J. Org. Chem., 1996, 61(21), , DOI: /jo

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1 J. Org. Chem., 1996, 61(21), , DOI: /jo Terms & Conditions Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machinereadable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at Copyright 1996 American Chemical Society

2 1>>')I -Xlht1t.x X Uxx 1 1t.t* U Xu.fjum-mt* St[ ~hi. ~f.,1h~1 vj '3-. x 1 -,S "Y t*5t*vv JLI 1 pi..h1..htt* x I6 5 Supporting Information Experimental Procedure General Considerations. All reactions were carried out using standard Schlenk techniques under an argon atmosphere. Toluene was distilled from molten sodium under argon. Sodium tert-butoxide was purchased form Aldrich Chemical Co. and was stored in a Vacuum Atmospheres Dry Box under nitrogen, and was weighed out in air. All reagents were commercially available and used without further purification. Preparative flash chromatography was performed using ICN Flash Silica Gel, mesh. Yields refer to the average of two isolated yields of 95% or higher purity as determined by GC, and 1 H NMR, and elemental analysis. All products were characterized by 1 H NMR, 13C NMR, and Infrared (IR) spectroscopy. New compounds were further characterized by C, H elemental analysis from E & R Microanalytical Laboratories, Corona Ave, Corona, NY NMR spectra were obtained on a Varian XL-300, Varian Unity 300, or a Varian VXR 500 MHz spectrometer. All 1 H NMR spectra are reported in 5 units, ppm down field from tetramethylsilane internal standard. All 13C spectra are reported in ppm relative to the central line of the triplet for CDC1 3 at 77 ppm. IR spectra were recorded on a Perkin-Elmer 1600 Series Fourier Transform spectrometer. Gas chromatography analyses were performed on a Hewlett-Packard 5890 Gas Chromatograph, with a FID, a 25 meter capillary column with a dimethylpolysiloxane stationary phase, and a 3392A integrator. Melting points were determined using a Haake Buchler Melting Point Apparatus and are uncorrected. Conversion of Bromopyridines to Aminopyridines General Procedure A. 2-Bromopyridine (1 mmol, 0.1 ml), amine (1.2 mmol), Pd 2 (DBA) 3, (0.02 mmol, 4 mol % Pd, 18 mg), 1,3-bis(diphenylphosphino)propane (dppp, 0.04 mmol, 16 mg), NaOtBu (1.4 mmol, 134 mg), and toluene (0.11 M with 2-bromopyridine, 9

3 1>>')I -Xlht1t.x X Uxx 1 1t.t* U XU jum-mht* St[ ~hi. ~f.,1h~1 vj '31 -. x 1 -,S "Y t*5t*vv JLI 1 pi..h1..htt* x 5 ml) were added to an oven-dried Schlenk flask which was purged with argon for approximately 5 minutes. The reaction mixture was then heated to 700 C under argon until the bromopyridine was consumed as determined by GC analysis. The reaction mixture was then allowed to cool to room temperature, taken up in diethyl ether (10 ml), washed 3 times with saturated brine (10 ml), dried over MgSO 4, and condensed in vacuo to give the crude product. Purification by flash column chromatography afforded the analytically pure product. General Procedure B. 3-Bromopyridine (1 mmol, 0.1 ml), the amine (1.2 mmol), Pd 2 (DBA) 3 (0.02 mmol, 4 mol % Pd, 18 mg), (±) BINAP (0.04 mmol, 25 mg), NaOtBu (1.4 mmol, 134 mg), and toluene (0.11 M with 3-bromopyridine, 9 ml) were added to an oven dried Schlenk flask which was purged with argon for approximately 5 minutes. The reaction mixture was heated to 700 under argon until the 3-bromopyridine was consumed as determined by GC analysis. The reaction was then cooled to room temperature, and taken up in 10 ml diethyl ether, washed 3 times with 10 ml saturated brine, dried over MgSO4, and condensed in vacuo to give the crude product. Purification by flash column chromatography afforded the analytically pure product. 2-(N-Benzyl, N'-methylamino)-pyridine (Table 1, entry 1). Procedure A was used to convert 2-bromopyridine and N-benzylmethylamine to the title product. Purification by flash column chromatography (15% EtOAc/Hex) gave the pure product as a clear oil (190 mg, 86% yield). 1 H NMR (300 MHz, CDC13): (m, 1 H), (m, 1 H), (m, 5 H), (m, 2 H), 4.80 (s, 2 H), 3.06 (s, 3 H): 13C{1H} NMR (75 MHz, CDC13): , 148.1, 138.9, 137.4, 128.7, 127.0, 111.9, 105.8, 53.3, 36.6; IR (neat): 3027, 2897, 1558, 1495, 1422, 1319 cm- 1. Analysis calculated for C13H14N2: C, 78.75; H, Found; C, 78.71; H,

