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Structure of a carboxylic acid
The 3D structure of the carboxyl group
A space-filling model of the carboxyl group Carboxylic acids are organic acids characterized by the presence of a carboxyl group, which has the formula -C(=O)OH, usually written -COOH or -CO2H.  Carboxylic acids are Brønsted-Lowry acids — they are proton donors. Salts and anions of carboxylic acids are called carboxylates.
1 Physical properties o 1.1 Solubility o 1.2 Boiling points o 1.3 Acidity o 1.4 Odor 2 Nomenclature o 2.1 Carboxylic acid radical 3 Characterization
1 Industrial routes o 5. Carboxylic acids tend to evaporate or boil as these dimers. but because of their tendency to form stabilised dimers.2 Laboratory methods o 5.• • • • • • • 4 Occurrence and applications 5 Synthesis o 5.02 % of all acetic acid molecules are dissociated. at room temperature. both of which increase enthalpy of vaporisation requirements significantly.” Smaller carboxylic acids (1 to 5 carbons) are soluble with water. These longer chain acids tend to be rather soluble in less-polar solvents such as ethers and alcohols. not only because of their increased surface area. Because they are both hydrogen-bond acceptors (the carbonyl) and hydrogen-bond donors (the hydroxyl).  Acidity Carboxylic acids are typically weak acids.3 Less-common reactions 6 Reactions o 6. they also participate in hydrogen bonding. Carboxylic acids usually exist as dimeric pairs in nonpolar media due to their tendency to “self-associate. For example. only 0. For boiling to occur.   Boiling points Carboxylic acids tend to have higher boiling points than water. whereas higher carboxylic acids are less soluble due to the increasing hydrophobic nature of the alkyl chain. meaning that they only partially dissociate into H+ cations and RCOO.1 Specialized reactions 7 Nomenclature and examples 8 See also 9 References 10 External links  Physical properties  Solubility Carboxylic acid dimers Carboxylic acids are polar.anions in neutral aqueous solution. . Together the hydroxyl and carbonyl group forms the functional group carboxyl. or the entire dimer arrangement must be vaporised. Electronegative substituents give stronger acids. either the dimer bonds must be broken.
Most common are acetic acid (vinegar) and butyric acid (rancid butter).  Nomenclature The simplest series of carboxylic acids are the alkanoic acids.77 4.5 1.27 4. Each of the carbonoxygen bonds in a carboxylate anion has partial double-bond character. where R is a hydrogen or an alkyl group. RCOOH.76 2.65 Trifluoroacetic acid (CF3CO2H) Oxalic acid (HO2CCO2H) Benzoic acid (C6H5CO2H) 0.Carboxylic Acids Formic acid (HCO2H) Acetic acid (CH3CO2H) Chloroacetic acid (CH2ClCO2H) pKa 3.  Carboxylic acid radical .86 Dichloroacetic acid (CHCl2CO2H) 1. The mono. esters of carboxylic acids tend to have pleasant odors and many are used in perfumes.and dicarboxylic acids have trivial names. Compounds may also have two or more carboxylic acid groups per molecule. especially the volatile derivatives.29 Trichloroacetic acid (CCl3CO2H) 0. On the other hand.2 Ionization of a carboxylic acid gives a carboxylate anion. which is stabilized because the negative charge is shared (delocalized) between the two oxygen atoms.  Odor Carboxylic acids often have strong odors.
conducted with iodide and alkoxide promoters. Carboxylic acids are used in the production of polymers. This method is effective for alkenes that generate secondary and tertiary carbocations. For simple alkanes. Benzoic acid from toluene and terephthalic acid from para-xylene. and phthalic acid from ortho-xylene are illustrative large-scale conversions.  Characterization Carboxylic acids are most readily identified as such by infrared spectroscopy. Base-catalyzed dehydrogenation of alcohols. the radical ·COOH group has only a separate fleeting existence. They are also pervasive in nature.g. • • • • Oxidation of aldehydes with air using cobalt and manganese catalysts. terephthalic acid (polymers). Oxidation of hydrocarbons using air. citric acid (beverages). fatty acids (coatings). solvents. e. isobutylene to pivalic acid. A characteristic νO-H band appears as a broad peak in the 2500 to 3000 cm−1 region. Allylic and benzylic compounds undergo more selective oxidations. Industrially important carboxylic acids include acetic acid (component of vinegar. Alkyl groups on a benzene ring oxidized to the carboxylic acid. Carbonylation is versatile method when coupled to the addition of water. By 1 H NMR spectrometry. In the Koch reaction. respectively and often with high pressures of carbon monoxide.  Synthesis  Industrial routes Industrial routes to carboxylic acids generally differ from those used on smaller scale because they require specialized equipment.  Occurrence and applications Many carboxylic acids are produced industrially on a large scale. maleic acid (polymers). and food additives. precursor to solvents and coatings). regardless of its chain length. Acetic acid and formic acid are produced by the carbonylation of methanol. They exhibit a sharp band associated with vibration of the C-O vibration bond (νC=O) between 1680 and 1725 cm−1. the method is nonselective but so inexpensive to be useful. ethylenediaminetetraacetic acid (chelating agent). propionic acid (food preservative). the addition of water and carbon monoxide to alkenes is catalyzed by strong acids. acrylic and methacrylic acids (precursors to polymers. the hydroxyl hydrogen appears in the 10-13 ppm region. pharmaceuticals. The acid dissociation constant of ·COOH has been measured using electron paramagnetic resonance spectrocopy. although it is often either broadened or not observed owing to exchange with traces of water. Esters of fatty acids are the main components of lipids and polyamides of aminocarboxylic acids are the main components of proteins. Acrylic acid is generated from propene. adipic acid (polymers).In the absence of an additional substituent (usually indicated by "R"). adhesives). usually . The required aldehydes are readily obtained from alkenes by hydroformylation.
