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Project Overview Chapter 17 Carboxylic Acids and Their Derivatives Nucleophilic Addition–Elimination at the Acyl Carbon Ch. 17 - 1 1. Introduction Carboxylic Acid Derivatives O O O O R OH R Cl R O R' carboxylic acid acid chloride acid anhydride O O R OR' R NR'2 ester amide Ch. 17 - 2 2. Nomenclature and Physical Properties Nomenclature of Carboxylic Acids and Derivatives ● Rules Carboxylic acid as parent (suffix): ending with “–oic acid” Carboxylate as parent (suffix): ending with “–oate” Ch. 17 - 3 Most anhydrides are named by dropping the word acid from the name of the carboxylic acid and then adding the word “anhydride” Acid chloride as parent (suffix): ending with “–oyl chloride” Ester as parent (suffix): ending with “–oate” Amide as parent (suffix): ending with “amide” Nitrile as parent (suffix): ending with “nitrile” Ch. 17 - 4 Examples O O OH OCH3 Ethanoic acid Methyl propanoate (acetic acid) O O O O NH'2 Ethanoic anhydride Ethanamide (acetic anhydride) Ch. 17 - 5 Examples O O Cl O Na Sodium benzoate Benzoyl chloride H3C C N Ethanenitrile Ch. 17 - 6 2C. Acidity of Carboxylic Acids O H R O pKa ~ 4-5 Compare ● pKa of H2O ~ 16 ● pKa of H2CO3 ~ 7 ● pKa of HF ~ 3 Ch. 17 - 7 When comparing acidity of organic compounds, we compare the stability of their conjugate bases. The more stable the conjugate base, the stronger the acid CH3COOH CH3CH2OH pKa 4.75 16 Ch. 17 - 8 O O + + H2O + H3O CH3 O H CH3 O A1 B1 + CH3CH2 O H + H2O CH3CH2 O + H3O A2 B2 Ch. 17 - 9 The conjugate base B1 is more stable (the anion is more delocalized) than B2 due to resonance stabilization O O O CH3 O CH3 O CH3 O ● Thus, A1 is a stronger acid than A2 Ch. 17 - 10 Acidity of Carboxylic Acids, Phenols and Alcohols H H O O O H O pKa = 4.20 pKa = ~ 10 pKa = ~ 17 Ch. 17 - 11 Acidity of Carboxylic Acids, Phenols and Alcohols O O H O O + H2O + + H3O O O Ch. 17 - 12 Acidity of Carboxylic Acids, Phenols and Alcohols O O H + + H3O + H2O O O O Ch. 17 - 13 Acidity of Carboxylic Acids, Phenols and Alcohols O O H + + H2O + H3O (NO resonance stabilization) Ch. 17 - 14 Question If you are given three unknown samples: one is benzoic acid; one is phenol; and one is cyclohexyl alcohol; how would you distinguish them by simple chemical tests? ● Recall: acidity of H H O O O H O > > Ch. 17 - 15 O O H + Na OH + H2O R O R O Na (soluable in water) O O Na H + NaOH (soluble in water) O H + NaOH No Reaction (immiscible with H O) 2 Ch. 17 - 16 O O H O O Na + NaHCO3 + CO2(g) + H2O (gas evolved) O H + NaHCO3 No Reaction O H + NaHCO3 No Reaction Ch. 17 - 17 O O O O Cl Cl Cl H > > > Cl OH Cl OH H OH H OH Cl H H H pKa 0.70 1.48 2.86 4.76 Stability of conjugate bases O O O O Cl Cl Cl H Cl > O > Cl O > H O > H O Cl H H H Ch. 17 - 18 O Cl O > > OH OH Cl 2-Chlorobutanoic acid 3-Chlorobutanoic acid (pKa = 2.85) (pKa = 4.05) O Cl OH 4-Chlorobutanoic acid (pKa = 4.50) Ch. 17 - 19 2D. Dicarboxylic Acids pKa (at 25oC) Common o Structure Name mp ( C) pK1 pK2 HO2C CO2H Oxalic acid 189 dec 1.2 4.2 HO2CCH2CO2H Malonic acid 136 2.9 5.7 HO2C(CH2)4CO2H Adipic acid 153 4.4 5.6 CO2H Phthalic acid 206-208 dec 2.9 5.4 CO2H Ch. 17 - 20 2J. Spectroscopic Properties of Acyl Compounds IR Spectra ● The C=O stretching band occurs at different frequencies for acids, esters, and amides, and its precise location is often helpful in structure determination ● Conjugation and electron-donating groups bonded to the carbonyl shift the location of the C=O absorption to lower frequencies Ch. 17 - 21 IR Spectra ● Electron-withdrawing groups bonded to the carbonyl shift the C=O absorption to higher frequencies ● The hydroxyl groups of carboxylic acids also give rise to a broad peak in the 2500-3100-cm-1 region arising from O– H stretching vibrations ● The N–H stretching vibrations of amides absorb between 3140 and 3500 cm-1 Ch. 17 - 22 Ch. 17 - 23 Ch. 17 - 24 1H NMR Spectra ● The acidic protons of carboxylic acids are highly deshielded and absorb far downfield in the δ 10-12 region ● The protons of the a carbon of carboxylic acids absorb in the δ 2.0-2.5 region Ch. 17 - 25 Ch. 17 - 26 13C NMR Spectra ● The carbonyl carbon of carboxylic acids and their derivatives occurs downfield in the δ 160-180 region (see the following examples), but not as far downfield as for aldehydes and ketones (δ 180- 220) ● The nitrile carbon is not shifted so far downfield and absorbs in the δ 115-120 region Ch. 17 - 27 13C NMR chemical shifts for the carbonyl or nitrile carbon atom O O O C C C H3C OH H3C OEt H3C Cl δ 177.2 δ 170.7 δ 170.3 O C H3C C N H3C NH2 δ 172.6 δ 117.4 Ch. 17 - 28 3. Preparation of Carboxylic Acids By oxidation cleavage of alkenes ● Using KMnO4 − 1. KMnO4, OH , heat Ph + 2. H3O OH O + Ph O OH ● Using ozonolysis HO OH O O 1. O3 2. H2O2 Ch. 17 - 29 By oxidation of aldehydes & 1o alcohols ● e.g. H OH 1. Ag2O O+ O 2. H3 O OH − 1. KMnO4, OH , heat OH + O 2. H3O O O H2CrO4 H or OH OH Ch. 17 - 30 By oxidation of alkyl benzene O R − 1. KMnO4, OH , heat OH + 2. H3O (R = 1o or 2o alkyl groups) Ch. 17 - 31 By oxidation of benzene ring ● e.g. O 1. O3, CH3COOH 2. H O 2 2 OH Ch. 17 - 32 By hydrolysis of cyanohydrins and other nitriles ● e.g. O O HCN NC OH H+ HO C OH Ph CH3 Ph CH3 H2O Ph CH3 O HCN H+ Br CN C OH H2O, heat Ch. 17 - 33 By carbonation of Grignard reagents ● e.g. Br MgBr Mg Et2O 1. CO2 + 2. H3O O OH Ch. 17 - 34 4. Acyl Substitution: Nucleophilic Addition-Elimination at the Acyl Carbon O O Nu + Nu R Y R Y O Y + R Nu (Y = leaving group, e.g. OR, NR2, Cl) This nucleophilic acyl substitution occurs through a nucleophilic addition-elimination mechanism Ch. 17 - 35 This type of nucleophilic acyl substitution reaction is common for carboxylic acids and their derivatives O O O O R OH R Cl R O R' carboxylic acid acid chloride acid anhydride O O R OR' R NR'2 ester amide Ch. 17 - 36 Unlike carboxylic acids and their derivatives, aldehydes & ketones usually do not undergo this type of nucleophilic acyl substitution, due to the lack of an acyl leaving group A good O leaving O O group R Y R H R R' a carboxylic acid derivative Not a good leaving group Ch. 17 - 37 Relative reactivity of carboxylic acid derivatives towards nucleophilic acyl substitution reactions ● There are 2 steps in a nucleophilic acyl substitution The addition of the nucleophile to the carbonyl group The elimination of the leaving group in the tetrahedral intermediate Ch. 17 - 38 ● Usually the addition step (the first step) is the rate-determining step (r.d.s.). As soon as the tetrahedral intermediate is formed, elimination usually occurs spontaneously to regenerate the carbonyl group ● Thus, both steric and electronic factors that affect the rate of the addition of a nucleophile control the reactivity of the carboxylic acid derivative Ch. 17 - 39 ● Steric factor e.g. O O reactivity of > Cl Cl ● Electronic factor The strongly polarized acid derivatives react more readily than less polar ones Ch. 17 - 40 ● Thus, reactivity of O O O O O > > > R Cl R O R' R OR' R NR'2 most least reactive reactive ● An important consequence of this reactivity It is usually possible to convert a more reactive acid derivative to a less reactive one, but not vice versa Ch. 17 - 41 5. Acyl Chlorides 5A. Synthesis of Acyl Chlorides Conversion of carboxylic acids to acid chlorides O O R OH R Cl ● Common reagents SOCl2 (COCl)2 PCl3 or PCl5 Ch. 17 - 42 ● Mechanism O Cl O Cl O O O Cl R OH R O Cl O O O Cl Cl R O O O O O Cl + CO2 + CO + Cl R O R Cl Cl O Ch. 17 - 43 Nucleophilic acyl substitution reactions of acid chlorides ● Conversion of acid chlorides to carboxylic acids O base O + H2O R Cl R OH Ch. 17 - 44 ● Mechanism O O OH H R O R OH R Cl H2O Cl H Cl H O B: O B H + R OH R OH Ch. 17 - 45 ● Conversion of acid chlorides to other carboxylic derivatives O R'OH (ester) pyridine R OR' O O R'2NH (amide) R Cl R NR'2 O O O R' O Na (acid anhydride) R O R' Ch. 17 - 46 6. Carboxylic Acid Anhydrides 6A. Synthesis of Carboxylic Acid Anhydrides O O + + R OH R' Cl N O O + Cl R O R' N H Ch. 17 - 47 O O O O + + Na Cl R O Na R' Cl R O R' O O OH 300oC O + H2O OH Succinic O Succinic O acid anhydride O O OH 230oC O + H2O OH Phthalic Phthalic anhydride O O acid (~100%) Ch.
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