CN112047974B - Photodegradable bridged silane and preparation method thereof - Google Patents
Photodegradable bridged silane and preparation method thereof Download PDFInfo
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- C07F7/02—Silicon compounds
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Abstract
The invention relates to a photodegradable bridged silane and a preparation method thereof. 1, 3-dimethyl-2-nitrobenzene is used as a raw material, 2-nitro-1, 3-phthalic acid is obtained through oxidation reaction, 2-nitro-1, 3-benzenedimethanol is obtained through reduction reaction of carboxylic acid groups, 2-nitro-1, 3-benzenedimethanol and chloroacetyl chloride are subjected to acylation reaction to obtain 2-nitro-1, 3-benzenedichloroacetate, and finally, the 2-nitro-1, 3-benzenedichloroacetate and amino-containing silane are subjected to substitution reaction to obtain the photodegradable bridged silane containing 2-nitrobenzyl. The photodegradable bridged silane obtained by the invention has good light response performance, can be used for designing and preparing light response functional materials, and has important application value. The synthesis process is simple, the raw materials are easy to obtain, the reaction conditions are mild, and the operability is high.
Description
Technical Field
The invention relates to photodegradable bridged silane and a preparation method thereof, belonging to the field of preparation of organic silicon compounds.
Background
The bridged polysiloxane is an organic-inorganic hybrid material, and has good application prospect in the fields of catalyst carriers, dielectric materials, luminescent materials, selective adsorption carriers and the like. The bridged silanes are monomers for preparing bridged polysiloxane materials, the structure of which can be represented by X3Si–R–SiX3Wherein X can be hydrogen, halogen, alkyl, alkoxy, acyloxy and other groups, R is an organic bridging group which has adjustability, and the physical and chemical properties of the bridging silane can be effectively adjusted and controlled through the chemical composition and structural design of the organic bridging group, so that the bridging silane with different functions or functions and corresponding polymer materials can be obtained, and the bridging silane has good development prospect in the field of new materials.
The degradable organic bridging group can endow the bridged polysiloxane material with degradable performance, and change the surface performance and the internal structure of the material. Currently, there are reports of bridged silane degradable by biological enzyme (J.Control. Release (2018)282, 62-75; Nanoscale (2015)7, 15046-15050; chem.Commun. (2015)51, 12324-12327; J.Mater. chem.B (2017)5, 4455-4469), and biological enzyme is a protein, has harsh requirements on environmental conditions, is easy to denaturize and inactivate, and can change the structure of the enzyme protein under the conditions of ultraviolet light, heat, surfactant, metal ions, strong acid, strong base, oxidant, reducing agent and the like, thereby reducing the applicability of the biological enzyme in degrading the bridged silane. Hydrolyzable bridged silanes (RSC Adv. (2018)8, 4914-4920; Mater. chem. Front. (2019)3, 111-119) have been reported in the literature, since the organic bridging group is susceptible to hydrolysis, it is not possible to prepare bridged polysiloxane materials using the conventional silane hydrolytic condensation method.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides photodegradable bridged silane and a preparation method thereof, the bridged silane contains 2-nitro-1, 3-phenylene optical functional organic groups, can be rapidly degraded under the illumination condition, can be used for preparing bridged polysiloxane materials with photodegradable performance, such as optical functional materials, adsorption and controlled release materials, photodegradable materials and the like, has the advantages of controllable time and space, high efficiency, convenient operation and the like, can realize the timed, quantitative and positioned degradation of compounds and materials thereof by adjusting illumination parameters, and has important technical advantages, so the photodegradable bridged silane has important application value in the fields of functional material design, controlled release, material degradation and the like. The invention also provides a simple and effective technical approach for preparing the photodegradable bridged silane, and the method has the advantages of easily available raw materials, mild reaction conditions and strong operability.
Description of terms:
a compound of formula II: 1, 3-dimethyl-2-nitrobenzene (II);
a compound of formula III: 2-nitro-1, 3-benzenedicarboxylic acid (iii);
a compound of formula IV: 2-nitro-1, 3-benzenedimethanol (iv);
a compound of formula V: 2-nitro-1, 3-benzenedichloroacetate (v);
a compound of formula VI: amino-containing silane (VI) in the structural formula, substituent X1、X2And X3Each independently selected from methoxy, ethoxy, acyloxy, methylEthyl, vinyl, isopropyl, phenyl, trifluoropropyl, Cl (CH)2)nOr NC (CH)2)m，n＝0～4，m＝1～4。
A compound of formula I: 2-nitro-1, 3-phenylene bridged silanes (I) in which the substituent X is1、X2And X3A compound of the same formula VI.
In the specification, the compound numbers are completely consistent with the structural formula numbers, have the same reference relationship, and are based on the structural formula of the compound.
Room temperature: means 25 ℃ plus or minus 5 ℃.
