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Патент USA US3084163

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3,984,153
United States Patent 0 "ice
1
2
3,084,153
According to a further feature of the invention there
is provided a process for the manufacture of the new
water-insoluble azo dyestu?s, as hereinbefore de?ned,
WATER-S?LUBLE MUNOAZO BENZOTHIAZQLE
<
idatented Apr. 2, 19%?»
DYESTUFFS
which comprises coupling a diazotised amine of the for
Brian Ribbons Fishwiek and Eric Leslie Johnson, Man
chester, England, assignors to Imperial Chemicai Indus 5 mula:
'
tries Limited, London, England, a corporation of Great
Britain
No Drawing. Filed Oct. 28, 1959, Ser. No. 84§,l8*6
Claims priority, application Great Britain Nov. 3, 1958
3 Claims. (Cl. 260-158)
1O
This invention relates to new azo dyestulis and more
7
S
1
particularly it relates to new water-insoluble azo dye
wherein B and X have the meanings stated above, with
stuifs which are valuable for the colouration of arti?cial
a coupling component of the formula:
textile materials.
According to the invention there are provided the new 15
water~insoluble azo dyestuffs of the formula:
wherein A, R and R’ have the meanings stated above.
The process of the invention may be conveniently
brought about by adding the amine to a solution of nitros
ylsulphuric acid, adding the diazo solution so obtained
to a solution of the coupling component in an aqueous
wherein A represents a substituted or unsubstituted 1:4 25 solution of hydrochloric acid, adding sodium hydroxide
and ?ltering off the azo dyestu? which is precipitated.
phenylene or 1:4-naphthylene nucleus which is free from
Those amines used in the process of the invention
sulphonic acid and carboxylic acid groups, R represents
wherein X represents a —CN group may be obtained by
hydrogen or a substituted or unsubstituted lower alkyl
treating the appropriate aminobenzonitrile with thiophos
radical or aralkyl radical, R’ represents a substituted or
unsubstituted lower alkyl radical, X represents a —-CN 30 gene, reacting the isothiocyanate so obtained with arm
monia and ?nally treating the thiourea so obtained with
or -—SCN group and the benzene ring B maybe further
a solution of bromine in chloroform.
substituted by groups other than sulphonic and carboxylic
Those amines used in the process of the invention
acid groups, provided that when R represents a [it-cyano
wherein X represents a —SCN group may be obtained
lower alkyl radical R’ does not represent either a ,B-cyano
35 by treating the appropriate aminothiocyanobenzene with
or a ?-acyloxy-lower alkyl radical.
a thiocyanate, for example sodium or ammonium thio
As examples of the substituents which may be present
cyanate and subsequently treating with chlorine or bro
in the 1:4-phenylene or 1:4-naphthylene nucleus repre
mine, or by treating the appropriate aminothiocyanoben
sented by A there may be mentioned lower alkyl, such
zene with thiophosgene, then with ammonia and ?nally
as methyl, lower alkoxy such as methoxy, halogeno such
as chloro and bromo, tri?uoromethyl and acylamino such 40 treating with bromine.
As speci?c examples of amines which may be used
as acetylamino.
in the process of the invention there may be mentioned
As examples of further substituents which may be pres
ent in the benzene nucleus B there may be mentioned
2-amino-?-thiocyanobenzthiazole,
lower alkyl, for example methyl, and halogeno for ex
45 2~arnino-6-cyanobenzthiazole,
ample chloro and bromo.
2-amino-4-chloroeo-cyanobenzthiazole,
As an example of an aralkyl radical represented by R
2-amino-4-bromo-6-cyanobenzthiazole,
there may be mentioned benzyl.
