5. For each of the following reactions use a different Grignard reagent with the molecular formula C₆H₁₃MgCl to react with an electrophile containing the functional group specified.Give the structure of the Grignard reagent, the electrophile, and the major organic product formed, and name the product.

a. formaldehyde

b. another aldehyde

c. a ketone

f. an epoxide

g. carbon dioxide

6. Give the reagent(s) or sequence of reagents that would best be used to accomplish each transformation in the synthetic sequence given.Assume that each compound is the major organic product formed.

 

a.	b.	c.
d.	e.

1. Show how the compound below can best be synthesized from benzene.The usual rules apply – you may use any reactants/reagents necessary; show the reactants and major organic product(s) for each reaction; if a reaction gives a mixture of structural isomers in comparable amounts draw them and assume that the desired isomer can be separated and carried on.

2. Show how each product can best be synthesized from the indicated starting material.The usual rules (as in #1) apply.

 

	product:	starting material:
a.		anisole
b.		nitrobenzene
c.	1-iodo-3-propylbenzene
d.	cyclohexylbenzene
e.		iodobenzene

6. Consider the following electrophilic aromatic substitution reaction.

a. Draw the major organic product(s) expected.

b. Draw the significant resonance structures of the positively charged intermediate leading to the major product (if you drew more than one isomer of product, just choose one).

7. The electrophilic aromatic substitution reaction shown below can give (among others) the two isomers shown below.Draw the significant resonance structures of the positively charged intermediate leading to each isomer, and indicate which isomer of product would predominate.

8. The reaction of benzene with an excess of tert-butyl chloride in the presence of AlCl₃ gives as the major product the compound for which the 13C NMR data is given below.Give the structure of the product.

13C: 148.56, 125.46, 34.81, 31.98 ppm.

9. Using the reagents listed below, synthesize one example of each of the following from benzene as efficiently as possible.You may use each set of reagents only once.The usual rules still apply: show the reactants and major organic product(s) for each reaction; if a reaction gives a mixture of structural isomers in comparable amounts draw them and assume that the desired isomer can be separated and carried on.

Reagents:

 

Cl2/FeCl3

Br2/FeBr3

I2/HNO3

acetyl chloride/ AlCl3

2-chloro-2-methylpropane/ AlCl3

HNO3/H2SO4

SO3/H2SO4

a. a 1,2-disubstituted aromatic compound

b. a 1,3-disubstituted aromatic compound

c. a 1,4-disubstituted aromatic compound

10. Give the structures of compounds A, B, C, D, and E in the reaction sequence below.Assume that each one is the major product formed in the reaction.

1. Show how the compound below can best be synthesized from benzene.The usual rules apply – you may use any reactants/reagents necessary; show the reactants and major organic product(s) for each reaction; if a reaction gives a mixture of structural isomers in comparable amounts draw them and assume that the desired isomer can be separated and carried on.

2. Make each of the following compounds from benzene.The usual rules apply.

 

a. benzene-1,4-dioic acid

b. 1-bromo-4-propylbenzene

c. 2-phenylpropanenitrile

4a. Draw an aromatic compound with the molecular formula C₇H­₈O.

b. Draw another compound with the same molecular formula that is not aromatic, and explain why it is not.

5. Consider the following electrophilic aromatic substitution reaction.

a. Draw the major organic products expected.

b. Choose one product, and draw the significant resonance structures of the positively charged intermediate leading to it.

9. Compound A, with the molecular formula C₉H₁₂, undergoes electrophilic aromatic substitution to form compounds B and C, two mono-bromo structural isomers, in comparable amounts.The 13C-NMR data for the products is given below.Give the structures of compounds A, B, and C.

Product B 13C-NMR: 149.32, 131.22, 128.51, 122.24, 32.69, 23.40 ppm

Product C 13C-NMR: 147.72, 129.85, 127.57, 125.52, 121.96, 121.87, 31.81, 25.40 ppm.

11. Give the structure of the major organic product(s) for each of the following reactions.If a mixture of structural isomers would be formed in comparable amounts, draw each one.If a racemic mixture would be formed just draw one enantiomer.

a.

b.

c.

d.

f.

h.

i.