B. Rissa® et al. / Tetrahedron 57 (2001) 2761±2768
2767
2
C, 65.01; H, 6.84; N, 6.28%. IR: n cm 3600±2700, 2250,
1
1
2
.73 (3H, s, CH3ax at C ), 1.80 (1H, d, J14.7 Hz, H4ax),
5
1
1720, 1660, 1600. H NMR 200 MHz (CDCl ): dppm: 0.94
.22 (1H, dd, JAB14.6 Hz, J
1.8 Hz, H ), 2.35
4eq
H4eqH6eq
3
(
J
1H, d, J12.9 Hz, H ), 2.45 (1H, dd, J12.9 Hz,
(3H, s, CH at C ), 1.03 (3H, s, CH at C ), 1.42 (3H, s, CH
3
6
ax
3
5
3
5
1.8 Hz, H ), 3.55 (1H, s, H ), 2 enolic form:
at C ), 1.75 (2H, AB, J15.0 Hz, H ), 2.30 (2H, AB,
H6eqH4eq
6eq
2
3
4
1
3
1.05 (3H, s, CH at C ), 1.20 (3H, s, CH at C ), 1.40
3
J13.2 Hz, H ), 3.05 (1H, s, H ). C NMR 50 MHz
3 3 3 3 5
eq
5
3
3
6 a
(
1H, d, J14.2 Hz, H4ax), 1.60 (3H, s, CH3ax at C ), 2.05
(CDCl ): dppm: 24.1 (CH at C ), 27.8 (2CH at C ), 36.0
(C ), 42.7(C ), 48.0 (C ), 61.4 (C ), 92.0 (CN), 122 (C ),
5 4 6 a 2
5
(
1H, d, J14.2 Hz, H ), 2.15 (2H, s, H ), 4.30 (1H, s, OH).
4
eq
6
1
3
C NMR 75 MHz (CDCl ) dppm: 2 ax±ax: 26.1 (CH at
3
138.2 (C ), 176.0 (CO H), 208.2 (C ).
3 2 1
3eq
C ), 28.6 (CH at C ), 32.6 (CH at C ), 30.5 (C ), 36.6
5
5
3
3
3ax
5
(
(
(
4
C ), 47.6 (C ), 52 (C ), 52.5 (C ), 113.5 (CN at C ), 121
ax
CNax at C ), 196 (C ), 2 eq±ax: 27.6 (CH at C ), 30.5
2 1 3eq 5
3.3.8. a-Phenyl-2-isophorone acetonitrile 5. White crys-
tals, mp 90±918C from petroleum ether. Anal. calcd for
C H NO: C, 80.60; H, 7.56; N, 5.53; O, 6.31%. Found:
3
4
2
6
3
C ), 32.0 (CH at C ), 33.0 (CH
3
at C ), 36.2 (C ),
3
5
3
3ax
5
17 19
2
1
5.2(C ), 49.7 (C ), 50.3 (C ), 105.0 (CN at C ), 120
3
C, 80.34; H, 7.54; N, 5.39; O, 6.48%. IR: n cm 2980±
2850, 2220, 1690, 1610. H NMR 200 MHz (CDCl3):
4
2
6
ax
1
(
CNeq at C ), 204 (C ), 2 enolic form: 25.8 (CH at C5),
2
1
3eq
2
4
1
8.6 (CH at C ), 32.3 (CH at C ), 32.3 (C ), 39.0 (C ),
3
dppm: 0.92 (3H, s, CH at C ), 1.03 (3H, s, CH at C ),
5
3
3ax
5
5
3
3
5
3
1.6 (C ), 46.6 (C ), 83.7 (CN at C ), 115.5 (CN at C ),
4
1.30 (3H, s, CH at C ), 1.75 (2H, AB, J15.7 Hz, H ),
6
2
3
3
3
4
1
22.2 (C ), 169.5 (C ). MS m/z (%), 190 ([M ], 10), 175
2.48 (2H, AB, J12.7 Hz, H ), 3.40 (1H, s, H ), 7.50 (5H,
m, H ). C NMR (CDCl ): dppm: 19.0 (CH at C ), 28.0
ar 3 3 3
2
1
6 a
1
3
(
[M2CH ], 41), 163 ([M2HCN], 13), 148 ([1752HCN],
3
2
2), 56 (100).
