Chapter 7 Alkenes: Structure and Reactivity

Alkene - Hydrocarbon With Carbon-Carbon Double Bond Also called an olefin but alkene is better Hydrocarbon that contains a C-C double bond Includes many naturally occurring materials Flavors, fragrances, vitamins

Why this Chapter? C=C double bonds are present in most organic and biological molecules To examine consequences of alkene stereoisomerism To focus on an important alkene reaction: electrophilic addition

7.1 Industrial Preparation and Use of Alkenes Ethylene and propylene are important organic chemicals produced

Thermal Cracking Thermal cracking may take place w/o catalyst at very high temperatures

7.2 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 CnH2n+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 C6H10 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 these don't affect the formula of equivalent hydrocarbons May be ignored in calculating degrees of unsaturation

Organonitrogen Compounds Nitrogen has three bonds So if it connects where H was, it adds a connection point Subtract one H for equivalent degree of unsaturation in hydrocarbon

Summary - Degree of Unsaturation Count pairs of H's below CnH2n+2 Add number of halogens to number of H's (X equivalent to H) Ignore oxygens (oxygen links H) Subtract N's - they have two connections

Degree of Unsaturation - Video http://www.youtube.com/watch?v=sssEQ1Esm6g&feature=player_embedded

7.3 Naming Alkenes Name the parent hydrocarbon Number the carbons in chain so that double bond carbons have lowest possible numbers

Naming Alkenes (Continued) Write the full name- Number substituents according to: 1) Position in chain, 2)Alphabetically Rings have “cyclo” prefix

Many Alkenes Are Known by Common Names

Naming Alkenes Examples - Video http://www.khanacademy.org/science/organic-chemistry/v/naming-alkenes-examples

7.4 Cis-Trans Isomerism in Alkenes Carbon atoms in a double bond are sp2-hybridized Three equivalent orbitals at 120º 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

7.5 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

Alkene Stereochemistry and the E,Z Designation (Continued): 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

Alkene Stereochemistry and the E,Z Designation (Continued): Cahn-Ingold-Prelog Rules Must rank atoms that are connected at comparison point Higher atomic number gets higher priority Br > Cl > S > P > O > N > C > H

Alkene Stereochemistry and the E,Z Designation (Continued): Cahn-Ingold-Prelog Rules 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

Alkene Stereochemistry and the E,Z Designation (Continued): Cahn-Ingold-Prelog Rules 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

Entgegen-Zusammen Naming Scheme - Video 1) Entgegen-Zusammen Naming Scheme for Alkenes Examples http://www.khanacademy.org/science/organic-chemistry/v/entgegen-zusammen-naming-scheme-for-alkenes-examples

7.6 Stability of Alkenes Cis alkenes are less stable than trans alkenes Compare heat given off on hydrogenation: Ho Less stable isomer is higher in energy And gives off more heat tetrasubstituted > trisubstituted > disubstituted > monosusbtituted hyperconjugation stabilizes

Stability of Alkenes (Continued): Comparing Stabilities of Alkenes Evaluate heat given off when C=C is converted to C-C More stable alkene gives off less heat trans-Butene generates 5 kJ less heat than cis-butene

Stability of Alkenes (Continued): Hyperconjugation Electrons in neighboring filled  orbital stabilize vacant antibonding  orbital – net positive interaction Alkyl groups are better than H

Stability of Alkenes - Video http://learning.hccs.edu/faculty/paul.clemens/chem2423/Organic%20Chemistry%20Lecture%20Videos/chapter-7/stability-of-alkenes

7.7 Electrophilic Addition of Alkenes General reaction mechanism of electrophilic addition Attack on electrophile (such as HBr) by bond of alkene Produces carbocation and bromide ion Carbocation is an electrophile, reacting with nucleophilic bromide ion

Electrophilic Addition of Alkenes (Continued): Electrophilic Addition Energy Path Two step process First transition state is high energy point First step is slower than second

Electrophilic Addition of Alkenes (Continued) The reaction is successful with HCl and with HI as well as HBr HI is generated from KI and phosphoric acid

Ethylene: Electrophilic Addition Reactions - Video http://learning.hccs.edu/faculty/paul.clemens/chem2423/Organic%20Chemistry%20Lecture%20Videos/chapter-7/reactions-of-ethylene-electrophilic-addition-reactions

7.8 Orientation of Electrophilic Additions: Markovnikov’s Rule In an unsymmetrical alkene, HX reagents can add in two different ways, but one way may be preferred over the other If one orientation predominates, the reaction is regioselective Markovnikov observed in the 19th century that in the addition of HX to alkene, the H attaches to the carbon with more H’s and X attaches to the other end (to the one with more alkyl substituents) This is Markovnikov’s rule

Example of Markovnikov’s Rule Addition of HCl to 2-methylpropene Regiospecific – one product forms where two are possible If both ends have similar substitution, then not regiospecific

Markovnikov’s Rule (restated) More highly substituted carbocation forms as intermediate rather than less highly substituted one Tertiary cations and associated transition states are more stable than primary cations

Markovnikov’s Rule (restated)

Markovnikov's Rule and Carbocations - Video 1) Markovnikov's Rule and Carbocations: Markovnikov's Rule and Carbocations. Figuring out which addition reaction is more likely. http://www.khanacademy.org/science/organic-chemistry/v/markovnikov-s-rule-and-carbocations

7.9 Carbocation Structure and Stability Carbocations are planar and the tricoordinate carbon is surrounded by only 6 electrons in sp2 orbitals the fourth orbital on carbon is a vacant p-orbital the stability of the carbocation (measured by energy needed to form it from R-X) is increased by the presence of alkyl substituents

Carbocation Structure and Stability (Continued) A plot of DH dissociation shows that more highly substitued alkyl halides dissociate more easily than less highly substituted ones

Carbocation Structure and Stability (Continued) A inductive stabilized cation species

Carbocation Stability - Video http://learning.hccs.edu/faculty/paul.clemens/chem2423/Organic%20Chemistry%20Lecture%20Videos/chapter-7/carbocation-stability

7.10 the Hammond Postulate If a carbocation intermediate is more stable than another, why is the reaction through the more stable one faster? the relative stability of the intermediate is related to an equilibrium constant (DGº) the relative stability of the transition state (which describes the size of the rate constant) is the activation energy (DG‡) the transition state is transient and cannot be examined What does the Hammond Postulate state? “the structure of a transition state resembles the structure of the nearest stable species. Transition states for endergonic steps structurally resemble products, and transition states for exergonic steps structurally resemble reactants”

The Hammond Postulate (Continued): Transition State Structures A transition state is the highest energy species in a reaction step By definition, its structure is not stable enough to exist for one vibration But the structure controls the rate of reaction So we need to be able to guess about its properties in an informed way We classify them in general ways and look for trends in reactivity – the conclusions are in the Hammond Postulate

Examination of the Hammond Postulate A transition state should be similar to an intermediate that is close in energy Sequential states on a reaction path that are close in energy are likely to be close in structure - G. S. Hammond

Competing Reactions and the Hammond Postulate Normal Expectation: Faster reaction gives more stable intermediate Intermediate resembles transition state

The Hammond Postulate and Selectivity - Video 1) Yale – Hammond Postulate: START at 40:45 http://www.youtube.com/watch?feature=player_detailpage&v=2vP4uPgWC9Q 2) The Hammond Postulate and Selectivity http://learning.hccs.edu/faculty/paul.clemens/chem2423/Organic%20Chemistry%20Lecture%20Videos/chapter-7/the-hammond-postulate-and-selectivity

7.11 Evidence for the Mechanism of Electrophilic Addition: Carbocation Rearrangments Carbocations undergo structural rearrangements following set patterns 1,2-H and 1,2-alkyl shifts occur Goes to give moststable carbocation Can go through less stable ions as intermediates

Hydride shifts in biological molecules

Carbocation Rearrangement - Video http://learning.hccs.edu/faculty/paul.clemens/chem2423/Organic%20Chemistry%20Lecture%20Videos/chapter-7/carbocation-rearrangement

Let’s Work a Problem Addition of HCl to 1-isopropylcyclohexene yields a rearranged product. Propose a mechanism, showing the structures of the intermediates and using curved arrows indicate electron flow in each step. The hydrogen is approached by the nucleophilic double bond. A new C-H bond is formed, along with a 3˚ carbocation. At the same time, Cl takes on 1more electron, making it a Cl anion. There is a “Methyl” shift, creating a new C-H bond with the 1st 3˚ carbocation to give an isomeric 3˚ carbocation that is less hindered. The Cl-ion then approaches the new carbocation. A Cl-C bond is formed which gives charged neutral product.