CN106478737A - The ferrum ferrum hydrogenation catalator thing of the trimethylene bridge of azepine containing functionalization and azepine carbenes and its synthetic method - Google Patents
The ferrum ferrum hydrogenation catalator thing of the trimethylene bridge of azepine containing functionalization and azepine carbenes and its synthetic method Download PDFInfo
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- CN106478737A CN106478737A CN201610860317.1A CN201610860317A CN106478737A CN 106478737 A CN106478737 A CN 106478737A CN 201610860317 A CN201610860317 A CN 201610860317A CN 106478737 A CN106478737 A CN 106478737A
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- ferrum
- azepine
- carbenes
- cabbeen
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 71
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 11
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- -1 methoxyl group Chemical group 0.000 claims abstract description 12
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical group COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims abstract description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000000376 reactant Substances 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- LXGRHJKRSXQMAE-UHFFFAOYSA-N 1-methyl-3-(2,4,6-trimethylphenyl)-2h-imidazole Chemical class C1=CN(C)CN1C1=C(C)C=C(C)C=C1C LXGRHJKRSXQMAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000000547 structure data Methods 0.000 description 4
- 241000972773 Aulopiformes Species 0.000 description 3
- 108010020056 Hydrogenase Proteins 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 235000019515 salmon Nutrition 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 108010022579 ATP dependent 26S protease Proteins 0.000 description 1
- QLUYMYXWJAOMQR-UHFFFAOYSA-N CCCN(C)C(CC)NC Chemical compound CCCN(C)C(CC)NC QLUYMYXWJAOMQR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 1
- 101001031591 Mus musculus Heart- and neural crest derivatives-expressed protein 2 Proteins 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007068 beta-elimination reaction Methods 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical class OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
Classifications
-
- 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
- C07F15/02—Iron 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- 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
-
- 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
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/842—Iron
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The ferrum ferrum hydrogenation catalator thing and its synthetic method of a kind of trimethylene bridge of azepine containing functionalization and azepine carbenes, belongs to that metal is organic, the energy and material science, and gained model chemical structure formula is as follows：In structural formula：R is methoxyl group or methyl formate base, L is 1 methyl 3 (2,4,6 trimethylphenyls) imidazoles 2 Cabbeen or 1,3 methylimidazole 2 Cabbeen or 1 vinyl 3 (2,4,6 trimethylphenyl) imidazoles 2 Cabbeen or 1 acrylic 3 (2,4,6 trimethylphenyls) imidazoles 2 Cabbeen.It is an advantage of the invention that：Prepare the ferrum ferrum hydrogenation catalator thing of the trimethylene bridge of azepine containing functionalization and azepine carbenes using the method, reaction condition is gentle, easy and simple to handle, and yield is high.The Fe of this model thingI‑FeIBonding electron density is big, is conducive to protonating, has potential superior catalytic hydrogen production potential.
Description
Technical field
The invention belongs to metal is organic, the energy and material science, the particularly trimethylene bridge of azepine containing functionalization and azepine
The ferrum ferrum hydrogenation catalator thing of carbenes and its synthetic method.
Background technology
With society and expanding economy, environmental pollution and energy shortage two hang-up have become as the great of facing mankind
Challenge.A large amount of consumption of the fossil energies such as coal, oil and natural gas, not only cause the increasingly depleted of non-renewable energy resources,
And make environmental pollution increasingly severe.People are in order to alleviate energy shortage and improve environment and always search for new replacement energy
Source, wherein hydrogen are undoubtedly a kind of environment amenable regenerative resource.But current product hydrogen methods are far away from the need of people
Ask, it is intended that can have a kind of catalyst of Cheap highly effective can proton reduction in catalytic water and produce hydrogen on a large scale.Ferrum
Ferrum hydrogenase be a kind of be present in multiple-microorganism and can be efficiently the native enzyme of hydrogen by proton reduction in water, because
This, people are devoted to the research to ferrum ferrum hydrogenase catalytic center 26S Proteasome Structure and Function in recent years, and the final purpose studied be for
Discovery a kind of by containing efficient " artificial enzyme " catalyst that abundant and cheap metallic iron is obtained, thus solve us being faced
Energy shortage and problem of environmental pollution.Referring to：Song,L.–C.Acc.Chem.Res.2005,38,21-28；Schilter,
D.；Camara,J.M.；Huynh,M.T.；Hammes-Schiffer,S.；Rauchfuss,T.B.Chem.Rev.2016,116,
8693-8749；Simmons,T.R.；Berggrena,G.；Bacchi,M.；Fontecave,M.；Artero,
V.Coord.Chem.Rev.2014,270-271,127-150；Lubitz,W.；Ogata,H.；Rüdiger,O.；Reijerse,
E.Chem.Rev.2014,114,4081-4148.
So far, people synthesized a series of nitrogen-containing hetero carbenes (NHC) ferrum ferrum hydrogenation catalator thing, this be because
For NHC part with the CN contained by natural enzyme catalysiss center-The electronic effect that part is similar to, and the electronics of NHC part and solid
Effect can be regulated and controled by structural change.But it is worthy of note that, these be obtained nitrogen-containing hetero Cabbeens model thing
In, great majority are derivants on butterfly-shaped two ferrum two sulfur cluster core for the trimethylene bridge bridging, and both nitrogen-containing hetero carbenes nitrogen-containing heteros
The derivant of trimethylene bridge is very few, referring to：Morvan,D.；Capon,J.-F.；Gloaguen,F.；Goff,A.L.；
Marchivie,M.；Michaud,F.；Schollhammer,P.；Talarmin,J.；Yaouanc,J.-
J.Organometallics 2007,26,2042-2052；Tye,J.W.；Lee,J.；Wang,H.-W.；Mejia-
Rodriguez,R.；Reibenspies,J.H.；Hall,M.B.；Darensbourg.M.Y.Inorg.Chem.2005,44,
5550-5552.In order to develop ferrum ferrum hydrogenase biomimetic chemistry further, we utilize azepine Cabbeen and full carbonyl azepine trimethylene two
Between the carbonyl of sulfur two ferrum parent model thing, ligand exchange reaction has synthesized the novel ferrum ferrum hydrogenation catalator thing of structure.This kind of mould
Type thing had both contained the azepine trimethylene bridge of functionalization, contained the strong carbenes of various electron donations again, and they are low for research and development price
Honest and clean and catalytic performance excellent " artificial enzyme " produces hydrogen catalyst and has potential using value.
Content of the invention
The purpose of the present invention is for above-mentioned technical Analysis, provides a kind of trimethylene bridge of azepine containing functionalization and azepine Cabbeen to join
The ferrum ferrum hydrogenation catalator thing of body and its synthetic method.The preparation process of model thing is easy, reaction condition is gentle and product is received
Rate is high, can be used to prepare multiple not only nitrogen-containing hetero carbenes but also the ferrum ferrum of the trimethylene bridge of azepine containing functionalization hydrogenation catalator thing.
Technical scheme：
The ferrum ferrum hydrogenation catalator thing of a kind of trimethylene bridge of azepine containing functionalization and azepine carbenes, its chemical structural formula is such as
Shown in lower：
In structural formula：R is methoxyl group or methyl formate base, and L is 1- methyl -3- (2,4,6- trimethylphenyl) imidazoles -2-
Cabbeen or 1,3- methylimidazole -2- Cabbeen or 1- vinyl -3- (2,4,6- trimethylphenyl) imidazoles -2- Cabbeen or 1- propylene
Base -3- (2,4,6- trimethylphenyl) imidazoles -2- Cabbeen.
The ferrum ferrum of a kind of trimethylene bridge of azepine containing functionalization and azepine carbenes hydrogenates the synthetic method of catalator thing, step
As follows：
1), under nitrogen protection, polysubstituted imidazole salts and oxolane are mixed and are stirred at room temperature uniformly, then slowly
Add highly basic, be stirred at room temperature, obtain reactant liquor；
2) by above-mentioned reactant liquor with filtering equipped with diatomaceous anaerobic post, and rinsed with oxolane, obtain filtrate；
3) under nitrogen protection, by [(μ-SCH2)2N(C6H4R-p)]Fe2(CO)6It is added in above-mentioned filtrate, then room temperature
Stirring, TLC monitoring reaction disappears to corresponding raw material point；
4) by above-mentioned reactant liquor decompressing and extracting solvent, use dichloromethane extraction residue, then use dichloromethane and oil
Ether mixed liquor carries out TLC separation for developing solvent, collects mass-tone band, obtains solid and be target product.
Step 1) in imidazole salts mix with oxolane after 15min is stirred at room temperature, highly basic be n-BuLi hexane solution
Or potassium tert-butoxide, 30-60min is stirred at room temperature after strengthening alkali.
Step 2) in oxolane consumption be 15mL.
Step 3) in [(μ-SCH2)2N(C6H4R-p)]Fe2(CO)6Amount ratio with imidazole salts is 1mmol:3-13mmol,
4-6 hour is stirred at room temperature.
Step 4) in the volume ratio of dichloromethane and petroleum ether be 1mL:2-4mL.
The invention has the beneficial effects as follows：Prepare the ferrum of the trimethylene bridge of azepine containing functionalization and azepine carbenes using the method
Ferrum hydrogenates catalator thing, and reaction condition is gentle, simple to operate and yield is higher, is suitable for multiple trimethylene bridges of azepine containing functionalization
And the ferrum ferrum of azepine carbenes hydrogenates the preparation of catalator thing, and the Fe of this class model thingI-FeIBonding electron density is big, has
Beneficial to protonation, there is potential superior catalytic hydrogen production potential.
Specific embodiment
For more fully understanding the present invention, the solution of the present invention will be further illustrated by specific embodiment below, but this
The protection domain of invention should include the full content of claim, not limited to this.
Embodiment 1：
The ferrum ferrum of a kind of trimethylene bridge of azepine containing functionalization and azepine carbenes hydrogenates the preparation method of catalator thing 1, institute
The chemical formula stating model thing is [(μ-SCH2)2N(C6H4OMe-p)]Fe2(CO)5(L) [L=1- methyl -3- (2,4,6- trimethyl
Phenyl) imidazoles -2- Cabbeen], preparation process is as follows：
Concrete preparation process is as follows：
1) add 1- methyl -3- (2,4,6- trimethylbenzene in the 100mL there-necked flask equipped with nitrogen conduit and stirring magneton
Base) imidazoles iodate 500mg (1.52mmol), oxolane 15mL, 15min is stirred at room temperature, obtains white suspension, Ran Houhuan
Hexane solution (2.5M) 1.0mL (2.50mmol) of slow Deca n-BuLi, suspension rapidly goes to salmon pink clear liquor, room temperature
Stirring 30min, obtains reactant liquor；
2) by above-mentioned reactant liquor with filtering equipped with diatomaceous anaerobic post, and rinsed with 15mL oxolane, obtain orange
Color solution；
3) under nitrogen protection, by [(μ-SCH2)2N(C6H4OMe-p)]Fe2(CO)6(A) 149mg (0.30mmol) adds
To in above-mentioned system, 6h is stirred at room temperature, solution gradually becomes brownish red, TLC monitoring reaction disappears to corresponding raw material point；
4) by above-mentioned reactant liquor decompressing and extracting solvent, use dichloromethane extraction residue, then use dichloromethane/petroleum ether
=1：4 (v/v) carry out TLC separation as developing solvent, collect mass-tone band, obtain the brown-red solid 1 of 104mg, yield
52%.
Product structure data characterization is as follows：Fusing point:180℃；Anal.Calcd for C27H27Fe2N3O6S2:C,48.74；
H,4.09；N,6.32.Found:C,48.92；H,3.95；N,6.36.IR(KBr disk):νC≡O:2034(vs),1981(vs),
1966 (vs), 1941 (vs), 1903 (s) cm-1.1H NMR(400MHz,CDCl3):2.14(s,6H),2.40(s,3H),3.73
(s,5H,3.89(s,2H),4.00(s,3H),6.51-7.06(m,8H)ppm.13C NMR(75MHz,CDCl3):18.69(s),
21.2 (s), 39.7 (s), 50.5 (s), 55.6 (s), 114.6-153.5 (m), 187.4 (s), 210.9 (s), 215.4 (s)
ppm.
Embodiment 2：
The ferrum ferrum of a kind of trimethylene bridge of azepine containing functionalization and azepine carbenes hydrogenates the preparation method of catalator thing 2, institute
The chemical formula stating model thing is [(μ-SCH2)2N(C6H4OMe-p)]Fe2(CO)5(L) [L=1,3- methylimidazole -2- Cabbeen],
Preparation process is as follows：
Concrete preparation process is as follows：
1) in the 100mL there-necked flask equipped with nitrogen conduit and stirring magneton, add 1,3- methylimidazole iodate
1.120g (5.00mmol), oxolane 20mL, are stirred at room temperature 15min, are subsequently adding potassium tert-butoxide 672mg (6.00mmol),
1h is stirred at room temperature, obtains pink reactant liquor；
2) by above-mentioned reactant liquor with filtering equipped with diatomaceous anaerobic post, and rinsed with 15mL oxolane, obtain redness
Solution；
3) under nitrogen protection, by [(μ-SCH2)2N(C6H4OMe-p)]Fe2(CO)6(A) 198mg (0.40mmol) adds
To in above-mentioned system, 4h is stirred at room temperature, TLC monitoring reaction disappears to corresponding raw material point；
4) by above-mentioned reactant liquor decompressing and extracting solvent, use dichloromethane extraction residue, then use dichloromethane/petroleum ether
=1:2 (v/v) carry out TLC separation as developing solvent, collect mass-tone band, obtain the brown-red solid 2 of 180mg, yield
80%.
Product structure data characterization is as follows：Fusing point:168℃；Anal.Calcd for C19H19Fe2N3O6S2:C,40.67；
H,3.41；N,7.49.Found:C,40.55；H,3.32；N,7.62.IR(KBr disk):νC≡O:2032(vs),1970(vs),
1940(vs),1915(s)cm-1.1H NMR(400MHz,CDCl3):3.76(s,3H),3.97(s,6H),4.05-4022(m,
4H),6.65-6.89(m,6H)ppm.13C NMR(75MHz,CDCl3):39.6(s),50.3(s),55.7(s),114.9-
153.1(m),185.0(s),210.5(s),214.8(s)ppm.
Embodiment 3：
The ferrum ferrum of a kind of trimethylene bridge of azepine containing functionalization and azepine carbenes hydrogenates the preparation method of catalator thing 3, institute
The chemical formula stating model thing is [(μ-SCH2)2N(C6H4OMe-p)]Fe2(CO)5(L) [L=1- vinyl -3- (2,4,6- front three
Base phenyl) imidazoles -2- Cabbeen], preparation process is as follows：
Concrete preparation process is as follows：
1) add 1,2- bis- (3- (2,4,6- trimethylbenzene in the 100mL there-necked flask equipped with nitrogen conduit and stirring magneton
Base) imidazoles bromate) ethane 756mg (and 1.35mmol, this bromate in original position occur β-elimination be converted into 1- vinyl -3- (2,
4,6- trimethylphenyls) imidazoles bromate intermedium), oxolane 20mL, 15min is stirred at room temperature, obtains milky suspension,
Then it is slowly added dropwise hexane solution (2.5M) 1.1mL (2.75mmol) of n-BuLi, suspension rapidly goes to salmon pink clarification
Liquid, is stirred at room temperature 45min, obtains reactant liquor；
2) by above-mentioned reactant liquor with filtering equipped with diatomaceous anaerobic post, and rinsed with 15mL oxolane, obtain orange
Color solution；
3) under nitrogen protection, by [(μ-SCH2)2N(C6H4OMe-p)]Fe2(CO)6(A) 198mg (0.40mmol) adds
To in above-mentioned system, 6h is stirred at room temperature, TLC monitoring reaction disappears to corresponding raw material point；
4) by above-mentioned reactant liquor decompressing and extracting solvent, use dichloromethane extraction residue, then use dichloromethane/petroleum ether
=1：3 (v/v) carry out TLC separation as developing solvent, collect mass-tone band, obtain the red solid 3 of 144mg, yield
53%.
Product structure data characterization is as follows：Fusing point:206℃；Anal.Calcd for C28H27Fe2N3O6S2:C,49.65；
H,4.02；N,6.20.Found:C,49.51；H,4.13；N,6.17.IR(KBr disk):νC≡O:2028(vs),1981(vs),
1946 (vs), 1920 (s) cm-1.1H NMR(400MHz,CDCl3):2.15(s,6H),2.39(s,3H),3.62-3.95(m,
7H),5.04-5.24(m.3H),6.53-7.45(m,8H)ppm.13C NMR(75MHz,CDCl3):18.8(s),21.2(s),
50.4(s),55.6(s),102.5-153.6(m),194.8(s),210.4(s),215.2(s)ppm.
Embodiment 4：
The ferrum ferrum of a kind of trimethylene bridge of azepine containing functionalization and azepine carbenes hydrogenates the preparation method of catalator thing 4, institute
The chemical formula stating model thing is [(μ-SCH2)2N(C6H4CO2Me-p)]Fe2(CO)5(L) [L=1- acrylic -3- (2,4,6- tri-
Aminomethyl phenyl) imidazoles -2- Cabbeen], preparation process is as follows：
Concrete preparation process is as follows：
1) add 1- pi-allyl -3- (2,4,6- trimethyl in the 100mL there-necked flask equipped with nitrogen conduit and stirring magneton
Phenyl) imidazoles bromate 614mg (2.00mmol), oxolane 15mL, 15min is stirred at room temperature, obtains white suspension, then
It is slowly added dropwise hexane solution (2.5M) 0.8mL (2.00mmol) of n-BuLi, suspension rapidly goes to salmon pink clear liquor, room
Temperature stirring 30min, obtains reactant liquor；
2) by above-mentioned reactant liquor with filtering equipped with diatomaceous anaerobic post, and rinsed with 15mL oxolane, obtain orange
Color solution；
3) under nitrogen protection, by [(μ-SCH2)2N(C6H4CO2Me-p)]Fe2(CO)6(B) 160mg (0.31mmol) adds
Enter in above-mentioned system, 5h is stirred at room temperature, solution gradually becomes brownish red, TLC monitoring reaction disappears to corresponding raw material point；
4) by above-mentioned reactant liquor decompressing and extracting solvent, use dichloromethane extraction residue, then use dichloromethane/petroleum ether
=1：2 (v/v) carry out TLC separation as developing solvent, collect mass-tone band, obtain the brown-red solid 4 of 135mg, yield
61%.
Product structure data characterization is as follows：Fusing point:184℃；Anal.Calcd for C30H29Fe2N3O7S2:C,50.09；
H,4.06；N,5.84.Found:C,50.19；H,3.95；N,5.88.IR(KBr disk):νC≡O:2035(vs),1967(vs),
1952(s)cm-1.1H NMR(400MHz,CDCl3):1.74 (s, 3H), 2.15 (s, 6H), 2.43 (s, 3H), 3.86-4.08 (m,
7H), 5.75 (s, 1H), 6.00 (s, 1H), 6.51 (s, 2H), 6.88-7.08 (m, 4H), 7.84 (s, 2H) ppm.13C NMR
(75MHz,CDCl3):12.6(s),18.9(s),21.2(s),48.8(s),51.6(s),54.5(s),113.7-149.9(m),
166.9(s),186.8(s),210.3(s),214.5(s)ppm.
It will be clear that the invention is not restricted to embodiment here, those skilled in the art according to the announcement of the present invention,
All should be within protection scope of the present invention by the conspicuously improved and modification that present inventive concept is made.
Claims (6)
1. the ferrum ferrum hydrogenation catalator thing of a kind of trimethylene bridge of azepine containing functionalization and azepine carbenes, its chemical structural formula is as follows
Shown：
In structural formula：R is methoxyl group or methyl formate base, and L is 1- methyl -3- (2,4,6- trimethylphenyl) imidazoles -2- Cabbeen
Or 1,3- methylimidazole -2- Cabbeen or 1- vinyl -3- (2,4,6- trimethylphenyl) imidazoles -2- Cabbeen or 1- acrylic -
3- (2,4,6- trimethylphenyl) imidazoles -2- Cabbeen.
2. the ferrum ferrum of a kind of trimethylene bridge of azepine containing functionalization and azepine carbenes hydrogenates the preparation method of catalator thing, its feature
It is that step is as follows：
1), under nitrogen protection, polysubstituted imidazole salts and oxolane are mixed and is stirred at room temperature uniformly, be then slowly added into
Highly basic, is stirred at room temperature, and obtains reactant liquor；
2) by above-mentioned reactant liquor with filtering equipped with diatomaceous anaerobic post, and rinsed with oxolane, obtain filtrate；
3) under nitrogen protection, by [(μ-SCH2)2N(C6H4R-p)]Fe2(CO)6It is added in above-mentioned filtrate, then room temperature is stirred
Mix, TLC monitoring reaction disappears to corresponding raw material point；
4) by above-mentioned reactant liquor decompressing and extracting solvent, use dichloromethane extraction residue, then use dichloromethane and petroleum ether to mix
Close liquid and carry out TLC separation for developing solvent, collect mass-tone band, obtain solid and be target product.
3. the ferrum ferrum of the trimethylene bridge of azepine containing functionalization and azepine carbenes hydrogenates the system of catalator thing according to claim 2
Preparation Method it is characterised in that：Step 1) in imidazole salts mix with oxolane after 15min be stirred at room temperature, highly basic is n-BuLi
Hexane solution or potassium tert-butoxide, are stirred at room temperature 30-60min after strengthening alkali.
4. the ferrum ferrum of the trimethylene bridge of azepine containing functionalization and azepine carbenes hydrogenates the system of catalator thing according to claim 2
Preparation Method it is characterised in that：Step 2) in oxolane consumption be 15mL.
5. the ferrum ferrum of the trimethylene bridge of azepine containing functionalization and azepine carbenes hydrogenates the system of catalator thing according to claim 2
Preparation Method it is characterised in that：Step 3) in [(μ-SCH2)2N(C6H4R-p)]Fe2(CO)6Amount ratio with imidazole salts is 1mmol:
3-13mmol, is stirred at room temperature 4-6 hour.
6. the ferrum ferrum of the trimethylene bridge of azepine containing functionalization and azepine carbenes hydrogenates the system of catalator thing according to claim 2
Preparation Method it is characterised in that：Step 4) in the volume ratio of dichloromethane and petroleum ether be 1mL:2-4mL.
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| CN108440607A (en) * | 2018-04-13 | 2018-08-24 | 南开大学 | A kind of double-core nickel hydrogenation catalator object of the third disulphide bridges of nitrogen-containing hetero ligand and preparation method thereof |
| CN109160926A (en) * | 2018-06-29 | 2019-01-08 | 中北大学 | Iron iron hydrogenates the preparation and application of enzyme mimics and its carbon nanotube composite analogy object |
| CN113333030A (en) * | 2021-05-31 | 2021-09-03 | 齐鲁工业大学 | N-heterocyclic carbene-based- [ Fe-Fe ] hydrogenase model compound and preparation method and application thereof |
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- 2016-09-28 CN CN201610860317.1A patent/CN106478737A/en active Pending
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| CN108440607A (en) * | 2018-04-13 | 2018-08-24 | 南开大学 | A kind of double-core nickel hydrogenation catalator object of the third disulphide bridges of nitrogen-containing hetero ligand and preparation method thereof |
| CN109160926A (en) * | 2018-06-29 | 2019-01-08 | 中北大学 | Iron iron hydrogenates the preparation and application of enzyme mimics and its carbon nanotube composite analogy object |
| CN109160926B (en) * | 2018-06-29 | 2020-11-03 | 中北大学 | Preparation and application of iron-iron hydrogenase simulant and carbon nano tube composite simulant thereof |
| CN113333030A (en) * | 2021-05-31 | 2021-09-03 | 齐鲁工业大学 | N-heterocyclic carbene-based- [ Fe-Fe ] hydrogenase model compound and preparation method and application thereof |
| CN113333030B (en) * | 2021-05-31 | 2022-11-15 | 齐鲁工业大学 | N-heterocyclic carbene-based- [ Fe-Fe ] hydrogenase model compound and preparation method and application thereof |
| CN116284154A (en) * | 2023-02-28 | 2023-06-23 | 四川轻化工大学 | Monophosphine ligand-containing [ iron-iron ] hydrogenase mimic, and synthetic method and application thereof |
| CN116284154B (en) * | 2023-02-28 | 2024-06-04 | 四川轻化工大学 | Monophosphine ligand-containing [ iron-iron ] hydrogenase mimic, and synthetic method and application thereof |
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