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Патент USA US2126180

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Patented Aug. ‘9, 1938
I _ 2,126,180
‘UNITED STATES
>
PATENT oFFIcE ‘
2,126,180
-
_
UREIDO N-DIARYL DioARBoXvtIdAmo
1
'
“
HALIDES
George Malcolm Dyson, Cheadle Hulme, and
Arnold Renshaw, Manchester, England, as
signors to Parke, Davis & Company, Detroit,
Mich., a corporation of Michigan
.
Q,\
r
‘
No Drawing. Original application‘January: I6, _
1929, Serial No. 333,020. PatentNo. 1,969,299,
dated August 7, 1934. Divided and this‘applii
cation July 25, 1934, Serial No.1 736,900.
In ~
Great Britain February ‘1,1928
4 Claims.
Our invention relates to ureido N-diaryl dicar
boxylic acid halides.
This application‘ is a division of application,
Serial N0.‘ 333,020, ?led January .16, 1929, now
Patent 1,969,299, of Aug. 7, 1934, and relates more
particularly to certain new diaryl diacidhalides
and the process of preparing the same.
H _,
We have found that by the action of thionyl
chloride, phosphorus pentachloride, phosphorus
trichloride and similar substances upon dicar
boxylic aryl ureas or dicarboxylic aryl thioureas
or their substitution products, a new series of
aryl urea acid halides is produced; we have also
found that similar substances may be produced
by the action of thionyl chloride, or-phosphorus
chlorides upon carboxyl substituted aryl isocya
nates or isothiocyanates followed by treatment
o‘f‘the carbimide or thiocarbimide aryl acyl hal
ides so obtained with amino aryl carboxylic acids,
20 amino carboxylic acid derivatives of 'quinoline,
(01. 2607-123)
in which either VRI or vRzirepresent hydrogen, *1
the other representing‘ .a- ' carboxyl substituted
aryl nucleus, R3 repres‘entsa carboxyl substituted
aryl nucleus, X represents S‘ or O, and in which
the aryl nuclei may be further substituted. These
urea or thiourea diaryl dicarboxylicacids‘ .are
treated with thionyl chloride in. excess until solu
tion is complete. Theexcess of thionyl chloride
is removed by distillation (with or without inert
liquid such as» benzene) thereby‘obtaining the 10
residual. diaryl urea '(or thiourea)‘ dicarboxylic
acid chlorides. . These diacid chloride compounds
are new compounds and form part of thevsubject
matter of this‘invention. The following are the
diacid chlorides whichcorrespond respectively-to 15
thediaryl ureal (orlthiourea) ‘dica‘rboaylic acids '
listed abovea.v 1.
I
,
1. N ,N! -~dipheny_l-urea - 3,3'~ dicarboxylic acid
.20
, benzthiazole or the like, followed by further treat
ment with thionyl chloride.
"D001
‘ According to our invention we may advan
COO]
.
tageously use as a. starting material a urea diaryl
.25
dicarboxylic acid or a thiourea diaryl dicarbo-xylic
acid. Examples of these bodies which can be
used in our, process are:
' 1. N,N-dip-henyl-urea-3,3'-dicarboxylic acid;
‘ "2‘: )N-benz‘thiazolyl-N‘-phenyllurea-6,3’- dicar
boxylic acid chloride;'
1
‘
2:5
, 2. N - benzthiazolyl-N’-phenyl-urea-6,3'-dicar
boxylic acid;
'
'
{3. N,N-diphenyl-urea-3,3'-dicarboxylic acid;
" 4. N - phenyl-N’-(4'-quinolyl) -urea-3,6'-dicar
boxylic acid;
>
30
'
0100
i
5. N,N'- dipheny1-2-methoxy-4'- nitro-3,3'- cli
35
carboxylic acid;
.
‘
"6. ‘N‘,N’ - diphenyl - thiourea - 3,3'- dicarboxylic
acid.
‘
‘
‘.3. N,N -'“ diphenylfurjea 3,3"- dicarboxylic acid
chloridep"
*f‘
-
r
Y
,
‘
35
"The above‘ diaryl urea (or thio-urea) dicar
boxylic acids may be represented by the follow
40
ing generic formula:
.
-
.
40
II“
/
N-Rz
(II-SKNEE-R1
0001
2
2,126,180
.
