Synthesis and characterization of novel 1,3-selenazine derivatives. BF3·Et2O-assisted reaction of primary selenoamides with α,β-unsaturated ketones

Article abstract of DOI:10.1039/a809131e

Reaction of primary selenoamides with α,β-unsaturated ketones in the presence of BF₃·Et₂O provided 5,6-dihydro-4H-1,3-selenazine derivatives in high yields. Among the 1,3-selenazine diastereomers bearing two asymmetric carbons at the

Full text of DOI:10.1039/a809131e

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Synthesis and characterization of novel 1,3-selenazine derivatives.
BF3ؒEt2O-assisted reaction of primary selenoamides with
á,â-unsaturated ketones
Mamoru Koketsu,* Takayuki Senda, Katsuhiro Yoshimura and Hideharu Ishihara*
Department of Chemistry, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu,
501-1193, Japan
Received (in Cambridge) 23rd November 1998, Accepted 8th January 1999
Reaction of primary selenoamides with α,β-unsaturated ketones in the presence of BF3ؒEt2O provided 5,6-dihydro-
4H-1,3-selenazine derivatives in high yields. Among the 1,3-selenazine diastereomers bearing two asymmetric
carbons at the C4 and C6 positions, the cis form is predominant.
1J(77Se–13C) values were observed at the C6 carbon of 3a, it was
Introduction
confirmed that 3a was formed by the nucleophilic addition of
the selenium atom of selenoamide not to the carbonyl carbon
of 2a but to the β-position of the carbonyl carbon of 2a. Simi-
larly, the one step reaction of other α,β-unsaturated ketones
with primary selenoamides gave 5,6-dihydro-4H-1,3-selenazine
derivatives in good to high yields (entries 1–13). There was no
difference in yield of 5,6-dihydro-4H-1,3-selenazine derivatives
from the corresponding aromatic (entries 1–8) and aliphatic
(entries 9–13) selenoamides. Even cyclohexenone (entries 8 and
13) afforded the 5,6-dihydro-4H-1,3-selenazine derivatives in
good yield without steric hindrance. However, the reaction of
selenoamide with 1,5-diphenylpenta-1,4-dien-3-one gave 6H-
1,3-selenazine 3n, and its yield was low (31.5%). 4-Methyl-
selenobenzamide was recovered in 60% yield (entry 14).
Many syntheses of heterocyclic compounds containing sulfur
or selenium1 have been reported because of their various inter-
esting biological activities. For example, 1,3-thiazine or thiazole
derivatives possess antitumor activity,2 antibacterial activity,3
human immunodefiency virus (HIV) inhibition,4 and other
notable activities. On the other hand, only a few reports have
been published on both selenium- and nitrogen-containing
heterocyclic compounds.5 This is mainly due to the fact that the
essential selenium-containing starting materials are less readily
available than the sulfur analogue intermediates. Only a few
practical applications of primary selenoamides6 to the syn-
thesis of heterocycles have been made owing to the difficulty in
preparing the primary selenoamides.
We have previously investigated the synthesis and character-
As for spectroscopic data for the obtained 1,3-selenazine
derivatives, in the IR spectra of 5,6-dihydro-4H-1,3-selenazine
ization of selenocarbonyl compounds7 and developed
a
convenient method for the synthesis of potassium seleno-
carboxylates.8 It was found that the selenobenzoates function
for a reagent of introducing selenium to nitriles to give primary
selenoamides under mild conditions.9 Here, we describe a con-
venient preparation and the spectroscopic characteristics of
novel 5,6-dihydro-4H-1,3-selenazine derivatives from primary
selenoamides.
derivatives, the absorption of the C᎐N bond of 3a–3h was
᎐
observed at 1594.1 3.2 cmϪ1 and that of 3i–3m was 1643.2
39.4 cmϪ1. In the mass spectra of 5,6-dihydro-4H-1,3-selen-
azine derivatives, the corresponding nitrile is observed as the
most stable fragment ion peak together with molecular peak.