4 - ~ -~ - - ~.. c- - -~ ~~rr ~ 2,2'-Dipyridylamine (entry 2).1 Procedure A was used to convert 2-bromopyridine and 2-aminopyridine to the title product. Purification of the crude product by flash column chromatography (25% EtOAc/Hex with 5%NEt 3 ) afforded the pure product as a white solid (132 mg, 87% yield). M.p O C; 1 H NMR (300 MHz, CDC1 3 ): (d, J = 4.9 Hz, 2 H), 8.15 (s, 1 H), (m, 4 H), 6.85 (t, J = 5.4 Hz, 2 H); 13C{1H} NMR (75 MHz, CDC13): , 147.9, 137.9, 116.5, (N-Morpholino)-pyridine (entry 3). Procedure A was used to convert 2- bromopyridine and morpholine to the title product. Purification by flash column chromatography (25% EtOAc/Hex) gave the pure product as a yellow oil (144 mg, 87% yield). 1 H NMR (300 MHz, CDCI3): (d, J = 4.9 Hz, 1 H), 7.49 (dt, J = 7.8 Hz, J = 1.9 Hz, 1 H), (m, 2 H), 3.82 (t, J = 4.9 Hz, 4 H), 3.49 (t, J = 4.9 Hz, 4 H): 13 C{ 1 H} NMR (75 MHz, CDCl3): , 148.0, 137.6, 113.9, 107.0, 66.8, 45.7; IR (neat): 2961, 2852, 1591, 1481, 1437 cm- 1. Analysis calculated for C9H12N20: C, 65.83; H, Found; C, 65.95; H, (Cyclohexylamino)-pyridine (entry 4). 2-Chloropyridine (1 mmol, ml), cyclohexylamine (1.2 mmol, 1.4 ml), Pd(OAc)2 (0.04 mmol, 9 mg), dppp (0.04 mmol, 16 mg), NaOtBu (1.4 mmol, 134 mg), in toluene (0.11 M with 2-chloropyridine, 9 ml) were heated to 700 C in a Schlenk flask under argon for 12 hours. The reaction was the allowed to cool to room temperature, diethyl ether (10 ml) was added to the reaction mixture which was then washed 3 times with saturated brine (10 ml), dried over MgSO4, and condensed in vacuo to give the crude product. Purification by flash column chromatography (25% EtOAc/Hex) afforded the pure product as a white solid (145 mg, 73% yield). M.p C; 1 H NMR (300 MHz, CDC1 3 ): (d, J = 4.2 Hz, 1 H), (m, 1 H), (m, 1 H), 6.36 (d, J = 8.4 Hz, 1 H), 6.36 (s, 1 H), (m, 1 H), (m, 2 H), (m, 3 H), (m, 2 H), (m, 3 H); 13C1H} NMR (300 MHz, CDC1 3 ): , 148.5, 137.5, 3

