GB2056475A

GB2056475A - Cationic Dyes

Info

Publication number: GB2056475A
Application number: GB8029734A
Authority: GB
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1978-07-25
Filing date: 1978-07-25
Publication date: 1981-03-18
Also published as: GB2056475B

Abstract

Cationic dyes have the general formula I <IMAGE> where R is unsubstituted or substituted alkyl, T is hydrogen or alkyl, A<(-)> is an equivalent of an anion, n is 1, 2 or 3 and X is an aminoaryl radical which may or may not possess one or more further substituents on the amino and/or the aryl moiety. The dyes are yellow to orange and may be used for dyeing paper (as claimed in G.B. Patent Publication No. 2002424), textiles of anionically modified fibers, leather, tannin-treated cotton, writing fluids, print pastes, silk, cellulose acetate and lignin-containing fibers.

Description

SPECIFICATION Cationic Dyes The present invention relates to novel cationic dyes.

According to the invention there are provided cationic dyes of the general formula I

where R is unsubstituted or substituted alkyl, T is hydrogen or alkyl, As is an equivalent of an anion, n is 1, 2 or 3 and X is an aminoaryl radical which may or may not possess one or more further substituents on the amino and/or the aryl moiety.

The radical X may in particular have the formula

where B1 forms a ring with the o-position of the aryl radical or B1 and B2 independently of one another are hydrogen or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl, or B1 and B2 conjointly with the N atom are a hetero-cyclic ring, B3 is hydrogen, alkyl, hydroxyl or alkoxy, B4 is hydrogen, chlorine, bromine or alkyl and B3 and B4 together are a fused benz ring.

In addition to hydrogen, examples of radicals B1 and B2 are alkyl of 1 to 8 carbon atoms which may be substituted by amino, alkoxy of 1 to 4 carbon atoms, chlorine, bromine, cyano, alkylamino of 1 to 4 carbon atoms, dialkylamino, where alkyl is of 1 to 4 carbon atoms, trialkylammonium, where alkyl is of 1 to 4 carbon atoms, alkanoyloxy of 1 to 8 carbon atoms, alkoxycarbonyl, where alkoxy is of 1 to 8 carbon atoms, alkylaminocarbonyloxy, where alkyl is of 1 to 4 carbon atoms, or alkanoylamino of 1 to 4 carbon atoms and further examples are allyl, cyclohexyl, benzyl which may be substituted by methyl or methoxy, phenylethyl and phenyl which may be substituted by methoxy, ethoxy or chlorine.

Specific examples in addition to the radicals B1 and B2 already mentioned are methyl, ethyl, nand iso-propyl, n-, iso- and tert.-butyl, hydroxyethyl, cyanoethyl, methoxyethyl, ethoxyethyl, aminoethyl, dimethylaminoethyl, trimethylammonium ethyl, chloroethyl, bromoethyl, acetoxyethyl, am inocarbonylethyl, dimethylaminocarbonylethyl, p-hydroxy-n-propyl, p-hydroxy-n-butyl and ,B- hydroxy-iso-butyl.

If B' forms a ring with the o-position of the aryl radical, X may in particular have the formula

where B5 is benzyl or alkyl of 1 to 4 carbon atoms, preferably methyl.

Examples of heterocyclic rings

are pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl and tetrahydropyrazolyl.

Specific examples of radicals R' are methyl, ethyl, n- and iso-propyl, n-, iso- and tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, chloroethyl, bromethyl, hydroxyethyl, methoxyethyl, ethoxyethyl, cyanoethyl, acetoxyethyl, aminocarbonylethyl, -hydrnxy-n-prnpyI, /3- hydroxy-n-butyl, P-hydroxy-iso-butyl, phenyl methyl, phenylethyl, p-methylphenyl methyl, pmethoxyphenyl methyl and p-ethoxyphenyl methyl.

Alkyl and alkoxy radicals B3 and B4 are, in particular, methyl, ethyl, ethoxy and methoxy. The compounds of the formula I may be prepared by condensing a compound of the formula II

with a compound of the formula Ill X-CHO (Ill) in a basic medium.

The condensation may be carried out in the presence or absence of a solvent. Examples of suitable solvents are primary, secondary and tertiary amines, halohydrocarbons, alcohols, glycols, glycol ethers, DMF, NMP, DMSO and HMPT, which may or may not be mixed with water or with one another.

Specific examples of suitable solvents are (aqueous) methylamine, ethylamine, piperidine, pyrrolidine, dimethylamine, diethylamine, triethylamine, methylene chloride, chloroform, carbon tetrachloride, chloroethane, 1,1 - and 1 ,2-dichloroethane, chlorobenzene, 1 ,2-dichlorobenzene, methanol, ethanol, n- and iso-propanol, n-, iso- and tert.-butanol, ethylene glycol, glycerol, butylglycol, ethylene glycol monomethyl ether, propylene diglycol, dimethylformamide, NMP, DMSO, and HMPT.

