Title 21. Carboxylic Acids and their Derivatives.pdf ✅

Carboxylic Acids and their Derivatives 363 21 Carboxylic Acids and their Derivatives QUICK LOOK Carboxylic acids are the compounds containing the carboxyl functional group C — C — OH || O       The carboxyl group is made up of carbonyl ( C O) > == and hydroxyl (—OH) group. Carbonyl Hydroxyl Carboxyl O O || || —C — —C — H —C — O — H + ≡≡ Carboxylic acids may be aliphatic or aromatic Comparison of Resonating Structures of Carboxylic Group and Carbonyl Group: Carbonyl group has two resonance structures (I and II) However, for a carboxyl group, three resonance structures (A, B and C) can be written. In both structures (A) and (C), the C–atom and the two O– atoms have eight electrons in their respective valence shells while in structure (B), C–atom has only six electrons. Therefore, structure (B) is less stable than structure (C), in other words the two important resonance structures of carboxyl group are structures (A) and (C). In both these structures, carboxyl carbon is electrically neutral. However in case of aldehydes and ketones, only one structure i.e. I is electrically neutral. As a result, the carboxyl carbon of the resonance hybrid is less positive and hence less electrophilic than the carbonyl carbon of aldehydes and ketones. However, it may be noted that like carbonyl group, carboxyl group is also polar due to resonance structures (B) and (C). Nomenclature: The aliphatic carboxylic acids are commonly known by their initial names, which have been derived from the source of the particular acid. Examples HCOOH Formic acid [Latin: Fermica = ant] CH COOH 3 Acetic acid [Latin: acetum = Vinegar] CH — CH — COOH 3 2 Propionic acid [Greek: Proton = First; Pion = Fat] CH (CH ) COOH 3 2 2 Butyric acid [Latin: Butyrum = Butter] CH (CH ) COOH 3 2 3 Valeric acid CH (CH ) COOH 3 2 14 Palmitic acid CH (CH ) COOH 3 2 16 Stearic acid Alternative system of nomenclature is naming the acids as the derivatives of acetic acids. The only exception being formic acid. Example CH — CH — COOH 3 2 Methyl acetic acid 3 3 (CH ) C — COOH Trimethyl acetic acid According to the IUPAC system of nomenclature, the suffix of the monocarboxylic acid is ‘oic acid’, which is added to the name of the alkane corresponding to the longest carbon chain containing the carboxyl group, e.g. HCOOHmethanoic acid CH — CH — CH — COOH 3 2 2 butanoic acid. The positions of side-chains (or substituents) are indicated by numbers, the numbering to be started from the side of the carboxyl group. 5 4 3 2 1 3 2 3 3 CH — CH— CH CH — COOH | | CH CH 3,4-dimethylpentanoic acid Naming of Acyl Groups, Acid Chlorides and Anhydrides: The group obtained from a carboxylic acid by the removal of the hydroxyl portion is known as an acyl group. The name of an acyl group is created by changing the - ic acid at the end of the name of the carboxylic acid to –yl, examples: Formic acid Formyl group O O || || H — C — O — H H — C — → O: ɺɺ O H ɺɺ— ɺɺ —C (A) O: − ɺɺ ɺɺ C—H + ɺɺ —C O H ɺɺ— ɺɺ —C + O: − ɺɺ ←→ ɺɺ ←→ (B) (C) ←→ (I) (II) C O: + − == ɺɺ ɺɺ C O == : ɺɺ Aromatic carboxylic acid (Where Ar is any aryl group) O O — H Ar — C Aliphatic carboxylic acid (Where R = H or any alkyl group) O O — H R — C
364 Quick Revision NCERT - CHEMISTRY Acid chlorides are named systematically as acyl chlorides. An acid anhydride is named by substituting anhydride for acid in the name of the acid from which it is derived. Naming of Salts and Esters: The name of the cation (in the case of a salt) or the name of the organic group attached to the oxygen of the carboxyl group (in the case of an ester) precedes the name of the acid. Naming of Amides and Imides: The names of amides are formed by replacing –oic acid (or –ic acid for common names) by amide or –carboxylic acid by carboxamide. If the nitrogen atom of the amide has any alkyl groups as substitutents, the name of the amide is prefixed by the capital letter N; to indicate substitution on nitrogen, followed by the name(s) of alkyl group(s). If the substituent on the nitrogen atom of an amide is a phenyl group, the ending for the name of the carboxylic acid is changed to anilide Some dicarboxylic acids form cylic amides in which two acyl groups are bonded to the nitrogen atom. The suffix imide is given to such compounds. Classification Carboxylic acids are classified as monocarboxylic acids, dicarboxylic acids, tricarboxylic acids etc. depending on the number of —COOH groups present in the molecule. 