Organic Chemistry

Paula Yurkanis Bruice

Chapter 11

Organometallic Compounds - all with Video Answers

Educators

SK

Chapter Questions

Problem 1

Which of the following reactions favor formation of the products?
$$\begin{aligned}
\mathrm{CH}_{3} \mathrm{MgBr}+\mathrm{H}_{2} \mathrm{O} & \rightleftharpoons \mathrm{CH}_{4}+\mathrm{HOMgBr} \\
\mathrm{CH}_{3} \mathrm{MgBr}+\mathrm{CH}_{3} \mathrm{OH} & \rightleftharpoons \mathrm{CH}_{4}+\mathrm{CH}_{3} \mathrm{OMgBr} \\
\mathrm{CH}_{3} \mathrm{MgBr}+\mathrm{NH}_{3} & \rightleftharpoons \mathrm{CH}_{4}+\mathrm{H}_{2} \mathrm{NMgBr} \\
\mathrm{CH}_{3} \mathrm{MgBr}+\mathrm{CH}_{3} \mathrm{NH}_{2} & \rightleftharpoons \mathrm{CH}_{4}+\mathrm{CH}_{3} \mathrm{NHMgBr} \\
\mathrm{CH}_{3} \mathrm{MgBr}+\mathrm{HC} \equiv \mathrm{CH} & \rightleftharpoons \mathrm{CH}_{4}+\mathrm{HC} \equiv \mathrm{CMgBr}
\end{aligned}$$

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Problem 2

Which is more reactive, an organolithium compound or an organosodium compound? Explain your answer.

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Problem 3

Which is more reactive, an organolithium compound or an organosodium compound? Explain your answer. $$\mathrm{GaCl}_{3} ?$$

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Problem 4

Describe two ways to synthesize ethylcyclohexane from alkyl bromides.

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Problem 5

Muscalure is the sex attractant of the common housefly. Flies are lured to traps filled with bait that contain muscalure and an insecticide. Eating the bait is fatal. How could you synthesize muscalure using 1-bromopentane as one of the starting materials?

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Problem 6

What bromo-substituted compound is required to react with $\left(\mathrm{CH}_{2}=\mathrm{CH}\right)_{2} \mathrm{CuLi}$ in order to form the following compound?

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Problem 7

What bromo-substituted compound would be required to react with $$\left(\mathrm{CH}_{2}=\mathrm{CH}\right)_{2} \mathrm{CuLi}$$ in order to form each of the following compounds?

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Problem 8

What alcohols are formed from the reaction of ethylene oxide with the following organocuprates followed by the addition of acid?

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Problem 9

What are the products of the following reactions?

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Problem 10

How could the following compounds be prepared, using cyclohexene as a starting material?

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Problem 11

Using any necessary reagents, show how the following compounds could be prepared using ethylene oxide
as one of the reactants: a. $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{OH}$
b. $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{Br}$ c. $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{D}$
d. $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{OH}$

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Problem 12

What is the product of each of the following reactions?

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Problem 13

What is the product of each of the following reactions?

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Problem 14

What aryl or vinylic halides would you use to synthesize the following compounds, using the alkenylorganoboron compound shown here?

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Problem 15

What hydrocarbon would you use to prepare the organoboron compound in Problem $14 ?$

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Problem 16

The Stille reaction is similar to the Suzuki reaction. It replaces the alkenyl-organoboron compound of the Suzuki reaction with an alkenyl-organotin compound. (R is an alkyl group such as methyl or butyl.) Unlike the alkenyl-organoboron compound that always has a trans configuration, the alkenyl-organotin compound can have a cis configuration. What is the product of the Stille reaction shown here?

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Problem 17

What is the product of each of the following reactions?

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Problem 18

What reactants are needed to synthesize each of the following compounds using a Heck reaction?

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Problem 19

What reactants are needed to synthesize each of the following compounds using a Heck reaction?

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Problem 20

Show how the Suzuki and/or Heck reactions can be used to prepare the following compounds:

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Problem 21

Identify two pairs of an alkyl bromide and an alkene that could be used in a Heck reaction to prepare the following compound:

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Problem 22

What products are obtained from metathesis of each of the following alkenes?

