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Патент USA US2115311

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2,115,311
Patented Apr. 26, 1938
UNITED STATES PATENT OFFICE
2,115,311
DYESTUFFS OF THE OXAZENE SERIES AND
A PROCESS OF PREPARING- THEM
Georg Kranzlein, Heinrich Greune, and Max
Thiele, Frankfort-on-the-Main, Germany, as
signors to General Aniline Works, Inc., New
York, N. Y., a corporation of Delaware
No Drawing. Application October 26, 1934, Se
rial No. 750,202.
In Germany June 6, 1928
9 Claims.
(Cl. 260-28)
This application is a continuation-in-part of
our co-pending application Serial No. 364,316,
?led May 18, 1929 (now U. S. P. 2,026,092 granted
December 31, 1935)‘.
for instance, those which have the following
constitution :
X
I j
The present invention relates to dyestuffs and
5
to a process of preparing them.
'
We have found as a surprising fact that benzo
"quinone derivatives of the following formula:
10
X
1
wherein Z means that the dyestuff may be sul
Y
fonated, X stands for hydrogen or halogen, Y
means hydrogen or alkyl and R represents an
aromatic group of the benzene or napthalene
series, the position of the sulfo group being
Y
undetermined. R1 for an aromatic group of the
benzene, diphenyl or naphthalene series, and '
wherein the two R1—N—R—chains are identical.
6
wherein X stands for hydrogen or halogen, Y
O stands for hydrogen or alkyl and the R’s stand for
aromatic groups of the benzene or naphthalene
series, having at least one unsubstituted position
adjacent to the NH-groups, the Ri’s stand for
aromatic groups of the benzene, diphenyl or
25 naphthalene series and wherein the two
'R1—N—R-—chains are identical, yield, when
being heated as such alone or with the addition
of an oxidizing agent and, if necessary, of a
catalyst, in a high-boiling solvent, bluish con
30 densation products, from which, by sulfonation,
water-soluble dyestuffs are obtained which dye
the ?ber valuable blue, bluish-gray or bluish
green tints.
To perform the reaction there may be used as
35 high-boiling solvents nitrobenzene, trichloroben
.zene or the like,vas_,oxidizing agents potassium
ferricyanide, pyrolusite, ferric chloride or similar
products and as catalysts there may be used
phosphorus pentachloride, antimony pentachlo
40
ride and others more.
The sulfonation may
’ ‘preferably be carried out by means of fuming sul
furic acid orvconcentrated sulfuric acid.
Instead of ‘?rst condensing and then introduc
Both by their excellent fastness to light and
their remarkable shades these new blue, bluish
gray and bluish-green dyestuffs are particularly 20
valuable for dyeing silk.
_
When reacting upon the said new sulfonated
dyestuffs in the manner indicated in U. S. Patent
No. 1,800,299 with the bases characterized in the
said patent, blue, bluish-gray and bluish-green
dye pigments are obtained which are very suit-.
able as nitrocellulose (varnish) -, cellon- and
alcohol lacquers.
'
The following examples serve to illustrate the
invention but they are not intended to limit it
thereto, the parts being by weight:
(1) 100 parts of 2.5-di(-para-aminodiphenyl
amino) -3.6-dichloro-lA-berizoquinone are heat
ed to boiling temperature for 8 hours with 12
parts of phosphorus pentachloride and 5 parts of
pyrolusite in 1000 parts of nitrobenzene.
After
cooling, the separated condensation product is
?ltered by suction, subsequently washed with al
cohol and dried.
