JPH1135544A - Production of linear dimers of acrylonitrile - Google Patents
Production of linear dimers of acrylonitrileInfo
- Publication number
- JPH1135544A JPH1135544A JP9214079A JP21407997A JPH1135544A JP H1135544 A JPH1135544 A JP H1135544A JP 9214079 A JP9214079 A JP 9214079A JP 21407997 A JP21407997 A JP 21407997A JP H1135544 A JPH1135544 A JP H1135544A
- Authority
- JP
- Japan
- Prior art keywords
- acrylonitrile
- ruthenium
- compound
- reaction
- producing
- 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.)
- Pending
Links
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000000539 dimer Substances 0.000 title claims description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 17
- -1 phosphine compound Chemical class 0.000 claims abstract description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003304 ruthenium compounds Chemical class 0.000 claims abstract description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 8
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000006471 dimerization reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 9
- VZXMCMGRKFXJJA-UHFFFAOYSA-N cycloocta-1,3-diene cycloocta-1,3,5-triene ruthenium Chemical compound [Ru].C1CCC=CC=CC1.C1CC=CC=CC=C1 VZXMCMGRKFXJJA-UHFFFAOYSA-N 0.000 claims description 3
- JKBPBRLDGFKIIA-UHFFFAOYSA-N 2-propylidenepropanedinitrile Chemical compound CCC=C(C#N)C#N JKBPBRLDGFKIIA-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- ZQOHAQBXINVHHC-HNQUOIGGSA-N (e)-hex-2-enedinitrile Chemical compound N#CCC\C=C\C#N ZQOHAQBXINVHHC-HNQUOIGGSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 abstract description 4
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000543 intermediate Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000000447 dimerizing effect Effects 0.000 abstract 2
- 239000004677 Nylon Substances 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 229920001778 nylon Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000002904 solvent Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Chemical class 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910000083 tin tetrahydride Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アクリロニトリル
直鎖二量体の１，４−ジシアノブテン及びアジポニトリ
ルの製法に関する。１，４−ジシアノブテン及びアジポ
ニトリルは、ナイロン６６原料のヘキサメチレンジアミ
ンの重要な中間体である。The present invention relates to a method for producing 1,4-dicyanobutene and adiponitrile, which are linear dimers of acrylonitrile. 1,4-dicyanobutene and adiponitrile are important intermediates of hexamethylenediamine from nylon 66.
【０００２】[0002]
【従来の技術】アクリロニトリルのルテニウム触媒によ
る直鎖二量化反応は、東京大学工学部の御薗生ら（Ｊ．
Ｃｈｅｍ．Ｓｏｃ．，Ｃｈｅｍ．，Ｃｏｍｍｕｎ．，ｐ
３５７［１９６７］）により見出されており公知であ
る。これは、エタノール等のプロトン性溶媒中、水素存
在下、三塩化ルテニウム等のルテニウム触媒によりアク
リロニトリルを直鎖二量化し、１，４−ジシアノブテン
やアジポニトリルを得る反応である。ルテニウム触媒に
よるアクリロニトリルの直鎖二量化反応は一段階でアク
リロニトリルの直鎖二量体を与える優れた方法である
が、ルテニウム触媒の触媒活性が低いうえ、ルテニウム
触媒の触媒活性維持に水素が必須であり、プロピオニト
リルが大量に副生するという欠点があった。2. Description of the Related Art The linear dimerization reaction of acrylonitrile with a ruthenium catalyst has been reported by Misono, et al.
Chem. Soc. Chem. Commun. , P
357 [1967]) and is known. This is a reaction in which acrylonitrile is linearly dimerized with a ruthenium catalyst such as ruthenium trichloride in a protic solvent such as ethanol in the presence of hydrogen to obtain 1,4-dicyanobutene or adiponitrile. The linear dimerization of acrylonitrile with a ruthenium catalyst is an excellent method to give a linear dimer of acrylonitrile in one step, but the catalytic activity of the ruthenium catalyst is low and hydrogen is essential to maintain the catalytic activity of the ruthenium catalyst. There is a drawback that propionitrile is produced in large quantities.
