tert-Butanol → HCID 22335628, compound

HRID 586638Notes

Reaction equation

HRID 586638 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)=[CH:10][N:11]3[C:15]=2[CH2:14][CH2:13][CH2:12]3)=[CH:4][CH:3]=1.C(N(CC)CC)C.[O:29]=[C:30](Cl)OC(Cl)(Cl)Cl.[C:37]([OH:41])([CH3:40])([CH3:39])[CH3:38]>C1COCC1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[C:9]([C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=3)=[C:10]([C:30]([O:41][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:29])[N:11]3[C:15]=2[CH2:14][CH2:13][CH2:12]3)=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 8471Triethylamine2×HCID 10426DiphosgeneHCID 14855804HCID 14855804, compound

Product 1

HCID 22335628HCID 22335628, compoundYield 38.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

7-(4-Chlorophenyl)-6-phenyl-2,3-dihydro-1H-pyrrolizine (Example 21 b, 0.75 g, 2.5 mmol), dissolved in THF (10 ml), is treated with triethylamine (0.3 ml, 0.25 g, 2.5 mmol). A solution of diphosgene (0.25 g, 1.25 mmol), dissolved in THF (5 ml), is added dropwise to this solution at RT, and it is stirred for 18 h. tert-Butyl alcohol (abs., 1.0 ml, 0.786 g, 10 mmol) and triethylamine (0.7 ml, 0.51 g, 5 mmol) are then added, and the mixture is stirred at RT for a further 48 h. The reaction mixture is partitioned between water (30 ml) and CHCl3 (60 ml), and the ether phase is washed with Na2CO3 solution (5%, 20 ml). After removal of the solvent in vacuo, an oily residue (0.7 g), which by TLC (SiO2, hexane/CH2Cl2 1:1) still contains starting material (Rf 0.75) in addition to product (Rf 0.3), is obtained from the THF/CHCl3 phase dried using Na2SO4 sicc. The residue is purified by CC (SiO2, hexane/CH2Cl2 1:1); 190 mg of the pure ester are obtained.

Workup

  1. additionis added dropwise to this solution at RT
  2. additionare then added
  3. customThe reaction mixture is partitioned between water (30 ml) and CHCl3 (60 ml)
  4. washthe ether phase is washed with Na2CO3 solution (5%, 20 ml)
  5. customAfter removal of the solvent in vacuo
  6. additionin addition to product (Rf 0.3)
  7. customis obtained from the THF/CHCl3 phase
  8. customdried
  9. customThe residue is purified by CC (SiO2, hexane/CH2Cl2 1:1)

Sources & evidence

ORD record
ord-04d796161fb74c2eab193564800a2262
Source dataset
uspto-grants-2005_08
Patent number
US06936632B2

Reaction notes

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