tert-Butanol → Ammonium Hydroxide

HRID 1866706Notes

Reaction equation

HRID 1866706 reaction equation
[O:1]=[C:2]1[NH:10][C:5]2=[N:6][CH:7]=[CH:8][CH:9]=[C:4]2[C:3]21[CH2:21][C:13]1[CH:14]=[N:15][C:16](C([O-])=O)=[CH:17][C:12]=1[CH2:11]2.[Na+].C([N:25]([CH2:28]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:37])C=CC=CC=1.[C:47]([OH:51])([CH3:50])([CH3:49])[CH3:48]>>[NH4+:6].[OH-:1].[O:1]=[C:2]1[NH:10][C:5]2=[N:6][CH:7]=[CH:8][CH:9]=[C:4]2[C:3]21[CH2:21][C:13]1[CH:14]=[N:15][C:16]([NH:25][C:28](=[O:37])[O:51][C:47]([CH3:50])([CH3:49])[CH3:48])=[CH:17][C:12]=1[CH2:11]2

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azide2×HCID 57974026(+/-)-Sodium 2'-oxo-1',2',5,7-tetrahydrospiro[cyclopenta[c]pyridine-6,3'-pyrrolo[2,3-b]pyridine]-3-carboxylate

Product 2

HCID 14923Ammonium HydroxideHCID 86616403(+/-)-Tert-butyl(2'-oxo-1',2',5,7-tetrahydrospiro[cyclopenta[c]pyridine-6,3'-pyrrolo[2,3-b]pyridin]-3-yl)carbamate

Procedure

To a suspension of (±)-sodium 2′-oxo-1′,2′,5,7-tetrahydrospiro[cyclopenta[c]pyridine-6,3′-pyrrolo[2,3-b]pyridine]-3-carboxylate from Step D (1.64 g, 5.83 mmol) and triethylamine (1.62 mL, 11.7 mmol) in tert-butanol (50 mL) was added diphenylphosphoryl azide (1.89 mL, 8.75 mmol) and the mixture was heated at reflux for 72 h. Additional diphenylphosphoryl azide (1.89 mL, 8.75 mmol) was added after 24 h and 56 h. The reaction mixture was concentrated in vacuo and then partitioned between CH2Cl2 (75 mL) and saturated NaHCO3 (100 mL). The organic layer was separated and the aqueous layer was further extracted with CH2Cl2 (2×50 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by silica gel chromatography, eluting with a gradient of CH2Cl2:MeOH:NH4OH—100:0:0 to 95:5:1, to give the title compound. MS: m/z=353 (M+1).

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 72 h
  3. concentrationThe reaction mixture was concentrated in vacuo
  4. custompartitioned between CH2Cl2 (75 mL) and saturated NaHCO3 (100 mL)
  5. customThe organic layer was separated
  6. extractionthe aqueous layer was further extracted with CH2Cl2 (2×50 mL)
  7. dry with materialThe combined organic layers were dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe crude product was purified by silica gel chromatography
  11. washeluting with a gradient of CH2Cl2

Sources & evidence

ORD record
ord-bfe594b2e6c3407ea617f0a57842479e
Source dataset
uspto-grants-2009_12
Patent number
US07629338B2

Reaction notes

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