CN113087667A - Synthesis method of imidazolidinone derivative - Google Patents
Synthesis method of imidazolidinone derivative Download PDFInfo
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- CN113087667A CN113087667A CN202110314112.4A CN202110314112A CN113087667A CN 113087667 A CN113087667 A CN 113087667A CN 202110314112 A CN202110314112 A CN 202110314112A CN 113087667 A CN113087667 A CN 113087667A
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- 150000008624 imidazolidinones Chemical class 0.000 title claims description 6
- 238000001308 synthesis method Methods 0.000 title abstract description 7
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical class O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- -1 amidine compound Chemical class 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000010189 synthetic method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 38
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 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 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 4
- 239000003049 inorganic solvent Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005059 halophenyl group Chemical group 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 239000011147 inorganic material Substances 0.000 claims description 2
- 125000006303 iodophenyl group Chemical group 0.000 claims description 2
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 2
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 57
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 239000003208 petroleum Substances 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 238000004809 thin layer chromatography Methods 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000005526 G1 to G0 transition Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 8
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- LZCZIHQBSCVGRD-UHFFFAOYSA-N benzenecarboximidamide;hydron;chloride Chemical compound [Cl-].NC(=[NH2+])C1=CC=CC=C1 LZCZIHQBSCVGRD-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- RXAOGVQDNBYURA-UHFFFAOYSA-N (4-chlorobenzenecarboximidoyl)azanium;chloride Chemical compound Cl.NC(=N)C1=CC=C(Cl)C=C1 RXAOGVQDNBYURA-UHFFFAOYSA-N 0.000 description 1
- HBMWQILXZYMGKB-UHFFFAOYSA-N 1-(8-fluoro-1,3,4,5-tetrahydropyrido[4,3-b]indol-2-yl)ethanone Chemical compound N1C2=CC=C(F)C=C2C2=C1CCN(C(=O)C)C2 HBMWQILXZYMGKB-UHFFFAOYSA-N 0.000 description 1
- CFCNTIFLYGKEIO-UHFFFAOYSA-N 2-isocyanoacetic acid Chemical compound OC(=O)C[N+]#[C-] CFCNTIFLYGKEIO-UHFFFAOYSA-N 0.000 description 1
- JQDATBKJKUWNGA-UHFFFAOYSA-N 4-fluorobenzenecarboximidamide;hydrochloride Chemical compound Cl.NC(=N)C1=CC=C(F)C=C1 JQDATBKJKUWNGA-UHFFFAOYSA-N 0.000 description 1
- AJOSDIDPIBJFAI-UHFFFAOYSA-N 4-methoxybenzenecarboximidamide;hydrochloride Chemical compound Cl.COC1=CC=C(C(N)=N)C=C1 AJOSDIDPIBJFAI-UHFFFAOYSA-N 0.000 description 1
- VRJJZMJUNZRSLS-UHFFFAOYSA-N Cl.N1=CC(=CC=C1)C1=CC=CC=C1C(=N)N Chemical compound Cl.N1=CC(=CC=C1)C1=CC=CC=C1C(=N)N VRJJZMJUNZRSLS-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002143 encouraging effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006452 multicomponent reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- XLMFDCKSFJWJTP-UHFFFAOYSA-N pentane-2,3-diol Chemical compound CCC(O)C(C)O XLMFDCKSFJWJTP-UHFFFAOYSA-N 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/70—One oxygen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthetic method of an imidazolinone derivative. The amidine compound and the polyalcohol compound are used as raw materials, the cobalt catalyst is used for catalyzing the high value of the polyalcohol to be converted into a series of imidazolone derivatives, a novel and green synthetic path which accords with the sustainable chemical principle is developed, the high value conversion of renewable resources is realized, and the synthetic requirement of the imidazolone derivatives is met. The synthesis method has the advantages of wide substrate applicability, good functional group compatibility, use of recyclable cheap metal catalyst and use of air as an oxidant, has the potential to prepare the imidazolone derivatives in one step on a large scale, and also provides an important way for converting biomass resources into high-value functional molecules.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthetic method of an imidazolidinone derivative.
