4.1 Introduction to Alkanes!

Chapter 4. Alkanes and Cycloalkanes! ! "

Junha Jeon !
Department of Chemistry ! University of Texas at Arlington ! Arlington, Texas 76019 ! " ! Chem 2321, Fall 13 !

! Hydrocarbons: compounds that are only composed of hydrogen and carbon!

Introduction to Alkanes!
! Hydrocarbons: compounds that are only composed of hydrogen and carbon! ! Alkanes: Saturated hydrocarbons do NOT contain any pi bonds!

Introduction to Alkanes!
! Hydrocarbons: compounds that are only composed of hydrogen and carbon! ! Alkanes: Saturated hydrocarbons do NOT contain any pi bonds!

4.2 Common Names!

! Common names

Nomenclature of Alkanes (IUPAC)!

! Common names

! Nomenclature: systematic names of chemical compounds !

! Nomenclature: systematic names of chemical compounds !

1 !

Parent Chain!
! Selection the parent chain: longest chain! ! ! ! ! ! ! ! ! !

Parent Names !
! Parent names for alkanes! ! ! ! ! ! ! ! ! !

Substituents!
! If two chains of equal length, choose the greater number of substituents (branched groups connected to the parent chain; side chains).! ! ! ! ! ! ! ! ! !

Cycloalkanes!
! Cyclic alkanes (ring structures)! ! ! ! ! ! ! ! !

Identifying and Naming Substituents!

! Identify the parent chain and substituents (side chains).! ! ! ! ! ! ! Naming of substituents: analogous to parent naming, yet add yl.! ! !

Identifying and Naming Substituents!

! Identify the parent chain and substituents (side chains).! ! ! ! ! ! ! Naming of substituents: analogous to parent naming, yet add yl.! ! !

2 !

Alkyl Groups!

Identifying and Naming Substituents: Which one?!

! Identify the parent chain and substituents: number of carbons! ! ! ! ! ! ! !

Complex Substituents!

Complex Substituents!

1. Number the longest carbon chain within the substituent. Start with the carbon directly attached to the main chain.! 2. Name the substituent (in this case butyl).! 3. Name and number the substituents side group (in this case 2-methyl).! Therefore, the name of this substituents is (2-methylbutyl). ! !

Common Name in Complex Substituents!

Common Name in Complex Substituents!

3 !

Common Name in Complex Substituents!

Systematic Name of an Alkane!

! the location of the methyl group is identied with a number, called a locant.!

Systematic Name of an Alkane!

Guidelines!
1.! ! ! ! ! ! 2.!

! the location of the methyl group is identied with a number, called a locant.!

Guidelines!
1.! ! ! ! ! ! 2.!

Guidelines!
3.! ! ! ! ! ! 4.!

4 !

Guidelines!
3.! ! ! ! ! ! 4.!

Guidelines!

5. A prex is used (di, tri, tetra, penta, etc.) if multiple substituents are identical.! 1,1,3-trimethylcyclohexane! ! ! ! List all substituents before the parent chain name in alphabetical order.! Prexes are not used for alphabetical purposes, except for the prex iso.!

Assembling the Entire Name!

One more!
!

parent substituents

5. A prex is used (di, tri, tetra, penta, etc.) if multiple substituents are identical.! 1,1,3-trimethylcyclohexane! ! List all substituents before the parent chain name in alphabetical order.! ! Prexes (di, tri, tetra, penta, etc.) are not used for alphabetical purposes." Only two prex that"are"used alphabetizing is""iso as in"isopropyl or isobutyl and neo as in neopentyl. "However, the prexes sec- and tert- are not used.!

6-Ethyl-4-methylnonane

4-Ethyl-6-methylnonane

One more!
!

One more!
!

parent substituents

parent substituents

6-Ethyl-4-methylnonane

4-Ethyl-6-methylnonane

6-Ethyl-4-methylnonane

4-Ethyl-6-methylnonane

5 !

One more!
!

Assembling the Entire Name!

1. Identify the parent chain.! ! 2. Identify and name substituents.!
parent substituents

! 3. Number the parent chain and assign a locant to each substituent.! ! 4. Arrange substituents alphabetically.! !

6-Ethyl-4-methylnonane

4-Ethyl-6-methylnonane

Assembling the Entire Name!

1. Identify the parent chain.! ! 2. Identify and name substituents.! ! 3. Number the parent chain and assign a locant to each substituent.! ! 4. Arrange substituents alphabetically.! ! !

Bicyclic System!
! Bicyclic compounds: containing two fused ring! ! ! ! ! ! ! Prex: bicyclo (the above should be bicycloheptane)! ! Bridgeheads: Identifying the constitution! of compounds!

Practice Problem"
!

! ! ! !

Bicyclic System: Bridgehead!

! Bicyclic compounds: containing two fused ring! ! ! ! ! ! ! Prex: bicyclo (the above should be bicycloheptane)! ! Bridgeheads: Identifying the constitution! of compounds! ! ! !

Bicyclic System!
! Bicyclic compounds: containing two fused ring! ! ! ! ! ! ! Prex: bicyclo (the above should be bicycloheptane)! ! Bridgeheads: Identifying the constitution! of compounds! ! ! Bicyclo[2.2.1]heptane! ! !

6 !

Bicyclic System: Substituents!

! To number the bicyclo parent chain, start at a bridgehead carbon and number the longest carbon chain connecters rst.! ! Without violating the rule above, give the substituents the lowest numbers possible.! ! ! ! ! ! ! ! ! 6-Methylbicyclo[3.2.1]octane ! !

Bicyclic System: Substituents!

! To number the bicyclo parent chain, start at a bridgehead carbon and number the longest carbon chain connecters rst.! ! Without violating the rule above, give the substituents the lowest numbers possible.! ! ! ! ! ! ! ! ! 6-Methylbicyclo[3.2.1]octane ! !

Name?!

Name? Two Bridgehead Carbons!

" !

4.3 Constitutional Isomers of Alkanes!

Constitutional Isomer?!

7 !

Constitutional Isomer?!

4.4 Relative Stability of Isomers!

Stable = low potential energy = low reactivity ! = little energy will be released upon reacting
" ! ! "

! The relative stability of constitutional isomers can be measured by combustion experiment: Heat of combustion (#H) change in enthalpy!

Yes!! Yes Single bonds freely rotate.

Relative Stability of Isomers!

Stable = low potential energy = low reactivity ! = little energy will be released upon reacting ! The relative stability of constitutional isomers can be measured by combustion experiment: Heat of combustion (#H) change in enthalpy!

Relative Stability of Isomers!

Stable = low potential energy = low reactivity ! = little energy will be released upon reacting ! The relative stability of constitutional isomers can be measured by combustion experiment: Heat of combustion (#H) change in enthalpy!

Relative Stability of Isomers!

Experimental result: branched alkanes are lower in energy (i.e. more stable)! than straight-chain alkanes

4.6 Three-Dimensional Representation: Newman Projections!

45! ! The relative stability of constitutional isomers can be measured by combustion experiment: Heat of combustion (#H) change in enthalpy!

45!

! To predict rotation about CC single bonds allows a compound to adopt a variety of possible three- dimensional shapes, called conformations.! ! Newman projection will help to visualize conformational variation of a molecule.!

8 !

4.6 Three-Dimensional Representation: Newman Projections!

4.6 Three-Dimensional Representation: Newman Projections!

45!

45!

45!

45!

! To predict rotation about CC single bonds allows a compound to adopt a variety of possible three- dimensional shapes, called conformations.! ! Newman projection will help to visualize conformational variation of a molecule.!

! To predict rotation about CC single bonds allows a compound to adopt a variety of possible three- dimensional shapes, called conformations.! ! Newman projection will help to visualize conformational variation of a molecule.!

Three-Dimensional Representation: Newman Projections!

Three-Dimensional Representation: Newman Projections!

45!

45!

! To predict rotation about CC single bonds allows a compound to adopt a variety of possible three-dimensional shapes, called conformations. (model)! ! Newman projection will help to visualize conformational variation of a molecule.!

Practice: Newman Projections!

4.7 Rotational Conformations!

! Dihedral Angle (torsional angle): 0 to 180 > an innite ! number of possible conformations with different energies. !

9 !

Rotational Conformations!
! Dihedral Angle (torsional angle): 0 to 180 > an innite ! number of possible conformations with different energies. !

Conformational Analysis of Ethane!

