DE1444613B - onoazo dye - Google Patents

Description

30th

or a radical of this type substituted by a low molecular weight alkyl or alkoxy group.

2. A compound according to claim 1, characterized in that the group R _{1 has} the formula

R, -C

40

in which R _{3 is} a phenyl radical, an alkyl radical having 3 to 9 carbon atoms or an alkoxy radical having 2 to 8 carbon atoms and R _{2 is} the radical

CH,

65

OCH, SO ₁ H

NH ₂

4. Compound of Formula

SO ₁ H

NH ₂ -

5. Compound of formula

SO ₃ H

O H

Il I s- \

C-N- / V-N = N

CH ₃ NH ₂

6. Compound of Formula

OCH ₃ NH ₂

7. Compound of Formula

SO ₃ H

NH,

8. Use of a compound according to any one of the preceding claims for dyeing vpn Polyurethane and natural and synthetic polyamide fibers.

means.

The invention relates to a group of organic compounds which can be used as dyes are and the structural formula

SO ₃ H

H HO

R ₁ -NR ₂ -N = N

(D

NH,

in which R _{1 is} an acyl radical without water-solubilizing, ion-forming groups, which has a molecular weight of 70 to 190, and R _{2 is} the radical

or

or a radical of this type substituted by a low molecular weight alkyl or alkoxy group. These compounds are obtained by using nitroaniline or a nitroaniline derivative with or without Gamma acid is diazotized and coupled in the acidic state (reaction I):

OH

NH

O ₂ NR ₂

N ₂ ⁺

SO, H

SO, H

O, N-R, -N =

NH ₂

that the nitro group is reduced to the corresponding amine (reaction II):

, SO ₃ H

HO

H ₂ NR ₂ -N = N

NH,

lightfast red and scarlet tones; their resistance to washing can be improved by the usual after-treatments can be increased. Dyeing can be done in a neutral solution with a high degree of exhaustion of the Dye done. Because of the possibility of neutral coloring, the compounds can be mixed in Baths with immediate dyes are used, and mixed fabrics of cellulose and Polyamide or polyurethane fibers can be dyed in a single bath.

Compounds of the above formula I are known from Austrian patent specification 202 549, where R ₁ denotes an alcyl radical, but R ₂ is a phenylene radical which is always substituted by an —SO _{3 H group.} The compounds are used to color preferably polyhydroxylated compounds such as cellulose, but also mixed fabrics made from them with, for example, super polyester.
A compound of the above formula I is also known from German patent specification 960 484, where R _{1 is} a triazinyl radical substituted with chlorine and a phenylamino group and R _{2 is} a phenylene radical substituted with an N -ethyl-N-phenyl-sulfaminyl group, the wool from weak acidic or neutral bath colors in blue-tinged red tones.

Among the nitranilines and nitraniline derivatives, the

to introduce the R ₂ residues that can be diazotized and coupled with gamma acid include m-nitroaniline, p-nitroaniline, 2-amino-4-nitrotoluene, 2-amino-5-nitrotoluene, 2-amino-4-nitroanisole, 2-Amino-5-nitroanisole and the like The m-compounds are used to produce scarlet and the p-compounds are used to produce red hues.

To form the R ₁ group in the compound of structural formula I, radicals are preferably used which, from the standpoint of size or mass, are so small that the compounds of structural formula I can dissolve in approximately neutral aqueous solutions. The R ₁ and R ₂ radicals should not contain any water-solubilizing, ion-forming groups, for example —SO ₃ H, —COOH or —SO ₂ —NH ₂ , because these groups cause excessive solubility which would interfere with the desired neutral coloring.

Aliphatic, alicyclic, aromatic and heterocyclic organic acyl radicals with a molecular weight of about 70 to 190 are used as R _{r radicals.} If the molecular weight of the R ₁ ^ group is greater than 190, the compound of structural formula I would be too insoluble in water to act as a dye. If the molecular weight of the R ₁ group is less than about 70, the compound cannot be used as a dye at about neutral pH because of its solubility.

If acid chlorides are used in reaction III, compounds of the formula are obtained

and that the amino group of the compound thus formed is reacted with an acid halide, acid anhydride, isocyanate or chloroformate (reaction III), the R ₁ group of which yields the compounds of structural formula I.

These compounds so prepared have unique, extremely valuable properties when used as colorants. Namely, they dye polyurethane and natural and synthetic polyamide fibers, e.g. B. nylon, silk and wool, in pure, SO ₁ H

HO

R ₃ -CNR ₂ -N = N-;

NH,

wherein R _{3 is} an alkyl, halogenated alkyl-aryl, cycloalkyl, aralkyl, alkoxyalkyl, chlorinated aryl, nitrated

ter aryl or a mononuclear, heterocyclic radical without water-solubilizing, ion-forming groups with a molecular weight in the range from 42 to 162 and R _{2 is} the radical

or such a radical substituted with a low molecular weight alkyl or alkoxyl group. Typical acid chlorides which can be used to introduce R ₃ residues are butyryl chloride, pentanoyl chloride, hexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride, decanoyl chloride, lauroyl chloride, chloroacetyl chloride, 2-chloropropinoyl chloride, toluyl chloride, anisoyl chloride, cyclohexane acetyl chloride, phenoxy acetyl chloride, phenoxy acetyl chloride, phenoxy acetyl chloride , Fluorobenzoyl chloride, hydrocinnamoyl chloride, naphthoyl chloride, methoxypropionyl chloride, 2 - chlorobenzoyl chloride, 2,4 - dichlorobenzoyl chloride, m - nitrobenzoyl chloride, ρ - nitrobenzoyl chloride and furoyl chloride.

