Organoiodine Compounds Research Articles

Asymmetric Hydroxylative Phenol Dearomatization Promoted by Chiral Binaphthylic and Biphenylic Iodanes

AbstractThe long‐standing quest for chiral hypervalent organoiodine compounds (i.e., iodanes) as metal‐free reagents for asymmetric synthesis continues. Although remarkable progress has recently been made in organoiodine‐catalyzed reactions using a terminal oxidant in stoichiometric amounts, there is still a significant need for “flaskable” chiral iodane reagents. Herein, we describe the synthesis of new iodobinaphthyls and iodobiphenyls, their successful and selective DMDO‐mediated oxidation into either λ3‐ or λ5‐iodanes, and the evaluation of their capacity to promote asymmetric hydroxylative phenol dearomatization (HPD) reactions. Most notably, a C2‐symmetrical biphenylic λ5‐iodane promoted the HPD‐induced conversion of the monoterpene thymol into the corresponding ortho‐quinol‐based [4+2] cyclodimer (i.e., bis(thymol)) with enantiomeric excesses of up to 94 %.

Asymmetric hydroxylative phenol dearomatization promoted by chiral binaphthylic and biphenylic iodanes.

The long-standing quest for chiral hypervalent organoiodine compounds (i.e., iodanes) as metal-free reagents for asymmetric synthesis continues. Although remarkable progress has recently been made in organoiodine-catalyzed reactions using a terminal oxidant in stoichiometric amounts, there is still a significant need for "flaskable" chiral iodane reagents. Herein, we describe the synthesis of new iodobinaphthyls and iodobiphenyls, their successful and selective DMDO-mediated oxidation into either λ(3)- or λ(5)-iodanes, and the evaluation of their capacity to promote asymmetric hydroxylative phenol dearomatization (HPD) reactions. Most notably, a C2-symmetrical biphenylic λ(5)-iodane promoted the HPD-induced conversion of the monoterpene thymol into the corresponding ortho-quinol-based [4+2] cyclodimer (i.e., bis(thymol)) with enantiomeric excesses of up to 94%.

A laboratory characterisation of inorganic iodine emissions from the sea surface: dependence on oceanic variables and parameterisation for global modelling

Abstract. Reactive iodine compounds play a significant role in the atmospheric chemistry of the oceanic boundary layer by influencing the oxidising capacity through catalytically removing O3 and altering the HOx and NOx balance. The sea-to-air flux of iodine over the open ocean is therefore an important quantity in assessing these impacts on a global scale. This paper examines the effect of a number of relevant environmental parameters, including water temperature, salinity and organic compounds, on the magnitude of the HOI and I2 fluxes produced from the uptake of O3 and its reaction with iodide ions in aqueous solution. The results of these laboratory experiments and those reported previously (Carpenter et al., 2013), along with sea surface iodide concentrations measured or inferred from measurements of dissolved total iodine and iodate reported in the literature, were then used to produce parameterised expressions for the HOI and I2 fluxes as a function of wind speed, sea-surface temperature and O3. These expressions were used in the Tropospheric HAlogen chemistry MOdel (THAMO) to compare with MAX-DOAS measurements of iodine monoxide (IO) performed during the HaloCAST-P cruise in the eastern Pacific ocean (Mahajan et al., 2012). The modelled IO agrees reasonably with the field observations, although significant discrepancies are found during a period of low wind speeds (< 3 m s−1), when the model overpredicts IO by up to a factor of 3. The inorganic iodine flux contributions to IO are found to be comparable to, or even greater than, the contribution of organo-iodine compounds and therefore its inclusion in atmospheric models is important to improve predictions of the influence of halogen chemistry in the marine boundary layer.

Asymmetric Organocatalytic Direct C(sp2)H/C(sp3)H Oxidative Cross‐Coupling by Chiral Iodine Reagents

An asymmetric organocatalytic direct C-H/C-H oxidative coupling reaction of N(1),N(3)-diphenylmalonamides has been well established by using chiral organoiodine compounds as catalysts, wherein four C-H bonds were stereoselectively functionalized to give structurally diverse spirooxindoles with high levels of enantioselectivity. More importantly, the findings indicated that chiral hypervalent organoiodine reagents can serve as alternative catalysts for the creation of enantioselective functionalization of inactive C-H bonds.

