Synthesis and characterization of exo-endo and endo-endo benzenesulfonylaziridines

Article abstract of DOI:10.1081/SCC-200028524

In the search for structural cyclic imide analogues of therapeutic interest, the synthesis, separation, and characterization of exo-endo 3 and endo-endo 4 stereoisomers of benzenesulfonylaziridines, not found in the literature, are described in this study

Full text of DOI:10.1081/SCC-200028524

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Synthesis and
Characterization of
Exo‐endo and Endo‐endo
Benzenesulfonylaziridines
a
a
Evilazio da Silva Andrade , Ricardo José Nunes
a
&
a
Marina Uieara
Departamento de Química , Universidade
Federal de SantaCatarina, UFSC, CEP , 88040‐900,
Florianópolis, Santa Catarina, Brazil
Published online: 10 Jan 2011.
To cite this article: Evilazio da Silva Andrade , Ricardo José Nunes & Marina
Uieara (2004) Synthesis and Characterization of Exo‐endo and Endo‐endo
Benzenesulfonylaziridines, Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic Chemistry, 34:17, 3073-3081, DOI:
10.1081/SCC-200028524
To link to this article: http://dx.doi.org/10.1081/SCC-200028524
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w
SYNTHETIC COMMUNICATIONS
Vol. 34, No. 17, pp. 3073–3081, 2004
Synthesis and Characterization of Exo-endo
and Endo-endo Benzenesulfonylaziridines
Evilazio da Silva Andrade, Ricardo Jos e´ Nunes,
and Marina Uieara
*
Departamento de Qu ´ı mica, Universidade Federal de Santa
Catarina, UFSC, Florian o´ polis, Santa Catarina, Brazil
ABSTRACT
In the search for structural cyclic imide analogues of therapeutic interest,
the synthesis, separation, and characterization of exo-endo 3 and endo-
endo 4 stereoisomers of benzenesulfonylaziridines, not found in the
literature, are described in this study. The benzenesulfonylaziridines
were synthesized through a 1,3-dipolar-type reaction of p-toluenesulfonyla-
zide and different norbornenesuccinimides.
Key Words: Benzenesulfonylaziridines.
*
Correspondence: Ricardo Jos e´ Nunes, Departamento de Qu ´ı mica, Universidade
Federal de SantaCatarina, UFSC, CEP, 88040-900, Florian o´ polis, Santa Catarina,
Brazil; E-mail: nunes@qmc.ufsc.br.
3
073
DOI: 10.1081/SCC-200028524
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

3
074
Andrade, Nunes, and Uieara
INTRODUCTION
The aziridines or azacyclopropanes are generally prepared through cyclic
[
1,2]
reactions.
synthesized through a method adapted by Nunes, from a method described
In the present study a series of benzenesulfonylaziridines was
3]
[
[4,5]
by Zalkow.
This study aimed to synthesize and characterize exo-endo 3 and endo-endo
stereoisomers of a series of benzenesulfonylaziridines. The benzenesulfony-
4
laziridines (Sch. 1) were obtained through a 1,3-dipolar-type reaction between
p-toluenesulfonylazide (previously prepared) and different endonorbornene-
succinimides 2. The endo-norbornenesuccinimides (Table 1) were prepared
through the Diels-Alder reaction between substituted N-phenylmaleimides 1
and cyclopentadiene according to the method described in the literature for
[6]
similar structures. The N-phenylmaleimides were prepared through the
[7]
reaction of a substituted aniline and maleic anhydride in acetic anhydride.
The endo-norbornenesuccinimides 2 showed only one spot on thin layer
chromatography (t. l. c.). The formation of exo-norbornenesuccinimide was
1
not observed at any time. Their structures were confirmed through H NMR
1
3
and C NMR spectroscopic analysis, CNH elemental analysis, and compari-
1
son of their H NMR spectra with those of the exo- and endo-norbornene-
[6,8–10]
succinimides and similar compounds given in the literature.
The
signal, in the form of a doublet, exhibited by the H2,6 hydrogens of all of
the endo-norbornenesuccinimides synthesized in this study, indicates the
existence of a coupling with the H1,7 hydrogens, which was not observed in
the case of exo-norbornenesuccinimide, due to the dihedral angle being
approximately 908.
