Sodium hydride → HCID 131724048, compound

HRID 398310Notes

Reaction equation

HRID 398310 reaction equation
[H-].[Na+].[C:3]([C:8]1[CH:22]=[CH:21][C:11]([CH2:12]P(=O)(OCC)OCC)=[CH:10][CH:9]=1)([O:5][CH2:6][CH3:7])=[O:4].[Si:23]([O:30][CH:31]1[C:36]2([CH3:53])[C:37]3[CH:42]=[C:41]([CH:43]=O)[C:40]([O:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH3:52])=[CH:39][C:38]=3[C:32]1([CH3:54])[CH2:33][CH2:34][CH2:35]2)([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24]>CN(C=O)C>[Si:23]([O:30][CH:31]1[C:36]2([CH3:53])[C:37]3[CH:42]=[C:41](/[CH:43]=[CH:12]/[C:11]4[CH:10]=[CH:9][C:8]([C:3]([O:5][CH2:6][CH3:7])=[O:4])=[CH:22][CH:21]=4)[C:40]([O:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH3:52])=[CH:39][C:38]=3[C:32]1([CH3:54])[CH2:33][CH2:34][CH2:35]2)([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 10979490Ethyl 4-((diethoxyphosphoryl)methyl)benzoateHCID 88114607HCID 88114607, compound

Product 1

HCID 131724048HCID 131724048, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

248 mg of NaH (about 50% in oil) were placed in 12 ml of abs. DMF under argon. 2.45 g of diethyl (4-carbethoxybenzyl)phosphonate were added thereto at 0° and the mixture was subsequently stirred at room temperature for about 2 hours until the H2 evolution had finished. The mixture was cooled to −10° C. and 2.20 g of (5RS,9SR,10RS)-10-t-butyldimethylsilyloxy-2-formyl-3-heptyloxy-5,9-dimethyl-6,7,8,9-tetrahydro-5,9-methano-5H-benzocycloheptene dissolved in 10 ml of abs. DMF were slowly added dropwise thereto. Then, the cooling bath was removed and the mixture was left to react at room temperature for 2 hours. It was then poured into ice/NH4Cl solution, extracted with diethyl ether, washed with NaCl solution, dried over Na2SO4 and concentrated. Flash chromatography on SiO2 (hexane/ethyl acetate 98/2) gave 2.32 g of ethyl (E)-4-[2-[(5RS,9SR,10RS)-10-t-butyldimethylsilyloxy-3-heptyloxy-5,9-dimethyl-6,7,8,9-tetrahydro-5,9-methano-5H-benzocyclohepten-2-yl]vinyl]benzoate as a yellowish oil.

Workup

  1. temperatureThe mixture was cooled to −10° C.
  2. customThen, the cooling bath was removed
  3. waitthe mixture was left
  4. customto react at room temperature for 2 hours
  5. extractionextracted with diethyl ether
  6. washwashed with NaCl solution
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-68a8e6639b0640aab9a1d516a044c1b7
Source dataset
uspto-grants-2003_08
Patent number
US06610877B1

Reaction notes

Loading…