CN103450123B - Method for preparing 2-furan formyl-3-aryl-4-ethoxycarbonyl-5-methyl-anti-form-2 and 3-dihydrofuran under catalytic action of niobium pentachloride - Google Patents
Method for preparing 2-furan formyl-3-aryl-4-ethoxycarbonyl-5-methyl-anti-form-2 and 3-dihydrofuran under catalytic action of niobium pentachloride Download PDFInfo
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Abstract
The invention provides a method for preparing 2-furan formyl-3-aryl-4-ethoxycarbonyl-5-methyl-anti-form-2 and 3-dihydrofuran under the catalytic action of niobium chloride. According to the method for preparing the 2-furan formyl-3-aryl-4-ethoxycarbonyl-5-methyl-anti-form-2 and 3-dihydrofuran under the catalytic action of the niobium chloride, the niobium chloride is used to serve as a catalyzer, and reaction is carried out under the reaction condition with low requirements to prepare the 2-furan formyl-3-aryl-4-ethoxycarbonyl-5-methyl-anti-form-2 and 3-dihydrofuran. The method for preparing the 2-furan formyl-3-aryl-4-ethoxycarbonyl-5-methyl-anti-form-2 and 3-dihydrofuran under the catalytic action of the niobium chloride has the advantages that the prepared product is easy to separate, the technique is simple, and little industrial waste is generated.
Description
Technical field
The present invention relates to a kind of chemical feedstocks synthetic method, be specifically related to the method that 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan is prepared in columbium pentachloride catalysis.
Technical background
Dihydrofuran ring is as a kind of heterogeneous ring compound, closely related with the life of the mankind.No matter be in natural compounds or synthetic compound, can look for the structure fragment of dihydrofuran, be exactly be its basic framework with 2,3 dihydro furan as one with important commercial value large class mycocide, and the nucleosides that furan nucleus is modified shows strong antiviral, antitumor efficacy.On the other hand, dihydrofuran derivative is also intermediate very useful in organic synthesis, can be converted to and manyly has bioactive compound by group further, can synthesize many different compounds by it.Because dihydrofuran has purposes widely in chemistry, for a long time, its synthetic method is subject to the attention of numerous chemist always, becomes the focus of organic synthesis.The compound of the dihydrofuran constitutional unit containing furan nucleus causes in pharmaceutical chemistry to be paid attention to widely, but it is low that existing most technique all also exists product yield, often producing cis-trans isomerism mixture causes stereoselectivity poor, cause the deficiency of the aspects such as product is not easily separated, purifying technique is complicated, trade waste is seriously polluted, the R and D therefore for the new synthesis technique of the cyclopropane ring derivative containing furan nucleus seem very necessary.
To compare traditional synthesis technique, the exploitation of the cyclopropane derivative new synthesis process constantly carried out in recent years is mainly carried out around the optimization of the exploitation of catalyzer and reaction conditions thereof, it is high that the selecting properly of catalyzer can solve industrial energy consumption effectively, the problems such as the yield of product is low, and trade waste disposal of pollutants is large.
Also there is not the report preparing 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan product with columbium pentachloride catalysis at present.
Summary of the invention
The present invention will provide a kind of under the condition of columbium pentachloride catalysis, prepare 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2; the method of 3-dihydrofuran; take columbium pentachloride as catalyzer; react under the reaction conditions of lower requirement; prepare 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan.Prepare the easily separated technique of product simple, trade waste is few.
One of the present invention prepares 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2; the method of 3-dihydrofuran; with bromination furancarbonyl methyl triphenyl arsine; 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate is raw material, is in a solvent to be prepared under the effect of catalyzer with columbium pentachloride.
The method preparing 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan of the present invention, preferably includes following steps:
A () controls bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate: the ratio of the amount of substance of columbium pentachloride is 1: (1-2): (1-2), and appropriate solvent;
B each mass component raw material described in step (a) drops in reaction vessel by (), be stirred to each component and fully dissolve, control temperature of reaction is 0-40 DEG C, and reaction times 3-6 hour, obtains reaction soln;
C (), by the reaction soln of (b) step, pours in cold water, crystallization is filtered, and obtains product 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan after oven dry.
Preparation method of the present invention, the aryl in preferred described 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate is selected from:
，
Wherein R is selected from: halogen, nitro, hydroxyl or C
1-C
3alkyl in any one.
