3. Experimental Section
All reactions were carried out under an inert atmosphere using oven-dried glassware. All solvents for the reactions were of reagent grade. Flash column chromatography was carried out using silica gel as the stationary phase. Melting points are uncorrected. The UV-Vis spectra were recorded using a Perkin Elmer Lambda 25 and the fluorescence measurements were recorded using a Shimadzu RF5301 instrument. The CV data were recorded at room temperature on a CH-Instruments 440 Electrochemical Analyser. CVs were recorded at a concentration of 1 × 10−4 M in CH2Cl2 containing tetra-n-butyl ammonium hexafluorophosphate (Bu4NPF6 0.1 M) as supporting electrolyte with a platinum working and counter electrodes and a silver wire as a quasi-reference electrode. The E½ values for the compounds were determined relative to the ferrocenium/ferrocene (Fc+/Fc) redox couple (used as an internal standard). The Fc+/Fc couple was adjusted to 0.0 V and the reduction potentials presented in Table 2 are relative to this value. Spartan ‘08 (Wavefunction Inc., Irvine, CA, USA) was used to model the structures of compounds 11 and 12 (analogues of 1 and 2 where the octyl and isobutyl chains have been shortened to a methyl unit to facilitate faster calculation times). The structures were optimized using RB3LYP/6-31G(D) methodology.
1-Chloro-2-nitro-4-(trifluoromethyl)benzene (3) (5.00 g, 24.27 mmol), p-phenylenediamine (4) (2.40 g, 22.17 mmol) and triethylamine (3 mL, 22.17 mmol) were dissolved in THF (60 mL) and were heated under reflux for 2 days. The NEt3·HCl salt which formed was removed by filtration and the organic solvent was removed under reduced pressure. The residue was dissolved in DCM, washed with water (2 × 100 mL) and dried with MgSO4, filtered and the solvent was concentrated under reduced pressure. Purification by column chromatography (silica gel: eluting with petroleum ether/ethyl acetate 7:3) afforded 5 as a red powder (3.50 g, 53%), mp 116–118 °C. 1H NMR (400 MHz, CDCl3) δ = 9.49 (s, 1H, NH), 8.42 (s, 1H, CH), 7.40 (d, 1H, J = 9.2 Hz, CH), 6.98 (d, 2H, J = 8.4 Hz, CH), 6.96 (d, 1H, J = 8.4 Hz, CH), 6.68 (d, 2H, J = 8.4 Hz, CH), 3.73 (s, 2H, NH). 13C NMR (100 MHz, CDCl3) δ = 146.8, 145.8, 131.6, 127.8, 127.6, 124.7, 116.7, 116.0. MS (FAB/NOBA (M + H)+) m/z 298.4. νmax/cm−1 3414s, 3349s, 3221w, 3016m, 2970w, 1738w, 1631s, 1573s, 1506s, 1357m, 1321s (C-NO2), 1226m, 1091m, 919s, 827m, 763s, 686s. Anal. Calc. for C13H10F3N3O2: C 52.52%, H 3.37%, N 14.14%. Found: C 52.50%, H 3.35%, N 14.08%.
Compound 5 (3.50 g, 11.79 mmol), Pd(C) 10% (0.30 g) and ammonium formate (4.50 g, 71.43 mmol) were dissolved in methanol (60 mL) and were left stirring at room temperature for 1 h. The Pd(C) was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was washed with DCM to precipitate the ammonium formate, which was removed by filtration. The organic solution was then concentrated under reduced pressure to produce a red solid (6) (3 g). No further purification was undertaken due to the instability of the compound.
Compound 6 (3.00 g, 11.24 mmol), boric anhydride (0.78 g, 11.24 mmol) and alloxan monohydrate (1.6 g, 11.20 mmol) were dissolved in glacial acetic acid (50 mL) and the resulting solution was stirred at room temperature for 1 h. The product was collected by adding DCM and then extracted from the reaction mixture. The mixture was dried over magnesium sulfate, filtered and the solvent was removed under reduced pressure. Purification by column chromatography (silica gel: eluting with DCM/petroleum ether 9:1) afforded 7 as a dark red powder (0.24 g, 55%), mp > 300 °C. 1H NMR (400 MHz, DMSO) δ = 11.52 (s, 1H, NH), 8.51 (s, 1H, CH), 8.03 (dd, 1H, J = 1.6 Hz, 9 Hz, CH), 7.09 (d, 1H, J = 8.8 Hz, CH), 7.00 (d, 2H, J = 8.4 Hz, CH), 6.78 (d, 2H, J = 8.4 Hz, CH), 5.63 (s, 2H, NH2). 13C NMR (100 MHz, DMSO) δ = 159.3, 155.6, 152.7, 150.1, 141.2, 137.5, 133.8, 129.9, 128.5, 127.9, 125.8, 125.5, 124.9, 123.1, 122.2, 118.7, 114.3. MS (FAB/NOBA (M + H)+) m/z 373.8. νmax/cm−1 3470w, 3347s, 3016m, 2970s, 2948w, 1737w, 1653m, 1538m, 1505m, 1446m, 1345w, 1293s, 1229w,1110s, 1065s, 903s, 841s, 765s. Anal Calc. for C17H10F3N5O2: C 54.69%, H 2.68%, N 18.76%. Found: C 54.42%, H 2.68%, N 17.67%.
