Regioselective synthesis of diazaspiro[4.4]nona- and tetrazaspiro[4.5]deca- 2,9-diene-6-one derivatives

Article abstract of DOI:10.1002/jhet.5570450134

(Chemical Equation Presented) Several 1,2-diazaspiro[4,4]nona-2,8-diene-6- one derivatives were synthesised via cycloaddition of nitrilimides to 3-aryliden-2(3H)-furanone derivatives. The formed products react with hydrazine hydrate to give the correspond

Full text of DOI:10.1002/jhet.5570450134

Jan-Feb 2008
279
Regioselective Synthesis of Diazaspiro[4.4]nona- and
Tetrazaspiro[4.5]deca-2,9-diene-6-one Derivatives
Ahmad M. Faraga, Yehya M. Elkholyb and Korany A. Alia
aDepartment of Chemistry, Faculty of Science, Cairo University, Giza 12613, Egypt
bDepartment of Chemistry, Faculty of Science, Helwan University, Ain-Helwan, Cairo,Egypt
Email: afarag49@yahoo.com
Received December 27, 2006
Ph
Ar
R
N
+
-
N
N
R
N
Ar
Ph
O
O
Ar
Ph
Ar
Ph
O
O
Ph
Ph
O
CONHNH2
CH2COPh
HCl/AcOH
N
NH
NH
N
N
Ph
N
Ph
Ph
Several 1,2-diazaspiro[4,4]nona-2,8-diene-6-one derivatives were synthesised via cycloaddition of
nitrilimides to 3-aryliden-2(3H)-furanone derivatives. The formed products react with hydrazine hydrate to
give the corresponding pyrazolecarbohydrazide derivatives which undergo intramolecure cyclization upon
treatment with HCl/AcOH mixture to affored 1,2,7,8-tetrazaspiro[4.5]deca-2,9-diene-6-one derivatives.
Molecular mechanics energy minimization techniques and related structural parameters for compound 8-
(4-methylphenyl)-1,3,4-triphenyl-7-oxa-1,2-diazaspiro[4.4]nona-2,8-diene-6-one 5a are reported.
J. Heterocyclic Chem., 45, 279 (2008).
was isolated. This regioselectivity was evidenced from
TLC and 1H nmr analysis of the crude reaction product.
INTRODUCTION
The considerable pharmacological importance of furan-
2-one derivatives have attracted a great deal of attention
[1-6]. The various changes in the structure of these
compounds are worth studying in order to synthesize less
toxic and more potent drugs. Thus, attachment of other
heterocyclic moieties, which are known to possess
pharmacological activity, to furan ring may lead to the
fulfillment of this objective. On the other hand, pyrazole
derivative are known to have significant biological and
pharmacological activity [7-9]. As an extension of our
research program aiming at the synthesis of a variety of
heterocyclic systems for biological screening [10-20], we
report here on the syntheses of some important diazo-
spiro[4.4]nona- and tetrazaspiro[4.5]deca-2,9-diene-6-one
derivatives.
Scheme 1
Cl
H
N
R
N
Ar
1
Et3N
Ph
+
-
O
+
N
O
R
N
Ar
X
3
2
N
N
R
Ar
RESULTS AND DISCUSSION
Ar
R
N
N
Ph
O
In the course of our investigation, we have found that 3-
phenylmethylene-5-arylfuran-2(3H)-ones 3, are excellent
building blocks for the synthesis of a variety spiropyr-
azole ring systems [21-23]. Thus, treatment of 3-phenyl-
methylene-5-arylfuran-2(3H)-ones 3 with nitrileimides
2a-i) generated in situ by the action of triethylamine on
hydrazonoyl chlorides 1a-i [24-26]), in benzene under
reflux, afforded the corresponding cycloadducts 5a-i in
good yields (Scheme 1). The reactions of 2 with 4 are
regioselective and, in each case, only one regioisomer of 5
Ph
O
O
O
X
X
5
4
4,5ꢀ Xꢀ
aꢀCH3ꢀ
bꢀOCH3ꢀ
Rꢀ
Arꢀꢀꢀꢀꢀꢀ
C6H5
C6H5
C6H5
4-CH3C6H4
4-ClC6H4
C6H5
4-CH3C6H4
4-ClC6H4
C6H5
C6H5
C6H5ꢀ
c
Hꢀ
COOEtꢀ
COOEtꢀ
COOEtꢀ
COOEtꢀ
COOEtꢀ
COOEtꢀ
CONHPh
dꢀ Hꢀ
eꢀ Hꢀ
fꢀ CH3ꢀ
gꢀCH3ꢀ
hꢀCH3ꢀ
iꢀ Hꢀ

280
A. M. Farag, Yehya M. Elkholy and K. A. Ali
Vol 45
The 1H nmr spectrum of compound 5a, taken as a typical
Scheme 2
example of the prepared series, displayed a singlet signal at
ꢀ 2.15 due to methyl protons and showed two singlet
signals in the region at ꢀ 5.01 and 5.23 assigned to the CH
protons of the pyrazole and furanone ring residues,
respectively, in addition to a multiplet at ꢀ 7.15-7.35
corresponding to the aromatic protons. Data produced using
MM2 method via energy minimization techniques followed
by molecular dynamics run for 20000 fs at room
temperature, in the form of Cartesian coordinations for all
representative atoms including H-atom (all atoms force
field) are normaly representive of x, y, z, coordinates
obtained from single crystal diffractions method [27-29].
