Potassium tert-butoxide → HCID 86661635, compound

HRID 1404655Notes

Reaction equation

HRID 1404655 reaction equation
[F:1][C:2]([F:32])([F:31])[C:3]([NH:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]([N:13]1[CH2:20][C:19]2[CH:21]=[CH:22][CH:23]=[CH:24][C:18]=2[CH:17](Br)[CH:16](Br)[C:15]2[CH:27]=[CH:28][CH:29]=[CH:30][C:14]1=2)=[O:12])=[O:4].CC(C)([O-])C.[K+]>C1COCC1.C(OCC)(=O)C>[F:32][C:2]([F:1])([F:31])[C:3]([NH:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]([N:13]1[CH2:20][C:19]2[CH:21]=[CH:22][CH:23]=[CH:24][C:18]=2[C:17]#[C:16][C:15]2[CH:27]=[CH:28][CH:29]=[CH:30][C:14]1=2)=[O:12])=[O:4]

Participants

5

Reactant 2

HCID 23665647Potassium tert-butoxideHCID 86661636HCID 86661636, compound

Product 1

HCID 86661635HCID 86661635, compoundYield 88.1%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Pyridine hydrobromide perbromide (0.948 g, 2.97 mmol) was added to a solution of 3 (1.05 g, 2.70 mmol) in CH2Cl2 (4 ml) at room temperature, and the reaction mixture was stirred overnight. The reaction mixture was diluted with CH2Cl2 (20 mL), washed with 5% aqueous hydrochloric acid (20 mL), dried over MgSO4, and solvent removed under vacuum. The residue was passed through a short pad of silica gel (CH2Cl2) to give 1.2 g of crude N-(trifluoroacetamidohexanoyl)-5,6,11,12-tetrahydro-11,12-dibromodibenzo[b,f]azocine (4) as an oil. Solution of crude 4 (1.2 g, 2.082 mmol) in THF (5 mL) was added to a solution of potassium t-butoxide (0.584 g, 5.21 mmol) in THF (10 ml) at room temperature, the reaction mixture was stirred for 1 hour, diluted with ethyl acetate (20 mL), washed with 5% aqueous hydrochloric acid, brine, dried over MgSO4, and the solvent was removed under reduced pressure. The crude product was purified by chromatography (hexanes:ethyl acetate, 2:1 to 1:1) to afford 0.76 g (1.834 mmol, 88%) of 5 as brown oil. 1H NMR: δ 7.68 (d, J=7.6 Hz, 1H), 7.45-7.21 (m, 7H), 6.79 (br s, 1H), 5.16 (d, J=14.4 Hz, 1H), 3.67 (d, J=13.6 Hz, 1H), 3.22-3.14 (m, 1H), 3.11-3.02 (m, 1H), 2.24-2.16 (m, 1H), 1.41-1.22 (m, 4H), 1.11-0.9 (m, 2H); MS: m/z 414 [M+]. Calcd for C23H21F3N2O2 414.

Workup

  1. washwashed with 5% aqueous hydrochloric acid, brine
  2. dry with materialdried over MgSO4
  3. customthe solvent was removed under reduced pressure
  4. customThe crude product was purified by chromatography (hexanes:ethyl acetate, 2:1 to 1:1)

Sources & evidence

ORD record
ord-9d277d71000b4e00a3635db141b824f5
Source dataset
uspto-grants-2014_12
Patent number
US08912322B2

Reaction notes

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