TWI860185B - Manufacture method of hydrogenated dicyclopentadiene diamine - Google Patents

Abstract

A manufacture method of hydrogenated dicyclopentadiene diamine, which uses dicyclopentadiene and carbon dioxide as raw materials, and reduces the reaction conditions through a metal catalyst to simplify the preparation process, maintain the absolute stereochemical selectivity of the product, and obtain high purity hydrogenated dicyclopentadiene diamine.

Description

Preparation method of hydrogenated dicyclopentadienediamine

The present invention relates to a method for preparing hydrogenated dicyclopentadienediamine, in particular to a method for preparing hydrogenated dicyclopentadienediamine from dicyclopentadiene.

Hydrogenated dicyclopentadiene can be used to synthesize a variety of biologically active compounds in the fields of organic synthesis and medicinal chemistry and has important application value.

Although several methods for preparing hydrogenated biscyclopentadienediamine have been disclosed in the prior art, such as using different metal catalysts and mixed gases to produce tricyclodecanedimethylamine monomers, the products are monomers containing structural isomers and stereochemical isomers, which cannot be separated or purified individually, and a high pressure and high temperature environment is required in the process.

Although the preparation methods of hydrogenated biscyclopentadienediamine in the prior art still have the disadvantages of complicated synthesis steps, low yield and poor selectivity, etc. Therefore, there is a need for a simple, efficient and absolutely stereochemically selective preparation method of hydrogenated biscyclopentadienediamine.

Therefore, the object of the present invention is to provide a method for preparing hydrogenated dicyclopentadienediamine to solve the problems of the prior art.

The present invention solves the problems of the prior art by providing a method for preparing hydrogenated dicyclopentadiene diamine, comprising a first step of thermally cracking dicyclopentadiene into cyclopentadiene, dripping a solution of an organic base and tetrahydrofuran into the cyclopentadiene obtained by thermal cracking to deprotonate it, and mixing the deprotonated solution with excess carbon dioxide to obtain dicyclopentadiene dioic acid and tricyclopentadiene trioic acid; a second step of thermally cracking dicyclopentadiene into cyclopentadiene trioic acid; and The dicyclopentadienedioic acid obtained in the first step is dissolved in a potassium hydroxide aqueous solution, and a metal catalyst is used to carry out a hydrogenation reaction in a hydrogen environment of 1 to 10 bar and 25 to 100° C. to obtain hydrogenated dicyclopentadienedioic acid; in the third step, the hydrogenated dicyclopentadienedioic acid and aluminum lithium hydroxide obtained in the second step are dissolved in tetrahydrofuran and heated to reflux to obtain hydrogenated dicyclopentadienediol; in the fourth step, The hydrogenated biscyclopentadiene diol obtained in the third step is dissolved in dichloromethane and then placed in an ice bath, and triethylamine and methylsulfonyl chloride are added to react, and hydrogenated biscyclopentadiene dimethanesulfonate is obtained by column chromatography; the fifth step is to add dimethylformamide to the hydrogenated biscyclopentadiene dimethanesulfonate, potassium phenylenediformimide and sodium iodide obtained in the fourth step under a nitrogen environment and heat to react, Dimethylformamide is removed by distillation under reduced pressure, and dicyclopentadienyl diphenyl dimethamide is purified by column chromatography to obtain dicyclopentadienyl diphenyl dimethamide. In the sixth step, a protic solvent and hydrazine hydrate are added to the dicyclopentadienyl diphenyl dimethamide obtained in the fifth step under a nitrogen environment to react until no solid is precipitated, and the mixture is washed with ether or methyl nitrile and vacuum filtered, and the obtained liquid is cycloconcentrated to obtain dicyclopentadienyl diamine.

In one embodiment of the present invention, a preparation method is provided, wherein the purity of the dicyclopentadiene in the first step is 80% to 99%.

In one embodiment of the present invention, a preparation method is provided, wherein the organic base in the first step is sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide or a mixture thereof.

In one embodiment of the present invention, a preparation method is provided, wherein in the first step, the molar ratio of the cyclopentadiene to the organic base is 0.1 to 1.5.