The technical scheme of the invention is as follows:
a photodegradable bridged silane having the structure shown in formula i:
in the structure of formula I, the substituent X1、X2And X3Each independently selected from methoxy, ethoxy, acyloxy, methyl, ethyl, vinyl, isopropyl, phenyl, trifluoropropyl, Cl (CH)2)nOr NC (CH)2)m，n＝0～4，m＝1～4。
According to the invention, the preparation method of the photodegradable bridged silane comprises the following steps:
(1) oxidizing a compound shown in a formula II by potassium permanganate in an alkaline aqueous solution to prepare a compound shown in a formula III;
(2) in a solvent A, reducing a compound shown in a formula III by a reducing agent to prepare a compound shown in a formula IV;
(3) preparing a compound shown in the formula V by acylation reaction of a compound shown in the formula IV and chloroacetyl chloride;
(4) nucleophilic substitution reaction is carried out on the compound of the formula V and the compound of the formula VI to prepare 2-nitro-1, 3-phenylene bridging silane (I);
in the structural formula of the compound of formula VI, substituent X1、X2And X3Each independently selected from methoxy, ethoxy, acyloxy, methyl, ethyl, vinyl, isopropyl, phenyl, trifluoropropyl, Cl (CH)2)nOr NC (CH)2)m，n＝0～4，m＝1～4。
According to the present invention, it is preferable that the oxidation reaction in the step (1) comprises: and (2) fully and uniformly mixing the compound shown in the formula II and an aqueous solution of alkali, heating, adding potassium permanganate in batches, cooling to room temperature after reaction, filtering the obtained reaction solution, slowly adding a hydrochloric acid solution into the filtrate, adjusting the pH of the solution to be 2-4, generating a large amount of white precipitate, and performing suction filtration to obtain a solid, namely the compound shown in the formula III.
According to the invention, preferably, the alkali in the step (1) is potassium hydroxide and sodium hydroxide, and the concentration is 0.1-1.0 mol/L; the molar ratio of the alkali to the compound of the formula II is 2-1: 1;
preferably, the heating temperature is 90-100 ℃.
According to the invention, the molar ratio of the compound of formula II to potassium permanganate in step (1) is preferably 1: 2-5, and more preferably 1: 3-4.
According to the invention, the reaction temperature in the step (1) is preferably 80-120 ℃, and further preferably 95-100 ℃; the reaction time is 24-72 h, and more preferably 30-48 h.
According to the present invention, it is preferred that the reaction step in step (2) is: dissolving a compound shown in a formula III in a solvent A, adding a reducing agent in batches under the condition of ice-water bath at 0-4 ℃, and then heating a reaction system to room temperature for reaction;
preferably, the solvent A is tetrahydrofuran, dichloromethane or trichloromethane; the ratio of the volume (L) of the solvent A to the mole (mol) of the compound shown in the formula III is 0.5-2: 1;
preferably, the reducing agent is borane tetrahydrofuran complex, and the concentration is 0.1-1.0 mol/L; the molar ratio of the reducing agent to the compound shown in the formula III is 3-5: 1;
preferably, the reaction time is 6-24 h, and further preferably 8-12 h.
According to the present invention, it is preferable that the post-treatment method of the reaction liquid obtained by the reduction reaction in the step (2) is as follows:
slowly adding a solvent B into a reactant obtained by the reduction reaction, removing the solvent after the solid is completely dissolved, dissolving the solvent in a solvent C again, sequentially washing an organic phase with a saturated sodium bicarbonate aqueous solution and deionized water for three times respectively, drying the organic phase by using a drying agent, performing suction filtration, evaporating the solvent, concentrating, and performing column chromatography purification to obtain a compound shown in the formula IV;
preferably, the solvent B is methanol; the molar ratio of the solvent B to the reducing agent is 1-2: 1;
preferably, the solvent C is ethyl acetate; the molar ratio of the solvent C to the compound of the formula III is 4-6: 1;
preferably, the drying agent is anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride or a molecular sieve;
preferably, in the column chromatography purification method, the stationary phase is silica gel, the eluent is a mixed solvent of n-hexane and ethyl acetate, and the volume ratio of n-hexane to ethyl acetate in the mixed solvent is 0.5-3: 1, and more preferably 1-2: 1.
According to the present invention, preferably, the step of preparing the compound of formula V by acylation of the compound of formula IV with chloroacetyl chloride in step (3) comprises: dissolving the compound of the formula III obtained in the step (2) in a solvent D, adding triethylamine, slowly dropwise adding chloroacetyl chloride in an ice water bath at 0-4 ℃, then heating a reaction system to room temperature for reaction, filtering to remove triethylamine salt after the reaction is finished, removing the solvent by rotary evaporation, washing with deionized water, drying with a drying agent, performing suction filtration, evaporating the solvent for concentration, and performing column chromatography purification to obtain a compound of the formula V;
preferably, the solvent D is n-hexane, cyclohexane, petroleum ether, tetrahydrofuran, toluene or benzene; the volume and molar ratio of the solvent D to the compound (mol) of the formula IV is 4-6: 1; the solvent D is subjected to anhydrous treatment;
preferably, the molar ratio of the compound shown in the formula IV to chloroacetyl chloride is 1: 2-4; the molar ratio of the chloracetyl chloride to the triethylamine is 1: 1;
preferably, the reaction time is 12-24 h.
Preferably, the drying agent is anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride or a molecular sieve;
preferably, in the column chromatography purification method, the stationary phase is silica gel, the eluent is a mixed solvent of n-hexane and ethyl acetate, and the volume ratio of n-hexane to ethyl acetate in the mixed solvent is 0.5-3: 1, and more preferably 1-2: 1.
