JP2008214330A - Selective oxidation method of alcohol using bismuthonium salt - Google Patents
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 23
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title description 20
- YRPWLKVCRKAUAO-UHFFFAOYSA-N bismuthonium Chemical class [BiH4+] YRPWLKVCRKAUAO-UHFFFAOYSA-N 0.000 title description 9
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 12
- 150000002576 ketones Chemical class 0.000 claims abstract description 9
- 150000001298 alcohols Chemical class 0.000 claims abstract description 7
- -1 tetrafluoroborate Chemical compound 0.000 claims description 13
- 150000003138 primary alcohols Chemical class 0.000 claims description 10
- 150000003333 secondary alcohols Chemical class 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- RAGWYBYSIJKINM-UHFFFAOYSA-N C1(=CC=CC=C1)[Bi+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical class C1(=CC=CC=C1)[Bi+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 RAGWYBYSIJKINM-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- NKLCNNUWBJBICK-UHFFFAOYSA-N dess–martin periodinane Chemical compound C1=CC=C2I(OC(=O)C)(OC(C)=O)(OC(C)=O)OC(=O)C2=C1 NKLCNNUWBJBICK-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 5
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 5
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 4
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 4
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 2
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 2
- 239000012027 Collins reagent Substances 0.000 description 2
- 241000134874 Geraniales Species 0.000 description 2
- 239000005792 Geraniol Substances 0.000 description 2
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 2
- 239000003810 Jones reagent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000006859 Swern oxidation reaction Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 150000001622 bismuth compounds Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 229940113087 geraniol Drugs 0.000 description 2
- JQOAQUXIUNVRQW-UHFFFAOYSA-N hexane Chemical compound CCCCCC.CCCCCC JQOAQUXIUNVRQW-UHFFFAOYSA-N 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NPRDHMWYZHSAHR-UHFFFAOYSA-N pyridine;trioxochromium Chemical compound O=[Cr](=O)=O.C1=CC=NC=C1.C1=CC=NC=C1 NPRDHMWYZHSAHR-UHFFFAOYSA-N 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- ACWMCRWUAMHPEO-UHFFFAOYSA-N triphenylbismuthane;dihydrate Chemical compound O.O.C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ACWMCRWUAMHPEO-UHFFFAOYSA-N 0.000 description 2
- BZXQRXJJJUZZAJ-UHFFFAOYSA-N (2,4,6-trimethylphenyl)boronic acid Chemical compound CC1=CC(C)=C(B(O)O)C(C)=C1 BZXQRXJJJUZZAJ-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- YQHJFPFNGVDEDT-UHFFFAOYSA-N 2-tert-butyl-1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(N(C)C)=NC(C)(C)C YQHJFPFNGVDEDT-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- OSGJIYNQSIPLAQ-UHFFFAOYSA-L difluoro(triphenyl)bismuth Chemical compound C=1C=CC=CC=1[Bi](F)(C=1C=CC=CC=1)(F)C1=CC=CC=C1 OSGJIYNQSIPLAQ-UHFFFAOYSA-L 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- RCBVKBFIWMOMHF-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium;pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1.O[Cr](=O)(=O)O[Cr](O)(=O)=O RCBVKBFIWMOMHF-UHFFFAOYSA-L 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000006502 papoula Nutrition 0.000 description 1
- 244000224362 papoula Species 0.000 description 1
- 239000011388 polymer cement concrete Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明はビスムトニウム塩を用いたアルコールの酸化法に関するものである。この酸化法は第一級アルコールをアルデヒドに，第二級アルコールをケトンに変換するものであって，有機合成の属する分野および他の分野において要求されている温和な条件下でのアルコール類の選択的酸化に供するものである。 The present invention relates to an alcohol oxidation method using a bismuthonium salt. This oxidation method converts primary alcohols to aldehydes and secondary alcohols to ketones. Selection of alcohols under the mild conditions required in the fields of organic synthesis and other fields. It is used for selective oxidation.
