CN110627826A - Four-electron homogeneous phase reducing agent, preparation method and application thereof - Google Patents
Four-electron homogeneous phase reducing agent, preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/02—Lithium compounds
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
- C07F7/0807—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms comprising Si as a ring atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
Abstract
The invention discloses a 2,3,4,5,2 ', 3', 4 ', 5' -octa-aryl spiro silole tetranegative ion compound with a structure shown in a formula (I),in the formula, Ar is C6～C10An aromatic group or a substituted aromatic group, preferably one of phenyl, 2, 6-dimethylphenyl or 2, 6-diisopropylphenyl. The reducing agent is used for diquinone, bis (triphenylphosphine) palladium dichloride, methyl iodide and oxygen systems to show high-efficiency reduction performance, and the thermal stability, the solubility and the chemical stability of the reducing agent are good; the preparation method is simple and the yield is high; safe in useThe aryl spiro silole compound is nontoxic, tasteless and environment-friendly, and has wider application prospect in homogeneous phase reducing agents. The invention further discloses a preparation method and application of the aryl spiro silole tetraanion compound.
Description
Technical Field
The invention relates to a homogeneous phase reducing agent, a preparation method and application thereof, in particular to a four-electron homogeneous phase reducing agent containing a spiro silole structure, a preparation method and application thereof.
Background
The reduction reaction is an important reaction in the field of synthetic chemistry, and is widely applied to metallurgy, chemical engineering, materials and biomedicine. The reducing agents commonly used today are mainly some alkali metals and alkaline earth metals, such as: metallic lithium (Li), sodium (Na), potassium (K), magnesium (Mg), and the like. However, the reducing agents of the above type are heterogeneous reducing agents, and they are immiscible with the reaction system, so that the reaction is slow to proceed, the reaction selectivity is poor, and excessive reduction is easily caused. The homogeneous phase reducing agent can avoid the problems, the homogeneous phase reducing agent and a reduction system can be mutually dissolved and quantitatively react, the reaction is easy to control, the obtained reduction product is single, and the yield is high.
At present, the commonly used homogeneous reducing agents are mainly naphthalene lithium, Birch reagent and samarium diiodide (Smi)2) And the like. Birch, 1944, reported that lithium and sodium metals were dissolved in liquid ammonia solventThe homogeneous system single electron reducing agent can efficiently reduce aldehyde and ketone, is named as a Birch reducing agent (see Birch, A, J.J.Chem.Soc. 1944.430), and has wide application in synthetic chemistry (see Birch, A, J.J.Chem.Soc.1946.593; J.Chem.Soc.1947.102). Samaric diiodide homogeneous one-electron reductants were reported in 1980 by h.b. Kagan (see Girard, p.; Namy, j.l.; Kagan, h.b.j.am. chem. soc.1980,102, 2693), which were named as Kagan reagents, can achieve highly efficient asymmetric reduction of imines, aldehydes, ketones, etc., into the most commonly used homogeneous one-electron reductants at present (see Krief, a.; Laval, a.m. chem. rev. 1999,99, 745). Lithium naphthalene is also a commonly used homogeneous reducing agent, and has found wide application, particularly in the fields of inorganic synthesis, elemental organic chemistry, and anionic polymerization (see Molander, g.a. chem.rev.1992,92, 29).
Compared with a single-electron homogeneous phase reducing agent, the multi-electron reducing agent can release a plurality of electrons simultaneously in the reduction reaction, can accelerate the reduction reaction and improve the selectivity of the reduction reaction, and particularly shows obvious advantages in the fields of element organic synthesis chemistry, metallurgy and pharmacy.
Chinese patent CN103274950A reports a homogeneous phase double electron reducing agent ammonium thiosulfate which can efficiently reduce nitrobenzene to prepare aniline. Specifically, nitrobenzene takes ammonium thiosulfate as a reducing agent in an alcoholic solution, and carries out reduction reaction at 30-100 ℃, and aniline is obtained after complete reaction and post-treatment.
It is disclosed in US5,831,097, EP0364752, US4,950,306 that certain alpha-hydroxycarbonyl compounds are effective reducing agents in the dye industry, provided that a sufficient amount of base needs to be added to the reaction medium.
