JP5991521B2 - Method for producing carbonyl compound - Google Patents
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- JP5991521B2 JP5991521B2 JP2012181888A JP2012181888A JP5991521B2 JP 5991521 B2 JP5991521 B2 JP 5991521B2 JP 2012181888 A JP2012181888 A JP 2012181888A JP 2012181888 A JP2012181888 A JP 2012181888A JP 5991521 B2 JP5991521 B2 JP 5991521B2
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- 150000001728 carbonyl compounds Chemical class 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 229910002367 SrTiO Inorganic materials 0.000 claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 150000001299 aldehydes Chemical class 0.000 claims description 7
- 239000012454 non-polar solvent Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 150000003333 secondary alcohols Chemical class 0.000 claims description 6
- 150000003138 primary alcohols Chemical class 0.000 claims description 5
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 40
- 239000003054 catalyst Substances 0.000 description 36
- 239000010948 rhodium Substances 0.000 description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 239000000758 substrate Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012429 reaction media Substances 0.000 description 11
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- -1 Aromatic alcohols Chemical class 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- WGQMUABRZGUAOS-UHFFFAOYSA-N (2,5-dimethoxyphenyl)methanol Chemical compound COC1=CC=C(OC)C(CO)=C1 WGQMUABRZGUAOS-UHFFFAOYSA-N 0.000 description 1
- IOWGHQGLUMEZKG-UHFFFAOYSA-N (2-bromophenyl)methanol Chemical compound OCC1=CC=CC=C1Br IOWGHQGLUMEZKG-UHFFFAOYSA-N 0.000 description 1
- WYLYBQSHRJMURN-UHFFFAOYSA-N (2-methoxyphenyl)methanol Chemical compound COC1=CC=CC=C1CO WYLYBQSHRJMURN-UHFFFAOYSA-N 0.000 description 1
- FSWNRRSWFBXQCL-UHFFFAOYSA-N (3-bromophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1 FSWNRRSWFBXQCL-UHFFFAOYSA-N 0.000 description 1
- CLECMSNCZUMKLM-UHFFFAOYSA-N (4-ethenylphenyl)methanol Chemical compound OCC1=CC=C(C=C)C=C1 CLECMSNCZUMKLM-UHFFFAOYSA-N 0.000 description 1
- QCZORVSTESPHCO-UHFFFAOYSA-N (4-ethynylphenyl)methanol Chemical compound OCC1=CC=C(C#C)C=C1 QCZORVSTESPHCO-UHFFFAOYSA-N 0.000 description 1
- MTXQKSQYMREAGJ-UHFFFAOYSA-N (4-methylsulfanylphenyl)methanol Chemical compound CSC1=CC=C(CO)C=C1 MTXQKSQYMREAGJ-UHFFFAOYSA-N 0.000 description 1
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- RRENWXJYWGKSKD-UHFFFAOYSA-N 1-[4-(hydroxymethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=C(CO)C=C1 RRENWXJYWGKSKD-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- ACUZDYFTRHEKOS-SNVBAGLBSA-N 2-Decanol Natural products CCCCCCCC[C@@H](C)O ACUZDYFTRHEKOS-SNVBAGLBSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- IIGNZLVHOZEOPV-UHFFFAOYSA-N 3-Methoxybenzyl alcohol Chemical compound COC1=CC=CC(CO)=C1 IIGNZLVHOZEOPV-UHFFFAOYSA-N 0.000 description 1
- MOOUWXDQAUXZRG-UHFFFAOYSA-N 4-(trifluoromethyl)benzyl alcohol Chemical compound OCC1=CC=C(C(F)(F)F)C=C1 MOOUWXDQAUXZRG-UHFFFAOYSA-N 0.000 description 1
- FKMVNGWJGSSDCF-UHFFFAOYSA-N 4-acetoxybenzyl alcohol Chemical compound CC(=O)OC1=CC=C(CO)C=C1 FKMVNGWJGSSDCF-UHFFFAOYSA-N 0.000 description 1
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 1
- ACUZDYFTRHEKOS-UHFFFAOYSA-N decan-2-ol Chemical compound CCCCCCCCC(C)O ACUZDYFTRHEKOS-UHFFFAOYSA-N 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 125000002350 geranyl group Chemical group [H]C([*])([H])/C([H])=C(C([H])([H])[H])/C([H])([H])C([H])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VEDDBHYQWFOITD-UHFFFAOYSA-N para-bromobenzyl alcohol Chemical compound OCC1=CC=C(Br)C=C1 VEDDBHYQWFOITD-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
本発明は、第１級アルコール又は第２級アルコールから、アルデヒド又はケトンを合成する、カルボニル化合物の製造方法に関する。 The present invention relates to a method for producing a carbonyl compound, in which an aldehyde or a ketone is synthesized from a primary alcohol or a secondary alcohol.
