C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:20]([OH:23])[CH:21]=[CH2:22].O[C:25]1[NH:29][N:28]=[C:27]([N:30]2[C:38](=[O:39])[C:37]3[C:32](=[CH:33][CH:34]=[CH:35][CH:36]=3)[C:31]2=[O:40])[CH:26]=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>CN(C=O)C>[CH2:20]([O:23][C:25]1[NH:29][N:28]=[C:27]([N:30]2[C:31](=[O:40])[C:32]3[C:37](=[CH:36][CH:35]=[CH:34][CH:33]=3)[C:38]2=[O:39])[CH:26]=1)[CH:21]=[CH2:22]To a mixture of triphenylphosphine (2.75 g, 10.5 mmol), allyl alcohol (0.714 ml, 10.5 mmol), and 2-(5-hydroxy-1H-pyrazol-3-yl)isoindoline-1,3-dione (2.000 g, 8.73 mmol) in DMF (25 mL) at RT was slowly added DIAD (2.04 ml, 10.5 mmol). After 18 hrs the solution was concentrated in vacuo, diluted with EtOAc, and washed with water and brine. The organic fraction was dried with sodium sulfate, concentrated in vacuo, and purified by silica gel chromatography using 40-70% Hexanes:EtOAc to afford 2-(5-(allyloxy)-1H-pyrazol-3-yl)isoindoline-1,3-dione as a light yellow solid. MH+=270.1. Step 2B: To a mixture of 2-(5-(allyloxy)-1H-pyrazol-3-yl)isoindoline-1,3-dione (0.684 g, 2.54 mmol) in EtOH (10 mL) at RT was added anhydrous hydrazine (0.319 ml, 10.2 mmol). The solution was heated at 50° C. for 18 hrs before cooling to 0° C. The resulting precipitate was removed by filtration. The filtrate was concentrated in vacuo to afford crude 5-(allyloxy)-1H-pyrazol-3-amine that was advanced without further purification. MS: Found M+H+=147.2.
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