CN115572311B

CN115572311B - Synthesis method for synthesizing selenium/sulfur compounds based on binaphthyl dithiol

Info

Publication number: CN115572311B
Application number: CN202211229145.XA
Authority: CN
Inventors: 孙喜玲; 刘银辉; 张吉
Original assignee: Anhui Zesheng Technology Co ltd
Current assignee: Anhui Zesheng Technology Co ltd
Priority date: 2022-09-30
Filing date: 2022-09-30
Publication date: 2023-04-28
Anticipated expiration: 2042-09-30
Also published as: CN115572311A

Abstract

The invention discloses a method for synthesizing selenium/sulfur compounds based on binaphthyl dithiol, and relates to the technical field of organic chemical synthesis. The synthesis method comprises the steps of generating an axial chiral binaphthyl dithiol catalyst under the combined action of triethylamine and phosphorus trichloride and under the combined action of alkylamine, chiral binaphthyl dithiol and selenium powder or sulfur powder; compared with the existing catalyst which catalyzes the reaction of some small organic molecules, the invention provides the synthesis of a new axial chiral binaphthyl dithiol compound containing polysulfide.

Description

Synthesis method for synthesizing selenium/sulfur compounds based on binaphthyl dithiol

Technical Field

The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a method for synthesizing selenium/sulfur compounds based on binaphthyl dithiol.

Background

The synthesis and application of binaphthol skeleton as catalyst is less studied, and compared with the research and development of binaphthol synthesis catalyst, the research and development of binaphthol skeleton is very lack, and the importance of sulfur in natural products and medicines, catalysts and ligands is seen in order, so that the development of binaphthol catalyst is very urgent and needed.

Fulvio Di Furia synthesized binaphthyl dithiol for the first time in 1989 (Tetrahedron letters 1989, 30, 2575-2576), and Ottorino De Lucchi (Tetrahedron letters 1991, 32, 4771-4774) utilized nucleophilic substitution of binaphthyl dithiol with 1, 3-dibromopropane, starting from 1991. The synthesis of binaphthyl dithiol was reported in 1993 as Ottorino De Lucchi (J. Org. Chem. 1993, 58, 7, 1748-1750) and enantiomerically pure binaphthyl dithiol was obtained. In the last twenty years from 1994, several scientists have performed different methods of synthesis of binaphthol. The most common method is the reduction of binaphthyl dithioesters using lithium aluminum hydride (Journal of the American Chemical society 2008, 130, 16888-168860). In 2009, eike b. Bauer first synthesized the racemate of binaphthyl aminodithiophosphane (Tetrahedron letters 2009, 50, 922-925) using binaphthyl dithiol, and tested the coordination chemistry and reactivity of binaphthyl aminodithiophosphane with rhodium, iridium and ruthenium. Besides, no other report exists on the synthesis and research of binaphthyl amino dithiophosphane, and the synthesis and research of the sulfur or selenide of binaphthyl amino dithiophosphane are not needed, so that the patent provides a good choice for making up the blank of the class. The synthesis of the sulfur or selenide of the aminodithiophosphane of binaphthyl as catalyst is therefore highly necessary.

Disclosure of Invention

The invention aims to provide a synthesis method of chiral binaphthyl dithiol-derived selenium/sulfide, which has the advantages of mild reaction conditions, economical and easy preparation of used raw materials, basically no toxicity, good repeatability, simple reaction operation, wide substrate application range and good economy.

The technical scheme adopted by the invention for achieving the purpose is as follows:

the chemical structural general formula of the chiral binaphthyl dithiol derivative selenium/sulfide is shown as formula I or formula II:

I，/>

II；

wherein X is selected from Se or S. According to the invention, different chiral binaphthyl dithiol derivative selenium/sulfide catalysts are synthesized for the first time by selecting different alkylamines. According to the synthesis method provided by the invention, binaphthyl dimethyl formyl is used as a starting material, binaphthyl dithiol and cheap and easily available alkylamine are used as substrates, and the chiral binaphthyl dithiol derivative selenium/sulfide catalyst is prepared by a one-pot method, so that a complex synthesis route is avoided in the reaction process; the substrate of the method provided by the invention has diversity, can be used for synthesizing binaphthyl dithiol derivative selenium/sulfide catalysts with various alkyl substituents, and the prepared chiral binaphthyl dithiol derivative selenium/sulfide has good catalytic activity and can be well applied to the synthesis of axial chiral selenium-containing diaryl derivatives as a catalyst.