In one embodiment of the present invention, a preparation method is provided, wherein the metal catalyst in the second step is platinum, palladium, rhodium, ammonium or nickel.

In one embodiment of the present invention, a preparation method is provided, wherein in the second step, the solution obtained after the hydrogenation reaction is further adjusted to be acidic with an aqueous hydrochloric acid solution, stirred and filtered to collect the hydrogenated biscyclopentadienedioic acid.

In one embodiment of the present invention, a preparation method is provided, wherein in the third step, the molar ratio of the hydrogenated biscyclopentadienedioic acid to the aluminum lithium hydroxide is 1:0.5 to 1:4.

In one embodiment of the present invention, a preparation method is provided, wherein in the fourth step, the molar ratio of triethylamine to hydrogenated biscyclopentadiene diol is 1:1 to 8:1, and the molar ratio of methylsulfonyl chloride to hydrogenated biscyclopentadiene diol is 1:1 to 4:1.

In one embodiment of the present invention, a preparation method is provided, wherein in the fifth step, the molar ratio of the potassium phenylenedimethamide salt to biscyclopentadiene dimethanesulfonate is 1:1 to 4:1, and the molar ratio of the sodium iodide to biscyclopentadiene dimethanesulfonate is 0.001 to 0.1.

In one embodiment of the present invention, a preparation method is provided, wherein in the sixth step, the molar ratio of the hydrogenated biscyclopentadienyl diphenyl dimethimide to the hydrated hydrazine is 1:0.5 to 1:4.

The technical means adopted by the present invention can simplify the preparation process, maintain the absolute stereochemical selectivity of the product, and obtain high-purity hydrogenated dicyclopentadienediamine.

The following describes the implementation of the present invention. The description is not intended to limit the implementation of the present invention, but is an example of the implementation of the present invention.

According to an embodiment of the present invention, a method for preparing hydrogenated dicyclopentadiene comprises a first step of heating dicyclopentadiene to 160°C to thermally crack it into cyclopentadiene, dropping a solution of an organic base and tetrahydrofuran into the cyclopentadiene obtained by thermal cracking to deprotonate it, mixing the deprotonated solution with excess carbon dioxide, and depressurizing the solution. After the mixture is concentrated by rotation, the solvent is removed, deionized water is added to dissolve the solid, and concentrated hydrochloric acid is added to adjust the pH of the aqueous solution to 3 to 4. The crude product including dicyclopentadienedioic acid, tricyclopentadiene triacid and a small amount of isomers obtained through the above steps is repeatedly hot-washed with acetone and vacuum-filtered to obtain dicyclopentadienedioic acid and tricyclopentadiene triacid.

In the first step, the deprotonated solution is mixed with excess carbon dioxide and then preferably left to stand for 24 hours.

The tricyclopentadiene triacid obtained in the first step also has high economic value and can be further collected and utilized.

According to the method for preparing hydrogenated dicyclopentadiene of the present invention, the purity of the dicyclopentadiene in the first step can be appropriately selected in the range of 80% to 99%, preferably 84%.

According to the method for preparing hydrogenated dicyclopentadiene of the present invention, the organic base in the first step can be sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide or a mixture thereof.

According to the method for preparing hydrogenated dicyclopentadiene of the present invention, the molar ratio of the cyclopentadiene to the organic base in the first step is 0.1 to 1.5, preferably the molar ratio of the cyclopentadiene to the organic base is 1:1.1.

According to an embodiment of the present invention, the method for preparing hydrogenated dicyclopentadiene comprises a second step of dissolving the dicyclopentadienedioic acid obtained in the first step in an aqueous potassium hydroxide solution, and performing a hydrogenation reaction in a hydrogen environment of 1 to 10 bar and 25 to 100° C. using a metal catalyst to obtain hydrogenated dicyclopentadienedioic acid.

According to the method for preparing hydrogenated dicyclopentadiene of the present invention, the metal catalyst in the second step is platinum, palladium, rhodium, ammonium or nickel.

According to the method for preparing hydrogenated dicyclopentadiene of the present invention, the metal catalyst in the second step can be Raney nickel, and the weight ratio of dicyclopentadiene to Raney nickel is 1:1.

According to another method for preparing hydrogenated dicyclopentadiene of the present invention, the metal catalyst in the second step can be a palladium-carbon catalyst, and the weight ratio of dicyclopentadiene to the palladium-carbon catalyst is 1:0.1.

According to the method for preparing hydrogenated dicyclopentadiene of the present invention, in the second step, the solution obtained after the hydrogenation reaction is further adjusted to be acidic with an aqueous hydrochloric acid solution, stirred and filtered to collect the hydrogenated dicyclopentadiene diacid.

According to an embodiment of the present invention, the method for preparing hydrogenated biscyclopentadiene comprises a third step of dissolving the hydrogenated biscyclopentadiene diacid and aluminum lithium hydroxide obtained in the second step in tetrahydrofuran and heating and refluxing the mixture, and removing the organic solvent to obtain hydrogenated biscyclopentadiene diol.

According to the method for preparing hydrogenated biscyclopentadiene of the present invention, the molar ratio of the hydrogenated biscyclopentadiene diacid to the aluminum lithium hydroxide in the third step is 1:0.5 to 1:4, preferably the molar ratio of the hydrogenated biscyclopentadiene diacid to the aluminum lithium hydroxide is 1:1.3.

The method for preparing hydrogenated dicyclopentadiene according to one embodiment of the present invention comprises a fourth step of adding dichloromethane to the hydrogenated dicyclopentadiene diol obtained in the third step to dissolve the mixture, placing the mixture in an ice bath, adding triethylamine and methanesulfonyl chloride to react, and obtaining hydrogenated dicyclopentadiene dimethanesulfonate by column chromatography.

According to the method for preparing hydrogenated biscyclopentadiene of the present invention, in the fourth step, the molar ratio of triethylamine to hydrogenated biscyclopentadiene diol is 1:1 to 8:1, and the molar ratio of methyl sulfonyl chloride to hydrogenated biscyclopentadiene diol is 1:1 to 4:1. Preferably, the molar ratio of triethylamine to hydrogenated biscyclopentadiene diol is 8:1, and the molar ratio of methyl sulfonyl chloride to hydrogenated biscyclopentadiene diol is 2:1.

According to an embodiment of the present invention, the method for preparing hydrogenated biscyclopentadiene comprises a fifth step of adding dimethylformamide to the hydrogenated biscyclopentadiene dimethanesulfonate, potassium phenylenediformimide and sodium iodide obtained in the fourth step under a nitrogen environment and heating to react, removing dimethylformamide by distillation under reduced pressure, and purifying by column chromatography to obtain hydrogenated biscyclopentadiene diphenylenediformimide.

According to the method for preparing hydrogenated biscyclopentadiene of the present invention, in the fifth step, the molar ratio of the potassium phenylenediformamide salt to hydrogenated biscyclopentadiene dimethanesulfonate is 1:1 to 4:1, and the molar ratio of the sodium iodide to hydrogenated biscyclopentadiene dimethanesulfonate is 0.001:1 to 0.1:1. The molar ratio of the potassium phenylenediformamide salt to hydrogenated biscyclopentadiene dimethanesulfonate is 4:1, and the molar ratio of the sodium iodide to hydrogenated biscyclopentadiene dimethanesulfonate is 0.05:1.

According to an embodiment of the present invention, the method for preparing hydrogenated biscyclopentadiene comprises a sixth step of adding a protic solvent and hydrated hydrazine to the hydrogenated biscyclopentadiene diphenylene dimethyl imide obtained in the fifth step under a nitrogen environment to react until no solid is precipitated, washing with ether or methyl nitrile, vacuum filtering, and cycloconcentrating the obtained liquid to obtain hydrogenated biscyclopentadiene diamine.

According to the method for preparing hydrogenated dicyclopentadiene of the present invention, the molar ratio of the hydrogenated dicyclopentadiene diphenylene dimethoxyimide to hydrazine hydrate in the sixth step is 1:0.5 to 1:4, preferably 1:4.

The technical means adopted by the present invention can simplify the preparation process, maintain the absolute stereochemical selectivity of the product, and obtain high-purity hydrogenated dicyclopentadienediamine.

The above description and explanation are only the description of the preferred embodiment of the present invention. Those with ordinary knowledge in this technology can make other modifications according to the scope of the patent application defined below and the above description. However, these modifications should still be within the spirit of the present invention and within the scope of the rights of the present invention.

Claims (10)

A method for preparing hydrogenated dicyclopentadiene diamine comprises: A first step, thermally cracking dicyclopentadiene into cyclopentadiene, dropping a solution of an organic base and tetrahydrofuran into the cyclopentadiene obtained by thermal cracking to deprotonate it, and mixing the deprotonated solution with excess carbon dioxide to obtain dicyclopentadiene diacid and tricyclopentadiene triacid; A second step, dissolving the dicyclopentadiene diacid obtained in the first step in a potassium hydroxide aqueous solution, and performing a hydrogenation reaction in a hydrogen environment of 1 to 10 bar and 25 to 100°C using a metal catalyst to obtain hydrogenated dicyclopentadiene diacid; The third step is to dissolve the hydrogenated biscyclopentadiene diacid and aluminum lithium hydroxide obtained in the second step in tetrahydrofuran and heat to reflux to obtain hydrogenated biscyclopentadiene diol; The fourth step is to add dichloromethane to dissolve the hydrogenated biscyclopentadiene diol obtained in the third step, then place in an ice bath, react by adding triethylamine and methylsulfonyl chloride, and obtain hydrogenated biscyclopentadiene dimethanesulfonate by column chromatography; The fifth step is to add dimethylformamide to the hydrogenated biscyclopentadiene dimethanesulfonate, potassium phenylenediformimide and sodium iodide obtained in the fourth step under a nitrogen environment and heat to react, remove dimethylformamide by reduced pressure distillation, and purify by column chromatography to obtain hydrogenated biscyclopentadiene diphenylenediformimide; In the sixth step, a protic solvent and hydrated hydrazine are added to the hydrogenated biscyclopentadienyl diphenyl dimethyl imide obtained in the fifth step under a nitrogen environment to react until no solid is precipitated, and the mixture is washed with ether or methyl nitrile and filtered by vacuum. The obtained liquid is cycloconcentrated to obtain hydrogenated biscyclopentadienyl diamine. The production method as described in claim 1, wherein the purity of the dicyclopentadiene in the first step is 80% to 99%. The preparation method as described in claim 1, wherein the organic base in the first step is sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide or a mixture thereof. The preparation method as described in claim 1, wherein in the first step, the molar ratio of the cyclopentadiene to the organic base is 0.1 to 1.5. The preparation method as described in claim 1, wherein the metal catalyst in the second step is platinum, palladium, rhodium, ammonium or nickel. The preparation method as described in claim 1, wherein in the second step, the solution obtained after the hydrogenation reaction is further adjusted to be acidic with an aqueous hydrochloric acid solution, stirred and filtered to collect the hydrogenated biscyclopentadienedioic acid. The preparation method as described in claim 1, wherein in the third step, the molar ratio of the hydrogenated biscyclopentadiene diacid to the aluminum lithium hydroxide is 1:0.5 to 1:4. The preparation method as described in claim 1, wherein in the fourth step, the molar ratio of triethylamine to hydrogenated biscyclopentadiene diol is 1:1 to 8:1, and the molar ratio of methylsulfonyl chloride to hydrogenated biscyclopentadiene diol is 1:1 to 4:1. The preparation method as described in claim 1, wherein in the fifth step, the molar ratio of the potassium phenylenediamine salt to hydrogenated biscyclopentadiene dimethanesulfonate is 1:1 to 4:1, and the molar ratio of the sodium iodide to hydrogenated biscyclopentadiene dimethanesulfonate is 0.001:1 to 0.1:1. The preparation method as described in claim 1, wherein in the sixth step, the molar ratio of the hydrogenated biscyclopentadienyl diphenyl dimethimide to hydrated hydrazine is 1:0.5 to 1:4.