JP6132643B2 - Pd compound supported catalyst - Google Patents
Pd compound supported catalyst Download PDFInfo
- Publication number
- JP6132643B2 JP6132643B2 JP2013090346A JP2013090346A JP6132643B2 JP 6132643 B2 JP6132643 B2 JP 6132643B2 JP 2013090346 A JP2013090346 A JP 2013090346A JP 2013090346 A JP2013090346 A JP 2013090346A JP 6132643 B2 JP6132643 B2 JP 6132643B2
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- JP
- Japan
- Prior art keywords
- compound
- group
- acid
- supported catalyst
- carbon
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 92
- 150000001875 compounds Chemical class 0.000 title claims description 43
- 150000001336 alkenes Chemical class 0.000 claims description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 37
- 229910052740 iodine Inorganic materials 0.000 claims description 31
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 239000011630 iodine Substances 0.000 claims description 25
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 15
- 238000010485 C−C bond formation reaction Methods 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
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- 150000002497 iodine compounds Chemical class 0.000 claims description 6
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- 150000001639 boron compounds Chemical class 0.000 claims description 3
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- 238000006243 chemical reaction Methods 0.000 description 51
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
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- 229910052757 nitrogen Inorganic materials 0.000 description 8
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 8
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- 238000003756 stirring Methods 0.000 description 7
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 125000000304 alkynyl group Chemical group 0.000 description 6
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 6
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 6
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
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- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229940032094 squalane Drugs 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 4
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- 235000021357 Behenic acid Nutrition 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 4
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
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- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 4
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
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- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 description 2
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- RRHPTXZOMDSKRS-PHFPKPIQSA-L (1z,5z)-cycloocta-1,5-diene;dichloropalladium Chemical compound Cl[Pd]Cl.C\1C\C=C/CC\C=C/1 RRHPTXZOMDSKRS-PHFPKPIQSA-L 0.000 description 1
- SHMUCLXLMZFUNG-UHFFFAOYSA-N 1,2-dibromocycloocta-1,5-diene Chemical compound BrC1=C(Br)CCC=CCC1 SHMUCLXLMZFUNG-UHFFFAOYSA-N 0.000 description 1
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- FREZLSIGWNCSOQ-UHFFFAOYSA-N 3-methylbutanoyl 3-methylbutanoate Chemical compound CC(C)CC(=O)OC(=O)CC(C)C FREZLSIGWNCSOQ-UHFFFAOYSA-N 0.000 description 1
- SQAHPYZABTWPNY-UHFFFAOYSA-N 3-phenylpropanoyl 3-phenylpropanoate Chemical compound C=1C=CC=CC=1CCC(=O)OC(=O)CCC1=CC=CC=C1 SQAHPYZABTWPNY-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- OCNZHGHKKQOQCZ-CLFAGFIQSA-N [(z)-octadec-9-enoyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC(=O)CCCCCCC\C=C/CCCCCCCC OCNZHGHKKQOQCZ-CLFAGFIQSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052800 carbon group element Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- UMOOTHVGGLVSOC-UHFFFAOYSA-N dec-9-enoyl dec-9-enoate Chemical compound C=CCCCCCCCC(=O)OC(=O)CCCCCCCC=C UMOOTHVGGLVSOC-UHFFFAOYSA-N 0.000 description 1
- HTWWKYKIBSHDPC-UHFFFAOYSA-N decanoyl decanoate Chemical compound CCCCCCCCCC(=O)OC(=O)CCCCCCCCC HTWWKYKIBSHDPC-UHFFFAOYSA-N 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- NWADXBLMWHFGGU-UHFFFAOYSA-N dodecanoic anhydride Chemical compound CCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCC NWADXBLMWHFGGU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- BVBRZOLXXOIMQG-UHFFFAOYSA-N fluoroborane Chemical compound FB BVBRZOLXXOIMQG-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229910001849 group 12 element Inorganic materials 0.000 description 1
- VIFSQFMBTOTLEE-UHFFFAOYSA-N hexa-2,4-dienoyl hexa-2,4-dienoate Chemical compound CC=CC=CC(=O)OC(=O)C=CC=CC VIFSQFMBTOTLEE-UHFFFAOYSA-N 0.000 description 1
- QWZBEFCPZJWDKC-UHFFFAOYSA-N hexadecanoyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCCCCCC QWZBEFCPZJWDKC-UHFFFAOYSA-N 0.000 description 1
- PKHMTIRCAFTBDS-UHFFFAOYSA-N hexanoyl hexanoate Chemical compound CCCCCC(=O)OC(=O)CCCCC PKHMTIRCAFTBDS-UHFFFAOYSA-N 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- AUONNNVJUCSETH-UHFFFAOYSA-N icosanoyl icosanoate Chemical compound CCCCCCCCCCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCCCCCCCCCC AUONNNVJUCSETH-UHFFFAOYSA-N 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- RAFYDKXYXRZODZ-UHFFFAOYSA-N octanoyl octanoate Chemical compound CCCCCCCC(=O)OC(=O)CCCCCCC RAFYDKXYXRZODZ-UHFFFAOYSA-N 0.000 description 1
- LJAGLQVRUZWQGK-UHFFFAOYSA-N oxecane-2,10-dione Chemical compound O=C1CCCCCCCC(=O)O1 LJAGLQVRUZWQGK-UHFFFAOYSA-N 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
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- RCRYHUPTBJZEQS-UHFFFAOYSA-N tetradecanoyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCCCC RCRYHUPTBJZEQS-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- XGOZKNCGVJSRKD-UHFFFAOYSA-N undec-10-enoyl undec-10-enoate Chemical compound C=CCCCCCCCCC(=O)OC(=O)CCCCCCCCC=C XGOZKNCGVJSRKD-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、脂肪酸及びその誘導体からのオレフィンの製造法や有機化合物の炭素−炭素結合形成反応などに有効なＰｄ化合物担持触媒であって、ヨウ素を含有するＰｄ化合物担持触媒に関する。 The present invention relates to a Pd compound-supported catalyst that is effective in a method for producing olefins from fatty acids and derivatives thereof, a carbon-carbon bond forming reaction of an organic compound, and the like, and that contains iodine.
Ｐｄを担持した触媒としては、ＰｄＣｌ2やＰｄ（ＯＡｃ）2などのＰｄ化合物をスルホン化ポリスチレン樹脂に担持した触媒（非特許文献１）や、二価のＰｄ化合物を高分子に担持させた高分子固定化Ｐｄ触媒が知られている（特許文献１）。一方、単体のＰｄとヨウ素を含有する触媒としては、金属ＰｄとＫＩを活性炭に担持した触媒（特許文献２）や、金属ＰｄとＫＩをアルミナに担持した触媒（特許文献３）、担持された触媒粒子が金属パラジウムとヨウ素を含む触媒（特許文献４）が知られている。 Examples of the catalyst supporting Pd include a catalyst in which a Pd compound such as PdCl 2 and Pd (OAc) 2 is supported on a sulfonated polystyrene resin (Non-patent Document 1), and a high catalyst in which a divalent Pd compound is supported on a polymer. A molecule-immobilized Pd catalyst is known (Patent Document 1). On the other hand, as a catalyst containing simple Pd and iodine, a catalyst in which metal Pd and KI are supported on activated carbon (Patent Document 2), a catalyst in which metal Pd and KI are supported on alumina (Patent Document 3), and the like were supported. A catalyst (patent document 4) in which catalyst particles contain metallic palladium and iodine is known.
本発明の課題は、脂肪酸及びその誘導体からのオレフィンの製造方法や有機化合物の炭素−炭素結合形成反応などに有効な、担体にＰｄ化合物を担持させてなるＰｄ化合物担持触媒（Ｐｄ化合物担持触媒）を提供することにある。 An object of the present invention is to provide a Pd compound-supported catalyst in which a Pd compound is supported on a support (Pd compound-supported catalyst), which is effective in a method for producing olefins from fatty acids and derivatives thereof, and a carbon-carbon bond forming reaction of organic compounds. Is to provide.
かかる課題に対し、本発明者らは、Ｐｄ化合物担持触媒であって、Ｐｄ化合物がヨウ素を含有するＰｄ化合物担持触媒を用いることで、脂肪酸及びその誘導体からのオレフィンの製造法における脱カルボニル反応や有機化合物の炭素−炭素結合形成反応の触媒活性が向上することを見出し、本発明の完成に至った。即ち、本発明は、担体にＰｄ化合物を担持させてなるＰｄ化合物担持触媒であって、Ｐｄ化合物がヨウ素を含有するＰｄ化合物担持触媒を提供する。 In response to this problem, the present inventors use a Pd compound-supported catalyst, which is a Pd compound-supported catalyst, and the Pd compound contains iodine, thereby allowing a decarbonylation reaction in a method for producing olefins from fatty acids and derivatives thereof. It has been found that the catalytic activity of the carbon-carbon bond forming reaction of the organic compound is improved, and the present invention has been completed. That is, the present invention provides a Pd compound-supported catalyst in which a Pd compound is supported on a carrier, wherein the Pd compound contains iodine.
本発明の触媒は、高い活性を有し、本発明の触媒を用いると、カルボン酸からのオレフィンの製造や、有機化合物の炭素−炭素結合形成が効率よく進行し、高収率で目的物を合成することができ、工業的にきわめて有利である。 The catalyst of the present invention has high activity. When the catalyst of the present invention is used, the production of olefins from carboxylic acids and the formation of carbon-carbon bonds of organic compounds proceed efficiently, and the target product can be obtained in high yield. It can be synthesized and is extremely industrially advantageous.
［Ｐｄ化合物担持触媒］
本発明のＰｄ化合物担持触媒は、Ｐｄ化合物がヨウ素を含有するＰｄ化合物担持触媒であって、ＸＰＳ装置により、下記条件にて測定することによって得られるＰｄ化合物のＰｄ ３ｄ5/2 結合エネルギーが３３６［ｅＶ］〜３３８［ｅＶ］である。
[Pd compound supported catalyst]
The Pd compound-supported catalyst of the present invention is a Pd compound-supported catalyst in which the Pd compound contains iodine, and the Pd 3d 5/2 binding energy of the Pd compound obtained by measurement under the following conditions with an XPS apparatus is 336. [EV] to 338 [eV].
本発明者らは、ヨウ素を含有する二価のＰｄ化合物の存在が、触媒活性に大きく寄与することを見出した。好ましいヨウ素を含有するＰｄ化合物としては、ヨウ素を含有する無機Ｐｄ化合物、有機Ｐｄ化合物が挙げられる。ヨウ素を含有する無機Ｐｄ化合物としては、ＰｄＩ2、ＰｄＩ2（ＣＯ)2、Ｘ2ＰｄＩ4(Ｘ＝Ｈ，Ｎａ，Ｋ，Ｌｉ)等が挙げられる。ヨウ素を含有する有機Ｐｄ化合物としては、Ｒ2ＰｄＩ2（ここでＲは炭素数１〜６の炭化水素基、ピリジン、ＰＲ’3、ＮＲ’3（ここでＲ’は炭素数１〜６の炭化水素基である)である）、 ＰｄＲ”n(ここでＲ”はＲ又はＲ’の水素原子の１つ又は２つ以上がヨウ素原子に置換された基である)等が挙げられる。ＰｄＲ” nで表されるＰｄ化合物としては、例えばＰｄ（ｐ-ＰｈＩ）2等が挙げられる。安定性及び触媒としての活性の観点から無機Ｐｄ化合物が好ましく、ＰｄＩ2がより好ましい。 The present inventors have found that the presence of a divalent Pd compound containing iodine greatly contributes to the catalytic activity. Preferable Pd compounds containing iodine include inorganic Pd compounds and organic Pd compounds containing iodine. Examples of the inorganic Pd compound containing iodine include PdI 2 , PdI 2 (CO) 2 , X 2 PdI 4 (X═H, Na, K, Li). Organic Pd compounds containing iodine include R 2 PdI 2 (where R is a hydrocarbon group having 1 to 6 carbon atoms, pyridine, PR ′ 3 , NR ′ 3 (where R ′ is a carbon number having 1 to 6 carbon atoms). PdR ″ n (wherein R ″ is a group in which one or more hydrogen atoms of R or R ′ are substituted with iodine atoms), and the like. Examples of the Pd compound represented by PdR ″ n include Pd (p-PhI) 2. From the viewpoint of stability and activity as a catalyst, inorganic Pd compounds are preferable, and PdI 2 is more preferable.
