy-

Y stands for oxygen, sulfur or the group NR * 65 phenylcyanate; Acylphenyl cyanates such as 4-acetylphe-

wherein R ^{s is} hydrogen, an aliphatic, nylcyanat; 4-methylmercapto-phenylcyanate and

aromatic or heterocyclic radical means SN.N-dimethylcarbamylphenyl cyanate; as well as oc and

and together with nitrogen and R ¹ and ge / 9-naphthyl cyanate and quinoline cyanates such as 5-Cy-

3 4

anatochinin, also bisfunctional cyanates such as α?; ::

1,3- or 1,4-di anatobenzene, 1,3-, 1,4-, 1,5-, 2,5-di- |

cyauatoaaphthalin, 4,4'-Dicyanatodiphenyi-methan- ^ / V_o —Γ - N -ΓΟ — CO—

-ethane (l, l); - ethane (l ^); - propaneC ^); 4,4'-dicyanato, N = / u - N ix »

dipehnyl; 4,4'-Dicyanatodiphenylsul £ on, -sulfid, -ether, 5

Non-functional cyanates such as i ^ S-tricyanatobenzene The process can be carried out, for example, as follows

iind the cyanic acid esters, for example, are listed below:

hole: / S ^ -Tribromäthylalkohol, ft / i-Dichloräthylal- The components are, optionally in one

alcohol, H (CF, -CF,) ₅ CH _S OH. Diluent, preferably in a molar ratio

Aliphatic "radicals R ¹ and R * are preferably io from about 1: 1, mixed together and, optionally, linear or branched, saturated or unsaturated with one another at temperatures of up to 150 ⁰ C, vbrsättigte hydrocarbon radicals having up to 25 carbon preferably 80 ⁰ C, heated. The reaction temperature of material atoms, which can contain up to 2 double or one triple, depends largely on the reactivity of the acid bond, and on the cycloaliphatic halide. The end products are isolated from residues with 5, 6, 7, 8, 10 or 12 carbon atoms in the 15 by known methods (distillation, crystalline ring system, which may also be substituted), optionally after the solution has been stripped off, for example, aryl (to to C ₂₀ in the mean. A number of the compound ring system according to the invention), aroxy (up to C ₁₀ in the ring system), fertilize III cannot be distilled without decomposition. The crude alkoxy (C ₁ -C,), nitro, halogen (fluorine, chlorine products are pure enough for further conversion - bromine, iodine), acyl (C ₁ -C ₈ , phenyl), alkyl -merkapto, 20 gen. The formation of the desired products is easy (C ₁ -C,), aryl mercapto- (phenyl), cyano-, rhodano-, controllable in the IR spectrum (strong bands at 5.6 carbon ester- (C ₁ -C ₁₁ , aryl to C ₁₀ in the ring system), and 5.9 to 5.95 μ).

Carbonamides Dialkylamino (C ₁ -C ₈ ) or acyl The compounds according to the invention are new and

amino (C ₁ ^, phenyl> radicals. have the general formula

The same as should be used for aromatic radicals R ^{1 and R *}
Definition as above for the corresponding radicals R.

specified apply. As heterocyclic radicals R ¹ and / X \

R * are preferably 5-, 6- or 7-membered ring I | J

systems with one or more heteroatoms such as R - \ O - C = N - CO - CO - YR ¹ J _n III O, N or S in the ring system into consideration. 3 °

As examples of the case where R ² together with N

and ^R1 is a heterocyclic, who also ^{(R> R> x} - ^{Y and "have the above} mentioned loading

May contain heteroatoms, be the morpholyl, interpretation). They show effectiveness as a crop protection

Piperidyl, pyrrolidyl and hexamethyleneimine residues medium,
called. 35

As a possible oxalic acid ester halo Example l

nides, oxalic acid thioester halides and oxalic acid. _o ~, _n , \ m η η 1

amidhalogenide be, for example, as a selection only ^{in e 'ne} solution of 18.7 g (0.1 MoI) Oxalsaure-

senannt phenyl ester chloride in 50 ml ether are

The fluorides, chlorides, bromides or iodides, at 40 temperature 17.4 g (0.1 mol) of trichloroethyl cyanate

For example, the following oxalic acid half-ester, -halbthio- getropfL Exothermic reaction, temperature rise

esters and half amides: methyl esters, ethyl esters, n-iso- ^{30 c} · E * ™ ^{rd to} complete the reaction

Propyl ester, n-iso-tert-butyl ester, benzyl ester, Phe-! Hour heated to reboot temperature.

