CN112920150A - Method for preparing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone by catalytic oxidation - Google Patents
Method for preparing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone by catalytic oxidation Download PDFInfo
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- C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
Abstract
The invention discloses a method for preparing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone by catalytic oxidation. The method comprises the following steps: the method comprises the steps of taking a titanium silicalite molecular sieve as a catalyst, hydrogen peroxide as an oxidant and water as a reaction medium, and carrying out catalytic oxidation on 2, 5-furandimethanol at 15-100 ℃ for 20-120 min to obtain 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one. The method obtains the 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone through one-step catalytic oxidation process under mild conditions, realizes cleaner and more economic catalytic process, has the yield up to 95.2 percent, low cost, less by-products, environmental protection, higher atom economy and reaction efficiency, is easy to separate products, and has good industrial application prospect.
Description
Technical Field
The invention relates to a method for preparing bioactive molecules 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one by catalytic oxidation of 2, 5-furandimethanol with a titanium silicalite molecular sieve under mild and green conditions, belonging to the technical field of chemical synthesis.
Background
With the obvious problems of continuous consumption of fossil resources, increasingly severe environmental pollution and the like, the biomass and the derivatives thereof are functionalized through a plurality of reaction ways (such as oxidation, reduction, amination and the like), are gradually applied to modern organic synthesis and industrial production of bulk and fine chemicals, and are expected to become sustainable substitutes of petroleum-based chemicals. The Achmatowicz rearrangement reaction is an expanded ring oxidation reaction, and furan derivatives (alkyl substituted furan, furfuryl alcohol, alkyl substituted furfuryl alcohol and the like) can be oxidized into more complex and functionalized 6-hydroxy-2H-pyran-3 (6H) -ketone, wherein 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone is included. These pyrones contain a variety of functional groups that can be further transformed, and are valuable synthetic intermediates that play a key role in the synthesis of antibacterial agents, monosaccharides and their analogs, natural products, and pharmaceuticals (RSC adv.,2016,6, 111564-111598).
Pyrones are produced by Achmatowicz rearrangement using N-bromosuccinimide (NBS) and m-chloroperoxybenzoic acid (m-CPBA) as the most commonly used oxidants, but the use of these oxidants generates quantitative organic by-products of m-chlorobenzoic acid or succinimide, leading to a reduction in product purity, requiring timely column chromatographic separations (Green chem.,2019,21, 64-68). Other reported catalytic systems are vanadyl acetylacetonate (VO (acac)2) Or tetra (isopropoxy) titanium (Ti (O)i-Pr)4) In combination with tert-butyl hydroperoxide (TBHP) (org.Lett.,2013,15, 5088-2) Methanol (MeOH) (J.Org.chem.,1988,53, 1607-1611), metal complex ([ in (COD) Cl)]2) The synthesis processes related to benzyl alcohol (adv. Synth. Catal.2018,360, 595-599) are almost homogeneous reactions, and homogeneous catalysts are difficult to separate from liquid-phase reaction products, especially when noble metal complexes are used as the catalysts, the separation problem needs to be paid attention to, otherwise, the products are not economically polluted, and the next reaction is influenced. In addition, the reaction system usually requires an organic solvent, which reduces the "green index" of the reaction withoutThe yield of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one obtained by the ball milling method under solvent conditions is not ideal, only 45% -63% (Synth. Commun. 2015,45, 348-354). With the increasing attention of people on the environmental and energy problems in the green and sustainable technical field, the development of an environment-friendly, efficient and high atom economy synthetic method becomes an urgent need for preparing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one.
Disclosure of Invention
The invention mainly aims to provide a method for preparing bioactive molecule 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one by catalytically oxidizing 2, 5-furandimethanol with a titanium silicalite molecular sieve under mild reaction conditions, and with environmental friendliness, economy and high efficiency, so that the defects of the prior art are overcome.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a method for preparing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone by catalytic oxidation, which comprises the following steps:
the method comprises the steps of taking a titanium silicalite molecular sieve as a catalyst, hydrogen peroxide as an oxidant and water as a reaction medium, and carrying out catalytic oxidation on 2, 5-furandimethanol at 15-100 ℃ for 20-120 min to obtain 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one.
In some embodiments, the catalytic oxidation process for preparing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one comprises: uniformly mixing 2, 5-furandimethanol, a titanium silicalite molecular sieve, hydrogen peroxide and water, stirring the obtained mixed reaction system at 15-70 ℃ for reaction for 20-60 min, and performing one-step catalytic oxidation to obtain 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one.
In some embodiments, the ratio of silicon to titanium in the titanium silicalite molecular sieve is (15-80): 1.
compared with the prior art, the invention has the beneficial effects that at least:
1) the invention provides a method for synthesizing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone by one-step high-efficiency catalysis of 2, 5-furandimethanol oxidation by using a heterogeneous catalyst titanium silicalite molecular sieve and a cheap and environment-friendly oxidant (hydrogen peroxide) under mild conditions and using water as a reaction medium, so as to realize a cleaner and more economic catalytic process. Compared with the existing reports, the invention has innovation and industrialized application prospect.
2) Compared with the background technology, the method has obvious advancement, aims at the defects in the synthesis reaction of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone, adopts a heterogeneous catalyst, uses cheap and environment-friendly hydrogen peroxide as an oxidant, uses cleaner water as a reaction medium, has mild reaction conditions, low cost, few byproducts, yield of 95.2 percent, easy separation of products, environment friendliness, reusability of the catalyst, higher atom economy and green index, and good industrial application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic representation of the product of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one prepared in example 1 of the present invention;
FIG. 2 is a liquid chromatography-time-of-flight mass spectrometry chromatogram of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one prepared in example 10 of the present invention;
FIG. 3 is a liquid chromatography-time-of-flight mass spectrometry combined mass spectrum of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one prepared in example 10 of the present invention;
FIG. 4 is a UV absorption vs. visible spectrum of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one prepared in example 12 of the present invention.
Detailed Description
As described above, in view of the drawbacks of the prior art in the synthesis reaction of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one, the present inventors have conducted extensive research and practice to provide a technical solution of the present invention, which provides a method for efficiently catalyzing the oxidation synthesis of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one from 2, 5-furandimethanol to achieve a cleaner and more economical catalytic process under mild conditions by using a heterogeneous catalyst titanium silicalite molecular sieve and an inexpensive and environmentally-friendly oxidant (hydrogen peroxide) and directly using clean water as a reaction medium. Compared with the existing reports, the invention has innovation and industrialized application prospect.
The reaction mechanism of the one-step catalytic oxidation of 2, 5-furandimethanol to prepare the bioactive molecule 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one may consist in the direct epoxidation of one double bond in furan ring, and the reaction formula is as follows:
wherein I is 2, 5-furandimethanol and II is 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one; the reaction temperature is 15-100 ℃, and the reaction time is 20-120 min.
The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a method for preparing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one by catalytic oxidation with mild reaction conditions, environmental friendliness, economy and high efficiency, comprising:
the method comprises the steps of taking a titanium silicalite molecular sieve as a catalyst, hydrogen peroxide as an oxidant and water as a reaction medium, and carrying out catalytic oxidation on 2, 5-furandimethanol at 15-100 ℃ for 20-120 min to obtain 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one.
In some embodiments, the catalytic oxidation process for preparing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one comprises: the method comprises the steps of taking a titanium silicalite molecular sieve as a catalyst, taking 2, 5-furandimethanol as a reaction raw material, reacting in the presence of a hydrogen peroxide oxidizing agent and water as a reaction medium under mild conditions (15-70 ℃ for 20-60 min), and obtaining the 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one through a one-step catalytic oxidation process.
In some more specific embodiments, the catalytic oxidation process for preparing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one comprises:
uniformly mixing 2, 5-furandimethanol, a titanium silicalite molecular sieve, hydrogen peroxide and water, stirring the obtained mixed reaction system at 15-70 ℃ for reaction for 20-60 min, and performing one-step catalytic oxidation to obtain 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one.
In some preferred embodiments, the ratio of silicon to titanium in the titanium silicalite catalyst is (15-80): 1, preferably, the silicon-titanium ratio is (30-50): 1.
in some preferred embodiments, the mass ratio of the titanium silicalite catalyst to the 2, 5-furandimethanol raw material is (0.1-20): preferably, the mass ratio of the catalyst to the raw materials is (0.4-5.0): 1.
in some preferred embodiments, the reaction feedstock, 2, 5-furandimethanol (BHMF), is obtained after reduction of 5-hydroxymethylfurfural.
In some preferred embodiments, the mass concentration of 2, 5-furandimethanol in the mixed reaction system is 1g/L to 50g/L, preferably 5g/L to 25 g/L. That is, the mass concentration of 2, 5-furandimethanol in the reaction medium water is 1g/L to 50g/L, and the substrate concentration is preferably 5g/L to 25 g/L.
In some preferred embodiments, the oxidant hydrogen peroxide is an aqueous hydrogen peroxide solution with a mass concentration of 30% to 50%.
In some preferred embodiments, the concentration of the oxidizing agent in the mixed reaction system is 0.02mol/L to 10mol/L, preferably 0.04mmol/L to 2 mol/L. That is, the concentration thereof in the reaction medium water is 0.02mol/L to 10mol/L, preferably 0.04mmol/L to 2 mol/L.
In some preferred embodiments, the temperature of the reaction is from 15 ℃ to 100 ℃, preferably from 25 ℃ to 70 ℃.
In some preferred embodiments, the reaction time is 20min to 120min, preferably 30min to 60 min.
Further, the process has a 2, 5-furandimethanol conversion of above 90% and a 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one yield of above 75%.
In conclusion, the method for synthesizing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone by using the heterogeneous catalyst titanium silicalite molecular sieve and the cheap and environmentally-friendly oxidant (hydrogen peroxide) under the mild condition and directly using water as a reaction medium and performing one-step high-efficiency catalysis on 2, 5-furandimethanol to oxidize and synthesize the 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone has the advantages of cleaner and more economic catalytic process, low cost, less byproducts, yield up to 95.2%, easiness in product separation, environmental friendliness, reusability of the catalyst, higher atom economy and green index and good industrial application prospect.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further explained with reference to the following embodiments and accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention, and that experimental conditions and set parameters therein are not to be considered as limitations of the basic embodiments of the invention. And the scope of the present invention is not limited to the following examples. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Unless otherwise specified, the raw materials and reagents in the examples of the present application were all purchased commercially.
Example 1
2, 5-furandimethanol (0.05g, 5g/L), titanium silicalite TS-1(Si/Ti molar ratio 30: 1, 0.1g), H2O2(30 wt%, 0.06mol/L) 10mL of H was added2O, and stirring at 30 ℃ for 30 min. After cooling, 5mL of the reaction solution was taken and fixed to a 100mL volumetric flask, and subjected to hplc determination through a 0.22 μm microporous membrane, the conversion rate of 2, 5-furandimethanol was 100%, and the yield of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one (structural formula shown below) was 95.2%, as shown in fig. 1, the product was yellow oily.
The nuclear magnetic characterization data of the product 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one is: 1H-NMR (400MHz, CDCl)3)：δ＝6.84(d,1H)，6.20(d,1H)，4.63(d,1H)，4.18(d,1H)，3.82(d,1H)，3.65(d,1H)。
Examples 2 to 5
The other process conditions and reaction steps were the same as in example 1, but different reaction temperatures were used, and the results are shown in Table 1.
TABLE 1 Experimental results of titanium silicalite molecular sieve catalytic conversion of 2, 5-furandimethanol at different reaction temperatures
Examples 6 to 8
The other process conditions and reaction steps were the same as in example 1, but different reaction times were used, and the results are shown in Table 2.
TABLE 2 Experimental results of titanium silicalite molecular sieve catalytic conversion of 2, 5-furandimethanol under different reaction time
Examples 9 to 11
The other process conditions and reaction steps were the same as in example 1, but different amounts of catalyst were used, i.e., the mass ratio of the titanium silicalite to the 2, 5-furandimethanol was different, and the results are shown in Table 3.
TABLE 3 Experimental results of titanium silicalite molecular sieve catalytic conversion of 2, 5-furandimethanol under different catalyst dosages
A liquid chromatography-time-of-flight mass spectrometry chromatogram of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one prepared in example 10 is shown in fig. 2, and a mass spectrum is shown in fig. 3.
Examples 12 to 14
The other process conditions and reaction steps were the same as in example 1, but with different substrate mass concentrations, the results are shown in Table 4.
TABLE 4 Experimental results of titanium silicalite molecular sieve catalytic conversion of 2, 5-furandimethanol under different substrate mass concentrations
See FIG. 4 for a UV absorption vs. VIS spectrum of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one prepared in example 12.
Examples 15 to 17
The other process conditions and reaction steps were the same as in example 1, but different concentrations of oxidizing agent hydrogen peroxide were used, and the results are shown in Table 5.
TABLE 5 Experimental results of titanium silicalite molecular sieve catalytic conversion of 2, 5-furandimethanol under different hydrogen peroxide concentrations
Examples 18 to 20
The other process conditions and reaction steps were the same as in example 1, but with titanium silicalite catalysts of different silicon to titanium ratios, the results are shown in table 6.
TABLE 6 catalytic conversion of 2, 5-furandimethanol with Ti-Si molecular sieve at different Si/Ti ratios
Comparative example 1
Commun, 2015,45, 348-: the oxidant used is m-chloroperoxybenzoic acid. In this comparative example, the yield of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one was not ideal, but only 45% to 63% when 2, 5-furandimethanol was completely converted.
Comparative example 2
CN 109180624A discloses a preparation method of 2-substituted 6-hydroxy-2H-pyran-3-ketone compounds, which adopts an organic solvent and takes cumene hydroperoxide as an oxidant under the action of a triisopropoxyl vanadyl homogeneous catalyst, but the yield is only 61-78%.
This comparative example does not relate to the conversion of 2, 5-furandimethanol nor does it produce the desired product of the present invention.
By the technical scheme, the 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone is obtained through one-step catalytic oxidation process under mild conditions, a cleaner and more economic catalytic process is realized, the yield is up to 95.2%, the cost is low, few by-products are generated, the method is environment-friendly, the atom economy and the reaction efficiency are higher, the product is easy to separate, and the method has good industrial application prospects.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention also conducted experiments using other raw materials, process operations, and process conditions described in the present specification with reference to the above-described embodiments 1 to 20, and obtained 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one with high selectivity as well.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A method for preparing 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -ketone by catalytic oxidation, which is characterized by comprising the following steps:
the method comprises the steps of taking a titanium silicalite molecular sieve as a catalyst, hydrogen peroxide as an oxidant and water as a reaction medium, and carrying out catalytic oxidation on 2, 5-furandimethanol at 15-100 ℃ for 20-120 min to obtain 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one.
2. The method of claim 1, comprising: uniformly mixing 2, 5-furandimethanol, a titanium silicalite molecular sieve, hydrogen peroxide and water, stirring the obtained mixed reaction system at 15-70 ℃ for reaction for 20-60 min, and performing one-step catalytic oxidation to obtain 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one.
3. The method according to claim 1 or 2, characterized in that: the silicon-titanium ratio in the titanium-silicon molecular sieve is (15-80): 1, preferably (30-50): 1.
4. the method according to claim 1 or 2, characterized in that: the mass ratio of the titanium silicalite molecular sieve to the 2, 5-furandimethanol is (0.1-20): 1, preferably (0.4-5.0): 1.
5. the method according to claim 1 or 2, characterized in that: the 2, 5-furandimethanol is obtained by reducing 5-hydroxymethyl furfural.
6. The method of claim 2, wherein: the mass concentration of the 2, 5-furandimethanol in the mixed reaction system is 1 g/L-50 g/L, preferably 5 g/L-25 g/L.
7. The method according to claim 1 or 2, characterized in that: the oxidant is aqueous hydrogen peroxide solution with the mass concentration of 30-50%.
8. The method according to claim 1 or 2, characterized in that: the concentration of the oxidant in the mixed reaction system is 0.02 mol/L-10 mol/L, preferably 0.04 mol/L-2 mol/L.
9. The method according to claim 1 or 2, characterized in that: the reaction temperature is 25-70 ℃; and/or the reaction time is 30-60 min.
10. The method according to claim 1 or 2, characterized in that: the conversion of 2, 5-furandimethanol in the process is above 90% and the yield of 6-hydroxy-6 (hydroxymethyl) -2H-pyran-3 (6H) -one is above 75%.
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| CN115433956A (en) * | 2022-09-29 | 2022-12-06 | 厦门大学 | Method for electrochemically synthesizing 2-ethyl-6-hydroxy-2H-pyrone |
| CN115504952A (en) * | 2022-07-07 | 2022-12-23 | 洛阳师范学院 | Preparation method of 6-methyl dihydro-2H-pyran-3 (4H) -one |
| CN115504952B (en) * | 2022-07-07 | 2024-05-14 | 洛阳师范学院 | Preparation method of 6-methyldihydro-2H-pyran-3 (4H) -one |
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Cited By (3)
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| CN115504952A (en) * | 2022-07-07 | 2022-12-23 | 洛阳师范学院 | Preparation method of 6-methyl dihydro-2H-pyran-3 (4H) -one |
| CN115504952B (en) * | 2022-07-07 | 2024-05-14 | 洛阳师范学院 | Preparation method of 6-methyldihydro-2H-pyran-3 (4H) -one |
| CN115433956A (en) * | 2022-09-29 | 2022-12-06 | 厦门大学 | Method for electrochemically synthesizing 2-ethyl-6-hydroxy-2H-pyrone |
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