Silicon-containing bisphospholene compounds, methods of making and using the same

Abstract

The present application relates to a silicon-containing bisphospholene compound and its preparation method and application. The silicon-containing bisphospholene compound has the following general structure: wherein R 1 ~R 3 are each independently a C1-C 10 alkyl group, R 4 ~R 7 are each independently a substituted or unsubstituted aryl group, the substituted aryl group being selected from any one or a combination of several of a C1-C 10 alkyl-substituted aryl group, a C1-C 10 alkoxy-substituted aryl group, and a halogen-substituted aryl group. The silicon-containing bisphospholene compound can be used not only in the preparation of halogen-free flame-retardant polyolefins, but also in the preparation of organophosphorus ligands.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic synthesis, in particular to a silicon-containing bisphospholene compound and a preparation method and application thereof. BACKGROUND

[0002] Organophosphines are increasingly important as ligands for transition metal catalysts and are widely used in cross-coupling reactions and asymmetric synthesis. Therefore, the design and synthesis of new organophosphine ligands and the development of corresponding preparation methods have a major impact on various fields of chemical science. In the past few decades, many effective preparation methods of organophosphorus compounds have been developed, among which metal-catalyzed carbon-carbon multiple bond hydrophosphination is a simple method for synthesizing organophosphines. Catalytic hydrophosphination of phosphorus-substituted unsaturated carbon-carbon bonds is relatively effective, and can quickly synthesize bidentate phosphine compounds, but due to the limitation of substrate diversity, the substrate application range of this method is greatly limited, especially the synthesis of bisphosphine compounds containing other heteroatoms.

[0003] On the other hand, polyolefins are high molecular compounds formed by the polyaddition reaction of olefins, which are a general term for a class of thermoplastic resins obtained by the polymerization or copolymerization of α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene and certain cyclic olefins. Due to the abundance of raw materials, low price, easy processing and molding, and excellent comprehensive performance, polyolefins are the largest production and most widely used polymer materials. Among them, polyethylene and polypropylene are the most important. Main varieties include polyethylene and some copolymers based on ethylene, such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid or acrylic ester copolymer, polypropylene and some propylene copolymers, poly-1-butene, poly-4-methyl-1-pentene, cyclic olefin polymer, etc. Olefins play a very important role in the development of industry as an important chemical raw material. However, general polyolefins have the disadvantages of flammability and aging, and only through modification can the defects be improved and the performance be improved. Polyolefins containing phosphorus and silicon generally have flame retardant properties. Therefore, it is particularly important to develop phosphorus and silicon-containing olefin monomers for the preparation of halogen-free flame retardants. SUMMARY

[0004] Therefore, it is necessary to provide a silicon-containing bisphospholene compound, which can be used not only in the preparation of halogen-free flame-retardant polyolefins, but also in the preparation of organophosphine ligands.

[0005] A silicon-containing bisphospholene compound has the following general structure:

[0006]

[0007] wherein R 1 ~R 3Each independently is C1 to C 10 Alkyl, R 4 ~R 7 Each aryl group can be independently substituted or unsubstituted, with the substituted aryl groups selected from C1 to C2. 10 Alkyl-substituted aryl, C1-C 10 Any one or a combination of alkoxy-substituted aryl groups and halogen-substituted aryl groups.

[0008] In one embodiment, the silicon-containing bisphosphine olefin compound satisfies any one or more of the following conditions:

[0009] (1) The silicon-containing bisphosphine olefin compound is Z-configured;

[0010] (2)R 1 ~R 3 Each is independently a C1 to C6 alkyl group;

[0011] (3)R 4 ~R 7 Each can be independently a substituted or unsubstituted phenyl, a substituted or unsubstituted pyridyl, or a substituted or unsubstituted thiophene.

[0012] A method for preparing a silicon-containing bisphosphine olefin compound includes the following steps:

[0013] Compound 1, compound 2, a first organic solvent, and a first basic reagent are mixed and reacted to prepare a silicon-containing bisphosphine olefin compound;

[0014] Wherein, the structural formula of compound 1 is The structural formula of compound 2 is as follows: The structural formula of the silicon-containing bisphosphine olefin compound is as follows: R 1 ~R 3 Each independently is C1 to C 10 Alkyl, R 4 ~R 7 Each aryl group can be independently substituted or unsubstituted, with the substituted aryl groups selected from C1 to C2. 10 Alkyl-substituted aryl, C1-C 10 Any one or a combination of alkoxy-substituted aryl groups and halogen-substituted aryl groups;

[0015] The first organic solvent is selected from any one or a combination of several of acetonitrile, toluene, xylene, mesitylene, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and diethyl ether.

[0016] In one embodiment, the preparation method satisfies any one or more of the following conditions:

[0017] (1) the first basic reagent is selected from any one or combination of n-butyllithium, sec-butyllithium, t-butyllithium, iso-butyllithium, lithium diisopropylamide, potassium carbonate, potassium phosphate, cesium carbonate, sodium methoxide, sodium ethoxide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, lithium bis(trimethylsilyl)amide, sodium hydroxide, and potassium hydroxide;

[0018] (2) the molar ratio of the compound 1, the first basic reagent, and the compound 2 is 1: (1-1.2): (1-1.2);

[0019] (3) the ratio of the amount of the first organic solvent to the compound 1 is (1 mL-10 mL): 1 mmol;

[0020] (4) the reaction temperature is -110°C-40°C;

[0021] (5) the reaction time is 1 h-24 h.

[0022] In one of the embodiments, the preparation method satisfies any one or several of the following conditions:

[0023] (1) the first organic solvent is selected from any one or combination of tetrahydrofuran, 2-methyltetrahydrofuran, and diethyl ether;

[0024] (2) the first basic reagent is selected from any one or combination of n-butyllithium and sec-butyllithium;

[0025] (3) the reaction temperature is -10°C-40°C;

[0026] (4) the reaction time is 10 h-24 h.

[0027] In one of the embodiments, the step of mixing and reacting the compound 1, the compound 2, the first organic solvent, and the first basic reagent comprises:

[0028] reacting the compound 1, the first organic solvent, and the first basic reagent at -10°C-40°C for 1 h-2 h, and then adding the compound 2 to continue the reaction for 10 h-15 h, wherein the first organic solvent comprises tetrahydrofuran, and the first basic reagent comprises n-butyllithium.

[0029] A preparation method of a silicon-containing bisphospholene compound comprises the following steps:

[0030] mixing and reacting a compound 4, a compound 5, a second organic solvent, and a second basic reagent to prepare the silicon-containing bisphospholene compound;

[0031] wherein the compound 4 has the following structural formula the compound 5 has the following structural formula

[0032] said silicon-containing diphospholane compound has a structural formula of R 1 ~R 3 each independently is C1-C 10 alkyl, R 4 ~R 7 each independently is substituted or unsubstituted aryl, the substituted aryl being selected from the group consisting of C1-C 10 alkyl-substituted aryl, C1-C 10 alkoxy-substituted aryl and halogen-substituted aryl in any one or combination of several;

[0033] said second organic solvent is selected from the group consisting of 1,2-dichloroethane, acetonitrile, chloroform, toluene, xylene, mesitylene, ethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane and diethyl ether in any one or combination of several.

[0034] In one of the embodiments, the preparation method satisfies any one or several of the following conditions:

[0035] (1) the second organic solvent and the compound 4 are used in a ratio of (1 mL-10 mL):1 mmol;

[0036] (2) the molar ratio of the compound 4, the second basic reagent and the compound 5 is 1:(0.01-1.5):(1-1.2);

[0037] (3) the reaction temperature is -110℃-40℃;

[0038] (4) the reaction time is 1h-24h;

[0039] (5) the second basic reagent is selected from the group consisting of n-butyllithium, sec-butyllithium, t-butyllithium, iso-butyllithium, lithium diisopropylamide, potassium carbonate, potassium phosphate, cesium carbonate, potassium t-butoxide, potassium methoxide, sodium methoxide, sodium ethoxide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, lithium bis(trimethylsilyl)amide, sodium hydroxide and potassium hydroxide in any one or combination of several.

[0040] In one of the embodiments, the preparation method satisfies any one or several of the following conditions:

[0041] (1) the second organic solvent is selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane and diethyl ether in any one or combination of several;

[0042] (2) the second basic reagent is selected from the group consisting of potassium t-butoxide, potassium methoxide and potassium bis(trimethylsilyl)amide in any one or combination of several;

[0043] (3) the reaction temperature is 10-30°C;

[0044] (4) the reaction time is 10-20h.

[0045] Use of a silicon-containing bisphospholene compound in the preparation of an organophosphorus ligand, a flame-retardant polyolefin, a metal halide coupling agent or a vinyl sulfide, the silicon-containing bisphospholene compound being the silicon-containing bisphospholene compound described above or a silicon-containing bisphospholene compound synthesized by the preparation method of the silicon-containing bisphospholene compound described above.

[0046] Experiments show that the silicon-containing bisphospholene compound described above not only can be used to prepare a flame-retardant polyolefin by free radical polymerization, but also can be used to prepare an organophosphorus ligand, which is widely used in cross-coupling reactions and asymmetric synthesis. DETAILED DESCRIPTION

[0047] In order to facilitate the understanding of the present application, the present application will be described more fully below with reference to the specific embodiments. The preferred embodiments of the present application are given in the specific embodiments. However, the present application can be realized in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0048] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application herein are only for the purpose of describing specific embodiments and are not intended to limit the present application.

[0049] The term "alkyl" refers to a saturated hydrocarbon containing primary (normal) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or a combination thereof. The phrase containing this term, for example, "C1-C10alkyl" means that each occurrence of an alkyl group can be independently a C1alkyl, a C2alkyl, a C3alkyl, a C4alkyl, a C5alkyl, a C6alkyl, a C7alkyl, a C8alkyl, a C9alkyl, or a C10alkyl. 10 The term "alkyl" refers to an alkyl group containing 1-10 carbon atoms, each occurrence of which can be independently a C1alkyl, a C2alkyl, a C3alkyl, a C4alkyl, a C5alkyl, a C6alkyl, a C7alkyl, a C8alkyl, a C9alkyl, or a C10alkyl. 10Alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1 -propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1 -butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1 -propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1 -butyl (-CH2CH2CH(CH3)2), 2-methyl-1 -butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3, and octyl (-(CH2)7CH3).

[0050] The term "alkoxy" refers to a group having an -O-alkyl group, i.e., an alkyl group as defined above attached to the parent structure through an oxygen atom. Phrases containing this term, e.g., "Ci-Cio alkoxy," "C1-C4 alkoxy," "C1-C5 alkoxy," "C1-C6 alkoxy," "C1-C7 alkoxy," "C1-C8 alkoxy," "C1-C9 alkoxy," and "C1-C10 alkoxy," mean that the alkyl portion of the alkoxy group can independently of each other be a C1 alkoxy, a C4 alkoxy, a C5 alkoxy, a C6 alkoxy, a C7 alkoxy, a C8 alkoxy, a C9 alkoxy, or a C10 alkoxy, respectively. 10 The term "alkoxy" refers to a group having an -O-alkyl group, i.e., an alkyl group as defined above attached to the parent structure through an oxygen atom. Phrases containing this term, e.g., "Ci-Cio alkoxy," "C1-C4 alkoxy," "C1-C5 alkoxy," "C1-C6 alkoxy," "C1-C7 alkoxy," "C1-C8 alkoxy," "C1-C9 alkoxy," and "C1-C10 alkoxy," mean that the alkyl portion of the alkoxy group can independently of each other be a C1 alkoxy, a C4 alkoxy, a C5 alkoxy, a C6 alkoxy, a C7 alkoxy, a C8 alkoxy, a C9 alkoxy, or a C10 alkoxy, respectively. 10 Alkoxy. Suitable examples include, but are not limited to: methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), and t-butoxy (-O-C(CH3)3 or -OTBu).

