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Current decarboxylative halogenation methods typically require expensive or toxic transition metal catalysts and have limited solvent compatibility. Herein, we report a novel transition-metal-free and solvent-tolerant decarboxylative iodination method by using iodine monochloride in the presence of potassium phosphate, which are effective to readily available aryl and heteroaryl carboxylic acids, and can be executed in a variety of solvents, including water. [ABSTRACT FROM AUTHOR]

Iodine value is an essential parameter for assessing the composition and quality of oils. A commonly used method for iodine value determination is the Wijs method. Recently, the HPLC method for assay of iodine monochloride via iodination of 2-chloroaniline with iodine monochloride has been reported. This study presents an approach for iodine value determination by HPLC via quantification of the unreacted iodine monochloride after reaction with oil samples, similar to the back titration approach in the Wijs method. Chromatographic conditions consist of gradient elution using water and acetonitrile on the C18 column with a detection wavelength of 304 nm. Oleic acid, with a known iodine value (83–103 gI/100 g), was used as a method development and validation reference compound. The method was validated as per International Conference on Harmonization guidelines and was accurate (98–102%), robust, and linear (r2 = 0.999) for oleic acid ranging from 5 to 20 mg. The repeatability and intermediate precision were within 1%. The validated method was applied for the iodine value determination of 10 cold-pressed oils. Thus, an HPLC method is developed, which offers minimal sample requirements, high accuracy, less manual intervention, and precision for the iodine value determination of oils. [ABSTRACT FROM AUTHOR]

Quantum chemical computations at M06-2X/def2-TZVPD level of theory were employed to compute structural and thermodynamic properties of gaseous donor-acceptor complexes IX·LB [X = I, Cl; LB = trimethylamine, triethylamine, pyridine, 2-aminopyridine, 4,4′-bipyridine, pyrazine, 1,2-bis(4-pyridyl)ethylene, 1,2-bis(4-pyridyl)ethane]. Iodine monochloride is a stronger Lewis acid compared to the molecular iodine. With respect to homogeneous gas phase dissociation into components, the complex of ICl with triethylamine is the most stable and the complex of I2 with pyrazine is the least stable. It is shown that dissociation enthalpies do not correlate with proton affinity of the Lewis base, but there is a good correlation between dissociation enthalpies and I–X bond lengthening upon complex formation. This allows to estimate the stability of the complex based on its structural data. [ABSTRACT FROM AUTHOR]

Iodine monochloride is conventionally determined using the sodium thiosulphate titration method. Recently, mono‐iodination of 2‐chloroaniline in N,N‐dimethylformamide has been reported in the presence of iodine monochloride. A reversed‐phase high‐performance liquid chromatography method for the assay of iodine monochloride on the C18 column has been developed via the iodination of 2‐chloroaniline. Chromatographic separation was achieved using gradient elution with water and acetonitrile as mobile phase at 1 ml/min flow rate and detection at 304 nm. The elution of 2‐chloro‐4‐iodoaniline was observed at 5.492 min. Under the given experimental conditions, an excess of 2‐chloroaniline dissolved in acetonitrile reacted with a known amount of pure iodine monochloride resulting in 2‐chloro‐4‐iodoaniline. The amount of 2‐chloro‐4‐iodoaniline formed is a measure of the initial iodine monochloride concentration, thus providing the assay of iodine monochloride. The method was validated as per the guidelines of the International Conference on Harmonization guidelines and found to be linear (r2 = 0.999) and accurate (98%–102%) for iodine monochloride concentrations ranging from 0.4 to 1.2 mg/ml. The intra‐day and inter‐day precision were within 1%. The validated method was successfully applied to determine the assay of commercially available iodine monochloride, Wijs solution, and in‐situ generated iodine monochloride samples. Thus, a novel, simple, accurate, and precise HPLC method has been developed for iodination monochloride assay. [ABSTRACT FROM AUTHOR]

The efficient regioselective bromination and iodination of the nonsteroidal anti-inflammatory drug (NSAID) carprofen were achieved by using bromine and iodine monochloride in glacial acetic acid. The novel halogenated carprofen derivatives were functionalized at the carboxylic group by esterification. The regioselectivity of the halogenation reaction was evidenced by NMR spectroscopy and confirmed by X-ray analysis. The compounds were screened for their in vitro antibacterial activity against planktonic cells and also for their anti-biofilm effect, using Gram-positive bacteria (Staphylococcus aureus ATCC 29213, Enterococcus faecalis ATCC 29212) and Gram-negative bacteria (Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 27853). The cytotoxic activity of the novel compounds was tested against HeLa cells. The pharmacokinetic and pharmacodynamic profiles of carprofen derivatives, as well as their toxicity, were established by in silico analyses. [ABSTRACT FROM AUTHOR]