nyl esters, naphthyl esters, alkyl ^ -C ^ -phenvlesters, Ha- cooling is made of little precipitated by-product

Logenphenylester, Nitrophenylester, Alkoxyphenyl- 45 cleaned ^{by Absau} 8 ^en and the solvent removed

ester; drawn the corresponding O-esters mentioned. _

Thioester; in each case mono- or di-methylamide, ethyl-. ³⁶ g of yellowish oil are ^{retained, which}

amide, allyl amide, durchknstalhsiert ^fen n-iso-propylamide, n-iso-tert-butyl ^{in the} P or can be distilled,

amide, benzylamide, phenylamide, naphthylamide, alkyl- ^{That obtained in both ways}
(Ci-C ^ -phenylamide, halophenylamide, nitrophe- 50

nylamide, alkoxyphenylamide, also methyl-phenyl- η η π

amide (N-methylanilide), methyl-benzylamide, Moφho- VV V

lid, pyrrolidide, piperazide and others. y γ II II I

The diluents used are those <f Λ - O - C - C - N = C - O - CH ₂ - CCl ₃ which do not react with oxalic acid ester halides, 55 \ = /
for example chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride, chlorobenzene; Ni has a melting point 61-63 ⁰ C (from light petrol) and trated hydrocarbons such as nitro-benzene. Coal b.p. from 150 to 152 ° C / O, 3 torr.
Hydrogen such as light gasoline, ligroin, benzene, toluene:. _, " _{N. xin} ,,, "..
Ethers such as diethyl ether, dioxane. 60 ^Αη3ΐ * ^{5 (ί} · C ₁₁ H ₇ Cl ₄ NO ₄ (359)

The method according to the invention is calculated on the basis of the following: C 36.7, H 2.0, Cl 39.6, N 3.9, O 17.9%;

the following exemplary reaction equation explained: found .. C 37.3, H 2.3, Cl 38.8, N 3.9, O 18.4%.

Example 2

OO 65

II I Analogously to Example 1 is obtained from 47.5 g (0.255 mol)

/ V_ OCN + Cl - C - C - OC ₆ H ₆ oxalic acid phenyl ester chloride and 43.5 g (0.255 mol)

\ / a-Naphthylcyanat after scratching the cooled

Reaction solution and suction of the then precipitated crystals 74 g des

Il

The reaction is refluxed for a further 4 hours. Then about 40 ml of ether are distilled off and 150 ml of light gasoline are added. After a while it crystallizes

from m.p. 94 to 96 ° C (from light spirit).

Addition of the filtrate precipitates a further 3 g of the product. Total yield as 77 g (= 86% of theory).

Analysis:

(353.5)

Calculated .. C 64.6, H 3.4, a 10.0, N 4.0, 0 18.2 %; found .. C 64.6, H 3.7, Cl 9.4, N 4.0, 0 18.3 %.

Example 3

To a solution of 37 g (0.2 mol) of oxalic acid phenyl ester chloride in 50 ml of ether, 23.8 g (0.2 mol) of phenyl cyanate in 25 ml of ether are added dropwise at room temperature. After the exothermic O - C - C - N = C - O

ίο off and is obtained by suction.

Yield: 52 g (= 85% of theory). Mp 43 to 45 ° C.
Analysis: C ₁₅ H ₁₀ ClNO ₄ (303.5)

Calculated .. C 59.3, H 3.3, Cl 11.7, N 4.6, O 21.1%; found .. C 59.2, H 4.1, Cl 11.0, N 4.8, O 22.0%.

Example 4

18.7 g (0.1 mol) of oxalic acid phenyl ester chloride,

ao dissolves in 50 ml of ether, are presented and 8 g (0.05 mol) of 1,4-dicyanatobenzene, dissolved in 30 ml of methylene chloride, are added dropwise. After 5 hours of reflux, boiling and cooling, about 100 ml of gasoline are added.

The failing one

V- 0-CCN = CO - € V- O - C = NC - C - O

is obtained by suction. Mp. 94 to 95 ⁰ C (from ether). Yield: 22.5 g (= 85% of theory).

Analysis: C ₁₄ H ₁₄ Cl ₂ N ₂ O ₈ (529)

Calculated. C 54.4, H 2.7, O 24.2, N 5.3, Cl 13.4%; found .. C 54.3, H 2.9, O 24.1, N 5.4, Cl 13.2%.

