4,4'-Diaminostilbene-2,2'-disulfonic acid derivatives

Abstract: The present invention provides new compounds having the formula: in which X is O or NH; M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine; each R 1 , independently, is an aminoacid residue from which a hydrogen atom on the amino group has been removed; and each R 3 , independently, is C 1 -C 3 alkyl or phenyl and the use thereof for inhibiting (quenching) the effect of anionic fluorescent whitening agents on substrates.

Description: The present invention relates to new compounds, in particular to new 4,4'-diaminostilbene-2,2'-disulphonic acid compounds which are useful for inhibiting (quenching) the effect of anionic fluorescent whitening agents on substrates. In WO 96/00221, there are described optical brightening agents for textiles, paper etc. The disclosed compounds have the formula: in which R a and R b are the same or different and each has the formula -NR c R d in which R c is hydrogen; C 1 -C 6 alkyl which is optionally substituted by at least one of mercapto, C 1 -C 6 thioalkyl, OH and SO 3 M' in which M' is hydrogen, a colourless cation or an amine-derived cation; or -R e (CO 2 M') x in which R e is an aliphatic moiety having 1-6 carbon atoms, those valencies not bonded with groups CO 2 M' being bonded with at least one of hydrogen, mercapto, C 1 -C 6 thioalkyl, OH and SO 3 M' in which M' has its previous significance and x is an integer from 1 to 4, provided that, when R c is C 1 -C 6 alkyl which is optionally substituted by at least one of mercapto, C 1 -C 6 thioalkyl, OH and SO 3 M', R c is substituted with at least both of OH and SO 3 M'; R d is R c , hydrogen or C 3 -C 6 alkyl, provided that R c and R d cannot both be hydrogen and that, when one of R c and R d is hydrogen, the other cannot be -(NHCH 2 CO 2 H); or R c and R d , together with the nitrogen atom, form a ring having from 5-6 members only, one of which is heterocyclic, which ring is singly substituted with -COOM' or -SO 3 M'; and each R f , independently, is hydrogen, methyl, C 1 -C 6 alkoxy or halogen. A new class of 4,4'-diaminostilbene-2,2'-disulphonic acid compounds has now been found which are useful for inhibiting (quenching) the effect of anionic fluorescent whitening agents on substrates. Accordingly, the present invention provides new compounds having the formula: in which X is O or NH; preferably NH, M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine; each R 1 , independently, is an aminoacid residue from which a hydrogen atom on the amino group has been removed; whereby the amino acid from which the amino acid residues R 1 are derived is glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hydroxyphenylalanine), diiodotyrosine, tryptophan (β-indolylalanine), histidine ((β-imidazolylalanine), α-aminobutyric acid, methionine, valine (α-aminoisovaleric acid), norvaline, leucine (α-aminoisocaproic acid), isoleucine (α-amino-β-methylvaleric acid), norleucine (α-amino-n-caproic acid), arginine, ornithine (α,δ-diaminovaleric acid), lysine (α,ε-diaminocaproic acid), aspartic acid (aminosuccinic acid), glutamic acid (α-aminoglutaric acid), threonine, hydroxyglutamic acid or taurine, or a mixture or an optical isomer thereof or iminodiacetic acid and each R 3 , independently, is C 1 -C 3 alkyl or phenyl. Preferably M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C 1 -C 4 alkylammonium, mono-, di- or tri-C 1 -C 4 hydroxyalkylammonium or ammonium that is di- or tri-substituted with a mixture of C 1 -C 4 alkyl and C 1 -C 4 hydroxyalkyl groups. Preferably each M is Na. Preferably, each of the aminoacid residues R 1 is the same. Specific examples of aminoacids from which such preferred aminoacid residues R 1 are derived include glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hydroxyphenylalanine), diiodotyrosine, tryptophan (β-indolylalanine), histidine ((β-imidazolylalanine), α-aminobutyric acid, methionine, valine (α-aminoisovaleric acid), norvaline, leucine (α-aminoisocaproic acid), isoleucine (α-amino-β-methylvaleric acid), norleucine (α-amino-n-caproic acid), arginine, ornithine (α,δ-diaminovaleric acid), lysine (α,ε-diaminocaproic acid), aspartic acid (aminosuccinic acid), glutamic acid (α-aminoglutaric acid), threonine, hydroxyglutamic acid and taurine, as well as mixtures and optical isomers thereof. Of these aminoacids from which such preferred aminoacid residues R 1 are derived, sarcosine, taurine, glutamic acid and aspartic acid are particularly preferred. A further preferred example of an aminoacid from which an aminoacid residue R 1 may be derived is iminodiacetic acid. The compounds of formula (1) are useful for inhibiting (quenching) the effect of anionic fluorescent whitening agents on substrates. The compounds of formula (1) may be produced by reacting, under known reaction conditions, cyanuric chloride, successively, in any