Still another object of the present invention is to provide a method for synthesizing the chiral binaphthyl dithiol-derived selenium/sulfide, comprising: mixing the chiral binaphthyl dithiol derivative with phosphorus trichloride, triethylamine and alkylamine, and generating the chiral binaphthyl dithiol derivative selenium/sulfide under the combined action of selenium powder or sulfur powder and a solvent.

The solvent includes methylene chloride.

Specifically, the synthesis method of the chiral binaphthyl dithiol derivative selenium/sulfide comprises the following steps:

dissolving phosphorus trichloride in dichloromethane, cooling to the low temperature of 0-2 ℃, dropwise adding triethylamine into the solution, reacting for 8-14 min, heating the system to room temperature, adding alkylamine, and stirring for 10-14 h; adding chiral binaphthyl mercaptan derivatives into the system at room temperature, stirring and reacting for 10-14 hours, then adding selenium powder or sulfur powder at room temperature, and continuously stirring and reacting for 10-14 hours; finally, the chiral binaphthyl dithiol derivative selenium/sulfide is obtained through reduced pressure distillation and column chromatography purification.

The chemical structure of the chiral binaphthyl dithiol derivative is shown as a formula III:

III。

further, the preparation method of the chiral binaphthyl dithiol derivative comprises the following steps:

under anhydrous and anaerobic condition, S' - (1)S) Dissolving 1,1 '-binaphthyl-2, 2' -N-dimethylformamide in ultra-dry tetrahydrofuran, placing the reaction system at 0-2 ℃, stirring for 3-8 min, slowly adding lithium aluminum hydride into the reaction system, slowly heating the reaction system to 45-55 ℃, stirring for reacting for 10-14 h, performing post-treatment reaction, placing the reaction at 0-2 ℃, slowly dripping saturated sodium sulfate aqueous solution into the reaction system for quenching reaction, adding anhydrous sodium sulfate again to absorb water in the reaction, and finally, using diatomite to filter liquid, and performing spin drying to obtain binaphthol.

S, S' - (1)S) -1,1 '-binaphthyl-2, 2' -N-dimethylThe molar ratio of formyl to lithium aluminum hydride is 1:4-6.

The ratio of phosphorus trichloride to methylene dichloride is 0.2-0.3 mol:1mL.

The molar ratio of triethylamine to phosphorus trichloride is 4-6:1.

The molar ratio of the alkylamine to the phosphorus trichloride is 0.9-1.1:1.

The alkylamine includes diisopropylamine or diisobutylamine.

The molar ratio of the chiral binaphthyl dithiol derivative to the phosphorus trichloride is 0.9-1.1:1.

The molar ratio of selenium powder or sulfur powder to phosphorus trichloride is 2-4:1.

The chiral binaphthyl dithiol derivative selenium/sulfide has a structure selected from one of the formulas A to D:

。

the specific preparation route of the chiral binaphthyl dithiol derivative selenium/sulfide is as follows:

，

wherein R is selected fromi-Pr ori-Bu; x is selected from Se or S.

The invention also discloses application of the chiral binaphthyl dithiol derivative selenium/sulfide serving as a catalyst in organic chiral catalytic reaction.

Still another object of the present invention is to provide the use of the chiral binaphthyl dithiol derivative selenium/sulfide as described above for preparing axial chiral selenium-containing biaryl derivatives.

Specifically, the synthesis method of the axial chiral selenium-containing diaryl derivative comprises the following steps:

at room temperature, adding a phenylacetylene substrate, a selenoaryl reagent, a catalyst and boron trifluoride diethyl etherate into a reaction tube, adding a solvent under the room temperature condition, reacting for a period of time in an argon atmosphere, performing post-treatment reaction, and then performing reduced pressure distillation and silica gel column purification to obtain a selenoaryl-substituted axial chiral product.

The synthetic route of the synthetic method of the axial chiral selenium-containing diaryl derivative is as follows:

。

more preferably, in the synthesis process of the axial chiral selenium-containing diaryl derivative, chiral binaphthyl dithiol derivative selenium/sulfide shown in the formula A is adopted(S)-A) is represented by the formula B-D(S)-B~(S)The chiral binaphthyl dithiol derivative selenium/sulfide shown in the D) is used in a compounding way and is used as a reaction catalyst.

