JP3750218B2 - Method for producing diester of dicarboxylic acid - Google Patents
Method for producing diester of dicarboxylic acid Download PDFInfo
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- JP3750218B2 JP3750218B2 JP24990296A JP24990296A JP3750218B2 JP 3750218 B2 JP3750218 B2 JP 3750218B2 JP 24990296 A JP24990296 A JP 24990296A JP 24990296 A JP24990296 A JP 24990296A JP 3750218 B2 JP3750218 B2 JP 3750218B2
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- diester
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Description
【０００１】
【発明の属する技術分野】
本発明は、不飽和炭化水素をカルボニル化してジカルボン酸のジエステルを製造する方法に関する。更に詳しくは、不飽和炭化水素、一酸化炭素及び亜硝酸エステルを白金族金属化合物の存在下で反応させて、不飽和炭化水素より炭素数が２多いジカルボン酸のジエステルを製造する方法に関する。
【０００２】
【従来の技術】
白金族金属系触媒の存在下、不飽和炭化水素、一酸化炭素及び亜硝酸エステルから、不飽和炭化水素より炭素数が２多いジカルボン酸のジエステルを液相反応で製造する方法としては、不飽和炭化水素と一酸化炭素とアルコールとを、白金族金属、亜硝酸エステル及びハロゲン化合物の存在下で、必要に応じて分子状酸素を導入しながら反応させる方法が知られている（特開昭５４−８１２１１号公報）。しかしながら、この方法では、目的のジカルボン酸ジエステルの選択率が満足できるものではなく、更に反応系に白金族金属以外にハロゲン化合物を添加するために、触媒の分離、回収、再生等も煩雑になるという問題がある。
【０００３】
【発明が解決しようとする課題】
本発明は、不飽和炭化水素、一酸化炭素及び亜硝酸エステルを白金族金属系触媒の存在下で液相で反応させて、不飽和炭化水素より炭素数が２多いジカルボン酸のジエステルを製造する方法において、相当するジカルボン酸のジエステルを高選択率及び高収量で、そして煩雑な触媒の後処理を引き起こすことなく（即ち、ハロゲン化合物を添加することなく）、製造できる方法を提供することを課題とする。
【０００４】
【課題を解決するための手段】
本発明の課題は、不飽和炭化水素、一酸化炭素及び亜硝酸エステルを、白金族金属化合物の存在下、ニトリル化合物溶媒中で反応させることを特徴とする不飽和炭化水素より炭素数が２多いジカルボン酸のジエステルの製造方法によって達成される。
【０００５】
【発明の実施の形態】
次に、本発明について詳細に説明する。
不飽和炭化水素としては、各種の脂肪族不飽和炭化水素が使用される。
脂肪族不飽和炭化水素としては、例えば、
エチレン、プロピレン、ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン、デセン、ウンデセン、ドデセン、トリデセン等の炭素数２〜１５のアルケン（各種異性体を含む）や、
シクロペンテン、シクロヘキセン、シクロヘプテン、シクロオクテン、シクロデセン、シクロドデセン、ノルボルネン等の炭素数５〜１５の環式アルケンや、アレン、ブタジエン、ペンタジエン、ヘキサジエン等の炭素数３〜８のアルカジエン（各種異性体を含む）や、
シクロペンタジエン、シクロヘキサジエン、ノルボルナジエン等の炭素数５〜１５の環式アルカジエン（各種異性体を含む）や、
アセチレン、メチルアセチレン等の炭素数２〜５のアルキンや、
スチレン等の芳香族基置換アルケンが挙げられる。
【０００６】
不飽和炭化水素が気体の場合、不飽和炭化水素に対する一酸化炭素の仕込み割合（一酸化炭素／不飽和炭化水素）はモル比で０．０１〜５０、好ましくは０．１〜５である。不飽和炭化水素が液体の場合、この割合は０．０１〜３０、好ましくは０．１〜５である。
