V. Fargeas et al. / Tetrahedron 60 (2004) 10359–10364
10363
(100); 69 (24); 55 (36); 43 (91). IR: 2995; 2936; 1602; 1445;
1317; 1308; 1159; 1085; 694.
MC1Z191; MC18Z208. SM (EI) m/z (%): 190 (21); 104
(67); 91 (100); 77 (30); 43 (100). HR MS: 190.0996
(C12H14O2; calcd 190.0994). IR: 3027; 2928; 1706; 1603;
1496; 1454; 1361; 1134; 785; 750; 699.
1.5.6. (7Z)-1-Phenylsulfonyl-decene-2,4-dione 26.
(Eluants: petroleum ether/ethyl acetate: 6/4) 0.15 g of 26
1
were obtained as a yellow oil (yieldZ80%). H NMR d
1.6.4. Decane-2,4-dione 24. (Eluants: petroleum ether/ethyl
acetate: 7/3) 265 mg of 24 were obtained as a yellow oil
(ppm): 0.93 (t, 3H, JZ7 Hz, H10); 1.90–2.15 (m, 2H, H9);
2.19–2.45 (m, 4H, H5 and H6); 4.02 (s, 2H, H1); 5.15–5.62
(m, 2H, H3 and H4); 5.70 (s, 1H, H3); 7.49–7.99 (m, 5H,
Har). 13C NMR d (ppm): 14.2 (C10); 20.5 (C9); 23.0 (C5 or
C6); 38.4 (C5 or C6); 64.5 (C1); 102.2 (C7 and C8); 126.3,
128.4, 129.4, 134.3, 138.5 (5C, Car), 179.8 (C4); 195.1 (C2).
MS (CI/NH3): MC18Z326; MC1Z309. MS (EI) m/z (%):
240 (56); 225 (12); 199 (15); 183 (29); 167 (26); 141 (77);
125 (31); 109 (53); 77 (100); 67 (48); 55 (46); 41 (75). IR:
2957; 2930; 1615; 1506; 1446; 1320; 1309; 1156; 1085.
1
(yieldZ90%). H NMR d (ppm): 0.86 (m, 3H, H10); 1.26
(m, 16H, H6–H9); 2.02 (m, 3H, H1); 2.22 (m, 2H, H5); 5.47
(s, 1H, H3). 13C NMR d (ppm): 14.2; 22.7; 25.2; 25.9; 29.1
(5C, Calk); 31.8 (C1); 38.5 (Calk); 99.9 (C3); 191.7 (C4);
194.5 (C2). MS (CI/NH3): MC1Z171; MC18Z188. MS
(EI) m/z (%): 170 (2); 113 (18); 100 (55); 85 (100); 72 (16);
43 (100). HR MS: 170.1304 (C10H18O2; calcd 170.130). IR:
2956; 2929; 2858; 1613; 1460; 1364.
1.6.5. (7Z)-Decene-2,4-dione 27. (Eluants: petroleum ether/
ethyl acetate: 7/3) 265 mg of 27 were obtained as a yellow
oil (yieldZ90%). H NMR d (ppm): 0.88 (t, 3H, JZ7 Hz,
1.6. General procedure for desulfonation
1
Turnings of sodium (0.46 g; 20 mmol; 12.2 equiv) were
added to mercury (7.3 g; 36.4 mmol; 22 equiv) at rt. 8.3 mL
of dry MeOH were then added to the corresponding
amalgam and the temperature was cooled to K50 8C. A
solution of 1,3-dione (1.7 mmol; 1 equiv) in 12 mL of
MeOH was added and the reaction mixture was stirred 2 h at
K20 8C before the hydrolysis was achieved with a saturated
aquous solution of NH4Cl (40 mL) at 0 8C. After filtration,
the aqueous phase was extracted with 3!10 mL Et2O
before drying on MgSO4. After evaporation of the solvent,
the crude residue was purified by a short flash chromato-
graphy to afford the desired compound. All compounds
were obtained under their enolic form.
H10); 1.95 (s, 3H, H1); 1.95 (m, 2H, H9); 2.25 (m, 4H, H5–
H6); 5.15–5.41 (m, 2H, H7–H8); 5.42 (s, 1H, H3). 13C NMR
d (ppm): 13 (C10); 20 (C9); 22 (C6); 24 (C1); 37 (C5); 99
(C3); 126 and 132 (C7 and C8); 190 and 192 (C2 and C4). MS
(CI/NH3): MC1Z169; MC18Z186. MS (EI) m/z (%):
168 (2); 110 (11); 100 (30); 85 (100); 67 (27); 55 (14); 43
(71). HR MS: 168.1154 (C10H16O2; calcd 168.1150). IR:
2956; 2863; 1713; 1620; 1454; 1360; 1142.
Acknowledgements
This program is supported by CPER of the Regional Council
of the Pays-de-la-Loire and by Ifremer. The authors thank
Dr. Patrick Durand (Ifremer) for constant support and
encouragements.
1.6.1. 1-Cyclohexyl-butane-1,3-dione 13. (Eluants:
CH2Cl2) 0.22 mg of 13 were obtained as a pale orange oil
1
(yieldZ77%). H NMR (CDCl3) d (ppm): 0.69–1.89 (m,
10H, Hcyclohexyl); 2.06 (s, 3H, H4); 2.22 (m, 1H, Hcyclohexyl);
0
References and notes
3.60 (s, 2H, H2 ); 5.48 (s, 1H, H2); 12.06 (s, 1H, OH).
13C NMR d (ppm): 24.0; 25.9; 27.8; 29.6 (4C, Ccyclohexyl);
28.5 (C4); 46.4 (C5); 98.1 (C2); 192.6 (C1 and C3). MS
(CI/NH3): MC1Z169. MS (EI) m/z (%): 168 (18); 113
(12); 85 (100); 55 (24); 43 (35). HR MS: 168.1167
(C10H16O2; calcd 168.1150). IR: 2966; 1612; 1492; 1364.
1. WO 0044718 A1 20000803 or Chem. Abstr. 133, 134246.
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1.6.2. 1-Phenyl-butan-1,3-dione 16. (Eluants: petroleum
ether/ethyl acetate: 7/3) 140 mg of 16 were obtained as a
pale yellow oil (yieldZ76%). 1H NMR d (ppm): 2.06
(s, 3H, H1); 5.03 (m, 1H, H3); 7.15–7.24 (m, 5H, Har) [10%
of the 1–3 diketone form is detected: 2.18 (s, 3H, H1); 6.20
(s, 2H, H3); 7.43–7.84 (m, 5H, Har)21]. 13C NMR d (ppm):
24.1 (C1); 47.0 (C3); 68.8 (C2); 75.2 (C4); 125.7 (2C, Car);
127.5 (Car); 128.5 (2C, Car); 144.5 (Car). MS (CI/NH3):
MC1Z163; MC18Z180. MS (EI) m/z (%): 146 (28); 105
(53); 77 (67); 43 (98). IR: 3436; 3062; 3030; 2925; 1713;
1603; 1494; 1449; 1360; 1323; 1158; 1083; 756; 701.
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1.6.3. 6-Phenyl-hexan-2,4-dione 19. (Eluants: petroleum
ether/ethyl acetate: 7/3) 224 mg of 19 were obtained as a
brown oil (yieldZ71%). 1H NMR d (ppm): 2.04 (s, 3H, H1);
2.65 (m, 2H, H5); 2.92 (m, 2H, H6); 5.48 (s, 1H, H3); 7.17–
7.29 (m, 5H, Har). 13C NMR d (ppm): 25.1 (C5); 31.8 (C1);
40.3 (C3); 100.3 (C6); 126.5 (Car); 128.6 (2C, Car); 128.8
(2C, Car); 140.9 (Car); 191.3 (C4); 193.5 (C2). MS (CI/NH3):
8. Beck, A. K.; Hoekstra, M. S.; Seebach, D. Tetrahedron Lett.
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3679–3682.
11. (a) Le Roux, C.; Mandrou, S.; Dubac, J. J. Org. Chem. 1996,