JP3795970B2 - Method for producing α, β-unsaturated aldehyde - Google Patents
Method for producing α, β-unsaturated aldehyde Download PDFInfo
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- JP3795970B2 JP3795970B2 JP21720196A JP21720196A JP3795970B2 JP 3795970 B2 JP3795970 B2 JP 3795970B2 JP 21720196 A JP21720196 A JP 21720196A JP 21720196 A JP21720196 A JP 21720196A JP 3795970 B2 JP3795970 B2 JP 3795970B2
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- reaction
- ion exchange
- exchange resin
- cationic ion
- unsaturated aldehyde
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- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 150000001299 aldehydes Chemical class 0.000 claims description 15
- 239000003729 cation exchange resin Substances 0.000 claims description 15
- 238000005882 aldol condensation reaction Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 14
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- ACWQBUSCFPJUPN-HWKANZROSA-N trans-2-methyl-2-butenal Chemical compound C\C=C(/C)C=O ACWQBUSCFPJUPN-HWKANZROSA-N 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
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- 238000006482 condensation reaction Methods 0.000 description 4
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BYGQBDHUGHBGMD-UHFFFAOYSA-N 2-methylbutanal Chemical compound CCC(C)C=O BYGQBDHUGHBGMD-UHFFFAOYSA-N 0.000 description 2
- GMLDCZYTIPCVMO-UHFFFAOYSA-N 2-methylidenebutanal Chemical compound CCC(=C)C=O GMLDCZYTIPCVMO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 2
- IQGZCSXWIRBTRW-ZZXKWVIFSA-N (2E)-2-ethyl-2-butenal Chemical compound CC\C(=C/C)C=O IQGZCSXWIRBTRW-ZZXKWVIFSA-N 0.000 description 1
- 239000001893 (2R)-2-methylbutanal Substances 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals 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
- 239000002585 base Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000007429 general method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、α，β−不飽和アルデヒドの製造方法に関する。本発明により製造されるα，β−不飽和アルデヒド、例えばチグリンアルデヒド（トランス−２−メチル−２−ブテナール）は、各種テルペン類の合成原料として有用である。また、チグリンアルデヒド誘導体であるチグリン酸（トランス−２−メチル−２−ブテン酸）は、香料、インク等の乾燥剤の合成原料として有用である。
【０００２】
【従来の技術】
α，β−不飽和アルデヒドの製造方法としては、▲１▼アセトアルデヒドとプロピオンアルデヒドとを、水酸化ナトリウムを用いて交差アルドール縮合反応させることによりチグリンアルデヒドを得る方法［ジャーナル オブ ザ ケミカルソサエティー（Journal of the Chemical Society)、３２６２頁（１９５７年）参照］、▲２▼２−エチルアクロレインを水素ガスの存在下、パラジウム触媒を用いて異性化させ、チグリンアルデヒドを得る方法（特開昭６１−３３１３７号公報参照）等が知られている。
【０００３】
【発明が解決しようとする課題】
