Methanol → HCID 11768642, compound

HRID 842960Notes

Reaction equation

HRID 842960 reaction equation
CO.[C:3](Cl)(=[O:7])[C:4](Cl)=O.[BH4-].[Na+].S(=O)(=O)(O)O.[C:16]12(CS(O)(=O)=O)C(C)(C)[CH:20]([CH2:21][CH2:22]1)[CH2:19][C:17]2=[O:18]>ClCCl.C(O)C.O>[C@@H:4]12[C:3](=[O:7])[O:18][CH2:17][C@@H:16]1[CH2:22][CH:21]=[CH:20][CH2:19]2

Participants

9

Reactant 5

HCID 887MethanolHCID 1118Sulfuric AcidHCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 65578Oxalyl chlorideHCID 4311764Sodium borohydride

Product 1

HCID 11768642HCID 11768642, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Cis-Cyclohexene-1,2-dicarboxylic anhydride (30.4 g, 200 mmol) in methanol (9 ml, 220 mmol) is heated at the boil for 1 h. Excess solyent is then evaporated. 33.2 g (180 mmol) of the resulting monomethyl ester are, at 0° C. and under argon, dissolved in 200 ml of dry dichloromethane and admixed dropwise with oxalyl chloride (32 g, 252 mmol). After the evolution of gas has ceased, stirring at room temperature is continued for 3 h. The solyent is then removed under reduced pressure and the residue is dissolved in 75 ml of THF. This solution is then added dropwise to a solution, kept at −40° C. and under argon, of sodium borohydride (13.6 g, 360 mmol) in 750 ml of absolute ethanol. After the evolution of gas has ceased, stirring at −40° C. is continued for 2 h, and the mixture is acidified to pH 2 using 4 N sulphuric acid and concentrated. The residue is admixed with 400 ml of water and extracted with MTBE. The ether phases are dried over magnesium sulphate, filtered and concentrated. The residue is then taken up in 200 ml of toluene, admixed with 10-camphorsulphonic acid (100 mg, 0.43 mmol) and heated in a water separator until TLC shows complete conversion. The solyent is then evaporated and the residue is distilled under reduced pressure (b.p.: 70° C./0.01 Torr).

Workup

  1. customExcess solyent is then evaporated
  2. customare, at 0° C. and under argon
  3. customThe solyent is then removed under reduced pressure
  4. dissolutionthe residue is dissolved in 75 ml of THF
  5. additionThis solution is then added dropwise to a solution
  6. stirringstirring at −40° C.
  7. waitis continued for 2 h
  8. concentrationconcentrated
  9. extractionextracted with MTBE
  10. dry with materialThe ether phases are dried over magnesium sulphate
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe solyent is then evaporated
  14. distillationthe residue is distilled under reduced pressure (b.p.: 70° C./0.01 Torr)

Sources & evidence

ORD record
ord-9b5cc258025542de83669aeba35efc3e
Source dataset
uspto-grants-2002_04
Patent number
US06376539B1

Reaction notes

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