CN111801297A - Process for producing ammonia, molybdenum complex compound, and benzimidazole compound - Google Patents
Process for producing ammonia, molybdenum complex compound, and benzimidazole compound Download PDFInfo
- Publication number
- CN111801297A CN111801297A CN201980016588.0A CN201980016588A CN111801297A CN 111801297 A CN111801297 A CN 111801297A CN 201980016588 A CN201980016588 A CN 201980016588A CN 111801297 A CN111801297 A CN 111801297A
- Authority
- CN
- China
- Prior art keywords
- molybdenum complex
- formula
- atom
- complex compound
- alkyl group
- 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.)
- Granted
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 62
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims description 93
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 92
- 239000011733 molybdenum Substances 0.000 title claims description 92
- 150000001875 compounds Chemical class 0.000 title claims description 44
- -1 benzimidazole compound Chemical class 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 55
- 239000003446 ligand Substances 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 150000002602 lanthanoids Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims 1
- UAWABSHMGXMCRK-UHFFFAOYSA-L samarium(ii) iodide Chemical compound I[Sm]I UAWABSHMGXMCRK-UHFFFAOYSA-L 0.000 abstract description 8
- NJQAVBPPWNSBBC-UHFFFAOYSA-N ditert-butyl-[[6-(ditert-butylphosphanylmethyl)pyridin-2-yl]methyl]phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CC1=CC=CC(CP(C(C)(C)C)C(C)(C)C)=N1 NJQAVBPPWNSBBC-UHFFFAOYSA-N 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 150000002751 molybdenum Chemical class 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 2
- RQWJHUJJBYMJMN-UHFFFAOYSA-N 4-(trifluoromethyl)benzene-1,2-diamine Chemical compound NC1=CC=C(C(F)(F)F)C=C1N RQWJHUJJBYMJMN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- PPWRHKISAQTCCG-UHFFFAOYSA-N 4,5-difluorobenzene-1,2-diamine Chemical compound NC1=CC(F)=C(F)C=C1N PPWRHKISAQTCCG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- DGDBSLKLKZTDSL-UHFFFAOYSA-N [I].[Mo] Chemical compound [I].[Mo] DGDBSLKLKZTDSL-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- NGJVBICXQZVNEF-UHFFFAOYSA-N cobalt(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene Chemical compound [Co+2].CC=1C(C)=C(C)[C-](C)C=1C.CC=1C(C)=C(C)[C-](C)C=1C NGJVBICXQZVNEF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- YOXHCYXIAVIFCZ-UHFFFAOYSA-N cyclopropanol Chemical compound OC1CC1 YOXHCYXIAVIFCZ-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- CRHWEIDCXNDTMO-UHFFFAOYSA-N ditert-butylphosphane Chemical compound CC(C)(C)PC(C)(C)C CRHWEIDCXNDTMO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- YGPXKCAQZYLASU-UHFFFAOYSA-N trifluoromethanesulfonate;2,4,6-trimethylpyridin-1-ium Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=CC(C)=[NH+]C(C)=C1 YGPXKCAQZYLASU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The method for producing ammonia of the present invention is a method for producing ammonia from a nitrogen molecule in the presence of a catalyst, a reducing agent, and a proton source. As the catalyst, use is made of, for example, [ MoI ]3(PNP)](PNP is 2, 6-bis (di-tert-butylphosphinomethyl) pyridine). As the reducing agent, samarium (II) iodide was used, and as the proton source, alcohol or water was used.
Description
Technical Field
The present invention relates to a method for producing ammonia, a molybdenum complex compound, and a benzimidazole compound.
Background
The Haber-Bosch (Haber-Bosch) process, which is an industrial process for converting nitrogen molecules into ammonia, is an energy-intensive process requiring reaction conditions of high temperature and high pressure. In contrast, in recent years, a method for producing ammonia from nitrogen molecules under mild conditions has been developed. For example, non-patent document 1 reports that 415 equivalents of ammonia based on the molybdenum complex as a catalyst is produced by adding a toluene solution of decamethylcyclocobaltocene as a reducing agent to a toluene solution of a molybdenum iodine complex having a PNP ligand as a catalyst and 2,4, 6-trimethylpyridine trifluoromethanesulfonate as a proton source in the presence of nitrogen gas at normal pressure at room temperature and then stirring, as shown in the following formula.
Documents of the prior art
Non-patent document
Non-patent document 1: bulb, chem, Soc, Jpn, 2017, vol, 90, pp1111-1118
Disclosure of Invention
Problems to be solved by the invention
However, in the above non-patent document 1, it is necessary to use a stoichiometric amount of a conjugate acid of expensive decamethylcobaltocene, Collidine (Collidine). Therefore, development of a method for producing ammonia at a lower cost is desired from an industrial viewpoint.