3 Monocarboxylic acid CH COOH 2 2 Dicarboxylic acid CH COOH | CH COOH 2 2 Tricarboxy lic acid CH COOH | CHCOOH | CH COOH Monocarboxylic acids of aliphatic series are commonly known as fatty acids such as palmitic acid (C15H31COOH) and stearic acid (C17H35COOH). The general formula for monocarboxylic acids is CnH2n+1COOH or CnH2nO2.Where n = number of carbon atoms. The carboxylic acids may be aliphatic or aromatic depending upon whether –COOH group is attached to aliphatic alkyl chain or aryl group respectively. Some of the important uses of Carboxylic Acids are Higher fatty acids are used in the manufacture of soaps. Soaps are sodium potassium salts of higher fatty acids such as stearic acid. Organic acids are used in foods, cold drinks, etc. For example, acetic acid is used as vinegar. Sodium salts of some organic acids are used as preservatives. Organic acids are used for the preparation of many drugs such as aspirin, phenacetin etc. Acetic acid is used as coagulant in the manufacture of rubber. Acetic acid is also used in the manufacture of various dye stuffs, perfumes and rayon. H O N O Pyrrolidine-2, 5-dione 1N-isoindole-1, 3(2H)-dione NH O O N-phenylacetamide NH H C3 O O NH N-phenylbenzamide N — CH3 N-ethyl-N-methyl-4-nitrobenzamide H C3 O CH3 cyclohexanecarboxamide NH2 O NH2 acetamide H C3 O Ethyl 4-methylbenzoate H C3 O O 1-phenylethanone sodium CH3 benzoate O O Na − + Dihydrofuran-2, 2-dione O O O succinic acid O OH O OH O O O 2-benz of uran-1, 3-dione COOH COOH phthalic acid Acetyl chloride H C3 Cl O O || C — OH Benzoic acid O || C — Benzoyl acid
Carboxylic Acids and their Derivatives 365 General Methods of Preparation 1. Oxidation of Alcohols, Aldehydes and Ketones 2 2 7 2 2 7 [O] [O] 2 K Cr O K Cr O Carboxylic acid alcohol RCH OH RCHO RCOOH → → [O] Aldehyde monocarboxylic acid RCHO RCOOH → Aldehyde can be oxidized to carboxylic acid with mild oxidising agents such as ammonical silver nitrate solution [Ag2O or Ag(NH ) OH ] 3 2 + − Methanoic acid cannot be prepared by oxidation method. Ketones can be oxidized under drastic conditions using strong oxidising agent like K Cr O . 2 2 7 Methyl ketones can also be converted to carboxylic acid through the halo form reaction. 2 R — C — CH 3I 3NaOH 3 2 H O || O ∆ + + → R — C — OH CHI 3NaI 3H O 3 2 || O + + + 2. Oxidation of Alkyl Benzenes: Although benzene and alkane are quite unreative towards the usual oxidizing agents (KMnO4, K2Cr2O7 etc). The benzene ring renders an aliphatic side chain quite susceptible to oxidation. The side chain is oxidised down to the ring and only a carboxyl group (COOH) remains to indicate the position of the original side chain. Potassium permanganate is generally used for this purpose, although potassium dichromate or dilute nitric acid can also be used. (Oxidation of a side chain is more difficult, however, than oxidation of an alkene and requires prolonged treatment with hot KMnO4) This reaction is used for two purposes (a) synthesis of carboxylic acids and (b) identification of alkyl benzenes. 3. Carbonation of Grignard Reagents: The Grignard synthesis of a carboxylic acid is carried out by bubbling gaseous CO2 into the ether solution of the Grignard reagent or by pouring the Grignard reagent on crushed dry ice (solid CO2). In the latter method dry ice serves not only as reagent but also as cooling agent. The Grignard reagent adds to the carbon–oxygen double bond of CO2 just as in the reaction with aldehydes and keotnes. The product is the magnesium salt of the carboxylic acid, from which the free acid is liberated by treatment with mineral acid. Grignard's reagent R — MgX + O || C || O H 2 R — COO Mg X R — COOH Mg X + → → + + − + + − The Grignard’s reagent can be prepared from primary, secondary, tertiary or aromatic halides. The method is limited only by the presence of other reactive group in the molecule. The following synthesis illustrates the application of this method. 