CN111777498A - Synthesis and purification method of 4- (4-hydroxyphenyl) cyclohexanone - Google Patents
Synthesis and purification method of 4- (4-hydroxyphenyl) cyclohexanone Download PDFInfo
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- CN111777498A CN111777498A CN201910259230.2A CN201910259230A CN111777498A CN 111777498 A CN111777498 A CN 111777498A CN 201910259230 A CN201910259230 A CN 201910259230A CN 111777498 A CN111777498 A CN 111777498A
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- hydroxyphenyl
- cyclohexanone
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- SLJYPZJZQIHNGU-UHFFFAOYSA-N 4-(4-hydroxyphenyl)cyclohexan-1-one Chemical compound C1=CC(O)=CC=C1C1CCC(=O)CC1 SLJYPZJZQIHNGU-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title claims description 5
- 238000003786 synthesis reaction Methods 0.000 title claims description 5
- 238000000746 purification Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000011403 purification operation Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- YXBPBFIAVFWQMT-UHFFFAOYSA-N 3-phenylcyclohexan-1-ol Chemical compound C1C(O)CCCC1C1=CC=CC=C1 YXBPBFIAVFWQMT-UHFFFAOYSA-N 0.000 description 1
- AFKMHDZOVNDWLO-UHFFFAOYSA-N 4-cyclohexylcyclohexan-1-ol Chemical compound C1CC(O)CCC1C1CCCCC1 AFKMHDZOVNDWLO-UHFFFAOYSA-N 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing and purifying 4- (4-hydroxyphenyl) cyclohexanone. 4,4 '-biphenol and catalyst palladium carbon are reacted with hydrogen in a reaction kettle to obtain 4- (4-hydroxyphenyl) cyclohexanone and 4, 4' -dicyclohexyl ketone. The purification is carried out by a method for purifying 4- (4-hydroxyphenyl) cyclohexanone, centrifugal separation, precipitation, drying and the like. The conversion rate of the raw material is 100 percent, the selectivity of the 4- (4-hydroxyphenyl) cyclohexanone reaches 76 percent, and the selectivity after the purification operation is more than 97 percent. The reaction product is single, the purification operation is simplified, the cost is reduced, and the economic benefit is great.
Description
Technical Field
The invention relates to the field of fine chemicals, in particular to a method for synthesizing and purifying 4- (4-hydroxyphenyl) cyclohexanone.
Background
4- (4-hydroxyphenyl) cyclohexanone is a medical intermediate with a chemical formula of
The preparation and purification difficulty is high, raw materials are not easy to purify, the conversion rate of the existing scheme is low, the conversion rate is 30-80%, the reaction product is complex, impurities are many, and the main impurities of the reaction comprise 4,4 ' -dicyclohexyl ketone, cyclohexyl cyclohexane, cyclohexyl benzene, 4-cyclohexyl cyclohexanol, 3-phenylcyclohexanol, 4,4 ' -dihydroxydicyclohexane, 4,4 ' -biphenol and the like except the target product 4- (4-hydroxyphenyl) cyclohexanone. And the method is difficult to separate from the target product, and has the defects of difficult purification and the like. 4- (4-hydroxyphenyl) cyclohexanone has great economic benefit, the current implementation method has high cost and large energy consumption, and new technology is urgently needed to improve the problems.
Disclosure of Invention
In order to solve the defects of low conversion rate, complex reaction product, difficult purification, difficult separation from a target product and the like in the prior art, high cost and high energy consumption, the invention provides a method for synthesizing 4- (4-hydroxyphenyl) cyclohexanone, which adopts 4,4 '-biphenol and palladium-carbon as a catalyst to react with hydrogen in a reaction kettle to obtain the 4- (4-hydroxyphenyl) cyclohexanone and the 4, 4' -dicyclohexylketone.
Preferably, the mass ratio of the 4, 4' -biphenol to the catalyst palladium carbon is 4.7-5.2: 0.29-0.33.
Preferably, in the reaction kettle, the hydrogenation gas is 0.95-1.0MPa, the reaction temperature is 130-150 ℃, and the reaction is continued for 50-75 minutes.
Preferably, the 4- (4-hydroxyphenyl) cyclohexanone is a main reaction product, and the 4, 4' -dicyclohexyl ketone is a reaction byproduct, and the reaction formula is as follows:
preferably, 30-40g of sec-butyl alcohol as a solvent is added into the reaction kettle.
The invention also provides a method for purifying the 4- (4-hydroxyphenyl) cyclohexanone, which comprises the following operation steps:
1) dissolving the reaction product with acetone, and removing the catalyst palladium carbon by a centrifugal filtration method;
2) drying the reactant in vacuum;
3) dissolving the reaction crude product in 3.8-4.1 wt% (mass fraction) of sodium hydroxide solution, and dropwise adding dilute hydrochloric acid until precipitation appears and the solution becomes turbid;
4) centrifugally drying to obtain 4- (4-hydroxyphenyl) cyclohexanone;
5) washing the 4- (4-hydroxyphenyl) cyclohexanone with deionized water, and repeating the operation for 3-4 times;
6) drying at 50-60 deg.C.
Preferably, the vacuum drying temperature is 35-45 ℃.
Preferably, the pH of the hydrochloric acid is 1.
Has the advantages that: the method adopts the Pd/C catalyst to produce the 4- (4-hydroxyphenyl) cyclohexanone by using the 4, 4' -biphenol in the sec-butyl alcohol solvent, under the operation condition, the conversion rate of the raw material is 100 percent, the selectivity of the target product 4- (4-hydroxyphenyl) cyclohexanone reaches 76 percent, and the selectivity after the purification operation is more than 97 percent. The reaction product is single, the purification operation is simplified, the cost is reduced, and the economic benefit is great.
Drawings
FIG. 1 is a schematic diagram of the synthesis and purification scheme of the present invention
FIG. 2 is a schematic diagram of a preferred synthesis and purification scheme of the present invention
Detailed Description
The invention is further described in the following examples, which show and describe the basic operating steps of the invention, together with the preferred proportions, in conjunction with the drawings, and there are variations and modifications which fall within the scope of the invention as claimed, without departing from the scope of the invention.
Example one
A method for synthesizing 4- (4-hydroxyphenyl) cyclohexanone comprises the following operation steps:
5g of 4, 4' -biphenol, 0.31g of palladium carbon as a catalyst and 30g of sec-butyl alcohol are put into a reaction kettle, and hydrogen of 1Mpa is introduced;
the temperature of the reaction kettle is 140 ℃, the rotating speed is 600r/min, and the reaction is continued for 1 h;
to obtain reaction products of 4- (4-hydroxyphenyl) cyclohexanone and 4, 4' -dicyclohexyl ketone.
Further, the 4- (4-hydroxyphenyl) cyclohexanone is a main reaction product, and the 4, 4' -dicyclohexyl ketone is the only reaction byproduct, and the reaction formula is as follows:
a method for purifying 4- (4-hydroxyphenyl) cyclohexanone comprises the following operation steps:
dissolving the reaction product with 20g of acetone, and removing the catalyst palladium carbon by a centrifugal filtration method;
vacuum drying at 40 deg.C;
dissolving the reaction crude product in 4 wt% (mass fraction) of sodium hydroxide solution, and dropwise adding dilute hydrochloric acid with the pH value of 1 until precipitation appears, so that the solution becomes turbid;
centrifuging to obtain 4- (4-hydroxyphenyl) cyclohexanone;
washing the 4- (4-hydroxyphenyl) cyclohexanone with deionized water, and repeating the operation for 3-4 times;
drying and drying at 60 ℃.
Claims (8)
1. The synthesis process of 4- (4-hydroxyphenyl) cyclohexanone features that 4,4 '-biphenol and Pd/C catalyst are reacted with hydrogen in a reactor to obtain 4- (4-hydroxyphenyl) cyclohexanone and 4, 4' -dicyclohexyl ketone.
