Patent GB-803361-A (GB)
Title: A process and products for the improvement of the optical properties of organic material
IPC: C09B23/10
Filed: 1955-01-21
Abstract: Compounds of general formula <FORM:0803361/III/1> in which A is an aromatic nucleus which may be substituted and in which 2 adjacent carbons are linked directly to B and the group <FORM:0803361/III/2> B is sulphur or the group <FORM:0803361/III/3> in which R1 is H or an organic substituent, R is an organic substituent, R2 is an organic substituent having at least 3 conjugated double bonds which are also in conjugation with the >C=N bond of the heterocyclic ring, and X is an acid residue, may be used in conjunction with washing agents for the treatment of organic materials.  Suitable washing agents are, for example, soaps; salts of sulphonate washing agents, such as sulphonated benzimidazoles substituted on the 2-carbon atom by high alkyl radicals; salts of monocarboxylic acid esters of 4-sulphophthalic acid with high fatty alcohols; salts of fatty alcohol sulphonates; alkylaryl sulphonic acids; or condensation products of high fatty acids with aliphatic hydroxy or amino sulphonic acids. Non-ionogenic washing agents, such as polyglycol ethers which are derived from ethylene oxide and high fatty alcohols, alkyl phenols or fatty amines may also be used.  The washing agents may also contain the customary additives for washing agents, such as alkali metal carbonates, phosphates, pyrophosphates, polyphosphates, metaphosphates, silicates, perborates or percarbonates. Suitable quantities of the amylimidazolium or arylthiazolium compounds to be added are 0.1-5 per cent by weight calculated on the washing agent, although in some cases 0.01 per cent or less may be effective. Specification 803,362, [Group IV (b)], is referred to.ALSO:Compounds of general formula <FORM:0803361/IV (a)/1> in which A is an aromatic nucleus which may have substituents and in which two adjacent carbon atoms are linked directly to B and the group <FORM:0803361/IV (a)/2> in which R1 is H or an organic substituent, R is an organic substituent, R2 is an organic substituent with at least three conjugated double bonds which are also in conjugation with the <FORM:0803361/IV (a)/3> bond of the heterocyclic ring, and X is an acid residue, are used as optical brightening agents for textile materials.  They may be added to the materials in the course of manufacture, for example, to a viscose solution to be used for the manufacture of films or threads or to a spinning mass, for example one comprising a linear synthetic polyamide or a spinning solution containing acetyl cellulose.  Specification 803,362, [Group IV (b)], is referred to.ALSO:Compounds of general formula <FORM:0803361/IV (b)/1> in which A is an aromatic nucleus which may have substituents and in which 2 adjacent carbon atoms are linked directly to B and the group <FORM:0803361/IV (b)/2> B is S or a group in which R1 is H or an organic substituent, R is an organic substituent, R2 is an organic substituent with at least 3 conjugated double bonds which are also in conjugation with the >C=N bond of the heterocyclic ring, and X is an acid residue, are used as optical brightening agents. They are advantageously prepared by treating suitably substituted arylimidazoles or thiazoles with agents capable of quaternating a thiazole or imidazole nitrogen atom, e.g. methyl iodide, ethyl bromide, isopropyl chloride, sec.-butyl bromide, dodecyl bromide, epichlorhydrin, dimethyl sulphate, benzyl chloride, p-chlorobenzyl chloride, menaphthyl chloride, toluene sulphonic acid esters, and compounds containing a water-solubilizing group such as halogen alkyl- or aralkyl sulphonic acids.  When salts of imidazoles or thiazoles are the basic materials alkaline oxides, such as ethylene oxide, propylene oxide or glycide, or lower alcohols such as methanol and ethanol can be used for quaternation.  The quaternation may be carried out by heating the components, for example to 50-200 DEG  C., advantageously in the presence of an inert solvent such as methanol, ethanol, dioxane, monomethyl glycol, benzene, toluene, nitrobenzene or mixtures of such solvents.  Instead of carrying out the quaternation as a final stage quaternated intermediate products may be used. Suitable intermediate products are, for example, arylimidazolium compounds which contain a methyl group on the m -carbon atom. Such compounds can be condensed with aldehydes.  Any water-solubilizing groups desired can be introduced by conventional methods before or after quaternation.  Further quaternary ammonium groups can be formed when the molecule contains further amino groups capable of quaternation. Alternatively, addition products of tertiary amines with halogen carboxylic acid-N-methylolamides can be used in which case the condensation can also be carried out in such a manner that reaction takes place first with a halogen carboxylic acid-N-methylolamide with subsequent addition of the tertiary amine. For the introduction of sulphonic acid groups the customary sulphonating agents such as concentrated sulphuric acid, sulphuric acid monohydrate, chlorsulphonic acid, and sulphuric acid containing sulphur trioxide may be used.  