CN111801297B - Method for producing ammonia, molybdenum complex compound, and benzimidazole compound - Google Patents
Method for producing ammonia, molybdenum complex compound, and benzimidazole compound Download PDFInfo
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- CN111801297B CN111801297B CN201980016588.0A CN201980016588A CN111801297B CN 111801297 B CN111801297 B CN 111801297B CN 201980016588 A CN201980016588 A CN 201980016588A CN 111801297 B CN111801297 B CN 111801297B
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- molybdenum complex
- substituted
- alkyl group
- producing ammonia
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 124
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 97
- 239000011733 molybdenum Substances 0.000 title claims abstract description 97
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 62
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- -1 benzimidazole compound Chemical class 0.000 title claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 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 52
- 125000003545 alkoxy group Chemical group 0.000 claims description 21
- 125000005843 halogen group Chemical group 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 125000004432 carbon atom Chemical group C* 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
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 150000004820 halides Chemical class 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
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 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
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- UAWABSHMGXMCRK-UHFFFAOYSA-L samarium(ii) iodide Chemical compound I[Sm]I UAWABSHMGXMCRK-UHFFFAOYSA-L 0.000 abstract description 6
- 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 24
- 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 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 244000309464 bull Species 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 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 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000003756 stirring Methods 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 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
- 239000007864 aqueous solution Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000002474 experimental method Methods 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
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 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
- 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 101100391181 Dictyostelium discoideum forH gene Proteins 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- DGDBSLKLKZTDSL-UHFFFAOYSA-N [I].[Mo] Chemical compound [I].[Mo] DGDBSLKLKZTDSL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 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
- 125000001352 cyclobutyloxy group Chemical group C1(CCC1)O* 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
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 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
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 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
- 125000000131 cyclopropyloxy group Chemical group C1(CC1)O* 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
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 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
- 239000007789 gas Substances 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
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 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
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 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
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011002 quantification Methods 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
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 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
- 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 according to the present application is a method for producing ammonia from nitrogen molecules in the presence of a catalyst, a reducing agent and a proton source. As catalysts, use is made, for example, of [ MoI ] 3 (PNP)](PNP is a molybdenum coordination compound of 2, 6-bis (di-tert-butylphosphinomethyl) pyridine). Samarium (II) iodide was used as the reducing agent, and alcohol or water was used as the proton source.
Description
Technical Field
The present application relates to a method for producing ammonia, a molybdenum complex compound, and a benzimidazole compound.
Background
The Haber (Haber-Bosch) process, which is an industrial process for converting nitrogen molecules into ammonia, is an energy-consuming process requiring high-temperature and high-pressure reaction conditions. 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 a molybdenum complex as a catalyst is produced by adding a toluene solution of decamethylcobaltocene 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 triflate as a proton source in the presence of nitrogen at normal pressure at room temperature and stirring the mixture as shown in the following formula.
Prior art literature
Non-patent literature
Non-patent document 1: bull. Chem. Soc. Jpn.2017, vol.90, pp1111-1118
Disclosure of Invention
Problems to be solved by the application
However, in the above non-patent document 1, it is necessary to use a stoichiometric amount of an expensive conjugated acid of decamethylcobaltocene or trimethylpyridine (Collidine). Therefore, from an industrial point of view, development of a cheaper method for producing ammonia is desired.
The present application has been made to solve the above problems, and a main object of the present application is to produce ammonia from nitrogen molecules relatively inexpensively.
Means for solving the problems
In order to achieve the above object, the present inventors studied a method for producing ammonia from nitrogen molecules using a molybdenum complex as a catalyst and samarium (II) iodide as a reducing agent, and as a result, found that alcohol and water can be used as proton sources, and completed the present application.
That is, the method for producing ammonia according to the present application is a method for producing ammonia from nitrogen molecules in the presence of a catalyst, a reducing agent and a proton source,
the catalyst is (A) a molybdenum complex having 2, 6-bis (dialkylphosphinomethyl) pyridine (wherein 2 alkyl groups may be the same or different, 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 having N, N-bis (dialkylphosphinomethyl) benzimidazole carbene (N, N-bis (dialkyl phosphinomethyl) benzimidozolide wherein 2 alkyl groups may be the same or different, 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 having bis (dialkylphosphinoethyl) arylphosphine (wherein 2 alkyl groups may be the same or different) as a PPP ligand, or (D) trans-Mo (N) 2 ) 2 (R 1 R 2 R 3 P) 4 (wherein R is 1 、R 2 、R 3 To alkyl or aryl groups, which may be identical or different, 2R' s 3 Can be linked to each other to form an alkylene chain),
as the reducing agent, a halide (II) of a lanthanide metal is used,
as the proton source, alcohol or water is used.
