JP6918577B2 - A method for producing an aromatic compound by a dehydrogenation reaction of a compound having a cycloalkane or cycloalkene structure using a heterogeneous palladium catalyst. - Google Patents
A method for producing an aromatic compound by a dehydrogenation reaction of a compound having a cycloalkane or cycloalkene structure using a heterogeneous palladium catalyst. Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 62
- 229910052763 palladium Inorganic materials 0.000 title claims description 31
- 239000003054 catalyst Substances 0.000 title claims description 27
- 150000001875 compounds Chemical class 0.000 title claims description 27
- 150000001491 aromatic compounds Chemical class 0.000 title claims description 20
- 238000006356 dehydrogenation reaction Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000001924 cycloalkanes Chemical class 0.000 title description 13
- 125000000392 cycloalkenyl group Chemical group 0.000 title 1
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 150000001925 cycloalkenes Chemical group 0.000 claims description 16
- 239000003125 aqueous solvent Substances 0.000 claims description 12
- 239000002516 radical scavenger Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- USNWAMPROKAEIT-UHFFFAOYSA-N [Na].C(C=C)(=O)O Chemical compound [Na].C(C=C)(=O)O USNWAMPROKAEIT-UHFFFAOYSA-N 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 239000000758 substrate Substances 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005698 Diels-Alder reaction Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical compound C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 0 COC(C(CC=CC1c2c*(*)ccc2)=C1C(OC)=O)=O Chemical compound COC(C(CC=CC1c2c*(*)ccc2)=C1C(OC)=O)=O 0.000 description 1
- LSEUFFJWMRTFIN-UHFFFAOYSA-N COC(c1cccc(-c2ccc[s]2)c1C(OC)=O)=O Chemical compound COC(c1cccc(-c2ccc[s]2)c1C(OC)=O)=O LSEUFFJWMRTFIN-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Description
本発明は、不均一系パラジウム触媒を用いたシクロアルカジエンまたはシクロアルケン構造を有する化合物の脱水素反応による芳香族化合物の製造方法に関するものである。 The present invention relates to a method for producing an aromatic compound by a dehydrogenation reaction of a compound having a cycloalkane or cycloalkene structure using a heterogeneous palladium catalyst.
ビアリール等の芳香族化合物は、生物活性物質や医薬品等の機能性材料を構成する基本骨格であり、系統的かつ簡便な合成法の開発は重要である。ジエンとアルキンのＤｉｅｌｓ‐Ａｌｄｅｒ 反応から調製されたシクロアルカジエン構造を有する化合物は、一般に、有機溶媒中、ＤＤＱ（2,3-ジクロロ-5,6-ジシアノ-p-ベンゾキノン）等の化学量論量の酸化剤により芳香環へと変換される。 Aromatic compounds such as biaryl are basic skeletons constituting functional materials such as bioactive substances and pharmaceuticals, and it is important to develop a systematic and simple synthetic method. Compounds with a cycloalkaziene structure prepared from the Diels-Alder reaction of diene and alkyne are generally stoichiometric such as DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone) in organic solvents. It is converted to an aromatic ring by an amount of oxidizing agent.
一方、遷移金属が触媒する脱水素反応は、水素(Ｈ２)のみが副生するアトムエコノミーに優れたクリーンな酸化法として注目されているが、シクロアルカジエン構造を有する化合物の芳香化反応に適用された例は少ない。有機溶媒中で行われた反応（非特許文献１）は報告されているが、工業的にも取り扱いやすく安価な水系溶媒中での報告はない。 On the other hand, the dehydrogenation reaction catalyzed by a transition metal is attracting attention as a clean oxidation method excellent in the atom economy in which only hydrogen (H 2) is produced as a by-product. There are few examples that have been applied. Although the reaction carried out in an organic solvent (Non-Patent Document 1) has been reported, there has been no report in an aqueous solvent which is industrially easy to handle and inexpensive.
従って、本発明の課題は、シクロアルカジエン構造を有する化合物を脱水素し、芳香族化合物を選択性良く製造する方法を提供することである。 Therefore, an object of the present invention is to provide a method for dehydrogenating a compound having a cycloalkaziene structure and producing an aromatic compound with good selectivity.
