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Патент USA US3096328

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3,096,318
Patented July 2., 1963
2
lized azo compounds can be metallized either on or off
the materials they color. Metalization can be carried
out, for example, by heating the non-metallized azo com
pound with a solution or dispersion of the metallizing
3,096,318
BENZOTHIAZOLE AZO ?-NAPHTHOL
DYE COMPOUNDS‘
_
James M. Straley, John G. Fisher, and Raymond C. Har
ris, Kingsport, Tenn., assignors to Eastman Kodak
Company, Rochester, N.Y., a corporation of New
agent. In the metallized azo compounds of our invention
the metal and the monoazo compound are combined in
the ratio out about one atom of metal to two molecules
of the nionoazo compound. The metallized azo com
pounds are referred to herein as 1:2 metal complexes.
Jersey
No Drawing. Filed Jan. 18, 1960, Ser. No. 2,827
10 Claims. (Cl. 260-146)
10 The manner in which metallization can be carried out
is fully described hereinafter.
Nickel chloride, nickel bromide, nickel sulfate, nickel
This invention relates to certain metallized and non
metallized benzothiazole azo ?~naphthol compounds, dea
void of a Water-solubilizing group, and their application
for the dyeing or coloring of acrylonitrile polymers, es
acetate, nickel formate, nickel thiocyanate [Ni(SCN)2],
cobaltous bromide, cobaltic chloride, cobaltous chloride,
pecially textile materials prepared from said polymers. 15 cobaltous acetate, cobalt thiocyanate [C01(SCN)2], chno~
mium ltri'chloride, chromium tribro-mide, chromic sulfate,
More particularly, the (azo compounds of our inven
chromic acetate and chromium thiocyanate [Cr-(SCN)3],
for example, are illustrative of the metallizing agents that
tion consist of the monoazo compounds having the for
mula:
s
OH
/
I
20
can be employed.
Both the non-metallized and the metallized azo com
pounds of our invention can be applied to polyacryloni
trile' textile materials in the form of an aqueous disper
sion. Coloration can also be eifected' by incorporating
the non-metallized or metallized azo compounds into the
17'
25 spinning dope, spinning the ?ber as usual and convert
ing the non-metallized azo compounds to their metal?ized
form if desired. Also the metallizing agent can be in.
corporated in the spinning dope, the ?ber spun as usual
wherein R represents an alkylene radical having 2 to 3
carbon atoms, R’ represents an alkyl radical having 1 to
and then treated in a dyebath containing one or more
of the non-metallized azo compounds to (form the metal
complex on the ?ber.
4 carbon atoms, X represents a member selected from
the group consisting of a thio radical and a sulfonyl radi
cal, N[R']2 collectively represents a member selected
The non-metallized monoazo compounds yield red to
from the group consisting of the morpholinyl and piper
violet shades on polyacrylonitrile materials. The metal
idyl radicals and Y represents a member selected from
l'ized compounds yield ?ast blue to violet shades on poly
the group consisting of a hydrogen atom, a halogen ‘atom,
35 acryl'onitrile materials, such as acrylic ?bers. The metal
the sulfamyl group, a
lized dyeings have better‘ fastness to washing than the
H
corresponding non-metallized dyeings and frequently
have improved fastness to light. Among the acrylonitrile
H
40 lized and metallized azo compounds of our invention are
-soiNa1ky1
group, a —-SO2N(\alkyl)2 group, a
polymers that can be dyed or colored with the non-metal
—C O Nalkyl
those disclosed in Straley and Giles ‘US. Patent 2,857,372
issued’October 21, 1958.
group, a -—CON(alky1)2 group or a
H
of the benzene series and wherein alkyl as used herein
represents an alkyl radical having 1 to 4 carbon atoms
and their metal complexes containing a metal selected
2-amjno-6-BJdimethylaminoethylthiobenzothiazole,
2-amino-6-p-diethylammoethylthiobenzothiazole,
Z-amirro-ti-?-di-n-propylamino ethylthiobenzo-thiazole,
2-amino-6-B-di~n-butylaminoethylthiobenzothiazole,
2-amino-l6-'y-dimethylaminopropylthiohenzothiazlole,
from the group consisting of cobalt, nickel and chro
mium, said azo compounds being devoid of a water-solu
bilizing group.
