Hydrochloric Acid → HCID 86740736, compound

HRID 1380675Notes

Reaction equation

HRID 1380675 reaction equation
[CH:1](NC(C)C)([CH3:3])[CH3:2].[C:8](=[O:10])=[O:9].[CH3:11][C:12]([CH3:14])=[O:13].[Li][CH2:16][CH2:17][CH2:18][CH3:19].[CH3:20][CH2:21][CH2:22][CH2:23][CH2:24][CH3:25].[CH3:26]OP(C)(C)(OC)N(C)C.CI.Cl.[CH2:39]1[CH2:43][O:42][CH2:41][CH2:40]1>>[CH2:43]([O:42][CH2:41][CH:14]1[CH:12]2[O:13][CH:21]([CH2:20][CH2:11]2)[CH:22]1[CH:23]([CH2:16][CH2:17][CH2:18][CH3:19])[CH:24]([CH3:25])[C:8]([O:10][CH3:26])=[O:9])[CH2:39][CH2:40][CH2:2][CH2:1][CH3:3]

Participants

9

Reactant 8

HCID 313Hydrochloric AcidHCID 6328Methyl iodideHCID 7912DiisopropylamineHCID 8028Tetrahydrofuran3×HCID 8058HexaneHCID 18522661Acetone cardiceHCID 23499210HCID 23499210, compoundHCID 178418339Butyllithium

Product 1

HCID 86740736HCID 86740736, compound

Procedure

A solution of dry diisopropyl amine (0.561 ml, 4.0 mmole) in dry THF (15 ml) was cooled and stirred in a bath at -78° (dry ice-acetone) under nitrogen and 1.65M n-BuLi in hexane (1.88 ml, 3.1 mmole) was added dropwise. After 5.0 minutes, a solution of the Example 63 methyl ester (1.06 g, 3.0 mmole) in dry THF (10 ml) was added dropwise in about 5 minutes. After another 15 minutes, a solution of dry hexamethylphosphorous amide (HMPA) (2.0 ml) in dry THF (2.0 ml) was added, followed by CH3I (1.68 ml, 27 mmole). After 3 hours, the mixture was poured into cold 10% hydrochloric acid (100 ml) and was extracted with ether (3×100 ml). The extracts were combined, washed with dilute brine, dried (MgSO4 anhydrous), evaporated and the resulting oil was flash chromatographed on silica gel (200 g, LPS-1), eluting with EtOAc-hexane (5:95) to afford, after drying in vacuo, the title compound (870 mg, 82%) as an oil, [α]D25 =(-) 3.73° (c, 3.3; CHCl3) with consistent IR, MS, H1 -NMR and C13NMR-spectral data.

Workup

  1. waitAfter another 15 minutes
  2. waitAfter 3 hours
  3. extractionwas extracted with ether (3×100 ml)
  4. washwashed with dilute brine
  5. dry with materialdried (MgSO4 anhydrous)
  6. customevaporated
  7. customchromatographed on silica gel (200 g, LPS-1)
  8. washeluting with EtOAc-hexane (5:95)
  9. customto afford
  10. customafter drying in vacuo
  11. custom3.73° (c, 3.3; CHCl3)

Sources & evidence

ORD record
ord-c6125467af124d458d6a7706c3d6084e
Source dataset
uspto-grants-1986_04
Patent number
US04582854

Reaction notes

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