It was unexpectedly found in chinese patent CN103315995A that certain α -hydroxycarbonyl compounds have efficient reducing power at low pH values and can therefore be used in mild environments (and/or in the presence of large amounts of non-aqueous (organic) solvents) to reduce various structures (including a variety of organic compounds). The patent reports that alpha-hydroxy carbonyl compounds capable of forming cyclic dimers can be used as homogeneous two-electron reducing agents to reduce and activate some prodrugs, and are widely applied to the field of drug research and development. Examples of alpha-hydroxycarbonyl compounds used are dihydroxyacetone, glycolaldehyde, glyceraldehyde, erythrose, xylulose, erythrulose, or 3-hydroxy-2-butanone.
In 2007, Cameron Jones reported in the journal of Science the world of the first monovalent magnesium compound (formula a), which was demonstrated by various chemical reactions to undergo a two-electron transfer reaction, to be converted to divalent magnesium in the presence of an oxidizing agent (see Science 2007,318,1754), and which, upon reduction of some substrates, such as organogermanium and aluminum compounds, showed superior performance in terms of selectivity to traditional heterogeneous and homogeneous one-electron reducing agents (see angelw. chem. int. ed.2009,48,9701; nat. chem. 2010,2, 865.).
Silole compounds (silacyclopentadiene compounds) are widely applied to the fields of optical instruments, chemical sensing, biological monitoring, cell imaging and stimulation nano response materials due to unique chemical and photoelectric properties, particularly, electrons can be easily obtained by the silole compounds due to the low LUMO orbital energy of the silole compounds, the silole compounds can be reduced by alkali metals to generate silole negative ion compounds, and the silole negative ion compounds are very active at room temperature and can easily react to generate silole polymers, so that the research on the chemical properties and the purposes of the silole compounds is limited.
Disclosure of Invention
The inventor finds that the four-electron homogeneous phase reducing agent with the spiro silole structure and high efficient reduction performance can be separated by adopting substituent with strong conjugation ability to delocalize negative ions on the silole ring and stabilizing the silole negative ion compound by using a specific oxygen-containing coordination solvent.
Therefore, one of the objects of the present invention is to provide a four-electron homogeneous reductant compound, the other object of the present invention is to disclose a method for preparing the compound, and the other object of the present invention is to disclose the use of the compound.
The four-electron homogeneous phase reducing agent is a 2,3,4,5,2 ', 3', 4 ', 5' -octa-aryl spiro silole tetra-negative ion compound, and the structure is shown as the formula (I):
in the formula, Ar is C6～C10An aromatic group or a substituted aromatic group.
Ar is preferably one of phenyl, 2, 6-dimethylphenyl or 2, 6-diisopropylphenyl.
And M is an alkali metal.
The M is selected from one of metallic lithium, sodium or potassium, and is preferably metallic lithium.
And the S is an oxygen-containing solvent and is complexed with the silole compound in a coordination bond form.
S is selected from one of tetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether, and ethylene glycol dimethyl ether is more preferable.
The invention also discloses a preparation method of at least one four-electron homogeneous phase reducing agent with the structure shown in the formula (I).
The preparation method of the four-electron homogeneous phase reducing agent is characterized in that an aryl spiro silole compound with a structure shown in a formula (II) is used as a raw material, the aryl spiro silole compound is obtained by reducing the aryl spiro silole compound with alkali metal in an oxygen-containing solvent at the temperature of-20 ℃, the molar mass ratio of the aryl spiro silole compound to the alkali metal to the oxygen-containing solvent is 1 (2-4): 8-10, and the reaction time is 0.5-2 h.
Wherein Ar of the starting compound of formula (II) is C6～C10An aromatic group or a substituted aromatic group, preferably one of phenyl, 2, 6-dimethylphenyl or 2, 6-diisopropylphenyl.
Aryl spirocyclic silole starting compounds of formula (II) may be prepared as described in the literature (Junghyun, Lee.; Sun Wang.2,5-Functionalized Spiro-Biloles as highlyupon effective Yellow-Light emititers in electroluminiscent devices. Adv. Funct. Mater.2006,16,681.).
The oxygen-containing organic solvent is one of tetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether, and ethylene glycol dimethyl ether is preferred.
The alkali metal is one of lithium, sodium or potassium, and is preferably metallic lithium.