しかしながら、上記▲１▼の方法は、多くの副生成物が生じ、目的物の収率が低いこと、反応条件の制御が困難であること、反応の後処理として、触媒として用いた塩基（水酸化ナトリウム）の中和が必要となる等の操作的な煩雑さを伴うこと等の問題点を有している。また、上記▲２▼の方法では、副反応として２−エチルアクロレインの水素付加反応が進行し、２−メチルブタナールが生成する。この２−エチルアクロレインの水素付加反応は、収率の低下を引き起こすのみならず、粗生成物の精製操作が複雑になるという欠点を伴う。さらに、この水素付加反応を抑制するためには、チオ尿素、チオフェン等のような硫黄化合物による触媒の不活性化が必要となる。したがって、これらの方法は、α，β−不飽和アルデヒドの工業的に優れた製造方法であるとは言い難い。
しかして、本発明の目的は、α，β−不飽和アルデヒドを簡便に、高純度、高収率で製造する方法を提供することにある。
【０００４】
【課題を解決するための手段】
本発明によれば、上記の目的は、アセトアルデヒドと一般式（Ｉ）
【０００５】
【化３】
（式中、Ｒはアルキル基を表す。）
で示されるアルデヒドとを、カチオン性イオン交換樹脂を用いて交差アルドール縮合反応させることを特徴とする一般式（II）
【０００７】
【化４】
（式中、Ｒは前記定義のとおりである。）
で示されるα，β−不飽和アルデヒドの製造方法を提供することによって達成される。
【０００９】
【発明の実施の形態】
上記一般式（Ｉ）および（II）においてＲが表すアルキル基は、直鎖状または分岐鎖状のいずれでもよく、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基等が挙げられる。
【００１０】
本発明において使用されるカチオン性イオン交換樹脂としては、例えば強酸性スルホン酸基を含有するものが挙げられる。スルホン酸基は、遊離のスルホン酸基であっても、部分的にアルカリ金属またはアルカリ土類金属の酸性塩として存在していてもよいが、一般に遊離のスルホン酸基が有利である。
【００１１】
本発明の反応は、溶媒の存在下または不存在下に行うことが可能である。使用する溶媒は、原料とのアルドール反応を起こす等の悪影響を与えない限り特に限定されるものではないが、例えばジクロロメタン、クロロホルム、四塩化炭素、１，２−ジクロロエタン、１，１，２，２−テトラクロロエタン等のハロゲン系炭化水素；ベンゼン、トルエン、キシレン、クメン、ヘプタン、オクタン等の炭化水素；ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン、ジメトキシエタン等のエーテル；アセトニトリル、プロピオニトリル等のニトリル等が挙げられる。溶媒の使用量はアセトアルデヒドに対して０．１〜１０重量倍が好ましく、０．１〜１．０重量倍がより好ましい。
【００１２】
反応は、常圧下または加圧下において行うことができるが、不活性ガスによる加圧下において行うのが好ましい。反応温度は０〜１５０℃の範囲が好ましく、８０〜１２０℃の範囲がより好ましい。また、反応時間は反応温度により異なるが、１０〜１２０分の範囲が好ましく、１０〜１００分の範囲がより好ましい。
【００１３】
カチオン性イオン交換樹脂と別離することにより得られた反応混合物からのα，β−不飽和アルデヒドの単離精製は、一般的方法により行うことができる。例えば、反応混合物を静置し、有機層と水層とを分液し、有機層を常圧下、必要ならば減圧下にて蒸留精製することにより行う。
【００１４】
【実施例】
以下に実施例により本発明をさらに詳細に説明するが、本発明はこれらの実施例によりなんら限定されるものではない。
【００１５】
実施例１
カチオン性イオン交換樹脂［ダウエックス−５０Ｗ（ＤＯＷＥＸ−５０Ｗ）；ダウケミカル社製］６２０ｍｇを１００ｍｌ容ステンレス製耐圧反応容器中に入れ、次いでアセトアルデヒドおよびプロピオンアルデヒドの等モル混合液３８．７ｇ（各３７９ｍｍｏｌ）を導入し、その後、窒素ガスにより１０ｋｇ／ｃｍ2 に加圧し、１２０℃にて１００分間反応させた。反応終了後、反応混合液とカチオン性イオン交換樹脂を濾別し、縮合反応により生成した水を分液ロートにより分液した。その後、有機層を常圧にて精密に蒸留し、チグリンアルデヒドを２２．３ｇ（２６６ｍｍｏｌ）得た。
収率：７０．２％
純度：９８．８％
沸点：１１８〜１２０℃
1Ｈ−ＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ3 ），δ：
１．７９（ｓ，３Ｈ），１．９７（ｄ，３Ｈ），６．６７（ｑ，１Ｈ），９．３８（ｓ，１Ｈ）
【００１６】
実施例２
カチオン性イオン交換樹脂［アンバーリスト−１５Ｅ（Ａｍｂｅｒｌｙｓｔ−１５Ｅ）；オルガノ社製］５０ｍｇを１００ｍｌ容ステンレス製耐圧反応容器中に入れ、次いでアセトアルデヒドおよびプロピオンアルデヒドの等モル混合液５４．７ｇ（各５３６ｍｍｏｌ）を導入し、その後、窒素ガスにより１０ｋｇ／ｃｍ2 に加圧し、１２０℃にて１００分間反応させた。反応終了後、反応混合液とカチオン性イオン交換樹脂を濾別し、縮合反応により生成した水を分液ロートにより分液した。その後、有機層を精密に蒸留し、チグリンアルデヒドを３２．４ｇ（３８６ｍｍｏｌ）得た。
収率：７２．０％
純度：９８．１％
【００１７】
実施例３
カチオン性イオン交換樹脂［アンバーライトＩＲ−１２０Ｂ（Ａｍｂｅｒｌｉｔｅ ＩＲ−１２０Ｂ）；オルガノ社製］６２ｍｇを１００ｍｌ容ステンレス製耐圧反応容器中に入れ、次いでアセトアルデヒドおよびプロピオンアルデヒドの等モル混合液４８．５ｇ（各４７５ｍｍｏｌ）を導入し、その後、窒素ガスにより１０ｋｇ／ｃｍ2 に加圧し、１２０℃にて１００分間反応させた。反応終了後、反応混合液とカチオン性イオン交換樹脂を濾別し、縮合反応により生成した水を分液ロートにより分液した。その後、有機層を精密に蒸留し、チグリンアルデヒドを２７．６ｇ（３２９ｍｍｏｌ）得た。
収率：６９．２％
純度：９８．５％
【００１８】
実施例４
