Iodine monochloride iodination

Introduction of iodine by Sandmeyer processes has been discussed [84AHC(35)83], Direct electrophilic iodination is also observed in the 3-position with reagents such as iodine monochloride, iodine-iodic acid-acetic acid, or molecular iodine. With excess reagent, or when C-3 is blocked, 6-iodination follows [84AHC(35)83 84MI15]. 

The iodine monochloride/iodine trichloride system is an example of a chemical equilibrium. When chlorine is passed over iodine crystals, in a U-tube, a brown liquid is formed. This is iodine monochloride, ICl(i). 

Iodination r-Butylhypoiodite. l,3-Diodo-5,S-dimethylhydantoin. Iodine. Iodine monochloride. Iodine-Morpholine complex. Iodine-Silver salt. N-Iodosuccinimide. Silver tri-fluoroacetate. Trifluoroacetylhypoiodite. 

ESTANO (Spanish) (7440-31-5) Finely divided material is combustible and forms explosive mixture with air. Contact with moisture in air forms tin dioxide. Violent reaction with strong acids, strong oxidizers, ammonium perchlorate, ammonium nitrate, bis-o-azido benzoyl peroxide, bromates, bromine, bromine pentafluoride, bromine trifluoride, bromine azide, cadmium, carbon tetrachloride, chlorine, chlorine monofluoride, chlorine nitrate, chlorine pentafluoride, chlorites, copper(II) nitrate, fluorine, hydriodic acid, dimethylarsinic acid, ni-trosyl fluoride, oxygen difluoride, perchlorates, perchloroethylene, potassium dioxide, phosphorus pentoxide, sulfur, sulfur dichloride. Reacts with alkalis, forming flammable hydrogen gas. Incompatible with arsenic compounds, azochloramide, benzene diazonium-4-sulfonate, benzyl chloride, chloric acid, cobalt chloride, copper oxide, 3,3 -dichloro-4,4 -diamin-odiphenylmethane, hexafluorobenzene, hydrazinium nitrate, glicidol, iodine heptafluoride, iodine monochloride, iodine pentafluoride, lead monoxide, mercuric oxide, nitryl fluoride, peroxyformic acid, phosphorus, phosphorus trichloride, tellurium, turpentine, sodium acetylide, sodium peroxide, titanium dioxide. Contact with acetaldehyde may cause polymerization. May form explosive compounds with hexachloroethane, pentachloroethane, picric acid, potassium iodate, potassium peroxide, 2,4,6-trinitrobenzene-1,3,5-triol. 

Many interhalogen compounds explode on contact with potassium. These include chlorine trilluoride, iodine monochloride, iodine monobromide, iodine pentalluoride, and others. A violent explosion occurs when chlorine monoxide comes in contact with potassium. Potassium bums spontaneously with fluorine, chlorine, and bromine vapor. Its mixture with liquid bromine can explode on impact, and mixture with iodine ignites. 

Detailed NMR studies have been carried out on l-selena-4-oxane and the adducts formed in the presence of iodine monochloride, iodine monobromide, chlorine, bromine, and iodine <1999JOC2630>. In deuterated chloroform solution the l-selena-4-oxane molecular complex 29 affords equimolar amounts of bipyramidal adduct 30 and the molecular complex 31 (Equation 1). No such mixture was observed in the solid state. When NMR studies were carried out on the corresponding bromine complex 32, an equilibrium between the complex 32 and adducts 33 and 31 was observed (Equation 2). 

Drepaul, L, Fagundez, V, Guiterrez, F. et al. (1996) Thermochemistry of molecular complexes of iodine monochloride, iodine monobromide, and bromine with benzene and benzene derivatives. J. Org. Chem., 61,3571-3572. 

Iodine monochloride, formed when iodine reacts with the iodate(V) ion in the presence of an excess of concentrated hydrochloric acid. 

Amino-3 5-diiodobenzoic acid. In a 2 litre beaker, provided with a mechanical stirrer, dissolve 10 g. of pure p-aminobenzoic acid, m.p. 192° (Section IX,5) in 450 ml. of warm (75°) 12 -5 per cent, hydrochloric acid. Add a solution of 48 g. of iodine monochloride (1) in 40 ml. of 25 per cent, hydrochloric acid and stir the mixture for one minute during this time a yellow precipitate commences to appear. Dilute the reaction mixtiue with 1 litre of water whereupon a copious precipitate is deposited. Raise the temperature of the well-stirred mixture gradually and maintain it at 90° for 15 minutes. Allow to cool to room tempera-tiue, filter, wash thoroughly with water and dry in the air the yield of crude acid is 24 g. Purify the product by dissolving it in dilute sodium hydroxide solution and precipitate with dilute hydrochloric acid the yield of air-dried 4-amino-3 5-diiodobenzoic acid, m.p. >350°, is 23 g. 

Iodine monochlorlde may be prepared as follows. Pass dry chlorine into 127 g. of iodine contained in a 125 ml. distilling flask until the weight has increased by 34-6 g. The chlorine should be led in at or below the surface of the iodine whilst the flask is gently shaken it is essential to have an excess of iodine. Distil the iodine chloride in an ordinary distillation apparatus use a filter flask, protected from atmospheric moisture by a calcium chloride (or cotton wool) guard tube, as a receiver. Collect the fraction b.p. 97-105° the jdeld is 140 g. Preserve the iodine monochloride in a dry, glass-stoppered bottle. 