N
R
Ar
N
Ph
O
O
5
X
NH2NH2
-ArCOCH3
Ph
O
R
R
Ph
H
N
NH2
N
-ArCOCH3
N
N
H
N
NH2
N
Ar
Ar
O
O
X
7
X
R
Ar
a
b
c
d
e
f
C6H5
C6H5
COOEt
COOEt
COOEt
COOEt
C6H5
C6H5
C6H5
4-CH3C6H4
C6H5
4-CH3C6H4
6
H
CH3
H
H
CH3
CH3
Treatment of 5-(2-phenyl-2-oxoethyl)-1,3,4-triphenyl-
4,5-dihydro-1H-pyrazole-5-carbohydrazide 6a with
a
mixture of hydrochloric acid and glacial acetic acid at
reflux temperature, afforded a single product (TLC)
identified as 1,3,4,9-tetraphenyl-1,2,7,8-tetraza-spiro[4.5]-
deca-2,9-diene-6-one 10 (Scheme 3). The IR spectrum of
the isolated product 10 showed a band at 3417 cm-1 due to
NH group and a strong absorption band at 1744 cm-1 due
to carbonyl group. These results indicate that the reaction
of 6a with hydrochloric acid and glacial acetic acid
proceeds, via the elimination of water molecule from the
non-isolable intermediate 9.
Figure 1. Molecular structure of 5a
Treatment of the 7-oxa-1,2-diazaspiro[4.4]nona-2,8-
diene-6-one derivatives 5a-f with hydrazine hydrate, in
ethanol at room temperature afforded the corresponding
1-aryl-4-phenyl-5-(2-Phenyl-2-oxoethyl)-pyrazole-5-carbo-
hydrazide derivatives 6a,b and ethyl 5-(hydrazino-
carbonyl)-5-(2-phenyl-2-oxoethyl)-1,4-diphenyl-4,5-
dihydro-1H-pyrazole-3-carboxylate derivatives 6c-f,
respectively (Scheme 2).
The structures of the isolated products were assigned on
the basis of their elemental analyses and spectral data. For
example, the ir spectra of compounds 6a,b showed, in
each case, two strong carbonyl absorption bands in the
region 1710-1680 cm-1 and showed three bands in the
region 3300-3430 cm-1 corresponding to NH and NH2
groups. The 1H nmr spectrum of compound 6b, taken as a
typical example of the prepared series, revealed two
singlet signals at ꢀ 2.15 and ꢀ 4.16 corresponding to
methyl and methylene protons, respectively, and two
broad bands (D2O-exchangeable) at ꢀ 8.78 and 3.87 due to
NH and NH2 protons, respectively, in addition to multiplet
signals in the region ꢀ 7.25-7.50 due to aromatic protons.
Moreover, the mass spectrum of compound 6a revealed a
peak at m/z 474 corresponding to its molecular ion.
Scheme 3
Ph
CONHNH2
CH2COPh
Ph
Ph
Ph
CONHNH2
..
