Oxygen → 2-Butene-1,4-diol diacetate

HRID 2399019Notes

Reaction equation

HRID 2399019 reaction equation
O.O.[C:3]([O-:6])(=[O:5])[CH3:4].[Li+].[C:8]([O:11][C:12](=[O:14])[CH3:13])(=[O:10])[CH3:9].[CH2:15]=[CH:16][CH:17]=[CH2:18].O=O>C([O-])(=O)C.[Ag+].C(O)(=O)C>[C:3]([O:6][CH2:15][CH:16]([O:11][C:8](=[O:10])[CH3:9])[CH:17]=[CH2:18])(=[O:5])[CH3:4].[C:3]([O:6][CH2:15][CH:16]=[CH:17][CH2:18][O:11][C:12](=[O:14])[CH3:13])(=[O:5])[CH3:4]

Participants

8

Reactant 4

HCID 977Oxygen2×HCID 78451,3-ButadieneHCID 7918Acetic AnhydrideHCID 23666338Lithium acetate dihydrate

Product 2

HCID 1404022-Butene-1,4-diol diacetateHCID 27350013,4-Diacetoxy-1-butene

Reagents, catalysts & solvents 2

HCID 11246Silver acetateCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
140 °C

Procedure

Another run was conducted according to the instant invention employing the same apparatus as that used in Example I. In this run, the reactor was charged with 7.6 grams (75 mmols) of lithium acetate dihydrate, 6.7 grams (40 mmols) of silver acetate, 50 ml of acetic acid, 25 ml of acetic anhydride, and 11.5 grams (213 mmols) of butadiene charged from the vapor phase. The reactor was placed in an oil bath, pressured to 30 psig with oxygen and heated to 140° C. About one hour was required to bring the temperature of the oil bath up to the desired reaction temperature. During the reaction period of 6.8 hours, the reactor was intermittently pressured with oxygen to 120 psig. At the end of the reaction period, the reactor was vented and there was collected 0.5 grams of unreacted butadiene in a cold trap. The reaction mixture was filtered to recover 4.3 grams of white solid. The filtrate was transferred to a distilling flask and the acetic acid removed by distillation at 75 mm mercury pressure. The distillation residue was taken up in ether, filtered through diatomaceous earth, washed with water, washed with a sodium carbonate solution and then dried over magnesium sulfate and filtered. The ether was removed on a rotary evaporator. The residue remaining weighed 18.2 grams and was analyzed by gas-liquid phase chromatography (GLC). The analysis showed that there was obtained 11.15 grams (64.8 mmols) of 1,2-diacetoxy-3-butene and 3.42 grams (19.9 mmols) of 1,4-diacetoxy-2-butene for a yield of diacetoxybutenes of 40 percent based on the butadiene charged.

Workup

  1. additioncharged from the vapor phase
  2. customThe reactor was placed in an oil bath
  3. customreaction temperature
  4. customDuring the reaction period of 6.8 hours
  5. customAt the end of the reaction period
  6. customthere was collected 0.5 grams of unreacted butadiene in a cold trap
  7. filtrationThe reaction mixture was filtered
  8. customto recover 4.3 grams of white solid
  9. customThe filtrate was transferred to a distilling flask
  10. customthe acetic acid removed by distillation at 75 mm mercury pressure
  11. filtrationfiltered through diatomaceous earth
  12. washwashed with water
  13. washwashed with a sodium carbonate solution
  14. dry with materialdried over magnesium sulfate
  15. filtrationfiltered
  16. customThe ether was removed on a rotary evaporator

Sources & evidence

ORD record
ord-63bf7da2320b4e72a6afca5523bcc6aa
Source dataset
uspto-grants-1977_05
Patent number
US04026924

Reaction notes

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