Preparation of 3-[(3, 3-dimethoxy-2, 7-dioxa-3-silanone-9-yl) oxy] propionitrile

Abstract

The invention discloses a preparation method of 3-[(3, 3-dimethoxy-2, 7-dioxa-3-silane-9-yl) oxy] propionitrile, which comprises the following steps: 1, adding 3-[(2-hydroxyethyl) oxy] propionitrile and a first organic solvent, cooling to 0-5 DEG C, adding sodium hydride in batches under the protection of nitrogen, heating to room temperature, stirring for 0.5-1 hour, controlling the temperature not to exceed 25 DEG C, dropwise adding bromopropene, reacting for 1-2 hours, cooling to 0-5 DEG C, cooling to 0-5 DEG C, cooling to 0-5 DEG C, cooling to 0-5 DEG C, cooling to 0-5 DEG C, adding sodium hydride in batches under the protection of nitrogen, heating to room temperature, stirring for 0.5-1 hour, and cooling to 0-5 DEG C to obtain a second organic solvent; after dropwise adding, filtering to remove insoluble substances, carrying out rotary evaporation to remove the solvent, and rectifying a crude product to obtain 3-{[2-(prop-2-alkenyl oxy) ethyl] oxy} propionitrile; and 2, adding 3-{[2-(propyl-2-alkenyl oxy) ethyl] oxy} propionitrile and a hydrosilylation catalyst, heating to 130-150 DEG C, dropwise adding trichlorosilane, carrying out a thermal reaction for 10-15 h after dropwise adding, dropwise adding a methanol solution dissolved with an acid-binding agent while controlling the temperature to be 10 DEG C or below, and carrying out molecular rectification treatment on a crude product after the reaction is completed to obtain a finished product. The method has the advantages that the synthesis method is simple and easy to implement, the post-treatment method is easy to operate, and the product purity is high.

Description

Technical Field

[0001] The present invention relates to the technical field of compound synthesis. Background Art

[0002] Organic synthesis plays an important role in various fields such as medicine and new materials. Organic synthesis has become one of the mainstream of contemporary chemical research. Designing and synthesizing compounds with expected excellent properties is the development trend in the field of chemistry today.

[0003] The applicant has been long-term committed to the related research and development of lithium battery electrolytes, lithium battery electrolyte additives, etc., especially constantly exploring compounds that may improve the performance of lithium batteries. Summary of the Invention

[0004] The technical problem to be solved by the present invention is: to provide a preparation method of 3-[(3,3-dimethoxy-2,7-dioxo-3-silanonan-9-yl)oxy]propanenitrile, which has simple operation and greatly improves the product purity.

[0005] To solve the above problems, the technical solution adopted by the present invention is: the preparation of 3-[(3,3-dimethoxy-2,7-dioxo-3-silanonan-9-yl)oxy]propanenitrile, including the following steps: First, add 3-[(2-hydroxyethyl)oxy]propanenitrile and a first organic solvent to a reaction vessel, cool down to 0-5°C, add sodium hydride in batches under nitrogen protection, then raise the temperature to room temperature and stir for 0.5h-1h, control the temperature not exceeding 25°C and dropwise add allyl bromide, after dropping, filter to remove insoluble substances, rotary evaporate to remove the solvent, and rectify the crude product to obtain 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile; Second, add 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile and a hydrosilylation catalyst to a reaction vessel, raise the temperature to 130-150°C, dropwise add trichlorosilane, after dropping, keep the temperature for reaction for 10-15h, then dropwise add a methanol solution dissolved with an acid-binding agent at a temperature controlled below 10°C, and after the reaction is completed, perform molecular rectification treatment on the crude product to obtain the finished product.

[0006] Further, in the preparation of the aforementioned 3-[(3,3-dimethoxy-2,7-dioxo-3-silanonan-9-yl)oxy]propanenitrile, in the first step, the molar ratio of 3-[(2-hydroxyethyl)oxy]propanenitrile, sodium hydride, and allyl bromide is 1:1.05-1.1:1.02-1.05.

[0007] Further, in the preparation of the aforementioned 3-[(3,3-dimethoxy-2,7-dioxo-3-silanonan-9-yl)oxy]propanenitrile, in the first step, the sodium hydride used is a sodium hydride / mineral oil mixture, in which the mass fraction of sodium hydride is 60%. The sodium hydride / mineral oil mixture is obtained by purchase.

