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Патент USA US3073846

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3,073,836
United States Patent Oif?ce
Patented Elan. "1’5, ‘(9G3
"3,073,836
ACYL HYDRAZINE DERIVATIVES 0F BIS(4-METH
YLAMlN0-3-METHYLBHENYDMETHANE
Jack M. Tim-,Mount Vernon, N.Y.
(% Dr. I. M. Hunsberger, Innwood, Amherst, Mass.)
No Drawing. Filed Aug..14, 1959, Ser. No. 833,690
v19 Claims. -‘(Cl. 260-495)
‘This invention relates to new coloring matters, more
particularly to the coloring matters of the-acylfhydrazine 10
derivatives of bis(4-methylaminmB-methyIphenyDmeth
ane having the structural formula
CH3
'CH:
1
III
I
15
NHNHC—R
wherein 5R is-acyclic vmonovalent radical of the aromatic 20
series, hothbenzenoid and .nonbenzenoid compoundspsuch
as' benzene series, :naphthalene series, pyridine .series, thio
phene series, turantseries,cycloheptatriene ‘series and syd
none series or any other cyclic compounds which exhibit -
25
aromatic nature.
R, as used here ‘and elsewhere herein, is a cyclic mono—
The new coloring matters are substantially :colorless or
non<dye colored, in their ‘normal state, ‘yet ‘are ‘capable
of generating‘ intense color immediately upon being
brought into suf?ciently intimate ;contact1with a proton
donating agent such as aluminum silicates, heteropoly
acids, and phenols. The contact may be achieved by the
valent radical group of the aromatic series as de?ned
above, such as any halogenated, nitrated, lower alkyl and
lower alkoxylated phenyl ‘group of which examples are
pounds produce a reddish purple color on being rubbed
with attapulgite clay, a blue color with n-propyl or octyl
gallate, and a violet color with phosphotungstic acid. 1
chloro-Z-thienyl, nitro-Z-thienyl, S-bromo-S-nitro-Z-thien
Y1 ‘and methyI-Z-thienyl; halogenated, and nitr'ate'd 'iju’ryl
chlorinated phenyl, chloronitrophenyl, chloromethylphen
yl and methoxyphenyl; halogenated, nitrated, ‘lower alkyl,
and lower a-lkoxylated pyrid-iyl group of which examples
use of solvents, and by :the use of pressure or 'heat with
are 2,6-'dichl'oro-'4-pyridyl, 2,6-dihydroxy-4-pyridyl, moth‘
or ‘without solvents.
The color varies ‘with solvents and ‘with ‘the ‘nature v‘of 35 ylpyridyl and tetrachloro-4-pyridy1; halogenated, nitrated,
and lower alkyl thienyl group of which examples are
the proton donating agents. In general the novel com
bis(4-methylamino-3-methylplrenyl)methyl-2-(2,4-dichl0=
robenzoyl)hydrazine in para?in oil or in chlorinated bi
phenyl gives a glue color on attapulgite clay. The color
group 'ofvwhic'h ‘examples are_2-furyl,_ S-nitro-Z-‘fhryl, 5-‘
40 bromoi2-fu'ryl and 5-chloro~3-hitro-2-furyl. .
with this clay is reddish purple, when the para?in oil is
replaced by methanol or ethanol.
‘The color Ifastness may be varied to some extent by 45
the choice of the proton donating agent. While the re
sistance to ‘fading of the reddish purple produced ‘by clays
is moderate, the violet color produced by phosphotungstic
1, I have accurately de?ned my invention, its ‘scope and
its uses. Now I shall proceed to illustrate but. ‘not limit
my ‘invention by the following working examples:
Example 1
An equimolar mixture of bis(4=methylaminoe3amethyl=
phenyl)methanol and benzoic acid hydrazide is dissolved
in about 20 times its weight of absolute ethanol and re
?uxed for about 8 hours. ‘The resultingfmixtu’re is evapo
acid is permanent.
The novel compounds of the present invention in their
substantially colorless forms produce unexpected vivid
rated to dryness. The dark ‘solid residue is disolved in
violet colors on being brought into contact with a hetero
boiling benzene and decolorizied with activated charcoal.