2. The method for synthesizing 4- (4-hydroxyphenyl) cyclohexanone as claimed in claim 1, wherein the mass ratio of 4, 4' -biphenol to palladium on carbon as a catalyst in a reaction kettle is 4.7-5.2: 0.29-0.33.
3. The method for synthesizing 4- (4-hydroxyphenyl) cyclohexanone as claimed in claim 1, wherein the reaction is continued for 50-75 min at a reaction temperature of 130-150 ℃ and a hydrogen gas pressure of 0.95-1.0MPa in the reaction vessel.
4. The method for synthesizing 4- (4-hydroxyphenyl) cyclohexanone as claimed in claim 1, wherein the 4- (4-hydroxyphenyl) cyclohexanone is a main reaction product, 4, 4' -dicyclohexyl ketone is a reaction by-product, and the reaction chemical formula is as follows:
5. the synthesis method of 4- (4-hydroxyphenyl) cyclohexanone according to claim 1, wherein 30-40g of sec-butyl alcohol as solvent is added into the reaction kettle.
6. A method for purifying 4- (4-hydroxyphenyl) cyclohexanone, which is characterized by comprising the following operation steps:
1) dissolving the reaction product with acetone, and removing the catalyst palladium carbon by a centrifugal filtration method;
2) vacuum drying the reaction product;
3) dissolving the reaction crude product in 3.8-4.1 wt% (mass fraction) of sodium hydroxide solution, and dropwise adding dilute hydrochloric acid until precipitation appears and the solution becomes turbid;
4) centrifugally drying to obtain 4- (4-hydroxyphenyl) cyclohexanone;
5) washing the 4- (4-hydroxyphenyl) cyclohexanone with deionized water, and repeating the operation for 3-4 times;
6) drying at 50-60 deg.C.
7. The method for purifying 4- (4-hydroxyphenyl) cyclohexanone as claimed in claim 6, wherein the vacuum drying temperature is 35-45 ℃.
8. The process according to claim 6, wherein the pH of the hydrochloric acid is 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910259230.2A CN111777498A (en) | 2019-04-04 | 2019-04-04 | Synthesis and purification method of 4- (4-hydroxyphenyl) cyclohexanone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910259230.2A CN111777498A (en) | 2019-04-04 | 2019-04-04 | Synthesis and purification method of 4- (4-hydroxyphenyl) cyclohexanone |
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| CN111777498A true CN111777498A (en) | 2020-10-16 |
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| CN201910259230.2A Pending CN111777498A (en) | 2019-04-04 | 2019-04-04 | Synthesis and purification method of 4- (4-hydroxyphenyl) cyclohexanone |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001089469A (en) * | 1999-09-20 | 2001-04-03 | Honshu Chem Ind Co Ltd | Method for preparing 4,4'-bicyclohexanedione monoketals |
| US6313351B1 (en) * | 1999-07-15 | 2001-11-06 | Honshu Chemical Industry Co., Ltd. | Process for producing alicyclic monoketones and process for producing alicyclic diketones |
| JP2006036752A (en) * | 2004-06-25 | 2006-02-09 | Arakawa Chem Ind Co Ltd | Catalytic hydrogenation method using microreactor |
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2019
- 2019-04-04 CN CN201910259230.2A patent/CN111777498A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6313351B1 (en) * | 1999-07-15 | 2001-11-06 | Honshu Chemical Industry Co., Ltd. | Process for producing alicyclic monoketones and process for producing alicyclic diketones |
| JP2001089469A (en) * | 1999-09-20 | 2001-04-03 | Honshu Chem Ind Co Ltd | Method for preparing 4,4'-bicyclohexanedione monoketals |
| JP2006036752A (en) * | 2004-06-25 | 2006-02-09 | Arakawa Chem Ind Co Ltd | Catalytic hydrogenation method using microreactor |
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Application publication date: 20201016 |