Acetyl chloride → (+)-O-Acetyl-D-malic Anhydride

HRID 516814Notes

Reaction equation

HRID 516814 reaction equation
[C:1]([OH:9])(=[O:8])[C@@H:2]([CH2:4][C:5]([OH:7])=O)[OH:3].[C:10](Cl)(=[O:12])[CH3:11]>>[C:10]([O:3][C@@H:2]1[CH2:4][C:5](=[O:7])[O:8][C:1]1=[O:9])(=[O:12])[CH3:11]

Participants

3

Reactant 2

HCID 6367Acetyl chlorideHCID 92824D-Malic acid

Product 1

HCID 9815264(+)-O-Acetyl-D-malic Anhydride

Conditions

Temperature
45 °C

Procedure

A mixture of D-malic acid (10 g, 75 mmol, Major Chemicals Co. Ltd. lot #KS00404) in acetyl chloride (30 mL, Aldrich cat #11,418-9) was heated to 45° C. for 6 h. The excess acetyl chloride was evaporated in vacuo and the residue was taken up in dichloromethane (10-15 mL). The volatiles were removed in vacuo and the residual oil was stored at 4° C. for 18 h. Under cold storage, the oil crystallized, giving rise to (R)-(+)-2-acetoxysuccinic anhydride (95a) as a white solid (11.7 g, quant yield); m.p. 52° C.; [α]D +23.82° (c 5.44, acetone); 1H-NMR (300 MHz, CDCl3) δ: 5.51 (dd, 1H, J 6 Hz, 9 Hz), 3.36 (dd, 1H, J 19 Hz, 9 Hz), 3.00 (dd, 1H, J 19 Hz, 6 Hz), 2.17 (s, 3H); 13C-NMR (75 MHz, CDCl3) δ: 169.61 (+), 167.66 (+), 166.21 (+), 67.51 (−), 35.10 (+), 20.16 (−).

Workup

  1. customThe excess acetyl chloride was evaporated in vacuo
  2. customThe volatiles were removed in vacuo
  3. customUnder cold storage, the oil crystallized

Sources & evidence

ORD record
ord-18af8f19171547eb91df3a25aa27221d
Source dataset
uspto-grants-2015_08
Patent number
US09115081B2

Reaction notes

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