Sodium Hydroxide → 2-Cyano-3-cyclobutyloxy-4,5-dimethoxyaniline

HRID 1004021Notes

Reaction equation

HRID 1004021 reaction equation
S(S([O-])=O)([O-])=O.[Na+].[Na+].[C:9]([C:11]1[C:16]([O:17][CH:18]2[CH2:21][CH2:20][CH2:19]2)=[C:15]([O:22][CH3:23])[C:14]([O:24][CH3:25])=[CH:13][C:12]=1[N+:26]([O-])=O)#[N:10].[OH-].[Na+]>O.[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.ClCCl>[C:9]([C:11]1[C:16]([O:17][CH:18]2[CH2:21][CH2:20][CH2:19]2)=[C:15]([O:22][CH3:23])[C:14]([O:24][CH3:25])=[CH:13][C:12]=1[NH2:26])#[N:10]

Participants

7

Reactant 3

HCID 14798Sodium HydroxideHCID 24489Sodium DithioniteHCID 184706322-Cyano-3-cyclobutyloxy-4,5-dimethoxynitrobenzene

Product 1

HCID 184706542-Cyano-3-cyclobutyloxy-4,5-dimethoxyanilineYield 86%

Reagents, catalysts & solvents 3

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of sodium dithionite (27.6 g, 0.144 mol) in water (100 ml) was added to a solution of 2-cyano-3-cyclobutyloxy-4,5-dimethoxynitrobenzene (4.0 g, 0.0143 mol) and tetra-n-butylammonium chloride (2.33 g, 0.0084 mol) in dichloromethane (100 ml) and the reaction stirred vigorously for 90 minutes. 2N aqueous sodium hydroxide solution (100 ml) and dichloromethane (100 ml) were then added and stirring continued for 5 minutes. The aqueous phase was extracted with further dichloromethane (400 ml) and the combined organic extracts dried (MgSO4), filtered and concentrated under reduced pressure to a volume of 50 ml. Ethereal hydrogen chloride was added and the resulting precipitate filtered and washed with diethyl ether. The solid was then partitioned between 2N aqueous sodium hydroxide (50 ml) and dichloromethane (100 ml) and the organic layer dried (MgSO4), filtered and evaporated under reduced pressure to give the subtitle compound as a yellow oil (2.99 g, 86%). Rf 0.75 (ethyl acetate). MS m/z 266 (MNH4)+.

Workup

  1. stirringstirring
  2. waitcontinued for 5 minutes
  3. extractionThe aqueous phase was extracted with further dichloromethane (400 ml)
  4. dry with materialthe combined organic extracts dried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure to a volume of 50 ml
  7. additionEthereal hydrogen chloride was added
  8. filtrationthe resulting precipitate filtered
  9. washwashed with diethyl ether
  10. customThe solid was then partitioned between 2N aqueous sodium hydroxide (50 ml) and dichloromethane (100 ml)
  11. dry with materialthe organic layer dried (MgSO4)
  12. filtrationfiltered
  13. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-af1a644be54b4dc0a96c2fe087b184eb
Source dataset
uspto-grants-2000_04
Patent number
US06048864

Reaction notes

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