Allyl bromide → tert-butyl 3-(3-(2-allyl-2H-tetrazol-5-yl)phenethoxy)propanoate

HRID 909923Notes

Reaction equation

HRID 909923 reaction equation
[CH2:1](Br)[CH:2]=[CH2:3].[N:5]1[NH:6][N:7]=[N:8][C:9]=1[C:10]1[CH:11]=[C:12]([CH:25]=[CH:26][CH:27]=1)[CH2:13][CH2:14][O:15][CH2:16][CH2:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19].C(=O)([O-])[O-].[K+].[K+]>C(#N)C.C(OCC)(=O)C>[CH2:1]([N:6]1[N:7]=[N:8][C:9]([C:10]2[CH:11]=[C:12]([CH:25]=[CH:26][CH:27]=2)[CH2:13][CH2:14][O:15][CH2:16][CH2:17][C:18]([O:20][C:21]([CH3:22])([CH3:24])[CH3:23])=[O:19])=[N:5]1)[CH:2]=[CH2:3].[CH2:1]([N:8]1[C:9]([C:10]2[CH:11]=[C:12]([CH:25]=[CH:26][CH:27]=2)[CH2:13][CH2:14][O:15][CH2:16][CH2:17][C:18]([O:20][C:21]([CH3:22])([CH3:24])[CH3:23])=[O:19])=[N:5][N:6]=[N:7]1)[CH:2]=[CH2:3]

Participants

7

Reactant 3

HCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 67076178tert-Butyl 3-(3-(2H-tetrazol-5-yl)phenethoxy)propanoate

Product 2

HCID 59290379tert-butyl 3-(3-(2-allyl-2H-tetrazol-5-yl)phenethoxy)propanoateHCID 59290403tert-butyl 3-(3-(1-allyl-1H-tetrazol-5-yl)phenethoxy)propanoate

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
65 °C

Procedure

Allyl bromide (0.4 mL) was added in one portion to tert-butyl 3-(3-(2H-tetrazol-5-yl)phenethoxy)propanoate [Example 7, Step ii)] (1.05 g) and potassium carbonate (905 mg) in acetonitrile (10 mL). The resulting mixture was stirred at 65° C. for 1 h. After cooling to rt, the reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (1×20 mL). The organic was dried over magnesium sulfate, filtered and evaporated to afford crude product. The crude product was purified by flash silica chromatography, elution gradient 0 to 80% ethyl acetate in isohexane to afford the subtitled compounds tert-butyl 3-(3-(2-allyl-2H-tetrazol-5-yl)phenethoxy)propanoate (427 mg) and tert-butyl 3-(3-(1-allyl-1H-tetrazol-5-yl)phenethoxy)propanoate (136 mg). Tert-butyl 3-(3-(2-allyl-2H-tetrazol-5-yl)phenethoxy)propanoate: 1H NMR (300 MHz, CDCl3) δ 8.02-7.96 (m, 2H), 7.44-7.30 (m, 2H), 6.12 (m, 1H), 5.45-5.37 (m, 2H), 5.26 (dt, J=6.2, 1.4 Hz, 2H), 3.70 (t, J=7.1 Hz, 2H), 3.70 (t, J=6.5 Hz, 2H), 2.95 (t, J=7.1 Hz, 2H), 2.49 (t, J=6.5 Hz, 2H), 1.43 (s, 9H). Tert-butyl 3-(3-(1-allyl-1H-tetrazol-5-yl)phenethoxy)propanoate: 1H NMR (300 MHz, CDCl3) δ 7.59 (s, 1H), 7.56-7.39 (m, 3H), 6.07 (ddt, J=5.5, 10.6 and 17.2 Hz, 1H), 5.39 (dt, J=1.5 and 10.4 Hz, 1H), 5.16 (dt, J=1.8 and 17.1 Hz, 1H), 5.06 (dt, J=1.6 and 5.5 Hz, 2H), 3.70 (t, J=6.7 Hz, 2H), 3.68 (t, J=6.4 Hz, 2H), 2.95 (t, J=6.8 Hz, 2H), 2.46 (t, J=6.4 Hz, 2H), 1.41 (s, 9H).

Workup

  1. temperatureAfter cooling to rt
  2. washwashed with water (1×20 mL)
  3. dry with materialThe organic was dried over magnesium sulfate
  4. filtrationfiltered
  5. customevaporated
  6. customto afford crude product
  7. customThe crude product was purified by flash silica chromatography, elution gradient 0 to 80% ethyl acetate in isohexane

Sources & evidence

ORD record
ord-ca10ce040665471bb0fb72db27a93558
Source dataset
uspto-grants-2011_09
Patent number
US08017602B2

Reaction notes

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