Background
The imidazolone compounds are nitrogen-containing heterocyclic compounds with good biological activity and pharmacological activity, are widely present in natural active products, and play an important role in human health and industrial and agricultural production. Many imidazolinone fungicides, herbicides, natural drugs, and the like have been found.
The construction of imidazolinone derivatives has been an attractive topic for the scientific community due to their encouraging properties. The conventional methods in the related art for imidazolinone functional molecules involve the following reactions: (1) cyclization reaction of diamide compounds; (2) cyclizing condensation reaction of amino ester and cyanamide; (3) intermolecular condensation cyclization reaction of 1, 3-dicarbonyl compound and guanidine; (4) pd catalyzed multicomponent reaction of isocyanoacetate with an amine. Although the synthesis method has the advantages of easily available raw materials and low price, the synthesis method needs to be carried out under the conditions of high temperature and high pressure, has higher requirements on equipment, and has the obvious defects of complicated steps, low yield, large amount of waste water and waste residue generated in the production process, serious environmental pollution and the like.
Therefore, it is necessary to develop a synthetic method of the imidazolidinone derivative; the method has high yield and is environment-friendly.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a method for synthesizing chiral beta-aryl substituted carboxylic acid derivatives, which has good selectivity and higher product yield.
In order to achieve the purpose, the invention adopts the technical scheme that: a synthetic method of an imidazolinone derivative comprises the following steps: : the method comprises the following steps: in a solvent, reacting a polyalcohol compound and an amidine compound in a cobalt catalyst and an alkaline substance to obtain the imidazolone derivative;
the structure of the polyalcohol compound is shown as the following formula compound I;
the structure of the ether compound is shown as a compound II in the following formula;
the structure of the imidazolone derivative is shown as a compound III in the following formula;
wherein R is1And R2Each is independently selected from one of alkyl, aryl and hydrogen;
R1and R2The same or different;
R1and R2Can form a ring;
R3one selected from the group consisting of alkyl, alkoxy, aryl, trifluoromethyl, amino, halogen and hydrogen.
According to some embodiments of the invention, the R is1Is selected from C1～C12Alkyl groups of (a); preferably, said R is1One selected from the group consisting of methyl, ethyl, propyl, n-butyl, and n-nonyl; preferably, said R is1Is selected from C6～C12Aryl of (a); more preferably, said R1One selected from phenyl and benzyl.
According to some embodiments of the invention, the R is2Is selected from C1～C12Alkyl groups of (a); preferably, said R is2One selected from the group consisting of methyl, ethyl, propyl, n-butyl, and n-nonyl; preferably, said R is2Is selected from C6～C12Aryl of (a); more preferably, said R2One selected from phenyl and benzyl.
According to some embodiments of the invention, the R is3Is selected from C1～C12One of alkyl, aryl and aryl derivatives of (a); preferably, said R is3One selected from the group consisting of pyridyl, phenyl and benzyl; preferably, said R is3Selected from methoxyphenyl; preferably, said R is3Selected from cyclopropane.
According to some embodiments of the invention, the R is3Selected from the group consisting of halophenyl; more preferably, the halogenated phenyl group includes one of a fluorinated phenyl group, a chlorinated phenyl group, a brominated phenyl group and an iodophenyl group.
According to some embodiments of the invention, the molar ratio of the polyol compound to the amidine compound is 1 to 10: 1.
the excessive polyol is beneficial to the reaction and improves the reaction yield.
According to some embodiments of the invention, the temperature of the reaction is between 25 ℃ and 130 ℃.
According to some embodiments of the invention, the reaction time is between 1h and 24 h.
According to some embodiments of the invention, the cobalt catalyst comprises a nanocobalt catalyst.
The cobalt catalyst has the advantage of being easily separated from the product and can be recycled for many times.
According to some embodiments of the invention, the nanocobalt catalyst comprises nanocobalt supported on an inorganic material.
According to some embodiments of the present invention, the inorganic material-supported nanocobalt includes at least one of alumina-supported nanocobalt, titania-supported nanocobalt, zinc oxide-supported nanocobalt, activated carbon-supported nanocobalt, and manganese oxide-supported nanocobalt.