4. N-phenyl-N’-(4’- quinolyl) -ure'a-'3,6'- dicar
boxylic acid chloride;
9
NHCONH
which can be used in our process there may be
mentioned 1,8-amino naphthol-3,6-disulphonic
acid, 1-naphthylamine-4,8-disulphonic acid, 1
naphthylamine-4,6,8-trisulphonic acid, chloro
naphthylamine sulphonic acid, bromo- or iodo
naphthylamine sulphonic acids, obtained by halo
C001
genating naphthylamine sulphonic acids by
known methods or by halogenating the acetyl
N
5. N,N’- diphenyl-2-methoxy-4’- nitro-3,3’- di
carboxylic chloride;
13
15
COCl
acids which can be used in our invention, there 15
C001
acid chloride;
9
COO]
10
thylamine sulphonic acids, 1,5-amino naphthol
7-sulphonic acid, 2,8-amino naphthol-3,6-disul
phonic acid.
Among the amino acenaphthene sulphonic
OCH:
6. N ,N’- diphenyl - thiourea - 3,3’ -dicarboxylic
20
naphthylamine sulphonic acids by known meth
ods and hydrolyzing the products; alkoxynaph
may be mentioned 4-amino acenaphthene-5-su1~
phonic acid
GHQ-CHI
20
'
‘
0001
Instead of using thionyl chloride, other thionyl
halides may be used, thus forming the corre
sponding diacid bromides,.iodides, etc.
It will
25 be understood also that instead of the thionyl
halides, phosphorus pentachloride, phosphorus
trichloride and the other corresponding halides
may be used.
H
The diacid chlorides are then reacted with a
30 primary aryl amine or advantageously with an
aminov naphthalene sulphonic acid or an amino
acenaphthene sulphonic acid oran amino arylido
naphthalene sulphonic acid to form the ureids in
accordance with our Patent No. 1,969,299 above
35 referred to.
In carrying out the process of our invention
we may react diaryl urea acid halides, formed
as above, with an amino acenaphthene sulphonic
acid or an amino naphthalene sulphonic acid or
40 with their substituents. The diaryl urea acid
halides may also be reacted with. the products
obtained by reducing the nitro-compounds ob
tained by the action on l-amino naphthalene sul
phonic acids of chlorides of nitro-arylfatty acids
and nitro-aryl chlorides, nitro-aryl ole?nicecar
boxylic acid chlorides, nitro-aryl sulpho-chlorides
or their substitution products, and in this way ob
tain symmetrical or unsymmetrical ureids which
. are of value as therapeutic agents or as inter
mediates for the production of colouring matters.
To form the substituted amino naphthalene
sulphonic acids, with which our diaryl urea acid
halides can be reacted to form the ureids of our
invention, we may react upon an amino naphtha
55 lene sulphonic acid with a nitro-aryl chloride,
do
for example, 2 nitro-cinnamyl chloride (Berichte
16, 34, Beilstein 2, 1414, 3rd edition), 3-nitro
cinnamyl chloride (German patents 288,272 and
288,273), 4-nitro-cinnamyl chloride (Berichte
1916, 49, 2688), 1-nitro~naphthalene-5-sulpho
chloride, 1:5:nitro-naphthoyl chloride, 2-nitro
phenylacetyl chloride (Berichte 43, 2547), 4
nitro-phenylacetyl chloride, nitro-benzoyl chlo
rides, nitro-anisoyl- chlorides, nitro-toluyl- chlo
65 rides, nitro-benzene sulpho-chlorides, chloroni
tro-benzoyl chlorides, bromonitro-benzo'yl chlo~
rides, iodonitro-benzoyl chlorides. The nitro
groups in the reaction products of the above
compounds with the amino naphthalene sulphonic
acids can be reduced to amino groups.
The
products can then be termed amino arylido naph
thalene sulphonic acids. These bodies reacted
with our diaryl urea acid‘halides produce the
. ureids of our invention.
Among the amino naphthalene sulphonic acids
HSOa
NH:
and 4-amino acenaphthene-3-sulphonic acid 25
~(Fleischer and Schranz, Ber. 55, 3253 (1922),
G. T. Morgan and V. E. Yarsley, Journal of the
Society of Chemical Industry, 44, 513T (1925),
4-amino acenaphthene-3:5-disulphonic acid (G.
