Chs.

7 & 8: Alkenes

Alkenes (olefins): hydrocarbons containing C=C. Unsaturated ± less than 4 single (sigma) bonds to C. Simplest alkene = ethene C-C bond length = 1.34Å average bond angle = ~120o .

H
C=C

H H

H

ethene (ethylene)

Orbital picture shows

&

bonding bond and above and below plane

± electron density is along axis of of molecule in bond.

pi bond - sideways overlap of p orbitals

H H

H H ethene (ethylene) sigma bond - electron density along bond axis

# the C chain of parent so that C=C has the lowest possible number (locant). propene. pentene. choose the way that gives the lowest #¶s to branch points. 5 4 3 2 1 Ex: CH3CH2CH=CHCH3 If more than one way of numbering gives lowest # to C=C. Nomenclature : IUPAC rules Alkenes 1. (Alkane name minus ±ane plus ±ene) 2. . Select the longest carbon chain containing the double bond as the parent. Name as ethene. butene.I. etc.

6 H3C 5 4 3 1 2 CH 3 CH3 NOT 1 H3C 2 3 4 6 5 CH 3 CH3 .

3. Write full name #¶ing substitutents & listing them alphabetically. H3C CH3 H3C CH3 CH3 2-pentene 2-methyl-3-hexene .

4. If two or more double bonds are present, choose as the parent the longest C chain containing both and use the prefixes di, tri, tetra, etc. before ±ene.

H H H CH3 H H3C

H H CH2 H

1,3-pentadiene

2-ethyl-1,3-butadiene

Cycloalkenes 1. Give double bond lowest locant ± 1. 2. Number substituents thru the double bond so that they have the lowest possible locants. 3. List the substituents alphabetically.
4-methylcyclohexne

1-ethyl-4-methyl-1,3-cyclohexadiene

5,5-dimethyl-1,3-cyclohexadiene

Common names CH2=CH2 CH3-CH=CH2 H2C=CHH2C=CH-CH2ethylene propylene vinyl allyl (IUPAC: ethenyl) (IUPAC: 2-propenyl)

Cis/trans stereoisomerism Occurs in alkenes because there is no rotation about C=C H H CH3 CH3 H3C is not the same as H H CH3 .II.

Geometric isomers (cis/trans) exist for every alkene which has nonidentical groups attached to both C atoms of double bond H3C CH3CH2 CH3 -no cis/trans isomerism H H3C CH3CH2 H cis-2 pentene H H CH3CH2 CH3 trans 2-pentene H cis: substituents on same side of double bond trans: substituents on opposite sides of double bond .

E nomenclature 1. Assign priority to groups on each C of double bond 2. use E (Entgenen -apart). high C low Z C low low high high C E C high low H CH3 CH2CH3 . If high priority groups on both C's are on opposite side of the double bond.As molecules get larger and more complex. cis/trans nomenclature gets complicated. use Z (Zusammen . For cpds like: H3C CH3 use Z. 3. If high priority groups on both C's are on same side of the double bond.together).

Assignment of priority: Cahn-Ingold-Prelog Sequence Rules 1. If priority cannot be established by rule #1. 2. make a similar comparison of the next atoms in each group. # instead. . higher atomic # = higher priority C(6) > H(1) N(7) > C(6) O(8) > N(7) D(2) > H(1) Isotopes = special case since they have the same atomic # Use atomic wt. Assign priorities of the atoms directly attached to C atoms of the double bond according to atomic #.

3. Multiply-bonded atoms are equivalent to the same # of singly bonded atoms H H H = -C C C H C C H Ex: H C CH3 H C -C C-H = -C C N -C N: = -C N C C C C N C H .

O = CH3 C O -C O H C H H O = H C H O -C O H H .

Designate the following molecules as E or Z Br Cl H H3C H Z E O OH H3C CH2OH H CH3 Br H Z .

The larger the groups on the double bond. the greater the E difference between cis and trans.III. E = 2-3 kJ/mol . Stability of alkenes a) cis vs trans Generally. cis isomers are less stable than trans isomers H H3C H trans 2-butene CH3 CH3 H3C H H cis 2-butene -less stable: higher E due to steric strain.

24/.8kJ .Energy difference is reflected in 1) interconversion equilibria and 2) heats of hydrogenation Interconversion equilibria: H H3C H at 298K: 76% CH3 acid cat.314J/K)(298K)ln(.76) § 2. CH3 H3C H 24% H G = -RTlnK = -(8.

cat H2.heats of hydrogenation: H2. cat trans 2-butane butane cis 2-butene .

8 kJ = G data) b) stability of mono .8 kJ.Hhyd (cis)= -120 kJ/mol Hhyd (trans) = -116 kJ/mol Energy difference = 4 kJ/mol (close to 2. 4kJ is from while 2.vs polysubstituted alkenes General trend: R2C=CR2 > R2C=CHR > RCH=RCH § R2C=CH2 > RCH=CH2 more stable lower Hhyd less stable higher Hhyd H data .

Explanation of observed stability trend: -hyperconjugation occurs when a pi orbital can overlap (partially) with a neighboring sp3 orbital. the pi orbital can interact with 3 sp3 orbitals. -greater bond strength for sp2-sp3 bonds than for sp3-sp3 bonds.) and CH3-CH2-CH=CH2 (monosub. In the figure.) 2 sp3-sp2 bonds vs 1 sp3-sp3 and 1 sp3-sp2 . ±only happens when C=C is substituted. Compare CH3-CH=CH-CH3 (disub.

hydrogenation (reduction) 3. radical addition . electrophilic addition 2. oxidation 4.Reactions of Alkenes ± 4 types we¶ll examine 1.

Br. I) H-HSO4 H-OH .Electrophilic Addition + nucleophile Y-Z electrophile Y z I. Addition of acid: H-B -acid catalyzed B H R2C=CHR + H-B R R H R H-B = HX (X=Cl.

+ R R H R H + B B H R R H R .A) Mechanism 1. R2C=CHR + H B + R R H R H + B Rate determining step 2.

For H-Br + (CH3)2C=CH2 .

Outline the mechanism: .

Rate law from RDS: rate = k[alkene][H-B] first order in alkene first order in H-B second order overall .

B) intermediate of rxn = carbocation structure of R3C+: R + R R -sp2 hybridized -empty p orbital -6 valence electrons 120o Relative stabilities of carbocations ± effect of alkyl groups R3C+ > R2CH+ > RCH2+ > CH3+ most stable least stable 3o > 2o > 1o > CH3+ .

Hyperconjugation Overlap between vacant p orbital and an adjacent C-H bond (sp3 orbital) H H + + H H = H H - Not possible in methyl cation The more R groups.How do alkyl groups stabilize the positive charge? 1. the more hyperconjugative interactions are possible. .

2. . the greater the stabilizing effect. the more alkyl groups. C) Orientation of addition There are two possible products from the addition of H-B B H R2C=CHR OR H B R2C=CHR + H-B R R H R + H-B R R H R observed product Rxn is regioselective: only one of two possible directions of addition is observed. Inductive effects alkyl groups donate e.density by induction toward (+) charge.

Predict the products: H-Br ether H-Cl ether .Markovnikov¶s Rule: For electrophilic addition of HB to an alkene. the acid H will become attached to the double bond C already bonded to the greater # of H¶s.

To understand: CH3 H3C H CH3 H-Br H3C H3C Br H H CH3 or H3C H Br H CH3 CH3 Q: What does it mean to obtain only one of two possible products? A: Favored product is formed faster. RDS for two possibilities: CH3 H3C H CH3 H-Br H3C + H H CH3 + Br- product H3C H CH3 H3C H CH3 H-Br H3C H3C + H CH3 + Br- .

‡ The rate is proportional to e (-Ea/RT).‡ Shown is the energy profile for the RDS ‡ The rate is determined by the activation energy ± energy difference between reactant and transition state of RDS. . the slower the reaction. The greater the Ea.

the TS resembles the product. it must be formed faster. Therefore its TS must be lower in energy than the TS of the nonMarkovnikov product. Could this have been predicted? Hammond Postulate: For an endothermic reaction step.Since the Markovnikov product is the favored product. . For an exothermic reaction step. with a lower Ea. that is. the TS resembles the reactant.

the lower the Ea. compare the carbocations arising from the Markovnikov and non-Markovnikov pathways. the faster the reaction. Markovnikov pathway H3C + H H CH3 + H CH3 3o carbocation H3C H H3C H3C Non-Markovnikov pathway 2o carbocation . the more stable the TS. so the more stable the carbocation. the TS resembles the carbocation product of that step. So.For the RDS in the add¶n of H-B.

TS Ea (Mark. pathway) < Ea (non-Mark. TS < E of non-Mark.stability of carbocations: 3o > 2o > 1o E of the Mark. pathway is faster than non-Mark pathway . pathway) So Mark.

What is its structure? Write the mechanism for the acid catalyzed reaction between 1-methylcyclohexene and water (the 3rd reaction) . H+ All three reactions pass through the same intermediate carbocation.Predict the products: H-Cl ether H2SO4 H2O H2O.

D. Rearrangement of carbocations In some cases. more than one product may be obtained as a result of rearrangement of the carbocation intermediate. CH3 H H3C H H + H Cl (CH3)2CH H CH3 predicted Mark. product Example: H-Cl ether CH3 H3C Cl CH2CH3 rearranged product major product .

H3C H CH3 CHCH3 + H3C 1. H3C CH3 + CH2CH3 Second Q: What carbocation is originally produced (product of Mark.2 hydride shift CH3 + CH2CH3 Justification: conversion of a 2o carbocation to a 3o carbocation with increase in stability CH3 H3C H 2o CHCH3 + H3C CH3 + 3o CH2CH3 . First ask: What intermediate carbocation produced the rearranged product? A. H3C H H CH3 H CH3 H3C C CHCH3 H + H-Cl H Third Q: How do you get from initial R+ to the rearranged R+? A. addition of H+)? A.Provide a mechanism for the formation of the second product.

Other possible rearrangement: 1.2-alkyl shift H-Cl Example: C H-Cl Cl- .

F2 is too reactive. Br2. I2 is slow & not as useful) X X X 2 R2C=CR2 A. Mechanism R R R + R Br Br R R R R (a vicinal dihalide) R R Br + R R + Br cyclic bromonium ion R R Br + R R + Br Br R R R R Br .II. Addition of X2 (X2 = Cl2.

R R Br + R R + Br Br R R R R Br OR R R Br + R R Br + Br R R R Br R . Stereochemistry of addition = anti due to cyclic intermediate: Br.B.must add to side opposite to first Br.

Predict the product and give a mechanism: Br2 CCl4 .

Br + R2C CR2 Cl (NaCl) Cl I(NaI) NO3(NaNO3) Br H2O OH Br Br Br Br Br R2C=CR2 Br I NO3 halohydrin formation .C. The Nu: in the 2nd step of the rxn can be any nucleophile.

H2O HO-CH2CH2-Br HO-CH2CH2-Cl 2-bromoethanol .a bromohydrin 2-chloroethanol .Halohydrin C X C OH H2C=CH2 Br2. H2O .a chlorohydrin Cl2.

2 products are possible. Br2.For asymmetrical alkenes. H2O R2C=CHR R Br OH H or R R R OH Br H R R observed product -halogen becomes attached to the double bond C already bonded to the greater # of H atoms .

To understand: Br R R Br + H R R H R + R + + resembles 2o carbocation resembles 3o carbocation has more (+) character = point of attack by nucleophile .

When nucleoophile (H2O) attacks in 2nd step.H+ Br R H R R : O: H . R H Br + R R . : OH 2 Br R H R R +O: H H + . it attacks the more highly substituted C atom..

H Br Br H OH + CH3 Br HBr CH3 . Br Br H OH2 + Br CH3 +O H H + Br 2.Mechanism for halohydrin formation: note regiochemistry and stereochemistry Br2 OH2 H OH CH3 Br 1. H + Br CH3 H Br +O H H CH3 3.

Addition of H2O ± hydration ± 2 methods A. oxymercuration . Hg(OAc)2. -regiochemistry = Markovnikov .demercuration 1. H 2O R 2C=CHR 2.non-stereospecific .III.

NaBH4 CH3CH2 CH3 OH + AcO-Hg-OAc + H H + -OAc HgOAc H H H H H H O+ OH2 -OAc O H H H + HgOAc HgOAc HgOAc H O H H NaBH4 (exact mechanism not known) H not stereospecific . H2O H3C Example: 2. Hg(OAc)2.1.syn & anti addition is observed .

Hydroboration ± oxidation ± non-Mark. Addition .syn stereochemistry BH3. OH- .B. THF H2O2 .

Since -BH2 is later replaced by -OH.H3C 1. H CH3 CH2CH3 HO H2O2.2O2H ----- D B2H FHT . H2B 2.kraM-non . CH3 CH2CH3 + BH3 H2B H3C D ----- H CH3 CH2CH3 D -BH2 and -H add to the same side of the dbl bond .mota C detutitsbus ssel eht ot dedda si 2HB )yrtsimehcoiger .3HB 2HB-H 3 HC2HC 3 HC2HC D :msinahceM D .syn stereochemistry -BH2 is added to the less substituted C atom and -H is added to the more highly substituted C atom because that reduces crowding in the transition state.dnob lbd eht fo edis emas eht ot dedda era 2HB dna H -( yrtsimehcoerets cirets ssel ni stluser . OH- H CH3 CH2CH3 H3C D H3C D 3 HC2HC H B 2H 3 D HC2HC H HO D 3 HC2HC -HO H .1 D CH2CH3 nys . non-Markonikov regiochemistry results. OH- HC HC H OH D -HO .2 H3C D OH H CH3 CH2CH3 H2B H3C D H CH3 CH2CH3 .2O2H H B2H .etats noitisnart ni gnidworc H3C CH3 BH3. THF H2O2.

Simmons-Smith reaction . Addition of carbene .IV.R2C: CR2 + R2C: carbene is generated "in situ" cyclopropyl ring Example: CHCl3 KOH or KOt-bu :CCl2 (dichlorocarbene) CH2I2 Zn(Cu) I-CH2-Zn-I (carbenoid .adds :CH2) .

Zn(Cu) trans H CH3 CHCl3 KOH CH3 H Cl CH3 H H trans CH3 trans . Zn(Cu) H H Cl CH3 H H cis cis CH3 CH3 cis Cl H3C H H CH3 CH2I2.Reaction of carbenes with alkenes is stereospecific: Cl H3C H CH3 H CHCl3 KOH CH3 CH2I2.

Ni H R R Addition is syn H R R R2C=CR2 + H2 H2. . Pd/C. cat. PtO2.Hydrogenation (reduction) catalyst = Pt.

Under the relatively mild rxn conditions (Rm temp. H2 phenyl groups: Pd/C H2 carbonyl groups: PtO2 H2 PtO2 H2 cyano groups: Pd/C .) which reduce C=C. other multiple bonds are not reduced.

via halohydrin via halohydrin CH3 Br2 H2O H Br OH CH3 O CH3 epoxide (oxirane) mechanism of epoxide formation: H H Br : O: OH- H Br . Epoxidation 1..Oxidation A. :O:CH3 : O: epoxide (oxirane) CH3 CH3 .

via peroxyacid O OH R O CH3 O epoxide (oxirane) CH3 .2.

Hydroxylation ± glycol formation (glycol = cpd with vicinal hydroxy groups) To get cis glycol: 1. pyridine 2. OsO4.B. NaHSO3 (aq) H H cis OH OH To get trans glycol: RCOOOH H HO O H H H3O+ H OH trans .

C. Oxidative Cleavage . ozonolysis 2. permanganate oxidation 3. periodate oxidation of glycols .3 types 1.

O3 2.1. Zn.H+ R1 O R2 + O R3 R4 R = alkyl. ozonolysis of alkenes R1 R2 R3 R4 1. H .

H+ or KMnO4.2. permanganate oxidation of alkenes R H R1 R2 H H R3 H KMnO4. neutral R O + OH O O R2 + R3 OH CO2 KMnO4. carbon dioxide RCOOH. carboxylic acid R2C=O. neutral R1 R = alkyl =CH2 =CHR =CR2 CO2. ketone . H+ or KMnO4.

NaHSO3 (aq) R1 R2 R3 R4 HO R1 R2 OH R3 R4 alkene HIO4 R1 O R2 O glycol R3 R4 . OsO4. periodate oxidation of glycols (result like ozonolysis) 1. pyr 2.3.

generates another free radical 3) termination: ends the polymer and doesn't produce a radical Ex: Combination of 2 radicals R + R R-R . RO-CH2-CH2. 2) propagation: attack of alkene by a free radical generates another free radical RO. + H2C=CH2 RO-CH2-CH2. . + H2C=CH2 RO-CH2-CH2-CH2-CH2.Radical Polymerization ± use fish hook arrows in mechanism H H RO-OR nH2C=CH2 RO H H n * 3 steps in any radical reaction: 1) initiation: generation of a free radical RO OR 2RO.

need to take into account the stability of radicals.OR 2RO. 2. RO CH-CH2-CH-CH2 observed product not observed . H2C=CHR RO-CHR-CH2 R R . RO-CH2-CHR . + .OR 2RO. 3. RO. RO CH2-CH-CH2-CHR R 1. RO-CHR-CH2 + H2C=CHR . + H2C=CHR 2.Polymerization of unsymmetrical alkenes ± to predict product. RO . . n H2C=CHR RO-OR RO CH2-CHR * or RO CHR-CH2 ?? n n * Mechanism for formation of first product: Mechanism for formation of second product: 1. RO. . RO . RO-CH2-CHR + H2C=CHR 3.

Q: Why do radicals in step 2 & step 3 always add to the less hindered C atom? A: So the more highly substituted radical is formed H R RO. 2o radical . + H2C=CHR or RO H H R H RO H H Order of radical stability: 3o > 2o > 1o >. 1o radical .CH3 so the more stable radical is formed. .