DE1445676A1 - Process for the preparation of hydantoins which are benzoyl-substituted in the 3-position - Google Patents

Description

Process for the production of hydantoins which are benzoyl-substituted in the 3-position (addendum to patent application D 40 530 IVd / 12 p, DAS 1 213 414) The subject of patent application D 39 046 IVd / 12 p (= DAS 1 207 391) is a process for producing heat 3-Benzoyl-5, 5-dimethylhydantoins of the general formula in which R denotes a hydrogen atom or alkyl, cycloalkyl, aryl, aralkyl or acyl groups, which is characterized in that a mixture of hydantoins of the general formula with approximately equivalent amounts of alkali or. Alkaline earth hydroxides in organic, water-immiscible solvents are dehydrated by azeotropic distillation and the anhydrous salts obtained are reacted with benzene halides at temperatures below 150 ° C. without isolation.

As alkali or. Alkaline earth hydroxides are preferably used Potassium or calcium hydroxide.

The additional patent application D 40 530 IVd / 12 p (. DAS 1 213 414) relates to a modified process for the preparation of hydantoins which are benzoyl-substituted in the 3-position and unsubstituted in the 5-position, which is characterized in that, as in the 3- Position of unsubstituted hydantoins are those of the following general formula used.

In a modification of the process for the preparation of hydantoins unsubstituted in the 3-position by mixing hydantoins unsubstituted in the 3-position with approximately equivalent amounts of alkali or alkali metals. Alkaline earth hydroxides in organic, water-immiscible solvents, dehydration by azeotropic distillation and reaction of the resulting anhydrous salts without isolation with benzoyl halides at temperatures below 150 ° C according to patent application D 40 530 IVd / 12 p (. DAS 1 213 414) has now been found that hydantoins which are unsubstituted in the 3-position are those of the general formula in which R is alkyl, cycloalkyl, arylalkyl and acyl groups, can be used.

The alkyl derivatives preferably include those having 1 to 5 carbon atoms in straight or branched chain, to the cycloalkyl derivatives "..J </ \ '.; t'"?: <<! <T. ' those with 5 to 11 carbon atoms, where the ring carbon atoms' '' J; '' .'.'-. '' "K .-, i ':' ''. t: .'.- '.' <f-- ; - ;.

Alkyl side chains with up to 5 carbon atoms can carry too den ....'- f - '.' f .... r .-. f,., .....-,: arylalkyl derivatives those with 7 to 12 carbon atoms (in particular with up to 4 carbon atoms per alkyl group), the aryl radicals of the arylalkyl groups mentioned additionally by one or two lower alkyl groups may be substituted, and the acyl groups include the residues of aliphatisohen Carboxylic acids with 2 to 6 carbon atoms and the benzoyl group. Connections with In principle, higher carbon numbers than those mentioned are accessible to the process, but technically more difficult to represent, with the production of the starting materials to be considered.

The derivatives of 3-benzoylhydantoin produced can advantageously as - '.' "';.)' .. '..' 'Activatorsinwashing and bleaching baths that are peroxides or peroxidic M6ttel included, can be used. They have been used as activators, as far as they have been so far Overlooks the particular advantage of good storage. stability in washing and Bleach.

~, nni-'7.

The compounds obtained by the methods of the invention are new, - "'" \. <' '' '. and cannot be produced by the previously known methods.

The hydantoins used as starting substances were after or based on the literature sources "Reports of the German Chemical Society" 6, Page 1278 and "Journal für Praxis Chemie" 2, 113, pages 252-254 and page 264 produced. The 1-methyl-hydantoin with a melting point of 157 to 158 ° C obtained by heating equimolar amounts of sarcosine and urea to 130 ° C and subsequent recrystallization from water in pure form. This representation. is contained in the first cited reference.

The 1-benzyl-hydantoin with a melting point of 139 ° C and the 1-cyclohexyl-hydantoin with a melting point of 183 ° C are, according to the applicant's knowledge, in the literature not described; they were based on the literature source named second above made from N-Benzylglyoin resp.

N-Cyclohexylglyoin, Potassium Oyanate, and Hydrochloric Acid. Here was a Solution of the glycine derivative in water at 30 ° C with potassium yanate in 50% excess. Sohuss added together over the molar amount and heated to 90 ° C. After that it was cooled again and acidified with concentrated hydrochloric acid. To complete of the ring closure was boiled for a further 30 minutes under rotary flow.

