Alkenes

C2H4 ethylene

CnH2n

unsaturated hydrocarbons

H C C H

H H

Functional group = carbon-carbon double bond sp2 hybridization => flat, 120o bond angles bond & bond => H2C=CH2 No rotation about double bond!

C3H6 propylene

CH3CH=CH2

C4H8 butylenes

CH3CH2CH=CH2 -butylene 1-butene CH3 CH3C=CH2 isobutylene 2-methylpropene

CH3CH=CHCH3 -butylene 2-butene

there are two 2-butenes:

H H C C H3C CH3
cis-2-butene

H CH3 C C H3C H
trans-2-butene

geometric isomers

(diastereomers)

C=C are called vinyl carbons

If either vinyl carbon is bonded to two equivalent groups, then no geometric isomerism exists.

CH3CH=CHCH3 yes

CH3CH2CH=CH2 no CH3 CH3CH=CCH2CH3 yes

(CH3)2C=CHCH3 no

Confusion about the use of cis- and trans-. According to IUPAC rules it refers to the parent chain.

H3C CH2CH3 C C H CH3

cis-

H3C Cl C C H Br

????????

E/Z system is now recommended by IUPAC for the designation of geometric isomerism.

1. Use the sequence rules to assign the higher priority * to the two groups attached to each vinyl carbon.
2. * * *

(Z)- zusammen
together

(E)- entgegen
opposite

H3C CH2CH3 C C H CH3

(Z)-

H3C Cl C C H Br

(E)-

Nomenclature, alkenes: 1. Parent chain = longest continuous carbon chain that contains the C=C.

alkane => change ane to ene

prefix a locant for the carbon-carbon double bond using the principle of lower number. 2. Etc. 3. If a geometric isomer, use E/Z (or cis/trans) to indicate which isomer it is.

H3C CH2CH3 C C H CH3

(Z)-3-methyl-2-pentene (3-methyl-cis-2-pentene)

H3C Cl C C H Br

(E)-1-bromo-1-chloropropene

CH3 CH3CH2 CHCH2CH3 \ / C=C 3-ethyl-5-methyl-3-heptene / \ CH3CH2 H (not a geometric isomer)

-ol takes precedence over ene

CH2=CHCH2-OH

2-propen-1-ol

CH3CHCH=CH2 OH

3-buten-2-ol

Physical properties: non-polar or weakly polar no hydrogen bonding relatively low mp/bp water insoluble ~ alkanes

Importance: common group in biological molecules

starting material for synthesis of many plastics

Syntheses, alkenes:

1. dehydrohalogenation of alkyl halides

2. dehydration of alcohols

3. dehalogenation of vicinal dihalide

4. (later)

3. dehalogenation of vicinal dihalides | | C C + Zn | | X X | | C=C +

ZnX2

eg.
CH3CH2CHCH2 + Zn Br Br CH3CH2CH=CH2 + ZnBr2

Not generally useful as vicinal dihalides are usually made from alkenes. May be used to protect a carbon-carbon double bond.

1. dehydrohalogenation of alkyl halides

| | C C + KOH(alc.) | | H X | | C=C

+ KX + H2O

a) b) c) d) e) f) g) h)

RX: 3o > 2o > 1o no rearragement may yield mixtures Saytzeff orientation element effect isotope effect rate = k [RX] [KOH] Mechanism = E2

rate = k [RX] [KOH]

=> both RX & KOH in RDS

R-I > R-Br > R-Cl element effect

=> CX broken in RDS R-H > R-D isotope effect => CH broken in RDS Concerted reaction: both the CX and CH bonds are broken in the rate determining step.

Mechanism = elimination, bimolecular E2

W
RDS

C H base:

+ H:base + :W

One step! Concerted reaction.

CH3CHCH3 Br

+ KOH(alc)

CH3CH=CH2
propylene

isopropyl bromide

CH3CH2CH2CH2-Br
n-butyl bromide

+ KOH(alc)

CH3CH2CH=CH2
1-butene

CH3CH2CHCH3 Br
sec-butyl bromide

+ KOH(alc)

CH3CH2CH=CH2 1-butene 19% + CH3CH=CHCH3 2-butene 81%

Problem 8.6. What akyl halide (if any) would yield each of the following pure alkenes upon dehydrohalogenation by strong base? CH3 KOH(alc) + CH3CCH3 X CH3 CH3CHCH2-X

isobutylene

or

1-pentene KOH(alc) + CH3CH2CH2CH2CH2-X note: CH3CH2CH2CHCH3 would yield a mixture! X 2-pentene KOH(alc) + CH3CH2CHCH2CH3 X 2-methyl-2-butene KOH(alc) + NONE!

KOH(alc) ?????????

CH3 CH3CH CCH3

PURE!