カチオン性イオン交換樹脂［ダウエックス−５０Ｗ（ＤＯＷＥＸ−５０Ｗ）；ダウケミカル社製］６．５ｇを充填し、加圧下（Ｎ2 、１０ｋｇ／ｃｍ2 ）、１００℃に加熱された反応管（内容積１２．０ｍｌ）中へ、アセトアルデヒドおよびプロピオンアルデヒドの等モル混合液を、流速４２ｍｌ／時間となるように送液ポンプを用いて８時間送液した（送液量３３６ｍｌ、２６９ｇ、各２．６４ｍｏｌ）。流出液の有機層を精密に蒸留し、チグリンアルデヒド１５３．１ｇ（１．８２ｍｏｌ）を得た。
収率：７０．０％
純度：９８．４％
【００１９】
実施例５
カチオン性イオン交換樹脂［アンバーリスト−１５Ｅ（Ａｍｂｅｒｌｙｓｔ−１５Ｅ）；オルガノ社製］６．０ｇを充填し、加圧下（Ｎ2 、１０ｋｇ／ｃｍ2 ）、１００℃に加熱された反応管（内容積１２．０ｍｌ）中へ、アセトアルデヒドおよびプロピオンアルデヒドの等モル混合液を、流速６０ｍｌ／時間となるように送液ポンプを用いて８時間送液した（送液量４８０ｍｌ、３８４ｇ、各３．７６ｍｏｌ）。流出液の有機層を精密に蒸留し、チグリンアルデヒド２２１．２ｇ（２．６３ｍｏｌ）を得た。
収率：６９．０％
純度：９８．１％
【００２０】
実施例６
カチオン性イオン交換樹脂［アンバーリスト−１５Ｅ（Ａｍｂｅｒｌｙｓｔ−１５Ｅ）；オルガノ社製］２００ｇを充填し、加圧下（Ｎ2 、１０ｋｇ／ｃｍ2 ）、１００℃に加熱された反応管（内容積４００ｍｌ）中へ、アセトアルデヒドおよびプロピオンアルデヒドの等モル混合液を、流速２０００ｍｌ／時間となるように送液ポンプを用いて１０時間送液した（送液量２００００ｍｌ、１６．０ｋｇ、各１５７ｍｏｌ）。流出液の有機層を精密に蒸留し、チグリンアルデヒド９．１０ｋｇ（１０８ｍｏｌ）を得た。
収率：６９．０％
純度：９８．１％
【００２１】
実施例７
カチオン性イオン交換樹脂［アンバーリスト−１５Ｅ（Ａｍｂｅｒｌｙｓｔ−１５Ｅ）；オルガノ社製］３８０ｍｇを５００ｍｌ容ステンレス製耐圧反応容器中に入れ、次いでアセトアルデヒドおよびブチルアルデヒドの等モル混合液１１７ｇ（各１．０ｍｏｌ）を導入し、その後、窒素ガスにより１０ｋｇ／ｃｍ2 に加圧し、１２０℃にて１００分間反応させた。反応終了後、反応混合液とカチオン性イオン交換樹脂を濾別し、縮合反応により生成した水を分液ロートにより分液した。その後、有機層を精密に蒸留し、２−エチルクロトンアルデヒドを６８．６ｇ（０．７０ｍｏｌ）得た。
収率：７０．０％
純度：９７．８％
沸点：１３２〜１３４℃
1Ｈ−ＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ3 ），δ：
１．５８（ｔ，３Ｈ），１．７５（ｑ，３Ｈ），２．０１（ｄ，３Ｈ），６．８１（ｑ，１Ｈ），９．４０（ｓ，１Ｈ）
【００２２】
【発明の効果】
本発明によれば、穏和な条件下、簡便にα，β−不飽和アルデヒドを工業的に有利に製造する方法が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an α, β-unsaturated aldehyde. The α, β-unsaturated aldehyde produced by the present invention, for example, tigulin aldehyde (trans-2-methyl-2-butenal) is useful as a raw material for synthesizing various terpenes. Further, tiglinic acid (trans-2-methyl-2-butenoic acid), which is a tiglinaldehyde derivative, is useful as a synthetic raw material for desiccants such as fragrances and inks.
[0002]
[Prior art]
As a method for producing α, β-unsaturated aldehyde, (1) a method of obtaining a tigulin aldehyde by cross-aldol condensation reaction between acetaldehyde and propionaldehyde using sodium hydroxide [Journal of the Chemical Society ( Journal of the Chemical Society), page 3262 (1957)], {circle around (2)} 2-ethylacrolein is isomerized using a palladium catalyst in the presence of hydrogen gas to obtain tiglinaldehyde (JP-A-61). No. 33137) is known.
[0003]
[Problems to be solved by the invention]
