Synthesis of 5H-1,2,3-triazolo[4,3-a][2]benzazepines from the Baylis-Hillman adducts of 2-alkynylbenzaldehydes

Article abstract of DOI:10.1002/jhet.5570410422

The facile synthesis of 5H-1,2,3-triazolo[4,3-a][2]benzazepines 5a-d by the intramolecular 1,3-dipolar cycloaddition reaction of 2-alkynylphenylallyl azides 4a-d is described. The latter were readily obtained from 2-alkynylbenzaldehydes 1a-d through the Baylis-Hillman adducts 2a-d followed by acetylation to compounds 3a-d and nucleophilic substitution by azide to compounds 4a-d.

Full text of DOI:10.1002/jhet.5570410422

Jul-Aug 2004
613
Synthesis of 5H-1,2,3-Triazolo[4,3-a][2]benzazepines from the
Baylis-Hillman Adducts of 2-Alkynylbenzaldehydes
Seung Ho Ko and Kee-Jung Lee*
Organic Synthesis Laboratory, School of Chemical Engineering,
Hanyang University, Seoul 133-791, Korea
Received January 15, 2004
The facile synthesis of 5H-1,2,3-triazolo[4,3-a][2]benzazepines 5a-d by the intramolecular 1,3-dipolar
cycloaddition reaction of 2-alkynylphenylallyl azides 4a-d is described. The latter were readily obtained
from 2-alkynylbenzaldehydes 1a-d through the Baylis-Hillman adducts 2a-d followed by acetylation to
compounds 3a-d and nucleophilic substitution by azide to compounds 4a-d.
J. Heterocyclic Chem., 41, 613 (2004).
1,2,3-Triazoles and 1,2,3-triazole containing hetero-
ature occurred in a SN2' fashion to give the required key
intermediates 2-alkynylphenylallyl azides 4a-d (63-80%).
The stereochemistry of the products was established by
comparing NMR values of olefinic and methylene protons
with literature values [15]. In all cases, the stereoselectivity
was found to be 100% (E)-selectivity, as determined by 1H
nmr analysis. Finally, the intramolecular 1,3-dipolar
cycloaddition reaction of azides with alkynes of 4a-d in
refluxing toluene produced good yields (72-77%) of the
corresponding 5H-1,2,3-triazolo[4,3-a][2]benzazepines
cycles are known to display a wide range of biological
activities such as anti-HIV activity [1], antimicrobial activ-
ity against Gram positive bacteria [2], selective β3 adrener-
gic receptor agonism [3], and antianxiety activity [4].
1,2,3-Triazoles have also found wide use in industrial
applications such as dyes, corrosion inhibition, photostabi-
lizers, photographic materials, and agrochemicals [5].
Therefore, it is important to develop new and more effi-
cient synthetic pathways to a diverse array of 1,2,3-triazole
pharmacophores. Several different methods have been
described for the synthesis of 1,2,3-triazoles, including the
intramolecular cyclization of bishydrazones or mixed
hydrazones, miscellaneous oxidations, as well as the most
important 1,3-dipolar cycloaddition of azides to alkynes
[5-10].
The Baylis-Hillman reaction has been the subject of
recent reviews [11] and continues to elicit attention. We
have demonstrated applications of this reaction in the syn-
thesis of 3-oxo-2,3-dihydro-1H-isoindoles from 2-cyano-
benzaldehyde [12] and 4H -t e t r a z o l o [ 1 , 5 -a] [ 1 ] b e n-
zazepines from 2-azidobenzaldehyde using intramolecular
1,3-dipolar cycloaddition reaction [13]. Here we report a
facile synthesis of 5H- 1 , 2 , 3 - t r i a z o l o [ 4 , 3 - a] [ 2 ] b e n-
zazepines 5 via treatment of the Baylis-Hillman acetate
adducts of 2-alkynylbenzaldehydes with azide followed
by intramolecular 1,3-dipolar cycloaddition reaction.