desired sequence, with each of 4,4'-diamino-2,2'-stilbene disulphonic acid, an amino compound capable of introducing a group in which R 3 has its previous significance, and a compound capable of introducing a group R 1 , in which R 1 has its previous significance. The starting materials are known compounds which are readily available. The following Examples further illustrate the present invention. Parts and percentages shown therein are by weight unless otherwise stated. Example 1 A) 18.81 g of cyanuric chloride (98% purity) are dissolved in 95 ml of acetone and poured on to 100 g of a mixture of ice and water. Over 30 minutes, a solution of 18.5 g of of diaminostilbene-di-sulphonic acid (100% purity) is added, dropwise, into 320 g of a mixture of ice and water at a temperature in the range of from -5°C. to 0°C. Finally, over 15 minutes, 50 ml of a 1 molar soda solution are added, dropwise, at this temperature, and the whole is stirred for a further 1 hour. 13.5 g of 4-aminoacetophenone are added and the mixture is heated to 50°C., over 90 minutes. During this procedure, the pH of the reaction mixture is held at 7-8 by the addition of sodium carbonate. In order to complete the reaction, the acetone is distilled off until the temperature of the reaction mixture has reached 66°C. The precipitated deposit is filtered warm with suction, washed with dilute aqueous sodium chloride (2%) and then with 300 ml of cold water. After drying, there remain 44.8 g (88% theory) of the compound of formula Elemental analysis of the compound having the formula (100) and having the empirical formula C 36 H 26 N 10 O 8 Cl 2 S 2 Na 2 . 6.0 H 2 O gives: Req.% C 42.57; H 3.77; N 13.79. Found % C 42.59; H 3.85; N 13.74. B) 5 g of the compound of formula (100) obtained in part A) are suspended in 100 ml of water. 1.3 g of taurine are added and the reaction mixture is heated to 90°C. and the pH is held at 9-10 using sodium carbonate. The reactants are allowed to further react at this pH and temperature for 15 hours. Finally, the reaction mixture is concentrated and the compound (113) is precipitated with acetone. After filtration with suction, washing with acetone and drying, there remain 5.9 g (81% theory) of the compound (101). Elemental analysis of the compound having the formula (101) and having the empirical formula C 40 H 36 N 12 Na 4 O 14 S 4 . 0.66 NaCl. 16.5 H 2 O gives: Req.% C 32.8; H 4.74; N 11.47; S 8.75; Cl 1.60; Na 7.32. Found % C 32.7; H 4.7; N 11.5; S 9.1; Cl 1.6; Na 7.4. The compound having the formula (101) effects a significant reduction in whiteness and fluorescence of pre-brightened paper treated with said compound. Example 2 Using an analogous procedure to that described in Example 1, compound (102) is produced by reacting the compound (100) with 0.9 g of sarcosine instead of taurine. The reaction is complete after 6 hours and the yield of the compound (102) is 93% of theory. Elemental analysis of the compound having the formula (102) and having the empirical formula C 42 H 36 N 12 Na 4 O 12 S 2 15 H 2 O gives: Req.% C 38.02; H 5.01; N 12.66. Found % C 38.10; H 4.87; N 12.65. The compound having the formula (102) effects a significant reduction in whiteness and fluorescence of pre-brightened paper treated with said compound. Example 3 10 g of the compound of formula (100) are reacted with 5.8 g of L-glutamic acid in a 6:9 by weight mixture of water and methylcellosolve at 120°C. in an oil bath, the pH being held at 8-9 by the addition of sodium carbonate. After 6 hours, the reaction is complete. The reaction mixture is dropped into acetone acidified with HCl, whereupon the compound of formula (103) precipitates out as the free acid. After filtration with suction and washing with acetone-water, the filtercake is converted into the corresponding hexa-sodium salt by the addition of the calculated amount of aqueous sodium hydroxide, and evaporation to dryness. The yield is 90% of theory. Elemental analysis of the compound having the formula (103) and having the empirical formula C 46 H 38 N 12 Na 6 O 10 S 2 . 0.3 NaCI. 17 H 2 O gives: Req.% C 35.9; H 4.71; N 10.92; S 4.16. Found % C 36.0; H 4.7; N 10.9; S 4.1. The compound having the formula (103) effects a significant reduction in whiteness and fluorescence of pre-brightened paper treated with said compound. Example 4 The compound of formula (104) is obtained in a yield of 87% of theory using the procedure described in Example 3, except that the L-glutamic acid is replaced by iminodiacetic acid. Elemental analysis of the compound having the formula (104) and having the empirical formula C 44 H 34 N 12 Na 6 O 16 S 2 . 0.8 NaCl. 15 H 2 O gives: Req.% C 35.1; H 4.28; N 11.16; S 4.26. Found % C 35.0; H 4.3; N 11.2; S 4.4. The compound having the formula (104) effects a significant reduction in whiteness and fluorescence of pre-brightened paper treated with said compound.

