Methanol → Acetic-formic anhydride

HRID 1707932Notes

Reaction equation

HRID 1707932 reaction equation
[CH:1]([O-:3])=[O:2].[Na+].[C:5](Cl)(=[O:7])C.[NH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[CH2:16][S:17]([NH:20][C:21]([CH3:24])([CH3:23])[CH3:22])(=[O:19])=[O:18].[CH3:25][OH:26]>C(OCC)C.C(Cl)Cl>[C:1]([O:3][CH:5]=[O:7])(=[O:2])[CH3:10].[CH3:24][C:21]([NH:20][S:17]([CH2:16][C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=1[NH:9][CH:25]=[O:26])(=[O:19])=[O:18])([CH3:22])[CH3:23]

Participants

8

Reactant 4

HCID 887MethanolHCID 6367Acetyl chlorideHCID 2723810Sodium FormateHCID 18960411HCID 18960411, compound

Product 2

HCID 75269Acetic-formic anhydrideHCID 18960405HCID 18960405, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Formic acetic anhydride was prepared by stirring a slurry of 34.4 g (0.42 mol) sodium formate in 35 mL ethyl ether and adding 24.9 mL (0.35 mol) of acetyl chloride dropwise keeping the temperature at 25° C. with intermittent cooling. After vigorous stirring for 5 hours the slurry was filtered into another reaction vessel and diluted with 100 mL CH2Cl2, then chilled to 0° C. A solution of 40 g (0.16 mol) 2-amino-N-(1,1-dimethylethyl)benzenemethanesulfonamide in 200 mL CH2Cl2 was then added dropwise keeping the temperature below 10° C. The mixture was then allowed to warm to room temperature and 50 mL methanol was added then stirred 18 hours. Evaporation of the solvent in vacuo left a residue that was taken up in chloroform, washed two times with NaHCO3 solution, dried (MgSO4) and stripped to dryness. The residue was triturated with n-butyl chloride and hexanes (1:1) and collected by filtration to afford 36.8 g of the title compound, m.p. 114°-115° C.

Workup

  1. customat 25° C.
  2. filtrationwas filtered into another reaction vessel
  3. additiondiluted with 100 mL CH2Cl2
  4. customthe temperature below 10° C
  5. temperatureto warm to room temperature
  6. stirringthen stirred 18 hours
  7. customEvaporation of the solvent in vacuo
  8. waitleft a residue that
  9. washwashed two times with NaHCO3 solution
  10. dry with materialdried (MgSO4)
  11. customThe residue was triturated with n-butyl chloride and hexanes (1:1)
  12. filtrationcollected by filtration

Sources & evidence

ORD record
ord-0c934ec129a9479c9dd54f91749e1d35
Source dataset
uspto-grants-1994_10
Patent number
US05356862

Reaction notes

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