(Diacetoxyiodo)benzene, also known as phenyliodine(III) diacetate (PIDA) is a

hypervalent iodine Iodane generally refers to any organic derivative of iodine. Without modifier, ''iodane'' is the systematic name for the parent hydride of iodine, HI. Thus, any organoiodine compound with general formula RI (e.g., iodomethane , or iodobenzene ) ...

chemical with the formula . It is used as an

oxidizing agent An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or "Electron acceptor, accepts"/"receives" an electron from a (called the , , or ). In ot ...

organic chemistry Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; ...

Preparation

This reagent was originally prepared by Conrad Willgerodt by reacting

iodobenzene Iodobenzene is an organoiodine compound consisting of a benzene ring substituted with one iodine atom. It is useful as a synthetic intermediate in organic chemistry. It is a volatile colorless liquid, although aged samples appear yellowish. Prepa ...

with a mixture of

acetic acid Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main component ...

and

peracetic acid Peracetic acid (also known as peroxyacetic acid, or PAA) is an organic compound with the formula CH3CO3H. This peroxy acid is a colorless liquid with a characteristic acrid odor reminiscent of acetic acid. It can be highly corrosive. Peracetic a ...

: :

CHI Chi or CHI may refer to: Greek *Chi (letter), the Greek letter (uppercase Χ, lowercase χ); Chinese *Chi (length), ''Chi'' (length) (尺), a traditional unit of length, about ⅓ meter *Chi (mythology) (螭), a dragon *Chi (surname) (池, pin ...

+ CHCOH + CHCOH → CHI(OCCH) + HO PIDA can also be prepared from

iodosobenzene Iodosobenzene or iodosylbenzene is an organoiodine compound with the empirical formula . This colourless solid compound is used as an oxo transfer reagent in research laboratories examining organic and coordination chemistry. Preparation and st ...

and

glacial acetic acid Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main component ...

: :

CHIO Chios (; el, Χίος, Chíos , traditionally known as Scio in English) is the fifth largest Greece, Greek list of islands of Greece, island, situated in the northern Aegean Sea. The island is separated from Turkey by the Chios Strait. Chios is ...

+ 2 CHCOH → CHI(OCCH) + HO More recent preparations direct from

iodine Iodine is a chemical element with the symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at , and boils to a vi ...

, acetic acid, and

benzene Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, ...

have been reported, using either

sodium perborate Sodium perborate is chemical compound whose chemical formula may be written , , or, more properly, ·. Its name is sometimes abbreviated as PBS (not to be confused with phosphate-buffered saline). The compound is commonly encountered in anhydr ...

potassium peroxydisulfate Potassium persulfate is the inorganic compound with the formula K2 S2O8. Also known as potassium peroxydisulfate, it is a white solid that is sparingly soluble in cold water, but dissolves better in warm water. This salt is a powerful oxidant, c ...

as the oxidizing agent: : CH + I + 2 CHCOH + KSO → CHI(OCCH) + KI + HSO + KHSO The PIDA molecule is termed

hypervalent In chemistry, a hypervalent molecule (the phenomenon is sometimes colloquially known as expanded Octet rule, octet) is a molecule that contains one or more main group elements apparently bearing more than eight electrons in their valence shells. P ...

as its iodine atom (technically a

) is in its +III

oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...

and has more than typical number of

covalent bond A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms ...

s. It adopts a

T-shaped molecular geometry In chemistry, T-shaped molecular geometry describes the structures of some molecules where a central atom has three ligands. Ordinarily, three-coordinated compounds adopt trigonal planar or pyramidal geometries. Examples of T-shaped molecules a ...

, with the

phenyl In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula C6 H5, and is often represented by the symbol Ph. Phenyl group is closely related to benzene and can be viewed as a benzene ring, minus a hydrogen ...

group occupying one of the three equatorial positions of a trigonal bipyramid (

lone pair In chemistry, a lone pair refers to a pair of valence electrons that are not shared with another atom in a covalent bondIUPAC ''Gold Book'' definition''lone (electron) pair''/ref> and is sometimes called an unshared pair or non-bonding pair. Lone ...

s occupy the other two) and the axial positions occupied by oxygen atoms from the

acetate An acetate is a salt (chemistry), salt formed by the combination of acetic acid with a base (e.g. Alkali metal, alkaline, Alkaline earth metal, earthy, Transition metal, metallic, nonmetallic or radical Radical (chemistry), base). "Acetate" als ...

groups. The "T" is distorted in that the phenyl-C to I to acetate-O bond angles are less than 90°. A separate investigation of the crystal structure confirmed that it has orthorhombic crystals in space group ''Pnn''2 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

hat A hat is a head covering which is worn for various reasons, including protection against weather conditions, ceremonial reasons such as university graduation, religious reasons, safety, or as a fashion accessory. Hats which incorporate mecha ...

can be described as a pentagonal-planar arrangement of three strong and two weak secondary bonds."

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 Trifluoroacetic acid (TFA) is an organofluorine compound with the chemical formula CF3CO2H. It is a structural analogue of acetic acid with all three of the acetyl group's hydrogen atoms replaced by fluorine atoms and is a colorless liquid with ...

PIFA can be used to carry out the

Hofmann rearrangement The Hofmann rearrangement (Hofmann degradation) is the organic reaction of a primary amide to a primary amine with one fewer carbon atom. The reaction involves oxidation of the nitrogen followed by rearrangement of the carbonyl and nitrogen to gi ...

under mildly acidic conditions, rather than the strongly basic conditions traditionally used. The Hofmann decarbonylation of an ''N''-protected

asparagine Asparagine (symbol Asn or N) is an α-amino acid that is used in the biosynthesis of proteins. It contains an α-amino group (which is in the protonated −NH form under biological conditions), an α-carboxylic acid group (which is in the depro ...

has been demonstrated with PIDA, providing a route to β-amino-L-

alanine Alanine (symbol Ala or A), or α-alanine, is an α-amino acid that is used in the biosynthesis of proteins. It contains an amine group and a carboxylic acid group, both attached to the central carbon atom which also carries a methyl group side c ...

derivatives. PIDA is also used in Suárez oxidation, where photolysis of hydroxy compounds in the presence of PIDA and iodine generates cyclic ethers. This has been used in several total syntheses, such as the total synthesis of (−)-majucin, (−)-Jiadifenoxolane A, and cephanolide A.

References

{{DEFAULTSORT:Diacetoxyiodo)benzene Reagents for organic chemistry Oxidizing agents Iodanes Acetates Phenyl compounds