DE2612791A1 - DISPERSE MONOAZO DYES - Google Patents

Description

PATENT LAWYERS

DR .-! NG. H. FINCKE DIPL.-ING. H. BOHR DIPL.-ING. S. STAEGEER DR. Rer. nat. R. KNEISSL

8 MONKS 5, 25. > '£ ΓΖ 1970 Müllerstrasse 31 Fernrjf: (089j * 2io060 Telegrams: Claims Munich Telex: 523903 ciaim d

Folder 2394-7 - Dr. ICI Case M 27691

IHPEHIAL CHEMICAL HfDTISTEIES LTD. London, UK

Disperse monoazo dyes

Priority: 25.3 «75 - Great Britain

The invention relates to disperse monoazo dyes which are used for dyeing synthetic textile materials, in particular Textile materials made from aromatic polyesters are used can be.

of the invention are disperse monoazo dyes

Formula:

609841/0998

A ¹ COOR ¹

suggested where X is nitro or cyano; X for Hydrogen, chlorine, bromine, cyano, nitro, lower alkoxy or liiederalkoxycarbonyl; 2 represents kethoxy or ethoxy; Z represents hydrogen, chlorine, bromine, lower alkyl or lower alkoxy stands; A and A each independently of one another for low

Λ 2
deralkylen and E and H o ^each independently of one another represent lower alkyl or hydroxyalkyl having 2 to 4 carbon atoms.

Throughout the Description Elederalkyl ¹¹ and "Ifiederalkoxy""ung, the terms" in the alkyl or alkoxy radicals with Ί to 4 carbon atoms, while the term "ITiederalkylen" refers to alkylene radicals with Λ to 6 carbon atoms.

Examples of lower alkyl radicals Z, R ¹ and H ² are methyl, ethyl, n-propyl and η-butyl. Examples of exederalkoxy radicals T and Z are methoxy and ethoxy. Examples of lower alkoxycarbonyl radicals Y are pfethoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, isopropoxycarbonyl, secondary butoxycarbonyl and isobutoxycarbonyl.

Λ 2 examples of hydroxyalkyl radicals R and R are ß-hydroxyethyl, 7-hydroxypropyl and <5-hydroxy-n-butyl. Beisnieie for

Λ 2
Lower alkylene radicals A and A are rfethylene, trimethylene., Propylene, tetramethylene, hexamethylene, ct, ß-dimethylethylene and especially ethylene.

A preferred class of dyes of the invention will be by those of the formula:

- 2 609841/0998

-f YN = N- / Y- N

E.C003 ²

1
formed, wherein Y is hydrogen, chlorine, bromine, nitro or

1 2

Cyano and Z, T, E and E have the meanings given above own.

According to the invention there is also a method of production proposed of the azo dyes according to the invention, which is carried out by using an amine of the orkel:

diazotized and the resulting diaso compound with a coupling component of the formula:

1 1

CCOH

A ² CCOR ²

12 1 2

couples, where X, T, Z, T, A, A, R and R are those given above Have meanings.

The method according to the invention can expediently thereby be carried out that the amine to a solution of urosyl sulfuric acid adds, if necessary, destroys any remaining nitrous acid by adding sulfamic acid, the resulting solution or suspension of the diazo compound

- 60984 1/0998

to a solution of the coupling component in water, the one Acid and / or a water-soluble organic liquid such as acetone, adds, if necessary the pH de3 Readjusts the mixture to facilitate coupling and isolates the resulting dye in the usual manner.

Specific examples of the amines mentioned are 2,4-dinitroaniline, 2-cyano-4-nitroaniline, 2, ^/ 4-binitro-6- (chloro-, bromo-, cyano-, nitro-, iaethoxy- or methoxycarbonyl -) - aniline and 2-gyano-4-nitro-6- (chloro-, bromo, cyano-, methoxy- or ethoxycarbonyl-) - aniline.

Specific examples of the coupling components mentioned are 2-kethoxy-N, N-di- (β-methoxycarbonylethyl) aniline, 2,5-dime thoxy-N, F-di- (ß-ethoxycarbonylethyl) aniline, 2-methoxy-5-methyl-I: T, Sr-di- [ß- (ß ' -hydroxyäthoxycarbonyl) äthylj aniline and 2-Ethoxy-5 ~ (chloro- or bromo-) - H ", H" -di (ß-ethoxycarbonylethyl) aniline.

