CN109232665A - A kind of azepine trimethylene type hydrogenation catalator object and preparation method thereof - Google Patents
A kind of azepine trimethylene type hydrogenation catalator object and preparation method thereof Download PDFInfo
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- CN109232665A CN109232665A CN201811146542.4A CN201811146542A CN109232665A CN 109232665 A CN109232665 A CN 109232665A CN 201811146542 A CN201811146542 A CN 201811146542A CN 109232665 A CN109232665 A CN 109232665A
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- iron
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- monophosphorus ligand
- activity center
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- 238000002360 preparation method Methods 0.000 title description 3
- 238000005984 hydrogenation reaction Methods 0.000 title description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 198
- 229910052742 iron Inorganic materials 0.000 claims abstract description 86
- 230000000694 effects Effects 0.000 claims abstract description 43
- 239000003446 ligand Substances 0.000 claims abstract description 42
- 108010020056 Hydrogenase Proteins 0.000 claims abstract description 41
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000010189 synthetic method Methods 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 66
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 35
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- -1 lithium triethylborohydride Chemical compound 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 9
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000284 extract Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 10
- 238000004809 thin layer chromatography Methods 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000005580 one pot reaction Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000007039 two-step reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000006324 decarbonylation Effects 0.000 description 2
- 238000006606 decarbonylation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 150000001538 azepines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- 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)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The present invention provides a kind of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand, belongs to synthesis technical field.The model object molecular formula is Fe2[(μ‑SCH2)2NC6H4‑4‑I](CO)5L, chemical structural formula areThe chemical equation of reaction isWherein, L is monophosphorus ligand P (C6H4‑4‑CH3)3、P(C6H4‑4‑F)3、P(C6H4‑3‑CH3)3、P(C6H4‑3‑F)3Or P (C4H3O)3.The synthetic method of the present invention also provides described azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand.Synthetic method operating process of the present invention is simple, reaction condition is mild, product yield is higher, is suitably adapted for a variety of azepine trimethylene class [iron iron] hydrogenase activity center model object Fe containing monophosphorus ligand2[(μ‑SCH2)2NC6H4‑4‑I](CO)5The synthesis of L, azepine trimethylene class [iron iron] the hydrogenase activity center model object that the present invention synthesizes have good catalysis hydrogen production potential and potential industrial application value.
Description
Technical field
The invention belongs to synthesis technical field, in specifically a kind of azepine trimethylene class [iron iron] hydrogenase activity containing monophosphorus ligand
Heart model object Fe2[(μ-SCH2)2NC6H4-4-I](CO)5L and its synthetic method.
Background technique
Currently, the world is faced with energy-related two serious problems.Firstly, with worldwide keen competition, fossil
The continuous consumption of fuel will lead to high cost.Secondly, combustion of fossil fuel causes the gas concentration lwevel in atmosphere constantly to increase,
Further increase will cause tremendous influence to world climate.In order to keep the rapid growth of China's economy, country is clear
It is proposed deeply promotes energy revolution, puts forth effort that production of energy Land use systems is pushed to change, Optimization of Energy Structure, improves using energy source effect
Rate, construction cleaning low-carbon, safe and efficient modern energy system.Hydrogen Energy is considered as 21 century most potential cleaning energy
There is highest combustion heat value in source, and the product to burn only has mainly since it is not carbon containing compared with other chemical fuels
Water will not cause any pollution to environment.The extensive use of Hydrogen Energy can not only alleviate the energy crisis got worse, but also
The problems such as can solve by traditional fuel burning bring environmental pollution and greenhouse effects, realize the clean conversion of the energy and resource
It is utilized with efficient.Researcher attempts to find efficient, low cost synthesis hydrogen a approach, and microorganism is sharp in nature
The mode that can be used for reference is provided with the efficient hydrogen manufacturing of [iron iron] hydrogenase, becomes the hot spot studied at present.