For example, the CIMS spectrum of 3c showed peaks at m/z (%,
fragment) 118 (100.0, [p-toluonitrile ϩ 1]ϩ), 180 (34.7, [M Ϫ p-
toluonitrile]ϩ), 280 (12.1, [M ϩ 1 Ϫ H2O]ϩ), 296 (7.9, [M ϩ 1
78Se isotope]ϩ), and 298 (16.0, [M ϩ 1]ϩ). In the 77Se NMR
spectra of 1,3-selenazine derivatives, 77Se signals were observed
in the range of δ 334.6 60.0, which are at a higher field com-
pared with 77Se signals of dihydroselenophenes (δ 480.0
96.4)10 and selenocarbonyl compounds (δ 1420–2131).11 The
77Se signals of 3d, 3g, 3h, 3l, and 3m are deshielded by approxi-
mately 50–100 ppm by the effect of the substituent at C6
compared with other 1,3-selenazines. 1J(77Se–13C) values of
3, which were observed for the C6 carbon, were 54.2 1.7
Hz. These values are typical for a C–Se single bond with an
sp3 carbon but not for a C–Se double bond with an sp2
carbon.12
Results and discussion
Because the selenoamide is considered to contain a seleno-
amide–selenoimidate tautomerism and bear two reactive sites,
its reactivity is of interest. The reaction of primary seleno-
amides with 2 equiv. of aldehydes is initiated by nucleophilic
addition of the nitrogen of the selenoamide to the carbonyl
carbon to give 1,3,5-oxaselenazines.5g On the other hand, the
reaction of the selenoamide with halomethyl ketone afforded
1,3-selenazole with attack of selenium on the ketone.5a,6d The
reaction of primary selenoamide 1 with α,β-unsaturated ketone
2 gives 1,3-selenazine derivative 3 in good yields under mild
conditions (Scheme 1). The results are summarized in Table 1.
The structure of 3 was confirmed by studies of IR, UV, 1H, 13C,
and 77Se NMR, HRMS, and/or elemental analysis. Because
Selenazines 3c, 3e–3g, and 3j–3l consist of diastereomers
containing two or three asymmetric centers at the C4, C6 and/
or C5 positions of the selenazine ring. NOE irradiation tech-
niques confirmed that the major diastereomer has a cis relation-
ship between the OH group at C4 and the substituent at C6.
The NOE spectra indicated the presence of diastereomers in a
ratio of approximately 74–90% (cis): 26–10% (trans). Irradi-
ation of the methyl group of C4 produced a positive NOE effect
on the hydrogen atoms at C6 and C5. The NOE effect between
CH3 at C4 and the hydrogen at C6 of 3f was 9.8%, and that for
3g was 14.2%, respectively.
R1
R2
R
Se
R3
BF3•Et2O
CH2Cl2
Se
R1
R4
+
N
R3
0 °C, 3h
R
NH2
R2
HO R4
O
1
2
3
Scheme 1
J. Chem. Soc., Perkin Trans. 1, 1999, 453–456
453

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Table 1 Preparation of 1,3-selenazines
Se
Se
BF3
R
NH
H
R
NH2
α,β-Unsaturated
ketone 2
Yield, %
+
+
O
Entry Selenoamide 1
(cis/trans)a
O
BF3
1
2
R
Se
O
1
R = 4-CH3C6H4
1a
N
HO
3a
73.4
H
H
2a
–BF3
N
OBF3H
N
O
R
Se
O
R
Se
R
Se
Se
N
2
3
1a
1a
HO
3b
87.9
2b
R
R
Se
O
O
R
Se
N
N
N
HO
H
3c
2c
O–
OH
93.3
3
R
Se
N
Scheme 2
HO3d
85.0
4
5
6
1a
1a
1a
2d
in Scheme 2. The Michael adduct was detected by 13C NMR
spectroscopy.13
O
R
Se
N
HO
2e
2f
3e
Experimental
General methods
70.5 (88.6:11.4)
R
Se
O
N
Primary selenoamides were synthesized in accordance with a
previously described procedure.9 The 77Se NMR (76 MHz)
spectra were obtained from a JEOL α-400 spectrometer, and
77Se chemical shifts are expressed in ppm deshielded with
respect to neat Me2Se in CDCl3. 1J(77Se–13C) values are the 77Se
satellites of the proton-decoupled 13C NMR spectra.
