CA2361682A1 - A method of preparing cyclohexanecaraboxylic acid using ¬2+4| diels-alder reaction - Google Patents
A method of preparing cyclohexanecaraboxylic acid using ¬2+4| diels-alder reaction Download PDFInfo
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- CA2361682A1 CA2361682A1 CA002361682A CA2361682A CA2361682A1 CA 2361682 A1 CA2361682 A1 CA 2361682A1 CA 002361682 A CA002361682 A CA 002361682A CA 2361682 A CA2361682 A CA 2361682A CA 2361682 A1 CA2361682 A1 CA 2361682A1
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- cyclohexene
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000005698 Diels-Alder reaction Methods 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 title 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 32
- JSSXHAMIXJGYCS-UHFFFAOYSA-N piperazin-4-ium-2-carboxylate Chemical compound OC(=O)C1CNCCN1 JSSXHAMIXJGYCS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008096 xylene Substances 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 4
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 abstract description 50
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 4
- 239000012847 fine chemical Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000011369 resultant mixture Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VUSWCWPCANWBFG-UHFFFAOYSA-N cyclohex-3-ene-1-carboxylic acid Chemical compound OC(=O)C1CCC=CC1 VUSWCWPCANWBFG-UHFFFAOYSA-N 0.000 description 2
- 150000005379 cyclohexanecarboxylic acid derivatives Chemical class 0.000 description 2
- -1 ethanol and methanol Chemical compound 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- WMJMABVHDMRMJA-UHFFFAOYSA-M [Cl-].[Mg+]C1CCCCC1 Chemical compound [Cl-].[Mg+]C1CCCCC1 WMJMABVHDMRMJA-UHFFFAOYSA-M 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- QCTBMLYLENLHLA-UHFFFAOYSA-N aminomethylbenzoic acid Chemical compound NCC1=CC=C(C(O)=O)C=C1 QCTBMLYLENLHLA-UHFFFAOYSA-N 0.000 description 1
- 229960003375 aminomethylbenzoic acid Drugs 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000008177 pharmaceutical agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
Abstract
Disclosed herein is a method of preparing cyclohexanecarboxylic acid in whic h 1,3-butadiene and acrylic acid are subjected to [2+4] Diels-Alder reaction t o produce 3-cyclohexene-1-carboxylic acid which is then hydrogenated. The [2+4 ] Diels-Alder reaction is carried out at a temperature of room temperature to 200 ~C in an aromatic hydrocarbon solvent, such as toluene or xylene. The hydrogenation is carried out at a temperature of room temperature to 150 ~C under a hydrogen pressure of 10 psi to 150 psi in the presence of the platin um of palladium catalyst. The disclosed method is featured in that it enables t he use of 1,3-butadiene as the raw material for fine chemicals, unlike the prio r methods. Moreover, the method disclosed is advantageous in that the reaction can be carried out in a relatively simple and easy manner and also the reaction by-products can be conveniently treated after the reaction.
Description
A METHOD OF PREPARING CYCLOHEXANECARBOXYLIC ACID
USING [2+4] DIELS-ALDER REACTION
Technical Field The present invention relates to a method of preparing cyclohexanecarboxylic acid in which 1,3 butadiene and acrylic acid are subjected to [2,4] Diels Alder reaction to produce 3-cyclohexene-1-carboxylic acid which is then hydrogenated with hydrogen in the presence of a platinum or palladium catalyst.
Background Art Cyclohexanecarboxylic acid is used as the raw material for synthetic organic materials, pharmaceutical agents, and fine chemicals. Cyclohexanecarboxylic acid derivatives are used as insecticides, tumor inhibitors, allergy inhibitors, and rheumatism inhibitors. For example, cyclohexanecarboxylic acid is known to be prepared by a synthesis process using carboxylation of cyclohexyl magnesium chloride, or by an industrial process using hydrogenation of benzoic acid.
Literature regarding [2+4] Diels-Alder reaction of 1,3-butadiene and acrylic acid includes Japanese Patent Publication Pyoung 5-301885 (1993), Japanese Patent Publication No. Sho 57-028165 (1982), and WO
86/04602(1986). In these patents, there are described the preparation of 3-cyclohexene-1-carboxylic acid with [2+4]
Diels-Alder reaction, and the application of such a compound to other compounds.
