JPH03101672A - Preparation of 2,5-furandicarboxyaldehyde - Google Patents
Preparation of 2,5-furandicarboxyaldehydeInfo
- Publication number
- JPH03101672A JPH03101672A JP23961489A JP23961489A JPH03101672A JP H03101672 A JPH03101672 A JP H03101672A JP 23961489 A JP23961489 A JP 23961489A JP 23961489 A JP23961489 A JP 23961489A JP H03101672 A JPH03101672 A JP H03101672A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- formula
- catalyst system
- copper salt
- hydroxymethyl
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- NSQYDLCQAQCMGE-UHFFFAOYSA-N 2-butyl-4-hydroxy-5-methylfuran-3-one Chemical compound CCCCC1OC(C)=C(O)C1=O NSQYDLCQAQCMGE-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- IZWIQVOZAJLLOH-UHFFFAOYSA-N furan-2-ylmethanediol Chemical compound OC(O)C1=CC=CO1 IZWIQVOZAJLLOH-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- AHIXHWRUDZFHEZ-UHFFFAOYSA-N furan-2,3-dicarbaldehyde Chemical compound O=CC=1C=COC=1C=O AHIXHWRUDZFHEZ-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は下記式（ｎ）で表される５−ヒドロキシメチル
−２−フランカルポキシアルデヒド（以下ＩＭＦと記す
）又は下記式（ｍｌ）で表されル２．５−ビスヒドロキ
シメチルフラン（以下ＢＨＭＦと記す）を酸化し、下記
式（ＩＶ）で表される２，５一フランジカルボキシアル
デヒド（以下ＦＤＡと記す）を製造する方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to 5-hydroxymethyl-2-furancarpoxyaldehyde (hereinafter referred to as IMF) represented by the following formula (n) or the following formula (ml). The present invention relates to a method for producing 2,5-furandicarboxyaldehyde (hereinafter referred to as FDA) represented by the following formula (IV) by oxidizing 2,5-bishydroxymethylfuran (hereinafter referred to as BHMF).
（Ｉ［ｒ）
ＦＤＡは高分子モノマー、架橋剤等として注目されてい
る。(I[r) FDA is attracting attention as a polymer monomer, crosslinking agent, etc.
〔従来の技術及び発明が解決しようとする課題〕ＦＤＡ
の製法として、従来、いろいろな方法が提案されている
。[Prior art and problems to be solved by the invention] FDA
Conventionally, various methods have been proposed for the production of .
例えば、ＩＭＦの酸化反応によりＦＤＡを得る方法とし
ては、無水クロム酸錯体を用いる方法（特開昭５４ −
９２６０号公報）、窒素酸化物を用いる方法（特開昭
５５ − ４９３６８号公報）、二酸化マンガンを用い
る方法（ソ連特許第２８２３３１号明細書）などが知ら
れている。また、５−クロロメチル−２−フルフラール
よりＦＤＡを得る方法として、ヘキサメチレンテトラミ
ンと反応させ、生威した４級塩を加水分解する方法（東
独特許第２６５４２号明細書）なども知られている。し
かしながら、これらの方法は反応試薬が比較的高価であ
り、かつ、原料に対して化学量論量必要であるため、経
済的な見地からははなはだ問題の多い方法である。また
、反応試薬の安全性、廃棄処理方法なども問題となるも
のが多い。For example, as a method for obtaining FDA by the oxidation reaction of IMF, there is a method using a chromic anhydride complex (Japanese Unexamined Patent Application Publication No. 54-119)
9260), a method using nitrogen oxides (JP-A-55-49368), and a method using manganese dioxide (USSR Patent No. 282331). Furthermore, as a method for obtaining FDA from 5-chloromethyl-2-furfural, a method is known in which the resulting quaternary salt is hydrolyzed by reaction with hexamethylenetetramine (East German Patent No. 26542). . However, these methods are very problematic from an economic standpoint because the reaction reagents are relatively expensive and are required in stoichiometric amounts relative to the raw materials. In addition, there are many problems such as the safety of reaction reagents and disposal methods.
本発明者はかかる問題点を解決するために鋭意検討を重
ねた結果、ＨＭＦ又はＢＨＭＦを酸化反応するにあたり
、特定の触媒系の存在下に、経済的に有利な酸素又は酸
素含有ガスを用いて酸化したところ、簡便で収率良くか
つ経済的に有利にＦＤ′Ａが得られることを見出し、本
発明を完或するに到った．
即ち本発明は、ＩＭＦ又はＢＨＭＰを、下記式（Ｉ）で
表される２，２．６．６−−テトラメチルピペリジンオ
キシル及び１価の銅塩よりなる触媒系の存在下に、酸素
又は酸素含有ガスを用いて酸化することを特徴とするＦ
ＤＡの製法を提供するものである。As a result of intensive studies to solve these problems, the present inventors have discovered that in oxidizing HMF or BHMF, an economically advantageous oxygen or oxygen-containing gas is used in the presence of a specific catalyst system. Upon oxidation, it was discovered that FD'A could be obtained easily, in good yield, and economically, and the present invention was completed. That is, the present invention provides IMF or BHMP with oxygen or oxygen in the presence of a catalyst system consisting of 2,2.6.6-tetramethylpiperidineoxyl represented by the following formula (I) and a monovalent copper salt. F characterized by being oxidized using a containing gas
This provides a method for producing DA.
（式中ＲはＨ、ＯＨ、炭素数１〜２０のアルコキシ基又
はペンジルオキシ基を表す．）
２．２．６．６−テトラメチルピペリジンオキシル類及
び１価の銅塩を触媒に用いて反応を行う方法に関しては
、アリルアルコール類についてはアルデヒドへの変換に
有効であることは知られているが｛ジャーナル オブ
アメリカン ケミカル ソサイアティ（Ｊｏｕｒｎａｌ
ｏｆ ＡｍｅｒｉｃａｎＣｈｅｍｉｃａｌ Ｓｏｃｉ
ｅｔｙ）， １０６． ３３７４（Ｉ９８４）） 、こ
の文献にはジオール類の酸化によりジアルデヒドを得る
方法については記載がなかった。また、ジオール類を化
学量論量の４−メトキシ−１−オキソー２．２．６．６
−テトラメチルビペリジニウム クロライドで酸化する
とラクトン及びアセタール類が生或することが報告され
ているが、ジアルデヒドの生或は報告されていなかった
｛ジャーナル オブ オーガニック ケミストリー（Ｊ
ｏｕｒｎａｌ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔ
ｒｙ）＋ ５０＋３９３０（Ｉ９８５） ）。即ち、
ＦＤＡを収率良く製造するにあたり、安価な触媒をもっ
て行う方法については全く知られていなかった。(In the formula, R represents H, OH, an alkoxy group having 1 to 20 carbon atoms, or a penzyloxy group.) 2.2.6.6-Tetramethylpiperidineoxyls and a monovalent copper salt are used as catalysts to carry out the reaction. Regarding the method of conversion, it is known that allyl alcohols are effective in converting them to aldehydes, but {Journal of
American Chemical Society (Journal)
of American Chemical Soci
ety), 106. 3374 (I984)), this document did not describe a method for obtaining dialdehydes by oxidizing diols. In addition, diols can be added in a stoichiometric amount of 4-methoxy-1-oxo2.2.6.6
- Tetramethylbiperidinium It has been reported that lactones and acetals are produced when oxidized with chloride, but the production of dialdehydes has not been reported {Journal of Organic Chemistry (J
our own organic chemist
ry)+50+3930(I985)). That is,
There was no known method for producing FDA with a high yield using an inexpensive catalyst.
