Diisopropylamine → HCID 178470409, compound

HRID 1243820Notes

Reaction equation

HRID 1243820 reaction equation
[N+:1](=[CH:3][C:4]([O:6][CH2:7][CH3:8])=[O:5])=[N-:2].C([N-]C(C)C)(C)C.[Li+].C([Li])CCC.C(NC(C)C)(C)C.[C:29]1([C:35]2([C:42]3[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=3)[CH2:40][CH2:39][C:38](=O)[CH:37]=[CH:36]2)[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1>O1CCCC1.C1(C)C=CC=CC=1.C(O)(=O)C>[C:29]1([C:35]2([C:42]3[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=3)[CH2:36][C:37]3[C:38](=[C:3]([C:4]([O:6][CH2:7][CH3:8])=[O:5])[NH:1][N:2]=3)[CH:39]=[CH:40]2)[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1

Participants

9

Reactant 5

HCID 7912DiisopropylamineHCID 12192Ethyl diazoacetateHCID 1382802-Cyclohexen-1-one, 4,4-diphenyl-HCID 2724682Lithium diisopropylamideHCID 178418339Butyllithium

Product 1

HCID 178470409HCID 178470409, compound

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

20 cm3 of ethyl diazoacetate, followed by slow addition of 210 cm3 of a solution of lithium diisopropylamide prepared beforehand from 140.7 cm3 of 1.6M n-butyllithium and 35.55 cm3 of diisopropylamine in solution in 35 cm3 of tetrahydrofuran are added dropwise to a solution, maintained at −78° C., of 35 g of 4,4-diphenylcyclohex-2-enone in 315 cm3 of tetrahydrofuran. After addition, the reaction mixture is stirred at a temperature in the region of −78° C. for 2 hours. 28.2 cm3 of glacial acetic acid are then added and the temperature is allowed to rise to the region of 20° C. 350 cm3 of toluene are then added and the resulting solution is successively washed with 200 cm3 of saturated aqueous sodium bicarbonate solution and 200 cm3 of water. The organic phase obtained is concentrated under reduced pressure in order to remove the tetrahydrofuran. The resulting toluene phase is refluxed for 4 hours in a round-bottomed flask surmounted with a Dean-Stark trap and then concentrated to dryness under reduced pressure. The residue obtained is purified by flash chromatography on silica gel (35–70 μm), eluting with a cyclohexane/ethyl acetate (80/20) mixture; 43.1 g of ethyl 6,6-diphenyl-6,7-dihydro-2H-indazole-3-carboxylate are obtained in the form of a white powder, the characteristics of which are as follows:

Workup

  1. additionare added dropwise to a solution
  2. additionAfter addition
  3. customto rise to the region of 20° C
  4. washthe resulting solution is successively washed with 200 cm3 of saturated aqueous sodium bicarbonate solution and 200 cm3 of water
  5. customThe organic phase obtained
  6. concentrationis concentrated under reduced pressure in order
  7. customto remove the tetrahydrofuran
  8. temperatureThe resulting toluene phase is refluxed for 4 hours in a round-bottomed flask
  9. concentrationconcentrated to dryness under reduced pressure
  10. customThe residue obtained
  11. customis purified by flash chromatography on silica gel (35–70 μm)
  12. washeluting with a cyclohexane/ethyl acetate (80/20) mixture

Sources & evidence

ORD record
ord-d69f4a1d9fec4677a27e126234984f3e
Source dataset
uspto-grants-2006_10
Patent number
US07119115B2

Reaction notes

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