アルデヒド、ケトン等のカルボニル化合物は、香料、医薬品、農薬等の中間体を得るために、工業的に有用であることが知られている。カルボニル化合物を製造する方法としては、アルコールを基質としてこれを酸化反応させる工程を備える方法が一般的である。例えば、白金、ルテニウム、ロジウム等の触媒の存在下に、アルコールからカルボニル化合物に変換する接触脱水素反応を利用した製造方法が知られている。この反応では、水素分子が生成する。
接触脱水素反応を用いる場合には、酸化剤を必要としない利点があるが、基質の構造によっては、副反応が併発する場合がある。具体的な副反応としては、ヒドロキシル基以外の他の官能基に対する酸化反応、生成した水素分子による他の官能基に対する還元反応、生成したカルボニル化合物によるアルドール反応等が挙げられる。
Carbonyl compounds such as aldehydes and ketones are known to be industrially useful for obtaining intermediates such as fragrances, pharmaceuticals, and agricultural chemicals. As a method for producing a carbonyl compound, a method comprising a step of oxidizing an alcohol as a substrate is common. For example, a production method using a catalytic dehydrogenation reaction in which an alcohol is converted to a carbonyl compound in the presence of a catalyst such as platinum, ruthenium, or rhodium is known. In this reaction, hydrogen molecules are generated.
When the catalytic dehydrogenation reaction is used, there is an advantage that an oxidant is not necessary, but side reactions may occur depending on the structure of the substrate. Specific examples of the side reaction include an oxidation reaction with respect to other functional groups other than the hydroxyl group, a reduction reaction with respect to other functional groups by the generated hydrogen molecules, an aldol reaction with the generated carbonyl compound, and the like.
特許文献１には、飽和第２級アルコールを、下記一般式（Ｉ）で表わされるハイドロタルサイトからなる担体と、このハイドロタルサイト担体に担持されたロジウムとを含む固体触媒の存在下、酸化剤を用いない条件で脱水素させて、飽和カルボニル化合物を製造する方法が開示されている。
［Ｍｇ８−ＺＡｌＺ（ＯＨ）１６］Ｚ＋［Ｘｎ− ｚ／ｎ］・ｍＨ２Ｏ （Ｉ）
（式中、Ｚは０＜Ｚ≦４の実数であり、Ｘｎ−はアニオンとその電荷を表し、ｎは１≦ｎ≦４の自然数であり、ｍは０≦ｍ≦１２の実数である。）
In Patent Document 1, a saturated secondary alcohol is oxidized in the presence of a solid catalyst containing a carrier composed of hydrotalcite represented by the following general formula (I) and rhodium supported on the hydrotalcite carrier. A method for producing a saturated carbonyl compound by dehydrogenation under a condition in which no agent is used is disclosed.
[Mg 8-Z Al Z ( OH) 16] Z + [X n- z / n] · mH 2 O (I)
(In the formula, Z is a real number of 0 <Z ≦ 4, X n− represents an anion and its charge, n is a natural number of 1 ≦ n ≦ 4, and m is a real number of 0 ≦ m ≦ 12. .)
また、非特許文献１には、Ｐｔ／ＴｉＯ２の存在下、水中にて芳香族アルコールに可視光を照射して、アルデヒドを合成する方法が開示されている。 Non-Patent Document 1 discloses a method for synthesizing an aldehyde by irradiating an aromatic alcohol with visible light in water in the presence of Pt / TiO 2 .
本発明の目的は、副反応を抑制しつつ、脱水素反応を円滑に進めて、カルボニル化合物を効率よく製造する方法を提供することである。 An object of the present invention is to provide a method for efficiently producing a carbonyl compound by smoothly proceeding with a dehydrogenation reaction while suppressing side reactions.
本発明は、以下に示される。
１．第１級アルコール又は第２級アルコール（基質）と、Ｒｕ原子が担持され且つＲｈ原子がドープされたＳｒＴｉＯ３（触媒）と、水とを含む反応系に、可視光線を照射して、該アルコールをアルデヒド又はケトンに変換する工程（反応工程）を備える、カルボニル化合物の製造方法において、
上記反応系は、（１）ｐＨが３〜５の範囲にある酸性水溶液のみを含む、又は、（２）ｐＨが３〜５の範囲にある酸性水溶液と、双極子モーメントが１．０Ｄ以下の非極性溶媒とを含むことを特徴とする、カルボニル化合物の製造方法。
２．上記非極性溶媒がトルエン又はヘキサンを含む上記１に記載のカルボニル化合物の製造方法。
３．上記酸性水溶液が、リン酸、硫酸又は塩酸の水溶液である上記１又は２に記載のカルボニル化合物の製造方法。
The present invention is shown below.
1. A reaction system comprising a primary alcohol or a secondary alcohol (substrate), SrTiO 3 (catalyst) supporting Ru atoms and doped with Rh atoms, and water is irradiated with visible light, and the alcohol is irradiated. In a method for producing a carbonyl compound, comprising a step (reaction step) of converting aldehyde into a aldehyde or ketone ,
The reaction system includes (1) only an acidic aqueous solution having a pH in the range of 3 to 5, or (2) an acidic aqueous solution having a pH in the range of 3 to 5 and a dipole moment of 1.0 D or less. The manufacturing method of a carbonyl compound characterized by including a nonpolar solvent .