[0008] Furthermore, for the preparation of the aforementioned 3-[(3,3-dimethoxy-2,7-dioxa-3-silanonan-9-yl)oxy]propanenitrile, in the first step, the first organic solvent is one or more of tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylformamide; the usage amount of the first organic solvent is 8 to 10 times the weight of 3-[(2-hydroxyethyl)oxy]propanenitrile.

[0009] Furthermore, for the preparation of the aforementioned 3-[(3,3-dimethoxy-2,7-dioxa-3-silanonan-9-yl)oxy]propanenitrile, in the second step, the hydrosilylation catalyst is a Pt-containing catalyst.

[0010] Furthermore, for the preparation of the aforementioned 3-[(3,3-dimethoxy-2,7-dioxa-3-silanonan-9-yl)oxy]propanenitrile, the Pt-containing catalyst is a chloroplatinic acid catalyst, and the effective Pt is 80 to 100 ppm after the addition of the catalyst.

[0011] Furthermore, for the preparation of the aforementioned 3-[(3,3-dimethoxy-2,7-dioxa-3-silanonan-9-yl)oxy]propanenitrile, in the second step, the acid-binding agent is selected from one of triethylamine, pyridine, and imidazole; the molar ratio of the acid-binding agent: methanol: 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile is 3.06 to 3.15: 3.06 to 3.15:1.

[0012] Furthermore, for the preparation of the aforementioned 3-[(3,3-dimethoxy-2,7-dioxa-3-silanonan-9-yl)oxy]propanenitrile, the molar ratio of trichlorosilane to 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile is 1.02 to 1.05:1.

[0013] The advantages of the present invention are: its synthesis method is simple and easy to implement, the post-treatment method is easy to operate, and the product purity is high. Specific Embodiments

[0014] The present invention will be further described in detail below through specific examples.

[0015] The reaction is shown as follows: ; ; .

[0016] Example 1: 11.5 g of 3-[(2-hydroxyethyl)oxy]propanenitrile and 100 g of tetrahydrofuran were added to a three-necked flask equipped with mechanical stirring and a thermometer. The temperature was lowered to 0 °C, and 4.4 g of sodium hydride / mineral oil mixture (sodium hydride mass fraction 60%) was added in 5 batches under nitrogen protection. Then the temperature was raised to room temperature and stirred for 0.5 h. While controlling the temperature not exceeding 25 °C, 12.6 g of allyl bromide was added dropwise. After the addition was completed, the insoluble matter was removed by filtration, the solvent was removed by rotary evaporation, and 13.9 g of 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile with a purity of 97% was obtained by rectifying the crude product.

[0017] 13.9 g of 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile and 0.1 g of chloroplatinic acid catalyst (effective Pt: 80 ppm) were added to a three-necked flask equipped with mechanical stirring, a dropping funnel, and a thermometer. The temperature was raised to 150 °C, and 12.4 g of trichlorosilane was slowly added dropwise. After the addition was completed, the reaction was kept at a constant temperature for 10 h. Then, while controlling the temperature below 10 °C, a triethylamine / methanol solution (8.8 g of methanol and 27.8 g of triethylamine) was added dropwise. After the reaction was completed, the crude product was treated by molecular rectification to obtain 15 g of the finished product with a purity of 98.6% and an overall yield of 57%.

[0018] Example 2: 23 g of 3-[(2-hydroxyethyl)oxy]propanenitrile and 184 g of N,N-dimethylformamide were added to a three-necked flask equipped with mechanical stirring and a thermometer. The temperature was lowered to 0 °C, and 8.4 g of sodium hydride / mineral oil mixture (sodium hydride mass fraction 60%) was added in 6 batches under nitrogen protection. Then the temperature was raised to room temperature and stirred for 0.5 h. While controlling the temperature not exceeding 25 °C, 24.7 g of allyl bromide was added dropwise. After the addition was completed, the insoluble matter was removed by filtration, the solvent was removed by rotary evaporation, and 28 g of 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile with a purity of 96.2% was obtained by rectifying the crude product.