Although a method of preparing cyclohexanecarboxylic acid by hydrogenation of 3-cyclohexene-1-carboxylic acid is not yet known, the following is known with respect to the preparation of cyclohexanecarboxylic acid derivatives by hydrogenation: For example, in Japanese Patent Publication No. Pyoung 9-40606(1997) and Japanese Patent Publication No. Sho 49-026261(1974), there is disclosed a method of preparing cyclohexanecarboxylic acid substituted at the 4-position by reducing benzoic acid substituted at the 4-position in the presence of an alkali and a hydrogenation catalyst. Moreover, German Patent Publication No. 2349056 A(1975) discloses a method of preparing 4-aminomethylcyclohexane by reducing p-aminomethyl benzoic acid using a ruthenium catalyst and an alkali.
Disclosure of the Invention The present invention is a method of preparing cyclohexanecarboxylic acid in which 1,3-butadiene and acrylic acid are subjected to [2+4] Diels-Alder reaction to obtain 3-cyclohexene-1-carboxylic acid which is then hydrogenated using a Pt or Pd catalyst and hydrogen. The method according to this invention is advantageous in that the reaction for preparing cyclohexanecarboxylic acid is carried out in a relatively simple manner and a side reaction does not substantially occur.
In [2+4] Diels-Alder reaction of the method according to this invention, examples of a solvent capable of being used include an aromatic hydrocarbon solvent, such as toluene, benzene, and xylene, and an inexpensive and easily available solvent, such as alcohol, such as ethanol and methanol, and water, and the like. The [2+4] Diels Alder reaction solvent is used in the amount of 1000 to 50000 based on the weight of acrylic acid. Moreover, the temperature for carrying out [2+4] Diels-Alder reaction is in the range of room temperature to 200°C. The [2+4]
Diels-Alder reaction of the method according to this invention produces cyclohexanecarboxylic acid in a yield of 950 or more.
The higher the reaction temperature, the faster the reaction rate, but some polymers are generally produced.
As a way to solve such a drawback, the use of 4-tert-butylcatecol (hereinafter, called "TBC") or hydroquinone as a polymerization inhibitor during the [2+4] Diels-Alder reaction results in the inhibition of the production of polymer.
After [2+4] Diels-Alder reaction, the obtained 3-cyclohexene-1-carboxylic acid is hydrogenated in the presence of a Pd or Pt catalyst and hydrogen. This hydrogenation is carried out at a temperature of room temperature to 100°C under a hydrogen pressure of 10 psi to 150 psi, in a solvent selected from the group consisting of ethanol, methanol, water, toluene, and xylene. The hydrogenation solvent is used in the amount of 1000 to 5000% based on the volume of 3-cyclohexene-1-carboxylic acid.
Consequently, unlike the prior methods for the preparation of cyclohexanecarboxylic acid, the method of this invention is significant in the preparation of fine chemicals using 1,3-butadiene. In addition, the method of the invention is advantageous in that the reaction for preparing cyclohexanecarboxylic acid is carried out in a relatively simple and easy manner and also the reaction by-products are conveniently treated.
Best Mode for Carrying Out the Invention The following examples are for illustration purposes 4 PCT/KR99/00739_ only and in no way limit the scope of this invention.
Examples In the following examples, 3-cyclohexene-1-carboxylic was synthesized using acrylic acid as dienophile, and 1,3 butadiene as dime. As a solvent for [2+4] Diels-Alder reaction, an aromatic hydrocarbon compound, such as toluene, benzene, or xylene, alcohol, or water, was used.
The molar ratio of 1,3-butadiene to dienophile is in the range of 1 to 1.4. TBC or hydroquinone, as a polymerization inhibitor, was used in the amount of zero to 10,000 ppm based on the weight of 1,3-butadiene. After producing 3-cyclohexene-1-carboxylic acid which is a [2+4]
Diels-Alder reaction product, hydrogenation of 3-cyclohexene-1-carboxylic acid was carried out using a Pd or Pt catalyst. The use of each of these catalysts showed the conversion of 1000.
Meanwhile, [2+4] Diels-Alder reaction was carried out in a pressure reactor, and hydrogenation was carried out in a hydrogen reactor or a pressure reactor. The analysis of the reaction product was performed by the Nuclear Magnetic Resonance(NMR) spectrum and the Gas Chromatography-Mass Spectroscopy Detector (GC-MSD) to confirm the product. When confirming the quantitative analysis value of the reaction product by gas chromatography, the analysis was carried out in accordance with the following conditions:
Capillary column: HP-20, 25mm X 0.20mm X 0.2~m.
