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Патент USA US2129014

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2,129,014‘
Patented Sept. 6, 1938
UNITED STATES PATENT OFFICE
2,129,014
DYESTUFFS OF THE ANTHRACENE SERIES
Frank Lodge and Colin Henry Lumsden, Blackley,
Manchester, England, assignors to Imperial
Chemical Industries Limited, a corporation of
Great Britain
No Drawing. Application January 13, 1933, Se
rial No. 651,623. In Great Britain January 29,
1932
16 Claims. (Cl. 260-243)
This invention relates to the manufacture of chlorine or bromine), the nitro-, sulpho- or
carboxy~ group, the hydroxy- or amino- group,
new anthracene and anthraquinone dyestuffs.
More particularly, this invention deals with or substituted hydroxy- or amino- groups. When
thioindigoid dyestuffs of the anthracene series an amino group is substituted the substituent
may be alkyl or acyl, and if acyl the acyl group
5 having the following general formula:
may form part of a ring structure, as in the lac
tam compounds hereinafter described.
According to the nature of the substituents the
products of the invention are vat or acid dye
i'AxtolJ/x
QYO 0Y9
wherein Z stands for an oxygen atom, a hydrogen
is atom or an intermediate stage of reduction; one
of the letters X and Y stands for an organic or
inorganic substituent; while the other letter
stands for hydrogen or the same or a different
substituent. For simplicity we shall hereinafter
refer to our novel compounds as ViS-Et-ViS-oc
substituted 1.2-thioindigoid compounds of the
anthracene series.
According to the invention we obtain new dye
stuffs of the general formulae:
Sig
|
|
Y
NR0}, OJ, C/TER
(IJH/
30
No. 377,740.
The ring-closure condensation to the thioin
digoid grouping according to the invention pro
ceeds with remarkable ease, and this is surpris
ing because with an anthraquinone-l-thioglycol
lic acid devoid of substituents in the 5 and 8 posi
tions ring-closure condensation does not readily
take place, if at all. Not only so, but known
methods for making thioindigoid dyestuffs of the
anthraquinone series involve a tedious production
of a 1.2- or 2.1-carboxy-anthraquinonyl-thiogly
collie acid. Hence great technical advantages ac
crue from the present invention.
The invention is illustrated, but not limited, 25
by the following examples, in which the parts‘
are by weight.
Example 1
on/
X
stuffs, or, suitably treated, they may be applied 10
by the methods described in the British patent,
5 parts of the compound
30
song-c0011
X
and
‘f
03 Q1
oo
s_T=—__T-~s
oo
/ U00 0040/
\oo
s
wherein the anthracene or anthraquinone resi
dues may contain other substituents, by treating
an anthracene or anthraquinone-l-thioglycollic
45 acid of the general formula:
?—*CHz-CO2H Y
/OE\
‘ O or O
X
s-om-Oom
/C°\
OH/
NH
H2O
X
where either X or Y stands for a substituent of
a kind hereinafter more particularly de?ned, and
‘5|!
35
00
\oo
X
/O on
if
\O 0/
(prepared in the manner described in British 40
Patent 398,162, are added with stirring to 30 parts
of chlorosulphonic acid at 20-25° C. The mix
ture is stirred for 20-24 hours at room tempera
ture. The original red-violet color of the solu
tion changes to dark green and hydrogen chloride 45
is evolved.
The product is isolated by pouring the reac
tion mixture into a mixture of ice and water,
?ltering the brown suspension and washing the
dyestuff with water until acid-free, and drying it. 50
\oo/
l
(X and Y having the same signi?cance as before), itself obtained by interaction of a halogen
acetic acid with the corresponding mercapto
compound, with chlorosulphonic acid or a mix
ture of chlorosulphonic acid and sulphuric acid.
The substituents represented by X and Y in
60" the above formula may be halogen (particularly
The so-obtained dyestuff is a brown-black
powder, soluble in concentrated sulphuric acid
to a dark green solution, and in alkaline hydro
sulphite to an orange-brown solution. Vatted on 55
cotton a valuable pure brown is obtained. The
dyestuff may be treated with aqueous alkali, to
open up the lactam rings, and may then be ap
plied to wool in the manner described in British
patent, No. 377,740.
60
2
2,129,014
Example 2
5 parts of the compound
The product is isolated as in Example 1. The
dyestuff dissolves in concentrated sulphuric acid
to a brown solution.
s OH2'-'C 0 OH
It vats readily to a brown
vat and dyes cotton thence in brown shades.
Example 5
5 parts of the compound
5
s CH2——CO OH
CH
10
(obtained by treating I-amino-S-mercapto-an
thraquinone—Gattermann, Liebig’s Annalen,
1912, vol. 393, page 168—with sodium chloro-ace
tate) are added with stirring to‘ 30 parts of
chlorosulphonic acid at 20-25° C. The mixture is
stirred for 20 hours at this temperature. The
original brown color of the reaction mixture
changes to an intense green.