2Jamino-6-~/-di-n-propylaminopropylthiobenzothiazole,
2-amino-6Jy-di-n-butylaminopropylthiobenzothiazole,
—-C ONR1
group, wherein R1 represents a monocyclic aryl nucleus 45
2-amino-6-'y-diethylaminopropylthiobenzothiazole,
Z-amino-?a ( ,B-dimethylamino-vt-methylethylthio) benzo
The non-metallized azo compounds of our invention
are prepared by \diazotizing a Z-aminobenzothiazole com
pound having the formula:
55
v
[amen-X
s
/
thiazole,
2—amino-6-'(B-diethylamino-u-methylethylthio ) benze
thiazole,
2-amino-6-,8-piperidylethylthiobenzothiazole,
2-amino-6-'y-piperidylpropylthiobenzothiazole,
2-amino-6-,8-morpholinylethylthiobenzothiazole,
Z-amino-6-'y-morpholmyflpnopylthiobenzothiazole
/ C-NH2
\N
wherein R, R’, X and N[R']2 collectively have the mean
ing previously assigned to them and coupling the diazoni
60
and the corresponding sulfonylbenz-othiazole compounds
such as
um compound obtained with a {3—naphthol compound hav
2-amino-6-,8-dimethylaminoethylsulfonylbenzothiazole,
2-amino-6-?-diethylaminoethylsulfonylbenzothiazole,
2-amino-6-?-di-n-propy1aminoethylsullfonylbenzothiazole,
2-amino-6-?-di-n-buty1aminoethylsulfonylbenzo
ing the formula:
OH
thiazole,
,
_
2-amino~6'-'y-dimethylami-nopropylsulfonylbenzothiazole,
70
2-amino~6-'y-dtethylaminopropylsulfonylbenzothiazole,
24amino-6-'y~di-n-butylaminopropylsulzfonylbenzothiazole,
, 2-amino-6~ (,8-dimethylamino-a-metl1ylethylsulfonyl)
vwherein Y is as de?ned lhereinbefore.
The non-metal
benzo-thiazole,
4,
2-amino-6~?-piperidylethylsulfonylbenzothiazole,
Z-amino-6-'y-piperidylpnopylsulfonylbenzothiazole,
Example 3
One gram of the non-metallized azo compound of Ex
ample 1, 15 cc. of acetone and 2 cc. of 28% aqueous
ammonium hydroxide were re?uxed together and a solu
for example, are illustrative of the Z-arninobenzothiazole 5 tion of 0.7 gram of Ni(OOCCH3)2.4H2O in 15 cc. of
2-arnino-6-B-morpholinylethylsulfonylbenzothiazole, and
2-amino-.6W-morphollinylpropylsulfonylbeuzothiazole,
compounds used in the preparation of the azo compounds
of our invention.
The following examples illustrate the invention.
Example 1
12.65 grams of 2-amino-6-B-dimethylaminoethylthio
50% aqueous acetone was added over a period of 15
minutes. Re?uxing was continued for three hours, while
stirring, after which the reaction mixture was poured into
400 cc. of water and the temperature brought to 80° ,C.
10 20 grams of sodium chloride were added, with stirring,
and then the reaction mixture was cooled to room tem
benzothiazole were dissolved in 120 cc. of water con~
perature. The metallized dye product, a 1:2 nickel com
plex in which nickel and the monoazo compound of
Example 1 are combined in the ratio of about one atom
taining 70 cc. of 96% H2504. To this solution was
added, with stirring, at 0° C. nitrosylsulfuric acid pre
pared from 3.9 grams of sodium nitrite in 25 cc. of 96% 15 of nickel to two molecules of the monoazo compound,
H2804. The reaction mixture thus obtained was sitrred
which precipitated was recovered by ?ltration, washed
2 hours longer while maintaining the temperature below
with a 5% aqueous sodium chloride solution and air-dried.