According to the invention, the 2-nitro-1, 3-phenylene bridged silane (I) is preferably prepared by substitution of a compound of the formula V with a compound of the formula VI in step (4) in the following reaction steps: dissolving the compound of formula VI obtained in the step (3) in a solvent E, adding triethylamine, heating to a certain temperature under the nitrogen atmosphere, continuing to react for a while, removing triethylamine salt through suction filtration, and removing the solvent through rotary evaporation to obtain the compound of formula I.
According to the present invention, preferably, the solvent E in step (4) is dichloromethane, chloroform, tetrahydrofuran, acetonitrile or toluene, and further preferably, the solvent E is acetonitrile or tetrahydrofuran; the volume and molar ratio of the solvent E to the compound (mol) of the formula V is 4-6: 1; the solvent E is subjected to anhydrous treatment.
According to the invention, the molar ratio of the compound of formula IV to the compound of formula V in step (4) is preferably 1: 2.
According to the invention, the compound of formula V and triethylamine in step (4) are preferably present in a molar ratio of 1: 1.
According to the present invention, it is preferable that the conditions of the substitution reaction in step (4) are: in a nitrogen atmosphere, the reaction temperature is 50-80 ℃, and further preferably 60-70 ℃; the reaction time is 3-6 h, and preferably 4-5 h.
The reaction route of the invention is as follows:
technical characteristics and beneficial effects of the invention
1. The 2-nitro-1, 3-phenylene bridging silane is synthesized for the first time, can perform a photocleavage reaction under 365nm ultraviolet irradiation, and can realize complete full-optical degradation under the illumination condition.
2. The photodegradable bridged silane disclosed by the invention has the advantages of simple synthesis process, readily available raw materials, mild reaction conditions and strong operability.
3. The bridged silane disclosed by the invention has rapid photodegradability, can be used for designing and preparing photoresponsive functional materials, and has important application value.
Drawings
FIG. 1 is a schematic representation of 2-nitro-1, 3-phenylene bridged silane prepared in example 11H nuclear magnetic resonance spectrogram.
FIG. 2 shows experimental examples in which 2-nitro-1, 3-phenylene bridged silanes were irradiated with 365nm UV light (90 mW/cm)2) Absorbance values as a function of illumination time.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are conventional methods unless otherwise specified, and the reagents and materials described therein are commercially available without otherwise specified.
Silica gel used in the examples: 200-300 mesh, available from Qingdao ocean chemical Co., Ltd.
Example 1
A process for the preparation of a photodegradable bridged silane comprising the steps of:
(1) 1, 3-dimethyl-2-nitrobenzene (15.1g, 0.10mol), sodium hydroxide (6.4g, 0.16mol) and water (800mL) were mixed well, heated to 100 ℃ and potassium permanganate (63.5g, 0.40mol) was added in portions. After 48h of reaction, the reaction mixture was cooled to room temperature, filtered, the filtrate was collected, hydrochloric acid was added with stirring to pH 2, resulting in a large amount of white precipitate, and the resulting product, 2-nitro-1, 3-benzenedicarboxylic acid, was filtered off with suction (20.6g, 96% yield), as a white product.
(2) 2-Nitro-1, 3-benzenedicarboxylic acid (5.0g, 23.6mmol) was dissolved in tetrahydrofuran (45mL) and 1.0M BH was slowly added dropwise under ice-bath conditions3THF solution (118mL, 118mmol) was reacted for 72 h. Methanol (236mL) was slowly added and, after complete dissolution of the solid, the solvent was removed and redissolved in ethyl acetate (100mL) and the organic phase was washed three times with saturated aqueous sodium bicarbonate and deionized water, respectively, and dried over anhydrous magnesium sulfate. Performing suction filtration and solvent evaporation concentration, and then performing column chromatography purification to obtain a product, wherein the conditions of the column chromatography purification are as follows: the stationary phase is silica gel, and the eluent is a mixed solvent of n-hexane and ethyl acetate, wherein the volume ratio of the n-hexane to the ethyl acetate in the mixed solvent is 1:1, so that the white product 2-nitro-1, 3-benzenedimethanol (3.28g, the yield is 76%) is obtained.
(3) 2-Nitro-1, 3-benzenedimethanol (1.1g, 6mmol) was dissolved in tetrahydrofuran (25mL), triethylamine (2.4g,24mmol) was added, chloroacetyl chloride (2.7g, 24mmol) was slowly added dropwise under ice bath conditions, and then the reaction was warmed to room temperature and reacted at room temperature for 12 hours. And (2) removing triethylamine salt through suction filtration, removing a solvent through rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, performing suction filtration, concentrating an evaporated solvent, and purifying by using column chromatography to obtain a product, wherein the conditions of column chromatography purification are as follows: the stationary phase is silica gel, the eluent is a mixed solvent of n-hexane and ethyl acetate, and the volume ratio of n-hexane to ethyl acetate in the mixed solvent is 1:1, 2-nitro-1, 3-benzenedichloroacetate (1.53g, 74% yield) was obtained by distillation.