The azo dyes according to the invention can be in the form of aqueous Dispersions for dyeing synthetic textile materials, such as those made of cellulose acetate, nylon and especially aromatic polyesters can be used, the Dyes applied by a dyeing, padding or printing process and using the conditions and other additives customarily used for dyeing such synthetic textile materials are used. At the end In such a process, the dyed textile material is rinsed with water and then preferably also cleaned, to remove loose dye from the surface of the fabric to remove. This cleaning treatment can be carried out in the usual manner by making the colored one The textile material is immersed in a warm aqueous alkaline solution of sodium hydrosulfite. With these special dyes however, is the presence of the sodium hydrosulfite not essential. In fact, cleaning can also be done

609841/0 998

be carried out by the dyed textile material for a few minutes in an alkaline solution (such as a solution of sodium carbonate or sodium hydroxide) with a Submerges pH between 8 and 12 and with a temperature between 60 and 85 "C.

When the dyes are applied to synthetic textile materials then ruby red to navy blue colorations with excellent fastness compared to the tests which are commonly applied to such dyed synthetic textile materials.

The dyes according to the invention can also be used for dyeing aromatic polyesters used in the cash register or on the synthetic textile material by a transfer printing process, in which, if necessary, work is carried out under vacuum or under wet or damp conditions.

The invention is illustrated by the following examples, in which the parts and percentages are expressed by weight are.

example 1

5.24 parts of 2,4-dinitro-6-bromoaniline become a solution of nitrosylsulfuric acid (obtained by dissolving 1.4 parts sodium nitrate in 20 parts sulfuric acid monohydrate at 55 ° C has been prepared) is added at a temperature of 25 ° C, and the resulting mixture is then stirred for 1 hour. The resulting solution of the diazo compound is then converted into a solution of 6.5 parts of 2,5-dimethoxy-N, l \ r-di- (β-methoxycarbonylethyl) aniline in a mixture of 60 parts of acetone and 120 parts of 1% strength aqueous hydrochloric acid at 5 ° C. were added. Finally, sodium acetate is added until the pH of the mixture is 5. The mixture is then 30 min at 5 * G touched. The precipitated dye is then filtered off, washed with water and dried.

609841/0998

261279Ί

The dye is dispersed in an aqueous Kediuia, and the resulting dispersion is incorporated into a printing paste which is applied in the usual manner to a polyethylene terephthalate textile material is applied. A navy blue print is obtained, which has excellent authenticity Light, wet treatments and dry heat treatments having.

Further dyes according to the invention are obtained by that the 6.5 parts of 2,5-Mmetho: xy-IT, N-di- (ß-metho: £ ycarbonylethyl) aniline, those used in Example 1 by equivalents of those listed in the second column of Table I. Coupling components are replaced. The hues obtained from the resulting dyes are in the listed in the third column of the table.

Table I.

Coupling component hue j ir 1 2,5-dimethoxy-li, N-di- (ß-ethoxycarbonyl-
ethyl) aniline navy blue violet 2 2,5-Diaetho3cy-N, N "-di (7-methoxycarbonyl- It propyl) aniline Il 3 2,5-3imetho3cy-H ", N-di-cinethoxycarbonyl- violet methyl) aniline 2,5-dimethoxy-K ", li-di- (ethoxycarbonyl- 11 methyl) aniline 5 2,5 ~ dimethoxy-IT, l! R-di- (ß-methyl-ß-meth- navy blue oxycarbonylethyl) aniline 6th 2,5-dimethoxy-rr _> N-di- [B- (B '-hydroxy- II ethoxycarbonyl) ethyllaniline 7th 2,5-dimethoxy-If, F-di- [ß- ( γ '-hydroxy-
propoxycarbonyl) ethyl aniline 8th 2-methoxy-IT, N ~ di- (ß-ffiethoxycarbonyl- ethyl) aniline 9 2-methoxy-ir, N-di ~ [ß- (ß '-hydroxyeth-
oxycarbonyl) ethyl] aniline

