tert-Butanol → HCID 67353414, compound

HRID 1478896Notes

Reaction equation

HRID 1478896 reaction equation
[CH2:1]([N:3]1[C:11]2[CH:10]=[C:9](C(O)=O)[N:8]=[CH:7][C:6]=2[CH:5]=[CH:4]1)[CH3:2].C([N:17]([CH2:20]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:29])C=CC=CC=1.[C:39]([OH:43])([CH3:42])([CH3:41])[CH3:40]>O1CCOCC1.[Cl-].[Na+].O>[CH2:1]([N:3]1[C:11]2[CH:10]=[C:9]([NH:17][C:20](=[O:29])[O:43][C:39]([CH3:42])([CH3:41])[CH3:40])[N:8]=[CH:7][C:6]=2[CH:5]=[CH:4]1)[CH3:2]

Participants

7

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 673540951H-Pyrrolo[3,2-c]pyridine-6-carboxylic acid, 1-ethyl-

Product 1

HCID 67353414HCID 67353414, compoundYield 45%

Reagents, catalysts & solvents 2

HCID 312751,4-DioxaneSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

In a 500 mL pear flask was added 1-ethyl-1H-pyrrolo[3,2-c]pyridine-6-carboxylic acid (1G, assumed 30.4 mmol) in dioxane (90 ml) and t-butanol (90 ml) to give a brown suspension. To this was then added triethylamine (5.5 ml, 40 mmol) and the mixture was then heated to 85° C. After 7 hours, the reaction did not change much from the 25% conversion achieved in the first two hours. An additional 4.3 ml of diphenylphosphoryl azide (0.65 eq.) was added the next morning and after 5 hours, the reaction has progressed significantly. Brine was added and the mixture was extracted twice with ethyl acetate. Combined organic layers were dried over MgSO4, filtered and concentrated. Crude product was purified by column chromatography (SiO2, eluting with a gradient of 20-30% EtOAc/hexanes) to give tert-butyl 1-ethyl-1H-pyrrolo[3,2-c]pyridin-6-ylcarbamate (1H, 3.6 g, 45%).

Workup

  1. customto give a brown suspension
  2. customachieved in the first two hours
  3. waitafter 5 hours
  4. extractionthe mixture was extracted twice with ethyl acetate
  5. dry with materialCombined organic layers were dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customCrude product was purified by column chromatography (SiO2
  9. washeluting with a gradient of 20-30% EtOAc/hexanes)

Sources & evidence

ORD record
ord-46c403edfdb44ec6a2b05232cf2daff5
Source dataset
uspto-grants-2016_08
Patent number
US09403819B2

Reaction notes

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