Patent GB-539937-A (GB)
Title: Improvements in the use of arylamines in photography
IPC: G03C5/30
Filed: 1940-03-26
Abstract: 539,937. Quaternary ammonium compounds. KODAK, Ltd. (Eastman Kodak Co.). March 26, 1940, No. 5407. [Class 2 (iii)] [Also in Group XX] A developing agent comprises a compound of the general formula wherein X is an NH 2  substituted NH 2  or OH group and is in the o- or p-position, R is hydrogen, substituted or unsubstituted alkyl, aryl, alkylene, heterocyclic, or cycloaliphatic group, or a group of the type -R<SP>1</SP>Q, R<SP>1</SP> is an organic grouping, and Q is a quaternary ammonium group to the nitrogen atom of which R' is attached. The group R may be attached to R<SP>1</SP> by one of the non-polar linkages of the nitrogen atom. The benzene ring may form part of a naphthalene or other polynuclear system, and the rings may be further substituted by one or more halogen atoms, or by alkyl, substituted alkyl, alkoxy, hydroxy or amino group. R<SP>1</SP> may be a group of the type -(CH 2 )n or -(CH 2 )nSO 2 O-, where n is 1, 2 or other integer and any of the hydrogen atoms can be replaced by alkyl or hydroxy groups. The quaternary ammonium groups may be a pyridium group. N-ethyl : N- #-bromethyl-p-aminophenol is prepared by the action of ethylene bromide on N-ethyl-p-aminophenol. N p - - hydroxyphenyl N - ethylaminoethyl-  pyridinium bromide is prepared by heating a solution of N-ethyl-N- #-bromethyl-p-aminophenol in dry pyridine to boiling. The following compounds are similarly prepared : (1) p-amino-m-methyl-N : N-di (ethyl- # - pyridinium chloride) - aniline; (2) N - ethyl - N - p - amino - m - - methylphenylaminoethyl pyridinium chloride ; (3) N - p - - hydroxy m - - methylphenylaminopropylquinolinium bromide; and the compound of the formula. Methyl N - p - amino - m - hydroxyphenyl - N-hydroxyphenylethylsulphonate is prepared by treating #-bromethane sulphonic acid with PCl 5 , distilling, esterifying with methyl alcohol, heating with p-(p<SP>1</SP>-nitro-m<SP>1</SP>-hydroxy phenylamino)-phenol, and reducing with hydrogen in the presence of nickel. The corresponding -N-methylpyridinium ester is prepared by heating the above compound with pyridine. The following compounds are similarly prepared: (1)N-methylpyridinium-N-p-hydroxyphenyl - N - allylaminoethylsulphonate; (2) N - - (N<SP>1</SP> - 4 - amino - 1 - naphthyl - N<SP>1</SP> - cyclohexylaminobutyryl) - pyridinium chloride ; and (3) N - ethylpyridinium - N<SP>1</SP> - ol -(or p<SP>1</SP>) amino -  phenyl : N' - α - tetrahydrophenylmethyl - p -  amino - benzene sulphonate. α - (o - hydroxyphenyl - N - methylamino) - N - methylpyridinium p-toluene sulphonate is prepared by reacting α - (o - hydroxyphenyl - N - methyl - amino) - pyridine with methyl - p - toluene sulphonate. # : #<SP>1</SP> - di(N - ethyl - pyridinium bromide) - N - hydroxyphenylamine and N - methylquinolium methylsulphate - 8 - sodium sulphonate 2 - N - p - aminophenyl - N - hydroxy - ethylamine are similarly prepared. N - p - aminophenyl - N - ethyl - # - sodium sulphonate - aminoethyltrimethyl ammonium  iodide is prepared by reacting the corresponding ethyldimethylamine with methyl iodide. N - # - (N - p - hydroxy - m - methylphenyl - N - methoxyethyl - amino) - #- hydroxy - n - propyl - N - methyl - N - ethyl - N - p - hydroxyphenylammonium methylsulphcnate and the compound of formula are similarly prepared. N - (o - amino - m - diethylaminophenylmethyl) - - N - triethylammonium chloride is prepared by reacting o-amino-m-diethylaminobenzyl chloride with excess of triethylamine. N - (8 - (N - ethyl - N - hydroxyethyl) - amino- 5 - hydroxy - 4 - chloro - 1 - naphthol - 2 - methyl)-pyridinium bromide is similarly prepared.  The acid radical attached to the nitrogen atom of the quaternary ammonium group may be halogen, sulphonate, sulphate, sulphite, or phosphate or groups of the type Specifications 2562/13, [Class 98 (ii)], 390,093, 395,718, 397,159, 416,566, 427,520, 447,748, 458,664, 458,665, [all in Group XX], 474,353, 478,933, 478,934, 478,942, 478,983, 478,984, 478,985, 478,986, 478,989, 478,990, 478,991 ; 493,952, 496,195, 496,196, 496,245, 502,960, 503,752 and 509,707, [all in Group XX], are referred to.