The resulting colorless crystalline products have the fol
polyacid such as phosphotungstic acid, phosphotung
lowing structural formula
stomolybdic acid, and phosphomolybdic acid. This is a
surprise and contrast to the blue colors produced by the 55
similar compounds disclosed in my copending companion
application Serial No. 677,165 ?led August 8, 1957, now
U.S. Patent 2,900,388.
The novel compounds of my invention are cheap to
manufacture, stable in storage and handling, and useful 60
as coloring agents.
'
One way to manufacture my compounds involves re
action of the selected acid hydrazide with bis(4-methyl
a'min'o-3-rnethylphenyl)methanol or bis(4-methyla_mino-3
methylphenyl)methylamine or with di(4-methylamino-3
methylphenyDketone followed by hydrogenation, suitably
in polar solvents such as methanol, ethanol and di-oxane
according to the following respective equations:
CH3
‘
(OHQNH
H
1
0-0
—
CH3
I
'
R-CONHNH:
NH(CH3)
CH3
-
CH3
Instead of benzoic acid hydrazide, naphthoic acid by
drazide or any other acid hy'drazide ofthe aromatic series,
especially with at least one electrophilic substituent group
on the ring, may be used, the corresponding product is
65 also a crystalline solid.
,
,
a
ExampIeZ
An equimolar mixture of 3-nitrobenzoic acid hydrazide
and bis(4-methylamino—3-inethylphenyl)methanol is dis
70 solved at least 30 times its 'w‘eig'h'twof absolute‘ ethanol
and re?uxed for about ten hours. The resulting solution
is concentrated by evaporation until the solids appear.
3,078,836
3
4
After cooling to about 0° C., the brownish dark solids
are separated by ?ltration, dissolved in su?icient hot ben
zene and treated with activated charcoal. The resulting
the oily residue is washed thoroughly with water to remove
pyridine and any chlorides, and then heated under re?ux
for two to three hours with 30 ml. of anhydrous hydrazine
and 250 ml. of ethanol. The resulting solution is poured
with stirring into a large volume of water. The white solid
light orange yellow crystalline solids have the following
structural formula:
ICE;
product is collected, having the formula:
CHI
I
No:
if
NHNHC
The method of Example 4 is repeated in using the mixed
dichlorobenzoic acid hydrazide instead of 2,4-dichloro
'benzoic acid hydrazide. The resulting White solids have
the following‘structural formula:
The 2-nitro and 4-nitro isomers, and m0n0chloro~
mononitro compounds may be prepared in'the same man—
ner with the corresponding acid hydrazide, and they are
also orange yellow solids. Since this is not a dye color, it
is to be considered as substantially colorless.
@CONHNH:
10
15_
CH3
|
CH3
H
7 Example 3
t‘)
An equimolar mixture of bis(4-methylamino-3-methyL 20
phenyl)methanol and 4-chlorobenzoic acid hydrazide is
dissolved in 19 times its weight of absolute ethanol and
01
:
or
re?uxed for about 6 hours. The reaction mixture is
Similar procedure may be used to prepare mixed m0n0~
evaporated to dryness. The greenish dark residue is treat
chloro or monobromo, trichloro or tribromo, and poly
25
ed with activated charcoal in hot benzene and the result
chloro or polybromo acyl hydrazine derivatives of bis(4
ing white crystalline solids have the following structural
methylamino-B-methylphenyl)methane by the use of cor
formula:
responding halogenated benzoic acid hydrazide.
Example 6
A mixture of bis(4-methylamino-3-methy1pheny1)meth
30
amine and p-toluic acid hydrazide in 1:1.1 molar propor—
tion is dissolved in 15 times its weight of absolute ethanol
and re?uxed for about 8 hours. The reaction mixture is
35 evaporated to dryness. The yellowish residue is thorough
ly washed with hot water to remove the unreacted hy
Other isomeric chloro compounds and bromo com
drazide, and dissolved in benzene and then run through
pounds may be prepared in the same manner with the
a paper column to remove the yellow color. A colorless
corresponding acid hydrazide; and they are all white solid
crystalline product is obtained, having the following struc
materials.