According to this ammonia production method, since alcohol and water can be used as proton sources and the reaction proceeds even at normal temperature (0 to 40 ℃), ammonia can be produced from nitrogen molecules at a lower cost than in the past.
Detailed Description
Preferred embodiments of the method for producing ammonia according to the present application are shown below.
The method for producing ammonia according to the present embodiment is a method for producing ammonia from nitrogen molecules 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, is used as a catalystMay be different, 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 molybdenum complex of a PCP ligand, (C) a molybdenum complex of a bis (dialkylphosphinoethyl) arylphosphine (wherein 2 alkyl groups may be the same or different) as a PPP ligand, or (D) trans-Mo (N) 2 ) 2 (R 1 R 2 R 3 P) 4 (wherein R is 1 、R 2 、R 3 To alkyl or aryl groups, which may be identical or different, 2R' s 3 Can be linked to each other to form an alkylene chain). Further, as the reducing agent, a halide (II) of a lanthanide metal is used, and as the proton source, alcohol or water is used.
The molybdenum complex compound of (a) may be a linear or branched alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and structural isomers thereof, or a cyclic alkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. The alkoxy group may be, for example, a linear or branched alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy group, structural isomers thereof, or a cyclic alkoxy group such as cyclopropoxy group, cyclobutoxy group, cyclopentoxy group, cyclohexyloxy group. The alkoxy group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The molybdenum complex compound of (a) may be, for example, a molybdenum complex compound represented by the formula (A1), (A2) or (A3). Examples of the alkyl group, the alkoxy group and the halogen atom include the same groups and atoms as those of the alkyl group, the alkoxy group and the halogen atom already exemplified. As R 1 And R is 2 Bulky alkyl groups (e.g., t-butyl, isopropyl) are preferred. The hydrogen atom on the pyridine ring is preferably unsubstituted or the hydrogen atom at the 4-position is substituted with a chain, cyclic or branched alkyl group having 1 to 12 carbon atoms.
(wherein R is 1 And R is 2 In which 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 with an alkyl group, an alkoxy group or a halogen atom
The molybdenum complex compound of (B) may be, for example, a molybdenum complex compound represented by the formula (B1). Examples of the alkyl group, the alkoxy group and the halogen atom include the same groups and atoms as those of the alkyl group, the alkoxy group and the halogen atom already exemplified. As R 1 And R is 2 Bulky alkyl groups (e.g., t-butyl, isopropyl) are preferred. 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. Molybdenum complex compounds of the formula (B2) are particularly preferred. In formula (B2), R is preferably 1 、R 2 And X is the same as in formula (B1), R 3 And R is 4 At least one of which is substituted with a fluoro group, R being more preferable 3 And R is 4 At least one of which is substituted by trifluoromethyl. The benzimidazole compound of formula (E) can be used as an intermediate for synthesizing the molybdenum complex compound of formula (B2). In formula (E), A is an anion, R 1 、R 2 And X is the same as in formula (B1), R 3 And R is 4 As in formula (B2). The anion of A is not particularly limited, and examples thereof include PF 6 - 、BF 4 - 、ClO 4 - Etc.
(wherein R is 1 And R is 2 In which 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 with an alkyl group, an alkoxy group or a halogen atom
The molybdenum complex compound of (C) may be, for example, a molybdenum complex compound 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 hydrogen atoms on these rings is substituted with an alkyl group or a halogen atom. Examples of the alkyl group and halogen atom include the same groups and atoms as those of the alkyl group and halogen atom already exemplified. As R 1 And R is 2 Bulky alkyl groups (e.g., t-butyl, isopropyl) are preferred. As R 3 Preferably, for example, phenyl.