HO
3f
92.1 (83.9:16.1)
O
R
Se
N
7
8
9
1a
1a
HO
3g
99.9 (74.2:25.8)
2g
R
Se
4-Hydroxy-4-methyl-2-(4-methylphenyl)-5,6-dihydro-4H-1,3-
selenazine (3a)
O
N
HO3h
2h
2b
4-Hydroxy-4-methyl-2-(4-methylphenyl)-5,6-dihydro-4H-1,3-
selenazine 3a was synthesized as follows: to a solution of
4-methylselenobenzamide (0.20 g, 1 mmol) in dry dichloro-
methane (10 mL) was added methyl vinyl ketone (0.070 g, 1
mmol) at 0 ЊC under an argon atmosphere. To this solution was
added BF3ؒEt2O (1.2 mmol). The reaction mixture was stirred
for 3 h, quenched with saturated sodium carbonate solution (40
mL), and extracted with dichloromethane (40 mL × 3). The
extracts were dried (Na2SO4) and evaporated to dryness. The
residue was purified by column chromatography on silica gel
using dichloromethane as the eluent to give 0.203 g (73.4%) of
3a as a yellow powder. When the temperature of the reaction
was raised to 25 ЊC or lowered to Ϫ25 ЊC, the yields of 3a were
46.8% and 49.0%, respectively. Further, when CHCl3, ether or
THF was used as a solvent instead of CH2Cl2, the yield of 3a
was low. Mp 89.0–89.6 ЊC; IR (KBr) 3160, 1594 cmϪ1; UV/Vis
(CH2Cl2) λmax (log (ε/dm3 molϪ1 cmϪ1)) 341 (2.42), 255 (3.98);
1H NMR (CDCl3) δ 1.28 (3H, s), 1.46–1.62 (1H, m), 1.88 (1H,
dt, J = 4.2, 9.6 Hz), 2.25 (3H, s), 2.99–3.07 (2H, m), 3.81 (1H, br
s), 7.07 (2H, d, J = 8.2 Hz), 7.54 (2H, d, J = 8.2 Hz); 13C NMR
(CDCl3) δ 18.3, 21.4, 24.9, 30.0, 85.1, 126.5, 129.1, 137.5, 141.0,
156.8; 77Se NMR (CDCl3) δ 245.0; Anal. Calc. for C12H15NOSe:
C, 53.53; H, 5.62; N, 5.20. Found: C, 53.49; H, 5.61; N, 5.03%).
81.1
R
Se
N
R = n-C5H11
1b
HO3i
99.9
R
Se
N
2c
10
11
12
13
14
1b
1b
1b
1b
1a
HO 3j
90.7
O
R
Se
N
2i
HO
3k
91.3 (83.5:16.5)
R
Se
2g
N
HO
3l
86.2 (89.6:10.4)
R
Se
2h
N
HO
3m
99.9
O
R'
Se
4-Ethyl-4-hydroxy-2-(4-methylphenyl)-5,6-dihydro-4H-1,3-
N
2j
selenazine (3b)
3n
3b–n were prepared following the same procedure as 3a. Mp
60.6–61.3 ЊC; IR (KBr) 3150, 1593 cmϪ1; UV/Vis (CH2Cl2) λmax
(log (ε/dm3 molϪ1 cmϪ1)) 345 (3.17), 260 (3.94); 1H NMR
(CDCl3) δ 1.02 (3H, t, J = 5.86 Hz, CH3), 1.62–1.74 (3H, m),
2.01–2.05 (1H, m), 2.36 (3H, s, CH3Ph), 2.86 (1H, br s, OH),
3.08–3.19 (1H, m), 7.17 (2H, d, J = 8.4 Hz, Ar), 7.64 (2H, d,
J = 8.4 Hz, Ar); 13C NMR (CDCl3) δ 7.1, 17.7, 21.3, 27.6, 30.3,
31.5
a Calculated from 1H NMR spectra.
Though the detailed mechanism of the above reaction has
not been clarified yet, the 5,6-dihydro-4H-1,3-selenazine form-
ation could be explained by the possible mechanism presented
454
J. Chem. Soc., Perkin Trans. 1, 1999, 453–456

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86.6, 126.5, 129.0, 137.6, 140.9, 156.4; 77Se NMR (CDCl3)
δ 250.4; HRMS: m/z = 283.04748, calc. for C13H17NOSe, found
283.04745.
