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R. P. Wurz et al. / Tetrahedron Letters 44 (2003) 8845–8848
(EI)+: 193.009605 (C5H2N3O2F3 calc. 193.009911). Phenyl
zomethyl phenyl ketone (4i). Yellow solid (112 mg, 94%):
Mp 39–40°C; Rf 0.49 (CHCl3); 1H NMR (400 MHz,
CDCl3) l 7.87–7.89 (m, 2H), 7.60–7.64 (m, 1H), 7.48–
7.52 (m, 2H); 13C NMR (100 MHz, CDCl3) l 183.1,
134.7, 134.0, 129.0, 128.2, 109.4; IR (solid) 2223 (CN),
2134 (CN2), 1646 (CꢀO), 1281, 1247, 633 cm−1. Cyanodi-
azomethyl (E)-cinnamyl ketone (4j). Pale pink solid (120
mg, 99%): Mp 108–109°C; Rf 0.41 (CHCl3); 1H NMR
(400 MHz, CDCl3) l 7.81 (d, J=15.5 Hz, 1H), 7.58–7.60
cyanodiazoacetate (4c). Yellow solid (108 mg, 93%): Mp
70–71°C; Rf 0.36 (CHCl3); H NMR (400 MHz, CDCl3)
1
l 7.38–7.43 (m, 2H), 7.27–7.31 (m, 1H), 7.16–7.18 (m,
2H); 13C NMR (100 MHz, CDCl3) l 160.1, 149.9, 129.7,
126.8, 121.2, 107.0, 52.0; IR (film) 2231 (CN), 2140
(CN2), 1731 (CꢀO), 1493, 1325, 1301, 1191, 1088 cm−1
.
Anal. calc. for C9H5N3O2: C 57.76, H 2.69, N 22.45;
found: C 57.63, H 2.58, N 22.50. Allyl cyanodiazoacetate
(m, 2H), 7.39–7.44 (m, 3H), 6.98 (d, J=15.5 Hz, 1H); 13
C
1
(4d). Yellow oil (91 mg, 86%): Rf 0.49 (CHCl3); H NMR
NMR (100 MHz, CDCl3) l 179.2, 145.5, 133.6, 131.6,
129.2, 129.1, 118.7, 108.7, 59.0 (CN2); IR (film) 2224
(CN), 2143 (CN2), 1649 (CꢀO), 1592, 1339, 1197, 989,
574 cm−1. Anal. calc. for C11H7N3O: C 67.00, H 3.58, N
21.31; found: C 66.91, H 3.53, N 21.13. 2-(Phenyl sulfon-
yl) diazoacetophenone (6). Pale yellow solid (174 mg,
98%): Mp 114–115°C; Rf 0.57 (CHCl3); 1H NMR (300
MHz, CDCl3) l 8.03–8.07 (m, 2H), 7.61–7.66 (m, 1H),
7.51–7.56 (m, 5H), 7.38–7.43 (m, 2H); 13C NMR (100
MHz, CDCl3) l 182.6, 141.4, 135.8, 134.3, 133.2, 129.2,
129.0, 128.2, 127.5, 83.3 (CN2); IR (film) 2114 (CN2),
1633 (CꢀO), 1449, 1328, 1143 cm−1. Anal. calc. for
C14H10N2S1O3: C 58.73, H 3.52, N 9.78; found: C 58.40,
H 3.38, N 9.93.
Procedure employing NaH as a base: NaH was rinsed
with hexanes (2×10 mL) and suspended in dry diethyl
ether (2.5 mL) while cooling to 0°C. Benzyl cyanoacetate
(100 mg, 0.57 mmol) in diethyl ether (2.5 mL) was then
added slowly dropwise to the NaH suspension, stirred 15
mins at 0°C, then 1 h at room temperature. The resulting
suspension was then cooled to 0°C and triflyl azide10 (1.0
mL, 0.85 M in hexane, 1.5 equiv.) was added slowly
dropwise. The reaction mixture was allowed to stir for 14
h, warming to room temperature then filtered and con-
centrated under reduced pressure. Purification was
achieved as above.