3 3 3 CH | H C — C — OH | CH →HCl 3 3 3 CH | H C — C — Cl | CH →Mg 3 3 3 CH | H C — C — MgCl | CH H + → 3 3 3 Trimethylacetic acid CH | H C — C — COOH | CH 4. Hydrolysis of Nitriles: Aliphatic nitriles are prepared by treatment of alkyl halides with sodium cyanide in a solvent that will dissolve both reactants. In dimethyl sulfoxide (DMSO), reaction occurs rapidly and exothermically at room temperature. The resulting nitrile is then hydrolysed to the acid by boiling with aqueous alkali or acid. 5. Use of Alkoxide H RO Na CO RCOONa RCOOH dark + − + ∆ + → → CH O Na CO CH COOH 3 3 − + → 8 210 C, pressure CH OH CO CH COOH 3 3 Co(CO) ° + → 6. Carbonylation of Alkenes H PO 3 4 CH CH CO H O CH CH COOH 2 2 2 3 2 300 400 C − ° = + + → H PO3 4 3 2 2 3 300 400 C 3 CH CH CH CO H O CH —CH —COOH | CH − ° == + + → 7. Oxidative Cleavage of Alkenes, Alkynes and Cyclo Alkenes 3 4 2 (i)O or KMnO RC CR RCOOH R 'COOH (ii) H O ≡≡ → + ′ OH R — COO NH3 − → +− H R — COOH NH4 + → + + DMSO R — Cl NaCN R — C N H O — + → ≡≡ + 2 n-butyl CH CH CH CH 2 2 2 3 Benzoic acid COOH hot KMnO4 → + CO2
366 Quick Revision NCERT - CHEMISTRY 3 2 (i)O CH C CCH 2CH COOH 3 3 3 (ii) H O ≡≡ → 4 (i)Alkaline KMnO (ii) H / RCH CHR 2RCOOH + ∆ == → KMnO / / H 4 + → ∆ 2 2 CH COOH | CH COOH Carboxylic Acid Derivatives: There are four carboxylic acid derivatives. These are generally represented as O || R — C — Z, where Z is halogen (usually Cl), OCOR , OR' ' or NH2 (or NHR' or 2 NR )' . When Z is halogen (usually Cl), the derivatives are called as acid chlorides. O || R — C — Cl When Z is OR′, the derivatives are called as esters. When Z is O || —O — C — R', the derivatives are called carboxylic anhydrides. Where Z is  NH2, the derivatives are called amides. When Z is NHR′ or NR2′ they are called N–substituted amides. Synthesis of Acid Derivatives: Carboxylic acid derivatives are exclusively prepared from carboxylic acids. The preparation methods of carboxylic acid derivatives are already discussed under the chemical reactions of carboxylic acids. Chemical Reactions of Acid Derivatives Acyl chloride: We have already seen that acyl chlorides are the most reactive of all acid derivatives. As a result, acyl chlorides are often selected as the starting material for the preparation any other acid derivative. Let us see how this is done. O O O O || || || || R —C —Cl R —C —O Na R —C —O —C—R' − + + → O O || || R — C — Cl R — OH R — C — O — R + → ' 3 2 O O || || R — C — Cl NH R — C — NH + → 2 O O || || R — C — Cl R NH R — C — NHR + → ' ' O O || || R — C — Cl R R NH R — C — NR R + → ′ ′′ ′ ′′ 3 2 6 5 6 5 3 O O || || H C — C — Cl H NC H C H NHC — CH HCl + → + Reaction of Acetyl Chloride with Olefins: Acetyl chlorides add on to the double bond of an olefin in the presence of a catalyst (AlCl3 or ZnCl2) to form a chloro ketone which on heating, eliminates a molecule of hydrogen chloride to form an unsaturated ketone. ZnCl2 H C — CH CH CH COCl H C — CH — CH — C — CH 3 2 3 3 2 3 == + → 3 2 3 3 2 3 2 O || H C — CH CH CH COCl H C — CH — CH — C — CH | Cl == + → 3 3 O || H C — CH CH — C — CH HCl → == + ∆ Conversion into acids: Hydrolysis. 2 An acid O O || || R — C — Cl H O R — C — OH HCl + → + Carboxylic acid anhydrides: Carboxylic acid anhydrides can be used to prepare esters and amides. R'OH O O O || || || R — C — O — C — R R — C — OR → ' NH3 Excess O || + → R — C — OH 2 4 O O || || R — C — NH R — C — O NH − + + Anhydrides can be hydrolysed to get back acids. H O2 O O O || || || R — C — O — C — R 2R — C — OH → Esters Ester Hydrolysis: Acid catalysed esterification is an essentially reversible reaction. If you follow the backward course of reactions of esterification it gives you the mechanism for ester hydrolysis. O || R — C — OR' H O2 H →+ O || R — C — OH R OH + ' Base promoted Hydrolysis of Esters Saponification: Esters undergo base promoted hydrolysis also. This reaction is known as saponification, because it is the way most of the soaps are manufactured. Refluxing an ester with Acetyl salicylic acid (aspirin) COOH OH 3 O || O — C — CH COOH + → CH COCl 3