DE2605622A1 - DISPERSE MONOAZO DYES - Google Patents

Description

PATENT LAWYERS

', .R, -I N G. H. FINCKE DIPL.-ING. H. BOHR DIPL.-ING. S. STAEGER £ R rough fWL Ii KNElSBl.

Patent attorneys Dr. Fincke · Bohr ■ Staeger ■ 8 Munich 5 · MOHerstraÖe

β Munich 5, February 12, 197ü M5llerstroße 31 Telephone: (089) 264060 Telegrams: Claims Munich Telex: 523903 Claim d

Mop «No. 23924 - Dr.K / Hö

Please indicate in the answer

Case Dd 27615

IMPERIAL CHEMICAL INDUSTRIES LTD. London - Great Britain

"Disperse monoazo dyes"

The invention relates to disperse monoazo dyes used for dyeing synthetic textile materials can be.

According to the invention, disperse monoazo dyes which are free from sulfonic acid groups and are excluded the formula

609335/10 26

Bank details: Bayer. Vereinsbank Munich, account 620 404 ■ Postal check account: Manchen 270 44-802

where E is the remainder of a coupling component the acylacetarylamide, pyrazolone, aminopyrazole, phenol, 2,6-dihydroxypyridine or arylamine series.

The terms relate throughout the description "Mederalkyl" and "lower alkoxy" refer to alkyl and alkoxy radicals, respectively with 1 to 4 carbon atoms.

The remainder of the coupling component E preferably has the formula

R ¹

1 2
wherein R and R each independently represent a hydrogen atom. or an optionally substituted hydrocarbon radical, in particular an optionally substituted lower alkyl radical, and the benzene ring can contain 3 additional substituents or form part of an optionally further substituted naphthalene or quinoline ring.

In particular, E is a radical of the formula

609835/1026

where W is hydrogen or a lower alkyl or lower alkoxy radical, V is hydrogen, chlorine or bromine or a lower alkyl, lower alkoxy, trifluoromethyl, cyano or acylamino radical or a radical of the formula -SOpT, preferably an acylamino radical of the formula -NHCOT ² or -NHSO ₂ T ³ , where T ^{2 is} hydrogen, alkyl, in particular lower alkyl, aryl or -NHT, T ^ is optionally substituted lower alkyl or aryl and T is hydrogen, alkyl or aryl, R is hydrogen or an optionally substituted lower alkyl or aryl. substituted alkyl radical and in particular lower alkyl radical and R stands for hydrogen or an optionally substituted alkyl and in particular lower alkyl radical or an optionally substituted aryl or cycloalkyl radical.

Examples of optionally substituted lower alkyl radicals Yr

4 and R are hydroxy lower alkyl, such as ß-hydroxyethyl,

SS or ¹ Jf-HyUrOXyPrOPyI and & hydroxybutyl, lower alkoxy lower alkyl, such as SS (methoxy or ethoxy) ethyl and g ^ -Methoxypropyl, cyano-lower alkyl, such as beta-cyanoethyl, aryl-lower alkyl, for example benzyl and beta as -Fhenylethyl, acyloxy-lower alkyl, such as ß-acetoxyethyl and 6-acetoxybutyl, carboxy-lower alkyl, such as ß-carboxyethyl and ά-carboxybutyl, lower alkoxycarbonyl-lower alkyl, such as ß-methoxycarbonylethyl, hydroxy-lower alkoxy-lower alkyl, such as e.g. ß- (ß'-hydroxyethoxy) -ethyl, lower alkoxy-lower alkoxy-lower alkyl, such as ß- (ß'-methoxyethoxy) -ethyl, Niederälkoxy-lower alkoxy-carbohyl-lower alkyl, such as ß- (ß'-methoxyethoxycarbonyl) -ethyl, acyloxy, in particular Niederalkylcarboriyloxy-lower alkyl, such as ß-acetoxyethyl and ί -Acetoxybutyl, chloro-lower alkyl, such as ^T-7 ChIOrOPrOPyI, and lower alkoxycarbonyloxy lower alkyl, such as beta-Ä'thoxycarbonyloxyäthyl.