>
2-amin0-4methyl-G-thiocyanobenzthiazole,
2-arnino-4-ethyl-6-thiocyanobenzthiazole,
2-amino-6-methyl-4-thiocyanobenzthiazole,
As examples of radicals which may be represented by
both R and R’ there may be mentioned the lower alkyl
radicals, methyl, ethyl, propyl and butyl and especially
2-amino-4-chloro-é-thiocyanobcnzthiazole and
there may be mentioned substituted lower alkyl radicals,
for example hydroXy lower alkyl radicals such as hy
2-amino-4-bromo~6-thiocyanobenzthiazole.
droxyethyl, hydroxypropyl, hydroxybutyl, lower alkoxy
As examples of coupling components which may be
lower alkyl radicals such as ethoxyethyl, methoxyethyl,
used in the process of the invention there may be men
methoxypropyl, methoxybutyl, cyano-lower alkyl radi
tioned
cals such as cyanomethyl, cyanoethyl, cyanopropyl,
cyanobutyl, acyloxy-lower alkyl radicals such as acetoxy
N : N-bis ( B-acetoxyethyl) -m-toluidine,
N: N-bis (?-hydroxyethyl) aniline,
ethyl, acetoxypropyl, acetoxybutyl, propionoxyethyl,
halogeno-lower alkyl radicals such as chloroethyl, bromo
ethyl, carbo-lower alkoxy-lower alkyl radicals such as 60
carbethoxymethyl, carbomethoxyethyl, carbethoxyethyl,
carbomethoxymethyl, lower Mkylsulphonyl-lower alkyl
radicals such as methylsulphonylethyl, ethylsulphonyl
ethyl, lower alkylcarbonyl radicals such as methylcar
bonylethyl, ethylcarbonylethyl, and various other sub
stituted lower alkyl radicals such as aminocarbonylethyl,
dihydroxypropyl, 'y-chloro-?-hydroxypropyl, 'y-bromo-?
hydroxypropyl, ?z'y-epoxypropyl, and ?-(4z6-diamino-s
triazin-Z-yl) ethyl.
N-B-cyanoethyl-N-B'-hydroxyethyl~m-toluidine,
l~N-?-hydroxyethylnaphthylamine,
Np’-cyanoethyl-N-B’-hydroxyethylaniline,
N : N-bis- ( B-chloroethyL) aniline,
N: N-bis- ( IS-carbethoxymethyb) aniline,
N : N-bis- ( B-carbethoxyethyb) aniline,
65
N: N-bis- ( B-carbethoxyethyl- ) m-toluidine,
N: N-bis- ( /3-methylsulphonylethyl-) aniline,
N : N~bis~ ( ,B-methylcarb onylethyl- ) m-toluidine,
N : N-bis»(y-chloro-?-hydroxypropyl-) aniline,
N : N-bis-('y-bromo-?-hydroxypropyl-) aniline,
3,084,153
4
3
acterised by alkylating monoazo dyestuffs having no acid
dissociating salt forming groups, of the general formula:
N: N-bis-(?-v-epoxypropyh)m-toluidine,
N-ethyl-N- ( ;8—hydroxyethy1-) aniline,
N-n-butyl-N-B-cyanoethyl-m-toluidine,
N-p-cyanoethyl-N-?'-methoxyethyl-m-toluidine,
N-?-acetoxyethyl-N-;8’-carbethoxyethylaniline,
R1
N
N-y-chloro-?-hydroxypropyl - N - ?’-hydroxyethyl-m
toluidine,
10
N-?-acetoxyethyl-N-?'-methylcarbonylethyl-m-toluidine,
N-?-annnocarbonylethyl-N-ethylaniline,
N-f3-y-dihydroxypropyl-N-ethylaniline,
N-cyclohexyl-N-p-hydroxyethylaniline,
N-benzyl-N-?-hydroxyethylaniline,
N:N-bis-(?-carbomethoxyethyl-)-m-chloroaniline,
N:N-bis-(p-acetoxyethyh)-m-acetylaminoaniline,
N : N-bis- (p-acetoxyethyL) -m-tri?uoromethyl aniline,
N-B-cyanoethyl-l-naphthylamine,
N-y-chloro-?-hydroxypropyl-1-naphthylamine,
dition that of R1 to R8 at least one R represents a sub
stituent which does not dissociate acid in neutral water or
that at least R9 or R10 represents a substituent with more
than one carbon atom. Neither of these two speci?ca
20 tions describes the azo dyestuffs which are described in
the present application. Compared with the nearest re
lated dyestu?s described in British Patent No. 787,369
the dyestu?s of the present application are superior in
respect of their a?'inity for textile materials comprising
25 cellulose acetate rayon and aromatic polyester ?bres.
