Diisopropylamine → HCID 21928739, compound

HRID 1243857Notes

Reaction equation

HRID 1243857 reaction equation
[N+:1](=[CH:3][C:4]([O:6][CH2:7][CH3:8])=[O:5])=[N-:2].[CH3:9][CH:10]1[CH2:15][C:14](=O)[CH:13]=[CH:12][C:11]1([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.C([N-]C(C)C)(C)C.[Li+].C([Li])CCC.C(NC(C)C)(C)C>O1CCCC1.C(OCC)C.C(O)(=O)C>[CH3:9][CH:10]1[C:15]2[NH:2][N:1]=[C:3]([C:4]([O:6][CH2:7][CH3:8])=[O:5])[C:14]=2[CH:13]=[CH:12][C:11]1([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Participants

9

Reactant 5

HCID 7912DiisopropylamineHCID 12192Ethyl diazoacetateHCID 2724682Lithium diisopropylamideHCID 21929307HCID 21929307, compoundHCID 178418339Butyllithium

Product 1

HCID 21928739HCID 21928739, compound

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-70 °C

Procedure

0.41 cm3 of ethyl diazoacetate is added dropwise to a solution, cooled to −78° C., of 0.8 g of 5-methyl-4,4-diphenylcyclohex-2-enone, which may be obtained according to J. Amer. Chem. Soc. 1995, 107, 5245–61, in 30 cm3 of tetrahydrofuran, followed by slow addition of 11.67 cm3 of lithium diisopropylamide solution prepared from 3 cm3 of 1.6M n-butyllithium and 0.67 cm3 of diisopropylamine in solution in 8 cm3 of tetrahydrofuran. After stirring the reaction mixture at a temperature in the region of −70° C. for 2 hours, 0.34 cm3 of glacial acetic acid is added and the temperature is allowed to rise to the region of 20° C. 100 cm3 of ethyl ether are added and the organic phases are then washed with five times 70 cm3 of distilled water, dried over sodium sulphate and concentrated to dryness under reduced pressure. The residue is dissolved in 25 cm3 of toluene, heated at a temperature in the region of 110° C. for 4 hours 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; 0.133 g of ethyl 7-methyl-6,6-diphenyl-6,7-dihydro-1H-indazole-3-carboxylate is obtained in the form of an off-white solid, the characteristics of which are as follows:

Workup

  1. custommay be obtained
  2. customto rise to the region of 20° C
  3. washthe organic phases are then washed with five times 70 cm3 of distilled water
  4. dry with materialdried over sodium sulphate
  5. concentrationconcentrated to dryness under reduced pressure
  6. dissolutionThe residue is dissolved in 25 cm3 of toluene
  7. temperatureheated at a temperature in the region of 110° C. for 4 hours
  8. concentrationconcentrated to dryness under reduced pressure
  9. customThe residue obtained
  10. customis purified by flash chromatography on silica gel (35–70 μm)
  11. washeluting with a cyclohexane/ethyl acetate (80/20) mixture

Sources & evidence

ORD record
ord-7de4c848949a4fc289c5301d5ff4cacf
Source dataset
uspto-grants-2006_10
Patent number
US07119115B2

Reaction notes

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