CN113680389A - 一种多齿β-二亚胺配体稀土金属催化剂及其制备方法和应用 - Google Patents
一种多齿β-二亚胺配体稀土金属催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN113680389A CN113680389A CN202110960306.1A CN202110960306A CN113680389A CN 113680389 A CN113680389 A CN 113680389A CN 202110960306 A CN202110960306 A CN 202110960306A CN 113680389 A CN113680389 A CN 113680389A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- rare earth
- earth metal
- metal catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 239000003446 ligand Substances 0.000 title claims abstract description 75
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 69
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 62
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- -1 rare earth metal ions Chemical class 0.000 claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 24
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 22
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 17
- 150000001420 substituted heterocyclic compounds Chemical class 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 39
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 20
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000007363 ring formation reaction Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 125000006657 (C1-C10) hydrocarbyl group Chemical group 0.000 claims description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 125000003554 tetrahydropyrrolyl group Chemical group 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- CPPGZWWUPFWALU-UHFFFAOYSA-N 1-isocyanato-3-methylbenzene Chemical compound CC1=CC=CC(N=C=O)=C1 CPPGZWWUPFWALU-UHFFFAOYSA-N 0.000 claims description 2
- FMDGXCSMDZMDHZ-UHFFFAOYSA-N 1-isocyanato-4-methoxybenzene Chemical compound COC1=CC=C(N=C=O)C=C1 FMDGXCSMDZMDHZ-UHFFFAOYSA-N 0.000 claims description 2
- GFNKTLQTQSALEJ-UHFFFAOYSA-N 1-isocyanato-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(N=C=O)C=C1 GFNKTLQTQSALEJ-UHFFFAOYSA-N 0.000 claims description 2
- MGOLNIXAPIAKFM-UHFFFAOYSA-N 2-isocyanato-2-methylpropane Chemical compound CC(C)(C)N=C=O MGOLNIXAPIAKFM-UHFFFAOYSA-N 0.000 claims description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 2
- VAYMIYBJLRRIFR-UHFFFAOYSA-N 2-tolyl isocyanate Chemical compound CC1=CC=CC=C1N=C=O VAYMIYBJLRRIFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- PTMBWNZJOQBTBK-UHFFFAOYSA-N pyridin-4-ylmethanol Chemical compound OCC1=CC=NC=C1 PTMBWNZJOQBTBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 2
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical class O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 33
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- 229910052769 Ytterbium Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052765 Lutetium Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical group CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WRXNJTBODVGDRY-UHFFFAOYSA-N 2-pyrrolidin-1-ylethanamine Chemical compound NCCN1CCCC1 WRXNJTBODVGDRY-UHFFFAOYSA-N 0.000 description 1
- HVLUYXIJZLDNIS-UHFFFAOYSA-N 2-thiophen-2-ylethanamine Chemical compound NCCC1=CC=CS1 HVLUYXIJZLDNIS-UHFFFAOYSA-N 0.000 description 1
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000001773 anti-convulsant effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000002365 anti-tubercular Effects 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 229960003965 antiepileptics Drugs 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- HEZQRPHEDDAJTF-UHFFFAOYSA-N chloro(phenyl)methanol Chemical compound OC(Cl)C1=CC=CC=C1 HEZQRPHEDDAJTF-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 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
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- RWIVICVCHVMHMU-UHFFFAOYSA-N n-aminoethylmorpholine Chemical compound NCCN1CCOCC1 RWIVICVCHVMHMU-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940005483 opioid analgesics Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229940002612 prodrug Drugs 0.000 description 1
- 239000000651 prodrug Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Images
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
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three 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
- C07D263/36—One oxygen atom
- C07D263/38—One oxygen atom attached in position 2
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/36—Yttrium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
技术领域
本发明涉及稀土金属催化剂,具体地,涉及一种多齿β-二亚胺配体稀土金属催化剂及其制备方法和应用。
背景技术
胺基甲酸酯作为一类重要的有机官能团,在多种生物以及药理活性分子的合成中的应用非常广泛,如农药杀菌剂、杀虫剂、类阿片类药物,同时也被用作组合化学中间体以及药物前体的离去基团。并且,胺基甲酸酯类官能团在抗肿瘤药物中普遍存在。氨基甲酸酯类化合物的合成反应主要是在催化剂或者助催化剂的存在下进行的,例如过渡金属催化剂(参照文献“Ricard,S.;Gagnon,A.;Daoust,B.ChemistrySelect 2018,3(17),4923-4929”)、碱、酸以及Lewis酸(参照文献“Ricard,S.;Gagnon,A.;Daoust,B.ChemistrySelect 2018,3(17),4923-4929”),上述催化剂虽然能够合成胺基甲酸酯类化合物,但是存在使用催化剂量大且难以分离产物的缺陷。
2-噁唑烷酮是一类重要的杂环化合物,它作为多用途中间体、手性助剂、生物活性化合物等,同时被广泛应用于农业、工业、医药等领域。2-噁唑烷酮因其众多生物活性如抗菌、消炎、抗真菌、抗惊厥、抗癌及抗结核从而受到广泛关注。合成2-噁唑烷酮的方法又很多,例如通过碱催化胺基甲酸酯成环(参照文献“Ziane,S.;Mazari,M.M.;Safer,A.M.;SadEl Hachemi Amar,A.;Ruchaud,S.;Baratte,B.;Bach,S.Russian Journal of OrganicChemistry 2019,55(7),1061-1069”)、过渡金属催化(参照文献“Yamada,T.;Sekine,K.;Mawatari,T.Synlett 2015,26(17),2447-2450”)和微波辐照(参照文献“Merino,O.;Santoyo,B.M.;Montiel,L.E.;Jiménez-Vázquez,H.A.;Zepeda,L.G.;Tamariz,J.Tetrahedron Letters 2010,51(29),3738-3742”)等,上述方法虽然能够合成2-噁唑烷酮类化合物,但是存在反应温度过高且催化剂在有机溶剂中难溶。
发明内容
本发明的目的是提供一种多齿β-二亚胺配体稀土金属催化剂及其制备方法和应用,以解决现有技术中胺基甲酸酯类化合物、2-噁唑烷酮类化合物的制备过程中存在的使用催化剂量大且难以分离产物以及催化反应温度高的缺陷。
为了实现上述目的,本发明提供了一种多齿β-二亚胺配体稀土金属催化剂,所述多齿β-二亚胺配体稀土金属催化剂的结构如式A或式B所示,
其中,RE为稀土金属离子,式C所示结构的化合物Het表示C4以上的杂环化合物或取代杂环化合物(化合物Het可以为饱和的杂环化合物,也可以为不饱和的杂环化合物,均在本发明的保护范围内;同样需要强调的是,该式代表的杂原子个数也不受到限定,如可以是多个,如两个,多个杂原子可以相同也可以不同),X为杂原子,Y为C或杂原子,n和m各自独立地为正整数;R1、R2、R3、R4、R5各自独立地选自H、C1-C30的烃基或C1-C30的取代烃基。
本发明还提供了一种如上述的多齿β-二亚胺配体稀土金属催化剂的制备方法,所述制备方法为:在保护气的存在下,将如式D或式E所示结构的配体、如式F所示结构的稀土三烷基配合物进行配位反应,以制得所述多齿β-二亚胺配体稀土金属催化剂;
其中,RE为稀土金属离子,式C所示结构的化合物Het表示C4以上的杂环化合物或取代杂环化合物,X为杂原子,Y为C或杂原子,n和m各自独立地为正整数;R1、R2、R3、R4、R5各自独立地选自H、C1-C30的烃基或C1-C30的取代烃基。
其中,如式D所示结构的配体、如式F所示结构的稀土三烷基配合物反应后生成的为如式A所示的多齿β-二亚胺配体稀土金属催化剂;如式D所示结构的配体、如式F所示结构的稀土三烷基配合物生成的为如式B所示的多齿β-二亚胺配体稀土金属催化剂。
本发明进一步提供了一种根据上述的多齿β-二亚胺配体稀土金属催化剂在制备如式J所示结构的胺基甲酸酯类化合物或如式M所示结构的2-噁唑烷酮类化合物中的应用;其中,所述胺基甲酸酯类化合物通过如式K所示结构的异氰酸酯类化合物与如式L所示结构的醇化合物在所述多齿β-二亚胺配体稀土金属催化剂的催化下进行加成反应而得,所述2-噁唑烷酮类化合物通过如式N所示结构的酯类化合物在所述多齿β-二亚胺配体稀土金属催化剂的催化下进行环化反应而得;
其中,所述R6、R7、R8各自独立地选自H、C1-C30的烃基或C1-C30的取代烃基。
在上述技术方案中,本发明通过将如式D或式E所示结构的配体、如式F所示结构的稀土三烷基配合物进行配位反应,制得如式A或式B所示结构的多齿β-二亚胺配体稀土金属催化剂,该多齿β-二亚胺配体稀土金属催化剂能在温和的条件下,高效催化异氰酸酯类与醇类化合物的加成反应生成胺基甲酸酯类化合物,也能进一步环化合成2-噁唑烷酮类化合物;该催化剂具有用量少、催化活性和催化效率高、绿色环保和催化条件温和的特点
另外,制备多齿β-二亚胺配体及稀土金属催化剂的方法具有合成步骤简单、条件温和、原料廉价易得的优点。
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本发明的进一步理解,并且构成说明书的一部分,与下面的具体实施方式一起用于解释本发明,但并不构成对本发明的限制。在附图中:
图1是实施例1中金属催化剂A1的单晶衍射图;
图2是实施例1中金属催化剂A1的核磁共振氢谱;
图3是实施例1中金属催化剂A1的核磁共振碳谱;
图4是实施例2中金属催化剂A2的单晶衍射图;
图5是实施例3中金属催化剂A3的单晶衍射图;
图6是实施例3中金属催化剂A3的核磁共振氢谱;
图7是实施例3中金属催化剂A3的核磁共振碳谱;
图8是实施例4中金属催化剂A4的单晶衍射图;
图9是实施例5中金属催化剂A5的单晶衍射图;
图10是实施例5中金属催化剂A5的核磁共振氢谱;
图11是实施例5中金属催化剂A5的核磁共振碳谱;
图12是实施例6中金属催化剂A6的单晶衍射图;
图13是实施例7中金属催化剂A7的单晶衍射图;
图14是实施例7中金属催化剂A7的核磁共振氢谱;
图15是实施例7中金属催化剂A7的核磁共振碳谱;
图16是实施例8中金属催化剂B1的单晶衍射图;
图17是实施例8中金属催化剂B1的核磁共振氢谱;
图18是实施例8中金属催化剂B1的核磁共振碳谱;
图19是实施例9中金属催化剂B2的单晶衍射图;
图20是实施例10中金属催化剂B3的单晶衍射图。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
本发明提供了一种多齿β-二亚胺配体稀土金属催化剂,所述多齿β-二亚胺配体稀土金属催化剂的结构如式A或式B所示,
其中,RE为稀土金属离子,式C所示结构的化合物Het表示C4以上的杂环化合物或取代杂环化合物,X为杂原子,Y为C或杂原子,n和m各自独立地为正整数;R1、R2、R3、R4、R5各自独立地选自H、C1-C30的烃基或C1-C30的取代烃基。
在本发明中,n表示碳链的长度,对n的具体数值不作限定,如可以为1-10,但是考虑到合成难度,优选地,n为1-3的正整数。
在本发明中,m表示碳链的长度,对m的具体数值不作限定,如可以为1-10,但是考虑到合成难度,优选地,m为1-2的正整数。
在本发明中,对所述RE的具体种类不作要求,但是为了得到更多种类的催化剂,优选地,所述RE选自Y3+、Yb3+、Gd3+、Er3+或Lu3+。
在本发明中,对所述化合物Het的具体种类不作要求,但是为了得到更多种类的催化剂,优选地,所述化合物Het为五元杂环化合物或六元杂环化合物,所述X选自S、N或O,Y选自C、S、N或O;其中,五元杂环化合物和六元杂环化合物上可以存在取代基,如2-甲基噻吩,对此并不作限定。从合成难度和原料的获取难度上考虑,更优选地,所述化合物Het选自四氢吡咯、噻吩、吗啉或吲哚。
在本发明中,对所述R1、R2、R3、R4、R5的的具体种类不作限定,但是从催化剂的制备难度上考虑,优选地,所述R1、R2、R3、R4、R5各自独立地选自H、C1-C10的烃基或C1-C10的取代烃基;更优选地,所述R1、R2、R3、R4、R5各自独立地选自H、甲基、乙基或异丙基。
在上述诸多实施方式的基础上,为了进一步便于得到所述多齿β-二亚胺配体稀土金属催化剂,优选地,所述多齿β-二亚胺配体稀土金属催化剂的结构如式A1、式A2或式B1所示;
本发明还提供了一种如上述的多齿β-二亚胺配体稀土金属催化剂的制备方法,所述制备方法为:在保护气的存在下,将如式D或式E所示结构的配体、如式F所示结构的稀土三烷基配合物进行配位反应,以制得所述多齿β-二亚胺配体稀土金属催化剂;
其中,RE为稀土金属离子,式C所示结构的化合物Het表示C4以上的杂环化合物或取代杂环化合物,X为杂原子,Y为C或杂原子,n和m各自独立地为正整数;R1、R2、R3、R4、R5各自独立地选自H、C1-C30的烃基或C1-C30的取代烃基。
在上述制备方法中,n表示碳链的长度,对n的具体数值不作限定,如可以为1-10,但是考虑到制备难度,优选地,n为1-3的正整数。
在本发明中,m表示碳链的长度,对m的具体数值不作限定,如可以为1-10,但是考虑到合成难度,优选地,m为1-2的正整数。
在上述制备方法中,对所述RE的具体种类不作要求,但是为从产率上考虑,优选地,所述RE选自Y3+、Yb3+、Gd3+、Er3+或Lu3+。
在上述制备方法中,对所述化合物Het的具体种类不作要求,但是为从产率上考虑,优选地,所述化合物Het为五元杂环化合物或六元杂环化合物,所述X选自S、N或O,Y选自C、S、N或O;其中,五元杂环化合物和六元杂环化合物上可以存在取代基,如2-甲基噻吩,对此并不作限定。从合成难度和原料的获取难度上考虑,更优选地,所述化合物Het选自四氢吡咯、噻吩、吗啉或吲哚。
在上述制备方法中,对所述R1、R2、R3、R4、R5的的具体种类不作限定,但是为从产率上考虑,优选地,所述R1、R2、R3、R4、R5各自独立地选自H、C1-C10的烃基或C1-C10的取代烃基;更优选地,所述R1、R2、R3、R4、R5各自独立地选自H、甲基、乙基或异丙基。
在上述诸多实施方式的基础上,为了进一步提高产率,优选地,所述配体的结构如式D1、式D2或式D3所示;所述稀土三烷基配合物为如式E1所示,
此外,在本发明中,对所述配体、所述稀土三烷基配合物的用量也不作具体限定,但是为了进一步保证反应物尽可能地完全反应,优选地,所述配体、所述稀土三烷基配合物的用量摩尔比为1:(1-1.1)。
同时,在本发明中,对所述配位反应的条件也不作具体限定,但是为了进一步保证反应物尽可能地完全反应,优选地,所述配位反应至少满足以下条件:反应温度为15-35℃,反应时间为6-18h。
此外,在上述方法中,为了进一步提高产率,优选地,所述配位反应于溶剂中进行,所述溶剂选自甲苯或正己烷。其中,所述溶剂的用量也可宽的范围内选择,但是为了进一步提高产率,所述稀土三烷基配合物、所述配体的用量比为1mmol:5-10mL。
在上述制备方法中,对所述保护气的种类也不作具体限定,但是为了进一步提高保护效果,优选地,所述保护气选自氮气、氦气和氩气中的至少一种。
在上述制备方法中,所述配体可以为市售品,也可以是现制现用,但是为了进一步提高所述配体的纯度,优选地,所述配体通过以下方法制备而得:以对甲苯磺酸为催化剂,将酮类化合物与胺类化合物于溶剂中进行接触反应,所述胺类化合物的结构如式H或式I所示,所述酮类化合物的结构如式G所示;
在上述配体的制备方法中,对各原料的用量不作具体限定,但是为了提高产率,优选地,所述酮类化合物、胺类化合物、对甲苯磺酸的用量摩尔比为10:(10-13):(0.3-0.4)。
在上述配体的制备方法中,对所述接触反应的条件不作具体限定,但是为了提高产率,优选地,所述接触反应至少满足以下条件:于150-200℃下回流反应4-30h。
在上述配体的制备方法中,对溶剂的用量和种类不作具体限定,但是为了提高产率,优选地,所述酮类化合物、溶剂的用量比为10mmoL:10-30mL,其中,所述溶剂选自甲苯、二甲苯、环己醇和N,N-二甲基甲酰胺中的至少一种。
本发明进一步提供了一种根据上述的多齿β-二亚胺配体稀土金属催化剂在制备如式J所示结构的胺基甲酸酯类化合物或如式M所示结构的2-噁唑烷酮类化合物中的应用;其中,所述胺基甲酸酯类化合物通过如式K所示结构的异氰酸酯类化合物与如式L所示结构的醇化合物在所述多齿β-二亚胺配体稀土金属催化剂的催化下进行加成反应而得,所述2-噁唑烷酮类化合物通过如式N所示结构的酯类化合物在所述多齿β-二亚胺配体稀土金属催化剂的催化下进行环化反应而得;
其中,所述R6、R7、R8各自独立地选自H、C1-C30的烃基或C1-C30的取代烃基。
在上述应用中,对所述R6、R7、R8的种类不作具体限定,但是从产率上考虑,优选地,所述R6、R7、R8各自独立地选自H、苯基、对甲基苯基、对氯苯基、对甲氧基和对溴苯基中的至少一种;更优选地,所述异氰酸酯类化合物选自苯基异氰酸酯、2-甲基苯基异氰酸酯、3-甲基苯基异氰酸酯、4-甲基苯基异氰酸酯、4-甲氧基苯基异氰酸酯、4-硝基苯基异氰酸酯、叔丁基异氰酸酯和环己基异氰酸酯中的至少一种,所述醇化合物选自苯甲醇、对溴基苯甲醇、对氯基苯甲醇、对甲基苯甲醇、2-苯乙醇、4-吡啶基甲醇、呋喃甲醇中的至少一种;所述酯类化合物选自如式N1、式N2、式N3和式N4结构化合物中的至少一种;进一步优选地,所述胺基甲酸酯类化合物的结构如式J1、式J2、式J3或式J4所示,所述2-噁唑烷酮类化合物的结构如式M1、式M2、式M3或式M4所示,
在上述加成反应中,对各原料的用量也不作具体限定,但是为了进一步提高产率,优选地,在所述加成反应中,所述异氰酸酯类化合物、醇化合物、所述多齿β-二亚胺配体稀土金属催化剂的用量摩尔比为1.0mmoL:(0.8-1.2mmoL):(0.3×10-3-0.5×10-3mmoL)。
在上述加成反应中,对反应条件也不作具体限定,但是为了进一步提高产率,优选地,所述加成反应至少满足以下条件:反应温度为15-35℃,反应时间为5-10min;
在上述环化反应中,对原料的用量也不作具体限定,但是为了进一步提高产率,优选地,在所述环化反应中,所述酯类化合物、所述多齿β-二亚胺配体稀土金属催化剂的用量摩尔比为1.0mmoL:(0.008-0.015mmoL)。
在上述环化反应中,对反应条件也不作具体限定,但是为了进一步提高产率,优选地,所述环化反应至少满足以下条件:反应温度为110-120℃,反应时间为2-3h。
以下将通过实例对本发明进行详细描述。以下实例中,核磁氢谱和核磁碳谱是通过瑞士Bruker AV400和Bruker AV 500MHz核磁共振仪测得,单晶衍射图谱通过Bruker AXS单晶衍射仪SMART APEXⅡ测得,高分辨质谱数据使用Agilent 6220-TOF质谱仪测得。
各个制备例中的配体前体均按照文献Zhu,X.;Li,Y.;Guo,D.;Wang,S.;Wei,Y.;Zhou,S.,Versatile reactivities of rare-earth metal dialkyl complexessupported by a neutral pyrrolyl-functionalized beta-diketiminatoligand.Dalton Trans 2018,47(11),3947-3957.中记载的方法制备而得。
制备例1
配体D1的制备:
将配体前体1(2.59g,10mmoL)与1-(2-氨乙基)吡咯烷(1.48g,13mmoL)溶于20mL甲苯中,完毕后加入0.3mmoL对甲苯磺酸,170℃下回流反应5小时,减压蒸馏反应液收取185℃的馏分,得到黄色油状物,称重3.02g,产率85%。
表征结果如下:1H NMR(400MHz,CDCl3)δ10.85(s,1H),7.26(s,1H),7.10(d,J=7.2Hz,2H),7.01(dd,J=6.8,6.8Hz,1H),4.64(s,1H),3.36(d,J=7.2Hz,2H),2.87(dt,J=13.6,6.8Hz,2H),2.60–2.42(m,8H),2.02(s,3H),1.61(s,3H),1.14(dd,J=18.4,6.8Hz).
13C NMR(126MHz,CDCl3)δ166.3,155.7,147.4,138.4,123.0,122.8,93.4,57.0,54.8,43.1,28.4,24.2,23.8,23.1,21.9,19.8.
HRMS(ESI):calcd for C23H37N3[M+H]+355.5700,found 355.5695.
制备例2
配体D2的制备:
将配体前体2(2.59g,10mmoL)与N-(2-氨乙基)吗啉(1.69g,13mmoL)溶于20mL甲苯中,完毕后加入0.3mmoL对甲苯磺酸,170℃下回流反应24小时,减压蒸馏反应液收取180℃的馏分,再用适量正己烷重结晶得到黄色晶体,称重2.92g,产率75%。
表征结果如下:1H NMR(400MHz,CDCl3)δ10.85(s,1H),7.12(d,J=7.6Hz,2H),7.03(dd,J=8.0,6.8Hz,1H),4.66(s,1H),3.77–3.71(m,1H),3.65–3.57(m,5H),3.38(dd,J=11.5,6.0Hz,2H),2.89(dt,J=14.0,6.8Hz,2H),2.49(t,J=6.8Hz,3H),2.46–2.41(m,4H),2.04(s,3H),1.64(s,4H),1.16(dd,J=14.8,6.8Hz,14H).
13C NMR(126MHz,CDCl3)δ166.04,155.18,147.07,137.98,122.69,93.28,66.92,59.10,53.87,40.53,28.11,23.91,22.91,21.70,19.67.
HRMS(ESI):calcd for C22H34N2O[M+H]+371.2937,found 371.2942.
制备例3
配体D3的制备
将配体前体3(2.59g,10mmoL)与2-噻吩乙胺(1.36g,12mmoL)溶于20mL甲苯中,完毕后加入0.3mmoL对甲苯磺酸,170℃下回流反应24小时,减压蒸馏反应液收取180℃的馏分,得到黄色油状物,称重2.84g,产率80%。
表征结果如下:1H NMR(500MHz,CDCl3,ppm):δ11.00(s,1H),7.11-7.09(m,3H),7.03-7.00(m,1H),6.86-6.8(dd,J=5.0,3.5Hz,1H),6.79(d,J=3.5Hz,1H),4.64(s,1H),3.49(t,J=7.0Hz,2H),3.00(t,J=7.0Hz,2H),2.88(sept,J=7.0Hz,2H),1.92(s,3H),1.63(s,3H),1.16(d,J=7.0Hz,6H),1.12(d,J=7.0Hz,6H).
13C NMR(125MHz,C6D6,ppm):δ166.6,155.4,147.4,141.6,138.4,127.2,125.7,124.0,123.6,123.4,94.2,45.1,32.0,28.6,24.3,23.3,21.9,19.1.
HRMS(ESI):calcd for C23H32O2S[M+H]+369.2359,found 369.2352.
实施例1
稀土金属催化剂A1的制备:
将配体D1(0.35g,1.0mmoL)与钇三烷基配合物(0.50g,1.0mmoL)混合与5mL正己烷中,25℃下反应12小时,抽真空除去溶剂,浓缩到2mL,25℃下下静置,得到黄色晶体0.37g,产率75%。
表征结果如下:1H NMR(500MHz,C6D6)δ7.14(t,J=4.5Hz,4H),4.88(s,1H),3.35–3.19(m,4H),2.89(t,J=5.5Hz,2H),2.37(t,J=5.5Hz,2H),1.85(dd,J=7.5,5.0Hz,2H),1.77(dd,J=5.0,2.0Hz,2H),1.68(s,3H),1.63(s,3H),1.42(d,J=7.0Hz,6H),1.36(dd,J=7.5,3.5Hz,2H),1.16(d,J=7.0Hz,6H),0.25–0.04(m,18H),-0.63(dd,J=11.5,3.0Hz,2H),-0.94(dd,J=11.5,3.0Hz,2H).
13C NMR(126MHz,C6D6)δ165.8,165.7,144.9,142.7,126.0,124.4,98.0,55.7,53.7,48.5,35.7,35.4,28.2,25.5,24.7,24.1,23.1,22.7,4.5.
Anal.Calcdfor C31H58N3Si2Y:C,60.26;H,9.46;N,6.80.Found:C,59.64;H,9.74;N,6.72.单晶衍射图见图1,核磁共振氢谱图见图2,核磁共振碳谱图见图3。
实施例2
稀土金属催化剂A2的制备:
将配体D1(0.35g,1.0mmoL)与镱三烷基配合物(0.50g,1.0mmoL)混合与5mL正己烷中,25℃下反应12小时,抽真空除去溶剂,浓缩到2mL,25℃下静置,得到红色晶体0.53g,产率76%。
表征数据如下:Anal.Calcdfor C31H58N3Si2Yb:C,53.04;H,8.33;N,5.99.Found:C,52.78;H,8.24;N,6.14.
单晶衍射图见图4。
实施例3
稀土金属催化剂A3的制备:
将配体D1(0.35g,1.0mmoL)与镥三烷基配合物(0.50g,1.0mmoL)混合与5mL正己烷中,25℃下反应12小时,抽真空除去溶剂,浓缩到2mL,25℃下静置,得到红色晶体0.48g,产率68%。
表征数据如下:1H NMR(500MHz,C6D6)δ7.15(dd,J=16.5,5.5Hz,4H),4.87(s,1H),3.56–3.11(m,4H),2.90(t,J=5.5Hz,2H),2.31(t,J=5.5Hz,2H),1.90(dd,J=11.0,5.5Hz,2H),1.82–1.51(m,9H),1.39(t,J=22.0Hz,9H),1.15(d,J=6.5Hz,6H),0.14(s,19H),-0.87(d,J=11.0Hz,2H),-1.11(d,J=11.0Hz,2H).
13C NMR(126MHz,C6D6)δ166.4,166.3,145.8,142.7,126.0,124.4,98.5,55.1,53.6,48.6,42.7,28.1,25.4,24.9,24.4,23.0,22.8,4.8.
Anal.Calcdfor C31H58N3Si2Lu:C,52.89;H,8.30;N,5.97.Found:C,52.94;H,8.55;N,6.12.
单晶衍射图见图5,核磁共振氢谱图见图6,核磁共振碳谱图见图7。
实施例4
稀土金属催化剂A4的制备:
将配体D1(0.35g,1.0mmoL)与钆三烷基配合物(0.50g,1.0mmoL)混合与5mL正己烷中,25℃下反应12小时,抽真空除去溶剂,浓缩到2mL,25℃下静置,得到红色晶体0.53g,产率77%
表征数据如下:Anal.Calcdfor C31H58N3Si2Gd:C,54.26;H,8.52;N,6.12.Found:C,54.19;H,8.70;N,6.17.