本発明の触媒中の、ヨウ素を含有する二価のＰｄ化合物の存在は、ＸＰＳ装置により、下記条件にて測定することにより決定される。ＸＰＳのＰｄ ３ｄ5/2 結合エネルギーのピーク位置により、ヨウ素を含有する二価のＰｄ化合物の存在を識別できる。またＸ線結晶回折測定装置により、下記条件にて測定することで、ヨウ素を含有する二価のＰｄ化合物の存在を識別することも可能である。但しその場合は、Ｐｄの粒径や担体種によっては見えないこともある。 The presence of the divalent Pd compound containing iodine in the catalyst of the present invention is determined by measuring under the following conditions using an XPS apparatus. The presence of the divalent Pd compound containing iodine can be identified by the peak position of the Pd 3d 5/2 binding energy of XPS. It is also possible to identify the presence of a divalent Pd compound containing iodine by measuring with an X-ray crystal diffraction measurement device under the following conditions. However, in that case, it may not be visible depending on the particle size of Pd and the type of carrier.
〈ＸＰＳ測定条件〉
ＰＨＩ Ｑｕａｎｔｅｒａ ＳＸＭ （ＵＬＶＡＣ−ＰＨＩ，ＩＮＣ）
Ｐａｓｓ ｅｎｅｒｇｙ；１１２ｅＶ、ｓｔｅｐ ｓｉｚｅ；０．２ｅＶ、積算４０回
測定範囲 Ｘ；５００μｍ、Ｙ；５００μｍ
ＰｄＩ2（和光純薬工業（株）製）
Ｐｄ ３ｄ5/2 結合エネルギー：３３７［ｅＶ］
ＰｄＩ2（和光純薬工業（株）製）、２８０℃焼成品
Ｐｄ ３ｄ5/2 結合エネルギー：３３６［ｅＶ］
Ｐｄ金属（和光純薬工業（株）製）
Ｐｄ ３ｄ5/2 結合エネルギー：３３５［ｅＶ］
<XPS measurement conditions>
PHI Quantera SXM (ULVAC-PHI, INC)
Pass energy; 112 eV, step size; 0.2 eV, total 40 times measurement range X: 500 μm, Y: 500 μm
PdI 2 (Wako Pure Chemical Industries, Ltd.)
Pd 3d 5/2 binding energy: 337 [eV]
PdI 2 (manufactured by Wako Pure Chemical Industries, Ltd.), 280 ° C. baked product Pd 3d 5/2 binding energy: 336 [eV]
Pd metal (Wako Pure Chemical Industries, Ltd.)
Pd 3d 5/2 binding energy: 335 [eV]
ヨウ素を含有するＰｄ化合物担持触媒のＸＰＳ装置により測定される、Ｐｄ ３ｄ5/2 結合エネルギーは、結晶構造、粒子径、担体種などにより、若干値が変わることがある。その場合、上述のようにＰｄ ３ｄ5/2 結合エネルギーが：３３６［ｅＶ］〜３３８［ｅＶ］が好ましい。 The Pd 3d 5/2 bond energy measured by an XPS apparatus of a Pd compound-supported catalyst containing iodine may vary slightly depending on the crystal structure, particle diameter, carrier type, and the like. In that case, as described above, the Pd 3d 5/2 binding energy is preferably 336 [eV] to 338 [eV].
〈Ｘ線結晶回折測定条件〉
リガク製ＲＩＮＴ２５００ＶＰＣにて測定
線源；ＣｕのＫα線、管電圧；４０ｋＶ；管電流；１２０ｍＡ、走査速度；１０ｄｅｇ／ｍｉｎ、発散スリット；１．０ｄｅｇ、散乱スリット；１．０ｄｅｇ、受光スリット；０．３ｍｍ、走査角度；５〜７０ｄｅｇ
ＰｄＩ2（和光純薬工業（株）製）
２θ＝１３、２４〜２８、３１〜３５［°］
ＰｄＩ2（和光純薬工業（株）製）、２８０℃焼成品
２θ＝１７、３０、３３〜３４［°］
Ｐｄ金属（和光純薬工業（株）製）
２θ＝４０、４５〜４７、６８［°］
<X-ray crystal diffraction measurement conditions>
Measurement source with RINT 2500VPC manufactured by Rigaku; Cu Kα line, tube voltage; 40 kV; tube current; 120 mA, scanning speed: 10 deg / min, diverging slit; 1.0 deg, scattering slit; 1.0 deg, light receiving slit; 3 mm, scanning angle; 5-70 deg
PdI 2 (Wako Pure Chemical Industries, Ltd.)
2θ = 13, 24-28, 31-35 [°]
PdI 2 (manufactured by Wako Pure Chemical Industries, Ltd.), 280 ° C. fired product 2θ = 17, 30, 33-34 [°]
Pd metal (Wako Pure Chemical Industries, Ltd.)
2θ = 40, 45-47, 68 [°]
ヨウ素を含有するＰｄ化合物担持触媒の担持量が１０質量％以下の場合やＰｄ化合物の結晶粒子径が５０ｎｍ以下の場合は、上記ピークの一つ以上が見られないこともある。 When the supported amount of the iodine-containing Pd compound-supported catalyst is 10% by mass or less, or when the crystal particle diameter of the Pd compound is 50 nm or less, one or more of the above peaks may not be seen.
ヨウ素を含有するＰｄ化合物担持触媒の、ヨウ素原子とパラジウム原子の組成比は、ＸＰＳ装置により測定される、Ｐｄ ３ｄ5/2 結合エネルギーが３３６［ｅＶ］〜３３８［ｅＶ］の範囲にあればよく、触媒の活性点数の関係などから、ＸＰＳ装置により測定される、ヨウ素原子とパラジウム原子のモル比が０．２〜１０が好ましく、１〜３がより好ましく、２がさらに好ましい。
［担体の詳細］
The composition ratio of iodine atom and palladium atom of the Pd compound-supported catalyst containing iodine is sufficient if the Pd 3d 5/2 bond energy is in the range of 336 [eV] to 338 [eV] as measured by an XPS apparatus. From the relationship of the number of active points of the catalyst, etc., the molar ratio of iodine atom to palladium atom measured by XPS apparatus is preferably 0.2 to 10, more preferably 1 to 3, and further preferably 2.
[Details of Carrier]
本発明の触媒に用いる担体としては、ヨウ素を含有するＰｄ化合物を担持する担体は、１５０℃以上の耐熱性を有し、有機溶媒及び反応原料に溶解せず、Ｐｄ化合物を高分散担持できる物質が好ましい。係る担体としては、オレフィン収率の観点から、酸化物又は活性炭が好ましい。酸化物としては、珪藻土、アルミナ、シリカ、シリカ−アルミナ、マグネシア、ジルコニア、チタニア、セリアあるいはそれらの複合酸化物が好ましく、シリカ、ジルコニア、チタニアがより好ましく、ジルコニア、チタニアが更に好ましく、ジルコニアが更により好ましい。活性炭としては、木質系、ヤシガラ系、泥炭系、石炭系等の原料を、水蒸気、二酸化炭素等のガスを用いる物理方法、又は、塩化亜鉛、リン酸等を用いる化学法等によって賦活化されたものが好適に用いられる。 As a carrier used for the catalyst of the present invention, a carrier carrying a Pd compound containing iodine has a heat resistance of 150 ° C. or higher, and is a substance that does not dissolve in an organic solvent and a reaction raw material and can carry a highly dispersed Pd compound. Is preferred. The carrier is preferably an oxide or activated carbon from the viewpoint of olefin yield. As the oxide, diatomaceous earth, alumina, silica, silica-alumina, magnesia, zirconia, titania, ceria or a composite oxide thereof is preferable, silica, zirconia, titania is more preferable, zirconia, titania is further preferable, and zirconia is further preferable. Is more preferable. As activated carbon, raw materials such as wood, coconut husk, peat, and coal were activated by a physical method using a gas such as water vapor or carbon dioxide, or a chemical method using zinc chloride, phosphoric acid, or the like. Those are preferably used.
担体の形態には特に制限はなく、例えば微粉末、粗粒子、ペレットなど、任意の物理的形態をとり得る。担体の比表面積は３０〜３０００ｍ2／ｇ程度であればよい。担体が細孔を有する場合、その細孔容積、平均細孔径や分布は任意であるが、平均細孔径は１〜１００ｎｍ程度が好ましい。本発明のヨウ素を含有するＰｄ化合物の担体上への担持量に特に制限はないが、反応活性の観点から、担体に対して好ましくは０．１質量％以上、より好ましくは１質量％以上、更に好ましくは３質量％以上であり、また、Ｐｄ化合物の高分散担持の観点から、好ましくは５０質量％以下であり、より好ましくは１５質量％以下であり、さらに好ましくは８質量％以下であり、反応活性の観点から、好ましくは０．１質量％以上であり、より好ましくは１質量％以上であり、更に好ましくは３質量％以上である。 There is no restriction | limiting in particular in the form of a support | carrier, For example, it can take arbitrary physical forms, such as a fine powder, a coarse particle, a pellet. The specific surface area of the carrier may be about 30 to 3000 m 2 / g. When the carrier has pores, the pore volume, average pore diameter and distribution are arbitrary, but the average pore diameter is preferably about 1 to 100 nm. The amount of the Pd compound containing iodine of the present invention supported on the carrier is not particularly limited, but from the viewpoint of reaction activity, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the carrier. More preferably, it is 3% by mass or more, and from the viewpoint of highly dispersed support of the Pd compound, it is preferably 50% by mass or less, more preferably 15% by mass or less, and further preferably 8% by mass or less. From the viewpoint of reaction activity, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more.
ヨウ素を含有するＰｄ化合物担持触媒は、Ｐｄ化合物の担体への分散性や結晶の安定性などの観点から、ヨウ素を含有しないＰｄ化合物が溶解され、担体が分散された溶媒中に、ヨウ素化合物を添加することで得られるＰｄ化合物担持触媒、または、ヨウ素化合物が溶解され、担体が分散された溶媒中に、ヨウ素を含有しないＰｄ化合物を添加することで得られるＰｄ化合物担持触媒が好ましい。 The iodine-containing Pd compound-supported catalyst is prepared by dissolving an iodine compound in a solvent in which a Pd compound not containing iodine is dissolved and the carrier is dispersed from the viewpoint of dispersibility of the Pd compound in the carrier and stability of crystals. A Pd compound-carrying catalyst obtained by adding or a Pd compound-carrying catalyst obtained by adding a Pd compound not containing iodine in a solvent in which the iodine compound is dissolved and the carrier is dispersed is preferable.
