Iodine addition product

Iodized Oil. Lipiodol. An iodine addition product of vegetable oils, contg 38-42% organically combined iodine. 

Addition of iodine to C=C bonds is of less preparative importance. It can be effected in ether, ethanol, CS2, CC14, or aqueous KI, or without a solvent. Iodine-addition products are unstable and most of them lose I2 even at room temperature. So the discussion that follows here is restricted to addition of chlorine and bromine. 

Oxidative dimerization of various 2-benzyloxy-2-thiazoline-5-ones (222) catalyzed by iodine and triethylamine is another example of the nucleophilic reactivity of the C-4 atom (469) (Scheme 112). Treatment of 212 with pyrrolidinocyclohexene yields the amide (223) (Scheme 113). The mechanism given for the formation of 223 is proposed by analogy with the reactivitx of oxazolones with enamines (4701. 4-Substituted 2-phenylthiazol-5(4Hi-ones react with A -morphoiino-l-cyclohexene in a similar manner (562j. Recently. Barret and Walker have studied the Michael addition products... 

Approximately 3 lb. of sodium bisulfite is required to reduce the iodine. Technical grade bisulfite may be used satisfactorily. Caution should be observed in adding the bisulfite, since evolution of sulfur dioxide can cause excessive foaming. This foaming occurs a short time after each addition and is most noticeable when the iodine is almost neutralized. Iodine and product clinging to the upper walls of the flask and in the condenser may be conveniently rinsed into the reaction mixture with a stream of water from a wash bottle. 

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 [//]. 

Terminal (perfluoroalkyl)alkynes react with iodine or iodine chloride to yield syn addition products bearing iodine on the terminal carbon [16 (equation 9). 

All diaziridines which contain at least one NH-group give, with chloral, w ell crystallized addition products in molar ratio l ." The adducts liberate tw-o equivalents of iodine and thus retain the CNN three-membered ring [Eq. (38)]. By treatment with alkali the chloro-... 

The same authors reported in a later study <2000H(3)69> that pyrazinone 340 is also a suitable starting material for a such transformation. The reaction proceeds in two steps the starting pyrazinone 340 when treated with benzonitrile oxide yields an addition product 341 which undergoes oxidative cyclization in the presence of iodine-potassium iodide to the ring-closed [l,2,4]oxadiazolo[4,5-tf]pyrazines 342. 

Attempts to alkylate C6o with methyl iodide did not give an addition product, probably because of insufficient reactivity of this electrophile system, due to the low electronegativity of iodine. On the other hand, the use of liquified chloromethane at 60 °C in a stainless steel autoclave afforded the methylated product, which consisted of only the 1,2 isomer, as expected from the small steric requirement of the methyl group (29). 

The reaction of trialkylboranes with 1,4-benzoquinones to give in quantitative yield 2-alkylhydroquinones was the first reaction of this type occurring without the assistance of a metal mediator [81,82], An ionic mechanism was originally proposed but rapidly refuted since the reaction is inhibited by radical scavengers such as galvinoxyl and iodine [83]. This procedure is in many cases superior to the more widely use organometallic additions. For instance, when primary and secondary alkyl radicals have been used and afford the addition products in high yield (Scheme 33) [84],... 

It is remarkable that the aromatic iodo-compounds can be converted via addition products with chlorine into organic iodine derivatives containing multivalent iodine (V. Meyer, Willgerodt). 

Dimethyl tricyclo[4.2.2.02 -5]deca-3,7-diene-9,10-dicarboxylate adds bromine and iodine only to the less hindered double bond to give the syn 1,2-addition product of the cyclobutene moiety79. The product composition from this compound depends on the temperature and the solvent. At high temperatures, the 1,2-addition predominates over the transannular reaction, but this predominance is small in a solvent like chloroform and is lost in a protic solvent such as acetic acid (equation 47). 

It is noteworthy that iodine addition in pyridine to 79 takes place regioselectively, with the iodine atom located exclusively in the product at C(7). Steric factors have been invoked again to explain the selectivity of the nucleophilic attack (equation 81). 

Among organic compounds, alkenes readily react with iodine, giving addition products. For example, iodine adds to ethylene, forming ethylene diiodide ... 

Trifluorovinylcopper reacted readily with perfluoroalkynes to give stereospecific syn addition products, which were quenched with iodine to afford the corresponding iodide [181] (Scheme 64). 

When iodine is dissolved in hydriodic acid or a soln. of a metallic iodide, there is much evidence of chemical combination, with the formation of a periodide. A. Baudrimont objected to the polyiodide hypothesis of the increased solubility of iodine in soln. of potassium iodide, because he found that an extraction with carbon disulphide removed the iodine from the soln. but S. M. Jorgensen showed that this solvent failed to remove the iodine from an alcoholic soln. of potassium iodide and iodine in the proportion KI I2, and an alcoholic soln. of potassium iodide decolorized a soln. of iodine in carbon disulphide. The hypothesis seemed more probable when, in 1877, G. S. Johnson isolated cubic crystals of a substance with the empirical formula KI3 by the slow evaporation of an aqueous-alcoholic soln. of iodine and potassium iodide over sulphuric acid. There is also evidence of the formation of analogous compounds with the other halides. The perhalides or poly halides—usually polyiodides—are products of the additive combination of the metal halides, or the halides of other radicles with the halogen, so. that the positive acidic radicle consists of several halogen atoms. The polyiodides have been investigated more than the other polyhalides. The additive products have often a definite physical form, and definite physical properties. J. J. Berzelius appears to have made the first polyiodide—which he called ammonium bin-iodide A. Geuther called these compounds poly-iodides and S. M. Jorgensen, super-iodides. They have been classified 1 as... 

Potassium iodide can also be obtained from the aq. extract of kelp or from the mother liquid remaining after the separation of sodium chloride and potassium sulphate from sea-water by evaporation. In E. Allary and J. Pellieux process,8 the liquid is evaporated to dryness and roasted in a special furnace so as to avoid a loss of iodine. The product is fractionally extracted with cold water, when a soln. is obtained which on evaporation gives a residue with 50 per cent, of alkali iodide. This product is extracted.in a special digester with 50 per cent, alcohol. The solvent dissolves little more than the iodides. The alcohol is distilled off, and on evaporation a residue containing about 34 per cent, of potassium iodide, and 66 per cent, of sodium iodide is obtained. To convert the latter into potassium iodide, the proper quantity of a soln. of potassium carbonate is added and carbon dioxide passed into the liquid whereby sodium bicarbonate is precipitated. The precipitate is separated by a filter press, and the small amount of sodium bicarbonate remaining in the soln. is separated by the addition of a little hydrochloric acid and the sodium chloride and potassium iodide separated by fractional crystallization. In E. Sonstadt s process, the mother liquid is treated with chlorine mixed with potassium chlorate or permanganate so as to convert the iodine into iodate. A soln. of a barium salt is added, and the barium iodate treated with potassium sulphate. Barium sulphate is precipitated, and the soln. of potassium iodate is evaporated to dryness and calcined to convert the iodate to iodide. The latter is purified by crystallization. 

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