Patent GB-1019230-A (GB)
Title: New monoazolyl-thiophene derivatives,process for their preparation and their use
IPC: B27K5/00
Filed: 1963-11-15
Abstract: A detergent composition contains an optical brightener of the general formula <FORM:1019230/C4-C5/1> wherein A is a benzene or naphthalene residue of which two vicinal cyclic carbon atoms are shared with the azole ring; X is the complement to an oxazole, thiazole or imidazole ring; R is a thiophene residue bound in the 2 position with the azole ring and in the 5 position with Z, and Z is a carboxyl group or a functionally modified carboxyl group.  The term "functionally modified carboxyl" group is defined to mean carboxylic acid halide, ester, nitrile, amide or hydrazide group; the residue A may be substituted by, for example, alkyl, alkenyl, alkoxy, halogen, nitrile, cyanoalkyl, carbalkoxy, carboxyalkyl, carbalkoxyalkyl, phenyl, phenylalkyl, cycloalkyl or sulphonic acid; and the thiophene ring R may be substituted by C1 to C7 hydrocarbon radicals. Specified detergent compositions are based on soaps, salts of sulphonated benzimidazole substituted at the 2-position by higher alkyl radicals, salts of monocarboxylic acid esters of 4-sulphophthalic acid with higher fatty alcohols, salts of fatty alcohol sulphonates, salts of alkylarylsulphonic acids, salts of condensation products of higher fatty acids with aliphatic hydroxysulphonic or aminosulphonic acids, or polyglycol ethers derived from ethylene oxide and higher fatty alcohols, alkylphenols or fatty amines.  The compositions may also contain alkali metal carbonates, phosphates, pyrophosphates, polyphosphates, metaphosphates, silicates, perborates or percarbonates.  In general the compositions contain 0.1 to 2% by weight of detergent of the new optical brighteners.ALSO:Compounds of the general formula <FORM:1019230/C2/1> wherein A is a benzene or naphthalene residue of which two vicinal cyclic carbon atoms are shared with the azole ring; X is the complement to an oxazole, thiazole or imidazole ring; and R is a thiophene residue bound in the 2 position with the azole ring and in the 5 position with Z; and Z is a carboxyl group or a "functionally modified carboxyl" group, are stated to be new compounds.  The term "functionally modified carboxy" group is defined to means carboxylic acid halide, ester, nitrile, amide or hydrazide group; the residue A may be substituted by, for example, alkyl, alkenyl, alkoxy, halogen, nitrile, cyanoalkyl, carbalkoxy, carboxyalkyl, carbalkoxyalkyl, phenyl, phenylalkyl, cycloalkyl or sulphonic acid; and the thiophene ring R may be substituted by C1 to C7 hydrocarbon radicals.  The monoazolyl-thiophene derivatives of the invention may be prepared by (A) reacting a thiophene monoesterified dicarboxylic acid halide of the formula <FORM:1019230/C2/2> wherein R1 represents a C1 to C4 alkyl ester group, with an ortho-amine of the formula <FORM:1019230/C2/3> wherein X4 represents a hydroxyl, mercapto or primary or secondary amino group, and, if desired, hydrolysing the resultant monoazolylthiophene C1-C4 alkyl ester compound to the carboxyl group or converting said ester product into another functionally modified carboxyl group; (B) reacting a thiophene monoesterified dicarboxylic acid of the formula <FORM:1019230/C2/4> with an ortho-amine of the above formula at 150 DEG  to 300 DEG  C. in the presence of a water-eliminating agent, especially boric acid, and, if desired, in the presence of a high boiling, polar, organic solvent and, if desired, hydrolysing or converting the ester product as in (A); or (C) reacting a thiophene compound of the formula <FORM:1019230/C2/5> with hydrogen chloride and formaldehyde or paraformaldehyde, or with dichloromethyl ether to yield a compound of the formula <FORM:1019230/C2/6> hydrolysing the chloromethyl group of this product to the hydroxymethyl group, oxidizing the latter to the carboxyl group, and, if desired, esterifying or converting the carboxyl group to a functionally modified carboxyl group.  The process (A) above may be performed in two stages:  the first being the condensation of the acid halide with the amine at an elevated temperature in the presence of an inert organic solvent to form the compound <FORM:1019230/C2/7> wherein X3 represents an oxygen or sulphur atom, an <FORM:1019230/C2/8> group or the residue of a secondary amine and the second stage being the heating, if desired after isolation of the acyl product of the first stage, of said product at about 150 DEG  to 300 DEG  C. in the presence of a water-eliminating agent, especially boric acid in the absence or presence of a high boiling, polar, organic solvent.  The compounds of the invention may be employed as optical brighteners.ALSO:Fibrous materials are optically brightened with monoazole thiophene compounds of the general formula <FORM:1019230/D1-D2/1> wherein A is a benzene or naphthalene residue of which two vicinal cyclic carbon atoms are shared with the azole ring; X is the complement to an oxazole, thiazole or imidazole ring; R is a thiophene residue bound in the 2 position with the azole ring and in the 5 position with Z; and Z is a carboxyl group or a "functionally modified carboxyl" group.  The term "functionally modified carboxyl" group is defined to mean carboxylic acid halide, ester, nitrile, amide or hydrazide group; the residue A may be substituted by, for example, alkyl, alkenyl, alkoxy, halogen, nitrile, cyanoalkyl, carbalkoxy, carboxyalkyl, carbalkoxyalkyl, phenyl, phenylalkyl, cycloalkyl or sulphonic acid; and the thiophene ring R may be substituted by C1 to C7 hydrocarbon radicals.  The brighteners may be applied by impregnating the material at an elevated temperature with a solution or dispersion of the compound and then centrifuging or squeezing the impregnated material before drying.  They may be applied in admixture with dyestuffs, chemical bleaches, dressing agents or detergents.  In an Example a polyamide fabric is immersed at 60 DEG C. in an aqueous solution, containing a dispersant, acetic acid and a compound of the formula <FORM:1019230/D1-D2/2> heated to the boil within 20 minutes and treated at the boil for 30 minutes prior to rinsing and drying.