DE1670815B2 - Process for the preparation of N, N'-di-chlorocarbonyl urea derivatives - Google Patents

Description

HN-C-NH

in which R is an ethylene radical which is optionally substituted by methyl, cyclohexyl or phenyl or denotes the propylene, 1,2-phenylene, 1,2-, 2,3- or 4,5-naphthylene radical, characterized in that that one mole of a cyclic urea derivative of the general formula 11 "

HN-C-NH

(Π)

in which R has the meaning already mentioned, in the presence of an organic solvent with at least 2 moles of phosgene.

2. The method according to claim 1, characterized in that the cyclic urine substance derivative used is used of the general formula II by reacting the corresponding diamine with phosgene manufactures and immediately continues to implement without insulation.

3. Process according to Claims 1 and 2, characterized in that the reaction is carried out in Presence of about 2 moles of a tertiary amine makes.

According to H.Ulrich, JN T i 11 ey and AAR S ayigh (J. Org. Chem., 29 [1963], pp. 2401 to 2404), the action of 1 mole of phosgene for each mole of a disecondary urea in organic solution produces this corresponding allophanoic acid chloride, in the case of using a cyclic urea, IB ethylene urea, practically exclusively, in the case of using an open-chain disecondary urea also the corresponding Ν, Ν'-dialkylchloroformamidine, depending on the length of the alkyl radical in more or less large amounts. When about 2 moles of phosgene were reacted with 1 mole of Ν, Ν'-di-n-butylurea, in which about 2 moles of triethylamine were added, the authors did not receive the corresponding Ν, Ν'-di-chlorocarbonylurea, but a mixture from 31 % allophanoic acid chloride and 69% Ν, Ν'-di-n-butylchlorformamidine-N-carbonyl chloride.

It has now been found that N, N'-di-chlorocarbonyl urea derivatives of the general formula I.

C N-C-N C Cl

in which R has the meaning already mentioned, in the presence of an organic solvent converts at least 2 moles of phosgene.

Since the cyclic urea derivatives mentioned can be obtained from the diamines on which they are based by reaction of the same with phosgene, one can also start from the cyclic urea derivatives mentioned in situ, ie the N, N'-dichlorocarbonyl urea derivatives of the general formula can be used I according to the invention also obtained directly by reacting corresponding diamines with the corresponding amount of phosgene, if appropriate in the presence of the corresponding amount of a tertiary amine, without isolating the compounds of the general formula II.
It is preferred to work in the presence of about 2 moles of a tertiary amine.

Cyclic ureas suitable for the process are e.g. B. ethylene urea, 2-methylethylene urea, 2.3 - Dimethylethylene urea, trimethylene urea. 2- cyclohexylethyl urea, 1- phenylethylene urea, o-phenylene urea, 1,2-naphthylene urea, 2,3 - naphthylene urea and 4,5 - naphthylene urea.

As tertiary amines, for. B. suitable trimethylamine, Triethylamine, tributylamine, N, N'-dimethylcyclohexylamine, Ν, Ν'-dimethylbenzylamine, pyridine, Quinoline, N-methyl-decahydroquinoline, N-methylmorpholine and preferably N, N-dialkylanilines such as N, N-dimethylaniline and N, N-diethylaniline.

It is advantageous to use an excess of about 5 to 50% of the stoichiometric amount of phosgene Amount, while more than 2 moles per mole of the compounds of the general formula II of tert-amine should be avoided because of the risk of side reactions with phosgene.

Suitable solvents are e.g. B. hydrocarbons such as benzene, toluene and tetrahydronaphthalene, Chlorinated hydrocarbons, such as methylene chloride, chloroform, Carbon tetrachloride, ethylene chloride, chlorobenzene and dichlorotoluene, and esters such as ethyl acetate and butyl acetate.

A suitable embodiment of the process consists in submitting phosgene with the solvent, a solution of a compound of the general formula II, optionally with cooling, to be added dropwise and the tert. Add amine at reaction temperature. But you can also change it this embodiment to the solution of the phosgene the tert. Add amine with cooling and then the cyclic urea derivative at reaction temperature Gradually add in dissolved or solid form. The reaction rate is generally in the second stage of the process, d. H. in the substitution of hydrogen on the second

Nitrogen atom, much less than in the first 2O ⁰ C in 3 ¹ /, hours a solution of 120 g (2MoI) stage. For this reason, ethylenediamine and 968 g (δ mol) N, N-dimethyl longer reaction times are required at low temperatures. Aniline in 500 ml of ethylene chloride is expediently added dropwise. Anes, towards the end of the reaction, higher temperatures should be used for 2 hours at room temperature. 5 then stirred ^{at 60 °} C. for 6 hours. For the purpose of the first stage of the reaction, excess phosgene is removed, and the ethylene retention temperature is expediently distilled off between about -10 and chloride. After adding 1.5 1 dry about +30 ^r C. After the addition of the tert. Amine methylene chloride is cooled to -5 ⁰ C, is finished once all the reactants or together with 11 of cold 20% hydrochloric acid and are given twice with the temperature can be up to reflux shaken xo 1 1 ice water. After drying and Eines the solvent, but generally not over the narrow organic phase, 364 g (= 86.4% 100 ⁼ C, are increased. Of theory) dicarboxylic acid dichloride of the ethylene

Obtained from the hydrourea formed during the reaction, melting point 99 to 100 ° C. (from benzene).
chloride of tert. Amine can be removed from the solution of the process product either by filtration or by 15

Shake off with ice water. In der B is ρ ie 1 3
Usually it is not possible to use the process products

to distill without decomposition. According to Example 2, a solution is made

The new process products can be obtained as between 148 g (2 mol) 1,2-diaminopropane and 968 g N ₁ N-di-

products for the production of high molecular weight substances 20 methylaniline in 500 ml of dry ethylene chloride

to serve. into the presented phosgene solution (660 g phosgene)

Example 1 tropi't. After working up the batch, 278 g

(= 61.8% of theory) dicarboxylic acid dichloride des

In 11 dry methylene chloride are obtained at -5 to methylethylene urea, m.p. 92 to 94 ° C.
O ⁰ C 250 g. (2.5 mol) phosgene introduced, then 86 g 25
(1 mol) ethylene urea registered and 242 g

(2 mol) N, N-dimethylaniline at 0 to "20 = C in 2 hours - Example 4
the dripped in. Then another 5 hours

stirred at room temperature. Then 500 ml. In 500 ml of dry chlorobenzene are at 4 to

Methylene chloride is added and 150 g (1.5 mol) of phosgene are passed in with excess 30 6 "C, then

Phosgene distilled off again. The reaction solution registered 67 g (0.5 mol) of benzimidazolone and 121 g

is cooled to -5 C, once with 500 ml of ice-cold, (1 mol) Ν, Ν-dimethylaniline in 2V ₂ hours

20% hydrochloric acid and twice with 500 ml of ice water at 25 ° C. each time are added dropwise. This is followed by 4 hours at 25 ° C.

shaken out. After drying and concentration, the mixture is stirred to 28 ° C. The excess phosgene will

ganic phase, 198 g (= 93.8% of theory) 35 by heating the batch to 3O ⁰ C in vacuo

Dicarboxylic acid dichloride of the ethylene urea obtained, the batch with 500 ml of methylene chloride

th, m.p. 97-99 ° C. diluted, ^{cooled to -5 0} C and with ice water

Example 2 shaken out. After drying and concentrating the

organic phase are 122 g (= 94.4% of

In 2.51 dry ethylene chloride at 5 ° C 40 theory) N.N-Benzimidazolon-dicarboxylic acid dichloride

660 g (6.6 mol) of phosgene presented. In addition, at 5 to is obtained. Mp. 149 to 15O ⁰ C (from chlorobenzene).

Claims (1)

Patent claims 1. Process for the preparation of N.N'-Dihi d lli in R one optionally by methyl, cyclohexyl or phenyl-substituted ethylene radical or the propylene, 1,2-phenylene, 1,2-, 2,3- or 4,5-naphthylene radical means, can be produced by lh Hffd d l 1. Process for the preparation of N.N-Di lenrest means d, one chlorocarbonyl urea derivatives of the general 5 1 mol of a cyclic urea denvates of all-Fl I mean formula II Formula I. y
common formula II