The aryl spiro silole tetraelectron homogeneous phase reducing agent obtained by the invention can be applied to some standard homogeneous phase reduction systems.
In order to illustrate the reduction performance of the invention, the inventor takes a spiro silole tetralithium salt as an example, and respectively reacts with diquinone, bis triphenylphosphine palladium dichloride, methyl iodide and oxygen, and proves that the spiro silole tetralithium salt can completely reduce the oxidant through nuclear magnetic resonance and X-ray energy spectrum characterization technologies.
The preparation and reduction processes of the aryl spiro silole compound are shown as the following formula, wherein 2 represents octaaryl spiro silole tetraanion, and 1 represents octaaryl spiro silole.
In the reaction, the octaaryl spiro silole tetraanions can completely reduce the above substrates of diquinone, bis triphenylphosphine palladium dichloride, methyl iodide and oxygen into lithium diphenolate, zero-valent palladium, methyl lithium and lithium oxide, and the octaaryl spiro silole tetraanions are oxidized into the octaaryl spiro silole and show efficient reduction performance.
The four-electron homogeneous phase reducing agent of the formula (I) has the following characteristics and advantages:
(1) has good thermal stability, and can not be decomposed even at the temperature of more than 200 ℃.
(2) Has good dissolvability and good dissolvability in a nonpolar solvent n-hexane.
(3) The chemical stability is good, further reaction with the reduction product can be avoided, and the reduction product can be conveniently recycled and reused by a chromatographic column and a recrystallization method.
(4) The preparation method is simple, does not need any catalyst, can be carried out within a short time (less than 2h) at a mild temperature (20 ℃ below zero to 20 ℃), has a yield of more than 95 percent, and is convenient for large-scale production.
(5) The reducing agent is safe to use, nontoxic, tasteless and environment-friendly.
The advantages endow the aryl spiro silole compound with wider application prospect on the homogeneous phase reducing agent, and have practical significance on silole chemistry and homogeneous phase reducing agent chemistry.
Drawings
FIG. 1 nuclear magnetic hydrogen spectrum of the product of example 1, 2,3,4,5,2 ', 3', 4 ', 5' -octaphenylspirocyclosilole tetralithium salt ((M))1H NMR C6D6)。
FIG. 2 Nuclear magnetic silicon Spectroscopy of 2,3,4,5,2 ', 3', 4 ', 5' -octaphenylspirocyclosilole tetralithium salt of product of example 1 ((S))29Si NMR C6D6)。
FIG. 3 nuclear magnetism of hydroquinone as a reduction product in example 2: (1H NMR CDCl3) Hydrogen spectrum.
FIG. 4 example 5X-ray electron spectroscopy (XPS) of the reaction product of spirocyclic silole tetralithium salt with bis triphenylphosphine palladium dichloride.
Detailed Description
The following examples are further illustrative of the technical solutions of the present invention, but the scope of the present invention is not limited by the examples.
1. Principal analytical method
Tetrahydrofuran, normal hexane, anhydrous ether and other common solvents used in the experiment are used, and before use, benzophenone is used as an indicator, and metal sodium is used for reflux dehydration under the protection of nitrogen; for experiments C6D6And CDCl3Purchased from cambridge isotope laboratories, usa. The chemical raw materials used in the experiment, namely tolane, n-butyllithium, alcohol and silane, are all pure reagent products and are respectively ordered from Aladdin and domestic reagent companies according to requirements. The NMR spectra were obtained at room temperature using a Bruker AV400 NMR spectrometer. The compound is prepared by1H NMR，13C NMR，29Si NMR was carried out to confirm the above results, and comparison of known compounds with the literature was carried out. Of all compounds1H NMR、13C NMR、29Si NMR and the likeThe nuclear magnetic data were measured on a Bruke AV 400M nuclear magnetic spectrometer at room temperature (298K) without specification, with chemical shifts referenced to deuterated solvents: delta1H(C6D6)＝ 7.15ppm，δ13C(C6D6) 128.00 ppm. Samples of compounds that were not sensitive to water oxygen in this experiment were formulated directly in air with untreated deuterated reagents.
