US2155493A - Monoazo dyestuffs - Google Patents

Description

Patented Apr. 25, 1939 UNITED STATES PATENT OFFICE 2,155,493 MONOAZO DYESTUFFS No Drawing. Application November 12, 1936, Se-

rial No. 110,458. In Great Britain November 7 Claims.

The present invention relates to the manufacture of new monoazo dyestuffs which are useful for the colouring of Wool.

It is known to make azo dyestuffs by coupling the diazo compounds of the butyl esters of aminobenzoic acids with sulphonated components, see British Specification 314,768.

An object of the present invention is to make new monoazo dyestuffs which will dye wool to give dyeings of improved fastness to washing and milling.

This object is attained by coupling a diazotised aminocarboxylic ester of the general formula where Ar is a divalent radicle of the benzene series and R is a long chain aliphatic radicle of at least 10 carbon atoms, and not more than 20, with a coupling component devoid of long chain aliphatic hydrocarbon residues and having at least one sulphonic or carboxylic group.

The first components used according to the present invention are, as will be seen, esters of aliphatic alcohols of 10-20 carbon atoms. These alcohols, which are used as starting materials in the making of the intermediates to be used according to the invention, comprise dodecyl alcohol, otherwise known as dodecenol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, all of which are saturated. Hexadecyl alcohol is the main or sole component of the alcohols obtained by the saponification of spermaceti. If the alcohol obtained by the saponification of spermaceti is regarded as hexadecyl alcohol, its purity will depend upon the purity of the spermaceti which has been saponified. With low grade spermaceti the alcohol obtained is a mixture which may contain also oleyl alcohol. When the term cetyl is used in this specification, it will be understood that it does not necessarily refer to pure cetyl alcohol.

The invention is not limited to the use of esters of the alcohols mentioned above, although in practice it will be found that it is at present limited to the use of alcohols containing an even number of carbon atoms. Dodecyl and tetradecyl alcohols are obtainable by reduction of the fatty acids obtained from coconut oil and palm oil. Other alcohols, e. g. olein or oleyl alcohol (better to be known as octadecenol) are likewise obtainable by reduction of the fatty acids of natural fats and oils (see here, for instance, Bouvaltt and Blane, Bull. Soc. Chim., series 3, vol. 31, page 1, pages 674 and 12 10). The invention contemplates the use of the said esters of any of these alcohols, whether in the pure state or as obtained as mixtures from the fatty acids of natural fats and oils. Convenient alternative description of the said esters is accordingly that they are those of primary alcohols resulting from the reduction of the fatty acid radicles of natural fats and oils or from the saponification of waxes.

The new dyestufis of the present invention are soluble in water and dye wool to give dyeings which are characterised by their superior fastness to washing and milling compared to the known dyestuffs of British Specification 314,768.

As coupling components we may use, for example, naphthol sulphonic acids, aminonaphthol sulphonic acids or their N-substituted derivatives, naphthylamine sulphonic acids, sulpho-arylpyrazalones and the like.

The invention is illustrated but not limited by the following examples, in which the parts are by weight.

Ewample 1 30.5 parts of dodecyl-p-aminobenzoate (melting point 77-78 C.) are diazotised as a suspension in 250 parts of water and 26 parts of 36% hydrochloric acid by the addition of '7 parts of sodium nitrite. The diazo suspension so obtained is then added to an aqueous solution of 30.5 parts of 2-naphthol-6:8-disulphonic acid kept alkaline to litmus during the addition by means of sodium carbonate. The dyestuff, which is salted out if necessary, is filtered off and preserved as paste or dried in any suitable way. When dry it forms a reddish orange powder which dissolves in water or in concentrated sulphuric acid to give orange solutions. It dyes wool in bright orange shades of excellent fastness to washing and milling and very good fastness to light.

If instead of dodecyl-p-aminobenzoate there is used dodecyl-m-aminobenzoate, rather yellower shades of orange are obtained on wool and having similar fastness properties to Washing, milling and light.

Example 2 The .diazo suspension prepared as in Example 1 from 30.5 parts of dodecyl-p-aminobenzoate is added to an aqueous solution of 36.1 parts of acetyl-H-acid (1-acetamino-8 -naphthol 3 :6 disulphonic acid) kept alkaline to litmus during the addition by means of sodium carbonate. The dyestuii is salted out if necessary and filtered ofi and dried. It dyes wool in red shades of very good fastness to washing, milling and light.

