ALDEHYDES AND KETONES

ACETONE is the simplest and most common ketone in our lives. It is used in nail polish
remover, paints, varnishes, and resins.

The aldehydes and ketones are closely related classes of compounds. Their structures
contain the carbonyl group, C=O, a carbonoxygen double bond.
z

Aldehydes have at least one hydrogen atom bonded to the carbonyl group

Ketones have only alkyl or aryl (aromatic, denoted Ar) groups bonded to the carbonyl group IUPAC Rules for Naming Aldehydes 1. To establish the parent name, select the longest continuous chain of carbon atoms that contains the aldehyde group. 2. The carbons of the parent chain are numbered starting with the aldehyde group. Since the al dehyde group is at the beginning (or end) of a chain, it is understood to be number 1. 3. Form the parent aldehyde name by dropping the -e from the corresponding alkane name and adding the suffix -al. 4. Other groups attached to the parent chain are named and numbered as we have done before. The first member of the homologous series, H2C=O, is METHANAL.

The name methanal is derived from the hydrocarbon methane, which

contains one carbon atom. The second member of the series is ETHANAL, the third member is propanal, and so on.

IUPAC Rules for Naming Ketones 1. To establish the parent name, select the longest continuous chain of carbon atoms that contains the ketone group. 2. Form the parent name by dropping the -e from the corresponding alkane name and adding the suffix -one. 3. If the chain is longer than four carbons, it is numbered so that the carbonyl group has the smallest number possible; this number is prefixed to the parent name of the ketone. 4. Other groups attached to the parent chain are named and numbered as we have done before. Two of the MOST WIDELY USED KETONES have special common names:

Propanone is called ACETONE, and butanone is known as METHYL ETHYL KETONE, or

MEK. Bonding and Physical Properties The carbonyl group in aldehydes and ketones is very polar, with the oxygen pulling electrons from the carbon. Unlike alcohols, aldehydes and ketones do not hydrogen-bond to themselves. They have lower boiling points than alcohols of comparable molar mass. Aldehydes and ketones with four or fewer carbons are at least partly water-soluble. Lower-molar-mass aldehydes have a penetrating, disagreeable odor, while higher-molarmass aldehydes and ketones are more fragrant, some being used in flavorings and perfumes. Chemical Properties of Aldehydes and Ketones The carbonyl group ( C=O) is the functional group of both aldehydes and ketones.

Associated with every functional group are characteristic reactions. Aldehydes undergo both oxidation and reduction reactions; Ketones undergo reduction reactions.

 Aldehydes are easily oxidized (OXIDATION) to carboxylic acids. Under similar conditions, ketones are unreactive. In the Tollens test, Ag+ is reduced (REDUCTION) to form metallic silver as the aldehyde is oxidized. In the Fehling and Benedict tests, Cu2+ is reduced to form Cu2O, a reddish-brown precipitate. Both aldehydes and ketones can be reducedALDEHYDES yield primary alcohols, while KETONES yield secondary alcohols. A HEMIACETAL is formed when an alcohol adds across an aldehyde carbonyl double bond. If an alcohol adds to a ketone, a HEMIKETAL is produced. Common Aldehydes and Ketones 1. Formaldehyde (methanal) is produced from methanol by air oxidation and is used primarily in the manufacture of polymers.

A poisonous, irritating gas that is highly soluble in water.

It is marketed as a 37% aqueous solution called formalin, which also contains 1015% methanol

Formaldehyde vapors are intensely irritating to the mucous membranes. Ingestion may
cause severe abdominal pains, leading to coma and death. 2. Acetaldehyde (ethanal) is used to produce acetic acid and 1-butanol. A volatile liquid with a pungent, irritating odor. It has a general narcotic action and, in large doses, may cause respiratory paralysis. Its principal use is as an intermediate in the manufacture of other chemicals, such as acetic acid and 1-butanol. Found in humans following ethanol (alcohol) consumption. This aldehyde is produced in the liver as the first step in detoxifying ethanol. Unfortunately, acetaldehyde is also a toxin; in fact, much of the physiological impact of heavy drinking actually comes from acetaldehyde. Paraldehyde is a controlled substance and has been used as a sedative. Metaldehyde is very attractive and highly poisonous to slugs and snails. o o For this reason, it is an active ingredient in some pesticides that are sold for lawn and garden use. Metaldehyde is also used as a solid fuel.