Scheme 1.

Synthesis and Characterization of Benzenesulfonylaziridines
3075
Table 1. Yield, mp, and CNH of endo-norbornenesuccinimides 2.
Calcd. (%)
found (%)
mp (8C)
mp Literature
Y
(%)
[
10–12]
Compound X
Formula mass
C H NO
239.27
C
H
N
2
a
71
63
67
73
75
62
70
79
90
143.9–144.9
144
75.30
74.94
65.82
65.50
58.46
58.51
75.87
75.80
71.36
71.23
56.62
57.23
63.38
63.28
76.38
76.37
76.38
76.47
5.48
4.96
4.42
4.52
3.60
3.68
5.97
6.02
5.61
5.72
3.80
3.30
4.25
4.91
6.41
6.72
6.41
6.65
5.85
5.95
5.12
5.10
4.55
4.49
5.53
5.45
5.20
5.11
4.40
4.26
9.85
9.43
5.24
5.33
5.24
5.21
1
5
13
2
H
2
4
2
3
2
4
2
4
2
4
2
4
2
2
2
3
b
141.4–142.9
—
C
15
H
2
12NO Cl
-Cl
c
,4-diCl
273.71
C H NO Cl
2
163.8–164.6
—
1
5
11
2
308.16
d
-CH3
158.2–158.6
157–158
171.6–173.0
169–170
153.4–154.6
156
C
16
H
253.30
15NO
2
e
-OCH
C
16
H
269.29
15NO
3
3
f
C H NBrO
15 12 2
-Br
g
318.16
188.9–189.2
190–191
188.3–188.7
—
15 12 2 4
C H N O
-NO2
h
,3-Dimethyl
284.27
H
267.32
C
17
17NO
2
i
-Ethyl
108.5–108.8
—
C
17
H
267.32
17NO
2
The p-toluenesulfonylazide was prepared from p-toluenesulfonyl chloride
1
and sodium azide, and its structure was confirmed through the H NMR spec-
troscopie (d ppm: -CH -Ph [(s: 2.48) e Ar-H (d: 7.38 7.85 J ¼ 8.2 Hz)] and
3
3]
[
melting point (208C).
The formation of isomers was initially detected by t. l. c. in all the reac-
1
tions of the benzenesulfonylaziridines and later confirmed through H NMR
1
3
and C NMR spectroscopies and CHN elemental analysis. The yield of the
reactions was 65% to 90%, as described in the experimental section. The
stereoisomers were separated and purified through column chromatography
and successive recrystalizations.
1
The H NMR spectrum in two dimensions (COSY) of the endo-endo-
aziridines shows a broad singlet for the H1,7 hydrogens and shows coupling
between these hydrogens and the H2,6 and H8,10 hydrogens. The H2,6 and
H8,10 hydrogens show multiplets due to a W coupling between them and con-
sequently to the coupling with the H hydrogens.
1
,7
1
On the other hand, the H NMR spectrum in two dimension (COSY) of
the exo-endo-aziridines shows coupling of H1,7 hydrogens only with the

3
076
Andrade, Nunes, and Uieara
H2,6 hydrogens. The spectrum also shows a sharp singlet for the H8,10
hydrogens with no coupling with the H1,7 hydrogens since the dihedral
angle between them is approximately 908. This is the principal difference
between the stereoisomers.
The results obtained with the aziridines synthesized in this study are con-
[4,5,13,14]
sistent with the results found in the literature for related structures.
the reaction of benzenesulfonylazides with cis-endo or cis-exo norbornene-
,6-dicarboxylic anhydride, the authors obtained exo- and endo-aziridines,
In
5
where the endo isomer was obtained in greater proportion (approximately in
the proportions of 70% : 30%). In the present study the endo-endo aziridine
was also obtained in greater proportion as described in the experimental part.
EXPERIMENTAL
Analytical-grade reagents were utilized and purified according to methods
[
15]
cited in the literature.
For the determination of the melting point (mp) a
Microqu ´ı mica device model MQRPF-301 (Florian o´ polis, Brazil) was utilized.
