* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With hydrogenchloride; triethylamine In water; acetone
D. Preparation of Bisphenol A Dicyanate A 456.60 gram portion of 4,4'-isopropylidene diphenol (2.00 moles), 444.91 grams of cyanogen bromide (4.20 moles) and 1,100 milliliters of acetone were added to a reactor and maintained under a nitrogen atmosphere with stirring. The stirred solution was cooled to -5°C, then 406.82 grams of triethylamine (4.02 moles) was added to the reactor over a 60 minute period and so as to maintain the reaction temperature at -5 to -3°C. After completion of the triethylamine addition, the reactor was maintained at -5 to -3°C for an additional twenty-five minutes followed by addition of the reactor contents to 1.5 gallons (5.685 l) of deionized water. After 5 minutes, the water and product mixture was multiply extracted with three 500 milliliter volumes of methylene chloride. The combined methylene chloride extract was washed with 500 milliliters of 0.05 percent by weight aqueous hydrochloric acid followed by washing with 500 milliliters of deionized water, then drying over anhydrous sodium sulfate. The dry methylene chloride extract was filtered and solvent removed by rotary evaporation under vacuum for 60 minutes at 100°C. Bisphenol A dicyanate (545.8 grams) was recovered in 98.1 percent yield as a light tan colored, crystalline solid. Infrared spectrophotometric analysis of a film sample of the product confirmed the product structure (disappearance of phenolic hydroxyl absorbance, appearance of cyanate absorbance).
98.1%
With hydrogenchloride; triethylamine In water; acetone
A. Preparation of Bisphenol A Dicyanate 4,4--Isopropylidene diphenol (456.60 grams, 4.0 hydroxyl equivalents), cyanogen bromide (444.91 grams, 4.20 moles) and acetone (1100 milliliters) were added to a reactor and maintained under a nitrogen atmosphere with stirring. The stirred solution was cooled to -5°C, then triethylamine (406.82 grams, 4.02 moles) was added over a 60 minute period and so as to maintain the reaction temperature at -5°C to -3°C. After completion of the triethylamine addition, the reactor was maintained at -5°C to -3°C for an additional 25 minutes followed by addition of the reactor contents to 1.5 gallons of deionized water. After 5 minutes, the water and product mixture was multiply extracted with three 500 milliliter volumes of methylene chloride. The combined methylene chloride extract was washed with 500 milliliters of 0.05 percent by weight aqueous hydrochloric acid followed by washing with 500 milliliters of deionized water, then drying over anhydrous sodium sulfate. The dry methylene chloride extract was filtered and solvent removed by rotary evaporation under vacuum for 60 minutes at 100°C. The bisphenol A dicyanate (545.8 grams) was recovered in 98.1 percent yield as a tan colored crystalline solid. Infrared spectrophotometric analysis of a film sample of the product confirmed the product structure (disappearance of phenolic hydroxyl absorbance, appearance of cyanate absorbance).
Reference：
[1] Patent: EP291552, 1988, A1,
[2] Patent: EP409069, 1991, A2,
[3] Journal of Crystallographic and Spectroscopic Research, 1990, vol. 20, # 3, p. 285 - 289
[4] Russian Journal of Organic Chemistry, 2009, vol. 45, # 1, p. 154 - 157
With triethylamine; sodium hydroxide; In dichloromethane; water; at 0 - 5℃;Large scale;
Example 12 (0284) 2850 g (25.0 mol relative to OH group) of 2,2-bis(4-hydroxyphenyl)propane (manufactured by Wako Pure Chemical Industries, Ltd.), 1119 g (28.0 mol) of sodium hydroxide (in an amount of 1.12 moles based on 1 mole of hydroxy group of the hydroxy group-substituted aromatic compound), and 75 g (0.74 mol) of triethylamine (in an amount of 0.03 moles based on 1 mole of hydroxy group of the hydroxy group-substituted aromatic compound) were dissolved in 34 kg of water, and the obtained solution was defined as solution 23. After the solution 22 (in which the amount of a cyanogen chloride was 1.43 moles based on 1 mole of hydroxy group of the hydroxy group-substituted aromatic compound) (cyanogen halide solution g) had been continuously supplied at a rate of 400 g/hr while keeping the liquid temperature at 0 C. to 2 C., the solution 23 was continuously supplied at a rate of 1636 g/hr while keeping the liquid temperature at 0 C. to 5 C. After completion of the supply of the solution 22 and the solution 23, the degree of reaction progress was 98.5%. The degree of reaction progress in the production of a cyanate ester with respect to the amount of a basic compound used is shown in Table 2. (0285) The obtained reaction solution was subjected to countercurrent extraction with water at a liquid temperature of 30 C. to 32 C. at a rate of 600 g/hr. After washing with water, the dichloromethane phase was concentrated under reduced pressure, and finally, it was concentrated and dried at 95 C. to obtain 3422 g of 2,2-bis(4-cyanatophenyl)propane of interest. The concentration of total chlorine in the obtained cyanate ester compound was 52 ppm. These results are shown in Table 4. In addition, conditions for the cyanation step are shown in Table 5, and the content of a method of using a cyanogen halide is shown in Table 6.
