Triethylamine → HCID 21472370, compound

HRID 2294958Notes

Reaction equation

HRID 2294958 reaction equation
[C:1]([C:3]1([OH:11])[CH:8]2[CH2:9][CH2:10][N:5]([CH2:6][CH2:7]2)[CH2:4]1)#[CH:2].I[C:13]1[CH:23]=[CH:22][C:16]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:15][CH:14]=1.C(N(CC)CC)C>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I.CN(C)C=O>[CH2:20]([O:19][C:17]([C:16]1[CH:22]=[CH:23][C:13]([C:2]#[C:1][C:3]2([OH:11])[CH:8]3[CH2:9][CH2:10][N:5]([CH2:6][CH2:7]3)[CH2:4]2)=[CH:14][CH:15]=1)=[O:18])[CH3:21]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 142891Ethyl 4-iodobenzoateHCID 36135173-Ethynyl-1-azabicyclo[2.2.2]octan-3-ol

Product 1

HCID 21472370HCID 21472370, compoundYield 46.4%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
65 °C

Procedure

A mixture of 3-ethynyl-3-hydroxyquinuclidine (604 mg), ethyl 4-iodobenzoate (1.1 g), bis(triphenylphosphine)-palladium (II) chloride (140 mg), copper (I) iodide (70 mg) and anhydrous triethylamine (4 ml) and anhydrous dimethylformamide (8 ml) was stirred under an atmosphere of argon. The reaction mixture was heated at 65° C. for 18 hours. The reaction mixture was cooled and the triethylamine and dimethylformamide removed by evaporation. To the residue was added 2M sodium hydroxide (25 ml) and the mixture extracted with dichloromethane. The organic phase was washed with water, saturated brine and dried (MgSO4). Evaporation gave a solid which was crystallised from acetonitrile to give 3-[2-(4-ethoxycarbonylphenyl)ethynyl]-3-hydroxyquinuclidine (553 mg) as a colourless solid, m.p. 176°-177° C.; microanalysis, found: C, 72.2; H, 7.3; N, 4.8%; C18H21NO3 requires: C, 72.2; H, 7.07; N, 4.68%; NMR (DMSO-d6): 1.32(3H, t), 1.49-2.01(5H, m), 2.68(4H, t), 2.78-3.14(2H, d of d), 4.32(2H, q), 5.66(1H, br.s), 7.49-7.58(2H, d) and 7.90-7.98(2H, d); m/Z 300 (M+H).

Workup

  1. temperatureThe reaction mixture was cooled
  2. customthe triethylamine and dimethylformamide removed by evaporation
  3. additionTo the residue was added 2M sodium hydroxide (25 ml)
  4. extractionthe mixture extracted with dichloromethane
  5. washThe organic phase was washed with water, saturated brine
  6. dry with materialdried (MgSO4)
  7. customEvaporation
  8. customgave a solid which
  9. customwas crystallised from acetonitrile

Sources & evidence

ORD record
ord-c5e49f8b0d0548cc982ce4b805e36669
Source dataset
uspto-grants-1997_11
Patent number
US05691349

Reaction notes

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