GUEST AUTHORS Ralph Daniels, Clyde C. Rush, ‘ond Ludwig Bauer University of Hlinois Chicago 12 The we of the Felling and Benedict tests for dotecting aliphatic aldehydes is recommended by all writers of textbooks! and laboratory mantials in organic chemistry. These tests employ a solution of copper(II) ion in alkaline medium. To keep the test solution homogeneous, the eoneenteation of eopper(I1) ion is held low, through complex formation with tar- trate ion in the Fehling test solution and with citrate ion in the Benedict test. ‘The tests proper involve the addition of a substance to the test solution and heating the reaction mixture to 100°C. According to the standard textbooks, aldehydes are oxidized to the corresponding earboxylie acids with re- duction of the copper(II) ion to copper(I) oxide, appears asa yellow to red precipitate. When subjected to the same treatment, ketones are not supposed to re- duce copper(II) ion ‘and the test solutions retain their blue color. Therefore, these test if the texts are interpreted literally, aro presumed to difezentiate between aldehydes and ketones ‘This simple interpretation for the test. reactions is not in accord with experimental facts. While the test reae- tions are positive for aldoses and reducing sugars, we have fomd that extrapolation to simple aliphatic ale dehydes is unwarranted. Exploratory experiments in Suggestions of material suitable for this column and guest columns fuitable for publiestion directly. are eagerly solicited. ‘Th honld be sent with ne many detaile as possible, and particularly ‘with references to moner textbooks, to Kaeol 7 Mysels, Depart ment of Chemistry, University of Southern California, Los Angeles 7, Caloris. “Sinee the purpose of thie column is to prevent tho spread ancl continntion of errors and not the evaluation af individual texts the source of errors discussed will ot he eited. ‘Tho error must ‘occur in atleast two independent standard books to be presented. The standard conditions employed in our laboratory involve ‘eating the reaeon mixture for theee minutes in bailing water bath. Further experimental details will be reported Fully shen this study fs completa Textbook Errors, 24 The Fehling and Benedict Tests ‘our laboratory have shown that under standard condi- tions® the changes observed in treating a substance with the test reagents fall into three eategories: (1) A colorless: aqueous solution admixed with a yellow to red precipitate results. The precipitate is Cu.0; its formation represents @ positive test. (2) Complex changes occur, with formation of a red or dark-brown, gummy precipitate. Tn this ease, the supernatant liquid may be blue, green, brown, yellow, or orange. Nevertheless, this constitutes a negative test because experiments in our laboratory indieate that the precipitate isnot copper(I) oxide. Apparently these changes have been mistaken for a positive test. (3). The blue solution of the test reagent remains, with or without the presence of a colorless immiscible onganie layer. This is negative test. ‘We subjected several aldehydes and ketones to these tests and found that carbonyl compounds eould be classified aecording to the color changes deseribed above Category (1): ghicose and the reducing sugars, achydrosyadip= aldehyrle, glyoxal and pyruvic aldehyde, Category (2): acetaldehyie,erotonaldel ‘and aldo ‘Category (3): benzaldchyde and aromatic aldehydes in general, isobutyraldehyde, 2-ethyl-hexanol, and acetone, A tentative conclusion can be drawn from these pre~ liminary experiments: Copper(ID) ion in Febling or Benedict test. solution will be reduced to copper() oxide by achydroxyaldehydes, e-hydroxy ketones and. ‘o-ketoaldehydes. Other aldehydes and ketones do not produce copper(I) oxide. We have found that the Tol- Tens’ test reagent. (an aqueous solution of diammine silver(I) hydroxide) is infallible for distinguishing al dehydes from ketones le, cinnamaldehye, It iv noteworthy that the Fehling test solution gives rite to iw extensive changes than does the Benedict test solution. Tn the caeo of the Fehling test, « tee of eopper (1) oxide may bo fommod if an exees of test compound is employed. Volume 37, Number 4, April 1960 | 205