N
HCl/AcOH
N
N
N
CH2CPh
O
Ph
Ph
8
6a
Ph
Ph
Ph
Ph
O
O
-H2O
N
NH
NH
N
NH
NH
N
N
Ph
Ph
OH
Ph
Ph
10
9

Jan-Feb 2008
Synthesis of Diazaspiro[4.4]nona- and Tetrazaspiro[4.5]deca-2,9-diene-6-one Derivatives
281
ArH's); MS (m/z): 452 (M+), 379, 360, 105, 77. Anal. Calcd for
C28H24N2O4 (452.507): C, 74.32; H, 5.34; N, 6.19%. Found: C,
74.20; H, 5.50; N, 6.00%.
Ethyl 6-oxo-1-(4-chlorophenyl-4,8-diphenyl-7-oxa-1,2-
diazaspiro[4.4]nona-2,8-diene-3-carboxylate (5e). Yield 70%;
mp 123 °C; ir (KBr) ꢀ/max cm-1 1807 (C=O of lactone), 1714
(C=O of ester). 1H nmr (ꢁ, ppm, CDCl3): 1.21 (t, 3H, ester-CH3),
4.22 (q, 2H, ester-CH2), 4.93 (s, 1H, CH-pyrazole), 5.30 (s, 1H,
CH-furanone), 7.15-7.41 (m, 14H, ArH's). Anal. Calcd for
C27H21N2O4Cl (472.925): C, 68.57; H, 4.47; N, 5.92; Cl, 7.50%.
Found: C, 68.70; H, 4.30; N, 6.10; Cl, 7.40%.
Ethyl 6-oxo-1,4-diphenyl-8-(4-methylphenyl)-7-oxa-1,2-
diazaspiro[4.4]nona-2,8-diene-3-carboxylate (5f). Yield 80%;
mp 110 °C; ir (KBr) ꢀ/max cm-1 1813 (C=O of lactone), 1728
(C=O of ester). 1H nmr (ꢁ, ppm, CDCl3) 1.23 (t, 3H, ester-CH3),
2.37 (s, 3H, CH3), 4.24 (q, 2H, ester-CH2), 4.95 (s, 1H, CH-
pyrazole), 5.27 (s, 1H, CH furanone), 7.16-7.34 (m, 14H, ArHs).
13C nmr )ꢁ, ppm, CDCl3): 14.06, 21.45, 61.29, 61.47, 99.68,
117.72, 123.91, 124.29, 125.34, 128.22, 128.37, 129.05, 129.16,
129.46, 129.59, 129.99, 134.66, 141.37, 141.96, 142.10, 154.61,
161.07,174.25. Anal. Calcd for C28H24N2O4 (452.507): C, 74.32;
H, 5.34; N, 6.19%. Found: C, 74.10; H, 5.50; N, 6.30%.
EXPERIMENTAL
All melting points were measured on a Gallenkamp melting
point apparatus and are uncorrected. The infrared spectra were
recorded in potassium bromide disks on a Pye Unicam SP 3300
and Shimadzu FT ir 8101 PC infrared spectrophotometers. The
nmr spectra were recorded on a Varian Mercury VX-300 nmr
spectrometer. 1H (300 MHz) and 13C nmr (75.46 MHz) were run
in deuterated chloroform (CDCl3) or dimethylsulphoxide
(DMSO-d6). Chemical shifts were related to that of the solvent.
Mass spectra were recorded on a Shimadzu GCMS-QP 1000 EX
mass spectrometer at 70 e.V. Elemental analyses were carried
out at the Microanalytical Center of Cairo University, Giza,
Egypt.
8-Aryl-1,3,4-triphenyl-7-oxa-1,2-diazaspiro[4.4]nona-2,8-
diene-6-one derivatives 5a,b. General procedure. To a
solution of the appropriate arylidenefuranone derivative 3 )10
mmol) and N-phenylbenzohydrazonyl chloride 1a,b (10 mmol),
in dry benzene (30 mL), was added triethylamine (10 mmol) and
the mixture was refluxed for 4 h then allowed to cool. The solid
that formed was collected by filtration, washed with methanol
and crystallization from ethanol.