Carrier gas: nitrogen Head pressure: 18 psig Oven: 80°C(Omin.) to 190°C, (3=10°C/min.
Detector and temperature: FID(280°C).
USING [2+4] DIELS-ALDER REACTION
Technical Field The present invention relates to a method of preparing cyclohexanecarboxylic acid in which 1,3 butadiene and acrylic acid are subjected to [2,4] Diels Alder reaction to produce 3-cyclohexene-1-carboxylic acid which is then hydrogenated with hydrogen in the presence of a platinum or palladium catalyst.
Background Art Cyclohexanecarboxylic acid is used as the raw material for synthetic organic materials, pharmaceutical agents, and fine chemicals. Cyclohexanecarboxylic acid derivatives are used as insecticides, tumor inhibitors, allergy inhibitors, and rheumatism inhibitors. For example, cyclohexanecarboxylic acid is known to be prepared by a synthesis process using carboxylation of cyclohexyl magnesium chloride, or by an industrial process using hydrogenation of benzoic acid.
Literature regarding [2+4] Diels-Alder reaction of 1,3-butadiene and acrylic acid includes Japanese Patent Publication Pyoung 5-301885 (1993), Japanese Patent Publication No. Sho 57-028165 (1982), and WO
86/04602(1986). In these patents, there are described the preparation of 3-cyclohexene-1-carboxylic acid with [2+4]
Diels-Alder reaction, and the application of such a compound to other compounds.
Although a method of preparing cyclohexanecarboxylic acid by hydrogenation of 3-cyclohexene-1-carboxylic acid is not yet known, the following is known with respect to the preparation of cyclohexanecarboxylic acid derivatives by hydrogenation: For example, in Japanese Patent Publication No. Pyoung 9-40606(1997) and Japanese Patent Publication No. Sho 49-026261(1974), there is disclosed a method of preparing cyclohexanecarboxylic acid substituted at the 4-position by reducing benzoic acid substituted at the 4-position in the presence of an alkali and a hydrogenation catalyst. Moreover, German Patent Publication No. 2349056 A(1975) discloses a method of preparing 4-aminomethylcyclohexane by reducing p-aminomethyl benzoic acid using a ruthenium catalyst and an alkali.
Disclosure of the Invention The present invention is a method of preparing cyclohexanecarboxylic acid in which 1,3-butadiene and acrylic acid are subjected to [2+4] Diels-Alder reaction to obtain 3-cyclohexene-1-carboxylic acid which is then hydrogenated using a Pt or Pd catalyst and hydrogen. The method according to this invention is advantageous in that the reaction for preparing cyclohexanecarboxylic acid is carried out in a relatively simple manner and a side reaction does not substantially occur.
In [2+4] Diels-Alder reaction of the method according to this invention, examples of a solvent capable of being used include an aromatic hydrocarbon solvent, such as toluene, benzene, and xylene, and an inexpensive and easily available solvent, such as alcohol, such as ethanol and methanol, and water, and the like. The [2+4] Diels Alder reaction solvent is used in the amount of 1000 to 50000 based on the weight of acrylic acid. Moreover, the temperature for carrying out [2+4] Diels-Alder reaction is in the range of room temperature to 200°C. The [2+4]
Diels-Alder reaction of the method according to this invention produces cyclohexanecarboxylic acid in a yield of 950 or more.
The higher the reaction temperature, the faster the reaction rate, but some polymers are generally produced.
As a way to solve such a drawback, the use of 4-tert-butylcatecol (hereinafter, called "TBC") or hydroquinone as a polymerization inhibitor during the [2+4] Diels-Alder reaction results in the inhibition of the production of polymer.
After [2+4] Diels-Alder reaction, the obtained 3-cyclohexene-1-carboxylic acid is hydrogenated in the presence of a Pd or Pt catalyst and hydrogen. This hydrogenation is carried out at a temperature of room temperature to 100°C under a hydrogen pressure of 10 psi to 150 psi, in a solvent selected from the group consisting of ethanol, methanol, water, toluene, and xylene. The hydrogenation solvent is used in the amount of 1000 to 5000% based on the volume of 3-cyclohexene-1-carboxylic acid.
