JP2020183347A - Method of producing lactone compound - Google Patents
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- JP2020183347A JP2020183347A JP2019086721A JP2019086721A JP2020183347A JP 2020183347 A JP2020183347 A JP 2020183347A JP 2019086721 A JP2019086721 A JP 2019086721A JP 2019086721 A JP2019086721 A JP 2019086721A JP 2020183347 A JP2020183347 A JP 2020183347A
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- lactone compound
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- -1 lactone compound Chemical class 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000007789 gas Substances 0.000 claims abstract description 45
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims abstract description 39
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 36
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 230000000737 periodic effect Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims description 37
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 9
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000010931 gold Substances 0.000 description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 10
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 9
- 229910003445 palladium oxide Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- MKUWVMRNQOOSAT-UHFFFAOYSA-N but-3-en-2-ol Chemical compound CC(O)C=C MKUWVMRNQOOSAT-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LBCZOTMMGHGTPH-UHFFFAOYSA-N 2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCO)C=C1 LBCZOTMMGHGTPH-UHFFFAOYSA-N 0.000 description 1
- PKZCRWFNSBIBEW-UHFFFAOYSA-N 2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CN PKZCRWFNSBIBEW-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BXCQGSQPWPGFIV-UHFFFAOYSA-N carbon monoxide;cobalt;cobalt(2+);methanone Chemical compound [Co].[Co+2].O=[CH-].O=[CH-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] BXCQGSQPWPGFIV-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- PQANGXXSEABURG-UHFFFAOYSA-N cyclohex-2-en-1-ol Chemical compound OC1CCCC=C1 PQANGXXSEABURG-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、ラクトン化合物の製造方法に関する。 The present invention relates to a method for producing a lactone compound.
従来、アリルアルコールのような二重結合と水酸基の両方を持つ化合物と一酸化炭素を直接反応させてγ−ブチロラクトン（ＧＢＬ）などのラクトン化合物を得る方法については、均一反応触媒を用いて実施されている。
例えば、非特許文献１には、触媒としてＲｕ（ＩＩＩ）−ＥＤＴＡ錯体を用いて、アリルアルコールをヒドロホルミル化（オキソ反応）することにより、γ−ヒドロキシブチルアルデヒドとともにγ−ブチロラクトンが生成することが記載されている。また、非特許文献２には、コバルトカルボニル（Ｃｏ２（ＣＯ）８）およびＴＯＮ，Ｎ，Ｎ’ ，Ｎ’−テトラメチルエチレンヂアミン（ＴＭＥＤＡ）の存在下アリルアルコールをヒドロホルミル化（オキソ反応）することにより、γ−ブチロラクトンが生成することが記載されている。
Conventionally, a method of directly reacting a compound having both a double bond and a hydroxyl group such as allyl alcohol with carbon monoxide to obtain a lactone compound such as γ-butyrolactone (GBL) has been carried out using a uniform reaction catalyst. ing.
For example, Non-Patent Document 1 describes that γ-butyrolactone is produced together with γ-hydroxybutyraldehyde by hydroformylating (oxo reaction) allyl alcohol using a Ru (III) -EDTA complex as a catalyst. Has been done. In addition, Non-Patent Document 2 describes hydroformylation (oxo reaction) of allyl alcohol in the presence of cobalt carbonyl (Co 2 (CO) 8 ) and TON, N, N', N'-tetramethylethylenediamine (TMEDA). It is described that γ-butyrolactone is produced by this.
また、アルデヒドの製造方法として、第５族〜第１０族の遷移金属から選ばれる一種以上の金属の酸化物からなる担体に第１１族の遷移金属を担持させた不均一系触媒の存在下で、オレフィン系不飽和化合物をヒドロホルミル化反応させてアルデヒドを製造する方法が提案されている（例えば、特許文献１参照）。 Further, as a method for producing an aldehyde, in the presence of a heterogeneous catalyst in which a transition metal of Group 11 is supported on a carrier made of an oxide of one or more metals selected from transition metals of Groups 5 to 10. , A method for producing an aldehyde by hydroformylating an olefin-based unsaturated compound has been proposed (see, for example, Patent Document 1).
上記の通り、従来、アリルアルコールのような二重結合と水酸基の両方を持つ化合物と一酸化炭素を直接反応させてγ−ブチロラクトン（ＧＢＬ）などのラクトン化合物を生成させる反応には、均一触媒が用いられていた。均一触媒は、反応後に得られた生成物と触媒との分離に手間がかかる。不均一触媒であれば、反応液と触媒とを濾過等の方法で簡単に分離できる。このため、不均一触媒の存在下で反応させることによりラクトン化合物が得られる製造方法が求められている。
しかし、従来、不均一触媒を用いてラクトン化合物を製造する方法は知られていなかった。
As described above, conventionally, a uniform catalyst has been used for a reaction in which a compound having both a double bond and a hydroxyl group such as allyl alcohol is directly reacted with carbon monoxide to produce a lactone compound such as γ-butyrolactone (GBL). It was used. In the homogeneous catalyst, it takes time and effort to separate the product obtained after the reaction from the catalyst. If it is a heterogeneous catalyst, the reaction solution and the catalyst can be easily separated by a method such as filtration. Therefore, there is a demand for a production method in which a lactone compound can be obtained by reacting in the presence of a heterogeneous catalyst.
However, conventionally, a method for producing a lactone compound using a heterogeneous catalyst has not been known.
本発明は、上記事情を鑑みてなされたものであり、不均一触媒の存在下で反応させることによりラクトン化合物が得られる製造方法を提供することを課題とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a production method for obtaining a lactone compound by reacting in the presence of a heterogeneous catalyst.
本発明者は、上記課題を解決するために鋭意検討した。
すなわち、通常、水素ガスと一酸化炭素ガスとの混合ガスと、不飽和アルコールとを反応させても、得られた化合物を脱水素反応させなければ環状ラクトンは得られない。これに対し、本発明者は、水素ガスと一酸化炭素ガスとを含む混合ガスと、特定の不飽和アルコールとを、不均一触媒の存在下で反応させることにより、得られた化合物を脱水素反応させることなく、ラクトン化合物が得られることを見出し、本発明を想到した。
すなわち、本発明は以下の事項に関する。
The present inventor has diligently studied to solve the above problems.