Ethyl 6-oxo-1,8-di(4-methylphenyl)-4-phenyl-7-oxa-1,2-
diazaspiro[4.4]nona-2,8-diene-3-carboxylate (5g). Yield
75%; mp 115 °C; ir (KBr) ꢀ/max cm-1 1805 (C=O of lactone),
1728 (C=O of ester). 1H nmr (ꢁ, ppm, CDCl3): 1.20 (t, 3H, ester-
CH3), 2.24 (s, 3H, CH3), 2.41 (s, 3H, CH3), 4.2 (q, 2H, ester-
CH2), 4.91 (s, 1H, CH pyrazole), 5.22 (s, 1H, CH furanone),
7.11-7.33 (m, 13H, ArHs). 13C nmr )ꢁ, ppm, CDCl3): 14.03,
21.46, 61.40, 78.81, 99.01, 99.24, 119.01, 124.08, 125.31,
125.36, 128.19, 128.47, 129.11, 129.18, 129.22, 129.52, 129.59,
129.98, 130.04, 134.38,134.66, 140.67, 141.59, 154.88,154.91,
160.85, 173.94. Anal. Calcd for C29H26N2O4 (466.539): C,
74.66; H, 5.61; N, .6.00%. Found: C, 74.40; H, 5.70; N, 6.20%.
Ethyl 6-oxo-1-(4-chlorophenyl)-8-(4-methylphenyl)-4-
phenyl-7-oxa-1,2-diazaspiro[4.4]nona-2,8-diene-3-carbox-
ylate (5h). Yield 78%; mp 113 °C; ir (KBr) ꢀ/max cm-1 1805
(C=O of lactone), 1732 (C=O of ester). 1H nmr (ꢁ, ppm, CDCl3):
1.22 (t, 3H, ester-CH3), 2.37 (s, 3H, CH3), 4.23 (q, 2H, ester-
CH2), 4.94 (s, 1H, CH- pyrazole), 5.25 (s, 1H, CH-furanone),
7.17-7.34 (m, 13H, ArHs). 13C nmr (ꢁ, ppm, CDCl3): 14.03,
21.46, 61.42, 61.48, 99.00,99.24, 119.01, 124.08, 125.31,
125.36, 128.19, 128.47, 129.03, 129.11, 129.18, 129.22, 129.52,
129.59, 129.98, 130.04, 134.38, 134.66, 140.67, 141.59, 142.88,
154.91, 160.85, 173.94. MS (m/z): 488 (M+2), 486 (M+), 458,
262, 119, 91, 77. Anal Calcd.for C28H23N2O4Cl (486.95): C,
69.06; H, 4.76; N, 5.75; Cl, 7.28%. Found: C, 69.13; H, 4.85; N,
5.82; Cl, 7.52%.
8-(4-Methylphenyl)-1,3,4-triphenyl-7-oxa-1,2-diazaspiro-
[4.4]nona-2,8-diene-6-one (5a). Yield 73%; mp 183-184 °C; ir
(KBr) ꢀ/max cm-1 1801 (C=O of lactone). 1H nmr (ꢁ, ppm,
CDCl3): 2.15 (s, 3H, CH3), 5.01 (s, 1H, CH-pyrazole), 5.23 (s,
1H, CH-furanone), 7.15-7.35 (m, 19H, ArHs). Anal. Calcd for
C31H24O2N2 (456.54): C, 81.55; H, 5.30; N, 6.14 Found: C,
81.70; H, 5.10; N, 6.00%.
8-(4-Methoxyphenyl)-1,3,4-triphenyl-7-oxa-1,2-diazaspiro-
[4.4]nona-2,8-diene-6-one (5b). Yield 75%; mp 220-222 °C; ir
1
(KBr) ꢀ/max cm-1 1805 (C=O of lactone). H nmr (ꢁ, ppm,
CDCl3): 3.88 (s, 3H, OCH3), 6.81 (s, 1H, CH-pyrazole), 6.99 (s,
1H, CH furanone), 7.13-7.35 (m, 19H, ArHs). 13C nmr )ꢁ, ppm,
CDCl3): 55.41, 97.69, 114.4, 120.73, 125.66, 127.04, 129.0,
129.8, 129.90, 133.8, 135.39. 156.97, 161.50. MS (m/z): 472
(M+), 444, 194, 135, 91, 77. Anal. Calcd for C31H24O3N2
(472.54): C, 78.80; H, 5.12; N, 5.93%. Found: C, 79.00; H,
5.30, N, 6.10%.