【０００３】その後アクリロニトリル二量化の技術とし
て、例えば、アルコール溶媒中、水素存在下、三塩化ル
テニウム−アルカリ金属水酸化物触媒系（特公昭４４−
２４５８５）、水素存在下、ハロゲン含有ルテニウム−
銅、銀、錫などの金属触媒系（特公昭４５−４０４
８）、カルボン酸ルテニウム又はルテニウム錯体と亜
鉛、スズなどのカルボン酸金属塩からなる触媒系（特公
昭５４−１２４５０）、ルテニウム化合物とスズヒドリ
ドの触媒系（特開平６−９５３１）、ルテニウム化合物
と特定の置換基を有する安息香酸からなる触媒系（特開
平８−７３４１９）等多くのアクリロニトリルの二量化
反応の触媒系が知られている。いずれの場合もアクリロ
ニトリルの転化率、直鎖二量体への選択率、触媒活性の
いずれも低く、また、反応速度も遅く実用的ではない。[0003] Then, as a technique for acrylonitrile dimerization, for example, a ruthenium trichloride-alkali metal hydroxide catalyst system (Japanese Patent Publication No. 44-44) in an alcohol solvent in the presence of hydrogen.
24585), in the presence of hydrogen, halogen-containing ruthenium-
Metal catalysts for copper, silver, tin, etc. (JP-B-45-404)
8), a catalyst system comprising ruthenium carboxylate or a ruthenium complex and a metal salt of a carboxylate such as zinc or tin (Japanese Patent Publication No. 54-12450), a catalyst system comprising a ruthenium compound and tin hydride (JP-A-6-9531), a ruthenium compound Many catalyst systems for dimerization of acrylonitrile are known, such as a catalyst system comprising benzoic acid having the following substituents (JP-A-8-73419). In each case, the conversion of acrylonitrile, the selectivity to the linear dimer, and the catalytic activity are all low, and the reaction rate is too low to be practical.
【０００４】[0004]
【発明が解決しようとする課題】上記のように、ルテニ
ウム触媒によるアクリロニトリルの二量化反応の問題点
として、ルテニウム触媒の活性が低いことと、アクリロ
ニトリルの還元体のプロピオニトリルが大量に副生する
ことがあげられる。そこでプロピオニトリルの副生を極
力抑え、かつ触媒活性が高いルテニウム触媒系が求めら
れている。As described above, the problems of the dimerization reaction of acrylonitrile using a ruthenium catalyst are that the activity of the ruthenium catalyst is low and that propionitrile, a reduced form of acrylonitrile, is produced in large quantities. There are things. Therefore, a ruthenium catalyst system which suppresses the by-product of propionitrile as much as possible and has a high catalytic activity is demanded.
【０００５】[0005]
【課題を解決するための手段】本発明者は、アクリロニ
トリルの二量化により直鎖二量体の１，４−ジシアノブ
テン及びアジポニトリルを製造するアクリロニトリルの
二量化反応について鋭意研究した結果、アクリロニトリ
ルを効率的に直鎖二量化するルテニウム触媒を見出し本
発明を完成するに至った。即ち、本発明は、アクリロニ
トリルの二量化により１，４−ジシアノブテン及び／又
はアジポニトリルからなるアクリロニトリルの直鎖二量
体の製造法において、ルテニウム化合物とＲ1 Ｒ2 Ｐ
（ＣＨ2 ）n ＣＯＯＨで示されるホスフィン化合物（Ｒ
1 ，Ｒ2 はアルキル基、フェニル基、ｎ＝１〜３を示
す）の存在下に、アクリロニトリルを二量化することを
特徴とするアクリロニトリルの直鎖二量体の製造法であ
る。DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies on the dimerization reaction of acrylonitrile to produce linear dimer 1,4-dicyanobutene and adiponitrile by dimerization of acrylonitrile. A ruthenium catalyst for linear dimerization was found, and the present invention was completed. That is, the present invention relates to a method for producing a linear dimer of acrylonitrile comprising 1,4-dicyanobutene and / or adiponitrile by dimerization of acrylonitrile, wherein a ruthenium compound and R 1 R 2 P
A phosphine compound represented by (CH 2 ) n COOH (R
1 , R 2 represents an alkyl group, a phenyl group, and n = 1 to 3). A process for producing a linear dimer of acrylonitrile, characterized in that acrylonitrile is dimerized.
