uses, see Ester (disambiguation). This article may be too technical for most readers to understand.

Please help improve this article to make it understandable to non-experts, without removing the technical details. The talk page may contain suggestions. (March 2013)

A carboxylate ester. R and R' denote any alkyl or aryl group Esters are chemical compounds consisting of a carbonyl adjacent to an ether linkage. They are derived by reacting an oxoacid with a hydroxyl compound such as an alcohol or phenol.[1] Esters are usually derived from an inorganic acid or organic acid in which at least one -OH (hydroxyl) group is replaced by an -O-alkyl (alkoxy) group, and most commonly from carboxylic acids and alcohols.[contradiction] That is, esters are formed by condensing an acid with an alcohol. Esters are ubiquitous. Most naturally occurring fats and oils (e.g. triglycerides) are the fatty acid esters of glycerol. Esters with low molecular weight are commonly used as fragrances and found in essential oils and pheromones. Phosphoesters form the backbone of DNA molecules. Nitrate esters, such as nitroglycerin, are known for their explosive properties, while polyesters are important plastics, with monomers linked by ester moieties.

Contents
[hide]

1 Nomenclature o 1.1 Etymology o 1.2 IUPAC nomenclature of Esters o 1.3 Orthoesters o 1.4 "Inorganic esters" 2 Structure and bonding 3 Physical properties and characterization o 3.1 Characterization and analysis 4 Applications and occurrence 5 Preparation o 5.1 Esterification of carboxylic acids o 5.2 Alcoholysis of acyl chlorides and acid anhydrides o 5.3 Alkylation of carboxylate salts o 5.4 Transesterification o 5.5 Carbonylation o 5.6 Addition of carboxylic acids to alkenes

5.7 Other methods 6 Reactions o 6.1 Addition of nucleophiles at carbonyl o 6.2 Reduction o 6.3 Claisen condensation and related reactions o 6.4 Other reactions o 6.5 Protecting groups 7 List of ester odorants 8 See also 9 References 10 External links

Nomenclature[edit]
Etymology[edit]
The word 'ester' was coined in 1848 by German chemist Leopold Gmelin,[2] probably as a contraction of the German Essigther - acetic ether.

IUPAC nomenclature of Esters[edit]

Main article: IUPAC nomenclature of organic chemistry#Esters Ester names are derived from the parent alcohol and the parent acid, where the latter may be an organic or an inorganic acid. Esters derived from the simplest carboxylic acids are commonly named according to the more traditional, so-called "trivial names" e.g. as formate, acetate, propionate, and butyrate, as opposed to the IUPAC nomenclature methanoate, ethanoate, propanoate and butanoate. Esters derived from more complex carboxylic acids are, on the other hand, more frequently named using the systematic IUPAC name, based on the name for the acid followed by the suffix -oate. For example the ester hexyl octanoate, also known under the trivial name hexyl caprylate, has the formula CH3(CH2)6CO2(CH2)5CH3.

Ethyl acetate derived from an alcohol (blue) and an acyl group (yellow) derived from a carboxylic acid.

The chemical formulas of organic esters are typically written in the format of RCO2R', where R and R' are the hydrocarbon parts of the carboxylic acid and alcohol, respectively. For example butyl acetate (systematically butyl ethanoate), derived from butanol and acetic acid (systematically ethanoic acid) would be written CH3CO2C4H9. Alternative presentations are common including BuOAc and CH3COOC4H9. Cyclic esters are called lactones, regardless of whether they are derived from an organic or an inorganic acid. One example of a (organic) lactone is gamma-valerolactone.

Orthoesters[edit]
An uncommon class of organic esters are the orthoesters, which have the formula RC(OR')3. Triethylorthoformate (HC(OC2H5)3) is derived, in terms of its name (but not its synthesis) from orthoformic acid (HC(OH)3) and ethanol.

"Inorganic esters"[edit]

A phosphoric acid ester Ester is a general term for the product derived from the condensation of an acid and an alcohol. Thus, the nomenclature extends to inorganic oxo acids, e.g. phosphoric acid, sulfuric acid, nitric acid and boric acid. For example, triphenyl phosphate is the ester derived from phosphoric acid and phenol. Organic carbonates, such as ethylene carbonate, are derived from carbonic acid and ethylene glycol.

