Epibromohydrin → (7-Nitro-2,3-dihydro-1,4-benzodioxin-2-yl)methanol

HRID 9726

Reaction equation

[N+:1]([C:4]1[CH:5]=[C:6]([OH:11])[C:7](=[CH:9][CH:10]=1)[OH:8])([O-:3])=[O:2].C(=O)(O)[O-].[K+].[CH2:17]([CH:19]1[O:21][CH2:20]1)Br>CN(C=O)C>[OH:21][CH2:20][CH:19]1[O:11][C:6]2[CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[CH:10]=[CH:9][C:7]=2[O:8][CH2:17]1

Participants

Conditions

Temperature: 90 °C

Procedure

17.6 g 4-nitrocatechol and 11.0 g potassium bicarbonate were stirred in 200 ml DMF at 10° C. 13.99 g epibromohydrin in 10 ml DMF were added dropwise and stirring was continued at 60° C. for another 17 hrs. DMF was evaporated and the residue diluted with 50 ml water and extracted with ethyl acetate. The combined organic phases were washed with caustic soda and water., dried and evaporated. The crude oily product was heated to 90° C. with 200 ml toluene and the supernatant decanted from insoluble parts. After cooling to RT the solution is again decanted from insoluble oils and left at RT for 3 d. A first crop of 0.75 g crystalline title product was obtained. The mother liquor was evaporated and the residue dissolved in 20 dichloromethane at RT. Seeding and chilling to 0° C. yielded another 2.78 g crystalline title product.

Workup

customDMF was evaporated
additionthe residue diluted with 50 ml water
extractionextracted with ethyl acetate
washThe combined organic phases were washed with caustic soda and water
custom, dried
customevaporated
customthe supernatant decanted from insoluble parts
temperatureAfter cooling to RT the solution
customis again decanted from insoluble oils
waitleft at RT for 3 d

Sources & evidence

ORD record: ord-bc98e3ec676947a9ac1de87fe6360973
Source dataset: uspto-grants-2006_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07091345B2

Linked notes

Loading…