JP5291472B2 - FIXED TRANSITION METAL CATALYST, PROCESS FOR PRODUCING THE SAME AND METHOD OF USING THE SAME - Google Patents
FIXED TRANSITION METAL CATALYST, PROCESS FOR PRODUCING THE SAME AND METHOD OF USING THE SAME Download PDFInfo
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- JP5291472B2 JP5291472B2 JP2009001641A JP2009001641A JP5291472B2 JP 5291472 B2 JP5291472 B2 JP 5291472B2 JP 2009001641 A JP2009001641 A JP 2009001641A JP 2009001641 A JP2009001641 A JP 2009001641A JP 5291472 B2 JP5291472 B2 JP 5291472B2
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- Japan
- Prior art keywords
- transition metal
- substrate
- metal catalyst
- reaction
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000003054 catalyst Substances 0.000 title claims description 93
- 229910052723 transition metal Inorganic materials 0.000 title claims description 88
- 150000003624 transition metals Chemical class 0.000 title claims description 88
- 238000000034 method Methods 0.000 title claims description 44
- 239000000758 substrate Substances 0.000 claims description 83
- 238000006243 chemical reaction Methods 0.000 claims description 81
- 229910052751 metal Inorganic materials 0.000 claims description 62
- 239000002184 metal Substances 0.000 claims description 62
- 150000004767 nitrides Chemical class 0.000 claims description 34
- 229910052717 sulfur Inorganic materials 0.000 claims description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 26
- 239000011593 sulfur Substances 0.000 claims description 26
- 125000004434 sulfur atom Chemical group 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- 150000003623 transition metal compounds Chemical group 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- 229920001021 polysulfide Polymers 0.000 claims description 6
- 239000005077 polysulfide Substances 0.000 claims description 6
- 150000008117 polysulfides Polymers 0.000 claims description 6
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910002704 AlGaN Inorganic materials 0.000 claims description 3
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229940016373 potassium polysulfide Drugs 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 35
- 239000002904 solvent Substances 0.000 description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 14
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 238000007341 Heck reaction Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- -1 sulfide ions Chemical class 0.000 description 11
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000012433 hydrogen halide Substances 0.000 description 6
- 229910000039 hydrogen halide Inorganic materials 0.000 description 6
- 238000001451 molecular beam epitaxy Methods 0.000 description 6
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 5
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 description 5
- 150000001502 aryl halides Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052594 sapphire Inorganic materials 0.000 description 5
- 239000010980 sapphire Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000000370 acceptor Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RWMJRMPOKXSHHI-UHFFFAOYSA-N ethenylboron Chemical class [B]C=C RWMJRMPOKXSHHI-UHFFFAOYSA-N 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- NMWSKOLWZZWHPL-UHFFFAOYSA-N 3-chlorobiphenyl Chemical group ClC1=CC=CC(C=2C=CC=CC=2)=C1 NMWSKOLWZZWHPL-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- FANSKVBLGRZAQA-UHFFFAOYSA-M dipotassium;sulfanide Chemical compound [SH-].[K+].[K+] FANSKVBLGRZAQA-UHFFFAOYSA-M 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007876 drug discovery Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical class P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical compound [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、遷移金属触媒を基板上に固定した固定型遷移金属触媒及びその製造方法並びにその使用方法に関する。 The present invention relates to a fixed transition metal catalyst having a transition metal catalyst fixed on a substrate, a method for producing the same, and a method for using the same.
遷移金属触媒を用いた化学反応は、従来法では構築し難かった結合、特に新たな炭素−炭素結合を簡便に構築することを可能とし、創薬化学、有機合成化学を始め様々な化学分野で広く用いられている。しかし、遷移金属触媒には、安全性、安定性、反応生成物に混入する微量の遷移金属の除去、廃液処理等が問題となる場合がある。特に、工業的規模で、遷移金属触媒を使用する場合には、生成物に混入する微量金属の除去の問題だけでなく、使用した遷移金属触媒の金属の回収や金属を含有する廃液の処理等が大きな問題であった。また、近年高まっている環境調和型プロセス開発に対する社会的要請に鑑みると、金属の回収や廃液の処理が極めて大きな問題となっている。 Chemical reactions using transition metal catalysts make it possible to easily construct bonds that were difficult to construct by conventional methods, especially new carbon-carbon bonds, in various chemical fields including drug discovery chemistry and organic synthetic chemistry. Widely used. However, there are cases where the transition metal catalyst has problems such as safety, stability, removal of a small amount of transition metal mixed in the reaction product, waste liquid treatment, and the like. In particular, when using transition metal catalysts on an industrial scale, not only the problem of removing trace metals mixed in the product, but also the recovery of used transition metal catalysts and the treatment of waste liquids containing metals, etc. Was a big problem. Further, in view of the social demand for environmentally conscious process development that has been increasing in recent years, metal recovery and waste liquid treatment are extremely serious problems.
このような遷移金属触媒が有する諸問題を解決するため、遷移金属触媒の特色を生かすことができ、かつ金属の回収や廃液処理の問題を解決できる新たな素材の開発が待たれている。この解決策の一つとして、遷移金属触媒を物理的な吸着により担体に担持させる方法がある。しかし、物理的な吸着による担持では微量の金属の流出を防止することができず、また担体に担持させる方法では均一系触媒に比べ活性が低いという問題もあり、新たな担持方法の開発が望まれている。 In order to solve various problems of such a transition metal catalyst, development of a new material that can make use of the characteristics of the transition metal catalyst and solve the problems of metal recovery and waste liquid treatment is awaited. One solution is to support a transition metal catalyst on a support by physical adsorption. However, the loading by physical adsorption cannot prevent a minute amount of metal from flowing out, and the method of loading on a carrier has a problem that the activity is lower than that of a homogeneous catalyst, and it is hoped that a new loading method will be developed. It is rare.
本発明者の一人は、共有結合や配位結合等の化学結合又はそれに近い状態で、遷移金属触媒を担体に強固に結合した固定型遷移金属触媒の開発を検討している。その過程において、ガリウム砒素基板が、遷移金属触媒を強固に固定すること、そしてその固定された触媒が高い活性を有することを見出している（特許文献１）。 One of the inventors of the present invention is studying the development of a stationary transition metal catalyst in which a transition metal catalyst is firmly bound to a support in a chemical bond such as a covalent bond or a coordinate bond or a state close thereto. In the process, it has been found that the gallium arsenide substrate firmly fixes the transition metal catalyst, and that the fixed catalyst has high activity (Patent Document 1).
しかしながら、ガリウム砒素基板は、毒性のある砒素が基板から溶出する可能性があり、実用化には向いていない。 However, the gallium arsenide substrate is not suitable for practical use because toxic arsenic may be eluted from the substrate.
そこで、本発明者らは、遷移金属触媒を強固に固定することができ、その固定された触媒が高い活性を有し、かつ毒性のない固定型遷移金属触媒及びその製造方法並びにその使用方法を提供することを目的とした。 Therefore, the inventors of the present invention are able to firmly fix the transition metal catalyst, and the fixed catalyst has high activity and has no toxicity. The purpose was to provide.
上記課題を解決するため、本発明者は鋭意検討した結果、窒化金属が、遷移金属触媒を強固に固定することができ、その固定された触媒が高い活性を有することを見出して本発明を完成させたものである。
すなわち、本発明の固定型遷移金属触媒は、マイクロ波を照射した状態で用いる固定型遷移金属触媒であって、少なくとも表面に金属窒化物層を有する基板又は金属窒化物からなる基板の表面に硫黄原子を介して遷移金属又は遷移金属化合物が結合していることを特徴とするものである。
In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, found that metal nitride can firmly fix the transition metal catalyst, and that the fixed catalyst has high activity, thereby completing the present invention. It has been made.
That is, the fixed type transition metal catalyst of the present invention is a fixed type transition metal catalyst used in a state of being irradiated with microwaves, and at least sulfur on the surface of a substrate having a metal nitride layer on the surface or a substrate made of metal nitride. A transition metal or a transition metal compound is bonded through an atom.
上記金属窒化物には、ＩＩＩ族金属窒化物を用いることができる。 Group III metal nitride can be used as the metal nitride.
