Properties and Reactions of -COOH Importance of the negative charge found on a carboxylate anion

Parkinson’s disease
Friday, November 27, 2020 07:01 PM • the best current treatment depends on the presence of a
PREPARATION OF CARBOXYLIC ACIDS carboxylate anion.
Oxidation of an Aldehyde or a Primary Alcohol • patients suffer from a dopamine deficiency in the brain.
• used to convert an aldehyde/primary alcohol to the corresponding carboxylic acid: ○ Dopamine needs to be administered to control symptoms of
this disease
• since dopamine carries a net positive charge, it cannot pass the
blood–brain barrier.
• Chemists solved this by connecting a carboxylic acid to
dopamine, creating levodopa (L-dopa) (positive ion)
• Balances the carboxylate’s negative charge
• has an overall zero ionic charge and can cross the blood–
Butyric acid (butanoic acid) brain barrier
○ obtained by oxidizing either 1-butanol/butanal with K2Cr2O7 in the presence of H2SO4 • in the brain, it is converted to dopamine and relieves
Parkinson’s symptoms.
first synthesized in the 1960s continues to be the drug

CHEMICAL PROPERTIES
structural formula
• consists of a carbonyl group and a hydroxyl group in combination. (Hybrid of alcohol and
hydroxy)
Aromatic acids carboxyl group
○ prepared by the same general method. • new functional group with properties different from those of both the carbonyl and hydroxyl
e.g. benzoic acid is obtained by oxidizing benzyl alcohol: groups.
• most acidic of any organic functional group
• OH group acts as a proton donor, even more effectively than phenol.
• commonly is involved in substitution-type reactions.
○ C=O retains its double-bond character
○ OH is replaced by another group or atom.
• react with many substances to produce derivatives
○ the hydroxyl group is replaced by (any)
Carboxylic acids
○ Can be obtained by the hydrolysis or saponification of esters. ▪ a halogen (Cl) ▪ an alkoxy group (OR)
▪ an acyloxy group (OOCR) ▪ an amino group (NH2)
Oxidation of Alkyl Groups Attached to Aromatic Rings
• When reacted with a strong oxidizing agent
◊ alkaline permanganate solution
◊ potassium dichromate and sulfuric acid
○ alkyl groups bonded to aromatic rings are oxidized to carboxyl groups.
• Regardless of the size or length of the alkyl group, the carbon atom adjacent to the ring
 remains bonded to the ring
 is oxidized to a carboxyl group.
• The remainder of the alkyl group goes either to
– carbon dioxide
– salt of a carboxylic acid.
e.g. sodium benzoate is obtained when toluene, ethylbenzene, or propylbenzene is
heated with alkaline permanganate solution:

ACID-BASE REACTIONS
Acids properties
• Due to the ability to form hydrogen ions in solution
1. Taste sour
2. Change blue litmus to red and affect other suitable indicators
3. Form water solutions with pH values of less than 7
4. Undergo neutralization reactions with bases to form water and a salt
▪ All are seen in low-molar mass carboxylic acids such as acetic acid.
• influenced by the size of the hydrocarbon chain attached to the carboxyl group.
○ e.g. stearic acid
▪ taste, effect on indicators, and pH are not detectable
▪ Due to: long hydrocarbon chain w/c makes the acid insoluble in water.
▪ reacts with a base to form water and a salt.

□ Since the reaction is conducted in an alkaline medium, a salt of the carboxylic

acid (sodium benzoate) is formed instead of the free acid

○ To obtain the free carboxylic acid, the reaction mixture is acidified with a strong mineral □ salts formed from this neutralization reaction have properties different from
acid (HCl or H2SO4) in a second step: those of the acids.
Sodium and potassium salts
○ soluble in water and dissociate completely in solution.
○ assist in the separation of carboxylic acids from other nonpolar compounds.
e.g.
▪ when a base like NaOH is added to a reaction mixture containing a carboxylic
acid, the carboxylic acid reacts, forming its sodium salt and water.
▪ salt dissolves in water, while the remaining nonpolar molecules stay in the
organic layer.
Hydrolysis of Nitriles ▪ Once the layers are separated, some mineral acid like HCl can be added to the
• Alkyl halide + KCN = nitrile + KX (by-product) carboxylic acid salt to re-form and to recover the acid.
Carboxylic acids
• Nitriles (RCN)
• generally react with sodium hydrogen carbonate to release carbon dioxide.
○ prepared by
○ used to distinguish a carboxylic acid from a phenol (weak acid).
▪ adding HCN to aldehydes and
• Phenols do not react with sodium hydrogen carbonate, although they will be neutralized by a
ketones
▪ reacting alkyl halides with KCN strong base.
○ can be hydrolyzed to carboxylic acids
SUBSITITUTION REACTIONS
▪ Has a by-product of ammonia
a. Acid Chloride Formation
○ Thionyl chloride (SOCl2) reacts with carboxylic acids to form acid chlorides.
○ a chlorine atom replaces an OH group.
biochemical syntheses.
• Most living cells form carboxylic acids by the oxidation of aldehydes—a common reaction in
organic chemistry.
• vitamin biotin provides a unique synthesis.
○ traps and then transfers carbon dioxide to an acceptor molecule to form a carboxylic acid.
• Malonic acid
○ Formed using
▪ Biotin

