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Патент USA US2136133

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2,136,133
Patented Nov. 8, 1938
UNITED STATES‘ PATENT
OFFICE
2,136,133‘ _
PYRAZO-LE-ANTHRONES AND PROCESS OF
.
MAKING SAME
Hermann- Hauser, Binningen, and Max Bummer,
Riehen, Switzerland, assignors to the ?rm So
ciety of Chemical Industry in Basle, Basel.
Switzerland '
No Drawing. Application January 21, 1937, Se
rial No. 121,710. In Switzerland February '7,
1936
7 Claims. (Cl. 260—312)
This invention relates to the manufacture of
pyrazole-anthrones by causing an anthraqui
none or a leuco-compound thereof, which con
5 .
l0.
tains in oc-DOSltiOIl a substituent capable of being
exchanged, to reactwith a hydrazine of the gen
eral formula H2N--NH--CH2——X wherein X indi
cates hydrogen, alkyl, aralkyl or aryl, and, if de
sired, treating the product thus obtained with an
agent for introducing 'substituents and/or a con
densing agent.
.
~
-
Suitable anthraquinones or their leuco-com
pounds containing in oc-IJOSltiOIl a substituent
capable of being exchanged are, for example, or
halogen-, a-amino-, a-hydroxya and a-alkoxy
15:
and containing a halogen atom may be caused to
react with primary and secondary aliphatic and
aromatic amines, for example alkylamines, am
inobenzenes, amino-naphthalenes and amino
anthraquinones.
The anthrimides obtainable
with amino-anthraquinones can be converted into
products containing the carbazole ring, for ex
ample'by the action of sulfuric acid or aluminium.
chloride in combination with alkali chlorides or
pyridine.
10
.
The products may also be treated with an alde
hyde, for instance formaldehyde or an halogen
H2N—-NI-I-—-CH2-—X wherein X indicates hydro
ating agent whereby further valuable products are 15
obtained.
The products may also be puri?ed by crystalli
zation or by conversion into their salts formed
from‘strong acids, or by treatment'with alkali
hypochlorite solution. They may also be con 20
verted by known methods into the leuco-deriva
tives, for example into the leuco-sulfuric acid
hydrazine, ethyl hydrazine,_benzyl hydrazine and
esters.
The products of the invention are in part val-,
anthraquinones
and their, leuco-compounds.
These may contain further substituents, for in
stance alkyl-r, nitro-, alkoxy- or, amino-groups,
as well as halogens, for example chlorine; or
bromine.
20.
instance by means of air or a perborate; further
more, the products obtainable by the invention
‘
_
Suitable hydrazines of the general formula
gen, alkyl, aralkyl or aryl, are forexample methyl
sulfates thereof. These benzyl hydrazines may
25. carry substituents in the phenyl radical, for ex
ample, halogen, nitro-groups, alkoxy-' and alkyl
groups.
The reaction of the anthraquinone or its leuco
compounds with the hydrazine occurs at a raised
30 temperature, preferably in the presence of a
solvent or diluent, such as pyridine or amyl alco
hol, as well as in the presence of a substance which
facilitates the reaction, for instance an alkali
carbonate.
.
'
The products obtainable by the invention may
be treated with an agent introducing substitu
ents and/or a condensing agent. For example,
those pyrazole-anthrones which contain an am
ino-group in the anthrone radical, if necessary
40 besides other substituents, may be mono- or
di'alkylated (CH3, CzI-Isand the like) or arylated.
Further, these amino-groups may also be acidyl
ated, whereby radicals of aliphatic or aromatic
carboxylic acids, for instance the radicals of
45 acetic acid, propionic acid, benzoic acids, naph
351
thoic acids and anthraquinone carboxylic acids,
can be introduced. For example also the product
obtained by reaction of 5-amino-l-chloranthra
quinone with methylhydrazine may be treated
an acylating agent, such as an anthraq'ui
50. with
none-Z-carboxylic acid halide .and an anthraqui
none-l-carboxylic acid halide, .or the product‘
formed. by the reaction of hydrazine with a leuco-‘
anthraquinone containing in . u-position .a' group
j capable of being exchanged may be oxidized, for
uable new intermediate products and in part 25
dyestu?s. The latter can be used for dyeing and
printing vegetable ?bres, for instance cotton, or
for coloring lacquers and plastic masses, as well
as for ‘dyeing arti?cial silk.
