Acetic Acid → HCID 85304764, compound

HRID 536699Notes

Reaction equation

CO[CH:3]([O:15][CH3:16])[C:4]1[C:9](CO)=[CH:8][C:7]2[O:12][CH2:13][O:14][C:6]=2[CH:5]=1.[CH3:17][O:18][C:19]([C:21]#[C:22][C:23]([O:25][CH3:26])=[O:24])=[O:20].CC(O)=O>>[O:15]1[CH:16]2[C:9]3[C:4]([CH:3]1[C:22]([C:23]([O:25][CH3:26])=[O:24])=[C:21]2[C:19]([O:18][CH3:17])=[O:20])=[CH:5][C:6]1[O:14][CH2:13][O:12][C:7]=1[CH:8]=3

Participants

Reactant 3

HCID 176Acetic Acid

HCID 12980Dimethyl acetylenedicarboxylate

HCID 9991266HCID 9991266, compound

Product 1

HCID 85304764HCID 85304764, compoundYield 176.5%

Procedure

The substrate 2 (23.7 g, 105 mmol) was dissolved in excess DMAD (251 g, 1.76 mol) and glacial AcOH (23.2 mL, 0.4 mol), and the mixture was stirred for 2 h at 80° C. Excess DMAD was removed by vacuum distillation, and flash chromatography (30% EtOAc/hexanes) gave 3 (56.4 g, 90%) as a yellow solid. On a smaller scale, 2 (5.53 g, 24.1 mmol) gave 3 in 92% yield (13.6 g): mp 117-119° C.; 1H NMR (300 MHz, CDCl3) δ 3.79 (s, 6H), 5.86 (s, 2H), 5.90 (d, J=1 Hz, 1H), 5.95 (d, J=1 Hz, 1H), 6.95 (s, 2H); 13C NMR (125 MHz, CDCl3) δ 53.0, 85.7, 102.2, 105.2, 141.4, 146.2, 152.5, 163.5. Anal. Calculated for C15H12O7: C, 59.21; H, 3.98. Found: C, 59.27; H, 4.11.

Workup

customExcess DMAD was removed by vacuum distillation, and flash chromatography (30% EtOAc/hexanes)

Sources & evidence

ORD record: ord-f4838a84f2c6485b8c2eb55d4b8975a8
Source dataset: uspto-grants-2014_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08859614B2

Reaction notes

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