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Патент USA US2115446

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2,115,446
Patented Apr. 26, 1938
UNITED ‘ STATES
PATENT OFFICE
2,115,446
VAT DYESTUFFS OF THE ANTHRAQUINONE
AZINE SERIES
'
Karl Koeberle and Joachim Mueller, Ludwigs
hafen- on-the-Rhine, Germany, assignors to
General Aniline Works, Inc., New York, N. Y.,
a corporation of Delaware
No Drawing. Application November 9, 1934, Se
rial No. 752,374. In Germany January 20,
1934
13 Claims.
vats.
The present invention relates to new vat dye
the dyestu?s are obtained in a state of high
We have found that valuable Vat dyestuffs
yielding blue vats are obtained by treating N
purity. They may be puri?ed, if desired, by way
suitable as initial materials for the purpose of the
present invention may be mentioned the N-alkyl
anthraquinone-1-2,2’,l’-azines
obtainable
1.2- or 2.1~alkylamino-halogenan
thraquinones with themselves, if desired in the
form of their leuco compounds, or those obtain
able by condensing one molecular proportion of
1-alkylamino-2-halogenanthraquinones with one
15 ‘molecular
proportion of l-amino-Z-halogenan
thraquinone or one molecular proportion 01' 1
halogen-2-alkylaminoanthraquinone with one
molecular proportion of l-halogen-Z-aminoan
thraquinone.
-
As dehydrogenating agents suitable for the
20
purpose of the present invention may be men
tioned halogens, agents supplying halogen, as
for example sulfuryl chloride, phosphorus penta
chloride, benzoyl chloride and the addition com
‘pound
of bromine and pyridine, furthermore py
25
rolusite in the presence of a mineral acid, lead
dioxide, lead tetraacetate, mixtures of concen
trated sulfuric and nitric acids and mixtures of
alkali metal bromides with chlorsulfonic acid or
oleum.
‘
of their salts with strong mineral acids or by
removing any impurities by heating them with
organic solvents.
The following examples will further illustrate
how the said invention may be carried out in
by. practice, but these examples are no limitation of
10 condensing
30
The outputs are generally very good, and
stuffs and a process of producing same.
alkyl-anthraquinone-azines with dehydrogenat
ing agents. As N-alkyl-anthraquinone-azlnes
5
(Cl. 260-31)
I
The reaction is, generally speaking, carried out
at elevated temperature, especially if halogens
the invention. The parts are by weight.
10
Example 1
23 parts of the N-alkyl-anthraquinone-1,2,2’,1’
azine from 1-methylamino-2-bromanthraquinone
and 1-amino-2-bromanthraquinone are heated
to from 100° to 110° C. for several hours in 230
parts of nitrobenzene, while stirring, after the
addition of 2 parts of iodine and 10 parts of bro
mine.
As soon as a sample withdrawn yields a
pure blue vat, the Whole is allowed to cool and
the reaction product which separates in the form
of reddish blue needles is ?ltered oiT by suction.
It yields a blue vat from which powerful clear
blue dyeings of excellent fastness properties are
obtained.
If 23 parts of bromine be employed instead of
10 parts, a dibromo derivative is obtained under
the same conditions. This yields somewhat more
greenishblue dyeings than the bromination prod~
not obtained according to the foregoing para
graph.
.
ry out the reaction in an organic diluent as for
example nitrobenzene or trichlorbenzene.
If halogens or agents supplying halogen are
Reaction products containing chlorine and
bromine and which likewise yield blue vats and
blue dyeings are obtained by employing suliuryl
chloride in addition to bromine. The reaction
products containing chlorine and bromine dis
solve in concentrated sulfuric acid usually to give
employed, a halogenation of the reaction prod
a brown coloration.
or agents supplying halogen are employed. In
the'latter case, it is of special advantage to'car
ucts may occur at the same time. The reaction
products obtained by the treatment with other
dehydrogenating agents maybe halogenated in
a separate operation. Besides, halogen-contain
ing reaction products are obtained by employing
halogenated N - al k y l — anthraquinone-l,2,2',l'
' azines as initial substances.
The reaction products are vat dyestuffs of ex
cellent fastness properties.
They yield in all
cases blue vats, whereas the initial substances
yield brown vats. Besides, the new dyestuffs
have a greater strength in color, yield clearer
shades of better fastness to chlorine, to light, to
the in?uence of the atmosphere and kier-boiling
and are less soluble in organic solvents than the
initial substances. They may advantageously be
55 employed .for dyeing vegetable ?bres from hot
15"
30"
.
By starting from the N-alkyl-anthraquinone~
1,2,2’,1’-azine from 1-brom-2-amino—3~?uoran
thraquinone and 1.3-dibrom-Z-methylaminoan
thraquinone, it is possible to prepare dyestuffs
containing ?uorine or ?uorine and other halo~
gens by treatment with halogen at above 100° C.
in the presence of nitrobenzene.
