F. Massicot et al. / Tetrahedron 57 (2001) 531±536
535
using the standard procedure described below for the syn-
thesis of 4,40-dimethylbiphenyl.
Acknowledgements
We are grateful to Mr Reibel Bernard for his excellent
technical assistance.
4.2. General procedure for homocouplings catalysed by
Ni±Al-bpy reagents
References
4.2.1. 4,40-Dimethylbiphenyl (2c). In an oven dried round-
bottomed ¯ask equipped with a magnetic stirrer, a re¯ux
condenser and a dropping funnel, nickel(II) acetylacetonate
(2.5 mmol), aluminium(III) acetylacetonate (2.5 mmol) and
2,20-bipyridine (12.5 mmol) were added to a degreased
suspension of sodium hydride (37.5 mmol) in 30 mL THF
and the mixture was stirred at 658C for 8 h. 4-Chlorotoluene
(25 mmol) and styrene (1.25 mmol) in 10 mL THF were
then added to the black suspension and the mixture was
further stirred at re¯ux for 3 h. After cooling to room-
temperature, water (1 mL) and dichloromethane (50 mL)
were added and the reaction mixture was ®ltered. After
drying over anhydrous MgSO4 and concentration in
vacuo, the crude product was puri®ed by column chroma-
tography on silica gel using hexanes as eluant and 2c was
isolated as a white solid, mp 1198C (lit.,18 120.7±121.58C),
in 99% yield.
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4.3. Homocoupling of 3-chlorophenol
4.3.1. 3,30-Dihydroxybiphenyl (2n). 3-Chlorophenol
(25 mmol) and styrene (1.25 mmol) in 10 mL THF were
added dropwise at room temperature to a degreased sus-
pension of sodium hydride (62.5 mmol) in 30 mL THF.
Nickel(II) acetylacetonate (2.5 mmol), aluminium(III)
acetylacetonate (2.5 mmol) and 2,20-bipyridine (12.5
mmol) were then added and the mixture was heated at
658C for 24 h. After cooling to room temperature, the reaction
mixture was acidi®ed with HCl 1N, extracted with dichloro-
methane (3£40 mL), dried over anhydrous magnesium sulfate
and the solvent removed under reduced pressure. The crude
product was puri®ed by column chromatography on silica gel
(AcOEt/Hexane10/90) to give 3,30-dihydroxybiphenyl 2n
as a white solid, mp 1248C (lit.,19 123±1258C), in 84% yield.
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4.4. Data for new compounds
4.4.1. 3,30-Bis(morpholino)biphenyl (2q). Obtained as a
colorless oil after column chromatography on silica gel
1
(Hexane/AcOEt50/50). H NMR (400 MHz, CDCl3) d
3
4
7.33 (dd, J3J08.2 Hz, 2H), 7.09 (d, J1.2 Hz, 2H),
3
3
4
7.08 (d, J8.0 Hz, 2H), 6.90 (dd, J8.0 Hz, J2.4 Hz,
2H), 3.90±3.84 (m, 8H); 3.25±3.18 (m, 8H). 13C NMR (100
MHz, CDCl3) d 151.54, 142.83, 129.37, 119.20, 114.88,
114.67, 66.86, 49.39. HR-EIMS calcd for C20H24N2O2
324.1837. Found 324.1830.
4.4.2. 5,50-Bis(morpholino)-3,30-bipyridine (2l). Obtained
as a white solid after column chromatography on silica gel
13. (a) Lourak, M.; Vanderesse, R.; Fort, Y.; Caubere, P. J. Org.
Chem. 1989, 54, 4840. (b) Lourak, M.; Vanderesse, R.; Fort,
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Becker, S.; Caubere, P. Tetrahedron 1994, 50, 11893.
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15. Massicot, F.; Schneider, R.; Fort, Y.; Illy-Cherrey, S.;
Tillement, O. Tetrahedron 2000, 56, 4765.
1
(MeOH/AcOEt10/90), mp 1948C. H NMR (400 MHz,
4
4
CDCl3) d 8.33 (d, J2.4 Hz, 2H), 8.31 (d, J1.2 Hz,
2H), 7.29 (brdd, 2H), 3.93±3.84 (m, 8H), 3.30±3.24 (m,
8H). 13C NMR (100 MHz, CDCl3) d 146.73, 139.25,
137.42, 133.89, 120.23, 66;42, 48.28. HR-EIMS calcd for
C18H22N4O2 326.1742. Found 326.1710.
16. (a) Brenner, E.; Fort, Y. Tetrahedron Lett. 1998, 37, 2090.