SOLUTIONS MANUAL
,Table Of Contents
Chapter 1 Bonding and Isomerism............................................................................................. 1
Chapter 2 Alkanes and Cycloalkanes; Conformational and Geometric Isomerism........... 19
Chapter 3 Alkenes and Alkynes................................................................................................ 37
Chapter 4 Aromatic Compounds.............................................................................................. 61
Chapter 5 Stereoisomerism....................................................................................................... 87
Chapter 6 Organic Halogen Compounds; Substitution and Elimination Reactions....... 109
Chapter 7 Alcohols, Phenols, and Thiols............................................................................... 123
Chapter 8 Ethers and Epoxides...............................................................................................141
Chapter 9 Aldehydes and Ketones.......................................................................................... 157
Chapter 10 Carboxylic Acids and Their Derivatives...............................................................187
Chapter 11 Amines and Related Nitrogen Compounds......................................................... 211
Chapter 12 Spectroscopy and Structure Determination....................................................... 233
Chapter 13 Heterocyclic Compounds...................................................................................... 247
Chapter 14 Synthetic Polymers................................................................................................ 263
Chapter 15 Lipids and Detergents........................................................................................... 279
Chapter 16 Carbohydrates.........................................................................................................291
Chapter 17 Amino Acids, Peptides, and Proteins................................................................... 317
Chapter 18 Nucleotides and Nucleic Acids............................................................................. 345
Summary of Synthetic Methods..................................................................................................... 361
Summary of Reaction Mechanisms................................................................................................375
Review Problems On Synthesis...................................................................................................... 381
Sample Multiple Choice Test Questions....................................................................................... 385
,
, 1
Bonding and Isomerism
Chapter Summary
An atom consists of a nucleus surrounded by electrons arranged in orbitals. The
electrons in the outer shell, or the valence electrons, are involved in bonding. Ionic
bonds are formed by electron transfer from an electropositive atom to an
electronegative atom.
Atoms with similar electronegativities form covalent bonds by sharing electrons. A
single bond is the sharing of one electron pair between two atoms. A covalent bond has
specific bond length and bond energy.
Carbon, with four valence electrons, mainly forms covalent bonds. It usually forms
four such bonds, and these may be with itself or with other atoms such as hydrogen, oxygen,
nitrogen, chlorine, and sulfur. In pure covalent bonds, electrons are shared equally, but in
polar covalent bonds, the electrons are displaced toward the more electronegative
element. Multiple bonds consist of two or three electron pairs shared between atoms.
Structural (or constitutional) isomers are compounds with the same
molecular formulas but different structural formulas (that is, different arrangements
of the atoms in the molecule). Isomerism is especially important in organic chemistry
because of the capacity of carbon atoms to be arranged in so many different ways:
continuous chains, branched chains, and rings. Structural formulas can be written so that
every bond is shown, or in various abbreviated forms. For example, the formula for n-
pentane (n stands for normal) can be written as:
H H H H H
H C C C C C H or CH3CH2CH2CH2CH3 or
H H H H H
Some atoms, even in covalent compounds, carry a formal charge, defined as the
number of valence electrons in the neutral atom minus the sum of the number of unshared
electrons and half the number of shared electrons. Resonance occurs when we can write
two or more structures for a molecule or ion with the same arrangement of atoms but
different arrangements of the electrons. The correct structure of the molecule or ion is a
resonance hybrid of the contributing structures, which are drawn with a double-
headed arrow ( ) between them. Organic chemists use a curved arrow ( ) to show the
movement of an electron pair.
A sigma ( ) bond is formed between atoms by the overlap of two atomic orbitals
along the line that connects the atoms. Carbon uses sp3-hybridized orbitals to form four
such bonds. These bonds are directed from the carbon nucleus toward the corners of a
tetrahedron. In methane, for example, the carbon is at the center and the four hydrogens
are at the corners of a regular tetrahedron with H–C–H bond angles of 109.5 .
In the chapter summaries, terms whose meanings you should know appear in boldface type.
