close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2411148

код для вставки
Patented Nov. 19,’ 1946
UNITED’ STATES- PATENT oFncE ‘
AN THRAQUINONE‘DYESTUFFS
Joseph B. Dickey and James G. McNally, Roch
ester, N. Y., assignors to Eastman Kodak Com
pany, Rochester, N. Y., a corporation of New
Jersey
‘
No Drawing. Application October 23, 194
Serial No. 507,486
5 Claims.
'
(Cl. 260-376)
2 ‘
l
'
' ‘ This invention relates to the manufacture of
new anthraquinone dyestu?s and to the coloration with such dyestuffs of materials made of or
containing cellulose derivatives.
We have found that anthraquinone dyestuffs 5
_NHCH2CH0HCH3
_.NHCH2c1-I2CH20H
containing both a hydroxyalkyl group’ (or rad-
_
icle) and a hydroxyalkyl group (or radicle) esteri?ed with an organic acid radicle are especially
suited for the coloration. of materials made of
mNHCHZCHOHCHzOH
-
‘
_
p
mNI-ICHZCHZCHZCHEQH‘ ’
_._N(Q2H40H) 2
;N(CH_ZCHOHCHZQH)Z
‘
H
a I
or containing cellulose derivatives, e; g. organic l0 and
derivatives of cellulose.
the
coloration
of
Such new dyestuffs and
materials
therewith
are
.
be‘ present in the Starting {iyestu? Include those
present in hydroxyalkyl 91111110 gTQupS i511011 as!
_NHCH2CH2OH
_
‘ _
set
_‘
‘
V
>,—’-N‘(CH2CH2CH2‘OH)2
'
‘
T
>
‘
" '.
forth in‘ our copending application Serial No.
‘aswell ‘as the hydrpxyalkyl groups pris?ntf lln
306,200, filed November 25, 1939, now Patent
hy‘lmxyalkyl arylamlm gmups’ Such as‘
2,338,908, of which the instant application is a l5 lowmg'
'continuation-in-part.
‘
‘
6
.
v
.
‘
The dyestuffs of our invention
can be _pre-
2
2
NHCH CH CH
pared in various ways, but are advantageously
prepared by esterifying a dyestu? containing two ‘
Q.
or more hydroxyalkyl groups, under controlled 20
“NH
conditions, so that at least one of the hydroxyalkyl groups remains unesteri?ed.
6 °'
-
NHcHz?lHoHa
Thus, in a
0H
l 7‘
dyestu? containing two hydroxyalkyl radicles,
one hydroxylakyl radicle can be esteri?ed by re-
_NH<:>TNHCHZCHOHCF’OH
acting the dyestu? with about one-molecular 25
equivalent of an organic acid anhydride, or an
and
‘
organic acid halide, or an organic acid (in this
‘
‘
latter case, in the presence of a suitable catalyst),
‘
i. e. with about enough of the organic acid an-
-
i
“NH.
l ‘
‘
‘
‘
hydridaorganic acid halide or organic acid to 30 Still other hydroxyalkyl ‘groups may be present
esterify substantially but one of the hydroxyin groups such 55 the followmg:
alkyl groups. The exact chemical reaction tak
ing place is not known. The probabilities are
“NH
O-CHzCHzOH
that both hydroxyalkyl groups are esteri?ed to
some extent. However, by employing about one 35
molecular equivalent of esterifying agent, the
—NH
ocnlcnonor‘non
esteri?ed product consists essentially of dyestu?
wherein but one of the hydroxyalkyl groups is
<50
esteri?ed and the other hydroxyalkyl group is
not esteri?ed.
-
/CHT—CEZ /H
40
Both aliphatic and aromatic (aryl) esterifying
agents can be employed. Usually a solvent or
diluent medium, nonreactive with the esterifying
agent, is present in the reaction mixture.
"'NH\‘
/ \
' CHz-CH: 0H
—NH—~CH2CHZ-NH—CH2CH2OH
and .
