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Carbonic Acids and Heterofunctional Compounds

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Carbonic Acids and Heterofunctional Compounds Taras Shevchenko National University of Kyiv The Institute of Biology and Medicine METHODICAL POINTING from the course “Biological and bioorganic chemistry” (part 1. Carboxylic acids and heterofunctional compounds (hydroxy-, oxy-, phenoloacids) for the studens of a 1 course with English of educating Compiler – the candidate of biological sciences, the associate professor Synelnyk Tatyana Borysivna Readers: It is ratified to printing by meeting of scientific advice of The Institute of Biology and Medicine (“____”________________ 2018, protocol №____) Kyiv-2018 2 1.1. CARBOXYLIC ACIDS ……………………………………………………. 3 1.1.1. General information ……………………………………………. 3 1.1.2. Nomenclature of carboxylic acids: systematic (substitute) and trivial (common) names …………………………. 4 1.1.3. Classification of carboxylic acids …………………………. 5 1.1.4. Properties of carboxylic acids……………………………….. 8 1.1.5. The common chemical properties of carboxylic acids. Carboxylic acid derivatives………………………….……………………… 9 1.1.6. Chemical properties of unsaturated acids ……………… 13 1.1.7. The most important representatives of saturated carboxylic acids ………………………….…………………………………….. 13 1.1.8. The most important representatives of unsaturated carboxylic acids: characteristics and properties of unsaturated fatty acids ………………………….………………………….………………… 15 1.1.9. Aromatic carboxylic acids…………………………………….. 16 1.1.10. Polycarboxylic acids…………………………………………… 17 1.2. HETEROFUNCTIONAL COMPOUNDS ………………………………. 18 1.2.1. General information ………………………………………….. 18 1.2.2. The chemical properties of heterofunctional compounds ………………………….………………………….……………… 19 1.2.3. Hydroxyacids ………………………….…………………………. 19 1.2.4. Phenolacids as an example of aromatic hydroxyacids . 26 1.2.5. Oxoacids ………………………….……………………………….. 30 1.2.6. Heterofunctional compounds of benzene series ………. 32 1.3. TEST QUESTIONS ………………………….……………………………. 37 3 1.1. CARBOXYLIC ACIDS 1.1.1. General information Carboxylic acids are the organic compounds whose characteristic functional group is the carboxyl group −COOH . In this group a carbon (C) atom is bonded to an oxygen (O) atom by a double bond and to a hydroxyl group (−OH) by a single bond. The carboxyl (COOH) group is so-named because of the carb onyl group (C=O) and hydr oxyl group (OH): So the common formula of carboxylic acid is: Carboxylic acids and their derivates are widespread in nature and are important for studying of biochemistry, pharmacology and other medical disciplines. They get into organism with food and further are converted into other substances. - the fatty acids are components of lipids - lactic acid (found in sour-milk products) and citric acid (found in citrus fruits), and many keto acids are important metabolic products that exist in most living cells. - p roteins are made up of amino acids , which also contain carboxyl groups. Some carboxylic acids and their salts are medical products: - isovaleric acid is a part of validol , - sodium benzoate is disinfectant , - aspirin, the ester of salicylic acid , is prepared from acetic acid. 4 1.1.2. Nomenclature of carboxylic acids: systematic (substitute) and trivial (common) n a m e s Systematic names of carboxylic acids are derived from the name of the longest carbon chain that contains the carboxyl group via dropping the final - e from the name of the parent alkane and adding the suffix -oic followed by the word “acid” (Fig. 1.1). The chain is numbered beginning with the carbon of the carboxyl group. (from “methane”) (from “ethane”) (from “propane”) (from “butane”) Fig 1.1. The systematic names of some carboxylic acids For example, the compound CH 3CH 2COOH has three carbon atoms and is called propanoic acid , from propan e, the name for a three-carbon chain, with -oic acid. If the carboxylic acid contains a carbon-carbon double bond , the ending is changed from -anoic acid to -enoic acid to indicate the presence of the double bond, and a number is used to show the location of the double bond . Most simple carboxylic acids were originally isolated from biological sources; because their structural formulas were often unknown at the time of isolation they were given names – trivial, or common names – that were generally derived from the names of the sources (Fig. 1.2). For example, CH 3CH 2CH 2COOH, butyric acid , first obtained from butter. formic acid a cetic acid propionic acid iso oil acid Fig 1.2. The trivial (common; blue color) and systematic names of some carboxylic acids 5 When common names are used, substituents on the hydrocarbon chain are designated by Greek letters rather than by numbers , and counting begins not with the carboxyl carbon but with the adjacent carbon . For example, the common name of the 4-aminobutanoic acid (IUPAC name) is γ- aminobutyric acid (abbreviated GABA ): This compound is an inhibitory neurotransmitter