(Bis(trifluoroacetoxy)iodo)benzene

(Bis(trifluoroacetoxy)iodo)benzene
Names
	Preferred IUPAC name Phenyl-λ3-iodanediyl bis(trifluoroacetate)
	Other names Phenyliodine bis(trifluoroacetate); PIFA
Identifiers
CAS Number	2712-78-9 ;
3D model (JSmol)	Interactive image;
ChemSpider	92428 ;
ECHA InfoCard	100.018.462
EC Number	220-308-0;
PubChem CID	102317;
UNII	659SFV27XS;
CompTox Dashboard (EPA)	DTXSID40181584 ;
	InChI InChI=1S/C10H5F6IO4/c11-9(12,13)7(18)20-17(6-4-2-1-3-5-6)21-8(19)10(14,15)16/h1-5H Key: PEZNEXFPRSOYPL-UHFFFAOYSA-N ; InChI=1/C10H5F6IO4/c11-9(12,13)7(18)20-17(6-4-2-1-3-5-6)21-8(19)10(14,15)16/h1-5H Key: PEZNEXFPRSOYPL-UHFFFAOYAA;
	SMILES FC(F)(F)C(=O)OI(OC(=O)C(F)(F)F)c1ccccc1;
Properties
Chemical formula	C10H5F6IO4
Molar mass	430.041 g·mol−1
Hazards
	GHS labelling:
Pictograms
Signal word	Warning
Hazard statements	H315, H319, H335
Precautionary statements	P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

(Bis(trifluoroacetoxy)iodo)benzene, C
₆H
₅I(OCOCF
₃)
₂, is a hypervalent iodine compound used as a reagent in organic chemistry. It can be used to carry out the Hofmann rearrangement under acidic conditions.^[1]

Preparation

The syntheses of all aryl hypervalent iodine compounds start from iodobenzene. The compound can be prepared by reaction of iodobenzene with a mixture of trifluoroperacetic acid and trifluoroacetic acid in a method analogous to the synthesis of (diacetoxyiodo)benzene:^[1]

It can also be prepared by dissolving diacetoxyiodobenzene (a commercially-available compound) with heating in trifluoroacetic acid:^[2]

Uses

It also brings around the conversion of a hydrazone to a diazo compound, for example in the diazo-thioketone coupling. It also converts thioacetals to their parent carbonyl compounds.

Hofmann rearrangement

The Hofmann rearrangement is a decarbonylation reaction whereby an amide is converted to an amine by way of an isocyanate intermediate. It is usually carried out under strongly basic conditions.^[3]^[4]

The reaction can also be carried out under mildly acidic conditions by way of the same intermediate using a hypervalent iodine compound in aqueous solution.^[1] An example published in Organic Syntheses is the conversion of cyclobutanecarboxamide, easily synthesized from cyclobutylcarboxylic acid, to cyclobutylamine.^[2] The primary amine is initially present as its trifluoroacetate salt, which can be converted to the hydrochloride salt to facilitate product purification.^[1]^[2]

References

^ ^a ^b ^c ^d Aubé, Jeffrey; Fehl, Charlie; Liu, Ruzhang; McLeod, Michael C.; Motiwala, Hashim F. (1993). "6.15 Hofmann, Curtius, Schmidt, Lossen, and Related Reactions". Heteroatom Manipulations. Comprehensive Organic Synthesis II. Vol. 6. pp. 598–635. doi:10.1016/B978-0-08-097742-3.00623-6. ISBN 9780080977430.
^ ^a ^b ^c 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; Collected Volumes, vol. 8, p. 132.
^ Wallis, Everett S.; Lane, John F. (1946). "The Hofmann Reaction". Organic Reactions. 3 (7): 267–306. doi:10.1002/0471264180.or003.07.
^ Surrey, Alexander R. (1961). "Hofmann Reaction". Name Reactions in Organic Chemistry (2nd ed.). Academic Press. pp. 134–136. ISBN 9781483258683.

[HA-1] Aubé, Jeffrey; Fehl, Charlie; Liu, Ruzhang; McLeod, Michael C.; Motiwala, Hashim F. (1993). "6.15 Hofmann, Curtius, Schmidt, Lossen, and Related Reactions". Heteroatom Manipulations. Comprehensive Organic Synthesis II. Vol. 6. pp. 598–635. doi:10.1016/B978-0-08-097742-3.00623-6. ISBN 9780080977430.

[OS-2] 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; Collected Volumes, vol. 8, p. 132.

[3] Wallis, Everett S.; Lane, John F. (1946). "The Hofmann Reaction". Organic Reactions. 3 (7): 267–306. doi:10.1002/0471264180.or003.07.

[4] Surrey, Alexander R. (1961). "Hofmann Reaction". Name Reactions in Organic Chemistry (2nd ed.). Academic Press. pp. 134–136. ISBN 9781483258683.

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