JP6845503B2 - Catalyst for allylation reaction - Google Patents
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- JP6845503B2 JP6845503B2 JP2017039618A JP2017039618A JP6845503B2 JP 6845503 B2 JP6845503 B2 JP 6845503B2 JP 2017039618 A JP2017039618 A JP 2017039618A JP 2017039618 A JP2017039618 A JP 2017039618A JP 6845503 B2 JP6845503 B2 JP 6845503B2
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- 239000003054 catalyst Substances 0.000 title claims description 98
- 238000005937 allylation reaction Methods 0.000 title claims description 41
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 92
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 82
- 239000000377 silicon dioxide Substances 0.000 claims description 40
- 239000011148 porous material Substances 0.000 claims description 35
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 32
- 150000003512 tertiary amines Chemical class 0.000 claims description 32
- XXROGKLTLUQVRX-UHFFFAOYSA-N hydroxymethylethylene Natural products OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 29
- 229910052763 palladium Inorganic materials 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000003446 ligand Substances 0.000 claims description 18
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 18
- 150000002989 phenols Chemical class 0.000 claims description 8
- 239000012038 nucleophile Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 2
- 150000004808 allyl alcohols Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 48
- 230000000694 effects Effects 0.000 description 37
- 238000000034 method Methods 0.000 description 24
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- -1 allyl compound Chemical class 0.000 description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 14
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- 230000000052 comparative effect Effects 0.000 description 12
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- 239000002184 metal Substances 0.000 description 11
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- 230000009471 action Effects 0.000 description 9
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- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 6
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
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- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 4
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- SCZZNWQQCGSWSZ-UHFFFAOYSA-N 1-prop-2-enoxy-4-[2-(4-prop-2-enoxyphenyl)propan-2-yl]benzene Chemical compound C=1C=C(OCC=C)C=CC=1C(C)(C)C1=CC=C(OCC=C)C=C1 SCZZNWQQCGSWSZ-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 0 CCN(CC)CCC* Chemical compound CCN(CC)CCC* 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- YHLVIDQQTOMBGN-UHFFFAOYSA-N methyl prop-2-enyl carbonate Chemical compound COC(=O)OCC=C YHLVIDQQTOMBGN-UHFFFAOYSA-N 0.000 description 2
- 239000012450 pharmaceutical intermediate Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- YNYMCUPQXZBCJN-UHFFFAOYSA-N 1-prop-2-enoxynaphthalene Chemical compound C1=CC=C2C(OCC=C)=CC=CC2=C1 YNYMCUPQXZBCJN-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003463 adsorbent Substances 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
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002691 malonic acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 125000005911 methyl carbonate group Chemical group 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- BVBBZEKOMUDXMZ-UHFFFAOYSA-N n,n-diethyl-3-triethoxysilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCN(CC)CC BVBBZEKOMUDXMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 241000894007 species Species 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、アリル化反応用触媒に関する。より詳しくは、アリル化合物を効率的に製造するためのメソポーラスシリカ担持型パラジウム触媒に関する。 The present invention relates to a catalyst for an allylation reaction. More specifically, the present invention relates to a mesoporous silica-supported palladium catalyst for efficiently producing an allyl compound.
アリル化合物は、医薬品中間体、及び機能性樹脂の前駆体として有用な化合物である。現在までに、塩化アリル、酢酸アリル、炭酸アリルなどのアリル化合物と遷移金属触媒から発生するπ−アリル金属種に対し、アルコール、アミン、マロン酸エステルなどの活性水素を有する求核剤とを反応させ、活性水素部位をアリル化する手法が知られている（非特許文献１）。 Allyl compounds are useful compounds as pharmaceutical intermediates and precursors of functional resins. To date, allyl compounds such as allyl chloride, allyl acetate, and allyl carbonate have reacted with π-allyl metal species generated from transition metal catalysts with nucleophilic agents having active hydrogen such as alcohols, amines, and malonic acids. A method of allylating the active hydrogen moiety is known (Non-Patent Document 1).
また、アリル化合物に関する特許文献１には、遷移金属触媒、錯化剤、及び３級アミン化合物の存在下、ヒドロキシル基を含有する化合物とカルボン酸アリルエステル化合物とを反応させる工程、を含み、前記反応工程において、反応系中に水を存在させて、有機相と水相とが二相分離した状態で、反応させる、アリルエーテルの製造方法が開示されている。該特許文献は、より詳細には、パラジウム―炭素を触媒とし、ホスフィン化合物と第３級アミンを共存させることで、酢酸アリルをアリル化剤とするフェノール類のアリル化反応を行う。しかしながら、第３級アミンは金属触媒と直接相互作用して活性を下げるほか、ホスフィン化合物や第３級アミンは回収再利用が困難であるとの問題がある。 Further, Patent Document 1 relating to an allyl compound includes a step of reacting a compound containing a hydroxyl group with a carboxylic acid allyl ester compound in the presence of a transition metal catalyst, a complexing agent, and a tertiary amine compound. In the reaction step, a method for producing allyl ether is disclosed in which water is present in the reaction system and the organic phase and the aqueous phase are separated into two phases to react. More specifically, the patent document conducts an allylation reaction of phenols using allyl acetate as an allylating agent by allowing a phosphine compound and a tertiary amine to coexist using palladium-carbon as a catalyst. However, there is a problem that the tertiary amine directly interacts with the metal catalyst to reduce the activity, and the phosphine compound and the tertiary amine are difficult to recover and reuse.
その他、パラジウム触媒及びアミンをシリカなどの金属酸化物表面に固定化することで、アミンと遷移金属との相互作用を抑制し、アリル化反応を効率化させる手法が知られている（非特許文献２）。しかし、固体表面へのパラジウム触媒とアミンの担持は無作為に進行するため、π−アリルパラジウム種に対して求核剤が攻撃するための最適な位置にパラジウムとアミンとを配置することは困難である。また、本手法では炭酸アリル、酢酸アリルなどをアリル化剤として用いることができるが、アリルアルコールをアリル化剤としている用いることができない。アリルアルコールは、安価であり、副生成物として水しか出すことがなく、環境調和性の観点で有用であるため、その利用が望まれる。 In addition, a method is known in which the interaction between the amine and the transition metal is suppressed and the allylation reaction is made more efficient by immobilizing the palladium catalyst and the amine on the surface of a metal oxide such as silica (Non-Patent Documents). 2). However, it is difficult to place palladium and amines in optimal positions for the nucleophile to attack the π-allylpalladium species, as the support of the palladium catalyst and amines on the solid surface proceeds randomly. Is. Further, in this method, allyl carbonate, allyl acetate and the like can be used as the allylating agent, but allyl alcohol cannot be used as the allylating agent. Allyl alcohol is inexpensive, produces only water as a by-product, and is useful from the viewpoint of environmental friendliness, so its use is desired.
以上のとおり、アリル化には（１）現在の技術では反応性の低いアリル基質であるアリルアルコールをアリル化剤としている用いることができないという問題、そして、（２）第３級アミンを用いる場合においては、第３級アミンは金属触媒と直接相互作用して活性を下げるほか、ホスフィン化合物や第３級アミンは回収再利用が困難であるという問題、という２つの問題が存在する。上記にもかかわらず、担体構造が固定化金属錯体と有機塩基との間の触媒作用に及ぼす影響は現在までにほとんど研究されていない。 As described above, for allylation, (1) the problem that allyl alcohol, which is a low-reactivity allyl substrate, cannot be used as an allylating agent in the current technology, and (2) when a tertiary amine is used. In the above, there are two problems that the tertiary amine directly interacts with the metal catalyst to reduce the activity, and that the phosphine compound and the tertiary amine are difficult to recover and reuse. Despite the above, the effect of carrier structure on catalysis between immobilized metal complexes and organic bases has been poorly studied to date.
