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With dihydrogen peroxide; In water; toluene; at 60 - 65℃; under 750.075 Torr; for 5h;Product distribution / selectivity; |
Example 1; Toluene, catalyst and 3-cyclohexene-l-carboxylic acid, 3-cyclohexen-l-ylmethyl ester ("Diene 221"), in the amounts described in Table I below, were charged in a 1 liter (L) continuous stirred tube reactor (CSTR) jacketed glass reactor equipped with a mechanical stirrer, thermocouple and reflux condenser.Table IThe temperature of the reaction was regulated at a temperature of from 60 0C (for initial 2.5 hours) to about 65 0C (for final 2.5 hours, including cooling time) by setting the temperature of the heating oil which is continuously pumped to the reactor jacket. Considering the exothermicity of the reaction between Diene 221 and H2O2, a water coil was mounted internally in the reactor in order to control the temperature of the reaction and maintain the temperature fixed at the desiderate value. The reaction is conducted at atmospheric pressure(abut 1 bar) and the magnetic stirrer speed is set at 600 rpm to ensure satisfactory contact between the organic and the aqueous phases.A mixture of a solution of hydrogen peroxide (30 wt percent concentration) and a buffering agent, as described in Table II below, was charged in a calibrated glass cylinder mounted on an HPLC pump suction side. The glass cylinder is connected to a balance in order to control its flow rate and the time needed to feed the solution into the reactor (60 minutes). <n="22"/>Table ?The hydrogen peroxide/buffering mixture solution was fed at a feed rate of 4.9 cc/minute with an HPLC pump for 1 hour; and when the feed is stopped (after 60 minutes) and an amount corresponding to 2.2/1 molar ratio respect to the Diene 221 has been added (10 percent H2O2 excess over stoichiometric ratio) , the reaction continues for 4 hours. This 4-hour time period is referred to herein as the "digestion" time.At the end of the digestion time period, the resulting mixture is cooled down to room temperature (about 25C) in 5-10 minutes and discharged into a 1.5 liter separatory funnel, leaving the two separate phases - an organic phase and an aqueous phase.The two phases were then analyzed and characterized using the analytical methods described as follows:Table III - Analytical methods and samples <n="23"/>The product obtained in toluene solution is a mixture of:3,4-epoxycyclohexylmethyl S^-epoxycyclohexanecarboxylate ("ERL4221") and monoepoxy of 3-cyclohexene-l-carboxylic acid, 3-cyclohexen-l-ylmethyl ester ("monoepoxy").The results of the reaction are described in Table IV below and also summarized in Table VI.Table IVThe ratio between monoepoxy product and monoepoxy product plus ERL4221 product is as described in Table V below:Table V; Comparative Example B; Comparative Example B was conducted using the same procedure as described in Example 2 except that no buffer was added to the reaction mixture. The results of this example are shown in Table VI. |
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With peracetic acid; sodium acetate; In toluene; at 90℃; for 0.166667h; |
(0056) 1431 ml of acetic acid and 1646 ml of 50 wt % hydrogen peroxide were placed in a 12L glass reaction flask, maintained at 45 C.; 280 ml of concentrated sulfuric acid was added dropwise over a duration of 90 min; then the mixture was stirred for 30 min. Temperature was maintained at 45 C., pressure was reduced to 10 ton, and distillation was performed for 2 hours to obtain peracetic acid solution. The peracetic acid solution was titrated with potassium permanganate solution and sodium thiosulfate solution, and the amount of peracetic acid in the peracetic acid solution was measured at 58.5 wt % and the amount of hydrogen peroxide at 3.4 wt %. Through HPLC analysis, the amount of acetic acid in the peracetic acid solution was determined to be 11.7 wt %. (0057) Sodium acetate was added to the peracetic acid solution to form a peracetic acid solution with 1.0 wt % sodium acetate. A 1.0 ml glass gastight syringe was fed with the solution and mounted to a syringe pump with a flow rate set to 6.65 mul/min. 3-cyclohexene-1-carboxylic acid, 3-cyclohexen-1-yl methyl ester (5.0 g) was mixed with toluene (10.0 g), and fed into another 1.0 ml glass gastight syringe, and then mounted to a syringe pump with a flow rate set to 8.35 gl/min (0058) The above two solutions were injected into a glass micro-reactor with an equivalent diameter of 0.2 mm, and heated to 90 C.; the reaction residue time was 40 sec. After 10 minutes of reaction, GC analysis was performed. The diolefin reactant conversion rate was 99.7%, the monoepoxide molar selectivity was 1.2%, the diepoxide molar selectivity was 95.8%, and the hydrolysate molar selectivity was 3.0%. |
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With sodium tungstate (VI) dihydrate; trioctylmethylammonium acetate; sodium dihydrogenphosphate dihydrate; sodium phosphate dibasic dodecahydrate; dodecatungstophosphoric acid hydrate; dihydrogen peroxide; In 5,5-dimethyl-1,3-cyclohexadiene; water; toluene; at 20 - 50℃; for 8h;pH 6.5;Inert atmosphere; |
To a flask equipped with a stirrer, a reflux condenser and a stirrer, while applying nitrogen purge, (A) 20 parts of water, 1.5 parts of 12-tungstophosphoric acid n hydrate (manufactured by NIPPON INORGANIC COLOUR & CHEMICAL CO.,LTD hereinafter the same), 0.5 parts of Sodium tungstate dihydrate (manufactured by NIPPON INORGANIC COLOUR & CHEMICAL CO.,LTD ., hereinafter the same), and 0.2 parts of disodium hydrogenphosphate · 12 hydrate (manufactured by Junsei Chemical Co., Ltd.) were added and dissolved, and the pH was adjusted to 6.5 with sodium dihydrogen phosphate dihydrate (manufactured by Aldrich), (E) then 110 parts of 3-cyclohexenyl methyl (3'-cyclohexenyl) carboxylate was added, (D) Further, 200 parts of toluene was added and while the mixture was stirred at room temperature (B) 2.9 parts of trioctyl methyl ammonium acetate (TOMAA-50, manufactured by Lion Akzo, concentration 50%, xylene solution,) was added and the temperature was raised to 50 C, (C) then 108 parts of 35% hydrogen peroxide aqueous solution (manufactured by Junsei Chemical Co., Ltd.) was added dropwise over 60 minutes. After completion of the dropwise addition, the mixture was stirred at 50 C for 7 hours, and the state of the reaction was confirmed by gas chromatography. Thereafter, 30% sodium hydroxide was added until the aqueous layer reached pH 8, and the aqueous layer was separated and drained. Further, 50 parts of 20% sodium thiosulfate aqueous solution was added and the mixture was stirred for 1 hour, then allowed to stand and the organic layer separated into two layers was taken out. (Post-treatment step) To the obtained organic layer, 40 parts of activated carbon (CAP SUPER manufactured by NORIT) was added and after stirring at room temperature for 2 hours, filtration under reduced pressure was carried out, the filtration residue was further washed with 100 parts of toluene and mixed with the preceding filtrate. The obtained solution was water-washed three times with 100 parts of water, and 116 parts of desired epoxy compound (EP1) was obtained by distilling off the organic solvent using a rotary evaporator. The epoxy compound obtained was of APHA less than 100 and the epoxy equivalent was 130 g / eq., and the viscosity was 227 mPa · s. Also the total chlorine was 45 ppm. |
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With dihydrogen peroxide; sodium acetate; acetic anhydride; In chloroform; at 13 - 30℃; for 9h;pH 3.7; |
(1) mixing a diene compound, a carboxylic acid substance, an alkaline salt, a solvent, and cooling to 13 C;(2) dropwise addition of hydrogen peroxide solution for 5h, and then continue the reaction for 4h, the temperature of the step is maintained at 30 C, the pH is maintained at 3.7;(3) standing, layering, obtaining the lower organic phase-1, adding the washing liquid, stirring for 30 min, washing the organic phase-1, maintaining the pH at 11; standing and layering, obtaining the lower organic phase-2;(4) First vacuum distillation purification, vacuum distillation under vacuum is -0.07MPa, temperature is 42 C, time is 0.75h, and then secondary film distillation purification, secondary film distillation temperature of the first film distillation is 50 C The distillation pressure was 220 Pa, the distillation time was 1 h, the secondary film distillation temperature was 90 C, the distillation pressure was 30 Pa, and the distillation time was 1 h.The diene compound isThe molar ratio of the carboxylic acid species to the diene compound was 2.4:1.The carboxylic acid substance is acetic anhydride, the acetic anhydride has a purity of 98%; the basic salt is sodium acetate; and the solvent is chloroform.The weight ratio of the diene compound to the solvent is 1:3.The concentration of the hydrogen peroxide was 35%; the molar ratio of the hydrogen peroxide to the diene compound was 3.6:1.The weight ratio of the washing liquid to the solvent was 1:3.The washing liquid includes an inorganic alkali solution and a reducing salt.The inorganic alkali solution is a sodium hydroxide solution; the concentration of the inorganic alkali solution is 30% by weight.The reducing salt is sodium sulfite; the reducing salt accounts for 1% by weight of the washing liquid. |
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