CHEM 2312 E2 practice i 1.

(32 points) Circle the letter on the right which corresponds to the answer to each question. There is only one correct answer for each question. (i) Which of the following would be the best synthesis of 3,5-dibromotoluene? A. p-CH3C6H4NH2, Br2, H2O; then HONO; then H3PO2 B. Toluene, Br2, Fe and heat C. Toluene, fuming HNO3, H2SO4; then NH3, H2S; then HONO; then CuBr D. m-Dibromobenzene, CH3Cl, AlCl3, heat (ii) Arrange the following in order of increasing acidity (weaker acid < stronger acid)
1

A B C D
OH NH2

OH

OH

E. iv<iii<ii<i F. iii<ii<i<iv G. ii<i<iii<iv H. iv<i<iii<ii (iii) Arrange the following in order of increasing basicity (weaker base < stronger base) I. i<iii<ii<iv J. iii<ii<i<iv K. ii<i<iii<iv L. iv<i<iii<ii

CN CN

E F G H I J K L M N O P Q R S T U V W X Y Z AA BB CC DD EE FF

ii
HN

iii
NH2

iv

NH2

N NO2

ii

iii

iv

(iv) Which of the following sets of substituents are all ortho/para directing for electrophilic aromatic substitution reactions? M. -NO2, -Cl, -OH N. -OMe, -NH2, -CN O. NHCOCH3, -Cl, -CO2H P. -NHCOCH3, -CH3, -Br

(v) Which of the following sequences is the correct order of reactivity (fastest > slowest) for the nitration of substituted benzenes, Ph-X? Q. CH3 > OH > NO2 > Cl S. OH > CH3 > NO2 > Cl R. OH > Cl > CH3 > NO2 T. OH > CH3 > Cl > NO2

(vi) Which of the following undergoes the fastest reaction with sodium hydroxide? U. bromobenzene W. 4-nitro-1-bromobenzene V. 3-nitro-1-bromobenzene X. 1,3-dinitrobenzene

(vii) Which of the following is the best approach to make 1-propylbenzene Y. benzene + 1-chloropropane, AlCl3 Z. benzene + 1-propanol, HF AA. benzene + propanoyl chloride, followed by HCl, Fe BB. toluene + ethane, HF (viii) Which of the following is most nucleophilic? CC. aniline DD. toluene EE. benzene FF. bromobenzene

2. (38 points) (a) Provide the structure of the major organic products of the following reactions.
1. NaOH 2. CO2+ 3. H3O

OH

K2Cr2O7 H2SO4,

Cl NaNH2

Cl HNO3, H2SO4

Cl

1. NaNO2, HCl 2. CuCN

CH3 NBS

NH2 O Br2

C8H9BrO

(b) Draw the keto intermediates in: (i) the Kolbe reaction of sodium phenoxide with carbon dioxide, and (ii) the Claissen rearrangement of allyl phenyl ether. (i) (ii)

3. (30 points) Provide a sequence of reactions to perform the following transformations, showing the reagents and structures of all isolated synthetic intermediates. The synthesis must use the given starting materials; you may also use benzene and any other starting materials with 3 or fewer carbon atoms. You may use any reagents. Do not show mechanisms or the structures of reactive intermediates. Shorter, more efficient syntheses are preferred; overly long or inefficient sequences will lose some credit.

CN

Br

O O

CO2H

Br