Patent GB-1114848-A (GB)
Title: 1-halophenyl pyrazolines,their production and use as optical brightening agents
IPC: C11D3/42
Filed: 1965-05-26
Abstract: Polymers of olefinic compounds may be optically brightened with compounds of the general formula <FORM:1114848/C3/1> wherein X is halogen or -CF3, Y is H, halogen, -CF3, C1- 4 alkyl, optionally esterified carboxyl, C1- 4 alkylsulphonyl, C1- 4 hydroxyalkylsulphonyl, -CN, or an optionally N-substituted sulphonic or carboxylic acid amide group, Z is H, halogen or C1- 4 alkyl, R is H, C1- 4 alkyl or a carbocyclic- or heterocyclic-aromatic radical which is unsubstituted or contains non-ionogenic and non-colour imparting substituents, and A is a phenyl radical which is unsubstituted or contains non-ionogenic and non-colour imparting substituents.  In examples: (56) highpressure polyethylene granulate containing 1-(31 - chlorophenyl) - 3 - (411 - chlorophenyl)-pyrazoline is extruded to form a tube; (57) polyvinyl chloride sheet is drawn from a gelatinized mixture of polyvinyl chloride, dioctyl phthalate, sodium pentaoctyl tripolyphosphate and (a) di-n-butyl dilauryl dioxystannate and 1 - (31 - chlorophenyl) - 3 - (411 - chlorophenyl)-pyrazoline; or (b) dibutyl-tin dilaurate and 1-(31 - bromophenyl) - 3 - phenyl - pyrazoline.ALSO:Soap and detergents may be optically brightened by the incorporation of compounds of the formula <FORM:1114848/C4-C5/1> wherein X is halogen or -CF3, Y is H, halogen, -CF3, C1-4 alkyl, optionally esterified carboxyl, C1-4 alkylsulphonyl, C1-4 hydroxyalkylsulphonyl, -CN, or an optionally N-substituted sulphonic or carboxylic acid amide group, Z is H, halogen or C1-4 alkyl, R is H, C1-4 alkyl or a carboxylic- or heterocyclic-aromatic radical which is unsubstituted or contains non-ionogenic and non-colour imparting substituents, and A is a phenyl radical which is unsubstituted or contains non-ionogenic and non-colour imparting substituents. The usual fillers and auxiliaries for washing agents may be present in addition.  The optical brighteners of the above general formula are stated to fluoresce, those having halogen substituents in A fluorescing blue to blue-green and those having no halogen substituents in A fluorescing violet to blue.  In general, solutions of the compounds in organic solvents are almost colourless but exhibit vivid violet to blue fluorescence.  In Example 56, a tube extruded from high-pressure polyethylene containing 1 - (31 - chlorophenyl) - 3 -(411-chlorophenyl)-pyrazoline exhibits blue-violet fluorescence in daylight.ALSO:The invention comprises compounds of the general formula <FORM:1114848/C2/1> wherein X is halogen or -CF3, Y is H, halogen, -CF3, C1- 4 alkyl, optionally esterified carboxyl, C1- 4 alkylsulphonyl, C1- 4 hydroxyalkylsulphonyl, -CN, or an optionally N-substituted sulphonic or carboxylic acid amide group, Z is H, halogen or C1- 4 alkyl, R is H, C1- 4 alky or a carbocyclic- or heterocyclic-aromatic radical which is unsubstituted or contains non-ionogenic and non-colour imparting substituents, and A is a phenyl radical which is unsubstituted or contains non-ionogenic and non-colour imparting substituents. The compounds are prepared by reacting a compound of the formula <FORM:1114848/C2/2> with a compound of the formula (II) R-CH = CH-CO-A or of the formula <FORM:1114848/C2/3> wherein W is Cl, Br or tertiary amino, the reaction being conducted in the presence of an acid binding agent when W is Cl or Br.  The compounds may be obtained as mixed crystals either by using a mixture of starting materials or by melting or recrystallizing mixtures of the compounds of the invention.ALSO:Textiles are optically brightened with compounds of the general formula <FORM:1114848/D1-D2/1> wherein X is halogen or -CF3, Y is H, halogen, -CF3, C1-4 alkyl, optionally esterfied carboxyl, C1-4 alkyl-sulphonyl, C1-4 hydroxyalkylsulphonyl, -CN, or an optionally N-substituted sulphonic or carboxylic acid amide group, Z is H, halogen or C1-4 alkyl, R is H, C1-4 alkyl or a carbocyclic - or heterocyclice - aromatic radical which is unsubstituted or contains non-ionogenic and non-colour imparting substituents, and A is a phenyl radical which is unsubstituted or contains non-ionogenic and non-colour importing substituents. The brigteners are preferably applied as aqueous dispersions which may also contain dispersing agents and organic acids.  Specified materials to be brightened are polyamides such as nylon and polycaprolactum, polyacrlyonitrile, cellulose esters such as cellulose acetate, and cotton.