Patent GB-832239-A (GB)
Title: Brightening agents comprising arylpyrazolines
Filed: 1956-10-10
Abstract: Soap or detergent compositions comprise as fluorescent brightening agents arylpyrazolines of general formula <FORM:0832239/III/1> and derivatives such as salts, esters, amides or nitriles thereof, wherein Ar denotes an aryl radical such as phenyl or naphthyl and X denotes hydrogen or an aryl radical.  The aromatic nuclei may be substituted by halogen, hydroxy C1-5 alkyl or alkoxy groups (for preparation see Group IV (b)).  Conventional additives such as perfume, dyes, white pigments and deodorants may be present. The brightening agent may be added to a soap base as a suspension in a soap solution or in an emulsifier, or may be incorporated in soap flakes.  Specification 827,745 is referred to.ALSO:The invention comprises arylpyrazolines of general formula <FORM:0832239/IV (b)/1> and derivatives such as salts, esters, amides or nitriles thereof, wherein Ar denotes an aryl radical such as phenyl or naphthyl and X denotes hydrogen or an aryl radical.  The aromatic nuclei may be substituted by halogen, hydroxy, C1-5 alkyl or alkoxy groups.  They may be prepared by the action of arylhydrazines on the salts of b -aminoethylaryl ketones, b -dialkylaminoethylaryl ketones, b -halogenethylaryl ketones or aryl-substituted vinylarylketones such as 1,3-diphenyl-propene-(1)-one-(3).  They act as brightening agents. In examples: (1) acetophenone is reacted with ammonium chloride and formaldehyde and the crude product, presumably b -aminoethyl phenyl ketone (hydrochloride), reacted with p-hydrazinobenzoic acid hydrochloride in the presence of sodium carbonate to give the sodium salt of 1 - p - carboxyphenyl - 3 - phenylpyrazoline; the free acid is obtained by acidification with HCl and the ethyl ester by the action of ethanol and thionyl chloride on the salt; 1-p-cyano-phenyl-3-p-chlorophenylpyrazoline is prepared by refluxing p-cyanophenylhydrazine and p-chlorophenyl-b -chloroethylketone in methanol with an acid-binding agent such as pyridine or ammonium carbonate; (3) b -chloropropionic acid is reacted with thionyl chloride and the product condensed with chlorobenzene in the presence of AlCl3 to give, presumably, b -chloroethyl p-chlorophenyl ketone, which is reacted with p-hydrazinobenzoic acid hydrochloride in the presence of pyridine in methanol solution to give 1-p-carboxyphenyl-3-p-chlorophenylpyrazoline; (5) 1 - p - carboxyphenyl - 3 - p-methylphenylpyrazoline, 1 - p - carboxyphenyl - 3 - p-methoxyphenylpyrazoline and 1-p-carboxyphenyl - 3 - p - hydroxyphenylpyrazoline are prepared by the action of p-hydrazinobenzoic acid hydrochloride on b -chloroethyl-p-methylphenyl ketone, b -chloroethyl-p-methoxyphenyl ketone and b -aminoethyl-p-hydroxyphenyl ketone respectively. Specifications 669,590, 669,591 and 827,745 are referred to.ALSO:Textile fibres such as cellulose fibres, wool or synthetic fibres, specifically polyacrylonitrile, acetate rayon and polyamide fibres and paper are treated with fluorescent brightening agents comprising arylpyrazolines of general formula <FORM:0832239/IV(c)/1> and derivatives such as salts, esters, amides or nitriles thereof, wherein Ar denotes an aryl radical such as phenyl or naphthyl and X denotes hydrogen or an aryl radical.  The aromatic nuclei may be substituted by halogen, hydroxy, C1-5 alkyl or alkoxy groups (for preparation see Group IV (b)).  The fibres may be introduced into aqueous solutions comprising the arylpyrazoline, sodium carbonate, a surface-active paraffin sulphonate and acetic acid.  Mention is also made of washing linen with soap containing an arylpyrazoline brightening agent.  Specifications 669,590, 669,591 and 827,745 are referred to.ALSO:Arylpyrazolines of general formula <FORM:0832239/IV (a)/1> or derivatives such as salts, esters, amides or nitriles thereof, wherein Ar denotes an aryl radical such as phenyl or naphthyl and X denotes hydrogen or an aryl radical are stated to be usable in the production of brightened articles of synthetic polycondensates according to the process of Specification 827,745. The aromatic nuclei may be substituted by halogen, hydroxy, C1-5 alkyl or alkoxy groups (for preparation see Group IV (b)).