アリル化合物を効率的に製造するためのメソポーラスシリカ担持型パラジウム触媒を提供する。 Provided is a mesoporous silica-supported palladium catalyst for efficiently producing an allyl compound.
上記したとおり、（１）アリルアルコールをアリル化剤としている用いることができないという問題、そして、（２）第３級アミンを用いる場合においては、第３級アミンは金属触媒と直接相互作用して活性を下げるほか、ホスフィン化合物や第３級アミンは回収再利用が困難であるという問題、という２つの難点が存在する。したがって、本発明者らはアリル化反応に対して高活性であり、アリルアルコールを含む様々なアリル化剤を適用することができるアリル化反応用触媒を作成することとした。本発明者らは、まず、アリルアルコールを含む様々なアリル化剤を適用可能であり、かつ高い触媒活性を示す金属酸化物担持型パラジウム触媒を提供することができないか検討した。 As mentioned above, (1) the problem that allyl alcohol cannot be used as an allylic agent, and (2) when a tertiary amine is used, the tertiary amine interacts directly with the metal catalyst. In addition to lowering the activity, there are two drawbacks: phosphine compounds and tertiary amines are difficult to recover and reuse. Therefore, the present inventors have decided to prepare a catalyst for the allylation reaction, which is highly active in the allylation reaction and to which various allylation agents including allylic alcohol can be applied. First, the present inventors investigated whether various allylic agents including allyl alcohol could be applied and a metal oxide-supported palladium catalyst exhibiting high catalytic activity could be provided.
本発明者らは、鋭意研究した結果、メソポーラスシリカに担持したホスフィン配位子を有するパラジウム錯体が、アリルアルコール、炭酸アリル、酢酸アリル、ハロゲン化アリルをアリル化剤とするβ−ケトエステル類、アルコール類、アミン類のアリル化反応に対して高活性を示すことを見出し、上記問題（１）及び（２）を解決することができることを見出すに至った。 As a result of diligent research, the present inventors have found that the palladium complex having a phosphine ligand supported on mesoporous silica is allyl alcohol, allyl carbonate, allyl acetate, β-ketoesters using allyl halide as an allylating agent, and alcohol. They have found that they show high activity against the allylation reaction of amines and amines, and have found that the above problems (1) and (2) can be solved.
すなわち、本開示の一実施形態に係るアリル化反応用触媒は、ホスフィン配位子を有するパラジウム錯体をメソポーラスシリカに固定化したアリル化反応用触媒である。 That is, the allylation reaction catalyst according to one embodiment of the present disclosure is an allylation reaction catalyst in which a palladium complex having a phosphine ligand is immobilized on mesoporous silica.
かかる触媒は、アリルアルコール、炭酸アリル、酢酸アリル、ハロゲン化アリルをアリル化剤とするβ−ケトエステル類、アルコール類、アミン類のアリル化反応に対して高活性を示すとの作用効果を奏する。 Such a catalyst exerts an action effect of exhibiting high activity against the allylation reaction of β-ketoesters, alcohols, and amines using allyl alcohol, allyl carbonate, allyl acetate, and allyl halide as an allylation agent.
本開示の一実施形態において、メソポーラスシリカに対し、さらに第３級アミンを固定化してもよい。 In one embodiment of the present disclosure, a tertiary amine may be further immobilized on mesoporous silica.
かかるメソポーラスシリカに対し、さらに第３級アミンを固定化するとの構成により、さらに優れた触媒特性を示す。 Further excellent catalytic properties are exhibited by the configuration in which a tertiary amine is further immobilized on the mesoporous silica.
本開示の一実施形態において、アリル化反応は、アリル化剤がアリルアルコールであってもよい。 In one embodiment of the present disclosure, in the allylation reaction, the allylating agent may be an allyl alcohol.
本開示の一実施形態に係るアリル化反応用触媒は、反応性が低いアリル化剤であるアリルアルコールを用いることを可能にするとの作用効果を奏する。 The allylation reaction catalyst according to one embodiment of the present disclosure has an effect of enabling the use of allyl alcohol, which is a low-reactivity allylation agent.
本開示の一実施形態において、アリル化反応の求核剤がアルコール類又はアミン類、であってもよい。 In one embodiment of the present disclosure, the nucleophile for the allylation reaction may be alcohols or amines.
本開示の一実施形態において、アリル化反応の求核剤が、β−ケトエステルまたはフェノール類であってもよい。 In one embodiment of the present disclosure, the nucleophile for the allylation reaction may be β-ketoesters or phenols.
本開示の一実施形態において、パラジウム錯体の前駆体は配位子末端にシリル基を有してもよい。 In one embodiment of the present disclosure, the precursor of the palladium complex may have a silyl group at the ligand end.
本開示の一実施形態において、パラジウム錯体は、配位子が二座型のホスフィン配位子であってもよい。 In one embodiment of the present disclosure, the palladium complex may be a bidentate phosphine ligand.
本開示の一実施形態において、メソポーラスシリカの空孔サイズは１．５ｎｍ以上５０ｎｍ以下であってもよい。なお、本明細書において単にメソポーラスシリカと言及する場合には、空孔サイズは１．５ｎｍ〜５０ｎｍである。 In one embodiment of the present disclosure, the pore size of mesoporous silica may be 1.5 nm or more and 50 nm or less. When simply referring to mesoporous silica in the present specification, the pore size is 1.5 nm to 50 nm.
本開示において、メソポーラスシリカの空孔サイズは、吸着質が脱離するときの相対圧と吸着量の関係である脱着等温線から細孔径を求めるＢＪＨ法により測定された値をいう。 In the present disclosure, the pore size of mesoporous silica refers to a value measured by the BJH method for determining the pore diameter from the desorption isotherm, which is the relationship between the relative pressure when the adsorbate is desorbed and the amount of adsorption.
本開示の一実施形態において、メソポーラスシリカの空孔サイズは１．５ｎｍ以上６ｎｍ以下であってもよい。 In one embodiment of the present disclosure, the pore size of mesoporous silica may be 1.5 nm or more and 6 nm or less.
本開示の一実施形態において、メソポーラスシリカの空孔サイズは１．５ｎｍ以上３．５ｎｍ以下であってもよい。 In one embodiment of the present disclosure, the pore size of mesoporous silica may be 1.5 nm or more and 3.5 nm or less.
本開示の一実施形態において、メソポーラスシリカの空孔サイズは１．５ｎｍ以上２ｎｍ以下であってもよい。 In one embodiment of the present disclosure, the pore size of mesoporous silica may be 1.5 nm or more and 2 nm or less.
