Toluene → 3-Chloro-9-bromo-8-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl methoxy)-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one

HRID 2275205

Reaction equation

HRID 2275205 reaction equation
[Br:1][C:2]1[C:22]([OH:23])=[CH:21][C:5]2[C:6]([CH3:20])([CH3:19])[C:7]3[NH:8][C:9]4[C:14]([C:15]=3[C:16](=[O:17])[C:4]=2[CH:3]=1)=[CH:13][CH:12]=[C:11]([Cl:18])[CH:10]=4.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:43][C:44]1([CH3:51])[O:48][C@@H:47]([CH2:49]O)[CH2:46][O:45]1.C1(C)C=CC=CC=1.C(OC(N=NC(OCC)=O)=O)C>C(OCC)(=O)C.C1COCC1>[Cl:18][C:11]1[CH:10]=[C:9]2[C:14]([C:15]3[C:16](=[O:17])[C:4]4[CH:3]=[C:2]([Br:1])[C:22]([O:23][CH2:49][C@H:47]5[CH2:46][O:45][C:44]([CH3:51])([CH3:43])[O:48]5)=[CH:21][C:5]=4[C:6]([CH3:20])([CH3:19])[C:7]=3[NH:8]2)=[CH:13][CH:12]=1

Participants

8

Reactant 5

HCID 1140TolueneHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 736057(+)-SolketalHCID 668346939-Bromo-3-chloro-8-hydroxy-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one

Product 1

HCID 668343203-Chloro-9-bromo-8-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl methoxy)-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-oneYield 52.5%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
50 °C

Procedure

Under nitrogen atmosphere, 9-bromo-3-chloro-8-hydroxy-6,6-dimethyl-5,6-dihydro-benzo[b]carbazol-11-one (Compound S2-4, 76 mg, 0.2 mmol) and triphenylphosphine (69 mg, 1.3 eq.) were added with THF (2 ml), and ((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-methanol (35 mg, 1.3 eq.) and 2.19 N toluene solution (118 μL, 1.3 eq.) of diethyl azodicarboxylic acid were added dropwise thereto, followed by stirring at 50° C. for 2 hr. After cooling, the reaction solution was added with ethyl acetate, washed with brine, dried over sodium sulfate and filtered. The residues obtained after concentration under reduced pressure were purified by silica gel column chromatography (ethyl acetate/dichloromethane) to give a solid, which was then washed with dichloromethane to obtain the title compound (brown powder, 53 mg).

Workup

  1. additionwere added dropwise
  2. temperatureAfter cooling
  3. washwashed with brine
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. customThe residues obtained
  7. concentrationafter concentration under reduced pressure
  8. customwere purified by silica gel column chromatography (ethyl acetate/dichloromethane)
  9. customto give a solid, which
  10. washwas then washed with dichloromethane

Sources & evidence

ORD record
ord-9d04b2c64be2458a95441a99e2ca50c4
Source dataset
uspto-grants-2015_09
Patent number
US09126931B2

Linked notes

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