CA1049002A - Disperse monoazo navy-blue dyes - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Disperse monoazo dyes, useful for the dyeing and printing of polyester fibers in navy-blue shades, having the formula:
wherein R1 is Hal or CN; R2 is CN or NO2; R3 is alkylene;
and R4 is a selected aliphatic, cycloaliphatic, or aromatic radical.

Description

l04sno2 ';UMMARY OF TH~ INV~.NrION
Therc is a ~reat necd in the tra~e ror disperse navy dyes for polyester having both good light- and sub-llm~tlon fastness comblned with satisfactory application propertles, such as buil~up and transfer. This lnvention supplle~ a class of monoazo disperse dycs which are l~seful for dye~n~ and ~rintin~ ~)olyester fiber~ in navy-bl~le shades.
It is an object of this invention to provide navy-blue monoazo disperse dyes. It is a further object to provide dyes having good to excellent sublimation and bulldup properties. It is a still further ob~ect to pro-vlde disperse dyes having g~od light- and dry cleaning fastness, good hydrolytie stability and good transfer properties on polyester fibers. These and other objects are fulfilled by the following invention, wherein the inventor has provided a new class of monoazo dyes of the formula: ~1 02N _ ~ _N=N ~ NH-R3-OR4

2 ~

wherein Rl is Br, Cl or CN; R2 is CN or N02; R3 is Cl 4 branched or straight-chain alkylene; R4 is cyclohexyl, Cl 4 alkylcyclohexyl, benzyl, furfuryl, tetrahydro-~ur~uryl or Cl 6 branched o-r straight-chain alkylene-R5;

R5 ls CN, OH~ -OCl_4alkyl~ -OR6, -OCOCl 4alkyl or -OCOR6;
~nd R6 is phenyl or phenyl substituted with 1-2 groups selected from C1J Br, NO~, C1 4alkyl, OCl_4alkyl and CF3.

.

lO~gO02 I)l"rAILf`l) DE"CRIPrION
The rnonoazo navy ~yes of this inventlon can be prepared by conventional diazotlzatlon and coupllng pro-cedures wherein a primary aromatic amine of the formula Rl whereln Rl and R2 are as deflned above, ls diazotlzed and coupled to an aromatic amine of the formula ,~
<~\ : ' wherein R3 and R4 are as defined above. In the case wherein R4 contains a readily hydrolyzable group, e.g., when R4 is Cl 6alkylene-OCOC1 4alkyl or Cl_6alkylene-OCOR6, whereln R6 is as defined above, coupling of the diazotized amine can also be made to an aromatic amine of the formula ~ NH-R3-OCl ~alkylene-OH
,' <~/\, .
followed by acylation of the primary hydroxy group of the re~ultant monoazo compound by conventional technlques with an aliphatic or aromatic carboxylic acid chloride, bromide or anhydride to yield the deslred dye.
The diazotization Or the primary aromatic amine can be carried out at from ~ to 25C., preferably at ~0~90~2 20-25C., by the act1on of nitrosylsulfuric ~cid in 70_96% aqlleous sulfuric acid. Collpl~ng is carrled out by dl~solvln~ the aroma~c amin~ coupler in an organic or aqueous or~anic solv~nt system (such as a mixture of methanol and water), cooling the resultant coupler solu-tlon to 15C. or less and then slowly adding the diazo solution to the cold couple r solution. After the coupling is complete, the disDerse dye is precipitated by raising the pH to about 1-3 wit~ a suitable salt or base, such as sodium acetate or sodium hydroxide. The precipitated monoazo dye is isolated by filtration. Examples of diazotizable amines which are useful in the present inven-tion are given in Table I.
In order that the invention may be comp]etely understood, the preparation of the coupling components employed in the preparation of the dyes of this invention are given hereinafter. The coupling components are pre-pared by known techniques, for example, by reacting a N-hydroxyalkyl-l-naphthylamine with an epoxide such as ethylene, propylene or butylene oxide, followed by alkylation of the resultant N-hydroxyalkoxyalkyl-l-naphthylamine with alkyl halides, alkyl sulfates, aralkyl halides, etc. The aforementioned n-hydroxyalkyl-l-naphthylamine can also be reacted with activated vinyl compounds such as acry]onitrile to form the N-cyanoalkoxy-al~yl-l-naphthylamine coupling components.
Alternatively, the coupling components can be synthesized by the well-known B~cherer reaction, which lnvolves the reversible replacement of a hydroxy group of a naphthol derivative by an amino group in the presence ~04900Z