In this communication, we investigate the reaction between seleno- and thiourea, derived from N-heterocyclic carbenes, with the interhalogen iodine monochloride. The formation of all three products was confirmed by NMR spectroscopy, while single-crystal X-ray analyses were able to establish a charge-transfer coordination type, which showed a linear Se/S-I-Cl arrangement, for all adducts formed. Based on a detailed crystallographic analysis, we can deduce the zwitterionic character of these compounds. [ABSTRACT FROM AUTHOR]

In this communication, we investigate the reaction between seleno- and thiourea, derived from N-heterocyclic carbenes, with the interhalogen iodine monochloride. The formation of all three products was confirmed by NMR spectroscopy, while single-crystal X-ray analyses were able to establish a charge-transfer coordination type, which showed a linear Se/S-I-Cl arrangement, for all adducts formed. Based on a detailed crystallographic analysis, we can deduce the zwitterionic character of these compounds.

We present for the first time a coherent ab initio study of 39 states of valence, Rydberg, and ionpair character of the diatomic interhalogen ICl species through large scale multireference variational methods including spin-orbit effects coupled with quantitative basis sets. Various avoided crossings are responsible for a non-adiabatic behaviour creating a wonderful vista for its theoretical description. Our molecular constants are compared with all available experimental data with the aim to assist experimentalists especially in the high energy regime of up to ~95 000 cm-1 . [ABSTRACT FROM AUTHOR]

The efficient regioselective bromination and iodination of the nonsteroidal anti-inflammatory drug (NSAID) carprofen were achieved by using bromine and iodine monochloride in glacial acetic acid. The novel halogenated carprofen derivatives were functionalized at the carboxylic group by esterification. The regioselectivity of the halogenation reaction was evidenced by NMR spectroscopy and confirmed by X-ray analysis. The compounds were screened for their in vitro antibacterial activity against planktonic cells and also for their anti-biofilm effect, using Gram-positive bacteria (Staphylococcus aureus ATCC 29213, Enterococcus faecalis ATCC 29212) and Gram-negative bacteria (Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 27853). The cytotoxic activity of the novel compounds was tested against HeLa cells. The pharmacokinetic and pharmacodynamic profiles of carprofen derivatives, as well as their toxicity, were established by in silico analyses.

Graphene intercalation materials are potentially promising for the implementation of the ultra-low power, excitonic-condensate-based Bilayer pseudoSpin Field-Effect Transistor (BiSFETs) concept, as well as other novel device concepts requiring a graphene interlayer dielectric. Using density functional theory, we study the structural and electronic properties of bilayer graphene intercalated with iodine monochloride (ICl) and iodine monobromide (IBr). We determine the structural configuration of ICl and IBr graphene intercalation compounds (GICs). We also conduct an in-depth exploration of inter-layer electronic coupling, using ab initio calculations. The presence of intercalants dopes the graphene layer. It also reduces, but does not eliminate, the electronic coupling between graphene layers, which may enable BiSFET operation. In addition, we present experimental results for ICl-GIC synthesis and characterization. [ABSTRACT FROM AUTHOR]

We present slice imaging data demonstrating the influence of clustering on the photodissociation dynamics of a diatomic molecule: iodine monochloride (ICl) was dissociated at 235 nm in He and Xe seed gasses, probing both Cl and I photofragment energy and angular distributions. We observe that the kinetic energy releases of both Cl and I fragments change from He to Xe seeding. For Cl fragments, the seeding in Xe increases the kinetic energy release of some Cl fragments with a narrow kinetic energy distribution, and leads to some fragments with rather broad statistical distribution falling off exponentially from near-zero energies up to about 2.5 eV. Iodine fragment distribution changes even more dramatically from He to Xe seeding: sharp features essentially disappear and a broad distribution arises reaching to about 2.5 eV. Both these observations are rationalized by a simple qualitative cluster model assuming ICl dissociation inside larger xenon clusters and 'on surface' of smaller Xe species. [ABSTRACT FROM AUTHOR]

