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Ammonium Acetate → Di(tert-butyl) [2-bromo-4-(bromomethyl)phenyl](hydroxy)methylphosphonate

HRID 1019161
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HRID 1019161 반응식
[P:1]([O-:12])([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])[O:2][C:3]([CH3:6])([CH3:5])[CH3:4].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[Br:23][CH2:24][C:25]1[CH:32]=[CH:31][C:28]([CH:29]=[O:30])=[C:27]([Br:33])[CH:26]=1.C([O-])(=O)C.[NH4+]>C1COCC1>[Br:33][C:27]1[CH:26]=[C:25]([CH2:24][Br:23])[CH:32]=[CH:31][C:28]=1[CH:29]([P:1](=[O:12])([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])[O:2][C:3]([CH3:5])([CH3:6])[CH3:4])[OH:30]
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참가 물질

6

반응물 4

HCID 517165Ammonium AcetateHCID 2733832Lithium hexamethyldisilazaneHCID 120160382-Bromo-4-(bromomethyl)benzaldehydeHCID 21959072Di-tert-butyl phosphite

생성물 1

HCID 12016039Di(tert-butyl) [2-bromo-4-(bromomethyl)phenyl](hydroxy)methylphosphonate수율 89%

시약·촉매·용매 1

HCID 8028
Tetrahydrofuran
용매
3회

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온도
-78 °C

실험 절차

Di-tert-butyl phosphite (14.8 g, 76.3 mmol, 1.05 eq) was dissolved in 200 ml THF at −78° C. under nitrogen and 72 ml (1.05 eq) of 1.06M Lithium bis(trimethylsilyl)amide in THF was added over 30 min. The mixture was left stirring at −78° C. under nitrogen for 30 min and then added to a solution of the compound of Step 3 (20.2 g, 72.7 mmol, 1 eq) in 200 ml THF at −78° C. The solution was warmed to 0° C. and then poured into 400 ml of half saturated aqueous ammonium acetate. The layers were separated and the aqueous layer was washed with 400 ml isopropyl acetate. The organic layers were combined, dried with sodium sulfate and the solvent removed. The crude solid was then triturated with 15% EtOAc/hexane for 2 hours and 30.4 g (89%) of the title compound was obtained.

후처리

  1. waitThe mixture was left
  2. temperatureThe solution was warmed to 0° C.
  3. customThe layers were separated
  4. washthe aqueous layer was washed with 400 ml isopropyl acetate
  5. dry with materialdried with sodium sulfate
  6. customthe solvent removed
  7. customThe crude solid was then triturated with 15% EtOAc/hexane for 2 hours

출처 및 근거

ORD 기록
ord-b9637d531e224aae95c6df0c31313aad
출처 데이터셋
uspto-grants-2002_11
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06486142B2

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