That is, usually, even if a mixed gas of hydrogen gas and carbon monoxide is reacted with an unsaturated alcohol, the cyclic lactone cannot be obtained unless the obtained compound is dehydrogenated. On the other hand, the present inventor dehydrogenates the obtained compound by reacting a mixed gas containing hydrogen gas and carbon monoxide gas with a specific unsaturated alcohol in the presence of a heterogeneous catalyst. The present invention was conceived by finding that a lactone compound can be obtained without reacting.
That is, the present invention relates to the following matters.
［１］ 水素ガスと一酸化炭素ガスとを含む混合ガスと、下記一般式（１）で表される不飽和アルコールとを、周期表第４周期の第４族〜第１４族の元素の酸化物からなる担体に、周期表第５周期または第６周期の８族〜１１族の金属または金属酸化物が担持された不均一触媒の存在下で反応させることを特徴とするラクトン化合物の製造方法。 [1] Oxidation of a mixed gas containing hydrogen gas and carbon monoxide and an unsaturated alcohol represented by the following general formula (1) in groups 4 to 14 of the 4th cycle of the periodic table. A method for producing a lactone compound, which comprises reacting a carrier made of a substance in the presence of a heterogeneous catalyst in which a metal or metal oxide of Groups 8 to 11 of the 5th or 6th period of the periodic table is supported. ..
［２］ 前記一般式（１）で表される不飽和アルコールが、アリルアルコールである［１］に記載のラクトン化合物の製造方法。 [2] The method for producing a lactone compound according to [1], wherein the unsaturated alcohol represented by the general formula (1) is allyl alcohol.
[３］ 前記担体が、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎのいずれかの元素の酸化物からなり、
前記担体に担持される金属が、Ａｕ、Ｒｈ、Ｐｄ、Ｉｒ、Ｒｕのいずれかの金属またはＲｈ、Ｐｄ、Ｉｒ、Ｒｕのいずれかの金属酸化物からなる［１］または［２］に記載のラクトン化合物の製造方法。
［４］ 前記不均一触媒が、Ｃｏ３Ｏ４からなる担体に、ＡｕまたはＰｄＯが担持されたものである［１］〜［３］のいずれかに記載のラクトン化合物の製造方法。
［５］ 前記混合ガスが、前記水素ガスと前記一酸化炭素ガスとを、モル比で９：１〜１：５の割合で含む［１］〜［４］のいずれかに記載のラクトン化合物の製造方法。
[3] The carrier is made of an oxide of any of Mn, Fe, Co, Ni, Cu, and Zn.
[1] or [2], wherein the metal supported on the carrier is composed of any metal of Au, Rh, Pd, Ir, Ru or a metal oxide of Rh, Pd, Ir, Ru. Method for producing a lactone compound.
[4] The method for producing a lactone compound according to any one of [1] to [3], wherein the heterogeneous catalyst is a carrier composed of Co 3 O 4 on which Au or PdO is supported.
[5] The lactone compound according to any one of [1] to [4], wherein the mixed gas contains the hydrogen gas and the carbon monoxide gas in a molar ratio of 9: 1 to 1: 5. Production method.
［６］ 反応容器に、溶媒と、前記不飽和アルコールと、前記不均一触媒とを入れ、前記反応容器内を前記混合ガス雰囲気とする工程と、
前記反応容器内で、前記混合ガスと前記不飽和アルコールとを反応させる反応工程とを有し、
前記溶媒が、テトラヒドロフラン、アセトン、酢酸エチルから選ばれるいずれかであることを特徴とする［１］〜［５］のいずれかに記載のラクトン化合物の製造方法。
[6] A step of putting the solvent, the unsaturated alcohol, and the heterogeneous catalyst in the reaction vessel to create the mixed gas atmosphere in the reaction vessel.
It has a reaction step of reacting the mixed gas with the unsaturated alcohol in the reaction vessel.
The method for producing a lactone compound according to any one of [1] to [5], wherein the solvent is any one selected from tetrahydrofuran, acetone, and ethyl acetate.
本発明のラクトン化合物の製造方法では、水素ガスと一酸化炭素ガスとを含む混合ガスと、特定の不飽和アルコールとを、不均一触媒の存在下で反応させる。このため、本発明のラクトン化合物の製造方法では、反応後に得られた目的物と触媒との分離が容易である。 In the method for producing a lactone compound of the present invention, a mixed gas containing hydrogen gas and carbon monoxide gas is reacted with a specific unsaturated alcohol in the presence of a heterogeneous catalyst. Therefore, in the method for producing a lactone compound of the present invention, it is easy to separate the target product obtained after the reaction from the catalyst.
以下、本発明のラクトン化合物の製造方法について詳細に説明する。なお、本発明は、以下に示す実施形態のみに限定されるものではない。
本実施形態のラクトン化合物の製造方法では、水素ガスと一酸化炭素ガスとを含む混合ガスと、下記一般式（１）で表される不飽和アルコールとを、不均一触媒の存在下で反応させる。
Hereinafter, the method for producing the lactone compound of the present invention will be described in detail. The present invention is not limited to the embodiments shown below.
In the method for producing a lactone compound of the present embodiment, a mixed gas containing hydrogen gas and carbon monoxide gas is reacted with an unsaturated alcohol represented by the following general formula (1) in the presence of a heterogeneous catalyst. ..
本実施形態のラクトン化合物の製造方法は、反応容器に、溶媒と、一般式（１）で表される不飽和アルコールと、不均一触媒とを入れ、反応容器内を混合ガス雰囲気とする工程と、反応容器内で、混合ガスと一般式（１）で表される不飽和アルコールとを反応させる反応工程とを有することが好ましい。 The method for producing a lactone compound of the present embodiment is a step of putting a solvent, an unsaturated alcohol represented by the general formula (1), and a heterogeneous catalyst in a reaction vessel to create a mixed gas atmosphere in the reaction vessel. , It is preferable to have a reaction step of reacting the mixed gas with the unsaturated alcohol represented by the general formula (1) in the reaction vessel.
（不飽和アルコール）
本実施形態の製造方法において、一般式（１）で表される不飽和アルコールは、出発物質として用いられる。一般式（１）で表される不飽和アルコール中のＲ１、Ｒ２、Ｒ３はそれぞれ、水素原子、炭素原子数１〜８のアルキル基、シクロヘキシル基、フェニル基から選ばれるいずれかである。
Ｒ１が、炭素原子数１〜８のアルキル基、シクロヘキシル基、フェニル基から選ばれるいずれかである場合、一般式（１）で表される不飽和アルコールは、シス体であってもよいし、トランス体であってもよいし、シス体とトランス体との混合物であってもよい。
(Unsaturated alcohol)
In the production method of the present embodiment, the unsaturated alcohol represented by the general formula (1) is used as a starting material. R 1 , R 2 , and R 3 in the unsaturated alcohol represented by the general formula (1) are any of hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, cyclohexyl groups, and phenyl groups, respectively. ..
When R 1 is any one selected from an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, and a phenyl group, the unsaturated alcohol represented by the general formula (1) may be a cis form. , It may be a trans form, or it may be a mixture of a cis form and a trans form.
一般式（１）で表される不飽和アルコール中において、Ｒ１、Ｒ２、Ｒ３としての炭素原子数１〜８のアルキル基は、立体障害が小さい方が反応に有利であるため、メチル基またはエチル基であることが好ましく、メチル基であることがより好ましい。
一般式（１）で表される不飽和アルコール中のｎは１〜３の整数である。分子内反応を行う上での反応速度を考慮すると、本実施形態の製造方法により合成されるラクトン化合物は、５員環または６員環のラクトン化合物であることが好ましい。このため、ｎは、１または２であることが好ましく、１であることが最も好ましい。
ｎが２または３の場合、複数のＲ３は全て同一であってよいし、一部あるいは全てが異なっていてもよい。
In the unsaturated alcohol represented by the general formula (1), the alkyl groups having 1 to 8 carbon atoms as R 1 , R 2 , and R 3 are methyl because the smaller the steric hindrance, the more advantageous for the reaction. It is preferably a group or an ethyl group, more preferably a methyl group.
N in the unsaturated alcohol represented by the general formula (1) is an integer of 1 to 3. Considering the reaction rate in carrying out the intramolecular reaction, the lactone compound synthesized by the production method of the present embodiment is preferably a 5-membered ring or 6-membered ring lactone compound. Therefore, n is preferably 1 or 2, and most preferably 1.
when n is 2 or 3, all of the plurality of R 3 is may be the same or some or all are different.
一般式（１）で表される不飽和アルコールとしては、具体的には、アリルアルコール、クロチルアルコール（２−ブテン−１−オール）、シンナミルアルコール（３−フェニル−１−プロパノール）、メタリルアルコール（２−メチル−１−プロパノール）、３−ブテン−２−オール、２−シクロヘキセン−１−オール、３−ブテン−１−オール、４−ペンテン−１−オール、５−ヘキセン−１−オールなどが挙げられ、本実施形態の製造方法により合成される目的物であるラクトン化合物の種類に応じて、適宜決定される。 Specific examples of the unsaturated alcohol represented by the general formula (1) include allyl alcohol, crotyl alcohol (2-butene-1-ol), cinnamyl alcohol (3-phenyl-1-propanol), and meta. Lyl alcohol (2-methyl-1-propanol), 3-butene-2-ol, 2-cyclohexene-1-ol, 3-butene-1-ol, 4-penten-1-ol, 5-hexene-1-ol Examples thereof include oars, which are appropriately determined according to the type of the lactone compound which is the target product synthesized by the production method of the present embodiment.
一般式（１）で表される不飽和アルコールとしては、上記の中でも特に、Ｒ１、Ｒ２、Ｒ３が全て水素原子であってｎが１であるアリルアルコールが好ましい。一般式（１）で表される不飽和アルコールが、アリルアルコールである場合、本実施形態の製造方法によって、有用性の高いラクトン化合物であるγ−ブチロラクトン（ＧＢＬ）が得られる。 As the unsaturated alcohol represented by the general formula (1), an allyl alcohol in which R 1 , R 2 and R 3 are all hydrogen atoms and n is 1 is particularly preferable. When the unsaturated alcohol represented by the general formula (1) is allyl alcohol, γ-butyrolactone (GBL), which is a highly useful lactone compound, can be obtained by the production method of the present embodiment.
（ラクトン化合物）
本実施形態の製造方法により合成される目的物であるラクトン化合物は、式（２）または式（３）で示される。
(Lactone compound)
The target lactone compound synthesized by the production method of the present embodiment is represented by the formula (2) or the formula (3).
（不均一触媒）
本実施形態の製造方法においては、不均一触媒として、周期表第４周期の第４族〜第１４族の元素の酸化物からなる担体に、周期表第５周期または第６周期の８族〜１１族の金属または金属酸化物が担持されたものを用いる。より好ましい担体としては、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎの酸化物が挙げられる。担体に担持されるより好ましい金属としては、Ａｕ、Ｒｈ、Ｐｄ、Ｉｒ、Ｒｕが挙げられる。担体に担持されるより好ましい金属酸化物としては、Ｒｈ、Ｐｄ、Ｉｒ、Ｒｕの酸化物が挙げられる。本実施形態の製造方法においては、不均一触媒として、１種のみを用いてもよいし、２種以上を用いてもよい。
(Heterogeneous catalyst)
In the production method of the present embodiment, as a heterogeneous catalyst, a carrier made of an oxide of an element of Group 4 to Group 14 of the 4th cycle of the periodic table is used, and Group 8 to the 6th cycle of the periodic table. A metal or metal oxide of Group 11 is supported. More preferable carriers include oxides of Mn, Fe, Co, Ni, Cu and Zn. More preferred metals supported on the carrier include Au, Rh, Pd, Ir and Ru. More preferable metal oxides supported on the carrier include oxides of Rh, Pd, Ir, and Ru. In the production method of the present embodiment, only one kind may be used or two or more kinds may be used as the heterogeneous catalyst.
不均一触媒の担体としては、オキソ反応に活性を持つ金属種の酸化物であることが、活性の点で好ましい。このことから、担体としては、Ｃｏ、Ｆｅ、Ｎｉから選ばれるいずれかの元素の酸化物を用いることがさらに好ましい。また、担体に担持される金属としては、金（Ａｕ）を用いることがさらに好ましい。金属酸化物としては、酸化パラジウム（ＰｄＯ）を用いることがさらに好ましい。なお、ＰｄＯなどの金属酸化物は、水素、一酸化炭素、有機化合物などの還元剤を用いて還元し、金属状態にしてから、不均一触媒の材料として用いてもよい。不均一触媒の担体としては、例えば、粉末状、粒子状など任意の形状のものを用いることができる。 As the carrier of the heterogeneous catalyst, an oxide of a metal species having activity in the oxo reaction is preferable in terms of activity. For this reason, it is more preferable to use an oxide of any element selected from Co, Fe, and Ni as the carrier. Further, it is more preferable to use gold (Au) as the metal supported on the carrier. It is more preferable to use palladium oxide (PdO) as the metal oxide. A metal oxide such as PdO may be used as a material for a heterogeneous catalyst after being reduced to a metallic state by using a reducing agent such as hydrogen, carbon monoxide, or an organic compound. As the carrier of the heterogeneous catalyst, for example, a carrier having an arbitrary shape such as powder or particulate can be used.