of aqu~o~s sulfite, bisulrite or sulfurous acid (e.g.
S2 + H20) (Or~anic ~eactions, Vol. I, Chapter 5, 1942J P. 105). Reaction of l-naphthol with 1 to 2 equlvalcnts Or a prlmar~ allphatlc amine of the formula H2N-R3-OR4, whereln R~ and R4 are as defined above, in the presence of aqueous sulfite or bisulfite at 120-150C.
provides excellent yieJds (75-90%) of high purity (~ 90~) product having the formula ~ NH-R3-OR4 <~ .
The latter process, thus, provides a high yield route for obtainin~ the desired coupling components which does not involve using l-naphthylamine as starting material.
This is a particularly desirable feature since 1-naphthylamine has recently been added to the growing list of industrial carcino~enic materials.
The aforementioned primary aliphatic amines, H2N-R3-OR4, can be readily prepared by reaction of the appropriate alcohol R4-OH, wherein R4 is as previously defined, with acrylonitrile, methacrylonitrile or crotononitrile followed by catalytic reduction of the cyano group. Alcohols, R4-OH, operable in the above process include, among others, cyclohexanol, methylcyclo-hexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 1-methox~-2-propanol, 2-propoxyethanol and 1-propoxy-2-propanol. Examples Or coupling components prepared by the aforementioned procedures and havin~ utility in the present invention are ~ive~ in Table II.
In the case where the coup~ing component has the formula:

~, , . . _ 10490~:

<~ NH-R3-OC1 6alkylene-OH
~>

as descrlbed herelnbefore, the resulting monoazo dye derlved therefrom can be acylated with an acld hallde or anhydride ln the presence of an organlc or lnorganlc acld acceptor, such as pyridlne, trlmethylamlne or potasslum carbonate, ln a sultable organic solvent to yleld the de~lred acylated dye. Polar nonhydroxylic solvents, such as dimethylformamlde, dlmethylacetamlde, dlmethylsulfoxide and dlethyleneglycol-dlmethylether, are useful ln the acylatlon. Pyrldine i8 particularly useful in the acylation ln that it acts as both reaction solvent and acid-blndlng agent Temperatures of from 0 to 25C. are operable in the acylation, the preferred range belng from 10 to 15C, Examples oi acylatlng agents hav~ng utlllty ln thls invention are given in Table III.
Table I
Examples of Amlnes Useful ln the Present Invention 2-chloro-4,6-dlnltroanlline 2-bromo-4,6-dlnitroanlline 2-chloro-6-cyano-4-nitroaniline 2-bromo-6-cyano-4-nitroaniline 2,6-dicyano-4-nitroanlline 2-cyano-4,6-dlnitroaniline ~04900Z

Table II
Examples of Couplers Useful in the Pres en' Invention _ ~O~ NH-R3-OR4 ~\
\~/ R
- ( CH2 ) 3 - C2H40 CH3 - ( CH2 ) 3 - -CH( CH3 ) CH20CH3 - ( C~I2 ) 3 - -CH( CH3 ) CH20C3H7 -n -( CH2)3- _~

