阅读说明：本技术 一种二恶唑酮类化合物的合成方法 (Synthesis method of dioxazalone compounds ) 是由 彭鹏鹏 刘鹏 杨世雄 田丽霞 王军 张茜 于 2020-06-02 设计创作，主要内容包括：本发明属于二恶唑酮类合成的技术领域,提出了一种二恶唑酮类化合物的合成方法,包括：将有机溶剂和咪唑混合,通入光气,蒸馏,除去有机溶剂,得到剩余混合物,过滤剩余混合物,0℃搅拌30-50min,过滤出沉淀,干燥结晶得到N,N'-羰基二咪唑；以乙酰氧肟酸或苯甲羟肟酸为原料,用溶剂溶解,加入步骤A制备的N,N'-羰基二咪唑,边加入边搅拌,在25-35℃反应35-50min,反应结束后萃取,干燥,减压除去溶剂,重结晶得到产物；以乙酰氧肟酸为原料,合成的产物为3-甲基-1,2,4-二恶唑-5-酮；以苯甲羟肟酸为原料,合成的产物为3-苯基-1,2,4-二恶唑-5-酮。通过上述技术方案,解决了现有技术中二恶唑酮类化合物合成方法副产物多,收率低的问题。(The invention belongs to the technical field of synthesis of dioxazalones, and provides a synthesis method of a dioxazalone compound, which comprises the following steps: mixing an organic solvent and imidazole, introducing phosgene, distilling, removing the organic solvent to obtain a residual mixture, filtering the residual mixture, stirring for 30-50min at 0 ℃, filtering out a precipitate, and drying and crystallizing to obtain N, N' -carbonyl diimidazole; dissolving acetohydroxamic acid or benzohydroxamic acid serving as a raw material with a solvent, adding the N, N' -carbonyldiimidazole prepared in the step A while stirring, reacting at 25-35 ℃ for 35-50min, extracting after the reaction is finished, drying, removing the solvent under reduced pressure, and recrystallizing to obtain a product; taking acetohydroxamic acid as a raw material, and synthesizing a product which is 3-methyl-1, 2, 4-dioxazole-5-ketone; takes benzohydroxamic acid as a raw material, and the synthesized product is 3-phenyl-1, 2, 4-dioxazole-5-ketone. By adopting the technical scheme, the problems of more byproducts and low yield of the synthetic method of the dioxazalone compound in the prior art are solved.)

1. A synthetic method of a dioxazalone compound is characterized by comprising the following steps:

A. preparation of N, N' -carbonyldiimidazole

Mixing an organic solvent and imidazole, introducing phosgene, distilling, removing the organic solvent to obtain a residual mixture, filtering the residual mixture to obtain a filter cake, washing the filter cake with the organic solvent to obtain a filtrate, distilling the filtrate to remove the organic solvent, cooling the residual filtrate to 0 ℃, stirring for 30-50min, filtering out a precipitate, washing with the organic solvent at 0 ℃, and drying and crystallizing at 4mbar and 30 ℃ to obtain N, N' -carbonyldiimidazole; the volume ratio of the organic solvent is 1: (1.2-1.35) dichloromethane and tetrahydrofuran;

B. preparation of bisoxazolones

Dissolving acetohydroxamic acid or benzohydroxamic acid serving as a raw material with a solvent, adding the N, N' -carbonyldiimidazole prepared in the step A while stirring, reacting at 25-35 ℃ for 35-50min, extracting after the reaction is finished, drying, removing the solvent under reduced pressure, and recrystallizing to obtain a product;

taking acetohydroxamic acid as a raw material, and synthesizing a product which is 3-methyl-1, 2, 4-dioxazole-5-ketone;

takes benzohydroxamic acid as a raw material, and the synthesized product is 3-phenyl-1, 2, 4-dioxazole-5-ketone.

2. The method for synthesizing a bisoxazolone compound according to claim 1, wherein phosgene is introduced at a rate of 20-20.6g/h and a temperature of 30-35 ℃ in step A, and the mixture is stirred for 1.5-2h after phosgene is introduced.

3. The method as claimed in claim 1, wherein the distillation in step A is carried out at 500-790mbar at 25-35 ℃.

4. The method for synthesizing a bisoxazolone compound according to claim 1, wherein the organic solvent is dried in step A, and the mass ratio of the organic solvent to the imidazole is (2-3): 1.

5. The method for synthesizing a bisoxazolone compound according to claim 1, wherein the molar ratio of imidazole to phosgene in step A is (3-4): 1.

6. The method for synthesizing a bisoxazolone compound according to claim 1, wherein the solvent in step B is dichloromethane, and the amount of dichloromethane added is 5-10ml of dichloromethane added to 1g of raw materials.

7. The method for synthesizing a bisoxazolone compound according to claim 1, wherein the molar ratio of the raw material to N, N' -carbonyldiimidazole in step B is (1.12-1.2): 1.

8. the method for synthesizing a bisoxazolone compound according to claim 1, wherein dichloromethane is used for extraction in step B.

9. The method for synthesizing a bisoxazolone compound according to claim 1, wherein in step B, anhydrous sodium sulfate is used for drying.

10. The method for synthesizing a bisoxazolone compound according to claim 1, wherein in the step B, the mass ratio of recrystallization is (7-10): 1 of a mixture of n-hexane and acetone.

Technical Field

The invention belongs to the technical field of synthesis of dioxazalones, and relates to a synthesis method of a dioxazalone compound.

Background

When the battery is charged and discharged rapidly, the electrolyte is easy to change in temperature, so that unstable factors are caused, the electrolyte is decomposed, the decomposed products can erode electrode materials, the formation of an SEI film can be influenced, and the service life of the battery is further influenced. The bisoxazolones have wide application, can be used for medicines, pesticides, polymer improvement, organic synthesis intermediates and the like, and can be particularly used as an electrolyte additive of a battery to improve the high-temperature storage and cycle performance of the battery. The known synthesis methods of the dioxazaolones compounds are various, mainly comprise Pictet-Spengler reaction, Diels-Alder reaction, Pauson-Khand reaction and the like, and mainly have the problems of more byproducts, low yield and repeated fine purification before being applied to battery electrolyte.

Disclosure of Invention

The invention provides a synthetic method of a dioxazalone compound, which solves the problems of more byproducts and low yield of the synthetic method of the dioxazalone compound in the prior art.

The technical scheme of the invention is realized as follows: a synthetic method of a dioxazalone compound comprises the following steps:

A. preparation of N, N' -carbonyldiimidazole

Mixing an organic solvent and imidazole, introducing phosgene, distilling, removing the organic solvent to obtain a residual mixture, filtering the residual mixture to obtain a filter cake, washing the filter cake with the organic solvent to obtain a filtrate, distilling the filtrate to remove the organic solvent, cooling the residual filtrate to 0 ℃, stirring for 30-50min, filtering out a precipitate, washing with the organic solvent at 0 ℃, and drying and crystallizing at 4mbar and 30 ℃ to obtain N, N' -carbonyldiimidazole; the volume ratio of the organic solvent is 1: (1.2-1.35) dichloromethane and tetrahydrofuran;

B. preparation of bisoxazolones

Dissolving acetohydroxamic acid or benzohydroxamic acid serving as a raw material with a solvent, adding the N, N' -carbonyldiimidazole prepared in the step A while stirring, reacting at 25-35 ℃ for 35-50min, extracting after the reaction is finished, drying, removing the solvent under reduced pressure, and recrystallizing to obtain a product;

taking acetohydroxamic acid as a raw material, and synthesizing a product which is 3-methyl-1, 2, 4-dioxazole-5-ketone;

takes benzohydroxamic acid as a raw material, and the synthesized product is 3-phenyl-1, 2, 4-dioxazole-5-ketone.

Further, the phosgene is introduced in the step A at a speed of 20-20.6g/h and a temperature of 30-35 ℃, and the phosgene is introduced and then stirred for 1.5-2 h.

Further, the distillation in step A was carried out at 500 and 790mbar, 25-35 ℃.

Further, in the step A, the organic solvent is dried, and the mass ratio of the organic solvent to the imidazole is (2-3): 1.

Further, the molar ratio of imidazole to phosgene in the step A is (3-4): 1.

Furthermore, the solvent in the step B is dichloromethane, the adding amount of the dichloromethane is calculated by the raw materials, and 5-10ml of dichloromethane is added into 1g of the raw materials.

Further, the molar ratio of the raw material to the N, N' -carbonyldiimidazole in the step B is (1.12-1.2): 1.

further, dichloromethane is used for extraction in the step B.

Further, anhydrous sodium sulfate is used for drying in the step B.

Further, the mass ratio of recrystallization in the step B is (7-10): 1 of a mixture of n-hexane and acetone.

The working principle and the beneficial effects of the invention are as follows:

1. the synthesis method is simple, high in yield and few in by-products.

2. In the invention, the existence of the azo hydrochloride by-product in the step A has negative influence on the preparation of the dioxazaolone compound in the step B, and the stirring performance of the reaction is improved through the design of organic solvents of dichloromethane and tetrahydrofuran in the step A, so that better space or time yield among reactants is realized, the reduction of the azo hydrochloride by-product is ensured, and the reaction is carried out more efficiently; with simultaneous use of dichloromethane and tetrahydrofuranWashing a filter cake or a precipitate, more effectively reducing the existence of byproducts, further providing better reaction conditions for the preparation of the bisoxazolone compound in the step B, and further improving the yield of 3-methyl-1, 2, 4-bisoxazolone-5-one or 3-phenyl-1, 2, 4-bisoxazolone-5-one; the structural formula of the 3-methyl-1, 2, 4-dioxazole-5-ketone is shown in the specificationThe structural formula of the 3-phenyl-1, 2, 4-dioxazol-5-one is shown in the specification

Drawings

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

FIG. 1 is a diagram showing the preparation of 3-methyl-1, 2, 4-dioxazol-5-one prepared in example 1 of the present invention¹H NMR spectrum.

FIG. 2 is a diagram showing the preparation of 3-methyl-1, 2, 4-dioxazol-5-one prepared in example 1 of the present invention¹³C NMR spectrum.

FIG. 3 is a drawing showing the preparation of 3-phenyl-1, 2, 4-bisoxazol-5-one prepared in example 3 of the present invention¹H NMR spectrum.

FIG. 4 is a drawing showing the preparation of 3-phenyl-1, 2, 4-bisoxazol-5-one prepared in example 3 of the present invention¹³C NMR spectrum.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Preparation of 3-methyl-1, 2, 4-bisoxazol-5-one

A. Mixing the components in a volume ratio of 1: 1.25, mixing dichloromethane and tetrahydrofuran, drying to obtain an organic solvent, mixing 170.2g of the organic solvent with 68.08g of imidazole, introducing phosgene at a rate of 20g/h for 1.27h at a temperature of 35 ℃, introducing phosgene, stirring for 1.5h, distilling at 700mbar and 30 ℃, removing the organic solvent to obtain a residual mixture, filtering the residual mixture to obtain a filter cake, washing the filter cake with the organic solvent to obtain a filtrate, distilling the filtrate at 700mbar and 35 ℃, removing the organic solvent, cooling the residual filtrate to 0 ℃, stirring for 40min, filtering out a precipitate, washing with the organic solvent at 0 ℃, drying and crystallizing at 4mbar and 30 ℃ to obtain 40.54g of N, N' -carbonyldiimidazole;

B. dissolving 21.58g of acetohydroxamic acid by 130ml of dichloromethane, adding the N, N' -carbonyldiimidazole prepared in the step A, stirring while adding, reacting for 45min at 30 ℃, extracting by dichloromethane after the reaction is finished, drying by anhydrous sodium sulfate, removing the solvent under reduced pressure, and adopting a mass ratio of 8: 1 mixture of n-hexane and acetone to give 20.76g of the product 3-methyl-1, 2, 4-bisoxazol-5-one in 82.12% yield.

Example 2

Preparation of 3-methyl-1, 2, 4-bisoxazol-5-one

A. Mixing the components in a volume ratio of 1: 1.2, mixing dichloromethane and tetrahydrofuran, drying to obtain an organic solvent, mixing 136.16g of the organic solvent and 68.08g of imidazole, introducing phosgene at a rate of 20.6g/h for 1.17h at a temperature of 30 ℃, introducing phosgene, stirring for 2h, distilling at 600mbar and 35 ℃, removing the organic solvent to obtain a residual mixture, filtering the residual mixture to obtain a filter cake, washing the filter cake with the organic solvent to obtain a filtrate, distilling the filtrate at 790mbar and 25 ℃, removing the organic solvent, cooling the residual filtrate to 0 ℃, stirring for 30-50min, filtering out a precipitate, washing with the organic solvent at 0 ℃, drying and crystallizing at 4mbar and 30 ℃ to obtain 38.92g of N, N' -carbonyldiimidazole;

B. dissolving 20.18g of acetohydroxamic acid in 101ml of dichloromethane, adding the N, N' -carbonyldiimidazole prepared in the step A, stirring while adding, reacting for 35min at 35 ℃, extracting with dichloromethane after the reaction is finished, drying with anhydrous sodium sulfate, removing the solvent under reduced pressure, and performing reaction according to a mass ratio of 7: 1 mixture of n-hexane and acetone to give 19.81g of the product 3-methyl-1, 2, 4-bisoxazol-5-one in 81.62% yield.

Example 3

Preparation of 3-phenyl-1, 2, 4-bisoxazol-5-one

A. Mixing the components in a volume ratio of 1: 1.35, mixing dichloromethane and tetrahydrofuran, drying to obtain an organic solvent, mixing 210g of the organic solvent with 68.08g of imidazole, introducing phosgene at a rate of 20g/h for 1.27h at a temperature of 32 ℃, introducing phosgene, stirring for 1.8h, distilling at 790mbar and 25 ℃, removing the organic solvent to obtain a residual mixture, filtering the residual mixture to obtain a filter cake, washing the filter cake with the organic solvent to obtain a filtrate, distilling the filtrate at 790mbar and 25 ℃, removing the organic solvent, cooling the residual filtrate to 0 ℃, stirring for 30-50min, filtering out a precipitate, washing with the organic solvent at 0 ℃, drying and crystallizing at 4mbar and 30 ℃ to obtain 42.16g N, N' -carbonyldiimidazole;

B. dissolving 42.79g of benzohydroxamic acid by 214ml of dichloromethane, adding the N, N' -carbonyldiimidazole prepared in the step A, stirring while adding, reacting for 50min at 25 ℃, extracting by dichloromethane after the reaction is finished, drying by anhydrous sodium sulfate, removing the solvent under reduced pressure, and preparing the aqueous solution by using a solvent prepared by the following steps of: 1 mixture of n-hexane and acetone to give 35.89g of the product 3-phenyl-1, 2, 4-bisoxazol-5-one, yield 84.62%.

Example 4

Preparation of 3-phenyl-1, 2, 4-bisoxazol-5-one

A. Mixing the components in a volume ratio of 1: 1.35, mixing dichloromethane and tetrahydrofuran, drying to obtain an organic solvent, mixing 205g of the organic solvent with 68.08g of imidazole, introducing phosgene at a rate of 20.5g/h for 1.3h at a temperature of 32 ℃, introducing phosgene, stirring for 1.8h, distilling at 750mbar and 30 ℃, removing the organic solvent to obtain a residual mixture, filtering the residual mixture to obtain a filter cake, washing the filter cake with the organic solvent to obtain a filtrate, distilling the filtrate at 750mbar and 30 ℃, removing the organic solvent, cooling the residual filtrate to 0 ℃, stirring for 30-50min, filtering out a precipitate, washing with the organic solvent at 0 ℃, and drying and crystallizing at 4mbar and 30 ℃ to obtain 39.73g N, N' -carbonyldiimidazole;

B. dissolving 39.65g of benzohydroxamic acid with 240ml of dichloromethane, adding the N, N' -carbonyldiimidazole prepared in the step A, stirring while adding, reacting for 35min at 30 ℃, extracting with dichloromethane after the reaction is finished, drying with anhydrous sodium sulfate, removing the solvent under reduced pressure, and adopting a mass ratio of 8: 1 mixture of n-hexane and acetone to give 33.38g of the product 3-phenyl-1, 2, 4-bisoxazol-5-one in 83.51% yield.

3-phenyl-1, 2, 4-bisoxazol-5-one has CAS number 19226-36-9.

The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.