CN108586547B - The preparation method of mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine - Google Patents
The preparation method of mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine Download PDFInfo
- Publication number
- CN108586547B CN108586547B CN201810779645.8A CN201810779645A CN108586547B CN 108586547 B CN108586547 B CN 108586547B CN 201810779645 A CN201810779645 A CN 201810779645A CN 108586547 B CN108586547 B CN 108586547B
- Authority
- CN
- China
- Prior art keywords
- nickel
- nitrogen heterocycle
- unsaturated nitrogen
- complex
- heterocycle carbine
- 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.)
- Active
Links
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 150000008301 phosphite esters Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 heterocyclic arene Chemical class 0.000 claims abstract description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 114
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 49
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 21
- 229910052794 bromium Inorganic materials 0.000 claims description 18
- 125000001246 bromo group Chemical group Br* 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 11
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical class [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- MJFCDPLEATUOPF-UHFFFAOYSA-L dichloronickel;triphenylphosphane Chemical class Cl[Ni]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MJFCDPLEATUOPF-UHFFFAOYSA-L 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- 239000000284 extract Substances 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 27
- 238000007259 addition reaction Methods 0.000 abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011777 magnesium Substances 0.000 abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 abstract description 16
- 230000002950 deficient Effects 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000003446 ligand Substances 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- 239000002904 solvent Substances 0.000 description 42
- 239000000047 product Substances 0.000 description 34
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 30
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 22
- UHOVQNZJYSORNB-MZWXYZOWSA-N deuterated benzene Substances [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 15
- 238000007789 sealing Methods 0.000 description 15
- 238000000921 elemental analysis Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000011097 chromatography purification Methods 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 230000005311 nuclear magnetism Effects 0.000 description 7
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- WVNMLOGVAVGQIT-UHFFFAOYSA-N 1-ethylbenzimidazole Chemical class C1=CC=C2N(CC)C=NC2=C1 WVNMLOGVAVGQIT-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 150000002829 nitrogen Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- MNEIJGDSFRHGMS-UHFFFAOYSA-N 1-(phenylmethyl)benzimidazole Chemical compound C1=NC2=CC=CC=C2N1CC1=CC=CC=C1 MNEIJGDSFRHGMS-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- WMVSVUVZSYRWIY-UHFFFAOYSA-N [(4-benzoyloxyiminocyclohexa-2,5-dien-1-ylidene)amino] benzoate Chemical compound C=1C=CC=CC=1C(=O)ON=C(C=C1)C=CC1=NOC(=O)C1=CC=CC=C1 WMVSVUVZSYRWIY-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 1
- AGQBRAMYVMKOBK-UHFFFAOYSA-N 4,5-bis(2,4,6-trimethylphenyl)-1H-imidazole Chemical class CC1=C(C(=CC(=C1)C)C)C1=C(N=CN1)C1=C(C=C(C=C1C)C)C AGQBRAMYVMKOBK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940054051 antipsychotic indole derivative Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XNYYNDAEXFUXBD-UHFFFAOYSA-N tert-butylbenzene ethene Chemical group C=C.C(C)(C)(C)C1=CC=CC=C1 XNYYNDAEXFUXBD-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
-
- 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
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- 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
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/08—Radicals containing only hydrogen and carbon atoms
-
- 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
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/10—Radicals substituted by halogen atoms or nitro radicals
-
- 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
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/12—Radicals substituted by oxygen atoms
-
- 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
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
- B01J2531/0233—Aza-Cp ligands, i.e. [CnN(5-n)Rn]- in which n is 0-4 and R is H or hydrocarbyl, or analogous condensed ring systems
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation method based on phosphite ester and mixed matching nickel (II) complex of unsaturated nitrogen heterocycle carbine, mixed matching nickel (II) coordination chemistry formula is Ni [P (OR1)3][(R2NCHCHNR2)C]X2.Mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine of the invention can in the presence of magnesium efficient catalytic styrene or substituted phenylethylene to the hydrogenation addition reaction of electron deficient heterocyclic arene to synthesize 1,1- diarylethane class compound, this is the first case using phosphite ester and unsaturated nitrogen heterocycle carbine as this complex-catalyzed type hydrogenation addition reaction of mixed matching nickel (II) of assistant ligand.
Description
The present invention be entitled mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine,
Preparation method and application, the applying date are on August 8th, 2016, and application No. is the division Shens of 201610641788.3 patent applications
Please, belong to product preparation method part.
Technical field
The present invention relates to a kind of nickel (II) complex and its applications in organic synthesis field, and in particular to one kind is based on
The preparation method of mixed matching nickel (II) complex of phosphite ester and unsaturated nitrogen heterocycle carbine.
Background technique
1,1- diarylethane class compound is widely present in drug molecule and bioactivity as important structural unit
In molecule, and the aryl ethylene of transition-metal catalyst catalysis is synthesis 1 to the hydrogenation addition reaction of aromatic hydrocarbons, 1- diarylethane
A kind of method of height Atom economy of class compound.In transition-metal catalyst, with the precious metal catalysts such as palladium, ruthenium, gold
System is compared, and nickel catalyst has significant cost advantage due to its cheap price in industrial applications.Therefore it develops
Nickel catalyst realizes that aryl ethylene synthesizes 1,1- diarylethane class compound to the hydrogenation addition reaction of aromatic hydrocarbons and receives
Concern.
It, will be particularly useful but relatively difficult to achieve in hydrogenation addition reaction of the nickel catalyst catalysis aryl ethylene to aromatic hydrocarbons
It is a very big challenge that electron deficient heterocyclic arene substrate, which applies to the reaction,.2010, Yoshiaki Nakao et al. was for the first time
The catalytic body formed with two (the pungent 1,5- diene of ring) nickel (0) and bis- (2,4,6- trimethylphenyl) imidazoles -2- carbenes of 1,3-
System makees solvent with n-hexane, and 130 DEG C of reactions are able to achieve styrene or substituted phenylethylene for 24 hours to a variety of electron deficients and rich electricity
Sub- heterocyclic arene, such as: the hydrogenation addition of indole derivatives, N- tolimidazole, benzoxazoles, benzothiazole, benzofuran
Reaction (referring to: Nakao, Y.; Kashihara, N.; Kanyiva, K. S.; Hiyama, T.Angew. Chem., Int. Ed.2010,49,4451).But the height that this method needs the n-hexane for being 69 DEG C by boiling point to be heated to 130 DEG C
Temperature, there are apparent security risks, can not industrialize；2012, Tiow-Gan Ong et al. still used two (pungent 1, the 5- bis- of ring
Alkene) nickel (0) and 1, the catalyst system of bis- (2,4, the 6- trimethylphenyl) imidazoles -2- carbenes compositions of 3-, using toluene as solvent,
100 DEG C of reactions can be achieved with the hydrogenation addition of styrene, substituted phenylethylene, 2- naphthalene ethylene to N- tolimidazole in 15 hours
Reaction (referring to: Shih, W. C.; Chen, W. C.; Lai, Y. C.; Yu, M. S.; Ho, J. J.; Yap, G.
