Potassium Carbonate → N4-allyl-2-chloroquinoline-3,4-diamine

HRID 606033

Reaction equation

HRID 606033 reaction equation
C(=O)([O-])[O-].[K+].[K+].S(S([O-])(=O)=O)([O-])(=O)=O.[Na+].[Na+].[CH2:17]([NH:20][C:21]1[C:30]2[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=2)[N:24]=[C:23]([Cl:31])[C:22]=1[N+:32]([O-])=O)[CH:18]=[CH2:19]>ClCCl.O.CC[N+]1C=CC(C2C=C[N+](CC)=CC=2)=CC=1.[Br-].[Br-]>[CH2:17]([NH:20][C:21]1[C:30]2[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=2)[N:24]=[C:23]([Cl:31])[C:22]=1[NH2:32])[CH:18]=[CH2:19]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 146045Sodium dithionateHCID 59007293N-allyl-2-chloro-3-nitroquinolin-4-amine

Product 1

HCID 59007304N4-allyl-2-chloroquinoline-3,4-diamineYield 64.6%

Reagents, catalysts & solvents 3

HCID 114742621,1'-Diethyl-4,4'-bipyridinium dibromideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

An aqueous solution (200 mL) of potassium carbonate (55.3 g, 400 mmol) and sodium dithionate (62.7 g, 360 mmol) was added dropwise over 30 minutes to a mixture of N-allyl-2-chloro-3-nitroquinolin-4-amine (21.0 g, 79.9 mmol) and ethyl viologen dibromide (1.80 g, 4.80 mmol) in dichloromethane (320 mL) and water (40 mL) under a nitrogen atmosphere. The dark blue-green mixture was stirred rapidly and was heated at reflux overnight. The mixture was transferred to a separatory funnel and the layers were separated. The aqueous layer was extracted with dichloromethane. The combined organic layers were filtered through CELITE filter agent, dried over magnesium sulfate, filtered, and concentrated to a dark oil. The crude product was purified by suction filter chromatography (silica gel, gradient elution from 3:1 to 1:3 hexanes/ethyl acetate, then 4:1 dichloromethane/ethyl acetate) to afford pure product N4-allyl-2-chloroquinoline-3,4-diamine (12.06 g) along with some impure product (3.10 g).

Workup

  1. temperaturewas heated
  2. temperatureat reflux overnight
  3. customThe mixture was transferred to a separatory funnel
  4. customthe layers were separated
  5. extractionThe aqueous layer was extracted with dichloromethane
  6. filtrationThe combined organic layers were filtered through CELITE
  7. filtrationfilter agent
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated to a dark oil
  11. customThe crude product was purified by suction
  12. filtrationfilter chromatography (
  13. washsilica gel, gradient elution from 3:1 to 1:3 hexanes/ethyl acetate

Sources & evidence

ORD record
ord-ad46a58806bb476ab51f9ae1f5a3a121
Source dataset
uspto-grants-2011_03
Patent number
US07915281B2

Linked notes

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