The present invention has been made to solve the above problems, and a main object thereof is to produce ammonia from nitrogen molecules at a relatively low cost.
Means for solving the problems
In order to achieve the above object, the present inventors have studied a method for producing ammonia from a nitrogen molecule using a certain molybdenum complex compound as a catalyst and samarium (II) iodide as a reducing agent, and as a result, have found that an alcohol and water can be used as a proton source, thereby completing the present invention.
That is, the method for producing ammonia of the present invention is a method for producing ammonia from a nitrogen molecule in the presence of a catalyst, a reducing agent and a proton source,
the catalyst is (A) a molybdenum complex compound having 2, 6-bis (dialkylphosphinomethyl) pyridine (wherein 2 alkyl groups may be the same or different and at least 1 hydrogen atom of the pyridine ring may be substituted with an alkyl group, an alkoxy group or a halogen atom) as a PNP ligand, (B) a molybdenum complex compound having N, N-bis (dialkylphosphinomethyl) benzimidazolecarbonine (N, N-bis (dialkylphosphinomethyl) benzimidazolidene (wherein 2 alkyl groups may be the same or different and at least 1 hydrogen atom of the benzene ring may be substituted with an alkyl group, an alkoxy group or a halogen atom) as a PCP ligand, (C) a molybdenum complex compound having bis (dialkylphosphinoethyl) arylphosphine (wherein 2 alkyl groups may be the same or different) as a PPP ligand, or (D) trans-Mo (N-N)2)2(R1R2R3P)4(wherein, R1、R2、R3Is an alkyl or aryl group which may be the same or different, 2R3May be linked to each other to form an alkylene chain),
as the reducing agent, a halide (II) of a lanthanoid metal is used,
as the proton source, alcohol or water is used.
According to this method for producing ammonia, since the reaction proceeds even at room temperature (0 to 40 ℃) using alcohol and water as proton sources, ammonia can be produced from nitrogen molecules at lower cost than in the past.
Detailed Description
Preferred embodiments of the method for producing ammonia of the present invention are shown below.
The method for producing ammonia according to the present embodiment is a method for producing ammonia from a nitrogen molecule in the presence of a catalyst, a reducing agent, and a proton source. In this method, (A) a molybdenum complex compound having 2, 6-bis (dialkylphosphinomethyl) pyridine (wherein 2 alkyl groups may be the same or different and at least 1 hydrogen atom of the pyridine ring may be substituted with an alkyl group, an alkoxy group or a halogen atom) as a PNP ligand, (B) a molybdenum complex compound having N, N-bis (dialkylphosphinomethyl) benzimidazole carbene (wherein 2 alkyl groups may be the same or different and at least 1 hydrogen atom of the benzene ring may be substituted with an alkyl group, an alkoxy group or a halogen atom) as a PCP ligand, (C) a molybdenum complex compound having bis (dialkylphosphinoethyl) arylphosphine (wherein 2 alkyl groups may be the same or different) as a PPP ligand, or (D) trans-Mo (N-N) is used as a catalyst2)2(R1R2R3P)4(wherein, R1、R2、R3Is an alkyl or aryl group which may be the same or different, 2R3May be linked to each other to form an alkylene chain). Further, as the reducing agent, a halide (II) of a lanthanoid metal is used, and as the proton source, alcohol or water is used.
In the molybdenum complex compound of (a), the alkyl group may be, for example, a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and structural isomers thereof, or a cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 6 carbon atoms. Examples of the alkoxy group include linear or branched alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, structural isomers thereof, and cyclic alkoxy groups such as cyclopropyloxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy. The alkoxy group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Examples of the molybdenum complex compound of (a) include molybdenum complexes represented by the formula (a1), (a2) or (A3). Examples of the alkyl group, alkoxy group and halogen atom include the same groups and atoms as those exemplified for the alkyl group, alkoxy group and halogen atom. As R1And R2Preferably, a bulky alkyl group (e.g., tert-butyl group or isopropyl group). The hydrogen atom on the pyridine ring is preferably unsubstituted, or the 4-position hydrogen atom is substituted by a chain, cyclic or branched alkyl group having 1 to 12 carbon atoms.
(in the formula, R1And R2Is an alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least 1 hydrogen atom on the pyridine ring may be substituted by an alkyl group, an alkoxy group or a halogen atom)
Examples of the molybdenum complex compound of (B) include a molybdenum complex compound represented by the formula (B1). Examples of the alkyl group, alkoxy group and halogen atom include the same groups and atoms as those exemplified for the alkyl group, alkoxy group and halogen atom. As R1And R2Preferably, a bulky alkyl group (e.g., tert-butyl group or isopropyl group). The hydrogen atom on the benzene ring is preferably unsubstituted, or the hydrogen atoms at the 5-and 6-positions are substituted with a chain, cyclic or branched alkyl group having 1 to 12 carbon atoms. Particularly preferred is a molybdenum complex compound of the formula (B2). In the formula (B2), R is preferred1、R2And X is the same as in formula (B1), R3And R4Is substituted with a fluoro group, more preferably R3And R4At least one of which is substituted with trifluoromethyl. Benzimidazolation of formula (E)The compound can be used as an intermediate for synthesizing a molybdenum complex compound of formula (B2). In formula (E), A is an anion, R1、R2And X is the same as in formula (B1), R3And R4The same as in formula (B2). The anion of A is not particularly limited, and examples thereof include PF6 -、BF4 -、ClO4 -And the like.