P. A.; Ong, T. G. Org. Lett.2012,14,2046).But this method and method before have one it is bright
Aobvious common drawback exactly needs to make catalyst using two (ring pungent 1,5- diene) nickel (0) very sensitive to oxygen and moisture,
Almost can not industrial operation, and the price of two (pungent 1, the 5- diene of ring) nickel (0) is relatively expensive, is unfavorable for answering on a large scale in industry
With.Therefore, it is necessary to research and develop easy use insensitive to oxygen and moisture and relatively cheap catalyst, carry out efficient catalytic aryl
Hydrogenation addition reaction of the ethylene to electron deficient heterocyclic arene.
Phosphite ester possess compared with traditional Phosphine ligands (such as: triphenylphosphine, tricyclohexyl phosphine) less expensive price and
Lower toxicity, but up to now, it is related to the research of mixed matching nickel (II) complex containing phosphite ester and N-heterocyclic carbine
Or it is few, it only reported the first mixed matching nickel (II) complex containing phosphite ester and saturation N-heterocyclic carbine at present, and
It was found that they can be reacted with efficient catalytic chlorohydrocarbon with connection boric acid neopentyl glycol ester, yet there are no based on phosphite ester and unsaturation
The report of mixed matching nickel (II) complex of N-heterocyclic carbine more has no that it applies to styrene catalyzed or substituted phenylethylene to scarce
The report of the hydrogenation addition reaction of electron heterocycles aromatic hydrocarbons.
Summary of the invention
The object of the present invention is to provide a kind of mixed matching nickel (II) based on phosphite ester and unsaturated nitrogen heterocycle carbine to match
Close object and preparation method thereof, can in the presence of magnesium efficient catalytic styrene or substituted phenylethylene to electron deficient heterocyclic arene
Hydrogenation addition reaction synthesizes 1,1- diarylethane class compound, catalytic activity, substrate applicability and can commercial operability
It will be better than the prior art.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: one kind be based on phosphite ester and unsaturated nitrogen heterocycle
Mixed matching nickel (II) complex of Cabbeen, general structure are as follows:
Wherein, R1For ethyl or isopropyl；R2For 2,4,6- trimethylphenyl, 2,6- diisopropyl phenyl or tertiary fourth
Base；X is bromine or chlorine.
Mixed matching nickel (II) coordination chemistry formula based on phosphite ester and unsaturated nitrogen heterocycle carbine of the invention is Ni
[P(OR1)3][(R2NCHCHNR2)C]X2；Preparation method is specific as follows:
When X is bromine, the method for preparing above-mentioned mixed matching nickel (II) complex includes the following steps, inert gas
In, two (phosphite ester) Nickel Bromides (II) and unsaturated nitrogen heterocycle carbine are dissolved in solvent, it is small to react 1~4 at room temperature
When；Then solvent is removed in vacuum, residue is extracted after n-hexane washs with toluene, shifts clear liquid and remove solvent toluene obtaining
Nickel (II) complex, as above-mentioned mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine.
When X is chlorine, the method for preparing above-mentioned mixed matching nickel (II) complex includes the following steps, inert gas
In, two (triphenylphosphine) Nickel Chlorides (II) and unsaturated nitrogen heterocycle carbine are dissolved in solvent, are reacted 2 hours at room temperature；
Then solvent is removed in vacuum, residue is extracted after n-hexane washs with toluene, is shifted clear liquid and is removed solvent toluene and contained
Mixed matching nickel (II) complex of triphenylphosphine and unsaturated nitrogen heterocycle carbine；Then by this mixed matching nickel (II) complex and Asia
Phosphate is dissolved in solvent, is reacted 1 hour at room temperature；Then solvent is removed in vacuum, residue is after n-hexane washs with first
Benzene extraction shifts clear liquid and removes solvent toluene obtaining nickel (II) complex, as above-mentioned to be based on phosphite ester and unsaturated nitrogen
Mixed matching nickel (II) complex of heterocycle carbine.
Mixed matching nickel (II) complex phosphorous acid ester prepared by the present invention possesses cheap price and low toxicity；Especially
It is the unsaturated nitrogen heterocyclic carbene ligand having because having stronger electron property, can be very good to stablize central metal,
Be conducive to improve the catalytic performance of complex；Especially compared with being saturated N-heterocyclic carbine, the electron of unsaturated nitrogen heterocycle carbine
Ability is relatively weak, weak with the binding ability of central metal, can be more sharp while stablizing central metal when being catalyzed reaction
In the coordination of central metal and reaction substrate.
In above-mentioned technical proposal, the inert gas is argon gas；Two (phosphite ester) Nickel Bromides (II) and unsaturated nitrogen
The molar ratio of heterocycle carbine is 1:1；The molar ratio of two (triphenylphosphine) Nickel Chlorides (II) and unsaturated nitrogen heterocycle carbine is 1:
1；The molar ratio of mixed matching nickel (II) complex and phosphite ester containing triphenylphosphine and unsaturated nitrogen heterocycle carbine is 1:1；It is molten
Agent is tetrahydrofuran, can dissolve unsaturated nitrogen heterocycle carbine, can also be dissolved based on phosphite ester and unsaturated nitrogen heterocycle carbine
Mixed matching nickel (II) complex and mixed matching nickel (II) complex containing triphenylphosphine and unsaturated nitrogen heterocycle carbine, and be free of
Reactive hydrogen is conducive to react pure progress.
The invention also discloses above-mentioned mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine
As single-component catalyst answering in hydrogenation addition reaction of the styrene catalyzed or substituted phenylethylene to electron deficient heterocyclic arene
With；Preferably, the hydrogenation addition reaction carries out in the presence of magnesium, in inert atmosphere.
