DE2115627A1 - Anthraquinoid disperse dyes - Google Patents

Description

0 1 1 I ^ R 0 * 7

Badische Anilin- & Soda-Fabrik AG- ZIIOD 4 /

TJnaere characters: O.Z. 27 4 ^ 1 Uoe / Fe 6700 Ludwigahafen, March 29, 1971

Anthractiinoid Diaperaionafarbatoffe

The invention relates to new anthraquinoid diaperaionafarbatoffees the formula

NH

in the

R is a straight-chain or branched di- or trivalent alkylenreat with 1 to 5 carbon atoms,

η the number 1 or 2 and

X is a hydroxyl group, an oyan group, an alkoxycarbonyl group with 1 to 6 O atoms in the alkoxy radical, an alkylthio group with 1 or 4 carbon atoms in the alkyl radical, a phenyl or a phenoxy group, which may be through Chlorine, bromine, alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 or 2 carbon atoms in the alkoxy radical, with alkoxycarbonyl, Alkylthio-, alkylaulfoxido-, alkylsulfone- and / or N-alkylsulfonamido groups with 1 to 4 carbon atoms in the Alkyl radical or a phenylthio group, which is optionally substituted in the phenyl radical by chlorine, bromine, alkyl or alkoxy groups with 1 to 2 carbon atoms can be mean.

It has been found that the new dyes of the formula (I) produce dyeings on linear polyester with high sublimation and lightfastness. Compared to the dyes known from German Patent 1 209 543 which have an unsubstituted alkyl group in the oxdiazole radical, the dyeings of the dyes of the invention show a significantly improved sublimation fastness.
18/71. -2-

209842/0951

-2- O.Z. 27

Divalent or trivalent alkylene radicals R are those with 1. Ms 5 carbon atoms, which can be straight-chain or branched, eg. B. radicals -CHp-, -CHp-CHp-, - (CHg) ₃ -, -CH-CH ₂ -, - (GHg) _4- -, -CH- (CH ₂ O ₂ -, -CH-CH ₂ -,

CH ₃

-, - (CH ₂ ) ₂ -CHC, - (CH ₂ J ₃ -CHC, -CH-CH ₂ -CHC

and

-CH-GIt:

The radicals -CHp-, -CHp-CHp-, -CH ₂ -CH ₂ -CH ₂ -, - (GHg) ₄ - and - (CHg) ₅ - are particularly preferred.

For X come as alkoxycarbonyl groups, for. B. the methoxy, Ethoxy, n- or i-butoxycarbonyl group, the 2-ethoxyethyl- carbonyl group, as thioalkyl groups, for example, methyl thio, ethylthio or the n- or i-butylthio group in Consideration.

Optionally substituted phenyl, phenoxy or phenylthio groups are also suitable for X.

As optionally substituted phenyl groups, apart from the unsubstituted phenyl group, the 2-, 3-, or 4-methylphenyl, the 2-, 3- or 4-chlorophenVl-, the 2-, 3- or 4-bromophenyl, the 2.4- or 3.4-dichlorophenyl, the 2-methyl-4-chlorophenyl-, the 4-chloro-2-methylphenyl-, the 2-, 3- or 4-methoxy or ethoxyphenyl, the 2.4 or to name the 3,4-dimethylphenyl groups.

As optionally substituted phenoxy or phenylthio groups come into consideration in addition to the unsubstituted groups, for example: the 2-,. 3- or 4-methylphenoxy-, the 2,4- or 3,4-dimethylphenoxy, the 2-, 3- or 4-chlorophenoxy, the 2-, 3- or 4-bromophenoxy, the 2,4-dichlorophenoxy, the 2,4-dibromophenoxy, the 4-chloro-2-methy! phenoxy, the 2-chloro-4-methylphenoxy-, the 2-, 3- or 4-methoxy- or -äthoxyphenoxy-, the 4-thiomethylphenoxy-, the 4-methylsulfoxido-phenoxy-, the 4-methylsulfon-phenoxy-, the 4- (li ^ Ä; thbxypropän) -sulfonamido-phenoxy-, the 2-, 3- or

•. -3-

209842/0951

-3- O.Z. 27

4-chlorophenylthio, the 2-, 3- or 4-bromophenylthio, the 2-, 3- or 4-methylphenylthio groups.