2. 2. The method for producing a carbonyl compound according to 1 above, wherein the nonpolar solvent contains toluene or hexane .
3. 3. The method for producing a carbonyl compound according to 1 or 2 above, wherein the acidic aqueous solution is an aqueous solution of phosphoric acid, sulfuric acid or hydrochloric acid .
本発明によれば、副反応を抑制しつつ、脱水素反応を円滑に進めて、カルボニル化合物を効率よく製造することができる。反応を、５０℃以下の低い温度で進めることができるので、プロセスの省エネルギー化を図ることができる。更に、使用した触媒は、反応工程の後、簡便な方法で分離除去できるので、生成したカルボニル化合物の精製を効率よく進めることができる。 ADVANTAGE OF THE INVENTION According to this invention, a dehydrogenation reaction can be advanced smoothly, suppressing a side reaction, and a carbonyl compound can be manufactured efficiently. Since the reaction can proceed at a low temperature of 50 ° C. or lower, energy saving of the process can be achieved. Furthermore, since the used catalyst can be separated and removed by a simple method after the reaction step, purification of the produced carbonyl compound can proceed efficiently.
本発明は、第１級アルコール又は第２級アルコールと、Ｒｕ原子が担持され且つＲｈ原子がドープされたＳｒＴｉＯ３と、水とを含む反応系に、可視光線を照射して、該アルコールをアルデヒド又はケトンに変換する工程（以下、「反応工程」という。）を備えるカルボニル化合物の製造方法である（下記スキーム参照）。
上記反応工程において、１級アルコール又は２級アルコール（以下、「アルコール」と表記する）は、本発明に係る基質であり、１価アルコール及び多価アルコールのいずれでもよい。そして、飽和アルコール及び不飽和アルコールのいずれでもよく、脂肪族アルコール、脂環式アルコール及び芳香族アルコールのいずれでもよい。即ち、ビニル基、アルキニル基、フェニル基、ナフチル基、アリル基、シンナミル基、ゲラニル基、アルキル基、シクロアルキル基等の炭化水素基を有するアルコールを用いることができる。また、アルコールは、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；アルコキシ基；エーテル結合；チオエーテル結合；エステル結合；カルボキシル基；カルボニル基；アルデヒド基；アミド結合；ニトロ基；シリル基；ニトロ基；アミノ基；ジアルキルアミノ基等を有する化合物であってもよい。更に、水又は有機溶剤への溶解性の可否も問わない。 In the reaction step, primary alcohol or secondary alcohol (hereinafter referred to as “alcohol”) is a substrate according to the present invention, and may be either monohydric alcohol or polyhydric alcohol. And any of saturated alcohol and unsaturated alcohol may be sufficient, and any of aliphatic alcohol, alicyclic alcohol, and aromatic alcohol may be sufficient. That is, an alcohol having a hydrocarbon group such as a vinyl group, an alkynyl group, a phenyl group, a naphthyl group, an allyl group, a cinnamyl group, a geranyl group, an alkyl group, or a cycloalkyl group can be used. Alcohols are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy group; ether bond; thioether bond; ester bond; carboxyl group; carbonyl group; aldehyde group; amide bond; A compound having a nitro group, an amino group, a dialkylamino group, or the like. Furthermore, the solubility in water or an organic solvent is not questioned.
本発明において好ましく用いられるアルコールは、以下に例示される。
脂肪族アルコールとしては、１−デカノール、ｔｒａｎｓ−シンナミルアルコール、ゲラニオール、ネロール、クロチルアルコール、２−デカノール等が挙げられる。
脂環式アルコールとしては、シクロオクタノール、シクロヘキサノール等が挙げられる。
芳香族アルコールとしては、ベンジルアルコール、２−メトキシベンジルアルコール、３−メトキシベンジルアルコール、４−メトキシベンジルアルコール、２，５−ジメトキシベンジルアルコール、４−トリイソプロピルシロキシベンジルアルコール、４−アセトキシベンジルアルコール、２−ブロモベンジルアルコール、３−ブロモベンジルアルコール、４−ブロモベンジルアルコール、４−メチルチオベンジルアルコール、４−アセチルベンジルアルコール、４−トリフルオロメチルベンジルアルコール、４−ニトロベンジルアルコール、４−ビニルベンジルアルコール、４−エチニルベンジルアルコール、α−メチル−４−メトキシベンジルアルコール、β−ナフチルメチルカルビノール等が挙げられる。
The alcohol preferably used in the present invention is exemplified below.
Examples of the aliphatic alcohol include 1-decanol, trans-cinnamyl alcohol, geraniol, nerol, crotyl alcohol, 2-decanol and the like.
Examples of the alicyclic alcohol include cyclooctanol and cyclohexanol.
