85% |
With potassium carbonate sesquihydrate In lithium hydroxide monohydrate; N,N-dimethyl-formamide at 85℃; |
2.4.1. 4,4’-[benzene-1,3-diylbis(oxy)]dibenzene-1,2-dicarbonitrile (1)
In a three-necked flask equipped with a magnetic stirrer, reflux condenser and thermometer 10.00 g (0.058 mol) of 4-nitrophthalonitrile, 3.2 g (0.029 mol) of resorcinol, 40 mL of DMF were added. Then, 10 g (0.072 mol) of K2CO3 1.5H2O preliminarily dissolved in 13.3 mL of deionized water and added to the reacting solution. The reaction was carried out for 1.5 h at the temperature of 85 °C. The precipitate formed was filtered off, washed with isopropyl alcohol and water. The final product was dried under vacuum. Yield: 85%, m.p. 185 °C (DSC). 1H NMR (250 MHz, DMSO-d6, δ, ppm): 8.13 (d, J = 8.8 Hz, 2H, H1), 7.92 (d, J = 2.6 Hz, 2H, H2), 7.60 (m, 1H, H6), 7.55 (dd, J = 8.8, 2.9 Hz, 2H, H3), 7.13 (m, 3H, H4, H5). FT-IR (ν, cm-1): 3079 (CAr-H), 2231 (CN), 1586 (CAr-CAr), 1249 (CAr-O-CAr). |
84.1% |
With potassium carbonate In (methylsulfinyl)methane at 20℃; for 24h; |
|
82% |
With potassium carbonate In (methylsulfinyl)methane at 70℃; for 8h; |
3.4.1. Synthesis of 4,4’-[1,3-Phenylenebis(oxy)]diphthalonitrile
Resorcinol (0.09 g, 0.86 mmol), potassium carbonate (0.12 g, 0.86 mmol) and 50 mLof dry DMSO were mixed in a two-necked flask and stirred at 70 C for 1 h. Then 4-nitrophthalonitrile (1, 0.30 g, 1.70 mmol) and potassium carbonate (0.18 g, 1.30 mmol) wereadded to the reaction mixture, after which stirring was continued for additional 7 h at aconstant temperature. After a lapse of time, the reaction mixture was cooled and pouredinto 150 mL of a 0.1 mol/L aqueous solution of HCl and left until a precipitate formed.The precipitate was filtered off and sequentially washed with distilled water (2 30 mL),0.1 mol/L HCl solution (2 30 mL) and distilled water (2 30 mL) to neutral pH, andthen recrystallized from ethanol. The output was a beige fluffy powder, soluble in acetone,ethanol, chloroform, DMF. Yield: 0.26 g (82%). FT-IR: nmax, cm1 3088, 2917, 2850 (Car-H);2243 (CN); 1586, 1474, 1389 (Car=Car); 1256 (Ar-O-Ar). 1H-NMR (500 MHz, CDCl3):δ, ppm 7.76 (dd, 2 H, J = 8.6); 7.55 (t, 1 H, J = 8.3); 7.32 (d, 2 H, 4J = 2.5); 7.29 (dd, 2 H,4J = 2.5, 3J = 8.3); 6.99 (dd, 2 H, 3J = 8.3, 4J = 2.2); 6.82 (m, 1 H, 4J = 2.2). 13C-NMR (100 MHz,acetone-d6): δ, ppm 160.66, 155.52, 135.65, 132.35, 122.03, 117.91, 117.66, 115.10, 114.74,112.85, 109.91. MS (MALDI-TOF): m/z 362.11 [M]+, calcd. 363.08 |
70% |
With potassium carbonate In (methylsulfinyl)methane at 20 - 70℃; for 430h; Inert atmosphere; |
Synthesis of 4, 4′-(1, 3-phenylenebis (oxy)) diphthalonitrile (3)
Compound 2 (1.272 g) was dissolved in dry DMSO (10 mL) andcompound 1 (4.00 g, 28.90 mmol) was added under inert atmosphere.Finely ground anhydrous potassium carbonate (8.00 g) was added tothis reaction mixture and stirred for 10 h at 70 °C. After stirring at roomtemperature for 7 days, the reaction was monitored by thin layerchromatography (TLC) as it proceeded under Ar. Finally, the reactionmixture was poured onto ice and crystalized from ethanol to form alight yellow precipitate. The pure product was dried using P2O5 under avacuum for 15 days. The yield was 2.80 g or 70%. The following FT-IR(ATR) signals were observed (υmax/cm-1): 3120/3093/3074 (Ar-CH), 2235 (C^N), 1587/1593 (C]C), 1310/1285/1247 (CeOeC). 1H NMR(DMSO-d6), δ (ppm): 8.14 (2H, d, Ar-H), 7.93 (2H, d, Ar-H), 7.61 (H, t,Ar-H), 7.56 (H, d, Ar-H), 7.57 (H, d, Ar-H) 7.15 (2H, s, Ar-H), 7.14 (H,s, Ar-H). Anal. calcd. for C22H10N4O2 C, 72.92; H, 2.78; N, 15.46, foundC, 72.65; H, 2.29; and N, 15.75%. LC-MS, m/z anal. calcd. 362.34,found [M]+: 362.09, and [M + H2O]+: 380.12. |
68.7% |
With potassium carbonate In (methylsulfinyl)methane at 40℃; for 12h; Inert atmosphere; |
2.3. Synthesis of phthalonitrile compound (CN)
To a 500 mL three-neck rounde-bottom flask was added resorcinol (16.52 g, 0.15 mol), 4-nitrophthalonitrile (51.94 g, 0.30 mol) and 180 mL DMSO. During the course of the reaction, the K2CO3 (62.19 g, 0.45 mol) was added in three portions at an interval of 20 min. Then the resulting mixture was heated at 40 °C for 12 h under nitrogen. After cooling, the product mixture was poured into water. The light yellow filtrate was collected by suction filtration and washed with large amount of water until the filtrate was neutral. The crude product (42.0 g) was purified by rinsing with CH2Cl2 in Buchner funnel and suction flask, and the filtrate was then dried by evaporation under a vacuum at 80 °C for 5 h to remove CH2Cl2. The yellow-white powder was obtained in 68.7 wt% yield (28.9 g), m. p. peak at 183 °C (sharp) (DSC) at a heat rate of 10 °C/min. FTIR (KBr), 2232 (C≡N), 1284 (Ar-O-Ar), 1248 (Ar-O-Ar). 1H NMR (400 MHz, DMSO-d6): 8.14-8.11 (d, 2H; Ar H), 7.92 (s, 2H; Ar H), 7.63-7.53 (m, 3H; Ar H), 7.15-7.12 (m, 3H; Ar H). |
65% |
Stage #1: 4-Nitrophthalonitrile; recorcinol In N,N-dimethyl-formamide at 20℃; for 1h;
Stage #2: With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 1h; |
Synthesis of 4,4-[1,3-phenylenebis(oxy)]diphthalonitrile (2).