,Table Of Contents
Chapter 1 Bonding and Isomerism............................................................................................. 1
Chapter 2 Alkanes and Cycloalkanes; Conformational and Geometric Isomerism........... 19
Chapter 3 Alkenes and Alkynes................................................................................................ 37
Chapter 4 Aromatic Compounds.............................................................................................. 61
Chapter 5 Stereoisomerism....................................................................................................... 87
Chapter 6 Organic Halogen Compounds; Substitution and Elimination Reactions....... 109
Chapter 7 Alcohols, Phenols, and Thiols............................................................................... 123
Chapter 8 Ethers and Epoxides...............................................................................................141
Chapter 9 Aldehydes and Ketones.......................................................................................... 157
Chapter 10 Carboxylic Acids and Their Derivatives...............................................................187
Chapter 11 Amines and Related Nitrogen Compounds......................................................... 211
Chapter 12 Spectroscopy and Structure Determination....................................................... 233
Chapter 13 Heterocyclic Compounds...................................................................................... 247
Chapter 14 Synthetic Polymers................................................................................................ 263
Chapter 15 Lipids and Detergents........................................................................................... 279
Chapter 16 Carbohydrates.........................................................................................................291
Chapter 17 Amino Acids, Peptides, and Proteins................................................................... 317
Chapter 18 Nucleotides and Nucleic Acids............................................................................. 345
Summary of Synthetic Methods..................................................................................................... 361
Summary of Reaction Mechanisms................................................................................................375
Review Problems On Synthesis...................................................................................................... 381
Sample Multiple Choice Test Questions....................................................................................... 385
,
, 1
Bonding and Isomerism
Chapter Summary
An atom consists of a nucleus surrounded by electrons arranged in orbitals. The
electrons in the outer shell, or the valence electrons, are involved in bonding. Ionic
bonds are formed by electron transfer from an electropositive atom to an
electronegative atom.
Atoms with similar electronegativities form covalent bonds by sharing electrons. A
single bond is the sharing of one electron pair between two atoms. A covalent bond has
specific bond length and bond energy.
Carbon, with four valence electrons, mainly forms covalent bonds. It usually forms
four such bonds, and these may be with itself or with other atoms such as hydrogen, oxygen,
nitrogen, chlorine, and sulfur. In pure covalent bonds, electrons are shared equally, but in
polar covalent bonds, the electrons are displaced toward the more electronegative
element. Multiple bonds consist of two or three electron pairs shared between atoms.
Structural (or constitutional) isomers are compounds with the same
molecular formulas but different structural formulas (that is, different arrangements
of the atoms in the molecule). Isomerism is especially important in organic chemistry
because of the capacity of carbon atoms to be arranged in so many different ways:
continuous chains, branched chains, and rings. Structural formulas can be written so that
every bond is shown, or in various abbreviated forms. For example, the formula for n-
pentane (n stands for normal) can be written as:
H H H H H
H C C C C C H or CH3CH2CH2CH2CH3 or
H H H H H
Some atoms, even in covalent compounds, carry a formal charge, defined as the
number of valence electrons in the neutral atom minus the sum of the number of unshared
electrons and half the number of shared electrons. Resonance occurs when we can write
two or more structures for a molecule or ion with the same arrangement of atoms but
different arrangements of the electrons. The correct structure of the molecule or ion is a
resonance hybrid of the contributing structures, which are drawn with a double-
headed arrow ( ) between them. Organic chemists use a curved arrow ( ) to show the
movement of an electron pair.
A sigma ( ) bond is formed between atoms by the overlap of two atomic orbitals
along the line that connects the atoms. Carbon uses sp3-hybridized orbitals to form four
such bonds. These bonds are directed from the carbon nucleus toward the corners of a
tetrahedron. In methane, for example, the carbon is at the center and the four hydrogens
are at the corners of a regular tetrahedron with H–C–H bond angles of 109.5 .
In the chapter summaries, terms whose meanings you should know appear in boldface type.
