Hydrochloric Acid → Z-2,2-dimethyl-5-carboxymethylene-1,3-dioxolan-4-one

HRID 1786781Notes

Reaction equation

[CH2-:1][C:2]([CH3:4])=[O:3].[CH2-]C(C)=O.[C:9]([OH:18])(=[O:17])[CH:10]([CH:12]([C:14]([OH:16])=[O:15])O)O.CC(C)([O-])C.[K+].Cl.O1CCOCC1>O1CCCC1.C(OCC)(=O)C>[CH3:1][C:2]1([CH3:4])[O:16][C:14](=[O:15])/[C:12](=[CH:10]/[C:9]([OH:18])=[O:17])/[O:3]1

Participants

Conditions

Temperature: -40 °C

Procedure

A solution of tartaric acid bis(acetonide) prepared as in Example 1 (1.84 g, 8.0 mmol) in anhydrous tetrahydrofuran (15 mL) was cooled to −40° C. A 1 M solution of potassium tert-butoxide in tetrahydrofuran (8.0 mL, 8 mmol) was added by syringe over the course of 5 min. The mixture was stirred an additional 20 min. at −40° C. after which 4 M HCl in dioxane (3.0 mL, 12 mmol) was added and the reaction was allowed to warm. Ethyl acetate (75 mL) and 1 N HCl (25 mL) were added. The organic layer was separated and washed with water (25 mL). Removal of volatiles on the rotary evaporator afforded the crude product (1.37 g, 99%). This material contained ca. 5% of a side-product presumed to be the E-stereoisomer and characterized by an NMR singlet at δ 5.48 as well as ca. 10% of recovered bis(acetonide) starting material. A 0.63 g sample of this material was crystallized from hot ethyl acetate to afford Z-2,2-dimethyl-5-carboxymethylene-1,3-dioxolan-4-one as fine white needles (0.37 g).

Workup

additionwas added
temperatureto warm
customThe organic layer was separated
washwashed with water (25 mL)
customRemoval of volatiles
customon the rotary evaporator
customafforded the crude product (1.37 g, 99%)
customA 0.63 g sample of this material was crystallized from hot ethyl acetate

Sources & evidence

ORD record: ord-356b8a02358b4df6a4ce5ed056919e97
Source dataset: uspto-grants-2009_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07507838B2

Reaction notes

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