JP7468865B2 - リン化コバルト触媒およびこれを用いた有機化合物の製造方法 - Google Patents
リン化コバルト触媒およびこれを用いた有機化合物の製造方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims description 141
- 239000010941 cobalt Substances 0.000 title claims description 37
- 229910017052 cobalt Inorganic materials 0.000 title claims description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 150000002894 organic compounds Chemical class 0.000 title description 21
- -1 amine compound Chemical class 0.000 claims description 51
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 34
- 239000002105 nanoparticle Substances 0.000 claims description 27
- 238000006268 reductive amination reaction Methods 0.000 claims description 27
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000000034 method Methods 0.000 description 18
- 229910052698 phosphorus Inorganic materials 0.000 description 18
- 239000011574 phosphorus Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 150000001869 cobalt compounds Chemical class 0.000 description 15
- 239000000758 substrate Substances 0.000 description 13
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010574 gas phase reaction Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 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 description 3
- 239000000843 powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 238000002253 near-edge X-ray absorption fine structure spectrum Methods 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910002514 Co–Co Inorganic materials 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000000369 bright-field scanning transmission electron microscopy Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000005315 distribution function Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical group [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 125000002345 steroid group Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Furan Compounds (AREA)
- Pyridine Compounds (AREA)
- Steroid Compounds (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
<有機化合物> <還元アミノ化化合物>
カルボニル化合物 第一級アミン化合物
<有機化合物> <水素化有機化合物>
ニトリル化合物 第一級アミン化合物
アルデヒド化合物 アルコール化合物
不飽和化合物 飽和化合物
Co2P NR(ナノロッド)の生成:
Co2P NP(ナノ六角柱)の生成
Co2Pは文献(Junfeng Liu and Andreu Cabot et al, J. Mater. Chem. A, 2018, 6, 11453-11462)に記載の方法に準じて生成した。まず、塩化コバルト(CoCl2)(1.0mmol)、ヘキサデシルアミン(10mmol)、トリフェニルホスファイト(10mmol)、1-オクタデセン(10.0mL)をシュレンクフラスコに加えて撹拌した。混合液をアルゴンフロー下で150℃1時間加熱した。続いて、温度を20分間で溶媒沸点(約290℃)まで上昇させ、その後2時間維持した後、200℃まで冷却し、水浴で急速に室温まで冷却し黒色生成物を得た。得られた黒色生成物をアセトンで洗浄し、沈殿させて回収し、更にクロロホルムとアセトンを用いて洗浄を行い、本発明の実施例触媒2を得た。得られた実施例触媒2を大気中で一日放置して乾燥させたが、スポンジ触媒で懸念されるような発火は生じなかった。
粉状Co2P:
市場から試薬のCo2Pを入手して比較例触媒1とした。比較例触媒1の平均粒子径は体積基準で測定されたメディアン径で70μmであった。
CoPナノ粒子の調製:
アルゴン雰囲気下で1mmolのCo(acac)2、5mL(15.6mmol)の1-オクタデセンと10mLのオレイルアミンをシュレンクフラスコ中に加えて120℃で攪拌後、5mL(11mmol)トリフェニルホスフィンを加えて340℃で4時間加熱した。混合物を室温まで冷やした後ヘキサンとエタノール(1:1)の混合溶液で上澄み液が透明になるまで洗浄し、得られた粉末を室温で一晩真空乾燥して比較例触媒2を得た。
ラネーCo:
富士フイルム和光純薬株式会社製ラネーコバルト(約48%)(製品コード189-00462)を比較例触媒3とした。
アンモニアによるアルデヒド化合物の還元アミノ化反応:
アルデヒド化合物の還元アミノ化反応はオートクレーブにて行った。オートクレーブに0.004gのCo2P NR触媒、基質として0.5mmolのベンズアルデヒド、アンモニア源として3mlの25wt%のNH3水溶液を加え、その後、水素の加圧雰囲気に切り替えて加熱し、反応を行った。
触媒の耐久性:
実施例触媒1を使用して、本発明触媒の耐久性を評価するため、反応に使用した触媒を濾過した後、前記の試験例1の例4と同じ反応を繰り返し、本発明触媒の耐久性を検証した。結果を表2に記す。
基質多様性:
続いて、Co2P NR触媒(実施例触媒1)を使用して、本発明触媒の基質多様性について評価を行った。反応条件は以下のとおり前記の試験例1の条件と同様である。結果を表3に記す。
ケトン化合物の還元アミノ化
続いて、立体障害のあるイミン中間体の水素化が困難なため、アルデヒドよりも還元アミノ化が困難なケトンについて、Co2P NR触媒(実施例触媒1)を使用して、本発明触媒の還元アミノ化性能について評価を行った。結果を表4に記す。
基質(ケトン化合物)多様性
続いて、Co2P NR触媒(実施例触媒1)を使用して、本発明触媒のケトン化合物が基質の場合の基質多様性について評価を行った。反応条件は以下のとおり前記の試験例4の条件と同様である。結果を表5に記す。
基質多様性:
続いて、Co2P NR(実施例触媒1)を使用して、本発明触媒の基質多様性について評価を行った。結果を表6に示す。
Claims (6)
- リン化コバルトのナノ粒子を有効成分とし、ナノ粒子が棒状であることを特徴とするアンモニア源の共存下でのカルボニル化合物の還元アミノ化触媒。
- リン化コバルトのナノ粒子の長辺が、短辺の10倍以上である請求項1記載の触媒。
- リン化コバルトのナノ粒子が、無機酸化物微粒子に担持されたものである請求項1または2に記載の触媒。
- カルボニル化合物を、アンモニア源の共存下で請求項1~3のいずれか1項に記載の触媒を用いて還元アミノ化することを特徴とするアミン化合物の製造方法。
- 加熱、常圧または加圧された水素含有雰囲気のもと、アンモニア源の共存下、湿式でカルボニル化合物を、請求項1~3のいずれか1項に記載の触媒を用いて還元アミノ化することを特徴とするアミン化合物の製造方法。
- アンモニア源がアンモニア水または酢酸アンモニウムである請求項5に記載のアミン化合物の製造方法。
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JP2013514306A (ja) | 2009-12-17 | 2013-04-25 | ビーエーエスエフ ソシエタス・ヨーロピア | グリコールアルデヒドとアミノ化剤との反応 |
US20170015558A1 (en) | 2015-07-13 | 2017-01-19 | Agency For Science, Technology And Research | Method for preparing transition metal phosphide |
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US20170015558A1 (en) | 2015-07-13 | 2017-01-19 | Agency For Science, Technology And Research | Method for preparing transition metal phosphide |
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Chemical Science,2020年06月09日,vol.11,p.6682-6689,SUPPLEMENTARY INFORMATION,DOI: 10.1039/dosc00247j |
Nano Energy,2014年,vol.9,p.373-382,DOI:10.1016/j.nanoen.2014.08.013 |
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