Dimethyl Sulfoxide → HCID 54005066, compound

HRID 1461401Notes

Reaction equation

HRID 1461401 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[C:11]([O:14][CH2:15][CH2:16][CH2:17][C@H:18]1[CH2:23][CH2:22][CH2:21][C:20]([CH2:24][CH2:25][CH2:26][CH2:27][OH:28])=[C:19]1[CH3:29])(=[O:13])[CH3:12].C(N(CC)CC)C>C(Cl)Cl.O>[C:11]([O:14][CH2:15][CH2:16][CH2:17][C@H:18]1[CH2:23][CH2:22][CH2:21][C:20]([CH2:24][CH2:25][CH2:26][CH:27]=[O:28])=[C:19]1[CH3:29])(=[O:13])[CH3:12]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 22841818HCID 22841818, compound

Product 1

HCID 54005066HCID 54005066, compoundYield 88.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-50 °C

Procedure

To a solution of 2.9 ml (30.6 mmole) of oxalyl chloride in 80 ml of CH2Cl2 at -50° C. was added a solution of 4.74 ml (61.2 mmole) of DMSO in 14.0 ml of CH2Cl2. This mixture was then stirred at -50° C. for another 5 minutes and added slowly with 4.1 g (15.3 mmole) of (R)-3-[3-(acetyloxy)propyl]-2-methyl-1-cyclohexene-1-butanol in 16.3 ml of CH2Cl2. The mixture was then stirred at -50° C. for another 35 minutes and added with 20.0 ml (143 mmole) of triethylamine to give a white suspension. After stirring at -50° C. for 5 minutes, the mixture was stirred at room temperature for 10 minutes, added with 20 ml of water and extracted with 2×300 ml of CH2Cl2. The combined extracts were then washed with 2×50 ml of water, brine, dried over Na2SO4, filtered and concentrated. The crude product was chromatographed on a silica gel column (6:1, hexane/EtOAc) to give 3.6 g (87.8%) of the unstable (R)-3-[3-(acetyloxy)propyl]-2-methyl-1-cyclohexene-1-butanal as an oil. [α]D25 =-17.11° (CHCl3, c=1.04). IR (CHCl3): 1725, 2725 cm-1. 1H NMR (200 MHz): δ1.25 (m, 1H), 1.61 (s, 3H), 1.56-1.75 (m, 10H), 1.91 (n, 2H), 2.05 (s, 3H), 1.95-2.10 (m, 2H), 2.40 (dt, J=1.8, 7.3 Hz, 2H), 4.06 (m, 2H), 9.77 (t, J=1.8 Hz, 1H). Mass spectrum: M+ (266). Anal. for C16H26O3 : Calc. for C, 72.14; H, 9.80. Found: C, 70.12; H, 9.72.

Workup

  1. stirringThe mixture was then stirred at -50° C. for another 35 minutes
  2. customto give a white suspension
  3. stirringAfter stirring at -50° C. for 5 minutes
  4. stirringthe mixture was stirred at room temperature for 10 minutes
  5. extractionextracted with 2×300 ml of CH2Cl2
  6. washThe combined extracts were then washed with 2×50 ml of water, brine
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude product was chromatographed on a silica gel column (6:1, hexane/EtOAc)

Sources & evidence

ORD record
ord-588ac847d0c845ddb93a8910c82774e4
Source dataset
uspto-grants-1991_12
Patent number
US05075327

Reaction notes

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