It forms a crystalline powder showing aviolet
luster on its ‘surface, is insoluble in water, some
. what soluble in-benzene to a reddish-violet solu
.tion, sparingly soluble in alcohol to a blue and in
nitrobenzene to a brownish-violet solution. By
45 ing the sulfo group by a subsequent operation as ‘ sulfonating it by means of sulfuric acid or fuming
50
above stated it is, of course, also possible to intro
duce the sulfo group already before the oxazine
sulfuric acid, a sulfonic acid is obtained which
has been formed, by starting, for instance, from,
ness to light and which has also in aqueous or
an amino-diaryl-amine-sulfonic acid.
soda alkaline solution a' great afinity for the
ordinary or previously mordanted textile ?ber,
_
Our invention leads to new valuable dyestuffs,
dyes silk and wool blue tints'of very good fast
a
,
2,115,311
The 2.5—di(-para ~aminopheriy1ami'no) -3.6-di
1.4-ben'zoquinone instead of chlora'nil, andtreat
chloro-lA-benzoquinone used as starting ma-.
ing them as described inthe ‘foregoing examples.
terial may be preparedr‘by condensing chloranil
We
with para-amino-diphenylamine in the presence
1. The process which comprises boiling in the
claim 2'
s
V
'
7
~
of alcohol. It forms a blackish-brown powder presence of nitrobenzene and a small. amount of 5
. melting at a temperature of about 300° C., being . phosphorus pentachloride and pyrolusite 2.5-di
(-para-amino-diphenylamino) - 3.6 -dichloro--1.4- .7
' insoluble in’ alcohol and glacial acetic acid, spar
' ingly soluble in ortho-dichlorobenzene.
Instead
of
‘
benzoquinone.
'10,
may also’ be used para-amino-N-methyldiphen
7
phenyl-alphaenaphthylamine,aminophenyl—beta
ylamine,
'
‘ meta — aminodiphenylamine,
amino
nodinaphthylamineor
(2)
the like.
‘
'
'
<
di (‘-para - amino adiphenylaQmino) -3.6-dichloro
'lA-btenzoduinbne and then sulfronatingr the.prod-'}' ' _
. naphthylamine, aminonaphthylphenylamine, ami
V
’
7 2. The process’ which comprises boiling in the
presence of nitrobenzene anda smallamount of 10" ’
phosphorus pentachloride. and pyrolusite 2.5- '
para-aminodiphenylamine there '
uct thus obtained.
V
3. A compound selected from the group ‘con-~ '15
‘sisting of the compounds of- the general formula: '
50 parts of 2L5-di(-2’ramino-diphe-nyla
, , mine) -3.6-dichloro¢1.firbenzoquinone-eobtainable
by condensation of' chloroanil with 'Z-amino- ..
.
X
7
’
Vdiphenylamine in alcohol—-are boiled‘for5 hours '
in
is introduced
600 parts of into
nitrobenzene.
the reaction
Aftercooling,
mass in order’
steam
to’ "
e270
remove the nitrobenzene, ‘the remaining solid 7'
residue is ?ltered o? Tand'dried." The? product‘;
forms ‘a bluishéblack powder. It is insoluble in p 7
water and dissolves inv concentrated sulfuric acid wherein X stands. for a radical of the groupcon-i
to an olive-‘green solution. - It dissolves in hot ' 'sisting of hydrogen and halogen, Y-for a radical‘ .25 r
trichlorobenzene toga violet. solution, having a
of the group consisting of hydrogen and'a'lkyl,
brown fluorescence.‘ By ,sulfonating the product _
7R foran‘aromatic group offthe benzene'or naph-~
in concentrated suliuric,._acid, a sulfonic acidiis
obtained which dyes silk, wool, cotton, viscose
arti?cial ?ber and paper fast bluish-gray tints.
pthalene series, R1 for an aromatic group of the
benzene, diphenyl or; naphthalene 'series' and
wherein- the two? R1—N+R-‘—chains are identical
~ '7
(3)" '100 'parts :of 2.5-di(-para-amino-ortho- V and the sulfonic? acid of. these compounds: ff 7 ., V
methcxydiphenylamine) ' _-3.6-dichloro-1.4-benzo
4:. The compounds of: the'i'general' sformulaii l, '
‘ quinone—ob-tainable by condensation of, para?’
aminororthofmethoxydiphenylamine with ch10
roanil—lare' 'boiledjfori3 hoursiin l500iparts of ' ,nitrobénzene. llgniorderto remove the nitroben
izreneysteam is then’introduced, the remaining
residue is ?ltered'off and: dried. It forms a dark
,violet rpowdervwhich dissolves- in concentrated
I
r
,7
"i 140
sulfuricacid'to a ‘green’ solution.’ It'is sparingly
soluble in organic solvents. .It dissolvesa little wherein Z means that the compounds contain s‘
in trichlorobenzene vto a blue solution, havinga ,sulfo groups, X stands for a radical of the group
consisting of hydrogen and halogen, Y for a radi
red ?uorescence.