- ( CH2 ) 3 - -CH2 ~

3 ~~\
-CH2CH( CH3 ) CH2~ \~/

- ( CH2 ) 3 - -CH2--- ( CH2 ) 3 - -CH2 -C ~H

- ( CH2 ) 3 - -C2H4CN
-cH2cH( CH3 ) CH2 - -C 2H4CN
-CH2CH( CH3 ) - -C2H4CN

-CH2CH( C2H5) - -C2H4cN
-CH2CH2CH(CH3)- C2H40C2H5 -( CH2 ) 3 - -C2H40C4Hg -n -CH2CH2CH(CH3) - --~--C(CH3)3 -CH2CH(CH3)CH2- -CH2CH(OC2H5)CH3 C~H5 -CH2CH2CH( CH3) - ~>

10490(~2 Table ~ Contlnue~) -(C~2)3- -CH2CH(OCH3)CH2CH3 -(CH2)3- C2H40C6H5 2 4 -C2H40coH4-(4 )~2 -C2H4- -C2H40C~34-(4')CH3 -(CH2)3- -C2H40C~H4-(4')Br -C2H4- -C2H4oc6H3-(2l)OCH3~(5l)CH3 Table III
Examples of Acylating r.gents Useful in . the Pre~ent Invention .
acetic anhydride n-butyric anhydride propionic anhydride benzoic anhydride acetyl chloride acetyl bromide benzoyl bromide benzoyl chloride 2-bromobenzoyl chloride

4-bromobenzoyl chloride p-anisoyl chloride p-tert.-butylbenzoyl chloride propionyl chloride butyryl chloride isobutyryl chloride o-chlorobenzoyl chloride m-chlorobenzoyl chloride p-chlorobenzoyl chloride 2,4-dichlorobenzoyl chloride 3,4-dichlorobenzoyl chloride 1049()0Z

Table ~II (Continued) 3,5-dimethcxybenzoyl chloride 3,5-dinitrobenzoyl chloride m-nlt-robenzoyl chloride p-nltrobenzoyl chloride o-toluoyl chloride m-toluoyl chloride p-toluoyl chloride m-trifluoromethylbenzoyl chloride The crude dyestuffs are conveniently converted into a commercially usable form by mixing the crude dye (e.g., ten parts on a 100% basis) with a~out 2.5 parts Or a lignin sulfonate dispersant and water in a colloid or sandmi~l Milling is continued unt~l a fine, stable, aqueous dispersion or paste is obtained wlth dye particle size reduced to approximately one micron.
The inventlon dyestufrs have excellent affinity and buildup properties on polyester textile materials, thus enabling deep navy-blue shades to be obtained. The resultlng colorations Æenerally have ~ood fastness to llght, to wet treatments and in particular to dry heat treatments such as those carried out at high temperature during pleating operations.
The inventioil dyes can be app~'ied to polyester riber by an aqueous procedure, preferably under pressure, or by padding polyester ribers with an aqueous dispersion of said dyes followed by dry heat (e.g., Thermosol) ~ixation. Both dyeing procedures are wideiy used in the trade. The present invention also encompasses polyester fibers dyed or printed with an invention dye.

_ 9 _ 104900~

In the foll~win~ examples, all parts ar~ eiven by wel~ht. ~xamples 21 an~ 24 are intended to lllustrate aqueous arld Thermosol dyeln~ procedures, respectively.

a) A mixture of 144 parts of l-naphthol, 100 parts of water, 210 parts Or diglycolamine (H2NC2H40C2H40H) and 12.8 parts of sulfur dioxide was heated at 135 + 5C.
for 20 hours. Aqueous sodium hydroxide was added in an amount sufficient to form the water-soluble sodium salt of any unreacted l-naphthol and the resulting mixture heated at 50-60C. for 1 hour. The crude product was extracted with benzene, and the benzene extract water-washed. Upon removal of the benzene, 190.5 parts (77.5%
yield) of N-(~-hydroxyethoxyethyl)-l-naphthylamine were obtained, which had a purity of 93.8%.
b) 2-Chloro-4,6-dinitroaniline (32.5 parts) was added in several portions to a stirred solution of 50.2 parts of nltrosylsulfuric acid (38~ active ingredient) and 90 parts of 73~ sulfuric acid at ?0-25C., and the mixture stirred for 3 hours. Excess nitrosylsulfuric acid was destroyed with urea. The diazo solution was then added dropwise to a c~ld (0 + 5C.) aqueous methanol solutlon of 34.6 parts of N-(B-hydroxyethoxyethyl)-l-naphthylamine. The resulting reddish-brown slurry was stirred at 0 + 5C. for 0.5 hour, and the pH ad~usted to approximately 2 by the dropwise addition of aqueous sodium hydroxide. The precipitated dye was collected by ~iltration, washed acid-free with water and dried to give 60.5 parts (88% yield) of product. Recrystalllza-tion from isopropanol-dimethylformamide provided an ~04!~00Z