609841/0998

261279

Continuation of the table

Coupling component e hue 10 2-methoxy-N, H-di- (ß-ätlioxycarbonyläthyl) - violet aniline 11 2-ethoxy-N, N-di- (ß-iaethoxycarbonylethyl) -
aniline Il 12th 2-lthoxy-W _t N-di- [ß- (ß'-hydroxyethoxy- η carbonyl) ethyl] aniline 13th 2-methoxy-5-chloro-N, li-di- (ß-methoxy- reddish carbonylethyl) aniline violet 1* 2-rfethoxy-5-chloro-N .ΪΓ-di- [ß- (3 '-hydroxy-
ethoxycarbonyl) ethyl] aniline Il 15th carbonylethyl) aniline It 16 2-Methosy-5 ~ bromo-Ii, N-di- [ß- (ß '-hydroxy- η ethoxycarbonyl) ethyl] aniline 17th 2-ethoxy- 5-chloro-N, H-di- (ß-methoxy- U carb onylethyl) aniline 18th 2 ~ ethoxy-5-chloro-Ii, N-di ~ [ß- (ß '-hydroxy- Il ethoxycarbonyl) ethyl] aniline 19th 2-methoxy-5-iaethyl-Ii, N-di- (ß-iaethoxy- bluish carbonylethyl) aniline violet 20th 2-methaxy-5-methyl-U _t N-di- (ß-ethoxy- 11 carbonylethyl) aniline 21 2-methoxy-5-methyl-N, N-di- Cß- (ß ^f - W. hydroxyethoxycarbonyl) ethyl] aniline 22nd 2-ethoxy-5-methyl-N, ff-di- (ß-methoxy- η carb onylethyl) aniline 23 2-ithoxy-5-methyl-ir,] T-di- [ß- (ß '- Il hydroxyethoxycarbonyl) ethyl] aniline

Further dyes according to the invention are obtained by that the 5.24 parts of 2,4-dinitro-6-bromoaniline of Example 1 replaced by equivalent characteristics of the amines listed in the second column of Table II. The ones from the The color shades obtained from the resulting dyes are listed in the third column of the table.

6 09841/0998

Table II

Affiin hue A. 2, 4-binitro-6-chloroaniline rotiCh
ina rineb lau B. 2,4-dinitroaniline j
violet C. 2,4-Dinitro-6-cyanoaniline greenish blue D. 2,4-, 6-trinitroaniline I! E. 2,4- Dinitro-6-methoxyaniline reddish-
navy blue F. 2,4-dinitro-6-methoxycarbonylaniline κ C- 2,4-dinitro-6-ethoxyaniline H 2,4-Dinitro-5-etho: cycarb onylaniline JI «J 2,4-Dinitro-6-n-propoxycarbonyl
aniline Jt K 2,4- Dinitro-6-isopropoxycarbonyl-
aailin reddish.-
inarine blue L. 2 ₁ 4 - Diaitro-6-n-butoxycarbonyl-
aniline t: M. 2,4- Dinitro-6- ^ -methylprop orycar-
bony! aniline 11 N 2,4-Dinitro-6-ct-methylpropoxy-
carbonylaniline ti P. 2-cyano-4-nitroaniline ■ purple Q 2-CyaD.o-4-nitro-6-chloroaniline reddish blue R. 2-cyano-4-nitro-6-bromoaniline 11 S. 2, G-dicyano-4-nitroaniline greenish blue

Further dyes according to the invention are obtained by adding those listed in the first column of Table III Amines diazotized and the resulting diazo compounds with each of the coupling components that act on the same Row of the second column of Table III, couples. Those obtained from the resulting dyes Color shades are listed in the third column of the table,

609841/0998

In this table the reference letters or refer to Besugsnumnern on the anine or coupling components that are listed in Tables II and I, respectively.

