1
810
NOVIKOV et al.
2
3
(
[
4
C , C ). Mass spectrum, m/z (I , %): 472 (3.6)
6.8 Hz), 3.34 d.d (2H, NCH , J = 7.5, 8.4 Hz), 4.09 d.d
rel
2
+
+
+
M + 2] , 471 (17) [M + 1] , 470 (47) [M] , 443 (13),
42 (19) [M – CO] , 206 (100), 182 (74).
(2H, NCH , J = 7.5, 8.4 Hz), 6.75–6.76 m (2H, Harom),
2
+
13
6.97–7.43 m (24H, Harom). C NMR spectrum (CDCl
),
3
δ , ppm: 34.8 (PhCH ); 37.6 (PhCH ); 41.8 (NCH );
C
2
2
2
Compound XIII. Yield 0.062 g (8%), mp 149–
3
'
4'
–
1
4
9.9 (NCH ); 64.9 (C ); 67.2 t (C , J = 22.9 Hz);
2 CF
1
1
50°C (from Et O). IR spectrum (CHCl ), ν, cm :
2
3
5'
1
119.5, 119.6, 125.5, 126.0, 126.1 (Carom); 126.3 t (C ,
695 (C=O), 3430 (NH). H NMR spectrum (CDCl ),
3
JCF = 248.8 Hz); 126.3, 126.4, 126.6, 127.8, 128.3,
δ, ppm: 1.09 t (3H, CH , J = 7.3 Hz), 3.21–3.31 m
3
1
1
28.5, 128.6, 128.7, 129.0, 139.2, 140.2, 140.4, 140.9,
(
2H, CH ), 6.11 br.s (1H, NH), 7.36–7.48 m (4H,
2
13
41.4, 142.7 (Carom); 154.6 (C=N). Mass spectrum, m/z
Harom), 7.69–7.78 m (4H, Harom). C NMR spectrum
+
+
9
(
I , %): 630 (3) [M + 2] , 629 (12), [M + 1] , 628 (23)
rel
(
1
(
CDCl ), δ , ppm: 14.4 (CH ); 35.5 (CH ); 62.8 (C );
3 C 3 2
+
+
[
M] , 538 (10), 537 (22), 524 (17) [M – PhCH CH ] ,
2 2
20.6, 125.9, 128.7, 129.9, 139.3, 144.9 (Carom); 166.9
C=O). Found, %: C 60.77; H 4.58; N 4.20.
+
4
21 (32), 420 (100) [M – 2PhCH CH ] , 205 (7), 105
2 2
+
(95) [PhCHCH ] . Found, %: C 84.03; H 5.45; N 4.53.
3
C H BrNO. Calculated, %: C 60.78; H 4.46; N 4.43.
1
6
14
C H F N . Calculated, %: C 84.05; H 5.45; N 4.46.
4
4
34
2
2
Following method a (reaction time 30 h), from 1 g
4.82 mmol) of Schiff base Ib we obtained 0.015 g
1.3%) of piperazine derivative VIIb.
3
,5-Dimethyl-9'H-spiro[oxazolidine-2,9'-
fluoren]-4-one (XVIII) and 3,5-dimethyl-9'H-spiro-
oxazolidine-4,9'-fluoren]-2-one (XIX). The reaction
(
(
[
9
H-Fluorene-9-carboxamide (XII) was obtained
was performed with 0.9 g (4.66 mmol) of compound
Ia and 1.5 ml (26.8 mmol) of acetaldehyde according
to method a (rection time 6 h); column chromatog-
raphy using hexane–ethyl acetate (25:1 to 3:1) as
eluent gave 0.204 g (17%) of compound Va), 0.072 g
from 0.7 g (2.60 mmol) of compound Ic (method a;
reaction time 25 h; eluent hexane–EtOAc, 9:1). Yield
0
.002 g (0.4%), mp 156–158°C; published data [19]:
1
mp 157–158°C. H NMR spectrum (CDCl ), δ, ppm:
3
4
(
.81 s (1H, 9-H), 5.19 br.s (2H, NH ), 7.36–7.50 m
2
(
6%) of XVIII, and 0.084 g (9%) of XIX.
4H, Harom), 7.74 d (2H, Harom, J = 7.3 Hz), 7.81 d (2H,
Compound XVIII. mp 156–158°C (from Et O). IR
Harom, J = 7.3 Hz). Mass spectrum, m/z (I , %): 209
2
rel
–
1
1
+
+
+
spectrum (CHCl ): ν 1725 cm (C=O). H NMR spec-
(
27) [M] , 166 (98) [C H ] , 165 (100) [C H ] .