不均一触媒としては、上記の中でも特に、触媒活性が高く、高い収率が得られるため、Ｃｏ３Ｏ４からなる担体に、ＡｕまたはＰｄＯが担持されたものを用いることが、特に好ましい。
不均一触媒として、Ｃｏ３Ｏ４からなる担体に、Ａｕが担持されたものを用いる場合、触媒中のＡｕの割合は、高い収率が得られるため、担体としての金属酸化物と担持される金属または金属酸化物の全金属原子中の１〜２０原子％であることが好ましく、５〜１５原子％であることがより好ましい。
不均一触媒として、Ｃｏ３Ｏ４からなる担体に、ＰｄＯが担持されたものを用いる場合、触媒中のＰｄＯの割合は、高い収率が得られるため、担体としての金属酸化物と担持される金属または金属酸化物の全金属原子中の１〜２０原子％であることが好ましく、５〜１５原子％であることがより好ましい。
As the heterogeneous catalyst, it is particularly preferable to use a carrier composed of Co 3 O 4 in which Au or PdO is supported, because the catalytic activity is particularly high and a high yield can be obtained.
When Au is supported on a carrier made of Co 3 O 4 as the heterogeneous catalyst, the ratio of Au in the catalyst is supported with the metal oxide as the carrier because a high yield can be obtained. It is preferably 1 to 20 atomic%, more preferably 5 to 15 atomic% of the total metal atoms of the metal or metal oxide.
When a carrier made of Co 3 O 4 on which PdO is supported is used as the heterogeneous catalyst, the proportion of PdO in the catalyst is supported with the metal oxide as the carrier because a high yield can be obtained. It is preferably 1 to 20 atomic%, more preferably 5 to 15 atomic% of the total metal atoms of the metal or metal oxide.
本実施形態の製造方法における不均一触媒の使用量は、一般式（１）で表される不飽和アルコール１００質量部に対して０．１〜２０質量部であることが安定して反応を進行させる上で好ましく、１〜１５質量部であることがより好ましく、５〜１０質量部であることがさらに好ましい。一般式（１）で表される不飽和アルコール１００質量部に対する不均一触媒の使用量が５質量部以上であると、効果的に反応性を向上させることができる。また、不均一触媒の使用量が１０質量部以下であると、経済的に好ましい。 The amount of the heterogeneous catalyst used in the production method of the present embodiment is stably 0.1 to 20 parts by mass with respect to 100 parts by mass of the unsaturated alcohol represented by the general formula (1), and the reaction proceeds stably. It is preferable that the amount is 1 to 15 parts by mass, more preferably 5 to 10 parts by mass. When the amount of the heterogeneous catalyst used with respect to 100 parts by mass of the unsaturated alcohol represented by the general formula (1) is 5 parts by mass or more, the reactivity can be effectively improved. Further, it is economically preferable that the amount of the heterogeneous catalyst used is 10 parts by mass or less.
本実施形態の製造方法において用いる不均一触媒は、混合ガスと一般式（１）で表される不飽和アルコールとを反応させて得た反応生成物から、例えば、濾過法、遠心分離法、デカンテーション法などにより、容易に分離できる。 The heterogeneous catalyst used in the production method of the present embodiment is obtained from a reaction product obtained by reacting a mixed gas with an unsaturated alcohol represented by the general formula (1), for example, by filtration, centrifugation, or decantation. It can be easily separated by a catalyst method or the like.
本実施形態の製造方法において使用する不均一触媒の製造方法は、不均一触媒の種類に応じて適宜決定できる。例えば、本実施形態において使用する不均一触媒は、以下に示す方法により製造できる。
まず、担体に担持される金属または金属酸化物の原料となる金属元素を含む化合物を、純水に溶解し、第１水溶液とする。次に、担体の原料となる元素を含む化合物を、水に溶解し、第２水溶液とする。その後、第１水溶液と第２水溶液と炭酸ナトリウム水溶液とを混合して攪拌し、沈殿物を得る。
The method for producing the heterogeneous catalyst used in the production method of the present embodiment can be appropriately determined according to the type of the heterogeneous catalyst. For example, the heterogeneous catalyst used in this embodiment can be produced by the method shown below.
First, a compound containing a metal or a metal element as a raw material for a metal oxide supported on a carrier is dissolved in pure water to prepare a first aqueous solution. Next, a compound containing an element as a raw material for the carrier is dissolved in water to prepare a second aqueous solution. Then, the first aqueous solution, the second aqueous solution, and the sodium carbonate aqueous solution are mixed and stirred to obtain a precipitate.
次に、沈殿物を乾燥させて焼成する。
沈殿物の乾燥は、例えば、大気雰囲気下５０〜１００℃で１〜１２時間乾燥させる方法により行うことができる。
また、沈殿物の焼成は、例えば、大気雰囲気下２００〜５００℃で０．５〜５時間加熱する方法により、行うことができる。
以上の工程により、担体と、担体に担持された金属または金属酸化物とからなる触媒が得られる。
The precipitate is then dried and calcined.
The precipitate can be dried, for example, by a method of drying in an air atmosphere at 50 to 100 ° C. for 1 to 12 hours.
Further, the precipitate can be calcined by, for example, heating at 200 to 500 ° C. for 0.5 to 5 hours in an air atmosphere.
Through the above steps, a catalyst composed of a carrier and a metal or metal oxide supported on the carrier is obtained.
（混合ガス）
本実施形態の製造方法においては、水素ガスと一酸化炭素ガスとを含む混合ガスを用いる。混合ガスは、水素ガスと一酸化炭素ガスとを含むものであればよく、水素ガスと一酸化炭素ガスの他に、窒素、アルゴン等の不活性ガスを含んでいてもよいが、空気、酸素等の酸化性ガスは含まない方が好ましい。
混合ガス中における水素ガスと一酸化炭素ガスとは、任意の割合とすることができる。混合ガス中における水素ガスと一酸化炭素ガスとの割合は、高い収率が得られるため、モル比で９：１〜１：５の割合で用いることが好ましく、２：１〜１：５の割合で用いることがより好ましい。
(Mixed gas)
In the production method of the present embodiment, a mixed gas containing hydrogen gas and carbon monoxide gas is used. The mixed gas may contain hydrogen gas and carbon monoxide gas, and may contain an inert gas such as nitrogen or argon in addition to hydrogen gas and carbon monoxide gas, but air and oxygen. It is preferable not to contain such an oxidizing gas.
The ratio of hydrogen gas and carbon monoxide gas in the mixed gas can be arbitrary. Since a high yield can be obtained, the ratio of hydrogen gas to carbon monoxide gas in the mixed gas is preferably 9: 1 to 1: 5 in terms of molar ratio, and is 2: 1 to 1: 5. It is more preferable to use it in proportion.
（溶媒）
本実施形態の製造方法において使用する溶媒としては、混合ガスと一般式（１）で表される不飽和アルコールとの反応に関与しない化学種を用いることができ、例えば、テトラヒドロフラン、ジオキサン、アセトン、メチルエチルケトン、シクロヘキサンノン、酢酸エチル、酢酸−ｎ−プロピル、酢酸−ｎ−ブチル、ｎ−へプタン、アセトニトリル、トルエン、キシレン、Ｎ−メチルピロリドン、γ−ブチロラクトン、Ｎ,Ｎ−ジメチルホルムアミド、Ｎ,Ｎ−ジメチルアセトアミドなどが挙げられる。これらの溶媒の中でも特に、高い収率が得られるため、テトラヒドロフラン、アセトン、酢酸エチルから選ばれるいずれかを用いることが好ましい。なお、不飽和アルコール自体が液体であり、生成するラクトンを溶解するものである場合には、溶媒を使用せず反応することもできる。
(solvent)
As the solvent used in the production method of the present embodiment, a chemical species that does not participate in the reaction between the mixed gas and the unsaturated alcohol represented by the general formula (1) can be used, and for example, tetrahydrofuran, dioxane, acetone, etc. Methylethylketone, cyclohexanenon, ethyl acetate, -n-propyl acetate, n-butyl acetate, n-heptane, acetonitrile, toluene, xylene, N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N − Dimethylacetamide and the like. Among these solvents, it is preferable to use any one selected from tetrahydrofuran, acetone, and ethyl acetate because a high yield can be obtained. When the unsaturated alcohol itself is a liquid and dissolves the lactone produced, the reaction can be carried out without using a solvent.
（反応条件）
本実施形態の製造方法において、反応容器内で、混合ガスと一般式（１）で表される不飽和アルコールとを不均一触媒の存在下で反応させる際の反応条件は、混合ガスと一般式（１）で表される不飽和アルコールとの反応が進行する範囲内で、一般式（１）で表される不飽和アルコールの種類などに応じて適宜決定できる。反応条件は、例えば、以下に示す（ａ）〜（ｃ）の条件を１つ以上満たすことが好ましい。
(Reaction condition)
In the production method of the present embodiment, the reaction conditions for reacting the mixed gas and the unsaturated alcohol represented by the general formula (1) in the reaction vessel in the presence of a heterogeneous catalyst are the mixed gas and the general formula. Within the range in which the reaction with the unsaturated alcohol represented by (1) proceeds, it can be appropriately determined according to the type of unsaturated alcohol represented by the general formula (1) and the like. As the reaction conditions, for example, it is preferable that one or more of the conditions (a) to (c) shown below are satisfied.
（ａ）反応圧力
反応圧力としては、例えば、反応容器内の圧力を２〜６ＭＰａとすることが好ましく、４〜６ＭＰａとすることがより好ましい。反応圧力が２〜６ＭＰａであると、高い収率が得られる。
（ｂ）反応温度
反応温度としては、６０℃未満では反応速度が遅く、１４０℃超では副反応が起こりやすくなるので、反応容器内の温度を６０〜１４０℃とすることが好ましく、８０〜１２０℃とすることがより好ましい。反応温度が８０〜１２０℃であると、適切な反応速度が得られやすく、高い収率が得られる。
（ｃ）反応時間
反応時間があまりに短いと、一般式（１）で表される不飽和アルコールの転化率が不十分となる場合がある。反応時間があまりに長いと、生成物が分解する可能性がある。このため、反応時間は、１〜４０時間とすることが好ましく、１０〜２０時間とすることがより好ましい。反応時間が１０〜２０時間であると、高い収率を確保でき、かつ良好な生産性が得られる。
(A) Reaction pressure As the reaction pressure, for example, the pressure in the reaction vessel is preferably 2 to 6 MPa, more preferably 4 to 6 MPa. When the reaction pressure is 2 to 6 MPa, a high yield can be obtained.
(B) Reaction temperature As the reaction temperature, the reaction rate is slow below 60 ° C., and side reactions are likely to occur above 140 ° C. Therefore, the temperature inside the reaction vessel is preferably 60 to 140 ° C., preferably 80 to 120 ° C. More preferably, the temperature is. When the reaction temperature is 80 to 120 ° C., an appropriate reaction rate can be easily obtained, and a high yield can be obtained.
(C) Reaction time If the reaction time is too short, the conversion rate of the unsaturated alcohol represented by the general formula (1) may be insufficient. If the reaction time is too long, the product may decompose. Therefore, the reaction time is preferably 1 to 40 hours, more preferably 10 to 20 hours. When the reaction time is 10 to 20 hours, a high yield can be ensured and good productivity can be obtained.
以下、実施例および比較例により本発明をさらに具体的に説明する。なお、本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.
（触媒１）
塩化金酸（ＨＡｕＣｌ４・４Ｈ２Ｏ、田中貴金属工業社製）４１１．８５ｍｇ（１ｍｍｏｌ）を純水（１ｍＬ）に溶解して第１水溶液を得た。
また、硝酸コバルト（ＩＩ）（Ｃｏ（ＮＯ３）２・６Ｈ２Ｏ）（東京化成社製）２．６１９ｇ（９ｍｍｏｌ）を純水（９９ｍＬ）に溶解して第２水溶液を得た。
また、炭酸ナトリウム（Ｎａ２ＣＯ３、富士フイルム和光純薬社製）２．６５ｇ（２５ｍｍｏｌ）を純水（１００ｍＬ）に溶解して炭酸ナトリウム水溶液を得た。
(Catalyst 1)
Chloroauric acid (HAuCl 4 · 4H 2 O, Tanaka Kikinzoku Co., Ltd.) to obtain a first aqueous solution by dissolving 411.85mg the (1 mmol) in pure water (1 mL).
Further, to obtain a second aqueous solution by dissolving cobalt nitrate (II) and (Co (NO 3) 2 · 6H 2 O) ( manufactured by Tokyo Kasei Kogyo Co., Ltd.) 2.619g (9mmol) in pure water (99 mL).
Further, 2.65 g (25 mmol) of sodium carbonate (Na 2 CO 3 , manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in pure water (100 mL) to obtain an aqueous sodium carbonate solution.
次に、第１水溶液と第２水溶液とを混合して混合溶液とした。この混合溶液のｐＨが８以上となるように、ｐＨ計（装置名:ＨＭ−３０Ｐ、東亜ディーケーケー社製）にてｐＨを確認しながら炭酸ナトリウム水溶液を添加し、５時間攪拌した。その後、吸引ろ過により沈殿物を得た。
次いで、得られた沈殿物を遠心瓶に入れ、純水（２００ｍＬ）を加えて激しく振った。続いて、遠心分離装置（装置名：Ｈ−３６、コクサン社製）を用いて遠心分離することにより、沈殿物を回収した。これを３回繰り返すことにより、沈殿物を洗浄した。
その後、沈殿物を、乾燥機（装置名:ＮＤＯ−５００Ｗ、東京理化器械社製）に入れて大気雰囲気下７０℃で一晩乾燥させ、焼成機（装置名:ＭＭＦ−１、アズワン社製）を用いて大気雰囲気下３００℃で４時間加熱して焼成した。
以上の工程により、Ｃｏ３Ｏ４担体にＡｕが担持された触媒１を得た。
Next, the first aqueous solution and the second aqueous solution were mixed to prepare a mixed solution. An aqueous sodium carbonate solution was added while checking the pH with a pH meter (device name: HM-30P, manufactured by Toa DKK) so that the pH of this mixed solution was 8 or more, and the mixture was stirred for 5 hours. Then, a precipitate was obtained by suction filtration.
Then, the obtained precipitate was placed in a centrifuge bottle, pure water (200 mL) was added, and the mixture was vigorously shaken. Subsequently, the precipitate was recovered by centrifugation using a centrifuge (device name: H-36, manufactured by Koksan Co., Ltd.). The precipitate was washed by repeating this three times.
After that, the precipitate was placed in a dryer (device name: NDO-500W, manufactured by Tokyo Rika Kikai Co., Ltd.) and dried overnight at 70 ° C. in an air atmosphere, and then a baking machine (device name: MMF-1, manufactured by AS ONE Corporation). Was heated at 300 ° C. for 4 hours in an air atmosphere and fired.
Through the above steps, a catalyst 1 in which Au was supported on a Co 3 O 4 carrier was obtained.
次に、以下に示す方法により、触媒１における触媒中のＡｕの割合を求めた。
触媒１を所定量（５ｍｇ）測り取り、濃塩酸（富士フイルム和光純薬社製）と濃硝酸（富士フイルム和光純薬社製）を混合して調製した王水（３ｍＬ）に完全に溶かした後、純水で規定量（１００ｍＬ）まで薄めた。その溶液のＡｕ濃度をマイクロ波プラズマ原子発光分光分析（ＭＰ−ＡＥＳ）装置（装置名：４１００ ＭＰ−ＡＥＳ、アジレント社製）により測定し、最初に測り取った触媒中に含まれるＡｕの量を算出した。
その結果、触媒１は、Ｃｏ３Ｏ４からなる担体に、１０原子％のＡｕが担持されたものであった。
Next, the ratio of Au in the catalyst in the catalyst 1 was determined by the method shown below.
The catalyst 1 was measured in a predetermined amount (5 mg) and completely dissolved in aqua regia (3 mL) prepared by mixing concentrated hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and concentrated nitric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). After that, it was diluted with pure water to a specified amount (100 mL). The Au concentration of the solution was measured by a microwave plasma atomic emission spectroscopic analysis (MP-AES) device (device name: 4100 MP-AES, manufactured by Azilent Co., Ltd.), and the amount of Au contained in the catalyst measured first was measured. Calculated.
As a result, the catalyst 1 was a carrier composed of Co 3 O 4 in which 10 atomic% Au was supported.
（触媒２）
硝酸パラジウム（Ｐｄ（ＮＯ３）２）水溶液（Ｐｄ：２００ｇ／Ｌ）（田中貴金属工業社製）５３２μＬ（１ｍｍｏｌ）を純水（１ｍＬ）で希釈して第１水溶液を得た。
また、硝酸コバルト（ＩＩ）（Ｃｏ（ＮＯ３）２・６Ｈ２Ｏ、東京化成社製）２．６１９ｇ（９ｍｍｏｌ）を純水（９９ｍＬ）に溶解して第２水溶液を得た。
また、炭酸ナトリウム（Ｎａ２ＣＯ３、富士フイルム和光純薬社製）２．６５ｇ（２５ｍｍｏｌ）を純水（１００ｍＬ）に溶解して炭酸ナトリウム水溶液を得た。
(Catalyst 2)
Palladium nitrate (Pd (NO 3 ) 2 ) aqueous solution (Pd: 200 g / L) (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) 532 μL (1 mmol) was diluted with pure water (1 mL) to obtain a first aqueous solution.
Further, to obtain cobalt nitrate (II) (Co (NO 3 ) 2 · 6H 2 O, manufactured by Tokyo Chemical Industry Co., Ltd.) a second aqueous solution by dissolving 2.619g of (9 mmol) in pure water (99 mL).
Further, 2.65 g (25 mmol) of sodium carbonate (Na 2 CO 3 , manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in pure water (100 mL) to obtain an aqueous sodium carbonate solution.
次に、第１水溶液と第２水溶液とを混合して混合溶液とした。この混合溶液のｐＨが８以上となるように、ｐＨ計（装置名:ＨＭ−３０Ｐ、東亜ディーケーケー社製）にてｐＨを確認しながら炭酸ナトリウム水溶液を添加し、３時間攪拌した。その後、吸引ろ過により沈殿物を得た。
次いで、得られた沈殿物を遠心瓶に入れ、純水（２００ｍＬ）を加えて激しく振った。続いて、遠心分離装置（装置名：Ｈ−３６、コクサン社製）を用いて遠心分離することにより、沈殿物を回収した。これを３回繰り返すことにより、沈殿物を洗浄した。
その後、沈殿物を、乾燥機（装置名:ＮＤＯ−５００Ｗ、東京理化器械社製）に入れて大気雰囲気下７０℃で一晩乾燥させ、焼成機（装置名:ＭＭＦ−１、アズワン社製）を用いて大気雰囲気下３００℃で４時間加熱して焼成した。
以上の工程により、Ｃｏ３Ｏ４担体にＰｄＯが担持された触媒２を得た。
Next, the first aqueous solution and the second aqueous solution were mixed to prepare a mixed solution. An aqueous sodium carbonate solution was added while checking the pH with a pH meter (device name: HM-30P, manufactured by Toa DKK) so that the pH of this mixed solution was 8 or more, and the mixture was stirred for 3 hours. Then, a precipitate was obtained by suction filtration.
Then, the obtained precipitate was placed in a centrifuge bottle, pure water (200 mL) was added, and the mixture was vigorously shaken. Subsequently, the precipitate was recovered by centrifugation using a centrifuge (device name: H-36, manufactured by Koksan Co., Ltd.). The precipitate was washed by repeating this three times.
After that, the precipitate was placed in a dryer (device name: NDO-500W, manufactured by Tokyo Rika Kikai Co., Ltd.) and dried overnight at 70 ° C. in an air atmosphere, and then a baking machine (device name: MMF-1, manufactured by AS ONE Corporation). Was heated at 300 ° C. for 4 hours in an air atmosphere and fired.
Through the above steps, a catalyst 2 in which PdO was supported on a Co 3 O 4 carrier was obtained.
次に、以下に示す方法により、触媒２における触媒中のＰｄＯの割合を求めた。
触媒２を所定量（５ｍｇ）測り取り、濃塩酸（富士フイルム和光純薬社製）と濃硝酸（富士フイルム和光純薬社製）を混合して調製した王水（３ｍＬ）に完全に溶かした後、純水で規定量（１００ｍＬ）まで薄めた。その溶液のＰｄ濃度をマイクロ波プラズマ原子発光分光分析（ＭＰ−ＡＥＳ）装置（装置名：４１００ ＭＰ−ＡＥＳ、アジレント社製）により測定し、最初に測り取った触媒中に含まれるＰｄの量を算出した。
その結果、触媒２は、Ｃｏ３Ｏ４からなる担体に、１０原子％のＰｄＯが担持されたものであった。
Next, the ratio of PdO in the catalyst in the catalyst 2 was determined by the method shown below.
The catalyst 2 was measured in a predetermined amount (5 mg) and completely dissolved in aqua regia (3 mL) prepared by mixing concentrated hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and concentrated nitric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). After that, it was diluted with pure water to a specified amount (100 mL). The Pd concentration of the solution was measured by a microwave plasma atomic emission spectroscopic analysis (MP-AES) device (device name: 4100 MP-AES, manufactured by Azilent Co., Ltd.), and the amount of Pd contained in the catalyst measured first was measured. Calculated.
As a result, the catalyst 2 had 10 atomic% of PdO supported on a carrier composed of Co 3 O 4 .
（実施例１）
反応容器（オートクレーブ）に、表１に示す溶媒（３ｍＬ、３７ｍｍｏｌ）と、表１に示す不飽和アルコールとしてのアリルアルコール（富士フイルム和光純薬社製）（０．２ｍＬ、３ｍｍｏｌ）と、表１に示す不均一触媒（２０ｍｇ）（アリルアルコール１００質量部に対して１１．５質量部）とを入れた。次いで、反応容器内の空気を、水素ガスと一酸化炭素ガスとを表１に示す割合（Ｈ２：ＣＯ）で含む混合ガスで置換し、反応容器内を混合ガス雰囲気とした。
その後、反応容器内で、表１に示す反応圧力（ＭＰａ）、反応温度（℃）、反応時間（時間）で、混合ガスとアリルアルコールとを反応させた。溶媒はいずれも富士フイルム和光純薬社製のものを使用した。
(Example 1)
In a reaction vessel (autoclave), the solvent shown in Table 1 (3 mL, 37 mmol), allyl alcohol as an unsaturated alcohol shown in Table 1 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (0.2 mL, 3 mmol), and Table 1 The heterogeneous catalyst (20 mg) shown in (11.5 parts by mass with respect to 100 parts by mass of allyl alcohol) was added. After the air in the reaction vessel, the percentage indicating the hydrogen gas and carbon monoxide gas in Table 1: was replaced with a mixed gas containing at (H 2 CO), the reaction vessel was a mixed gas atmosphere.
Then, the mixed gas and allyl alcohol were reacted in the reaction vessel at the reaction pressure (MPa), reaction temperature (° C.), and reaction time (hours) shown in Table 1. The solvent used was that manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
得られた反応液の組成をガスクロマトグラフィー（装置名:６８５０ＧＣ、アジレント社製）により分析し、以下に示す方法により、不飽和アルコールの転化率および目的物であるラクトン化合物の収率を算出した。
その結果を表１に示す。なお、反応液からの触媒の分離は、ガラスフィルターを使用した濾過により分離できた。
The composition of the obtained reaction solution was analyzed by gas chromatography (device name: 6850GC, manufactured by Agilent), and the conversion rate of unsaturated alcohol and the yield of the target lactone compound were calculated by the methods shown below. ..
The results are shown in Table 1. The catalyst could be separated from the reaction solution by filtration using a glass filter.
（実施例２〜実施例１５）
使用した触媒、溶媒、混合ガスの割合または反応温度を、表１に記載の通り変更したこと以外は、実施例１同様に反応させた。得られた反応液の組成を、実施例１同様にして分析し、実施例１同様にして不飽和アルコールの転化率およびラクトン化合物の収率を算出した。その結果を表１に示す。なお、反応液からの触媒の分離は、ガラスフィルターを使用した濾過により分離できた。
(Examples 2 to 15)
The reaction was carried out in the same manner as in Example 1 except that the ratio of the catalyst, solvent and mixed gas used or the reaction temperature was changed as shown in Table 1. The composition of the obtained reaction solution was analyzed in the same manner as in Example 1, and the conversion rate of unsaturated alcohol and the yield of the lactone compound were calculated in the same manner as in Example 1. The results are shown in Table 1. The catalyst could be separated from the reaction solution by filtration using a glass filter.