According to some embodiments of the invention, the molar ratio of the polyol compound to the cobalt catalyst is 1: 0.02-0.08.
The catalyst in proper proportion can improve the reaction yield, and the yield is reduced due to over-high or over-low of the catalyst.
According to some embodiments of the invention, the alkaline substance comprises at least one of an organic alkaline substance and an inorganic alkaline substance.
According to some embodiments of the invention, the organic basic substance comprises at least one of a sodium alkoxide and an amine.
According to some embodiments of the invention, the sodium alkoxide comprises at least one of sodium methoxide, sodium tert-butoxide, and potassium tert-butoxide.
According to some embodiments of the invention, the amine comprises triethylamine.
According to some embodiments of the invention, the inorganic basic substance comprises at least one of an alkali metal hydroxide and a carbonate.
According to some embodiments of the invention, the alkali metal hydroxide comprises at least one of sodium hydroxide, cesium hydroxide and potassium hydroxide.
According to some embodiments of the invention, the carbonate salt comprises at least one of potassium carbonate, sodium carbonate and cesium carbonate.
According to some embodiments of the invention, the solvent comprises at least one of an organic solvent and an inorganic solvent.
According to some embodiments of the invention, the organic solvent comprises at least one of a nitrile solvent, an amide solvent, an ether solvent, a pyridine solvent, an alcohol solvent, and an aromatic hydrocarbon solvent.
According to some embodiments of the invention, the nitrile solvent comprises acetonitrile.
According to some embodiments of the invention, the amide-based solvent comprises at least one of N-methylformamide, formamide, N-ethylformamide, and N, N-dimethylformamide.
According to some embodiments of the invention, the ethereal solvent comprises tetrahydrofuran.
According to some embodiments of the invention, the pyridine-based solvent comprises pyridine.
According to some embodiments of the invention, the alcoholic solvent comprises at least one of tert-amyl alcohol, isopropyl alcohol, isobutyl alcohol and methanol.
According to some embodiments of the invention, the aromatic hydrocarbon solvent comprises at least one of toluene and para-xylene.
According to some embodiments of the invention, the inorganic solvent comprises water.
According to some embodiments of the invention, the volume ratio of the solvent to the polyol compound is 1 to 2: 1.
according to some embodiments of the invention, the synthesis method further comprises the steps of: and after the reaction is finished, removing the solvent and purifying to obtain the imidazolone derivative.
According to some embodiments of the invention, the method of purification is thin layer chromatography.
According to some embodiments of the present invention, the stationary phase used in the thin layer chromatography is silica gel, the eluent used in the thin layer chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is petroleum ether: the ethyl acetate is (0.5-50): 1.
The method for synthesizing the imidazolidinone derivative according to the embodiment of the present invention has at least the following beneficial effects: the method takes amidine compounds and polyalcohol compounds as raw materials, obtains the imidazolone derivatives through the high-value conversion of the polyalcohol under the action of a cobalt catalyst, develops a novel and green synthetic path which accords with the sustainable chemical principle, realizes the high-value conversion of renewable resources, and meets the synthetic requirements of the imidazolone derivatives; has great application prospect in the industry of preparing the imidazolone derivative on a large scale.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a product obtained in the first embodiment of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of a product obtained in the first embodiment of the present invention;
FIG. 3 is a NMR chart of a product obtained in example two of the present invention;
FIG. 4 is the NMR spectrum of the product obtained in example two of the present invention;
FIG. 5 is the NMR spectrum of the product obtained in example III of the present invention;
FIG. 6 is the NMR spectrum of the product obtained in example III of the present invention;
FIG. 7 is a NMR spectrum of a product obtained in example four of the present invention;
FIG. 8 is the NMR spectrum of the product obtained in example four of the present invention;
FIG. 9 is the NMR spectrum of the product obtained in example five of the present invention;
FIG. 10 is the NMR spectrum of the product obtained in example V of the present invention;
FIG. 11 is a NMR spectrum of a product obtained in example VI of the present invention;
FIG. 12 is a NMR spectrum of a product obtained in example six of the present invention;
FIG. 13 is a NMR chart of a product obtained in example VII of the present invention;
FIG. 14 is a NMR spectrum of a product obtained in example VII of the present invention;
FIG. 15 is a NMR spectrum of a product obtained in example VIII of the present invention;
FIG. 16 is the NMR spectrum of the product obtained in example eight of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The preparation method of the cobalt nano catalyst comprises the following steps: first, 5.89g of KMnO4, 8.8g of MnSO4, 100mL of water, 3mL of concentrated nitric acid were added to a 250mL round bottom flask and refluxed at 100 ℃ for 24 hours. Filtering and washing to obtain black solid. A second step; a250 mL round-bottomed flask was charged with 50mg of cobalt chloride, 700mg of the previously prepared black solid, and 30mL of water, and the mixture was stirred for 1 hour. The pH of the mixture was adjusted to 13 by adding sodium hydroxide solution, followed by centrifugation and drying. Calcining the obtained mixture in a tubular furnace at 800 ℃ for 4h to obtain the carbon material-supported cobalt nano catalyst, and preparing the cobalt catalyst supported by other materials in the same way.
The first embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
after 0.25 mmol of benzamidine hydrochloride, 0.375 mmol of 1, 2-cyclohexanediol, 0.6 mmol of cesium carbonate, 60mg of cobalt metal catalyst supported on activated carbon (mass fraction of activated carbon: 3%) and 1 ml of pyridine were added to a schlenk tube (schlenk tube), and the mixture was stirred at 130 ℃ under air for 12 hours, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure, followed by separation and purification by thin layer chromatography using silica gel as a stationary phase and a mixed solvent of petroleum ether and ethyl acetate as an eluent (petroleum ether: ethyl acetate: 5:1, v/v), to obtain the desired product in 89% yield.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the first embodiment of the invention are respectively shown in fig. 1 and fig. 2, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ7.98(d,J＝7.0Hz,2H),7.59-7.46(m,3H),2.05(m,8H).
13C NMR(126MHz,CDCl3):δ190.88,157.94,131.77,128.94,128.63,127.00,78.76,37.66,26.26.
IR(KBr):3053,1674,1556,1471,1345,763,695cm-1.
MS(EI,m/z):214.10[M]+.
from the above data, it is concluded that the structure of the product of example one of the present invention is shown in the following formula:
the second embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
adding 0.25 mmol of 4-methoxybenzamidine hydrochloride, 0.45 mmol of 1,2 cyclohexanediol, 0.5 mmol of potassium hydroxide, 45 mg of aluminum oxide supported cobalt metal catalyst (the mass fraction of aluminum oxide is 3%) and 1 ml of tert-amyl alcohol into a schlenk tube, stirring and reacting for 12 hours at 110 ℃ under air conditions, stopping heating and stirring, cooling to room temperature, carrying out reduced pressure rotary evaporation to remove the solvent, and separating and purifying by thin-layer chromatography to obtain the target product, wherein the stationary phase of the thin-layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 5:1, v/v), and the yield of the obtained product is 84%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the second embodiment of the invention are respectively shown in fig. 3 and 4, and the structural characterization data are as follows:
1H NMR(500MHz,DMSO):δ7.95(d,J＝8.7Hz,2H),7.07(d,J＝8.8Hz,2H),3.83(s,3H),3.44(s,1H),1.92–1.80(m,6H),1.75(m,2H).
13C NMR(126MHz,DMSO):δ190.66,162.62,130.09,129.54,121.35,114.57,76.03,55.90,37.60,25.95.
IR(KBr):2917，1712，1613，1435，1251，839，754cm-1.
MS(EI,m/z):244.10[M]+.
from the above data, it is concluded that the structure of the product obtained in example two of the present invention is shown in the following formula:
the third embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
0.25 mmol of 4-fluoro benzamidine hydrochloride, 0.5 mmol of 1,2 cyclohexanediol, 0.5 mmol of sodium methoxide, 60mg of titanium dioxide supported nano cobalt catalyst (the mass fraction of titanium dioxide is 3%) and 1 ml of methanol are added into a schlenk tube, after stirring and reacting for 10 hours under the condition of air at 120 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, the solvent is removed by reduced pressure rotary evaporation, and then the mixture is separated and purified by thin layer chromatography, the target product is obtained, the stationary phase of the thin layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 7:1, v/v), and the yield of the product is 83%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the third embodiment of the invention are respectively shown in fig. 5 and 6, and the structural characterization data are as follows:
1H NMR(500MHz,DMSO):δ8.04(s,2H),7.37(t,J＝7.8Hz,2H),1.80(m,8H).
13C NMR(126MHz,DMSO):δ189.53,164.62(d,J＝250Hz),130.11(d,J＝7.6Hz),125.70,116.44,116.32(d,J＝22.0Hz),76.80,37.53,25.95.
IR(KBr):3746，2872，2357，1703，1441，1290，851，664cm-1.
HRMS(ESI):Calcd.for C13H13FN2O[M+39]+:271.0643；found:271.0643.
according to the above data, the structure of the product obtained in the third embodiment of the present invention is deduced to be shown as the following formula:
the fourth embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
after 0.25 mmol of 3-pyridinebenzamidine hydrochloride, 60mg of activated carbon-supported nanocobalt catalyst (the mass fraction of activated carbon is 3%), 0.375 mmol of 1,2 pentanediol, 0.3 mmol of triethylamine and 10 hours are added into a schlenk tube, heating and stirring are stopped, the mixture is cooled to room temperature, the solvent is removed by reduced pressure rotary evaporation, and then the mixture is separated and purified by thin-layer chromatography to obtain the target product, wherein the stationary phase of the thin-layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate is 3:1, v/v), and the yield of the obtained product is 87%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the fourth embodiment of the invention are respectively shown in fig. 7 and 8, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ9.22(s,1H),8.80(d,J＝4.2Hz,1H),8.35(d,J＝8.0Hz,1H),7.49(dd,J＝7.8,4.9Hz,1H),2.10(m,4H),2.04-1.93(m,4H).
13C NMR(126MHz,CDCl3):δ190.49,155.80,152.27,148.06,134.72,125.02,123.86,78.92,37.69,26.25.
IR(KBr):3441，2929，1709，1450，1089，706cm-1.
MS(EI,m/z):215.10[M]+.
from the above data, it is concluded that the structure of the product obtained in example four of the present invention is shown in the following formula:
the fifth embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
0.25 mmol of benzamidine hydrochloride, 0.375 mmol of 2, 3-butanediol, 0.5 mmol of potassium tert-butoxide, 60mg of activated carbon-supported cobalt catalyst (the mass fraction of activated carbon is 3%) and 1 ml of pyridine are added into a schlenk tube, and after stirring and reacting for 10 hours at 130 ℃ under air conditions, heating and stirring are stopped, the mixture is cooled to room temperature, the solvent is removed by rotary evaporation under reduced pressure, and then the mixture is separated and purified by thin-layer chromatography, wherein the stationary phase of the thin-layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 8:1, v/v), and the yield of the product is 65%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the fifth embodiment of the invention are respectively shown in fig. 9 and fig. 10, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ7.99(d,J＝7.3Hz,2H),7.52(d,J＝7.6Hz,3H),1.50(s,6H)；
13C NMR(126MHz,CDCl3):δ190.69,158.39,132.02,128.98,128.38,127.07,69.07,24.02；
IR(KBr):3755，2923，2854，2369，1727，1459，1296，703；
MS(EI,m/z):188.10[M]+.
from the above data, it is concluded that the structure of the product obtained in example five of the present invention is shown in the following formula:
the sixth embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
0.25 mmol of benzamidine hydrochloride, 0.375 mmol of 1, 2-diphenyl-1, 2-diol, 0.25 mmol of potassium hydroxide, 60mg of cobalt catalyst and 1 ml of pyridine are added into a schlenk tube, after stirring and reacting for 12 hours under air conditions at 130 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, the solvent is removed by reduced pressure rotary evaporation, and then the mixture is separated and purified by thin layer chromatography, so that the target product is obtained, wherein the stationary phase of the thin layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 6:1, v/v), and the yield of the target product is 85%.
