GB1586820A

GB1586820A - Asymmetrical xanthene dyestuffs process for their manufacture and use

Info

Publication number: GB1586820A
Application number: GB5225377A
Authority: GB
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1976-12-17
Filing date: 1977-12-15
Publication date: 1981-03-25
Also published as: IT1088595B; BE862012A; NL7713739A; DE2657218A1; JPS5375224A; FR2374382A1

Description

(54) ASYMMETRICAL XANTHENE DYESTUFFS, PROCESS FOR THEIR MANUFACTURE AND USE (71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of 6230 Frankfurt/Main 80, Postfach 80 03 20, Federal Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to asymmetrical xanthene dyestuffs, and a process for their manufacture and use for dyeing and printing wool, silk and synthetic fibres containing basic groups.

German Patent Specification No. 916,724 describes a process for the manufacture of asymmetrical xanthene dyestuffs which comprises reacting compounds of the formula

(in which R1 represents hydrogen, an aliphatic or cycloaliphatic radical, R2 represents an aromatic or a heterocyclic radical and X is an exchångeable atom or group and in which the benzene nucleus carrying the sulphonic group may contain further substituents), at elevated temperature with primary or secondary amines and optionally sulphonating the substitution products obtained. In this process red to blue dyestuffs are obtained which are suitable for dyeing wool and synthetic polyamide fibres.

The present invention provides novel and valuable asymmetrical xanthene dyestuffs of the formula (I)

in which R, represents a hydrogen atom, a lower alkyl group, for example methyl or ethyl, a p-cyanoethyl, P-hydroxyethyl, or sulphomethyl group, R2 represents a hydrogen atom, a lower alkyl group, for example methyl or ethyl, or a lower hydroxyalkyl group, for example a p-hydroxyethyl, A- or y-hydroxypropyl group, R3 represents a hydrogen atom, a lower alkoxy group, a sulphonic or carboxy group, or a halogen atom, for example chlorine or bromine, R4 represents a hydrogen atom, a lower alkyl group, for example methyl or ethyl, a halogen atom, for example chlorine, fluorine or bromine, a trifluoromethyl, cyano or a lower alkoxy group, for example methoxy or ethoxy, an aryloxy group, for example phenoxy, a hydroxy, carboxy, or carbonamide group, a carboxylic acid mono or dialkyl amide group in which the alkyl radicals are lower alkyl radicals, a lower alkylsulphonyl group, an arylsulphonyl group for example phenylsulphonyl, an amino group, a mono- or dialkylamino group in which the alkyl radicals are lower alkyl radicals, an arylamino group, for example phenylamino, an acylamino group of a lower alkyl or alkenyl carboxylic acid or of an arylcarboxylic acid, for example benzoic acid, or of a lower alkane-sulphonic acid or of an arylsulphonic acid, for example a benzene- or toluene-sulphonic acid, or a nitro or lower hydroxyalkylsuiphonyl group, Rs represents hydrogen, a lower alkyl group, for example methyl or ethyl, a halogen atom, for example chlorine, fluorine or bromine, a trifluoromethyl, cyano or a lower alkoxy group, for example methoxy or ethoxy, a lower alkylsulphonyl group, for example methyl- or ethylsulphonyl, an arylsulphonyl group, for example phenylsulphonyl, or a hydroxy group, the radicals R, R2, Ra, R4 and R5 as defined above being either identical or different from one another, n=l, 2 or 3, M represents the equivalent of a hydrogen, sodium, potassium, calcium, magnesium, ammonium, or tetramethylammonium cation, Y represents a hydrogen atom, a sulphonic, sulphato, carboxy, sulphonamido or carbamido group or a mono- or dialkyl-sulphonamido or mono or dialkyl-carbonamido group wherein each alkyl radical is a lower alkyl radical or a cyano or hydroxy group, and when R4 or R5 or both represent hydrogen the benzene nucleus a may also contain a fused benzene ring thus, for example, forming a naphthalene ring of formulae