Example 4
40 tural formula:
H;
An equimolar mixture of bis(4-methylamino-3-methyl
pheny1)methanol and 2,4-dichlorobenzoic acid hydrazide
is dissolved in thirty times its weight of absolute alcohol
and re?uxed for a few hours until no more free hydrazide
can be detected by the use of ethyl glyoxylate. The reac~
tion mixture is evaporated to dryness. The dark solid
residue is treated with activated charcoal in hot benzene
and the resulting colorless crystalline solids have the fol
lowing structural formula:
CH3
|
‘
'
OH;
l
1'1
45,
c1
0
H
|
w...a@_t©mm
.LHNH.l_@CH.
I
O
Instead of p-toluic acid hydrazide, other cyclic car
boxylic acid hydrazide of the aromatic series may be used
60 to prepare the corresponding acyl hydrazine.
Example 7
(om) HN-Q-C-GNH (CH3)
.
CH;
H
An equimolar mixture of isonicotinic acid hydrazide and
bis(4-methylarnino-3-methylphenyl)methanol is dissolved
55 in about 20 times its weight of absolute ethanol and re
NHNHC-QCI
Similarly, the other isomeric dichloro compounds or
dibromo compounds may be prepared using the same mo 60
lecular proportion, and they are all white crystalline solid
?uxed for about 7 hours. After removal of the solvent,
the dark solid residue is treated with activated charcoal.
The resulting colorless grainy solids have the following
structural formula:
'
H
I
materials, such as 2,3; 2,5; 2,6; 3,4; and 3,5-dihalo acyl
hydrazines.
Example 5
O
Chlorine is passed into 56 g. of benzoyl chloride con 65
N
/
taining 0.4 g. of ?ne iron powder and 0.2 g. of iodine at
50° to 60° C. until there is an increase in weight of 32
The isonicotinic acid hydrazide maybe replaced by one
g. After removal of the hydrogen chloride and free
of the following compounds: the hydrazide of nicotinic
chlorine by passing a current of air through the mixture,
acid, picolinic acid, tetrachloroisonicotinic acid, 2,6-di
the net in weight is reduced to 28 g., which corresponds 70 chloroisonicotinio acid, 2,6-dihydroxyisonicotinic acid,
NHNHé
to the theoretical quantity of the dicblorobenzoyl chlo~
ride. The resulting product is esteri?ed by refluxing with
3,S-dichloro-2,6-dihydroxyisonicotinic acid and lower
alkylated pyridine carboxylic acid in the same molar pro
250 ml. of absolute ethanol and 40 ml. of pyridine for
portion. Each of the products is a colorless crystalline
about one hour. After removal of ethanol by evaporation 75 material.
8,073,838
6
5v
Example 8
What
1. A compound
is claimed of
is: the formula
'
The procedure of Example 6 is repeated in using 2
thiophenic acid hydrazide instead of ‘prtoluoic acid hy
drazide instead of petoluoic acid hydra‘zide. The result
ing product is a white, crystalline solid, having the follow
ing structural formula:
16
wherein R is a member selected from the group consist
ing of phenyl, naphthyl, 'pyridyl; thien‘yl' and furyl and
their halogen, lower alkyl, lower alkoxy and nitro sub
stitution derivatives.
15)
‘
'
‘
2- A QQIHPQHBSI of the-lemma
CH3
.
CH3
In place Qt Z-thiQRhmiQ acid hydrazide, one of the hy
drazides' of ’ thj'e'lfollowing ~acids
useddn same
molar proportioni halogenated, nitrat'ed, or lower alkyl
and thiophenis acids- Ther are all substantially. v<=<>;l_<1~_r
less crystalline solids. assent the nitrederiratives which are
20
l
'
.
yellow in color.
Example 9
The procedure of Example 1 is repeated in employing
25
1'31
30
|
l
.
H
.
.
.
'
wherein R is chlorinated pyridyl.
3. A compound of the formula
2-=furoic acid hydrazide in lieu of benzoic acid hydrazide.
