CN108484518B - 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound and preparation method thereof - Google Patents
2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound and preparation method thereof Download PDFInfo
- Publication number
- CN108484518B CN108484518B CN201810445407.3A CN201810445407A CN108484518B CN 108484518 B CN108484518 B CN 108484518B CN 201810445407 A CN201810445407 A CN 201810445407A CN 108484518 B CN108484518 B CN 108484518B
- Authority
- CN
- China
- Prior art keywords
- methylbenzoxazole
- reaction
- compound
- copper
- trimethylphenylseleno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention relates to a 2- (2, 4, 6-trimethylbenzene seleno) -5-methylbenzoxazole compound and a preparation method thereof, in an organic solvent, 5-methylbenzoxazole and 2, 4, 6-trimethyliodobenzene are used as reaction raw materials, elemental selenium is used as a selenylation reagent, and the 2- (2, 4, 6-trimethylbenzene seleno) -5-methylbenzoxazole compound is obtained through a series reaction under the co-promotion action of a copper catalyst and alkali. The method has simple reaction conditions and high yield and purity of the product, develops a new synthetic route and method for the 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound, and has good application potential and research value.
Description
Technical Field
The invention belongs to the technical field of organic compound synthesis, and particularly relates to a 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound and a preparation method thereof.
Background
Selenium has the functions of resisting cancer and oxidation, enhancing human immunity, antagonizing harmful heavy metals, regulating vitamin absorption, regulating protein synthesis in human body and enhancing reproductive function, is also an important component of peroxidase in muscle and seminal plasma, and is called as 'anticancer king' of human body trace elements by scientists.
To date, a number of pharmaceutical molecules containing a selenide structure have been developed in a number of specific application areas such as medicine, chemical: ebselen (Ebselen) is a novel anti-inflammatory agent developed by the first pharmaceutical agent in japan and Nattermann, germany, and is currently in clinical phase III research; a selenium-containing tegafur thiophosphate compound with antitumor activity, a selenized and modified south isatis root polysaccharide compound with the inhibiting effect on various tumor cell strains. Even in the agricultural field, the selenoether compounds are structurally broad-spectrum in fungicides and herbicides, such as selenotriazolamides, which are used as herbicides for crops. A large number of scientific researches show that selenium is an active ingredient constituting glutathione peroxidase, is used as a free radical inhibitor, effectively prevents the oxidative damage of islet beta cells, promotes the metabolism of sugar, reduces blood sugar and urine sugar, and improves the symptoms of diabetics, and cysteine and methionine required by a human body are selenium-containing compounds.
Because of the importance of the compounds containing selenide structures, a great deal of research on the synthesis of the compounds, especially the synthesis of asymmetric diaryl selenide compounds, has been carried out, and a plurality of synthetic routes and methods have been explored at present:
in 2009, VP Reddy et al (chip Oxide nanoparticles-catalyst Coupling of Diaryl Diselenide with Aryl Halides unit Ligand-Free conditions. org lett.2009, 11, 951-953.) reported that nano Copper Oxide Catalyzed the synthesis of an asymmetric diarylselenide compound with a diaryldiselenide compound under strongly alkaline conditions, however, this reaction requires the prior preparation of a diaryldiselenide compound, of the formula:
VG Ricordi et al (Glycerols a Recyclable Solvent for Copper-Catalyzed Cross-Coupling Reactions of Diaryl Diselenides with Aryl boron acids. Green chem.2012, 14, 1030-1034.) in 2012 reported that cuprous iodide catalyzes arylboronic acids and Diaryl diselenide compounds to obtain asymmetric Diaryl selenide compounds under the condition of strong polar Solvent DMSO, and had the defect that the reaction requires the preparation of arylboron reagents and Diaryl Diselenides in advance, which increases the synthesis cost, and the reaction formula is as follows:
