Formaldehyde → Chloromethyl benzoate

HRID 1360623Notes

Reaction equation

HRID 1360623 reaction equation
C=O.C([Cl:11])(=O)C1C=CC=CC=1.[C:12]([O:15][CH2:16]C)(=[O:14])[CH3:13].[CH3:18][CH2:19][CH2:20][CH2:21][CH2:22]C>[Cl-].[Zn+2].[Cl-]>[Cl:11][CH2:16][O:15][C:12](=[O:14])[C:13]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

5

Reactant 3

HCID 712Formaldehyde2×HCID 7412Benzoyl chlorideHCID 21226206Ethyl acetate hexane

Product 1

HCID 79257Chloromethyl benzoate

Reagents, catalysts & solvents 1

HCID 3007855ZincchlorideCatalyst

Procedure

Para-formaldehyde (4.5 g) and zinc chloride (catalytic amount) were mixed together at 0° C. Benzoyl chloride (0.142 mole, 20 g) was added dropwise over 1 hour. The reaction was warmed to ambient temperature, then was heated to 55° C. for 10 hours. The progress of the reaction was followed by TLC (silica gel, 5/95, ethyl acetate/hexane). Since the starting material was still seen, an additional 1 g para-formaldehyde was added. The reaction was continued stirring at 55° C. for an additional 10 hours, cooled and flash chromatographed on 500 g silica gel, eluting with a solvent mixture of 2% ethyl acetate and 98% hexane. The solvent was evaporated in vacuo. Since the product had a low boiling point, the rotovapor bath temperature was not above 35° C. The desired product, 11.82 g (49%) was obtained as clear oil. MS (ES+): m/e 171 (M+H).

Workup

  1. temperaturewas heated to 55° C. for 10 hours
  2. temperaturecooled
  3. customflash chromatographed on 500 g silica gel
  4. washeluting with a solvent mixture of 2% ethyl acetate and 98% hexane
  5. customThe solvent was evaporated in vacuo
  6. customwas not above 35° C

Sources & evidence

ORD record
ord-a97a07a8a9ba482ebccb0c16139f3dc7
Source dataset
uspto-grants-2011_02
Patent number
US07879825B2

Reaction notes

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