Патент USA US2040857

2,040,857
Patented May 19, 1936
, UNITED STATES PATENT OFFICE
2,040,857
ACYLAMINO DERIVATIVES OF THE
ANTHRAPYRIMIDINE SERIES
Max Albert Kunz, Mannheim, and Karl Koeberle,
Ludwigshafen-on-the-Rhine,
Germany,
as
signors to General Aniline Works, Inc., New
York, N. Y., a corporation of Delaware
No Drawing. Application January 14, 1932,
Serial No. 586,692. In Germany January 21,
1931
35 Claims. (Cl. 260-32)
The present invention relates to new compounds ganic radicle, according to the following formu
which are acylamino derivatives of the anthra
lee:
pyrimidine series, and process of producing same.
We have found that anthrapyrimidines to which
an organic radicle is attached by means of an
D
acylamino, in particular a carboxylamino group,
are valuable coloring matters, in particular vat
dyestu?s, and intermediate products for the
preparation thereof and may also be used as
10
pigments. The said anthrapyrimidine derivatives
can be produced by condensation of an acylami
noanthraquinone containing a further nitrogen
atom in an alpha position and convertible into
anthrapyrimidines with compounds capable of
4-amino-L9 anthrapyrimidine
‘
15 forming the pyrimidine ring, for example acid
amides, or ammonia in case acylaminoanthra
quinone-1(N).2-oxazoles are employed as initial
4-acylamino-L9
anthrapyrimidine.
4-acylamino-1.Q-anthrapyrimidine is obtained.
Finally by condensing for example 5-halogen-1.9
materials, whereby the pyrimidine ring is formed,
anthrapyrimidine with benzamide, 5-benzoylami
or by acylation of aminoanthrapyrimidines, or
no-l.9-anthrapyrimidine is obtained according to
20 by condensation of negatively substituted an
the following formulae:—
thrapyrimidines with acid amides. They may
further be prepared by condensing l-nitroanthra
quinone carboxylic or sulphonic acids or halides
thereof with amines, reducing the nitro group and
25 condensing the reduction products with acid
amides to form the pyrimidine ring. Several of
the aforesaid methods may also be combined.
For example by heating 1-amino-5-benzoyl
aminoanthraquinone with formamide, 5-benzoyl
amino-1.9-anthrapyrimidine is obtained accord
ing to the following formula:-- -
H
V
- H
l
I
/G\
N N
/C\
N \N
\
II
—-_>
H
25
l
30
—HY
I
NH O
HQN~COCQH3
O
CsHl
(Y being a halogen)
35
15
35
As results from the aforedescribed methods of
producing the new derivatives of anthrapyrimi
dine, most various kinds of initial materials may
be used, for example amino-anthrapyrimidines,
halogenanthrapyrimidines, u-aminoanthraquin
40
ones substituted by a further amino group or
halogen and a—nitroanthraquinone carboxylic
and sulphonic acids and substitution products
thereof. When starting from aminoanthrapy
rimidines or u-aminoanthraquinones containing
a further amino group and subsequently form
45
1 ing the pyrimidine ring, the new compounds are
l-amino-E-benzoylamino-
anthraquinone.
5-benzoylamino-L9
anthrapynmidme.
_
_
_
50
By acylating 4-amino-1.9eanthrapyrimidine by
means of a carboxylic acid halide of the formula
55 X-—CO+R, wherein X is halogen and R. an or
formed by condensation with organic acids
whereby in case such acids of higher molecular
weight are used, these are preferably employed 50
in the form of their anhydrides or still better in
the form of their halides, in particular chlorides.
Halogenanthrapyrimidines or the corresponding
a-aminohalogenanthraquinones, when used as
starting materials, are to be condensed with the,
_
‘
As substitu
.,
amides of the organic acids. In the following2‘,o4o,s57
we densation of anthrapyrimidines.
will give a series of organic acids which either in ents in the Py-C position, alkyl, aryl, aralkyl,
' the free state or in the form of their amides, an
amino, substituted amino, alkoxy and aryloxy
hydrides or halides have proved suitable for the groups and in particular halogen are valuable. '
purpose of ourinvention: aliphatic mono- and The aforesaid anthrapyrimidines substituted on
'poly-carboxylic acids, such as formid'acetic, chlor
the Py-C atom by organic radicles maybe pro
acetic, butyric, propionic, valeric, palmitic, stearic, duced by employing another acid amide than
. oxalic, molanic, succinic, adipic, suberic, pyroa
formamide, for example acetic amide, for the
cemic, lactic, citric, maleic,ioleic acids cycloali-' condensation with an alpha-aminoanthraquin
10 phatic acids, such as hexa-hydrobenzoic acid and
one. It is, however, more suitable to produce
naphthrenic acids; aromatic carboxylic and sul
these substituted anthrapyrimidines from the
phonic acids for example benzene .mono and poly
corresponding anthraquinone-l (N) .2-oxazoles by
carboxylic- and sulphonic acids, such as benzoic, heating them with ammonia under pressure. 'A
phthalic, isophthalic and , terephthalic ‘acids, the further convenient method for producing these
15 various mono- and poly-carboxylic and sulphonic
substituted anthrapyrimidines consists in start 15
" acids derived from naphthalene, anthracene, an
ing from anthrapyrimidones which may already
thraquinone, ?uorene, ?uorenone, phenanthrene, contain an acylamino, amino, nitro, alkyl, alkoxy,
benzanthrone, anthanthrone, the various dian
aryloxy group or a halogen atom in the anthra
thrones, ms-benzdianthrone, ms-naphthodian quinone nucleus,‘ with agents capable of replac
20 throne, ms-anthradianthrone, the said‘acids of
ing oxygen or hydroxy groups by halogen, such 20
the, heterocyclic series, such as those derived as the halides of phosphorus or sulphur, for ex
from pyridine, quinoline, acridine, acridone, .ane ample phosphorus pentachloride, tribromide, tri
thraquinone-benzacridone, anthraquinonethio chloride, thionyl chloride and the like, or Demo
.xanthrone, pyrazolanthrone, anthrapyrimidone,
trichloride, antimony pentachloride and‘arsenic .
anthrapyridone, and pyrolanthrone. Substitu
pentachloride, In the Py-C-halogenanthrapy 25
tion products of the aforesaid acids may be used rimidines thus obtained the halogen atom can
as well, for example their alkyl, aryl and acyl . readily be replaced by organic radicals either
.370
derivatives, suchas toluic acids, xylene carboxylic‘
acids, mesitylenic acid, cinnamic acid, hydrocin
namic acid, benzoyl-formic acid, b'enzoyl-acetic
acid, acetyl-benzoic acid, diphenylcarboxylic
acid, .diphenylmethane carboxylic acid, benzo
phenone carboxylic acid, anthraquinonoyl-ben
zoic acid. Moreover, the halogen derivative of
F the aforesaid acids, viz. their fluorine, chlorine,
bromine and iodine derivatives, the aforesaid
. acids when substituted by‘nitro, hydroxy, alkoxy,
aryloxy' or amino groups or amino groups in
which the hydrogen atoms are replaced by or
ganic radicles, such asalkyl, aryl or acyl groups,
may be used. Further,‘ there, may be used acids
of the aforedescribed kind when substituted by
cyano, thiocyano, mercapto or substituted mer
‘capto groups, viz. . the thiocyanates. and thio
directly byv condensation with amino or hydroxy
compounds, or by way of the corresponding diazo
compounds which may be. obtained from the 30
amines prepared from the halogen compounds by
heating them with ;ammonia.
By 'way of the -
diazo compounds other substituents, such“. as
mercapto, cyano and like substituents, can read
ily be introduced into the Py-C position of the ‘
anthrapyrimidines.
The preparation of the acylaminoanthrapyrim—v
idines by condensation of aminoanthrapyrimi
dines with organic acids, anhydrides or,’ halides,
or halogenanthrapyrimidines with acid " amides, 40
and the corresponding,v condensation of the am
inoanthraquinones
or halogenanthraquinones
with organic acids, anhydrides or halides, or acid
amides, before the formation of the pyrimidine
45
ethers, or acids containing a further carboxylic ring, is best» carried out :in 'an, inert organic‘ sol 45
group-which is esteri?ed or in which the hydroxy vent or diluent, in particular aromatic solvent
group is replaced by the amino group. When. or diluent of high boiling point, for example ni
it is intended to produce compounds of the kind trobenzene, halogenbenzenes, nitro-and halogen
59
the anthrapyrimidine nucleus which as stated
above are preferably prepared by condensing an
described‘ in'which the acyl groupis attached to
u-nitroanthra‘quinone carboxylic or sulphonic
acid chloride with amines, reducing the nitro
group and condensing the amino body formed
5,5 with an acid-amide to form the pyrimidine ring,
asami'nes all compounds corresponding to the
aforesaid'acids but containing an amino group
instead'of the. acid group, may be used. By ap
propriate selection of the reaction conditions,
60 several different acylamino groups may also be
introduced into the anthrapyrimidine molecule.
