Ch4 Alkanes

*Contain only aliphatic hydrocarbons (C-C and C-H sigma bond), no functional group, less reactive

*2 categories – Acyclic alkanes- CnH2n+2, (eg. undecane)Cyclohexane CnH2n(in rings) (cyclohexane)

4.1A Acyclic Alkanes-1-5 C- Methane, Ethane, Propane, Butane,Pentane. Sp3 hybrid bonds

*Isomers- same molecular formula but different structural formula

*Bends in a carbon chain don’t matter to identify alkanes-different ways to arrange.eg. butane and
isobutene.- constitutional isomers(differ in the ways the atoms are connected to each other, eg, n-utane
and isobutene, C4H10, and ethanol with bimethyl ether C2H6O (CH3CH2OH, CH3OCH3)

*Constitutional isomers ( C atom connected to different functional groups- 2 different compounds)

Stereoisomers (

*Classification – how many the C atom bonded to other C atoms – Primary(1),

Secondary(2),Tertiary(3),Quanternary(4). H atom –primary(on C bonded to another C), secondary ( on C
bonded to 2 other C) etc

Exercise: Problem 4.4 p.117

4.1B – Acyclic Alkanes with more than 5 C- add CH2 (methylene) to the chain.

*Homologous seris – only differ by a CH2 group

Exercise.4.6, 4.8

4.2 Cycloalkanes-CnH2n-carbon rings (2 H less than n-alkanes)

4.3 Nomenclature- Naming of alkanes-IUPAC system- systematic(IUPAC), generic(official approved),

trade name(used in market)eg. 2-[4-(2-methylpropyl)phenyl]propanoic acid(ibuprofen)(Advil)

*alkyl group- carbon substituents – 1 hydrogen removed from alkane.(eg. propyl or isopropyl group)

(eg. remove primary H from butane, butyl, remove sec H, sec-butyl

Remove primary H from isobutene, isobutyl, remove tertiary H, ter-butyl

4.4B – Naming Acyclic Alkane- IUPAC system

a. find longest chain, if same, choose one with more substituents

b.Label with C with numbers with first substituents the lowest number and alphabetic order

c.Identify parent(No. of C), add in C number label and substituent

* substituent name and numbers+parent+suffix

Ex.4.2

4.5 Naming Cycloalkanes

Find parent cycloalkanes(No, of C in the ring)- 1 substituent(no C number needed), 2 or more (use
lowest numbers) then alphabetic order

*If both ring and straight chains in one compound-more C in straight chain-acyclic, more C in ring-Cyclo

Ex. 4.15, 4.16

4.6 Common names- Mainly for synthetic organic compounds- more descriptive in shape and structure.
Eg. Dodecahedrane (12 five membered rings resemble dodecahedron, ending with ane showing it is an
alkane)

4.7 Fossil Fuels-Alkanes occur in nature, primarily as natural gas and protroleum.

*Natural gas – 60% methane . Petroleum – hydrocarbons (gasoline C5H12-C12H26;kerosene C12H26-

C16H34;diesel fuel:C15H32-C18H38)- non polar and water insoluble but will dissolve oil in birds causing
environmental problems.

4.8Physical properties

Boiling point:*C-C and C-H bonds only: only have weak van der Waals force-low boiling point

*Boiling point increases

a) as C number increase due to increase in surface area

b) in isomers with less branching- because of increase of surface area

Melting point: low melting point because of being non-polar

Melting point increases as

a) increase in C number because of increase of asurface area

b) increase in symmetry (More symmetrical, higher melting point. More structured, more difficult
to break)

Solubility:Insoluble in water (non-polar, water is polar, like dissolves like), soluble in organic solvents.

4.9 Conformations of Acyclic alkanes- Ethane- the stereochemistry (3-dimension)

*Conformations: Different arrangements of atoms that are interconverted by rotation about single
bonds –a) eclipsed conformation: C-H bonds directly aligned with C-H bond on adjacent Carbon.

b) staggered conformation: C-H bond bisects the H-C-H bond on next C atom.
 *Rotate the atoms on one Carbon by 60o converts an eclipsed conformation to staggered
conformation.

*Newman projection: End-on representation for conformation p.132

*Staggered conformations are more stable(because of lower energy)

Ex. 4.18

*Electron-electron repulsion between bonds in eclipsed conformation increases its energy

a) Torsional strain – increase in energy due to eclipsing interactions. An energy of max and minimum
alternate every 60o.

b)Steric strain- increase in energy when atoms are forced too close to one another (eg. CH3 group).
Eclipsed conformation has higher energy than gauche and staggered.

c)Angle strain-increase in energy when tetrahedral bond angles deviates from the optimum angle of
109.5

4.10 Conformation of Butane- have several C-C bonds, more rotation possibilities C2-C3 bond rotation

*Staggered conformation withTwo larger groups(CH3) 180 from each other – anti

*Staggered conformation with two larger group (CH3) 60 from each other – gauche. Gauche
conformation are higher in energy because steric strain

*Rotate one C by 60 keeping other C fixed, continue- 6 possible conformation F. 4.9 p.134. Remember
the graph on page 136.Staggered (Min E)->Gauche->Eclipsed (Max E)

*Barrier to rotation- the energy difference between the lowest and highest energy due to conformation.
That is why the skeletal structure in zigzag shape because of staggered conformation(most stable)

Ex. Problem 4.21, 4.22, 4.23

4.11 Introduction to Cycloalkanes

*Cycloalkanes with more than 3 C could not be flat due to angle strain (Baeyer strain theory). They are
puckered to reduce energy- reduce torsional strain and angle strain (Tetrahedrane (4C)cannot be
produced due to too high angle strain (60), cubane(8C)(90) is stable at room temperature.
Dodecahedrane(108) is very stable.

4.12 Cyclohexane- most common ring size in natural occurring compounds

* Chair conformation: internal bond angle 120>109.5(no angle strain), all H are aligned (no torsional
strain). 3C puckered up and 3C puckered down alternating. Called up C’s and down C’s.
*Two different types of H – Axial H-above and below the ring

- Equatorial H- in the plane of the ring

*how to draw p.139-140. EX. 4.24

4.12B- Ring-Flipping – cyclohexane not in single conformation, ring flipping – 2 process

Chair form->boat-> second chair form

*Axial and equatorial H – interconverted during a ring flip.

4.13 Substituted cycloalkanes- equatorial position has more room than axial position for larger
substituents.

*Distributed cycloalkane-C-C roatation restricted, two different 1,2-dimethylcyclohexane- one same side
or opposite side- stereoisomers – cis(same side) and trans(opposite side) (only different atoms oriented
in space)

4.14 Oxidation of Alkane – Oxidation (loss of electron) Reduction (gain electron)

Determine oxidation – starting compound and compare C-H and C-Z bonds(Z a more electronegative
element). Oxidation: more C-Z bonds or less C-H bonds. Reduction: more C-H bonds and less C-Z bonds

4.15 Lipds-resemble alkanes, many C-H and C-C bonds – non polar

Wax- 2 long alkyl chains joined by single oxygen containing functional grou

PGF- prostaglandins- many C-C and C-H with a COOH

Cholesterol-4 rings and one plar OH group