Synthesis of 3-(3″-aminobenzoylamido)-1-(2′,4′,6′- trichlorophenyl)pyrazol-5-one, an intermediate in the synthesis of the purple component of color photographic materials

Article abstract of DOI:10.1007/s11167-005-0274-3

Catalytic reduction of 3-(3″-nitrobenzoylamido)-1-(2′,4′, 6′-trichlorophenyl)pyrazol-5-one with hydrogen and hydrazine hydrate to 3-(3″-aminobenzoylamido)-1-(2′,4′,6′-trichlorophenyl) pyrazol-5-one, the key intermediate in the synthesis of the purple component of color photographic and motion-picture materials, was studied.

Full text of DOI:10.1007/s11167-005-0274-3

Russian Journal of Applied Chemistry, Vol. 78, No. 2, 2005, pp. 278 280. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005,
pp. 284 286.
Original Russian Text Copyright
2005 by Yutilov, Smolyar, Minkina.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of 3-(3"-Aminobenzoylamido)-1-(2 , 4 , 6 -trichloro-
phenyl)pyrazol-5-one, an Intermediate in the Synthesis
of the Purple Component of Color Photographic Materials
Yu. M. Yutilov, N. N. Smolyar, and L. V. Minkina
Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine,
Donetsk, Ukraine
Received August 4, 2004
Abstract Catalytic reduction of 3-(3"-nitrobenzoylamido)-1-(2 , 4 , 6 -trichlorophenyl)pyrazol-5-one with hy-
drogen and hydrazine hydrate to 3-(3"-aminobenzoylamido)-1-(2 , 4 , 6 -trichlorophenyl)pyrazol-5-one, the key
intermediate in the synthesis of the purple component of color photographic and motion-picture materials,
was studied.
It is known that the protectable purple component,
3-[3-(2", 4"-di-tert-pentyl)phenoxyacetamido]benzoyl-
amido-1-(2 ,4 ,6 -trichlorophenyl)pyrazol-5-one I, shows
high photographic properties [1, 2]. One of procedures
for its synthesis is labor-consuming and involves
use of difficultly available chemicals [3].
The most facile route to I is based on the reaction
of 3-(3"-aminobenzoylamido)-1-(2 , 4 , 6 -trichloro-
phenyl)pyrazol-5-one II with 2,4-di(tert-pentyl)phen-
oxyacetyl chlolride III, with a 75% yield of the target
product [4]:
OCH2C(O)Cl
NHC(O)
NHC(O)
N
N
O
O
NH
CO
CH2
O
NH2
N
N
+
Cl
Cl
Cl
Cl
Cl
Cl
I
II
III
Intermediate II is formed by reduction of 3-(3"-
nitrobenzoylamido)-1-(2 , 4 , 6 -trichlorophenyl)pyr-
azol-5-one IV, which is, in turn, prepared by acyla-
tion of 3-amino-1-(2 , 4 , 6 trichlorophenyl)pyrazol-
5-one V with m-nitrobenzoyl chloride VI in 80%
yield [4]:
NHC(O)
N
NH2
C(O)Cl
N
O
O
NO2
N
N
+
Cl
Cl
Cl
Cl
NO2
Cl
Cl
IV
V
VI
1070-4272/05/7802-0278 2005 Pleiades Publishing, Inc.