With hydrogenchloride; triethylamine; In water; acetone;
D. Preparation of Bisphenol A Dicyanate A 456.60 gram portion of 4,4'-isopropylidene diphenol (2.00 moles), 444.91 grams of cyanogen bromide (4.20 moles) and 1,100 milliliters of acetone were added to a reactor and maintained under a nitrogen atmosphere with stirring. The stirred solution was cooled to -5C, then 406.82 grams of triethylamine (4.02 moles) was added to the reactor over a 60 minute period and so as to maintain the reaction temperature at -5 to -3C. After completion of the triethylamine addition, the reactor was maintained at -5 to -3C for an additional twenty-five minutes followed by addition of the reactor contents to 1.5 gallons (5.685 l) of deionized water. After 5 minutes, the water and product mixture was multiply extracted with three 500 milliliter volumes of methylene chloride. The combined methylene chloride extract was washed with 500 milliliters of 0.05 percent by weight aqueous hydrochloric acid followed by washing with 500 milliliters of deionized water, then drying over anhydrous sodium sulfate. The dry methylene chloride extract was filtered and solvent removed by rotary evaporation under vacuum for 60 minutes at 100C. Bisphenol A dicyanate (545.8 grams) was recovered in 98.1 percent yield as a light tan colored, crystalline solid. Infrared spectrophotometric analysis of a film sample of the product confirmed the product structure (disappearance of phenolic hydroxyl absorbance, appearance of cyanate absorbance).
98.1%
With hydrogenchloride; triethylamine; In water; acetone;
A. Preparation of Bisphenol A Dicyanate 4,4--Isopropylidene diphenol (456.60 grams, 4.0 hydroxyl equivalents), cyanogen bromide (444.91 grams, 4.20 moles) and acetone (1100 milliliters) were added to a reactor and maintained under a nitrogen atmosphere with stirring. The stirred solution was cooled to -5C, then triethylamine (406.82 grams, 4.02 moles) was added over a 60 minute period and so as to maintain the reaction temperature at -5C to -3C. After completion of the triethylamine addition, the reactor was maintained at -5C to -3C for an additional 25 minutes followed by addition of the reactor contents to 1.5 gallons of deionized water. After 5 minutes, the water and product mixture was multiply extracted with three 500 milliliter volumes of methylene chloride. The combined methylene chloride extract was washed with 500 milliliters of 0.05 percent by weight aqueous hydrochloric acid followed by washing with 500 milliliters of deionized water, then drying over anhydrous sodium sulfate. The dry methylene chloride extract was filtered and solvent removed by rotary evaporation under vacuum for 60 minutes at 100C. The bisphenol A dicyanate (545.8 grams) was recovered in 98.1 percent yield as a tan colored crystalline solid. Infrared spectrophotometric analysis of a film sample of the product confirmed the product structure (disappearance of phenolic hydroxyl absorbance, appearance of cyanate absorbance).