(400 MHz, CDCl3) l 5.85–5.94 (m, 1H), 5.27–5.38 (m,
2H), 4.74 (dt, J=5.9, 1.3 Hz, 2H); 13C NMR (100 MHz,
CDCl3) l 161.1, 130.8, 119.9, 107.3, 67.6; IR (film) 2230
(CN), 2134 (CN2), 1717 (CꢀO), 1368, 1133, 739 cm−1
.
Benzyl cyanodiazoacetate (4e). Pale pink solid (99 mg,
86%): Mp 37–38°C; Rf 0.41 (CHCl3); 1H NMR (400
MHz, CDCl3) l 7.39 (s, 5H), 5.30 (s, 2H); 13C NMR (100
MHz, CDCl3) l 161.3, 134.5, 129.0, 128.8, 128.6, 107.3,
68.7; IR (film) 2231 (CN), 2135 (CN2), 1706 (CꢀO), 1379,
1316, 1116 cm−1. (1R,2S,5R)-Menthyl cyanodiazoacetate
(4f). Yellow oil (102 mg, 71%): [h]D −92.9o (c 0.62,
1
CHCl3); Rf 0.59 (CHCl3); H NMR (400 MHz, CDCl3) l
4.80–4.87 (m, 1H), 2.01–2.04 (m, 1H), 1.81–1.85 (m, 1H),
1.67–1.72 (m, 2H), 1.42–1.51 (m, 2H), 1.04–1.12 (m, 2H),
0.83–0.92 (m, 7H), 0.78 (d, J=7.0 Hz, 3H); 13C NMR
(100 MHz, CDCl3) l 161.0, 107.6, 78.4, 47.0, 41.0, 34.1,
31.6, 26.6, 23.7, 22.1, 20.8, 16.6; IR (film) 2229 (CN),
2130 (CN2), 1706 (CꢀO), 1456, 1240, 1127, 950, 737 cm−1
.
(Z)-Pent-2-enyl cyanodiazoacetate (4g). Yellow oil (392
1
mg, 84%): Rf 0.55 (CHCl3); H NMR (300 MHz, CDCl3)
l 5.62–5.71 (m, 1H), 5.41–5.49 (m, 1H), 4.76 (d, J=6.7
Hz, 2H), 2.06–2.11 (m, 2H), 0.93–0.98 (m, 3H); 13C NMR
(75 MHz, CDCl3) l 161.2, 138.6, 121.2, 107.4, 62.6, 20.8,
13.9; IR (film) 2229 (CN), 2132 (CN2), 1713 (CꢀO), 1265,
1124, 918 cm−1. 2-(2-Methyl-allyloxy)-benzyl cyanodiazo-
acetate (4h). Yellow oil (382 mg, 91%): Rf 0.40 (CHCl3);
1H NMR (300 MHz, CDCl3) l 7.30–7.35 (m, 2H), 6.96
(t, J=7.5 Hz, 1H), 6.89 (d, J=8.6 Hz, 1H), 5.39 (s, 2H),
5.05 (d, J=24.5 Hz, 2H), 4.48 (s, 2H), 1.84 (s, 3H); 13C
NMR (75 MHz, CDCl3) l 161.3, 157.0, 140.7, 130.5,
123.0, 120.7, 112.8, 111.9, 107.4, 71.9, 64.7, 19.5; IR
(film) 2229 (CN), 2131 (CN2), 1717 (CO), 1495, 1243,
1126 cm−1. Anal. calc. for C14H13N3O3: C 61.99, H 4.83,
N 15.49; found: C 62.02, H 5.03, N 15.38. Cyanodia-
15. For cyanoacetate synthesis see: (a) Nahmany, M.; Mel-
man, A. Org. Lett. 2001, 3, 3733–3735; cyanomethyl
ketones see: (b) Krauss, J. C.; Cupps, T. L.; Wise, D. S.;
Townsend, L. B. Synthesis 1983, 308–309; (c) Chen, Y.;
Sieburth, S. M. Synthesis 2002, 2191–2194; phenyl
cyanoacetate see: (d) Bruice, T. C.; Hegarty, A. F.;
Felton, S. M.; Donzel, A.; Kundu, N. G. J. Am. Chem.
Soc. 1970, 92, 1370–1378.