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Патент USA US2132829

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Patented Oct. 11, 1938
2,132,829 ,
_, UNITED STATES PATENT OFFICE
' 2,132,829
, DYEST’UFFS
THE‘ ANTHRAQUINONE
‘ OFv
NAPHTHACRIDONE SERIES AND PROCESS
OF MAKING SAME
Wilhelm Moscr, Riehen, near Basel, and Walter
Fioroni, Binningen, near Basel, Switzerland,
assignors to the ?rm of Society of Chemical
(in
v is
Industry in Basle, Basel, Switzerland
3
‘
No Drawing. Application January 9, 1937, Serial
No. 119,888. In Switz erland January 10, 1936
( Cl. 260-276)
The compounds which contain at least once
This invention relates to the manufacture of the atom grouping
new dyestu?s of theanthraquinone naphthacri
done series by, treating with a condensing agent
an anthraquinone derivative which has at least 1
{'5 mol of the atom grouping
1 Claim.
10
T20
in which the one a: stands for hydrogen and the
have not yet been described. They may be ob
other :10 for‘ a COOR-group, OR. ‘being OH, 0'
tained by the known analogous processes, for ex
ample by condensing an aminoanthraquinone
alkyl or halogen. The new anthraquinonenaph
thacridones thus produced contain at least once
the atom grouping
20
with an a-chlornaphthalene, the parent materials
being so chosen that one of them contains in the
[ii-position adjacent to the u-position a COOR
group (R representing H or alkyl).
25
Such compounds are, for example, the con
densation products from l-aminoanthraquinone
Z-carboxylic acid ethyl ester and a-chloronaph
thalene; 1 mol 1:4-diaminoanthraquinone and 2 30
mol 1-ch1oronaphthalene-2 -carboxylic acid ethyl
ester ; 1 mol 1:5-diaminoanthraquinone and 2
mol 1-ch1oro-naphthalene~2-carboxylic acid ethyl
ester; 1 mol 1-amino-4~benzoy1aminoanthraqui
none and 1 mol 1-chloronaphthalene-2-carbox
and are valuable dyestuffs or intermediate prod
ucts for obtaining dyestuffs.’ These dyestuffs rep
resent therefore the N-a:a'-anthraquinonenaph
O thacridones. The new dyestuffs are distinguished
from the comparablevnaphthacridone dyestuffs
by valuable properties,particularly by their level—
ling capacity. They are dark powders dissolving
45 in sulfuric acid to orange, to browmto olive and
black-blue solutions, yielding with ' hydrosul?te
and caustic soda solution, brown to‘ brown-red,
violet-red and Bordeaux red vats, and dyeing the
vegetable ?ber Bordeaux red to violet; to green,
to grey and brown tints.
'
'
35
ylic acid ethyl ester; 1 mol 1-amino-5-benzoyla
minoanthraquinone and 1 mol l-chloronaphtha
lene-Z-carboxylic acid ethyl ester; the conden
sation product from 1 mol 1 :4-dich1oronaphtha
lene and 2 mol l-aminoanthraquinone-Z-carbox
ylic acid ethyl ester; the condensation product
from 1 mol 4:4’-diamino-1 :1'-dianthraquinonyl-
,
amine and 2 mol 1-chloronaphthalene-2-carboX
ylic acid.
As condensing agents capable of converting the
above compounds into acridone derivatives there
come into question those which are used for simi
lar reactions provided that they do not simul
taneously have a sulio-nating action. Such agents
45
or processes are, for example, the treatment with 60
2
2,132,829
reducing agents in the presence of alkalies, for
instance vatting (if :1: stands for a COOH-group
or a COO-alkyl group); agents which convert
the COOR-group into the CO-halogen group and
then close the ring; agents which withdraw water
or the like.