However, in the method (1), many by-products are produced, the yield of the target product is low, the reaction conditions are difficult to control, and the base (water) used as a catalyst as a post-treatment of the reaction. (Sodium oxide) has a problem that it involves operational complexity such as necessitating neutralization. In the method (2), a hydrogenation reaction of 2-ethylacrolein proceeds as a side reaction to produce 2-methylbutanal. This hydrogenation reaction of 2-ethylacrolein not only causes a decrease in yield, but also has the disadvantage that the purification operation of the crude product becomes complicated. Furthermore, in order to suppress this hydrogenation reaction, it is necessary to deactivate the catalyst with a sulfur compound such as thiourea or thiophene. Therefore, it cannot be said that these methods are industrially excellent production methods for α, β-unsaturated aldehydes.
Therefore, an object of the present invention is to provide a method for producing an α, β-unsaturated aldehyde simply and with high purity and high yield.
[0004]
[Means for Solving the Problems]
According to the present invention, the object is to achieve acetaldehyde and general formula (I)
[0005]
[Chemical 3]
(In the formula, R represents an alkyl group.)
A cross-aldol condensation reaction with an aldehyde represented by the general formula (II) using a cationic ion exchange resin
[0007]
[Formula 4]
(Wherein R is as defined above.)
It is achieved by providing a method for producing an α, β-unsaturated aldehyde represented by the formula:
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The alkyl group represented by R in the above general formulas (I) and (II) may be linear or branched, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group Group, decyl group and the like.
[0010]
Examples of the cationic ion exchange resin used in the present invention include those containing a strongly acidic sulfonic acid group. The sulfonic acid group may be a free sulfonic acid group or partly present as an alkali metal or alkaline earth metal acid salt, but generally a free sulfonic acid group is preferred.
[0011]
The reaction of the present invention can be carried out in the presence or absence of a solvent. The solvent to be used is not particularly limited as long as it does not cause an adverse effect such as causing an aldol reaction with the raw material. For example, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2 -Halogen hydrocarbons such as tetrachloroethane; hydrocarbons such as benzene, toluene, xylene, cumene, heptane, octane; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, dimethoxyethane; acetonitrile, propionitrile And nitriles. 0.1-10 weight times is preferable with respect to acetaldehyde, and, as for the usage-amount of a solvent, 0.1-1.0 weight times is more preferable.
