Triethyl phosphite → Diethyl 3,3-bis(3-bromophenyl)azetidin-1-ylphosphonate

HRID 1429273Notes

Reaction equation

HRID 1429273 reaction equation
CS(O[CH2:6][C:7]([C:19]1[CH:24]=[CH:23][CH:22]=[C:21]([Br:25])[CH:20]=1)([C:12]1[CH:17]=[CH:16][CH:15]=[C:14]([Br:18])[CH:13]=1)[CH2:8][N:9]=[N+]=[N-])(=O)=O.[P:26]([O:33]CC)([O:30][CH2:31][CH3:32])[O:27][CH2:28][CH3:29].P(=N)(OCC)(OCC)OCC>C1(C)C=CC=CC=1.C1COCC1.C1(C)C=CC=C(C)C=1>[Br:18][C:14]1[CH:13]=[C:12]([C:7]2([C:19]3[CH:24]=[CH:23][CH:22]=[C:21]([Br:25])[CH:20]=3)[CH2:8][N:9]([P:26](=[O:33])([O:30][CH2:31][CH3:32])[O:27][CH2:28][CH3:29])[CH2:6]2)[CH:17]=[CH:16][CH:15]=1

Participants

7

Reactant 3

HCID 31215Triethyl phosphiteHCID 580319303-Azido-2,2-bis(3-bromophenyl)propyl methanesulfonateHCID 86660806Triethyl phosphorimidate

Product 1

HCID 58032038Diethyl 3,3-bis(3-bromophenyl)azetidin-1-ylphosphonateYield 71.4%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 7929M-XyleneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
150 °C

Procedure

To a solution of 3-azido-2,2-bis(3-bromophenyl)propyl methanesulfonate (1.3 g, 2.66 mmol) in anhydrous toluene (10 mL) and anhydrous THF (5 mL) under N2 was added triethyl phosphite (0.49 mL, 2.79 mmol) at 25° C. The mixture was stirred for 18 h. The reaction was concentrated by rotary evaporation in a dried apparatus. The residue was dried in vacuo, and used in the next reaction without further purification. The crude triethyl phosphorimidate was dissolved in anhydrous m-xylene (5 mL) under N2 and heated in an oil bath at 150° C. for 12 h. After cooled to room temperature, the solvent was removed by rotary evaporation (vacuum pump assisted) to give a thick light orange oil which was purified by prep-TLC (eluent with EtOAc: dichloromethane=1:5) to afford 960 mg of diethyl 3,3-bis(3-bromophenyl)azetidin-1-ylphosphonate (1.9 mmol, 71% after two steps). LC/MS: [M+1]=504. 1HNMR (CDCl3), 400 MHz: δ 1.25-1.36 (m, 6H), 4.05-4.39 (m, 4H), 4.40 (d, 2H, J=5.2

Workup

  1. concentrationThe reaction was concentrated by rotary evaporation in a dried apparatus
  2. customThe residue was dried in vacuo
  3. customused in the next reaction without further purification
  4. temperatureAfter cooled to room temperature
  5. customthe solvent was removed by rotary evaporation (vacuum pump assisted)
  6. customto give a thick light orange oil which
  7. customwas purified by prep-TLC (eluent with EtOAc: dichloromethane=1:5)

Sources & evidence

ORD record
ord-2aaff5b6d3144870b914c438c391d18e
Source dataset
uspto-grants-2015_01
Patent number
US08937150B2

Reaction notes

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