本発明者らは、上記課題を解決するために鋭意研究した結果、回収・再利用可能な不均一系パラジウムを触媒として、水系溶媒中でシクロアルカジエン構造を有する化合物の脱水素反応が進行し、それにより芳香族化合物が製造できることを見出した。また、本発明者らは、シクロアルカジエン構造を有する化合物だけでなく、シクロアルケン構造を有する化合物についても同様の脱水素反応が進行することを見出し、本発明を完成させた。 As a result of diligent research to solve the above problems, the present inventors proceeded with the dehydrogenation reaction of a compound having a cycloalkaziene structure in an aqueous solvent using recoverable / reusable heterogeneous palladium as a catalyst. , It has been found that an aromatic compound can be produced thereby. Further, the present inventors have found that the same dehydrogenation reaction proceeds not only with a compound having a cycloalkene structure but also with a compound having a cycloalkene structure, and completed the present invention.
すなわち、本発明は、シクロアルカジエンまたはシクロアルケン構造を有する化合物を、水系溶媒中で不均一系パラジウム触媒を用いて脱水素することを特徴とする芳香族化合物の製造方法である。 That is, the present invention is a method for producing an aromatic compound, which comprises dehydrogenating a compound having a cycloalkane or cycloalkene structure in an aqueous solvent using a heterogeneous palladium catalyst.
また、本発明は、下記化学式で表される化合物である。
本発明の芳香族化合物の製造方法は、温和な条件でも反応が進行し、かつ、選択性や収率が良く、芳香族化合物を得ることができる。 In the method for producing an aromatic compound of the present invention, the reaction proceeds even under mild conditions, and the selectivity and yield are good, so that an aromatic compound can be obtained.
本発明の芳香族化合物の製造方法（以下、「本発明方法」という）は、シクロアルカジエンまたはシクロアルケン構造を有する化合物を、水系溶媒中で不均一系パラジウム触媒を用いて脱水素する方法である。以下、本発明方法の構成について説明する。 The method for producing an aromatic compound of the present invention (hereinafter referred to as "the method of the present invention") is a method of dehydrogenating a compound having a cycloalkane or cycloalkene structure in an aqueous solvent using a heterogeneous palladium catalyst. be. Hereinafter, the configuration of the method of the present invention will be described.
（基質）
本発明方法で用いる基質は、シクロアルカジエンまたはシクロアルケン構造を有する化合物であって、脱水素により芳香族化合物となるものであれば特に限定されない。シクロアルカジエンまたはシクロアルケン構造を有する化合物としては、例えば、シクロヘキサジエンまたはシクロヘキセン構造を有する化合物が好ましく、シクロヘキセンやシクロヘキサジエンの水素がアリール基、フェニル基、アルキル基、エステル、複素環で置換されている化合物がより好ましい。また、シクロアルカジエンまたはシクロアルケン構造を有する化合物において、環構造における炭素は、窒素、酸素、硫黄等で置換されていて、複素環を形成していても良い。
(Substrate)
The substrate used in the method of the present invention is not particularly limited as long as it is a compound having a cycloalkane or cycloalkene structure and becomes an aromatic compound by dehydrogenation. As the compound having a cycloalkane or cycloalkene structure, for example, a compound having a cyclohexene or cyclohexene structure is preferable, and the hydrogen of cyclohexene or cyclohexene is substituted with an aryl group, a phenyl group, an alkyl group, an ester or a heterocycle. The compound is more preferable. Further, in a compound having a cycloalkane or cycloalkene structure, carbon in the ring structure may be substituted with nitrogen, oxygen, sulfur or the like to form a heterocycle.
（水系溶媒）
本発明方法で用いる水系溶媒は、特に限定されないが、例えば、水、エタノール、メタノール、酢酸、ギ酸等のプロトン性極性溶媒が好ましく、特に水が好ましい。また、これらの水系溶媒は複数の溶媒を混合しても良い。
(Aqueous solvent)
The aqueous solvent used in the method of the present invention is not particularly limited, but for example, a protic polar solvent such as water, ethanol, methanol, acetic acid, and formic acid is preferable, and water is particularly preferable. Further, these aqueous solvents may be a mixture of a plurality of solvents.