第一級アルコールをアルデヒドに，第二級アルコールをケトンに酸化する反応は有機合成上最も重要な反応の１つであり，Ｊｏｎｅｓ試薬，Ｓａｒｅｔｔ試薬，Ｃｏｌｌｉｎｓ試薬などの酸化クロムを利用する酸化剤が用いられてきた。そして，アルコールのアルデヒドあるいはケトンへの酸化反応が極めて重要であるため，より有用な酸化法の開発を意図して活発な研究が行われ，数多くの優れた方法が次々と開発されている。例えば，Ｃｏｒｅｙらはジクロロメタン中，ピリジニウムクロロクロマート（以下，ＰＣＣ）を用いてアルコールを酸化し，高収率でアルデヒドを得ている（非特許文献１参照）。同じくＣｏｒｅｙらはジクロロメタン中，ピリジニウムジクロマート（以下，ＰＤＣ）を用いてデカノールを酸化し，収率９８％でデカナールを得ている（非特許文献２参照）。酸化クロムのような重金属化合物に代わる酸化剤として，超原子価ヨウ素化合物である１，１，１−トリアセトキシ−１，１−ジヒドロ−１，２−ベンゾヨードキソール−３（１Ｈ）−オン（以下，Ｄｅｓｓ−Ｍａｒｔｉｎペルヨージナン）が開発され，アルコールの選択的な酸化剤として用いられている（非特許文献３参照）。また，ジメチルスルホキシド（以下，ＤＭＳＯ）を活性化してアルコールと反応させ，アルデヒドに導く方法がある。その中でもオキザリルジクロリドを活性化剤として用いるＳｗｅｒｎ酸化は広く利用されている（非特許文献４参照）。 The reaction that oxidizes primary alcohol to aldehyde and secondary alcohol to ketone is one of the most important reactions in organic synthesis. Oxidizing agents using chromium oxide such as Jones reagent, Sarett reagent, Collins reagent, etc. Has been used. Since the oxidation reaction of alcohol to aldehyde or ketone is extremely important, active research has been conducted with the aim of developing more useful oxidation methods, and many excellent methods have been developed one after another. For example, Corey et al. Oxidize alcohol using pyridinium chlorochromate (hereinafter, PCC) in dichloromethane to obtain an aldehyde in high yield (see Non-Patent Document 1). Similarly, Corey et al. Oxidized decanol using pyridinium dichromate (hereinafter referred to as PDC) in dichloromethane to obtain decanal in a yield of 98% (see Non-Patent Document 2). 1,1,1-triacetoxy-1,1-dihydro-1,2-benzoiodoxol-3 (1H) -one, a hypervalent iodine compound, as an oxidant to replace heavy metal compounds such as chromium oxide (Hereinafter, Dess-Martin periodinane) has been developed and used as a selective oxidizing agent for alcohol (see Non-Patent Document 3). Further, there is a method in which dimethyl sulfoxide (hereinafter referred to as DMSO) is activated and reacted with alcohol to lead to aldehyde. Among them, Swern oxidation using oxalyl dichloride as an activator is widely used (see Non-Patent Document 4).
一方，超原子価ビスマス化合物はその酸化能力とビスマス元素の低い毒性から，酸化剤として注目されている。例えば，Ｃｈａｌｌｅｎｇｅｒらはトリフェニルビスマスジヒドロキシドを用いてアルコールを対応するアルデヒド，ケトンに酸化している（非特許文献５参照）。Ｂａｒｔｏｎらは（Ｐｈ３ＢｉＣｌ）２Ｏを，ＤｏｄｏｎｏｖはＰｈ３Ｂｉ（ＯＡｃ）２を用いて中性もしくは塩基性条件下，対応するカルボニル化合物を得ている（非特許文献６，７参照）。また，テトラアリールビスムトニウム塩を用いたアルコールの酸化も報告されている（非特許文献８参照）。On the other hand, hypervalent bismuth compounds are attracting attention as oxidizing agents because of their oxidizing ability and low toxicity of bismuth elements. For example, Challenger et al. Uses triphenylbismuth dihydroxide to oxidize alcohol to the corresponding aldehyde and ketone (see Non-Patent Document 5). Barton et al. (Ph 3 BiCl) 2 O and Dodonov obtained Ph 3 Bi (OAc) 2 to obtain the corresponding carbonyl compounds under neutral or basic conditions (see Non-Patent Documents 6 and 7). Moreover, the oxidation of alcohol using a tetraaryl bismuthonium salt has also been reported (see Non-Patent Document 8).
