Hydrochloric Acid → 6-Allyloxy-1,3-dihydro-1-hydroxy-2,1-benzoxaborole

HRID 529199Notes

Reaction equation

HRID 529199 reaction equation
[OH:1][C:2]1[CH:11]=[CH:10][C:5]2[CH2:6][O:7][B:8]([OH:9])[C:4]=2[CH:3]=1.[H-].[Na+].Br[CH2:15][CH:16]=[CH2:17].Cl>CN(C=O)C>[CH2:17]([O:1][C:2]1[CH:11]=[CH:10][C:5]2[CH2:6][O:7][B:8]([OH:9])[C:4]=2[CH:3]=1)[CH:16]=[CH2:15]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 529192911,3-Dihydro-2,1-benzoxaborole-1,6-diol

Product 1

HCID 529192936-Allyloxy-1,3-dihydro-1-hydroxy-2,1-benzoxaboroleYield 63.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

H181 (200 mg, 1.33 mmol) was dissolved in DMF (8.0 mL) and cooled to 0° C. with ice bath. To this solution under nitrogen were added in sequence NaH (60% in mineral oil, 213 mg, 5.33 mmol) and 3-bromoprop-1-ene (0.46 mL, 5.33 mmol). The reaction mixture was stirred for 5 h then treated with 1.0 M HCl (10.0 mL). After extraction with ethyl acetate, the organic phase was washed with water and brine, and dried over anhydrous Na2SO4. The residue after rotary evaporation was purified by column chromatography over silica gel to give the title compound (160.5 mg, 63.5% yield). 1H NMR (400 MHz, CDCl3): δ 7.25 (d, J=8.4 Hz, 1H), 7.23 (d, J=2.4 Hz, 1H), 7.09 (dd, J=8.1 & 2.4 Hz, 1H), 6.12-6.02 (m, 1H), 5.42 (dd, J=17.2 & 1.6 Hz, 1H), 5.29 (dd, J=17.2 & 1.6 Hz, 1H), 5.06 (s, 2H) and 4.57 (d, J=2.8 Hz, 2H) ppm; Mp: 79-81° C.

Workup

  1. extractionAfter extraction with ethyl acetate
  2. washthe organic phase was washed with water and brine
  3. dry with materialdried over anhydrous Na2SO4
  4. customThe residue after rotary evaporation
  5. customwas purified by column chromatography over silica gel

Sources & evidence

ORD record
ord-e8e2367f04a046e49cf40048da931433
Source dataset
uspto-grants-2016_05
Patent number
US09346834B2

Reaction notes

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