(4) 2-Nitro-1, 3-benzenedicloro ate (2.0g, 6mmol) was dissolved in anhydrous acetonitrile (25mL), triethylamine (1.2g, 12mmol) and α -aminopropyltriethoxysilane (2.6g, 12mmol) were added, and the reaction was continued for 6h by heating to 80 ℃ under a nitrogen atmosphere. The triethylamine salt was removed by suction filtration and the solvent removed by rotary evaporation to give 2-nitro-1, 3-phenylene bridged silane (3.9g, 92% yield).
FIG. 1 is a schematic representation of the 2-nitro-1, 3-phenylene bridged silane prepared in this example1H nuclear magnetic resonance spectrogram.1H NMR(400MHz,DMSO)δ7.77–7.67(m,3H),5.30–5.22(m,4H),3.75(q,J＝7.0Hz,12H),3.52–3.43(m,4H),2.73–2.61(m,4H),1.54(dd,J＝16.1,8.6Hz,4H),1.15(dd,J＝9.2,4.8Hz,18H),0.56(dd,J＝9.3,7.4Hz,4H).
The reaction scheme of this example is as follows:
example 2
A process for the preparation of a photodegradable bridged silane comprising the steps of:
(1) 1, 3-dimethyl-2-nitrobenzene (15.1g, 0.10mol), sodium hydroxide (6.4g, 0.16mol) and water (800mL) were mixed well, heated to 95 ℃ and potassium permanganate (63.5g, 0.40mol) was added in portions. After 42h of reaction, the temperature was reduced to room temperature, and the filtrate was collected, and hydrochloric acid was added with stirring to pH 2 to give a large amount of white precipitate, and the white product, 2-nitro-1, 3-benzenedicarboxylic acid (18.6g, 88% yield), was obtained by suction filtration.
(2) 2-Nitro-1, 3-benzenedicarboxylic acid (5.0g, 23.6mmol) was dissolved in tetrahydrofuran (60mL) and 1.0M BH was slowly added dropwise under ice-bath conditions3THF solution (94.4mL, 94.4mmol) was reacted for 10 h. Methanol (188mL) was slowly added, the solid was completely dissolved, the solvent was removed, the mixture was redissolved in ethyl acetate (100mL), and the organic phase was washed three times with saturated aqueous sodium bicarbonate solution and deionized water, respectively, and dried over anhydrous magnesium sulfate. Performing suction filtration and solvent evaporation concentration, and then performing column chromatography purification to obtain a product, wherein the conditions of the column chromatography purification are as follows: the stationary phase is silica gel, the eluent is a mixed solvent of n-hexane and ethyl acetate, and the mixed solvent isThe volume ratio of n-hexane to ethyl acetate in the reagent was 1:1, and a white product, 2-nitro-1, 3-benzenedimethanol (3.11g, 72% yield), was obtained.
(3) 2-Nitro-1, 3-benzenedimethanol (1.1g, 6mmol) was dissolved in tetrahydrofuran (50mL), triethylamine (1.8g,18mmol) was added, chloroacetyl chloride (2.0g, 18mmol) was slowly added dropwise under ice bath conditions, and then the reaction was warmed to room temperature and reacted at room temperature for 20 hours. And (2) removing triethylamine salt through suction filtration, removing a solvent through rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, performing suction filtration, concentrating an evaporated solvent, and purifying by using column chromatography to obtain a product, wherein the conditions of column chromatography purification are as follows: the stationary phase is silica gel, the eluent is a mixed solvent of n-hexane and ethyl acetate, the volume ratio of the n-hexane to the ethyl acetate in the mixed solvent is 1:1, and the 2-nitro-1, 3-dichlorobenzeneacetate (1.47g, the yield is 73%) is obtained by distillation.
(4) 2-Nitro-1, 3-benzenedicloro ate (2.0g, 6mmol) was dissolved in tetrahydrofuran (50mL), triethylamine (1.2g, 12mmol) and α -aminopropyltrimethoxysilane (2.2g, 12mmol) were added, and the reaction was continued for 6h by heating to 66 ℃ under a nitrogen atmosphere. The triethylamine salt was removed by suction filtration and the solvent removed by rotary evaporation to give 2-nitro-1, 3-phenylene bridged silane (2.7g, 91% yield).
The reaction scheme of this example is as follows:
example 3
A process for the preparation of a photodegradable bridged silane comprising the steps of:
(1) 1, 3-dimethyl-2-nitrobenzene (15.1g, 0.10mol), sodium hydroxide (6.4g, 0.16mol) and water (800mL) were mixed well, heated to 90 ℃ and potassium permanganate (63.5g, 0.40mol) was added in portions. After 42h of reaction, the temperature was reduced to room temperature, and the filtrate was collected, and hydrochloric acid was added with stirring to pH 2 to produce a large amount of white precipitate, and the white product, 2-nitro-1, 3-benzenedicarboxylic acid (18.1g, yield 86%), was obtained by suction filtration.
(2) 2-Nitro-1, 3-benzenedicarboxylic acid (2.5g,11.8mmol) was dissolved in tetrahydrofuran (60mL) and 1M BH was slowly added dropwise under ice-bath conditions3THF solution (47.2mL, 47.2mmol) was reacted for 8 h. Methanol (94.4mL) was slowly added and, after the solid was completely dissolved, the solvent was removed and redissolved in ethyl acetate (100mL) and the organic phase was washed three times with saturated aqueous sodium bicarbonate and deionized water, respectively, and dried over anhydrous magnesium sulfate. Performing suction filtration and solvent evaporation concentration, and then performing column chromatography purification to obtain a product, wherein the conditions of the column chromatography purification are as follows: the stationary phase is silica gel, and the eluent is a mixed solvent of n-hexane and ethyl acetate, wherein the volume ratio of the n-hexane to the ethyl acetate in the mixed solvent is 1:1, so that the white product 2-nitro-1, 3-benzenedimethanol (1.42g, the yield is 66%) is obtained.
(3) 2-Nitro-1, 3-benzenedimethanol (1.1g, 6mmol) was dissolved in tetrahydrofuran (50mL), triethylamine (1.8g,18mmol) was added, chloroacetyl chloride (2.0g, 18mmol) was slowly added dropwise under ice bath conditions, and then the reaction was warmed to room temperature and reacted at room temperature for 18 hours. And (2) removing triethylamine salt through suction filtration, removing a solvent through rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, performing suction filtration, concentrating an evaporated solvent, and purifying by using column chromatography to obtain a product, wherein the conditions of column chromatography purification are as follows: the stationary phase is silica gel, the eluent is a mixed solvent of n-hexane and ethyl acetate, the volume ratio of the n-hexane to the ethyl acetate in the mixed solvent is 1:1, and the 2-nitro-1, 3-phenyldichloroacetate (1.41g, the yield is 70%) is obtained by distillation.
(4) 2-Nitro-1, 3-benzenedicloro ate (2.0g, 6mmol) was dissolved in anhydrous acetonitrile (40mL), triethylamine (1.2g, 12mmol) and α -aminopropyltrimethylsilane (1.57g, 12mmol) were added, and the mixture was heated to 70 ℃ under a nitrogen atmosphere and the reaction was continued for 4 h. The triethylamine salt was removed by suction filtration and the solvent removed by rotary evaporation to give 2-nitro-1, 3-phenylene bridged silane (2.9g, 90% yield).
The reaction scheme of this example is as follows:
example 4
A process for the preparation of a photodegradable bridged silane comprising the steps of:
(1) 1, 3-dimethyl-2-nitrobenzene (15.1g, 0.10mol), sodium hydroxide (6.4g, 0.16mol) and water (800mL) were mixed well, heated to 95 ℃ and potassium permanganate (63.5g, 0.40mol) was added in portions. After 40h of reaction, the reaction mixture was cooled to room temperature, filtered, the filtrate was collected, hydrochloric acid was added with stirring to pH 2, resulting in a large amount of white precipitate, and the white product, 2-nitro-1, 3-benzenedicarboxylic acid (16.9g, yield 80%), was obtained by suction filtration.
(2) 2-Nitro-1, 3-benzenedicarboxylic acid (2.5g, 11.8mmol) was dissolved in tetrahydrofuran (60mL) and 1M BH was slowly added dropwise under ice-bath conditions3THF solution (35.4mL, 35.4mmol) was reacted for 8 h. Methanol (35.4mL) was slowly added and, after the solid was completely dissolved, the solvent was removed and redissolved in ethyl acetate (100mL), and the organic phase was washed three times with saturated aqueous sodium bicarbonate solution and deionized water, respectively, and dried over anhydrous magnesium sulfate. Performing suction filtration and solvent evaporation concentration, and then performing column chromatography purification to obtain a product, wherein the conditions of the column chromatography purification are as follows: the stationary phase is silica gel, and the eluent is a mixed solvent of n-hexane and ethyl acetate, wherein the volume ratio of the n-hexane to the ethyl acetate in the mixed solvent is 1:1, so that the white product 2-nitro-1, 3-benzenedimethanol (1.4g, yield 65%) is obtained.
(3) 2-Nitro-1, 3-benzenedimethanol (2.2g, 12mmol) was dissolved in tetrahydrofuran (50mL), triethylamine (2.4g,24mmol) was added, chloroacetyl chloride (2.7g, 24mmol) was slowly added dropwise under ice bath conditions, and then the reaction was warmed to room temperature and reacted at room temperature for 18 hours. And (2) removing triethylamine salt through suction filtration, removing a solvent through rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, performing suction filtration, concentrating an evaporated solvent, and purifying by using column chromatography to obtain a product, wherein the conditions of column chromatography purification are as follows: the stationary phase is silica gel, the eluent is a mixed solvent of n-hexane and ethyl acetate, the volume ratio of the n-hexane to the ethyl acetate in the mixed solvent is 1:1, and the 2-nitro-1, 3-phenyldichloroacetate (2.62g, the yield is 65%) is obtained by distillation.
(4) 2-Nitro-1, 3-benzenedicloro ate (2.0g, 6mmol) was dissolved in anhydrous acetonitrile (40mL), triethylamine (1.2g, 12mmol) and α -aminopropyltriethylsilane (2.08g, 12mmol) were added, and the reaction was continued for 3h by heating to 60 ℃ under a nitrogen atmosphere. The triethylamine salt was removed by suction filtration and the solvent removed by rotary evaporation to give 2-nitro-1, 3-phenylene bridged silane (2.8g, 87% yield).
The reaction scheme of this example is as follows:
example 5
A process for the preparation of a photodegradable bridged silane comprising the steps of:
(1) 1, 3-dimethyl-2-nitrobenzene (15.1g, 0.10mol), sodium hydroxide (6.4g, 0.16mol) and water (800mL) were mixed well, heated to 90 ℃ and potassium permanganate (63.5g, 0.40mol) was added in portions. After 36h of reaction, the temperature was reduced to room temperature, and the filtrate was collected, and hydrochloric acid was added with stirring to pH 2 to give a large amount of white precipitate, and the white product, 2-nitro-1, 3-benzenedicarboxylic acid (16.5g, yield 78%), was obtained by suction filtration.
(2) 2-Nitro-1, 3-benzenedicarboxylic acid (6.3g, 29.5mmol) was dissolved in tetrahydrofuran (60mL) and 1M BH was slowly added dropwise under ice-bath conditions3THF solution (88.5mL, 88.5mmol) was reacted for 6 h. Methanol (88.5mL) was slowly added and, after the solid was completely dissolved, the solvent was removed and redissolved in ethyl acetate (100mL), and the organic phase was washed three times with saturated aqueous sodium bicarbonate solution and deionized water, respectively, and dried over anhydrous magnesium sulfate. Performing suction filtration and solvent evaporation concentration, and then performing column chromatography purification to obtain a product, wherein the conditions of the column chromatography purification are as follows: the stationary phase is silica gel, and the eluent is a mixed solvent of n-hexane and ethyl acetate, wherein the volume ratio of the n-hexane to the ethyl acetate in the mixed solvent is 1:1, so that the white product 2-nitro-1, 3-benzenedimethanol (3.4g, yield 63%) is obtained.
(3) 2-Nitro-1, 3-benzenedimethanol (2.2g, 12mmol) was dissolved in tetrahydrofuran (50mL), triethylamine (2.4g,24mmol) was added, chloroacetyl chloride (2.7g, 24mmol) was slowly added dropwise under ice bath conditions, and then the reaction was warmed to room temperature and reacted at room temperature for 12 hours. And (2) removing triethylamine salt through suction filtration, removing a solvent through rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, performing suction filtration, concentrating an evaporated solvent, and purifying by using column chromatography to obtain a product, wherein the conditions of column chromatography purification are as follows: the stationary phase is silica gel, the eluent is a mixed solvent of n-hexane and ethyl acetate, the volume ratio of the n-hexane to the ethyl acetate in the mixed solvent is 1:1, and the 2-nitro-1, 3-phenyldichloroacetate (2.54g, the yield is 63%) is obtained by distillation.
(4) 2-Nitro-1, 3-benzenedicloro ate (2.0g, 6mmol) was dissolved in anhydrous acetonitrile (40mL), triethylamine (1.2g, 12mmol) and α -aminopropyldimethylethylsilane (2.6g, 12mmol) were added, and the mixture was heated to 50 ℃ under a nitrogen atmosphere and the reaction was continued for 2 h. The triethylamine salt was removed by suction filtration and the solvent removed by rotary evaporation to give 2-nitro-1, 3-phenylene bridged silane (2.6g, 80% yield).
The reaction scheme of this example is as follows:
comparative example
A process for the preparation of a photodegradable bridged silane comprising the steps of:
(1) 1, 3-dimethyl-2-nitrobenzene (15.1g, 0.10mol), sodium hydroxide (6.4g, 0.16mol) and water (800mL) were mixed well, heated to 80 ℃ and potassium permanganate (63.5g, 0.40mol) was added in portions. After 12h of reaction, the reaction mixture was cooled to room temperature, filtered, the filtrate was collected, hydrochloric acid was added with stirring to pH 2, resulting in a large amount of white precipitate, and the white product, 2-nitro-1, 3-benzenedicarboxylic acid (11.8g, 56% yield), was obtained by suction filtration.
In this step, the oxidation reaction of 1, 3-dimethyl-2-nitrobenzene is insufficient due to the low reaction temperature, resulting in a decrease in the yield of 2-nitro-1, 3-benzenedicarboxylic acid.
(2) 2-Nitro-1, 3-benzenedicarboxylic acid (6.3g, 29.5mmol) was dissolved in tetrahydrofuran (60mL) and 1M BH was slowly added dropwise under ice-bath conditions3THF solution (59.0mL, 59.0mmol) was reacted for 4 h. Slowly adding methanol (59.0mL), dissolving the solid completely, removing solvent, dissolving in ethyl acetate (100mL), and sequentially saturating the organic phaseAnd an aqueous sodium bicarbonate solution and deionized water were each washed three times and dried over anhydrous magnesium sulfate. Performing suction filtration and solvent evaporation concentration, and then performing column chromatography purification to obtain a product, wherein the conditions of the column chromatography purification are as follows: the stationary phase is silica gel, and the eluent is a mixed solvent of n-hexane and ethyl acetate, wherein the volume ratio of the n-hexane to the ethyl acetate in the mixed solvent is 1:1, so that the white product 2-nitro-1, 3-benzenedimethanol (2.4g, yield 45%) is obtained.
In the step, the reaction time is short, so that the 2-nitro-1, 3-phthalic acid does not fully participate in the reduction reaction, and the yield of the reduction product 2-nitro-1, 3-benzenedimethanol is low.
(3) 2-Nitro-1, 3-benzenedimethanol (2.2g, 12mmol) was dissolved in tetrahydrofuran (50mL), triethylamine (1.8g,18mmol) was added, chloroacetyl chloride (2.0g, 18mmol) was slowly added dropwise under ice bath conditions, and then the reaction was warmed to room temperature and reacted at room temperature for 12 hours. And (2) removing triethylamine salt through suction filtration, removing a solvent through rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, performing suction filtration, concentrating an evaporated solvent, and purifying by using column chromatography to obtain a product, wherein the conditions of column chromatography purification are as follows: the stationary phase is silica gel, the eluent is a mixed solvent of n-hexane and ethyl acetate, the volume ratio of the n-hexane to the ethyl acetate in the mixed solvent is 1:1, and the 2-nitro-1, 3-phenyldichloroacetate (2.18g, the yield is 54%) is obtained by distillation.
In the step, because the theoretical molar ratio of the reaction of the raw materials of the 2-nitro-1, 3-benzenedimethanol and the chloracetyl chloride is 1:2, the yield of the final product is reduced when the charging molar ratio of the chloracetyl chloride is less than the ratio.
(4) 2-Nitro-1, 3-benzenedicloro ate (2.0g, 6mmol) was dissolved in anhydrous acetonitrile (40mL), triethylamine (1.2g, 12mmol) and α -aminopropyltriethoxysilane (2.6g, 12mmol) were added, and the reaction was continued for 2h by heating to 40 ℃ under a nitrogen atmosphere. The triethylamine salt was removed by suction filtration and the solvent removed by rotary evaporation to give 2-nitro-1, 3-phenylene bridged silane (2.1g, 66% yield).
In the step, since the substitution reaction rate of 2-nitro-1, 3-benzene di-chlorate and alpha-aminopropyl triethoxysilane is slowed down when the reaction temperature is low, the reaction cannot be fully completed within 2 hours of reaction time, resulting in low final yield.
Test examples
Photoresponsiveness test of 2-nitro-1, 3-phenylene-bridged silanes
Dissolving the prepared 2-nitro-1, 3-phenylene bridging silane in tetrahydrofuran to obtain a tetrahydrofuran solution of the 2-nitro-1, 3-phenylene bridging silane with the concentration of 0.1g/L, and carrying out a photoresponsiveness test on the obtained tetrahydrofuran solution under the irradiation of ultraviolet light with the wavelength of 365 nm. The obtained 2-nitro-1, 3-phenylene bridging silane generates a photocleavage reaction under the irradiation of ultraviolet light, and the specific photocleavage reaction process is as follows:
the specific experimental steps are as follows:
the 2-nitro-1, 3-phenylene-bridged silane prepared in example 1 was dissolved in tetrahydrofuran to give a solution of 2-nitro-1, 3-phenylene-bridged silane at a concentration of 0.1g/L in tetrahydrofuran, and the solution of 2-nitro-1, 3-phenylene-bridged silane in tetrahydrofuran was placed under a light source at 365nm (90 mW/cm)2) Irradiating for 0min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, and 50min, respectively, sampling, and measuring its absorbance value by ultraviolet-visible spectrophotometry. The results are shown in FIG. 2.
As can be seen from FIG. 2, the characteristic absorption peak of 2-nitro-1, 3-phenylene bridged silane at 300nm appeared with increasing light irradiation time and gradually increased due to the generation of nitrosobenzyl compound after light irradiation. The phenomenon that the ultraviolet absorption spectrum changes along with the change of illumination time proves that the 2-nitro-1, 3-phenylene bridging silane generates photochemical reaction under 365nm ultraviolet light and has photodegradation behavior.
