JPH01121232A - Production of asymmetric ketone - Google Patents
Production of asymmetric ketoneInfo
- Publication number
- JPH01121232A JPH01121232A JP62280559A JP28055987A JPH01121232A JP H01121232 A JPH01121232 A JP H01121232A JP 62280559 A JP62280559 A JP 62280559A JP 28055987 A JP28055987 A JP 28055987A JP H01121232 A JPH01121232 A JP H01121232A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- aldehyde
- olefin
- catalyst
- mole
- 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
- 150000002576 ketones Chemical class 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 239000012327 Ruthenium complex Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 238000007086 side reaction Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 4
- 239000003905 agrochemical Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- -1 Grignard reagent Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910002090 carbon oxide Inorganic materials 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000006606 decarbonylation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- BMFYCFSWWDXEPB-UHFFFAOYSA-N cyclohexyl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1 BMFYCFSWWDXEPB-UHFFFAOYSA-N 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000003997 cyclic ketones Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000006324 decarbonylation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 2
- 238000006464 oxidative addition reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 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
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- BGTOWKSIORTVQH-HOSYLAQJSA-N cyclopentanone Chemical class O=[13C]1CCCC1 BGTOWKSIORTVQH-HOSYLAQJSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004460 silage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 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
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、非対称ケトンの製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing asymmetric ketones.
非対称ケトンを製造する方法としては、−船釣に芳香族
化合物へのフリーデルタラフドアシレージョンによる方
法、酸ハライドとグリニヤール試薬などの有機金属化合
物との反応による方法、アルコール類の酸化反応等多く
の公知の方法が知られている。There are many methods for producing asymmetric ketones, such as - Free delta rough silage to aromatic compounds by boat fishing, reaction of acid halides with organometallic compounds such as Grignard reagent, oxidation reaction of alcohols, etc. A known method is known.
これに対し、近年−酸化炭素の利用技術の１つとして工
業的に重要なオレフィンのヒドロホルミル化反応による
アルデヒドの製造が注目されているが、その反応中間体
としてアシル金属錯体の存在が指摘されている。このア
シル錯体はアルデヒドの金属への酸化的付加により生成
する。これらの事実をもとにオレフィンのアルデヒドに
よるヒドロアシル化による非対称ケトンの製造方法が提
案されている。この反応については従来ロジウム、白金
、イリジウム錯体による分子内に二重結合を有するアル
デヒドの分子内環化による環状ケトンの合成が知られて
いる。例えばある文献Ｉ（Ｔｅｔｒａｈｅｄｒｏｎ Ｌ
ｅｔｔ、＋ １９７２年１２８７頁、 Ｊ、Ａｍｅｒ。On the other hand, in recent years, the production of aldehydes through the hydroformylation reaction of olefins, which is industrially important as one of the technologies for utilizing carbon oxide, has attracted attention, but the existence of acyl metal complexes as reaction intermediates has been pointed out. There is. This acyl complex is formed by the oxidative addition of an aldehyde to a metal. Based on these facts, a method for producing asymmetric ketones by hydroacylation of olefins with aldehydes has been proposed. Regarding this reaction, synthesis of a cyclic ketone by intramolecular cyclization of an aldehyde having a double bond in the molecule using a rhodium, platinum, or iridium complex is known. For example, a certain document I (Tetrahedron L
ett, + 1972, p. 1287, J, Amer.
Ｃｈｅｍ、 Ｓｏｃ、、１９８０年１０２巻１９０頁）
ではシクロペンタノン誘導体合成が報告されており、そ
の詳細な反応機構に関しては他の文献ＩＩ （Ｊ、 Ａ
ｍｅｒ、Ｃｈｅｍ。Chem, Soc, 1980, vol. 102, p. 190)
reported the synthesis of cyclopentanone derivatives, and the detailed reaction mechanism can be found in other documents II (J, A
mer, Chem.
Ｓｏｃ、、 １９８０年１０２巻５８２４頁）に述べら
れている。Soc, 1980, Vol. 102, p. 5824).