If
an organic acid anhydride or an organic acid
——NH—CHzCHr—O-QH2CH2OH_
‘- V‘
The starting dyestuffs containing the hydroxy
halide is employed as an esterifying agent, the
alkyl groups are described in the prior‘art. In
esteri?cation is advantageously effected in the
the case of. anthraquinone compounds, hydroxy
presence of a tertiary amine, such as pyridine or
alkylamino denvatives can be prepared by con
dimethylaniline- The tertiary amine tends to 50 densing a leuco anthraquinone with-a hydroxy
?ombine With the hydrogen halide or the organic
alkylamine, such as ethanolamine, diethanola
acid generated during the esteri?cation reaction.
Still other diluent agents, such as ethylene chloride, dioxane or ethyl acetate, may be present.
Illustrative hydroxyalkyl groups which may 55
mine’) propanommine, butanohmme, cyglghex
anolamine, etc., and oxidizing the resulting leuco
compound to the non-leuco form. Suitable leuco
anthraquinones include, for example, leuco qui-,
2,411,148
3
etc.
Esteri?cation agents, which can be employed in
the preparation of our new dyestu?s, include, for
example, acetic anhydride, propiom'c anhydride,
propionyl chloride, acetyl chloride, benzoyl chlo
ride, methoxy acetic anhydride, butyrie anhy
dride, succinic anhydride, tetrahydrofuroyl chlo
ride, phthalic anhydride, palmitic acid chloride,
furoic anhydride, adipic anhydride, oleic acid
‘4
The dye can be represented by the following for
mula:
nizarin, leuco 1,4,5-trihydroxy anthraquinone,
Cl
chloride, furoic acid chloride, methyl chloro car
It dyed cellulose acetate silk blue.
Example 4
carbonate, allyl chloro carbonate, formic acid
3.26 g. (0.01- mole) of IA-di-p-hydroxyethyla
with sulfuric acid catalyst and glycollic acid with 15 mino anthraquinone were placed in 50 cc. of ethyl
sulfuric acid catalyst,
acetate, together: with 1.68 g. (0.01 mole) of
The following examples will serve to illustrate
methoxy acetic anhydride. The mixture was re
further our invention.
?uxed for 30 minutes. It was then cooled and
Example 1
diluted with a large quantity of water. The dye
was ?ltered o? and dried in the air. A yield‘ of
0.1 gram mole of 1,4-di-B-hydroxyethylamino
3'
g. was obtained. The dye can be» represented by
arithraquinone is reacted in pyridine with 10
the following formula:
grams of chloroacetic acid.
bonate, ethyl chloro carbonate, tetrahydrofuroyl
carbonate, cyclohexyl carbonate, furoyl chloro
25
anthraquinone is obtained and colors cellulose
acetate silk blue.
'
>
0.1 gram mole of 1,4-di'-.6-hydroxyethylamino
anthraquinone can similarly be reacted with 0.1 30
gram mole of propionyl chloride, valeric anhy
dride and caproie anhydride, respectively, to ob
The dye colored cellulose acetate. silk blue. 1
tain compounds wherein one hydroxyethyl group
is convert'ed'to
'
35
Example 5
3.26 g. (0.01 mole) of lA-di-p-hydroxyethyl
amino anthraquinone were placedin 50 cc. of
ethyl acetate together with 1.58 g. (0.01 mole) of
butyric anhydride. The mixture was re?uxed for
30 minutes. It was then cooled. and diluted with
40 a large volume of water. The dye was ?ltered
off and dried in the air. Theyield was 3 g. The
dye can be represented by the following formula:
El)
respectively.
45
. C\
Example 2
0.1 gram mole vof 1,4—di-p-hydroxyethylamino
anthraquinone is reacted in pyridine with about
0.1 gram mole (slight excess) of maleic vanhy
dride. A hydroxyethyl group is converted. to
NH-OHz-CHzOH
NH-cHPoLHT-m-o-mm
50
,
l
i
The dye colored cellulose acetate silk blue.
