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2,414,155
Patented Jan. 14, 1947
UNITED STATES PATENT OFFICE
‘ 3,414,155
ANTHRAQUINONE DYESTUFFS
. Frank Lodge, Blackley, Manchester, England, as
'
Signor to Imperial Chemical Industries Limited,
a corporation of Great Britain
’
No Drawing. Application Mayp17, 1944, Serial No.
‘536,023. In Great Britain May 18, 1943
2 Claims. (Cl. 260—276)
1
2
This invention relates to the manufacture of
new anthraquinone dyestuffs and in particular it
relates to the manufacture of new anthraquinone
dyestuffs in the molecule of which an anthraqui
none-2:1-(N) -acridone nucleus is united through
an -—NHYNI-I—- bridge, wherein Y stands for
-—COAr— or -ArCO—-, Ar being an arylene radi
cal, to a l-arylaminoanthraquinone carbazole
nucleus.
(N) - benzacridone, 4-o-chlorobenzoylaminoan
thraquinone-2: 1- (N) -benzacridone, 4- (3' :5'-di
chloro - 4' - bromobenzoylamino) anthraquinone
2: 1- (N) -benzacridone, 5-o-chlorobenzoylamino
anthraquinone-Z : 1- (N) -benzacridone, 5-m-bro
mobenzoylaminoanthraquinone-2:1 - (N) - benz
acridone, 4 - (p-bromo-u-naphthoylamino) - an
thraquinone-Z : 1- (N) -benzacridone,
and
‘ bromobenzoylaminoanthraquinone - 2:1 -
51-p
(N)
-
“ According to the invention we manufacture 10 benzacridone. These substances may be made by
acylation of the appropriate aminoanthraqui
none-2:1-(N) -acridone with the appropriate halo
new anthraquinone dyestuffs of the formula:
XNHYNHZ
wherein X is an anthraquinone-2z1-(N) -acridone
nucleus attached to the adjacent --NH-group in
the 3-, 4-, 5-, 6-, 7- or S-positions, Y is either
—COAr- or -—ArCO—, Ar being an arylene radi
cal, and Z is a l-arylaminoanthraquinone carba
zole nucleus attached to the adjacent ——NH—
group in the 4-, 5-, or 8-positions, by a process
genoaroyl halide.
“
As examples of carboxyarylaminoanthraqui
none-2:1-(N) -acridones which may also be used
as starting materials there may be mentioned
4 - p - carboxyanilinoanthraquinone - 2:1 - (N) -
benzacridone and 5-m-carboxyanilinoanthraqui
none-2 : 1- (N) -benzacridone.
These substances
may be made by condensation of the appropri
‘ which comprises either interacting a 3-, 4-, 5-,
ate halogenoanthraquinone-Z:1 - (N) - benzacri
6-, 'l- or 8-halogeno-aroylaminoanthraquinone
2:1-(N)-acridone with a 4-, 5-, or 8-amino—1
arylaminoanthraquinone carbazole, or interacting
a 3-, 4-, 5-, 6-, 7- or 8-aminoanthraquinone-2:1
(N) -acridone with a 4-, 5-, or 8_-carboxyaryl
done with the appropriate carboxyarylamine.
or
for example alkyl and alkoxyl groups.
The anthraquinone-Z : 1- (N) -acridone nucleus
may carry, besides the -—NHYNHZ ‘group, also
other groups, provided they are such as not to
take part in the reaction or reactions whereby
amino-l-arylaminoanthraquinone carbazole, or
the —NI—IYNHZ group is generated and which are
its amide-forming derivatives or with a 4-, 5-, or
not detrimental to the value of‘ the product as a
8-halogenoaroylamino - >1 - arylaminoanthraqui
vat dyestu? i. e. are not for example, changed
none carbazole, or interacting a 3-, 4-, 5-, 6-, '7 30, in the vatting process. Suitable substituents are
8-carboXyarylaminoanthraquinone-2: 1- (N) -
acridone, or its amide-forming derivatives with a
4-, 5- or B-amino-l-arylaminoanthraquinone car
By a, l-arylaminoanthraquinone ,carbazole we
mean the carbazole resulting from the cyclisation
bazole.
‘
.
of a 1-arylaminoanthraquinone. Amino-l-aryL
The ' anthraquinone-2:1-(N) -acridone nucleus 35 aminoanthraquinone carbazoles may be made as
may be for example an anthraquinone-2:1-_(N)
described for example, in Swiss Patent Speci?ca
benzacridone nucleus or an anthraquinone-2:1
tion No. 221,928. ‘Suitable amino-l-arylamino
(N) —cz- or -/3-naphthacridone nucleus. Suitable
aminoanthraquinone-Z : 1- (N) -acridones
which
may be used as ‘starting materials include 3
aminoanthraquinone-2 : 1- (N) -benzacridone, 4
amino-anthraquinone-Z : 1- (N) -benzacridone, 4
anthraquinone carbazoles for use as starting ma
terials in the process of the invention include 4
amino-1-p-tolylaminoanthraquinone carbazole, 5
amino-1—c-naphthylaminoanthraquinone carba
zole and 4-amino-1—p-naphthylaminoanthraqui
aminoanthraquinone -‘ 2:1 - (N) -p-methy1benz
acridone, 5 - aminoanthraquinone - 2:1 - (N)
benzacridone and 8 - aminoanthraquinone - 2:1
(N) - benzacridone.
none carbazole.
ing materials may be made by acylation of the
Or again, as said, there
corresponding amino-l-arylaminoanthraquinone
may be used as starting materials halogenoaroyl
aminoanthraquinone-2: l-(N) -acridones.
carbazole by means of the appropriate halogeno
aroyl halide. Suitable halogenoaroylamino-l
Suit
able halogenoaroylaminoanthraquinone-2: 1- (N) -
arylaminoanthraquinone carbazoles include 4-p
acridones which may be used include 3-p-bromo
bromobenZoylamino-l - ,8 '- naphthylamino - an
benzoylaminoanthraquinone-2 :11- (N), -- benzacri
thraquinone carbazole, 4-m-bromobenzoylamino
1-,B-naphthylaminoanthraquinone carbazole, 4
done, 4-p-bromobenzoylaminoanthraquinone-2 : 1
(N) -benzacridone, 4-p- (p'-brimophenyl) ~benz
o-chlorobenzoylamino-l - 1S - naphthylaminoan
oylaminoanthraquinone-Z : 1- (N) - benzacridone,
4 - m - bromobenzoylaminoanthraquinone - 2:1
Halogenoaroylamino - 1 - aryl
45 aminoanthraquinone carbazoles for use as start
55
thraquinone carbazole, 4-p-(p'-bromophenyl)
2,414,155
3
4
benzoylamino - 1 - p - naphthylaminoanthraqui
washed on the ?lter with ethanol. It is then
boiled with dilute hydrochloric acid, refiltered,
none carbazole, and 5-m-bromobenzoylamino-1
c-naphthylaminoanthraquinone carbazole.
Carbo-xyarylamino - l-arylaminoanthraquinohe
carbazoles for use in the process of the invention
may be made by condensation of the appropriate
halogeno-l-arylaminoamthraquinone carbazole
with the appropriate carboxyarylamine. Suit
able carboxyarylamino - l - arylaminoanthraqui
none carbazoles which may be used include 4-p
carboxyanilino-l - p - naphthylamino-anthraqui
washed with water and dried. Dark brown crys
tals are obtained which give a greenish solution
in concentrated sulphuric acid. Cotton is dyed
from its dull red vat in greyish brown shades of
very good fastness properties, especially to soda
boiling and to light.
A similar greyish brown vat dyestu? is ob
tained from e-m-bromobenzoylamino-l-p-naph
thylaminoanthraquinone carbazole while 5-p
none carbazole, 4-m-carboxyanilino-l-p-tolyl
bromobenzoylamino- 1 -p-naphthylaminoanthra
aminoanthraquinone carbazole arid- 5-p-carboxy
quinone carbazole yields a khaki dyestuff.
anilino-143-naphthylaminoanthraquinone
car
Example 2
bazole.
15
52' parts of 4-p-bromobenzoylaminoanthraqui
Like the anthraquinone-Zzl-(N)-acridone nu
none-2:1-(N) -benzacridone, 33 parts of ll-amino
cleus the l-arylaminoanthraquinone carbazole
nucleus (which may also be named a 1:2-phthal
oylcarbazole nucleus) may carry sub-stituents in
addition to those taking part in the reactions
whereby the XNHYNH-group is
generated.
These substitue'rits may be in any position pro
vided one of the 4, 5 or 8 (i. e. the at) positions
of the anthraquincne nucleus is left free for the
bridging group and they may vbe of any nature
such as not to interfere in the bridging reaction
or in the subsequent use of the product as a
vat dyestu?. Again suitable substituents are the
neutral groups, for example alkyl and alkoxyl
groups.
The group Y, as said, may be —COAr-— or
—ArCO'— and Ar stands for an arylene radi
cal. Suitable arylene radicals are for example
122-, 1:3- and lie-phenylene, 4:4'-diphenylene
and lza-naphthylene.
As suitable amide-forming derivatives of the
1 - p - tolylaminoanthraquinone
carbazole
(ob
tained by hydrolysing the corresponding benzoyl
amino compound with caustic potash in boiling
,B-ethoxyethanol), 12 parts of anhydrous sodium
carbonate, 2 parts of cuprous chloride and 800
parts of nitrobenzene are-stirred and boiled dur
ing 12 hours. The mixture is then diluted with
nitrobenzene, ?ltered cold, washed with nitro
benzene, then with ethanol, and the dyestu? is
?nally boiled with dilute hydrochloric acid to
remove copper, ?ltered, washed and dried.
It
is purified by extraction of impurities in boiling“
pyridine when a black powder remains which
yields a dull brownish red vat and dyes cotton
in greenish grey shades of very good fastness.
Example 3
24 parts of 5-o—chlorobenzoylaminoanthra
quinone-2zl-(N)-benzacridone, 18 parts of 5
4-, 5-, or 8-carboxyarylamino-l-arylamino-an
amino - 1~[i-naphthylaminoanthraquinone car
thraquinone carbazole or of the 3-, 41-, 55-, 6-, '7
bazole, 6 parts of anhydrous sodium carbonate,
1 partof cuprous chloride and 600 parts of ni
or
8-carboxyarylaminoanthraquinone-2: 1 -'(N) -
acridone there may be mentioned the acid chlo
rides or bromides.‘
The process of the invention may be carried
into effect by heating the chosen pair of reactants
together, preferably in the presence of a solvent
of high boiling point, for example nitrobenzene
or naphthalene.
In cases where one of the re
actants is an acid. chloride such heating together
is sufficient to bring about the formation of the
desired dyestuff in good yield. In other cases
however it is advisable to carry out the inter
action in the presence also of an'acid binding
agent, for example sodium carbonate; and also
of a catalyst, preferably a copper salt, for exam
ple cuprous chloride.
The products of the invention are vat dyestu?s
which dye textile materials in shades varying
from reddish-brown to a bluish- or greenish
gray of very good iastness to light, to chlorine
and to‘ soda-boiling.
'
trobenzene are stirred and boiled for 12 hours.
The mixture is then cooled, diluted with ethanol ‘
and ?ltered. The product is washed with ehanol,
boiled with dilute hydrochloric acid, re?ltered,
washed with Water and dried. It“ is puri?ed by
extraction of impurities with boiling pyridine
when the dyestuff remains as dark brown crystals
yielding an olive solution in concentrated sul
phuric acid. It yields a violet coloured vat and
dyes cotton in fast reddish brown shades.
Example 4
'78 parts of 5-m-bromobenzoylaminoanthra
quinone-2z1-(N)-benzacridone, 54 parts of 4
amino - l-c-naphthylaminoanthraquinone car
bazole, 18 parts of anhydrous sodium carbonate,
3 parts of cuprous chloride and 1750 parts of
nitrobenzene are stirred and boiled for 12 hours.
The product is isolated as in Examples 2 and 3‘
and is purified !by extraction of impurities with
The invention is illustrated but not limited 60 hot pyridine. Dark violet brown crystals are ob
tained which yield a green colour in concentrated
by the following examples in which parts are
sulphuric
acid and dye cotton in dull .violet brown
by weight:
Example 1
22.5 parts of 4-aminoanthraquinone-2:l-(N)
ben-‘zacridone, 36.4 parts of e-p-bromobenzoyh
amino-1-c-naphthylaminoanthraquinone carba
zole (obtained by condensing Ll-chloro-l-p-bro
mobcnzoylaminoanthraquinone with p-naphthyl
shades of good fastness properties.
In a similar manner 5-o-chlorobenzoylamino
and 5-p-bromo-benzoylamino - anthraquinone
amine and cyclising the product in 90% sulphuric
acid), 8 parts of anhydrous sodium carbonate, 2
2:1-(N)-benzacridones yield reddish brown and
grey brown vat dyestuffs respectively.
Example 5
52 parts of 4-p-bromobenzoylaminoanthra
quinone-2:1-(N)—benzacridone, 36 parts of 4
parts‘ of cuprous chloride and ‘750 parts of nitro
amino - 1-,8-naphthylaminoanthraquinone car
benzene are stirred and boiled under a reflux
bazole (obtained by hydrolysing the correspond
ing benzoylamino derivative with caustic potash
condenser for 12 hours. The product is cooled,
diluted with 500 parts of ethanol, ?ltered and 75 in hot ,e-ethoxyethanol), 12 parts of anhydrous
2,414,155
6
5
sodium‘ carbonate, 2 parts of cuprous chloride
and 1200 parts of nitrobenzene are stirred and
boiled gently during 12 hours. After cooling and
diluting with ethanol the ‘product is ?ltered,
.
H
of cuprous chloride ‘and 1000 parts of nitroben
zene are stirred and boiled for 18 hours.
The
product is cooled, ?ltered, washed with ethanol
There is thus obtained as
and‘ dried. It is then boiled ‘with. dilute hydro
residue, at blue-black, ?nely crystalline powder
chloricacid, re?ltered, washed with water and
dried.‘ The dyestu? is puri?ed by extraction with
soluble in concentrated sulphuric acid to give a
greenish coloured solution. Cotton is dyed from
its dull reddish violet vat in very fast greenish
boiling pyridine and erystallising the residue
from nitrobenzene when a red brown crystalline
powder is obtained. It yields a green colour in
concentrated sulphuric acid and dyes cotton fro
'
G‘rey vat dyestu?‘s may also be obtained by
substituting the 4-p-bromobenzoylaminoanthra
a brownish red vat in corinth shades. .
quinone-2:1-(N)-benzacridone in the above ex
2
amples by 4-m-bromobenzoylamino or by 4-0
chlorobenzoylaminoanthraquinone - 2:1 - (N)
benzacridone.
.
no-14,9tnaphthylaminoanthriquinone carbazole,
12 parts of anhydrous ‘sodium carbonate, Zparts
boiling with pyridine, and ?ltering at 50° C. to
'
'~
. 34 parts of 3-aminoanthraquinone-2:1-(N)
washed and dried. The dyestu? is puri?ed by
grey shades.
V
benzacridone, 55 parts of 4-p-bromobenzoylami
washed with ethanol, extracted with hot dilute
hydrochloric acid to remove copper, re?ltered,
remove impurities.
Emampleijil‘i
Example 10
.
i
.
"
-
' 12 parts of the acid chlorideof 4-p-carboxy
20
,
anilinoanthraquinone - 2:1 - (N) - benzacridone
(prepared by condensation of the corresponding
4-aminoacridone with p-bromomethylbenzoate
followed by hydrolysis of the product with caustic
potash in boiling s-ethoxyethanol solution and
treating the so-‘obtained 4-p-carboxyani'linoan
Example ‘6
60 parts of 4-p-(p'-bromophenyl)-benzoyl
aminoanthraquinone-2:l-(N) - benzacridone, 36
parts of 4-amino-1 - B - naphthylaminoanthra
quinone carbazole, 12 parts of anhydrous sodium
carbonate, 3 parts of cuprous chloride and 1000
thraquinone-2z1-(N)-benzacridone with a solu
tion of thionyl chloride in nitrobenzene) are
parts of nitrobenzene are stirred and boiled for
boiled in 200 parts of nitrobenzene with 9 parts
15 hours.‘ The mixture is then cooled and ?l
of 4-amino-1- ,3 r-naphthyla’minoanthraquinone
tered. The product is washed with nitrobenzene, 30 carbazole. After cooling, the product is ?ltered
then with ethanol, boiled with dilute hydrochloric
off, washed on the ?lter with hot nitrobenzene
acid, ?ltered, washed with water and dried. _ It is
then ethanol and dried, The product is identical
puri?ed by extraction with boiling pyridine when
with the dyestuff described in Example 1.
the dyestuff remains as a dark ‘greenish grey
‘powder, yielding a dull greyish green solution in 35
concentrated sulphuric acid‘. From a red vat it
dyes cotton in greenish grey shades.
‘
lino-1-s-naphthylaminoanthraquinone carbazole
(prepared by treating the reaction product from
'
Similarly a-grey-green vat dye is obtained by
using 58 parts of 4-(p-bromo - a - naphthoyl
amino) - anthraquinone-Zzl-(N) - benzacridone 40
(obtained by acylating é-aminoanthraquinone
’ Example 11
20 parts of the acid chloride of 4-p-carboxyani
4-amino-1-p-naphthylaminoanthraquinone car
bazole and p-bromobenzoic acid with thionyl
chloride in nitrobenzene solution) and 13 parts
of 4-aminoanthraquinone-2 : 1- (N) -benzacridone
2: 1- (N) -benzacridone with‘ 4-bromo-1-naphthoyl
are boiled in 400 parts of nitrobenzene. After
chloride).
cooling, the product is ?ltered off, Washed with
Example 7
45 ethanol and dried. Recrystallisation from nitro
benzene gives a dyestuff identical with the prod
34 parts of 4-aminoanthraquinone-2:l-(N)
uct described in Example 5.
benzacridone, 62 parts of 4-p-(p'-bromophenyl) benzoylamino - 1 - ,8 - naphthylamihoanthraqui
Example 12
none carbazole, 12 parts of anhydrous sodium
53 parts of 3-p-bromobenzoylaminoanthra
carbonate, 3 parts of cuprous chloride and 1000 50
quinone-2:l-(N) -benzacridone, 36 parts of 4~
parts of nitrobenzene are stirred and boiled dur
ing 15 hours. The product is isolated and
puri?ed as is that described in Example 6 and a
dark brown crystalline powder is obtained which
yields a green solution in concentrated sulphuric
acid, a red vat and dyes cotton dark brown
shades.
Example 8
amino - 1 - 5 -naphthylaminoanthraquinone car
bazole, 12 parts of anhydrous sodium carbonate,
2 parts of cuprous chloride and 1000 parts of ni
trobenzene are stirred together and boiledfor 12
hours. The mixture is then cooled and ?ltered.
The product on the ?lter is washed with ethanol,
boiled with dilute hydrochloric‘ acid, re?ltered,
washed with water and dried. It is puri?ed by
35.5 parts of 4-aminoanthraquinone-2:l-(N) 60 extraction with boiling pyridine when the dye
stu? remains as a dark brown crystalline powder
p-methylbenzacridone, 54.5 parts of 4-p-bromo»
benzoylamino-l-p- naphthylaminoanthraquinone
carbazole, 15 parts of anhydrous sodium car
bonate, 1.5 parts of cuprous chloride and 1000
parts of naphthalene are stirred at 210-15° for
18 hours. After cooling, the product is diluted
with solvent naphtha and ?ltered at 90° C. washed
with ethanol, extracted with hot dilute hydro
chloric acid, refiltered, washed and dried. The
product is puri?ed by boiling with pyridine.
There is thus obtained a black crystalline pow
which yields a greyish green solution in concen
trated sulphuric acid. From a dull brown violet
vat it dyes cotton in corinth shades.
Example 13
I 26 parts of 4-p-bromobenzoylaminoanthraqui
none-2:1-(N) -benzacridone, 18 parts of 5-amino
> ,1 - s - naphthylaminoanthraquinoneV carbazole, 6
parts of anhydrous sodium carbonate, 1 part of
cuprous chloride and 500 parts of nitrobenzene
der soluble to give a green solution in concen
are stirred and boiled for 12 hours.
trated sulphuric acid. It yields a red vat and
dyes cotton in dark brown shades very similar to
is then cooled, diluted with ethanol and ?ltered.
The product is washed with ethanol, boiled with
the product described in Example 1.
The mixture
75 dilute hydrochloric acid, re?ltered, washed with
2,414,155
7
8
water and dried. It yields a reddish vat and dyes
wherein R vin each case stands for a nucleus of
the benzene and naphthalene series and Ar is an
cotton in dull corinth shades.
_
'
Similarly a dull corinth dyestuff. is obtained by
arylene radical of the group consisting ‘of l:2-,
using 26 parts of 4-m-bromobenzoylaminoan
17:3- ‘and 1:4-phenylene, 4:4'-diphenylene and
thraquinone-Zzl-(N)-benzacridcne in the above 5 1 :4-naphthylene, and in which the remaining X’s
example in place of the 4-p‘-bromobenzoylamino
and Yr’s in the respective nuclei stand for hydro
anthraquinone-Z : 1- (N) -benzacridone.
‘
gen, which dye textile ?bers in shades varying
from reddish-brown to blue- and greenish-gray
Example 14
of very good fastness to light, to chlorine and to
' 59 parts of 4-(3':5'-dichloro-4'-bromobenzoyl- 10
amino) anthraquinone-2: l- (N) -benzacri_done, 36
parts of ll-amino-1-p-naphthylaminoanthraqul
soda ash boiling.
‘
' I,
I
2. The anthraquinone vat dye of the following
formula
'
none carbazole, 12 parts of anhydrous sodium
carbonate, 2 parts of cuprous chloride and 1200
parts of nitrobenzene are stirred and boiled for 15
12 hours. The nitrobenzene is removed by dis
tilling in steam and the product is boiled with
dilute hydrochloric acid,~=>?ltered, washed and
dried. The product dyes cotton in bluish grey
shades from a reddish vat.
I claim:
I
20
'1. The anthraquinone vat dyes which contain,
the nucleus
I R
*
IITH
C
25
I
I!
EN
X 0 (1/
A
/O
80
‘ @NHYO,
-—X
X
0
X
linked in one of the positions X through a radi- 35 which dyes cotton from a dull reddish-violet alka
cal ‘of the group consisting of -NH-CO-Ar-NH
line hydrosul?te vat in very fast greenish-gray
and —-NH—Ar—-CO—~NI-I—— to one of the posi
tions Y in the nucleus
shades.
'
FRANK LODGE.
40
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