609835 / 1.0 26

According to the invention there is also a method for proposed preparation of the azo dyes defined above, which is carried out by adding 2,6-dicyano-3,5-dimethylaniline diazotized and the resulting diazo compound with a coupling component defined above couples, the coupling component being free of sulfonic acid groups is.

The diazotization and coupling can be carried out by methods customary for these reactions uses v / earth. For example, the inventive The process can be carried out expediently by adding sodium nitrite to a solution or dispersion of the amine in a strong inorganic acid or an aqueous solution of the same or that the amine is added with nitrosylsulfuric acid stirs and the resulting solution or dispersion of the diazo component to form a solution of the coupling component added in water or in a mixture of water and a water-miscible organic liquid, if necessary adjusts the pK of the mixture to facilitate the coupling component and finally the resulting Dye isolated by conventional methods.

The following should be mentioned as examples of coupling components: Acy lace tarylamide, such as, for example, acetoacetanilide and acetoacet-2,5-dimethoxyanilide; Aminopyrazoles, such as, for example, 1-phenyl-3-methyl-15-aminopyrazole; Pyrazolones, such as, for example, l ^ -dimethyl-S-pyrazolone, but in particular l-phenyl-3- (methyl, carbonamido or carbomethoxy) -5-pyrazolone, in which the phenyl radical is optionally substituted, for example, by methyl, methoxy, ethoxy, chlorine, Bromine, nitro, sulfonamido or acetylamino is substituted; 2,6-dihydroxypyridines, such as, for example, S-cyano-iJ-methyl-ajo-dihydroxypyridine and 1-A "thy 1-3-cyano-4-diethyl-6-hydroxypyrid-2-one; phenols, such as, for example

609835 / 1.026

o-cresol, resorcinol and 3-acetylaminophenol; but in particular arylamines of the naphthylamineines, such as z.3. 1-naphthylamine, and especially the aniline series, such as 2,5-Dlir.ethoxyanilin, Ν, Ν-diethylaniline, N, N-di- (ß-hydroxyethyl) -mtoluidine, N, N-di- (ß-cyanoethyl) -aniline, N-ethyl-N- (ß-ethoxyethyl) -aniline, NjN-Di-Cß-carbometnoxyethyl) -xn toluidine, N-Zß- (ß'-kethoxyethoxycarbonyl) -ethyl7-iri-toluidine, 2-kethoxy- 5-acetylamino-N- / ß- (ß ^l -methoxyethoxycarbonyl) -ethy17-aniline, N, N-di- (ß-acetoxyethyl) -n-toluidine, N-ethyl-N- (ß-cyanoethyl) -aniline, N-ethyl-N- ( & -acetoxybutyl) -aniline and N-ethyl-N-benzyl-m-toluidine.

A preferred class of dyes according to the invention includes the dyes of the formula

OL CH

■ IfcN

wherein W, V, Fr and R have the meanings given above.

A second preferred class of dyes according to the invention includes the dyes of the formula

A ¹ - COOX ¹

609835 / 1.026

-G-

wherein W and V have the meanings given above,

1 2
A. and A each independently represent lower alkylene radicals having 1 to 6 carbon atoms, and X and X each independently represent lower alkyl radicals.

Preferably V is hydrogen, lower alkyl, lower alkoxy

"5 p
or -NnCOT, where T is lower alkyl.

A third preferred class of dyes according to the invention includes the dyes of the formula

• <'V »* H

where W is hydrogen, lower alkyl or lower alkoxy, V is hydrogen, lower alkyl, lower alkoxy or -NHCOT ^, where T ⁵ is lower alkyl, and R ^ and R ° are each independently hydrogen, lower alkyl, Niece ralkylcarbonyloxy-lower alkyl, lower alkoxycarbonyl-alkyl , Hydroxy-lower alkyl, lower alkylcarbonyl-lower alkyl, i ^ -Chlor ß-hydroxypropyl, cyclopentyl, cyclohexyl, cyano-lower alkyl, lower alkoxycarbonyl-lower alkoxycarbonyl-lower alkyl, cyano-lower alkoxy-lower alkyl, lower alkoxy-lower alkyl, lower alkoxy carbonyl-lower alkylthio-lower alkyl, lower alkoxy-lower alkoxy, Lower alkoxycarbonyloxy lower alkyl, phenyl lower alkyl, chloro lower alkyl, lower alkoxy lower alkoxy lower alkoxycarbonyl lower alkyl, cyano lower alkoxycarbonyl lower alkyl, lower alkylsulfonylamino lower alkyl, lower alkylsulfonyl lower alkyl, carboxy lower alkyl and hydroxy lower alkoxycarbonyl lower alkyl.