5° C. The diazonium solution thus prepared was added
It dyes acrylic ?bers such as Verel and Orlon 42 blue
slowly to a solution of 7 grams of ,B-naphthol in 100 cc.
shades which have good fastness to light, washing and gas.
of 2% aqueous NaOH and the temperature was kept 20
Example 4
below 10° C. by the intermittent addition of ice. The
mineral acid present was neutralized with sodium car
A polyacrylonitrile textile fabric ‘dyed red with a 1%
bonate ‘and then the reaction mixture was stirred for
dyeing (by Weight of pure dye) of the dye product of
2 hours longer. The dye compound formed was re
Example 1 was padded with a 3% aqueous solution of
covered by ?ltration, washed with water and dried. It 25 nickel thiocyanate under conditions such that a 60 to
has the formula:
100% pick up, based on the weight of the fabric, was
obtained. The polyacrylonitrile fabric was then aged in
a steam chest under 5 psi. pressure for 10 minutes
as‘
s
0H
after which it was scoured at 60° C. with soap and water,
30 rinsed well with water and dried. A 1:2 metal complex
/Nomorr,s~
/
\
I
OH:
O——N=N——
in which nickel and the monoazo compound of Example
\
1 are combined in the ratio of about one atom of nickel
to two molecules of the monoazo compound is formed in
situ on the polyacrylonitrile fabric being dyed. The
35 polyacrylonitrile fabric was dyed a blue shade having
and colors acrylic ?bers brownish-red shades. The 1:2
nickel complex of this dye compound yields fast blue
good fastness to light, washing and gas.
dyeings on acrylic ?bers such as Orlon 42 ‘and Verel,
as do the 1:2 cobalt and 1:2 chromium complexes.
‘aqueous solution of cobalt thiocyanate or chromium thio
When the above example is repeated using a 3%
40
cyanate in place of the nickel thiocyanate solution, the
polyacrylontirile fabric is likewise :dyed a blue shade
having good fastness to light, washing and gas. The 1:2
cobalt complex and the 1:2 chromium complex, respec
benzothiazole were added to 25 cc. of water and 37 cc.
tively, of the monoazo compound of Example 1 are
of 96% sulfuric acid and stirred below 50° C. to ‘com
formed in situ on the polyacrylonitrile fabric being dyed.
45
plete solution. 5 cc. of 30% H202 were added at 50-60"
Example 5
C. and then the reaction mixture was raised to 90° C.,
maintained at this temperature for 1 hour and cooled.
Example 1 was repeated using 14.05 grams of 2~amino~
12 cc. of 96% sulfuric acid and 60 grams of ice were
6-B-diethylaminoethylthiobenzoth-iazole in place of 2
added. A nitrosyl sulfuric acid solution prepared ‘from
amino~6-[3-dimethylarninoethylthiobenzothiazole. The dye
50
2.6 grams of sodium nitrite and 17.6 cc. of 96% sulfuric
compound obtained dyed polyacryonitrile textile fabrics
acid was added, with stirring, at 0-5“ C. and the re
dull red shades. When it is metallized on a polyacrylo
action mixture was maintained at this temperature for 3
nitrile ?ber, such as Verel or Orlon ‘42, for example, with
hours. The diazonium solution thus prepared was added
nickel or cobalt thiocyanate, for example, blue shades
below 5° C. to a solution of 5.1 grams of ?-naphthol
having
good t?asmess to light, gas and washing are ob
in 200 cc. of 2% aqueous sodium hydroxide. After 2 55 tained. In each instance a 1:2 metal complex is formed
hours the reaction mixture was made strongly basic with
in situ on the polyacrylonitrile fabric being dyed.
