DE1941054A1 - Water-insoluble monoazo dyes and process for their preparation - Google Patents

Description

DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KOHLER DIPL-ING. C. GERNHARDT

MÖNCHEN HAMBURG

-UEFON = 555476 80OQ MO N Ch EN 15, -1 2. August 1969

RUEGRAMME: KARPATENT N USSBAUMSTRASSE

V /. 14412/69 7 / de

Martin Marietta Corporation New York, N.Y. (V. St. A.)

Water-insoluble monoazo dyes and process for their preparation

The invention relates to water-insoluble monoazo dyes and processes for their preparation.

The dyes according to the invention can be represented by the general formula

in which X is 01 or Br, Y is methoxy or ethoxy and Z denotes methyl, ethyl, n-propyl or Represents isopropyl.

009809/1183

The method according to the invention for the preparation of the water-insoluble monoazo dyes include, in particular, the coupling of equimolar amounts of a diazotized one Compound of the general formula

° 2 ^N "

NO ₂ and a compound of the general formula

under acidic conditions to produce a dye of the above general formula I, wherein X, Y and Z have the meanings given above.

The dyes according to the invention are particularly for use as disperse dyes for dyeing fibers from synthetic linear polyesters such as polyethylene terephthalate textile fibers, in very desirable blue shades using the usual printing or thermal setting dyeing processes Suitable · The dyes according to the invention can also be used for dyeing lextile fibers made of acetate or Polyamides (nylon) can be used.

009809/1153

Compared to other blue disperse dyes for textile fibers made from synthetic linear polyesters the dyes according to the invention can be synthesized very economically.

There is currently a large one in the textile industry Need for dyes, with which textile fibers made of synthetic linear polyesters in blue shades with a can be colored slightly greenish, which do not glow red under incandescent light and are desirable Have authenticity properties. Many attempts have been made to use blue dyes for synthetic fibers to produce linear polyesters which meet these requirements, but all such dyes which

who have become known are missing one or the other desired

Properties.

For example, the familiar blue dye comes from the formula

^ (II)

NHCOCH ₅ GHOOOCH

closer to meeting the above requirements than other known dyes and is a very popular dye. However, if this dye is made on textile fibers Polyethylene terephthalate is applied, which he has The blue coloration gives less sublimation fastness than is desirable, a greater red cast than this is desired and shows a moderate red glow

009009 / 1.1 * 3

under incandescent lamp light .. This dye is also proportional as a result of the multiple process steps required expensive to manufacture "

The dyes according to the invention have various advantages over the aforementioned dye of the formula II. For example, they are more economical to produce than the dye according to the formula II. If they are used in polyethylene terephthalate, have the resulting from the dyes according to 'the invention blue dyeings - better sublimate fastness, less v Red tinge and less red flashing under incandescent lamp light than colorations with the dye according to the formula

The dyes according to the invention have others as well desirable properties. If the dyes. According to the invention, for example, dispersed and on! Textile goods made of cotton / polyethylene terephthalate are applied by the usual thermosol dyeing process, the remains Cotton undyed (reserved) and the blue-colored polyethylene terephthalate component has excellent wash fastness, technically acceptable light fastness, excellent dry rub fastness, excellent resistance to nitrogen oxides, and very good fastness to sublimation. "' The colorations also withstand permanent resin finishing under pressure (see US patent specification 2 974 432), whereby the lightfastness, the washfastness and the resistance to nitrogen oxides are only marginal is decreased and the resistance to ozone remains unchanged.

It is particularly surprising that the dyes have good dyeing properties according to the invention,

x) excellent resistance to ozone

009809/1153

because the blue dye Br OCH,

O ₀ NON = NO-nC (III)

which has a somewhat similar structure to the dyes according to the invention when it is applied to polyethylene terephthalate. is applied ', only poor dry rub fastness, more red cast than the dyes according to the invention and a very objectionable red glow under incandescent light Has.

The method according to the invention is explained in more detail below.

The dyes according to the invention can be prepared by adding equimolar amounts of diazotized ^

O ₂ N - <q ^ NH ₂

and from

NHGOZ

⁰ VO

where X, Y and Z have the meanings given above, be coupled.