(in the formula, R1And R2Is an alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, at least 1 hydrogen atom on the benzene ring may be substituted by an alkyl group, an alkoxy group or a halogen atom)
Examples of the molybdenum complex compound of (C) include molybdenum complexes represented by the formula (C1). Examples of the alkyl group include the same groups as those already exemplified. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a group in which at least 1 atom of the hydrogen atoms in the ring is substituted with an alkyl group or a halogen atom. Examples of the alkyl group and the halogen atom include the same groups and atoms as those exemplified for the alkyl group and the halogen atom. As R1And R2Preferably, a bulky alkyl group (e.g., tert-butyl group or isopropyl group). As R3Preferably, for example, phenyl.
(in the formula, R1And R2Are alkyl groups which may be the same or different, R3Is aryl, X is an iodine atom, a bromine atom or a chlorine atom)
Examples of the molybdenum complex (D) include molybdenum complexes represented by the formulae (D1) and (D2). As the alkyl group and the aryl group, mention may be made ofThe same groups are exemplified. In the formula (D1), R is preferred1And R2Is aryl (e.g. phenyl) and R3Is an alkyl group having 1 to 4 carbon atoms (e.g., methyl group), or R1And R2Is an alkyl group having 1 to 4 carbon atoms (e.g., methyl group) and R3Is aryl (e.g., phenyl). In the formula (D2), R is preferred1And R2Is aryl (e.g., phenyl) and n is 2.
(in the formula, R1、R2And R3Is an alkyl or aryl group which may be the same or different, n is 2 or 3)
In the method for producing ammonia according to the present embodiment, nitrogen gas at normal pressure is preferably used as the nitrogen molecule. Nitrogen gas is inexpensive and therefore can be used in large excess relative to other reagents.
In the method for producing ammonia according to the present embodiment, when an alcohol is used as a proton source, the alcohol may be a diol, or ROH (R is a linear, cyclic or branched alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom substituted with a fluorine atom, or a phenyl group which may have an alkyl group) may be used. Examples of the diol include ethylene glycol, propylene glycol, and diethylene glycol, and among these, ethylene glycol is preferable. Examples of ROH include linear or branched alkyl alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, and tert-butanol; cyclic alkyl alcohols such as cyclopropyl alcohol, cyclopentyl alcohol and cyclohexyl alcohol; fluorine atom-containing alcohols such as trifluoroethyl alcohol and tetrafluoroethyl alcohol; phenol derivatives such as phenol, cresol and xylenol.
In the method for producing ammonia of the present embodiment, ammonia can be produced from nitrogen molecules in a solvent. The solvent is not particularly limited, and examples thereof include cyclic ether solvents, chain ether solvents, nitrile solvents, hydrocarbon solvents, and the like. Examples of the cyclic ether solvent include tetrahydrofuran (hereinafter, abbreviated as THF or THF), dioxane, and the like. Examples of the chain ether solvent include diethyl ether. Examples of the nitrile solvent include acetonitrile and propionitrile. Examples of the hydrocarbon solvent include aromatic hydrocarbons such as toluene, and saturated hydrocarbons such as hexane.
In the method for producing ammonia according to the present embodiment, the reaction temperature is preferably room temperature (0 to 40 ℃). The reaction atmosphere does not need to be a pressurized atmosphere, and may be a normal pressure atmosphere. The reaction time is not particularly limited, but may be set within a range of usually several minutes to several 10 hours.
In the method for producing ammonia of the present embodiment, the amount of the catalyst to be used may be appropriately used in the range of 0.00001 to 0.1 equivalent to the reducing agent, and is preferably 0.0005 to 0.1 equivalent, and more preferably 0.005 to 0.01 equivalent. The amount of proton source used is preferably 0.5 to 5 equivalents, more preferably 1 to 2 equivalents, relative to the reducing agent.
In the method for producing ammonia according to the present embodiment, the lanthanoid metal used as the halide (II) of the lanthanoid metal includes La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, but Sm is preferable among them, and chlorine, bromine, and iodine are preferable among them as the halogen. As the halide (II) of the lanthanide metal, samarium (II) halide is preferable, and samarium (II) iodide is more preferable.
