Basic Organic Chemistry II

1
Organic Chemistry Review

• Part II

2
Functional Groups

1. Hydrocarbons
2. Derivatives of Hydrocarbons

3
Functional Groups

• Organic molecules may have functional groups
  attached.
• A functional group is a group of atoms of a
  particular arrangement that gives the entire
  molecule certain chemical characteristics.
• Functional groups are named according to the
  composition of the group.

4
Functional Groups

• Organic chemists use the letter "R" to indicate
  an organic molecule.
• The "R" can be any organic molecule.

5
Hydrocarbons

• The simplest organic compounds.
• Contain only carbon and hydrogen,
• Can be straight-chain, branched chain, or cyclic
  molecules.
• Carbon tends to form four bonds in a tetrahedral
  geometry.

6
Hydrocarbons

• Two classifications
• Aliphatics
• Aromatics
• Aliphatic - hydrocarbons which do not contain an
  aromatic ring.

7
Hydrocarbons

• Aromatic - Aromatic hydrocarbons contain a set of
  covalently bound atoms with specific
  characteristics
• A delocalized conjugated p system, with the
  common arrangement of alternating single and
  double bonds

8
Aliphatics

1. Alkanes
2. Cycloalkanes
3. Alkenes
4. Alkynes

9
Alkanes

• IUPAC ending is ane

10
Alkanes

• Saturated hydrocarbons.
• Are hydrocarbons which contain only single bonds.
• All alkanes are insoluble in water, but dissolve
  in organic solvents.
• Density, viscosity, melting point boiling
  points increase as the molecular weight/size of
  the hydrocarbon increases.

11
Alkanes

• Contain single covalent bonds.
• Have the same structural formula
• Cn H2n2
• All carbons have single bonds therefore the
  molecular geometry is tetrahedral.

12
Alkanes

• The names of alkanes start with the name of the
  alkane but end with the suffix ane.

13
Alkanes

• Each atom in an alkane uses all its 4 valence
  electrons in forming single bonds with other
  atoms.
• Alkyl groups may be used as substituents for
  hydrogens.

14
Alkanes

• Alkyl groups form the branches of straight chain
  hydrocarbons.
• Can have more than one alkyl group for hydrogens.
• For multiple substituents of the same type, use
  the following prefixes
• di-
• tri-
• tetra-
• penta-
• hexa-

15
Alkanes
16
Alkanes

• Other functional groups can be used as
  substituents.
• More than one substituent requires a prefix.
• Any hydrogen can be substituted by

• Halogens
• Alcohols
• Amines
• Nitriles
• Thiols
• Aldehydes
• Ketones

17
Alkanes

• Any carbon can be substituted by
• Carboxylic Acids
• Esters
• Amides
• Thioesters
• Addition of other atoms
• Ethers
• Thioethers
• Disulfides

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Cycloalkanes

• the prefix cyclo- and the ending ane

19
Cycloalkanes

• Saturated hydrocarbons.
• Form one or more rings fused together.
• A single carbon in a ring may have two hydrogen
  atoms.
• Are insoluble in water, but dissolve in organic
  solvents.
• Have higher boiling points, melting points, and
  densities than alkanes.

20
Cycloalkanes

• All have the same general formula
• CnH2n
• The carbon atoms in cycloalkanes are sp3
  hybridized.
• Each atom in a cycloalkane uses all its 4 valence
  electrons in forming covalent bonds with other
  atoms.

21
Cycloalkanes

• Can have more than one alkyl group to make
  straight chains.
• For multiple alkyl groups of the same type, use
  prefixes.

22
Cycloalkanes

• Many functional groups can be used as
  substituents.
• More than one substituent requires a prefix.
• Any hydrogen or carbon atom can be substituted
  by

23
Cycloalkanes

• The names follow those of the alkanes with the
  prefix cyclo- .

24
Cycloalkanes
25
Cycloalkanes
26
Cycloalkanes
27
Alkenes

• IUPAC ending is ene

28
Alkenes

• Also known as olefins.
• Are unsaturated hydrocarbons and are generally
  very reactive.
• Are insoluble in water, but dissolve in organic
  solvents.
• Ethene, propene and butene are gases at room
  temperature. The remaining are liquids.
• Boiling points increases with molecular mass
  (chain length). The higher the molecular mass,
  the higher the boiling point.