'.The anthrapyrimidines or the corresponding
anthraquinones which are used in‘ the prepara
' ' tion of the new compounds, may contain any of
.65
the substituents. which as stated above may be
presentin the. acid'component, also connected
to the Py-C atom, in particular halogen, alkyl,
aryl, 'aralkyl, amino, substituted amino, hy-v
derivatives of homologues of benzene, naphtha
lene and its halogen-1 derivatives and the like. 50'
The condensation is best carried out at, temper;
atures above 100° C. and may be accelerated by
the addition of condensing catalysts, such as metal
and metal compounds, for example copper and
iron, their oxides and salts thereof, such as their 65
acetates and carbonates. Acid binding agents are
also preferably added, for example pyridine, quin
oline, tertiary organic bases, such as dimethyl- '
aniline, sodium and potassium carbonates, ace
tates and phosphates. The formation ,of the 60
pyrimidine ring when starting from anthraquin
ones can be carried out in the absence as well as
in the presence of indifferent diluents, for exam
ple phenol, nitrobenzene, trichlorbenzene or .in
the case of anthraquinone-l(N)’.2-oxazoles water
or alcohol may be used as diluents.
Agents which
accelerate reaction, for example anhydrous boric
oxide, oxalic acid, potash, zinc chloridercopper 5
dr‘oxy, alkoxy, nitro and ‘cyano groups. 'In ad:
70 dition to the said substituents the 2-position in ' and its salts, may be added. Therea'ction prod
nets are usually obtained in good yields and in 70
the anthrapyrimidine may be substituted by a , a crystalline form. If necessary. they may be‘
2'-anthrapyrimidine'radical. That is to say the
puri?ed by the usual methods, as for example ‘
’ ‘invention includes the production of acylamino by' crystallization or treatment with" oxidiz
compounds of 2-2'-dianthrapyrimid'yls which
latteri'products‘are obtainable by alkaline con
ing agents, for example in the form of‘ their
aqueous pastes with hypochlorite solution. They 75
2,040,857
dissolve inconcentrated sulphuric acid,. usually
to give a yellow to orange coloration. They are
comparatively di?icultly soluble in the usual or
A reaction product of similar color is likewise
obtained from 4-chlor-1.9-anthrapyrimidine by
heating with benzamide.
ganic solvents and, contrasted with the anthra
pyridones and anthrapyrimidones, are insoluble
in alkalies. With alkaline hydrosulphite solu
tions they usually yield violet brown vat solu
tions from which vegetable, animal and arti?cial
?bres are usually dyed greenish yellow to violet
10 shades.
The shades produced with the acylaminoan
Example 2 I
5 parts of 4-amino-1.9-anthrapyrimidine are
suspended in 100 parts of nitrobenzene. After
adding 6 parts of'l-aminoanthraquinone-2-car
thrapyrimidines prepared in the aforesaid man‘
ner may be varied by halogenation.
The halogenation may be carried out by a
15 variety of methods, as for example in inorganic
or organic media, such as sulphuric acid and its
boxylic acid chloride, the whole is heated to 120°
C. for several hours while stirring, then for a 10
short time at 150° C. and then for from 1 to 2
hours at the boiling point. The whole is allowed
to cool and the reaction product which separates
in the form of yellow red needles is ?ltered off
by suction. The yield is almost theoretical. 15
derivatives, for example chlorsulphonic, and al
kylsulphonic acids, water, nitrobenzene, chlor
The product dissolves in concentrated sulphuric
acid giving an orange coloration, yields a dark
brown vat and dyes cotton red shades having very
benzene and the like, or in the absence of dilu
20 ents, or in the presence of halogen transferrers,
as for example iodine, sulphur, iodine chloride,
good fastness.
The corresponding acylamine from 4-amino
selenium, dimethylaniline, antimony, iron, iron
chloride and aluminium chloride. The reaction
products are usually obtained in good yields and
1.9-anthrapyrimidine and anthraquinone-2-car
boxylic acid dyes green yellow shades as does that
with pyrazolanthrone-Z-carboxylic acid and also
the meta-methoxy—4-benzoylamino derivative.
25
in a good state of purity; when necessary they
may be puri?ed by the usual methods, as for ex
ample by crystallization, by boiling with organic
solvents or by treatment with alkali metal hypo
chlorites or other oxidizing agents. The halo
genacylaminoanthrapyrimidines differ from the
30
initial materials free from or poor in halogen
usually as regards shade of color and are in part
superior thereto as regards fastness to washing
and chlorine. Thus for example, from S-benzoyl
amino-1.9-anthrapyrimidine (which gives yellow
35
40
one, 2 parts of formamide and 4 parts of phenol
are boiled for several hours while stirring. When 30
the solution has become orange yellow in color, it
is allowed to cool, diluted with from 6 to 7 parts
of ethyl alcohol, allowed to cool and the reaction
product which separates in a crystalline form is
?ltered off by suction. It crystallizes from nitro 35'
benzene, preferably with an addition of a little
dyeings) a clear orange is obtained by chlorina
tion and from the acylamine derived from 4-am
benzoyl chloride, in the form of yellowish needles
ino-1.9-anthrapyrimidine and diphenyl-4-car
boxylic acid (which gives greenish yellow dyeings)
dissolves in concentrated sulphuric acid giving an
orange coloration and yields clear yellow dyeings 40
a halogenation product which gives clear green
of good fastness from a brown vat.
ish yellow dyeings is obtained by treatment with
bromine or sulphuryl chloride, the said product
being completely fast to chlorine in contrast to
the initial material and superior to the latter as
regards fastness to washing, kier boiling and
light.
The following examples will further illustrate
50
Example 3
1 part of 1-amino-5-benzoylaminoanthraquin
of
5 - benzoylamino - 1.9 - anthrapyrimidine.
It
Example 4
24,’? parts of 5-methylamino-1.9-anthrapyrim
idine (obtainable by heating 5—chlor-1.9-anthra
pyrimidine which may be prepared from l-chlor
5-aminoanthraquinone with formamide, with
methylamine under pressure) are heated at be
the nature of this invention but the invention is
not restricted to these examples. The parts are
tween 1400 to 150° C. with 120 parts of parachlor
benzoylchloride until the reaction mass has be
by weight.
Example 1 _
come orange. The Whole is then allowed to cool
.an worked up as usual. The reaction product
obtained is a dark brown powder, dissolves in cen
36 parts of 1-amino-4-benzoylaminoanthra
centrated sulphuric acid, gives a yellow solution
quinone are heated to from 180° to 185° C. with
with an olive tinge and dyes current shades from
55 125 parts of formamide for 8 hours while stirring.
After cooling the reaction product is ?ltered by
suction, washed with alcohol and dried. The
reaction product obtained in the form of yellow
needles in good yields dissolves in concentrated
60 sulphuric acid giving an orange coloration. It
crystallizes from nitrobenzene, if necessary with
'
In the same manner 5-ethyl and 5—propylam-,
ino-1.9—anthrapyrimidine which are obtainable
from 5-chlor-1.9-anthrapyrimidine by means of
ethyl or propylamine, may be subjected to acyla~
ion.
Similar reaction products are obtained in an
the addition of a little benzoyl chloride, in the
form of. green yellow needles. The 4-benzoyl
analogous manner by starting fromv alkylation
products of aminoanthrapyrimidines obtained in
amino-LQ-anthrapyrimidine with alkaline hy
sulphuric acid by means of alcohols.
65 drosulphite yields a’ violet brown vat solution
from which cotton is dyed powerful clear green
yellow shades of very good fastness. A brown
ammoniacal vat yields powerful brilliant green
70
a brown vat.
yellow shades on wool.
The reaction may also be carried, out in the
presence of diluents, as for example phenol. The
product is identical with the reaction product
obtainable from 4-amino-l.9-anthrapyrimidine
(obtainable by boiling IA-diaminoanthraquinone
with. benzoyl. chloride.
75 with formamide in phenol)
50
.65
'
Example 5
5 parts of 4-amino—1.9-anthrapyrimidine in 50
parts of ortho-dichlo-rbenzene, are heated to
boiling, after the addition of 10 parts of para 70
chlorbenzoyl chloride, and the whole is boiled
until there is no further lightening in color,
which is usually the case after a few hours.
The
whole is then' allowed to cool and the reaction
product-which separates in a theoretical yieldin 75
“2,040,857
the form of lustrous crystal spa‘ngies‘ ls’?ltered
gene or thiophosgeiie or perchlormethyl mer;
7 off by suction. 'It dissolvesin sulphuricv acid
captan.‘
giving .a golden yellow coloration,'cry’stallizes in
the form of needles .and yields in violet brown vat
from which vegetable and animal ?bres are dyed
clear green yellow shades of good fastness and
excellently fast to washing.
Reaction products which crystallize well and
i
..
»
.
Example 8
65 parts of 2-amino-C-phenyl-LQ-anthrapy
rimidine (obtainable from C-phenylanthraquin
one-2.1-oxazo1e by treatment with ammonia ac
cording to the following formulae‘:
110,
can 7
10
4
15
O
20 'yield green yellow dyeings .are likewise obtained
in quantitative yields from 4-amino-1.9-anthra
pyrimidine and ortho-chlorbenzoyl chloride or
2.4-dichlorbenzoy1 chloride.
7
V
The corresponding condensation product from
25
5-amino-1.9-anthrapyrimidine and ortho-chlor
benzoyl chloride gives reddish yellow dyeings.
-Tre acylamine obtainable from anthrapyrlm
.idine by nitration by means of nitric acid in sul
phuric acid, reduction of the nitro compound to
yields in a crystalline form is ?ltered off by suc
with para-chlorbenzoyl chloride dyes cotton yel
.
,
the reaction mixture, which is originally orange
red, has become yellow, allowed to cool and the
reaction product which separates in excellent
tion. It dissolves in concentrated sulphuric acid
giving a golden yellow coloration and dyes cot
ton green yellow shadesof good fastnessfrom
a brown vat. The reaction proceeds according
30 the amine and treatment of the amino compound
low shades.
1000 parts of nitrobenzene and 58 parts of an‘
thraquinone-2-carboxylicacid chloride are heated
to boiling for some hours while stirring until
to the following formulae:
'
(‘1013s
7 Example 6'
.
7
o
247 parts of 4-amino-1.9-anthrapyrimidine in
35 2000 parts of ortho-dichlorbenzene are heated
slowly while stirring after the addition of 5700
parts of meta-methoxybenzcyl chloride, and then
ti
A
~NH1 + oioo-
—->
boiled for a short time. The reaction product
which separates in a crystalline form in excellent
40 yields is ?ltered o? by suction an may be crys- '
tallized from trichlorbenzene. It dissolves in
concentrated sulphuric acid giving an orange
coloration, and gives a violet red brown vat from
which cotton is dyed powerful green yellow clear
shades of very good fastness.
The condensation product with beta-naphthoyl
<5\
'
l|\I/ \N
(I)
A
H
_N.0C_
,
/\
V chloride (yellow needles) also dyes cotton green
ish yellow shades from a red brown vat. The
acylamine from 2 molecular proportions of 4
60 aminoanthrapyrimidine and 1 molecular propor
tion of isoterephthaloyl chloride also gives yel
low dyeings.
‘
'
+7110]
2 - benzoylamin'o-C - phenyl - 1 . 9 -anthrapyrimi-.
‘dine forms yellow needles and dissolves in con
centrated sulphuric acid giving a golden yellow
Example 7
2 parts of 4-amino-1.9-anthrapyrimidine in 40
coloration. '
e
55 parts of trichlorbenzene are heated to boiling for
The reaction product of anthraquinOne-Z-‘car
several hours while stirring after the addition of
10 parts of acetic anhydride. The whole is then
dipyrimidine (obtainable from 1.9.4.10-anthradi
allowed to cool and is worked up in the usual
manner. The'acetyl derivative obtained forms
yellow crystals, dissolves in concentrated sul
phuric acid giving a golden yellow coloration and
quinone) by nitration by means of a mixture of
nitric‘ and sulphuric acids and reduction of the
nitro compound) is alsoa yellow crystalline pow 60
pyrimidine (obtainable ‘from l-.5ediaminoanthra
yields comparatively pale green yellow dyeings
der which dissolves in concentrated’ sulphuric’
on cotton and wool from an orange vat.
acid giving an orange coloration. .
A green yellow reaction product the acetyl-p
2-benzoylaminoé1.9-anthrapyrimidine and 2
chlorbenzoyl-amino derivative, is obtained there
from by treatment with para-chlorbenzoyl chlo
anthraquinone- beta- carboxylamino- 1 -. 9 -anthra
ride. It dissolves in concentrated sulphuric acid
giving a golden yellow solution, and furnishes .a
brown-violet vat.
70
boxylic- acid chloride on amino-1.9.4.10-anthra :55
'7
,
The product from 4-amino-1.9#-anthrapyrimi
dine and oxalyl chloride is a green yellow crys
talline powder which is very di?icultly soluble.
The reaction product of the above amino com
pound with chlorcarbonic acid ethyl ester is also
75 yellow’ as is also the reaction product with phos
pyrimidine (obtainable from' .anthraquinone-2.1
oxazole by'treatment with ammonia and conver
65
sion of the Z-amino-l.Q-anthrapyrimidine formed
with Z-anthraquinone- carboxylic‘ acid chloride)
yield pale yellow dyeings on'cot'ton from orange
brown
vats.’
"
‘
‘
Example 9
'
'
30 parts of chlor-4-amino-1.9-anthrapyrinii
dine (prepared from 4-arnino-LQ-anthrapyrimi
dine by treatment with chlorine in chlorsulphonic
acid-irmithe-epresence of iodine-andsulnhur as
70'
5
9,040,857
transferrers) in 500 parts of naphthalene‘ are
heated to boiling, after the addition of 100 parts
of benzamide, 60 parts of potash and 3 parts of
para-para'-dicarboxylic acid obtained in "an
copper oxide, while stirring until there is no fur
ther formation of ‘dyestuffp The whole is then
allowed to cool and is worked up in the usual
manner. The resulting reaction product is an
analogous manner is in the form of yellow needles
and dyes cotton greenish yellow shades from 'a
brownish violet vat. Similar shades are obtained
from the corresponding derivatives of diphenyl
mono-carboxylic acid or of naphthalene-1.4-di
carboxylic acid or naphthalene-1.5-dicarboxylic
olive yellow powder, dissolves in concentrated
acid or of diphenyl-ether carboxylic acids, or of
sulphuric acid giving an orange coloration and
10 dyes cotton yellow from a violet brown vat.
diphenylsulphide or phenylsulphide carboxylic
acids.
By treating the reaction product with para
chlor-benzoyl chloride, a benzoylamino-para
10
Example 3
360 parts of para-aminobenzoyl-4-amino-1.9
chlorbenzoylamino-LQ-anthrapyrimidine giving anthrapyrimidine (obtainable by reducing the
15
yellow dyeings is obtained.
Example 10
247 parts of 4-amino-1.Q-anthrapyrimidine are
boiled for a short time in 2500 parts of nitroben
zene with 220 parts of orthotoluylchloride ‘while
para-nitrobenzoyl-‘l-amino-l.Q-anthrapyrimidine
described in Example 11) are boiled for a short
time in 3000 parts of nitrobenzene with 170 parts
of benzoyl chloride while stirring. The reaction
product is ?ltered off by suction after cooling.
stirring. The mass is allowed to cool and ?ltered
20 by suction. The resulting reaction product which
The resulting (para-benzoylamino-benzoyl) “l
amino-1.9-anthrapyrimidine which is obtained
with a very good yield and in a state of high
is a crystalline yellow powder dissolves in con
centrated sulphuric acid to give an orange solu
tion, furnishes a dark violet brown vat and crys
tallizes from organic solvents of high boiling
point in the form of yellow needles. From the
vat it dyes animal and vegetable ?bres strong ‘
purity, crystallizes in yellow needles which dis
brilliant greenish yellow shades of excellent fast
obtained by employing,instead of benzoyl chlo- -
ness to washing and boiling.
In an analogous manner similar reaction prod
ride, in an analogous manner para-chlorobenzoyl 30
chloride or 2.5-dichlorbenzoyl chloride or oxalyl
chloride or meta-methoxybenzoyl chloride.
solve in concentrated sulphuric acid giving an
orange solution and dye cotton powerful clear
30 ucts which mostly dye yellow shades are obtained
from ll-amino-l.Q-anthrapyrimidine and other
carboxylic acids, for example the para-cyanben
yellow shades of excellent fastness from a warm
violet brown vat.
.
1
Reaction products dyeing similar shades are
zoyl-‘l-amino-l.Q-anthrapyrimidine, the para-?u
The acylamine obtained from para-amino
benzoyl - 4 - amino - 1.9 - anthrapyrimidine
and
anthraquinone-beta-carboxylic acid in an anal
orobenzoyl-‘l-amino-1.9-anthrapyrimidine (yel ogous manner dyes yellow shades. ‘Use may also 35
low needles), para-methoxybenzoyl-4-amino-1.9- . be made of carboxylic acids having a still higher
anthrapyrimidine and the corresponding meth
molecular weight, as for example carboxylic acids
oxy derivative, meta-methylbenzoyl-4-amino-1.9
derived from thiazolanthrone, benzanthrone or
anthrapyrimidine, 3.4-dichlorobenzoyl-4-amino anthraquinone
- thioxanthone. Carboxylic acids . 40
1.9-anthrapyrimidine and the corresponding 2.5
from anthrapyrimidine, as .for example 1.9
40 and 2.3-dichloro derivatives, 3.4.5-trichloroben
anthrapyrimidine-2-carboxylic acid (obtainable
zoyl-4-amino-1.9-anthrapyrimidine, and also the
corresponding cinnamoyl derivative.
Example 11
125 parts of 4-amino-1.9-anthrapyrimidine are
boiled for a short time in 1250 parts of nitro
benzene with 125 parts of para-nitrobenzoylchlo
ride while stirring. The reaction product is ?l
tered off by suction after cooling. It is obtained
50 in the form of yellow needles and in .a nearly
quantitative yield. It dissolves in concentrated
sulphuric acid giving an orange solution and dyes
cotton strong yellowish brown shades from a dark
ester and formamide and saponi?cation of the
resulting anthrapyrimidine -2- carboxylic ester 45
melting above 360° C.) may also be employed.
Example 14
250 parts of 5-amino-1.9-anthrapyrimldine
(bluish red needles obtainable by saponifying the 50
5 - benzoylaminoanthrapyrimidine described ‘in
Example 3) are boiled fora short time in‘ 5000
parts of nitrobenzene with ‘250 parts of para
chlorobenzoyl chloride while stirring. The reac
prepared in an analogous manner is in the form
tion product is ?ltered off by suction after cooling. 55
It crystallizes in yellow needles and dyes cotton
clear greenish yellow shades of excellent fastness
of yellow needles. It dyes strong clear yellow
from a brownish violet vat.
brownish violet vat.
The para-methyl-meta-nitrobenzoyl derivative
shades. Meta-nitrobenzoyl-4-amino-1.Q-anthra
pyrimidine dyes orange yellow shades.
Example 12
250 parts of 4-amino-1.9-anthrapyrimidine are
boiled in 3000 parts of nitrobenzene with 145 parts
of diphenyl-para-para’-di-carboxylic acid chlo
ride while stirring, until no more dyestuff is
formed. The mass is allowed to cool and worked
up in the usual manner. The reaction product
of which an excellent yield is obtained, is in the
form of yellow needles, dissolves in concentrated
sulphuric acid giving an orange solution and dyes
cotton yellow shades of excellent fastness from a
dark violet vat. The crude product may be puri
?ed by treating an aqueous paste thereof with
aqueous sodium hypochlorite solution.