de?ned, are valuable for dyeing textile materials comprise
ing arti?cial ?bres, for example cellulose ester ?bres such
as cellulose acetate rayon and cellulose triacetate rayon, 30
adiparnide and the polymer from caprolactam, polyvinyl
wherein R1 to R8 represent hydrogen or substituents which
do not dissociate acid in neutral water, R9 and R10 repre
cycle-aliphatic or aromatic substituents, wherein two
The new water-insoluble azo dyestuifs, as hereinbefore
polyamide ?bres such as ?bres from polyhexamethylene
R11
15 neighbouring substituents R can form a ring with the con
methoxybenzene,
1- [N-B-hyd roxyethylamino] -2-methoxy-5 -methylbenzene
and
R9
sent hydrogen, aliphatic, araliphatic, heterocyclic-aliphatic,
1- [N : N-bis- ( IS-hydroxyethyh) amino] -3-acetamido-6
1- [N-B-hydroxyethylamino] -5 -hydroxy-n aphthalene.
/
\
'
N-?-carbomethoxyethyl-N-?’-cyanotheyl-m-toluidine,
N-ethyl-N-?-methylsulphonylethylaniline,
N-?-carbomethoxyethyl-N-ethylaniline,
Ila
The invention is illustrated but not limited by the fol
lowing examples in which the parts and percentages are
by weight:
Example 1
1.4 parts of sodium nitrite are added, with stirring,
to 22 parts of sulphuric acid at a temperature between 20°
and 27° C. during 30 minutes and the solution so ob
?bres such as polyacrylonitrile ?bres and modi?ed poly
tained is stirred for a further 15 minutes. The solution
acrylonitrile ?bres, and aromatic polyester ?bres such as
is
added with stirring to a suspension of 4.14 parts
polyethyleneterephthalate ?bres. For dyeing such textile 35 of then
2-amino-6-thiocyano-benzthiazole in 34 parts of an
materials it is preferred to use the new azo dyestuffs in a
85% aqueous solution of sulphuric acid, at a temperature
?nely dispersed form which may be obtained by milling
of
-3° C. 40 parts of water are then added and the
the azo dyestu?fs with water in the presence of a dispersing
mixture is stirred at 0° C. for 5 minutes. The diazo
agent, for example the sodium salt of the condensation
solution so obtained is then added to a solution of 5.58
product of formaldehyde and naphthalene-?-sulphonic 40 parts
of N:N-bis-(?-acetoxyethyl-)m-toluidine in a mix
acid. If desired the dispersed aqueous paste of the dye
ture
of
100 parts of water, 10 parts of a 2 N aqueous solu
stuff so obtained may be dried to form a re-dispersible
tion of hydrochloric acid and 50 parts of acetone at a
powder which may be obtained in a non-dusting form by
temperature of 5° C. 50 parts of a 40% aqueous solu
any of the processes known for forming non-dusting pow
tion of sodium hydroxide solution are then added, the mix
ders.
ture stirred for 30 minutes and the precipitated dyestu?
The new azo dyestu?s, as hereinbefore de?ned, have .45
?ltered oil. The dyestu? paste is stirred with 300 parts
excellent at?nity for arti?cial textile materials which they
of water, sodium carbonate is added until the mixture is
dye in orange to greenish-blue shades possessing excellent
neutral to litmus and the precipitated dyestuff is then
fastness to light, washing and to dry heat treatments.
