506
LETTERS
SYNLETT
1
13
(2) Keller, H. J.; Niebl, R.; Renner, G.; von der Ruhr, D.; Kilic, A. K.;
(11) All new compounds were characterized by IR, MS, H- and
NMR, elemental analysis and/or HRMS.
C
Schweitzer, D. Z. Naturforsch. 1989, 44b, 327.
(12) For recent investigations to utilize 18 in the synthesis of discrete
molecular weight dendrimers via the aryl amination protocol see:
Louie, J.; Hartwig, J. F.; Fry, A. J. J. Am. Chem. Soc. 1997, 119,
11695.
(3) Effenberger, F. Acc. Chem. Res. 1989, 22, 27.
(4) Stickley, K. R.; Blackstock, S. C. J. Am. Chem. Soc. 1994, 116,
11576. Krusic, P. J.; Wasserman, E. J. Am. Chem. Soc. 1991, 113,
2322. Miller, J. S.; Dixon, D. A.; Calabrese, J. C.; Vazquez, C.;
Krusic, P. J.; Ward, M. D.; Wasserman, E.; Harlow, R. L. J. Am.
Chem. Soc. 1990, 112, 381. Thomaides, J.; Maslak, P.; Breslow,
R. J. Am. Chem. Soc. 1988, 110, 3970.
(13) Spectroscopic data of : colorless solid; m.p. 169-171 °C; R =
21
f
1
0.24 (Alox/N-TLC, hexanes/ethyl acetate = 9 : 1 (v/v)); H NMR
(400 MHz, CDCl ) δ = 7.29 (dd, J = 7.3 Hz, J = 8.1 Hz, 2H), 6.97
3
(d, J = 8.1 Hz, 2H), 6.88 (t, J = 7.3 Hz, 1H), 6.20 (s, 1H), 3.30 (s,
13
(5) Effenberger, F.; Prossel, G.; Auer, E.; Fischer, P. Chem. Ber.
1970, 103, 1456. Effenberger, F.; Auer, E.; Fischer, P. Chem. Ber.
1970, 103, 1440. Effenberger, F.; Niess, R. Chem. Ber. 1968, 101,
3787. Biemans, H. A. M.; Zhang, C.; Smith, P.; Kooijman, H.;
Smeets, W. J. J.; Spek, A. L.; Meijer, E. W. J. Org. Chem. 1996,
61, 9012. Wolff, J. J.; Limbach, H.-H. Liebigs Ann. Chem. 1991,
691. Praefcke, K.; Kohne, B.; Korinth, F.; Psaras, P.; Nasielski, J.;
Verhoeven, C.; Nasielski-Hinkens, R. Liebigs Ann. Chem. 1989,
617.
8H). C NMR (100 MHz, CDCl ) δ = 153.1 (s), 151.2 (s), 129.1
3
(d), 116.2 (d), 119.9 (d), 98.5 (d), 49.9 (t), 49.4 (t); IR (KBr) ν =
-1
3058 cm ; 3035, 2956, 2820, 1590, 1499, 1448, 1382, 1335,
1310, 1271, 1234, 1205, 1152, MS (EI, 70 eV) m/z (%): 558 (28,
+
M ), 426 (81), 266 (14), 120 (25), 44 (100); C
H N : calc.: C
36 42 6
77.38, H 7.58, N 15.04; found C 76.91, H 7.44; N 14.69. EI-
HRMS: calc. for C N 558.3471; found 558.3486.
H
36 42
6
(14) Typical procedure: In a Schlenk tube with screw cap were
introduced under argon 1,2,4,5-tetrabromobenzene (22) (276 mg,
0.70 mmol), morpholine (2) (292 mg, 3.36 mmol), sodium tert-
butoxide (376 mg, 3.92 mmol), Pd (dba) (19 mg, 0.02 mmol),
(6) Wagaw, S.; Rennels, R. A.; Buchwald, S. L. J. Am. Chem. Soc.
1997, 119, 8451. Hartwig, J. F. Synlett 1997, 329. Marcoux, J. F.;
Wagaw, S.; Buchwald, S. L. J. Org. Chem. 1997, 62, 1568.
Wolfe, J. P.; Wagaw, S.; Buchwald, S. L. J. Am. Chem. Soc. 1996,
118, 7215. Driver, M. S.; Hartwig, J. F. J. Am. Chem. Soc. 1996,
118, 7217. Guram, S.; Rennels, R. A.; Buchwald, S. L. Angew.
Chem. 1995, 107, 1456; Angew. Chem. Int. Ed. Engl. 1995, 34,
1348.
2
3
BINAP (39 mg, 0.06 mmol), and toluene (5 ml). The sealed tube
was kept at 100 °C for 2 d. The reaction mixture was diluted with
brine and extracted with CH Cl . After evaporation of the
2
2
solvents the organic residues were extracted with diethyl ether
dissolving compound 16 only. Column chromatography of the
residue (SiO ; CH Cl /hexanes/ethyl ether = 8 : 2 : 2 (v/v/v)) gave
2
2
2
analytically pure 23 (210 mg, 0.50 mmol, 72%). Compound 16
(7) For Pd-catalyzed polycondensations between 1,3-bisanilines and
6 see: Kanbara, T.; Izumi, K.; Nakadani, Y.; Narise, T.;
Hasegawa, K. Chem. Lett. 1997, 1185.
was obtained after chromatography of the ether extracts (SiO ,
2
hexanes/diethyl ether = 3 : 7 (v/v) yielding analytically pure 16
(50 mg, 0.15 mmol, 21%).
: colorless plates (CHCl /pentane); m.p. >300 °C; R = 0.3
23
(8) Diercks, R.; Armstrong, J. C.; Boese, R.; Vollhardt, K. P. C.
Angew. Chem. 1986, 98, 270; Angew. Chem. Int. Ed. Engl. 1986,
25, 268. Boese, R.; Green, J. R.; Mittendorf, J.; Mohler, D. L.;
Vollhardt, K. P. C. Angew. Chem. 1992, 104, 1643; Angew. Chem.
Int. Ed. Engl. 1992, 31, 1643.
3
f
1
(SiO -TLC, CH Cl /hexanes/diethylether = 8 : 2 : 2 (v/v/v)); H
2
2
2
NMR (200 MHz, CDCl ) δ = 6.53 (s, 2H), 3.80 (‘t’, J ~ 4.5 Hz, 16
3
13
H), 3.15 (‘t’, J ~ 4.5 Hz, 16 H); C NMR (100 MHz, CDCl ) δ =
139.6 (s), 109.3 (d), 67.6 (t), 50.3 (t); IR (KBr) ν = 2965 cm ;
3
-1
2794, 1514, 1438, 1258, 1209, 1113, 972, 934, 915; MS (EI, 70
eV) m/z (%): 419 (25); 418 (100, M ), 360 (2), 302 (2), 243 (4);
(9) Rinz, P.; Lansky, A.; Haumann, T.; Boese, R.; Noltemeyer, M.;
Knieriem, B.; de Meijere, A. Angew. Chem. 1997, 109, 1343;
Angew. Chem. Int. Ed. Engl. 1997, 36, 1289.
+
C
H N O : calc.: C 63.13, H 8.19, N 13.39; found: C 62.73, H
22 34 4 4
7.99, N 13.19.
: colorless plates (CH Cl /hexanes), m.p. 125-126 °C; R : 0.3
10
(10) Synthesis of 1,2,3-tri-bromobenzene 17: Tietze, L. F.; Eicher, Th.
Reaktionen und Synthesen Thieme: Stuttgart, 1991, p. 501. The
morpholinobenzenes 7, 10, 12, 14, and 16 have been previously
synthesized by non-catalytic methods: 7 and 12: Kawaguchi, M.;
Ohashi, J. Synthesis 1985, 701. 10: Axe, W. N.; Freeman, C. J.
Am. Chem. Soc. 1934, 56, 478. 14: Effenberger, F.; Niess, R.
Angew. Chem. 1967, 79, 1100; Angew. Chem. Int. Ed. Engl. 1967,
6, 1067. 16: Baroni, S.; Rivera, E.; Stradi, R.; Sacarello, M. L.
Tetrahedron Lett. 1980, 21, 889.
16
(SiO -TLC, hexanes/ethyl acetate = 3 : 7 (v/v)); H NMR (200
2
2
f
1
2
MHz, CDCl ) δ = 6.83-6.9 (m, 1 H), 6.52-6.57 (m, 2 H), 3.79-3.87
3
13
(m, 12 H); C NMR (200 MHz, CDCl ) δ = 147.7 (s), 145.4 (s),
3
138.1 (s), 119.0 (d), 109.8 (d), 107.7 (d), 67.6 (t), 66.9 (t), 50.5 (t),
-1
50.2 (t), 50.1 (t); IR (KBr) ν = 2957 cm , 2850, 1602, 1506, 1448,
+
1253, 1117; MS (70 eV) m/z (%): 333 (85, M ), 249 (13), 248
(100), 190 (30), 132 (37); C
H N O calc.: C 64.84, H 8.16, N
18 27 3 3
12.60; found: C 64.79, H 8.11, N 12.77.