Find that people have synthesized a series of azepine trimethylene classes [iron iron] containing monophosphorus ligand and hydrogenated enzyme activity by literature survey
Property center model object, but usually first need by two-step reaction, synthesize full carbonyl azepine trimethylene class [iron iron] hydrogenase first
Activated centre model object obtains the azepine trimethylene class [iron containing monophosphorus ligand using oxidation decarbonylation or the mode being heated to reflux
Iron] hydrogenase activity center model object, the total yield of two-step reaction is lower.
Summary of the invention
It is an object of the invention to: the difficult, properties for the preparation of existing [iron iron] hydrogenase activity center model object
Can be lower the problems such as, provides a kind of azepine trimethylene class [iron iron] the hydrogenase activity center model object containing monophosphorus ligand and its synthesis
Method, being somebody's turn to do [iron iron] hydrogenase activity center model object has good electron Phosphine ligands, can be improved catalytic activity and tool
There is potential industrial application value.Synthetic method of the invention is simple, one pot reaction, easy to operate, mild condition, yield compared with
Height can be used for synthesizing a variety of azepine trimethylene class [iron iron] hydrogenase activity center model objects containing monophosphorus ligand.,
In order to realize the above goal of the invention, the specific technical proposal of the invention is:
A kind of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand, the model object are Fe2[(μ-
SCH2)2NC6H4-4-I](CO)5L, structural formula are as follows:
Wherein, L is P (C6H4-4-CH3)3、P(C6H4-4-F)3、P(C6H4-3-CH3
)3、P(C6H4-3-F)3、P(C4H3O)3)。
The synthesis side of the invention further relates to described azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand
Method, comprising the following steps:
1) under inert gas conditions, by Fe2S2(CO)6It is dissolved in tetrahydrofuran solvent and is cooled to -78 DEG C；
2) it is slowly added to lithium triethylborohydride solution, trifluoroacetic acid is added after reacting 10~15min, the reaction was continued 10~15
Monophosphorus ligand L is added after min, after warming naturally to room temperature, continues to be stirred to react 3 hours；
3) in round-bottomed flask, paraformaldehyde and paraiodoaniline are dissolved in dichloromethane solvent, under the conditions of being protected from light,
After reacting 3 hours in 40 DEG C of water-baths, it is slow added into thionyl chloride, room temperature reaction removed dichloromethane solvent after one hour.
4) compound obtained in step (3) is added in step (2), adds triethylamine, continue that reaction 12 is stirred at room temperature
Hour.
5) tetrahydrofuran solvent is removed, and residue is extracted, finally carries out TLC separation, collects mass-tone band to get arriving
Azepine trimethylene class [iron iron] hydrogenase activity center model object of the present invention containing monophosphorus ligand.
Preferably, the Fe2S2(CO)6, tetrahydrofuran, lithium triethylborohydride amount ratio be 1mmol:15~
30mL:2~2.1mL.
Preferably, the amount ratio of the trifluoroacetic acid, lithium triethylborohydride is 0.16~0.2mL:2.0mL.
Preferably, described L, Fe2S2(CO)6The mass ratio of the material be 1~1.1mmol:1mmol.
Preferably, the methylene chloride: paraiodoaniline: paraformaldehyde: the amount ratio of thionyl chloride is 15~25mL:10
Mmol:25mmol:40mmol.
Preferably, the Fe2S2(CO)6, triethylamine amount ratio be 1mmol:0.3mL
Preferably, the cooling is cooled down using liquid nitrogen, acetone bath.
Preferably, the removing tetrahydrofuran solvent and dichloromethane solvent are in such a way that rotation is evaporated off.
Preferably, the extracting solution that the residue extracts is methylene chloride, the solvent of the TLC separation is volume
Than for 1:5 or 1:6 methylene chloride and petroleum ether.
Preferably, using L, (CH in the center model object of synthetic method synthesis2Cl)2NC6H4-4-I、Fe2S2(CO)6Substance
Amount ratio be 1~1.1mmol:2~2.5mmol:1mmol.
The invention has the following advantages:
(1), existing azepine trimethylene class [iron iron] the hydrogenase activity center model object and this hair containing monophosphorus ligand having disclosed
Bright [iron iron] hydrogenase activity center model object structure is not identical, and model object synthesized by the present invention is noval chemical compound；
(2), existing technology is to synthesize azepine trimethylene class [iron iron] hydrogenase center die containing monophosphorus ligand by two-step reaction
Type object Fe2[(μ-SCH2)2NC6H4-4-I](CO)5L, synthesis step is longer, and by-product is more, and yield is lower, higher cost；This
Invention one pot reaction can be achieved with, and synthetic method is simple, easy to operate, and yield is higher；
(3), existing technology be first synthesize full carbonyl azepine trimethylene class [iron iron] hydrogenase activity center model object, then by its
It is heated to reflux with monophosphorus ligand or carries out Reaction of carbonyl substitution under decarbonylation reagent existence condition and obtain the azepine containing Phosphine ligands
Trimethylene class [iron iron] hydrogenase activity center model；The present invention is ingenious to utilize one pot reaction, first synthesizes an important intermediate
Fe2[(μ- SH)2](CO)5L does not have to separate the intermediate, it directly can be obtained with the progress condensation reaction of double halides and contain
Azepine trimethylene class [iron iron] hydrogenase activity center model of monophosphorus ligand；
(4), azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand is synthesized using the method for the present invention,
Synthetic method is simple, one pot reaction, mild condition, yield are higher；The present invention is suitable for synthesizing a variety of azepines containing monophosphorus ligand
The synthesis of trimethylene class [iron iron] hydrogenase activity center model object；The azepine trimethylene class containing monophosphorus ligand of the method for the present invention synthesis
[iron iron] hydrogenase activity center model object has good properties activity, has potential industrial application value.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of model object 1 in embodiment 1；
Fig. 2 is the nuclear magnetic resonance phosphorus spectrum of model object 1 in embodiment 1；
Fig. 3 is the acid adding cyclic voltammogram of compound 1 in embodiment 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, to this hair
It is bright to be further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, is not used to
Limit the present invention.
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive spy
Other than sign and/or step, it can combine in any way.Any feature disclosed in this specification, unless specifically stated,
By other and other effects or there can be similar purpose alternative features to be replaced, that is, unless specifically stated, each feature is a system
Arrange an example in equivalent or similar characteristics.
Embodiment 1
A kind of synthetic method of azepine trimethylene class [iron iron] the hydrogenase activity center model object 1 containing Phosphine ligands, the model object 1
Chemical formula be Fe2[(μ-SCH2)2NC6H4-4-I](CO)5[P(C6H4-4-CH3)3], chemical synthesis process is as follows:
Specific synthesis step is as follows:
Under the conditions of inert gas shielding, 344mg Fe is added into the flask equipped with stirring magneton2S2(CO)6(1mmol) and 15
The tetrahydrofuran solvent of mL obtains wine-colored solution, obtained solution is cooled to -78 DEG C with liquid nitrogen bath, under stirring condition
It is slowly added to 2mL lithium triethylborohydride (1M in THF) solution, after reacting 15min, 0.16mL trifluoroacetic acid (2 is added
Mmol), after the reaction was continued 15min, the P (C of 304mg is added6H4-4-CH3)3(1.0mmol) is added after 3h is stirred at room temperature
630mg I-4-C6H4N(CH2Cl)2(2mmol) and 0.28mL triethylamine continues that reaction 12h is stirred at room temperature.Revolving removes tetrahydro
THF solvent extracts residue with methylene chloride, is then carried out with the solvent that methylene chloride/petroleum ether volume ratio is 1:5 thin
Layer chromatography separation collects mass-tone band to get model object 1 is arrived.
Attached drawing 1, attached drawing 2 and attached drawing 3 are the nuclear magnetic resonance spectroscopy of model object 1, phosphorus spectrum and acid adding cyclic voltammogram, Detailed description of the invention benefit
Can successfully it be synthesized with the method for the present invention with very high azepine trimethylene class [iron iron] hydrogenase containing monophosphorus ligand of purity
There is the model object 1 of activated centre model object, synthesis electro-catalysis to produce hydrogen activity.
The structured data of model object 1 is characterized as below:
1H NMR(δ,ppm,500MHz,CDCl3): 7.57 (m, 6H, PhH), 7.44 (d, J=4.0Hz, PhH), 7.22 (s,
6H, PhH), 6.33 (d, J=4.0Hz, PhH), 3.94 (d, J=6.0Hz, 2H, 2NCHaHeS), 2.98 (d, J=6.0Hz, 2H,
2NCHaHeS),2.37(s,10H,3CH3,NH).31P NMR(162MHz,CDCl3, 85%H3PO4):61.84(s).
Embodiment 2
A kind of synthetic method of azepine trimethylene class [iron iron] the hydrogenase activity center model object 2 containing monophosphorus ligand, the model
The chemical formula of object 2 is Fe2[(μ-SCH2)2NC6H4-4-I](CO)5[P(C6H4-4-F)3], chemical synthesis process is as follows:
Specific synthesis step is as follows:
Under the conditions of inert gas shielding, 344mg Fe is added into the flask equipped with stirring magneton2S2(CO)6(1mmol) and
The tetrahydrofuran solvent of 30mL obtains wine-colored solution, obtained solution is cooled to -78 DEG C with liquid nitrogen bath, stirring condition
Under be slowly added to 2.1mL lithium triethylborohydride (1M in THF) solution, after reacting 15min, 0.2mL trifluoroacetic acid is added
After the reaction was continued 15min, the P (C of 348mg is added in (2.5mmol)6H4-4-F)3(1.1mmol) is added after 3h is stirred at room temperature
788mg I-4-C6H4N(CH2Cl)2(2.5mmol) and 0.3mL triethylamine continues that reaction 12h is stirred at room temperature.Revolving removes tetrahydro
THF solvent extracts residue with methylene chloride, is then carried out with the solvent that methylene chloride/petroleum ether volume ratio is 1:5 thin
Layer chromatography separation collects mass-tone band to get model object 2 is arrived.
2 structured data of model object is characterized as below:
1H NMR(δ,ppm,400MHz,CDCl3): 7.63 (m, 6H, PhH), 7.45 (d, J=4.0Hz, PhH), 7.13 (s,
6H, PhH), 6.33 (d, J=4.0Hz, PhH), 4.00 (d, J=6.0Hz, 2H, 2NCHaHeS), 3.18 (d, J=6.0Hz, 2H,
2NCHaHeS).31P NMR(162MHz,CDCl3, 85%H3PO4):58.07(s).
Embodiment 3
A kind of synthetic method of azepine trimethylene class [iron iron] the hydrogenase activity center model object 3 containing monophosphorus ligand, the model
The chemical formula of object 3 is Fe2[(μ-SCH2)2NC6H4-4-I](CO)5[P(C6H4-3-Me)3], chemical synthesis process is as follows:
Specific synthesis step is as follows:
Under the conditions of inert gas shielding, 344mg Fe is added into the flask equipped with stirring magneton2S2(CO)6(1mmol) and
The tetrahydrofuran solvent of 20mL obtains wine-colored solution, obtained solution is cooled to -78 DEG C with liquid nitrogen bath, stirring condition
Under be slowly added to 2mL lithium triethylborohydride (1M in THF) solution, after reacting 15min, 0.18mL trifluoroacetic acid is added
After the reaction was continued 15min, the P (C of 304mg is added in (2.2mmol)6H4-3-CH3)3(1.0mmol) is stirred at room temperature after 3h and adds again
Enter 630mg I-4-C6H4N(CH2Cl)2(2mmol) and 0.28mL triethylamine continues that 12 h of reaction are stirred at room temperature.Revolving removes four
Hydrogen THF solvent extracts residue with methylene chloride, is then carried out with the solvent that methylene chloride/petroleum ether volume ratio is 1:6
TLC separation collects mass-tone band to get model object 3 is arrived.
