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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
20-5
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20-7
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
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
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
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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
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
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)
20-22
Conjugated Systems
End Chapter 20
20-23
Chapter 21
20-24
Aromatic Compounds
H A Kek ul structure A Keku l structu re show ing all atoms as a line-angle formula
20-25
20-26
N N
Purine
N
N
N
Pyrimidine
Acridine
20-27
Benzene
Resonance
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
2 1
20-30
CH2 CH3
CH3
CH=CH2
Toluen e
Styrene
20-31
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
20-32
3 + substituents on benzene
For
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 CH2 CH3
1
PAHs
Polynuclear
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
20-34
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
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Reactions of Benzene
Sulfonation
H + H2 SO4 SO3 H + H2 O Benzenes ulfon ic acid
1 . H2 SO4 2 . NaOH
20-37
Phenols
The
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
N H
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Phenols as Antioxidants
Vitamin E is a natural antioxidant BHT and BHA are synthetic antioxidants
OH O
3
OH
Scavengers for radicals Form stable radicals (delocalize electron) Break chain propagation cycle Prevent further formation of hydroperoxides
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Phenols as Antioxidants
Phenols
Scavengers for radicals Form stable radicals (delocalize electron) Break chain propagation cycle Prevent further formation of hydroperoxides
OH O
3
OH