A solution of naphthalene dianhydride (8) (0.30 g, 1.34 mmol) in dry DMF (50 mL) was heated to 140 °C under N2 atmosphere. octylamine (0.19 g, 1.34 mmol) was then added drop wise. The reaction mixture was heated under reflux for 24 h. Compound 7 (0.50 g, 1.34 mmol) was then added. After 5 days heating under reflux, the reaction mixture was cooled and the DMF was removed under reduced pressure. Purification by column chromatography (silica gel: eluting with DCM/acetone 9:1) and subsequent recrystallization from diethyl ether afforded 1 as a yellow/brown powder (0.10 g, 10%), mp 190–192 °C. 1H NMR (400 MHz, CDCl3) δ = 11.65 (s, 1H, NH), 8.75 (s, 4H, CHNDI), 8.61 (s, 1H, CHar), 8.12 (dd, 1H, J = 2.1 Hz, 9.2 Hz, CHar), 7.82 (d, 2H, J = 8.6 Hz, CHar), 7.63 (d, 2H, J = 8.6 Hz, CHar), 6.98 (d, 1H, J = 9.2 Hz, CHar), 4.09 (t, 1H, J = 7.4 Hz, 9.5 Hz CH2). 1.69 (br, 2H, CH2), 1.23–135 (br, 10H, CH2), 0.87 (t, 3H, J = 5.2 Hz, 7Hz, CH3). 13C NMR (100 MHz, CDCl3) δ = 162.8, 162.7, 159.1, 131.3, 130.5, 128.5, 126.7, 126.5, 117.8, 40.2, 31.2, 28.7, 28.6, 27.4, 26.5, 22.1, 13.9. MS [FAB/NOBA (M + H)+] m/z: 735.8. HRMS (FAB/NOBA), C39H29N6O6F3: Calcd: 735.2179, found. 735.2173. νmax/cm−1 3357w, 3082m, 2923m, 2855w, 1791w, 1716m, 1659s, 1595s, 1549m, 1333s, 1305m, 1248m, 1202s, 1166s, 1129m, 1068s, 841m, 767s.
Naphthalene dianhydride (8) (0.36 g, 1.35 mmol) was dissolved in dry DMF (30 mL). The solution was heated to about 140 °C under N2 atmosphere. To this octylamine (0.18 g, 1.35 mmol) was added drop wise for about 10 min and the reaction mixture was heated under reflux for 24 h. Compound 9 (0.3 g, 0.68 mmol) was added and the mixture was left heating under reflux for another 4 days. The reaction mixture was cooled down and the DMF was removed under reduced pressure. Purification by column chromatography (silica gel: eluting with 100% DCM) followed by recrystallization from diethyl ether afforded 2 as a yellow/brown product (0.06 g, 11%), mp 190–192 °C (dec). 1H NMR (400 MHz, CDCl3) δ = 8.78 (s, 4H, CHNDI), 8.59 (d, 1H, J = 1.2 Hz, CHar), 8.04 (dd, 1H, J = 2 Hz, 9 Hz, CHar), 7.89 (d, 2H, J = 8.4 Hz, CHar), 7.76 (d, 1H, J = 8.8 Hz, CHar), 7.28 (d, 2H, J = 8.4 Hz, CHar), 4.62 (br, 2H, CH2). 4.21 (t, 2H, J = 7.6 Hz, 9.3 Hz, CH2), 2.48 (m, 1H, CH), 1.76 (m, 2H, CH2), 1.44–1.22 (m, 12H, CH2), 1.08 (d, 6H, J = 6.8 Hz, CH3), 0.88 (t, 3H, J = 6.6 Hz, 75Hz, CH3). 13C NMR (100 MHz, CDCl3) δ = 162.9, 162.8, 131.6, 131.4, 130.9, 130.8, 128.5, 127.0, 126.7, 116.7, 44.8, 41.1, 31.8, 29.3, 29.2, 28.1, 27.5, 27.1, 22.3, 20.1, 14.1. MS (FAB/NOBA (M + H)+) m/z 804.6. νmax/cm−1 3062w, 2925m, 2855w, 1707s, 1660s, 1594m, 1558s, 1450s, 1340m, 1222m, 1170m, 1124m, 1002m, 820m, 767s, 717m. Anal. Calc. for C44H39F3N6O6: C 65.66%, H 4.88%, N 10.44%. Found: C 65.16%, H 5.01%, N 9.99%.
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