The new acridone derivatives which contain
reactive groups may further be condensed with
certain compounds, for instance the new acridone
10 derivative of the formula
15
Example 1
39.3 parts of 1-a-naphthylaminoanthraquinone
Z-carboxylic acid are introduced into a mixture of
400 parts of toluene and 13 parts of thionyl chlo
ride. The mixture is heated to 50° C. and kept
for 1 hour at 50-52° C., then heated under re?ux
and kept thus for 1A1 hour. The Whole is then
?ltered hot, the solid matter washed with toluene,
alcohol and water and treated after separation
of the undecomposed carboxylic acid with dilute 10
caustic soda solution, then Washed with hot water
until neutral and dried. The dyestuffs thus ob
tained, which may be regarded as anthraquinone
2:2’: 1: 1'-naphthacridone of the formula
15
20
21
Y
25
O
20
NH:
will react with compounds having reactive halo
30 gen atoms, for instance a-chloranthraquinones.
The anthrimides thus obtained may then under
go further reactions which are characteristic of
H../
r | l
AO/
25
O
Y
30
0
the anthrimides, for example they may be sub
jected to carbazolation. In spite of the presence
35
of the carbazol ring the dyestuffs thus obtained
belong to the N-a:u’~anthraquinonenaphthacri
done. Particularly valuable among the N-meu
anthraquinonenaphthacridones are quite gener
ally those which correspond to the general for
40 mula
may be crystallized from nitrobenzene in crystals
of Bordeaux colour which dye cotton Bordeaux 35
in a violet vat. The solution in sulfuric acid is
orange and when poured into water yields Bor
deaux colored ?ocks. ,
The 1 - a -naphthylaminoanthraquinone- 2 -car
boxylic acid may be prepared as follows:
44 parts of 1-aminoanthraquinone-2-carboxylic
45
@Y)1
50
z
0
z
in which one :1: stands for a hydrogen atom and
the other :1: stands for a NI-I-y group, wherein 11
55 represents a radical selected from the group of
radicals consisting of aroyl radicals, anthraqui
nonyl radicals and the carbazolanthraquinonyl
radicals deriving therefrom, which products are
dark powders, dissolving in sulfuric acid to
orange, to brown, to olive and black-blue solu
tions, yielding with hydrosul?te and caustic soda
solution brown to brown-red, violet-red and Bor
deaux red vats, and dyeing the vegetable ?ber
Bordeaux red to violet, to green, to grey and
65 brown tints.
The new acridone derivatives may be halogen
ated, nitrated and subsequently reduced and if
desired acylated, new dyestuffs being obtained.
Acridone clerivatives'may be produced which in
addition to the acridone grouping here charac~
terized contain other acridone groupings. ,
The following examples illustrate the inven
tion, the parts being by weight; the ratio of parts
by weight to parts by volume is that which exists
75 between the kilo and the litre:
40
acid ethyl ester, 24 parts of anhydrous sodium
carbonate, 1.5 parts of anhydrous cupric chloride
and 125 parts of l-chloronaphthalene are together
boiled under re?ux for 4 hours; the mass is then 45
distilled with steam, the residue ?ltered, the solid
matter washed neutral with hot water, treated
with hydrochloric acid, again washed until neu
tral and ?nally dried. The l-a-napthylamino
anthraquinone-2-carboxylic acid ethyl ester is a 50
dark violet powder soluble in sulfuric acid to an
olive solution which on dilution with water yields
red-brown ?ocks.
42 parts of 1-a-naphthylaminoanthraquinone
2-carboxylic acid ethyl ester are heated to boiling 55
with 600 parts of alcohol and 15 parts of 30 per
cent. sodium hydroxide solution for 1 hour under
re?ux and then ?ltered hot. The ?ltrate is di
luted with water and the alcohol distilled. The
solution is ?ltered from a little residue, the ?ltrate 60
is acidi?ed with hydrochloric acid and ?ltered;
the solid matter is washed neutral and dried.
The crude 1-a-naphthylaminoanthraquinone-Z
carboxylic acid thus obtained may be puri?ed, for
example by extraction with alcohol. It behaves 65
towards sulfuric acid as does the ester.