Structure and bonding[edit]

Esters contain a carbonyl center, which gives rise to 120C-C-O and O-C-O angles. Unlike amides, esters are structurally flexible functional groups because rotation about the C-O-C bonds has a low barrier. Their flexibility and low polarity is manifested in their physical properties; they tend to be less rigid (lower melting point) and more volatile (lower boiling point) than the corresponding amides.[3] The pKa of the alpha-hydrogens on esters is around 25.[4]

Physical properties and characterization[edit]

Esters are more polar than ethers but less polar than alcohols. They participate in hydrogen bonds as hydrogen-bond acceptors, but cannot act as hydrogen-bond donors, unlike their parent alcohols. This ability to participate in hydrogen bonding confers some water-solubility. Because of their lack of hydrogen-bond-donating ability, esters do not self-associate. Consequently esters are more volatile than carboxylic acids of similar molecular weight.[3]

Characterization and analysis[edit]

Esters are usually identified by gas chromatography, taking advantage of their volatility. IR spectra for esters feature an intense sharp band in the range 17301750 cm1 assigned to C=O. This peak changes depending on the functional groups attached to the carbonyl. For example, a benzene ring or double bond in conjugation with the carbonyl will bring the wavenumber down about 30 cm1.

Applications and occurrence[edit]

Esters are widespread in nature and are widely used in industry. In nature, fats are, in general, triesters derived from glycerol and fatty acids.[5] Esters are responsible for the aroma of many fruits, including apples, durians, pears, bananas, pineapples, and strawberries.[6] Several billion kilograms of polyesters are produced industrially annually, important products being polyethylene terephthalate, acrylate esters, and cellulose acetate.[7]

Representative triglyceride found in a linseed oil, a triester (triglyceride) derived of linoleic acid, alpha-linolenic acid, and oleic acid.

Preparation[edit]
Esterification is the general name for a chemical reaction in which two reactants (typically an alcohol and an acid) form an ester as the reaction product. Esters are common in organic chemistry and biological materials, and often have a characteristic pleasant, fruity odor. This leads to their extensive use in the fragrance and flavor industry. Ester bonds are also found in many polymers.

Esterification of carboxylic acids[edit]

The classic synthesis is the Fischer esterification, which involves treating a carboxylic acid with an alcohol in the presence of a dehydrating agent:

RCO2H + R'OH

RCO2R' + H2O

The equilibrium constant for such reactions is about 5 for typical esters, e.g., ethyl acetate.[8] The reaction is slow in the absence of a catalyst. Sulfuric acid is a typical catalyst for this reaction. Many other acids are also used such as polymeric sulfonic acids. Since esterification is highly reversible, the yield of the ester can be improved using Le Chatelier's principle:

using the alcohol in large excess (i.e., as a solvent) using a dehydrating agent: sulfuric acid not only catalyzes the reaction but sequesters water (a reaction product). Other drying agents such as molecular sieves are also effective. removal of water by physical means such as distillation as a low-boiling azeotropes with toluene, in conjunction with a Dean-Stark apparatus.

Reagents are known that drive the dehydration of mixtures of alcohols and carboxylic acids. One example is the Steglich esterification, which is a method of forming esters under mild conditions. The method is popular in peptide synthesis, where the substrates are sensitive to harsh conditions like high heat. DCC (dicyclohexylcarbodiimide) is used to activate the carboxylic acid to further reaction. DMAP (4-dimethylaminopyridine) is used as an acyl-transfer catalyst.[9]

Another method for the dehydration of mixtures of alcohols and carboxylic acids is the Mitsunobu reaction: RCO2H + R'OH + P(C6H5)3 + R2N2 RCO2R' + OP(C6H5)3 + R2N2H2 Carboxylic acids can be esterified using diazomethane: RCO2H + CH2N2 RCO2CH3 + N2 Using this diazomethane, mixtures of carboxylic acids can be converted to their methyl esters in near quantitative yields, e.g., for analysis by gas chromatography. The method is useful in specialized organic synthetic operations but is considered too expensive for large scale applications.

Alcoholysis of acyl chlorides and acid anhydrides[edit]

Alcohols react with acyl chlorides and acid anhydrides to give esters: RCOCl + R'OH RCO2R' + HCl (RCO)2O + R'OH RCO2R' + RCO2H

The reactions are irreversible simplifying work-up. Since acyl chlorides and acid anhydrides also react with water, anhydrous conditions are preferred. The analogous acylations of amines to give amides are less sensitive because amines are stronger nucleophiles and react more rapidly than does water. This method is employed only for laboratory-scale procedures, as it is expensive.

Alkylation of carboxylate salts[edit]

Although not widely employed for esterifications, salts of carboxylate anions can be alkylating agent with alkyl halides to give esters. In the case that an alkyl chloride is used, an iodide salt can catalyze the reaction (Finkelstein reaction). The carboxylate salt is often generated in situ. In difficult cases, the silver carboxylate may be used, since the silver ion coordinates to the halide aiding its departure and improving the reaction rate. This reaction can suffer from anion availability problems and, therefore, can benefit from the addition of phase transfer catalysts or highly polar aprotic solvents such as DMF.

Transesterification[edit]
Transesterification, which involves changing one ester into another one, is widely practiced: RCO2R' + CH3OH RCO2CH3 + R'OH Like the hydrolysation, transesterification is catalysed by acids and bases. The reaction is widely used for degrading triglycerides, e.g. in the production of fatty acid esters and alcohols. Poly(ethylene terephthalate) is produced by the transesterification of dimethyl terephthalate and ethylene glycol:[7] (C6H4)(CO2CH3)2 + 2 C2H4(OH)2 1/n {(C6H4)(CO2)2(C2H4)}n + 2 CH3OH

Carbonylation[edit]
Alkenes undergo "hydroesterification" in the presence of metal carbonyl catalysts. Esters of propionic acid are produced commercially by this method: C2H4 + ROH + CO C2H5CO2R The carbonylation of methanol yields methyl formate, which is the main commercial source of formic acid. The reaction is catalyzed by sodium methoxide: CH3OH + CO CH3O2CH

Addition of carboxylic acids to alkenes[edit]

In the presence of palladium-based catalysts, ethylene, acetic acid, and oxygen react to give vinyl acetate: C2H4 + CH3CO2H + 1/2 O2 C2H3O2CCH3 + H2O

Direct routes to this same ester are not possible because vinyl alcohol is unstable.

Other methods[edit]

Favorskii rearrangement of -haloketones in presence of base Baeyer-Villiger oxidation of ketones with peroxides Pinner reaction of nitriles with an alcohol Nucleophilic abstraction of a metal-acyl complex Hydrolysis of orthoesters in aqueous acid Cellulolysis via esterification [10]

Reactions[edit]
Esters react with nucleophiles at the carbonyl carbon. The carbonyl is weakly electrophilic but is attacked by strong nucleophilies (amines, alkoxides, hydride sources, organolithium compounds, etc.). The C-H bonds adjacent to the carbonyl are weakly acidic but undergo deprotonation with strong bases. This process is the one that usually initiates condensation reactions. The carbonyl oxygen is weakly basic (less so than in amides) but forms adducts.

Addition of nucleophiles at carbonyl[edit]

Esterification is a reversible reaction. Esters undergo hydrolysis under acid and basic conditions. Under acidic conditions, the reaction is the reverse reaction of the Fischer esterification. Under basic conditions, hydroxide acts as a nucleophile, while an alkoxide is the leaving group. This reaction, saponification, is the basis of soap making.

The alkoxide group may also be displaced by stronger nucleophiles such as ammonia or primary or secondary amines to give amides: RCO2R' + NH2R" RCONHR" + R'OH This reaction is not usually reversible. Hydrazines and hydroxylamine can be used in place of amines. Esters can be converted to isocyanates through intermediate hydroxamic acids in the Lossen rearrangement. Sources of carbon nucleophiles, e.g., Grignard reagents and organolithium compounds, add readily to the carbonyl.

Reduction[edit]
Compared to ketones and aldehydes, esters are relatively resistant to reduction. The introduction of catalytic hydrogenation in the early part of the 20th century was a breakthrough; esters of fatty acids are hydrogenated to fatty alcohols. RCO2R' + 2 H2 RCH2OH + R'OH A typical catalyst is copper chromite. Prior to the development of catalytic hydrogenation, esters were reduced on a large scale using the Bouveault-Blanc reduction. This method, which is largely obsolete, uses sodium in the presence of proton sources. Especially for fine chemical syntheses, lithium aluminium hydride is used to reduce esters to two primary alcohols. The related reagent sodium borohydride is slow in this reaction. DIBAH reduces esters to aldehydes.[11]

Claisen condensation and related reactions[edit]

As for aldehyde and aldehydes, the hydrogen atoms on the carbon adjacent (" to") the carboxyl group in esters are sufficiently acidic to undergo deprotonation, which in turn leads to a variety of useful reactions. Deprotonation requires relatively strong bases, such as alkoxides. Deprotonation gives a nucleophilic enolate, which can further react, e.g., the Claisen condensation and its intramolecular equivalent, the Dieckmann condensation. This conversion is exploited in the malonic ester synthesis, wherein the diester of malonic acid reacts with an electrophile (e.g., alkyl halide), and is subsequently decarboxylated. Another variation is the FrterSeebach alkylation.