The dyeings and
printings produced are very fast.
'
The following examples illustrate the invention,
the parts being by weight unless stated other
wise, and the parts by weight being related to the
parts by volume as is the kilo to the litre:—
35
Example 1
24 parts of l-chloranthraquinone, 18 parts of
an aqueous solution containing about 30 per cent.
of methyl hydrazine, 10 parts of calcined sodium
carbonate and 150 parts of pyridine are heated to
gether to boiling for 12 hours. The mass of the
formula
45
is ?ltered when cold and freed from inorganic 50
constituents by boiling it with Water. In this
manner the product is obtained in the form of
beautifully crystalline, yellow-needles which melt ,
at 188-189° C. In concentrated sulfuric acid it
dissolves to an orange solution. When the solu
2
2,136,133
tion is poured into water yellow ?ocks are ob
tained. In alcohol it dissolves to some extent to
a yellow solution of intensely green ?uorescence.
Example 2
13 parts of 1:5-aminochloranthraquinone, 18
parts of an aqueous methyl hydrazine?solution.
of about 30 per cent. strength, 5 parts of calcined
sodium carbonate and 150 parts of pyridine are
10 together heated to boiling for 170 hours. After
cooling, the new compound of the ‘formula
I|\|I—-‘1TI—CH!
separates in part in the form of small yellow
needles, while the mixture is still hot. When dry
it is a yellow powder which dissolves in concen
trated sulfuric acid to a red solution. In a
yellow-olive vat it dyes cotton very strong and
very pure yellow tints which are of very good
fastness to washing chlorine and bowking.
If the product of Example 3 is caused to react
with anthraquinone~2-carboxylic acid-chloride
vthere is obtained a dyestuff much greener than 10
that described above. In either case benzoyl
chloride may be used instead of the anthraqui
none-2-carboxylic acid-chloride, whereby com
pounds are obtained which are also of pure yellow
and crystallize very beautifully.
15
15
_
l
1
HzN
~
Example 6
.
0
~
which has separated in the‘form of orange crys?
3 parts. of the product obtained as described
in Example 2 are mixed with 3 parts of benzoyl
20 tals is ?ltered and washed with hot water. . It '
dissolves in concentrated sulfuric acid to an chloride and 120 parts of ortho-dichlorobenzene 20
orange solution and melts at '234-2'35° 0.‘
Example 3
'
'
'
26 parts of l:4-amino-chloranthraquinone, 20
and the mixture is heated for half~an-hour to
boiling. .The product of the reaction of the
formula
25 parts of an aqueous solution of about 30 per cent.
strength of methyl hydrazine, 300 parts of pyri
dine and 10 parts of calcined sodium-carbonate
are heated together to boiling for 10 hours. The
mass is then introduced into water and the prod
30 uct of reaction thus precipitated of the formula
W
85
is ?ltered. It dissolves in concentrated sulfuric
acid to a yellow solution having a green ?uores
cence, from which, on dilution with some water,
it is obtained in. the form of small needles.
The pyrazole-anthrones which are obtained
from 1z4-amino-chloranthraquinone and ethyl
hydrazine or benzylhydrazine behave analogously.
Example
4
r
.
7
12 parts of l-chlor-anthraquinone, 10 parts of
an aqueous methyl hydrazine solution of about 30
per cent. strength, 5 parts .of calcined ‘sodium
carbonate and 120 parts of amyl alcohol are
The
yellow product is ?ltered when cold and the
50 heated together to boiling for 10 hours.
