JP6638934B2 - Method for producing furfural or furfural derivative - Google Patents
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- JP6638934B2 JP6638934B2 JP2015246219A JP2015246219A JP6638934B2 JP 6638934 B2 JP6638934 B2 JP 6638934B2 JP 2015246219 A JP2015246219 A JP 2015246219A JP 2015246219 A JP2015246219 A JP 2015246219A JP 6638934 B2 JP6638934 B2 JP 6638934B2
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 33
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000002904 solvent Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 239000010931 gold Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- -1 aldehyde compound Chemical class 0.000 description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 6
- 229960001545 hydrotalcite Drugs 0.000 description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- AHIXHWRUDZFHEZ-UHFFFAOYSA-N furan-2,3-dicarbaldehyde Chemical compound O=CC=1C=COC=1C=O AHIXHWRUDZFHEZ-UHFFFAOYSA-N 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VOZFDEJGHQWZHU-UHFFFAOYSA-N (5-methylfuran-2-yl)methanol Chemical compound CC1=CC=C(CO)O1 VOZFDEJGHQWZHU-UHFFFAOYSA-N 0.000 description 2
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DSMRYCOTKWYTRF-UHFFFAOYSA-N 3-methylfuran-2-carbaldehyde Chemical compound CC=1C=COC=1C=O DSMRYCOTKWYTRF-UHFFFAOYSA-N 0.000 description 1
- BLHZUMDWLLFLJC-UHFFFAOYSA-N 4-methylfuran-2-carbaldehyde Chemical compound CC1=COC(C=O)=C1 BLHZUMDWLLFLJC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Furan Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、フルフラール又はフルフラール誘導体の製造方法に関するものである。 The present invention relates to a method for producing furfural or a furfural derivative.
近年、化石資源の燃焼により発生した二酸化炭素を原因とした地球温暖化が世界的な問題となっている。このような中、化石資源代替バイオマスの活用を探る研究が進められている。
フルフラール類は、化石資源代替バイオマスの中でも石油製基幹物質の代替となる可能性を有しており、特に注目を集めている化合物の一つである。フルフラールはフラン系樹脂の原料や反応溶媒、接着剤などに利用することができる。
In recent years, global warming caused by carbon dioxide generated by burning fossil resources has become a global problem. Under such circumstances, research is being conducted to explore the use of biomass alternatives to fossil resources.
Furfural is one of the compounds that has attracted particular attention because it has the potential to replace petroleum basic substances among fossil resource alternative biomass. Furfural can be used as a raw material of a furan-based resin, a reaction solvent, an adhesive, and the like.
フルフラール又はフルフラール誘導体を得るには、経済上及び環境上の観点から、強力な酸化剤を用いることなく、酸素分子（Ｏ２）を酸化剤とし、触媒の存在下、対応するフルフリルアルコール誘導体を酸化してアルデヒド化合物であるフルフラール又はフルフラール誘導体とする方法を用いることが望ましい。 In order to obtain furfural or a furfural derivative, from an economic and environmental point of view, without using a strong oxidizing agent, an oxygen molecule (O 2 ) is used as an oxidizing agent, and a corresponding furfuryl alcohol derivative is obtained in the presence of a catalyst. It is desirable to use a method of oxidation to furfural or a furfural derivative as an aldehyde compound.
酸素を酸化剤として、アルコールからアルデヒド化合物を製造するには、種々の貴金属触媒が用いられている。
例えば、非特許文献１には、酸素を酸化剤とし、金及び2,2,6,6-テトラメチルピペリジン-1-オキシル（ＴＥＭＰＯ）を触媒として用いて、フルフリルアルコールからフルフラールを製造する方法が開示されている。しかしながら非特許文献１に記載された方法では、反応が均一系で進行するため反応後に生成物から触媒を分離する操作が煩雑になるという問題がある。
Various noble metal catalysts have been used to produce aldehyde compounds from alcohols using oxygen as an oxidizing agent.
For example, Non-Patent Document 1 discloses a method for producing furfural from furfuryl alcohol using oxygen as an oxidizing agent and gold and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a catalyst. Is disclosed. However, the method described in Non-Patent Document 1 has a problem that since the reaction proceeds in a homogeneous system, the operation of separating the catalyst from the product after the reaction becomes complicated.