The new dyes can be poured through in a manner known per se Condensation of i-amino - ^ - nitroanthraquinone - ^ - carboxylic acid chloride with an acid hydrazide of the formula

O
H ₂ N -MH-SR- (X) _n (II),

in which R, X and η have the abovementioned meaning, or of 1-amino-4-nitroanthraquinone-2-carboxylic acid hydrazide with an acid chloride of the formula

Cl - CO - R - (X) _n (III).

to the bishydrazide, subsequent ring closure in the presence of Dehydrating agents to 1,3,4-0xdiazole and reduction the nitro group to the amino group.

Examples of dehydrating agents are thionyl chloride, Acetic anhydride and benzoyl chloride into consideration.

The reduction of the nitro group can, for. B. with disodium sulfide, Sodium hydrogen sulfide, sodium dithionite or ammonium sulfide solution take place in aqueous suspension.

If mixtures of the hydrazides of the formula (II) or the acid chlorides of the formula (III) are used, the result is direct Dye mixtures.

The new dyes dye fibers made of linear aromatic polyesters in bright blue and deep shades according to the HT process.

The parts and percentages given below relate to weight.

example 1

a) 16.3 parts of i-amino ^ -nitro-anthraquinone - ^ - carboxylic acid hydrazide are with 9.3 parts of phenoxyacetic acid chloride

2 0 9 8 4 2/0951 ~ ⁴ ~

-4- ο.ζ. 27

Stirred in 75 parts of N-methylpyrrolidone "at room temperature. The crystals precipitated after the addition of methanol are filtered off with suction and washed with methanol. This gives 18 parts of N- (i-amino ^ -nitro ^ -anthrachinoyl) -N'-phenoxyacetylhydrazine.

Id) 23 parts of the product from a) are stirred in 70 parts of nitrobenzene with 12 parts of thionyl chloride for 3 hours under reflux at 160 ⁰ C,! Repeatedly cooling and precipitating with methanol, 20 parts of 2- (1 '-Aniiuo-4 nitro ¹ -2'-anthraquinonyl) -5-phenoxymethyl-1,3,4-oxdiazole obtained in the form of a red powder.

c) 10 parts of the product prepared according to b) are suspended in 100 parts water and 17 parts of 60 conclude sodium sulfide for 3 hours at 80 ⁰ O stirred. After cooling and suction, 6 parts of a blue dye powder of the formula are obtained

L * J! W.

OHo-

which fiber material made of polyester with very good sublimation and light fastness dyes blue.

Example 2

a) 99 parts of 1-amino-4-nitro-anthraquinone-carboxylic acid (2) chloride and 90 parts of CJ-phenoxycaproic acid hydrazide are ^{stirred in 1000 parts of nitrobenzene at 70 0} O for 4 hours. Cooling compartment is suctioned off and washed with methanol. 124 parts of N (1-amino-4-nitro-2-anthraChInOyI) -N ¹ - <J -phenoxycapryloylhydrazine are obtained in this way.

b) 124 parts of the product from a) are boiled in 400 parts of nitrobenzene, 60 parts of thionyl chloride at 160 ⁰ G under reflux. After cooling and addition of methanol 116 parts fall 2- (t-Araino-4'-nitro-2 '-antlira-- lihi nonyl) -? - (cJ ~ phenoxy) ~ pen1y -] - 1 _r' ⁷ -, 4-oxdiar; ("l ouch,

2 0 9 BA 2/0 ^r ib 1

BATH ORIGINAL

O.Z. 27

c) 106 parts of the product from b) are stirred in 1000 parts of water and 200 T _e ilen alcohol with 170 parts of 60 #igem sodium sulfide at 80 ⁰ G 3 hours. After cooling and filtering off with suction, 87 parts of a blue dye powder of the formula are obtained

0 NH

0 NH,

which fiber material made of aromatic polyester in clear blue tones with very good light and sublimation fastness on colors.