—CO—NH
$1501 3
(g
~
25
30
which separates in the form of small yellow
needles dissolves in concentrated sulfuric acid 35
to a red solution. It cannot be vatted with
caustic soda solution and hydrosul?te. It may
be used as a varnish colour.’
Example 7
5 parts-of 5—amino~-1:19-(N-methyD-pyrazolan
throne-obtainable, for instance, as described in
Example 2, 5' parts of 2-chloranthraquinone, 120
parts of nitrobenzene,-10 parts of anhydrous so
dium acetate and 0.5 part of cupric ‘acetate are
mixed together and the mixture is heated to
boiling for 12 hours. The product of the reaction
of the formula
"
'
‘
I?I~l|\I-—CHa
50
solid matter washed with alcohol and hot water.
By recrystallization from about '5 times its weight
of pyridine the washed product is obtained in a
It is
identical with the product obtained as described
55 puri?ed form and melts at 188—-189° C.
in Example 1.
‘
55
'
Example 5
60
3 parts of the product obtained as described
in Example 2, 4 parts of anthraquinone-Z-car
boxylic acid chloride and 120 parts of ortho
dichlorobenzene are together heated to boiling
for about 1 hour. The product of the formula
65
70
if
I!“
@V.
Ac O-HN‘l
7
is ?ltered When the mass is cold. It dissolves in 60
concentrated sulfuric» acid to an olive-green solu
tion from which, when poured into» water, red
?ocks precipitate. The vat prepared from this
dyestuff dyes cotton Bordeaux red. The dyeings
show very good fastness to washing.
65
Example 8
3 parts of 4.-amino-1:9-(N-methyl)-pyrazol
anthrone of melting point 236—237° (3., which 70
may be obtained for instance by recrystallizing
from pyridine the product obtained as described
in Example 3, are mixed with 4 parts of an
75
thraquinone-2-carboxylic acid chloride and 120
parts of ortho-dichlorobenzene and the mixture 75
53
is heated to boiling for‘half-an-‘hour'; The prod-I
not of the formula
'
N——N-—CHa
obtained which, however, are of weaker color
with the exception of the dyestu? from 5-amino
@900
10
I If one uses instead of 1:2-chloranthraquinon'e
carboxylic acid the 2:3-chloranthraquinone-car
boxylic acid for the acylation similar dyestuffs are
1:9-(N-methyl) -pyrazolanthrone and 2:3-Chlo
ranthraquinone-carboxy1ic acid-chloride which
dyes cotton in a red-brown vat strong and pure
greenish-yellow. The properties of fastness are
good.
10
'
Example 11
36 parts of 1:4-chlorobenzoylamino-anthra
quinone, 15 parts of an aqueous solution of methyl
which separates in the form;v of; small yellow;
needles is ?ltered cold, It dyes cotton in a'yellowr
olive vat strong greenish-yellow tints, ;§I?he,_dye.
ings show very goodiastnessto chlorine, wash
ing and kier-boiling.
Example .9 “
4 parts of 8-amino-1z9-(N-methyl)-'pyrazol-i
20
hydrazine containing about 5 parts of methyl
hydrazine and 15 parts of anhydrous sodium
acetate, are added to 360 parts of pyridine and
the whole is heated to boiling for 10 hours.-_.
When the mass is cold the product of the vre}
action of the formula
’
V
.
.20
~
anthrone of melting point 230“ C.,-which' may
be obtained, for. instance, by the reaction of 1:8
amino-chloranthraquinone with methyl ~hydra-"
25
26 zine as described in Example 2, are‘ mixed ‘with 5?
parts of anthraquinone-2~carboxylic a'cid-chlo'-*
80
ride and 160 parts‘of trichloro-benzene and the
mixture is heated to boiling'for half-ah-hour;
The product of the formula,
is separated by ?ltration and freed from in
organic constituents by extraction with boiling
30
water. It is a bright yellow-green crystalline
powder which,’ after one recrystallization from
pyridine melts at 299-301° C.
