Hydrochloric Acid → Ethyl 3-(1-adamantyl)-2,2-difluoro-3-hydroxypropionate

HRID 1506742Notes

Reaction equation

Br[C:2]([F:9])([F:8])[C:3]([O:5][CH2:6][CH3:7])=[O:4].BrC(Br)C.[CH:14]12[CH2:23][CH:18]3[CH2:19][CH:20]([CH2:22][CH:16]([CH2:17]3)[CH:15]1C=O)[CH2:21]2.B(OC)(OC)[O:27][CH3:28].Cl>[Zn].C(OCC)(=O)C.O1CCCC1>[C:14]12([CH:28]([OH:27])[C:2]([F:9])([F:8])[C:3]([O:5][CH2:6][CH3:7])=[O:4])[CH2:15][CH:16]3[CH2:17][CH:18]([CH2:19][CH:20]([CH2:22]3)[CH2:21]1)[CH2:23]2

Participants

Conditions

Temperature: 60 °C

Procedure

A mixture of 40 g of ethyl bromodifluoroacetate, 3.7 g of dibromoethane and 50 g of tetrahydrofuran was added dropwise to a mixture of 13 g of zinc, 29 g of 2-adamantanecarbaldehyde, 60 mL of trimethyl borate, and 50 g of tetrahydrofuran at a temperature of 50° C., followed by stirring for 10 hours at 60° C. Thereafter, 100 g of 5 wt % hydrochloric acid was added to quench the reaction. Ethyl acetate, 200 g, was added to the reaction solution, from which the organic layer was extracted. The organic layer was washed with saturated sodium chloride water and then with water. The reaction solution after washing was concentrated under reduced pressure, obtaining 23 g of the target compound, ethyl 3-(1-adamantyl)-2,2-difluoro-3-hydroxypropionate as oily matter (yield 54%).

Workup

customto quench
customthe reaction
extractionwas extracted
washThe organic layer was washed with saturated sodium chloride water
washThe reaction solution after washing
concentrationwas concentrated under reduced pressure

Sources & evidence

ORD record: ord-b89605732213476995ce4694213b3fdd
Source dataset: uspto-grants-2015_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09221742B2

Reaction notes

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