Carboxylic acids react with bases to form carboxylate salts. Thus. precursor to aspirin. potassium permanganate. fermentation of ethanol is used in the production of vinegar.  Less-common reactions Many reactions afford carboxylic acids but are used only in specific cases or are mainly of academic interest: • • Disproportionation of an aldehyde in the Cannizzaro reaction Rearrangement of diketones in the benzilic acid rearrangement involving the generation of benzoic acids are the von Richter reaction from nitrobenzenes and the Kolbe-Schmitt reaction from phenols. generally with acid. Such reactions are sometimes called "Reppe chemistry": HCCH + CO + H2O → CH2=CHCO2H • • Some long chain carboxylic acids are obtained by the hydrolysis of triglycerides obtained from plant or animal oils.  Laboratory methods Preparative methods for small scale reactions for research. amides. and water: . or potassium dichromate. in which the hydrogen of the hydroxyl (-OH) group is replaced with a metal cation. and alcohols. Hydrocarboxylations involve the simultaneous addition of water and CO.involving additional hydrolytic steps. These methods are related to soap making. or for production of small amounts of fine chemicals often employ expensive consumable reagents. potassium permanganate. carboxylate salts. acid chlorides. Carboxylic acids can also be obtained by the hydrolysis of nitriles. Jones reagent. The method is amenable to laboratory conditions compared to the industrial use of air. carbon dioxide. which is “greener” since it yields less inorganic side products such as chromium or manganese oxides. or amides. Oxidative cleavage of olefins by ozonolysis. esters. or sodium chlorite.  Reactions The most widely practiced reactions convert carboxylic acids into esters.or base-catalysis. Carbonation of a Grignard and organolithium reagents: RLi + CO2 RCO2Li RCO2Li + HCl RCO2H + LiCl • • Halogenation followed by hydrolysis of methyl ketones in the haloform reaction The Kolbe-Schmitt reaction provides a route to salicylic acid. • • • • oxidation of primary alcohols or aldehydes with strong oxidants such as potassium dichromate. instruction. acetic acid found in vinegar reacts with sodium bicarbonate (baking soda) to form sodium acetate.
so acetic acid.  Nomenclature and examples The carboxylate anion R-COO– is usually named with the suffix -ate. Thus the α-carbon is easily halogenated in the Hell-VolhardZelinsky halogenation.. Straight-Chained. In common nomenclature.g. The Dakin-West reaction converts an amino acid to the corresponding amino ketone. In the Barbier-Wieland degradation.CH3COOH + NaHCO3 → CH3COO−Na+ + CO2 + H2O Carboxylic acids also react with alcohols to give esters. This process is heavily used in the production of polyesters. In IUPAC nomenclature. carboxylic acids are converted to thioesters.. The conversion of amino acids into peptides is a major biochemical process that requires ATP. octadecanoic acid). The Schmidt reaction converts carboxylic acids to amines.1.1) and decarboxylases (EC 4. The hydroxyl group on carboxylic acids may be replaced with a chlorine atom using thionyl chloride to give acyl chlorides. but this conversion typically does not occur by direct reaction of the carboxylic acid and the amine.4. Instead esters are typical precursors to amides. Similarly carboxylic acids are converted into amides. Saturated Carboxylic Acids Carbon atoms 1 2 Common name Formic acid Acetic acid IUPAC name Chemical formula Common location or use Methanoic acid Ethanoic acid HCOOH CH3COOH Insect stings Vinegar . stearic acid). Enzymes that catalyze these reactions are known as carboxylases (EC 6. the protons on the α-carbon are labile due to ketoenol tautomerization. Carboxylic acids are reduced to aldehydes via the ester and DIBAL. In nature.1). for example. Carboxylic acids are decarboxylated in the Hunsdiecker reaction. The carboxylic acid can be reduced to the alcohol by hydrogenation or using stoichiometric hydride reducing agents such as lithium aluminum hydride. carboxylic acids have an -oic acid suffix (e.  Specialized reactions • • • • • • • As with all carbonyl compounds. the suffix is usually -ic acid (e. the alpha-methylene group in an aliphatic carboxylic acid is removed in a sequence of reaction steps. Many acids undergo decarboxylation. becomes acetate ion. effectively a chainshortening  . via the acid chloride in the Rosenmund reduction and via the thioester in the Fukuyama reduction.g.
and oils 20 Arachidic acid Eicosanoic acid CH3(CH2)18COOH Peanut oil . waxes.3 4 5 6 7 8 Propionic acid Propanoic acid Butyric acid Valeric acid Caproic acid Butanoic acid Pentanoic acid Hexanoic acid CH3CH2COOH CH3(CH2)2COOH Rancid butter CH3(CH2)3COOH Valerian CH3(CH2)4COOH Goat fat CH3(CH2)5COOH CH3(CH2)6COOH Coconuts and breast milk Enanthic acid Heptanoic acid Caprylic acid Octanoic acid Pelargonic acid Capric acid 9 Nonanoic acid CH3(CH2)7COOH Pelargonium 10 Decanoic acid CH3(CH2)8COOH Coconut oil and hand wash soaps. soaps. 12 Lauric acid Dodecanoic acid CH3(CH2)10COOH 14 Myristic acid Tetradecanoic acid Hexadecanoic acid Octadecanoic acid CH3(CH2)12COOH Nutmeg 16 Palmitic acid CH3(CH2)14COOH Palm oil 18 Stearic acid CH3(CH2)16COOH Chocolate.
found in wine .3-tricarboxylic acid (tricarballylic acid. with even number of carbons o Docosahexaenoic acid – nutritional supplement o Eicosapentaenoic acid – nutritional supplement Amino acids – the building blocks of proteins Keto acids – acids of biochemical significance that contain a ketone group o Acetoacetic acid o Pyruvic acid • • • • • • Aromatic carboxylic acids o Benzoic acid – C6H5COOH. used in polymer synthesis Fatty acids – medium to long-chain saturated and unsaturated monocarboxylic acids.Other carboxylic acids include: • • Short-chain unsaturated monocarboxylic acids o Acrylic acid (2-propenoic acid) – CH2=CHCOOH.an alpha hydroxy type o Salicylic acid – a beta hydroxy type found in many skin care products Dicarboxylic acids – containing two carboxyl groups o Adipic acid – the monomer used to produce nylon o Aldaric acid – a family of sugar acids o Fumaric acid o Glutaric acid o Maleic acid o Malic acid – found in apples o Malonic acid o Oxalic acid – found in many foods o Succinic acid – a component of the citric acid cycle o Tartronic acid Tricarboxylic acids – containing three carboxyl groups o Citric acid – found in citrus fruits o Isocitric acid o Aconitic acid o Propane-1.2. carballylic acid) Alpha hydroxy acids – containing a hydroxy group o Glyceric acid o Glycolic acid o Lactic acid (2-hydroxypropanoic acid) – found in sour milk o Tartaric acid . sodium benzoate. the sodium salt of benzoic acid is used as a food preservative o Mandelic acid .
the free encyclopedia (Redirected from Acid chloride) Jump to: navigation.1 Nucleophilic reactions o 4.2 Electrophilic reactions .Acyl chloride From Wikipedia. where R is an organic radical group. search General chemical structure of an acyl chloride Example of an acyl chloride: acetyl chloride or ethanoyl chloride In organic chemistry. A specific example of an acyl chloride is acetyl chloride. Contents [hide] • • • • 1 Nomenclature 2 Properties 3 Synthesis 4 Reactions o 4. an acyl chloride has the reactive functional group -CO-Cl and has the general formula RCOCl. an acyl chloride (or acid chloride) is an organic compound which is a reactive derivative of a carboxylic acid. As part of its molecular structure. CH3COCl. Acyl chlorides are a subset of acyl halides and undergo many of the same chemical reactions.
 Synthesis Acyl chlorides are generally prepared in the same manner as alkyl chlorides: by replacing the corresponding hydroxy substituents with chlorides. or phosphorus pentachloride (PCl5): R-COOH + SOCl2 → R-COCl + SO2 + HCl 3 R-COOH + PCl3 → 3 R-COCl + H3PO3 R-COOH + PCl5 → R-COCl + POCl3 + HCl The reaction with thionyl chloride may be catalyzed by dimethylformamide. acetyl chloride. the mechanism with thionyl chloride is illustrative: . In this reaction. Thus: acetyl chloride CH3COCl benzoyl chloride C6H5COCl When other functional groups take priority.g. 51 °C). b. Like all carbonyl compounds. The reaction mechanism involving thionyl chloride and phosphorus pentachloride are similar.p. driving the reaction forward.p.p. Excess thionyl chloride (b. Acyl chlorides are often prepared by reacting a carboxylic acid with thionyl chloride (SOCl2).• • 5 Hazards 6 References  Nomenclature Where the acyl chloride moiety takes priority. b. the sulfur dioxide (SO2) and hydrogen chloride (HCl) generated are both gases which can leave the reaction vessel. 118 °C. acyl chlorides are named by taking the name of the parent carboxylic acid. and substituting -ic acid for -yl chloride. acyl chlorides are considered prefixes — chlorocarbonyl-: (chlorocarbonyl)acetic acid ClOCCH2COOH  Properties Acyl chlorides tend to be liquids. infrared spectroscopy reveals a band near 1800 cm−1. 79 °C) is easily evaporated as well. phosphorus trichloride (PCl3). which may react with atmospheric moisture to give fumes in air. Lacking the ability to form hydrogen bonds. acetic acid. they have lower boiling points than similar carboxylic acids (e.
The iminium intermediate reacts with the carboxylic acid. DMF reacts with oxalyl chloride in the first step to give the iminium intermediate. .Another method involves the use of oxalyl chloride: R-COOH + ClCOCOCl → R-COCl + CO + CO2 + HCl The reaction is catalysed by dimethylformamide. and regenerating the DMF catalyst. abstracting an oxygen atom.
In contrast. such as the Appel reaction: R-COOH + Ph3P + CCl4 → R-COCl + Ph3PO + HCCl3 and the use of cyanuric chloride (C3N3Cl3):  Reactions  Nucleophilic reactions Acyl chlorides are very reactive. or an amine respectively. With carbon nucleophiles such as Grignard reagents. due to their lesser reactivity. it will be readily replaced with the nucleophile. since both the oxygen and chlorine are strongly electron withdrawing. and coupling with the alcohol or amine) are fast and irreversible. often leading to low yields. A notable exception is the reaction of acyl halides with certain organocadmium reagents which stops at the ketone stage. and to catalyze the reaction. . both reactions involved in preparing esters and amides via acyl chlorides (acyl chloride formation. The use of a base. including acid anhydrides. or excess amine (when preparing amides) is desirable to remove the hydrogen chloride byproduct. and amides by reacting acid chlorides with: a salt of a carboxylic acid. Since a chloride ion is a good leaving group. an alcohol. to give a carboxylic acid: R-COCl + HO-H → R-COOH + HCl Acyl chlorides can be used to prepare carboxylic acid derivatives. This makes the two-step route often preferable to the single step reaction with the carboxylic acid. acyl chlorides generally react first to the ketone and then with a second equivalent to the tertiary alcohol. giving the carbon a large partial positive charge. The presence of the chlorine on the carbonyl carbon makes it a very good electrophile.Finally. This means even a weak nucleophile can attack the carbon. e. aqueous sodium hydroxide or pyridine. While it is often possible to obtain esters or amides from the carboxylic acid with alcohols or amines. The nucleophilic reaction with Gilman reagents (lithium diorganocopper compounds) also afford ketones. the reactions are reversible. Acid chlorides of aromatic acids are generally less reactive those of alkyl acids and thus somewhat more rigorous conditions are required for reaction. The simplest reaction is with water. esters. methods that do not form HCl are also known.g.
they are generally toxic and special precautions should be taken while handling them. a bulky hydride donor. and the AlCl3 catalyst is regenerated:  Hazards Because acyl chlorides are such reactive compounds. to give aryl ketones: The first step is the dissociation of the chlorine atom: This is followed by nucleophilic attack of the arene toward the acyl group: Finally. Lithium tri-tert-butoxyaluminium hydride. . acyl chlorides participate in Friedel-Crafts acylations.Acyl chlorides are reduced by strong hydride donors such as lithium aluminium hydride and diisobutylaluminium hydride to give primary alcohols.  Electrophilic reactions With Lewis acid catalysts like ferric chloride or aluminium chloride. They are lachrymatory chemicals because they can react with water at the surface of the eye producing hydrochloric and organic acids irritating to the eye. as does the Rosenmund reduction using hydrogen gas over a poisoned palladium catalyst. Similar problems can result if one inhales acyl chloride vapors. a chlorine atom reacts to form HCl. reduces acyl chlorides to aldehydes.
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