Ethyl 6-oxo-1,8-Diaryl-4-phenyl-7-oxa-1,2-diazaspiro[4.4]-
nona-2,8-diene-3-carboxylate (5c-h). General procedure. To
a solution of the appropriate arylidenefuranone derivative 3 (5
mmol), and the corresponding hydrazonyl chloride 1c-e (5
mmol), in dry benzene (20 mL) was added triethylamine (0.8
mL, 6 mmol) and the mixture was refluxed for 6 h, then allowed
to cool. The solvent was removed under reduced pressure and
solid that formed was collected by filtration, washed with
methanol and finally recrystallized from ethanol.
6-Oxo-N,1,4,8-tetraphenyl-7-oxa-1,2-diazaspiro[4.4]nona-
2,8-diene-3-carboxamide (5i). To a solution of the benzylidene-
furanone 3a (3 mmol) and the hydrazonyl chloride 1i (3 mmol)
in dry benzene (20 mL) was added triethylamine (3 mmol) and
the mixture was refluxed for 4 h. The solvent was removed
under reduced pressure and the solid that formed was collected
washed with methanol and recrystallization from ethanol. Yield
78%; mp 180 °C; ir (KBr) ꢀ/max cm-1 3394 (NH), 1850 (C=O of
lactone), 1681 carbonyl of (CO-NHPh). MS (m/z) 485 (M+),
457, 363, 335, 259, 231, 105, 77. 1H nmr (ꢁ, ppm, CDCl3): 5.05
(s, 1H, CH-pyrazole), 5.33 (s, 1H, CH furanone), 7.25-7.45 (m,
20H, ArHs), 8.5 (s, 1H, NH). Anal. Calcd for C31H23N3O3
(485.540). C, 76.68; H, 4.77; N, 8.65%. Found: C, 76.9; H,
4.50; N, 8.30%.
Ethyl 6-oxo-1,4,8-triphenyl-7-oxa-1,2-diazaspiro[4.4]nona-
2,8-diene-3-carboxylate (5c). Yield 83%; mp 105-106 °C; ir
(KBr) ꢀ/max cm-1 1809 (C=O of lactone), 1724 (C=O of ester) .1H
nmr (ꢁ, ppm, CDCl3): 1.21 (t, 3H, CH3), 4.23 (q, 2H, CH2), 4.96
(s, 1H, CH-pyrazole), 5.32 (s, 1H, CH-furanone), 7.15-7.48 (m,
15H, ArH's). Anal. Calcd for C27H22N2O4 (438.48): C, 73.96; H,
5.05; N, 6.39%. Found: C, 73.70; H, 5.20; N, 6.20%.
Ethyl 6-oxo-4,8-diphenyl-1-(4-methylphenyl)-7-oxa-1,2-
diazaspiro[4.4]nona-2,8-diene-3-carboxylate (5d). Yield
70%; mp 115-116 °C; ir (KBr) ꢀ/max cm-1 1805 (C=O of lactone),
1712 (C=O of ester). 1H nmr (ꢁ, ppm, CDCl3): 1.20 (t, 3H, ester-
CH3), 2.47 (s, 3H, CH3), 4.21(q, 2H, ester-CH2), 4.92 (s,1H,CH-
pyrazole), 5.30 (s, 1H, CH-furanone), 7.16-7.39 (m, 14H,

282
A. M. Farag, Yehya M. Elkholy and K. A. Ali
Vol 45
Synthesis of 5-(2-Phenyl-2-oxoethyl)-1,3,4-triphenyl-4,5-
Ethyl 5-(hydrazinocarbonyl)-5-[2-(4-methylphenyl)-2-oxo-
ethyl]-1-(4-methylphenyl)-1-phenyl-1,4-dihydropyrazole-3-
carboxylate (6f). Yield 85%; mp 120 °C; ir (KBr) ꢀ/max cm-1
dihydro-1H-pyrazole 5-carbohydrazide and Ethyl 5-(hydra-
zinocarbonyl)-5-[2-phenyl-2-oxoethyl]-1,4-diphenyl-4,5-
dihydro-1H-pyrazole-3-carboxylate derivatives 6a,b and 6c-
f. General Procedure. Hydrazine hydrate (80%, 2 mL) was
added to a stirred solution of the appropriate spiropyrazolo-
furanone derivatives 5a-f (0.5 gm) in absolute ethanol (20 mL)
and the reaction mixture was stirred for 4 hours. The color of
spiropyrazolofuranone derivative disappears and white
precipitate was formed. The precipitated solid was collected by
filtration, washed with ethanol and crystalized from absolute
ethanol.