Example 2
10.25 grams of 2-amino~6-y-diethyleminopropylthio
ammonium hydroxide. The solid reaction product which
precipitated was recovered by ?ltration, washed with
water and air-dried. 1-[6’-7-diethylaminopropylsulfonyl
benzothiazole-2’-azo] -2-naphthol, having the formula:
Example 6
60
Example 1 was repeated using 14.75 grams of Z-amino
6-~/-diethylaminopropylthiobenzothiazole in place of 2
amino~6qoedimethylaminoethylthiobenzothiazole. The dye
compound obtained dyed polyacrylonitrile textile fabrics
dull red shades.
OH
When it is metallized on a polyacrylo
nitrile ?ber, such as Verel or Orlon 42, for example,
65 with nickel or cobalt thiocyanate, for example, blue
shades having good fastness to light, gas and washing
are obtained.
In each instance a 1:2 metal complex is
formed in situ on the polyacrylonitrile fabric being dyed.
Example 7
70
was obtained.
It colors acrylic ?bers such as Orlon 42
and Verel red shades. The 1:2 nickel, the 1:2 cobaltrand
the 1:2 chromium complexes of this dye compound yield
fast violet shades on Verel and Orlon 42 acrylic ?bers.
Example 1 was repeated using 13.35 grams of 2-amino
6w-dimethylaminopropylthiobenzothiazo-le in place of 2
amino-6-B~dimethylaminoethylthiobenzothiazole. The dye
compound obtained dyed polyacrylonitrile textile fabrics
Metallization can be effected either on or off the ?ber. 75 dull red shades.
When it is metallized on a polyacrylo
3,098,318
S
nitrile ?ber, such as Verel or Orlon 42, for example,
with nickel or cobalt thiocyanate, for example, blue
shades having good fastness to light, gas, and washing
are obtained.
Color
2-Aminobenzothiazole
Compound
In each instance a 1:2 metal complex is
Coupler
Original
Final
formed in situ on the polyacrylonitrile fabric being dyed.
Example 8
G-B-di-n-butylamino-
Example 1 was repeated using 13.35 grams‘ of Z-amino
ethylsulfonyl.
ethylsullouyl.
6-?-dimethylamino - 0c - methylethylthiobenzothiazole in
6-?-dimethylamino-
place of 2-amino-6-?-dimethylaminoethylthiobenzothia
G-?-dimethylamino-
ethylthio.
zole. The dye compound obtained dyed polyacrylonitrile
textile fabrics red shades. When it is met-allized on a
polyacrylonitrile ?ber, such as Verel or Orlon 42, for ex
D0 _________________ _-
Do ______ __
ample, with nickel or cobalt thiocyanate, for example,
blue shades having ‘good fastness to light, gas and wash 15
ing are obtained.
red ____ __
In each instance a 1:2 metal complex
6-bromo-2-naphthol. _ _ ___do_ _ __
blue.
?~naphthol __________ .. ___do____
H
3-CONCH3-2
naphthol.
naphthol.
3-OON(n—C4Hg)2»2naphthol.
3-CON(CzH5)z-2-
Do.
Do.
___do____
Do.
___do_.__
Do.
___do____
Do.
D0 ______ __
D0 _________________ __
6-sulfamyl-2-naphthol. ___do.___
6-S0zN(Il~C4H9)z-2_.._dO____
D0.
DO.
Do _________________ __
6_SO2NGH3-2—
DO _________________ ..-
6~SOzNCzH5-2-
De _________________ __
6-SO2N(n-C4H9)-2-
is formed in situ on the polyacrylonitrile fabric being
naphthol.
H
dyed.
Example 9
of 96% H2504. ‘0.72 gram of sodium nitrite in 5 cc. of
96% H2804 were added, with stirring, at 0-100 C. The
resulting reaction mixture was stirred below 5° C. for
2- hours and then added to a solution of 2.93 grams of 25
the o-methoxyanilide of 2-hydroXy-3-naphthoic acid in
50 cc. of water containing 3 grams of sodium hydroxide,
6-?-di—n-propylamino~
naphthol.
