DE1793128C3 - Process for the preparation of new iminocarbonic acid ester derivatives - Google Patents

Description

if necessary in an inert solvent, ^t JJ ^ 5 ^ X _1I0 ^ _III Uthytater, 2Cy «ia. implements. ^ S JJ ^^ u ^ rpholide and diethylamide; Cyanate

"~ phenyl sulfonic acid, esters, amides such as 4-cyanato-

benzölsulfonsäureäthylesterAlkoyyphenylcyanatewie

Cyanic acid esters do not combine with acid chlorides 2-methoxy-, 3-methox; ' ^¥ """"*'

■ m (Angewandte Chemie. 79. p. 230 [1967]). Only ₃₀ phenoxyphenylcyanaU

with a benzoyl chloride-SbCl ^ complex, acyloxyphenyl cyanates can be obtained

Nter ring closure from 2 mol of cyanate and 1 mol of acylphenylcyanate such as 4-acetylphenylcy

of the complex mentioned pyrylium salts produce thylmercapto-phenylcyanate and 3-N N Di

(Chemical Reports, 100, p. 3739 [1967]). amylpheny cyanate; sow e «- ^ Jj ^ JP ^ W

Surprisingly, a process for 35 and Chmolmcyanate such as 5-Cyana ^ toch.noIm, terner

Production of new iminocarbonate derivatives bisfunctional Ie Cyanate ™ J £ ^^ £ g * ™ ^

found, which consists in the fact that one cyanic acid benzene, 1,3-, 14-, 15-, 2 5-D ^^ JP ™ Brille ¹ ^, ^.

Less of the general form. ÄffiÄ ^ SÄ

R (OCN) 40 diphenyl sulfone, sulfide, ether and the cyanate esters

^{K (UC1N} '"for example the following alcohols: / W-Tnchlorathyl-

in which R stands for a haloalkyl radical or a counter alcohol, ^^ - ^. ^^ ¹ ^^ '/ ^^ " ¹ " ^ ⁰¹¹¹ ' optionally substituted aromatic radical, which also includes ethyl alcohol, ^ -dichloroethyl alcohol, can be linked to heterocyclic radicals and _

May contain bridge members, stands and η 1 or 2 45 H (Cf ₂ Lt-; | _s Ln ₂ un.

means with Trichlorrhodari of the general formula. hknow

The production of trichloromodane is known.

_C j The diluents used are those

I that do not react with Trichlorrhodan, for example

_cl _ _s _ _{c == N} --d 50 chlorinated hydrocarbons such as methylene chloride,

Carbon tetrachloride, chlorobenzene; nitrated carbon

at temperatures from about -20 to about 120 ^° C., hydrogen such as nitrobenzene; ^{K "} W ™ ^sse _Ä f ^ol J ^e <" £ preferably about -10 to about 100 "C, given light gasoline, ligroin, benzene, toluene. Ether as if in an inert solvent, converts. Diethyl ether. . ,,. _m

Haloalkyl radicals R are, for. B. Hydrocarbon 55 The inventive method is based on the following residues with up to 12 carbon atoms, the preferred example explains: wise in ^ position, chlorine, bromine, fluorine or iodine y

carry atoms. . , / "V_ ηΓΝχΠ-ς-Γ = Ν-Π

The aromatic radicals R are aromatic <^ j ^ ~ OCN + Cl ^ c in ^ i ^

Hydrocarbon residues with up to 20 carbon 60 \ = /

atoms in the ring system into consideration. The aromatic ι ι

Residues R can be used as substituents, for example _> / V_q r = NSC = N Cl

wear: alkyl, aryl, alkylamino, dialkylamino, \ _ /

Acylamino, nitro, halogen, alkoxy, aroxy, acyl

oxy, carbonyl, carboxyl, carbon ester, carbon 65 The components are, preferably in one

amide, sulfonyl, sulfonic ester, sulfonamide acyl, diluent and preferably in the molar ratio

Cyano, rhodanide, alkyl mercapto, aryl mercaptonis 1: 1, put together and with one another

or acyl mercapto groups. Further, the aro- temperatures can be heated up to 120 ⁰ C.