Preferably, the method comprises the steps of,(S)-A and(S)the molar ratio of the-B is 1:0.3-0.4;(S)-A and(S)the molar ratio of the C is 1:0.9-1;(S)-A and(S)the molar ratio of D is 1:0.5-0.6. In the application example of the synthesized chiral binaphthyl dithiol derivative selenium/sulfide, the method of combination and compound use is adopted to catalyze and synthesize the axial chiral selenium-containing diaryl derivative, so that the chiral binaphthyl dithiol derivative has higher catalytic activity and wider application prospect.

Compared with the prior art, the invention has the following beneficial effects:

according to the synthesis method provided by the invention, different chiral binaphthyl dithiol derivative selenium/sulfide catalysts are synthesized for the first time by selecting different alkylamines, binaphthyl dimethyl formyl is taken as a starting raw material, one-step preparable binaphthyl dithiol and cheap and easily available alkylamines are taken as substrates, and the chiral binaphthyl dithiol derivative selenium/sulfide catalysts are prepared by a one-pot method, so that a complex synthesis route is avoided in the reaction process; and the reaction substrates have diversity, and can synthesize binaphthyl dithiol derivative selenium/sulfide catalysts with various alkyl substituents. Meanwhile, the prepared binaphthyl dithiol derivative selenium/sulfide has good catalytic activity, and can be well applied to organic chiral catalytic reaction.

Therefore, the invention provides a synthesis method of chiral binaphthyl dithiol-derived selenium/sulfide, which has the advantages of mild reaction conditions, economical and easy preparation of used raw materials, basically no toxicity, good repeatability, simple reaction operation, wide substrate application range and good economy.

Drawings

FIG. 1 is a schematic illustration of an embodiment of the present invention(S)-nuclear magnetic hydrogen profile of a;

FIG. 2 is a schematic illustration of the preparation of an embodiment of the present invention(S)-nuclear magnetic carbon profile of a;

FIG. 3 is a schematic illustration of the preparation of an embodiment of the present invention(S)-nuclear magnetic hydrogen profile of B;

FIG. 4 is a schematic illustration of the preparation of an embodiment of the present invention(S)-nuclear magnetic carbon spectrogram of B;

FIG. 5 shows the preparation of an embodiment of the present invention(S)-nuclear magnetic hydrogen profile of C;

FIG. 6 is a schematic illustration of the preparation of an embodiment of the present invention(S)-nuclear magnetic carbon spectrogram of C;

FIG. 7 is a schematic illustration of an embodiment of the present invention(S)-nuclear magnetic hydrogen profile of D;

FIG. 8 is a schematic diagram of an embodiment of the present invention(S)-nuclear magnetic carbon spectrogram of D;

FIG. 9 is a nuclear magnetic resonance hydrogen spectrum of product I prepared in the examples of the present invention;

FIG. 10 is a nuclear magnetic resonance spectrum of the product I prepared in the example of the present invention;

FIG. 11 is an HPLC diagram of the racemic structure of product I prepared in the examples of the present invention;

FIG. 12 is an HPLC diagram of the chiral structure of product I prepared in the examples of the present invention;

FIG. 13 shows the results of infrared spectrum test of the modified hydrotalcite prepared in example 5 and example 6 of the present invention.

Detailed Description

The technical solution of the present invention will be described in further detail with reference to the specific embodiments, but it should be understood that these examples are only for illustrating the present invention to aid understanding of the disclosure of the present invention, and are not intended to limit the scope of the present invention, nor the scope of protection of the present invention is limited to the following examples.

The source of the raw materials in the following examples is not particularly limited, and may be prepared by a preparation method well known to those skilled in the art or commercially available.

In this embodiment, the hydrogen nuclear magnetic resonance spectrum of the compound ¹ H NMR ¹³ C NMR) was determined from Bruker AVANCE III HD 400 with deuterated chloroform as solvent. Chemical shift (δ) is referenced in ppm with tetramethylsilane as an internal standard, the multiplicity is as follows: s=singlet, d=doublet, t=triplet, q=quadruple, m=multiplet.

