CN115626905B - 一种由邻炔基苯酚合成苯并呋喃酮的方法 - Google Patents
一种由邻炔基苯酚合成苯并呋喃酮的方法 Download PDFInfo
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- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical compound C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
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- 239000003054 catalyst Substances 0.000 claims abstract description 22
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010931 gold Substances 0.000 claims abstract description 22
- 229910052737 gold Inorganic materials 0.000 claims abstract description 22
- 239000012363 selectfluor Substances 0.000 claims abstract description 22
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 238000003786 synthesis reaction Methods 0.000 claims description 12
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
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- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 5
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- CUCUKLJLRRAKFN-UHFFFAOYSA-N 7-Hydroxy-(S)-usnate Chemical compound CC12C(=O)C(C(=O)C)C(=O)C=C1OC1=C2C(O)=C(C)C(O)=C1C(C)=O CUCUKLJLRRAKFN-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- IIUZTXTZRGLYTI-UHFFFAOYSA-N Dihydrogriseofulvin Natural products COC1CC(=O)CC(C)C11C(=O)C(C(OC)=CC(OC)=C2Cl)=C2O1 IIUZTXTZRGLYTI-UHFFFAOYSA-N 0.000 description 1
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- DDUHZTYCFQRHIY-UHFFFAOYSA-N Negwer: 6874 Natural products COC1=CC(=O)CC(C)C11C(=O)C(C(OC)=CC(OC)=C2Cl)=C2O1 DDUHZTYCFQRHIY-UHFFFAOYSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
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- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
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- OTAFHZMPRISVEM-UHFFFAOYSA-N chromone Chemical compound C1=CC=C2C(=O)C=COC2=C1 OTAFHZMPRISVEM-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
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- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- DDUHZTYCFQRHIY-RBHXEPJQSA-N griseofulvin Chemical compound COC1=CC(=O)C[C@@H](C)[C@@]11C(=O)C(C(OC)=CC(OC)=C2Cl)=C2O1 DDUHZTYCFQRHIY-RBHXEPJQSA-N 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 229960001797 methadone Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- LNGFWDFUPRZMJI-VEHFIHCQSA-N methyl (2s)-5,7-dichloro-5'-methoxy-6-methyl-3,3'-dioxo-4-[(1r,4r,5r,6s)-4,5,6-trihydroxy-2-methoxycarbonylcyclohex-2-en-1-yl]oxyspiro[1-benzofuran-2,6'-cyclohexa-1,4-diene]-1'-carboxylate Chemical compound COC(=O)C1=C[C@@H](O)[C@@H](O)[C@H](O)[C@@H]1OC1=C(C(=O)[C@]2(O3)C(=CC(=O)C=C2OC)C(=O)OC)C3=C(Cl)C(C)=C1Cl LNGFWDFUPRZMJI-VEHFIHCQSA-N 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- ICTZCAHDGHPRQR-UHFFFAOYSA-N usnic acid Natural products OC1=C(C)C(O)=C(C(C)=O)C2=C1C1(C)C(O)=C(C(=O)C)C(=O)C=C1O2 ICTZCAHDGHPRQR-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种由邻炔基苯酚合成苯并呋喃酮的方法。本方法是以邻炔基苯酚和醇为原料，三苯基膦氯化金为金催化剂，1‑氯甲基‑4‑氟‑1,4‑二氮杂双环[2.2.2]辛烷二(四氟硼酸)盐(selectfluor)为氧化剂，三氟甲磺酸为助催化剂，在氩气气氛、70℃、乙腈溶液中，高效合成苯并呋喃酮化合物。
Description
技术领域
本发明涉及一种由邻炔基苯酚合成苯并呋喃酮的方法。
背景技术
苯并呋喃-3(2H)-酮代表了合成某些具有广泛生物和药理活性的天然产物及其衍生物的关键结构。2,2-二取代苯并呋喃酮核心存在于多种药物中，常规用于治疗不同的疾病，如灰黄霉素(抗真菌剂)、墨沙酮(杀菌剂)、Sch 202596(抗阿尔茨海默病)和松萝酸(抗生素)等(参见：Firoozi,N.,Roshan,Z.,&Mohammadizadeh,M.R.Facile Chemoselectivesynthesis of 2-(2-(Methoxycarbonyl)-3-oxo-2,3-dihydrobenzofuran-2-yl)benzoicacids and 3H,3’H-Spiro[benzofuran-2,1′-isobenzofuran]-3,3′-dionederivatives.Applied Organometallic Chemistry.2017,32(1),e3963.)。目前合成苯并呋喃酮的方法主要有，N-杂环卡宾(NHC)和碱催化亲核取代或加氢酰化Stetter重排级联反应构建苯并呋喃酮。(参见：a)He,J.,Zheng,J.,Liu,J.,She,X.,&Pan,X.N-HeterocyclicCarbene Catalyzed Nucleophilic Substitution Reaction for Construction ofBenzopyrones and Benzofuranones.Organic Letters.2006,8(20),4637–4640.b)Padmanaban,M.,Biju,A.T.,&Glorius,F.Efficient Synthesis of Benzofuranones:N-Heterocyclic Carbene(NHC)/Base-Catalyzed Hydroacylation–Stetter–RearrangementCascade.Organic Letters.2011,13(20),5624–5627.)。可见光诱导和单线态氧介导的将苯并吡喃酮光化学转化为苯并呋喃酮的方法(参见：Brahmachari,G.,&Karmakar,I.Visible Light-Induced and Singlet Oxygen-Mediated Photochemical Conversionof4-Hydroxy-α-benzopyrones to 2-Hydroxy-3-oxo-2,3-dihydrobenzofuran-2-carboxamides/carboxylates Using Rose Bengal as a Photosensitizer.The Journalof Organic Chemistry.2020,85(14),8851–8864.)。而以稳定易得的邻炔基苯酚和甲醇为原料，采用条件温和的催化方式，为获得苯并呋喃酮打开一种新的思路与方法。
发明内容
要解决的技术问题
本发明要解决的技术问题是提供一种由邻炔基苯酚制备苯并呋喃酮的方法及其应用。
技术方案
本发明的合成路线如下：
一种由邻炔基苯酚合成苯并呋喃酮的方法，它是以邻炔基苯酚和醇为原料，三苯基膦氯化金为金催化剂，selectfluor为氧化剂，三氟甲磺酸为助催化剂，在氩气气氛、70℃、乙腈溶液中，高效合成苯并呋喃酮化合物。
上述的制备方法，所述的邻炔基苯酚中的R1基团是氢、甲基、酯基，R2基团是氢、甲基、叔丁基、氟、三氟甲基、甲氧基；ROH中的R基团可以是甲基、乙基、丙基、异丙基、正丁基、异丁基等。
上述的制备方法，所述的溶液乙腈是经过氢化钙重蒸处理的。
上述的制备方法，所述的邻炔基苯酚与醇的摩尔比是1:5。
上述的制备方法，所述的金催化剂用量是邻炔基苯酚摩尔数的5％的摩尔量。
上述的制备方法，所述的氧化剂selectfluor用量是邻炔基苯酚摩尔数的200％的摩尔量。
上述的制备方法，所述助催化剂三氟甲磺酸是邻炔基苯酚摩尔数的1-2倍，最优摩尔数为1.5。
典型反应如下：
本发明的方法反应条件温和，从稳定易制备的邻炔基苯酚直接得到苯并呋喃酮化合物。
具体实施方式
原料合成：
原料邻炔基苯酚的合成
通用步骤：
根据文献(Alonso-Maranon,L.；Martinez,M.M.；Sarandeses,L.A.；Gomez-Bengoa,E.；Perez Sestelo,J.Indium(III)-Catalyzed Synthesis of Benzo[b]furansby Intramolecular Hydroalkoxylation of ortho-Alkynylphenols:Scope andMechanistic Insights.J.Org.Chem.2018,83,7970-7980.)进行合成，具体操作如下，首先取一个250mL的圆底烧瓶，称取10mmol的2-碘苯酚，0.2mmol的双三苯基磷二氯化钯，0.4mmol的碘化亚铜，然后加入100mL四氢呋喃、25mL三乙胺溶解，搅拌均匀，再加入20mmol的末端炔烃。将装置置于室温搅拌条件下，反应过夜。反应结束后，使用氯化铵水溶液和二氯甲烷对反应液进行萃取处理，然后将有机相收集并用无水硫酸钠干燥、过滤、减压蒸馏得到粗产物，最后使用正己烷与乙酸乙酯洗脱液进行柱层析提纯粗产物，得到所需的邻炔基苯酚。
利用下述实施例将有助于理解本发明，但并不限制本发明的内容。
实施例1
依次称取(38.8mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，甲醇(32mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物36.5mg，(洗脱液：正己烷-乙酸乙酯，50:1，下同)，产率76％，1H NMR(600MHz,CDCl3)δ7.69(t,J＝7.8Hz,1H),7.65(d,J＝5.4Hz,3H),7.38(d,J＝5.7Hz,3H),7.24(d,J＝8.4Hz,1H),7.11(t,J＝7.5Hz,1H),3.44(s,3H).13C NMR(151MHz,CDCl3)δ196.7,171.0,139.0,133.9,129.6,128.6,126.4,125.4,122.7,119.4,113.1,106.9,52.6.HRMS(ESI)calc.for C15H12O3 +[M+H]+:241.0859,found 241.0855.
实施例2
依次称取(41.6mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，甲醇(32mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物34.6mg，产率68％，1HNMR(600MHz,CDCl3)δ7.68(t,J＝7.8Hz,1H),7.64(d,J＝7.6Hz,1H),7.53(d,J＝8.1Hz,2H),7.23(d,J＝8.3Hz,1H),7.19(d,J＝8.0Hz,2H),7.10(t,J＝7.4Hz,1H),3.43(s,3H),2.34(s,3H).13C NMR(151MHz,CDCl3)δ196.8,171.0,139.6,139.0,130.9,129.3,126.4,125.4,122.6,119.5,113.1,107.0,52.6,21.3.HRMS(ESI)calc.for C16H14O3 +[M+H]+:255.1016,found 255.1014.
实施例3
依次称取(50.0mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，甲醇(32mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物40.3mg，产率68％，1H NMR(600MHz,CDCl3)δ7.68(t,J＝8.5Hz,1H),7.64(d,J＝8.5Hz,1H),7.57(d,J＝8.6Hz,2H),7.40(d,J＝8.6Hz,2H),7.23(d,J＝8.4Hz,1H),7.10(t,J＝7.5Hz,1H),3.44(s,3H),1.30(s,9H).13C NMR(151MHz,CDCl3)δ196.9,171.0,152.7,139.0,130.9,126.1,125.6,125.4,122.5,119.5,113.1,107.1,52.6,34.7,31.2.HRMS(ESI)calc.for C19H20O3 +[M+H]+:297.1485,found 297.1485.
实施例4
依次称取(52.8mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，甲醇(32mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物38.5mg，产率62％，1H NMR(600MHz,CDCl3)δ7.55(d,J＝8.6Hz,2H),7.50(d,J＝6.6Hz,1H),7.42(s,1H),7.39(d,J＝8.6Hz,2H),7.13(d,J＝8.4Hz,1H),3.42(s,3H),2.34(s,3H),1.29(s,9H).13CNMR(151MHz,CDCl3)δ197.1,169.4,152.6,140.1,132.2,131.1,126.1,125.6,124.7,119.4,112.7,107.3,52.6,34.7,31.2,20.6.HRMS(ESI)calc.for C20H22O3 +[M+H]+:311.1642,found 311.1640.
实施例5
依次称取(50.5mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，甲醇(32mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物34.1mg，产率57％，1H NMR(600MHz,CDCl3)δ8.40(d,J＝10.6Hz,1H),8.35(s,1H),7.62(dd,J＝9.8Hz,2H),7.40(m,J＝6.2Hz,3H),7.29(d,J＝9.2Hz,1H),3.92(s,3H),3.43(s,3H).13C NMR(151MHz,CDCl3)δ195.5,173.4,165.6,140.2,133.2,129.9,128.8,127.8,126.4,125.1,119.5,113.2,108.2,52.8,52.4.HRMS(ESI)calc.for C17H14O5 +[M+H]+:299.0914,found299.0914.
实施例6
依次称取(42.4mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，甲醇(32mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物37.7mg，产率73％，1H NMR(600MHz,CDCl3)δ87.70(t,J＝7.8Hz,1H),7.67-7.61(m,3H),7.24(d,J＝8.4Hz,1H),7.12(t,J＝7.5Hz,1H),7.06(t,J＝8.7Hz,2H),3.41(s,3H).13C NMR(151MHz,CDCl3)δ196.5,170.9,164.4,162.8,139.2,129.9(d,JC-F＝3.0Hz),128.5(d,JC-F＝9.1Hz),125.4,122.8,119.3,115.6,(d,JC-F＝22.7Hz),113.1,106.4,52.6.19F NMR(565MHz,CDCl3)δ-111.79.HRMS(ESI)calc.for C15H11FO3 +[M+H]+:259.0765,found 259.0763.
实施例7
依次称取(42.4mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，甲醇(32mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物40.8mg，产率79％，1HNMR(600MHz,CDCl3)δ7.71(t,J＝7.1Hz,1H),7.66(d,J＝7.7Hz,1H),7.42(d,J＝8.3Hz,1H),7.38-7.33(m,2H),7.25(d,J＝8.4Hz,1H),7.13(t,J＝7.8Hz,1H),7.07(t,J＝9.7Hz,1H),3.43(s,3H).13C NMR(151MHz,CDCl3)δ196.1,170.9,163.7,162.0,139.2,136.5(d,JC-F＝7.6Hz),130.3(d,JC-F＝7.6Hz),125.5,122.9,122.1(d,JC-F＝3.0Hz),119.2,116.6(d,JC-F＝21.1Hz),113.8(d,JC-F＝24.2Hz),113.1,106.1,52.7.19F NMR(565MHz,CDCl3)δ-112.06.HRMS(ESI)calc.for C15H11FO3 +[M+H]+:259.0765,found 259.0763.
实施例8
依次称取(52.4mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，甲醇(32mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物24.7mg，产率40％，1H NMR(600MHz,CDCl3)δ7.77(d,J＝8.0Hz,2H),7.73(t,J＝7.8Hz,1H),7.65(t,J＝8.8Hz,3H),7.27(d,J＝9.4Hz,1H),7.15(t,J＝7.4Hz,1H),3.43(s,3H).13C NMR(151MHz,CDCl3)δ196.0,171.0,139.4,138.0,131.7(q,JC-F＝96.6Hz),127.0,125.6(q,JC-F＝10.6Hz),125.5,123.0,119.1,113.1,106.1,52.8.19F NMR(565MHz,CDCl3)δ-62.84.HRMS(ESI)calc.for C16H11F3O3 +[M+H]+:309.0733,found 309.0736.
实施例9
依次称取(44.8mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，甲醇(32mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物33.5mg，产率62％，1HNMR(600MHz,CDCl3)δ7.70-7.67(m,1H),7.65(d,J＝8.5Hz,1H),7.29(t,J＝8.2Hz,1H),7.23(d,J＝8.4Hz,1H),7.21(s,2H),7.11(t,J＝7.8Hz,1H),6.92(d,J＝11.7Hz,1H),3.81(s,3H),3.44(s,3H).13C NMR(151MHz,CDCl3)δ196.5,171.0,159.8,139.0,135.4,129.7,125.4,122.7,119.4,118.7,115.4,113.1,111.9,106.7,55.4,52.7.HRMS(ESI)calc.forC16H14O4 +[M+H]+:271.0965,found 271.0959.
实施例10
依次称取(44.8mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg,0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，甲醇(32mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物22.2mg，产率41％，1H NMR(600MHz,CDCl3)δ7.68(t,J＝7.8Hz,1H),7.64(d,J＝7.6Hz,1H),7.57(d,J＝8.8Hz,2H),7.22(d,J＝8.3Hz,1H),7.10(t,J＝7.4Hz,1H),6.90(d,J＝8.8Hz,2H),3.79(s,3H),3.41(s,3H).13C NMR(151MHz,CDCl3)δ196.9,170.9,160.7,139.0,127.9,125.9,125.4,122.6,119.5,114.0,113.1,106.9,55.3,52.5.HRMS(ESI)calc.for C16H14O4 +[M+H]+:271.0965,found 271.0959.
实施例11
依次称取(47.6mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，甲醇(32mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物20.1mg，产率35％，1H NMR(600MHz,CDCl3)δ7.55(d,J＝8.9Hz,2H),7.49(d,J＝8.4Hz,1H),7.42(s,1H),7.12(d,J＝8.4Hz,1H),6.89(d,J＝8.9Hz,2H),3.79(s,3H),3.40(s,3H),2.34(s,3H).13C NMR(151MHz,CDCl3)δ197.1,169.3,160.6,140.1,132.2,127.8,126.2,124.8,119.4,114.0,112.6,107.1,55.3,52.5,20.6.HRMS(ESI)calc.for C17H16O4 +[M+H]+:285.1121,found 285.1122.
实施例12
依次称取(38.8mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，乙醇(46mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物36.1mg，产率71％，1HNMR(600MHz,CDCl3)δ7.67(dt,J＝21.0,8.0Hz,4H),7.40-7.36(m,3H),7.23(d,J＝8.4Hz,1H),7.10(t,J＝7.5Hz,1H),3.67(q,J＝7.4Hz,2H),1.28(t,J＝7.0Hz,3H).13C NMR(151MHz,CDCl3)δ196.9,171.0,139.0,134.5,129.5,128.6,126.4,125.4,122.6,119.5,113.1,107.0,61.2,15.3.HRMS(ESI)calc.for C16H14O3 +[M+H]+:255.1016,found255.1014.
实施例13
依次称取(38.8mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，丙醇(60mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物37.1mg，产率69％，1HNMR(600MHz,CDCl3)δ7.69(t,J＝7.8Hz,1H),7.66-7.64(m,J＝4.2Hz,3H),7.37(dd,3H),7.23(d,J＝8.4Hz,1H),7.10(t,J＝7.4Hz,1H),3.57(t,J＝6.7Hz,2H),1.68(h,J＝7.4Hz,2H),0.95(t,J＝7.4Hz,3H).13C NMR(151MHz,CDCl3)δ197.0,171.0,139.0,134.6,129.5,128.6,126.4,125.4,122.5,119.5,113.1,106.9,67.0,23.0,10.5.HRMS(ESI)calc.forC17H16O3 +[M+H]+:269.1172,found 269.1172.
实施例14
依次称取(38.8mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，丁醇(74mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物41.8mg，产率74％，1HNMR(600MHz,CDCl3)δ7.69(t,J＝7.8Hz,1H),7.66-7.62(m,3H),7.40-7.36(d,3H),7.23(d,J＝8.4Hz,1H),7.12-7.09(t,1H),3.60(t,2H),1.66-1.60(m,2H),1.44-1.38(m,J＝7.5Hz,2H),0.90(t,J＝7.4Hz,3H).13C NMR(151MHz,CDCl3)δ197.0,171.0,139.0,134.6,129.5,128.6,126.4,125.4,122.5,119.5,113.0,106.9,65.1,31.7,19.1,13.8.HRMS(ESI)calc.for C18H18O3 +[M+H]+:283.1329,found 283.1328.
实施例15
依次称取(38.8mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，异丙醇(60mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物27.9mg，产率52％，1HNMR(600MHz,CDCl3)δ7.70-7.63(m,4H),7.37(dd,J＝5.2,1.9Hz,3H),7.22(d,J＝8.4Hz,1H),7.09(t,J＝7.1Hz,1H),3.94(dt,J＝12.5,6.3Hz,1H),1.30(d,J＝6.1Hz,3H),1.23(d,J＝6.2Hz,3H).13C NMR(151MHz,CDCl3)δ197.1,170.7,138.9,135.0,129.4,128.5,126.5,125.4,122.4,119.6,113.1,107.7,70.3,24.2,23.9.HRMS(ESI)calc.for C17H16O3 +[M+H]+:269.1172,found 269.1171.
实施例16
依次称取(38.8mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，三氟甲磺酸(45mg，0.3mmol)，异丁醇(74mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物39.5mg，产率70％，1HNMR(600MHz,CDCl3)δ7.69(t,J＝7.8Hz,1H),7.66-7.63(m,3H),7.39-7.36(m,3H),7.23(d,J＝8.4Hz,1H),7.11(t,J＝7.6Hz,1H),3.40-3.35(m,J＝6.6,3.0Hz,2H),1.95(dt,J＝13.4,6.7Hz,1H),0.94(dd,J＝8.8,6.7Hz,6H).13C NMR(151MHz,CDCl3)δ197.1,171.0,139.0,134.7,129.5,128.5,126.4,125.4,122.5,119.6,113.1,106.9,71.6,28.6,19.2.HRMS(ESI)calc.for C18H18O3 +[M+H]+:283.1329,found 283.1328.
实施例17
依次称取(38.8mg，0.2mmol)，金催化剂Ph3PAuCl(5.0mg，0.01mmol)，氟试剂selectfluor(141.7mg，0.4mmol)，乙酸(60mg，1.0mmol)和乙腈(2.0mL)于10mL反应瓶中，将反应瓶移出手套箱，于70℃反应3小时。干法上样，柱层析(200-300目层析硅胶)得到产物22.0mg，产率41％，1H NMR(600MHz,CDCl3)δ7.72-7.65(m,4H),7.43(d,J＝5.2Hz,3H),7.24(d,J＝8.6Hz,1H),7.18(t,J＝7.4Hz,1H),2.23(s,3H).13C NMR(151MHz,CDCl3)δ194.5,169.2,168.7,138.1,132.8,129.9,128.7,125.8,125.2,123.0,119.8,112.4,101.8,20.6.HRMS(ESI)calc.for C16H12O4 +[M+Na]+:291.0628,found 291.0628.
Claims (6)
1.一种由邻炔基苯酚合成苯并呋喃酮的方法，其特征是：它是以邻炔基苯酚1和醇2为原料，三苯基膦氯化金为金催化剂，selectfluor为氧化剂，三氟甲磺酸为助催化剂，在氩气气氛、70℃、乙腈溶液中，高效合成苯并呋喃酮化合物，所述苯并呋喃酮化合物结构式如下：
其中，R1为连接在苯环上的H、4-CH3、4-CO2CH3中的任意一种；R2为连接在苯环上的H、para-CH3、para-t-Bu、para-F、para-CF3、para-OCH3、meta-F、meta-OCH3中的任意一种；R为Me、Et、n-Pr、n-Bu、i-Pr、i-Bu中的任意一种；
合成路线如下：
2.根据权利要求1所述的合成苯并呋喃酮的方法，其特征是：所述的溶液乙腈是经过氢化钙重蒸处理的。
3.根据权利要求1所述的合成苯并呋喃酮的方法，其特征是：邻炔基苯酚与醇的摩尔比是1:5。
4.根据权利要求1所述的合成苯并呋喃酮的方法，其特征是：所述的金催化剂用量是邻炔基苯酚摩尔数的5％的摩尔量。
5.根据权利要求1所述的合成苯并呋喃酮的方法，其特征是：所述的氧化剂selectfluor用量是邻炔基苯酚摩尔数的200％的摩尔量。
6.根据权利要求1所述的合成苯并呋喃酮的方法，其特征是：所述助催化剂三氟甲磺酸是邻炔基苯酚摩尔数的1-2倍。
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| JP2007051099A (ja) * | 2005-08-18 | 2007-03-01 | Univ Of Tokushima | 新規ポリフェノール化合物 |
| CN111100101A (zh) * | 2019-12-23 | 2020-05-05 | 浙江万里学院 | 一种3-苯并呋喃酮类化合物的催化合成方法 |
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|---|
| Catalytic Transformations of Alkynes into either a-Alkoxy or a-Aryl Enolates: Mannich Reactions by Cooperative Catalysis and Evidence for Nucleophile-Directed Chemoselectivity;Rajkumar Lalji Sahani et al.;Angew. Chem. Int. Ed.;第57卷;第14878-14882页 * |
| Flexible Synthesis of Benzofuranones from ortho-Alkynyl Phenols or Benzofurans;Wenqian Du et al.;Eur. J. Org. Chem.;第26卷;1-6 * |
| Gold-Catalyzed Fluorination–Hydration: Synthesis of a-Fluorobenzofuranones from 2-Alkynylphenol Derivatives;Qiang Wang et al.;Chem. Eur. J.;第22卷;第14736-14745页 * |
| STUDIES ON SYNTHESIS OF 3(2H)-BENZOFURANONE DERIVATIVES;Sa´ ndor Bokotey et al.;SYNTHETIC COMMUNICATIONS;第32卷(第15期);第2325-2343页 * |
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