Claims: A compound having the formula: in which X is O or NH; M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine; each R 1 , independently, is an amino acid residue from which a hydrogen atom on the amino group has been removed; whereby the amino acid from which the amino acid residues R 1 are derived is glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hydroxyphenylalanine), diiodotyrosine, tryptophan (β-indolylalanine), histidine ((β-imidazolylalanine), α-aminobutyric acid, methionine, valine (α-aminoisovaleric acid), norvaline, leucine (α-aminoisocaproic acid), isoleucine (α-amino-β-methylvaleric acid), norleucine (α-amino-n-caproic acid), arginine, ornithine (α,δ-diaminovaleric acid), lysine (α,ε-diaminocaproic acid), aspartic acid (aminosuccinic acid), glutamic acid (α-aminoglutaric acid), threonine, hydroxyglutamic acid or taurine, or a mixture or an optical isomer thereof or iminodiacetic acid and each R 3 , independently, is C 1 -C 3 alkyl or phenyl. A compound according to claim 1 in which X is NH. A compound according to either of the preceding claims in which each of the amino acid residues R 1 is the same. A compound according to claim 3 in which the amino acid from which the amino acid residues R 1 are derived is glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hydroxyphenylalanine), diiodotyrosine, tryptophan (β-indolylalanine), histidine ((β-imidazolylalanine), α-aminobutyric acid, methionine, valine (α-aminoisovaleric acid), norvaline, leucine (α-aminoisocaproic acid), isoleucine (α-amino-β-methylvaleric acid), norleucine (α-amino-n-caproic acid), arginine, ornithine (α,δ-diaminovaleric acid), lysine (α,ε-diaminocaproic acid), aspartic acid (aminosuccinic acid), glutamic acid (α-aminoglutaric acid), threonine, hydroxyglutamic acid or taurine, or a mixture or an optical isomer thereof. A compound according to claim 4 in which the amino acid from which the amino acid residues R 1 are derived is sarcosine, taurine, glutamic acid or aspartic acid. A compound according to any of claims 1 to 3 in which the amino acid from which each amino acid residue R 1 is derived is iminodiacetic acid. A compound according to any of the preceding claims in which M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C 1 -C 4 alkylammonium, mono-, di- or tri-C 1 -C 4 hydroxyalkylammonium or ammonium that is di- or tri-substituted with a mixture of C 1 -C 4 alkyl and C 1 -C 4 hydroxyalkyl groups. A compound according to claim 7 in which each M is Na. Use of the compound of formula (1), according to claim 1, for inhibiting (quenching) the effect of anionic fluorescent whitening agents on substrates.

Inventors: METZGER GEORGES, REINEHR DIETER, ROHRINGER PETER, METZGER, GEORGES, REINEHR, DIETER, ROHRINGER, PETER
Applicants: CIBA SC HOLDING AG, CIBA SPECIALTY CHEMICALS HOLDING INC.
Application year: 1998
Main classification: C07D251
IPC codes: C11D3, D21H21, C07D251, D06L3