In particular, dyestuffs of formula (I) may be mentioned in which Rj is hydrogen, methyl, ethyl, p-cyanoethyl, p-hydroxyethyl or sulphomethyl, R2 is hydrogen, methyl, ethyl, p-hydroxyethyl, or p-hydroxypropyl, Ra is hydrogen, chlorine, methoxy, carboxy or sulphonic, R4 is hydrogen, fluorine, chlorine, bromine, trifluoromethyl, hydroxy, methoxy, nitro, amino, phenylamino, methylsulphonyl, ,B- hydroxyethylsulphonyl, carboxy or carboxylic acid dimethylamide, R5 is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, hydroxy, methoxy, ethoxy, trifluoromethyl, cyano, methylsulphonyl, or phenylsulphonyl, Y is hydroxy, cyano, sulphonic, sulphamoyl, carboxy, carbamoyl or sulphato, the aforesaid radicals being either identical or different from each other, and M, n and a have the aforesaid meanings, M preferably representing hydrogen, sodium or potassium, or advantageously sodium.

The novel compounds of formula (I) are valuable red to blue dyestuffs which are characterized especially by high brilliancy and light-stability and in this respect are superior to the dyestuffs described in German Patent Specification No. 916,724.

The aforesaid dyestuffs of formula (I) especially preferred are those in which Ri is hydrogen, R2 is methyl, R3 is hydrogen, R4 is hydrogen, methyl, ethyl, methoxy, ethoxy, hydroxy, or chlorine, Rs is hydrogen, methyl, ethyl, methoxy, ethoxy, or chlorine, n=2, M is hydrogen or sodium and Y is hydrogen, sulphonic, carboxy, said radicals being either identical or different from one another.

The invention also provides a process for the manufacture of the novel compounds of formula (I), which comprises reacting a compound of the formula (II)

(in which R1, R3, R4, R,, M and a have the aforesaid meanings and X represents a halogen atom, preferably chlorine or bromine, or a lower alkoxy group, for example methoxy or ethoxy) with an amine of the formula (III)

(in which R2, n and Y have the aforesaid meanings), in a polar solvent, optionally in the presence of an acid-binding agent, at a temperature of from 60 to 1500C, preferably 80 to 1200C.

The term "lower" in the above definitions of formulae (I), (II), and (III) indicates that the alkyl or alkenyl moieties of the radicals or groups referred to contain from 1 to 4 carbon atoms.

In the process of the invention for the manufacture of the dyestuffs of formula (I) the starting amines of formula (III) may be used in excess but preferably in a stoichiometric amount. The use of a stoichiometric amount of amine has the advantage that the waste waters from the dyestuff production are free or practically free from amine and no excess of amine is present in the dyestuff or in the dyeing process. A residue of amine in the dyestuff would have the further serious disadvantage that said dyestuffs cannot be used in combination dyeings with reactive dyes because of a possible secondary reaction of the amine with the reactive dye.

Suitable solvents in the process of the invention are preferably water or organic polar compounds which do not contain acid groups, for example alkanols having from 1 to 6 carbon atoms, for example methanol, ethanol, isobutanol, dihydroxyalkanols having from 2 to 6 carbon atoms, for example ethylene glycol or propylene glycol, C2-C4-alkyl ethers or hydroxy-(C2-C4-alkyl)ethers of these compounds, for example diglycol; dimethylformamide, acetonitrile, formamide, or N-methylpyrrolidone.

Acid-binding agents which may be used in the process of the invention are especially inorganic and organic substances having an alkaline reaction, for example alkali metal or alkaline earth metal salts of weak or medium inorganic and organic acids, preferably the sodium, potassium, calcium or magnesium salts, for example the salts of carbonic acid, acetic acid, boric acid, phosphoric acid, or the hydroxides or oxides of said alkali metals and alkaline earth metals or of aluminium; organic bases for example tertiary amines or aromatic heterocyclic nitrogen-containing bases, for example triethanolamine or pyridine.Inorganic compounds that may be mentioned in particular are: sodium and potassium hydroxide, calcium and magnesium hydroxide, calcium and magnesium oxide, aluminium oxide and aluminium trihydroxide, sodium, potassium and calcium carbonate, sodium bicarbonate, sodium phosphate, disodium hydrogen phosphate, sodium borates for example sodium metaborate or sodium tetraborate, and sodium acetate.

The reaction time is generally from'2 to 5 hours, and generally depends on the chosen reaction temperature and the reactivity of the starting compounds. Within the indicated limits, the reaction temperature can however be freely chosen and in general depends on the solvent used, provided that the reaction is not carried out under pressure. Reaction temperatures near the upper limit can be used when the rate of reaction of the starting materials at low temperature is too slow.

In addition to the sulphonic group in the 9-phenyl radical of the xanthene molecule, the dyestuffs of the invention may contain one or more further sulphonic groups the positions of which can clearly be defined in the dyestuff molecule.

Hence, dyestuffs of the invention having a definite constitution can be prepared by a predetermined synthesis.

This is not possible with the known dyestuffs; therefore the sulphonic groups of the dyestuffs of German Patent Specification No. 916,724 are introduced by subsequent sulphonation whereby a statistical distribution of the sulphonic groups can only be obtained. In the contradistinction thereto, the process of the present invention provides uniform dyestuffs which contain together with the aforesaid 2'sulphonic group in the 9-phenyl radical, a sulphonic group in the benzene nucleus a in meta position to the amino group as another sulphonic group bound to an aromatic nucleus. Surprisingly, the dyestuffs of the invention having a specific constitution results in an especially good fastness to light and very high brilliancy.

Compounds of formula (I) of this type cannot be prepared by known subsequent sulphonation process wherein higher sulphonated dyestuffs are formed in addition to the monosulphonated products. When dyeing wool or synthetic polyamide fibres, these higher sulphonated products have a poorer affinity than the dyestuffs of the present invention and consequently dyeings of lower tinctorial strength are obtained with the known dyestuffs and more strongly coloured waste waters are produced.

The novel dyestuffs of formula (I) are excellently suitable for dyeing and printing wool, silk or synthetic fibres carrying basic groups, for example polyamide fibres and basically modified polyester, polyacrylonitrile or regenerated protein fibres. They dye these materials brilliant red to blue shades. The dyeings and prints are distinguished by outstanding fastness properties, especially high fastness to light and alkalies. The dyestuffs of the invention are especially suitable for exhaustion dyeing.

The dyestuffs can be applied by known dyeing and printing processes for said fibres and by dyeing processes for xanthene dyes containing sulphonic groups. As regards their dyeing properties, the dyestuffs of the invention are characterized by an excellent levelling power.

The starting compounds of formula (II) are preferably prepared by the process of our copending patent application No. 52254/77 filed concurrently herewith; this process is characterized by reacting a compound of formula

with an amine of formula

wherein R1, R3, R4, R5, M, X and a are defined as above, in a polar solvent at an elevated temperature, preferably, in water at a temperature of from 70 to 140"C, and in a strongly acid range, for example at a pH of from 0.3 to 4.

The following examples illustrate the invention, the parts and percentages being by weight and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the litre.

EXAMPLE 1 11.4 Parts of the compound of the formula

together with 3.2 parts of the sodium salt of N-methylaminoethanesulphonic acid were dissolved in 100 parts of water and 2.1 parts of anhydrous sodium carbonate were added while stirring. The reaction mixture was heated to reflux-temperature and refluxed for 4 hours while stirring. 0.5 Parts of kieselguhr were then added and the hot mixture was filtered. For salting out, 10 parts of sodium chloride were added to the filtrate at 200 C, the precipitate was filtered with suction, washed with 100 parts of a cold aqueous 10% sodium chloride solution and dried. 16 Parts of a dyestuff of the formula

were obtained having a good solubility in water.It dyed wool, synthetic polyamide fibres, silk, basically modified polyacrylonitrile or polyester fibres brilliant violet shades by the usual dyeing and printing processes for water-soluble xanthene dyes, the colourations being distinguished by a very intense shade and high fastness to light.