in 2016, RU Kumar et al (Metal free synthesis of Diaryl selectides using SeO)2As a selenium source tetrahedron letters.2016, 57, 4138-:
in 2015, Longzhi Zhu et al (Copper-media Remote C-H Bond study of quench on the C5 position. org Lett.2015, 17, 5528-E5531.) reported arylselenylation reactions of C5-C-H bonds of quinoline under transition metal Copper catalysis using diaryl diselenide as the arylselenylation reagent, the reaction formula is as follows:
vanessa G.Ricordi et al (Copper-catalyst Direct aryl selection of anilides by C-H Bond Cleavage.adv.Synth.Catal.2015, 357, 933-939.) report Copper Catalyzed arylselenylation of a diaryldiselenide with an aniline at the para-C-H Bond to give a diarylselenide compound of the formula:
in 2017, a topic group of people in (Copper-catalyzed ipso-selection of aromatic carboxylic acids, org. biomol. chem., 2017, 15, 9718-:
benzoxazole class of very important nitrogen-containing fused heterocyclic compounds are important lead frameworks and synthons for organic synthesis, and the benzoxazole frameworks are widely present in natural products and candidate drug molecules, such as a natural product UK-1 of bisbenzoxazole and a divalent cation carrier A23187; the compounds derived from the compounds have extremely high biological activity, and have remarkable anti-tumor, anti-inflammatory, antibacterial and bactericidal effects, melatonin receptor antagonist and the like, so the compounds are always the research hotspots in the fields of pesticides and medicines. However, the research method for introducing the arylseleno functional group on the benzoxazole skeleton has not been reported so far, and the need for continuous research and exploration still exists, which is the basis and the motivation for the completion of the present invention.
Disclosure of Invention
The applicant intends to show that the solution according to the invention is implemented under the funding of the national science foundation (number: 21602158), here denoted thank you.
The first technical problem to be solved by the invention is the problem of the synthetic route of the 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound.
The second technical problem to be solved by the invention is that the preparation process of the 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound is suitable for large-scale industrial production.
In order to solve the technical problems, the invention provides the following technical scheme:
a2- (2, 4, 6-trimethylbenzene seleno) -5-methylbenzoxazole compound and a preparation method thereof are disclosed, in an organic solvent, 5-methylbenzoxazole with a structure shown as a formula (I) and 2, 4, 6-trimethyliodobenzene with a structure shown as a formula (II) are used as reaction raw materials, elemental selenium is used as a selenylation reagent, and under the co-promotion action of a copper catalyst and alkali, the C-H bond arylseleno of the compound shown as the formula (I) is subjected to a tandem reaction to obtain the 2- (2, 4, 6-trimethylbenzene seleno) -5-methylbenzoxazole compound with the structure shown as the formula (III).
The above reaction process can be represented by the following reaction formula:
the molar ratio of the 5-methylbenzoxazole with the structure shown in the formula (I) to the 2, 4, 6-trimethyliodobenzene with the structure shown in the formula (II) is 1: 1-1: 5, and the preferential ratio is 1: 3; the molar ratio of the 5-methylbenzoxazole with the structure shown in the formula (I) to the elemental selenium is 1: 1-1: 5, and the preferable ratio is 1: 3.
(1) Copper catalyst
The copper catalyst in the invention is at least one of cuprous chloride, cuprous iodide, cuprous bromide, copper oxide, cupric chloride, cupric bromide, cupric fluoride, copper trifluorosulfonate, copper acetylacetonate, copper acetate, copper powder and cuprous thiocyanate, preferably cupric acetate; the amount of copper catalyst used is, on a molar basis, from 1 to 10%, preferably 10%, of the amount of compound of formula (I) used.
(2) Alkali
The alkali in the invention is at least one of lithium carbonate, cesium carbonate, potassium carbonate, sodium carbonate, ammonium bicarbonate, sodium acetate, lithium acetate, potassium phosphate, sodium tert-butoxide, potassium fluoride, sodium fluoride, lithium tert-butoxide or potassium tert-butoxide, and preferably ammonium bicarbonate; the ratio of the ammonium bicarbonate to the formula (I) is 1: 1-1: 5, preferably 1: 3, calculated on a molar basis.
