Trimethyl orthoformate → HCID 86679260, compound

HRID 1519685Notes

Reaction equation

HRID 1519685 reaction equation
[CH:1]([O:6][CH3:7])([O:4][CH3:5])OC.CC1(C)C2(CS(O)(=O)=O)C(CC1CC2)=O.C([C:25]1[CH:30]=[CH:29][C:28]([C:31]#[C:32][C:33]2[CH:43]=[CH:42][C:36]([C:37]([O:39][CH2:40][CH3:41])=[O:38])=[CH:35][CH:34]=2)=[CH:27][CH:26]=1)=O.C(=O)([O-])O.[Na+]>C(Cl)(Cl)Cl.CO>[CH3:7][O:6][CH:1]([O:4][CH3:5])[C:25]1[CH:26]=[CH:27][C:28]([C:31]#[C:32][C:33]2[CH:34]=[CH:35][C:36]([C:37]([O:39][CH2:40][CH3:41])=[O:38])=[CH:42][CH:43]=2)=[CH:29][CH:30]=1

Participants

7

Reactant 4

HCID 9005Trimethyl orthoformateHCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 516892Sodium BicarbonateHCID 86679257HCID 86679257, compound

Product 1

HCID 86679260HCID 86679260, compoundYield 67%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6212ChloroformSolvent

Procedure

Trimethyl orthoformate (51 g) and (+)-CSA (2.3 g) were added to a methanol (0.40 L)-chloroform (0.10 L) mixed solution of ethyl 4-[(4-formylphenyl)ethynyl]benzoate (27 g) as obtained in Example 10-(1), and the mixture was stirred for 3 hours at room temperature. A saturated aqueous solution of sodium hydrogen carbonate was added to the reaction mixture, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, and then the desiccant was filtered out. Then, the solvent was distilled off under reduced pressure, and the resulting residue was purified by OH type silica gel chromatography (gradient elution with hexane/ethyl acetate=95/5→80/20) to obtain ethyl 4-{[4-(dimethoxymethyl)phenyl]ethynyl}benzoate (white solid) (21 g, 67%).

Workup

  1. customas obtained in Example 10-(1)
  2. extractionthe mixture was extracted with chloroform
  3. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  4. filtrationthe desiccant was filtered out
  5. distillationThen, the solvent was distilled off under reduced pressure
  6. customthe resulting residue was purified by OH type silica gel chromatography (gradient elution with hexane/ethyl acetate=95/5→80/20)

Sources & evidence

ORD record
ord-3c99620bc79945d1aa7c6b6e017ac72b
Source dataset
uspto-grants-2015_07
Patent number
US09073821B2

Reaction notes

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