Notes
J . Org. Chem., Vol. 64, No. 2, 1999 673
purification. Yields in the tables refer to isolated yields of
compounds estimated to be greater than 99% pure as determined
by 1H NMR (CDCl3) and 13C NMR (CDCl3) as well as reversed
phase HPLC. Elemental analyses were conducted in-house on
samples purified by hot column chromatography using the
technique described by Kauffman.19 Melting points were re-
corded on a TA Instruments Model 2910 differential scanning
calorimeter and are reported as peak maximum values. Experi-
mental procedures are illustrated by the following typical
reactions.
130.36, 133.32, 145.58, 148.35, 149.79, 160.87. Anal. Calcd for
C
20H19NO: C, 83.01; H, 6.62; N, 4.84; O, 5.53. Found: C, 82.83;
H, 6.76; N, 4.69; O, 5.72.
N-(4-Bip h en ylyl)-N-(3-m eth oxyp h en yl)-3,4-d im eth ylben -
1
zen a m in e (6c): method A, white solid; mp 104.7 °C; H NMR
2.28 (s, Me), 2.35 (s, Me), 3.79 (s, OMe), 6.61-7.69 (aromatic);
13C NMR 19.65, 20.43, 55.68, 108.04, 109.87, 116.59, 123.49,
124.04, 127.17, 127.19, 128.37, 129.17, 130.18, 130.83, 130.93,
132.49, 135.13, 138.10, 141.16, 145.59, 147.73, 149.64, 160.85.
Anal. Calcd for C27H25NO: C, 85.45; H, 6.64; N, 3.69; O, 4.22.
Found: C, 85.01; H, 6.82; N, 3.84; O, 4.33.
Meth od A. Gen er a l P r oced u r e for Mon oa r yla tion Ull-
m a n n Con d en sa tion s. To a 500 mL round-bottomed flask
containing 70 mL of toluene equipped with a mechanical stirrer,
an argon gas purge, and a Dean-Stark trap under a reflux
condenser were added in the following order while maintaining
good stirring 110 mmol of the diarylamine, 110 mmol of the aryl
iodide, 4 mmol of 1,10-phenanthroline, 4 mmol of cuprous
chloride, and 860 mmol of potassium hydroxide flakes.20 The
reaction mixture was rapidly heated over the course of 30 min
to the reflux temperature of 125 °C and maintained at that
temperature until qualitative HPLC analysis revealed the
conversion to be substantially complete. Usually 4-5 h are
sufficient. The reaction mixture was cooled to 75 °C and
partitioned between 200 mL of toluene and 150 mL of deionized
water. After washing with an additional amount of water, the
organic phase was decolorized by slurry treating it over 3 h at
75 °C with 36 g of Filtrol-24,21 an acid leached bentonite clay,
and 24 g of Alcoa CG-20 alumina. The adsorbents were then
removed by hot filtration, and the solvent was removed by rotary
evaporation. The product was subjected to further purification
by hot column chromatography with heptane elution.
Meth od B. Gen er a l P r oced u r e for Dou ble Ar yla tion
Ullm a n n Con d en sa tion s. These reactions were run in an
identical manner as described in method A with the exception
that a 10% excess of 2 equiv of the amine component with respect
to the iodide was employed. A reaction temperature of 125 °C
was maintained until HPLC analysis showed qualitative comple-
tion. Workup proceeded as before.
Meth od C. Gen er a l P r oced u r e for Bis(a r yla tion ) Ull-
m a n n Con d en sa tion s. These reactions were run in an identical
manner as described in method A with the exception that a 10%
excess of 2 equiv of the iodide component with respect to the
amine was utilized. Again, a reaction temperature of 125 °C was
maintained until HPLC analysis indicated substantial qualita-
tive completion. Workup proceeded as before.
N,N′-Dip h en yl-N,N′-bis(3-m eth ylp h en yl)-[1,1′-bip h en yl]-
4,4′-d ia m in e (3a ): method B, white solid; mp 169.1 °C; 1H NMR
2.30 (s, Me), 6.87-7.26 (m, aromatic); 13C NMR 21.83, 122.05,
123.02, 124.22, 124.42, 124.60, 125.50, 127.63, 129.46, 129.59,
134.99, 139.52, 147.20, 148.05, 148.21. Anal. Calcd for
C38H32N2: C, 88.63; H, 6.24; N, 5.42. Found: C, 88.49; H, 6.32;
N, 5.57.
