(Diacetoxyiodo)benzene

1,1′-[(Phenyl-λ3-iodanediyl)bis(oxy)]di(ethan-1-one) Bis(acetoxy)(phenyl)iodaneBis(acetato-O)phenyliodineBis(acetoxy)iodobenzene (BAIB)(Diacetoxyiodo)benzeneI,I-DiacetatoiodobenzeneIodobenzene diacetateIodosobenzene I,I-diacetatePhenyliodine(III) diacetate (PIDA)Phenyliodo diacetate (diacetoxyiodo)benzene.svg 3240-34-4 correct FDA AY2C9T5FRZ 76724 69182 221-808-1 CC(=O)OI(C1=CC=CC=C1)OC(=O)C 1S/C10H11IO4/c1-8(12)14-11(15-9(2)13)10-6-4-3-5-7-10/h3-7H,1-2H3 ZBIKORITPGTTGI-UHFFFAOYSA-N 10 11 1 4 white powder 163–165 reacts soluble in acetic acid, acetonitrile, dichloromethane orthorhombic Pnn2 15.693(3) Å 8.477(2) Å 8.762(2) Å T-shaped molecular geometry (Bis(trifluoroacetoxy)iodo)benzene (Diacetoxyiodo)benzene, also known as phenyliodine(III) diacetate (PIDA) is a hypervalent iodine chemical with the formula C 6 H 5 I(OCOCH 3 ) 2. It is used as an oxidizing agent in organic chemistry. Preparation This reagent was originally prepared by Conrad Willgerodt C. Willgerodt Conrad Willgerodt Zur Kenntniss aromatischer Jodidchloride, des Jodoso- und Jodobenzols German Chem. Ber. 1892 25 2 3494–3502 10.1002/cber.189202502221 https://zenodo.org/record/1425674 by reacting iodobenzene with a mixture of acetic acid and peracetic acid: 1963 43 62 Iodosobenzene Diacetate J. G. Sharefkin H. Saltzman 10.15227/orgsyn.043.0062 cv5p0660 5 660 (Diacetoxyiodo)benzene Encyclopedia of Reagents for Organic Synthesis Moriarty Robert M. Chany Calvin J. Kosmeder Jerome W. Du Bois Justin 2001 John Wiley & Sons 9780470842898 10.1002/047084289x.rd005m.pub2 C6H5I + CH3CO3H + CH3CO2H → C6H5I(O2CCH3)2 + H2O PIDA can also be prepared from iodosobenzene and glacial acetic acid: C6H5IO + 2 CH3CO2H → C6H5I(O2CCH3)2 + H2O More recent preparations direct from iodine, acetic acid, and benzene have been reported, using either sodium perborate Unexpected, Drastic Effect of Triflic Acid on Oxidative Diacetoxylation of Iodoarenes by Sodium Perborate. A Facile and Efficient One-Pot Synthesis of (Diacetoxyiodo)arenes Md. Delwar Hossain Tsugio Kitamura J. Org. Chem. 2005 70 17 6984–6986 10.1021/jo050927n 16095332 or potassium peroxydisulfate New and Direct Approach to Hypervalent Iodine Compounds from Arenes and Iodine. Straightforward Synthesis of (Diacetoxyiodo)arenes and Diaryliodonium Salts Using Potassium μ-Peroxo-hexaoxodisulfate Bull. Chem. Soc. Jpn. Md. Delwar Hossain Tsugio Kitamura 2007 80 11 2213–2219 10.1246/bcsj.80.2213 as the oxidizing agent: Iodine Chemistry and Applications Tatsuo Kaiho John Wiley & Sons 2015 9781118878651 Oxidizing Agents Toshifumi Dohi Yasuyuki Kita 277–302 https://books.google.com/books?id=tWrIBAAAQBAJ&pg=PA283 C6H6 + I2 + 2 CH3CO2H + K2S2O8  → C6H5I(O2CCH3)2 + KI + H2SO4 + KHSO4 The PIDA molecule is termed hypervalent as its iodine atom (technically a hypervalent iodine) is in its +3 oxidation state and has more than typical number of covalent bonds. Iodine Chemistry and Applications Tatsuo Kaiho John Wiley & Sons 2015 9781118878651 Hypervalent Iodine Toshifumi Dohi Yasuyuki Kita 103–158 https://books.google.com/books?id=tWrIBAAAQBAJ&pg=PA103 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°. Iodobenzene diacetate Chow-Kong Lee Thomas C. W. Mak Wai-Kee Li John F. Kirner Acta Crystallogr. B 1977 33 5 1620–1622 10.1107/S0567740877006694 free 1977AcCrB..33.1620L 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. The bond lengths around the iodine atom were 2.08 Å to the phenyl carbon atom and equal 2.156 Å 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–oxygen 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." Secondary bonding. Part 5. The crystal and molecular structures of phenyliodine(III) diacetate and bis(dichloroacetate) Nathaniel W. Alcock Rachel M. Countryman Steinar Esperås Jeffery F. Sawyer J. Chem. Soc., Dalton Trans. 