DE1644520A1 - Process for the preparation of dyes of the anthraquinone series - Google Patents

Description

CASSELLAFARBWERKEMAiNKUR 1 64A520 _{Ref 2} soi

AktienGESELtSCHAFT *

FRANKFURT (MAIN) -FECHENHEIm file number: P 16 44 520.8

Process for the preparation of dyes of the anthraquinones ihe

It has been found that valuable dyes of the anthraquinone series can be used the general formula

0 OH

COCk

0 R.
receives, in the

R is the residue of an aromatic amine of the formula

A-CH ₂ A- CH - S ₁ ( B ^ NH-

CO or, H ₀ C jCO

NH-

represents where

A is a - (CH ₀ ) -, a -CH ₀ -O- or a - (

R. an optionally branched alkylene rust with 2 to 6 C-A'ioaen, R- denotes an optionally branched alkyl radical with 1 to β carbon atoms, η represents one of the numbers 0 to 6 and the anthraquinone nucleus and the phenyl radical B also have one or more halogen atony and / or odor Can contain alkyl groups if you have a l, 4-dihyuroxy-anthraohinone, its leuco compound or an 1-hydroxy-4-halogenanthraohinone with an aromatic amine of the general formula

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A-CH ₀ A-CH-R ₁ ( B \ NH ₀

J 2 Ji 1— \ / ~ 2

R ₂

in which A, R ₁ , R 0 and η have the meaning given above, condensed in a molar ratio of about 1: 1, optionally in the presence of acid-binding agents.

These dyes can also be obtained by mixing a l-hydroxy-4-amino-anthraehinone with the derivatives of the above named amines which contain a halogen atom instead of the amino group, reacts.

The dyes which can be prepared according to the invention are particularly suitable for dyeing and printing structures made of synthetic materials, such as polyamide, cellulose acetate or cellulose triacetate, and in particular made of polyester materials such as polyethylene glycol terephthalate. According to the customary dyeing and printing processes, they produce strong dyeings and prints with very good fastness properties, in particular excellent lightfastness and sublimation fastness. The production of prints on the materials mentioned can be carried out in such a way that the printed goods are steamed in the presence of a carrier at temperatures between about 80 to 110 ° C. or even in the absence of a carrier at about 110 to or even after the so-called heat setting process at about 170 to 230 ⁰ C is treated. The dyeing is expediently carried out from an aqueous suspension in the presence of carrier

ern between about 100 to HO ⁰ C, in the absence of

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Carriers between about 110 to 140 ° C and also according to the so-called thermosetting process at about 170 to 230 ^° C.

The amines of the type identified above which are required as starting materials are preferably prepared in such a way that

one in the patent ... (application C 39 625 IVd / l2p)

Addition products of aryl-conjugated olefins to lactams described in the usual manner are nitrated and reduced.

Example 1; μ

A mixture of 450 parts by weight of ethyl alcohol, 43.2 parts by weight 1,4-dihydroxy-anthraquinone, 10.8 parts by weight of leuco-1,4-dihydroxy-anthraquinone, 49.2 parts by weight of N-methyl - ^ - ip-aminophenethylJ- ^ f-hutyrolaktam and 27 parts by weight of boric acid is heated to a gentle boil for 24 hours. The remaining leuco compound of the resulting dye * after adding 2.25 parts by weight of iCupper acetate and 13.5 parts by weight of piperidine are oxidized to the reaction mixture by introducing air at 60 ° C. for 8 hours. The dye is then suctioned off, first washed out with ethyl alcohol and then 'with water. He is now going to get unimplemented To remove 1,4-dihydroxy-anthraquinone, whipped with 1200 parts by weight of water and, after adding 234 parts by weight of sodium hydroxide solution 33 ° Be, stirred at 95 for one hour. then the dye is filtered off again, washed neutral with water and dried. It represents a blue powder that in conc. Sulfuric acid with a greenish blue color dissolves.

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0.3 parts by weight of the dye are brought into a sufficient powder distribution in the usual manner and dispersed in 3000 parts by weight of water. In the dyeing liquor thus obtained 100 parts by weight brings a polyester fabric based on polyethylene glycol terephthalate and dyeing is a 1 1/2 hours at 120 to 130 ⁰ C. After subsequent rinsing * and reductive after-treatment with a 0.2% alkaline sodium dithionite for 15 minutes at 60 to 70 ° G and finishing in the usual way gives a blue-violet dyeing with very good fastness properties,

Dyes with similarly valuable coloristic properties are obtained if, in paragraph 1 of this example, the N-methyl-t <- (p-amino-phenathylj- ^ f-butyrolactam is replaced by an equimolecular amount of one of the following amines: N- (p- Amino-phenethyl) -ß-propiolactam
N-methyl - «/ - - (p-aminophenethyl) -β-propiolactam N-methyl-dL - (o-bromo-p-aminophenethyl) -y-butyrolactam N-isopropyl or. Nn.Butyl-JL- (p-aminophenethyl) -y-butyrolactam N-methyl- «IL- / 2- (p-aminophenyl J-propylZ- ^ butyrolaktam N- (p-aminophenethyl) - < / -valerolactam
N- (»-Bromo-p-amino-phenethyl / -t-caprolactam N -_ / 2- (p-amino-phenyl) -propyl / -f-caprolactam

N-methyl ^ N-ethyl or. N-n. Propyl- <£ - (p-aminophenethyl) - £ -eapro-

lactam N-Me thy 1 - ^ - / 2- (p-amino-phenyl J-propyly-'ia-oenantholaktam N (p-amino-phenethyl) - ^ »- caprylolaktam N-ethyl-Λ - (p-aminophenethyl) -A> -caprylolactam N- (p-Amino-phenethyl) - <* - pelargolakt am

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N-methyl- (k- (p-aminophenethyl) morpholone N- (p-Amino-phenäthy1) -thi omorpho1on.