しかしながら，Ｊｏｎｅｓ試薬，Ｓａｒｅｔｔ試薬，Ｃｏｌｌｉｎｓ試薬，ＰＣＣ，ＰＤＣは，いずれも毒性の高い重金属酸化物を酸化剤として利用している。しかも，反応終了後，重金属酸化物を目的物から完全に除去する操作が煩雑であるという問題点を有している。Ｄｅｓｓ−Ｍａｒｔｉｎペルヨージナンを用いる方法は，高収率で目的物を得ることができるが，Ｄｅｓｓ−ＭａｒｔｉｎペルヨージナンおよびＤｅｓｓ−Ｍａｒｔｉｎペルヨージナンの加水分解物に強い爆発性が報告されている。そのため，この方法の使用には細心の注意が必要であり，利用し易い方法とは言い難い。Ｓｗｅｒｎ酸化は，毒性の強い重金属酸化物や爆発性の酸化剤を使用しない優れた方法である。しかしながら，活性化ＤＭＳＯとアルコールとが反応した中間体は極めて不安定であり，そのため，厳密な温度管理下（−７８℃）で反応を行わなければならない。また，副生するジメチルスルフィドの悪臭が強いため，大量合成には不向きであるなどの問題点が残されている。トリフェニルビスマスジヒドロキシドやテトラアリールビスムトニウム塩などの超原子価ビスマス化合物を酸化剤として用いて高収率で目的物を得るためには，長い反応時間や高い反応温度が必要であり，到底満足できるものではない。温和な条件下，短時間で反応を完了することができるアルコールの酸化法が強く求められている。 However, Jones reagent, Sarett reagent, Collins reagent, PCC, and PDC all use highly toxic heavy metal oxides as oxidizing agents. Moreover, there is a problem that the operation of completely removing the heavy metal oxide from the target product after the reaction is complicated. Although the method using Dess-Martin periodinane can obtain the target compound in high yield, strong explosive properties have been reported for Dess-Martin periodinane and the hydrolyzate of Dess-Martin periodinane. For this reason, the use of this method requires careful attention and is not easy to use. Swern oxidation is an excellent method that does not use highly toxic heavy metal oxides or explosive oxidants. However, the intermediate obtained by reacting activated DMSO with alcohol is extremely unstable, and therefore the reaction must be performed under strict temperature control (−78 ° C.). In addition, the odor of dimethyl sulfide as a by-product is strong, so it is not suitable for mass synthesis. Long reaction time and high reaction temperature are necessary to obtain the desired product in high yield using hypervalent bismuth compounds such as triphenylbismuth dihydroxide and tetraarylbismuthonium salt as oxidizing agents. It is not satisfactory. There is a strong demand for an oxidation method of alcohol that can complete the reaction in a short time under mild conditions.
そこで，発明者らは鋭意研究を重ねた結果，本発明を完成するに至った。 Thus, the inventors have intensively researched and completed the present invention.