Consequently, unlike the prior methods for the preparation of cyclohexanecarboxylic acid, the method of this invention is significant in the preparation of fine chemicals using 1,3-butadiene. In addition, the method of the invention is advantageous in that the reaction for preparing cyclohexanecarboxylic acid is carried out in a relatively simple and easy manner and also the reaction by-products are conveniently treated.
Best Mode for Carrying Out the Invention The following examples are for illustration purposes 4 PCT/KR99/00739_ only and in no way limit the scope of this invention.
Examples In the following examples, 3-cyclohexene-1-carboxylic was synthesized using acrylic acid as dienophile, and 1,3 butadiene as dime. As a solvent for [2+4] Diels-Alder reaction, an aromatic hydrocarbon compound, such as toluene, benzene, or xylene, alcohol, or water, was used.
The molar ratio of 1,3-butadiene to dienophile is in the range of 1 to 1.4. TBC or hydroquinone, as a polymerization inhibitor, was used in the amount of zero to 10,000 ppm based on the weight of 1,3-butadiene. After producing 3-cyclohexene-1-carboxylic acid which is a [2+4]
Diels-Alder reaction product, hydrogenation of 3-cyclohexene-1-carboxylic acid was carried out using a Pd or Pt catalyst. The use of each of these catalysts showed the conversion of 1000.
Meanwhile, [2+4] Diels-Alder reaction was carried out in a pressure reactor, and hydrogenation was carried out in a hydrogen reactor or a pressure reactor. The analysis of the reaction product was performed by the Nuclear Magnetic Resonance(NMR) spectrum and the Gas Chromatography-Mass Spectroscopy Detector (GC-MSD) to confirm the product. When confirming the quantitative analysis value of the reaction product by gas chromatography, the analysis was carried out in accordance with the following conditions:
Capillary column: HP-20, 25mm X 0.20mm X 0.2~m.
Carrier gas: nitrogen Head pressure: 18 psig Oven: 80°C(Omin.) to 190°C, (3=10°C/min.
Detector and temperature: FID(280°C).
Split ratio: 40:1 Make up gas flow rate: 38m1.
Moreover, the ratio of the components was used in terms of the area ratio of gas chromatography.
Example 1 Into a 1 liter pressure reactor were charged acrylic acid (72g, 1 mol), xylene 2888 and TBC 75mg. Then; while stirring the contents of the reactor, 1,3-butadiene 75g was introduced into the reactor. After that, a temperature of the resultant mixture was elevated to 120 °C and left to react at this temperature for 3 hours. Thereafter, the analysis of the reaction product by NMR spectrometry and gas chromatography confirmed that 3-cyclohexen-1-carboxylic acid was obtained in a yield of 990.
Example 2 The procedure of Example 1 was repeated five times with a reaction temperature and a molar ratio varying for each time as described in Table 1 below. For each time, 3 cyclohexene-1-carboxylic acid was obtained in a yield described in Table 1.
Moreover, the ratio of the components was used in terms of the area ratio of gas chromatography.
Example 1 Into a 1 liter pressure reactor were charged acrylic acid (72g, 1 mol), xylene 2888 and TBC 75mg. Then; while stirring the contents of the reactor, 1,3-butadiene 75g was introduced into the reactor. After that, a temperature of the resultant mixture was elevated to 120 °C and left to react at this temperature for 3 hours. Thereafter, the analysis of the reaction product by NMR spectrometry and gas chromatography confirmed that 3-cyclohexen-1-carboxylic acid was obtained in a yield of 990.
Example 2 The procedure of Example 1 was repeated five times with a reaction temperature and a molar ratio varying for each time as described in Table 1 below. For each time, 3 cyclohexene-1-carboxylic acid was obtained in a yield described in Table 1.
Table 1 Effect of the varying reaction temperatures and molar ratios of reactants on a yield of 3-cyclohexene-1 carboxylic acid 1,3- Temperature (°C) Reaction Time Yield (o BD(g)/AA(g)' (hr) 1 0 72/73 1401.5 99 *1,3-BD: 1,3-butadiene, AA:acrylic acid Example 3 Into a 1 liter pressure reactor were charged acrylic acid (72g, 1 mol) and toluene 2888. Then, 1,3-butadiene 75g was introduced into the reactor. After that, a temperature of the resultant mixture was elevated to 120 °C and left to react at this temperature for 6 hours. Thereafter, the analysis of the reaction product by NMR spectrometry and gas chromatography confirmed that 3-cyclohexene-1-carboxylic acid was obtained in a yield of 980.
