Chem 334 - Fall 2001
Organic Chemistry I
Dr. Carl C. Wamser

Chapter 5 Notes: Alkene Structure, Elimination Reactions

Alkenes

• C=C double bond
• Cn H2n - general formula
• unsaturated
  not "saturated" with maximum hydrogens
  unsaturated fats have some double bonds (easier to digest)
• note that cycloalkanes also are Cn H2n

Unsaturated Compounds

• alkenes & polyenes (dienes, trienes, etc.)
• arenes - aromatic rings
• alkynes - triple bonds
• combinations - e.g., enynes

Bonding Trends

Bond Lengths in Angstroms (Bond Strengths in kcal/mole)

Compound	Hybrid	C-C bond	C-H bond
ethane	sp3	1.54 (88)	1.11 (98)
ethylene	sp2	1.34 (172)	1.10 (104)
acetylene	sp	1.21 (230)	1.08 (125)

• multiple bonds are stronger
• shorter bonds are stronger

Alkene Nomenclature

• parent alkene is the longest continuous carbon chain that includes the double bond
• number from the end that gives the double bond the lower number
• use -en- instead of -an-
• use only the first number of the double bond
• name substituents as usual

Cycloalkene Nomenclature

• double bond assumed at C1-C2
• number in the direction that gives substituents lower numbers

3-methylcyclohexene

5,5-dimethyl-1,3-cyclopentadiene

Alkene Structure

• C=C double bond is one sigma bond and one pi bond
• sp2 hybridization (trigonal planar)
• pi bond doesn't rotate
• unlike ethane, ethene has no other conformers

Cis-Trans Isomers

• another example of stereoisomers
• 2-butene has two isomers:

trans-2-butene

cis-2-butene

Cis-Trans Isomers

• an alkene can have cis-trans isomers only when each C in the double bond is attached to 2 different groups

Stereochemistry Designation

cis or trans ?

• note that cis-trans works unambiguously only for disubstituted alkenes
• cis and trans can be used to follow the structure of the parent chain in some cases
• E,Z designation is more general and always works

E,Z Designation

• assign priorities to the two groups on each C of the double bond
  ( one high priority, one low priority for each C )
• if the the two high priority groups are on the same side, it is Z
• if the the two high priority groups are on opposite sides, it is E

Priority Rules

• consider just each atom bonded to the C
• higher atomic number is higher priority
• for a tie, consider each atom bonded next in turn
• for a double bond, consider it like two identical atoms

Practice Nomenclature

(E)-3,4-dimethyl-2-octene

(Z)

Relative Stabilities

• greater substitution leads to greater stability
• tetrasubstituted > trisubstituted > disubstituted > monosubstituted
• trans typically more stable than cis

Elimination Reactions - Preparation of Alkenes

• dehydrogenation (loss of H2 from an alkane)
• dehydration (loss of H2O from an alcohol)
• dehydrohalogenation (loss of HX from an alkyl halide)

Dehydration

• regioselectivity - Zaitsev Rule (prefer more stable alkene)
• stereoselectivity
• mechanism - carbocation intermediate
• reactivity: 3° > 2° > 1°
• carbocation rearrangements - hydride shifts, alkyl shifts

Dehydrohalogenation

• base-promoted elimination
• E2 mechanism - concerted, bimolecular
• stereoselectivity - anti elimination
• E1 elimination for 3° alkyl halides in absence of base