Dyes of similar coloristic properties can be used also obtained if in the above example the 1,4-dihydroxy- Anthraquinone and the leuco-1,4-dihydroxy-anthraehinone replaced are given by equimolecular amounts of:

1,4-dihydroxy-6-chloro >> or -6-bromo-anthraehinone and leuco-1,4-dihydroxy-ö-chloro-, or -6-bromo-anthraquinone,!, ^ - dihydroxy-öjV-dichloro-anthrachihon and leuco-1,4-dihydroxy-6,7-diehlor-anthraehinone or through

l ^ -dihydroxy-o-methyl-anthraquinone and leuco-1,4-dihydroxy-6-methy1-anthraquinone.

Example 2:

A mixture of 200 parts by weight of water, 200 parts by weight of ethyl alcohol, 38.4 parts by weight of 1,4-dihydroxy-anthraehinone, 9.6 parts by weight of leuco-1,4-dihydroxy-anthraehinone, 40.8 parts by weight of N- (p-amino-phenethyl) - # "- butyrolactam and 24 parts by weight Boric acid is heated to a gentle boil for 24 hours. After cooling, the resulting dye is sucked off, first washed out with ethyl alcohol and then with water. He is now to unreacted 1,4-dihydroxy-anthraquinone to remove, as described in Example 1, Paragraph 1, aftertreated with alkaline. The dye restores after drying a dark blue powder, which is in conc. Sulfuric acid with a greenish blue color.

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Polyester fabric is coated with a printing paste containing 30 parts by weight of the dye (based on 1000 parts by weight of printing paste) and contains thickening, printed and dried. After steaming at 1.5 atm for 15 minutes, Rinse and finish in the usual way a strong blue-violet print with excellent fastness properties.

Dyes with also very good fastness properties are obtained if the N- (p-amino-phenethyl) -y <-butyrolactam in paragraph 1 of this example is replaced by an equimolecular amount of:

N-methyl-oL -, / 2- (p-aminophenyl) -propyl / -ß-propiolactam N-ethyl or. Nn-hexyl-tC - (p-aminö-phenethyl) -if ^ butyrolactam N-methyl- (m-methyl-p-aminophenethyl) - ^ - butyrolactam N-methyl - «^ - (p-aminophenethyl) - (/ - valerolaktam N- (p-amino-phenethyl) - £ -caprolaktam N- (ο, ο'-dichloro-p-amino-phenethyl) - £ -eaprolaktam N-methyl 1 - ^ - / 2- ( p-amino (phenyl) propyl / - £ -caprolactam ψ N- (p-amino-phenethyl) -4j-oenantholaktam N-methyl-oL- / 2- (p-aminophenyl) -propyl / - ^ -caprylo Lactam N-methyl - **. - (p-aminophenethyl) -cü-pelargolactam N- (p-aminophenethyl) -morpholone

N — methyl - «/ - - (p-amino-phenethyl) -thiomorpholone.

Example 5?

A mixture of 150 parts by weight of nitrobenzene, 10.3 parts by weight 1-hydroxy-4-chloro-anthraquinone, 10.9 parts by weight of N-methyl-oC-ip-aminophenethyl) - ^ - butyrolactam,

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6.0 parts by weight of sodium carbonate, 4.4 parts by weight of sodium acetate, 0.5 part by weight of copper acetate and 0.5 part by weight Copper powder is heated to 210 ° for 24 hours. The nitrobenzene is then removed by steam distillation removed, sucked off the resulting dye, washed out with water and dried. Recrystallized from monomethyl glycol eggs, it forms dark blue crystals, which are in conc. Dissolve sulfuric acid with a greenish blue color.

The dye provides dyeings on polyester fabric that are used in their coloristic properties are identical to those of the dye which is obtained according to Example 1, Paragraph 1.

The same dye is obtained if, in the above example, the l-hydroxy-4-chloro-anthraquin © n and the N-methyl-Λ * - (p-amino-phenethyl) - ^ - butyrolaktaia is replaced by equimolecular Amounts of l-hydroxy-4-amino-anthrac »Iiiii © n and N-methyl- * £ / - (p-bromo-phenathy 1) -Jj * -butyrolactam.

.- '■ r r q

Claims (1)

Claim Process for the preparation of anthraquinone dyes general formula O OH 0
in which R is the radical of an aromatic amine of the formula A - CH. A-CH-R ₁ ( B \ _ NH- H ₀ C CO or H ₀ C CO represents where A is a - (CHg) _n -, a -CHg-O- or a -CHg-S bridge, R, an optionally branched alkylene radical with 2 to 6 carbon atoms, Ro denotes an optionally branched alkyl radical with 1 to 6 carbon atoms, η represents one of the numbers 0 to 6 and the anthraquinone nucleus and the phenyl radical B also have one or more halogen atoms and / or may contain alkyl groups, characterized in that a 1,4-dihydroxy-anthraquinone, its leuco compound or a l-hydroxy-4-halo-anthraquinone with an aromatic amine in the general formula A-CH ₂ A-CH H ₀ C CO or H ₀ C CO in which A, R ₁ , R 0 and η have the meaning given above, condensed in a molar ratio of about 1: 1, optionally in the presence of acid-binding agents. 9 O 9 ^ / 3/1 ^ Q 9.196η