单晶衍射图见图8。
实施例5
稀土金属催化剂A5的制备:
将配体D2(0.39g,1.0mmoL)与钇三烷基配合物(0.50g,1.0mmoL)混合与5mL正己烷中,25℃下反应12小时,抽真空除去溶剂,浓缩到3mL,25℃下下静置,得到黄色晶体0.36g,产率72%。
表征结果如下:1H NMR(500MHz,C6D6)δ7.22–7.04(m,3H),4.88(s,1H),3.91(t,J=10.5Hz,2H),3.57(d,J=12.0Hz,2H),3.32–3.14(m,2H),3.03(d,J=12.0Hz,2H),2.83(t,J=5.5Hz,2H),2.33(s,2H),1.86(t,J=10.0Hz,2H),1.63(d,J=3.5Hz,7H),1.40(d,J=7.0Hz,6H),1.15(d,J=6.8Hz,8H),0.10(d,J=3.4Hz,18H),-0.56(d,J=11.5Hz,2H),-0.76(dd,J=11.6,2.6Hz,2H).
13C NMR(126MHz,C6D6)δ166.09,165.30,144.98,142.62,126.13,124.47,98.25,64.72,55.83,52.81,45.53,37.84,37.52,28.28,25.48,24.68,24.16,22.55,4.48.
Anal.Calcdfor C31H58N3OSi2Y:C,58.74;H,9.22;N,6.63.Found:C,58.48;H,9.31;N,6.77.
单晶衍射图见图9,核磁共振氢谱图见图10,核磁共振碳谱图见图11。
实施例6
稀土金属催化剂A6的制备:
将配体D2(0.39g,1.0mmoL)与镱三烷基配合物(0.50g,1.0mmoL)混合与5mL正己烷中,25℃下反应12小时,抽真空除去溶剂,浓缩到3mL,25℃下下静置,得到黄色晶体0.54g,产率75%。
表征数据如下:Anal.Calcdfor C31H58N3OSi2Yb:C,51.85;H,8.14;N,5.85.Found:C,51.54;H,8.25;N,5.76.
单晶衍射图见图12。
实施例7
稀土金属催化剂A7的制备:
将配体D2(0.39g,1.0mmoL)与镥三烷基配合物(0.50g,1.0mmoL)混合与5mL正己烷中,25℃下反应12小时,抽真空除去溶剂,浓缩到3mL,25℃下下静置,得到黄色晶体0.49g,产率69%。
表征结果如下:1H NMR(500MHz,C6D6)δ7.23–7.02(m,10H),4.87(s,1H),3.85(t,J=9.7Hz,2H),3.60–3.42(m,2H),3.36–3.17(m,2H),3.09(d,J=12.0Hz,2H),2.85(t,J=5.7Hz,2H),2.30(s,2H),1.95(dd,J=15.3,6.0Hz,2H),1.62(s,6H),1.41(d,J=6.8Hz,6H),1.30–1.04(m,7H),0.85(t,J=7.0Hz,1H),0.10(d,J=3.1Hz,18H),-0.77(d,J=11.8Hz,2H),-0.94(d,J=11.9Hz,2H).
13C NMR(126MHz,C6D6)δ166.78,165.94,145.72,142.70,126.15,124.46,98.75,64.06,54.52,52.49,45.63,44.72,28.16,25.40,24.80,24.49,22.59,4.72.
Anal.Calcdfor C31H58N3OSi2Lu:C,51.72;H,8.12;N,5.84.Found:C,51.60;H,8.23;N,5.84.
单晶衍射图见图13,核磁共振氢谱图见图14,核磁共振碳谱图见图15。
实施例8
稀土金属催化剂B1的制备:
将配体D3(0.61g,1.0mmoL)与钇三烷基配合物(0.50g,1.0mmoL)混合与15mL甲苯中,25℃下反应12小时,真空除去溶剂,加入2mL甲苯和5mL正己烷混合提取,25℃下下静置,得到黄色晶体0.33g,产率54%。
表征结果如下:1H NMR(500MHz,C6D6,ppm):δ7.25(d,J=4.5Hz,1H),6.96-6.87(m,3H),6.77(d,J=4.5Hz,1H),4.95(s,1H),4.36(s,1H),3.84(s,1H),3.30-2.73(m,8H),1.84(s,3H),1.48(s,3H,),1.20-1.04(m,10H),0.77-0.74(m,6H),0.32(s,9H),–0.51(s,1H),–0.64(s,1H).
13C NMR(125MHz,C6D6,ppm):δ177.7,166.5,162.8,151.0,145.1,141.8,134.8,126.3,124.5,121.1,99.5,69.6,49.1,35.1,34.2,27.9,25.2,23.9,21.2,4.2.
Anal.Calcd for C31H49N2OSSiY:C,60.56;H,8.03;N,4.56.Found:C,60.24;H,7.97;N,4.58.
单晶衍射图见图16,核磁共振氢谱图见图17,核磁共振碳谱图见图18。
实施例9
稀土金属催化剂B2的制备:
将配体D3(0.61g,1.0mmoL)与镱三烷基配合物(0.50g,1.0mmoL)混合与15mL甲苯中,25℃下反应12小时,真空除去溶剂,加入2mL甲苯和5mL正己烷混合提取,25℃下下静置,得到黄色晶体0.21g,产率63%。
表征数据如下:Anal.Calcd for C31H49N2OSSiYb:C,53.27;H,7.07;N,4.01.Found:C,52.80;H,7.26;N,3.94.
单晶衍射图见图19。
实施例10
稀土金属催化剂B3的制备:
将配体D3(0.61g,1.0mmoL)与铒三烷基配合物(0.50g,1.0mmoL)混合与15mL甲苯中,25℃下反应12小时,真空除去溶剂,加入2mL甲苯和5mL正己烷混合提取,25℃下下静置,得到黄色晶体0.45g,产率65%。
表征数据如下:Anal.Calcd for C31H49N2OSSiEr:C,53.72;H,7.13;N,4.04.Found:C,53.28;H,6.92;N,4.38.