5 - -~~~~ ~ ~ b' - II-l" '- -- F t" 112.5, 106.8, 50.3, 33.5, 25.9, 25.1; IR (KBr): 3263, 2924, 2850, 1609, 1519, 1486 cm- 1. Analysis calculated for C 11 H 1 6 N 2 : C, 74.96; H, Found: C, 74.84; H, (N-Benzyl, N'-methylamino)-pyrldine (entry 5). Procedure B was used to convert 3-bromopyridine and N-benzylmethylamine to the title product. Purification of the crude product by flash column chromatography (35% EtOAc/Hex) afforded the pure product as a pale yellow oil that solidified on standing (154 mg, 77% yield). M.p C; 1 H NMR (300 MHz, CDCl 3 ): (d, J = 2.8 Hz, 1 H), 7.97 (d, J = 4.3 Hz, 1 H), (m, 5 H), 7.09 (dd, J = 4.0 Hz, J = 7.95 Hz, 1 H), 6.97 (ddd, J = 1.6 Hz, J = 3.4, J = 8.5 Hz, 1 H), 4.55 (s, 2 H), 3.06 (s, 3 H); 13 ClH} NMR (75 MHz, CDC1 3 ): , 138.0, 137.9, 134.9, 128.8, 127.2, 126.7, 123.5, 118.6, 56.2, 38.5; IR (neat): 3025, 2896, 1585, 1496, 1453, 1351 cm- 1. Analysis calculated for C 13 H 14 N 2 : C, 78.75; H, Found: C, 78.92; H, (N-Methyl, N'-phenylamino)-pyridine (entry 6). Procedure B was used to convert 3-bromopyridine and N-methylaniline to the title product. Purification of the crude product by flash column chromatography (25% EtOAc/Hex) afforded the product as a pale yellow oil (141 mg, 77% yield). 1 H NMR (300 MHz, CDCI 3 ): (d, J = 2.0 Hz, 1 H), 8.14 (dd, J = 1.46 Hz, J = 4.24 Hz, 1 H), 7.33 (dd, J = 6.92 Hz, J = 8.4 Hz, 2 H), 7.22 (dd, J = 1.4 Hz, J = 3.0 Hz, 2 H), (m, 4 H), 3.34 (s, 3 H); 13C{1H} NMR (75 MHz, CDC1 3 ): , 145.2, 141.3, 140.7, 129.7, 124.9, 123.6, 13.4, 122.5, 40.2; IR (neat): 3036, 2941, 2883, 2815, 1600, 1577, 1495, 1421, 1344 cm- 1. Analysis calculated for C 12 H 12 N 2 : C, 78.17; H, Found: C, 78.37; H, (cyclohexylamino)-pyridine (entry 7). Procedure B was used to convert 3- bromopyridine and cyclohexylamine to the title product. Purification of the crude product by flash column chromatography (35% EtOAc/Hex) afforded the product as a yellow solid (135 mg, 82% yield). M.p C; 1 H NMR (300 MHz, CDC1 3 ): (d, J = 2.8, 1 H),

6 1> I '. I X 1t,11t.,t*1 Uxx.t* UXU jum-mht* St[ SJ1 5 t"hhi.. v.~f.,1h~1 - x ,S - "*ti Y JL 1 JE,1h..ht* L~ Iu~~x (dd, J = 1.3 Hz, J = 2.3 Hz, 1 H), 7.05 (dd, J = 4.4 Hz, J = 7.9 Hz, 1 H), 6.84 (ddd, J = 1.3 Hz, J = 2.8 Hz, J = 8.3 Hz, 1 Hz), 3.55 (s, 1 H), (m, 1H), (m, 2 H), (m, 3 H), (m, 5 H); 13 C{1H} NMR (125 MHz, CDCl 3 ): , 138.2, 136.4, 123.6, 118.6, 51.4, 33.2, 25.8, 24.8; IR (KBr): 3225, 2931, 2849, 1584, 1537, 1484, 1325 cm- 1. Analysis calculated for C 11 H 16 N 2 : C, 74.84; H, Found: C, 75.16; H, (n-Hexylamino)-pyridine (entry 8). Procedure B was used to convert 3- bromopyridine and 3 equivalents of n-hexylamine (3 mmol, 0.4 ml) to the title product. Purification by flash column chromatography (35% EtOAc/Hex) afforded the pure product as a yellow solid (119 mg, 67% yield). M.p ; 1H NMR (300 MHz, CDC1 3 ): (d, J = 2.9 Hz, 1 H),7.94 (dd, J = 1.2 Hz, J = 4.3 Hz, 1 H), 7.08 (dd, J = 4.6, J = 16.6 Hz, 1 H), 3.64 (s, 1 H), 3.43 (ddd, J = 1.3 Hz, J = 2.9 Hz, J = 8.2 Hz, 1 H), (m, 2 H), (m, 2 H), (m, 6 H), (m, 3 H); 13C NMR{1H} (75 MHz, CDC13): , 138.2, 135.9, 123.7, 118.2, 43.5, 31.6, 29.3, 26.8, 22.6, 14.0; IR (neat): 3258, 2929, 1584, 1472, 1414, 1314 cm- 1. Analysis calculated for C1 Hi 8 N 2 : C, 74.11; H, Found: C, 74.31; H, (N-Morpholino)-pyridine (entry 9). Procedure B was used to convert 3- bromopyridine and morpholine to the title product. Purification of the crude product by flash column chromatography (100% EtOAc) afforded the product as a pale yellow oil (125 mg, 75% yield). 1 H NMR (300 MHz, CDC1 3 ): (s, 1H), 8.14 (t, J = 2.9 Hz, 1 H), 7.18 (t, J = 2.3 Hz, 2 H), 3.88 (t, J = 4.8 Hz, 4 H), 3.19 (t, J = 4.9 Hz, 4 H); 13 C0 1 H} NMR (75 MHz, CDC13): , 141.2, 138.4, 123,7, 122.3, 66.8, 48.7; IR (neat): 3037, 2962, 2855, 1593, 1498, 1242, 1121, 928, 800, 707 cm- 1. Analysis calculated for C 9 H 12 N 2 0: C, 65.83; H, Found: C, 65.67; H, (N-methyl, N'-phenyl)-quinoline (entry 10). Procedure B was used to convert 3- bromoquinoline and N-methylaniline to the title product. Purification by flash column 5