Aromatic alcohols include benzyl alcohol, 2-methoxybenzyl alcohol, 3-methoxybenzyl alcohol, 4-methoxybenzyl alcohol, 2,5-dimethoxybenzyl alcohol, 4-triisopropylsiloxybenzyl alcohol, 4-acetoxybenzyl alcohol, 2 -Bromobenzyl alcohol, 3-bromobenzyl alcohol, 4-bromobenzyl alcohol, 4-methylthiobenzyl alcohol, 4-acetylbenzyl alcohol, 4-trifluoromethylbenzyl alcohol, 4-nitrobenzyl alcohol, 4-vinylbenzyl alcohol, 4 -Ethynyl benzyl alcohol, (alpha) -methyl-4-methoxy benzyl alcohol, (beta) -naphthylmethyl carbinol, etc. are mentioned.
上記反応工程において、Ｒｕ原子が担持され且つＲｈ原子がドープされたＳｒＴｉＯ３（以下、「Ｒｕ／ＳｒＴｉＯ３：Ｒｈ」と表記する）は、本発明に係る触媒であり、カルボニル化合物への高い変換効率を与える。このＲｕ／ＳｒＴｉＯ３：Ｒｈにおいて、Ｒｈ原子のドープ量は、ＳｒＴｉＯ３に対して、好ましくは０．５〜１．５モル％、より好ましくは１．０〜１．２５モル％である。また、Ｒｕの担持量は、Ｒｕ／ＳｒＴｉＯ３：Ｒｈを１００質量％とした場合に、好ましくは０．１〜１．５質量％、より好ましくは０．７〜１．０質量％である。 In the above reaction step, Ru atom-supported and Rh atom-doped SrTiO 3 (hereinafter referred to as “Ru / SrTiO 3 : Rh”) is a catalyst according to the present invention, and is highly converted to a carbonyl compound. Give efficiency. In this Ru / SrTiO 3 : Rh, the doping amount of Rh atoms is preferably 0.5 to 1.5 mol%, more preferably 1.0 to 1.25 mol% with respect to SrTiO 3 . The amount of Ru supported is preferably 0.1 to 1.5% by mass, more preferably 0.7 to 1.0% by mass, with Ru / SrTiO 3 : Rh being 100% by mass.
上記触媒の使用量は、触媒反応としてより実用的であることから、上記アルコール１モルに対して、好ましくは１０〜３５ｇ、より好ましくは１０〜３０ｇである。 Since the usage-amount of the said catalyst is more practical as a catalytic reaction, Preferably it is 10-35g with respect to 1 mol of said alcohol, More preferably, it is 10-30g.
本発明に係る反応工程においては、水の存在が不可欠である。この「水」は、単に水であってよいし、基質（アルコール）ではない媒質を溶解させてなる水溶液であってもよい。本発明では、反応系は、（１）ｐＨが３〜５の範囲にある酸性水溶液のみを含む、又は、（２）ｐＨが３〜５の範囲にある酸性水溶液と、双極子モーメントが１．０Ｄ以下の非極性溶媒とを含むこととし、上記媒質として、水に溶解して酸性水溶液を与える化合物を用いる。尚、本発明においては、一般的な有機合成において、有機溶媒として用いられる化合物であって、水に溶解しない有機化合物を併用してもよい。以下、水又は水を含む混合液体を、「反応媒体」として説明する。 In the reaction process according to the present invention, the presence of water is essential. The “water” may be simply water or an aqueous solution in which a medium that is not a substrate (alcohol) is dissolved. In the present invention, the reaction system includes (1) only an acidic aqueous solution having a pH of 3 to 5 or (2) an acidic aqueous solution having a pH of 3 to 5 and a dipole moment of 1. A nonpolar solvent of 0D or less is contained, and a compound that dissolves in water to give an acidic aqueous solution is used as the medium. In the present invention, an organic compound that is used as an organic solvent in general organic synthesis and does not dissolve in water may be used in combination. Hereinafter, water or a mixed liquid containing water will be described as a “reaction medium”.
上記反応媒体のｐＨ（２５℃）は、反応性の観点から、３〜５である。
水に溶解して酸性水溶液を与える化合物としては、リン酸、硫酸、塩酸等が挙げられる。
The pH (25 ° C.) of the reaction medium is 3 to 5 from the viewpoint of reactivity.
Examples of the compound that dissolves in water to give an acidic aqueous solution include phosphoric acid, sulfuric acid, hydrochloric acid and the like.
上記非極性溶媒は、双極子モーメントが１．０Ｄ以下の化合物であり、例えば、トルエン、ヘキサン等が特に好ましい。 The nonpolar solvent is a compound having a dipole moment of 1.0 D or less , and for example, toluene, hexane and the like are particularly preferable.
上記反応媒体が、非極性溶媒を含有する場合、その割合の上限は、反応性の観点から、反応媒体の全体に対して、好ましくは７０質量％である。 When the said reaction medium contains a nonpolar solvent , the upper limit of the ratio is preferably 70 mass% with respect to the whole reaction medium from the viewpoint of reactivity.
上記反応媒体の使用量は、特に限定されないが、反応系におけるアルコールの使用量の割合が、反応媒体の全体に対して、０．５〜２０質量％の範囲となるように選択することが好ましい。 The amount of the reaction medium used is not particularly limited, but is preferably selected so that the proportion of the alcohol used in the reaction system is in the range of 0.5 to 20% by mass with respect to the entire reaction medium. .
