PAPER
Silylcyanation of Ketones Catalyzed by N-Morpholine N-Oxide
215
1
+
H NMR (CDCl , 200 MHz): = 0.17 (s, 9 H), 1.86 (s, 3 H), 7.36–
HRMS (EI): m/z calcd for C H NOSi (M ): 195.1079; found:
3
10 17
7
.53 (m, 5 H).
195.1073.
1
3
C NMR (CDCl , 100 MHz): = 0.89, 33.40, 71.45, 121.43,
3
1
-Trimethylsilyloxy-1-indancarbonitrile (Entry 8)
1
24.45, 128.49, 141.86.
–
1
IR (neat): 2360 cm (C≡N).
+
HRMS (EI): m/z calcd for C H NOSi (M ): 219.1079; found:
2
1
2
17
1
H NMR (CDCl , 200 MHz): = 0.12 (s, 9 H), 2.29–2.42 (m, 1 H),
3
19.1086.
2
.57–2.70 (m, 1 H), 2.82–3.08 (m, 2 H), 7.24–7.55 (m, 4 H).
1
3
2
-(4 -Cholorophenyl)-2-trimethylsilyloxyphenylpropanenitrile
C NMR (CDCl , 100 MHz): = 1.12, 29.37, 42.79, 76.46, 121.04,
3
(
Entry 2)
124.08, 125.44, 127.71, 129.94, 142.08, 142.58
–1
IR (neat): 2366 cm (C≡N).
+
HRMS (EI): m/z calcd for C H NOSi (M ): 231.1079; found:
1
3
17
1
H NMR (CDCl , 200 MHz): = 0.21 (s, 9 H), 1.85 (s, 3 H), 7.40–
231.1079.
3
7
.48 (m, 4 H).
1
3
1-Trimethylsilyloxy-1,2,3,4-tetrahydronaphthalene-1-carboni-
trile (Entry 9)
IR (neat): 2356 cm (C≡N).
C NMR (CDCl , 100 MHz): = 1.00, 33.45, 71.01, 121.18,
3
1
26.04, 128.79, 134.55, 140.68.
–
1
Anal. Calcd for C H ClNOSi: C, 56.79; H, 6.35; N, 5.52. Found:
C, 56.86; H, 6.69; N, 5.51.
12
16
1
H NMR (CDCl , 200 MHz): = 0.24 (s, 9 H), 1.85–2.41 (m, 4 H),
3
2
.83 (t, 2 H, 7.00 Hz), 7.07–7.28 (m, 3 H), 7.60–7.67 (m, 1 H).
1
3
2
-Trimethylsilyloxy-2-(4 -nitrophenyl)phenylpropanenitrile
C NMR (CDCl , 100 MHz): = 1.33, 18.69, 28.32, 37.73, 69.87,
3
(
Entry 3)
122.11, 126.63, 128.02, 129.06, 129.26, 135.68, 136.11.
–1
IR (neat): 2360 cm (C≡N).
1
1-Trimethylsilyloxy-1-cyclohexanecarbonitrile (Entry 10)
IR (neat): 2352 cm (CN).
H NMR (CDCl , 200 MHz): = 0.25 (s, 9 H), 1.88 (s, 3 H), 7.77
d, 2 H, J = 9.2 Hz), 8.30 (d, 2 H, J = 9.2 Hz).
3
–1
(
1
1H NMR (CDCl
.02–2.08 (m, 2 H).
, 200 MHz): = 0.23 (s, 9 H), 1.51–1.68 (m, 8 H),
3
3
C NMR (CDCl , 100 MHz): = 1.07, 29.31, 76.43, 120.98,
3
2
1
24.02, 127.26, 129.89, 142.54.
1
3
C NMR (CHCl , 100 MHz): = 1.37, 22.59, 24.48, 39.31, 70.59,
3
Anal. Calcd for C H N O Si: C, 54.52; H, 6.10; N, 10.60. Found:
C, 54.44; H, 6.47; N, 10.50.
12
16
2
3
1
21.91.
2
-Methyl-2-trimethylsilyloxyoctanenitrile (Entry 11)
2
-(4 -Methoxyphenyl)-2-trimethylsilyloxyphenylpropaneni-
–
1
IR (neat): 2350 cm (C≡N).
trile (Entry 4)
IR (neat): 2362 cm– (C≡N).
