Acetic Acid → 3,4-Diacetoxy-1-butene

HRID 54727

Reaction equation

HRID 54727 reaction equation
[C:1]([O:4][C:5](=O)[CH3:6])(=[O:3])[CH3:2].[CH2:8](N(CC)CC)[CH3:9].[C:15]([OH:18])(=[O:17])[CH3:16].O1CC1C=C>COCCOCCOC>[C:15]([O:18][CH:6]([CH2:5][O:4][C:1](=[O:3])[CH3:2])[CH:8]=[CH2:9])(=[O:17])[CH3:16]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 7918Acetic AnhydrideHCID 8471TriethylamineHCID 13586Vinyloxirane

Product 1

HCID 27350013,4-Diacetoxy-1-buteneYield 93%

Reagents, catalysts & solvents 1

HCID 8150DiglymeSolvent

Conditions

Temperature
125 °C

Procedure

A 100-mL autoclave was charged with 45.25 g (0.44 mol) acetic anhydride, 1.62 g (0.016 mol) of triethylamine, 1.94 g (0.032 mol) acetic acid and 3.44 g of diglyme. The autoclave was purged with helium twice, then the vessel was pressurized to 6.2 bars (75 psig) with helium followed by agitation. The reaction mixture was heated to 125° C. Then 31.35 mL (0.40 mol) of 3,4-epoxy-1-butene was introduced to the reactor via syringe pump over 10 seconds. A first sample was taken at 1 min, then sequential samples were obtained every 15 min during the course of 2.25 hrs for analysis by GC. GC analysis of the crude mixture after 2.25 hrs revealed a 93% yield of 3,4-diacetoxy-1-butene with a 95% selectivity and 1.9% 3,4-epoxy-1-butene. The reaction was observed to be first order in 3,4-epoxy-1-butene with a first order rate constant of 0.029 min-1 (Table A). This example demonstrates the catalytic effect of a tertiary amine with two molar equivalents of acetic acid as a co-catalyst (Table B).

Workup

  1. customThe autoclave was purged with helium twice
  2. customsequential samples were obtained every 15 min during the course of 2.25 hrs for analysis by GC

Sources & evidence

ORD record
ord-70dd7ad6f11f4b0da7d032c3ae8f2484
Source dataset
uspto-grants-1997_04
Patent number
US05623086

Linked notes

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