The dyestuff is isolatedlas in Example 1.
It
dissolves in concentrated sulphuric acid to an
intense green solution. With alkali hydrosulphite
the product vats readily to a clear orange vat.
Cotton is dyed from the vat in reddish-brown
shades.
25
Example 3
5 parts of the compound
s CHz-C OOH
s
\
10
011/
HzC
IlTH
\C O/
l
15
(obtained from the compound described in Ex
ample 1 by boiling with ammonia and zinc dust,
?ltering the pale solution obtained to free from
zinc, and precipitating the product by adding
hydrochloric acid) are added with stirring to 30 20
parts of chlorosulphonic acid at 20-25° C. and
stirred for 20-24 hours at 20-25° C.
The product is isolated as in Example 1. The
shade on cotton is brown.
25
Example 6
5 parts of the compound
s CH1~C 0 011
/CO:O
30
/CO
O0
SOaNa
3.5 (obtained by treating l-mercapto-anthraquinone
5-sulphonic acid-—Gattermann, loc. cit., page
1'78—with sodium chloro-acetate) are added with
stirring to 30 parts of chlorosulphonic acid at
20~25° C.
The mixture is stirred for 20—24 hours
at 20-25” C. The dyestu? is isolated by pouring
on to ice and water, ?ltering oil the dark brown
suspension and washing acid-free with 10% brine
solution, and is then dried at 50-100° C. The
product is a dark brown powder, soluble in cold
water to a grey-brown solution.
It dyes wool
from an acid bath.
' Example 4
5 parts of the compound
00
H1O
/ \II.TH
30
s CH2—O o o H
00
01
obtained by diazotization and subjection to Sand
meyer reaction of 5-amino-anthraquinone-1
thioglycollic acid are dissolved in 30 parts of
chlorosulphonic acid at 20—25° C. and stirred 18
hours at room temperature.
The product is isolated as in Example 1. When
dry it forms a brown-black powder which dis
solved in concentrated sulphuric acid with a
brown color. It vats readily to a clear orange
brown vat and dyes cotton thence in brown shades.
In the above preparation 30 parts of a mixture
of chlorosulphonic acid and monohydrate in equal
parts may be employed to give the same product.
Example 7
The dyestuff paste from Example 2, before dry
ing, is heated with 50 parts of nitrobenzene until
all water is removed. 5 parts of benzoyl chloride
are added to the nitrobenzene mixture at 100° C.
and the Whole warmed to 200° C. for 1 hour.
\CO/
obtained according to British Patent 398,162, are
added to 30 parts of chlorosulphonic acid at 20-25“
C. The mixture is stirred for 20-24 hours at
20~25° C. and the temperature is then raised to
50° C. for 2 hours. The original violet colored
solution changes to brown.
65
The
-
product is ?ltered at 100° C., washed successively
with nitrobenzene and alcohol, and dried.
The benzoylated dyestuff is a chocolate-brown
powder which dissolves in concentrated sulphuric
acid with greenish color. It vats readily to an O
C:
orange-brown solution and dyes cotton thence
in khaki brown shades. Its constitution most
probably corresponds to the formula:
5
HN—CO 70
75
75
3
2,129,014
Example 8
5 parts of the compound
s cHl—o 0 on
o o\
0001:
c0
wherein A
anthracene
are linked
both cases
represents identical radicals of the
series to which the thiophene groups
in the 1.2-1'.2' positions and X in
represents identical substituents in
corresponding alpha positions of the benzene UK
rings of the anthracene nuclei remote from the
3 benzene rings to which the thiophene groups are
‘attached.
2. Thioindigoid compounds of the formula
10
10
/ S\
X—~A
o=c
/S\
A-X
prepared by condensing 5-chloro-anthraquinone
thioglycollic acid with anthranilic acid, are dis
solved in 30 parts of chlorosulphonic acid at room
temperature and stirred 18 hours.
The product is isolated as in Example 1. When
dry, it forms .a brown-black powder soluble in
concentrated sulphuric acid with brown color.
It vats readily to a dark green solution and
dyes cotton thence in purple-brown shades.
Other typical bodies to which the reaction may
be applied are:
SCHr-COOH
CO\
15
wherein A represents identical radicals of the
anthracene series to which the thiophene groups
are linked in the l.2-1’.2’ positions and X in
both cases represents identical substituents se
lected from the group consisting of halogen,
nitro, sulpho, carboxy, hydroxy, alcoxy, amino,
alkylamino, acylamino and the amino group of
a lactam ring, said substituents being present in
an alpha position of the benzene rings of the
anthracene nuclei remote from the benzene rings
to which the thiophene groups are attached.