(3) Organic solvent
The reaction solvent in the invention is an organic solvent, and the organic solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, polyethylene glycol, dichloromethane, ethyl acetate, pyridine, N-hexane, 1, 4-dioxane, 1, 2-dichloroethane, toluene, tetrahydrofuran, methanol, diethyl ether, carbon tetrachloride, chloroform and N-butanol, preferably N, N-dimethylformamide.
(4) Reaction temperature
In the production process of the present invention, the reaction temperature is 80 to 140 ℃ and may be, for example, but not limited to, 80 ℃, 100 ℃, 120 ℃ and 140 ℃, and the reaction temperature is preferably 140 ℃.
(5) Reaction time
In the production method of the present invention, the reaction time is not particularly limited, and a suitable reaction time can be determined by, for example, detecting the residual percentage of the objective product or raw material by liquid chromatography, and is usually 15 to 24 hours, such as 15 hours, 17 hours, 19 hours, 21 hours, 23 hours, or 24 hours, but is not limited thereto, and the reaction time is preferably 24 hours.
(6) Separating and purifying
The mixture obtained after the reaction can be further separated and purified to obtain a purer final product. The method for separation and purification is well known to those skilled in the art, and for example, extraction, column chromatography, distillation, filtration, centrifugation, washing, fractionation and adsorption, or a combination of at least two methods can be used for separation and purification, such as extraction and column chromatography.
Of course, if desired, the reaction mixture obtained can also be introduced directly into other processes for direct reaction to produce other products. Alternatively, the reaction mixture may be subjected to one or more of pretreatment, for example, concentration, extraction and distillation under reduced pressure, prior to introduction into other processes, to obtain a crude product or a pure product, which is then introduced into other processes.
In a preferred embodiment, the post-treatment step after the reaction is completed may be as follows: after the reaction is finished, cooling the reaction liquid, adding ethyl acetate for filtration, concentrating under reduced pressure, separating the concentrate by column chromatography (wherein the silica gel is 300-400-mesh silica gel), taking the mixed liquid of petroleum ether and ether as an eluent, collecting the eluent, and concentrating to obtain the target product.
The preparation method of the 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound provided by the invention has the following beneficial effects:
a) the reaction is efficient, the yield is high, the post-treatment is simple, and the operation is simple and convenient;
b) the alkali and copper catalysts are cheap and easy to obtain;
c) elemental selenium is used as a selenylation reagent;
d) the reaction efficiency is higher after the reaction is amplified.
The invention takes easily prepared 5-methylbenzoxazole with a structure shown as (I) and 2, 4, 6-trimethyliodobenzene with a structure shown as formula (II) as reaction raw materials, takes elemental selenium as a selenylation reagent, and reacts under the co-promotion action of a transition metal copper catalyst and alkali in a nitrogen reaction atmosphere to obtain the 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound with a structure shown as formula (III). The reaction conditions and the post-treatment operation are simple, and the method is suitable for large-scale industrial production.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.
The data and purity of the novel compounds given in the following examples were determined by nuclear magnetic resonance.
