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Helvetica Chimica Acta – Vol. 88 (2005)
Data of 9b: Colorless solid. Rf (SiO2, pentane/CH2Cl2 3 :1) 0.42. M.p. 47–498. IR (film): 2956m (CH,
stretch.), 1724s (C=O), 1376m (CH3, def.), 1213, 1172s (CꢀO). 1H- and 13C-NMR: Table. GC/MS: 318 (28,
M+), 289 (5, [MꢀC2H5]+), 245 (10, [MꢀC3H5O2]+), 205 (18, [MꢀC8H17]+), 131 (36, [205ꢀC3H6O2]+), 112
(100, C8Hþ16). HR-MS 341.244629+1.39 ppm (C21H34NaOþ2 , [M+Na]+: calc. 341.245649).
Data of 10: Colorless liquid. Rf (SiO2, pentane/CH2Cl2 3 :1) 0.61. IR. (film): 2956m (CH, stretch.), 1724s
(C=O), 1376m (CH3, def.), 1213, 1172s (CꢀO). 1H- and 13C-NMR: Table. MS/GC: 318 (5, M+), 273 (21, [Mꢀ
CO2H]+), 245 (20, [MꢀCO2Et]+), 230 (100, [245ꢀCH3]+), 205 (25, [MꢀC8H17]+), 131 (73, [205ꢀC3H6O2]+),
117 (50, [131ꢀCH2]+), 91 (45, [117ꢀC2H4]+). HR-MS: 341.244790+0.92 ppm (C21H34NaOþ2 , [M+Na]+; calc.
341.245649).
rel-(1aR,4S,6aS)- and rel-(1aR,4R,6aS)-1,1a,2,3,4,5,6,6a-Octahydro-4-octylcyclopropa[f]indene-1-carbox-
ylic Acid 12 and 13, resp.). A mixture of EtOH (100 ml) and 1
then 9a (0.5 g, 1.46 mmol) was added slowly. The mixture was kept at r.t. and stirred for 4–6 h (TLC monitor-
ing). Then the mixture was acidified with 1 HCl. The EtOH was evaporated and the residual aq. phase
M NaOH (60 ml) was stirred for a while, and
M
extracted with AcOEt (2×) and H2Cl2 (1×). The combined org. extract was washed with H2O, dried (MgSO4),
and evaporated and the residue purified by CC (silica gel, CH2Cl2 (! impurities) then Et2O): 0.3 g (71%) of
12. Colorless solid which was recrystallized from hexane/CH2Cl2. As described for 12, 13 was prepared from
9b in 75% yield.
Data of 12: Rf (SiO2, AcOEt/CH2Cl2 1:5) 0.49. M.p. 90–938. IR (film): 2956m (CH, stretch.), 1724s (C=O),
1
3
1376m (CH3, def.), 1213, 1172s (CꢀO). H-NMR (400.1 MHz, CDCl3): 0.89 (t, J=6.8, Me(CH2)7); 1.26 (br. s,
3
Me(CH2)7); 1.44 (t, J=4.2, HꢀC(1)); 1.82 (br. s, HꢀC(1a), HꢀC(6a)); 1.32 (m,HꢀC(4)), 2.31 (br. s, CH2(2),
CH2(6)); 1.87 (dd, J=5.8, 13.2, HbꢀC(3), HbꢀC(5)); 2.25 (dd, J=8.3, 13.2, HaꢀC(3), HaꢀC(5)). 13C-NMR
(100.6 MHz, CDCl3): 14.02 (q, Me(CH2)7); 22.69 (d, C(1)); 23.27 (t, MeCH2(CH2)6), 23.37 (2t, C(2), C(6));
24.20 (2d, C(1a), (6a)), 28.28 (t, Me(CH2)5CH2CH2), 29.34, 29.72, 29.89 (3t, Me(CH2)2(CH2)3(CH2)2); 31.85 (t,
MeCH2CH2(CH2)5); 36.21 (d, C(4)); 36.87 (t, Me(CH2)6CH2); 42.47 (2t, C(3), C(5)); 128.84 (2s, C(2a),
C(5a)); 181.06 (s, C=O). EI-MS: 290 (100, M+), 177 (70, [MꢀC8H17]+), 207 (10, [MꢀC6H11]+), 131 (40, [177ꢀ
HCO2H]+), 105 (30, [131ꢀC2H4]+). HR-MS 290.224146+1.50 ppm (C19H30Oþ2 ; calc. 290.224580).
Data of 13: Rf (SiO2, AcOEt/CH2Cl2 1:5) 0.45. M.p. 94–968. IR (film): 2956m (CH, stretch.), 1724s (C=O),
1
3
1376m (CH3, def.), 1213, 1172s (CꢀO). H-NMR (400.1 MHz, CDCl3): 0.86 (t, J=6.8, Me(CH2)7); 1.24 (br. s,
Me(CH2)7); 1.38 (t, 3J=4.2, HꢀC(1)); 1.80 (br. s, HꢀC(1a), HꢀC(6a)); 2.10 (m, HꢀC(4)); 2.30 (br. s, CH2(2),
CH2(6)); 1.75 (dd, J=5.8, 15.1,HbꢀC(3), HbꢀC(5)); 2.35 (dd, J=6.6, 15.1,HaꢀC(3), HaꢀC(5)). 13C-NMR (100.6
MHz, CDCl3): 14.51 (q, Me(CH2)7); 22.69 (t, MeCH(CH2)6); 23.29 (d, C(1)); 23.37 (2d, C(1a), C(6a)); 24.15 (2t,
C(2), C(6)); 28.21 (t, Me(CH2)5CH2CH2), 29.34, 29.66, 29.84 (3t, Me(CH2)2(CH2)3(CH2)2); 31.87 (t, MeCH2CH2-
(CH2)5), 35.66 (d, C(4)); 37.05 (t, Me(CH2)6CH2); 42.53 (2t, C(3), C(5)); 129.00 (2s, C(2a), C(5a)); 180.75 (s, C=
O). EI-MS: 290 (100, M+), 207 (12, [MꢀC6H11]+), 177 (75, [MꢀC8H17]+), 131 (45, [177ꢀHCO2H]+), 105 (25,
[131ꢀC2H4]+). HR-MS: 290.224421+0.55 ppm (C19H30Oþ2 ; calc. 290.224580).
Z. H. gratefully acknowledges the technical support from Mrs. M. Trinoga and help with the manuscript by
Prof. W. Gärtner, Max-Planck-Institut für Bioanorganische Chemie, Mülheim, Germany.
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