Acetic Acid → Butanal, 4-(acetyloxy)-2-methylene-

HRID 1703502Notes

Reaction equation

HRID 1703502 reaction equation
C(OCC=CCOC(=O)C)(=O)C.C(O)(=O)C.C([O:20][CH2:21][CH:22]([CH:29]=O)[CH2:23][CH2:24][O:25][C:26](=[O:28])[CH3:27])(=O)C>C1C=CC=CC=1>[CH:21]([C:22]([CH2:23][CH2:24][O:25][C:26](=[O:28])[CH3:27])=[CH2:29])=[O:20]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 1404022-Butene-1,4-diol diacetateHCID 227617662-Formylbutane-1,4-diyl diacetate

Product 1

HCID 11083989Butanal, 4-(acetyloxy)-2-methylene-Yield 90.3%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A solution of 1,4-diacetoxy-2-butene (170 g.) and hydridocarbonyltris(triphenylphosphine) rhodium (I) (0.5 g.) in benzene (340 g.) was heated in a bomb at 75° C. under 2000 psig of a synthesis gas (50% by volume H2 and 50% by volume CO gas). After a few hours, the bomb was cooled and vented and the benzene was removed from the reaction product by distillation. The resulting crude 1,4-diacetoxy-2-formylbutane was then heated to 120°-130° C. in a distillation apparatus under a vacuum of 5 mm Hg. and a distillate (190.3 g. b.p. 60°-80° C.) was collected. The distillate on redistillation gave acetic acid, 2-formyl-4-acetoxybutene (127.1 g., 90.3% yield, b.p. 77°-79° C./ 6 mm Hg) and 1,4-diacetoxy-2-formyl butane (12.5 g., 6.2% yield, b.p. 110°-113° C./ 1 mm Hg.

Workup

  1. waitAfter a few hours
  2. temperaturethe bomb was cooled
  3. customthe benzene was removed from the reaction product by distillation
  4. temperatureThe resulting crude 1,4-diacetoxy-2-formylbutane was then heated to 120°-130° C. in a distillation apparatus under a vacuum of 5 mm Hg
  5. distillationand a distillate (190.3 g. b.p. 60°-80° C.) was collected
  6. distillationThe distillate on redistillation

Sources & evidence

ORD record
ord-3bd0c561003e4f88985468e86817c9d6
Source dataset
uspto-grants-1978_11
Patent number
US04124619

Reaction notes

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