~
7
.
~
‘ Whenpsulfonated inlstr'ong‘sulfuric acid, the 7 ‘cal of the group consisting of hydrogen and .alkyl', ‘d7.’ "
reaction productlyieldsg-a dyestuff-sulfonic acid ' ‘R and Ri'iorran aromatic'group of the benzene 45
fwhich dyes silk, wool, cotton and‘ viscose arti?cial 'or naphthalene ‘seriesQand wherein the '1 two
.jR1~—N—R¢—chains are identical, dyéingwbolarid: ' ~
?berjetc. blue tints pr fastness to‘ light.‘ .
; ‘ (4)
100v parts of'2.5-di(-para-amino-[para]? isilk clear tints of good fastness to light.‘
e 1‘
5. A'compound selected from the 'group‘con
V phenyl] —diphenylamine) -3.6-dichloro-1.4-benzo—
"quinoneéobtainable by condensation of para
,amino- (para’—phenyl) -diphenylamine with chlor
sisting of the compounds ofthe general formula... :50 , :
i'anil in alcohol—are_boiled for. 5' hours in 71000 _
parts of'nitrobenzene.w After cooling of the re
action mass, the solvent
removed by introduc-j . '
7 tion of steam, the distillation residue isolated by
filtration and dried.
s v
r
..
P1
The reactionsproduct forms a darkéviolet'pow
der which isljsparingly’solublein organic solvents
.
"
.
X
it‘
s” wherein X stands for a radical of the group con-5;: 7 ,
and shows a red ?uorescence intrichlorobenzene. 7 sisting of hydrogen and halogemY for a radical '60‘- V
. It dissolves in? concentrated sulfuric acid to an 1 ‘ of : the , group-7 consisting. of fhydrogen and ' alkyl
~ 1 oliveegreen solution. ' 'By sulfonation iniconcemr ' '
trated sulfuric acid'or fumingsulfuric acid; a
and wher'einthe ‘e i
I
g
'
.
~
_.;
*
.
' '_'sulfonic ‘acid is, obtained, which’ dyes ,Wool, silk, . ~
' '65
cotton,lviscose arti?cial"?ber'etcfiblue tints of
.
r
p
7 'agroups stand inxpi ‘051m position'an‘d-the
1 Similar dyestuffs are’, obtained'by
parent. acids of ‘these compounds.‘
.
A
good fastness tolig'ht;
" materials which have been prepared 'Vbymeajns of .
mitotic]
.
s
6. The compounds of; the generalfformulaz? ' r
'
p,
"
r
X
I‘
‘
'
‘
‘
.
2,115,311
wherein Z means that the compounds contain
sulfo groups, X stands for a radical of the group
consisting of hydrogen and halogen, Y for a radi
8. The compound of the formula:
cal of the group consisting of hydrogen and alkyl
5 and wherein the
M0
10
wherein Z means that the dyestuff contains sulfo
groups, dyeing silk, wool, cotton, viscose arti?cial
groups stand in 111 or m position, dyeing wool and
silk clear tints of good fastness to light.
?ber and paper fastbluesgray tints.
9. The compound of the formula:
15
15
20
~
con?rmed
wherein Z means that the dyestu? contains sulfo
7. The compound of the formula:
25
0.1
30
O @IK /O\UNH\O
EN
0
0
“I z
\N/
groups, dyeing wool, silk, cotton, viscose arti?cial
?ber, etc. blue tints of good fastness to light.
GEORG KRANZLEIN.
HEINRICH GREUNE.
MAX TI-IIELE.
I
wherein Z means that the dyestu? contains sulfo
groups, dyeing silk and wool blue tints of good
35 fastness to light.
35
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