1-Amino-4-nitroanthraquinone-2-carboxylic acid hydrazide is obtained as described in Example 1 with a carboxylic acid chloride of the formula

Gl - CO - R - (X)

in which R, X and η have the meaning given in the table, implemented in a ratio of 1: 1 mol and the conversion product into the anthraquinone derivative of the formula

convicted. Ex. R

O NH,

R- (X)

Coloration on η linear polyester material

- (OH ₂ ) ₃ -

-SG ₀ II

2 "ί? 7 ^Η 9

blue blue

2 O 9 8 A 2 / O Q δ I

-6-

Ex. R

-G- X

O.Z. 27

coloring on η linear polyoley stone material

j) -G-0- (GH ₂

3 - SO,

blue

blue

blue

According to the information in Example 2, 1-amino-4-nitroanthraclainon-carboxylic acid (2) caloride is used with a hydrazine of the formula

- NH - GO - R -

in which R, X and η die. meaning given in the following table have converted in a ratio of 1: 1 mol and the Dmsetzungprodutt into the anthraquinone derivative of the formula

N_N

convicted.
Ex. R

Coloring on η linear polyester material

- (GH ₂ ) ₃ -

GH ₂ -

(GH ₂ ) ₃ -

- (ch ₂ ) ₅ -oh;

-OH-GH -OH
OH-,

-OH OH

-Q

-O

blue

blue

blue

blue

blue

blue

Π 9 H 4 2 i 0 9 5

-7-

BAD ORrQINAL

Ex. R

O.Z. 27

Coloring on η linear polyester material

14th

ch-gh: blue

15 16 17 18

19 20 21 22

23

24 25

GH ₂ -

-OH ₂ -

-OH ₂ -

-GH ₂ -

Oil

-o-cy-ci

OH,

) -G1

GH

oil

GH

"blue

Il Il

- (GH ₂ ) ₂ -

7 ~ ^S0 2 " ^NH (

2 U 9 I- A 2

-H-

Claims (4)

-8- O.Z. 27 431 Patronage sayings
1. Anthraquinoid disperse dyes of the formula in the R is a straight-chain or branched di- or trivalent alkylene radical with 1 to 5 carbon atoms, η the number 1 or 2 and X is a hydroxyl group, a cyano group, an alkoxy carbonyl group with 1 "to 6 carbon atoms in the alkoxy radical, an alkylthio group with 1 to 4 carbon atoms in the alkyl radical, a phenyl or a phenoxy group, which optionally by chlorine, bromine, alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 or 2 carbon atoms in the alkoxy radical, with Altoxycarbonyl-, alkylthio-, allrylsulfoxido-, alkylsulfone- and / or ÜT-alkylsulfonamido groups with 1 to 4 C atoms in the allryl radical can be substituted, or one Phenylthio group, which is optionally substituted in the phenyl radical by chlorine, bromine, alkyl or alkoxy groups with 1 oxCer 2 carbon atoms in the alkyl radical can be substituted, "mean. 2. Paraffin of the formula according to claim 1, in which E - _2m with m = 1 to 5 and X is an η-butyl, phenoxy, 2,4-dichlorophenoxy or 4-chloro-2-methylphenoxy group and η = 1 mean. 3- Process for the preparation of dyes of the formula in claim 1, in which R is a straight-chain or branched di- or trivalent alkylene radical with 1 to 5 carbon atoms, η the number 1 or 2, X a hydroxyl group, a cyano group, an AlTcoxycarbonyl group, with 1 to 6 carbon atoms in the alkoxy radical, an alkylthio group with 1 to 4 carbon atoms, an optionally substituted phenoxy, phenylthio or phenyl group, dadu denoted crude without t that a) 1-amino- -9-209842 / 0951 -9- O.Z. 27 431 4-Nitro-anthraquinone-2-carboxylic acid chloride with an acid hydrazide the formula H ₀ N - NH - 0 - R - (X) d. , ι η or b) 1-Amino-4-nitro-antarac "i.e.inone-2-carboxylic acid hydrazide with an acid chloride of the formula Cl-OR- (X) _n in which R, X and n 'have the meaning given above, is converted into an N, N ^f -bisacylated hydrazine, the reaction product is then treated with agents which remove water and then the nitro group is reduced. 4. Use of the dyes according to claim 1 as disperse dyes for dyeing textile material made of linear polyesters. Badische Anilin- & Soda-Fabrik AG ItO 20SS42 / OH5 1