[触媒の製造方法]
本発明のＰｄ化合物担持触媒の製造方法は、特に限定されないが、Ｐｄ化合物が水や有機溶媒に難溶性であることから、担体の存在下、ヨウ素を含有しない可溶性Ｐｄ化合物と可溶性ヨウ素化合物を混合し、沈殿法によりＰｄ化合物担持触媒を製造する方法が好ましい。
[Catalyst production method]
The method for producing the Pd compound-supported catalyst of the present invention is not particularly limited, but since a Pd compound is hardly soluble in water or an organic solvent, a soluble Pd compound not containing iodine and a soluble iodine compound are mixed in the presence of a carrier. A method of producing a Pd compound-supported catalyst by a precipitation method is preferred.
ヨウ素を含有しない可溶性Ｐｄ化合物としては、特に限定されないが、酢酸パラジウム、臭化パラジウム、塩化パラジウム、シアン化パラジウム、硝酸パラジウム、酸化パラジウム、硫酸パラジウム、トリフルオロ酢酸パラジウム、ジクロロビス(アセトニトリル)パラジウム、ジクロロジアミノパラジウム、ジクロロ(1,5-シクロオクタジエン)パラジウム、ヘキサクロロパラジウム酸ナトリウム 、ヘキサクロロパラジウム酸カリウム、ジブロモビス(アセトニトリル)パラジウム、ジブロモジアミノパラジウム、ジブロモ(1,5-シクロオクタジエン)パラジウム、ヘキサブロモパラジウム酸ナトリウム、ヘキサブロモパラジウム酸カリウム、テトラブロモパラジウム酸ナトリウム、テトラブロモパラジウム酸カリウム、アセチルアセトンパラジウム、テトラアミン硝酸パラジウム、テトラキスアセトニトリルパラジウムテトラフルオロボラン、トリス(ジベンジリデンアセトン)ジパラジウム、ビス（ジベンジリデンアセトン）パラジウム、ジアミン硝酸パラジウムなどが挙げられる。 Soluble Pd compounds not containing iodine are not particularly limited, but include palladium acetate, palladium bromide, palladium chloride, palladium cyanide, palladium nitrate, palladium oxide, palladium sulfate, palladium trifluoroacetate, dichlorobis (acetonitrile) palladium, dichloromethane. Diaminopalladium, dichloro (1,5-cyclooctadiene) palladium, sodium hexachloropalladate, potassium hexachloropalladate, dibromobis (acetonitrile) palladium, dibromodiaminopalladium, dibromo (1,5-cyclooctadiene) palladium, hexabromopalladium Acid sodium, potassium hexabromopalladate, sodium tetrabromopalladate, potassium tetrabromopalladate, acetylacetone palladium, Toraamin palladium nitrate, tetrakis acetonitrile palladium tetra fluoro borane, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, etc. diamine palladium nitrate and the like.
上記の中でも容易に高収率で担持触媒を得る観点から、酢酸パラジウム、臭化パラジウム、塩化パラジウム、シアン化パラジウム、硝酸パラジウム、酸化パラジウム、硫酸パラジウム、トリフルオロ酢酸パラジウムが好ましく、酢酸パラジウム、臭化パラジウム、塩化パラジウム、シアン化パラジウムがより好ましく、酢酸パラジウムが更に好ましい。 Of these, palladium acetate, palladium bromide, palladium chloride, palladium cyanide, palladium nitrate, palladium oxide, palladium sulfate, and palladium trifluoroacetate are preferred from the viewpoint of easily obtaining a supported catalyst in high yield. Palladium chloride, palladium chloride, and palladium cyanide are more preferable, and palladium acetate is more preferable.
可溶性ヨウ素化合物としては、特に限定されるものではないが、第１族元素〜第１４族元素から選ばれる元素のヨウ化物、又は下記一般式（１）で示される４級アンモニウム化合物が挙げられる。
［Ｒ1−(Ｙ)n］4Ｎ+Ｉ- （１）
（ここで、Ｒ1は炭素数１〜２２の炭化水素基を示し、Ｙは−Ｚ−(ＣＨ2)m−で示される基を示し、Ｚはエーテル基、イミノ基、アミド基又はエステル基、より具体的には−Ｏ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−又は−ＯＣＯ−、ｍは１〜６の数を示し、ｎは０又は１を示し、複数個のＲ1、Ｙ及びｎはそれぞれ同一でも異なっていても良い。また、［Ｒ1−(Ｙ)n］同士の間で環状構造を形成していてもよい。）
Although it does not specifically limit as a soluble iodine compound, The quaternary ammonium compound shown by the iodide of the element chosen from a 1st group element-a 14th group element, or following General formula (1) is mentioned.
[R 1 − (Y) n ] 4 N + I − (1)
(Wherein R 1 represents a hydrocarbon group having 1 to 22 carbon atoms, Y represents a group represented by —Z— (CH 2 ) m —, and Z represents an ether group, an imino group, an amide group or an ester group. More specifically, —O—, —NH—, —CONH—, —NHCO—, —COO— or —OCO—, m represents a number of 1 to 6, n represents 0 or 1, R 1 , Y and n may be the same or different from each other, and a cyclic structure may be formed between [R 1- (Y) n ].
第１族元素〜第１４族元素から選ばれる元素のヨウ化物としては、特に限定されるものではないが、触媒活性の観点から、第１族元素、第１１族元素及び第１２族元素から選ばれる元素のヨウ化物が好ましい。具体的にはＫＩ、ＣｕＩ、ＬｉＩ、ＮａＩ、ＺｎＩ2等を挙げることができ、ＫＩ、ＮａＩが好ましく、ＫＩがより好ましい。 An iodide of an element selected from Group 1 to Group 14 elements is not particularly limited, but is selected from Group 1 elements, Group 11 elements and Group 12 elements from the viewpoint of catalytic activity. The elemental iodides are preferred. Specifically KI, there may be mentioned CuI, LiI, NaI, and ZnI 2 or the like, KI, NaI is preferred, KI is more preferable.
一般式（１）で示される４級アンモニウム化合物としては、容易に高収率で担持触媒を得る観点から、Ｒ1が炭素数１〜７のアルキル基、又はベンジル基（好ましくは炭素数１〜７のアルキル基）であって、ｎが０である４級アンモニウム化合物が好ましく、Ｅｔ4Ｎ+Ｉ-、（ｎ−Ｂｕｔｙｌ）4Ｎ+Ｉ-（ここでＥｔはエチル基、ｎ−Ｂｕｔｙｌはｎ−ブチル基を示す）等がより好ましく、特にＥｔ4Ｎ+Ｉ-が好ましい。 As the quaternary ammonium compound represented by the general formula (1), R 1 is an alkyl group having 1 to 7 carbon atoms or a benzyl group (preferably having a carbon number of 1 to 1) from the viewpoint of easily obtaining a supported catalyst in high yield. Quaternary ammonium compounds wherein n is 0, Et 4 N + I − , (n-Butyl) 4 N + I − (where Et is an ethyl group, n-Butyl is n-butyl group) is more preferable, and Et 4 N + I − is particularly preferable.
触媒調製に用いる溶媒は、特に限定されず、上記した可溶性ヨウ素化合物及び可溶性Ｐｄ化合物を溶解させるものであればなんでも良いが、一般的には、水、メタノール、エタノールなどが挙げられる。 The solvent used for preparing the catalyst is not particularly limited, and any solvent can be used as long as it dissolves the above-mentioned soluble iodine compound and soluble Pd compound. In general, water, methanol, ethanol and the like can be mentioned.
上記のような方法で調製された触媒は、触媒上に付着した溶媒を留去できれば特に問題ないが、触媒の安定性の観点から、３０〜３５０℃で２４時間乾燥することが好ましく、３０℃〜２５０℃で２４時間乾燥することがより好ましく、７０〜２００℃で２４時間乾燥することがさらに好ましい。また、乾燥は不活性ガス雰囲気下で行うのが好ましい。 The catalyst prepared by the above method is not particularly problematic as long as the solvent adhering to the catalyst can be distilled off, but is preferably dried at 30 to 350 ° C. for 24 hours from the viewpoint of catalyst stability. It is more preferable to dry at ˜250 ° C. for 24 hours, and further preferable to dry at 70 to 200 ° C. for 24 hours. Further, drying is preferably performed in an inert gas atmosphere.
本発明のＰｄ化合物担持触媒は、固体触媒、すなわち反応系に不溶な状態で用いることが好ましい。触媒回収の容易さの観点から、Ｎ−複素環カルベン系配位子、２，２−ビピリジルやピリジン等のピリジン系配位子、含酸素系配位子、有機リン系配位子等の触媒を溶解させる配位子を含まないことが好ましい。 The Pd compound-supported catalyst of the present invention is preferably used in a solid catalyst, that is, in a state insoluble in the reaction system. From the viewpoint of ease of catalyst recovery, catalysts such as N-heterocyclic carbene-based ligands, pyridine-based ligands such as 2,2-bipyridyl and pyridine, oxygen-containing ligands, and organic phosphorus-based ligands It is preferable not to include a ligand that dissolves.
[オレフィンの製造方法]
本発明のＰｄ化合物担持触媒は、脂肪酸又はその誘導体からのオレフィンの製造方法に好適に用いられる。このオレフィン製造方法は、β水素原子を有するカルボン酸又はその誘導体を原料とし、本発明の触媒を用いて脱カルボニル化を行なう方法である。
[Olefin production method]
The Pd compound-supported catalyst of the present invention is suitably used in a method for producing an olefin from a fatty acid or a derivative thereof. This olefin production method is a method of decarbonylation using a carboxylic acid having a β hydrogen atom or a derivative thereof as a raw material and using the catalyst of the present invention.
本発明に用いられるβ水素原子を有するカルボン酸またはその誘導体は、カルボニル基のβ位に少なくとも１つの水素原子を有するものであれば特に限定されず、飽和体でも不飽和体でも、一部環状になったものでも、ヘテロ原子を含むものでも、カルボニル基を複数有するものでもよいが、オレフィン収率の観点から、飽和１価カルボン酸またはその誘導体が好ましい。β水素原子を有するカルボン酸誘導体としては、β水素原子を有するカルボン酸無水物、β水素原子を有するカルボン酸ハロゲン化物、β水素原子を有するカルボン酸エステル、β水素原子を有するカルボン酸アミドが挙げられ、オレフィン収率の観点から、β水素原子を有するカルボン酸又はβ水素原子を有するカルボン酸無水物が好ましく、β水素原子を有するカルボン酸無水物がより好ましい。 The carboxylic acid having a β hydrogen atom or a derivative thereof used in the present invention is not particularly limited as long as it has at least one hydrogen atom at the β-position of the carbonyl group. However, from the viewpoint of olefin yield, a saturated monovalent carboxylic acid or a derivative thereof is preferable. Examples of the carboxylic acid derivative having a β hydrogen atom include a carboxylic acid anhydride having a β hydrogen atom, a carboxylic acid halide having a β hydrogen atom, a carboxylic acid ester having a β hydrogen atom, and a carboxylic acid amide having a β hydrogen atom. From the viewpoint of olefin yield, a carboxylic acid having a β hydrogen atom or a carboxylic acid anhydride having a β hydrogen atom is preferable, and a carboxylic acid anhydride having a β hydrogen atom is more preferable.
β水素原子を有するカルボン酸の具体例としては、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、３−フェニルプロピオン酸、アジピン酸、アゼライン酸、エイコサン酸、９−デセン酸、１０−ウンデセン酸、オレイン酸、２，４−ヘキサジエン酸、３−メチルブタン酸、６−オクタデシン酸、ヒドノカルピン酸、ゴルリン酸、リシノール酸等が挙げられる。 Specific examples of the carboxylic acid having a β hydrogen atom include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 3-phenylpropionic acid, adipic acid, azelaic acid, and eicosane. Examples include acid, 9-decenoic acid, 10-undecenoic acid, oleic acid, 2,4-hexadienoic acid, 3-methylbutanoic acid, 6-octadecinic acid, hydonocarpic acid, golphosphoric acid, ricinoleic acid and the like.
β水素原子を有するカルボン酸無水物の具体例としては、カプロン酸無水物、カプリル酸無水物、カプリン酸無水物、ラウリン酸無水物、ミリスチン酸無水物、パルミチン酸無水物、ステアリン酸無水物、ベヘン酸無水物、３−フェニルプロピオン酸無水物、アジピン酸無水物、アゼライン酸無水物、エイコサン酸無水物、９−デセン酸無水物、１０−ウンデセン酸無水物、オレイン酸無水物、２，４−ヘキサジエン酸無水物、３−メチルブタン酸無水物、６−オクタデシン酸無水物、ヒドノカルピン酸無水物、ゴルリン酸無水物、リシノール酸無水物、コハク酸無水物等、あるいはギ酸、酢酸、プロピオン酸、酪酸と上記β水素原子を有するカルボン酸の具体例で挙げられたカルボン酸とが縮合した無水物、又は、上記β水素原子を有するカルボン酸の具体例で挙げられたカルボン酸において、異なるカルボン酸同士が縮合したカルボン酸無水物が挙げられる。 Specific examples of carboxylic acid anhydrides having β hydrogen atoms include caproic acid anhydride, caprylic acid anhydride, capric acid anhydride, lauric acid anhydride, myristic acid anhydride, palmitic acid anhydride, stearic acid anhydride, Behenic anhydride, 3-phenylpropionic anhydride, adipic anhydride, azelaic anhydride, eicosanoic anhydride, 9-decenoic anhydride, 10-undecenoic anhydride, oleic anhydride, 2,4 -Hexadienoic anhydride, 3-methylbutanoic anhydride, 6-octadesinic anhydride, hydnocarpinic anhydride, gorulinic anhydride, ricinoleic anhydride, succinic anhydride, etc., or formic acid, acetic acid, propionic acid, butyric acid And an anhydride obtained by condensing the carboxylic acid mentioned in the specific example of the carboxylic acid having the β hydrogen atom, or a catalyst having the β hydrogen atom. In the carboxylic acid listed in the specific examples of carbon acids include carboxylic anhydride between different carboxylic acid are condensed.
本発明に用いられるβ水素原子を有するカルボン酸無水物の製造方法は、特に制限されるものではないが、例えばカルボン酸を塩化チオニルや塩化ホスホニル、無水酢酸、トリフルオロ酢酸無水物、塩化アセチル等で脱水する方法、カルボン酸ハロゲン化物とカルボン酸アルカリ金属塩又はアルカリ土類金属塩とを反応させる方法、アルデヒドを酸化する方法等が挙げられ、カルボン酸ハロゲン化物とカルボン酸アルカリ金属塩又はアルカリ土類金属塩とを反応させる方法、カルボン酸を無水酢酸で脱水する方法が好ましい。 The method for producing a carboxylic acid anhydride having a β hydrogen atom used in the present invention is not particularly limited. For example, carboxylic acid may be thionyl chloride, phosphonyl chloride, acetic anhydride, trifluoroacetic anhydride, acetyl chloride, or the like. For example, a method of reacting a carboxylic acid halide with a carboxylic acid alkali metal salt or an alkaline earth metal salt, a method of oxidizing an aldehyde, etc., and a carboxylic acid halide and a carboxylic acid alkali metal salt or alkaline earth. A method of reacting a metal salt and a method of dehydrating a carboxylic acid with acetic anhydride are preferred.
β水素原子を有するカルボン酸ハロゲン化物の具体例としては、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、３−フェニルプロピオン酸、アジピン酸、アゼライン酸、エイコサン酸、９−デセン酸、１０−ウンデセン酸、オレイン酸、２，４−ヘキサジエン酸、３−メチルブタン酸、６−オクタデシン酸、ヒドノカルピン酸、ゴルリン酸、リシノール酸等の塩素化物、臭素化物、ヨウ素化物が挙げられる。 Specific examples of carboxylic acid halides having β hydrogen atoms include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 3-phenylpropionic acid, adipic acid, azelaic acid Chlorinated products such as eicosanoic acid, 9-decenoic acid, 10-undecenoic acid, oleic acid, 2,4-hexadienoic acid, 3-methylbutanoic acid, 6-octadesinic acid, hydnocarpinic acid, goluric acid, ricinoleic acid, bromide, Iodide is mentioned.
β水素原子を有するカルボン酸エステルの具体例としては、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、３−フェニルプロピオン酸、アジピン酸、アゼライン酸、エイコサン酸、９−デセン酸、１０−ウンデセン酸、オレイン酸、２，４−ヘキサジエン酸、３−メチルブタン酸、６−オクタデシン酸、ヒドノカルピン酸、ゴルリン酸、リシノール酸等のアルキルエステル、例えばメチルエステル、エチルエステル等が挙げられる。 Specific examples of the carboxylic acid ester having a β hydrogen atom include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 3-phenylpropionic acid, adipic acid, azelaic acid, Alkyl esters such as eicosanoic acid, 9-decenoic acid, 10-undecenoic acid, oleic acid, 2,4-hexadienoic acid, 3-methylbutanoic acid, 6-octadesinic acid, hydnocarpinic acid, gorulinic acid, ricinoleic acid, such as methyl ester, An ethyl ester etc. are mentioned.
β水素原子を有するカルボン酸アミドの具体例としては、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、３−フェニルプロピオン酸、アジピン酸、アゼライン酸、エイコサン酸、９−デセン酸、１０−ウンデセン酸、オレイン酸、２，４−ヘキサジエン酸、３−メチルブタン酸、６−オクタデシン酸、ヒドノカルピン酸、ゴルリン酸、リシノール酸等のアミド又は置換アミド、例えばモノメチルアミド、ジメチルアミド、ジエチルアミド等が挙げられる。 Specific examples of the carboxylic acid amide having a β hydrogen atom include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 3-phenylpropionic acid, adipic acid, azelaic acid, Amides or substituted amides such as eicosanoic acid, 9-decenoic acid, 10-undecenoic acid, oleic acid, 2,4-hexadienoic acid, 3-methylbutanoic acid, 6-octadesinic acid, hydnocarpinic acid, golphosphoric acid, ricinoleic acid, such as monomethyl Examples include amide, dimethylamide, diethylamide and the like.
β水素原子を有するカルボン酸またはその誘導体としては、オレフィン収率の観点から、カルボン酸またはカルボン酸残基の炭素数（カルボン酸無水物の場合は少なくとも１つのカルボン酸残基の炭素数）が３以上のものが好ましく、８以上のものがより好ましく、１２以上のものが更に好ましい。またオレフィン収率の観点から、２２以下のものが好ましく、２０以下のものがより好ましく、１８以下のものが更に好ましい。なお、不飽和カルボン酸またはその誘導体を原料に用いた場合は、原料よりも二重結合の数が１つ多いオレフィンとなる。 As the carboxylic acid having β hydrogen atom or a derivative thereof, from the viewpoint of olefin yield, the carbon number of the carboxylic acid or carboxylic acid residue (in the case of carboxylic anhydride, the carbon number of at least one carboxylic acid residue) is 3 or more are preferable, 8 or more are more preferable, and 12 or more are more preferable. From the viewpoint of olefin yield, those of 22 or less are preferred, those of 20 or less are more preferred, and those of 18 or less are more preferred. In addition, when unsaturated carboxylic acid or its derivative is used as a raw material, it becomes an olefin having one more double bond than the raw material.
本発明のＰｄ化合物担持触媒を用いた脂肪酸又はその誘導体からのオレフィンの製造方法において、Ｐｄ化合物担持触媒の使用量は、反応条件に応じて適宜定められるが、オレフィンを高収率で得る観点、及び、経済性の観点から、β水素原子を有するカルボン酸またはその誘導体１モルに対し、パラジウム化合物として０．００００１モル以上が好ましく、０．０００１モル以上がより好ましく、０．００１モル以上がさらに好ましく、０．００５モル以上が更に好ましい。またオレフィンを高収率で得る観点、及び、経済性の観点から、０．５モル以下が好ましく、０．１モル以下がより好ましく、０．０５モル以下がさらに好ましく、０．０３モル以下が更に好ましい。 In the method for producing an olefin from a fatty acid or a derivative thereof using the Pd compound-supported catalyst of the present invention, the amount of the Pd compound-supported catalyst is appropriately determined according to the reaction conditions, but a viewpoint of obtaining the olefin in a high yield, From the viewpoint of economy, the palladium compound is preferably 0.00001 mol or more, more preferably 0.0001 mol or more, and further 0.001 mol or more, based on 1 mol of a carboxylic acid having β hydrogen atom or a derivative thereof. Preferably, 0.005 mol or more is more preferable. In addition, from the viewpoint of obtaining an olefin in a high yield and economical viewpoint, 0.5 mol or less is preferable, 0.1 mol or less is more preferable, 0.05 mol or less is more preferable, and 0.03 mol or less is preferable. Further preferred.
本発明のＰｄ化合物担持触媒を用いて脂肪酸又はその誘導体からオレフィンを製造する脱カルボニル反応の温度は、活性及び安定性を向上させる観点から、１００℃以上が好ましく、１５０℃以上がより好ましく、２００℃以上がさらに好ましい。また活性及び安定性を向上させる観点から、４００℃以下が好ましく、３５０℃以下がより好ましく、３００℃以下がさらに好ましい。本発明の触媒は好ましくは配位子を用いないため、高温での使用も可能である。 The temperature of the decarbonylation reaction for producing an olefin from a fatty acid or a derivative thereof using the Pd compound-supported catalyst of the present invention is preferably 100 ° C or higher, more preferably 150 ° C or higher, from the viewpoint of improving activity and stability. More preferably, it is not lower than ° C. Moreover, from a viewpoint of improving activity and stability, 400 degrees C or less is preferable, 350 degrees C or less is more preferable, and 300 degrees C or less is more preferable. Since the catalyst of the present invention preferably does not use a ligand, it can be used at a high temperature.
本発明のＰｄ化合物担持触媒を用いて脂肪酸又はその誘導体からオレフィンを製造する場合、反応の圧力は、脂肪酸又はその誘導体が高選択的に、且つ速い反応速度で目的とするオレフィンに変換されれば特に制限されるものではなく、減圧下から加圧下の広い圧力範囲で行うことができるが、良好な反応速度を得る観点から、２００ｋＰａ（絶対圧）以下であることが好ましく、１６０ｋＰａ（絶対圧）以下がより好ましく、１１０ｋＰａ（絶対圧）以下が更に好ましい。また良好な反応速度を得る観点から、１０ｋＰａ（絶対圧）以上がより好ましく、２０ｋＰａ（絶対圧）以上が更に好ましい。 When an olefin is produced from a fatty acid or a derivative thereof using the Pd compound-supported catalyst of the present invention, the reaction pressure is such that the fatty acid or the derivative thereof is converted to the desired olefin at a high reaction rate with high selectivity. The pressure is not particularly limited and can be carried out in a wide pressure range from reduced pressure to increased pressure. From the viewpoint of obtaining a good reaction rate, it is preferably 200 kPa (absolute pressure) or less, and 160 kPa (absolute pressure). The following is more preferable, and 110 kPa (absolute pressure) or less is still more preferable. Moreover, from a viewpoint of obtaining a favorable reaction rate, 10 kPa (absolute pressure) or more is more preferable, and 20 kPa (absolute pressure) or more is more preferable.
本発明のＰｄ化合物担持触媒を用いて脂肪酸又はその誘導体からオレフィンを製造する場合、脱カルボニル反応は、不活性ガス雰囲気下で行われる。不活性ガスとしては、窒素、一酸化炭素、二酸化炭素、アルゴン、ヘリウム等が挙げられる。不活性ガスは反応容器中を流通させてもよく、また反応容器内をこれらのガスで置換した後、密閉して反応を行ってもよい。 When an olefin is produced from a fatty acid or a derivative thereof using the Pd compound-supported catalyst of the present invention, the decarbonylation reaction is performed in an inert gas atmosphere. Examples of the inert gas include nitrogen, carbon monoxide, carbon dioxide, argon, helium and the like. The inert gas may be circulated in the reaction vessel, or after the inside of the reaction vessel is replaced with these gases, the reaction may be carried out in a sealed state.
脂肪酸又はその誘導体から目的とするオレフィンへの変換は、反応後の溶液を1Ｈ−ＮＭＲやガスクロマトグラフィーで分析することにより確認することができる。本発明のＰｄ化合物担持触媒を用いたオレフィンの製造方法においては、溶媒、酸化防止剤、助触媒成分等の他の成分があってもよい。 Conversion of the fatty acid or its derivative to the desired olefin can be confirmed by analyzing the solution after the reaction by 1 H-NMR or gas chromatography. In the olefin production method using the Pd compound-supported catalyst of the present invention, there may be other components such as a solvent, an antioxidant and a promoter component.
本発明の方法により得られるオレフィンとしては、末端に二重結合を持つ構造のみでなく、それらから異性化した内部に二重結合を持つ内部オレフィンであってもよい。反応で生成したオレフィンは通常の後処理により精製・単離して取り出すことができる。 The olefin obtained by the method of the present invention is not limited to a structure having a double bond at the terminal, but may be an internal olefin having a double bond isomerized therefrom. The olefin produced by the reaction can be purified and isolated by ordinary post-treatment.
[炭素−炭素結合形成方法１]
本発明のＰｄ化合物担持触媒は、１種類以上の有機化合物の分子間又は分子内炭素−炭素結合形成反応に好適に用いられる。例えば、有機ホウ素化合物からボロン酸を含む官能基が脱離した有機残基と、有機ハロゲン化合物からハロゲンを含む官能基が脱離した有機残基との間に、炭素−炭素結合を形成する反応が挙げられる。
[Carbon-carbon bond forming method 1]
The Pd compound-supported catalyst of the present invention is suitably used for an intermolecular or intramolecular carbon-carbon bond forming reaction of one or more organic compounds. For example, a reaction that forms a carbon-carbon bond between an organic residue from which a functional group containing boronic acid is eliminated from an organic boron compound and an organic residue from which a functional group containing halogen is eliminated from an organic halogen compound. Is mentioned.
上記有機ホウ素化合物は、反応収率の観点から、下記一般式（２）
Ｒ2−Ｂ（ＯＨ）2 （２）
（式中、Ｒ2は、直鎖、分岐または環状のアルキル基、アルケニル基、アルキニル基、置換若しくは無置換のフェニル基、ベンジル基、フリル基、ナフチル基、アントラセニル基、ピリジル基、ピリミジル基、インドリル基、ベンズイミダゾリル基、キノリル基、ベンゾフラニル基、インダニル基、インデニル基、ジベンゾフラニル基またはメチレンジオキシフェニル基を表し、これらの基は１個又はそれ以上の置換基を有してもよい。）で表されるものが好ましく、アルキル基、アルケニル基、アルキニル基、置換若しくは無置換のフェニル基又はベンジル基がより好ましく、置換若しくは無置換のフェニル基がさらに好ましい。置換基の例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等の炭素原子数１〜６のアルキル基；メトキシ基、エトキシ基、ｎ−プロピロキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｎ−ペンチロキシ基、ｎ−ヘキシロキシ基等の炭素原子数１〜６のアルコキシ基；ベンジル基；９−フルオレニルメトキシカルボニル基；ブトキシカルボニル基；ベンジルオキシカルボニル基；ニトロ基；またはフッ素、塩素、臭素、ヨウ素等のハロゲン原子などが挙げられ、好ましくは、炭素原子数１〜３のアルキル基、メトキシ基、ベンジル基、９−フルオレニルメトキシカルボニル基、ブトキシカルボニル基、ベンジルオキシカルボニル基、ニトロ基またはフッ素原子である。
From the viewpoint of reaction yield, the organic boron compound is represented by the following general formula (2).
R 2 —B (OH) 2 (2)
(Wherein R 2 represents a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, substituted or unsubstituted phenyl group, benzyl group, furyl group, naphthyl group, anthracenyl group, pyridyl group, pyrimidyl group, Represents an indolyl group, a benzimidazolyl group, a quinolyl group, a benzofuranyl group, an indanyl group, an indenyl group, a dibenzofuranyl group or a methylenedioxyphenyl group, and these groups may have one or more substituents .) Is preferable, an alkyl group, an alkenyl group, an alkynyl group, a substituted or unsubstituted phenyl group or a benzyl group is more preferable, and a substituted or unsubstituted phenyl group is more preferable. Examples of the substituent include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group and n-hexyl group; methoxy group, An alkoxy group having 1 to 6 carbon atoms such as ethoxy group, n-propyloxy group, isopropoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group; benzyl group; 9-fluorenylmethoxycarbonyl group; A butoxycarbonyl group; a benzyloxycarbonyl group; a nitro group; or a halogen atom such as fluorine, chlorine, bromine or iodine, preferably an alkyl group having 1 to 3 carbon atoms, a methoxy group, a benzyl group, 9- A fluorenylmethoxycarbonyl group, a butoxycarbonyl group, a benzyloxycarbonyl group, a nitro group or a fluorine atom;
上記有機ハロゲン化合物は、下記一般式（３）
Ｒ3−Ｘ （３）
（式中、Ｒ3は、直鎖、分岐または環状のアルキル基、アルケニル基、アルキニル基、置換若しくは無置換のフェニル基、ベンジル基、フリル基、ナフチル基、アントラセニル基、ピリジル基、ピリミジル基、インドリル基、ベンズイミダゾリル基、キノリル基、ベンゾフラニル基、インダニル基、インデニル基、ジベンゾフラニル基またはメチレンジオキシフェニル基を表し、これらの基は１個又はそれ以上の置換基を有してもよい。）で表されるものが好ましく、アルキル基、アルケニル基、アルキニル基、置換若しくは無置換のフェニル基又はベンジル基がより好ましく、置換若しくは無置換のフェニル基がさらに好ましい。置換基の例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等の炭素原子数１〜６のアルキル基；メトキシ基、エトキシ基、ｎ−プロピロキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｎ−ペンチロキシ基、ｎ−ヘキシロキシ基等の炭素原子数１〜６のアルコキシ基；ベンジル基；９−フルオレニルメトキシカルボニル基；ブトキシカルボニル基；ベンジルオキシカルボニル基；ニトロ基；またはフッ素、塩素、臭素、ヨウ素等のハロゲン原子などが挙げられ、好ましくは、炭素原子数１〜３のアルキル基、メトキシ基、ベンジル基、９−フルオレニルメトキシカルボニル基、ブトキシカルボニル基、ベンジルオキシカルボニル基、ニトロ基またはフッ素原子である。Ｘは、ヨウ素原子、臭素原子、又は塩素原子が好ましく、ヨウ素原子がより好ましい。
The organic halogen compound has the following general formula (3)
R 3 -X (3)
(Wherein R 3 represents a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, substituted or unsubstituted phenyl group, benzyl group, furyl group, naphthyl group, anthracenyl group, pyridyl group, pyrimidyl group, Represents an indolyl group, a benzimidazolyl group, a quinolyl group, a benzofuranyl group, an indanyl group, an indenyl group, a dibenzofuranyl group or a methylenedioxyphenyl group, and these groups may have one or more substituents .) Is preferable, an alkyl group, an alkenyl group, an alkynyl group, a substituted or unsubstituted phenyl group or a benzyl group is more preferable, and a substituted or unsubstituted phenyl group is more preferable. Examples of the substituent include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group and n-hexyl group; methoxy group, An alkoxy group having 1 to 6 carbon atoms such as ethoxy group, n-propyloxy group, isopropoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group; benzyl group; 9-fluorenylmethoxycarbonyl group; A butoxycarbonyl group; a benzyloxycarbonyl group; a nitro group; or a halogen atom such as fluorine, chlorine, bromine or iodine, preferably an alkyl group having 1 to 3 carbon atoms, a methoxy group, a benzyl group, 9- A fluorenylmethoxycarbonyl group, a butoxycarbonyl group, a benzyloxycarbonyl group, a nitro group or a fluorine atom; X is preferably an iodine atom, a bromine atom, or a chlorine atom, and more preferably an iodine atom.
本発明のＰｄ化合物担持触媒を用いた炭素−炭素結合形成方法１において、Ｐｄ化合物担持触媒の使用量は、反応収率の観点から、有機ハロゲン化合物１モルに対し、パラジウム化合物として０．０００００１モル以上が好ましく、０．００００１モル以上がより好ましく、０．０００１モル以上がさらに好ましく、０．００１モル以上が特に好ましい。また反応収率の観点から、０．２モル以下が好ましく、０．０５モル以下がより好ましく、０．０１モル以下がさらに好ましく、０．００３モル以下が特に好ましい。 In the carbon-carbon bond forming method 1 using the Pd compound-supported catalyst of the present invention, the amount of the Pd compound-supported catalyst is 0.000001 mol as a palladium compound with respect to 1 mol of the organic halogen compound from the viewpoint of reaction yield. The above is preferable, 0.00001 mol or more is more preferable, 0.0001 mol or more is further preferable, and 0.001 mol or more is particularly preferable. Moreover, from a viewpoint of reaction yield, 0.2 mol or less is preferable, 0.05 mol or less is more preferable, 0.01 mol or less is more preferable, 0.003 mol or less is especially preferable.
本発明のＰｄ化合物担持触媒を用いて炭素−炭素結合形成方法１を行う温度は、活性を向上させる観点から、１０℃以上が好ましく、２０℃以上がより好ましく、５０℃以上がさらに好ましい。また活性を向上させる観点から、２００℃以下が好ましく、１５０℃以下がより好ましい。 From the viewpoint of improving activity, the temperature at which the carbon-carbon bond forming method 1 is performed using the Pd compound-supported catalyst of the present invention is preferably 10 ° C or higher, more preferably 20 ° C or higher, and further preferably 50 ° C or higher. Moreover, from a viewpoint of improving activity, 200 degrees C or less is preferable and 150 degrees C or less is more preferable.
本発明のＰｄ化合物担持触媒を用いて上記のように炭素−炭素結合を形成する場合、反応の圧力は特に制限されるものではなく、減圧下から加圧下の広い圧力範囲で行うことができる。 When the carbon-carbon bond is formed as described above using the Pd compound-supported catalyst of the present invention, the reaction pressure is not particularly limited, and the reaction can be performed in a wide pressure range from reduced pressure to increased pressure.
