JPWO2020175309A1 - アミド化合物の水素化に用いる水素添加反応用触媒およびこれを用いたアミン化合物の製造方法 - Google Patents
アミド化合物の水素化に用いる水素添加反応用触媒およびこれを用いたアミン化合物の製造方法 Download PDFInfo
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- JPWO2020175309A1 JPWO2020175309A1 JP2021502133A JP2021502133A JPWO2020175309A1 JP WO2020175309 A1 JPWO2020175309 A1 JP WO2020175309A1 JP 2021502133 A JP2021502133 A JP 2021502133A JP 2021502133 A JP2021502133 A JP 2021502133A JP WO2020175309 A1 JPWO2020175309 A1 JP WO2020175309A1
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- Prior art keywords
- catalyst
- rhodium
- compound
- molybdenum
- amide compound
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- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- -1 amide compound Chemical class 0.000 title claims abstract description 88
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 102
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 102
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 56
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011733 molybdenum Substances 0.000 claims abstract description 41
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract 3
- 239000010948 rhodium Substances 0.000 claims description 113
- 229910052703 rhodium Inorganic materials 0.000 claims description 80
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 63
- 239000002904 solvent Substances 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 150000003284 rhodium compounds Chemical class 0.000 claims description 22
- 239000005078 molybdenum compound Substances 0.000 claims description 21
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 21
- 239000002808 molecular sieve Substances 0.000 claims description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 abstract description 42
- 230000000694 effects Effects 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 description 52
- 230000009467 reduction Effects 0.000 description 36
- 239000000243 solution Substances 0.000 description 30
- 238000000034 method Methods 0.000 description 28
- 239000000758 substrate Substances 0.000 description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 22
- 239000002245 particle Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000010304 firing Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
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- 238000003756 stirring Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
