An improved procedure for the iodination of phenols using sodium iodide and tert-butyl hypochlorite

Kometani, Tadashi; Watt, David S.; Ji, Tae H.; Fitz, T. A.

doi:10.1021/jo00225a079

Cited by 49 publications

(27 citation statements)

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“…Contrasting to the use of some iodinating agents, 24,[40][41][42] which in general lead to products of poly-iodination, phenol (4a) furnished para-iodophenol 13a 24 in good yields by reaction with complexes 1a, 1b and 1c (entries 5-7). We also examined the iodination of the phenols 4b, 4c and 4d, bearing electron withdrawing substituents at the para position (NO 2 , CO 2 CH 3 and Cl) (entries [8][9][10][11][12][13][14][15][16]) and the desired products 13b, 24 13c 24 and 13d 24 were obtained in good yields by using complexes 1a-d. However, only starting material was observed when highly deactivated phenol 5a was allowed to react with complex 1a (entry 17).…”

Section: Resultsmentioning

confidence: 99%

“…12,13 Continuing interest of organic chemists in iodination reactions are due to the versatility of iodinated compounds as building blocks in a variety of synthetic transformations in medicinal chemistry, as well as in the biomedical sciences as imaging agents in non-invasive medical diagnostic techniques due to the possible release of the long-lived radioactive 129 I isotope. [14][15][16][17][18] In the 1950's the hormone thyroxine and its analogues were prepared as radioiodinated photoprobes. [19][20][21][22][23] A broad range of procedures are described in the literature for the iodination of phenols, involving the use of NIS, ICl, I 2 and iodides salts in the presence of an oxidant, in acid or basic conditions.…”

Section: Introductionmentioning

confidence: 99%

“…Iodine in the presence of amines react readily with benzophenone, cinnamates and chalcones leading to α,β-diamino-benzylacetophenones and α,β-diamino-benzylacetones derivatives. 37 While in most cases complexes of I 2 with amines are generated and used in situ, 13,14 a stable and easily to handle complex 1a ( Figure 1) was prepared by Rice 38 just mixing of morpholine, KI and I 2 in water. Recently Perez et al 39 described the use of this complex as iodinating reagent to prepare 2-hydroxy-3-iodo-naphthoquinone from lawsone in 87% yield, but did not evaluate the scope of this new iodinating agent using other phenols as substrates.…”

Section: Introductionmentioning

confidence: 99%

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Iodination of phenols in water using easy to handle amine-iodine complexes

Frota¹,

Canavez²,

Gomes³

et al. 2009

J. Braz. Chem. Soc.

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A reação entre o iodo e a N-metil-piperazina ou a tiomorfolina em água, na presença de KI, levou a formação de complexos amina-iodo estáveis e de fácil manipulação, tal qual o complexo morfolina-iodo, previamente descrito na literatura. Entretanto, o complexo formado entre o iodo e a N,N-tetrametiletilenodiamina mostrou-se pouco estável, enquanto que nenhum complexo foi isolado quando a piperidina foi usada como base. Estes resultados mostram que a presença do segundo heteroátomo na estrutura das aminas é fundamental para a formação e estabilidade desses complexos. Neste trabalho descrevemos, pela primeira vez, o emprego dos complexos morfolina-iodo, N-metil-piperazina-iodo e tiomorfolina-iodo como agentes de iodação de vários fenóis substituídos, conduzindo a uma série de produtos iodados em rendimentos variando de bons a excelentes.The reaction between iodo and N-methyl-piperazine or thiomorpholine in water, in the presence of KI, led to the formation of stable and easy to handle amine-iodine complexes, as the complex morpholine-iodo previously reported in the literature. However, the complex obtained using N,Ntetrametylethylenediamine proved less stable, while no complex was formed when piperidine was used as base. These results show that the presence of a second heteroatom in the structure of amines is of fundamental importance for the formation and stability of these complexes. In this work we describe, for the first time, the use of complexes morpholine-iodo, N-methyl-piperazine-iodo and thiomorpholine-iodo as iodinating reagents of several substituted phenols, leading to iodinated products in good to excellent yields.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Iodination of phenols in water using easy to handle amine-iodine complexes

Frota¹,

Canavez²,

Gomes³

et al. 2009

J. Braz. Chem. Soc.

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“…6,7 The selectivities displayed by the radical hydrocarbon iodination led Tanner and Gidley to propose a chain reaction involving an iodonyl radical as the hydrogen atom abstracting species. 6,7 The selectivities displayed by the radical hydrocarbon iodination led Tanner and Gidley to propose a chain reaction involving an iodonyl radical as the hydrogen atom abstracting species.…”

Section: Original Commentarymentioning

confidence: 99%

tert-Butyl Hypoiodate

Simpkins

Wirth

2009

Encyclopedia of Reagents for Organic Synthesis

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“…As a model study for the radioiodination (19) and acylation processes needed for biochemical studies, the iodination (20,21) of succinimidyl ester 16A followed by treatment with n-butylamine, a surrogate for a lysine residue, led, as shown in Scheme 111, to a mixture of monoand diiodinated products (18A and 19A) that could not be separated. For characterization purposes, the iodination of ester 20A, separation of the mono-and diiodinated esters, saponification, and coupling with n-butylamine furnished either pure 18A or 19A.…”

Section: Chemical Synthesismentioning

confidence: 99%

Photoaffinity heterobifunctional crosslinking reagents based on N-(azidobenzoyl)tyrosines

Imai¹,

Kometani²,

Crocker³

et al. 1990

Bioconjugate Chem.

Self Cite

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New heterobifunctional cross-linking reagents that possessed a photoactive terminus, an electrophilic terminus, and a linking arm between the two termini that had a radiolabeled, enzymatically cleavable bond were synthesized. In a model study, succinimidyl N-[N'-(4-azidobenzoyl)tyrosyl]-beta-alanate (16A) was coupled to n-butylamine (a Lys surrogate), iodinated, and cleaved with chymotrypsin in the presence of tyrosylamide to afford the desired adduct (N-(N'-(4-azidobenzoyl)-3-iodotyrosyl)tyrosinamide, thereby demonstrating the feasibility of the enzymatic cleavage. In a biochemical study, succinimidyl N-[N'-(3-azido-5-nitrobenzoyl)tyrosyl]-beta-alanate (16C) was coupled to Lys-75 of calmodulin (CaM), and the radioiodinated monoadduct was successfully photo-cross-linked, in a calcium-dependent manner, to the human erythrocyte plasma membrane Ca2+,Mg2(+)-ATPase and to a synthetic fragment (M13) containing the CaM-binding region of myosin light-chain kinase. In the latter case, densitometry readings indicated 20% cross-linking efficiency.

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An improved procedure for the iodination of phenols using sodium iodide and tert-butyl hypochlorite

Cited by 49 publications

References 1 publication

Iodination of phenols in water using easy to handle amine-iodine complexes

Iodination of phenols in water using easy to handle amine-iodine complexes

tert-Butyl Hypoiodate

Photoaffinity heterobifunctional crosslinking reagents based on N-(azidobenzoyl)tyrosines

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