单晶衍射图见图20。
应用例1
在氩气保护以及25℃下,在15mL的反应瓶中加入异氰酸酯类化合物(底物1,1.0mmoL)和醇类化合物化合物(底物2,1.0mmoL),混合后加入稀土金属配合物(0.4×10- 3mmoL),搅拌10min,反应结束后用正己烷洗涤,干燥至恒重,液体产物可通过柱层析分离纯化得到,流动相为乙酸乙酯:石油醚=1:10;具体原料和产物结果见表1。
表1
应用例2
在氩气保护以及25℃下,在15mL的反应瓶中加入稀土金属催化剂(0.01mmoL),用0.3ml甲苯溶解后加入胺基甲酸酯化合物化合物(底物,1.0mmoL),在115℃下搅拌2h,反应结束后用正己烷洗涤,干燥至恒重;具体结果见表2。
表2
比较例1
在氩气保护以及25℃下,在15mL的反应瓶中加入表1中序号1中的底物1和底物2各1.0mmoL,搅拌1小时,表征后显示无表1中序号1的产物。
比较例2
在氩气保护以及25℃下,在15mL的反应瓶中加入表2中序号1中的底物(1.0mmoL),用0.3ml甲苯溶解后,在115℃下搅拌2.5h,表征后显示无表2中序号1的产物。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。
Claims (10)
2.根据权利要求1所述的多齿β-二亚胺配体稀土金属催化,其中,所述RE选自Y3+、Yb3+、Gd3+、Er3+或Lu3+;所述化合物Het为五元杂环化合物或六元杂环化合物,所述X选自S、N或O,Y选自C、S、N或O;n为1-3的正整数,m为1-2的正整数;所述R1、R2、R3、R4、R5各自独立地选自H、C1-C10的烃基或C1-C10的取代烃基。
6.根据权利要求4或5所述的制备方法,其中,所述配体、所述稀土三烷基配合物的用量摩尔比为1:(1-1.1);
优选地,所述配位反应至少满足以下条件:反应温度为15-35℃,反应时间为6-18h;
优选地,所述配位反应于溶剂中进行,所述溶剂选自甲苯或正己烷;
优选地,所述保护气选自氮气、氦气和氩气中的至少一种。
9.根据权利要求8所述的应用,其中,所述R6、R7、R8各自独立地选自H、苯基、对甲基苯基、对氯苯基、对甲氧基和对溴苯基中的至少一种;
优选地,所述异氰酸酯类化合物选自苯基异氰酸酯、2-甲基苯基异氰酸酯、3-甲基苯基异氰酸酯、4-甲基苯基异氰酸酯、4-甲氧基苯基异氰酸酯、4-硝基苯基异氰酸酯、叔丁基异氰酸酯和环己基异氰酸酯中的至少一种,所述醇化合物选自苯甲醇、对溴基苯甲醇、对氯基苯甲醇、对甲基苯甲醇、2-苯乙醇、4-吡啶基甲醇、呋喃甲醇中的至少一种;所述酯类化合物选自如式N1、式N2、式N3和式N4结构化合物中的至少一种;
优选地,所述胺基甲酸酯类化合物的结构如式J1、式J2、式J3或式J4所示,所述2-噁唑烷酮类化合物的结构如式M1、式M2、式M3或式M4所示,
10.根据权利要求8所述的应用,其中,在所述加成反应中,所述异氰酸酯类化合物、醇化合物、所述多齿β-二亚胺配体稀土金属催化剂的用量摩尔比为1.0mmoL:(0.8-1.2mmoL):(0.3×10-3-0.5×10-3mmoL);
优选地,所述加成反应至少满足以下条件:反应温度为15-35℃,反应时间为5-10min;
优选地,在所述环化反应中,所述酯类化合物、所述多齿β-二亚胺配体稀土金属催化剂的用量摩尔比为1.0mmoL:(0.008-0.015mmoL);
优选地,所述环化反应至少满足以下条件:反应温度为110-120℃,反应时间为2-3h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110960306.1A CN113680389B (zh) | 2021-08-20 | 2021-08-20 | 一种多齿β-二亚胺配体稀土金属催化剂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110960306.1A CN113680389B (zh) | 2021-08-20 | 2021-08-20 | 一种多齿β-二亚胺配体稀土金属催化剂及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113680389A true CN113680389A (zh) | 2021-11-23 |
CN113680389B CN113680389B (zh) | 2023-09-05 |
Family
ID=78580999
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110960306.1A Active CN113680389B (zh) | 2021-08-20 | 2021-08-20 | 一种多齿β-二亚胺配体稀土金属催化剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113680389B (zh) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101186617A (zh) * | 2007-11-23 | 2008-05-28 | 中国科学院上海有机化学研究所 | 含氮配体稀土催化剂及在聚酯合成中的应用 |
US20100173075A1 (en) * | 2008-08-05 | 2010-07-08 | Air Products And Chemicals, Inc. | High Coordination Sphere Group 2 Metal B-Diketiminate Precursors |
CN102380419A (zh) * | 2011-09-15 | 2012-03-21 | 安徽师范大学 | 用于合成羟基磷酸酯的催化剂、制备及其使用方法 |
CN103936793A (zh) * | 2013-01-10 | 2014-07-23 | 光明创新(武汉)有限公司 | 含卡宾配体的催化剂及其制备方法与其在复分解反应中的应用 |
CN104031596A (zh) * | 2014-06-27 | 2014-09-10 | 重庆中科力泰高分子材料股份有限公司 | 一种低成型温度水性聚氨酯胶粘剂及其制备方法 |
CN105637003A (zh) * | 2013-10-15 | 2016-06-01 | 路博润先进材料公司 | 用无锡催化剂制备的热塑性聚氨酯 |
CN108570065A (zh) * | 2016-06-30 | 2018-09-25 | 苏州大学张家港工业技术研究院 | 基于β–二亚胺基二价稀土硼氢配合物合成硼酸酯的方法 |
US20200165282A1 (en) * | 2017-06-21 | 2020-05-28 | Instituto Superior Técnico | Tridentate iminopyrrolyl nickel complexes and their use as catalysts for the reaction of polymerisation of ethylene to hyperbranched polyethylene |
-
2021
- 2021-08-20 CN CN202110960306.1A patent/CN113680389B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101186617A (zh) * | 2007-11-23 | 2008-05-28 | 中国科学院上海有机化学研究所 | 含氮配体稀土催化剂及在聚酯合成中的应用 |