A metal‐free method for the construction of oxazolidine‐2,4‐diones and oxindoles was discussed. Using iodine monochloride (ICl) as both the reaction promoter and iodide source, the iodolactonization of N‐Boc acrylamides proceeded readily and provided the corresponding iodo oxazolidine‐2,4‐diones and oxazolidin‐2‐ones in good isolated yields. The obtained oxazolidine‐2,4‐diones can be used as key intermediates in the synthesis of toloxatone. When N‐alkyl‐N‐arylacrylamide derivatives were subjected to the same reaction, iodocarbocyclization products 3,3‐disubstituted oxindoles were obtained. The obtained oxindoles can be used as key intermediates in the synthesis of the alkaloids (±)‐esermethole and (±)‐physostigmine. A metal‐free method for the construction of oxazolidine‐2,4‐diones and oxindoles is reported herein. The resulting products can be used as key intermediates in synthesis of bioactive compounds such as toloxatone, (±)‐esermethole, and (±)‐physostigmine. [ABSTRACT FROM AUTHOR]

Gum arabic, a plant polysaccharide was oxidized with periodate to produce aldehyde groups by the cleavage of diols present in the sugar units. The oxidized gum was then iodinated with iodine monochloride (ICl) and the interaction between electrophilic iodine, I + and reactive carbonyl groups of the modified gum was studied.Results of titrimetric estimation performed to determine the extent of oxidation and aldehyde content in the oxidized gum showed that degree of oxidation ranged between 19.68–50.19% which was observed to increase with periodate concentration; the corresponding aldehyde content was calculated to be 5.15–40.42%. Different strengths of ICl were used to iodinate the oxidized gum and the iodine content of the complexes varied from 6.11–11.72% as determined by iodometric titration. Structure elucidation of the iodine complexes conclusively established the attachment of ICl molecules to CHO groups. A reaction scheme has been proposed suggesting an electrophilic addition of the reagent to the aldehyde groups, a mechanism that was also supported by iodide ion release studies. [ABSTRACT FROM AUTHOR]

A protocol has been developed to achieve selective and direct synthesis of α-iodoketones under mild condition, from the reaction of aminoalkynols with iodine monochloride. The scope of the reaction was investigated using various aminoalkynols with iodine monochloride and the corresponding α-iodoketones were obtained selectively without forming iodocyclized and/or addition products. [ABSTRACT FROM AUTHOR]

The electronic absorption spectra of aqueous solutions of iodine monochloride ICl are studied. The spectra of as-prepared solutions display the absorption band associated with hydrated ICl molecules. An additional band indicating that molecular iodine was formed in the solution emerges in the spectrum as dissolution takes place. Only the band belonging to iodine monochloride remains in the absorption spectra, and no additional bands appear after chloride anions Cl are added to the solution. The absorption spectrum becomes more complex when ICl is dissolved in an alkaline medium. The band belonging to molecular iodine emerges in the spectra at low alkali concentrations, while being transformed to other shorter-wavelength bands at high alkali concentrations (рН ≥ 12). [ABSTRACT FROM AUTHOR]

The reaction of the piperazine mono-adduct, N(CH2CH2)2NC60, with diiodine produced well ordered, black crystals of (I2N(CH2CH2)2NI2)C60·2.884(C6H6)·0.116I2, which contains two nearly linear N–I–I units. Reaction of N(CH2CH2)2NC60 with iodine monochloride produced two materials: the dihalogen adduct, (ClIN(CH2CH2)2NICl)C60·2.3(CS2)·0.7(CH2Cl2), when crystallization occurred rapidly from carbon disulfide/dichloromethane solution or the salt, [(N(CH2CH2)2NH)C60+][ICl2−]·CS2, when crystallization happened more slowly from toluene/dichloromethane solution where hydrolysis of the iodine monochloride by adventitious water presumably occurred. [ABSTRACT FROM AUTHOR]

Herein, we present some aspects regarding the iodination/bromination of 4-hydroxycoumarin or itsO-methyl orO-acetyl derivatives with iodine monochloride or iodine monobromide as halogenation reagents. Also, the investigation of photochemical transformation of the three 3-iodocoumarins was investigated for the first time. [ABSTRACT FROM AUTHOR]

The article offers information on chlorination of 3-arylsydnones with the application of iodine monochloride.

