Bromoform → HCID 131737063, compound

HRID 59672Notes

Reaction equation

[OH-].[Na+].[CH3:3][O:4][CH2:5][C:6]1[C:15]([C:16]([O:18][CH3:19])=[O:17])=[C:14]2[C:9]([CH:10]=[CH:11][CH2:12][O:13]2)=[CH:8][CH:7]=1.[CH:20](Br)([Br:22])[Br:21].C(OCC)(=O)C>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.[Cl-].[Na+].O>[Br:21][C:20]1([Br:22])[C@H:10]2[C@@H:11]1[CH2:12][O:13][C:14]1[C:9]2=[CH:8][CH:7]=[C:6]([CH2:5][O:4][CH3:3])[C:15]=1[C:16]([O:18][CH3:19])=[O:17]

Participants

Conditions

Temperature: 60 °C

Procedure

Aqueous sodium hydroxide solution (50% w/v, 1.63 mL) was added slowly to a vigorously stirred mixture of methyl 7-methoxymethyl-2H-chromene-8-carboxylate (Intermediate 9, 0.875 g), benzyltriethylammonium chloride (0.173 g) and bromoform (15 mL). The resultant mixture was vigorously stirred and heated at 60° C. for 3 hours. After cooling, the mixture was poured into a mixture of brine and ethyl acetate. The aqueous layer was further extracted with ethyl acetate and the combined organic layers were dried (MgSO4) and filtered. The filtrate was evaporated to dryness and the residue was purified by chromatography on silica, eluting with a mixture of TBME and cyclohexane with a gradient of 0-35% to give methyl cis-(1aRS,7bSR)-1,1-dibromo-5-methoxymethyl-1,1a,2,7b-tetrahydrocyclopropa[c]chromene-4-carboxylate (1.06 g) as a white solid.

Workup

temperatureAfter cooling
extractionThe aqueous layer was further extracted with ethyl acetate
dry with materialthe combined organic layers were dried (MgSO4)
filtrationfiltered
customThe filtrate was evaporated to dryness
customthe residue was purified by chromatography on silica
washeluting with a mixture of TBME and cyclohexane with a gradient of 0-35%

Sources & evidence

ORD record: ord-af975f829a5442ab94932d2b4b8ddf42
Source dataset: uspto-grants-2016_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09440943B2

Reaction notes

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