Iodine, in ethyl

Replacement of silver nitrite by inexpensive sodiiunor potassium nitrite enhances the imlity of this process Treatment of alkenes v/ith sodiiun nitrite and iodine in ethyl acetate and water in the presence of ethylene glycol gives conjngatednitroalkenesin49-82% yield The method for generation of nitryl iodide is improved by the treatment of iodme v/ith potassium nitrite complexed v/ith 18-crovm-6 in THF under sonicadon, as shovmin Eq 2 32 ... 

All of the discussion we have just applied to the dissolving of iodine in ethyl alcohol applies equally well to the dissolving of iodine in carbon... 

I2 (C2H5OH). Pickering8 and Waentig1 reported for the heat of solution of solid iodine in ethyl alcohol —1.7 and —1.9, respectively. The solution is brown. 

In the work reported here, which was directed toward the attainment of an isotopic enrichment of the trivalent actinide and lanthanide elements, the problem was compounded by the fact that these elements do not readily form appropriate compounds, like iodine in ethyl iodide. They do form some stable organic chelates, and, indeed, it is possible to obtain a Szilard-Chalmers reaction with such compounds. However, their radiation damage resistance does not appear adequate to permit useful production of an isotope like 247Cm, which requires a thermal neutron exposure ap-... 

The chemical fate of a hot-atom produced by a nuclear reaction was perhaps first studied by Szilard and Chalmers (1934) who carried out the reaction on iodine in ethyl iodide. They observed that... 

Iodine in ethyl esters of the fatty acids of poppyseed oil 1%. 

Following the above mechanical use of nuclear recoil, purely chemical effects of nuclear recoil were observed by Szilard and Chalmers (1934a, b) in 1934. They used (n,y) reaction of iodine in ethyl iodide. The product of neutron capture, I, could be chemically extracted into an aqueous phase after mixing ethyl iodide with water. 

Long chain a-bromo-to-carboxylic acids were converted to their 128-iodo-derivatives in quantitative yield simply by sonolysis of the acid with 128-iodine in ethyl acetate solution for 20 min [183]. Furthermore, investigations showed that the system would tolerate up to 7.5 % volume water. As yet there are no examples of this simple procedure being used in place of the commonly used Finkelstein method [184] for preparation of alkyl iodides from the equivalent bromide. 

While the sodium ethoxide solution is cooling, prepare a solution of 7 7 g. of finely powdered iodine in 60 ml. of ether. When this solution is ready, add 9 ml. (9 6 g.) of ethyl malonate to the ethanolic sodium ethoxide solution, mix w ell and then allow to stand for 30-60 seconds not longer) then cautiously add the ethereal solution of the iodine, mixing thoroughly during the addition in order to avoid local overheating by the heat of the reaction. (If, after the ethyl malonate has been added to the sodium ethoxide, a considerable delay occurs before the iodine is added, the yield of the final product is markedly decreased.)... 

The observation in 1949 (4) that isobutyl vinyl ether (IBVE) can be polymerized with stereoregularity ushered in the stereochemical study of polymers, eventually leading to the development of stereoregular polypropylene. In fact, vinyl ethers were key monomers in the early polymer Hterature. Eor example, ethyl vinyl ether (EVE) was first polymerized in the presence of iodine in 1878 and the overall polymerization was systematically studied during the 1920s (5). There has been much academic interest in living cationic polymerization of vinyl ethers and in the unusual compatibiUty of poly(MVE) with polystyrene. 

Replacement of iodine in (perfluoroalkyl)ethyl iodides predominates over the usual conversion to olefins when the reagent is very nucleophilic and weakly basic Soft nucleophiles like sodium thiocyanate and sodium thiolates react well in displacements [46, 47] (equation 42)... 

Reaction.—A delicate test for ethyl alcohol is the lodofornt reaction. Pour a few drops of alcohol into a test-tube and add about 5 c.c of a solution of iodine in potassium iodide, and then dilute caustic soda solution until the iodine colour vanishes. Shake up and narm very gently to about 6o°. If no turbidity 01 precipitate appears at once, set the test-tube aside for a time. Yellow crystals of iodoform will ultimately deposit, which have a peculiar odoui, and a characteiistic star shape nhen viewed under the microscope. The same reaction is given with... 

Though many solutions are colorless and closely resemble pure water in appearance, the differences among solutions are great. This can be demonstrated with the five pure substances, sodium chloride (salt), iodine, sugar, ethyl alcohol, and water. Two of these substances, ethyl alcohol and water, are liquids at room temperature. Let s investigate the properties of the solutions these two substances form. 

First we can investigate, qualitatively, the extent to which the solids dissolve in the liquids. By adding a small piece of each solid to a milliliter of liquid, we easily discover that sugar dissolves both in water and ethyl alcohol, sodium chloride dissolves readily in water but not in ethyl alcohol, and iodine does not dissolve much... 

Thus we find great variation among solutions. Iodine dissolves in ethyl alcohol, coloring the liquid brown, but does not dissolve readily in water. Sodium chloride does not dissolve readily in ethyl alcohol but does dissolve in water, forming a solution that conducts electric current. Sugar dissolves readily both in ethyl alcohol and in water, but neither solution conducts electric current. These differences are very important to the chemist, and variations in electrical conductivity are among the most important. We shall investigate electrical conductivity further but, first, we need to explore the electrical nature of matter. 

We have, in this chapter, encountered a number of properties of solids. In Table 5-II, we found that melting points and heats of melting of different solids vary widely. To melt a mole of solid neon requires only 80 calories of heat, whereas a mole of solid copper requires over 3000 calories. Some solids dissolve in water to form conducting solutions (as does sodium chloride), others dissolve in water but no conductivity results (as with sugar). Some solids dissolve in ethyl alcohol but not in water (iodine, for example). Solids also range in appearance. There is little resemblance between a transparent piece of glass and a lustrous piece of aluminum foil, nor between a lump of coal and a clear crystal of sodium chloride. 

The heat of solution of iodine in benzene is +4.2 kcal/mole (heat is absorbed). Assuming the increase in randomness is the same when iodine dissolves in liquid benzene as it is in ethyl alcohol and in CC14, justify the prediction that the solubility of I2 in benzene is higher than in CC14 but lower than in alcohol. 

Attempted iodocyclization with iodine in moist acetonitrile of ethyl 2-hydroxypent-4-enoate (59) to give the iodotetrahydrofuran (62) gave instead a 2 1 mixture (80%) of syn- and -lactones (60) and (61). Labelling studies with H2 0 indicated that the probable mechanism of the reaction involved initial attack of the ester group upon the iodonium ion (63) to yield a mixture of epimeric carbocations (64), which upon attack by water would yield the orthoesters (65), elimination of ethanol from which giving the epimeric y-lactones (60, 61). ... 

Amiodarone (Figure 8.2) is an efficacious drug that causes a number of side-effects. The presence of iodine in the molecule is unusual and hypo- and hyperthyroidism have been reported in patients. Although the loss of iodine is relatively slow the relatively large daily dose size and long half-life of the drug and its de-ethylated metabolite suggest that the presence of iodine in the molecule is responsible for its toxicity [3]. 

Oxidation of the acetyl group in 2-acetyl-3,S-dialkyl derivatiyes of 1 and 2 with iodine in pyridine, and of the formyl group in 5-ethyl-2-formyl- and 2-formylthieno[2,3-6]thiophene, and 4-formyl- and 6-formylthieno[3,4-6]thiophene (194 and 195) with silver oxide, was performed to verify the structures of the acetylation and formylation products. 

The solubility of the halogens in organic solvents.—L. Bruner33 has measured the solubility of iodine in mixtures of ethyl alcohol and water at 15° ... 

The tinctura iodi of the British Pharmacopoeia is a soln. of half an ounce of iodine, and a quarter of an ounce of potassium iodide in a pint of rectified spirit. P. Wantig found the mol. ht. of soln. —1 941 Cals., and S. U. Pickering —1 714 per 880 mol. of ethyl alcohol. C. Lowig found that alcoholic tincture of bromine is slowly decomposed in darkness, rapidly in light. Alcoholic soln. of iodine, according to H. E. Barnard, are stable in light and in darkness, but according to J. M. Eder they decompose 1000 times more slowly than chlorine water under similar conditions T. Budde has shown that hydriodic acid, acetic ester, and aldehyde are formed, and the electrical conductivity of the soln. increases. J. H. Mathews and E. H. Archibald and W. A. Patrick found a freshly prepared AT-soln. to have an electrical conductivity of 2 4 XlO-6 reciprocal ohms and a sat. soln., 1 61 X10 4 reciprocal ohms at 25°. The decomposition is accelerated by the presence of platinum. The heat of soln. decreases with concentration from —7 92 to —7 42 cals, respectively for dilute and sat. soln. in methyl alcohol, and likewise from —4 88 to —5 22 cals, for similar soln. in ethyl alcohol. The solubility of iodine in aq. soln. of propyl alcohol is not very different from that in ethyl alcohol. 

P. Walden34 has studied soln. of iodine in acetaldehyde, hydrazine hydrate, and acetonitrile J. H. Mathews, soln. of iodine in pyridine, ethyl, allyl, and plienyl isothiocyanic esters, and phenyl isocyanate while H. A. Allen has studied soln. of bromine and iodine in various oils. 

Similarly with the raising of the b.p. in violet or reddish-violet soln. of iodine in benzophenone, carbon disulphide, ethyl chloride, chloroform, carbon tetrachloride, ethylene chloride or benzene or in brown soln. of ethyl alcohol, methyl alcohol, thymol, ethyl ether, methylal, or acetone. The values for the last three solvents were rather low, presumably because of the chemical action of solute on solvent. High values with benzene are attributed to the formation of a solid soln. of solvent and solid. Confirmatory results were found by J. Hertz with naphthalene, and by E. Beckmann and P. Wantig with pyridine. The results by I. von Ostromisslensky (o-nitrotoluene), by G. Kriiss and E. Thiele (glacial acetic acid), and by H. Gautier and G. Charpy indicate polymerization, but they are not considered to be reliable. 

An equimolecular mixture of mercury(I) fluoride and iodine fluorinated ethyl 2,3,3-tri-bromopropanoate to give ethyl 2,3-dibromo-2-fluoropropanoate in 19% yield at 150 C and reduced pressure for 2 hours,63 while treatment of methyl 2,3-dibromopropanoate with the mixture of mercury(I) fluoride and iodide at 150 C for 2.5 hours provides methyl 2-bromo-3-fluoropropanoate in 23 % yield.64... 

Our synthesis started with ethyl 5-methyl-4-isoxazole carboxylate (50), prepared from ethyl acetoacetate and DMF dimethyl acetal (Scheme 5.4).14 Ester 50 was reduced with LiAlH4 and the resulting alcohol was oxidized to afford aldehyde 51. Enone 52 was obtained from aldehyde 51 using conditions developed by McCurry and Singh.15 The next step was the aromatization of the cyclohexane ring of 52 to produce the aromatic "A" ring of the monomer. Treatment of enone 52 with iodine in the presence of sodium ethoxide produced phenol 53.16... 

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