2. Raw material source and specification
3. Preparation of starting compounds for 2,3,4,5,2 ', 3', 4 ', 5' -octaphenylspirocyclosiloles
Under the protection of nitrogen, adding metallic lithium (0.28g, 40.0mmol) into tolane (7.0g, 40.0mmol) dissolved in 100mL of anhydrous ether at room temperature for 2h, and filtering out residual metallic lithium; slowly dripping 100mL of toluene solution of silicon tetrachloride (1.7g, 10.0mmol) into the system at-20 ℃, maintaining the room temperature for reaction for 1h, slowly heating to the room temperature, and continuously heating to 100 ℃ for reaction for 2 h; then cooling to room temperature, concentrating the solution to 20mL, placing in a refrigerator at-40 ℃ for crystallization to obtain 3.3g of 2,3,4,5,2 ', 3', 4 ', 5' -octaphenyl spiro silole as a yellow-green solid, wherein the yield is 90% for later use.
EXAMPLE 12 preparation of lithium salt of 3,4,5,2 ', 3', 4 ', 5' -octaphenylspirocyclosilole
Metallic lithium (0.30g, 44.0mmol) was added to 2,3,4,5,2 ', 3', 4 ', 5' -octaphenylspirocyclosilole (7.4g, 10.0mmol) dissolved in 50mL of ethylene glycol dimethyl ether at room temperature under nitrogen. Reacting for 2h, concentrating the solution to 10mL, and placing the solution in a refrigerator at the temperature of minus 40 ℃ for crystallization to obtain 11.3g of orange red solid 2,3,4,5,2 ', 3', 4 ', 5' -octaphenyl spiro silole tetralithium salt, wherein the yield is 95%.
Subjecting the obtained product to nuclear magnetic hydrogen spectrum (1H NMR C6D6) As in fig. 1. As can be seen from the figure, δ -6.87-7.47 ppm is the peak of spiro silole eight phenyl groups, δ -2.98 and δ -3.07 ppm are the peaks of methylene and methyl groups on ethylene glycol dimethyl ether, and the peak is obviously changed from the peak of free ethylene glycol dimethyl ether (δ -3.12 and δ -3.33 ppm). The glycol dimethyl ether is used as a coordination solvent to play a role in stabilizing spiro silole tetralithium salt.
Nuclear magnetic silicon spectrum of the product: (29Si NMR C6D6) As shown in fig. 2, δ -13.28ppm is a typical silicon peak range of the four-coordinate silicon, consistent with the target product.
Comparative example 1
Metallic lithium (0.30g, 44.0mmol) was added to 2,3,4,5,2 ', 3', 4 ', 5' -octaphenylspirosilole (7.4g, 10.0mmol) dissolved in 50mL of n-hexane at room temperature under nitrogen. Reacting for 2h, concentrating the solution to 10mL, placing the solution in a refrigerator at the temperature of minus 40 ℃ for crystallization, and obtaining the corresponding spirocyclic silole tetralithium salt without separation through nuclear magnetic tracking.
The method is characterized in that the generated spiro silole tetralithium salt is very active in a nonpolar solvent n-hexane, and the nonpolar solvent n-hexane cannot coordinate stable metal lithium ions, so that the final product spiro silole tetralithium salt cannot be separated.
Comparative example 1'
Metallic lithium (0.30g, 44.0mmol) was added to 2,3,4,5,2 ', 3', 4 ', 5' -octaphenylspirocyclosilole (7.4g, 10.0mmol) dissolved in 50mL of toluene at room temperature under nitrogen. Reacting for 2h, concentrating the solution to 10mL, placing the solution in a refrigerator at the temperature of minus 40 ℃ for crystallization, providing nuclear magnetic detection, and obtaining the corresponding spirocyclic silole tetralithium salt without separation.
It is shown that the generated spiro silole tetralithium salt is very active in toluene and cannot be effectively separated.
EXAMPLE 2 reaction of spirocyclic Silole Tetralithium salt with diquinone
The procedure for the preparation of the tetra lithium salt of 2,3,4,5,2 ', 3', 4 ', 5' -octaphenylspirocyclosilole is as in example 1.
A solution of diquinone (0.027g, 0.25mmol) in 10mL of tetrahydrofuran was added dropwise to octaphenylspirocyclosilole tetralithium salt (0.80g, 0.50mmol) obtained in example 1 at room temperature, and the color of the system gradually changed to colorless. The nuclear magnetism of the crude product after being dried by pumping shows that hydroquinone negative ions are generated (the peak is 9.83ppm at sigma), and the spirocyclic silole tetralithium salt is completely converted into the spirocyclic silole compound (as shown in figure 3).
The spiro silole tetralithium salt can effectively reduce diquinone by being used as a homogeneous four-electron reducing agent, and shows the property of the homogeneous reducing agent.
Comparative example 2 reaction of lithium metal with diquinone under the same conditions
Adding metallic lithium (0.35g, 0.50mmol) into 10mL of biquinone (0.027g, 0.25mmol) solution dissolved in tetrahydrofuran at room temperature, reacting for 2h, wherein the color of the system is not obviously changed, reacting for 24h, gradually changing to be colorless, and carrying out nuclear magnetic monitoring to ensure that the biquinone is completely reduced.
Compared with common heterogeneous reducing agent metallic lithium, the spiro silole tetralithium salt serving as the homogeneous four-electron reducing agent can efficiently reduce diquinone in a shorter time, and shows the property superior to that of the traditional heterogeneous reducing agent.
Comparative example 2 reaction of lithium naphthalide with diquinone under the same conditions
Lithium naphthalide (0.75g, 0.50mmol) is added into 10mL of diquinone (0.027g, 0.25mmol) dissolved in tetrahydrofuran at room temperature, after 6h reaction, the system gradually becomes colorless, and the diquinone is completely reduced under nuclear magnetic monitoring.
Compared with common homogeneous phase one-electron reducing agent naphthalene lithium, the spiro silole tetralithium salt as the homogeneous phase four-electron reducing agent can efficiently reduce diquinone in a shorter time, and shows the property superior to that of the traditional homogeneous phase reducing agent.
EXAMPLE 3 reaction of spirocyclic Silole Tetralithium salt with methyl iodide
The procedure for the preparation of the tetra lithium salt of 2,3,4,5,2 ', 3', 4 ', 5' -octaphenylspirocyclosilole is as in example 1.
A solution of iodomethane (0.07g, 0.5mmol) dissolved in 5mL of tetrahydrofuran was added dropwise to the spirocyclothiapyrroletetralithium salt (0.40g, 0.25mmol, product of example 1) obtained in example 1 at room temperature, and the color of the system gradually changed to colorless. The drying to obtain a crude product shows that a reduction product methyllithium (MeLi) is generated, and the spiro silole tetralithium salt is completely converted into the spiro silole compound.
The spiro silole tetralithium salt can effectively reduce methyl iodide by being used as a homogeneous four-electron reducing agent, and shows the property of the homogeneous reducing agent.
Comparative example 3 reaction of lithium naphthalene with methyl iodide under the same conditions
Lithium naphthalide (0.75g, 0.50mmol) was added to a solution of 5mL of iodomethane (0.07g, 0.5mmol) in tetrahydrofuran at room temperature and after 2h reaction the color of the system gradually changed to colorless and no separation was observed by nuclear magnetic monitoring to give methyllithium product.
Because lithium naphthalene is a common homogeneous one-electron reducing agent, the selectivity is poor, methyl iodide is easy to be subjected to transition reduction, a plurality of byproducts are generated, the final reduction product is very complex, and a single product cannot be obtained.
EXAMPLE 4 reaction of spirocyclosilole tetralithium salt with oxygen
The procedure for the preparation of the tetra lithium salt of 2,3,4,5,2 ', 3', 4 ', 5' -octaphenylspirocyclosilole is as in example 1.
At room temperature, exposing spiro silole tetralithium salt (0.40g, 0.25mmol) in the air for 2h, gradually changing the system into light yellow, and separating to obtain spiro silole compound.
The spiro silole tetralithium salt serving as a homogeneous four-electron reducing agent can effectively reduce common oxidant oxygen and shows the property of the homogeneous reducing agent.
EXAMPLE 5 reaction of Spirocyclic Silole Tetralithium salt with bis-triphenylphosphine Palladium dichloride
The procedure for the preparation of the tetra lithium salt of 2,3,4,5,2 ', 3', 4 ', 5' -octaphenylspirocyclosilole is as in example 1.