Since iodine monochloride attacks cork and rubber, the use of an all-glass apparatus is recommended. If it should come into contact with the skin, an elective antidote is dilute hydrochloric acid (1 1). 

This simplified method gives 2-aminothiazole in good yield (50 to 70%) (311, 330), Other reactants can replace iodine, for example, chlorine, bromine, sulfuryl chloride, chlorosulfonic acid, or sulfur monochloride also give good results. 

Iodine monochloride Aluminum foil, organic matter, metal sulfides, phosphorus, potassium, rubber, sodium... 

The iodination reaction can also be conducted with iodine monochloride in the presence of sodium acetate (240) or iodine in the presence of water or methanolic sodium acetate (241). Under these mild conditions functionalized alkenes can be transformed into the corresponding iodides. AppHcation of B-alkyl-9-BBN derivatives in the chlorination and dark bromination reactions allows better utilization of alkyl groups (235,242). An indirect stereoselective procedure for the conversion of alkynes into (H)-1-ha1o-1-alkenes is based on the mercuration reaction of boronic acids followed by in situ bromination or iodination of the intermediate mercuric salts (243). 

However, in strong hydrochloric acid, these reagents, as weU as iodic acid, oxidize iodine to iodine monochloride or to the ICl ion. 

Iodine monochloride [7790-99-0] ICl, mol wt 162.38, 78.16% I, is a black crystalline soHd or a reddish brown Hquid. SoHd ICl exists ia two crystalline modifications the a-form, as stable mby-red needles, d = 3.86 g/mL and mp 27.3°C and as metastable brownish red platelets, d = 3.66 g/mL, mp 13.9°C and bp 100°C (dec). Iodine monochloride is used as a halogenation catalyst and as an analytical reagent (Wij s solution) to determine iodine values of fats and oils (see Fats and fatty oils). ICl is prepared by direct reaction of iodine and Hquid chlorine. Aqueous solutions ate obtained by treating a suspension of iodine ia moderately strong hydrochloric acid with chlorine gas or iodic acid (118,119). 

The aHphatic iodine derivatives are usually prepared by reaction of an alcohol with hydroiodic acid or phosphoms trHodide by reaction of iodine, an alcohol, and red phosphoms addition of iodine monochloride, monobromide, or iodine to an olefin replacement reaction by heating the chlorine or bromine compound with an alkaH iodide ia a suitable solvent and the reaction of triphenyl phosphite with methyl iodide and an alcohol. The aromatic iodine derivatives are prepared by reacting iodine and the aromatic system with oxidising agents such as nitric acid, filming sulfuric acid, or mercuric oxide. 

Ma.nufa.cture. Sulfur monochloride is made commercially by direct chlorination of sulfur, usually in a heel of sulfur chloride from a previous batch. The chlorination appears to proceed stepwise through higher sulfur chlorides (S Cl2, where x > 2). If conducted too quickly, the chlorination may yield products containing SCI2 and S Cl2 as well as S2CI2. A catalyst, eg, iron, iodine, or a trace of ferric chloride, faciUtates the reaction. The manufacture in the absence of Fe and Fe salts at 32—100°C has also been reported (149—151). 

The decomposition of sulfuryl chloride is accelerated by light and catalyzed by aluminum chloride and charcoal. Many of the reactions of sulfuryl chloride are explainable on the basis of its dissociation products. Sulfuryl chloride reacts with sulfur at 200°C or at ambient temperature in the presence of aluminum chloride producing sulfur monochloride. It hberates bromine or iodine from bromides or iodides. Sulfuryl chloride does not mix readily with water and hydrolyzes rather slowly. 

Pyridazines form complexes with iodine, iodine monochloride, bromine, nickel(II) ethyl xanthate, iron carbonyls, iron carbonyl and triphenylphosphine, boron trihalides, silver salts, mercury(I) salts, iridium and ruthenium salts, chromium carbonyl and transition metals, and pentammine complexes of osmium(II) and osmium(III) (79ACS(A)125). Pyridazine N- oxide and its methyl and phenyl substituted derivatives form copper complexes (78TL1979). 

Iodine monochloride, purchased from J. T. Baker Chemical Company, was used without further purification. 

Molecular iodine is not a very powerful halogenating agent. Only very reactive aromatics such as anilines or phenolate anions are reactive toward iodine. Iodine monochloride can be used as an iodinating agent. The greater electronegativity of the... 

Bromine trifluoride and pentafluoride Chlorine trifluoride Iodine monochloride... 

Interhalogen compounds such as iodine monochloride have been added to fluoroalkyl-substituted alkenes. The observed unidirectional regiochemistry can be explained by the polarity ot the double bond [14] (equation 7)... 

Iodine monochloride adds unidirectionally to perfluoropropene-2-ol to form a chlorohydrin, which easily dehydrochlonnates to yield lodopentafluoroacetone [/5] (equation 8). 

Like simple elemental halogens, iodine monochloride reacts with conjugated fluorodienes to yield mostly 1,4-addition products. These bidirectional reactions lead to mixtures of regioisomers, as shown in Table 5 [//]. 

The reaction of 2H-nonatluoro-2-methylpropane with iodine monochloride in sulfolane in the presence of potassium fluoride produces 2-chlorononafluoro-2-methylpropane in 92% yield at 50% conversion [2d]. 

Chlor-jod, n. iodine chloride, specif, iodine monochloride, -kali, n. chloride of potash (potassium hypochlorite) potassium chloride. -kalilOsung, /. Pharm.) solution of chlorinated potassa, Javelle water, -kalium, n. potassium chloride. 

---