5-Hydroxy-3-(4-methylphenyl)-4-aza-2-selenabicyclo[3.3.1]non-
3-ene (3h)
Mp 115.1–117.0 ЊC; IR (KBr) 3264, 1596 cmϪ1; UV/Vis (CH2-
1
Cl2) λmax (log (ε/dm3 molϪ1 cmϪ1)) 300 (2.82), 263 (3.93); H
4-Hydroxy-4,5,6-trimethyl-2-(4-methylphenyl)-5,6-dihydro-4H-
1,3-selenazine (3c)
NMR (CDCl3) δ 1.60–1.65 (2H, m), 1.77–1.811 (2H, m), 1.93
(1H, d, J = 10.6 Hz), 1.99 (2H, s), 2.07 (1H, d, J = 12.5 Hz), 2.34
(3H, s, CH3Ph), 3.49–3.53 (1H, m), 3.90 (1H, br s, OH), 7.16
(2H, d, J = 7.9 Hz, Ar), 7.64 (2H, d, J = 7.9 Hz, Ar); 13C NMR
(CDCl3) δ 18.9, 21.2, 33.3, 34.1, 36.2, 39.4, 82.9, 126.4, 128.9,
137.3, 140.6, 158.0; 77Se NMR (CDCl3) δ 380.2; HRMS:
m/z = 295.04555, calc. for C14H17NOSe, found 295.04745.
Mp 110.0–111.8 ЊC; IR (KBr) 3288, 1594 cmϪ1; UV/Vis
(CH2Cl2) λmax (log (ε/dm3 molϪ1 cmϪ1)) 343 (2.25), 260 (3.96);
1H NMR (CDCl3) δ 0.86 (3H, d, J = 6.6 Hz, CH3), 1.37 (3H, s,
CH3), 1.46 (3H, d, J = 7.0 Hz, CH3), 1.64–1.77 (1H, m, CH),
2.36 (3H, s, PhCH3), 3.05 (1H, br s, OH), 3.88–4.01 (1H, m,
CH), 7.17 (2H, d, J = 8.2 Hz, Ar), 7.65 (2H, d, J = 8.2 Hz, Ar);
13C NMR (CDCl3) δ 7.4,19.1, 21.3, 25.8, 36.8, 38.3, 90.3, 126.4,
129.0, 137.1, 140.9, 158.4; 77Se NMR (CDCl3) δ 299.3; HRMS:
m/z = 297.06312, calc. for C14H19NOSe, found 297.06309.
4-Ethyl-4-hydroxy-2-pentyl-5,6-dihydro-4H-1,3-selenazine (3i)
IR (Neat) 3408, 1713 cmϪ1; UV/Vis (CH2Cl2) λmax (log (ε/dm3
1
molϪ1 cmϪ1)) 305 (3.34), 245 (3.34); H NMR (CDCl3) δ 0.89
(3H, t, J = 6.6 Hz, CH3), 0.97 (3H, t, J = 7.5 Hz, CH3), 1.32 (4H,
t, J = 3.6 Hz), 1.47–1.57 (1H, m), 1.58–1.65 (4H, m), 1.98 (1H,
dt, J = 4.2, 13.9 Hz), 2.34–2.42 (2H, m), 2.99–3.03 (2H, m),
3.95 (1H, br s, OH); 13C NMR (CDCl3) δ 7.09, 13.9, 17.2, 22.3,
27.5, 27.7, 29.8, 31.0, 43.5, 86.2, 160.7; 77Se NMR (CDCl3)
δ 252.9; HRMS: m/z = 263.07877, calc. for C11H21NOSe, found
263.07871.
4-Hydroxy-4,6,6-trimethyl-2-(4-methylphenyl)-5,6-dihydro-4H-
1,3-selenazine (3d)
Mp 92.0–93.3 ЊC; IR (KBr) 3316, 1590 cmϪ1; UV/Vis (CH2Cl2)
1
λmax (log (ε/dm3 molϪ1 cmϪ1)) 340 (2.07), 260 (3.96); H NMR
(CDCl3) δ 1.51 (3H, s, CH3), 1.63 (3H, s, CH3), 1.64 (3H, s,
CH3), 1.79 (1H, d, J = 14.0 Hz), 1.84 (1H, d, J = 14.0 Hz), 2.36
(3H, s, CH3Ph), 2.88 (1H, br s, OH), 7.18 (2H, d, J = 7.8 Hz,
Ar), 7.68 (2H, d, J = 7.8 Hz, Ar); 13C NMR (CDCl3) δ 21.3,
28.9, 33.0, 34.7, 41.7, 46.9, 88.7, 127.0, 129.0, 137.6, 141.0,
158.6; 77Se NMR (CDCl3) δ 439.4; Anal. Calc. for C14H19NOSe:
C, 56.56; H, 6.44; N, 4.71. Found: C, 56.27; H, 6.47; N, 4.63%.