[0051] "Aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl. For polycyclic compounds, at least one ring must be an aromatic ring system. For example, "C5~C5..." 20 "Aryl" refers to an aryl group containing 5 to 20 carbon atoms. Each time it appears, it can independently be C5 aryl, C6 aryl, C7 aryl, C8 aryl, C9 ... 10 Aryl, C 14 Aryl, C 18 Aryl or C 20 Aryl groups. Suitable examples include, but are not limited to: benzene, biphenyl, naphthalene, anthracene, phenanthrene, dinaphthalene, triphenylene and their derivatives.

[0052] "Halogen" or "halogen group" refers to F, Cl, Br or I.

[0053] In this invention, "one or more" refers to any one, two, or more of the listed items. "More than two" refers to any two or more of the listed items.

[0054] When a numerical range is disclosed in this invention, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Further, when the range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Moreover, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed in this invention should be understood to include any and all subranges to which they are incorporated.

[0055] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0056] The terms "comprising" and "having," and any variations thereof, used in embodiments of this invention are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units is not limited to the steps or units listed, but may optionally include steps or units not listed, or may optionally include other steps or components inherent to such processes, methods, products, or devices.

[0057] In this invention, the reference to "embodiment" means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this invention can be combined with other embodiments.

[0058] The present application provides a silicon-containing bisphospholene compound according to one embodiment, having the following general structure:

[0059]

[0060] wherein R 1 ~R 3 each independently is a C1-C 10 alkyl, R 4 ~R 7 each independently is a substituted or unsubstituted aryl, the substituted aryl being selected from any one or a combination of C1-C 10 alkyl-substituted aryl, C1-C 10 alkoxy-substituted aryl, and halogen-substituted aryl.

[0061] In some embodiments, R 1 ~R 3 each independently is a C1-C6alkyl. Further, R 1 ~R 3 each independently is a C1-C4alkyl. In one specific example, R 1 ~R 3 each independently is a methyl, ethyl, propyl, butyl, and the like.

[0062] In some embodiments, R 1 ~R 3 are the same.

[0063] In some embodiments, R 4 ~R 7 each independently is a substituted or unsubstituted C5-C 20 aryl. Further, R 4 ~R 7 each independently is a substituted or unsubstituted C5-C 10 aryl. In one specific example, R 4 ~R 7 each independently is a substituted or unsubstituted phenyl, a substituted or unsubstituted pyridyl, or a substituted or unsubstituted thienyl.

[0064] In some embodiments, the substituted aryl is selected from any one or a combination of C1-C6alkyl-substituted aryl, C1-C6alkoxy-substituted aryl, and halogen-substituted aryl. In one specific example, the substituted aryl is a methyl-substituted phenyl, an ethyl-substituted phenyl, a methoxy-substituted phenyl, and the like.

[0065] In some embodiments, R 4 ~R 7 are the same.

[0066] The metal complex synthesized from the above-mentioned silicon-containing diphospholene compound can be used as a chiral selective catalyst in the field of organic or polymer compound synthesis. When R1-R3 are alkyl groups, the selectivity of the catalyst is better. Similarly, when R4-R7 are all substituted or unsubstituted aryl groups, the selectivity of the catalyst is better.

[0067] In some embodiments, the silicon-containing diphospholene compound is in Z configuration. The silicon-containing diphospholene compound in Z configuration is more stable in structure and has more applications.

[0068] The above-mentioned silicon-containing diphospholene compound can not only be used in the preparation of halogen-free flame-retardant polyolefins, but also be used in the preparation of organophosphorus ligands.

[0069] In addition, the metal complex synthesized from the above-mentioned silicon-containing diphospholene compound can be used as a chiral selective catalyst in the field of organic or polymer compound synthesis.

[0070] The present application also provides a preparation method of the silicon-containing diphospholene compound of an embodiment, comprising the following steps:

[0071] Mixing and reacting the compound 1, the compound 2, the first organic solvent and the first basic reagent to prepare the silicon-containing diphospholene compound;

[0072] The compound 1 has the structural formula of The compound 2 has the structural formula of The silicon-containing diphospholene compound has the structural formula of R 1 ~R 3 Each independently is C1-C 10 alkyl, R 4 ~R 7 Each independently is substituted or unsubstituted aryl, and the substituted aryl is selected from any one or combination of C1-C 10 alkyl-substituted aryl, C1-C 10 alkoxy-substituted aryl and halogen-substituted aryl;

[0073] The first organic solvent is selected from any one or combination of acetonitrile (MeCN), toluene (Toluene), xylenes, mesitylene, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), 1,4-dioxane (1,4-Dioxane) and diethyl ether (Et2O).

[0074] Furthermore, in some embodiments, the first organic solvent is selected from one or a combination of several of tetrahydrofuran, 2-methyltetrahydrofuran, and diethyl ether. Even further, the first organic solvent is tetrahydrofuran. Experiments have shown that by optimizing the type of the first organic solvent, the yield of the prepared silicon-containing bisphosphine olefin compound can be further improved.

[0075] In some embodiments, the ratio of the first organic solvent to compound 1 is (1 mL to 10 mL): 1 mmol. For example, the ratio of the first organic solvent to compound 1 is 1 mL: 1 mmol, 2 mL: 1 mmol, 3 mL: 1 mmol, 4 mL: 1 mmol, 5 mL: 1 mmol, 6 mL: 1 mmol, 7 mL: 1 mmol, 8 mL: 1 mmol, 9 mL: 1 mmol, 10 mL: 1 mmol, or any range of two of these values. Further, the ratio of the first organic solvent to compound 1 is (5 mL to 7 mL): 1 mmol. Even further, the ratio of the first organic solvent to compound 1 is 6 mL: 1 mmol.