Novel molecular-level evidence of iodine binding to natural organic matter from Fourier transform ion cyclotron resonance mass spectrometry

Major fractions of radioiodine (129I) are associated with natural organic matter (NOM) in the groundwater and surface soils of the Savannah River Site (SRS). Electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) was applied to elucidate the interactions between inorganic iodine species (iodide and iodate) and a fulvic acid (FA) extracted from a SRS surface soil. Iodate is likely reduced to reactive iodine species by the lignin- and tannin-like compounds or the carboxylic-rich alicyclic molecules (CRAM), during which condensed aromatics and lignin-like compounds were generated. Iodide is catalytically oxidized into reactive iodine species by peroxides, while FA is oxidized by peroxides into more aliphatic and less aromatic compounds. Only 9% of the total identified organo-iodine compounds derived from molecules originally present in the FA, whereas most were iodine binding to newly-produced compounds. The resulting iodinated molecules were distributed in three regions in the van Krevelen diagrams, denoting unsaturated hydrocarbons, lignin and protein. Moreover, characteristics of these organo-iodine compounds, such as their relatively low O/C ratios (<0.2 or <0.4) and yet some degree of un-saturation close to that of lignin, have multiple important environmental implications concerning possibly less sterically-hindered aromatic ring system for iodine to get access to and a lower hydrophilicity of the molecules thus to retard their migration in the natural aquatic systems. Lastly, ~69% of the identified organo-iodine species contains nitrogen, which is presumably present as NH2 or HNCOR groups and a ring-activating functionality to favor the electrophilic substitution. The ESI-FTICR-MS technique provides novel evidence to better understand the reactivity and scavenging properties of NOM towards radioiodine and possible influence of NOM on 129I migration.

Is soil natural organic matter a sink or source for mobile radioiodine ( 129I) at the Savannah River Site?

129I is one of the three major radiation risk contributors to the public as a consequence of past nuclear processing activities at Department of Energy (DOE) facilities. Elevated levels of 129I are present in the surface soils of F-Area of Savannah River Site, which used to be an isotope separation facility for the production of nuclear weapons components. The 129I in soils is thought to be bound predominantly to soil organic matter (SOM). Measurements of stable 127I and radioactive 129I in humic acids (HAs) and fulvic acids (FAs) obtained by five successive alkaline, two glycerol and one citric acid–alkaline extraction, demonstrated that these extractable humic substances (HS) together account for 54–56% and 46% of the total 127I and 129I in the soil, respectively. The remainder was likely bound to residual SOM. The iodine content (μg-I/g-C) generally decreased with each subsequent extract, while 129I/ 127I increased concurrently. The coincident variations in chemical compositions, aromaticity (estimated by UV spectroscopy), functional groups (e.g., aliphatic), degree of humification, relative migration in the hydrophobic interaction column, and molecular weight indicated that: (1) iodine in different HAs was bound to a small-size aromatic subunit (∼10 kDa); (2) the large-size subunit (∼90 kDa), which likely linked the small-size unit through some weak chemical forces (hydrogen bonds, hydrophobic or electrostatic interactions), determined the relative mobility of iodine bound to organic matter; (3) from the strong correlation between iodine content and aromaticity in the HAs, we suggested that iodine incorporation into the SOM via covalent aromatic C–I bond is the key mechanism controlling iodine behavior in this system. However, this relationship is not universal for all fractions of organic matter as evidenced from the different slopes of this relationship at the two sampling sites, as well as from the different relationships for HAs and FAs, respectively. These differences in iodination are due to different SOM molecular sizes, compositions, and availability of preferred iodination sites. 129I in the soil downstream from the contaminated site and near a wetland abruptly dropped below our detection limit (0.5 pCi- 129I/g-soil), which suggests that the high SOM in the plume soil around the 129I-contaminated F-Area might be a natural barrier to scavenge radioiodine released from the nuclear waste repository by forming organo-iodine compounds. Soil resuspension experiments showed that mobile 129I was mostly associated with a low average molecular weight amphiphilic organic carrier (13.5–15 kDa). SOM clearly behaves as a sink for iodine at the Savannah River Site F-Area. However, this work demonstrates that a small fraction of the SOM can also behave as a source, namely that a small fraction that may be readily dispersible under some environmental conditions and presumably release iodine in the organic-colloidal form. This radioiodinated organo-colloid likely can get into the groundwater through infiltration or surface runoff where it might migrate further into the wetlands. Results from this study provide the geochemical basis for future 129I migration controls, remediation, and/or land–groundwater management strategies.

