1: 21%
2: 16%
3: 13% |
With tris-(dibenzylideneacetone)dipalladium(0); tris(o-methoxyphenyl)phosphine; caesium carbonate; Trimethylacetic acid In toluene at 100℃; Schlenk technique; Inert atmosphere; |
3.2. Synthesis of Os1~5
DPP (209.60 mg, 0.399 mmol, 1.5 equiv), Cz (150 mg, 0.266 mmol, 1 equal), PivOH(8.15 mg, 30% mol), anhydrous Cs2CO3 (173.50 mg, 0.533 mmol), Pd2(dba)3 (3.70 mg,1.5 mol%), and tris(o-methoxyphenyl) phosphine (2.90 mg, 3 mol%) were added into aSchlenk tube. The mixture in the Schlenk tube was evacuated and argon-filled three times.Next, 5 mL toluene was added into the tube via a syringe and the air in the Schlenk tubewas removed by freeze-vacuum-thaw cycles three times. The argon-filled tube was thenplaced in an oil pot at 100 C for 24 h. Removal of the toluene by rotary evaporator affordedthe crude product, which was purified by CC on silica gel using a mixture of CH2Cl2 andhexane as an eluent (The volume ratio CH2Cl2/hexane gradually increased from 0.8 to 3)and successively gave Os1~5, O1 (58 mg, yield 21%), O2 (42 mg, yield 16%), O3 (35 mg,yield 13%), O4 (32 mg, yield 12%), O5 (26 mg, yield, 10%).O1 (DPP-Cz-DPP): 1H NMR (400MHz, CDCl3) 9.11 (dd, J = 16.9, 3.6 Hz), 8.93-8.88 (m),8.16-8.07 (m), 7.86 (s), 7.70-7.54 (m), 7.30-7.27 (m), 4.64 (s), 4.18-4.02 (m), 2.48-2.25 (m),2.08-1.86 (m), 1.31 (ddd, J = 67.7, 37.5, 27.1 Hz), 0.99-0.85 (m), 0.78 (t, J = 6.9 Hz).MALDI-TOF MS (m/z): [M]+ calcd. For C89H119N5O4S4, 1451.188, found 1449.904.Elemental analysis: calcd for: C89H119N5O4S4, C, 73.66; H, 8.27; N, 4.83%. Found: C,73.54; H, 8.22; N, 4.79%.O2 (DPP-(Cz-DPP)2): 1H NMR (400 MHz, CDCl3) 9.11 (s), 8.91 (dd, J = 3.8, 1.0 Hz),8.13 (dd, J = 11.7, 8.4 Hz), 7.87 (s), 7.71-7.54 (m), 7.28 (dd, J = 5.0, 4.0 Hz), 4.7 -4.58 (m),4.13 (dd, J = 23.3, 15.6 Hz), 2.35 (dd, J = 9.5, 4.5 Hz), 2.01 (dd, J = 8.9, 4.1 Hz), 1.44-1.10 (m),1.00-0.85 (m), 0.79 (t, J = 6.9 Hz).MALDI-TOF MS (m/z): [M]+ calcd. For C148H198N8O6S6, 2377.596, found 2376.625.Elemental analysis: calcd for: C148H198N8O6S6 C, 74.76; H, 8.39; N, 4.71%. Found: C,74.68; H, 8.32; N, 4.75%.O3 (DPP-(Cz-DPP)3): 1H NMR (400 MHz, CDCl3) 9.09 (d, J = 14.8 Hz), 8.90 (d,J = 3.3 Hz), 8.12 (s), 7.87 (s), 7.63 (dd, J = 21.8, 16.8 Hz), 4.65 (s), 4.11 (d, J = 37.9 Hz), 2.36 (d,J = 7.4 Hz), 2.05 (s), 1.43-1.15 (m), 0.99-0.86 (m), 0.79 (t, J = 6.5 Hz).MALDI-TOF MS (m/z): [M]+ calcd. For C207H277N11O8S8, 3304.003, found 3302.268.Elemental analysis: calcd for: C207H277N11O8S8, 75.25; H, 8.45; N, 4.4.66%. Found: C,75.28; H, 8.42; N, 4.69%.O4 (DPP-(Cz-DPP)4): 1H NMR (400 MHz, CDCl3) 9.11 (d, J = 16.8 Hz, 8H), 8.94 (d,J = 3.1 Hz, 2H), 8.19-8.09 (m, 8H), 7.90 (s, 4H), 7.7-7.56 (m, 22H), 7.33-7.29 (m, 2H), 4.68 (s,4H), 4.14 (d, J = 39.6 Hz, 20H), 2.39 (s, 8H), 1.99 (d, J = 55.5 Hz, 18H), 1.48-1.15 (m, 176H),1.03-0.89 (m, 60H), 0.84-0.78 (m, 24H).MALDI-TOF MS (m/z): [M]+ calcd. For C266H356N14O10S10, 4230.411, found 4231.378. Elemental analysis: calcd for: C266H356N14O10S10, 75.52; H, 8.48; N, 4.64%. Found: C,75.48; H, 8.45; N, 4.69%.O5 (DPP-(Cz-DPP)5):1H NMR (400 MHz, CDCl3) 9.13 (d, J = 16.1 Hz, 10H), 8.94(d, J = 3.1 Hz, 2H), 8.13 (d, J = 8.4 Hz, 10H), 7.90 (s, 5H), 7.72-7.59 (m, 27H), 7.32-7.29 (m,2H), 4.67 (s, 5H), 4.14 (d, J = 39.0 Hz, 24H), 2.39 (s, 10H), 2.06 (s, 24H), 1.45-1.16 (m, 216H),1.04-0.91 (m, 72H), 0.82 (dd, J = 6.7, 4.4 Hz, 30H).MALDI-TOF MS (m/z): [M]+ calcd. ForC325H435N17O12S12, 5156.818, found 5156.625.Elemental analysis: calcd for: C325H435N17O12S12, 75.70; H, 8.50; N, 4.62%. Found: C,75.68; H, 8.47; N, 4.64%. |