本発明により提供される触媒を用いるアリル化反応からは、医薬品中間体や機能性樹脂の前駆体として有用なアリル化合物を、安価かつ環境調和に優れた方法で製造することができる。また、本発明の触媒は、メソポーラスシリカに担持した触媒であるため、反応後の生成物からの分離が容易である。したがって、本発明方法は工業的に多大な効果をもたらす発明ということができる。 From the allylation reaction using the catalyst provided by the present invention, an allylic compound useful as a precursor of a pharmaceutical intermediate or a functional resin can be produced by an inexpensive and environmentally friendly method. Further, since the catalyst of the present invention is a catalyst supported on mesoporous silica, it can be easily separated from the product after the reaction. Therefore, it can be said that the method of the present invention is an invention that brings about a great effect industrially.
以下、本出願で開示される発明の各実施形態について、図面を参照しつつ説明する。但し、本発明は、その要旨を逸脱しない範囲において様々な形態で実施することができ、以下に例示する実施形態の記載内容に限定して解釈されるものではない。 Hereinafter, embodiments of the invention disclosed in the present application will be described with reference to the drawings. However, the present invention can be implemented in various forms without departing from the gist thereof, and is not construed as being limited to the description contents of the embodiments exemplified below.
以下の実施形態によりもたらされる作用効果とは異なる他の作用効果であっても、本明細書の記載から明らかなもの、または、当業者において容易に予測し得るものについては、当然に本発明によりもたらされるものと理解される。 Other effects different from those brought about by the following embodiments, which are obvious from the description of the present specification or which can be easily predicted by those skilled in the art, are naturally according to the present invention. It is understood to be brought about.
本発明におけるアリル化反応用触媒は、メソポーラスシリカ、又はあらかじめ第３級アミンを担持させたメソポーラスシリカに対して、下記化学式１で示される、トリエトキシシリル基を配位子末端に有するパラジウム触媒を有機溶媒中で反応させることにより合成することができる。
本触媒において使用されるメソポーラスシリカ（通常、メソポーラスシリカは空孔サイズが１．５ｎｍ以上５０ｎｍ以下である）は、構造内にメソ孔を有するものであれば、どのようなものでも用いることができる。ただ、１．５ｎｍ〜６ｎｍ程度の空孔サイズであることが好ましく、さらにその中で１．５ｎｍ〜３．５ｎｍの空孔サイズであることが好ましい。そして、反応空間の場という観点からは、２ｎｍ以下が最も好ましい空孔サイズである。 As the mesoporous silica used in this catalyst (usually, the mesoporous silica has a pore size of 1.5 nm or more and 50 nm or less), any mesoporous silica having a mesoporous structure in the structure can be used. .. However, the pore size is preferably about 1.5 nm to 6 nm, and more preferably the pore size is 1.5 nm to 3.5 nm. From the viewpoint of the field of the reaction space, 2 nm or less is the most preferable pore size.
なお、空孔サイズは、吸着質が脱離するときの相対圧と吸着量の関係である脱着等温線から細孔径を求めるＢＪＨ法により測定された値をいう。ポーラスシリカのような多孔体の表面積や細孔径分布に関する情報は、測定したガス吸着量から半経験的理論計算によって求めることができる。ガス吸着量の測定には重量法と容量法があり、容量法には定容法と定圧法の二つがある。ＢＪＨ法は定容法であり、定容法は一定容積の基準容器内に吸着ガスを溜めた後、試料部へ吸着ガスを導入し、基準容器部と試料部を合わせた容積における開放前後の圧力差に基づき、吸着量を求め、窒素ガス吸着量の解析から空孔の細孔径分布を求める手法である。 The pore size refers to a value measured by the BJH method for determining the pore diameter from the desorption isotherm, which is the relationship between the relative pressure when the adsorbent is desorbed and the amount of adsorption. Information on the surface area and pore size distribution of porous bodies such as porous silica can be obtained from the measured gas adsorption amount by semi-empirical theoretical calculation. There are two methods for measuring the amount of gas adsorbed, the gravimetric method and the volumetric method, and the volumetric method is the constant volume method and the constant pressure method. The BJH method is a constant volume method. In the constant volume method, after accumulating the adsorbed gas in a standard container having a fixed volume, the adsorbed gas is introduced into the sample part, and before and after opening the combined volume of the reference container part and the sample part. This is a method of obtaining the adsorption amount based on the pressure difference and obtaining the pore size distribution of the pores from the analysis of the nitrogen gas adsorption amount.
上記した空孔サイズは、ホスフィン配位子を有するパラジウム錯体をメソポーラスシリカに固定化されており、かかるメソポーラスシリカにおける限られた空間が、所定の反応空間として調整されたために、反応空間内における協調的触媒作用によって、金属錯体および有機塩基が蓄積され、非多孔質またはより大きなメソポーラスシリカ担持触媒よりも高い性能を示す、との機序に基づくと考えられる（図１）。 In the above-mentioned pore size, a palladium complex having a phosphine ligand is immobilized on mesoporous silica, and the limited space in the mesoporous silica is adjusted as a predetermined reaction space, so that the coordination in the reaction space is achieved. It is believed to be based on the mechanism that metal complexes and organic bases are accumulated by catalytic catalysis and exhibit higher performance than non-porous or larger mesoporous silica-supported catalysts (Fig. 1).
ここで、本開示における触媒は、大きく２つに分けられる（図２）。図２の左側は、第三級アミンを固定せずＰＰ−Ｐｄを固定したメソポーラスシリカ担持触媒であり、図２の右側は、第三級アミンとＰＰ−Ｐｄとを（同一表面上に）固定したメソポーラスシリカ担持触媒である。 Here, the catalyst in the present disclosure can be roughly divided into two (Fig. 2). The left side of FIG. 2 is a mesoporous silica-supported catalyst in which PP-Pd is fixed without fixing the tertiary amine, and the right side of FIG. 2 is a catalyst in which the tertiary amine and PP-Pd are fixed (on the same surface). It is a mesoporous silica-supported catalyst.
図３を参照する。上記の触媒の分類に対応し、大きく２つに分けられる（図３における（Ａ）及び（Ｂ）である）。図３の（Ａ）では、第三級アミンとＰＰ−Ｐｄとを（同一表面上に）固定したメソポーラスシリカ担持触媒において炭酸アリルメチルが反応することによりアリル化活性種が生成し、ここに塩基により活性化された求核剤が反応する。図３（Ｂ）では、第三級アミンを固定せずＰＰ−Ｐｄを固定したメソポーラスシリカ担持触媒においてアリルアルコールが反応することによりアリル化活性種が生成し、ここに求核剤が反応する。 See FIG. Corresponding to the above classification of catalysts, they can be roughly divided into two ((A) and (B) in FIG. 3). In FIG. 3 (A), an allylating active species is produced by the reaction of allylmethyl carbonate in a mesoporous silica-supported catalyst in which a tertiary amine and PP-Pd are immobilized (on the same surface), and an allylating active species is produced therein by a base. Activated nucleophiles react. In FIG. 3B, an allylating active species is produced by the reaction of allyl alcohol in a mesoporous silica-supported catalyst in which PP-Pd is immobilized without immobilizing a tertiary amine, and a nucleophile reacts there.