【０００６】[0006]
【発明の実施の形態】本発明はアクリロニトリルの二量
体の製造法において前記したようにルテニウム化合物と
ホスフィン化合物を触媒として使用することを特徴とす
る。このルテニウム化合物としてはルテニウム炭化水素
化合物、特にルテニウム原子上に炭化水素化合物が少な
くとも１つ共有結合もしくは配位結合するルテニウムの
錯体化合物が好ましい。その錯体化合物としては、ルテ
ニウムシクロオクタジエンシクロオクタトリエン、ルテ
ニウムジアクリルシクロオクタジエン、ルテニウムシク
ロヘキサジエンヘキサトリエンなどがあげられる。この
錯体化合物は予め合成したものを反応容器に仕込んでも
よく、また錯体を構成する三塩化ルテニウム、シクロオ
クタジエン等と還元剤として亜鉛等を反応容器に仕込
み、反応容器中で反応させて錯体を生成させ、そのまま
単離することなく、触媒として使用することもできる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is characterized in that a ruthenium compound and a phosphine compound are used as catalysts in a process for producing an acrylonitrile dimer as described above. The ruthenium compound is preferably a ruthenium hydrocarbon compound, particularly a ruthenium complex compound in which at least one hydrocarbon compound has a covalent bond or a coordinate bond on a ruthenium atom. Examples of the complex compound include ruthenium cyclooctadiene cyclooctatriene, ruthenium diacrylcyclooctadiene, ruthenium cyclohexadiene hexatriene, and the like. The complex compound may be prepared in advance in a reaction vessel, or ruthenium trichloride, cyclooctadiene, etc. constituting the complex and zinc or the like as a reducing agent are charged in the reaction vessel, and reacted in the reaction vessel to form the complex. It can be produced and used as a catalyst without isolation as it is.
【０００７】本発明に用いられるホスフィン化合物は、
一般式（Ｒ1 Ｒ2 Ｐ（ＣＨ2 ）n ＣＯＯＨ）で表わさ
れ、具体的にはＰｈ2 ＰＣＨ2 ＣＯＯＨ、Ｐｈ2 Ｐ（Ｃ
Ｈ2 ）2 ＣＯＯＨ、Ｐｈ2 Ｐ（ＣＨ2 ）3 ＣＯＯＨなど
があげられる。上記一般式のＲ1 ，Ｒ2 はアルキル基、
フェニル基で、ｎ＝１〜３である。上記触媒の使用量は
アクリロニトリル１モルに対し、ルテニウム化合物０．
０００５モル以上、好ましくは０．００１モル以上、ホ
スフィン化合物０．０００５モル以上、好ましくは０．
００１モル以上である。使用量の上限について、特に制
限ないが、コスト等の面からアクリロニトリル１モルに
対し夫々０．０１モル以下とするのが適当である。The phosphine compound used in the present invention is
It is represented by the general formula (R 1 R 2 P (CH 2 ) n COOH), and specifically, Ph 2 PCH 2 COOH, Ph 2 P (C
H 2 ) 2 COOH and Ph 2 P (CH 2 ) 3 COOH. R 1 and R 2 in the above general formula are alkyl groups,
In the phenyl group, n = 1 to 3. The amount of the above catalyst used is 0.1 mol of ruthenium compound per 1 mol of acrylonitrile.
0005 mol or more, preferably 0.001 mol or more, and 0.0005 mol or more, preferably 0.1 mol or more, of the phosphine compound.
001 mol or more. The upper limit of the amount used is not particularly limited, but is preferably 0.01 mol or less for 1 mol of acrylonitrile, in terms of cost and the like.