If chloroformates are used in reaction III, compounds of the formula are obtained

O H

HO

R ₄ -OC- NR ₂ -N = N

SO ₃ H

(III)

NH,

If isocyanates are used in reaction III, compounds of the formula are obtained

SO ₃ H

wherein R ₄ . an alkyl, halogenated alkyl, alkoxyalkyl, alkoxyalkoxyalkyl, phenoxyalkyl, cycloalkyl, aralkyl, aryl radical of the benzene series, alkoxyaryl radical of the benzene series, chlorinated aryl radical of the benzene series, alkylaryl radical of the benzene series, a heterocyclic radical or a heterocyclic alkyl radical without water-solubilizing, ion-forming groups with a molecular weight in the range from 26 to 146 and R ₂ the remainder

HOH HO

I Il I

-NCNR ₂ -N = N

(IV)

NH ₂

wherein R _{5 is} an alkyl or aryl radical (of the benzene or naphthalene series), a cycloalkyl, aralkyl or heterocyclic radical without water-solubilizing, ion-forming groups with a molecular weight in the range from 27 to 147 and R _{2 is} the radical

or

or such a radical substituted by a low molecular weight alkyl or alkoxy group. Typical isocyanates useful in introducing the R ₅ groups are butyl isocyanate, hexyl isocyanate, phenyl isocyanate, toluyl isocyanate, naphthyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate, thiazolyl isocyanate, and the like.

For reasons of accessibility and production costs of the intermediate products and other economic Manufacturing considerations form the compounds having the structural formula

O H

HO

R ₆ -CNR ₇ -N = N

SO ₃ H

(V)

NH,

a preferred group, where R _{6 is} a phenyl radical, a low molecular weight alkyl radical (with about 3 to 9 carbon atoms) or a low molecular weight alkoxy radical (with about 2 to 8 carbon atoms) and R _{7 is} the radical

or

or

or such a radical substituted with a low molecular weight alkyl or alkoxyl group. Typical chloroform esters are e.g. B. those of the ethyl, isopropyl, butyl, amyl, isoamyl, valeryl, Hexyl, octyl, benzyl, cyclohexyl, phenylethyl, morpholylethyl, furfuryl, tetrahydrofurfuryl, 2-Äthoxyäthyl- and Äthoxyäthoxyäthylalkohols and the chloroform esters of various phenols, z. B. those of phenol, cresol, methoxyphenol, chlorophenol, nitrophenol and the like.

CH,

or

OCH,

are.

The following examples show how the compounds according to the invention are made and used can be. The proportions are as parts by weight, the temperatures in degrees Celsius and the percentages given as percent by weight. The compounds obtained according to Examples 1 to 5 are special preferred dyes.

example 1

Bathroom with excellent depletion of color in strong scarlet tint and very good light- and has wash resistance.

Example3

In Example 1, the 25 parts of benzoyl chloride can be replaced by 25 parts of butyl chloroformate, see above that there is a connection with the formula:

A solution of 1000 parts of water and 35.8 parts of the dye with the structural formula CH ₃ -CH ₂ -CH ₂ -CH ₂ -O-

SO ₃ H

NH ₇

is obtained by coupling diazotized p-nitroaniline with 7-amino-1-naphthol-3-sulfonic acid in the acidic Condition prepares for a reduction of the nitro group with a reducing reagent, e.g. B. sodium sulfide, in alkaline solution follows. 5 parts of sodium carbonate are added to the solution at a temperature of 25 ° C added. Then 25 parts of benzoyl chloride are added with vigorous stirring for 30 minutes long and at the same time 100 parts of 10% sodium hydroxide solution added so that the pH of the reacting mixture is maintained at 9.5-10.0. If all of the benzoyl chloride is reacted, the suspension is heated to 60 ° C, filtered and dried. The product is a red-brown solid with the structural formula

SO ₃ H

40

NH,

It is a red solid that is filled with colored polyamide fibers, e.g. B. nylon, in an approximately neutral bath with excellent exhaustion results in strong scarlet tones that are very lightfast and washfast.

Example 4

A solution of 37.2 parts of the dye with the structural formula

H ₂ N

HO

N = N

SO ₃ H

CH,

NH,

NH,

This compound dyes polyamide fibers, e.g. B. nylon, wool and silk in an approximately neutral bath with excellent exhaustion in a clear, red hue. The color of nylon is excellent Lightfastness and good wash resistance.