なお、一酸化炭素は純粋なものでもよく、又窒素ガス等の不活性ガスで希釈されていても差し支えない。
【０００７】
亜硝酸エステルとしては、亜硝酸メチル、亜硝酸エチル、亜硝酸プロピル、亜硝酸ブチル、亜硝酸ペンチル、亜硝酸ヘキシル、亜硝酸ヘプチル、亜硝酸オクチル、亜硝酸ノニル、亜硝酸デシル等の炭素数１〜１０の亜硝酸アルキルエステル（各種異性体を含む）や、亜硝酸シクロペンチル、亜硝酸シクロヘキシル等の炭素数５〜１５の亜硝酸シクロアルキルエステルが使用される。
亜硝酸エステルは、反応原料液の０．１〜８０重量％、好ましくは１〜３０重量％使用される。なお、反応原料液は、亜硝酸エステル、ニトリル化合物溶媒及び触媒、更に不飽和炭化水素（液体の場合）及び／又はアルコールを含有するものである。
【０００８】
これらの亜硝酸エステルは必ずしも亜硝酸エステルの形でなくてもよく、反応系内で亜硝酸エステルを形成する物質を使用してもよい。例えば、亜硝酸エステルの代わりに、アルコールと窒素酸化物（一酸化窒素、二酸化窒素、三酸化二窒素、四酸化二窒素等）又は硝酸とを使用することができる。また、亜硝酸エステルとアルコールを併用してもよい。この場合、使用されるアルコールは亜硝酸エステルと同じアルコキシ基を有するアルコールから選ばれる。
【０００９】
触媒として使用される白金族金属化合物としては、パラジウム、白金等の白金族金属の塩化物や硫酸塩、又はこれら化合物と各種化合物との複合錯体が挙げられるが、中でも特にパラジウムの塩化物や硫酸塩、又はこれら化合物と各種化合物との複合錯体が好ましい。具体的には、例えば、ＰｄＣｌ2 、ＰｄＳＯ4 、Ｎａ2 ＰｄＣｌ4 、Ｈ2 ＰｄＣｌ4 、Ｐｄ（ＣＨ3 ＣＮ）2 Ｃｌ2 、Ｐｄ（ＰｈＣＮ）2 Ｃｌ2 、Ｐｄ（ＮＨ3 ）4 Ｃｌ2 が挙げられる。
触媒は、反応原料液の０．０１〜１０重量％、好ましくは０．１〜５．０重量％使用される。
【００１０】
溶媒として使用されるニトリル化合物（即ち、ニトリル化合物溶媒）としては、アセトニトリル、プロピオニトリル、ブチロニトリル、カプロニトリル、マロノニトリル、サクシノニトリル、グルタロニトリル、アジポニトリル等の炭素数２〜１０の脂肪族モノ又はジニトリル（各種異性体を含む）や、シアノベンゼン（ベンゾニトリル）、ジシアノベンゼン等の芳香族モノ又はジニトリルなどが挙げられる。ニトリル化合物溶媒を用いない場合（例えば、アルコール、エーテル又はエステルを溶媒に用いた場合）は、目的とするジカルボン酸ジエステルの選択率又は收量が低くなる。
ニトリル化合物溶媒は、反応原料液の２０〜９９重量％、好ましくは５０〜９５重量％使用される。
【００１１】
本発明では、ニトリル化合物溶媒に少量のアルコールを添加して反応を行うことによって、目的物の收量を一層高めることができる。このアルコールとしては、使用される亜硝酸エステルと同じアルコキシ基を有するアルコールが好適であり、例えば、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール等の炭素数１〜１０のアルカノール（各種異性体を含む）や、シクロペンタノール、シクロヘキサノール等の炭素数５〜１０のシクロアルカノールが使用される。
アルコールの添加量は、ニトリル化合物溶媒に対して０〜５０容量％、特に０．１〜５０容量％、更には０．１〜３０容量％であることが好ましい。
【００１２】
本発明の反応は、例えば、耐圧製の反応器に、ニトリル化合物溶媒、亜硝酸エステル及び触媒を入れ、更に不飽和炭化水素（液体の場合）及び／又はアルコールを入れた後に、一酸化炭素を圧入して極めて温和な条件で行われる。即ち、反応温度は室温から１５０℃、好ましくは４０〜１００℃で、反応圧力は常圧から３００気圧、好ましくは１０〜１００気圧である。なお、不飽和炭化水素が気体の場合、不飽和炭化水素は一酸化炭素と同様に反応器に圧入される。
【００１３】
このようにして、一酸化炭素及び亜硝酸エステルを白金族金属化合物の存在下で液相で反応させて、不飽和炭化水素より炭素数が２多いジカルボン酸のジエステルを製造することができる。例えば、エチレンからコハク酸ジエステル、プロピレンからメチルコハク酸ジエステル、ブテンからエチルコハク酸ジエステルあるいはジメチルコハク酸ジエステルが得られ、またアセチレンからマレイン酸ジエステルがそれぞれ得られる。
反応後、生成したジカルボン酸ジエステルは、得られる反応液から蒸留等により分離精製される。
【００１４】
【実施例】
