Patent GB-912266-A (GB)
Title: Polyvinyl alcohol photographic silver halide emulsions
Inventor: SPRUNG JOSEPH ASHER
IPC: C07D217/22
Filed: 1960-01-18
Abstract: N-alkyl (C14, C16 or C18)-dimethylamines are prepared by heating the long chain primary amine with paraformaldehyde and formic acid in benzene.  Diamines are prepared by condensing 1,10-dibromodecane with ethylene diamine, morpholine, n-dibutylamine or diethylamine. Ethyl-a -aminolaurate is prepared as its hydrochloride by saturating the acid in ethanol with hydrogen chloride.  The product may be dissolved in methanol and saturated with ammonia to give the amide.  Tertiary amines having carbamyl groups in the long chain are prepared by reacting hexadecyl amine with methyl N,N-dimethylglycinate or with sodium N,N-diethylglycinate, by reacting 3-dimethylaminopropylamine (or the corresponding diethyl compound) with C8 to C18 acids or with sebacyl chloride, or by reacting myristoyl halide with 6-aminoquinoline or 2-aminopyridine.  A secondary amine is prepared from benzylamine and tetradecylbromide.  Amidines are prepared by reacting C8 to C18 primary amines or p-tetradecyloxyaniline with S-methyl isothiouronium p-toluene sulphonate.  Biguanides are obtained by reacting dicyandiamide with dodecylamine or hexadecylamine p-toluene sulphonate, 4-decoxyaniline or the condensation product of polyoxymethylene and aniline.  Quaternary ammonium compounds of the type R-N(R1)2.R2X are obtained by quaternizing a tertiary amine with a compound R2X wherein R1 is methyl or ethyl, R is long chain alkyl which may be interrupted by carbamyl, phenoxy, phenoxyethoxy, phenoxy carbamyl or -SO2NH- groups, or R is a substituted or unsubstituted succinimidopropyl group, R2 is alkyl which may be substituted by phenyl, carboxylic acid ester amide or substituted amide, or benzoyl groups or is benzthiazolyl or quinolyl and X is an anion.  Quaternary pyridinium and benzthiazolium salts which may have a carboxylic acid ester or substituted amide group in the ring and, on the quaternary N atom an alkyl group which may have a phenyl, carboxylic acid ester or amide substituent, are prepared by quaternizing the corresponding bases.  Quaternary hydrazine compounds are prepared by heating N,N-dimethyl hydrazine with a C12 to C18 alkyl halide; the free amino group may then be acylated.  Similar acylated quaternary hydrazines are prepared from palmitic or stearic acid dimethyl hydrazide and methyl p-toluene sulphonate.  A ternary sulphonium compound is prepared from tetradecyl-ethyl sulphide and methyl iodide.  Substituted amino carboxylic acids are obtained by reacting C10 to C18 primary or secondary amines with halo-carboxylic acids or alkyl sulphonic acids, including e -benzoylamino-a -bromo-caproic acid (followed by hydrolysis of the benzoyl group), in certain instances both the hydrogen atoms of the amino groups being replaced by acidic groups. Alternatively, the long chain halide may be reacted with an amino-carboxylic acid.  a -Decyl-glycine and its N-b -hydroxy ethyl derivative are prepared from a -bromo-lauric acid and concentrated ammonium hydroxide or b -amino ethanol respectively. d -Hexadecylaminobutyric acid is prepared by refluxing N-hexadecyl-2-pyrrolidone in hydrobromic acid.  a  - Octadecenyl - N - (g -dimethylaminopropyl)-mono-succinamide is prepared by alkaline hydrolysis of N - (g  - dimethylaminopropyl) succinimide with sodium hydroxide.  Betaines, which may contain more than one carboxyl group and in which the amino N-atom may form part of a ring or which may be substituted by ether, hydroxy, amido, sulphonamido, succinimido or further amine containing groups, are prepared in general by heating a tertiary amine with a halo-carboxylic acid in the presence of sodium hydroxide, or with a halo-carboxylic ester in the presence of a basic ion exchange resin.  Betaines also are produced by reacting hexadecyl-dimethyl-2-bromoethyl ammonium bromide with aqueous sodium sulphite or sodium thiosulphate in ethanol.  A carboxy sulphonium betaine is prepared from tetradecyl-ethyl sulphide and chloracetic acid.  N-Lauroyl-arginine is prepared from arginine and lauroyl chloride.  An amidine is prepared from dodecyltaurine and cyanamide. Bis[5 - amino - 1;2;4-triazolyl-3]disulphide is prepared by oxidizing imino-thiourazole with alkaline potassium persulphate. 2-Undecyl-benzimidazole is prepared by heating o-phenylene diamine and lauric acid.  Acylated heterocyclic or benzene amino compounds are obtained by acylating 2-aminobenzimidazole, histidine or its methyl ester, guanine, 5 - amino - tetrazole, 6 - amino - 2 - mercapto - benzthiazole, 5-amino-2-mercapto-benzimidazole or a hydroxy-amino-benzoic acid with long chain acid halides such as decanoyl chloride or tetradecanoyl chloride, or by acylating 6-amino-2-mercapto-benzthiazole with octadecenyl-succinic anhydride. Similarly, both amino groups of cystine or its ethyl ester are acylated with C8 to C16 acid chlorides. S-tetradecyl thiourea hydrobromide is prepared from thiourea and tetradecyl bromides. Amides of thioglycolic acid are obtained by heating the acid with C12 to C18 primary amines. 2-Mercapto-quinolines or 1-mercapto - isoquinolines having a nuclear lauramido substituent are obtained by treating the corresponding 2-(or 1)chloro compounds with thiourea. 2-Mercapto-4-hydroxy-6-tridecyl-pyrimidine is prepared by heating ethyl tetradecanoyl acetate with excess thiourea.  Quaternary ammonium compounds are produced by heating 2-bromoethyl-hexadecyl-dimethyl ammonium bromide with thiourea, and by heating hexadecyl-dimethylamine with p-(b -bromoethoxy)-phenol, with benzimidazole, 5-nitrobenzimidazole or imidazole having a chloromethyl substituent, or with thiazole, benzthiazole, triazole or tetrazole having a 2 - halo - acetamido substituent.  a -Hydroxymyristic acid is prepared by heating the a -bromo compound in aqueous potassium hydroxide.  Alkyl sulphates are prepared from myristyl or octadecyl alcohol and chlorosulphonic acid.