上記反応工程においては、アルコール、触媒及び水を含む反応系に、波長が４２０ｎｍ以上の可視光線が照射される。可視光線の光源は、特に限定されないが、キセノンランプ、クリプトンランプ等を用いることができる。使用する光源の種類によっては、必要に応じて、紫外線等の、短波長の光をカットするフィルターを用いてもよい。 In the reaction step, visible light having a wavelength of 420 nm or more is irradiated to a reaction system containing an alcohol, a catalyst, and water. The light source of visible light is not particularly limited, and a xenon lamp, a krypton lamp, or the like can be used. Depending on the type of light source used, a filter that cuts short-wavelength light such as ultraviolet rays may be used as necessary.
可視光線の照度は、特に限定されないが、反応性の観点から、好ましくは１００，０００〜３００，０００ルクス、より好ましくは１５０，０００〜３００，０００ルクスである。 The illuminance of visible light is not particularly limited, but is preferably 100,000 to 300,000 lux, more preferably 150,000 to 300,000 lux from the viewpoint of reactivity.
上記反応工程における反応系の温度は、アルコールの種類により、適宜、選択されるが、好ましくは５℃〜５０℃、より好ましくは５℃〜３０℃である。反応を、加熱を伴わない温度（例えば、２０℃〜２７℃）で進めることができるという点で、プロセスの省エネルギー化を図ることができる。 Although the temperature of the reaction system in the said reaction process is suitably selected according to the kind of alcohol, Preferably it is 5 to 50 degreeC, More preferably, it is 5 to 30 degreeC. Energy saving of the process can be achieved in that the reaction can proceed at a temperature that does not involve heating (for example, 20 ° C. to 27 ° C.).
上記反応系の雰囲気は、通常、不活性ガス雰囲気であり、窒素ガス、アルゴンガス等を用いることが好ましい。尚、反応系に酸素ガスを含むと、カルボニル化合物の収率が低下する場合がある。 The atmosphere of the reaction system is usually an inert gas atmosphere, and it is preferable to use nitrogen gas, argon gas, or the like. In addition, when oxygen gas is included in the reaction system, the yield of the carbonyl compound may decrease.
尚、上記反応系は、少なくとも基質、触媒及び反応媒体を含むが、基質の種類によっては、基質が反応媒体の一部又は全部に溶解する場合、基質が反応媒体に全く溶解せず、基質、触媒及び反応媒体が独立して含まれる場合がある。いずれの場合も、反応系を撹拌しながら可視光線を照射してよいし、反応系を静置した状態で可視光線を照射してもよい。
即ち、本発明に係る反応工程では、反応系の形態に関わらず、反応系に可視光線を照射することにより、目的のアルデヒド又はケトンを得ることができる。また、一部の基質を除いてカルボニル基がカルボキシル基に変性することもない。
The reaction system includes at least a substrate, a catalyst, and a reaction medium. However, depending on the type of substrate, when the substrate is dissolved in part or all of the reaction medium, the substrate is not dissolved in the reaction medium at all. A catalyst and reaction medium may be included independently. In either case, visible light may be irradiated while stirring the reaction system, or visible light may be irradiated while the reaction system is left standing.
That is, in the reaction step according to the present invention, the target aldehyde or ketone can be obtained by irradiating the reaction system with visible light regardless of the form of the reaction system. Further, except for some substrates, the carbonyl group is not modified to a carboxyl group.
上記反応工程により得られた反応液には、通常、生成したカルボニル化合物、未反応のアルコール、触媒及び反応媒体が含まれる。カルボニル化合物を単離する場合には、上記反応液を、従来、公知の、濾過、蒸留、クロマト分離等を含む、回収工程又は精製工程に供すればよい。また、反応液に含まれる触媒は、再利用が可能であるので、カルボニル化合物を連続的に製造する場合には、同じ反応系を利用することができる。 The reaction solution obtained by the above reaction step usually contains the produced carbonyl compound, unreacted alcohol, catalyst and reaction medium. When isolating a carbonyl compound, the reaction solution may be subjected to a conventionally known recovery step or purification step including filtration, distillation, chromatographic separation, and the like. In addition, since the catalyst contained in the reaction solution can be reused, the same reaction system can be used when the carbonyl compound is continuously produced.
本発明の製造方法によれば、カルボニル化合物の収率は、好ましい態様において、好ましくは４０％以上、より好ましくは６０％以上、更に好ましくは８０％以上とすることができる。尚、上記「収率」とは、基質として用いたアルコールのモル量に基づき算出される値である。 According to the production method of the present invention, in a preferred embodiment, the yield of the carbonyl compound is preferably 40% or more, more preferably 60% or more, and further preferably 80% or more. The “yield” is a value calculated based on the molar amount of alcohol used as a substrate.
