Boron tribromide → HCID 86760088, compound

HRID 908055Notes

Reaction equation

HRID 908055 reaction equation
[C:1]12([C:11]3[CH:12]=[C:13]([C:25]4[CH:37]=[CH:36][C:28](/[CH:29]=[CH:30]/[C:31]([O:33][CH2:34][CH3:35])=[O:32])=[CH:27][C:26]=4[CH3:38])[CH:14]=[CH:15][C:16]=3[O:17]CC3C=CC=CC=3)[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.B(Br)(Br)Br.CCOC(C)=O.CCCCCC>C(Cl)Cl>[C:1]12([C:11]3[CH:12]=[C:13]([C:25]4[CH:37]=[CH:36][C:28](/[CH:29]=[CH:30]/[C:31]([O:33][CH2:34][CH3:35])=[O:32])=[CH:27][C:26]=4[CH3:38])[CH:14]=[CH:15][C:16]=3[OH:17])[CH2:8][CH:7]3[CH2:9][CH:3]([CH2:4][CH:5]([CH2:6]3)[CH2:10]1)[CH2:2]2

Participants

5

Reactant 3

HCID 25134Boron tribromideHCID 21226206Ethyl acetate hexaneHCID 67389604HCID 67389604, compound

Product 1

HCID 86760088HCID 86760088, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A mixture of 1.44 g (2.84 mmol) of ethyl (E)-4-[3-(1-adamantyl)-4-benzyloxyphenyl]-3-methylcinnamate was stirred in 10 ml of CH2Cl2 at −78° C. under Ar while 8.0 ml of 1.0 M BBr3 in CH2Cl2 was added slowly over a period of 0.5 hour. The reaction mixture was stirred for 2 hours more, at which time the reaction was complete. The mixture was extracted with EtOAc, washed with brine and water, dried (MgSO4), filtered, and concentrated. Flash column chromatography (20% EtOAc/hexane) yielded a pale-yellow solid (0.86 g, 73%: m.p. 193-195° C.; Rf0.47 (20% EtOAc/hexane); 1H NMR (300 MHz, CDCl3) δ 1.78, 2.14 (2 s, 12, AdCH2), 2.09 (s, 3, AdCH), 1.35 (t, J=7.2 Hz, 3 CH3), 2.31 (s, 3, ArCH3), 4.27 (q, J=7.6 Hz, 2, CH2), 4.94 (s, 1, OH), 6.46 (d, J=16.4 Hz, 1, HC═CCO), 6.71 (d, J=8.4 Hz, 1, ArH), 7.03 (dd, J=8.4, 1.6 Hz, 1, ArH), 7.16 (d, J=2.8 Hz, 1, ArH), 7.25 (s, 1, ArH), 7.39 (dd, J=9.2, 2.4 Hz, 1, ArH), 7.41 (s, 1, ArH), 7.71 ppm (d, J=16.0 Hz, 1, C═CHCO).

Workup

  1. additionwas added slowly over a period of 0.5 hour
  2. extractionThe mixture was extracted with EtOAc
  3. washwashed with brine and water
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customFlash column chromatography (20% EtOAc/hexane) yielded a pale-yellow solid (0.86 g, 73%

Sources & evidence

ORD record
ord-819b25d57ace48e890c53a9b378e68cc
Source dataset
uspto-grants-2011_09
Patent number
USRE042700E1

Reaction notes

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