Dichloromethane → HCID 11588348, compound

HRID 731999Notes

Reaction equation

HRID 731999 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]2[C:6]3[C:11]([CH:12]([CH3:26])[N:13]([C:16](=[O:25])[C:17]4[CH:22]=[CH:21][C:20]([O:23]C)=[CH:19][CH:18]=4)[C:14]=2[CH:15]=1)=[CH:10][C:9]([F:27])=[CH:8][CH:7]=3.C1CCCCC=1.B(Br)(Br)Br.ClCCl>>[F:1][C:2]1[CH:3]=[CH:4][C:5]2[C:6]3[C:11]([CH:12]([CH3:26])[N:13]([C:16]([C:17]4[CH:22]=[CH:21][C:20]([OH:23])=[CH:19][CH:18]=4)=[O:25])[C:14]=2[CH:15]=1)=[CH:10][C:9]([F:27])=[CH:8][CH:7]=3

Participants

5

Reactant 4

HCID 6344DichloromethaneHCID 8079CyclohexeneHCID 25134Boron tribromideHCID 68815094HCID 68815094, compound

Product 1

HCID 11588348HCID 11588348, compoundYield 99%

Procedure

4-[(3,8-Difluoro-6-methylphenanthridin-5(6H)-yl)carbonyl]phenol—A stirred suspension of 3,8-difluoro-5-(4-methoxybenzoyl)-6-methyl-5,6-dihydrophenanthridine (0.20 g, 0.55 mmol) and cyclohexene (1.64 g, 20.0 mmol) was treated at room temperature under nitrogen with a solution of 1.0 M boron tribromide in dichloromethane (4.0 mL, 4.0 mmol). After stirring for approximately two hours at room temperature, the reaction was cooled to −20° C. and quenched with methanol (5 mL). The solvent was evaporated in vacuo to a dark oil. The dark oil was purified by preparative liquid chromatography on a Biotage® 40 Mi column of pre-packed silica gel (90 g), eluting with a gradient of between 5% and 30% methyl tert-butyl ether in hexane at a flow rate of 50 mL/min to afford, after evaporation of the solvent in vacuo and trituration with diethyl ether-hexane, the title compound (0.19 g, 0.54 mmol, 99%) as a homogeneous, colorless, racemic solid, m.p. 193-195° C.; MS [(+ESI), m/z]: 352 [M+H]+; MS [(−ESI), m/z]: 350 [M−H]−; 1H NMR (400 MHz, DMSO-d6) δ: 1.21 (d, J=7.0 Hz, 3H), 5.71 (q, J=6.8 Hz, 1H), 6.55 (dd, J=10.5, 2.5 Hz, 1H), 6.70 (d, J=8.6 Hz, 2H), 7.06 (td, J=8.6, 2.6 Hz, 1H), 7.16 (d, J=8.6 Hz, 2H), 7.27 (td, J=8.8, 2.7 Hz, 1 H), 7.38 (dd, J=9.2, 2.7 Hz, 1H), 7.97 (dd, J=9.0, 6.4 Hz, 1H), 8.01 (dd, J=9.1, 6.0 Hz, 1H), 10.04 (s, 1H).

Workup

  1. temperaturethe reaction was cooled to −20° C.
  2. customquenched with methanol (5 mL)
  3. customThe solvent was evaporated in vacuo to a dark oil
  4. customThe dark oil was purified by preparative liquid chromatography on a Biotage® 40 Mi column of pre-packed silica gel (90 g)
  5. washeluting with a gradient of between 5% and 30% methyl tert-butyl ether in hexane at a flow rate of 50 mL/min
  6. customto afford
  7. customafter evaporation of the solvent in vacuo and trituration with diethyl ether-hexane

Sources & evidence

ORD record
ord-e4b46d7de3f54ae296aea960cd88a211
Source dataset
uspto-grants-2009_09
Patent number
US07585871B2

Reaction notes

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