?ltered off, washed with water and dried. When dispersed
The dyestuifs as hereinbefore de?ned wherein the sub
stituent X occupies the 6-position of the benzthiazole nu 50 in aqueous medium the dyestutf dyes cellulose acetate,
polyamide and aromatic polyester textile materials in
cleus and wherein the benzene nucleus B is not further
bluish-red shades possessing good fastness to light. The
substituted or is further substituted only by halogen (for
dyeings on aromatic polyester textile materials possess
example chlorine) are of great value because of their
excellent
fastness to dry heat treatments.
especially high ai?nity for arti?cial textile materials.
Example 2
The dyestuifs as hereinbefore de?ned wherein at least 55
one of the radicals R and R’ is a substituted lower alkyl
In place of the 5 .58 parts of N:N-bis-(?-acetoxyethyh)
radical have especially high light fastness.
m-toluidine used in Example 1 there are used 5.86 parts
We have further found that the dyestuffs wherein one
of NzN-bis-(B-carbethoxyethyl)aniline. The dyestuff so
of the radicals R and R’ is a B-cyanoethyl radical or at
obtained, when dispersed in aqueous medium, dyes aro
least one of the radicals R and R’ is a ?-carbo-lower al 60 matic polyester textile materials in red shades possessing
koxy-ethyl radical (for example a ?-carbethoxyethyl radi~
excellent fastness to light and to dry heat treatments.
cal) are of particular value in the dyeing of polyethylene
Example 3
terephthalate ?bres. Dyestuffs in which R and R’ repre
In place of the 5.58 parts of N:N-bis(?-acetoxyethyl)
sent ?-carbo-lower alkoxy-ethyl radicals or ,B-acyloxy-ethyl
radicals wherein the acyl group is derived from a lower 65 rn-toluidine used in Example 1 there are used 4.14 parts
alkyl carboxylic acid (for example a ?-acetoxyethyl radi
of N-?-cyanoethyl-N-?'-hydroxyethyl-m-toluidine. The
cal) are of particular value in the dyeing of cellulose ace
dyestuft' so obtained, when dispersed in aqueous medium,
dyes cellulose acetate and polyamide textile materials and
British Patent No. 440,113 describes and claims a proc
aromatic polyester textile materials in bluish-red shades
ess for the manufacture of azo dyestuffs by coupling a 70 possessing excellent fastne‘ss to dry heat treatments.
tate ?bres.
diazotised Z-aminothiazole compound with an amine cou
Example 4
pling in p-position to the amino group.
In place of the 5.58 parts of N:N-bis-(?-acetoxyethyl-)
British Patent No. 787,369 describes and claims inter
m~toluidine used in Example 1 there are used 4.36 parts
she a process for the production of water-soluble azo
dyestu?s in which the azo dyestufI" forms the cation char 75 of N-,8-cyanoethyl-N-?-methoxyethyl-m~toluidinc. The
3,084,153
5
I
6
,
listed in the second column of the table and coupling
with the coupling components listed in the third column
of the table by the method described in Example 1.
product so obtained is (6-thiocyanobenzthiazol-Z-yl)-azo
(2-methyl-4-N-?-cyanoethyl- N - ?-methoxyethylaminoben
zene). When dispersed in aqueous medium it dyes aro
matic polyester textile materials in red shades possessing
outstanding fastness to light and to dry heat treatments.
Example 5
Amine
Coupling component
textile material
In place of the 4.14 parts of 2-amino-6-thiocyanobenz
thiazole used in Example 1 there are used 3.5 parts of 2
2-amino-6-eyanobenz
amino-‘G-cyanobenzthiazole and in place of the 5.58 parts
thlazole.
of N:N-bis(,8-acetoxyethyl-)m-toluidine there are used
do _______________ ..