[0076] In some embodiments, the first alkaline reagent is selected from n-butyllithium (… n BuLi), sec-butyllithium ( s BuLi), tert-butyllithium ( t BuLi), isobutyllithium ( iso BuLi), lithium diisopropylamino (LDA), potassium carbonate (K2CO3), potassium phosphate (K3PO4), cesium carbonate (Cs2CO3), sodium methoxide (MeONa), sodium ethoxide (EtONa), sodium bis(trimethylsilyl)amino (NaHMDS), potassium bis(trimethylsilyl)amino (KHMDS), lithium bis(trimethylsilyl)amino (LiHMDS), sodium hydroxide (NaOH), and potassium hydroxide (KOH) are any one or a combination of several of these.

[0077] Furthermore, the first basic reagent is selected from any one or a combination of n-butyllithium and sec-butyllithium. Even further, the first basic reagent is n-butyllithium. Experiments have shown that by optimizing the type of the first basic reagent, the yield of the prepared silicon-containing bisphosphine olefin compound can be further improved.

[0078] In some examples, the molar ratio of compound 1, the first basic reagent and compound 2 is 1: (1-1.2): (1-1.2). For example, the molar ratio of compound 1, the first basic reagent and compound 2 is 1:1:1, 1:1:1.05, 1:1:1.1, 1:1:1.15, 1:1:1.2, 1:1.1:1, 1:1.1:1.1, 1:1.1:1.2, 1:1.2:1, 1:1.2:1.05, 1:1.2:1.1, 1:1.2:1.15, 1:1.2:1.2 or a range between any two of these values. Further, the molar ratio of compound 1, the first basic reagent and compound 2 is 1:1:1.

[0079] In some embodiments, the reaction temperature is -110°C to 40°C. Further, the reaction temperature is -10°C to 40°C. Still further, the reaction temperature is 10°C to 30°C. Still further, the reaction temperature is 25°C. Too high reaction temperature will result in too violent reaction and lower selectivity of the reaction, and more by-products. Therefore, in the present embodiment, the reaction temperature is preferably -110°C to 40°C.

[0080] In some embodiments, the reaction time is 1h to 24h. Further, the reaction time is 10h to 24h. For example, the reaction time is 10h, 12h, 15h, 16h, 18h, 20h, 22h, 24h or a range between any two of these values.

[0081] In some embodiments, the step of mixing compound 1, compound 2, the first organic solvent and the first basic reagent comprises:

[0082] In some embodiments, the step of mixing compound 1, compound 2, the first organic solvent and the first basic reagent comprises:

[0083] In some embodiments, the preparation method further comprises a step of purification. In one embodiment, the step of purification comprises: adding water to the reaction system to quench the reaction, and then sequentially extracting, collecting the organic phase, removing the solvent in the organic phase, and column chromatography separation.

[0084] The preparation method of the above-mentioned silicon-containing bisphospholene compound has at least the following advantages:

[0085] (1) The preparation method of the above-mentioned silicon-containing bisphospholene compound takes cis-1,2-bis(dialkylphosphine) ethylene as an initial raw material, reacts with chlorosilane under the action of a first organic solvent and a first basic reagent, to obtain a silicon-containing bisphospholene compound in a high yield, and the process is simple, has few steps, and is easy for industrial production.

[0086] (2) The reaction reagent of the preparation method of the above-mentioned silicon-containing bisphospholene compound is commercially available, and no noble metal is used.

[0087] (3) The preparation method of the above-mentioned silicon-containing bisphospholene compound has mild reaction conditions, low energy consumption, and is green and environmentally friendly.

[0088] The application further provides a preparation method of a silicon-containing bisphospholene compound according to another embodiment, comprising the following steps:

[0089] Mixing and reacting compound 4, compound 5, a second organic solvent and a second basic reagent to prepare a silicon-containing bisphospholene compound;

[0090] The structural formula of compound 4 is The structural formula of compound 5 is The structural formula of the silicon-containing bisphospholene compound is R 1 ~R 3 Each is independently a C1~C 10 alkyl group, R 4 ~R 7 Each is independently a substituted or unsubstituted aryl group, and the substituted aryl group is selected from any one or a combination of C1~C 10 alkyl-substituted aryl group, C1~C 10 alkoxy-substituted aryl group and halogen-substituted aryl group;

[0091] The second organic solvent is selected from any one or a combination of 1,2-dichloroethane (DCE), acetonitrile (MeCN), chloroform (CHCl3), toluene (Toluene), xylene (Xylenes), mesitylene, ethylene glycol dimethyl ether (DME), tetrahydrofuran (THF), 2-methyltetrahydrofuran (MeTHF), 1,4-dioxane (1,4-Dioxane) and diethyl ether (Et2O).

[0092] Further, in some embodiments, the second organic solvent is selected from any one or a combination of tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane and diethyl ether. Further, the second organic solvent is tetrahydrofuran. Experimental results show that by optimizing the type of the second organic solvent, the yield of the prepared silicon-containing bisphospholene compound can be further improved.

[0093] In some embodiments, the ratio of the second organic solvent to compound 4 is (1 mL-10 mL): 1 mmol. For example, the ratio of the second organic solvent to compound 4 is 1 mL: 1 mmol, 2 mL: 1 mmol, 3 mL: 1 mmol, 4 mL: 1 mmol, 5 mL: 1 mmol, 6 mL: 1 mmol, 7 mL: 1 mmol, 8 mL: 1 mmol, 9 mL: 1 mmol, 10 mL: 1 mmol, or a range between any two of these values. Further, the ratio of the second organic solvent to compound 4 is (5 mL-7 mL): 1 mmol. Further still, the ratio of the second organic solvent to compound 4 is 6 mL: 1 mmol.