また、上記ＩＩＩ族金属窒化物に、ＡｌＮ、ＧａＮ、ＩｎＮ、ＡｌＧａＮ、ＩｎＧａＮ、ＩｎＡｌＮ及びＡｌＩｎＧａＮからなる群から選択された１種の窒化物を用いることができる。 Further, as the group III metal nitride, one kind of nitride selected from the group consisting of AlN, GaN, InN, AlGaN, InGaN, InAlN, and AlInGaN can be used.
また、本発明においては、上記遷移金属に、Ｍｎ、Ｆｅ、Ｒｕ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ及びＹｂからなる群から選択された１種の金属を用いることができる。 In the present invention, the transition metal is selected from the group consisting of Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, and Yb. These metals can be used.
本発明の固定型遷移金属触媒は、以下の方法を用いて製造することができる。
すなわち、本発明の固定型遷移金属触媒の製造方法は、マイクロ波を照射した状態で用いる固定型遷移金属触媒の製造方法であって、少なくとも表面に金属窒化物層を有する基板又は金属窒化物からなる基板の表面に硫黄原子を結合させる硫黄終端処理と、該硫黄原子に遷移金属又は遷移金属化合物を結合させる金属定着処理とを行うことを特徴とする。
The stationary transition metal catalyst of the present invention can be produced using the following method.
That is, the method for producing a fixed type transition metal catalyst of the present invention is a method for producing a fixed type transition metal catalyst used in a state of being irradiated with microwaves, and includes at least a substrate or metal nitride having a metal nitride layer on the surface. A sulfur termination treatment for bonding sulfur atoms to the surface of the substrate and a metal fixing treatment for bonding a transition metal or a transition metal compound to the sulfur atoms are performed.
本発明の製造方法においては、上記硫黄終端処理において、上記基板の表面に硫黄原子を蒸着させて硫黄原子を上記基板の表面に結合させることができる。 In the manufacturing method of this invention, in the said sulfur termination process, a sulfur atom can be vapor-deposited on the surface of the said board | substrate, and a sulfur atom can be combined with the surface of the said board | substrate.
また、本発明の製造方法においては、上記硫黄終端処理において、上記基板の表面に硫化物の水溶液を接触させて硫黄原子を上記基板の表面に結合させることもできる。 In the production method of the present invention, in the sulfur termination treatment, an aqueous solution of sulfide may be brought into contact with the surface of the substrate to bond sulfur atoms to the surface of the substrate.
また、本発明の製造方法においては、上記硫化物に、硫化ナトリウム、硫化カリウム、硫化アンモニウム、硫化水素ナトリウム、硫化水素カリウム、硫化水素アンモニウム、多硫化ナトリウム、多硫化カリウム、多硫化アンモニウムからなる群から選択された少なくとも１種を用いることができる。 Further, in the production method of the present invention, the sulfide is composed of sodium sulfide, potassium sulfide, ammonium sulfide, sodium hydrogen sulfide, potassium hydrogen sulfide, ammonium hydrogen sulfide, sodium polysulfide, potassium polysulfide, and ammonium polysulfide. At least one selected from can be used.
また、本発明の製造方法においては、上記硫黄終端処理に先立って、上記基板の表面の酸化膜を除去する酸化膜除去処理を行うこともできる。 Moreover, in the manufacturing method of this invention, prior to the said sulfur termination process, the oxide film removal process which removes the oxide film on the surface of the said board | substrate can also be performed.
また、本発明の製造方法においては、上記金属定着処理の後に、上記金属定着処理を行った上記基板を加熱する、加熱定着処理を行うこともできる。 In the manufacturing method of the present invention, after the metal fixing process, a heat fixing process in which the substrate subjected to the metal fixing process is heated can be performed.
また、本発明者らは、本発明の固定型遷移金属触媒を、マイクロ波を照射した状態で用いることにより、従来の、オイルバス等を用いた反応容器を外部加熱する方法に比べ非常に短時間で反応を完結させることができることを見出した。
すなわち、本発明の固定型遷移金属触媒の使用方法は、少なくとも表面に金属窒化物層を有する基板又は金属窒化物からなる基板の表面に硫黄原子を介して遷移金属又は遷移金属化合物が結合している固定型遷移金属触媒の使用方法であって、上記固定型遷移金属触媒を含む反応液にマイクロ波を照射した状態で反応を進行させることを特徴とする。
In addition, the present inventors use the stationary transition metal catalyst of the present invention in a state irradiated with microwaves, which is much shorter than the conventional method of externally heating a reaction vessel using an oil bath or the like. We have found that the reaction can be completed in time.
That is, in the method of using the fixed transition metal catalyst of the present invention, a transition metal or a transition metal compound is bonded to a surface of a substrate having a metal nitride layer on the surface or a substrate made of a metal nitride via a sulfur atom. A method of using the fixed transition metal catalyst, wherein the reaction is allowed to proceed in a state where the reaction liquid containing the fixed transition metal catalyst is irradiated with microwaves.
本発明の固定型遷移金属触媒は、遷移金属触媒が基板に強固に固定され、高い触媒活性を有し、繰り返して使用することもできる。さらに窒化金属は、耐溶剤性や耐熱性に優れており安定であり、また毒性物質が生成することもない。そのため、従来大きな問題となっていた、生成物に混入する微量金属の除去の問題や、使用した遷移金属触媒の金属の回収や金属を含有する廃液の処理、安全性等の問題を解決することが可能である。 In the fixed transition metal catalyst of the present invention, the transition metal catalyst is firmly fixed to the substrate, has a high catalytic activity, and can be used repeatedly. Furthermore, metal nitride is excellent in solvent resistance and heat resistance, is stable, and does not generate toxic substances. Therefore, solve the problems of removal of trace metals mixed in the product, recovery of the metal of the transition metal catalyst used, treatment of waste liquid containing metal, safety, etc. Is possible.
また、本発明の固定型遷移金属触媒をマイクロ波を照射した状態で使用すると、従来の外部加熱方法に比べ、反応速度を増大させることができ、反応時間を短縮することが可能となる。これにより、遷移金属触媒を用いる反応の製造効率を向上させることが可能となる。なお、ガリウム砒素基板では、マイクロ波を照射すると、２００℃以上の高温となると分解して砒素が発生する可能性があるが、本発明では高温でも安定な窒化金属を基板に用いているので、安全である。 In addition, when the stationary transition metal catalyst of the present invention is used in a state of being irradiated with microwaves, the reaction rate can be increased and the reaction time can be shortened as compared with the conventional external heating method. Thereby, it becomes possible to improve the production efficiency of the reaction using the transition metal catalyst. In addition, in a gallium arsenide substrate, there is a possibility that arsenic is generated when it is heated to a temperature of 200 ° C. or higher when irradiated with microwaves. It is safe.
本発明の固定型遷移金属触媒は、マイクロ波を照射した状態で用いる固定型遷移金属触媒であって、少なくとも表面に金属窒化物層を有する基板又は金属窒化物からなる基板の表面に硫黄原子を介して遷移金属又は遷移金属化合物が結合していることを特徴とするものである。
The stationary transition metal catalyst of the present invention is a stationary transition metal catalyst used in a state of being irradiated with microwaves, and at least sulfur atoms are present on the surface of a substrate having a metal nitride layer on the surface or a substrate made of metal nitride. A transition metal or a transition metal compound is bonded thereto.
本発明で用いる基板は、少なくとも表面に金属窒化物層を有する基板又は金属窒化物からなる基板である。本発明で用いる金属窒化物は、金属が硫黄原子と結合可能であれば特に限定されない。好ましくはＩＩＩ族金属窒化物である。ＩＩＩ族金属窒化物は通常、１０００℃以上の高温で製造するため、耐熱性に優れ安定である。ＩＩＩ族金属窒化物としては、ＡｌＮ、ＧａＮ、ＩｎＮ、ＡｌＧａＮ、ＩｎＧａＮ、ＩｎＡｌＮそしてＡｌＩｎＧａＮ等を用いることができる。さらに好ましくは、ＧａＮである。 The substrate used in the present invention is a substrate having a metal nitride layer at least on its surface or a substrate made of metal nitride. The metal nitride used in the present invention is not particularly limited as long as the metal can be bonded to a sulfur atom. Group III metal nitride is preferred. Group III metal nitrides are usually produced at a high temperature of 1000 ° C. or higher, and thus are excellent in heat resistance and stable. As the group III metal nitride, AlN, GaN, InN, AlGaN, InGaN, InAlN, AlInGaN, or the like can be used. More preferably, it is GaN.
本発明では、これらのＩＩＩ属金属窒化物を、有機金属気相成長法（ＭＯＣＶＤ法）、分子線エピタキシー法（ＭＢＥ）あるいはハイドライド気相エピタキシー法（ＨＶＰＥ）等を用い、サファイア等の単結晶基板の上に成長させたものを、触媒担持用の基板として用いることができる。また、ＩＩＩ属金属窒化物の単結晶と触媒担持用の基板として用いることもできる。 In the present invention, these group III metal nitrides are formed on a single crystal substrate such as sapphire using a metal organic chemical vapor deposition method (MOCVD method), a molecular beam epitaxy method (MBE), a hydride vapor phase epitaxy method (HVPE), or the like. A substrate grown on the substrate can be used as a substrate for supporting a catalyst. Further, it can be used as a substrate for supporting a group III metal nitride single crystal and catalyst.
本発明で用いる好ましい基板として、サファイアの単結晶基板の表面にＧａＮ層を成長させた基板である。ＧａＮ層の厚さは、０．００１μｍ〜１０００μｍ、より好ましくは０．１μｍ〜１０μｍである。以下、特に断らない限り、表面にＧａＮ層を有する基板をＧａＮ基板という。 A preferred substrate used in the present invention is a substrate having a GaN layer grown on the surface of a sapphire single crystal substrate. The thickness of the GaN layer is 0.001 μm to 1000 μm, more preferably 0.1 μm to 10 μm. Hereinafter, unless otherwise specified, a substrate having a GaN layer on the surface is referred to as a GaN substrate.
本発明で用いる遷移金属には、原子番号が２１〜３０（Ｓｃ〜Ｚｎ）、３９〜４８（Ｙ〜Ｃｄ）、５７〜８０（Ｌａ〜Ｈｇ）である金属を挙げることができる。好ましくは、Ｍｎ、Ｆｅ、Ｒｕ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ及びＹｂからなる群から選択された１種の金属である。より好ましくは、硫黄原子との親和性の大きいルテニウム、パラジウム、そしてイッテルビウムである。また、遷移金属化合物には、遷移金属の酸化物、塩化物、そして配位子部分に有機物質を含有する錯体等が含まれるが、遷移金属錯体が好ましい。遷移金属錯体としては、例えば、パラジウムのホスフィン錯体を挙げることができる。 Examples of the transition metal used in the present invention include metals having atomic numbers of 21 to 30 (Sc to Zn), 39 to 48 (Y to Cd), and 57 to 80 (La to Hg). Preferably, it is one metal selected from the group consisting of Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, and Yb. More preferred are ruthenium, palladium, and ytterbium, which have a high affinity for sulfur atoms. In addition, transition metal compounds include transition metal oxides, chlorides, and complexes containing an organic substance in the ligand moiety, and transition metal complexes are preferred. Examples of the transition metal complex include palladium phosphine complexes.
また、基板上に固定される遷移金属の量には特に制限はなく、基板に結合している硫黄原子の量を増やすことにより、固定される遷移金属の量を増やすことができる。触媒活性を発現させるためには、基板の単位ｍ２当り、少なくとも５００ｍｇ程度が必要である。 Moreover, there is no restriction | limiting in particular in the quantity of the transition metal fixed on a board | substrate, By increasing the quantity of the sulfur atom couple | bonded with the board | substrate, the quantity of the transition metal fixed can be increased. In order to express the catalytic activity, at least about 500 mg is required per unit m 2 of the substrate.
次に、本発明の固定型遷移金属触媒の製造方法について説明する。
本発明の固定型遷移金属触媒の製造方法は、マイクロ波を照射した状態で用いる固定型遷移金属触媒の製造方法であって、少なくとも表面に金属窒化物層を有する基板又は金属窒化物からなる基板の表面に硫黄原子を結合させる硫黄終端処理と、該硫黄原子に遷移金属又は遷移金属化合物を結合させる金属定着処理とを行うことを特徴とするものである。
Next, the manufacturing method of the fixed type transition metal catalyst of this invention is demonstrated.
The method for producing a fixed-type transition metal catalyst of the present invention is a method for producing a fixed-type transition metal catalyst used in the state of being irradiated with microwaves, and is a substrate having at least a metal nitride layer on the surface or a substrate made of a metal nitride A sulfur termination treatment for bonding a sulfur atom to the surface of the metal and a metal fixing treatment for bonding a transition metal or a transition metal compound to the sulfur atom are performed.
本発明において、硫黄終端処理とは、基板表面に硫黄原子を結合させる処理をいう。硫黄終端処理には、基板の表面に硫黄原子を蒸着させて硫黄原子を基板の表面に結合させる方法（以下、物理的硫黄終端処理という。）や、基板の表面に硫化物の水溶液を接触させて硫黄原子を上記基板の表面に結合させる方法（以下、化学的硫黄終端処理という。）を用いることができる。 In the present invention, the sulfur termination treatment refers to a treatment for bonding sulfur atoms to the substrate surface. For sulfur termination, sulfur atoms are vapor-deposited on the surface of the substrate to bind the sulfur atoms to the surface of the substrate (hereinafter referred to as physical sulfur termination treatment), or an aqueous solution of sulfide is brought into contact with the surface of the substrate. Thus, a method of bonding sulfur atoms to the surface of the substrate (hereinafter referred to as chemical sulfur termination treatment) can be used.
物理的硫黄終端処理には、ＭＢＥ法を用いることができる。具体的には、文献（S.J.Danishefsky, et al.,J.Amer.Chem.Soc.,118,2843(1996)）に記載されたマルチステップ硫黄終端法（multi-step sulfur termination method）を用いることができる。ＭＢＥ法では、硫黄源に単体硫黄を用い、超高真空中で硫黄層を成長させる。ＭＢＥ法を用いることにより、硫黄原子の基板表面への配列を数ｎｍレベルで制御することができる。 The MBE method can be used for physical sulfur termination. Specifically, the multi-step sulfur termination method described in the literature (SJDanishefsky, et al., J. Amer. Chem. Soc., 118, 2843 (1996)) should be used. Can do. In the MBE method, simple sulfur is used as a sulfur source, and a sulfur layer is grown in an ultrahigh vacuum. By using the MBE method, the arrangement of sulfur atoms on the substrate surface can be controlled at the level of several nm.
一方、化学的硫黄終端処理は、硫化物の水溶液を用いるものであり、基板表面の処理を安価に行うことができる。硫化物は水溶液中で硫化物イオン（Ｓ２−）、硫化水素化物イオン（ＨＳ−）を生成する化合物であり、硫化ナトリウム（Ｎａ２Ｓ）、硫化カリウム（Ｋ２Ｓ）、硫化アンモニウム（（ＮＨ４）２Ｓ）、硫化水素ナトリウム（ＮａＳＨ）、硫化水素カリウム（ＫＳＨ）、硫化水素アンモニウム（ＮＨ４ＳＨ）からなる群から選択された少なくとも１種の化合物を用いることができる。より好ましくは硫化水素ナトリウムである。この硫化物を含む水溶液中に基板を浸漬し、室温（２０℃）〜１００℃の温度範囲で、１０分〜１２時間加熱することにより処理を行う。 On the other hand, chemical sulfur termination treatment uses an aqueous solution of sulfide, and the substrate surface can be treated at low cost. A sulfide is a compound that generates sulfide ions (S 2− ) and hydride sulfide ions (HS − ) in an aqueous solution. Sodium sulfide (Na 2 S), potassium sulfide (K 2 S), ammonium sulfide (( At least one compound selected from the group consisting of NH 4 ) 2 S), sodium hydrogen sulfide (NaSH), potassium hydrogen sulfide (KSH), and ammonium hydrogen sulfide (NH 4 SH) can be used. More preferred is sodium hydrogen sulfide. The substrate is immersed in this aqueous solution containing sulfide, and the treatment is performed by heating at a temperature range of room temperature (20 ° C.) to 100 ° C. for 10 minutes to 12 hours.
なお、化学的硫黄終端処理には、多硫化物（一般式Ｓｎ ２−で表され、ｎが２以上の多硫化物イオンを含む化合物）、具体的には多硫化アンモニウム（（ＮＨ４）２Ｓｎ）を使用することも可能である。しかし、多硫化アンモニウムはアンモニウムイオンを含み、さらに硫黄が硫化物に比べ多量に含まれているので廃液の処理が大きな問題となるので、好ましくない。 In addition, for chemical sulfur termination treatment, polysulfide (a compound containing a polysulfide ion represented by the general formula S n 2- , where n is 2 or more), specifically, ammonium polysulfide ((NH 4 )). it is also possible to use 2 S n). However, ammonium polysulfide is not preferred because it contains ammonium ions and further contains a large amount of sulfur as compared to sulfides.
本発明の製造方法では、触媒として用いる金属を担体である基板に結合させる金属定着処理を行う。金属定着処理は、基板表面に結合している硫黄原子に遷移金属又は遷移金属化合物を結合させることである。金属定着処理は、有機溶媒中に硫黄終端処理を行った基板を浸漬し、その溶媒に金属源となる遷移金属又は遷移金属化合物を加え、加熱することにより行う、例えば、ＧａＮ基板とパラジウムの組み合わせの場合、非プロトン溶媒が好ましく、例えば、アセトニトリル、酢酸エチル、アセトン、キシレン、トルエン、ベンゼン、ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド（ＤＭＳＯ）、テトラヒドロフラン（ＴＨＦ）、クロロホルム、ジクロロメタン及びその混合溶媒からなる群から選択された溶媒を用いることが好ましい。より好ましくはアセトニトリルである。また、パラジウム源は、酢酸パラジウム、塩化パラジウム、臭化パラジウム、ヨウ化パラジウム、硝酸パラジウム、酸化パラジウム硫酸パラジウム、硫化パラジウム等を用いることができる。処理は、室温（２０℃）〜１５０℃の温度範囲で、０．５〜２４時間行う。 In the production method of the present invention, a metal fixing process is performed in which a metal used as a catalyst is bonded to a substrate serving as a carrier. The metal fixing process is to bond a transition metal or a transition metal compound to sulfur atoms bonded to the substrate surface. The metal fixing process is performed by immersing a sulfur-terminated substrate in an organic solvent, adding a transition metal or transition metal compound as a metal source to the solvent, and heating, for example, a combination of a GaN substrate and palladium. In this case, an aprotic solvent is preferable, for example, consisting of acetonitrile, ethyl acetate, acetone, xylene, toluene, benzene, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), chloroform, dichloromethane and a mixed solvent thereof. It is preferred to use a solvent selected from the group. More preferred is acetonitrile. As the palladium source, palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium nitrate, palladium oxide palladium sulfate, palladium sulfide and the like can be used. The treatment is performed at a temperature range of room temperature (20 ° C.) to 150 ° C. for 0.5 to 24 hours.
また、本発明の製造方法においては、硫黄終端処理に先立って、上記基板の表面の酸化膜を除去する酸化膜除去処理を行うことが好ましい。酸化膜除去には、基板の種類に応じて酸又は塩基を用いることができる。例えば、ＧａＮ基板の場合、水酸化ナトリウム水溶液を用いることができる。具体的には１〜４０重量％の水酸化ナトリウム水溶液を用い、室温（２０℃）〜１００℃の温度範囲で、１０分〜１２時間、ＧａＮ基板を水酸化ナトリウム水溶液に浸漬して行う。十分に酸化膜除去を行うことにより、単位面積当たりに導入できる硫黄原子を増加させることができ、さらには単位面積当たりの遷移金属触媒の量を増加させることができる。これにより、転化率の増加、そして繰り返し使用回数の増加が期待できる。 Moreover, in the manufacturing method of this invention, it is preferable to perform the oxide film removal process which removes the oxide film on the surface of the said board | substrate prior to a sulfur termination process. For removing the oxide film, an acid or a base can be used depending on the type of the substrate. For example, in the case of a GaN substrate, an aqueous sodium hydroxide solution can be used. Specifically, a 1-40 wt% sodium hydroxide aqueous solution is used, and the GaN substrate is immersed in the sodium hydroxide aqueous solution at a temperature range of room temperature (20 ° C.) to 100 ° C. for 10 minutes to 12 hours. By sufficiently removing the oxide film, sulfur atoms that can be introduced per unit area can be increased, and further, the amount of the transition metal catalyst per unit area can be increased. As a result, an increase in the conversion rate and an increase in the number of repeated use can be expected.
また、本発明の製造方法においては、金属定着処理の後に、金属定着処理を行った基板を加熱する、加熱定着処理を行うことが好ましい。この加熱定着処理を行うことにより、基板に固定した遷移金属触媒が、反応時に溶出することを防止することができる。この処理は、有機溶媒中で、８０℃〜１８０℃の温度範囲で行う。例えば、ＧａＮ基板とパラジウムの組み合わせでは、溶媒には非極性溶媒のキシレン、デカリン等を用い、１３０〜１５０℃の温度範囲で、１０分〜１２時間行う。 In the production method of the present invention, it is preferable to perform a heat fixing treatment in which the substrate subjected to the metal fixing treatment is heated after the metal fixing treatment. By performing this heat fixing treatment, it is possible to prevent the transition metal catalyst fixed on the substrate from being eluted during the reaction. This treatment is performed in an organic solvent at a temperature range of 80 ° C to 180 ° C. For example, in the case of a combination of a GaN substrate and palladium, xylene, decalin, or the like, which is a nonpolar solvent, is used as the solvent, and the reaction is performed at a temperature range of 130 to 150 ° C. for 10 minutes to 12 hours.
本発明の固定型遷移金属触媒は、従来の粉末状の触媒に比し、優れた触媒活性を有する。さらにマイクロ波を照射した状態で反応を進行させることにより、その触媒活性を格段に向上させることができ、かつ繰り返して触媒を使用することを可能とする。本発明者らは、ＧａＮ基板を用いた場合、従来の粉末状触媒や、ＧａＮ基板のみでは反応に用いる溶媒の温度がマイクロ波を照射しても溶媒のみの場合の温度上昇と大きな違いがないのに対し、遷移金属触媒を結合させたＧａＮ基板では顕著な温度上昇が起きることを実験により確認している。本発明者らはマイクロ波照射によりこの溶媒の顕著な温度上昇が触媒活性の向上に寄与しているものと考えている。 The fixed transition metal catalyst of the present invention has superior catalytic activity as compared with conventional powdery catalysts. Furthermore, by proceeding the reaction in the state of being irradiated with microwaves, the catalytic activity can be remarkably improved and the catalyst can be used repeatedly. When the present inventors use a GaN substrate, the temperature rise of the solvent used in the reaction with the conventional powdered catalyst or the GaN substrate alone is not significantly different from the temperature rise in the case of the solvent alone even when irradiated with microwaves. On the other hand, it has been confirmed by experiments that a significant temperature rise occurs in the GaN substrate combined with the transition metal catalyst. The present inventors consider that the remarkable temperature increase of the solvent due to microwave irradiation contributes to the improvement of the catalytic activity.