Example 4 The procedure of Example 3 was repeated four times with a reaction solvent and a reaction temperature varying for each time as described in Table 2 below: For each time, 3-cyclohexene-1-carboxylic acid was obtained in a yield described in Table 2.
Table 2 Effect of the varying kinds of solvents and reaction temperatures on a yield of 3-cyclohexene-1-carboxylic acid Solvent Yield(o) Reaction Time Reaction (hr) Temperature (°C) Xylene 99 4.5 120 Toluene 98 6 120 Ethanol 66 8 100 Water 98 8 100 None 99 7 100 Example 5 The procedure was repeated four times with a reaction temperature varying for each time as described in Table 3.
For each time, 3-cyclohexene-1-carboxylic acid was obtained in a yield described in Table 3.
-g-Table3 Effect of the, varying reaction temperatures on a yield of 3-cyclohexene-1-carboxylic acid Reaction Temperature Yield (%) Reaction Time ( ~C) (hr) Example 6 The reaction was carried out for 3 hours under the same conditions as those in Example 3 except that anhydrous aluminum trichloride (A1C13) as a catalyst was further used. 3-Cyclohexene-1-carboxylic acid was obtained in a yield of 940.
Example 7 3-Cyclohexene-1-carboxylic acid 53g prepared in Example 1 was dissolved in xylene 1258. The resultant mixture was hydrogenated at room temperature in the presence of a 5oPd/C catalyst (3 wto) under a hydrogen pressure of 85 psi. Cyclohexanecarboxylic acid was obtained in a yield of 95o at one hour after starting hydrogenation and in a yield of 99o at 2 hours after starting hydrogenation.
Example 8 The procedure of Example 7 was repeated four times with the amount of catalyst varying for each time as WO 00/46174 PCT/KR99/00739 _ described in Table 4 below. For each time, cyclohexanecarboxylic acid was obtained in a yield described in Table 4.
Table 4 Effect of the varying amounts catalyst on a yield of of cyclohexanecarboxylic acid Amount of Amount of Amount of Reaction Yield reactant' solvent catalyst time(hr) (%) 53 125 1.6(3wt%) 1 95 58 140 1.2(2wt%) 2 95 45 105 0.5(lwt%) 3 92 43 100 0.2(0.5wt%)6 72 tteactant:~-cyclonexene-1-carboxylic acid Example 9 3-Cyclohexene-1-carboxylic acid lOg prepared in Example 3 was dissolved in toluene 0.5 liter. Then, the resultant mixture was hydrogenated in the presence of 0.2 g of a 5%Pd/C catalyst (3 wto) under a hydrogen pressure of 10 psi. Cyclohexanecarboxylic acid was obtained in a yield of 970.
Example 10 The procedure of Example 9 was repeated three times with a hydrogen pressure varying for each time as described in Table 5 below. For each time, cyclohexanecarboxylic acid was obtained in a yield described in Table 5:
Table 5 Effect of the. varying hydrogen pressures on a yield of cyclohexanecarboxylic acid Hydrogen pressure (psi) Yield (%) Example 11 The procedure of Example 9 was repeated three times with the ratio of reactant to solvent varying for each time as described in Table 6 below. For each time, cyclohexanecarboxylic acid was obtained in a yield described in Table 6.
Table 6 Effect of the varying ratios of reactant to solvent on a yield of cyclohexanecarboxylic acid Reactant/Solvent Yield (~) Example 12 The procedure of Example 9 was repeated three times with the amount of catalyst varying for each time as described in Table 7 below. For each time, cyclohexanecarboxylic acid was obtained in a yield WO 00/46174 PCT/KR99/00739 _ described in Table 7.
Table 7 Effect of the varying amounts of catalyst on a yield of cyclohexanecarboxylic acid Amount of catalyst Yield (o) 0.1 80 0.2 97 0.5 100 Example 13 The procedure of Example 9 was repeated except that 3o Pd/C catalyst was used instead of 5o Pd/C catalyst.
Cyclohexanecarboxylic acid was obtained in a yield of 100%.
