Benzyl Alcohol → Oxalyl chloride

HRID 2422694Notes

Reaction equation

HRID 2422694 reaction equation
[C:1]([Cl:6])(=[O:5])[C:2]([Cl:4])=[O:3].[CH3:7][CH:8]1[CH2:10][CH:9]1[C:11]([OH:13])=[O:12].CN(C=O)C.[CH2:19](O)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.N1C=CC=CC=1>ClCCl.C1(C)C=CC=CC=1.C1COCC1>[C:1]([Cl:6])(=[O:5])[C:2]([Cl:4])=[O:3].[CH3:7][C@@H:8]1[CH2:10][C@H:9]1[C:11]([O:13][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)=[O:12]

Participants

10

Reactant 5

HCID 244Benzyl AlcoholHCID 1049PyridineHCID 6228DimethylformamideHCID 65578Oxalyl chloride2×HCID 998732-Methylcyclopropanecarboxylic acid

Product 2

HCID 65578Oxalyl chlorideHCID 67180743(1R,2r)-benzyl2-methylcyclopropanecarboxylate

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

A 2.0 M oxalyl chloride in dichloromethane solution is prepared by adding with stirring 98% oxalyl chloride (110.0 mL) to anhydrous dichloromethane (600.0 mL). The resulting solution of oxalyl chloride (1.20 mol) is added dropwise over 1 h to a stirring solution of 2-methylcyclopropanecarboxylic acid (commercially available product which is a cis-trans mixture, 120.0 g, 1.20 mol) in toluene (800.0 mL) containing DMF (0.6 mL, 7.8 mmol). The mixture is stirred 2 h at room temperature; then it is added dropwise to a solution of benzyl alcohol (114.0 mL, 1.10 mol), anhydrous THF (800.0 mL), and pyridine (194.0 mL, 2.41 mol) over 1.5 h. The mixture is stirred 1 h longer after addition, partitioned between ethyl acetate (2 L) and 10% aqueous potassium carbonate (2 L); and the organic phase is washed (10% aqueous potassium carbonate (2 L) and brine (2 L)), dried (MgSO4) and evaporated to a liquid. Chromatography over silica gel, eluting with 5% ethyl acetate in hexanes, provides the major product, racemic benzyl trans-2-methyl-cyclopropanecarboxylate as a clear, colorless liquid (193.8 g, 93%).

Workup

  1. additionby adding
  2. stirringThe mixture is stirred 1 h
  3. additionlonger after addition
  4. custompartitioned between ethyl acetate (2 L) and 10% aqueous potassium carbonate (2 L)
  5. washand the organic phase is washed (10% aqueous potassium carbonate (2 L) and brine (2 L))
  6. dry with materialdried (MgSO4)
  7. customevaporated to a liquid
  8. washChromatography over silica gel, eluting with 5% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-834651e122e04caea28c97f461deb4bd
Source dataset
uspto-grants-2011_06
Patent number
US07960419B2

Reaction notes

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