阅读说明：本技术 一种合成硅基磷簇合物的方法及其产品 (Method for synthesizing silicon-based phosphorus cluster compound and product thereof ) 是由 李岩 刘承欢 朱可可 王华兰 韩伟纯 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种合成硅基磷簇合物的方法,包括步骤：(1)惰性气体保护下,向反应器内加入极性溶剂、金属还原剂M、红磷和催化剂,搅拌加热反应；(2)将步骤(1)所得反应体系冷却并维持在-20℃以下,加入卤代硅烷,然后自然升温至室温并继续反应,反应完毕后经后处理得到如下式(I)所示产物；<Image he="284" wi="700" file="DDA0002547805940000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,Silyl代表通式R<Sup>1</Sup>R<Sup>2</Sup>R<Sup>3</Sup>Si,R<Sup>1</Sup>、R<Sup>2</Sup>、R<Sup>3</Sup>基团分别独立选自饱和烷烃基、不饱和烃基、烷氧基或芳基。本发明还公开了所述方法合成的硅基磷簇合物。(The invention discloses a method for synthesizing a silicon-based phosphorus cluster compound, which comprises the following steps: (1) under the protection of inert gas, adding a polar solvent, a metal reducing agent M, red phosphorus and a catalyst into a reactor, and stirring and heating for reaction; (2) cooling the reaction system obtained in the step (1) and maintaining the temperature below-20 ℃, adding halogenated silane, naturally heating to room temperature and continuing to react, and carrying out post-treatment after the reaction is finished to obtain a product shown as the following formula (I); wherein Silyl represents the formula R 1 R 2 R 3 Si，R 1 、R 2 、R 3 The groups are respectively and independently selected from saturated alkyl, unsaturated alkyl, alkoxy or aryl. The invention also discloses a silicon-based phosphorus cluster compound synthesized by the method.)

1. A method for synthesizing silicon-based phosphorus clusters, comprising the steps of:

(1) under the protection of inert gas, adding a polar solvent, a metal reducing agent M, red phosphorus and a catalyst into a reactor, and stirring and heating for reaction;

(2) cooling the reaction system obtained in the step (1) and maintaining the temperature below-20 ℃, adding halogenated silane, naturally heating to room temperature and continuing to react, and carrying out post-treatment after the reaction is finished to obtain a product shown as the following formula (I);

wherein Silyl represents the formula R¹R²R³Si，R¹、R²、R³The groups are respectively and independently selected from saturated alkyl, unsaturated alkyl, alkoxy or aryl.

2. The method according to claim 1, wherein in the step (1), the polar solvent is at least one of dimethyl glycol ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, tetrahydrofuran, 2-methyl-tetrahydrofuran, and 1, 4-dioxane;

the metal reducing agent M is at least one of lithium, sodium and potassium or an alloy containing at least one of lithium, sodium and potassium;

the catalyst is at least one of naphthalene, 1-methylnaphthalene and 2-methylnaphthalene, and the molar ratio of the addition amount of the catalyst to the addition amount of red phosphorus is 1-6: 100.

3. The method according to claim 1 or 2, wherein in the step (1), the heating temperature is 60 to 130 ℃, and the reaction time is 3 to 18 hours.

4. The method of claim 1, wherein the halosilane has the formula R¹R²R³SiX, wherein R¹、R²、R³The groups are respectively and independently selected from saturated alkyl, unsaturated alkyl, alkoxy or aryl, and X is halogen.

5. The method of claim 1 or 4, wherein R in Silyl is¹、R²、R³The carbon number of the groups is 1-12 independently.

6. The method according to claim 1, wherein the molar ratio of the metal reducing agent M to the red phosphorus to the halosilane is 3:7:3 to 5.

7. The method of claim 1, wherein in the step (2), the cooling temperature is-78 to-20 ℃, and the time for continuing the reaction is 0.5 to 2 hours.

8. The method according to claim 1, wherein in the step (2), the post-processing is: filtering and collecting filtrate under the protection of inert gas, removing the solvent under reduced pressure, and finally washing by a non-polar solvent to obtain the product.

9. The method according to claim 8, wherein the nonpolar solvent is an alkane and/or a cycloalkane, and the carbon number of the nonpolar solvent is not less than 6.

10. A silicon-based phosphorus cluster compound synthesized according to the method of any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of organic silicon, in particular to a method for synthesizing a silicon-based phosphorus cluster compound and a product thereof.

Background

P₇R₃The compound is a compound which has a plurality of P centers to form an inorganic cage-shaped inner core and is substituted by organic functional groups at the periphery. When R is silicon base, the compound has good stability and organic solvent solubility, can be used for constructing functional group inorganic phosphorus cluster derivatives with other topological structures, and is expected to be used as a precursor for preparing catalysts and nano materials. (Angew. chem. ed. Engl.,1981,20, 33; Angew. chem. Ed. Engl.,1982,21,863) although this class of compounds has been studied for many years, its preparation process is not perfect and its functional group derivatives are of very limited variety, affecting its popularization in the fields of synthetic chemistry and material chemistry.

The traditional preparation method of the compound is (taking P as the raw material)₇(SiMe₃)₃For example): formation of liquid alloys with white phosphorus (P) in ether solvents such as dimethyl glycol ether (DME) with sodium and potassium metals₄) Reaction to produce M₃P₇Then, further reacting with trimethylchlorosilane (Me)₃SiCl) to obtain the product. (Z.anorg. allg.chem.1978,440,171) the reaction formula is shown below:

this method has significant drawbacks, such as: 1) the reducing agent in the system is active sodium-potassium alloy, so that the system is easy to catch fire or explode and has higher danger; 2) the use of toxic and flammable white phosphorus as a source of phosphorus is hazardous.

Schmidbaur et al improved the preparation method by replacing white phosphorus with cheap and readily available red phosphorus and replacing DME with toluene, instead of the nonpolar solvent, to perform the silylation reaction, and obtain the product P in higher yield₇(SiMe₃)₃。(Phosphorus,Sulfur Silicon Relat.Elem.1995,102,217-219)

However, this method still has drawbacks, such as: 1) the reducing agent sodium-potassium alloy used in the system still has higher danger; 2) the reaction time is long, and the steps are more; 3) drying under reduced pressure halfway to obtain M₃P₇The (M ═ Na, K) salts mix with large amounts of unreacted sodium potassium alloy and form larger solidsAgglomeration requires manual pulverization under an inert atmosphere. These all impose limitations on practical operation.

Most of the compounds reported at present are trimethylsilyl-substituted P₇ ^3-Clusters, other different silicon-based functional groups (-SiR)₃) The derivatives of (a) have not been developed. Only Hassler et al have reported the preparation of P by a silicon-based exchange reaction₇(SiPh₃)₃(Angew. chem.1982,94,869) and incomplete substitution products [ (Me)₃Si)₃Si]₂P₇(SiMe₃)。(J.Organomet.Chem.,2011,696,652)

Disclosure of Invention

Based on the above reasons, the invention provides a method for synthesizing silicon-based phosphorus cluster compound, and the silicon-based phosphorus cluster compound is prepared by continuous reaction in a one-pot method, has universality, is shorter, efficient, safe and feasible compared with the traditional method.

A method of synthesizing silicon-based phosphorus clusters comprising the steps of:

(1) under the protection of inert gas, adding a polar solvent, a metal reducing agent M, red phosphorus and a catalyst into a reactor, and stirring and heating for reaction;

(2) cooling the reaction system obtained in the step (1) and maintaining the temperature below-20 ℃, adding halogenated silane, naturally heating to room temperature and continuing to react, and carrying out post-treatment after the reaction is finished to obtain a product shown as the following formula (I);

wherein Silyl represents the formula R¹R²R³Si，R¹、R²、R³The groups are respectively and independently selected from saturated alkyl, unsaturated alkyl, alkoxy or aryl. The saturated alkyl group may be a methyl group, an ethyl group, a propyl group, etc., the unsaturated alkyl group may be a vinyl group, an allyl group, etc., the alkoxy group may be a methoxy group, an ethoxy group, etc., and the aryl group may be a phenyl group, a substituted phenyl group, etc.

The inert gas in the present invention may be at least one of nitrogen gas and rare gas, and the rare gas may be argon gas or the like.

In the step (1), the polar solvent may be one commonly used in the art, and specifically may be at least one of dimethyl glycol ether (DME), propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, tetrahydrofuran, 2-methyl-tetrahydrofuran, and 1, 4-dioxane. The polar solvent is preferably DME.

In the step (1), the metal reducing agent M may be a metal reducing agent commonly used in the art, and specifically may be at least one of lithium, sodium, and potassium, or an alloy containing at least one of lithium, sodium, and potassium, such as a sodium-potassium alloy. The metal reducing agent M is preferably Na.

In the step (1), the catalyst is at least one of naphthalene, 1-methylnaphthalene and 2-methylnaphthalene, and naphthalene is preferred. The molar ratio of the addition amount of the catalyst to the addition amount of the red phosphorus is preferably 1-6: 100.

One preferable substance combination of the reaction system in the step (1) is as follows: the polar solvent is DME, the metal reducing agent M is Na, and the catalyst is naphthalene. The obtained product has the highest purity and the method is the safest.

In the step (1), the heating temperature can be adjusted according to the actual reflux condition, and is preferably 60-130 ℃.

In the step (1), the reaction time is only 3-18 h.

The general formula of the halogenated silane is R¹R²R³SiX, wherein R¹、R²、R³The groups are respectively and independently selected from saturated alkyl, unsaturated alkyl, alkoxy or aryl, and X is halogen such as F, Cl, Br, I and the like. The saturated alkyl group may be a methyl group, an ethyl group, a propyl group, etc., the unsaturated alkyl group may be a vinyl group, an allyl group, etc., the alkoxy group may be a methoxy group, an ethoxy group, etc., and the aryl group may be a phenyl group, a substituted phenyl group, etc.

Preferably, R in Silyl¹、R²、R³The carbon number of the groups is 1-12 independently. Preferably, R in the halosilane¹、R²、R³The carbon number of the groups is 1-12 independently.

Preferably, the molar ratio of the metal reducing agent M to the red phosphorus to the halogenated silane is 3:7: 3-5.

In the step (2), the cooling temperature is preferably-78 to-20 ℃.

In the step (2), the continuous reaction time is only 0.5-2 h.

In the step (2), the post-treatment is preferably: filtering and collecting filtrate under the protection of inert gas, removing the solvent under reduced pressure, and finally washing by a non-polar solvent to obtain the product.

The nonpolar solvent is preferably an alkane and/or cycloalkane, and the nonpolar solvent is preferably one having a carbon number of not less than 6. The non-polar solvent can be hexane, pentane, heptane, cyclohexane and the like, and is preferably cyclohexane, and the purity of the obtained product is highest.

The invention also provides a silicon-based phosphorus cluster compound synthesized by the method.

Compared with the prior art, the invention has the main advantages that: compared with the traditional method, the method disclosed by the invention has the advantages that a proper metal reducing agent, a polar solvent and a catalyst are selected, a special synthesis method is combined, a good synergistic effect is exerted, and the effects of few steps, safety in operation, high reaction efficiency, high product purity, good product group universality and the like are achieved.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.