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sulfuric acid; triethylamine; In n-Undecane; at 185 - 191℃; for 5.5h;Product distribution / selectivity; |
EXAMPLE 6 A dehydration catalyst was prepared by blending 101 g (1.00 mol) of triethylamine and 103 g (1.05 mol) of sulfuric acid. In a 3-liter flask equipped with a stirrer, a thermometer, and a distillation line provided with a water outlet and kept at a constant temperature, were placed 840 g (4.24 mol) of the hydrogenated biphenol, 2350 g of undecane, and 159 g of the above-prepared dehydration catalyst, and the flask was heated. Formation of water was detected from around the time when the inner temperature exceeded 110C. The heating was further continued until the temperature reached the boiling point of undecane (inner temperature: 185C to 191C), and dehydration was conducted under normal pressure. By-product water was distilled off and discharged from the system via the water outlet. After a lapse of five and a half hours, a substantially theoretical amount of water (151 g) was distilled, whereby the reaction was completed. Using a 10-tray Oldershaw distillation column, undecane was distilled off from the resulting reaction mixture, and the residue was further subjected to distillation at an inner temperature of 136C to 141C and an inner pressure of 10 Torr (1.33 kPa), to thereby yield 473.9 g of bicyclohexyl-3,3'-diene. The ratio in content of the target compound to isomers was 92:8 as determined by gas chromatography. |
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potassium hydrogensulfate; In Isopropylbenzene; at 166 - 170℃; for 6.5h;Product distribution / selectivity; |
COMPARATIVE EXAMPLE 2 In a 3-liter flask equipped with a stirrer, a thermometer, and a distillation line provided with a water outlet and kept at a constant temperature, were placed 640 g (3.23 mol) of the hydrogenated biphenol, 375 g (2.75 mol) of potassium hydrogen sulfate, and 1485 g of cumene, and the flask was heated. Formation of water was detected from around the time when the inner temperature exceeded 125C. The heating was further continued until the temperature reached the boiling point of cumene (inner temperature: 166C to 170C), and dehydration was conducted under normal pressure. By-product water was distilled off and discharged from the system via the water outlet. In this process, potassium hydrogen sulfate was solid and most thereof was not dissolved in the liquid reaction mixture under the reaction conditions. After a lapse of six and a half hours, only about one-third of the theoretical amount of water (35.9 g) was distilled, and the reaction was discontinued. |
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sodium hydrogen sulfate; In 1,2,4-Trimethylbenzene; at 176 - 178℃; for 2.83333h;Product distribution / selectivity; |
COMPARATIVE EXAMPLE 4 In a 3-liter flask equipped with a stirrer, a thermometer, and a distillation line provided with a water outlet and kept at a constant temperature, were placed 126 g (0.93 mol) of sodium hydrogen sulfate and 2160 g of pseudocumene, and the flask was heated. From the time when the liquid in the flask boiled and the inner temperature reached 176C, 280 g (1.41 mol) of the hydrogenated biphenol was added intermittently over 50 minutes, and dehydration was then conducted while the boiling state was maintained (inner temperature: 176C to 178C) under normal pressure for two hours, but there was not observed distillation of water, whereby the reaction was finished. The resulting liquid reaction mixture was cooled to room temperature to find that unreacted hydrogenated biphenol deposited. Thus, filtration was conducted to recover 1969 g of a filtrate. The filtrate had a concentration of the target compound bicyclohexyl-3,3'-diene of 0.3% as determined through gas chromatography, to find that the total weight of the target compound (bicyclohexyl-3,3'-diene) and isomers thereof in the reaction mixture was 5.7 g (0.03 mol, in a yield of 2%). Accordingly, the filtrate was not subjected to gas chromatography-mass spectrometry (GC/MS) and further purification through distillation. |
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phosphoric acid; In n-Undecane; at 189 - 194℃; for 5.5h;Product distribution / selectivity; |