609835 / 1D 28

The azo dyes according to the invention can be used for dyeing synthetic textile materials, in particular textile materials from secondary cellulose acetate and cellulose triacetate, polyamide, such as Pclyhexamethylene adipamide, and especially aromatic polyester, such as polyethylene terephthalate, be used. These materials can take the form of threads, fibers, or woven or knitted Have materials.

The azo dyes can optionally be applied to the synthetic textile materials together with one or more other disperse dyes can be applied by methods commonly used for applying disperse dyes can be used on such textile materials. So the dyes in the form of aqueous dispersions by dyeing, Padding or printing methods are applied using such conditions and additives as are customary used when carrying out such processes. Alternatively, the dyes can be based on the synthetic ones Textile materials are applied by solvent dyeing processes, for example by making a solution or dispersion of the dye in perchlorethylene, which optionally contains a smaller amount of water ', applies to the textile material, preferably at an increased Temperature. The dyes can also be used for melt coloring "synthetic polymers, for example by delayed injection techniques in which the colored polymers are then spun into fibers or filaments can. Finally, the dyes can also be applied to synthetic textile materials by transfer printing. and possibly under reduced air pressure or under damp or wet conditions.

609835 / 1D26

If the azo dyes according to the invention on synthetic Textile materials are applied, then they result in yellow to purple colorations, which have excellent fastness to light and wet and dry heat treatments, both before and after heat setting. The dyes also have high color strength, excellent dyeing behavior and a good leveling temperature range and excellent build-up properties on synthetic textile materials, especially textile materials made of aromatic polyesters, so that deep color tones can easily be obtained.

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

EXAMPLE 1

1.71 parts of 2,6-dicyano-3,5-dimethylaniline are added to a solution of lütrosyls sulphurous acid, which has been obtained by dissolving 0.7 parts of sodium nitrite in 8 parts of sulfuric acid monohydrate, the temperature during mixing due to external factors Cooling is kept at -5 ° C. The mixture is then stirred at -5 to 0 ^° C. for 2 hours. The resulting solution of the diazo compound is then added to a solution of 2.06 parts of NjN-diethyl-in-aminoacetanilide in a mixture of 100 parts of water, 10 parts of a 5 strength aqueous hydrochloric acid and 30 parts of ice, the mixture is 30 min at Stirred from 0 to 5 ^° C., and the precipitated dye is then filtered off, washed with water and dried.

609835 / 1X126

If it is dispersed in an aqueous medium, then The dye dyes textile materials made of an aromatic polyester in ruby red shades with an excellent one Fastness to light, wet treatments and dry heat treatments.

The 2,6-dicyano-3,5-dimethylaniline used in the above example was obtained even by using a mixture of 25.7 parts of acetylacetamine and 18.9 parts of kalononitrile and 20 parts of water was stirred for 18 hours. The unusual one Solid was then filtered off, washed with V / ater, extracted with an 8 # aqueous sodium hydroxide solution, washed with water and finally dried, whereby 13.5 parts of the desired product were obtained.

In the following table are further examples of the invention Dyes indicated that can be obtained by adding the 2.06 parts of the coupling component of Example 1 by an equivalent amount of one of the coupling components indicated in the second column of the table replaced. The third column of the table shows the shades that are obtained when the dyes can be applied to a textile material made of an aromatic polyester.