75
from 1-aminoanthraquinone-2-carboxylicv ethyl
The corresponding derivative of benzophenone
Example 15
60
24.’? parts of '7.-amino-LQ-anthrapyrimidine
(obtainable by the reaction of formamlde on 1
aminoanthraquinone-‘l-sulphuric acid and re
placing the sulphuric acid group by the amino
group) are heated for a short time to boiling while 65
stirring in 250 parts nitrobenzene with 20 parts
of benzoyl chloride, the reaction mixture then
being worked up as usual. The reaction product
obtained in the form of yellow needles yields green
yellow dyeings of very good fastness, in particu 70
lar against washing, on cotton from a dark violet
brown vat.
The acyl compound obtained in an analogous
manner from 4-amino-LQ-anthrapyrimidine and
para-brombenzoic acid dyes strong brilliant
75
‘25040. 857
igreenish “yellow :shades. tYellow' dyeings are also
obtained vbTy the products‘pr‘oduced from para
iodbenzoyl chloride or rbrom-‘l-naphthoyl chlo
ride (obtainable by bromin‘ating uénaphthoici'acid
"amino ‘4 119 -; anthrapyrlmidi'nes’furnishi orang'e
dyeings. The para-phenylbenzoylamine deriva
tive dyes strong reddish yellow shades.
-in glacial acetic acid and heating’ the product
'
>with:.thionyl chloride) vand 4-amino-L9-anthra
:pyrimidine.
Yellow orange orred shades arepro
Example 18
25 parts of 5-amino-LQ-anthrapyrimidine are
short time in 500 parts'of
nitrobenzene with 30 parts of anthraquinoné-Z
.duced by the acyl compounds produced from '4
fa‘mino-1.9-anthrapyrimidine and'the chlorides of V ‘heated to boiling for a
P10. sebacic, adipic, stearic, pyroracemic, hexahydro
benzoic,
benzanthrone - 2 icarboxylic, ' anthrai
-Quinone-l-carboxylic, salicylic, cresotinic,_2.4.5~
vtrichlorbenzoic, "cliphe'nyl carboxylic, diphenyl
'Tniethane'carboxyli'c, anthanthrone carboxylic and
phuric acid’ to give a red solution'and dyes cotton
carboxylic acid.
,The acyl co'mpound'of thesaid anthrapyrimidine
clear yellow shades from a brown red vat.
Land -Z-aminQanthraquinone - 3 - carboxylic acid
‘ chloride dyes brown ‘shades. A yellow dyeing re
is obtained by the use of 1-chloranthraquinone-2
carboxylic acid chloride instead of anthraqui
none-2-carboxylic acid’ chloride, ;whereas the
15 fallo - ms -.naphthodianthrone
lactionproduct is obtained from lmolecular pro
“,portion of: phosgene, 1 molecular proportion of
.?éaminoanthraquinone and 1 molecular propor
tion of 4-amino-LQ-anthrapyrimidine..
"25
carboxylic acid‘ chloride. The reaction product "
worked up in'the usual manner is, a yellow crys-'
talline powder dissolving in concentrated sul
.YIristead of 7.-amin0-1.9-anthrapyrimidine men
tioned in the ?rst‘ paragraph of this example its
substitution products, for example its halogen and
methyl derivatives can be subjected to benzoyla
tion, the products obtained likewise dye yellow
shades.
.
’
A product dyeing more greenish yellow shades.
acylamino
compound produced by means of -1- .
_
aminoanthraquinone -'2-carboxylic acid chloride '
dyes clear strong red brown shades.
Example 19
24.7 parts ofe-aniino-LQV-anthrapyrimidine are
heated to boiling in 250 parts of orthodichlor
benzene ‘after the addition of 35 parts of 4'
bromdiphenyl-4-carboxylic acid chloride until
Example 16
a sample of the reaction product melts at about.
310° C. The reaction mixture is then Worked up
250 parts- of S-amino-LQ-anthrapyrimidine
Vareheated vto boiling for ashort time in 5000
parts of .nitr’obenzene with .110 parts of iso
phthaloylchloride. The yellow crystalline reac
tion product obtained by ?ltration of. the reaction
.mixture dissolves in concentrated sulphuric acid
to give an-orange red solution and. crystallizes
_ .from organic solvents of high boiling point. .It
_dyes c0tton>strong golden yellow shades of very
40 '1 goodfastness from a red vatlhaving a violet tinge.
‘Dyestu?'s‘furnishing similar shades and having
similar properties are obtained by the use of
terephthaloylhchloride orvthe mixture of iso- and
terephthaloyl chloride. .Dyestu?‘s .dyeing 'more
greenish. yellow- shades are obtained by employ
as usual. “Thedyestu? thus obtained dyes the
vegetable ?bre from a brown violet vat strong
greenish yellow shades.
Similar dyeings are‘ obtained from the acyl-,- .
amines of 4-amino-1.Q-anthrapyrimidine pro
duced by means of other diphenyl-4-carboxylic
.acids substituted in‘the 4' Position, vfor example 7.
the 4'-ethyl, -4’-.chloro and 4'-benzoyl derivatives.
The acylamine produced by the action of para
chlorbenzoyl chloride on the anthrapyrimidine
produced from 1.4-diamino-p-methoxy anthra
quinone with formamide, dyes the‘vegetable ?bre
yellow shades which are also obtained by means
of the acylamine produced in an analogous‘
ing' suecinic, adipic or sebacic acid chloride as manner from 'para-chlorbenzoyl chlorldeeand' the
LQ-anthrapyrimidine derivative produced from
acylating agent. The’acylamino derivatives ob
tained by means of diphenyl .p.p’r-.dicarboxylici lA-diaminor- 2 - bromanthraquinone or ‘1.4;- di
and benzophenoner-pp’-dicarboxylic'acid chloride
,dye" cotton orange or. golden yellow‘ shades.
amino - 2 - methylanthraquinone and formamide.
The anthrapyrimidine derivative produced from
1.4 - diamino - 5 - nitroanthraquinone and form
Example 17
amide furnishes on condensationwith benzoyl
chloride a dyestuff dyeing reddish yejllow'shades.
.250 parts of‘ 5-amino-LQ-anthrapyrimidine are
The dyestuffs obtainable from 5-amino-L4-di
heated while stirring for a short time to'boiling benzoyl‘diaminoanthraquinone
‘Vin 4000,1p‘arts ,of nitrobenzene with 260 parts of vfurnishes rose red ‘shades.
paraébrombenzoyl ‘chloride. The reaction prod
uct,
para-bromben‘z‘oyl-?-amino-1.9-anthrapy
rimidine, obtainediby'?ltration of the reaction
.mixture after cooling and workingyup as usual,
icr’ystallizes ‘from trichlorbenzene in small yellow
‘needles dissolvingin concentrated sulphuric acid
.to a red solution. Greenish yellow dyeings of
" good fastness are-obtained with‘ the said product
:65Jfroml1a red .vat with a violet tinge.
'Similar ‘dyeings
are
obtained ‘from
para
15 parts of 1-‘amino-8-benzoylaminoanthra
quinone (obtainable by partial benzoylation of
1.8-diaminoanthraquinone) are heated to boiling
for several hours with 30 parts of formamide in 60
parts of phenol While distilling ‘011’ the water
formed. "When the reaction mixture has become 65
yellow, it is allowed to cool and the 8-benzoyl
amino-1.9-anthrapyrimidine formed ?ltered off.
cyanbenzoyl 4'5 ; amino- 1.9~anthrapyrimidine the
It is a powder. crystallizing from high boiling'sol
rimi'dine and the meta chlorbenzoyl-S-amino
vents in. yellow needles, dissolves in concentrated
sulphuric acid to give a golden yellow solution. and
‘ ILQ-anthrapyrimi'dine.
Slightly more greenish dyes cotton yellow shades from a brown violet.
shades furnishthe 2'.4’-dichlorbenzoyl, the 3'.4’
vat.
' dichlorbenzoyl ‘ and in ‘particular the 2'.5'.-di
In an analogous ._manner the (2'.5’-dichlor
chlorbenzoyl ‘-"5 - amino - 1.9 — 'anthrapyrimidine.
"The "para'imethylbenzoyl ‘and ,B-naphthoyl-5
55
Example ‘20 .
iodbenzoyl-5eamino-‘l.Q-anthrapyrimidine, para
170" 'ortho lchlorb'enzoyl — 5 - amino - 1.9 - anthrapy
'
and formami'de
benzoyl)~5-amino-1.9-anthrapyrimidine from 1-‘
amino - (2'.5' -‘ dichlorbenzoyl) - -5'- amino'an -
7
2,040,857
It may also be replaced by dimethylaniline or
other tertiary bases or other acid binding agents
thraquinone, the (para-chlorbenzoyl) -4-amino
1.9-anthrapyrimidine from l-amino-(para-chlor
benzoyl) -4—aminoanthraquinone, the (benzan
thraquinone - 6' - carboxyl)
such as sodium carbonate and acetate.
anthrapyrimidine from l-amino-(benzanthra
quinone-6' -carboxyl) -5-aminoanthraquinone is
obtained.