Example 1
Synthesis of 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole
At room temperature, 2, 4, 6-trimethyliodobenzene (1.2mmol, 3equiv), elemental selenium (1.2mmol, 3equiv), 5-methylbenzoxazole (0.4mmol, 1equiv), Cu (OAc)2(0.04mmol), ammonium bicarbonate (1.2mmol, 3equiv) were added to the reaction tube, then nitrogen was charged and replaced three times, under a nitrogen reaction environment, then 2mL of DMF reaction solvent was added, stirred at 140 ℃ reaction temperature for 24 h. After the reaction is monitored by thin-layer chromatography, the reaction mixture is cooled, ethyl acetate is added for dilution, the diluted solution is transferred to a separating funnel, saturated saline solution is used for extraction, a water phase and an organic phase are separated, the water phase is extracted for 3 times by the ethyl acetate, the organic phase is combined, 5g of anhydrous sodium sulfate is added, the mixture is kept still for 30min, 5mL of ethyl acetate is used for washing a filter cake for 3 times each time, then the solvent is removed by spinning off, and the product is obtained by column chromatography separation (eluent: petroleum ether: ether ═ 98: 2), is a yellow solid, has the melting point of 119-. The data of the nuclear magnetic resonance hydrogen spectrum of the obtained product are as follows:
1H NMR(500MHz，CDCl3)：δ7.38(s 1H)，7.26-7.24(m，1H)，7.03(s，2H)，7.00(d，J＝8.3Hz，1H)，2.51(s，6H)，2.41(s，3H)，2.32(s，3H)；
the data of the nuclear magnetic resonance carbon spectrum of the obtained product are as follows:
13C NMR(125MHz，CDCl3)：δ158.4，150.9，143.5，142.6，140.2，133.9，129.2，124.8，123.4，118.8，109.3，24.4，21.4，21.1；
theoretical calculations and experimental results of high resolution mass spectrometry performed on the product are as follows:
HRMS(ESI)：calcd for C17H17NOSe[M+H]+332.0548，found 332.0547。
example 2
Amplified synthesis of 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole
At room temperature, 2, 4, 6-trimethyliodobenzene (12mmol, 3equiv), elemental selenium (12mmol, 3equiv), 5-methylbenzoxazole (4mmol, 1equiv), Cu (OAc)2(0.4mmol), ammonium bicarbonate (12mmol, 3equiv) were added to the reaction tube, then nitrogen was charged and replaced three times, under a nitrogen reaction environment, then 20mL of DMF reaction solvent was added, stirred at 140 ℃ reaction temperature for 24 h. After the reaction was monitored by thin layer chromatography, the reaction mixture was cooled, then ethyl acetate was added to dilute the reaction mixture, the diluted solution was transferred to a separatory funnel, extracted with saturated brine, the aqueous phase and the organic phase were separated, the aqueous phase was extracted with ethyl acetate 3 times, the organic phases were combined, 25g of anhydrous sodium sulfate was added, the mixture was allowed to stand for 30min, the filter cake was washed with 50mL of ethyl acetate 3 times each time, then the solvent was spun off, and the product was isolated by column chromatography (eluent: petroleum ether: ether ═ 98: 2) at a yield of 90% and a product weight of 1.191 g.
As can be seen from the above examples 1-2, when the method of the present invention is employed, 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole can be obtained in high yield and high purity.
Examples 3 to 14
Examples 3 to 14 were each carried out in the same manner as in example 1 with the highest product yield except that the catalyst copper acetate therein was replaced with the following copper catalyst, respectively, and the yields of the copper compound used and the corresponding product are shown in table 1 below.
TABLE 1
As can be seen from Table 1 above, the product yields are all greatly reduced when other copper compounds are used. Thus, the catalyst copper acetate used in the invention has high catalytic performance for the reaction.
Examples 15 to 27
Examples 15-27 were each carried out in the same manner as example 1 with the highest product yield except that the alkali ammonium bicarbonate therein was replaced with the following inorganic base, respectively, and the yields of the alkali compound and the corresponding product used are shown in table 2 below.
TABLE 2
| Numbering | Alkali | Reaction yield (%) |
| Example 15 | Lithium carbonate | Is not reacted |
| Example 16 | Sodium carbonate | Is not reacted |
| Example 17 | Cesium carbonate | Is not reacted |
| Example 18 | Potassium phosphate | Is not reacted |
| Example 19 | Sodium phosphate | Is not reacted |
| Example 20 | Lithium tert-butoxide | Is not reacted |
| Example 21 | Sodium tert-butoxide | Is not reacted |
| Example 22 | Potassium tert-butoxide | Is not reacted |
| Example 23 | Sodium acetate | Is not reacted |
| Example 24 | Lithium acetate | Is not reacted |
| Example 25 | Potassium acetate | Is not reacted |
| Example 26 | Potassium fluoride | Is not reversedShould be taken |
| Example 27 | Sodium fluoride | Is not reacted |
As can be seen from Table 2 above, almost none of the bases reacted when used, thus demonstrating that ammonium bicarbonate was the key factor in the success of the reaction and was most effective in the reaction system.
