SYNTHESIS OF NEW SPIROPYRROLIDINES AND MICHAEL ADDITION PRODUCTS USING PHASE TRANSFER CATALYZED ADDITION OF SCHIFF BASES TO 9-ARYLMETHYLENEFLUORENES

Full text of DOI:10.1135/cccc19940489

New Compounds
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SYNTHESIS OF NEW SPIROPYRROLIDINES
AND MICHAEL ADDITION PRODUCTS
USING PHASE TRANSFER CATALYZED ADDITION
OF SCHIFF BASES TO 9-ARYLMETHYLENEFLUORENES
Kostadinka POPANDOVA-YAMBOLIEVA
Department of Organic Chemistry,
University of Sofia, 1126 Sofia, Bulgaria
Received February 9, 1993
Accepted May 11, 1993
As a continuation of our previous studies concerned with the reactivity of benzylidene-
and furfurylidenefluorenes in addition reactions1,2, in the present work we have pre-
pared a series of new spiropyrrolidines by reactions of 9-arylmethylenefluorenes I
with aryl- (II) and furylazomethines (IV) and some Michael addition products by using
diphenylmethyleneazomethines VI (refs3 – 5) and VIII (Scheme 1). The structure B was
assigned to the furylspiropyrrolidines Va – Vf based on 1H NMR data.
The reaction was carried out at room temperature with an excess of aqueous sodium
hydroxide and a catalytic amount of triethylbenzylammonium chloride (TEBA).
An attempt at synthesis of an analogous reaction product by interaction of Schiff
base IV with 1,1,2-triphenylethene has not been successful and the starting 1,1,2-tri-
phenylethene was isolated unchanged.
EXPERIMENTAL
Melting points were determined on a Kofler hot stage apparatus and were not corrected. IR spectra
1
were measured on a Specord 71 instrument (Zeiss, Jena). H NMR spectra were recorded on a Tesla
BS 487-C (80 MHz) spectrometer, using CDCl3 solution and TMS as an internal standard. For thin
layer chromatography (TLC), the solvent system used was hexane–acetone (4 : 1 v/v). The starting
9-arylmethylenefluorenes (Ia – If) were prepared from fluorene and the corresponding aromatic alde-
hydes. 4-Methyl-N-(4-methylbenzylidene)benzylamine (IIb) and 4-chloro-N-(4-chlorobenzy-
lidene)benzylamine (IIc) were prepared as reported6. N-Furfurylidenefurfurylamine (IV) was obtained
by reported procedure7. N-Diphenylmethylenebenzylamine (VI) was prepared from benzophenone and
benzylamine8, N-diphenylmethylene-(2-furfuryl)amine (VIII) was described previously9.
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New Compounds
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SCHEME 1
2′,4′,5′-Triarylfluorene-9-spiro-3′-pyrrolidines IIIa – IIIc
and 4′-Aryl-2′,5′-bis(2-furyl)-fluorene-9-spiro-3′-pyrrolidines Va – Vf
Aqueous sodium hydroxide (50%, 3 ml) was added to a stirred solution of II (20 mmol), 9-aryl-
methylenefluorene I (10 mmol) and TEBA (0.23 g, 1 mmol) in dimethylsulfoxide (5 ml). The reac-
tion mixture was green and was stirred at room temperature for 1 h. After 3 h, water (100 ml) was
added. The solid was filtered, washed with water until neutral and recrystallized. Some physico-
chemical properties of the obtained products are summarized in Table I and their characteristic IR
1
bands and H NMR spectra are presented in Table II.
2-Aryl-2-fluorenyl-1-phenyl-N-(diphenylmethylene)ethylamines VII and IX
Aqueous sodium hydroxide (50%, 3 ml) was added to a stirred solution of VI, or VIII (10 mmol),
respectively, 9-arylmethylenefluorene I (10 mmol) and TEBA (0.23 g, 1 mmol) in acetonitrile (5 ml).
The reaction mixture was stirred for 10 min and water (100 ml) was added. After 24 h, the solid was
filtered, washed with water and recrystallized from methanol–ethyl acetate. Characteristic data for the
1
so obtained compounds are in Table I, their IR and H NMR spectra are given in Table II.
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TABLE I
Characteristic data for compounds III, V, VII, and IX
Calculated/Found
Formula
(M.w.)
M.p., °Ca
(Yield, %)
Compound
% C
% H
% N
IIIa
IIIb
IIIc
Va
C36H31N
(447.6)
174 – 176
90.52
90.22
6.54
6.83
2.93
2.89
(44)
C34H25NCl2
(518.4)
171 – 173
78.83
78.81
4.83
4.94
2.70
2.84
(60)
C35H27NCl2
(523.3)
173 – 175
78.97
78.98
5.07
5.36
2.63
2.52
(54)
C30H23NO2
(429.3)
189 – 191
83.99
84.25
5.36
5.10
3.26
3.36
(33)
Vb
C31H25NO2
(443.5)
187 – 189
83.94
84.22
5.68
5.95
3.16
3.14
(40)
Vc
C30H22NO2Cl
(463.8)
189 – 190
77.69
77.74
4.74
4.73
3.02
3.06
(46)
Vd
C31H25NO3
(459.5)
196 – 198
81.02
81.11
5.48
5.25
3.05
2.89
(47)
Ve
C32H28N2O2
(472.6)
179 – 181
81.33
81.54
5.97
6.01
5.93
5.84
(61)
Vf
C28H21NO3
(419.5)
149 – 150
80.17
80.42
5.05
5.01
3.34
3.33
(50)
VIIa
VIIb
VIIc
IXb
C40H31N
(525.7)
178 – 179
91.39
91.68
5.94
5.67
2.66
2.68
(47)
C41H33N
(539.7)
189 – 191
91.24
91.58
6.16
6.12
2.60
2.51
(42)
C40H30NCl
(560.2)
151 – 152
85.80
85.66
5.36
5.55
2.50
2.27
(48)
C38H29NO
(515.6)
195 – 196
88.51
88.42
5.67
5.70
2.72
2.72
(23)
a
b
Recrystallized from methanol–ethyl acetate. A total of 10% of compound X (m.p. 94 – 95 °C,
reported5 m.p. 106 °C) was isolated from the mother liquor. IR (chloroform): ν(C=N) = 1 630 cm−1.
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