The structural and electronic properties of the global minimum structures of neutral, anionic and cationic CLi( n = 2-20; μ = 0, ±1) clusters were systematically investigated using the unbiased CALYPSO structure searching method in conjunction with density functional theory calculations at the B3LYP/6-311+G* level of theory. It was found that the ground-state structures of neural CLi clusters exhibit linear and planar configurations at n = 2 and 3, respectively, above which three-dimensional configurations are preferred with C and several Li atoms encapsulated into the Li cages. There were only minor differences in the structure between the neutral and charged CLi clusters, which is in accordance with the calculated results of ionization potential and electron affinity. However, the addition/removal of one electron to/from the neutral species had a significant effect on the stabilities of the resulting charged clusters. The averaged binding energy indicated that cationic CLi clusters show relatively higher stabilities. Pronounced odd-even alternations were observed in the fragmentation energy, second-order energy difference and HOMO-LUMO energy gaps. Finally, detailed chemical bonding of the CLi cluster was analyzed based on the AdNDP method, and static polarizabilities of CLi clusters are discussed. [ABSTRACT FROM AUTHOR]

Grindstone technique has been found to be a highly efficient for thiocyanation of aromatic and heteroaromatic compounds with Iodine mono chloride/KHSO4, Potassium metaperiodate/KHSO4. The methods offered selective thiocyanation of aromatic and heteroaromatic compounds in good yields with remarkable rate accelerations. The developed protocols under nonconventional (sonication and grindstone) methods are also promising compared with the existing procedures. [ABSTRACT FROM AUTHOR]

Grindstone technique has been found to be a highly efficient for thiocyanation of aromatic and heteroaromatic compounds with Iodine mono chloride/KHSO4, Potassium metaperiodate/KHSO4. The methods offered selective thiocyanation of aromatic and heteroaromatic compounds in good yields with remarkable rate accelerations. The developed protocols under nonconventional (sonication and grindstone) methods are also promising compared with the existing procedures. [ABSTRACT FROM AUTHOR]

This paper presents an efficient methodology for the synthesis of flavones via the oxidative cyclization of 2′-hydroxychalcones in the presence of iodine monochloride with DMSO under ultrasound irradiation. Ultrasonic irradiation enhances the cyclization reaction and leads to reduced reaction time at lower reaction temperatures while generating flavones with high yields. [ABSTRACT FROM AUTHOR]

A novel and convenient synthesis of 1-naphthaldehydes through iodine monochloride promoted cascade reactions of 1-phenylpent-4-yn-2-ols is presented. Compared with literature procedures, this new method has advantages such as simple operation procedure, mild reaction conditions, good efficiency, and excellent regio-selectivity. [ABSTRACT FROM AUTHOR]

Acetylated gum Arabic (AGA) derivatives with different degrees of substitution (DS 0.97-2.74) were synthesized using acetyl chloride and a base under varying reaction conditions. The AGA derivatives were obtained in the form of microspheres and thereafter stable iodine products were prepared by doping the microspheres with an iodinating agent, iodine monochloride (ICl). The reaction between electrophilic iodine and polar carbonyl groups was studied by FT-IR, 1 H-NMR, and UV-VIS spectroscopies. The products were also characterized by DSC, TGA and SEM studies. The incorporated iodine was released in aqueous medium as iodide ions (I − ). A reaction scheme has been proposed for the iodination and de-iodination of the gum derivatives. This work suggests that the iodine derivatives of modified gum Arabic could be used as a source of iodide ions which is the nutritional form of iodine. [ABSTRACT FROM AUTHOR]

Following a route described by Müllen et al. we improved the preparation of 1,2,3-tris(3″-iodobiphenyl-2′-yl)benzene ( 4). During the required iododesilylation with iodine monochloride the unexpected formation of a mono-chlorinated compound 6 as major product was observed, when an excess of the iodination reagent was employed. The reaction mechanism for the formation of this compound involving an oxidizing process is discussed. X-ray crystallography of the subsequent alkynylated product 7 proves the location of the chlorine atom at the central benzene ring. The related compound 5 was likewise investigated by X-ray analysis revealing a preferred solid-state conformation ('2-up-1-down') different from that of the chlorinated compound ('propeller' conformation). Compound 7 showed remarkable conformational dynamics in solution as observed by 1H NMR spectroscopy. Temperature-dependent measurements allowed the calculation of an energy difference of two major conformers of ca. 2 kJ/mol and a rotational barrier Δ Grot of ca. 77 kJ/mol. These values were convincingly confirmed by DFT calculations. A subsequent Sonogashira reaction of 4 with a suitable bipyridine derivative provided a unique trivalent bipyridine derivative. [ABSTRACT FROM AUTHOR]

