Synthesis of 4H-Tetrazolo[1,5-a][1]benzazepines from the Baylis-Hillman Adducts of 2-Azidobenzaldehyde

Article abstract of DOI:10.1002/jhet.5570400622

Novel heterocycles, 4H-tetrazolo[1,5-a][1]benzazepines 6 were prepared by the intramolecular 1,3-dipolar cycloaddition reaction of azidophenylcyanomethyl compounds 5. The latter were readily obtained from 2-azidobenzaldehyde through the Baylis-Hillman add

Full text of DOI:10.1002/jhet.5570400622

Nov-Dec 2003
1103
Synthesis of 4H-Tetrazolo[1,5-a][1]benzazepines from the
Baylis-Hillman Adducts of 2-Azidobenzaldehyde
Chang Hoon Lee, Young Seok Song, Hyun In Cho, Je Woo Yang
*
and Kee-Jung Lee
Department of Chemical Engineering, Hanyang University, Seoul 133-791, Korea
Received August 21, 2003
Novel heterocycles, 4H-tetrazolo[1,5-a][1]benzazepines 6 were prepared by the intramolecular 1,3-dipo-
lar cycloaddition reaction of azidophenylcyanomethyl compounds 5. The latter were readily obtained from
2-azidobenzaldehyde through the Baylis-Hillman adducts 3 followed by acetylation to compounds 4 and
nucleophilic substitution by cyanide to compounds 5.
J. Heterocyclic Chem., 40, 1103 (2003).
Tetrazole and tetrazole containing heterocycles are
reagents toward synthetically useful compounds has been
studied [8]. Among them, adducts have been applied to
provide convenient access to benzannulated or other hete-
rocyclic systems. These include indolizines [9], quinolines
[10], chromenes [11], thiochromenes [12], indenes [13],
pyridopyrimidones [14], 1,4-oxazepin-7-ones [15],
coumarins [16], isobenzofuranones [17] and isoindoles
[18]. We herein describe a facile synthesis of 4H-tetrazolo-
[1,5-a][1]benzazepines via the treatment of the acetates of
Baylis-Hillman adducts of 2-azidobenzaldehyde with
cyanide followed by intramolecular 1,3-dipolar cycloaddi-
tion reaction.
The reaction of 2-azidobenzaldehyde (1) with 3.0 molar
equivalents of methyl acrylate in the presence of 0.1 molar
equivalents of 1,4-diazabicyclo[2,2,2]octane (DABCO) in
dioxane at room temperature afforded the adduct, methyl
3-(2-azidophenyl)-3-hydroxy-2-methylenepropanoate (3a)
in 57% yield. Similarly, the treatment of 1 with ethyl acry-
late, methyl vinyl ketone and acrylonitrile in the presence
of DABCO gave the corresponding adducts 3b-d in 43-
53% yields. In the cases of acrolein, acrylamide, and
phenyl vinyl sulfone, adducts were not produced.
Generally, the reactions were very slow (7-9 days) at room
temperature whereas at reflux temperature the conversions
were unsuccessful. The acetates of adducts 4a-d were pro-
duced by the reaction of 3a-d with acetic anhydride in the
presence of a catalytic amount of N,N-dimethylamino-
pyridine (DMAP) in dichloromethane at room temperature
for 3 hours in excellent yields (95-98%). Nucleophilic sub-
stitution reaction of the acetates 4a-c with potassium
cyanide in aqueous dimethyl sulfoxide at room tempera-
known to exhibit a wide range of biological activities such
as analeptic [1], anti-inflammartory [1,2], antimicrobial
[1,3], antilipemic [4] and antiallergic [1,2] properties.
They can serve as metabolically stable surrogates for a car-
boxylic acid group [5], and as simple lipophilic spacers.
The most common method for the preparation of tetrazoles
is the 1,3-dipolar cycloaddition reaction of azides with
nitriles [6].