[0019] 28 g of 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile and 0.2 g of chloroplatinic acid catalyst (effective Pt: 100 ppm) were added to a three-necked flask equipped with mechanical stirring, a dropping funnel, and a thermometer. The temperature was raised to 150 °C, and 25.7 g of trichlorosilane was slowly added dropwise. After the addition was completed, the reaction was kept at a constant temperature for 10 h. Then, while controlling the temperature below 10 °C, a triethylamine / methanol solution (18.2 g of methanol and 57.4 g of triethylamine) was added dropwise. After the reaction was completed, the crude product was treated by molecular rectification to obtain 30.2 g of the finished product with a purity of 98.9% and an overall yield of 57.4%.

[0020] Example 3: 115 g of 3-[(2-hydroxyethyl)oxy]propanenitrile and 1150 g of dimethyl sulfoxide were added to a three-necked flask equipped with a mechanical stirrer and a thermometer. The temperature was lowered to 0 °C, and 44 g of a sodium hydride / mineral oil mixture (sodium hydride mass fraction 60%) was added in 5 batches under nitrogen protection. Then the temperature was raised to room temperature and stirred for 0.5 h. While controlling the temperature not exceeding 25 °C, 126 g of allyl bromide was added dropwise. After the addition was completed, the insoluble matter was removed by filtration, the solvent was removed by rotary evaporation, and 139 g of 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile with a purity of 97% was obtained by fractional distillation of the crude product.

[0021] 139 g of 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile and 1 g of chloroplatinic acid catalyst (effective Pt: 90 ppm) were added to a three-necked flask equipped with a mechanical stirrer, a dropping funnel and a thermometer. The temperature was raised to 150 °C, and 124 g of trichlorosilane was slowly added dropwise. After the addition was completed, the reaction was kept at the same temperature for 10 h. Then, while controlling the temperature below 10 °C, an imidazole / methanol solution (87.8 g of methanol and 186.6 g of imidazole) was added dropwise. After the reaction was completed, the crude product was treated by molecular distillation to obtain 138 g of the finished product with a purity of 98.4% and a total yield of 52.5%.

[0022] Example 4: 230 g of 3-[(2-hydroxyethyl)oxy]propanenitrile and 2070 g of tetrahydrofuran were added to a three-necked flask equipped with a mechanical stirrer and a thermometer. The temperature was lowered to 0 °C, and 88 g of a sodium hydride / mineral oil mixture (sodium hydride mass fraction 60%) was added in 5 batches under nitrogen protection. Then the temperature was raised to room temperature and stirred for 0.5 h. While controlling the temperature not exceeding 25 °C, 249.3 g of allyl bromide was added dropwise. After the addition was completed, the insoluble matter was removed by filtration, the solvent was removed by rotary evaporation, and 270 g of 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile with a purity of 97% was obtained by fractional distillation of the crude product.

[0023] 270 g of 3-{[2-(prop-2-enyloxy)ethyl]oxy}propanenitrile and 1 g of chloroplatinic acid catalyst (effective Pt: 80 ppm) were added to a three-necked flask equipped with a mechanical stirrer, a dropping funnel and a thermometer. The temperature was raised to 150 °C, and 240.7 g of trichlorosilane was slowly added dropwise. After the addition was completed, the reaction was kept at the same temperature for 10 h. Then, while controlling the temperature below 10 °C, an imidazole / methanol solution (170.6 g of methanol and 362.5 g of imidazole) was added dropwise. After the reaction was completed, the crude product was treated by molecular distillation to obtain 270.4 g of the finished product with a purity of 98.1% and a total yield of 51.4%.

[0024] Example 5: Add 11.5 g of 3-[(2-hydroxyethyl)oxy]propionitrile and 92 g of dimethyl sulfoxide into a three-necked flask equipped with mechanical stirring and a thermometer. Cool the mixture to 0 °C, and add 4.2 g of sodium hydride / mineral oil mixture (mass fraction of sodium hydride: 60%) in 5 batches under nitrogen protection. Then, raise the temperature to room temperature and stir for 0.5 h. While controlling the temperature not exceeding 25 °C, dropwise add 12.7 g of allyl bromide. After the addition is complete, filter to remove the insoluble matter, rotary evaporate to remove the solvent, and subject the crude product to rectification to obtain 13.8 g of 3-{[2-(prop-2-enyloxy)ethyl]oxy}propionitrile with a purity of 95%.