以下、本発明について、実施例を挙げて具体的に説明する。本発明は、これらの実施例に何ら制約されない。
尚、各実験例において触媒として用いた化合物を下記に示す。
（１）触媒Ａ（Ｒｕ／ＳｒＴｉＯ３：Ｒｈ）
Ｒｈを１．０モル％ドープさせたＳｒＴｉＯ３に、Ｒｕを０．７質量％担持させたもの
（２）触媒Ｂ（Ｐｔ／ＳｒＴｉＯ３：Ｒｈ）
Ｒｈを０．２モル％ドープさせたＳｒＴｉＯ３に、Ｐｔを０．７質量％担持させたもの
（３）触媒Ｃ（Ｒｕ，Ｐｔ／ＮａＮｂＯ３：Ｉｒ）
Ｉｒを０．５モル％ドープさせたＮａＮｂＯ３に、Ｒｕを０．７質量％及びＰｔを１．０質量％担持させたもの
（４）触媒Ｄ（Ｒｕ／ＣｕＧａＳ２）
ＣｕＧａＳ２に、Ｒｕを１．７質量％担持させたもの
（５）触媒Ｅ（Ｒｕ／ＡｇＧａＳ２）
ＡｇＧａＳ２に、Ｒｕを１．０質量％担持させたもの
（６）触媒Ｆ（Ｐｔ／ＳｒＴｉＯ３：Ｉｒ）
Ｉｒを０．２モル％ドープさせたＳｒＴｉＯ３に、Ｐｔを０．３質量％担持させたもの
（７）触媒Ｇ（Ｐｔ／ＮａＮｂＯ３：Ｉｒ）
Ｉｒを０．５モル％ドープさせたＮａＮｂＯ３に、Ｐｔを０．３質量％担持させたもの
（８）触媒Ｈ（Ｒｕ／ＣｕＧａＳ２）
ＣｕＧａＳ２に、Ｒｕを１．０質量％担持させたもの
（９）触媒Ｉ（Ｒｕ／Ｃ）
Ｃに、Ｒｕを５．０質量％担持させたもの
Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples.
In addition, the compound used as a catalyst in each experiment example is shown below.
(1) Catalyst A (Ru / SrTiO 3 : Rh)
What supported 0.7 mass% of Ru on SrTiO 3 doped with 1.0 mol% of Rh (2) Catalyst B (Pt / SrTiO 3 : Rh)
What supported 0.7 mass% of Pt on SrTiO 3 doped with 0.2 mol% of Rh (3) Catalyst C (Ru, Pt / NaNbO 3 : Ir)
What supported 0.7 mass% of Ru and 1.0 mass% of Pt on NaNbO 3 doped with 0.5 mol% of Ir (4) Catalyst D (Ru / CuGaS 2 )
CuGaS 2 supporting 1.7% by mass of Ru (5) Catalyst E (Ru / AgGaS 2 )
AgGaS 2 carrying 1.0% by mass of Ru (6) Catalyst F (Pt / SrTiO 3 : Ir)
What supported 0.3 mass% of Pt on SrTiO 3 doped with 0.2 mol% of Ir (7) Catalyst G (Pt / NaNbO 3 : Ir)
What supported 0.3 mass% of Pt on NaNbO 3 doped with 0.5 mol% of Ir (8) Catalyst H (Ru / CuGaS 2 )
CuGaS 2 carrying 1.0% by mass of Ru (9) Catalyst I (Ru / C)
C loaded with 5.0% by mass of Ru
実施例１
窒素ガスを封入したバルーンと、ホウ硅酸ガラス製の窓（厚さ２ｍｍ）とを装着したガラス製フラスコに、フッ素樹脂製の磁気撹拌子、５．３ｍｇのＲｕ／ＳｒＴｉＯ３：Ｒｈ（触媒Ａ）、６９ｍｇ（０．５ｍｍｏｌ）の４−メトキシベンジルアルコール、５ｍＬのリン酸水溶液（ｐＨ３．４）、及び、１０ｍＬのトルエン（双極子モーメント：０．３６Ｄ）を、順次、収容した（２５℃）。これらを撹拌して、４−メトキシベンジルアルコールがトルエンに溶解し、触媒が、トルエン層と水層との界面に分散しているのを確認した後、フラスコを密閉し、フラスコ全体をアルミニウム箔で覆った。そして、フラスコ内の減圧と窒素ガス導入とを５回繰り返し、フラスコ内を窒素ガス雰囲気とした。
次に、上記フラスコを、２５℃の水浴中に配置し、フラスコ内の原料を撹拌しながら、キセノンランプ（出力３００Ｗ）及びカットフィルターを用いて、４２０ｎｍを超える波長の光を、ガラス窓を介して照射した（照度１．６８×１０５ルクス）。尚、反応の追跡をガスクロマトグラフ・質量分析装置又はガスクロマトグラフ装置により行った。
２４時間反応させた後、ミリポア社製メンブランフィルター（孔径０．４５μｍ）により、濾別し、濾液の有機相（トルエン溶液）を回収するとともに、フィルター上の残渣及び濾液の水相を酢酸エチルで洗浄した。次いで、洗浄液（酢酸エチル溶液）と、上記濾液の有機相（トルエン溶液）とを組み合わせて、濃縮、乾燥し、４−メトキシベンズアルデヒドを得た。内部標準として１，１，２，２−テトラクロロエタンを、測定溶媒として重クロロホルムを用いて１Ｈ ＮＭＲ測定を行い、収率９２％を得た。
A glass flask equipped with a balloon filled with nitrogen gas and a window made of borosilicate glass (thickness 2 mm), a magnetic stirrer made of fluororesin, 5.3 mg of Ru / SrTiO 3 : Rh (catalyst A) ), 69 mg (0.5 mmol) of 4-methoxybenzyl alcohol, 5 mL of phosphoric acid aqueous solution (pH 3.4), and 10 mL of toluene (dipole moment: 0.36D) were sequentially accommodated (25 ° C.). . These were stirred and 4-methoxybenzyl alcohol was dissolved in toluene, and after confirming that the catalyst was dispersed at the interface between the toluene layer and the aqueous layer, the flask was sealed, and the entire flask was covered with aluminum foil. Covered. And the pressure reduction in a flask and nitrogen gas introduction were repeated 5 times, and the inside of a flask was made into nitrogen gas atmosphere.