analytlcally pure sample, m p 192-193C, having an absorptivlty (a ~ of ~2 llters g lcm 1 at a wave-length (~ max ) of 612 rn~. The dye was of this fornula:

~Cl N~C2N40C2~40 EXAMPI,E 2 Trimethylamine (30.4 parts~ was added to a cold (10-15C ) solutlon of 93.5 parts of the monoazo dye obtained in b~ above in 238 parts of dimethylform-amide. Acetic anhydride (41 parts~ was added dropwise over 15 minutes at 10-15C. The resultlng mixture was stirred for llhour at 10-15C. The pH of the mixture was then ad~usted to 5,5 by the dropwise addition of hydrochloric acid The reaction mixture was then heated to 80-85C, water was added, and the mixture was allowed to cool slowly to 25C. The precipitated solids were i801ated by filtration and recrystallized from isopropanol-dimethylformamide to give 94.5 parts (93,5~¢ yield~ of bronze-colored solid, m p 133-135C., having an max, ~ f 85 liters g ~lcm -1 20 length (j3 max ~ f 612 m~l. The dye was of the formula:
Cl N2 ~

Benzoyl chloride (5,34 parts~ was added drop-wise to a cold (0-10C~ solution of 16 1 parts of the lO~!~OOZ

monoazo ~ye obtalned in Example l(b) above in 100 parts or pyridine. The resulting solution was stirred at 10-20C. for 5 hours. The dye was then precipitated by the dropwise addition of ~ater. The resultant solids were lsolated by filtration and recrystallized from isopropanol-dimethylformamide to give 17 parts of product, m.p. 183-186C., having an absorptivity (a a ) Or 70 liters g.~lcm.~l at a wavelength (~ max ) f 617 m~.
The dye was of thls formula:

Cl O~N- ~ -N=~ NHc2H4oc2H4ococ6H5 2 ~ ~

2-Chloro-4,6-dinitroaniline was dlazotized as described in Example 1, part (b) above and coupled to an N~ cyanoethoxyethyl)-l-naphthylamine coupling component, thus provlding a monoazo dye, m.p. 190-192C., havln~ ar~ absorptivity (a ) of 88 liters g. lcm.

at a wavelength (~ max ) f 608 m~. The dye was of this formula:
~Cl 02N- ~ N--N- ~ -NHC2H40c2H4cN

The dyes shown in Table 4 were prepared by procedures similar to those described in Examples l to 4. The R groups refer to the R groups of the aforesaid formula.

a~

. ~, ~ ~.
0 ,1 c~ 0 ~ ~ 0 ~ a~ 0 _ K ~ U~ L~
~ -- ~D ~O~O ~ ~O ~O ~O ~O ~ ~O ~O

~ P:
oc~l VC~ I
~1~ a~ O o P:~ ^ ~ _ ~ ~ U~ O O
~t V ~ ~ ~ ~ p:: Z ~
i~; P; J ~ ~ v~ --r ~ ~ ) O O
~ _ ~ C~
,, v~`J v v ~ ' v V ~g V~ VN V~ V~
~ l l l ~ I I I I I I
E~

I, , , , , , , m, _ N ~ N C~.l V CU ~ :~
~ p N tq m ~q ~3 V V ~ V ~3 V P:~ ~ CU N
-- -- -- -- -- --~ -- V -- V ~

