CN104370975B - A kind of butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things and preparation method thereof - Google Patents
A kind of butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things and preparation method thereof Download PDFInfo
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Abstract
A kind of butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, it is that the class using the synthesis of μ CO intermediate molecule internal condensation is with Fe2(μ S) (μ PR) is [FeFe] hydrogenase model thing of skeleton, and this class model thing bridge formation atom is respectively S atom and P atom, and it has a chemical structural formula as follows:In structural formula: n represents that the number of carbon atom herein is 0 or 1；R is chlorine, phenyl, methoxyl group, ethyoxyl, diethylamino or 4 bromine butoxy.This method provides the benefit that: this butterfly-shaped [Fe2SP] the preparation method technique of type hydrogenation catalator thing is simple, and cheaper starting materials is easy to get, and reaction condition is gentle, can prepare multiple [Fe2SP] type hydrogenation catalator thing to be to expand application in ferrum ferrum hydrogenase biomimetic chemistry field.
Description
Technical field
The invention belongs to that metal is organic and energy science field, a kind of butterfly-shaped two ferrum sulfur phosphorus hydrogenase models
Thing and preparation method thereof.
Background technology
Ferrum ferrum hydrogenase is in one is present in multiple-microorganism body and has efficient catalytic proton reduction generation hydrogen
The metalloenzyme of gas ability, has just caused the research interest that people are dense since being found, is attempted to pass through
Ferrum ferrum hydrogenase biomimetic chemistry is studied and is catalyzed generation hydrogen for " artificial enzyme " synthesizing a kind of Cheap highly effective
Gas, to alleviate significant problem (Ogino, the H. such as the most serious energy shortage and environmental pollution；Inomata,S.；
Tobita,H.Chem.Rev.1998,98,2093-2122；Fontecilla-Camps,J.C.；
Volbeda,A.；Cavazza,C.；Nicolet,Y.Chem.Rev.2007,107,4273-4303；
Darensbourg,M.Y.；Lyon,E.J.；Smee,J.J.Coord.Chem.Rev.2000,
206-207,533-561).Up to now, the ferrum ferrum hydrogenase model thing of document report mostly contains [Fe2S2]
Butterfly-shaped skeleton, but containing [Fe2SP] research of framework compound is the most little, and the overwhelming majority is all opened
Chain compound, structurally differs greatly (Evans, D.J. with ferrum ferrum hydrogenase activity center；Pickett,
C.J.Chem.Soc.Rev.,2003,32,268-275；Simmons T.R.；Berggren,G.；
Bacchi,M.；Fontecave,M.；Artero,V.Coord.Chem.Rev.2014,270-271,
127-150)。
Butterfly-shaped ferrum sulfur μ-CO intermediate has the highest reactivity, it is possible to multiple organic and inorganic and golden
Belong to organic substrates generation necleophilic reaction, and itself skeleton is similar with ferrum ferrum hydrogenase activity center, therefore may be used
To expect that they researchs in terms of ferrum ferrum hydrogenase bionic catalysis have significant application value (Seyferth, D.；
Womack,G.B.；Dewan,J.C.Organometallics,1985,4,398-400；Song Licheng,
The Advances In Chemistry of novel butterfly-shaped Fe/E/ μ-CO (E=S, Se, Te) bunch salt, Chinese science collecting of B
Learn, 2008,38,10,851-866；Song,L.-C.Trends.Organomet.Chem.1999,
3,1-20).We utilize butterfly-shaped ferrum sulfur μ-CO intermediate the most electrophilic with phosphorus trihalide and phenylphosphonic dichloride
Reagent reacting, is generating [Fe2SP] continuously add alkali after open chain type compound and promote its intramolecular condensation cyclization,
Generate the Novel iron ferrum hydrogenase model thing increasingly similar with native iron ferrum hydrogenase activity center.
Summary of the invention
It is an object of the invention to for above-mentioned technical Analysis, it is provided that a kind of butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things
Preparation method, these butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things use the method or right of intramolecular condensation cyclization
The method that P-X (X=Cl, Br) functional group carries out modifying is prepared, and technique is simple, cheaper starting materials is easy to get, instead
Answer mild condition, multiple [Fe can be prepared2SP] type hydrogenation catalator thing with expand in ferrum ferrum hydrogenase biomimetic chemistry
The application in field.
Technical scheme:
A kind of butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, it is to use the synthesis of μ-CO intermediate molecule internal condensation
One class is with Fe2(μ-S) (μ-PR) is [FeFe]-hydrogenase model thing of skeleton, this class model thing bridge formation atom
Being respectively S atom and P atom, it has a chemical structural formula as follows:
In structural formula: n represents that the number of carbon atom herein is 0 or 1；R be chlorine, phenyl, methoxyl group, ethyoxyl,
Diethylamino or 4-bromine butoxy.
A kind of preparation method of described butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, step is as follows:
1) in nitrogen displacement is equipped with the reaction bulb stirring magneton, tri-iron dodecacarbonyl is added in organic solvent
And mix homogeneously, obtain mixed liquor；
2) in above-mentioned mixed liquor, add hydroxy thiol and triethylamine, react 15min, obtain reactant liquor；
3) add in above-mentioned reactant liquor and continue reaction 6h after electrophilic reagent, add triethylamine be stirred overnight or
Backflow 4h, obtains the suspension of redness；
4) in above-mentioned suspension, continuously add triethylamine or triethylamine and methanol or triethylamine and diethylamine is follow-up
Continuous reaction 6h；
5) decompressing and extracting solvent, uses dichloromethane extraction residue, with the dichloromethane that volume ratio is 1:7-
Petroleum ether carries out TLC separation as developing solvent, collects red mass-tone band, obtains red solid and is and contains
[Fe2SP] compound of skeleton.
Described step 1) in organic solvent be oxolane or ether；Tri-iron dodecacarbonyl and the use of organic solvent
Amount ratio is 3mmol:30mL.
Described step 2) in hydroxy thiol be o-hydroxy thiophenol or adjacent mercapto benzyl alcohol；Mixed liquor, hydroxy thiol
It is 30mL:3mmol:3mmol with the amount ratio of triethylamine.
Described step 3) in electrophilic reagent be Phosphorous chloride., phenyl dichloro phosphorus or phosphorus tribromide；Reactant liquor,
Electrophilic reagent, the amount ratio of triethylamine are 30mL:4.5mmol:3mmol.
Described step 4) in the amount ratio of suspension and triethylamine be 30mL:3mmol；Suspension, triethylamine,
The amount ratio of methanol is 30mL:3mmol:5mmol；Suspension, triethylamine, the amount ratio of diethylamine are
30mL:3mmol:5mmol。
The functional modification of the present invention is that addition methanol or diethylamine reaction obtain under the conditions of triethylamine.The present invention
When middle use phosphorus tribromide is as electrophilic reagent, it has unexpectedly been found that solvents tetrahydrofurane, ether can be transferred through C-O
Bond fission participates in reaction, obtains the functional modification product of novelty.
This method provides the benefit that: this butterfly-shaped [Fe2SP] the preparation method technique of type hydrogenation catalator thing is simple,
Cheaper starting materials is easy to get, and reaction condition is gentle, can prepare multiple [Fe2SP] type hydrogenation catalator thing with expand at ferrum ferrum
The application in hydrogenase biomimetic chemistry field.
Detailed description of the invention
For being more fully understood that the present invention, the solution of the present invention will be further illustrated by specific embodiment below,
But protection scope of the present invention should include the full content of claim, is not limited to this.
Embodiment 1:
The preparation method of a kind of described butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, the chemical formula of described model thing is
[μ-SC6H4OP(Ph)-μ]Fe2(CO)6, preparation process is as follows:
Concrete preparation process is as follows:
1), under nitrogen protection, in the 100mL round bottom Schlenk flask equipped with stirring magneton, 1.5 are added
G tri-iron dodecacarbonyl (3.0mmol) and 30mL oxolane, obtain mixed liquor；
2) in above-mentioned mixed liquor, 0.3mL o-hydroxy thiophenol (3.0mmol) and 0.42mL is added under stirring
Triethylamine (3.0mmol), solution is green, 15min is stirred at room temperature, obtains reactant liquor；
3) in above-mentioned reactant liquor, add 0.60mL phenylphosphonic dichloride (4.5mmol) continue afterwards to react 6h,
Add 0.42mL triethylamine (3.0mmol) back flow reaction 4h；
4) in above-mentioned suspension, continuously add 0.42mL triethylamine (3.0mmol) continue afterwards to react 6h；
5) decompressing and extracting solvent, uses dichloromethane extraction residue, with the dichloromethane that volume ratio is 1:7-
Petroleum ether carries out TLC separation as developing solvent, collects red mass-tone band, obtains red solid 166mg
It is containing [Fe2SP] framework compound, productivity 10.8%.
Product structure data characterization is as follows: fusing point: 125-126 DEG C；Anal.Calcd for C18H9Fe2O7PS:
C,42.23；H,1.77.Found:C,42.15；H,1.56.IR(KBr disk):νC≡O 2069(s),
2029(vs),1979(vs)cm-1.1H NMR(400MHz,CDCl3):8.07-8.01(m,2H),
7.80-7.79(m,1H),7.68-7.61(m,3H),7.33-7.26(m,1H),7.05-6.95(m,
2H)ppm.31P NMR(161.9MHz,CDCl3):260.73(s)ppm.13C NMR(100MHz,CDCl3):
209.26(s),154.02(s),137.09(s),133.86(s),132.30(s),132.00(s),
130.50(s),129.03(s),122.69(s),120.41(s),115.31(s),115.07(s)
ppm.
Embodiment 2:
The preparation method of a kind of described butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, the chemical formula of described model thing is
[μ-SC6H4OP(Cl)-μ]Fe2(CO)6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 1, and difference is: step 3) in 15min is stirred at room temperature
After, change into adding 0.39mL Phosphorous chloride. (4.5mmol), after adding 0.42mL triethylamine, change room into
Temperature is stirred overnight post processing reaction, obtains red solid 182mg containing [Fe2SP] framework compound, productivity 12.9%.
Product structure data characterization is as follows: fusing point: 106-107 DEG C；Anal.Calcd for C12H4ClFe2O7PS:
C,30.64；H,0.86.Found:C,30.85；H,1.02.IR(KBr disk):νC≡O 2077(vs),
2040(vs),1995(vs)cm-1.1H NMR(400MHz,CDCl3): 7.74 (d, J=7.7Hz,
1H),7.40-7.26(m,1H),7.09-7.03(m,2H)ppm.31P NMR(161.9MHz,CDCl3):
299.25(s)ppm.13C NMR(100MHz,CDCl3):208.50(s),208.16(s),155.02
(s),133.84(s),131.07(s),123.50(s),120.43(s),114.47(s),114.21
(s)ppm.
Embodiment 3:
The preparation method of a kind of described butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, the chemical formula of described model thing is
[μ-SC6H4OP(OMe)-μ]Fe2(CO)6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 2, and difference is: step 4) in add triethylamine after change
For adding 0.42mL triethylamine (3.0mmol) and 0.2mL methanol (5.0mmol) reaction 6h, obtain red solid
Body 147mg is containing [Fe2SP] framework compound, productivity 10.5%.
Product structure data characterization is as follows: fusing point: 118-119 DEG C；Anal.Calcd for C13H7Fe2O8PS:
C,33.51；H,1.51.Found:C,33.37；H,1.48.IR(KBr disk):νC≡O 2076(s),
2031(vs),1989(vs),1962(vs)cm-1.1H NMR(400MHz,CDCl3):7.74-7.72
(m,1H),7.34-7.26(m,1H),7.01-6.95(m,2H),5.30(s,3H).ppm.31P NMR
(161.9MHz,CDCl3):222.18(s)ppm.13C NMR(100MHz,CDCl3):209.42(s),
208.48(s),152.79(s),134.23(s),130.76(s),122.95(s),120.39(s),
120.35(s),115.65(s),69.97(s),69.83(s)ppm.
Embodiment 4:
The preparation method of a kind of described butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, the chemical formula of described model thing is
[μ-SC6H4OP(NEt2)-μ]Fe2(CO)6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 3, and difference is: step 4) in change 0.42mL tri-into
Ethamine (3.0mmol) and 0.25mL diethylamine (5.0mmol) reaction 6h, obtain red solid 118mg,
Productivity 7.7%.
Product structure data characterization is as follows: fusing point: 113-114 DEG C；Anal.Calcd for
C16H14Fe2NO7PS:C,37.90；H,2.78；N,2.76.Found:C,37.62；H,2.56；
N,3.01.IR(KBr disk):νC≡O 2069(s),2027(vs),1979(vs)cm-1.1H NMR(400
MHz,CDCl3): 7.78 (d, J=7.7Hz, 1H), 7.33-7.31 (m, 1H), 7.00-6.93 (m,
2H), 3.67-3.59 (m, 4H), 1.37 (t, J=7.1Hz, 6H) ppm.31P NMR(161.9MHz,
CDCl3):265.08(s)ppm.13C NMR(100MHz,CDCl3):209.37(s),154.64(s),
133.47(s),129.89(s),122.04(s),119.72(s),114.59(s),114.37(s),
46.06(s),46.04(s),13.42(s)ppm.
Embodiment 5:
The preparation method of a kind of described butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, the chemical formula of described model thing is
[μ-SC6H4OP(OCH2CH2CH2CH2Br)-μ]Fe2(CO)6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 2, and difference is: by 0.43ml phosphorus tribromide (4.5mmol)
Replace 0.39mL Phosphorous chloride. (4.5mmol), obtain red solid 237mg, productivity 15.6%.
Product structure data characterization is as follows: fusing point: 136-137 DEG C；Anal.Calcd for
C16H12BrFe2O8PS:C,32.74；H,2.06.Found:C,32.52；H,2.17.IR(KBr
disk):νC≡O 2072(s),2030(vs),1983(vs)cm-1.1H NMR(400MHz,CDCl3):7.76
(d, J=7.8Hz, 1H), 7.37-7.33 (m, 1H), 7.04-7.00 (m, 2H), 4.49-4.45 (m,
2H), 3.54 (t, J=6.2Hz, 2H), 2.39-1.85 (m, 4H) .ppm.31P NMR(161.9MHz,
CDCl3):287.80(s)ppm.13C NMR(100MHz,CDCl3):208.89(s),208.84(s),
153.61(s),133.51(s),130.27(s),122.88(s),119.65(s),115.60(s),
115.36(s),71.96(s),71.83(s),33.06(s),29.19(s),28.81(s)ppm.
Embodiment 6:
The preparation method of a kind of described butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, the chemical formula of described model thing is
[μ-SC6H4OP(OCH2CH3)-μ]Fe2(CO)6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 2, and difference is: solvent ether (30mL) is replaced four
Hydrogen furan (30mL), obtains red solid 206mg, productivity 14.3%.
Product structure data characterization is as follows: fusing point: 129-130 DEG C；Anal.Calcd for C14H9Fe2O8PS:
C,35.04；H,1.89.Found:C,35.10；H,2.00.IR(KBr disk):νC≡O 2065(vs),
2021(vs),1998(vs),1958(s)cm-1.1H NMR(400MHz,CDCl3): 7.75 (d, J=7.7
Hz,1H),7.36-7.32(m,1H),7.03-6.99(m,2H),4.55-4.43(m,2H),1.59
(t, J=7.0Hz, 3H) ppm.31P NMR(161.9MHz,CDCl3):286.52(s)ppm.13C NMR
(100MHz,CDCl3):208.95(s),153.70(s),133.54(s),130.23(s),122.84
(s),119.72(s),115.70(s),115.47(s),69.45(s),69.33(s),16.42(s)
ppm.
Embodiment 7:
The preparation method of a kind of described butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, the chemical formula of described model thing is
[μ-SC6H4CH2OP(Ph)-μ]Fe2(CO)6)6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 1, and difference is: by 420mg neighbour's mercapto benzyl alcohol (3.0
Mmol) replace 0.3mL o-hydroxy thiophenol (3.0mmol), obtain red solid 124mg, productivity 7.8%.
Product structure data characterization is as follows: fusing point: 119-120 DEG C；Anal.Calcd for C19H11Fe2O7PS:
C,43.38；H,2.11.Found:C,43.47；H,2.30.IR(KBr disk):νC≡O 2060(s),
2020(vs),1985(vs)cm-1.1H NMR(400MHz,CDCl3):7.96-7.89(m,3H),7.62
(s,3H),7.37(s,3H),5.10(2s,2H)ppm.31P NMR(161.9MHz,CDCl3):
281.90(s)ppm.13C NMR(100MHz,d6-DMSO):209.86(s),136.73(s),135.97
(s),134.12(s),132.89(s),132.79(s),132.46(s),131.12(s),129.40
(s),129.07(s),128.97(s),126.99(s),126.78(s),126.62(s),26.81
(s)ppm.