3 structured data of model object is characterized as below:
1H NMR(δ,ppm,400MHz,CDCl3): 6.35-7.57 (m, 16H, PhH), 3.95 (d, J=6.0Hz, 2H,
2NCHaHeS),3.01(s,2H,2NCHaHeS),2.35(s,9H,3CH3).31P NMR(162MHz,CDCl3, 85% H3PO4):
63.86(s).
Embodiment 4
A kind of synthetic method of azepine trimethylene class [iron iron] the hydrogenase activity center model object 4 containing monophosphorus ligand, the model
The chemical formula of object 4 is Fe2[(μ-SCH2)2NC6H4-4-I](CO)5[P(C6H4-3-F)3], chemical synthesis process is as follows:
Specific synthesis step is as follows:
Under the conditions of inert gas shielding, 344mg Fe is added into the flask equipped with stirring magneton2S2(CO)6(1mmol) and
The tetrahydrofuran solvent of 20mL obtains wine-colored solution, obtained solution is cooled to -78 DEG C with liquid nitrogen bath, stirring condition
Under be slowly added to 2mL lithium triethylborohydride (1M in THF) solution, after reacting 15min, 0.18mL trifluoroacetic acid is added
After the reaction was continued 15min, the P (C of 348mg is added in (2.2mmol)6H4-3-F)3(1.0mmol) is added after 3 h are stirred at room temperature
630mg I-4-C6H4N(CH2Cl)2(2mmol) and 0.28mL triethylamine continues that reaction 12h is stirred at room temperature.Revolving removes tetrahydro
THF solvent extracts residue with methylene chloride, is then carried out with the solvent that methylene chloride/petroleum ether volume ratio is 1:5 thin
Layer chromatography separation collects mass-tone band to get model object 4 is arrived.
4 structured data of model object is characterized as below:
1H NMR(δ,ppm,400MHz,CDCl3): 6.36-7.47 (m, 16H, PhH), 4.00 (d, J=6.0Hz, 2H,
2NCHaHeS),3.22(s,2H,2NCHaHeS).31P NMR(162MHz,CDCl3, 85%H3PO4):66.68(s).
Embodiment 5
A kind of synthetic method of azepine trimethylene class [iron iron] the hydrogenase activity center model object 4 containing monophosphorus ligand, the model
The chemical formula of object 5 is Fe2[(μ-SCH2)2NC6H4-4-I](CO)5[P(2-C4H3O)3], chemical synthesis process is as follows:
Specific synthesis step is as follows:
Specific synthesis step is as follows:
Under the conditions of inert gas shielding, 344mg Fe is added into the flask equipped with stirring magneton2S2(CO)6(1mmol) and 20
The tetrahydrofuran solvent of mL obtains wine-colored solution, obtained solution is cooled to -78 DEG C with liquid nitrogen bath, under stirring condition
It is slowly added to 2mL lithium triethylborohydride (1M in THF) solution, after reacting 15min, 0.18mL trifluoroacetic acid is added
After the reaction was continued 15min, the P (2-C of 232mg is added in (2.2mmol)4H3O)3(1.0mmol) is added after 3h is stirred at room temperature
630mg I-4-C6H4N(CH2Cl)2(2mmol) and 0.28mL triethylamine continues that reaction 12h is stirred at room temperature.Revolving removes tetrahydro
THF solvent extracts residue with methylene chloride, is then carried out with the solvent that methylene chloride/petroleum ether volume ratio is 1:5 thin
Layer chromatography separation collects mass-tone band to get model object 5 is arrived.