SYNTHESIS OF 3-(3"-AMINOBENZOYLAMIDO)-1-(2 , 4 , 6 -TRICHLOROPHENYL)PYRAZOL-5-ONE 279
Yield and melting point of amino compound II prepared by catalytic reduction of IV under various conditions
Yield, %
mp,*
C
Reductant
Catalyst
T,
C
cNaOH, wt %
94.5
95.7
95.1
94.9
96.4
94.8
96.8
95.0
95.7
92.5
93.0
96.2
97.03
97.1
297 299
298 300
298 300
297 300
298 300
297 299
297 299
296 298
298 300
285 287
269 273
296 298
296 298
295 298
H2
H2
H2
H2
H2
Raney Ni
Raney Ni
5% Pd/C
5% Pd/BaSO4
5% Pt/C
20
0.5
2
2
2
1
1
3
2
2
6
0.5
2
4
6
20
20
20
20
20
20
30
40
40
50
40
40
40
H2
H2
5% Pt/BaSO4
5% Pt/C
N2H4 H2O
N2H4 H2O
N2H4 H2O
N2H4 H2O
N2H4 H2O
N2H4 H2O
N2H4 H2O
Raney Ni
Raney Ni
Raney Ni
Raney Ni
5% Pd/C
5% Pd/BaSO4
5% Pt/BaSO4
*
According to [6], the melting point of II is 297 300 C.
To diminish the corrosive effect of HCl released
in the acylation of II, it is bound by adding triethyl-
amine [5]; this also favors preparation of pure I.
NaOH solutions, the yield of II was 94.5 and 95.7%,
respectively. In reduction of IV with hydrogen in 2%
aqueous NaOH in the presence of 5% Pd/C and 5%
Pd/BaSO4, the yield of II was 95.1 and 94.9%.
Among the known procedures for reduction of IV
to II, of particular interest is the hydrogenation on
Raney nickel [6]. Some alternative reduction proce-
dures are also feasible [6], e.g., those with iron in hy-
drochloric or acetic acid, with sodium or ammonium
sulfide and with hydrogen in acetic acid in the pres-
ence of Pd/C. The last procedure allows preparation of
amine II in a high yield without degradation processes
such as, e.g., hydrolytic cleavage of the amide group
occurring in other procedures. Other possible side
processes are acetylation of the NH2 group with acetic
acid (when reduction of IV is performed in this me-
dium) and formation of sulfur (in reduction of IV with
sodium sulfide) negatively affecting the photographic
properties of II. Being environmentally clean, reduc-
tion with hydrogen on Raney nickel has a drawback:
The conditions of reduction of IV in alkaline alcoholic
solution (1 20 wt % Raney nickel, 20 110 C, 1
20 atm of H2) give rise to an explosion hazard.
The reduction of IV with hydrogen in 1% aqueous
NaOH in the presence of 5% Pt/C and 5% Pt/BaSO4
under the similar conditions affords II in 96.4 and
94.8% yield, respectively. At a higher (3%) NaOH
concentration, the yield of II in reduction of IV in
the presence of 5% Pt/C increased to 96.8%. The con-
ditions of reduction of IV and the yield and melting
point of II are listed in the table.
In view of the problems associated with the use of
hydrogen, we attempted to replace it with hydrazine
hydrate. In our experiments, we used the same cat-
alysts as in the reduction with H2. Along with the cat-
alyst, we varied the reaction temperature and NaOH
concentration.
Reduction of nitro compound IV with hydrazine
hydrate in 2% aqueous NaOH at 30 and 40 C in
the presence of Raney Ni affords II in 95 and 95.7%
yield. When the reduction of IV with hydrazine hy-
drate is performed at 40 C in the presence of the same
catalyst but in 6% aqueous NaOH, the yield of II
decreases.
To eliminate these drawbacks, we attempted to
improve the procedure for reduction of IV with hy-
drogen. For this purpose, we performed the reduction
under the normal conditions (H2 pressure 1 atm, room
temperature) in aqueous-alcoholic NaOH solutions.
As catalysts, along with Raney nickel, we also tested
5% Pd/C, 5% Pt/C, 5% Pd/BaSO4, and 5% Pt/BaSO4.
The yield of II increases, respectively, to 96.2
and 96.3% when compound IV is reduced with hy-
drazine hydrate at 40 C in the presence of Pd/C (in
2% aqueous NaOH) or Pd/BaSO4 (in 4% aqueous
NaOH).
In reduction of IV with hydrogen under normal
conditions in homogeneous 0.5% and 2% aqueous
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 78 No. 2 2005

280
YUTILOV et al.
Raney nickel appeared to be the most effective in
Reduction of IV with hydrazine hydrate in 0.5
6.0% aqueous NaOH solutions at 30 50 C. A 10.0-g
(23.4-mmol) portion of IV was mixed with a solution
of 0.5 6 g of NaOH in 100 ml of water, and 2.0 g
of a catalyst (Raney nickel, 5% Pd/C. 5% Pt/C,
5% Pd/BaSO4, or 5% Pt/BaSO4) was added. Then
40 ml (0.8 mol) of 98 100% hydrazine hydrate was
added in portions with vigorous stirring and heat-
ing to 30 50 C. After heating for 3 4 h under these
conditions, the catalyst was filtered off, and the fil-
trate was acidified with 2% H2SO4 to pH 6. The pre-
cipitate was filtered off, washed with a small amount
of water, and dried.
aqueous NaOH at a 25-fold excess of hydrazine hy-
drate. In this case, the yield of II is the highest, and
its melting point and chromatographic characteristics
are identical to those of an authentic sample [7].
At a smaller (15-fold) excess of hydrazine hydrate,
or with an alkaline alcoholic solution used, the reduc-
tion of IV to II is incomplete.
EXPERIMENTAL
The purity of II was checked by high-velocity
microcolumn liquid chromatography on a Milikhrom
device equipped with a UV detector. A 64 2-mm
stainless steel column ( 3000 TP) was packed with
Separon (particle diameter 4 m). The best system for
elution of II was acetone water hexane, 86 : 12 : 2
(by volume). The chromatographing conditions were
as follows: sensitivity range 1.6, measurement time
CONCLUSIONS
(1) Preparative procedures were suggested for the
reduction of 3-(3"-nitrobenzoylamido)-1-(2 , 4 , 6 -tri-
chlorophenyl)pyrazol-5-one with hydrogen or hy-
drazine hydrate in aqueous NaOH in the presence of
Raney nickel, 5% Pd/C, 5% Pt/C, 5% Pd/BaSO4, or
5% Pt/BaSO4 to obtain 3-(3"-aminobenzoylamido)-1-
(2 , 4 , 6 -trichlorophenyl)pyrazol-5-one.
0.15 s, wavelength
in the STOP mode 280 nm,
1
eluent feed rate 200 l min , and paper feed rate
1
1800 mm h . The retention time of II under these
conditions was 48 s.
(2) A procedure was developed for prompt anal-
ysis of the quality of the amine with a Milikhrom
liquid chromatograph.
Reduction of IV with hydrogen in 0.5 3.0%
aqueous NaOH solutions at 20 C. A 10.0-g (23.4-
mmol) portion of IV was dissolved in 200 ml of
water containing 1 6 g (25 150 mmol) of NaOH and
subjected to catalytic hydrogenation in the presence
of a catalyst (Raney nickel, 5% Pd/C, 5% Pt/C, 5%
Pd/BaSO4, or 5% Pt/BaSO4). To do this, the reaction
vessel was first purged with nitrogen to remove air,
and then nitrogen was replaced with hydrogen. The re-
duction was performed at 25 C and an H2 pressure of
1 atm with continuous stirring until the hydrogen up-
take ceased (200 ml). The catalyst was filtered off, and
the filtrate was acidified with a solution of hydrochlo-
ric or acetic acid to pH 6. The precipitate was filtered
off, washed with a small amount of water, and dried.
REFERENCES
1. Theys, R.D. and Sosnovsky, Y., Chem. Rev., 1997,
vol. 97, no. 1, pp. 83 132.
2. Arient, J. and Dostal, J., Chem. Listy, 1988, vol. 82,
no. 12, pp. 1254 1281.
3. US Patent 3812145.
4. US Patent 2600788.
5. US Patent 3823156.
6. JPN Appl. 58-140075.
7. USSR Inventor’s Certificate, no. 1441734.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 78 No. 2 2005