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WO2004047990A1 - Catalyseur destines a la preparation d'esters carboxyliques et processus de preparation d'esters carboxyliques avec ce catalyseur - Google Patents

Catalyseur destines a la preparation d'esters carboxyliques et processus de preparation d'esters carboxyliques avec ce catalyseur Download PDF

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Publication number
WO2004047990A1
WO2004047990A1 PCT/JP2003/015089 JP0315089W WO2004047990A1 WO 2004047990 A1 WO2004047990 A1 WO 2004047990A1 JP 0315089 W JP0315089 W JP 0315089W WO 2004047990 A1 WO2004047990 A1 WO 2004047990A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
carboxylic acid
producing
acid ester
compound
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.)
Ceased
Application number
PCT/JP2003/015089
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English (en)
Japanese (ja)
Inventor
Yoshihiro Watanabe
Yasushi Kuroda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to AU2003284456A priority Critical patent/AU2003284456A1/en
Publication of WO2004047990A1 publication Critical patent/WO2004047990A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction

Definitions

  • the present invention discloses a carboxylic acid ester using an aldehyde compound as a raw material.
  • the present invention relates to a novel catalyst used in production. Further, the present invention relates to a method for producing a carbonate by performing a dimerization reaction of a starting aldehyde compound using the catalyst.
  • the present invention can be used for reactions using various aldehydes as raw materials, and is particularly effective when dimerizing acetoaldehyde to produce ethyl acetate.
  • Lanthanide triflate compounds, ittium triflate compounds and scandium triflate compounds have also been proposed as cocatalysts (see Japanese Patent Application Laid-Open No. 11-140016).
  • these catalyst systems are used at temperatures higher than around room temperature. It is known that the life is extremely short, and the conversion of raw materials and the productivity of the target product are extremely low. Therefore, use at a low temperature of 15 to 5 ° C is inevitable. Since this reaction is exothermic, cooling is required to maintain a low temperature. Low-temperature use is not economical for industrial-scale production because of the investment in equipment such as refrigerators and the cost of operating the equipment.
  • the present invention provides a system for synthesizing a carboxylic acid ester from an aldehyde compound as typified by the Teishinko reaction, which does not require a special cooling device, and allows a reaction at a temperature higher than room temperature.
  • One of the issues is to provide a catalyst with high selectivity and long life.
  • Another object of the present invention is to provide a method for producing a carboxylic acid ester using the catalyst. Disclosure of the invention
  • the present inventors have conducted intensive studies in order to achieve the above-mentioned object, and as a result, it has been found that dimerization of an aldehyde compound can be achieved by simultaneously using an aluminum alkoxide and a sulfonic acid and / or a specific metal sulfonate. They have found that they are useful as catalysts for the production of carboxylic esters by the reaction, that they can be reacted without maintaining low temperatures, and that they have high selectivity.
  • a catalyst for producing a carboxylic acid ester used for producing a carboxylic acid ester by a dimerization reaction of an aldehyde compound, comprising an aluminum alkoxide compound, a sulfonic acid and / or a sulfonic acid and / or a periodic table of the sulfonic acid.
  • a catalyst for producing a carboxylic acid ester comprising at least one compound selected from salts of Group 4 metals.
  • a catalyst for producing a carboxylic acid ester used for producing a carboxylic acid ester by a dimerization reaction of an aldehyde compound, comprising an aluminum alkoxide compound, sulfonic acid and z or 10 or 10 of the periodic table of the sulfonic acid.
  • a catalyst for the production of a carboxylic acid ester comprising at least one compound selected from salts of a Group 14 metal.
  • Sulfonic acid and / or a salt of a metal of Groups 4 to 14 of the periodic table of the sulfonic acid is selected from the group consisting of trifluoromethansulfonate, copper trifluorometanesulfonate, silver trifluorometanesulfonate,
  • a method for producing a carboxylic acid ester by dimerization of an aldehyde compound comprising a step of contacting the aldehyde compound with the catalyst for producing a sulfonic acid ester according to the above [1] or [2].
