2-Hexanone → HCID 14174973, compound

HRID 1649971Notes

Reaction equation

HRID 1649971 reaction equation
[CH3:1][C:2]1([CH3:13])[C@@H:7]2[CH2:8][CH2:9][C@@H:10]([CH3:12])[CH2:11][C@H:6]2[O:5][CH2:4][S:3]1.C([Li])CCC.[CH3:19][C:20](=[O:25])[CH2:21][CH2:22][CH2:23][CH3:24].[Cl-].[NH4+]>O1CCCC1.CCCCCC.O>[OH:25][C@@:20]([C@H:4]1[S:3][C:2]([CH3:13])([CH3:1])[C@@H:7]2[CH2:8][CH2:9][C@@H:10]([CH3:12])[CH2:11][C@H:6]2[O:5]1)([CH2:21][CH2:22][CH2:23][CH3:24])[CH3:19]

Participants

8

Reactant 4

HCID 115832-HexanoneHCID 25517Ammonium ChlorideHCID 11745675HCID 11745675, compoundHCID 178418339Butyllithium

Product 1

HCID 14174973HCID 14174973, compoundYield 96.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

A vigorously stirred solution of (4aR,7R,8aR)-hexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin (9 g, 0.045 mole, prepared as described by ELIEL et al. Org. Synth. 65, 215 [1987]) in 130 ml of anhydrous tetrahydrofuran was cooled to -78° C. under an ar8on atmosphere and butyllithium (3.168 g, 0.0195 mole) dissolved in 32 ml of hexane was added dropwise over a period of 15 minutes. The solution was further stirred for additional 15 minutes. The temperature of the solution was allowed to slowly reach 0° C. and further stirred for 15 minutes. The solution was cooled again to -78° C. under the argon atmosphere, the stirring was continued and 2-hexanone (4.5 g, 0.045 mole) dissolved in 25 ml of anhydrous tetrahydrofuran was added dropwise over a period of 20 minutes. The solution was further stirred for additional 4 hours. The temperature of the solution was allowed to slowly reach the room temperature, 10 ml of water were added dropwise over a period of 10 minutes and then 15 ml of a saturated solution of ammonium chloride in water were added at once. The reaction mixture was S partitioned between diethyl ether and water. The ether portion was washed with brine, dried over anhydrous Na2SO4 which was then removed by filtration, and evaporated to leave 13.1 g of a thick syrup. This thick syrup was dissolved in 10 ml of hexane-ethyl acetate (9:1 v:v) solvent and chromatographed on 1000 g of silica gel (230-400 mesh ASTM). The 5 liters of hexane-ethyl acetate that were eluted, were evaporated in vacuo to leave a viscous colorless liquid residue. This liquid was distilled at reduced pressure. The fraction distilling at 95°-97° C. and 0.05 Torr was collected yielding 6.2 g (45.9%) of the title compound, which shows [α]365 =-28.91° (C=1.61 in CHCl3). Anal. Calcd. for C17H32O2S: C,67.96; H,10.74; O,10.65; S,10.65, Found: C,68.20; H,10.63; O,10.47; S,10.56.

Workup

  1. additionwas added dropwise over a period of 15 minutes
  2. customwas allowed to slowly reach 0° C.
  3. stirringfurther stirred for 15 minutes
  4. additionwas added dropwise over a period of 20 minutes
  5. stirringThe solution was further stirred for additional 4 hours
  6. additionwere added dropwise over a period of 10 minutes
  7. custompartitioned between diethyl ether and water
  8. washThe ether portion was washed with brine
  9. dry with materialdried over anhydrous Na2SO4 which
  10. customwas then removed by filtration
  11. customevaporated

Sources & evidence

ORD record
ord-0464de849d434d40bd7b61bb205949a4
Source dataset
uspto-grants-1990_05
Patent number
US04922032

Reaction notes

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