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The document summarizes key information about carbonyl compounds, specifically aldehydes and ketones. It discusses their structures, naming conventions, methods of preparation from alcohols, physical and chemical properties, and common uses. Aldehydes contain a carbonyl group bonded to the first carbon in an alkyl chain, while ketones have the carbonyl group within the chain. Both can be prepared by oxidizing primary or secondary alcohols, respectively. Their properties include solubility in water, boiling points, and participation in reactions like reductions, additions, and condensations. Common aldehydes and ketones are used as solvents, flavors, fragrances, and in chemical synthesis.
The document summarizes key information about carbonyl compounds, specifically aldehydes and ketones. It discusses their structures, naming conventions, methods of preparation from alcohols, physical and chemical properties, and common uses. Aldehydes contain a carbonyl group bonded to the first carbon in an alkyl chain, while ketones have the carbonyl group within the chain. Both can be prepared by oxidizing primary or secondary alcohols, respectively. Their properties include solubility in water, boiling points, and participation in reactions like reductions, additions, and condensations. Common aldehydes and ketones are used as solvents, flavors, fragrances, and in chemical synthesis.
The document summarizes key information about carbonyl compounds, specifically aldehydes and ketones. It discusses their structures, naming conventions, methods of preparation from alcohols, physical and chemical properties, and common uses. Aldehydes contain a carbonyl group bonded to the first carbon in an alkyl chain, while ketones have the carbonyl group within the chain. Both can be prepared by oxidizing primary or secondary alcohols, respectively. Their properties include solubility in water, boiling points, and participation in reactions like reductions, additions, and condensations. Common aldehydes and ketones are used as solvents, flavors, fragrances, and in chemical synthesis.
The carbonyl group is formed by joining together the
C atom and the O atom by a double bond.
Compounds having the aldehyde and ketone functional groups are named carbonyl compounds. Differences among aldehydes and ketones are due to the positioning of the carbonyl group in their molecules. The C=O group in aldehydes is always located at the end of the alkyl stem, so aldehydes can be represent as
R C H O Unlike aldehydes, the ketone carbonyl group is situated away from the ends of the parent carbon chain. This means that the carbonyl group in ketones is sandwiched between two alkyl stems and is represented as
The group stamped a polar region in the aldehyde and ketone molecules. Most reactions of aldehydes and ketones will be centred at the carbonyl group.
R C R O Nomenclature: The names of aldehydes and ketones are simply derived by dropping "-e" from the root and adding "-al" or "-one" respectively. A position number is needed for ketones since the carbonyl group may be on any number of several carbons in the "middle" of a chain. The carbonyl on the aldehyde is always on the number one carbon so no position number is needed.
Aldehyde -al Propanal Ketone -one Propanone or acetone (common name) Preparation of Aldehydes and Ketones Aldehydes can be prepared by the oxidation of primary alcohols with hot, acidified potassium manganate (VII) solution or potassium dichromate(VI) solution.
R-C-OH + (O) R-C=O + H2O H H H aldehyde Ketones are prepared by the oxidation of secondary alcohols by hot acidified KMnO4 solution. Ketones resist oxidation, thus distillation is not required.
R1-C-OH + (O) R1-C=O + H2O R2 H R2 Ketone Physical Properties of Aldehydes and Ketones Physical Properties of Aldehydes and Ketones a). Solubility in water The small aldehydes and ketones are freely soluble in water but solubility falls with chain length. For example, methanal, ethanal and propanone - the common small aldehydes and ketones - are miscible with water in all proportions. The reason for the solubility is that although aldehydes and ketones can't hydrogen bond with themselves, they can hydrogen bond with water molecules.
As chain lengths increase, the hydrocarbon "tails" of the molecules start to get in the way. By forcing themselves between water molecules, they break the relatively strong hydrogen bonds between water molecules without replacing them by anything as good. This makes the process energetically less profitable, and so solubility decreases.
b). Boiling points The other aldehydes and the ketones are liquids, with boiling points rising as the molecules get bigger. The size of the boiling point is governed by the strengths of the intermolecular forces. The other aldehydes and the ketones are liquids, with boiling points rising as the molecules get bigger. The size of the boiling point is governed by the strengths of the intermolecular forces.
c). Density of aldehyde and ketones is lesser than water. d). Aldehydes and ketones are polar molecules. The bond angles and hybridization are the same. They also have dipole-dipole intermolecular bonding. Because of this, they are held together with greater attraction than you would find with alkanes of similar size and molecular weight. e). They dont have hydrogen bonding but form hydrogen bonding with the compound which have hydrogen bonding. f). They are excellent organic solvents.
Chemical Properties of Aldehydes and Ketones Chemical Properties of Aldehydes and Ketones Reduction Variety of agents can reduce aldehydes and ketones to alcohols NaBH 4 and H 2 commonly used
Condensation Reactions Aldehydes and ketones react with derivatives of ammonia in condensation reactions. Aldehydes and ketones react with hydroxylamine at room temperature to form an oxime. C= O+ H2N- ON C=N-OH+H2O hydroxylamine oxime Aldehydes and ketones react with hydrazine at room temperature to form a hydrazone. C= O+ H2N- NH C=N-OH+H2O hydrazine hydrazone Aldehydes and ketones react with phenylhydrazine, at room temperature to form a phenylhydration. C= O+ H2N- H- C=N-N- + H2O H H phenylhydrazine phenyldrazone The most important condensation reaction is with 2, 4-dinitrophenyldrazine to form a yellow- orange precipatate of 2, 4- dinitrophenylhydrazone. O2N O2N C= O+ H2N- H- NO2 C=N-N- NO2+ H2O H H
A solution of 2, 4- dinitrophenylhydrazine in methanol and sulphuric acid is called Bradys reagent. The formation of a yellow- orange precipitate is a chemical test for the presence of the carbonyl group in aldehydes and ketones.
2, 4-dinitrophenyldrazine 2, 4- dinitrophenylhydrazone Hydration Formaldehyde dissolves readily in water Acetaldehyde somewhat also Form hydrates
Addition Reactions Aldehydes and ketones react with hydrogen cyanide in sodium hydroxide solution at 10-20 celcius to form cyanohydrin. H H CH3-C=O+H-C= N CH3-C-OH C= 2- hydroxypropanenitrile (ethanal cyanohydrin) The reaction can also be carried put by adding dilute sulphuric acid to a mixture of carbonyl compound and potassium cyanide at 10-20 celcius. The CN group in cyanohydrin can be hydrolysed by heating with a dilute acid to form a hydroxyacid. This is a method to prepare 2- hydroxycarboxylic acid. H + H CH3-C=OH+H-H2O CH3-C-OH C= N COOH 2-hydroxycarboxylic acid This is a useful way to add a carbon atom to the carbon chain. The CN group can also be reduced to an amine group using hydrogen gas in the presence of hot nickel catalyst or by using lithium tetrahydridoaluminate (III)
Oxidation Aldehydes are oxidised rather easily to carboxylic acids by heating with acidified potassium manganate (VII) or potassium dichromate (VI) solution. H OH R-C=O+[O] R-C=O Aldehyde carboxylic acid In alkaline conditions, the aldehyde is oxidised to the salt of the corresponding carboxylic acid. The carboxylic acid is formed upon addition of a dilute acid. H O- R-C=O+[O]+OH- R-C=O+H2O Aldehyde salt of carboxylic acid O OH R-C=O+H+ R-C=O carboxylic acid Benzaldehyde is oxidised to benzoic acid, which is soluble in hot water, but when cooled, will precipitate out as a white solid. H OH -C=O+[O] -C=O Benzaldehyde benzoic acid
Ketones resist oxidation under normal conditions. However they undergo oxidative cleavage when boiled for a long time to form a mixture of products. There will be a loss of carbon atoms in the form of carbon dioxide. An important industrial application of the oxidation of ketones is the oxidation of cyclohexanone by nitric acid to hexanedioic acid, which is a monomer in the synthesis of nylon-6,6.
O O O HO-C-CH2CH2CH2CH2-C-OH
cyclohexanone hexanedioic acid Tollens reagent When adding the aldehyde or ketone to Tollens' reagent, the test tube is put in a warm water bath. If the reactant under test is an aldehyde, Tollens' test results in a silver mirror. If the reactant is a ketone, it will not react because a ketone cannot be oxidized easily. A ketone has no available hydrogen atom on the carbonyl carbon that can be oxidized - unlike an aldehyde, which has this hydrogen atom.
Fehling reagent An aldehyde is added to the Fehling solution and the mixture is heated. The aldehyde oxidizes to an acid and cupric ions, which were complexed with the tartrate ion, are reduced to cuprous ions, which precipitate as red cuprous oxide. Ketones (except alpha hydroxy ketones such as are present in ketoses and other metabolites) and aromatic aldehydes do not respond to the Fehling test. Benedict's test Benedict's reagent will detect the presence of aldehydes. Benedict's reagent contains blue copper(II) ions (Cu 2+ ) which are reduced to copper(I) (Cu + ). These are precipitated as red copper(I) oxide which is insoluble in water.
Uses of Aldehydes and Ketones
Hundreds of aldehydes and ketones are used as flavoring, odouring and preserving agents e.g., vanillin and cinnamonaldehyde (flavors). Glyceraldehyde is an intermediate in carbohydrate metabolism and testosterone and progesterone are hormones that relate to the biological role of these compounds. Aldehydes and ketones are being used by chemists daily basically to synthesize other compounds. In industry these compounds are used as solvents. Uses of Aldehydes A 40% formaldehyde known as formalin solution can be used to preserve dead animals. It is also used in the manufacture of polymeric plastics like bakelite, melamine and urea- formaldehyde glues. Formaldehyde is used in the tanning of leather, decolouring of vat dyes and as a reducing agent in silvering of mirrors. It is also used in manufacture of plywood. Paraldehyde is a sweet smelling liquid used in medicine as a hypnotic.
Acetaldehyde is used primarily as a starting material in the manufacture of acetic acid, ethyl acetate, vinyl acetate, polymers and drugs.
It is also used in silvering of mirrors.
Mataldehyde a polymer of acetaldehyde is used as a solid fuel and for killing slugs when mixed with bran.
Benzaldehyde is an almond extract used as a flavoring agent as well as in perfumery.
It is used in the manufacture of dyes like malachite green.
In the chemical industry it is also used as a starting material for making a number of organic compounds such as cinnamic acid, benzoic acid, benzoyl chloride etc.
Uses of ketones Acetone is a common fingernail polish remover and is a solvent for lacquers and varnishes. Acetone is used as a cleaning fluid and is very flammable. It is also used to prepare a number of compounds such as chloroform, ketene acetic anhydride etc. It finds further use in the manufacture of smokeless powders cordite, celluloid. 2-Butanone (MEK, methyl ethyl ketone) finds use as a solvent and paint stripper. Carvone is used as spearmint flavoring. It is used as caraway seed flavoring.