Patent GB-671917-A (GB)
Title: Mono and polymeric amides of alkylenimines and acetoacetic acid and process of producing same
IPC: C07D203/18
Filed: 1947-11-27
Abstract: Polymeric amides of alkylenimines and acetoacetic acid are made by acylating a monoalkylenimine with diketene and polymerizing the product or by acylating a polyalkylenimine with diketene. Reaction proceeds readily at room temperature.  Azinidine, 2-methyl-, 2-ethyl-, 2,3-dimethyl-, 2,2-dimethyl-, 2,2,3 - trimethyl -, and 2,2 - dimethyl - 3 - propyl-aziridine are specified alkylenimines. Completely or partially acylated polymers may be obtained the latter products forming thermo-reversible gels and, depending on the alkylenimine chosen and the proportions of reactants taken from water soluble to water insoluble amides in which from 5 to 100 per cent of the secondary amino groups are acylated are obtained.  Water soluble products are usually obtained from water soluble polyalkylemines. Insoluble products may be moulded.  In examples (1) diketene is added to aqueous polyethylenimine at 40-50 DEG  C., on cooling in ice water a colourless gel is formed which liquefies at about 75 DEG  C. and regells at about 65 DEG  C. and may be used as a gelatin extender in silver halide photographically-active emulsions for azo dye formation, e.g. an ammoniacal solution of the gel is treated with aqueous dianisidine diazonium chloride-zinc chloride complex to give a dark yellow colour and in colour photography since it is capable of azomethine formation; (2) diketene is added over a period of half an hour to aqueous polyethylenimine, the temperature rising to 75 DEG C. and the mixture is kept alkaline with additions of 40 per cent aqueous NaOH, the cooled product does not gel but gelling is effected by adjusting the pH to 6 with acetic acid and adding 2 per cent aqueous adipic acid dihydrozide acidified by acetic acid and in (3) diketene is added over a period of about 1 1/2 hours to monomeric ethylenimine at below 60 DEG  C., the product polymerized in situ and is largely insoluble in water although a water soluble polymer may be made at a lower temperature.  In the Specification as open to inspection under Sect. 91, other acylating agents are specified, e.g. 1-butene-1,3-diones including 2,4-dimethyl-, 2,4-diisopropyl-, 2,4-di-n-butyl-, 2-n - butyl - 4 - methyl, 4 - n - butyl - 2 - methyl -, 2 - n - hexyl - 4 - methyl -, 4 - n - decyl -, 2,4-di - n - decyl, 2,4 - di - n - hexadecyl - and 2,4-diphenyl - 1 - butene - 1,3 - dione.  This subject-matter does not appear in the Specification as accepted.ALSO:Amides of alkylenimines and acetoacetic acid are made by acylating an alkylenimine with diketene.  Aziridine, 2-methyl aziridine, 2-ethyl-, 2,3-dimethyl-, 2,2-dimethyl-, 2,2,3-trimethyl- and 2,2-dimethyl-3-propyl-aziridine are specified alkylenimines. Reaction proceeds at room temperature the products readily polymerizing.  In example (3) ethylenimine is added to diketene at below 60 DEG  C. and after 1 1/2 hours reaction ceased and polymerization suddenly occurred.  In the Specification as open to inspection under Sect. 91, other acylating agents are specified, e.g. 1-butene-1,3-diones including 2,4-dimethyl - 1 - butene - 1,3 - dione, 2,4 - di-isopropyl-, 2,4-di-n-butyl-, 2-n-butyl-4-methyl-, 4 - n - butyl - 2 - methyl-, 2 - n - hexyl - 4-methyl-, 4-n-decyl-, 2,4-di-n-decyl-, 2,4-di-n-hexadecyl-, and 2,4 - diphenyl - 1 - 1,3-dione.  This subject-matter does not appear in the Specification as accepted.ALSO:Polymeric amides of alkylenimines and acetoacetic acid made by acylating a monomeric alkylenimine with diketene and polymerizing the product or by acylating a polyalkylenimine with diketene may form azo dyes.  For further details of the preparation of the amides (see Group IV (a)).  In example 1 a gel made by treating aqueous polyethylenimine with diketene at 40-50 DEG  C. with subsequent cooling in ice water is dissolved in aqueous ammonia and aqueous dianisidine diazonium chloride-zinc chloride complex added to give a dark yellow colour.