N,N′-Diph en yl-N,N′-bis(3-m eth oxyph en yl)-[1,1′-biph en yl]-
4,4′d ia m in e (3b): method B, white solid; mp 128.5 °C; 1H NMR
3.72 (s, OMe), 6.55-7.02 (m, aromatic); 13C NMR 55.64, 108.54,
110.31, 116.98,,123.38, 124.58, 124.96, 127.69, 129.63, 130.21,
135.29, 147.02, 147.99, 149.40, 160.89. Anal. Calcd for
C38H32N2O2: C, 83.18; H, 5.88; N, 5.11; O, 5.83. Found: C, 83.65;
H, 5.68; N, 5.08; O, 5.72.
N,N-Bis(4-b ip h en ylyl)-3,4-d im et h ylb en zen a m in e (6d ):
method A, white solid; mp 221.9 °C; 1H NMR 2.20 (s, Me), 2.33
(s, Me), 6.93-7.33 (aromatic); 13C NMR (saturated solution)
19.17, 19.84, 123.02, 123.56, 126.61, 126.71, 126.72, 127.69,
128.71, 130.54, 132.09, 134.79, 137.73, 140.68, 145.13, 147.23.
Anal. Calcd for C32H27N: C, 90.31; H, 6.39; N, 3.29. Found: C,
90.51; H, 6.46; N, 3.23.
N,N-Bis(3,4-d im et h ylp h en yl)-4-b ip h en yla m in e
(6e):
method A, white solid; mp 114.3 °C; 1H NMR 2.21 (s, Me), 2.26
(s, Me), 6.88-7.43 (m, aromatic); 13C NMR (saturated solution)
19.12, 19.84, 122.35, 122.43, 126.04, 126.49, 126.51, 127.47,
128.64, 130.33, 131.28, 133.72, 137.45, 140.76, 145.49, 147.75.
Anal. Calcd for C28H27N: C, 89.08; H, 7.21; N, 3.71. Found: C,
88.80; H, 7.13; N, 3.82.
N -P h e n y l-N -(3,4-d im e t h y lp h e n yl)-4-b ip h e n yla m in e
(6f): method A, white solid; mp 116.7 °C; 1H NMR 2.22 (s, Me),
2.27 (s, Me), 6.90-7.28 (m, aromatic); 13C NMR 19.57, 20.27,
122.75, 123.25, 123.62, 124.23, 126.95, 127.00, 127.07, 128.03,
129.10, 129.53, 130.86, 132.29, 134.88, 138.07, 141.13, 145.68,
147.83, 148.29. Anal. Calcd for C26H23N: C, 89.36, H, 6.63, N
4.01. Found: C, 89.43, H, 6.32, N, 4.01.
N-(3-Meth ylp h en yl)-N-p h en yl-4-br om o-1,1′-bip h en yl-4′-
a m in e (6g): method C, white solid; mp 142.0 °C; 1H NMR 2.27
(s, Me), 6.88 (t, J ) 7.2 Hz, aromatic), 6.95 (m, aromatic), 7.02
(t, J ) 7.2 Hz, aromatic), 7.08-7.29 (m, aromatic), 7.41 (d, J )
8.7 Hz, aromatic), 7.42 (d, J ) 8.7 Hz, aromatic), 7.51 (d, J )
8.4 Hz, aromatic).13C NMR 21.84, 121.26, 122.33, 123.37, 123.98,
124.56, 124.89, 125.77, 127.92, 128.58, 129.56, 129.69, 132.22,
133.82, 139.64, 140.00, 147.86, 148.03, 148.06. Anal. Calcd for
C25H20BrN: C, 72.47; H, 4.87; N, 3.38. Found: C, 72.40; H, 4.90;
N, 3.34.
N,N-Bis(4-m eth ylp h en yl)ben zen a m in e (9a ): method C,
white solid; mp 108.1 °C (lit.23 mp 108 °C); 1H NMR 2.29 (s, Me),
6.88-7.15 (m, aromatic); 13C NMR 20.78, 121.70, 122.97, 124.46,
129.01, 129.82, 132.28, 145.48, 148.29. Anal. Calcd for
C20H19N: C, 87.87; H, 7.01; N, 5.12. Found: C, 87.60; H, 7.18;
N,5.04.
