Triethylamine → Benzyl 7-(diethoxyphosphoryl)-3,7-diazabicyclo[4.1.0]heptane-3-carboxylate

HRID 73558Notes

Reaction equation

HRID 73558 reaction equation
[CH:1]12[NH:7][CH:6]1[CH2:5][CH2:4][N:3]([C:8]([O:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[O:9])[CH2:2]2.[P:18](Cl)(=[O:25])([O:22][CH2:23][CH3:24])[O:19][CH2:20][CH3:21].C(N(CC)CC)C>C(Cl)Cl>[CH2:20]([O:19][P:18]([N:7]1[CH:1]2[CH:6]1[CH2:5][CH2:4][N:3]([C:8]([O:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[O:9])[CH2:2]2)([O:22][CH2:23][CH3:24])=[O:25])[CH3:21]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 13139Diethyl chlorophosphateHCID 21874358HCID 21874358, compound

Product 1

HCID 59455678Benzyl 7-(diethoxyphosphoryl)-3,7-diazabicyclo[4.1.0]heptane-3-carboxylateYield 21%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of benzyl 3,7-diazabicyclo[4.1.0]heptane-3-carboxylate (1.0 equiv.) in DCM (0.26M) was added diethyl phosphorochloridate (1.3 equiv.) and triethyl amine (1.5 equiv.). The reaction was stirred for 24 h, then concentrated to dryness. Added water and ethyl acetate, the organics were extracted, dried with Na2SO4, and concentrated. The crude was purified via silica gel column chromatography eluting with ethyl acetate and hexanes (50% to 100% ethyl acetate) to yield benzyl 7-(diethoxyphosphoryl)-3,7-diazabicyclo[4.1.0]heptane-3-carboxylate as a clear oil in 21% yield. LCMS (m/z): 369.0 (MH+).

Workup

  1. concentrationconcentrated to dryness
  2. extractionAdded water and ethyl acetate, the organics were extracted
  3. dry with materialdried with Na2SO4
  4. concentrationconcentrated
  5. customThe crude was purified via silica gel column chromatography
  6. washeluting with ethyl acetate and hexanes (50% to 100% ethyl acetate)

Sources & evidence

ORD record
ord-a4002285b69e47adb35c52e551f7657b
Source dataset
uspto-grants-2014_09
Patent number
US08829193B2

Reaction notes

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