[0094] In some embodiments, the molar ratio of compound 4, the second basic reagent, and compound 5 is 1:(0.01-1.5):(1-1.2). For example, the molar ratio of compound 4, the second basic reagent, and compound 5 is 1:0.01:1, 1:0.01:1.05, 1:0.01:1.1, 1:0.01:1.15, 1:1.01:1.2, 1:0.05:1, 1:0.05:1.05, 1:0.05:1.1, 1:0.05:1.15, 1:0.05:1.2, 1:0.1:1, 1:0.1:1.05, 1:0.1:1.1, 1:0.1:1.15, 1:0.1:1.2, 1:0.15:1, 1:0.15:1.05, 1:0.15:1.1, 1:0.15:1.15, 1:0.15:1.2, 1:1:1, 1:1:1.05, 1:1:1.1, 1:1:1.15, 1:1:1.2, or a range between any two of these values. Further, the molar ratio of compound 4, the second basic reagent, and compound 5 is 1:(0.05-0.15):(1-1.2). Further still, the molar ratio of compound 4, the second basic reagent, and compound 5 is 1:0.1:1.

[0095] In some embodiments, the second basic reagent is selected from any one or a combination of several of n-butyllithium, sec-butyllithium, t-butyllithium, iso-butyllithium, lithium diisopropylamide, potassium carbonate, potassium phosphate, cesium carbonate, potassium tert-butoxide, potassium methoxide, sodium methoxide, sodium ethoxide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, lithium bis(trimethylsilyl)amide, sodium hydroxide, and potassium hydroxide. Further, the second basic reagent is selected from any one or a combination of several of potassium tert-butoxide, potassium methoxide, and potassium bis(trimethylsilyl)amide. Further still, the second basic reagent is potassium tert-butoxide. Experimental results have shown that the yield of the prepared silicon-containing bisphosphole compound can be further improved by optimizing the type of the second basic reagent.

[0096] In some embodiments, the reaction temperature is -110°C to 40°C. Further, the reaction temperature is -10°C to 40°C. Still further, the reaction temperature is 10°C to 30°C. For example, the reaction temperature is 10°C, 12°C, 15°C, 18°C, 20°C, 22°C, 25°C, 28°C, 30°C, or a range defined by any two of these values. Still further, the reaction temperature is 20°C to 30°C. Still further, the reaction temperature is 25°C.

[0097] In some embodiments, the reaction time is 1h to 24h. Further, the reaction time is 10h to 20h. For example, the reaction time is 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, or a range defined by any two of these values. Further, the reaction time is 12h to 15h.

[0098] In some embodiments, the preparation method further comprises a purification step. In one embodiment, the purification step comprises adding water to quench the reaction in the reaction system, and then sequentially extracting, collecting the organic phase, removing the solvent in the organic phase, and column chromatography separation.

[0099] The preparation method of the above-mentioned silicon-containing bisphospholene compound has at least the following advantages:

[0100] (1) The preparation method of the above-mentioned silicon-containing bisphospholene compound uses bis(diaromatic phosphorus) acetylene as the initial raw material, reacts with a trisubstituted silane under the action of a second basic reagent and a second organic solvent, to obtain a type of silicon-containing bisphospholene compound in high yield, and the process is simple, the steps are few, and the industrial production is easy.

[0101] (2) The reaction reagents of the preparation method of the above-mentioned silicon-containing bisphospholene compound are commercially available, and do not need to use noble metals.

[0102] (3) The preparation method of the above-mentioned silicon-containing bisphospholene compound has mild reaction conditions, low energy consumption, and is green and environmentally friendly.

[0103] The application also provides an application of the silicon-containing bisphospholene compound in an embodiment in preparing an organophosphorus ligand, a flame-retardant polyolefin, a metal halide coupling agent, or a vinyl sulfide.

[0104] In order to make the purpose and advantages of the present application more clear, the silicon-containing diphospholene compound and its effects of the present application are further described in detail below in combination with specific examples. It should be understood that the specific examples described herein are only used to explain the present application and should not be used to limit the present application. The following examples do not include other components except for inevitable impurities if not otherwise specified. The drugs and instruments used in the examples are selected according to the conventional selection in the art if not otherwise specified. The experimental methods in the examples are implemented according to the conventional conditions, for example, the conditions described in the literature, books or the methods recommended by the manufacturers if not otherwise specified.

[0105] Examples 1-16 and Comparative Examples 1-6

[0106] Examples 1-16 and Comparative Examples 1-6 respectively provide a silicon-containing diphospholene compound, and the synthesis process is as follows:

[0107] Under the protection of nitrogen, a Schlenk flask is added with compound 1a (2.5 mmol) and a first organic solvent (10 mL), the mixture is stirred at T1 temperature, then a solution of a first basic reagent (2.5 mmol) dissolved in the first organic solvent (1 mL) is added dropwise, and after reaction at T2 temperature for t1 time, a solution of compound 2a (2.5 mmol) dissolved in the first organic solvent (4 mL) is added dropwise at T3 temperature, and the reaction is stirred at T4 temperature for t2 time. After the reaction is completed, water is added to quench the reaction, then ethyl acetate is used for extraction (10 mL x 3), the organic phase is collected, the solvent in the organic phase is removed, and column chromatography is used for separation and purification to obtain compound 3a.

[0108] The synthesis process is as shown below:

[0109]

[0110] In the preparation process of the silicon-containing diphospholene compound of each example and comparative example, the type of the first organic solvent, the type of the first basic reagent, and the temperature and time parameters are specifically shown in Table 1.

[0111] Table 1 Synthesis process parameters of the silicon-containing diphospholene compound 3a of each example and comparative example

[0112]

[0113]

[0114] Examples 17-33 and Comparative Examples 8-9

[0115] Examples 17-33 and Comparative Examples 8-9 respectively provide a preparation method of a silicon-containing diphospholene compound, which comprises the following steps:

[0116] Under the protection of nitrogen, a Schlenk flask was added with compound 4a (5 mmol), compound 5a (5 mmol), a second basic reagent (0.5 mmol) and a second organic solvent (30 mL), stirred at a temperature T5, reacted for a time t3, after the reaction was completed, water was added to the reaction system to quench the reaction, then extracted with ethyl acetate (10 mL x 3), the organic phase was collected, the solvent in the organic phase was removed, and compound 3a was obtained after column chromatography separation and purification.

