Patent GB-1113603-A (GB)
Title: Stabilising photographic emulsions
IPC: G03C1/43
Filed: 1965-05-28
Abstract: In Preparations, (1), 2-hydroxyethylisothiuronium chloride is prepared by condensing 2-chloroethanol with thiourea; the corresponding bromide (4) is similarly made using 2-bromoethanol, and the corresponding nitrate (2), perchlorate (7), formate (6), acetate (11), trichloracetate (3) and N - (p - hydroxyphenyl) aminoacetate (12) are obtained by reaction of 2-hydroxyethylisothiuronium chloride or bromide with silver nitrate, silver perchlorate, potassium formate, silver acetate, potassium trichloracetate or potassium N - (p - hydroxyphenyl) aminoacetate.  3 - Hydroxypropylisothiuronium bromide (5), 2 - ethylaminoethylisothiuronium chloride (23), 2 - dimethylaminoethylisothiuronium chloride hydrochloride (24), 2-hydroxypropylisothiuronium trichloracetate (25) and N-butylcarbamoyloxyethylisothiuronium chloride (27) are made by reacting thiourea with, respectively, 3-bromo-1-propanol, ethylaminoethyl chloride, 2-dimethylaminoethyl chloride hydrochloride, propylene oxide and trichloracetic acid, and 2-chloroethyl N-butylcarbamate.  Isothiureidoacetic acid (8), 2 - isothiureidopropionic acid (9) and 3-isothiureidobutyric acid (10) are prepared by condensing thiourea with sodium chloracetate, propiolactone and butyrolactone respectively.  In further Preparations, (13) and (14), compounds of the general formula <FORM:1113603/C2/1> where R1 and R11 are each selected from the values phenyl, p-hydroxyphenyl, p-methylphenyl, o-, m- or p-nitrophenyl, o-, m- or p-chlorophenyl and o-, m- or p-methoxyphenyl, by condensing 2-morpholinoethanethiol with benzalacetophenone or a suitably substituted benzalacetophenone.  The corresponding hydrochlorides are obtained by treating the compounds with hydrogen chloride.  b  - (2 - Diethylaminoethylthio) - b  - phenylpropiophenone hydrochloride (15) is made by condensing benzalacetophenone with b -diethylaminoethanethiol and reacting with HCl.  b  - (3 - Diethylamino - 2 - hydroxypropylthio) - b  - phenyl - p - methroxypropiophenone hydrochloride (16) is prepared by condensing 3-diethylamino - 2 - hydroxypropanethiol with benzal p-methoxyacetophenone and reacting with HCl.  b  - Carboxymethylthio - b  - phenylpropiophenone (17) and the corresponding p-hydroxyand p-methoxypropiophenone compounds (18) are made by condensing mercaptoacetic acid with benzalacetophenone, benzal p-hydroxyacetophenone and benzal p-methoxyacetophenone respectively. In other Preparations, hydrochlorides of compounds of the general formula <FORM:1113603/C2/2> where M is morpholino, R12 is -CH2CH2-, R10 and R11 are each selected from the values carboxymethyl, carboxyethyl, cyano and carbamyl and R9 is hydrogen, phenyl or p-methoxyphenyl, are obtained by condensing 2-morpholinoethanethiol with dimethyl benzalmalonate (19), dimethyl p-methoxybenzalmalonate (20), diethyl benzalmalonate (21), diethyl methylenemalonate (22), benzalmalonodinitrile (28), methylenemalonodinitrile (29), ethyl benzal cyanoacetate (30), ethyl methylene cyanoacetate (31), ethyl benzalcarbamyl acetate (32), ethyl methylenecarbamyl acetate (33), diethyl methylenemalonate (35) and dimethyl methylenemalonate (36), and then treating the product with hydrogen chloride.  Hydrochlorides of compounds of the above general formula where R10 and R11 are each carbomethoxy, R12 is -CH2CH(OH)CH2-, M is diethylamino and R9 is hydrogen (37) or phenyl (38) are made by condensing 3-diethylamino -2-hydroxypropanethiol with dimethyl benzalmalonate or dimethyl methylenemalonate, and the compound where R10 and R11 are both carboethoxy, R12 is -CH2CH2-, M is piperidino and R9 is phenyl (34) is made by condensing 2-piperidinoethanethiol with diethyl benzalmalonate, the products obtained being treated with hydrogen chloride.