3
1
3
10
13
9
trum (CDCl ), δ, ppm: 1.66 d (3H, CH , J = 6.0 Hz),
3
3
N-(2-Phenylethyl)-9H-fluorene-9-carboxamide
XI) was obtained from 0.71 g (2.5 mmol) of com-
pound Id (method a; reaction time 70 h; eluent
2
.47 s (3H, NCH ), 4.90 q (1H, 5-H, J = 6.0 Hz), 7.32–
3
(
1
3
7.66 m (8H, Harom). C NMR spectrum (CDCl ), δ ,
3
C
5
2
ppm: 19.2 (CH ); 25.3 (NCH ); 74.2 (C ); 99.7 (C );
3
3
hexane–EtOAc, 1:1). Yield 0.015 g (2%), mp 188–
1
120.3, 120.4, 123.5, 124.2, 128.6, 128.7, 130.8, 131.1,
39.8, 140.4, 141.6, 142.3 (Carom); 172.5 (C=O). Found,
1
91°C (from EtOAc). H NMR spectrum (CDCl ), δ,
3
1
ppm: 2.68 t (2H, PhCH , J = 6.5 Hz), 3.35–3.42 q (2H,
2
%
: C 76.68; H 5.63; N 5.38. C H NO . Calculated,
17 15 2
NCH , J = 6.5 Hz), 4.80 s (1H, 9-H), 5.21 br.s (1H,
2
%
: C 76.96; H 5.70; N 5.28.
Compound XIX. IR spectrum (CHCl
NH), 6.91–6.92 m (2H, Harom), 7.16–7.18 m (3H,
Harom), 7.34 t (2H, Harom), 7.45 t (2H, Harom), 7.62 d
2H, Harom, J = 7.3 Hz), 7.78 d (2H, Harom, J = 7.3 Hz).
–
1
): ν 1780 cm
), δ, ppm: 0.98 d
, J = 6.3 Hz), 2.39 s (3H, CH ), 4.91 q (1H,
5-H, J = 6.3 Hz), 7.34–7.72 m (8H, Harom). C NMR
spectrum (CDCl ), δ , ppm: 14.8 (CH ); 27.0 (NCH );
3
1
(
(C=O). H NMR spectrum (CDCl
3
1
3
C NMR spectrum (CDCl ), δ , ppm: 35.2 (PhCH );
(3H, CH
3
3
3
C
2
9
13
4
1
(
2
(
0.7 (NCH ); 56.1 (C ); 120.2, 125.4, 126.3, 127.7,
2
28.3, 128.5, 128.7, 138.5, 141.3, 141.4 (Carom); 170.5
3
C
3
3
+
5
4
C=O). Mass spectrum, m/z (I , %): 313 (14) [M] ,
75.2 (C ); 79.2 (C ); 120.4, 120.6, 124.0, 125.1,
127.8, 128.3, 129.8, 130.1, 140.3, 140.9, 141.8 (Carom);
158.6 (C=O).
rel
+
+
09 (3), 166 (100) [C H ] , 165 (87) [C H ] , 105
13 10 13 9
+
50) [PhCHCH ] .
3
N-{5',5'-Difluoro-1'-(2-phenylethyl)-9H,9''H-
3-Methyl-5-phenyl-9'H-spiro[oxazolidine-2,9'-
fluoren]-4-on (XX) and 3-methyl-5-phenyl-9'H-
spiro[oxazolidine-4,9'-fluoren]-2-one (XXI). The
reaction was performed with 0.9 g (4.66 mmol) of
compound Ia and 1 ml (9.84 mmol) of benzaldehyde
dispiro[fluorene-9,3'-pyrrolidine-4',9''-fluoren]-2'-
ylidene}-2-phenylethanamine (XIV) was obtained
from 1.14 g (4.02 mmol) of compound Id (method b;
reaction time 9 h; eluent hexane–ethyl acetate, 1:3 to
2
:1). Yield 0.130 g (10%), mp 168–169°C (from according to method a (reaction time 6 h); column
–
1
EtOAc–Et O). IR spectrum (CHCl ): ν 1695 cm
chromatography using hexane–ethyl acetate (50:1 to
3:1) gave 0.217 g (18%) of imidazolidinone Va and
0.561 g (37%) of a mixture of compounds XX and
2
3
1
(
(
C=N). H NMR spectrum (CDCl ), δ, ppm: 2.48 t
2H, PhCH , J = 6.8 Hz), 2.72 t (2H, PhCH , J =
3
2
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006