4-Cyanobenzoic acid → HCID 21920371, compound

HRID 1244778Notes

Reaction equation

[C:1]([C:3]1[CH:11]=[CH:10][C:6]([C:7](O)=O)=[CH:5][CH:4]=1)#[N:2].[CH3:12][N:13]([C:15]([NH2:17])=[S:16])[NH2:14].O=P(Cl)(Cl)Cl.C([O-])(O)=O.[Na+]>O1CCOCC1>[CH:3]1([N:17]=[C:15]2[S:16][C:7]([C:6]3[CH:10]=[CH:11][C:3]([C:1]#[N:2])=[CH:4][CH:5]=3)=[N:14][N:13]2[CH3:12])[CH2:11][CH2:10][CH2:6][CH2:5][CH2:4]1

Participants

Conditions

Temperature: 95 °C

Procedure

To a mixture of 4-cyanobenzoic acid (74.8 mmol, 11 g), 2-methylthiosemicarbazide (5a) (74.8 mmol, 13.42 g) in anhydrous dioxane (110 mL) at 70° C., POCl3 (89.65 mmol, 76.76 mL) was added, and the mixture was warmed at 95° C. for 4 hours. The solvent was removed by distillation under reduced pressure to give a crude material which was basified at pH 8-7 with a saturated solution of NaHCO3. The aqueous phase was extracted with dichloromethane. The organic layer was washed with water and saturated solution of NaCl, dried over magnesium sulfate, filtered, and distilled to give a residue which was purified by silica gel chromatography (eluted with a gradient of cyclohexane/ethyl acetate finishing with the ratio 90:10) to afford 8.5 g of the title compound. Yield: 42%.

Workup

customThe solvent was removed by distillation under reduced pressure
customto give a crude material which
extractionThe aqueous phase was extracted with dichloromethane
washThe organic layer was washed with water and saturated solution of NaCl
dry with materialdried over magnesium sulfate
filtrationfiltered
distillationdistilled
customto give a residue which
customwas purified by silica gel chromatography (
washeluted with a gradient of cyclohexane/ethyl acetate finishing with the ratio 90:10)

Sources & evidence

ORD record: ord-bcbc0364f62e43a9b2043bacef1cab87
Source dataset: uspto-grants-2006_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07122565B2

Reaction notes

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