Example 14 The procedure of Example 9 was repeated except that ethanol was used instead of toluene. Cyclohexanecarboxylic acid was obtained in a yield of 1000.
Industrial Applicability The method of this invention produces cyclohexanecarboxylic acid by subjecting 1,3-butadiene and acrylic acid to [2+4] Diels-Alder reaction to produce 3-cyclohexene-1-carboxylic acid, and then hydrogenating the obtained 3-cyclohexene-1-carboxylic acid. Thus, the method of this invention is advantageous in that the reaction is carried out in a relatively simple manner, and also a side reaction does not occur.
WO 00/46174 PCT/KR99/0073~
In the method of this invention, [2+4] Diels-Alder reaction of 1,3-butadiene and acrylic acid is carried out using an aromatic hydrocarbon solvent, such as toluene, benzene, or xylene, at a temperature of room temperature to 200 °C. In addition, hydrogenation of 3-cyclohexene-1-carboxylic acid is carried out using an inexpensive and easily available solvent, such as alcohol, such as ethanol or methanol, or water, and the like, under very low pressure, such as a hydrogen pressure of 10 psi to 150 psi, and the reaction yield is 95% or more. Consequently, this invention is advantageous in that it enables the production of fine chemicals using 1,3-butadiene, unlike the prior methods for the preparation of cyclohexanecarboxylic acid. Moreover, other advantages of this invention are that the reaction is carried out in a relatively simple and easy manner, and also the reaction by-products are conveniently treated after the reaction.
Although the preferred embodiments of the invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Example 4 The procedure of Example 3 was repeated four times with a reaction solvent and a reaction temperature varying for each time as described in Table 2 below: For each time, 3-cyclohexene-1-carboxylic acid was obtained in a yield described in Table 2.
Table 2 Effect of the varying kinds of solvents and reaction temperatures on a yield of 3-cyclohexene-1-carboxylic acid Solvent Yield(o) Reaction Time Reaction (hr) Temperature (°C) Xylene 99 4.5 120 Toluene 98 6 120 Ethanol 66 8 100 Water 98 8 100 None 99 7 100 Example 5 The procedure was repeated four times with a reaction temperature varying for each time as described in Table 3.
For each time, 3-cyclohexene-1-carboxylic acid was obtained in a yield described in Table 3.
-g-Table3 Effect of the, varying reaction temperatures on a yield of 3-cyclohexene-1-carboxylic acid Reaction Temperature Yield (%) Reaction Time ( ~C) (hr) Example 6 The reaction was carried out for 3 hours under the same conditions as those in Example 3 except that anhydrous aluminum trichloride (A1C13) as a catalyst was further used. 3-Cyclohexene-1-carboxylic acid was obtained in a yield of 940.
Example 7 3-Cyclohexene-1-carboxylic acid 53g prepared in Example 1 was dissolved in xylene 1258. The resultant mixture was hydrogenated at room temperature in the presence of a 5oPd/C catalyst (3 wto) under a hydrogen pressure of 85 psi. Cyclohexanecarboxylic acid was obtained in a yield of 95o at one hour after starting hydrogenation and in a yield of 99o at 2 hours after starting hydrogenation.
Example 8 The procedure of Example 7 was repeated four times with the amount of catalyst varying for each time as WO 00/46174 PCT/KR99/00739 _ described in Table 4 below. For each time, cyclohexanecarboxylic acid was obtained in a yield described in Table 4.
Table 4 Effect of the varying amounts catalyst on a yield of of cyclohexanecarboxylic acid Amount of Amount of Amount of Reaction Yield reactant' solvent catalyst time(hr) (%) 53 125 1.6(3wt%) 1 95 58 140 1.2(2wt%) 2 95 45 105 0.5(lwt%) 3 92 43 100 0.2(0.5wt%)6 72 tteactant:~-cyclonexene-1-carboxylic acid Example 9 3-Cyclohexene-1-carboxylic acid lOg prepared in Example 3 was dissolved in toluene 0.5 liter. Then, the resultant mixture was hydrogenated in the presence of 0.2 g of a 5%Pd/C catalyst (3 wto) under a hydrogen pressure of 10 psi. Cyclohexanecarboxylic acid was obtained in a yield of 970.
