Ethyl diazoacetate → HCID 21929636, compound

HRID 1243846Notes

Reaction equation

HRID 1243846 reaction equation
[N+:1](=[CH:3][C:4]([O:6][CH2:7][CH3:8])=[O:5])=[N-:2].[CH3:9][O:10][C:11]1[CH:16]=[CH:15][C:14]([C:17]2([C:24]3[CH:29]=[CH:28][C:27]([O:30][CH3:31])=[CH:26][CH:25]=3)[CH2:22][CH2:21][C:20](=O)[CH:19]=[CH:18]2)=[CH:13][CH:12]=1.C([N-]C(C)C)(C)C.[Li+].C([Li])CCC>O1CCCC1.CCCCCC.C(NC(C)C)(C)C.C(OCC)C.C(O)(=O)C>[CH3:31][O:30][C:27]1[CH:26]=[CH:25][C:24]([C:17]2([C:14]3[CH:13]=[CH:12][C:11]([O:10][CH3:9])=[CH:16][CH:15]=3)[CH2:18][C:19]3[NH:2][N:1]=[C:3]([C:4]([O:6][CH2:7][CH3:8])=[O:5])[C:20]=3[CH:21]=[CH:22]2)=[CH:29][CH:28]=1

Participants

10

Reactant 4

HCID 12192Ethyl diazoacetateHCID 2724682Lithium diisopropylamideHCID 219290734,4-Bis(4-methoxyphenyl)-2-cyclohexen-1-oneHCID 178418339Butyllithium

Product 1

HCID 21929636HCID 21929636, compound

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 3283Diethyl EtherSolventHCID 7912DiisopropylamineSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-70 °C

Procedure

0.9 cm3 of ethyl diazoacetate is added, dropwise, to a solution, cooled to −78° C., of 2 g of 4,4-bis(4-methoxyphenyl)cyclohex-2-enone in 50 cm3 of tetrahydrofuran, followed by slow addition of 13 cm3 of a lithium diisopropylamide solution prepared beforehand from 6.5 cm3 of 1.6 M n-butyllithium in hexane and 1.46 cm3 of diisopropylamine in solution in 15 cm3 of tetrahydrofuran. After stirring the reaction mixture at a temperature in the region of −70° C. for 3 hours, 1.2 cm3 of glacial acetic acid are added and the temperature is allowed to rise to the region of 20° C. 250 cm3 of ethyl ether are then added and the resultant mixture is then washed with twice 200 cm3 of distilled water and then dried over sodium sulphate and concentrated to dryness under reduced pressure. The residue is dissolved in 65 cm3 of toluene and then heated at a temperature in the region of 110° C. for 1.5 hours, followed by concentrating to dryness under reduced pressure. The residue obtained is purified by flash chromatography on a silica gel (35–70 μm), eluting with a cyclohexane/ethyl acetate (70/30) mixture to give 0.48 g of ethyl 6,6-bis(4-methoxyphenyl)-6,7-dihydro-1H-indazole-3-carboxylate in the form of a yellow foam, the characteristics of which are as follows:

Workup

  1. customprepared
  2. customto rise to the region of 20° C
  3. washthe resultant mixture is then washed with twice 200 cm3 of distilled water
  4. dry with materialdried over sodium sulphate
  5. concentrationconcentrated to dryness under reduced pressure
  6. dissolutionThe residue is dissolved in 65 cm3 of toluene
  7. temperatureheated at a temperature in the region of 110° C. for 1.5 hours
  8. concentrationby concentrating to dryness under reduced pressure
  9. customThe residue obtained
  10. customis purified by flash chromatography on a silica gel (35–70 μm)
  11. washeluting with a cyclohexane/ethyl acetate (70/30) mixture

Sources & evidence

ORD record
ord-a5106ae3d1a34ce983e9588b02610969
Source dataset
uspto-grants-2006_10
Patent number
US07119115B2

Reaction notes

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