1979 1979 5 854–860 10.1039/DT9790000854 Unconventional reactions 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: Almond M. R. Stimmel J. B. Thompson E. A. Loudon G. M. 132 66 1988 cv8p0132 Hofmann Rearrangement Under Mildly Acidic Conditions Using [I,I-Bis(Trifluoroacetoxy)]Iodobenzene: Cyclobutylamine Hydrochloride from Cyclobutanecarboxamide 10.15227/orgsyn.066.0132 8 132 frameless|500px|center PIFA can be used to carry out the Hofmann rearrangement under mildly acidic conditions, 6.15 Hofmann, Curtius, Schmidt, Lossen, and Related Reactions Jeffrey Aubé Charlie Fehl Ruzhang Liu Michael C. McLeod Hashim F. Motiwala Heteroatom Manipulations Comprehensive Organic Synthesis II 2014 6 598–635 10.1016/B978-0-08-097742-3.00623-6 9780080977430 rather than the strongly basic conditions traditionally used. Everett S. Wallis Lane John F. The Hofmann Reaction Org. React. 1946 3 7 267–306 10.1002/0471264180.or003.07 Hofmann Reaction 134–136 Name Reactions in Organic Chemistry Alexander R. Surrey 2nd Academic Press 1961 9781483258683 https://books.google.com/books?id=JSESBQAAQBAJ&pg=PA134 The Hofmann decarbonylation of an N-protected asparagine has been demonstrated with PIDA, providing a route to β-amino-L-alanine derivatives. Rearrangement of Nα-Protected L-Asparagines with Iodosobenzene Diacetate. A Practical Route to β-Amino-L-alanine Derivatives Lin-hua Zhang Goss S. Kauffman Jaan A. Pesti Jianguo Yin J. Org. Chem. 1997 62 20 6918–6920 10.1021/jo9702756 PIDA is also used in Suárez oxidation, where photolysis of hydroxy compounds in the presence of PIDA and iodine generates cyclic ethers.Concepción José I. Francisco Cosme G. Hernández Rosendo Salazar José A. Suárez Ernesto Intramolecular hydrogen abstraction. Iodosobenzene diacetate, an efficient and convenient reagent for alkoxy radical generation Tetrahedron Letters 1984 25 18 1953–1956 10.1016/S0040-4039(01)90085-1Courtneidge John L. Lusztyk Janusz Pagé Daniel Alkoxyl radicals from alcohols. Spectroscopic detection of intermediate alkyl and acyl hypoiodites in the Suárez and Beebe reactions Tetrahedron Letters 1994 35 7 1003–1006 10.1016/S0040-4039(00)79950-3Dorta R. L. Francisco C.G. Freire R. Suárez E. Intramolecular hydrogen abstraction. The use of organoselenium reagents for the generation of alkoxy radicals Tetrahedron Letters 1988 29 42 5429–5432 10.1016/S0040-4039(00)82887-7 This has been used in several total syntheses, such as the total synthesis of (−)-majucin, (−)-Jiadifenoxolane A,Condakes Matthew L. Hung Kevin Harwood Stephen J. Maimone Thomas J. Total Syntheses of (−)-Majucin and (−)-Jiadifenoxolane A, Complex Majucin-Type Illicium Sesquiterpenes Journal of the American Chemical Society 2017 139 49 17783–17786 10.1021/jacs.7b11493 29148748 5729088 free 2017JAChS.13917783C and cephanolide A.Qing Zhineng Mao Peng Wang Tie Zhai Hongbin Asymmetric Total Syntheses of Cephalotane-Type Diterpenoids Cephanolides A–D Journal of the American Chemical Society 2022 144 23 10640–10646 10.1021/jacs.2c03978 35653731 2022JAChS.14410640Q 249314606 References Category:Reagents for organic chemistry Category:Oxidizing agents Category:Iodanes Category:Acetates Category:Phenyl compounds Category:Iodine(III) compounds