N[C:2]1[N:6]([C:7]2[CH:12]=[CH:11][C:10]([O:13][CH2:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[C:9]([C:19]#[N:20])[CH:8]=2)[N:5]=[CH:4][C:3]=1[C:21]([O:23][CH2:24][CH3:25])=[O:22].[ClH:26].N([O-])=O.[Na+]>[Cu]Cl.C(OCC)(=O)C>[Cl:26][C:2]1[N:6]([C:7]2[CH:12]=[CH:11][C:10]([O:13][CH2:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[C:9]([C:19]#[N:20])[CH:8]=2)[N:5]=[CH:4][C:3]=1[C:21]([O:23][CH2:24][CH3:25])=[O:22]To a solution (15 ml) of ethyl 5-amino-1-(3-cyano-4-neopentyloxyphenyl)pyrazole-4-carboxylate (2.09 g) obtained in Example 31 in con. hydrochloric acid was added an aqueous solution (4 ml) of sodium nitrite (0.62 g) with stirring under ice-cooling. To this diazonium salt solution was gradually added copper (I) chloride (1.49 g) under ice-cooling. After the dropwise addition, the reaction mixture was heated at 60° C. for 1 hour. After the completion of the reaction, the reaction mix was enacted with ethyl acetate, washed with water and dried over magnesium sulfate. The solvent was evaporated under reduced pressure and the obtained residue was applied to silica gel column chromatography to give 0.74 g of ethyl 5chloro-1-(3-cyano-4-neopentyloxyphenyl)pyrazole-4-carboxylate, melting point 90-92° C.
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