The structure and CAS numbers of the partial raw materials used in the examples of the present invention are shown in Table 1:

TABLE 1 raw material structure

Chemical structure of raw materials	CAS number
		189084-89-7
	2411718-67-5
		1255094-08-6

Example 1:

preparation of chiral binaphthyl dithiol derivative selenium/sulfide shown in formula A:

the synthetic route is as follows:

the preparation process comprises the following steps:

under anhydrous and anaerobic condition, S' - (1)S) Dissolving 1,1 '-binaphthyl-2, 2' -N-dimethylformamide (1.0 equiv) in ultra-dry tetrahydrofuran, placing the reaction system at 0 ℃, stirring for 5 min, slowly adding lithium aluminum hydride (5.0 equiv) into the reaction system, slowly heating the reaction system to 50 ℃, stirring for 12 h post-treatment reaction, placing the reaction at 0 ℃, slowly dripping saturated sodium sulfate aqueous solution into the reaction system to quench the reaction, adding anhydrous sodium sulfate again to absorb water in the reaction, and finally, using diatomite to filter liquid, and spin-drying to obtain the productS) -binaphthol;

under anhydrous and anaerobic conditions, 0.65 mmol of phosphorus trichloride was dissolved in ultra-dry DCM (2.6 mL), the reaction was cooled to 0deg.C, and 3.25 mmol Et was added dropwise thereto ₃ N;10 After min, the reaction was warmed to room temperature and 0.65 mmol diisopropylamine was added, followed by stirring 12. 12 h; adding 0.65 mmol to the system at room temperatureS) After stirring reaction of binaphthyl dithiol for 12 h, adding 1.95 mmol of selenium powder at room temperature, and stirring reaction for 12 h; filtering with diatomite after the reaction is completed, concentrating in vacuum, and spin-drying; the crude product was purified on silica gel (EtOAc: petroleum ether=1:200, v/v) to give a white solid(S)-A, yield thereof was found to be 33%.

¹ H NMR (400 MHz, Chloroform-d) δ 8.03 (d, J = 8.5 Hz, 1H), 8.00 – 7.90 (m, 4H), 7.78 (dd, J = 8.6, 0.8 Hz, 1H), 7.50 (dddt, J = 22.8, 8.1, 6.8, 1.2 Hz, 2H), 7.29 (ddd, J = 8.4, 6.8, 1.3 Hz, 1H), 7.23 – 7.12 (m, 2H), 6.95 (d, J = 8.6 Hz, 1H), 3.70 (dp, J = 20.8, 6.8 Hz, 2H), 1.51 (d, J = 6.9 Hz, 6H), 1.27 (d, J = 6.9 Hz, 6H)； ¹³ C NMR (101 MHz, CDCl ₃ ) δ 141.82, 141.70, 134.67, 134.60, 134.16, 133.45, 133.23, 133.20, 132.80, 130.09, 129.68, 129.66, 129.16, 128.91, 128.89, 128.59, 128.57, 128.32, 128.17, 127.67, 127.24, 127.16, 127.12, 127.10, 126.79, 51.24, 27.06, 23.38, 23.18. As shown in fig. 1-2.

Example 2:

preparation of chiral binaphthyl dithiol derivative selenium/sulfide shown in formula B:

the synthetic route is as follows:

the preparation process comprises the following steps:

under anhydrous and anaerobic conditions, 0.65 mmol of phosphorus trichloride was dissolved in ultra-dry DCM (2.6 mL), the reaction was cooled to 0deg.C, and 3.25 mmol Et was added dropwise thereto ₃ N;10 After min, the reaction was warmed to room temperature and 0.65 mmol diisopropylamine was added, followed by stirring 12. 12 h; adding 0.65 mmol to the system at room temperatureS) After stirring reaction 12 h of binaphthyl dithiol, adding 1.95 mmol of sulfur powder at room temperature, and stirring reaction 12 h; after completion of the reaction, it was filtered through celite, concentrated in vacuo, and the crude product was purified by silica gel (EtOAc: petroleum ether=1:200, v/v) to give a white solid(S)The yield of-B was 40%.

¹ H NMR (400 MHz, Chloroform-d) δ 8.03 (d, J = 8.5 Hz, 1H), 7.99 – 7.90 (m, 4H), 7.78 (d, J = 8.5 Hz, 1H), 7.58 – 7.39 (m, 2H), 7.32 – 7.26 (m, 1H), 7.23 – 7.12 (m, 2H), 6.96 (d, J = 8.5 Hz, 1H), 3.57 (dp, J = 22.7, 6.8 Hz, 2H), 1.49 (d, J = 6.8 Hz, 6H), 1.25 (d, J = 6.8 Hz, 6H); ¹³ C NMR (101 MHz, CDCl ₃ ) Delta 141.65, 141.61, 134.68, 134.61, 134.06, 134.03, 133.45, 133.43, 133.31, 133.28, 132.76, 132.74, 130.29, 130.27, 129.62, 129.59, 128.94, 128.89, 128.81, 128.79, 128.55, 128.53, 128.29, 128.28, 128.16, 127.70, 127.68, 127.17, 127.16, 127.12, 127.07, 127.05, 126.79, 126.77, 50.35, 23.11. As shown in fig. 3-4.

