3,4-Dichlorophenol → HCID 67508935, compound

HRID 1400057Notes

Reaction equation

HRID 1400057 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]23[CH:13]([CH2:14][OH:15])[CH:12]2[CH2:11][N:10]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:9]3)=[CH:4][CH:3]=1.BrC1C=CC(C23C(COC)C2CN(C(OC(C)(C)C)=O)C3)=CC=1.[Cl:46][C:47]1[CH:48]=[C:49](O)[CH:50]=[CH:51][C:52]=1[Cl:53].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[Cl:46][C:47]1[CH:48]=[C:49]([CH:50]=[CH:51][C:52]=1[Cl:53])[O:15][CH2:14][CH:13]1[C:8]2([C:5]3[CH:4]=[CH:3][C:2]([Br:1])=[CH:7][CH:6]=3)[CH:12]1[CH2:11][N:10]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:9]2

Participants

7

Reactant 5

HCID 72583,4-DichlorophenolHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 67509194HCID 67509194, compoundHCID 67980755HCID 67980755, compound

Product 1

HCID 67508935HCID 67508935, compoundYield 74.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of tert-butyl 1-(4-bromophenyl)-6-(hydroxymethyl)-3-aza-bicyclo[3.1.0]hexane-3-carboxylate (500 mg, 1.31 mmol) obtained in Step 4 of Intermediate IX, in dry THF (10 mL), were sequentially added 3,4-dichlorophenol (428.0 mg, 2.62 mmol), triphenylphosphine (688.4 mg, 2.62 mmol) and diethyl azodicarboxylate (0.414 mL, 2.62 mmol) at 0° C. under nitrogen atmosphere. The reaction mixture was stirred at r.t. overnight. After the completion of the reaction as confirmed by TLC, the reaction mixture was quenched with 1N NaOH (3 mL). The compound was extracted with ethylacetate. The organic layer was washed with water, separated, dried over Na2SO4 and concentrated in vacuo to afford the crude compound, which was purified by column chromatography (silica gel, 2:8 EtOAc:Pet. ether) to afford the title compound (500 mg, 74%) as a viscous oil.

Workup

  1. customat 0° C.
  2. customAfter the completion of the reaction
  3. customthe reaction mixture was quenched with 1N NaOH (3 mL)
  4. extractionThe compound was extracted with ethylacetate
  5. washThe organic layer was washed with water
  6. customseparated
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated in vacuo
  9. customto afford the crude compound, which
  10. customwas purified by column chromatography (silica gel, 2:8 EtOAc:Pet. ether)

Sources & evidence

ORD record
ord-5eac66b94bae430e8a7da3a211367308
Source dataset
uspto-grants-2014_12
Patent number
US08906913B2

Reaction notes

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