EXAMPLE 2 54 Parts of the compound of the formula

14 parts of N-methylaminoethane-sulphonic acid, 32 parts of anhydrous sodium carbonate 2 parts of kieselguhr and 300 parts of water were heated to refluxtemperature. The reaction solution, which rapidly turned red-violet, was refluxed for a further 4 hours. The solution was adjusted to pH7 by adding dilute hydrochloric acid, and clarified by passing it through a paper filter. The filtrate was spray-dried in known manner.

10 Parts of a dyestuff powder containing 68% of the dyestuff of the formula

were obtained. The dyestuff was very readily soluble in water and dyed wool very brilliant red-violet shades from an acidified aqueous dyebath.

When using equivalents amounts of sodium bicarbonate, potassium carbonate, sodium hydroxide, calcium hydroxide, magnesium oxide, aluminium hydroxide, sodium acetate, sodium tetraborate, trisodium phosphate, triethylamine, or pyridine, instead of anhydrous sodium carbonate the corresponding salts of the above sodium dyestuff were obtained which were also excellently suitable for dyeing wool.

EXAMPLE 3 60.5 Parts of a compound of the formula

and 14 parts of N-ethylamino-acetic acid in the form of the sodium salt were refluxed in 200 parts of methanol for 4 hours while stirring; after cooling, the reaction mixture was stirred into 500 parts of water. 100 Parts of sodium chloride were added to the aqueous methanolic solution at room temperature and the whole was stirred for I hour. The precipitated product was filtered with suction, washed with 100 parts of an aqueous 20 /,, sodium chloride solution and dried at 600 C. 80 Parts of a dyestuff powder containing 80 /, of the dyestuff of the formula

were obtained, which dyed wool in known manner very brilliant red-violet shades having very good fastness to light.

EXAMPLE 4 The reaction was carried out as described in Example 3, except that the sodium salt of N-ethylaminoacetic acid was replaced by an equivalent amount of the sodium salt of aminoacetic acid. A dyestuff of the formula

was obtained, which dyed wool brilliant red shades.

EXAMPLE 5 When the reaction was carried out as described in Example 3, but replacing the methanol as solvent by the same amount of ethanol, isopropanol, isobutanol, glycol, diglycol, N-methylpyrrolidone (2), dimethylformamide, acetonitrile, or formamide, the dyestuff of the formula indicated in Example 3 was likewise obtained in good yield and purity.

EXAMPLE 6 11.4 parts of a compound of the formula

3.5 parts of N-ethylaminoethane-sulphonic acid in the form of its sodium salt, 2.1 parts of anhydrous sodium carbonate and 100 parts of isobutanol were heated to 150"C in an autoclave and stirred for 2 hours at said temperature. After cooling and pressure release, the isobutanol was distilled- off under reduced pressure. The residue was dried at 600C and ground. 17 Parts of the dyestuff of the formula

were obtained. It dyed wool brilliant violet shades fast to light.

EXAMPLE 7 A dyestuff was prepared as described in Example 6 but, instead of the sodium salt of N-ethylaminoethane-sulphonic acid, the equivalent amount of the potassium salt of N-(p-hydroxyethyl)-aminoethane-sulphonic acid and instead of sodium carbonate the equivalent amount of anhydrous potassium carbonate were used.

The dyestuff obtained had the formula

and dyed wool brilliant blue-violet shades.

EXAMPLE 8 58 Parts of the compound of the formula

12 parts of N-methylamino-butyric acid and 8 parts of magnesium oxide in 200 parts of water were refluxed for 5 hours while stirring. 5 Parts of kieselguhr were then added, the hot reaction mixture was filtered and the filtrate was spray-dried in known manner. 75 Parts of a dyestuff of the formula

were obtained which dyed wool very brilliant red shades by known dyeing processes.

EXAMPLES 9 to 14 By using any one of the amines indicated in the following Table instead of Nmethylamino-butyric acid as described in Example 8, valuable dyestuffs were likewise obtained, which dyed wool very brilliant shades as indicated in the Table.

