under reduced pressure. The residue was extracted with CH2Cl2
repeatedly. In cases where the amine products might be distilled
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was purified by column chromatography on silica gel to give the
amines.
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General procedure for N–N bond cleavage of hydrazines under
basic conditions
The aqueous solution of titanium(III) trichloride (40 mmol, 30 mL,
18% aqueous solution) was basified by an aqueous solution of
NaOH (20%) or ammonia (25%) to about pH 10. Then hydrazine
(10 mmol) in organic solvent (EtOH, THF or DMF, 10 mL)
was added and the mixture was stirred for 4–6 h under reflux.
After cooling to room temperature, the solvents were removed
under reduced pressure. The residue was extracted with CH2Cl2
repeatedly. In cases where the amine products might be distilled,
the distillate was also extracted with CH2Cl2. The organic phases
were combined. The solvent was evaporated and the residue was
purified by column chromatography on silica gel to give the amines.
General procedure for N–N bond cleavage of hydrazines under
neutral conditions
The aqueous solution of titanium(III) trichloride (40 mmol, 30 mL,
18% aqueous solution) was adjusted to about pH 7 via aqueous
solution of NaOH (20%) or ammonia (25%). Then hydrazine
(10 mmol) in organic solvent (EtOH, THF or DMF, 10 mL) was
added and the mixture was stirred for 4–6 h under reflux. After
cooling to room temperature, the reaction mixture was basified,
while cooling in an ice-bath, with an aqueous solution of NaOH
(20%) to pH >10. The solvents were removed under reduced
pressure. The residue was extracted with CH2Cl2 repeatedly.
In cases where the amine products might be distilled out, the
distillate was also extracted with CH2Cl2. The organic phases
were combined. The solvent was evaporated and the residue was
purified by column chromatography on silica gel to give the amines.
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Acknowledgements
We thank the Natural Science Foundation of China (21021001,
21072134) and Program for Changjiang Scholars and Innovative
Research Team in University (IRT0846) for financial support, and
the Analytical & Testing Centre of Sichuan University for NMR
and MS measurements.
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4982 | Org. Biomol. Chem., 2011, 9, 4977–4982
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