また、エチレンとアルデヒド類からエチルアルキルケト
ンの合成に関しては、文献ｍ、 ｒｖ、 ｖ（Ｊ、八ｍ
ｅｒ； Ｃｈｅｍ、 Ｓｏｃ、＋ １９７６年９８巻１
２８１頁。Regarding the synthesis of ethyl alkyl ketones from ethylene and aldehydes, see the literature m, rv, v (J, 8m
er; Chem, Soc, + 1976 Volume 98 1
281 pages.
Ｊ、 Ｏｒｇａｎｏｍｅｔａｌ、 Ｃｈｅｍ、＋ １９
８２年２４０巻２８５頁および、１９８０年１９２巻２
５７頁）に述べられている。J, Organometal, Chem, +19
1982, vol. 240, p. 285 and 1980, vol. 192, 2.
(page 57).
これらの反応ではロジウム触媒の活性が高いことが知ら
れている。It is known that rhodium catalysts have high activity in these reactions.
しかしながら、上述した従来の方法には、以下のような
問題がある。However, the conventional method described above has the following problems.
すなわち、フリーデルタラフト法、グリニヤール試薬を
用いる方法は実験室レベルの反応では有効であるが、工
業化レベルでは反応が複雑で困難さを伴う。That is, the Friedelta raft method and the method using a Grignard reagent are effective in laboratory-level reactions, but the reactions are complex and difficult in industrial-scale reactions.
一方、アルデヒドとオレフィンとの反応によりケトンを
製造する場合、オレフィンとアルデヒドの種類を選ぶこ
とで非対称ケトンを合成できる点で注目される。しかし
、ロジウム錯体触媒による方法ではアルデヒドが触媒に
より脱カルボニル化することにより、炭素数が１つ減少
したオレフィンあるいはアルカンを生成する副反応がさ
けられず収率の低下を招く。On the other hand, when producing ketones by reacting aldehydes with olefins, it is noteworthy that asymmetric ketones can be synthesized by selecting the types of olefins and aldehydes. However, in the method using a rhodium complex catalyst, the aldehyde is decarbonylated by the catalyst, resulting in a side reaction of producing an olefin or alkane with one carbon number reduced, resulting in a decrease in yield.
さらに、従来の方法は、分子内環化による環状 ゛ケト
ンを与えるものでそれは分子間反応による非対称ケトン
の製造には適用できない欠点がある。Furthermore, the conventional method provides a cyclic ketone by intramolecular cyclization, which has the disadvantage that it cannot be applied to the production of asymmetric ketones by intermolecular reaction.
本発明は、上記従来技術では触媒の開発が鍵であること
に着目してなされたものであり、副反応を抑制し高い収
率で非対称ケトンを製造することができる方法を提供す
るものである。The present invention has been made by focusing on the fact that the development of catalysts is the key to the above-mentioned conventional techniques, and provides a method that can suppress side reactions and produce asymmetric ketones in high yields. .
本発明は、オレフィンとアルデヒドとを一酸化炭素雰囲
気中で、白金金属錯体を含む触媒の存在下で反応させる
ことを特徴とする非対称ケトンの製造方法である。The present invention is a method for producing an asymmetric ketone, which is characterized by reacting an olefin and an aldehyde in a carbon monoxide atmosphere in the presence of a catalyst containing a platinum metal complex.
本発明では、アルカリ土類金属触媒に酸化的付加をし、
アシル金属中間体を与える段階が重要な反応となる。こ
の際、アシル金属中間体は反応条件により容易に脱カル
ボニル化反応をし、炭素数の１つ少ない化合物を与える
副反応がおこる。In the present invention, oxidative addition is performed on an alkaline earth metal catalyst,
The important reaction is the step that provides the acyl metal intermediate. At this time, the acyl metal intermediate easily undergoes a decarbonylation reaction depending on the reaction conditions, and a side reaction occurs to give a compound having one less carbon number.
この副反応を抑制するために反応系を一酸化炭素雰囲気
にすることに特徴がある。A feature of this method is that the reaction system is placed in a carbon monoxide atmosphere in order to suppress this side reaction.