次に、実施例及び比較例を挙げて本発明を具体的に説明する。ジカルボン酸ジエステル（コハク酸ジエステル）の選択率は次式により求めた。
【００１５】
【数１】
【数２】
実施例１
内容積３００ｍｌの回転攪拌式ステンレス鋼製オートクレーブに、アセトニトリル８０ｍｌ、塩化パラジウム（ＰｄＣｌ2 ）０．１８ｇ及び亜硝酸ｎ−ブチル２０ｇを入れ、密封後、エチレン３０気圧と一酸化炭素２０気圧をそれぞれ圧入した。次いで、内容物を攪拌下で１００℃に加熱・保持して、１時間反応を行った。反応終了後、ガスクロマトグラフィーにより反応液及び反応ガスの分析を行った。
その結果、コハク酸ジｎ−ブチルが５７ｍｍｏｌ生成していて、他の生成物は二酸化炭素が２．７ｍｍｏｌ生成しているのみであった。コハク酸ジｎ−ブチルの選択率はＣＯ基準で９７％、エチレン基準で１００％であった。
【００１８】
実施例２
アセトニトリル量を７５ｍｌに変え、ｎ−ブタノール５ｍｌを添加したほかは、実施例１と同様に反応と分析を行った。
その結果、コハク酸ジｎ−ブチルが９５ｍｍｏｌ生成していて、他の生成物は二酸化炭素が３．９ｍｍｏｌ生成しているのみであった。コハク酸ジｎ−ブチルの選択率はＣＯ基準で９８％、エチレン基準で１００％であった。
【００１９】
実施例３〜５
アセトニトリル量、ｎ−ブタノール量、一酸化炭素圧入量及びエチレン圧入量を表１記載のように変えたほかは、実施例２と同様に反応と分析を行った。その結果を表１に示す。
実施例１〜５の結果を表１に示す。
【００２０】
【表１】
実施例６
アセトニトリル量、一酸化炭素圧入量及びエチレン圧入量を表２記載のように変えたほかは、実施例１と同様に反応と分析を行った。
その結果、コハク酸ジｎ−ブチルが２８ｍｍｏｌ生成していて、他の生成物は二酸化炭素が０．９ｍｍｏｌ生成しているのみであった。コハク酸ジｎ−ブチルの選択率はＣＯ基準で９８％、エチレン基準で１００％であった。
【００２２】
実施例７、８
アセトニトリル量及びｎ−ブタノール量を表２記載のように変えたほかは、実施例６と同様に反応と分析を行った。その結果を表２に示す。
【００２３】
比較例１
アセトニトリルをｎ−ブタノール９０ｍｌに代えたほかは、実施例６と同様に反応と分析を行った。
その結果、コハク酸ジｎ−ブチルが３２ｍｍｏｌ生成していたが、他の生成物として、ジｎ−ブトキシエタン２．１ｍｍｏｌ、炭酸ジｎ−ブチル２．１ｍｍｏｌ、シュウ酸ジｎ−ブチル１．３ｍｍｏｌ、二酸化炭素５．１ｍｍｏｌが生成していた。コハク酸ジｎ−ブチルの選択率はＣＯ基準で７６％、エチレン基準で９４％であった。
【００２４】
比較例２
塩化パラジウムを５％Ｐｄ／Ｃ（活性炭にパラジウム金属が５重量％担持された触媒）２ｇに代えたほかは、実施例６と同様に反応と分析を行った。
その結果、コハク酸ジｎ−ブチルは全く生成していなかった。
【００２５】
実施例９、１０
反応温度を表２記載のように変えたほかは、実施例６と同様に反応と分析を行った。その結果を表２に示す。
実施例６〜１０及び比較例の結果を表２に示す。
【００２６】
【表２】
【発明の効果】
本発明により、白金族金属系触媒の存在下、不飽和炭化水素、一酸化炭素及び亜硝酸エステルから、不飽和炭化水素より炭素数が２多いジカルボン酸のジエステルを、ハロゲン化合物を添加することなく、高選択率及び高収量で製造することができる。このため、触媒の分離、回収、再生等が容易になって、工業的に優れたジカルボン酸のジエステルの製造方法を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing diesters of dicarboxylic acids by carbonylation of unsaturated hydrocarbons. More specifically, the present invention relates to a method for producing a diester of a dicarboxylic acid having 2 carbon atoms more than an unsaturated hydrocarbon by reacting an unsaturated hydrocarbon, carbon monoxide and a nitrite in the presence of a platinum group metal compound.
[0002]
[Prior art]
In the presence of a platinum group metal-based catalyst, as a method for producing diesters of dicarboxylic acids having 2 carbon atoms higher than unsaturated hydrocarbons from unsaturated hydrocarbons, carbon monoxide and nitrite esters by liquid phase reaction, A method is known in which hydrocarbon, carbon monoxide, and alcohol are reacted in the presence of a platinum group metal, a nitrite, and a halogen compound while introducing molecular oxygen as necessary (Japanese Patent Laid-Open No. 54). -81211). However, this method does not satisfy the selectivity of the target dicarboxylic acid diester, and further adds a halogen compound to the reaction system in addition to the platinum group metal, so that separation, recovery, regeneration and the like of the catalyst become complicated. There is a problem.
[0003]
[Problems to be solved by the invention]
In the present invention, an unsaturated hydrocarbon, carbon monoxide, and a nitrite are reacted in the liquid phase in the presence of a platinum group metal catalyst to produce a diester of a dicarboxylic acid having 2 carbon atoms more than the unsaturated hydrocarbon. It is an object of the present invention to provide a method capable of producing the corresponding diester of a dicarboxylic acid with high selectivity and high yield and without causing complicated post-treatment of the catalyst (that is, without adding a halogen compound). And
[0004]
[Means for Solving the Problems]
An object of the present invention is to have unsaturated carbon, carbon monoxide and nitrite react in an nitrile compound solvent in the presence of a platinum group metal compound, which has two more carbon atoms than an unsaturated hydrocarbon. This is achieved by a method for producing a diester of a dicarboxylic acid.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in detail.
As the unsaturated hydrocarbon, various aliphatic unsaturated hydrocarbons are used.
Examples of aliphatic unsaturated hydrocarbons include:
Alkenes having 2 to 15 carbon atoms (including various isomers) such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and tridecene,
Cyclic alkenes having 5 to 15 carbon atoms such as cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, norbornene, and alkadienes having 3 to 8 carbon atoms such as allene, butadiene, pentadiene, hexadiene (including various isomers) Or
C5-C15 cyclic alkadienes (including various isomers) such as cyclopentadiene, cyclohexadiene, norbornadiene,
C2-C5 alkyne such as acetylene and methylacetylene,
Aromatic group-substituted alkenes such as styrene can be mentioned.
[0006]
When the unsaturated hydrocarbon is a gas, the charge ratio of carbon monoxide to the unsaturated hydrocarbon (carbon monoxide / unsaturated hydrocarbon) is 0.01 to 50, preferably 0.1 to 5, in molar ratio. When the unsaturated hydrocarbon is a liquid, this ratio is 0.01 to 30, preferably 0.1 to 5.
Carbon monoxide may be pure or may be diluted with an inert gas such as nitrogen gas.
[0007]
Examples of nitrites include methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, hexyl nitrite, heptyl nitrite, octyl nitrite, nonyl nitrite, decyl nitrite and the like. 10 to 10 nitrous acid alkyl esters (including various isomers), and cycloalkyl nitrite having 5 to 15 carbon atoms such as cyclopentyl nitrite and cyclohexyl nitrite.
The nitrite is used in an amount of 0.1 to 80% by weight, preferably 1 to 30% by weight of the reaction raw material liquid. The reaction raw material liquid contains a nitrite ester, a nitrile compound solvent and a catalyst, and further an unsaturated hydrocarbon (in the case of a liquid) and / or an alcohol.
[0008]
These nitrites are not necessarily in the form of nitrites, and substances that form nitrites in the reaction system may be used. For example, alcohol and nitrogen oxides (nitrogen monoxide, nitrogen dioxide, dinitrogen trioxide, dinitrogen tetroxide, etc.) or nitric acid can be used instead of nitrite. Moreover, you may use nitrite and alcohol together. In this case, the alcohol used is selected from alcohols having the same alkoxy group as the nitrite ester.
[0009]
Examples of the platinum group metal compound used as a catalyst include chlorides and sulfates of platinum group metals such as palladium and platinum, and complex complexes of these compounds with various compounds. Salts or complex complexes of these compounds with various compounds are preferred. Specifically, for example, PdCl 2 , PdSO 4 , Na 2 PdCl 4 , H 2 PdCl 4 , Pd (CH 3 CN) 2 Cl 2 , Pd (PhCN) 2 Cl 2 , Pd (NH 3 ) 4 Cl 2 Can be mentioned.
The catalyst is used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5.0% by weight, based on the reaction raw material liquid.
[0010]
Examples of the nitrile compound used as the solvent (that is, the nitrile compound solvent) include aliphatic monomonomers having 2 to 10 carbon atoms such as acetonitrile, propionitrile, butyronitrile, capronitrile, malononitrile, succinonitrile, glutaronitrile, adiponitrile, or the like. Examples include dinitriles (including various isomers), aromatic mono- or dinitriles such as cyanobenzene (benzonitrile) and dicyanobenzene. When the nitrile compound solvent is not used (for example, when alcohol, ether or ester is used as the solvent), the selectivity or yield of the target dicarboxylic acid diester is lowered.
The nitrile compound solvent is used in an amount of 20 to 99% by weight, preferably 50 to 95% by weight, based on the reaction raw material liquid.
[0011]
In the present invention, by carrying out the reaction by adding a small amount of alcohol to the nitrile compound solvent, the yield of the target product can be further increased. As this alcohol, an alcohol having the same alkoxy group as the nitrite used is suitable. For example, 1 carbon atom such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol and the like. 10 to 10 alkanols (including various isomers) and cycloalkanols having 5 to 10 carbon atoms such as cyclopentanol and cyclohexanol are used.
The amount of alcohol added is preferably 0 to 50% by volume, particularly 0.1 to 50% by volume, and more preferably 0.1 to 30% by volume with respect to the nitrile compound solvent.
[0012]
In the reaction of the present invention, for example, a nitrile compound solvent, a nitrite ester and a catalyst are put into a pressure-resistant reactor, and further, an unsaturated hydrocarbon (in the case of a liquid) and / or an alcohol are added, and then carbon monoxide is added. It is carried out under extremely mild conditions. That is, the reaction temperature is from room temperature to 150 ° C., preferably from 40 to 100 ° C., and the reaction pressure is from atmospheric pressure to 300 atm, preferably from 10 to 100 atm. When the unsaturated hydrocarbon is a gas, the unsaturated hydrocarbon is injected into the reactor in the same manner as carbon monoxide.
[0013]
In this way, carbon monoxide and a nitrite can be reacted in the liquid phase in the presence of a platinum group metal compound to produce a diester of a dicarboxylic acid having 2 more carbon atoms than the unsaturated hydrocarbon. For example, succinic diester is obtained from ethylene, methyl succinic diester is obtained from propylene, ethyl succinic diester or dimethyl succinic diester is obtained from butene, and maleic diester is obtained from acetylene.
After the reaction, the produced dicarboxylic acid diester is separated and purified from the resulting reaction solution by distillation or the like.
[0014]
【Example】
Next, the present invention will be specifically described with reference to examples and comparative examples. The selectivity of dicarboxylic acid diester (succinic acid diester) was determined by the following formula.
[0015]
[Expression 1]
[Expression 2]
Example 1
In a 300 ml rotary stirring stainless steel autoclave, 80 ml of acetonitrile, 0.18 g of palladium chloride (PdCl 2 ) and 20 g of n-butyl nitrite are put, and after sealing, 30 atm of ethylene and 20 atm of carbon monoxide are injected. did. Next, the contents were heated and held at 100 ° C. with stirring, and reacted for 1 hour. After completion of the reaction, the reaction solution and the reaction gas were analyzed by gas chromatography.
As a result, 57 mmol of di-n-butyl succinate was produced, and the other products were only produced 2.7 mmol of carbon dioxide. The selectivity for di-n-butyl succinate was 97% on a CO basis and 100% on an ethylene basis.
[0018]
Example 2
The reaction and analysis were performed in the same manner as in Example 1 except that the amount of acetonitrile was changed to 75 ml and 5 ml of n-butanol was added.
As a result, 95 mmol of di-n-butyl succinate was generated, and the other products were only 3.9 mmol of carbon dioxide. The selectivity for di-n-butyl succinate was 98% on a CO basis and 100% on an ethylene basis.
[0019]
Examples 3-5
The reaction and analysis were performed in the same manner as in Example 2 except that the amount of acetonitrile, the amount of n-butanol, the amount of carbon monoxide injected, and the amount of ethylene injected were changed as shown in Table 1. The results are shown in Table 1.
The results of Examples 1 to 5 are shown in Table 1.
[0020]
[Table 1]
Example 6
The reaction and analysis were performed in the same manner as in Example 1 except that the amount of acetonitrile, the amount of carbon monoxide injected, and the amount of ethylene injected were changed as shown in Table 2.
As a result, 28 mmol of di-n-butyl succinate was produced, and the other product was only 0.9 mmol of carbon dioxide. The selectivity for di-n-butyl succinate was 98% on a CO basis and 100% on an ethylene basis.
[0022]
Examples 7 and 8
The reaction and analysis were performed in the same manner as in Example 6 except that the amount of acetonitrile and the amount of n-butanol were changed as shown in Table 2. The results are shown in Table 2.
[0023]
Comparative Example 1
The reaction and analysis were performed in the same manner as in Example 6 except that acetonitrile was replaced with 90 ml of n-butanol.
As a result, 32 mmol of di-n-butyl succinate was produced, but as other products, di-n-butoxyethane 2.1 mmol, di-n-butyl carbonate 2.1 mmol, di-n-butyl oxalate 1.3 mmol , 5.1 mmol of carbon dioxide was produced. The selectivity for di-n-butyl succinate was 76% on a CO basis and 94% on an ethylene basis.
[0024]
Comparative Example 2
The reaction and analysis were performed in the same manner as in Example 6 except that 2 g of palladium chloride was replaced with 2 g of 5% Pd / C (a catalyst in which 5 wt% of palladium metal was supported on activated carbon).
As a result, di-n-butyl succinate was not produced at all.
[0025]
Examples 9, 10
The reaction and analysis were performed in the same manner as in Example 6 except that the reaction temperature was changed as shown in Table 2. The results are shown in Table 2.
Table 2 shows the results of Examples 6 to 10 and the comparative example.
[0026]
[Table 2]
【The invention's effect】
According to the present invention, in the presence of a platinum group metal catalyst, diesters of dicarboxylic acids having 2 carbon atoms higher than unsaturated hydrocarbons from unsaturated hydrocarbons, carbon monoxide and nitrites can be added without adding a halogen compound. Can be produced with high selectivity and high yield. For this reason, separation, recovery, regeneration and the like of the catalyst are facilitated, and an industrially excellent method for producing a diester of dicarboxylic acid can be provided.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24990296A JP3750218B2 (en) | 1996-09-20 | 1996-09-20 | Method for producing diester of dicarboxylic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24990296A JP3750218B2 (en) | 1996-09-20 | 1996-09-20 | Method for producing diester of dicarboxylic acid |
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| Publication Number | Publication Date |
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| JPH1095750A JPH1095750A (en) | 1998-04-14 |
| JP3750218B2 true JP3750218B2 (en) | 2006-03-01 |
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| JP24990296A Expired - Fee Related JP3750218B2 (en) | 1996-09-20 | 1996-09-20 | Method for producing diester of dicarboxylic acid |
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| PT103640B (en) * | 2007-01-18 | 2007-10-02 | Inst Superior Tecnico | METHOD OF CONVERSION, IN SOFT AND AQUEOUS CONDITIONS, OF GASEOUS ALKANS AND LIQUIDS IN CARBOXYLIC ACIDS |
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