1-Chloro-4-(4-chlorophenylamino)-phthalazine → 1-(4-Chlorophenylamino)-4-(4-pyridylthio)phthalazine

HRID 1070535Notes

Reaction equation

HRID 1070535 reaction equation
Cl[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([NH:12][C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][CH:14]=2)=[N:4][N:3]=1.[SH:20][C:21]1[CH:26]=[CH:25][N:24]=[CH:23][CH:22]=1>C(OCC)(=O)C>[Cl:19][C:16]1[CH:17]=[CH:18][C:13]([NH:12][C:5]2[C:6]3[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=3)[C:2]([S:20][C:21]3[CH:26]=[CH:25][N:24]=[CH:23][CH:22]=3)=[N:3][N:4]=2)=[CH:14][CH:15]=1

Participants

4

Reactant 2

HCID 120756491-Chloro-4-(4-chlorophenylamino)-phthalazineHCID 178418431pyridine-4-thiol

Product 1

HCID 223972711-(4-Chlorophenylamino)-4-(4-pyridylthio)phthalazine

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

1-Chloro-4-(4-chlorophenylamino)-phthalazine (R. D. Haworth and S. Robinson, J. Chem. Soc. 1948, pp.777-782) (2.00 g; ˜6.12 mmol) can be melted together with one equivalent of 4-mercaptopyridine at about 140° C. for about 10-30 min. to yield a residue which is dissolved in ethyl acetate, washed with aqueous sodium carbonate and then evaporated in vacuo. The residue can be purified by chromatography on silica gel using a gradient of pure methylene chloride to 50% acetone in methylene chloride to yield pure 1-(4-chlorophenylamino)-4-(4-pyridylthio)phthalazine. The intermediate thioether can be stirred as a solution in acetic acid as 30% aqueous hydrogen peroxide is added in small portions until TLC analysis indicates that all starting material has been consumed. The crude product is isolated by dilution with ethyl acetate, washing with aqueous carbonate solution to remove acetic acid and evaporation in vacuo. Pure invention compound can be obtained by chromatography on the residue on silica gel using methylene chloride/acetone gradients.

Workup

  1. customto yield a residue which
  2. washwashed with aqueous sodium carbonate
  3. customevaporated in vacuo
  4. customThe residue can be purified by chromatography on silica gel using a gradient of pure methylene chloride to 50% acetone in methylene chloride

Sources & evidence

ORD record
ord-a4921a71952b4d43ad5ea66ca7ff579f
Source dataset
uspto-grants-2005_06
Patent number
US06903101B1

Reaction notes

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