809835/1026

example Coupling component hue CVl N, N-di (ß-acetoxyethyl) aniline Reddish orange 3 N ^ -DKß-acetoxyethyD-m-toluidine Scarlet fever N, N-di (β-n-propylcarbonyloxy) -m-toluidine ti 5 N, N-di (ß-methoxycarbonylethyl) aniline Reddish orange cn
j-% 6th 3-acetylamino-N, N-di (ß-methoxycarbonylethyl) aniline Bluish red CO
00 7th N, N-diethyl-m-toluidine Il co
cn 8th N-ethyl-N- (ß-hydroxyethyl) -m-toluidine It 9 N-ethyl-N- (ß-methoxycarbonylethyl) aniline Scarlet fever to
Cf) 10 N, N-Di (β-hydroxyethyl) -m-toluidine Red 11 N-ethyl-N- (ß-methoxycarbonylethyl) -m-toluidine It 12th N, N-diethylanilline ti 13th N-ethyl-N- (ß-acetylethyl) -m-toluldin It m N-ethyl-N- (ß-acetoxyethyl) -m-toluidine ti 15th N-ethyl-N- (α> -hydroxy-n-pentyl) -m-toluidine Bluish red

example Coupling component Hue- Red Red 16 N-ethyl-N- (4-acetoxy-n-butyl) -m-toiuidine Bluish red Il violet 17th N-ethyl-N-Co *. -methyl-ß-methoxycarbonylethyl) -m- Scarlet fever toluidine Red 18th N-Ethyl-N - (^ f-chloro-ß-hydroxypropyl) -m-toluidine U Bluish red 19th 3-methoxy-N, N-diethylaniline Bluish red Il W /
ο
co 20th 3-methoxy-N-ethyl-N- (ß-hydroxyethyl) aniline Il CX)
GJ 21 N-cyclopentylaniline Il cn 22nd N-ethyl-N-Cβ-cyanoethyl) aniline Il iMmA
O
NJ 23 N, N-di (ß-propionyloxyethyl) ~ m-toluldine O> 24 N / -Ethyl-N- / ß- (ß'-me thoxycarbony la thoxycarbonyl) - ethy 17-m-toluidine 25th N-Ethyl-N- / S .- (ß ^f -cyanoethoxy) -äthyl_7-m-toluidine 26th N-Ethyl-N-Zß- (ß'-niethoxycarbonyläthylthio) -äthyi7- m-toluidine 27 N-ethyl-N- (ß-methoxyethyI) -m-toluidine 28 N-methyl-N- (ß-hydroxyethyl) -2 _} 5-dimethylaniline 29 N, N-Di.ä thy 1-2,5-dime thoxy aniline

Ρ) ο co 00 CaJ

example Coupling component hue 30th 3-acetylamino-N- (ß-cyanoethyl) -N- / ß- (ß'-methoxyethoxycarbonyl) - äthy Ij-aniline Scarlet fever 31 3-acetylamino-N- / ß- (ß'-ethoxyethox-ycarbonyl) -ethyl7-aniline ti 32 3-acetylamino-N, N-di- (ß-hydroxyethyl) aniline ruby 33 3- (N-Ethylureido) -N, N-di- (ß-acetoxyethyl) aniline Bluish red 34 N-ethyl-N- (ß-methoxycarbonyloxyethyl) aniline Red 35 2-methoxy-5-acetylamino-N- ^ ß- (ß'-methoxyethoxycarbonyl) - ethy17-aniline violet 36 3- (methylsulfonylamino) aniline Reddish orange 37 N-ethyl-N-benzyl-m-toluidine Red 38 S-chloro-N-ethyl-N-Cβ-chloroethyl) aniline Scarlet fever 39 3-bromo-N, N-di- (β-hydroxyethyl) aniline 11 40 3-ureidoaniline Il 41 2,5-dimethyl-N- (ß-methoxycarbonylethyl) aniline Il 42 3-acetylamino-N, N-di- (ß-acetoxyethyI) aniline Bluish red 43 NjN-Di-Cß-ethoxycarbonyläthyD-m-toluidln Scarlet fever · 44 2-Ethoxy-5-acetylamino-N, N-dl- (ß-acetoxyethyl) aniline violet

