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Патент USA US2136300

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Patented Nov. 8, 1938
2,136,300
UNITED STATES
PATENT OFiFICIE
2,136,300‘
AZO DYESTUFFS
Johann Heinrich Helberger, Cologne-Mulheim,
and Heinrich Ohlendorf, Dessau, Germany, as
signors to General Aniline Works, Inc., New
York, N. Y., a corporation" of Delaware‘
No Drawing. Application October 12, 1935, Se
rial No. 44,799. In Germany October 20, 1934
2 Claims. (01. 260—155)
The present invention relates to new azo dye
ity ofltheirshades combined with the very good
stuffs, more particularly it relates to azo dye
fastness to lightv and excellent dischargeability,
stuffs which may be represented by the general and they ful?l a long felt want in the ?eld of
formula:
5 k
CH2
\
TH CH0}?
/CH2
10?;
H 1i
;
15"
'
.
dischargeable dyestuffs for'cellulose acetate.
The invention is illustrated by the following
examples, but .not restricted thereto:
Example 1
A hydrochloric acid solution prepared in the
usual manner from 13.8,parts by weight of p-ni 10
traniline and 6.9 parts by weight of sodium
nitrite isintroducedintoan ice-cold, hydrochloric
acid solution of 21.5 parts by weight of py-3-hy
droxytetrahydro — 7 - hydroxynaphthopyridine, or
N
|
R
of the corresponding quantity of the hydrochlo
ride of this compound in about 300 parts by weight
of water. The coupling proceeds very quickly,
wherein R stands for the radical of a diazotized
aromatic diazotization component, such as a
radical of the benzene or naphthalene series.
Our new dyestuffs are obtainable by coupling
in an acid medium py-S-hydroxytetrahydro-"I
and after a short time the formation of the dye
stu?‘ is complete, The excess mineral acid is neu
tralized with the aid of sodium carbonate or
hydroxynaphthopyridine of the formula:
isolated by pressing.
The dyestuff corresponds to the following for
sodium acetate, and the insoluble dyestu? is
20’
mula:
HOE
25.
30
with aromatic diazo compounds.
Dyestuffs of especial technical interest are ob
tained when using diazotization components of the
kind generally used in the manufacture of azo
dyestuffs which are intended to ?nd application
for.1 dyeing and. printing cellulose esters and
ethers, especially cellulose acetate silk. Such di
4 ,azotization components are for example amino
35
llloz
'benzene compounds free fromgroups inducing
solubility in water, such as the sulfonic acid or
carboxylic acid group, but which may bear in
the nucleus other substituents, such as the nitro
40
When dyed in the usual manner on acetate arti
?cial silk from a slightly foaming soap bath,
beautiful clear blue shades are obtained which
. group, an alkyl group, an alkoxy group, the hy- j can be discharged to a pure white.
When instead of the 4-nitraniline the 2-chloro
' 'droxy group, and halogen. The cellulose acetate
dyestuffs thus obtained generally yield clear violet ei-nitraniline is used as diazotizing component, a
to blue to green shades of good fastness to light
and of very good dischargeability.
,0, Compared with similarly constituted dyestuffs
dyestulf is obtained which dyes acetate arti?cial
silk beautiful clear turquoise bue shades of good
" those obtained in accordance with the present
When using 5-nitro-2-anisidine and other de
rivatives of 4-nitraniline, dyestuffs exhibiting sim
invention are distinguished by their clarity and
byrtheir» shades, which‘ are distinctly turned to
theiblue to green part of the spectrum, and it is
55,‘remarkable that with the aid of certain bases,
such as with p-nitranilines, dinitranilines and the
like;-the-re are» obtainable shades which have‘been
unknown up to the present in the series of mono
azodyestu?s for. acetate. arti?cial silk. The new
?onidyestu?‘s are technically valuable due to the clar
dischargeability.
ilar properties are obtained.
The py - 3 - hydroxytetrahydro - '7 - hydroxy
naphthopyridine can be prepared as follows:
55
320rparts by weight of 1,5-amino-naphthol are
suspended in 1000 parts by weight of n-butyl al
cohol; thereinto areslowly introduced, while stir
ring, 240 parts by Weight of epichlorohydrin at
80—90° C., and thereupon thev reaction mixture 60
v
2
2,136,300
is heated to boiling for some hours, whereby
crystals of the hydrochloride of py-3-hydroxy
hydrochloric acid solution of 21.5 parts by weight
of Dy-3-hydroxytetrahydro-7-hydroxynaphtho
tetrahydro - 7 - hydroxynaphthopyridine
pyridine.
The dyestuff obtained having the following for
soon
begin to separate. When the quantity of the
crystals no longer increases the reaction mixture
is allowed to cool and the crystals are separated
by ?ltration. For the manufacture of the free
base the hydrochloride is dried, dissolved in
mula:
NH CHOH
water, ?ltered, and from the ?ltrate the free
OH:
10 base is precipitated with the aid of sodium ace
tate. The py-3-hydroxytetrahydro-7-hydroxy
naphthopyridine is thus obtained in the form of
a nearly white crystal powder.
Example 2
15
I
OH 1hr
16.4 parts by weight of 5-nitro-2-aminophenol
15
N
I
are diozotized in the usual manner with 6.9 parts
by weight of sodium nitrite in hydrochloric acid
solution, and the suspension of the diazo com
20 pound is poured into a hydrochloric acid solu
tion of 21.5 parts by Weight of py-3-hydroxy
tetrahydro-'l-hydroxynaphthopyridine in about
' 100 parts by weight of water. While stirring, the
free mineral acid is gradually neutralized by the
addition of sodium acetate, until the coupling
is complete.
The dyestuff corresponding to the following
dyes cellulose acetate silk bluish green shades.
We claim:
1. The dyestuif of the following formula:
CH2
formula:
/Cg2 HOH
30
CH2
TH T
C
35
OH N: QNO:
I
o1
dyeing cellulose acetate silk bluish-green shades.
2. A20 dyestuffs of the general formula
O—on
/CH2EHOH
NH
Oz
is isolated by pressing. It dyes cellulose acetate
arti?cial silk from a soap bath clear greenish
blue shades which are dischargeable to a pure
white.
In the following table there are set out fur
ther combinations prepared in accordance with
the present invention and the shades obtained‘
therewith on cellulose acetate arti?cial silk:
55
Diazotization component
p-Nitraniline _________________________ __
50
wherein R stands for a member selected from
Coupling component
shgif?‘éligilgie?te
Py-B-hydroxytetrahydro-7-hydroxynaphtho-
m-Nitroaniline . ____________ _.
5-nitro~4-chloro-2-anisidine_ _ _ .
Clear blue.
5-nitro-2-toluidine
4~nitto—2—toluidlne ___________ __
4-nitro-2~chloraniline_____
Clear blue.
Violet.
Do.
-
Clear bluish-green.
5-nitro-2-aminophenol ____ _ _
Greenish blue.
5-nitro-2~aminobenzene-sulfo
Greenv
2, 4~dinitraniline ______________________ __
60
Violet.
Do.
65
Example 3
29 parts by Weight of 6-bromo-2A-dinitro-L
aminobenzene are stirred into a nitrosyl sulfuric
70 acid solution prepared by introducing '7 parts by
Weight of soda nitrite into 120 parts by weight
of concentrated sulfuric acid, and after this the
mass is strongly diluted by pouring onto ice. The
sulfuric acid diazo solution is then introduced, if
75 necessary after ?ltering the same, into a cold
the ‘group consisting of the radicals of benzene
and nitr0-, alkyl-, alkoXy-, hydroxy- and halo
gen-substituted benzene, the benzene radical be
ing directly attached to the azo group, dyeing
cellulose esters and ethers generally blue to green 70
shades of good fastness to light and very good
dis'chargeability.
JOHANN HEINRICH HELBERGER.
HEINRICH OHLENDORF.
75
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