The present invention further discloses a kind of method for preparing 1,1- diarylethane class compound, including following step
Suddenly, in an inert gas atmosphere, catalyst, magnesium chips, electron deficient heterocyclic arene, styrene or substitution are successively added into reactor
The mixed solvent of styrene, tetrahydrofuran and toluene, addition reaction obtain 1,1- diarylethane class compound；The catalyst
For above-mentioned mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine.
Further, after reaction, it is terminated and is reacted with water, reaction product is extracted with ethyl acetate, and passes through gas-chromatography
Analysis or column chromatography for separation purification, obtain product yield, can carry out quantitative analysis.
In above-mentioned technical proposal, the inert gas is argon gas.
In above-mentioned technical proposal, the temperature of the addition reaction is 100 DEG C, and the time is 12 hours.
In above-mentioned technical proposal, the electron deficient heterocyclic arene is benzothiazole, N- tolimidazole, N- ethyl benzo
Imidazoles, N- benzyl benzimidazole.
In above-mentioned technical proposal, the substituted phenylethylene be p-methylstyrene, to methoxy styrene, to tert-butyl benzene
Ethylene, pfluorostyrene.
In above-mentioned technical proposal, catalyst, magnesium chips, heterocyclic arene, styrene or substituted phenylethylene molar ratio be 0.05:
0.5: 1: 1.5, according to embodiments of the present invention, when reaction substrate is benzothiazole and styrene, with the meter of substance, styrene
Dosage be 1.5 times of benzothiazole, the dosage of magnesium is 0.5 times of benzothiazole, and the dosage of catalyst is 5 mol %, solvent
The dosage of tetrahydrofuran is 0.5 milliliter, the dosage of toluene is 0.1 milliliter, and reaction temperature is 100 DEG C, and the reaction time is 12 small
When, it can be obtained under the shorter reaction time in relatively mild reaction temperature, less catalyst amount and with the yield of 95 % or more
To 1- phenyl -1- benzothiazole ethane, reaction condition is greatly optimized, and improve the operability of reaction.Therefore originally
Invention also discloses above-mentioned mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine in preparation 1,1-
Application in diarylethane class compound.
The principle of the present invention are as follows: nickel (II) complex can generate nickel (0) complex under the action of magnesium during the reaction,
This complex can hydrogenation addition reaction of the styrene catalyzed with high selectivity or substituted phenylethylene to electron deficient heterocyclic arene
And generate 1,1- diarylethane class compound.
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages:
(1) present invention is with two (phosphite ester) Nickel Bromides (II) or two (triphenylphosphine) Nickel Chlorides cheap and easy to get
It (II) is nickel source, by being prepared for for the first time in reacting for room temperature normal pressure based on phosphorous with unsaturated nitrogen heterocycle carbine or phosphite ester
Mixed matching nickel (II) complex of acid esters and unsaturated nitrogen heterocycle carbine has clear structure, and stable in the air, reaction is simple
Easy to operate, product is easily purified, yield is high, is conducive to synthesize and apply on a large scale.
(2) mixed matching nickel (II) complex disclosed by the invention based on phosphite ester and unsaturated nitrogen heterocycle carbine, can
Hydrogenation addition reaction with efficient catalytic styrene or substituted phenylethylene to electron deficient heterocyclic arene, to synthesize 1,1- diaryl second
Alkyl compound, catalytic activity, substrate applicability and operability are superior to the prior art；According to the embodiment of the present invention, when anti-
Answer substrate be benzothiazole and styrene when, with the meter of substance, the dosage of styrene is 1.5 times of benzothiazole, the use of magnesium
Amount is 0.5 times of benzothiazole, and the dosage of catalyst is 5 mol %, and the dosage of solvents tetrahydrofurane is 0.5 milliliter, toluene
Dosage is 0.1 milliliter, and reaction temperature is 100 DEG C, and the reaction time is 12 hours, and through gas chromatographic analysis, yield is 99 %；It takes
Obtained unexpected technical effect.
(3) styrene realized the present invention provides the first by nickel (II) composition catalyst, in the presence of magnesium metal
Or hydrogenation addition reaction of the substituted phenylethylene to electron deficient heterocyclic arene, it is that the synthesis of 1,1- diarylethane class compound provides
One new method；Compared with prior art, there is significant advantage on extensive synthesis application, more conducively industrialization is answered
With.
Specific embodiment
The present invention will be further described below with reference to examples:
[P (the OR of embodiment one: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=2,4,6- trimethylphenyls, X=
Bromine) synthesis
By unsaturated nitrogen heterocycle carbine (R2NCHCHNR2) C(0.3042g, 1.0 mMs) it is added to two (phosphorous triethylenetetraminehexaacetic acids
Ester) Nickel Bromide (II) (0.5500 gram, 1.0 mMs) tetrahydrofuran solution in, at room temperature react 2 hours, be removed in vacuum
Solvent washs residue with n-hexane, and gained residue is extracted with toluene, shifts clear liquid and removes solvent toluene, obtains red solid
Body, yield are 68 %.
Elemental analysis is carried out to product, the results are shown in Table 1:
1 elemental analysis result of table
| C:(%) | H:(%) | N:(%) | |
| Theoretical value | 46.99 | 5.84 | 4.06 |
| Actual value | 47.16 | 5.93 | 4.01 |
Nuclear-magnetism characterization is carried out to product, as a result as follows:
Product is dissolved in C6D6In (about 0.4 mL), tube sealing, at room temperature in measuring table on Unity Inova-400 type NMR instrument
Sign: 1H NMR (400 MHz, C6D6): δ 6.87 (s, 4H), 6.18 (s, 2H), 4.05 (q, J = 7.0 Hz,
6H), 2.48 (s, 12H), 2.15 (s, 6H), 1.06 (t, J = 7.0 Hz, 9H) ppm。
[P (the OR of embodiment two: Ni1)3][(R2NCHCHNR2)C]X2(R1=isopropyl, R2=2,4,6- trimethylphenyls, X
=bromine) synthesis
By unsaturated nitrogen heterocycle carbine (R2NCHCHNR2) C(0.3042g, 1.0 mMs) being added to two, (phosphorous acid three is different
Propyl ester) Nickel Bromide (II) (0.6350 gram, 1.0 mMs) tetrahydrofuran solution in, at room temperature react 3 hours, vacuum is removed
Solvent is removed, residue is washed with n-hexane, gained residue is extracted with toluene, is shifted clear liquid and is removed solvent toluene, obtains red
Solid, yield are 72 %.
