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Chapter 20

Conjugated Systems
20-1

Conjugated Dienes
from heats of hydrogenation, we can compare relative stabilities of conjugated and unconjugated dienes
N ame 1-Butene 1-Penten e cis- 2-Butene trans- 2-Buten e 1,3-Butadien e t rans- 1,3-Pentad iene 1,4-Pentadien e Structural Formula H0 kJ (kcal)/mol -127 (-30.3) -126 (-30.1) -120 (-28.6) -115 (-27.6) -237 (-56.5) -226 (-54.1) -254 (-60.8)

20-2

Conjugated Dienes
conjugation of the double bonds in 1,3-butadiene gives an extra stability of approximately 17 kJ (4.1 kcal)/mol
2 + 2 H2 catalyst 2 H 0 = 2(-127 kJ/mol) = -254 kJ/mol) + 2 H2 catalyst H 0 = -237 kJ/mol

20-3

Conjugated Dienes

the pi system of butadiene is derived from the combination of four 2p atomic orbitals; there are two bonding MOs and two antibonding MOs

20-4

Conjugated Systems
systems containing conjugated double bonds, not just those of dienes, are more stable than those containing unconjugated double bonds
O O

2-Cyclohexenone (more s table)

3-Cycloh exenone (less s table)

20-5

1,2- and 1,4-Addition


Addition

of 1 mol of HBr to butadiene at -78C gives a mixture of two constitutional isomers


CH2 = CH- CH= CH2 + HBr 1,3-Butadiene Br H Br H CH2 = CH- CH- CH 2 + CH2 - CH= CH- CH 2 3-Bromo-1-butene 1-Bromo-2-butene 90% 10% (1,2-addition) (1,4-addition) -78C

we account for these products by the following twostep mechanism

20-6

1,2- and 1,4-Addition


the key intermediate is a resonance-stabilized allylic carbocation
CH2 =CH-CH=CH2 + H-Br + H CH2 =CH-CH-CH2 _ Br Br H CH2 =CH-CH-CH2 (1,2-Ad dition) Br Br H CH2 -CH=CH-CH2 (1,4-Ad dition) H + CH2 -CH=CH-CH2 _

20-7

1,2- and 1,4-Addition


Addition

of 1 mole of Br2 to butadiene at -15C also gives a mixture of two constitutional isomers
CH 2 = CH - C H = CH2 + Br 2 1,3-Butadiene Br Br -15C Br + Br

CH 2 - C H - CH = CH 2 3,4-Dibromo-1-butene (54%) (1,2-addition)

CH 2 - C H = CH - CH 2 1,4-Dibromo-2-butene (46%) (1,4-addition)

we account for the formation of these 1,2- and 1,4addition products by a similar mechanism
20-8

Experimental Information
for addition of HBr at -78C and Br2 at -15C, the 1,2addition products predominate; at higher temperatures (40 to 60C), the 1,4-addition products predominate if the products of the low temperature addition are warmed to the higher temperature, the product composition becomes identical to the higher temperature distribution; the same result can be accomplished using a Lewis acid catalyst, such as FeCl3 or ZnCl2 if either pure 1,2- or pure 1,4- addition product is dissolved in an inert solvent at the higher temperature and a Lewis acid catalyst added, an equilibrium mixture of 1,2- and 1,4product forms; the same equilibrium mixture is obtained regardless of which isomer is used as the starting material

20-9

1,2- and 1,4-Addition


We

interpret these results using the concepts of kinetic and thermodynamic control of reactions Kinetic control: the distribution of products is determined by their relative rates of formation
in addition of HBr and Br2 to a conjugated diene, 1,2addition occurs faster than 1,4-addition
+ CH2 = CH-CH-CH3 a 2 allylic carb ocation (greater contribu tion ) + CH 2 -CH=CH-CH 3 a 1 allylic carbocation (less er con trib ution)

20-10

1,2- and 1,4-Addition


Thermodynamic

control: the distribution of products is determined by their relative stabilities


in addition of HBr and Br2 to a butadiene, the 1,4addition product is more stable than the 1,2-addition product
Br BrCH2 CHCH=CH2 3,4-D ibromo-1-bu tene (less stable alk ene) + H BrCH2 C C CH2 Br H

(E)-1,4-D ib romo-2-b utene (more stab le alkene)

20-11

1,2- and 1,4-Addition


Figure

20.3 Kinetic vs thermodynamic control

20-12

UV-Visible Spectroscopy
Region of Spectrum near ultraviolet visib le Energy Wavelength (nm) k cal/mol k J/mol 200-400 400-700 299-598 171-299 71.5 - 143 40.9 - 71.5