Other reactions[edit]

Phenyl esters react to hydroxyarylketones in the Fries rearrangement. Specific esters are functionalized with an -hydroxyl group in the Chan rearrangement. Esters with -hydrogen atoms can be converted to alkenes in ester pyrolysis.

Protecting groups[edit]
As a class, esters serve as protecting groups for carboxylic acids. Protecting a carboxylic acid is useful in peptide synthesis, to prevent self-reactions of the bifunctional amino acids. Methyl and ethyl esters are commonly available for many amino acids; the t-butyl ester tends to be more expensive. However, t-butyl esters are particularly useful because, under strongly acidic conditions, the t-butyl esters undergo elimination to give the carboxylic acid and isobutylene, simplifying work-up.

List of ester odorants[edit]

Many esters have distinctive fruit-like odors, and many occur naturally in the essential oils of plants. This has also led to their commonplace use in artificial flavorings and fragrances when those odors aim to be mimicked. Ester Name Allyl hexanoate Benzyl acetate Formula Odor or occurrence pineapple pear, strawberry, jasmine

Bornyl acetate

pine

Butyl acetate Butyl butyrate Butyl propanoate Ethyl acetate Ethyl butyrate Ethyl hexanoate Ethyl cinnamate Ethyl formate Ethyl heptanoate Ethyl isovalerate Ethyl lactate Ethyl nonanoate Ethyl pentanoate Geranyl acetate Geranyl butyrate Geranyl pentanoate Isobutyl acetate

apple, honey bee pineapple pear drops nail polish remover, model paint, model airplane glue banana, pineapple, strawberry pineapple, waxy-green banana cinnamon lemon, rum, strawberry apricot, cherry, grape, raspberry apple butter, cream grape apple geranium cherry apple cherry, raspberry, strawberry

Isobutyl formate Isoamyl acetate Isopropyl acetate Linalyl acetate Linalyl butyrate Linalyl formate

raspberry pear, banana (flavoring in Pear drops) fruity lavender, sage peach apple, peach

Methyl acetate

glue

Methyl anthranilate

grape, jasmine

Methyl benzoate Methyl butyrate (methyl butanoate) Methyl cinnamate Methyl pentanoate (methyl valerate) Methyl phenylacetate Methyl salicylate (oil of wintergreen) Nonyl caprylate Octyl acetate Octyl butyrate Amyl acetate (pentyl acetate) Pentyl butyrate (amyl butyrate) Pentyl hexanoate (amyl

fruity, ylang ylang, feijoa pineapple, apple, strawberry strawberry flowery honey Modern root beer, wintergreen, Germolene and Ralgex ointments (UK) orange fruity-orange parsnip apple, banana apricot, pear, pineapple apple, pineapple

caproate) Pentyl pentanoate (amyl valerate) Propyl acetate Propyl hexanoate Propyl isobutyrate Terpenyl butyrate

apple pear blackberry, pineapple, cheese, wine rum cherry

See also[edit]

Cyanate ester Oligoester Polyolester Transesterification Transamidification

References[edit]
1. 2. Jump up ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006) "esters". Jump up ^ Leopold Gmelin, Handbuch der Chemie, vol. 4: Handbuch der organischen Chemie (vol. 1) (Heidelberg, Baden (Germany): Karl Winter, 1848), page 182. Original text: b. Ester oder sauerstoffsure Aetherarten. Ethers du troisime genre. Viele mineralische und organische Sauerstoffsuren treten mit einer Alkohol-Art unter Ausscheidung von Wasser zu neutralen flchtigen therischen Verbindungen zusammen, welche man als gepaarte Verbindungen von Alkohol und Suren-Wasser oder, nach der Radicaltheorie, als Salze betrachten kann, in welchen eine Sure mit einem Aether verbunden ist. Translation: b. Ester or oxy-acid ethers. Ethers of the third type. Many mineral and organic acids containing oxygen combine with an alcohol upon elimination of water to [form] neutral, volatile ether compounds, which one can view as coupled compounds of alcohol and acidwater, or, according to the theory of radicals, as salts in which an acid is bonded with an ether. 3. ^ Jump up to: a b March, J. Advanced Organic Chemistry 4th Ed. J. Wiley and Sons, 1992: New York. ISBN 0-471-60180-2.

4. 5.