[0117] The synthesis process is as follows:

[0118]

[0119] In the preparation process of the silicon-containing diphosphene compound of each example and comparative example, the types of the second organic solvent, the types of the second basic reagent, the temperature and the time parameters are shown in Table 2.

[0120] Table 2: Synthesis process parameters of each example

[0121]

[0122]

[0123] Example 34

[0124] The present example provides a preparation method of a silicon-containing diphosphene compound, and the specific process is as follows:

[0125]

[0126] Under the protection of nitrogen, a Schlenk flask was added with compound 4a (5 mmol), compound 5a (5 mmol), a second basic reagent (0.5 mmol) and a second organic solvent (30 mL), stirred at a temperature T5, reacted for a time t3, after the reaction was completed, water was added to the reaction system to quench the reaction, then extracted with ethyl acetate (10 mL x 3), the organic phase was collected, the solvent in the organic phase was removed, and compound 3a was obtained after column chromatography separation and purification.

[0127] The nuclear magnetic resonance data of compound 3a is as follows:

[0128] 1H NMR (400 MHz, CDCI3) δ 7.35 ~ 7.21 (m, 16H), 7.20 ~ 7.11 (m, 4H), 6.83 (d, J = 17.6 Hz, 1H), 1.28 ~ 1.04 (m, 12H), 0.89 ~ 0.66 (m, 15H).

[0129] 31 P NMR (162 MHz, CDCI3) δ 5.75 (d, J = 8.8 Hz), -26.37 (d, J = 8.8 Hz).

[0130] Example 35

[0131] This example provides a silicon-containing bisphospholene compound, and the specific synthesis process is as follows:

[0132]

[0133] Under nitrogen protection, a Schlenk flask was added with compound 1a (25 mmol), tetrahydrofuran (100 mL), stirred at 25°C, and then a solution of n-butyl lithium (25 mmol) in tetrahydrofuran (10 mL) was added dropwise. After 1 hour of reaction at 25°C, a solution of compound 2b (25 mmol) dissolved in tetrahydrofuran (40 mL) was added dropwise at 25°C, and the reaction was stirred at 25°C for 12 hours. After the reaction was completed, water was added to quench the reaction, and then ethyl acetate was used for extraction, the organic phase was collected, the solvent in the organic phase was removed, and column chromatography was used for separation and purification to obtain compound 3b, white solid, mass 9.01 g, yield 77%.

[0134] The nuclear magnetic resonance data of compound 3b is as follows:

[0135] 1H NMR (400 MHz, CDCI3) δ 7.45 ~ 7.39 (m, 8H), 7.29 ~ 7.17 (m, 12H), 5.64 (d, J = 9.5 Hz, 1H), 0.13 (s, 9H).

[0136] 31 P NMR (162 MHz, CDCI3) δ -5.23 (d, J = 8.3 Hz), -28.35 (d, J = 8.3 Hz).

[0137] Example 36

[0138] This example provides a silicon-containing bisphospholene compound, and the specific synthesis process is as follows:

[0139]

[0140] Under the protection of nitrogen, a Schlenk flask was added with compound 4a (25 mmol), compound 5a (25 mmol), potassium tert-butoxide (2.5 mmol) and tetrahydrofuran (150 mL), and stirred at 25°C for 12 hours. After the reaction was completed, water was added to quench the reaction, and then extracted with ethyl acetate (10 mL x 3). The organic phase was collected, and the solvent in the organic phase was removed. Compound 3a was obtained by column chromatography separation and purification, white solid, mass 11.45 g, yield 77%.

[0141] The nuclear magnetic characterization data of compound 3a are as follows:

[0142] 1 H NMR (400 MHz, CDCl3) δ 7.35-7.21 (m, 16H), 7.20-7.11 (m, 4H), 6.83 (d, J = 17.6 Hz, 1H), 1.28-1.04 (m, 12H), 0.89-0.66 (m, 15H).

[0143] 31 P NMR (162 MHz, CDCl3) δ 5.75 (d, J = 8.8 Hz), -26.37 (d, J = 8.8 Hz).

[0144] Example 37

[0145] This example provides a silicon-containing bisphosphole compound, and the synthesis process is as follows:

[0146]

[0147] Under the protection of nitrogen, a Schlenk flask was added with compound 1b (25 mmol), compound 2a (25 mmol), n-butyllithium (2.5 mmol) and tetrahydrofuran (150 mL), and stirred at 25°C for 12 hours. After the reaction was completed, water was added to quench the reaction, and then extracted with ethyl acetate (10 mL x 3). The organic phase was collected, and the solvent in the organic phase was removed. Compound 3c was obtained by column chromatography separation and purification, white solid, mass 12.81 g, yield 79%.

[0148] The nuclear magnetic characterization data of compound 3c are as follows:

[0149] 1 H NMR (400 MHz, CDCl3) δ 7.35-7.21 (m, 16H), 6.83 (d, J = 17.6 Hz, 1H), 2.35 (s, 12H) 1.28-1.04 (m, 12H), 0.89-0.66 (m, 15H).

[0150] 31 P NMR (162 MHz, CDC13) δ 5.75 (d, J = 8.8 Hz), -26.27 (d, J = 8.8 Hz).

[0151] Example 38

[0152] This embodiment provides a silicon-containing bisphospholene compound, and the synthesis process is specifically as follows:

[0153]

[0154] Under the protection of nitrogen, a Schlenk flask was added with compound 4b (25 mmol), compound 5a (25 mmol), potassium tert-butoxide (2.5 mmol) and tetrahydrofuran (150 mL), and stirred at 25°C for 12 hours. After the reaction was completed, water was added to quench the reaction, and then extracted with ethyl acetate (10 mL x 3), and the organic phase was collected, the solvent in the organic phase was removed, and column chromatography was used for separation and purification to obtain compound 3c, white solid, mass 13.3 g, yield 82%.