Example 3 A suspension of 33.5 parts of dodecyl-3-amino- 4-methoxy-l-benzoate (M. P. 50 C.) in 250 parts of water and 26 parts of 36% hydrochloric acid is diazotised by the addition of 6.9 parts of sodium nitrite. The solution of the diazo compound so obtained is filtered if necessary and added to a cooled aqueous solution (5 C.) of 30.5 parts of 2-naphtho1-6:S-disulphonic acid kept alkaline to litmus during the addition by means of sodium carbonate. The dyestuff formed is at first gelatinous but after the addition of salt and stirring for 20-30 hours it separates in a filterable condition and is filtered off, Washed with 10% brine and dried. The new dyestuif dyes wool in bright reddish orange shades of excellent fastness to washing and milling and very good fastness to light.

If in the above example instead of 30.5 parts of 2-naphthol-6 B-disulphonic acid there are used 36.1 parts of l-acetamino-8-naphthol-4:G-disulphonic acid, a new dyestuff is obtained which dyes'wool in bright red shades of excellent fastness' to severe washing and milling and very good light fastness.

' Example 4 30.5 parts of dodecyl-p-aminobenzoate are diazotised as in Example 1 and the resulting diazo compound is added to an ice-cold aqueous solution of 25.4 parts of l-(4'-sulphophenyl) -3- methyl-5-pyrazalone which is kept alkaline during the addition by means of sodium carbonate. When coupling is complete the mixture is heated to 50 C., salted with 20% common salt, cooled to 15-20 C. and the dyestuff filtered oil. After washing the dyestufi paste with 15% brine it is dried or preserved as a paste. When dry the new dyestuff forms a yellowish brown, slightly waxy solid which dissolves in hot water to a yellow solution and in concentrated sulphuric acid toa greenish yellow solution. It dyes wool in yellow shades of very good fastness to severe washing, milling and light.

Example 5 A mixture of 31.9 parts of dodecyl-3-amino-4- methyl-l-benzoate (M. P. 55-55.5 C.), 500 parts of water and 26 parts of 36% hydrochloric acid off, washed with 5% brine and dried. it dyes wool in bright greenish yellow shades of excellent iastness to severe washing and milling and very.

good fastness to light.

Example 6 A suspension of 33.5 parts of dodecyl-B-aminoi-methoxy-l-benzoate in 250 parts of water and 26 parts of 36% hydrochloric acid is diazotised by the addition of 6.9 parts of sodium nitrite. The solution of the diazo compound so-obtained is filtered if necessary and added to an ice-cold aqueous solution (5 C.) of 25.4 parts of 1-(4'- sulphophenyl)-3-methyl-5-pyrazalone which is kept alkaline to litmus during the addition by means of sodium carbonate. After stirring for some hours the mixture is heated to 50 C. and the dyestuff filtered ofi, washed with a little 5% brine and. dried. The new dyestufi is a reddishyellow powder when dried which dissolves in hot Water to a reddish-yellow solution and in concentrated sulphuric acid to a reddish-yellow solution. It dyes wool in reddish-yellow shades of very good fastness to severe washing, milling and light.

Example 7 30.5 parts of dodecyl-p-aminobenzoate are diazotised as a suspension in 250 parts of water and 26 parts of 36% hydrochloric acid by the addition of 7 parts of sodium nitrite. The diazo suspension so-obtained is then added to a cooled aqueous solution of 32.3 parts of 1-(2':5-dichloro-4'-sulphophenyl) -3-methyl-5-pyrazalone which is kept alkaline to litmus during the addition by means of sodium carbonate. When coupling is complete the coupling mixture is at first like a thin jelly but after salting with 5% common salt (weight for volume) and stirring for several hours the dyestuff separates in granular form and is filtered off and dried. The new dyestuff when dry is a yellow powder. It dissolves in hot water to a yellow solution and in concentrated sulphuric acid to a yellow solution. It dyes wool in greenishyellow shades of excellent fastness to severe washing, milling and light.

Further examples of dyestuffs made according to the present invention are listed in the following table.

Example Diazo component Coupling component Shade on wool 3 Oety1-m-aminobenzoate l-amino-8-naphthol-3zfi rlisulphonic acid Dull violet. 9 Dodecyl-3-amino-4-methoxy-1-ben- 2-N-fl-h1y(d)roxyethylamino-S-napnthol-fi-sulphonic acid (alkaline Brown.

zoate. coup e 10 do 1(2:5-dichloro-4'-sulpl1opheny1)-3-methyl-5-pyrazalone Yellow. 11 do l-naphthol-3:fi-dis'ulphonic acid Scarlet. 12 ,do. l-(4-sulphophenyl)-fi-pyrazalone-Ii-carboxylic acid Yellow 13 d 1-(4-sulphopl1enyl)-3-metl1yl-5-pyraza1one Do.

l-benzoylamino-8-naphthol-3zfi-disulphonic acid Very bluish red, l-acetamino-8naphthol-4:6-disulphonic acid Crimson red. do 2-N-acetyl-N-B-hydroxy-ethylamino-8-naphthol-o-sulphonic acid. Red-brown. Dod'ecyl-2-chloro-5-am1no-l-benzoate l-acetamino-8-naphthol-4zfi-disulphonic acid Dull red. o l-naphthol-3:6-disu1phonic acid Orange-brown.

