Triphenylphosphine → 1-(Diphenylmethyl)-3-methylazetidin-3-amine

HRID 519212Notes

Reaction equation

HRID 519212 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N:20]([C:23]1([CH3:40])[CH2:26][N:25]([CH:27]([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH2:24]1)=[N+]=[N-]>C1COCC1.O>[CH:27]([N:25]1[CH2:26][C:23]([NH2:20])([CH3:40])[CH2:24]1)([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1

Participants

5

Reactant 2

HCID 11776TriphenylphosphineHCID 86727622HCID 86727622, compound

Product 1

HCID 100151051-(Diphenylmethyl)-3-methylazetidin-3-amineYield 84.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of triphenylphosphine (3.97 g, 15.14 mmol) and 3-azido-1-benzhydryl-3-methyl-azetidine (2.1 g, 7.57 mmol) in THF (20 mL) and water (2 mL) was stirred for 48 h. The solvent was removed in vacuo and a solution of hydrochloric acid (1M, 100 mL) was added to the residue. The aqueous solution was washed with DCM (50 mL) and the aqueous solution was basified to pH 8 with a solution of sodium hydroxide in water (1M). Then, the aqueous solution was extracted with EtOAc (3×50 mL). The combined organic phase was concentrated in vacuo and the residue was purified by column chromatography on silica gel (eluting with 10-100% EtOAc in petroleum ether) to give crude 1-benzhydryl-3-methyl-azetidin-3-ylamine (1.6 g, 6.37 mmol, 84%). 1H NMR (CDCl3, 400 MHz): δ7.40-7.33 (m, 4H), 7.21-7.25 (m, 4H), 7.12-7.18 (m, 2H), 4.22-4.30 (m, 1H), 3.10-3.20 (m, 2H), 2.80-2.92 (m, 2H), 1.41-1.47 (m, 3H). The two NH2 protons were not observed in CDCl3.

Workup

  1. customThe solvent was removed in vacuo
  2. additiona solution of hydrochloric acid (1M, 100 mL) was added to the residue
  3. washThe aqueous solution was washed with DCM (50 mL)
  4. extractionThen, the aqueous solution was extracted with EtOAc (3×50 mL)
  5. concentrationThe combined organic phase was concentrated in vacuo
  6. customthe residue was purified by column chromatography on silica gel (eluting with 10-100% EtOAc in petroleum ether)

Sources & evidence

ORD record
ord-60411530ab9d45c8a7f753b0323cf044
Source dataset
uspto-grants-2015_08
Patent number
US09115151B2

Reaction notes

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