本発明は，塩基の存在下，第一級アルコールあるいは第二級アルコールと，下記構造式（２）
（式中Ｒ１，Ｒ２，Ｒ３，Ｒ４，Ｒ５は水素，アルキル基，アルケニル基，アルキニル基，アルコキシ基のいずれかであり，置換されていても良く，Ｒ６はハロゲン，ニトロ基などの電子吸引性基であり，Ｘはハロゲン，アセタート，トリフルオロアセタート，トリフルオロメタンスルホナート，ｐ−トルエンスルホナート，テトラフルオロボラート，ヘキサフルオロホスファート，ビス（トリフルオロメタンスルホニル）イミドから選択される。ただし，Ｒ１＝Ｒ２＝Ｒ３＝Ｒ４＝Ｒ５＝水素は除く）で示される４つのフェニル基の１つに置換基を導入したビスムトニウム塩を反応せしめ，第一級アルコールをアルデヒドに，第二級アルコールをケトンに導くことを特徴とするアルコール類の新規酸化法である。(In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are any of hydrogen, alkyl group, alkenyl group, alkynyl group and alkoxy group, and may be substituted, R 6 is halogen, nitro X is an electron-withdrawing group such as a group, from halogen, acetate, trifluoroacetate, trifluoromethanesulfonate, p-toluenesulfonate, tetrafluoroborate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imide Except that R 1 = R 2 = R 3 = R 4 = R 5 = excluding hydrogen) is reacted with a bismuthonium salt having a substituent introduced into one of the four phenyl groups This is a novel method for oxidizing alcohols characterized in that alcohol is converted to aldehyde and secondary alcohol is converted to ketone.
本発明で使用し得るビスムトニウム塩の１つである，下記構造式（３） The following structural formula (3), which is one of the bismuthonium salts that can be used in the present invention
で示されるメシチルトリフェニルビスムトニウムテトラフルオロボラートを取り上げ，本発明の有用性を例示する。メシチルトリフェニルビスムトニウムテトラフルオロボラートは，ボロントリフルオリド−エチルエーテルコンプレックスの存在下，トリフェニルビスマスジフルオリドとメシチルボロン酸を反応させることにより，容易に得られる。The usefulness of the present invention is illustrated by taking mesityltriphenylbismuthonium tetrafluoroborate represented by the following formula. Mesityltriphenylbismuthonium tetrafluoroborate can be easily obtained by reacting triphenylbismuth difluoride with mesitylboronic acid in the presence of boron trifluoride-ethyl ether complex.
本発明に係る酸化反応は下記反応式に従って進行する。 The oxidation reaction according to the present invention proceeds according to the following reaction formula.
この反応で使用し得る塩基は，炭酸カリウム，炭酸ナトリウム，ＤＢＵ，トリエチルアミン，１，１，３，３−テトラメチルグアニジン，２−ｔｅｒｔ−ブチル−１，１，３，３−テトラメチルグアニジンなどが挙げられるが，１，１，３，３−テトラメチルグアニジンおよびＤＢＵがより好ましい。使用しうる溶媒は，ジクロロメタン，クロロホルム，トリクロロエタン，トルエン，ベンゼン，アセトニトリル，ＴＨＦ，アセトンあるいはこれらの混合溶媒などが挙げられる。反応温度は−７８℃から使用するビスムトニウム塩の分解温度まで適宜選択されるが，室温で十分な反応速度が得られる。反応時間はアルコール，使用するビスムトニウム塩，使用する溶媒により異なり，１分から１２時間の間で選択されるが，好ましくは３０分から６時間である。 Bases that can be used in this reaction include potassium carbonate, sodium carbonate, DBU, triethylamine, 1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, and the like. Among them, 1,1,3,3-tetramethylguanidine and DBU are more preferable. Solvents that can be used include dichloromethane, chloroform, trichloroethane, toluene, benzene, acetonitrile, THF, acetone, and mixed solvents thereof. The reaction temperature is appropriately selected from -78 ° C to the decomposition temperature of the bismuthonium salt used, but a sufficient reaction rate can be obtained at room temperature. The reaction time varies depending on the alcohol, the bismuthonium salt used, and the solvent used, and is selected from 1 minute to 12 hours, preferably 30 minutes to 6 hours.