Example 2
10 parts of 1-(a1-naphthylamino-[n-carboxylic
acid ethyl ester) -4-benzoylaminoanthraquinone 70
ground wet are vatted in 600 parts of Water by
means of 30 parts of sodium hydroxide solution
of 30 per cent. strength and 15 parts of sodium
hydrosul?te for 1 hour at 65-70° C.; the mass is
?ltered, the ?ltrate oxidized by blowing in air 75
v3
2,132,829
and again ?ltered; the solid matter is washed
neutral and dried. The dyestuff thus obtained
ter is ?ltered, washed and dried.‘ There is ob
tained the diacridone of the probable formula
is a bi-benzoylamino-l-a-naphthanthraquinone
acridone of the formula
.
I)
10
H
0
ll
15
)0l
EN
10
I
1/0/\[j/
0
,
O
/
0:0
(3:0
l
I
15
l
N
I.
H
.
20
It is a dark powder which dyes cotton very fast
and level greenish gray in a violet red vat, the
sulfuric acid solution is orange and when poured
into water yields green-gray ?ocks.
sponding 4- (4’-chloro) -benzoylaminoanthraqui
none or 4- (3'-methoxy) -benzoylaminoanthraqui
none derivatives instead of the 1-(u1-1-lfl2tphthY1
amino-pi-carboxylic acid-ethyl ester) -¢l-benzoyl
30 aminoanthraquinone, or exchanging the aroyl
radicals of the benzene series for other acyl radi
cals, such as those of the phenoxy-acetic acid or
of the iurane carboxylic acid.
The 1-(a1-naphthylamino-?1-carboxylic acid
35 ethyl ester) -4=-benzoylaminoanthraquinone may
be made as follows:
U: w
Similar
25 products are obtained when using the corre
v
34.2 parts of 1-amino-4-benzoylaminoanthra
quinone, 23.4 parts of l-chloronaphthalene-Z
in the form of a bluish gray powder which yields
25
a violet vat dyeing cotton av very fast gray. The
solution in sulfuric acid is orange and when
poured into water yields violet gray ?ocks.
The 1:5-(di-ou-naphthylamino - [31 - carboxylic
acid ethyl ester)-anthraquinone may be made
as follows:—
~30
‘
A mixture of 23.8 parts of 1:5-diaminoanthra
quinone, 47 parts of l1-chloronaphthalene-2-car
boxylic acid ethyl ester, 24 parts of anhydrous 35
sodium carbonate and 1 part of anhydrous cupric
chloride is added to 200 parts of nitrobenzene
and the whole is boiled for 20 hours under reflux.
The operation of working up‘ is the same as that
carboxylic acid ethyl ester, 12 parts of anhydrous . described in Example 2. The- crystallized red
sodium carbonate and 0.6 part of anhydrous body dissolves in sulfuric acid to an olive solu
cupric chloride are mixed together in 240 parts
tion and‘ is precipitated therefrom by water in
of nitrobenzene and the mixture is boiled for 20
hours under re?ux. When the mixture is cooled
it is ?ltered and the solid matter is washed with
a little nitrobenzene, then with toluene and alco
a yellow red form.
‘
‘
Example 4,
10 parts of the compound of the formula
45
hol and ?nally with water and then treated with
hydrochloric acid, washed neutral and dried.
The crystalline blue body thus obtained is a
acid ethyl
ester)-4—benzoylaminoanthraquinone. It dis
- 1- (ou-naphthylamino—;31ecarboxylic
solves to an olive brown solution in sulfuric acid;
when this solution is poured into water yellow
brown ?ocks are produced.
T h e 4 - benzoylamino- a : a ' - naphthanthraqui
noneacridone can also be produced by condensing
the 1-(a1~naphthylamino-?1-carboxylic acid) -4
benzoylaminoanthraquinone as indicated in Ex
ample 1.
An isomeric 5-benzoylamino-otzw-naphthan
60 thraquinoneacridone which dyes brown tints from
t rr
A0 000cm
O
H
l
60
a violet vat can be obtained from 1-amino-5
benzoylaminoanthraquinone.