[0155] The nuclear magnetic characterization data of compound 3c are as follows:

[0156] 1 H NMR (400 MHz, CDC13) δ 7.35-7.21 (m, 16H), 6.83 (d, J = 17.6 Hz, 1H), 2.35 (s, 12H) 1.28-1.04 (m, 12H), 0.89-0.66 (m, 15H).

[0157] 31 P NMR (162 MHz, CDC13) δ 5.75 (d, J = 8.8 Hz), -26.27 (d, J = 8.8 Hz).

[0158] Example 39

[0159] This embodiment provides an application of a silicon-containing bisphospholene compound, and the process is specifically as follows:

[0160]

[0161] Under the protection of nitrogen, a Schlenk flask was added with compound 3a (297 mg, 0.5 mmol), sulfur powder (64 mg, 2.0 mmol) and N,N-dimethylformamide (3 mL), and stirred at room temperature for 1 hour. 10 mL of water was added for liquid separation, and extracted with ethyl acetate (10 mL x 3). The organic phase was combined, dried with anhydrous sodium sulfate, rotary evaporated, and column chromatography was used for purification to obtain white solid compound 6, mass 263 mg, yield 80%.

[0162] The nuclear magnetic characterization data of compound 6 are as follows:

[0163] 1 H NMR (400 MHz, CDCl3) δ 7.44-7.28 (m, 20H), 6.76 (d, J = 17.6 Hz, 1H), 1.59-1.46 (m, 6H), 1.42-1.28 (m, 6H), 0.89-0.75 (m, 9H), 0.66-0.54 (m, 6H).

[0164] 31 P NMR (162 MHz, CDCl3) δ 50.22 (d, J = 11.6 Hz), 30.67 (d, J = 11.6 Hz).

[0165] In recent years, a development trend of synthesizing chiral ligands is to introduce heteroatoms such as nitrogen, oxygen or sulfur on the basis of chiral phosphine ligands to generate multi-tooth mixed functional group ligands. The mixed functional groups in such ligands not only can be complexed with metal centers to generate chiral metal complexes with strong rigidity, but also can be complexed with substrates to generate active intermediate complexes in the process of catalytic reaction, and are applied to various organic reactions. Chalcogen phosphine is an important organophosphorus compound, which has a wide range of applications in the fields of industry, organic synthesis, polymer science, medicine and coordination chemistry, such as hydroformylation, Heck reaction and the like.

[0166] Example 40

[0167] The embodiment provides an application of a silicon-containing bisphosphole compound, and a specific process is as follows:

[0168]

[0169] Under nitrogen protection, a Schlenk flask was added with compound 3a (297 mg, 0.5 mmol) and DCM (5 mL), and then H2O2 aqueous solution (30%, 3 mL) was added dropwise, and the reaction was stirred at room temperature for 3 hours. 5 mL of water was added for liquid separation, and DCM (5 mL x 3) was extracted. The organic phases were combined, dried over anhydrous sodium sulfate, and then rotary evaporated and purified by column chromatography to obtain white solid compound 7, with a mass of 310 mg and a yield of 99%.

[0170] The nuclear magnetic characterization data of compound 7 are as follows:

[0171] 1 H NMR (400 MHz, CDCl3) δ 7.37-7.19 (m, 16H), 7.23-7.15 (m, 4H), 6.80 (d, J = 17.6 Hz, 1H), 1.26-1.02 (m, 12H), 0.91-0.64 (m, 15H).

[0172] 31 P NMR (162 MHz, CDC13) δ 27.69 (d, J = 6.9 Hz), 22.33 (d, J = 6.9 Hz).

[0173] Several classic "named" reactions used in organic synthesis involve the stoichiometric use of phosphorus-based reagents, including the Wittig reaction (olefin formation), the Staudinger reaction (amine and its derivatives formation), and the Mitsunobu reaction (hydroxyl group substitution by other nucleophiles). The value of these reactions in organic synthesis is generally the construction of macromolecular compounds using reagents that are compatible with many different functional groups under mild conditions, and are widely used.

[0174] Example 41

[0175] This example provides an application of a silicon-containing bisphospholene compound, the specific process is as follows:

[0176]

[0177] To compound 3a (0.178 g, 0.30 mmol) in anhydrous toluene (10 mL) was added CrCl3(THF)3(0.105 g, 0.28 mmol) under nitrogen protection. Then the reaction was stirred at 80°C for 8 hours, forming a blue precipitate. After filtering out the precipitate, washing with n-hexane and drying in vacuum, blue powder compound 8 was obtained, mass 170 mg, yield 91.1%.

[0178] The characterization data of compound 8 are as follows: Calcd for C 76 H 96 Cl6Cr2P4Si2(%) : C, 60.60; H, 6.42. Found: C, 59.34; H, 6.33.

[0179] Metal-promoted organic halide coupling reactions are one of the most attractive and practical processes in carbon-carbon bond formation. In recent years, low-valent transition metals and organotransition metals play an important role in coupling agents in such reactions. Representative ones include Ullmann reaction, Cr-promoted coupling reaction, etc., and diphosphine complexes are widely used as ligands. The above compound 8 can be used as a ligand in coupling agents, and can be applied in Ullmann reaction, Cr-promoted coupling reaction, to prepare biphenyl substances.

[0180] Example 42

[0181] This example provides an application of a silicon-containing bisphospholene compound, the specific process is as follows:

[0182]

[0183] Compound 3a (0.5 mmol) and DCM (1.5 mL) were added to a sealed tube under nitrogen protection, then azobisisobutyronitrile AIBN (0.01 mmol) was added, and the reaction was stopped after the reaction in an 80°C oil bath for 24 hours. The reaction system was cooled to room temperature. After removing the solvent by distillation under reduced pressure, dichloromethane (0.5-1.0 mL) was added for dissolution, then ice methanol (20-25 mL) was added dropwise, and the polymer was precipitated slowly. The supernatant was filtered off, and the bottom product was rinsed with ice methanol (10 mL) for 2-3 times until the color of the polymer no longer changed, to obtain polymer 9 with a yield of 80%. The molecular weight distribution PDI of polymer 9 was 1.61, and the molecular weight Mn was 10100.

