Sodium hydride → Methyl 8-methoxycarbonyl-8-methylsulfonyl-12-acetoxyheptadecanoate

HRID 2083281Notes

Reaction equation

HRID 2083281 reaction equation
[H-].[Na+].[CH3:3][O:4][C:5](=[O:21])[CH:6]([S:17]([CH3:20])(=[O:19])=[O:18])[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][C:13]([O:15][CH3:16])=[O:14].I[CH2:23][CH2:24][CH2:25][CH:26]([O:32][C:33](=[O:35])[CH3:34])[CH2:27][CH2:28][CH2:29][CH2:30][CH3:31]>CN(C)C=O>[CH3:3][O:4][C:5]([C:6]([S:17]([CH3:20])(=[O:19])=[O:18])([CH2:23][CH2:24][CH2:25][CH:26]([O:32][C:33](=[O:35])[CH3:34])[CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][C:13]([O:15][CH3:16])=[O:14])=[O:21]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 21317518HCID 21317518, compoundHCID 54054723Dimethyl-2-methylsulfonylazelate

Product 1

HCID 21317603Methyl 8-methoxycarbonyl-8-methylsulfonyl-12-acetoxyheptadecanoateYield 98.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A suspension of 57% sodium hydride/mineral oil (3.84 g., 0.091 mole) is washed by decantation with petroleum ether to remove the mineral oil. The residual solid is suspended in dry dimethylformamide (100 ml.) and treated with a solution of dimethyl-2-methylsulfonylazelate (23.5 g., 0.08 mole) in dry dimethylformamide (60 ml.) added dropwise at ambient temperature under a nitrogen atmosphere. The resulting solution is stirred for 1 hour at room temperature, cooled to ~10° C., and treated with 1-iodo-4-acetoxynonane (30 g., 0.096 mole) added at such a rate as to maintain an internal temperature less than 35° C. After 19 hours at ambient temperature, the reaction mixture is filtered. Collected sodium iodide (17.1 g.) is washed with ether. The combined filtrate and washings are concentrated in vacuo at ~ 100° C. yielding a residual oil which is partitioned between ether and dilute hydrochloric acid. The organic extract is washed with water and saturated brine, dried over magnesium sulfate and evaporated in vacuo leaving the title compound as a viscous oil (37.7 g., 98%), pmr (CDCl3) δ 2.0 (s, 3H), 3.0 (s, 3H), 3.65 (s, 3H), 3.81 (s, 3H) and 4.9 (b, H).

Workup

  1. washis washed by decantation with petroleum ether
  2. customto remove the mineral oil
  3. additionadded dropwise at ambient temperature under a nitrogen atmosphere
  4. temperaturecooled to ~10° C.
  5. additionadded at such a rate as
  6. temperatureto maintain an internal temperature less than 35° C
  7. waitAfter 19 hours at ambient temperature
  8. filtrationthe reaction mixture is filtered
  9. washCollected sodium iodide (17.1 g.) is washed with ether
  10. concentrationThe combined filtrate and washings are concentrated in vacuo at ~ 100° C.
  11. customyielding a residual oil which
  12. customis partitioned between ether and dilute hydrochloric acid
  13. extractionThe organic extract
  14. washis washed with water and saturated brine
  15. dry with materialdried over magnesium sulfate
  16. customevaporated in vacuo

Sources & evidence

ORD record
ord-60fceb05b7cf4ac69cc7173a51c1fe9d
Source dataset
uspto-grants-1978_04
Patent number
US04085125

Reaction notes

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