in the central nervous system of humans. Salts of carboxylic acids are named in the same manner as are the salts of inorganic compounds: the cation is named first and then the anion , as in sodium chloride . For carboxylic acids, the name of the anion is derived by changing the ending -oic acid of the IUPAC name or -ic acid of the common name to -ate. Some examples are: - sodium acetate , CH 3COONa; - ammonium formate , HCOONH 4; - potassium butanoate ( potassium butyrate ), CH 3CH 2CH 2COOK. 1.1.3. Classification of carboxylic acids Carboxylic acids can be classified depending on the nature of hydrocarbon radical: • saturated acids are the acids, which have only simple bonds in molecule: formic acid, butanoic acid (Tab. 1.1); • unsaturated acids are the acids, which have both as simple bonds and double bonds in molecule: oleic acid, linoleic acid, linolenic acid, arachidonic acid (Tab. 1.2) ; • aromatic acids are the acids, which contain aromatic ring: benzoic acid . According to another classification, which is based on the number of carboxyl groups , carboxylic acids can be divided into: • monocarboxylic acids , which have one carboxylic group in molecule: acetic acid, formic acid, butanoic acid; • dicarboxylic acids , which have two carboxylic group in molecule: oxalic acid, malonic acid (Tab. 1.3). 6 Table 1.1. The names of some saturated monocarboxylic acids Structural formula Name of nomenclature trivial substitute rational O formic acid methanoic acid - H C OH O acetic acid etanoic acid acetic acid H3C C OH O propionic propanoic acid methylacetic acid C H3C CH2 acid OH O oil acid butanoic acid ethylacetic acid CH C H3C CH2 2 OH iso oil acid 2- dimethylacetic acid methylpropanoic acid O valeric acid pentanoic acid propylacetic acid CH CH C H3C CH2 2 2 OH 4 3 2 1 O iso valeric 3-methylbutanoic methylethylacetic H C CH CH C acid acid acid 3 2 OH CH3 CH 3-(CH 2)4-COOH capronic hexanoic acid n-butylacetic acid acid CH 3-(CH 2)10 -COOH lauric acid dodecanoic acid CH 3-(CH 2)12 -COOH myristic tetradecanoic acid acid CH 3-(CH 2)14 -COOH palmitic hexadecanoic acid acid CH 3-(CH 2)16 -COOH stearic acid octadecanoic acid 7 Table 1.2. The names of some unsaturated monocarboxylic acids Structural formula Name of nomenclature trivial substitute CH2=CH-COOH acrylic acid propenoic acid methacrylic acid 2-methylpropenoic acid CH 2 C COOH CH 3 CH2=CH-CH2-COOH vinyl acetic acid 3-butenoic acid H crotonic acid trans-2-butenoic acid COOH C C H CH 3 H iso crotonic acid cus-2-butenoic acid H C C COOH CH 3 CH propiolic acid propionoic acid C COOH 4 3 2 1 tetrolic acid 2-butynoic acid CH 3 C C COOH oleic acid cus-9-octadecenoic acid CH (CH 2)7 CH 3 CH (CH ) COOH 2 7 (CH ) Linoleic acid cus-9-cus-12-octadecadienoic CH 3 2 4 CH acid CH CH 2 CH CH (CH 2)7 COOH linolenic acid cus-9-cus-15-octadecatrienoic CH CH 2 CH 3 acid CH CH CH 2 CH CH 2 CH CH (CH ) COOH 2 7 8 Table 1.3. The names of some dicarboxylic acids Structural formula Name of nomenclature trivial substitute HOOC-COOH oxalic acid ethandioic acid HOOC-CH 2-COOH malonic acid propandioic acid HOOC-CH 2-CH 2-COOH succinic acid butandioic acid HOOC-CH 2-CH 2-CH 2-COOH glutaric acid pentandioic acid HOOC-CH 2-CH 2-CH 2-CH 2-COOH adypinic acid hexandioic acid HOOC-(CH 2)5-COOH pimelic acid heptadioic acid HOOC-(CH 2)6-COOH cork acid octandioic acid maleic acid cus-butendioic acid H H C C HOOC COOH H fumaric acid trans-butendioic acid COOH C C H HOOC COOH phthalic acid 1,2-benzoldicarbonic acid COOH COOH iso phthalic acid 1,3-benzoldicarbonic acid COOH 1.1.4. Properties of carboxylic acids Acidity. Carboxylic acids donate H + (hydrogen ion, also called a proton), to another compound, termed a base . Carboxylic acids are generally more acidic than other organic compounds with hydroxyl groups but are generally weaker than the familiar mineral acids (e.g., hydrochloric (HCl), sulfuric (H 2SO 4) or nitric (HNO 3) acids). 9 Solubility. The solubility of carboxylic acids in water is similar to that of alcohols, aldehydes and ketones: • acids with fewer than about five carbons dissolve in water; • those with a higher molecular weight are insoluble throw the larger hydrocarbon chain, which is hydrophobic. The sodium, ammonium, and potassium salts of carboxylic acids, however, are generally quite soluble in water – so, almost any carboxylic acid can be made to dissolve in water by converting it to salt, which is easily done by adding a strong base — most commonly sodium hydroxide (NaOH) or potassium hydroxide (KOH). Boiling point. Carboxylic acids have much higher boiling points than hydrocarbons, alcohols, ethers, aldehydes or ketones with similar molecular weight. So, formic acid boils at 101 °C whereas ethanol (ethyl alcohol), C 2H5OH – at 78.5 °C, although the two have nearly identical molecular weights. This difference is due to two molecules of a carboxylic acid form two hydrogen bonds with each other (two alcohol molecules can form only one).
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