The Baylis-Hillman reaction is one of the most powerful
carbon-carbon bond forming reactions in organic chem-
istry [7]. Most Baylis-Hillman reactions involve the reac-
tion of activated alkenes and carbonyl compounds to pro-
duce the Baylis-Hillman adducts viz allylic alcohol deriva-
tives [7]. Besides the usefulness of these adducts them-
selves, further derivatization with various nucleophilic
ture for 3 hours occurred in a S 2' fashion to give the
N
required key intermediates azidophenylcyanomethyl com-

1104
C. H. Lee, Y. S. Song, H. I. Cho, J. W. Yang and K.-J. Lee
Vol. 40
to afford 904 mg (57%) of 3a as an oil; ir (neat): 3452, 2108,
pounds 5a-c in 100% (E)-selectivity as evidenced by the
H nmr spectral analysis in comparison with literature val-
-1
1
1
1704, 1634, 1588 cm ; H nmr (deuteriochloroform): δ 3.22 (d,
1H, J = 5.5 Hz), 3.76 (s, 3H), 5.68 (s, 1H), 5.82 (d, 1H, J = 5.5
Hz), 6.33 (s, 1H), 7.15-7.19 (m, 2H), 7.26-7.38 (m, 1H), 7.45-
ues [19,20] in moderate yields (48-55%). Unfortunately,
4d did not undergo nucleophilic substitution at room or
elevated temperature. The 1,3-dipolar cycloaddition of
azidophenylcyanomethyl compounds 5a-c in refluxing
toluene produced excellent yields (85-88%) of the corre-
sponding 4H-tetrazolo[1,5-a][1]benzazepines 6a-c . The
infrared spectra of 6a-c showed the disappearance of
13
7.48 (m, 1H); C nmr (deuteriochloroform): δ 52.0, 67.8, 117.9,
124.9, 126.4, 128.0, 129.0, 131.9, 137.2, 140.9, 166.8; ms: m/z
+
(%) 233 (M , 4), 206 (26), 205 (39), 175 (39), 144 (100).
Anal. Calcd. for C H N O : C, 56.65; H, 4.75; N, 18.02.
11 11
3 3
Found: C, 56.41; H, 4.57; N, 17.79.
Ethyl 3-(2-Azidophenyl)-3-hydroxy-2-methylenepropanoate
(3b).
-1
absorption for azide (2124-2132 cm ) and cyano (2248-
-1
2260 cm ) bands. To our knowledge, this is the first
The procedure was the same as described above except using
ethyl acrylate (2b) (2.21 ml, 20.40 mmoles) instead of methyl
acrylate. Yield: 874 mg (52%); oil; ir (neat): 3436, 2124, 1712,
example of the synthesis of the 4H-tetrazolo[1,5-a][1]ben-
zazepine ring system.
-1 1
With a view to study the application of Baylis-Hillman
acetate 4d, we finally examined the isomerization of 4d
with a catalytic amount of trimethylsilyl trifluoromethane-
sulfonate (TMSOTf) [20]. This reaction provided a simple
and convenient direct synthesis of the 4-acetoxymethylte-
trazolo[1,5-a]quinoline (8) via the intermediate 2-(ace-
toxymethyl)-3-(2-azidophenyl)-2-propenenitrile (7) fol-
lowed by cycloaddition of the azido group to the neighbor-
ing nitrile by known method [21].
In summary, outlined here is a new route to 4H-tetra-
zolo[1,5-a][1]benzazepines by an intramolecular 1,3-dipo-
lar cycloaddition of readily available azidophenyl-
cyanomethyl compounds from the Baylis-Hillman adducts
of 2-azidobenzaldehyde.