5-(2-Phenyl-2-oxoethyl)-1,3,4-triphenyl-4,5-dihydro-1H-
pyrazole-5-carbohydrazide (6a). Yield 80%; mp 175 °C; ir
(KBr) ꢀ/max cm-1 3300-3430 (NH, NH2), 1710, 1680 (2 C=O); 1H
nmr (ꢁ, ppm,CDCl3): 8.76 (s, 1H, NH), 3.75 (s, 2H, NH2), 4.15
(s, 2H, CH2), 4.83 (s, 1H, CH pyrazole), 7.25-7.51 (m, 20H,
ArHs). MS (m/z): 474 (M+), 456, 415, 336, 309, 194, 130, 91,
77, 51. Anal. Calcd for C30H26N4O2 (474.559): C, 75.92; H,
5.47; N, 11.80%. Found: C, 76.30; H, 5.70; N, 11.90%.
5-[2-(4-Methylphenyl)-2-oxoethyl]-1,3,4-triphenyl-4,5-
dihydro-1H-pyrazole-5-carbohydrazide (6b). Yield 82%;
mp.130 °C; ir (KBr) ꢀ/max cm-1 3300-3430 (NH, NH2), 1710
(C=O), 1680 (C=O). 1H nmr (ꢁ, ppm, CDCl3): 2.15 (s, 3H, CH3),
8.78 (s, 1H, NH), 3.78 (s, 2H, NH2), 4.16 (s, 2H, CH2), 4.84 (s,
1H, CH pyrazole), 7.25-7.50 (m, 19H, ArHs). Anal. Calcd for
C31H28N4O2 (488.58): C, 76.20; H, 5.77; N, 11.46%. Found: C,
76.60; H, 6.00; N, 11.60%.
1
3494, 3352 (NH, NH2), 1705, 1689 (2C=O); H nmr (ꢁ, ppm,
CDCl3): 1.15 (t, 3H, ester-CH3), 2.29 (s, 6H, 2CH3), 2.74 (s, 1H,
NH), 3.87 (s, 2H, NH2), 4.16 (s, 2H, CH2), 4.18 (q, 2H, ester-
CH2), 4.84 (s, 1H, CH pyrazole), 6.9-7.82 (m, 13H, ArHs).
Anal. Calcd for C29H30N4O4 (498.62): C, 69.86; H, 6.01; N,
11.23%. Found: C, 70.10; H, 6.21; N, 11.40 %.
Cyclization of 5-(2-Phenyl-2-oxoethyl)-1,3,4-triphenyl-4,5-
dihydro-1H-pyrazole-5-carbohydrazide. Synthesis of 1,3,4,9-
tetraphenyl-1,2,7,8-tetrazaspiro[4.5]deca-2,9-diene-6-one (10).
A mixture of glacial acetic acid (5 mL), hydrochloric acid (34%,
10 mL) and pyrazole-5-carbohydrazide 6a (20 mmol) was
refluxed for 5 hour. The reaction mixture was allowed to cool
and poured into ice-cold water. The precipitated solid was
collected by filtration, washed with water and crystallized from
ethanol. Yield 50%; mp 158 °C; ir (KBr) ꢀ/max cm-1 3417 (NH),
1
1744 (C=O); H nmr (ꢁ, ppm, DMSO-d6): 3.46 (s, 1H, CH-
pyridazine), 5.80 (s, 1H, CH-pyrazole), 7.31-7.88 (m, 20H,
ArHs), 8.66 (s, 1H, NH), 12.23 (s, 1H, NH). Anal. Calcd for
C30H24N4O (456.54): C, 78.92; H, 5.30; N, 12.27%. Found: C,
79.10; H, 4.90; N, 12.53%. 13C nmr (ꢁ, ppm, DMSO-d6): 47.81,
70.54, 95.62, 114.83, 115.18, 116.31, 122.12, 125.07, 126.81,
126.93, 127.09, 127.34, 127.65, 128.07, 128.26, 128.50, 128.72,
128.86, 129.26, 129.56, 129.88, 131.97, 132.69, 133.77, 135.85,
136.97, 137.65, 142.41, 148.52, 177.88.
