GB1599297A

GB1599297A - Anthraquinone disperse dyestuffs

Info

Publication number: GB1599297A
Application number: GB28982/77A
Authority: GB
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1977-07-11
Filing date: 1977-07-11
Publication date: 1981-09-30
Also published as: JPS5417934A

Description

(54) ANTH RAQUINONE DISPERSE DYESTUFFS (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London, SW1P 3JF, a British Company 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 particulary described in and by the following statement:- This invention relates to anthraquinone disperse dyestuffs for the colouration of synthetic textile materials.

UK Patent Specification No. 1437444 describes and claims a compound of the formula

wherein X1 and X2 each are an amino or hydroxyl group, Y is a halogen atom, W is an oxygen or sulphur atom, Z is -CN, or a group of the formulaCONHR or VOOR in which R is a hydrogen atom, an alkyl group unsubstituted or substituted with a C1-C4 alkoxy group, a phenyl group or a halogen atom, or a phenyl group unsubstituted or substituted by a C,--C, alkyl or C1-C4 alkoxy group or a halogen atom, n is an integer of from 1 to 7, and m is 0, 1 or 2.

According to the present invention there are provided anthraquinone disperse dyestuffs having the formula:

wherein R is an alkyl group: Z represents a --COOR', --CN or -CONR"R"' group; R' represents an optionally substituted hydrocarbon radical which may contain hetero atoms. and R" represents hydrogen or an alkyl or substituted alkyl group and R"' represents an optionally substituted hydrocarbon radical which may contain hetero atoms.

The preferred meaning of R is ethyl or, more especially, methyl, and of Z is COOR' where R' is methyl or ethyl. The two oxygen atoms are preferably attached to the benzene ring in para position to each other.

As examples of alkyl or substituted alkyl radicals represented by R", there may be mentioned C1-C4 alkyl or C2-C4 hydroxyalkyl groups, e.g. methyl, ethyl, n- or i-propyl. n-, i- or t-butyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl and 2-, 3- or 4hydroxy butyl.

As examples of optionally substituted hydrocarbon radicals represented by R' and R"', there may be mentioned C1-C4 alkyl or C2-C4 hydroxyalkyl, C1-C4 alkoxy-C2-C4 alkyl, C2-C4 alkenyl, cyclohexyl, phenyl or phenyl substituted, e.g.

by halogen, methyl or methoxy.

As particular examples of the radicals represented by R', R" and R"' there may be mentioned methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, cyclohexyl, allyl, phenyl, p-methoxyphenyl, m-chloro phenyl, m-tolyl, A-hydroxyethyl, - methoxypropyl, p-methoxyethyl and p-ethoxyethyl.

According to a further feature of the invention there is provided a process for the manufacture of the anthraquinone disperse dyestuffs as defined above which comprises reacting an anthraquinone compound of the formula:

with a compound of the formula:

wherein W is a halogen atom and R and Z have the meanings defined above.

The anthraquinone compounds of formula (II) which may be employed in the above process are 1 - amino - 2 - (4 - hydroxyphenoxy) - 4 hydroxyanthraquinone and 1 - amino - 2 - (3 - hydroxyphenoxy)- 4hydroxyanthraquinone.

Examples of the compound of formula (III) which may be used are ethyl (F- chloropropionate, allyl a-chloropropionate, cyclohexyl ct-chloropropionate.

methyl cr-chlorobutyrate, a-chloropropionitrile and a-chloro-N,Ndiethylpropionamide.

The reaction between the anthraquinone compounds of formula (II) and the compound of formula (III) may be carried out in an inert solvent and in the presence of an acid-binding agent. Examples of suitable inert solvents are toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene.

trichloroethylene, tetrachloroethylene, dimethylformamide, dimethylacetamide, and dimethylsulphoxide. Suitable acid-binding agents are, for example, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and calcium carbonate. Alternatively, the reaction may be carried out in a basic inert solvent such as pyridine or quinoline, in which case no acid-binding agent is necessary.

In general the reaction may be carried out at a temperature from 50" to 1 800C.

The dyestuffs are isolated from the reaction mixture by conventional means.

According to a still further feature of the invention there is provided a process for the manufacture of the dyestuffs herein defined which comprises reacting the anthraquinone compound of the formula:

with a compound of the formula:

wherein R and Z have the meanings defined above.

Examples of the compounds of formula (V) which may be used are ethyl cg-(4- hydroxyphenoxy)propionate, allyl a-(4-hydroxyphenoxy)propionate, cyclohexyl a- (4-hydroxyphenoxy)propionate and methyl -(4-hydroxyphenoxy)butyrate.

The reaction between the anthraquinone compound of formula (IV) and the compound of formula (V) may be carried out in an inert solvent and in the presence of an acid-binding agent, and under the reaction condition, as hereinbefore described, for carrying out the reaction between an anthraquinone compound of formula (II) and compound of formula (III).

The compounds of formula (V) which are used in the above process may be obtained by reaction in alcoholic medium of a dihydroxybenzene with a compound of formula (III) as hereinbefore defined, a process which is more fully described in German Offenlegungsschriften P2824828 4.

The dyestuffs of the present invention are valuable for dyeing synthetic textile materials, in particular secondary cellulose acetate and cellulose triacetate textile materials, polyamide (such as polyhexamethyleneadipamide) textile materials and, above all, aromatic polyester (such as polyethylene terephthalate) textile materials.

Such materials can be in the form of filaments, fibres or woven or knitted materials.

The said anthraquinone dyestuffs can be applied to synthetic textile materials optionally in conjunction with other disperse dyestuffs by methods which are conventionally employed in applying disperse dyestuffs to such textile materials.

Thus, the dyestuffs in the form of aqueous dispersions can be applied by noncontinuous dyeing, or by padding or printing processes using the other additives which are conventionally used in carrying out such processes and heating to fix the dyestuffs on the material. At the conclusion of the said processes the coloured textile materials are usually rinsed in water and then preferably given a clearing treatment in order to remove loose dyestuff from the surface of the textile material.

Whilst this clearing treatment can comprise immersion in a warm aqueous alkaline solution of sodium hydrosulphite it is found that the presence of the sodium hydrosulphite is not essential and that treatment for a few minutes in aqueous alkaline solution having a pH of at least 8, preferably between 10 and 13.5, and at a temperature from 50 to 850C (for example, in an aqueous solution of sodium carbonate or sodium hydroxide) completely removes loose dyestuff.

The dyestuffs of the present invention are also valuable for the colouration of blends of aromatic polyester fibres and cellulose fibres, in conjunction with a reactive dyestuff for the cellulose fibres, using any of the conventional dyeing, padding or printing processes already referred to. The coloured aromatic polyester/cellulose unions so obtained are rinsed in water and may then be given an alkaline clearing treatment at a pH of at least 8 and at a temperature from 50 to 85"C as described above. In the case of printed polyester/cellulose unions this alkaline clearing treatment leaves any white unprinted areas essentially free from staining by unfixed disperse dyestuff.

The disperse anthraquinone dyestuffs according to the present invention can also be applied to synthetic textile materials by solvent methods of dyeing, for example, by applying a solution or dispersion of the dyestuff in perchloroethylene, optionally containing a minor amount to water, to the textile material preferably at an elevated temperature. The said dyestuffs can also be used in the melt colouration of synthetic polymers, for example, by the late injection technique, the coloured polymers then being melt spun into fibres or filaments. The said dye stuffs can also be applied to synthetic textile materials by the process of transfer colour printing, optionally under reduced air pressure or under wet or humid conditions.

When applied to synthetic textile materials the dyestuffs of the present invention give bright red shades which have excellent fastness to light and to wet and dry heat treatments, both before and after heat setting. The dyestuffs also have high tinctorial strength, excellent dyeing, levelling, temperature range and excellent build-up properties on synthetic textile materials, thus enabling heavy depths of shade to be readily obtained.

As compared with the dyes of UK Specification No. 1437444, the new dyes are superior in build up and give cleaner whites on clearing with dilute alkali.

The invention is illustrated but not limited by the following Examples in which parts and percentages are by weight.

Example 1 A mixture of 10.5 parts of 1 - amino - 2 - (p - hydroxyphenoxy)- 4 hydroxyanthraquinone, 4.2 parts of potassium carbonate and 10 parts of dimethylformamide are heated together at 1 150C for 1 hour. 12.3 Parts of ethyl a chloropropionate are then added and stirring and heating at 115"C are continued for a further hour, The reaction mixture is finally cooled to 800C, 150 parts of methanol are added and the resulting solution is allowed to cool, when I - amino 2 - [p - ( - ethoxycarbonyl)ethoxyphenoxy] -4 - hydroxyanthraquinone (7 parts) crystallises out. The dyestuff has m.p. 134"C.

