DE1221213B - Process for the preparation of isocyanide dihalides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day;

C07c

German class:. 12 ο-22

1221213
F40571IVb / 12o
23rd August 1963
July 21, 1966

It is known that salts of monosubstituted dithiocarbamic acids can be used in various ways, z. B. with heavy metal salts, chlorocarbonic acid esters, phosgene, sodium chloride, sodium chloride or iodine, in the Can transfer mustard oils (see Houben - Weyl, Methods of Organic Chemistry, 4th edition, Vol. X, Pp. 869 to 873).

It is also known that mustard oils can be converted into the corresponding isocyanide dichlorides by chlorination can convert (see Chemical Reports, 7, p. 1228, vol. 1874, and Annalen der Chemie, 663, p. 46, vol. 1963).

It has now been found that isocyanide dihalides are obtained if one, if appropriate, is used substituted alkyl, cycloalkyl or aryl radical monosubstituted dithiocarbamic acid salts chlorinated. the The reaction can be illustrated by the following reaction scheme, in which cyclohexyldithiocarbamidsaures Sodium is chlorinated:

• NHC - S - Na + 4 Cl ₂

Process for the production of
Isocyanide dihalides

, Cl

) -n = c;

+ NaCl + HCl + 2 SCl ₂

It is also not necessary that the dithiocarbamic acids Salts as pure starting materials Applicant;

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Engelbert Kühle,

Dr. Bertram Anders, Cologne-Stammheim

are present, but the dithiocarbamic acids salts can also be present in the same way as they are in their Incurred production, z. B. in the reaction of 2 moles of a primary amine with 1 mole of carbon disulfide, This procedure can be illustrated by the following reaction scheme, in which again Cyclohexyldithiocarbamidsaures salt is chlorinated, which is obtained by reacting 2 moles of cyclohexylamine and 1 mole of carbon disulfide was obtained:

■ NH ₂ + CS ₂

4CL,

NH ₅ , • HS - C - NH

S.
H y- NCCl ₂ + <H> - NH ₂ • HCl + HCl + 2 SCl ₂

The monosubstituted dithiocarbamic acids salts, which contain an optionally substituted alkyl, cycloalkyl or contain aryl radical, z. B. be substituted by alkoxy groups, halogen, etc. if the dithiocarbamic acid salts, as described above, by reacting a primary amine with Carbon disulfide prepared can be used as the amine z. B. the following connections are used: Methylamine, ethylamine, isobutylamine, dodecylamine, 3-ethoxypropylamine, cyclopentylamine, cyclohexylamine, Aniline, toluidine, anisidine, chloroaniline, 1-naphthylamine, ethylenediamine, 1,6-hexamethylenediamine or 1,4-phenylenediamine if primary diamines are used become, such as B. ethylenediamine or p-phenylenediamine can also have two dithiocarbamide salt groups be contained in the molecule.

The dithiocarbamic acids salts, ammonium or alkali metal cations or ammonium cations can be used as cations contain the amine used, as z. B. in the production of dithiocarbamic acids Salts from the amine by reaction with carbon disulfide are described above.

The process according to the invention is expediently carried out in an inert and under the reaction conditions non-halogenable organic solvents such as methylene chloride, chloroform, carbon tetrachloride, Chlorobenzene or dichlorobenzene, carried out by adding the anhydrous dithiocarba-

609 590/400

slurried mid-acid salt in the solvent and at 0 to 50 ° C, preferably 10 to 30 ° C, chlorinated, z. B. with chlorine or sulfuryl chloride. Stronger cooling is sometimes useful here. After the Reaction sucks off the resulting salt and wins the isocyanide dihalide z. B. by distillation.

The isocyanide dihalides can be used as pesticides, e.g. B. as nematicides or soil fungicides, be used. But they also serve as intermediate products for the production of new organic products Links.

example 1

198 g of cyclohexylamine are dissolved in 450 ml of carbon tetrachloride and, while cooling at 5 to 40 ° C., 90 g of carbon disulfide are added dropwise. The mixture is stirred for a while and the excess carbon disulfide is distilled off up to a transition temperature of 75 ° C. (about 75 ml). The reaction mixture is cooled and a total of 284 g of chlorine is passed in at 10 to 30 ° C. over the course of 4 hours. The chlorination is very exothermic at the beginning, but becomes weaker when the evolution of hydrogen chloride begins. After a small initial run, 142 g of isocyanide dichloride = 79%, based on the cyclohexylamine used, are obtained. Kp. 79bis82 ₁₃ ° C.

Example 2

55 g of sodium cyclohexyldithiocarbamic acid dried at 120 ° C. are suspended in 400 ml of carbon tetrachloride and charged with a total of 80 g of chlorine while cooling at 5 to 15 ° C. The mixture is stirred for 1.5 hours, sodium chloride is filtered off with suction, concentrated in vacuo and, by distillation, 30 g = 60% cyclohexyl isocyanide dichloride with a boiling point of ₁₄ 80 to 82 ^° C. is obtained.

Example 3

36 g of ammonium phenyldithiocarbamic acid are mixed in 200 ml of carbon tetrachloride below 12 ° C. with 55 g of chlorine. After stirring lstündigem is filtered off and concentrated in a vacuum, and by subsequent distillation 13.5 g = 40 ° / ₀ of theory ίο phenyl isocyanide dichloride of boiling. _16100-103 ° C

Example 4

To the solution of 99 g of cyclohexylamine in 250 ml of carbon tetrachloride, 40 g of carbon disulfide are added dropwise with cooling at 10.degree. To 30.degree. The mixture is stirred for 1 hour and then 268 g of sulfuryl chloride are added at 5 to 28 ° C. while cooling with ice water. After several hours of stirring, the precipitated cyclohexylamine hydrochloride is suctioned off, the filtrate is concentrated in vacuo and the cyclohexyl isocyanide dichloride is distilled in vacuo at bp ₁₂ 80 to 82 ° C. In an analogous manner, when the cyclohexylamine is replaced by methylamine or n-propylamine or n-butylamine the following compounds:

CH ₃ -NCCl ₂
nC ₃ H ⁷ -NCCl ₂
nC ₄ H _e - NCCl ₂

B.p. 75 to 79 ° C
B.p. 125 to l27 ° C
Bp _M 40 to 45 ° C

Claims (2)

Patent claims: 1. A process for the preparation of isocyanide dihalides, characterized in that that one is monosubstituted by an optionally substituted alkyl, cycloalkyl or aryl radical dithiocarbamic acid salts chlorinated. 2. The method according to claim 1, characterized in that the chlorination in the temperature range from 0 to 50 ° C, preferably from 10 to 30 ° C. 609 590/400 7.66 © Bundesdruckerei Berlin