The connection

can be achieved by converting a molecular fraction of

NHCOZ

made with two molecular fractions of benzyl chloride where X and Z have the meaning given above. This can advantageously be carried out by that one for about 6 to 18 hours at about 75 to 110 ° C from a composition

NHCOZ,

an excess of benzyl chloride, i.e. more than 2 molar fractions of benzyl chloride per molecular fraction of Y used, enough alkali, such as

NHCOZ

₂ or NaOH to keep the aqueous medium alkaline throughout the reaction, as well as enough water to dissolve the alkali, heat and the resulting compound

009809711 S3

in which Y and Z have the meaning given above. Usually about 10 to 15 molecular proportions of benzyl chloride per molecular proportion of Y

NHCOZ:. ...

applied, and the excess of benzyl chloride serves as a solvent for that

Y ^:

NHCOZ
After heating it can

CH ₂ -O

KHCOZ

separated from the composition containing the same in any desired manner, e.g. B. by Vacuum distill the water and excess benzyl chloride and wash the remaining solids with it Water to remove water soluble salts, or it can

009809/1113

- 8 by! Decanting the benzyl chi or ids and the

NC layer

^XgH 2- O

NHCOZ ^{ά w}

and evaporating the benzyl chloride from the bed and recovering the resulting contaminants.

The resulting

NHGOZ

is dissolved in organic acid, e.g. B. in a 1: 5 acid table (1 part by volume of propionic acid to 5 parts by volume Acetic acid) or in acetic acid before it is coupled with the diazo component.

The 4-alkoxy-3-aminoacylanilides given above of the general formula Y can be

NHCOZ

on the one hand by the process described in US Pat. No. 2,083,308, namely by acylating Y with »to form

r \ HO-cz.

ICOZ

Nitrating the acylamino compound to form Y

-NO

NHCOZ

and reducing the acylamino nitro compound to formation of the corresponding 4-alkoxy-3-aminoacylanilide, where .Y and Z have the meaning given above.

The invention is explained in more detail below with the aid of examples.

Example 1 The blue dye of the formula

*O.

NHCOGH,
can be made as follows.

6-Bromo-2,4-dinitroaniline is diazotized by adding 12 ml of 96% H ₂ SO. and 1.1 g NaNO ₂ in a vessel, heated to 70-75 ° G, held at 70-75 ° G for 10 minutes and then cooled to 20 ° C, whereupon at 15-20 ° G 0.015 gram molecular weight 6-Bromo-2,4-ainitroaniline are added, stirred for 2 hours at 13-17 ° C and then poured onto 55 g of ice at less than 5 ° 0 and 0.2 g of sulfamic acid are added to the diazo compound obtain.

2- (N, N-dibenzyl) amino-4-acetylaminoanisole is prepared by adding 50 g of benzyl chloride, 5 g of 2-amino-4-acetylaminoanisole, 6 g of Na ₂ GO and 6 ml of H ₀ O are given, heated to 110 ° G and

- ίο -

is stirred for 12 hours at this temperature. The water and benzyl chloride are then removed by vacuum distillation, and the remaining Solids are washed with water to remove salts.

0.016 gram molecular weight of the 2- (N, N-dibenzyl) amino-4-acetylaminoanisole is placed in a beaker, then 30 ml of 1: 5 acid mixture are added and stirred to dissolve, then 11 ml of 30 # v / Aqueous liatrium acetate and then 2 g of sodium lignosulfonate are added, then it is cooled to 5-9 ° 0, and the mixture is allowed to run into the above diazo compound at 10 ° C or less, and finally it is ^{stirred for 1 hour at about 4 0} C, and then the dye obtained by filtering and washing with water until it is acid free.

Example 2

The blue dye of the formula 01 OCH ₃ .

Ή = N

can be made as follows.

This example corresponds to example 1 above, except that 0.015 gram molecular weight is 6-chloro-2,4-dinitroaniline instead of the 6-bromo-2,4-dinitroaniline used in Example 1 can be used.

001109 /! TS3

- 11 examples 3 to, 16

The blue dyes listed in the table below are produced in a manner analogous to the process according to
Example 1 prepared, wherein in each case one mole part of the
4 * -Alkoxy-3'-affiinöaGylanilids indicated in column 2 of the table was reacted with two molar parts of benzyl chloride to form the coupling component indicated in column 3, and the nitrohalogenaniline indicated in column 4 was diazotized and equimolar amounts of the resulting Diazo compound and the coupling component of the
Column 3 were coupled to under acidic conditions
to form the dye indicated in column 5.

