[{"@context":"http:\/\/schema.org\/","@type":"BlogPosting","@id":"https:\/\/wiki.edu.vn\/en\/wiki21\/diacetoxyiodobenzene-wikipedia\/#BlogPosting","mainEntityOfPage":"https:\/\/wiki.edu.vn\/en\/wiki21\/diacetoxyiodobenzene-wikipedia\/","headline":"(Diacetoxyiodo)benzene – Wikipedia","name":"(Diacetoxyiodo)benzene – Wikipedia","description":"before-content-x4 From Wikipedia, the free encyclopedia after-content-x4 Chemical compound (Diacetoxyiodo)benzene, also known as phenyliodine(III) diacetate (PIDA) is a hypervalent iodine","datePublished":"2017-01-09","dateModified":"2017-01-09","author":{"@type":"Person","@id":"https:\/\/wiki.edu.vn\/en\/wiki21\/author\/lordneo\/#Person","name":"lordneo","url":"https:\/\/wiki.edu.vn\/en\/wiki21\/author\/lordneo\/","image":{"@type":"ImageObject","@id":"https:\/\/secure.gravatar.com\/avatar\/c9645c498c9701c88b89b8537773dd7c?s=96&d=mm&r=g","url":"https:\/\/secure.gravatar.com\/avatar\/c9645c498c9701c88b89b8537773dd7c?s=96&d=mm&r=g","height":96,"width":96}},"publisher":{"@type":"Organization","name":"Enzyklop\u00e4die","logo":{"@type":"ImageObject","@id":"https:\/\/wiki.edu.vn\/wiki4\/wp-content\/uploads\/2023\/08\/download.jpg","url":"https:\/\/wiki.edu.vn\/wiki4\/wp-content\/uploads\/2023\/08\/download.jpg","width":600,"height":60}},"image":{"@type":"ImageObject","@id":"https:\/\/upload.wikimedia.org\/wikipedia\/commons\/thumb\/2\/26\/PIFA_synthesis_by_exchange.png\/500px-PIFA_synthesis_by_exchange.png","url":"https:\/\/upload.wikimedia.org\/wikipedia\/commons\/thumb\/2\/26\/PIFA_synthesis_by_exchange.png\/500px-PIFA_synthesis_by_exchange.png","height":"64","width":"500"},"url":"https:\/\/wiki.edu.vn\/en\/wiki21\/diacetoxyiodobenzene-wikipedia\/","wordCount":4812,"articleBody":"     (adsbygoogle = window.adsbygoogle || []).push({});before-content-x4From Wikipedia, the free encyclopedia       (adsbygoogle = window.adsbygoogle || []).push({});after-content-x4Chemical compound(Diacetoxyiodo)benzene, also known as phenyliodine(III) diacetate (PIDA) is a hypervalent iodine chemical with the formula C6H5I(OCOCH3)2. It is used as an oxidizing agent in organic chemistry.       (adsbygoogle = window.adsbygoogle || []).push({});after-content-x4Preparation[edit]This reagent was originally prepared by Conrad Willgerodt[3] by reacting iodobenzene with a mixture of acetic acid and peracetic acid:[4][5]C6H5I \u00a0 + \u00a0 CH3CO3H \u00a0 + \u00a0 CH3CO2H \u00a0 \u2192 \u00a0 C6H5I(O2CCH3)2 \u00a0 + \u00a0 H2OPIDA can also be prepared from iodosobenzene and glacial acetic acid:[5]C6H5IO \u00a0 + \u00a0 2\u00a0CH3CO2H \u00a0 \u2192 \u00a0 C6H5I(O2CCH3)2 \u00a0 + \u00a0 H2OMore recent preparations direct from iodine, acetic acid, and benzene have been reported, using either sodium perborate[6] or potassium peroxydisulfate[7] as the oxidizing agent:[8]C6H6 \u00a0 + \u00a0 I2 \u00a0 + \u00a0 2\u00a0CH3CO2H \u00a0 + \u00a0 K2S2O8 \u00a0 \u2192 \u00a0 C6H5I(O2CCH3)2 \u00a0 + \u00a0 KI \u00a0 + \u00a0 H2SO4 \u00a0 + \u00a0 KHSO4The PIDA molecule is termed hypervalent as its iodine atom (technically a hypervalent iodine) is in its +III oxidation state and has more than typical number of covalent bonds.[9]  It adopts a T-shaped molecular geometry, with the phenyl group occupying one of the three equatorial positions of a trigonal bipyramid (lone pairs occupy the other two) and the axial positions occupied by oxygen atoms from the acetate groups.  The “T” is distorted in that the phenyl-C to I to acetate-O bond angles are less than 90\u00b0.[1]  A separate investigation of the crystal structure confirmed that it has orthorhombic crystals in space group Pnn2 and reported unit-cell dimensions in good agreement with the original paper.[1][2]  The bond lengths around the iodine atom were 2.08\u00a0\u00c5 to the phenyl carbon atom and equal 2.156\u00a0\u00c5 bonds to the acetate oxygen atoms. This second crystal structure determination explained the distortion in the geometry by noting the presence of two weaker intramolecular iodine\u2013oxygen interactions, resulting in an “overall geometry of each iodine [that] can be described as a pentagonal-planar arrangement of three strong and two weak secondary bonds.”[2]       (adsbygoogle = window.adsbygoogle || []).push({});after-content-x4Unconventional reactions[edit]One use of PIDA is in the preparation of similar reagents by substitution of the acetate groups. For example, it can be used to prepare (bis(trifluoroacetoxy)iodo)benzene (phenyliodine(III) bis(trifluoroacetate), PIFA) by heating in trifluoroacetic acid:[10][8]PIFA can be used to carry out the Hofmann rearrangement under mildly acidic conditions,[11] rather than the strongly basic conditions traditionally used.[12][13]  The Hofmann decarbonylation of an N-protected asparagine has been demonstrated with PIDA, providing a route to \u03b2-amino-L-alanine derivatives.[14]PIDA is also used in Su\u00e1rez oxidation, where photolysis of hydroxy compounds in the presence of PIDA and iodine generates cyclic ethers.[15][16][17] This has been used in several total syntheses, such as the total synthesis of (\u2212)-majucin, (\u2212)-Jiadifenoxolane A,[18] and cephanolide A.[19]References[edit]^ a b c Lee, Chow-Kong; Mak, Thomas C. W.; Li, Wai-Kee; Kirner, John F. (1977). “Iodobenzene diacetate”. Acta Crystallogr. B. 33 (5): 1620\u20131622. doi:10.1107\/S0567740877006694.^ a b c d Alcock, Nathaniel W.; Countryman, Rachel M.; Esper\u00e5s, Steinar; Sawyer, Jeffery F. (1979). “Secondary bonding. Part 5. The crystal and molecular structures of phenyliodine(III) diacetate and bis(dichloroacetate)”. J. Chem. Soc., Dalton Trans. 1979 (5): 854\u2013860. doi:10.1039\/DT9790000854.^ Willgerodt, C. (1892). “Zur Kenntniss aromatischer Jodidchloride, des Jodoso- und Jodobenzols”. Chem. Ber. (in German). 25 (2): 3494\u20133502. doi:10.1002\/cber.189202502221.^ Sharefkin, J. G.; Saltzman, H. (1963). “Iodosobenzene Diacetate”. Organic Syntheses. 43: 62. doi:10.15227\/orgsyn.043.0062.; Collective Volume, vol.\u00a05, p.\u00a0660^ a b Moriarty, Robert M.; Chany, Calvin J.; Kosmeder, Jerome W.; Du Bois, Justin (2001). “(Diacetoxyiodo)benzene”. Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. doi:10.1002\/047084289x.rd005m.pub2. ISBN\u00a09780470842898.^ Hossain, Md. Delwar; Kitamura, Tsugio (2005). “Unexpected, Drastic Effect of Triflic Acid on Oxidative Diacetoxylation of Iodoarenes by Sodium Perborate. A Facile and Efficient One-Pot Synthesis of (Diacetoxyiodo)arenes”. J. Org. Chem. 70 (17): 6984\u20136986. doi:10.1021\/jo050927n. PMID\u00a016095332.^ Hossain, Md. Delwar; Kitamura, Tsugio (2007). “New and Direct Approach to Hypervalent Iodine Compounds from Arenes and Iodine. Straightforward Synthesis of (Diacetoxyiodo)arenes and Diaryliodonium Salts Using Potassium \u03bc-Peroxo-hexaoxodisulfate”. Bull. Chem. Soc. Jpn. 80 (11): 2213\u20132219. doi:10.1246\/bcsj.80.2213.^ a b Dohi, Toshifumi; Kita, Yasuyuki (2015). “Oxidizing Agents”.  In Kaiho, Tatsuo (ed.). Iodine Chemistry and Applications. John Wiley & Sons. pp.\u00a0277\u2013302. ISBN\u00a09781118878651.^ Dohi, Toshifumi; Kita, Yasuyuki (2015). “Hypervalent Iodine”.  In Kaiho, Tatsuo (ed.). Iodine Chemistry and Applications. John Wiley & Sons. pp.\u00a0103\u2013158. ISBN\u00a09781118878651.^ Almond, M. R.; Stimmel, J. B.; Thompson, E. A.; Loudon, G. M. (1988). “Hofmann Rearrangement Under Mildly Acidic Conditions Using [I,I-Bis(Trifluoroacetoxy)]Iodobenzene: Cyclobutylamine Hydrochloride from Cyclobutanecarboxamide”. Organic Syntheses. 66: 132. doi:10.15227\/orgsyn.066.0132.; Collective Volume, vol.\u00a08, p.\u00a0132^ Aub\u00e9, Jeffrey; Fehl, Charlie; Liu, Ruzhang; McLeod, Michael C.; Motiwala, Hashim F. (2014). “6.15 Hofmann, Curtius, Schmidt, Lossen, and Related Reactions”. Heteroatom Manipulations. Comprehensive Organic Synthesis II. Vol.\u00a06. pp.\u00a0598\u2013635. doi:10.1016\/B978-0-08-097742-3.00623-6. ISBN\u00a09780080977430.^ Wallis, Everett S.; Lane, John F. (1946). “The Hofmann Reaction”. Org. React. 3 (7): 267\u2013306. doi:10.1002\/0471264180.or003.07.^ Surrey, Alexander R. (1961). “Hofmann Reaction”. Name Reactions in Organic Chemistry (2nd\u00a0ed.). Academic Press. pp.\u00a0134\u2013136. ISBN\u00a09781483258683.^ Zhang, Lin-hua; Kauffman, Goss S.; Pesti, Jaan A.; Yin, Jianguo (1997). “Rearrangement of N\u03b1-Protected L-Asparagines with Iodosobenzene Diacetate. A Practical Route to \u03b2-Amino-L-alanine Derivatives”. J. Org. Chem. 62 (20): 6918\u20136920. doi:10.1021\/jo9702756.^ Concepci\u00f3n, Jos\u00e9 I.; Francisco, Cosme G.; Hern\u00e1ndez, Rosendo; Salazar, Jos\u00e9 A.; Su\u00e1rez, Ernesto (1984). “Intramolecular hydrogen abstraction. Iodosobenzene diacetate, an efficient and convenient reagent for alkoxy radical generation”. Tetrahedron Letters. 25 (18): 1953\u20131956. doi:10.1016\/S0040-4039(01)90085-1.^ Courtneidge, John L.; Lusztyk, Janusz; Pag\u00e9, Daniel (1994). “Alkoxyl radicals from alcohols. Spectroscopic detection of intermediate alkyl and acyl hypoiodites in the Su\u00e1rez and Beebe reactions”. Tetrahedron Letters. 35 (7): 1003\u20131006. doi:10.1016\/S0040-4039(00)79950-3.^ Dorta, R. L.; Francisco, C.G.; Freire, R.; Su\u00e1rez, E. (1988). “Intramolecular hydrogen abstraction. The use of organoselenium reagents for the generation of alkoxy radicals”. Tetrahedron Letters. 29 (42): 5429\u20135432. doi:10.1016\/S0040-4039(00)82887-7.^ Condakes, Matthew L.; Hung, Kevin; Harwood, Stephen J.; Maimone, Thomas J. (2017). “Total Syntheses of (\u2212)-Majucin and (\u2212)-Jiadifenoxolane A, Complex Majucin-Type Illicium Sesquiterpenes”. Journal of the American Chemical Society. 139 (49): 17783\u201317786. doi:10.1021\/jacs.7b11493. PMC\u00a05729088. PMID\u00a029148748.^ Qing, Zhineng; Mao, Peng; Wang, Tie; Zhai, Hongbin (2022). “Asymmetric Total Syntheses of Cephalotane-Type Diterpenoids Cephanolides A\u2013D”. Journal of the American Chemical Society. 144 (23): 10640\u201310646. doi:10.1021\/jacs.2c03978. PMID\u00a035653731. S2CID\u00a0249314606.       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