  • a method for producing a carboxylic acid ester comprising a step of contacting the aldehyde compound with the catalyst for producing a sulfonic acid ester according to the above [1] or [2].
  • the sulfonic acid in the present invention is “a compound in which a hydrogen atom of a hydrocarbon is substituted with a sulfonate group—SO 3 H, and also includes a sulfonic anhydride”.
  • the sulfonic acid that can be used in the present invention is not particularly limited as long as it is a sulfonic acid defined above.
  • methanesulphonic acid ethanesulphonic acid, propanesulphonic acid, n-butanesulphonic acid, n-pentanesulphonic acid, n-hexansnolephonic acid, cyclohexansnolephonic acid, n-pentanesnorephonic acid, n-octanesnolefonic acid , Chloromethan sulfonic acid, dichloromethan sulfonic acid, tricrome rometan sulfonic acid, fluoromethan sulfonic acid, diphnoleolomethan sulfonic acid, trifluoromethan sulfonic acid, trifluoromethan sulfonic acid, perfluorobuta Sulfonic acid, 2,3,5,6—tetrafluorocyclohexanesulfonic acid, 2,3,4,5,6_pentafluorocyclohexanesnorenoic acid, benzenesn
  • a polymer containing a sulfonic acid group can also be used, and specific examples thereof include a copolymer of perfluorovinyl ether containing a sulfonyl fluoride group and tetrafluoroethylene.
  • phenololenomethanosulfonate diphnoleolomethane stannolefonic acid, triphenylenelomethane stannolefonic acid, perphnoreolobutanesnolefonic acid, 2,3,5,6-tetrafnoroleolocyclohexanesulfonic acid, 2,3 , 4,5,6_Pentaph / reolocyclohexanosolephonic acid, 2,3,5,6—Tetrafnorolobenzenesnolephonic acid, 2,3,4,5,6 Acids, fluorinated hydrocarbon sulfonic acids such as copolymers of vinylol ether with vinylphenol containing a snolephoninolefolenoleide group and tetrafluoroethylene.
  • fluoromethansnolefonic acid diphnolelomethanesulphonic acid, triflightolenomethanesnolefonic acid, perphleololobutanesulphonic acid, 2,3,5,6—tetrafluorocyclohexanesnolefonic acid, 2 , 3,4,5,6-Pentaphthalenosulfuric acid It is a fluorinated saturated alkyl sulfonic acid such as hexansorenoic acid, most preferably trifluoromethanesnolephonic acid.
  • sulfonic acids may be condensed acid anhydrides, and the sulfonic acids before condensation may be the same or different.
  • sulfonic acids may be condensed acid anhydrides, and the sulfonic acids before condensation may be the same or different.
  • trifluoromethanesulfonic anhydride, perfluorobutanesulfonic anhydride, 2,3,5,6-tetrafluorobenzenesulfonic anhydride and the like can be mentioned.
  • the sulfonic acid salt used in combination with the aluminum alkoxide compound in the present invention is not particularly limited as long as it is a salt of a metal belonging to Groups 4 to 14 of the periodic table of sulfonic acid described above. Sulfonates of Group 10-14 metals are more preferred.
  • the periodic table used here is It is based on the IUPAC inorganic chemical nomenclature revised in 1989.
  • Preferred sulfonates used in the present invention are Group 10-10 metal such as Ni, Cu, Zn, Pd, Ag, Pt, Au, Sn, Pb. It is a salt. More preferred are copper trifluoromethanesulfonate, silver trifluoromethanesulfonate, zinc trifluoromethanesulfonate, and tin trifluoromethanesulfonate.
  • sulfonic acids sulfonic anhydrides and z or salts of the sulfonic acids may be used alone or in combination of two or more.
  • the metal salt of sulfonic acid that can be used in the present invention is synthesized by a known method. There is no particular limitation on the synthesis method. Generally, it is synthesized by heating by reacting a metal oxide with an aqueous sulfonic acid solution. For example, in the case of copper trifluoromethanesulfonate, it is synthesized by heating copper oxide and an aqueous solution of trifluoromethanesulfonate, dried, and then dried under vacuum at 100 to 200 ° C. .
  • the aluminum alkoxide compound is not particularly limited as long as it contains an alkoxide-aluminum bond in its structure.
  • a typical example is aluminum-trium alkoxide, but also includes those partially aluminum-halogen bonded or condensed. It does not need to be a single compound, and includes a mixture thereof.
  • alkoxide moiety is an optionally branched alkoxy group having 1 to 8 carbon atoms are preferred.
  • Specific examples include aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, aluminum triisopropoxide, aluminum trim-n-butoxide, and aluminum tri-sec.
  • the aluminum alkoxide compound contains a condensate of the aluminum alkoxide compound.
  • a part of the compound as exemplified above is condensed to form a form containing a bond of aluminum dimethyl oxygen and aluminum.
  • R represents each independently an alkyl group which may be the same or different, preferably an alkyl group having 8 or less carbon atoms.
  • the condensate is not limited to the compounds of the following formulas (I), (11), and (III), but includes one or more aluminum dimethyloxy-aluminum bonds as exemplified herein. Show. > l-0-AI (I)
  • solubility in a solvent is increased.
  • Aluminum trialkoxides especially aluminum triethoxides
  • a suitable condensate may increase solubility.
  • the condensation proceeds too much, the number of active alkoxy-aluminum bonds becomes extremely small.
  • Such a condensate of an aluminum alkoxide compound is not necessarily a single compound, but is likely to be a mixture of several compounds, but may be a mixture.
  • the most preferred condensate of the aluminum alkoxide compound is a solution obtained by a method of reacting aluminum particles, aluminum trichloride and 95% ethanol in a solvent. Although the structure of the condensate obtained by this method is not always clear, A 1 o O 4
  • the aldehyde compound is represented by “X—CHO” Compound.
  • X includes a group such as an aliphatic, aromatic, or heterocyclic ring.
  • Aliphatic groups include alkenyl, alkyl, and alkynyl groups.
  • Alkenyl groups include ethel, propenyl, buteninole, and pentenyl groups, and alkyl groups include methyl, ethyl, propanyl, butanyl, pentanyl, cyclopentinole, and cyclohexynole groups.
  • a halogen may be substituted, such as a phenyl group, a tolyl group, a xylenyl group, a naphthyl group, an anthracenyl group or a 2,6-dichlorotolyl group.
  • the heterocyclic group include an alkylpyridinyl group and a methylthiazolyl group.
  • the aldehyde compound used as a raw material in the present invention is preferably one or a mixture of two or more selected from compounds represented by R 1 —CHO.
  • R 1 represents any of hydrogen, an optionally branched alkyl group having 1 to 7 carbon atoms, a phenyl group, and a 2-furyl group.
  • aldehydes do not require special high purity products and can be used as they are available in the industrial grade. However, it is preferable that the amount of water and alcohol be small. Generally less than 1% for both
  • the value be equal to or less than the numerical value 10000 ppm.
  • synthesis of carboxylic acid ester by dimerization of an aldehyde compound means that a single ester is given in the case of the same aldehyde, but a variety of esters are formed when different aldehydes are used. Means to do so.
  • the catalyst may be brought into contact with the aldehyde compound to cause a reaction.
  • liquid aldehyde compounds examples include contacting the compound directly with the catalyst or contacting the compound with the catalyst in a solution of an aldehyde compound dissolved in an inert solvent. At this time, it is preferable to use a carboxylic acid ester expected to be formed as a solvent, since the subsequent purification step is facilitated.
  • the reaction temperature may be a temperature at which the aldehyde compound as a raw material and the carboxylic acid ester as a product can be easily handled, and is preferably in the range of 120 ° C to 200 ° C.
  • the dimerization reaction of the aldehyde compound is an exothermic reaction, it is necessary to remove heat to maintain the temperature. Therefore, it is necessary to use a cooling device to keep the temperature lower than room temperature, which is costly to do this industrially.
  • a conventionally known catalyst system when the reaction temperature is high, the aldol reaction tends to proceed, and the selectivity of a target carboxylic acid ester may be reduced.
  • the catalyst of the present invention is characterized in that the aldol reaction does not proceed sufficiently even when the reaction is carried out at a temperature higher than around normal temperature, and that the carboxylic acid ester maintains a high selectivity. Therefore, it is preferable to use the catalyst of the present invention and to carry out the reaction at a reaction temperature in the range of 30 ° C. to 100 ° C., because it is economically effective and highly effective. Within this range, it is possible to cool with, for example, water cooled by natural cooling. Maintaining temperatures below 30 ° C requires more expensive cooling costs. On the other hand, if the reaction is carried out at a temperature of 100 ° C. or higher, the aldole reaction tends to proceed, which lowers the yield of the desired product.
  • an aluminum alkoxide compound and a sulfonic acid and / or a metal salt of the sulfonic acid are prepared using an aldehyde compound as a raw material.