EXAMPLE 5 In a 3-liter flask equipped with a stirrer, a thermometer, and a distillation line provided with a water outlet and kept at a constant temperature, were placed 840 g (4.24 mol) of the hydrogenated biphenol, 170 g (1.73 mol) of phosphoric acid, and 2350 g of undecane, and the flask was heated. Formation of water was detected from around the time when the inner temperature exceeded 110C. The heating was further continued until the temperature reached the boiling point of undecane (inner temperature: 189C to 194C), and dehydration was conducted under normal pressure. By-product water was distilled off and discharged from the system via the water outlet. In this process, p-toluenesulfonic acid was fully dissolved in the liquid reaction mixture under the reaction conditions. After a lapse of five and a half hours, a substantially theoretical amount of water (150 g) was distilled, whereby the reaction was completed. Using a 10-tray Oldershaw distillation column, undecane was distilled off from the resulting reaction mixture, and the residue was further subjected to distillation at an inner temperature of 138C to 141C and an inner pressure of 10 Torr (1.33 kPa) and thereby yielded 474.2 g of bicyclohexyl-3,3'-diene. The ratio in content of the target compound to isomers was 87:13 as determined by gas chromatography. |
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ammonium bisulphate; In Isopropylbenzene; at 165 - 170℃; for 6.5h;Product distribution / selectivity; |
COMPARATIVE EXAMPLE 1 In a 5-liter flask equipped with a stirrer, a 20-tray Oldershaw distillation column, and a thermometer were placed 1000 g (5.05 mol) of the hydrogenated biphenol, 40 g (0.265 mol) of ammonium hydrogen sulfate, and 2800 g of cumene, and the flask was heated. Formation of water was detected from around the time when the inner temperature exceeded 115C. The heating was further continued, and the reaction was continued to raise the temperature to the boiling point of cumene (inner temperature: 165C to 170C), and dehydration was conducted under normal pressure while by-product water was distilled off as an overhead from the distillation column. In this process, ammonium hydrogen sulfate was solid and most thereof was not dissolved in the liquid reaction mixture under the reaction conditions. After a lapse of six and a half hours, 94% of the theoretical amount of water (170.9 g) was distilled, whereby the reaction was completed. After the completion of reaction, cumene was distilled off under reduced pressure, and the system was further evacuated to a pressure of 10 Torr (1.33 kPa), followed by distillation at an inner temperature of 137C to 141C, to yield 590 g of bicyclohexyl-3,3'-diene. The ratio in content of the target compound to isomers was 81:19 as determined by gas chromatography. |
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With sodium acetate;sulfuric acid; triethylamine; In 1,2,4-Trimethylbenzene; at 168 - 171℃; for 5h;Product distribution / selectivity; |
EXAMPLE 7 A dehydration catalyst was prepared by blending 145.4 g (1.44 mol) of triethylamine and 118 g (1.20 mol) of sulfuric acid. In a 3-liter flask equipped with a stirrer, a thermometer, and a distillation line provided with a water outlet and kept at a constant temperature, were placed 840 g (4.24 mol) of the hydrogenated biphenol, 0.16 g (0.0019 mol) of sodium acetate, 2350 g of pseudocumene, and 157 g of the above-prepared dehydration catalyst, and the flask was heated. Formation of water was detected from around the time when the inner temperature exceeded 110C. The heating was further continued until the temperature reached the boiling point of pseudocumene (inner temperature: 168C to 171C), and dehydration was conducted under normal pressure. By-product water was distilled off and discharged from the system via the water outlet. After a lapse of five hours, a substantially theoretical amount of water (150 g) was distilled, whereby the reaction was completed. Using a 10-tray Oldershaw distillation column, pseudocumene was distilled off from the resulting reaction mixture, and the residue was further subjected to distillation at an inner temperature of 138C to 143C and an inner pressure of 10 Torr (1.33 kPa) and thereby yielded 479.3 g of bicyclohexyl-3,3'-diene. The ratio in content of the target compound to isomers was 90:10 as determined by gas chromatography. |
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sulfuric acid; 1,8-diazabicyclo[5.4.0]undec-7-ene; In pseudocymene; at 115 - 170℃; for 3h;Industry scale;Product distribution / selectivity; |
A dehydration catalyst was prepared by mixing and stirring 70 g (0.68 mol) of 95 percent by weight sulfuric acid with 55 g (0.36 mol) of 1,8-diazabicyclo[5.4.0]undecene-7 (DBU). In a 3-liter flask equipped with a stirrer, a thermometer, and a distillation line provided with a water outlet and kept at a constant temperature, were placed 1000 g (5.05 mol) of hydrogenated biphenol (i.e., <strong>[20601-38-1]4,4'-dihydroxybicyclohexyl</strong>) represented by following Formula (3a) : [Show Image] , 125 g (0.68 mol in terms of sulfuric acid) of the above-prepared dehydration catalyst, and 1500 g of pseudocumene, and the flask was heated. Formation of water was detected around the time when the inner temperature became higher than 115C. The heating was further continued until the