一方、非特許文献２には、反応後、反応溶液からろ過により容易に分離回収可能なハイドロタルサイト（ＨＴ）固定化金ナノ粒子触媒（以下、「Ａｕ／ＨＴ」ということもある）を用いて、各種ベンジル型、アリル型、又は脂肪族二級アルコール類を、高選択的に対応するアルデヒド及びケトンへと酸化できることが記載されている。 On the other hand, Non-Patent Document 2 uses a hydrotalcite (HT) -immobilized gold nanoparticle catalyst (hereinafter, also referred to as “Au / HT”) that can be easily separated and recovered from the reaction solution by filtration after the reaction. It is described that various benzyl type, allyl type, or aliphatic secondary alcohols can be oxidized to corresponding aldehydes and ketones with high selectivity.
また、特許文献１、２には、分子状酸素を酸化剤とし、脂肪族アルコール、脂環式アルコール、芳香族アルコール及び複素環式アルコールから対応するアルデヒドを製造する方法に関し、触媒として、担体に担持したルテニウム触媒を用いることが開示されており、多数の例示された複素環式アルコールには、フルフリルアルコールも含まれている。 Patent Documents 1 and 2 disclose a method for producing a corresponding aldehyde from an aliphatic alcohol, an alicyclic alcohol, an aromatic alcohol and a heterocyclic alcohol using molecular oxygen as an oxidizing agent. The use of a supported ruthenium catalyst is disclosed, and a number of the exemplified heterocyclic alcohols also include furfuryl alcohol.
しかしながら、酸素を酸化剤とし、非特許文献２に記載されたＡｕ／ＨＴを用いて、フルフラール又はフルフリルアルコール誘導体を酸化した場合、転化率が低く、低収率であることが判明した。
また、特許文献１，２において好ましい担持触媒とされている炭素担持ルテニウム触媒（以下、「Ｒｕ／Ｃ」とすることもある）を用いた場合、過剰な酸化反応により生成したカルボン酸が原料とエステル反応するか、あるいは、エステル重合が生じることにより、溶媒に不溶の副生成物を生じ、収率が低下するという問題があることが判明した。
However, when the furfural or furfuryl alcohol derivative was oxidized using Au / HT described in Non-Patent Document 2 using oxygen as an oxidizing agent, it was found that the conversion was low and the yield was low.
Further, in the case of using a ruthenium-on-carbon catalyst (hereinafter, also referred to as “Ru / C”) which is a preferred supported catalyst in Patent Documents 1 and 2, a carboxylic acid generated by an excessive oxidation reaction is used as a raw material. It has been found that there is a problem in that the ester reaction or the ester polymerization causes a by-product insoluble in the solvent and the yield is reduced.
本発明は、これらの知見に基づいてなされたものであり、酸素を酸化剤とし、フルフリルアルコール又はフルフリルアルコール誘導体を酸化して、フルフラール又は対応するフルフラール誘導体を得る方法において、転換率が高く、且つ、過剰な酸化反応を起こさない適切な触媒を用いることにより、高収率かつ高選択的にフルフラール又は対応するフルフラール誘導体を製造しうる方法を提供することを目的とする。 The present invention has been made based on these findings, using oxygen as an oxidizing agent, oxidizing furfuryl alcohol or a furfuryl alcohol derivative to obtain furfural or a corresponding furfural derivative, and a high conversion rate. An object of the present invention is to provide a method capable of producing furfural or a corresponding furfural derivative with high yield and high selectivity by using an appropriate catalyst that does not cause an excessive oxidation reaction.
本発明者らは、上記の課題を解決するために鋭意検討した結果、アルミナ担持ルテニウム触媒を用いることによって上記目的を達成できることを見出し、本発明を完成させるに至った。
すなわち、本発明は以下のとおりである。
［１］酸素を酸化剤とし、触媒の存在下、下記の一般式（１）で示されるフルフリルアルコール又はフルフリルアルコール誘導体を酸化して下記の一般式（２）で示されるフルフラール又はフルフラール誘導体を生成させる方法であって、前記触媒として、アルミナ担持ルテニウム触媒を用いることを特徴とするフルフラール又はフルフラール誘導体の製造方法。
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above objects can be achieved by using a ruthenium catalyst supported on alumina, and have completed the present invention.
That is, the present invention is as follows.