Example 3
10
parts
of
l:5-(di-ai-naphthylamino-pl-car
65
boxylic acid ethyl ester) -anthra.quinone in ?nely
\H/
0
000?:H5
NH_
65
subdivided form" are vatted in a solution of 600
parts of water, 100‘ parts of pyridine, 15 parts of
- sodium hydrosul?te and 35 parts of sodium hy
x70 droxide solution of 30 per cent. strength for 1
hour at 30-40“ 0., ring closure occurs to pro
duce the dinaphthacridone. The whole is ?l
tered from a little residue and the ?ltrate is oxi
dized by passing air through it at Bil-40° C. When
175 the oxidation of the dyestuff is complete the lat
are vatted in a ?nely subdivided form in a solu
tion of 600 parts of Water, 100 parts of pyridine,
21 parts of sodium hydrosul?te and 50 parts of
sodium hydroxide solution of 30 per cent. strength
75
4
2,132,829
for 1 hour at 40-50’ C. After ?ltration the dye
stu? is precipitated from the ?ltrate by blowing
in air; it is ?ltered, washed neutral and dried.
The dark green diacridone thus obtained of the
formula
dissolves in concentrated sulfuric acid to a black
ish-blue solution and dyes cotton from a warm
vat olive tints.
The parent material for this example is made
as follows:—
22.8 parts of 4:4’-diamino-1:1’-dianthraqui
nonylamine, 23.6 parts of l-chloronaphthalene
Z-carboxylic acid ethyl ester, 12 parts of anhy
drous sodium carbonate and 0.6 part of anhy
drous cupric chloride are added to 240 parts of
10
nitrobenzene and the whole is boiled for 20 hours
under re?ux. After cooling at small quantity of
impurities is ?ltered from the solution and the
latter is Washed with nitrobenzene and the ?l
15
trate freed from nitrobenzene by steam, again 15
?ltered and the solid matter is Washed until neu
tral and dried. The new condensation product
is thus obtained in the ‘form, of a dark powder.
20
Example 5
20
26 parts of 5-aminoanthraquinone-l:1’:2:2’
naphthacridone of the formula
25
25
21
1/
35
dissolves in sulfuric acid to an olive solution and
when precipitated therefrom by water forms
green ?ocks. Cotton is dyed green in a red vat.
10 parts of the above diacridone from 4:4’
40 diamino-l:1’-dianthraquinonylamine are intro
duced at ordinary temperature into 150 parts of
sulfuric acid of 66° Bé., the whole is stirred for
some hours at 30-40” C., then poured onto ice,
sucked oif, washed neutral, and dried.
The dyestuif thus obtained, probably the car
45
bazol. of the formula
50
N/ I
l
.30
GO
/
(obtained by saponi?cation of the corresponding
benzoylamino compound in sulfuric acid of 66° 40
Bé. at 90° C.) are boiled for 20 hours in a re?ux
apparatus with 17.2 parts of l-chloroanthraqui
none, 8 parts of anhydrous sodium carbonate, and
0.4 part of anhydrous copper chloride in 250 parts
by weight of nitrobenzene. After cooling the 45
mixture is sucked off, washed with little nitro
benzene, then with toluene and alcohol and ?nally
with water, until neutral and then dried.
The new condensation product thus obtained of
the formula
C>
55
60
65
65
70
75
dissolves in concentrated sulfuric acid to brown
orange solutions.
When precipitated in Water
5
2,132,829
there are formed violet ?ocks.‘ Cotton is dyed
from a red vat brownish-violet tints.
10 parts of this condensation product are intro
duced at 140° C. into a mixture from 80 parts of
The dark brown condensation product of the
formula
7
aluminium chloride and 20 parts of sodium chlo
ride, the whole is stirred for 1/2 hour at 140-150“
C., taken up in water and hydrochloric acid,
heated to the boil, ?ltered hot and washed neu
tral While hot, and then dried.
