tert-Butanol → Ammonium Hydroxide

HRID 1097429Notes

Reaction equation

HRID 1097429 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=[N:14][C:15](C(O)=O)=[CH:16][CH:17]=[C:12]1[CH2:11]2.C([N:24]([CH2:27]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:36])C=CC=CC=1.[C:46]([OH:50])([CH3:49])([CH3:48])[CH3:47]>>[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=[N:14][C:15]([NH:24][C:27](=[O:36])[O:50][C:46]([CH3:49])([CH3:48])[CH3:47])=[CH:16][CH:17]=[C:12]1[CH2:11]2

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 57974096(+/-)-2'-Oxo-1',2',5,7-tetrahydrospiro[cyclopenta[b]pyridine-6,3'-pyrrolo[2,3-b]pyridine]-2-carboxylic acid

Product 2

HCID 14923Ammonium HydroxideHCID 86616405(+/-)-tert-Butyl (2'-oxo-1',2',5,7-tetrahydrospiro[cyclopenta[b]pyridine-6,3'-pyrrolo[2,3-b]pyridin]-2-yl)carbamate

Procedure

To a suspension of (±)-2′-oxo-1′,2′,5,7-tetrahydrospiro[cyclopenta[b]pyridine-6,3′-pyrrolo[2,3-b]pyridine]-2-carboxylic acid from Step E (224 mg, 0.796 mmol) and triethylamine (0.333 mL, 2.39 mmol) in tert-butanol (5 mL) was added diphenylphosphoryl azide (0.258 mL, 1.20 mmol) and the mixture was heated at reflux for 1 h. The reaction mixture was concentrated in vacuo and then partitioned between CH2Cl2 (20 mL) and saturated NaHCO3 (20 mL). The organic layer was separated and the aqueous layer was further extracted with CH2Cl2 (2×20 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 1 h
  3. concentrationThe reaction mixture was concentrated in vacuo
  4. custompartitioned between CH2Cl2 (20 mL) and saturated NaHCO3 (20 mL)
  5. customThe organic layer was separated
  6. extractionthe aqueous layer was further extracted with CH2Cl2 (2×20 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-d0398311cb1143abbbc83377385254f0
Source dataset
uspto-grants-2012_03
Patent number
US08143266B2

Reaction notes

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