Carboxylic Acids and

1
Chapter 18

• Carboxylic Acids and
• Derivatives

2
Derivatives of Carboxylic Acids

• Carboxylic acid backbone

3

• Carboxylic acid

4

• Ester

5

• Amide

6

• Anhydride

7

• Carbonyl compound Any compound that contains a
  carbonyl group (CO).
• Carbonyl groups are strongly polarized, with a
  partial positive charge on carbon and partial
  negative charge on oxygen.

8
(No Transcript)
9

• Carbonyl group
• Carboxyl group
• Polarity
• Hydrogen bonding

10
Nomenclature

• methanoic acid, HCOOH
• formic acid
• nettles, ants
• ethanoic acid, CH3COOH
• acetic acid
• vinegar 5 acetic acid

11

• benzoic acid
• salicylic acid

12

• butanoic acid, CH3CH2CH2COOH
• butyric acid
• rancid butter
• oxalic acid, HOOCCOOH
• dicarboxylic acid
• rhubarb

13

• citric acid
• tricarboxylic acid
• lactic acid
• CH3CHCOOH
• OH
• a-hydroxyacid

14
IUPAC Carboxylic acids

• Longest chain containing COOH
• -COOH is always carbon 1

15
IUPAC -- Esters

• Carboxylic acid alcohol ? ester water
• alcohol common name carboxylate ion name
• propanoic acid methyl alcohol
• methyl propanoate

16

• decanoic acid ethyl alcohol
• ethyl decanoate
• acetic acid cyclopentyl alcohol
• cyclopentyl acetate

17
Common Esters

• wintergreen methyl salicylate
• pineapple ethyl butanoate
• apricot pentyl butanoate

18

• banana isopentyl acetate (isoamyl acetate)
• apple ethyl pentanoate
• rum isobutyl propanoate

19

• raspberry isobutyl formate
• rose benzyl butanoate
• orange octyl acetate

20

• peach benzyl acetate
• grape methyl o-aminobenzoate

21
IUPAC -- Amides

• amine carboxyl
• acetamide
• N-methylacetamide
• N,N-dimethylacetamide

22

• m-toluic acid
• DEET (N,N-diethyl-m-toluamide)

23
Physical Properties

• Boiling point intermolecular forces
• hydrogen bonding
• dimer formation
• highest boiling point (except for ionic)
• Solubility polarity
• polar because of carboxyl group
• soluble to 41 CO ratio

24
Solubility Switch

• alkylamine acid ? alkylammonium salt
• (insoluble) (soluble)
• (not charged) (charged)
• carboxylic acid base
• ? carboxylate ion water
• (insoluble) (soluble)
• (not charged) (charged)

25
Summary
0

• Boiling point
• hydrocarbonsltethersltaldehydes and
  ketonesltestersltamideslt3 amineslt1 and 2 amines
• lt alcoholsltcarboxylic acidsltammonium and
  carboxylate salts
• Solubility (C4 rule)
• hydrocarbonsltethersltaldehydes and
  ketonesltestersltamideslt3 amineslt1 and 2 amines
• ltalcoholsltcarboxylic acidsltammonium and
  carboxylate salts

26
Redox Reactions

• Primary alcohol
• ? aldehyde
• ? carboxylic acid
• Secondary alcohol
• ? ketone
• Tertiary alcohol
• ? no reaction

27
Substitution ReactionsEsterification

• carboxylic acid alcohol ? ester water
• acetic acid methyl alcohol
• ? methyl acetate water

28
Substitution ReactionsAmide Formation

• carboxylic acid amine ? amide water
• acetic acid methylamine
• ? N-methylacetamide water

29

• benzoic acid ethyl alcohol
• ? ethyl benzoate water

30
Hydrolysis of Esters(add H2O)

• Acid-catalyzed (reversible)
• Ester water ? carboxylic acid alcohol
• methyl acetate H2O
• ? acetic acid methanol

31

• Base-catalyzed (not reversible)
• (saponification)
• Ester water ? carboxylate ion alcohol
• methyl acetate H2O
• ? acetate ion methanol

32
Hydrolysis of Amides(add H2O)

• Acid-catalyzed (reversible)(digestion)
• Amide water
• ? carboxylic acid ammonium ion
• methyl acetamide H2O
• ? acetic acid methylammonium ion

33

• Base-catalyzed (not reversible)
• Amide water ? carboxylate ion amine
• methyl acetamide H2O
• ? acetate ion methylamine

34

• Carboxylic acid in acid -COOH
• Carboxylic acid in base -COO-
• Amine in acid -NH3
• Amine in base -NH2

35
Phosphate esters

• Phosphoric acid, H3PO4
• (Low pH or acidic solution)

36

• Phosphate ion, PO43-
• (High pH or basic solution)

37

• Methyl phosphate

38
Phosphorylation

• AMP
• (R adenine)

39

• ADP (R adenine)

40

• ATP (R adenine)