Next, the flask was placed in a 25 ° C. water bath, and light of a wavelength exceeding 420 nm was passed through a glass window using a xenon lamp (output 300 W) and a cut filter while stirring the raw materials in the flask. (Illuminance 1.68 × 10 5 lux). The reaction was traced by a gas chromatograph / mass spectrometer or a gas chromatograph.
After reacting for 24 hours, the mixture was filtered through a membrane filter (pore size: 0.45 μm) manufactured by Millipore, and the organic phase (toluene solution) of the filtrate was recovered. Washed. Subsequently, the washing liquid (ethyl acetate solution) and the organic phase (toluene solution) of the filtrate were combined and concentrated and dried to obtain 4-methoxybenzaldehyde. 1 H NMR measurement was performed using 1,1,2,2-tetrachloroethane as an internal standard and deuterated chloroform as a measurement solvent, and a yield of 92% was obtained.
比較例１
Ｒｕ／ＳｒＴｉＯ３：Ｒｈ（触媒Ａ）に代えて、Ｐｔ／ＳｒＴｉＯ３：Ｒｈ（触媒Ｂ）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は５．８％であった。
Comparative Example 1
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that Pt / SrTiO 3 : Rh (catalyst B) was used instead of Ru / SrTiO 3 : Rh (catalyst A). The yield was 5.8%.
比較例２
Ｒｕ／ＳｒＴｉＯ３：Ｒｈ（触媒Ａ）に代えて、Ｒｕ，Ｐｔ／ＮａＮｂＯ３：Ｉｒ（触媒Ｃ）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は３．４％であった。
Comparative Example 2
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that Ru, Pt / NaNbO 3 : Ir (catalyst C) was used instead of Ru / SrTiO 3 : Rh (catalyst A). The yield was 3.4%.
比較例３
Ｒｕ／ＳｒＴｉＯ３：Ｒｈ（触媒Ａ）に代えて、Ｒｕ／ＣｕＧａＳ２（触媒Ｄ）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は２．８％であった。
Comparative Example 3
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that Ru / CuGaS 2 (catalyst D) was used instead of Ru / SrTiO 3 : Rh (catalyst A). The yield was 2.8%.
比較例４
Ｒｕ／ＳｒＴｉＯ３：Ｒｈ（触媒Ａ）に代えて、Ｒｕ／ＡｇＧａＳ２（触媒Ｅ）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は１．４％であった。
Comparative Example 4
4-methoxybenzaldehyde was obtained in the same manner as in Example 1, except that Ru / AgGaS 2 (catalyst E) was used instead of Ru / SrTiO 3 : Rh (catalyst A). The yield was 1.4%.
比較例５
Ｒｕ／ＳｒＴｉＯ３：Ｒｈ（触媒Ａ）に代えて、Ｐｔ／ＳｒＴｉＯ３：Ｉｒ（触媒Ｆ）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は６．９％であった。
Comparative Example 5
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that Pt / SrTiO 3 : Ir (catalyst F) was used instead of Ru / SrTiO 3 : Rh (catalyst A). The yield was 6.9%.
比較例６
Ｒｕ／ＳｒＴｉＯ３：Ｒｈ（触媒Ａ）に代えて、Ｐｔ／ＮａＮｂＯ３：Ｉｒ（触媒Ｇ）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は１．８％であった。
Comparative Example 6
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that Pt / NaNbO 3 : Ir (catalyst G) was used instead of Ru / SrTiO 3 : Rh (catalyst A). The yield was 1.8%.
比較例７
Ｒｕ／ＳｒＴｉＯ３：Ｒｈ（触媒Ａ）に代えて、Ｒｕ／ＣｕＧａＳ２（触媒Ｈ）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は１．４％であった。
Comparative Example 7
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that Ru / CuGaS 2 (catalyst H) was used instead of Ru / SrTiO 3 : Rh (catalyst A). The yield was 1.4%.