I. O

Isolation is carried out by known methods (distillation, crystallization), if appropriate after stripping of the solvent. In general, the crude preparation solution is used for further reactions. Identification is easily possible via the IR spectrum (characteristic bands at 5.85 and 6.1 µ).

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

Cl

Cl

0-C = NSC = N-CIJ ₁ ,

where R and u are as defined above. They show effectiveness as pesticides.

example 1

1§5 g (0.1 mol) of trichlorohodane are placed in 50 ml of ether and 15.4 g at room temperature (0.1 mol) p-chlorophenyl cyanate added. After an hour The solvent is removed by heating under reflux. This leaves 18 g (= 57% of theory) raw

Analysis of the crude product: C ₈ H ₄ Cl ₄ N ₂ OS (318).

Calculated:

C 30.2, H 1.26, Cl 44.6, N 8.8, O 5.05, S 10.1%;

Molecular weight 318; found:

C 30.6, H 1.8, Cl 43.6, N 8.9, O 5.7, S 10.4%;

Molecular weight 322.

IR spectrum: characteristic bands at 5.85 and 6.1 μ.

Examples 2 to 4

Analogously to Example 1, one obtains in each case by reaction with trichlorohodane

2. Phenylcyanate that

Cl Cl

I!

) —C = N-S-C = N-Cl

Cl

Cl

Cl

-C = N-S-C = N-Cl

as a gradually crystallizing oil. The product is pure enough for further conversions. Decomposition occurs when attempting distillation.

3. β, ρ, β- trichloroethyl cyanate that

Cl
Cl ₃ C-CH ₂ -OC = NSC = N-Cl

4. «-Naphthylcyanat das

^{ci ci}

\ / - O - C = N - S - C = N - Cl Identification in each case by the IR spectra.

Claims (1)

ascneri residues R with 5- or 6-link systems which also contain heteroatoms such as N, O or S Claim:. «Jn ^ e ^^^ ^ ι · _t μ As bridge members, for example, alkylene Process for the production of new iminocons- "-" with 1 to 6 carbon atoms (preferably acid ester derivatives, characterized by 5 f "^ carbon atoms), furthermore oxygen, sulfur, draws that cyanic acid esters are called the all- * ™ ^s ^ ° carbonate. common formula ™ " * u From iron compounds used cyanine <tis η"" ¹ a _R. , -, like as rvuJS »" n- _ - _.. _β , _ηΓ ΝΠ säureesteir are known. It can for that he R (OCN), _jo J _n ^ _{6 method} z. B. the following Cyansauj - ,, «r a in which R is a haloalkyl radical or a given aromatic radical, optionally substituted mono- and polyalkylphenylphenates, which also /, ^ 'X, visododecyl-, ^ cyclohexyl-, 2-tert-be linked to heterocyclic radicals and? f _tv f, T ^ 'u-methyl-, 2,4-dimethyl-, 3,5-dime bridging members, and η For Buty ^K fi "means: 4. _A llyl-2-methoxyphenyl cyanate ; 1 or 2 stands, with Trichlorrhodan the general, 5 JyK _h ^ ™ _e '^ ₆ 4-Cyanatodiphenyl; Dialkyi formula arSnophenylcyanate like 4-Dimethylamino-, 4-Dime- thvlamino-3-methylphenylcyanate; Acylammophenyl V ¹ _cvanate such as acetylaminophenyJcyanat ;; NitrophenyJ- _ri ς-Λ-N-Cl 20 cyanates such as 4-nitro-, 3-nitro-, 4-nitro-3-methyl, Cl-S CN Ll 20 ^ _Nitro . _{6th methy} , .phenylcyanate; Halophenyl cyanates such as 2-chloro, 3-chloro, 4-chloro 2 4-pichloro,