Ethyl 5-(hydrazinocarbonyl)-5-[2-phenyl-2-oxoethyl]-1,4-
diphenyl-4,5-dihydro-1H-pyrazole-3-carboxylate (6c). Yield
70%; mp 128 °C; ir (KBr) ꢀ/max cm-1 3394, 3317 (NH, NH2),
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[1] Lim, S-G; Kwon, B-I; Choi, M-G ; Jun; C-H, Synlett,
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1
1712, 1689 (2 C=O); H nmr (ꢁ, ppm, CDCl3): 1.13 (s, 3H,
ester-CH3), 2.67 (s, 2H, CH2), 2.74 (s, 1H, NH), 3.64 (s, 1H,
CH-pyrazole), 3.87 (s, 2H, NH2), 4.12 (q, 2H, ester-CH2), 7.25-
7.41 (m, 15H, ArHs). MS (m/z): 470 (M+), 452, 411, 390, 365,
233, 130, 105, 77, 51. 13C nmr (ꢁ, ppm, CDCl3): 13.91, 39.79,
58.10, 60.59, 75.26, 89.27, 119.72, 122.09, 124.09, 125.10,
127.87,128.25, 128.37, 128.59, 128.84,128.90, 129.17, 129.30,
129.65, 131.86, 134.49, 140.95, 141.92, 141.97, 161.66, 170.63.
Anal. Calcd for C27H26N4O4 (470.52): C, 68.92; H, 5.57; N,
11.90%. Found: C, 69.10; H, 6.01 N, 12.00%.
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Ethyl 5-(hydrazinocarbonyl)-5-[2-phenyl)-2-oxoethyl]-1(4-
methylphenyl)-4-phenyl-1H-pyrazole-3-carboxylate (6d).
Yield 75%; mp 160 °C; ir (KBr) ꢀ/max cm-1 3355, 3300 (NH,
NH2), 1712, 1687 (2C=O). 1H nmr (ꢁ, ppm, CDCl3): 1.15 (t, 3H,
ester-CH3), 2.74 (s, br, 1H, NH), 2.54 (s, 3H, CH3), 3.87 (s, 2H,
NH2),4.16 (s, 2H, CH2), 4.18 (q, 2H, ester-CH2), 4.94 (s, br, 1H,
CH-pyrazole), 7.17-7.29 (m, 14H, ArHs). Anal. Calcd for
C28H28N4O4 (484.55).: C, 69.40; H, 5.82; N, 11.56%. Found:
C, 69.80; H, 6.10; N, 11.80%.
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P.; Kubota, H.; Kinet, J. P; Fleig, A.; Yamada T.; Penner, R. Mol.
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Ethyl 5-(hydrazinocarbonyl)-5-[2-(4-methylphenyl)-2-oxo-
ethyl]-1,4-diphenyl-1H-pyrazole-3-carboxylate (6e). Yield
83%; mp 198 °C; ir (KBr) ꢀ/max cm-1 3327, 3276 (NH, NH2),
1718, 1697 (2C=O). 1H nmr (ꢁ, ppm, CDCl3): 1.14 (t, 3H, ester-
CH3), 2.32 (s, br, 1H, NH), 2.62 (s, 3H, CH3), 3.87 (s, 2H, NH2),
4.13 (s, 2H, CH2), 4.18 (q, 2H, ester-CH2), 4.80 (s, br., 1H, CH-
pyrazole), 7.17-7.38 (m, 14H, ArHs). 13C nmr (ꢁ, ppm, CDCl3):
13.94, 20.92, 39.89, 59.47, 60.94, 89.12, 120.10, 124.31, 124.98,
127.90, 128.62, 129.11, 129.21, 129.28, 134.52, 138.28, 13880,
141.06, 142.00, 161.63, 170.46. Anal. Calcd for C28H28N4O4
(484.55): C, 69.40; H, 5.82; N, 11.56%. Found: C, 69.70; H,
5.60; N, 11.70%.
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