[0012]
The reaction can be performed under normal pressure or under pressure, but is preferably performed under pressure with an inert gas. The reaction temperature is preferably in the range of 0 to 150 ° C, more preferably in the range of 80 to 120 ° C. Moreover, although reaction time changes with reaction temperature, the range for 10 to 120 minutes is preferable, and the range for 10 to 100 minutes is more preferable.
[0013]
Isolation and purification of the α, β-unsaturated aldehyde from the reaction mixture obtained by separating from the cationic ion exchange resin can be performed by a general method. For example, the reaction mixture is allowed to stand, the organic layer and the aqueous layer are separated, and the organic layer is purified by distillation under normal pressure, if necessary, under reduced pressure.
[0014]
【Example】
EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
[0015]
Example 1
Cationic ion exchange resin [Dowex-50W (DOWEX-50W); manufactured by Dow Chemical Co., Ltd.] 620 mg was placed in a 100 ml stainless steel pressure-resistant reaction vessel, and then 38.7 g (379 mmol each) of an equimolar mixture of acetaldehyde and propionaldehyde. Then, the pressure was increased to 10 kg / cm 2 with nitrogen gas, and the mixture was reacted at 120 ° C. for 100 minutes. After completion of the reaction, the reaction mixture and the cationic ion exchange resin were separated by filtration, and water produced by the condensation reaction was separated using a separatory funnel. Thereafter, the organic layer was precisely distilled at normal pressure to obtain 22.3 g (266 mmol) of tiglinaldehyde.
Yield: 70.2%
Purity: 98.8%
Boiling point: 118-120 ° C
1 H-NMR (270 MHz, CDCl 3), δ :
1.79 (s, 3H), 1.97 (d, 3H), 6.67 (q, 1H), 9.38 (s, 1H)
[0016]
Example 2
Cationic ion exchange resin [Amberlyst-15E (Amberlyst-15E); manufactured by Organo Corporation] 50 mg was placed in a 100 ml stainless steel pressure-resistant reaction vessel, and then 54.7 g (536 mmol each) of an equimolar mixture of acetaldehyde and propionaldehyde. After that, it was pressurized to 10 kg / cm 2 with nitrogen gas and reacted at 120 ° C. for 100 minutes . After completion of the reaction, the reaction mixture and the cationic ion exchange resin were separated by filtration, and water produced by the condensation reaction was separated using a separatory funnel. Thereafter, the organic layer was distilled precisely to obtain 32.4 g (386 mmol) of tigulin aldehyde.
Yield: 72. 0 %
Purity: 98.1%
[0017]
Example 3
62 mg of a cationic ion exchange resin [Amberlite IR-120B (manufactured by Organo)] was placed in a 100 ml stainless steel pressure-resistant reaction vessel, and then 48.5 g of an equimolar mixture of acetaldehyde and propionaldehyde (each 475 mmol) was introduced, and then pressurized to 10 kg / cm 2 with nitrogen gas and reacted at 120 ° C. for 100 minutes. After completion of the reaction, the reaction mixture and the cationic ion exchange resin were separated by filtration, and water produced by the condensation reaction was separated using a separatory funnel. Thereafter, the organic layer was precisely distilled to obtain 27.6 g (329 mmol) of tigulin aldehyde.
Yield: 69.2%
Purity: 98.5%
[0018]
Example 4
Cationic ion exchange resin [Dowex-50W (DOWEX-50W); manufactured by Dow Chemical Co., Ltd.] 6.5 g, reaction tube heated to 100 ° C. under pressure (N 2 , 10 kg / cm 2 ) (contents) 12.0 ml), an equimolar mixture of acetaldehyde and propionaldehyde was fed for 8 hours using a feed pump so that the flow rate was 42 ml / hour (liquid feed amount 336 ml, 269 g, 2.64 mol each). ). The organic layer of the effluent was distilled precisely to obtain 153.1 g (1.82 mol) of tiglinaldehyde.