1627, 1580 cm ; H nmr (deuteriochloroform): δ 1.27 (t, 3H, J =
7.0 Hz), 3.27 (d, 1H, J = 5.5 Hz), 4.21 (q, 2H, J = 7.0 Hz), 5.67 (s,
1H), 5.81 (d, 1H, J = 5.5 Hz), 6.33 (s, 1H), 7.14-7.19 (m, 2H),
13
7.32-7.38 (m, 1H), 7.45-7.48 (m, 1H); C nmr (deuteriochloro-
form): δ 14.0, 61.0, 67.9, 117.9, 124.9, 126.1, 128.0, 129.1,
+
132.0, 137.2, 141.2, 166.4; ms: m/z (%) 247 (M , 6), 220 (12),
219 (57), 190 (38), 162 (13), 146 (40), 118 (100), 91 (33).
Anal. Calcd. for C
H N O : C, 58.29; H, 5.30; N, 17.00.
12 13 3 3
Found: C, 58.12; H, 5.11; N, 16.73.
3-[(2-Azidophenyl)hydroxymethyl]-3-buten-2-one (3c).
The procedure was the same as described in 3a except using
methyl vinyl ketone (2c) (1.70 ml, 20.40 mmoles) instead of
methyl acrylate. Yield: 635 mg (43%); mp 54-56°; ir (neat):
-1
1
3324, 2135, 1677 cm ; H nmr (deuteriochloroform): δ 2.38 (s,
3H), 3.36 (d, 1H, J = 5.5 Hz), 5.80 (s, 1H), 5.84 (d, 1H, J = 5.5
Hz), 6.18 (s, 1H), 7.14-7.19 (m, 2H), 7.32-7.37 (m, 1H), 7.44-
13
EXPERIMENTAL
7.47 (m, 1H); C nmr (deuteriochloroform): δ 26.4, 67.6, 118.0,
124.9, 127.1, 128.0, 128.9, 132.2, 137.1, 148.9, 200.4; ms: m/z
+
(%) 189 (M -N , 41), 147 (100), 118 (88), 104 (95), 91 (36).
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
H and C nmr spectra were measured on a Gemini 300 spec-
trometer. All chemical shifts are reported in parts per million (δ)
relative to tetramethylsilane.
The 2-azidobenzaldehyde (1) was prepared following the liter-
ature procedure [22].
2
Anal. Calcd. for C H N O : C, 60.82; H, 5.10; N, 19.34.
Found: C, 60.68; H, 4.80; N, 19.03.
11 11
3 2
3-(2-Azidophenyl)-3-hydroxy-2-methylenepropanenitrile (3d).
The procedure was the same as described in 3a except using
acrylonitrile (2d) (1.34 ml, 20.40 mmoles) instead of methyl acry-
late and stirring for 9 days. Yield: 722 mg (53%); mp 67-69°; ir
(potassium bromide): 3456, 2236, 2132, 1584 cm ; H nmr (deu-
teriochloroform): δ 2.75 (d, 1H, J = 5.3 Hz), 5.55 (d, 1H, J = 5.3
Hz), 6.06 (d, 1H, J = 1.3 Hz), 6.09 (d, 1H, J = 1.3 Hz), 7.18-7.26
(m, 2H), 7.39-7.51 (m, 2H); C nmr (deuteriochloroform): δ
69.2, 116.8, 118.2, 125.1, 125.3, 127.9, 129.9, 130.0, 130.6,
137.2; ms: m/z (%) 172 (M -N , 100), 143 (84), 117 (99), 89 (34).
-1 1
13
1
13
+
2
Anal. Calcd. for C H N O: C, 59.99; H, 4.03; N, 27.99.
Found: C, 59.76; H, 4.28; N, 27.71.
10
8 4
Methyl 3-Acetoxy-3-(2-azidophenyl)-2-methylenepropanoate (4a).
Methyl 3-(2-Azidophenyl)-3-hydroxy-2-methylenepropanoate (3a).