[1] Furfural alcohol or a furfural derivative represented by the following general formula (2) by oxidizing furfuryl alcohol or a furfuryl alcohol derivative represented by the following general formula (1) in the presence of a catalyst using oxygen as an oxidizing agent , Wherein a ruthenium-on-alumina catalyst is used as the catalyst.
［式中、Ｒはプロトン、メチル基、又はホルミル基である。］
［２］前記酸化反応の圧力が、０．１〜１０ＭＰａであることを特徴とする［１］に記載のフルフラール又はフルフラール誘導体の製造方法。
［３］前記酸化反応の温度が、０〜１５０℃であることを特徴とする［１］又は［２］に記載のフルフラール又はフルフラール誘導体の製造方法。
[Wherein, R is a proton, a methyl group, or a formyl group. ]
[2] The method for producing furfural or a furfural derivative according to [1], wherein the pressure of the oxidation reaction is 0.1 to 10 MPa.
[3] The method for producing furfural or a furfural derivative according to [1] or [2], wherein the temperature of the oxidation reaction is 0 to 150 ° C.
本発明のフルフラール又はフルフラール誘導体の製造法によれば、アルミナ担持ルテニウム触媒を用いることで、常圧の酸素を酸化剤として活用することが可能となり、フルフリルアルコール又はフリフリルアルコール誘導体から高収率および高選択性でフルフラール又はフルフラール誘導体を得ることができる。 According to the method for producing furfural or a furfural derivative of the present invention, by using an alumina-supported ruthenium catalyst, it becomes possible to utilize oxygen at normal pressure as an oxidizing agent and obtain a high yield from furfuryl alcohol or a furfuryl alcohol derivative. Furfural or furfural derivatives can be obtained with high selectivity.
以下、本発明について詳細に説明する。
本発明において原料（基質）として用いる一般式（１）
Hereinafter, the present invention will be described in detail.
General formula (1) used as a raw material (substrate) in the present invention
［式中、Ｒはプロトン、メチル基、又はホルミル基である。］
で示されるフルフリルアルコール又はフルフリルアルコール誘導体は、特に限定されないが、例えばフルフリルアルコール、５−ヒドロキシメチルフルフラール、３−メチルフルフリルアルコール、４−メチルフルフリルアルコール、５−メチルフルフリルアルコール等が挙げられる。
これらの中でも、フルフリルアルコールや５−ヒドロキシメチルフルフラールは、例えば非可食の木質バイオマスから得られる環境調和型の化学原料として工業的に有用である。
[Wherein, R is a proton, a methyl group, or a formyl group. ]
The furfuryl alcohol or furfuryl alcohol derivative represented by is not particularly limited, but includes, for example, furfuryl alcohol, 5-hydroxymethylfurfural, 3-methylfurfuryl alcohol, 4-methylfurfuryl alcohol, 5-methylfurfuryl alcohol, and the like. Is mentioned.
Among these, furfuryl alcohol and 5-hydroxymethylfurfural are industrially useful as environmentally friendly chemical raw materials obtained from, for example, non-edible woody biomass.
また、本発明により製造される一般式（２） The general formula (2) produced by the present invention
［式中、Ｒはプロトン、メチル基、又はホルミル基である。］
で示されるフルフラール又はフルフラール誘導体は、前記のフルフリルアルコール又はフルフリルアルコール誘導体のそれぞれに対応して、フルフラール、ジホルミルフラン、３−メチルフルフラール、４−メチルフルフラール、５−メチルフルフラール等が挙げられる。
[Wherein, R is a proton, a methyl group, or a formyl group. ]
Furfural or furfural derivatives represented by are, for example, furfural, diformylfuran, 3-methylfurfural, 4-methylfurfural, 5-methylfurfural, etc., corresponding to the above furfuryl alcohol or furfuryl alcohol derivative, respectively. .
本発明においては、酸素を酸化剤として用い、上記一般式（１）で示されるフルフリルアルコール誘導体を酸化して、上記一般式（２）で示されるフルフラール誘導体を製造する際に、アルミナ担持ルテニウム触媒を用いることにより、過剰な酸化反応を起こさずに、高収率かつ高選択的に、対応するフルフラール誘導体を得ることがきる。 In the present invention, when oxygen is used as an oxidizing agent to oxidize a furfuryl alcohol derivative represented by the above general formula (1) to produce a furfural derivative represented by the above general formula (2), ruthenium supported on alumina is used. By using a catalyst, the corresponding furfural derivative can be obtained with high yield and high selectivity without causing excessive oxidation reaction.
