CN113214306B - Preparation method of double-amino-silicon ether compound and double-amino-silicon ether compound - Google Patents

Preparation method of double-amino-silicon ether compound and double-amino-silicon ether compound Download PDF

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CN113214306B
CN113214306B CN202110330316.7A CN202110330316A CN113214306B CN 113214306 B CN113214306 B CN 113214306B CN 202110330316 A CN202110330316 A CN 202110330316A CN 113214306 B CN113214306 B CN 113214306B
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CN113214306A (en
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单良
王宙东
张国平
孙蓉
王旷宇
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Shenzhen Institute of Advanced Electronic Materials
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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 Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen

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Abstract

The preparation method takes the available chloro-silicon ether compound or the silicon ether compound as the initial raw material, and the initial raw material reacts with an alkenyl Grignard reagent to construct a C-Si bond, so that the preparation method does not need noble metal catalyst catalysis, and has the advantages of low production cost, mild and controllable reaction conditions, safety, environmental protection, high efficiency and suitability for large-scale industrial production. In addition, the preparation method is particularly suitable for preparing double-end amino silicon ether compounds containing large steric hindrance aryl and heterocyclic substituent groups with electron withdrawing or electron pushing effects, and can obtain target products in high yield.

Description

Preparation method of double-amino-silicon ether compound and double-amino-silicon ether compound
Technical Field
The application relates to the technical field of preparation of silyl ether, in particular to a preparation method of a double-end amino silyl ether compound and the double-end amino silyl ether compound prepared by the preparation method.
Background
In the chemical industry, the double-end amino silicon ether compound can be used as a diamine monomer for producing a block copolymer, for example, the double-end amino silicon ether compound reacts with dianhydride to introduce silicon ether into polyimide, so that the obtained silicon-containing polyimide has excellent heat resistance and chemical stability of polyimide, and the silicon ether has easy processability, low hygroscopicity and good adhesiveness. Furthermore, the double-ended aminosilicone ether compounds have good molecular flexibility and reactivity, which can be used as softeners in hair care and textile formulations.
Currently, the industrial application range of double-end amino silyl ether compounds is limited by the production cost. The reported synthesis method of the double-end amino silicon ether compound has the problems of higher production cost, complicated steps and low yield of the double-end amino siloxane product with large steric hindrance. For example, in chinese patent application with application publication No. CN 102276639a, a process for preparing double-ended amino (poly) silyl ether is provided, which comprises protecting amino groups of primary aliphatic hydrocarbon groups with phthalic anhydride to obtain N-aliphatic hydrocarbon group imide, then subjecting the N-aliphatic hydrocarbon group imide and hydrogen-containing silyl ether to addition reaction under the action of platinum catalyst to build C-Si bond to obtain double-ended amino silyl ether, then subjecting the double-ended amino silyl ether to polymerization reaction with silicon monomer under the action of acid catalyst to obtain double-ended amino silyl ether, and finally subjecting the double-ended amino silyl ether to reflux deprotection in ethanol solution of hydrazine hydrate to obtain double-ended amino silyl ether. The method has the defects that: in the first aspect, expensive platinum catalyst is needed in the process of constructing the C-Si bond, and the method has the defect of high production cost; in the second aspect, the construction of C-Si bonds by platinum catalyst catalytic addition has obvious limitation, and when a silicon atom is connected with a group with large steric hindrance (such as aryl), the yield of the product is low, so that the method is not suitable for large-scale industrial production; in the third aspect, for the step of polymerizing a bisphenol imide silyl ether with a silicon monomer under acid catalysis to obtain a bisphenol imide polysilicone ether, the strong acid may damage the siloxane bond, thereby risking the structural integrity of the product.
Disclosure of Invention
In view of the problems in the prior art, the present application provides a method for preparing a double-ended amino silicon ether compound, and a double-ended amino silicon ether compound prepared by the method, wherein the double-ended amino silicon ether compound comprises silicon ether terminated by amino groups and silicon ether polymer terminated by amino groups.
In a first aspect, the present application provides a method for preparing a double-ended amino silyl ether compound, the method comprising the steps of:
(A) Subjecting a compound a represented by formula (1) to nucleophilic substitution reaction with a compound b represented by formula (2) to obtain a compound c represented by formula (3);
(B) Mixing the compound c, an organoboron compound and hydrogen peroxide under alkaline conditions to perform a borohydride oxidation reaction to obtain a compound d shown in a formula (4);
(C) Reacting the compound d with a compound e represented by formula (5) to obtain a compound f represented by formula (6); and
(D) Subjecting the compound f to a reduction reaction to obtain a final product represented by formula (7);
wherein, the formulas (1) to (5) are as follows:
in the formulas (1) to (7), n is not less than 0;
R 1 、R 2 、R 3 and R is 4 Independently of each other, at least one selected from aliphatic hydrocarbon groups, aryl groups, substituted aryl groups, heterocyclic groups or substituted heterocyclic groups, R 5 Is a chlorine atom or an alkoxy group, and when n is 0, R 5 Is an alkoxy group;
R 6 at least one selected from an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, or a substituted heterocyclic group;
R 7 and R is 8 Independently of each other, at least one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a substituted aryl group, a heterocyclic group and a substituted heterocyclic group;
R 11 at least one selected from a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a substituted aryl group, a heterocyclic group, and a substituted heterocyclic group.
In some embodiments of the present application, in formulas (1) to (7), 1.ltoreq.n.ltoreq.50.
In some embodiments of the present application, in formulas (1) to (7), 1.ltoreq.n.ltoreq.10.
In some embodiments of the present application, the R 1 Said R is 2 Said R is 3 And said R 4 Independently of each other, at least one selected from methyl, ethyl or phenyl.
In some embodiments of the present application, when n is greater than 0, the R 5 Is a chlorine atom.
In some embodiments of the present application, the R 6 Is methylene.
In some embodiments of the present application, the R 7 And said R 8 Are all hydrogen atoms.
In some embodiments of the present application, the R 11 At least one selected from the group consisting of the following structural formulae:
In some embodiments of the present application, step (a) comprises the steps of: dissolving the compound a in an organic solvent to obtain an organic solution containing the compound a, and then mixing the compound b with the organic solution containing the compound a under anhydrous and anaerobic conditions at a temperature of 0 ℃ or lower to perform nucleophilic substitution reaction.
In some embodiments of the present application, the molar equivalent of compound a to compound b is 1: (2-8).
In some embodiments of the present application, step (B) comprises the steps of:
(B1) Dissolving the compound c in an organic solvent to obtain an organic solution containing the compound c, and then mixing the organic solution containing the compound c with the organoboron compound under anhydrous and anaerobic conditions to perform a reaction; and
(B2) When the compound c is consumed in the step (B1), the temperature is controlled to be 35 ℃ or lower, and then an alkaline agent and hydrogen peroxide are added to perform a reaction to obtain a compound d represented by the formula (4).
In some embodiments of the present application, the organoboron compound is represented by formula (8) below:
in formula (8), R 9 And R is 10 Independently of each other, at least one selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, a hydrocarbyloxy group, and a borane group.
In some embodiments of the present application, the organoboron compound is selected from at least one of the compounds represented by the following structural formulas:
in some embodiments of the present application, the organoboron compound is selected from at least one of the compounds represented by the following structural formulas:
in some embodiments of the present application, in step (B), the molar equivalent of the basic agent, the organoboron compound, and the compound c is (1-20): (1-6): 1.
in some embodiments of the present application, in step (B), the volume ratio of the alkaline reagent to hydrogen peroxide is (1-3): (1-3).
