反應簡介

傅-克?；磻侵敢活愒诼芬姿顾嶙鳛榇呋瘎┑臈l件下，芳烴與酰氯或酸酐進行?；姆磻Ｔ摲磻捎隰驶娮有挠绊?，一般不會像烷基化反應生成多重?；a物，僅通過親電芳香取代形成單酰化產物。[1,2]

圖1. 傅-克酰基化反應

反應機理

Ⅰ. 路易斯酸催化劑（AlCl3）和?；穆仍有纬山j合物，氯的解離形成?；颊x子。

Ⅱ. ?；x子（RCO+）繼續對芳環進行繼續對芳烴進行親電攻擊。隨著絡合物的形成，其芳香性暫時消失。

Ⅲ. 中間態去質子化，恢復芳環的芳香性。電荷轉移至氯離子形成HCl，AlCl3催化劑重新形成。[1]

圖2. AlCl3傅-克?；磻獧C理

應用

傅-克?；磻蓱糜谝韵禄衔锏暮铣桑?/p>

1. 二芳基乙酸衍生物[4]

2. 聚醚醚酮（PEEK）或mPEK[5]

3. 1,5-雙（4-氟苯甲?；?2,6-二甲基萘[6]

4. 芳香酮[7]

5. 不對稱芳香胺[8]

6. 環酮，例如1-四烯酮和1-茚滿酮[9]

7. 2-乙?；?6-甲氧基萘，用于合成非甾體抗炎鎮痛新藥萘普生及萘普酮的關鍵中間體[10]

研究進展

1.PVP-TfOH已經作為傅-克?；磻懈咝乙子诤筇幚淼墓腆w超強酸催化劑體系得以應用。在溫和的反應條件下，芳烴和乙醛酸通過傅-克?；磻?，實現了無溶劑一鍋法合成二芳基乙酸衍生物。[4]

圖3. 芳烴和乙醛酸通過傅-克?；磻?，無溶劑一鍋法合成二芳基乙酸衍生物

2. 一種基于咪唑的離子液體可作為催化劑，催化芳烴與乙酰氯進行傅-克?；磻?span style="vertical-align: super;">[11]

3. 據報道三氟甲磺酸鉺是一種含有給電子基團且可用于微波輔助下芳烴的傅-克?；母咝Т呋瘎?span style="vertical-align: super;">[12]

4. 虎皮楠生物堿是一類結構高度復雜多樣的三萜類生物堿，可通過分子內的傅-克?；磻苯忧铱焖俚臉嫿?a name="OLE_LINK2" style="color: rgb(0, 107, 180);">ACDE環系統。[13]

5. 酸催化的的多米諾傅-克?；磻捎糜诟咝嫿ㄅ_灣杉醌的6,5,6-ABC三環骨架結構。還可用于二萜(±)-甲萘醌B和(±)-二氯酮的合成。[14]

6. 通過親電傅克酰基化縮聚反應可合成兩種含1,4-萘單元的單體，新型聚（芳基酮）和聚（芳基醚酮砜）。[15]

7. 據研究，SBA-15中三苯基錫的甲苯和乙酸酐可發生傅-克酰基化反應。[16]

8. 離子液體1-異丁基-3-甲基咪唑二氫磷酸([i-BMIM]H2PO4)中的三氟甲磺酸銦在芳香族化合物與酸酐的傅-克?；磻酗@示出強力的催化活性。[17]

9. 25,27-二烷氧基杯芳烴的傅-克?；磻Ｊ褂悯Ｂ群虯lCl3在1,2-二氯乙烷中直接?；撌宥』紵N，以高產率區域選擇性地提供相應的二?；苌?。[18]

參考文獻：

1.Fox MA, Whitesell JK. 1994. Organic Chemistry. Boston: Jones and Bartlett.

2.Li JJ. 2009. Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications. Springer.

3.Sartori G, Maggi R. Advances in Friedel-Crafts Acylation Reactions. https://doi.org/10.1201/9781420067934

4.Prakash G, Paknia F, Kulkarni A, Narayanan A, Wang F, Rasul G, Mathew T, Olah GA. 2015. Taming of superacids: PVP-triflic acid as an effective solid triflic acid equivalent for Friedel?Crafts hydroxyalkylation and acylation. Journal of Fluorine Chemistry. 171102-112. https://doi.org/10.1016/j.jfluchem.2014.08.020

5.Baek J, Lyons CB, Tan L. 2004. Grafting of Vapor-Grown Carbon Nanofibers via in-Situ Polycondensation of 3-Phenoxybenzoic Acid in Poly(phosphoric acid). Macromolecules. 37(22):8278-8285. https://doi.org/10.1021/ma048964o

6.Ohno M, Takata T, Endo T. 1995. Synthesis of a novel naphthalene-based poly(arylene ether-ketone) by polycondensation of 1,5-bis(4-fluorobenzoyl)-2,6-dimethylnaphthalene with bisphenol a. J. Polym.Sci. A Polym.Chem.. 33(15):2647-2655. https://doi.org/10.1002/pola.1995.080331511

7.de Noronha RG, Fernandes AC, Rom?o CC. 2009. MoO2Cl2 as a novel catalyst for Friedel?Crafts acylation and sulfonylation. Tetrahedron Letters. 50(13):1407-1410. https://doi.org/10.1016/j.tetlet.2009.01.039

8.Nordlander JE, Payne MJ, Njoroge FG, Balk MA, Laikos GD, Vishwanath VM. 1984.Friedel-Crafts acylation with N-(trifluoroacetyl)-.alpha.-amino acid chlorides.Application to the preparation of .beta.-arylalkylamines and 3-substituted 1,2,3,4-tetrahydroisoquinolines. J.Org.Chem.. 49(22):4107-4111. https://doi.org/10.1021/jo00196a001

9.Tran PH, Huynh VH, Hansen PE, Chau DN, Le TN. 2015. An Efficient and Green Synthesis of 1-Indanone and 1-Tetralone via Intramolecular Friedel-Crafts Acylation Reaction. Asian Journal of Organic Chemistry. 4(5):482-486. https://doi.org/10.1002/ajoc.201402274

10.Kobayashi S, Komoto I. 2000. Remarkable Effect of Lithium Salts in Friedel?Crafts Acylation of 2-Methoxynaphthalene Catalyzed by Metal Triflates. Tetrahedron. 56(35):6463-6465. https://doi.org/10.1016/s0040-4020(00)00610-4

11.Cai M, Wang X. 2014. Activity of Imidazolium-Based Ionic Liquids as Catalysts for Friedel-Crafts Acylation of Aromatic Compounds. Asian J. Chem.. 26(18):5981-5984. https://doi.org/10.14233/ajchem.2014.16354

12.Tran PH, Hansen PE, Nguyen HT, Le TN. 2015. Erbium trifluoromethanesulfonate catalyzed Friedel?Crafts acylation using aromatic carboxylic acids as acylating agents under monomode-microwave irradiation. Tetrahedron Letters. 56(4):612-618. https://doi.org/10.1016/j.tetlet.2014.12.038

13.Wang W, Li G, Wang S, Shi Z, Cao X. 2015. Direct and Short Construction of the ACDE Ring System of Daphenylline. Chem. Asian J.. 10(2):377-382. https://doi.org/10.1002/asia.201403152

14.Tang S, Xu Y, He J, He Y, Zheng J, Pan X, She X. 2008. Application of a Domino Friedel?Crafts Acylation/Alkylation Reaction to the Formal Syntheses of (±)-Taiwaniaquinol B and (±)-Dichroanone. Org.Lett.. 10(9):1855-1858. https://doi.org/10.1021/ol800513v

15.Wen H, Wang P, Cheng S, Yan T, Cai M. 2015. Synthesis and characterization of novel organosoluble poly(aryl ether ketone)s and poly(aryl ether ketone sulfone)s containing 1,4-naphthylene units. High Performance Polymers. 27(6):705-713. https://doi.org/10.1177/0954008314557707

16.Deng Q, Qin Z, Yang Y, Song W. 2015. Synthesis, characterization of triphenyltin grafted on SBA-15 mesoporous silica and its catalytic performance for the synthesis of 4-methylacetophenone. Chinese Journal of Chemical Engineering. 23(2):384-388. https://doi.org/10.1016/j.cjche.2013.12.001

17.Tran PH, Hansen PE, Hoang HM, Chau DN, Le TN. 2015. Indium triflate in 1-isobutyl-3-methylimidazolium dihydrogen phosphate: an efficient and green catalytic system for Friedel?Crafts acylation. Tetrahedron Letters. 56(17):2187-2192. https://doi.org/10.1016/j.tetlet.2015.03.051

18.Skácel J, Budka J, Eigner V, Lhoták P. 2015. Regioselective Friedel?Crafts acylation of calix[4]arenes. Tetrahedron. 71(13):1959-1965. https://doi.org/10.1016/j.tet.2015.02.021

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