■ Table III

Amine 3, 6, 8th, Coupling components , 14-, 19, , 19, 20, , 15, 17, 21 I.
Shades j R. 1, 6, 19th 9, 12, 13 , 19, 20, purple to
reddish blue S. 1 until 22nd , 20 including 13, 15, blue to
greenish blue A. 1, 6, 8th, 9, 13, 14 , 19, 20, 21 21 reddish purple
to navy blue B. 1, 6, 19th , 21 9, 11, 13
22nd rubirurct to
violet C. 1, 6, 19th , 20 9, 13, 14 greenish blue
to narine blue D. ¹ · 6, 13th 6, 8, 11,
22nd dd E. 19th 4,
, 20 8th,
7th reddish purple
to navy blue F. 1, 6, 8th, 21 reddish purple
until bluish
violet P. 20th 2,
, 21 19 ruby red to
violet Q purple to
blue

Further dyes according to the invention are obtained by replacing the 5.24 parts of 2,4-dinitro-6-bromoaniline from Example 1 with an equivalent amount of 2,4-dinitro-6-chloroaniline and by replacing the 6.5 parts of 2, 5-Diaietho '' - 7-II, lJ * - di-Cit-methoxycarbonylethyl) aniline from Example 1 was replaced by equivalent Ifengen of the coupling components listed in Table IV. The shades obtained from the resulting dyes are listed in the second column of the table.

~ Q -

B0 9841/0998

! Table IV

Clutch component hue 2,5-3im ^ thoxy- ¥, N-di- (ß-n-propoxycarbonyl-
ethyl) aniline
2,5-dimethoxy-H ",? F-di- (ß-isopropoxy-
carb onyi ethyl) ani1ine
2,5-DiJneth.oxy-IT, N-di- (ß-n-butoxycarbonyl-
ethyl) aniline
2,5-diaethxy-] Sr, H-di- [ß- (ß '-methyl-n-
pr opoxycarb onyl) äthy ±] ani I in
2,5-dimethozy-H, N-di-Jß- (α '-ae thy 1-n-
propoxycarbonyl) ethyllaniline
2,5-3inietlioxy-ir, N ~ ai ~ (cS-iüettioxycarbonyl-
butyl) aniline
2,5-Diaietho3! 3r-ir, ir-di- Cß - (<S '-hydroxybut-
oxycarbonyl) ethyl] aniline
2,5-riiaetaoxy-ir, l! R-di-JJ3- (S '-hydroxy-
propo2ycarbonyl) ätb.ylj aniline
2,5-Oimethoxy-H, U-di- [ß- (α ^l -methyl-ß '-
hydroxypropoxycarbonyl) ethyl] aniline reddish
navy blue
π
It
U
navy blue
reddish
aiarine blue
ti
It

6Q9841 / 0998

Claims (1)

PATENT CLAIMS: wherein X is nitro or cyano; T represents hydrogen, chlorine, bromine, cyano, nitro, Klederalkxy or Siederalkoxycarbonyl; T is methoxy or ethoxy; Z for hydrogen, chlorine, bromine, lower alkyl or lower Λ ?
alkoxy stands; A and A are each independent of one another Ί 2 are l-lower alkylene; and R and R are each independent each other represent lower alkyl or hydroxyalkyl having 2 to 4 carbon atoms. 2. Dyes according to claim 1, characterized in that Ί 2
A and A each represent ethylene groups. 3 · dyes according to claim 2, characterized in that the formula: -N = N have, above Y. for hydrogen, chlorine, bromine, nitro Ί 2 or cyano and Z, T, R and R are those in claim 1 have given meanings. Process for the preparation of the dyestuffs according to Claim 1, characterized in that an amine of the formula: 609841/0998 diazotized and the resulting BiazoTrerbund with a coupling component from JOriael: coupling, where X, T, Z, T, A ¹ , A ² , S ¹ "and E ^{2 have} the meanings given in Artspruch 1 Besxtzen. 5. Use of the dyestuffs according to Claim 1 for dyeing of synthetic Tesrfcil materials by a Färoe-, Drive block or printer. 6. Use according to claim 5 »characterized in that the synthetic textile material from an aromatic Polyester is made. 7. The method according to claim 5 or 6, characterized in that that the dyed textile material then with an alkaline solution with a pH between 8 and and is treated at a temperature between 60 and 85 ° C. PATENT LAWYERS DR.-ING. H. FINCKE, DIPL.-ING. H. BOHR DIPL-ING. S. STAEGER, DR. Rer. nat. R. KNEISSIi 609841/0998