Example 10 The procedure of Example 9 was repeated three times with a hydrogen pressure varying for each time as described in Table 5 below. For each time, cyclohexanecarboxylic acid was obtained in a yield described in Table 5:
Table 5 Effect of the. varying hydrogen pressures on a yield of cyclohexanecarboxylic acid Hydrogen pressure (psi) Yield (%) Example 11 The procedure of Example 9 was repeated three times with the ratio of reactant to solvent varying for each time as described in Table 6 below. For each time, cyclohexanecarboxylic acid was obtained in a yield described in Table 6.
Table 6 Effect of the varying ratios of reactant to solvent on a yield of cyclohexanecarboxylic acid Reactant/Solvent Yield (~) Example 12 The procedure of Example 9 was repeated three times with the amount of catalyst varying for each time as described in Table 7 below. For each time, cyclohexanecarboxylic acid was obtained in a yield WO 00/46174 PCT/KR99/00739 _ described in Table 7.
Table 7 Effect of the varying amounts of catalyst on a yield of cyclohexanecarboxylic acid Amount of catalyst Yield (o) 0.1 80 0.2 97 0.5 100 Example 13 The procedure of Example 9 was repeated except that 3o Pd/C catalyst was used instead of 5o Pd/C catalyst.
Cyclohexanecarboxylic acid was obtained in a yield of 100%.
Example 14 The procedure of Example 9 was repeated except that ethanol was used instead of toluene. Cyclohexanecarboxylic acid was obtained in a yield of 1000.
Industrial Applicability The method of this invention produces cyclohexanecarboxylic acid by subjecting 1,3-butadiene and acrylic acid to [2+4] Diels-Alder reaction to produce 3-cyclohexene-1-carboxylic acid, and then hydrogenating the obtained 3-cyclohexene-1-carboxylic acid. Thus, the method of this invention is advantageous in that the reaction is carried out in a relatively simple manner, and also a side reaction does not occur.
WO 00/46174 PCT/KR99/0073~
In the method of this invention, [2+4] Diels-Alder reaction of 1,3-butadiene and acrylic acid is carried out using an aromatic hydrocarbon solvent, such as toluene, benzene, or xylene, at a temperature of room temperature to 200 °C. In addition, hydrogenation of 3-cyclohexene-1-carboxylic acid is carried out using an inexpensive and easily available solvent, such as alcohol, such as ethanol or methanol, or water, and the like, under very low pressure, such as a hydrogen pressure of 10 psi to 150 psi, and the reaction yield is 95% or more. Consequently, this invention is advantageous in that it enables the production of fine chemicals using 1,3-butadiene, unlike the prior methods for the preparation of cyclohexanecarboxylic acid. Moreover, other advantages of this invention are that the reaction is carried out in a relatively simple and easy manner, and also the reaction by-products are conveniently treated after the reaction.
Although the preferred embodiments of the invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (11)
1. A method of preparing cyclohexanecarboxylic acid, comprising : subjecting 1,3-butadiene and acrylic acid to [2+4] Diels-Alder reaction to synthesize 3-cyclohexene-1-carboxylic acid; and catalytic hydrogenating the 3-cyclohexene-1-carboxylic acid.
2. The method of Claim 1, wherein the [2+4] Diels-Alder reaction is carried out at a temperature of room temperature to 200°C.
3. The method of Claim 1, wherein the [2+4] Diels-Alder reaction is carried out in a solvent selected from the group consisting of water, ethanol, toluene, benzene, and xylene or under the condition using no solvent.
4. The method of Claim 3, wherein the [2+4] Diels-Alder reaction solvent is used in the amount of 100% to 5000% based on the weight of acrylic acid.
5. The method of Claim 1, wherein the [2+4] Diels-Alder reaction is carried out in the presence of 4-tert-butylcatechol or hydroquinone, as a polymerization inhibitor.
6. The method of Claim 1, wherein the catalytic hydrogenation is carried out at a temperature of room temperature to 100°C.
7. The method of Claim 1, wherein the catalytic hydrogenation is carried out in the presence of a Pt or Pd catalyst.
8. The method of Claim 7, wherein the hydrogenation catalyst is used in the amount of 0.5 to 5% based on the weight of 3-cyclohexene-1-carboxylic acid.
9. The method of Claim 1, wherein the catalytic hydrogenation is carried out under a hydrogen pressure of 10 psi to 150 psi.
10. The method of Claim 1, wherein the catalytic hydrogenation is carried out in a solvent selected from the group consisting of ethanol, methanol, water, toluene, and xylene or under the condition using no solvent.