The readily available acetylenic benzaldehydes 1a-d,
whose preparation has been previously described [14], pro-
vided a convenient starting point for the synthesis of this
ring system, as shown in Scheme I. Treatment of 2-alkynyl-
benzaldehydes 1 a-d with 3.0 molar equivalents of methyl
acrylate in the presence of 1.0 molar equivalent of 1,4-diaz-
abicyclo[2,2,2]octane (DABCO) in neat at room tempera-
ture afforded the adducts, methyl 3-(2-alkynylphenyl)-3-
hydroxy-2-methylenepropanoates 2a-d in good yields (81-
84%). The reaction of adducts 2a-d with acetic anhydride
in the presence of catalytic amount of N, N- d i m e t h y l-
aminopyridine (DMAP) in dichloromethane at room tem-
perature gave the Baylis-Hillman acetate adducts 3a-d (76-
96%). Nucleophilic substitution reaction of the acetates 3 a-
d with sodium azide in dimethyl sulfoxide at room temper-

614
S. H. Ko and K.-J. Lee
Vol. 41
Methyl 3-Hydroxy-2-methylene-3-(2-phenylethynyl)phenyl-
propanoate (2b).
5 a-d. The infrared spectra of 5a-d showed the disappear-
ance of absorption of carbon-carbon triple bond and azide
1
bands. In the H nmr spectra, the charateristic chemical
The procedure was the same as described in the preparation of
2a with 2-(phenylethynyl)benzaldehyde 1b (1.24 g, 6 mmoles)
except reaction time (5 days). Yield: 1.47 g (84%); oil; ir (neat):
shift of the methine proton of C7 were found at δ = 7.92-
8.03 as a singlet, and two methylene protons of C5 were
observed at δ = 5.26-5.36 as a singlet. The possible tau-
tomeric structure 6 was ruled out by two-dimensional
NOESY experiment. In 5b, correlation between C7
methine peak (s, δ = 8.03 ppm) and aromatic proton (m, δ =
7.55-7.57 ppm) was observed; a correlation between the C5
methylene protons (s, δ = 5.30 ppm) and any aromatic pro-
tons was not observed.
In summary, application of the Baylis-Hillman reaction
to 2-alkynylbenzaldehydes provides convenient access to
new substituted 5H-1, 2, 3-triazolo[4, 3-a][2]benzazepine
derivatives by the intramolecular 1,3-dipolar cycloaddi-
tion of readily available 2-alkynylphenylallyl azides.
-1
1
3431, 2217, 1711, 1633, 1493, 1439 cm ; H nmr (deuteriochlo-
roform): δ 3.28 (d, 1 H, J = 5.19 Hz), 3.75 (s, 3 H), 5.68 (s, 1 H),
13
6.15 (d, 1 H, J = 4.88 Hz), 6.34 (s, 1 H), 7.26-7.58 (m, 9 H);
nmr (deuteriochloroform): δ 51.97, 70.71, 87.04, 94.57, 121.63,
C
122.96, 126.45, 126.72, 126.94, 127.63, 128.39, 128.80, 131.47,
+
132.25, 141.25, 142.56, 167.09; ms: m/z (%) 292 (M , 36), 260
(22), 232 (56), 231 (100), 203 (72), 202 (47), 178 (30).
Anal. Calcd for C
H, 5.27.
H O : C, 78.06; H, 5.52. Found: C, 77.73;
19 16 3
Methyl 3-[2-(1-Hexyn-1-yl)]phenyl-3-hydroxy-2-methylene-
propanoate (2c).