4-Hydroxy-4,5,6-trimethyl-2-pentyl-5,6-dihydro-4H-1,3-
selenazine (3j)
IR (Neat) 3246, 1624 cmϪ1; UV/Vis (CH2Cl2) λmax (log (ε/dm3
1
molϪ1 cmϪ1)) 302 (2.31), 242 (3.42); H NMR (CDCl3) δ 0.81
(3H, d, J = 6.8 Hz, CH3), 0.89 (3H, t, J = 7.1 Hz, CH3), 1.29
(3H, s, C4-CH3), 1.22–1.37 (4H, m, (CH2)2), 1.40 (3H, d, J = 7.0
Hz, CH3), 1.54–1.67 (3H, m), 2.42 (2H, t, J = 7.5 Hz), 3.78–3.91
(1H, m), 3.88 (br, 1H, OH); 13C NMR (CDCl3) δ 7.2, 13.9, 19.1,
22.3, 26.1, 27.7, 31.0, 36.3, 38.3, 43.0, 89.6, 162.9; 77Se NMR
(CDCl3) δ 303.6; HRMS: m/z = 277.09442, calc. for C12H23-
NOSe, found 277.09437.
cis-4-Hydroxy-6-isopropyl-4-methyl-2-(4-methylphenyl)-5,6-
dihydro-4H-1,3-selenazine (3e)
Mp 79.5–80.6 ЊC; IR (KBr) 3261, 1599 cmϪ1; UV/Vis (CH2Cl2)
1
λmax (log (ε/dm3 molϪ1 cmϪ1)) 349 (1.68), 257 (4.02); H NMR
(CDCl3) δ 1.01 (6H, d, J = 6.8 Hz, C6-C(CH3)2), 1.34 (3H, s,
CH3), 1.35 (1H, t, J = 13.4 Hz), 1.85 (1H, q, J = 6.4 Hz), 1.97
(1H, dd, J = 6.4, 13.4 Hz), 2.34 (3H, s, CH3Ph), 3.37–3.49 (1H,
m, C6), 4.01 (1H, br s, OH), 7.15 (2H, d, J = 8.1 Hz, Ar), 7.65
(2H, d, J = 8.1 Hz, Ar); 13C NMR (CDCl3) δ 19.8, 20.4, 21.2,
24.0, 33.7, 36.4, 45.3, 88.4, 126.5, 128.9, 137.2, 140.6, 157.6; 77Se
NMR (CDCl3) δ 306.5; Anal. Calc. for C15H21NOSe: C, 57.87;
H, 6.80; N, 4.50. Found: C, 57.92; H, 6.78; N, 4.30%).
cis-4-Hydroxy-4-methyl-2-pentyl-6-propyl-5,6-dihydro-4H-1,3-
selenazine (3k)
IR (Neat) 3242, 1626 cmϪ1; UV/Vis (CH2Cl2) λmax (log (ε/dm3
1
molϪ1 cmϪ1)) 301 (2.46), 244 (3.45); H NMR (CDCl3) δ 0.89
(3H, t, J = 6.4 Hz, CH3), 0.94 (3H, t, J = 7.1 Hz, CH3), 1.29 (3H,
s, C4-CH3), 1.29–1.48 (6H, m), 1.51–1.69 (4H, m), 1.73–
1.86 (1H, m), 1.96 (1H, dt, J = 4.1, 13.5 Hz), 2.41 (2H, t, J = 7.0
Hz), 3.41–3.56 (1H, m, C6), 4.30 (1H, br s, OH); 13C NMR
(CDCl3) δ 13.8, 13.9, 20.3, 22.3, 24.8, 27.7, 31.0, 36.6, 39.3, 39.7,
43.0, 87.3, 161.4; 77Se NMR (CDCl3) δ 345.1; HRMS: m/z =
291.11007, calc. for C13H25NOSe, found 291.11001.
