| 96.8% |
Stage #1: dimethyl aminoterephthalate With hydrogenchloride; sodium nitrite In methanol; water at 10℃; for 1h;
Stage #2: With aminosulfonic acid In methanol; water for 0.333333h;
Stage #3: N-(4-nitrophenyl)-3-oxobutanamide With sodium acetate In methanol; water at 10℃; for 2h; |
1 Production Example of compound (25)
First, while replacement with nitrogen was performed, 100 parts of propylene glycol monomethyl ether was heated, and refluxed at a solution temperature of 120°C or more. A mixture of 100 parts of styrene, 1.2 parts of β-mercaptopropionic acid, and 1.0 part of tert- butylperoxybenzoate [organic peroxide polymerization initiator PERBUTYL Z (registered trademark) (made by NOF CORPORATION) ] was dropped into the solution over 3 hours. After dropping was completed, the solution was stirred for 3 hours. While the solution temperature was raised to 170°C, distillation was performed at normal pressure. After the solution temperature reached 170°C, distillation was performed under a reduced pressure of 1 hPa for 1 hour. Thus, thesolvent was removed to obtain a polymer solid product. The solid product was dissolved in tetrahydrofuran, and reprecipitated with n-hexane. The precipitated solid was filtered to obtain a polymer resin unit (79).; Next, 3.11 parts of p-nitroaniline (80) was added to 30 parts of chloroform, and the obtained solution was cooled with ice to 10°C or less. Then, 1.89 parts of diketene (81) was added thereto. Subsequently, the solution was stirred at 65°C for 2 hours. After the reaction was completed, the product was extracted with chloroform, and condensed to obtain 4.70 parts of a compound (82) (yield of 94.0%).; Next, 40.0 parts of methanol and 5.29 parts ofconcentrated hydrochloric acid were added to 4.25 parts of 2-aminodimethyl terephthalate (83), and the mixed solution was cooled with ice to 10°C or less. Asolution in which 2.10 parts of sodium nitrite was dissolved in 6.00 parts of water was added to the solution to make a reaction for 1 hour at the same temperature as above. Next, 0.990 parts of sulfamic acid was added to the solution, and the solution was stirred for 20 minutes (diazonium salt solution). 4.51 parts of the compound (82) was added to 70.0 parts of methanol. The obtained solution was cooled with ice to10°C or less, and the diazonium salt solution was added. Subsequently, a solution in which 5.83 parts of sodium acetate was dissolved in 7.00 parts of water was added to make a reaction for 2 hours at 10°C or less. After the reaction was completed, 300 parts of water was added to the reaction solution, and the reactionsolution was stirred for 30 minutes. Then, a solid was filtered, and refined by recrystallization from N,N- dimethylformamide to obtain 8.71 parts of a compound (84) (yield of 96.8%) .; Next, 8.58 parts of the compound (84) and 0.40 parts of palladium-activated carbon (5% of palladium) were added to 150 parts of N, -dimethylformamide, and stirred for 3 hours at 40°C under a hydrogen gas atmosphere(reaction pressure of 0.1 to 0.4 MPa) . After the reaction was completed, the solution was filtered, and condensed to obtain 6.99 parts of a compound (85)(yield of 87.5%) .; Next, 6.50 parts of the compound (85) was added to 30.0 parts of chloroform. The solution was cooled with ice to 10°C or less, and 0.95 parts of diketene (81) was added. Subsequently, the solution was stirred for 2 hours at 65°C. After the reaction was completed, the reaction product was extracted with chloroform, and condensed to obtain 7.01 parts of an azo compound intermediate product (86) (yield of 94.2%).; Next, 15.0 parts of methanol and 1.48 parts ofconcentrated hydrochloric acid were added to 1.78 parts of 2- ( 4-nitrophenyl) ethanol (87), and the solution was cooled with ice to 10°C or less. A solution in which 1.08 parts of sodium nitrite was dissolved in 3.00 parts of water was added to the solution to make a reaction for 1 hour at the same temperature as above. Next, 0.380 parts of sulfamic acid was added to the reaction solution, and the reaction solution was stirred for 20 minutes (diazonium salt solution) . A solution in which 7.18 parts of potassium carbonate was dissolved in 7.00 parts of water and 6.50 parts of the compound (86) were added to 70.0 parts of N,N- dimethylformamide . The obtained solution was cooled with ice to 10°C or less. The diazonium salt solution was added thereto to make a reaction for 2 hours at10°C or less. After the reaction was completed, 300 parts of water was added to the solution, and the solution was stirred for 30 minutes. Then, a solid was filtered, and refined by recrystallization from N,N- dimethylformamide to obtain 7.62 parts of a compound(88) (yield of 91.0%) .; Next, 0.689 parts of the compound (88) was added to 100 parts of dehydrated N-methylpyrrolidone, and the solution was heated to 100°C to dissolve the compound(88). After the dissolution, the temperature was dropped to 50°C. 10.0 parts of the polymer (A)dissolved in 30 parts of dehydrated N-methylpyrrolidone was added, 0.349 parts of l-ethyl-3- ( 3- dimethylaminopropyl) carbodiimide-hydrochloric acid salt was added, and the solution was stirred for 3 hours at 50°C. The solution temperature was gradually returned to normal temperature, and stirring was performed overnight to complete the reaction. After the reaction was completed, the solution was condensed, and separated with chloroform. After extraction, refining by silica gel column chromatography, and reprecipitation with methanol were subsequentlyperformed to obtain 8.51 parts of the compound (25) .; From the measurements using the apparatuses, it was found that the obtained product has the structure represented by the formula above. The results of analysis are shown below.; Result of analysis of compound (25) having bisazoskeleton unit[1] Results of measurement of molecular weight (GPC) : weight average molecular weight (Mw) = 17993, number average molecular weight (Mn) = 10742[2] Result of measurement of acid value:0 mgKOH/g[3] Results of XH NMR (400 MHz, CDC13 at roomtemperature) (see Figure 1): δ [ppm] = 15.65 (s, 1H) , 14.76 (s, 1H) , 11.49 (s, 1H) , 11.40 (s, 1H) , 8.62 (s, 1H) , 8.15 (d, 1Ή), 7.80 (d, 1H) , 7.74 (d, 2Ή) , 7.64 (d, 2H) , 7.37-6.27 (m, 550H) , 4.24 (br, 1H) , 4.07 (s, 3H) , 3.98 (s, 3H) , 3.73 (br, 1H) , 3.24-2.84 (m, 10H) , 2.69 (s, 3H), 2.57 (s, 3H) , 2.45-0.77 (m, 330H) |
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