Recent progress in electrophilic cyclizations has led to the development of many electrophilic cyclizing agents. Among them, iodine monochloride (ICl) has recently emerged as one of the most promising. In this Review, we highlight the advances in iodine monochloride mediated electrophilic cyclizations from 2000 to 2014. In addition, the different transformations of organoiodine compounds (the usual products of these electrophilic cyclizations) are discussed. [ABSTRACT FROM AUTHOR]

Iodine monochloride (ICl) was discovered to be a highly efficient, green oxidant, which can oxidize aldose hemiacetals, diarylmethanols, arylalkylmethanols, anddialkylmethanols to the corresponding aldose lactones, diarylmethanones, arylalkylmethanones, and dialkylmethanones, respectively, in high yields. ICl as a green, metal-free oxidant is characterized by mild reaction condition, short reaction time, good yield, and broad scope. [ABSTRACT FROM AUTHOR]

In a total residence time of three minutes, ibuprofen was assembled from its elementary building blocks with an average yield of above 90 % for each step. A scale-up of this five-stage process (3 bond-forming steps, one work-up, and one in-line liquid-liquid separation) provided ibuprofen at a rate of 8.09 g h−1 (equivalent to 70.8 kg y−1) using a system with an overall footprint of half the size of a standard laboratory fume hood. Aside from the high throughput, several other aspects of this synthesis expand the capabilities of continuous-flow processing, including a Friedel-Crafts acylation run under neat conditions and promoted by AlCl3, an exothermic in-line quench of high concentrations of precipitation-prone AlCl3, liquid-liquid separations run at or above 200 psi to provide solvent-free product, and the use of highly aggressive oxidants, such as iodine monochloride. The use of simple, inexpensive, and readily available reagents thus affords a practical synthesis of this important generic pharmaceutical. [ABSTRACT FROM AUTHOR]

The reaction of thymidine, 3-mono-, and 3,3′,5′-trialkylsubstitued thymidine analogues with iodine monochloride (ICl) was investigated. Treatment with ICl resulted in rapid deglycosylation, anomerization, and isomerization of thymidine and 3-substituted thymidine analogues under various reaction conditions leading to the formation of the nucleobases as the major products accompanied by minor formation of α-furanosidic-, α-pyranosidic-, and β-pyranosidic nucleosides. On the other hand, 3,3′,5′-trisubstitued thymidine analogues were only deglycosylated and anomerized. These results are similar to those observed for the acidic hydrolysis of the glycoside bond in nucleosides, but were presumably caused by the Lewis acid character of an iodine electrophile. [ABSTRACT FROM PUBLISHER]

A new, mild route for the assembly of 3-iodo-1- azaspiro[4.5]deca-6,9-diene-2,8-diones via an electrophilic ipsocyclization strategy is presented. In the presence of iodine monochloride, water, and sodium bicarbonate, a variety of N-arylacrylamides underwent the intramolecular electrophilic ipso-cyclization reaction to afford the corresponding 3-iodo-1- azaspiro[4.5]deca-6,9-diene-2,8-diones in moderate to good yield. [ABSTRACT FROM AUTHOR]

The major discovery here is a robust and water-stable metal--organic framework (MOF) material capable of The major discovery here is a robust and water-stable metal-organic framework (MOF) material capable of reversible binding of the volatile and reactive molecules of ICl and I2. The immobilization of I2 and ICl, as well as their controllable release thus achieved, is to facilitate the wide-ranging applications of these volatile species as catalysts and reagents in chemical and industrial processes. The framework material TMBP·CuI (hereafter TCuI) can be conveniently prepared in quantitative yields by heating CuI and the organic linker TMBP (3,3',5,5'-tetramethyl-4,4'-bipyrazol) in acetonitrile. The microporous three-dimensional net of TCuI features CuI chains that contribute to efficient and reversible binding of ICl and I2 molecules, to result in the stoichiometrically well-defined adducts of TCuI·ICl and TCuI·I2, respectively. Moreover, the confinement of a volatile compound like ICl within the MOF medium provides unique opportunities to enhance its reactivity and selectivity as a chemical reagent, as is exemplified by the iodination reactions examined herein. With this exemplary study, we intend to stimulate interest in further exploring MOFs and other porous media (e.g., porous polymers) for entrapping ICl and other volatile reagents (e.g., Br2, SCl2, S2Cl2, and SOCl2) and for potentially novel reactivity associated with the porous medium. [ABSTRACT FROM AUTHOR]

Abstract: We report a new method to modify electrical properties of carbon nanotubes (CNTs). Single-, double- and multi-wall CNTs were subjected to treatment with a polar interhalogen compound, i.e. iodine monochloride (ICl) for 8h at room temperature or briefly at 350°C to assess kinetics and thermodynamics of the reactions. The results showed a powerful p-doping, which enabled us to decrease electrical resistance of the material by more than 60% eventually reaching specific conductivity of 1.24Sm2 g−1. Functionalization of CNTs with halogen atoms resulted in evident changes to the material microstructure and composition. To illustrate viability of this technique for manufacturing highly conductive wires, we have produced an ICl-doped CNT-based USB cable. The tests unequivocally revealed that the cable could be successfully used for power or data transmission on the verge of USB 2.0 capabilities. [Copyright &y& Elsevier]

A synthesis of iodo-substituted dibenzocyclohepten-5-ones by the iodine monochloride (or iodine)-induced intramolecular 7-endo-dig cyclization of 1-([1,1'-biphenyl]-2-yl)alkynones is reported. Detailed investigations on the substituent effects during the electrophilic iodocyclization of the alkynones show that they play a crucial role in determining the reaction pathways of the cyclization. By modifying the substitution pattern on the alkynone substrates, the cyclization takes place regioselectively, leading to either dibenzocyclohepten-5-ones, via a 7-endo-dig cyclization, or spiroconjugated compounds, via a 6-endo-dig cyclization. [ABSTRACT FROM AUTHOR]

High abundances of iodine monoxide (IO) are known to exist and to participate in local photochemistry of the marine boundary layer. Of particular interest are the roles IO plays in the formation of new particles in coastal marine environments and in depletion episodes of ozone and mercury in the Arctic polar spring. This paper describes a ground-based instrument that measures IO at mixing ratios less than one part in 1012. The IO radical is measured by detecting laser-induced fluorescence at wavelengths longer that 500 nm. Tunable visible light is used to pump the A²Π3/2 (v' = 2) ← X²Π3/2 (v'' = 0) transition of IO near 445 nm. The laser light is produced by a solid-state, Nd:YAG-pumped Ti:Sapphire laser at 5 kHz repetition rate. The laser-induced fluorescence instrument performs reliably with very high signal-to-noise ratios (>10) achieved in short integration times (<1 min). The observations from a validation deployment to the Shoals Marine Lab on Appledore Island, ME are presented and are broadly consistent with in situ observations from European Coastal Sites. Mixing ratios ranged from the instrumental detection limit (<1 pptv) to 10 pptv. These data represent the first in situ point measurements of IO in North America. [ABSTRACT FROM AUTHOR]

[Display omitted] • The rovibrational structure of the H' 1 (1 D 2) ion-pair state of I35Cl was observed. • The set of the Dunham-type spectroscopic constants of H' 1 (1 D 2) were determined. • An accurate RKR potential energy curve was constructed. • The transition dipole moment function of H' 1 (1 D 2) – A 3Π 1 was determined. The H' 1 (1 D 2) ion-pair state of I35Cl, which correlates to the I+ (1 D 2) + Cl− (1 S 0) dissociation limit, was analyzed spectroscopically by H' 1 (1 D 2) ← A 3Π 1 ← X 1Σ+ optical–optical double resonance excitation. In total, 751 transitions covering 0 ≤ v H' ≤ 20 and 10 ≤ J H' ≤ 41 were observed. An e / f -parity splitting (Ω-type doubling) in the H' 1 (1 D 2) state was observed. By fitting 656 transitions to Dunham type expansion, Dunham coefficients for the H' 1 (1 D 2) state were determined to be Y 00 = 51615.194(14), Y 10 = 184.2440(59), Y 20 = −0.63083(67), Y 30 = 0.001400(21), Y 01 = 0.05780468(82), Y 11 = −2.2465(19) × 10−4, and Y 21 = −2.227(88) × 10−7 cm−1. The vibration-dependent Ω-type doubling constants were determined to be q 0 = 1.97(17) × 10−5, q 1 = 8.76(38) × 10−6, and q 2 = −3.498(18) × 10−7 cm−1. The electronic transition dipole moment function of the H' 1 (1 D 2) – A 3Π 1 transition in the range of 2.977–3.683 Å was determined experimentally by analyzing the dispersed ultraviolet (UV) fluorescence spectra combined with the fluorescence lifetime of the H' 1 (1 D 2) state. [ABSTRACT FROM AUTHOR]