照射するマイクロ波の周波数や出力は、そして照射方法は特に限定されるものではなく、反応温度を所定の範囲に維持できるように制御すれば良い。通常、周波数は1〜３００ＧＨｚの範囲、好ましくは２．４５ＧＨｚを用いることができる。また、出力は、１〜１０００Ｗ、より好ましくは１０〜５００Ｗである。また、照射方法は連続照射でも間欠照射でも良い。連続照射の場合、照射時間は、１秒〜２４時間、より好ましくは１秒〜１２時間である。反応方法としては、耐圧性の反応容器内に、反応基質、溶媒、触媒等を入れ混合した後、この反応容器に所定の出力のマイクロ波を照射して所定の反応温度まで昇温させた後、出力を制御してその所定の反応温度を維持せしめて反応を進行させる。 The frequency and output of the microwave to be irradiated and the irradiation method are not particularly limited, and may be controlled so that the reaction temperature can be maintained within a predetermined range. Usually, the frequency is in the range of 1 to 300 GHz, preferably 2.45 GHz. Moreover, an output is 1-1000W, More preferably, it is 10-500W. The irradiation method may be continuous irradiation or intermittent irradiation. In the case of continuous irradiation, the irradiation time is 1 second to 24 hours, more preferably 1 second to 12 hours. As a reaction method, a reaction substrate, a solvent, a catalyst, and the like are mixed in a pressure-resistant reaction vessel, and then heated to a predetermined reaction temperature by irradiating a microwave of a predetermined output to the reaction vessel. The reaction is allowed to proceed while maintaining the predetermined reaction temperature by controlling the output.
本発明の固定型遷移金属触媒は、遷移金属触媒が触媒活性を有する反応であれば、いかなる反応にも適用できる。また、液相反応だけでなく、気相反応にも用いることができる。本発明の触媒は、濾過。デカンテーション、遠心分離等により反応液から分離することができる。触媒を分離した反応液は、濃縮や抽出等の通常の処理方法により目的物が分離され、さらに、各種の精製手段により精製され単離される。 The fixed transition metal catalyst of the present invention can be applied to any reaction as long as the transition metal catalyst has a catalytic activity. Moreover, it can be used not only for liquid phase reactions but also for gas phase reactions. The catalyst of the present invention is filtered. The reaction solution can be separated by decantation, centrifugation or the like. From the reaction solution from which the catalyst has been separated, the target product is separated by a usual processing method such as concentration and extraction, and further purified and isolated by various purification means.
なお、実施例ではヘック（Heck）反応や鈴木反応に適用しているが、これらの反応に限定されるものではない。それらの反応は、炭素−炭素結合、炭素−水素結合、炭素−窒素結合、炭素−酸素結合、炭素−硫黄結合を生成するモデル反応として本発明の固定型遷移金属触媒の評価に用いているだけであり、接触還元反応、不斉合成反応、置換反応にも適用可能である。特に有害な遷移金属触媒の混入を抑制できることから、医薬品及びその中間体等の製造に必要な反応に好適に用いることができる。 In addition, although applied to Heck reaction and Suzuki reaction in the Example, it is not limited to these reactions. These reactions are only used for the evaluation of the fixed transition metal catalyst of the present invention as a model reaction that generates carbon-carbon bonds, carbon-hydrogen bonds, carbon-nitrogen bonds, carbon-oxygen bonds, and carbon-sulfur bonds. It is also applicable to catalytic reduction reaction, asymmetric synthesis reaction, and substitution reaction. Since especially harmful transition metal catalysts can be prevented from being mixed, it can be suitably used for reactions required for production of pharmaceuticals and intermediates thereof.
ここで、ヘック反応は、文献（H.A.Dieck and R.F.Heck, J.Am.Chem.Soc., 96,1133(1974) ：R.F.Heck,Acc.Chem.Rev.,12,146(1979)）に記載されているように、アリールハライド又はアルケニルハライドと、アルケン類との縮合反応であり、例えば、ハロゲン化ベンゼンとアクリル酸エステルとの反応により、桂皮酸エステルを製造する反応である。この反応の触媒には、従来、粉末状のパラジウム錯体が用いられている。この反応における、アリールハライド又はアルケニルハライドとしては、塩素原子、臭素原子又はヨウ素原子を挙げることができる。また、アリールハライドのアリール基としては、置換又は非置換のフェニル基、ナフチル基、ピリジン基、フリル基などの芳香族基を挙げることができ、これらの置換基としては反応に悪影響を与えないものであれば特に制限はなく、例えば、置換又は非置換の炭素数１〜２０、好ましくは１〜１０のアルキル基、置換又は非置換の炭素数１〜２０，好ましくは１〜１０のアルコキシ基、置換又は非置換の炭素数１〜２０，好ましくは１〜１０のアルコキシカルボニル基等を挙げることができる。また、アルケニルハライドのアルケニル基としては、置換又は非置換のビニル基であり、そのビニル基の置換基としては、置換又は非置換の炭素数１〜２０，好ましくは１〜１０のアルキル基、置換又は非置換の炭素数１〜２０，好ましくは１〜１０のアルケニル基、置換又は非置換の炭素数６〜１０のアリール基、置換又は非置換の炭素数７〜２０、好ましくは７〜１２のアラルキル基等を挙げることができる。また、アルケン類としては、少なくとも１個の水素原子を有するエチレン誘導体を挙げることができる。好ましくは、置換又は非置換のアクリル酸エステル誘導体である。そのアクリル酸エステル誘導体のエステル残基としては、置換又は非置換の炭素数１〜２０、好ましくは１〜１０のアルキル基を挙げることができる。また、この反応ではハロゲン化水素が発生するため、反応系にハロゲン化水素受容体を存在させておくことが好ましい。好ましいハロゲン化水素受容体としては、トリエチルアミン、Ｎ，Ｎ−ジエチルアミノベンゼン等の３級アミンを挙げることができる。また、好ましい溶媒は、アセトニトリルやテトラヒドロフラン等の極性非プロトン性溶媒である。なお、用いるパラジウム触媒の量は、ヨードベンゼンに対して、０．０１〜１０モル％、より好ましくは０．１〜０．５モル％である。 Here, the Heck reaction is described in literature (HADieck and RFHeck, J. Am. Chem. Soc., 96, 1133 (1974): RFHeck, Acc. Chem. Rev., 12, 146 (1979)). As shown, a condensation reaction between an aryl halide or an alkenyl halide and an alkene, for example, a reaction for producing a cinnamic acid ester by a reaction between a halogenated benzene and an acrylic acid ester. Conventionally, a powdery palladium complex has been used as a catalyst for this reaction. Examples of the aryl halide or alkenyl halide in this reaction include a chlorine atom, a bromine atom, and an iodine atom. Examples of the aryl group of the aryl halide include aromatic groups such as a substituted or unsubstituted phenyl group, naphthyl group, pyridine group, and furyl group, and these substituents do not adversely affect the reaction. If it is, there will be no restriction | limiting in particular, For example, a substituted or unsubstituted C1-C20, preferably 1-10 alkyl group, a substituted or unsubstituted C1-C20, preferably a 1-10 alkoxy group, Examples thereof include a substituted or unsubstituted alkoxycarbonyl group having 1 to 20, preferably 1 to 10 carbon atoms. In addition, the alkenyl group of the alkenyl halide is a substituted or unsubstituted vinyl group, and the substituent of the vinyl group is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Or an unsubstituted alkenyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted carbon group having 7 to 20 carbon atoms, preferably 7 to 12 carbon atoms. Examples thereof include an aralkyl group. Examples of alkenes include ethylene derivatives having at least one hydrogen atom. A substituted or unsubstituted acrylate derivative is preferable. Examples of the ester residue of the acrylate derivative include a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Further, since hydrogen halide is generated in this reaction, it is preferable that a hydrogen halide acceptor be present in the reaction system. Preferable hydrogen halide acceptors include tertiary amines such as triethylamine and N, N-diethylaminobenzene. A preferred solvent is a polar aprotic solvent such as acetonitrile or tetrahydrofuran. In addition, the quantity of the palladium catalyst to be used is 0.01-10 mol% with respect to iodobenzene, More preferably, it is 0.1-0.5 mol%.
また、鈴木反応は、文献（N.Miyaura,et al.,Synth.Commun.,11,513(1981)：Ni.Miyaura and A.Suzuki,Chem.Rev.,95,2457(1995)）に記載されているように、アリールボロン誘導体又はビニルボロン誘導体と、炭素―炭素二重結合を持つハライド又はスルホネートとの縮合反応であり、例えば、ハロゲン化ベンゼンとフェニルボロンとを縮合させてビフェニル誘導体を製造する反応である。この反応の触媒には、従来、粉末状のパラジウム錯体が用いられている。アリールボロン誘導体又はビニルボロン誘導体のボロン誘導体としては、特に限定されるものではないが、オルトホウ酸のモノ−、ジ−もしくはトリ−エステル又はこれらの誘導体を挙げることができる。アリールボロン誘導体のアリール基としては、置換又は非置換のフェニル基、ナフチル基、ピリジン基、フリル基等の芳香族基を挙げることができる。これらの置換基としては反応に悪影響を与えないものであれば特に制限はなく、例えば、塩素原子、臭素原子、そしてヨウ素原子等のハロゲン原子、置換又は非置換の炭素数１〜２０、好ましくは１〜１０のアルキル基、置換又は非置換の炭素数１〜２０、好ましくは１〜１０のアルコキシ基等を挙げることができる。ビニルボロン誘導体のビニル基としては、置換又は非置換のビニル基を挙げることができる。また、炭素―炭素二重結合を持つハライドのハロゲンとしては、塩素原子、臭素原子又はヨウ素原子を挙げることができる。炭素―炭素二重結合を持つスルホネートのスルホネートとしては、スルホン酸又はその誘導体を挙げることができ、例えば、スルホン酸のナトリウム塩、カリウム塩等の各種金属塩、そしてアンモニウム塩を挙げることができる。また、炭素―炭素二重結合を持つ基としては、脂肪族の炭素―炭素二重結合、芳香族の炭素―炭素二重結合を持つ基を挙げることができ、例えば、置換又は非置換のビニル基、置換又は非置換のアリール基を挙げることができる。アリール基としては、前記の置換又は非置換のフェニル基、ナフチル基、ピリジン基、フリル基等の芳香族基を挙げることができる。また、この反応ではハロゲン化水素が発生する場合、反応系にハロゲン化水素受容体を存在させておくことが好ましい。好ましいハロゲン化水素受容体としては、トリエチルアミン、Ｎ，Ｎ−ジエチルアミノベンゼン等の３級アミンを挙げることができる。また、好ましい溶媒は、ジメチルホルムアミド又はジメチルスルホキシドである。なお、用いるパラジウム触媒の量は、ヨードベンゼンに対して、０．０１〜１０モル％、より好ましくは０．１〜０．５モル％である。 The Suzuki reaction is also described in literature (N. Miyaura, et al., Synth. Commun., 11, 513 (1981): Ni. Miyaya and A. Suzuki, Chem. Rev., 95, 2457 (1995)). As described above, it is a condensation reaction between an aryl boron derivative or a vinyl boron derivative and a halide or sulfonate having a carbon-carbon double bond, for example, a reaction in which a halogenated benzene and phenyl boron are condensed to produce a biphenyl derivative. is there. Conventionally, a powdery palladium complex has been used as a catalyst for this reaction. The boron derivative of the aryl boron derivative or the vinyl boron derivative is not particularly limited, and examples thereof include mono-, di-, or tri-esters of orthoboric acid or derivatives thereof. Examples of the aryl group of the aryl boron derivative include aromatic groups such as a substituted or unsubstituted phenyl group, naphthyl group, pyridine group, and furyl group. These substituents are not particularly limited as long as they do not adversely affect the reaction. For example, halogen atoms such as chlorine atom, bromine atom and iodine atom, substituted or unsubstituted carbon atoms of 1 to 20, preferably A 1-10 alkyl group, a substituted or unsubstituted C1-C20, Preferably a 1-10 alkoxy group etc. can be mentioned. Examples of the vinyl group of the vinyl boron derivative include a substituted or unsubstituted vinyl group. In addition, examples of the halide halogen having a carbon-carbon double bond include a chlorine atom, a bromine atom, and an iodine atom. Examples of the sulfonate having a carbon-carbon double bond include sulfonic acid or a derivative thereof, and examples thereof include various metal salts such as sodium salt and potassium salt of sulfonic acid, and ammonium salt. Examples of the group having a carbon-carbon double bond include an aliphatic carbon-carbon double bond and a group having an aromatic carbon-carbon double bond, such as a substituted or unsubstituted vinyl. And a group or a substituted or unsubstituted aryl group. Examples of the aryl group include aromatic groups such as the above-described substituted or unsubstituted phenyl group, naphthyl group, pyridine group, and furyl group. Further, when hydrogen halide is generated in this reaction, it is preferable that a hydrogen halide acceptor be present in the reaction system. Preferable hydrogen halide acceptors include tertiary amines such as triethylamine and N, N-diethylaminobenzene. A preferred solvent is dimethylformamide or dimethyl sulfoxide. In addition, the quantity of the palladium catalyst to be used is 0.01-10 mol% with respect to iodobenzene, More preferably, it is 0.1-0.5 mol%.
また、本発明の固定型遷移金属触媒は、基板上に薄膜として形成できることから、基板の形状に合わせて板状、筒状等の種々の形状に製造することができる。また、反応容器の内面に薄膜を形成することにより、固定型遷移金属触媒を有する反応容器を製造することもできる。また、フロー式あるいはバッチ式の反応形式にも用いることができる。 Further, since the fixed transition metal catalyst of the present invention can be formed as a thin film on a substrate, it can be produced in various shapes such as a plate shape and a cylindrical shape in accordance with the shape of the substrate. Moreover, the reaction container which has a fixed type transition metal catalyst can also be manufactured by forming a thin film in the inner surface of a reaction container. It can also be used in a flow type or batch type reaction format.
以下、実施例を用いて本発明をさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。
参考例１（ヘック反応／オイルバス加熱）
（固定型遷移金属触媒の製造）
サファイア（０００１）単結晶基板上にＭＯＣＶＤ法を用いてＧａＮ層を成長させ、その基板に塩基処理、硫黄終端処理、パラジウム定着処理、加熱処理を順次行って、固定型遷移金属触媒を製造した。
EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to a following example.
Reference Example 1 (Heck reaction / oil bath heating)
(Manufacture of fixed transition metal catalysts)
A GaN layer was grown on the sapphire (0001) single crystal substrate by MOCVD, and a base treatment, sulfur termination treatment, palladium fixing treatment, and heat treatment were sequentially performed on the substrate to produce a fixed transition metal catalyst.
具体的には、ＧａＮ層の成長は、トリメチルガリウムとアンモニアを用いて基板温度９００〜１１００℃の条件で行った。 Specifically, the GaN layer was grown using trimethylgallium and ammonia at a substrate temperature of 900 to 1100 ° C.
酸化膜除去処理は、基板を４０％又は２０％の水酸化ナトリウム溶液に浸漬し、攪拌しながら６０℃で６時間加熱することにより行った。 The oxide film removal treatment was performed by immersing the substrate in a 40% or 20% sodium hydroxide solution and heating at 60 ° C. for 6 hours while stirring.
硫黄終端処理は、塩基処理した基板を５％硫化水素ナトリウム水溶液に浸漬し、攪拌しながら６０℃で０．５時間加熱することにより行った。 The sulfur termination treatment was performed by immersing the base-treated substrate in a 5% aqueous sodium hydrogen sulfide solution and heating it at 60 ° C. for 0.5 hours while stirring.
パラジウム定着処理は、硫黄終端処理した基板をアセトニトリル中に浸漬し、酢酸パラジウムを加え、攪拌しながら８０℃で１２時間加熱することにより行った。 The palladium fixing treatment was performed by immersing the sulfur-terminated substrate in acetonitrile, adding palladium acetate, and heating at 80 ° C. for 12 hours with stirring.
加熱定着は、パラジウム定着処理した基板をキシレン中に浸漬し、攪拌しながら１３０℃で１２時間加熱することにより行った。 The heat-fixing was performed by immersing the palladium-fixed substrate in xylene and heating at 130 ° C. for 12 hours while stirring.
（ヘック反応）
ヨードベンゼン（０．５ｍｍｏｌ）、アクリル酸メチル（１．２５当量）、及びトリエチルアミン（１．２５当量）のアセトニトリル（３ｍＬ）溶液に、固定型遷移金属触媒（５ｍｍ×５ｍｍ）を０．２ｍｏｌ％加えた。混合物をアルゴン雰囲気下、オイルバスを用いて加熱し、１００℃で４時間攪拌した。反応終了後、反応液に水を加え、ジクロロメタンで抽出した。有機層を飽和食塩水で洗い、硫酸ナトリウムで乾燥した。溶媒を減圧下で留去し、残渣をシリカゲルクロマトグラフィー（ｎ−ヘキサン：酢酸エチル＝５：１）で精製し、トランス−桂皮酸メチルを得た。なお、必要に応じて、トランス−桂皮酸メチルを取り出すことなく、反応液を一定量取り出し、液体クロマトグラフィーを用いて分析した。以下、特に断らない限り、反応前後のクロマトグラムの面積比から転化率を算出した。また、固定型遷移金属触媒の量は、ヨードベンゼンに対し０．２モル％である。ここで、転化率は、（Ｃ０−Ｃｆ）／Ｃ０×１００（％）で定義され、Ｃ０は反応前のヨードベンゼンのモル数、Ｃｆは反応後のヨードベンゼンのモル数である。
(Heck reaction)
To a solution of iodobenzene (0.5 mmol), methyl acrylate (1.25 equivalent), and triethylamine (1.25 equivalent) in acetonitrile (3 mL) was added 0.2 mol% of a stationary transition metal catalyst (5 mm × 5 mm). It was. The mixture was heated using an oil bath under an argon atmosphere and stirred at 100 ° C. for 4 hours. After completion of the reaction, water was added to the reaction solution and extracted with dichloromethane. The organic layer was washed with saturated brine and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (n-hexane: ethyl acetate = 5: 1) to obtain trans-methyl cinnamate. If necessary, a certain amount of the reaction solution was taken out without taking out trans-methyl cinnamate and analyzed using liquid chromatography. Hereinafter, unless otherwise specified, the conversion rate was calculated from the area ratio of the chromatogram before and after the reaction. The amount of the fixed transition metal catalyst is 0.2 mol% with respect to iodobenzene. Here, the conversion rate is defined by (C 0 -C f ) / C 0 × 100 (%), where C 0 is the number of moles of iodobenzene before the reaction, and C f is the number of moles of iodobenzene after the reaction. is there.
反応終了後、反応液から固定型遷移金属触媒を一旦取り出し、洗浄後、再度触媒として使用した。 After completion of the reaction, the fixed transition metal catalyst was once taken out from the reaction solution, washed, and used again as a catalyst.
また、比較のため、パラジウム担持カーボン（以下、Ｐｄ/Ｃと略す。）（和光純薬製）を用いた。 For comparison, palladium-supported carbon (hereinafter abbreviated as Pd / C) (manufactured by Wako Pure Chemical Industries, Ltd.) was used.
（結果）
ヘック反応の転化率の結果を表１に示す。従来のＰｄ/Ｃに比べ、本発明の固定型遷移金属触媒は、高い転化率を有していた。また、繰り返し使用が可能なことを確認した。特に、基板１の場合のように、高濃度の塩基を用いて酸化膜の除去を十分に行うことにより、再使用しても高い転化率が得られることを確認した。
(result)
Table 1 shows the results of the Heck reaction conversion. Compared with conventional Pd / C, the fixed transition metal catalyst of the present invention had a high conversion rate. It was also confirmed that repeated use was possible. In particular, as in the case of the substrate 1, it was confirmed that a high conversion rate can be obtained even by reuse by sufficiently removing the oxide film using a high concentration of base.
参考例２（ヘック反応／オイルバス加熱）
硫黄終端処理を、ＭＢＥ法で行った以外は、表１中の基板１と同様にして固定型遷移金属触媒を製造した。
Reference Example 2 (Heck reaction / oil bath heating)
A stationary transition metal catalyst was produced in the same manner as the substrate 1 in Table 1 except that the sulfur termination treatment was performed by the MBE method.
（結果）
転化率は、１回目が８８％、２回目が８８％、３回目が７９％であり、再使用が可能であった。
(result)
The conversion rate was 88% for the first time, 88% for the second time, 79% for the third time, and could be reused.
実施例１（ヘック反応／オイルバス加熱、マイクロ波加熱）
参考例１のヘック反応において、オイルバス又はマイクロ波を用いて加熱し、反応温度の反応速度への影響を調べた。オイルバスの反応温度は８０℃と１３０℃、マイクロ波照射では８０℃、１３０℃、１７５℃とした。
Example 1 (Heck reaction / oil bath heating, microwave heating)
In the Heck reaction of Reference Example 1, heating was performed using an oil bath or microwave, and the influence of the reaction temperature on the reaction rate was examined. The reaction temperature of the oil bath was 80 ° C. and 130 ° C., and microwave irradiation was 80 ° C., 130 ° C., and 175 ° C.
マイクロ波の照射は、バイオタージ社のマイクロ波反応装置（Initiator8、周波数２．４５ＧＨｚ）を用い、出力を変化させて所定温度に維持する出力可変方式で行った。 Microwave irradiation was performed by a variable output method using a microwave reaction apparatus (Initiator8, frequency 2.45 GHz) manufactured by Biotage, Inc., by changing the output and maintaining it at a predetermined temperature.
（結果）
表２に反応時間と転化率の関係を示す。マイクロ波を照射した場合、１３０℃では４時間、１７５℃では１時間で転化率１００％が得られた。一方、オイルバスでは、１３０℃でも７時間で３８％程度の転化率しか得られなかった。これにより、マイクロ波を照射することにより、オイルバスで加熱する方法に比べ、非常に短時間で反応を完結できることがわかった。
(result)
Table 2 shows the relationship between the reaction time and the conversion rate. When microwave irradiation was performed, a conversion rate of 100% was obtained at 130 ° C. for 4 hours and at 175 ° C. for 1 hour. On the other hand, in the oil bath, only a conversion rate of about 38% was obtained in 7 hours even at 130 ° C. As a result, it was found that the reaction can be completed in a very short time by irradiating microwaves, compared with the method of heating in an oil bath.
実施例２（ヘック反応／マイクロ波加熱）
マイクロ波照射による溶媒の温度上昇について、触媒の影響を調べた。溶媒にはアセトニトリルを用い、マイクロ波の出力は３０Ｗとした。
Example 2 (Heck reaction / microwave heating)
The influence of the catalyst on the temperature increase of the solvent by microwave irradiation was investigated. Acetonitrile was used as the solvent, and the microwave output was 30 W.
（結果）
照射時間と溶媒の温度との関係を表３に示す。表３中、ＡからＩの記号は、以下のものを指す。
Ａ：溶媒のみ
Ｂ：溶媒＋ＧａＮ層を形成したサファイア基板（ＧａＮ基板）
Ｃ：溶媒＋サファイア基板
Ｄ：溶媒＋ＧａＡｓ基板
Ｅ：溶媒＋ＡｌＮ基板
Ｆ：溶媒＋パラジウムを固定した実施例１の固定型遷移金属触媒
Ｇ：溶媒＋Ｐｄ／Ｃ
Ｈ：溶媒＋酢酸パラジウム
Ｉ：溶媒＋硫黄終端処理したＧａＮ基板
ここで、ＧａＡｓ基板は、住友電気工業社製単結晶（００１）面方位基板、ＡｌＮ基板は、トクヤマ社製セラミック多結晶焼結体を用いた。
表３から明らかなように、パラジウムを固定した本発明の固定型遷移金属触媒が溶媒中に存在すると、顕著に溶媒の温度が上昇することがわかった。
(result)
Table 3 shows the relationship between the irradiation time and the solvent temperature. In Table 3, symbols A to I indicate the following.
A: Solvent only B: Solvent + Sapphire substrate with GaN layer (GaN substrate)
C: solvent + sapphire substrate D: solvent + GaAs substrate E: solvent + AlN substrate F: fixed transition metal catalyst of Example 1 with solvent + palladium fixed G: solvent + Pd / C
H: solvent + palladium acetate I: solvent + sulfur-terminated GaN substrate Here, the GaAs substrate is a single crystal (001) orientation substrate manufactured by Sumitomo Electric Industries, Ltd., and the AlN substrate is a ceramic polycrystalline sintered body manufactured by Tokuyama Corp. Was used.
As apparent from Table 3, it was found that when the fixed transition metal catalyst of the present invention in which palladium was fixed was present in the solvent, the temperature of the solvent was remarkably increased.
