Patent GB-655258-A (GB)
Title: Process for improving materials in the form of fibre or film and manufacture of coumarin derivatives for use therein
IPC: D06L4/60
Filed: 1947-06-03
Abstract: The sulphonic acid derivative, obtained by reacting 4-methyl-7-aminocoumarin with formaldehyde-bisulphite solution, is dissolved in methanol and added to a cellulose acetate spinning solution.  On spinning, fibres having a bright appearance are obtained.  The Specification refers generally to the use of compounds of the general formula <FORM:0655258/IV (a)/1> (in which A is an amino-substituted benzene nucleus of which two vicinal carbon atoms are in the lactone ring, and R and R1 are hydrogen or an alkyl or aralkyl group) and which contain at least one sulphonic acid group. Many such compounds are specified (see Group IV (b)).  The Specification as open to inspection under Sect. 91 refers also to the use of compounds of the above general formula, but in which A may be any aromatic nucleus, and R and R1 may also be aryl, and in which there may be any acid or non-ionogenic water-solubilizing group. This subject-matter does not appear in the Specification as accepted.ALSO:Water - soluble derivatives of amino-coumarines are prepared by introducing a sulphonic acid group or a radical containing a sulphoric acid group into a compound of the general formula <FORM:0655258/IV (b)/1> in which A is an amino-substituted benzene nucleus of which two vicinal carbon atoms form part of the lactone ring, R and R1 are hydrogen or an alkyl or aralkyl group which may be substituted.  Types of compounds specified are compounds of the formula <FORM:0655258/IV (b)/2> in which R2 is H or an alkyl or aralkyl radical and R3 is H or a hydrocarbon radical and Me is a cation, prepared by treating the corresponding amino-coumarin with an aldehydebisulphite compound, or an aldehyde and sulphur dioxide; and compounds of the first general formula above in which A, R or R1 contains a sulphonic acid group or a sulphuric acid ester group, obtained by treating the appropriate amino-coumarin with a sulphonating agent, or by treating the amino-coumarin with a halogenated alkyl or aralkyl sulphonic acid.  In examples: (1) sodium bisulphite solution, formaldehyde and 4-methyl-7-amino-coumarine are boiled under reflux and the product separated by cooling and salting out; (2) 4 - methyl - 7 - ethylamino - coumarin is reacted with sodium bisulphite solution and formaldehyde in the presence of sodium carbonate; (3) 4-methyl-7-amino-coumarin is reacted with sodium bisulphite solution and benzaldehyde; (4) 4-methyl-7-aminocoumarin is condensed with sodium benzyl chloride-4-sulphonate; (5) 4-methyl-7-aminocoumarin is condensed with benzyl chloride and then sulphonated with sulphuric acid monohydrate; (6) 4 - methyl - 7 - (ethyl - benzylamino)-coumarin is sulphonated with fuming sulphuric acid; (7) 4-methyl-7-aminocoumarin is reacted with furfurol bisulphite; (8) 3-benzyl-4-methyl-7-ethylamino-coumarin is sulphonated with sulphuric acid monohydrate; (9) 4-methyl-7-ethylamino-coumarin is sulphonated with chlorosulphonic acid, and (10) 4-methyl-7-aminocoumarin is condensed with sodium b -bromethane sulphonate.  The Specification as open to inspection under Sect. 91 comprises also a process for introducing acid or non-ionogenic water-solubilizing groups into a compound of the first general formula above but in which A is any aromatic nucleus, and R and R1 may also be aryl, and refers to the following specific methods-compounds in which A, R or R1 contains the group -NR2-SO3Me (in which R2 is H or an alkyl, aryl or aralkyl group and Me is a cation), obtained by treating a primary or secondary amino-coumarin with sulphur trioxide in presence of pyridine; compounds in which A, R or R1 contains an alkyl or aralkyl group containing a carboxylic group, obtained by reacting the amino-coumarin with an aliphatic halogen-carboxylic acid or an aralkyl halide containing a carboxylic group in the aryl residue; condensation products of compounds which contain a primary amino group in A, R or R1 with a carbonyl compound containing a water-solubilizing group or group convertible into a water-solubilizing group, e.g. aldehyde- or ketone-sulphonic acids, reducing sugars, and crotonaldehyde which is subsequently additively combined at the double bond with bisulphite; condensation products of compounds which contain a primary or secondary amine group in A, R or R1 with an N-methylolamide of a carboxylic acid containing at least one water-solubilizing group or with a mixture of formaldehyde and an amide of such an acid, e.g. a carboxylic acid containing a quaternary ammonium group, or a sulpho-carboxylic acid; compounds in which the amino group present in A, R or R1 contains a polyglycol ether residue obtained, for example, by the action of ethylene oxide; compounds of the formula <FORM:0655258/IV (b)/3> which may be obtained by condensing the amino-coumarin having a primary or secondary amine group with a mercapto compound in the presence of an aldehyde or ketone in which the mercapto compound or the aldehyde or ketone contains a water-solubilizing group; and water-soluble salts of the formula <FORM:0655258/IV (b)/4> obtained from a primary or secondary aminocoumarine and a dicarboxylic acid or anhydride thereof. Examples are given of the preparation of each of the above types of compound.  The Specification comprises also the subject-matter of Specification 655,296.  This subject-matter does not appear in the Specification as accepted.ALSO:Textile materials, e.g. wool, silk, polyamide fibres, cotton, linen, regenerated cellulose and synthetic polymers, undyed, dyed or printed, e.g. discharge prints, are brightened by treating them with a substantially colourless blue to violet fluorescent compound which has the general formula <FORM:0655258/IV (c)/1> (in which A is an amino-substituted benzene nucleus of which two vicinal carbon atoms form part of the lactone ring, and R and R1 are H or an alkyl or aralkyl radical) and which contains at least one sulphonic acid group.  Many such compounds are specified (see Group IV (b)).  Examples are given of the treatment of (12) wool with the condensation product of 4-methyl-7 - amino - coumarin and formaldehyde - bisulphite; (13) silk with the condensation product of formaldehyde-bisulphite and 4-methyl-7-amino-coumarin; (14) cotton with the condensation product of formaldehyde-bisulphite and 4 - methyl - 7 - ethylamino - coumarin; and (15) the product obtained by condensing 4-methyl-7-amino-coumarin with sodium benzyl chloride-4-sulphonate; (16) nylon with the condensation product of 4-methyl-7-ethylamino-coumarin and formaldehyde-bisulphite; (17) a discharge print on dyed cotton fabric with the condensation product of formaldehyde bisulphite and 4-methyl-7-amino-coumarin; and (22) regenerated cellulose staple fibre cloth with an anti-creasing liquor which contains a condensation product of formaldehyde-bisulphite and 4-methyl-7-ethylaminocoumarin.  The Specification as open to inspection under Sect. 91 refers also to the use of compounds of the above general formula, but in which A is any aromatic nucleus, R and R1 may also be aryl, and which contain any acid or non-ionogenic water-solubilizing group including sulphamic groups, carboxylic groups, an N-methylolamide group containing at least one solubilizing group, polyglycol ether groups, groups obtained by condensing the amino group of the amino-coumarin, in the presence of an aldehyde or ketone, with a mercapto compound, one of the reagents containing a solubilizing group, and groups obtained by condensing the amino group with a dicarboxylic acid or anhydride.  The Specification also includes the subject-matter of Specification 655,296.  This subject-matter does not appear in the Specification as accepted.