しかしながら、本発明者らは、ジアルデヒドであるＦＤ
Ａを得るための出発原料となるＨＭＦ又はＢＨＭＦの酸
化反応を前記一般式｛１）で表される２．２，６．６−
−テトラメチルピペリジンオキシルと１価の銅塩よりな
る触媒系存在下に、酸素又は酸素含有ガスにより酸化を
行ったところ、収率良＜ ＦＤＡが生威することを見出
し、本発明を完威したものである．
以下に本発明の詳細な内容を説明する．本発明において
、反応原料として用いられるＩＭＦ ， ＢＨＭＦは、
それぞれヘキソースの脱水反応、フルフリルアルコール
とホルマリンの反応により合威できる。また反応触媒に
用いる前記一般式（Ｉ）で表される２．２，６．６−テ
トラメチルピペリジンオキシルは、２．２，６．６−テ
トラメチルピペリジン又は４−ヒドロキシ−２．２．６
．６−テトラメチルピペリジンよりジャーナル オプオ
ーガニックケ業ストリー（Ｊｏｕｒｎａ１ ｏｆ Ｏｒ
ｇａ−ｎｉｃ Ｃｈｅｍｉｓｔｒｙ）． ５０． １３
３４（Ｉ９８５）に記載の方法によって合戒できる。更
に反応触媒に用いる１価の銅塩としては特に塩化第一銅
が好ましい。However, we found that the dialdehyde FD
The oxidation reaction of HMF or BHMF, which is the starting material for obtaining A, is carried out using the 2.2,6.6-
- When oxidation was carried out with oxygen or oxygen-containing gas in the presence of a catalyst system consisting of tetramethylpiperidineoxyl and a monovalent copper salt, it was discovered that FDA was produced in good yield, and the present invention was completed. It is something. The detailed content of the present invention will be explained below. In the present invention, IMF and BHMF used as reaction raw materials are:
They can be combined by the dehydration reaction of hexose and the reaction of furfuryl alcohol and formalin, respectively. 2.2,6.6-tetramethylpiperidineoxyl represented by the general formula (I) used as a reaction catalyst is 2.2,6.6-tetramethylpiperidine or 4-hydroxy-2.2.6
．． 6-Tetramethylpiperidine from Journal 1 of Or
ga-nic chemistry). 50. 13
34 (I985). Further, as the monovalent copper salt used as a reaction catalyst, cuprous chloride is particularly preferable.
前記一般式（Ｉ）で表される２．２．６．６−テトラメ
チルピペリジンオキシルと１価の銅塩の量比としては１
／０．２〜１０のモル比で使用することが望ましい，
２．２．６．６−テトラメチルピペリジンオキシルは
原料に対して０．０１〜２０モル％使用することが望ま
しい。The quantitative ratio of 2.2.6.6-tetramethylpiperidineoxyl represented by the general formula (I) and the monovalent copper salt is 1.
It is desirable to use it at a molar ratio of /0.2 to 10.
2.2.6.6-Tetramethylpiperidineoxyl is preferably used in an amount of 0.01 to 20 mol% based on the raw materials.
本発明の酸化反応に用いられる溶媒としては、有機溶媒
であれば特に制限は無いが、Ｎ．Ｎ−ジメチルホルムア
ミド、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルアセト
アミド、１−メチル−２ビロリドンなどの非プロトン性
極性溶媒が特に有効である。The solvent used in the oxidation reaction of the present invention is not particularly limited as long as it is an organic solvent. Aprotic polar solvents such as N-dimethylformamide, dimethylsulfoxide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidone are particularly effective.
本発明において、酸素又は酸素含有ガスの導入法は特に
制限はないが、反応原料と触媒を含む溶媒中に導入する
ことが望ましい。In the present invention, the method of introducing oxygen or oxygen-containing gas is not particularly limited, but it is desirable to introduce it into a solvent containing reaction raw materials and a catalyst.
本発明の反応温度はＯ〜５０゜Ｃの範囲が好適な範囲と
して選ばれる。この温度より高くても低くても収率が低
下する。反応時間は反応条件により適宜選択されるが通
常０．５〜１０時間である．〔発明の効果〕
本発明は、高分子七ノマー、架橋剤等として注目される
ＦＤＡについて、ＩＭＦ又はＢＨＭＦより製造するにあ
たり、前記一般式（Ｉ）で表される２，２，６．６−テ
トラメチルピペリジンオキシル及び１価の銅塩を触媒に
用い、経済的に有利な酸素又は酸素含有ガスにて反応さ
せることにより、簡便で収率良くかつ経済的に有利に２
．５−フランジカルボキシアルデヒド（ＦＤＡ）を製造
する方法を提供することができる。The reaction temperature of the present invention is preferably selected from a range of 0 to 50°C. The yield decreases whether the temperature is higher or lower than this temperature. The reaction time is appropriately selected depending on the reaction conditions, but is usually 0.5 to 10 hours. [Effects of the Invention] The present invention provides 2,2,6.6- represented by the general formula (I) when producing FDA from IMF or BHMF, which is attracting attention as a polymer heptanomer, a crosslinking agent, etc. By using tetramethylpiperidine oxyl and a monovalent copper salt as a catalyst and reacting in economically advantageous oxygen or oxygen-containing gas, 2 can be easily and economically advantageously produced with good yield.