Embodiment 8:
The preparation method of a kind of described butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, the chemical formula of described model thing is
[μ-SC6H4CH2OP(Cl)-μ]Fe2(CO)6, preparation process is as follows:
Concrete preparation process is substantially the same manner as Example 2, and difference is: by 420mg neighbour's mercapto benzyl alcohol (3.0
Mmol) replace 0.3mL o-hydroxy thiophenol (3.0mmol), obtain red solid 137mg, productivity 9.4%.
Product structure data characterization is as follows: fusing point: 96-97 DEG C；Anal.Calcd for C13H6ClFe2O7PS:
C,32.24；H,1.25.Found:C,32.48；H,1.29.IR(KBr disk):νC≡O 2077(s),
2042(vs),2012(vs),1984(vs)cm-1.1H NMR(400MHz,d6-DMSO):7.92-7.80(m,
1H), 7.45-7.29 (m, 3H), 5.20 (2d, J=20.3Hz, 2H) ppm.31P NMR(161.9MHz,
CDCl3):286.57(s)ppm.13C NMR(100MHz,CDCl3):209.12(s),208.67(s),
138.34(s),136.80(s),136.51(s),134.90(s),130.86(s),129.11(s),
128.82(s),70.52(s),70.39(s).ppm.
Claims (6)
1. butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, it is characterised in that: it is to use μ-CO intermediate to divide
One class of sub-internal condensation synthesis is with Fe2(μ-S) (μ-PR) is [FeFe]-hydrogenase model thing of skeleton, such
Model thing bridge formation atom is respectively S atom and P atom, and it has a chemical structural formula as follows:
In structural formula: n represents that the number of carbon atom herein is 0 or 1；R be chlorine, phenyl, methoxyl group, ethyoxyl,
Diethylamino or 4-bromine butoxy.
2. a preparation method for butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things as claimed in claim 1, its feature exists
As follows in step:
1) in nitrogen displacement is equipped with the reaction bulb stirring magneton, tri-iron dodecacarbonyl is added in organic solvent
And mix homogeneously, obtain mixed liquor；
2) in above-mentioned mixed liquor, add hydroxy thiol and triethylamine, react 15min, obtain reactant liquor；
3) add in above-mentioned reactant liquor and continue reaction 6h after electrophilic reagent, add triethylamine be stirred overnight or
Backflow 4h, obtains the suspension of redness；
4) in above-mentioned suspension, continuously add triethylamine or triethylamine and methanol or triethylamine and diethylamine is follow-up
Continuous reaction 6h；
5) decompressing and extracting solvent, uses dichloromethane extraction residue, with the dichloromethane that volume ratio is 1:7-
Petroleum ether carries out TLC separation as developing solvent, collects red mass-tone band, obtains red solid and is and contains
[Fe2SP] framework compound.
The preparation method of the most butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, it is characterised in that:
Described step 1) in organic solvent be oxolane or ether；Tri-iron dodecacarbonyl and the amount ratio of organic solvent
For 3mmol:30mL.
The preparation method of the most butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, it is characterised in that:
Described step 2) in hydroxy thiol be o-hydroxy thiophenol or adjacent mercapto benzyl alcohol；Mixed liquor, hydroxy thiol and three
The amount ratio of ethamine is 30mL:3mmol:3mmol.
The preparation method of the most butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, it is characterised in that:
Described step 3) in electrophilic reagent be Phosphorous chloride., phenyl dichloro phosphorus or phosphorus tribromide；Reactant liquor, electrophilic
Reagent, the amount ratio of triethylamine are 30mL:4.5mmol:3mmol.
The preparation method of the most butterfly-shaped two ferrum sulfur phosphorus hydrogenase model things, it is characterised in that:
Described step 4) in the amount ratio of suspension and triethylamine be 30mL:3mmol；Suspension, triethylamine, methanol
Amount ratio be 30mL:3mmol:5mmol；Suspension, triethylamine, the amount ratio of diethylamine are
30mL:3mmol:5mmol。
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