Alkenes: Structure and Reactivity

Calculating Degree of Unsaturation

Relates molecular formula to possible structures

Degree of unsaturation: number of multiple bonds or rings
Formula for a saturated acyclic compound is C nH2n+2
Alkene has fewer hydrogens than an alkane with the same
number of carbons CnH2n because of double bond
Each ring or multiple bond replaces 2 H's

Example: C6H10
Saturated is C6H14
therefore 4 H's are not present
This has two degrees of unsaturation
Two double bonds?
or triple bond?
or two rings?
or ring and double bond?

Degree of Unsaturation With Other

Elements
Organohalogens (X: F, Cl, Br, I)
Halogen replaces hydrogen
C4H6Br2 and C4H8 have one degree of
unsaturation

Degree of Unsaturation (Continued)

Organoxygen compounds (C,H,O) Oxygen forms
2 bonds
When 2 bonds are to different things, these
don't affect unsaturation, and can be
ignored
When oxygen forms a double bond to the
same ion, assume that 2 H are lost (1
degree of unsaturation)

Organonitrogen Compounds
Nitrogen is trivalent, acts like of a carbon
To determine degree of unsaturation when N is present, use the
following general formula to determine how many H the compound
should have:
(2 x number of C) + 2 + (Number of N)
Next, subtract the actual number of H then divide by 2

Cis-Trans Isomerism in Alkenes

Carbon atoms in a double bond are sp2-hybridized
Three equivalent orbitals at 120 separation in plane
Fourth orbital is atomic p orbital
Combination of electrons in two sp2 orbitals of two
atoms forms bond between them
Additive interaction of p orbitals creates a bonding
orbital
Subtractive interaction creates a anti-bonding
orbital
Occupied orbital prevents rotation about -bond
Rotation prevented by bond - high barrier, about 268
kJ/mole in ethylene

Cis-Trans Isomerism in Alkenes

(Continued)

Rotation of bond is prohibitive

This prevents rotation about a carbon-carbon
double bond (unlike a carbon-carbon single bond).
Creates possible alternative structures

Cis-Trans Isomerism in Alkenes

(Continued)

the presence of a carbon-carbon double bond can

create two possible structures
cis isomer - two similar groups on same side of the
double bond
trans isomer - similar groups on opposite sides
Each carbon must have two different groups for these
isomers to occur

Cis-Trans Isomerism in Alkenes

(Continued)
Cis-Trans Isomerization requires that end groups differ
in pairs
Bottom pair cannot be superposed without breaking
C=C

Alkene Stereochemistry and the E,Z

Designation
Cis-Trans naming system discussed thus far
only works with disubstituted alkenes
Tri- and Tetra substituted double bonds
require more general method
Method referred to as the E,Z system

E,Z Stereochemical Nomenclature

Priority rules of
Cahn, Ingold, and
Prelog
Compare where
higher priority
groups are with
respect to bond
and designate as
prefix
E -entgegen,
opposite sides
Z - zusammen,
together on the
same side

Cahn-Ingold-Prelog Rules
RULE 1
Must rank atoms that are connected at
comparison point
Higher atomic number gets higher priority
Br > Cl > S > P > O > N > C > H

Cahn-Ingold-Prelog Rules
RULE 2
If atomic numbers are the same, compare at next
connection point at same distance
Compare until something has higher atomic number
Do not combine always compare

Cahn-Ingold-Prelog Rules
RULE 3
Multiple-bonded atoms are equivalent to the same
number of single-bonded atoms
Substituent is drawn with connections shown and no
double or triple bonds
Added atoms are valued with 0 ligands themselves

Stability of Alkenes
Cis alkenes are more polar, less stable than trans
alkenes
Compare heat given off on hydrogenation: Ho
Less stable isomer is higher in energy
And gives off more heat
hyperconjugation of R groups stabilize the pi bond

Effects of Increasing Alkene

Substitution
Increasing substitution on alkene carbon atoms
increases stability (again, hyperconjugation)
This will become very important when we
begin to look at possible products resulting
from elimination reactions.

17

Stability of Alkenes (Continued):

Hyperconjugation
Electrons in neighboring filled orbital stabilize
vacant antibonding orbital net positive interaction
Alkyl groups are better than H