The procedure was the same as described in the preparation of
2a with 2-(1-hexyn-1-yl)benzaldehyde 1c (1.12 g, 6 mmoles)
except reaction time (11 days). Yield: 1.37 g (84%); oil; ir (neat):
-1
1
EXPERIMENTAL
3406, 2219, 1718, 1619, 1445 cm ; H nmr (deuteriochloro-
form): δ 0.93 (t, 3 H, J = 7.17 Hz), 1.41-1.59 (two m, 4 H), 2.41
(t, 2 H, J = 7.02 Hz), 3.32 (d, 1 H, J = 4.88 Hz), 3.76 (s, 3 H), 5.60
(s, 1 H), 6.03 (d, 1 H, J = 4.88 Hz), 6.32 (s, 1 H), 7.19-7.48 (m, 4
All reagents and solvents were reagent grade or were purified
by standard methods before use. Silica gel 60 (70-230 mesh
ASTM) used for column chromatography was supplied by E.
Merck. Analytical thin layer chromatography (tlc) was per-
formed on silica gel with fluorescent indicator coated on alu-
minium sheets. Melting points were taken using an
Electrothermal melting point apparatus and are uncorrected.
Microanalyses were obtained using a Carlo Erba EA 1180 ele-
ment analyzer. Mass spectra were obtained using a ThermoQuest
Polaris Q mass spectrometer operating at 70 eV. Infrared spectra
were recorded on a Nicolet Magna 550 FTIR spectrometer. The
13
H); C nmr (deuteriochloroform): δ 13.56, 19.16, 21.95, 30.67,
51.92, 70.64, 78.21, 95.81, 122.50, 126.19, 126.52, 127.42,
+
127.81, 132.18, 141.19, 142.20, 167.08; ms: m/z (%) 272 (M ,
12), 255 (17), 229 (41), 212 (38), 197 (37), 183 (56), 169 (62),
141 (89), 115 (100).
Anal. Calcd for C
H O : C, 74.97; H, 7.40. Found: C, 74.83;
17 20 3
H, 7.18.
Methyl 3-Hydroxy-3-[2-(3-hydroxypropyn-1-yl)]phenyl-2-
methylenepropano-ate (2d).
1
13
H and C nmr spectra were measured on a Gemini 300 spec-
trometer using deuteriochloroform. The NOESY spectrum was
obtained on a 300 MHz Bruker spectrometer. All chemical shifts
are reported in parts per million (δ) relative to tetramethylsilane.
The 2-ethynylbenzaldehyde (1a) [14a], 2-(2-phenylethynyl)-
benzaldehyde (1b) [14b], 2-(1-hexyn-1-yl)benzaldehyde (1c)
[14c] and 2-(3-hydroxypropyn-1-yl)benzaldehyde (1d) [14d]
were prepared following the literature procedure.
The procedure was the same as described in the preparation of
2a with 2-(3-hydroxypropyn-1-yl)benzaldehyde 1d (0.96 g, 6
mmoles) except reaction time (3 days). Yield: 1.05g (81%); oil;
-1
1
ir (neat): 3473, 3411, 2140, 1723, 1695, 1634, 1429 cm ;
H
nmr (deuteriochloroform): δ 2.51 (t, 1 H, J = 4.27 Hz), 3.37 (d, 1
H, J = 4.88 Hz), 3.75 (s, 3 H), 4.46 (d, 2 H, J = 4.27 Hz), 5.72 (s,
1 H), 6.08 (d, 1 H, J = 4.58 Hz), 6.33 (s, 1 H), 7.22-7.50 (m, 4
13
H); C nmr (deuteriochloroform): δ 51.33, 52.08, 70.00, 83.17,
Methyl 3-(2-Ethynylphenyl)-3-hydroxy-2-methylenepropanoate
(2a).
92.53, 121.32, 126.19, 126.66, 127.60, 128.73, 132.20, 141.32,
142.88, 167.20; ms: m/z (%) 228 (10), 200 (100), 168 (60), 129
(54), 115 (48).