For the CHN analysis, a CHN elemental analyzer Perkin Elmer 2400 (Boston,
1
13
MA, USA) was utilized. H NMR and C NMR spectra were recorded using a
Brucker AC-200F (Rheinstetten, Germany) (at 200 MHz and 50 MHz, respect-
ively). CDCl was used as the solvent with tetramethylsilane (TMS) as the
3
internal standard; chemical shifts (d) were in parts per million. In the t. l. c.,
aluminium sheets with silica gel 60 F-254 with 0.2 mm thickness were utilized.
All benzenesulfonylaziridines were purified by column chromatography with
silica gel 60 (230–400 mesh) purchased from Merck.
General Experimental Procedure
0
(2R,6S,8S,10R) 3a and (2R,6S,8R,10S) 4a 9-(4 -Methylphenylsulfonyl)-4-
phenyl-4,9-diazatetracycle[5.3.1.0
2
,6 8,10
ꢀ 0
]undecane-3,5-dione
p-Toluenesulfonylazide (4.14 g, 0.0210 mol) was added to a mixture
of 4-phenyl-4-aza-tricycle[5.2.1.02,6-endo]dec-8-ene-3,5-dione 2a (4.00 g,
0
.0167 mol) in acetonitrile (20 mL). The reaction was refluxed (15 hours)
and the solvent was evaporated in vacuo. The solid residue was triturated
with methanol: chloroform (3 : 7) and filtered off with suction to give the
mixture of 3a and 4a. The two products were isolated by column chromato-
graphy (silica gel, ethyl acetate : acetone : hexane, 6 : 3 : 11). Yield: 91%.
Ratio 3a/4a ¼ 35%/65%. mp 250.1–251.38C 3a and 253.0–254.98C 4a.
Anal. Calcd. for C
H
N O S: C, 64.69; H, 4.94; N, 6.86; O, 15.66; S,
20 2 4
2
2

Synthesis and Characterization of Benzenesulfonylaziridines
3077
7
.85. Found: C, 63.85; H, 4.98; N, 6.72 3a and C, 64.59; H, 4.97; N, 6.92 4a.
1
H NMR d ppm: CH -11 (d: 1.22 and 1.85, J ¼ 10.5 Hz); CH -Ph (s: 2.46);
2
3
CH-8 (s sharp: 3.06); CH-7 (s broad: 3.12); CH-6 (m: 3.32); ArH (m: 7.15–
1
3
7
CH-8 (39.49); CH-6 (47.89); C Ar (127.41; 128.73; 129.84; 130.13; 130.54;
.80). C NMR d ppm: CH -Ph (22.39); CH -11 (32.31); CH-7 (38.05);
3 2
1
35.06; 145.62); C 55 O (175.98) 3a. H NMR d ppm: CH -11 (m: 2.01 and
1
2
2
.41); CH -Ph (s: 2.32); CH-7 (s broad: 3.11); CH-8 (t: 3.24 J ¼ 2.5 Hz);
3
1
3
CH-6 (t: 3.59 J ¼ 2.0 Hz); ArH (m: 7.00–7.56). C NMR d ppm: CH -Ph
3
(
(
(
22.30); CH -11 (40.74); CH-7 (48.76); CH-8 (50.36); CH-6 (55.98); C Ar
2
126.70; 127.68; 128.04; 128.34; 129.14; 129.35; 129.88; 130.09); C 55 O
175.76) 4a.