7 - -~~~~ ~ ~ l - II-l" 'b'- -- F t" chromatography (15% EtOAc/Hex) afforded the pure product as a bright yellow oil that solidified on standing (199 mg, 85% yield). M.p C; 1H NMR (300 MHz, CDC1 3 ): (d, J = 3.1 Hz, 1 H), 7.99 (d, J = 7.7 Hz, 1 H), 7.67 (d, J = 6.6 Hz, 1 H), (m, 3 H), 7.34 (t, J = 7.7 Hz, 2 H), (m, 3 H), 3.44 (s, 3 H); 13C NMR{ 1 H} (75 MHz, CDC1 3 ): , 143.1, 142.4, 129.6, 128.9, 126.9, 126.5, 123.3, 122.2, 119.4, 40.5; IR (neat): 3059, 2944, 2883, 2813, 1591, 1494, 1430, 1379, 1357, 1303 cm- 1. Analysis calculated for C 16 Hi4N 2 : C, 82.02; H, Found: C, 82.17; H, (N-morpholino)-pyridine (entry 11). 4-bromopyridine hydrochloride (1 mmol, 194 mg), morpholine (1.2 mmol, 0.1 ml), Pd(OAc) 2 (0.04 mmol, 9 mg), dppp (0.04 mmol, 16 mg), NaOtBu (2.4 mmol, 230 mg), in toluene (0.11 M with bromopyridine, 9 ml) were heated to 700 C in an oven dried Schlenk flask under argon for 1 hour. The reaction solution was then cooled to room temperature, taken up in 20 ml diethyl ether, and then washed 3 times with 10 ml 10% HCI. The aqueous layers were basified to ph = 12 with 4N NaOH, and then extracted 3 times with 20 ml diethyl ether. The organic extracts were dried over Na 2 SO4 for 30 minutes, and condensed to give the pure product as a white solid (150 mg, 91% yield). M.p C; 1 H NMR (300 MHz, CDC1 3 ): (dd, J = 1.6 Hz, J = 4.9 Hz, 2 H), 6.67 (dd, J = 1.6 Hz, J = 4.9 Hz, 2 H), 3.84 (t, J = 4.9 Hz, 4 H), 3.29 (t, J = 4.9 Hz, 4 H); 13C NMR{1H} (75 MHz, CDCl 3 ): , 150.5, 108.4, 66.5, 46.3; IR (KBr): 2955, 2884, 2825, 1596, 1537, 1502, 1443, 1367, 1237 cm- 1. Analysis calculated for C 9 H 1 2 N 2 0: C, 65.78; H, Found: C, 65.81; H, (n-hexylamino)-pyridine (entry 12). 4-bromopyridine hydrochloride (1 mmol, 194 mg), n-hexylamine (1.2 mmol, 0.1 ml), Pd(OAc) 2 (0.04 mmol, 9 mg), (±) BINAP (0.04 mmol, 25 mg), NaOtBu (2.4 mmol, 230 mg), in toluene ( 0.11 M with bromopyridine, 9 ml) were heated to 700 C in an oven dried Schlenk flask under argon for 2 hours. The reaction mixture was then allowed to cool to room temperature, taken up in 10 ml diethyl ether, washed 3 6