‘The
(dichloranthraquinone -
benzacridone- - 3' - carboxyl)
'
The (diphenyl - para - carboxylic) - 4 - amino -
- 5 - amino - 1.9 -
1.9-anthrapyrimidine dyeing strong clear green
ish yellow shades from a violet vat is obtained
by heating 4-amino-L9-anthrapyrimidine and
2.1 -
diphenyl-4-carboxylic acid chloride in a mixture
- 4 - amino - 1.9 -
anthrapyrimidine is obtained by partial acylation
10 by means of benzoic acid anhydride of the acyl
of nitrobenzene and pyridine. The acylamines
prepared in an analogous manner from 4-amino
10
1.9-anthrapyrimidine and 4’-nitrodiphenyl-4
amine prepared from 1.4-diaminoanthraquinone
carboxylic acid (obtainable by nitration of di
phenyl-para-carboxylic acid by means of nitric
carboxylic acid.
acid in crude chloroacetic acid) or dichlordi
pheny1-4-carboxylic acid (obtainable by chlorin 15
ating diphenylcarboxylic acid in trichlorben
and dichloranthraquinone-2.1-benzacridone-3'
The
4-benzoylamino-2-amino - C - phenyl-1.9
15 anthrapyrimidine is obtained by heating 4-ben
zoylamino-C-phenyl-Z.l-oxazol with ammonia.
zene with chlorine in the presence of iodine at
between 135° and 140° C.) or with quinoline-6
Example 21
carboxylic acid likewise dye yellow shades.
The reaction products may be isolated by dis 20
tilling off the diluent, if desired under reduced
26.2 parts of 2-amino-C-methyl-1.Q-anthra
pyrimidine (obtained by heating anthraquinone
20
pressure or by means of steam, or by means of
C-methyl—2.1-oxazol with ammonia) are heated
steam under reduced pressure. They are readily
soluble in some diluents miscible with water, such 25
as chloroacetic acid, and can be reprecipitated
from such solutions by dilution with water.
to boiling for a short time in 200 parts of nitro
benzene with 30 parts of anthraquinone-2-car
The reaction proceeds ac
cording to the following formulae:
25 boxylic acid chloride.
30
OH:
I
30
/
If \i
a ¢°
if
NI
O “a
AO/NH,
‘(DAG
0AY / \OAO
Y
Y
)(
+
35
____>
+ H01
.35
l
o
40
40 After completion of the reaction which may be
recognized by the evolution of hydrogen chloride
ceasing, the reaction mixture is Worked up as
usual. The acylamine obtained in yellow needles
issolves in concentrated sulphuric acid to give
45 a yellow solution and dyes the vegetable ?bre
In order to increase the property of printing
of the dyestuffs they may be mixed. intimately
with glycerine or other additions improving the
property of printing such as anthra?avinic acid
or mixtures of such additions.
45
Example 23
yellow shades from a violet brown vat.
The 2 - benzoylamino - C - methyl - 1.9 - an -
thrapyrimidine as well as the C-ethyl and the
50
C-propyl derivative likewise dye yellow shades.
The
para - chlorbenzoyl - 4 - amino - C - phen~
yl-LQ-anthrapyrimidine (obtainable by heating
4 - amino - C - pheny
- 1.9 - anthrapyrimidine
with para-chlorbenzoyl chloride) dyes cotton
55 reddish yellow shades from a violet vat.
The
C-naphthyl and the C-para-chlorphenyl deriva
tive dye similar shades as do also the isomeric
acylamines of the 5-amino-1.9-anthrapyrimidine
series.
60
36 parts of 4-chlor-Z-methyl-C-phenyl-1.9
anthrapyrimidine (obtainable by diazotizing 4 50
amino - 2 - methyl - C - phenyl — 1.9 - anthra -
pyrimidine and replacing the diazo group by
chlorine) are heated at about 150° C. for about 2
hours in 100 parts of nitrobenzene after the ad 55
dition of 5 parts of potash, 1 part of copper ace
tate and 50 parts of para-toluene sulphamide
and then heated for several hours at about 180“
C. After cooling, the 2-methyl—4—para-toluene
sulphamide - C - phenyl ? 1.9 - anthrapyrimidine
Example 22
247 parts of of amino-1.9-anthrapyrimidine are
heated to boiling while thoroughly stirring in
1000 parts of nitrobenzene after the addition of
65 240 parts of crude pyridine and 190 parts of para
chlorbenzoylchloride, the mixture being kept at
the said temperature until the separation of dye
stu? does not anymore increase. The mixture
is then allowed to cool and the reaction product
separated in the form of pure yellow needles ?l
The yield is about that required by.
tered off.
theory. The dyestuff is practically identical with
the product described in Example 5.
Pyridine alone may also be employed as diluent
instead of the mixture thereof with nitrobenzene.
is ?ltered oil. It is a yellow crystalline powder,
dissolves in concentrated sulphuric acid to give
a brown violet solution and dyes cotton yellow
shades from a brown violet vat.
The 4 - para - toluenesulphamide — 2 - methyl -
65
1.9-anthrapyrimidine obtained in an analogous
manner dyes greenish yellow shades.
Example 24
7.0
20 parts of 5-amino-4'~benzoylamido-1.1’
anthrimidecarbazol (obtainable by partial sa
poni?cation by means of sulphuric acid at be
tween 35° and 50° C. of 5.4’-dibenzoyldiamino
l.l’-anthrimidecarbazol) are heated to boiling
—
v2,040,857 '
for :severalhours with 100 parts of ‘formamide in
200‘ parts of phenol. The reaction‘proceeds .ac
cording to the formulae:
.‘Eammple 2ft ’ "
24.7 ‘parts of :5eamino-l.9+anthrapyrimidine
10
15'
N
‘20
As soon as a sample yields yellow brown dyeings
fast to chlorine, the. reaction mixture is allowed’ :areheatedto boiling ‘while stirring in 200 parts
of-nitrobenzene with~35 parts of 4"-bromdiphenyl- '
to cool and the '4-benzoylamino-5.IO-pyrimidino
1.1’-anthrimidecarbazol formed ?ltered off. It fI-CELI'bOXYllC acid chloride (obtainable by brom
inating diphenyl-‘i-carboxylic acid and treating
is a brown crystalline powder, dissolvesin con
centrated sulphuric acid to give a red solution the product with phosphorus pentachloride).
and dyes cotton from a brown vat strong yel-' When the reaction mixture has become yellow
£30 low
orange, it is allowed to cool and the (.4’-bromdi~
brown shades of very good fastness.
.
phenyl-4—carboxyl) -5-a_.mino- 1.9 -anthrapyrimi
w A brown dyeing benzoylaminoanthrapyrimi
dine separated in yellow needles ?ltered off. It
‘ dine derivative is obtained in'an analogous man
dyes cotton golden orange :shades of very good
ner from 5-amino-4’-benzoylamino—8-methoxy
35
benzoyl-diamino-8-methoxy-1.1'-anthrimidecar
v'I'he same product is also obtained .by the action
bazol in a manner analogous to that described
carboxyl)—1-aminoanthraquinone. “In-an analo~
in the foregoing paragraph.
The reaction product obtained in an analogous
manner from 5-amino-5'-benzoylamino-1.1'—an
40
thrimidecarbazol dyes golden orange shades.
By 7 condensation of a-aminoacylaminoanthri
mides with'formamide in an analogous manner
the
acylaminopyrimidinoanthrimides
are
ob
L45 tained, as are also obtained the benzoylamino
pyrimidinoanthrapyrimidines by the action of
formamide on a-aminobenzoylaminopyrimidino
anthraquinones.
V
In the same manner by the action of formamide
50 on other a-aminoacylaminoanthraquinone de
rivatives, such as the a-aminoacylamino deriva
tives of benzanthraquinone, dianthraquinonyls,
anthraquinoneacridones, phthaloyl carbazol or
other carbazols containing the anthraquinone
nucleus for example anthraquinonethioazols and
the anthraquinoneazines, corresponding acyl
aminopyrimidine derivatives are obtained.
460
100 parts of 5-amino-1.9-anthrapyrimidine are
heated for a short time while stirringat between
125° and 130° C. in 500 parts of 2.5-dichlorben
zoylchloride. As soon as the reaction mixture
has become pure yellow in color, it is allowed
to cool and the excess of dichlorbenzoylchloride
?ltered o?". 'The 2'5'-dichlorbenzoyl-5-amino
1.9-anthrapyrimidine is identical with the prod
uct described in Example '17.
The
'
5-acetylamino-1.9-anthrapyrimidine
is
obtained in an analogous manner by heating 5
amino-1.9-anthrapyrimidine in :acetic acid an
hydride, as is obtained the phenylacetyl-5.-amino—
LQ-anthrapyrimidine by the action of phenyl
.acetic acid "chloride.
.
of formamide ‘on 5-amino-(4'-bromdiphenyl-4 173'5
gous manner the acylamines of aminoanthrapy
rimidines and 4-, 5-, and 8-aminoanthraquinone
l-carboxylic acids can be prepared.
The latter
aminoanthraquinonecarboxylic acids can’ be ob-'
tained by treating the corresponding ‘chloro
aminoanthraquinones or chlorbenzoylaminoan
filo
thraquinones with cuprous cyanide and subse
quent saponi?cation.
~
. 1145
‘Example 27
.18 parts’ of (1'-benzene-4’~carboxylic acid
chloride) -1.-aminoanthraquinone (obtainable by
condensation-of l-chloranthraquinone with para :150
aminobenzoic acid and treating the product with
thionyl chloride) are heated to boiling for a short
time in 500‘ parts. of nitrobenzene after the addi
tion of 12 parts of ‘ll-amino-LQ-anthrapyrimi-‘j
dine and allowed to cool after the evolution of
hydrogen chloride .has ceased. The’ reaction
.product recovered-in the usual manner dissolves
Example 25
5 65
fastness against washing’and boiling ‘with soda.