29
Alkenes

• Are hydrocarbons which contain one or more double
  bonds.
• Double bonds are
• Have the same structural formula
• CnH2n

30
Alkenes

• The main centers are the carbons of the double
  bond.
• The geometry of each carbon in the center is
  trigonal planar.
• This portion of the molecule is flat, with bond
  angles of 120 degrees.

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Alkenes

• All the alkenes with 4 or more carbon atoms in
  them show structural isomerism.

32
Alkenes

• The carbon-carbon double bond does not rotate.
• Substituents groups on the molecule are locked on
  either one side of the molecule or opposite each
  other.

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Alkenes

• The names of alkenes start with the name of the
  alkane but end with the suffix ene.
• For alkenes above propene, the position of the
  double bond must be specified in the name.

34
Alkenes

• Can have more than one alkyl group to form
  branches.
• For more than one alkyl group, use prefixes.

35
Alkenes

• Many functional groups can be used as
  substituents.
• More than one substituent requires a prefix.
• Any hydrogen or carbon atom can be substituted
  by

36
Alkenes

• For multiple double bonds, use the following
  prefixes
• di-
• tri-
• tetra-
• penta-
• hexa-

37
Alkenes

• A diene is a hydrocarbon chain that has two
  double bonds that may or may not be adjacent to
  each other.

38
Alkenes Examples
39
Alkenes Examples
40
Alkynes

• IUPAC ending is yne

41
Alkynes

• Also known as acetylenes.
• Are unsaturated hydrocarbons and are generally
  very reactive.
• Are insoluble in water but quite soluble in
  organic solvents of low polarity (e.g. ligroin,
  ether, benzene, carbon tetrachloride, etc.).
• Alkynes of four or fewer carbon atoms are gases.
  The rest are liquids.
• Their boiling points increase with increasing
  number of carbons.

42
Alkynes

• Are hydrocarbons which contain one or more triple
  bonds.
• Triple bonds are
• Have the same structural formula
• CnH2n-2

43
Alkynes

• The main centers are the carbons of the triple
  bond.
• The geometry of the center is linear.
• This portion of the molecule is linear, with bond
  angles of 180 degrees.

44
Alkynes

• All the alkynes with 4 or more carbon atoms in
  them show structural isomerism.

45
Alkynes

• The names of alkynes start with the name of the
  alkane but end with the suffix yne.
• For alkynes above propyne, the position of the
  triple bond must be specified in the name.

46
Alkynes

• Many functional groups can be used as
  substituents.
• Only one substituent is allowed.
• Any hydrogen or carbon atom can be substituted
  by

47
Alkynes

• For multiple double bonds, use the following
  prefixes
• di-
• tri-
• tetra-
• penta-
• hexa-

48
Alkynes Examples
49
Aromatics

• Structures that meet Huckels Rule

50
Aromatics

• Coplanar structures, with all the contributing
  atoms in the same plane.
• Are arranged in one or more rings.
• Benzene rings are not a common motif.
• The three general requirements for a compound to
  be aromatic are
• The compound must be cyclic.
• Each element within the ring must have a
  p-orbital that is perpendicular to the ring,
  hence the molecule is planar.
• The compound must follow Hückel's Rule.

51
Aromatics

• The number of p delocalized electrons must follow
  Hückel's Rule.
• number of p electrons 4n 2
• where n 0, 1, 2, 3, and so on
• The number of p delocalized electrons is an even
  number, but not a multiple of 4 to be an aromatic
  compound.

52
Aromatics

• The most common examples of aromatic hydrocarbons
  are organic compounds, which contain one or more
  benzene rings.

Benzene
53
Aromatics

• Benzene follows Huckels Rule

54
Aromatics

• Each atom in benzene uses all its 4 valence
  electrons in forming covalent bonds with other
  atoms.
• Other functional groups can be used as
  substituents.
• More than one substituent requires a prefix.

55
Aromatics

• Any hydrogen or carbon atom can be substituted
  by

56
Aromatics

• When two substituents are attached to the benzene
  ring
• Ortho, meta, or para can be used to indicate
  where the two substituents are on the benzene
  ring.
• Three classifications
• ortho- (o-) position 1, 2-
• meta- (m) posotion 1, 3-
• para- (p) position 1, 4-

57
Aromatics
58
Aromatics Examples
o-dihydroxybenzene, m-dihydroxybenzene,
p-dihydroxybenzene
59
Aromatics Examples
60
Aromatics Examples
61
Aromatics Examples
62
Aromatics Examples
63
Summary of Hydrocarbon
64
Summary of Hydrocarbon
65
Summary of Hydrocarbon
66
Derivatives of Hydrocarbons

• Are formed when there is a substitution of a
  functional group at one or more carbon atoms.