To a stirred solution of 3a (933 mg, 4.0 mmoles) in
dichloromethane (10 ml) was added acetic anhydride (0.57 ml,
6.0 mmoles) and N,N-dimethylaminopyridine (98 mg, 0.8
mmoles) at room temperature. After stirring at same temperature
for 3 hours the reaction mixture was diluted with water (10 ml)
and extracted with dichloromethane (3 x 10 ml). The combined
organic layers were dried over anhydrous magnesium sulfate and
the solvent was evaporated in vacuo to afford 1.08 g (98%) of 4a
To a stirred solution of 2-azidobenzaldehyde (1) (1.0 g, 6.80
mmoles) in dioxane (10 ml) was added methyl acrylate (2a) (1.84
ml, 20.40 mmoles) and DABCO (76 mg, 0.68 mmoles) at room
temperature. After stirring at same temperature for 7 days the
reaction mixture was diluted with water (10 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 chro-
matographed on silica gel eluting with hexane/ethyl acetate (7 :1)
-1
1
as an oil; ir (neat): 2132, 1751, 1724, 1634, 1584 cm ; H nmr

Nov-Dec 2003
Synthesis of 4H-Tetrazolo[1,5-a][1]benzazepines from the Baylis-Hillman Adducts
1105
(deuteriochloroform): δ 2.11 (s, 3H), 3.74 (s, 3H), 5.65 (s, 1H),
(deuteriochloroform): δ 17.2, 52.9, 117.1, 118.7, 123.3, 125.0,
125.2, 129.8, 131.1, 139.2, 139.7, 165.8; ms: m/z (%) 214 (M -
+
6.44 (s, 1H), 6.91 (s, 1H), 7.11-7.19 (m, 2H), 7.30-7.40 (m, 2H);
13
C nmr (deuteriochloroform): δ 20.9, 52.0, 68.2, 118.3, 124.7,
N , 28), 199 (100), 155 (14), 128 (28).
2
127.4, 128.2, 128.7, 129.6, 138.0, 138.5, 165.3, 169.2; ms: m/z
(%) 275 (M , 0.3), 248 (47), 247 (40), 205 (100), 188 (22), 146
Anal. Calcd. for C
Found: C, 59.21; H, 3.98; N, 22.89.
H N O : C, 59.50; H, 4.16; N, 23.13.
12 10 4 2
+
(34), 145 (51).
Anal. Calcd. for C
Ethyl 3-(2-Azidophenyl)-2-cyanomethyl-2-propenoate (5b).
H N O : C, 56.72; H, 4.76; N, 15.27.
13 13 3 4
The procedure was the same as described in 5a using 4b (868
Found: C, 56.50; H, 4.58; N, 15.17.
mg, 3.0 mmoles). Yield: 370 mg (48%); mp 69-70°; ir (potassium
Ethyl 3-Acetoxy-3-(2-azidophenyl)-2-methylenepropanoate (4b).
-1
1
bromide): 2260, 2132, 1712, 1642, 1596 cm ; H nmr (deuteri-
ochloroform): δ 1.40 (t, 3H, J = 7.0 Hz), 3.41 (s, 2H), 4.36 (q, 2H,
J = 7.0 Hz), 7.24-7.26 (m, 2H), 7.32-7.35 (m, 1H), 7.44-7.50 (m,
The procedure was the same as described in 4a using 3b (989
mg, 4.0 mmoles). Yield: 1.12 g (97%); oil; ir (neat): 2128, 1751,
-1
1
13
1720, 1638, 1584 cm ; H nmr (deuteriochloroform): δ 1.24 (t,
3H, J = 7.0 Hz), 2.11 (s, 3H), 4.18 (q, 2H, J = 7.0 Hz), 5.62 (s,
1H), 6.43 (s, 1H), 6.92 (s, 1H), 7.11-7.19 (m, 2H), 7.30-7.40 (m,
1H), 7.94 (s, 1H); C nmr (deuteriochloroform): δ 14.2, 17.2,
61.9, 117.2, 118.6, 123.6, 124.9, 125.3, 129.8, 131.0, 139.1,
+
139.4, 165.2; ms: m/z (%) 228 (M -N , 15), 199 (100), 155 (8),
2
13
2H); C nmr (deuteriochloroform): δ 14.0, 20.9, 61.0, 68.2,
128 (17).
118.2, 124.7, 127.1, 128.4, 128.8, 129.7, 138.0, 138.8, 164.9,
Anal. Calcd. for C
Found: C, 60.80; H, 4.52; N, 21.63.
H N O : C, 60.93; H, 4.72; N, 21.86.
13 12 4 2
+
169.2; ms: m/z (%) 261 (M -N , 23), 219 (100), 173 (18), 146
2
(58), 145 (67), 117 (10).
4-(2-Azidophenyl)-3-cyanomethyl-3-buten-2-one (5c).
Anal. Calcd. for C
H N O : C, 58.13; H, 5.23; N, 14.53.
14 15 3 4
Found: C, 58.35; H, 5.02; N, 14.18.
The procedure was the same as described in 5a using 4c (778
mg, 3.0 mmoles). Yield: 373 mg (55%); mp 96-98°; ir (potassium
bromide): 2256, 2128, 1673, 1634, 1592 cm ; H nmr (deuteri-
3-[(2-Azidophenyl)acetoxymethyl]-3-buten-2-one (4c).
-1
1
The procedure was the same as described in 4a using 3c (869
ochloroform): δ 2.54 (s, 3H), 3.39 (s, 2H), 7.27-7.29 (m, 2H),
13
mg, 4.0 mmoles). Yield: 1.02 g (98%); oil; ir (neat): 2124, 1743,
7.40-7.42 (m, 1H), 7.48-7.53 (m, 1H), 7.81 (s, 1H); C nmr
-1
1
1685 cm ; H nmr (deuteriochloroform): δ 2.10 (s, 3H), 2.36 (s,
(deuteriochloroform): δ 15.6, 25.3, 117.3, 118.6, 125.2, 129.9,
+
3H), 5.84 (s, 1H), 6.27 (s, 1H), 6.94 (s, 1H), 7.09-7.18 (m, 2H),
131.4, 132.4, 139.1, 139.7, 139.9, 196.8; ms: m/z (%) 198 (M -
13
7.26-7.38 (m, 2H); C nmr (deuteriochloroform): δ 21.0, 26.2,
N , 86), 183 (100), 158 (42), 156 (46), 128 (52).
2
67.8, 118.4, 124.7, 126.9, 128.1, 129.0, 129.5, 138.0, 146.4,
Anal. Calcd. for C
H N O: C, 63.71; H, 4.46; N, 24.77.
12 10 4
+
169.3, 197.1; ms: m/z (%) 231 (M -N , 12), 189 (50), 147 (11),
Found: C, 63.90; H, 4.58; N, 24.51.
2
146 (100), 118 (10).
5-Carbomethoxy-4H-tetrazolo[1,5-a][1]benzazepine (6a).
Anal. Calcd. for C
H N O : C, 60.22; H, 5.05; N, 16.21.
13 13 3 3
Found: C, 60.38; H, 4.81; N, 15.93.
A stirred solution of 5a (242 mg, 1.0 mmoles) in 20 ml of
toluene was heated at reflux temperature for 30 hours and the sol-
vent was evaporated in vacuo. The residue was crystallized from
hexane/diethyl ether to give 201 mg (83%) of 6a as a solid; mp
3-Acetoxy-3-(2-azidophenyl)-2-methylenepropanenitrile (4d).