Example No. amine shade on wool

CH, 9 HN brilliant red CH2-CH2-OSO3H /CH3 10 HN 10 HN brilliant red CH2-CH2-SO2NH2 OH 7CH2-CH-CH3 Il HN I I HN brilliant bluish red CH2-C112-SO3 H CH3 12 HN brilliant red CH 2-CONH2 13 H2N-CH2-CH2-OH red CH3 14 HN 14 HN brilliant red CH2-CH2&num;;N EXAMPLES 15 to 33 According to the process of the invention, for example in a manner analogous to that of the preceding Examples and preferably according to Examples 1 and 2, valuable dyestuffs of formula (I) as listed in the following Table were prepared by using the respective starting xanthene and amino compounds of formulae (II) and (III). These dyestuffs dyed wool the shades indicated in the Table. Example shade on wool or No. dyestuff polyamide fibres

c','3 CH3 CH3 1o N-CH CH2 SO3A'a yellowish red 15 SO3H o r o 16 CH2 SO3Ma red O )c) CH3O o6 C2 H4 CA' CH3 17 A'&commat;{)1$NCH2 O SO3 Ha yellowish red ;;e t c6 Example shade on wool or No. dyestuff polyamide fibers

C2 H4 OH -cl 18 "! yellowish red f CwO3w 3 3 COOH CH3 re 19 CC e 503 Ma SO3 L CH3 TO SO3M red 20 cws&commat;c e t-t V J W oE o Example shade on wool or No. dyestuff polyamide fibres

CH3 . 0 3 = -o 8r .0 A'- CH2COMa 22 yellowish red SO ' Ma 0 CM CH3 O ? i ? red 23 F C oi N en Example shade on wool No. dyestuff polyamide fibres

OC2Hs C1H NH0 N- CH2 COOMa 24 HoOcC - red violet 503 Ma '5 o o O g % S 25 O)SO3) - cH COOM red CH3 502 26 !!NH&commat;;Oc)II$KNCH2 COOMa yellowish red T II5F$03 e Example shade on wool or No. dyestuff polyamide fibres

CH3 OH NH0 N- CH2 COOMa 27 reddish blue HO 503 Ma 1 -ci -c p 5 c . ~ . X ~ C: r 5 ~ O 28 A1OC C e CH3 SO3 Ma SO3 bluish red CH3 29 C612 g0)%NH&commat;{)tmM C'W2 COOMa bluish red 0 03e C2H b %MNHCȯcO)$KWCW2 Cw 4 U 'Va reddish blue t F (E N on Example shade on wool or No. dyestuff polyamide fibers

31 02N /vH red E; -cl < , D D 4'- 0 06/2 SOs 9 h) 503e 0 O M N- Cll2CH2 SO3Ma bluish red NH0 33 N t, t, CH3 CH3 34 N- Cfl2- C112-SO3 Na bluish red SO3N tDFso3e

Claims

WHAT WE CLAIM IS:

1. A xanthene dyestuff of the formula (I)

in which R, represents a hydrogen atom, a lower alkyl group, a -cyanoethyl, ss- hydroxyethyl, or sulphomethyl group, R2 represents.a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group, R3 represents a hydrogen atom, a lower alkoxy group, a sulphonic acid or carboxy group, or a halogen atom, R4 represents a hydrogen atom, a lower alkyl group, a halogen atom, a trifluoromethyl, cyano, or a lower alkoxy group, an aryloxy group, a hydroxy, carboxy or carbonamide group, a carboxylic acid mono or dialkylamide group containing lower alkyl groups, a lower alkylsulphonyl group, an arylsulphonyl group, an amino group, a mono- or dialkylamino group containing lower alkyl groups, an arylamino group, an acylamino group of a lower alkyl carboxylic acid or of a lower alkenyl carboxylic acid or of an arylcarboxylic acid or of a lower alkanesulphonic acid or of an arylsulphonic acid, or a nitro, or a lower hydroxyalkylsulphonyl group, R5 represents hydrogen, a lower alkyl group, a halogen atom, a trifluoromethyl, cyano or a lower alkoxy group, a lower alkylsulphonyl group, an arylsulphonyl group or a hydroxy group, n=l, 2 or 3, M represents the equivalent of a hydrogen, sodium, potassium, calcium, magnesium, ammonium, or tetramethylammonium cation, Y represents a hydrogen atom, a sulphonic acid, sulphato, carboxy, sulphonamido or carbamido group or a mono- or dialkylsulphonamido or a mono- or dialkyl-carbonamido group in which each alkyl is a lower alkyl group or a cyano or hydroxy group, and the radicals R1, R2, R3, R4, R5 and Y as defined above are identical or different from one another, and when R4 or R5 or both represent hydrogen the benzene nucleus a may also contain a fused benzene ring.

2. A xanthene dyestuff as claimed in claim 1 in which in the formula (I) R1 is hydrogen, methyl, ethyl, p-cyanoethyl, A-hydroxyethyl or sulphomethyl, R2 is hydrogen, methyl, ethyl, p-hydroxyethyl, or p-hydroxypropyl, R3 is hydrogen, chlorine, methoxy, carboxy or sulphonic, Ra is hydrogen, fluorine, chlorine or bromine, trifluoromethyl, hydroxy, methoxy, nitro, amino, phenylamino, methylsulphonyl, P hydroxyethylsulphonyl, carboxy or a carboxylic acid dimethylamide group, Rs is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, hydroxy, methoxy, ethoxy, trifluoromethyl, cyano, methylsulphonyl or phenylsulphonyl, Y is hydroxy, cyano, a sulphonic acid, sulphonic acid amide, carboxylic acid, carboxylic acid amide or sulphato group, and M n and a have the meanings indicated in claim 1.

3. Xanthene dyestuff as claimed in claim I or claim 2, in which R, is hydrogen, R2 is methyl, R3 is hydrogen, R4 is hydrogen, methyl, ethyl, methoxy, ethoxy, hydroxy or chlorine, Rs is hydrogen, methyl, ethyl, methoxy, ethoxy, or chlorine, n=2, M is hydrogen or sodium, Y is hydrogen or a sulphonic acid or carboxylic acid group and a has the meaning defined in claim 1.

4. Dyestuffs as claimed in any one of claims 1, 2 or 3, in which M in formula (2) represents hydrogen, sodium or potassium.

5. A dyestuff as claimed in claim I having the formula

in which M has the meaning as defined in claim 1 or claim 4.

6. A dyestuff as claimed in claim I having the formula

in which M has the meaning as defined in claim I or claim 4.

7. A dyestuff as claimed in claim I having the formula

in which M has the meaning as defined in claim 1 or claim 4.

8. A dyestuff as claimed in claim 1 having the formula

in which M has the meaning as defined in claim 1 or claim 4.

9. Any one of the dyestuffs as claimed in Claim I obtained substantially as described and exemplified herein.

10. A process for the manufacture of a dyestuff of the formula given in claim I, which comprises reacting a compound of the formula (II)

in which R1, R3, R4, R5, M and a have the meanings defined in claim I and X represents a halogen atom or a lower alkoxy group, with an amine of the formula (III)

in which R2, n and Y have the meanings defined in claim 1, in a polar solvent, optionally in the presence of an acid-binding agent, at a temperature of from 60 to 150"C.

I I. A process as claimed in claim 10 wherein X in the formula II represents chlorine or bromine.

12. A process as claimed in claim 10 or 11 conducted substantially as described and exemplified herein.

13. A process as claimed in claim 10, wherein any of the solvents and acid binding agents specifically mentioned herein are used.

14. Use of dyestuffs as claimed in claim 1 for dyeing and printing wool, silk, or synthetic fibres containing basic groups.

15. A process for dyeing and printing wool, silk or synthetic fibres containing basic groups wherein a xanthene dye of formula (I) given in claim 1 is applied to the fibrous material and fixed.

16. A process as claimed in claim 15 wherein the material is made of or contains wool, silk, polyamides, basically modified polyester or polyacrylonitrile or regenerated protein fibres.

17. A process as claimed in claim 15 or 16 carried out substantially as described herein.

18. Materials of wool, silk or synthetic fibres containing basic groups which have been dyed with a dyestuff as claimed in claim 1 or by the process claimed in claim 15.

19. A dyestuff of the formula given in claim 1 prepared by a process as claimed in any one of claims 10 to 13.