Using the formation constants of 74 charge-transfer complexes in which iodine and iodine monochloride act as acceptors, quantitative structure-property relationships models were developed for predicting these constants for the first time. The procedure was based on reducing a large number of the descriptors based on the variable importance in projection and subsequent selection by stepwise regression and genetic algorithm. The most important variables influencing the charge-transfer interactions were identified and interpreted. Models were obtained by linear methods of multiple linear regression and partial least squares regression and the nonlinear method of radial basis function-partial least squares. The best predictions were obtained with the Gaussian radial basis function with σ = 0.9 and LV = 10. The obtained results confirm the capability of the proposed approach to give predictive models for K. [ABSTRACT FROM AUTHOR]

Electrophilic intramolecular twofold iodoarylation was developed from the reaction of diynes and diynyl diethers and amines with iodine monochloride under mild conditions, which produced bis(2H-hydronaphthalene and chromene) and 2H-quinoline bearing an alkenyl iodide moiety in good to excellent yields. These compounds underwent Pd-catalyzed cross-coupling reactions with arylboronic add and indium tris(arylthiolate) to produce the functionalized styrene derivatives. [ABSTRACT FROM AUTHOR]

Spiro compounds: An iodine monochloride‐induced intramolecular cyclization of 1‐[4′‐methoxy(1,1′‐biphenyl)2‐yl]alkynones has been developed (see scheme). An electrophilic iodocyclization selectively takes place at the ipso position (versus the ortho electrophilic aromatic substitution) to afford 4′H‐spiro(cyclohexa[2,5]diene‐1,1′‐naphthalene)‐4,4′‐diones, a new group of spiroconjugated compounds. [ABSTRACT FROM AUTHOR]

Unprecedented results are obtained from bromination of the normal/non-bridged and abnormal/bridged Biginelli compound of salicyldehyde. Bromination with 2,4,4,6-tetrabromocyclohexa-2,5-dienone yields a bridged monobromo-derivative and a bridged dibromo-derivative, respectively, whereas bromination with bromine and acetic acid gives a mixture of those two products in each case. Bromination with N-bromosuccinimide gives a third product, namely a tribromo-derivative, in addition to those two products. Iodination of both the substrates using iodine monochloride (Wijs solution) furnishes a bridged monoiodo-derivative only. [ABSTRACT FROM PUBLISHER]

Low-lying excited state potential energy curves (PECs), nonadiabatic coupling terms, and transition dipole moments of ICl have been obtained by a spin-orbit configuration interaction method. The angular momentum polarization parameters of photofragments can be calculated from these properties of the molecule. The first-rank parameter Im[a1(1)(//,⟂)] of the ground state photofragment Cl(2P3/2) in the first absorption band (490-560 nm) is very sensitive to the PECs of the low-lying excited states, especially the A(1) and B(0+) states. The phase part of the calculated parameter Im[a1(1)(//,⟂)] agrees well with experiment. We further clarify the characteristics of avoided crossing between the X(0+) and B(0+) states. We calculated the product fraction of Cl*(2P1/2) and the anisotropy parameter β to demonstrate the effect of photoabsorption caused by the z(1) state, which supports a recent experimental analysis. © 2012 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

Abstract: Substituted furans are conveniently synthesized from acyclic secondary 1-alkyl-2-alkynylallylic alcohol precursors via an ICl-promoted cyclization reaction. The furans generated by this method incorporate both iodine and chlorine atoms which may be useful for further elaborations via many known methods. The methodology is suitable for generating a wide array of furan products which can serve as useful building blocks for the synthesis of various biologically active molecules. [Copyright &y& Elsevier]

ICl-SiO2 as a new reactive system was prepared by treatment of iodine monochloride with activated silica gel in chloroform. ICl-SiO2 in a heterogeneous system efficiently converted thiols to the corresponding disulfides under mild conditions in high yields at room temperature.[image omitted] [ABSTRACT FROM AUTHOR]

A single pot conversion of carboxylic acids into the corresponding 4-chlorobutyl esters has been achieved by a novel procedure. The intermediate acid chlorides are not isolated. The double bond and aromatic methoxy group survive the mild reaction conditions. In almost all the examples studied the products are purified by simple flash chromatography. [ABSTRACT FROM AUTHOR]

