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With hydrogen In water; isopropyl alcohol at 140℃; for 8h; Autoclave; |
2 [Example 2]
[Example 2]Into a vessel of a stainless autoclave having a content volume of 100 mL were added 5.00 g (26.85 mmol) of 4,4'-biphenol, 0.65 g of a Raney nickel catalyst (manufactured by Tokyo Chemical Industry Co., Ltd., weighed as water slurry) and 15.00 g of 2-propanol at a room temperature of about 25°C. An atmosphere in the vessel containing the resultant mixture was purged sufficiently with a hydrogen gas, then, the mixture was heated up to 140°C and the hydrogen gas pressure was adjusted to 7 kg/cm2. The mixture was stirred while thermally insulated for 8 hours while controlling so that the hydrogen gas pressure in the system was kept at 7 kg/cm2 by additionally adding a hydrogen gas as needed. Thereafter, the resultant mixture was cooled down to room temperature, and the atmosphere was purged with a nitrogen gas. Then, into the system purged with a nitrogen gas was added 25.00 g of tetrahydrofuran, the resultant mixture was stirred, then, solid components were removed by filtration. The resultant filtrate was analyzed by a liquid chromatography internal standard method (internal standard: n-propyl benzoate), and the content of the compound (2-1) in the filtrate was calculated. As a result, the yield of the compound (2-1) based on 4,4'-biphenol was 98.4% by mol. Further, the resultant filtrate was analyzed by gas chromatography and the production rate of the compound (2-1) as the intended product was calculated, to find 86% by mol with respect to the raw material 4,4'-biphenol, and the production rate of bicyclohexanediol as a by-product which is difficult to be separated and removed was calculated, to find 7.7 % by mol with respect to the raw material 4,4'-biphenol. |
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With nickel-aluminum alloy; sodium hydroxide In water |
4 (4 '-hydroxyphenyl) cyclohexanone (I), its preparation steps as follow: 4,4-biphenyldiphenol is catalytically hydrogenated by palladium-carbon catalyzed hydrogenation with aluminum-nickel alloy or palladium-carbon under basic conditions to give 4 (4'-hydroxyphenyl) cyclohexanol. The phenolic hydroxyl groups are protected with benzyl, oxidized by acidic chromium trioxide, deprotection gave 4 (4'-hydroxyphenyl) cyclohexanone. the preparation method of 4 (4 '-hydroxyphenyl) cyclohexanone (I) according to claim 2, the molar ratio of the raw materials of the hydrogenation reaction 4, 4-biphenyldiphenol, sodium hydroxide and aluminum-nickel alloy is 1: 7: 14 and solvent is water. the preparation method of 4 (4 '-hydroxyphenyl) cyclohexanone (I) according to claim 2, The raw materials for protecting the phenolic hydroxyl groups are BnCl, BnBr. the preparation method of 4 (4 '-hydroxyphenyl) cyclohexanone (I) according to claim 2, The oxidation reaction catalyst is concentrated sulfuric acid-chromium trioxide and the solvent is acetone and water. the preparation method of 4 (4 '-hydroxyphenyl) cyclohexanone (I) according to claim 2, The deprotection is carried out with Pb / C hydro debenzylation. |
93.69 g |
With nickel/aluminium alloy; water; potassium hydroxide at 90 - 95℃; for 2h; |
1) Synthesis of 4- (4-hydroxycyclohexane) phenol
Under stirring, 8000 ml of water, 72 g of 4,4'-diphenol and 120 g of potassium hydroxide were added into a 10 L three-necked flask and the temperature of the system was raised to 90 ° C.- After 95 ° C, 280g of Al-Ni was added in batches (the temperature of the mixture was kept at 90 ° C to 95 ° C). The mixture was incubated at 90 ° C to 95 ° C for 2h and then sampled until the concentration of 4,4'-diphenol 2) Post-treatment of 4- (4-hydroxycyclohexane) phenol: The reaction system is cooled to below 30 ° C, filtered, and the filter cake is rinsed twice with 200 ml each time. The combined filtrates are concentrated (70-75 ° C, -0.08 (~0.09MPa), and then concentrated to about 10L (the remaining 6L system) to stop concentration; concentrated residue was extracted three times with methyl tert-butyl ether, each 1000ml (each stirring 30min, standing 10min); aqueous The pH was adjusted to 1 with 6mol / L hydrochloric acid, and the mixture was stirred for 2h. The filtrate was filtered and the filtrate was rinsed twice with 100ml of water each time. The filter cake was drained and dried (60-75 , -0.08MPa -0.09MPa, 12h ) Gave 93.69 g of high purity 4- (4-hydroxycyclohexane) phenol. |