By this procedure the following benzenesulfonylaziridines were prepared:
0
2,6 8,10
(
2R,6S,8S,10R) 3b and (2R,6S,8R,10S) 4b 9-(4 -Methylphenylsulfonyl)-
00
4-(4 -chlorophenyl)-4,9-diazatetracycle[5.3.1.0
dione
ꢀ 0
]undecane-3,5-
Yield: 70%. Ratio 3b/4b ¼ 30%/70%. mp 230.3–231.88C 3b and
49.7–251.38C 4b. Anal. Calcd. for C Cl N O S: C, 59.66; H, 4.33;
N, 6.33; O, 14.44; S, 7.24; Cl, 8.00. Found: C, 59.76; H, 4.40; N, 6.05; 3b
2
H
19
2
2
2
4
1
and C, 59.88; H, 4.72; N, 6.16 4b. H NMR d ppm: CH -11(d: 1.19 and
2
1
3
7
.86, J ¼ 10,6 Hz); CH -Ph (s: 2.46); CH-8 (s sharp: 3.03); CH-7 (s broad:
3
.11); CH-6 (m: 3.31); ArH (d: 7.11 and 7.46, J ¼ 8.6); ArH (d: 7.35 and
1
3
.77, J ¼ 8.2). C NMR d ppm: CH -Ph (21.64); CH -11 (31.51); CH-7
3
2
(
37.25); CH-8 (38.75); CH-6 (47.12); C Ar (127.93; 129.58; 129.81; 134.28;
1
34.92; 144.95); C 55 O (174.99) 3b. H NMR d ppm: CH -11 (d: 1.93 and
1
2
2
.32, J ¼ 10.0); CH -Ph (s: 2.34); CH-7 (s broad: 3.10); CH-8 (m: 3.22);
3
1
3
CH-6 (s: 3.56); ArH (m: 7.04–7.54). C NMR d ppm: CH3-Ph (21.58);
CH -11 (40.03); CH-7 (47.98); CH-8 (49.63); CH-6 (55.17); C Ar (127.22;
2
1
28.26; 128.72; 129.43; 131.10; 132.52; 133.12; 145.08); C 55 O (174.86) 4b.
0
(
2R,6S,8S,10R) 3c and (2R,6S,8R,10S) 4c 9-(4 -Methylphenylsulfonyl)-4-
2,6 8,10
00
00
(3 ,4 -dichloro phenyl)-4,9-diazatetracycle[5.3.1.0
undecane-3,5-dione
ꢀ 0
]
Yield: 75%. Ratio 3c/4c ¼ 40%/60%. mp 203.5–204.98C 3c and
06.9–207.58C 4c. Anal. Calcd. for C Cl N O S: C, 55.35; H,
.81; N, 5.87; O, 13.40; S, 6.72; Cl, 14.85. Found: C, 55.05; H, 3.77; N,
2
3
6
1
3
H
18
2
2
2
2
4
1
.02 3c and C, 55.15; H, 3.84; N, 5,79 4c. H NMR d ppm: CH -11(m:
2
.22 and 1.83); CH -Ph (s: 2.45); CH-8 (s sharp: 3.01); CH-7 (s broad:
3
1
.11); CH-6 (m: 3.31); ArH (m: 7.04–7.79). C NMR d ppm: CH -Ph
3
3
(21.95); CH -11 (32.30); CH-7 (38.08); CH-8 (39.47); CH-6 (47.87); C Ar
2

3
078
Andrade, Nunes, and Uieara
1
127.19; 128.72; 130.53; 130.79; 135.09; 139.99); C 55 O (176.12) 3c. H NMR
(
d ppm: CH -11 (m: 1.97 and 2.35); CH -Ph (s: 2.35); CH-7 (s broad: 3.13);
2
3
1
CH-8 (s: 3.24); CH-6 (s: 3.60); ArH (m: 7.08–7.65). C NMR d ppm:
3
CH -Ph (21.60); CH -11 (40.16); CH-7 (47.98); CH-8 (49.67); CH-6
3
2
(
55.13); C Ar (125.11; 127.60; 128.05; 129.46; 130.13; 131.36; 131.89;
32.66; 145.14); C 55 O (174.59) 4c.