The hydrogen spectrum and the carbon spectrum of the obtained product are respectively shown in fig. 11 and fig. 12, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ8.06–8.03(m,2H),7.62–7.57(m,4H),7.55(ddd,J＝6.5,3.7,1.2Hz,1H),7.51-7.47(m,2H),7.35-7.30(m,4H),7.29-7.25(m,2H).
13C NMR(126MHz,CDCl3):δ186.17,140.15,132.27,128.98,128.52,128.15,128.05,127.89,127.39,127.29,79.59.
IR(KBr):3435,2923,1712,1619,1459,1251,766,694.
MS(EI,m/z):312.10[M]+.
the structure of the obtained product is deduced according to the data as shown in the following formula:
the seventh embodiment of the invention is: a synthetic method of an imidazolinone derivative comprises the following steps:
0.25 mmol of cyclopropyl amidine hydrochloride, 0.375 mmol of 2, 3-butanediol, 0.75 mmol of potassium carbonate, 60mg of manganese dioxide-supported cobalt catalyst (the mass fraction of manganese dioxide is 3%) and 1 ml of N, N-dimethylformamide are added into a schlenk tube, and after stirring and reacting for 12 hours under air conditions at 120 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, the solvent is removed by rotary evaporation under reduced pressure, and then the mixture is separated and purified by thin-layer chromatography, so that the target product is obtained, wherein the stationary phase of the thin-layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 6:1, v/v), and the yield of the product is 68%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the seventh embodiment of the invention are respectively shown in fig. 13 and 14, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ1.82–1.73(m,1H),1.35(s,6H),1.20–1.12(m,2H),1.12–1.03(m,2H).
13C NMR(126MHz,CDCl3):δ191.16,157.62,66.39,23.88,10.66,8.61.
IR(KBr):3749，3152，2962，2357，1685，1492，1303，649.
MS(EI,m/z):152.10[M]+.
from the above data, it is concluded that the product obtained in example seven of the present invention has the following structure:
the eighth embodiment of the present invention is: a synthetic method of an imidazolinone derivative comprises the following steps:
after 0.25 mmol of 4-chlorobenzamidine hydrochloride, 0.5 mmol of pentane-2, 3-diol, 0.5 mmol of sodium hydroxide, 60mg of zinc oxide-supported cobalt catalyst (the mass fraction of zinc oxide is 3%) and 1.5 ml of pyridine were added to a schlenk tube, and the mixture was stirred at 120 ℃ under air for 12 hours, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure, followed by separation and purification by thin layer chromatography using silica gel as a stationary phase and a mixed solvent of petroleum ether and ethyl acetate as an eluent (petroleum ether: ethyl acetate: 4:1, v/v), to obtain a yield of the desired product of 72%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the example eight of the invention are respectively shown in fig. 15 and 16, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ7.95(d,J＝8.5Hz,2H),7.52(d,J＝8.5Hz,2H),1.93(d,J＝7.4Hz,2H),1.47(s,3H),0.85(d,J＝7.4Hz,3H).
13C NMR(126MHz,CDCl3):δ189.86,162.81,138.38,129.36,128.42,126.63,72.97,30.91,22.87,8.23.
IR(KBr):3737，2917，2363，1712，1584，1438，1107，851，586.
HRMS(ESI):Calcd.for C12H13ClN2O[M+1]+:237.0789；found:237.0787.