US20100173075A1 (en) * | 2008-08-05 | 2010-07-08 | Air Products And Chemicals, Inc. | High Coordination Sphere Group 2 Metal B-Diketiminate Precursors |
CN102380419A (zh) * | 2011-09-15 | 2012-03-21 | 安徽师范大学 | 用于合成羟基磷酸酯的催化剂、制备及其使用方法 |
CN103936793A (zh) * | 2013-01-10 | 2014-07-23 | 光明创新(武汉)有限公司 | 含卡宾配体的催化剂及其制备方法与其在复分解反应中的应用 |
CN105637003A (zh) * | 2013-10-15 | 2016-06-01 | 路博润先进材料公司 | 用无锡催化剂制备的热塑性聚氨酯 |
CN104031596A (zh) * | 2014-06-27 | 2014-09-10 | 重庆中科力泰高分子材料股份有限公司 | 一种低成型温度水性聚氨酯胶粘剂及其制备方法 |
CN108570065A (zh) * | 2016-06-30 | 2018-09-25 | 苏州大学张家港工业技术研究院 | 基于β–二亚胺基二价稀土硼氢配合物合成硼酸酯的方法 |
US20200165282A1 (en) * | 2017-06-21 | 2020-05-28 | Instituto Superior Técnico | Tridentate iminopyrrolyl nickel complexes and their use as catalysts for the reaction of polymerisation of ethylene to hyperbranched polyethylene |
Non-Patent Citations (1)
Title |
---|
XIANCUI ZHU等: "Versatile reactivities of rare-earth metal dialkyl complexes supported by a neutral pyrrolylfunctionalizedβ-diketiminato ligand", 《DALTON TRANS.》, vol. 47, pages 3947 * |
Also Published As
Publication number | Publication date |
---|---|
CN113680389B (zh) | 2023-09-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Ley et al. | A polymer-supported [1, 3, 2] oxazaphospholidine for the conversion of isothiocyanates to isocyanides and their subsequent use in an Ugi reaction | |
Dong et al. | 2, 4, 6-Trihydroxybenzoic acid-catalyzed oxidative Ugi reactions with molecular oxygen via homo-and cross-coupling of amines | |
Suntrup et al. | Copper (I) complexes bearing mesoionic carbene ligands: influencing the activity in catalytic halo-click reactions | |
CN109012748B (zh) | 吡啶取代吡咯基稀土金属催化剂及其制备方法和应用 | |
Janus et al. | Chiral protic imidazolium salts with a (−)-menthol fragment in the cation: synthesis, properties and use in the Diels–Alder reaction | |
Pan et al. | Enantioselective Synthesis of Chiral Amides by a Phosphoric Acid Catalyzed Asymmetric Wolff Rearrangement | |
CN113444024A (zh) | 无催化剂无溶剂合成多取代脲类、硫脲类和手性脲类、硫脲类化合物的方法 | |
CN113680389B (zh) | 一种多齿β-二亚胺配体稀土金属催化剂及其制备方法和应用 | |
Kumar et al. | Phosphomolybdic acid-Al2O3: A mild, efficient, heterogeneous and reusable catalyst for regioselective opening of oxiranes with amines to β-amino alcohols | |
Shinde et al. | N-Arylation of ferrocenyl 2, 4-thiazolidinedione conjugates via a copper-catalysed Chan–Lam cross coupling reaction with aryl boronic acids and their optoelectronic properties | |
CN114835652B (zh) | 一种光催化条件下合成亚胺基苯并三唑类化合物的方法 | |
Durham et al. | Ruthenium-catalyzed [2+ 2] cycloaddition reactions of a 2-oxa-3-azabicyclo [2.2. 1] hept-5-ene with unsymmetrical alkynes | |
CN103748065B (zh) | 2-烯基胺化合物的制造方法 | |
CN107868087B (zh) | 一种制备吡咯并吲哚类衍生物的方法 | |
JP2021191734A (ja) | 尿素誘導体の製造方法 | |
CN101486673B (zh) | 一种光学活性2-(2-硝基-乙基)-吡咯的合成方法 | |
CN107573276B (zh) | 一种3-乙基-5-羟基-1,3-二芳基吲哚酮的合成方法 | |
CN111440198A (zh) | 1,10a-二氢-2H-吡啶[1,2-d][1,4]硫氮卓类化合物及其制备方法 | |
CN110759845B (zh) | 一种1,2,3,5-四取代氮杂茂化合物的微波合成方法 | |
CN117677597A (zh) | 在Mn-PNN络合物的存在下将酯氢化为醇 | |
US8901336B2 (en) | Catalysts, methods of making catalysts, and methods of use | |
WO2012040853A1 (en) | Group 5 metal complexes useful for amine functionalization and synthetic process for manufacture thereof | |
CN114539319B (zh) | 一种手性膦-双环亚磷酰胺酯配体及其制备方法与应用 | |
KR102590897B1 (ko) | 키랄 감마-락탐 화합물의 제조방법 및 이를 위한 금속 착체 | |
CN115160162B (zh) | 一种α氨基β酮酸酯的不对称氢化方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |