For ketones

These coloration changes are given by most compounds which possess the -CHj-CO— group for further examples, see Tests 4 (a) and (b) for Ketones, p. 344. 

Sulphuric add test. Heat 0 5 g. of citric acid or a citrate with 1 ml. of H2SO4 CO and COg are evolved and the mixture turns yellow, but does not char. Acetone dicarboxylic acid, OC(CH2COOH)g, is also formed, and is tested for after heating the mixture for 1 minute cool, add a few ml. of water and make alkaline with NaOH solution. Add a few ml. of a freshly prepared solution of sodium nitroprusside and note the intense red coloration (see Test 4 a) for ketones, p. 346). 

Acetone-Alkali coloration. Dissob-e a few crystals in i-2 ml. of acetone and add a few drops of aqueous XaOlI solution. A deep violet coloration is produced, and is turned red by acetrc acid but destroyed by mineral acids (see Test 4(6) for Ketones, p. 346, and also Test 2(0) p. 274). 

The following experimental procedure is suitable for ketones boiling above 175-200°. 

This is then a general synthesis for ketones and the corresponding disconnection is... 

Organoaluminum compounds such as triphenylaluminum (527) are used for ketone synthesis[387]. On the other hand, the reaction of /-BuiAl affords the corresponding alcohol 528 by reductive carbonylation[388]. 

Ketones can be prepared by trapping (transmetallation) the acyl palladium intermediate 402 with organometallic reagents. The allylic chloride 400 is car-bonylated to give the mixed diallylic ketone 403 in the presence of allyltri-butylstannane (401) in moderate yields[256]. Alkenyl- and arylstannanes are also used for ketone synthesis from allylic chlorides[257,258]. Total syntheses of dendrolasin (404)f258] and manoalide[259] have been carried out employing this reaction. Similarly, formation of the ketone 406 takes place with the alkylzinc reagent 405[260],... 

A few of the common names acceptable for ketones m the lUPAC system are... 

Section 17 1 The substitutive lUPAC names of aldehydes and ketones are developed by identifying the longest continuous chain that contains the carbonyl group and replacing the final e of the corresponding alkane by al for aldehydes and one for ketones The chain is numbered m the direction that gives the lowest locant to the carbon of the carbonyl group... 

Reaction is acid catalyzed Equilibrium constant normally favorable for aide hydes unfavorable for ketones Cyclic acetals from vicinal diols form readily... 

As with other reversible nucleophilic addition reactions the equilibria for aldol additions are less favorable for ketones than for aldehydes For example only 2% of the aldol addition product of acetone is present at equilibrium... 

In a reaction related to the mixed Claisen condensation nonenolizable esters are used as acylatmg agents for ketone enolates Ketones (via their enolates) are converted to p keto esters by reaction with diethyl carbonate... 

The carbon-oxygen double bond of the carbonyl group is opened, and the hydrogen sulfite radical is added. An increase in temperature reverses the reaction more easily for ketones than for aldehydes. 

Ketones with aromatic nucleus 2.70 -760.65 -1- 50.478N Add to values of AN, AB calculated for ketone... 

The dienol is unstable, and two separate processes have been identified for ketonization. These are a 1,5-sigmatropic shift of hydrogen leading back to the enone and a base-catalyzed proton transfer which leads to the / ,y-enone. The deconjugated enone is formed because of the kinetic preference for reprotonation of the dienolate at the a carbon. Photochemical deconjugation is a synthetically useful way of effecting isomerization of a,) -unsaturated ketones and esters to the j ,y-isomers. 

As is clear from the preceding examples, there are a variety of overall reactions that can be initiated by photolysis of ketones. The course of photochemical reactions of ketones is veiy dependent on the structure of the reactant. Despite the variety of overall processes that can be observed, the number of individual steps involved is limited. For ketones, the most important are inter- and intramolecular hydrogen abstraction, cleavage a to the carbonyl group, and substituent migration to the -carbon atom of a,/S-unsaturated ketones. Reexamination of the mechanisms illustrated in this section will reveal that most of the reactions of carbonyl compounds that have been described involve combinations of these fundamental processes. The final products usually result from rebonding of reactive intermediates generated by these steps. 

Skladany, G.J., J.M. Thomas, G. Fisher and R. Ramachandran. The Design, Economics and Operation of a Biological Treatment System for Ketone Contaminated Ground and Solvent Recovery Process Waters. Presented at the 42nd Annual Purdue Industrial Waste Conference, Purdue University, West Lafayette, Indiana, 1987. 

Stereoselective epoxidation can be realized through either substrate-controlled (e.g. 35 —> 36) or reagent-controlled approaches. A classic example is the epoxidation of 4-t-butylcyclohexanone. When sulfonium ylide 2 was utilized, the more reactive ylide irreversibly attacked the carbonyl from the axial direction to offer predominantly epoxide 37. When the less reactive sulfoxonium ylide 1 was used, the nucleophilic addition to the carbonyl was reversible, giving rise to the thermodynamically more stable, equatorially coupled betaine, which subsequently eliminated to deliver epoxide 38. Thus, stereoselective epoxidation was achieved from different mechanistic pathways taken by different sulfur ylides. In another case, reaction of aldehyde 38 with sulfonium ylide 2 only gave moderate stereoselectivity (41 40 = 1.5/1), whereas employment of sulfoxonium ylide 1 led to a ratio of 41 40 = 13/1. The best stereoselectivity was accomplished using aminosulfoxonium ylide 25, leading to a ratio of 41 40 = 30/1. For ketone 42, a complete reversal of stereochemistry was observed when it was treated with sulfoxonium ylide 1 and sulfonium ylide 2, respectively. ... 

In a German patent issued in 1929, Bergs described a synthesis of some 5-substituted hydantoins by treatment of aldehydes or ketones (1) with potassium cyanide, ammonium carbonate, and carbon dioxide under several atmospheres of pressure at 80°C. In 1934, Bucherer et al. isolated a hydantoin derivative as a by-product in their preparation of cyanohydrin from cyclohexanone. They subsequently discovered that hydantoins could also be formed from the reaction of cyanohydrins (e.g. 3) and ammonium carbonate at room temperature or 60-70°C either in water or in benzene. The use of carbon dioxide under pressure was not necessary for the reaction to take place. Bucherer and Lieb later found that the reaction proceeded in 50% aqueous ethanol in excellent yields for ketones and good yields for aldehydes. ... 

Propose structures for ketones or aldehydes that have the following NMR spectra ... 

The real value of aldol dehydration is that removal of water from the reaction mixture can be used to drive the aldol equilibrium tow ard product. Even though the initial aldol step itself may be unfavorable, as it usually is for ketones, the subsequent dehydration step nevertheless allows many aldol condensations to be... 

Acetal (Section 19.10) A functional group consisting of two -OR groups bonded to the same carbon, R2C(OR )2-Acetals are often used as protecting groups for ketones and aldehydes. 

Test blood for glucose and urine for ketones as directed by the health care provider. Keep a record of test results and bring this record to each visit to the health care provider or clinic. 

Further oxidation of the product to a carboxylic acid (Section 19.6) can be avoided by using a mild oxidizing agent. There is less risk of further oxidation for ketones than for aldehydes, because a C—C bond would have to be broken for a carboxylic acid to form. 

Aldehydes and ketones For aldehydes, identify the parent hydrocarbon include the C of—CHO in the count of carbon atoms. Then change the final -e of the hydrocarbon name to -al. The C in the —CHO group is always carbon l, at the end of a carbon chain, and is not explicitly numbered. For ketones, change the -e of the parent hydrocarbon to -one and number the chain in the order that gives the carbonyl group the lower number. Thus, CH3CH2CH2COCH3 is 2-pentanone. 

---