3. Acetone and methyl ethyl ketone (MEK) are formed by oxidation from the secondary alcohols 2-propanol and 2-butanol, respectively. These ketones are excellent organic solvents and are found in many commercial products such as paints, lacquers, varnishes, and fingernail polish remover.

CARBOXYLIC ACIDS AND ESTERS

Whenever we eat food with a sour or tart taste, it is very likely that at least one carboxylic acid is present in that food. For example, citric acid is present in lemons, acetic acid is present in vinegar, and lactic acid is present in sour milk. Carboxylic acids are also important compounds in biochemistry: Citric acid is found in our blood Lactic acid is produced in our muscles during the breakdown of glucose. In the world around us, we use carboxylic acid salts as preservatives, especially in cheeses and breads, and to treat skin irritations like diaper rash and athletes foot. Carboxylic acid derivatives known as ESTERS are responsible for the sweet and pleasant odors and tastes of our food. We frequently use these compounds as artificial flavors in foods in place of more expensive natural extracts.

I. CARBOXYLIC ACIDS
The functional group of the carboxylic acids is called a CARBOXYL GROUP and is represented in the following ways: O C OH COOH or CO2H O C OH OH

Carboxylic acids can be either aliphatic or aromatic O RC OH O CH3C OH O ArC

A. Nomenclature and Sources of Aliphatic Carboxylic Acids

Unfortunately, the IUPAC method is neither the only nor the most-used method for naming acids.

Organic acids are usually known by COMMON NAMES: i. Methanoic, ethanoic, and propanoic acids are called formic, acetic, and propionic acids, respectively. These names often refer to a natural source of the acid and are not systematic. FORMIC ACID gets its name from the Latin word formica, meaning ant. This acid contributes to the stinging sensation of ant bites. ACETIC ACID is found in vinegar and gets its name from the Latin word for vinegar. The name BUTYRIC ACID comes from the Latin term for butter, since it is a constituent of butterfat. ii. The 6-, 8-, and 10-carbon acids are found in goat fat; their names are derived from the Latin word for goat. These three acidscaproic, caprylic, and capricalong with butyric acid have characteristic and disagreeable odors. iii. In a similar way, the names of the 12-, 14-, and 16-carbon acidslauric, myristic, and palmiticcome from plants from which the corresponding acid has been isolated. The name stearic acid comes from a Greek word meaning beef fat or tallow, which is a good source of this acid.

iv.

Many of the carboxylic acidsprincipally, those with even numbers of carbon atoms ranging from 4 to about 20 exist in combined form in plant and animal fats. These are called fatty acids.

v.

Another nomenclature method uses letters of the Greek alphabet (, , , .) to name certain acid derivatives, especially hydroxy, amino, and halogen acids. When Greek letters are used, the carbon atoms, beginning with the one adjacent to the carboxyl group, are labeled , , , .

vi.

When numbers are used (the IUPAC System), the numbers begin with the carbon in the COOH group.

B. Physical Properties of Carboxylic Acids Carboxyl groups can also hydrogen-bond to each other at two places. This strong noncovalent bonding causes high boiling points for carboxylic acids. Smaller saturated monocarboxylic acids (less than 10 carbons) are liquids at room temperature, while larger carboxylic acids (greater than 10 carbons) are solids. Carboxylic acids are weak acids; the carboxylic acid is in equilibrium with its conjugate base. Since carboxylic acids are common in biochemistry, their ionization can have important physiological consequences: a. METABOLIC ACIDOSIS, a life-threatening condition, is related to carboxylic acid ionization. o o o Whenever central energy metabolism is active, carboxylic acids are produced. As the acids are formed, they release hydrogen ions. Under most circumstances, this extra acidity is controlled by readjustments of lung and kidney function. o However, if too many acids are formed, blood acidity goes out of control and metabolic acidosis develops. o Just a small drop in blood pH (to a Ph of below about 7.3) may lead to shock or death. o Conditions that result in metabolic acidosis include uncontrolled diabetes, kidney failure, and ethylene glycol poisoning.

