Triphenylphosphine → HCID 15942621, compound

HRID 902342Notes

Reaction equation

HRID 902342 reaction equation
[N:1]([CH2:4][C@@H:5]1[O:11][C:10]2[C:12]([C:16]3[C:21]([Cl:22])=[CH:20][CH:19]=[CH:18][C:17]=3[Cl:23])=[CH:13][CH:14]=[CH:15][C:9]=2[CH2:8][CH2:7][CH2:6]1)=[N+]=[N-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1.O>[Cl:23][C:17]1[CH:18]=[CH:19][CH:20]=[C:21]([Cl:22])[C:16]=1[C:12]1[C:10]2[O:11][C@@H:5]([CH2:4][NH2:1])[CH2:6][CH2:7][CH2:8][C:9]=2[CH:15]=[CH:14][CH:13]=1

Participants

5

Reactant 2

HCID 11776TriphenylphosphineHCID 86609129HCID 86609129, compound

Product 1

HCID 15942621HCID 15942621, compoundYield 80.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (2R)-2-azidomethyl-9-(2,6-dichloro-phenyl)-2,3,4,5-tetrahydro-benzo[b]oxepine (0.24 g, 0.689 mmol) in tetrahydrofuran (10 mL) and water (1 mL) was added polymer-bound triphenylphosphine (˜3 mmol/g, 0.69 g, 2.068 mmol) and the reaction mixture stirred at room temperature for 20 hours. The brown suspension was then filtered through celite, the filter cake washed with ethyl acetate (50 mL) and the combined filtrates concentrated under reduced pressure to afford a yellow syrup. Purification by flash chromatography using a solvent gradient of 0 to 5% ammonia saturated methanol solution in dichloromethane gave 179 mg (80%) of {[(2R)-9-(2,6-dichlorophenyl)-2,3,4,5-tetrahydro-1-benzoxepin-2-yl]methyl}amine as a colorless syrup. The product was dissolved in 2-propanol (1 mL) and diethyl ether (3 mL), a solution of hydrogen chloride (1.0 M in diethyl ether, 0.55 mL, 0.55 mmol) was added followed by hexane (4 mL). The resulting white precipitate was filtered to afford 182 mg (73%) of {[(2R)-9-(2.6-dichlorophenyl)-2,3.4,5-tetrahydro-1-benzoxepin-2-yl]methyl}amine hydrochloride as a white solid. MS (ESI) m/z 322 ([M+H]+).

Workup

  1. filtrationThe brown suspension was then filtered through celite
  2. washthe filter cake washed with ethyl acetate (50 mL)
  3. concentrationthe combined filtrates concentrated under reduced pressure
  4. customto afford a yellow syrup
  5. customPurification by flash chromatography

Sources & evidence

ORD record
ord-75919a60d95843c1881734ff5959c68a
Source dataset
uspto-grants-2008_04
Patent number
US07365095B2

Reaction notes

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