The 1-Cyolohexyl-hydantoin was also obtained by heating equimolar Quantities of N-cyclohexylglycine and urea produced at 160 ° C. The two methods The substances shown are identical to one another.

Example 1 1-methyl-3-benzoylhydantoin 114 g of 1-methylhydantoin (melting point 157 to 158 ° C), 1,000 ccm of toluene, 40 g of caustic soda and 40 g of distilled water are heated to the boil while stirring. The solution water as well as the resulting Water of reaction are distilled off azeotropically. The anhydrous mixture is left expediently cool slightly and 147 g of benzoyl chloride are added dropwise with stirring. the The reaction is terminated by brief refluxing. After that, the retired Sucked off table salt, clarified the filtrate with charcoal and for the most part in a vacuum constricted. By adding ether, 1-methyl-3-benzoylhydantoin can crystallize accelerate. After suctioning off, it is washed with ether and dried.

Yields 157 g (-72% of theory). Melting point 86 to 87 ° C.

Example 1 1-Benzyl-3-benzoylhydantoin The basic structure of this benzoyl compound, 1-benzylhydantoin is not described in the literature. However, he let himself be according to the procedure described in the Journal of Practical Chemistry (2). 113, pages 252 to 254, analogous to 1-methyl-hydantoin. The melting point was found to be 139 ° C. The quantitative determination showed for Found Calculated C = 63.44% C = 63.16% H-5, 08% H-5, 26% N-14, 67% N-14, 60% The benzoylation was according to the invention carried out as follows: t92 g of 1-benzylhydantoin, 1,000 com of toluene, 56 g Caustic potash and 40 g of distilled water are heated to the boil while stirring. That The water of solution and the water of reaction formed are distilled off azeotropically. You let it cool a little and 147 g of benzoyl chloride are added dropwise with stirring. The implementation is terminated by refluxing. Thereafter, potassium chloride is excreted from the body suctioned off, the filtrate ge-RI with charcoal and concentrated in vacuo. By adding Ether accelerates the crystallization of 1-benzyl-3-benzoylhydantoin. In the end one sucks off and rinsed with Xther.

Yields 203 g (= 69% of theory). Melting point 97 to 99 ° C.

Example 3'-cyclohexyl-3-benzoylhydantoin 1-Cyolohexylhydantoin was carried out in an analogous manner according to that in the Journal for practical chemistry (2) 113, pages 252 to 254 shown method.

A melting point of 183 ° C. was found for 1-cyclohexylhydantoin and the quantitative analysis showed a good agreement with the calculated Amounts Found: Calculated C = 59.3% C = 59.3% H = 7.9% H = 7.7% N-15.8% N-15.4% The benzoylation was carried out as in Examples 1 and 2.

Claims (3)

Patent claims 1.) Modification of the process for the preparation of hydantoins which are benzoyl-substituted in the 3-position by mixing in the 3-position. unsubstituted hydantoins - with approximately equivalent amounts of alkali - or. Alkaline earth hydroxides in organic, water-immiscible solvents, dehydration by azeotropic distillation and reaction of the anhydrous salts obtained without isolation with benzoyl halides at temperatures below 150 ° C according to patent application D 40 530 IVd / 12p (DAS 1 213 414), characterized in that one than hydantoins unsubstituted in the 3-position are those of the general formula in which R is alkyl, cycloalkyl, arylalkyl and acyl groups, is used. 2.) Compounds of the general formula in which R can mean: an alkyl group with 2 to 5 carbon atoms in a straight or branched chain, a cycloalkyl group with 5 to 11 carbon atoms in which the ring carbon atoms can carry alkyl side chains with up to 5 carbon atoms, an arylalkyl group with 7 to 12 carbon atoms in which the aryl radicals can additionally be substituted by dhe or two lower alkyl groups or an acyl group which is derived from aliphatic carboxylic acids having 2 to 6 carbon atoms or from benzoic acid. 3.) Compounds of the general formula too in which R can mean: an alkyl group with 1 to 5 carbon atoms in a straight or branched chain, a cycloalkyl group with 5 to 11 carbon atoms in which the ring carbon atoms can carry alkyl side chains with up to 5 carbon atoms, an arylalkyl group with 7 to 12 carbon atoms in which the aryl create can additionally be substituted by one or two lower alkyl groups or an acyl group which is derived from aliphatic carboxylic acids with 2 to 6 carbon atoms or from benzoic acid.