Ö0S809 / 1U3

Bei-4-alkoxy-3-amipo coupling dinitrohalogen dye
game acylanilide component aniline

2-amino-4-propionylamino-anisole

dito

2-Amino-4-n- "bu tyry latn-in o- • anisole

2- (N, N-di- 6-bromo-2,4-

benzyl) -ami- dinitroaniline

no-4-propi-

onyl amino

anisol

dito

6-chloro-2,4-dinitroaniline

2- (N, N-di- 6-bromo-2,4-

"benzyl) -ami- dinitroaniline

no-4-n-tm-

tyrylamino

anisol

O ₂ N-

-N = N

N0_ NHCOC ₉ H

OCH

NO,

NHC0C _o H

OCH,

3 / CH ₂ 2

rO

O ₀ N- / NN = N-

dito

dito

6-chloro-2,4-dinitroaniline

OCH.

-N = N -,
⁽ 2

NO ₀ NHCOCH ₂ CH ₂ CL

Coupling dinitrohalogen dye component aniline

tmtyyyl-am ino-

2- (N, N-M- 6-bromo-2,4- ■ benzyl) amidinitroaniline , no-4-iso- '"butyryl-aminoanisole

Br

O ₂ N-

Supreme Court

'2 NHOOCH

⁰ H ₂ -Q

OH ₂ -Q

CH ,.

2-imimo-4-iso

■ biatyryl

aaisol

2- (N, N-Di- 6-ChIOr ^, 4-benzyl) -amidinitroani- "o-4-isoDU-lin tyryl amino anisole

2 ~ amino ~ 4-acetyl- 2- (N, N-di- 6-bromo-2,4-

axninophenetol benzyl) -amino- dinitroani-

■ 4-acetylaminoline phenetol

OCH

^ CH,

0 ₂ Ν- / ~ Λ-Ν = N ~ Q ~ N <

NO- / / ^GH 3

■ ^d NHCOCH ^/

O ₂ N

-N = N-

N:

^ CH,

rO

^ CH ₂ -Q

dito

dito

6-chloro-2,4-

dinitroani-

lin

Q ₂ N-

OC ₂ H ₅

N = N- ^ VN

NO ₂ NHCOCH ₃

CH,

rO

-OH ₂ -Q

Bei-4-alkoxy-3-amino coupling dinitrohalogen dye

game acylanilide component aniline

2-amino-4-propionylaraino-phenetol

2- (N ₁ N-Di-

benzyl) -

amino-4-

"propionyl-

aminophene-

tol

6-bromo-2,4 dinitroani lin Br
O ₂ N- ^ VN = N -

OC ₂ H ₅

CH ₂ -Q

₂ NHCOC ₂ H

dito

2-amino ~ 4-'n-'bu-

tyryl amino

phenetoi

dito

2- (N ₁ N-Di-

benzyl) -

amino-4-n-

butyryl

aminophene-

tol

6-chloro-2,4-

dinitroani-

lin

6-bromo-2,4-dinitroani lin

H . N -0- ₂ IdOOO ₂

f- _H = _H - £> H

· ° ^Η ε-Ο

NHCOCH ₂ CH ₂ CH

dito

dito

6-Ohlor-2,4 dinitroani lin

Cl, OC ₂ H ₅ ^ N = N - / Λ-

IiHCOCH

NO ₂ NHCOCH ₂ CH ₂ CH ₃

Case-4-alkoxy-3-amino coupling dinitrohalogen game acylanilide component aniline

No. ;

- dye

2-amino-4-isobutyryl-aminophenetol

2- (N, N-Di-

"benzyl) -.

amino-4-

isobuty

ryl-amino-

phenetol

6-bromo-2,4-

dinitro

aniline

O ₂ N-

Br

N = N-

- * 16 ditto

dito

6-Ohlor-2,4-

dinitro

aniline

If = W -

■ Λ '"Γ ι ■■» ■

Unless otherwise stated, all parts given are parts by weight. The following is the usage and the testing of the dyes described.

There were 17 # 5 parts of the dried dye Example 1, 10.2 parts of sodium lignosulfonate, 10.2 parts Place glycerin and 54 parts water in a ball mill and grind until the dye particles were substantially uniform in sizes averaging 1-2 microns. Sufficient water was then added to make the total up to 100 parts, whereby a 17 * 5 ^ dispersion of the dye was obtained.