Decyl-p-arnino-benzoate l-acetamino-B-naphthol-M-disulphonic acid Red. Dodecyl 3 amino 4 methoxy 1'- l-naphthol-3:G-disulphonic acid Reddish-orange.

benzoate. do l(4-sulphophenyl)-5-pyrazalone-ii-carboxylic acid Yellow. do l-acetamino-B-naphthol-i:fi-disulphonic acid Bright red.

is heated to 65 C. and then cooled with stirring to 5 C. The dispersion so-obtained is then diazotised by the addition of 6.9 parts of sodium nitrite. The diazo solution so-obtained is filtered if necessary and then added to a cooled aqueous solution of 32.3 parts of l-(2':5'-dichloro-4'-sulphophenyl)-B-niethyl-S-pyrazalone, which 'is kept alkaline to litmus during the addition by means of sodium carbonate. Coupling is rapid and when complete the new dyestufiis-filtered The compounds used as first components according to this invention can be obtained by re-. acting the appropriate nitroaroyl chloride with a suitable long chain aliphatic alcohol, in an inert solvent, such as, for example, dry toluene, to give the corresponding nitroaryl carboxylic ester, followed by reduction of the nitro group with, for example, iron and aqueous hydrochloric acid.

As many apparently widely difierent embodiments of-this invention may be'made'without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. A compound represented by the formula in which X is the radicle of a coupling component from the group consisting of naphthol monoand di-sulfonic acids, amino-naphthol monoand disulfonic acids, acylamino-naphthol monoand disulfonic acids, alkyl-amino-naphthol monoand di-sulfonic acids, pyrazolone sulfonic acids, pyrazolone carboXylic acids, and the halogen derivatives of said acids; Ar is the residue of benzene; Y is one of a group consisting of hydrogen, methyl, methoxy and chloro; and R is a long chain aliphatic hydrocarbon radicle of at least 10 and not more than 20 carbon atoms.

2. A compound represented by the formula in which X is the radicle of a coupling component from the group consisting of naphthol monoand di-sulfonic acids, amino-naphthol monoand disulfonic acids, acylamino-naphthol monoand disulfonic acids, alkyl-amino-naphthol monoand di-sulfonic acids, pyrazolone sulfonic acids, pyrazolone carboxylic acids, and the halogen derivatives of said acids; Ar is connected to the azo bridge in one of the positions meta and para to the ester group and is the residue of benzene; Y is one of a group consisting of hydrogen, methyl, methoxy and chloro; and R is along chain aliphatic hydrocarbon radicle of at least 10 and not more than 20 carbon atoms.

3. A compound represented by the formula in which X is the radicle of a coupling component from the group consisting of naphthol monoand di-sulfonic acids, amino-naphthol monoand disulfonic acids, acylamino-naphthol monoand disulfonic acids, alkyl-amino-naphthol monoand di-sulfonic acids, pyrazolone sulfonic acids, pyrazolone carboxylic acids, and the halogen derivatives of said acids; Ar is the residue of benzene and the azo bridge is connected to the benzene ring in one of the positions meta and para to the ester group; and Y is one of the group consisting of hydrogen, methyl, methoxy and chloro.

4. A compound represented by the formula CnHu-O O C O OH:

in which X is the radicle of a coupling component from the group consisting of naphthol monoand di-sulfonic acids, amino-naphthol monoand disulfonic acids, acylamino-naphthol monoand disulfonic acids, alkyl-amino-naphthol monoand di-sulfonic acids, pyrazolone sulfonic acids, pyrazolone carboxylic acids, and the halogen derivatives of said acids.

5. A compound represented by the formula in which X is the residue after coupling of 2- naphthol-628-di-sulfonic acid; Ar is the residue of benzene connected to the azo bridge in one of the positions meta and para to the ester group; Y is one of a group consisting of hydrogen, methyl, methoxy and chloro; and R is a long chain aliphatic hydrocarbon radicle of at least 10 and not more than 20 carbon atoms.

6. A compound represented by the formula in which R is a long chain aliphatic hydrocarbon radicle of at least 10 and not more than 20 carbon atoms; Ar is the residue of benzene and Y is one of a group consisting of hydrogen, methyl, methoxy and chloro; with a coupling component which is devoid of long chain aliphatic residues and is one of a group consisting of naphthol monoand di-sulfonic acids, amino-naphthol monoand di-sulfonic acids, acylamino-naphthol monoand di-sulfonic acids, alkyl-amino-naphthol monoand di-sulfonic acids, pyrazolone sulfonic acids, pyrazolone carboxylic acids, and the halogen derivatives of said acids.

ARTHUR HOWARD KNIGHT. FRANK LODGE.