tert-Butanol → HCID 58902321, compound

HRID 1640143Notes

Reaction equation

HRID 1640143 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([CH:11]=[C:12]([C:14]#[N:15])[CH:13]=1)C(O)=O)([CH3:4])([CH3:3])[CH3:2].C1C=CC(OP(OC2C=CC=CC=2)([N:25]=[N+]=[N-])=O)=CC=1.[C:35]([OH:39])([CH3:38])([CH3:37])[CH3:36].C1[CH2:44][O:43]CC1>>[C:1]([C:5]1[CH:6]=[C:7]([NH:25][C:44](=[O:43])[O:39][C:35]([CH3:38])([CH3:37])[CH3:36])[CH:11]=[C:12]([C:14]#[N:15])[CH:13]=1)([CH3:2])([CH3:3])[CH3:4]

Participants

5

Reactant 4

HCID 6386tert-ButanolHCID 8028TetrahydrofuranHCID 123414Diphenylphosphoryl azideHCID 247296293-tert-Butyl-5-cyanobenzoic acid

Product 1

HCID 58902321HCID 58902321, compoundYield 86%

Conditions

Temperature
0 °C

Procedure

To a suspension of 3-tert-butyl-5-cyanobenzoic acid (4.5 g, 0.022 mol) in THF (235 mL) at 0° C. was added TEA (11.1 mL, 0.0797 mol) and diphenylphosphonic azide (6.20 mL, 0.0288 mol). The reaction mixture was allowed to stir at 0° C. for 15 min then allowed to warm to rt. After 2 h, the solvents were evaporated and the residue was redissolved in EtOAc. The solution was washed with saturated NaHCO3 solution and brine, dried over Na2SO4, filtered and concentrated. To the residue was added tert-butyl alcohol (108 mL, 1.13 mol). The reaction mixture was allowed to stir at 85° C. under an atmosphere of nitrogen for 3 h and then concentrated. The residue was purified by column chromatography to give tert-butyl (3-tert-butyl-5-cyanophenyl)carbamate (5.21 g, 86%) as a white solid. 1H NMR (400 MHz, d6-DMSO) δ: 9.62(s, 1H), 7.75 (m, 1H), 7.41 (m,1 H), 7.32 (m,1H), 1.46 (s, 9H), and 1.23 (s, 9H). LCMS ES− 273.4

Workup

  1. temperatureto warm to rt
  2. waitAfter 2 h
  3. customthe solvents were evaporated
  4. dissolutionthe residue was redissolved in EtOAc
  5. washThe solution was washed with saturated NaHCO3 solution and brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. stirringto stir at 85° C. under an atmosphere of nitrogen for 3 h
  10. concentrationconcentrated
  11. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-2db59bdb80ee453db53935d66c9d194c
Source dataset
uspto-grants-2012_02
Patent number
US08110687B2

Reaction notes

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