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CN101747302B - A kind of synthetic method of polysubstituted benzofuran compound - Google Patents

A kind of synthetic method of polysubstituted benzofuran compound Download PDF

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CN101747302B
CN101747302B CN2008102392420A CN200810239242A CN101747302B CN 101747302 B CN101747302 B CN 101747302B CN 2008102392420 A CN2008102392420 A CN 2008102392420A CN 200810239242 A CN200810239242 A CN 200810239242A CN 101747302 B CN101747302 B CN 101747302B
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CN101747302A (en
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余荣
李志平
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Renmin University of China
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Renmin University of China
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Abstract

The invention discloses a method for synthesizing polysubstituted benzofuran compounds shown in a general formula I. In the method, in a system containing a catalyst {Fe} and a peroxide oxidant, compounds show in a general formula II are reacted with compounds shown in a general formula III to generate the compounds shown in the general formula I. In the method, industrial raw materials of phenoland derivatives thereof and the like can be directly used to construct the compounds with a polysubstituted benzofuran structure. The method has the advantages of simple and convenient operation; only by one step, the benzofuran compounds can be directly synthesized at high yield; the product is easy to purify; and the method is creative, is superior to other traditional organic synthesis methodsand has good application prospect.

Description

A kind of compound method of polysubstituted benzofuran compounds
Technical field
The present invention relates to a kind of compound method of polysubstituted benzofuran compounds.
Background technology
Cumarone, English benzofuran, as in the furan derivatives most important one type, it is present in a large amount of natural products widely, and has very high biological activity.For example: from samphire A Mi fennel seed
Figure G2008102392420D00011
The compound 1 that extracts is widely used in treatment stenocardia and vasodilation, and compound 2 also is very effective anticancer component.
In a word, the cumarone structural compounds is at natural product chemistry, and scientific domains such as life chemistry and pharmaceutical chemistry all have very important research and using value.Early stage synthesis strategy mainly concentrates on the several reactions of figure below:
Figure G2008102392420D00012
Visible by figure, the many and reaction substrate of the synthetic cumarone structural compounds step of conventional measures all compares harshness with condition.
Summary of the invention
The compound method that the purpose of this invention is to provide the polysubstituted benzofuran compounds shown in formula (I) general structure.
The compound method of the polysubstituted benzofuran compounds shown in formula provided by the present invention (I) general structure; Be in the system that contains catalyzer and peroxide oxidant; Beta-diketon shown in phenol shown in the formula (II) and the formula (III) is reacted, obtain the compound shown in the formula (I);
Figure G2008102392420D00021
Formula (I)
Figure G2008102392420D00022
Formula (II) formula (III)
Wherein:
R 1Be selected from alkyl, haloalkyl, alkenyl, halogenated alkenyl, alkynyl group, halo alkynyl group, aromatic base, the substituted aromatic base of methoxyl group, the substituted aromatic base of alkyl, alkoxyl group, amino, the substituted amino of an alkyl, anilino, imidazolyl, halo imidazolyl, pyridyl, halogenated pyridyl, furyl, halofuryl, thienyl and halogenated thiophene base;
R 2Be selected from alkyl, haloalkyl, alkenyl, halogenated alkenyl, alkynyl group, halo alkynyl group, aromatic base, the substituted aromatic base of methoxyl group, the substituted aromatic base of alkyl, alkoxyl group, amino, the substituted amino of an alkyl, anilino, imidazolyl, halo imidazolyl, pyridyl, halogenated pyridyl, furyl, halofuryl, thienyl and halogenated thiophene base;
R 3Be selected from hydrogen, halogen, alkyl, alkenyl, alkynyl group, phenyl, benzyl, imidazolyl and thienyl;
Said catalyzer is any or its arbitrary combination in following four kinds of molysite: divalent inorganic molysite, 3 valency inorganic molysites, the organic molysite of 0 valency and the organic molysite of divalent.
Said oxygenant is the superoxide shown in the formula (IV):
R 4-O-O-R 5
Formula (IV)
Wherein:
R 4Be selected from hydrogen, the tertiary butyl, phenyl, halogenophenyl, the substituted acyl group of phenyl, the substituted alkyl of phenyl;
R 5Be selected from hydrogen, the tertiary butyl, phenyl, halogenophenyl, the substituted acyl group of phenyl, the substituted alkyl of phenyl;
Said R 1Be preferably C 1-C 10Alkyl, C 1-C 10Alkenyl, C 1-C 10Alkynyl group, phenyl ring number be 1-5 aromatic base, C 1-C 10Alkoxyl group, anilino, pyridyl, thienyl or furyl;
Said R 2Be preferably C 1-C 10Alkyl, C 1-C 10Alkenyl, C 1-C 10Alkynyl group, phenyl ring number be 1-5 aromatic base, C 1-C 10Alkoxyl group, anilino, pyridyl, thienyl or furyl;
Said R 3Be preferably hydrogen, halogen, methyl, ethyl, allyl group, propargyl, phenyl, benzyl, imidazolyl and thienyl;
Said R 4Be preferably hydrogen, the tertiary butyl, phenyl, phenyl formyl radical or propyloxy phenyl base;
Said R 5Be preferably hydrogen, the tertiary butyl, phenyl, phenyl formyl radical or propyloxy phenyl base.
Said catalyzer is preferably FeCl 2, FeBr 2, FeI 2, FeCl 36H 2O, FeCl 3, FeBr 3, Fe (CH 3COO) 2, Fe (CO) 5, Fe 2(CO) 9And Fe 3(CO) 12In any or its arbitrary combination.
Said reaction can or be open under the conditions of air at starvation to be carried out.
In the said reaction; The mol ratio of beta-diketon shown in the formula (III) and peroxide oxidant is 1: 1～1: 6, and { mol ratio of Fe} ({ Fe} refers to the organic or inorganic molysite that is used as catalyzer among the present invention) and the beta-diketon shown in the formula (III) is more than or equal to 1:100 and smaller or equal to 1: 5 for catalyzer.
The mol ratio of the beta-diketon shown in phenol shown in the formula (II) and the formula (III) is 1:1～1:2.
Said reaction can be carried out under reflux state, and the reaction times is 0.2-10 hours.
Said being reflected in the solvent carried out, and said solvent can be 1,2-ethylene dichloride, toluene, chlorobenzene, second eyeball or chloroform.Temperature of reaction is boiling point ± 20 ℃ of said organic solvent.
{ reaction under Fe} (≤20%) and the peroxide oxidant effect just can obtain complicated polysubstituted benzofuran compounds at catalytic amount for beta-diketon and phenol.{ it is a kind of brand-new synthetic route that Fe}/oxidizer system direct activation industrial raw material phenol is constructed very important polysubstituted benzofuran structural compounds, has good application prospects to utilize the cheap metal of catalytic amount.
The primitive reaction formula is following:
Figure G2008102392420D00031
Experiment showed, that method of the present invention can directly use the compound of structure such as industrial raw material phenol derivmives blend biology polysubstituted benzofuran class formation.This method has realized using the metal that is dirt cheap, and { Fe} direct oxidation activation industrial raw material phenol derivmives blend is biological; This is an initiative progress in metal c h bond activation field; And what this method was used is very cheap and easy to get; Eco-friendly iron, this provides new research direction for metal activation c h bond mechanism.The inventive method is easy and simple to handle, only needs a step, and just directly high yield is synthesized benzofuran compounds, and product is easy to purifying, and method is initiative, is that other traditional organic syntheses are not available, and application prospect is optimistic.
Embodiment
Synthesizing of embodiment 1, compound 2-phenyl-3-acyl group oxyethyl group-cumarone
Figure G2008102392420D00041
Under the high pure nitrogen protection, in the Schlenk of 20mL reaction tubes (a kind of glassware of using always during the anhydrous and oxygen-free operation), add 0.5mmol1-oxyethyl group-3-phenylpropanedione (R1 is a phenyl in the formula (III), and R2 is the compound of ethyl) (Acros company; CAS:94-02-0); 1 of 1mL (5mmol), 2-ethylene dichloride, 0.75mmol phenol (Alfa company; CAS:108-95-2), 0.05mmol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) t-butylperoxy ether (oxygenant) (the Acros company of (catalyzer) and 1mmol; CAS:110-05-4), with above-mentioned mixed solution stirring reaction 1 hour under 100 ℃ of reflux states, obtain the garnet reaction mixture; Add a little silica gel again; Then said mixed solution rotary evaporation is formed powder, then separate (silica gel: 200-300 order, eluent are that volume ratio is 1: 20 a ETHYLE ACETATE and molten 200mL of mixing of sherwood oil) with the acidic silica gel post; Promptly obtain straight product compound 2-phenyl-3-acyl group oxyethyl group benzo furans, productive rate is 78%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1718，1453，1443，1290，1223，1195，1090，1071，1049，833，792，766，747，740，736，715，702，684cm -1；
1H?NMR(ppm)δ?8.08-8.00(m，3H)，7.52-7.45(m，4H)，7.34-7.31(m，2H)，4.40(q，J＝7.2Hz，2H)，1.39(t，J＝7.2Hz，3H)；
13C?NMR(ppm)δ?163.9，160.6，153.7，130.1，129.4，127.9，127.0，125.1，123.9，122.6，111.0，60.5，14.1；
MS(EI)m/z(％)：266(M +)，238，221(100)，194，165，139，105，86，77，29；
HRMS(ESI)calcd?for?C 17H 15O 3(M ++H)：267.10157；found：267.10150.
Synthesizing of embodiment 2, compound 2-phenyl-3-acyl group oxyethyl group-5-methyl-cumarone
Synthetic route and separation method are basically with embodiment 1; Wherein, used beta-diketon is 1-oxyethyl group-3-phenylpropanedione (R1 is a phenyl in the formula (III), and R2 is the compound of ethyl) (Acros company; CAS:94-02-0) (0.5mmol); Phenolic cpd be p-methyl phenol (1.5eq, 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 71%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1718，1563，1491，1465，1445，1377，1351，1283，1202，1157，1047，1029，831，709，681cm -1；
1H?NMR(ppm)δ?8.01-7.98(m，2H)，7.84(s，1H)，7.46-7.36(m，4H)，7.15-7.12(m，1H)，4.39(q，J＝7.2Hz，2H)，2.47(s，3H)，1.38(t，J＝7.2Hz，3H)；
13C?NMR(ppm)δ?164.1，160.7，152.2，133.5，130.0，129.8，129.4，127.9，127.2，126.4，122.3，110.5，60.5，21.5，14.2；
MS(EI)m/z(％)：280(M +)，252，235(100)，208，178，152，102，28；
HRMS(ESI)calcd?for?C 18H 17O 3(M ++H)：281.11722；found：281.11783.
Synthesizing of embodiment 3, compound 2-phenyl-3-acyl group oxyethyl group-5-benzyl-cumarone
Figure G2008102392420D00052
Synthetic route and separation method are basically with embodiment 1, and wherein, used beta-diketon is 1-oxyethyl group-3-phenylpropanedione (Acros company; CAS:94-02-0) (0.5mmol); Phenolic cpd be the 4-benzylphenol (1.5eq, 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 92%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1718，1494，1468，1445，1260，1228，1203，1151，1072，1028，830，737，690，682cm -1；
1H?NMR(ppm)δ?8.01-7.97(m，2H)，7.88(s，1H)，7.45-7.39(m，4H)，7.31-7.14(m，6H)，4.35(q，J＝7.2Hz，2H)，4.10(s，2H)，1.32(t，J＝7.2Hz，3H)；
13C?NMR(ppm)δ?164.0，160.9，152.5，141.4，137.0，130.1，129.7，129.4，128.9，128.5，128.0，127.3，126.3，126.1，122.5，110.9，108.8，60.5，41.9，14.1；
MS(EI)m/z(％)：356(M +)，327，311(100)，252，207，178，155，105，77，29；
HRMS(ESI)calcd?for?C 24H 21O 3(M ++H)：357.14852；found：357.14937.
Synthesizing of embodiment 4, compound 2-phenyl-3-acyl group oxyethyl group-5-chloro-cumarone
Synthetic route and separation method be basically with embodiment 1, wherein, used beta-diketon be 1-oxyethyl group-3-phenylpropanedione (Acros company, CAS:94-02-0) (0.5mmol), phenolic cpd be para-chlorophenol (1.5eq, 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 50%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1722，1442，1222，1195，1074，1043，815，772，742，708，701，685，681cm -1；
1H?NMR(ppm)δ?8.04-8.00(m，3H)，7.50-7.43(m，4H)，7.33-7.25(m，1H)，4.42(q，J＝7.2Hz，2H)，1.41(t，J＝7.2Hz，3H)；
13C?NMR(ppm)δ?163.4，162.0，152.1，130.6，129.7，129.6，129.2，128.6，128.1，125.5，122.4，112.1，108.6，60.9，14.2；
MS(EI)m/z(％)：300(M +)，274，255(100)，228，219，200，163，105，77，28；
HRMS(ESI)calcd?for?C 17H 14Cl 1O 3(M ++H)：301.06260；found：301.06320.
Synthesizing of embodiment 5, compound 2-phenyl-3-acyl group oxyethyl group-7-allyl group-cumarone
Figure G2008102392420D00071
Synthetic route and separation method are basically with embodiment 1, and wherein, used beta-diketon is 1-oxyethyl group-3-phenylpropanedione (Acros company; CAS:94-02-0) (0.5mmol); Phenolic cpd be the ortho position chavicol (1.5eq, 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 62%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1716，1559，1486.1427，1372，1276，1228，1196，1028，992，914，832，746，687cm -1；
1H?NMR(ppm)δ?7.95-7.81(m，3H)，7.39-7.34(m，3H)，7.20-7.04(m，2H)，6.02-5.93(m，1H)，5.10-5.00(m，2H)，4.32(q，J＝7.2Hz，2H)，3.60(d，J＝6.6Hz，2H)，1.29(t，J＝7.2Hz，3H)；
13C?NMR(ppm)δ?164.0，160.4，152.3，135.6，130.1，129.5，129.4，128.1，128.0，127.0，125.2，124.2，123.6，120.7，116.4，60.6，33.7，14.2；
MS(EI)m/z(％)：306(M +)，278，261(100)，251，202，178，152，127，105，77，29；
HRMS(ESI)calcd?for?C 20H 19O 3(M ++H)：307.13287；found：307.13341.
Synthesizing of embodiment 6, compound 2-phenyl-3-acyl group oxyethyl group-7-benzyl-cumarone
Figure G2008102392420D00072
Synthetic route and separation method are basically with embodiment 1, and wherein, used beta-diketon is 1-oxyethyl group-3-phenylpropanedione (Acros company; CAS:94-02-0) (0.5mmol); Phenolic cpd be the ortho position benzylphenol (1.5eq, 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 80%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1714，1558，1277，1228，1085，1071，829，782，700，691cm -1；
1H?NMR(ppm)δ?8.01-7.90(m，3H)，7.48-7.45(m，3H)，7.30-7.12(m，7H)，4.40(q，J＝7.2Hz，2H)，4.29(s，2H)，1.39(t，J＝7.2Hz，3H)；
13C?NMR(ppm)δ?164.0，152.3，139.8，130.2，129.7，129.5，128.9，128.6，128.5，128.2，128.0，127.0，126.2，125.6，124.8，124.2，120.8，60.6，35.7，14.2；
MS(EI)m/z(％)：356(M +)，327，311，252，239，178，156，105(100)，77，29；
HRMS(ESI)calcd?for?C 24H 21O 3(M ++H)：357.14852；found：357.14854.
Embodiment 7, compound 2-phenyl-3-acyl group oxyethyl group-4,5-phenyl-cumarone synthetic
Figure G2008102392420D00081
Synthetic route and separation method be basically with embodiment 1, wherein, used beta-diketon be 1-oxyethyl group-3-phenylpropanedione (Acros company, CAS:94-02-0) (0.5mmol), phenolic cpd be beta naphthal (1.5eq, 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 59%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1719，1397，1340，1266，1236，1207，1187，1093，1034，1025，801，770，697，678，676cm -1；
1H?NMR(ppm)δ?8.59(d，J＝8.4Hz，1H)，7.88(d，J＝8.1Hz，1H)，7.81-7.78(m，2H)，7.72(d，J＝9.0Hz，1H)，7.62-7.54(m，2H)，7.49-7.38(m，4H)，4.46(q，J＝7.2Hz，2H)，1.29(t，J＝7.2Hz，3H)；
13C?NMR(ppm)δ?166.2，156.0，151.7，131.0，129.9，129.4，128.9，128.3，127.9，127.5，127.0，126.5，124.8，124.2，111.9，61.5，13.8；
MS(EI)m/z(％)：316(M +)，287，270，244，215(100)，213，189，150，107，77，29；
HRMS(ESI)calcd?for?C 21H 17O 3(M ++H)：317.11722；found：317.11742.
Embodiment 8, compound 2-phenyl-3-acyl group oxyethyl group-4,5-is synthetic to bromophenyl-cumarone
Figure G2008102392420D00091
Synthetic route and separation method are basically with embodiment 1, and wherein, used beta-diketon is 1-oxyethyl group-3-phenylpropanedione (Acros company; CAS:94-02-0) (0.5mmol); Phenolic cpd be 6-bromo-beta naphthal (1.5eq, 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 65%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1719，1491，1396，1379，1332，1237，1192，1115，1097，904，808，690，682cm -1；
1H?NMR(ppm)δ?8.54(d，J＝9.0Hz，1H)，8.02(s，1H)，7.79-7.76(m，2H)，7.64-7.61(m，3H)，7.46-7.43(m，3H)，4.43(q，J＝7.2Hz，2H)，1.28(t，J＝7.2Hz，3H)；
13C?NMR(ppm)δ?165.8，157.1，151.7，132.3，130.8，129.8，129.6，129.5，128.3，128.2，126.3，126.0，125.9，121.1，118.7，112.9，111.4，61.5，13.8；
MS(EI)m/z(％)：394(M +)，366，349，293，269，213(100)，147，107，77，29；
HRMS(ESI)calcd?for?C 21H 16Br 1O 3(M ++H)：395.02773；found：395.02905.
Synthesizing of embodiment 9, compound 2-p-methoxyphenyl-3-acyl group oxyethyl group-cumarone
Figure G2008102392420D00092
Synthetic route and separation method are basically with embodiment 1; Wherein, Used beta-diketon is that (0.5mmol), phenolic cpd is phenol (1.5eq to 1-methoxyl group-3-p-methoxyphenyl propanedione (R1 is a p-methoxyphenyl in the formula (III), and R2 is the compound of methyl); 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 63%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1718，1504，1452，1260，1223，1177，1088，1030，803，786，739，711，695cm -1；
1H?NMR(ppm)δ?7.93-7.89(m，3H)，7.39-7.36(m，1H)，7.21-7.18(m，2H)，6.88(d，J＝8.7Hz，2H)，3.81(s，3H)，3.73(s，3H)；
13C?NMR(ppm)δ?164.6，161.1，153.4，131.0，127.1，124.8，123.8，122.5，121.9，113.5，110.9，55.2，51.4；
MS(EI)m/z(％)：282(M +)，267，251(100)，224，195，152，141，98，63，39；
HRMS(ESI)calcd?for?C 17H 15O 4(M ++H)：283.09649；found：283.09706.
Embodiment 10, compound 2-rubigan-3-acyl group methoxyl group-4,5-phenyl-cumarone) synthetic
Figure G2008102392420D00101
Synthetic route and separation method are basically with embodiment 1, and wherein, used beta-diketon is that (R1 is a rubigan to 1-methoxyl group-3-rubigan propanedione in the formula (III); R2 is the compound of methyl) (0.5mmol); Phenolic cpd be beta naphthal (1.5eq, 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 52%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1721，1717，1653，1506，1095，839，831，801，772.761，718，698，680cm -1；
1H?NMR(ppm)δ?8.42(d，J＝8.7Hz，1H)，7.81(d，J＝7.8Hz，1H)，7.67-7.61(m，3H)，7.53-7.49(m，2H)，7.46-7.42(m，1H)，7.39-7.31(m，2H)，3.87(s，3H)；
13C?NMR(ppm)δ?166.4，155.0，151.9，135.5，131.1，129.1，129.0，128.7，128.4，127.4，126.7，125.0，124.2，120.9，111.8，52.3；
MS(EI)m/z(％)：336(M +)，305，286，270，249(100)，213，187，163，151，125，107，28；
HRMS(ESI)calcd?for?C 20H 14Cl 1O 3(M ++H)：337.06260；found：337.06367.
Embodiment 11, compound 2-synthesize methyl furan base-3-acyl group methoxyl group-cumarone
Synthetic route and separation method are basically with embodiment 1; Wherein, Used beta-diketon is that (0.5mmol), phenolic cpd is phenol (1.5eq to 1-methoxyl group-3-to methyl furan base propanedione (R1 is that R2 is the compound of methyl to the methyl furan base in the formula (III)); 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 20%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1706，1561，1445，1346，1234，1300，1105，1051，1018，939，872，740cm -1；
1H?NMR(ppm)δ?8.01-7.98(m，1H)，7.77-7.76(m，1H)，7.55-7.52(m，1H)，7.32-7.23(m，2H)，6.23-7.21(m，2H)，3.97(s，3H)，2.45(s，3H)；
13C?NMR(ppm)δ?164.1，155.3，153.3，142.7，126.5，125.1，124.1，122.5，118.3，11.1，109.1，51.5，14.0；
MS(EI)m/z(％)：256(M +)，235，225，213，199，169，139，115，88，84，63，43，32，28(100)；
HRMS(ESI)calcd?for?C 15H 13O 4(M ++H)：257.08084；found：257.08045.
Synthesizing of embodiment 12, compound 2-methyl-3-acyl group oxyethyl group-cumarone
Figure G2008102392420D00112
Synthetic route and separation method are basically with embodiment 1; Wherein, used beta-diketon is methyl aceto acetate (R1 is a methyl in the formula (III), and R2 is the compound of ethyl) (Alfa company; CAS:141-97-9) (0.5mmol); Phenolic cpd be phenol (1.5eq, 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 81%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1711，1597，1478，1453，1384，1287，1235，1181，1105，1083，1007，931，785，749，741cm -1；
1H?NMR(ppm)δ?7.97-7.94(m，1H)，7.42-7.39(m，1H)，7.29-7.25(m，2H)，4.40(q，J＝7.2Hz，2H)，2.76(s，3H)，1.44(t，J＝7.2Hz，3H)；
13C?NMR(ppm)δ?164.5，163.5，153.5，126.2，124.2，123.7，121.7，110.7，60.2，31.8，14.4；
MS(EI)m/z(％)：204(M +)，191，175，159，131，119，103，88，86(100)，51，47，35；
HRMS(ESI)calcd?for?C 12H 13O 3(M ++H)：205.08592；found：205.08562.
Synthesizing of embodiment 13, compound 2-normal-butyl-3-acyl group methoxyl group-cumarone
Figure G2008102392420D00121
Synthetic route and separation method are basically with embodiment 1; Wherein, used beta-diketon is normal-butyl methyl acetate (R1 is a normal-butyl in the formula (III), and R2 is the compound of methyl) (Alfa company; CAS:30414-54-1) (0.5mmol); Phenolic cpd be phenol (1.5eq, 0.75mmol), 0.05mol (10%) FeCl 36H 2O (Alfa company, CAS:10025-77-1) (catalyzer) and 1mmol t-butylperoxy ether (Acros company; CAS:110-05-4) (oxygenant), solvent are 1 of 1mL, 2-ethylene dichloride (Acros company; CAS:107-06-2) (solvent); Under 100 ℃ of reflux states, the reaction times is 1 hour, and productive rate is 67%.
This compound infrared, nuclear-magnetism and mass-spectrometric data are following:
IR(neat)：v max1716，1588，1478，1453，1437，1385，1369，1281，1237，1207，1171，797，696，676cm -1；
1H?NMR(ppm)δ?7.89-7.86(m，1H)，7.36-7.34(m，1H)，7.26-7.16(m，2H)，3.85(s，3H)，3.08(t，J＝7.2Hz，2H)，1.77-1.70(m，2H)，0.92(t，J＝7.2Hz，3H)；
13C?NMR(ppm)δ?167.4，164.9，153.6，126.1，124.3，123.7，121.8，110.8，51.3，29.9，21.3，13.8；MS(EI)m/z(％)：218(M +)，203，188(100)，186，171，159，145，131，102，91，77，63，50，39，29；
HRMS(ESI)calcd?for?C 13H 15O 3(M ++H)：219.10157；found：219.10222.

Claims (3)

1. the compound method of compound shown in the general formula I is in the system that contains catalyzer and peroxide oxidant, and compound shown in compound shown in the general formula I I and the general formula III is reacted, and obtains compound shown in the general formula I;
Figure FSB00000659691500011
Wherein: R 1, R 2, R 3Be following any one:
1) R 1Be phenyl, R 2Be ethyl, R 3Be hydrogen;
2) R 1Be p-methoxyphenyl, R 2Be methyl, R 3Be hydrogen;
3) R 1Be methyl, R 2Be ethyl, R 3Be hydrogen;
Said catalyzer is FeCl 3.6H 2O;
Said peroxide oxidant is the superoxide shown in the general formula I V;
R 4-O-O-R 5
Formula IV
Wherein: R 4, R 5Be the tertiary butyl.
2. method according to claim 1 is characterized in that: said being reflected in the solvent carried out, and said solvent is 1, the 2-ethylene dichloride.
3. method according to claim 1 is characterized in that: the reaction times of said reaction is 1 hour.
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