[0184] The above polymer 9 contains phosphorus and silicon, and has flame retardance.

[0185] The technical features of the above-described embodiments can be combined in any manner. For the sake of brevity, not all possible combinations of the technical features in the above-described embodiments are described, but as long as the combinations of the technical features do not contradict each other, they should be considered within the scope of the present disclosure.

[0186] The above-described embodiments only express several implementation manners of the present application, facilitate the understanding of the technical solutions of the present application in detail, but should not be understood as a limitation on the protection scope of the present patent. It should be pointed out that, for those skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are all within the protection scope of the present application. It should be understood that, based on the technical solutions provided by the present application, the technical solutions obtained by logical analysis, reasoning or limited experiments by those skilled in the art are all within the protection scope of the appended claims of the present application. Therefore, the protection scope of the present patent should be subject to the contents of the appended claims, and the description can be used to explain the contents of the claims.

Claims

1. A process for the preparation of a silicon-containing bisphospholene compound, characterized by, The method comprises the following steps: mixing and reacting compound 1, compound 2, a first organic solvent and a first basic reagent to prepare a silicon-containing bisphospholene compound; wherein the compound 1 has the structural formula , the compound 2 has the structural formula , and the silicon-containing bisphospholene compound has the structural formula R 1 R 3 each independently is C1-C 10 alkyl, R 4 R 7 each independently is substituted or unsubstituted C5-C 20 aryl, substituted C5-C 20 aryl selected from the group consisting of C1-C 10 alkyl-substituted C5-C 20 aryl, C1-C 10 alkoxy-substituted C5-C 20 aryl, and halogen-substituted C5-C 20 aryl in any one or more combinations thereof, or, R 4 R 7 each independently is pyridyl or thienyl; the first organic solvent is selected from any one or a combination of multiple of xylene, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane and diethyl ether; the first basic reagent is selected from any one or a combination of both of n-butyllithium and sec-butyllithium, and the reaction temperature is -10°C to 40°C.

2. The process for the preparation of a silicon-containing bisphospholene compound according to claim 1, characterized in that, The preparation method satisfies any one or more of the following conditions: (1) the molar ratio of the compound 1, the first basic reagent and the compound 2 is 1:(1-1.2):(1-1.2); (2) the dosage ratio of the first organic solvent to the compound 1 is (1mL-10mL):1mmol; (3) the reaction time is 1h-24h.

3. The process for the preparation of a silicon-containing bisphospholene compound according to claim 2, characterized in that, The preparation method satisfies any one or more of the following conditions: (1) the first organic solvent is selected from any one or a combination of multiple of tetrahydrofuran, 2-methyltetrahydrofuran and diethyl ether; (3) the reaction time is 10h-24h.

4. The process for the preparation of a silicon-containing bisphospholene compound according to any one of claims 1 to 3, characterized in that, The step of mixing and reacting the compound 1, the compound 2, the first organic solvent and the first basic reagent comprises: reacting the compound 1, the first organic solvent and the first basic reagent at -10°C to 40°C for 1h-2h, then adding the compound 2 to continue the reaction for 10h-15h, the first organic solvent is selected from tetrahydrofuran, and the first basic reagent is selected from n-butyllithium.

5. The process for the preparation of a silicon-containing bisphospholene compound according to any one of claims 1 to 3, characterized in that, R 1 ~R 3 each independently C1-C6alkyl; and / or, R 4 ~R 7 each independently is substituted or unsubstituted phenyl, substituted phenyl is selected from the group consisting of C1-C4alkyl-substituted phenyl, C1-C4alkoxy-substituted phenyl, and halogen-substituted phenyl. 10 alkyl-substituted phenyl.

6. A process for the preparation of a silicon-containing bisphospholene compound, characterized by, The method comprises the following steps: mixing and reacting compound 4, compound 5, a second organic solvent and a second basic reagent to prepare the silicon-containing bisphospholene compound; wherein the compound 4 has the structural formula , the compound 5 has the structural formula , and the silicon-containing bisphospholene compound has the structural formula , R 1 R 3 each independently is C1-C 10 alkyl, R 4 R 7 each independently is substituted or unsubstituted C5-C 20 aryl, substituted C5-C 20 aryl selected from the group consisting of C1-C 10 alkyl-substituted C5-C 20 aryl, C1-C 10 alkoxy-substituted C5-C 20 aryl, and halogen-substituted C5-C 20 aryl, or a combination of one or more of any of the foregoing, or R 4 R 7 each independently is pyridyl or thienyl; the second organic solvent is selected from any one or a combination of multiple of tetrahydrofuran, 2-methyltetrahydrofuran and diethyl ether; the second basic reagent is selected from any one or a combination of both of potassium tert-butoxide and potassium methoxide, and the reaction temperature is 10°C to 30°C.

7. The process for the preparation of a silicon-containing bisphospholene compound according to claim 6, characterized in that, The preparation method satisfies any one or more of the following conditions: (1) the dosage ratio of the second organic solvent to the compound 4 is (1mL-10mL):1mmol; (2) the molar ratio of the compound 4, the second basic reagent and the compound 5 is 1:(0.01-1.5):(1-1.2); (4) the reaction time is 1h-24h.

8. The process for the preparation of a silicon-containing bisphospholene compound according to claim 6 or 7, characterized in that, The preparation method satisfies any one or more of the following conditions: (1) the second organic solvent is selected from tetrahydrofuran; (2) the second basic reagent is selected from potassium tert-butoxide; (3) the reaction time is 10h-20h.

9. The process for the preparation of a silicon-containing bisphospholene compound according to claim 6 or 7, characterized in that, R 1 ~R 3 each independently is C1-C6alkyl; and / or, R 4 ~R 7 each independently is substituted or unsubstituted phenyl, substituted phenyl being selected from the group consisting of C1-C4alkyl-substituted phenyl, C1-C4alkoxy-substituted phenyl, and halogen-substituted phenyl. 10 alkyl-substituted phenyl.

Images