Example 3:

preparation of chiral binaphthyl dithiol derivative selenium/sulfide shown in formula C:

the synthetic route is as follows:

the preparation process comprises the following steps:

under anhydrous and anaerobic conditions, 0.157 mmol of phosphorus trichloride was dissolved in overdry DCM (0.6 mL), the reaction system was cooled to 0deg.C, and 0.785 mmol of Et was added dropwise thereto ₃ N;10 After min, the reaction was warmed to room temperature and 0.157 mmol of diisobutylamine was added, followed by stirring 12. 12 h; 0.157 mmol of the catalyst was added to the system at room temperatureS) After stirring reaction 12 h of binaphthyl dithiol, adding 0.471 mmol of selenium powder at room temperature, and stirring reaction 12 h; after completion of the reaction, it was filtered through celite, concentrated in vacuo, and the crude product was purified by silica gel (EtOAc: petroleum ether=1:200, v/v) to give a white solid(S)The yield of-C was 55%.

¹ H NMR (400 MHz, Chloroform-d) δ 8.03 (d, J = 8.6 Hz, 1H), 7.99 – 7.90 (m, 4H), 7.83 (d, J = 8.6 Hz, 1H), 7.51 (dt, J = 21.4, 7.5 Hz, 2H), 7.30 (t, J = 7.7 Hz, 1H), 7.19 (t, J = 7.4 Hz, 2H), 7.00 (d, J = 8.4 Hz, 1H), 3.17 (td, J = 13.6, 8.9 Hz, 2H), 3.02 (td, J = 14.6, 6.1 Hz, 2H), 1.94 (dq, J = 8.4, 6.4 Hz, 2H), 0.89 (dd, J = 6.7, 3.9 Hz, 12H)； ¹³ C NMR (101 MHz, CDCl ₃ ) δ 142.10, 142.06, 141.86, 141.81, 134.19, 134.16, 133.85, 133.78, 133.54, 133.52, 133.25, 133.22, 132.88, 132.86, 132.72, 132.69, 131.35, 129.86, 129.83, 129.01, 128.96, 128.84, 128.82, 128.58, 128.56, 128.32, 128.04, 127.61, 127.60, 127.32, 127.30, 127.19, 127.16, 126.85, 126.83, 54.98, 26.14, 26.11, 20.35, 20.04. As shown in fig. 5-6.

Example 4:

preparation of chiral binaphthyl dithiol derivative selenium/sulfide shown in formula D:

the synthetic route is as follows:

the preparation process comprises the following steps:

under anhydrous and anaerobic conditions, 0.157 mmol of phosphorus trichloride was dissolved in overdry DCM (0.6 mL), the reaction system was cooled to 0deg.C, and 0.785 mmol of Et was added dropwise thereto ₃ N;10 After min, the reaction was warmed to room temperature and 0.157 mmol of diisobutylamine was added, followed by stirring 12. 12 h; 0.157 mmol of the catalyst was added to the system at room temperatureS) After stirring reaction 12 h with binaphthyl dithiol, 0.471 mmol of sulfur powder is added under room temperature condition, and stirring reaction 12 h is carried out; after completion of the reaction, it was filtered through celite, concentrated in vacuo, and the crude product was purified by silica gel (EtOAc: petroleum ether=1:200, v/v) to give a white solid(S)The D yield was 47%.

¹ H NMR (400 MHz, Chloroform-d) δ 8.03 (d, J = 8.6 Hz, 1H), 7.94 (ddd, J = 11.8, 8.3, 3.5 Hz, 4H), 7.83 (d, J = 8.6 Hz, 1H), 7.58 – 7.43 (m, 2H), 7.30 (ddd, J = 8.3, 6.8, 1.2 Hz, 1H), 7.25 – 7.14 (m, 2H), 7.01 (d, J = 8.5 Hz, 1H), 3.04 (dtd, J = 41.2, 13.9, 7.5 Hz, 4H), 2.03 – 1.81 (m, 2H), 0.88 (d, J = 6.6 Hz, 12H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 142.11, 142.07, 141.78, 141.73, 134.11, 134.08, 133.84, 133.77, 133.54, 133.52, 133.28, 133.25, 133.03, 133.00, 132.68, 132.65, 131.65, 131.63, 129.80, 129.77, 128.75, 128.71, 128.70, 128.55, 128.53, 128.31, 128.30, 128.05, 127.66, 127.64, 127.26, 127.25, 127.16, 127.13, 126.86, 126.85, 54.17, 26.06, 26.02, 20.39, 20.06. As shown in fig. 7-8.

Example 5:

the preparation of chiral binaphthol-derived selenium/sulfide of formula B differs from example 2 in that: the sulfur powder is replaced by the load type elemental sulfur with equal sulfur dosage.

Wherein the supported elemental sulfur is prepared by hydrotalcite or modified hydrotalcite supported sulfur; the modified hydrotalcite comprises sodium dodecyl sulfate and sodium dimethyl dithiocarbamate modified hydrotalcite. According to the invention, sodium dodecyl sulfate and sodium dimethyldithiocarbamate modified hydrotalcite are adopted, the particle size distribution of the prepared modified hydrotalcite is obviously narrowed, sulfur can be better loaded to prepare the active elemental sulfur, and the modified hydrotalcite is applied to a synthesis method of chiral binaphthyl dithiol derivative selenium/sulfide, so that the synthesis yield of the chiral binaphthyl dithiol derivative selenium/sulfide is obviously improved. The reason for this may be that the modified hydrotalcite has a beneficial change in structure, a significantly narrowed particle size distribution, and can better form supported elemental sulfur, so that the modified hydrotalcite is applied to the preparation of chiral binaphthyl dithiol derivative selenium/sulfide, can be more uniformly distributed in a reaction system, effectively increases the reaction efficiency of related reaction steps, and further increases the yield of the product.

Specifically, the preparation method of the supported elemental sulfur comprises the following steps:

grinding hydrotalcite or modified hydrotalcite to 350-500 meshes, adding water, stirring to prepare 8-12% suspension slurry, slowly adding sodium sulfite with the sulfur content of 0.9-1.1wt% of hydrotalcite or modified hydrotalcite and sodium sulfide with the molar ratio of 1.8-2.2 times of sodium sulfite under stirring, adjusting pH to 2.5-3.5 by using 0.4-0.6M sulfuric acid, and reacting for 4-6 hours at room temperature; and then centrifugally dewatering to obtain a filter cake, drying and crushing to 200-400 meshes to obtain the supported elemental sulfur.

In this embodiment, modified hydrotalcite is used in the preparation process of the supported elemental sulfur, and specifically:

grinding modified hydrotalcite to 420 meshes, adding water, stirring to prepare suspension slurry with the concentration of 10%, slowly adding sodium sulfite with the sulfur content of 1wt% of the modified hydrotalcite and sodium sulfide with the molar ratio of 2 times of the sodium sulfite under stirring, adjusting the pH to 3.2 by adopting sulfuric acid with the concentration of 0.5M, and reacting at room temperature for 5; and then centrifugally dewatering to obtain a filter cake, drying and crushing to 360 meshes to obtain the supported elemental sulfur.

Further, the preparation method of the modified hydrotalcite comprises the following steps:

placing the water-taking talcum into a muffle furnace to calcine for 5-6 h at 480-520 ℃, then placing the talcum into boiling water, heating and refluxing, slowly dripping 0.01-0.02M modifier aqueous solution under the condition of intense stirring, adjusting the pH to 9-10, continuously heating and refluxing for 2-4 h after dripping, aging for 0.5-1.5 h, centrifuging for 5-10 min at the rotating speed of 3500-4500 r/min, separating to obtain a solid, and drying for 24h at 70-80 ℃ to obtain the modified hydrotalcite.

The mass ratio of the modifier to the hydrotalcite is 1:0.8-1.2; the modifier comprises sodium dodecyl sulfate and sodium dimethyldithiocarbamate, and the molar ratio of the sodium dodecyl sulfate to the sodium dimethyldithiocarbamate is 1:0.6-0.8.

The preparation method of the modified hydrotalcite in this embodiment is as follows:

calcining Talc in muffle furnace at 500 deg.C for 5.5 hr, heating and refluxing, slowly dripping 0.014M modifier (1:1 mass ratio of sodium dodecyl sulfate and sodium dimethyldithiocarbamate to hydrotalcite, 1:0.75 mol ratio), adjusting pH to 10, continuously heating and refluxing for 3.5 hr, aging for 1 hr, centrifuging at 4200r/min rotation speed for 6min, separating to obtain solid, and drying at 80deg.C for 24 hr to obtain modified hydrotalcite.

Example 6:

the preparation of chiral binaphthol-derived selenium/sulfide of formula B differs from example 5 in that: the supported elemental sulfur was prepared in this example.

The process for the preparation of supported elemental sulphur differs from example 5 in that: modified hydrotalcite was prepared in this example.

The preparation of the modified hydrotalcite differs from example 5 in that: an equimolar amount of sodium lauryl sulfate was used instead of sodium dimethyl dithiocarbamate.

Example 7:

The preparation method of the supported elemental sulfur is different from that of the embodiment 5 in that: hydrotalcite is adopted to replace modified hydrotalcite.

Example 8:

an application example of chiral binaphthyl dithiol derivative selenium/sulfide is that the catalyst is applied to an example of organic chiral catalytic reaction, and the synthetic route of a specific application scene is as follows:

the preparation process comprises the following steps:

under the condition of no water and oxygen, at room temperature, a benzene alkyne substrate I-0 (0.05 mmol), a selenoaryl reagent substrate I-1 (0.06 mmol),(S)Adding (0.005 mmol) of A and (0.05 mmol) of boron trifluoride diethyl etherate into a reaction tube, adding ultra-dry dichloromethane (1 mL) at room temperature, reacting in argon atmosphere for two days, performing post-treatment reaction, and purifying by vacuum distillation and silica gel column to obtain selenoaryl-substituted axial chiral product I (36% yield, 9% ee;)α] _D ²⁰ = -104.00 (c = 0.1, CHCl ₃ )）。 ¹ H NMR (400 MHz, Chloroform-d) δ 8.23 (dd, J = 26.7, 8.2 Hz, 2H), 7.70 (dd, J = 7.9, 1.4 Hz, 1H), 7.52 (t, J = 7.6 Hz, 1H), 7.40 (m, 2H), 7.23 (d, J= 4.2 Hz, 2H), 7.18 – 6.98 (m, 3H), 6.68 (d, J = 7.7 Hz, 1H), 3.04 (q, J = 8.1 Hz, 2H), 2.75 (t, J = 7.6 Hz, 2H), 1.97 (s, 3H); ¹³ C NMR (101 MHz, CDCl ₃ ) δ 141.81, 135.83, 135.03, 134.71, 133.96, 132.50, 131.31, 130.08, 129.34, 128.73, 127.87, 127.40, 127.19, 126.42, 126.31, 12454, 121.85, 117.49, 32.11, 29.76, 24.72; as shown in fig. 9-10. In the experimental process, HPLC is adopted to separate enantiomer, and experimental parameters are set: chromatographic Column, chiralcel Column IC, column temperature 30 ℃, mobile phase: n-hexane isopropanol=60:40 (v/v), flow rate 1 mL/min, secondary retention time: 18.13 min, main retention time: 13.95 min, er=45.7:54.3. As shown in fig. 11-12.

Example 9:

an example of application of a class of chiral binaphthyl dithiol-derived selenium/sulfide differs from example 8 in that: in equimolar amounts(S)-A and(S)-substitution of a mixture of B in a mixture of(S)-A and(S)the molar ratio of B is 1:0.35.

Example 10:

an example of the use of chiral binaphthol-like derived selenium/sulfide differs from example 8 in that: in equimolar amounts(S)-A and(S)-substitution of a mixture of C in a mixture of(S)-A and(S)the molar ratio of C is 1:1.

Example 11:

an example of the use of chiral binaphthol-like derived selenium/sulfide differs from example 8 in that: in equimolar amounts(S)-A and(S)-D, in the mixture, instead of the mixture of D(S)-A and(S)the molar ratio of D is 1:0.5.

Test example 1:

the yields of the compounds prepared in examples 1 to 7 are shown in table 1:

TABLE 1 yield results

Sample of	Yield/%
		Example 1	33
Example 2	40
		Example 3	55
Example 4	47
		Example 5	68
Example 6	56
		Example 7	49

As can be seen from the data analysis in Table 1, example 5 produced(S)The yield of B is significantly higher than that of example 2 and higher than that of example 6, while the effect of example 7 is better than that of example 2, and the effect of example 6 is better than that of example 7, indicating that the use of hydrotalcite as carrier material to support sulfur and then for the synthesis of the compound can effectively improve the reaction efficiency of the relevant steps in the chiral binaphthol derivative selenium/sulfide synthesis process, resulting in higher product yields; the hydrotalcite is improved by adopting the modifier, so that the structure of the hydrotalcite can be further improved, the sulfur-carrying capacity of the modified hydrotalcite is further improved, the modified hydrotalcite is better applied to a compound synthesis method, and the yield of a product is obviously improved; meanwhile, the sodium dimethyldithiocarbamate in the modifier has better effect of improving the product yield.

Test example 2:

the yields of the compounds synthesized in the application examples of examples 8 to 11 are shown in Table 2:

table 2 results of yields in examples of application

Sample of	Yield/%
		Example 8	36
Example 9	48
		Example 10	64
Example 11	53

As can be seen from the data analysis in Table 2, the compounds prepared by the present invention(S)A is used as a catalyst and applied to synthesis of axial chiral selenium-containing diaryl derivatives, and has certain catalytic activity; in the application scenario provided in examples 9 to 11, the yield of the synthesized target product was significantly higher than that of example 8, indicating that the use of(S)-B、(S)-C or(S)-D are respectively from(S)The compound use of the-A is applied to the synthesis of axial chiral selenium-containing diaryl derivatives, the synergistic enhancement effect is generated, the synthesis effect of target products can be obviously improved, and the product yield is obviously improved.

Test example 3:

characterization of modified hydrotalcite properties

Infrared sign

The test was performed using fourier infrared spectroscopy, and the sample was mixed with potassium bromide and tabletted, followed by infrared testing.

The above-described test was conducted on the modified hydrotalcite prepared in examples 5 to 6, and the results are shown in fig. 13. As can be seen from the analysis of the figure, in comparison with the infrared test spectrum of the modified hydrotalcite prepared in example 6, in the infrared spectrum of the modified hydrotalcite prepared in example 5, 1313cm ^-1 An infrared characteristic absorption peak of C-N bond appears nearby at 1283cm ^-1 An infrared characteristic absorption peak having a C=S bond at 1130cm appears nearby ^-1 The infrared characteristic absorption peak of the C-S bond appears nearby, and the above results indicate that the modified hydrotalcite in example 5 was successfully prepared.

Characterization of particle size distribution

The test was performed using a laser particle size distribution instrument, model BT9300, available from instrument co.

The above test was performed on the modified hydrotalcite prepared in example 5 to example 6, and the results are shown in table 3:

TABLE 3 particle size test results

Sample of	Particle size distribution Range (μm)
		Example 5	2.94-15.67
Example 6	1.23-18.15

From the data analysis in Table 3, the particle size distribution of the modified hydrotalcite prepared in example 5 was significantly smaller than that of example 6, indicating that the modified hydrotalcite prepared using sodium dimethyldithiocarbamate as a modifier had a narrower particle size distribution.

The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.

The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. The chemical structural general formula of the chiral binaphthyl dithiol derivative selenium/sulfide is shown as formula I or formula II:

I，/>

II；

wherein X is selected from Se or S.

2. The method for synthesizing chiral binaphthyl dithiol derivative selenium/sulfide according to claim 1, which comprises the following steps: mixing chiral binaphthyl dithiol derivatives with phosphorus trichloride, triethylamine and alkylamine, and generating chiral binaphthyl dithiol derivative selenium/sulfide under the combined action of selenium powder or sulfur powder and a solvent; the chemical structure of the chiral binaphthyl dithiol derivative is shown as a formula III:

III。

3. the method for synthesizing chiral binaphthol derivative selenium/sulfide according to claim 2, wherein the solvent comprises dichloromethane.

4. The method for synthesizing chiral binaphthyl dithiol derivative selenium/sulfide according to claim 2, wherein the molar ratio of triethylamine to phosphorus trichloride is 4-6:1.

5. The method for synthesizing chiral binaphthyl dithiol derivative selenium/sulfide according to claim 2, wherein the molar ratio of the alkylamine to the phosphorus trichloride is 0.9-1.1:1.

6. The method for synthesizing chiral binaphthol derivative selenium/sulfide according to claim 2, wherein the alkylamine comprises diisopropylamine or diisobutylamine.

7. Use of chiral binaphthyl dithiol derivative selenium/sulfide as a catalyst in the preparation of axial chiral selenium-containing diaryl derivatives as described in claim 1; the synthesis method of the axial chiral selenium-containing diaryl derivative comprises the following steps:

8. The use according to claim 7, wherein the catalyst further comprises a mixture of two chiral binaphthol-derived selenium/sulfide compounds.