CN103214506A - Benzofuran or naphthofuran derivative and preparation method thereof - Google Patents

Benzofuran or naphthofuran derivative and preparation method thereof Download PDF

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CN103214506A
CN103214506A CN2013101218748A CN201310121874A CN103214506A CN 103214506 A CN103214506 A CN 103214506A CN 2013101218748 A CN2013101218748 A CN 2013101218748A CN 201310121874 A CN201310121874 A CN 201310121874A CN 103214506 A CN103214506 A CN 103214506A
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oxygen
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structural formula
silica
benzo
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CN103214506B (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 invention relates to a benzofuran or naphthofuran derivative and a preparation method thereof. A structural formula of the derivative is shown in the specification, wherein R1 is OCH3, OC2H5 or CH3, and R2 is CH3 or C6 H5, or R1 and R2 are the same and are (CH2)3, CH2C(CH3)2CH2. The reaction is a typical [3+2] cycloaddition, aryne is produced to participate in the reaction to synthesize the benzofuran or naphthofuran derivative, the requirement of the atomic economic reaction can be met, a completely novel through is provided for establishing a skeleton of benzofuran or naphthofuran, the synthesis method of organic heterocyclic compound is enriched, and the research of the synthesis method of the benzofuran or naphthofuran derivative is not reported in any literature.

Description

Cumarone or aphthofurans derivative and preparation method thereof
Technical field
A kind of cumarone of the present invention 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 intermediates, natural product and the organic photoelectrical material, thereby the synthetic of heteroaromatic compound is that modern methodology of organic synthesis is learned one of focus of being paid close attention to.Furan derivative has very strong biological activity, and it extensively is present in the natural and non-natural product.2-aryl cumarone analog derivative demonstrates good biological activity and pharmacologically active, comprises antitumour activity, anti-rheumatoid disease activity, anti-virus activity, anti-mycotic activity, immunosuppressive activity, anti-platelet activity, insecticidal activity, anti-inflammatory activity, the activity of antifeedant, preventing cancer activity.It is poly-active that these compounds also have calcium to stop [And excite the development of plants activity.
Since the replacement benzofuran compound limited amount that extracts in the natural product, and content is very few, so this compounds of synthetic will seem extremely important.
At present, mainly the method for synthetic cumarone mainly contains traditional method, palladium catalysis is synthetic, copper catalysis is synthetic and other precious metal catalysts are synthetic.Traditional method plays an important role in synthetic biologically active cumarone, but the ubiquity route is long, and substrate and reaction conditions require too high, and it is limited to replace functional group's expansion.By the transfer catalysis of metal, though synthetic method is efficient and general,, the environment of reaction system is relatively harsher, the price comparison height of spent catalyzer.
Referring to following document:
[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. ?Antiviral?Res.? 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. ?Cancer?Lett.? 2000,? 155,?79.
[12]?Gubin,?J.;?de?Vogelae,?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
One of purpose of the present invention has been to provide new cumarone of a class or aphthofurans derivative.
Two of purpose of the present invention is to provide the preparation method of cumarone or aphthofurans derivative.
For achieving the above object, reaction mechanism of the present invention is: benzo two (oxygen two silicon are luxuriant) ( 1) or oxygen two silica-based naphthalenes ( 6) react with two acetic acid iodobenzene salt, trifluoromethanesulfonic acid, generation phenyl [adjacent (the silica-based oxygen two silica-based fused phenyls of hydroxyl dimethyl)] three fluosulfonic acid iodide ( 2) or phenyl [adjacent (the hydroxyl dimethyl is silica-based) naphthyl] three fluosulfonic acid iodide ( 7), add Diisopropylamine successively, iodine ylide compound 4a-f, tetrabutyl ammonium fluoride (TBAF)/tetrahydrofuran (THF) (THF) generates the aryne intermediate earlier 3Or 8, with iodine ylide compound [3+2] cycloaddition reaction takes place immediately, generate oxygen two silica-based benzofuran derivative 5a-fOr aphthofurans derivative 9a-f
Figure 2013101218748100002DEST_PATH_IMAGE001
Figure 893337DEST_PATH_IMAGE002
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:
Figure 2013101218748100002DEST_PATH_IMAGE003
；
The structural formula of described aphthofurans derivative is:
Figure 623527DEST_PATH_IMAGE004
；
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
A kind of method for preparing above-mentioned benzo or aphthofurans derivative is characterized in that this method has following steps:
A. two acetic acid iodobenzene salt are dissolved in the methylene dichloride, under inert atmosphere and ice-water bath, add trifluoromethanesulfonic acid, reacted room temperature reaction 1～2 hour 0.5～1 hour; Then under ice-water bath, this reaction soln is joined in the dichloromethane solution of benzo two (oxygen two silicon are luxuriant) or oxygen two silica-based naphthalenes, continue ice-water bath reaction 0.5～1 hour, room temperature reaction 3～4 hours is adding Diisopropylamine, iodine ylide compound at last successively, tetrabutyl ammonium fluoride TBAF/ tetrahydrofuran THF solution, react end in 3～18 hours, separate and purify, obtaining solid is oxygen two silica-based benzofuran derivative or aphthofurans derivative; The structural formula of described two acetic acid iodobenzene salt is: PhI (OAc) 2The structural formula of described benzo two (oxygen two silicon are luxuriant) is:
Figure 2013101218748100002DEST_PATH_IMAGE005
The structural formula of described oxygen two silica-based naphthalenes is: The structural formula of described Diisopropylamine is: i-Pr 2NH; The structural formula of described iodine ylide compound is: Wherein: R 1For: OCH 3, OC 2H 5, CH 3R 2For: CH 3, C 6H 5R 1=R 2For: (CH 2) 3, CH 2C (CH 3) 2CH 2The mol ratio of described two acetic acid iodobenzene salt, trifluoromethanesulfonic acid, benzo two (oxygen two silicon are luxuriant) or oxygen two silica-based naphthalenes, Diisopropylamine, iodine ylide 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 are luxuriant) or oxygen two silica-based naphthalenes, produces benzyne and naphthalyne at ambient temperature, further with the addition reaction of iodine ylide 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 promptly can participate in reaction, and different iodine ylide compounds can influence its productive rate, but productive rate is generally higher.Therefore, present method is a kind of effective means that makes up cumarone or aphthofurans skeleton, has enriched the synthetic method of organic heterocyclic molecule.
Embodiment
One: two acetic acid iodobenzene of embodiment salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), benzo two (oxygen two silicon are luxuriant) ( 1, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4a, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), the gained benzofuran derivative is: 2-methyl-5,6-oxygen two silica-based-3-benzofurancarboxylic acid methyl esters ( 5a), yield 83%, the structure of this compound is:
Figure 860790DEST_PATH_IMAGE008
Molecular formula: C 15H 20O 4Si 2
Chinese named: Chinese named: 2-methyl-5,6-oxygen two silica-based-3-benzofurancarboxylic acid methyl esters
English name: 2-Methyl-5,6-oxadisilole-3-benzofuran carboxylic acid, methyl ester
Molecular weight: 320.09
Outward appearance: white powder
Proton nmr spectra (500 MHz, 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 (125 MHz, CDCl 3): δ 1.3,1.4, and 14.7,51.6,108.7,113.1,124.7,127.8,142.4,143.7,155.2,164.3,165.0 ppm.
 
Two: two acetic acid iodobenzenes of embodiment salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), benzo two (oxygen two silicon are luxuriant) ( 1, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4b, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), the gained benzofuran derivative is: 2-methyl-5,6-oxygen two silica-based-3-benzofurancarboxylic acid ethyl esters ( 5b), yield 91%, the structure of this compound is:
Figure 2013101218748100002DEST_PATH_IMAGE009
Molecular formula: C 16H 22O 4Si 2
Chinese named: 2-methyl-5,6-oxygen two silica-based-3-benzofurancarboxylic acid ethyl esters
English name: 2-Methyl-5,6-oxadisilole-3-benzofuran carboxylic acid, ethyl ester
Molecular weight: 334.11
Outward appearance: white powder
Proton nmr spectra (500 MHz, CDCl 3): δ 0.39 (s, 6H), 0.40 (s, 6H), 1.45 (t, J=7.0 Hz, 3H), 2.78 (s, 3H), 4.43 (q, J=7.0 Hz, 2H), 7.60 (s, 1H), 8.18 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl 3): δ 1.35,1.42, and 14.6,14.8,60.5,109.0,113.1,124.8,128.0,142.4,143.7,155.2,164.0,164.6 ppm.
 
Three: two acetic acid iodobenzenes of embodiment salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), benzo two (oxygen two silicon are luxuriant) ( 1, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4c, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), the gained benzofuran derivative is: 2-methyl-3-ethanoyl-5,6-oxygen two silica-based cumarones ( 5c), yield 85%, the structure of this compound is:
Figure 547599DEST_PATH_IMAGE010
Molecular formula: C 15H 20O 3Si 2
Chinese named: 2-methyl-3-ethanoyl-5,6-oxygen two silica-based cumarones
English name: 2-Methyl-3-acetyl-5,6-oxadisilole benzofuran
Molecular weight: 304.10
Outward appearance: white powder
Proton nmr spectra (500 MHz, 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 (125 MHz, CDCl 3): δ 1.3,1.5, and 15.7,31.4,113.3,117.6,124.5,127.8,142.8,144.0,155.1,163.3,194.3 ppm.
 
Four: two acetic acid iodobenzenes of embodiment salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), benzo two (oxygen two silicon are luxuriant) ( 1, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4d, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), the gained benzofuran derivative is: 2-phenyl-3-ethanoyl-5,6-oxygen two silica-based cumarones ( 5d), yield 73%, the structure of this compound is:
Figure 2013101218748100002DEST_PATH_IMAGE011
Molecular formula: C 20H 22O 3Si 2
Chinese named: 2-phenyl-3-ethanoyl-5,6-oxygen two silica-based cumarones
English name: 2-Phenyl-3-acetyl-5,6-oxadisilole benzofuran
Molecular weight: 366.11
Outward appearance: white powder
Proton nmr spectra (500 MHz, 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 (125 MHz, CDCl 3): δ 1.3,1.5, and 30.7,113.5,118.4,125.6,128.5,128.9,129.8,130.3,130.8,143.1,145.2,155.5,161.0,195.9 ppm.
 
Five: two acetic acid iodobenzenes of embodiment salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), benzo two (oxygen two silicon are luxuriant) ( 1, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4e, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), the 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:
Figure 183111DEST_PATH_IMAGE012
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 (500 MHz, 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 (125 MHz, CDCl 3): δ 1.4,1.5, and 22.7,24.1,38.1,113.5,116.4,124.9,125.3,143.5,144.9,156.2,171.7,195.3 ppm.
 
Six: two acetic acid iodobenzenes of embodiment salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), benzo two (oxygen two silicon are luxuriant) ( 1, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4f, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), the 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:
Figure 2013101218748100002DEST_PATH_IMAGE013
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 (500 MHz, 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 (125 MHz, CDCl 3): δ 1.3,1.4, and 28.7,35.4,38.0,52.4,113.5,115.2,124.8,125.1,143.4,144.7,156.5,170.7,194.5 ppm.
 
Seven: two acetic acid iodobenzenes of embodiment salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), oxygen two silica-based naphthalenes ( 6, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4a, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), gained aphthofurans derivative is: 2-methyl-3-naphtho-[2,3- b] methyl furoate ( 9a), yield 62%, the structure of this compound is:
Figure 450144DEST_PATH_IMAGE014
Molecular formula: C 15H 12O 3
Chinese named: 2-methyl-3-naphtho-[2,3- b] methyl furoate
English name: 2-Methyl naphtho[2,3- b] furan-3-carboxylic acid, methyl ester
Molecular weight: 240.08
Outward appearance: yellow powder
Proton nmr spectra (500 MHz, 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 (125 MHz, CDCl 3): δ 14.9,51.6, and 106.6,108.5,119.9,124.5,125.2,126.7,127.9,128.5,131.1,131.2,152.7,164.9,166.8 ppm.
 
Eight: two acetic acid iodobenzenes of embodiment salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), oxygen two silica-based naphthalenes ( 6, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4b, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), gained aphthofurans derivative is: 2-methyl-3-naphtho-[2,3- b] furyl ethyl formate ( 9b), yield 55%, the structure of this compound is:
Figure 2013101218748100002DEST_PATH_IMAGE015
Molecular formula: C 16H 14O 3
Chinese named: 2-methyl-3-naphtho-[2,3- b] furyl ethyl formate
English name: 2-Methyl naphtho[2,3- b] furan-3-carboxylic acid, ethyl ester
Molecular weight: 254.09
Outward appearance: yellow powder
Proton nmr spectra (500 MHz, CDCl 3): δ 1.50 (t, J=7.0 Hz, 3H), 2.82 (s, 3H), 4.47 (q, J=7.0 Hz, 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 (125 MHz, CDCl 3): δ 14.6,14.7, and 60.5,106.5,108.6,119.9,124.5,125.2,126.8,127.9,128.5,131.0,131.2,152.7,164.5,166.6 ppm.
 
Nine: two acetic acid iodobenzenes of embodiment salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), oxygen two silica-based naphthalenes ( 6, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4c, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), gained aphthofurans derivative is: 2-methyl-3-ethanoyl naphtho-[2,3- b] furans ( 9c), yield 60%, the structure of this compound is:
Figure 711361DEST_PATH_IMAGE016
Molecular formula: C 15H 12O 2
Chinese named: 2-methyl-3-ethanoyl naphtho-[2,3- b] furans
English name: 2-Methyl-3-acetyl naphtho[2,3- b] furan
Chinese named: 2-phenyl-3-ethanoyl-5,6-oxygen two silica-based cumarones
Molecular weight: 224.08
Outward appearance: yellow powder
Proton nmr spectra (500 MHz, 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 (125 MHz, CDCl 3): δ 15.9,31.4, and 106.8,117.2,119.9,124.7,125.5,126.8,127.9,128.5,130.3,131.2,152.6,166.0,194.1 ppm.
 
Ten: two acetic acid iodobenzenes of embodiment salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), oxygen two silica-based naphthalenes ( 6, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4d, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), gained aphthofurans derivative is: 2-phenyl-3-ethanoyl naphtho-[2,3- b] furans ( 9d), yield 62%, the structure of this compound is:
Figure 2013101218748100002DEST_PATH_IMAGE017
Molecular formula: C 20H 14O 2
Chinese named: 2-phenyl-3-ethanoyl naphtho-[2,3- b] furans
English name: 2-Phenyl-3-acetyl naphtho[2,3- b] furan
Molecular weight: 286.10
Outward appearance: yellow powder
Proton nmr spectra (500 MHz, 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=7.5 Hz, 1H), 8.03-8.04 (m, 1H), 8.63 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl 3): δ 29.9,106.9,118.0,121.2,124.7,125.7,127.5,127.9,128.8,128.9,130.0,130.2,131.1,131.4,131.9,152.8,163.2,195.5 ppm.
 
Embodiment 11: two acetic acid iodobenzene salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), oxygen two silica-based naphthalenes ( 6, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4e, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), gained aphthofurans derivative is: 3, the 4-dihydrobenzo [ b] naphtho-[2,3- d] furans-1 ( 2H)-ketone ( 9e), yield 40%, the structure of this compound is:
Figure 193289DEST_PATH_IMAGE018
Molecular formula: C 16H 12O 2
Chinese named: 3, the 4-dihydrobenzo [ b] naphtho-[2,3- d] furans-1 ( 2H)-ketone
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 (500 MHz, 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 (125 MHz, CDCl 3): δ 22.5,24.2, and 37.9,107.2,116.2,120.2,124.0,124.9,125.6,128.1,128.6,131.45,131.51,153.5,174.0,194.8 ppm.
 
Embodiment 12: two acetic acid iodobenzene salt (1.5～2.5 eq), trifluoromethanesulfonic acid (3.5～4.5 eq), oxygen two silica-based naphthalenes ( 6, 1.0 eq), Diisopropylamine (3.0～4.0 eq), iodine ylide compound ( 4f, 4.0～5.0 eq), TBAF/THF(3.0～4.0 eq), gained aphthofurans derivative is: 3,3-dimethyl-3, the 4-dihydrobenzo [ b] naphtho-[2,3- d] furans-1 ( 2H)-ketone ( 9f), yield 45%, the structure of this compound is:
Figure DEST_PATH_IMAGE019
Molecular formula: C 18H 16O 2
Chinese named: 3,3-dimethyl-3, the 4-dihydrobenzo [ b] naphtho-[2,3- d] furans-1 ( 2H)-ketone
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 (500 MHz, 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 (125 MHz, CDCl 3): δ 28.9,35.3,38.1,52.3,107.2,115.0,120.1,123.9,124.9,125.6,128.1,128.6,131.4,131.5,153.9,173.1,194.1 ppm.

Claims (2)

1. benzo or aphthofurans derivative is characterized in that the structural formula of described benzofuran derivative is:
；
The structural formula of described aphthofurans derivative is:
Figure 2013101218748100001DEST_PATH_IMAGE004
；
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
2. method for preparing benzo according to claim 1 or aphthofurans derivative is characterized in that this method has following steps:
A. two acetic acid iodobenzene salt are dissolved in the methylene dichloride, under inert atmosphere and ice-water bath, add trifluoromethanesulfonic acid, reacted room temperature reaction 1～2 hour 0.5～1 hour; Then under ice-water bath, this reaction soln is joined in the dichloromethane solution of benzo two (oxygen two silicon are luxuriant) or oxygen two silica-based naphthalenes, continue ice-water bath reaction 0.5～1 hour, room temperature reaction 3～4 hours is adding Diisopropylamine, iodine ylide compound at last successively, tetrabutyl ammonium fluoride TBAF/ tetrahydrofuran THF solution, react end in 3～18 hours, separate and purify, obtaining solid is oxygen two silica-based benzofuran derivative or aphthofurans derivative; The structural formula of described two acetic acid iodobenzene salt is: PhI (OAc) 2The structural formula of described benzo two (oxygen two silicon are luxuriant) is:
Figure 2013101218748100001DEST_PATH_IMAGE006
The structural formula of described oxygen two silica-based naphthalenes is:
Figure DEST_PATH_IMAGE008
The structural formula of described Diisopropylamine is: i-Pr 2NH; The structural formula of described iodine ylide compound is:
Figure DEST_PATH_IMAGE010
Wherein: R 1For: OCH 3, OC 2H 5, CH 3R 2For: CH 3, C 6H 5R 1=R 2For: (CH 2) 3, CH 2C (CH 3) 2CH 2The mol ratio of described two acetic acid iodobenzene salt, trifluoromethanesulfonic acid, benzo two (oxygen two silicon are luxuriant) or oxygen two silica-based naphthalenes, Diisopropylamine, iodine ylide 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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CN105061372A (en) * 2015-07-17 2015-11-18 湖南大学 Synthetic methods of naphthopyran compounds
CN106163284A (en) * 2014-02-07 2016-11-23 北京强新生物科技有限公司 3 substituted carbonyl naphtho-[2,3 b] furan derivatives or its pharmaceutically acceptable salts
CN108409777A (en) * 2018-04-23 2018-08-17 上海大学 Benzisothiazole derivatives or naphtho- Isothizole derivatives and its synthetic method
CN110407784A (en) * 2019-05-16 2019-11-05 上海大学 2- sweet-smelling formacyl benzofuran derivatives or 2- sweet-smelling formacyl aphthofurans derivative and its synthetic method
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CN106163284A (en) * 2014-02-07 2016-11-23 北京强新生物科技有限公司 3 substituted carbonyl naphtho-[2,3 b] furan derivatives or its pharmaceutically acceptable salts
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CN105061372A (en) * 2015-07-17 2015-11-18 湖南大学 Synthetic methods of naphthopyran compounds
CN108409777A (en) * 2018-04-23 2018-08-17 上海大学 Benzisothiazole derivatives or naphtho- Isothizole derivatives and its synthetic method
CN110407784A (en) * 2019-05-16 2019-11-05 上海大学 2- sweet-smelling formacyl benzofuran derivatives or 2- sweet-smelling formacyl aphthofurans derivative and its synthetic method
CN114539200A (en) * 2022-02-22 2022-05-27 陕西科技大学 Synthesis method of tetrahydroxanthone

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