Patent GB-609812-A (GB)
Title: Improvements in the manufacture of n-substituted ª‰-aminovinyl derivatives of heterocyclic nitrogen compounds
IPC: C09B23/01
Filed: 1945-01-11
Abstract: N-Substituted b -aminovinyl derivatives of heterocyclic nitrogen compounds are prepared by heating together (a) an alkyl orthoformate, (b) a primary or secondary amine or a formylarylamide, and (c) a quaternary salt of a heterocyclic nitrogen compound having a reactive alkyl group attached to the carbon atom in the 2- or 4-position to the quaternary nitrogen atom or having such group attached to both of such carbon atoms. The reagents may be heated together with or without an organic liquid diluent.  The salts (e.g. acetate or hydrochloride) of the amines may be used.  Methyl, ethyl, n-propyl, n-butyl, or n-amyl orthoformate may be used.  The amine may be aniline, p-methoxyaniline, m-toluidine, p-toluidine, a -naphthylamine, b -naphthylamine, N-methylaniline, N-ethylaniline, piperidine, 1 : 2 : 3 : 4-tetrahydroquinoline, or a heterocyclic primary or secondary amine containing an amino group in the a - or g -position to an intracyclic nitrogen atom, e.g. 2-aminothiazole, 2-aminopyridine, 2 - aminoquinoline or 2 - aminobenzthiazole. Formanilide or an N-naphthylformamide may also be used.  The quaternary salt may be of 2-methylthiazole or a derivative (e.g. 2 : 4-dimethylthiazole, 2 - methyl - 4 - phenylthiazole, 2-methyl-4-(2-thienyl)-thiazole, 2-methylbenzthiazole, 5-chloro-2-methylbenzthiazole, 2 : 5 : 6-trimethylbenzthiazole, or 2-methyl-a - (or -b -) naphthathiazole), of 2-methylselenazole or a derivative, of 2-methyloxazole or a derivative, of 2-methylthiazoline or a derivative, of a 2-methyl-3 : 3-dialkylindolenine, or of 2- or 4-methyl-pyridine or -quinoline or derivatives thereof.  2- or 4-ethyl, -benzyl, or -cyanomethyl derivatives may also be used.  The usual quaternary salts (including n-propobromides) may be used. 2-(b -Anilinovinyl)-b -naphthathiazole metho-p-toluenesulphonate is prepared by heating together 2-methyl-b -naphthathiazole metho-p-toluenesulphonate, ethyl orthoformate and aniline. 2-(b -Anilinovinyl)-pyridine methiodide, 2-(b -Anilinovinyl)-benzoxazole ethiodide, 2-(b -anilinovinyl)-benzoxazole metho-p-toluenesulphonate and etho - p - toluenesulphonate, 2-(b -(p-toluidino)-vinyl)-benzoxazole metho-p-toluenesulphonate, 2 - (b - methylanilinovinyl) - pyridine methiodide, 2-(b -(11-piperidino)-vinyl)-pyridine methoperchlorate, 2-(b -(21-pyridylamino)-vinyl)-pyridine ethiodide, 2 - (b  - (21 - thiazolylamino) - vinyl) pyridine ethiodide, 2-(b -(41-pyridylamino)-vinyl) - pyridine methiodide, 2 - (b  - (21 - pyridylamino) - vinyl) - benzoxazole metho - p - toluenesulphonate, 2 - (b  - (21 - thiazolylamino) - vinyl) - benzoxazole metho - p - toluenesulphonate, 2 - (b  - (1 - morpholyl) - vinyl) - pyridine methoperchlorate, 2-(b -81-quinolylamino)-vinyl)-pyridine methiodide, 2 - (b  - (p - anisidino) - vinyl) - quinoline e etho - p - toluenesulphonate, 2 - (b  - (21 - naphthylamino)-vinyl)-quinoline etho-p-toluenesulphonate, 2-(b -(p-anisidino)-vinyl-benzoxazole etho-p-toluenesulphonate, 2-(b -(p-anisidino)-vinyl)-benzthiazole etho - p - toluenesulphonate, 2 - (b  - (21 - naphthylamino) - vinyl) - benzthiazole etho - p - toluene - sulphonate 4 - b  - anilinovinylpyridine ethiodide, and 2 - b  - anilinovinylthiazoline ethiodide are similarly prepared. 2-(b -Anilinovinyl)-benzoxazole etho-p-toluenesulphonate is also prepared by heating together 2-methylbenzoxazole etho-p-toluenesulphonate, ethyl orthoformate, formanilide and ethyl alcohol.  