67
Derivatives of Hydrocarbons

• Prefixes
• Haloalkanes
• Alcohols
• Ethers
• Amines
• Nitriles
• Thiols
• Thioethers
• Disulfides
• Aldehydes
• Ketones
• Carboxylic Acids
• Esters
• Amides
• Thioesters

68
Prefixes

• For multiple substituents of the same type, use
  the following prefixes
• di-
• tri-
• tetra-
• penta-
• hexa-

69
Haloalkanes

• The alkyl halides have the general form
• where the R in the general form is typically an
  alkyl group with a halogen replacing one of the
  hydrogens.
• X is written as
• F fluoro
• Cl chloro
• Br bromo
• I iodo

70
Haloalkanes

• Classify according to the number of carbons
  bonded directly to the alkyl halide.

71
Haloalkanes

• There can be multiple substitutions of halogens
  for hydrogens, and also variations where alkenes,
  alkynes or aromatics are involved.

72
C O Bonds Organic Compounds

1. Alcohols
2. Ethers

73
Alcohols

• IUPAC ending is ol

74
Alcohols

• Are organic compounds containing a hydroxyl
  group, -OH, substituted for a hydrogen atom.
• The center of the alcohol functional group is the
  oxygen.
• Have two lone pairs of electrons on the oxygen.
• This forces the molecular geometry on the alcohol
  oxygen to be BENT. This portion of the molecule
  is flat, with bond angles of 109 degrees.

75
Alcohols

• Are organic compounds containing a hydroxyl
  group, -OH, substituted for a hydrogen atom.
• The names of alcohols start with the name of the
  alkane but end with the suffix ol.
• Can have more than one hydroxyl group for
  hydrogens, and also variations where alkenes,
  alkynes or aromatics are involved.
• Use a prefix for multiple hydroxyl groups.

76
Alcohols

• Are classified according to the number of carbon
  atoms attached directly to the carbon containing
  the hydroxyl group.

77
Ethers

• oxy.IUPAC ending .ane

78
Ethers

• Are compounds with the general formula
• The center of the ether functional group is the
  oxygen.
• Have two lone pairs of electrons on the oxygen.
• This forces the molecular geometry on the ether
  oxygen to be BENT. This portion of the molecule
  is flat, with bond angles of 109 degrees.

79
Ethers Examples
80
Ethers Examples
81
Summary of Alcohols Ethers
82
C - S Bonds Organic Compounds

1. Thiols
2. Thioethers
3. Disulfides

83
Thiols

• IUPAC endingthiols

84
Thiols

• Are sometimes called sulfides.
• Are organic compounds containing a sulfhydryl
  group, -SH, substituted for a hydrogen atom.
• Are the sulfur analogue of alcohols. Sulfur takes
  the place of oxygen in the hydroxyl group of an
  alcohol.
• Are stronger acids than alcohols.
• The SH functional group itself is referred to as
  either a thiol group or a sulfhydryl group.

85
Thiols

• The center of the thiol functional group is the
  sulfur.
• Have two lone pairs of electrons on the sulfur.
• This forces the molecular geometry on the thiol
  sulfur to be BENT. The CSH angles approach 90.

86
Thiols

• Classified according to the number of carbon
  atoms bonded directly to the carbon containing
  the thiol group.
• The names of thiols start with the name of the
  alkyl but end with the suffix thiol.

87
Thiols

• Can have more than one sulfhydryl group, and also
  variations where alkenes, alkynes or aromatics
  are involved.
• Use a prefix for multiple thiol groups.

88
Thiols Examples
89
Thioethers

• IUPAC ending.sulfide

90
Thioethers

• Are sometimes called sulfides.
• Are compounds with the general formula
• The center of the thioether functional group is
  the sulfur.
• A thioether is similar to an ether except that it
  contains a sulfur atom in place of the oxygen.

91
Thioethers

• Have two lone pairs of electrons on the sulfur.
• This forces the molecular geometry on the
  thioether sulfur to be BENT.
• This portion of the molecule is flat, with bond
  angles of 90 degrees.

90
92
Thioethers Examples
93
Thioethers Examples
94
Disulfides

• IUPAC ending..disulfide

95
Disulfides

• Another class of sulfur containing molecules that
  have important biological implications.
• Have the generic formula
• Are products from the oxidation of two thiols.