[0025] Add 13.8 g of 3-{[2-(prop-2-enyloxy)ethyl]oxy}propionitrile and 0.1 g of chloroplatinic acid catalyst (effective Pt: 100 ppm) into a three-necked flask equipped with mechanical stirring, a dropping funnel, and a thermometer. Raise the temperature to 150 °C, and dropwise add 12.4 g of trichlorosilane. After the addition is complete, keep the temperature for reaction for 10 h. Then, while controlling the temperature below 10 °C, dropwise add an imidazole / methanol solution (9.0 g of methanol and 19.1 g of imidazole). After the reaction is completed, subject the crude product to molecular rectification to obtain 14 g of the finished product with a purity of 98.5% and an overall yield of 53.2%.

[0026] It can be obtained from the above examples that the preparation method of 3-[(3,3-dimethoxy-2,7-dioxo-3-silanon-9-yl)oxy]propionitrile according to the present invention has a simple and feasible synthesis method, an easy-to-operate post-treatment method, and a high product purity.

Claims

1. Preparation of 3-[(3,3-dimethoxy-2,7-dioxa-3-silanononan-9-yl)oxy]propanenitrile, comprising the following steps:

1. Add 3-[(2-hydroxyethyl)oxy]propionitrile and a first organic solvent to a reaction vessel, cool down to 0-5 °C, add sodium hydride in batches under nitrogen protection, then raise the temperature to room temperature and stir for 0.5-1 h, control the temperature not exceeding 25 °C and dropwise add allyl bromide. After the addition is complete, filter to remove insoluble substances, rotary evaporate to remove the solvent, and rectify the crude product to obtain 3-{[2-(prop-2-enyloxy)ethyl]oxy}propionitrile; 2. Add 3-{[2-(prop-2-enyloxy)ethyl]oxy}propionitrile and a hydrosilylation catalyst to a reaction vessel, raise the temperature to 130-150 °C, dropwise add trichlorosilane. After the addition is complete, keep the temperature for reaction for 10-15 h, then dropwise add a methanol solution containing an acid-binding agent while controlling the temperature below 10 °C. After the reaction is completed, subject the crude product to molecular rectification to obtain the finished product.

2. Preparation of 3-[(3,3-dimethoxy-2,7-dioxo-3-silanononan-9-yl)oxy]propanenitrile according to claim 1, characterized in that: In the first step, the molar ratio of 3-[(2-hydroxyethyl)oxy]propionitrile, sodium hydride, and allyl bromide is 1:1.05-1.1:1.02-1.

05.

3. Preparation of 3-[(3,3-dimethoxy-2,7-dioxo-3-silanonan-9-yl)oxy]propanenitrile according to claim 1, characterized in that: In the first step, the sodium hydride used is a sodium hydride / mineral oil mixture, in which the mass fraction of sodium hydride is 60%.

4. Preparation of 3-[(3,3-dimethoxy-2,7-dioxo-3-silanon-9-yl)oxy]propionitrile according to claim 1, characterized in that: In the first step, the first organic solvent is one or more of tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide; the usage amount of the first organic solvent is 8-10 times the weight of 3-[(2-hydroxyethyl)oxy]propionitrile.

5. Preparation of 3-[(3,3-dimethoxy-2,7-dioxa-3-silanononan-9-yl)oxy]propanenitrile according to claim 1, characterized in that: In the second step, the hydrosilylation catalyst is a Pt-containing catalyst.

6. Preparation of 3-[(3,3-dimethoxy-2,7-dioxo-3-silanonan-9-yl)oxy]propionitrile according to claim 5, characterized in that: The Pt-containing catalyst is a chloroplatinic acid catalyst, and the effective Pt is 80-100 ppm after the catalyst is added.

7. Preparation of 3-[(3,3-dimethoxy-2,7-dioxa-3-silanononan-9-yl)oxy]propanenitrile according to claim 4, characterized in that: In the second step, the acid-binding agent is selected from one of triethylamine, pyridine, and imidazole; the molar ratio of the acid-binding agent: methanol: 3-{[2-(prop-2-enyloxy)ethyl]oxy}propionitrile is 3.06-3.15: 3.06-3.15:

1.

8. Preparation of 3-[(3,3-dimethoxy-2,7-dioxa-3-silanonan-9-yl)oxy]propionitrile according to claim 1, characterized in that: The molar ratio of trichlorosilane to 3-{[2-(prop-2-enyloxy)ethyl]oxy}propionitrile is 1.02-1.05:1.