N,N-Bis(4-m et h ylp h en yl)-4-b r om ob en zen a m in e (9b ):
method C, white solid; mp 104.3 °C (lit.24 mp 103.5-104.5 °C).
N,N-Bis(3,4-dim eth ylph en yl)-4-br om oben zen eam in e (9c):
method C, light tan powder; mp 125.3 °C; 1H NMR 2.16 (s, Me),
2.22 (s, Me), 6.78-7.22 (m, aromatic); 13C NMR 19.50, 20.22,
113.62, 122.73, 124.15, 126.43, 130.82, 132.04, 132.20, 138.00,
145.62, 148.03. Anal. Calcd for C22H22BrN: C, 69.48; H, 5.83;
Br 21.01; N, 3.68. Found: C, 69.38; H, 5.87; Br, 20.97; N, 3.78.
N,N,N-Tr is(3,4-d im et h ylp h en yl)a m in e (9d ): method C,
light yellow solid; mp 133.6 °C; 1H NMR 2.15 (s, Me), 2.25 (s,
Me), 6.75-7.25 (m, aromatic); 13C NMR 19.07, 19.85, 121.51,
125.23, 130.16, 130.33, 137.23, 146.14. Anal. Calcd for
C24H27N: C, 87.49; H, 8.26; N, 4.25. Found: C, 87.04; H, 7.82;
N, 4.12.
N,N-Dip h en yl-3,5-d im eth ylben zen a m in e (6a ): method A,
1
white solid; mp 136.5 °C (lit.22 mp 130-132 °C); H NMR 2.24
(6H s, Me), 6.64-7.28 (aromatic); 13C NMR 21.68, 122.72, 122.76,
124.40, 125.23, 129.48, 139.23, 148.11, 148.45. Anal. Calcd for
C20H19N: C, 87.87; H 7.01; N 5.12. Found: C, 88.23; H, 7.01; N,
5.02.
N,N-Bis(3,4-d im et h ylp h en yl)-4-b ip h en yla m in e
(9e):
method C, white solid; mp 114.1 °C; 1H NMR 2.21 (s, Me), 2.26
(s, Me), 6.88-7.43 (m, aromatic); 13C NMR (saturated solution)
19.12, 19.84, 122.35, 122.43, 126.04, 126.49, 126.51, 127.47,
128.64, 130.33, 131.28, 133.72, 137.45, 140.76, 145.49, 147.75.
Anal. Calcd for C28H27N: C, 89.08; H, 7.21; N, 3.71. Found: C,
88.91; H, 7.15; N, 3.89.
N-P h en yl-N-(3-m eth oxyp h en yl)-4-m eth ylben zen a m in e
1
(6b): method A, white solid; mp 66.6 °C; H NMR 2.30 (s, Me),
3.68 (s, OMe), 6.48-7.28 (aromatic); 13C NMR 21.27, 55.61
107.95, 109.66, 116.34, 122.89, 124.40, 125.60, 129.55, 130.13,
N,N,N-Tr is(4-br om op h en yla m in e) (9f): method C, white
solid; mp 143.8 °C (lit.25 mp 144.5-146.5 °C).
(19) Kauffman, J . M.; Bjorkman, C. O. J . Chem. Educ. 1976, 53,
33.
(20) The flake form of KOH is preferred because, although it is
slightly less pure than the pellet form, it contains less water.
(21) Available from Harshaw/Filtrol Partnership, Cleveland, OH.
(22) Haga, K.; Oohashi, M.; Kanfko, R. Bull. Chem. Soc. J pn. 1984,
57, 1586-1590.
(23) Sato, N.; Yoshikawa, M. Chem. Phys. 1992, 160, 289-297.
(24) Barton, D. H. R.; Haynes, R. K.; Leclerc, G.; Magnus, P. D.;
Menzies, I. D. J . Chem. Soc., Perkin Trans. 1 1975, 2055-2065.
(25) Baker, N.; Doherty, W.; Kelley, W.; Newmeyer, W.; Rogers, J .;
Spalding, R.; Walter, R. J . Org. Chem. 1965, 30, 3714-3718.