temperature reached the boiling point of pseudocumene (inner temperature: 162C to 170C), to carry out dehydration under normal pressure. By-product water was distilled out and discharged out of the system via the water outlet. Under the reaction conditions, the dehydration catalyst was liquid and finely dispersed in the reaction liquid. After a lapse of three hours, a substantially theoretical amount of water (180 g) was distilled, whereby the reaction was deemed to complete. Using a 10-tray Oldershaw distillation column, pseudocumene was distilled off from the reaction mixture after the completion of the reaction, and the residue was further subjected to distillation at an inner temperature of 137C to 140C and an inner pressure of 10 Torr (1.33 kPa), to thereby yield 731 g of bicyclohexyl-3,3'-diene. A result of gas chromatography analysis showed the fact that the prepared bicyclohexyl-3,3'-diene contained isomers thereof (the fact was also confirmed by gas chromatography-mass spectrometry (GC-MS) analysis), and the content ratio of bicyclohexyl-3,3'-diene represented by following Formula (2a): [Show Image] to the isomers thereof was 91:9, as determined by gas chromatography (see Fig. 5). In a reactor were placed 243 g of the prepared bicyclohexyl-3,3'-diene (inclusive of its isomers) and 730 g of ethyl acetate. Thereafter, 274 g of a 30 percent by weight solution of peroxyacetic acid in ethyl acetate (water content: 0.41 percent by weight) was added dropwise in the reactor over three hours while blowing nitrogen gas into the gas phase and controlling the inner temperature of the reaction system to 37.5C. After the completion of dropwise addition of the peroxyacetic acid solution, aging was conducted at 40C for one hour, whereby the reaction was completed. The crude reaction mixture upon the completion of reaction was washed with water at 30C, and low-boiling compounds were removed from the washed reaction mixture at a temperature of 70C and a pressure of 20 mmHg to give 270 g of an alicyclic epoxy compound in a yield of 93%. This compound was found to have a viscosity (25C) of 84 mPa.s. The prepared alicyclic epoxy compound had an oxirane oxygen concentration of 15.0 percent by weight. The 1H-NMR measurement of the alicyclic epoxy compound showed that a peak derived from an internal double bond and appearing at delta of around 4.5 to 5 ppm disappeared, and a peak of proton derived from epoxy group appeared at delta of around 3.1 ppm, to find that the compound was 3,4,3',4'-diepoxybicyclohexyl represented by following Formula (1a): [Show Image] The prepared alicyclic epoxy compound was found to contain 3,4,3',4'-diepoxybicyclohexyl and isomers thereof and have an isomer percentage of 9%, as determined by gas chromatography (see Fig. 1). The isomer percentage was calculated according to the following equation: |
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potassium hydrogensulfate; at 180 - 220℃; for 7h;Neat (no solvent); Industry scale; |
In a 10-liter four-necked flask equipped with a stirrer, a 20-tray distillation column, and a thermometer were placed 6 kg of hydrogenated biphenol and 620 g of potassium hydrogen sulfate. Next, the flask was heated to 180C to melt the hydrogenated biphenol, followed by stirring. The reaction was continued while by-product water was distilled out as an overhead from the distillation column. After a lapse of three hours, the reaction system was evacuated to a pressure of 10 Torr (1.33 kPa), and water and bicyclohexyl-3,3'-diene were continuously distilled out of the system from the uppermost tray of the distillation column. The water and bicyclohexyl-3,3'-diene distilled out of the system were separated into two layers in a decanter, and the upper layer alone was recovered. Thereafter, the reaction temperature was raised to 220C over four hours, and the reaction was deemed to complete at the time when distillation of water and bicyclohexyl-3,3'-diene was ceased. A crude distillate of bicyclohexyl-3,3'-diene was obtained in a yield of 4507 g. In a 5-liter four-necked flask equipped with a stirrer, a 20-tray distillation column, and a thermometer was placed 4500 g of the crude distillate of bicyclohexyl-3,3'-diene, and the temperature of the flask was raised to 180C on an oil bath. The reaction system was then evaluated to a pressure of 10 Torr (1.33 kPa) to distil off water, thereafter bicyclohexyl-3,3'-diene was purified by distillation over five hours at a reflux ratio of 1, while keeping the temperature of the uppermost tray of the distillation column at 145C, to thereby yield 4353 g of a colorless transparent liquid. The liquid was analyzed by gas chromatography to find that the prepared bicyclohexyl-3,3'-diene contains isomers and a content ratio of the bicyclohexyl-3,3'-diene to the isomers was 80:20. In a reactor were placed 243 g of the prepared bicyclohexyl-3,3'-diene (inclusive of its isomers) and 730 g of ethyl acetate. Thereafter, 274 g of a 30 percent by weight solution of peroxyacetic acid in ethyl acetate (water content: 0.41 percent by weight) was added dropwise over three hours while blowing nitrogen gas into the gas phase and controlling the inner temperature of the reaction system to 37.5C. After the completion of dropwise addition of the peroxyacetic acid solution, aging was conducted at 40C for one hour, whereby the reaction was completed. The crude reaction mixture upon the completion of reaction was washed with water at 30C, from which low-boiling compounds were removed at a temperature of 70C and a pressure of 20 mmHg, to give 267 g of an alicyclic epoxy compound in a yield of 92%. This compound was found to have a viscosity (25C) of 63 mPa.s. The prepared alicyclic epoxy compound had an oxirane oxygen concentration of 14.9 percent by weight. The 1H-NMR measurement of the alicyclic epoxy compound showed that a peak derived from an internal double bond and appearing at delta of around 4.5 to 5 ppm disappeared and a peak of proton derived from epoxy group appeared at delta of around 3.1 ppm, to find that the compound is 3,4,3',4'-diepoxybicyclohexyl. The prepared alicyclic epoxy compound was found to contain 3,4,3',4'-diepoxybicyclohexyl and isomers thereof and have an isomer percentage of 21%, as determined by gas chromatography (see Fig. 4). The isomer percentage was calculated according to the following equation |
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phosphoric acid; In n-Undecane; at 110 - 194℃; for 5.5h;Industry scale;Product distribution / selectivity; |
In a 3-liter flask equipped with a stirrer, a thermometer, and a distillation line provided with a water outlet and kept at a constant temperature, were placed 840 g (4.24 mol) of hydrogenated biphenol, 170 g (1.73 mol) of phosphoric acid, and 2350 g of undecane, and the flask was heated. Formation of water was detected from around the time when the inner temperature became higher than 110C. The heating was further continued until the temperature reached the boiling point of undecane (inner temperature: 189C to 194C), and dehydration was conducted under normal pressure. By-product water was distilled off and discharged from the system via the water outlet. In this process, p-toluenesulfonic acid was fully dissolved in the reaction liquid under the reaction conditions. After a lapse of five and a half hours, a substantially theoretical amount of water (150 g) was distilled out, whereby the reaction was deemed to complete. Using a 10-tray Oldershaw distillation column, undecane was distilled off from the resulting reaction mixture, and the residue was further subjected to distillation at an inner temperature of 138C to 141C and an inner pressure of 10 Torr (1.33 kPa) and thereby yielded 474.2 g of bicyclohexyl-3,3'-diene. The prepared bicyclohexyl-3,3'-diene contained isomers with a content ratio of bicyclohexyl-3,3'-diene to the isomers of 87:13, as determined by gas chromatography. In a reactor were placed 243 g of the prepared bicyclohexyl-3,3'-diene (inclusive of its isomers) and 730 g of ethyl acetate, and 274 g of a 30 percent by weight solution of peroxyacetic acid in ethyl acetate (water content: 0.41 percent by weight) was added dropwise in the reactor over three hours while blowing nitrogen gas into the gas phase and controlling the inner temperature of the reaction system to 37.5C. After the completion of dropwise addition of the peroxyacetic acid solution, aging was conducted at 40C for one hour, whereby the reaction was completed. The crude reaction mixture upon the completion of reaction was washed with water at 30C, and low-boiling compounds were removed from the washed reaction mixture at a temperature of 70C and a pressure of 20 mmHg to yield 261 g of an alicyclic epoxy compound in a yield of 90%. This compound was found to have a viscosity (25C) of 75 mPa.s. The prepared alicyclic epoxy compound had an oxirane oxygen concentration of 15.0 percent by weight. The 1H-NMR measurement of the alicyclic epoxy compound showed that a peak derived from an internal double bond and appearing at delta of around 4.5 to 5 ppm disappeared and a peak of proton derived from epoxy group appeared at delta of around 3.1 ppm, to find that the compound is 3,4,3',4'-diepoxybicyclohexyl. The prepared alicyclic epoxy compound was found to contain 3,4,3',4'-diepoxybicyclohexyl and isomers thereof and to have an isomer percentage of 14%, as determined by gas chromatography (see Fig. 2). The isomer percentage was calculated according to the following equation: [Show Image] |
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ammonium bisulphate; In Isopropylbenzene; at 115 - 170℃; for 6.5h;Industry scale;Product distribution / selectivity; |