3. Thioindigoid compounds of the formula
00/
30
30
H
on
SCHPCOOH
co
wherein AQ represents identical radicals of the
10 CI
00/
H
N112
S 0112-0 0 OH
anthraquinone series to which the thiophene
groups are linked in the 1.2- 1’.2’ positions and
X in both cases represents identical substituents
selected from the group consisting of halogen,
nitro, sulpho, carboxy, hydroxy, alkoxy, amino,
40
The process of forming the initial materials
used in Examples 1 and 4, and alluded to brie?y
by reference to British Patent 398,162, consists
alkylamino, acylamino and the amino group of
a lactam ring, said substituents being present
in an alpha position of the benzene rings of the
anthraquinone nuclei remote from the benzene
rings to which the thiophene groups are at
tached.
4. Thioindigoid compounds of the formula
essentially of the following steps.
1-nitro-anthraquinone-5 or 8-sodium-sulfonate
is fused in a large excess of crystalline sodium
sul?de at a temperature of about 140° C. under a
re?ux column. The resultant 1-amino-2.5- or
2.8-dirnercapto-anthraquinone is isolated as so
dium salt and reacted with an excess of sodium
chloro-acetate. The resultant amino-anthra
quinone-dithioglycollic acid is then lactamized by
boiling in dilute hydrochloric acid.
It will be understood that many variations and
modi?cations are possible in our preferred mode
of operation without departing from the spirit
of this invention.
In the claims below it should be understood
that where new products, dyestuifs, or articles of
65
70
manufacture are claimed, we mean to include
50
wherein AQ represents identical radicals of the
anthraquinone series to which the thiophene
groups are linked in the 1.2- 1’.2' positions and
Y in both cases represents identical amino radi
cals which are present in an alpha position of the
benzene nuclei of the anthraquinone group re 60
mote from the benzene ring to which the thio
phene groups are attached.
5. The compound whose constitution corre
sponds to the following formula
65
these bodies not only in substance, but also in
whatever state they exist when applied to ma
terial dyed, printed, or pigmented therewith.
We claim:
1. Thioindigoid compounds of the formula
wherein R in both cases represents identical
75
acidyl radicals.
75
‘2,129,014
6. The compound whose constitution corre
sponds to the following formula
CO
taining in one of the positions 5 and 8 an amino
group.
CO
0
\UJJO
Ol-Q
\
Grin
\oo/
00/
10
O
7. A 1.2-anthraquinone-thioindigoid compound
carrying a lactam ring in the corresponding
alpha-beta positions of the benzene ring of the
. anthraquinone nuclei remote from the benzene
rings to which the thiophene groups are at
tached, the amino group of the lactam ring in
all cases being attached in the alpha position, said
lactam ring being hydrolyzable to the alpha
aminoabeta-thioglycollic acid.
8. An anthraquinone-1.2-thioindigoid dyestuff
substituted in the 5.6 positions by the lactam
corresponding to o-amino-thioglycollic acid.
9. The compound of the formula
13. A process for producing a 1.2-thioindigoid
compound of the anthraquinone series, which
comprises reacting with chlorosulphonic acid
upon a 5-amino-anthraquinone-l-thioglycollic
acid.
14. A process for producing a 1.2-thioindigoid
compound of the anthraquinone series, which
comprises reacting with chlorosulphonic acid
upon a 5-amino-anthraquinone-l-thioglycollic
acid, recovering the reaction product free of acid
and water, and reacting upon the same further
with benzoyl chloride in an inert organic liquid
medium.
25
S
30
HnC
said compound being adapted to dye cotton by
the vatting process, and Wool by the process of
opening the lactam ring and relactamizing on
the ?ber.
10. A process for producing a 1.2-thioindigoid
compound of the anthracene series, which com
prises reacting with a dehydrating agent com
prising essentially chlorosulphonic acid upon a
l-thioglycollic acid of the anthracene series con
taining a substituent in at least one of the 5.8
positions.
11. A process for producing a 1.2-thioindigoid
compound of the anthraquinone series, which
comprises reacting with chlorosulphonic acid
15. A process for producing a 1.2-thioindigoid
compound of the anthraquinone series, which
comprises reacting with chlorosulphonic acid
upon a 1-anthraquinone-thioglycol1ic acid car
rying in one of the pairs of positions 5.6 and 8.7
a lactam ring corresponding to an alpha-amino
beta-thioglycollic acid.
compound of the anthraquinone series, which
comprises reacting with chlorosulphonic acid
upon the compound which corresponds to the
formula
'
upon a 1-anthraquinone-thioglycollic acid car
rying in at least one of the positions 5 and 8 a
substituent of the group consisting of halogen,
nitro, sulpho, carboxy, hydroxy, alcoxy, amino,
alkylamino, acylamino and the amino group of
a lactam ring.
12. The process for producing a 1.2-thioindi
goid compound of the anthraquinone series which
comprises reacting with chlorosulphonic acid
upon a 1-anthraquinone-thiog1yco11ic acid con
,
16. A process for producing a 1.2-thioindigoid
S___
H2O
\
Oic0\(JO/O
/
blIH
CO
FRANK LODGE.
COLIN HENRY LUMSDEN.
60
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