4-Nitrophthalonitrile (1.00 g, 5.78 mmol), resorcinol (0.32 g,2.89 mmol), and DMF (100 mL) were placed in a three-necked flask equipped with a magnetic stirrer, a thermometer, and a refl uxcondenser. After the substances were completely dissolved, thereaction mixture was stirred for 1 h at 20 °C. Then potassium carbonate (1.00 g, 7.26 mmol) was introduced by equal portions.The mixture was stirred for 48 h at ~20 °C, after which it waspoured into 300 mL of a 0.1 M solution of NaOH and filtered off . The obtained pale yellow precipitate was washed with water,a 10% solution of alkali, and water again to the neutral pH, andwashed from the fi lter with DMF. Then DMF was distilled offin vacuo. The subsequent purifi cation was performed by recrystallizationfrom ethanol (65% yield). 1 NMR (CDCl3), δ: 7.76(dd, 2 H, H(12,18), J = 8.6 Hz); 7.55 (t, AX2 pattern, 1 H, H(6),J = 8.3 Hz); 7.32 (d, 2 H, H(7,13), 4J = 2.5 Hz); 7.29 (dd, 2 H,H(9,17), 4J = 2.5 Hz, 3J = 8.3 Hz); 6.99 (dd, 2 H, H(3,5), 3J == 8.3 Hz, 4J = 2.2 Hz); 6.82 (m, AX2 pattern, 1 H, 4J = 2.2 Hz).13 NMR (acetone-d6), δ: 160.66 ((8,16)); 155.52 ((2,4));135.65 ((12,18)); 132.35 ((6)); 122.03 ((7,9,13,17); 117.91((20,22); 117.66 ((19,21)); 115.10 ((10,14)); 114.74 ((3,5));112.85 ((1)); 109.91 ((11,15)). MS MALDI-TOF, found:362.11 [M]+. C22H10N4O2. Calculated: M = 362.08. |
65% |
With potassium carbonate In N,N-dimethyl-formamide at 25℃; for 48h; |
4.3.1. Synthesis of 4,4’-[1,3-phenylenebis(oxy)]diphthalonitrile (2)
4-Nitrophthalonitrile (1.00 g, 5.77 mmol) and resorcinol (0.32 g,2.88 mmol) were dissolved in 100 ml of dry DMF. After stirring for 1 h atroom temperature, finely ground anhydrous potassium carbonate(0.99 g, 2.5 mmol) was added to the described solution. The reactionmixture was stirred at 25 C for 48 h and then it was poured into 300 mlof 0.1 M NaOH aqueous solution. The resulting precipitate were filteredoff and washed with deionized water (2 30 ml), 0.1 M aqueous solutionof NaOH (2 30 ml) and finally with deionized water (2 30 ml)until neutral pH. Obtaining coarse crude crystals were recrystallizedform ethanol to remove any residual of reagents. The pure product wasobtained as light yellow powder and it was soluble in chloroform,ethanol, and acetone. Yield 0.68 g (65%) mp 190 C. FT-IR: max, cm 13088, 2917, 2850 (Car - H); 2243 (C- - -N); 1586, 1474, 1389 (Car Car);1256 (Ar-O-Ar). 1H NMR (500 MHz, CDCl3): , ppm 7.76 (dd, 2 H,J 8.6); 7.55 (t, 1 , J 8.3); 7.32 (d, 2 , 4J 2.5); 7.29 (dd, 2 ,4J 2.5, 3J 8.3); 6.99 (dd, 2 , 3J 8.3, 4J 2.2)); 6.82 (m, 1 ,4J 2.2). 13C NMR (100 MHz, Acetone-d6): , ppm 160.66, 155.52,135.65, 132.35, 122.03, 117.91, 117.66, 115.10, 114.74, 112.85,109.91. MS (MALDI-TOF): m/z 362.11 [M], calcd. 363.08. |
|
With potassium carbonate In (methylsulfinyl)methane |
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