according to the above data, the structure of the product obtained in the eighth embodiment of the present invention is deduced to be shown as the following formula:
in conclusion, the amidine compound and the polyalcohol compound are used as raw materials, the cobalt catalyst is used for catalyzing the high value of the polyalcohol to be converted into a series of imidazolone derivatives, a novel and green synthetic path which accords with the sustainable chemical principle is developed, the high value conversion of renewable resources is realized, and the synthetic requirement of the imidazolone derivatives is met. The synthesis method has the advantages of wide substrate applicability, good functional group compatibility, use of recyclable cheap metal catalyst and use of air as an oxidant, has the potential to prepare the imidazolone derivatives in one step on a large scale, and also provides an important way for converting biomass resources into high-value functional molecules.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
While the embodiments of the present invention have been described in detail with reference to the description and the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A synthetic method of an imidazolidinone derivative is characterized by comprising the following steps: the method comprises the following steps: in a solvent, reacting a polyalcohol compound and an amidine compound in a cobalt catalyst and an alkaline substance to obtain the imidazolone derivative;
the structure of the polyalcohol compound is shown as the following formula compound I;
the structure of the ether compound is shown as a compound II in the following formula;
the structure of the imidazolone derivative is shown as a compound III in the following formula;
wherein R is1And R2Each is independently selected from one of alkyl, aryl and hydrogen;
R1and R2The same or different;
R1and R2Can form a ring;
R3one selected from the group consisting of alkyl, alkoxy, aryl, trifluoromethyl, amino, halogen and hydrogen.
2. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the R is1Is selected from C1～C12Alkyl or C6～C12Aryl of (a); preferably, said R is2One selected from the group consisting of methyl, ethyl, propyl, n-butyl, n-nonyl, phenyl and benzyl.
3. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the R is2Is selected from C1～C12Alkyl or C6～C12OfA group; preferably, said R is2One selected from the group consisting of methyl, ethyl, propyl, n-butyl, n-nonyl, phenyl and benzyl.
4. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the R is3Is selected from C1～C12One of alkyl, aryl and aryl derivatives of (a); preferably, said R is3One selected from the group consisting of a cyclopropane group, a pyridyl group, a substituted or unsubstituted phenyl group and a benzyl group; preferably, the substituted phenyl is selected from methoxyphenyl or halophenyl; more preferably, the halogenated phenyl group includes one of a fluorinated phenyl group, a chlorinated phenyl group, a brominated phenyl group and an iodophenyl group.
5. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the molar ratio of the polyalcohol compound to the amidine compound is 1-10: 1.
6. the method of claim 1, wherein the imidazolinone derivative is synthesized by: the reaction temperature is 25-130 ℃; preferably, the reaction time is 1-24 h.
7. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the cobalt catalyst comprises a nanocobalt catalyst; preferably, the nanocobalt catalyst comprises nanocobalt supported on an inorganic material; more preferably, the inorganic material-supported nanocobalt includes at least one of alumina-supported nanocobalt, titania-supported nanocobalt, zinc oxide-supported nanocobalt, activated carbon-supported nanocobalt, and manganese oxide-supported nanocobalt.
8. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the molar ratio of the cobalt catalyst to the polyol compound is 0.02-0.08: 1.
9. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the alkaline substance comprises at least one of an organic alkaline substance and an inorganic alkaline substance; preferably, the organic basic substance includes at least one of sodium alkoxide and amine; more preferably, the sodium alkoxide includes at least one of sodium methoxide, sodium tert-butoxide, and potassium tert-butoxide; more preferably, the amine comprises triethylamine; further preferably, the inorganic basic substance includes at least one of an alkali metal hydroxide and a carbonate; still further preferably, the alkali metal hydroxide comprises at least one of sodium hydroxide, cesium hydroxide and potassium hydroxide; still further preferably, the carbonate includes at least one of potassium carbonate, sodium carbonate, and cesium carbonate.
10. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the solvent comprises at least one of an organic solvent and an inorganic solvent; preferably, the organic solvent includes at least one of a nitrile solvent, an amide solvent, an ether solvent, a pyridine solvent, an alcohol solvent, and an aromatic hydrocarbon solvent; more preferably, the nitrile based solvent comprises acetonitrile; more preferably, the amide-based solvent includes at least one of N-methylformamide, formamide, N-ethylformamide, and N, N-dimethylformamide; more preferably, the ethereal solvent comprises tetrahydrofuran; more preferably, the pyridine-based solvent includes pyridine; more preferably, the alcoholic solvent includes at least one of t-amyl alcohol, isopropyl alcohol, isobutyl alcohol, and methanol; more preferably, the aromatic hydrocarbon solvent includes at least one of toluene and p-xylene; further preferably, the inorganic solvent comprises water.
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