CN113214204B - Synthesis method of 2-pyrone compound and alpha, beta-unsaturated chain ester compound - Google Patents
Synthesis method of 2-pyrone compound and alpha, beta-unsaturated chain ester compound Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
- C07D309/38—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms one oxygen atom in position 2 or 4, e.g. pyrones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
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- C07C67/00—Preparation of carboxylic acid esters
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/46—Preparation of carboxylic acid esters from ketenes or polyketenes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
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Abstract
The invention provides a synthetic method of a 2-pyrone compound 3 and an alpha, beta-unsaturated chain ester compound 4, belonging to the technical field of organic synthesis. The synthesis method adopts potassium tert-butoxide to catalyze lignin and cyclopropenone to prepare the 2-pyrone compound through a [3+3] cycloaddition reaction. In an organic solvent, taking potassium tert-butoxide as a catalyst, and reacting a lignin compound 1 with a cyclopropenone compound 2 under a heating condition to obtain a 2-pyrone compound 3; when R is aryl, alpha, beta unsaturated chain ester compound 4 is also generated; the method selectively breaks beta-O-4 bonds in a lignin model to synthesize 2-pyrone compounds; the used raw materials are simple and easy to obtain, the adopted catalyst is cheap, the source is wide and easy to obtain, the dosage is small, the reaction condition is relatively mild, and the product can be obtained with high yield.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthesis method of 2-pyrone compounds and alpha, beta-unsaturated chain ester compounds.
Background
Lignin is one of the main components of lignocellulosic biomass, an alternative and sustainable source of aromatic and cyclic hydrocarbons. Oxidative cleavage of lignin (C-C and C-O) occurs mainly on alkyl and/or alkenyl side chains, resulting in hydroxyl-, aldehyde-and carboxyl-substituted phenolic compounds. Oxidative cleavage occurs at CPh-C, C α -H, C α -C β and C β -O positions in lignin. In this way, the oxidative cleavage of CPh-C forms acrolein and quinone compounds; c alpha-H and C alpha-C beta cleavage produces ketones and aromatic aldehydes; oxidative cleavage of the β -O-4 bond, i.e., C β -O cleavage, produces different monomers-phenols and aromatic aldehydes/esters/carboxylic acids, etc.
The lignin depolymerization reaction employs several methods, i.e., alkali/acid hydrolysis, pyrolysis, oxidation, and reduction reactions. Base-catalyzed hydrolysis is a widely used method of producing lignin oils (using NaOH and KOH catalysts) industrially at 200 ℃. about.200 ℃. It is reported that base catalysis can generally be used to produce 20-23% yields. The base catalyzed depolymerization portion consists primarily of catechol (catechol, alkylated catechol, and methoxy catechol), guaiacol, and eugenol.
Disclosure of Invention
The invention aims to provide a simple and efficient synthesis method of 2-pyrone compounds under mild conditions.
In order to achieve the purpose, the invention provides a synthetic method of a 2-pyrone compound 3 and an alpha, beta unsaturated chain ester compound 4, which comprises the following steps:
in an organic solvent, taking potassium tert-butoxide as a catalyst, and reacting a lignin compound 1 with a cyclopropenone compound 2 under a heating condition to obtain a 2-pyrone compound 3; when R is aryl, alpha, beta unsaturated chain ester compound 4 is also generated. The reaction equation is expressed as follows:
wherein R is C1-C4 alkyl, C6-C8 aryl; r1Is hydrogen, C1-C4 alkyl; r2Is C1-C4 alkyl, C1-C4 alkoxy and halogen.
Further, in the above technical solution, the R is methyl, phenyl, 2-methoxyphenyl, 4-acetylphenyl; r1Is hydrogen or methyl; r1Is methyl, methoxy, fluorine or chlorine.
Further, in the above technical solution, the organic solvent is an aprotic polar solvent.
Further, in the above technical solution, the aprotic polar solvent is selected from DCE, DMA, DME, DMF, dioxane.
Further, in the above technical solution, the aprotic polar solvent is selected from DME.
Further, in the above technical scheme, when DBU, potassium acetate, potassium carbonate, triethylamine and sodium methoxide are used as the base catalyst to replace potassium tert-butoxide, the effect is poor.
Further, in the above technical scheme, the molar ratio of the lignin compound 1, the cyclopropenone compound 2 and the potassium tert-butoxide is 1: 1-2.2: 0.05-0.1.
Further, in the above technical scheme, the heating temperature is 30-80 ℃.
Further, in the above technical solution, the reaction is performed under the protection of an inert gas, and the inert gas is nitrogen or argon.
The invention has the beneficial effects that:
the present invention utilizes KOtBu catalyzes lignin 1 and cyclopropenone 2 to pass through (3 + 3)]And (3) performing cycloaddition reaction to prepare the 2-pyrone compound 3. The method selectively breaks a beta-O-4 bond in a lignin model to synthesize a 2-pyrone compound 3, and the residual ArO part in lignin 1 continuously reacts with cyclopropenone 2 to generate an alpha, beta-unsaturated chain ester compound 4; the method uses simple and easily-obtained raw materials, and the adopted catalyst is cheap, has wide and easily-obtained sources, small using amount and relatively mild reaction conditions, and can obtain two products with high yield.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to limit the scope of the present invention in any way.
General synthetic method of 2-pyrone compound 3
Under an argon atmosphere, 0.1mmol of Compound 1, 0.2mmol of Compound 2 and 10 mol% KO were added to a vacuum-sealed tubetBu, adding an organic solvent, sealing the vacuum tube, and placing the tube in an oil bath at 50-80 ℃ to stir until the reaction. After the reaction is finished, adding water for quenching, extracting by ethyl ether for three times, combining ethyl ether layers, decompressing and removing the organic solvent to obtain a crude product, and purifying by PE/EA silica gel column chromatography to obtain a compound 3 and a compound 4. The use of an alkyl ether 1(R is an alkyl group) does not result in the product 4, while the use of an alkyl aryl ether 1(R is an aryl group) results in a good yield of the product 4, which may be responsible for the difference in nucleophilicity of RO-formed after C-O cleavage.
Example 1
Under an argon atmosphere, compound 1a (0.1mmol), compound 2a (0.1mmol) and a base (1.1mg, 0.01mmol) were added to a vacuum sealed tube, a solvent (1.0mL) was added, the vacuum sealed tube was sealed, the reaction was kept in an oil bath at a certain temperature, the reaction was stirred until completion (12 to 36h), the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3 aa.
Example 2
Under an argon atmosphere, compound 1a (0.1mmol), compound 2a (0.2mmol) and KO were added to a vacuum sealed tubetBu (1.1mg, 0.01mmol), DME (1.0mL) was added, the tube was sealed under vacuum, the mixture was put in an oil bath at 30 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3 aa. Yellow solid (mp 162-; (64mg, yield 98%);1H NMR(400MHz,CDCl3)δ7.97-7.95(m,2H),7.58-7.46(m,3H),7.38-7.17(m,10H),6.89(s,1H).13C NMR(101MHz,CDCl3)δ162.7,158.4,152.8,137.9,133.9,131.5,131.0,130.8,129.1,128.8,128.8,128.5,128.1,127.8,125.7,123.3,105.1.HRMS(ESI,m/z):calcd for C23H17O2 +[M+H]+:325.1223,found 325.1217.
example 3
Under argon atmosphere, compound 1b (0.1mmol) and compound 2a (0.2 mm) were added to a vacuum sealed tubeol) and KOtBu (1.1mg, 0.01mmol), DME (1.0mL) was added, the tube was sealed under vacuum, placed in an oil bath at 50 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3aa and compound 4 ba. 3aa yellow solid (mp 162 ═ 164 ℃ C.); (32mg, yield 99%), 4ba: yellow solid (mp ═ 107-; (25mg, yield 83%).1H NMR(400MHz,CDCl3)δ7.91(s,1H),7.31-7.27(m,2H),7.25-7.19(m,3H),7.15-6.96(m,10H).13C NMR(101MHz,CDCl3)δ166.5,151.4,142.1,135.7,134.6,132.2,131.0,130.0,129.5,129.5,128.9,128.4,128.2,125.9,121.8.HRMS(ESI,m/z):calcd for C21H17O2 +[M+H]+:301.1223,found 301.1223.
Example 4
Under an argon atmosphere, compound 1c (0.1mmol), compound 2a (0.2mmol) and KO were added to a vacuum sealed tubetBu (1.1mg, 0.01mmol), DME (1.0mL) was added, the tube was sealed under vacuum, the mixture was put in an oil bath at 50 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3aa and compound 4 ca. 3aa yellow solid (mp 162 ═ 164 ℃ C.); (32mg, yield 99%). 4ca: yellow liquid; (25mg, yield 76%).1H NMR(400MHz,CDCl3)δ7.96(s,1H),7.29(s,5H),7.16-7.08(m,4H),7.06-6.98(m,3H),6.91-6.84(m,2H),3.77(s,3H).13C NMR(101MHz,CDCl3)δ166.2,151.4,141.9,140.5,135.8,134.8,132.0,130.9,130.2,129.4,128.7,128.4,128.1,126.9,123.0,120.9,112.7,56.2.HRMS(ESI,m/z):calcd for C22H19O3 +[M+H]+:331.1329,found 331.1329.
Example 5
Under an argon atmosphere, compound 1d (0.1mmol), compound 2a (0.2mmol) and KO were added to a vacuum sealed tubetBu (1.1mg, 0.01mmol), DME (1.0mL) was added, the vacuum sealed tube was sealed, placed in an oil bath at 50 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3aa and compound 4 da. 3aa yellow solid (mp 162 ═ 164 ℃ C.); (32mg, yield 99%). 4da yellow solid (mp ═ 102 ℃ 104 ℃); (34mg, yield 98%).1H NMR(400MHz,CDCl3)δ7.98(s,1H),7.92(d,J＝8.5Hz,2H),7.34-7.31(m,3H),7.26-7.25(m,2H),7.20-7.16(m,3H),7.14-7.10(m,2H),7.04-7.02(m,2H),2.52(s,3H).13C NMR(151MHz,CDCl3)δ197.0,165.9,155.0,142.9,135.3,134.8,134.3,131.6,131.0,130.0,129.9,129.8,129.0,128.5,128.3,122.0,26.7.HRMS(ESI,m/z):calcd for C23H19O3 +[M+H]+:343.1329,found 343.1329.
Example 6
Under an argon atmosphere, in a vacuum sealed tube, compound 1e (0.1mmol), compound 2a (0.2mmol) and KO were addedtBu (1.1mg, 0.01mmol), DME (1.0mL) was added, the tube was sealed under vacuum, the mixture was put in an oil bath at 80 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3EA and compound 4 ba. 3ea yellow liquid; (34mg, yield 99%).1H NMR(400MHz,CDCl3)δ7.72-7.69(m,2H),7.56-7.49(m,3H),7.30-7.26(m,3H),7.21-7.14(m,5H),7.11-7.07(m,2H),1.92(s,3H).13C NMR(101MHz,CDCl3)δ162.6,156.7,156.5,137.0,134.3,133.2,130.7,129.9,129.4,128.7,128.5,128.3,128.0,127.8,127.5,125.5,112.3,16.6.HRMS(ESI,m/z):calcd for C24H19O2 +[M+H]+339.1380, found 339.1380.4ba: yellow solid (mp 107-.
Example 7
Under an argon atmosphere, compound 1f (0.1mmol), compound 2a (0.2mmol) and KO were added to a vacuum sealed tubetBu (1.1mg, 0.01mmol), DME (1.0mL) was added, the vacuum sealed tube was sealed, the mixture was put in an oil bath at 80 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3EA and compound 4 ca. 3ea yellow liquid (24mg, 71% yield), 4ca yellow liquid (24mg, 72% yield).
Example 8
Under an argon atmosphere, 1g (0.2mmol) of the compound, 2a (0.2mmol) of the compound and KO were added to a vacuum sealed tubetBu (2.2mg, 0.02mmol), DME (2.0mL) was added, the vacuum sealed tube was sealed, the mixture was put in an oil bath at 30 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3 ga. Yellow solid (mp ═ 88-89 ℃); (67mg, yield 99%).1H NMR(400MHz,CDCl3)δ7.85(d,J＝8.1Hz,2H),7.33-7.30(m,5H),7.28-7.25(m,5H),7.22-7.20(m,2H),6.85(s,1H),2.46(s,3H).13C NMR(101MHz,CDCl3)δ162.9,158.7,153.0,141.3,138.1,134.1,131.0,129.8,128.8,128.8,128.5,128.0,127.7,125.7,122.8,104.4,21.6.HRMS(ESI,m/z):calcd for C24H19O2 +[M+H]+:339.1380,found 339.1371.
Example 9
Under argon atmosphere, add compound 1h (0.2mmol)Compound 2a (0.2mmol) and KOtBu (2.2mg, 0.02mmol), DME (2.0mL) was added, the tube was sealed under vacuum, the mixture was put in an oil bath at 30 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3 ha. Yellow solid (mp ═ 166-; (53mg, yield 75%).1H NMR(400MHz,CDCl3)δ7.85(d,J＝8.8Hz,2H),7.29-7.12(m,10H),6.97(d,J＝8.8Hz,2H),6.72(s,1H),3.87(s,3H).13C NMR(101MHz,CDCl3)δ163.0,161.9,158.6,153.2,138.2,134.1,131.1,128.8,128.8,128.5,128.1,127.7,127.4,124.1,122.1,114.5,103.7,55.6.HRMS(ESI,m/z):calcd for C24H19O3 +[M+H]+:355.1329,found 335.1320.
Example 10
Under an argon atmosphere, compound 1i (0.2mmol), compound 2a (0.2mmol) and KO were added to a vacuum sealed tubetBu (2.2mg, 0.02mmol), DME (2.0mL) was added, the vacuum sealed tube was sealed, the mixture was put in an oil bath at 30 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3 ia. Yellow solid (mp 192 ═ 194 ℃); (66mg, yield 96%).1H NMR(400MHz,CDCl3)δ7.83-7.80(m,2H),7.21-7.04(m,12H),6.69(s,1H).13C NMR(101MHz,CDCl3)δ164.4(d,J＝252.3Hz),162.6,157.5,152.8,137.9,133.9,131.0,129.0,128.8,128.5,128.1,127.9,127.8(d,J＝3.5Hz),123.2,116.3(d,J＝22.0Hz),104.8.19F NMR(377MHz,CDCl3)δ-108.68～-108.82(m).HRMS(ESI,m/z):calcd for C23H16FO2 +[M+H]+:343.1129,found 343.1123.
Example 11
Under an argon atmosphere, compound 1j (0.2mmol), compound 2a (0.2mmol) and KO were added to a vacuum sealed tubetBu (2.2mg, 0.02mmol), DME (2.0mL) was added and the mixture was sealedAnd (3) placing the tube in an oil bath at 30 ℃, stirring until the reaction is finished, removing the organic solvent under reduced pressure to obtain a crude product, and purifying by silica gel column chromatography (PE: EA is 10:1) to obtain the compound 3 ja.
Yellow solid (mp ═ 172 ℃) 174 ℃; (65mg, yield 90%).1H NMR(400MHz,CDCl3)δ7.75(d,J＝8.6Hz,2H),7.36(d,J＝8.5Hz,2H),7.18-7.16(m,3H),7.15-7.12(m,4H),7.11-7.10(m,1H),7.09-7.05(m,2H),6.72(s,1H).13C NMR(101MHz,CDCl3)δ162.5,157.3,152.7,137.8,137.0,133.8,131.0,130.0,129.4,129.0,128.8,128.6,128.1,127.9,127.0,123.7,105.3.HRMS(ESI,m/z):calcd for C23H16ClO2 +[M+H]+:359.0833,found 359.0830.
Example 12
Under an argon atmosphere, compound 1k (0.2mmol), compound 2a (0.2mmol) and KO were added to a vacuum sealed tubetBu (2.2mg, 0.02mmol), DME (2.0mL) was added, the vacuum sealed tube was sealed, the mixture was put in an oil bath at 30 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3 ka. Yellow solid (mp ═ 138 ℃.); (67mg, yield 99%).1H NMR(400MHz,CDCl3)δ7.65(s,1H),7.60(d,J＝7.6Hz,1H),7.26(t,J＝7.6Hz,1H),7.19-7.15(m,4H),7.14-7.12(m,5H),7.08-7.07(m,2H),6.73(s,1H),2.33(s,3H).13C NMR(101MHz,CDCl3)δ162.8,158.6,152.9,138.9,138.0,134.0,131.7,131.4,131.0,128.9,128.8,128.4,128.0,127.7,126.3,123.1,122.9,105.0,21.5.HRMS(ESI,m/z):calcd for C24H19O2 +[M+H]+:339.1380,found 339.1364.
Example 13
Under an argon atmosphere, compound 1l (0.2mmol), compound 2a (0.2mmol) and KO were added to a vacuum sealed tubetBu (2.2mg, 0.02mmol), DME (2.0mL) was added, the tube was sealed under vacuum, the mixture was put in an oil bath at 30 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3 la. Yellow solid (mp ═ 128 ℃.); (70mg, yield 99%).1H NMR(400MHz,CDCl3)δ7.38-7.34(m,2H),7.29-7.25(m,1H),7.20-7.04(m,10H),6.93-6.90(m,1H),6.73(s,1H),3.77(s,3H).13C NMR(101MHz,CDCl3)δ162.7,160.2,158.2,152.8,137.9,133.9,132.9,131.0,130.1,128.8,128.8,128.5,128.1,127.8,123.3,118.1,117.0,110.8,105.4,55.6.HRMS(ESI,m/z):calcd for C24H19O3 +[M+H]+:355.1329,found 355.1320.
Example 14
Under an argon atmosphere, compound 1m (0.2mmol), compound 2a (0.2mmol) and KO were added to a vacuum sealed tubetBu (2.2mg, 0.02mmol), DME (2.0mL) was added, the vacuum sealed tube was sealed, placed in an oil bath at 30 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3 ma. Yellow solid (mp ═ 115 ℃ -; (67mg, yield 98%).1H NMR(400MHz,CDCl3)δ7.59(d,J＝7.8Hz,1H),7.51(d,J＝9.8Hz,1H),7.37-7.32(m,1H),7.19-7.16(m,3H),7.15-7.10(m,5H),7.10-7.05(m,3H),6.74(s,1H).13C NMR(101MHz,CDCl3)δ163.22(d,J＝247.0Hz),162.38,156.85(d,J＝2.9Hz),152.5,137.7,133.7,133.7(d,J＝8.1Hz),130.9,130.7(d,J＝8.2Hz),128.9,128.8,128.5,128.1,127.9,124.0,121.3(d,J＝2.9Hz),117.7(d,J＝21.2Hz),112.7(d,J＝23.9Hz),105.8.19F NMR(377MHz,CDCl3)δ-111.50～-111.60(m).HRMS(ESI,m/z):calcd for C23H16FO2 +[M+H]+:343.1129,found 343.1121.
Example 15
Under an argon atmosphere, compound 1n (0.2mmol), compound 2a (0.2mmol) and KO were added to a vacuum sealed tubetBu (2.2mg, 0.02mmol), DME (2.0mL) was added, the tube was sealed under vacuum, the mixture was put in an oil bath at 30 ℃, stirred until the reaction was completed, and the organic solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography (PE: EA ═ 10:1) to obtain compound 3 na. Yellow solid (mp ═ 147-; (65mg, yield 90%).1H NMR(400MHz,CDCl3)δ7.80(s,1H),7.70-7.67(m,1H),7.36-7.28(m,2H),7.20-7.04(m,10H),6.74(s,1H).13C NMR(101MHz,CDCl3)δ162.4,156.7,152.6,137.7,135.3,133.7,133.2,130.9,130.8,130.3,129.0,128.8,128.5,128.1,128.0,125.7,124.0,123.7,105.8.HRMS(ESI,m/z):calcd for C23H16ClO2 +[M+H]+:359.0833,found 359.0826.
The foregoing is directed to the preferred embodiment of the present invention and is not intended to limit the invention to the specific embodiment described. It will be apparent to those skilled in the art that various modifications, equivalents, improvements and the like can be made without departing from the spirit of the invention, and these are intended to be included within the scope of the invention.
Claims (8)
1. A synthetic method of a 2-pyrone compound 3 and an alpha, beta-unsaturated chain ester compound 4 is characterized by comprising the following steps:
when R is alkyl: in an organic solvent, taking potassium tert-butoxide as a catalyst, and reacting a lignin compound 1 with a cyclopropenone compound 2 under a heating condition to obtain a 2-pyrone compound 3;
wherein R is C1-C4 alkyl; r1Is hydrogen, C1-C4 alkyl; r2Is C1-C4 alkyl, C1-C4 alkoxy, halogen;
when R is aryl: in an organic solvent, taking potassium tert-butoxide as a catalyst, and reacting a lignin compound 1 with a cyclopropenone compound 2 under a heating condition to obtain a 2-pyrone compound 3 and an alpha, beta unsaturated chain ester compound 4;
wherein R is C6-C8 aryl; r1Is hydrogen, C1-C4 alkyl; r2Is C1-C4 alkyl, C1-C4 alkoxy and halogen.
2. The method for synthesizing 2-pyrone compounds 3 and α, β -unsaturated chain ester compounds 4 according to claim 1, wherein: when R is alkyl, it is selected from methyl; when R is aryl, it is selected from phenyl; r1Hydrogen and methyl; r is2Is methyl, methoxy, fluorine or chlorine.
3. The method for synthesizing 2-pyrone compounds 3 and α, β -unsaturated chain ester compounds 4 according to claim 1, wherein: the organic solvent is an aprotic polar solvent.
4. The method for synthesizing 2-pyrone compounds 3 and α, β -unsaturated chain ester compounds 4 according to claim 3, wherein the method comprises the following steps: the aprotic polar solvent is selected from the group consisting of DCE, DMA, DME, DMF, dioxane.
5. The method for synthesizing 2-pyrone compounds 3 and α, β -unsaturated chain ester compounds 4 according to claim 4, wherein: the aprotic polar solvent is selected from DME.
6. The method for synthesizing 2-pyrone compounds 3 and α, β -unsaturated chain ester compounds 4 according to claim 1, wherein: the molar ratio of the lignin compound 1, the cyclopropenone compound 2 and the potassium tert-butoxide is 1: 1-2.2: 0.05-0.1.
7. The method for synthesizing 2-pyrone compounds 3 and α, β -unsaturated chain ester compounds 4 according to any one of claims 1 to 6, wherein: the heating temperature is 30-80 ℃.
8. The method for synthesizing 2-pyrone compounds 3 and α, β -unsaturated chain ester compounds 4 according to any one of claims 1 to 6, wherein: the reaction is carried out under the protection of inert gas, and the inert gas is nitrogen or argon.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110526795A (en) * | 2019-08-08 | 2019-12-03 | 河南师范大学 | The butylene lactone or butylene lactam compound and its method of asymmetric synthesis and ligand that γ-alkenyl replaces |
| CN111960909A (en) * | 2019-08-08 | 2020-11-20 | 河南师范大学 | Gamma-alkenyl substituted butenolide or butenolactam compound, asymmetric synthesis method and ligand thereof |
| CN111646964A (en) * | 2020-06-24 | 2020-09-11 | 四川大学 | Novel method for synthesizing 2H-pyran-2-one derivative by base catalysis |
Non-Patent Citations (2)
| Title |
|---|
| Dimethyl(2-oxo-2-phenylethyl)sulfonium inner salt;Akagawa, Kengo;《e-EROS Encyclopedia of Reagents for Organic Synthesis》;20161231;第1-4页 * |
| Product class 1: cyclopropenium salts, cyclopropenones and heteroatom analogues, and cyclopropenyl radicals and anions;Merino, P.;《Science of Synthesis》;20081230;第11-48页 * |
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