The procedure was the same as described in 4a using 3d (801
mg, 4.0 mmoles). Yield: 920 mg (95%); yellow solid after crys-
tallization from hexane; mp 76-78°; ir (potassium bromide):
-1
1
137-139°; ir (potassium bromide): 1708, 1631, 1603 cm ;
H
nmr (deuteriochloroform): δ 3.89 (s, 3H), 4.12 (s, 2H), 7.57-7.69
-1
1
13
2229, 2135, 1755, 1584 cm ; H nmr (deuteriochloroform): δ
2.18 (s, 3H), 6.06 (d, 1H, J = 1.1 Hz), 6.07 (d, 1H, J = 1.1 Hz),
6.59 (s, 1H), 7.18-7.25 (m, 2H), 7.40-7.45 (m, 1H), 7.51-7.54 (m,
(m, 3H), 7.83 (s, 1H), 8.11 (d, 1H, J = 7.9 Hz); C nmr (deuteri-
ochloroform): δ 21.2, 52.9, 123.5, 125.9, 128.8, 129.3, 131.2,
+
132.2, 137.8, 137.9, 153.3, 165.1; ms: m/z (%) 242 (M , <1), 214
13
+
1H); C nmr (deuteriochloroform): δ 20.8, 69.3, 115.9, 118.2,
(M -N , 30), 199 (100), 155 (9), 128 (24), 101 (6).
2
121.9, 125.2, 126.8, 127.5, 130.3, 132.8, 137.4, 169.0; ms: m/z
Anal. Calcd. for C
H N O : C, 59.50; H, 4.16; N, 23.13.
12 10 4 2
+
(%) 214 (M -N , 2), 155 (43), 154 (100), 127 (29).
Found: C, 59.29; H, 4.02; N, 23.03.
2
Anal. Calcd. for C
H N O : C, 59.50; H, 4.16; N, 23.13.
12 10 4 2
5-Carbethoxy-4H-tetrazolo[1,5-a][1]benzazepine (6b).
Found: C, 59.26; H, 3.89; N, 22.85.
The procedure was the same as described in 6a using 5b (256
Methyl 3-(2-Azidophenyl)-2-cyanomethyl-2-propenoate (5a).
mg, 1.0 mmoles). Yield: 218 mg (85%); mp 166-168°; ir (potas-
-1 1
To a stirred solution of 4a (826 mg, 3.0 mmoles) in dimethyl
sulfoxide (40 ml) and water (20 ml) was added potassium
cyanide (293 mg, 4.5 mmoles) at room temperature. After stirring
at same temperature for 3 hours the reaction mixture was diluted
with water (20 ml) and extracted with dichloromethane (3 x 30
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 (7:1) to afford 363 mg (51%) of 5a as a solid
after crystallization from hexane; mp 67-69°; ir (potassium bro-
sium bromide): 1700, 1638, 1603 cm ; H nmr (deuteriochloro-
form): δ 1.39 (t, 3H, J = 7.0 Hz), 4.12 (s, 2H), 4.34 (q, 2H, J =
7.0 Hz), 7.27-7.67 (m, 3H), 7.82 (s, 1H), 8.11 (d, 1H, J = 7.9
13
Hz); C nmr (deuteriochloroform): δ 14.2, 21.2, 62.1, 123.5,
126.0, 129.2, 129.3, 131.1, 132.2, 137.5, 137.6, 153.4, 164.7;
+
+
ms: m/z (%) 256 (M , <1), 228 (M -N , 16), 199 (100), 155
2
(10), 128 (19).
Anal. Calcd. for C
H N O : C, 60.93; H, 4.72; N, 21.86.
13 12 4 2
Found: C, 60.68; H, 4.51; N, 21.53.
5-Acetyl-4H-tetrazolo[1,5-a][1]benzazepine (6c).
-1
1
mide): 2248, 2124, 1716, 1634, 1592 cm ; H nmr (deuteri-
ochloroform): δ 3.42 (s, 2H), 3.91 (s, 3H), 7.24-7.27 (m, 2H),
7.33-7.35 (m, 1H), 7.45-7.50 (m, 1H), 7.95 (s, 1H); C nmr
The procedure was the same as described in 6a using 5c (226
mg, 1.0 mmoles) except reaction time (70 hours). Yield: 192 mg
13

1106
C. H. Lee, Y. S. Song, H. I. Cho, J. W. Yang and K.-J. Lee
Vol. 40
-1
Winchester and G. Fleet, Tetrahedron Lett., 36, 7507 (1995); [d] Z. P.
