Iodides, test for

Cyclododecanone (2.0 g, 11 mmol) is added to m-chloroperbenzoic acid (4.2 g, 21 mmol) in 25 ml of dry chloroform (CAUTION). The reaction mixture is heated at reflux for 48 hours after which time a starch-iodide test for peroxide is negative. After the mixture is cooled in ice-water, the precipitated m-chlorobenzoic acid is removed by filtration and the chloroform is evaporated to dryness. The residue is taken up in 60 ml of ether, washed three times with 20-ml portions of aqueous potassium carbonate, and once with brine. After drying and removal of solvent there remains crude dodecanolide (1.9 g,... 

The helical structure of amylose also serves as the basis for an interesting and useful reaction. The inside of the helix is just the right size and polarity to accept an iodine (I2) molecule. When iodine is lodged within this helix, a deep blue starch-iodine complex results (Figure 23-19). This is the basis of the starch-iodide test for oxidizers. The material to be tested is added to an aqueous solution of amylose and potassium iodide. If the material is an oxidizer, some of the iodide (I-) is oxidized to iodine (I2), which forms the blue complex with amylose. 

Chlorine is more potent an oxidant than is bromine but less so than fluorine (Clifford, 1961a). Thus, chlorine is able to oxidize both bromide and iodide ions to Br2 and I2, respectively, whereas fluorine oxidizes chloride, bromide, and iodide to their corresponding halogens. The oxidizing ability of chlorine is the basis for the starch-iodide test for chlorine. Here, a mixture of potassium iodide, soluble starch, and zinc chloride produces a blue-violet color in the presence of chlorine. Unfortunately, and like many spot tests, this is a nonspecific test and gives a positive result with many oxidants, for example, bromine. 

The strength of a hypochlorite solution is usually expressed in terms of available chlorine. As explained above, available chlorine refers to the amount of chlorine that has the same oxidizing power as the active agent found in a given solution. In analysis by the starch-iodide test, for example, we have... 

Sodium Iodide Test for Alkyl Chlorides and Bromides... 

Nitrous add reacts rapidly but not instantaneously with amines. Consequently, in testing for completion of the reaction (presence of mreacted nitrous acid), the starch-iodide test for free nitrous add should not be applied until 5 minutes after the addition of a portion of the sodium nitrite solution. 

The solid has a layer structure (p. 434). Lead(ir) iodide, like lead(Il) chloride, is soluble in hot water but on cooling, appears in the form of glistening golden spangles . This reaction is used as a test for lead(II) ions in solution. 

The experimental conditions necessary for the preparation of a solution of a diazonium salt, diazotisation of a primary amine, are as follows. The amine is dissolved in a suitable volume of water containing 2 5-3 equivalents of hydrochloric acid (or of sulphuric acid) by the application of heat if necessary, and the solution is cooled in ice when the amine hydrochloride (or sulphate) usually crystallises. The temperature is maintained at 0-5°, an aqueous solution of sodium nitrite is added portion-wise until, after allowing 3-4 minutes for reaction, the solution gives an immediate positive test for excess of nitrous acid with an external indicator—moist potassium iodide - starch paper f ... 

Recovery of the wopropyl alcohol. It is not usually economical to recover the isopropyl alcohol because of its lo v cost. However, if the alcohol is to be recovered, great care must be exercised particularly if it has been allowed to stand for several days peroxides are readily formed in the impure acetone - isopropyl alcohol mixtures. Test first for peroxides by adding 0-6 ml. of the isopropyl alcohol to 1 ml. of 10 per cent, potassium iodide solution acidified with 0-6 ml. of dilute (1 5) hydrochloric acid and mixed with a few drops of starch solution if a blue (or blue-black) coloration appears in one minute, the test is positive. One convenient method of removing the peroxides is to reflux each one litre of recovered isopropyl alcohol with 10-15 g. of solid stannous chloride for half an hour. Test for peroxides with a portion of the cooled solution if iodine is liberated, add further 5 g. portions of stannous chloride followed by refluxing for half-hour periods until the test is negative. Then add about 200 g. of quicklime, reflux for 4 hours, and distil (Fig. II, 47, 2) discard the first portion of the distillate until the test for acetone is negative (Crotyl Alcohol, Note 1). Peroxides generally redevelop in tliis purified isopropyl alcohol in several days. 

A simple test for ether peroxides is to add lOmL of the ether to a stoppered cylinder containing ImL of freshly prepared 10% solution of potassium iodide containing a drop of starch indicator. No colour should develop during one minute if free from peroxides. Alternatively, a 1% solution of ferrous ammonium sulfate, O.IM in sulfuric acid and O.OIM in potassium thiocyanate should not increase appreciably in red colour when shaken with two volumes of the ether. 

Apparently the role of methanol is to intercept unstable species which otherwise tend to polymerize or rearrange. The methoxy peroxide (72) can be isolated in crystalline form if desired, but it is preferable to treat the methylene dichloride solution at 0° with zinc dust and acetic acid until the mixture shows a negative potassium iodide test. The resulting crude seco-aldehyde (73) is then cyclized to (74) by stirring with neutral alumina in benzene at room temperature for 3 hr. ° Wechter has recently reported a number of transformations of a 5yS-hydroxy-6yS-formyl-B-norpregnane prepared in 8% yield by photolysis and hydrolysis of a 5a-hydroxy-6 -azidopregnane. 

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... 

A few- reagents react with the N—-H groups of the diaziridines. It is easy to decide w hether the resulting compounds still contain a true diaziridine ring by testing for the characteristic property of such rings to liberate from iodide solution two equivalents of iodine. 

We have seen in Experiment 8 that silver chloride has low solubility in water. This is also true for silver bromide and silver iodide. In fact, these low solubilities provide a sensitive test for the presence of chloride ions, bromide ions, and iodide ions in aqueous solutions. If silver nitrate... 

A mixture of 280 g. (1.52 moles) of commercial benzidine and 880 cc. (10.23 moles) of concentrated hydrochloric acid (sp. gr. 1.182) is placed in a 5-I. round-bottomed flask and wanned on a steam bath for one to two hours, with occasional shaking, to form the dihydrochloride. The flask is then equipped with a mechanical stirrer and a dropping funnel, and cooled, with stirring, to — ro° in an ice-salt bath. When this temperature has been reached, the benzidine dihydrochloride is tetrazotized over a period of two hours with a solution of 232 g. (3.19 moles) of 95 per cent sodium nitrite in 800 cc. of water, until a faint test for nitrous acid with starch-iodide paper is obtained after twenty minutes. During this reaction, the temperature is kept below —5 °. 

Testing for excess of nitrous acid at the end of the reaction. For this purpose starch-potassium iodide papers are best used, and these indicate nitrite in acid solution by turning blue instantaneously. With some practice, the nitrite reaction can be clearly distinguished from the coloration caused by certain diazo compounds, such as those bearing nitro substituents. The latter react only after 0.5 to 2 seconds. Often the difference becomes more marked after dilution of the diazo solution with concentrated hydrochloric acid. A properly conducted diazotization should exhibit on completion a very weak nitrite reaction, corresponding to an excess of about 10 4 m. 

Halide exchange, sometimes call the Finkelstein reaction, is an equilibrium process, but it is often possible to shift the equilibrium." The reaction is most often applied to the preparation of iodides and fluorides. Iodides can be prepared from chlorides or bromides by taking advantage of the fact that sodium iodide, but not the bromide or chloride, is soluble in acetone. When an alkyl chloride or bromide is treated with a solution of sodium iodide in acetone, the equilibrium is shifted by the precipitation of sodium chloride or bromide. Since the mechanism is Sn2, the reaction is much more successful for primary halides than for secondary or tertiary halides sodium iodide in acetone can be used as a test for primary bromides or chlorides. Tertiary chlorides can be converted to iodides by treatment with excess Nal in CS2, with ZnCl2 as catalyst. " Vinylic bromides give vinylic iodides with retention of configuration when treated with KI and a nickel bromide-zinc catalyst," or with KI and Cul in hot HMPA." ... 

Students usually identify the existence of anions such as carbonate, iodide and sul-fate(VI) by adding a barium/silver(I)/lead(II) solution to the unknown, followed by a dilute acid or vice-versa in qualitative analysis practical work sessions and examinations. Mat r students had difficulty understanding the roles of the bar-ium/silver(I)/lead(II) solution and the dilute acid in the tests for anions. For example, 20% believed that the addition of aqueous barium nitrate(V) followed by dilute nitric(V) acid was to test for sulfate(VI) only. Another 25% believed that to test for a carbonate, acid had to be added directly to the unknown sample, while 20% believed that the addition of barium nitrate(V) invalidated the test for carbonates. When the students were asked the purpose of adding dilute nitric(V) acid following die addition of silver nitrate(V) solution (in one question) and lead(II) nitrate(V in another question) to the unknown solutions, 22% and 35%, respectively, indicated... 

An alternative method of removing the aniline is to add 30 ml. of concentrated sulphiu-ic acid carefully to the steam distillate, cool the solution to 0-5°, and add a concentrated solution of sodium nitrite until a drop of the reaction mixture colours potassium iodide - starch paper a deep blue instantly. As the diazotisation approaches completion, the reaction becomes slow it will therefore be necessary to test for excess of nitrous acid after an interval of 5 minutes, stirring all the wUle. About 12 g. of sodium nitrite are usually required. The diazotised solution is then heated on a boOing water bath for an hour (or until active evolution of nitrogen ceases), treated with a solution of 60 g. of sodium hydroxide in 200 ml. of water, the mixture steam-distiUed, and the quinoline isolated from the distillate by extrac-tkm with ether as above. 

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