The medium may be rendered basic by using, for example, an alkali, alcoholate or amine. Specific examples are magnesium oxide, calcium oxide, dimethylamine, diethylamine, di-n-propylamine, di-iso propylamine, di-n-butylamine, di-iso-butylamine, N-methylaniline, N-ethylaniline, methylamine, ethylamine, n- and iso-propylamine, n-, iso- and tert.-butylamine, aniline, triethylamine, trimethylamine, dimethylaniline, pyridine, a-"B- and y-picoline, or a methanolate, ethanolate, n- and iso-propanolate and n-, iso- and tert.-butanolate.

As may be seen, the base and the solvent can be identical.

Further details of the condensation reaction may be found in the examples, where parts and percentages are by weight, unless stated otherwise.

A compound of the formula II may be obtained from compound of the formula IV

by quaternizing with R-A, where A is a radical removable as an onion.

Examples of anions Ao, which can also be introduced into the quaternized products by double decomposition, are chloride, bromide, sulfate, methosulfate, ethosulfate, toluenesulfonate, benzenesulfonate, nitrate, phosphate, acetate, format, hydroxyl, tetrafluoborate, bisulfate, aminosulfate, hydrogen phosphate, metaphosphate, bicarbonate, tetrachlorozincate, chloroacetate, hydroxyacetate, propionate, trichloroacetate, benzoate and phthalate.

A compound of the formula IV is obtained when a compound of the formula

is reacted with a lactone or lactam of the formula

where Z is --O, --NHH- or --N alkyl.

The invention in a particular embodiment provides cationic dyes of the formula

where R is alkyl of 1 to 12 carbon atoms, alkyl of 2 to 4 carbon atoms which may be substituted by hydroxyl, alkoxy of 1 to 4 carbon atoms, alkanoyloxy of 1 to 4 carbon atoms, carbamoyl, cyano, chlorine or bromine, benzyl, which is unsubstituted or substituted by methyl, methoxy, ethoxy or chlorine, or phenylethyl, T is hydrogen or alkyl of 1 to 4 carbon atoms, nis 1,2or3, X is a radical of the formula

B' and B2 independently of one another are alkyl of 1 to 8 carbon atoms, alkyl of 2 to 4 carbon atoms which is substituted by trialkylammonium, where alkyl is of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, bromine, cyano, alkanoyloxy of 1 to 8 carbon atoms, alkoxycarbonyl, where alkoxy is of 1 to 8 carbon atoms, alkylaminocarbonyloxy, where alkyl is of 1 to 4 carbon atoms, or alkanoylamino, where alkanoyl is of 1 to 4 carbon atoms, allyl, cyclohexyl, benzyl which is unsubstituted or substituted by methyl or methoxy, phenylethyl, phenyl which is unsubstituted or substituted by methyl, methoxy or chlorine, or a radical of the formula

B3 is hydrogen, methyl, ethyl, hydroxyl, methoxy or ethoxy, B4 is hydrogen, chlorine, methyl or ethyl, B5 is hydrogen, alkyl of 1 to 4 carbon atoms or benzyl, Be is hydrogen, methyl or phenyl, the radicals B7 independently of one another are hydrogen, aikyl of 1 to 4 carbon atoms, or alkyl of 2 or 3 carbon atoms substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms,

is pyrrolidino, piperidino, morpholino, piperazine, N-methylpiperazino or hydroxyethylpiperazino, B is straight-chain or branched C2 to C8 alkylene, q is O, 1. 2 or 3 and Ao is an anion.

The radicals X1 preferably have the formula

where B1 and B2 are preferably unsubstituted alkyl, especially of 1 to 4 carbon atoms, and preferentially methyl or ethyl.

R is preferably methyl, ethyl or benzyl.

Particularly preferred dyes for use according to the invention have the general formula:

where B1, B2, n and As have the above meanings.

The compounds of the formula I are yellow to orange and may be used as basic dyes for dyeing, in particular mass-dyeing, paper, dyeing textiles of anionically modified fibers, leather, tannin-treated cotton, writing fluids, print pastes, silk, cellulose acetate and lignin-containing fibers. Suitable substrates include bleached and unbleached sulfite cellulose, bleached and unbleached sulfate cellulose and groundwood. On paper, the dyes of the formula I are distinguished by high substantivity, good resistance to bleeding, fairly good lightfastness and high brilliance. Paper dyed with a dye of formula I and other related cationic dyes is disclosed and claimed in our copending GB patent application No. 31008/78 (Publication No. 2002424) from which this application is divided. All the information contained in that application is hereby incorporated in the present application.