It is to be understood that the present invention is not limited to the above-described embodiments, and various modifications can be made within the technical scope of the present invention.
Examples
Hereinafter, examples of the present invention will be described. The following examples do not at all limit the present invention.
[ Experimental examples 1 to 21]
Ammonia (table 1) is produced from a nitrogen molecule in the presence of a reducing agent and a proton source using a molybdenum complex compound (1a) (shown in the chemical formula in table 1 outside the column) as a catalyst. In the following experimental examples, when ammonia exceeding 2 equivalents with respect to the molybdenum metal in the catalyst was generated, it was judged that ammonia was catalytically generated. The molybdenum complex (1a) was synthesized by referring to a publicly known literature (Bull. chem. Soc. Jpn.2017, vol.90, pp 1111-1118).
[ Table 1]
aReference to reducing agentb1mL of THF was usedcWithout catalystdUsing CoCp2As reducing agents
In Experimental example 1, under a nitrogen atmosphere at normal pressure, at room temperature, a molybdenum complex (1a) (1.7mg, 0.002mmol) as a catalyst and SmI as a reducing agent were added2(thf)2(solid crystals, 0.36mmol, 180 equivalents relative to molybdenum) in tetrahydrofuran (6mL), ethylene glycol (20. mu.L, 0.36mmol, 180 equivalents, 1 equivalent (1-fold mol) relative to the reducing agent) was added as a hydrogen ion source, followed by stirring for 18 hours. Then, an aqueous potassium hydroxide solution (30 mass%, 5mL) was added, distillation was performed under reduced pressure, and the distillate was recovered with an aqueous sulfuric acid solution (0.5M, 10 mL). The amount of ammonia in the aqueous sulfuric acid solution was determined by the indophenol method (Analytical Chemstry,1967, vol.39, pp 971-974). As a result, 43.8 equivalents of ammonia was produced with respect to the catalyst (molybdenum complex).
In examples 2 to 6, the amount of ethylene glycol used in example 1 was set to 0.5 to 5 equivalents relative to the reducing agent. As a result, it was found that the yield hardly changed when the amount of ethylene glycol used was 1 to 5 equivalents based on the reducing agent. In addition, in experimental example 1, the amount of ammonia generated was examined at reaction times of 1 minute and 15 minutes, and as a result, the reaction was substantially completed in 15 minutes at 35% and 62% based on the reducing agent, respectively. The TOF calculated from the results was about 1300/h at the maximum.
In Experimental example 7, the solvent amount in Experimental example 1 was reduced to 1mL, but the reaction proceeded without any problem.
In examples 8 to 12, the solvent in example 1 was changed from THF to dioxane, acetonitrile, diethyl ether, toluene, and hexane. When these solvents are used, ammonia can be obtained catalytically, although the yield is slightly lower than that of THF. In addition, in experimental example 13, an experiment was performed in which ethylene glycol was used as both a proton source and a solvent, and as a result, 4.9 equivalents of ammonia was generated with respect to molybdenum in an amount of 8% based on the reducing agent. Therefore, it was confirmed that ammonia was catalytically generated even when ethylene glycol was used as a solvent.
In experimental examples 14 to 19, the proton source in experimental example 3 was changed from ethylene glycol to various alcohols (methanol, ethanol, isopropanol, tert-butanol, trifluoroethanol, phenol). As a result, although the yield was slightly lower than that of ethylene glycol, it was confirmed that ammonia was catalytically produced.
In experimental example 20, the reaction was carried out without using the molybdenum complex (1a) in experimental example 1, and as a result, ammonia was not produced. In experimental example 21, decamethylcyclopentadiene was used as a reducing agent, and as a result, ammonia was not generated.
[ Experimental examples 22 to 29]
In experimental examples 22 to 29, ammonia synthesis was attempted using various molybdenum complex compounds shown in table 2 as catalysts in place of the catalyst of example 1. The chemical formula of each catalyst is shown outside the column of table 2. In Experimental example 29, 0.01mmol of the catalyst was used. The results are shown in table 2.
