Acetic Anhydride → Ethyl ethoxymethyleneacetoacetate

HRID 1583954Notes

Reaction equation

[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[CH:10](OCC)(OCC)[O:11][CH2:12][CH3:13].C(OC(=O)C)(=O)C>>[CH2:12]([O:11][CH:10]=[CH:5][C:3](=[O:4])[CH2:2][C:1]([O:7][CH2:8][CH3:9])=[O:6])[CH3:13]

Participants

Reactant 3

HCID 7918Acetic Anhydride

HCID 8868Ethyl Acetoacetate

HCID 31214Ethyl orthoformate

Product 1

HCID 54463595Ethyl ethoxymethyleneacetoacetateYield 70%

Procedure

Using the procedure of Crombie et al., Journ. of Chem. Soc. Perkin Trans. 1, 464-471 (1979), a solution of ethyl acetoacetate (26 g, 0.20 mol), triethyl orthoformate (29.6 g, 0.20 mol) and acetic anhydride (41 g, 0.40 mol) was refluxed for 90 minutes. Distillation under reduced pressure gave the product (1): 26 g, 70% yield; bp=85°-98° C. at 0.5 mm Hg (The following value is reported in the Crombie et al. publication: bp=85° C. at 0.25 mm Hg); NMR (CDCl3) δ 1.2-1.5 (m,6H), 2.4-2.5 (d,3H), 4.0-4.6 (m,4H), 7.7 (d,1H). The signals were split into pairs of closely spaced lines indicative of the cis and trans isomers.

Workup

distillationDistillation under reduced pressure

Sources & evidence

ORD record: ord-58c86ba9456942dfa5d1d28ff4065b67
Source dataset: uspto-grants-1985_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04555517

Reaction notes

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