比較例８
Ｒｕ／ＳｒＴｉＯ３：Ｒｈ（触媒Ａ）に代えて、Ｒｕ／Ｃ（触媒Ｉ）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は４．９％であった。
Comparative Example 8
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that Ru / C (catalyst I) was used instead of Ru / SrTiO 3 : Rh (catalyst A). The yield was 4.9%.
以下の実験（実施例２〜４及び比較例９〜１０）では、溶媒を変えて、４−メトキシベンジルアルコールから４−メトキシベンズアルデヒドを製造した。 In the following experiments (Examples 2 to 4 and Comparative Examples 9 to 10), 4-methoxybenzaldehyde was produced from 4-methoxybenzyl alcohol by changing the solvent.
実施例２
トルエンに代えて、ヘキサン（双極子モーメント：０．０Ｄ）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は６８％であった。
Example 2
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that hexane (dipole moment: 0.0D) was used instead of toluene. The yield was 68%.
参考例１
トルエンに代えて、ジクロロメタン（双極子モーメント：１．６０Ｄ）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は２６％であった。
Reference example 1
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that dichloromethane (dipole moment: 1.60 D) was used instead of toluene. The yield was 26%.
実施例３
トルエンを不使用とした以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は７７％であった。
Example 3
The same operation as in Example 1 was performed except that toluene was not used to obtain 4-methoxybenzaldehyde. The yield was 77%.
比較例９
リン酸水溶液（ｐＨ３．４）を不使用としたこと、即ち、トルエン１０ｍＬのみを用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は２％であった。
Comparative Example 9
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that the phosphoric acid aqueous solution (pH 3.4) was not used, that is, only 10 mL of toluene was used. The yield was 2%.
比較例１０
リン酸水溶液（ｐＨ３．４）及びトルエンを不使用とし、ジクロロメタン（双極子モーメント：１．６０Ｄ）１０ｍＬのみを用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は１％未満であった。
Comparative Example 10
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that phosphoric acid aqueous solution (pH 3.4) and toluene were not used, and only 10 mL of dichloromethane (dipole moment: 1.60 D) was used. The yield was less than 1%.
以下の実験では、水のｐＨ（２５℃）を変化させて、４−メトキシベンジルアルコールから４−メトキシベンズアルデヒドを製造した。
参考例２
リン酸水溶液（ｐＨ３．４）に代えて、リン酸水溶液（２５℃におけるｐＨ１．４）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は３１％であった。
Reference example 2
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that a phosphoric acid aqueous solution (pH 1.4 at 25 ° C.) was used instead of the phosphoric acid aqueous solution (pH 3.4). The yield was 31%.
参考例３
リン酸水溶液（ｐＨ３．４）に代えて、リン酸水溶液（２５℃におけるｐＨ５．３）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は５７％であった。
Reference example 3
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that a phosphoric acid aqueous solution (pH 5.3 at 25 ° C.) was used instead of the phosphoric acid aqueous solution (pH 3.4). The yield was 57%.
参考例４
リン酸水溶液（ｐＨ３．４）に代えて、水（２５℃におけるｐＨ７．０）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は５９％であった。
Reference example 4
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that water (pH 7.0 at 25 ° C.) was used instead of the phosphoric acid aqueous solution (pH 3.4). The yield was 59%.
参考例５
リン酸水溶液（ｐＨ３．４）に代えて、炭酸カリウム水溶液（２５℃におけるｐＨ８．２）を用いた以外は、実施例１と同じ操作を行い、４−メトキシベンズアルデヒドを得た。収率は５６％であった。
Reference Example 5
4-methoxybenzaldehyde was obtained in the same manner as in Example 1 except that a potassium carbonate aqueous solution (pH 8.2 at 25 ° C.) was used instead of the phosphoric acid aqueous solution (pH 3.4). The yield was 56%.
以下の実験（実施例４〜２５）では、基質及び反応条件を変えて、カルボニル化合物を製造した。その結果を表４及び表５に示す。
本発明の製造方法により製造されたカルボニル化合物は、香料、医薬品、農薬等の製造原料等として好適である。 The carbonyl compound produced by the production method of the present invention is suitable as a raw material for producing fragrances, pharmaceuticals, agricultural chemicals and the like.
Claims (3)
上記反応系は、（１）ｐＨが３〜５の範囲にある酸性水溶液のみを含む、又は、（２）ｐＨが３〜５の範囲にある酸性水溶液と、双極子モーメントが１．０Ｄ以下の非極性溶媒とを含むことを特徴とする、カルボニル化合物の製造方法。 A reaction system containing primary alcohol or secondary alcohol, SrTiO 3 on which Ru atoms are supported and doped with Rh atoms, and water is irradiated with visible light to convert the alcohol into aldehyde or ketone. In the method for producing a carbonyl compound comprising the step of:
The reaction system includes (1) only an acidic aqueous solution having a pH in the range of 3 to 5, or (2) an acidic aqueous solution having a pH in the range of 3 to 5 and a dipole moment of 1.0 D or less. The manufacturing method of a carbonyl compound characterized by including a nonpolar solvent .
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