tert-Butanol → HCID 10761938, compound

HRID 1107638Notes

Reaction equation

HRID 1107638 reaction equation
[CH2:1]([O:8][C:9]1[C:18]2[C:13](=[CH:14][C:15]([C:19]#[N:20])=[CH:16][CH:17]=2)[CH:12]=C(C(O)=O)C=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC[N:26]([CH2:29]C)[CH2:27][CH3:28].C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:38])C=CC=CC=1.[CH3:48][C:49]([OH:52])([CH3:51])[CH3:50]>>[C:49]([O:52][C:29]([NH:26][C:27]1[CH:28]=[C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[C:18]2[C:13](=[CH:14][C:15]([C:19]#[N:20])=[CH:16][CH:17]=2)[CH:12]=1)=[O:38])([CH3:51])([CH3:50])[CH3:48]

Participants

5

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 10542456HCID 10542456, compound

Product 1

HCID 10761938HCID 10761938, compoundYield 87%

Conditions

Temperature
25 °C

Procedure

A solution of 14 (500 mg, 1.65 mmol) in freshly distilled t-BuOH (165 mL) was treated with Et3N (0.276 mL, 1.98 mmol, 1.2 equiv) and 5 g of activated 4 Å molecular sieves. Diphenylphosphoryl azide (0.426 mL, 1.98 mmol, 1.2 equiv) was added and the reaction mixture was warmed at reflux for 14 h. The mixture was cooled to 25° C. and the solvent was removed under vacuum. The residue was dissolved in EtOAc and the organic phase was washed with 10% aqueous HCl, dried (Na2SO4), and concentrated in vacuo. Chromatography (SiO2, 3×20 cm, 20% EtOAc-hexane) afforded 15 (534 mg, 618 mg theoretical, 87%) as a white crystalline solid: mp 145° C. (white needles, 10% EtOAc-hexane); 1H NMR (CDCl3, 250 MHz) δ8.26 (d, 1H, J=8.7 Hz), 8.01 (s, 1H), 7.45 (m, 7H), 7.23 (s, 1H), 6.84 (s, 1H), 5.21 (s, 2H), 1.57 (s, 9H); 13C NMR (CDCl3, 62.5 MHz) δ154.9, 152.5, 138.1, 136.1, 133.6, 132.6, 128.6, 128.2, 127.4, 124.1, 123.6, 123.5, 119.3, 110.5, 106.5, 101.7, 81.1, 70.4, 28.3; IR (KBr) vmax 3327, 2980, 2223, 1701, 1586, 1545, 1420, 1369, 1341, 1251, 1160, 1107, 1064, 1002, 910, 820, 744, 694 cm-1 ; FABHRMS (NBA) m/z 374.1641 (M+, C23H22N2O3 requires 374.1630).

Workup

  1. temperaturethe reaction mixture was warmed
  2. temperatureat reflux for 14 h
  3. customthe solvent was removed under vacuum
  4. dissolutionThe residue was dissolved in EtOAc
  5. washthe organic phase was washed with 10% aqueous HCl
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-1af1013e9d0f4c4da533fd4e177ea7aa
Source dataset
uspto-grants-2000_05
Patent number
US06060608

Reaction notes

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