実施例３（ヘック反応／マイクロ波加熱：再使用）
参考例１の固定型遷移金属触媒を繰り返し使用して、転化率を調べた。この際、使用した固定型遷移金属触媒はアセトニトリルで十分に洗浄して用いた。
Example 3 (Heck reaction / microwave heating: reuse)
The conversion rate was examined by repeatedly using the fixed transition metal catalyst of Reference Example 1. At this time, the fixed transition metal catalyst used was thoroughly washed with acetonitrile.
（結果）
表４に示すように、３回目の使用であっても、２時間以内で反応を完結できることがわかり、繰り返し使用が可能なことを確認した。
(result)
As shown in Table 4, it was found that even in the third use, the reaction could be completed within 2 hours, and it was confirmed that repeated use was possible.
実施例４（ヘック反応／マイクロ波加熱（無溶媒））
実施例１において、ヨードベンゼンを５ｍｍｏｌとし、溶媒を用いず、マイクロ波を照射して１７５℃で１時間反応させた。
Example 4 (Heck reaction / microwave heating (no solvent))
In Example 1 , iodobenzene was adjusted to 5 mmol, and the reaction was performed at 175 ° C. for 1 hour by irradiation with microwaves without using a solvent.
（結果）
無溶媒で行っても、１時間で転化率は１００％となった。これより、マイクロ波を照射することにより、一度に大量に製造することが可能なことを確認した。また、実施例３の場合、触媒量はヨードベンゼンの０．２モル％であるのに対し、本実施例ではヨードベンゼンの０．０２モル％である。すなわち、無溶媒で行うことにより、触媒量を１／１０としても反応を完結させることができることを確認した。
(result)
Even in the absence of solvent, the conversion reached 100% in 1 hour. From this, it was confirmed that a large amount could be manufactured at a time by irradiating with microwaves. In Example 3, the catalyst amount is 0.2 mol% of iodobenzene, whereas in this example, it is 0.02 mol% of iodobenzene. That is, it was confirmed that the reaction could be completed even when the amount of catalyst was reduced to 1/10 by carrying out the process without solvent.
実施例５（ヘック反応／マイクロ波加熱（触媒種の比較））
実施例１において、マイクロ波の出力を３０Ｗとし、１時間照射した。比較として、Ｐｄ/Ｃと、高分子担持触媒（Aldrich社製 品番596930）を用いた。
Example 5 (Heck reaction / microwave heating (comparison of catalyst species))
In Example 1 , the microwave output was set to 30 W and irradiation was performed for 1 hour. For comparison, Pd / C and a polymer-supported catalyst (product number 596930 manufactured by Aldrich) were used.
（結果）
実施例１の固定型遷移金属触媒の転化率が２８％であるのに対し、Ｐｄ/Ｃと高分子担持触媒では１％以下であった。
(result)
The conversion rate of the fixed transition metal catalyst of Example 1 was 28%, while that of Pd / C and the polymer-supported catalyst was 1% or less.
実施例６（鈴木反応／マイクロ波加熱）
ヨードベンゼン（０．５ｍｍｏｌ）のメタノール（３ｍＬ）溶液にアルゴン雰囲気下、トリエチルアミン（１２．５当量）、フェニルボロン酸（２．５当量）、及び参考例１の固定型遷移金属触媒（５ｍｍ×５ｍｍ）を加え、マイクロ波照射を行った。出力可変方式を用い、１３０℃で１時間照射した。なお、必要に応じて、３−クロロビフェニルを取り出すことなく、反応液を一定量取り出し、液体クロマトグラフィーを用いて、転化率を算出した。また、固定型遷移金属触媒の量は、ヨードベンゼンに対し０．２モル％である。ここで、転化率は、（Ｄ０−Ｄｆ）／Ｄ０×１００（％）で定義され、Ｄ０は反応前のヨードベンゼンのモル数、Ｄｆは反応後のヨードベンゼンのモル数である。
Example 6 (Suzuki reaction / microwave heating)
A solution of iodobenzene (0.5 mmol) in methanol (3 mL) under an argon atmosphere, triethylamine (12.5 equivalents), phenylboronic acid (2.5 equivalents), and the fixed transition metal catalyst of Reference Example 1 (5 mm × 5 mm) ) And microwave irradiation was performed. Irradiation was performed at 130 ° C. for 1 hour using a variable output system. If necessary, a certain amount of the reaction solution was taken out without taking out 3-chlorobiphenyl, and the conversion was calculated using liquid chromatography. The amount of the fixed transition metal catalyst is 0.2 mol% with respect to iodobenzene. Here, the conversion rate is defined by (D 0 -D f ) / D 0 × 100 (%), D 0 is the number of moles of iodobenzene before the reaction, and D f is the number of moles of iodobenzene after the reaction. is there.
（結果）
マイクロ波を照射することにより、１時間で１００％の転化率が得られた。
(result)
The conversion rate of 100% was obtained in 1 hour by irradiation with microwaves.
実施例７（鈴木反応／マイクロ波加熱）
参考例１の固定型遷移金属触媒を繰り返し使用して、転化率を調べた。この際、使用した固定型遷移金属触媒はメタノールで十分に洗浄して用いた。
Example 7 (Suzuki reaction / microwave heating)
The conversion rate was examined by repeatedly using the fixed transition metal catalyst of Reference Example 1. At this time, the fixed transition metal catalyst used was thoroughly washed with methanol.
（結果）
表５に示すように、３回目の使用であっても、１．５時間以内で反応を完結できることがわかり、繰り返し使用が可能なことを確認した。
(result)
As shown in Table 5, it was found that the reaction could be completed within 1.5 hours even in the third use, and it was confirmed that repeated use was possible.
実施例８（鈴木反応／マイクロ波加熱）
アリールハライドの脱離基を変えた場合のマイクロ波照射の影響を調べた。アリールハライドには、ヨードベンゼン、ブロモベンゼン、クロロベンゼンを用いた。なお、クロロベンゼンについては、トリエチルアミンに代えてフッ化カリウム（ＫＦ）を３．０当量用い、ターシャリーブチルホスフィンを０．１当量、そして溶媒にはＴＨＦを用いた。マイクロ波照射は、出力可変方式を用い、１３０℃で行った。
Example 8 (Suzuki reaction / microwave heating)
The influence of microwave irradiation when the leaving group of aryl halide was changed was investigated. As the aryl halide, iodobenzene, bromobenzene, and chlorobenzene were used. For chlorobenzene, 3.0 equivalents of potassium fluoride (KF) was used instead of triethylamine, 0.1 equivalents of tertiary butylphosphine, and THF was used as the solvent. Microwave irradiation was performed at 130 ° C. using a variable output method.
（結果）
ブロモベンゼンとクロロベンゼンの場合、オイルバスによる加熱では、反応が進行しなかった。これに対し、マイクロ波を照射することにより、表６に示すように反応を進行させることが可能なことがわかった。
(result)
In the case of bromobenzene and chlorobenzene, the reaction did not proceed by heating with an oil bath. On the other hand, it was found that the reaction can proceed as shown in Table 6 by irradiation with microwaves.
Claims (11)
少なくとも表面に金属窒化物層を有する基板又は金属窒化物からなる基板の表面に硫黄原子を介して遷移金属又は遷移金属化合物が結合している、固定型遷移金属触媒。 A stationary transition metal catalyst used in a state irradiated with microwaves,
A fixed transition metal catalyst in which a transition metal or a transition metal compound is bonded to a surface of a substrate having a metal nitride layer on the surface or a substrate made of a metal nitride via sulfur atoms.
少なくとも表面に金属窒化物層を有する基板又は金属窒化物からなる基板の表面に硫黄原子を結合させる硫黄終端処理と、該硫黄原子に遷移金属又は遷移金属化合物を結合させる金属定着処理とを行う、固定型遷移金属触媒の製造方法。 A method for producing a stationary transition metal catalyst used in a state irradiated with microwaves,
A sulfur termination treatment for bonding sulfur atoms to the surface of a substrate having a metal nitride layer on the surface or a substrate made of metal nitride and a metal fixing treatment for bonding a transition metal or a transition metal compound to the sulfur atoms are performed. A method for producing a stationary transition metal catalyst.
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