本発明のＰｄ化合物担持触媒を用いて上記のように炭素−炭素結合を形成する反応は、不活性ガス雰囲気下で行われる。不活性ガスとしては、窒素、二酸化炭素、アルゴン、ヘリウム等が挙げられる。不活性ガスは反応容器中を流通させてもよく、また反応容器内をこれらのガスで置換した後、密閉して反応を行ってもよい。反応はバッチ反応でも連続反応でも行うことができる。 The reaction for forming a carbon-carbon bond as described above using the Pd compound-supported catalyst of the present invention is performed in an inert gas atmosphere. Examples of the inert gas include nitrogen, carbon dioxide, argon, helium and the like. The inert gas may be circulated in the reaction vessel, or after the inside of the reaction vessel is replaced with these gases, the reaction may be carried out in a sealed state. The reaction can be carried out either batchwise or continuously.
目的とする炭素−炭素結合の形成は、反応後の溶液を例えばガスクロマトグラフィーで分析することにより確認することができる。本発明のＰｄ化合物担持触媒を用いた炭素−炭素結合形成においては、溶媒、酸化防止剤、助触媒成分等の他の成分があってもよい。 Formation of the target carbon-carbon bond can be confirmed by analyzing the solution after the reaction, for example, by gas chromatography. In the carbon-carbon bond formation using the Pd compound-supported catalyst of the present invention, there may be other components such as a solvent, an antioxidant, and a promoter component.
反応生成物は常法により精製して取り出すことができる。例えば、吸着、水洗、蒸留等の通常の後処理により精製・単離して取り出すことができる。 The reaction product can be purified and removed by a conventional method. For example, it can be purified and isolated by ordinary post-treatment such as adsorption, washing and distillation.
[炭素−炭素結合形成方法２]
本発明のＰｄ化合物担持触媒は、オレフィン化合物から二重結合の末端Ｈが一つ脱離した有機残基と、有機ハロゲン化合物からハロゲンを含む官能基が脱離した有機残基との間に、炭素−炭素結合を形成する反応にも有用である。
[Carbon-carbon bond formation method 2]
The Pd compound-supported catalyst of the present invention has an organic residue in which one terminal H of a double bond is eliminated from an olefin compound and an organic residue in which a functional group containing halogen is eliminated from an organic halogen compound, It is also useful for reactions that form carbon-carbon bonds.
上記オレフィン化合物は、反応収率の観点から、下記一般式（４）
Ｒ4−ＣＨ＝ＣＨ2 （４）
（式中、Ｒ4は、直鎖、分岐または環状のアルキル基、アルケニル基、アルキニル基、置換若しくは無置換のフェニル基、ベンジル基、フリル基、ナフチル基、アントラセニル基、ピリジル基、ピリミジル基、インドリル基、ベンズイミダゾリル基、キノリル基、ベンゾフラニル基、インダニル基、インデニル基、ジベンゾフラニル基またはメチレンジオキシフェニル基を表し、これらの基は１個又はそれ以上の置換基を有してもよい。）で表されるものが好ましく、アルキル基、アルケニル基、アルキニル基、置換若しくは無置換のフェニル基又はベンジル基がより好ましく、置換若しくは無置換のフェニル基がさらに好ましい。置換基の例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等の炭素原子数１〜６のアルキル基；メトキシ基、エトキシ基、ｎ−プロピロキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｎ−ペンチロキシ基、ｎ−ヘキシロキシ基等の炭素原子数１〜６のアルコキシ基；ベンジル基；９−フルオレニルメトキシカルボニル基；ブトキシカルボニル基；ベンジルオキシカルボニル基；ニトロ基；またはフッ素、塩素、臭素、ヨウ素等のハロゲン原子などが挙げられ、好ましくは、炭素原子数１〜３のアルキル基、メトキシ基、ベンジル基、９−フルオレニルメトキシカルボニル基、ブトキシカルボニル基、ベンジルオキシカルボニル基、ニトロ基またはフッ素原子である。
The olefin compound is represented by the following general formula (4) from the viewpoint of reaction yield.
R 4 —CH═CH 2 (4)
(Wherein R 4 represents a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, substituted or unsubstituted phenyl group, benzyl group, furyl group, naphthyl group, anthracenyl group, pyridyl group, pyrimidyl group, Represents an indolyl group, a benzimidazolyl group, a quinolyl group, a benzofuranyl group, an indanyl group, an indenyl group, a dibenzofuranyl group or a methylenedioxyphenyl group, and these groups may have one or more substituents .) Is preferable, an alkyl group, an alkenyl group, an alkynyl group, a substituted or unsubstituted phenyl group or a benzyl group is more preferable, and a substituted or unsubstituted phenyl group is more preferable. Examples of the substituent include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group and n-hexyl group; methoxy group, An alkoxy group having 1 to 6 carbon atoms such as ethoxy group, n-propyloxy group, isopropoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group; benzyl group; 9-fluorenylmethoxycarbonyl group; A butoxycarbonyl group; a benzyloxycarbonyl group; a nitro group; or a halogen atom such as fluorine, chlorine, bromine or iodine, preferably an alkyl group having 1 to 3 carbon atoms, a methoxy group, a benzyl group, 9- A fluorenylmethoxycarbonyl group, a butoxycarbonyl group, a benzyloxycarbonyl group, a nitro group or a fluorine atom;
上記有機ハロゲン化合物は、反応性の観点から、前記一般式（３）が好ましい。 The organic halogen compound is preferably the general formula (3) from the viewpoint of reactivity.
本発明のＰｄ化合物担持触媒を用いた炭素−炭素結合形成方法２において、Ｐｄ化合物担持触媒の使用量は、反応収率の観点から、有機ハロゲン化合物１モルに対し、パラジウム化合物として０．０００００１モル以上が好ましく、０．００００１モル以上がより好ましく、０．０００１モル以上がさらに好ましく、０．０１モル以上が更により好ましい。また反応収率の観点から、０．２モル以下が好ましく、０．１モル以下がより好ましく、０．０５モル以下がさらに好ましく、０．０２モル以下が更により好ましい。 In the carbon-carbon bond forming method 2 using the Pd compound-supported catalyst of the present invention, the amount of the Pd compound-supported catalyst is 0.000001 mol as a palladium compound with respect to 1 mol of the organic halogen compound from the viewpoint of reaction yield. The above is preferable, 0.00001 mol or more is more preferable, 0.0001 mol or more is further preferable, and 0.01 mol or more is even more preferable. Moreover, from a viewpoint of reaction yield, 0.2 mol or less is preferable, 0.1 mol or less is more preferable, 0.05 mol or less is more preferable, 0.02 mol or less is still more preferable.
本発明のＰｄ化合物担持触媒を用いて炭素−炭素結合形成方法２を行う温度は、活性を向上させる観点から、１０℃以上が好ましく、２０℃以上がより好ましく、５０℃以上がさらに好ましい。また活性を向上させる観点から、２００℃以下が好ましく、１５０℃以下がより好ましく、１２０℃以下がさらに好ましい。 From the viewpoint of improving activity, the temperature at which the carbon-carbon bond forming method 2 is performed using the Pd compound-supported catalyst of the present invention is preferably 10 ° C or higher, more preferably 20 ° C or higher, and further preferably 50 ° C or higher. Moreover, from a viewpoint of improving activity, 200 degrees C or less is preferable, 150 degrees C or less is more preferable, and 120 degrees C or less is further more preferable.
本発明のＰｄ化合物担持触媒を用いて上記のように炭素−炭素結合を形成する場合、反応の圧力は特に制限されるものではなく、減圧下から加圧下の広い圧力範囲で行うことができる。 When the carbon-carbon bond is formed as described above using the Pd compound-supported catalyst of the present invention, the reaction pressure is not particularly limited, and the reaction can be performed in a wide pressure range from reduced pressure to increased pressure.
本発明のＰｄ化合物担持触媒を用いて上記のように炭素−炭素結合を形成する反応は、不活性ガス雰囲気下で行われる。不活性ガスとしては、窒素、二酸化炭素、アルゴン、ヘリウム等が挙げられる。不活性ガスは反応容器中を流通させてもよく、また反応容器内をこれらのガスで置換した後、密閉して反応を行ってもよい。反応はバッチ反応でも連続反応でも行うことができる。 The reaction for forming a carbon-carbon bond as described above using the Pd compound-supported catalyst of the present invention is performed in an inert gas atmosphere. Examples of the inert gas include nitrogen, carbon dioxide, argon, helium and the like. The inert gas may be circulated in the reaction vessel, or after the inside of the reaction vessel is replaced with these gases, the reaction may be carried out in a sealed state. The reaction can be carried out either batchwise or continuously.
目的とする炭素−炭素結合の形成は、反応後の溶液を例えばガスクロマトグラフィーで分析することにより確認することができる。本発明のＰｄ化合物担持触媒を用いた炭素−炭素結合形成においては、溶媒、酸化防止剤、助触媒成分等の他の成分があってもよい。 Formation of the target carbon-carbon bond can be confirmed by analyzing the solution after the reaction, for example, by gas chromatography. In the carbon-carbon bond formation using the Pd compound-supported catalyst of the present invention, there may be other components such as a solvent, an antioxidant, and a promoter component.
反応生成物は常法により精製して取り出すことができる。例えば、吸着、水洗、蒸留等の通常の後処理により精製・単離して取り出すことができる。 The reaction product can be purified and removed by a conventional method. For example, it can be purified and isolated by ordinary post-treatment such as adsorption, washing and distillation.
実施例１
(触媒の調製）
Ｐｄ（ＯＡｃ）2（和光純薬工業（株）製））０．３４ｇ（１．５ｍｍｏｌ）をメタノール（キシダ化学（株）製）（８５．０ｇ）に溶かした後、担体としてＳｉＯ2（富士シリシア化学（株）製ＣＡＲｉＡＣＴ Ｑ-５０）（１０．８ｇ）を加え、０．５時間攪拌した。次に予め調製しておいた１質量％ＫＩ メタノール溶液（ＫＩはＳＩＧＭＡ ＡＬＤＲＩＣＨ（株）製、メタノールはキシダ化学（株）製））を０．５時間かけて５２．０ｇ（ＫＩとして３．１５ｍｍｏｌ）滴下した。４時間室温で攪拌した後、０．２μｍテフロン製メンブランフィルターでろ過した。得られた固体をメタノール及びイオン交換水で十分洗浄した後、窒素雰囲気下、１１０℃、２０ｋＰａで１日乾燥した。得られたＰｄ化合物担持触媒は、Ｐｄ化合物と担体の質量比がＰｄＩ2／ＳｉＯ2＝５／１００であった。
Example 1
(Preparation of catalyst)
After dissolving 0.34 g (1.5 mmol) of Pd (OAc) 2 (manufactured by Wako Pure Chemical Industries, Ltd.) in methanol (manufactured by Kishida Chemical Co., Ltd.) (85.0 g), SiO 2 (Fuji Siricia Chemical Co., Ltd. CARiACT Q-50) (10.8 g) was added and stirred for 0.5 hour. Next, 52.0 g (KI as 3.15 mmol as KI) of 1% by mass KI methanol solution prepared in advance (KI is manufactured by SIGMA ALDRICH Co., Ltd. and methanol is manufactured by Kishida Chemical Co., Ltd.) over 0.5 hours. ) Added dropwise. After stirring for 4 hours at room temperature, the mixture was filtered through a 0.2 μm Teflon membrane filter. The obtained solid was sufficiently washed with methanol and ion-exchanged water, and then dried at 110 ° C. and 20 kPa for 1 day in a nitrogen atmosphere. The obtained Pd compound-supported catalyst had a mass ratio of Pd compound to carrier of PdI 2 / SiO 2 = 5/100.