Example 5

17.4 g (0.1 mol) of trichloroethyl cyanate, dissolved in 25 ml of carbon tetrachloride, are added dropwise to 13.7 g (0.1 mol) of ethyl oxalate chloride dissolved in 25 ml of carbon tetrachloride. After 3Vr.stündigem stirring at 70 ⁰ C and removal of the solvent 30 g iV yellowish oil remain, the practically pure

OO Cl

Il! I I!

CjH ₆ - Ο - C - Ο - N = C-Ο - CHj- CCl ₃

that partially decomposes when distilled. B.p. 131-133 ° C / 0.9 torr.

CjH ₆ OCCN = CO

as a yellow oil that is only purified by being absorbed in ether, clarifying with Α coal and re-concentrating, as it decomposes during distillation. Analysis of the product purified in this way: C ₁₆ H ₁₂ ClNO ₄ (305.5)

Calculated .. C 59.0, H 3.9, Cl 11.6, N 4.6, O 20.9%; found .. C 59.0, H 4.3, Cl 12.1, N 4.6, O 20.8%.

Example 7

18.4 g (0.1 mol) of oxalic acid anilide chloride are dissolved in 100 ml of ether and 16.9 g (0.1 mol) of a-naphthyl cyanate, dissolved in 50 ml of ether, are added at room temperature. Temperature rise to 28 ^° C. The reaction solution is left to stand for 2 days, little impurities which have precipitated out are filtered off, gasoline is added and the mixture is cooled ^{to 0 ° C.}
The

OO Cl

Analysis: C ₇ H ₇

Calculated. .C27.0, H 2.3, Cl45.7, N 4.5, 0 20.6%; found .. C 27.9, H 2.5, Cl 45.4, N 5.0, O 19.8%.

Example 6

Analogously to Example 5, 16.9 g (0.1 mol) of a-naphthyl cyanate and 13.7 g (0.1 mol) of ethyl oxalate are obtained 28 g des

NH-C-C-N = C-O

of melting point 124 to 125 ^° C. (from isopropyl ether / benzene) precipitates and is obtained by suction. _b5 Yield: 28 g (= 79% of theory). Analysis: C ₁₉ H ₁₃ ClN ₂ O ₃ (352.5)

Calculated. C 64.7, H 3.7, Cl 10.12, O 13.6, N 7.9%; found .. C 64.4, H 3.9. Cl 9.7. O 1 V9. N 7 Q ° /

refluxed in 100 ml of ether for 7 hours. The

Example 8 Half of the solvent is then removed

pulled, 70 ml of gasoline are added. Over night

16.9g (0.1 mol) Λ-naphthyl cyanate and 26g (0.1 mol) crystallize in the refrigerator 32 g (= 76% of theory) Oxalic acid 4-tert-butylbiophenyl ester chloride are 5 des

S-C-C-N = C-O-

from the melting point 71 to 73 ° C (from petroleum ether). Analysis: C ₈₃ H ₂₀ ClNO ₃ S (425.5) Calculated. C 64.9, H 4.7, Cl 8.3, N 3.3, 011.3, S 7 5 ° / '

found ".. C 64.9, H 4.8, Cl 8.3, N 3.2, 011.4, S 7.1%.

Example 9

Analogously to Example 7, 14.8 g (0.1 mol) of 2,4-dimethylphenyl cyanate and 18.4 g (0.1 mol) of oxalao are obtained acid anilide chloride 27 g (= 73% of theory) des

O O

Cl

NH-C-C-N = C-

from melting point 111 to 112 ° C (from ether / light gasoline). Analysis: C ₁₇ H ₁₅ ClN ₂ O ₃ (330.5)

Calculated .. C61.8, H4.5, C110.8, N8.5, 014.5%; found .. C 61.9, H 4.9, Cl 10.5, N 8.7, 014.5%.

CH ₃

B e i s ρ i e 1 '10

Analogously to Example 8, phenyl cyanate and oxalic acid 4-tert-butylphenylthio-ester chloride with 72% Yield the oily

CH,

Cl

H ₃ C - C -Y V- SCCN = CO - / \

CH ₈ which decomposes during distillation

«09609/118

Claims (1)

1 2 possibly a further heteroatoms Claim: can form heterocyclic ring system, and ,, ,, _TT τ · t. ι X for halogen and process for the production of mino-coal _n ^ _T j ^ i ₈ 3 _s t _en t acid ester derivatives of the general formula 5 (υ. found, which is characterized in that one ι \ Cyanic acid ester of the general formula