When dispersed in aqueous medium the dyestuff dyes aromatic polyester textile materials in red shades and has excellent build-up properties. Any unfixed dyestuff on the surface of the dyed textile material is readily removed by washing the material in a 0.2% aqueous solution of sodium hydroxide at 800 C. The resulting coloured textile material has excellent fastness of the tests conventionally applied to such textile materials.

Example 2 A mixture of 7 parts of 1 - amino - 2 - (p - hydroxyphenoxy) - 4hydroxyanthraquinone, 2.8 parts of potassium carbonate and 10 parts of dimethylformamide are heated together at 115"C for 1 hour. 7.4 parts of methyl a-chloropropionate are then added and stirring and heating at 11 50C are continued for a further hour. The reaction mixture is finally cooled to 80 , 100 parts of methanol are added and the resultant solution allowed to cool when 2.4 parts of I -amino - 2 - [p - (a - methoxycarbonyl) ethoxyphenoxy] - 4 - hydroxyanthraquinone crystallises out. The dyestuff has m.p. 1470C.

Example 3 A mixture of 6.9 parts of 1 - amino - 2 - (p - hydroxyphenoxy) - 4 hydroxyanthraquinone, 2.8 parts of potassium carbonate and 5 parts of dimethylformamide are heated together at 1150 for 1 hour. 7.2 parts of ethoxyethyl - tr - chloropropionate are then added and stirring and heating at 11 SOC are continued for a further two hours. The reaction mixture is finally cooled to 80"C, 50 parts of methanol are added and the resultant solution allowed to cool when 1.5 parts of 1 - amino - 2 - [p - (a - ethoxyethoxy carbonyl)ethoxyphenoxy] - 4- hydroxyanthraquinone crystallises out. The dyestuff has m.p. 128"C.

Example 4 A mixture of 6.4 parts of 1 - amino - 2 - (p - hydroxyphenoxy)- 4 hydroxyanthraquinone, 3.5 parts of potassium carbonate and 10 parts of dimethylformamide are heated together at 1 150C for I hour. 10 parts of allyl - ( chloropropionate are then added and the reaction is continued at 115"C for a further hour. The reaction mixture is cooled to 80"C, 150 parts of methanol are added and the resultant solution allowed to cool when 3 Darts of I - amino - 2 [p - a - allyloxycarbonyl)ethoxyphenoxyl - 4 - hydroxyanthraquinone crystallises out. The dyestuff has m.p. 112"C.

Example 5 A mixture of 6.9 parts of 1 - amino - 2 - (p - hydroxyphenoxy)- 4 hydroxyanthraquinone, 2.8 parts of potassium carbonate and 10 parts of dimethylformamide are heated together at 1150C for 1 hour. 10 parts of cyclohexyl - a - chloropropionate are then added and the reaction is continued at 115"C for a further hour. The reaction mixture is cooled to 800C, 100 parts of methanol are added and the resultant solution allowed to cool when 5.8 parts of 1 amino - 2 - [p - (a - cyclohexoxycarbonyllethoxyphenoxyl - 4 hydroxyanthraquinone crystallises out. The dyestuff has m.p. 134"C.

Example 6 A mixture of 1 - amino - 2 - (p - hydroxyphenoxy) - 4 hydroxyanthraquinone, 2.8 parts of potassium carbonate and 5 parts of dimethylformamide are heated together at 115"C for 1 hour. 6.6 parts of N,Ndiethyl - a - chloropropionate are then added and the reaction continued at 11 50C for a further hour. The reaction mixture is then cooled to 800C, 100 parts of methanol are added and the resultant solution allowed to cool when 5.5 parts of I amino - 2 - [p - (a - N,N - diethylcarboxamido) ethoxyphenoxy] - 4hydroxyanthraquinone crystallises out. The dyestuff has m.p. 1580C.

Example 7 A mixture of 40 parts of methyl - a - hydroxyphenoxy)propionate, 60 parts of dimethylformamide and 28 parts of potassium carbonate are heated together at 90"C for 1 hour. 31.8 parts of 1 - amino - 2 - bromo - 4 - hydroxyanthraquinone are then added and stirring and heating continued for 16 hours.