___dO____
DO.
__.do-___
Do.
?-naphthol __________ _. __.do__._
Do.
naphthol.
eth thio.
sulfon
.
?-li-morpholinyl-ethyl
0.
G-?-morpholinyl-cthyl-
It colors
Do.
G-B-piperidyl-ethylthio.6-y-piperidyl-propylthio.
(S-B-piperidyl-ethyl
?'yepiperidyl-propyl-
s
polyacrylonitrile violet shades. The 1:2 nickel and the
1:2 cobalt complexes of this dye color acrylic ?bers
such as Verel and Orlon 42 blue shades having good 35
fastness to light, gas and Washing. The 1:2 chromium
complex yields blue-violet shades on said ?bers.
.__do._-_
H
sulfonyl.
the temperature being kept below 10° C. by the addition
of ice. After 2 hours’ stirring, without further cooling,
the acid present was neutralized with Na2CO3. The dye
compound which precipitated was recovered by ?ltration,
naphthol.
H
‘2.93 grams of 2-amino-6-7-diethylaminopropylthioben 20
zothiazole were dissolved in 24 cc. of water and 14 cc.
washed with cold water and dried at 60° C.
B-naphthol .......... __
etliylthio.
?-?-di-n-butylamino-
H
3-CON-phenyl-2-
___do.-__ reddish
naphthol.
blue.
?-naphthol __________ __ ___<1o____ blue.
__.__do ______________ __ .__do____
violet.
fonyl;
6w-morpholinyl-
.____do ______________ _. ___do____
blue.
tS-y-morpholinyl~
___--do ______________ __ ___do_--_
violet.
propylthio.
propylsulfonyl.
Example 10
‘2.93 grams of 2-:amino-6-,B-piperidylethyl-thiobenzothia 4:0 The non-metalliz-ed lazo compounds disclosed in the fore
going tabulation can also be metallized with a suitable
zole were diazotized and the di-azonium compound ob
cobalt :or chromium metallizing agent, especially cobalt
tained was coupled with 2.52 grams of N,N-dimethy1-2
thiocyanate and chromium thiocyanate, to form the 1:2
hydroxynaphthalene-6-sulfonamide. Diazotization, cou
cobalt and the 1:2 chromium complexes thereof. The 1:2
pling and recovery of the dye compound formed were
carried out in accordance with the procedure described 45 cobalt complexes yield about the same colors as the corre—
sponding 1:2 nickel complexes. In the case of the 1:2
in Example 9. The dye compound obtained colors poly
chromium complexes the color is ordinarily redder. As
acrylonitrile red shades. The 1:2 nickel and the 1:2 co
previously noted metallization can be effected either on or
balt complexes of this dye color acrylic ?bers such as
off the ?ber.
Verel and Orlon 42 blue shades having good fastness to
The Z-aminobenzothiazole compounds used in prepar
light, gas and was-hing. The 1:2 chromium complex 50
ing the iazo compounds of our invention are new com;
yields violet shades on said ?bers.
pounds. They are described and claimed in copen-ding
Example 11
Straley and Fisher US. application Serial No. 2,869, ?led
January 18, 1960, now abandoned.
2.8 grams or Z-amino-6-5-diethylaminoethylthiobenzo
The Zeaminobenzothiazole compounds wherein X is a
thiazole were diazotized and the diazonium compound 55
thio radical can ‘be prepared by reacting the hydrochloride
obtained was coupled with 2.24 grams of 6-b-romo-2-nap-h
salt form of a'compound having the formula:
thol. Diazotizati'on, coupling and recovery of the dye‘
compound formed were carried out in accordance with
the procedure described in Example 9. The dye com
pound obtained colors polyacrylonitrile red shades. The 60 wherein R, R’ and N [R']2 have the meaning previously
1:2 nickel and the 1:2 cobalt complexes of this dye color
assigned to them and Z represents a chlorine or bromine
acrylic ?bers such as Verel and Orlon 42 blue shades
atom with 2-amino-6~mercaptobenzothiazole or its alkali
having good fastness to light, gas and Washing. The 1:2
chromium complex yields violet shades on said ?bers.
The following tabulation further illustrates the iazo 65
metal ‘salts. The non-salt form of the compounds having
the formula:
compounds that can be prepared from the Z-aminobenzo
can be employed but inasmuch as these compounds'lare
thiazole compounds of our invention ‘and sets forth (1)
more easily prepared in their salt form, such as the hydro
the colors the non-metallized azo compounds yield on
chloride salt form, the use of the hydrochloride salt form
polyacryloni-trile textile fabrics made of Orion 42 or
Verel acrylic ?ber and (2) the colors obtained when- the 70 is shown in the examples given hereinafter.‘
Z-amino - 6 ~mercaptobenzothiazole is a known com
non-metallized dyeings are metallized with nickel th1io~v
cyana-te to obtain the 1:2 nickel complex in situ on the
pound. It can be prepared by reacting 2-amino-64thi0~
polyacrylonitrile textile material ‘being dyed. “Original”
refers to the non-metallized dyeing and “Final” refers to
the metallized dyeing.
cyanobenzothiazole with sodium sul?de. As shown here
inafter the Z-amino-6-mercaptobenzo-thiazole thus formed
75 can be used, in situ, without being separately isolated.
3,096,318
851
J
The Z-an?nohenzothiazole compounds wherein X is a
sulfonyl radical can be prepared by reacting the corre
2-amino-6-B-piperidylethylthiobenzothiazole having the
formula :
sponding compounds wherein X is a thio radical with hy
drogen peroxide in an acid medium.
The following examples illustrate the preparation of
the Z-aminobenzothiazole compounds.
Example 12
N
68.4 grams of 2-amino-6-thiocyanobenzothiazole, 160
was obtained as a solid melting at 78-81° C.
grams of INaZS-9H2O and 700 cc. of water were re?uxed 1O
together for ten minutes.
Example 18
A solution of 57.1 grams of the
The general procedure set forth in Example 12 was fol
hydrochloride of 'y-dirnethylaminopropyl chloride
lowed using B-morpholinyle-thyl chloride hydrochloride in
[ (CH3) ZNCHZ'CHZCHZCl - HCl]
place of 'y-dimethylaminopropyl chloride hydrochloride.
and 27.8 grams of NaHCOB in 400 cc. of water was added 15 2-amino-6-?-morpholinylethylthiobenzothiazole was ob
tained as a solid melting at 71-73 °.
over a period of about 15 minutes. Re?uxing was con
tinue-d for one hour ‘further after which the reaction mix
Example 19 i
ture was allowed to stand overnight. The reaction prod
uct which precipitated was recovered by ?ltration, washed
with cold water and air-dried. 69.4 grams of 2-amino-6
The general procedure set forth in Example 12 was
followed using ry-diethylaminopropyl chloride hydrochlo
ride in place of 'y-dimethylaminopr-opyl chloride hydro
'y-dimethylaminopropylthiobenzothiazole having the for
chloride
mula:
2 - amino - 6 - 'y - diethylaminopropylthiobenzo
thiazole was obtained as ‘a solid melting at 82-84" C.
s
(oHmNomomoHrs-
25
/
Example 20
The general procedure set forth in Example 12 was fol'
lowed using 'y-di-n-propylaminopropyl chloride hydro
chloride in place of ly-dimethylaminopropyl chloride hy
drochloride.
30
and melting at 113.5-1l6° C. were thus obtained.
