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Organic Lecture Series Carboxylic Acids Chapter 17 111 Organic Lecture Series Structure • The functional group of a carboxylic acid is a carboxyl group O O C COOH CO2 H OH OH Alternative representations for a carboxyl group – the general formula for an aliphatic carboxylic acid is RCOOH; that for an aromatic carboxylic acid is ArCOOH 222 Organic Lecture Series Nomenclature • IUPAC names: drop the -e from the parent alkane and add the suffix -oic acid O HCOOH CH COOH 3 OH Methanoic acid Ethanoic acid 3-Methylbutanoic acid (Formic acid) (Acetic acid) (Isovaleric acid) – if the compound contains a carbon-carbon double bond, change the infix -an- to -en- O O O OH OH OH Propenoic acid t rans-2-Butenoic acid t rans-3-Phenylpropenoic acid (Acrylic acid) (Crotonic acid) (Cinnamic acid) 333 Organic Lecture Series • The carboxyl group takes precedence over most other functional groups OH O O O O H N OH OH 2 OH (R)-5-Hydroxyhexanoic 5-Oxohexanoic acid 4-Aminobutanoic acid acid O O δδδ βββ OH γγγ ααα 5 3 1 OH O H 4 2 γγγ-hydroxybutyric Acid GHB 444 Organic Lecture Series Nomenclature – dicarboxylic acids : add the suffix -dioic acid to the name of the parent alkane containing both carboxyl groups O O O HO OH HO OH O Ethanedioic acid Propanedioic acid (Oxalic acid) (Malonic acid) O O O O HO HO OH HO OH OH O O Butanedioic acid Pentanedioic acid Hexanedioic acid (Succinic acid) (Glutaric acid) (Adipic acid) 555 Organic Lecture Series Nomenclature – if the carboxyl group is bonded to a ring, name the ring compound and add the suffix -carboxylic acid 2 1 COOH 3 HOOC COOH 2-Cyclohexenecarboxylic t rans-1,3-Cyclopentanedicarboxylic acid acid – benzoic acid is the simplest aromatic carboxylic acid – use numbers to show the location of substituents COOH COOH COOH COOH OH COOH COOH Benzoic 2-Hydroxybenzoic 1,2-Benzenedicarboxylic 1,4-Benzenedicarboxylic acid acid acid acid (Salicylic acid) (Phthalic acid) (Terephthalic acid) 666 Organic Lecture Series Nomenclature – when common names are used, the letters α, β, γ, δ, etc. are often used to locate substituents O O O δδδ γγγ βββ ααα H2 N OH 5 3 1 OH OH 4 2 NH2 4-Aminobutanoic acid (S)-2-Aminopropanoic acid (γγγ-Aminobutyric acid, GABA) [(S)-ααα-Aminopropionic acid; L-alanine] 777 Organic Lecture Series Physical Properties • In the liquid and solid states, carboxylic acids are associated by hydrogen bonding into dimeric structures 888 Physical Properties Organic Lecture Series • Carboxylic acids have significantly higher boiling points than other types of organic compounds of comparable molecular weight –they are polar compounds and form very strong intermolecular hydrogen bonds 999 Physical Properties Organic Lecture Series • Carboxylic acids are more soluble in water than alcohols , ethers, aldehydes, and ketones of comparable molecular weight –they form hydrogen bonds with water molecules through their C=O and OH groups 101010 Organic Lecture Series Physical Properties Molecular Boiling Weight Point Solubility Structure Name (g/mol) (°C) (g/100 g H2O) CH3 COOH Acetic acid 60.1 118 Infinite CH3 CH2 CH2 OH 1-Propanol 60.1 97 Infinite CH3 CH2 CHO Propanal 58.1 48 16 CH3 ( CH2 )2 COOH Butanoic acid 88.1 163 Infinite CH3 (CH2 ) 3 CH2 OH 1-Pentanol 88.1 137 2.3 CH3 ( CH2 )3 CHO Pentanal 86.1 103 Slight CH3 ( CH2 )4 COOH Hexanoic acid 116.2 205 1.0 CH3 (CH2 ) 5 CH2 OH 1-Heptanol 116.2 176 0.2 CH3 ( CH2 )5 CHO Heptanal114.1 153 0.1 111111 Organic Lecture Series Physical Properties – water solubility decreases as the relative size of the hydrophobic portion of the molecule increases 121212 Organic Lecture Series Acidity • Carboxylic acids are weak acids – values of p Ka for most aliphatic and aromatic carboxylic acids fall within the range 4 to 5 • The greater acidity of carboxylic acids relative