1. Chapter 12 Organic Compounds with Oxygen and Sulfur
12.1
Alcohols, Phenols, Thiols, and Ethers

2. Alcohols
An alcohol contains a hydroxyl group (–OH) that replaces a hydrogen atom in a hydrocarbon. A phenol contains a hydroxyl group (–OH) attached to a benzene ring.

3. Naming Alcohols The names of alcohols
in the IUPAC system replace the -e with -ol
with common names use the name of the alkyl group followed by alcohol
Formula
IUPAC
Common Name
CH4
methane
CH3─OH
methanol
methyl alcohol
CH3─CH3
ethane
CH3─CH2─OH
ethanol
ethyl alcohol

4. Naming Alcohols

5. Naming of Alcohols
Step 1 Name the longest carbon chain with the –OH group. Name an aromatic alcohol as a phenol. CH3CH2CH2OH propanol OH CH3CHCH2CH3 butanol CH3 OH CH3CHCH2CH2CHCH3 hexanol

6. Naming of Alcohols
Step 2 Number the chain starting at the end closer to the –OH. CH3CH2CH2OH 1-propanol OH CH3CHCH2CH3 2-butanol CH3 OH CH3CHCH2CH2CHCH3 2-hexanol

7. Naming of Alcohols
Step 3 Give the location and name of each substituent relative to the –OH group. CH3CH2CH2OH 1-propanol OH CH3CHCH2CH3 2-butanol CH3 OH CH3CHCH2CH2CHCH3 5-methyl-2-hexanol

8. Some Typical Alcohols | “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

9. Learning Check Name the following compounds: 1. CH3—CH2—CH2—CH2—OH
OH CH3
| |
2. CH3—CH—CH—CH2—CH3 3.

10. Solution Step 1 Name the longest carbon chain with the –OH group.
Name an aromatic alcohol as a phenol.
1. CH3—CH2—CH2—CH2—OH butanol
OH CH3
| |
2. CH3—CH—CH—CH2—CH pentanol
cyclopentanol

11. Solution Step 2 Number the chain starting at the end closer to the
–OH.
1. CH3—CH2—CH2—CH2—OH butanol
OH CH3
| |
2. CH3—CH—CH—CH2—CH pentanol
cyclopentanol

12. Solution Step 3 Give the location and name of each substituent
relative to the –OH group.
1. CH3—CH2—CH2—CH2—OH butanol
OH CH3
| |
2. CH3—CH—CH—CH2—CH methyl-2-pentanol
cyclopentanol

13. Phenols in Medicine Phenol is
the IUPAC name for benzene with a hydroxyl group
used in antiseptics and disinfectants
Phenol Resorcinol Hexylresorcinol

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

15. Naming Phenols
Step 1 Name the longest carbon chain with the –OH group.
Name an aromatic alcohol as a phenol.
phenol phenol

16. Naming Phenols
Step 2 Number the chain starting at the end closer to the
–OH.
phenol phenol

17. Naming Phenols Step 3 Give the location and name of each substituent
relative to the –OH group.
3-chlorophenol bromophenol

18. Learning Check
Write the structure of each of the following: A. 3-pentanol B. ethyl alcohol C. 4-methylphenol

19. Solution Write the structure of each of the following:
A. 3-pentanol OH |
CH3—CH2—CH—CH2—CH3
B. ethyl alcohol CH3—CH2—OH
C. 4-methylphenol O H C 3

20. Thiols Thiols contain sulfur are similar to alcohols
contain a thiol (–SH) group
often have strong odors
are found in cheese, onions, garlic, and oysters
are used to detect gas leaks

21. Thiols
Thiols are named in the IUPAC system by adding thiol to the alkane name of the longest carbon chain.

22. Ethers An ether contains an –O– between two carbon groups
has a common name that gives the alkyl names of the attached groups, followed by ether
CH3OCH3 CH3CH2OCH3

23. Learning Check
Write the structure of the following: A. 3-pentanol B. ethanethiol C. diethyl ether

24. Solution OH | A. 3-pentanol CH3CH2CHCH2CH3
B. ethanethiol CH3CH2SH
C. diethyl ether CH3CH2OCH2CH3

25. Ethers as Anesthetics Anesthetics inhibit pain signals to the brain
like diethyl ether, CH3CH2OCH2CH3, were used for over a century, but caused nausea and were flammable
developed by the 1960s were nonflammable
Cl F F Cl F H
HCCOCH HCCOCH
F F F H F H
Ethrane (enflurane) Penthrane

26. Chapter 12 Organic Compounds with Oxygen and Sulfur
12.2 Properties of Alcohols and Ethers

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

28. Learning Check OH | A. CH3—CH—CH2—CH3 B. CH3—CH2—CH2—OH
Classify each alcohol as primary, secondary, or tertiary. OH |
A. CH3—CH—CH2—CH3
B. CH3—CH2—CH2—OH
C. CH3—CH2—C—CH2—CH3
CH3

29. Solution | A. CH3—CH—CH2—CH3 secondary B. CH3—CH2—CH2—OH primary
C. CH3—CH2—C—CH2—CH3 tertiary
CH3

30. Solubility of Alcohols in Water
contain polar OH groups and form hydrogen bonds with other alcohol molecules
that have one to three carbons are soluble in water
solubility in water decreases with increasing number of carbons

31. Solubility of Ethers in Water
do not have a polar OH group, but have a COC group
do not form hydrogen bonds
with less than four carbons are slightly soluble in water
with more than four carbons are not soluble in water

32. Solubility of Alcohols and Ethers in Water

33. Solubility of Phenols Phenols are slightly soluble in water
have an OH group that can form hydrogen bonds with water
can react with water to produce phenoxide ions
were once used as antiseptics
+ H2O H3O+

34. Learning Check
Indicate whether each of the following is soluble in water
and explain why.
A. CH3CH2CH2CH2CH2CH2OH
B. CH3OCH2CH3
C. CH3CH2OH

35. Solution Indicate whether each of the following is soluble in water
and explain why.
A. CH3CH2CH2CH2CH2CH2OH Not soluble
Alcohols with long carbon chains (nonpolar) are not soluble.
B. CH3OCH2CH Slightly soluble
Ethers with less than four carbons are only slightly soluble in water.
C. CH3CH2OH Soluble
Short-chain alcohols form hydrogen bonds with water.

36. Chapter 12 Organic Compounds with Oxygen and Sulfur
12.3
Reactions of Alcohols and Thiols

37. Dehydration of Alcohols
Alcohols undergo
dehydration when heated with an acid catalyst
the loss of –H and –OH from adjacent carbon atoms, producing an alkene
H OH
| | H+, heat
H—C—C—H H—C=C—H + H2O
| | | |
H H H H
alcohol alkene

38. Oxidation of 1 Alcohols
Alcohols undergo oxidation, increasing the number of carbon and oxygen bonds.
Primary alcohols are oxidized to produce an aldehyde.
1 bond to O bonds to O
H OH H O
| | oxidation | ||
H—C—C—H H—C—C—H
| | |
H H H
1 alcohol aldehyde

39. Oxidation of 1 Alcohols
Alcohols undergo oxidation, increasing the number of carbon and oxygen bonds.
Aldehydes can further oxidize to produce a carboxylic acid.
1 bond to O bonds to O
H O H O
| || oxidation | ||
H—C—C—H H—C—C—OH
| |
H H
aldehyde carboxylic acid

40. Oxidation of 2 Alcohols
Secondary alcohols are oxidized to produce a ketone.
To indicate the process of oxidation, [O] is placed over the reaction arrow.
1 bond to O bonds to O
H OH H H O H
| | | [O] | || |
H—C—C—C—H H—C—C—C—H
| | | | |
H H H H H
2 alcohol ketone

41. Oxidation of Tertiary 3 Alcohols
Tertiary (3) alcohols do not readily oxidize. OH CH3CCH3 [O] no product CH3 no H to oxidize 3 alcohol no reaction

42. Oxidation and Reduction
In an oxidation,
there is an increase in the number of C–O bonds
there is a loss of H
In a reduction,
there is a decrease in the number of C–O bonds
there is a gain of H

43. Oxidation and Reduction

44. Methanol Poisoning Methanol is also known as methyl alcohol
is highly toxic and found in windshield washer fluid, Sterno, and paint strippers
is rapidly absorbed and oxidized to formaldehyde and then formic acid
O O
[O] [O]
CH3OH HCH HCOH
methyl alcohol formaldehyde formic acid

45. Ethanol, CH3CH2OH Ethanol
acts as a depressant and kills or disables more people than any other drug
is metabolized at a rate of 12–15 mg/dL per hour by a social drinker
is metabolized at a rate of 30 mg/dL per hour by an alcoholic

46. Effect of Alcohol on the Body

47. Oxidation of Thiols When thiols undergo oxidation,
an H atom is lost from each of two –SH groups
the product is a disulfide
protein in hair is cross-linked by disulfide bonds found in the amino acid cysteine

48. Learning Check OH [O] CH3CHCH2CH3 O
Select the product for the oxidation of OH
[O]
CH3CHCH2CH3 O
A. CH3CH=CHCH B. CH3CCH2CH3
C. CO2 + H2O D. CH3CHCH2CH3

49. Solution OH [O] CH3CHCH2CH3 O The answer is B. CH3CCH2CH3
Select the product for the oxidation of OH
[O]
CH3CHCH2CH3 O
The answer is B CH3CCH2CH3

50. Learning Check
Select the product when CH3–CH2–CH2–OH undergoes each of the following reactions: [O] [O] CH3—CH2 —CH2OH B. C. 1) CH3—CH=CH2 2) CO2 + H2O O || 3) CH3—CH2—C—H O 4) CH3—CH2—C—OH

51. Solution
Select the product when CH3–CH2–CH2–OH undergoes each of the following reactions: O [O] B. 3) || CH3—CH2—CH2OH CH3—CH2—C—H [O] C. 4) || CH3—CH2—C—OH

52. Learning Check
Give the primary product for the reaction of 2-propanol when it undergoes A. oxidation B. dehydration

53. Solution
OH CH3CHCH3 = 2-propanol = C3H8O A. oxidation OH O [O] 2CH3CHCH3 + 9O2 CH3CCH3 + 6CO2 + 8H2O B. dehydration H+, heat CH3CHCH3 CH3CH=CH2 + H2O

54. Chapter 12 Organic Compounds with Oxygen and Sulfur
12.4
Aldehydes and Ketones

55. Carbonyl Group in Aldehydes and Ketones
A carbonyl group
consists of a carbon-oxygen polar double bond
has a very electronegative oxygen atom
has two lone pair electrons on the O atom
has partial positive charge on C and partial negative charge on O

56. Carbonyl Group in Aldehydes and Ketones
A carbonyl group
in an aldehyde is attached to at least one H atom
in a ketone is attached to two carbon groups

57. Naming Aldehydes An aldehyde
has an IUPAC name in which the -e in the alkane name is changed to -al
has a common name for the first four aldehydes that use the following prefixes:
1 carbon, form
2 carbons, acet
3 carbons, propion
4 carbons butyr
followed by aldehyde

58. Naming Aldehydes

59. Naming Aldehydes

60. Naming Aldehydes Give the IUPAC name for the following aldehydes: O ||
CH3CH2CH2CHCH |
CH3

61. Naming Aldehydes Step 1 Name the longest carbon chain containing the
carbonyl group by replacing the e in the
alkane name with al. O ||
CH3CH2CH2CHCH |
CH3
pentanal
benzaldehyde

62. Naming Aldehydes Step 2 Name and number substituents by counting the
carbonyl group as carbon 1. O ||
CH3CH2CH2CHCH |
CH3
2-methylpentanal
3,4-dichlorobenzaldehyde

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

64. Naming Ketones When naming the following ketones
in the IUPAC system, the -e in the alkane name is replaced with -one
with a common name, the alkyl groups attached to the carbonyl group are named alphabetically, followed by ketone
O O
CH3 CCH CH3CCH2CH3
propanone butanone
(dimethyl ketone) (ethyl methyl ketone)

65. Naming Ketones

66. Naming Ketones
Name the following ketones using the IUPAC system. O || CH3CH2CHCH2CCH3 | CH3

67. Naming Ketones
Step 1 Name the longest carbon chain that contains the carbonyl group by replacing the e in the alkane name with one. O || CH3CH2CHCH2CCH3 | CH3 hexanone
pentanone

68. Naming Ketones
Step 2 Number the carbon chain starting from the end nearer the carbonyl group and indicate its location. O || CH3CH2CHCH2CCH3 | CH3 2-hexanone
pentanone

69. Naming Ketones
Step 3 Name and number any substituents on the carbon chain. O || CH3CH2CHCH2CCH3 | CH3 4-methyl-2-hexanone
2,3-dimethylcylcopentanone

70. Ketones in Common Use
Acetone (propanone) is a solvent used in nail polish remover.
Butanedione is the butter flavoring used in margarine.

71. Learning Check
Classify each as an aldehyde or ketone. O O || || A. CH3—CH2—C—CH3 B. CH3—C—H CH3 O | || C. CH3—C—CH2—C—H D. | CH3

72. Solution
Classify each as an aldehyde or ketone. O O || || A. CH3—CH2—C—CH3 B. CH3—C—H CH3 O | || C. CH3—C—CH2—C—H D. | CH3
ketone
aldehyde
aldehyde
ketone

73. Learning Check
Classify each as an aldehyde, ketone, alcohol, or ether. O A. CH3CH2CCH3 B. CH3OCH3 CH3 O OH C. CH3CCH2CH D. CH3CHCH3 CH3

74. Solution
Classify each as an aldehyde, ketone, alcohol, or ether. O A. CH3CH2CCH3 B. CH3OCH3 CH3 O OH C. CH3CCH2CH D. CH3CHCH3 CH3
ketone ether
aldehyde alcohol

75. Learning Check
Give the IUPAC name for each of the following ketones. O A. CH3CH2CH2CH2CCH3 B. ClCH2CH2CCH3

76. Solution Give the IUPAC name for each of the following ketones.
Step 1 Name the longest carbon chain that contains the
carbonyl group by replacing the e in the alkane name
with one. O
A. CH3CH2CH2CH2CCH3 pentanone
B. ClCH2CH2CCH3 butanone

77. Solution Give the IUPAC name for each of the following ketones.
Step 2 Name the carbon chain starting from the end nearer the
carbonyl group and indicate its location. O
A. CH3CH2CH2CH2CCH3 2-pentanone
B. ClCH2CH2CCH3 2-butanone

78. Solution Give the IUPAC name for each of the following ketones.
Step 3 Name and number any substituents on the carbon chain. O
A. CH3CH2CH2CH2CCH3 2-pentanone
B. ClCH2CH2CCH3 4-chloro-2-butanone

79. Learning Check
Give the IUPAC name for the following aldehyde compounds. O || A. CH3—CH2—CH2—C—H CH3 O | || B. CH3—C—CH2—C—H | CH3

80. Solution
Give the IUPAC name for the following aldehyde compounds. Step 1 Name the longest carbon chain containing the carbonyl group by replacing the e in the alkane name with al. O || A. CH3—CH2—CH2—C—H butanal CH3 O | || B. CH3—C—CH2—C—H butanal | CH3

81. Solution
Give the IUPAC name for the following aldehyde compounds. Step 2 Name and number substituents by counting the carbonyl group as carbon 1. O || A. CH3—CH2—CH2—C—H butanal CH3 O | || B. CH3—C—CH2—C—H 3,3-dimethylbutanal | CH3

82. Learning Check
Draw the structural formulas for each: A. 4-methylpentanal B. 2,3-dichloropropanal C. 3-methyl-2-butanone

83. Solution
Draw the structural formulas for each: CH3 O A. 4-methylpentanal CH3CHCH2CH2CH Cl O B. 2,3-dichloropropanal ClCH2CHCH CH3 O C. 3-methyl-2-butanone CH3CHCCH3

84. Chapter 12 Organic Compounds with Oxygen and Sulfur
12.5 Properties of Aldehydes and Ketones
In Tollens’ test, a silver mirror forms when the oxidation of an aldehyde reduces silver ion to metallic silver. The silvery surface of a mirror is formed in a similar way.

85. Physical Properties
The polar carbonyl group provides dipole-dipole interactions. + - + - C=O C=O Because the electronegative oxygen atom forms hydrogen bonds with water molecules, aldehydes and ketones with one to four carbons are very soluble.

86. Solubility of Aldehydes and Ketones in Water

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

88. Learning Check
Indicate whether each is soluble or insoluble in water. A. CH3—CH2—CH3 B. CH3—CH2—OH O || C. CH3—CH2—CH2—C—H D. CH3—C—CH3

89. Solution
Indicate whether each is soluble or insoluble in water. A. CH3—CH2—CH3 insoluble B. CH3—CH2—OH soluble O || C. CH3—CH2—CH2—C—H soluble D. CH3—C—CH3 soluble

90. Oxidation of Aldehydes
Primary alcohols can be oxidized to aldehydes, which can be easily oxidized to carboxylic acids. Secondary alcohols can be oxidized to ketones, which cannot be further oxidized.

91. Tollens’ Test In 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.

92. Tollens’ Test

93. Benedict’s Test
In Benedict’s test, Benedict’s reagent, which contains Cu2+, reacts with aldehydes that have an adjacent OH group.

94. Benedict’s Test In Benedict’s test,
an aldehyde is oxidized to a carboxylic acid, while Cu2+ is reduced to give red Cu2O(s).
The blue Cu2+ in Benedict’s solution forms a brick-red solid of Cu2O in a positive test for many sugars and aldehydes with adjacent hydroxyl groups.

95. Reduction of Aldehydes and Ketones
Aldehydes and ketones can be reduced by sodium borohydride, NaBH4, or H2. The reduction of aldehydes and ketones decreases the number of carbon–oxygen bonds by addition of hydrogen or loss of oxygen.

96. Learning Check
Write the structure and name of the organic product when each is mixed with Tollens’ reagent. A. butanal B. acetaldehyde C. ethyl methyl ketone

97. Solution
A. O O || Tollens’ || CH3—CH2—CH2—C—OH CH3—CH2—CH2—C—OH butanal butanoic acid B. O O || Tollens’ || CH3—C—H CH3—C—OH acetaldehyde acetic acid C. Ethyl methyl ketone + Tollens’ No reaction Ketones are not oxidized by Tollens’ reagent.

98. Chapter 12 Organic Compounds with Oxygen and Sulfur
12.6 Chiral Molecules

99. Isomers
Molecules are structural isomers when they have the same molecular formula, but different bonding arrangements.

100. Stereoisomers
Stereoisomers have identical molecular formulas, but they are not structural isomers. In stereoisomers, the atoms are bonded in the same sequence but differ in the way they are arranged in space. When stereoisomers have mirror images that are different, they are said to have “handedness.”

101. Chiral Molecules Have Handedness
have the same number of atoms arranged differently in space
have one or more chiral carbon atoms, each of which is bonded to four different groups
are like your hands
Try to superimpose your thumbs,
palms, back of hands, and little fingers.

102. Some Everyday Chiral and Achiral Objects

103. Chiral Carbon Atoms Are 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.

104. 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.

105. Learning Check A. C H l B. C. B r
Identify each as a chiral or an achiral compound. A. C H 2 3 l B. C. B r

106. Solution chiral achiral chiral A. C H l B. C. B r
Identify each as a chiral or an achiral compound.
chiral achiral chiral A. C H 2 3 l B. C. B r

107. Fischer Projections A Fischer projection
is a two-dimensional representation of a three-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

108. Drawing Fischer Projections

109. 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.

110. Learning Check
Indicate whether each pair is a mirror image that cannot be superimposed (enantiomers).

111. Solution
Indicate whether each pair is a mirror image that cannot be superimposed (enantiomers).
Yes No

112. Concept Map – Organic Molecules with O and S