The molybdenum complex (1b) was synthesized by referring to a publicly known literature (Bull. chem. Soc. Jpn.2017, vol.90, pp 1111-1118). The molybdenum complexes (1c) and (2) were synthesized by referring to the publicly known literature (nat. chem.2011, vol.3, pp 120-125). The molybdenum complex (3a) was synthesized by referring to a publicly known literature (nat. Commun.2017, vol.8, airticle No. 14874). The molybdenum complex (3b) was synthesized by referring to a publicly known literature (j.am. chem. soc.2015, vol.137, pp 5666-5669). The molybdenum complex (5a) was synthesized by referring to publicly known documents (Inorg. chem.1973, vol.12, pp 2544-2547). The molybdenum complex (5b) was synthesized by referring to publicly known literature (J.Am.chem.Soc.1972, vol.94, pp 110-114). The molybdenum complex (4) was synthesized as follows. Pyridine (0.4mmol, 38. mu.L) and water (0.4mmol, 7. mu.L) were added to a THF solution (16mL) of the molybdenum complex (1a) (0.2mmol, 174.4mg) under a nitrogen atmosphere of 1 atm, and the mixture was stirred at 50 ℃ for 14 hours. Then, the reaction solution was concentrated under vacuum, dried and solidified, and the solid was washed with benzene (5mL, 3 times). The residue was then extracted with THF (5mL, 2 times), concentrated under vacuum, dried and solidified. The solid was dissolved in dichloromethane (4mL), filtered through celite, and hexane (20mL) was added to conduct recrystallization for 4 days, whereby 46.1mg (0.059mmol, 30% yield) of 4 (molybdenum complex (4)) was obtained as pale yellow crystals.
[ Table 2]
aReference to reducing agentb0.01mmol of catalyst was used
In experimental examples 22 to 23, molybdenum complex compounds (1b) to (1c) having a PNP ligand were used as catalysts. It was found that ammonia was catalytically produced regardless of whether X in the molybdenum complex compounds (1b) to (1c) was any of an iodine atom, a bromine atom and a chlorine atom.
In experimental examples 24 to 27, as the catalyst, a dinuclear molybdenum complex (2) having a PNP ligand, a molybdenum complex (3a) having a PCP ligand, a molybdenum complex (3b) having a PPP ligand, and a Mo (IV) oxo complex (4) having a PNP ligand were used. It was found that ammonia was catalytically produced by using any of the molybdenum complex compounds (2), (3a), (3b) and (4). Among these, particularly the molybdenum complex (3a) can give good results.
In experimental examples 28 to 29, mononuclear molybdenum complexes (5a) to (5b) were used as catalysts. It was found that ammonia was catalytically produced by using either of the trans-form mononuclear molybdenum complex compounds (5a) and (5 b).
[ Experimental example 30]
Experimental example 30 is an example using water as a proton source (see the following formula). Relative to the molybdenum complex (1a) (0.002mmol) and SmI2(thf)2(solid)Bulk crystal, 0.36mmol, 180 equivalents relative to molybdenum) in THF (4mL), and water (0.36mmol, 180 equivalents relative to molybdenum) in THF (2mL) was added dropwise over 0.5 hour at room temperature using a syringe pump under a nitrogen atmosphere of 1 atm while stirring. After stirring at room temperature for further 17.5 hours after completion of the dropwise addition, the amounts of ammonia and hydrogen were determined. As a result, 43% of ammonia (26.8 equivalents relative to molybdenum) and 39% of hydrogen (36.0 equivalents relative to molybdenum) were produced. Therefore, it is found that ammonia is catalytically generated even when water is used as a proton source.
[ Experimental examples 31 to 38]
In Experimental examples 31 to 38, a molybdenum complex was used as a catalyst in a reducing agent (SmI)2) And a proton source in THF at room temperature to produce ammonia from the nitrogen molecule (table 3). In experimental example 31, a reaction was carried out using the molybdenum complex compound (1a) having a PNP ligand as a catalyst and diethylene glycol as a proton source. In experimental examples 32 to 37, a reaction was carried out using a molybdenum complex compound (3a) having a PCP ligand as a catalyst and diethylene glycol as a proton source. In experimental example 38, a reaction was carried out using the molybdenum complex compound (3a) having a PCP ligand as a catalyst and water as a proton source. The results are shown in table 3.
[ Table 3]
Based on Smi2(thf)2The yield of (A) was found.
Average of multiple experiments (at least 2 cases).
# THF (2mL) was used as the solvent. Use H2O as a proton source.
From the results of experimental examples 31 and 32, it is understood that the molybdenum complex compound (3a) having a PCP ligand has higher catalytic activity than the molybdenum complex compound (1a) having a PNP ligand. From the results of experimental examples 32 to 37, it was found that ammonia was obtained at a high ratio when the molybdenum complex (3a) was used as a catalyst and diethylene glycol was used as a proton source. From the results of experimental examples 33 and 38, it is understood that when the molybdenum complex compound (3a) having a PNP ligand is used as a catalyst, ammonia is obtained as a proton source at a higher ratio when water is used than when diethylene glycol is used. Among the experimental examples shown in the present specification, the best results were obtained in experimental example 38.
[ Experimental examples 39 to 41]
In Experimental examples 39 to 41, a molybdenum complex was used as a catalyst in the presence of a reducing agent (SmI)2) And a proton source (H)2O) ammonia was produced from nitrogen molecules in THF at room temperature (table 4). In experimental example 39, the reaction was carried out using the molybdenum complex (3a) as a catalyst, in experimental example 40, using the molybdenum complex (3c) having fluorine atoms at the 5-and 6-positions of the benzimidazole carbene ring as a catalyst, and in experimental example 41, using the molybdenum complex (3d) having a trifluoromethyl group at the 5-position of the benzimidazole carbene ring as a catalyst.
As a representative example, experimental example 41 will be described. For the molybdenum complex (3d) (0.025. mu. mol) and SmI2(thf)2(solid crystals, 1.44mmol, 57600 equivalents relative to molybdenum) in THF (2mL), a solution of water (1.44mmol, 57600 equivalents relative to molybdenum) in THF (1mL) was added under a nitrogen atmosphere of 1 atm at room temperature, and the mixture was stirred at room temperature for 22 hours. Then, the gas phase was analyzed by Gas Chromatography (GC) to quantify hydrogen, and as a result, 4700 equivalents of hydrogen was generated with respect to the catalyst (molybdenum complex). An aqueous potassium hydroxide solution (30% by mass, 5mL) was added thereto, and the mixture was distilled under reduced pressure, and the distillate was recovered with an aqueous sulfuric acid solution (0.5M, 10 mL). The amount of ammonia in the aqueous sulfuric acid solution was measured by the indophenol method (Analy)Clinical Chemstry,1967, vol.39, pp 971-974). As a result, 16000 equivalents of ammonia was produced with respect to the catalyst (molybdenum complex). Reactions were carried out in the same manner as in experimental example 41 except that in experimental examples 39 and 40, the molybdenum complexes (3a) and (3c) were used in place of the molybdenum complex (3 d). The results are shown in table 4. As is clear from table 4, the catalytic activity was higher in the molybdenum complexes (3c) and (3d) than in the molybdenum complex (3a), and higher in the molybdenum complex (3d) than in the molybdenum complex (3 c).
[ Table 4]
Based on Smi2(thf)2The yield of (A) was found.
Here, the procedure for synthesizing the molybdenum complex (3d) used in Experimental example 41 is described below with reference to the following scheme.
Synthesis of Compound 1
The synthesis of compound 1 is shown below. Di-tert-butylphosphine (2.25g, 14.9mmol) and paraformaldehyde (450mg, 15.0mmol) were stirred under a nitrogen atmosphere at 60 ℃ for 16 hours. Then, 150mL of dichloroethane and 1, 2-diamino-4-trifluoromethylbenzene (1.06g, 6.02mmol) were added, and the mixture was stirred at 60 ℃ for 24 hours under a nitrogen atmosphere. Then, selenium (1.26g, 16.0mmol) was added, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere. The reaction mixture was concentrated, and the resulting solid was separated by silica gel column chromatography (dichloromethane: hexane ═ 1/1). The recovered fraction was concentrated and dried under vacuum to solidify and isolate compound 1 as a white solid at 2.48g (3.81mmol, 63% yield).1H NNR(CDCl3)：7.08(d，J＝8.4Hz，1H)，6.81(s，1H)，6.66(d，J＝8.4Hz，1H)，5.01-4.99(m，1H)，4.81-4.77(m，1H)，3.39-3.33(m，4H)，1.45(d，J＝15.2Hz，18H)，1.43(d，J＝15.2Hz，18H)，31P NMR(CDCl3)：79.9(s)，79.6(s)。
Synthesis of Compound 2
The synthesis of compound 2 is shown below. Compound 1(2.48g, 3.81mmol), triethyl orthoformate (10mL), ammonium hexafluorophosphate (629mg, 3.86mmol) was stirred under air at 120 ℃ for 3 hours. Then, concentrate and use CH2Cl2/Et2O mixed solution (4mL/8 mL. times.2), Et2O (10 mL. times.1) wash. Drying under vacuum resulted in the isolation of compound 2 as a white solid at 2.58g (3.20mmol, 84% yield).1H NNR(CDCl3)：10.13(s，1H)，8.16(s，1H)，8.11(d，J＝8.4Hz，1H)，7.89(d，J＝8.4Hz，1H)，5.08-5.04(m，4H)，1.48(d，J＝16.0Hz，18H)，1.47(d，J＝16.4Hz，18H)，31P NMR(CDCl3)：81.7(s)，80.7(s)，-135.1～-152.7(m)。
Synthesis of Compound 3
The synthesis of compound 3 is shown below. Compound 3(2.58g, 3.20mmol) and tris (dimethylamino) phosphine (1.5mL) were stirred in dichloromethane (40mL) at room temperature for 4 hours under a nitrogen atmosphere. Then, concentration and washing with toluene (7mL × 3) were performed, and drying under vacuum was performed, thereby isolating compound 3 as a white solid in 1.66g (2.56mmol, 80% yield).1H NNR(CDCl3)：9.81(s，1H)，8.27(s，1H)，8.15(d，J＝8.4Hz，1H)，7.88(d，J＝8.4Hz，1H)，4.72-4.70(m，4H)，1.23(d，J＝12.0Hz，18H)，1.21(d，J＝12.0Hz，18H)，31P NMR(CDCl3)：25.9(s)，25.1(s)，-139.4～-152.6(m)。
Synthesis of molybdenum Complex Compound (3d)
The following shows the synthesis of the molybdenum complex (3 d). Compound 3(1.30g, 2.00mmol) and potassium bis (trimethylsilyl) amide salt (561mg, 2.81mmol) were stirred in toluene (45mL) at room temperature under an argon atmosphere for 1 hour. Then, using diatomiteAfter filtration, MoCl was added3(thf)3(756mg, 1.81mmol) and stirred at 80 ℃ for 26 h. The reaction solution was concentrated until 5mL, filtered using filter paper and dried to solidify under vacuum. The obtained solid was washed with toluene (5 mL. times.2), and then dissolved in CH2Cl2(20mL) and filtered using celite. Hexane (30mL) was slowly added to the filtrate and left standing for 5 days to form brown crystals. The supernatant was removed, washed with hexane (5mL × 3), and dried under vacuum to isolate the molybdenum complex (3d) as brown crystals at 381mg (0.54mmol, 30% yield). Anal.calcd.for C26H43N2F3P2Cl3Mo·1/2CH2Cl2：C，42.59；H，5.93；N，3.75Found：C，42.79；H，5.74；N，3.91。
The molybdenum complex (3c) used in experimental example 40 can be synthesized by using 1, 2-diamino-4, 5-difluorobenzene in place of 1, 2-diamino-4-trifluoromethylbenzene in the synthesis scheme of the molybdenum complex (3 d).
[ Experimental example 42]
In experimental example 42, ammonia was produced on a larger scale. In a 1000mL four-necked flask, the amount of the molybdenum complex (3a) (0.100mmol, 63.8mg) and SmI were measured2(thf)2(solid crystals, 36.0mmol, 19.7g, 360 equivalents relative to molybdenum) in THF (270mL), water (36.0mmol, 360 equivalents relative to molybdenum) in THF (20mL) was added under a stream of nitrogen at room temperature while stirring with a mechanical stirrer (220rpm), and then stirred at room temperature for 8 minutes. The reaction solution was concentrated, dried and solidified by an evaporator. To the obtained solid was added an aqueous potassium hydroxide solution (30 mass%, 20mL), and the mixture was distilled under reduced pressure, and the distillate was recovered with an aqueous solution (about 10mL) of 96% concentrated sulfuric acid (5.04mmol, 515 mg). The recovered aqueous solution was concentrated using an evaporator and dried under vacuum overnight. As a result, (NH) was obtained in an amount of 668mg (5.06mmol, 84% yield)4)2SO4White solid of (2). This corresponds to the formation of 101 equivalents of ammonia relative to the catalyst (molybdenum complex). Anal.calcd.forh8N2O4S：H，6.10；N，21.20Found：H，6.06；N，20.98。
In addition, experimental examples 1 to 19 and 22 to 42 correspond to examples of the present invention, and experimental examples 20 and 21 correspond to comparative examples.
The present application takes japanese patent application No. 2018-36967, applied on day 1 at 3/2018 and japanese patent application No. 2018-158595, applied on day 27 at 8/2018 as the basis for claiming priority, the entire contents of which are incorporated in the present specification by reference.
Industrial applicability
The present invention can be used for the production of ammonia.
Claims (11)
1. A process for producing ammonia from a nitrogen molecule in the presence of a catalyst, a reducing agent and a proton source,
the catalyst is (A) a molybdenum complex compound having 2, 6-bis (dialkylphosphinomethyl) pyridine as a PNP ligand, (B) a molybdenum complex compound having N, N-bis (dialkylphosphinomethyl) benzimidazolecarbonine as a PCP ligand, (C) a molybdenum complex compound having bis (dialkylphosphinoethyl) arylphosphine as a PPP ligand, or (D) trans-Mo (N2)2(R1R2R3P)4The molybdenum complex compound represented by the formula (I), wherein 2 alkyl groups in the 2, 6-bis (dialkylphosphinomethyl) pyridine may be the same or different, at least 1 hydrogen atom of the pyridine ring may be substituted by an alkyl group, an alkoxy group or a halogen atom, 2 alkyl groups in the N, N-bis (dialkylphosphinomethyl) benzimidazole carbene may be the same or different, at least 1 hydrogen atom of the benzene ring may be substituted by an alkyl group, an alkoxy group or a halogen atom, 2 alkyl groups in the bis (dialkylphosphinoethyl) arylphosphine may be the same or different, and the trans-Mo (N, 6-bis (dialkylphosphinomethyl) pyridine2)2(R1R2R3P)4In, R1、R2、R3Is an alkyl or aryl group which may be the same or different, 2R3Can be linked to each other to form an alkylene chain,
as reducing agent, a halide (II) of a lanthanide metal is used,
as the proton source, alcohol or water is used.