Elemental analysis is carried out to product, the results are shown in Table 2:
2 elemental analysis result of table
| C:(%) | H:(%) | N:(%) | |
| Theoretical value | 49.21 | 6.33 | 3.83 |
| Actual value | 49.43 | 6.39 | 3.72 |
Nuclear-magnetism characterization is carried out to product, as a result as follows:
Product is dissolved in C6D6In (about 0.4 mL), tube sealing, at room temperature in measuring table on Unity Inova-400 type NMR instrument
Sign:1H NMR (400 MHz, C6D6): δ 6.86 (s, 4H), 6.12 (s, 2H), 5.16 (dt, J = 12.3,
6.1 Hz, 3H), 2.46 (s, 12H), 2.16 (s, 6H), 1.21 (d, J = 6.2 Hz, 18H) ppm。
[P (the OR of embodiment three: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=2,6- diisopropyl phenyl, X=
Bromine) synthesis
By unsaturated nitrogen heterocycle carbine (R2NCHCHNR2) C(0.3883g, 1.0 mMs) it is added to two (phosphorous triethylenetetraminehexaacetic acids
Ester) Nickel Bromide (II) (0.5500 gram, 1.0 mMs) tetrahydrofuran solution in, at room temperature react 1 hour, be removed in vacuum
Solvent washs residue with n-hexane, and gained residue is extracted with toluene, shifts clear liquid and removes solvent toluene, obtains red solid
Body, yield are 73 %.
Elemental analysis is carried out to product, the results are shown in Table 3:
3 elemental analysis result of table
| C:(%) | H:(%) | N:(%) | |
| Theoretical value | 51.19 | 6.77 | 3.62 |
| Actual value | 51.31 | 6.80 | 3.57 |
Nuclear-magnetism characterization is carried out to product, as a result as follows:
Product is dissolved in C6D6In (about 0.4 mL), tube sealing, at room temperature in measuring table on Unity Inova-400 type NMR instrument
Sign:1H NMR (400 MHz, C6D6): δ 7.35 – 7.23 (m, 6H), 6.61 (s, 2H), 3.97 (q, J =
7.0 Hz, 6H), 3.46 (t, J = 13.5 Hz, 4H), 1.63 (d, J = 6.6 Hz, 12H), 1.03 (dd,J = 14.2, 7.0 Hz, 21H) ppm。
Example IV: Ni [P (OR1)3][(R2NCHCHNR2)C]X2(R1=isopropyl, R2=2,6- diisopropyl phenyl, X=
Bromine) synthesis
By unsaturated nitrogen heterocycle carbine (R2NCHCHNR2) C(0.3883g, 1.0 mMs) being added to two, (phosphorous acid three is different
Propyl ester) Nickel Bromide (II) (0.6350 gram, 1.0 mMs) tetrahydrofuran solution in, at room temperature react 1 hour, vacuum is removed
Solvent is removed, residue is washed with n-hexane, gained residue is extracted with toluene, is shifted clear liquid and is removed solvent toluene, obtains red
Solid, yield are 64 %.
Elemental analysis is carried out to product, the results are shown in Table 4:
4 elemental analysis result of table
| C:(%) | H:(%) | N:(%) | |
| Theoretical value | 52.97 | 7.16 | 3.43 |
| Actual value | 53.25 | 7.29 | 3.33 |
Nuclear-magnetism characterization is carried out to product, as a result as follows:
Product is dissolved in C6D6In (about 0.4 mL), tube sealing, at room temperature in measuring table on Unity Inova-400 type NMR instrument
Sign:1H NMR (400 MHz, C6D6): δ 7.34 – 7.26 (m, 6H), 6.59 (s, 2H), 5.03 (t, J =
12.3 Hz, 3H), 3.52 – 3.38 (m, 4H), 1.62 (d, J = 6.6 Hz, 12H), 1.17 (d, J =
6.2 Hz, 18H), 1.04 (d, J = 6.9 Hz, 12H) ppm。
[P (the OR of embodiment five: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=tert-butyl, X=bromine) synthesis
By unsaturated nitrogen heterocycle carbine (R2NCHCHNR2) C(0.1802g, 1.0 mMs) it is added to two (phosphorous triethylenetetraminehexaacetic acids
Ester) Nickel Bromide (II) (0.5500 gram, 1.0 mMs) tetrahydrofuran solution in, at room temperature react 3 hours, be removed in vacuum
Solvent washs residue with n-hexane, and gained residue is extracted with toluene, shifts clear liquid and removes solvent toluene, obtains orange red
Solid, yield are 62 %.
Elemental analysis is carried out to product, the results are shown in Table 5:
5 elemental analysis result of table
| C:(%) | H:(%) | N:(%) | |
| Theoretical value | 36.08 | 6.41 | 4.95 |
| Actual value | 36.19 | 6.47 | 4.91 |
Nuclear-magnetism characterization is carried out to product, as a result as follows:
Product is dissolved in C6D6In (about 0.4 mL), tube sealing, at room temperature in measuring table on Unity Inova-400 type NMR instrument
Sign:1H NMR (400 MHz, C6D6): δ 6.61 (s, 2H), 6.52 (s, 1H), 4.23-4.30 (m, 3H),
4.05-4.12 (m, 6H), 2.34 (s, 10H), 2.15 (s, 18H), 1.21 (t, J = 7.0 Hz, 5H),
0.94 (t, J = 7.0 Hz, 9H) ppm。
[P (the OR of embodiment six: Ni1)3][(R2NCHCHNR2)C]X2(R1=isopropyl, R2=tert-butyl, X=bromine) synthesis
By unsaturated nitrogen heterocycle carbine (R2NCHCHNR2) C(0.1802g, 1.0 mMs) being added to two, (phosphorous acid three is different
Propyl ester) Nickel Bromide (II) (0.6350 gram, 1.0 mMs) tetrahydrofuran solution in, at room temperature react 4 hours, vacuum is removed
Solvent is removed, residue is washed with n-hexane, gained residue is extracted with toluene, is shifted clear liquid and is removed solvent toluene, obtains orange red
Color solid, yield are 66 %.
Elemental analysis is carried out to product, the results are shown in Table 6:
6 elemental analysis result of table
| C:(%) | H:(%) | N:(%) | |
| Theoretical value | 39.51 | 6.96 | 4.61 |
| Actual value | 39.64 | 7.01 | 4.56 |
Nuclear-magnetism characterization is carried out to product, as a result as follows:
Product is dissolved in C6D6In (about 0.4 mL), tube sealing, at room temperature in measuring table on Unity Inova-400 type NMR instrument
Sign:1H NMR (400 MHz, C6D6): δ 6.61 (s, 2H), 6.51 (s, 0.6H), 5.25-5.29 (m, 1H),
5.01-5.04 (m, 3H), 2.36 (s, 6H), 2.19 (s, 18H), 1.37 (t, J = 5.9 Hz, 6H),
1.09 (d, J = 4.1 Hz, 18H) ppm。
[P (the OR of embodiment seven: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=tert-butyl, X=chlorine) synthesis
By unsaturated nitrogen heterocycle carbine (R2NCHCHNR2) C(0.1802 grams, 1.0 mMs) it is added to two (triphenylphosphines)
In the tetrahydrofuran solution of Nickel Chloride (II) (0.6521 gram, 1.0 mMs), reacts 2 hours, be removed in vacuum molten at room temperature
Agent washs residue with n-hexane, and gained residue is extracted with toluene, shifts clear liquid and removes solvent toluene, obtains pink solid
Body, yield are 75 %.Again by pink solid (0.4284 gram, 0.75 mM) and triethyl phosphite (0.1246 gram, 0.75
MM) mixing, tetrahydrofuran is added as solvent, reacts 1 hour at room temperature, vacuum pumps solvent, surplus with n-hexane washing
Excess, gained residue are extracted with toluene, are shifted clear liquid and are removed solvent toluene, and orange/yellow solid is obtained, and yield is 88 %.
Elemental analysis is carried out to product, the results are shown in Table 7:
7 elemental analysis result of table
| C:(%) | H:(%) | N:(%) | |
| Theoretical value | 42.80 | 7.61 | 5.87 |
| Actual value | 42.93 | 7.69 | 5.82 |
Nuclear-magnetism characterization is carried out to product, as a result as follows:
Product is dissolved in C6D6In (about 0.4 mL), tube sealing, at room temperature in measuring table on Unity Inova-400 type NMR instrument
Sign:1H NMR (400 MHz, C6D6): δ 6.61 (s, 2H), 6.52 (s, 1H), 4.23-4.30 (m, 3H),
4.05-4.12 (m, 6H), 2.34 (s, 10H), 2.15 (s, 18H), 1.21 (t, J = 7.0 Hz, 5H),
0.94 (t, J = 7.0 Hz, 9H) ppm。
[P (the OR of embodiment eight: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=2,4,6- trimethylphenyls, X=
Bromine) the styrene catalyzed hydrogenation addition reaction with benzothiazole
Under argon gas protection, catalyst (10.4 milligrams, 0.015 mM, 5 mol%), magnesium chips are sequentially added in reaction flask
(3.6 milligrams, 0.15 mM), benzothiazole (33 microlitres, 0.3 mM), styrene (52 microlitres, 0.45 mM), four
Hydrogen furans (0.5 milliliter) and toluene (0.1 milliliter) make solvent, react 12 hours at 100 DEG C, are terminated and are reacted with water, and reaction produces
Object is extracted with ethyl acetate, and is 99 % through gas chromatographic analysis product yield, column Chromatographic purification is (with ethyl acetate/petroleum ether body
Product is solvent than the mixed solvent for being 1: 20), yield is 96 %.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): δ 8.01 (d,J = 8.1 Hz, 1H), 7.76 (d, J =
8.0 Hz, 1H), 7.45 – 7.24 (m, 7H), 4.58 (q, J = 7.2 Hz, 1H), 1.86 (d, J = 7.2
Hz, 3H) ppm。
[P (the OR of embodiment nine: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=2,4,6- trimethylphenyls, X=
Bromine) hydrogenation addition reaction of the catalysis p-methylstyrene to benzothiazole
Under argon gas protection, catalyst (10.4 milligrams, 0.015 mM, 5 mol%), magnesium chips are sequentially added in reaction flask
(3.6 milligrams, 0.15 mM), benzothiazole (33 microlitres, 0.3 mM), p-methylstyrene (57 microlitres, 0.45 mmoles
You), tetrahydrofuran (0.5 milliliter) and toluene (0.1 milliliter) make solvent, react 12 hours at 100 DEG C, terminates reaction with water,
Reaction product is extracted with ethyl acetate, and column Chromatographic purification (is exhibition with the mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 20
Open agent), yield is 92 %.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): δ 8.06 (d,J = 8.1 Hz, 1H), 7.81 (d, J =
8.4 Hz, 1H), 7.56 – 7.44 (m, 1H), 7.35 (d, J = 20.5 Hz, 3H), 7.20 (d, J = 7.9
Hz, 2H), 4.60 (t, J = 10.7 Hz, 1H), 2.38 (s, 3H), 1.90 (d, J = 7.2 Hz, 3H)
ppm。
[P (the OR of embodiment ten: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=2,4,6- trimethylphenyls, X=
Bromine) hydrogenation addition reaction of the catalysis p-tert-butylstyrene to benzothiazole
Under argon gas protection, catalyst (10.4 milligrams, 0.015 mM, 5 mol%), magnesium chips are sequentially added in reaction flask
(83 microlitres, 0.45 in the least for (3.6 milligrams, 0.15 mM), benzothiazole (33 microlitres, 0.3 mM), p-tert-butylstyrene
Mole), tetrahydrofuran (0.5 milliliter) and toluene (0.1 milliliter) make solvent, react 12 hours at 100 DEG C, is terminated instead with water
It answers, reaction product is extracted with ethyl acetate, the column Chromatographic purification (mixed solvent for being 1: 20 with ethyl acetate/petroleum ether volume ratio
For solvent), yield is 93 %.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): δ 8.05 (d,J = 8.2 Hz, 1H), 7.81 (d, J =
8.0 Hz, 1H), 7.50 – 7.45 (m, 1H), 7.43 – 7.31 (m, 5H), 4.61 (q, J = 7.2 Hz,
1H), 1.91 (d, J = 7.2 Hz, 3H), 1.35 (s, 9H) ppm。
[P (the OR of embodiment 11: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=2,4,6- trimethylphenyls, X=
Bromine) hydrogenation addition reaction of the catalysis pfluorostyrene to benzothiazole
Under argon gas protection, catalyst (10.4 milligrams, 0.015 mM, 5 mol%), magnesium chips are sequentially added in reaction flask
(3.6 milligrams, 0.15 mM), benzothiazole (33 microlitres, 0.3 mM), pfluorostyrene (54 microlitres, 0.45 mmoles
You), tetrahydrofuran (0.5 milliliter) and toluene (0.1 milliliter) make solvent, react 12 hours at 100 DEG C, terminates reaction with water,
Reaction product is extracted with ethyl acetate, and column Chromatographic purification (is exhibition with the mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 20
Open agent), yield is 88 %.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): δ 8.05 (d,J = 8.1 Hz, 1H), 7.82 (d, J =
7.5 Hz, 1H), 7.53 – 7.44 (m, 1H), 7.37 (t, J = 11.8 Hz, 3H), 7.14 – 6.96 (m,
2H), 4.60 (q, J = 7.2 Hz, 1H), 1.88 (d, J = 7.2 Hz, 3H) ppm。
[P (the OR of embodiment 12: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=2,4,6- trimethylphenyls, X=
Bromine) hydrogenation addition reaction of the catalysis pfluorostyrene to N- tolimidazole
Under argon gas protection, catalyst (10.4 milligrams, 0.015 mM, 5 mol%), magnesium chips are sequentially added in reaction flask
(3.6 milligrams, 0.15 mM), N- tolimidazole (40 milligrams, 0.3 mM), pfluorostyrene (54 microlitres, 0.45
MM), tetrahydrofuran (0.5 milliliter) and toluene (0.1 milliliter) make solvent, react 12 hours at 100 DEG C, terminated with water
Reaction, reaction product are extracted with ethyl acetate, the column Chromatographic purification (mixed solvent for being 1: 2 with ethyl acetate/petroleum ether volume ratio
For solvent), yield is 80 %.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): δ 7.81-7.79 (m, 1H), 7.22-7.21 (m, 3H), 7.14
– 7.12 (m, 2H), 6.93-6.89 (m,2H), 4.30 (q, J = 6.8 Hz, 1H), 3.34 (s, 3H),
1.80 (d, J = 6.8 Hz, 3H) ppm。
[P (the OR of embodiment 13: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=2,4,6- trimethylphenyls, X=
Bromine) hydrogenation addition reaction of the catalysis to methoxy styrene to N- tolimidazole
Under argon gas protection, catalyst (10.4 milligrams, 0.015 mM, 5 mol%), magnesium chips are sequentially added in reaction flask
(3.6 milligrams, 0.15 mM), N- tolimidazole (40 milligrams, 0.3 mM), to methoxy styrene (61 microlitres,
0.45 mM), tetrahydrofuran (0.5 milliliter) and toluene (0.1 milliliter) make solvent, reacted 12 hours at 100 DEG C, use water
Reaction is terminated, reaction product is extracted with ethyl acetate, (the mixing for being 1: 2 with ethyl acetate/petroleum ether volume ratio of column Chromatographic purification
Solvent is solvent), yield is 78 %.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): δ 7.81-7.79 (m, 1H), 7.22-7.17 (m, 3H), 7.08
(d, J = 8.6 Hz, 2H), 6.77 (d, J = 8.6 Hz, 2H), 4.42 (q, J = 7.0 Hz, 1H), 3.70
(s, 3H), 3.41 (s, 3H), 1.80 (d, J = 7.0 Hz, 3H) ppm。
[P (the OR of embodiment 14: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=2,4,6- trimethylphenyls, X=
Bromine) the styrene catalyzed hydrogenation addition reaction to N- ethyl benzo imidazole
Under argon gas protection, catalyst (10.4 milligrams, 0.015 mM, 5 mol%), magnesium chips are sequentially added in reaction flask
(3.6 milligrams, 0.15 mM), N- ethyl benzo imidazole (44 milligrams, 0.3 mM), styrene (52 microlitres, 0.45 mmoles
You), tetrahydrofuran (0.5 milliliter) and toluene (0.1 milliliter) make solvent, react 12 hours at 100 DEG C, terminates reaction with water,
Reaction product is extracted with ethyl acetate, and column Chromatographic purification (is exhibition with the mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 2
Open agent), yield is 63 %.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): δ 7.85-7.83 (m, 1H), 7.35-7.16 (m, 8H), 4.29
(q, J = 7.0 Hz, 1H), 3.96 (m, 2H), 1.85 (d, J = 7.0 Hz, 3H), 0.99 (t, J = 7.5
Hz, 3H) ppm。
[P (the OR of embodiment 15: Ni1)3][(R2NCHCHNR2)C]X2(R1=ethyl, R2=2,4,6- trimethylphenyls, X=
Bromine) the styrene catalyzed hydrogenation addition reaction to N- benzyl benzimidazole
Under argon gas protection, catalyst (10.4 milligrams, 0.015 mM, 5 mol%), magnesium chips are sequentially added in reaction flask
(3.6 milligrams, 0.15 mM), N- ethyl benzo imidazole (63 milligrams, 0.3 mM), styrene (52 microlitres, 0.45 mmoles
You), tetrahydrofuran (0.5 milliliter) and toluene (0.1 milliliter) make solvent, react 12 hours at 100 DEG C, terminates reaction with water,
Reaction product is extracted with ethyl acetate, and column Chromatographic purification (is exhibition with the mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 2
Open agent), yield is 75 %.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): δ 7.88 (d,J = 8.1 Hz, 1H), 7.25-7.15 (m,
11H), 6.88-6.86 (m, 2H), 5.17 (d, J = 16.8 Hz, 1H), 4.98 (d, J = 16.8 Hz,
1H), 4.19 (q, J = 7.2 Hz, 1H), 1.81 (d, J = 7.2 Hz, 3H) ppm。
Claims (2)
1. the preparation method of mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine, feature exist
In:
When X is bromine, in inert gas, two (phosphite ester) Nickel Bromides (II) are dissolved in unsaturated nitrogen heterocycle carbine
In tetrahydrofuran, react 1~4 hour at room temperature；Then tetrahydrofuran is removed in vacuum, residue is after n-hexane washs with first
Benzene extraction shifts clear liquid and removes toluene obtaining the mixed matching nickel (II) based on phosphite ester and unsaturated nitrogen heterocycle carbine
Complex；The molar ratio of two (phosphite ester) Nickel Bromides (II) and unsaturated nitrogen heterocycle carbine is 1:1；
When X is chlorine, in inert gas, two (triphenylphosphine) Nickel Chlorides (II) are dissolved in unsaturated nitrogen heterocycle carbine
In tetrahydrofuran, react 2 hours at room temperature；Then tetrahydrofuran is removed in vacuum, residue is after n-hexane washs with toluene
Extraction shifts clear liquid and removes toluene obtaining mixed matching nickel (II) complex containing triphenylphosphine and unsaturated nitrogen heterocycle carbine；
Then this mixed matching nickel (II) complex and phosphite ester are dissolved in tetrahydrofuran, are reacted 1 hour at room temperature；Then vacuum
Remove tetrahydrofuran, residue extracts after n-hexane washs with toluene, shift clear liquid and remove toluene obtain it is described based on Asia
Mixed matching nickel (II) complex of phosphate and unsaturated nitrogen heterocycle carbine；Two (triphenylphosphine) Nickel Chlorides (II) and unsaturation
The molar ratio of N-heterocyclic carbine is 1:1；Mixed matching nickel (II) complex and Asia containing triphenylphosphine and unsaturated nitrogen heterocycle carbine
The molar ratio of phosphate is 1:1；
The general structure of described mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine is as follows:
Wherein, R1For ethyl or isopropyl；R2For 2,4,6- trimethylphenyl, 2,6- diisopropyl phenyl or tert-butyl；X
For bromine or chlorine.
