CN103214506B - Cumarone or aphthofurans derivative and preparation method thereof - Google Patents

Cumarone or aphthofurans derivative and preparation method thereof Download PDF

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CN103214506B
CN103214506B CN201310121874.8A CN201310121874A CN103214506B CN 103214506 B CN103214506 B CN 103214506B CN 201310121874 A CN201310121874 A CN 201310121874A CN 103214506 B CN103214506 B CN 103214506B
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oxygen
derivative
aphthofurans
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silica
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CN103214506A (en
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陈雅丽
徐迪
张亚娟
张�杰
郑晓杏
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University of Shanghai for Science and Technology
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Abstract

The present invention relates to a kind of cumarone or aphthofurans derivative and preparation method thereof.The structural formula of this derivative is: wherein, R 1for: OCH 3, OC 2h 5, CH 3r 2?for: CH 3, C 6h 5r 1?=R 2: (CH 2) 3, CH 2c (CH 3) 2cH 2such reaction is typical [3+2] cycloaddition reaction, aryne produces and namely can participate in reaction, synthesis benzo or aphthofurans derivative, meet the requirement of atom economic reaction, for structure benzo or aphthofurans skeleton provide a kind of brand-new thinking, enriched the synthetic method of organic heterocyclic molecule, the synthetic method of this research benzofuran derivative or aphthofurans derivative has no bibliographical information.

Description

Cumarone or aphthofurans derivative and preparation method thereof
Technical field
The present invention a kind of cumarone or aphthofurans derivative and preparation method thereof.
Background technology
Aromatic heterocycle is a kind of important and common basic skeleton structure in a lot of pharmaceutical intermediate, natural product and organic photoelectrical material, and thus, the synthesis of heteroaromatic compound is one of focus of paying close attention to of modern organic synthesis methodology.Furan derivative has very strong biological activity, and it is extensively present in natural and unnatural products.2-arylbenzofuran analog derivative demonstrates good biological activity and pharmacologically active, comprises antitumour activity, anti-rheumatoid disease activity, the activity of anti-virus activity, anti-mycotic activity, immunosuppressive activity, anti-platelet activity, insecticidal activity, anti-inflammatory activity, antifeedant, preventing cancer activity.It is poly-active that these compounds also have calcium to stop [and excite development of plants active.
Due to the replacement benzofuran compound limited amount extracted in natural product, and content is very few, and therefore this compounds of synthetic will seem extremely important.
At present, the method for main synthesis cumarone mainly contains traditional method, palladium chtalyst synthesis, copper catalyzes and synthesizes and other precious metal catalysts synthesize.Traditional method has in biological activity cumarone in synthesis and plays an important role, but ubiquity route is long, and substrate and reaction conditions require too high, replaces functional group's expansion limited.By the transfer catalysis of metal, although synthetic method is efficient and general, the environment of reaction system is harsher, and the price comparison of spent catalyzer is high.
See following documents:
[1]Navarro,E.;Alonso,S.J.;Trujillo,J.;Jorge,E;Perez,C. J.Nat.Prod. 2001, 64,134.
[2]Ikeda,R.;Nagao,T.;Okabe,H.;Nakano,Y.;Matsunaga,H.;Katana,M.;Mori,M. Chem.Pharm.Bull. 1998, 46,871.
[3]Craigo,J.;Callahan,M.;Huang,R.C.C.;DeLucia,A.L. AntiviralRes. 2000, 47,19.
[4]Carter,G.A.;Chamberlain,K.;Wain,R.L. Ann.Appl.Biol. 1978, 88,57.
[5]Gordaliza,M.;Castro,M.;Lopez-Vazaquez,M.;Feliciano,A.S.;Faircloth,G.T. Bioorg.Med.Chem.Lett. 1997, 7,2781.
[6]Chen,C.C.;Hsin,W.C.;Ko,F.N.;Huang,Y.L.;Ou,J.C.;Teng,C.M. J.Nat.Prod. 1996, 59,1149.
[7]Masuda,S.;Hasuda,H.;Tokoroyama,T. Chem.Pharm.Bull. 1994, 42,2500.
[8]Findlay,J.A.;Buthelezi,S.:Li,G;Seveck,M.;Miller,J.D. J.Nat.Prod. 1997, 60,1214.
[9]Day,S.H.;Chiu,N.Y.;Tsao,L.T.;Wang,J.P.;Lin,C.N. J.Nat.Prod. 2000, 63,1560.
[10]Ward,R.S. Nat.Prod.Rep. 1995, 12,183.
[11]Oikannen,S.I.;Pajari,A.M.;Mutanen,M. CancerLett. 2000, 155,79.
[12]Gubin,J.;deVogelae,H.;Inion,H.;Houben,C.;Lucchetti,J.;Mahaux,J.;Rosseels,G.;Peiren,M.;Polstre,P.;Chatelain,P.;Clinet,M. J.Med.Chem. 1993, 36,1425.
[13]Alonso,F.;Beletskaya,I.P.;Yus,M. Chem.Rev. 2004, 104,3079。
Summary of the invention
An object of the present invention there are provided the new cumarone of a class or aphthofurans derivative.
Two of object of the present invention is the preparation method providing cumarone or aphthofurans derivative.
For achieving the above object, reaction mechanism of the present invention is: benzo two (oxygen two silicon is luxuriant) ( 1) or the silica-based naphthalene of oxygen two ( 6) react with iodobenzene diacetate salt, trifluoromethanesulfonic acid, generation phenyl [adjacent (the silica-based fused phenyl of the silica-based oxygen of hydroxyl dimethyl two)] three fluosulfonic acid iodide ( 2) or phenyl [adjacent (hydroxyl dimethyl is silica-based) naphthyl] three fluosulfonic acid iodide ( 7), add Diisopropylamine successively, iodonium ylides compound 4a-f, tetrabutyl ammonium fluoride (TBAF)/tetrahydrofuran (THF) (THF), first generates Aryne intermediates 3or 8, there is [3+2] cycloaddition reaction with iodonium ylides compound immediately, generate the silica-based benzofuran derivative of oxygen two 5a-for aphthofurans derivative 9a-f.
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A kind of benzo or aphthofurans derivative, is characterized in that the structural formula of described benzofuran derivative is:
；
The structural formula of described aphthofurans derivative is:
；
Wherein, R 1for :-(CH 2) 3, CH 2c (CH 3) 2cH 2,-OCH 3,-OC 2h 5or-CH 3
R 2for: (CH 2) 3, CH 2c (CH 3) 2cH 2,-CH 3or-C 6h 5
Prepare a method for above-mentioned benzo or aphthofurans derivative, it is characterized in that the method has following steps:
A. iodobenzene diacetate salt is dissolved in methylene dichloride, under inert atmosphere and ice-water bath, add trifluoromethanesulfonic acid, react 0.5 ~ 1 hour, room temperature reaction 1 ~ 2 hour; Then under ice-water bath, this reaction soln is joined in the dichloromethane solution of benzo two (oxygen two silicon is luxuriant) or the silica-based naphthalene of oxygen two, continue ice-water bath reaction 0.5 ~ 1 hour, room temperature reaction 3 ~ 4 hours, is finally adding Diisopropylamine successively, iodonium ylides compound, tetrabutyl ammonium fluoride TBAF/ tetrahydrofuran THF solution, react end in 3 ~ 18 hours, separating-purifying, obtain solid and the silica-based benzofuran derivative of oxygen two or aphthofurans derivative; The structural formula of described iodobenzene diacetate salt is: PhI (OAc) 2; The structural formula of described benzo two (oxygen two silicon is luxuriant) is: ; The structural formula of the described silica-based naphthalene of oxygen two is: ; The structural formula of described Diisopropylamine is: i-Pr 2nH; The structural formula of described iodonium ylides compound is: ; Wherein: R 1for: OCH 3, OC 2h 5, CH 3; R 2for: CH 3, C 6h 5; R 1=R 2for: (CH 2) 3, CH 2c (CH 3) 2cH 2; The mol ratio of described iodobenzene diacetate salt, trifluoromethanesulfonic acid, benzo two (oxygen two silicon is luxuriant) or the silica-based naphthalene of oxygen two, Diisopropylamine, iodonium ylides compound, tetrabutyl ammonium fluoride TBAF is: 1.5 ~ 2.5:3.5 ~ 4.5:1.0:3.0 ~ 4.0:4.0 ~ 5.0:3.0 ~ 4.0.
The inventive method is benzyne or naphthalyne precursor with benzo two (oxygen two silicon is luxuriant) or the silica-based naphthalene of oxygen two, produces benzyne and naphthalyne at ambient temperature, further with the addition reaction of iodonium ylides compound initial ring, generates cumarone or aphthofurans derivative.This synthetic method has that speed of response is fast, reaction conditions is gentle, advantages of environment protection.
Analyze theoretically, such reaction is typical [3+2] cycloaddition reaction, and aryne produces and namely can participate in reaction, and different iodonium ylides compounds can affect its productive rate, but productive rate is general higher.Therefore, present method is a kind of effective means building cumarone or aphthofurans skeleton, has enriched the synthetic method of organic heterocyclic molecule.
Embodiment
Embodiment one: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), benzo two (oxygen two silicon is luxuriant) ( 1, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4a, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained benzofuran derivative is: the silica-based-3-benzofurancarboxylic acid methyl esters of 2-methyl-5,6-oxygen two ( 5a), yield 83%, the structure of this compound is:
Molecular formula: C 15h 20o 4si 2
Chinese named: Chinese named: the silica-based-3-benzofurancarboxylic acid methyl esters of 2-methyl-5,6-oxygen two
English name: 2-Methyl-5,6-oxadisilole-3-benzofurancarboxylicacid, methylester
Molecular weight: 320.09
Outward appearance: white powder
Proton nmr spectra (500MHz, CDCl 3): δ 0.38 (s, 6H), 0.40 (s, 6H), 2.77 (s, 3H), 3.96 (s, 3H), 7.59 (s, 1H), 8.14 (s, 1H) ppm.
Carbon-13 nmr spectra (125MHz, CDCl 3): δ 1.3,1.4,14.7,51.6,108.7,113.1,124.7,127.8,142.4,143.7,155.2,164.3,165.0ppm.
Embodiment two: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), benzo two (oxygen two silicon is luxuriant) ( 1, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4b, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained benzofuran derivative is: the silica-based-3-benzofurancarboxylic acid ethyl ester of 2-methyl-5,6-oxygen two ( 5b), yield 91%, the structure of this compound is:
Molecular formula: C 16h 22o 4si 2
Chinese named: the silica-based-3-benzofurancarboxylic acid ethyl ester of 2-methyl-5,6-oxygen two
English name: 2-Methyl-5,6-oxadisilole-3-benzofurancarboxylicacid, ethylester
Molecular weight: 334.11
Outward appearance: white powder
Proton nmr spectra (500MHz, CDCl 3): δ 0.39 (s, 6H), 0.40 (s, 6H), 1.45 (t, j=7.0Hz, 3H), 2.78 (s, 3H), 4.43 (q, j=7.0Hz, 2H), 7.60 (s, 1H), 8.18 (s, 1H) ppm.
Carbon-13 nmr spectra (125MHz, CDCl 3): δ 1.35,1.42,14.6,14.8,60.5,109.0,113.1,124.8,128.0,142.4,143.7,155.2,164.0,164.6ppm.
Embodiment three: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), benzo two (oxygen two silicon is luxuriant) ( 1, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4c, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained benzofuran derivative is: the silica-based cumarone of 2-methyl-3-ethanoyl-5,6-oxygen two ( 5c), yield 85%, the structure of this compound is:
Molecular formula: C 15h 20o 3si 2
Chinese named: the silica-based cumarone of 2-methyl-3-ethanoyl-5,6-oxygen two
English name: 2-Methyl-3-acetyl-5,6-oxadisilolebenzofuran
Molecular weight: 304.10
Outward appearance: white powder
Proton nmr spectra (500MHz, CDCl 3): δ 0.39 (s, 6H), 0.41 (s, 6H), 2.66 (s, 3H), 2.79 (s, 3H), 7.62 (s, 1H), 8.17 (s, 1H) ppm.
. carbon-13 nmr spectra (125MHz, CDCl 3): δ 1.3,1.5,15.7,31.4,113.3,117.6,124.5,127.8,142.8,144.0,155.1,163.3,194.3ppm.
Embodiment four: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), benzo two (oxygen two silicon is luxuriant) ( 1, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4d, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained benzofuran derivative is: the silica-based cumarone of 2-phenyl-3-ethanoyl-5,6-oxygen two ( 5d), yield 73%, the structure of this compound is:
Molecular formula: C 20h 22o 3si 2
Chinese named: the silica-based cumarone of 2-phenyl-3-ethanoyl-5,6-oxygen two
English name: 2-Phenyl-3-acetyl-5,6-oxadisilolebenzofuran
Molecular weight: 366.11
Outward appearance: white powder
Proton nmr spectra (500MHz, CDCl 3): δ 0.41 (s, 6H), 0.42 (s, 6H), 7.54 (s, 1H), 7.55 (s, 2H), 7.70 (s, 1H), 7.72-7.74 (m, 2H), 8.33 (s, 1H) ppm.
Carbon-13 nmr spectra (125MHz, CDCl 3): δ 1.3,1.5,30.7,113.5,118.4,125.6,128.5,128.9,129.8,130.3,130.8,143.1,145.2,155.5,161.0,195.9ppm.
Embodiment five: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), benzo two (oxygen two silicon is luxuriant) ( 1, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4e, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained benzofuran derivative is: 3,4-dihydro-7,8-oxygen two silica-based-1 ( 2H)-dibenzopyrone ( 5e), yield 38%, the structure of this compound is:
Molecular formula: C 16h 20o 3si 2
Chinese named: 3,4-dihydro-7,8-oxygen two silica-based-1 ( 2H)-dibenzopyrone
English name: 3,4-Dihydro-7,8-oxadisilole-1 ( 2H)-dibenzofuranone
Molecular weight: 316.10
Outward appearance: white powder
Proton nmr spectra (500MHz, CDCl 3): δ 0.386 (s, 6H), 0.390 (s, 6H), 2.26-2.31 (m, 2H), 2.61-2.64 (m, 2H), 3.04-3.06 (m, 2H), 7.64 (s, 1H), 8.27 (s, 1H) ppm.
Carbon-13 nmr spectra (125MHz, CDCl 3): δ 1.4,1.5,22.7,24.1,38.1,113.5,116.4,124.9,125.3,143.5,144.9,156.2,171.7,195.3ppm.
Embodiment six: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), benzo two (oxygen two silicon is luxuriant) ( 1, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4f, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained benzofuran derivative is: 3,3-dimethyl-3,4-dihydro-7,8-oxygen two silica-based-1 ( 2H)-dibenzopyrone ( 5f), yield 43%, the structure of this compound is:
Molecular formula: C 18h 24o 3si 2
Chinese named: 3,3-dimethyl-3,4-dihydro-7,8-oxygen two silica-based-1 ( 2H)-dibenzopyrone
English name: 3,3-Dimethyl-3,4-dihydro-7,8-oxadisilole-1 ( 2H)-dibenzofuranone
Molecular weight: 344.13
Outward appearance: white powder
Proton nmr spectra (500MHz, CDCl 3): δ 0.388 (s, 6H), 0.393 (s, 6H), 1.20 (s, 6H), 2.50 (s, 2H), 2.91 (s, 2H), 7.65 (s, 1H), 8.26 (s, 1H) ppm.
Carbon-13 nmr spectra (125MHz, CDCl 3): δ 1.3,1.4,28.7,35.4,38.0,52.4,113.5,115.2,124.8,125.1,143.4,144.7,156.5,170.7,194.5ppm.
Embodiment seven: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), the silica-based naphthalene of oxygen two ( 6, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4a, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained aphthofurans derivative is: 2-methyl-3-naphtho-[2,3- b] methyl furoate ( 9a), yield 62%, the structure of this compound is:
Molecular formula: C 15h 12o 3
Chinese named: 2-methyl-3-naphtho-[2,3- b] methyl furoate
English name: 2-Methylnaphtho [2,3- b] furan-3-carboxylicacid, methylester
Molecular weight: 240.08
Outward appearance: yellow powder
Proton nmr spectra (500MHz, CDCl 3): δ 2.81 (s, 3H), 4.00 (s, 3H), 7.43-7.48 (m, 2H), 7.80 (s, 1H), 7.89-7.91 (m, 1H), 7.98-8.00 (m, 1H), 8.39 (s, 1H) ppm.
Carbon-13 nmr spectra (125MHz, CDCl 3): δ 14.9,51.6,106.6,108.5,119.9,124.5,125.2,126.7,127.9,128.5,131.1,131.2,152.7,164.9,166.8ppm.
Embodiment eight: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), the silica-based naphthalene of oxygen two ( 6, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4b, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained aphthofurans derivative is: 2-methyl-3-naphtho-[2,3- b] furyl ethyl formate ( 9b), yield 55%, the structure of this compound is:
Molecular formula: C 16h 14o 3
Chinese named: 2-methyl-3-naphtho-[2,3- b] furyl ethyl formate
English name: 2-Methylnaphtho [2,3- b] furan-3-carboxylicacid, ethylester
Molecular weight: 254.09
Outward appearance: yellow powder
Proton nmr spectra (500MHz, CDCl 3): δ 1.50 (t, j=7.0Hz, 3H), 2.82 (s, 3H), 4.47 (q, j=7.0Hz, 2H), 7.44-7.48 (m, 2H), 7.80 (s, 1H), 7.90-7.91 (m, 1H), 7.98-8.00 (m, 1H), 8.41 (s, 1H) ppm.
Carbon-13 nmr spectra (125MHz, CDCl 3): δ 14.6,14.7,60.5,106.5,108.6,119.9,124.5,125.2,126.8,127.9,128.5,131.0,131.2,152.7,164.5,166.6ppm.
Embodiment nine: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), the silica-based naphthalene of oxygen two ( 6, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4c, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained aphthofurans derivative is: 2-methyl-3-ethanoyl naphtho-[2,3- b] furans ( 9c), yield 60%, the structure of this compound is:
Molecular formula: C 15h 12o 2
Chinese named: 2-methyl-3-ethanoyl naphtho-[2,3- b] furans
English name: 2-Methyl-3-acetylnaphtho [2,3- b] furan
Chinese named: the silica-based cumarone of 2-phenyl-3-ethanoyl-5,6-oxygen two
Molecular weight: 224.08
Outward appearance: yellow powder
Proton nmr spectra (500MHz, CDCl 3): δ 2.73 (s, 3H), 2.84 (s, 3H), 7.46-7.48 (m, 2H), 7.84 (s, 1H), 7.91-7.93 (m, 1H), 7.99-8.01 (m, 1H), 8.41 (s, 1H) ppm.
Carbon-13 nmr spectra (125MHz, CDCl 3): δ 15.9,31.4,106.8,117.2,119.9,124.7,125.5,126.8,127.9,128.5,130.3,131.2,152.6,166.0,194.1ppm.
Embodiment ten: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), the silica-based naphthalene of oxygen two ( 6, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4d, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained aphthofurans derivative is: 2-phenyl-3-ethanoyl naphtho-[2,3- b] furans ( 9d), yield 62%, the structure of this compound is:
Molecular formula: C 20h 14o 2
Chinese named: 2-phenyl-3-ethanoyl naphtho-[2,3- b] furans
English name: 2-Phenyl-3-acetylnaphtho [2,3- b] furan
Molecular weight: 286.10
Outward appearance: yellow powder
Proton nmr spectra (500MHz, CDCl 3): δ 2.43 (s, 3H), 7.46-7.51 (m, 3H), 7.57-7.58 (m, 2H), 7.81-7.83 (m, 2H), 7.92 (s, 1H), 7.94 (d, j=7.5Hz, 1H), 8.03-8.04 (m, 1H), 8.63 (s, 1H) ppm.
Carbon-13 nmr spectra (125MHz, CDCl 3): δ 29.9,106.9,118.0,121.2,124.7,125.7,127.5,127.9,128.8,128.9,130.0,130.2,131.1,131.4,131.9,152.8,163.2,195.5ppm.
Embodiment 11: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), the silica-based naphthalene of oxygen two ( 6, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4e, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained aphthofurans derivative is: 3,4-dihydrobenzo [ b] naphtho-[2,3- d] furans-1 ( 2H)-one ( 9e), yield 40%, the structure of this compound is:
Molecular formula: C 16h 12o 2
Chinese named: 3,4-dihydrobenzo [ b] naphtho-[2,3- d] furans-1 ( 2H)-one
English name: 3,4-Dihydrobenzo [ b] naphtho [2,3- d] furan-1 ( 2H)-one
Molecular weight: 236.08
Outward appearance: yellow powder
Proton nmr spectra (500MHz, CDCl 3): δ 2.30-2.35 (m, 2H), 2.65-2.68 (m, 2H), 3.08-3.10 (m, 2H) 7.47-7.49 (m, 2H), 7.87 (s, 1H), 7.91-7.93 (m, 1H), 8.00-8.01 (m, 1H), (8.53 s, 1H) ppm.
Carbon-13 nmr spectra (125MHz, CDCl 3): δ 22.5,24.2,37.9,107.2,116.2,120.2,124.0,124.9,125.6,128.1,128.6,131.45,131.51,153.5,174.0,194.8ppm.
Embodiment 12: iodobenzene diacetate salt (1.5 ~ 2.5eq), trifluoromethanesulfonic acid (3.5 ~ 4.5eq), the silica-based naphthalene of oxygen two ( 6, 1.0eq), Diisopropylamine (3.0 ~ 4.0eq), iodonium ylides compound ( 4f, 4.0 ~ 5.0eq), TBAF/THF(3.0 ~ 4.0eq), gained aphthofurans derivative is: 3,3-dimethyl-3,4-dihydrobenzo [ b] naphtho-[2,3- d] furans-1 ( 2H)-one ( 9f), yield 45%, the structure of this compound is:
Molecular formula: C 18h 16o 2
Chinese named: 3,3-dimethyl-3,4-dihydrobenzo [ b] naphtho-[2,3- d] furans-1 ( 2H)-one
English name: 3,3-Dimethyl-3,4-dihydrobenzo [ b] naphtho [2,3- d] furan-1 ( 2H)-one
Molecular weight: 264.12
Outward appearance: yellow powder
Proton nmr spectra (500MHz, CDCl 3): δ 1.23 (s, 6H), 2.53 (s, 2H), 2.94 (s, 2H) 7.45-7.50 (m, 2H), 7.87 (s, 1H), 7.91-7.93 (m, 1H), 8.00-8.01 (m, 1H), (8.51 s, 1H) ppm.
Carbon-13 nmr spectra (125MHz, CDCl 3): δ 28.9,35.3,38.1,52.3,107.2,115.0,120.1,123.9,124.9,125.6,128.1,128.6,131.4,131.5,153.9,173.1,194.1ppm.

Claims (1)

1. a preparation method for benzo or aphthofurans derivative, the structural formula of this benzofuran derivative is:
；
The structural formula of described aphthofurans derivative is:
；
Wherein, R 1for :-(CH 2) 3, CH 2c (CH 3) 2cH 2,-OCH 3,-OC 2h 5or-CH 3
R 2for: (CH 2) 3, CH 2c (CH 3) 2cH 2,-CH 3or-C 6h 5; The method has following steps: dissolve in methylene dichloride by iodobenzene diacetate salt, under inert atmosphere and ice-water bath, adds trifluoromethanesulfonic acid, reacts 0.5 ~ 1 hour, room temperature reaction 1 ~ 2 hour; Then under ice-water bath, this reaction soln is joined in the dichloromethane solution of benzo two (oxygen two silicon is luxuriant) or the silica-based naphthalene of oxygen two, continue ice-water bath reaction 0.5 ~ 1 hour, room temperature reaction 3 ~ 4 hours, is finally adding Diisopropylamine successively, iodonium ylides compound, tetrabutyl ammonium fluoride TBAF/ tetrahydrofuran THF solution, react end in 3 ~ 18 hours, separating-purifying, obtain solid and the silica-based benzofuran derivative of oxygen two or aphthofurans derivative; The structural formula of described iodobenzene diacetate salt is: PhI (OAc) 2; The structural formula of described benzo two (oxygen two silicon is luxuriant) is: ; The structural formula of the described silica-based naphthalene of oxygen two is: ; The structural formula of described Diisopropylamine is: i-Pr 2nH; The structural formula of described iodonium ylides compound is: ; Wherein: R 1for: OCH 3, OC 2h 5, CH 3; R 2for: CH 3, C 6h 5; R 1=R 2for: (CH 2) 3, CH 2c (CH 3) 2cH 2; The mol ratio of described iodobenzene diacetate salt, trifluoromethanesulfonic acid, benzo two (oxygen two silicon is luxuriant) or the silica-based naphthalene of oxygen two, Diisopropylamine, iodonium ylides compound, tetrabutyl ammonium fluoride TBAF is: 1.5 ~ 2.5:3.5 ~ 4.5:1.0:3.0 ~ 4.0:4.0 ~ 5.0:3.0 ~ 4.0.
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