Example 13
Example 12 was repeated using 57.8 grams of Z-diethyl
aminoethyl chloride hydrochloride in place of v-dimethyl
aminopropyl chloride hydrochloride.
lowed using ?-di-n-butylaniinoethyl chloride hydrochlo
ride in place of y-dimethylaminopropyl chloride hydro
35
2 - amino - 6 - b‘ - di - u - butylaminoethylthio
In using the compounds of our invention wherein X is
a sulfonyl radical we prefer to make and use them with
92—94° C. were obtained.
out isolation. This procedure is illustrated in Example 2.
40
Following the directions given herein 2-amino-6-[i-di-n
propylaminoethylthiobenzothiazole, 2-arnino-6-7-di-n-bu
10 grams of Z-amino-G-B-diethylaminoethylthiobenzo—
thiazole were slurried in 10 cc. of glacial acetic acid. Ten
cc. of 30% H202 were added portionwise. The tempera
ture rose to 100° C. when about half the H202 had been 45
added. The reaction mixture was then cooled to 55° C.
was allowed to stand at room temperature until the forma
chloride.
benzothiazole was obtained as a ‘gummy solid.
71 grams of 2
and the remainder of the H202 was gradually added.
After all the H202 had been added the reaction mixture
Example 21
The general procedure set forth in Example 12 was fol
amino-6~?~diethylaminoethylthiobenzothiazole melting at
Example 14
2 - amino - 6 - 'y - n - propylaminopropyl
thiobenzothiazole was obtained as a gummy solid.
tylaminopropylthiobenzothiazole,
2-amino-6-f5-diethyl
amino _ a - methylethylthiobenzothiazole,
2 - amino - 6
'y - piperidyl - propylthiobenzothiazole', 2 - amino - 6 - 'y
morpholinylpropylthiobenzothiazole, 2-amino-6-[3-dimeth
ylaminoethylsulfonylbenzothiazole, 2-amino-6-y-dimeth
ylaminopropylsulfonylbenzothiazole, 2-amino-6-y-diethyl
aminopropylsulfonylbenzothiazole, 2-amino-6-?-di-n-pro
pylaminoethylsulfonylbenzothiazole and 2-amjno-6-?-di
tion of crystals ceased. The reaction product was re 50 n-butylaminoethylsulfonylbenzothiazole, vfor example, can
covered by ?ltration and recrystallized from ethanol.
2-amino-6-?-diethylaminoethylsulfonylbenzothiazole was
also be prepared.
The non-metallized and metallized azo compounds de
thus obtained in the form of white crystals melting at
scribed herein can be applied to acrylonitrile polymers,
57.5-58.5° C.
such as polyacrylonitrile and acrylonitrile graft polymers,
The procedure set forth in ‘Example 14 is of general ap 55 in the form of an aqueous dispersion.
plicability for the preparation of the compounds of our
The following example illustrates one satisfactory way
invention wherein X is a sulfonyl radical.
in which the non-metallized azo compounds can be used
to dye an acrylonitrile polymer textile material. .1 gram
Example 15
of dye is dissolved by warming in 6 cc. of methyl Cello
Example 12 was repeated using 52.8 grams of 2-dimeth 60 solve. A 2% aqueous solution of a nonionic surfactant,
ylaminoethyl chloride hydrochloride in place of 'y-dimeth
such as lgepal CA (a polymerized ethylene oxide-alkyl
ylamino-propyl chloride hydrochloride. 2-amino-6-?-di
phenol
condensation product), is added slowly until a
methylaminoethyl thiobenzothiazole melting at 110-112"
?ne emulsion is obtained and then the dye mixture is
C. was obtained.
Example 16
The general procedure set forth in Example 12 was
followed using ,B-dimethylamino-u-methylethyl chloride
hydrochloride in place of 'y-dimethylaminopropyl chloride
hydrochloride. 2-amino-6-?-dimethylamino-a-methyleth
ylthiobenzothiazole was obtained as a gummy solid.
Example 17
The general procedure set forth in Example 12 was
brought to a volume of 200 cc. with warm water. 5 cc.
65 of a 5% aqueous solution of formic acid or acetic acid are
added and then 10 grams of fabric made from an acrylic
?ber is entered and in the .case of Orlon 42 the dyeing is
carried out at the boil for one hour.