(wherein R is 1 And R is 2 R is alkyl which may be the same or different 3 Is aryl, X is an iodine atom, a bromine atom or a chlorine atom
The molybdenum complex compound represented by the formula (D1) or (D2) is exemplified as the molybdenum complex compound of the formula (D). Examples of the alkyl group and the aryl group include the same groups as those already exemplified. In formula (D1), R is preferably 1 And R is 2 Is aryl (e.g. phenyl) and R 3 Is an alkyl group having 1 to 4 carbon atoms (e.g., methyl group), or R 1 And R is 2 Is an alkyl group having 1 to 4 carbon atoms (e.g., methyl) and R 3 Is aryl (e.g., phenyl). In formula (D2), R is preferably 1 And R is 2 Is aryl (e.g., phenyl) and n is 2.
(wherein R is 1 、R 2 And R is 3 Alkyl or aryl which may be the same or different, n being 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 is inexpensive and therefore can be used in a 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, a diol may be used as the alcohol, or ROH (R is a chain, cyclic or branched alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have an alkyl group, the hydrogen atom of which may be substituted with a fluorine atom) may be used. Examples of the diol include ethylene glycol, propylene glycol, and diethylene glycol, but among them, ethylene glycol is preferable. Examples of the ROH include chain 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; alcohols containing fluorine atoms such as trifluoroethyl alcohol and tetrafluoroethyl alcohol; phenol derivatives such as phenol, cresol and xylenol.
In the method for producing ammonia according to 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 a normal temperature (0 to 40 ℃). The reaction atmosphere is not necessarily a pressurized atmosphere, and may be an atmospheric pressure atmosphere. The reaction time is not particularly limited, but is usually set in a range of several minutes to several 10 hours.
In the method for producing ammonia according to the present embodiment, the catalyst may be used in an amount within a range of 0.00001 to 0.1 equivalent, preferably 0.0005 to 0.1 equivalent, more preferably 0.005 to 0.01 equivalent, to the reducing agent. The proton source is preferably used in an amount of 0.5 to 5 equivalents relative to the reducing agent, but more preferably 1 to 2 equivalents.
In the method for producing ammonia according to the present embodiment, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu is preferable as the lanthanide metal used as the lanthanide metal halide (II), and Sm is preferable as the halogen, chlorine, bromine, and iodine are preferable as the halogen. The halide (II) of the lanthanide metal is preferably samarium (II) halide, more preferably samarium (II) iodide.
The present application is not limited to the above embodiments, and can be implemented in various embodiments as long as the present application is within the technical scope of the present application.
Examples
Hereinafter, examples of the present application will be described. In addition, the following examples do not limit the present application at all.
Experimental examples 1 to 21
Ammonia (table 1) was produced from nitrogen molecules in the presence of a reducing agent and a proton source using molybdenum complex (1 a) (chemical formula shown outside the column of table 1) as a catalyst. In the following experimental example, when ammonia was generated in an amount exceeding 2 equivalents relative to molybdenum metal in the catalyst, it was determined that ammonia was generated catalytically. The molybdenum complex (1 a) was synthesized by reference to a known document (Bull. Chem. Soc. Jpn.2017, vol.90, pp 1111-1118).
TABLE 1
a Reductant datum b 1mL of THF was used c No catalyst d Using CoCp 2 As a reducing agent
In Experimental example 1, molybdenum complex (1 a) (1.7 mg,0.002 mmol) as a catalyst and SmI as a reducing agent were reacted at room temperature under a nitrogen atmosphere at normal pressure 2 (thf) 2 (solid Crystal, 0.36mmol,180 equivalent to molybdenum) in tetrahydrofuran (6 mL) was added as a hydrogen ion source(20. Mu.L, 0.36mmol,180 equivalents relative to the reducing agent, 1 equivalent (1-fold mol)) and then stirred for 18 hours. Then, an aqueous potassium hydroxide solution (30% by mass, 5 mL) was added thereto, and the mixture was distilled under reduced pressure, whereby a distilled solution 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 relative to the catalyst (molybdenum complex) were produced.
In examples 2 to 6, the amount of ethylene glycol used in example 1 was set to be 0.5 to 5 equivalents relative to the reducing agent. As a result, it was found that the yield was hardly changed when the amount of ethylene glycol was 1 to 5 equivalents relative to the reducing agent. In experimental example 1, the amounts of ammonia produced at the reaction times of 1 minute and 15 minutes were examined, and as a result, the reaction was substantially completed at 15 minutes with 35% and 62% of the reducing agent as a reference, respectively. The TOF calculated from this result is up to about 1300/h.