2. the system of mixed matching nickel (II) complex according to claim 1 based on phosphite ester and unsaturated nitrogen heterocycle carbine
Preparation Method, it is characterised in that: the inert gas is argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810779645.8A CN108586547B (en) | 2016-08-08 | 2016-08-08 | The preparation method of mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810779645.8A CN108586547B (en) | 2016-08-08 | 2016-08-08 | The preparation method of mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine |
| CN201610641788.3A CN106279297B (en) | 2016-08-08 | 2016-08-08 | Mixed matching nickel (II) complex, preparation method and application based on phosphite ester and unsaturated nitrogen heterocycle carbine |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610641788.3A Division CN106279297B (en) | 2016-08-08 | 2016-08-08 | Mixed matching nickel (II) complex, preparation method and application based on phosphite ester and unsaturated nitrogen heterocycle carbine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108586547A CN108586547A (en) | 2018-09-28 |
| CN108586547B true CN108586547B (en) | 2019-09-10 |
Family
ID=57665926
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810771458.5A Active CN108822160B (en) | 2016-08-08 | 2016-08-08 | The application of mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine |
| CN201810779645.8A Active CN108586547B (en) | 2016-08-08 | 2016-08-08 | The preparation method of mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine |
| CN201810766390.1A Active CN108840838B (en) | 2016-08-08 | 2016-08-08 | A method of preparing 1,1- diarylethane class compound |
| CN201610641788.3A Active CN106279297B (en) | 2016-08-08 | 2016-08-08 | Mixed matching nickel (II) complex, preparation method and application based on phosphite ester and unsaturated nitrogen heterocycle carbine |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810771458.5A Active CN108822160B (en) | 2016-08-08 | 2016-08-08 | The application of mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810766390.1A Active CN108840838B (en) | 2016-08-08 | 2016-08-08 | A method of preparing 1,1- diarylethane class compound |
| CN201610641788.3A Active CN106279297B (en) | 2016-08-08 | 2016-08-08 | Mixed matching nickel (II) complex, preparation method and application based on phosphite ester and unsaturated nitrogen heterocycle carbine |
Country Status (1)
| Country | Link |
|---|---|
| CN (4) | CN108822160B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108654695B (en) * | 2017-03-29 | 2021-04-06 | 天津大学 | Indole [3,2-a ] oxazolidine-labeled ruthenium carbene catalyst, and preparation method and application thereof |
| CN110305171B (en) * | 2019-07-28 | 2021-09-28 | 苏州大学 | Preparation and application of mixed nickel (II) complex containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand |
| CN110330535B (en) * | 2019-07-28 | 2022-04-15 | 苏州大学 | N-heterocyclic carbene-based mixed nickel (II) complex and application thereof |
| CN111420709B (en) * | 2020-04-23 | 2023-06-06 | 苏州大学 | Application of N-heterocyclic carbene-based mixed nickel (II) complex in synthesis of 2-linear alkyl benzothiazole compound |
| WO2022155981A1 (en) * | 2021-01-25 | 2022-07-28 | 苏州大学 | USE OF N-HETEROCYCLIC CARBENE-BASED COMPOUNDED NICKEL (II) COMPLEX IN SYNTHESIS OF α-BENZYL BENZOFURAN COMPOUND |
| WO2022155980A1 (en) * | 2021-01-25 | 2022-07-28 | 苏州大学 | METHOD FOR SYNTHESIZING α-BENZYL BENZOFURAN COMPOUND |
| CN112645909A (en) * | 2021-01-25 | 2021-04-13 | 苏州大学 | Method for synthesizing alpha-benzyl benzofuran compound |
| CN112675919B (en) * | 2021-01-25 | 2023-06-13 | 苏州大学 | Application of N-heterocyclic carbene-based mixed nickel (II) complex in synthesis of alpha-benzyl benzofuran compound |
| CN114380824B (en) * | 2022-01-30 | 2023-04-07 | 苏州大学 | Method for synthesizing 2-phenyl-5-benzyl-imidazo [1,2-a ] pyridine compound |
| WO2024026596A1 (en) * | 2022-07-31 | 2024-02-08 | 苏州大学 | METHOD FOR SYNTHESIZING α-LINEAR ALKYL SUBSTITUTED HETEROARENE |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1136123A3 (en) * | 2000-03-23 | 2002-11-27 | Institut Francais Du Petrole | Catalytic composition and catalytic process of dimerisation, codimerisation and oligomerisation of olefins |
| CN104098607A (en) * | 2014-07-07 | 2014-10-15 | 苏州大学 | Complex and application of monophosphine monoazacyclo-carben nickel containing tricyclic hexyl phosphine |
| CN105732684A (en) * | 2016-04-08 | 2016-07-06 | 苏州大学张家港工业技术研究院 | Method for preparing arylboronic acid neopentyl glycol ester |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6348249A (en) * | 1986-08-18 | 1988-02-29 | Kanzaki Paper Mfg Co Ltd | Diarylethane derivative and production thereof |
| CN101486736A (en) * | 2009-02-27 | 2009-07-22 | 苏州大学 | Asymmetric bis-(N-heterocyclic carbene) nickel (II) dihalide and preparation thereof |
| CN105061124B (en) * | 2015-07-27 | 2017-03-22 | 苏州大学 | Diarylmethane compound preparation method |