1000 parts of water are added and the solution filtered and the filtrates acidified with hydrochloric acid. The precipitate so formed is collected by filtration, added to 300 parts of ethanol containing 3 parts of concentrated sulphuric acid and the mixture heated under reflux for 3 hours. On cooling the product crystallised to give 22 parts of 1 - amino - 2 - [p - (a - ethoxycarbonyl)ethoxyphenoxy] - 4 - hydroxyanthraquinone. The dyestuff has m.p. 134"C.

WHAT WE CLAIM IS: 1. Anthraquinone disperse dyestuffs having the formula:

wherein R is an alkyl group, Z represents a -COOR', -CN or -CONR"R"' group; R' represents an optionally substituted hydrocarbon radical which may contain hetero atoms, and R" represents hydrogen or an alkyl or substituted alkyl group and R"' represents an optionally substituted hydrocarbon radical which may contain hetero atoms.

2. Dyestuffs as claimed in claim 1 wherein R is methyl.

3. Dyestuffs as claimed in claim 1 or claim 2 wherein Z is COOR' wherein R' is methyl or ethyl.

4. Dyestuffs as claimed in any preceding claim wherein the two oxygen atoms are attached to the benzene ring in para position to each other.

5. Dyestuffs as claimed in claim 1 and hereinbefore particularly described in any of the Examples.

6. A process for the manufacture of the anthraquinone disperse dyestuffs defined in claim 1 which comprises reacting an anthraquinone compound of the formula:

with a compound of the formula:

wherein W is a halogen atom and R and Z have the meanings defined in claim 1.

7. A process for the manufacture of the anthraquinone disperse dyestuffs defined in claim 1 which comprises reacting the anthraquinone compound of the formula:

with a compound of the formula:

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

dimethylformamide and 28 parts of potassium carbonate are heated together at 90"C for 1 hour. 31.8 parts of 1 - amino - 2 - bromo - 4 - hydroxyanthraquinone are then added and stirring and heating continued for 16 hours.

1000 parts of water are added and the solution filtered and the filtrates acidified with hydrochloric acid. The precipitate so formed is collected by filtration, added to 300 parts of ethanol containing 3 parts of concentrated sulphuric acid and the mixture heated under reflux for 3 hours. On cooling the product crystallised to give 22 parts of 1 - amino - 2 - [p - (a - ethoxycarbonyl)ethoxyphenoxy] - 4 - hydroxyanthraquinone. The dyestuff has m.p. 134"C.

WHAT WE CLAIM IS: 1. Anthraquinone disperse dyestuffs having the formula:

wherein R is an alkyl group, Z represents a -COOR', -CN or -CONR"R"' group; R' represents an optionally substituted hydrocarbon radical which may contain hetero atoms, and R" represents hydrogen or an alkyl or substituted alkyl group and R"' represents an optionally substituted hydrocarbon radical which may contain hetero atoms.
2. Dyestuffs as claimed in claim 1 wherein R is methyl.
3. Dyestuffs as claimed in claim 1 or claim 2 wherein Z is COOR' wherein R' is methyl or ethyl.
4. Dyestuffs as claimed in any preceding claim wherein the two oxygen atoms are attached to the benzene ring in para position to each other.
5. Dyestuffs as claimed in claim 1 and hereinbefore particularly described in any of the Examples.
6. A process for the manufacture of the anthraquinone disperse dyestuffs defined in claim 1 which comprises reacting an anthraquinone compound of the formula:

with a compound of the formula:

wherein W is a halogen atom and R and Z have the meanings defined in claim 1.
7. A process for the manufacture of the anthraquinone disperse dyestuffs defined in claim 1 which comprises reacting the anthraquinone compound of the formula:

with a compound of the formula:

wherein R and Z have the meaning stated in claim 1.
8. A process as claimed in claim 6 or claim 7 substantially as herein described in any of the Examples
9. Anthraquinone disperse dyestuffs as defined in claim 1 whenever obtained by a process claimed in claims 6, 7 or 8.
10. A process for colouring synthetic textile materials which comprises applying an aqueous dispersion of a dyestuff as defined in claim I to the material by non-continuous dyeing, or by padding or printing processes, and heating to fix the dyestuff on the material.
11. A process as claimed in claim 10 wherein the coloured material is treated to remove loose dyestuff from the material.
12. A process as claimed in claim 11 wherein the material is treated with dilute aqueous alkali to remove loose dyestuff.
13. A process as claimed in claim 12 wherein the material is a polyester/cellulose anion and colouration is carried out in conjunction with a reactive dyestuff for the cellulose material.
14. Textile materials whenever coloured by a process claimed in any of claims 10 to 13.