CN103450123A - Method for preparing 2-furan formyl-3-aryl-4-ethoxycarbonyl-5-methyl-anti-form-2 and 3-dihydrofuran under catalytic action of niobium chloride - 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 chlorideDownload PDFInfo
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- CN103450123A CN103450123ACN2013104386590ACN201310438659ACN103450123ACN 103450123 ACN103450123 ACN 103450123ACN 2013104386590 ACN2013104386590 ACN 2013104386590ACN 201310438659 ACN201310438659 ACN 201310438659ACN 103450123 ACN103450123 ACN 103450123A
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- YHBDIEWMOMLKOO-UHFFFAOYSA-IpentachloroniobiumChemical compoundCl[Nb](Cl)(Cl)(Cl)ClYHBDIEWMOMLKOO-UHFFFAOYSA-I0.000titleclaimsabstractdescription38
- 238000000034methodMethods0.000titleclaimsabstractdescription30
- YLQBMQCUIZJEEH-UHFFFAOYSA-NFuranChemical compoundC=1C=COC=1YLQBMQCUIZJEEH-UHFFFAOYSA-N0.000titleabstract5
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- 238000006243chemical reactionMethods0.000claimsabstractdescription43
- -1furancarbonyl methyl triphenyl arsineChemical compound0.000claimsdescription41
- YMWUJEATGCHHMB-UHFFFAOYSA-NDichloromethaneChemical compoundClCClYMWUJEATGCHHMB-UHFFFAOYSA-N0.000claimsdescription24
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- MVPPADPHJFYWMZ-UHFFFAOYSA-NchlorobenzeneChemical compoundClC1=CC=CC=C1MVPPADPHJFYWMZ-UHFFFAOYSA-N0.000claimsdescription10
- 238000002425crystallisationMethods0.000claimsdescription10
- 230000008025crystallizationEffects0.000claimsdescription10
- XLYOFNOQVPJJNP-UHFFFAOYSA-NwaterSubstancesOXLYOFNOQVPJJNP-UHFFFAOYSA-N0.000claimsdescription10
- WSLDOOZREJYCGB-UHFFFAOYSA-N1,2-DichloroethaneChemical compoundClCCClWSLDOOZREJYCGB-UHFFFAOYSA-N0.000claimsdescription7
- 239000002994raw materialSubstances0.000claimsdescription6
- 230000035484reaction timeEffects0.000claimsdescription6
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- 125000003118aryl groupChemical group0.000claimsdescription2
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- KCVMLPGIPLETQZ-SJLPKXTDSA-Nethyl (2R,3R)-2-(furan-2-carbonyl)-5-methyl-3-phenyl-2,3-dihydrofuran-4-carboxylateChemical compoundCCOC(=O)C1=C(O[C@H]([C@@H]1C2=CC=CC=C2)C(=O)C3=CC=CO3)CKCVMLPGIPLETQZ-SJLPKXTDSA-N0.000description11
- 238000006555catalytic reactionMethods0.000description7
- JKTCBAGSMQIFNL-UHFFFAOYSA-N2,3-dihydrofuranChemical compoundC1CC=CO1JKTCBAGSMQIFNL-UHFFFAOYSA-N0.000description5
- 238000003786synthesis reactionMethods0.000description5
- 239000002699waste materialSubstances0.000description4
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- 230000015572biosynthetic processEffects0.000description3
- UMVYIMMSPIKCDD-SJLPKXTDSA-Nethyl (2R,3R)-2-(furan-2-carbonyl)-3-(4-hydroxyphenyl)-5-methyl-2,3-dihydrofuran-4-carboxylateChemical compoundCCOC(=O)C1=C(O[C@H]([C@@H]1C2=CC=C(C=C2)O)C(=O)C3=CC=CO3)CUMVYIMMSPIKCDD-SJLPKXTDSA-N0.000description3
- OYNHBXKAOMKFET-SJLPKXTDSA-Nethyl (2R,3R)-2-(furan-2-carbonyl)-5-methyl-3-(4-nitrophenyl)-2,3-dihydrofuran-4-carboxylateChemical compoundCCOC(=O)C1=C(O[C@H]([C@@H]1C2=CC=C(C=C2)[N+](=O)[O-])C(=O)C3=CC=CO3)COYNHBXKAOMKFET-SJLPKXTDSA-N0.000description3
- 150000002240furansChemical class0.000description3
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
Description
Technical field
The present invention relates to a kind of chemical feedstocks synthetic method, be specifically related to the method that columbium pentachloride catalysis prepares 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan.
Technical background
The dihydrofuran ring is as a kind of heterogeneous ring compound, closely related with the mankind's life.No matter be in natural compounds or synthetic compound, can look for the structure fragment of dihydrofuran, as the large class mycocide with important commercial value is exactly to take 2,3 dihydro furan as its basic framework, and the nucleosides that furan nucleus is modified has shown strong antiviral, antitumor efficacy.On the other hand, dihydrofuran derivative is also intermediate very useful in organic synthesis, and further group is converted to many bioactive compounds that have, and by it, is set out and can be synthesized many different compounds.Purposes is widely arranged in chemistry due to dihydrofuran, and for a long time, its synthetic method is subject to numerous chemists' attention always, becomes the focus of organic synthesis.The compound of the dihydrofuran constitutional unit that contains furan nucleus has caused widely in pharmaceutical chemistry to be paid attention to, but it is low that existing most technique all exists product yield, often producing the cis-trans isomerism mixture causes stereoselectivity poor, therefore 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 for the new synthesis technique of the cyclopropane ring derivative that contains furan nucleus seem very necessary.
Traditional synthesis technique of comparing, the exploitation of the cyclopropane derivative new synthesis process of constantly carrying out in recent years is mainly around the optimization of the exploitation of catalyzer and reaction conditions thereof and carry out, 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 the trade waste disposal of pollutants is large.
The report for preparing 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan product with columbium pentachloride catalysis is not also arranged at present.
Summary of the invention
The present invention will provide a kind of 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2 that prepare under the condition of columbium pentachloride catalysis; the method of 3-dihydrofuran; to take columbium pentachloride as catalyzer; under the low reaction conditions required, reacted; 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.
A kind of 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2 that prepare of the present invention; the method of 3-dihydrofuran; with bromination furancarbonyl methyl triphenyl arsine; 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate is raw material, under the effect that the columbium pentachloride of take in solvent is catalyzer, is prepared from.
The method for preparing 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan of the present invention preferably includes following steps:
(a) control 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) described each mass component raw material of step (a) is dropped in reaction vessel, be stirred to each component and fully dissolve, the control temperature of reaction is 0-40 ℃, and reaction times 3-6 hour, obtain reaction soln;
(c) by the reaction soln of (b) step, to pour 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 C1-C3alkyl in any.
Preparation 2-furancarbonyl of the present invention-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2; the method of 3-dihydrofuran, preferably control 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, its described solvent is any 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 that each feed composition bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate and stirring solvent are dissolved to abundant, then when stirring, slowly adds the catalyzer columbium pentachloride and is reacted.
Prepare the method for 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan as the further improved columbium pentachloride catalysis of the present invention, 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 can reduce the usage quantity of solvent, reduce the infringement of reaction solvent to environment and personnel.
Prepare 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2 as the further improved columbium pentachloride catalysis of 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, for first dropping into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate and stirring solvent to fully dissolving, then slowly adds columbium pentachloride and is reacted when stirring.Can effectively improve reaction efficiency by above-mentioned feeding method, thereby improve the reaction yield of 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan, and Reaction time shorten.
Columbium pentachloride catalysis provided by the present invention prepares 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2; the method of 3-dihydrofuran be take columbium pentachloride as catalyzer; can under the low reaction conditions required, be reacted; industrial energy consumption can be solved effectively high; the problems such as the yield of product is low, and the 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, and 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: the reaction conditions gentleness, 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, below in conjunction with embodiment, the present invention is described in further detail, 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 in accordance with the following steps 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan:
(a) control bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-phenyl-ethyl propenoate: columbium pentachloride: the ratio of the amount of substance of methylene dichloride is 1:1:2:2;
(b) the ratio raw material of each amount of substance step (a) taken drops in reaction vessel simultaneously, is stirred to each component and fully dissolves, and controlling temperature of reaction is that 0 ~ 40 ℃ of reaction times is 5 ~ 6 hours, obtains reaction soln;
(c) step (b) is reacted to the complete reaction soln made and pour in cold water, 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 to magnetic resonance detection, nuclear magnetic data:1h NMR (400 MHz, CDCl3)δ(ppm): 1.04 (t,j=7.1 Hz, 3H, CH3), 2.41 (d,j=1.4 Hz, 3H, CH3), 3.98 (q, 2H, CH2), 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) control bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-phenyl-ethyl propenoate: columbium pentachloride: the ratio of the amount of substance of methylene dichloride is 1:2:2:4;
(b) the ratio raw material of each amount of substance step (a) taken drops in reaction vessel simultaneously, is stirred to each component and fully dissolves, and the control temperature of reaction is 0-40 ℃, and the reaction times is within 5-6 hour, to obtain reaction soln;
(c) step (b) is reacted to the complete reaction soln obtained and pour 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 73%.
Gained invention product is carried out to magnetic resonance detection, nuclear magnetic data:1h NMR (400 MHz, CDCl3)δ(ppm): 1.04 (t,j=7.1 Hz, 3H, CH3), 2.41 (d,j=1.4 Hz, 3H, CH3), 3.98 (q, 2H, CH2), 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 in accordance with the following steps 2-furancarbonyl-3-phenyl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan:
(a) control bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-phenyl-ethyl propenoate: columbium pentachloride: the ratio of the amount of substance of methylene dichloride is 1:2:2:4;
(b) the bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-phenyl-ethyl propenoate and the methylene dichloride that first drop into are stirred to abundant dissolving, then slowly adding columbium pentachloride when stirring is reacted, controlling temperature of reaction is 0-40 ℃, reaction times is 3-4 hour, obtains reaction soln;
(c), step (b) is reacted to the complete reaction soln obtained and pour 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, CDCl3)δ(ppm): 1.04 (t,j=7.1 Hz, 3H, CH3), 2.41 (d,j=1.4 Hz, 3H, CH3), 3.98 (q, 2H, CH2), 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) control bromination furancarbonyl methyl triphenyl arsine: 2-ethoxycarbonyl-3-phenyl-ethyl propenoate: columbium pentachloride: the ratio of the amount of substance of ethylene dichloride is 1:2:2:3;
(b) first drop into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-phenyl-ethyl propenoate and ethylene dichloride and be stirred to abundant dissolving, then slowly adding columbium pentachloride when stirring is reacted, at 0-40 ℃ of temperature, reaction 3-4 hour, obtain reaction soln;
(c) step (b) is reacted to the complete reaction soln obtained and pour 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 75%.
Nuclear magnetic data:1h NMR (400 MHz, CDCl3)δ(ppm): 1.04 (t,j=7.1 Hz, 3H, CH3), 2.41 (d,j=1.4 Hz, 3H, CH3), 3.98 (q, 2H, CH2), 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) take bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-(4-chloro-phenyl-)-ethyl propenoate, columbium pentachloride and the ethylene dichloride that the ratio of amount of substance is 1:2:2:4;
(b) first drop into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-(4-chloro-phenyl-)-ethyl propenoate and ethylene dichloride and be stirred to abundant dissolving, then slowly adding columbium pentachloride when stirring is reacted, be reaction 3-4 hour under 0-40 ℃ of condition in temperature, obtain reaction soln;
(c) step (b) is reacted to the complete reaction soln obtained and pour in cold water, 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, CDCl3)δ(ppm): 1.03 (t,j=7.1 Hz, 3H, CH3), 2.42 (d,j=1.4 Hz, 3H, CH3), 4.01 (q, 2H, CH2), 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 in accordance with the following steps 2-furancarbonyl-3-(4-nitrophenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan:
(a) control 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) first drop into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-(4-nitrophenyl)-ethyl propenoate and chloroform and be stirred to abundant dissolving, then slowly adding columbium pentachloride when stirring is reacted, be reaction 3-4 hour under 0-40 ℃ of condition in temperature, obtain reaction soln;
(c) step (b) is reacted to the complete reaction soln obtained and pour in cold water, 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, CDCl3)δ(ppm): 1.04 (t,j=7.1 Hz, 3H, CH3), 2.43 (d,j=1.4 Hz, 3H, CH3), 3.97 (q,j=7.1 Hz, 2H, CH2), 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 in accordance with the following steps 2-furancarbonyl-3-(4-hydroxy phenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan:
(a) control 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) first drop into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-(4-hydroxy phenyl)-ethyl propenoate and chlorobenzene and be stirred to abundant dissolving, then slowly adding columbium pentachloride when stirring is reacted, be reaction 3-4 hour under 40 ℃ of conditions of 0-in temperature, obtain reaction soln;
(c) step (b) is reacted to the complete reaction soln obtained and pour in cold water, 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, CDCl3)δ(ppm): 1.05 (t,j=7.1 Hz, 3H, CH3), 2.42 (d,j=1.4 Hz, 3H, CH3), 3.98 (q, 2H, CH2), 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 in accordance with the following steps 2-furancarbonyl-3-(4-aminomethyl phenyl)-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan:
(a) control 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) first drop into bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-(4-aminomethyl phenyl)-ethyl propenoate and methylene dichloride and be stirred to abundant dissolving, then slowly adding columbium pentachloride when stirring is reacted, be reaction 3-4 hour under 0-40 ℃ of condition in temperature, obtain reaction soln;
(c) step (b) is reacted to the complete reaction soln obtained and pour in cold water, 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, CDCl3)δ(ppm): 1.03 (t,j=7.1 Hz, 3H, CH3), 2.37 (s, 3H, CH3), 2.42 (d,j=1.4 Hz, 3H, CH3), 4.00 (q,j=7.1 Hz, 2H, CH2), 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 (7)
1. one kind 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, under the effect that the columbium pentachloride of take in solvent is catalyzer, is prepared from.
2. the method for 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) control 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) described each mass component raw material of step (a) is dropped in reaction vessel, be stirred to each component and fully dissolve, the control temperature of reaction is 0-40 ℃, and reaction times 3-6 hour, obtain reaction soln;
(c) by the reaction soln of (b) step, to pour 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 the described method for preparing 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan of claim 1 or 2, it is characterized in that the aryl in described 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate is selected from:
Wherein R is selected from: halogen, nitro, hydroxyl or C1-C3alkyl in any.
4. preparation 2-furancarbonyl according to claim 1 and 2-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2; the method of 3-dihydrofuran, it 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 for preparing 2-furancarbonyl-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2,3 dihydro furan according to claim 1 and 2, is characterized in that described solvent is any in chlorobenzene, methylene dichloride, ethylene dichloride, chloroform.
6. the method for 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.
7. preparation 2-furancarbonyl according to claim 2-3-aryl-4-ethoxycarbonyl-5-methyl-trans-2; the method of 3-dihydrofuran; it is characterized in that described step (b) is that each feed composition bromination furancarbonyl methyl triphenyl arsine, 2-ethoxycarbonyl-3-substituted-phenyl-ethyl propenoate and stirring solvent are dissolved to abundant, then when stirring, slowly add the catalyzer columbium pentachloride and reacted.
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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 |
| US20120046421A1 (en)* | 2010-08-17 | 2012-02-23 | Uchicago Argonne, Llc | Ordered Nanoscale Domains by Infiltration of Block Copolymers |
| US20130197280A1 (en)* | 2009-12-29 | 2013-08-01 | Ei Du Pont De Nemours And Company | Synthesis of fluorinated olefins from fluorinated alcohols |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| US20130197280A1 (en)* | 2009-12-29 | 2013-08-01 | Ei Du Pont De Nemours And Company | Synthesis of fluorinated olefins from fluorinated alcohols |
| US20120046421A1 (en)* | 2010-08-17 | 2012-02-23 | Uchicago Argonne, Llc | Ordered Nanoscale Domains by Infiltration of Block Copolymers |
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| ZHANG HUI 等: "Highly Stereoselective Synthesis of trans-3-Aryl-4-carbethoxy-2,3-dihydro-2-fur-2"-oyl-5-methylfurans", 《CHINESE JOURNAL OF CHEMISTRY》* |
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