-
2016
- 2016-08-08 CN CN201810771458.5A patent/CN108822160B/en active Active
- 2016-08-08 CN CN201810779645.8A patent/CN108586547B/en active Active
- 2016-08-08 CN CN201810766390.1A patent/CN108840838B/en active Active
- 2016-08-08 CN CN201610641788.3A patent/CN106279297B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1136123A3 (en) * | 2000-03-23 | 2002-11-27 | Institut Francais Du Petrole | Catalytic composition and catalytic process of dimerisation, codimerisation and oligomerisation of olefins |
| CN104098607A (en) * | 2014-07-07 | 2014-10-15 | 苏州大学 | Complex and application of monophosphine monoazacyclo-carben nickel containing tricyclic hexyl phosphine |
| CN105732684A (en) * | 2016-04-08 | 2016-07-06 | 苏州大学张家港工业技术研究院 | Method for preparing arylboronic acid neopentyl glycol ester |
| CN105732684B (en) * | 2016-04-08 | 2018-01-02 | 苏州大学张家港工业技术研究院 | A kind of method for preparing aryl boric acid DOPCP |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108822160A (en) | 2018-11-16 |
| CN108840838A (en) | 2018-11-20 |
| CN108840838B (en) | 2019-09-10 |
| CN108822160B (en) | 2019-09-17 |
| CN108586547A (en) | 2018-09-28 |
| CN106279297A (en) | 2017-01-04 |
| CN106279297B (en) | 2018-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108586547B (en) | The preparation method of mixed matching nickel (II) complex based on phosphite ester and unsaturated nitrogen heterocycle carbine | |
| Pinaka et al. | Using sustainable metals to carry out “green” transformations: Fe-and Cu-catalyzed CO2 monetization | |
| CN110330535B (en) | N-heterocyclic carbene-based mixed nickel (II) complex and application thereof | |
| Aydemir et al. | Novel neutral phosphinite bridged dinuclear ruthenium (II) arene complexes and their catalytic use in transfer hydrogenation of aromatic ketones: X-ray structure of a new Schiff base, N3, N3′-di-2-hydroxybenzylidene-[2, 2′] bipyridinyl-3, 3′-diamine | |
| Tan et al. | Synthesis and structure of an air-stable organobismuth triflate complex and its use as a high-efficiency catalyst for the ring opening of epoxides in aqueous media with aromatic amines | |
| EP3092075A1 (en) | Iron(ii) catalysts containing tridentate pnp ligands, their synthesis, and use thereof | |
| CN106423281B (en) | Application of the rare earth silicon amide in catalysis prepares spiral shell [cyclopropane -1,3 '-indoles] compound | |
| CN108525704A (en) | Catalyst and its preparation method and application for hydroformylation of olefin | |
| CN107973812B (en) | A method of preparing aryl boric acid neopentyl glycol esters compound | |
| Miyaki et al. | Synthesis and reaction of ruthenium (II) complexes containing heteroatom donor (O, N, and P) tethered to η6-arene ring | |
| Yao et al. | Catalytic hydrogenation of carbonyl and nitro compounds using an [N, O]-chelate half-sandwich ruthenium catalyst | |
| Liang et al. | Tungsten (II)− Carbene Complex Functions as a Dicationic Synthon: Efficient Constructions of Furan and Pyran Frameworks from Readily Available α, δ-and α, ε-Alkynols | |
| Aydemir et al. | New active ruthenium (II) complexes based N3, N3′-bis (diphenylphosphino)-2, 2′-bipyridine-3, 3′-diamine and P, P′-diphenylphosphinous acid-P, P′-[2, 2′-bipyridine]-3, 3′-diyl ester ligands for transfer hydrogenation of aromatic ketones by propan-2-ol | |
| Borowski et al. | Homogeneous hydrogenation of arenes catalyzed by the bis (dihydrogen) complex [RuH2 (H2) 2 (PCy3) 2] | |
| Chang et al. | Pyridine N-oxide promoted hydrosilylation of carbonyl compounds catalyzed by [PSiP]-pincer iron hydrides | |
| CN108002966A (en) | A kind of method of synthesis 1,2- diarylethane class compounds | |
| Galland et al. | Enantiopure 1-rH-2-c, 5-t-diphenylphospholane as ligand in Rh-catalyzed asymmetric hydrogenation | |
| Zhang et al. | Low Coordination State RhI‐Complex as High Performance Catalyst for Asymmetric Intramolecular Cyclopropanation: Construction of penta‐Substituted Cyclopropanes | |
| CN105732684B (en) | A kind of method for preparing aryl boric acid DOPCP | |
| Choi et al. | Solvent effects on the asymmetric Pauson–Khand-type reaction by rhodium | |
| Planas et al. | Carbon–oxygen and carbon–sulfur bond activation of vinyl esters, ethers and sulfides by low valent ruthenium complexes | |
| CN106582852B (en) | A kind of preparation method of double phosphine-rhodium (I) chiral catalysts of ferrocene | |
| Daley et al. | Substrate effects on the mechanism of enantioselective hydrogenation using ruthenium bis (phosphine) complexes as catalyst: A mechanistic investigation of the hydrogenation of α, β-unsaturated acids and esters based on deuterium labeling studies | |
| Lavi et al. | Iridium complexes of acridine-based PNP-type pincer ligands: Synthesis, structure and reactivity | |
| Dobrota et al. | Chiral 1, 2, 5-triphenylphospholanium tetrafluoroborate as ligand precursor in Rh-catalyzed asymmetric hydrogenation of methyl (Z)-2-acetamidocinnamate |
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 |