8 1>>')I -Xlht1t.x X Uxx 1 1t.t* U XU jum-mht* St[ ~hi. ~f.,1h~1 vj '31 -. x 1 -,S "Y t*5t*vv JLI 1 pi..h1..htt* x 5 times with saturated brine, and dried over Na 2 SO 4 for 30 minutes, and condensed in vacuo to give the title product. Purification by flash column chromatography (EtOAc) gave the pure product as a white solid (119 mg, 67 % yield). M.p C; 1H NMR (300 MHz, CDC1 3 ): (dd, J = 1.5 Hz, J = 4.8 Hz, 2 H), 6.42 (dd, J = 1.5 Hz, J = 4.8 Hz, 2 H), 4.12 (s, 1 H), 3.14 (dd, J = 1.5 Hz, J = 6.3 Hz, 2 H), (m, 2 H), (m, 6 H), (m, 3 H); 13C NMR{ 1 H} (125 MHz, CDCl 3 ): , 149.9, 107.4, 42.6, 31.5, 29.1, 26.6, 22.5, 1.9; IR (KBr): 3237, 2919, 2849, 1608, 1525, 1461, 1349 cm- 1. Analysis calculated for C 11 H 18 N 2 : 0, 74.11; H, Found: C, 74.14; H, (n-Hexylamino)-pyridine (table 2, entry 1). Procedure B was used to convert 2- bromopyridine and 3 equivalents of n-hexylamine (3 mmol, 0.4 ml) to the title product. Purification by flash column chromatography (15% EtOAc/Hex with 5%NEt3) afforded the pure product as a yellow oil (131 mg, 74% yield). 1 H NMR (300 MHz, CDC13): (d, J = 4.1 Hz, 1 H), (m, 1 H), 6.54 (t, J = 6.0 Hz, 1 H), 6.36 (d, J = 8.5 Hz, 1 H), 4.45 (s, 1 H), 3.24 (dd, J = 6.9 Hz, J = 12.8 Hz, 2 H), (m, 2H), (m, 6 H), (m, 3 H); 13C{1H} NMR (125 MHz, CDCI 3 ): , 148.3, 137.5, 112.6, 106.4, 42.4, 31.7, 29.6, 26.9, 22.7, 14.1; IR (neat): 3261, 2927, 2865, 1605, 1575, 1456 cm- 1. Analysis calculated for C 11 Hl 8 N 2 : C, 74.11; H, Found: C, 74.12; H, N, N-(di-2-Pyridyl)-hexylamine (entry 2). 2-Bromopyridine (1 mmol, 0.1 ml), n- hexylamine (0.5 mmol, ml), Pd 2 (DBA) 3 (0.02 mmol, 8 mol % Pd, 18 mg), (±) BINAP (0.04 mmol, 25 mg), and NaOtBu (1.2 mmol, 130 mg) in toluene (0.1 M with 2,6- dibromopyridine, 5 ml) were heated to 700 C in an oven dried Schlenk flask under argon for 1 hour. The reaction mixture was allowed to cool to room temperature, and was then taken up in 10 ml diethyl ether, washed 3 times with 10 ml saturated brine, dried over MgSO 4, and condensed in vacuo to give the title product. Purification by flash column chromatography (10% EtOAc/Hex) afforded the pure product as a yellow oil (91 mg, 71% yield). 1 H NMR (300 7

9 - -~~~~ ~ ~ b' - II-l" '- -- F t" MHz, CDC13); (dt, J = 0.9 Hz, J = 1.9 Hz, 2 H), (m, 2 H), 7.08 (dd, J = 0.7 Hz, J = 8.4 Hz, 2 H), (m, 2 H), (m, 3 H), (m, 2 H), (m, 6H), (m, 3 H); 13C{ 1 H} NMR (75 MHz, CDC13): , 148.4, 137.3, 116.9, 114.9, 48.6, 31.8, 28.4, 26.9, 22.8, 14.2; IR (KBr): 2927, 2856, 1582, 1468, 1422 cm- 1. Analysis calculated for C 16 H 2 1 N 3 : C, 75.26; H, Found: C, 75.40; H, trans-n,n,n'-(tri-2-pyridyl)-1,2-cyclohexyldiamine (entry 3). 2-Bromopyridine (3 mmol, 0.3 ml), trans-1,2-cyclohexyldiamine (1 mmol, 0.12 ml), Pd 2 (DBA) 3 (0.015 mmol, 6 mol % Pd, 14 mg), BINAP (0.03 mmol, 20 mg), and NaOtBu (3.4 mmol, 327 mg) were heated to 700 C in an oven dried Schlenk flask under argon for 18 hours. The reaction mixture was allowed to cool to room temperature, and was then taken up in 10 ml diethyl ether, washed 3 times with 10 ml saturated brine, dried over MgSO4, and condensed in vacuo to give the crude product. Purification by flash column chromatography (15% EtOAc/Hex, with 5% NEt3) afforded the pure product as a yellow solid (258 mg, 77% yield). M.p C; 1 H NMR (300 MHz, CDC13): (d, J = 4.1 Hz, 2 H), 7.93 (d, J = 4.4 Hz, 1 H), 7.37 (dt, J = Hz, J = 7.76 Hz, 2 H), 7.19 (dt, J = 7.74 Hz, J = 1.77 Hz, 1 H), 6.86 (dd, J = 6.55 Hz, J = 5.2 Hz, 2 H), 6.58 (d, J = 8.06 Hz, 2 H), 6.37 (dd, J = 6.2 Hz, J = 5.2 Hz, 1 H), 6.09 ( d, J = 8.4 Hz, 1 H), 5.49 (d, J = 7.4 Hz, 1 H), 5.03 (dt, J = 11.4 Hz, J = 3.7 Hz, 1, H), (m, 1 H), (m, 1 H), (m, 1 H), (m, 3 H), (m, 3 H); 13C{1H} NMR (75 MHz, CDCl3): , 157.8, 148.4, 148.0, 137.6, 136.8, 117.8, 117.7, 111.7, 107.4, 59.7, 53.8, 33.9, 32.0, 26.2, 24.9; FT-IR (nujol): 2971, 2880, 2836, 1465, 1376 cm- 1 ; Analysis calculated for C21 H23N5: C, 73.02; H, Found: C, 73.29; H, N, N, N', N'-(tetra-2-Pyridyl)-1,3-diaminopropane (entry 4). 2-Bromopyridine (2 mmol, 0.2 ml), 1,3-diaminopropane (0.5 mmol, 0.04 ml), Pd 2 (DBA) 3 (0.01 mmol, 4 mol % Pd, 9 mg), (±) BINAP (0.02 mmol, 13 mg), and NaOtBu (2.2 mmol, 212 mg) were heated to 700 C in an oven dried Schlenk flask under argon for 2 hours. The reaction mixture was 8