【０００８】本発明における反応方法としては、アクリ
ロニトリル、ルテニウム化合物、ホスフィン化合物を反
応容器に仕込み、撹拌下に所定温度に加熱して反応を行
う。反応において原料のアクリロニトリルが溶媒を兼ね
るので、他の溶媒は特に必要としないが、触媒がアクリ
ロニトリルに溶解しない場合は触媒を溶解する溶剤を使
用して均一系とする。その際の溶媒としては炭化水素
系、アルコール系、ハロゲン系、ニトリル系、エーテル
系等の有機溶媒を使用することができる。反応原料の仕
込は、窒素やアルゴンのような不活性気体の気流下、も
しくは水素ガス気流下で行うことが望ましい。反応器と
しては、圧力がかけられるようなタイプが望ましく、オ
ートクレーブなどが反応容器として適する。反応に際し
ては水素が存在していることが必要である。水素は反応
容器にガスとして裝入してもよく、また分解して水素が
生成する蟻酸などの水素供与体を反応系に添加して水素
を発生させてもよい。水素（Ｈ2 ）はアクリロニトリル
１モルに対し、０．３モル以上存在させる。反応温度
は、低すぎると反応速度が遅く、また高すぎるとアクリ
ロニトリルの重合や触媒の失活が起こりアクリロニトリ
ルの直鎖二量体の選択率が低くなるため、好適には、６
０〜２００℃であり、好ましくは１００〜１５０℃の反
応温度が望ましい。本反応の反応時間は、温度、水素圧
力、溶媒により異なるが、１〜１０時間が好適である。As a reaction method in the present invention, an acrylonitrile, a ruthenium compound, and a phosphine compound are charged into a reaction vessel and heated to a predetermined temperature with stirring to carry out the reaction. Since acrylonitrile as a raw material also functions as a solvent in the reaction, other solvents are not particularly required. However, when the catalyst does not dissolve in acrylonitrile, a homogeneous solvent is used using a solvent that dissolves the catalyst. As a solvent at this time, an organic solvent such as a hydrocarbon solvent, an alcohol solvent, a halogen solvent, a nitrile solvent, or an ether solvent can be used. The reactants are preferably charged under an inert gas stream such as nitrogen or argon, or a hydrogen gas stream. As the reactor, a type in which pressure is applied is desirable, and an autoclave or the like is suitable as a reaction vessel. The reaction requires the presence of hydrogen. Hydrogen may be charged as a gas into the reaction vessel, or hydrogen may be generated by adding a hydrogen donor such as formic acid, which is decomposed to generate hydrogen, to the reaction system. Hydrogen (H 2 ) is present in an amount of 0.3 mol or more based on 1 mol of acrylonitrile. If the reaction temperature is too low, the reaction rate is slow, and if it is too high, polymerization of acrylonitrile and deactivation of the catalyst occur, and the selectivity of the linear dimer of acrylonitrile is lowered.
The reaction temperature is 0 to 200 ° C, preferably 100 to 150 ° C. The reaction time of this reaction varies depending on the temperature, hydrogen pressure, and solvent, but is preferably 1 to 10 hours.
【０００９】[0009]
【実施例】以下に実施例を用いてさらに詳しく本発明を
説明するが、本発明はこれら実施例に限定されるもので
はない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００１０】実施例１ ０．１リットルのオートクレーブに磁気撹拌子を入れ、
アクリロニトリル５０ｍｍｏｌ、ルテニウムシクロオク
タジエンシクロオクタトリエン（Ｒｕ（ｃｏｄ）（ｃｏ
ｔ））０．２１ｍｍｏｌ、Ｐｈ2 ＰＣＨ2 ＣＯＯＨを
０．２１ｍｍｏｌ加え、ついで水素を５０ｍｍｏｌ導入
した。温度１４０℃で撹拌しながら８０分間反応を行っ
た。オートクレーブを室温まで冷却し、反応粗液をガス
クロマトグラフィーで定量分析した。反応成績を表１に
示す。Example 1 A magnetic stirrer was placed in a 0.1 liter autoclave.
Acrylonitrile 50 mmol, ruthenium cyclooctadiene cyclooctatriene (Ru (cod) (co
t)) 0.21 mmol, 0.21 mmol of Ph 2 PCH 2 COOH were added, and then 50 mmol of hydrogen was introduced. The reaction was performed for 80 minutes while stirring at a temperature of 140 ° C. The autoclave was cooled to room temperature, and the reaction crude liquid was quantitatively analyzed by gas chromatography. The reaction results are shown in Table 1.
【００１１】実施例２ ０．１リットルのオートクレーブに磁気撹拌子を入れ、
水素気流中、アクリロニトリル１００ｍｍｏｌ、Ｒｕ
（ｃｏｄ）（ｃｏｔ）０．１５ｍｍｏｌ、Ｐｈ2ＰＣＨ2
ＣＯＯＨを０．１５ｍｍｏｌ加えた。温度１４０℃で
撹拌しながら４時間反応を行った。オートクレーブを室
温まで冷却し、反応粗液をガスクロマトグラフィーで定
量分析した。反応成績を表１に示す。Example 2 A magnetic stirrer was placed in a 0.1 liter autoclave.
In a hydrogen stream, acrylonitrile 100 mmol, Ru
(Cod) (cot) 0.15 mmol, Ph 2 PCH 2
0.15 mmol of COOH was added. The reaction was performed for 4 hours while stirring at a temperature of 140 ° C. The autoclave was cooled to room temperature, and the reaction crude liquid was quantitatively analyzed by gas chromatography. The reaction results are shown in Table 1.