polyurethane, linear, Mn = 4E4, product of oligo(butylene glycol adipate) (Mn = 1000) reaction with 4,4'-diphenylmethane diisocyanate and butane-1,4-diol[ No CAS ]
[ 1156-51-0 ]
linear polyurethane, cross-linked poly(bisphenol A) cyanurate, semi-interpenetrating network, formed from oligo(butylene glycol adipate)/4,4'-diphenylmethane diisocyanate/butane-1,4-diol/bisphenol A dicyanate ester, 50 wt. % cross-linked poly(cyanurate)[ No CAS ]
polyurethane, linear, Mn = 4E4, product of oligo(butylene glycol adipate) (Mn = 1000) reaction with 4,4'-diphenylmethane diisocyanate and butane-1,4-diol[ No CAS ]
[ 1156-51-0 ]
linear polyurethane, cross-linked poly(bisphenol A) cyanurate, semi-interpenetrating network, formed from oligo(butylene glycol adipate)/4,4'-diphenylmethane diisocyanate/butane-1,4-diol/bisphenol A dicyanate ester, 75 wt. % cross-linked poly(cyanurate)[ No CAS ]
3-(2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl)phenyl cyanate[ No CAS ]
[ 1156-51-0 ]
Yield
Reaction Conditions
Operation in experiment
With 2,2'-azobis(isobutyronitrile);
A 180.0 gram (80 percent by weight, pbw) portion of bisphenol A dicyanate prepared using the method of Example 2-D and an 11.25 gram (5 pbw) portion of 3-(2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl)phenyl cyanate prepared using the method of Example 1-B were added to the reactor and maintained under a nitrogen atmosphere. The reactor contents were heated to a 110C solution. Then stirring commenced and dropwise addition of 33.75 grams (15 pbw) of 2-ethylhexyl acrylate and 0.45 gram of azobisisobutyronitrile as a solution commenced over a 35 minute period. After an additional 120 minutes of reaction at the 110C reaction temperature, the product was recovered as a hazy, light amber colored solution.
3-bromo-l -(4-methoxyphenyl)-4-methyl-lH-pyrrole (437.8 mg, 1.64 mmol) was dissolved in THF (20 ml) and the mixture was cooled to -78 C. n-BuLi (1.6 M, 1 .13 ml, 1.81 mmol) was added at -78 C under N2 and the mixture was stirred for 20 min. A solution of 2,2-bis-(4-cyanatophenyl)propane(549.4 mg, 1.97 mmol) in THF (4.5 ml) was added. The mixture was stirred at -78 C for 30 min and the cooling bath was then removed. NH4C1 (sat, aq) was added and the aqueous mixture was extracted with EtOAc. After flash chromatography l -(4-methoxyphenyl)-4-methyl-lH-pyrrole-3-carbonitrile (78.5 mg, 0.37 mmol) was obtained.
NaH (18.35 mg, 0.76 mmol) was stirred in dry THF (1 ml) at 0 C and 2-bromo-3-(4- methoxyphenyl)-lH-indole (210 mg, 0.69 mmol) dissolved in dry THF (4.5 ml) was added dropwise. The mixture was stirred at 0 C for 5 min and then 2,2-bis-(4-cyanatophenyl)propane (251 mg, 0.90 mmol) dissolved in dry THF (4.5 ml) was added dropwise. Water was added and this mixture was stirred for 30 min. Brine was added and the aqueous mixture was extracted with DCM. The solvent was concentrated and the crude product was purified on silica (EtOAc/n-Heptane 1 :4). 198 mg 2-bromo-3-(4- methoxyphenyl)-lH-indole-l-carbonitrile was obtained.
With sodium hydride; In tetrahydrofuran; at 0℃; for 0.0833333h;
Step (a): NaH (18.35 mg, 0.76 mmol) was stirred in dry THF (1 ml) at 0 C. and 2-bromo-3-(4-methoxyphenyl)-1H-indole (210 mg, 0.69 mmol) dissolved in dry THF (4.5 ml) was added dropwise. The mixture was stirred at 0 C. for 5 min and then 2,2-bis-(4-cyanatophenyl)propane (251 mg, 0.90 mmol) dissolved in dry THF (4.5 ml) was added dropwise. Water was added and this mixture was stirred for 30 min Brine was added and the aqueous mixture was extracted with DCM. The solvent was concentrated and the crude product was purified on silica (EtOAc/n-Heptane 1:4). 198 mg 2-bromo-3-(4-methoxyphenyl)-1H-indole-1-carbonitrile was obtained.
With triethylamine; In dimethyl sulfoxide; at 120 - 150℃;Microwave irradiation;
4-(3-(4-methoxyphenyl)-lH-indol-2-yl)-3,5-dimethylisoxazole (37 mg, 0.12 mmol) and 2,2-bis- (4-cyanatophenyl)propane (0.6 eq) were mixed in a vial. 1.8 ml DMSO and Et3N (3 eq) were added and the mixture was heated at 120 C in microwave. 2,2-bis-(4-cyanatophenyl)propane (5.7 eq) and Et3N (40 eq) were added and the mixture was heated at 150 C for 25 min in microwave. Brine was added and the aqueous layer was extracted with EtOAc 6x. The combined organic layers were dried over Na2S04 and concentrated. The crude product was taken up in DCM, filtered through cotton wool and purified on silica (EtOAc/n-Heptane 1 :9-2:8). 25.7 mg 2-(3,5-dimethylisoxazol-4-yl)-3-(4-methoxyphenyl)-lH-indole-l- carbonitrile was obtained as a yellowish solid.