Example 6'
The dye compound obtained colors cellulose ace 55
3.26 g. (0.01 mole) of lA-di-p-hydroxyethyl
tate silk blue.
amino anthraquinone were placed in. 50. cc. of
0.1 gram mole of 1,4-di-p-hydroxyethylamino
ethyl acetate together with 2.26 g... (01.01>mole). of
anthraquinone can similarly be reacted with 5
grams of formic acid to convert one of the hy
droxyethyl groups to a
group. The dye compound obtained colors cellu
lose acetate silk blue.
Example. 3
benzoic anhydride. The mixture was refluxed- for
30 minutes. The mixture was then cooled and
diluted with a large volume of aqueous sodium
hydroxide (5 per cent by‘weight)‘. The dye was
?ltered off, washed with water and dried. The
yield was‘ 3.55 g. The dye melted in hot water.
The dye can be represented by the following
formula:
‘
U
blirkorrrc-m-o?'
16.4 g. (0.05 mole) of IA-di-B-hydroxyethyla
mino anthraqui-none were placed in 185 cc‘. of
ethyl? acetate. To the resulting mixture were 70
added 5.1 g. (0.05 mole) of acetic anhydride. The
resulting mixture was re?uxed‘ for one hour. The
mixture was: then diluted with _11 liters of‘ water.
The. dye was ?ltered‘ off‘ and dried in the air; The
o
yield was 13 g; The dye melted'at 170° to 180° C, 75n. ltcolored cellulose- acetate silk blue-green.
NH-CHrGHz-O-jiI-Cdis
2,411,148
5
6
Example 7
a.
three hours.. The resulting mixture was allowed
to stand for a period of about 12 hours. The dye
3.26 g. (0.01 mole) of 1,4-di-p-hydroxyethyl
amino anthraquinone were placed in 50 cc. of
ethyl ‘acetate-along with 1.86 g. (0.01 mole) of
valeric anhydride. The mixture was re?uxed for
was then ?ltered off, washed with cold water and ‘
dried in the air.
The" dye had the following
formula:
'
.
one hour. It was then cooled and diluted with
2 liters of water. The dye was ?ltered off, washed ‘
with water and dried in the air._ The yield was
3.2 g. The dye can be represented by the follow
ing formula:
‘
.
10
CCl) IIIH-GHz-CHr-OH
Example '12
15
3.26 g. (0.01 mole) of 1,4'-di—,3-hydroxyethyl
amino anthraquinone were placed in 15 cc. of dry
o
pyridine. To the resulting mixture were added
20 dropwise 2.26 g. (0.01 mole) of benzoic anhydride
The dye colored cellulose acetate silk blue.
dissolved in pyridine. The resulting mixture was
Example 8
re?uxed for two hours. It was then cooled and
diluted with cold water. Sodium chloride was
16.3 g. (0.05 mole) of 1,4-di-p-hydroxyethyl
added to the diluted mixture to salt out the dye.
amino anthraquinone were placed in 250 cc. of
ethyl acetate together with 6.5 g. (0.05 mole) of 25 The dye was ?ltered off and dried in the air.
In a manner similar to that illustrated above,
propionic anhydride. The mixture was re?uxed
still other dyes containing both a hydroxyalkyl
for one hour. The mixture was then cooled and
group and a hydroxyalkyl radicle esteri?ed with
diluted with 4 liters of water. The dye was ?l
an organic acid radicle can be prepared.
tered off, washed with water and dried in the air.
The dyestuffs may be sulfated so as to convert
The yield was 15.3 g. The dye can be represented 30
any alkyl group into sulfo alkyl groups. Sulfa
by the following formula:
NH-CHz-OHz-O-(?l-Cdln ‘
O
NH-CHFCHPOH
C
tion may be effected by treatment with strong
sulfuric acid.
The dyestuffs produced according to this inven
35 tion have valuable dyeing properties for organic
derivatives of cellulose. They are of greatest
importance in the coloration of textile materials
containing organic derivatives of cellulose, such
as cellulose acetate, cellulose propionate, or cellu
40 lose butyrate.