本発明にて用いる触媒としては、ルテニウム、カルボニ
ル、Ｒｕ＋ （Ｇｏ） ＋ ２およびルテニウムにオレ
フィンが配位した錯体が、脱カルボニル化反応を抑制し
、反応収率を高める上で好ましい。すなわち、触媒とし
て、ＲＬＩ：１（ＧＯ）＋２およびＲｕ （ＣＯＤ）
（ＣＯＴ）（ＣＯＤ： シクロオクタジエン、ＣＯＴ
ニジクロオクタトリエン）が用いられる。As the catalyst used in the present invention, ruthenium, carbonyl, Ru + (Go) + 2, and a complex in which ruthenium is coordinated with an olefin are preferable in terms of suppressing the decarbonylation reaction and increasing the reaction yield. That is, as catalysts, RLI:1(GO)+2 and Ru(COD)
(COT) (COD: cyclooctadiene, COT
dichlorooctatriene) is used.
また本発明において原料となるアルデヒド類は、一般式
ＲＣ）ｌで示すことができる。Ｒ基としては水素あるい
はメチル、エチルプロピル等のアルキル基さらにフェニ
ル基および置換基を有するフェニル基例えばｐ−クロロ
フェニル、ｐ−メチルフェニル基等を挙げることができ
る。Further, the aldehydes used as raw materials in the present invention can be represented by the general formula RC)l. Examples of the R group include hydrogen, alkyl groups such as methyl and ethylpropyl, phenyl groups, and phenyl groups having substituents, such as p-chlorophenyl and p-methylphenyl groups.
また、オレフィン類としては一般式ＲＣ１１＝ ＣＩＩ
Ｒ’で示すことができる化合物、例えばエチレン、プ
ロピレン、ブテン、イソブチン等の化合物およびシクロ
ペンテン、シクロヘキセン等の環状化合物を挙げること
ができる。In addition, as olefins, the general formula RC11= CII
Examples of compounds that can be represented by R' include compounds such as ethylene, propylene, butene, and isobutyne, and cyclic compounds such as cyclopentene and cyclohexene.
本発明は溶媒がなくても反応は可能であるが、通常はト
ルエン、ヘンゼン等の有機溶媒を用いることができる。In the present invention, the reaction can be carried out without a solvent, but usually an organic solvent such as toluene or Hensen can be used.
本発明に用いる触媒の濃度は、アルデヒド化合物に対し
０．０１〜１０モル％であり、特に０．５〜３モル％の
範囲が好ましい。そしてオレフィン化合物はアルデヒド
化合物に対し等モル−２０倍モルであり、オレフィンの
種類にもよるが５倍モル〜１０倍モルが好ましい。The concentration of the catalyst used in the present invention is 0.01 to 10 mol%, particularly preferably 0.5 to 3 mol%, based on the aldehyde compound. The olefin compound is used in an amount equivalent to -20 times the mole of the aldehyde compound, and preferably 5 times to 10 times the mole, although it depends on the type of olefin.
本発明の反応は一酸化炭素の雰囲気にて行う必要がある
。−酸化炭素は、触媒の失活を抑える働きをするととも
にアシル金属中間体から脱カルボニルによる副反応を抑
制する役割を果している。The reaction of the present invention needs to be carried out in an atmosphere of carbon monoxide. - Carbon oxide serves to suppress the deactivation of the catalyst and also to suppress side reactions due to decarbonylation of the acyl metal intermediate.
このことは−酸化炭素の代りにアルゴンを用いた場合目
的とする生成物の収率が極端に下がることおよび同位体
標識したアルデヒド化合物、Ｐｈ−” ＣＩＯを原料に
１２ＣＯ雰囲気中にオレフィンと反応させると生成物の
ケトンに同位体標識されたカルボニル基を有するケトン
とされていないカルボニル基を有するケトンとの混合物
が得られることから明らかである。This means that - if argon is used instead of carbon oxide, the yield of the desired product will be extremely low, and if an isotopically labeled aldehyde compound, Ph-"CIO, is used as a raw material to react with an olefin in a 12CO atmosphere. This is clear from the fact that a mixture of ketones with isotopically labeled carbonyl groups and ketones with non-isotopically labeled carbonyl groups is obtained.
また、本発明では、−酸化炭素の雰囲気を、常圧から１
００ ｋｇｃｍ２の範囲にするが、通常は１０〜３０
ｋｇｃｍ２の範囲にする鴫がよい。また、反応温度は１
００〜２５０℃、好ましくは２００℃前後がよい。反応
時間は、反応条件により異なるが通常１０〜５０時間の
範囲で行う。Further, in the present invention, the atmosphere of -carbon oxide is changed from normal pressure to 1
00 kgcm2, but usually 10-30
It is best to keep it within the range of kgcm2. Also, the reaction temperature is 1
00 to 250°C, preferably around 200°C. The reaction time varies depending on the reaction conditions, but is usually carried out in the range of 10 to 50 hours.
本発明にかかる非対称ケトンの製造方法によれば、オレ
フィンとアルデヒドとを一酸化炭素雰囲気中で、白金金
属錯体を含む触媒の存在下で反応させるので、とりわけ
脱カルボニル化反応を抑制し、極めて高い収率で非対称
ケトンを容易に得ることができるものである。According to the method for producing an asymmetric ketone according to the present invention, an olefin and an aldehyde are reacted in a carbon monoxide atmosphere in the presence of a catalyst containing a platinum metal complex. The asymmetric ketone can be easily obtained in high yield.
以下、本発明の実施例について説明する。 Examples of the present invention will be described below.
（実施例１）
内容積１００ｍ７！の電磁撹拌式オートクレーブにベン
ズアルデヒド０．５３ ｇ （５ｍｎ＋ｏＡ） 、オレ
フィンとしてシクロヘキセン４．０５ｍ ｌ （４０
ｍｍｏ １． ）、Ｒｕ錯体としてＲｕ３（Ｃｏ） ＋
２を０．０３２ｇ （０，０５ｍｍｏｎ！ ）を仕込
み、−酸化炭素で反応器を置換した後、これを２０ ｋ
ｇｃｍ２となるように圧入した。次いで、これを撹拌し
ながら２００°Ｃで４８時間反応させた。反応後、室温
まで冷却して、排気してから生成物を精密減圧蒸留して
単離した。生成物は赤外線吸収（ＩＲ）、核磁気共鳴（
ＮＭＲ）スペクトルにより、シクロへキシルフェニルケ
トンであることがわかった。また、その収率は５０％で
あった。(Example 1) Internal volume 100m7! 0.53 g (5 mn+oA) of benzaldehyde and 4.05 ml (40 mn+oA) of benzaldehyde and 4.05 ml (40
mmo 1. ), Ru3(Co) + as Ru complex
After charging 0.032g (0.05mmon!) of 2 and replacing the reactor with -carbon oxide, this was heated to 20k
It was press-fitted so that it was gcm2. Next, this was reacted at 200°C for 48 hours while stirring. After the reaction, the reaction mixture was cooled to room temperature, evacuated, and the product was isolated by precision vacuum distillation. The product is characterized by infrared absorption (IR), nuclear magnetic resonance (
NMR) spectrum revealed that it was cyclohexyl phenyl ketone. Moreover, the yield was 50%.
（実施例２）
触媒としてＲＬＩ３（Ｇｏ）＋２の代わりにＲｕ （Ｃ
ＯＤ） （ＣＯＴ）０．１５ｍｍｏＡを用いた以外は実
施例１と同様にしてシクロへキシルフェニルケトンを得
た。その収率は、４０％であった。(Example 2) Ru (C
Cyclohexyl phenyl ketone was obtained in the same manner as in Example 1 except that 0.15 mmoA (OD) (COT) was used. The yield was 40%.
（実施例３〜４）
アルデヒド類としてベンズアルデヒドの代わりにｐ−ク
ロロベンズアルデヒド、ｐ−）リルアルデヒドを用いた
以外は実施例１と同様の条件で反応を行ったところ、下
記第１表に示す生成物を同表中（）内に示す収率で得た
。(Examples 3 to 4) A reaction was carried out under the same conditions as in Example 1 except that p-chlorobenzaldehyde and p-)lyraldehyde were used instead of benzaldehyde as the aldehyde, resulting in the products shown in Table 1 below. The product was obtained in the yield shown in parentheses in the same table.
（実施例５）
オレフィン類として１−ヘキセンを用いた以外は実施例
１と同様の条件で反応を行った。反応酸生成物の分析を
行ったところ末端および内部付加したケトンが２．９：
１の比で得られた。この反応における生成物及びその収
率は上記第１表に併記した通りであった。(Example 5) A reaction was carried out under the same conditions as in Example 1 except that 1-hexene was used as the olefin. Analysis of the reaction acid product revealed that the terminal and internally added ketones were 2.9:
It was obtained with a ratio of 1. The products in this reaction and their yields were as listed in Table 1 above.