本発明で用いるアルミナ担持ルテニウム触媒は、反応後、ろ過により容易に系中から分離することができ、洗浄および乾燥後、再び反応に用いることができる。
アルミナ担持ルテニウム触媒としては、市販されているものを用いることができ、例えば、和光純薬工業製、シグマアルドリッチ社製、Ａｌｆａ Ａｅｓａｒ社製などのいずれも市販品が挙げられる。
The alumina-supported ruthenium catalyst used in the present invention can be easily separated from the system by filtration after the reaction, and can be used again for the reaction after washing and drying.
As the alumina-supported ruthenium catalyst, a commercially available one can be used, and examples thereof include commercially available products such as those manufactured by Wako Pure Chemical Industries, Sigma-Aldrich, and Alfa Aesar.
本発明に用いられるルテニウム触媒の触媒量は特に限定されないが、経済性と反応性の観点から、反応基質に対して、ルテニウム原子で１ｍｏｌ％〜３０ｍｏｌ％が好ましく、５ｍｏｌ％〜１０ｍｏｌ％がより好ましい。
なお、市販品のアルミナ担持ルテニウム触媒におけるルテニウムの担持量は、５重量％のものが一般的であり、酸化反応に用いる際には、反応基質に対するルテニウム原子に換算して用いられる。
The amount of the ruthenium catalyst used in the present invention is not particularly limited, but is preferably 1 mol% to 30 mol%, more preferably 5 mol% to 10 mol% with respect to the reaction substrate, based on the reaction substrate, from the viewpoint of economy and reactivity. .
The amount of supported ruthenium in a commercially available ruthenium-supported alumina catalyst is generally 5% by weight, and when used in an oxidation reaction, it is used in terms of a ruthenium atom relative to a reaction substrate.
本発明では、酸素の存在下で行われ、過酸化水素等の酸化剤を必要としない。そのため安全かつ安価にフルフラール誘導体を製造できる。
本発明に用いられる酸素としては、市販の精製ガスだけでなく、空気中に含まれる酸素を用いてもよい。酸素は、市販のガス採集袋に導入して常圧で用いることができる。また、より効率よく反応させるために、酸素ガスとして反応容器に供されることが好ましい。
The present invention is performed in the presence of oxygen and does not require an oxidizing agent such as hydrogen peroxide. Therefore, a furfural derivative can be produced safely and inexpensively.
As oxygen used in the present invention, not only commercially available purified gas but also oxygen contained in air may be used. Oxygen can be introduced into a commercially available gas collection bag and used at normal pressure. Further, in order to make the reaction more efficient, it is preferable that the oxygen gas is supplied to the reaction vessel.
本発明に用いられる溶媒としては、水、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、ヘキサン、トルエン、アセトン、メチルイソブチルケトン、クロロホルム、ジクロロメタン、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等が挙げられる。特に限定されないが、非プロトン性有機溶媒が好ましく、中でもトルエン、メチルイソブチルケトンがより好ましく、トルエンがさらに好ましい。 Examples of the solvent used in the present invention include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, hexane, toluene, acetone, methyl isobutyl ketone, chloroform, dichloromethane, N, N-dimethylformamide, and dimethyl sulfoxide. And the like. Although not particularly limited, an aprotic organic solvent is preferable, and among them, toluene and methyl isobutyl ketone are more preferable, and toluene is further more preferable.
本発明の反応濃度は特に限定されないが、経済性と反応性の観点から０．０５ｍｏｌ／Ｌ〜５ｍｏｌ／Ｌが好ましく、０．１ｍｏ／Ｌ〜１ｍｏｌ／Ｌがより好ましく、０．２ｍｏｌ／Ｌ〜０．５ｍｏｌ／Ｌがさらに好ましい。 The reaction concentration of the present invention is not particularly limited, but is preferably from 0.05 mol / L to 5 mol / L, more preferably from 0.1 mol / L to 1 mol / L, and more preferably from 0.2 mol / L, from the viewpoint of economy and reactivity. 0.5 mol / L is more preferred.