T. Morgan and V. E. Yarsley, Journal of the 30
Society of Chemical Industry, 44, 513T (1925),
and 4-amino acenaphthene-trisulphonic acids,
obtained‘ by further sulphonation of 4-amino
acenaphthene-5-sulphonic acid with oleum or
of 4-nitro-acenaphthene-5-sulphonic acid with 35
oleum and reduction of the N02 group.
The ?nished products may be puri?ed in any
suitable manner, as, for instance, by solution in
glacial acetic acid, or any other suitable solvent,
and precipitation of the substance from solution 40
by acetone, ether or other suitable precipitant.
As an example of this synthetic process, the
following manner of preparing a urea compound
is cited:
45
Example
m-Amino benzoic acid is dissolved in a dilute
aqueous solution of caustic soda and phosgene
gas passed into the solution so obtained which
may be‘arti?cially cooled; or, alternatively, the 50
solution of sodium m-amino benzoate istreated
with a solution of phosgenein an inert solvent
such as tetrachlorethane or toluene; or, alterna
tively, them-amino benzoic acid may be dissolved
in a mixture of non-aqueous solvents of which 55
pyridine forms a component part, and treated
with phosgene alone or in solution. In each
case, the compound diphenyl urea-3,3'-dic'ar
boxylic acid separates and is removed and dried.
The dry diphenyl urea 3,3’ dicarboxylic acid 60
is heated with thionyl chloride in excess until
solution is complete. The excess of thionyl chlo
ride is removed by distillation (with or. without
an inert liquid such as benzene) and the residual
diphenyl urea 3,3’ dicarboxylic acid chloride 65
(1 mol.) is stirred for several hours with an
aqueous solution of the sodium salt of m-amino
paratoluyl naphthylamine-4,6,8-trisu1phonic acid
(0.9 mol.) with or without thevaddition of a mild
alkali such as sodium carbonate, or sodium ace 70
tate, until the solution ceases to give a red color
ation when treated with sodium nitrite, hydro
chloric acid and resorcinol. The solution is ?l
tered from tar, evaporated to dryness, preferably
in vacuum, and extracted with methyl alcohol, 75
2,126,180
the clear methyl alcoholic solution is poured into
a large bulk of absolute ethyl alcohol and the
precipitated compound ?ltered off and dried.
3
2. Diary] dicarboxylic acid halides having the
formula
Income
The reactions taking place in the foregoing
N——-R2
5 example may be illustrated as follows:
04X
@coomwoocmO-ooon
\NH——R1
|
NH:
IIIH
10
00 +
|
11TH
in which one of the groups R1 and R2 repre
‘ sents‘ hydrogen, the other representing R4COI-Ial, 10
Where R3 and R4 represent organic radicals con
taining an aryl nucleus attached to N of the
s0o1¢——»
(Thionyl Chloride)
formula by way of carbon and with the groups
COHal attached to the aryl nuclei thereof, and
X is an element of the group consisting of sul 15
15
phur and oxygen.
20
NE
I
('30
NH:
—~OONH
7
3. Diary] dicarboxylic acid halides having the
formula
some
.
+2
~>
20
NH
I
\
SOaNE
0001
25
25
in which one of the groups R1 and R2 repre
CHa
sents hydrogen, the other representing R4COC1,
—OONH
CONH
>
SOaN?
30
NH
.
00/
\N
'
some
H
mula by way of carbon and with the groups COCl
attached to the aryl nuclei thereof, and X is an 30
element of the group consisting of sulphur and
oxygen.
SOaNa
-
where R3 and R4 represent organic radicals con
taining an‘aryl nucleus attached‘to N of the for
o
H
7
_
4. Diaryl dicarboxylic acid halides having the
001m
8 OaNa
formula
.
i
.
'
CsHsCOG]
CH;
;
35
SOaNa
40
SCENE
40
The process and reactions with the thioureas
are similar.
What we claim as our invention is:
1. Diphenyl urea 3,3’--dicarboxylic acid chlo
> 45 ride:
in which one of the groups R1 and R2 repre
sents hydrogen, the other representing C6H5COC1
and X is an element of the group consisting
of sulphur and oxygen.
45
GEORGE MALCOLM DYSON.
ARNOLD RENSHAW.
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