Research Spotlight: Ozone‐destroying iodine measured in Arctic atmosphere

Iodine in the atmosphere can destroy ozone and can also accelerate bromine‐catalyzed ozone depletion. Iodine has been measured in the Antarctic atmosphere at levels that cause significant ozone depletion. Mahajan et al. now report detailed measurements of iodine in the Arctic lower troposphere above Hudson Bay. They observed episodes of elevated levels of iodine monoxide as well as other iodine compounds. They suggest that the iodine monoxide probably originated from organoiodine compounds released from ice and seawater algae in areas of open water surrounded by sea ice in Hudson Bay. The emissions of these iodinated compounds will probably grow if sea ice cover in the Arctic continues to decrease. (Journal of Geophysical Research‐Atmospheres, doi:10.1029/2009JD013665, 2010)

ChemInform Abstract: Preparation of Quinone-Imide Ketals from Amides with Hypervalent Organoiodine Compounds.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Hypervalent iodine(III) reagents in organic synthesis

This review summarizes the chemistry of hypervalent iodine(III) compounds with emphasis of their synthetic applications. The preparation and reactions of (difluoroiodo)arenes, (dichloroiodo)arenes, iodosylarenes, (bis(acyloxy)iodo)arenes, and aryliodine(III) organosulfonates are overviewed. Application of these reagents allows mild and highly selective oxidative transformations in a facile and environmentally friendly manner. Some of these useful transformations can be carried out using organoiodine(III) compounds as catalysts or recyclable reagents.

A new source of volatile organoiodine compounds in surface seawater

Volatile organoiodine compounds (VOIs) are the main carrier of iodine from the oceans to the atmosphere. We have identified a novel, sea‐surface source of the short‐lived VOIs CH2I2, CHClI2 and CHI3 in a series of laboratory experiments. These compounds were formed when seawater, collected during winter in the North Sea, was exposed to ambient levels of ozone. The VOIs are produced from the reaction of marine dissolved organic matter with hypoiodous acid/molecular iodine, which are formed at the sea surface when ozone reacts with dissolved iodide. The same three VOIs were formed when we incubated seawater of different productivity levels with molecular iodine during a cruise in the tropical Atlantic Ocean. We suggest that the presence of dissolved iodide, dissolved organic matter and ozone can lead to the sea‐surface production of CH2I2, CHClI2 and CHI3. As such, this process could provide a ubiquitous source of iodine to the marine atmosphere.

Chemistry of polyvalent iodine.

Starting from the early 1990’s, the chemistry of polyvalent iodine organic compounds has experienced an explosive development. This surging interest in iodine compounds is mainly due to the very useful oxidizing properties of polyvalent organic iodine reagents, combined with their benign environmental character and commercial availability. Iodine(III) and iodine(V) derivatives are now routinely used in organic synthesis as reagents for various selective oxidative transformations of complex organic molecules. Several areas of hypervalent organoiodine chemistry have recently attracted especially active interest and research activity. These areas, in particular, include the synthetic applications of 2-iodoxybenzoic acid (IBX) and similar oxidizing reagents based on the iodine(V) derivatives, the development and synthetic use of polymer-supported and recyclable polyvalent iodine reagents, the catalytic applications of organoiodine compounds, and structural studies of complexes and supramolecular assemblies of polyvalent iodine compounds. The chemistry of polyvalent iodine has previously been covered in four books1–4 and several comprehensive review papers.5–17 Numerous reviews on specific classes of polyvalent iodine compounds and their synthetic applications have recently been published.18–61 Most notable are the specialized reviews on [hydroxy(tosyloxy)iodo]benzene,41 the chemistry and synthetic applications of iodonium salts,29,36,38,42,43,46,47,54,55 the chemistry of iodonium ylides,56–58 the chemistry of iminoiodanes,28 hypervalent iodine fluorides,27 electrophilic perfluoroalkylations,44 perfluoroorgano hypervalent iodine compounds,61 the chemistry of benziodoxoles,24,45 polymer-supported hypervalent iodine reagents,30 hypervalent iodine-mediated ring contraction reactions,21 application of hypervalent iodine in the synthesis of heterocycles,25,40 application of hypervalent iodine in the oxidation of phenolic compounds,32,34,50–53,60 oxidation of carbonyl compounds with organohypervalent iodine reagents,37 application of hypervalent iodine in (hetero)biaryl coupling reactions,31 phosphorolytic reactivity of o-iodosylcarboxylates,33 coordination of hypervalent iodine,19 transition metal catalyzed reactions of hypervalent iodine compounds,18 radical reactions of hypervalent iodine,35,39 stereoselective reactions of hypervalent iodine electrophiles,48 catalytic applications of organoiodine compounds,20,49 and synthetic applications of pentavalent iodine reagents.22,23,26,59 The main purpose of the present review is to summarize the data that appeared in the literature following publication of our previous reviews in 1996 and 2002. In addition, a brief introductory discussion of the most important earlier works is provided in each section. The review is organized according to the classes of organic polyvalent iodine compounds with emphasis on their synthetic application. Literature coverage is through July 2008.

A method for measuring semi- and non-volatile organic halogens by combustion ion chromatography

Recent studies have shown that various semi- and non-volatile organohalogen compounds are ubiquitous in the environment: these include halogenated dioxins including chlorinated dioxins, other persistent organic pollutants (POPs), brominated flame retardants (BFRs), and perfluorooctane sulfonate (PFOS). However, monitoring and assessment of these compounds by the analyses of individual compounds and their isomers is onerous because of their low environmental concentrations and large number of compounds. In this study, we have developed a new method that is capable of screening and monitoring an array of organohalogen compounds efficiently by combustion ion chromatography (CIC)—the new analyzer that serially connects combustion furnace and ion chromatograph. Analyzer performance was evaluated in terms of its applicability, reproducibility, and sensitivity as limit of detection (LOD). Recoveries of organochlorine, organobromine, and organoiodine compounds by the CIC were between 97 and 105%; those of organofluorine compounds were from 86 to 91%. In all cases, the relative standard deviation of five analyses was 4% or smaller. The analyzer would exhibit good sensitivity for various environmental matrices (e.g., 2.8–31 ng-X/g-soil, 1.4–16 ng-X/L-water, and 9.2 – 100 ng-X / m N 3 -gas ). The method is fast and can provide information regarding the occurrence of organohalogen compounds within 1 or 2 days after sampling. Applicability of the new method for the assessment of contamination in flue gas and fly ash was also demonstrated. Our results show that the method is efficient to investigate emission sources and areas contaminated by organohalogen compounds.

The formation of oxygen-containing perfluorocyclohexadien-1-yliodine tetrafluorides

The electrophilic oxygenation of pentafluorophenyl iodo compounds C 6F 5IF n with iodine in different valencies ( n = 0, 2, 4) using XeF 2–H 2O in HF allowed access to new organoiodine(V) compounds, namely isomeric oxopentafluorocyclohexadien-1-yliodine tetrafluorides, C 6(O)F 5IF 4.

Abiotic Source of Reactive Organic Halogens in the Sub-Arctic Atmosphere?

Recent theoretical studies indicate that reactive organic iodocarbons such as CH2I2 would be extremely effective agents for tropospheric Arctic ozone depletion and that iodine compounds added to a Br2/BrCl mixture have a significantly greater ozone (and mercury) depletion effect than additional Br2 and BrCl molecules. Here we report the first observations of CH2I2, CH2IBr, and CH2ICl in Arctic air, as well as other reactive halocarbons including CHBr3, during spring at Kuujjuarapik, Hudson Bay. The organoiodine compounds were present atthe highest levels yet reported in air. The occurrence of the halocarbons was associated with northwesterly winds from the frozen bay, and, in the case of CHBr3, was anticorrelated with ozone and total gaseous mercury (TGM), suggesting a link between inorganic and organic halogens. The absence of local leads coupled with the extremely short atmospheric lifetime of CH2I2 indicates that production occurred in the surface of the sea-ice/overlying snowpack over the bay. We propose an abiotic mechanism for the production of polyhalogenated iodo- and bromocarbons, via reaction of HOI and/or HOBr with organic material on the quasi-liquid layer above sea-ice/snowpack, and report laboratory data to support this mechanism. CH2I2, CH2IBr, and other organic iodine compounds may therefore be a ubiquitous component of air above sea ice where they will increase the efficiency of bromine-initiated ozone and mercury depletion.

Development of Novel Oxidation Reactions in Water Using Hypervalent Iodine Reagents

AbstractFor Abstract see ChemInform Abstract in Full Text.

超原子価ヨウ素試薬を用いる水中での新規酸化反応の開発

Various aqueous oxidation reactions have been developed since economic and environmental concerns encourage the use of water as a reaction medium. Hypervalent iodine compounds have been used extensively in organic synthesis due to not only low toxicity, ready availability, and easy handling, but also reactivities similar to those of heavy metal reagents or anodic oxidation. However, most of the hypervalent iodine oxidation reactions have been carried out only in limited organic solvents because both the solubility and the reactivity of organo-iodine (III or V) compounds have remarkably been decreased in water. In this article, we report novel activation methods of hypervalent iodine species in water and their application to the development of environmentally benign oxidation reactions using polymer-supported iodine (III) reagents. Furthermore, these methods enabled us to replace iodine (V) reagents, such as Dess-Martin periodinane (DMP) and ο-iodoxybenzoic acid (IBX) with much safer (non-explosive) and commercially available iodine (III) reagents.

Dioxin-like potencies and extractable organohalogens (EOX) in medical, municipal and domestic waste incinerator ashes in Japan

Ash samples collected from medical, municipal and small-scale domestic incinerators in Japan were tested for dioxin-like activity using bioassay technique (ethoxyresorufin- O-deethylase: EROD assay) and for extractable organohalogens (EOX) using instrumental neutron activation analysis in order to estimate potential toxicity and responsible chemicals in those samples. Crude extracts and fractions cleaned-up for dioxin analysis from the samples were used for the analysis. The ranges of dioxins in the ashes were between 2.23 and 12.29 ng TEQ/g (dry weight). Relative potency ranges estimated by EROD assay in the medical incinerator ashes were 3.8–17.6 times higher than the results of conventional chemical analysis. EOX analysis suggested that ash samples contained plenty of organochlorine compounds apart from chlorinated dioxins. In addition, medical waste incinerator ashes were considered to have relatively higher amount of organoiodine compounds. In the cleaned-up fractions, bioassay potency ranges were lower than those in the crude extracts. However, some samples still exhibited higher potency than expected from chemical analysis. Though some polycyclic aromatic hydrocarbons were found in the fractions, the amounts were relatively low (0.39–10.56 ng/g). The results imply that some bioactive organohalogens that cannot be detected in the conventional chemical analysis might have potential for dioxin-like toxicity, and contribute to higher bioassay activities. The combination of the chemical analysis with the bioassay and EOX provides rough figure of dioxin-like toxicity and suggests types of organohalogen compounds that should be identified as a part of dioxin analysis for control emission from an incineration plant.

Synthesis and characterization of novel polyvalent organoiodine compounds

Synthesis and characterization of soluble analogues of iodosylbenzene PhIO and (tosyliminoiodo)benzene PhINTs are reported. The syntheses of 4-trifluoromethyl-2-(tertbutylsulfonyl)iodosylbenzene (3) and 4-trifluoromethyl-2-(tert-butylsulfonyl)(tosylimino)iodobenzene (4) increase the repertoire of available soluble organoiodine(III) based oxo- and nitrene precursors. We also report the synthesis of a new organoiodine(V) compound, 4-trifluoromethyl-2-(tert-butylsulfonyl)iodylbenzene.

Organoiodine formation during humification in peatlands

Although two billion people in the world are suffering from iodine deficiency there is little information on the chemical fate of iodine in the terrestrial environment. Here we show that peatlands play a major role in terrestrial iodine cycling. Chemical data from two peat profiles from Patagonia, Chile imply that transformation of iodine from its inorganic form to organoiodine compounds during early humification in peatlands is a key process in storage of iodine in the terrestrial environment. Once bound in peat, iodine remains stable for thousands of years. In the earth’s peatlands, net accumulation of iodine since the last glacial period is estimated to be 12–36 teragrams (1 Tg=1012 g). These data suggest that peatlands are a major reservoir of iodine in terrestrial ecosystems. Our novel model of iodine distribution in the terrestrial environment demonstrates the key role of peatlands in burial and reemission of organically bound iodine.

Determination of iodine species in milk using ion chromatographic separation and ICP-MS detection

A combination of ion chromatography (IC) and inductively coupled plasma-mass spectrometry (ICP-MS) was used to determine iodine species in Thuringian milk samples. The developed method allows the fast and sensitive determination of iodine species with limits of determination for iodide and iodate <2 µg/L. Iodide was identified as the main iodine species in milk, but in a few samples also traces of iodate and several unidentified, presumably organoiodine compounds were observed as well. In addition, the total iodine concentration in the samples was determined by ICP-MS and gives an idea about the actual iodine state in Thuringian milk.