Sulfuric Acid → HCID 12148783, compound

HRID 902579Notes

Reaction equation

HRID 902579 reaction equation
[CH:1](NC(C)C)(C)C.[Li]CCCC.[CH3:13][O:14][C:15](=[O:24])[C:16]([C:18]12[CH2:23][CH:22]1[CH2:21][CH2:20][CH2:19]2)=O.S(=O)(=O)(O)O.[Cl-].[Na+]>CCCCCC.[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1>[CH3:13][O:14][C:15](=[O:24])[C:16]([C:18]12[CH2:23][CH:22]1[CH2:21][CH2:20][CH2:19]2)=[CH2:1]

Participants

9

Reactant 5

HCID 1118Sulfuric AcidHCID 5234Sodium ChlorideHCID 7912DiisopropylamineHCID 12148782HCID 12148782, compoundHCID 178418339Butyllithium

Product 1

HCID 12148783HCID 12148783, compoundYield 85%

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

1.4 ml (10 mmol) diisopropylamine and 65 ml (100 mmol) 1.55 M n-BuLi solution in hexane were added under argon at −78° C. to a well-stirred suspension of 37.5 g (105 mmol) methyltriphenylphosphonium bromide in 400 ml anhydrous tetrahydrofuran (THF). The reaction mixture was allowed to heat to room temperature, cooled again and then at −78° C. a solution of 16.8 g (100 mmol) 2-(bicyclo-[3.1.0]hex-1-yl)-2-oxoacetic acid methyl ester in 20 ml THF was added dropwise so that the temperature did not exceed −50° C. The solution was then stirred for 10 hours at room temperature and acidified with 5% sulphuric acid. After the addition of 50 ml saturated sodium chloride solution the organic phase was separated off, the aqueous phase extracted with diethyl ether and the combined organic phase washed with saturated sodium chloride solution. 10 mg 2,6-di-t-butyl-p-cresol (BHT) were added for stabilizing, then the solvent was distilled off and the residue purified by column chromatography (pentane/diethyl ether 20:1). 15.7 g (85% yield) of BCHAM was obtained as colourless liquid.

Workup

  1. temperaturecooled again
  2. customdid not exceed −50° C
  3. customwas separated off
  4. extractionthe aqueous phase extracted with diethyl ether
  5. washthe combined organic phase washed with saturated sodium chloride solution
  6. addition10 mg 2,6-di-t-butyl-p-cresol (BHT) were added
  7. distillationthe solvent was distilled off
  8. customthe residue purified by column chromatography (pentane/diethyl ether 20:1)
  9. custom15.7 g (85% yield) of BCHAM was obtained as colourless liquid

Sources & evidence

ORD record
ord-1d417ff0ef734534acad4304bdee0aa2
Source dataset
uspto-grants-2008_04
Patent number
US07365222B2

Reaction notes

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