Glycolic Acid → Acetyl chloride, [[(1,1-dimethylethyl)dimethylsilyl]oxy]-

HRID 1700411Notes

Reaction equation

C(O)(=O)CO.FC(F)(F)S([O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])(=O)=O.[C:21](Cl)(=O)[C:22]([Cl:24])=[O:23]>N1C=CC=CC=1.ClCCl.CN(C=O)C>[Si:12]([O:11][CH2:21][C:22]([Cl:24])=[O:23])([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13]

Participants

Conditions

Temperature: 0 °C

Procedure

Glycolic acid (5.0 g, 66 mmol) in pyridine (65 ml) was purged with argon and then treated with tert-butyldimethylsilyl trifluoromethanesulfonate (42 g, 36 ml, 158 mmol) at 0° C., and the mixture was stirred for 2.5 hours. The 2-phase mixture was separated and the upper phase diluted with diethyl ether. This solution was cooled to 0° C., washed briefly with 10% hydrochloric acid, dried (MgSO4) and evaporated to the disilyl material (18 g, 97%). The disilyl material (3.48 g, 12.4 mmol) in dichloromethane (30 ml) at 0° C. was treated with DMF (6 drops) followed by oxalyl chloride (1.84 g, 1.30 ml, 14.50 mmol). After stirring for 3.5 hours, the solution was evaporated and the crude material purified by bulb-to-bulb distillation to afford the title product (60 mbar, 120° C.<T<150° C.) (0.95 g, 37%) contaminated with tert-butyldimethylsiloxane.

Workup

customThe 2-phase mixture was separated
additionthe upper phase diluted with diethyl ether
washwashed briefly with 10% hydrochloric acid
dry with materialdried (MgSO4)
customevaporated to the disilyl material (18 g, 97%)
stirringAfter stirring for 3.5 hours
customthe solution was evaporated
distillationthe crude material purified by bulb-to-bulb distillation

Sources & evidence

ORD record: ord-c401812cefe5415daf29406346374c7d
Source dataset: uspto-grants-2002_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06350775B1

Reaction notes

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