本発明の反応圧力は０．１ＭＰａ〜１０ＭＰａが好ましく、工業的な観点から０．１ＭＰａがより好ましい。 The reaction pressure of the present invention is preferably 0.1 MPa to 10 MPa, and more preferably 0.1 MPa from an industrial viewpoint.
本発明の反応温度は０℃〜１５０℃が好ましく、５０℃〜１２０℃がより好ましく、反応性の観点から８０℃〜１００℃がさらに好ましい。 The reaction temperature of the present invention is preferably from 0C to 150C, more preferably from 50C to 120C, and even more preferably from 80C to 100C from the viewpoint of reactivity.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例及び比較例に用いた触媒における「５ｍｏｌ％」は、いずれも、反応基質に対するルテニウム原子又は金原子の量を示す。 Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In addition, "5 mol%" in the catalysts used in Examples and Comparative Examples each indicates the amount of ruthenium atoms or gold atoms with respect to the reaction substrate.
反応の転化率および収率の決定は以下の方法で行った。
反応粗生成物に内部標準物質として正確に秤量したピラジンを加え、重クロロホルムに溶解することでサンプルを調製した。このサンプルのプロトンスペクトルをＪＥＯＬ ＲＥＳＯＮＡＮＣＥ社製の核磁気共鳴スペクトル装置ＥＣＡ−５００を用いて測定した。得られた粗生成物スペクトルのピーク面積を内部標準スペクトルのピーク面積と比較することで転化率および収率を決定した。
The conversion and yield of the reaction were determined by the following methods.
A precisely weighed pyrazine was added as an internal standard substance to the reaction crude product, and dissolved in deuterated chloroform to prepare a sample. The proton spectrum of this sample was measured using a nuclear magnetic resonance spectrometer ECA-500 manufactured by JEOL RESONANCE. The conversion and yield were determined by comparing the peak area of the obtained crude product spectrum with the peak area of the internal standard spectrum.
（実施例１）
フルフリルアルコール（１ｍｍｏｌ，９８ｍｇ）にトルエン（５ｍＬ）を加え、Ｒｕ／Ａｌ２Ｏ３（和光純薬工業製）（５ｍｏｌ％Ｒｕ）を懸濁させた。酸素ガスを充填したガス採集袋を取り付け、アスピレーターを用いて反応容器内部を酸素置換した。反応液を強く撹拌しながら８０℃で２４時間反応させた後、ろ過により触媒を除去し、母液を減圧留去した。得られた生成物を分析した結果、原料は完全に消失し、目的のフルフラ−ルの収率は９８％であった。
また、溶媒に不溶な副生成物の生成はなかった。
(Example 1)
Tolufuryl alcohol (1 mmol, 98 mg) was added with toluene (5 mL), and Ru / Al 2 O 3 (manufactured by Wako Pure Chemical Industries) (5 mol% Ru) was suspended. A gas collection bag filled with oxygen gas was attached, and the inside of the reaction vessel was replaced with oxygen using an aspirator. After the reaction was allowed to react at 80 ° C. for 24 hours with vigorous stirring, the catalyst was removed by filtration, and the mother liquor was distilled off under reduced pressure. As a result of analyzing the obtained product, the raw material was completely disappeared, and the yield of the target furfural was 98%.
In addition, there was no generation of a by-product insoluble in the solvent.
（実施例２）
基質に５−メチルフルフリルアルコール（１ｍｍｏｌ，１１２ｍｇ）を用いる以外は実施例１と同様の手法で行った。得られた生成物を分析した結果、原料は完全に消失し、目的の５−メチルフルフラールの収率は９５％であった。
また、溶媒に不溶な副生成物の生成はなかった。
(Example 2)
The procedure was performed in the same manner as in Example 1 except that 5-methylfurfuryl alcohol (1 mmol, 112 mg) was used as the substrate. As a result of analyzing the obtained product, the raw material completely disappeared, and the yield of the desired 5-methylfurfural was 95%.
In addition, there was no generation of a by-product insoluble in the solvent.
（実施例３）
基質に５−ヒドロキシメチルフルフラール（１ｍｍｏｌ，１２６ｍｇ）を用いる以外は実施例１と同様の手法で行った。得られた生成物を分析した結果、原料は完全に消失し、目的のジホルミルフランの収率は９９％であった。
また、溶媒に不溶な副生成物の生成はなかった。
(Example 3)
The procedure was performed in the same manner as in Example 1 except that 5-hydroxymethylfurfural (1 mmol, 126 mg) was used as the substrate. As a result of analyzing the obtained product, the raw material completely disappeared, and the yield of the target diformylfuran was 99%.
