ALKENES: Unsaturated hydrocarbon General formula: CnH2n Functional group is the double bond Cis-Trans Isomerism The rigidity

dity of the double bond gives rise to cis-trans isomerism. Cis groups are on the same side of the double bond Trans groups are on opposite side of the double bond Vinyl group formed when a H is removed from ethylene (= ethene).

Example: H C C H H H H H C C H H H C C H Vinyl chloride Cl

Ethene

Vinyl group

Propene: The sp2-hybridized carbons of the C=C are called vinylic carbons. The Hs on the vinylic carbons are vinylic hydrogens. The sp3-hybridized carbon atoms next to the double bond are known as allylic carbons. The hydrogen atoms bonded to allylic carbons are called allylic hydrogens. H atoms in vinylic positions are less reactive than H atoms in allylic positions. Terminal alkene has the double bond at the end of a chain. Internal alkene has the double bond somewhere in the middle of a carbon chain.

Relative Stabilities of Alkenes: Alkenes react with H2 in the presence of a metal catalyst to give the corresponding alkane. Hydrogenation Exothermic reaction
Example: H C C H H H H2 Metal catalyst H = -

CH3CH3

A terminal alkene is less stable than an internal alkene. A trans-alkene, in which the largest substitutents on the double bond are farther apart from each other, is more stable than the corresponding cis-alkene in which the larger substituents are closer together. Catalytic Hydrogenation Reduction reaction Exothermic reaction heat is evolved. The more stable the alkene, the less heat is evolved. H2 adds to the double bond in the presence of a metal catalyst, such as Pd, Pt or Ni.

 The stability of alkenes increases with the number of alkyl groups that are substituted on the carbon atoms of the double bond. Alkenes in which bulky substituents are trans to each other are more stable than the corresponding cis alkenes. Heterogeneous catalysis catalyst is present as a separate solid phase, thus making the reaction mixture a heterogeneous one. Procedure: The alkene is stirred in the presence of the metal catalyst while H2 is bubbled into the reaction mixture. Syn-addition H2 adds to the same side of the double bond. bond in an alkene is a site of electron density. bond will be attractive to an electron-poor species (electrophile). Alkene is a nucleophile, species which is electron-rich and therefore attracted to an electron-poor species.

ELECTROPHILIC ADDITION Composed of two steps: 1. Addition of an electrophile (H+) to the double bond to form a carbocation intermediate. 2. The nucleophile (X-) attacks the carbocation intermediate to form the addition product. The slowest step is the rate-determining step. The rate-determining step is the formation of the carbocation intermediate. Markovnikovs Rule For the addition of a hydrogen halide to a double bond, the major product is that isomer which results from the formation of the more stable carbocation intermediate. The carbocation forms on the more substituted carbon. Stability of Carbocations The stability of carbocation intermediates increases as the number of alkyl substituents bonded to the positively charged carbon atom increases. Order of stability of carbocations: 3o > 2o > 1o > H3C+ Most stable least stable ELECTROPHILIC ADDITION: 1. Addition of HX (HX = HCl, HBr, or HI) = Hydrohalogenation reaction

H C C + HX C C X
2. Addition of Br2 to alkenes = Bromination

Br C C + Br2 C C Br

Anti Addition of Bromine: Trans product is formed. The Br- can only attack on the opposite side of the bromonium ion. Anti addition is an addition reaction in which the two components that add to the double bond end up trans to each other (or are anti to each other). 3. Acid-catalyzed addition of water Hydration reaction = addition of water Water adds to alkenes in the presence of acids to form alcohols.

C C

+ H2O

H C C OH

4. Reaction with diborane (B2H6) = Hydroboration B2H6 dimer of BH3, in the absence of Lewis bases; dissociates easily in the presence of ethers Hydroboration goes through a 4-centered transition state (with 4 atoms undergoing changes in bonding at the same time). The product from the addition of borane to an alkene is an organoborane. Boron will add to the less substituted atom of the doubly bonded C atoms. Stereochemistry of Hydroboration Reactions B and H end up bonded to the same side of the molecule. Syn addition an addition reaction in which the incoming groups are added to the same side of the molecule. 5. Oxymercuration-Demercuration

Oxymercuration: R CH CH2 + Hg(OOCCH3)2 Hg H2O R CH CH2 OH OOCCH3

Demercuration: Hg OOCCH3 R CH CH2 OH NaBH4

-

H OH R CH CH2 OH

6. Cationic polymerization

Oxidation of Alkenes: 1. Reaction with ozone 2. Oxidation with MnO4- or OsO4 3. Oxidation with peroxy acids Ozonolysis reaction between an alkene and ozone wherein the C=C bond is broken and a C=O bond is formed on each fragment.

R1 C C R2

R3 R4

O3

R1 C O R2 + O C

R1 R2

Ozonolysis products depend on conditions used: 1. Reductive work-up uses a reducing agent such as Zn or dimethyl sulfide [(CH3)2S]; products will be aldehydes and ketones 2. Oxidative work-up uses an oxidizing agent, such as H2O2; will give carboxylic acids and ketones
[Reductive work-up] Zn or (CH3)2S H3C C O + O C H3C H3C C O + O C CH3 CH3 OH H

H3C C C H3C

H CH3

O3

H2O2, NaOH, H2O

[Oxidative work-up] H3C

Oxidation of alkenes with MnO4- or OsO4 Cold, dilute, basic KMnO4 aqueous solution oxidizes multiple bonds: Product is cis-1,2-diol. Baeyer test for unsaturation purple permanganate ion is reduced to MnO2, a brown solid; indicates presence of double or triple bonds. OsO4 expensive and highly toxic reagent; will also oxidize alkenes to cis-1,2-diols Oxidation with peroxy acids: Alkenes react with peroxy acids to give 3-membered cyclic ethers known as epoxides or oxiranes. MCPBA m-chloroperoxybenzoic acid; commonly used peroxy acid since it is commercially available and is stable enough to store for long periods of time.