すなわち、図１を再び参照すると、ノンポーラスな場合において、離脱基の活性、アリル化剤であるホスフィン配位子を有するパラジウム錯体の活性、アミンを用いて図示した塩基の活性が、別々の箇所において生じるのに対して、メソポーラスな空間を調整することで、離脱基の活性、アリル化剤であるホスフィン配位子を有するパラジウム錯体の活性、塩基の活性が、被アリル化化合物へ協調的に作用する結果、より効率的に反応が促進される。かかる機序を具体的に説明したのが図３（Ａ）と（Ｂ）であり、各活性部位が協調的に作用するメソポーラスな空間の範囲が、上記で定められた本発明の空孔サイズである。 That is, referring to FIG. 1 again, in the non-porous case, the activity of the leaving group, the activity of the palladium complex having the phosphine ligand which is the allylating agent, and the activity of the base illustrated by using the amine are different. By adjusting the mesoporous space, the activity of the leaving group, the activity of the palladium complex having the phosphine ligand which is the allylating agent, and the activity of the base are coordinated to the asymmetric compound. As a result of the action, the reaction is promoted more efficiently. 3 (A) and 3 (B) specifically explain such a mechanism, and the range of the mesoporous space in which each active site acts cooperatively is the pore size of the present invention defined above. Is.
本触媒を用いることで促進させることできるアリル化反応の形態としては、化学式２で示されるアリル化剤と、β−ケトエステルやフェノール類とを、適切な有機溶媒中あるいは無溶媒条件下、触媒活性種発生のための無機塩基存在のもとで、一定時間加温撹拌する実験方法が挙げられる。
化学式２で示されるアリル化剤が有する置換基Ｘとしては、例えばハロゲン、カルボキシラート基、ヒドロキシ基、炭酸アルキル基などが挙げられるが、アセタート基、炭酸メチル基、ヒドロキシ基が望ましい。 Examples of the substituent X contained in the allylating agent represented by the chemical formula 2 include a halogen, a carboxylate group, a hydroxy group and an alkyl carbonate group, and an acetate group, a methyl carbonate group and a hydroxy group are preferable.
アリル化反応で用いられるのは、アルコール類、β―ケトエステル、アミン類、であり、アルコール類としては、フェノール類が挙げられる。アミン類はアニリン類、ピペリジン、モルホリンが挙げられる。 Alcohols, β-ketoesters and amines are used in the allylation reaction, and examples of alcohols include phenols. Examples of amines include anilines, piperidines, and morpholines.
アリル化反応で用いられるβ―ケトエステルとしては、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸プロピル等が挙げられるが、アセト酢酸エチルが好ましい。 Examples of the β-ketoester used in the allylation reaction include methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate and the like, but ethyl acetoacetate is preferable.
アリル化反応で用いられるフェノール類としては、フェノール、１―ナフトール、２―ナフトール、ビスフェノールＡ等が挙げられるが、ビスフェノールＡが好ましい。 Examples of the phenols used in the allylation reaction include phenol, 1-naphthol, 2-naphthol, bisphenol A and the like, but bisphenol A is preferable.
触媒反応は無溶媒条件下でも効率的に進行するが、有機溶媒中で反応する場合、有機溶媒としては、トルエン、キシレン、ベンゼン、メシチレン、ヘキサン、オクタン、テトラヒドロフラン等が挙げられるが、トルエンが好ましい。これらは単独で使用しても、２種以上を混合使用してもよい。その使用量は基質に対して重量比０．１倍〜１０００倍、好ましくは１倍〜１００倍の範囲から選ばれる。 The catalytic reaction proceeds efficiently even under solvent-free conditions, but when the reaction is carried out in an organic solvent, examples of the organic solvent include toluene, xylene, benzene, mesitylene, hexane, octane, tetrahydrofuran and the like, but toluene is preferable. .. These may be used alone or in combination of two or more. The amount used is selected from the range of 0.1 to 1000 times, preferably 1 to 100 times, the weight ratio with respect to the substrate.
触媒反応の条件には、特に制約はないが、通常、反応は０℃〜１５０℃、好ましくは５０℃〜１００℃の範囲で行われる。 The conditions of the catalytic reaction are not particularly limited, but the reaction is usually carried out in the range of 0 ° C. to 150 ° C., preferably 50 ° C. to 100 ° C.
触媒反応における反応時間は、用いる触媒の量や反応温度等により左右され、一概に定めることはできないが、通常は０．１時間〜８０時間の範囲で、好ましくは０．１時間〜３０時間の範囲で行われる。 The reaction time in the catalytic reaction depends on the amount of the catalyst used, the reaction temperature, etc., and cannot be unconditionally determined, but is usually in the range of 0.1 hours to 80 hours, preferably 0.1 hours to 30 hours. It is done in the range.
触媒活性種発生のために使用される無機塩基としては、アルカリ金属あるいはアルカリ土類金属の炭酸塩、酢酸塩、水酸化物が挙げられるが、炭酸ナトリウム、炭酸カリウム、炭酸セシウムを用いるほうがよく、特に炭酸カリウムが好ましい。これらは単独で使用しても、２種以上を混合使用してもよい。その使用量は触媒が有するパラジウムに対してモル比０．１倍〜２０倍、好ましくは０．５倍〜１０倍の範囲から選ばれる。 Examples of the inorganic base used for generating catalytically active species include carbonates, acetates, and hydroxides of alkali metals or alkaline earth metals, but it is better to use sodium carbonate, potassium carbonate, and cesium carbonate. Potassium carbonate is particularly preferable. These may be used alone or in combination of two or more. The amount used is selected from the range of 0.1 to 20 times, preferably 0.5 to 10 times, the molar ratio of palladium contained in the catalyst.
本触媒がより促進されるアリル化反応で得られるアリル化生成物は、例えば、アリルアセト酢酸エチル、アセトジアリル酢酸エチル、アリルフェニルエーテル、１―アリルオキシナフタレン、２―アリルオキシナフタレン、ビスフェノールＡジアリルエーテルなどが例示される。 The allylation products obtained by the allylation reaction in which this catalyst is further promoted include, for example, ethyl allylate acetate, ethyl acetodialyl acetate, allylphenyl ether, 1-allyloxynaphthalene, 2-allyloxynaphthalene, and bisphenol A diallyl ether. Etc. are exemplified.
本触媒を用いるアリル化反応の実施態様は、反応器に触媒、無機塩基、基質、アリル化剤、溶媒を入れて混合し、内部を不活性ガスで置換して所定の温度で反応を行うものである。反応終了後、ろ過、溶媒を留去し、蒸留、クロマト分離、再結晶や昇華等の通常の方法によって、得られたアリル化生成物を取り出すことができる。必要に応じ、反応終了後に有機溶媒を追添してもよい。 In the embodiment of the allylation reaction using this catalyst, a catalyst, an inorganic base, a substrate, an allylating agent, and a solvent are put into a reactor, mixed, and the inside is replaced with an inert gas to carry out the reaction at a predetermined temperature. Is. After completion of the reaction, the obtained allylation product can be taken out by a usual method such as filtration, distillation of solvent, distillation, chromatographic separation, recrystallization and sublimation. If necessary, an organic solvent may be added after the reaction is completed.