Preparation 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2 of the present invention; the method of 3-dihydrofuran, preferably controls bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate: columbium pentachloride: the ratio of the amount of each component materials of solvent is 1: (1-2): (1-2): (2-4).
Method of the present invention, solvent described in it is any one in chlorobenzene, methylene dichloride, ethylene dichloride, chloroform.
Solvent of the present invention is preferably methylene dichloride.
Method of the present invention; preferred described step (b) is dissolved to abundant at each feed composition bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate and stirring solvent, then while stirring, slowly adds catalyzer columbium pentachloride and react.
The method of 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan is prepared in the columbium pentachloride catalysis improved further as the present invention, and described solvent is preferably methylene dichloride.It is compared with chlorobenzene, ethylene dichloride, chloroform; methylene dichloride can improve 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2; the reaction yield of 3-dihydrofuran, and the usage quantity that can reduce solvent, reduce the infringement of reaction solvent to environment and personnel.
2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2 is prepared in the columbium pentachloride catalysis improved further as the present invention; the method of 3-dihydrofuran; in preferred described step (b), the feeding sequence of bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate, columbium pentachloride and solvent is first drop into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate and stirring solvent to fully dissolving, and then while stirring, slowly adds columbium pentachloride and reacts.Effectively can improve reaction efficiency by above-mentioned feeding method, thus improve the reaction yield of 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan, and Reaction time shorten.
2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2 is prepared in columbium pentachloride catalysis provided by the present invention; the method of 3-dihydrofuran take columbium pentachloride as catalyzer; can react under the reaction conditions of lower requirement; can effectively solve industrial energy consumption high; the problems such as the yield of product is low, and trade waste disposal of pollutants is large.Prepare 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan; And reaction product 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan is easy to separating-purifying, productive rate can reach more than 60%.
Technical solution of the present invention can be expressed as follows:
The present invention compared with prior art has following advantages: reaction conditions is gentle, and stereoselectivity is high, and productive rate is better, and product is easy to purifying etc.
embodiment
In order to deepen the understanding of the present invention, be described in further detail the present invention below in conjunction with embodiment, following examples only for explaining the present invention, do not form limiting the scope of the present invention.The ratio of amount of substance.
embodiment 1
Prepare 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan in accordance with the following steps:
A () controls bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-phenyl-acryloyl acetoacetic ester: columbium pentachloride: the ratio of the amount of substance of methylene dichloride is 1:1:2:2;
The ratio raw material of b each amount of substance that step (a) takes by () drops in reaction vessel simultaneously, is stirred to each component and fully dissolves, and control temperature of reaction is 0 ~ 40 DEG C of reaction times is 5 ~ 6 hours, obtains reaction soln;
C step (b) is reacted complete obtained reaction soln and is poured in cold water by (), crystallization is filtered, and obtains 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan after oven dry.
The product yield of gained 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan is 63%.
Gained invention product is carried out magnetic resonance detection, nuclear magnetic data:
1h NMR (400 MHz, CDCl
3)
δ(ppm): 1.04 (t,
j=7.1 Hz, 3H, CH
3), 2.41 (d,
j=1.4 Hz, 3H, CH
3), 3.98 (q, 2H, CH
2), 4.43 (dd,
j=1.4 Hz, 4.9 Hz, 1H, CH), 5.41 (d,
j=4.9 Hz, 1H, CH), 6.58 (dd,
j=1.6 Hz, 3.6 Hz, 1H, ArH), 7.11-7.37 (m, 6H, Ar-H), 7.62 (dd,
j=0.5 Hz, 1.6 Hz, 1H, ArH). above digital proof gained compound is target compound.
embodiment 2
This example prepares 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan in accordance with the following steps:
A () controls bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-phenyl-acryloyl acetoacetic ester: columbium pentachloride: the ratio of the amount of substance of methylene dichloride is 1:2:2:4;
The ratio raw material of b each amount of substance that step (a) takes by () drops in reaction vessel simultaneously, and be stirred to each component and fully dissolve, control temperature of reaction is 0-40 DEG C, and the reaction times is obtain reaction soln in 5-6 hour;
C step (b) is reacted the complete reaction soln obtained and is poured in cold water by (), crystallization is filtered, and obtains 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan after oven dry.The product yield of gained 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan is 73%.
Gained invention product is carried out magnetic resonance detection, nuclear magnetic data:
1h NMR (400 MHz, CDCl
3)
δ(ppm): 1.04 (t,
j=7.1 Hz, 3H, CH
3), 2.41 (d,
j=1.4 Hz, 3H, CH
3), 3.98 (q, 2H, CH
2), 4.43 (dd,
j=1.4 Hz, 4.9 Hz, 1H, CH), 5.41 (d,
j=4.9 Hz, 1H, CH), 6.58 (dd,
j=1.6 Hz, 3.6 Hz, 1H, ArH), 7.11-7.37 (m, 6H, Ar-H), 7.62 (dd,
j=0.5 Hz, 1.6 Hz, 1H, ArH). above digital proof gained compound is target compound.
embodiment 3
Prepare 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan in accordance with the following steps:
A () controls bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-phenyl-acryloyl acetoacetic ester: columbium pentachloride: the ratio of the amount of substance of methylene dichloride is 1:2:2:4;
B bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-phenyl-acryloyl acetoacetic ester and methylene dichloride that () first drops into are stirred to abundant dissolving, then while stirring, slowly add columbium pentachloride to react, controlling temperature of reaction is 0-40 DEG C, reaction times is 3-4 hour, obtains reaction soln;
C (), reacts by step (b) to the complete reaction soln obtained and pours in cold water, crystallization is filtered, and obtains 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan after oven dry.The product yield of gained 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan is 71%.
Nuclear magnetic data:
1h NMR (400 MHz, CDCl
3)
δ(ppm): 1.04 (t,
j=7.1 Hz, 3H, CH
3), 2.41 (d,
j=1.4 Hz, 3H, CH
3), 3.98 (q, 2H, CH
2), 4.43 (dd,
j=1.4 Hz, 4.9 Hz, 1H, CH), 5.41 (d,
j=4.9 Hz, 1H, CH), 6.58 (dd,
j=1.6 Hz, 3.6 Hz, 1H, ArH), 7.11-7.37 (m, 6H, Ar-H), 7.62 (dd,
j=0.5 Hz, 1.6 Hz, 1H, ArH). above digital proof gained compound is target compound.
embodiment 4
This example prepares 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan in accordance with the following steps:
A () controls bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-phenyl-acryloyl acetoacetic ester: columbium pentachloride: the ratio of the amount of substance of ethylene dichloride is 1:2:2:3;
B () is first dropped into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-phenyl-acryloyl acetoacetic ester and ethylene dichloride and is stirred to abundant dissolving, then while stirring, slowly add columbium pentachloride to react, at temperature 0-40 DEG C, react 3-4 hour, obtain reaction soln;
C step (b) is reacted the complete reaction soln obtained and is poured in cold water by (), crystallization is filtered, and obtains 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan after oven dry.The product yield of gained 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan is 75%.
Nuclear magnetic data:
1h NMR (400 MHz, CDCl
3)
δ(ppm): 1.04 (t,
j=7.1 Hz, 3H, CH
3), 2.41 (d,
j=1.4 Hz, 3H, CH
3), 3.98 (q, 2H, CH
2), 4.43 (dd,
j=1.4 Hz, 4.9 Hz, 1H, CH), 5.41 (d,
j=4.9 Hz, 1H, CH), 6.58 (dd,
j=1.6 Hz, 3.6 Hz, 1H, ArH), 7.11-7.37 (m, 6H, Ar-H), 7.62 (dd,
j=0.5 Hz, 1.6 Hz, 1H, ArH). above digital proof gained compound is target compound.
embodiment5
This example prepares 2-furancarbonyl-3-(4-chloro-phenyl-)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan in accordance with the following steps:
A ratio that () takes amount of substance is bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-(4-chloro-phenyl-)-ethyl propenoate, columbium pentachloride and the ethylene dichloride of 1:2:2:4;
B () is first dropped into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-(4-chloro-phenyl-)-ethyl propenoate and ethylene dichloride and is stirred to abundant dissolving, then while stirring, slowly add columbium pentachloride to react, under temperature is 0-40 DEG C of condition, reacts 3-4 hour, obtains reaction soln;
C step (b) is reacted the complete reaction soln obtained and is poured in cold water by (), crystallization is filtered, and obtains 2-furancarbonyl-3-(4-chloro-phenyl-)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan after oven dry.The product yield of gained 2-furancarbonyl-3-(4-chloro-phenyl-)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan is 78%.
Nuclear magnetic data:
1h NMR (400 MHz, CDCl
3)
δ(ppm): 1.03 (t,
j=7.1 Hz, 3H, CH
3), 2.42 (d,
j=1.4 Hz, 3H, CH
3), 4.01 (q, 2H, CH
2), 4.43 (dd,
j=1.4 Hz, 4.9 Hz, 1H, CH), 5.42 (d,
j=4.9 Hz, 1H, CH), 6.58 (dd,
j=1.6 Hz, 3.6 Hz, 1H, ArH), 7.11-7.37 (m, 5H, Ar-H), 7.63 (dd,
j=0.5 Hz, 1.6 Hz, 1H, ArH). above digital proof gained compound is target compound.
embodiment6
Prepare 2-furancarbonyl-3-(4-nitrophenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan in accordance with the following steps:
A () controls bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-(4-nitrophenyl)-ethyl propenoate: columbium pentachloride: the ratio of the amount of substance of chloroform is 1:2:2:4;
B () is first dropped into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-(4-nitrophenyl)-ethyl propenoate and chloroform and is stirred to abundant dissolving, then while stirring, slowly add columbium pentachloride to react, under temperature is 0-40 DEG C of condition, reacts 3-4 hour, obtains reaction soln;
C step (b) is reacted the complete reaction soln obtained and is poured in cold water by (), crystallization is filtered, and obtains 2-furancarbonyl-3-(4-nitrophenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan after oven dry.The product yield of gained 2-furancarbonyl-3-(4-nitrophenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan is 67%.
Nuclear magnetic data:
1h NMR (400 MHz, CDCl
3)
δ(ppm): 1.04 (t,
j=7.1 Hz, 3H, CH
3), 2.43 (d,
j=1.4 Hz, 3H, CH
3), 3.97 (q,
j=7.1 Hz, 2H, CH
2), 4.63 (dd,
j=1.4 Hz, 4.9 Hz, 1H, CH), 5.41 (d,
j=4.9 Hz, 1H, CH), 6.62 (dd,
j=1.7 Hz, 3.6 Hz, 1H, ArH), 7.32 (dd,
j=0.5 Hz, 3.6 Hz, 1H, ArH), 7.42 (d,
j=6.9 Hz, 2H, ArH), 7.63 (dd,
j=0.5 Hz, 1.6 Hz, 1H, ArH), 8.21 (d,
j=6.9 Hz, 2H, ArH). above digital proof gained compound is target compound.
embodiment7
Prepare 2-furancarbonyl-3-(4-hydroxy phenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan in accordance with the following steps:
A () controls bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-(4-hydroxy phenyl)-ethyl propenoate: columbium pentachloride: the ratio of the amount of substance of chlorobenzene is 1:2:2:6;
B () is first dropped into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-(4-hydroxy phenyl)-ethyl propenoate and chlorobenzene and is stirred to abundant dissolving, then while stirring, slowly add columbium pentachloride to react, under temperature is 0-40 DEG C of conditions, reacts 3-4 hour, obtains reaction soln;
C step (b) is reacted the complete reaction soln obtained and is poured in cold water by (), crystallization is filtered, and obtains 2-furancarbonyl-3-(4-hydroxy phenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan after oven dry.The product yield of gained 2-furancarbonyl-3-(4-hydroxy phenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan is 72%.
Nuclear magnetic data:
1h NMR (400 MHz, CDCl
3)
δ(ppm): 1.05 (t,
j=7.1 Hz, 3H, CH
3), 2.42 (d,
j=1.4 Hz, 3H, CH
3), 3.98 (q, 2H, CH
2), 4.40 (dd,
j=1.4 Hz, 4.9 Hz, 1H, CH), 5.40 (d,
j=4.9 Hz, 1H, CH), 6.58 (dd,
j=1.6 Hz, 3.6 Hz, 1H, ArH), 6.76-7.16 (m, 5H, Ar-H), 7.63 (dd,
j=0.5 Hz, 1.6 Hz, 1H, ArH), 10.43 (s, 1H, OH). and above digital proof gained compound is target compound.
embodiment8
Prepare 2-furancarbonyl-3-(4-aminomethyl phenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan in accordance with the following steps:
A () controls bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-(4-aminomethyl phenyl)-ethyl propenoate: columbium pentachloride: the ratio of the amount of substance of methylene dichloride is 1:2:2:3;
B () is first dropped into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-(4-aminomethyl phenyl)-ethyl propenoate and methylene dichloride and is stirred to abundant dissolving, then while stirring, slowly add columbium pentachloride to react, under temperature is 0-40 DEG C of condition, reacts 3-4 hour, obtains reaction soln;
C step (b) is reacted the complete reaction soln obtained and is poured in cold water by (), crystallization is filtered, and obtains 2-furancarbonyl-3-(4-aminomethyl phenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan after oven dry.The product yield of gained 2-furancarbonyl-3-(4-aminomethyl phenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan is 76%.
Nuclear magnetic data:
1h NMR (400 MHz, CDCl
3)
δ(ppm): 1.03 (t,
j=7.1 Hz, 3H, CH
3), 2.37 (s, 3H, CH
3), 2.42 (d,
j=1.4 Hz, 3H, CH
3), 4.00 (q,
j=7.1 Hz, 2H, CH
2), 4.41 (dd,
j=1.4 Hz, 4.9 Hz, 1H, CH), 5.41 (d,
j=4.9 Hz, 1H, CH), 6.58 (dd,
j=1.7 Hz, 3.6 Hz, 1H, ArH), 7.22 (dd,
j=0.5 Hz, 3.6 Hz, 1H, ArH), 7.62 (d,
j=6.9 Hz, 2H, ArH), 7.11-7.20 (m, 4H, Ar-H). and above digital proof gained compound is target compound.
Claims (6)
1. prepare 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2 for one kind, the method of 3-dihydrofuran, with bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate is raw material, is in a solvent to be prepared under the effect of catalyzer with columbium pentachloride; Described solvent is any one in chlorobenzene, methylene dichloride, ethylene dichloride, chloroform.
2. the method preparing 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan according to claim 1, is characterized in that comprising the steps:
A () controls bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate: the ratio of the amount of substance of columbium pentachloride is 1: (1-2): (1-2), and appropriate solvent;
B each mass component raw material described in step (a) drops in reaction vessel by (), be stirred to each component and fully dissolve, control temperature of reaction is 0-40 DEG C, and reaction times 3-6 hour, obtains reaction soln;
C (), by the reaction soln of (b) step, pours in cold water, crystallization is filtered, and obtains product 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan after oven dry.
3. according to claim 1 or 2, prepare 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2; the method of 3-dihydrofuran, is characterized in that the substituted-phenyl in described 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate is selected from:
，
Wherein R is selected from: halogen, nitro, hydroxyl or C
1-C
3alkyl in any one.
4. preparation 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2 according to claim 1 and 2; the method of 3-dihydrofuran, is characterized in that described control bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate: columbium pentachloride: the ratio of the amount of substance of solvent is 1: (1-2): (1-2): (2-4).
5. the method preparing 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan according to claim 5, is characterized in that described solvent is methylene dichloride.
6. preparation 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2 according to claim 2; the method of 3-dihydrofuran; it is characterized in that described step (b) is dissolved to abundant at each feed composition bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate and stirring solvent, then while stirring, slowly add catalyzer columbium pentachloride and react.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037425A (en) * | 2007-04-25 | 2007-09-19 | 上海大学 | 2-furoyl-3-aryl-4-ethoxy acetyl-5-methyl-trans-2,3-Dihydrofuran and preparation method thereof |
| US20120046421A1 (en) * | 2010-08-17 | 2012-02-23 | Uchicago Argonne, Llc | Ordered Nanoscale Domains by Infiltration of Block Copolymers |
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| CN101037425A (en) * | 2007-04-25 | 2007-09-19 | 上海大学 | 2-furoyl-3-aryl-4-ethoxy acetyl-5-methyl-trans-2,3-Dihydrofuran and preparation method thereof |
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| Highly Stereoselective Synthesis of trans-3-Aryl-4-carbethoxy-2,3-dihydro-2-fur-2"-oyl-5-methylfurans;ZHANG Hui 等;《Chinese Journal of Chemistry》;20070716;第25卷(第7期);第968-972页 * |
| NbCl5催化的有机化学反应;侯俊涛 等;《河北师范大学学报/自然科学版》;20110531;第35卷(第3期);第289-295页 * |
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