! The lowest and highest conformations:

torsional! stain! (12 kJ/mol)!

dihedral angle = 0!

Conformational Analysis of Ethane: Torsional Strain Energy!

Conformational Analysis of Ethane: Torsional Strain Energy!

! Torsional strain can be explained ! via i) VSEPR theory: minimizing electrostatic repulsion between electron pairs ! ii) Molecular Orbital Theory: in the staggered conformation, the bonding! and antibonding MOs of neighboring carbons overlap.!

Conformational Analysis of Ethane: Torsional Strain Energy!

! Torsional strain can be explained ! via i) VSEPR theory: minimizing electrostatic repulsion between electron pairs ! ii) Molecular Orbital Theory: in the staggered conformation, the bonding! and antibonding MOs of neighboring carbons overlap.!

Conformational Analysis of Propane!

10 !

Conformational Analysis of Propane!

Conformational Analysis of Propane!

= 4 kJ/mol = ? kJ/mol ! = ? kJ/mol !

Conformational Analysis of Propane!

Conformational Analysis of Butane!

= 4 kJ/mol = 6 kJ/mol !

Three Staggered Conformations!

Anti Conformation!

3.8 kJ/mol!

anti conformation! dihedral angle! = 180!

gauche interaction! dihedral angle! = 60!

gauche interaction! dihedral angle! = 60!

11 !

Two Degenerated Gauche Conformations!

Three Eclipsed Conformations!

3.8 kJ/mol!

anti conformation! dihedral angle! = 180!

gauche interaction! dihedral angle! = 60!

gauche interaction! dihedral angle! = 60!

Two Degenerated Eclipsed Conformations!

Eclipsing Interaction of Two Methyl Groups!

Eclipsing Interaction of Two Methyl Groups!

Relative Energy Costs of Butanes Rotational Conformations!

12 !

4.9 Cycloalkanes!

Can you remember?!

Stable = low potential energy = low reactivity ! = little energy will be released upon reacting ! The relative stability of constitutional isomers can be measured by combustion experiment: Heat of combustion (#H) change in enthalpy!

! sp3 hybridization ! Angle Strain vs. Stability! !

Cycloalkanes: Heats of Combustion per CH2 Group!

Cyclopropane!
! Angle strain:! a. Bond angles of 60 cause electron pair repulsion in adjacent bonds! b. Inefcient sigma bond overlap! : bent bond (banana bond) ! Torsional strain:! Eclipsing CH bonds all the way around the ringsee Newman projection! ! !

Cyclopropane!
! Angle strain:! a. Bond angles of 60 cause electron pair repulsion in adjacent bonds! b. Inefcient sigma bond overlap! : bent bond (banana bond) ! Torsional strain:! Eclipsing CH bonds all the way around the ringsee Newman projection! ! !

Cyclobutane!
! Angle strain: less than cyclopropane! ! Torsional strain: morethan cyclopropane!

13 !

Cyclobutane!
! Angle strain: less than cyclopropane! ! Torsional strain: more than cyclopropane a slightly puckered conformation!

Cyclopentane!
! only 5 kJ/mol less stable than cyclohexane per CH2 group!

Cyclopentane!
! Angle strain: less than cyclopropane and cyclobutane close to the optimal value! ! Torsional strain: the minimal but signicant!

Cyclopentane!
! Angle strain: less than cyclopropane and cyclobutane close to the optimal value! ! Torsional strain: the minimal but signicant!

4.10 Conformations of Cyclohexane!

Conformations of Cyclohexane!

Demo! chem 3-D via RDC! ! Utilize a molecular model set!!

In both chair and Boat conformations," ! Angle strain (ring strain): zero (109.5)!! In only chair conformation," ! Torsional strain: zero! all adjacent C-H bonds are staggered.

In both chair and Boat conformations," ! Angle strain (ring strain): zero (109.5)!! In only chair conformation," ! Torsional strain: zero! all adjacent C-H bonds are staggered.

14 !

Chair Conformation!

Boat Conformation!

" ! No Angle strain (ring strain): 109.5! " ! No Torsional strain: all adjacent C-H bonds are staggered.

" ! No Angle strain (ring strain): 109.5! ! Two types of Torsional strain:! 1. eclipsed C-H bonds! 2. agpole interactions!

Twisted Boat Conformation!

To alleviate the torsional strain in the Boat conformation,! ! ! ! ! ! ! or other possible conformations. !

Conformational Analysis of Cyclohexane!

! Ground state ! conformation

4.11 Drawing Chair Conformations!

Drawing Chair Conformations!

! It is critical to draw a CHAIR properly; Use three sets of parallel lines.! ! ! !

! It is critical to draw a CHAIR properly; Use three sets of parallel lines.! ! ! !

15 !

Drawing Chair Conformations! ! SIX of the atoms attached to the chair are axial: Axial groups point straight up
and down alternating around the ring. ! ! ! ! ! ! ! !

Drawing Chair Conformations! ! The other SIX atoms attached to a chair are in equatorial positions: angles
parallel to the sets of parallel lines making up the chair itself! ! ! ! ! ! ! Overall, ! !

Drawing Chair Conformations! ! The other SIX atoms attached to a chair are in equatorial positions: angles
parallel to the sets of parallel lines making up the chair itself! ! ! ! ! ! ! Overall, ! !

4.12 Monosubstituted Cyclohexane! ! Begin with the ground state conformation (energetically most stable):!
!Chair conformation (two possibilities)! !

ring ip"

require 45 kJ/mol!!

Ring Flip !

Ring Flip ! ! Flipping a chair is the result of CC single bonds rotating only.! ! Affecting the axial or equatorial position of the substituents.!
!

no direct way!

Newman projection!

16 !

Stability of Chair Conformations!

Stability of Chair Conformations!

3!

1! 3!

! 1,3-diaxial interactions:! steric hindrance !

3! 3!

(electron repulsion)!
1!

X = CH3!

1,3-Diaxial Interaction: Gauche Interaction!

Equatorial Substituent: Anti Interaction!

equatorial!

Steric Hindrance! ! Conformational equilibrium depends upon the steric hindrance, resulting from
1,3-diaxial interaction.! !

1,3-Diaxial Interactions!

X =!

17 !

4.13 Disubstituted Cyclohexane --- Additional Feature!

Disubstituted Cyclohexane --- Additional Feature!

X Y

X Y

! Conguration: the spatial arrangement of the atoms of a molecular entity the

three-dimensional orientation of substituents! !

! Conguration: the spatial arrangement of the atoms of a molecular entity the

three-dimensional orientation of substituents (cf. conformation, see p41)" !

Disubstituted Cyclohexane --- Additional Feature!

1,2-Disubstituted Cyclohexane: Chair Conformations!

X Y
1! 2!

! Conguration: the spatial arrangement of the atoms of a molecular entity the

three-dimensional orientation of substituents (cf. conformation, see p41)" !

X Y

X Y

X Y

X Y

1,3-Disubstituted Cyclohexane: Chair Conformations!

1,3-Disubstituted Cyclohexane: Chair Conformations!

1,3-diaxial interaction!

18 !

1,3-Disubstituted Cyclohexane: Chair Conformations!

1,3-Disubstituted Cyclohexane: Chair Conformations!

cistrans Stereoisomerism"

cistrans Stereoisomerism"

Haworth projections! ! cis: two groups are on the same side.! ! trans: two groups are on opposite sides." More generally, ! cis-trans Isomerism: differ in the positions of atoms (or groups) relative to a reference plane ! cis: two groups are on the same side.! ! trans: two groups are on opposite sides." More generally, ! cis-trans Isomerism: differ in the positions of atoms (or groups) relative to a reference plane different compounds

cistrans Stereoisomerism"

cistrans Stereoisomerism"

19 !

4.15 Polycyclic Systems: Dacaline!

! Decalin: a bicyclic system composed of two fused six-membered rings! ! ! ! ! ! ! ! ! cis- and trans-decalin: a stereoisomeric relationship ! ! not interconvertible by ring ip!

Dacaline in Steroids!

Dacaline in Steroids!

Norbornane!

Diamond Structure!

Diamond Structure is Useful for Conformational Analysis!

H H H H H gauche butane anti butane H H H H H H H H H H anti butane H H H H

gauche butane

20 !

Anti Conformation!

anti conformation! dihedral angle! = 180!

gauche interaction! dihedral angle! = 60!

gauche interaction! dihedral angle! = 60!

21 !