CD N) N>

example Coupling component hue 45
46
47
48
49
50
51
52
53
54
55
56
57
58 3-chloro-N-ethyl-H- (ß ~ Tiethoxycarbonyloxyethyl) -aniline
2-ethoxy-5-formylamino-N-Zß- (ß'-ethoxyethoxy carbonyl) -äthy17-
aniline
3- (N, N-Dläthylureido) -N, N-diethylanal
2 ~ Methoxy-5-acetylamino-N-ethyl-N-Zfr- (ß'-niethoxyethoxycarbonyl) -
ethyl7-aniline
2-kethoxy-5-acetylamino-N- / ß- (ß '- {ß''- methoxyethoxy ^ -ethoxy-
carbonyl) ethylj-arilin
J-acetyl-NjN-di-Cβ-acetoxy (ethyl) aniline
N, N-Di-Zß- (p-bromobenzoyloxy) -ethy17-aniline
N-ethyl ~ N- (m-methylsulfonylbenzyl) -aniline
2-methyl-5- (methylsulfonylamino) aniline
N-Methyl-N-Cß-cyanoäthyD-anllln
N-rn-Butyl-N-Cβ-cyanoethyD-m-toluidine
N-ethyl-N- (β, T ^ -dihydroxypropyl) -m-toluidine
N-ethyl-N - / ^, ß-di- (ethoxycarbonyl) -ethyl7-aniline
N-Ethy1-N- (ß-phenylathyI) -aniline Reddish orange
Reddish purple
ruby
Bluish purple
violet
orange
It
Scarlet fever
orange
ti
Scarlet fever
Red
Or an pe
Scarlet fever

example Coupling component hue Red 59 3-trifluoromethyl-N, N-diethylanine Scarlet fever Il 60 N, N-di- / ß- (cyanomethoxycarbonyl) -ü. thy l7-aniline 11 It 61 2-methoxy-5-bensoylamino-N, N-di- (ß ~ acetoxyethyl) aniline violet Scarlet fever ¹ 62 3-acetylamino-N, N-di-Zß- (methylsulfonyloxy) -ethyl? -Aniline Red orange cn 63 3- (ß-Chloropropionylantf.no) -Ν, Ν-dläthylaniline Bluish red Scarlet fever σ
co 64 3- (Isopropionylamino) -N, N-dibenzylaniline Il OO
LO
tn 651 N-ethyl-N-Cβ-succinimidoethyD-m-tolduldin Il \ J f 66 N-Ethyl-N-Zß- (methylsulfonylamino) -ethyl7-m-toluidine Bluish red O
ro 67 N-ethyl-N- (ß-ethylsulfonylethyl) -m-toluidine cr> 68 3-ethoxycarbonyl-N, N-diethylaniline 69 3-cyano-N, N-diethylaniline 70 3-Ethylthio-N, N-di- (ß-methoxy carbonyle! Thy I) aniline 71 3- (N-Ethylacetylamino) -N, N-di- (ß-methoxycarbonylethyl) - aniline 72 3- (Dimethylaminosulfonylamino) -N, N-diethylaniline

example Coupling component N-phenylmorpholine hue Red 73 N-phenylpyrrolidine Il 74 l-phenyl ~ 3 ~ methyl-5-pyrazolone yellow 75 1- (N-ß-hydroxyethylamino) naphthalene violet 76 3-cyano-4-methyl-2,6-dlhydroxypyridine Green-yellow Ib O) 77 phenol
• acetoacetanilide
1-phenyl-3-diethyl-5-aminopyra2ol Ge Ib
Il
It 09835/1 78
79
80 p-cresol It ο
ΙΌ 81 Resorcinol Ge Ib Ii ch -b raun O) 82 N, N-di- (ß-ethoxycarbonylethyl) aniline orange 83 N, N-Di-Cβ-methoxycarbonylethyl, I-m-toluidine Scarlet fever 84 3-acetylamino-Ν, Ν-di- (ß-ethoxycarbonylathyI) aniline Bluish red 85 3-ureido-N, N-di- (β-methoxycarbonylethyl) aniline Il 86