Spirocyclothiapyrrole tetralithium salt (0.40g, 0.25mmol) and bis triphenylphosphine palladium dichloride (0.36g, 0.50mmol) were dissolved in 10mL tetrahydrofuran at room temperature and reacted for 2h, the system was completely pale yellow, and a black precipitate was formed at the bottom of the reaction flask. The black precipitate was characterized by X-ray electron spectroscopy (XPS) as shown in figure 4,
wherein the peak appearance (335.1ev and 340.9ev) of the X-ray energy spectrum Pdo3d is completely matched with that of the zero-valent palladium. The spiro silole tetralithium salt is used as a four-electron homogeneous phase reducing agent, and can efficiently reduce inorganic metal compounds.
Comparative example 5 reaction of lithium metal with bis-triphenylphosphine palladium dichloride under the same conditions
Metallic lithium (0.7g, 1.0mmol) and bis (triphenylphosphine) palladium dichloride (0.36g, 0.50mmol) are dissolved in 10mL of tetrahydrofuran at room temperature, and the reaction is carried out for 12h, so that the system is faded, and divalent palladium is reduced to zero-valent palladium.
Compared with a heterogeneous metal lithium reducing agent, the spiro silole tetralithium salt serving as the homogeneous four-electron reducing agent can effectively reduce a common divalent palladium compound of high-valence metal salt in a shorter time.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A four-electron homogeneous phase reducing agent is characterized in that the reducing agent is a 2,3,4,5,2 ', 3', 4 ', 5' -octa-aryl spiro silole tetra-negative ion compound, and the structure of the reducing agent is shown in a formula (I):
in the formula, Ar is C6～C10An aromatic or substituted aromatic group; m is an alkali metal; s is an oxygen-containing solvent and is complexed with the silole compound in the form of a coordination bond.
2. The homogeneous reducing agent according to claim 1, wherein in formula (I), Ar is one of phenyl, 2, 6-dimethylphenyl or 2, 6-diisopropylphenyl.
3. The homogeneous reducing agent according to claim 1, wherein in formula (I), M is selected from one of lithium, sodium or potassium metals.
4. Homogeneous reducing agent according to claim 3, characterized in that M is selected from metallic lithium.
5. The homogeneous reducing agent according to claim 1, wherein in formula (I), S is one selected from tetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether.
6. The homogeneous reducing agent according to claim 5, wherein S is selected from ethylene glycol dimethyl ether.
7. The preparation method of the homogeneous reducing agent according to claim 1, wherein the reducing agent is prepared by using an aryl spiro silole compound with a structure of formula (II) as a raw material, reducing the aryl spiro silole compound with alkali metal in an oxygen-containing solvent at a temperature of-20 ℃ to 20 ℃, wherein the aryl spiro silole compound, the alkali metal and the oxygen-containing solvent have a molar mass ratio of 1 (2-4) to (8-10), and a reaction time of 0.5-2 h,
wherein Ar in the raw material compound of the formula (II) is C6～C10An aromatic or substituted aromatic group; the oxygen-containing organic solvent is one of tetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether.
8. The method according to claim 7, wherein the starting compound (II) is one selected from phenyl, 2, 6-dimethylphenyl and 2, 6-diisopropylphenyl.
9. The method of claim 7, wherein the oxygen-containing organic solvent is selected from the group consisting of ethylene glycol dimethyl ether.
10. Use of a four-electron homogeneous reducing agent according to any one of claims 1 to 6, wherein the reducing agent is used in the reduction of diquinone, oxygen, methyl iodide, bis-triphenylphosphine palladium dichloride and benzophenone.
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Non-Patent Citations (3)
| Title |
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| ZHENGANG HAN ET AL: "Isolable 1,1-Disubstituted Silole Dianion: a Homogeneous Two-Electron-Transfer Reducing Reagent", 《INORGANIC CHEMISTRY》 * |
| ZHENGANG HAN ET AL: "Synthesis and NMR characterization of a spirosilole tetra-anion: a homogeneous four-electron reductant", 《MAIN GROUP METAL CHEMISTRY》 * |
| 毛林燕等: "噻咯类有机小分子光电材料", 《化学进展》 * |
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| CN113173945A (en) * | 2021-03-10 | 2021-07-27 | 西北师范大学 | Method for constructing organic phase electrochemical luminescence system of rigid spirocyclic silole compound |
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