The following Examples illustrate the invention.

Example 1 41 g of 4,5-dimethyl-o-phenylenediamine, 26 g of butyrolactone and 5 ml of glacial acetic acid are heated at 2000C until 11 ml of H20 have distilled off. The mixture is allowed to cool and 30 mlof dimethyl sulfate are slowly added dropwise at 90-11 00C. This mixture is kept for 1 hour at 900C, after which 30 ml of piperidine are introduced dropwise and 55 g of p-dimethylaminobenzaldehyde are added. The reaction batch is kept at 900C for 1 hour.

40 ml of glacial acetic acid are then added and the homogeneous solution is poured out onto dilute sodium acetate solution.

Yield: 60 g of the dye of the formula

Example 2 The following dye is prepared by a method similar to that described above. The anion is acetate and the cation is

Example 3 The following dye is prepared by an analogous method, starting from 4,5-dimethyl-o-phenylene diamine and 8-valerolactone. The anion is acetate and the cation is

Example 4 41 g of 4,5-dimethyl-o-phenylenediamine, 30 g of y-valerolactone and 5 ml of glacial acetic acid are heated at 2000C until 11 ml of H20 have distilled off. The mixture is allowed to cool and 30 ml of dimethyl sulfate are slowly added dropwise at 90-11 00C. The batch is kept at 900C for 1 hour, after which 30 ml of piperidine are introduced dropwise and 55 g of p-dimethylaminobenzaldehyde are added. The reaction mixture is kept at 900C for 1 hour, 40 ml of glacial acetic acid are added and the homogeneous solution is poured out onto dilute sodium acetate solution.

Yield: 70 g of the dye of the formula

Claims

1. A cationic dye of the general formula:

where R is unsubstituted or substituted alkyl, T is hydrogen or alkyl, n is 1, 2 or 3, As is an equivalent of an anion and X is an aminoaryl radical which may or may not possess one or more further substituents on the amino and/or the aryl moiety.

2. A compound as claimed in claim 1 and having the general formula.

where R is alkyl of 1 to 12 carbon atoms, alkyl of 2 to 4 carbon atoms which may be substituted by hydroxyl, alkoxy of 1 to 4 carbon atoms, alkanoyloxy of 1 to 4 carbon atoms, carbamoyl, cyano, chlorine or bromine, benzyl which is unsubstituted or substituted by methyl, methoxy, ethoxy or chlorine, or phenylethyl, T is hydrogen or alkyl of 1 to 4 carbon atoms, nis 1,2or3, X is a radical of the formula

B1 and B2 independently of one another are alkyl of 1 to 8 carbon atoms, alkyl of 2 to 4 carbon atoms which is substituted by trialkylammonium, where alkyl is of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, bromine, cyano, alkanoyloxy of 1 to 8 carbon atoms, alkoxycarbonyl, where alkoxy is of 1 to 8 carbon atoms, alkylamino-carbonyloxy, where alkyl is of 1 to 4 carbon atoms, or alkanoylamino, where alkanoyl is of 1 to 4 carbon atoms, allyl, cyclohexyl, benzyl which is unsubstituted or substituted by methyl or methoxy, phenylethyl, phenyl which is unsubstituted or substituted by methyl, methoxy or chlorine or a radical of the formula

B3 iS hydrogen, methyl, ethyl, hydroxyl, methoxy or ethoxy, B4 is hydrogen, chlorine, methyl or ethyl, B5 is hydrogen, alkyl of 1 to 4 carbon atoms or benzyl, B6 is hydrogen, methyl or phenyl, the radicals B7 independently of one another are hydrogen, alkyl of 1 to 4 carbon atoms, or alkyl of 2 or 3 carbon atoms substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms,

is pyrrolidino, piperidino, morpholino, piperazino, N-methylpiperazino or N-P-hydroxyethylpiperazino, B is straight-chain or branched C2to C8 alkylene, qisO,1,2or3and As is an anion.

3. A compound as claimed in claim 1 or claim 2 where R is methyl, ethyl or benzyl.

4. A compound as claimed in any preceding claim where T is hydrogen or methyl.

5. A compound as claimed in any preceding claim where n is 1 or 2.

6. A compound as claimed in any preceding claim where X is a radical of the formula

and B' and B2 are each as defined in claim 2.

7. A compound as claimed in claim 6, where B1 and B2 independently of one another are methyl, ethyl. p-chloroethyl or a radical of the formula

p is 2, 3, 4, 5 or 6, and B7 and q are each as defined in claim 2.

8. The compound of the formula

9. The compound of the formula

10. Anionically modified fibers, leather, tannin-treated cotton, writing fluids, print pastes, silk.

cellulose acetate and lignin-containing fibers when dyed with a compound as claimed in any preceding claim.