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- 239000002815 homogeneous catalyst Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229960003975 potassium Drugs 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 239000001506 calcium phosphate Substances 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- 229940078499 tricalcium phosphate Drugs 0.000 description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- KYWXRBNOYGGPIZ-UHFFFAOYSA-N 1-morpholin-4-ylethanone Chemical compound CC(=O)N1CCOCC1 KYWXRBNOYGGPIZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229910017311 Mo—Mo Inorganic materials 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
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- 239000008187 granular material Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- ZCUTVPBDJKANGE-UHFFFAOYSA-N molybdenum rhodium Chemical compound [Mo].[Rh] ZCUTVPBDJKANGE-UHFFFAOYSA-N 0.000 description 2
- YJEJUIVHAMABCA-UHFFFAOYSA-J molybdenum(4+);oxalate Chemical compound [Mo+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O YJEJUIVHAMABCA-UHFFFAOYSA-J 0.000 description 2
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 2
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
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- 229910003450 rhodium oxide Inorganic materials 0.000 description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 150000003511 tertiary amides Chemical class 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- YJRQILVMFCZHHL-UHFFFAOYSA-N 1-(1-phenylethyl)piperidine Chemical compound C=1C=CC=CC=1C(C)N1CCCCC1 YJRQILVMFCZHHL-UHFFFAOYSA-N 0.000 description 1
- MUTDXQJNNJYAEG-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(dimethylamino)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)N(C)C MUTDXQJNNJYAEG-UHFFFAOYSA-N 0.000 description 1
- SERBNUYNEAQHNJ-UHFFFAOYSA-N 2-phenyl-n-(2-phenylethyl)acetamide Chemical compound C=1C=CC=CC=1CCNC(=O)CC1=CC=CC=C1 SERBNUYNEAQHNJ-UHFFFAOYSA-N 0.000 description 1
- ACSAKRLPJQIBFB-UHFFFAOYSA-N 2-phenyl-n-(2-phenylethyl)ethanamine Chemical compound C=1C=CC=CC=1CCNCCC1=CC=CC=C1 ACSAKRLPJQIBFB-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
- KFBXVBQQAUQWAY-UHFFFAOYSA-N 4-(cyclohexylmethyl)morpholine Chemical compound C1COCCN1CC1CCCCC1 KFBXVBQQAUQWAY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 1
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- SIRWNZIGHZQJAM-UHFFFAOYSA-N cyclohexyl(morpholin-4-yl)methanone Chemical compound C1COCCN1C(=O)C1CCCCC1 SIRWNZIGHZQJAM-UHFFFAOYSA-N 0.000 description 1
- 229960001985 dextromethorphan Drugs 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical group 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 125000005616 oxoacid group Chemical group 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003281 rhenium Chemical class 0.000 description 1