'1.1'-a'nthrimidecarbazol (obtained from 5.4'-di
in concentrated sulphuric acid to give a yellow
solution and dyes- cotton red orange shades of
good fastness from a brown violet vat. Instead 60
of para-aminobenzoic acid other carboxylic acids
of aromatic. amines may be used for the prepara
tion of' the acylating component such as amino
anthraquinonecarboxylic acids or pyrimidinoan
thraquinone carboxylic acids.
Example 28
10 parts of 5-aminoanthraquinone-2.1'-carb
aminoanthraquinone (obtainable by acylating 70
a-aminoanthraquinone with 5-nitroanthraquin
one-2-carboxylic acid and reducing the acylation
product) are heated to boiling for several hours
with .1200 partsqof formamide in;400_,parts of
75
9 .
2,040,857‘
diiieYobtainable by brominati'ng 5-amino-L9-ané
phenol. The reaction proceeds according to the
following formula:
thrapyrimidine in chlorsulphonic acid) are‘ heated
10
15
15.
to boiling for a short time in 3000 parts of nitro
The reaction mixture is then diluted with ethyl
20 alcohol and worked up as usual.
product,
the
The reaction .
benzene with 220 parts of 2.5-dichlorbenzoy1 20
l’-anthraquinone-Z-carbaminm ‘
5.10-anthrapyrimidine, is a brown yellow powder
which is dif?cultly soluble and may be puri?ed
by means of oxidizing agents, ‘for. example by
chloride after the addition of 100 parts of cal
cined soda. After cooling the reaction mixture is,
worked up as usual. The dyestu? obtained dis
solves in concentrated sulphuric acid to give a
ings of a very good fastness from a brown violet
solves in concentrated sulphuric acid to give an'
olive yellow solution and furnishes yellow dyeings
vat...
~
>
>
r
The _‘ 5-benzoylamino - B - naphthoylamino-1.9
‘ .
vanthrapyrimidine is obtained in an analogous
The reaction may also be carried out in tri
An addition of
boric oxide, zinc chloride'or copper salts acceler
manner by the action of ?-naphthoyl chloride on
obtained in an analogous manner by treating‘
toluene . sulphamide, benzoylating the product
on'cotton from a brown violet vat.
25
golden yellow solution and furnishes yellow dye
25 means of an alkali'metal hypochlorite. ‘.It dis
30 chlorbenzene or nitrobenzene'.
amino- 5 -'benzoylamino - 1.9 - anthrapyrimidine
which may be prepared by condensing the afore
ates the reaction.‘ Similar reaction products are, said brom-5-aminoanthrapyrimidine with para
acylamines of other m-aminoanthraquinone car
35 boxylic acids with formamide;
_
thus obtained and partially saponifying the 35
‘
latter product.
In the same manner m-aminoacylaminopyrim
idinoanthraquinone may be converted by means
401
a
A similar reaction product is also obtained by
treating 1 molecular proportion of the corre- '
of formamide into acylaminopyridinoanthrapy
spending , diamino-l.Q-anthrapyrimidine with 1
rimidines.
molecular proportion of benzoyl chloride and 1
molecular proportion of B-naphthoyl chloride. A
Example 29 ~
100 parts of '3-amino-l.Q-anthrapyrimidineV reaction product is obtained in the form of orange
needles dyeing cotton orange shades from a brown
(obtainable by condensation of 1.3-diarr'1ino
anthraquinone with formamide) ar'e‘heated to violet vatby reaction of parachlorbenzoyl chlo
(boiling in 1000 parts of nitrobenzene with 120 3 ride‘ on polychlor-S-amino-LQ-anthrapyrimidine 45
parts of para-chlorbcnzoylchloride until the’ which may be prepared by saponi?cation .by
coloration of the reaction mixture has become means of sulphuric acid of the chlorination prod
olive yellow. After cooling, the reaction product uct of 5-benzoylam1no-1.9-anthrapyrimidine;
separated in crystalline form is ?ltered off. It
Example 31
50
‘dissolves in concentrated sulphuric acid to give
24.’? parts of 2-amino-C-phenyl-1.9-anthra
a golden yellow solution’ and dyes cotton yellow
shades from a brown Vat. The reaction product pyrimidine are heated to boiling for a short time
in 250 parts of nitrobenzene with 30 parts of
obtained ‘by acylation of 'G-amino-lLQ-anthra
pyrimidine by means of- para-chlorbenzoylchlo - anthraquinone-l-sulpho chloride. After cooling
ride dyes yellow shades.
_
a
r
'- r - a
"The-product’ obtained by acylation of ,diami‘noé
the acylation product is ?ltered off. It is a yellow 55
'
powder, dyes cotton yellow shades from a brown >
1.94anthrapyrimidine (prepared by'lco'ndensing
vat and dissolves in concentrated sulphuric acid
to give a golden yellow solution.
A similar reaction product is obtained by the
the ldichlo'ranthrapyrimidine,'produced by chlo
rinating B-chlQr-anthrapyrimidine in trichlor
employment of the isomeric anthraquinone-2- 59
sulpho chloride. Yellow dyeing acylation prod
60 benzene in the'presence of iodine, with ;para-~
toluene sulphamide and saponi?cation by means
of sulphuric acid) by means ofbenzoyl chloride
dyes orange shades. The product obtainedyrby
acylating by means of l-a‘minoanthraquinoneé2—
65
ucts are obtained in an analogous manner by the
action of benzene-, 0-, or p-toluene sulpho chlo
1.9.5.l0-anthradipyrimidine which may be pro
ride on rI—amino-l.Q-anthrapyrimidine.
Identical reaction products are obtained by
condensation of the corresponding halogen
anthrapyrimidines with the corresponding sul
duced-by acting on "1 .5-diaminoanthraquinone -
phamides.
'carboxylic acid chloride the polyamino-l.9.5_.10
anthradipyrimidine (obtainable by ‘chlorinating
with formamide, condensing the chlorination
product with ‘para-toluene 'sulphamide ‘and sa
36.7
ponifying the condensation product by means of
sulphuric acid) dyes brown shades.
H
7
Example ~30
‘
’
,
' ‘325-partsiofbromo-5-a1nino-LQ-anthrapyrimi
parts ,of - 4-benzoylamino-L9-anthra- 70
pyrimidone are heated for several hours, while
stirring,
at between 130° and 135° C. in 200
parts of nitrobenzene with 22 parts of
phosphorus pentachloride. After completion of 75
1,0
the v,reaction the reaction mixtureis , worked on
manner- The reaction». product’
_
,
, lawmnle 3:45
1111. 5151.18, usual
which according to analysis is a C-chlor-4
100 parts of, a 10 per cent aqueous- paste of the
ben'zoylamino-LQ-anthrapyrimidjne, dissolves in
. acylamine
' concentrated sulphuric acid to give a’ golden" yeli
~ ‘ low solution and dyes cotton strong, clear greenish
violet
vat.
'
'
‘ ‘
'
'
4-amino-1LQ-anthrapyrimidine '
tion of 30 parts of bromine, are heated to boiling:
yellow shades of very good ‘fastn'ess from asbrown '
1
from
and diphenyl-4.l-carboxylic acid, afteran' addi
on a waterbath under a re?ux condenser while
‘
\stii-‘ring.v 'When 'a sample withdrawn vyields
I’
a
By the condensation of the aforesaid chlorine '
dyeing entirely stable to chlorine (which is usu
:10 ation product with a
or ,B-aminoanthraquinones '
new dyestuffs dyeing different shades are-0b
tained.
.‘
'
'
>
‘
ally the ‘case after‘a few hours) the excess of
bromide is removed by the usual methods and
'7
' the reaction product containing bromine is ?l
By treating the 5-benzoylamino-l.9-anthra
tered off by suction. It dissolves in concentrated
.pyrimidone (obtainable by condensingd-amino- ' sulphuric acid giving an orange coloration and
yields greenish yellowv clear dyeings of very good
manner described in the ?rst paragraph of this fastness on vegetable ?bres from a cold or warm.
11,5 5-benzoylaminoanthraquinone vvith urea) in the
. example a dyestuff is' obtained crystallizing in
violet blue vat.
Similarly,
yellow needles and. furnishing yellow dyeings on
1. cotton,
20,
in a corresponding manner from the isomeric
.
jC-jCh-lor-B-Z'?f-dic
Y " : thrapyrimidine is
v
_
v
‘
obtained in an analogous man
dyestuif ' from. .5-amino-L'Q-anthrapyriinidine' is
V
superior iii-its vfastnes'sftd
' ‘nor by’ treating ' 8-‘2'15' -dichlorbenzoylaIl,1-inO-1;9-.
. anthrapyrimidone with
.
the bromination product obtainable '
phosphorus, pentachloa
ride. ‘It dyes the vegetable ?bre yellow shades,
from a dark violet vat.
,
e
washing V and boiling’.
.
.
.
'20.
with soda to the dyestu? free‘ from bromine.
lbf-tléampk?