1
1
H NMR (CDCl , 200 MHz): = 0.22 (s, 9 H), 0.91 (t, 3 H, J = 6.60
3
1
Hz), 1.31–1.54 (m, 8 H), 1.57 (s, 3 H), 1.68–1.74 (m, 2 H).
H NMR (CDCl , 200 MHz): = 0.17 (s, 9 H), 1.86 (s, 3 H), 3.84
s, 3 H), 6.95 (d, 2 H, J = 8.8 Hz), 7.50 (d, 2 H, J = 8.8 Hz).
3
1
3
(
C NMR (CDCl , 100 MHz): = 1.15, 13.88, 22.38, 24.09, 28.76,
3
1
3
28.84, 31.47, 43.25, 69.56, 121.91.
C NMR (CDCl , 100 MHz): = 0.98, 33.31, 55.21, 71.18, 113.80,
3
+
1
21.70, 125.96, 133.95, 159.72.
HRMS (EI): m/z calcd for C H NOSi (M ): 227.1705; found:
1
2
25
+
227.1710.
HRMS (EI): m/z calcd for C H NO Si (M ): 249.1185; found:
1
3
19
2
2
49.1183.
2
-Trimethylsilyloxy-2-furan-2-ylpropanenitrile (Entry 12)
–
1
IR (neat): 2355 cm (CN).
3
-(4 -Methoxyphenyl)-2-methyl-2-trimethylsilyloxyphenylpro-
1
panenitrile (Entry 5)
IR (neat): 2368 cm (C≡N).
H NMR (CDCl , 200 MHz): = 0.09 (s, 9 H), 1.93 (s, 3 H), 6.37–
3
–1
6.40 (m, 1 H), 6.49–6.51 (m, 1 H), 7.42–7.44 (m, 1 H).
1
13
H NMR (CDCl , 200 MHz): = 0.15 (s, 9 H), 1.51 (s, 3 H), 2.92
C NMR (CDCl , 100 MHz): = 0.49, 28.37, 65.89, 108.14,
3
3
(
d, 2 H, J = 3.4 Hz), 3.80 (s, 3 H), 6.88 (d, 2 H, J = 8.8 Hz), 7.22 (d,
110.68, 120.23, 143.09, 151.63.
2
H, J = 8.4 Hz).
+
HRMS (EI): m/z calcd for C H NO Si (M ): 209.0812; found:
227.0888.
1
0
15
2
1
3
C NMR (CDCl , 100 MHz): = 1.06, 28.64, 48.21, 55.21, 69.98,
3
1
13.57, 121.76, 126.76, 131.66, 158.98.
Acknowledgment
2
6
-Methyl-2-trimethylsilyloxy-4-phenylbut-3-enenitrile (Entry
)
The authors warmly thank Korea Science and Engineering Founda-
tion for the financial support (F01-2000-6-123-01-2). One of us
(G.R.) thanks the Management, Correspondent, Principal and HOD,
Chemistry of Crescent Engineering College, Chennai, India for per-
mitting him to do PDF research.
–1
IR (neat): 2360 cm (C≡N).
1
H NMR (CDCl , 200 MHz): = 0.24 (s, 9 H), 1.74 (s, 3 H), 6.16
3
(
d, 1 H, J = 15.83 Hz), 6.92 (d, 1 H, J = 15.8 Hz), 7.31–7.41 (m, 5
H).
1
3
C NMR (CDCl , 100 MHz): = 1.30, 30.79, 69.89, 120.60,
3
1
26.82, 128.53, 128.70, 129.47, 130.89, 135.06.
References
1
-Trimethylsilyloxycyclohex-2-enecarbonitrile (Entry 7)
(1) Dr. G. Rajagopal is a Brain Pool Scientist from Department
of Chemistry, Crescent Engineering College, Chennai 600
048, India, and is assisted by a grant from the Korean
Federation of Science and Technology Societies and Korea
Science and Engineering Foundation.
–1
IR (neat): 2355 cm (C≡N).
1
H NMR (CDCl , 200 MHz): = 0.24 (s, 9 H), 1.77–1.87 (m, 2 H),
3
1
.94–2.11 (m, 4 H), 5.77 (m,1 H), 5.94–5.99 (m, 1 H).
1
3
C NMR (CDCl , 100 MHz): = 1.40, 18.26, 24.20, 36.86, 66.71,
3
1
21.75, 127.53, 132.49.
Synthesis 2004, No. 2, 213–216 © Thieme Stuttgart · New York