4-Hydroxy-3-nitrobenzaldehyde → HCID 178427954, compound

HRID 2218408Notes

Reaction equation

HRID 2218408 reaction equation
[NH2:1][C:2]1[C:7]([NH2:8])=[C:6]([CH3:9])[C:5]([Cl:10])=[CH:4][N:3]=1.[OH:11][C:12]1[CH:19]=[CH:18][C:15]([CH:16]=O)=[CH:14][C:13]=1[N+:20]([O-:22])=[O:21].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C(#N)C>[Cl:10][C:5]1[C:6]([CH3:9])=[C:7]2[N:8]=[C:16]([C:15]3[CH:18]=[CH:19][C:12]([OH:11])=[C:13]([N+:20]([O-:22])=[O:21])[CH:14]=3)[NH:1][C:2]2=[N:3][CH:4]=1

Participants

5

Reactant 3

HCID 181694-Hydroxy-3-nitrobenzaldehydeHCID 521998p-Toluenesulfonic acid monohydrateHCID 445580925-Chloro-4-methylpyridine-2,3-diamine

Product 1

HCID 178427954HCID 178427954, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

2,3-Diamino-5-chloro-4-methylpyridine (prepared by a method similar to Example 206a) (3.2 g, 20.3 mmol), was dissolved in acetonitrile (150 ml). 4-Hydroxy-3-nitrobenzaldehyde (3.1 g) was added, followed by p-toluenesulfonic acid monohydrate (0.7 g) and the resulting mixture was heated to reflux overnight. The solvent was then removed in vacuo and the residue dissolved in a mixture of dichloromethane and methanol (1:1). To this solution was added silica gel and the solvents were evaporated in vacuo. The silica-supported product mixture was then applied to column chromatography, eluting with first dichloromethane and then a mixture of dichloromethane and methanol 4:1. This afforded the title compound of approx. 75% purity. This material was suspended in hot EtOAc and filtered while still hot. The collected solid was approx. 95% pure. An analytical sample was prepared by semi-preparative HPLC-C18.

Workup

  1. temperaturethe resulting mixture was heated
  2. temperatureto reflux overnight
  3. customThe solvent was then removed in vacuo
  4. dissolutionthe residue dissolved in a mixture of dichloromethane and methanol (1:1)
  5. additionTo this solution was added silica gel
  6. customthe solvents were evaporated in vacuo
  7. washeluting with first dichloromethane
  8. additiona mixture of dichloromethane and methanol 4:1

Sources & evidence

ORD record
ord-79953738c5d54090bcc319c66741c52b
Source dataset
uspto-grants-2008_08
Patent number
US07410966B2

Reaction notes

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