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- MWZNPHHDRLXXHO-UHFFFAOYSA-N rhodium;hydrate Chemical compound O.[Rh] MWZNPHHDRLXXHO-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- ODWFEWNDEQNIIS-UHFFFAOYSA-N sodium rhodium(3+) Chemical compound [Na+].[Rh+3] ODWFEWNDEQNIIS-UHFFFAOYSA-N 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
Description
本発明の触媒を構成するロジウムは、特に限定されないが、例えば、ロジウム粒子が好ましい。ここでロジウム粒子とは、金属ロジウムまたは酸化ロジウムの少なくとも1種から選ばれるロジウムの粒子であり、好ましくは金属ロジウムの粒子である。
本発明の触媒を構成するモリブデンは、特に限定されないが、MO3のような酸化物としてのモリブデンを含んでいても良いが、好ましくは金属モリブデンの粒子である。
本発明の触媒の使用状態である還元状態ではRh、Mo共に金属状態で含有していることが好ましい。前述の非特許文献5ではRh、Moがこのような金属状態で、換言すれば0価の状態においてRh、Mo共に優れた水素化性能を発揮することが報告されている。
本発明の触媒における、ロジウムとモリブデンの組成比は、金属としてのロジウム(Rh):金属としてのモリブデン(Mo)のモル数のモル数換算で、モル比[Rh:Mo]=1:0.01〜1が好ましく、より好ましくは1:0.05〜0.5、更に好ましくは1:0.05〜0.2である。
本発明の触媒の担体(母材)はハイドロキシアパタイト(HAP)である。その吸着能は、いわゆるBET値として0.1〜300m2/gであってもよく、平均粒径としては0.02〜100μmであってもよい。本発明においては、ハイドロキシアパタイトの吸着能は、0.5〜180m2/g であることが好ましく、さらに30〜100m2/gであることが好ましい。なお、本発明の触媒の担体としては、ハイドロキシアパタイトに代えて、クロロアパタイト、フルオロアパタイト等のその他のアパタイトを用いることができることは言うまでもない。
本発明の触媒は、上記したロジウムとモリブデンがハイドロキシアパタイトに担持されていればよく、効果を損なわない範囲で、遷移金属やアルカリ金属やアルカリ土類金属などを触媒成分やハイドロキシアパタイト成分として常法に従って含有させてもよい。
本発明の触媒のうち、ロジウムとモリブデンがハイドロキシアパタイトに担持されたことを特徴とするアミド化合物の水素添加反応用触媒は、溶媒中で、ロジウムとモリブデンをハイドロキシアパタイトに担持させた後、これを乾燥することにより製造できる(以下、「本発明方法」という)。なお、乾燥後焼成処理を施しても良い。
本発明の触媒は、アミド化合物の水素添加反応用である。そのため、本発明の触媒は、アミド化合物に接触させれば、水素添加(還元)してアミン化合物を製造することができる。
本発明の触媒は活性成分であるロジウムがハイドロキシアパタイトに担持されているため、反応中においても担持されたロジウムが大きな粒子になりにくい。また、本発明の触媒は、例えば、水素添加後に反応液から濾過、遠心分離等の物理的な分離手法により容易に回収することができる。回収された本発明の触媒はそのまま、あるいは、必要により、洗浄、乾燥、焼成等を施した後、再利用することができる。洗浄、乾燥、焼成等は本発明の触媒の製造の際と同様に行えばよい。
Rh−Mo/HAPの調製:
蒸留水80mlの入った100mlナスフラスコに、エヌ・イー ケムキャット社製(K3[RhCl6])・3H2Oaqを0.2mmol加え、3分間超音波処理を行った後、強攪拌しながら和光純薬社のHAP(商品名「リン酸三カルシウム」)1.0gを加えて80℃まで加熱し、この状態で15時間攪拌した後、1.5時間静置して室温まで放冷した。放冷した前記溶液に(NH4)6Mo7O24・4H2Oaq(40mM)を25ml(Mo含有量:1.0mmol)滴下した後、50℃まで加熱した後3時間攪拌した。攪拌後濾過し、蒸留水を約1L用いて濾過洗浄を行った。濾過洗浄を行った濾物を120℃で8時間以上乾燥し、Rh−Mo/HAPを得た(Rh:0.2mmol/g、Mo:0.017mmol/g)。
比較用バイメタル/HAP触媒の調製:
レニウム塩としてNH4ReO4を、バナジウム塩としてNH4VO3を、白金塩としてK2PtCl4を、パラジウム塩としてK2PdCl6を、ルテニウム塩としてK2RuCl6を使用した他、製造例1と同様にしてRh−Re/HAP触媒、Rh−V/HAP触媒、Pt−Mo/HAP触媒、Pd−Mo/HAP触媒、Ru−Mo/HAP触媒を得た。
比較用Rh/HAPの調製:
蒸留水80mlの入った100mlナスフラスコに、エヌ・イー ケムキャット社製K3[RhCl6]を0.2mmol加え、3分間超音波処理を行った後、強攪拌しながら和光純薬社のHAP(商品名「リン酸三カルシウム」)1.0gを加えて70℃まで加熱し、この状態で15時間攪拌した後、1.5時間静置して室温まで放冷した。放冷した前記溶液を濾過し、蒸留水を約1L用いて濾過洗浄を行った。濾過洗浄を行った濾物を120℃で8時間以上乾燥し、Rh/HAPを得た。
比較用Mo/HAPの調製:
蒸留水80mlの入った100mlナスフラスコに(NH4)6Mo7O24・4H2Oaq(40mM)を25ml(Mo含有量:1.0mmol)滴下した後、50℃まで加熱した後3時間攪拌した。攪拌後濾過し、蒸留水を約1L用いて濾過洗浄を行った。濾過洗浄を行った濾物を120℃で8時間以上乾燥し、Mo/HAPを得た。
比較用Rh−Mo/SiO2(非特許文献4記載の触媒)の調製:
蒸留水80mlが入った100mlフラスコ中にRhCl3・3H2Oを0.4mmol、担体であるSiO2(Fuji Silysia G−6)を1.0g加え、室温にて3時間撹拌を行った。攪拌後、エバポレーターを用いて溶媒を除去し、その後120℃にて8時間以上乾燥させた。乾燥後得られたRh/SiO2を、(NH4)6Mo7O24・4H2Oを0.4mmol溶解させた蒸留水70ml中に加え、再度室温にて3時間攪拌を行った。その後、エバポレーターを用いて溶媒を除去し、120℃にて8時間以上乾燥後、大気中、電気炉にて500℃にて3時間焼成しRh−Mo/SiO2を得た。
水素添加反応:
反応に使用するオートクレーブに製造例1で得た触媒と溶媒のDME(1,2−dimethoxyethane)を5ml加え、水素ガスで20atmに加圧し、160℃に加熱し1時間還元処理を行った。その後、遠心分離機(2000rpm、1分間)にかけ、上澄み液をピペットで取り出して除いた。そこにDME5mlを加えて、1分間超音波処理を行った。この洗浄工程をもう一度繰り返した後、最後に上澄み液を取り除き、反応前還元処理を行った。
水素添加反応:
表2の各基質について、製造例1で得られたRh−Mo/HAPを実施例1と同様にして反応前還元処理した後、溶剤としてのDMEを5mL、還元剤としての水素ガス、和光純薬社のモレキュラーシーブス4Åを使用し、適宜条件を変えて水素化反応を行った。反応後、ガスクロマトグラフを用いて各基質に対する転化率、選択率を測定し結果を表2、表3に記した。
Rh−Mo/HAPの調製:
実施例1において、(NH4)6Mo7O24・4H2Oaq(40mM)を25ml(Mo含有量:1.0mmol)に代えて、表4に記載の量の(NH4)6Mo7O24・4H2Oaq(40mM)を用いる以外は、実施例1と同様にしてRh−Mo/HAPを得た。
水素添加反応:
製造例10〜14で得られたRh−Mo/HAPを実施例1と同様にして反応前還元処理したものを0.05g、溶媒である1,2−ジメトキシエタン(DME)5mL、基質であるN−アセチルモルホリン0.5mmol、和光純薬社のモレキュラーシーブス4Å :0.1gを、50mLのステンレス製オートクレーブに加えて以下の条件で水素化反応を行った。反応後、ガスクロマトグラフを用いて収率を測定した。結果を表6に記す。
触媒の耐久性:
反応時間を12時間に変えた他、実施例1のEntry1と同じ条件で水素化反応を行い、反応後の触媒を濾過して再利用し、これを繰り返して本発明の耐久性について検証した。転化率、収率はガスクロマトグラフを用いて測定した。結果を表7に記す。
水素添加反応:
下記反応式の様に、製造例1で得たRh−Mo/HAPを使用し、実施例1における基質を下記のイミド(アミド結合を有する化合物)0.3mmolに、触媒量を0.3gに、反応時の水素の圧力を50barに、温度を160℃に、反応時間を48時間に変更してイミド化合物の水素化反応を行った。反応後、ガスクロマトグラフを用いて収率を測定したところ、収率60%でアミン化合物を得ることができた。
水素添加反応:
実施例5における基質を0.1mmol、触媒を0.1g、溶媒を10ml、モレキュラーシーブス0.2gを、反応温度を60℃、水素圧を0.6MPa、反応時間を144時間として反応装置(柴田科学社製ケミストプラザCPP−2210)にて水素化反応を行ったところ、収率は18%となった。
水素添加反応:
実施例6における溶媒を15ml、モレキュラーシーブスを1.0gとした以外は同様に反応させたところ収率は41%となった。実施例6と7の結果から基質から発生する水分量よりも過剰なモレキュラーシーブを投入することで収率が向上することが分かった。
触媒中のRh、Moの状態の解析:
本発明の触媒について、Rh、Moの状態を以下のとおり解析した。実施例1において反応前に水素還元したRh−Mo/HAPについてXAFSスペクトルの測定を行ったところ、Mo−K端EXAFSスペクトルを高速フーリエ変換して得られたMoとMo近傍元素の距離は2.66Å(0.266nm)であった。
以 上
Claims (10)
- ロジウムとモリブデンがハイドロキシアパタイトに担持されたことを特徴とするアミド化合物の水素添加反応用触媒。
- アミド化合物が、2級以上のアミド化合物または芳香族置換基を含むアミド化合物である請求項1に記載のアミド化合物の水素添加反応用触媒。
- アミド化合物を、請求項1または2の何れかに記載のアミド化合物の水素添加反応用触媒に接触させて水素添加し、アミン化合物を得ることを特徴とするアミン化合物の製造方法。
- 水素添加を、100℃以下で行うものである請求項3に記載のアミン化合物の製造方法。
- 水素添加を、5MPa以下で行うものである請求項3または4に記載のアミン化合物の製造方法。
- 更に、アミド化合物をモレキュラーシーブスにも接触させる請求項3〜5の何れかに記載のアミン化合物の製造方法。
- アミド化合物が、2級以上のアミド化合物または芳香族置換基を含むアミド化合物である請求項3〜6の何れかに記載のアミン化合物の製造方法。
- 溶媒中で、ロジウムとモリブデンをハイドロキシアパタイトに担持させた後、これを乾燥することを特徴とする請求項1または2の何れかに記載のアミド化合物の水素添加反応用触媒の製造方法。
- ハイドロキシアパタイトとロジウム化合物を含有する溶媒液とを混合した後、モリブデン化合物を含有する溶媒液を混合して、ロジウムとモリブデンを溶媒中でハイドロキシアパタイトに担持させるものである請求項8記載のアミド化合物の水素添加反応用触媒の製造方法。
- 溶媒が、水である請求項8または9の何れかに記載のアミド化合物の水素添加反応用触媒の製造方法。
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