A solution of 2-ethynylbenzaldehyde 1a (0.78 g, 6 mmoles),
methyl acrylate (1.55 g, 18 mmoles) and DABCO (0.67 g, 6
mmoles) was stirred in a stoppered flask for four days at room
temperature. The reaction mixture was diluted with water (20 ml)
and extracted with dichloromethane (3 x 20 ml). The combined
organic layers were dried over anhydrous magnesium sulfate and
the solvent was evaporated in vacuo. The resulting mixture was
chromatographed on silica gel eluting with hexane/ethyl acetate
(10:1) to afford 1.05 g (81%) of 2a as an oil; ir (neat): 3435,
Anal. Calcd for C
H O : C, 68.28; H, 5.73. Found: C, 68.03;
14 14 4
H, 5.50.
Methyl 3-Acetoxy-3-(2-ethynyl)phenyl-2-hydroxy-2-methylene-
propanoate (3a).
To a stirred solution of 2 a (0.87 g, 4 mmoles) in
dichloromethane (20 ml) was added acetic anhydride (0.57 ml, 6
mmoles) and N,N-dimethylaminopyridine (98 mg, 0.8 mmoles)
at room temperature. After stirring at the same temperature for 1
hour the reaction mixture was diluted with water (10 ml) and
extracted with dichlorormethane (3 x 10 ml). The combined
organic layers were dried over anhydrous magnesium sulfate and
the solvent was evaporated in vacuo. The resulting mixture was
chromatographed on silica gel eluting with hexane/ethyl acetate
(10:1) to afford 0.99 g (96%) of 3a as an oil; ir (neat): 3276,
-1
1
3280, 2104, 1715, 1629, 1435 cm ; H nmr (deuteriochloro-
form): δ 3.30 (s, 1 H), 3.77 (s, 3 H), 3.79 (s, 1 H), 5.66 (s, 1 H),
13
6.07 (s, 1 H), 6.34 (s, 1 H), 7.20-7.57 (m, 4 H); C nmr (deuteri-
ochloroform): δ 52.02, 70.43, 81.27, 82.26, 120.68, 126.53,
126.83, 127.55, 129.16, 132.89, 140.97, 143.04, 166.96; ms: m/z
+
(%) 216 (M , 16), 199 (14), 157 (33), 129 (36), 128 (100).
Anal. Calcd for C
H O : C, 72.21; H, 5.59. Found: C, 69.93;
13 12 3
-1
1
H, 5.30.
2108, 1738, 1719, 1633, 1439 cm ; H nmr (deuteriochloro-

Jul-Aug 2004
Synthesis of 5H-1,2,3-Triazolo[4,3-a][2]benzazepines
615
organic layers were dried over anhydrous magnesium sulfate and
the solvent was evaporated in vacuo. The resulting mixture was
chromatographed on silica gel eluting with hexane/ethyl acetate
(7:1) to afford 0.45 g (68%) of 4a as a solid after crystallization
with hexane; mp 63-64°; ir (potassium bromide): 3252, 2116,
2100, 1715, 1625, 1431 cm ; H nmr (deuteriochloroform): δ
3.39 (s, 1 H), 3.91 (s, 3 H), 4.13 (s, 2 H), 7.36-7.59 (m, 4 H), 8.23
13
(s, 1 H); C nmr (deuteriochloroform): δ 47.18, 52.58, 81.08,
83.43, 122.60, 127.99, 128.95, 129.22, 133.14, 136.54, 142.66,
form): δ 2.23 (s, 3 H), 3.33 (s, 1 H), 3.74 (s, 3 H), 5.69 (s, 1 H),
13
6.47 (s, 1 H), 7.11 (s, 1 H), 7.29-7.55 (m, 4 H); C nmr (deuteri-
ochloroform): δ 20.58, 52.08, 71.15, 82.33, 82.69, 121.79,
126.81, 127.32, 128.13, 128.84, 133.08, 138.52, 139.76, 165.36,
+
169.23; ms: m/z (%) 258 (M , 93), 215 (31), 199 (86), 161 (72),
-1
1
128 (100).
Anal. Calcd for C
H, 5.19.
H
15 14
O : C, 69.76; H, 5.46. Found: C, 69.55;
4
Methyl 3-Acetoxy-2-methylene-3-(2-phenylethynyl)phenyl-
propanoate (3b).