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 • vitamin biotin provides a unique synthesis.
○ traps and then transfers carbon dioxide to an acceptor molecule to form a carboxylic acid.
• Malonic acid
○ Formed using
▪ Biotin
▪ the synthesis of fatty acids depends on biotin.
 essential for human good health
Acid chlorides
PHYSICAL PROPERTIES
• consists of a carboxylic acid & hydrocarbon group (-R). • extremely reactive substances.
• must be kept away from moisture
Polarity: polar • they will hydrolyze back to the
○ Affect the chemical and physical properties carboxylic acid:

Solubility • more reactive than acids

○ determined by the highly soluble polar carboxyl group • can be used in place of acids to prepare
▪ 1-4C = water soluble esters and amides:
▪ 5-8C = slightly water soluble
 0.1 g acid/100 g water
▪ ≥8C = virtually insoluble in water
□ the water insolubility of the nonpolar hydrocarbon chain is dominant.

Boiling points b. Acid Anhydride Formation

○ comparatively high boiling points ○ Inorganic anhydrides
□ due to intermolecular attractions resulting from hydrogen bonding • formed by elimination of a molecule of water from
▪ Formic acid = 101°C. an acid/base
▪ Carbon dioxide
□ nonpolar substance of similar molar mass to formic acid organic anhydride
○ formed by the elimination of a molecule of water from two molecules of a carboxylic
□ remains in the gaseous state until it is cooled to -78°C
acid
▪ acetic acid (molar mass 60 g/mol) = 118°C
▪ Nonpolar butane (molar mass 58 g/mol) = -0.6°C

Acetic anhydride
○ most commonly used organic anhydride
○ prepared by the reaction of acetyl chloride with sodium acetate:

○ highly reactive
○ used to synthesize amides and esters, although not as often as the acid chlorides in
organic syntheses.
○ In living cells, acid anhydrides commonly activate carboxylic acids for further reaction.

c. Ester Formation
○ Products: ester & water
 organic compound formed by the reaction of an acid with an alcohol or
a phenol

Acetic acid Nonpolar butane

• molar mass 60 g/mol • molar mass 58 g/mol
• BP 118°C • BP -0.6°C
*molar-mass determinations on gaseous acetic acid (near its boiling point) show 120 g/mol
○ indicating that 2 molecules are joined to form a dimer (CH3COOH)2: • looks like the familiar acid–base neutralization reaction.
. ○ not the case because the alcohol does not yield OH ions and the ester is a molecular,
not ionic, substance, unlike a salt

Esterification
▪ forward reaction of an acid and an alcohol
▪ one of the most important reactions of carboxylic acids
□ biologically significant substances are esters
• Acidity Hydrolysis.
▪ reverse reaction of an ester with water
○ generally weak acids
▪ only slightly ionized in water
▪ ionize in water to produce hydronium
ions and anions.
○ More acidic than phenol
▪ acetic acid ionization constant: 1.8 x 10-5
□ 1.3% ionized for a 0.10 M solution
▪ phenol ionization constant: 1.3 x 10-10
□ 0.00036% ionized for a 0.10 M
solution

Saturated monocarboxylic acids

• <10 carbon atoms = liquids @ room temp
• >10 carbon atoms = wax like solids.

Physiological consequences of ionization

Metabolic acidosis
• life-threatening condition
• related to carboxylic acid ionization.
○ Whenever central energy metabolism is active, carboxylic acids are produced.
○ As the acids are formed, they release hydrogen ions.
○ Under most circumstances, this extra acidity is controlled by readjustments of lung and
kidney function.
○ if too many acids are formed
▪ blood acidity goes out of control and metabolic acidosis develops.

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 ▪ blood acidity goes out of control and metabolic acidosis develops.
▪ Just a small drop in blood pH (to a pH of below about 7.3) may lead to shock or
death.
○ Conditions that result in metabolic acidosis
▪ uncontrolled diabetes
▪ kidney failure
▪ ethylene glycol (antifreeze) poisoning.
○ Treatments
▪ focus on bringing the hydrogen ion concentration (and blood pH) back under control.

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