1
0
2R,6S,8S,10R) 3d and (2R,6S,8R,10S) 4d 9-(4 -Methylphenylsulfonyl)-4-
(
00
2,6 8,10
(4 -methylphenyl)-4,9-diazatetracycle[5.3.1.0
ꢀ 0
]undecane-3,5-dione
Yield: 80%. Ratio 3d/4d ¼ 40%/60%. mp 230.7–231.28C 3d and
44.9–246.48C 4d. Anal. Calcd. for C23 N O S: C, 65.37; H, 5.26; N,
.63; O, 15.15; S, 7.59. Found: C, 64.79; H, 5.17; N, 6.69 3d and C, 64.80;
2
6
H
22
2
4
1
H, 5.19; N, 6.70 4d. H NMR d ppm: CH -11(d: 1.20 and 1.82 J ¼ 10.0);
2
CH -Ph (s: 2.39); CH -Ph (s: 2.45); CH-8 (s sharp: 3.03); CH-7 (s broad:
3
3
3
.09); CH-6 (m: 3.28); ArH (d: 7.00 and 7.27 J ¼ 8.10); ArH (d: 7.34 and
3 3 2
1
3
7
.77 J ¼ 8.10). C NMR d ppm: CH -Ph (21.19); CH -Ph (21.61); CH -11
(
31.49); CH-7 (37.33); CH-8 (38.67); CH-6 (47.08); C Ar (126.44; 127.95;
1
28.69; 129.78; 130.00; 134.24; 139,19; 144.85); C 55 O (175.40) 3d. H
1
NMR d ppm: CH -11 (d: 1.93 and 2.33 J ¼ 9.90); CH -Ph (s: 2.33); CH -
2
3
3
Ph (s: 2.41); CH-7 (s broad: 3.08); CH-8 (m: 3.22); CH-6 (m: 3.55); ArH
(
1
3
m: 7.03–7.47). C NMR d ppm: CH -Ph (21.90); CH -11 (40.66); CH-7
3 2
(
48.73); CH-8 (50.36); CH-6 (55.96); C Ar (126.55; 129.15; 129.94;
30.09; 130.72; 133.34; 138.21; 145.61); C 55 O (175.89) 4d.
1
0
2,6 8,10
(
2R,6S,8S,10R) 3e and (2R,6S,8R,10S) 4e 9-(4 -Methylphenylsulfonyl)-4-
00
(4 -methoxyphenyl)-4,9-diazatetracycle[5.3.1.0
undecane-3,5-dione
ꢀ 0
]
Yield: 70%. Ratio 3e/4e ¼ 30%/70%. mp 232.3–233.68C 3e and
24.6–225.38C 4e. Anal. Calcd. For: C N O S: C, 63.00; H, 5.07;
N, 6.39; O, 18.23; S, 7.31. Found: C, 63.50; H, 4.97; N, 6.57 3e and C,
2
H
22
2
3
2
5
1
6
CH -Ph (s: 2.46); CH-8 (s sharp: 3.04); CH-7 (s broad: 3.10); CH-6 (m:
2.90; H, 5.21; N, 6.76 4e. H NMR d ppm: CH -11(m: 1.26 and 1.61);
2
3
1
3
3
.29); O-CH (s: 3.83); ArH (m: 7.00–7.80). C NMR d ppm: CH -Ph
3 3
(
O-CH (55.49); C Ar (114.75; 128.00; 129.82; 144.88); C 55 O (175.59) 3e.
21.66); CH -11 (31.56); CH-7 (37.38); CH-8 (38.74); CH-6 (47.10);
2
3
1
H NMR d ppm: CH -11 (d: 1.95 and 2.30 J ¼ 10.0); CH -Ph (s: 2.33);
2
3
CH-7 (s broad: 3.10); CH-8 (s: 3.22); CH-6 (s: 3.54); O-CH (s: 3.85); ArH
3
1
3
(
ppm: CH -Ph (21.72); CH -11 (40.05); CH-7 (48.08); CH-8 (49.75); CH-6
d: 7.00 and 7.50 J ¼ 8.4); ArH (d: 7.08 and 7.42 J ¼ 8.0). C NMR d
3
2

Synthesis and Characterization of Benzenesulfonylaziridines
3079
(
55.33); O-CH (55.53); C Ar (113.96; 125.59; 127.51; 128.53; 129.49;
3
1
32.73; 145.03; 159.92); C 55 O (175.89) 4e.