The dye colored cellulose acetate silk blue.
The dyestuffs can also be em
ployed to dye cellulose ethers, for example, ethyl
or benzyl cellulose. The new dyestuifs may also
Example 9
be employed in the coloration of mixed materials
100 g. (0.31 mole) of 1,4-di-p-hydroxyethylamino
anthraquinone were placed in 500 cc. of dry pyri
or ethers in admixture with other textile ?bers,
for example wool, silk or other animal ?bers, or
cotton, regenerated cellulose or other cellulosic
materials. Such other ?bers may be colored by
the same dyestuffs as the cellulose esters and
dine. The mixture was heated to re?uxing, and
35 g. (0.34 mole) of acetic anhydride were run
into the mixture over a period of 30 minutes.
comprising one or more of the aforesaid esters
After the addition of the acetic anhydride, the 50 ethers when they possess the requisite a?inity,
mixture was re?uxed for one hour. The mixture
was then cooled and diluted with 10 liters of
water. Sodium chloride was added to the diluted
or they may be colored in the same or different
shades by means of other dyestu?s, before, after
or simultaneously with the coloration of the cellu
mixture to salt out the dye. The dye was ?ltered
lose esters or ethers.
55
off and dried in the air. The yield was 93 g.
The dyes are ordinarily applied to the textile
materials
in the form of an aqueous suspension
Example 10
which may be prepared by grinding the dye to a
paste in the presence of soap or other suitable
3.26 g. (0.01 mole) of 1,4-di-p-hydroxyethyl
amino anthraquinone were placed in 15 cc. of
dispersing agent, and dispersing the resulting
dry pyridine. To the resulting mixture were
added dropwise 1.3 g. (0.01 mole) of propionic
anhydride dissolved in pyridine. The resulting
mixture was refluxed for one hour. The mixture
was then cooled and poured into 300 to 500 cc.
of water. Sodium chloride was added to the
paste in water. Dyeing operations may be con
ducted at a temperature of 80° to 85° C., but any
suitable temperature may be employed. In ac
cordance with the usual dyeing practice, the ma
terial to be dyed will ordinarily be added to the
dye bath at a temperature lower than that at
diluted mixture to salt out the dye. The dye was
?ltered off, washed with water and dried in the
which the main portion of the dyeing is to be
effected, e. g. a temperature of from 45° to 55° C.,
air.
'
Example 11
l g. of 1-p-hydroxyethylamino~4-p-chloracet
oxyethylamino anthraquinone (obtained accord
ing to Example 1) was heated in water for one
hour. 1 g. of sodium bicarbonate was then added
following which the temperature of the dye bath
will be raised to that selected for carrying out
.the operation. The temperature at which the
dyeing operation is directed will vary depending
upon the particular material being dyed. Dis
persing or solubilizing agents that can be em
ployed for preparing suspensions of the dyes in
to the mixture and boiling was continued for 75 clude soap, sulphoricinoleic acid, salts of sul
2,411,148
8
phoricinoleic acid and of sulphonated oleic acid,
4. The anthraquinone' dyestu? having the
formula:
etc.
What we claim as our invention and desire to
be secured by Letters Patent of the United States
is:
1. Anthraquinone dyestu?s containing in the
l-position a hydroxyalkylamino group esteri?ed
with an organic acid radical and in the 4-position
a hydroxyalkylamino group.
2. Anthraquinone dyestuffs containing in the
' l-position a hydroxyalkylamino group esteri?ed
with a lower alkyl monocarboxylic acid radical
and in the 4-position a hydroxyalkylamino group.
3. The anthraquinone dyestuff having the
formula:
H
(I) N-—GHzCH'a-—-O~—(HJ—CHqCL
0
N-CHzCH2OH
H
N-CHzCHzOH
JOSEPH B. DICKEY.
H
JAMES G. MCNALLY. _
Документ
Категория
Без категории
Просмотров
0
Размер файла
455 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа