CN102241576B - Method for preparing 2,2'-di(4-ketocyclohexyl) propane by catalytic oxidation - Google Patents
Method for preparing 2,2'-di(4-ketocyclohexyl) propane by catalytic oxidation Download PDFInfo
- Publication number
- CN102241576B CN102241576B CN 201110103347 CN201110103347A CN102241576B CN 102241576 B CN102241576 B CN 102241576B CN 201110103347 CN201110103347 CN 201110103347 CN 201110103347 A CN201110103347 A CN 201110103347A CN 102241576 B CN102241576 B CN 102241576B
- Authority
- CN
- China
- Prior art keywords
- propane
- ketocyclohexyl
- hydrogenated bisphenol
- preparing
- acetonitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 17
- -1 4-ketocyclohexyl Chemical group 0.000 title claims abstract description 13
- 239000001294 propane Substances 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title abstract description 12
- 230000003197 catalytic effect Effects 0.000 title abstract 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 36
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002699 waste material Substances 0.000 abstract description 2
- NQEDLIZOPMNZMC-UHFFFAOYSA-N 4-propylcyclohexan-1-one Chemical compound CCCC1CCC(=O)CC1 NQEDLIZOPMNZMC-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing 2,2'-di(4-ketocyclohexyl) propane by catalytic oxidation. The method comprises the following step of: oxidizing hydrogenated bisphenol A into 2,2'-di(4-ketocyclohexyl) propane in an acetonitrile solvent in the presence of an aluminum sesquioxide catalyst. According to the method for preparing the 2,2'-di(4-ketocyclohexyl) propane, hydrogenated bisphenol A is oxidized into 2,2'-di(4-ketocyclohexyl) propane in an acetonitrile solvent by catalyzing, high temperature is not required, the catalyst is cheap, a small number of three wastes are produced,convenience is brought to operate, and the product yield is over 85 percent.
Description
Technical field
The present invention relates to a kind of 2,2 '-preparation method of two (4-oxo cyclohexyl) propane.
Background technology
2,2 '-two (4-oxo cyclohexyl) propane is a kind of important organic intermediate, can be for the preparation of medicine, polymkeric substance, polymerization starter, oxidation inhibitor etc., and of many uses.About its preparation method mainly contain (1) in acetic acid solvent with the Hydrogenated Bisphenol A hypochlorite oxidation; (2) in the mixed solvent of methyl alcohol and acetic acid with the Hydrogenated Bisphenol A hypochlorite oxidation; (3) in the alkylated aromatic hydrocarbons solvent, with copper, chromium oxide catalyst, with Hydrogenated Bisphenol A at 240 ℃ of dehydrogenation oxidations; (4) in alkyl benzene solvent, with Pd/C or Pd/Al
2O
3Catalyzer, at 170 ℃, 5 normal atmosphere are with dihydroxyphenyl propane hydrogenation oxidation.Hypochlorite oxidation is used in method (1), (2), and waste water is many, is difficult to process; Method (3) oxidizing temperature is too high, the difficult preparation of catalyzer; At high-pressure oxidation, the catalyzer cost is high with precious metal for method (4), operation inconvenience.
Summary of the invention
The object of the present invention is to provide that a kind of yield is high, maneuverable 2,2 in the production '-the catalyzed oxidation preparation method of two (4-oxo cyclohexyl) propane.
Technical solution of the present invention is:
A kind of 2,2 '-the catalyzed oxidation preparation method of two (4-oxo cyclohexyl) propane, it is characterized in that: in acetonitrile solvent, in the presence of aluminum trioxide catalyst, with hydrogen peroxide Hydrogenated Bisphenol A is oxidized to 2,2 '-two (4-oxo cyclohexyl) propane.
The weight ratio of acetonitrile, hydrogen peroxide, aluminium sesquioxide, Hydrogenated Bisphenol A is: acetonitrile: hydrogen peroxide: aluminium sesquioxide: Hydrogenated Bisphenol A=(3-10): (2-5): (0.05-0.2): 1.
Oxidizing reaction temperature is 40-60 ℃.Oxidation time is 3-10 hour.
By preparation 2,2 of the present invention '-two (4-oxo cyclohexyl) propane method, in acetonitrile solvent, be 2 with the Hydrogenated Bisphenol A catalyzed oxidation, 2 '-two (4-oxo cyclohexyl) propane, need not high temperature, catalyzer is cheap, the three wastes are few, convenient operation, and product yield is more than 85%.
The invention will be further described below in conjunction with embodiment.
Embodiment
Embodiment 1
The 10g Hydrogenated Bisphenol A is dissolved in the 70g acetonitrile, adds the 1g aluminum trioxide catalyst, drip the 20g hydrogen peroxide, drip rear 40 ℃ of oxidizing reactions 6 hours.Reaction finishes, and be down to room temperature and filter out catalyzer, the aftertreatment of filtrate process, analysis, calculating, 2,2 '-two (4-oxo cyclohexyl) propane yield is 85.8%.
Embodiment 2
The 10g Hydrogenated Bisphenol A is dissolved in the 30g acetonitrile, adds the 0.5g aluminum trioxide catalyst, drip the 10g hydrogen peroxide, drip rear 60 ℃ of oxidizing reactions 3 hours.Reaction finishes, and be down to room temperature and filter out catalyzer, the aftertreatment of filtrate process, analysis, calculating, 2,2 '-two (4-oxo cyclohexyl) propane yield is 86.5%.
Embodiment 3
The 10g Hydrogenated Bisphenol A is dissolved in the 100g acetonitrile, adds the 2g aluminum trioxide catalyst, drip the 30g hydrogen peroxide, drip rear 50 ℃ of oxidizing reactions 10 hours.Reaction finishes, and be down to room temperature and filter out catalyzer, the aftertreatment of filtrate process, analysis, calculating, 2,2 '-two (4-oxo cyclohexyl) propane yield is 85.3%.
Claims (2)
1. one kind 2, the catalyzed oxidation preparation method of two (the 4-oxo cyclohexyl) propane of 2-is characterized in that: in acetonitrile solvent, in the presence of aluminum trioxide catalyst, with hydrogen peroxide Hydrogenated Bisphenol A is oxidized to two (the 4-oxo cyclohexyl) propane of 2,2-; The weight ratio of acetonitrile, hydrogen peroxide, aluminium sesquioxide, Hydrogenated Bisphenol A is: acetonitrile: hydrogen peroxide: aluminium sesquioxide: Hydrogenated Bisphenol A=(3-10): (2-5): (0.05-0.2): 1; Oxidizing reaction temperature is 40-60 ℃.
2. according to claim 12, the catalyzed oxidation preparation method of two (the 4-oxo cyclohexyl) propane of 2-, it is characterized in that: oxidation time is 3-10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110103347 CN102241576B (en) | 2011-04-25 | 2011-04-25 | Method for preparing 2,2'-di(4-ketocyclohexyl) propane by catalytic oxidation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110103347 CN102241576B (en) | 2011-04-25 | 2011-04-25 | Method for preparing 2,2'-di(4-ketocyclohexyl) propane by catalytic oxidation |
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| Publication Number | Publication Date |
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| CN102241576A CN102241576A (en) | 2011-11-16 |
| CN102241576B true CN102241576B (en) | 2013-05-29 |
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| CN 201110103347 Expired - Fee Related CN102241576B (en) | 2011-04-25 | 2011-04-25 | Method for preparing 2,2'-di(4-ketocyclohexyl) propane by catalytic oxidation |
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| CN105198738B (en) * | 2015-09-18 | 2017-04-05 | 南通柏盛化工有限公司 | Hydrogen peroxide oxidation synthesizes the method for 2 carboxyl anthraquinones |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697389A1 (en) * | 1994-08-09 | 1996-02-21 | New Japan Chemical Co.,Ltd. | Process for producing alicyclic diketone compounds |
| CN1923778A (en) * | 2006-09-14 | 2007-03-07 | 烟台万润精细化工有限责任公司 | Cyclohexanol derivative, cyclohexanone derivative and preparation method |
| CN101020627A (en) * | 2007-01-22 | 2007-08-22 | 河北大学 | Process of synthesizing 1,4-cyclohexyl dione |
| CN101337870A (en) * | 2008-08-08 | 2009-01-07 | 西安瑞联近代电子材料有限责任公司 | Method for synthesizing 4-(4'-n-alkyl cyclohexyl)cyclohexanone |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3668540B2 (en) * | 1995-09-22 | 2005-07-06 | ダイセル化学工業株式会社 | Method for producing ketone |
| JP4186554B2 (en) * | 2002-02-04 | 2008-11-26 | 住友化学株式会社 | Method for producing carbonyl compound and catalyst thereof |
-
2011
- 2011-04-25 CN CN 201110103347 patent/CN102241576B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697389A1 (en) * | 1994-08-09 | 1996-02-21 | New Japan Chemical Co.,Ltd. | Process for producing alicyclic diketone compounds |
| CN1923778A (en) * | 2006-09-14 | 2007-03-07 | 烟台万润精细化工有限责任公司 | Cyclohexanol derivative, cyclohexanone derivative and preparation method |
| CN101020627A (en) * | 2007-01-22 | 2007-08-22 | 河北大学 | Process of synthesizing 1,4-cyclohexyl dione |
| CN101337870A (en) * | 2008-08-08 | 2009-01-07 | 西安瑞联近代电子材料有限责任公司 | Method for synthesizing 4-(4'-n-alkyl cyclohexyl)cyclohexanone |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2003-292465A 2003.10.15 |
| JP特开平9-87227A 1997.03.31 |
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| CN102241576A (en) | 2011-11-16 |
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Address after: 226221 No.1 Shanghai Road, Binjiang fine chemical industry park, Qidong City, Nantong City, Jiangsu Province Patentee after: Nantong Baisheng Pharmaceutical Co.,Ltd. Address before: 226221 No.1 Shanghai Road, Binjiang fine chemical industry park, Qidong City, Nantong City, Jiangsu Province Patentee before: NANTONG BAISHENG CHEMICAL Co.,Ltd. |
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