C. Classification of Carboxylic Acids Various other kinds of carboxylic acids are known 1. Unsaturated Carboxylic Acids

An unsaturated acid contains one or more carboncarbon double bonds. The first member of the homologous series of unsaturated carboxylic acids that contains
one carboncarbon double bond is ACRYLIC ACID, CH2=CHCOOH.

The IUPAC name for CH2=CHCOOH is PROPENOIC ACID.

2. Aromatic Carboxylic Acids

In an aromatic carboxylic acid, the carbon of the carboxyl group (

directly to a carbon in an aromatic ring.

COOH) is bonded

The parent compound of this series is benzoic acid.

3. Dicarboxylic Acids

Acids of both the aliphatic and aromatic series that contain two or more carboxyl groups
are known.

Those with two COOH groups are called DICARBOXYLIC ACIDS. The simplest member of the aliphatic series is OXALIC ACID.

Oxalic acid is found in various plants, including spinach, cabbage, and rhubarb. Among its many uses are bleaching straw and leather and removing rust and ink stains. Although oxalic acid is poisonous, the amounts present in the previously mentioned vegetables are usually not harmful.

The next member in the homologous series is malonic acid.

Malonic acid is now made synthetically but was originally prepared from malic acid, which is commonly found in apples and many fruit juices.

The IUPAC names for dicarboxylic acids are formed by modifying the corresponding
hydrocarbon names to end in -dioic acid.

Thus, the two-carbon acid is ethanedioic acid (derived from ethane).

Names and Formulas of Selected Dicarboxylic Acids COMMON NAME Oxalic acid Malonic acid Succinic acid Glutaric acid Adipic acid Pimelic acid Fumaric acid Maleic acid 4. Hydroxy Acids IUPAC NAME Ethanedioic acid Propanedioic acid Butanedioic acid Pentanedioic acid Hexanedioic acid Heptanedioic acid trans-2-Butenedioic acid cis-2-Butenedioic acid FORMULA HOOCCOOH HOOCCH2COOH HOOC(CH2)2COOH HOOC(CH2)3COOH HOOC(CH2)4COOH HOOC(CH2)5COOH HOOCCH=CHCOOH HOOCCH=CHCOOH

Lactic acid, found in sour milk, sauerkraut, and dill pickles, has the functional groups of
both a carboxylic acid and an alcohol.

Lactic acid is the end product when our muscles use glucose for energy in the absence of
oxygen, a process called glycolysis.

Salicylic acid is both a carboxylic acid and a phenol. It is of special interest because a family of useful drugsthe salicylatesare
derivatives of this acid.

The salicylates include aspirin and function as analgesics (pain relievers) and as
antipyretics (fever reducers). 5. Amino Acids

The BIG DADDY of all carboxylic acids.

 About 20 biologically important amino acids, each with a different group represented by R,
are found in nature. (In amino acids, R does not always represent an alkyl group.)

The immensely complicated protein molecules, found in every form of life, are built from
amino acids D. Chemical Properties of Carboxylic Acids

Because the carboxyl group is a WEAK ACID, carboxylic acids have a sour taste, affect
pH indicators, form water solutions with a pH of less than 7, and undergo neutralization reactions.

Carboxylic acids react with bases to form salts. Sodium and potassium salts of carboxylic acids are water soluble. This property is used to distinguish carboxylic acids from other organic compounds.

II. ESTER
An ESTER is an organic compound formed by the reaction of an acid with an alcohol or a phenol

The forward reaction of an acid and an alcohol is called ESTERIFICATION The reverse reaction of an ester with water is called HYDROLYSIS. Esterification is one of the most important reactions of carboxylic acids.

A. Nomenclature of Esters

The general formula for an ester is RCOOR, where R may be a hydrogen, an alkyl group,
or an aryl group and R may be an alkyl group or an aryl group, but not a hydrogen.

Esters are found throughout nature. Esters are alcohol derivatives of carboxylic acids. They are named in much the same way as salts. The alcohol part is named first, followed by the name of the acid modified to end in
-ate.

The -ic ending of the organic acid name is replaced by the ending -ate. Thus, in the IUPAC System, ethanoic acid becomes ethanoate. In the common names, acetic acid becomes acetate

Names, and Odors of Selected Esters IUPAC name Isopentyl ethanoate Ethyl butanoate Isobutyl methanoate Octyl ethanoate Methyl 2-hydroxybenzoate Common name Isoamyl acetate Ethyl butyrate Isobutyl formate Octyl acetate Methyl salicylate Odor or flavor Banana, pear Pineapple Raspberry Orange Wintergreen

B. Occurrence and Physical Properties of Esters

Low- to intermediate-molar-mass esters are liquids with characteristically fruity or

fragrant aromas.

Esters such as ethyl acetate, butyl acetate, and isoamyl acetate are good solvents and
commonly used in paints, varnishes, and lacquers. C. Chemical Properties of Esters

The most important reaction of esters is hydrolysiswater is used to split esters into alcohols
and carboxylic acids.

Adding a strong acid (e.g., HCl, H2SO4) will speed up hydrolysisacid hydrolysis. When a strong base is used to speed up hydrolysis, the process is called alkaline hydrolysis or saponification. Alkaline hydrolysis yields a carboxylic acid salt. This reaction is called SAPONIFICATION because a soap is formed when the carboxylic acid salt has a long alkyl chain.

D. Glycerol Esters

Fats and oils are esters of glycerol and predominantly LONG-CHAIN CARBOXYLIC
ACIDS (fatty acids).

A triacylglycerol or triglyceride is a glycerol that has been esterified with three fatty acids,
generally three different fatty acids.

Fatty acids generally have long carbon chains (4 to about 20 carbon atoms) and almost
always contain an even number of carbons.

Fatty acids may be either saturated or unsaturated, with from one to four double bonds. Fatty acid double bonds are generally cis isomers. Fats are solids at room temperature, while oils are liquids Triacylglycerols are the principal energy-storage molecules in the human body. Unsaturated fatty acids yield saturated fatty acids. Low-cost vegetable oils form fats.
E. Soaps and Synthetic Detergents

In the broadest sense possible, a detergent is simply a cleansing agent. Soap has been used as a cleansing agent for at least 2000 years and is thereby classified
as a detergent under this definition.

However, beginning about 1930, a number of new cleansing agents that were superior in
many respects to ordinary soap began to appear on the market.

Because they were both synthetic organic products and detergents, they were called
synthetic detergents, or syndets.

A soap is distinguished from a synthetic detergent on the basis of chemical composition,

not on the basis of function or usage. Soaps

 Salts of long-chain fatty acids are called soaps. However, only the sodium and potassium salts
Fat or oil + NaOH = soap + glycerol

of carboxylic acids that contain 1218 carbon atoms are of great value as soaps, because of their abundance in fats. The reaction proceeds as follows:

The

fatty acid anion combines properties described as hydrophilic (water-loving) and a hydrophobic (water-fearing) group.

The hydrophilic end is the polar, negatively charged carboxylate group. The hydrophobic end is the long hydrocarbon group. Thehydrocarbon group is soluble in oils and greases, but not in water. The hydrophilic carboxylate group is soluble in water.

The cleansing action of a soap is explained in this fashion:

When the soap comes into contact with grease on a soiled surface, the hydrocarbon end of the soap dissolves in the grease, leaving the negatively charged carboxylate end exposed on the grease surface.

Because the negatively charged carboxylate groups are strongly attracted by water, small droplets are formed, and the grease is literally lifted or floated away from the soiled object.

The cleansing property of a soap is due to its ability to act as an emulsifying agent
between water and water-insoluble greases and oils.

Ordinary soap is a good cleansing agent in soft water, but it is not satisfactory in hard
water because insoluble calcium, magnesium, and iron salts are formed.

Synthetic detergents also combine hydrophilic and hydrophobic properties. Long alkyl chains contribute the hydrophobic property. Most detergents produced today are biodegradable. Biodegradable
refers to organic microorganisms in the environment. substances that are readily decomposed by

Soap and Fighting Infection

Our skin is constantly collecting microorganisms as we go through each day. Both bacteria and viruses adhere to outer skin layers, attaching to breaks between skin
cells and sticking to skin oils.

These microbes can then be transferred from hands to mouth or nasal passages or eyes,
continuing the chain of infection.

To stop this process, it might be anticipated that a potent antibacterial agent is needed. The best way to break the chain of infection is handwashing for about 20 seconds with
soap and water.

The soap breaks the adhesion between pathogens and the skin in the same way it
dissolves grease.