96
Disulfides

• The center of a disulfide functional group has
  two sulfur atoms single bonded to each other and
  to two different carbon atoms.
• Have two lone pairs of electrons on each sulfur.
• This forces the molecular geometry on the
  thioether sulfur to be BENT.

97
Disulfides

• Are named by naming the R groups attached to the
  sulfur atoms followed by the suffix -disulfide.

Dimethyldisulfide
98
Disulfides Examples
99
Disulfides Examples
100
Disulfides Examples
101
Carbon and Nitrogen Organic Compounds

1. Amines
2. Nitriles

102
Amines

1. IUPAC ending .amine
2. Prefix is amino

103
Amines

• Are organic compounds that contain nitrogen and
  are basic.
• The general form of an amine is
• R represents an alkyl group, but either or both
  of the hydrogens may be replaced by other groups
  and still retain its class as an amine.

104
Amines

• The center of the amine functional group is the
  nitrogen.
• Have one lone pair of electrons on the nitrogen
  in addition to the single bonds.
• This forces the molecular geometry on the amine
  nitrogen to be trigonal pyramid.
• This portion of the molecule is not flat, with
  bond angles of 109 degrees.

105
Amines

• The common names for simple aliphatic amines
  consist of the alkyl group followed by the suffix
  -amine.
• The amino group (-NH2) is named as a substituent
  in more complicated amines, such as those that
  incorporate other functional groups or in which
  the alkyl groups cannot be simply named.

106
Amines

• Are classified according to the number of carbon
  atoms bonded directly to the nitrogen atom.

107
Amines Examples
108
Amines Examples
109
Nitriles

1. IUPAC ending is ..nitrile
2. Prefix is ..cyano

110
Nitriles

• Are organic compounds that have a
  functional group.
• Have one lone pair of electrons on the nitrogen
  in addition to one triple bond with a carbon
  atom.
• This forces the molecular geometry on the cyano
  nitrogen to be linear.

111
Nitriles

• The common names for simple nitriles consist of
  the alkane/alkyl followed by the suffix -nitrile.
  
• The cyano group (-CN) is also used
  interchangeably.

112
Nitriles Examples
113
Carbonyl Organic Compounds

1. Aldehydes
2. Ketones

114
Aldehydes (CHO)

• IUPAC ending is al

115
Aldehydes

• Are compounds containing a carbonyl group with a
  hydrogen attached at end and an organic group of
  carbons at the other side.
• The center of the aldehyde functional group is
  the carbon double bond oxygen.

116
Aldehydes

• Have two lone pairs of electrons on the oxygen.
• With three atoms attached to this carbon, the
  molecular geometry is trigonal planar.
• This portion of the molecule is flat, with bond
  angles of 120 degrees.

117
Aldehydes

• IUPAC name includes the prefix from the alkyl
  groups and the suffix al.

118
Aldehydes

• IUPAC name for cyclic aldehydes includes the
  prefix cyclo and the suffix carbaldehyde.

119
Aldehydes Examples
120
Ketones

• IUPAC ending is one

121
Ketones

• Are compounds containing a carbonyl group with
  two hydrocarbon groups attached to it.
• The center of the ketone functional group is the
  carbon double bond oxygen.

122
Ketones

• Have two lone pairs of electrons on the oxygen.
• With three atoms attached to this carbon, the
  molecular geometry is trigonal planar.
• This portion of the molecule is flat, with bond
  angles of 120 degrees.

123
Ketones

• IUPAC name includes the prefix from the alkyl
  group and the suffix -one.
• For more than one ketone group, use a prefix.

124
Ketones Examples
125
Summary of Aldehydes Ketones
126
Carboxyl Derivatives

1. Carboxylic Acids
2. Esters
3. Amides
4. Thioesters

127
Carboxyl Derivatives

• Are derivatives of carboxylic acids.
• Can be distinguished from aldehydes and ketones
  by the presence of a group containing an
  electronegative heteroatom - usually oxygen,
  nitrogen, or sulfur bonded directly to the
  carbonyl carbon.

128
Carboxyl Derivatives

• Have two sides
• The carbonyl group attach to an alkyl group. This
  is called an acyl group.
• The heteroatom-containing group, refer to as the
  acyl X' group

129
Carboxylic Acids

• IUPAC ending is oic acid

130
Carboxylic Acids

• Are important intermediate products for the
  production of esters and amides.
• Are hydrocarbon derivatives for which the
  functional group is the carboxyl group.
• The center of the acid functional group is the
  carbon double bonded to an oxygen and single
  bonded to a hydroxyl group.