0
2R,6S,8S,10R) 3f and (2R,6S,8R,10S) 4f 9-(4 -Methylphenylsulfonyl)-4-
(
00
2,6 8,10
(4 -bromophenyl)-4,9-diazatetracycle[5.3.1.0
ꢀ 0
]undecane-3,5-dione
Yield: 65%. Ratio 3f/4f ¼ 25%/75%. mp 217.2–218.18C 3f and 219.2–
2
1
3
20.08C 4f. Anal. Calcd. for: C H BrN O S: C, 54.22; H, 3.94 N, 5.75; O,
2
2
19
2 4
3.12; S, 6.58; Br, 6.39. Found: C, 54.42; H, 4.21; N, 6.02 3f and C, 54.55; H,
1
.98; N, 5.64 4f. H NMR d ppm: CH -11(d: 1.20 and 1.88 J ¼ 10.7); CH -Ph
2
3
(
s: 2.46); CH-8 (s sharp: 3.02); CH-7 (s broad: 3.11); CH-6 (m: 3.30); ArH (d:
1
3
7
Ph (21.66); CH -11 (31.55); CH-7 (37.24); CH-8 (38.79); CH-6 (47.16);
.05 and 7.61 J ¼ 8.6); ArH (d: 7.34 and 7.77 J ¼ 8.2). C NMR d ppm: CH3-
2
O-CH3 (55.49); C Ar (123.00; 127.99; 128.19; 129.83; 130.00; 132.61;
1
34.33; 144.88); C 55 O (174.94) 3f. H NMR d ppm: CH -11 (d: 1.95 and
1
2
6
2
.35 J ¼ 9.0); CH -Ph (s: 2.35); CH-7 (s broad: 3.10); CH-8 (m: 3.23); CH-
3
(m: 3.57); ArH (d: 7.07 and 7.36 J ¼ 8.0); ArH (d: 7.45 and 7.59
1
3
J ¼ 8.7). C NMR d ppm: CH -Ph (21.62); CH -11 (40.06); CH-7 (48.00);
3
2
CH-8 (49.65); CH-6 (55.19); C Ar (121.20; 127.50; 128.26; 129.45; 131.73;
32.54; 145.09); C 55 O (174.80) 4f.
1
0
2R,6S,8S,10R) 3g and (2R,6S,8R,10S) 4g 9-(4 -Methylphenylsulfonyl)-4-
(
00
2,6 8,10
(4 -nitrophenyl)-4,9-diazatetracycle[5.3.1.0
ꢀ 0
]undecane-3,5-dione
Yield: 65%. Ratio 3g/4g ¼ 20%/80%. mp 266.7–266.98C 3g and 216.9–
2
2
6
17.18C 4g. Anal. Calcd. for: C H N O S: C, 58.27; H, 4.23; N, 9.27; O,
2
2 19 3 6
1.16; S, 7.07. Found: C, 58.81; H, 4.58; N, 7.54 3g and C, 58.11; H, 4.69; N,
1
.66 4g. H NMR d ppm: CH -11(d: 1.25 and 1.90 J ¼ 10.0); CH -Ph (s: 2.46);
2
3
CH-8 (s sharp: 3.04); CH-7 (s broad: 3.14); CH-6 (m: 3.37); ArH (d: 7.26 and
1
3
7
.48 J ¼ 8.6); ArH (d: 7.76 and 8.37 J ¼ 8.6). C NMR d ppm: CH -Ph (21.65);
3
CH -11 (31.55); CH-7 (37.13); CH-8 (38.91); CH-6 (47.23); C Ar (124.55;
2
1
27.27; 127.92; 129.83; 134.34; 136.75; 145.05; 147.31); C 55 O (174.47) 3g. H
1
NMR d ppm: CH -11 (d: 2.00 and 2.33 J ¼ 10.0); CH -Ph (s: 2.32); CH-7 (s
2
3
broad: 3.14); CH-8 (m: 3.29); CH-6 (m: 3.59); ArH (d: 7.02 and 7.34 J ¼ 8.3);
1
3
ArH (d: 7.77 and 8.35 J ¼ 9.1). C NMR d ppm: CH -Ph (21.56); CH -11
3
2
(
40.22); CH-7 (48.05); CH-8 (49.63); CH-6 (55.09); C Ar (123.87; 126.25;
128.12; 129.47; 132.34; 138.20; 145.24; 146.08); C 55 O (174.50) 4g.

