CA1091655A - Dicyano azo dyes having ether substituted aniline couplers - Google Patents

Abstract

TITLE
DICYANO AZO DYES HAVING ETHER SUBSTITUTED ANILINE COUPLERS

Abstract of the Disclosure This invention relates to blue dyes containing a 2,6-dicyano-4-nitrophenylazo moiety in combination with an aniline coupler containing m-acylamido groups and polyether groups on the coupler nitrogen atom. The dyes have excellent fastness properties and very desirable blue shades when dyed on polyester and cellulose acetate fibers.

Description

~g~655 This invention relates to blue dyes containing a 2,6-dicyano-4-nitrophenylazo moiety in combination with an aniline coupler containing m-acylamido group and polyether group on the coupler nitrogen atom. The dyes have excellent properties includ-ing fastness and very desirable blue shades on polyester andcellulose acetate fibers.
The dyes of this invention have the following general formula:
ÇN

OzN~ -N=N
=~ t=- zH40C2H40Rz CN NHCOR
wherein R is selected from alkoxy of 1-4 carbons, phenyl, and straight or branched chain alkyl of 1-4 ca}bons which may be sub-stituted with phenoxy and phenyl.
Rl is straight chain or branched chain alkyl of 1-6 carbons- and R2 is straight chain or branched chain alkyl of 1-4 carbons.
The present dyes exhibit improved properties such as dyeability by a variety of methods, build, exhaustion, leveling, pH stability, fas~ness to light, wash and sublimation, depth of shade and color uniformity under various wavelength light, essen-tially no blooming, and uniformity of dyeing under a variety of temperature and pressure conditions.
Various exemplary dyes of the present invention are shown in Table 1 herein. A particularly good dye is that of the formula ~09~655 ~N
02N~ N=N-~ /a-~-CzH40C2H40C2H5 This invention will be further illustrated by the follow-ing examples although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.

Preparation of the Couplers 1. Preparation of 3~-{[2-(2-ethoxyethyoxy)ethyl]ethyl amino}
acetanilide To m-acetamidoaniline (30.0 g.) is added 2-(2-ethoxyethoxy)-- ethanol (250 ml.) and Raney nickel (25.0 g). The mixture is heated for 12 hr. at 175~C. and 200 psi. nitrogen in an autoclave. The Raney nickel is removed by filtration. To this product is added potassium carbonate (27.6 g.) and iodoethane (46.8 g.) and the reaction mixture is heated at 120C. for 3 hr. The reaction mixture is drowned into water (800 ml.) and extracted with chloroform. The excess solvent is removed by distillation. The product is a brown viscous oil.
The following specific couplers were prepared as in Example 1:

3'-1Ethyl[2-(2-isobutoxyethoxy)ethyl]amino}benzanilide.

3'-{[2-(2-Ethoxyethoxy)ethyl]ethylamino}benzanilide.
EXAMPLE`4 3'-{Ethyl[2-(2-isopropoxyethoxy)ethyl]amino}acetanilide.

3'-{[2-(2-methoxyethoxy)ethyl]ethylamino}benza~ilide.

3'-{[2-(2-butoxyethoxy)ethyl]ethylamino}acetanilide.

~916S5 Preparation of Dyes Sodium nitrite (7.2 g.) is added gradually to 50 ml. of conc.
H2S04. The solution is cooled and 100 ml. of 1:5 acid (1 part propionic and 5 parts acetic) is added below 15C. To this mixture is added 2,6-dibromo-4-nitroaniline (29.6 g.
0.1 m.) followed by 100 ml. of 1:5 acid, all below 5C. The reaction mixture is stirred at 0-5C. for 2 hr. The couplers of Examples 1-6 above (0.01 moles) are dissolved in 40 ml.
of 1:5 acid, chilled to below 5C., and to each is added a 0.01 mole aliquot of the above diazonium salt solution. The coupling mixtures are allowed to stand for 1 hr. The dyes are precipitated by the addition of water, collected by filtration, washed with water and dried in air. If needed, the dyes are purified by slurrying in hot methanol, cooling, filtering and washing with methanol.
EXAMPLES 7-12 - Replacement of Bromine Atoms With Cyano Groups A mixture of (0.002 m) of each bromo dye corresponding to Examples 1-6, 0.4 g. cuprous cganide, and 30 ml. of N,N-dimethylformamide is heated at 95-100C. for 30 min. The reaction mixture is drowned in water. The resulting dicyano dyes are collected by filtration, washed with water and dried in air.
These cyano dyes are shown in Table 1 and produce bright blue shades on polyester fibers. Similar preparations are employed for the other dyes 13-21 of Table 1.

~as~6ss Table 1 ÇN

02N~ o-N=N-~ -N
=~ \CzH40C2HoOR~
CN NHCOR

EY~ample No. R Rl R2 6 5 C2H5 CH2CH(CH3)2 CH3 C2H5 CH(CH3)2 12 CH3 C2H5 C4Hg-n 13 CH2CH(CH3)2 CH2CH2C 3 C2H5 14 C2H5 CH2CH(CH3)2 C2H5 16 CH3 C~l(CH3)C2H5 C2H5 17 CH3 CH(CH3)C4Hg-n C2H5 The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims (3)

We Claim:

1. A compound having the formula:

wherein R is selected from alkoxy of 1-4 carbons, phenyl, and straight or branched chain alkyl of 1-4 carbons which may be substituted with phenoxy and phenyl;
R1 is straight chain or branched chain alkyl of 1-6 carbons; and R2 is straight chain or branched chain alkyl of 1-4 carbons.

2. A compound of Claim 1 having the formula wherein R is straight chain or branched chain alkyl of 1-4 carbons.

3. A compound of Claim 1 having the formula