cn o co

example Coupling component hue 87 3- (N-methylureido) -N, N-di- (ß-methoxycarbony la "thy 1) - aniline Bluish red 88 3-proplonylamino-N, N-di- (ß-methoxycarbonylathy 1) - aniline dd 89 3- (methoxycarbonylamino) -N, N-di- (ß-methoxycarbonyl- ethyl) aniline t! 90 3- (methylsulfonylamino) -NjN-di-Cß-methoxycarbonyl- ethyl) aniline Red 91 3-methoxy-N, N-di- (ß-methoxycarbonylethyl) aniline Scarlet fever 92 3-ethoxy-N, N-di- (β-methoxycarbonylathyI) aniline 11 93 3-chloro-N, N-di- (β-methoxycarbonylethyl) aniline orange 94 3-bromo-N, N-di- (ß-methoxycarbonylethyl) aniline Il. 95 3-cyano-N, N-di- (ß-methoxycarbonylethyl) aniline It 96 3-methylsulfonyl-N, N-di- (ß-methoxycarbonylethyl) aniline 97 3-sulfamoyl-N, N-di- (β-methoxycarbonylethyl) aniline ti
I.

to ro cn

example Coupling component Color cjn 98 2-methyl-N, N-di ~ (β-methoxycarbonylethyl) aniline Scarlet fever 99 2-methoxy-N, N-di- (β-methoxycarbonylethyl) aniline Red 100 2-methoxy-5-methyl-N, N-di (β-methoxycarbonylsthy1) aniline Il 101 2,5-dimethoxy-N, N-di- (β-methoxycarbonylathyI) aniline Bluish red 102 2-methoxy-5-acetylamino-N, N-di- (ß-methoxycarbonylathyI) - aniline violet 103 3-methyl-N, N-di ~ Zß- (ß'-methoxyethoxy carbonyl) -ethy XJ- anllin Scarlet fever 104 3-methyl-NjN-di-Zß-Cß ¹ -hydroxyethoxycarbonyl) -üthyl7- aniline Il 105 3-methyl-N- (ß-carboxyüthyI) -N- (ß-ethoxycarbonylethyl) - aniline Il 106 N-ethyl-N- (ß-carboxyethyl) aniline Il 107 3-Methy1-N-Cß-cyanoethyl) -N- (ß-carboxyäthy1) -aniline orange 108 2-methoxy-5-acetylamino-N, N-di- / ß- (ß'-methoxyiithoxy- carbonyl) ethyI7-aniline violet

example Coupling component hue 109 J-acetylamino-NjN-di-Zß-Cß'-methoxyethoxycarbonyl) - ethylj-aniline Bluish red at
ο 110 3-acetylamino-N, N-di- / ß- (cyanomethoxycarbonyl) - CD
co ethyl7-aniline Red co cn
* >>

ΙΌ C73 O

Claims (2)

PATENT CLAIMS 1. Disperse monoazo dyes that are free from sulfonic acids groups are and the formula CN N = N-E CN where E is the remainder of a coupling component the acylacetarylamide, pyrazolone, aminopyrazole, Phenol, 2,6-dihydroxypyridine or arylamine series. 2. -Disperse monoazo dyes according to claim 1, characterized in that they have the formula N = N CH CN .V have, wherein W is hydrogen or a lower alkyl or lower alkoxy radical, V is hydrogen, chlorine or bromine or a lower alkyl, lower alkoxy, trifluoromethyl, cyano or acylamino radical or radical of the formula -SOpT, in particular an acylamino radical 609835/1026 -2C- ■ of the formula -NHCOT * or -NKSO ₂ T ³ , where T ² '.hydrogen, alkyl, especially lower alkyl, aryl Ii τ or -NHT, T ^{J is} optionally substituted 4 is lower alkyl or aryl and T is hydrogen, alkyl or aryl, R for hydrogen or an optionally substituted alkyl and in particular lower alkyl radical and R is hydrogen or a optionally substituted alkyl and, in particular, nickel alkyl radical or an optionally substituted one Aryl or cycloalkyl! Radical. Process for the preparation of the dyestuffs according to Claim 1, characterized in that 2,6-dicyano-3,5-dimethylaniline is used diazotized and the resulting diazo component with a coupling component according to Definition of claim 1 that is free of sulfonic acid groups is, couples. Use of the dyestuffs according to Claim 1 or 2 for dyeing textile materials. PÄTENTÄHWXttf DR-U) QH FINCKE. DIPL.- INQ. HG. S. STAEGER. DR. Do. Mt. It 609835/1026