The resulting white crystalline solids have the following
structural formula:
(OHQHNGm-G-NMOHQ)
O
NHNH C-R
wherein R is tetrachloro-4-pyridyl.
4. A compound of the formula
35
The hydrazides of nitrated, or halogenated furoic acid‘
may be used to replace the furoic acid hydrazide in the
same molar ratio. The corresponding acyl hydrazines
are substantially colorless solids except the nitro com 40
pounds which are yellow.
Example '10
wherein R is chlorinated phenyl.
5. 1 - bis(4 - methylamino - 3 - methylphenyDmethylQ
An attapulgite clay known as Attasorb RVM marketed
by Minerals and Chemicals of America is sieved on to a 45
sheet of white paper. When a colorless solution contain
ing' 1% coloring material of Example 3 in ethanol is
dropped on the clay, a deep redish purple spot is produced
7. 1 - bis(4 - methyl-amino - 3 - methylplienynmethyl
50
The compound of Example 4 in the form of ?ne powder
,is placed on a sheet of white paper.
6. l - bis(4 - methylamino - 3 - methylphenyl)methyl
2-(2,4-dichlorobenzoyl)hydrazine.
2- (3 ,4-dichlorobenzoyl ) hydrazine.
immidiately.
Example 11
2-dichlorobenzoylhydrazine.
8. 1 - bis(4 - methylamino - 3 - methylphenyl)methyl~
Z-nitrobenzoylhydrazine.
-
9. 1 - bis(4 - methylamino - 3 - methy1phenyl)methy-l
When an ethanol
2-( 3-nitrobenzoyl) hydrazine.
solution containing about ‘0.6% phosphotungstic acid is
l0. 1 - bis(4 - methylamino - 3 - methylphenyDmethyl
dropped on this compound, a vivid violet color is pro
duced.
Z-chloronitrobenzoylhydrazine.
11. 1 - bis(4 - methylamino - 3 - methylphenyl)methyl
2~benzoylhydrazine.
Example 12
The compound of Example 1 in the form of ?ne White
12. A compound of the formula
powder is spread on a piece of white paper. N-propyl
or N-octyl gallate is then sieved on top of it. On being 60
put on a hot iron, or exposed to infra-red radiation, the
mixture immediately turns reddish blue.
CH3
OH;
Example 13
A piece of chemically neutral and white cotton or ?lter 65
wherein R is 2,6~dihydroxy-3,5-dihalo-4-pyridyl.
paper is impregnated with 1% colorless benzene solution
13. A compound of the ‘formula I
of the coloring material in Example 4 and dried. On
being dipped into a 50° to 60° C. water bath containing
CH3
.
CH3
0.5% phosphotungstic acid. The colorless treated fabrics
'
It
turn vivid violet instantaneously and permanently, yet the 70
water bath remains crystal clear and colorless.
From the foregoing examples the one skilled in the arts
_
| .
would have little or no dif?culty to produce any aromatic
acyl hydrazine derivatives and utilize them in ‘generating
any desired shades of colors.
NHNH(%—R
75 wherein R is halogenated furyl.
3,073,836
7
14. A compound of the formula
CH3
'8
‘
16. A compound of the formula
CH:
1
CH3
Iii
|
(om) BIN-@C-QNHGJHQ
5
Nmgg
(0H,)HN-
O
CH;
H
J>©mncm>
‘
0
NHNHg-R
\N
wherein R is 4-pyridyl.
17. 1 - bis(4 - methylamino - 3 - methylphenyDmethyl
I
Z-(halogenated thienoy1)hydrazine.
15. A compound of the formula
18. 1 - bis(4 - methylamino - 3 - methylphenyDmethyl
‘Em
2-(nitrated furoyl)hydrazine.
_
19. 1 - bis(4 - methylamino - 3 - methylpheny1)methyl
15 2-(2,6-dihydroxyisonicotinyl)hydrazine.
References Cited in the ?le of this patent
UNITED STATES PATENTS
ll
NHNH C-R
wherein R is 2,6-dichloro-4-pyridyl.
20 2,741,534
-
" 900,388
Pedersen _______ -4 ____ __ Apr. 10, 1956
Tien _________________ __ Aug. 18, 1959
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