DE1670815A1 - Process for the production of new urea carboxylic acid chlorides - Google Patents

Description

Process for the production of new urea carbonic acid chlorides.

The present invention relates to a method of manufacture new urea carboxylic acid chlorides by converting disecondary cyclic ureas with phosgene.

According to H. Ulrich, J. N. Tilley and A. A. R. Sayigh (J. Org. Chem. 29 (1963), 2401 to 2404) is formed when one mole of phosgene acts on one Mole of a disecondary urea in organic solution the corresponding allophanic acid chloride, in the case of using a cyclic urea, e.g. B. Ethylenurea, practical exclusively, in the case of the use of an open-chain disecondary urea in addition, the corresponding N, N'-dialkylchloroformamidine, depending on the length of the Alkyl radical in more or less large amounts. When implementing about two Mol Pnosgen with a Hol N, N'-di-n-butylurea, with about two moles of triethylamine were added, the authors did not receive the corresponding urea dicarboxylic acid dichloride, or a mixture of 31% allophanoic acid chloride and 69% N, N'-di-n-butylchloroformamidine-N-carbonychloride.

It has now been found that an'oid nitrogen atoms can be obtained by chlorocarbon oil substituted ureas, d. H. Urea dicarboxylic acid dichloride, the are not yet described in the literature, are obtained in good yields by that - in contrast to the open-chain ureas - one mole of a disecondary cyclic urea at least 2 moles of phosgene, preferably in the presence of one approximately stoichiometric amount of a tert. Amines, can act.

Since the disecondary cyclic ureas from the underlying them Diamines can also be obtained by reacting the latter with phosgene start from disecondary cyclic ureas in situ, d. That is, the urea dicarboxylic acid dichlorides can be used according to the invention also directly by reacting diamines with the corresponding Amount of phosgene in the presence of the appropriate amount of a tert. Amine obtained.

The invention therefore relates to a method for producing new ones Urea carboxylic acid chlorides by converting disecondary cyclic ureas with phosgene, expediently in the presence of an organic solvent, which thereby it is known that one mole of a disecondary cyclic urea, optionally in situ, at least 2 moles of phosgene, preferably in the presence of about 2 moles of a tert. Amine, can act.

Disecondary cyclic ureas suitable for the process are z. B.: A @ ethylene urea, 2-methylethylene urea, 2, 3-dimethylethylene urea, Trimethylene urea, 2-cyclohexylethylene urea, 2-phenylethylene urea, o-phenylene urea, 1, 2-naphthylene urea, 2, 3-naphthylene urea and 4, 5-naphth; lenurea.

As tertiary amines, for. B. suitable: trimethylamine, triethylamine, Tributylamine, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine pyridine, quinoline, N-methyl-decahydroquinoline, N-methylmorpholine and preferably N, N-dialkylaniline, such as N, N-dimethylaniline and N, N-diethylaniline.

It is advantageous to use an excess of phosgene of about 5 - 50% of the stoichiometric amount, while an excess of tert. Amin because of the Risk of side reaction with phosgene should be avoided.

The reaction is carried out because of the low boiling point of phosgene expediently in solvents. Suitable for this 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 method is phosgene to submit with the solvent, a solution of the disecondary urea, geoegangut while cooling, drop in -and the tert. Add amine at reaction temperature. But you can also in a modification of this embodiment to the solution of the Phosgene the tert. Add amine with cooling and then the disecondary urea add gradually at reaction temperature in dissolved or solid form. the Reaction rate is generally in the second stage of the Procedure, d. H. in the substitution of hydrogen on the second nitrogen atom, essential less than in the first stage. Therefore, at low temperature are for this longer response times required. It is useful towards the end of the reaction apply higher temperatures.

The reaction temperature is expediently in the first stage of the reaction between about -10 and about + 30 ° C. After the addition of the tert. Amine has ended or all reactants are combined, the temperature can be up to reflux of the solvent, but generally not above 100 ° C.

Of the tert hydrochloride formed in the reaction.

Amine can either filter the solution of the process product or separated by shaking with ice water. Usually it is not possible to distill the iiarnstoffdicarbonsäuredichloride without decomposition.

The new process products are intended as intermediate products for manufacture of high molecular weight substances are used.

Example 1: In 1 1 dry methylene chloride at -5 to 0 ° C 25Q g (2.5 mol) of phosgene were introduced, then 86 g (1 mol) of ethylene urea were introduced and 242 g (2 mol) of N, N-dimethylaniline were added dropwise at 0 to 20 ° C. in 2 hours. The mixture is then stirred for a further 5 hours at room temperature. Then 500 ml Methylene chloride added and again with excess phosgene distilled off. The reaction solution is cooled to -5 ° G, once with 500 ml of ice-cold, 20% hydrochloric acid and extracted twice with 500 ml of ice water each time. After drying and concentrating the organic phase, 198 g (= 93.8% of theory) of dicarboxylic acid dichloride are obtained of the ethylene urea obtained, pp 97-99 °.

Example 2: In 2, 5 1 dry ethylene chloride at 5 ° C 660 g (6.6 mol) of phosgene presented. For this purpose, a solution is made at 5-20 ° C in 3 1/2 hours of 120 g (2 mol) of ethylenediamine and 968 g (8 mol) of N, N-dimethylaniline in 500 ml Ethylene chloride was added dropwise. Then 2 hours at room temperature, then -6 Stirred at 60 ° C. for hours. To remove excess phosgene, 1 1 ethylene chloride distilled off. After adding 1.5 l of dry methylene chloride is cooled to -5 ° C, once with 1 liter of cold 20% hydrochloric acid and twice with Shake out 1 liter of ice water each time. After drying and concentration of the organic phase 364 g (= 86.4% of theory)) of the ethylene urea are obtained, melting point 99-100 ° (au @ benzene).

Example 3: As in Example 2, a solution of 148 g (2nd Mol) 1,2-diaminopropane and 968 g of N, N-dimethylaniline in 500 ml of dry ethylene chloride added dropwise to the submitted phosgene solution (660 g of phosgene). After processing the Approach are 218 g (= 61.8% of theory) of dicarboxylic acid dichloride of Propylenharnatoffs obtained, m.p. -94 °.

Example 4: 150 g are added to 500 ml of dry chlorobenzene at 4-6 ° C (1.5 mol) of phosgene are introduced, then 67 g (0.5 mol) of benzimidazolone are entered and 121 g (1 mol) of N, N-dimethylaniline were added dropwise at 25 ° C. in the course of 2 1/2 hours. Then is stirred at 25-28 ° C for 4 hours. The excess phosgene is after heating the batch is sucked off to 30 ° C. in a vacuum, the batch with 500 ml of methylene chloride diluted, cooled to -5 ° and shaken out with bis-water.

After drying and reducing the organic phase, 122 g (= 94.4% of Theory) N, N-Benzimidazslen-dicarboxylic acid dichloride obtained. Mp 149-150 ° (from chlorobenzene).

Claims (1)

Claim: Process for the production of new urea carboxylic acid chlorides by reacting disecondary cyclic ureas with phosgene, conveniently in the presence of an organic solvent, characterized in that one mole of one disecondary cyclic urea, optionally in situ, at least two moles Phosgene, preferably in the presence of about two moles of a tert. Amines lets.