+
142.72, 167.23; ms: m/z (%) 241 (M , 18), 181 (14), 155 (100),
127 (55), 126 (26), 115 (11).
The procedure was the same as described in the preparation of 3a
with 2b (1.17 g, 4 mmoles) except reaction time (4 hours). Yield:
-1 1
1.18 g (88%); oil; ir (neat): 2217, 1742, 1719, 1633, 1493 cm ; H
nmr (deuteriochloroform): δ 2.12 (s, 3 H), 3.70 (s, 3 H), 5.74 (s, 1
13
H), 6.49 (s, 1 H), 7.23 (s, 1 H), 7.31-7.58 (m, 9 H); C nmr (deu-
A n a l. Calcd for C
Found: C, 64.49; H, 4.38; N, 17.18.
H N O : C, 64.72; H, 4.60; N, 17.42.
13 11 3 2
Methyl 2-Azidomethyl-3-(2-phenylethynyl)phenyl-2-propenoate
(4b).
teriochloroform): δ 20.91, 52.01, 71.28, 86.37, 86.60, 94.77,
122.91, 126.80, 127.32, 127.56, 128.34, 131.48, 131.62, 132.29,
The procedure was the same as described in the preparation of
4a with 3b (1.00 g, 3 mmoles) except reaction time (6 hours).
Yield: 0.70 g (73%); mp 67-69°; ir (potassium bromide): 2104,
2073, 1715, 1622 cm ; H nmr (deuteriochloroform): δ 3.92 (s, 3
13
H), 4.17 (s, 2 H), 7.36-7.56 (m, 9 H), 8.38 (s, 1 H); C nmr (deu-
teriochloroform): δ 47.16, 52.47, 86.99, 95.93, 122.66, 123.91,
127.48, 128.11, 128.41, 128.66, 128.95, 131.25, 131.80, 135.87,
+
142.94, 143.22, 167.31; ms: m/z (%) 317 (M , 33), 288 (42), 274
+
132.49, 138.66, 139.13, 165.48, 169.31; ms: m/z (%) 334 (M , 2),
-1
1
292 (17), 259 (40), 231 (71), 215 (100), 203 (54), 187 (18).
O : C, 75.43; H, 5.43. Found: C, 75.14;
H, 5.23.
Anal. Calcd for C
H
21 18
4
Methyl 3-Acetoxy-3-[2-(1-hexyn-1-yl)]phenyl-2-methylene-
propanoate (3c).
(59), 230 (100), 203 (26), 155(75), 127(36).
A n a l. Calcd for C
The procedure was the same as described in the preparation of
3a with 2c (1.09 g, 4 mmoles) except reaction time (2 hours).
Yield: 1.14 g (91%); oil; ir (neat): 2233, 1750, 1727, 1633, 1439
H N O : C, 71.91; H, 4.76; N, 13.24.
19 15 3 2
Found: C, 71.68; H, 4.49; N, 12.91.
Methyl 2-Azidomethyl-3-[2-(1-hexyn-1-yl)]phenyl-2-
propenoate (4c).
-1
1
cm ; H nmr (deuteriochloroform): δ 0.93 (t, 3 H, J = 7.17 Hz),
1.42-1.60 (two m, 4 H), 2.12 (s, 3 H), 2.42 (t, 2 H, J = 7.02 Hz),
3.73 (s, 3 H), 5.63 (s, 1 H), 6.45 (s, 1 H), 7.10 (s, 1 H), 7.23-7.43
The procedure was the same as described in the preparation of
4a with 3c (0.94 g, 3 mmoles) except reaction time (54 hours).
13
(m, 4 H); C nmr (deuteriochloroform): δ 13.53, 19.17, 20.87,
22.03, 30.58, 51.94, 71.35, 77.67, 96.17, 123.68, 126.45, 127.35,
127.51, 127.99, 132.33, 138.73, 138.92, 162.52, 169.23; ms: m/z
-1
Yield: 0.71 g (80%); oil; ir (neat): 2225, 2100, 1712, 1633 cm ;
1
H nmr (deuteriochloroform): δ 0.95 (t, 3 H, J = 7.17 Hz), 1.45-
1.63 (two m, 4 H), 2.46 (t, 2 H, J = 7.02 Hz), 3.90 (s, 3 H), 4.13
+
(%) 314 (M , 24), 255 (100), 254 (81), 239 (46), 223 (50), 195
13
(s, 2 H), 7.31-7.47 (m, 4 H), 8.24 (s, 1 H); C nmr (deuteriochlo-
(79), 165 (98), 153 (59), 141(35).
Anal. Calcd for C
H, 7.29.
H
19 22
O : C, 72.59; H, 7.05. Found: C, 72.38;
4
roform): δ 13.61, 19.15, 21.78, 30.52, 47.12, 52.16, 78.34, 97.25,
124.72, 127.01, 127.51, 128.81, 132.23, 135.75, 143.35, 143.53,
+
167.27; ms: m/z (%) 297 (M , 5), 268 (15), 255 (100), 194 (21),
Methyl 3-Acetoxy-3-[2-(3-acetoxypropyn-1-yl)]phenyl-2-meth-
ylenepropanoate (3d).
180 (34), 168 (44), 155(45), 127 (24).
A n a l. Calcd for C
H N O : C, 68.67; H, 6.44; N, 14.13.
17 19 3 2
Found: C, 68.55; H, 6.20; N, 13.77.
The procedure was the same as described in the preparation of
3a with 2d (0.97 g, 4 mmoles) except the amount of acetic anhy-
dride (1.14 ml, 12 mmoles) and reaction time (3 hours). Yield:
1.01 g (76%); mp 61-62°; ir (potassium bromide): 1738, 1707,
Methyl 2-Azidomethyl-3-[2-(3-acetoxypropyn-1-yl)]phenyl-2-
propenoate (4d).
-1
1
1637 cm ; H nmr (deuteriochloroform): δ 2.12 (s, 3 H), 2.13(s,
3 H), 3.73 (s, 3 H), 4.91 (s, 2 H), 5.71 (s, 1 H), 6.47 (s, 1 H), 7.03
The procedure was the same as described in the preparation of
4a with 3d (0.99 g, 3 mmoles) except reaction time (7 hours).
13
(s, 1 H), 7.28-7.47 (m, 4 H); C nmr (deuteriochloroform): δ
-1
Yield: 0.59 g (63%); oil; ir (neat): 2093, 1745, 1719, 1633 cm ;
1
20.60, 20.72, 52.09, 52.47, 70.92, 83.42, 88.34, 121.67, 126.69,
127.33, 128.05, 128.72, 132.57, 138.34, 139.52, 165.22, 169.08,
+
170.05; ms: m/z (%) 330 (M , 7), 228 (53), 211 (68), 169 (100),
H nmr (deuteriochloroform): δ 2.14 (s, 3 H), 3.91 (s, 3 H), 4.12
13
(s, 2 H), 4.93 (s, 2 H), 7.35-7.52 (m, 4 H), 8.17 (s, 1 H); C nmr
(deuteriochloroform): δ 20.70, 47.15, 52.56, 83.88, 89.13,
122.56, 127.97, 128.82, 129.03, 129.32, 132.74, 136.22, 142.44,
+
142.65, 167.13, 170.13; ms: m/z (%) 313 (M , 16), 270 (100),
141 (75), 115 (36).
Anal. Calcd for C
H, 5.26.
H
18 18
O : C, 65.45; H, 5.49. Found: C, 65.20;
6
182 (16), 154 (15).
A n a l. Calcd for C
H N O : C, 61.34; H, 4.83; N, 13.41.
16 15 3 4
Found: C, 61.45; H, 4.70; N, 13.19.
Methyl 2-Azidomethyl-3-(2-ethynylphenyl)-2-propenoate (4a).
To a stirred solution of 3a (0.78 g, 3 mmoles) in dimethyl sul-
foxide (15 ml) was added sodium azide (0.29 g, 4.5 mmoles) at
room temperature. After stirring at the same temperature for 15
hours the reaction mixture was diluted with water (10 ml) and
extracted with dichloromethane (3 x 20 ml). The combined
6-Carbomethoxy-5H-1,2,3-triazolo[4,3-a][2]benzazepine (5a).
A stirred solution of 4a (0.24 g, 1 mmole) in toluene (3 ml)
was heated at reflux temperature for 8 hours and the solvent was
evaporated in vacuo. The residue was chromatographed on silica

616
S. H. Ko and K.-J. Lee
Vol. 41
gel eluting with hexane/ethyl acetate (5:1) to afford 0.18 g (73%)
of 5a as a solid; mp 122-123°; ir (potassium bromide): 1696,
A n a l. Calcd for C
H
N O : C, 61.34; H, 4.83; N, 13.41.
3 4
16 15
Found: C, 61.16; H, 4.60; N, 13.22.
REFERENCES AND NOTES
Author to whom correspondence should be addressed.
-1
1637, 1610 cm ; H nmr (deuteriochloroform): δ 3.90 (s, 3 H),
1
13
5.36 (s, 2 H), 7.54-7.73 (m, 4 H), 7.92 (s, 1 H), 7.96 (s, 1 H);
nmr (deuteriochloroform): δ 44.82, 52.83, 126.15, 127.76,
C
128.92, 129.40, 130.54, 131.32, 132.53, 136.29, 142.29, 142.37,
+
165.12; ms: m/z (%) 241 (M , 26), 181 (12), 155 (100), 127 (57),
*
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Elsevier Science Oxford, 1996; Vol. 4, pp 1-126.
[6] R. Fuks, H. G. Viehe, In Chemistry of Acetylenes, ed. H. G.
Viehe; Marcel Dekker, New York, 1969, pp 425-593.
[7] J. Bastide and O. Henri-Rousseau, In The Chemistry of The
Carbon-Carbon Triple Bond, ed. S. Patai; Interscience Publishers,
London, 1978, pp 447-552.
[8] K. Tezuka, P. Compain and O. R. Martin, S y n l e t t, 1837
(2000)
[9] W. H. Pearson, S. C. Bergmeier, S. Degan, K. -C. Lin, Y. -F.
Poon, J. M. Schkeryantz and J. P. Williams, J. Org. Chem., 55, 5719
(1990).
126 (26), 115 (9).
A n a l. Calcd for C
Found: C, 64.53; H, 4.53; N, 17.28.
H N O : C, 64.72; H, 4.60; N, 17.42.
13 11 3 2
6-Carbomethoxy-1-phenyl-5H-1, 2, 3-triazolo[4, 3-a][2]ben -
zazepine (5b).
The procedure was the same as described in the preparation of
5a with 4b (0.32 g, 1 mmole). Yield: 0.24 g (77%); mp 172-173°;
-1
ir (potassium bromide): 1704, 1631 cm ; H nmr (deuteriochloro-
1
form): δ 3.92 (s, 3 H), 5.30 (s, 2 H), 7.34-7.57 (m, 9 H), 8.03 (s, 1
13
H); C nmr (deuteriochloroform): δ 44.85, 52.80, 126.45, 128.00,
128.28, 128.63, 129.27, 129.75, 130.30, 130.97, 131.33, 131.68,
+
132.59, 142.50, 142.59, 145.18, 165.02; ms: m/z (%) 317 (M , 45),
288 (56), 274 (75), 230 (100), 202 (35), 155 (59), 127 (61).
A n a l. Calcd for C
H N O : C, 71.91; H, 4.76; N, 13.24.
19 15 3 2
Found: C, 71.78; H, 4.62; N, 13.02.
1 - B u t y l - 6 - c a r b o m e t h o x y - 5H- 1 , 2 , 3 - t r i a z o l o [ 4 , 3 - a] [ 2 ] b e n -
zazepine (5c).
The procedure was the same as described in the preparation of
5a with 4c (0.30 g, 1 mmole). Yield: 0.23 g (75%); oil; ir (neat):
-1
1
1707, 1629 cm ; H nmr (deuteriochloroform): δ 0.91 (t, 3 H, J =
7.32 Hz), 1.34-1.42 (m, 2 H), 1.69-1.73 (m, 2 H), 2.82 (t, 2 H, J =
7.78 Hz), 3.89 (s, 3 H), 5.26 (s, 2 H), 7.52-7.61 (m, 4 H), 7.93 (s,
13
1 H); C nmr (deuteriochloroform): δ 13.73, 22.51, 25.53,
31.38, 44.77, 52.72, 126.91, 128.67, 129.02 129.98, 131.46,
131.91, 132.31, 142.26, 142.35, 145.83, 165.08; ms: m/z (%) 297
[10] D. Seebach, D. Enders, R. Dach and R. Pieter, Chem. Ber.,
110, 1879 (1977).
+
(M , 6), 268 (16), 255 (100), 194 (23), 180 (32), 168 (50), 167
(40), 166 (34), 155 (48), 115 (13).
A n a l. Calcd for C
[11a] S. E. Drewes and G. H. P. Roos, Terahedron, 44, 4653
(1988); [b] D. Basavaiah, P. D. Rao and R. S. Hyma, Tetrahedron, 52,
8001 (1996); [c] J. N. Kim and K. Y. Lee, Curr. Org. Chem., 6, 627
(2002); [d] D. Basavaiah, A. J. Rao and T. Satyanarayana, Chem. Rev.,
1 0 3, 811 (2003); [e] E, Ciganek, In Organic Reactions, ed. L. A.
Paquette; Wiley, New York, 1997, Vol. 51, pp 201-350.
[12] Y. S. Song, C. H. Lee and K. -J. Lee, J. Hetrocyclic Chem.,
40, 939 (2003).
[13] C. H. Lee, Y. S. Song, H. I. Cho, J. W. Yang and K. -J. Lee,
J. Hetrocyclic Chem., 40, 1103 (2003).
[14a] W. B. Austin, N. Bilow, W. J. Kelleghan and K. S. Y. Lau, J.
Org. Chem., 46, 2280 (1981); [b] K. R. Roesch and R. C. Larock, J.
Org. Chem., 67, 86 (2002); [c] G. Dyker, W. Stirner and G. Henkel,
Eur. J. Org. Chem., 1433 (2000).
H N O : C, 68.67; H, 6.44; N, 14.13.
17 19 3 2
Found: C, 68.32; H, 6.19; N, 13.87.
1-Acetoxymethyl-6-carbomethoxy-5H-1, 2, 3-triazolo[4, 3-a]-
[2]benzazepine (5d).
The procedure was the same as described in the preparation of
5a with 4d (0.31 g, 1 mmole) except reaction time (4 hours).
Yield: 0.23 g (72%); mp 148-150°; ir (potassium bromide): 1742,
-1
1
1711, 1631 cm ; H nmr (deuteriochloroform): δ 2.12 (s, 3 H),
3.90 (s, 3 H), 5.26 (s, 2 H), 5.31 (s, 2 H), 7.56-7.72 (m, 4 H), 7.95
13
(s, 1 H); C nmr (deuteriochloroform): δ 20.90, 44.89, 52.85,
57.69, 125.53, 128.88, 129.60, 130.47, 132.19, 132.34, 134.54,
+
139.70, 142.11, 142.20, 164.87, 170.64; ms: m/z (%) 31 (M ,
17), 281 (26), 270 (100), 166 (18), 154 (20).
[15] A. Patra, A. K. Roy, S. Batra and A. P. Bhaduri, Synlett,
1819 (2002).