Absorption

of radiation in these regions give us information about conjugation of carbon-carbon and carbon-oxygen double bonds and their substation

20-13

UV-Visible Spectroscopy
typically, UV-visible spectra consist of one or a small number of broad absorptions

20-14

UV-Visible Spectroscopy
Beer-Lambert

law: the relationship between absorbance, concentration, and length of the sample cell (cuvette)
Beer-Lambert Law: A = e c l
A = absorbance (unitless): a measure of the extent to which a compound absorbs radiation of a particular Io wavelength
Absorbance (A) = log I

e = molar absorptivity (M-1cm-1): a characteristic property of a compound; values range from zero to 106 M-1cm-1 l = length of the sample tube (cm)
20-15

UV-Visible Spectroscopy
the visible spectrum of b-carotene (the orange pigment in carrots) dissolved in hexane shows intense absorption maxima at 463 nm and 494 nm, both in the blue-green region

b-carotene m ax 463 (log e 5.10); 494 (log e4.77)

20-16

UV-Visible Spectroscopy the visible spectrum of a near infrared dye dissolved in methanol shows intense absorption maxima at 779 nm (=250000 l/mol.cm). Calculate the concentration in mg/ml of this dye that gives an absorbance of 0.98 at 779 nm.

20-17

UV-Visible Spectroscopy
Absorption

of UV-Vis radiation results in promotion of electrons from a lower-energy (occupied MO) to a higher-energy (unoccupied MO)
the energy of this radiation is sufficient to promote electrons in a pi (p) orbital to a pi antibonding (p*) MO it is generally no sufficient to affect electrons in the much lower-energy sigma bonding (s) MOs following are three examples of conjugated systems
O O 1,3-Butadien e 3-Bu ten-2-on e H Ben zaldehyde

20-18

UV-Visible Spectroscopy
UV-Visible

spectroscopy of carbonyls

simple aldehydes and ketones show only weak absorption in the UV due to an n to p* electronic transition of the carbonyl group if the carbonyl group is conjugated with one or more carbon-carbon double bonds, intense absorption occurs due to a p to p* transition
O O O

2-Pentanone m ax 180 nm (e 900)

3-Penten-2-one m ax 224 nm (e 12,590)

Acetophenone ma x 246 nm (e 9,800)

20-19

UV-Visible Spectroscopy

20-20

UV-Visible Spectroscopy
Figure 20.5 A p to p* transition in excitation of 1,3butadiene

20-21

UV-Visible Spectroscopy
Wavelengths and energies required for p to p* transitions of ethylene and three conjugated polyenes
En ergy m ax Structural Formula (nm) [kJ (kcal)/mol] 165 217 268 290 724 (173) 552 (132) 448 (107) 385 (92)

N ame Ethylene 1,3-Butadiene (3E)-1,3,5-Hexatrien e (3E,5E)-1,3,5,7-Octatetraene

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Conjugated Systems
End Chapter 20
20-23

Chapter 21

Benzene and Derivatives

20-24

Aromatic Compounds

Aromatic compound: a hydrocarbon that contains one or more benzene-like rings


Arene: a term used to describe aromatic compounds Ar-: a symbol for an aromatic group derived by removing an -H from an arene Kekul structure for benzene (1872)
H H C C H C C C C H H

H A Kek ul structure A Keku l structu re show ing all atoms as a line-angle formula

20-25

Problem 52, p. 301

20-26

Heterocyclic Aromatic Compounds

Aromatic Compounds with atoms other than C in the rings

N N
Purine

N
N

N
Pyrimidine

Acridine

20-27

Benzene
Resonance

structure for benzene (1930s)

Resonance Theory gave first really good description of the structure of benzene Resonance structures can be written as two or more Lewis structures; the real molecule or ion is a resonance hybrid of these structures Each individual Lewis structure is called a contributing structure Use double-headed arrow to show that actual structure is a resonance hybrid of two or more Lewis structures

20-28

Benzene
Two contributing structures for benzene
H H C C H C C H C C H H H H C C H C C H C C H H

Resonance hybrid has characteristics of each Lewis contributing structure Not alternating double and single bonds Length of carbon-carbon bond in benzene is midway between that of a carbon-carbon single bond and a double bond

20-29

Nomenclature
Common names for these monosubstituted benzenes are also retained O O
OH OCH3 NH2 C-H C-OH

Phen ol

A nisole

A niline

Ben zaldehyde

Benzoic acid

Phenyl group (C6H5- or Ph-): the substituent group derived by loss of an H from benzene
4

C6 H5 Ph enyl group 1-Ph enylcyclohexene

2 1

4-Phen yl-1-b utene

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One substituent on benzene


Monosubstituted alkylbenzenes are named as derivatives of benzene; for example, ethylbenzene IUPAC system uses common names for some simple monosubstituted alkylbenzenes;

CH2 CH3

CH3

CH=CH2

Eth ylb enzene

Toluen e

Styrene

20-31

Two substituents on benzene


When

two substituents occur on a benzene ring, three isomers are possible To show location of substituents:
Number the atoms of the ring OR Use the locators ortho (o), meta (m), and para (p)
COOH 1 Br 2
1

CH3
2 3

CH2 CH3
4 3

CH3 2-Bromobenzoic acid (o-Bromoben zoic acid) 1,3-D imethylben zene (m- Xylen e)

2 1

Cl 1-Ch loro-4-ethylbenzen e (p-Chloroeth ylb enzene)

20-32

3 + substituents on benzene
For

three or more substituents on benzene:

If a substituent is part of special molecules, name the molecule as a derivative of it Number the substituents to give the lowest numbers and list them in alphabetical order before the ending "benzene"
CH3
1 2

OH NO2 Br
6 1 2

NO2 Br
3 4 3 2

3 4

5 4

Cl 4-Ch loro-2nitrotoluen e

Br 2,4,6-Trib romoph enol

Br CH2 CH3
1

2-Bromo-1-ethyl-4n itroben zene


20-33

PAHs
Polynuclear

aromatic hydrocarbon (PAH)

a hydrocarbon that contain two or more benzene rings, with each pair of rings sharing two adjacent carbon atoms

N aphth alene

An thracene

Phen anthrene

Benzo[a]pyren e

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Reactions of Benzene

Aromatic substitution Remove H from ring and replace it with another atom or group
Some groups can be substituted directly on the ring are the halogens, the nitro (-NO2) group, and the sulfonic acid (-SO3H) group

Halogenation
H + Cl2 Benzen e FeCl3 Cl + HCl Ch lorobenzen e

20-35

Reactions of Benzene

Nitration
H2 SO4

H + HNO3

NO2 + H2 O N itrob enzene

20-36

Reactions of Benzene
Sulfonation
H + H2 SO4 SO3 H + H2 O Benzenes ulfon ic acid

Used in the preparation of synthetic detergents


CH3 ( CH2 ) 1 0 CH2 D odecylben zene CH3 ( CH2 ) 1 0 CH2 SO3 Na
+

1 . H2 SO4 2 . NaOH

Sodiu m 4-d od ecylben zenesu lfonate, S D S (an an ion ic detergent)

20-37

Phenols
The

functional group of a phenol is a hydroxyl group bonded to a benzene ring


name substituted phenols either as derivatives of phenol or by common names

OH

OH

OH OH

OH

OH

OH Phen ol 3-Methylph enol 1,2-Benzened iol (m- Cres ol) (Catech ol) 1,3-Benzened iol (Resorcinol) OH 1,4-Benzen ediol (Hydroq uinone)

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Examples of Phenols

Some phenols found in nature


OH H3 CO O CH OH OH CH2 (CH2 ) 1 3 CH3 U ru shiol (Poison ivy)

2-Isoprop yl-5methylphen ol (Thymol)


CH3 O HO

HO 4-Hyd roxy-3-meth oxybenzald ehyde (V anillin)


O C

N H

Cap saicin (from variou s types of pepp ers )

20-39

Phenols as Antioxidants
Vitamin E is a natural antioxidant BHT and BHA are synthetic antioxidants
OH O
3

OH

H OCH3 Butylated hydroxyanisole (BHA)

HO Vitamin E Butylated hydroxytolu ene (BHT)

Scavengers for radicals Form stable radicals (delocalize electron) Break chain propagation cycle Prevent further formation of hydroperoxides
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Autoxidation of Compounds containing C=C to hydroperoxides

General reaction: Conversion of R-H group to an R-O-O-H (hydroperoxide) Requires oxygen


H light CH2 CH=CH-CH + O2 or h eat Oxygen Section of a fatty acid h yd rocarbon chain O-O-H CH2 CH=CH-CH-CH2 A hydroperoxid e

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Phenols as Antioxidants
Phenols

interfere with radical propagation

Scavengers for radicals Form stable radicals (delocalize electron) Break chain propagation cycle Prevent further formation of hydroperoxides
OH O
3

OH

H OCH3 Butylated hydroxyanisole (BHA) 20-42

HO Vitamin E Butylated hydroxytolu ene (BHT)

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