In Experimental example 7, the amount of the solvent in Experimental example 1 was reduced to 1mL, but the reaction was performed without problems.
In examples 8 to 12, the solvent in example 1 was changed from THF to dioxane, acetonitrile, diethyl ether, toluene, hexane. When these solvents are used, ammonia can be obtained catalytically although the yield is slightly lower than THF. 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, ammonia was 8% based on the reducing agent, and 4.9 equivalents were formed with respect to molybdenum. Therefore, even in the case of using ethylene glycol as a solvent, the ammonia was confirmed to be produced catalytically.
In examples 14 to 19, the proton source in example 3 was changed from ethylene glycol to various alcohols (methanol, ethanol, isopropanol, t-butanol, trifluoroethanol, phenol). As a result, although the yield was slightly lower than that of ethylene glycol, it was confirmed that ammonia was produced catalytically.
In example 20, the reaction was performed without using the molybdenum complex (1 a) in example 1, and as a result, ammonia was not produced. In experimental example 21, decamethylcobaltocene 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 coordination compounds shown in table 2 as catalysts instead of the catalyst of example 1. The chemical formulas of the respective catalysts are shown outside the columns of table 2. In Experimental example 29, 0.01mmol of the catalyst was used. The results are shown in table 2.
The molybdenum complex (1 b) was synthesized by reference to a known document (Bull. Chem. Soc. Jpn.2017, vol.90, pp 1111-1118). The molybdenum complex compounds (1 c) and (2) were synthesized by reference to the known literature (Nat. Chem.2011, vol.3, pp 120-125). The molybdenum complex (3 a) was synthesized by referring to a known document (Nat. Commun.2017, vol.8, airticle No. 14874). The molybdenum complex (3 b) was synthesized with reference to a known document (J.Am.chem. Soc.2015, vol.137, pp 5666-5669). The molybdenum complex (5 a) was synthesized by reference to a known document (Inorg. Chem.1973, vol.12, pp 2544-2547). The molybdenum complex (5 b) was synthesized by reference to a known document (J.Am.chem.Soc.1972, vol.94, pp 110-114). The molybdenum complex (4) was synthesized as follows. Pyridine (0.4 mmol, 38. Mu.L), water (0.4 mmol, 7. Mu.L) and a THF solution (16 mL) of molybdenum complex (1 a) (0.2 mmol,174.4 mg) were added under a nitrogen atmosphere at 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 (5 ml,3 times). Then, the residue was extracted with THF (5 ml,2 times) and concentrated under vacuum to dryness for solidification. The solid was dissolved in methylene chloride (4 mL), and after filtration through celite, hexane (20 mL) was added and recrystallization was performed for 4 days, whereby 46.1mg (0.059 mmol,30% yield) of 4 (molybdenum complex (4)) was obtained as pale yellow crystals.
TABLE 2
a Reductant datum b 0.01mmol of catalyst was used
In experimental examples 22 to 23, molybdenum complex compounds (1 b) to (1 c) having PNP ligands were used as catalysts. It is found that ammonia is produced catalytically regardless of whether X of the molybdenum complex compounds (1 b) to (1 c) is any one 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 (3 a) having a PCP ligand, a molybdenum complex (3 b) having a PPP ligand, and a Mo (IV) oxo complex (4) having a PNP ligand were used. It is found that ammonia is produced catalytically regardless of the use of any one of the molybdenum complex compounds (2), (3 a), (3 b) and (4). Among them, particularly the molybdenum complex (3 a) can obtain good results.
In experimental examples 28 to 29, mononuclear molybdenum coordination compounds (5 a) to (5 b) were used as catalysts. It is known that ammonia is produced catalytically regardless of the use of either of the trans-type mononuclear molybdenum coordination compounds (5 a) and (5 b).
Experimental example 30
Experimental example 30 is an example using water as a proton source (see the following formula). Relative to molybdenum coordination compound (1 a) (0.002 mmol) and SmI 2 (thf) 2 (solid crystals, 0.36mmol,180 equivalents to molybdenum) in THF (4 mL), and water (0.36 mmol,180 equivalents to molybdenum) in THF (2 mL) was added dropwise over 0.5 hour under nitrogen at 1 atm and stirred at room temperature using a syringe pump. After stirring at room temperature for 17.5 hours further after completion of the dropwise addition, quantification of ammonia and hydrogen was performed. As a result, ammonia 43% (26.8 equivalents to molybdenum) and hydrogen 39% (36.0 equivalents to molybdenum) were produced. Therefore, it is known that ammonia is produced catalytically even when water is used as a proton source.
