1. LECTURE 2
THEME: Structure and chemical properties of carboxylic acids. Heterofunctional compounds.
Lecturer: Yevheniya. B. Dmukhalska

2. Plan
Nomenclature of carboxylic acids
Physical properties of carboxylic acids.
Classification of carboxylic acids
Methods of preparation of carboxylic acids
Chemical properties of carboxylic acids.
Heterofunctional compounds.
Hydroxy-acids, nomenclature, isomerism, chemical properties and specific reactions for hydroxy-acids.
Introduction of optical isomerous. Mirror (optical) isomerism. Asymmetric carbon atom. Properties of enantiomers.

3. Carboxylic acids
Carboxylic acids are compounds whose characteristic functional group is the carboxyl group - COOH , example:
Common formula of carboxylic acid:

4. Nomenclature of carboxylic acids
Formula
Common Name
IUPAC Name
HCO2H
formic acid
methanoic acid
CH3CO2H
acetic acid
ethanoic acid
CH3CH2CO2H
propionic acid
propanoic acid
CH3(CH2)2CO2H
butyric acid
butanoic acid
CH3(CH2)3CO2H
valeric acid
pentanoic acid
CH3(CH2)4CO2H
caproic acid
hexanoic acid
CH3(CH2)5CO2H
enanthic acid
heptanoic acid
CH3(CH2)6CO2H
caprylic acid
octanoic acid
CH3(CH2)7CO2H
pelargonic acid
nonanoic acid
CH3(CH2)8CO2H
capric acid
decanoic acid

5. Classification of carboxylic acids :
1. By the nature of hydrocarbon radical
a) saturated acids;
b) unsaturated acids
c) aromatic acid
2. By the number of carboxyl groups
a) monocarboxylic acids;
b) dicarboxylic acids.

6. Saturated acids
are acids, which have only simple bonds in molecule. Example:
methanoic (formic) acid
ethanoic (acetic) acid
propanoic (propionic acid) acid
stearic acid (octadecanoic acid)
CH3-(CH2)16-COOH

7. Unsaturated acid
is an acid, which has both as simple bonds and duble bonds in molecule. Example:
CH2=CH-COOH

8. Aromatic acid
is acid, which contain aromatic ring. Example: benzoic acid.

9. Monocarboxylic acid
is acid, which has one carboxylic group in molecule. Example: acetic acid, formic acid, buthanic acid.

10. Dicarboxylic acid
is acid, which has two carboxylic group in molecule. Example: oxalic acid, malonic acid.

11. The names of some saturated monocarboxylic acids
Structural formula
Name of nomenclature
trivial
substitute
rational
formic acid
methanoic acid -
acetic acid
etanoic acid
propionic acid
propanoic acid
methylacetic acid
oil acid
butanoic acid
ethylacetic acid
iso oil acid
2-methylpropanoic acid
dimethylacetic acid
valeric acid
pentanoic acid
propylacetic acid
iso valeric acid
3-methylbutanoic acid
methylethylacetic acid
CH3-(CH2)4-COOH
capronic acid
hexanoic acid
n-butylacetic acid
CH3-(CH2)10-COOH
lauric acid
dodecanoic acid
CH3-(CH2)12-COOH
myristic acid
tetradecanoic acid
CH3-(CH2)14-COOH
palmitic acid
hexadecanoic acid
CH3-(CH2)16-COOH
stearic acid
octadecanoic acid

12. The names of some unsaturated monocarboxylic acids
Structural formula
Name of nomenclature
trivial
substitute
CH2=CH-COOH
acrylic acid
propenoic acid
methacrylic acid
2-methylpropenoic acid
CH2=CH-CH2-COOH
vinyl acetic acid
3-butenoic acid
crotonic acid
trans-2-butenoic acid
iso crotonic acid
cus-2-butenoic acid
propiolic acid
propionoic acid
tetrolic acid
2-butynoic acid
oleic acid
cus-9-octadecenoic acid
Linoleic acid
cus-9-cus-12-octadecadienoic acid
linolenic acid
cus-9-cus-15-octadecatrienoic acid

13. Structural formula Name of nomenclature trivial substitute
The names of some dicarboxylic acids
Structural formula
Name of nomenclature
trivial
substitute
HOOC-COOH
oxalic acid
ethandioic acid
HOOC-CH2-COOH
malonic acid
propandioic acid
HOOC-CH2-CH2-COOH
succinic acid
butandioic acid
HOOC-CH2-CH2-CH2-COOH
glutaric acid
pentandioic acid
HOOC-CH2-CH2-CH2-CH2-COOH
adypinic acid
hexandioic acid
HOOC-(CH2)5-COOH
pimelic acid
heptadioic acid
HOOC-(CH2)6-COOH
cork acid
octandioic acid
maleic acid
cus-butendioic acid
fumaric acid
trans-butendioic acid
phthalic acid
1,2-benzoldicarbonic acid
iso phthalic acid
1,3-benzoldicarbonic acid

14. Methods of preparation of carboxylic acids.
Oxidation of alkylbenzenes.
Oxidation of primary alcohols.
Oxidation of aldehydes.

15. 4. Synthesis of carboxylic acids by the hydrolysis of nitriles.

16. Properties of Carboxylic Acids
Physical Properties of Carboxylic Acids
Formula
IUPAC Name
Melting Point
Boiling Point
HCO2H
methanoic acid
8.4 ºC
101 ºC
CH3CO2H
ethanoic acid
16.6 ºC
118 ºC
CH3CH2CO2H
propanoic acid
-20.8 ºC
141 ºC
CH3(CH2)2CO2H
butanoic acid
-5.5 ºC
164 ºC
CH3(CH2)3CO2H
pentanoic acid
-34.5 ºC
186 ºC
CH3(CH2)4CO2H
hexanoic acid
-4.0 ºC
205 ºC
CH3(CH2)5CO2H
heptanoic acid
-7.5 ºC
223 ºC
CH3(CH2)6CO2H
octanoic acid
16.3 ºC
239 ºC
CH3(CH2)7CO2H
nonanoic acid
12.0 ºC
253 ºC
CH3(CH2)8CO2H
decanoic acid
31.0 ºC
219 ºC

17. Solubility of carboxylic acids

18. Chemical properties of carboxylic acids.

19. Reduction reaction.
Carboxylic acids are reduced to primary alcohols by the powerful reducing agent lithium aluminum hydride.

22. Salt formation
Sodium butanoate
Magnesium acetate
Calcium acetate

23. α-halogenation of carboxylic acids
This method of α bromination of carboxylic acids is called the Hell–Volhard– Zelinsky reaction.

24. Substitution of the Hydroxyl Group
Except reaction 3

25. 1. ESTERIFICATION
This page looks at esterification - mainly the reaction between alcohols and carboxylic acids to make esters.

26. Reaction with halo-compounds:
2. Formation of acyl chlorides. Formation of acyl chlorides. Thionyl chloride reacts with carboxylic acids to yield acyl chlorides.
Reaction with halo-compounds:

27. 3. Preparation of Acid Anhydrides

28. 4. The formation amides.

29. Formation of the biuret and a biuret reaction
urea

30. Decarboxylation of carboxylic acids.
The loss of a molecule of carbon dioxide from a carboxylic acid is known as decarboxylation.

33. 8. Carboxylic acid derivatives.
These classes of compounds are classified as carboxylic acid derivatives. All may be converted to carboxylic acids by hydrolysis.

34. Sphingosine Monofunctional group – contains only 1 functional group.
Functional groups are groups of atoms found within molecules that are involved in the chemical reactions characteristic of those molecules.
There are mono-, poly- and heterofunctional group in the structure of organic compounds:
Monofunctional group – contains only 1 functional group.
C2H5—OH
Polyfunctional group – contains several similar functional group.
Heterofunctional group – contains several different functional group.
Sphingosine

35. Biological role:
Heterofunctional compounds are widespread in the nature. They are in fruits and vegetable leafs. Also they are formed in body. So, the lactic acid is product of transformation glucose (glycolysis) in human body. A malic and citric acid formed in a cycle of tricarboxylic acids, which is also known as citric acid cycle or Krebs' cycle. Hydroxo acids such as: pyruvic acid, acetoacetic acid, oxaloacetic acid, -ketoglutaric acid are important in metabolism of carbohydrates.

36. Hydroxyacids
Hydroxyacids are the derivatives of carboxyl acids that contain –OH group (1 or more).
β α
2-hydroxypropanoic acid
α-hydroxypropanoic acid

37. α,α’-dihydroxysuccinic acid, 2,3-dihydroxybutandioic acid,
glycolic acid,
hydroxyacetic acid,
hydroxyethanoic acid
tartaric acid
α,α’-dihydroxysuccinic acid,
2,3-dihydroxybutandioic acid,
lactic acid,
α- hydroxypropanoic acid,
2- hydroxypropanoic acid
malic acid,
hydroxysuccinic acid
hydroxybutanedioic acid
citric acid,
2-hydroxy-1,2,3-propantricarboxylic acid

38. Methods of preparation of hydroxyacids:
Hydrolysis of α-halogenoacids
Oxidations of diols and hydroxyaldehydes
Hydration of α,β-unsaturated carboxylic acids
Hydrolysis of hydroxynitriles (cyanohydrins)
lactic acid
β-hydroxypropanoic acid

39. Physical and chemical properties of hydroxycarboxylic acid
For physical properties of hydroxycarboxylic acids are colorless liquids or crystalline substance, soluble in water.
Chemical properties:
Carboxyl group can react forming:
a) salts:
sodium β-hydroxypropanoic acid

41. Ester formation: Methyl-β-hydroxypropanoate Methyl-β-methoxylpropanoat
β-ethanoatepropanoic acid

42. a) hydrohalogens (HCl, HBr, HI, HF)
c) Amides formation:
II. –OH group reaction:
a) hydrohalogens (HCl, HBr, HI, HF)
b) can oxidize
amide of β-hydroxypropanoic acid
β-oxopropanoic acid

43. Related to heat of: lactic acid 1. α-hydroxyacids lactide

44. Decomposition α-hydroxyacids
Ethanal
formic acid

45. 3,4,5-trihydroxybenzoic acid,
Phenolacids.
Phenolacids are the derivatives of aromatic carboxyl acids that contain –OH group (1 or more).
salicylic acid,
2-hydroxybenzoic acid
o-hydroxycinnamic acid
4-hydroxybenzoic acid
3,4,5-trihydroxybenzoic acid,
gallic acid

46. Phenolacids are the derivatives of aromatic carboxyl acids that contain –OH group (1 or more).
Decarboxylation

48. Representatives of hydroxyacids:
Lactic acid is a trivial name because at first it was extracted from milk. It is present in yogurt, sour milk and other milk products. It can form in muscles during hard and prolonged work. Salts of milk acid are used in medicine.
Malic acid. It is present in green apples and
some berries. It takes part in biological processes in human organisms and organisms of other alive creatures. It is used in medicine for synthesis of some medical preparations.
Tartaric acid . It is present in grape. It is used in medicine for synthesis of some medical preparations.

49. Citric acid. It is present in. orange, lemon and other. citric fruits
Citric acid . It is present in orange, lemon and other citric fruits. It takes part in biological processes in human organism.

50. Oxoacids
To oxoacids include aldehydo- and ketonoacids. These compounds include in the structure of the carboxyl group, aldehyde functional group or ketone functional group.
acetoacetic acid,
3-oxobutanoic acid,
β-ketobutyric acid
glyoxylic acid,
oxoethanoic acid
Pyroracemic (pyruvic) acid,
2-oxopropanoic acid
oxalacetic acid,
oxobutanedioic acid,
ketosuccinic acid
γ-ketovaleric acid,
4-oxopentanoic acid,
levulinic acid
ketoglutaric acid

52. Chemical properties of oxoacids
Decarboxylation of α-oxoacids
Decarboxylation of β-oxoacids

53. Thank you for attention