Chapter 3
Functional Groups Alkanes
Hydrocarbons
Alkanes, alkenes, alkynes, benzene
cyclic
Functional Groups
Alkyl Halides, amines, alcohols,
ethers
Functional Groups
Carbonyl Compounds
Aldehydes and ketones
Carboxylic acids and derivatives
Functional Groups
Aromatics
Other Aromatics
Functional Groups
Alkanes and Cycloalkanes
Nomenclature/structure acyclic
alkanes with 1-3 carbons
Nomenclature/structure of acyclic
alkanes with 4-5 carbons
Alkyl Substituents
Replace ane of alkane with yl.
Common Names
Propyl and Isopropyl
Butyl, isobutyl, sec-butyl, tert-butyl
Primary, Secondary, and Tertiary Carbons
A primary carbon is bonded to one carbon.
A
. secondary carbon is bonded to two carbons.
A tertiary carbon is bonded to three carbons.
A quaternary carbon in bonded to four carbons
Alkanes Systematic Nomenclature
First identify the longest continuous chain
(the parent hydrocarbon).
Add the Name of the Substituent
Number the chain in the direction that gives the
substituent as low a number as possible.
List Substituents in Alphabetical Order
The correct name is the one that contains the
lowest of the possible numbers (5+3 < 4+6)
Multiple Substituents
Chain is numbered in the direction that puts the lowest number in the name.
Start numbering from the end that has the earliest branch point
Substituents are listed in alphabetical order (di- and tri- are not alphabetized).
Cycloalkanes
Skeletal structures do not show Cs and Hs bonded to Cs.
Bond angles in cyclic alkanes
Not 108o
Not 120o
We will revisit this when discussing bond rotations
and eclipssed vs staggered conformations
Angle Strain in cylcoalkanes
Angle strain results from poor orbitalorbital overlap because
bonds have to deviate from the ideal (109.5) bond angle.
Mono-Substituted Cycloalkanes
A number is not needed.
Di-Substituted Cycloalkanes
Substituents are stated in alphabetical order.
Lowest possible sum of substituent numbering
#1 goes to first-listed substituent.
Nomenclature of Alkyl Halides
Nomenclature of Ethers
Common
aprotic solvent
used in
chemical
synthesis
The substituents are listed in alphabetical order.
Nomenclature of Alcohols
1-propanol
2-propanol
2-butanol
Classification of Alcohols
Primary alcohol = OH is on a primary carbon.
Secondary alcohol = OH is on a secondary carbon.
Tertiary alcohol = OH is on a tertiary carbon.
Diols
Propylene diol used extensively
Systematic Names of Alcohols
Pay attention to the number of the substituent
only if you get the same number for the
functional group in both directions.
Begin numbering from the end of the chain with the earliest branch point
A Substituent is a Prefix
A Functional Group is a Suffix
Classification of Amines
The classification depends on how many groups are bonded to N.
Primary amine = one group bonded to N
Secondary amine
Tertiary amine
= two groups bonded N
= three groups bonded N
Common Names of Amines
Substituents are in alphabetical order followed
by amine.
They are all written as one word.
Dont forget acid/base properties
of amines
Some special amines
Summary of Nomenclature
The Structure of an Alkyl Halide
The CX bond of an alkyl halide becomes longer and weaker
as the size of the halogen increases.
The Structure of an Alcohol
Resembles the Structure of Water
An alcohol is structurally like water with one H replaced by an R.
The Structure of an Ether
Resembles the Structure of an Alcohol
An ether is structurally like water with both Hs replaced by Rs.
Boiling Points
The greater the attractive forces between molecules,
the higher the boiling point.
attractive forces
van der Waals forces
dipoledipole interactions
hydrogen bonds
Boiling Points
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
-167.7 C
-88.6 C
-42.1 C
-0.5 C
36.1 C
induced dipole-induced dipole
68.7 C
interactions
98.4 C
van der Waals forces
125.7 C
The greater the surface area of the molecule, the higher the bp.
Branching Lowers the Boiling Point
cigar
tennis ball
DipoleDipole Interactions
Dipoledipole interactions are
stronger than van der Waals forces.
Diethylether
35 = oC
Hydrogen Bonds in H2O and NH3
CH4 167.7 C
H2O 100 C
no hydrogen bonds
hydrogen bonds
Hydrogen bonds are stronger than
other dipoledipole interactions.
Compounds with Similar Shapes and Properties
Often Have Similar Physiological Activities
Drugs bind to their receptors by van der Waals interactions,
dipole-dipole interactions, and hydrogen bonding.
Solubility
like dissolves like
Polar compounds dissolve in polar solvents (H2O).
Nonpolar compounds dissolve in nonpolar solvents (hexane).
Solvation
Solvation is the interaction between solute molecules and solvent molecules.
Competing effects with increasing
carbon count
Competing effects with increasing
carbon count
Conformational Analysis of
alkane and cycloalkanes
Rotation Occurs About
Single ()Bonds
Staggered and Eclipsed Conformers
of Ethane
Rotation Can Occur About the
Three CarbonCarbon Bonds in Butane
Rotation About C-2C-3 in Butane
[Link]
Steric strain is repulsion between the electron clouds of atoms or groups.
Cyclopropane
Cyclobutane
Molecules twist out of a planar arrangement
to minimize angle strain and the number of eclipsed hydrogens.
Cyclopentane
Molecules twist out of a planar arrangement to
minimize angle strain and the number of eclipsed hydrogens.
Chair Conformer of Cyclohexane
The chair conformer of cyclohexane is completely free of strain.
All bond angles are 111 and all adjacent bonds are staggered.
Axial and Equatorial Bonds
Ring Flip
Cyclohexane interconverts between two stable chair conformers.
Ring Flip
Cyclohexane interconverts between two stable chair conformers.
Conformers of Cyclohexane
Ring flip we will only talk about the two chair conformations
Conformers of Monosubstituted
Cyclohexanes
1,3-Diaxial Interactions
Cis and Trans Isomers
Conformers of Disubstituted
Cyclohexanes
1,4-dimethylcyclohexane
Each Isomer Has
Two Chair Conformers
1,2-dimethylcyclohexane
1,3-dimethylcyclohexane
cis-1-tert-butyl-3-methylcyclohexane
trans-1-tert-butyl-3-methylcyclohexane