1O
The carbazol thus obtained of the formula
HN/ l
I
'00
15
15
CO
EN
20
20
O:
‘
/
25
=0
30
30
dissolves in sulfuric acid to a brown solution
which when poured into water yields brown
?ocks. This vat dye is red; cotton is dyed red 35
35 dissolves in concentrated sulfuric acid to red
brown solutions; when precipitated in water there
are formed brown ?ocks.
Cotton is dyed from
violet~brown vat fast brown tints.
40
Example 6
10 parts of a dicarboxylic acid of the formula
0 O
brown tints by it.
The compound here used as parent material
may be made as folloWs:—-'
16 parts of l:4-dichloronaphthalene, 48 parts
of l-aminoanthraquinone-Z—carboxylic acid ethyl
ester, 20 parts of anhydrous sodium carbonate
and 0.8 part of cupric chloride are added to 160
parts of nitrobenzene and the whole is boiled for
20 hours under re?ux. After cooling the mass
is ?ltered from impurities and the ?ltrate dis pp. 5
tilled with steam to separate the nitrobenzene.
The residue is ?ltered and the solid matter is
washed with hot water and dried. The dark
brown condensation product thus obtained dis
solves in sulfuric acid to a brown solution which
when poured into Water yields brown ?ocks.
50
The free dicarboxylic acid is obtainable by
treating the above diester in alcohol with caus
tic soda solution.
Example 7
0.5 part of the dyestuff made as ‘described in
Example 2 is formed into a paste with 3 volumes
of caustic soda solution of 36° Bé. and 100 parts
of water at 25-30° C.; there is then added 1 part
of hydrosul?te powder cone. and the vatting proceeds for 1/2 hour at the above temperature.
The dye bath is prepared as follows:
900 parts by volume of liquor, 1 mol. of caus
tic soda solution of 36° Bé. and 0.5 part of hy
drosul?te conc. Into this bath is poured the
vatted dyestuff and dyeing is continued for 1
hour at 40-500 C. After dyeing the goods are
wrung out, oxidized in the air, rinsed and de
veloped with 5 parts of soap, 2 parts of anhy
drous sodium carbonate per litre for 1/2 hour at
CI 01
70 are treated in 160 parts of toluene with '7 parts
of phosphorus pentachloride'for 1 hour at 50-55°
C.; the whole is then boiled for 1/4 hour under re
?ux.
After cooling the mass is ?ltered and the
solid matter washed with toluene and alcohol and
75- ?nally with Water until neutral; it is then dried.
55
60
65
70
boiling temperature. Cotton is dyed fast green
ish gray tints.
Example 8
0.5 part of the dyestuff described in Example 3
is heated at 50-60o C. with 6 parts by volume of 75
2,132,829
caustic soda solution of 36° B'é. and 100 parts of
Water; there is then added 1 part of hydrosul?te
conc. powder at 50-60° C.
Reduction is contin
ued for 20 minutes. The dye bath consisting of
900 parts of water is mixed with 6 parts by vol
ume of caustic soda solution of 36° Bé. and 0.5
per cent. of hydrosul?te conc. at 50-60° C. and
then the vatted dyestu? is added.
50 parts of
cotton are now entered and handled for 1 hour
10 at 50—60° C. The dyed goods. are then wrung
out and oxidized in the air for 1/2 hour. After
the oxidation the goods are rinsed well with
water and developed for 1/2 hour with 5 parts of
soap and 2 parts of anhydrous sodium carbonate.
The cotton is dyed fast gray.
What we claim is:—
‘The dyestuif of the formula
0
20
HN/ I
25
3
21:0
\i/ I
35
i’ TH>
40
45
C
which product is a dark powder, dissolving in
sulfuric acid to a blackish blue solution and in
Water with addition of hydrosul?te and caustic
soda solution to a brown solution, and dyeing
cotton from thevat fast level olive tints.
WILI-IELM MOSER.
WALTER FIORONI.
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