阅读说明：本技术 一种2,2’-双二苯基膦基-1,1’-联萘的合成方法 (Synthetic method of 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl ) 是由 严文忠 于 2020-07-01 设计创作，主要内容包括：一种2,2’-双二苯基膦基-1,1’-联萘的合成方法,通过如下方法实现：步骤一：1,1’-联-2-萘酚通过BUCHERER反应生成1,1’-联萘-2,2’-二胺；步骤二：1,1’-联萘-2,2’-二胺通过Sandmeyer反应生成联萘二溴；步骤三：联萘二溴与二苯基氯化膦通过格式反应生成2,2’-双二苯基膦基-1,1’-联萘(BINAP)。本发明均使用大宗化工原料,价格低廉易得,有效降低了生产成本；该发明不仅原料易得,反应收率较高,后处理简单,有利于工业放大,具有较强的工业应用前景。(A synthetic method of 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl is realized by the following steps: the method comprises the following steps: 1,1' -binaphthyl-2, 2' -diamine is generated by 1,1' -binaphthyl-2-naphthol through BUCHEER reaction; step two: generating binaphthyl dibromide by the Sandmeyer reaction of 1,1 '-binaphthyl-2, 2' -diamine; step three: the binaphthyl dibromide and diphenyl phosphine chloride react to generate 2,2 '-bis-diphenylphosphino-1, 1' -Binaphthyl (BINAP) through a Grignard reaction. The invention uses a large amount of chemical raw materials, has low price and easy obtainment and effectively reduces the production cost; the method has the advantages of easily obtained raw materials, higher reaction yield, simple post-treatment, contribution to industrial amplification and stronger industrial application prospect.)

1. A synthetic method of 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl is characterized by comprising the following steps: the method is realized by the following steps: the method comprises the following steps: 1,1' -binaphthyl-2, 2' -diamine is generated by 1,1' -binaphthyl-2-naphthol through BUCHEER reaction; step two: generating binaphthyl dibromide by the Sandmeyer reaction of 1,1 '-binaphthyl-2, 2' -diamine; step three: the binaphthyl dibromide and diphenyl phosphine chloride react to generate 2,2 '-bis-diphenylphosphino-1, 1' -Binaphthyl (BINAP) through a Grignard reaction.

2. The method for synthesizing 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl according to claim 1, wherein: the BUCHEER reaction in the first step is as follows: in aqueous solution, 1,1' -bi-2-naphthol and ammonia water react at 150 ℃ in the presence of sodium bisulfite as an auxiliary agent to generate 1,1' -binaphthyl-2, 2' -diamine; wherein the mol ratio of the 1,1' -bi-2-naphthol, the ammonia water and the sodium bisulfite is 1:5: 5.

3. The method for synthesizing 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl according to claim 1, wherein: the Sandmeyer reaction in step two is as follows: adding 1,1 '-binaphthyl-2, 2' -diamine and hydrobromic acid into a reactor at room temperature, adding a certain amount of water, stirring to completely dissolve, cooling the temperature of the reactor to-5 ℃, slowly dropwise adding a sodium nitrite solution while stirring, keeping stirring at a low temperature for 30min, adding a cuprous bromide hydrobromic acid solution, keeping stirring at a low temperature for 30min, heating to 70 ℃, reacting for 2.5 h, precipitating crystals, quenching the reaction by using a sodium carbonate aqueous solution, filtering, and recrystallizing to obtain binaphthyl dibromo; wherein, the mol ratio of the 1,1 '-binaphthyl-2, 2' -diamine, the hydrobromic acid and the sodium nitrite is 1:1.5: 1.

4. The method for synthesizing 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl according to claim 1, wherein: the format reaction in the third step is as follows: adding magnesium chips into a reactor, evacuating air in the reactor by using nitrogen, adding an anhydrous tetrahydrofuran solution to immerse the magnesium chips, slowly dropwise adding a binaphthyl dibromo tetrahydrofuran solution under the condition of stirring, supplementing half of the anhydrous tetrahydrofuran after dropwise adding is finished, heating to 70 ℃, and refluxing for 30min to obtain a Grignard reagent for later use; under the condition of stirring, cooling the prepared Grignard reagent to-5 to-10 ℃, slowly dripping tetrahydrofuran solution of diphenyl phosphine chloride, slowly heating to room temperature for reaction for 2 hours after dripping is finished, slowly dripping ammonium chloride aqueous solution after the reaction is finished, quenching the reaction, extracting and separating, and recrystallizing to obtain BINAP; when the Grignard reagent is prepared, the molar ratio of binaphthyl dibromide to magnesium chips to diphenyl phosphine chloride is 1:2.4: 1.8-2.