11. The method of Claim 10, wherein the hydrogenation solvent is used in the amount of 100% to 5000% based on the volume of 3-cyclohexene-1-carboxylic acid.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR19990004025 | 1999-02-05 | ||
| KR1019990037508A KR20000056975A (en) | 1999-02-05 | 1999-09-03 | A method of preparing cyclohexanecarboxlic acid using [2+4] Diels-Alder reaction |
| KR1999/4025 | 1999-09-03 | ||
| KR1999/37508 | 1999-09-03 | ||
| PCT/KR1999/000739 WO2000046174A1 (en) | 1999-02-05 | 1999-12-04 | A method of preparing cyclohexanecaraboxylic acid using [2+4] diels-alder reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2361682A1 true CA2361682A1 (en) | 2000-08-10 |
Family
ID=26634676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002361682A Abandoned CA2361682A1 (en) | 1999-02-05 | 1999-12-04 | A method of preparing cyclohexanecaraboxylic acid using ¬2+4| diels-alder reaction |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1187801A4 (en) |
| JP (1) | JP2002539083A (en) |
| KR (1) | KR20000056975A (en) |
| CN (1) | CN1348437A (en) |
| AU (1) | AU1513800A (en) |
| BR (1) | BR9917235A (en) |
| CA (1) | CA2361682A1 (en) |
| HU (1) | HUP0200112A3 (en) |
| PL (1) | PL350029A1 (en) |
| WO (1) | WO2000046174A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100496763B1 (en) * | 2002-04-23 | 2005-06-22 | 한국과학기술연구원 | Method to produce cyclohexanecarboxylic acid by the hydrogenation of benzoic acid at the aqueous phase |
| KR20040026964A (en) * | 2002-09-27 | 2004-04-01 | 금호석유화학 주식회사 | Synthesis of cyclohexyl phenyl ketone from 1,3-butadiene and acrylic acid |
| CN101768074B (en) * | 2009-12-29 | 2017-09-26 | 大连九信精细化工有限公司 | A kind of new method for synthesizing 4 carboxymethyl cyclohexane-carboxylic acids |
| DE102010040282A1 (en) * | 2010-09-06 | 2012-03-08 | Evonik Röhm Gmbh | Functional materials with controllable viscosity or reversible crosslinking via aza-Diels-Alder reactions with bishydrazones or conjugated bis-Schiff bases |
| US9115155B1 (en) * | 2014-03-20 | 2015-08-25 | Eastman Chemical Company | Low-pressure synthesis of cyclohexanedimethanol and derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54157546A (en) * | 1978-05-30 | 1979-12-12 | Mitsui Toatsu Chem Inc | Preparation of 3-cyclohexenecarboxylic acid |
-
1999
- 1999-09-03 KR KR1019990037508A patent/KR20000056975A/en not_active Application Discontinuation
- 1999-12-04 BR BR9917235-6A patent/BR9917235A/en not_active Application Discontinuation
- 1999-12-04 WO PCT/KR1999/000739 patent/WO2000046174A1/en not_active Application Discontinuation
- 1999-12-04 PL PL99350029A patent/PL350029A1/en unknown
- 1999-12-04 CN CN99816019A patent/CN1348437A/en active Pending
- 1999-12-04 EP EP99957434A patent/EP1187801A4/en not_active Withdrawn
- 1999-12-04 JP JP2000597247A patent/JP2002539083A/en active Pending
- 1999-12-04 AU AU15138/00A patent/AU1513800A/en not_active Abandoned
- 1999-12-04 CA CA002361682A patent/CA2361682A1/en not_active Abandoned
- 1999-12-04 HU HU0200112A patent/HUP0200112A3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000046174A1 (en) | 2000-08-10 |
| EP1187801A4 (en) | 2002-09-18 |
| CN1348437A (en) | 2002-05-08 |
| EP1187801A1 (en) | 2002-03-20 |
| KR20000056975A (en) | 2000-09-15 |
| BR9917235A (en) | 2001-11-27 |
| AU1513800A (en) | 2000-08-25 |
| HUP0200112A3 (en) | 2003-02-28 |
| PL350029A1 (en) | 2002-10-21 |
| JP2002539083A (en) | 2002-11-19 |
| HUP0200112A2 (en) | 2002-05-29 |
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