Patent GB-991202-A (GB)
Title: Improvements relating to 3-phenyl-7-pyrazolyl coumarins and their use as optical brightening agents
IPC: C07D405/04
Filed: 1962-04-25
Abstract: The invention comprises 3-phenyl-7-pyrazolyl-(11)-coumarins of the formula <FORM:0991202/C2/1> wherein each R1, R2, R3, R4 represents hydrogen or an aliphatic, alicyclic, araliphatic or aromatic radical, R4 hydrogen or an alkyl (1-5 C), and R5 a phenyl group which may be substituted in the position by chlorine or methyl and in the m position by -SO3H, -SO2NH2, <FORM:0991202/C2/2> which are prepared (1) by condensing a 3-phenyl-7-hydrazinocoumarin or salts, hydrazino-sulphonic acids or N-acyl hydrazino compounds thereof with a compound having an a -g -dicarbonyl group such as 1,3-diketones, b -ketoaldehydes or acetals and hydroxymethylene ketones; b -dialdehydes or acetals, a -alkoxy methylene aldehydeacetals and a -alkoxymethylene aldehyde acetals or other compounds containing a grouping reacting like an aliphatic a -g -dicarbonyl radicals are specified also addition products of the a ,g -dicarbonyl compounds with acid alkali metal salts of sulphurous acid; (2) by reacting 7-hydrazine-3-phenylcoumarins with compounds containing an a ,b -alkinyl carbonyl group, such as a ,b -alkinyl ketones or aldehydes, or acetals thereof or a -halogen-a ,b -alkenyl ketones, or their aldehydes or acetals; (3) by condensing 3-phenyl-7-hydrazine coumarins with compounds having a ,b -alkenyl carbonyl groups or their equivalent e.g. chalcones, Mannich bases to form 7-pyrazolinyl-3-phenyl coumarins followed by dehydrogenation; or (4) by condensing benzaldehydes with an hydroxy or alkoxy group in the 2-position and a substituted or unsubstituted pyrazole group in the 4-position with an acetic acid derivative having a phenyl or substituted phenyl radical at the a -carbon atom to form the corresponding b -phenylacrylic acid and closing the ring with the carboxylic function of the acrylic acid radical to form the coumarin ring.  The 3-phenyl substituent sulphonic acid, sulphamide, or N-substituted sulphonamide groups may be present in the starting component or by treatment of the product.  The products are colourless to weakly yellow crystalline compounds with a violet fluorescence in organic solvents and are suitable as optical brightening agents. Examples of the preparation and use of the compounds as brightening agents are given.ALSO:3 - Phenyl - 7 - pyrazolyl - (11) coumarins of formula <FORM:0991202/C3/1> wherein each of R1,R2,R3,R4 represents hydrogen or an aliphatic, alicyclic, araliphatic or aromatic radical, R4 hydrogen or an alkyl (1-5 C) and R5 a phenyl group which may be substituted in the p position by chlorine or methyl and in the m position by -SO3H, -SO2NH2, -SO2.NH.CH3, -SO2.NH.CH2. CH3, -SO2.NH.CH2CH2OH, -SO2.NH.CH2 CH2OCH3, -SO2.NH.CH2CH2OCH2CH3, <FORM:0991202/C3/2> , -SO2.NH. <FORM:0991202/C3/3> , -SO2-N.(CH3)2, or -SO2.N.(CH2CH3)2 (see Division C2) are used as optical brightening agents for polymers and copolymers, e.g. polymeric and copolymeric acrylonitrile, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyethylene, polypropylene, polymethacrylate and copolymers thereof and polymeric esters of terephthalic acid and polyvalent alcohols. They may be added before or after polymerization and examples describe the addition of 3-phenyl-7 - [31 - methyl - pyrazolyl - (11)] - coumarin, to polyethylene terephthalate, and polyamide chips derived from e -caprolactam; of 3-phenyl-7 - [31,51 - dimethylpyrazolyl - (11)] - coumarin to a mixture of hexanediamine adipate, sebacic acid and titanium dioxide which is then polycondensed; of 3 - phenyl - 2 - pyrazolyl - (11)-coumarin to a mixture of polyvinyl chloride, dioctylphthalate, di-n-butyl dilauryl dioxystannate and sodium pentaoctyl tripolyphosphate which is mixed and made into foil; and of 3 - phenyl - 7 - [31 - methylpyrazolyl - (11)]- coumarin to polyvinyl chloride, titanium dioxide, di-octyl phthalate, dibutyl-tin-dilaurate, and sodium pentaoctyl tripolyphosphate.ALSO:Optical brightening agents comprise 3-phenyl-7-pyrazolyl-(11) coumarins of formula <FORM:0991202/D1-D2/1> wherein each of R1, R2, R3, R4 each represents hydrogen or an aliphatic, alicyclic, araliphatic, or aromatic radical, R4 hydrogen or an alkyl (1-5C) and R5 a phenyl group which may be substituted in the p position by chlorine or methyl and in the m position by -SO3H, -SO2NH2, -SO2.NH. CH2.CH3, -SO2.NH.CH2CH2OH, -SO2.NH. CH2CH2OCH3, -SO2.NH.CH2CH2OCH2CH3, -SO2.NH.CH2CH2N. (CH2CH3)2, -SO2.NH. (CH2)3. N(CH3)2, -SO2-N(CH3)2 or -SO2.N.(CH2CH3)2 (see Division C2) and are used for cellulose acetate, particularly cellulose triacetate fibres or incorporated in dressings such as finishings for textile fibres such as polyvinyl alcohol or in resins used for textile treatment. They may be applied from an aqueous bath.  In examples 3-phenyl-7-[31, 51-dimethylpyrazolyl-(11)] coumarin in a bath with olein alcohol pentadecyl glycol ether is used to treat staple fibre fabric of polyadipic acid hexamethylanediamide; 3-phenyl-7-[31-methylpyrazolyl-(11)]-coumarin in a bath with the above ether is used to treat a fabric of polyterephthalic acid glycol ester; 3-(m-tolyl)-7-[31-methylpyrazolyl-(11)]-coumarin is used to treat uncoloured acetyl cellulose yarn; 3-phenyl-7-[51-methylpyrazolyl-(11)] coumarin and a synthetic washing agent are used to wash uncoloured nylon fabric; 3-(p-chlorophenyl)-7-[31-methyl-pyrazolyl-(11)] coumarin, o-dichlorobenzene and octyl-phenol dodecaglycol ether used to treat polyethylene terephthalate fabric; 3-(p-tolyl)-7-[31, 51-dimethylpyrazolyl-(11)]-coumarin and nonylphenol dodecaglycol ether used to foulard a polyethylene terephthalate fabric.