Roberts, Caserio - Basic Principles of Organic Chemistry (2nd edition, 1977)

do20 21 The Resonance and Molecular-Orbital Methods and Their Applications. Pericyclic Reactions

21-31 Which c~rrlpoundin each of the following pairs would lose chloride ion more readily and form a carbonium ion? Explain.

21-32 Devise an atomic-orbital model for cyclooctatetraene in accord with the geometry expressed by formula 25a (Section 21-9A) and explain why electron delocalization is not likely to be important for a structure with this geometry.

21-33 The conjugated 1,3,5,7,9-cyclodecapentaene with the double-bond configuration as in 53 is far less stable than either azulene, 54,or bicyclo[4.4.1]-1.3,5.7,9- undecapentaene, 55.Explain why this is so on the basis of the VB method (molecular models will be helpful).

21-34 1,3-Diazole (imidazole) is a planar molecule with substantial delocalization (resonance) energy.

a. Devise an atomic orbital model of imidazole and sketch o.ut the rr molecular orbitals you would expect for the molecule on the basis of those in Figure 21-13.

b. 1,3-Diazole is relatively acidic and forms the anion C3N2H33,Which is the acidic hydrogen? Draw valence-bond structures for the anion and indicate which ones should be expected to contribute most to the hybrid structure.

21-35 Predict which of the following molecules would have some degree of resonance stability by applying the Huckel (417+ 2) n--electron rule.

c. 2,4-Cyclopentadienone is not a stable compound and readily polymerizes.

21-37" 1,2-Propadiene is represented in Figure 13-4 as if it were two isolated Huckel ring systems. This molecule also may be represented as a stable Mobius system of 477. electrons. Draw an orbital diagram of 1,2-propadiene to indicate this relationship. If 1,2-propadiene twisted so that the hydrogens on the ends all were in the same plane, 57,would it be a Huckel or a Mobius polyene, or neither?

21-38 Bicyclo[2.2.0]-l(4)-hexene is highly strained and quite unstable. When it decomposes at room temperature, tetracycl0[6.2.2.0~~~.0~,~]-3(6)-dodeceneisformed.1°

a.Write a structural formula for the product.

b.Show a reasonable sequence by which it might be formed, with the knowledge that bicyclo[2.2.0]-l(4)-hexene is an extraordinarily reactive dienophile in [4 + 21

cycloadditions.

21-39 Bicyclo[2.2.0]-2,5-hexadiene is much less stable than its isomer, benzene, yet it does not rearrange to benzene except at elevated temperatures. Give a reason for this observation.

21-40 Show the expected stereochemistry of the product of each of the following thermally concerted reactions:

a. 2-trans,4-cis,6-cis,8-trans-decatetraene --+ 7,8-dimethyl-1,3,5-cyclooctatriene

CH3 C6H5

l0Numbering such as l(4) means that the double bond comes between carbons 1 and 4 and is used only where necessary to avoid ambiguity.

Supplementary Exercises

b. Determine whether the reactions in Part a are thermally allowed

21-43* Tetracyanoethene undergoes [2 + 21 cycloaddition with cisand trans-l- methoxypropene. The following facts are known about these reactions.

1 . Addition is several thousand times faster in CH3CN (a quite polar solvent) than in cyclohexane.

2.The [2 + 21 addition product becomes less stereospecific as the solvent is changed from nonpolar to polar.

3.The cisand trans-I-methoxypropenes are interconverted by tetracyanoethene at a rate comparable to the [2 + 21 addition rate with tetracyanoethene.

4.In methanol, only a small amount of [2 +21 cycloadduct is formed and the principal product is HC(CN),C(CN),CH(CH,)CH(OCH,),.

a.Write the structures for the [2 + 21 addition.

b.What do Facts 1 and 2 indicate about the mechanism? Write the possible steps involved.

c.Draw an energy diagram for the reaction in a polar solvent as a function of a reaction coordinate in the style of Figure 13-1. This diagram should agree with Fact 3. (Be sure you study the legend of Figure 13-1 before drawing your diagram.)

d. Account for the formation of HC(CN)2C(CN)2CH(CH3)CH(OCH3)2along with a [2 + 21 cycloadduct in methanol (a polar solvent). Would you expect any CH30C

(CN),C(CN),CH(CH3)CH20CH3to be formed? Explain.

22 Arenes. Electrophilic Aromatic Substitution

Th e names that have been given to these and other more elaborate types of polynuclear aromatic hydrocarbons are for the most part distressingly uninformative with respect to their structures.'

give on introduction of a third substituent? Name each isomer, using chlorine as the third substituent.

Exercise 22-3 Name each of the following compounds by the IUPAC system:

22-2 PHYSICAL PROPERTIES OF ARENES

Th e pleasant odors of the derivatives of many arenes is the origin of the name aromatic hydrocarbons. T h e arenes themselves generally are quite toxic; some are carcinogenic and inhalation of their vapors should be avoided. Th e volatile arenes are highly flammable and burn with a luminous sooty flame, in contrast to alkanes and alkenes, which usually burn with a bluish flame leaving little carbon residue.

Th e more common arenes and their physical properties are given in Table 22-1. They are less dense than water and are highly insoluble. Boiling

IA thorough summary of names and numbering systems has been published by A. M. Patterson, L. T. Capell, and D. F. Walker, Ring Index, 2nd ed., American Chemical Society, 1960. Less complete but useful summaries are given in various handbooks of chemistry.

22-2 Physical Properties of Arenes

Table 22-1

Physical Properties of Arenes

benzene

methylbenzene (toluene) ethyl benzene

propylbenzene

isopropyl benzene [ ( I -methylethyl) benzene] tert-butyl benzene [(2,2-dimethylethyl)benzene] 1,2-dimethyl benzene (ortho-xylene) 1,3-dimethylbenzene (meta-xylene) 1,4-dimethylbenzene (para-xylene) 1,3,5-trimethylbenzene (mesitylene) 1,2,4,5-tetramethyl benzene (durene) naphthalene

anthracene phenanthrene

points increase fairly regularly with increasing molecular weight, but there is little correlation between melting point and molecular weight. Th e melting point is highly dependent on the symmetry of the compound; thus benzene melts 100"higher than methylbenzene, and the more symmetrical 1,4-dimethyl- benzene (para-xylene) has a higher melting point than either the 1,2- or the 1,3-isomer. This latter fact is utilized in the separation by fractional crystallization of 1,4-dimethylbenzene from mixtures of isomers produced from petroleum.

22-3 SPECTRAL PROPERTIES OF ARENES

22-3A Infrared Spectra

Th e presence of a phenyl group in a compound can be ascertained with a fair degree of certainty from its infrared spectrum. For example, in Figure 22-1 we see the infrared spectra of methylbenzene, and of 1,2- 1,3-, and 1,4-di- methylbenzene. That each spectrum is of a benzene derivative is apparent from certain common features. Th e two bands near 1600 cm-I and 1500 cm-l, although of variable intensity, have been correlated with the stretching vibrations of the carbon-carbon bonds of the aromatic ring; also, the sharp bands near 3030 cm-l are characteristic of aromatic C-I3 bonds. Other bands in the

22 Arenes. Electrophilic Aromatic Substitution

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