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

HRID 1429273
ノート
印刷プレビュー

反応式

HRID 1429273 の反応式
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
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

7

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 1140Toluene溶媒
HCID 7929
M-Xylene
溶媒
HCID 8028Tetrahydrofuran溶媒

反応条件

温度
150 °C

実験手順

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

後処理

  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)

出典と根拠

ORDレコード
ord-2aaff5b6d3144870b914c438c391d18e
出典データセット
uspto-grants-2015_01
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08937150B2

反応ノート

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