C~ N CU C\J C~J CU C~J N CU C~J
C~J O O O O O O O O O O O
~;Z Z 5C S; Z IZ; Si; Z ~ iZ Z

~; I V V C~ V V V V

O ¦ o ~I N
Z 11~ ~O ~ 0 ) ~ 'I ~I ~ ~I ~I ' ~049002 _ ,4 -~ 6 u~

~1 X-~ ~n ~1 ~ ~ ~D U~
E; 6 .~

~ 1~
^

5: ~: ~ O ~
~; V ~ C~ `-- C~ C~ V
~ o~ o~,. ~ 3 ~
~ ~ C~ C~C~

,, ~ , . . .
E~ ~1 CU
~ æ z o o o z; o P; C~ C~ Z Z Z C~ :Z

.-: . , æ z ~; ~ m c~ ~ m c~

0 c~ o F~' MPT,E ?~ A~UEOUS~RE:SSURE ) DYI~ING PROCEDIJR~
_. _ Five grams of commercially available "Dacron"*
5)~ polyester fabric were put into an autoclave containin~:
an aqueous dye paste (15i' active ingredient) containlng the d~ of Example 1 . . . . . . . . . . . 0.1 gram "Avitone"* T sodium hydrocarbon sulfonate (10~
solution) . . . . . . . . . . . . . . . . . 1.0 ml.
"Merpol" HCS long-chain alcohol-ethylene oxide adduct (lO~o solution) . . . . . . . . . . . 0.5 ml. 0 ethylenediaminetetraacetic acid sodium salt (1~
solution) . . . . . . . . . . . . . . . . 1.25 ml.
butyl benzoate carrier (10~ emulsion) . . . . . 1.5 ml.
water .................................. to 75 ml.
acetic acid . . . . . . . . . . . . . to ad~ust the pH to 5.5.
The temperature was raised to 265F. for 1 hour to effect dyeing. The dyed fabric was rinsed in water and then dried. It exhibited a navy shade of good fastness to light and excellent fastness to sublimation.
EXAMPrE 24- THERMOSOL PROCEDURE
"Dacron" polyester fabric was immersed for flfteen minutes at 82 C. in an aqueous bath containing 1~ of a commercially available ether-alcohol sulfate surface-active agent (detergent) and l~o of tetrasodium pyrophosphate. The fabric was rinsed in cold water, dried and then padded at 50-60~ pickup, based on the dry fabric weight, in a dye bath containing:
an aqueous dye paste (155~ active ingredient) containing the dye of Example 2 . . . . . 50 grams purified natural gum thickener . . . . . . . . 20 grams water . . . . . . . . . . . . . . . . . . . to 1 liter.
* denotes trade mark -` 104900Z

'l`he pa(ldc(3 material was passed through an infrared pre-dr~er, then ~Icate~ to arl~ held at 2l3C. for 90 seconds.
The fabr:ic was rinsed in water at 27C., scoured for 5 minutes at ~3C. in water containing 1~ of a commercially available ether-alcohol sulfate detergent, rinsed in water at 27C., and dried. The polyester fabric was d~ed to an attractive navy shade having excellent fastness to sublimation.

*

Claims (6)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A dye of the structure where R1 is Halogen or CN; R2 is CN or NO2; R3 is lower alkylene; R4 is cyclohexyl, alkylcyclohexyl, benzyl, furfuryl, tetrahydrofurfuryl, or alkylene-R5; R5 is CN, OH, -O-alkyl, -OR6, -O-?-alkyl, or -O-?-R6; and R6 is phenyl or phenyl substituted with 1-2 groups selected from Cl, Br, NO2 C1-4 alkyl, O-C1-4 alkyl and CF3.

2. The dye of Claim 1 wherein R6 is phenyl substituted with 1-2 groups selected from Cl, Br, NO2, C1-4 alkyl, O-C1-4 alkyl and CF3.

3. A dye of the formula

4. A dye of the formula

5. A dye of the formula .

6. A dye of the formula .