2. The method for producing ammonia according to claim 1, wherein the molybdenum complex compound of (A) is a molybdenum complex compound represented by the following formula (A1), (A2) or (A3),
in the formula, R1And R2Is an alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least 1 hydrogen atom on the pyridine ring may be substituted by an alkyl group, an alkoxy group or a halogen atom.
3. The process for producing ammonia according to claim 1, wherein the molybdenum complex compound of the formula (B) is a molybdenum complex compound represented by the following formula (B1),
in the formula, R1And R2Is an alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least 1 hydrogen atom on the benzene ring may be substituted by an alkyl group, an alkoxy group or a halogen atom.
4. The method for producing ammonia according to claim 3, wherein at least one of the 5-position and the 6-position of the benzimidazole carbene ring of the formula (B1) is substituted with a trifluoromethyl group.
5. The method for producing ammonia according to claim 1, wherein the molybdenum complex compound of formula (C) is a molybdenum complex compound represented by formula (C1),
in the formula, R1And R2Is an alkyl group which may be the same or different，R3Is aryl, and X is iodine atom, bromine atom or chlorine atom.
6. The method for producing ammonia according to claim 1, wherein the molybdenum complex compound of (D) is a molybdenum complex compound represented by formula (D1) or (D2),
in the formula, R1、R2And R3Is an alkyl or aryl group which may be the same or different, and n is 2 or 3.
7. The method for producing ammonia according to any one of claims 1 to 6, wherein nitrogen gas at normal pressure is used as the nitrogen molecules.
8. The method for producing ammonia according to any one of claims 1 to 7, wherein the alcohol is a diol or ROH, and R is a C1-6 linear, cyclic or branched alkyl group whose hydrogen atom may be substituted with a fluorine atom, or a phenyl group which may have an alkyl group.
9. The method for producing ammonia according to any one of claims 1 to 8, wherein the halide (II) of a lanthanoid metal is a samarium (II) halide.
10. A molybdenum complex compound represented by the formula (B2),
in the formula, R1And R2Is an alkyl group which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, R is3And R4At least one of which is substituted with trifluoromethyl.
11. A benzimidazole compound represented by the formula (E),
wherein A is an anion, R1And R2Are alkyl groups which may be the same or different, R3And R4At least one of which is substituted with trifluoromethyl.
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| PCT/JP2019/007793 WO2019168093A1 (en) | 2018-03-01 | 2019-02-28 | Ammonia manufacturing method, molybdenum complex, and benzimidazole compound |
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| JP2023126983A (en) * | 2020-07-27 | 2023-09-13 | 国立大学法人 東京大学 | Method for producing ammonia |
| JP2023126984A (en) * | 2020-07-27 | 2023-09-13 | 国立大学法人 東京大学 | Method for producing ammonia |
| WO2022025046A1 (en) * | 2020-07-27 | 2022-02-03 | 国立大学法人東京大学 | Method for manufacturing ammonia |
| US20230295813A1 (en) * | 2020-08-14 | 2023-09-21 | Nissan Chemical Corporation | Ammonia production method and ammonia production apparatus |
| WO2022034927A1 (en) * | 2020-08-14 | 2022-02-17 | 国立大学法人東京大学 | Ammonia production method and ammonia production apparatus |
| JPWO2022210925A1 (en) * | 2021-03-30 | 2022-10-06 | ||
| WO2022210567A1 (en) * | 2021-03-30 | 2022-10-06 | 国立大学法人東京大学 | Method for producing ammonia, molybdenum complex used in said production method, and ligand that is raw material of said molybdenum complex |
| WO2022230898A1 (en) * | 2021-04-27 | 2022-11-03 | 出光興産株式会社 | Method for producing nitrogen-containing compound |
| ES2952082B2 (en) * | 2022-03-21 | 2024-03-04 | Univ Alcala Henares | MONOCYCLOPENTADIENYL COMPLEXES FOR AMMONIA SYNTHESIS |
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| JP2015124153A (en) * | 2013-12-25 | 2015-07-06 | 国立大学法人名古屋大学 | Method for manufacturing alcohol by hydrogenation of carboxylic acid compound, ruthenium complex used for manufacturing method |
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| JP2013159568A (en) * | 2012-02-02 | 2013-08-19 | Toyota Motor Corp | Dinuclear molybdenum complex, method of synthesizing the same, and ammonia synthesis method |
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| JP2015124153A (en) * | 2013-12-25 | 2015-07-06 | 国立大学法人名古屋大学 | Method for manufacturing alcohol by hydrogenation of carboxylic acid compound, ruthenium complex used for manufacturing method |
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