Esters

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. 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
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 o 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
Etymology
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

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 gammavalerolactone.
Orthoesters
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"
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

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

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

Esters are usually identified by gas chromatography, taking advantage of their volatility. IR spectra for esters feature an intense sharp band in the range 1730 1750 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

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
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

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]

Esters

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Esters are chemical compounds consisting of a carbonyl adjacent to an ether linkage.

IUPAC nomenclature of Esters

Structure and bonding

Physical properties and characterization

Characterization and analysis

Applications and occurrence

Esterification of carboxylic acids

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