Jump up ^ Chemistry of Enols and Enolates - Acidity of alpha-hydrogens Jump up ^ Isolation of triglyceride from nutmeg: G. D. Beal "Trimyristen" Organic Syntheses, Coll. Vol. 1, p.538 (1941). Link 6. Jump up ^ McGee, Harold. On Food and Cooking. 2003, Scribner, New York. 7. ^ Jump up to: a b Wilhelm Riemenschneider1 and Hermann M. Bolt "Esters, Organic" Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi:10.1002/14356007.a09_565.pub2 8. Jump up ^ Roger J. Williams, Alton Gabriel, Roy C. Andrews The Relation Between the Hydrolysis Equilibrium Constant of Esters and the Strengths of the Corresponding Ac ids J. Am. Chem. Soc., 1928, volume 50, 1267. doi:10.1021/ja01392a005 9. Jump up ^ B. Neises and W. Steglich, "Esterification of Carboxylic Acids with Dicyclohexylcarbodiimide/4-Dimethylaminopyridine: tert-Butyl ethyl fumarate", Org. Synth.; Coll. Vol. 7: 93 10. Jump up ^ Ignatyev, Igor; Charlie Van Doorslaer, Pascal G.N. Mertens, Koen Binnemans, Dirk. E. de Vos (2011). "Synthesis of glucose esters from cellulose in ionic liquids". Holzforschung 66 (4): 417425. doi:10.1515/hf.2011.161. 11. Jump up ^ W. Reusch. "Carboxyl Derivative Reactivity". Virtual Textbook of Organic Chemistry.

External links[edit]

An introduction to esters Molecule of the month: Ethyl acetate and other esters [hide]

v t e

Functional groups

Acetyl Acetoxy Acryloyl Acyl Alcohol Aldehyde Alkane Alkene Alkyne Alkoxy group Amide

Amine Azo compound Benzene derivative Carbene Carbonyl Carboxylic acid Cyanate Disulfide Dioxirane Ester Ether Epoxide Haloalkane Hydrazone Hydroxyl Imide Imine Isocyanate Isonitrile Isothiocyanate Ketone Methyl Methylene bridge Methylene group Methine Nitrile Nitrene Nitro compound Nitroso compound

Organophosphorus Oxime Peroxide Phosphonous and Phosphonic acid Pyridine derivative Selenol Selenonic acid Sulfone Sulfonic acid Sulfoxide Tellurol Thial Thiocyanate Thioester Thioether Thioketone Thiol Urea See also Chemical classification

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ester, any one of a group of organic compounds with general formula RCO2R (where R and R
are alkyl groups or aryl groups) that are formed by the reaction between an alcohol and an acid. For example, when ethanol and acetic acid react, ethyl acetate (an ester) and water are formed; the reaction is called esterification. Ethyl acetate

acetate , one of the most important forms of

artificial cellulose-based fibers; the ester of acetic acid. The first patents for the production of fibers from cellulose acetate appeared at the beginning of the 20th cent. ..... Click the link for more information. is used as a solvent. Methyl acetate, formed by the reaction between methanol and acetic acid, is a sweet-smelling liquid used in making perfumes, extracts, and lacquers. Esters react with water (hydrolysis

hydrolysis , chemical reaction of

a compound with water, usually resulting in the formation of one or more new compounds. The most common hydrolysis occurs when a salt of a weak acid or weak base (or both) is dissolved in water. ..... Click the link for more information. ) under basic conditions to form an alcohol and an acid. When heated with a hydroxide certain esters decompose to yield soap and glycerin; the process is called saponification. Common fats and oils

fats and oils, group of organic substances

that form an important part of the diet and also are useful in many industries. The fats are usually solid, the oils generally liquid at ordinary room temperatures. ..... Click the link for more information. are mixtures of various esters, such as stearin

stearin ,

fat that is the triglyceride of stearic acid, CH3(CH2)16CO2H, i.e., the tristearate ester of glycerol. It is a white crystalline solid at ordinary temperatures and is insoluble in water and very slightly soluble ..... Click the link for more information. , palmitin

palmitin , fat that is the triglyceride of palmitic

acid, CH3(CH2)14CO2H, i.e., the tripalmitate ester of glycerol. ..... Click the link for more information. , and linolein, formed from the alcohol glycerol

glycerol, glycerin, glycerine, or 1,2,3-propanetriol , CH2OHCHOHCH2OH,

colorless, odorless, sweet-tasting, syrupy liquid. Glycerol is a trihydric alcohol. It melts at 17. ..... Click the link for more information. and fatty acids

fatty acid, any of the organic

carboxylic acids present in fats and oils as esters of glycerol. Molecular weights of fatty acids vary over a wide range. The carbon skeleton of any fatty acid is unbranched. Some fatty acids

are saturated, i.e. ..... Click the link for more information. . Naturally occurring esters of organic acids in fruits and flowers give them their distinctive odors. Esters perform important functions in the animal body; e.g., the ester acetylcholine is a chemical transmitter of nerve stimuli.
The Columbia Electronic Encyclopedia Copyright 2013, Columbia University Press. Licensed from Columbia University Press. All rights reserved. www.cc.columbia.edu/cu/cup/

ester
Any of a class of organic compounds that can react with water ( see hydrolysis) to produce an alcohol and an organic or inorganic acid. They are formed by the reverse process, esterification, in which acid reacts with alcohol to form an ester and water. Esters of carboxylic acids, the most common esters, contain the acid's carbonyl group (C=O; see functional group); the carbon's fourth bond is with the alcohol's oxygen atom. Hydrolysis of esters in the presence of an alkali (saponification) is used to make soaps from fats and oils. Carboxylic acid esters of low molecular weight are colourless, volatile liquids with pleasant odours; they give flavour and fragrance to fruits and flowers and are used as synthetic flavours and fragrances. Others, such as ethyl acetate and butyl acetate, are used as solvents for lacquers, paints, and varnishes. Certain polymers are esters, including Lucite (polymethyl methacrylate) and Dacron (polyethylene terephthalate). Esters of alcohols and inorganic acids include nitrate esters (e.g., nitroglycerin), which are explosive; phosphate esters, including such biologically important compounds as nucleic acids; and others that are used as flame retardants, solvents, plasticizers, gasoline and oil additives, and insecticides.
For more information on ester, visit Britannica.com. Britannica Concise Encyclopedia. Copyright 1994-2008 Encyclopdia Britannica, Inc.

ester
Chem any of a class of compounds produced by reaction between acids and alcohols with the elimination of water. Esters with low molecular weights, such as ethyl acetate, are usually volatile fragrant liquids; fats are solid esters

Collins Discovery Encyclopedia, 1st edition HarperCollins Publishers 2005

ester [estr]
(organic chemistry) The compound formed by the elimination of water and the bonding of an alcohol and an organic acid.

McGraw-Hill Dictionary of Scientific & Technical Terms, 6E, Copyright 2003 by The McGraw-Hill Companies, Inc.

Warning! The following article is from The Great Soviet Encyclopedia (1979). It might be outdated or ideologically biased.

Ester
any of a number of organic compounds, such as C2H5OCOCH3 or C5H11ONO, that are derived from acids by replacing the hydroxyl group (OH) with an alcohol, enol, or phenol radical (OR).

Esters are structural analogues of the salts of oxygen acids, but where a metal atom would be attached to the salt, a hydrocarbon group (R) is attached to the ester. The nomenclature for the salts and esters is similar; for example, NaOCOCH3 is called sodium acetate, and C2H5OCOCH3 is known as ethyl acetate. Like salts, esters form products of incomplete and complete replacement with dibasic and multibasic acids; thus, there are acid esters, such as monomethylsulfate (HOSO2OCH3), and complete (neutral) esters, such as dimethylsulfate (CH3OSO2OCH3). Esters differ greatly from salts in their properties, however. Typical organic compounds, esters are usually volatile liquids. In some instances, they have a fruity or flowery fragrance. Virtually insoluble in water, they are readily soluble in organic solvents. Esters are hydrolyzed by the action of water to form the corresponding alcohol and acid, in accordance with the general formula RCOOR + H2O RCOOH + HOR The reaction is catalyzed by acids and even more so by bases. When alkaline catalysts are used, salts of acids are formed instead of free acids; the reaction is irreversible. Of the other reactions in which esters display acylating properties, the most common are transesterification, alcoholysis, and double exchange reactions. Some estersfor example, those formed by the lower aliphatic alcohols and such acids as sulfuric, trifluoroacetic, phosphoric, and phthalic acids also have alkylating properties (seeDIMETHYL SULFATE and ). Esters are usually obtained by esterification (see). They may also be formed by the acylation of alcohols by various acid derivatives (including acid halides and anhydrides), by the action of acid salts on alkyl halides, as in the reaction C2H5I + AgONO C2H5ONO + AgI or by the action of acids on olefins, as in the reaction HOSO2OH + CH2=CH2 HOSO2OCH2CH3 Esters of glycerin and the higher carboxylic acids are the principal components of fats, and esters of the higher monohydric aliphatic alcohols and carboxylic acids are the main components of waxes. Other estersmainly those of the terpene alcoholsare components of essential oils. Esters are used in technology as plastic monomers (acrylates and vinyl acetates), plasticizers for plastics (dioctyl and dibutyl phthalates), detergents (alkyl sulfates), solvents (amyl, butyl, and ethyl acetates), extraction agents and pesticides (esters of phosphoric acid), explosives (esters of nitric acid and polyhydric alcohols, such as nitroglycerin), pharmaceuticals (validol and aspirin), and fragrances (benzyl acetate and terpenyl acetate). Many esters of high molecular weight (including polyethylene terephthalate and cellulose acetates) are used in industry as plastics, lacquers, and synthetic fibers (seeALKYD RESINS and POLYESTER FIBER).

REFERENCES
Nesmeianov, A. N., and N. A. Nesmeianov. Nachala organicheskoi khimii, books 12. Moscow, 196970. Chichibabin, A. E. Osnovnye nachala organicheskoi khimii, 7th ed., vol. 1. Moscow, 1963.
The Great Soviet Encyclopedia, 3rd Edition (1970-1979). 2010 The Gale Group, Inc. All rights reserved.

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ESTERIFICATION OF CARBOXYLIC ACIDS

This page looks at esterification - the reaction between alcohols and carboxylic acids to make esters.

What are esters?

Esters have a hydrocarbon group of some sort replacing the hydrogen in the -COOH group of a carboxylic acid. We shall just be looking at cases where it is replaced by an alkyl group, but it could equally well be an aryl group (one based on a benzene ring). A common ester - ethyl ethanoate The most commonly discussed ester is ethyl ethanoate. In this case, the hydrogen in the -COOH group has been replaced by an ethyl group. The formula for ethyl ethanoate is:

Notice that the ester is named the opposite way around from the way the formula is written. The "ethanoate" bit comes from ethanoic acid. The "ethyl" bit comes from the ethyl group on the end.
Note: In my experience, students starting organic chemistry get more confused about writing names and formulae for esters than for almost anything else - particularly when it comes to less frequently met esters like the ones coming up next. Take time and care to make sure you understand!

A few more esters In each case, be sure that you can see how the names and formulae relate to each other.

Remember that the acid is named by counting up the total number of carbon atoms in the chain - including the one in the COOH group. So, for example, CH3CH2COOH is propanoic acid, and CH3CH2COO is the propanoate group.
Note: You can find more about naming acids and esters by following this link to a different part of this site. Use the BACK button on your browser to return to this page.

Making esters
The chemistry of the reaction Esters are produced when carboxylic acids are heated with alcohols in the presence of an acid catalyst. The catalyst is usually concentrated sulphuric acid. Dry hydrogen chloride gas is used in some cases, but these tend to involve aromatic esters (ones containing a benzene ring). If you are a UK A level student you won't have to worry about these. The esterification reaction is both slow and reversible. The equation for the reaction between an acid RCOOH and an alcohol R'OH (where R and R' can be the same or different) is:

So, for example, if you were making ethyl ethanoate from ethanoic acid and ethanol, the equation would be:

Note: The mechanism for the esterification reaction is covered in the catalysis section of this site. It is not required for any UK A level chemistry syllabus. If you follow this link, use the BACK button on your browser to return to this page.

Doing the reactions On a test tube scale Carboxylic acids and alcohols are often warmed together in the presence of a few drops of concentrated sulphuric acid in order to observe the smell of the esters formed. You would normally use small quantities of everything heated in a test tube stood in a hot water bath for a couple of minutes. Because the reactions are slow and reversible, you don't get a lot of ester produced in this time. The smell is often masked or distorted by the smell of the carboxylic acid. A simple way of detecting the smell of the ester is to pour the mixture into some water in a small beaker. Esters are virtually insoluble in water and tend to form a thin layer on the surface. Excess acid and alcohol both dissolve and are tucked safely away under the ester layer. Small esters like ethyl ethanoate smell like typical organic solvents (ethyl ethanoate is a common solvent in, for example,

glues). As the esters get bigger, the smells tend towards artificial fruit flavouring - "pear drops", for example. On a larger scale If you want to make a reasonably large sample of an ester, the method used depends to some extent on the size of the ester. Small esters are formed faster than bigger ones. To make a small ester like ethyl ethanoate, you can gently heat a mixture of ethanoic acid and ethanol in the presence of concentrated sulphuric acid, and distil off the ester as soon as it is formed. This prevents the reverse reaction happening. It works well because the ester has the lowest boiling point of anything present. The ester is the only thing in the mixture which doesn't form hydrogen bonds, and so it has the weakest intermolecular forces.
Note: Follow this link if you aren't sure about hydrogen bonding. Use the BACK button on your browser to return to this page.