to alcohols (both compounds that contain an OH group) is due to resonance stabilization of the carboxylate anion: O O O H H 3 C OH H 3 C O H 3 C O 131313 Organic Lecture Series Acidity – electron-withdrawing substituents near the carboxyl group increase acidity through their inductive effect Formula: CH3 COOH ClCH2 COOH Cl2 CHCOOH Cl3 CCOOH Name: Acetic Chloroacetic Dichloroacetic Trichloroacetic acid acid acid acid K p a: 4.76 2.86 1.48 0.70 Increasing acid strength 141414 Organic Lecture Series – the form of a carboxylic acid present in aqueous solution depends on the pH of the solution O - O O OH- O OH - - R-C-OH R-C-OH + R-C-O + R-C-O H+ H predominant present in equal predominant species when concentrations when species when the pH of the the pH of the the pH of the solution is solution is equal to solution is 2.0 or less K 7.0 or greater the p a of the acid [A-] pH = pKa + log10 [HA] 151515 Organic Lecture Series For organic acids in equilibrium: HA H+ + A- Henderson-Hasselbalch equation: [A-] pH = pKa + log10 [HA] 161616 Reaction with Bases Organic Lecture Series Carboxylic acids, whether soluble or insoluble in water, react with NaOH, KOH, and other strong bases to give water- soluble salts - + COOH + NaOH COO Na + H2 O H2 O Benzoic acid Sodium benzoate (slightly soluble (60 g/100 mL water) in water) Acid + Base Salt + water 171717 Organic Lecture Series Reaction with Bases • They also form water-soluble salts with ammonia and amines - + COOH+ NH3 COO NH4 H2 O Benzoic acid Ammonium benzoate (slightly soluble (20 g/100 mL water) in water) 181818 Reaction with Bases Organic Lecture Series • Carboxylic acids react with sodium bicarbonate and sodium carbonate to form water-soluble salts and carbonic acid – carbonic acid, in turn, breaks down to carbon dioxide and water - + + CH3 COOH NaHCO3 CH3 COO Na + H2 CO3 H CO 2 3 CO2 + H2 O - + + + CH3 COOH NaHCO3 CH3 COO Na CO2 + H2 O 191919 Organic Lecture Series Preparation • Carbonation of Grignard reagents – treatment of a Grignard reagent with carbon dioxide followed by acidification gives a carboxylic acid O MgBr + C O Carbon dioxide O O HCl C-O - [MgBr]+ C-OH + Mg2 + H2 O A magnesium carboxylate Cyclopentane- carboxylic acid 202020 Reduction Organic Lecture Series • The carboxyl group is very resistant to reduction – it is not affected by catalytic hydrogenation under conditions that easily reduce aldehydes and ketones to alcohols, and reduce alkenes and alkynes to alkanes; it is not reduced by NaBH 4 • Lithium aluminum hydride reduces a carboxyl group to a 1°alcohol – reduction is carried out in diethyl ether, THF, or other nonreactive, aprotic solvent O 1. LiAlH4 + COH CH2 OH+ LiOH Al(OH) 3 2. H2 O 4-Hydroxymethyl- cyclopentene 212121 Organic Lecture Series Selective Reduction – carboxyl groups are not affected by catalytic reduction under conditions that reduce aldehydes and ketones O O OH O Pt OH + H2 OH 25°C, 2 atm 5-Oxohexanoic acid 5-Hydroxyhexanoic acid (racemic) – nor are carboxyl groups reduced by NaBH 4 O O OH O NaBH4 C6 H5 OH C6 H5 OH H2 O 5-Oxo-5-phenylpentanoicacid 5-Hydroxy-5-phenylpentanoicacid (racemic) 222222 Organic Lecture Series Fischer Esterification • Esters can be prepared by treating a carboxylic acid with an alcohol in the presence of an acid catalyst, commonly H2SO 4, ArSO 3H*, or gaseous HCl O O H2 SO4 OH + HO O + H2 O Ethanoic acid Ethanol Ethyl ethanoate (Acetic acid) (Ethyl alcohol) (Ethyl acetate) O * H 3 C S OH O Toluene Sulfonic Acid T s O H 232323 Organic Lecture Series Fischer Esterification Fischer esterification is an equilibrium reaction: by careful control of experimental conditions, it is possible to prepare esters in high yield if the alcohol is inexpensive relative to the carboxylic acid, it can be used in excess to drive the equilibrium to the right alternatively, water can be removed by azeotropic distillation and a Dean-Stark trap 242424 Organic Lecture Series Fischer Esterification a key intermediate in Fischer esterification is the tetrahedral carbonyl addition intermediate formed by addition of ROH to the C=O group H TCAI O R C OCH3 O H + H+ O H O RC OH + HOCH3 R C OCH3 + HOH Refer to mechanism worksheet 252525 Organic Lecture Series Acid Chlorides • The functional group of an acid halide is a carbonyl group bonded to a halogen atom – among the acid halides, acid chlorides are by far the most common and the most widely used OO O C-Cl - C- X CH3 CCl Functional group Acetyl Benzoyl of an acid halide chloride chloride 262626 Organic Lecture Series Acid Chlorides – acid chlorides are most often prepared by treating a carboxylic acid with thionyl chloride O O OH + SOCl2 Cl + SO2 + HCl Butanoic acid Thionyl chloride Butanoyl chloride 272727 Organic Lecture Series Acid Chlorides • The mechanism for this reaction is divided into two steps. Step 1: reaction with SOCl 2 transforms OH, a poor leaving group, into a chlorosulfite group, a good leaving group O O OO R-C-O-H + Cl-S-ClR C O S Cl + H-Cl A chlorosulfite group 282828 Organic Lecture Series Acid Chlorides Step 2: attack of chloride ion gives a tetrahedral carbonyl addition intermediate, which collapses to give the acid chloride O O R CO S Cl + Cl - O:- O O - R C O S Cl R-C-Cl + SO2 + Cl Cl A tetrahedral carbonyl addition intermediate Note: the reaction is irreversible 292929 Organic Lecture Series Decarboxylation • Decarboxylation: loss of CO 2 from a carboxyl group – carboxylic acids, if heated to a very high temperature , undergo thermal decarboxylation O decarboxylation R-C-OH R-H + CO heat 2 – most carboxylic acids, however, are quite resistant to moderate heat and melt or even boil without decarboxylation 303030 Organic Lecture Series Decarboxylation The most important exceptions are carboxylic acids that have a carbonyl group beta to the carboxyl group
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  • Experiment 2: Two Step Synthesis of Ethyl 4-Methoxycinnamate

    Experiment 2: Two Step Synthesis of Ethyl 4-Methoxycinnamate

    Experiment 2: Two step synthesis of ethyl 4-methoxycinnamate Background Why is ethyl 4-methoxycinnamate (1) interesting? First, it is the analog of octyl 4-methoxycinnamate (2), a UV light blocker found in Bain de Soleil All Day Sunblock and Coppertone Sport. The derivatives of 4-methoxycinnamic acid absorb UVB radiation due to their high level of conjugation. They are also oil soluble. UVB radiation promotes dermal cell DNA damage causing skin cancer. Octyl 4-methoxycinnamate is used in sunscreen over ethyl 4-methoxycinnamate because of its higher molar absorptivity ε and its greater lipophilicity. O R O O R = -CH3CH3 ethyl 4-methoxycinnamate (1) R = octyl 4-methoxycinnamate (2) Figure 1: Derivatives of 4-methoxycinnamic acid Second, a two step synthesis is put forth so that you can practice multi-step synthesis using a variety of laboratory techniques before diving into Honors Cup. Step 1 is the Verley-Doebner modification of the Knoevenagel condensation.1 The Knoevenagel condensation reaction dates from 1896 and is a facile one-step method of forming new carbon- carbon bonds under mild reaction conditions. It utilizes a weak amine base such as piperidine to initially form an enolate anion derived from a 1,3-dicarbonyl compound. The enolate subsequently acts as a nucleophile in the condensation with another carbonyl compound. This carbonyl is often an aldehyde and the reaction mechanism bears striking similarity to that of the aldol condensation. The isolated product is generally an α,β-conjugated carboxylic acid, formed via ready dehydration of the intermediate β-hydroxydicarbonyl compound and subsequent saponification and decarboxylation.