．． A method of producing 5-furandicarboxaldehyde (FDA) can be provided.
以下、実施例にて本発明を更に詳細に説明するが、本発
明はこれらの実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１
１００ｓ７の４つロフラスコに、５−ヒドロキシメチル
−２−フラン力ルボキシアルデヒド（ＩＩＭＦ）１．２
６ｇｒ （Ｉ０ｍａ＋ｏｌ） 、４−メトキシ−２．２
，６．６ −テトラメチルピペリジンオキシル０．１８
６ ｇｒ （ １ｌＩＩＩｌｏ■）、塩化第一銅０．９
９ｇｒ （Ｉ＋＋＋ｍｏｌ）、及びジメチルホルムアミ
ド２５−を入れ、２０゜Ｃにて撹拌下酸素を５０ＷＬ！
／ｓｉｎの速度でフラスコの底の部分より導入した。５
時間後、酸素導入を停止し、約３０一のクロロホルム及
び約２０ｇｒのＩＮ塩酸水溶液を加えて、分層した。ク
ロロホルム層をよく水洗し、ｐＨを中性とし硫酸マグネ
シウムで乾燥したのち、クロロホルムを減圧下に留去し
た。Example 1 1.2 5-hydroxymethyl-2-furanic carboxyaldehyde (IIMF) was added to a 100s7 four-bottle flask.
6gr (I0ma+ol), 4-methoxy-2.2
,6.6-tetramethylpiperidineoxyl0.18
6 gr (1lIIIlo■), cuprous chloride 0.9
Add 9gr (I+++mol) and 25-dimethylformamide, and add 50WL of oxygen while stirring at 20°C!
The solution was introduced from the bottom of the flask at a rate of /sin. 5
After an hour, the introduction of oxygen was stopped, and about 30 grams of chloroform and about 20 grams of IN hydrochloric acid aqueous solution were added to separate the layers. The chloroform layer was thoroughly washed with water, the pH was made neutral, and the layer was dried over magnesium sulfate, and then the chloroform was distilled off under reduced pressure.
得られた褐色の残留物は０．９５ｇｒであり、２．５−
フランジカルボキシアルデヒドの純度は７２％であった
（収率５５％）。得られた残留物をクロロホルムで再結
晶したところ融点１１０℃であり、ＮＭＲによりＦＤ＾
であることを確認した。The brown residue obtained was 0.95 gr, 2.5-
The purity of furandicarboxaldehyde was 72% (yield 55%). When the obtained residue was recrystallized from chloroform, it had a melting point of 110°C, and it was found to be FD^ by NMR.
It was confirmed that
ＮＭＲ（｝容媒ＣＤＣｈ）： δ７．４（ｓ），
６９．９（ｓ）実施例２
実施例１において溶媒として用いたジメチルホルムアミ
ドの代わりにジメチルスルホキシドを用いた以外は実施
例ｌと同様に行った結果、ＦＤＡの収率は６２％であっ
た。NMR (}vessel CDCh): δ7.4(s),
69.9(s) Example 2 The same procedure as in Example 1 was performed except that dimethyl sulfoxide was used instead of dimethylformamide used as the solvent in Example 1, and the yield of FDA was 62%.
実施例３
実施例２において、５−ヒドロキシメチル−２−フラン
カルボキシアルデヒド（ＩＭＦ） １．２６ｇｒ（Ｉ０
ｍｍｏｌ）の代わりに２．５−ビスヒドロキシメチルフ
ラン（ＢＨＭＰ） １．２８ｇｒ（Ｉ０ｍｍｏｌ）を用
いた以外は実施例２と同様に行った結果、ＦＤＡの収率
は５６％であった。Example 3 In Example 2, 1.26 gr of 5-hydroxymethyl-2-furancarboxaldehyde (IMF) (IO
Example 2 was repeated except that 1.28 gr (10 mmol) of 2.5-bishydroxymethylfuran (BHMP) was used instead of 2.5-bishydroxymethylfuran (BHMP), and the yield of FDA was 56%.