4.36 parts of N-B-cyanoethyl-N~?-methoxyethyl-m-tolui
dine. The product so obtained is (6-cyanobenzthiazol-2
nobenzene) when dispersed in aqueous medium it dyes
aromatic polyester textile materials in red shades possess
ing outstanding vfastness to light and to dry-heat treat
o ______________ __
In place of the 4.14 parts of 2-amino-6-thiocyanobenz—
benzthlazole.
thiazole used in Example 1 there are used 4.42 parts of
do ______________ -_
Z-amino-4~thiocyano-6-methylbenzthiazole and in place
of the 5.58 parts of N:N-bis-(B-acetoxyethyl)-m-toluidine
2-arnino-6~eyanobenz~
there are used 644 .parts of NzN-bis-(B-acetoxyethyl)-m
13.2
aminoacetanilide. The dyestuff so obtained, when dis
persed in aqueous medium, dyes cellulose acetate, cel
lulose triacetate and aromatic polyester materials in red
_.___do ______________ ._
_-___do ______________ .
In place of the 4.14 parts of 2-amino-6~thiocyanobenz
thiazole used in Example 1 there are used 4.84 parts of
2-amino-4-chloro-6-thiocyanobenzthiazole and in place of
the 5.58 parts of NzN-bis-(B-acetoxyethyl)-m-toluidine
there are used 4.36 parts of N-?-cyanoethyl-N-B'-meth
oxyethyl-m-toluidine. The dyestuff so obtained, when
dispersed in aqueous medium, dyes cellulose acetate, cel 40
lulose triacetate and aromatic polyester textile materials
in bluish red shades, possessing excellent fastness to dry
heat treatments and good fastness to light.
The 2~amino-4-chloro-6-thiocyanobenzthiazole is ob
tained by treating an acetic acid solution of o-chloro
aniline with 2 mol. equivs. of potassium th-iocyanate and
1 mol. equiv. of bromine, buffering the resulting mixture
crystallisation from butanol.
Example 8
in place of the 4.14 parts of 2-amino-6-thiocyanobenz~
idme.
N : N-bis- (B-rnethoxy
D0.
Red.
Red. '
Scarlet.
Red.
Red.
Red.
Reddish violet.
Bluish red.
Do.
Do.
Do.
oxyethyD-m-tolu
ethyl) -1n-t0lnidine.
N: N-bis-(?-aeetoxy
ethyl) -m-chlor0
aniline.
_-___do ______________ __
N-?-cyanoethyl-N
B’-carbethoxyethyl
Red.
m-toluidine.
_-___do ______________ __
N :N-bis-(B-acetoxy
Scarlet.
_-___do ______________ __
N : N-bis-(B~acetoxy
Reddish violet.
2-amino-6-eyanobenz
thiazole.
_-___do ______________ __
_.___do ______________ __
_.___do ______________ -.
_
2-amino6-thioeyano
benzthiazole.
__ - _ _do ______________ _ _
. __ - -do ______________ __
ethyD-rn-tri?uoro
methylaniline.
ethyl) -m~amino
aeetanilide.
N-?-eyanoethyl-m
Orange.
chloroaniline.
N: N-bis-(carbometh
oxymethyhaniline.
N-cyanornethyl-N
B-carbomethoxy
ethylaniline.
N-B-eyanoethyl-N
B’-carbomethoxy
ethylaniline.
N :N-dimeth ylaniline _
Reddish orange.
Do.
Red.
Bluish-red.
NzN-bis-(carbethoxy
Reddish-orange.
methyl) aniline.
N-methyl-N-B-(4: 6<
diamino-s-triazin
Red.
2-yl)ethylaniline.
_-___do ______________ ._
N : N-bis- (B-methoxy
Bluish red.
_.___do ______________ __
N : N-bis-(B~acet0xy
Red.
ethyD-m-toluidine.
ethyl) ~m-ehloro
aniline.