次に、本発明の効果を確認するために行った比較例につ
いて説明する。Next, a comparative example conducted to confirm the effects of the present invention will be described.
（比較例１）
オートクレーブを一酸化炭素雰囲気の代わりにアルゴン
にして実施例１と同じ条件下で反応を行った。目的生成
物であるシクロへキシルフェニルケトンは５％の収率で
得られた。副生成物としてベンゼンが得られたが、他に
数種の未同定の化合物が得られた。(Comparative Example 1) A reaction was carried out under the same conditions as in Example 1, using an argon atmosphere instead of carbon monoxide in the autoclave. The desired product, cyclohexyl phenyl ketone, was obtained in a yield of 5%. Benzene was obtained as a by-product, as well as several other unidentified compounds.
（比較例２）
ベンズアルデヒドとして１３Ｇで同位体標識したＰｈ−
” ＣＩＯを用いた以外は実施例１と同じ条件で反応を
行った。生成物であるＰｈ−１３Ｃ−Ｃ６Ｈ＋ ＋ と
Ｐｈ−”Ｃ−ＣＪ＋＋が１：２の割合で得られた。(Comparative Example 2) Ph- isotopically labeled with 13G as benzaldehyde
The reaction was carried out under the same conditions as in Example 1 except that ``CIO'' was used. The products Ph-13C-C6H++ + and Ph-''C-CJ++ were obtained in a ratio of 1:2.
以上説明した如く、本発明に係る非対称ケトンの製造方
法によれば、非対称ケトンをアルデヒドとオレフィンと
から収率よく低コストで製造することができる。しかも
、従来の方法では脱カルボニル化等の副反応のおこりう
る反応系であるが、本発明では、−酸化炭素雰囲気で行
うことによりこの副反応を抑制できるので工業的効果は
大である。これらの非対称ケトンは機能性溶剤あるいは
種々の医農薬品の中間体であるので、これらを効ｚ
率よく製造すること１士ゼ極めて有益なものである。As explained above, according to the method for producing an asymmetric ketone according to the present invention, an asymmetric ketone can be produced from an aldehyde and an olefin with high yield and at low cost. Moreover, in the conventional method, the reaction system is one in which side reactions such as decarbonylation may occur, but in the present invention, this side reaction can be suppressed by carrying out the reaction in a -carbon oxide atmosphere, so that the industrial effect is great. Since these asymmetric ketones are functional solvents or intermediates for various pharmaceutical and agricultural products, it is extremely useful to produce them efficiently.
Claims (2)
で、白金属金属錯体を含む触媒の存在下で反応させるこ
とを特徴とする非対称ケトンの製造方法。(1) A method for producing an asymmetric ketone, which comprises reacting an olefin and an aldehyde in a carbon monoxide atmosphere in the presence of a catalyst containing a platinum metal complex.
特徴とする特許請求の範囲第１項記載の非対称ケトンの
製造方法。(2) The method for producing an asymmetric ketone according to claim 1, wherein the platinum metal complex is a ruthenium complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62280559A JPH01121232A (en) | 1987-11-06 | 1987-11-06 | Production of asymmetric ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62280559A JPH01121232A (en) | 1987-11-06 | 1987-11-06 | Production of asymmetric ketone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01121232A true JPH01121232A (en) | 1989-05-12 |
Family
ID=17626725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62280559A Pending JPH01121232A (en) | 1987-11-06 | 1987-11-06 | Production of asymmetric ketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01121232A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040026964A (en) * | 2002-09-27 | 2004-04-01 | 금호석유화학 주식회사 | Synthesis of cyclohexyl phenyl ketone from 1,3-butadiene and acrylic acid |
-
1987
- 1987-11-06 JP JP62280559A patent/JPH01121232A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040026964A (en) * | 2002-09-27 | 2004-04-01 | 금호석유화학 주식회사 | Synthesis of cyclohexyl phenyl ketone from 1,3-butadiene and acrylic acid |
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