CN108863971B - 2- (2, 4, 6-trimethylphenylseleno) -1, 3-oxazole-5 ethyl carboxylate compound and preparation method thereof - Google Patents
2- (2, 4, 6-trimethylphenylseleno) -1, 3-oxazole-5 ethyl carboxylate compound and preparation method thereof Download PDFInfo
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- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
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Abstract
The invention relates to a 2- (2, 4, 6-trimethylphenylseleno) -1, 3-oxazole-5 carboxylic acid ethyl ester compound and a preparation method thereof, wherein in an organic solvent, 1, 3-oxazole-5 carboxylic acid ethyl ester 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-trimethylphenylseleno) -1, 3-oxazole-5 carboxylic acid ethyl ester 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) -1, 3-oxazole-5 carboxylic acid ethyl ester 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) -1, 3-oxazole-5 carboxylic acid ethyl ester 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.
In addition, 1, 3-oxazole compounds are an important aromatic ring containing multiple heteroatoms, are important lead frameworks and synthons for organic synthesis, and the parent nucleus of the 1, 3-oxazole compounds is widely present in many natural products and bioactive drug molecules, such as: commercial etoxazole (etoxazole) and insect growth regulator (2, 5-bis (2, 4-dichlorophenyl) -1, 3, 4-oxazole) are continuously researched by pharmacologists, a large number of 1, 3-oxazole derivatives are synthesized, and have wide biological activity, so that a new space is developed for the development of medicine and pesticide chemistry, and a new way is provided for searching for a novel high-efficiency and low-toxicity medicine, however, a research method for introducing an arylseleno functional group to a 5-carboxylate-1, 3-oxazole framework is not reported so far, and the need of continuous research and exploration still exists, which is the basis and the motive force for completing the 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 a synthetic route of the 2- (2, 4, 6-trimethylphenylseleno) -1, 3-oxazole-5 carboxylic acid ethyl ester compound.
The second technical problem to be solved by the invention is that the preparation process of the 2- (2, 4, 6-trimethylphenylseleno) -1, 3-oxazole-5 carboxylic acid ethyl ester 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) -1, 3-oxazole-5 ethyl carboxylate compound and a preparation method thereof are disclosed, in an organic solvent, 1, 3-oxazole-5 ethyl carboxylate with a structure shown in a formula (I) and 2, 4, 6-trimethyliodobenzene with a structure shown in 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 2- (2, 4, 6-trimethylbenzene seleno) -1, 3-oxazole-5 ethyl carboxylate compound with a structure shown in a formula (III) is obtained through the series connection reaction of C-H bond arylseleno of the compound shown in the formula (I).
The above reaction process can be represented by the following reaction formula:
the molar ratio of the 1, 3-oxazole-5 carboxylic acid ethyl ester with the structure shown in the formula (I) to the 2, 4, 6-trimethyl iodobenzene with the structure shown in the formula (II) is 1: 1-1: 5, and the preferable ratio is 1: 3; the molar ratio of the 1, 3-oxazole-5 carboxylic acid ethyl ester with the structure shown in the formula (I) to the elemental selenium is 1: 1-1: 5, and preferably 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 chloride; 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, preferably potassium phosphate; the ratio of the amount of potassium phosphate to the amount of formula (I) is 1: 1 to 1: 5, preferably 1: 3, 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) -1, 3-oxazole-5 carboxylic acid ethyl ester 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 1, 3-oxazole-5 carboxylic acid ethyl ester with a structure shown in formula (I) and 2, 4, 6-trimethyl iodobenzene with a structure shown in 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-trimethyl phenylseleno) -1, 3-oxazole-5 carboxylic acid ethyl ester compound with a structure shown in 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) -1, 3-oxazole-5 carboxylic acid ethyl ester compound
2, 4, 6-trimethyliodobenzene (1.2mmol, 3equiv), elemental selenium (1.2mmol, 3equiv), ethyl 1, 3-oxazole-5-carboxylate (0.4mmol, 1equiv), copper chloride (0.04mmol), potassium phosphate (1.2mmol, 3equiv) were added to the reaction tube at room temperature, then nitrogen was charged and replaced three times, and under a nitrogen reaction environment, 2ml of an N-dimethylformamide reaction solvent was then added, and stirred at a reaction temperature of 140 ℃ for 24 hours. 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, 5g of anhydrous sodium sulfate was added, the mixture was allowed to stand for 30min, the filter cake was washed with 5mL of ethyl acetate 3 times each time, then the solvent was spun off, and the product was obtained by column chromatography (eluent: petroleum ether: ether ═ 98: 2), which was a yellow solid, with a melting point of 68-69 ℃, a yield of 68%, and a weight of 92 mg.
The data of the nuclear magnetic resonance hydrogen spectrum of the obtained product are as follows:
1H NMR(500MHz，CDCl3)：δ7.62(s1H)，7.01(s，2H)，4.34(q，J＝7.1Hz，2H)，2.48(s，6H)，2.30(s，3H)，1.35(t，J＝7.1Hz，3H)。
the data of the nuclear magnetic resonance carbon spectrum of the obtained product are as follows:
13C NMR(125MHz，CDCl3)：δ159.3，157.4，145.2，143.3，140.6，135.5，129.3，129.0，123.2，61.3，24.3，21.1，14.2。
theoretical calculations and experimental results of high resolution mass spectrometry performed on the product are as follows:
HRMS(ESI)：calcd for C15H17NO3Se[M+H]+340.0447，found 340.0463。
example 2
Amplified synthesis of 2- (2, 4, 6-trimethylphenylseleno) -1, 3-oxazole-5 carboxylic acid ethyl ester compound
2, 4, 6-trimethyliodobenzene (12mmol, 3equiv), elemental selenium (12mmol, 3equiv), ethyl 1, 3-oxazole-5-carboxylate (4mmol, 1equiv), copper chloride (0.4mmol), potassium phosphate (12mmol, 3equiv) were added to a reaction tube at room temperature, then nitrogen gas was charged and replaced three times, under a nitrogen gas reaction environment, then 20mL of N, N-dimethylformamide reaction solvent was added, and stirred at a reaction temperature of 140 ℃ for 24 hours. 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 obtained by column chromatography (eluent: petroleum ether: ether ═ 98: 2), with a yield of 77%, and a product weight of 1.044 g.
As can be seen from the above examples 1-2, when the method of the present invention is employed, the ethyl 2- (2, 4, 6-trimethylphenylseleno) -1, 3-oxazole-5 carboxylate compound 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 copper chloride catalyst was replaced with the copper catalyst as follows, respectively, and the yields of the copper compound used and the corresponding products are shown in table 1 below.
TABLE 1
| Numbering | Copper catalyst | Reaction yield (%) |
| Example 4 | Is not reacted | |
| Example 5 | Cuprous chloride | 29 |
| Example 6 | Copper acetate | 24 |
| Example 7 | Cuprous bromide | 44 |
| Example 8 | Copper oxide | 26 |
| Example 9 | Cuprous iodide | 33 |
| Example 10 | Copper bromide | 14 |
| Example 11 | Copper fluoride | 55 |
| Example 12 | Copper triflate | 31 |
| Example 13 | Copper acetylacetonate | 25 |
| Example 14 | Copper powder | Is not reacted |
| Example 15 | Cuprous thiocyanate | 19 |
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 chloride used in the invention has high catalytic performance for the reaction.
Examples 15 to 28
Examples 15 to 28 were each carried out in the same manner as in example 1 with the highest product yield except that the base potassium phosphate therein was replaced with the following inorganic base, respectively, and the yields of the base compound used and the corresponding products are shown in the following table 2.