10 1>>')I -Xlht1t.x X Uxx 1 1t.t* U XU jum-mht* St[ ~hi. ~f.,1h~1 vj '3-. x 1 -,S "Y t*5t*vv JLI 1 pi..h1..htt* x 36 5 allowed to cool to room temperature, and was then taken up in diethyl ether (10 ml), washed 3 times with saturated brine (10 ml), dried over MgSO4, and condensed in vacuo to give the crude product. Purification by flash column chromatography (25% EtOAc/Hex, with 5% NEt3) afforded the pure product as a clear oil that solidified on standing (135 mg, 70% yield). M.p C; 1H NMR (300 MHz, CDC13): (dd, J = 1.2 Hz, J = 4.9 Hz, 4 H), 7.47 (dt, J = 1.7 Hz, J = 7.5 Hz, 4 H), 7.07 (d, J = 8.4 Hz, 4 H), 6.81 (dt, J = 3.4 Hz, J = 4.5 Hz, 4 H), 4.29 (t, J = 7.4 Hz, 4 H), 2.10 (dt, J = 7.5 Hz, J = Hz, 2 H); 13C{lH} NMR (75 MHz, CDCl3): , 148.3, 137.1, 116.9, 114.8, 46.2, 26.8; FT-IR (KBr): , , , , , , , , , , , , 767.3, cm- 1. Analysis calculated for C23H22N6: C, 72.23; H, 5.8. Found: C, 71.98; H, ,6-Di-(anilino)-pyridine (entry 5).2 2,6-Dibromopyridine (1 mmol, 237 mg), aniline (2.4 mmol, 0.2 ml), Pd 2 (dba)s (0.04 mmol, 8 mol % Pd, 36 mg), dppp (0.08 mmol, 32 mg), and NaOtBu (2.8 mmol, 268 mg) in toluene (0.05 M with 2,6-dibromopyridine, 18 ml) were heated to 900 C in an oven dried Schlenk flask under argon for 18 hours. The reaction mixture was allowed to cool to room temperature, and was then taken up in diethyl ether (20 ml), washed 3 times with saturated brine (20 ml), dried over MgSO 4, and condensed in vacuo to give the title product. Purification by flash column chromatography (15% EtOAc/Hex with 5% NEt) afforded the pure product as a brown solid (225 mg, 86% yield). M.p C; 1 H NMR (300 MHz, CDCI3); (m, 9 H), (m, 2 H), 6.42 (s, 2 H), 6.31 (d, J = 8.0 Hz, 2 H); 1 3 C11H} NMR (75 MHz, CDCl3): , 140.8, 139.5, 129.3, 122.6, 120.5, 99.1; IR (KBr): 3401, 3248, 1584, 1501, 1443, 1302 cm- 1. (1) Aldrich catalog, [ ], reported m.p C (2) Acta Crystallographica, C 50 (12) (1994)

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