In a 5-liter flask equipped with a stirrer, a 20-tray Oldershaw distillation column, and a thermometer were placed 1000 g (5.05 mol) of hydrogenated biphenol, 40 g (0.265 mol) of ammonium hydrogen sulfate, and 2800 g of cumene, and the flask was heated. Formation of water was detected from around the time when the inner temperature became higher than 115C. The heating was further continued and the reaction was continued to raise the temperature to the boiling point of cumene (inner temperature: 165C to 170C), and dehydration was conducted under normal pressure while by-product water was distilled out as an overhead from the distillation column. In this process, ammonium hydrogen sulfate was solid and most thereof was not dissolved in the reaction liquid under the reaction conditions. After a lapse of six and a half hours, 94% of the theoretical amount of water (170.9 g) was distilled out, whereby the reaction was deemed to complete. After the completion of reaction, cumene was distilled off under reduced pressure, and the system was further evacuated to a pressure of 10 Torr (1.33 kPa), followed by distillation at an inner temperature of 137C to 141C, to yield 590 g of bicyclohexyl-3,3'-diene. The prepared bicyclohexyl-3,3'-diene was found to contain isomers and to have a content ratio of bicyclohexyl-3,3'-diene to the isomers of 81:19, as determined by gas chromatography. In a reactor, 243 g of the prepared bicyclohexyl-3,3'-diene (inclusive of its isomers) and 730 g of ethyl acetate were placed. Thereafter, 274 g of a 30 percent by weight solution of peroxyacetic acid in ethyl acetate (water content: 0.41 percent by weight) was added dropwise in the reactor over three hours while blowing nitrogen gas into the gas phase and controlling the inner temperature of the reaction system to 37.5C. After the completion of dropwise addition of the peroxyacetic acid solution, aging was conducted at 40C for one hour, whereby the reaction was completed. The crude reaction mixture upon the completion of reaction was washed with water at 30C, and low-boiling compounds were removed from the washed reaction mixture at a temperature of 70C and a pressure of 20 mmHg, to give 269 g of an alicyclic epoxy compound in a yield of 92%. This compound was found to have a viscosity (25C) of 69 mPa.s. The prepared alicyclic epoxy compound had an oxirane oxygen concentration of 14.9 percent by weight. The 1H-NMR measurement of the alicyclic epoxy compound showed that a peak derived from an internal double bond and appearing at delta of around 4.5 to 5 ppm disappeared and a peak of proton derived from epoxy group appeared at delta of around 3.1 ppm, to find that the compound is 3,4,3',4'-diepoxybicyclohexyl. The prepared alicyclic epoxy compound was found to contain 3,4,3',4'-diepoxybicyclohexyl and isomers thereof and have an isomer percentage of 17%, as determined by gas chromatography (see Fig. 3). The isomer percentage was calculated according to the following equation: [Show Image] |
| 731 g |
With 1,2,4-Trimethylbenzene; sulfuric acid; 1,8-diazabicyclo[5.4.0]undec-7-ene; at 115 - 170℃; under 760.051 Torr; for 3h; |
A dehydration catalyst was prepared by mixing, with stirring, 70 g (0.68 mol) of 95 weight percent sulfuric acid and 55 g (0.36 mol) of 1,8-diazabicyclo[5.4.0]undecene-7 (DBU). (0141) A 3-L flask was charged with 1000 g (5.05 mol) of hydrogenated biphenol (4,4?-dihydroxybicyclohexyl), 125 g (0.68 mol in terms of sulfuric acid) of the above-prepared dehydration catalyst, and 1500 g of pseudocumene, and was heated, where the flask was equipped with a stirrer, a thermometer, and a distillation pipe being packed with a dehydrating agent and thermally insulated. Water production was observed from around the time point when the internal temperature exceeded 115 C. The heating (temperature rise) was further continued up to the boiling point of pseudocumene (to an internal temperature of 162 C. to 170 C.), and dehydration reaction was performed under normal atmospheric pressure. The by-produced water was distilled and discharged through the dehydration tube out of the system. The dehydration catalyst was liquid and was finely dispersed in the reaction mixture under the reaction conditions. Approximately the stoichiometric amount (180 g) of water was distilled after a lapse of 3 hours, and this was defined as reaction completion. The reaction mixture after reaction completion was subjected to distillation using an Oldershaw distilling column including 10 plates to distill off pseudocumene, was further subjected to distillation at an internal temperature of 137 C. to 140 C. and an internal pressure of 10 Torr (1.33 kPa), and yielded 731 g of bicyclohexyl-3,3?-diene. |
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