Aniline → sodium 4-methylbenzenesulfonate

HRID 1978244Notes

Reaction equation

C(C1C=CC([C:9]2[CH:18]=[C:17]([CH3:19])[CH:16]=[CH:15][C:10]=2[S:11]([O-:14])(=[O:13])=[O:12])=CC=1)#N.C(C1C=C(C(C)(C)C)C=C(C(C)(C)C)C=1[O-])(C)(C)C.[Na+:39].NC1C=CC=CC=1>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].CC(P(C(C)(C)C)[C]1[CH][CH][CH][CH]1)(C)C.CC(P(C(C)(C)C)[C]1[CH][CH][CH][CH]1)(C)C.[Fe]>[O:14]([S:11]([C:10]1[CH:15]=[CH:16][C:17]([CH3:19])=[CH:18][CH:9]=1)(=[O:13])=[O:12])[Na:39]

Participants

Conditions

Temperature: 110 °C

Procedure

4-Cyanodiphenylamine (Takeuchi, H.; Takano, K. J. Chem. Soc. Perkin Trans. 1 1986, 611-618. 4-Cyanophenyltosylate (271 mg, 1.02 mmol), Pd(DBA)2 (11.7 mg, 0.02 mmol), DBtPF (14.5 mg, 0.03 mmol) and sodium 2,4,6-tri-t-butylphenoxide (346 mg, 1.22 mmol) were suspended in 2 mL of toluene in a screw-capped vial. The vial was sealed with a cap containing a PTFE septum and removed from the dry box. Aniline (102 μL, 1.12 mmol) was added to the reaction mixture by syringe. The vial was heated in a 110° C. oil bath for 16 hours. Over this time, a large amount of solid (presumably NaOTs) formed. The reaction was cooled to room temperature. The crude reaction was diluted with toluene (50 mL) and washed with water (50 mL, 1×) followed by brine (50 mL, 1×). The organic layer was dried over Na2SO4, filtered, and concentrated in vacuo. Purified product was obtained in 82% yield after silica gel chromatography using 10% EtOAc in hexanes. 1H NMR: (CDCl3) δ 7.41 (d, J=8.7 Hz, 214), 7.33 (m, 2H) 6.08 (m, 3H), 6.96 (d, J=8.7 Hz, 2H), 6.43 (bs, 1H); 13C{1H} NMR: (CDCl3) δ 148.01, 139.64, 133.50, 129.38, 123.56, 120.87, 120.01, 114.64, 100.63.

Workup

customThe vial was sealed with a cap
customremoved from the dry box

Sources & evidence

ORD record: ord-6d99b2aa3eb745758664c72c074232ed
Source dataset: uspto-grants-2001_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06235938B1

Reaction notes

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