2-methyl-2-butene

CH3 CH3CHCHCH3 X

KOH(alc)

CH3 H2C CHCHCH3

CH3 CH3CH CCH3

CH3 CH3CH2CCH3 X

KOH(alc)

CH3 CH3CH2C CH2

CH3 CH3CH CCH3

No alkyl halide will yield 2-methyl-2-butene as the only product of dehydrohalogenation

Saytzeff orientation: Ease of formation of alkenes:

R2C=CR2 > R2C=CHR > R2C=CH2, RCH=CHR > RCH=CH2 > CH2=CH2

Stability of alkenes:
R2C=CR2 > R2C=CHR > R2C=CH2, RCH=CHR > RCH=CH2 > CH2=CH2
CH3CH2CHCH3 + Br sec-butyl bromide KOH(alc) CH3CH2CH=CH2 1-butene 19% + CH3CH=CHCH3 2-butene 81% RCH=CH2

RCH=CHR

KOH (alc)

CH3CH2CH2CHBrCH3 CH3CH2CH=CHCH3 + CH3CH2CH2CH=CH2 71% 29%

CH3 CH3CH2CCH3 + KOH(alc) Br

CH3 CH3 CH3CH=CCH3 + CH3CH2C=CH2 71% 29%

CH3 CH3 CH3 CH3CHCHCH3 + KOH(alc) CH2=CHCHCH3 + CH3CH=CCH3 Br major product

Order of reactivity in E2: 3o > 2o > 1o

CH3CH2-X

CH2=CH2
CH3CH=CH2

3 adj. Hs
6 adj. Hs & more stable alkene 9 adj. Hs & most stable alkene

CH3CHCH3 X CH3 CH3CCH3 X

CH3 CH=CCH3

Elimination unimolecular E1
RDS

1)

C C H W

C C H

+ :W

2)

C C H

-H

C C

Elimination, unimolecular

E1

a) b) c) d) e) f) g)

RX: 3o > 2o > 1o rearragement possible may yield mixtures Saytzeff orientation element effect no isotope effect rate = k [RW]

E1:
Rate = k [RW] => only RW involved in RDS R-I > R-Br > R-Cl element effect => CX is broken in RDS R-H R-D no isotope effect => CH is not broken in the RDS

Elimination, unimolecular

E1

a) b) c) d) e) f) g)

RX: 3o > 2o > 1o rearragement possible may yield mixtures Saytzeff orientation element effect no isotope effect rate = k [RW]

carbocation
CW broken in RDS CH not broken in RDS only R-W in RDS

alkyl halide + base substitution or elimination?

X C C H :Z E2

SN2

R-X +

base

????????

1) If strong, conc. base: CH3 > 1o => SN2 R-Z 3o > 2o => E2 alkene(s)

2) If weak, dilute base:

3o > 2o > 1o => SN1 and E1 R-Z + alkene(s)

3) If KOH(alc.) 3o > 2o > 1o => E2 alkene(s)

SN2 CH3CH2CH2-Br 1o CH3 CH3CCH3 Br 3o E2 CH3 CH3C=CH2 + NaOCH3 CH3CH2CH2-O-CH3

+ NaOCH3

+ HOCH3

CH3CH2CH2-Br

E2 KOH(alc) CH3CH=CH2

CH3 CH3CHCHCH3 + dilute OHBr

CH3 CH3CCH2CH3 OH CH3 CH3C=CHCH2 CH3 CH2=CCH2CH3

SN1

+ CH3 CH3CHCHCH3 [1,2-H] CH3 CH3CCH2CH3

E1

E1

2. dehydration of alcohols: | | CC | | H OH | | acid, heat C = C

H2O

a) ROH: 3o > 2o > 1o b) acid is a catalyst c) rearrangements are possible d) mixtures are possible e) Saytzeff f) mechanism is E1 note: reaction #3 for alcohols!

Mechanism for dehydration of an alcohol = E1

1) C C H OH + H C C H OH2

RDS 2) C C H OH2 C C H + H2O

3)

C C H

C C

+ H

CH3CH2-OH CH3 CH3CCH3 OH

+ 95% H2SO4, 170oC CH2=CH2 CH3 CH3C=CH2

+ 20% H2SO4, 85-90oC

CH3CH2CHCH3 + 60% H2SO4, 100oC CH3CH=CHCH3 OH + CH3CH2CH=CH2

CH3CH2CH2CH2-OH + H+, 140oC

rearrangement!

CH3CH2CH=CH2
+ CH3CH=CHCH3

Synthesis of 1-butene from 1-butanol: CH3CH2CH2CH2-OH + HBr CH3CH2CH2CH2-Br SN2 E2 KOH(alc) CH3CH2CH=CH2 only! To avoid the rearrangement in the dehydration of the alcohol the alcohol is first converted into an alkyl halide.

Syntheses, alkenes:

1. dehydrohalogenation of alkyl halides

E2
2. dehydration of alcohols E1 3. dehalogenation of vicinal dihalide

4. (later)

R-OH

H+

R-X

KOH

(alc.)

Alkene Zn

vicinal dihalide

Alkyl halides: nomenclature syntheses: 1. from alcohols a) HX b) PX3

2. halogenation of certain alkanes 3.

4.
5. halide exchange for iodide reactions: 1. nucleophilic substitution 2. dehydrohalgenation 3. formation of Grignard reagent 4. reduction

Alcohols: nomenclature syntheses later reactions 1. HX

2. PX3
3. dehydration 4. as acids 5. ester formation 6. oxidation