In addition, there was no generation of a by-product insoluble in the solvent.
（実施例４）
溶媒にメチルイソブチルケトン（５ｍＬ）を用いる以外は実施例３と同様の手法で行った。得られた生成物を分析した結果、原料の転化率は９７％であり、目的のジホルミルフランの収率は７２％であった。
また、溶媒に不溶な副生成物の生成はなかった。
(Example 4)
The procedure was performed in the same manner as in Example 3 except that methyl isobutyl ketone (5 mL) was used as the solvent. As a result of analyzing the obtained product, the conversion of the raw material was 97%, and the yield of the target diformylfuran was 72%.
In addition, there was no generation of a by-product insoluble in the solvent.
（参考例）
溶媒に水（５ｍＬ）を用いる以外は実施例３と同様の手法で行った。得られた生成物を分析した結果、原料の転化率は４８％であり、目的のジホルミルフランの収率は２１％であった。
また、溶媒に不溶な副生成物の生成はなかった。
( Reference example )
The procedure was performed in the same manner as in Example 3, except that water (5 mL) was used as the solvent. As a result of analyzing the obtained product, the conversion of the raw material was 48%, and the yield of the target diformylfuran was 21%.
In addition, there was no generation of a by-product insoluble in the solvent.
（比較例１）
触媒にＲｕ／Ｃ（和光純薬工業製）（５ｍｏｌ％Ｒｕ）を用いる以外は実施例３と同様の手法で行った。得られた生成物を分析した結果、原料は全て消失し、目的ジホルミルフランの収率は７５％であった。
また溶媒に不溶な副生成物が生じていた。
(Comparative Example 1)
The procedure was performed in the same manner as in Example 3, except that Ru / C (manufactured by Wako Pure Chemical Industries) (5 mol% Ru) was used as the catalyst. As a result of analyzing the obtained product, all the raw materials disappeared, and the yield of the target diformylfuran was 75%.
Further, a by-product insoluble in the solvent was generated.
（比較例２）
触媒にハイドロタルサイト担持金触媒（Ａｕ／ＨＴ）（和光純薬工業製）（５ｍｏｌ％Ａｕ）を用いる以外は実施例３と同様の手法で行った。得られた生成物を分析した結果、転化率は１９％であり、目的ジアルデヒドの収率は７％であった。
なお、溶媒に不溶な副生成物の生成はなかった。
これらの結果を、以下の表１に記載する。
(Comparative Example 2)
The same procedure as in Example 3 was performed except that a hydrotalcite-supported gold catalyst (Au / HT) (manufactured by Wako Pure Chemical Industries, Ltd.) (5 mol% Au) was used as the catalyst. As a result of analyzing the obtained product, the conversion was 19%, and the yield of the objective dialdehyde was 7%.
In addition, there was no generation of a by-product insoluble in the solvent.
These results are set forth in Table 1 below.
以上のとおり、アルミナ担持ルテニウム触媒を用いた実施例１〜４では、転化率及び収率がいずれも高い結果が得られた。また、溶媒は、水よりも、非プロトン性有機溶媒が好ましいことがわかる。
これに対して、比較例１の反応はアルミナ担持ルテニウム触媒の代わりに炭素担持ルテニウム触媒を用いたため、原料はほぼ消失したが、目的物の収率が低くなるとともに、溶媒に不溶の副生成物が生じた。
また、比較例２の反応は、アルミナ担持ルテニウム触媒の代わりにハイドロタルサイト担持金触媒を用いたため、転化率が低く、低収率であった。
As described above, in Examples 1 to 4 using the alumina-supported ruthenium catalyst, high conversion rates and high yields were obtained. Further, it is understood that the solvent is preferably an aprotic organic solvent rather than water.
In contrast, in the reaction of Comparative Example 1, since the ruthenium catalyst supported on carbon was used instead of the ruthenium catalyst supported on alumina, the raw materials almost disappeared, but the yield of the target product was reduced and the by-product insoluble in the solvent was obtained. Occurred.
In the reaction of Comparative Example 2, the conversion was low and the yield was low because the gold catalyst supported on hydrotalcite was used instead of the ruthenium catalyst supported on alumina.
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