>
‘
Bysapo-nifying it with sulfuric acid of 90 per
cent. strength’ at‘ 90-95“ C. there is obtained 4 35
amino-l : 9- (N-methyl) '-pyrazolanthrone which
is identical withv the product of the ‘reaction’ of
1:4—amino-chloranthraquinone with methyl hy
drazine described in Example 3. It, dyes acetate;
which separates in the form ofv pure. yellow
silk very strong and pure greenish-yellow tints. 40
40 needles dyes cotton in an olive-green vat strong
and pure greenish-yellow. The dyeings show
good fastness to chlorine, washing and kier
boiling.
4.5
.
V
Example 10
5 parts of the 5-amino-lz9-(N-methyl) -pyra
zolanthrone described in Example 2, vare mixed
with 4 parts of 1-chloro-2-anthraquinone-car
boxylic acid-chloride and 120 parts of trichloro
50 benzene and the mixture ‘is heated for half-an
hour at 170-180” C. The product‘ ‘of the reaction
of the formula
'
‘I
,
Example 12
~
37 parts of 1:3_-dibromanthraquinone, 20 parts
of an aqueous methyl hydrazine solution of about
30 per cent. strength and 15 parts of sodium 45
acetate are mixed with 185 parts of pyridine
and the mixture is heated ‘to boiling for 10 hours.
The product crystallizes from the cold mass in
the form of yellow tables. It melts at 249-250°
C. and is the 1:9-(N-methyl)-pyrazol-3-brom- 50
anthrnve oi the formula .
'
~
N——-N——CH3
OW
'
55
55
By reaction with l-aminoanthraquinone in
nitrobenzene and in presence of an agent which 60
eliminates hydrogen halide, there is obtained
from this body a vat-dyestuff which dyes cotton
orange.
65 separates from the cooling'mass and is ?ltered.
It dissolves in- concentrated sulfuric acid to a
red solution; when this solution is ‘introduced in
to water yellow ?ocks separate? The dyestu?
dyes cotton yellow in a vat. The dyeings show
70 good fastness to chlorine, washing, kier-boiling
and light.
If instead of '5-amino-1z9-(N-methyl)—pyra
zolanthrone there is used the 4‘ or BVamino-de
rivative, similar dyestu?svare ‘obtained; they dye
75
cotton very pure yellow.
-
1' l
-
..
Example 13
65
22.3 parts of l-aminoanthraquinone, 25 parts
of isophthalic acid-chloride and 300 parts of
ortho-diéhlorobenzehe are mixed together and
the mixture is heated for half-an-hour to boiling.
The mass, is stirred when cold and the product 70
of the reaction is isolated by ?ltration. 4 parts
of this product are mixed with 2.5 parts of 5
amino - 1:9 - (N - methyl) -pyrazolanthrone
ob‘
tained, for ‘instance as described in Example 2,-;
and: 150‘ parts of ortho-dichlorobenzene, and :the 75
4
2,136,138
mixture is heated for half-an-hour to boiling.
The new dyestuff is isolated by cooling. and ?l
tration. It is of the formula
at 180~190° C. The new dyestuff of the formula
N————N—-CH3
@153 ‘i
1.0
10
is ?ltered from the cold mixture. It dissolves in
15
concentrated sulfuric acid to an orange solution.
Cotton is dyed in a yellow-olive vat greenish
15
yellow tints.
Example 16
Cotton is dyed pure yellow tints both without
soaping and after soaping.
The dyeings show
20 ‘ very good fastness to chlorine, washing and kier
boiling, and are characterized by the remarkable
preservation of the ?ber on exposure to light,
which indeed is essentially better than the cot
ton dyeing obtainable by means of 1:5-dibenzoyl
2
diaminoanthraquinone.