(2CH at C ), 32.9 (C ), 45.8 (C ), 51.2 (C ), 129.8 (C ),
3 5 5 4 6 2
1
1
([M 2CH ], 10), 195 (41), 180 (36), 168 (29), 154 (32),
43.4 (C ), 193.8 (C ). MS m/z (%), 253([M ], 46), 238
3 1
1
3.3.4. Ethyl a-ethoxycarbonyl-2-isophorone acetate 3a.
Colourless oil. Anal. calcd for C H O : C, 64.84; H,
3
43 (100).
1
6
24
5
8
.16; O, 27.00%. Found: C, 64.85; H, 8.19; O, 26.78%.
2
1
1
IR: n cm : 2850±3000, 1730, 1665, 1645. H NMR
00 MHz (CDCl ): dppm: 1.04 (6H, s, CH at C ), 1.22
3.3.9. 4,4,6-Trimethyl-2-oxo-bicyclo[4,1,0] heptane 7,7-
dicarbonitrile 6. White crystals, mp 50±518C from hexane.
Anal. calcd for C H N O: C, 71.29; H, 6.93; N, 13.86%.
2
3
3
5
(
6H, t, J7 Hz, 2CH ethoxy), 1.94 (2H, s, H ), 2.32 (2H,
3
4
12 14
2
2
1
s, H ), 4.20 (4H, q, J7 Hz, 2CH ethoxy), 4.85 (1H, s, H ).
6 2 a
Found: C, 71.11; H, 6.84; N, 13.92%. IR: n cm 2850±
2990, 2230, 1610. H NMR 400 MHz (CDCl ): dppm: 0.88
1
3
1
C NMR 50 MHz (CDCl ): dppm: 14.0 (CH ethoxy), 22.4
3
3
3
(
CH at C ), 28.1 (2CH at C ), 32.9 (C ), 46.8 (C ), 48.3
4
(3H, s, CH at C ), 1.05 (3H, s, CH at C ); 1.50 (3H, s, CH
3
3
3
3
5
5
3
5
3
5
(
1
(
C ), 50.4 (C ), 60.5 (CH ethoxy), 129 (C ), 158.4 (C ),
2
at C ), 1.70 (1H, d, J16.0 Hz, H ), 2.00 (1H, d, J16.0 Hz,
6
a
2
3
3
4
1
3
68.3 (CO ester), 169 (CO ester), 196 (C ); MS m/z (%) 296
1
H ), 2.45 (2H, J 13.0 Hz, H ), 3.80 (1H, s, H ). C NMR
3 3
4 AB 6 2
1
[M ], 8), 204 (100), 148 (20), 178 (10).
100 MHz (CDCl ): dppm: 24.4, 27.0 (2CH at C5), 30.6
(
CH at C ), 35.6 (C ), 41.1 (C ), 42.5 (C ), 58.7 (C ),
3 3 5 4 6 2
00
66.3 (C ), 86.5 (C ), 110.9 (CN), 111.1 (CN), 178.1 (C ).
3 1 1
3.3.5. Ethyl-2-isophorone acetate 3b. Colourless oil. Anal.
calcd for C H O : C, 69.61; H, 8.99; O, 21.40%. Found: C,
1
1
MS m/z (%), 202 ([M ], 27), 187 ([M 2CH ], 17), 160
3
1
9
20
3
2
9.83; H, 9.19; O, 21.23%. IR: n cm : 3600±2700, 1720,
1
6
1
(21), 147 (69), 133 (44), 119 (28), 41 (100).
1
670, 1630. H NMR 200 MHz (CDCl ): dppm: 1.04 (6H, s,
3
gemCH at C ), 1.25 (3H, t, J7 Hz, CH ethoxy), 1.94 (3H,
3.3.10. 9-Carbethoxy-2,4,4-trimethyl bicyclo[4,3,0]nona-
1,6-dien-8-one 7. White crystals, mp 124±1258C from
petroleum ether. Anal. calcd for C H O : C, 72.58; H,
3
5
3
s, CH at C ), 2.30 (4H, s, CH at C and C ), 3.37 (2H, s,
3
3
2
4
6
1
3
H ), 4.12 (2H, q, J7 Hz, CH ethoxy). C NMR 50 MHz
a
2
15 20
3
1
(
CDCl ): dppm: 14.0 (CH ethoxy), 22.5 (CH at C ), 28.0
3
8.06%. Found: C, 72.65; H, 8.12%. H NMR 250 MHz
(CDCl ): dppm: 0.98 (6H, s, gemCH at C ), 1.35 (3H, t,
3
3
3
(
2CH at C ), 32.8 (C ), 47.4 (C ), 48.4 (C ), 50.5 (C ), 61.5
6
3
5
5
4
a
3
3
4
(
1
1
CH ethoxy), 128.9 (C ), 156.6 (C ), 168.5 (CO ester),
2
J11.0 Hz, CH ethoxy), 2.20 (2H, s, H ), 2.55 (2H, d,
J
AB 3 3 2
2
3
3
5
1
96.9 (C ). MS m/z (%) 224 ([M ]), 178 (100), 163 (20),
50 (35).