Specifications 561,172 and 585,707 are referred to.ALSO:N-substituted b -aminovinyl derivatives of heterocyclic nitrogen compounds are prepared by heating together: (a) an alkyl orthoformate; (b) a primary or secondary amine or a formylarylamide; and (c) a quaternary salt of a heterocyclic nitrogen compound having a reactive alkyl group attached to the carbon atom in the 2- or 4- position to the quaternary nitrogen atom or having such group attached to both of such carbon atoms. The reagents may be heated together with or without an organic liquid diluent.  The salts (e.g. acetate or hydrochloride) of the amines may be used.  Methyl, ethyl, n-propyl, n-butyl, or n-amyl orthoformate may be used.  The amine may be aniline, p-methoxyaniline, m-toluidine, p-toluidine, a -naphthylamine, b -naphthylamine, N-methylaniline, N-ethylaniline, piperidine, 1 : 2 : 3 : 4-tetrahydroquinoline, or a heterocyclic primary or secondary amine containing an amino group in the a - or g -position to an intracyclic nitrogen atom, e.g. 2-aminothiazole, 2-aminopyridine, 2-aminoquinoline, or 2-aminobenzthiazole. Formanilide or an N-naphthylformamide may also be used.  The quaternary salt may be of 2-methylthiazole or a derivative (e.g. 2 : 4-dimethylthiazole, 2-methyl-4-phenylthiazole, 2-methyl-4-(2-thienyl)-thiazole, 2-methylbenzthiazole, 5-chloro-2-methylbenzthiazole, 2 : 5 : 6-trimethylbenzthiazole, or 2-methyl-a - (or -b -) naphthathiazole), of 2-methylselenazole or a derivative, of 2-methyloxazole or a derivative, of 2-methylthiazoline or a derivative, of a 2-methyl-3 : 3-dialkylindolenine, or of 2- or 4-methyl-pyridine or -quinoline or derivatives thereof.  2- or 4- ethyl, -benzyl, or -cyanomethyl derivatives may also be used.  The usual quaternary salts (including n-propobromides) may be used. 2-(b -Anilinovinyl-b -naphthathiazole metho-p-toluenesulphonate is prepared by heating together 2-methyl-b -naphthathiazole metho-p-toluenesulphonate, ethyl orthoformate, and aniline. 2-b -Anilinovinyl)-pyridine methiodide, 2-(b -anilinovinyl)-benzoxazole ethiodide, 2-(b -anilinovinyl)-benzoxazole metho-p-toluenesulphonate and etho-p-toluenesulphonate, 2 - (b  - (p-toluidino) - vinyl) - benzoxazole metho - p - toluenesulphonate, 2 - (b  - methylanilinovinyl)-pyridine methiodide, 2-(b -(11-piperidino)-vinyl)-pyridine methoperchlorate, 2-(b -(21-pyridylamino) - vinyl) - pyridine ethiodide, 2 - (b  - (21 - thiazolylamino) - vinyl) - pyridine ethiodide, 2-(b -(41-pyridylamino) - vinyl) - pyridine methiodide, 2 - (b -(21 - pyridylamino) - vinyl) - benzoxazole metho - p - toluenesulphonate, 2 - (b  - (21 - thiazolylamino)-vinyl) - benzoxazole metho - p - toluenesulphonate, 2 - (b  - (1 - morpholyl) - vinyl) - pyridine methoperchlorate, 2 - (b  - 81 - quinolylamino) - vinyl)-pyridine methiodide, 2-(b -(p-anisidino)-vinyl)-quinoline etho - p - toluenesulphonate, 2 - (b -(21 - naphthylamino) - vinyl) - quinoline etho - p - toluenesulphonate, 2 - (b  - (p - anisidino) - vinylbenzoxazole etho-p-toluenesulphonate, 2-(b -(p-anisidino) - vinyl) - benzthiazole etho - p - toluenesulphonate, 2 - (b  - (21 - naphthylamino) - vinyl)-benzthiazole etho-p-toluenesulphonate, 4-b -anilinovinyl pyridine ethiodide, and 2-b -anilinovinylthiazoline ethiodide are similarly prepared.  2 - (b  - Anilinovinyl) - benzoxazole etho - p - toluenesulphonate is also prepared by heating together 2-methylbenzoxazole etho-p-toluenesulphonate, ethyl orthoformate, formanilide, and ethyl alcohol.  Specifications 561,172 and 585,707 are referred to.