得られた触媒は、ＸＰＳ測定（ＰＨＩ Ｑｕａｎｔｒａ ＳＸＭ （ＵＬＶＡＣ−ＰＩ．ＩＮＣ））より、Ｐｄ ３ｄ5/2 結合エネルギーが３３７［ｅＶ］であり、ヨウ素原子とパラジウム原子のモル比がＩ/Ｐｄ＝２であった。
Ｘ線結晶回折（以下、ＸＲＤと略記する）（リガク製、ＲＩＮＴ２５００ＶＰＣ）測定より、２θ＝１７、３０、３４[°]であった。
From the XPS measurement (PHI Quantra SXM (ULVAC-PI. INC)), the obtained catalyst has a Pd 3d 5/2 binding energy of 337 [eV] and a molar ratio of iodine atom to palladium atom of I / Pd = 2.
From X-ray crystal diffraction (hereinafter abbreviated as XRD) (Rigaku, RINT 2500 VPC) measurement, 2θ = 17, 30, and 34 °.
（オレフィンの製造）
５０ｍＬナス型フラスコに攪拌子と、ステアリン酸無水物（東京化成工業（株）製）４．１３ｇ（７．５ｍｍｏｌ）、上記で調製した５質量％ＰｄＩ2／ＳｉＯ2 １．４４ｇ（ＰｄＩ2として０．１９ｍｍｏｌ）を加え、窒素置換した後、３０ｋＰａを維持しながら、２２５℃で攪拌を行った。２時間後、加熱をやめ、内部標準としてアニソール３３．３ｍｇを加え、1Ｈ−ＮＭＲ（バリアン社製，ＭＥＲＣＵＲＹ４００）測定を行った。末端オレフィンのビニルプロトン、内部オレフィンのビニルプロトン、及び内部標準であるアニソールのメチル基の積分比を比較することにより求めた原料及び生成物の定量値に基づいて、原料転化率、オレフィン選択率及びオレフィン収率を算出した。ステアリン酸無水物の転化率は４３モル％であり、仕込みステアリン酸無水物に対してオレフィンが収率２５モル％で得られた。
(Olefin production)
In a 50 mL eggplant-shaped flask, 4.13 g (7.5 mmol) of stearic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.44 g of 5 mass% PdI 2 / SiO 2 prepared above (as PdI 2) 0.19 mmol) was added and the atmosphere was replaced with nitrogen, followed by stirring at 225 ° C. while maintaining 30 kPa. After 2 hours, the heating was stopped, 33.3 mg of anisole was added as an internal standard, and 1 H-NMR (Mercury 400, manufactured by Varian) was measured. Based on the quantitative values of the raw materials and products obtained by comparing the integral ratios of the terminal olefin vinyl proton, the internal olefin vinyl proton, and the internal standard anisole methyl group, the raw material conversion rate, olefin selectivity, and The olefin yield was calculated. The conversion of stearic anhydride was 43 mol%, and an olefin was obtained in a yield of 25 mol% with respect to the charged stearic anhydride.
実施例２〜４、比較例１
触媒の種類を表１に示す触媒に変えた以外は実施例１と同様に触媒を調製し、オレフィンを製造して測定を行った（ＺｒＯ2（第一稀元素化学工業（株）製ＲＣ−１００）、ＴｉＯ2（堺化学工業（株）製ＳＳＰ−Ｍ）、Ｃ（Ｎｏｒｉｔ（株）製ＣＡＳＰ））。
Examples 2-4, Comparative Example 1
A catalyst was prepared in the same manner as in Example 1 except that the type of catalyst was changed to the catalyst shown in Table 1, and olefin was produced and measured (ZrO 2 (RC-1 manufactured by Daiichi Rare Element Chemical Co., Ltd.). 100), TiO 2 (SSP-M manufactured by Sakai Chemical Industry Co., Ltd.), C (CASP manufactured by Norit Co., Ltd.)).
得られた触媒は、ＸＰＳ測定（ＰＨＩ Ｑｕａｎｔｒａ ＳＸＭ （ＵＬＶＡＣ−ＰＩ．ＩＮＣ））より、Ｐｄ ３ｄ5/2結合エネルギー及びヨウ素原子とパラジウム原子のモル比がＺｒＯ2 (３３７［ｅＶ］、Ｉ／Ｐｄ＝２）、ＴｉＯ2（３３７［ｅＶ］、Ｉ／Ｐｄ＝２）、Ｃ（ ３３７［ｅＶ］、Ｉ／Ｐｄ＝２）であった。 From the XPS measurement (PHI Quantra SXM (ULVAC-PI. INC)), the obtained catalyst has a Pd 3d 5/2 bond energy and a molar ratio of iodine atom to palladium atom of ZrO 2 (337 [eV], I / Pd = 2), TiO 2 (337 [eV], I / Pd = 2), C ( 337 [eV], I / Pd = 2).
実施例１〜４及び比較例１の結果を併せて表１に示す。なお比較例１のＰｄＩ2はＰｄＩ2（和光純薬工業（株）製）をそのまま触媒として使用した。 The results of Examples 1 to 4 and Comparative Example 1 are shown together in Table 1. In addition, PdI 2 (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a catalyst for PdI 2 of Comparative Example 1 as it was.
実施例５
(触媒の調製）
Ｐｄ（ＯＡｃ）2（和光純薬工業（株）製）０．３４ｇ（１．５ｍｍｏｌ）をメタノール（キシダ化学（株）製）（８５．０ｇ）に溶かした後、担体としてＣ（Ｎｏｒｉｔ（株）製ＣＡＳＰ）（１０．８ｇ）を加え、０．５時間攪拌した。次に予め調製しておいた１質量％ＫＩ メタノール溶液（ＫＩはＳＩＧＭＡ ＡＬＤＲＩＣＨ（株）製、メタノールはキシダ化学（株）製））を０．５時間かけて５２．０ｇ（ＫＩとして３．１５ｍｍｏｌ）滴下した。４時間室温で攪拌した後、０．２μｍテフロン製メンブランフィルターでろ過した。得られた固体をメタノール及びイオン交換水で十分洗浄した後、窒素雰囲気下、１１０℃、２０ｋＰａで１日乾燥した。得られた触媒は質量比ＰｄＩ2／Ｃ＝５／１００のものである。
Example 5
(Preparation of catalyst)
After dissolving 0.34 g (1.5 mmol) of Pd (OAc) 2 (manufactured by Wako Pure Chemical Industries, Ltd.) in methanol (manufactured by Kishida Chemical Co., Ltd.) (85.0 g), C (Norit (stock) ) CASP) (10.8 g) was added and stirred for 0.5 hour. Next, 52.0 g (KI as 3.15 mmol as KI) of 1% by mass KI methanol solution prepared in advance (KI is manufactured by SIGMA ALDRICH Co., Ltd. and methanol is manufactured by Kishida Chemical Co., Ltd.) over 0.5 hours. ) Added dropwise. After stirring for 4 hours at room temperature, the mixture was filtered through a 0.2 μm Teflon membrane filter. The obtained solid was sufficiently washed with methanol and ion-exchanged water, and then dried at 110 ° C. and 20 kPa for 1 day in a nitrogen atmosphere. The obtained catalyst has a mass ratio of PdI 2 / C = 5/100.
（オレフィンの製造）
５０ｍＬナス型フラスコに攪拌子と、ステアリン酸（花王（株）製，ＬＵＮＡＣ Ｓ９８）４．２７ｇ（１５．０ｍｍｏｌ）、上記で調製した５質量％ＰｄＩ2／Ｃ １．４２ｇ（ＰｄＩ2として０．１８５ｍｍｏｌ）、内部標準用にスクアラン（ＳＩＧＭＡ ＡＬＤＲＩＣＨ社製）０．６３ｇ（１．５ｍｍｏｌ）を加え、窒素置換した後、３０ｋＰａを維持しながら、２８０℃で攪拌を行った。２時間後、加熱をやめ、反応終了溶液をガスクロマトグラフィーにて分析した。
(Olefin production)
In a 50 mL eggplant-shaped flask, 4.27 g (15.0 mmol) of stearic acid (manufactured by Kao Corporation, LUNAC S98), 1.42 g of 5% by mass PdI 2 / C prepared above (PdI 2 was reduced to 0.42 g). 185 mmol), 0.63 g (1.5 mmol) of squalane (manufactured by SIGMA ALDRICH) was added for internal standard, and the atmosphere was purged with nitrogen, followed by stirring at 280 ° C. while maintaining 30 kPa. After 2 hours, the heating was stopped and the reaction completed solution was analyzed by gas chromatography.
＜ガスクロマトグラフィー＞
ガスクロマトグラフィーはＡｇｉｌｅｎｔ社製「ＨＰ６８９０」及びＦｒｏｎｔｅｅｒＬＡＢ製「Ｕｌｔｒａ−Ａｌｌｏｙ−１（０．２５ｍｍφ＊３０ｍ×０．１５μｍ-thickness）」を用い、下記の条件で測定した。
昇温条件 ；６０℃で２分保持後、１分間に１０℃の速度で６０℃から３５０℃まで昇温し、３５０℃で５分間保持した。
キャリアガス ；ヘリウム
流量 ；０．８ｍＬ／分
注入口温度 ；３００℃
検出器（ＦＩＤ）温度；３５０℃
注入量 ；１μＬ
スプリット ；２０：１
内部標準物質 ；スクアラン
<Gas chromatography>
Gas chromatography was measured under the following conditions using “HP6890” manufactured by Agilent and “Ultra-Alloy-1 (0.25 mmφ * 30 m × 0.15 μm-thickness)” manufactured by FronterLAB.
Temperature rising condition: After holding at 60 ° C. for 2 minutes, the temperature was raised from 60 ° C. to 350 ° C. at a rate of 10 ° C. per minute and held at 350 ° C. for 5 minutes.
Carrier gas; helium flow rate; 0.8 mL / min inlet temperature; 300 ° C
Detector (FID) temperature: 350 ° C
Injection volume: 1 μL
Split; 20: 1
Internal reference material: Squalane
表２に示すように、ステアリン酸の転化率は９４モル％であり、仕込みステアリン酸に対してオレフィンが収率７８モル％で得られた。 As shown in Table 2, the conversion rate of stearic acid was 94 mol%, and an olefin was obtained in a yield of 78 mol% with respect to the stearic acid charged.
実施例６、比較例５ａ
触媒の種類を表２に示すように変えた以外は実施例５と同様に触媒を調製し、オレフィンを製造して分析を行った。ＴｉＯ2は堺化学工業（株）製 ＳＳＰ−Ｍ であり、ＰｄＩ2は和光純薬工業（株）製をそのまま触媒として使用した。
Example 6, Comparative Example 5a
A catalyst was prepared in the same manner as in Example 5 except that the type of catalyst was changed as shown in Table 2, and olefin was produced and analyzed. TiO 2 was SSP-M manufactured by Sakai Chemical Industry Co., Ltd., and PdI 2 was directly used as a catalyst manufactured by Wako Pure Chemical Industries, Ltd.