Demko and K. B. Sharpless, Angew. Chem. Int. Ed., 41, 2110 (2002); [e]
Z. P. Demko and K. B. Sharpless, Angew. Chem. Int. Ed., 41, 2113
(2002).
(85%); mp 151-152°; ir (potassium bromide): 1669, 1631 cm ;
1
H nmr (deuteriochloroform): δ 2.53 (s, 3H), 4.08 (s, 2H), 7.59-
13
7.71 (m, 4H), 8.13 (d, 1H, J = 7.9 Hz); C nmr (deuteriochloro-
form): δ 19.3, 25.4, 123.6, 126.0, 129.3, 131.4, 132.0, 132.3,
[7] For recent reviews, see: [a] S. E. Drewes and G. H. P. Roos,
Tetrahedron, 44, 4653 (1988); [b] D. Basavaiah, P. D. Rao and R. S.
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Reactions, Vol. 51, L. A. Paquette, ed, Wiley, New York, 1999, pp 201-
350.
+
137.6, 137.7, 153.5, 195.0; ms: m/z (%) 198 (M -N , 100), 183
2
(13), 155 (84), 128 (37).
Anal. Calcd. for C
H N O: C, 63.71; H, 4.46; N, 24.77.
12 10 4
Found: C, 63.50; H, 4.19; N, 24.52.
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Kumaragurubaran, Tetrahedron Lett., 42, 477 (2001); [k] D. Basavaiah,
N. Kumaragurubaran and D. S. Sharada, Tetrahedron Lett., 42, 85 (2001).
[9a] M. L. Bode and P. T. Kaye, J. Chem. Soc., Perkin Trans. 1,
2612 (1990); [b] M. L. Bode and P. T. Kaye, J. Chem. Soc., Perkin Trans.
1, 1809 (1993).
[10a] O. B. Familoni, P. T. Kaye and P. J. Klaas, Chem. Commun.,
2563 (1998); [b] J. N. Kim, K. Y. Lee, H. S. Kim and T. Y. Kim, Org.
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and Y. M. Chung, Tetrahedron Lett., 42, 8341 (2001).
[11] P. T. Kaye and X. W. Nocanda, J. Chem Soc., Perkin Trans. 1,
1331 (2000).
4-Acetoxymethyltetrazolo[1,5-a]quinoline (8).
To a stirred solution of 4d (242 mg, 1.0 mmoles) in
dichloromethane (5 ml), was added trimethylsilyl trifluo-
romethanesulfonate (222 mg, 1.0 mmoles) at room tempera-
ture. After 90 hours at reflux temperature, the reaction mixture
was diluted with water (5 ml) and extracted with
dichloromethane (3 x 10 ml). The combined organic layer was
dried (MgSO ), the solvent was evaporated and the crude thus
4
obtained was crystallized from hexane/diethyl ether to provide
157 mg (65%) of 8 as a pure solid; mp 186-187°; ir (potassium
-1
1
bromide): 1740, 1617, 1535 cm ; H nmr (deuteriochloro-
form): δ 2.20 (s, 3H), 5.64 (s, 2H), 7.71-7.77 (m, 1H), 7.87-
7.93 (m, 1H), 7.97( s, 1H), 7.99 (d, 1H, J = 8.0 Hz), 8.70 (d,
13
1H, J = 8.0 Hz); C nmr (deuteriochloroform): δ 20.9, 61.1,
116.8, 121.5, 123.7, 128.2, 129.1, 130.3, 131.2, 131.5, 146.6,
+
170.6; ms: m/z (%) 242 (M , <1), 216 (82), 173 (100), 156
(38), 128 (48).
Anal. Calcd. for C
H N O : C, 59.50; H, 4.16; N, 23.13.
12 10 4 2
Found: C, 59.27; H, 3.89; N, 22.85.
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(2000).
[16] P. T. Kaye, M. A. Musa and X. W. Nocanda, Synthesis, 531
(2003).
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Author to whom correspondence should be addressed.
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*
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