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BOTVINNIK et al.
13C NMR spectra ( C, ppm) of condensation products Ib, IVa, IVb, V, and VI
Ph
Comp.
no.
CH3, C C,
CH
C O CH CH C N
CH2
C C
Ci
Co, Cm
Cp
Ib
136.6, 142.5,
143.7
113.0 (N Ph), 125.8, 118.8 (N Ph),
126.8, 128.9, 129.0, 121.3, 127.5a
129.1
62.8
42.0
128.2,a 148.9
133.3
IVa 133.9, 134.6,
137.9, 142.2,
142.5b
127.3, 127.7, 127.8, 126.3, 126.4,
127.9, 128.0, 128.3, 127.1c
128.5, 128.6
44.6, 44.9, 22.1, 114.8b 202.5 130.0, 148.1
50.1, 61.0 22.2,
30.6
141.8
IVb 133.5, 134.8,
139.7, 140.5,
127.9, 128.2, 128.5, 123.3, 126.2,
128.7, 129.3, 129.8c 126.6, 127.2,
127.4
44.6, 44.9, 32.6 117.7b 201.9 130.8, 149.7
60.2
142.3
142.7, 142.8b
V
119.9 (5-Ph) 128.3, 128.7, 132.6c 128.2, 130.8a
133.7 (1-Ph)
86.3, 177.8 130.3,a
91.2
147.9
VI
119.6, 141.3,
143.3
113.4 (N Ph), 125.4, 121.9 (N Ph),
128.1, 128.6, 128.9, 127.4, 131.0
131.3
63.9
46.2
82.7,
94.3
141.3
a
b
c
Alternative assignment is possible.
One of these signals belong to carbon atom of the C C bond.
Some signals overlap.
1
(100) [M COCH CHPh PhCH CH]+, 245 (24)
[M COCH CHPh PhCH CH i-Pr]+, 131 (58)
[COCH CHPh]+, 115 (15), 103 (48) [PhCH CH]+,
91 (36) [PhCH2]+, 77 (24) [Ph]+, 43 (12).
structure in [9]). H NMR spectrum, , ppm: 6.69
7.58 m (17H, 3Ph, CH CH), 5.47 d.d (1H, CH, J =
5.5, 12.2 Hz), 3.76 d.d (1H, CH2, J = 12.3, 17.1 Hz),
2.97 d.d (1H, CH2, J = 5.5, 17.0 Hz).
Reaction of 1,5-diphenyl-1-penten-4-yn-3-one
(V) with phenylhydrazine. To a solution of 0.696 g
(3 mmol) of ketone V in 10 ml of acidified alcohol we
added 0.3 ml (0.324 g, 3 mmol) of phenylhydrazine,
and the mixture was refluxed for 20 min and left
overnight. The oily material was separated, 5 ml of
glacial acetic acid was added, and the mixture was
left to stand for 24 h. The crystals of dihydropyrazole
VI were filtered off, washed with alcohol, and dried
Reaction of 1,5-diphenyl-1,4-pentadien-3-one
(III) with phenylhydrazine in ethanol. To a solution
of 2 g (8.5 mmol) of ketone III in 40 ml of ethanol
we added with stirring 0.84 ml (0.92 g, 8.5 mmol) of
phenylhydrazine. The mixture was stirred for 3 h
under reflux and was left overnight. The precipitate
of IVb was filtered off through a glass filter, washed
with ethanol, dried in air, and recrystallized from
1
ethyl acetate. Yield 0.8 g (33%), mp 240 C. H NMR
1
in air. Yield 0.35 g (35%), mp 145 C. H NMR spec-
spectrum, , ppm: 6.80 7.70 m (26H, 5Ph, CH ),
6.54 d (1H, COCH , J = 16.3 Hz), 4.73 d (1H, 4-H,
J = 9.7 Hz), 3.71 3.84 m (1H, 5-H), 3.42 3.62 m
(2H, CH2), 2.88 3.04 m (1H, 6-H).
trum, , ppm: 6.85 7.60 m (15H, 3Ph), 5.31 d.d (1H,
CH, J = 7.2, 9 Hz), 3.71 d.d (1H, CH2, J = 9, 15 Hz),
3.02 d.d (1H, CH2, J = 7.2, 15 Hz).
1,5-Diphenyl-1-penten-4-yn-3-one 2,4-dinitro-
phenylhydrazone (VII) [8]. To a solution of 0.696 g
(3 mmol) of ketone V in 15 ml of alcohol acidified
with acetic acid we added 0.6 g (3 mmol) of 2,4-di-
nitrophenylhydrazine. The precipitate was filtered
off, washed with alcohol, and dried in air. Yield 1 g
Reaction of 1,5-diphenyl-1,4-pentadien-3-one
(III) with phenylhydrazine in acetic acid. To a solu-
tion of 1.5 g (6.5 mmol) of ketone III in 50 ml of
glacial acetic acid we added 0.64 ml (0.702 g,
6.5 mmol) of phenylhydrazine, and the mixture was
left overnight. The precipitate of dihydropyrazole Ib
was filtered off, washed with alcohol, dried in air,
and recrystallized from ethyl acetate. Yield 1.5 g
(71%), mp 155 C; published data: mp 151 153 C [7],
152 153 C [9] (compound Ib was assigned hydrazone
1
(80%), mp 232 C [8]. H NMR spectrum, , ppm:
12.5 br.s (0.75H, NH), 11.9 br.s (0.25H, NH), 9.12 m
(1H, 3-H) and 8.00 8.45 m (2H, 5-H, 6-H) (signals
from the 2,4-dinitrophenyl group); 7.05 7.85 m (12H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 3 2001