cis-4-Hydroxy-4-methyl-2-(4-methylphenyl)-6-pentyl-5,6-
dihydro-4H-1,3-selenazine (3f)
Mp 66.9–67.7 ЊC; IR (KBr) 3178, 1590 cmϪ1; UV/Vis (CH2Cl2)
1
λmax (log (ε/dm3 molϪ1 cmϪ1)) 342 (2.37), 258 (4.01); H NMR
(CDCl3) δ 0.90 (3H, t, J = 6.8 Hz), 1.30–1.33 (6H, m, (CH2)3),
1.33 (3H, s, CH3), 1.34–1.42 (2H, m), 1.62–1.68 (1H, m), 1.77–
1.84 (1H, m), 1.98 (1H, dd, J = 4.4, 13.6 Hz), 2.33 (3H, s,
CH3Ph), 3.48–3.53 (1H, m, C6), 4.02 (1H, br s, OH), 7.13
(2H, d, J = 8.1 Hz, Ar), 7.63 (2H, d, J = 8.1 Hz, Ar); 13C
NMR (CDCl3) δ 13.8, 21.2, 22.3, 24.2, 26.7, 31.4, 37.4, 37.4,
39.1, 87.8, 126.5, 128.8, 137.1, 140.5, 157.1; 77Se NMR (CDCl3)
δ 339.4; HRMS: m/z = 339.11007, calc. for C17H25NOSe, found
339.11003.
cis-4-Hydroxy-4-methyl-2-pentyl-6-phenyl-5,6-dihydro-4H-1,3-
selenazine (3l)
IR (Neat) 3198, 1634 cmϪ1; UV/Vis (CH2Cl2) λmax (log (ε/dm3
1
molϪ1 cmϪ1)) 292 (3.41), 241 (3.95); H NMR (CDCl3) δ 0.89
(3H, t, J = 6.8 Hz, CH3), 1.32–1.34 (4H, m, (CH2)2), 1.43 (3H, s,
CH3), 1.61–1.66 (2H, m, CH2), 1.92 (1H, t, J = 13.7 Hz), 2.12
(1H, dd, J = 4.0,13.7 Hz), 2.46 (2H, t, J = 7.1 Hz), 4.61 (1H, dd,
J = 4.0, 13.7 Hz, C6), 4.63 (br, 1H, OH), 7.24–7.34 (5H, m, Ar);
13C NMR (CDCl3) δ 13.9, 22.3, 25.2, 27.6, 31.0, 38.7, 39.4, 42.7,
87.7, 127.5, 127.7, 128.8, 140.9, 162.1; 77Se NMR (CDCl3)
δ 395.6; HRMS: m/z = 325.09442, calc. for C16H23NOSe, found
325.09437.
cis-4-Hydroxy-4-methyl-2-(4-methylphenyl)-6-phenyl-5,6-
dihydro-4H-1,3-selenazine (3g)
Mp; 105.3–106.3 ЊC; IR (KBr) 3260, 1597 cmϪ1; UV/Vis (CH2-
Cl2) λmax (log (ε/dm3 molϪ1 cmϪ1)) 342 (2.59), 259 (4.08); H
1
NMR (CDCl3) δ 1.49 (3H, s, CH3), 1.96 (1H, t, J = 13.6 Hz),
2.19 (1H, dd, J = 4.4, 13.6 Hz), 2.36 (3H, s, CH3Ph), 3.13 (1H,
br s, OH), 4.69 (1H, dd, J = 4.4, 13.6 Hz, C6), 7.18 (2H, d,
J = 7.8 Hz, Ar), 7.24–7.29 (1H, m, Ar), 7.33–7.38 (4H, m, Ar),
7.66 (2H, d, J = 7.8 Hz, Ar); 13C NMR (CDCl3) δ 21.4, 24.9,
38.6, 40.2, 88.4 (C4), 126.6, 127.7, 127.9, 128.9, 129.1, 136.9,
140.9, 141.1, 157.6; 77Se NMR (CDCl3) δ 387.4; Anal. Calc. for
C18H19NOSe: C, 62.60; H, 5.55; N, 4.06. Found: C, 62.32; H,
5.47; N, 3.99%).