Experimental examples 31-38
In examples 31 to 38, molybdenum complex was used as a catalyst in the presence of a reducing agent (Smi 2 ) And a proton source, ammonia was produced from the nitrogen molecules in THF at room temperature (table 3). In experimental example 31, a reaction was performed using molybdenum complex (1 a) having a PNP ligand as a catalyst and diethylene glycol as a proton source. In experimental examples 32 to 37, the reaction was performed using molybdenum complex (3 a) having PCP ligand as a catalyst and diethylene glycol as a proton source. In experimental example 38, a reaction was performed using a molybdenum complex (3 a) having a PCP ligand as a catalyst and water as a proton source. The results are shown in table 3.
TABLE 3
* Based on SmI 2 (thf) 2 Yield of (2).Average of multiple experiments (at least 2).
THF (2 mL) was used as solvent. Use H 2 O is used as a proton source.
From the results of examples 31 and 32, it was found that the molybdenum complex (3 a) having a PCP ligand had higher catalytic activity than the molybdenum complex (1 a) 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 molybdenum complex (3 a) was used as a catalyst and diethylene glycol was used as a proton source. From the results of examples 33 and 38, it was found that when the molybdenum complex (3 a) having a PNP ligand was used as a catalyst, ammonia was obtained at a higher rate when water was used as a proton source than when diethylene glycol was used. In addition, among the experimental examples shown in the present specification, experimental example 38 gave the best results.
Experimental examples 39-41
In experimental examples 39 to 41, molybdenum complex was used as a catalyst in the presence of a reducing agent (Smi 2 ) And proton source (H) 2 O) in THF, ammonia was produced from the nitrogen molecules at room temperature (table 4). In example 39, the above molybdenum complex (3 a) was used as a catalyst, in example 40, a molybdenum complex (3 c) having fluorine atoms at the 5-and 6-positions of the benzimidazole carbene ring was used as a catalyst, and in example 41, a molybdenum complex (3 d) having a trifluoromethyl group at the 5-position of the benzimidazole carbene ring was used as a catalyst, and the reaction was performed.
As a representative example, experimental example 41 will be described. For molybdenum coordination compound (3 d) (0.025. Mu. Mol) and SmI 2 (thf) 2 (solid crystals, 1.44mmol, 57600 eq. To molybdenum) in THF (2 mL) was added water (1.44 mmol, 57600 eq. To molybdenum) in THF (1 mL) at room temperature under a nitrogen atmosphere at 1 atm and 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 relative to the catalyst (molybdenum complex) were produced. Aqueous potassium hydroxide (30% by mass, 5 mL) was added thereto, and the mixture was distilled under reduced pressure, whereby a distilled solution was recovered with aqueous sulfuric acid (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, 16000 equivalents of ammonia relative to the catalyst (molybdenum complex) were produced. A reaction was performed in the same manner as in example 41 except that molybdenum complex compounds (3 a) and (3 c) were used instead of molybdenum complex compound (3 d) in examples 39 and 40. The results are shown in table 4. As is clear from table 4, the catalytic activity of the molybdenum complex (3 c) and (3 d) was higher than that of the molybdenum complex (3 a), and the catalytic activity of the molybdenum complex (3 d) was higher than that of the molybdenum complex (3 c).
TABLE 4
Based on Smi 2 (thf) 2 Yield of (2).
Here, the procedure for synthesizing the molybdenum complex (3 d) used in experimental example 41 will be described below with reference to the following schemes.
Synthesis of Compound 1
The synthesis of compound 1 is shown below. Di-tert-butylphosphine (2.25 g,14.9 mmol) and paraformaldehyde (450 mg,15.0 mmol) were stirred under nitrogen at 60℃for 16 hours. Then, 150mL of dichloroethane, 1, 2-diamino-4-trifluoromethylbenzene (1.06 g,6.02 mmol) was added thereto and stirred under nitrogen at 60℃for 24 hours. Selenium (1.26 g,16.0 mmol) was then added and stirred at room temperature under nitrogen for 24 hours. The reaction was concentrated and the resulting solid was separated by column chromatography on silica gel (dichloromethane: hexane=1/1). The recovered fraction was concentrated, dried and solidified under vacuum to isolate compound 1 as a white solid in 2.48g (3.81 mmol,63% yield). 1 H NNR(CDCl 3 )：δ7.08(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)， 31 P NMR(CDCl 3 )：δ79.9(s)，79.6(s)。
Synthesis of Compound 2
The synthesis of compound 2 is shown below. Compound 1 (2.48 g,3.81 mmol), triethyl orthoformate (10 mL), ammonium hexafluorophosphate (629 mg,3.86 mmol) was stirred under air at 120℃for 3 hours. Then, the mixture was concentrated and used as CH 2 Cl 2 /Et 2 O mixed solution (4 mL/8 mL. Times.2), et 2 O (10 mL. Times.1) was washed.Drying was performed under vacuum, whereby compound 2 was isolated as a white solid in 2.58g (3.20 mmol,84% yield). 1 H NNR(CDCl 3 )：δ10.13(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)， 31 P NMR(CDCl 3 )：δ81.7(s)，80.7(s)，-135.1～-152.7(m)。
Synthesis of Compound 3
The synthesis of compound 3 is shown below. Compound 3 (2.58 g,3.20 mmol) and tris (dimethylamino) phosphine (1.5 mL) were stirred in dichloromethane (40 mL) under nitrogen at room temperature for 4 hours. Then, concentration was performed and washed with toluene (7 ml×3), and dried under vacuum, whereby compound 3 was isolated as a white solid in 1.66g (2.56 mmol,80% yield). 1 H NNR(CDCl 3 )：δ9.81(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)， 31 P NMR(CDCl 3 )：δ25.9(s)，25.1(s)，-139.4～-152.6(m)。
Synthesis of molybdenum Complex (3 d)
The synthesis of the molybdenum complex (3 d) is shown below. Compound 3 (1.30 g,2.00 mmol) and potassium bis (trimethylsilyl) amide (560 mg,2.81 mmol) were stirred in toluene (45 mL) under argon at room temperature for 1 hour. Then, after filtration using celite, moCl was added 3 (thf) 3 (756 mg,1.81 mmol) was stirred at 80℃for 26 hours. The reaction solution was concentrated up to 5mL, filtered using filter paper and dried under vacuum to solidify. The resulting solid was washed with toluene (5 mL. Times.2) and dissolved in CH 2 Cl 2 (20 mL) and filtered using celite. Hexane (30 mL) was slowly added to the filtrate and left to stand for 5 days to give brown crystals. The supernatant was removed, washed with hexane (5 mL. Times.3), and dried under vacuum to isolate molybdenum complex (3 d) as brown crystals at 381mg (0.54 mmol,30% yield). Anal calcd.for C 26 H 43 N 2 F 3 P 2 Cl 3 Mo·1/2CH 2 Cl 2 ：C，42.59；H，5.93；N，3.75Found：C，42.79；H，5.74；N，3.91。
The molybdenum complex (3 c) used in experimental example 40 can be synthesized by using 1, 2-diamino-4, 5-difluorobenzene instead 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 large scale. In a 1000mL four-necked flask, the molybdenum complex (3 a) (0.100 mmol,63.8 mg) and SmI were placed in a flask 2 (thf) 2 (solid crystals, 36.0mmol,19.7g, 360 eq. To molybdenum) in THF (270 mL) was added and after stirring under a nitrogen stream at room temperature, a THF solution (20 mL) of water (36.0 mmol, 360 eq. To molybdenum) was stirred with a mechanical stirrer (220 rpm) and then stirred at room temperature for 8 minutes. The reaction solution was concentrated, dried and solidified by an evaporator. To the resulting solid was added an aqueous potassium hydroxide solution (30% by mass, 20 mL), and the mixture was distilled under reduced pressure, and the distillate was recovered with an aqueous solution (about 10 mL) of 96% concentrated sulfuric acid (5.04 mmol,515 mg). The recovered aqueous solution was concentrated using an evaporator and dried under vacuum overnight. As a result, as 668mg (5.06 mmol,84% yield), there was obtained (NH) 4 ) 2 SO 4 Is a white solid. This corresponds to the formation of 101 equivalents of ammonia relative to the catalyst (molybdenum complex). Anal calcd.forH 8 N 2 O 4 S：H，6.10；N，21.20Found：H，6.06；N，20.98。
Further, examples 1 to 19 and 22 to 42 correspond to examples of the present application, and examples 20 and 21 correspond to comparative examples.