N-?-cyanomethyl-l
naphthylamine.
ethyl) -l-naphthyl
Reddish violet.
Violet-brown.
amine.
Red.
N : N-bis- (B-acetoxy
ethyD-l-naphthyl
and the dyeings possess excellent fastness to dry heat treat
ments and good fastness to light.
Reddish-brown.
amine.
The 2-amino-4-chloro-6-cyanobenzthiazole is obtained
_.___do .............. _.
aniline with thiophosgene, treating the 2-chl01'o-4-cyan0
N: N-bis-(?-acetoxy
ethyl) -rn-amino
acetanilide.
Bluish-red.
N : N-bis- ('y-chloro-?
D0.
hydroxy-n-propyb
m-toluidine.
_-___do ______________ __
ring-closing the resulting N-(2-chloro-4-eyanophenyD
using the dyestu?s obtained by diazotising the amines 75
N: N-dimethylaniline
_-___do ______________ __
noacetanilide. The dyestu? so obtained, when dispersed
in aqueous medium, dyes cellulose acetate, cellulose tri
acetate and aroma-tic polyester materials in violet shades
shades obtained on aromatic polyester textile materials
N-ethyl-N-B-amino
carbonylethyl
N: N-bls-(B-carbeth
are used 6.44 parts of N:N-bis-(?-acetoxyethyl)-m-ami
thiourea by re?uxing with bromine in chloroform.
The following table gives further examples of the
N: N-bis-(B-amino
earb onyle th yl) -m‘
toluidiue.
_.___do ______________ __
Z-amino-4-chloro-6-cyanobenzthiazole and in place of the
5.58 parts of NzN-bis-(?-acetoxyethyl)-m-toluidine there
phenylisothiocyanate so produced with ammonia, and 70
hydroxyethylaniline
N-ethyl-N-B-carbo
methoxyethyl
aniline.
N-n-butyl-N-B-cyano
ethyl-m-toluidine.
N : N-bis-(?-earb
ethoxyethyD-m
toluidine.
N-B-hydroxyethyl
N -,8’-aminocarbon
ylethyl'rn-toluidine.
N-n-butyl-N-B-cyano
ethyl-m-toluidine
thiazole used in Example 1 there are used 4.20 parts of
by treating a chloroform solution of 2-chloro-4-cyano
bis(?-hydroxy
ethyl) aniline.
N: N-bis(?-earheth
oxyethyl) aniline.
N-B-eyanoetl1y1-N-B
_-___do ______________ __
_.___do ______________ _
with sodium acetate and treating with a further 2 mol.
the precipitate by extraction with hot dilute acid and re
oxyethyDm
aniline.
Example 7
equivs. of potassium thiocyanate and 1 mol. equiv. of
bromine. The mixture is poured into water and the 2 50
amino-4-chloro~6~thiocyanobenzthiazole is isolated from
6.
_.___do ______________ __
shades and the dyeings obtained possess excellent fast 30
ness to dry heat treatments and good fastness to light.
Bluish-red.
_.___do ______________ ..
beéizthiazole.
20
N-?-eyanoethyl-N-B
hydroxyethyl-m
toluidine.
3 : 5-di1nethyl-N :N
2-amino-6-thioeyano
Example 6
Yellowish—red.
hydroxyethylaniline.
_-___do ______________ _.
_-___do ______________ __
ments.
N—B-cyanoethyl-N-B
toluidlne.
N : N-bis-(?-acet
yl)azo-(2-methyl-4-N-?ecyanoethyl-N-[i-methoxyethylami
Shade on aro
matic polyester
_____do ______________ __
N : N-bis-(B-acetoxy
ethyl) aniline.
.____d0 ______________ __
_-___do ______________ __
N-B-cyanoethyl-m
chloroanilina.
Orange-brown.
Red.
Orange-brown.
Orange.
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