2
296
W.-Y. Chen, J. Lu
LETTER
–
1 1
(
13) Hajipour, A. R.; Mirjalili, B. B. F.; Zarei, A.; Khazdooz, L.;
Ruoho, A. E. Tetrahedron Lett. 2004, 45, 6607.
14) Zolfigol, M. A. Tetrahedron 2001, 57, 9509.
15) Zolfigol, M. A.; Bamoniri, A. Synlett 2002, 1621.
16) Zolfigol, M. A.; Madrakian, E.; Ghaemi, E. Molecules 2002,
cm . H NMR (CDCl ): d = 7.69–7.58 (m, 2 H), 7.48–7.40
3
(m, 3 H), 7.29–7.25 (m, 2 H), 6.92 (d, J = 7.8 Hz, 1 H), 6.74
(d, J = 7.8 Hz, 2 H), 5.41 (d, J = 8.4 Hz, 1 H), 4.02 (d, J = 8.4
Hz, 1 H). HRMS: m/z calcd for C H N : 208.1000; found:
208.1004.
2-(N-Benzylamino)-2-(4-chlorophenyl)acetonitrile (3k):
colorless oil. IR (KBr): n = 3312, 2238, 1596, 1468 cm . H
NMR (CDCl ): d = 7.49 (d, J = 8.4 Hz, 2 H), 7.39–7.28 (m,
7 H), 4.73 (s, 1 H), 3.99 (AB q, J = 12.8 Hz, 2 H). HRMS:
m/z calcd for C H ClN : 256.0767; found: 256.0764.
2-(N-Benzylamino)-2-(4-methoxyphenyl)acetonitrile (3l):
colorless oil. IR (KBr): n = 3325, 3031, 2923, 2231, 1598,
1491 cm . H NMR (CDCl ): d = 7.44 (d, J = 8.8 Hz, 2 H),
(
(
(
1
4
12
2
7
, 734.
17) Mirjalili, B. F.; Zolfigol, M. A.; Bamoniri, A. Molecules
002, 7, 751.
–
1 1
(
(
(
(
2
3
18) Zolfigol, M. A.; Shirini, F.; Choghamarani, A. G.;
Mohammadpoor-Baltork, I. Green Chem. 2002, 4, 562.
19) Salehi, P.; Dabiri, M.; Zolfigol, M. A.; Fard, M. A. B.
Tetrahedron Lett. 2003, 44, 2889.
1
5
13
2
–
1 1
20) Preparation of Silica Sulfuric Acid.
3
A 50-mL round-bottomed flask was charged with silica gel
7.41–7.29 (m, 5 H), 6.92 (d, J = 8.4 Hz, 2 H), 4.70 (s, 1 H),
4.00 (AB q, J = 12.8 Hz, 2 H), 3.82 (s, 3 H), 1.83 (s, 1 H).
HRMS: m/z calcd for C H N O: 252.1263; found:
(
15 g) and a magnetic stirrer. Chlorosulfonic acid (5.83 g, 50
mmol) was added dropwise at r.t. The HCl gas was
conducted over an adsorbing solution. After the addition was
complete, the resulting mixture was stirred until no HCl gas
was evolved from the vessel. The product (silica sulfuric
acid) of 19.0 g was obtained.
1
6
16
2
252.1259.
2-(N-4-Chloroanilino)-2-(4-chlorophenyl)acetonitrile (3m):
mp 122–124 °C. IR (KBr): n = 3307, 3064, 2237, 1595, 1491
–
1 1
cm . H NMR (CDCl ): d = 7.54 (d, J = 8.8 Hz, 2 H), 7.44
3
(
21) Typical Reaction Procedure.
(d, J = 8.4 Hz, 2 H), 7.23 (d, J = 8.4 Hz, 2 H), 6.69 (d, J = 9.2
Hz, 2 H), 5.38 (d, J = 8.4 Hz, 1 H), 4.05 (d, J = 8.4 Hz, 1 H).
HRMS: m/z calcd for C H Cl N : 276.0221; found:
A mixture of benzaldehyde (1 mmol), aniline (1 mmol),
trimethylsilyl cyanide (1.5 mmol) and silica sulfuric acid (95
mg, 0.25 mmol) in CH Cl (2 mL) was stirred at r.t. for an
1
4
10
2
2
276.0219.
2
2
appropriate time. After completion of the reaction, as
indicated by TLC, the reaction mixture was filtered and
washed with CH Cl . The combined organic layers were
2-(N-4-Chloroanilino)-2-(4-methoxyphenyl)acetonitrile
(3o): mp 108–110 °C. IR (KBr): n = 3328, 3032, 2237, 1596,
–
1 1
1493 cm . H NMR (CDCl ): d = 7.49 (d, J = 8.8 Hz, 2 H),
2
2
3
washed with brine, dried over anhyd Na SO , concentrated
7.22 (d, J = 8.8 Hz, 2 H), 6.97 (d, J = 8.4 Hz, 2 H), 6.69 (d,
J = 8.8 Hz, 2 H), 5.31 (d, J = 7.6 Hz, 1 H), 4.00 (d, J = 7.6
Hz, 1 H), 3.84 (s, 3 H). HRMS: m/z calcd for C H ClN O:
2
4
in vacuo and purified by column chromatography on silica
gel to furnish 2-(N-anilino)-2-phenylacetonitrile (3a) in
1
5
13
2
88%; mp 72–73 °C. IR (KBr): n = 3369, 2236, 1606, 1498
272.0716; found: 272.0717.
Synlett 2005, No. 15, 2293–2296 © Thieme Stuttgart · New York