Claims (9)
1. A process for preparing a bridged silane having the structure shown in formula I:
Ⅰ，
in the structure of formula I, the substituent X1、X2And X3Each independently selected from methoxy, ethoxy, acyloxy, methyl, ethyl, vinyl, isopropyl, phenyl, trifluoropropyl, Cl (CH)2)nOr NC (CH)2)m，n=0~4，m=1~4；
The method comprises the following steps:
(1) fully and uniformly mixing a compound shown in a formula II and an aqueous solution of alkali, heating, adding potassium permanganate in batches, cooling to room temperature after reaction, filtering the obtained reaction solution, slowly adding a hydrochloric acid solution into the filtrate, adjusting the pH of the solution to be 2-4, generating a large amount of white precipitate, and performing suction filtration to obtain a solid, namely a compound shown in a formula III;
Ⅱ Ⅲ；
(2) dissolving a compound shown in the formula III in a solvent A, adding a reducing agent in batches under the condition of ice-water bath at 0-4 ℃, and then heating a reaction system to room temperature for reaction for 6-12 hours to prepare a compound shown in the formula IV;
Ⅳ；
(3) dissolving the compound of the formula IV obtained in the step (2) in a solvent D, adding triethylamine, slowly dropwise adding chloroacetyl chloride in an ice water bath at 0-4 ℃, then heating a reaction system to room temperature for reaction, filtering to remove triethylamine salt after the reaction is finished, removing the solvent by rotary evaporation, washing with deionized water, drying with a drying agent, performing suction filtration, evaporating the solvent for concentration, and performing column chromatography purification to obtain a compound of the formula V;
Ⅴ；
(4) dissolving the compound of the formula V obtained in the step (3) in a solvent E, adding triethylamine and a compound of the formula VI, heating to 50-80 ℃ in a nitrogen atmosphere, continuing to react for 3-6 h, performing suction filtration to remove triethylamine salt, and performing rotary evaporation to remove the solvent to obtain a compound of the formula I;
in the structural formula of the compound of formula VI, substituent X1、X2And X3Each independently selected from methoxy, ethoxy, acyloxy, methyl, ethyl, vinyl, isopropyl, phenyl, trifluoropropyl, Cl (CH)2)nOr NC (CH)2)m，n=0~4，m=1~4；
Ⅵ 。
2. The process for the preparation of the bridged silane of claim 1, wherein the reaction in step (1) is carried out in one or more of the following conditions:
A. the alkali is potassium hydroxide and sodium hydroxide, and the concentration is 0.1-1.0 mol/L; the molar ratio of the alkali to the compound of the formula II is 2-1: 1;
B. heating to 90-100 deg.C;
C. the molar ratio of the compound shown in the formula II to the potassium permanganate is 1: 2-5;
D. the reaction temperature is 80-120 ℃, and the reaction time is 24-72 h.
3. The preparation method of the bridged silane as claimed in claim 1, wherein the molar ratio of the compound of formula II to potassium permanganate in step (1) is 1: 3-4, the reaction temperature is 95-100 ℃, and the reaction time is 30-48 h.
4. The process for the preparation of the bridged silane of claim 1, wherein the reaction in step (2) is carried out in one or more of the following conditions:
A. the solvent A is tetrahydrofuran, dichloromethane or trichloromethane; the volume of the solvent A and the molar ratio of the compound in the formula III are 0.5-2L: 1 mol;
B. the reducing agent is a borane tetrahydrofuran complex, and the concentration is 0.1-1.0 mol/L; the molar ratio of the reducing agent to the compound shown in the formula III is 3-5: 1;
C. carrying out post-treatment on the reaction liquid obtained in the step (2), wherein the method comprises the following steps:
and (3) slowly adding a solvent B into the reactant obtained by the reaction, removing the solvent after the solid is completely dissolved, dissolving the solvent in a solvent C again, sequentially washing the organic phase with a saturated sodium bicarbonate aqueous solution and deionized water for three times respectively, drying the organic phase by using a drying agent, performing suction filtration, evaporating the solvent, concentrating, and performing column chromatography purification to obtain the compound shown in the formula IV.
5. The preparation method of the bridged silane, according to claim 4, characterized in that in the post-treatment process of the reaction solution obtained in the step (2), the solvent B is methanol, the molar ratio of the solvent B to the reducing agent is 1-2: 1, the solvent C is ethyl acetate, the molar ratio of the solvent C to the compound of the formula III is 4-6: 1, the drying agent is anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride or a molecular sieve, in the column chromatography purification method, the stationary phase is silica gel, the eluent is a mixed solvent of n-hexane and ethyl acetate, and the volume ratio of n-hexane to ethyl acetate in the mixed solvent is 0.5-3: 1.
6. The process for the preparation of the bridged silane of claim 1, wherein the reaction in step (3) is carried out in one or more of the following conditions:
A. the solvent D is n-hexane, cyclohexane, petroleum ether, tetrahydrofuran, toluene or benzene; the volume and molar ratio of the solvent D to the compound of the formula IV is 4-6L: 1 mol;
B. the molar ratio of the compound shown in the formula IV to chloroacetyl chloride is 1: 2-4; the molar ratio of the chloracetyl chloride to the triethylamine is 1: 1;
C. the reaction time is 12-24 h;
D. the drying agent is anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride or a molecular sieve;
E. in the column chromatography purification method, a stationary phase is silica gel, an eluant is a mixed solvent of n-hexane and ethyl acetate, and the volume ratio of the n-hexane to the ethyl acetate in the mixed solvent is 0.5-3: 1.
7. The preparation method of the bridged silane, according to claim 1, characterized in that in the column chromatography purification method of step (3), the stationary phase is silica gel, the eluent is a mixed solvent of n-hexane and ethyl acetate, and the volume ratio of n-hexane to ethyl acetate in the mixed solvent is 1-2: 1.
8. The process for the preparation of the bridged silane of claim 1, wherein the reaction in step (4) is carried out in one or more of the following conditions:
A. the solvent E is dichloromethane, trichloromethane, tetrahydrofuran, acetonitrile or toluene, and the volume and molar ratio of the solvent E to the compound of the formula V is 4-6L: 1 mol;
B. the molar ratio of the compound shown in the formula VI to the compound shown in the formula V is 1: 2;
C. the molar ratio of the compound shown in the formula V to triethylamine is 1: 1.
9. The method for preparing bridged silane according to claim 1, wherein the solvent E in step (4) is acetonitrile or tetrahydrofuran, and the reaction temperature is 60-70 ℃ and the reaction time is 4-5 h under nitrogen atmosphere.
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