（比較例１）
触媒１を使用しないこと以外は、実施例１同様にして反応させた。得られた反応液の組成を、実施例１同様にして分析し、実施例１同様にして不飽和アルコールの転化率およびラクトン化合物の収率を算出した。その結果を表１に示す。
(Comparative Example 1)
The reaction was carried out in the same manner as in Example 1 except that the catalyst 1 was not used. The composition of the obtained reaction solution was analyzed in the same manner as in Example 1, and the conversion rate of unsaturated alcohol and the yield of the lactone compound were calculated in the same manner as in Example 1. The results are shown in Table 1.
（ラクトン化合物の収率）
ラクトン化合物の収率は、ガスクロマトグラフィー（ＧＣ）を用いて内標準法により決定した。まず、目的生成物であるラクトン化合物の標準物質に基づいて検量線を作成した。内標準物質にはトリデカン（富士フイルム和光純薬社製）を用いた。
(Yield of lactone compound)
The yield of the lactone compound was determined by an internal standard method using gas chromatography (GC). First, a calibration curve was prepared based on the standard substance of the lactone compound, which is the target product. Tridecane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the internal standard substance.
（不飽和アルコールの転化率）
不飽和アルコールとしてのアリルアルコールの転化率は、検量線に基づき、以下に示す式を用いて算出した。
転化率（％）＝[（仕込み時のアリルアルコール（モル）−反応液中のアリルアルコール（モル））／仕込み時のアリルアルコール（モル）]×１００
(Conversion rate of unsaturated alcohol)
The conversion rate of allyl alcohol as an unsaturated alcohol was calculated using the formula shown below based on the calibration curve.
Conversion rate (%) = [(Allyl alcohol (mol) at the time of preparation-Allyl alcohol (mol) in the reaction solution) / Allyl alcohol (mol) at the time of preparation] × 100
表１に示すように、水素ガスと一酸化炭素ガスとを含む混合ガスと、アリルアルコールとを、触媒１または触媒２の存在下で反応させることにより、ラクトン化合物であるγ−ブチロラクトンが得られた。
これに対し、不均一触媒を用いずに混合ガスと、アリルアルコールとを反応させた比較例１では、γ−ブチロラクトンが得られなかった。
なお、理由は定かではないが、反応溶媒にｎ−ヘプタンのようなアルカン（飽和脂肪族炭化水素）を含むと収率が低い結果となった。そのため、反応溶媒にはアルカン（飽和脂肪族炭化水素）を含まない方が好ましい。
As shown in Table 1, γ-butyrolactone, which is a lactone compound, is obtained by reacting a mixed gas containing hydrogen gas and carbon monoxide gas with allyl alcohol in the presence of catalyst 1 or catalyst 2. It was.
On the other hand, in Comparative Example 1 in which the mixed gas was reacted with allyl alcohol without using a heterogeneous catalyst, γ-butyrolactone could not be obtained.
Although the reason is not clear, the yield was low when an alkane (saturated aliphatic hydrocarbon) such as n-heptane was contained in the reaction solvent. Therefore, it is preferable that the reaction solvent does not contain alkane (saturated aliphatic hydrocarbon).
Claims (6)
前記担体に担持される金属が、Ａｕ、Ｒｈ、Ｐｄ、Ｉｒ、Ｒｕのいずれかの金属またはＲｈ、Ｐｄ、Ｉｒ、Ｒｕのいずれかの金属酸化物からなる請求項１または請求項２に記載のラクトン化合物の製造方法。 The carrier is made of an oxide of any of Mn, Fe, Co, Ni, Cu, and Zn.
The first or second claim, wherein the metal supported on the carrier is made of any of Au, Rh, Pd, Ir, and Ru or a metal oxide of Rh, Pd, Ir, and Ru. Method for producing a lactone compound.
前記反応容器内で、前記混合ガスと前記不飽和アルコールとを反応させる反応工程とを有し、
前記溶媒が、テトラヒドロフラン、アセトン、酢酸エチルから選ばれるいずれかである請求項１〜請求項５のいずれか一項に記載のラクトン化合物の製造方法。 A step of putting the solvent, the unsaturated alcohol, and the heterogeneous catalyst in the reaction vessel to create the mixed gas atmosphere in the reaction vessel.
It has a reaction step of reacting the mixed gas with the unsaturated alcohol in the reaction vessel.
The method for producing a lactone compound according to any one of claims 1 to 5, wherein the solvent is selected from tetrahydrofuran, acetone, and ethyl acetate.
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|---|---|---|---|---|
| JPH0211582A (en) * | 1988-05-10 | 1990-01-16 | Shell Internatl Res Maatschappij Bv | Production of lactone |
| JP2008517995A (en) * | 2004-10-27 | 2008-05-29 | ダニスコ エイ／エス | process |
| JP2009241060A (en) * | 2008-03-11 | 2009-10-22 | Mitsubishi Chemicals Corp | Heterogeneous catalyst for use in conversion reaction of olefinic unsaturated compound, process for producing derivative of olefinic unsaturated compound, and process for producing aldehyde or amine |
| WO2017170808A1 (en) * | 2016-03-31 | 2017-10-05 | 国立大学法人九州大学 | Method for producing four-membered ring lactone and heterogeneous catalyst |
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| JPH0211582A (en) * | 1988-05-10 | 1990-01-16 | Shell Internatl Res Maatschappij Bv | Production of lactone |
| JP2008517995A (en) * | 2004-10-27 | 2008-05-29 | ダニスコ エイ／エス | process |
| JP2009241060A (en) * | 2008-03-11 | 2009-10-22 | Mitsubishi Chemicals Corp | Heterogeneous catalyst for use in conversion reaction of olefinic unsaturated compound, process for producing derivative of olefinic unsaturated compound, and process for producing aldehyde or amine |
| WO2017170808A1 (en) * | 2016-03-31 | 2017-10-05 | 国立大学法人九州大学 | Method for producing four-membered ring lactone and heterogeneous catalyst |
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