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Problem 23

Draw the product of ring-closing metathesis for each of the following compounds:

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Problem 24

What compound undergoes metathesis to form each of the following compounds?

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Problem 25

What compound undergoes metathesis to form each of the following compounds?

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Problem 26

What new products are obtained from metathesis of the following alkyne?

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Problem 27

What are the products of the following reactions?

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Problem 28

Which of the following alkyl halides could be successfully used to form a Grignard reagent?

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Problem 29

The coupling of an alkyne with an aryl halide in the presence of a palladium catalyst and triethylamine is called a Sonogashira reaction. What reactants couple to form this product?

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Problem 30

Identify A through $\mathbf{H}$.

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Problem 31

Using the given starting material, any necessary inorganic reagents and catalysts, and any carbon-containing compounds with no more than three carbons. indicate how each of the following compounds can be prepared:

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Problem 32

What alkyl halide reacts with lithium divinylcuprate $\left[\left(\mathrm{CH}_{2}=\mathrm{CH}\right)_{2} \mathrm{CuLi}\right]$ for the synthesis of each of the following compounds?

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Problem 33

What are the products of the following reactions?

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Problem 34

What vinylic halide couples with styrene $\left(\mathrm{C}_{6} \mathrm{H}_{5}-\mathrm{CH}=\mathrm{CH}_{2}\right)$ in order to synthesize each of the following compounds using a Heck reaction?

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Problem 35

The following compound undergoes an intramolecular reaction to form ethene and a product with a five-membered ring. Identify the product and the catalyst used to carry out the reaction.

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Problem 36

Using ethynylcyclohexane as a starting material and any other needed reagents, how can the following compounds be synthesized?

SK

Sara Kolms

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Problem 37

What are the products of the following reactions?

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Problem 38

Using the given starting material, any necessary inorganic reagents and catalysts, and any carbon-containing compounds with no more than two carbons, indicate how each of the following compounds can be prepared:

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Problem 39

Dimerization is a side reaction that occurs during the preparation of a Grignard reagent. Propose a mechanism that accounts for the formation of the dimer.

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Problem 40

A student added an equivalent of 3,4 -epoxy- 4 -methylcyclohexanol to a solution of methylmagnesium bromide in diethyl ether, and then added dilute hydrochloric acid. He expected that the product would be 1,2 -dimethyl- 1,4 -cyclohexanediol. He did not get any of the expected product. What product did he get?

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Problem 41

Using the given starting material, any necessary inorganic reagents, and any carbon-containing compounds with no more than two carbons, indicate how each of the following compounds can be prepared

SK

Sara Kolms

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Problem 42

a. Which of the following compounds cannot be prepared by a Heck reaction?
b. For those compounds that can be prepared by a Heck reaction, what starting materials are required?

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Problem 43

What is the maximum yield of 2 -pentene that can be formed in the reaction shown on page $523 ?$

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Problem 44

Bombykol is the sex pheromone of the silk moth. Show how bombykol can be synthesized from the following compounds.

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Problem 45

a. Metathesis of which of the following sets of alkenes leads to the highest yield of a single alkene?
1. 1-butene and 1-pentene 2. 2-butene and 3-hexene 3. 2-butene and 1-pentene
b. What kinds of alkenes should be used in metathesis reactions that use two different alkenes as starting materials?

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Problem 46

key step in the synthesis of naproxen, an NSAID more commonly known by its brand name, Aleve (Section 3.9), is a coupling reaction of 2-bromo- 6-methoxynaphthalene to form 2-methoxy-6-vinylnaphthalene. Show three different coupling reactions, and the required reagents, that could be used to carry out this step.

SK

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Problem 47

A dibromide loses only one bromine when it reacts with sodium hydroxide. The dibromide forms toluene $$\left(\mathrm{C}_{6} \mathrm{H}_{5}-\mathrm{CH}_{3}\right)$$ when it reacts with magnesium shavings in ether followed by treatment with dilute acid. Give possible structures for the dibromide.

SK

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Problem 48

What starting material is required in order to synthesize each of the following compounds by ring-closing metathesis?

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Problem 49

What product is obtained from ring-opening metathesis polymerization of each of the following compounds?

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