Iodine → (2R)-5-iodo-1,3-dihydrospiro[indene-2,3'-pyrrolo[2,3-b]pyridin]-2'(1'H)-one

HRID 334845Notes

Reaction equation

HRID 334845 reaction equation
N([O-])=O.[Na+].N[C:6]1[CH:7]=[C:8]2[C:21](=[CH:22][CH:23]=1)[CH2:20][C@:10]1([C:18]3[C:13](=[N:14][CH:15]=[CH:16][CH:17]=3)[NH:12][C:11]1=[O:19])[CH2:9]2.C1(C)C=CC(S(O)(=O)=O)=CC=1.[I-:35].[K+].[OH-].[Na+].II.S([O-])([O-])(=O)=S.[Na+].[Na+]>O.C(#N)C>[I:35][C:6]1[CH:7]=[C:8]2[C:21](=[CH:22][CH:23]=1)[CH2:20][C@:10]1([C:18]3[C:13](=[N:14][CH:15]=[CH:16][CH:17]=3)[NH:12][C:11]1=[O:19])[CH2:9]2

Participants

10

Reactant 7

HCID 807IodineHCID 4875Potassium IodideHCID 6101p-Toluenesulfonic acidHCID 14798Sodium HydroxideHCID 24477Sodium ThiosulfateHCID 23668193Sodium NitriteHCID 53260812(R)-5-Amino-1,3-dihydrospiro[indene-2,3'-pyrrolo[2,3-b]pyridin]-2'(1'H)-one

Product 1

HCID 58118662(2R)-5-iodo-1,3-dihydrospiro[indene-2,3'-pyrrolo[2,3-b]pyridin]-2'(1'H)-one

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 6342AcetonitrileSolvent

Procedure

A solution of sodium nitrite (107 g, 1.55 mol) in water (500 mL) was added dropwise over 15 min to a solution of (2R)-5-amino-1,3-dihydrospiro[indene-2,3′-pyrrolo[2,3-b]pyridin]-2′(1′H)-one (195 g, 0.776 mol) and p-toluenesulfonic acid (443 g, 2.33 mol) in acetonitrile (1.94 L) at 23° C. After stirring for 30 min, a solution of potassium iodide (322 g, 1.94 mol) in water (500 mL) was then added over 15 minutes. The resulting mixture was stirred at 23° C. for 40 minutes, then diluted with water (2 L) and basified by the addition of solid NaOH (98.0 g, 2.44 mol) with stirring. Iodine by-product was reduced by the addition of 10% aqueous sodium thiosulfate solution and stirring for an additional 30 minutes. The solids were collected by filtration, washed with water, and dried under nitrogen atmosphere to give the title compound, which was used without further purification. MS: m/z=363.1 (M+1).

Workup

  1. stirringThe resulting mixture was stirred at 23° C. for 40 minutes
  2. stirringwith stirring
  3. stirringstirring for an additional 30 minutes
  4. filtrationThe solids were collected by filtration
  5. washwashed with water
  6. customdried under nitrogen atmosphere

Sources & evidence

ORD record
ord-a7cc1e67be2845c58ccdd7e088417037
Source dataset
uspto-grants-2014_11
Patent number
US08883807B2

Reaction notes

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