In the case of ma
terials made of Verel acrylic ?ber the dyebath tempera
70 ture should not exceed 90° C. in order to avoid damage
to the ?ber. The dyed material is then washed well with
water and dried.
The metallized dyeing can be obtained
in accordance with the procedure described in Example 4.
A 3% solution of a salt, other than the thiocyanate salt,
followed using ?-piperidylethyl chloride hydrochloride in
place of 'y-dimethylaminopropyl chloride hydrochloride. 75 can be used. However, we have found the use of the
3,096,31 s
l0
thiocyanates of nickel, cobalt and chromium to be particu
an alkyl radical having 1 to 4 carbon atoms and their 1:2
larly advantageous.
metal complexes containing a metal selected from the
group consisting of cobalt, nickel and chromium, said azo
compounds being devoid of a water-solubilizing group.
The premetallized azo dyes can be applied in the same
general manner as the non-metallized azo dyes.
How
2. Compounds according to claim 1 wherein X is a
ever, in order to mitigate the possibility of demetalliza
tion during dyeing 5 cc. of a 5% aqueous solution of a
thio radical.
weak acid such as boric acid is used instead of formic
acid or acetic acid. Except for this change the dyeing
3. Compounds according to claim 1 wherein Y is a
hydrogen atom.
4. The non-metallized monoazo compounds having the
conditions are the same.
'
The non-metallized and metallized azo compounds de 10 formula set forth in claim 1.
5. The 1:2 nickel complex form of the monoazo com
scribed herein are devoid of water solubilizing groups
pounds having the formula set forth in claim 1. .
such as the carboxylic acid and the sulfonic acid groups.
Any other ‘suitable method known to the art can be used
6. The azo compound having the formula:
to apply them to acrylonitrile polymeric materials.
The dyeings obtained with the chromium complexes 15
tend to be redder than those obtained with the nickel
and cobalt complexes.
The invention has been described in detail with par
ticular reference to preferred embodiments thereof, but it
CH;
will be understood that variations and modi?cations can 20
7. The 1:2 nickel complex of the azo compound set
be e?ected within the spirit and scope of the invention as
forth in claim 6.
described hereinabove and ‘as de?ned in the appended
8. The azo compound having the formula:
claims.
We claim:
1. The azo compounds selected from the group con 25
sisting of the monoazo compounds ‘having the formula:
0&3
NCHzOHrGHaS-
s
/ \
O?s
OH
N
OH
/O_N=N
9‘. The azo compound having the formula:
0t?‘
s
/NOH2OH:|S
Y
on
/\
I 02115
°_'N=N_
wherein R represents an alkylene radical having 2 to 3 35
carbon atoms, R’ represents an alkyl radical having 1 to 4
carbon atoms, X represents a member selected from the
group consisting of a thio radical and a sulfonyl radical,
I 10. The azo compound having the formula:
N[R’]2 collectively represents a member selected from
the group consisting of the morpholinyl and piperidyl 40
radicals and Y represents a member selected from the
group consisting of a hydrogen atom, a bromine atom,
the sulfamyl group, a
N/
H
—-S0:Nalky1
group, -a ——SO2N(a1kyl)2 group, a
45
References Cited in the ?le of this patent
UNITED STATES PATENTS
H
-0 oNalkyl
group, a -CON(-alkyl)2 group and a
50
H
—-0 ON R1
group, wherein R1 represents a member selected from
the group consisting of a phenyl group and a methoxy
phenyl group and {wherein alkyl as used herein represents 55
2,128,256
2,402,538
2,868,774
2,875,190
2,916,482
Krzikall-a et a1. _______ __ Aug. 30,
Dreyfus ____________ __ June 25,
Straley et al. ________ __ Jan. 13,
Straley et a1. ________ __ Feb. 24,
Straley et a1. _________ __ Dec. 8,
1938
1946
1959
1959
1959
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