Yield: 70.0%
Purity: 98.4%
[0019]
Example 5
Cationic ion exchange resin [Amberlyst-15E (Amberlyst-15E); manufactured by Organo Corporation] 6.0 g, and heated to 100 ° C. under pressure (N 2, 10 kg / cm 2 ) (internal volume 12) 0.0 ml), an equimolar mixture of acetaldehyde and propionaldehyde was fed for 8 hours using a feed pump at a flow rate of 60 ml / hour (amount of liquid fed 480 ml, 384 g, 3.76 mol each). The organic layer of the effluent was precisely distilled to obtain 221.2 g (2.63 mol) of tiglinaldehyde.
Yield: 69.0%
Purity: 98.1%
[0020]
Example 6
Cationic ion exchange resin [Amberlyst-15E (Amberlyst-15E); manufactured by Organo Corporation] 200 g was charged in a reaction tube (internal volume 400 ml) heated to 100 ° C. under pressure (N 2, 10 kg / cm 2 ) . To the solution, an equimolar mixture of acetaldehyde and propionaldehyde was fed for 10 hours using a feeding pump so that the flow rate was 2000 ml / hour (feeding amount 20000 ml, 16.0 kg, 157 mol each). The organic layer of the effluent was distilled precisely to obtain 9.10 kg (108 mol) of tiglinaldehyde.
Yield: 69.0%
Purity: 98.1%
[0021]
Example 7
380 mg of a cationic ion exchange resin [Amberlyst-15E (Amberlyst-15E); manufactured by Organo Corporation] was placed in a 500 ml stainless steel pressure-resistant reaction vessel, and then 117 g (1.0 mol each) of an equimolar mixture of acetaldehyde and butyraldehyde. It was introduced and then pressurized to 10 kg / cm 2 with nitrogen gas, and reacted for 100 minutes at 120 ° C.. After completion of the reaction, the reaction mixture and the cationic ion exchange resin were separated by filtration, and water produced by the condensation reaction was separated using a separatory funnel. Thereafter, the organic layer was distilled precisely to obtain 68.6 g (0.70 mol) of 2-ethylcrotonaldehyde.
Yield: 70.0%
Purity: 97.8%
Boiling point: 132-134 ° C
1 H-NMR (270 MHz, CDCl 3), δ :
1.58 (t, 3H), 1.75 (q, 3H), 2.01 (d, 3H), 6.81 (q, 1H), 9.40 (s, 1H)
[0022]
【The invention's effect】
According to the present invention, there is provided a method for industrially advantageously producing an α, β-unsaturated aldehyde easily under mild conditions.
Claims (1)
で示されるアルデヒドとを、カチオン性イオン交換樹脂を用いて交差アルドール縮合反応させることを特徴とする一般式（II）
で示されるα，β−不飽和アルデヒドの製造方法。Acetaldehyde and general formula (I)
A cross-aldol condensation reaction with an aldehyde represented by the general formula (II) using a cationic ion exchange resin
The manufacturing method of the alpha, beta-unsaturated aldehyde shown by these.
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|---|---|---|---|
| JP21720196A JP3795970B2 (en) | 1996-08-19 | 1996-08-19 | Method for producing α, β-unsaturated aldehyde |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21720196A JP3795970B2 (en) | 1996-08-19 | 1996-08-19 | Method for producing α, β-unsaturated aldehyde |
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| Publication Number | Publication Date |
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| JP3795970B2 true JP3795970B2 (en) | 2006-07-12 |
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| EP1997796A1 (en) * | 2007-06-01 | 2008-12-03 | DSMIP Assets B.V. | Aldol condensation reaction and catalyst therefore |
| US8742177B2 (en) * | 2011-12-28 | 2014-06-03 | Rohm And Haas Company | Catalyst and process to produce branched unsaturated aldehydes |
| CN103804160B (en) * | 2014-01-27 | 2016-03-02 | 南京运华立太能源科技有限公司 | The preparation method of 3-methyl-3-amylene-2-ketone |
| WO2022019142A1 (en) * | 2020-07-20 | 2022-01-27 | 花王株式会社 | α,β-UNSATURATED ALDEHYDE PRODUCTION METHOD |
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