  • a catalyst consisting of a combination of one or more compounds selected from the group consisting of: a) a reaction temperature controlled at 30 ° C to 100 ° C
  • a method is also provided.
  • the obtained carboxylic acid ester, the catalyst and the solvent can be separated by distillation or the like. If necessary, the catalyst may be deactivated with water, and the precipitated solid content may be separated by decantation. In addition, a generally known solid-liquid separation method such as centrifugation may be used. As described above, if a carboxylic acid ester expected to be formed is used as a solvent, the solvent and the product can be purified together, which is often economical.
  • Example 1 The same operation as in Example 1 was performed except that 0.16 g (0.45 mmo 1) of copper trifluormethane sulfonate was added. The results are shown in Table 1.
  • Example 1 the same operation as in Example 1 was performed except that hot water of 35 ° C was flowed into the jacket instead of hot water of 50 ° C. The results are shown in Table 1.
  • Example 1 silver trifluoromethanesulfonate, tin trifluoromethanesulfonate, and trifluoromethansulfonate (all manufactured by Wako Pure Chemical Industries, Ltd. 3 mmo 1), and otherwise the same operation as in Example 1 was performed. The results are shown in Table 1. (Example 8)
  • Example 1 0.148 g (0.3 mmo 1) of scandium trifluoromethanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of copper trifluoromethanesulfonate. Otherwise, the same operation as in Example 1 was performed. The results are shown in Table 1.
  • n-hexanal (Wako Pure Chemical Industries, Ltd.) toluene solution (hexane as an internal standard substance) was placed in a well-dried flask with a reflux condenser and thermometer, and with a jacket. 170 g was added, warm water at 50 ° C was flowed into the jacket, and the temperature of the solution was brought to 50 ° C while stirring. 0.92 g (4.5 mmol) of aluminum isopropoxide (Wako Pure Chemical Industries, Ltd.) and 0.1 llg (0.3 mmo1) of copper trifluormethane sulfonate were added thereto. And stirred.
  • n-hexana monohydrate was obtained at 7.2 m 0 1%
  • n-hexyl caproate was obtained at 85.5 mo 1%.
  • the conversion rate of n-hexanal is 91.8%
  • the selectivity of n-hexyl caproate is 93.1%.
  • Example 1 instead of copper trifluoromethanesulfonate, 0.041 g (0.3 mmo1) of zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was used. The same operation as in Example 1 was performed. The results are shown in Table 1.
  • Example 4 in place of copper trifluoromethanesulfonate, 0.041 g (0.3 mm 01) of zinc chloride was used, and otherwise the same operation as in Example 1 was performed. . The results are shown in Table 1. (Comparative Example 4)
  • Comparative Examples 1 to 3 showed that when the reaction temperature was higher than room temperature, the conversion of the starting aldehyde compound was low.
  • Examples 8 and 9 and Comparative Example 4 show that W Scandium methanesulfonate is used. According to the results in Table 1, Comparative Example 4 having a lower reaction temperature is superior to Examples 8 and 9, but Examples 8 and 9 do not require a cooling device, and are superior in overall cost. I have. Industrial applicability
  • a reaction at a temperature higher than room temperature is possible, and a catalyst having high selectivity and long life is provided. Is done.
  • the present invention also provides a method for producing a carboxylic acid ester using the catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un catalyseur destiné à la synthèse d'esters carboxyliques à partir d'aldéhydes via une réaction de Tishchenko ou une réaction similaire, qui permet de se passer d'une unité de refroidissement, qui permet une synthèse à une température supérieure à une température ordinaire et qui présente une haute sélectivité et une longue durée de vie. Cette invention concerne un catalyseur destiné à la préparation d'esters carboxyliques par dimérisation d'aldéhydes, qui est constitué d'un alcoxyde d'aluminium et d'au moins un composé sélectionné parmi des acides sulfoniques et des sels de ceux-ci avec des métaux des groupes 4 à 14 du tableau périodique. Cette invention concerne aussi la préparation d'esters carboxyliques par dimérisation d'aldéhydes avec ce catalyseur et, un processus de préparation d'esters carboxyliques dans lequel la synthèse est menée à une température de réaction commandée comprise entre 300 C et 1000 C.
PCT/JP2003/015089 2002-11-27 2003-11-26 Catalyseur destines a la preparation d'esters carboxyliques et processus de preparation d'esters carboxyliques avec ce catalyseur Ceased WO2004047990A1 (fr)

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AU2003284456A AU2003284456A1 (en) 2002-11-27 2003-11-26 Catalyst for the preparation of carboxylic esters and process for the preparation of carboxylic esters with the same

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JP2002-344407 2002-11-27
JP2002344407A JP2004174394A (ja) 2002-11-27 2002-11-27 カルボン酸エステル製造用触媒および該触媒を使用したカルボン酸エステルの製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112206820A (zh) * 2020-09-30 2021-01-12 润泰化学（泰兴）有限公司 一种用异丁醛一步法制异丁酸异丁酯的复合金属氧化物催化剂及其制备

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5838233A (ja) * 1981-09-01 1983-03-05 Chisso Corp 反応混合物の処理法
JPH11140017A (ja) * 1997-11-12 1999-05-25 Tokuyama Sekiyu Kagaku Kk エステルの製造法
JPH11140016A (ja) * 1997-11-12 1999-05-25 Tokuyama Sekiyu Kagaku Kk エステルの製造方法
WO2003010136A1 (fr) * 2001-07-25 2003-02-06 Showa Denko K. K. Complexes organometalliques, catalyseurs les contenant et procede de preparation d'esters carboxyliques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5838233A (ja) * 1981-09-01 1983-03-05 Chisso Corp 反応混合物の処理法
JPH11140017A (ja) * 1997-11-12 1999-05-25 Tokuyama Sekiyu Kagaku Kk エステルの製造法
JPH11140016A (ja) * 1997-11-12 1999-05-25 Tokuyama Sekiyu Kagaku Kk エステルの製造方法
WO2003010136A1 (fr) * 2001-07-25 2003-02-06 Showa Denko K. K. Complexes organometalliques, catalyseurs les contenant et procede de preparation d'esters carboxyliques

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112206820A (zh) * 2020-09-30 2021-01-12 润泰化学（泰兴）有限公司 一种用异丁醛一步法制异丁酸异丁酯的复合金属氧化物催化剂及其制备
CN112206820B (zh) * 2020-09-30 2022-11-22 润泰化学（泰兴）有限公司 一种用异丁醛一步法制异丁酸异丁酯的复合金属氧化物催化剂及其制备

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TW200417544A (en) 2004-09-16
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