.
mixed, together and the mixture is heated for
halt-an-hour to boiling; the product is ?ltered
when cold. It melts at 254-256? C. and dissolves
in concentrated sulfuric acid to an orange solu
tion, which, when poured into water, yields yel
Example 14
3
5 parts of 4-amino-lz9-(N-methyl)-pyrazol
anthrone and 50 parts of acetic anhydride are 20.
57 parts of l-chloranthraquinone-2-carboxylic
25
low ?ocks. It dyes acetate silk very strong and
pure greenish-yellow tints. This dyestuff is the
acetyl derivative of the formula
acid and 25 parts of ‘calcined sodium carbonate
30.
are mixed with 626 parts of an aqueous solution
of methyl hydrazine made, for example, by dis
solving 32 parts of methyl hydrazine in 570 parts
9.5
40
of water and adding 24 parts of caustic alkali,
‘ the mixture is heated for 18 hours to boiling, then
?ltered hot and from the ?ltrate the product is
isolated by acidifying with hydrochloric acid. By
recrystallization from 6 times its weight of pyri
dine the product of the formula
35
Example 17
2.5 parts of 5-amino-1z9-(N-methyl) -pyrazo
lanthrone, 4 parts of an acid-chloride of the for
mum
* ‘6 ‘BO
45.
0
@Q ~
is obtained in the form of small yellow needles
5,0 which melt above 300° C.
In concentrated sul
furic acid the product dissolves to a pure orange
solution.
stu?s.
It may be used for making vat-dye
2.6 parts of 4-amino-1:9-(N-methyl) -pyrazol
anthrone and 3.8 parts of a compound of the
formula
@jijgcom
(I)
65
:T
thraquinone with para-hydroxybenzoic acid in
amyl alcohol and in presence of potassium car
Example 15
55
(this compound melts at 1.68—l70° C.; it may be
made for instance by the reaction of l-chloran
bonate and subsequent action of phosphorous
pentachloride) and ‘120 parts of ortho-dichloro 55
benzene are mixed. together and the mixture is
heated for vhalf-an-hour to boiling. The product
of the reaction of the formula
., V
(H)
oo~
(which can for instance be made by condensa
tion of anthraquinone-2-carboxylic acid-chloride
with toluene, oxidation of the methyl group to
70 the carboxyl group by means of chlorine in nitro
benzene at 160-1’70° C., and ?nally the conversion
of the carboxylic ‘acid into the above acid-chlo
ride by means of phosphorous penta-chloride.)
are :mixed with 150 parts of ortho-dichlorobene
76 ' zene and the mixture is heated for half-an-hour
III
C00
|
o
when dry is a yellow crystalline powder. It may
be vatted at 40-50° C. and dyes cotton at 25_—30° C.
strong and pure yellow.
75
2,136,133
What we claim is:-
1. Process for the manufacture of pyrazole
anthrones, consisting in causing anthraquinones
which contain in a-position substituents capable
of being exchanged, to react with hydrazines of
the general formula H2N--NH—CH2X wherein X
wherein A is an anthraquinonyl radical.
6. Monopyrazole-anthrones of the formula
is a member of the group consisting of hydrogen,
alkyl, aralkyl and aryl.
2. Process for the manufacture of pyrazole
10
10 anthrones, consisting in causing anthraquinones
which are substituted in u-position by halogen,
to react with hydrazines of the general formula
H2N--NH-CH2X wherein X is a member of the
group consisting of hydrogen, alkyl, aralkyl and
15
wherein A is an anthraquinonyl radical.
7. Monopyrazole-anthrone of the formula
15
aryl.
3. Process for the manufacture of pyrazole
anthrones, consisting in causing anthraquinones
which are substituted in a-position by halogen, to
react with methyl hydrazine of the formula
20
H2N—NH——CH3.
20
.
4. Process for the manufacture of pyrazole
anthrones, consisting in causing 1-ch1oro-5
amino-anthraquinone to react with methyl hy
drazine of the formula H2N——NI-I—-CH3.
5. Monopyrazole-anthrones of the formula
25
HERMAN N HAUSER.
MAX BOMMER.
30
30
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