3
080
Andrade, Nunes, and Uieara
0
(
2R,6S,8S,10R) 3h and (2R,6S,8R,10S) 4h 9-(4 -Methylphenylsulfonyl)-4-
2,6 8,10
00
00
(2 ,3 -dimethylphenyl)-4,9-diazatetracycle[5.3.1.0
undecane-3,5-dione
ꢀ 0
]
Yield: 75%. Ratio 3h/4h ¼ 40%/60%. mp 225.6–225.98C 3h and dec
1
2
32.08C 4h. H NMR d ppm: CH -11(d: 1.21 and 1.88 J ¼ 10.5); 2-CH -Ph
2
3
(
CH-7 (s broad: 3.20); CH-6 (m: 3.35); ArH (m: 6.67–7.81). C NMR d
m: 2.11); 3-CH -Ph (s: 2.33); 4-CH -Ph (s: 2.46); CH-8 (s sharp: 3.11);
3 3
1
3
ppm: 2-CH -Ph (14.88); 3-CH -Ph (22.36); 4-CH -Ph (21.14); CH -11
3
3
3
2
(
32.38); CH-7 (38.08); CH-8 (38.90); CH-6 (47.93); C Ar (125.84; 126.17;
27.09; 128.55; 130.53; 132.01; 134.88; 135.47; 139.35; 144.61); C 55 O
176.08) 3h. H NMR d ppm: 3-CH -Ph and CH -11 (s: 1.94); 4-CH -Ph
3 2 3
1
1
(
and CH -11 (s: 2.11); 2-CH -Ph (s: 2.35); CH-7 (s broad: 3.10); CH-8 (s:
2
3
1
3
3
.32); CH-6 (m: 3.56); ArH (m: 7.14–7.76). C NMR d ppm: 2-CH -Ph
3
(
15.07); 3-CH -Ph (22.32); 4-CH -Ph (21.16); CH -11 (40.54); CH-7
3 3 2
(
48.96); CH-8 (50.55); CH-6 (56.24); C Ar (126.62; 129.26; 130.24;
30.99; 131.99; 133.33; 134.05; 138.32; 145.76); C 55 O (175.76) 4h.
1
0
2,6 8,10
(
2R,6S,8S,10R) 3i and (2R,6S,8R,10S) 4i 9-(4 -Methylphenylsulfonyl)-4-
00
(3 -ethylphenyl)-4,9-diazatetracycle[5.3.1.0
ꢀ 0
]undecane-3,5-dione
Yield: 73%. Ratio 3i/4i ¼ 40%/60%. mp 189.1–191.08C 3i and 155.7–
1
1
1
56.58C 4i. H NMR d ppm: CH -11 and 3-CH CH -Ph (s broad: 1.25); CH -
2
2
3
2
1 (m: 1.82); CH -Ph (s: 2.44); CH-8 (s sharp: 2.69); CH-7 and 3-CH CH -Ph
1
3
2
3
3
(
s broad: 3.09); CH-6 (s: 3.29); ArH (m: 6.99–7.76). C NMR d ppm:
-CH CH -Ph (15.78 and 29.26); 4-CH -Ph (22.36); CH -11 (32.26); CH-7
3
2
3
3
2
(
38.11); CH-8 (39.45); CH-6 (47.86); C Ar (126.63; 126.87; 128.65;
29.49; 129.99; 130.49; 132.02; 135.22; 145.56; 146.47); C 55 O (176.11) 3i.
1
1
H NMR d ppm: 3-CH CH -Ph (t: 1.29); CH -11 (d: 1.97 and 2.33
2
3
2
J ¼ 14.00); CH -Ph (s: 2.33); CH CH -Ph (m: 2.72); CH-7 (s broad: 3.09);
3
3
2
1
3
CH-8 (s: 3.24); CH-6 (s: 3.57); ArH (m: 7.02–7.50). C NMR d ppm:
-CH CH -Ph (16.12 and 29.48); CH -Ph (22.28); CH -11 (40.70); CH-7
3
2
3
3
2
(
48.73); CH-8 (50.32); CH-6 (55.97); C Ar (124.04; 124.62; 126.31;
26.80; 127.99; 129.17; 130.04; 133.30; 135.26; 145.57); C 55 O (175.84) 4i.
1
REFERENCES
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2
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2
. March, J. Advanced Organic Chemistry — Reactions, Mechanisms, and
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3
. Nunes, R.J. The Chemistry and Biological Activity of Cyclic Imidoben-
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4
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6
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2
,4
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7
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1
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1
0. Salakhov, M.S.; Musaeva, N.F.; Suleimanov, S.N.; Bairamov, A.A. Kin-
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4
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1
944, 66, 404–406.
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1
1
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Received in the USA May 25 2004