Examples 28 to 42
Examples 28 to 42 were each carried out in the same manner as in example 1 with the highest product yield except that the organic solvent N, N-dimethylformamide therein was replaced with the following organic solvents, respectively, and the organic solvents used and the yields of the corresponding products are shown in Table 3 below.
TABLE 3
As can be seen from table 3 above, when other organic solvents were used, the yield was still significantly reduced, except that the reaction could occur in the strongly polar solvent DMSO; without any product under non-polar or even weakly coordinating solvent conditions. This demonstrates that the proper choice of organic solvent has a significant, even decisive influence on whether the reaction can proceed.
In summary, it is clear from all the above embodiments that, when the method of the present invention is adopted, i.e. a complex reaction system composed of a copper compound as a catalyst (especially copper acetate), a base (especially ammonium bicarbonate) and a suitable organic solvent (especially N, N-dimethylformamide) is used, the 2, 4, 6-trimethyliodobenzene, elemental selenium and 5-methylbenzoxazole can be subjected to a tandem reaction to synthesize the 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound with high yield and high purity, and a completely new synthetic route is provided for the efficient and rapid synthesis of the compounds.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments are modified or some or all of the technical features are equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A preparation method of a 2- (2, 4, 6-trimethylbenzene seleno) -5-methylbenzoxazole compound is characterized in that 5-methylbenzoxazole and 2, 4, 6-trimethyliodobenzene are used as reaction raw materials in an organic solvent, elemental selenium is used as a selenylation reagent, and under the common promotion action of a copper catalyst and alkali, the 2- (2, 4, 6-trimethylbenzene seleno) -5-methylbenzoxazole compound is obtained through a series reaction;
the 5-methylbenzoxazole is:
the 2, 4, 6-trimethyl iodobenzene is prepared from the following components:
the 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound is as follows:
the copper catalyst is copper acetate;
the alkali is ammonium bicarbonate;
the organic solvent is N, N-dimethylformamide.
2. The production method according to claim 1, wherein the amount of the copper catalyst is 10% by mole of the amount of the 5-methylbenzoxazole.
3. The method of claim 1, wherein: the molar ratio of the 5-methylbenzoxazole to the base is 1: 1-1: 5.
4. The method of claim 1, wherein: the molar ratio of the 5-methylbenzoxazole to the 2, 4, 6-trimethyliodobenzene is 1: 1-1: 5.
5. The method of claim 1, wherein: the molar ratio of the 5-methylbenzoxazole to the elemental selenium is 1: 1-1: 5.
6. The method of claim 1, wherein the reaction temperature is 80-140 ℃.
7. The method of claim 1, wherein the reaction time is 15 to 30 hours.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810165275 | 2018-02-19 | ||
| CN2018101652759 | 2018-02-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108484518A CN108484518A (en) | 2018-09-04 |
| CN108484518B true CN108484518B (en) | 2021-06-15 |
Family
ID=63353889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810445407.3A Active CN108484518B (en) | 2018-02-19 | 2018-05-04 | 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484518B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357805B (en) * | 2019-06-19 | 2020-11-17 | 温州医科大学 | Preparation method of N-methyl-3-phenylseleno maleimide compound |
| CN110982806B (en) * | 2019-08-30 | 2022-09-02 | 浙江工业大学 | Protein aryl derivative and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387311A (en) * | 2014-12-03 | 2015-03-04 | 温州大学 | Synthetic method of 3-arylselanyl indole compound |
| CN106565629A (en) * | 2016-10-27 | 2017-04-19 | 温州大学 | Synthesis method of 2-phenylselenic benzothiazole compound |
| CN107056727A (en) * | 2017-03-29 | 2017-08-18 | 温州医科大学 | A kind of oxadiazole compound of 5 arylseleno of 2 aryl 1,3,4 and preparation method |
| CN107188841A (en) * | 2017-05-16 | 2017-09-22 | 温州医科大学 | A kind of synthetic method of asymmetric diaryl list selenide compound |
-
2018
- 2018-05-04 CN CN201810445407.3A patent/CN108484518B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387311A (en) * | 2014-12-03 | 2015-03-04 | 温州大学 | Synthetic method of 3-arylselanyl indole compound |
| CN106565629A (en) * | 2016-10-27 | 2017-04-19 | 温州大学 | Synthesis method of 2-phenylselenic benzothiazole compound |
| CN107056727A (en) * | 2017-03-29 | 2017-08-18 | 温州医科大学 | A kind of oxadiazole compound of 5 arylseleno of 2 aryl 1,3,4 and preparation method |
| CN107188841A (en) * | 2017-05-16 | 2017-09-22 | 温州医科大学 | A kind of synthetic method of asymmetric diaryl list selenide compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108484518A (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107056727B (en) | 2-aryl-5-arylseleno-1, 3, 4-oxadiazole compound and preparation method thereof | |
| CN109651225B (en) | Preparation method of 1-methyl-3-morphinyl-4-arylmercapto maleimide compound | |
| CN107188841B (en) | A kind of synthetic method of asymmetry diaryl list selenide compound | |
| CN107188846B (en) | A kind of synthetic method of arylseleno heterocyclic compound | |
| CN108484518B (en) | 2- (2, 4, 6-trimethylphenylseleno) -5-methylbenzoxazole compound and preparation method thereof | |
| CN108675961B (en) | 1-methyl-2- (2, 4, 6-trimethylphenylseleno) benzimidazole compound and preparation method thereof | |
| CN108675948A (en) | A kind of beta-hydroxy selenide compound and preparation method | |
| CN108864097B (en) | 2-arylseleno theophylline compound and preparation method thereof | |
| CN108863878A (en) | A kind of beta-hydroxy selenide compound and preparation method | |
| CN108558785B (en) | 5-aryl-2-arylseleno-1, 3-oxazole compound and preparation method thereof | |
| CN107033048B (en) | A kind of synthetic method of aryl methyl selenide compound | |
| CN108912045B (en) | 2-phenylselenoquinoline compound and preparation method thereof | |
| CN108863971B (en) | 2- (2, 4, 6-trimethylphenylseleno) -1, 3-oxazole-5 ethyl carboxylate compound and preparation method thereof | |
| CN108912026B (en) | Alkynyl alkyl selenide compound and preparation method thereof | |
| CN109761918B (en) | N1- (2,2, 2-trifluoro-1-aryl ethyl) -triazole derivative and synthesis method thereof | |
| CN111620800B (en) | Method for preparing aryl methyl selenide compound by decarboxylation, selenylation and methylation of aromatic carboxylic acid | |
| CN108440384B (en) | Process for the preparation of trifluoromethylated derivatives of isoindolones | |
| CN115850142A (en) | Synthesis method of 7Z vitamin D compound | |
| CN106905358B (en) | Preparation of vitamin D3Process for preparing analogue intermediates | |
| CN108689892A (en) | 3- sulfonylations-indane ketone compounds and preparation method thereof | |
| CN108658822B (en) | Aryl alkyl selenide compound and preparation method thereof | |
| CN111793013B (en) | Synthetic method for preparing aryl methyl selenide compound from selenium methyl bunnt salt and arylboronic acid | |
| CN111925310A (en) | 3-amino-4-arylseleno maleimide compound and preparation method thereof | |
| CN114349813A (en) | Preparation method of cherokee rose fruit sapogenin (RLMS) structure-modified compound | |
| CN106496087B (en) | A kind of method by the decarboxylation coupling reaction one pot process compound of class containing selenium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |