Sodium hydride → HCID 86753062, compound

HRID 2392941Notes

Reaction equation

HRID 2392941 reaction equation
[H-].[Na+].[CH2:3]([O:5][C:6](=[O:19])/[CH:7]=[C:8](\[CH3:18])/[CH2:9]P(OCC)(OCC)=O)[CH3:4].[Br:20]/[C:21](=[C:24](/[C:26]1[CH:35]=[CH:34][C:33]2[C:32]([CH3:37])([CH3:36])[CH2:31][CH2:30][C:29]([CH3:39])([CH3:38])[C:28]=2[CH:27]=1)\[CH3:25])/[CH:22]=O>C1COCC1>[CH2:3]([O:5][C:6](=[O:19])/[CH:7]=[C:8](\[CH3:18])/[CH:9]=[CH:22]/[C:21](/[Br:20])=[C:24](\[C:26]1[CH:35]=[CH:34][C:33]2[C:32]([CH3:37])([CH3:36])[CH2:31][CH2:30][C:29]([CH3:39])([CH3:38])[C:28]=2[CH:27]=1)/[CH3:25])[CH3:4]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 6000084Ethyl 4-(diethoxyphosphoryl)-3-methylbut-2-enoateHCID 86753061HCID 86753061, compound

Product 1

HCID 86753062HCID 86753062, compoundYield 38.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

290 mg of NaH (50% in mineral oil) was suspended in 8 ml of abs. THF and treated at 0° C. with 1.69 g of 4-(diethoxyphosphinyl)-3-methyl-crotonic acid ethyl ester. When the development of H2 had ceased (1/2 hour at 0° C.), 1.04 g of (E)-2-bromo-3-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-naphthalen-2-yl)-but-2-enal, dissolved in 8 ml of abs. THF, was added and stirring continued for 3/4 hour at 0° C. and for 1 hour at room temperature. The reaction mixture was then quenched with crashed ice and extracted with EtOEt. Twice washing with brine, drying over Na2SO4 and evaporation of the solvent afforded the crude product which was purified by flash chromatography (silica gel, hexane/AcOEt=98:2) to give 527 mg of (2E,4E,6E)-6-bromo-3-methyl-7-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-naphthalen-2-yl)-octa-2,4,6-trienoic acid ethyl ester as yellow crystals of m.p. 97°-98.5° C.

Workup

  1. dissolutiondissolved in 8 ml of abs
  2. customThe reaction mixture was then quenched with crashed ice
  3. extractionextracted with EtOEt
  4. washTwice washing with brine
  5. dry with materialdrying over Na2SO4 and evaporation of the solvent
  6. customafforded the crude product which
  7. customwas purified by flash chromatography (silica gel, hexane/AcOEt=98:2)

Sources & evidence

ORD record
ord-c8b12afcede54e3daa65f66e1c1df3be
Source dataset
uspto-grants-1998_09
Patent number
US05801253

Reaction notes

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