以下にメシチルトリフェニルビスムトニウムテトラフルオロボラートを用いた酸化反応の結果を示す。
エントリー１，２，３，５の結果が示すように，温和な条件下，短時間で第一級アルコールから高収率で対応するアルデヒドを得ることができた。また，エントリー４，６の結果が示すように，第二級アルコールから，高収率で対応するケトンを得ることができた。エントリー５，６の結果が示すように，非共役系アルコールの酸化にはトルエンを溶媒として用いることにより，高収率で目的物を得ることができた。このように本発明は，第一級アルコール，第二級アルコールのどちらも効率よく酸化することができる。 As the results of entries 1, 2, 3, and 5 show, the corresponding aldehyde was obtained in high yield from the primary alcohol in a short time under mild conditions. As shown in the results of entries 4 and 6, the corresponding ketone could be obtained in high yield from the secondary alcohol. As shown in the results of entries 5 and 6, the target product could be obtained in high yield by using toluene as a solvent for the oxidation of non-conjugated alcohols. Thus, the present invention can efficiently oxidize both primary alcohols and secondary alcohols.
次に，不飽和芳香族アルコール，不飽和鎖状アルコール，非共役系アルコールの共存下における酸化反応の選択性について示す。 Next, the selectivity of the oxidation reaction in the presence of unsaturated aromatic alcohol, unsaturated chain alcohol, and non-conjugated alcohol is shown.
反応終了後，目的物の１Ｈ ＮＭＲを測定し，その積分比から相対的な反応比を算出した。その結果を以下に示す。After completion of the reaction, 1 H NMR of the target product was measured, and the relative reaction ratio was calculated from the integration ratio. The results are shown below.
上表が示すように，いずれの反応も非共役系アルコールとの共存下，不飽和アルコールが選択的に酸化されている。 As shown in the above table, unsaturated alcohol is selectively oxidized in any reaction in the presence of non-conjugated alcohol.
さらに，第一級アルコールと第二級アルコールの共存下における酸化反応の選択性について示す。また，比較例としてＤｅｓｓ−Ｍａｒｔｉｎペルヨージナンを用いた酸化反応の結果も示す。 Furthermore, we show the selectivity of the oxidation reaction in the presence of primary and secondary alcohols. Moreover, the result of the oxidation reaction using Dess-Martin periodinane is also shown as a comparative example.
上表が示すように，ビスムトニウム塩を用いた酸化反応では，不飽和アルコール，非共役系アルコールのいずれの場合も第一級アルコールが選択的に酸化され，対応するアルデヒドが優先的に得られた。また，Ｄｅｓｓ−Ｍａｒｔｉｎペルヨージナンよりも格段に優れた選択性を有していることが示された。 As shown in the above table, in the oxidation reaction using bismuthonium salt, primary alcohol was selectively oxidized in both unsaturated alcohol and non-conjugated alcohol, and the corresponding aldehyde was obtained preferentially. . Moreover, it was shown that it has the selectivity far superior to Dess-Martin periodinane.
上記のごとく，本発明はビスムトニウム塩を用いた第一級アルコールをアルデヒドに，第二級アルコールをケトンに変換するアルコールの酸化法に関するものである。本発明は，有機合成の属する分野および他の分野において要求されている温和な条件下でのアルコール類の選択的酸化に供するものである。本発明の酸化法を用いることにより，温和な条件下，短時間でアルコール類を選択的に酸化することができる。 As described above, the present invention relates to an alcohol oxidation method using a bismuthonium salt to convert a primary alcohol into an aldehyde and a secondary alcohol into a ketone. The present invention provides for the selective oxidation of alcohols under the mild conditions required in the fields of organic synthesis and other fields. By using the oxidation method of the present invention, alcohols can be selectively oxidized in a short time under mild conditions.