Technical Field

The invention belongs to the technical field of synthesis of organic phosphine compounds, and particularly relates to a synthesis method of 2,2 '-bis (diphenylphosphino) -1,1' -binaphthyl.

Background

With the development of new drugs and new material industries, efficient, green and atom-economical synthesis processes are becoming more important. In recent years, new catalytic systems have been rapidly developed in scientific research as well as industrial applications. The catalyst in the chemical reaction can effectively accelerate the reaction rate and improve the yield and the selectivity of the reaction, thereby realizing the long-term goal of green chemistry. It is noteworthy that organophosphine ligands that regulate the catalytic reaction play a crucial role in novel catalytic systems. Therefore, the organic phosphine ligand becomes a novel chemical product with wide application and is a fine chemical product with high added value, the market capacity reaches billion scales, and the organic phosphine ligand belongs to the key support range of the national industrial technical policy. 2,2 '-bis (diphenylphosphino) -1,1' -binaphthyl (BINAP for short) is taken as an important organic phosphine ligand, and plays a key role in important catalytic reactions such as Buchwald-Hartwig amination and Suzuki coupling since catalytic reactions are introduced in the last 80 th century. At present, BINAP has already realized the industrialization, is widely applied to in the synthesis of multiple new medicines and new materials, has important social meaning and broad market prospect.

There are three common synthetic methods for 2,2 '-bisdiphenylphosphino-1, 1' -binaphthyl: the Noyori/Takasago method, Merck Inc. method, Monsanto method, described in detail below, respectively:

the Noyori/Takasago method comprises the following reaction route:

the first methods for synthesizing BINAP were reported in 1980 by Noyori and Takasago (patents JP59020294 and EP135392), and their synthesis methods are shown in the figure. The Noyori/Takasago method takes binaphthyl Bis (BINOL) as a raw material, and generates a binaphthyl dibromo intermediate through high-temperature bromination, because the reaction temperature reaches 320 ℃, the method has extremely strict requirements on production equipment, and the bromination reaction yield is only 45%, so that the industrial application of the method is limited.

The Merck method comprises the following reaction route:

the second method was developed in the United states by Merck, 1994 (patents US252306 and US 5399771). The starting material of the method is binaphthol BINOL, and the binaphthol is firstly esterified with trifluoromethanesulfonic anhydride to generate a 2,2 '-bistrifluoromethane-1, 1' -binaphthyl intermediate. And then, coupling the triflate intermediate with diphenylphosphine hydrogen under the catalysis of nickel to obtain 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl. The reaction condition of the method is relatively mild, but the diphenyl phosphine hydrogen with high activity adopted in the process is sensitive to air, the operation is relatively difficult, and the industrial scale-up production is inconvenient. Meanwhile, equivalent quantities of trifluoromethanesulfonic anhydride and nickel catalyst are needed in the reaction route, and the trifluoromethanesulfonic anhydride and nickel catalyst are high in market price, so that the production cost of the method is high.

The Monsanto method comprises the following reaction route:

the third method is developed by Monsanto company (patent US5902904), and 2,2 '-bistrifluoromethane-1, 1' -binaphthyl intermediate and diphenyl phosphonium chloride are subjected to a catalytic coupling reaction in the presence of an excessive amount of zinc powder to obtain the product BINAP. The method shields the use of high-activity raw material diphenylphosphine hydrogen, and reduces the process difficulty. However, the Monsanto process also requires expensive trifluoromethanesulfonic anhydride and nickel catalysts, so that the process is still expensive to produce.

In 2014, Chinese patent (CN104370963) reported a new method for synthesizing 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl. The 4-methyl benzene sulfonic anhydride adopted by the method replaces trifluoromethanesulfonic anhydride in Merck and Monsanto methods, so that the production cost is reduced to a certain extent. However, the method uses nickel and noble metal palladium as a mixed catalyst to complete the final step of catalytic coupling reaction, which makes the production cost of the new coupling method still high. Meanwhile, the catalytic coupling method requires an inert atmosphere (such as nitrogen and argon) to protect the reaction system, so that the catalytic coupling synthesis process (Merck method, Monsanto method and chinese patent CN104370963) still has great operation difficulty.

Patent CN108586528B reports a synthesis method of 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl. The method is prepared by reacting 2,2 '-bis-ethoxy-1, 1' -binaphthyl with metal lithium and then reacting with diphenyl phosphine chloride, active lithium metal is used as a reactant, careful quenching treatment is needed after the reaction is finished, and great operation difficulty is still provided. In view of the wide market prospect of 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl, people are prompted to research a process route with lower cost, simpler operation and higher product purity.

Disclosure of Invention

In order to solve the problems, the invention provides a method for synthesizing 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl, which has the advantages of high yield, low production cost, simple post-treatment, high product purity and suitability for process amplification. In addition, the method does not need expensive trifluoromethanesulfonic anhydride and noble metal catalysts, does not need inert atmosphere protection, and is simple in subsequent treatment and environment-friendly.

The purpose of the invention is realized by the following way, and the reaction route is as follows:

a synthetic method of 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl is realized by the following steps: the method comprises the following steps: 1,1' -binaphthyl-2, 2' -diamine is generated by 1,1' -binaphthyl-2-naphthol through BUCHEER reaction; step two: generating binaphthyl dibromide by the Sandmeyer reaction of 1,1 '-binaphthyl-2, 2' -diamine; step three: the binaphthyl dibromide and diphenyl phosphine chloride react to generate 2,2 '-bis-diphenylphosphino-1, 1' -Binaphthyl (BINAP) through a Grignard reaction.

The BUCHEER reaction in the first step is as follows: in aqueous solution, 1,1' -bi-2-naphthol and ammonia water react at 150 ℃ in the presence of sodium bisulfite as an auxiliary agent to generate 1,1' -binaphthyl-2, 2' -diamine; wherein the mol ratio of the 1,1' -bi-2-naphthol, the ammonia water and the sodium bisulfite is 1:5: 5.

The Sandmeyer reaction in step two is as follows: adding 1,1 '-binaphthyl-2, 2' -diamine and hydrobromic acid into a reactor at room temperature, adding a certain amount of water, stirring to completely dissolve, cooling the temperature of the reactor to-5 ℃, slowly dropwise adding a sodium nitrite solution while stirring, keeping stirring at a low temperature for 30min, adding a cuprous bromide hydrobromic acid solution, keeping stirring at a low temperature for 30min, heating to 70 ℃, reacting for 2.5 h, precipitating crystals, quenching the reaction by using a sodium carbonate aqueous solution, filtering, and recrystallizing to obtain binaphthyl dibromo; wherein, the mol ratio of the 1,1 '-binaphthyl-2, 2' -diamine, the hydrobromic acid and the sodium nitrite is 1:1.5: 1.

The format reaction in the third step is as follows: adding magnesium chips into a reactor, evacuating air in the reactor by using nitrogen, adding an anhydrous tetrahydrofuran solution to immerse the magnesium chips, slowly dropwise adding a binaphthyl dibromo tetrahydrofuran solution under the condition of stirring, supplementing half of the anhydrous tetrahydrofuran after dropwise adding is finished, heating to 70 ℃, and refluxing for 30min to obtain a Grignard reagent for later use; under the condition of stirring, cooling the prepared Grignard reagent to-5 to-10 ℃, slowly dripping tetrahydrofuran solution of diphenyl phosphine chloride, slowly heating to room temperature for reaction for 2 hours after dripping is finished, slowly dripping ammonium chloride aqueous solution after the reaction is finished, quenching the reaction, extracting and separating, and recrystallizing to obtain BINAP; when the Grignard reagent is prepared, the molar ratio of binaphthyl dibromide to magnesium chips to diphenyl phosphine chloride is 1:2.4: 1.8-2.

The invention has the following beneficial effects:

the invention prepares 2,2 '-bis-diphenylphosphino-1, 1' -binaphthyl by BUCHEER reaction, Sandmeyer reaction and Grignard reaction, does not need to use high-activity diphenylphosphine hydrogen as a phosphonating reagent, but adopts more stable and cheaper diphenyl phosphine chloride, does not need to use three expensive methanesulfonic anhydride as raw materials, does not need to use active lithium metal, uses a large amount of chemical raw materials, has low price and is easy to obtain, and effectively reduces the production cost; the method has the advantages of easily obtained raw materials, higher reaction yield, simple post-treatment, contribution to industrial amplification and stronger industrial application prospect.

Drawings

FIG. 1 is a schematic representation of 2,2 '-bisdiphenylphosphino-1, 1' -binaphthyl prepared in example 1¹H-NMR spectra

FIG. 2 is a schematic representation of 2,2 '-bisdiphenylphosphino-1, 1' -binaphthyl prepared in example 1¹³C-NMR spectra

FIG. 3 is a schematic representation of 2,2 '-bisdiphenylphosphino-1, 1' -binaphthyl prepared in example 1³¹P-NMR spectra

Detailed Description