P-Phenylenediamine → N1-(4-phenylphthalazin-1-yl)benzene-1,4-diamine

HRID 911193Notes

Reaction equation

[C:1]1([NH2:8])[CH:6]=[CH:5][C:4]([NH2:7])=[CH:3][CH:2]=1.Cl[C:10]1[C:19]2[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=2)[C:13]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)=[N:12][N:11]=1>O>[C:20]1([C:13]2[C:14]3[C:19](=[CH:18][CH:17]=[CH:16][CH:15]=3)[C:10]([NH:7][C:4]3[CH:5]=[CH:6][C:1]([NH2:8])=[CH:2][CH:3]=3)=[N:11][N:12]=2)[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1

Participants

Conditions

Temperature: 110 °C

Procedure

Benzene-1,4-diamine (0.337 g, 3.12 mmol) and 1-chloro-4-phenylphthalazine (0.500 g, 2.08 mmol) were treated with 7.5 mL 2-BuOH in a sealed tube and heated to 110° C. The reaction quickly became a solid, yellow mass. After several hours, the reaction was cooled and diluted with water. The slurry was then partitioned between DCM and 1N NaOH. The aqueous layer was extracted into DCM (2×). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The resulting material was purified by silica gel chromatography, ISCO, 40 g, 0-10% MeOH/MC to give N1-(4-phenylphthalazin-1-yl)benzene-1,4-diamine as an orange-brown solid. MS m/z=313 [M+H]+. Calc'd for C20H16N4: 312.4.

Workup

customThe reaction
waitAfter several hours
temperaturethe reaction was cooled
customThe slurry was then partitioned between DCM and 1N NaOH
extractionThe aqueous layer was extracted into DCM (2×)
dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
filtrationfiltered
concentrationconcentrated in vacuo
customThe resulting material was purified by silica gel chromatography, ISCO, 40 g, 0-10% MeOH/MC

Sources & evidence

ORD record: ord-bcfda895cf39420e999e7eca80a096f1
Source dataset: uspto-grants-2011_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08022221B2

Reaction notes

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