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

HRID 1429273
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HRID 1429273 반응식
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
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참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 1140Toluene용매
HCID 7929
M-Xylene
용매
HCID 8028Tetrahydrofuran용매

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온도
150 °C

실험 절차

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

후처리

  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)

출처 및 근거

ORD 기록
ord-2aaff5b6d3144870b914c438c391d18e
출처 데이터셋
uspto-grants-2015_01
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08937150B2

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