Example2

In example 1, the p-nitroaniline can be replaced by the m-nitroaniline, with a new one Combination with the structural formula results in:

SO, H

O H

Il I

C-N

HO

N = N

in 1000 parts of water is prepared by coupling diazotized 2-amino-5-nitrotoluene with 7-amino-1-naphthol-3-sulfonic acid in the acidic state and then coupling the nitro group with z. B. sodium sulfide is reduced in alkaline solution. (5 parts) of sodium carbonate are added thereto at a temperature of 25 ⁰ C. Then 25 parts of benzoyl chloride are added with vigorous stirring over 30 minutes, 100 parts of 10% sodium hydroxide solution being added at the same time such that the pH of the reacting mixture is maintained at 9.5-10.0. When all of the benzoyl chloride has reacted, the suspension is heated to 60 ° C., filtered and dried. The product is a red-brown solid with the structural formula

NH,

It is a red solid that has nylon, wool, silk and other polyamide fibers in a roughly neutral

CH,

NH,

209 512/325

He dyes nylon with excellent exhaustion the color in a neutral bath in bluish red tones; the coloring shows a very good light and color Wash fastness.

Example 5

A solution of 38.8 parts of the dye with the structural formula

SO, H

H, N

OCH, NH ₂

in 1000 parts of water is prepared in that diazotized 2 - amino - 5 - nitroanisole with 7 - amino-1 - Naphthol - 3 - sulfonic acid coupled under acidic conditions and then the nitro group with a reducing reagent, e.g. B. sodium sulfide, is reduced in alkaline solution. 5 parts of sodium carbonate are added at a temperature of 25 ° C. Then 25 parts of benzoyl chloride under vigorous Stirring added for 30 minutes, whereby

10

at the same time 100 parts of 10% sodium hydroxide solution are added so that the pH of the reacting mixture is maintained at 9.5-10.0. When all of the benzoyl chloride reacted is, the suspension is heated to 60 ° C, filtered and dried. The product is a red one Solid with the structural formula

IO

15th

SO ₃ H

OCH ₃ NH ₂

20 He dyes nylon, wool and silk in a neutral bath with good exhaustion in bluish-red tones. The color of the nylon shows excellent lightfastness and good wash resistance.

The following table lists further neutral acid dyes for polyamide fibers with the structural formula I and by the reactant, which _{supplies the organic acyl radical R 1} (R ₁ precursor), by the nitroaniline or its derivative, which contains the connecting radical R ₂ (R ₂ Precursors), and characterized by the hue obtained on nylon.

No. R ₁ precursors R ₂ precursors Color of nylon 6th Butyryl chloride m-nitroaniline Scarlet fever 7th Hexanoyl chloride m-nitroaniline Scarlet fever 8th Octanoyl chloride m-nitroaniline Scarlet fever 9 o-chlorobenzoyl chloride m-nitroaniline Scarlet fever 10 m-nitrobenzoyl chloride m-nitroaniline Scarlet fever 11th Cinnamoyl chloride m-nitroaniline Scarlet fever 12th Butyryl chloride p-nitroaniline Red 13th Hexanoyl chloride p-nitroaniline Red 14th Octanoyl chloride p-nitroaniline Red 15th Lauroyl chloride p-nitroaniline Red 16 o-chlorobenzoyl chloride p-nitroaniline Red 17th 2,4-dichlorobenzoyl chloride p-nitroaniline Red 18th m-nitrobenzoyl chloride p-nitroaniline Bluish red 19th p-nitrobenzoyl chloride p-nitroaniline Bluish red 20th Cinnamoyl chloride p-nitroaniline Bluish red 21 Phenylacetyl chloride p-nitroaniline Red 22nd Phenoxyacetyl chloride p-nitroaniline Red 23 Phenyl isocyanate p-nitroaniline Red 24 1-naphthyl isocyanate p-nitroaniline Red 25th Furoyl chloride p-nitroaniline Red 26th Ethyl chloroformate p-nitroaniline Red scarlet • 27 Isopropyl chloroformate p-nitroaniline Red scarlet 28 Isoamyl chloroformate p-nitroaniline Red scarlet 29 n-hexyl chloroformate p-nitroaniline Red scarlet 30th 2-chloropropionyl chloride p-nitroaniline Red 31 Benzoyl chloride 2-amino-4-nitrotoluene Red

The formulas for dyes in the table are:

Example 8

OHH O

ch ₃ - (ch ₂ ) ₆ -cn- / Vn - ^ \

NH ₂ example 11

Example 23

SO, H

HIGH

NH,

Example 25

O H

SO ₃ H

SO, H 20

NH,

OHH O

CH = CH-C-N- / VN =

Example 22 Example 29

NH, OH
CH ₃ - (CH ₂ ) ₅ -OCN

NH ₂

O H

O-CH, -C-N

HO

N = N

SO ₃ H

Example 30

O N

SO, H

"C1-CH, -CH, -C-N

NH, NH,

Claims (3)

Claims: 1. Compound of formula 3. Compound of the formula CH ₃ -CH ₂ -CH ₂ -CH ₂ -O SO, H H HO R ₁ -NR ₂ -N = N- NH, wherein R _{1 is} an acyl radical without water-solubilizing ion-forming groups, which has a molecular weight of 70 to 190, and R _{2 is} the radical 20th