以下，本発明を実施例により更に詳細に説明する。なお，本発明の範囲は，かかる実施例に限定されないことは言うまでもない。本発明の範囲内では変形が可能なことは当業者には明らかであろう。 Hereinafter, the present invention will be described in more detail with reference to examples. Needless to say, the scope of the present invention is not limited to such embodiments. It will be apparent to those skilled in the art that variations are possible within the scope of the invention.
実施例１ メシチルトリフェニルビスムトニウムテトラフルオロボラートを用いたｐ−ニトロベンジルアルコールの酸化
メシチルトリフェニルビスムトニウムテトラフルオロボラート（２１３ｍｇ，０．３３ｍｍｏｌ），ｐ−ニトロベンジルアルコール（４５．５ｍｇ，０．３０ｍｍｏｌ），およびＣＨ２Ｃｌ２（１０ｍｌ）の混合物に１，１，３，３−テトラメチルグアニジン（３８ｍｇ，０．３３ｍｍｏｌ）を加えて室温で１時間攪拌した。アルコールが消費されたことをＴＬＣで確認した後，反応混合物を減圧下で濃縮し，残渣を短いシリカゲルカラム（流出溶媒：ヘキサン−ヘキサン／酢酸エチル）にかけると，ｐ−ニトロベンズアルデヒド（４５ｍｇ，０．３３ｍｍｏｌ）が得られた。収率９９％。Example 1 Oxidation of p-nitrobenzyl alcohol with mesityltriphenylbismuthonium tetrafluoroborate Mesityltriphenylbismutonium tetrafluoroborate (213 mg, 0.33 mmol), p-nitrobenzyl alcohol (45 0.5 mg, 0.30 mmol) and CH 2 Cl 2 (10 ml) were added 1,1,3,3-tetramethylguanidine (38 mg, 0.33 mmol) and stirred at room temperature for 1 hour. After confirming that the alcohol was consumed by TLC, the reaction mixture was concentrated under reduced pressure, and the residue was applied to a short silica gel column (eluent: hexane-hexane / ethyl acetate) to obtain p-nitrobenzaldehyde (45 mg, 0 .33 mmol) was obtained. Yield 99%.
以下に得られたｐ−ニトロベンズアルデヒドの物性値を示す。
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ８．０８（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），８．４０（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），１０．１７（ｓ，１Ｈ）The physical property values of the obtained p-nitrobenzaldehyde are shown below.
1 H NMR (CDCl 3 ) δ 8.08 (d, J = 8.8 Hz, 2H), 8.40 (d, J = 8.8 Hz, 2H), 10.17 (s, 1H)
実施例２
メシチルトリフェニルビスムトニウムテトラフルオロボラートを用いたゲラニオールの酸化
メシチルトリフェニルビスムトニウムテトラフルオロボラート（２１３ｍｇ，０．３３ｍｍｏｌ），ゲラニオール（４６．３ｍｇ，０．３０ｍｍｏｌ），およびＣＨ２Ｃｌ２（１０ｍｌ）の混合物に１，１，３，３−テトラメチルグアニジン（３８ｍｇ，０．３３ｍｍｏｌ）を加えて室温で３０分間攪拌した。アルコールが消費されたことをＴＬＣで確認した後，反応混合物を減圧下で濃縮し，残渣を短いシリカゲルカラム（流出溶媒：ヘキサン−ヘキサン／酢酸エチル）にかけると，ゲラニアール（４５ｍｇ，０．３３ｍｍｏｌ）が得られた。収率９８％。Example 2
Oxidation of geraniol using mesityltriphenylbismuthonium tetrafluoroborate Mesitiltriphenylbismuthonium tetrafluoroborate (213 mg, 0.33 mmol), geraniol (46.3 mg, 0.30 mmol), and CH 2 1,1,3,3-Tetramethylguanidine (38 mg, 0.33 mmol) was added to a mixture of Cl 2 (10 ml) and stirred at room temperature for 30 minutes. After confirming that the alcohol was consumed by TLC, the reaction mixture was concentrated under reduced pressure, and the residue was applied to a short silica gel column (elution solvent: hexane-hexane / ethyl acetate) to obtain geranial (45 mg, 0.33 mmol). was gotten. Yield 98%.