Example 2
23 parts of the initial material employed in Ex
ample 1 are dissolved in 230 parts of chlorsul
fonic acid after the addition of 2 parts of iodine 50
and 10 parts of bromine, warmed to from 60° to
65° C. and kept at the said temperature until a
sample withdrawn yields a blue vat. The whole
is allowed to cool, the reaction mixture is poured
into water, ?ltered by suction and the ?lter cake
2,115,446
Washed until ' ‘neutral-
The 7 resulting dyestuff a brown solution and‘ yields a pure blue vat from
1 which contains 2 atoms of bromine per molecule J which at between 40° and 60° C. the vegetable
yields blue dyeings of very good iastnessprop~ _ ?bre is dyed strong; clear blue; shades of very
. erties on ‘vegetable ?bres from a blue vat. '
good fastness properties.
. 7 Example.” 3 I'
o,
7 »
'
a . :Erample 6‘ '
j
‘ ~
>1
.7
‘a
10 parts of i the N-alkyl-anthraquinone
. employed
23 partsofthe
every
?nely'divi'ded
compound
as :initial
material
in Example
1 ‘in :7 1;1,2;2',1'-azine obtainable by treating 1.3-dibro'm
230 parts of nitrobenzene are‘heated for 3 hours” Z-methyIaminoanthraquinone ' with sodium‘ ace
‘while stirring'at ‘7590. after the addition of 2 tate in nitrobenzene in the presence of a little
parts of iodine and 35 parts of sulfuryl chloride; ' copper acetate which contains bromine and'yields
and then for another 2 hours at’ 100° C.’ When
a brown vat,’ are dissolved in 100 parts of nitro-_
the reaction is completed the whole is allowed
benzene. After theaddition of one part of iodine _ V
and 15 parts of sulfuryl chloride, the mixture is ,
7 v to cool and thevreacrtion product is,isolated vby
15' ?ltration’ by suction or by distilling off’ the sol
' heated-for 3Ihours at about 75° C‘. and then for.
vent; if desiredrwith steam. Ablue'crystalline
r
'20
further2 hours at. about 95°’ Ci Aftercooling,
the reaction product containing 3 atoms of chlo- L
powder containing 2 atoms of chlorine 'per mole
cule is obtained which7dissolves in concentrated.
sulfuric acid giving an orange coloration; it yields
a blue-greenvat from which vegetable-?bres are
dyed powerful greenish blue shades of excellent
' rine and 2 atoms of bromine is ?ltered off by Sue
tion and freed from nitrobenzene for example; 7, V
by washing with ethanol. It is a greengblue pow .20'
der which from a blue vat dyes'vegetable ?bres
fastness to kier boiling that is the 'usual soda ’' powerful blue'shades of excellent fastness.
boiling stability test and chlorine. "
A vat dyestuif containing '2. atomsjof chlorine
a
_ .A reaction product containing one to't'wo chlo
’ 25
and 2 atoms of bromine having similar properties.
rine atoms having similarproperties is obtained , is-obtained if the compound obtainable: by treatev
by carrying out the reaction with} chlorine in tri _ ting 1.3~dibrom-2-ethylaminoanthraquinone with.
chlorbenzene.
‘
'
'
'
>7
sodium acetate in nitrobenzene in the presence
>
‘ If the reaction described in the ?rst paragraph
of a little’ copper acetate whichyieldsa'brown
or this example be carried out ‘at 40° C’. while
vat, is chlorinated in the manner describedabova
a0 lengthening the duration of the reaction to_from' '
‘
V6 to 10‘hours, a N-methyl-N-dihydroanthraqui
7
‘
10 ‘parts of the compoundemployed
noneazine containing 3 to 4 chlorine atoms is ob
' tainedi which yields somewhat more reddish dye-'
35
Example
‘
A 30
initial
material in Example 6 are dissolved in 100, parts
ings than the product, obtainable'raccording to the
of nitrobenzene. Afterrthe addition of lpart of
?rst paragraphiof this example and which is en
iodine and 15 partsnof bromine, the mixture. is;
.
heated for 3 hours at’ about 75° C. andj;_for-fu_r-f
' tirely fast to chlorine:
'ther 2 hours at about 95° C.
Example 4; . V
After ‘cooling, the ’
reaction product containing Zjbromine atoms'is" 7
45.6. parts of the initial material employedin, '?ltered off by suction. andfreed from nitroben: '
40' Example 3 are heated for 6 hours ‘at about 100° zene for example by Washing with ethanol. It
C. in 46Qparts of nitrobenzene after the addition ' ‘is argreen blue powder'whichv from a blue vatg)
, oft-2 parts" ofiodine and'60'parts of bromine. dyes vegetable ?bres powerful blue shades of exe' ’ ’
’ The reaction product obtained. in beautiful
.cellent
~ > needles’ is a; dibromo derivative according to anal-
a"cellent fastness properties which are essentially
.
fastnes's.
‘
.
i
a
A‘ vat dyestuif having‘similar properties con-n
.
ysis and yields on vegetable ?bres ‘from a blue 1 taining 2 atoms of bromine is obtained if the_N-:
vat at’ 60° C. clear, greenish blue dyeings of ex-, alkyl-anthraquinone-1,2,2’,1’-azine
obtainable
.50
superior, especially-as regards fastness to chlo- V none with sodium acetate in nitrobenzene in the?
rine, to the 'dyeings obtained with the initial ‘ma-. presence. of a little copper- acetate which yields a
brown vat,.is treated with bromine in the man
Vterial
. A reaction
free from'halog/en;
product having similarproperties
, .; i‘ . V V
is
‘- obtained when carrying outthe treatment with
' bromine in other organic diluents, such as tri
’
h 55
chlorbenzene'
‘
'
'
;
~
7A1 mono-bromo deriva tive isiobtained when em-.
by treating 1.3édibrom-2—ethylaminoanthraqui§
' ner described above.
50:
Eirdmplre 8 I
‘ 10 parts of pyrolusitei'are introduced'into a so‘ '
lution of723 parts of theicondensation’ product} ' '
ploying in the process describedjin the ?rst para- ' employed as initial material inrExample 1 in 300“, '
graph of this example .‘16 partsfofbromineg It. parts of sulfuric acid. lThe reaction 'mixtureiis _
yields somewhat more reddish blue dyeings than V heated at 80° C. until a samplerwithdrawn yields
thew dibromo derivative of improved fastness to a blue vat. After cooling,‘the whole is ?ltered
' 76o chlorine as compared-with the initial material
‘
. V off'b-y suction, the ?ltrate pouredinto water,jthe
The treatment with bromine may also be car > dyestuff precipitated filtered ‘off by'suction and“.
' ried out in‘ chlorsulfonic. acid. Onxgr‘indin'gv the washed with water. 'It is‘ algreen-blue powderf V
?nely divided initial materialiin a ball mill with which yields a>b1ue vat and which dyes’ cotton‘ '
bromine in the presence. of iodine a bromo deriva-v clear powerful blue shades of very good'fastnessi '
I 65
tive is likewise obtained.’
.
,
.
.
properties.
7. _
Example 9
'
Example 5
'
1 23 parts’ of the initial material employed 'in
Example 1 are heated‘ to boiling for about 5
’'
5 parts of’ the condensation product employed
as initial material in Example v1 arerboiled'with
a .mixture'of 50 parts of nitrobenzenegand 10'
hours in'200 parts of nitrobenzene after the addié ‘parts of 'benzoyl chloride for 5 hours.- After
.tion 01350 parts of benzoyl chloride and 2 parts working ‘up blue-violet’ ‘needles 7 substantially‘ w
of ‘iodine. “After coolingythe reaction? product, chlorine free are obtained which dissolve in con-5‘
whichisksubsta‘ntially'chlorine free, separated in. centrated sulfuric acid giving a brown'coloration
lustrous bronze crystalline needles is ?ltered off. ~ and which dye cotton from‘ a blue vat clear blue i
.It dissolves’ in concentrated sulfuric acid to give’ shades of very good fastness properties.
.
2,115,446
5. Aprocess of producing vat dyestuffs of the
anthraquinone-azine series which comprises heat
ing N-alkylanthraquinone-1,2,2’,1'-azines with a
Example 10
10 parts of the N-alkyl-anthraquinone-1,2,2’,1’
azine obtained by treating 1-methylamino-2
bromanthraquinone with sodium acetate in the
chlorinating agent.
6. A process of producing vat dyestuffs of the
anthraquinone-azine series which comprises heat
presence of nitrobenzene and a little copper oxide
are boiled with 100 parts of nitrobenzene after the
ing N-alkylanthraquinone-1,2,2’,1'-azines with
addition of 1 part of iodine for 5 hours. The dye
stulf thus obtained which after working up the
reaction mixture forms blue crystals, dyes from
10 a blue vat vegetable ?bres blue shades of ex
cellent fastness.
sulfuryl chloride.
benzoyl chloride.
7
8. Vat dyestuffs of the anthraquinone-azine
series yielding blue vats containing up to two
alkyl groups of low molecular weight attached to 15
the nitrogen atoms of the azine ring obtainable
according to the process claimed in claim 1 exist
ing in the crystalline state in the form of blue
needles, dissolving in concentrated sulphuric acid
15 to Example 5 are suspended in 100 parts of nitro
benzene. After the addition of 10 parts of bro
mine and 2 parts of iodine, the mixture is heated
for several hours at 120° to» 125° C. After cooling,
the reaction product which contains 2 atoms of
20 bromine per molecule separates in crystalline
form and is ?ltered off by suction. It dissolves
in concentrated sulfuric acid giving a pitch brown
with a brown coloration and dyeing cotton clear 20
blue shades of very good fastness to chlorine.
9. Vat dyestuffs of the anthraquinone-azine
series yielding blue vats containing up to two
alkyl groups of low molecular weight attached to
coloration. It dyes vegetable ?bres from a blue
vat greenish blue shades of very good fastness.
the nitrogen atoms of the azine ring and contain 25
ing halogen obtainable according to a process cov
ered by claim 1 existing in the crystalline state in
the form of blue needles, dissolving in concen
trated sulphuric acid with a brown coloration and
dyeingcotton clear blue shades of very good fast 30
Example 12
A mixture of 50 parts of the compound obtain
able according to Example 5, 500 parts of nitro
benzene, 75 parts of sulfuryl ‘chloride and 2 parts
30 of iodine is heated for several hours at 75° to 85°
C. After cooling, the reaction product which con
tains 3 atoms of chlorine is isolated in the usual
manner.
‘
anthraquinone-azine series which comprises heat 10
ing N-alkylanthraquinone-l,2,2',l’-azinesi with
Example 11
20 parts of the compound obtainable according
25
7
7. A process of producing vat dyestuffs of the
ness to chlorine.
10. Vat dyestuffs of the anthraquinone-l,2,2',l’
azine series yielding blue vats containing up to
two alkyl groups of low molecular weight at
tached to the nitrogen atoms of the azine ring and 35
containing halogen atoms of different kind ob
tainable according to a process covered by claim‘l
existing'in the crystalline state in the form of blue
It dissolves in concentrated sulfuric
acid giving a yellow brown coloration. It dyes
35 vegetable ?bres from a blue vat clear powerful
blue shades of excellent fastness.
Example 1 3
12 parts of the reaction product obtainable ac ' needles dissolving in concentrated sulphuric acid
40 cording to Example 5 are suspended in 200 parts with a brown coloration and dyeing cotton clear 40
of nitrobenzene. After the addition of 10 parts of blue shades of very good fastness to chlorine.
sulfuryl chloride and 1 part of iodine, the reaction
11. Vat dyestuffs of the anthraquinone-1,2,2’,1'
mixture is heated, while stirring, at 70° to- 75° C. azine series yielding blue vats containing up to
for 3 hours. Then, after the addition of 15 parts two alkyl groups of low molecular we1ght at
45 of bromine, the temperature is raised to 120° to
tached to: the nitrogen atoms of the azine ring and 45
125° C. and the whole kept at this temperature containing chlorine obtainable according to a
for another 3 hours. After cooling, the dyestuif process covered by claim 5 existing in the crystal
separated is ?ltered off by suction. It contains 4 line state in the form of blue needles dissolving in
atoms of chlorine and 1 atom of bromine and dis
concentrated sulphuric acid with a brown colora
50 solves in concentrated sulfuric acid giving a brown 7‘ tion and dyeing cotton clear blue shades of very
coloration. It dyes vegetable ?bres from a blue
good fastness to chlorine. '
vat blue shades of excellent fastness.
12. Vat dyestuffs of the anthraquinone-1,2,2',‘1'
What we claim is:
azine series yielding blue vats containing up to
1. A process of producing vat dyestuffs of the two alkyl groups of low molecular weight at
55 anthraquinone-azine series which comprises ' tached to the nitrogen atoms of the azine ring and
treating N-alkyl - anthraquinone-1,2,2',1’-azines
with halogenating agents.
2. A process of producing vat dyestuffs of the
anthraquinone-azine
60
series which
comprises
heating N - alkylanthraquinone - 1,2,2’,1’ - azines
with halogenating agents in an organic diluent.
3. A process of producing vat dyestuffs of the
anthraquinone-azine
series
which
comprises
heating N - alkylanthraquinone - 1,2,2’,1’ - azines
with bromine in an organic diluent.
'
4. A process of producing vat dyestuffs of the
anthraquinone-azine series
which
comprises
heating N - alkylanthraquinone - 1,2,2’,1' - azines
with bromine in an organic diluent in the pres
70 ence of a halogen transferrer.
containing bromine obtainable according to the
process of claim 3 existing in the crystalline state
in the form of blue needles dissolving in concen
trated sulphuric acid with a brown coloration and 60
dyeing cotton clear blue shades of very good fast
ness to chlorine.
'
13. Trichlor-N-methyl-anthraquinone-1,2,2',1'
azines obtainable by heating N-methylanthra
quinone-1,2,2',1'-azines with sulphuryl chloride in 65
the presence of nitrobenzene and a little iodine
acting as catalyst.
KARL KOEBE'RLE.
J OACI-HM MUELLER.
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