Water → Ethyl E-2-phosphono-3-[2-(1-tridecynyl)phenyl]propenoate

HRID 265241노트

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HRID 265241 반응식
C([O:3][P:4]([O:32]CC)(/[C:6](=[CH:12]/[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[C:19]#[C:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])/[C:7]([O:9][CH2:10][CH3:11])=[O:8])=[O:5])C.Br[Si](C)(C)C.CC(C)=O.CCCCCCC.O>C(Cl)Cl.CC(C)=O>[P:4](/[C:6](=[CH:12]/[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[C:19]#[C:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])/[C:7]([O:9][CH2:10][CH3:11])=[O:8])([OH:32])([OH:5])=[O:3]

참가 물질

7

반응물 4

HCID 962Water2회HCID 76113BromotrimethylsilaneHCID 15284941Ethyl 2-(diethoxyphosphinyl)-3-[2-(1-tridecynyl)phenyl]-2-E-propenoateHCID 21879760Acetone heptane

생성물 1

HCID 67708256Ethyl E-2-phosphono-3-[2-(1-tridecynyl)phenyl]propenoate수율 47.6%

시약·촉매·용매 2

HCID 180Acetone용매HCID 6344Dichloromethane용매

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온도
0 °C

실험 절차

Ethyl 2-(diethoxyphosphinyl)-3-[2-(1-tridecynyl)phenyl]-2-E-propenoate (0.50 g, 1.02 mmol) prepared according to Example 5 was dissolved in dry CH2Cl2 (3 ml) and CD2Cl2 (2 ml, dried over activated neutral alumina) and cooled to 0° C. Bromotrimethylsilane (0.31 ml, 2.35 mmol) was added over a two to three minute period. The progress of the reaction was monitored by 31 p NMR, to follow disappearance of the starting material. After about 5 hours, the solvent was removed under reduced pressure. Acetone-heptane (5.5 ml, 10:1) containing 0.045 ml (2.5 mmol) water was added and the reaction was stirred for 1.5 hours. At the end of this time the solvent was stripped. Since NMR indicated incomplete reaction, acetone (5 ml) containing water (0.05 ml, 2.8 mmol) was added and stirring was continued for two hours. After stripping the solvent, the reaction was still incomplete. It required 2.5 more hours under these conditions to complete the reaction. The solvent was stripped off and the residue was chromatographed on silica eluting with 10% chloroform and 20% methanol in heptane. Fractions containing product were recrystallized from heptane yielding a white solid, 0.211 g, 0.486 mmol, 47.6% yield; mp 68°-69° C.; 1H NMR (CDCl3) ∂0.86 (m, 3H), 1.09 to 1.63 (several m, 21H), 2.40 (t, J=7.1 Hz, 2H), 4.19 (q, J=7.1 Hz, 2H), 7.17 to 7.44 (several m, 4H), 8.15 (d, J=24.7 Hz, 1H), 8.81 (br s, 2.7H); FAB mass spectrum m/z 434 (M+H)+.

후처리

  1. customthe solvent was removed under reduced pressure
  2. additionwas added
  3. additionwas added
  4. stirringstirring
  5. waitwas continued for two hours
  6. customthe reaction
  7. customthe residue was chromatographed on silica eluting with 10% chloroform and 20% methanol in heptane
  8. additionFractions containing product
  9. customwere recrystallized from heptane yielding a white solid, 0.211 g, 0.486 mmol, 47.6% yield

출처 및 근거

ORD 기록
ord-07d6f62192e34a4eb18562720eca2118
출처 데이터셋
uspto-grants-1997_07
특허 번호
US05648349

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