The present application is based on claims priority from japanese patent application No. 2018-36967 filed on 3 months 1 and japanese patent application No. 2018-158595 filed on 27 months 8, 2018, which are incorporated by reference in their entirety.
Industrial applicability
The present application can be used for the production of ammonia.
Claims (11)
1. A process for producing ammonia from nitrogen molecules in the presence of a catalyst, a reducing agent and a proton source,
the catalyst is (A) a molybdenum complex having 2, 6-bis (dialkylphosphinomethyl) pyridine as PNP ligand, (B) a molybdenum complex having N, N-bis (dialkylphosphinomethyl) benzimidazole carbene as PCP ligand, (C) a molybdenum complex having bis (dialkylphosphinoethyl) arylphosphine as PPP ligand, or (D) trans-Mo (N) 2 ) 2 (R 1 R 2 R 3 P) 4 Molybdenum complex compounds represented, wherein 2 alkyl groups in the 2, 6-bis (dialkylphosphinomethyl) pyridine are the same or different, at least 1 hydrogen atom of the pyridine ring is substituted or not substituted by an alkyl group, an alkoxy group or a halogen atom, 2 alkyl groups in the N, N-bis (dialkylphosphinomethyl) benzimidazole carbene are the same or different, at least 1 hydrogen atom of the benzene ring is substituted or not substituted by an alkyl group, an alkoxy group or a halogen atom, or is not substituted by an alkyl group, an alkoxy group or a halogen atom, 2 alkyl groups in the bis (dialkylphosphinoethyl) arylphosphine are the same or different, and trans-Mo (N 2 ) 2 (R 1 R 2 R 3 P) 4 Wherein R is 1 、R 2 、R 3 Are the same or different alkyl or aryl groups, 2R 3 Are linked to each other to form an alkylene chain or are not linked to each other to form an alkylene chain,
as the 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 represented by the following formula (A1), (A2) or (A3),
wherein R is 1 And R is 2 And X is an iodine atom, a bromine atom or a chlorine atom, and at least 1 hydrogen atom on the pyridine ring is substituted with an alkyl group, an alkoxy group or a halogen atom or is not substituted with an alkyl group, an alkoxy group or a halogen atom.
3. The method for producing ammonia according to claim 1, wherein the molybdenum complex compound represented by the following formula (B1),
wherein R is 1 And R is 2 And X is an iodine atom, a bromine atom or a chlorine atom, and at least 1 hydrogen atom on the benzene ring is substituted with an alkyl group, an alkoxy group or a halogen atom or is not substituted with 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 represented by the formula (C1),
wherein R is 1 And R is 2 R are identical or different alkyl radicals 3 Is aryl, X is iodine atom, bromine atom or chlorine atom.
6. The method for producing ammonia according to claim 1, wherein the molybdenum complex compound represented by the formula (D1) or (D2),
wherein R is 1 、R 2 And R is 3 Are identical or different alkyl or aryl groups, n being 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 molecule.
8. The method for producing ammonia according to any one of claims 1 to 6, wherein the alcohol is a diol or ROH, and R is a chain, cyclic or branched alkyl group having 1 to 6 carbon atoms, in which a hydrogen atom is substituted or unsubstituted with a fluorine atom, or a phenyl group having an alkyl group or not having an alkyl group.
9. The method for producing ammonia according to any one of claims 1 to 6, wherein the halide (II) of a lanthanide metal is samarium (II) halide.
10. A molybdenum complex compound represented by the formula (B2),
wherein R is 1 And R is 2 Is the same or different alkyl, X is an iodine atom, a bromine atom or a chlorine atom, R 3 And R is 4 At least one of which is substituted by trifluoromethyl.
11. A benzimidazole compound represented by the formula (E),
wherein A is an anion, R 1 And R is 2 R are identical or different alkyl radicals 3 And R is 4 At least one of which is substituted by 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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