比較例５ｂ
（オレフィンの製造）
Ｄｅａｎ−Ｓｔａｒｋ管を備えた１００ｍＬ四ツ口フラスコに、ステアリン酸（花王（株）製，ＬＵＮＡＣ Ｓ９８）４０ｇ（１４０ｍｍｏｌ）、５質量％Ｐｄ／Ｃ （ＳＩＧＭＡ ＡＬＤＲＩＣＨ（株）社製）４．０ｇ（Ｐｄとして１．９ｍｍｏｌ）を加え、窒素バブリングしながら、２８０℃で攪拌を行った。２時間後、加熱をやめ、反応終了溶液をガスクロマトグラフィーにて分析した。
Comparative Example 5b
(Olefin production)
In a 100 mL four-necked flask equipped with a Dean-Stark tube, 40 g (140 mmol) of stearic acid (manufactured by Kao Corporation, LUNAC S98), 5 mass% Pd / C (manufactured by SIGMA ALDRICH Co., Ltd.) 4.0 g ( 1.9 mmol) was added as Pd, and the mixture was stirred at 280 ° C. while bubbling with nitrogen. After 2 hours, the heating was stopped and the reaction completed solution was analyzed by gas chromatography.
＜ガスクロマトグラフィー＞
ガスクロマトグラフィーはＡｇｉｌｅｎｔ社製「ＨＰ６８９０」及びＦｒｏｎｔｅｅｒＬＡＢ製「Ｕｌｔｒａ−Ａｌｌｏｙ−１（０．２５ｍｍφ＊３０ｍ×０．１５μｍ-thickness）」を用い、下記の条件で測定した。
昇温条件 ；６０℃で２分保持後、１分間に１０℃の速度で６０℃から３５０℃まで昇温し、３５０℃で１５分間保持した。
キャリアガス ；ヘリウム
流量 ；０．８ｍＬ／分
注入口温度 ；３００℃
検出器（ＦＩＤ）温度；３５０℃
注入量 ；２μＬ
スプリット ；５０：１
内部標準物質 ；スクアラン
ステアリン酸の転化率は２０モル％であり、仕込みステアリン酸に対してオレフィンが収率５モル％で得られた。
<Gas chromatography>
Gas chromatography was measured under the following conditions using “HP6890” manufactured by Agilent and “Ultra-Alloy-1 (0.25 mmφ * 30 m × 0.15 μm-thickness)” manufactured by FronterLAB.
Temperature rising condition: After holding at 60 ° C. for 2 minutes, the temperature was raised from 60 ° C. to 350 ° C. at a rate of 10 ° C. per minute and held at 350 ° C. for 15 minutes.
Carrier gas; helium flow rate; 0.8 mL / min inlet temperature; 300 ° C
Detector (FID) temperature: 350 ° C
Injection volume: 2 μL
Split; 50: 1
Internal standard substance: Squalane The conversion of stearic acid was 20 mol%, and an olefin was obtained in a yield of 5 mol% with respect to the stearic acid charged.
実施例５、実施例６、比較例５ａ及び５ｂの結果を併せて表２に示す。 Table 2 shows the results of Example 5, Example 6, and Comparative Examples 5a and 5b.
実施例７
(鈴木-宮浦カップリング反応：有機ホウ素化合物とハロゲン化
アリールの炭素−炭素結合形成反応）
５０ｍＬナス型フラスコに攪拌子と、ヨウ化ベンゼン（和光純薬工業（株）製）２．０４ｇ（１０．０ｍｍｏｌ）、フェニルホウ素酸（和光純薬工業（株）製）１．４６ｇ（１２．０ｍｍｏｌ）、体積比でメチル−２−ピロリドン（ＮＭＰ）（和光純薬工業（株）製）／Ｈ2Ｏ＝５／２の溶液を２５ｍＬ、炭酸ナトリウム（和光純薬工業（株）製）１．２７ｇ（１２．０ｍｍｏｌ）、実施例５と同様にして調製した５質量％ＰｄＩ2／Ｃ ７２．０ｍｇ（ＰｄＩ2として０．０１ｍｍｏｌ）を加え、窒素置換した後、１０３ｋＰａ、１２０℃で攪拌を行った。４時間後、加熱をやめ、反応終了溶液をガスクロマトグラフィーにて分析した。
Example 7
(Suzuki-Miyaura coupling reaction: Carbon-carbon bond formation reaction between organoboron compounds and aryl halides)
In a 50 mL eggplant-shaped flask, a stirring bar, 2.04 g (10.0 mmol) of benzene iodide (manufactured by Wako Pure Chemical Industries, Ltd.), 1.46 g of phenylboric acid (manufactured by Wako Pure Chemical Industries, Ltd.) (12. 0 mmol), 25 mL of a solution of methyl-2-pyrrolidone (NMP) (manufactured by Wako Pure Chemical Industries, Ltd.) / H 2 O = 5/2 by volume ratio, sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) 1 .27 g (12.0 mmol) and 5 mass% PdI 2 / C 72.0 mg (0.01 mmol as PdI 2 ) prepared in the same manner as in Example 5 were added, and the atmosphere was replaced with nitrogen, followed by stirring at 103 kPa and 120 ° C. went. After 4 hours, the heating was stopped and the reaction completed solution was analyzed by gas chromatography.
＜ガスクロマトグラフィー＞
ガスクロマトグラフィーはＡｇｉｌｅｎｔ社製「ＨＰ６８９０」及びＦｒｏｎｔｅｅｒＬＡＢ製「Ｕｌｔｒａ−Ａｌｌｏｙ−１（０．２５ｍｍφ＊３０ｍ×０．１５μｍ-thickness）」を用い、下記の条件で測定した。
昇温条件 ；６０℃で２分保持後、１分間に１０℃の速度で６０℃から３５０℃まで昇温し、３５０℃で５分間保持した。
キャリアガス ；ヘリウム
流量 ；０．８ｍＬ／分
注入口温度 ；３００℃
検出器（ＦＩＤ）温度；３５０℃
注入量 ；１μＬ
スプリット ；２０：１
内部標準物質 ；スクアラン
ヨウ化ベンゼンの転化率は１００モル％であり、用いたヨウ化ベンゼンに対してビフェニルが収率９９モル％で得られた。
<Gas chromatography>
Gas chromatography was measured under the following conditions using “HP6890” manufactured by Agilent and “Ultra-Alloy-1 (0.25 mmφ * 30 m × 0.15 μm-thickness)” manufactured by FronterLAB.
Temperature rising condition: After holding at 60 ° C. for 2 minutes, the temperature was raised from 60 ° C. to 350 ° C. at a rate of 10 ° C. per minute and held at 350 ° C. for 5 minutes.
Carrier gas; helium flow rate; 0.8 mL / min inlet temperature; 300 ° C
Detector (FID) temperature: 350 ° C
Injection volume: 1 μL
Split; 20: 1
Internal standard substance: Squalane The conversion of iodobenzene was 100 mol%, and biphenyl was obtained in a yield of 99 mol% with respect to the iodobenzene used.
比較例７
触媒の種類を表３に示す触媒に変えた以外は実施例７と同様に行った。５質量％Ｐｄ／Ｃ （ＳＩＧＭＡ ＡＬＤＲＩＣＨ（株）製）をそのまま触媒として使用した。実施例７、比較例７の結果を併せて表３に示す。
Comparative Example 7
The same procedure as in Example 7 was performed except that the catalyst type was changed to the catalyst shown in Table 3. 5% by mass Pd / C (manufactured by SIGMA ALDRICH Co., Ltd.) was used as a catalyst as it was. The results of Example 7 and Comparative Example 7 are shown together in Table 3.
実施例８
（ヘック反応：アルケンと有機ハロゲン化合物の炭素−炭素結合形成反応）
５０ｍＬナス型フラスコに攪拌子と、ヨウ化ベンゼン（和光純薬工業（株）製）２．０４ｇ（１０．０ｍｍｏｌ）、スチレン（キシダ化学（株）製）１．２５ｇ（１２．０ｍｍｏｌ）、体積比でメチル−２−ピロリドン（ＮＭＰ）（和光純薬工業（株）製）／Ｈ2Ｏ＝５／２の溶液を２５ｍＬ、トリブチルアミン（和光純薬工業（株）製）２．２３ｇ（１２．０ｍｍｏｌ）、実施例５と同様にして調製した５質量％ＰｄＩ2／Ｃ ０．７２ｇ（ＰｄＩ2として０．１ｍｍｏｌ）を加え、窒素置換した後、１０３ｋＰａ、１００℃で攪拌を行った。４時間後、加熱をやめ、反応終了溶液をガスクロマトグラフィーにて分析した。
Example 8
(Heck reaction: carbon-carbon bond formation reaction between alkene and organic halogen compound)
In a 50 mL eggplant-shaped flask, 2.04 g (10.0 mmol) of benzene iodide (manufactured by Wako Pure Chemical Industries, Ltd.), 1.25 g (12.0 mmol) of styrene (manufactured by Kishida Chemical Co., Ltd.), volume 25 mL of a solution of methyl-2-pyrrolidone (NMP) (manufactured by Wako Pure Chemical Industries, Ltd.) / H 2 O = 5/2, 2.23 g of tributylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (12 0.0 mmol) and 0.72 g (0.1 mmol as PdI 2 ) of 5 mass% PdI 2 / C prepared in the same manner as in Example 5 were added, and the atmosphere was purged with nitrogen, followed by stirring at 103 kPa and 100 ° C. After 4 hours, the heating was stopped and the reaction completed solution was analyzed by gas chromatography.
＜ガスクロマトグラフィー＞
ガスクロマトグラフィーはＡｇｉｌｅｎｔ社製「ＨＰ６８９０」及びＦｒｏｎｔｅｅｒＬＡＢ製「Ｕｌｔｒａ−Ａｌｌｏｙ−１（０．２５ｍｍφ＊３０ｍ×０．１５μｍ-thickness）」を用い、下記の条件で測定した。
昇温条件 ；６０℃で２分保持後、１分間に１０℃の速度で６０℃から３５０℃まで昇温し、３５０℃で５分間保持した。
キャリアガス ；ヘリウム
流量 ；０．８ｍＬ／分
注入口温度 ；３００℃
検出器（ＦＩＤ）温度；３５０℃
注入量 ；１μＬ
スプリット ；２０：１
内部標準物質 ；スクアラン
<Gas chromatography>
Gas chromatography was measured under the following conditions using “HP6890” manufactured by Agilent and “Ultra-Alloy-1 (0.25 mmφ * 30 m × 0.15 μm-thickness)” manufactured by FronterLAB.
Temperature rising condition: After holding at 60 ° C. for 2 minutes, the temperature was raised from 60 ° C. to 350 ° C. at a rate of 10 ° C. per minute and held at 350 ° C. for 5 minutes.
Carrier gas; helium flow rate; 0.8 mL / min inlet temperature; 300 ° C
Detector (FID) temperature: 350 ° C
Injection volume: 1 μL
Split; 20: 1
Internal reference material: Squalane
ヨウ化ベンゼンの転化率は１６モル％であり、仕込みヨウ化ベンゼンに対してスチルベンが収率１６モル％で得られた。 The conversion of iodobenzene was 16 mol%, and stilbene was obtained in a yield of 16 mol% with respect to the charged iodobenzene.
実施例８の結果を表４に示す。 The results of Example 8 are shown in Table 4.
Claims (8)
A method for forming an intermolecular or intramolecular carbon-carbon bond between an organoboron compound and an organohalogen compound using the Pd compound-supported catalyst according to any one of claims 2 to 5 and not claiming claim 1.
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