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temperature for 30 minutes. To the mixture was added 1.0 mL
(10 mmol) of THF and the temperature was slowly elevated to
110 ꢀC. Aer reuxing for 24 h, 10 mL of saturated NaHCO3
solution and 10 mL of dichloromethane were added and stirred
for 1 h. The mixture was extracted with 3 Â 10 mL of
dichloromethane and dried over Na2SO4. The solvent was
removed under reduced pressure, and the residue was isolated
by column chromatography on silica using CH2Cl2/hexanes
(1 : 4 v/v) as eluent to give yellow liquid (100 mg, yield 68%).
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Kinetic experiments
The reaction of 4-uoroaniline with THF was selected in the
kinetic study for the simplication of NMR. Diphenylmethane
was added into the reaction mixture as an internal standard for
integral. To a solution of 0.13 mL (1.2 mmol) of TiCl4 in 8 mL of
dry toluene was added 0.10 mL (1.0 mmol) of 4-uoroaniline.
The mixture was stirred at room temperature for 0.5 h and 2.0
mL (20 mmol) of THF was added to gain a condition of pseudo-
rst order reaction. The well-mixed solution was then divided
into four portions for parallel experiments that were terminated
aer 1 h, 2 h, 3 h and 4 h respectively. Aer reuxing for
a certain period of time, the solution was quenched with satu-
rated NaHCO3 solution, extracted with dichloromethane and
dried over Na2SO4, and the solvent was removed under reduced
pressure. Proton spectra were obtained under consistent
conditions and the integral of the signals at 6.95 and 6.48 ppm
were adopted to measure the amount of unreacted 4-uo-
roaniline, using diphenylmethane as the internal standard for
integral. The concentration of 4-uoroaniline at different reac-
tion time were used to gain the rst order rate constant.
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Acknowledgements
The project is funded by the Natural Science Foundation of
Tianjin, China (14JCYBJC19700).
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4366 | RSC Adv., 2017, 7, 4363–4367
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