To a coloration on a mixed fabric of 65 S * polyethylene he t ephthal and run at 55 f> Cotton, a dye bath was prepared containing 249 »g of the 5 17.5 56 dispersion described above, the dye according to Example 1 and 5, 7 g of sodium alginate as a migration inhibitor and contained enough water to obtain 3.8 l of liquor. The fabric was padded through the dye liquor at room temperature, then squeezed off between nip rollers to a liquid content of 60 J6, based on the weight of the fabric, and pre-dried practically to dryness. The dye was fixed by exposing the fabric to dry heat in a thermosol oven at 212 ° C for 90 seconds. Then the fabric was immersed in an aqueous bath containing 2 g / l 50 pounds for 10 minutes at 71 ° C -ige aqueous NaOH, 2 g / l sodium hydrosulphite and 1 g / l soap contained. It was then rinsed with water, and then the fabric was immersed for 1 minute at 60 ° C. in an aqueous bath containing 2 % sodium and 2% J * contained glacial acetic acid and the fabric was washed and dried. The color produced

009S09M1S3

was a medium navy blue on the polyether e phthalate, while the cotton was left blank.

A portion of the dyed fabric was set aside for permanent sizing or finishing under pressure and the remainder tested as follows. "Pattern" and "blotchiness" were read on the "Gray" scale, on which a rating of 5 is optimal. The sublimation was "tested for 1 minute, the sublimation began at 211 ° G, and in. 223 ° 0, a" in a Rhodiaceta- ^ll Scorch Tester blotchiness "of 4 is measured, which means a very good sublimation fastness. (In contrast, in this regard, a similarly produced dyeing with the aforementioned dye of the formula (II) resulted in the onset of sublimation at 202 ° C. and a "mottling" of 4 at 212 ° C. The dyeing had excellent dry rub fastness, excellent wash fastness (Pattern 5 and blotchiness 5 according to the AATCC washing test No. 3) ι very good resistance to ozone (very slight change after two treatments) and to gases (nitrogen oxides) (color change 5 after two treatments) as well as acceptable lightfastness (slight change after 20 hours in a carbon-arc lightfastness tester) The coloration showed a slight red glow under incandescent lamp light, but much less than one A similarly produced coloration with the dye of the formula (II). The coloration also had a much less reddish cast than the coloration with the dye of the formula (II).

A portion of the dyed polyester / cotton blend fabric was given a resin armor according to US Pat. No. 2,974 with Dimethyloldihydroxyäthylenurstoffhara subjected, and

009809/1153

the finished fabric was tested as follows. BIe ozone resistance after, two treatments was unchanged. The gas resistance after two treatments was only very slightly deteriorated. The wash fastness was still very good (Pattern 4-5 and blotchiness 4 according to the AAföC washing test ITr. 3). The lightfastness was still acceptable (Change after 20 hours in a carbon arc lightfastness tester).

009800/1183

Claims (1)

Patent to sayings y Water-insoluble McnoeeoiariB toff the general formula HHCOZ 0Η ₂ - in which X is Cl or Br, Y is methoxy or ethoxy and Z is methyl, ethyl, n-propyl or isopropyl. 2. Dye according to Claim 1, characterized in that «Y is methoxy. 3. Dye according to claim 1, characterized in that that Z is methyl. 4. Dye according to claim 1, characterized in that Y is methoxy and Z is methyl. 5. Dye according to claim 1, characterized in that X is Br 1st, Y is methoxy and Z is methyl. 6. Process for the preparation of a water-insoluble monoazo dye by coupling equimolar amounts of a diazotized amine of the formula XO ₂ H -Q -NH ₂ HO ₂ 001109 / IUI and a coupling component under acidic conditions, characterized in that the coupling component NHCOZ ^CH 2 "O and that the dye produced is general formula X
> - N = N - (' V N <(I) NHCOZ ^CH 2 ~ O in which X is Cl or Br, Y is methoxy or ethoxy and Z is methyl, ethyl, n-propyl or isopropyl represents. - 7. The method according to claim 6, characterized in that that the coupling component OCH ₃ - N < N) H ₂ -O NHCOCH ₅ έ \ -J and that the resulting dye has the general formula 009809/1153 NHCOCH, having. 8. Process for the preparation of a water-insoluble Monoazo dye by coupling equimolar amounts of diazotized 6-bromo-2,4-dinitroaniline and a coupling component under acidic conditions, characterized in that that the coupling component of 2- (N, N-dibenzyl) -amino-4-acetylamino-anisole to produce the dye of the formula O ₂ N - <VNeN GOCH consists. 9. The method according to claim 6, characterized in that that the coupling component is a compound of the general formula .0H ₂ -O NHGOZ d. used by heating a compound of the general formula 009809 / Π83 NHCOZ an excess of benzyl chloride and water under alkaline conditions at about 75 to 110 ° C for about 6 to 18 hours. Is produced, wherein Y methoxy or Ethoxy and Z denotes methyl, ethyl, n-propyl or isopropyl represents. 009809/1153