CN117229237A - Preparation method for constructing polysubstituted furan compounds from phenylacetylene compounds and benzaldehyde compounds - Google Patents
Preparation method for constructing polysubstituted furan compounds from phenylacetylene compounds and benzaldehyde compounds Download PDFInfo
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- CN117229237A CN117229237A CN202311200999.XA CN202311200999A CN117229237A CN 117229237 A CN117229237 A CN 117229237A CN 202311200999 A CN202311200999 A CN 202311200999A CN 117229237 A CN117229237 A CN 117229237A
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- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000002240 furans Chemical class 0.000 title claims abstract description 11
- 150000003935 benzaldehydes Chemical class 0.000 title claims description 9
- -1 polysubstituted furan compound Chemical class 0.000 claims abstract description 28
- 229940126214 compound 3 Drugs 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940125904 compound 1 Drugs 0.000 claims abstract description 16
- 229940125782 compound 2 Drugs 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 238000004440 column chromatography Methods 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical group O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 14
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method for constructing a polysubstituted furan compound by using a phenylacetylene compound and a benzaldehyde compound, which relates to the technical field of preparation methods of polysubstituted furan compounds, and the method comprises the steps of reacting a compound 1 with a compound 2 at a predetermined temperature under the conditions of a catalyst, a solvent and an additive to generate a solution containing a compound 3; the solution containing the compound 3 is extracted, dried, distilled under reduced pressure, separated and purified by column chromatography to obtain the compound 3, and a nonmetallic catalyst is used to enable the phenylacetylene compound 1 and the benzaldehyde compound 2 to react to generate the polysubstituted furan compound, so that the reaction process is simple, the operation is easy, the raw materials are easy to obtain, the cost is low, and the method is green and safe.
Description
Technical Field
The invention belongs to the technical field of preparation methods of polysubstituted furan compounds, and particularly relates to a preparation method for constructing a polysubstituted furan compound by using phenylacetylene compounds and benzaldehyde compounds.
Background
In the field of organic chemistry, polysubstituted furans are important five-membered heterocyclic compounds, which are ubiquitous in a variety of biologically active natural molecules and can be used to build many drug molecules or as synthetic intermediates. Therefore, the development of efficient synthesis technology of polysubstituted furans has attracted extensive attention from researchers.
In the prior art, the application number is as follows: 201310234976.0A Chinese patent invention discloses a preparation method of a polysubstituted furanone compound, and in particular discloses a preparation method of a polysubstituted furanone compound, which comprises the steps of adding metal salt, alkyl substituted ketone and alpha, beta-unsaturated carboxylic acid into an organic solvent, heating to 120-150 ℃, reacting completely, and post-treating to obtain the polysubstituted furanone compound, wherein the metal salt consists of monovalent copper salt and divalent copper salt.
Disclosure of Invention
In view of the above, the invention provides a preparation method for constructing a polysubstituted furan compound by taking phenylacetylene compounds and benzaldehyde compounds as substrates, wherein the preparation method is simple to operate, does not need complex reaction substrates and metal catalysts.
The technical scheme adopted for solving the technical problems is as follows:
a preparation method for constructing polysubstituted furan compounds by phenylacetylene compounds and benzaldehyde compounds comprises the following steps,
s1: reacting the compound 1 with the compound 2 under the conditions of a catalyst, a solvent and an additive at a preset temperature to generate a solution containing the compound 3;
s2: extracting, drying, distilling under reduced pressure, separating and purifying the solution containing the compound 3 by column chromatography to obtain the compound 3; the synthetic route is as follows:
the R is 1 The method comprises the following steps: hydrogen, methyl, methoxy, fluoro, trifluoromethyl
R 2 The method comprises the following steps: hydrogen, methyl, fluorine, chlorine, trifluoromethyl.
Preferably, the catalyst is selenium dioxide.
Preferably, the solvent is one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide.
Preferably, the additive is one of sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide, sodium methoxide, potassium methoxide, tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide.
Preferably, the predetermined temperature is 60 ℃ to 100 ℃.
Preferably, the molar ratio of the compound 1 to the compound 2 to the catalyst is: 1:2-5:2-3.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method for constructing a polysubstituted furan compound by using phenylacetylene compounds and benzaldehyde compounds, which comprises the steps of reacting a compound 1 with a compound 2 at a predetermined temperature under the condition of a catalyst, a solvent and an additive to generate a solution containing a compound 3; the solution containing the compound 3 is extracted, dried, distilled under reduced pressure, separated and purified by column chromatography to obtain the compound 3, and a nonmetallic catalyst is used to enable the phenylacetylene compound 1 and the benzaldehyde compound 2 to react to generate the polysubstituted furan compound, so that the reaction process is simple, the operation is easy, the raw materials are easy to obtain, the cost is low, and the method is green and safe.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the first embodiment.
FIG. 2 is a nuclear magnetic resonance chart of the first embodiment.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the second embodiment.
FIG. 4 is a nuclear magnetic resonance chart of a second embodiment.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of example III.
FIG. 6 is a nuclear magnetic resonance spectrum of a third embodiment.
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of example IV.
FIG. 8 is a nuclear magnetic resonance spectrum of a fourth embodiment.
FIG. 9 is a nuclear magnetic resonance hydrogen spectrum of example five.
FIG. 10 is a nuclear magnetic resonance chart of a fifth embodiment.
FIG. 11 is a nuclear magnetic resonance hydrogen spectrum of a sixth embodiment.
FIG. 12 is a nuclear magnetic resonance spectrum of a sixth embodiment.
FIG. 13 is a nuclear magnetic resonance hydrogen spectrum of example seven.
FIG. 14 is a nuclear magnetic resonance spectrum of a seventh embodiment.
FIG. 15 is a nuclear magnetic resonance hydrogen spectrum of example eight.
FIG. 16 is a nuclear magnetic resonance spectrum of example eight.
FIG. 17 is a nuclear magnetic resonance hydrogen spectrum of example nine.
FIG. 18 is a nuclear magnetic resonance spectrum of example nine.
FIG. 19 is a hydrogen nuclear magnetic resonance spectrum of example ten.
FIG. 20 is a nuclear magnetic resonance spectrum of example ten.
Detailed Description
The technical scheme and technical effects of the embodiments of the present invention are further described in detail below with reference to the accompanying drawings.
A preparation method for constructing polysubstituted furan compounds by phenylacetylene compounds and benzaldehyde compounds comprises the following steps,
s1: reacting the compound 1 with the compound 2 under the conditions of a catalyst, a solvent and an additive at a preset temperature to generate a solution containing the compound 3;
s2: extracting, drying, distilling under reduced pressure, separating and purifying the solution containing the compound 3 by column chromatography to obtain the compound 3; the synthetic route is as follows:
the R is 1 The method comprises the following steps: hydrogen, methyl, methoxy, fluoro, trifluoromethyl
R 2 The method comprises the following steps: hydrogen, methyl, fluorine, chlorine, trifluoromethyl.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method for constructing a polysubstituted furan compound by using phenylacetylene compounds and benzaldehyde compounds, which comprises the steps of reacting a compound 1 with a compound 2 at a predetermined temperature under the condition of a catalyst, a solvent and an additive to generate a solution containing a compound 3; the solution containing the compound 3 is extracted, dried, distilled under reduced pressure, separated and purified by column chromatography to obtain the compound 3, and a nonmetallic catalyst is used to enable the phenylacetylene compound 1 and the benzaldehyde compound 2 to react to generate the polysubstituted furan compound, so that the reaction process is simple, the operation is easy, the raw materials are easy to obtain, the cost is low, and the method is green and safe.
Further, the catalyst is selenium dioxide, the selenium dioxide is used as an oxidant and a catalyst/accelerator in the reaction, and under alkaline conditions, the selenium dioxide catalyzes the coupling of benzaldehyde and phenylacetylene to form an alkynone intermediate. Subsequently, the alkynone intermediate forms a resonant built-up diene, which undergoes an addition coupling reaction with another molecule of benzaldehyde to form a built-up dienone intermediate. Finally, the intermediate forms a polysubstituted furan product by intramolecular cyclization reactions.
Further, the solvent is one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide.
Further, the additive is one of sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide, sodium methoxide, potassium methoxide, tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide, so as to provide a proper alkaline environment to promote the reaction.
Further, the predetermined temperature is 60 ℃ to 100 ℃.
Further, the molar ratio of the compound 1 to the compound 2, the catalyst and the solvent is as follows: 1:2-5:2-3.
Furthermore, in the step S1, argon and nitrogen are required to be filled as a shielding gas during the reaction, so as to isolate air and prevent oxygen from affecting the reaction.
Further, in the step S1, the progress of the reaction is monitored by thin layer chromatography until the reaction is completed.
Further, in the step S2, the specific extraction step is as follows: extracted with ethyl acetate and saturated brine.
Further, in the step S2, the drying is performed with anhydrous sodium sulfate.
Further, in the step S2, the specific steps of separation and purification by column chromatography are as follows: the residue after distillation under reduced pressure was separated and purified by silica gel column chromatography using petroleum ether/ethyl acetate (40:1) as a mobile phase to give compound 3.
Examples one to ten:
compound 1 (2 mmol,204 mg), compound 2 (6 mmol, 630 mg), selenium dioxide (4 mmol,444 mg), sodium ethoxide (4 mmol,272 mg), DMSO (2 mmol,10 mL) were added sequentially to a 10mL round bottom flask, the round bottom flask was filled with argon, the reaction was carried out at 80 ℃ for 10h, and the progress of the reaction was monitored by thin layer chromatography until the reaction was complete; extraction with ethyl acetate and saturated brine, drying over anhydrous sodium sulfate, evaporation of the solvent under reduced pressure, and purification of the residue by silica gel column chromatography using petroleum ether/ethyl acetate (40:1) as the mobile phase gave compound 3 in 83% yield.
The yields of starting compound 1, compound 2 and product compound 3 and compound 3 are shown in table 1:
TABLE 1
The compound 3 obtained in examples one to ten was subjected to nuclear magnetic characterization, and the following data were obtained:
implementing the following steps: 1 HNMR(400MHz,CDCl 3 ,ppm)δ7.78-7.75(m,2H),7.62-7.60(m,2H),7.48-7.45(m,2H),7.43-7.40(m,2H),7.39-7.36(m,2H),7.35-7.22(m,5H),6.81(s,1H)； 13 C NMR(100MHz,CDCl 3 ,ppm)δ152.56,147.90,134.33,131.12,130.54,128.78,128.73,128.71,128.44,127.56,127.53,127.34,126.15,124.54,123.83,109.49.HRMS calcd for C 22 H 17 O[M+H] + 297.1274；found:297.1275.
embodiment two: 1 H NMR(400MHz,CDCl 3 ,ppm)δ7.67-7.65(m,2H),7.54-7.52(m,2H),7.33-7.25(m,4H),7.21-7.08(m,6H),6.92(s,1H),2.30(s,3H)； 13 C NMR(100MHz,CDCl 3 ,ppm)δ152.58,147.84,137.16,131.44,131.39,130.73,129.52,128.86,128.68,128.51,127.60,127.52,126.21,124.64,123.94,109.71,21.39.HRMS calcd forC 23 H 19 O[M+H] + 311.1431；found:311.1434.
embodiment III: 1 H NMR(400MHz,CDCl 3 ,ppm)δ7.79-7.77(m,2H),7.46-7.40(m,4H),7.31-7.16(m,8H),6.70(s,1H),2.19(s,3H)； 13 C NMR(100MHz,CDCl 3 ,ppm)δ152.08,147.81,136.89,134.15,131.25,130.60,130.37,130.16,128.79,128.47,127.90,127.52,127.06,126.16,124.68,123.79,123.76,110.33,20.13.HRMS calcdfor C 23 H 19 O 2 [M+H] + 327.1380；found:327.1385.
embodiment four: 1 H NMR(400MHz,CDCl 3 ,ppm)δ7.76-7.74(m,2H),7.59-7.56(m,2H),7.43-7.39(m,4H),7.33-7.23(m,4H),7.10-7.04(m,2H),6.77(s,1H)； 13 C NMR(100MHz,CDCl 3 ,ppm)δ162.19(d,J＝244.9Hz,1C),152.63,147.91,130.94,130.36(d,J＝8.0Hz,1C),130.33,130.27,128.80,128.51,127.66,127.64,126.11,123.84,123.51,115.71(d,J＝21.2Hz,1C),109.35.HRMS calcd for C 22 H 16 FO[M+H] + 315.1180；found:315.1172.
fifth embodiment: 1 H NMR(400MHz,CDCl 3 ,ppm)δ7.77-7.75(m,2H),7.64-7.61(m,2H),7.59-7.56(m,4H),7.44-7.40(m,2H),7.36-7.29(m,4H),6.81(s,1H)； 13 C NMR(100MHz,CDCl 3 ,ppm)δ153.07,148.63,138.07,130.62,130.23,129.45,128.87,128.84,128.64,128.06,127.84,126.43,125.67(q,J＝3.8Hz,1C),123.89,123.06,122.89,108.82.HRMS calcd for C 23 H 16 F 3 O[M+H] + 365.1148；found:365.1147.
example six: 1 H NMR(400MHz,CDCl 3 ,ppm)δ7.65(d,J＝8.0Hz,2H),7.50-7.45(m,4H),7.39-7.31(m,3H),7.22(d,J＝8.0Hz,2H),7.11(d,J＝8.0Hz,2H),6.75(s,1H),2.38(s,3H),2.35(s,3H)； 13 C NMR(100MHz,CDCl 3 ,ppm)δ152.51,147.78,137.31,134.54,129.42,129.11,128.67,128.62,128.43,127.94,127.13,126.11,123.73,108.64,21.35,21.33.HRMS calcd for C 24 H 21 O[M+H] + 325.1587；found:325.1587.
embodiment seven: 1 H NMR(400MHz,CDCl 3 ,ppm)δ7.50-7.48(m,1H),7.44-7.28(m,9H),7.25-7.19(m,1H),6.99-6.90(m,2H),6.78(s,1H)； 13 C NMR(100MHz,CDCl 3 ,ppm)δ163.23(d,J＝243.9Hz,1C),162.84(d,J＝243.6Hz,1C),151.64(d,J＝3.2Hz,1C),146.93(d,J＝3.0Hz,1C),133.64,132.80(d,J＝8.5Hz,1C),132.30(d,J＝8.4Hz,1C),130.45(d,J＝8.4Hz,1C),130.04(d,J＝8.4Hz,1C),128.90,128.74,127.82,125.68,121.64(d,J＝2.9Hz,1C),119.57(d,J＝2.9Hz,1C),114.58(d,J＝21.3Hz,1C),114.52(d,J＝21.2Hz,1C),112.76(d,J＝23Hz,1C),110.75(d,J＝23.4Hz,1C),110.69.HRMS calcd for C 22 H 15 F 2 O[M+H] + 333.1086；found:333.1084.
example eight: 1 H NMR(400MHz,CDCl 3 ,ppm)δ7.69-7.66(m,2H),7.55-7.51(m,2H),7.42-7.31(m,5H),7.10-7.06(m,2H),7.00-6.95(m,2H),6.70(s,1H)； 13 C NMR(100MHz,CDCl 3 ,ppm)δ162.33,(d,J＝246.0Hz,1C),162.21(d,J＝246.5Hz,1C),151.76,147.10,134.02,128.82,128.64,127.99(d,J＝7.9Hz,1C),127.49,127.29(d,J＝3.3Hz,1C),126.84(d,J＝3.0Hz,1C),125.57(d,J＝8.0Hz,1C),124.28,115.85(d,J＝21.8Hz,1C),115.53(d,J＝21.6Hz,1C),109.06.HRMS calcdfor C 22 H 15 F 2 O[M+H] + 333.1086；found:333.1086.
example nine: 1 H NMR(400MHz,CDCl 3 ,ppm)δ7.66-7.63(m,2H),7.51-7.48(m,2H),7.43-7.34(m,7H),7.27-7.24(m,2H),6.76(s,1H)； 13 C NMR(100MHz,CDCl 3 ,ppm)δ151.74,147.07,133.77,133.36,129.33,129.04,128.88,128.81,128.72,128.64,127.67,127.29,125.13,125.05,110.00.HRMS calcd for C 22 H 15 Cl 2 O[M+H] + 365.0495；found:365.0497.
example ten: 1 HNMR(400MHz,CDCl 3 ,ppm)δ7.87-7.85(d,J＝8.0Hz,2H),7.14-7.67(m,4H),7.57-7.55(d,J＝8.4Hz,2H),7.45-7.39(m,5H),6.94(s,1H)； 13 C NMR(100MHz,CDCl 3 ,ppm)δ151.95,147.41,134.04,133.44,133.37,129.70(q,J＝15Hz,1C),129.38(q,J＝15Hz,1C),129.13,128.80,128.16,126.80,126.16,126.02(q,J＝3.8Hz,1C),125.62(q,J＝3.9Hz,1C),124.09,122.88,122.84,111.78.HRMS calcdfor C 24 H 15 F 6 O[M+H] + 433.1022；found:433.1025.
by characterization of compound 3 prepared in examples one to ten above, it can be seen that the desired product can be prepared by the preparation method of the present invention.
Comparative example one (catalyst-free selenium dioxide)
A10 mL round bottom flask was charged with compound 1 (2 mmol,204 mg), compound 2 (6 mmol, 630 mg), sodium ethoxide (4 mmol,272 mg), DMSO (2 mmol,10 mL) and argon was reacted at 80℃for 10h to give comparative product one.
Comparative examples two to eleven (acidic or basic catalyst did not react)
A10 mL round bottom flask was charged with compound 1 (2 mmol,204 mg), compound 2 (6 mmol,636 mg), catalyst (4 mmol,444 mg), sodium ethoxide (4 mmol,272 mg), DMSO (2 mmol,10 mL) and argon was charged to react at 80℃for 10h to give comparison products II to eleven.
Thin layer chromatography monitoring is carried out on the comparison products one to eleven obtained in the comparison examples one to eleven, and no polysubstituted furan compounds are generated.
The foregoing disclosure is illustrative of the preferred embodiments of the present invention, and is not to be construed as limiting the scope of the invention, as it is understood by those skilled in the art that all or part of the above-described embodiments may be practiced with equivalents thereof, which fall within the scope of the invention as defined by the appended claims.
Claims (6)
1. A preparation method for constructing polysubstituted furan compounds by using phenylacetylene compounds and benzaldehyde compounds is characterized by comprising the following steps: comprises the following steps of the method,
s1: reacting the compound 1 with the compound 2 under the conditions of a catalyst, a solvent and an additive at a preset temperature to generate a solution containing the compound 3;
s2: extracting, drying, distilling under reduced pressure, separating and purifying the solution containing the compound 3 by column chromatography to obtain the compound 3;
the synthetic route is as follows:
the R is 1 The method comprises the following steps: hydrogen, methyl, methoxy, fluoro, trifluoromethyl
R 2 The method comprises the following steps: hydrogen, methyl, fluorine, chlorine, trifluoromethyl.
2. The method for preparing the polysubstituted furan compound by using the phenylacetylene compound and the benzaldehyde compound according to claim 1, which is characterized in that: the catalyst is selenium dioxide.
3. The method for preparing the polysubstituted furan compound by using the phenylacetylene compound and the benzaldehyde compound according to claim 1, which is characterized in that: the solvent is one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide.
4. The method for preparing the polysubstituted furan compound by using the phenylacetylene compound and the benzaldehyde compound according to claim 1, which is characterized in that: the additive is one of sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide, sodium methoxide, potassium methoxide, tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide.
5. The method for preparing the polysubstituted furan compound by using the phenylacetylene compound and the benzaldehyde compound according to claim 1, which is characterized in that: the predetermined temperature is 60 ℃ to 100 ℃.
6. The method for preparing the polysubstituted furan compound by using the phenylacetylene compound and the benzaldehyde compound according to claim 1, which is characterized in that: the molar ratio of the compound 1 to the compound 2 to the catalyst is as follows: 1:2-5:2-3.
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