以下、実施例により本発明を更に具体的に説明するが、本発明は以下の実施例に制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
［メソポーラスシリカの調製］
メソポーラスシリカ（以下、単に「ＭＳ」という。）は非特許文献（Science 1995、 267、 865.）に記載された方法に基づき、用いる一級アミンのアルキル鎖の長さの異なる４種類ＭＳ（Ｃ８）、ＭＳ（Ｃ１０）、ＭＳ（Ｃ１２）、ＭＳ（Ｃ１８）を合成した。一例としてＭＳ（Ｃ１２）を挙げて説明する。ドデシルアミン（Ｃ１２、５３．８ｍｍｏｌ）を脱イオン水（１００ｇ）とエタノール（８２ｇ）溶媒に室温で溶解した。次に、テトラエトキシシラン（ＴＥＯＳ、２００ｍｍｏｌ）を溶液に加え、室温で３０分間撹拌した。反応混合物を室温で３０時間据えき、ろ過し、脱イオン水で洗浄した後、抽出を行い、ＭＳ（Ｃ１２）を生成した。
[Preparation of mesoporous silica]
Mesoporous silica (hereinafter referred to simply as "MS") is based on the method described in non-patent documents (Science 1995, 267, 865.), and four types of MS (C8) having different lengths of alkyl chains of primary amines are used. , MS (C10), MS (C12), MS (C18) were synthesized. As an example, MS (C12) will be described. Dodecylamine (C12, 53.8 mmol) was dissolved in deionized water (100 g) and ethanol (82 g) solvent at room temperature. Next, tetraethoxysilane (TEOS, 200 mmol) was added to the solution, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was allowed to stand at room temperature for 30 hours, filtered, washed with deionized water, and then extracted to produce MS (C12).
［パラジウム錯体前駆体ＰＰ-Ｐｄの調製］
また、パラジウム錯体前駆体ＰＰ-Ｐｄは、非特許文献（Catal. Sci. Technol.、 2016、 6、 5380.）に記載された方法に基づいて合成した。なお、本明細書では、ビスホスフィンパラジウム錯体をＰＰ−Ｐｄとも称する。
[Preparation of Palladium Complex Precursor PP-Pd]
In addition, the palladium complex precursor PP-Pd was synthesized based on the method described in the non-patent document (Catal. Sci. Technol., 2016, 6, 5380.). In addition, in this specification, a bisphosphine palladium complex is also referred to as PP-Pd.
以下、実施例１〜２及び比較例１と、実施例３〜７及び比較例２とを実施例として挙げる。実施例１〜２及び比較例１は、第三級アミンを固定せずＰＰ−Ｐｄを固定したメソポーラスシリカ担持触媒に関するものであり、以下かかる実施例１〜２における反応スキームをスキーム１とも称する。他方、後者の実施例３〜７及び比較例２は、第三級アミンとＰＰ−Ｐｄとを（同一表面上に）固定したメソポーラスシリカ担持触媒に関するものであり、以下かかる実施例３〜７における反応スキームをスキーム２とも称する。 Hereinafter, Examples 1 and 2 and Comparative Example 1 and Examples 3 to 7 and Comparative Example 2 will be given as Examples. Examples 1 and 2 and Comparative Example 1 relate to a mesoporous silica-supported catalyst in which PP-Pd is fixed without fixing a tertiary amine, and the reaction schemes in Examples 1 and 2 are also referred to as Scheme 1 below. On the other hand, the latter Examples 3 to 7 and Comparative Example 2 relate to a mesoporous silica-supported catalyst in which a tertiary amine and PP-Pd are immobilized (on the same surface), and are described below in Examples 3 to 7. The reaction scheme is also referred to as scheme 2.
［スキーム１］
［実施例１］
担持触媒ＭＳ（Ｃ１２）／ＰＰ-Ｐｄの調製
事前に１２０度で３時間減圧乾燥させたＭＳ（Ｃ１２）（０．５ｇ）に対して、ＰＰ-Ｐｄ（０．２７ｍｍｏｌ）をトルエン（１０ｍＬ）中、５０度で２０時間反応させた後、溶媒を減圧下で留去し、減圧乾燥させることで担持触媒ＭＳ（Ｃ１２）／ＰＰ-Ｐｄを得た。
[Scheme 1]
[Example 1]
Preparation of supported catalyst MS (C12) / PP-Pd PP-Pd (0.27 mmol) in toluene (10 mL) with respect to MS (C12) (0.5 g) previously dried under reduced pressure at 120 ° C. for 3 hours. After reacting at 50 ° C. for 20 hours, the solvent was distilled off under reduced pressure and dried under reduced pressure to obtain a supported catalyst MS (C12) / PP-Pd.
表１に、元素分析の結果を示す。
表２には、固定化されたＰＰ−Ｐｄ系の化学構造を決定するために行ったＥＸＡＦＳ測定のカーブフィッティング解析により得られたパラメータを示す。
なお、ＰＰ−Ｐｄの固定化後においてもメソポーラス構造を維持していることは、小角ＸＲＤ分析によっても確認した。また、触媒がＭＳに担体されていることは、元素分析で窒素及び炭素量から確認したほか、ＳＥＭによる粒子内のリン及びパラジウムの存在から確認した。 It was also confirmed by small angle XRD analysis that the mesoporous structure was maintained even after the immobilization of PP-Pd. In addition, it was confirmed by elemental analysis that the catalyst was carried by MS from the amounts of nitrogen and carbon, and also from the presence of phosphorus and palladium in the particles by SEM.
［実施例１］ 触媒反応
ガラス製反応容器に、実施例１である担持触媒ＭＳ（Ｃ１２）／ＰＰ-Ｐｄ（３．０μｍｏｌ）、炭酸カリウム（０．５０ｍｍｏｌ）、トルエン（２．０ｍＬ）、アセト酢酸エチル（１．０ｍｍｏｌ）、炭酸アリルメチル（２．５ｍｍｏｌ）をいれ、アルゴン雰囲気下、７０度で６０分間激しく撹拌した。反応後、反応溶液の一部を重クロロホルムに溶解させＮＭＲ測定を行うことでアセト酢酸エチルの転化率、アセトアリル酢酸エチル、アセトジアリル酢酸エチルの収率、ターンオーバー数を算出した。その結果、アセトアリル酢酸エチルの収率が４９％、アセトジアリル酢酸エチルの収率が１２％であり、ターンオーバー数が１９０であった。
[Example 1] Catalyst reaction In a glass reaction vessel, the supported catalyst MS (C12) / PP-Pd (3.0 μmol), potassium carbonate (0.50 mmol), toluene (2.0 mL), acetoaceto, which are the first examples. Ethyl acetate (1.0 mmol) and allylmethyl carbonate (2.5 mmol) were added, and the mixture was vigorously stirred at 70 ° C. for 60 minutes under an argon atmosphere. After the reaction, a part of the reaction solution was dissolved in deuterated chloroform and NMR measurement was performed to calculate the conversion rate of ethyl acetoacetate, the yield of ethyl acetoallyl acetate and ethyl acetodialyl acetate, and the number of turnovers. As a result, the yield of ethyl acetoallyl acetate was 49%, the yield of ethyl acetodialyl acetate was 12%, and the turnover number was 190.
