Aldehyde iodoform test

Aldehydes are easy to oxidize, but ketones are more challenging. The two important oxidation reactions of ketones are the oxidation with a strong oxidant and the iodoform test. 

Phenylhydrazone formation indicates a carbonyl compound. Since the negative Tollens test rules out an aldehyde, (A) must be a ketone. A negative iodoform test rules out the CH,C=0 group, and the reduction product, pentane, establishes the C s to be in a continuous chain. The compound is CHjCHjCOCHjCH,. 

Aldehydes Alkanes Benedict s test Dichromate test 2,4-Dinitrophenylhydrazine (2,4-DNP) Fehling test Iodoform test Oxime Permanganate test Semicarbazone Tollen s test No test Positive for all aldehydes Positive for all aldehydes Positive for all aldehydes (and ketones) Positive for all aldehydes Positive only for acetaldehyde Positive for all aldehydes (and ketones) Positive for all aldehydes Positive for all aldehydes (and ketones) Positive for all aldehydes... 

Methyl ketones can be distinguished from other ketones by the iodoform test. The methyl ketone is treated with iodine in a basic solution. Introduction of the first iodine atom increases the acidity of the remaining methyl protons, so halogenation stops only when the triiodo compound has been produced. The base then allows the relatively stable triiodomethyl carban-ion to leave and a subsequent proton transfer gives iodoform, a yellow crystalline solid of mp 119-123°C. The test is also positive for fragments easily oxidized to methyl ketones, such as CH3CHOH— and ethanol. Acetaldehyde also gives a positive test because it is both a methyl ketone and an aldehyde. 

Note cautiously the characteristic odour of acetaldehyde which this solution possesses. Then with the solution carry out the following general tests for aldehydes described on p. 341 Test No. I (SchiflF s reagent). No. 3 (Action of sodium hydroxide). No. 4 (Reduction of ammoniacal silver nitrate). Finally perform the two special tests for acetaldehyde given on p. 344 (Nitroprusside test and the Iodoform reaction). 

The presence of iodoform is detected by its characteristic odor or by formation of crysts. Other ketones, as well as aldehydes and alcohol interfere and should be detd separately. Description of qualitative test is given in Ref 16, p 619... 

You will be given an unknown that may be any of the aldehydes or ketones listed in Table 1. At least one derivative of the unknown is to be submitted to the instructor but if you first do the bisulfite and iodoform characterizing tests, the results may suggest derivatives whose melting points will be particularly revealing. 

Iodoform, CHI3, tri-iodomethane, is formed when alcohol and certain other compounds (66) are treated with iodine in the presence of an alkali. It can be prepared by adding iodine to a warm aqueous solution of alcohol or acetone which contains sodium carbonate. The iodoform, which separates as a yellow precipitate, is purified by crystallization from dilute alcohol. It crystallizes in yellow, lustrous, six-sided plates, which melt at 119 , and have a peculiar, very characteristic odor. The reactions by which alcohol is converted into iodoform are analogous to those as the result of which chloroform is obtained from alcohol. The formation of iodoform is often used as a test for ethyl alcohol, but as other substances, such as acetone, isopropyl alcohol, and aldehyde yield iodoform when warmed in alkaline solution with iodine, the test is not reliable unless it is known that the other substances which respond to it are absent. Most of the compounds which yield iodoform when treated in this way contain the group CH3.C linked to oxygen. 

Among aldehydes, acetaldehyde is quite reactive. This reaction makes it possible to distinguish methyl ketones from methylcarbinols (both classes of substances give a positive iodoform reaction). As the reaction is carried out in an alkaline medium, certain substances are hydrolyzed and their products then give a positive test. Such substances are, for example, geminal dihalo derivatives (1,1-dichloroethane, 2,2-dibromopropane, 2,2-dibromo-but e) and certain methyl derivatives (oximes, addition compounds with hydrogen sulfite). 

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