Claims (1)
ヒド又は２，５−ビスヒドロキシメチルフランを、下記
式（ I ）で表される２，２，６，６−テトラメチルピ
ペリジンオキシル及び１価の銅塩よりなる触媒系の存在
下に、酸素又は酸素含有ガスを用いて酸化することを特
徴とする２，５−フランジカルボキシアルデヒドの製法
。 ▲数式、化学式、表等があります▼・・・（ I ） （式中ＲはＨ、ＯＨ、炭素数１〜２０のアルコキシ基又
はベンジルオキシ基を表す。）[Scope of Claims] 5-hydroxymethyl-2-furancarboxaldehyde or 2,5-bishydroxymethylfuran is combined with 2,2,6,6-tetramethylpiperidineoxyl represented by the following formula (I) and 1 1. A method for producing 2,5-furandicarboxaldehyde, which comprises oxidizing it using oxygen or an oxygen-containing gas in the presence of a catalyst system consisting of a copper salt having a hydric acid. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R represents H, OH, an alkoxy group having 1 to 20 carbon atoms, or a benzyloxy group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23961489A JPH03101672A (en) | 1989-09-14 | 1989-09-14 | Preparation of 2,5-furandicarboxyaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23961489A JPH03101672A (en) | 1989-09-14 | 1989-09-14 | Preparation of 2,5-furandicarboxyaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03101672A true JPH03101672A (en) | 1991-04-26 |
Family
ID=17047358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23961489A Pending JPH03101672A (en) | 1989-09-14 | 1989-09-14 | Preparation of 2,5-furandicarboxyaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03101672A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001072732A2 (en) * | 2000-03-27 | 2001-10-04 | E.I. Dupont De Nemours And Company | Oxidation of 5-(hydroxymethyl) furfural to 2,5-diformylfuran and subsequent decarbonylation to unsubstituted furan |
| US7432382B2 (en) * | 2004-12-10 | 2008-10-07 | Archer-Daniels-Midland Company | Conversion of 2,5-(hydroxymethyl)furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
| US7700788B2 (en) | 2006-10-31 | 2010-04-20 | Battelle Memorial Institute | Hydroxymethyl furfural oxidation methods |
| WO2012004069A1 (en) * | 2010-07-06 | 2012-01-12 | Evonik Degussa Gmbh | Process for producing 2,5-diformylfuran and derivatives thereof |
-
1989
- 1989-09-14 JP JP23961489A patent/JPH03101672A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001072732A2 (en) * | 2000-03-27 | 2001-10-04 | E.I. Dupont De Nemours And Company | Oxidation of 5-(hydroxymethyl) furfural to 2,5-diformylfuran and subsequent decarbonylation to unsubstituted furan |
| WO2001072732A3 (en) * | 2000-03-27 | 2002-07-25 | Du Pont | Oxidation of 5-(hydroxymethyl) furfural to 2,5-diformylfuran and subsequent decarbonylation to unsubstituted furan |
| US7432382B2 (en) * | 2004-12-10 | 2008-10-07 | Archer-Daniels-Midland Company | Conversion of 2,5-(hydroxymethyl)furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
| US7579490B2 (en) | 2004-12-10 | 2009-08-25 | Archer-Daniels-Midland Company | Conversion of 2,5-(hydroxymethyl)furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
| US7700788B2 (en) | 2006-10-31 | 2010-04-20 | Battelle Memorial Institute | Hydroxymethyl furfural oxidation methods |
| US8193381B2 (en) | 2006-10-31 | 2012-06-05 | Battelle Memorial Institute | Hydroxymethyl furfural oxidation methods |
| US8193382B2 (en) | 2006-10-31 | 2012-06-05 | Battelle Memorial Institute | Hydroxymethyl furfural oxidation methods |
| WO2012004069A1 (en) * | 2010-07-06 | 2012-01-12 | Evonik Degussa Gmbh | Process for producing 2,5-diformylfuran and derivatives thereof |
| DE102010030991A1 (en) * | 2010-07-06 | 2012-01-12 | Evonik Degussa Gmbh | Process for the preparation of 2,5-diformylfuran and its derivatives |
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