12 Hz, H ), 2.58 (3H, s, CH at C ), 4.27 (2H, q,
2 9 7
1
J11 Hz, CH ethoxy), 4.75 (1H, s, H ), 5.22 (1H, s, H ).
C NMR 62 MHz (CDCl ): dppm: 14.0 (CH ethoxy), 28.0
3 3
1
3
3.3.6. Ethyl a-cyano-2-isophorone acetate 4a. Yellowish
oil. Anal. calcd for C H NO : C, 67.45; H, 7.68; N, 5.62;
O, 19.25%. Found: C, 67.43; H, 7.82; N, 5.48; O, 19.06%.
(2CH at C ), 32.2 (C ), 32.5 (CH at C ), 36.6 (C ), 46.0
3 4 4 3 2 5
(C ), 60.0 (C ), 67.5 (CH ethoxy), 104.5 (C ), 133.0 (C ),
3 9 2 7 1
1
4
19
3
147 (C ), 151 (C ), 170.0 (CO ester), 190 (C ), MS m/z (%),
6 2 8
2
1
1
1
248 ([M ], 100), 233 ([M 2CH ], 10), 219 (40), 203 (19),
1
IR: n cm : 2850±2980, 2230, 1740, 1660, 1600. H NMR
00 MHz (CDCl ): dppm: 1.02 (3H, s, CH at C ), 1.04 (3H,
3
2
187 (18), 159 (14), 43 (24).
3
3
5
s, CH at C ), 1.38 (3H, t, J8.4 Hz, CH ethoxy), 1.41 (3H,
3
5
3
s, CH at C ), 1.83 (2H, AB, J15 Hz, H ), 2.53 (2H, AB,
3.3.11. a-Cyano-2-isophorone acetamide 8a. White
crystals, mp 170±1728C from petroleum ether. Anal. calcd
for C H N O : C, 65.45; H, 7.27; N, 12.73%. Found: C,
3
3
4
J13.4 Hz, H ), 4.32 (2H, q, J8.4 Hz, CH ethoxy), 4.80
6
2
1
3
(1H, s, H ). C NMR 50 MHz (CDCl ): dppm: 14.4 (CH
a 3 3
ethoxy), 21.4 (CH at C ), 28.4 (2CH at C ), 33.7(C ), 39.4
12 16
2
2
2
1
65.51; H, 7.21; N, 12.61%. IR:n cm 3550±3600, 2220,
1640, 1600. H NMR 400 MHz, (DMSO-d ): dppm: 0.95
3
3
3
5
5
1
(
1
4
C ), 47.9 (C ), 60.5 (C ), 57 (CH ethoxy), 99.6 (CN),
4
6
a
2
6
1
19.3 (C ), 149 (C ), 198 (C ), MS m/z (%) 249 ([M ],
6), 43 (100).
(3H, s, CH at C ), 1.04 (3H, s, CH at C ), 1.29 (3H, s,
5
2
3
1
3
5
3
CH ), 1.75 (2H, d, J13.8 Hz, H ), 2.30 (2H, d, J13.8 Hz,
H ), 3.05 (1H, s, H ). C NMR 100 MHz, (DMSO-d ):
6 a 6
3
4
1
3
3.3.7. a-Cyano-2-isophorone acetic acid 4b. Orange crys-
tals, mp 186±1888C from hexane/ethylacetate, 6:4. Anal.
dppm: 17.8, 25.9 (2CH at C ), 31.9 (CH at C ), 34.8
3 5 3 3
(C ), 40.2 (C ), 44.2 (C ), 57.9 (C ), 93.7 (CN), 122 (C ),
5 4 6 a 2
calcd for C H NO : C, 65.16; H, 6.79; N, 6.33%. Found:
15
133.3 (C ), 165.5 (CONH ), 167.0 (C ).
3 2 1
1
2
3