131
Carboxylic Acids

• Each oxygen atom has a pair of lone electrons.
• With three atoms attached to this carbon, the
  molecular geometry is trigonal planar. This
  portion of the molecule is flat, with bond angles
  of 120 degrees.
• An additional molecular geometry is centered on
  the oxygen of the - OH group. This is bent.

132
Carboxylic Acids

• In the IUPAC system, the e ending in alkane is
  removed from the name of the parent chain and is
  replaced -anoic acid for the COOH acidic bond
  system.

133
Carboxylic Acids

• Cyclic carboxylic acids that are saturated are
  called cycloalkane carboxylic acids.
• Dicarboxylic acids are known as alkanedioic acids.

134
Carboxylic Acids
135
Carboxylic Acids Examples
136
Carboxylic Acids Examples
137
Esters

• IUPAC ending oate

138
Esters

• Are compounds with the general formula
• The center of the ester functional group is the
  carbon double bonded to an oxygen and single
  bonded to an oxygen attached to an alkyl group.

139
Esters

• Each oxygen atom has a pair of lone electrons.
• With three atoms attached to this carbon, the
  molecular geometry is trigonal planar. This
  portion of the molecule is flat, with bond angles
  of 120 degrees.
• An additional molecular geometry is centered on
  the oxygen with all single bonds. This is bent.

140
Esters

• Complex esters are more frequently named using
  the systematic IUPAC name, based on the name for
  the alkyl group followed by the suffix oate.
• Cyclic esters are called lactones.

141
Esters Examples
142
Esters Examples
143
Esters Examples
144
Amides

• IUPAC ending is amide

145
Amides

• Also known as an acid amide.
• Are formed when carboxylic acids react with
  amines.
• Are nitrogen-containing organic compounds with
  the general formula

146
Amides

• The center of the amide functional group is the
  carbon double bonded to oxygen and single bonded
  to nitrogen.
• Classified according to the number of carbons
  attached directly to the nitrogen atom

147
Amides

• The oxygen atom has two lone pair of electrons.
• The nitrogen atom has one pair of lone electrons.
• With three atoms attached to this carbon, the
  molecular geometry is trigonal planar. This
  portion of the molecule is flat, with bond angles
  of 120 degrees.

148
Amides

• The molecular geometry centered on the nitrogen
  is bent and also flat as an extension of the
  trigonal planar geometry.

149
Amides

• In the IUPAC system
• For primary amides, the e is removed from the
  alkane name and the suffix -amide is added.

150
Amides

• For 2 and 3 amides, alkyl groups attached to
  the nitrogen are named as substituents.
• The letter N is used to indicate they are
  attached to the nitrogen.
• For more than one of the same substituent groups,
  use a prefix.

151
Amides
152
Amides
153
Amides Example
154
Amides Example
155
Amides Example
156
Amides Example
157
Thioesters

1. IUPAC ending.-thioate or -carbothioate
2. Prefix.thio ending.-ate or -carboxylate

158
Thioesters

• Are the product of esterification between a
  carboxylic acid and a thiol.
• Are compounds with the functional group
• The center of the thioester functional group is
  the carbon double bonded to an oxygen and single
  bonded to sulfur attached to an alkyl group or
  hydrogen.

159
Thioesters

• The oxygen and sulfur atoms, each, have two sets
  of lone pairs electrons.
• With three atoms attached to this carbon, the
  molecular geometry is trigonal planar. This
  portion of the molecule is flat, with bond angles
  of 120 degrees.

160
Thioesters

• The molecular geometry centered on the sulfur is
  bent and also flat as an extension of the
  trigonal planar geometry.

161
Thioesters

• In the IUPAC system, the name consist of the
  alkyl group followed by the alkane with the
  suffix thioate or carbothioate
• Alkyl groups attached to the sulfur are named as
  substituents. The letter S is used to indicate
  they are attached to the sulfur.

S-Methyl ethanethioate (IUPAC)
162
Thioesters

• For common names, the name consist of the alkyl
  group followed by the prefix thio before the
  common name with the suffix ate or -carboxylate.
• Alkyl groups attached to the sulfur are named as
  substituents. The letter S is used to indicate
  they are attached to the sulfur.

S-PENTACHLOROPHENYL PENTACHLORO-1,3-BUTADIENE-1-TH
IOCARBOXYLATE
163
Thioesters Examples
164
Thioesters Examples
165
Summary of Carboxyl Derivatives
166
Summary of Functional Groups