Abstract: The removal of Hg0 by the homogenous gas-phase reaction and particle-induced reaction was investigated under various conditions. Iodine monochloride was found to be efficient for Hg0 oxidation, with the apparent 2nd-order rate constant of about 10.5(±0.3)×10−17 cm3 molecules−1 s−1 and 5.7(±0.3)×10−17 cm3 molecules−1 s−1 at 273K and 373K, respectively. The pilot-scale tests showed that the removal of Hg0 by ICl increased significantly in presence of flyash. It was predicted that over 90% of Hg0 removal efficiency can be obtained with 0.2ppmv ICl and 20g/m3 flyash in flue gas. Though the reaction between Hg0 and ICl was by far faster than that of Hg0/Cl2, the major product was found to be HgCl2 rather than HgI2, which implicated that iodine might partly act as the accelerant in Hg0 oxidation by facilitating the formation of certain intermediates. The results indicated that using ICl to oxidize elemental mercury in coal-fired flue gas can save the consumption of iodine, and it appeared to be a promising oxidant to enhance the removal of Hg0. [Copyright &y& Elsevier]

A novel, simple, sensitive spectrophotometric method is proposed for the determination of cobalt(II). Chloromine-T with iodine in acetic acid produces iodine monochloride, which oxidizes promethazine hydrochloride and diphenylamine to absorbing cations. Those would associate later with cobalt complex to form an ion pair, [Ph+] [CoCl4]- and [Dh2+] [CoCl4]- 2 in acid medium. These appear to provide exceptional color stability to the systems. The results compare favorably with those of reported method. The conditions required for the determination of cobalt(II) are described and related analytical parameters are also calculated. [ABSTRACT FROM AUTHOR]

Abstract: Phase-vanishing reactions are triphasic reactions, which involve a reagent, a liquid perfluoroalkane as a phase screen and a substrate. Aromatization, isomerization and halogenation of neat substrates under phase-vanishing conditions gave the expected products in good to excellent yields. In tandem single-phase–phase-vanishing reaction, two reactants, placed in the top phase, afforded the intermediate, which in a subsequent phase-vanishing reaction reacted with the reagent from the bottom phase to give the final product. The reaction worked well under solvent-free conditions on liquid substrates and intermediates. With solids, results were better if an additional solvent was employed. [Copyright &y& Elsevier]

A new short and highly efficient synthesis of (5)-2,3-dimethoxy-N[(1-ethyl-2-pyrrolidinyl)methyl]-5-iodobenzamide (epidepride, 1) from 3-methoxy-salicylaldehyde (o-vanillin, 2) and 3-methoxysalicyclic acid (6) was achieved by employing a new iodination method with iodine monochloride and iodine nitrate under basic conditions. [ABSTRACT FROM AUTHOR]

The pathway of the iodination of methoxybenzene by electrophilic iodine monochloride (ICl) was studied by using density functional theory (DFT) calculations at the B3LYP/6–311G* and MP2/6–311G*//B3LYP/6–311G* levels. The iodination occurs in the position para to the methoxy group, and proceeds in two steps. Initially, a π-complex forms between ICl and aromatic ring of methoxybenzene. With a barrier of 60.81 kcal mol-1 (1 kcal = 4.184 kJ), the π-complex can be activated to an intermediate σ-complex with energy 42.02 kcal mol-1 higher than that of the π-complex. The σ-complex then transforms easily (barrier 3.56 kcal mol-1) into the final products, 1-iodo-4-methoxybenzene and HCl. The total iodination is slightly exothermic. Accompanying to the I&bond;Cl bond breaking and C&bond;I bond formation, a hydrogen atom migrates first to iodine and then to chlorine. According to NBO charge, Wiberg bond index and molecular orbital analysis, both charge separation and charge transfer occur during the iodination. Solvent effects were examined with the IEFPCM method and the B3LYP/6–311G* level. The results imply that polar solvents should play a key role in lowering the energy barrier, and favor the ion-pair route of the iodination reaction. Copyright © 2005 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Abstract: The formation of charge-transfer (CT) complexes between N-methyl-6,7-methylenedioxy-tetrahydro-4-isoquinolone (MMDTIQ, the model molecule of alkaloids) and iodine monochloride has been studied with the density functional B3LYP method. The competition for ICl between n-donor(s) and π-donor in the same molecule has been compared for the first time. The results indicate that the electron-donating ability of various donor sites decreases in the following order: amino nitrogen>carbonyl oxygen>etheric oxygen≉aromatic ring. Complexes with a stoichiometry of 1:1 to 1:5 (MMDTIQ–ICl) might form. Among complexes with a given stoichiometry, the one in which the phenyl ring is involved in the binding is always the least stable. According to these results, in order to ensure an alkaloid iodinated, the amount of ICl should be far beyond that of alkaloids and a low polar solvent should be used, which is quite in agreement with our recent experimental results. [Copyright &y& Elsevier]