H
,
V
e
' Substitution products of the aforesaid 45-, 5"
'50 ' parts ‘or the; initial material’ employedim
23'
paragraph 10f Example. 3.4 are Suspended in_, 500.
mayi
be subjected to chlorination in the aforedescribed‘ parts of nitrobenzene." After adding 1.5. rparts'of
manner- for example, the ’5-benz<l>ylamino—li— iodine and '75 parts of sulphuryl. chloride; the.
methoxy-1,-9—anthranyr1mid0ne. the ls-diben- ' suspension isheated tic-8Q? C. while.’ stirring. kept '
zoyldiamino-5,lo-anthrapyriniidone
7 ' (obtainable atthe 'said temperature for from 3 to 4 hours, 30
,
from 55 ‘amino - 1.4 - dibenzoyldiamihoanthraquiw heated‘ for'from im 2 hours at 9.0: ,c- and then -,
none) , the 4-benzoylam1nd-3-lncthy1-LQ-anthra allowed to cool. The chlorination product formed ' r
‘ and 8-benzoylamino-1.9>anthrapyrimidones‘
pyrimidone
.u
O
is ?l??ied off by suction-i It is a'yellow crystal.
l?fom'‘ l-aminoA-benzoylamino-ii
line powder which dissolves in concentrated, $1111..
" 'methylanthraquinone); ‘the 'acylaminoanthrapy
rimidones substituted in the acyl radical, such as
phuric‘ acid giving an ‘orange coloration and dyes,v
the chlorbenzoylaminog, nitrqbenzoylaminor. a1
~ kylbenzoylaminm, 'allgoxyben‘zpylaminog phenyl
cotton clear, powerful yellow shades entirely'fast
to chlorine and washin'g'from; a blue violet vat.
benzoylamino-fand jarylaminoanthrapyrimidones. '
45
ample diphenylethercarboxylic acids, diarylsul
phide, ‘ carboxylic ,acids, for example diphenyl
sulphidecarboxylic acids, the‘carboxy-lic acids of
anthraquinones benzanthrone, benzanthraqub
'l 50
Example‘ 3-6
To the aforesaid chlorination also acyl derivatives
of aminoanthrapyrimidones and‘; or,her acids. may ' 100 parts of 5-benzoylamino=1.Q-anthrapyrimi
besubjected, for example such as. re obtainable. 7 dine. are introduced, at from O“ to 5.“ C- while
by means of naphthoic acids, benzophenone.
ca_r—, stirring into. a'suspension‘of 100 parts of bromine
boxylic acid, diarylethercarboxylic acids, for ex- and 3' parts of iodine in 1000 parts of chlorsul
phonic, acid. , The whole is, heated to from 20° to
30° Grand kept at this temperature for about 2
hours; the reaction product is then worked up
by precipitation in water‘and ?ltration by suc-.
n'one's, acridones, anthraquinoneacridones, an? tion. The resulting bromination productjyields, '
orange dyeings, on cotton from a brown violetvat.
thraquinonethioxanthones, anthanthrones, allo
V
’ ms-naphthodianthrones. and the
v
5:5 hydrobenzoic acid.
56
Example 37
like or aliphatic
or ‘Cycloaliphatic ,carboxylic acids for example.
acetic acidyoxalic acid, succinic acid and hexa
OI 2-amin0-1-9-anthrapyrimidme are:
heated to. boiling; tor a. short time in- 2.00.- parts or '
nitrobenzene with 20 partsot meta-gehmrbenzoyr
Ezrample; 33"’
chloride. The meta-worbenzoyhz-aminoelizs
20c partsof 5-benzoylamino-li.Q-anthrapyrimiQ ‘ anthrapyrimidine formedis. ?ltered. on? from» the,
dine in 1000 partslotf trichlcrbenzene are heated cold reaction-mixture. I, , terms; yellow needles.
'
60 to 1409 ‘C. after the addition of; 5 parts-oi iodine dhsssglvesv in concentrated sulphuric. acid to give;
and are kept atthe said temperature i'or from; *1 yellow’ solution and dyes, cotton yellow shades, 60.
V 2 to 3 hour'srwhile leading in
from a brown vat.
,
chlorine. ‘The re-.
7 action mixture is, allowed to cool and, thejreaction
65
product’ which has, separated in. the; form of; or
ange red crystals is ?ltered, oiI try/‘suction. It;
dissolves in concentrated sulphuricacid giving; an
orange coloration and dyes vegetable ?bres clear,
powerful golden orange shades diver-y good fast- '
_ ness from a brown
70
violet vat.
.
'
.
Similarly‘ dyeing products
obtained by the:
of an, equivalent amount. or: 2-5-dichlQt-.
2.3-dich1or1, 3;;4-dich1_or or trichlorbenzoyl chloé
ride insteah of the.‘ 20 parts. of meta-'chlQrben-zoyl; .65.
chloride-1 By the when of, halosentoluie acid
¢h1°ride or halosenterephthalqyl;
amino-.LQ-anthrapyrimidine likewi
ride on. 2
products
The corresponding,chlorination product of 44 ' are obtained dyeing yellowv shades.
‘benrgoyalamino-l.Q-anthrapyIimidine gives green
yellow, 'dyeinga, that of. . 2-anthraquinouer?ecara
baminq?-phenyl-1.-9,-anthrapyrimidine. gives yep,
low dyeings as does
,75, benzoyl) -amino-l .VQFanthrapXrimidine.
.What we, claim is:_
>
- ~
>
r
70
1, A process ofanproducing- coloring matters,
which
'
'
V
'
comprises condensingv an, amlnoanthraa ‘
pyrimidine with an organic acylating agent.
2. A process of producing coloring matters,
Winch. comp?ses: condensing. an.
75;
a’
1 1'
2,040,857
pyrimidine with an organic carboxylic acid chlo
in which up to two hydrogen atoms are replaced’ I
by the group
.
,
>
.
'
ride.
3. A process of producing coloring matters,
which comprises condensing an aminoanthra
pyrimidine with an organic carboxylic acid chlo
ride in an inert organic, liquid diluent.
4. A process of producing coloring matters,
which comprises condensing an aminoanthra
pyrimidine with an organic carboxylic acid chlo
10 ride above 100° C. in an inert organic, liquid
5. A process of producing coloring matters,
which comprises condensing an aminoanthra
pyrimidine with an organic carboxylic acid chlo
15 ride above 100° C. in an inert organic, liquid dilu
diluent.
-
'
p0
in which R stands for the radical of a cyclic com
pound containing at least one ‘six-membered ring
to which may be attached further rings contain- '
ent in the presence of an acid binding agent.
6. A process of producing coloring matters,
which comprises condensing an aminoanthra
pyrimidine with an organic carboxylic acid chlo
20 ride above 100° C. in an inert organic, liquid dilu
ent in the presence of a tertiary base.
ing from ?ve to six members, which product
dissolvesrin concentrated sulphuric acid to give
yellow to red solutions and dye the vegetable
?bre greenish yellow to violet shades from violet
brown vats.
12. An anthrapyrimidine
derivative
corre
sponding to the formula:
_
H
'7. A process of producing coloring matters,
which comprises condensing an aminoanthra
pyrimidine with an organic 'carboxylic acid chlo
25 ride above 100° C. in an inert organic, liquid
diluent in the presence of pyridine.
I
8. An anthrapyrimidine to which an organic
radical is attached by means of an acylamino
'30
group which product dissolves in concentrated
30 sulphuric acid to give yellow to red solutions.
9. An anthrapyrimidine to which an organic
radical is attached by means of the group
0
_.1\|T_C_
Y
35
in which up to two hydrogen atoms are replaced
by the group
35
wherein Y stands for hydrogen or an alkyl group
which product dissolves in concentrated sulphuric
H
acid to give yellow to red solutions.
10. An anthrapyrimidine derivative correspond
40
ing to the formula:
in which R stand for an aromatic radical which
H
product dissolves in concentrated sulphuric acid
I
to give yellow to red solutions and dye the vege
table ?bre greenish yellow to violet shades from 45
violet brown vats.
l3._An anthrapyrimidine derivative corre-
/O\
if I?
45
40
/\
sponding to the formula:
50
50
in which up to two hydrogen atoms are replaced
by the group
¢o
—N——C—~R
55
i
in which Y stands for hydrogen or an alkyl group
and R for an organic radical which product dis
60
60
solves in concentrated sulphuric acid to give yel
low to red solutions and dye the vegetable ?bre
greenish yellow to violet shades from violet brown . in which up to two hydrogen atoms are replaced
by the group
vats.
11. An anthrapyrimidine derivative correspond
ing to the formula:
H
t
if}
70
A0
Y
75
70
in which Rstands for a radical of the benzene ~
,
series, which product dissolves in concentrated
sulphuric ‘acid to give yellow to red solutions and
dyethevegetable ?bre greenish yellow to orange
75
shades from violet brown vats.
e 12'
'
2,040,857
l4.‘ An anthrapyrimidine derivative -'corresponding to the formula:
‘ I
:
' 17.15111 anthrapyrimidine derivativewcorrel
"
sponding to theeformulaze
7H
5
t
'
a
V
'
.
y
t
‘Y
' '
~
,
'
—N—C€R
'
n
r
.,
5:
~.
Y
i“ T
< 110
in which upto two hydrogen atoms are replaced
r
by the group.
w
.
e :-
20 in which R stands for a benzenerradical substi-
'
_
1_;_
' in which up to two hydrogen atoms are replaced
15 by‘ the. group
’
If.’
l
H
10
r.:'
'
I
‘e
15
'-'—%;—C:R
in Which R Stands for?’ m-chlorbenzene radical’ > 20
uted by a substituent selected from the group
consisting of halogen, cyano, nitro, alkyl, alkoxy,
phenyl, amino and Substituted amino groups,
Whlch product dissolves ‘in concentrated 5111.
phurie acid-t9 give yellow to red 501111110115‘ and '
dye the vegetable ?breigreenish yellowrto orange
which product dissolves in concentrated sulphuric
Shades from Violet brown Vats-
25 acid to give yellow to red solutions and dye the
vegetable'?bre greenish yellow to orange shades
from violet brown vats.