Larger esters tend to form more slowly. In these cases, it may be necessary to heat the reaction mixture under reflux for some time to produce an equilibrium mixture. The ester can be separated from the carboxylic acid, alcohol, water and sulphuric acid in the mixture by fractional distillation.
Note: Providing full details for organic preparations (including all the steps necessary in cleaning up the product) is beyond the scope of this site. If you need this sort of detail, you should be looking at an organic practical book.

Where would you like to go now?

To the carboxylic acids menu . . . To the menu of other organic compounds . . . To Main Menu . . .

Jim Clark 2004 ESTERIFICATION OF CARBOXYLIC ACIDS This page looks at esterification - the reaction between alcohols and carboxylic acids to make esters. What are esters? Esters have a hydrocarbon group of some sort replacing the hydrogen in the -COOH group of a carboxylic acid. We shall just be looking at cases where it is replaced by an alkyl group, but it could equally well be an aryl group (one based on a benzene ring). A common ester - ethyl ethanoate The most commonly discussed ester is ethyl ethanoate. In this case, the hydrogen in the -COOH group has been replaced by an ethyl group. The formula for ethyl ethanoate is:

Notice that the ester is named the opposite way around from the way the formula is written. The "ethanoate" bit comes from ethanoic acid. The "ethyl" bit comes from the ethyl group on the end. Note: In my experience, students starting organic chemistry get more confused about writing names and formulae for esters than for almost anything else - particularly when it comes to less frequently met esters like the ones coming up next. Take time and care to make sure you understand!

A few more esters In each case, be sure that you can see how the names and formulae relate to each other.

Remember that the acid is named by counting up the total number of carbon atoms in the chain - including the one in the COOH group. So, for example, CH3CH2COOH is propanoic acid, and CH3CH2COO is the propanoate group.
Note: You can find more about naming acids and esters by following this link to a different part of this site. Use the BACK button on your browser to return to this page.

Making esters
The chemistry of the reaction Esters are produced when carboxylic acids are heated with alcohols in the presence of an acid catalyst. The catalyst is usually concentrated sulphuric acid. Dry hydrogen chloride gas is used in some cases, but these tend to involve aromatic esters (ones containing a benzene ring). If you are a UK A level student you won't have to worry about these. The esterification reaction is both slow and reversible. The equation for the reaction between an acid RCOOH and an alcohol R'OH (where R and R' can be the same or different) is:

So, for example, if you were making ethyl ethanoate from ethanoic acid and ethanol, the equation would be:

Note: The mechanism for the esterification reaction is covered in the catalysis section of this site. It is not required for any UK A level chemistry syllabus. If you follow this link, use the BACK button on your browser to return to this page.

Doing the reactions On a test tube scale Carboxylic acids and alcohols are often warmed together in the presence of a few drops of concentrated sulphuric acid in order to observe the smell of the esters formed. You would normally use small quantities of everything heated in a test tube stood in a hot water bath for a couple of minutes. Because the reactions are slow and reversible, you don't get a lot of ester produced in this time. The smell is often masked or distorted by the smell of the carboxylic acid. A simple way of detecting the smell of the ester is to pour the mixture into some water in a small beaker. Esters are virtually insoluble in water and tend to form a thin layer on the surface. Excess acid and alcohol both dissolve and are tucked safely away under the ester layer. Small esters like ethyl ethanoate smell like typical organic solvents (ethyl ethanoate is a common solvent in, for example,

glues). As the esters get bigger, the smells tend towards artificial fruit flavouring - "pear drops", for example. On a larger scale If you want to make a reasonably large sample of an ester, the method used depends to some extent on the size of the ester. Small esters are formed faster than bigger ones. To make a small ester like ethyl ethanoate, you can gently heat a mixture of ethanoic acid and ethanol in the presence of concentrated sulphuric acid, and distil off the ester as soon as it is formed. This prevents the reverse reaction happening. It works well because the ester has the lowest boiling point of anything present. The ester is the only thing in the mixture which doesn't form hydrogen bonds, and so it has the weakest intermolecular forces.
Note: Follow this link if you aren't sure about hydrogen bonding. Use the BACK button on your browser to return to this page.

Larger esters tend to form more slowly. In these cases, it may be necessary to heat the reaction mixture under reflux for some time to produce an equilibrium mixture. The ester can be separated from the carboxylic acid, alcohol, water and sulphuric acid in the mixture by fractional distillation.
Note: Providing full details for organic preparations (including all the steps necessary in cleaning up the product) is beyond the scope of this site. If you need this sort of detail, you should be looking at an organic practical book.

Where would you like to go now?

To the carboxylic acids menu . . . To the menu of other organic compounds . . . To Main Menu . . .

Jim Clark 2004