（水素捕捉剤）
本発明方法においては、水系溶媒に更に水素捕捉剤を添加することが、選択性や収率の点から好ましい。水素捕捉剤は、脱水素後に発生する水素を捕捉できるものであれば特に限定されないが、例えば、アクリル酸、アクリル酸ナトリウム、アクリル酸メチル、酢酸ビニル、１−ヘキセン等の炭素―炭素二重結合をもつ化合物または炭素―炭素三重結合をもつ化合物が好ましく、特にアクリル酸が好ましい。この水素捕捉剤は、本発明方法を行っている間、発生する水素を捕捉するのに十分な量が系内に存在していれば良いが、例えば、理論的に基質から発生する水素量に対して、１当量以上、好ましくは１〜５０当量、より好ましくは３〜１０当量である。
(Hydrogen scavenger )
In the method of the present invention, it is preferable to further add a hydrogen scavenger to the aqueous solvent from the viewpoint of selectivity and yield. The hydrogen trapping agent is not particularly limited as long as it can trap hydrogen generated after dehydrogenation, and is, for example, a carbon-carbon double bond such as acrylic acid, sodium acrylate, methyl acrylate, vinyl acetate, and 1-hexene. A compound having a carbon-carbon triple bond or a compound having a carbon-carbon triple bond is preferable, and acrylic acid is particularly preferable. This hydrogen scavenger may be used in an amount sufficient to capture the generated hydrogen during the method of the present invention, but for example, theoretically, the amount of hydrogen generated from the substrate may be used. On the other hand, it is 1 equivalent or more, preferably 1 to 50 equivalents, and more preferably 3 to 10 equivalents.
（不均一系パラジウム触媒）
本発明方法で用いる不均一系パラジウム触媒は、水系溶媒中でシクロアルカジエンまたはシクロアルケン構造を有する化合物からの脱水素が進行するものであれば特に限定されないが、例えば、活性炭、カーボンナノチューブ、グラファイト、グラフェン等のカーボン、アルミナ、シリカ等の担体にパラジウムを担持させたものが挙げられる。この不均一系パラジウム触媒は、本発明方法を行っている間、系内に存在していれば良いが、例えば、基質であるシクロアルカジエンまたはシクロアルケン構造を有する化合物に対して、１〜５０ｍｏｌ％、好ましくは３〜２０ｍｏｌ％である。なお、このような不均一系触媒は、反応後の触媒の分離、分離した触媒の再使用が容易である。
(Homogeneous palladium catalyst)
The heterogeneous palladium catalyst used in the method of the present invention is not particularly limited as long as dehydrogenation from a compound having a cycloalkane or cycloalkene structure proceeds in an aqueous solvent, and is, for example, activated carbon, carbon nanotubes, and graphite. , Graphene and other carbon, alumina, silica and other carriers supported with palladium. This heterogeneous palladium catalyst may be present in the system during the method of the present invention, and is, for example, 1 to 50 mol with respect to a compound having a cycloalkane or cycloalkene structure as a substrate. %, preferably 3 to 20 mol%. In such a heterogeneous catalyst, it is easy to separate the catalyst after the reaction and reuse the separated catalyst.
上記した不均一系パラジウム触媒の中でもカーボンにパラジウムを担持させたものが好ましく、特に活性炭にパラジウムを担持させたものが好ましい。なお、活性炭は比表面積値が大きく、担持するパラジウムの分散性を向上することができ、安価で高活性の不均一系触媒を得ることができる。 Among the above-mentioned heterogeneous palladium catalysts, those in which palladium is supported on carbon are preferable, and those in which palladium is supported on activated carbon are particularly preferable. The activated carbon has a large specific surface area value, can improve the dispersibility of the supported palladium, and can obtain an inexpensive and highly active heterogeneous catalyst.
また、上記した活性炭にパラジウムを担持させた不均一系パラジウム触媒の中でも下記（ａ）および（ｂ）の性質を有するものが好ましい。
（ａ）パラジウムを活性炭に対しパラジウム金属換算で１〜２０ｗｔ％、好ましくは５〜１５ｗｔ％含有する
なお、パラジウム量が少なすぎると反応性が低下することがあり、多すぎても使用量にみあった活性が得られないことがある。また、パラジウム量が多すぎると触媒上のパラジウム同士が凝集してしまうことがあり、その場合パラジウム粒子全体の表面積が低下して活性も低下してしまうことがある。
Further, among the heterogeneous palladium catalysts in which palladium is supported on the above-mentioned activated carbon, those having the following properties (a) and (b) are preferable.
(A) Palladium is contained in 1 to 20 wt%, preferably 5 to 15 wt% in terms of palladium metal with respect to activated carbon. If the amount of palladium is too small, the reactivity may decrease, and if it is too large, the amount used may be considered. The desired activity may not be obtained. Further, if the amount of palladium is too large, the palladium on the catalyst may agglomerate with each other, and in that case, the surface area of the entire palladium particles may decrease and the activity may decrease.
（ｂ）活性炭の比表面積値（ＢＥＴ値）が５００〜２,０００ｍ２／ｇ、好ましくは８００〜１,５００ｍ２／ｇである
なお、活性炭の比表面積値が小さすぎるとパラジウムの分散性が低下してしまい反応性が低下してしまうことがある。また、理由は定かではないが、比表面積値が大きすぎても、本発明方法では反応性が低下することがある。
(B) specific surface area of the activated carbon (BET value) is 500~2,000m 2 / g, preferably still a 800~1,500m 2 / g, the dispersibility of the specific surface area is too small palladium charcoal It may decrease and the reactivity may decrease. Further, although the reason is not clear, even if the specific surface area value is too large, the reactivity may decrease in the method of the present invention.
上記した性質を有する活性炭にパラジウムを担持させた不均一系触媒としては、公知の方法に従って調製しても良いし、例えば、［Ｐ９−Ｔｙｐｅ］（パラジウム含量；１０ｗｔ％、比表面積値；１,０００ｍ２／ｇ）、［Ｋ−タイプ触媒］（パラジウム含量；１０ｗｔ％、比表面積値；１,１００ｍ２／ｇ）、［ＵＬ−Ｔｙｐｅ］（パラジウム含量；１０ｗｔ％、比表面積値１,１５０ｍ２／ｇ）、［Ｐ６０−Ｔｙｐｅ］（パラジウム含量；１０ｗｔ％、比表面積値１,５５０ｍ２／ｇ）（いずれもエヌ・イー ケムキャット（株）製）等の市販品を利用することもできる。
また、これら触媒は、反応の前に水素等の還元雰囲気下で活性化しても良い。
The heterogeneous catalyst in which palladium is supported on activated carbon having the above-mentioned properties may be prepared according to a known method, and for example, [P9-Type] (palladium content; 10 wt%, specific surface area value; 1, 000m 2 / g), [K-type catalyst] (palladium content; 10 wt%, specific surface area value; 1,100 m 2 / g), [UL-Type] (palladium content: 10 wt%, specific surface area value 1,150 m 2) / G), [P60-Type] (palladium content; 10 wt%, specific surface area value 1,550 m 2 / g) (both manufactured by N.E. Chemcat Co., Ltd.) and the like can also be used.
Further, these catalysts may be activated in a reducing atmosphere such as hydrogen before the reaction.
（脱水素反応）
本発明方法において、脱水素反応は、シクロアルカジエンまたはシクロアルケン構造を有する化合物を、水系溶媒中で不均一系パラジウム触媒存在下で行われる。反応条件は特に限定されず、例えば、反応温度、反応時間、雰囲気等の条件を適宜制御して行えば良い。
また、本発明方法を行う前に、Ｄｉｅｌｓ−Ａｌｄｅｒ反応を行い、本発明方法の基質となるシクロアルカジエンまたはシクロアルケン構造を有する化合物を調製し、そのまま同じ系で、本発明方法を行うことも可能である。
(Dehydrogenation reaction)
In the method of the present invention, the dehydrogenation reaction is carried out by mixing a compound having a cycloalkane or cycloalkene structure in an aqueous solvent in the presence of a heterogeneous palladium catalyst. The reaction conditions are not particularly limited, and for example, conditions such as reaction temperature, reaction time, and atmosphere may be appropriately controlled.
Further, before carrying out the method of the present invention, a Diels-Alder reaction may be carried out to prepare a compound having a cycloalkane or cycloalkene structure as a substrate of the method of the present invention, and the method of the present invention may be carried out as it is in the same system. It is possible.
（反応温度）
本発明方法の反応温度は、脱水素反応が進行するのであれば特に限定されないが、６０〜２００℃が好ましく、特に７０〜１５０℃が好ましい。
(Reaction temperature)
The reaction temperature of the method of the present invention is not particularly limited as long as the dehydrogenation reaction proceeds, but is preferably 60 to 200 ° C, particularly preferably 70 to 150 ° C.
（反応時間）
本発明方法の反応時間は、特に限定されないが、例えば、１〜４８時間、好ましくは６〜２６時間である。また、反応の際には撹拌をすることが好ましい。
(Reaction time)
The reaction time of the method of the present invention is not particularly limited, but is, for example, 1 to 48 hours, preferably 6 to 26 hours. Further, it is preferable to stir during the reaction.
（雰囲気）
本発明方法での反応雰囲気は、パラジウム触媒存在下で脱水素反応が進行するものであれば特に限定されないが、例えば、アルゴンや窒素等の不活性雰囲気で行われることが好ましく、特にアルゴンが好ましい。
(atmosphere)
The reaction atmosphere in the method of the present invention is not particularly limited as long as the dehydrogenation reaction proceeds in the presence of a palladium catalyst, but it is preferably carried out in an inert atmosphere such as argon or nitrogen, and argon is particularly preferable. ..
（反応容器）
本発明方法で用いる容器は、特に限定されず、試験管、フラスコ等、反応のスケールにあわせたものを用いれば良い。また、本発明方法においては、同一容器内で、基質であるシクロアルカジエンまたはシクロアルケン構造を有する化合物の合成を行い、更に、脱水素反応を行うこともできる。
(Reaction vessel)
The container used in the method of the present invention is not particularly limited, and a test tube, flask, or the like may be used according to the scale of the reaction. Further, in the method of the present invention, a compound having a cycloalkane or cycloalkene structure as a substrate can be synthesized in the same container, and a dehydrogenation reaction can be further carried out.
以上説明した本発明方法により、シクロアルカジエンまたはシクロアルケン構造を有する化合物が脱水素され、芳香族化合物が得られる。脱水素した後は、冷却、ろ過等をし、更に、常法に従って精製等を行っても良い。なお、芳香族化合物が得られたかどうかはＮＭＲ等公知の方法で確認することができる According to the method of the present invention described above, a compound having a cycloalkane or cycloalkene structure is dehydrogenated to obtain an aromatic compound. After dehydrogenation, cooling, filtration, etc. may be performed, and further purification may be performed according to a conventional method. Whether or not an aromatic compound has been obtained can be confirmed by a known method such as NMR.
また、本発明方法を終了した後は、ろ過、遠心分離等で不均一系パラジウム触媒を回収し、再利用することができる。 Further, after the method of the present invention is completed, the heterogeneous palladium catalyst can be recovered and reused by filtration, centrifugation or the like.
以下、本発明を実施例を挙げて詳細に説明するが、本発明はこれら実施例に何ら限定さえるものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
実 施 例 １
内容量１７ｍＬの試験管（Ｃｈｅｍｉｓｔａｔｉｏｎ（登録商標）用）中で、基質である１（０．１ｍｍｏｌ）、１０％Ｐｄ／Ｃ（エヌ・イー ケムキャット（株）製のＫ−タイプ触媒）（５ｍｏｌ％）、表１の水素捕捉剤（ａｃｃｅｐｔｏｒ）、水（１ｍＬ）の順に加え、セプタムで密封した。試験管内部の気体をＡｒ ｂａｌｌｏｏｎで３回置換した。Ａｒ雰囲気下、Ｃｈｅｍｉｓｔａｔｉｏｎ（登録商標）（東京理化器械（株）製）を用いて、１２０℃で６時間、加熱攪拌した。反応終了後、反応液を室温まで放冷し、飽和炭酸水素ナトリウム水溶液（１ｍＬ）を加え、メンブランフィルター（Ｍｉｌｌｉｐｏｒｅ社製、製品名：Ｍｉｌｌｅｘ−ＬＨ、０．２０ｍｍ）でろ過した。反応容器内部とフィルター上の触媒を酢酸エチル（１０ｍＬ）で３回と蒸留水（１０ｍＬ）で３回洗浄し、ろ液と合わせた。ろ液を二層に分離後、水層を酢酸エチル（１０ｍＬ）で抽出した。有機層を合わせて、蒸留水（１０ｍＬ）で２回洗浄し、無水硫酸マグネシウムで乾燥、ろ過した。ろ液を減圧留去し、脱水素化された芳香族化合物２が表１の収率で得られた。収率は内標物質として１，２−メチレンジオキシベンゼンを用いて、Ｈ１−ＮＭＲにより算出した。
Example 1
Substrate 1 (0.1 mmol), 10% Pd / C (K-type catalyst manufactured by NE Chemcat Co., Ltd.) (5 mol%) in a test tube (for Chemistation®) having an internal volume of 17 mL. ), The hydrogen scavenger (acceptor) in Table 1, and water (1 mL) were added in this order, and the mixture was sealed with a septum. The gas inside the test tube was replaced with Ar balloon three times. Under an Ar atmosphere, using Chemistation (registered trademark) (manufactured by Tokyo Rika Kikai Co., Ltd.), the mixture was heated and stirred at 120 ° C. for 6 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, a saturated aqueous sodium hydrogen carbonate solution (1 mL) was added, and the mixture was filtered through a membrane filter (manufactured by Millipore, product name: Millex-LH, 0.20 mm). The catalyst inside the reaction vessel and on the filter were washed 3 times with ethyl acetate (10 mL) and 3 times with distilled water (10 mL) and combined with the filtrate. After separating the filtrate into two layers, the aqueous layer was extracted with ethyl acetate (10 mL). The organic layers were combined, washed twice with distilled water (10 mL), dried over anhydrous magnesium sulfate, and filtered. The filtrate was distilled off under reduced pressure to obtain the dehydrogenated aromatic compound 2 in the yield shown in Table 1. Yield using 1,2-methylenedioxybenzene as internal standard substance was calculated by H 1 -NMR.
本発明方法は、水素捕捉剤を添加しなくても進行するが、水素捕捉剤を添加することで、目的物の収率は高く、副生成物が少なくなった。特に水素捕捉剤としてアクリル酸を用いた場合、目的物の収率はより高く、副生成物がより少なくなった。 The present invention can proceed even without addition of hydrogen scavenger, the addition of hydrogen scavenger, the yield of the desired product is high, by-products is low. In particular , when acrylic acid was used as the hydrogen scavenger , the yield of the target product was higher and the amount of by-products was lower.
実 施 例 ２
実施例１の水素捕捉剤を全てアクリル酸にして添加量と反応温度を変更したときの結果を表２に示す。収率は、粗生成物をシリカゲルカラムクロマトグラフィーで精製した単離収率である。
Example 2
Table 2 shows the results when all the hydrogen scavengers of Example 1 were changed to acrylic acid and the addition amount and the reaction temperature were changed. The yield is the isolated yield obtained by purifying the crude product by silica gel column chromatography.
本発明方法は、種々の水素捕捉剤量、反応温度で進行することが分かった。水素捕捉剤は１当量以上加えれば、例１の場合と比較して目的化合物１の収率は良くなることが分かった。 It was found that the method of the present invention proceeds at various amounts of hydrogen scavengers and reaction temperatures. It was found that when 1 equivalent or more of the hydrogen scavenger was added, the yield of the target compound 1 was improved as compared with the case of Example 1.
実 施 例 ３
実施例１の基質を変更したときの結果を表３に示す。収率は、粗生成物をシリカゲルカラムクロマトグラフィーで精製した単離収率である。
Actual example 3
Table 3 shows the results when the substrate of Example 1 was changed. The yield is the isolated yield obtained by purifying the crude product by silica gel column chromatography.
本発明方法は、種々の基質で進行することが分かった。 It has been found that the method of the present invention proceeds with various substrates.
実 施 例 ４
実施例１の基質を変更したときの結果を表４に示す。収率は、粗生成物をシリカゲルカラムクロマトグラフィーで精製した単離収率である。
Example 4
Table 4 shows the results when the substrate of Example 1 was changed. The yield is the isolated yield obtained by purifying the crude product by silica gel column chromatography.
本発明方法は、種々の基質で進行することが分かった。 It has been found that the method of the present invention proceeds with various substrates.
実 施 例 ５
実施例１の基質（Ｓｕｂｓｔｒａｔｅ）を変更したときの結果を表５に示す。収率は、粗生成物をシリカゲルカラムクロマトグラフィーで精製した単離収率である。
Example 5
Table 5 shows the results when the substrate of Example 1 was changed. The yield is the isolated yield obtained by purifying the crude product by silica gel column chromatography.
本発明方法は、種々の基質で進行することが分かった。 It has been found that the method of the present invention proceeds with various substrates.
実 施 例 ６
Ｄｉｅｌｓ‐Ａｌｄｅｒ 反応からの同一容器内での脱水素反応：
Ｄｉｅｌｓ‐Ａｌｄｅｒ 反応の生成物であるシクロヘキサジエン誘導体（式１の基質）を単離せずに、同一容器でそのまま脱水素反応を行った（式５）。収率は、粗生成物をシリカゲルカラムクロマトグラフィーで精製した単離収率である。
Example 6
Dehydrogenation reaction in the same vessel from the Diels-Alder reaction:
The cyclohexadiene derivative (the substrate of the formula 1), which is the product of the Diels-Alder reaction, was not isolated, but the dehydrogenation reaction was carried out as it was in the same container (formula 5). The yield is the isolated yield obtained by purifying the crude product by silica gel column chromatography.
Ｄｉｅｌｓ‐Ａｌｄｅｒ 反応の生成物であるシクロヘキサジエン誘導体を単離せずにそのまま本発明方法を行っても目的物を収率良く得ることができた。 Even if the method of the present invention was carried out as it was without isolating the cyclohexadiene derivative which is the product of the Diels-Alder reaction, the desired product could be obtained in good yield.
実 施 例 ７
触媒の繰り返し使用：
実施例１の例６の反応を繰り返し行った際の収率と反応後に回収できた触媒の回収率を表６に示す。触媒の回収方法は反応後の溶液を室温まで放冷し、飽和炭酸水素ナトリウム水溶液（１ｍＬ）を加え、吸引ろ過（桐山ロート（４０ｍｍ、１μｍ））した。反応容器内部、ろ紙上の触媒を酢酸エチル（１０ｍＬ）と蒸留水（１０ｍＬ）で洗浄し、ろ液と合わせた。ろ取した触媒をメタノール（１０ｍＬ）で５回と蒸留水（１０ｍＬ）で５回洗浄し、デシケータ内で減圧して２４時間乾燥した。２の収率は内標物質として１，２−メチレンジオキシベンゼンを用いて、Ｈ１−ＮＭＲにより算出した。
Example 7
Repeated use of catalyst:
Table 6 shows the yield when the reaction of Example 6 of Example 1 was repeated and the recovery rate of the catalyst recovered after the reaction. As a method for recovering the catalyst, the solution after the reaction was allowed to cool to room temperature, a saturated aqueous sodium hydrogen carbonate solution (1 mL) was added, and suction filtration (Kiriyama funnel (40 mm, 1 μm)) was performed. The catalyst inside the reaction vessel and on the filter paper was washed with ethyl acetate (10 mL) and distilled water (10 mL), and combined with the filtrate. The collected catalyst was washed 5 times with methanol (10 mL) and 5 times with distilled water (10 mL), depressurized in a desiccator, and dried for 24 hours. 2 The yield using 1,2-methylenedioxybenzene as internal standard substance was calculated by H 1 -NMR.
本発明方法では触媒を繰り返し使用しても収率良く目的物を得ることができた。 In the method of the present invention, the desired product could be obtained in good yield even if the catalyst was repeatedly used.
本発明方法は、種々の医薬、農薬、その他種々の工業分野において有用な芳香族化合物を温和な条件で安全に製造することができる。
以 上
The method of the present invention can safely produce aromatic compounds useful in various pharmaceuticals, pesticides, and other various industrial fields under mild conditions.
that's all
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