15. An
sponding '50 theformula:
V
anthrapyrimidine
V
.
.
‘13'; All" 'anthrapyrimidin‘ei derivative
.
'~
'
correr 25v
a
‘ '
'
derivative
corre
sponding to the formula:
30
30
i
O\ .
as
'35
iniwhi'ch’up to two hydrogen atoms are replaced >
(')>
40.
bythegroup‘
_
,
2
m WhlCh up to two hydrogen atoms are replaced
by the group
:
.
up
.
.'
> >
V
Y
e
‘
f
..
,
_
O.
' _N_OfR -'
a’
w
'
r I
~
V
?,
40
I
a
o
. _
in which R stands for a 2.5-dichlorbenzene radi
7
~
‘ '
phuric acid to give yellow to red solutions and
anthrapyrimidine
derivative
dye the vegetable ?bre greenish yellow to orange
shades from violet brown vats. '
19. An anthrapyrimidine derivative corre
sponding to the formula:
'
corre-
‘e
"
V
t
'
V ' sponding to the formula:
V
._
__
“
_
V
"
‘
,
x
l'
’
‘ (g
r
V
7
V
If
‘
Z
V '
/
N
\
NV
|
C\ V
A
|
r
Z_
Z
~Z_
oz
'
55
7
“
\H/
V :7 r .
0
' 'e '
V
>
i
'~
7 G5- in which up to two hydrogen atoms are replaced
7
‘
V
“N_O_R '
in'wh-iclr R stands fora p-chlorben'z'ene radical,
'which" product dissolves ‘in ‘concentrated . sul
50
.
'
55
by the group
.v
a
yellow to orange shades from violet brown vats.
V
‘
.
—N—c-R
50 solutions and dye the vegetable ?bre greenish
_ '70
. g
,
,
in ‘which R stands for a benzene radical 'substltuted by chlorine, which product dissolves in'con-, centrated sulphuric acid to give yellow to ,red
6O
"by
%
cal, which product dissolves in concentrated sul- 45
H
16. An
>
to
H
V
.3
>‘
"
in whichX stands 'for' hydrogen or an alkyl-groupy
at most two Zv’s for the acylamino ‘group
‘
V
l
V
V
l
)5
'
-
-
j
a 75 shades from violet brown ‘vats.
'
65
—N——C/—R
in which R stands for an aromatic radical and
wherein up to two of the remaining Z’s may be 70
halogen, the other Z’s being hydrogen, which
product dissolves'in concentrated’ sulphuric acid
phuric‘ acid to'give yellow to red solutions and dye ‘ to give yellow to red solutions and dye the vege
the vegetable ?bre greenish yellow‘ to orange
'60
table ?bre g’l‘eBm'Sh yellow ‘00 orangevshades from
violet brown vats.
51-3
-' '20; An anthrapyrimidine' derivative ‘corre
spondingto the rormulaz'
‘
'
table'?bre greenish yellow to orange shades 'from
violet
brown
vats.
‘
‘a
._
.
»
,
‘
23.,An anthrapyrim1dine derivative corre
'
sponding to the formula:
10
in which X stands for hydrogen or an alkyl group,
at most two Z’s for the acylamino group
in which X stands for hydrogen or an alkyl group,
15
at most two Z’s for the'acylamino group
0
%
—--III—--C—R
in which R stands for a radical of vtlrie‘benzene
20 series, and wherein up to'_ two of the remaining
Z’s may be halogen, the other Z’s being hydrogen,
which product ‘dissolves in concentratedlsulphuric
.
v
.
H
V
20,
V
in which R stands {for a p-chlorbenzene radical,
and wherein up to two‘of the remaining Z’s may 7
be halogen, the other Z’sbeing hydrogen in con
acid to give yellow to red solutions and dye the . centrated'sulphuric acid‘ to give yellow ‘to redso
vegetable ?bre greenish yellow to orange shades lutions' and. dye the vegetable ‘?bre greenish'yelé,
from violet brown vats. ‘i
low to orange shades from violet brown vats.
derivative corre
> 21. An anthrapyrimidin
24. An anthrapyrirni‘dine derivative corre
sponding to the formulazf
sponding to the iormulaz‘q:
135
in which X stands for hydrogen or an alkyl group; _
‘at most two Z’s for the acylamino group
40
H ‘_:
in which R stands for a benzene’ radical which is
substituted by halogen or a cyano group, and
wherein upmto-two'oi the‘ remaining/21s may be
halogen, -lt_he other as ‘being hydrogen“ in con
centrated ‘sulphuric acid to give yellow to red
solutions and dye the vegetable fibre-greenish
yellow to orange shades from violet brown vats.
22. An anthrapyrimidine derivative corre
’
in which R stands for arm-chlorbenzene radical,
and wherein up to two of-the remaining Z’s may
be halogen, the other _;>Z’s being hydrogen in con
centrated sulphuric/acid’ to/give yellow to red,
yellow
solutions
to. orange
and dye
shades'from‘
the ,vegetable
violet ?bre
browngreenish
vats.
25. An anthrapyrimidine derivative corre
sponding to the?ormula:
spending to the, iorrnula:
60
in which X stands for hydrogen or an alkyl group,
in which X stands for hydrogen or an alkyl group,
65
at most two Z’sii’orthe apylamino group
at most two Z’s for the 'acylamino group
'
r
O
0
I
70
‘in’ which? 'R3 stands‘ ‘for a ‘benzene’ lradical" ‘substi
tuted by; chlorine‘, and wherein up't'otwo ofiithe
remaining :Z’s 'may ‘be Lhalogen, the other i‘éz’s
being hydrogenlini concentrated sulphuric acid
to give yellow to red solutions 'anddyefthe vege
Hi
.
in which R stands for a 2.5lf-dichlorbenzene radi
cal, and wherein up to two of the remaining Z’s
may be halogen, the other. Z’s being hydrogen in
concentrated sulphuric acid to give yellow to red
solutionsrand dye the vegetable fibre greenish yel
low to "orange shades from violet brown vats.
50
2,0493 57
1 26.; An anthrapyrimidine derivative correspond
ing to the formula:
~
> i Z
substituted by chlorine,‘ which products dissolve in
concentrated sulphuric acid to givevyellqwétosred‘
solutions and dye the vegetable ?bre greenish yel
low to orange shades from violet brown vats.
30. The anthrapyrimidine derivative corre
' sponding to the formula:
| ..
" 6
10
‘ in which a hydrogen atom in one of the alpha?
positions is replaced by the acylamino group
'
r
,
o
7
-
'15
_.1;I._QZR ' '
t
'
'20
a
‘
,
wherein R is .an aromatic radical, which products
dissolve in concentrated ‘sulphuric acid to give
yellow to red solutions’ and dye the vegetable
a yellow solution and dyeing cotton from‘a violet
?bre greenish yellow to violet shades from violet
brown vat yellow "shades.
brown vats.
>
'
‘ 27, An anthrapyrimidinederivative correspond
2.5
ing tothe formulas‘
'
‘.
-
'
'.
dissolving in concentrated sulphuric acid'to give
- .0
' " ‘
=31.- An .authrapyrimidine - derivative _' corre
sponding tocthe to mula:
r
L 2.5
\N a
[30'
35
in which R stands for an aromatic radical, which
products dissolve in concentrated sulphuric acid
'
4
0
'
iiofgive yellow to red 2solutions. and dye the
vegetable ?bre greenish; yellow'to violet shades
7 'from violet brown vats.
28. 'An anthrapyrimidine derivative corre
sponding to the formula? 1 -
45_
.
7
in which R stands 101' a benzene radical Vwhich'is
substituted by halogen or a cyano group, dissolv
ing in concentrated sulphuric acid to give a yellow
solution and ‘ dyeing cotton-1mm a violet ' brown
vat
yellowg?hades.
.
>
‘
‘
'
32. The anthrapyriinidine derivative “66m:
sponding to the formula: _V
E7\
N/ \N
v’ iicilf
50
a
/
o
u-c'f-a
-
a
dissolving in concentrated sulphuric acid‘ to ‘give
55
in which R stands for a benzene radical which
is substituted by halogen or a cyano group, which
a yellow solution anddyeing cotton from a violet
brown vat yellow shades.
38. An anthrapynmidine derivative corre
products dissolve in concentrated sulphuric acid 7
to give yellow to red‘ solutions and dye the sponding to the forinula:
_vegetable ?bre greenish yellow to orange shades
' from violet brown vats.
' 29. An anthrapyrimidine derivative correspond
ing tothe formula: '
765'
70
lit
570
in which}; stands for a benzencradicaiwhich is
substituted by halogen or a cyano'group, dissolv
ing in concentrated sulphuric acid to. give a yel
75 in which R stands for a benzene radical which is
low solution and dyeing cotton from " a violet
brown vat yellow shades.
v
.
a
7'
2,040,857
34. An anthrapyrimidine
sponding to the formula:
derivative
corre-
15
35. The anthrapyrimidine derivative corre
sponding to the formula:
H
H
\
5
\
N/ \N
N/ \N
10
01
5
1°
01
in which R stands for a. benzene radical which
is Substituted by chlorine, dissolving in concem
trated sulphuric acid to give a yellow solution
and dyeing cotton from a. violet brown vat yel10w shades.
I _
dissolving in concentrated s‘?phuric acid to give 15
a. yellow solution and dyeing cotton from a. violet
brown vat yellow Shades'
MAX ALBERT KUNZ.
KARL KOEBERLE.