TABLE 2
| Numbering | Alkali | Reaction yield (%) |
| Example 15 | Ammonium bicarbonate | Is not reacted |
| Example 16 | Lithium carbonate | Is not reacted |
| Example 17 | Sodium carbonate | Is not reacted |
| Example 18 | Cesium carbonate | Is not reacted |
| Example 19 | Potassium carbonate | Is not reacted |
| Example 20 | Sodium phosphate | Is not reacted |
| Example 21 | Lithium tert-butoxide | Is not reacted |
| Example 22 | Sodium tert-butoxide | Is not reacted |
| Example 23 | Potassium tert-butoxide | Is not reacted |
| Example 24 | Sodium acetate | Is not reacted |
| Example 25 | Lithium acetate | Is not reacted |
| Example 26 | Potassium acetate | Is not reacted |
| Example 27 | Potassium fluoride | Is not reacted |
| Example 28 | Sodium fluoride | Is not reacted |
As can be seen from Table 2 above, almost none of the bases reacted when other bases were used, thus demonstrating that potassium phosphate is a key factor in the success of the reaction and is most effective for the reaction system.
Examples 29 to 43
Examples 29 to 43 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
| Numbering | Solvent(s) | Reaction yield (%) |
| Example 29 | Dimethyl sulfoxide | 18 |
| Example 30 | Methanol | Is not reacted |
| Example 31 | Polyethylene glycol | Is not reacted |
| Example 32 | Methylene dichloride | Is not reacted |
| Example 33 | Ethyl acetate | Is not reacted |
| Example 34 | Pyridine compound | Is not reacted |
| Example 35 | N-hexane | 24 |
| Example 36 | 1, 4-dioxahexaalkane | Is not reacted |
| Example 37 | 1, 2-dichloroethane | Is not reacted |
| Example 38 | Toluene | Is not reacted |
| Example 39 | Tetrahydrofuran (THF) | Is not reacted |
| Example 40 | Ether (A) | Is not reacted |
| EXAMPLE 41 | Carbon tetrachloride | Is not reacted |
| Example 42 | Chloroform | Is not reacted |
| Example 43 | N-butanol | Is not reacted |
As can be seen from table 3 above, when other organic solvents were used, the reaction was able to occur with dimethyl sulfoxide, but the yield was still significantly reduced, except in the strongly polar solvent; 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 examples 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 chloride), a base (especially potassium phosphate), and a suitable organic solvent (especially N, N-dimethylformamide), the ethyl 1, 3-oxazole-5-carboxylate, elemental selenium and 2, 4, 6-trimethyliodobenzene can be subjected to a tandem reaction to synthesize the ethyl 2- (2, 4, 6-trimethylphenylseleno) -1, 3-oxazole-5-carboxylate compound with high yield and high purity, thereby providing a completely new synthetic route for the efficient and rapid synthesis of the compound.
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-trimethylphenylseleno) -1, 3-oxazole-5 ethyl carboxylate compound is characterized in that 1, 3-oxazole-5 ethyl carboxylate and 2, 4, 6-trimethyliodobenzene are used as reaction raw materials in an organic solvent, elemental selenium is used as a selenylation reagent, and the 2- (2, 4, 6-trimethylphenylseleno) -1, 3-oxazole-5 ethyl carboxylate compound is obtained through a series reaction under the coactivation effect of a copper catalyst and alkali;
the ethyl 1, 3-oxazole-5-carboxylate is:
the 2, 4, 6-trimethyl iodobenzene is prepared from the following components:
the 2- (2, 4, 6-trimethylphenylseleno) -1, 3-oxazole-5 ethyl carboxylate compound is:
the copper catalyst is copper chloride;
the base is potassium phosphate;
the organic solvent is N, N-dimethylformamide.
2. The preparation method according to claim 1, wherein the copper catalyst is used in an amount of 10% by mole based on the amount of ethyl 1, 3-oxazole-5-carboxylate.
3. The method of claim 1, wherein: the molar ratio of the 1, 3-oxazole-5 carboxylic acid ethyl ester to the base is 1: 1 to 1: 5.
4. The method of claim 1, wherein: the molar ratio of the 1, 3-oxazole-5 carboxylic acid ethyl ester to the 2, 4, 6-trimethyl iodobenzene is 1: 1-1: 5.
5. The method of claim 1, wherein: the molar ratio of the 1, 3-oxazole-5 carboxylic acid ethyl ester 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.
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| 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 |
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