In some embodiments of the present application, in step (C), the compound d is reacted with the compound e under the action of a reagent g, wherein the reagent g comprises a compound g 1 And Compound g 2 The compound g 1 Is a compound represented by the following formula (9), wherein the compound g 2 Is a compound represented by the following formula (10) and/or a salt of a compound represented by the formula (10):
wherein in formula (9), R 12 And R is 13 Independently of each other, at least one selected from the group consisting of alkoxy, substituted alkoxy, aryloxy, substituted aryloxy, heterocyclyloxy, substituted heteroaryloxy and amino;
In formula (10), R 14 At least one selected from aliphatic hydrocarbon groups, aryl groups, substituted aryl groups, heterocyclic groups or substituted heterocyclic groups.
In some embodiments of the present application, in formula (9), R 12 And R is 13 Independently of each other, at least one of methoxy, ethoxy or isopropoxy.
In some embodiments of the present application, in formula (10), R 14 At least one selected from alkyl, aryl or substituted aryl, e.g. R 14 Phenyl, also denoted as R 14 Is cyclohexyl.
In some embodiments of the present application, the step (C) comprises the steps of:
(C1) Combining said compound d, said compound e and said compound g 2 Dissolving in an organic solvent to obtain an organic mixed solution; and
(C2) Adding the compound g to the organic mixed solution of step (C1) under a protective gas atmosphere of 10-100 DEG C 1 The mixing reaction is carried out until the compound d is consumed, to obtain a compound f represented by formula (6).
In some embodiments of the present application, in step (C1), the compound d, the compound e, and the compound g 2 Molar equivalent of 1: (2-6): (2-6).
In some embodiments of the present application, in step (C2), the molar ratio of the compound g1 to the organic mixed solution compound d is (1 to 8): 1.
In some embodiments of the present application, in step (D), the subjecting compound f to a hydrode-deprotection reduction reaction is treating compound f with hydrazine hydrate.
In a second aspect, the present application provides a double-ended aminosilicone ether compound prepared by the method as described in the first aspect, the double-ended aminosilicone ether compound comprising a silyl ether terminated with an amino group, a silyl ether oligomer, and a silyl ether polymer.
The present application provides a process for the preparation of a double-ended aminosilicone ether compound, and double-ended aminosilicone ether compounds prepared by the process, which can be used to prepare a variety of molecular weight sized silyl ether compounds, such as double-ended aminosilicone ether, as well as double-ended aminosilicone ether. The preparation method takes the obtained chloro-silicon ether compound or the silicon ether compound as the initial raw material, and the initial raw material reacts with the compound b to construct the C-Si bond without catalysis of a noble metal catalyst, so that the preparation method has the advantages of low production cost, mild and controllable reaction conditions, safety, environmental protection, high efficiency and suitability for large-scale industrial production. In addition, the preparation method is particularly suitable for preparing double-end amino silicon ether compounds containing large steric hindrance aryl and heterocyclic substituent groups with electron withdrawing or electron pushing effects, and can obtain target products in high yield.
Drawings
Technical solutions and other advantageous effects of the present application will be made apparent from the following detailed description of specific embodiments of the present application with reference to the accompanying drawings.
FIG. 1 is a nuclear magnetic resonance spectrum of the final product obtained in example 1 of the present application.
Detailed Description
The present application aims to provide a method for producing a double-ended aminosilane ether compound, which can be used for producing various molecular weight silyl ether compounds, and a double-ended aminosilane ether compound, wherein the method is particularly suitable for producing a double-ended aminosilane ether compound having a large steric hindrance aryl group and a heterocyclic substituent having an electron withdrawing or electron pushing effect, and can obtain a target product in a high yield.
In the description of the present application, the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; accordingly, it should be considered that the description of the range format has specifically disclosed all possible subranges and single numbers within that range, e.g., for a range of degrees of polymerization n of 1.ltoreq.n.ltoreq.10, that a description of the range from 1 to 10 has specifically disclosed subranges, e.g., 1.ltoreq.n.ltoreq.3, 1.ltoreq.n.ltoreq.8, 2.ltoreq.n.ltoreq.4, 5.ltoreq.n.ltoreq.10, etc., as well as single numbers within the range, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, regardless of any range applicable. In addition, numerical ranges referred to in this application are meant to include any reference numbers (fractional or integer) within the indicated range.
The term "degree of polymerization" refers to an index of the molecular size of a polymer, based on the number of repeating units, and is a numerical value representing the number of repeating units contained in a polymer macromolecular chain, represented by n. It will be appreciated that when the product produced is a double-ended polysilicone ether, in particular when the double-ended polysilicone ether is a high polymer having a molecular weight of greater than 1500, the product may be composed of a mixture of a set of homologs of different degrees of polymerization (within a particular range) and of different structural morphologies, the degree of polymerization n of the product being referred to as its average degree of polymerization.
The term "double-end amino silicon ether compound" refers to a compound with a structure shown in a formula (7), and comprises double-end amino silicon ether and double-end amino polysilicone ether, wherein the term "double-end amino silicon ether" refers to a compound with a polymerization degree n of 1 in the formula (7), such as 1, 3-bis (3 '-aminopropyl) -1, 3-tetraphenyl disilyl ether, and 1, 3-bis (3' -aminopropyl) -1, 3-dimethyl-1, 3-diphenyl disilyl ether; "double amino polysilicone ether" refers to a compound of formula (7) having a degree of polymerization n of a value greater than 1, such as 1, 5-bis (3' -aminopropyl) -polydiphenylsilyl ether, and such as bis (3-aminopropyl) -polydiphenylsilyl ether. For formula (7), the polymerization degree n satisfies, for example, the condition 1. Ltoreq.n.ltoreq.10, or the condition 1. Ltoreq.n.ltoreq.100, or the condition 100. Ltoreq.n.ltoreq.1000, or the condition 1000. Ltoreq.n.ltoreq.10000.
The term "aliphatic hydrocarbon group" refers to a functional group containing only two atoms of carbon and hydrogen, and is a radical remaining after one hydrogen atom of the corresponding hydrocarbon is lost, and aliphatic hydrocarbon groups are the general term for all hydrocarbon groups except aromatic hydrocarbon groups, and include saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups. "aliphatic hydrocarbon groups" include, but are not limited to, methyl, ethyl, propyl, isopropyl, and the like.
The term "alkyl" refers to a saturated aliphatic hydrocarbon group, which is an aliphatic hydrocarbon group formed by the loss of one hydrogen atom in an alkane molecule.
The term "substituted alkyl" means that the hydrogen atom or atoms on the alkyl group are optionally substituted with other groups, which may be, for example, halogen atoms, allowing multiple degrees of substitution to occur.
The term "alkoxy" refers to the radical R a -O-, wherein R a -is an alkyl group.
The term "hydrocarbyloxy" means R b -O-, wherein R b Is an aliphatic hydrocarbon group. The "hydrocarbyloxy group" may be, for example, methoxy, ethoxy, isopropoxy, tert-butoxy, pentyloxy, or the like.
The term "aryl" refers to the generic term for monovalent radicals, usually denoted by Ar-, that remain after removal of a hydrogen atom from the aromatic nucleus carbon of an aromatic hydrocarbon molecule. "aryl" includes, but is not limited to, phenyl.
The term "substituted aryl" means that the hydrogen atom or atoms on the aryl group are optionally substituted with other groups, which may be, for example, halogen atoms, allowing multiple degrees of substitution to occur.
The term "aryloxy" refers to the group Ar-O-, wherein Ar-is aryl. "aryloxy" includes, but is not limited to, phenoxy.
The term "substituted aryloxy" means that the hydrogen atom or atoms on the aryloxy group are optionally substituted with other groups, which may be, for example, halogen atoms, allowing multiple degrees of substitution to occur.
The term "heterocyclic group" refers to a group formed by losing one hydrogen atom from a cyclic compound composed of a carbon atom and a non-carbon atom, and the non-carbon atom may be, for example, a nitrogen atom, an oxygen atom, a sulfur atom, or the like.
The term "substituted heterocyclyl" means that the hydrogen atom or atoms on the heterocyclyl are optionally substituted with other groups, which may be, for example, halogen atoms, allowing multiple degrees of substitution to occur.
The term "organoboron compound" refers to a class of organic compounds containing a carbon-boron bond or a boron atom, for example, an organic compound capable of participating in a borohydride reaction and containing a boron atom, and in the embodiments of the present application, the organoboron compound has a structure represented by formula (8).
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present invention. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the scope of the present application.
Unless otherwise indicated, the starting materials and reagents used in the following examples are commercially available or may be prepared by methods known in the art.
The application relates to a preparation method of a double-end amino silicon ether compound, which comprises the following steps:
(A) Subjecting a compound a represented by formula (1) to nucleophilic substitution reaction with a compound b represented by formula (2) to obtain a compound c represented by formula (3);
(B) Mixing a compound c, an organoboron compound and hydrogen peroxide under alkaline conditions to perform an addition reaction to obtain a compound d represented by formula (4);
(C) Reacting the compound d with a compound e represented by formula (5) to obtain a compound f represented by formula (6); and
(D) Subjecting the compound f to a deprotecting group reduction reaction to obtain a final product represented by formula (7);
wherein, the formulas (1) to (5) are as follows:
the following description is made of the formulas (1) to (7):
wherein n.gtoreq.0, for example 1.ltoreq.n.ltoreq.50, and for example 1.ltoreq.n.ltoreq.10.
R 1 、R 2 、R 3 And R is 4 Independently of each other selected from aliphatic hydrocarbon radicals, aryl radicals, substituted aryl radicals, heterocyclic radicals or radicalsAnd at least one of the substituted heterocyclic groups. In some embodiments, R 1 、R 2 、R 3 And R is 4 Independently of each other, at least one selected from methyl, ethyl or phenyl.
R 5 Is a chlorine atom or an alkoxy group, and when n is 0, R 5 Is an alkoxy group. In some embodiments, when n is greater than 0, R 5 Is a chlorine atom.
R 6 At least one selected from an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, and a substituted heterocyclic group. In some embodiments, R 6 Is methylene.
R 7 And R is 8 Independently of each other, at least one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a substituted aryl group, a heterocyclic group and a substituted heterocyclic group. In some embodiments, R 7 And R is 8 Are all hydrogen atoms.
R 11 At least one selected from aliphatic hydrocarbon groups, aryl groups, substituted aryl groups, heterocyclic groups or substituted heterocyclic groups. In some embodiments, R 11 At least one compound selected from the following structural formulas:
in some embodiments of the present application, step (a) comprises the steps of:
(A1) Compound a is dissolved in an organic solvent to obtain an organic solution containing compound a, and then compound b is mixed with the organic solution containing compound a under anhydrous and anaerobic conditions at a temperature of 0 ℃ or lower to perform nucleophilic substitution reaction.
Specifically, the organic solvent may be at least one of methanol, ethanol, isopropanol, ethyl acetate, methylene chloride, toluene, tetrahydrofuran, and n-hexane, for example.
(A2) After the nucleophilic substitution reaction in step (A1) is completed, the reactant is subjected to post-treatment to obtain the compound c.
Specifically, the post-treatment of step (A2) includes quenching, washing, drying, concentrating, and purifying operations. The purification may be, for example, at least one of reduced pressure distillation, silica gel column chromatography, and crystallization purification.
Illustratively, step (a) is specifically: (A1) Dissolving compound a in tetrahydrofuran to obtain a tetrahydrofuran solution containing 1.0 molar equivalent of compound b; under the anhydrous and anaerobic condition, 2-8 mol equivalent of compound b is cooled to below 0 ℃, tetrahydrofuran solution containing 1.0 mol equivalent of compound a is slowly added dropwise, and the reaction process is monitored by High Performance Liquid Chromatography (HPLC); (A2) After the nucleophilic substitution reaction in the step (A1) is finished, adding a saturated ammonium chloride solution or a hydrochloric acid solution with the concentration of 0.5mol/L into the reactant for quenching, then washing with a saturated sodium chloride solution, drying with anhydrous magnesium sulfate, concentrating an organic phase until no solvent exists, and finally distilling and purifying at the temperature of less than 100Pa and the temperature of 10-120 ℃ to obtain the compound c.
As an alternative embodiment, step (a) is specifically: (A1) Dissolving compound a in tetrahydrofuran to obtain a tetrahydrofuran solution containing 1.0 molar equivalent of compound b; under the anhydrous and anaerobic condition, 2-8 mol equivalent of compound b is cooled to below 0 ℃, tetrahydrofuran solution containing 1.0 mol equivalent of compound b is slowly added dropwise, and the reaction process is monitored by High Performance Liquid Chromatography (HPLC); (A2) After the nucleophilic substitution reaction in step (A1) is completed, a saturated ammonium chloride solution or a hydrochloric acid solution of 0.5mol/L is added to the reaction mixture to quench, and then the reaction mixture is washed with a saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and the organic phase is concentrated to be free of solvent to obtain a concentrate, which is concentrated to be free of solvent after passing through silica gel of 8 to 10 times the weight of the compound a, and then at least one organic solvent selected from methanol, ethanol, isopropanol, ethyl acetate, dichloromethane, toluene, tetrahydrofuran and n-hexane is added to crystallize and purify to obtain the compound c.
In some embodiments of the present application, step (B) comprises the steps of:
(B1) The compound c is dissolved in an organic solvent to obtain an organic solution containing the compound c, and then the organic solution containing the compound c is mixed with an organoboron compound under anhydrous and anaerobic conditions to perform a reaction.
Specifically, the organic solvent may be at least one of methanol, ethanol, isopropanol, ethyl acetate, methylene chloride, toluene, tetrahydrofuran, and n-hexane, for example. In some embodiments, the molar ratio of organoboron compound to compound c is (1-6): 1.
in some embodiments of the present application, the organoboron compound is represented by formula (8) below:
in formula (8), R 9 And R is 10 Independently of each other, at least one selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, a hydrocarbyloxy group, and a borane group.
In some embodiments, the organoboron compound is selected from at least one of the compounds represented by the following structural formulas:
in some embodiments, the organoboron compound is selected from at least one of the compounds represented by the following structural formulas:
in some embodiments, step (B) comprises the steps of:
(B1) Dissolving the compound c in an organic solvent to obtain an organic solution containing the compound c, and then mixing the organic solution containing the compound c with the organoboron compound under anhydrous and anaerobic conditions to perform a reaction; and
(B2) After the compound c is consumed in the step (B1), the temperature is controlled below 35 ℃, and then an alkaline reagent and hydrogen peroxide are added to perform a mixing reaction.
Specifically, the alkaline agent may be at least one of sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, and preferably at least one of 1mol/L to 6mol/L of an aqueous sodium bicarbonate solution, an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution. In some embodiments, the molar ratio of alkaline reagent to compound c is (1-20): 1. in some embodiments, the volume ratio of alkaline reagent to hydrogen peroxide is 1:1.
(B3) After the completion of the mixing reaction in step (B2), the reactants are subjected to post-treatment to obtain compound d.
Specifically, the post-treatment of step (A2) includes washing, drying, concentrating, and purifying operations. The purification may be, for example, at least one of reduced pressure distillation, silica gel column chromatography, and crystallization purification.
Illustratively, step (B) is specifically: (B1) Dissolving 1.0 molar equivalent of compound c in 5-30 times of dry tetrahydrofuran to obtain an organic solution containing the compound c, then adding 1-6 molar equivalents of an organoboron compound into the organic solution containing the compound c under anhydrous and anaerobic conditions, stirring and reacting under reflux, and monitoring the whole reaction process by adopting HPLC; (B2) After the compound c in the step (B1) is consumed, controlling the temperature below 35 ℃, adding 1-20 molar equivalents of alkaline reagent into the reaction system, then adding 30% (mass percent) hydrogen peroxide solution which is equal to the alkaline reagent in volume, and stirring for reaction for 1-8 h; (B3) After the reaction of the step (B2) is finished, adding a saturated sodium chloride solution into the reactant for washing, drying by using anhydrous magnesium sulfate, concentrating an organic phase until no solvent exists, and finally distilling and purifying under the condition of less than 100Pa and at the temperature of 10-100 ℃ to obtain the compound d. Wherein the distillative purification operation in step (B3) can be replaced by silica gel column chromatography and crystallization purification, with specific reference to the alternative embodiment of step (a) above.
In some embodiments of the present application, in step (C), the test is performedReacting compound d with compound e under the action of a reagent g, wherein the reagent g comprises a compound g 1 And Compound g 2 Compound g 1 Compound g being a compound represented by the following formula (9) 2 Is a compound represented by the following formula (10) and/or a salt of a compound represented by the formula (10):
wherein in formula (9), R 12 And R is 13 Independently of each other, at least one selected from the group consisting of alkoxy, substituted alkoxy, aryloxy, substituted aryloxy, heterocyclyloxy, substituted hetero-epoxy and amino. In some embodiments of the present application, R 12 And R is 13 Independently of each other, at least one of methoxy, ethoxy or isopropoxy.
In formula (10), R 14 At least one selected from alkyl, aryl or substituted aryl. For example R 14 Is cyclohexyl, as R 14 Is phenyl. In some embodiments of the present application, step (C) comprises the steps of:
(C1) The compound d, the compound e, and the compound g2 are mixed and then dissolved in an organic solvent to obtain an organic mixed solution.
Specifically, the organic solvent may be at least one of methanol, ethanol, isopropanol, ethyl acetate, methylene chloride, toluene, tetrahydrofuran, or n-hexane, for example. Preferably compound e, compound g 2 The molar ratio of the compound d is (2-6): (2-6): 1.
(C2) Adding a compound g into the organic mixed solution in the step (C1) under the atmosphere of protective gas at the temperature of 10-100 DEG C 1 The mixing reaction is carried out until the compound d is consumed to obtain a reactant.
In particular, the shielding gas is preferably nitrogen, compound g 1 The molar ratio of the organic mixed solution compound d is (1-8): 1 molar ratio.
(C3) Working up the reaction product obtained in step (C2) to obtain compound f.
Specifically, the post-treatment of step (C3) includes filtration to remove solids, washing, drying, concentration, and purification operations. The purification may be, for example, crystallization purification.
Illustratively, step (C) is specifically: (C1) Compound d, compound e and compound g 2 According to 1: (2-6): (2-6) and then dissolving in dry tetrahydrofuran to obtain an organic mixed solution; (C2) Dropwise adding a compound g into the organic mixed solution in the step (C1) in a nitrogen protection atmosphere at the temperature of 10-100 DEG C 1 Stirring and reacting until the compound d is consumed, so as to obtain a reactant; (C3) Filtering the reactant in the step (C2) to remove solids, washing the filtrate with saturated sodium chloride solution, drying the filtrate with anhydrous magnesium sulfate, concentrating the organic phase until no solvent exists, and finally adding an organic mixed solvent for crystallization and purification to obtain a compound f, wherein the organic mixed solvent is a mixture prepared from one or more of ethyl acetate, tetrahydrofuran, acetone, methylene dichloride and toluene, and petroleum ether in a ratio of 1: (1-10) by volume ratio.
In some embodiments of the present application, step (D) comprises the steps of:
(D1) Dissolving the compound f in an organic solvent to obtain an organic solution containing the compound f, then adding hydrazine hydrate, and carrying out reflux reaction under a protective gas atmosphere until the compound f is consumed, so as to obtain a reactant.
Specifically, the organic solvent may be at least one of methanol, ethanol, isopropanol, ethyl acetate, methylene chloride, toluene, tetrahydrofuran, and n-hexane, for example. The shielding gas may be, for example, nitrogen. For example, the molar ratio of compound f to hydrazine hydrate is 1: (2-10).
(D2) Post-treatment is carried out on the reactant obtained in the step (D1) to obtain a final product shown in a formula (7).
Specifically, the post-treatment of step (D2) includes filtration, concentration, and purification operations, wherein the purification may be, for example, distillation under reduced pressure, salting-out purification, and the like.
Illustratively, step (D) is specifically: (D1) Compound f was dissolved in tetrahydrofuran to obtain an organic solution containing compound f, and then 85% hydrazine hydrate was added, wherein the molar ratio of compound f to 85% hydrazine hydrate was 1:5, carrying out reflux reaction for 3-24 h under the nitrogen protection atmosphere of 50-120 ℃, and monitoring the whole reaction process by HPLC until the compound f is completely consumed, and obtaining a reactant; (D2) Filtering the reactant in the step (D1) to remove solids, concentrating the filtrate until no organic solvent exists, and finally distilling and purifying at the temperature of less than 100Pa and 10-120 ℃ to obtain a final product.
As an alternative embodiment of step (D2), step (D2) may also be: filtering the reactant of the step (D1) to remove solids, then concentrating the filtrate to be free of an organic solvent, then adding 10% sulfuric acid (mass concentration) to form a salt, filtering to collect a filter cake, dissolving the filter cake in toluene and adjusting the pH to 10 to 14 with an alkaline solution, then drying the organic phase with anhydrous magnesium sulfate, filtering again, and concentrating the filtrate to be free of a solvent to obtain a final product.
The preparation method of the double-ended amino silicon ether compound of the present application is described in detail below with reference to each specific example.
Example 1: preparation of 1, 3-bis (3' -aminopropyl) -1, 3-tetraphenyl disilyl ether
The embodiment provides a preparation method of 1, 3-bis (3' -aminopropyl) -1, 3-tetraphenyl disilyl ether, which specifically comprises the following steps:
s1, taking a three-mouth bottle with a thermometer and a constant pressure dropping funnel, adding 600mL of 1mol/L allylmagnesium bromide (CAS number 1730-25-2, corresponding to compound b) into the three-mouth bottle under the protection atmosphere of nitrogen, and cooling to 0 ℃; 100g (221.49 mmol) of 1, 3-dichloro-1, 3-tetraphenyl disiloxane (CAS number 7756-87-8, corresponding to Compound a) was dissolved in 300mL of anhydrous tetrahydrofuran to obtain a tetrahydrofuran solution, the tetrahydrofuran solution was added to a dropping funnel, allyl magnesium bromide was slowly added dropwise with stirring to cause a Grignard reaction, the temperature in the three-necked flask did not exceed 10℃throughout the Grignard reaction, and stirring was continued until the reaction ceased; after the reaction is finished, slowly dripping 300mL of saturated ammonium chloride solution into the reactant in the three-mouth bottle to quench, and then stirring and separating liquid and taking an organic phase; the organic phase was washed twice with a saturated sodium chloride solution, 300mL of the saturated sodium chloride solution was consumed each time, then the organic phase was dried with anhydrous magnesium sulfate, the dried organic phase was concentrated to be free of solvent to prepare a pale yellow oily liquid, and finally the oily liquid was distilled under reduced pressure under a condition of 80Pa to obtain 95.3g of a colorless oily liquid (corresponding to the compound c), which was allowed to stand for a long time to obtain a white solid in a yield of 92.9%.
Wherein, the reaction formula of the step S1 is as follows:
s2, taking a four-mouth bottle provided with a thermometer, a constant-pressure dropping funnel and a return pipe, adding 95g (205.30 mmol,1 molar equivalent) of the compound c prepared in the step S1 into the four-mouth bottle under the protection atmosphere of nitrogen, and dissolving with 950mL of anhydrous tetrahydrofuran to obtain a tetrahydrofuran solution; to the tetrahydrofuran solution was added in portions 2.5 molar equivalents of a 1mol/L borane tetrahydrofuran solution (commercially available under CAS number 14044-65-6), and then the whole mixed system was heated to conduct a reflux reaction; when the HPLC detects that the compound c in the reflux reaction system is completely consumed, the whole reflux reaction system is cooled to 30 ℃, 520mL of 3mol/L sodium carbonate aqueous solution is slowly added dropwise into the reflux reaction system, and the temperature in a four-mouth bottle is ensured not to exceed 35 ℃ in the whole dropping process; sodium carbonate (Na) 2 CO 3 ) Immediately after completion of the dropwise addition of the aqueous solution, 520mL of 30% hydrogen peroxide (H) 2 O 2 ) The solution is stirred to react, and the temperature in the whole reaction process is not more than 35 ℃; after the reaction, the organic phase was taken, washed twice with 300mL of saturated sodium chloride solution each time, then dried over anhydrous magnesium sulfate, concentrated to be solvent-free, and finally distilled under reduced pressure under 60Pa to obtain 89.5g of colorless oily liquid (corresponding to the compound d) in a yield of 87.4%.
Wherein, the reaction formula of the step S2 is as follows:
s3, another three-mouth bottle with a thermometer and a constant pressure dropping funnel is taken, 89g (178.44 mmol,1 mol equivalent) of the compound d prepared in the step S2 is added into the three-mouth bottle under the protection of nitrogen, then 2.5 mol equivalent of tricyclohexylphosphine (CAS No. 2622-14-2) and 2.5 mol equivalent of phthalimide (CAS No. 85-41-6) are added, and 890mL of anhydrous toluene is added, so that the compound d, tricyclohexylphosphine and phthalimide are fully dissolved in the anhydrous toluene to prepare an organic mixed solution; cooling the organic mixed solution to 10 ℃, slowly dropwise adding 2.5 molar equivalents of diisopropyl azodicarboxylate (CAS number 2446-83-5), naturally heating the reaction system to room temperature after the dropwise adding is finished, and reacting under the stirring condition until the compound d is consumed, so as to obtain a reactant; the reaction was filtered to remove solids, then the organic phase was washed twice with 300mL of saturated sodium chloride solution each time, then the organic phase was dried over anhydrous magnesium sulfate, and the dried organic phase was concentrated to be solvent-free, and finally purified by crystallization with an organic solvent to obtain 111.7g of compound f as a white solid in 82.6% yield, wherein the organic solvent was tetrahydrofuran and petroleum ether according to 1:3 volume ratio.
Wherein, the reaction formula of the step S3 is as follows:
s4, taking a three-mouth bottle with a thermometer, adding 111g (146.63 mmol,1 mol equivalent) of the compound f prepared in the step S3 into the three-mouth bottle, and then adding 1.1L of methanol to enable the compound f to be fully dissolved in the methanol to obtain a methanol solution containing the compound f; to a methanol solution containing the compound f, 5 equivalents of 85% hydrazine hydrate were added, followed by heating under a nitrogen atmosphere to proceedCarrying out reflux reaction, wherein the reflux reaction is carried out under the stirring condition until the compound f is consumed, and stopping the reaction to obtain a reactant; naturally cooling the reactant to room temperature, filtering to remove solids, concentrating the filtrate until no solvent exists, and finally distilling under reduced pressure under the condition of 65Pa to obtain 64.6g of final product with the yield of 88.6%, wherein the nuclear magnetism detection result of the final product is shown in figure 1, 1 H-NMR(CDCl 3 400M): δ (ppm) =1.03 (s, 4H), 1.40 (m, 4H), 2.54 (t, 4H), 7.33 (t, 8H), 7.41 (dd, 4H), 7.52 (m, 8H); the nuclear magnetic detection result shows that the final product is 1, 3-bis (3' -aminopropyl) -1, 3-tetraphenyl disilyl ether.
Wherein, the reaction formula of the step S4 is as follows:
example 2: preparation of 1, 3-bis (3' -aminopropyl) -1, 3-dimethyl-1, 3-diphenyldisilyl ether
The embodiment provides a preparation method of 1, 3-bis (3' -aminopropyl) -1, 3-dimethyl-1, 3-diphenyl disilyl ether, which comprises the following steps:
s1, taking a three-mouth bottle with a thermometer and a constant pressure dropping funnel, adding 400mL of 1mol/L allylmagnesium bromide (CAS number 1730-25-2, corresponding to compound b) into the three-mouth bottle under the protection atmosphere of nitrogen, and cooling to 0 ℃; 50g (152.74 mmol) of 1, 3-dichloro-1, 3-dimethyl-1, 3-diphenyl disilyl ether (CAS number 3582-72-7, corresponding to Compound a) was dissolved in 300mL of anhydrous tetrahydrofuran to obtain a tetrahydrofuran solution, the tetrahydrofuran solution was added to a dropping funnel, allyl magnesium bromide was slowly added dropwise with stirring to cause a Grignard reaction, the temperature in the three-necked flask did not exceed 10℃throughout the Grignard reaction, and stirring was continued until the reaction stopped; after the reaction is finished, 150mL of saturated ammonium chloride solution is slowly added dropwise into the reactant in the three-mouth bottle for quenching, and then the mixture is stirred and separated, and an organic phase is taken; the organic phase was washed twice with a saturated sodium chloride solution, 200mL of the saturated sodium chloride solution was consumed each time, then the organic phase was dried with anhydrous magnesium sulfate, the dried organic phase was concentrated to be free of solvent to prepare a pale yellow oily liquid, and finally the oily liquid was distilled under reduced pressure under a condition of 100Pa to obtain 46.7g of a colorless oily liquid (corresponding to the compound c) in a yield of 90.3%.
Wherein, the reaction formula of the step S1 is as follows:
s2, taking a four-mouth bottle provided with a thermometer, a constant pressure dropping funnel and a return pipe, adding 46g (135.85 mmol, 1mol equivalent) of the compound c prepared in the step S1 into the four-mouth bottle under the protection atmosphere of nitrogen, and dissolving the compound c with 460mL of anhydrous tetrahydrofuran to obtain a tetrahydrofuran solution; to the tetrahydrofuran solution was added in portions 2.5 molar equivalents of a 1mol/L borane tetrahydrofuran solution (commercially available under CAS number 14044-65-6), and then the whole mixed system was heated to conduct a reflux reaction; when the HPLC detects that the compound c in the reflux reaction system is completely consumed, the whole reflux reaction system is cooled to 30 ℃, 340mL of 3mol/L sodium carbonate aqueous solution is slowly added dropwise into the reflux reaction system, and the temperature in a four-mouth bottle is ensured not to exceed 35 ℃ in the whole dropping process; sodium carbonate (Na) 2 CO 3 ) Immediately after the completion of the dropwise addition of the aqueous solution, 340mL of 30% hydrogen peroxide (H) 2 O 2 ) The solution is stirred to react, and the temperature in the whole reaction process is not more than 35 ℃; after the reaction, the organic phase was taken, washed twice with 150mL of saturated sodium chloride solution each time, then dried over anhydrous magnesium sulfate, concentrated to be solvent-free, and finally distilled under reduced pressure under 80Pa to obtain 43.2g of colorless oily liquid (corresponding to the compound d) in a yield of 84.8%.
Wherein, the reaction formula of the step S2 is as follows:
s3, another three-mouth bottle with a thermometer and a constant pressure dropping funnel is taken, 43g (114.78 mmol,1 mol equivalent) of the compound d prepared in the step S2 is added into the three-mouth bottle under the protection of nitrogen, then 2.5 mol equivalent of tricyclohexylphosphine (CAS No. 2622-14-2) and 2.5 mol equivalent of phthalimide (CAS No. 85-41-6) are added, and 430mL of anhydrous toluene is added, so that the compound d, tricyclohexylphosphine and phthalimide are fully dissolved in the anhydrous toluene to prepare an organic mixed solution; cooling the organic mixed solution to 10 ℃, slowly dropwise adding 2.5 molar equivalents of diisopropyl azodicarboxylate (CAS number 2446-83-5), naturally heating the reaction system to room temperature after the dropwise adding is finished, and reacting under the stirring condition until the compound d is consumed, so as to obtain a reactant; the reaction was filtered to remove solids, then the organic phase was washed twice with 130mL of saturated sodium chloride solution each time, then the organic phase was dried over anhydrous magnesium sulfate, then the dried organic phase was concentrated to be solvent-free, and finally purified by crystallization with an organic solvent to obtain 61.3g of compound f as a white solid in 84.4% yield, wherein the organic solvent was tetrahydrofuran and petroleum ether according to 1:5 volume ratio.
Wherein, the reaction formula of the step S3 is as follows:
s4, another three-mouth bottle with a thermometer is taken, 61g (96.39 mmol,1 mol equivalent) of the compound f prepared in the step S3 is added, and 610mL of methanol is added to make the compound f fully dissolved in the methanol, so as to obtain a methanol solution containing the compound f; adding 5 molar equivalents of 85% hydrazine hydrate into a methanol solution containing a compound f, heating under a nitrogen protection atmosphere to perform a reflux reaction, and stopping the reaction under stirring until the compound f is consumed to obtain a reactant; naturally cooling the reactant to room temperature, filtering to remove solids, concentrating the filtrate until no solvent is present, and distilling under reduced pressure at 90Pa30.8g of the final product was obtained in a yield of 85.7%, and the nuclear magnetic detection result of the final product was: 1 H-NMR (CDCl 3, 400M): δ (ppm) =0.24 (s, 6H), 0.85 (s, 4H), 1.41 (m, 4H), 2.56 (t, 4H), 7.31 (t, 4H), 7.40 (dd, 2H), 7.51 (m, 4H); the nuclear magnetic detection result shows that the final product is 1, 3-bis (3' -aminopropyl) -1, 3-dimethyl-1, 3-diphenyl disilyl ether.
Wherein, the reaction formula of the step S4 is as follows:
example 3: preparation of 1, 5-bis (3' -aminopropyl) -polydiphenylsilyl ether
The embodiment provides a preparation method of 1, 5-bis (3' -aminopropyl) -polydiphenylsilyl ether, which comprises the following steps:
s1, taking a three-mouth bottle with a thermometer and a constant pressure dropping funnel, adding 380mL of 1mol/L allyl magnesium bromide (CAS number 1730-25-2, corresponding to compound b) into the three-mouth bottle under the protection atmosphere of nitrogen, and cooling to 0 ℃; 90g (138.51 mmol) of 1, 5-dichloro-polydiphenylsilyl ether (CAS number 7756-88-9, corresponding to Compound a) are dissolved in 300mL of anhydrous tetrahydrofuran to obtain a tetrahydrofuran solution, the tetrahydrofuran solution is added to a dropping funnel, allyl magnesium bromide is slowly added dropwise with stirring to cause a Grignard reaction, the temperature in the three-necked flask is no more than 10 ℃ during the whole Grignard reaction, and stirring is continued until the reaction is stopped; after the reaction is finished, 270mL of saturated ammonium chloride solution is slowly added dropwise into the reactant in the three-mouth bottle for quenching, and then the mixture is stirred and separated, and an organic phase is taken; the organic phase was washed twice with a saturated sodium chloride solution, each time consuming 270mL of the saturated sodium chloride solution, then the organic phase was dried with anhydrous magnesium sulfate, the dried organic phase was concentrated to be free of solvent to prepare a pale yellow oily liquid, and the oily liquid was dissolved in 900mL of an organic solvent, wherein the organic solvent was petroleum ether and methylene chloride according to 3:1, purifying the mixture by a 720g silica gel column, and concentrating the purified organic phase until no solvent exists, thereby obtaining 80.7g of compound c which is white solid with the yield of 88.1%.
Wherein, the reaction formula of the step S1 is as follows:
s2, taking a four-mouth bottle provided with a thermometer, a constant-pressure dropping funnel and a return pipe, adding 80g (121.02 mmol, 1mol equivalent) of the compound c prepared in the step S1 into the four-mouth bottle under the protection atmosphere of nitrogen, and dissolving the compound c with 800mL of anhydrous tetrahydrofuran to obtain a tetrahydrofuran solution; to the tetrahydrofuran solution was added in portions 2.5 molar equivalents of a 1mol/L borane tetrahydrofuran solution (commercially available under CAS number 14044-65-6), and then the whole mixed system was heated to conduct a reflux reaction; when the HPLC detects that the compound c in the reflux reaction system is completely consumed, the whole reflux reaction system is cooled to 30 ℃, then 300mL of 3mol/L sodium carbonate aqueous solution is slowly added dropwise, and the temperature in a four-mouth bottle is ensured not to exceed 35 ℃ in the whole dropping process; sodium carbonate (Na) 2 CO 3 ) Immediately after the completion of the dropwise addition of the aqueous solution, 300mL of 30% hydrogen peroxide (H) 2 O 2 ) The solution is stirred to react, and the temperature in the whole reaction process is not more than 35 ℃; after the reaction was completed, the organic phase was taken, washed twice with a saturated sodium chloride solution, each time consuming 240mL of the saturated sodium chloride solution, then dried over anhydrous magnesium sulfate, concentrated to be free of solvent, and finally distilled under reduced pressure under 50Pa to obtain 70.8g of a colorless oily liquid (corresponding to the compound d) in a yield of 83.9%.
Wherein, the reaction formula of the step S2 is as follows:
s3, another three-mouth bottle with a thermometer and a constant pressure dropping funnel is taken, 70g (100.42 mmol,1 mol equivalent) of the compound d prepared in the step S2 is added into the three-mouth bottle under the protection of nitrogen, then 2.5 mol equivalent of tricyclohexylphosphine (CAS No. 2622-14-2) and 2.5 mol equivalent of phthalimide (CAS No. 85-41-6) are added, and 700mL of anhydrous toluene is added, so that the compound d, tricyclohexylphosphine and phthalimide are fully dissolved in the anhydrous toluene to prepare an organic mixed solution; cooling the organic mixed solution to 10 ℃, slowly dropwise adding 2.5 molar equivalents of diisopropyl azodicarboxylate (CAS number 2446-83-5), naturally heating the reaction system to room temperature after the dropwise adding is finished, and reacting under the stirring condition until the compound d is consumed, so as to obtain a reactant; the reaction was filtered to remove solids, then the organic phase was washed twice with 210mL of saturated sodium chloride solution each time, then the organic phase was dried over anhydrous magnesium sulfate, then the dried organic phase was concentrated to be solvent-free, and finally purified by crystallization with an organic solvent to give 83.5g of compound f as a white solid in 87.1% yield, wherein the organic solvent was ethyl acetate and petroleum ether according to 1:4 volume ratio.
Wherein, the reaction formula of the step S3 is as follows:
s4, another three-mouth bottle with a thermometer is taken, 83g (86.88 mmol,1 equivalent) of the compound f prepared in the step S3 is added, and 830mL of methanol is added to make the compound f fully dissolved in the methanol, so as to obtain a methanol solution containing the compound f; adding 5 equivalents of 85% hydrazine hydrate into a methanol solution containing a compound f, heating under the protection of nitrogen to perform reflux reaction, and stopping the reaction under the stirring condition until the compound f is consumed to obtain a reactant; naturally cooling the reaction mixture to room temperature, filtering to remove solids, concentrating the filtrate to obtain a pale yellow viscous oily liquid, adding 200mL of 10% (mass fraction) sulfuric acid to the oily liquid to form salt, filtering to collect a filter cake, dissolving the filter cake in anhydrous toluene, and adding saturated potassium hydroxideThe aqueous solution was adjusted to pH 10, the organic phase was dried over anhydrous magnesium sulfate, then filtered again to collect the filtrate, and the filtrate was concentrated to be solvent-free to obtain the final product as a white bulk solid in 80.6% yield as a nuclear magnetic resonance detection result: 1 H-NMR (CDCl 3, 400M): δ (ppm) =1.09 (s, 4H), 1.52 (m, 4H), 2.61 (t, 4H), 7.38 (b, 12H), 7.47 (b, 6H), 7.55 (b, 12H); the nuclear magnetic detection result shows that the final product is 1, 5-bis (3' -aminopropyl) -polydiphenylsilyl ether, and the amino propyl polydiphenylsiloxane is also called.
Wherein, the reaction formula of the step S4 is as follows:
example 4: preparation of bis (3' -aminopropyl) -polydiphenylsilyl ether
The embodiment provides a preparation method of bis (3 '-aminopropyl) -polydiphenylsilyl ether, wherein the polymerization degree n of the bis (3' -aminopropyl) -polydiphenylsilyl ether is 5-10, and the preparation method specifically comprises the following steps:
s1, taking a three-mouth bottle with a thermometer and a constant pressure dropping funnel, adding 250mL of 1mol/L allylmagnesium bromide (CAS number 1730-25-2, corresponding to compound b) into the three-mouth bottle under the protection atmosphere of nitrogen, and cooling to 0 ℃; 100g (152.74 mmol) of dichloro-poly-diphenyl-silyl ether (corresponding to compound a, commercially available) was dissolved in 1000mL of anhydrous tetrahydrofuran to obtain a tetrahydrofuran solution, the tetrahydrofuran solution was added to a dropping funnel, allylmagnesium bromide was slowly added dropwise with stirring to cause a grignard reaction, the temperature in the three-necked flask did not exceed 10 ℃ throughout the grignard reaction, and stirring was continued until the reaction ceased; after the reaction is finished, slowly dripping 200mL of saturated ammonium chloride solution into the reactant in the three-mouth bottle to quench, and then stirring and separating liquid and taking an organic phase; the organic phase was washed twice with a saturated sodium chloride solution, each time consuming 500mL of the saturated sodium chloride solution, then the organic phase was dried with anhydrous magnesium sulfate, the dried organic phase was concentrated to be solvent-free to prepare a pale yellow solid, and the pale yellow solid was dissolved in 2000mL of an organic solvent to obtain an organic solution, wherein the organic solvent was tetrahydrofuran and petroleum ether according to 1:1, then passing the organic solution through a 800g silica gel column for purification, and finally concentrating the organic phase collected by purification to be solvent-free to obtain 90.6g of compound c (CAS No. 97947-62-1) as a white solid.
Wherein, the reaction formula of the step S1 is as follows:
s2, taking a four-mouth bottle with a thermometer, a constant-pressure dropping funnel and a return pipe, adding 90g of the compound c prepared in the step S1 into the four-mouth bottle under the protection atmosphere of nitrogen, and dissolving the compound c with 900mL of anhydrous tetrahydrofuran to obtain a tetrahydrofuran solution; to the tetrahydrofuran solution was added in portions 2.5 molar equivalents of a 1mol/L borane tetrahydrofuran solution (commercially available under CAS number 14044-65-6), and then the whole mixed system was heated to conduct a reflux reaction; when the HPLC detects that the compound c in the reflux reaction system is completely consumed, the whole reflux reaction system is cooled to 30 ℃, then 200mL of 3mol/L sodium carbonate aqueous solution is slowly added dropwise, and the temperature in a four-mouth bottle is ensured not to exceed 35 ℃ in the whole dropping process; sodium carbonate (Na) 2 CO 3 ) Immediately after completion of the dropwise addition of the aqueous solution, 200mL of 30% hydrogen peroxide (H) 2 O 2 ) The solution is stirred to react, and the temperature in the whole reaction process is not more than 35 ℃; after the reaction, the organic phase was taken, washed twice with 300mL of saturated sodium chloride solution each time, then dried over anhydrous magnesium sulfate, concentrated to be solvent-free, and finally distilled under reduced pressure under 35Pa to obtain 87.2g of a pale yellow viscous oily liquid (corresponding to the compound d).
Wherein, the reaction formula of the step S2 is as follows:
s3, another three-mouth bottle with a thermometer and a constant pressure dropping funnel is taken, 87g of the compound d prepared in the step S2 is added into the three-mouth bottle under the protection of nitrogen, 55g of tricyclohexylphosphine (CAS number 2622-14-2) and 30g of phthalimide (CAS number 85-41-6) are added, 870mL of anhydrous toluene is added, and the compound d, tricyclohexylphosphine and phthalimide are fully dissolved in the anhydrous toluene to prepare an organic mixed solution; cooling the organic mixed solution to 10 ℃, slowly dropwise adding 35g of diisopropyl azodicarboxylate (CAS number 2446-83-5), naturally heating the reaction system to room temperature after the dropwise adding is finished, and reacting under stirring until the consumption of the compound d is finished to obtain a reactant; the reaction was filtered to remove solids, then the organic phase was washed twice with 300mL of saturated sodium chloride solution each time, then the organic phase was dried over anhydrous magnesium sulfate, and the dried organic phase was concentrated to no solvent to obtain 100.3g of compound f as an off-white solid.
Wherein, the reaction formula of the step S3 is as follows:
S4, another three-mouth bottle with a thermometer is taken, 100g of the compound f prepared in the step S3 is added into the three-mouth bottle, and then 500mL of isopropanol is added to enable the compound f to be fully dissolved in the isopropanol, so that an isopropanol solution containing the compound f is obtained; adding 20mL of 85% hydrazine hydrate into an isopropanol solution containing a compound f, heating under the protection atmosphere of nitrogen to perform reflux reaction, and stopping the reaction under the stirring condition until the compound f is consumed to obtain a reactant; naturally cooling the reaction mixture to room temperature, filtering to remove solids, concentrating the filtrate to obtain pale yellow oily liquid, adding 300mL of 10% (mass fraction) sulfuric acid into the oily liquid, stirring vigorously to form salt, filtering to collect filter cake, and dissolving the filter cake in anhydrous nailIn benzene, the pH was adjusted to 10 with saturated aqueous potassium hydroxide, the organic phase was dried over anhydrous magnesium sulfate, then filtered again to collect the filtrate, and the filtrate was concentrated to be solvent-free to obtain 54.9g of an off-white block solid as a final product whose nuclear magnetic resonance detection result was: 1 H-NMR (CDCl 3, 400M): δ (ppm) =1.09 (s, 4H), 1.53 (m, 4H), 2.62 (t, 4H), 7.38 (b), 7.47 (b), 7.55 (b); the nuclear magnetic resonance detection result shows that the final product is bis (3' -aminopropyl) -polydiphenylsilyl ether, and the CAS number corresponding to the final product is 97947-62-1.
Wherein, the reaction formula of the step S4 is as follows:
the preparation method of the double-end amino-silicon ether compound and the double-end amino-silicon ether compound provided by the embodiment of the application are described in detail. The principles and embodiments of the present application are described herein with reference to specific examples, the description of which is only for aiding in understanding the technical solution of the present application and its core ideas; those of ordinary skill in the art will appreciate that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the scope of the corresponding technical solutions of the embodiments of the present application.

Claims (20)

1. A method for preparing a double-ended amino silyl ether compound, which is characterized by comprising the following steps:
(A) Subjecting a compound a represented by formula (1) to nucleophilic substitution reaction with a compound b represented by formula (2) to obtain a compound c represented by formula (3);
(B) Mixing the compound c, an organoboron compound and hydrogen peroxide under alkaline conditions to perform a borohydride oxidation reaction to obtain a compound d shown in a formula (4);
(C) Reacting the compound d with a compound e represented by formula (5) to obtain a compound f represented by formula (6); and
(D) Subjecting the compound f to a reduction reaction to obtain a double-end amino silicon ether compound shown in a formula (7);
wherein, the formulas (1) to (7) are as follows:
(1)
(2)
(3)
(4)
(5)
(6)
(7)
in the formulas (1) to (7), n is more than or equal to 1 and less than or equal to 10;
wherein R is 1 、R 2 、R 3 And R is 4 Independently of each other, at least one selected from the group consisting of aliphatic hydrocarbon groups, aryl groups and substituted aryl groups, the substituents of the substituted aryl groups being selected from the group consisting of halogen atoms, R 5 Is a chlorine atom;
R 6 at least one selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, a substituted alkylene group, an arylene group and a substituted arylene group, the substituents of the substituted alkylene group and the substituted arylene group being selected from the group consisting of halogensAn atom;
R 7 and R is 8 Independently of each other, at least one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, and a substituted aryl group, the substituent of the substituted aryl group being selected from the group consisting of a halogen atom;
R 11 at least one selected from the group consisting of an alkylene group and a group represented by the following structural formula:
；/>；/>；/>；
；/>； />。
2. the method of claim 1, wherein R is 1 Said R is 2 Said R is 3 And said R 4 Independently of each other, at least one selected from methyl, ethyl or phenyl.
3. The method of claim 1, wherein R is 6 Is methylene.
4. The method of claim 1, wherein R is 7 And saidR 8 Are all hydrogen atoms.
5. The method according to any one of claims 1 to 4, wherein the step (a) comprises the steps of: dissolving the compound a in an organic solvent to obtain an organic solution containing the compound a, and then mixing the compound b with the organic solution containing the compound a under anhydrous and anaerobic conditions at a temperature of 0 ℃ or lower to perform nucleophilic substitution reaction.
6. The process of claim 5, wherein the molar equivalent of compound a to compound b is 1: (2-8).
7. The method according to any one of claims 1 to 4, wherein step (B) comprises the steps of:
(B1) Dissolving the compound c in an organic solvent to obtain an organic solution containing the compound c, and then mixing the organic solution containing the compound c with the organoboron compound under anhydrous and anaerobic conditions to perform a reaction; and
(B2) When the compound c is completely reacted in the step (B1), the temperature is controlled to 35 ℃ or less, and then an alkaline agent and hydrogen peroxide are added to perform the reaction to obtain the compound d represented by the formula (4).
8. The production method according to claim 7, wherein the organoboron compound is represented by the following formula (8):
(8)
in formula (8), R 9 And R is 10 Independently of each other, at least one selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group and a hydrocarbyloxy group.
9. The method of claim 8, wherein the organoboron compound is selected from at least one of the compounds of the following structural formula:
；/>；/>；/>；/>；/>the method comprises the steps of carrying out a first treatment on the surface of the Or->。
10. The method according to claim 7, wherein the organoboron compound is selected from at least one of the compounds represented by the following structural formulae:
；/>the method comprises the steps of carrying out a first treatment on the surface of the Or->。
11. The method according to claim 7, wherein in the step (B), the molar ratio of the alkaline agent, the organoboron compound and the compound c is (1 to 20): (1-6): 1.
12. the method according to claim 11, wherein in the step (B), the volume ratio of the alkaline agent to hydrogen peroxide is (1 to 3): (1-3).
13. The process according to any one of claims 1 to 4, wherein in step (C), the compound d is reacted with the compound e under the action of a reagent g consisting of a compound g 1 And Compound g 2 Composition of the compound g 1 Is a compound represented by the following formula (9), wherein the compound g 2 Is a compound represented by the following formula (10) and/or a salt of a compound represented by the formula (10):
(9)；
(10)；
wherein in formula (9), R 12 And R is 13 Independently of each other, at least one selected from the group consisting of an alkoxy group, a substituted alkoxy group, an aryloxy group, a substituted aryloxy group, a heterocyclic oxy group, a substituted hetero epoxy group, and an amine group, the substituent of the substituted alkoxy group, the substituent of the substituted aryloxy group, and the substituent of the substituted hetero epoxy group being selected from halogen atoms;
in formula (10), R 14 At least one selected from aliphatic hydrocarbon groups, aryl groups, substituted aryl groups, heterocyclic groups or substituted heterocyclic groups, wherein the substituent of the substituted aryl groups and the substituent of the substituted heterocyclic groups are selected from halogen atoms.
14. The process according to claim 13, wherein in the formula (9), R 12 And R is 13 Independently of each other, at least one of methoxy, ethoxy or isopropoxy.
15. The process according to claim 13, wherein in the formula (10), R 14 At least one selected from alkyl, aryl or substituted aryl, wherein the substituent of the substituted aryl is selected from halogen atoms.
16. The method of claim 13, wherein R 14 Selected from cyclohexyl or phenyl.
17. The method of claim 13, wherein step (C) comprises the steps of:
(C1) Combining said compound d, said compound e and said compound g 2 Dissolving in an organic solvent to obtain an organic mixed solution; and
(C2) Adding the compound g to the organic mixed solution of step (C1) under a protective gas atmosphere of 10-100 DEG C 1 The mixing reaction is carried out until the compound d is consumed, to obtain a compound f represented by formula (6).
18. The process according to claim 17, wherein in step (C1), the compound d, the compound e and the compound g 2 The molar ratio of (2) is 1: (2-6): (2-6).
19. The process according to claim 17, wherein in step (C2), the compound g 1 The molar ratio to the compound d is (1 to 8): 1.
20. the process according to any one of claims 1 to 4, wherein in step (D), the reduction of the compound f is carried out by treating the compound f with hydrazine hydrate.
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