Hydrochloric Acid → Ammonium Hydroxide

HRID 550985Notes

Reaction equation

HRID 550985 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]2[C:17](=[CH:18][CH:19]=1)[CH2:16][C@@:6]1([C:14]3[C:9](=[N:10][CH:11]=[CH:12][CH:13]=3)[NH:8][C:7]1=[O:15])[CH2:5]2.[C:20]1(Cl)[C:26](=O)C(Cl)=C(Cl)[C:22](=O)[C:21]=1Cl.Cl.C(=O)/C=C/C.[OH-].[Na+]>>[NH4+:1].[OH-:15].[CH3:22][C:21]1[CH:20]=[CH:26][C:19]2[C:2](=[CH:3][C:4]3[CH2:5][C@:6]4([C:14]5[C:9](=[N:10][CH:11]=[CH:12][CH:13]=5)[NH:8][C:7]4=[O:15])[CH2:16][C:17]=3[CH:18]=2)[N:1]=1

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 8371ChloranilHCID 14798Sodium HydroxideHCID 447466CrotonaldehydeHCID 54776259(S)-5-amino-1,3-dihydrospiro[indene-2,3-pyrrolo[2,3-b]pyridin]-2(1H)-one2×

Product 2

HCID 14923Ammonium HydroxideHCID 58026265(S)-2-Methyl-6,8-dihydrospiro[cyclopenta[g]quinoline-7,3'-pyrrolo[2,3-b]pyridin]-2'(1'H)-one

Procedure

(S)-5-Amino-1,3-dihydrospiro[indene-2,3′-pyrrolo[2,3-b]pyridin]-2′(1′H)-one (6.10 g, 24.3 mmol, described in Intermediate 3) and p-chloranil (5.97 g, 24.3 mmol) were suspended in a mixture of 1-BuOH (6 mL) and conc. hydrochloric acid (6 mL, 73 mmol), and the mixture was heated to reflux. Crotonaldehyde (2.04 g, 29.1 mmol) in 1-BuOH (4 mL) was added dropwise over 20 min. After a further 20 min at reflux, the mixture was allowed to cool to ambient temperature, 10 N NaOH (7.3 mL, 73 mmol) was added, and the neutralized mixture was concentrated in vacuo to give a brown residue. The crude product was purified by silica gel chromatography, eluting with a gradient of CH2Cl2:MeOH:NH4OH-100:0:0 to 95:4.5:0.5, to give the title compound. MS: m/z=302 (M+1).

Workup

  1. temperaturethe mixture was heated to reflux
  2. temperatureAfter a further 20 min at reflux
  3. concentrationthe neutralized mixture was concentrated in vacuo
  4. customto give a brown residue
  5. customThe crude product was purified by silica gel chromatography
  6. washeluting with a gradient of CH2Cl2

Sources & evidence

ORD record
ord-be49281aff86459095daa6dc8b2d9766
Source dataset
uspto-grants-2011_05
Patent number
US07947677B2

Reaction notes

Loading…