5 structured data of model object is characterized as below:
1H NMR(δ,ppm,400MHz,CDCl3):7.74(s,3H,furylH),6.96(s,3H,furylH),6.50(s,3H,
), furylH 7.45 (d, J=4.0Hz, PhH), 6.37 (d, J=4.0Hz, PhH), 4.11 (d, J=6.0Hz, 2H,
2NCHaHeS), 3.44(s,2H,2NCHaHeS)。
Claims (10)
1. a kind of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand, which is characterized in that the mould
Type object is Fe2[(μ-SCH2)2NC6H4-4-I](CO)5L, structural formula are as follows:
Wherein, L is P (C6H4-4-CH3)3、P(C6H4-4-F)3、P(C6H4-3-CH3)3、P(C6H4-3-F)3、P(C4H3O)3。
2. a kind of conjunction of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand as described in claim 1
At method, which comprises the following steps:
1) under inert gas conditions, by Fe2S2(CO)6It is dissolved in tetrahydrofuran solvent and is cooled to -78 DEG C；
2) it is slowly added to lithium triethylborohydride solution, trifluoroacetic acid is added after reacting 10~15min, the reaction was continued 10~
Monophosphorus ligand L is added after 15min, after warming naturally to room temperature, continues to be stirred to react 3 hours；
3) in round-bottomed flask, paraformaldehyde and paraiodoaniline are dissolved in dichloromethane solvent, under the conditions of being protected from light, 40
After reacting 3 hours in DEG C water-bath, it is slow added into thionyl chloride, removes dichloromethane solvent after reacting at room temperature 1h；
4) compound obtained in step 3) is added in step 2), adds triethylamine, it is small to continue to be stirred at room temperature reaction 12
When；
5) tetrahydrofuran solvent is removed, and residue is extracted, finally carries out TLC separation, collects mass-tone band to get arriving
Azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand.
3. the synthesis side of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand as claimed in claim 2
Method, which is characterized in that the Fe2S2(CO)6, tetrahydrofuran, lithium triethylborohydride amount ratio be 1mmol:15~30mL:2
~2.1mL.
4. the synthesis side of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand as claimed in claim 2
Method, which is characterized in that the trifluoroacetic acid, lithium triethylborohydride amount ratio be 0.16~0.2mL:2.0mL.
5. the synthesis side of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand as claimed in claim 2
Method, which is characterized in that the monophosphorus ligand L, (CH2Cl)2NC6H4-4-I、Fe2S2(CO)6The mass ratio of the material be 1~
1.1mmol:2.0~2.5mmol:1.0mmol.
6. the synthesis side of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand as claimed in claim 2
Method, which is characterized in that the Fe2S2(CO)6, triethylamine amount ratio be 1mmol:0.3mL.
7. the synthesis side of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand as claimed in claim 2
Method, which is characterized in that the methylene chloride: paraiodoaniline: paraformaldehyde: the amount ratio of thionyl chloride is 15~25mL:
10mmol:25mmol:40mmol.
8. the synthesis side of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand as claimed in claim 2
Method, which is characterized in that the cooling is cooled down using liquid nitrogen, acetone bath；The removing tetrahydrofuran solvent and methylene chloride
Solvent is in such a way that rotation is evaporated off.
9. the synthesis side of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand as claimed in claim 2
Method, which is characterized in that the extracting solution that the residue extracts is methylene chloride, and the solvent of the TLC separation is volume
Than the methylene chloride and petroleum ether mixtures for 1:5 or 1:6.
10. the synthesis of azepine trimethylene class [iron iron] hydrogenase activity center model object containing monophosphorus ligand as claimed in claim 2
Method, which is characterized in that the synthetic method is suitable for other azepine trimethylene class [iron iron] hydrogenase activities containing monophosphorus ligand
The synthesis of center model object.
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| CN115304648A (en) * | 2022-08-17 | 2022-11-08 | 西安交通大学 | Iron-iron hydrogenase model compound containing porphyrin ring system and synthesis method and application thereof |
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| CN115304648A (en) * | 2022-08-17 | 2022-11-08 | 西安交通大学 | Iron-iron hydrogenase model compound containing porphyrin ring system and synthesis method and application thereof |
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