なお、本明細書において、転化率、収率、ターンオーバー数（ＴＯＮ）は、以下の計算式により計算している。
［実施例２］
ガラス製反応容器に、担持触媒ＭＳ（Ｃ１２）／ＰＰ-Ｐｄ（４．０μｍｏｌ）、炭酸カリウム（０．５０ｍｍｏｌ）、酢酸アリルエチル（４．０ｍｍｏｌ）、アリルアルコール（１０ｍｍｏｌ）をいれ、アルゴン雰囲気下、８０度で１３時間激しく撹拌した。反応後、反応溶液の一部を重クロロホルムに溶解させＮＭＲ測定を行うことでアセト酢酸エチルの転化率、アセトアリル酢酸エチル、アセトジアリル酢酸エチルの収率、ターンオーバー数を算出した。その結果、アセトアリル酢酸エチルの収率が５１％、アセトジアリル酢酸エチルの収率が１７％であり、ターンオーバー数が８２０であった。
[Example 2]
A supported catalyst MS (C12) / PP-Pd (4.0 μmol), potassium carbonate (0.50 mmol), allyl ethyl acetate (4.0 mmol), and allyl alcohol (10 mmol) were placed in a glass reaction vessel under an argon atmosphere. The mixture was vigorously stirred at 80 ° C. for 13 hours. After the reaction, a part of the reaction solution was dissolved in deuterated chloroform and NMR measurement was performed to calculate the conversion rate of ethyl acetoacetate, the yield of ethyl acetoallyl acetate and ethyl acetodialyl acetate, and the number of turnovers. As a result, the yield of ethyl acetoallyl acetate was 51%, the yield of ethyl acetodialyl acetate was 17%, and the turnover number was 820.
［比較例１］
担持触媒ＭＳ（Ｃ１２）／ＰＰ-Ｐｄ（３．０μｍｏｌ）の代わりに、市販の非多孔性シリカ（Ａｅｒｏｓｉｌ３００）を用いてＳｉＯ2／ＰＰ−Ｐｄを用いた。それ以外の条件は実施例１と同一の条件としてアセト酢酸エチルの転化率、アセトアリル酢酸エチル、アセトジアリル酢酸エチルの収率、ターンオーバー数を算出した。アセト酢酸エチルの転化率は３８％、アセトアリル酢酸エチルの収率が３５％、アセトジアリル酢酸エチルの収率が３％、ターンオーバー数が１１０であった。
[Comparative Example 1]
Instead of the supported catalyst MS (C12) / PP-Pd (3.0 μmol), SiO 2 / PP-Pd was used using commercially available non-porous silica (Aerosil 300). Other than that, the conversion rate of ethyl acetoacetate, the yield of ethyl acetoallyl acetate and ethyl acetodialyl acetate, and the number of turnovers were calculated under the same conditions as in Example 1. The conversion rate of ethyl acetoacetate was 38%, the yield of ethyl acetoallyl acetate was 35%, the yield of ethyl acetodialyl acetate was 3%, and the turnover number was 110.
上記の結果を表３にまとめた。
上記にて示した通り、細孔な直径を有するメソポーラスシリカ担持触媒を用いた場合、通常のシリカを用いた比較例１に比して高い性能を示すことが理解できる。これは、メソポーラス材料という限られた空間、すなわち所定の反応空間が調整され、かかる反応空間内における協調的触媒作用によって、金属錯体および有機塩基が蓄積されることで、非多孔質またはより大きなメソポーラスシリカ担持触媒よりも高い性能を示すとの機序に基づくものであると考えられる（なお、かかる機序につき図１を用いてスキーム２の考察にて記す）。 As shown above, it can be understood that when a mesoporous silica-supported catalyst having a pore diameter is used, higher performance is exhibited as compared with Comparative Example 1 using ordinary silica. This is because the limited space of mesoporous materials, that is, a predetermined reaction space, is adjusted, and metal complexes and organic bases are accumulated by cooperative catalysis in such reaction space, resulting in non-porous or larger mesoporous materials. It is considered to be based on the mechanism that the performance is higher than that of the silica-supported catalyst (the mechanism is described in the discussion of Scheme 2 using FIG. 1).
なお、後述するとおり実施例３〜７においては、同一表面上に第三級アミンを固定するスキームにて触媒反応を実施しているものの、後述する機序には共通する点があると考えられ、そうであるならば、以下の実施例３〜実施例７が比較例２との間で有意な結果を有することも併せ考えると、実施例上、スキーム１においても、少なくとも１．６ｎｍ〜５．３ｎｍという空孔サイズを有するメソポーラスシリカ担持触媒（同一表面上に第三級アミンを固定しない）において顕著な作用効果を奏する。 As will be described later, in Examples 3 to 7, although the catalytic reaction is carried out by a scheme in which the tertiary amine is immobilized on the same surface, it is considered that there are common points in the mechanisms described later. If so, considering that the following Examples 3 to 7 have significant results with Comparative Example 2, at least 1.6 nm to 5 in Scheme 1 as well as in Examples. It exerts a remarkable effect on a mesoporous silica-supported catalyst having a pore size of .3 nm (without fixing a tertiary amine on the same surface).
さらに、後述する同一表面上に第三級アミンを固定した実験結果に鑑みれば、同一表面上に第三級アミンを固定しない本スキーム（スキーム１）においても、ＭＳの細孔径が小さい触媒ほど、細孔径の大きな触媒に比べ高活性となると考えられる。 Furthermore, in view of the experimental results of fixing the tertiary amine on the same surface, which will be described later, even in this scheme (Scheme 1) in which the tertiary amine is not fixed on the same surface, the smaller the pore size of the MS, the smaller the catalyst. It is considered that the activity is higher than that of a catalyst having a large pore size.
さらに、アリル化剤としてアリルアルコールを用いる反応（上記実施例２参照）では、担体のシラノール基による反応の促進が確認された。 Furthermore, in the reaction using allyl alcohol as the allylating agent (see Example 2 above), it was confirmed that the silanol group of the carrier promoted the reaction.
そして、本明細書の上記「１．６ｎｍ〜５．３ｎｍという空孔サイズを有するメソポーラスシリカ担持触媒（同一表面上に第三級アミンを固定しない）において作用効果を奏する」との開示に基づけば、当業者にとって１．５ｎｍ〜６ｎｍ程度の空孔サイズを有するメソポーラスシリカ担持触媒においても本開示における作用効果と類似する作用効果、すなわち、比較例との間で、相当程度に反応が促進されるという作用効果、を奏することと理解可能である。 Then, based on the above-mentioned disclosure of the present specification, "it exerts an action effect in a mesoporous silica-supported catalyst having a pore size of 1.6 nm to 5.3 nm (without fixing a tertiary amine on the same surface)". For those skilled in the art, a mesoporous silica-supported catalyst having a pore size of about 1.5 nm to 6 nm also has an action effect similar to that of the present disclosure, that is, a reaction is promoted to a considerable extent with a comparative example. It can be understood that it produces the effect.
さらに、本明細書の上記開示に基づけば、当業者にとって１．５ｎｍ〜５０ｎｍ程度の空孔サイズを有する同様のメソポーラスシリカ担持触媒においても、少なくとも比較例との比較では所定の作用効果を奏することが理解可能である。 Further, based on the above disclosure of the present specification, even a similar mesoporous silica-supported catalyst having a pore size of about 1.5 nm to 50 nm for those skilled in the art can exert a predetermined action and effect at least in comparison with a comparative example. Is understandable.
［スキーム２］
下記の実施例３〜７は、メソポーラスシリカに対し、さらに第３級アミンを固定化した触媒を用いる実施例である。
[Scheme 2]
Examples 3 to 7 below are examples in which a catalyst in which a tertiary amine is further immobilized on mesoporous silica is used.
［実施例３］
担持触媒ＭＳ（Ｃ８）／ＮＥｔ2／ＰＰ-Ｐｄの調製
事前に１２０度で３時間減圧乾燥させたＭＳ（Ｃ８）（０．５ｇ）に対して、３―ジエチルアミノプロピルトリエトキシシラン（０．８０ｍｍｏｌ）をトルエン（１０ｍＬ）中、４０度で１時間反応させた後、減圧下で溶媒を留去することで担持触媒ＭＳ／ＮＥｔ2を調製した。これに対し、続けてＰＰ-Ｐｄ（０．２７ｍｍｏｌ）をトルエン（１０ｍＬ）中５０度で２０時間反応させ、溶媒を減圧下で留去し、減圧乾燥させることで担持触媒ＭＳ（Ｃ８）／ＮＥｔ2／ＰＰ-Ｐｄを得た。
[Example 3]
Preparation of supported catalyst MS (C8) / NEt 2 / PP-Pd 3-diethylaminopropyltriethoxysilane (0.80 mmol) with respect to MS (C8) (0.5 g) previously dried under reduced pressure at 120 ° C. for 3 hours. ) Was reacted in toluene (10 mL) at 40 ° C. for 1 hour, and then the solvent was distilled off under reduced pressure to prepare a supported catalyst MS / NEt 2. On the other hand, PP-Pd (0.27 mmol) was subsequently reacted in toluene (10 mL) at 50 ° C. for 20 hours, the solvent was distilled off under reduced pressure, and the mixture was dried under reduced pressure to carry the catalyst MS (C8) / NEt. 2 / PP-Pd was obtained.
［実施例４］
担持触媒ＭＳ（Ｃ１０）／ＮＥｔ2／ＰＰ-Ｐｄの調製
メソポーラスシリカとしてＭＳ（Ｃ８）の代わりにＭＳ（Ｃ１０）を用いる以外は実施例３に記載と同様の方法により、担持触媒ＭＳ（Ｃ１０）／ＮＥｔ2／ＰＰ-Ｐｄを得た。
[Example 4]
Preparation of supported catalyst MS (C10) / NEt 2 / PP-Pd The supported catalyst MS (C10) was prepared by the same method as described in Example 3 except that MS (C10) was used instead of MS (C8) as the mesoporous silica. / Net 2 / PP-Pd was obtained.
［実施例５］
担持触媒ＭＳ（Ｃ１２）／ＮＥｔ2／ＰＰ-Ｐｄの調製
メソポーラスシリカとしてＭＳ（Ｃ８）の代わりにＭＳ（Ｃ１２）を用いる以外は実施例３に記載と同様の方法により、担持触媒ＭＳ（Ｃ１２）／ＮＥｔ2／ＰＰ-Ｐｄを得た。
[Example 5]
Preparation of supported catalyst MS (C12) / NEt 2 / PP-Pd The supported catalyst MS (C12) was prepared by the same method as described in Example 3 except that MS (C12) was used instead of MS (C8) as the mesoporous silica. / Net 2 / PP-Pd was obtained.
［実施例６］
担持触媒ＭＳ（Ｃ１８）／ＮＥｔ2／ＰＰ-Ｐｄの調製
メソポーラスシリカとしてＭＳ（Ｃ８）の代わりにＭＳ（Ｃ１８）を用いる以外は実施例３に記載と同様の方法により、担持触媒ＭＳ（Ｃ１８）／ＮＥｔ2／ＰＰ-Ｐｄを得た。
[Example 6]
Preparation of supported catalyst MS (C18) / NEt 2 / PP-Pd The supported catalyst MS (C18) was prepared by the same method as described in Example 3 except that MS (C18) was used instead of MS (C8) as the mesoporous silica. / Net 2 / PP-Pd was obtained.
［実施例７］
担持触媒ＳＢＡ―１６／ＮＥｔ2／ＰＰ-Ｐｄの調製
メソポーラスシリカとしてＭＳ（Ｃ８）の代わりにＳＢＡ―１６を用いる以外は実施例３に記載と同様の方法により、担持触媒ＳＢＡ―１６／ＮＥｔ2／ＰＰ-Ｐｄを得た。
[Example 7]
Preparation of supported catalyst SBA-16 / Net 2 / PP-Pd By the same method as described in Example 3 except that SBA-16 is used instead of MS (C8) as the mesoporous silica, the supported catalyst SBA-16 / Net 2 / PP-Pd was obtained.
実施例３〜７で合成した担持型触媒を、元素分析、ＸＡＦＳ、ＮＭＲ、窒素吸着測定により同定した。 The supported catalysts synthesized in Examples 3 to 7 were identified by elemental analysis, XAFS, NMR, and nitrogen adsorption measurement.
表４に、担持型触媒の元素分析測定の結果を記した。
触媒として、他の担持型触媒を用いる以外は実施例１に記載と同じ方法で触媒反応を実施した。結果を、それぞれの触媒の空孔サイズとともに表５に示した。
また、上記実施例における反応式を示す。
上記実施例３〜７及び比較例２の結果を参照すると、１．６ｎｍ〜５．３ｎｍという空孔サイズを有するメソポーラスシリカ担持触媒（であって同一表面上に第三級アミンを固定するもの）は、実施例１〜２にて示した、Ｐｄ錯体のみを固定した触媒（ＭＳ／ＰＰ−Ｐｄ）と比較して、顕著に活性が向上することが分かる。また、ＭＳの細孔径が小さい触媒ほど、細孔径の大きな触媒に比べ、高活性となることを発見した。 With reference to the results of Examples 3 to 7 and Comparative Example 2 above, a mesoporous silica-supported catalyst having a pore size of 1.6 nm to 5.3 nm (which immobilizes a tertiary amine on the same surface). It can be seen that the activity is significantly improved as compared with the catalyst (MS / PP-Pd) in which only the Pd complex is immobilized, which is shown in Examples 1 and 2. It was also found that a catalyst having a smaller pore diameter of MS has a higher activity than a catalyst having a larger pore diameter.
そして、本明細書の「１．６ｎｍ〜５．３ｎｍという空孔サイズを有するメソポーラスシリカ担持触媒（であって同一表面上に第三級アミンを固定するもの）」において作用効果を奏する、との上記開示に基づけば、当業者にとって１．５ｎｍ〜６ｎｍ程度の空孔サイズを有するメソポーラスシリカ担持触媒においても本開示における作用効果と類似する作用効果、すなわち、比較例との間で、相当程度に反応が促進されるという作用効果、を奏することと理解可能である。 Then, it is said that it exerts an action and effect in "a mesoporous silica-supported catalyst having a pore size of 1.6 nm to 5.3 nm (which fixes a tertiary amine on the same surface)" of the present specification. Based on the above disclosure, even a mesoporous silica-supported catalyst having a pore size of about 1.5 nm to 6 nm for those skilled in the art has an action effect similar to that of the present disclosure, that is, to a considerable extent with a comparative example. It can be understood that it exerts an action effect that the reaction is promoted.
さらに、本明細書の上記開示に基づけば、当業者にとって１．５ｎｍ〜５０ｎｍ程度の空孔サイズを有する同様のメソポーラスシリカ担持触媒においても、少なくとも比較例との比較では所定の作用効果を奏することが理解可能である。 Further, based on the above disclosure of the present specification, even a similar mesoporous silica-supported catalyst having a pore size of about 1.5 nm to 50 nm for those skilled in the art can exert a predetermined action and effect at least in comparison with a comparative example. Is understandable.