5-Hydroxy-3-pentyl-4-aza-2-selenabicyclo[3.3.1]non-3-ene (3m)
IR (Neat) 3214, 1619 cmϪ1; UV/Vis (CH2Cl2) λmax (log (ε/dm3
molϪ1 cmϪ1)) 304 (3.14), 236 (3.43); 1 H NMR (CDCl3) δ 0.90
(3H, t, J = 7.1 Hz), 1.33–1.37 (5H, m), 1.54–1.67 (3H, m), 1.73–
1.80 (2H, m), 1.88–2.02 (4H, m), 2.45 (2H, q, J = 7.6 Hz), 3.80–
3.83 (1H, m), 4.58 (1H, br s, OH); 13C NMR (CDCl3) δ 13.8,
18.9, 22.3, 27.9, 31.0, 33.2, 34.4, 35.9, 39.5, 43.5, 82.4, 163.3;
J. Chem. Soc., Perkin Trans. 1, 1999, 453–456
455

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77Se NMR (CDCl3) δ 385.7; HRMS: m/z = 275.07877, calc. for
C12H21NOSe, found 275.07873.
5 (a) V. I. Cohen, Synthesis, 1979, 66; (b) V. I. Cohen, J. Heterocycl.
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A. Couture and P. Grandclaudon, J. Org. Chem., 1988, 53, 4852;
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N. Kambe and N. Sonoda, Chem. Lett., 1990, 913; (h) V. S.
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Chem. Soc. Jpn., 1985, 58, 1448; (b) V. I. Cohen, Synthesis, 1978,
768; (c) K. Shimada, S. Hikage, Y. Takeishi and Y. Takikawa, Chem.
Lett., 1990, 1403; (d) L.-L. Lai and D. H. Reid, Synthesis, 1993, 870;
(e) X.-R. Zhao, M.-D. Ruan, W.-Q. Fan and X.-J. Zhou, Synth.
Commun., 1994, 24, 1761.
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Chem. Soc. Jpn., 1990, 63, 835; (b) H. Ishihara, M. Yoshimi and
S. Kato, Angew. Chem., Int. Ed. Engl., 1990, 29, 530; (c) S. Kato,
H. Kageyama, Y. Kawamura, T. Murai and H. Ishihara, Chem. Ber.,
1992, 125, 417; (d) S. Kato, T. Komuro, T. Kanda, H. Ishihara and
T. Murai, J. Am. Chem. Soc., 1993, 115, 3000; (e) Y. Kawahara,
S. Kato, T. Kanda, T. Murai and H. Ishihara, J. Chem. Soc., Chem.
Commun., 1993, 3, 277; ( f ) S. Kato, T. Kawachi, K. Ibi, S. Nakaiida,
K. Kawai, T. Kanda, T. Murai and H. Ishihara, Heteroatom Chem.,
1995, 6, 215.
2-(4-Methylphenyl)-4-(2-phenylvinyl)-6-phenyl-6H-1,3-selen-
azine (3n)
Mp 54.5–56.0 ЊC; IR (KBr) 1599 cmϪ1; UV/Vis (CH2Cl2) λmax
(log (ε/dm3 molϪ1 cmϪ1)) 292 (4.33), 243 (4.13); 1H NMR
(CDCl3) δ 2.39 (3H, s, CH3Ph), 4.97 (1H, d, J = 6.0 Hz), 5.23
(1H, d, J = 1.1 Hz), 5.34 (1H, d, J = 6.0 Hz), 6.93 (1H, d,
J = 15.8 Hz), 7.20–7.45 (6H, m, Ar), 7.54 (2H, dd, J = 1.3, 7.0
Hz, Ar), 7.93 (2H, dd, J = 1.3, 7.0 Hz, Ar); 13C NMR (CDCl3)
δ 21.4, 38.0, 108.8, 126.8, 127.6, 127.7, 128.2, 128.6, 128.8,
129.0, 129.3, 129.5, 136.9, 137.3, 141.8, 142.3, 148.4, 161.5; 77Se
NMR (CDCl3) δ 350.1; HRMS: m/z = 415.08386, calc. for
C25H21NOSe, found 415.08381.
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peaks were observed at δ = 193.7 and 207.0, which were assigned to
the 13C᎐NH2 and the carbonyl carbon resonance of the Michael
᎐
adduct, respectively. 13C NMR (CDCl3) δ 18.4, 21.7, 29.8, 44.1,
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᎐
᎐
4 R. Jansen, B. Kunze, H. Reichenbach, E. Jurkiewicz, G. Hunsmann
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