【００１２】実施例３ ０．１リットルのオートクレーブに磁気撹拌子を入れ、
窒素気流中、アクリロニトリル３０ｍｍｏｌ、Ｒｕ（ａ
ｌｌｙｌ）2 （ｃｏｄ）０．１５ｍｍｏｌ、Ｐｈ2 ＣＨ
2 ＣＯＯＨを０．１５ｍｍｏｌ加え、ついで水素を導入
し、水素置換を数回行う。温度１２０℃で撹拌しながら
８０分間反応を行った。オートクレーブを室温まで冷却
し、反応粗液をガスクロマトグラフィーで定量分析し
た。反応成績を表１に示す。Example 3 A magnetic stirrer was placed in a 0.1 liter autoclave.
In a nitrogen stream, acrylonitrile 30 mmol, Ru (a
llyl) 2 (cod) 0.15 mmol, Ph 2 CH
0.15 mmol of 2 COOH is added, and then hydrogen is introduced, and hydrogen replacement is performed several times. The reaction was performed for 80 minutes while stirring at a temperature of 120 ° C. The autoclave was cooled to room temperature, and the reaction crude liquid was quantitatively analyzed by gas chromatography. The reaction results are shown in Table 1.
【００１３】実施例４ ０．１リットルのオートクレーブに磁気撹拌子を入れ、
窒素気流中、アクリロニトリル３０ｍｍｏｌ、Ｒｕ（ｃ
ｏｄ）（ｃｏｔ）０．１８ｍｍｏｌ、Ｐｈ2 ＰＣＨ2 Ｃ
ＯＯＨを０．１８ｍｍｏｌ、テトラヒドロフラン（ＴＨ
Ｆ）を１．５ｍｌ、蟻酸を１６ｍｏｌ加え、温度１２０
℃で撹拌しながら３時間反応を行った。オートクレーブ
を室温まで冷却し、反応粗液をガスクロマトグラフィー
で定量分析した。反応成績を表１に示す。Example 4 A magnetic stirrer was placed in a 0.1 liter autoclave.
In a nitrogen stream, acrylonitrile 30 mmol, Ru (c
od) (cot) 0.18 mmol, Ph 2 PCH 2 C
0.18 mmol of OOH and tetrahydrofuran (TH
F), 1.5 ml of formic acid and 16 mol of formic acid were added.
The reaction was carried out for 3 hours while stirring at ℃. The autoclave was cooled to room temperature, and the reaction crude liquid was quantitatively analyzed by gas chromatography. The reaction results are shown in Table 1.
【００１４】[0014]
【表１】 比較例１のものは特開平８−７３４１９の実施例１２に
したがって製造したものである。[Table 1] Comparative Example 1 was manufactured according to Example 12 of JP-A-8-73419.
【００１５】[0015]
【発明の効果】本発明により、公知のアクリロニトリル
二量化による直鎖二量体製法におけるアクリロニトリル
の転化率が低い、ルテニウム化合物の触媒活性が低い、
更に、反応速度が遅いという問題点を解決し、高い触媒
活性によりアクリロニトリル直鎖二量体を効率よく製造
することができる。According to the present invention, the conversion of acrylonitrile in the known linear dimer production process by acrylonitrile dimerization is low, the catalytic activity of the ruthenium compound is low,
Furthermore, the problem that the reaction rate is low can be solved, and an acrylonitrile linear dimer can be efficiently produced with high catalytic activity.
Claims (5)
−ジシアノブテン及び／又はアジポニトリルからなるア
クリロニトリルの直鎖二量体の製造法において、ルテニ
ウム化合物とＲ1 Ｒ2 Ｐ（ＣＨ2 ）n ＣＯＯＨで示され
るホスフィン化合物（Ｒ1 ，Ｒ2 はアルキル基、フェニ
ル基、ｎ＝１〜３を示す）の存在下に、アクリロニトリ
ルを二量化することを特徴とするアクリロニトリルの直
鎖二量体の製造法。1. The method according to claim 1, wherein the dimerization of acrylonitrile results in 1,4
A process for producing a linear dimer of acrylonitrile comprising dicyanobutene and / or adiponitrile, wherein a ruthenium compound and a phosphine compound represented by R 1 R 2 P (CH 2 ) n COOH (R 1 and R 2 are alkyl groups, phenyl A process for producing a linear dimer of acrylonitrile, wherein acrylonitrile is dimerized in the presence of a group (n = 1 to 3).
化合物である請求項１記載のアクリロニトリルの直鎖二
量体の製造法。2. The method for producing a linear dimer of acrylonitrile according to claim 1, wherein the ruthenium compound is a ruthenium hydrocarbon compound.
シクロオクタジエンシクロオクタトリエン、ルテニウム
ジアリルシクロオクタジエン、ルテニウムシクロヘキサ
ジエンヘキサトリエンである請求項２記載のアクリロニ
トリルの直鎖二量体の製造法。3. The process for producing a linear dimer of acrylonitrile according to claim 2, wherein the ruthenium hydrocarbon compound is ruthenium cyclooctadiene cyclooctatriene, ruthenium diallylcyclooctadiene or ruthenium cyclohexadiene hexatriene.
ウム化合物を０．０００５モル以上、ホスフィン化合物
を０．０００５モル以上使用する請求項１〜３記載のア
クリロニトリルの直鎖二量体の製造法。4. The process for producing a linear dimer of acrylonitrile according to claim 1, wherein at least 0.0005 mol of the ruthenium compound and at least 0.0005 mol of the phosphine compound are used per 1 mol of acrylonitrile.
２００℃で行う請求項１〜４記載のアクリロニトリルの
直鎖二量体の製造法。5. The acrylonitrile dimerization reaction of 60 to 60
The method for producing a linear dimer of acrylonitrile according to claim 1, which is carried out at 200 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9214079A JPH1135544A (en) | 1997-07-23 | 1997-07-23 | Production of linear dimers of acrylonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9214079A JPH1135544A (en) | 1997-07-23 | 1997-07-23 | Production of linear dimers of acrylonitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1135544A true JPH1135544A (en) | 1999-02-09 |
Family
ID=16649904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9214079A Pending JPH1135544A (en) | 1997-07-23 | 1997-07-23 | Production of linear dimers of acrylonitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1135544A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013510807A (en) * | 2009-11-14 | 2013-03-28 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Process for preparing Ru (0) -olefin complexes |
-
1997
- 1997-07-23 JP JP9214079A patent/JPH1135544A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013510807A (en) * | 2009-11-14 | 2013-03-28 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Process for preparing Ru (0) -olefin complexes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Garland et al. | A heterogeneous ligand-accelerated reaction: enantioselective hydrogenation of ethyl pyruvate catalyzed by cinchona-modified platinum/aluminum oxide catalysts | |
| CN1093848C (en) | Hydroformylation process | |
| Tsuji et al. | Dodecacarbonyltriruthenium catalysed carbonylation of amines and hydroamidation of olefins | |
| CN1422248A (en) | Process for the carbonylation of pentenenitrile | |
| US5726334A (en) | Process for the preparation of ruthenium hydrogenation catalysts and products thereof | |
| EP0269395B1 (en) | Ruthenium-phosphine complex catalysts | |
| US3484475A (en) | Dimerisation and hydrodimerisation of alpha,beta - olefinically unsaturated compounds | |
| JPH0579659B2 (en) | ||
| RU2223949C2 (en) | Preparing aminonitrile and catalytic composition | |
| US6020517A (en) | Process for production of benzonitrile and benzyl alcohol | |
| JPH1135544A (en) | Production of linear dimers of acrylonitrile | |
| CN1294119A (en) | Improved catalytic process | |
| CN1069960A (en) | The preparation method of alcohols | |
| US20130281747A1 (en) | Cobalt phosphine alkyl complexes for the asymmetric hydrogenation of alkenes | |
| CN1252786A (en) | Process to prepare a pentenoic acid derivative | |
| US4918222A (en) | Process for synthesis of N-acetylglycine | |
| JP3815795B2 (en) | Method for producing 3-pentenoic acid ester by carbonylation of alkoxybutene | |
| JPH06184082A (en) | Production of norcamphane dicarbonitrile | |
| US6841507B2 (en) | Aminonitrile production | |
| JP2001031633A (en) | Production of n-acylamino acid | |
| US4831159A (en) | Process for hydroformylation of n-vinyl-2-pyrrolidinone | |
| US6680403B1 (en) | Process for hydrogenating dinitriles in aminonitriles | |
| JPH05331076A (en) | Production of cyclododecene | |
| JPS63503543A (en) | Asymmetric hydrogenation method for carbonyl compounds | |
| JP2718740B2 (en) | Process for producing bis (aminomethyl) cyclohexanes |