With triethylamine; In dimethyl sulfoxide; at 120 - 150℃; for 0.416667h;Microwave irradiation;
Step (e): 4-(3-(4-methoxyphenyl)-1H-indol-2-yl)-3,5-dimethylisoxazole (37 mg, 0.12 mmol) and 2,2-bis-(4-cyanatophenyl)propane (0.6 eq) were mixed in a vial. 1.8 ml DMSO and Et3N (3 eq) were added and the mixture was heated at 120 C. in microwave. 2,2-bis-(4-cyanatophenyl)propane (5.7 eq) and Et3N (40 eq) were added and the mixture was heated at 150 C. for 25 min in microwave. Brine was added and the aqueous layer was extracted with EtOAc 6×. The combined organic layers were dried over Na2SO4 and concentrated. The crude product was taken up in DCM, filtered through cotton wool and purified on silica (EtOAc/n-Heptane 1:9-2:8). 25.7 mg 2-(3,5-dimethylisoxazol-4-yl)-3-(4-methoxyphenyl)-1H-indole-1-carbonitrile was obtained as a yellowish solid.
NaH (6.11 mg, 0.25 mmol) was stirred in dry THF (1 ml) at 0 C and 5-chloro-2-(2,4- dimethylthiophen-3-yl)-3-(4-methoxyphenyl)-lH-indole (72 mg, 0.20 mmol) dissolved in dry THF (2 ml) was added dropwise and the mixture was stirred at 0 C for 5 min. 2,2-bis-(4-cyanatophenyl)propane (70.8 mg, 0.25 mmol) dissolved in dry THF (2 ml) was added dropwise and the mixture was stirred at room temperature for 9 h.. NH4C1 (aq, sat) was added followed by brine and the aqueous mixture was extracted with DCM. The solvent was concentrated and the crude product was purified on silica(EtOAc/n-Heptane 1 :9). 72 mg 5-chloro-2-(2,4-dimethylthiophen-3-yl)-3-(4-methoxyphenyl)-lFI-indole- 1 -carbonitrile was obtained
Step (a): NaH (6.11 mg, 0.25 mmol) was stirred in dry THF (1 ml) at 0 C. and 5-chloro-2-(2,4-dimethylthiophen-3-yl)-3-(4-methoxyphenyl)-1H-indole (72 mg, 0.20 mmol) dissolved in dry THF (2 ml) was added dropwise and the mixture was stirred at 0 C. for 5 min. 2,2-bis-(4-cyanatophenyl)propane (70.8 mg, 0.25 mmol) dissolved in dry THF (2 ml) was added dropwise and the mixture was stirred at room temperature for 9 h. NH4Cl (aq, sat) was added followed by brine and the aqueous mixture was extracted with DCM. The solvent was concentrated and the crude product was purified on silica (EtOAc/n-Heptane 1:9). 72 mg 5-chloro-2-(2,4-dimethylthiophen-3-yl)-3-(4-methoxyphenyl)-1'-1-indole-1-carbonitrile was obtained.
Step (g): 4-(3-(4-methoxyphenyl)-l ,4,5,6-tetrahydrocyclopenta[b]pyrrol-2-yl)-3,5- dimethylisoxazole (35 mg, 0.11 mmol) was dissolved in THF (3 mL) under nitrogen. NaH (10.9 mg, 0.45 mmol) was added followed by 4,4'-(propane-2,2-diyl)bis(cyanatobenzene) (63.2 mg, 0.23 mmol). The mixture was stirred at room temperature for 16 h and was then cooled to 0 C. Water and EtOAc were added. The phases were partitioned and the aqueous phase was extracted with EtOAc. The combined organic phases were washed with brine, dried over Na2S04 and concentrated. The crude product was purified on silica using an EtOAc/«-heptane gradient (1 :9 - 2:8) as mobile phase. 2.6 mg 2-(3,5-dimethylisoxazol-4-yl)-3-(4-methoxyphenyl)-5,6- dihydrocyclopenta[b]pyrrole-l(4H)-carbonitrile was obtained as a white solid.
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