以下に得られたゲラニアールの物性値を示す。
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ１．６１（ｓ，３Ｈ），１．６９（ｓ，３Ｈ），２．１７（ｓ，３Ｈ），２．１９−２．２３（ｍ，４Ｈ），５．０７（ｔ，Ｊ＝５．６Ｈｚ，１Ｈ），５．８８（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），９．９９（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ）The physical property values of geranial obtained are shown below.
1 H NMR (CDCl 3 ) δ 1.61 (s, 3H), 1.69 (s, 3H), 2.17 (s, 3H), 2.19-2.23 (m, 4H), 5.07 (T, J = 5.6 Hz, 1H), 5.88 (d, J = 8.2 Hz, 1H), 9.99 (d, J = 8.2 Hz, 1H)
実施例３
メシチルトリフェニルビスムトニウムテトラフルオロボラートを用いた３−ペンタノールの酸化
メシチルトリフェニルビスムトニウムテトラフルオロボラート（３５．５ｍｇ，０．０５５ｍｍｏｌ），３−ペンタノール（４．４ｍｇ，０．０５０ｍｍｏｌ），および重トルエン（１ｍｌ）の混合物に１，１，３，３−テトラメチルグアニジン（６．３ｍｇ，０．０５５ｍｍｏｌ）を加えて室温で３時間攪拌した。アルコールが消費されたことをＮＭＲで確認した後，内部標準試料（ＤＭＦ）を用いて３−ペンタノンの収率を決定した。収率９９％。Example 3
Oxidation of 3-pentanol using mesityltriphenylbismuthonium tetrafluoroborate Mesityltriphenylbismuthonium tetrafluoroborate (35.5 mg, 0.055 mmol), 3-pentanol (4.4 mg, 0.055 mmol), and 1,1,3,3-tetramethylguanidine (6.3 mg, 0.055 mmol) were added to a mixture of heavy toluene (1 ml), and the mixture was stirred at room temperature for 3 hours. After confirming that the alcohol was consumed by NMR, the yield of 3-pentanone was determined using an internal standard sample (DMF). Yield 99%.
以下に得られた３−ペンタノンの物性値を示す。
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ１．０７（ｔ，Ｊ＝７．８Ｈｚ，６Ｈ），２．４３（ｑ，Ｊ＝７．８Ｈｚ，４Ｈ）The physical property values of 3-pentanone obtained are shown below.
1 H NMR (CDCl 3 ) δ 1.07 (t, J = 7.8 Hz, 6H), 2.43 (q, J = 7.8 Hz, 4H)
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| WO2009113217A1 (en) * | 2008-03-11 | 2009-09-17 | 国立大学法人京都大学 | Novel cationic photopolymerization initiator |
| WO2011040531A1 (en) | 2009-10-01 | 2011-04-07 | 日立化成工業株式会社 | Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device |
| WO2011132702A1 (en) | 2010-04-22 | 2011-10-27 | 日立化成工業株式会社 | Organic electronic material, polymerization initiator and thermal polymerization initiator, ink composition, organic thin film and production method for same, organic electronic element, organic electroluminescent element, lighting device, display element, and display device |
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| WO2009113217A1 (en) * | 2008-03-11 | 2009-09-17 | 国立大学法人京都大学 | Novel cationic photopolymerization initiator |
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| WO2011040531A1 (en) | 2009-10-01 | 2011-04-07 | 日立化成工業株式会社 | Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device |
| WO2011132702A1 (en) | 2010-04-22 | 2011-10-27 | 日立化成工業株式会社 | Organic electronic material, polymerization initiator and thermal polymerization initiator, ink composition, organic thin film and production method for same, organic electronic element, organic electroluminescent element, lighting device, display element, and display device |
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