1. Organic I Prof. Dr. Abdellatif M. Salaheldin Chemistry Department

2. Chapter 5 Alcohols, Phenols, Ethers, Aldehydes, Ketones and Thiols

3. Alcohols
In an alcohol, a hydroxyl group (—OH) is attached to a carbon chain.
In a phenol, a hydroxyl group (—OH) is attached to a benzene ring.

4. Classification of Alcohols
Alcohols are classified as primary, secondary, or tertiary.
Classification is determined by the number of alkyl groups attached to the carbon bonded to the hydroxyl. Primary (1º) Secondary (2º) Tertiary (3º) 1 group groups groups H CH CH | | |
CH3—C—OH CH3—C—OH CH3—C—OH | | | H H CH3

5. Naming Alcohols
The IUPAC system replaces the -e in the name of the alkane main chain with –ol.
Common names for simple alcohols use the alkyl name followed by alcohol.
CH4 methane CH3OH methanol (methyl alcohol)
CH3CH3ethane CH3CH2OH ethanol (ethyl alcohol)

6. Naming Alcohols
In the IUPAC names for longer chains, the chain is numbered from the end nearest the -OH group. CH3—CH2—CH2—OH 1-propanol OH | CH3—CH—CH2—CH butanol CH OH | | CH3—CH—CH2—CH—CH methyl-2-pentanol

7. Some Typical Alcohols OH | “rubbing alcohol” CH3—CH—CH3
2-propanol (isopropyl alcohol)
antifreeze HO—CH2—CH2—OH
1,2-ethanediol (ethylene glycol)
glycerol HO—CH2—CH—CH2—OH
1,2,3-propanetriol

8. Naming Phenols A phenol is a benzene ring with a hydroxyl group.
For two substituents, assign C-1 to the carbon attached to the –OH.
Number the ring to give the lowest numbers.
The prefixes o, m, and p are used for common names.

9. Examples of Phenols

10. Phenols in Medicine
Many phenols are used as antiseptics and disinfectants.

11. Derivatives of Phenol
Compounds of phenol are the active ingredients in the essential oils of cloves, vanilla, nutmeg, and mint.

12. Thiols Thiols are carbon compounds that contain the –SH group.
In the IUPAC name, thiol is added to the alkane name of the longest carbon chain.

13. Naming Thiols
In thiols with long carbon chains, the chain is number to locate the -SH group. CH3—CH2—CH2—SH 1-propanethiol SH | CH3—CH—CH3 2-propanethiol

14. Thiols in Nature Thiols: Often have strong or disagreeable odors.
Are used to detect gas leaks.
Are found in onions, oysters, and garlic.

15. Ethers Ethers contain an -O- between two carbon groups.
Simple ethers are named by listing the alkyl names in alphabetical order followed by ether. CH3—O—CH dimethyl ether CH3—O—CH2—CH3 ethyl methyl ether CH3—CH2—O—CH2—CH3 diethyl ether

16. IUPAC Names for Ethers
In the IUPAC system, the shorter alkyl group and the oxygen are named as an alkoxy group attached to the longer alkane.
methoxy propane
CH3—O—CH2—CH2—CH3
Numbering the longer alkane gives
1-methoxypropane.

17. Boiling Points of Alcohols
Alcohols contain a strongly electronegative O in the OH groups.
Thus, hydrogen bonds form between alcohol molecules.
Hydrogen bonds contribute to higher boiling points for alcohols compared to alkanes and ethers of similar mass.

18. Boiling Points of Ethers
Ethers have an O atom, but there is no H attached.
Thus, hydrogen bonds cannot form between ether molecules.

19. Solubility of Alcohols and Ethers in Water
Alcohols and ethers are more soluble in water than alkanes because the oxygen atom can hydrogen bond with water.
Alcohols with 1-4 C atoms are soluble, but alcohols with 5 or more C atoms are not.

20. Reactions of Alcohols
Alcohols undergo combustion with O2 to produce CO2 and H2O.
2CH3OH + 3O CO H2O + Heat
Dehydration removes H- and -OH from adjacent carbon atoms by heating with an acid catalyst.
H OH
| | H+, heat
H—C—C—H H—C=C—H + H2O
| | | |
H H H H
alcohol alkene

21. Formation of Ethers
Ethers form when dehydration takes place at low temperature. H+
CH3—OH + HO—CH CH3—O—CH3 + H2O
Two Methanol Dimethyl ether

22. Oxidation and Reduction
In organic chemistry, oxidation is a loss of hydrogen atoms or a gain of oxygen.
In an oxidation, there is an increase in the number of C-O bonds.
Reduction is a gain of hydrogen or a loss of oxygen. The number of C-O bonds decreases.

23. Oxidation of Primary Alcohols
In the oxidation [O] of a primary alcohol, one H is lost from the –OH and another H from the carbon bonded to the OH.
[O]
Primary alcohol Aldehyde
OH O
| [O] ||
CH3—C—H CH3—C—H + H2O | H
Ethanol Ethanal
(ethyl alcohol) (acetaldehyde)

24. Oxidation of Secondary Alcohols
The oxidation of a secondary alcohol removes one H from –OH and another H from the carbon bonded to the –OH.
[O]
Secondary alcohol Ketone
OH O
| [O] ||
CH3—C—CH CH3—C—CH3 + H2O | H
2-Propanol Propanone
(Isopropyl alcohol) (Dimethylketone; Acetone)

25. Oxidation of Tertiary Alcohols
Tertiary alcohols are resistant to oxidation. [O]
Tertiary alcohols no reaction OH
| [O]
CH3—C—CH3 no product |
CH no H on the C-OH to oxidize
2-Methyl-2-propanol

26. Ethanol CH3CH2OH Ethanol: Acts as a depressant.
Kills or disables more people than any other drug.
Is metabolized at a rate of mg/dl per hour by a social drinker.
Is metabolized at a rate of 30 mg/dl per hour by an alcoholic.

27. Oxidation of Alcohol in the Body
Enzymes in the liver oxidize ethanol.
The aldehyde produced impairs coordination.
A blood alcohol level over 0.4% can be fatal O || CH3CH2OH CH3CH CO2 + H2O Ethyl alcohol acetaldehyde

28. Oxidation of alcohols in liver

29. Breathalyzer test K2Cr2O7 (potassium dichromate)
This orange colored solution is used in the Breathalyzer test (test for blood alcohol level)
Potassium dichromate changes color when it is reduced by alcohol
K2Cr2O7 oxidizes the alcohol

30. Breathalyzer reaction
orange-red green
8H++Cr2O72-+3C2H5OH→2Cr3++3C2H4O+7H2O
dichromate ethyl chromium (III) acetaldehyde
ion alcohol ion
(from K2Cr2O7)

31. Production of ethanol from grain by fermentation
Grain seeds are grounded and cooked → mash
Malt (the dried sprouts of barley) or special mold is added → source of the enzyme diastase that catalyzes the conversion of starch to malt sugar, maltose
diastase
(C6H10O5)2x + H2O → x C12H22O11
starch maltose
Pure yeast culture is added
C12H22O11 + H2O → 2 C6H12O6
maltose glucose
C6H12O6 → 2 CH3CH2OH + 2 CO2
glucose ethanol carbon dioxide

32. Preparation of alcohols
Ethanol is made by hydration of ethylene (ethene) in the presence of acid catalyst

33. Isopropyl
is produced by addition of water to propylene (1-propene)

34. Methanol is made commercially from carbon monoxide and hydrogen
CO + 2H2 → CH3OH

35. Oxidation of Thiols.
Mild oxidizing agens remove two hydrogen atoms from two thiol molecules.
The remaining pieces of thiols combine to form a new molecule, disulfide, with a covalent bond between two sulfur atoms.
R – S – H H – S – R+I2 → RS – SR+2HI
2 RSH + H2O2 → RS – SR + 2 H2O

36. Aldehydes and Ketones
The carbonyl group is found in aldehydes and ketones.
In an aldehyde, an H atom is attached to a carbonyl group.
In a ketone, two carbon groups are attached to a carbonyl group.

37. The Polar Carbonyl Group
The carbonyl group (C=O):
Consists of a sigma and pi bond.
Has a partially negative O and a partially positive C.
Has polarity that influences the properties of aldehydes and ketones.

38. Naming Aldehydes
In the IUPAC names for aldehydes, the -e in the corresponding alkane is replaced by –al.
Common names use a prefix with aldehyde: form (1C), acet (2C), propion (3), and butyr (4C)

39. Aldehydes in Flavorings
Several naturally occurring aldehydes are used as flavorings for foods and fragrances.

40. Naming Ketones
In the IUPAC name, the -e in the alkane name is replaced with –one.
In the common name, add the word ketone after naming the alkyl groups attached to the carbonyl group O O || || CH3—-C—CH CH3—C—CH2—CH3 Propanone Butanone (Dimethyl ketone; (Ethyl methyl ketone) Acetone)

41. Physical Properties
The polar carbonyl group provides dipole-dipole interactions.
+  + -
C=O C=O
Without an H on the oxygen atom, aldehydes and ketones cannot form hydrogen bond.
Aldehydes and ketones can form hydrogen bonds with the water molecules.

42. Comparison of Boiling Points
Aldehydes and ketones have higher boiling points than alkanes and ethers of similar mass, but lower boiling points than alcohols.

43. Solubility in Water
The electronegative O atom of the carbonyl group of aldehydes and ketones forms hydrogen bonds with water.

44. Comparison of Physical Properties

45. Types of Isomers

46. Chiral Objects
Chiral compounds have the same number of atoms arranged differently in space.
A chiral carbon atom is bonded to four different groups.
Your hands are chiral. Try to superimpose your thumbs, palms, back of hands, and little fingers.

47. Mirror Images
The mirror images of chiral compounds cannot be superimposed.
When the H and I atoms are aligned, the Cl and Br atoms are on opposite sides.

48. Achiral Structures are Superimposable
When the mirror image of an achiral structure is rotated, the structure can be aligned with the initial structure. Thus this mirror image is superimposable.

49. Some Everyday Chiral and Achiral Objects

50. Fischer Projections A Fischer projection:
Is a 2-dimensional representation of a 3-dimensional molecule.
Places the most oxidized group at the top.
Uses vertical lines in place of dashes for bonds that go back.
Uses horizontal lines in place of wedges for bonds that come forward.

51. Drawing Fischer Projections

52. D and L Notations
By convention, the letter L is assigned to the structure with the —OH on the left.
The letter D is assigned to the structure with the —OH on the right.

53. Oxidation Aldehydes are easily oxidized to carboxylic acids. O O
CH3—C—H CH3—C—OH
Acetaldehyde Acetic acid

54. Hydrate formation
Hydrate formation is the reason that aldehydes are oxidized ([O]=-2H=oxidation) to carboxylic acids in aqueous media.
O OH O
|| H2O | [O] ||
RCH ↔ RC – OH → RCOH | H

55. Tollens’ Test
Tollens’ reagent, which contains Ag+, oxidizes aldehydes, but not ketones.
Ag+ is reduced to metallic Ag, which appears as a “mirror” in the test tube.

56. Tollens’ reagent detects an aldehyde
Tollens’ reagent (a solution of Ag+ in aqueous NH3) can be used to detect the presence of the aldehyde group in the unknown sample.
As the oxidation of the aldehyde proceeds, silver metal is deposited on the walls of the reaction flask as a shiny mirrow.
If upon addition of the Tollens’ reagent to the unknown, the test tube becomes silvery, the unknown is an aldehyde.
RCHO + 2Ag(NH3)2+ +2OH- → RCOO- + NH4+ + 2Ag + 3NH3 + H2O
an Tollens’ salt of a silver
aldehyde reagent carboxylic acid mirrow

57. Benedict’s Test
Benedict’s reagent, which contains Cu2+, reacts with aldehydes that have an adjacent OH group.
When an aldehyde is oxidized to a carboxylic acid, Cu2+ is reduced to give Cu2O(s).

58. Test for glucose (Benedict’s test)

59. Addition Reactions
Polar molecules can add to the carbonyl groups of aldehydes and ketones.
The negative part of the added molecule bonds to the positive carbonyl carbon.
The positive part of the added molecule bonds to the negative carbonyl oxygen.
| +  +  |
—C=O X—Y — C—O—X | Y

60. Acetal Formation
Alcohols add to the carbonyl group of aldehydes and ketones.
The addition of two alcohols forms acetals.

61. Hemiacetal Formation
The addition of one alcohol to an aldehyde or ketone forms an intermediate called a hemiacetal.
Usually, hemiacetals are unstable and difficult to isolate.

62. Cyclic Hemiacetals
Stable hemiacetals form when the C=O group and the —OH are both part of five- or six-atom carbon compounds.