Compounds containing sulphonic acid groups, for example N-methylolamides of sulphocarboxylic acids, may also be used.  The introduction of polyglycol ether chains can be effected in the customary manner by reaction with ethylene oxide or polyglycols.  Among the arylimidazolium compounds obtainable by the above-described methods are the following:-(a) compounds of general formula <FORM:0803361/IV (b)/3> in which the two residues A are the same or different aromatic nuclei, which may be substituted, R is alkyl or aralkyl and may be substituted, R3 is a divalent bridge containing at least one double bond which forms an uninterrupted series of conjugated double bonds with the >C=N double bonds of the imidazole rings, m and n are 1 or 2, and X is an anion; these compounds are described and claimed in Specification 803,362; (b) compounds of general formula <FORM:0803361/IV (b)/4> in which A is an aromatic nucleus which may be substituted, R is an alkyl or aralkyl residue which may be substituted, R1 is hydrogen or an alkyl, aryl or aralkyl residue which may be substituted, R4 is an aryl residue and X is an anion; examples of compounds within this general formula are <FORM:0803361/IV (b)/5> and <FORM:0803361/IV (b)/6> (c) compounds of general formula <FORM:0803361/IV (b)/7> in which R5 is an aromatic residue and K is 1 or 2.  In the examples: (a) <FORM:0803361/IV (b)/8> is prepared by reacting a ,b -di-(N-methyl-benzimdiazyl-(2)-ethylene with p-toluene sulphonic acid ethyl ester; instead of the N-methylderivative the N-benzyl-derivative can be used to give the corresponding product; (b) <FORM:0803361/IV (b)/9> is obtained by reacting a ,b -di-[benzimidazyl-(2)]-ethylene with p-toluene sulphonic acid; products with similar properties are obtained from 6,61-dimethyl- or 6,61-dichloro-a ,b -di-[benzimidazyl-(2)]-ethylene; (c) a quaternary ammonium compound is obtained similarly by reacting a ,b  - di - [N - methyl - benzimidazyl - (2)]-ethylene with dimethyl sulphate; (d) the compound of formula given in (b) is boiled with water under reflux to give the compound of formula <FORM:0803361/IV (b)/100> (e) the compound of formula <FORM:0803361/IV (b)/111> is obtained by condensing 1-amino-2-nitro-4-methoxybenzene with p-nitrobenzoyl chloride in pyridine, reducing the nitro group to an amino group, condensing the product with p-methoxy benzoyl chloride and quaternation with p-toluene sulphonic acid ethyl ester; (f) 2 - [41 - (411 - methoxy - benzoyl) - aminophenyl] - 6 - methyl - N - ethyl - benzthiazole - p-toluene sulphonate is obtained by reacting 2 - [41 - (411 - methoxybenzoyl) - aminophenyl] - 6 - methyl - benzthiazole with p - toluene sulphonic acid ethyl ester; other quaternary compounds are obtained by quaternation of 2-[41-(411 - methoxy - benzoyl) - aminophenyl] - 6 - methylbenzthiazole with p-toluene sulphonic acid methyl ester or with dimethyl sulphate, or by quaternation of 2-(41-benzoylamino)-phenyl-6-methyl-benzthiazole with p-toluene sulphonic acid ethyl or methyl ester or with dimethyl sulphate; and (g) 2-styryl-N-ethyl-benzthiazole-p-toluene sulphonate of formula <FORM:0803361/IV (b)/122> is obtained by reacting 2-styrylbenzthiazole and p-toluene sulphonic acid ethyl ester.  The compounds of the above general formula are used as optical brightening agents (Group XL (a)) in the treatment of textile materials (Groups IV (a) and IV (c)), paper (Group VIII), textile finishes (Group V) and food (Group VI) and in cleansing compositions (Group III).ALSO:Compounds of general formula <FORM:0803361/IV (c)/1> in which A is an aromatic nucleus which may have substituents and in which 2 adjacent carbon atoms are linked directly to B and the group <FORM:0803361/IV (c)/2> B is S or a group <FORM:0803361/IV (c)/3> in which R1 is H or an organic substituent, R is an organic substituent, R2 is an organic substituent with at least 3 conjugated double bonds which are also in conjugation with the >C = N bond of the heterocyclic ring, and X is an acid residue, are used as optical brightening agents for textiles.  The material to be treated may be saturated with a solution, especially an aqueous solution, or a dispersion of the compound concerned.  The compounds may also be applied in admixture with dyestuffs or as additions to dyebaths, printing, discharge or reserve pastes, in admixture with chemical bleaching agents or with finishing agents. They may also be used in conjunction with washing agents, e.g. soaps, salts of sulphonate washing agents, polyglycol ethers derived from ethylene oxide and high molecular fatty alcohols, alkyl phenols or fatty amines.  The washing agents may also contain the customary additions to washing agents, such as alkali carbonates, phosphates, pyrophosphates, polyphosphates, metaphosphates, silicates, perborates or percarbonates.  Suitable quantities