本触媒における反応は、図２右側、図３（Ａ）にて示された反応である。ノンポーラスな場合において、離脱基の活性、アリル化剤であるところのホスフィン配位子を有するパラジウム錯体の活性、アミンを用いて図示した塩基の活性が、別々の箇所において生じるのに対して、メソポーラスな空間を調整することで、離脱基の活性、アリル化剤であるところのホスフィン配位子を有するパラジウム錯体の活性、塩基の活性が、被アリル化化合物へ協調的に作用する結果、より効率的に反応が促進される（図１）。これは、ホスフィン配位子を有するパラジウム錯体をメソポーラスシリカに固定化されており、かかるメソポーラスシリカにおける限られた空間が、所定の反応空間として調整されたために、反応空間内における協調的触媒作用によって、金属錯体および有機塩基が蓄積され、非多孔質またはより大きなメソポーラスシリカ担持触媒よりも高い性能を示す、との機序に基づく。 The reaction in this catalyst is the reaction shown in FIG. 2 right and FIG. 3 (A). In the non-porous case, the activity of the leaving group, the activity of the palladium complex with the phosphine ligand, which is the allylating agent, and the activity of the base illustrated with the amine occur at different locations, whereas By adjusting the mesoporous space, the activity of the leaving group, the activity of the palladium complex having the phosphine ligand which is the allylating agent, and the activity of the base act cooperatively on the allylated compound, resulting in more. The reaction is efficiently promoted (Fig. 1). This is because the palladium complex having the phosphine ligand is immobilized on the mesoporous silica, and the limited space in the mesoporous silica is adjusted as a predetermined reaction space, so that the catalytic action in the reaction space is cooperative. , Metal complexes and organic bases are accumulated and exhibit higher performance than non-porous or larger mesoporous silica-bearing catalysts.
［実施例８］
ガラス製反応容器に、担持触媒ＭＳ（Ｃ１０）／ＮＥｔ2／ＰＰ-Ｐｄ（４．０μｍｏｌ）、炭酸カリウム（１０ｍｍｏｌ）、ビスフェノールＡ（４．０ｍｍｏｌ）、酢酸アリル（１０．０ｍｍｏｌ）をいれ、アルゴン雰囲気下、８５度で４時間激しく撹拌した。反応後、クロロホルムとアセトンを加え、ろ過した後、ろ液を減圧下で濃縮したところ１．２１ｇのビスフェノールＡジアリルエーテルが得られた。本アリル化では、収率９８％でビスフェノールＡジアリルエーテルが得られ、総ＴＯＮは１９６０という目覚ましいものであった。
[Example 8]
Put the supported catalyst MS (C10) / NEt 2 / PP-Pd (4.0 μmol), potassium carbonate (10 mmol), bisphenol A (4.0 mmol), and allyl acetate (10.0 mmol) in a glass reaction vessel, and argon. In an atmosphere, the mixture was vigorously stirred at 85 ° C. for 4 hours. After the reaction, chloroform and acetone were added, the mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain 1.21 g of bisphenol A diallyl ether. In this allylation, bisphenol A diallyl ether was obtained in a yield of 98%, and the total TON was as remarkable as 1960.
かかる実験結果により、フェノール類、フェノール誘導体も求核剤として使用することができることが分かる。 From such experimental results, it can be seen that phenols and phenol derivatives can also be used as nucleophiles.
以上迄に記載した本開示をまとめる。本開示により、本開示のホスフィン配位子を有するパラジウム錯体をメソポーラスシリカに固定化したアリル化反応用触媒によれば、（１）アリルアルコールをアリル化剤としている用いることができないという問題を解決することができる。 This disclosure described above is summarized. According to the present disclosure, according to the catalyst for allylation reaction in which a palladium complex having a phosphine ligand of the present disclosure is immobilized on mesoporous silica, (1) the problem that allyl alcohol cannot be used as an allylation agent can be solved. can do.
そして、従来は（２）第３級アミンを用いる場合においては、第３級アミンは金属触媒と直接相互作用して活性を下げるほか、ホスフィン化合物や第３級アミンは回収再利用が困難であるという問題があったが、ホスフィン配位子を有するパラジウム錯体をメソポーラスシリカに固定化したアリル化反応用触媒であって該メソポーラスシリカに対し、さらに第３級アミンを固定化することで、かかる問題を解決可能であることがわかった。 Conventionally, (2) when a tertiary amine is used, the tertiary amine directly interacts with the metal catalyst to reduce the activity, and the phosphine compound and the tertiary amine are difficult to recover and reuse. However, it is a catalyst for an allylation reaction in which a palladium complex having a phosphine ligand is immobilized on mesoporous silica, and a tertiary amine is further immobilized on the mesoporous silica. Turned out to be solvable.
また、メソポーラスシリカ担持触媒（であって同一表面上に第三級アミンを固定するもの）は、実施例１〜２にて示した、Ｐｄ錯体のみを固定した触媒（ＭＳ／ＰＰ−Ｐｄ）と比較して、さらに活性が向上することが分かった。 The mesoporous silica-supported catalyst (which has a tertiary amine immobilized on the same surface) is the same as the catalyst (MS / PP-Pd) in which only the Pd complex is immobilized, which is shown in Examples 1 and 2. In comparison, it was found that the activity was further improved.
また、ＭＳの細孔径が小さい触媒ほど、細孔径の大きな触媒に比べ、高活性となることがわかった。 It was also found that the catalyst having a smaller pore diameter of MS has higher activity than the catalyst having a larger pore diameter.
これらの記載された作用効果は、いずれもホスフィン配位子を有するパラジウム錯体をメソポーラスシリカに固定化されており、かかるメソポーラスシリカにおける限られた空間が、所定の反応空間として調整されたために、反応空間内における協調的触媒作用によって、金属錯体および有機塩基が蓄積され、非多孔質またはより大きなメソポーラスシリカ担持触媒よりも高い性能を示す、との機序に基づくものである。 All of these described effects are reactions because a palladium complex having a phosphine ligand is immobilized on mesoporous silica, and the limited space in the mesoporous silica is adjusted as a predetermined reaction space. It is based on the mechanism that metal complexes and organic bases are accumulated by cooperative catalysis in space and exhibit higher performance than non-porous or larger mesoporous silica-supported catalysts.
Claims (6)
前記パラジウム錯体の配位子が二座型のホスフィン配位子を有する、アリル化反応用触媒。 A catalyst for allylation reaction in which a palladium complex having a phosphine ligand is immobilized on mesoporous silica .
A catalyst for an allylation reaction, wherein the ligand of the palladium complex has a bidentate phosphine ligand .
請求項１に記載のアリル化反応用触媒。 Further immobilize a tertiary amine on mesoporous silica,
The catalyst for allylation reaction according to claim 1.
請求項１に記載のアリル化反応用触媒。 In the allylation reaction, the allylating agent is allyl alcohol.
The catalyst for allylation reaction according to claim 1.
請求項１から３のいずれかに記載のアリル化反応用触媒。 The nucleophile for the allylation reaction is β-ketoester or phenols.
The catalyst for allylation reaction according to any one of claims 1 to 3.
請求項１から４のいずれか１項に記載のアリル化反応用触媒。 The precursor of the palladium complex has a silyl group at the ligand terminal.
The catalyst for an allylation reaction according to any one of claims 1 to 4.
請求項１から５のいずれか１項に記載のアリル化反応用触媒。 The pore size of the mesoporous silica is 1.5 nm to 50 nm.
The catalyst for an allylation reaction according to any one of claims 1 to 5.
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