Allyl bromide → HCID 86644271, compound

HRID 2088362Notes

Reaction equation

HRID 2088362 reaction equation
[CH2:1]([O:3][C:4](=[O:11])[CH2:5][NH:6][C:7](=[O:10])NN)[CH3:2].[C:12](=[N:25][NH:26][C:27]([NH2:29])=[O:28])([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.CC(C)([O-])C.[K+].C(Br)C=C>C1COCC1.CCOCC>[CH2:1]([O:3][C:4](=[O:11])[CH2:5][NH:6][C:7](=[O:10])[CH2:27][NH:26][NH:25][CH:12]=[CH2:13])[CH3:2].[C:12](=[N:25][NH:26][C:27]([NH2:29])=[O:28])([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

Participants

6

Reactant 3

HCID 7841Allyl bromideHCID 23665647Potassium tert-butoxideHCID 86644269HCID 86644269, compound

Product 1

HCID 86644271HCID 86644271, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of semicarbazone 5i, (50 mg, 0.15 mmol) in THF (0.5 mL), potassium t-butoxide (25 mg, 0.18 mmol) was added at 0° C. under argon. The reaction mixture was stirred for 1 h, treated drop-wise with allyl bromide (20 μL, 0.18 mmol), stirred for 3 h at room temperature (22° C.) under argon, diluted in Et2O (5 mL) and extracted with NaHCO3 (2×2 mL) and brine (2×2 mL). The organic phase was dried over MgSO4, concentrated in-vacuo and purified by flash chromatography using 2:1 Hexane:EtOAc [Rf (6i): 0.45] to yield a an oil (35 mg, 60%). 1H NMR (CDCl3) δ: 1.23 (t, J=7 Hz, 3H), 3.86 (dd, J=1.6 Hz, 3.8 Hz, 2H), 4.05 (d, J=5.7 Hz, 2H), 4.16 (q, J=7 Hz, 2H), 4.78 (dd, J=1 Hz, 10 Hz, 1H), 4.92 (dd, J=1 Hz, 10 Hz, 1H) 5.33-5.43 (m, 1H), 6.89 (t, J=5.5 Hz, 1H), 7.18-7.42 (m, 10H); 13C NMR (CDCl3) δ: 13.8, 42.2, 47.9, 60.8, 116.3, 127.8, 128.2, 128.3, 128.7, 129.3, 129.6, 132.4, 135.6, 138.4, 157.7, 158.4, 170.2; LCMS (ESI) Calcd. for C21H23N3O3, M+: 365.4. Found (M+H)+366.1.

Workup

  1. stirringstirred for 3 h at room temperature (22° C.) under argon
  2. extractionextracted with NaHCO3 (2×2 mL) and brine (2×2 mL)
  3. dry with materialThe organic phase was dried over MgSO4
  4. concentrationconcentrated in-vacuo
  5. custompurified by flash chromatography

Sources & evidence

ORD record
ord-e21dd3e38a4c411eab742b6f976edc0b
Source dataset
uspto-grants-2013_05
Patent number
US08435954B2

Reaction notes

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