Deck 16: Carbonyl Chemistry 1: Addition Reactions

Question 1

What are the missing reagents in the reaction sequence shown here?

A)1. Na₂Cr₂O₇, H₂SO₄, H₂O
2. NH₂OH , trace acid
B)1. LiAlH₄
2. H₂O
3. NH₂OH, trace acid
C)1. NaBH₄, MeOH
2. NH₃ , then H₃O⁺
D)NH₃ , then H₃O+
E) None of these

Answer 1

1. Na₂Cr₂O₇, H₂SO₄, H₂O
2. NH₂OH , trace acid

Question 2

Which of the following structures is a hydrate?

A)
B)
C)
D)
E)

Answer 2

Question 3

Rank these carbonyl compounds in order of increasing C=O stretching frequency in their IR spectra:

A) I< II < III < IV
B)I< IV < II < III
C)I < II < IV < III
D)III < II < IV < I
E)IV < I < II < III

Answer 3

I< IV < II < III

Question 4

Which of the following compounds corresponds to the spectrum shown here?

A)
B)
C)
D)
E)

Question 5

Give the correct IUPAC name for the following carbonyl compound.

A) bicyclo[2.2.2]oct-7-en-2,5-dione
B) tricyclo[2.2.2]oct-2-en-5,7-dione
C) bicyclo[2.2.2]oct-5-en-1,4-dione
D) bicyclo[2.2.2]oct-7-en-1,4-dione
E) tricyclo[2.2.2]hex-2-en-3,5-dione

Question 6

Which of the hydrates shown is most stable?

A)
B)
C)
D)
E)

Question 7

Which of the following compounds cannot be used to form an imine?

A)
B)
C)
D)
E)NH₃

Question 8

Which of these factors is least important in determining the regiochemistry of hydration of carbonyl compounds?

A) the greater strength of the C-O versus the O-O bond.
B) the pH under which the reaction takes place
C) the greater ability of oxygen to accommodate a negative charge in the intermediate
D) the greater orbital overlap at carbon for the π* orbital of the carbonyl
E) All these factors are important in determining the regiochemistry of the addition.

Question 9

Which of these compounds does not contain an acetal group?

A)
B)
C)
D)
E) All are acetals.

Question 10

For which of the following compounds do you expect the aldehyde to be more stable than its hydrate?

A) I
B) II
C) III
D) I, II, and IV
E) III and IV

Question 11

Which of the following is the major product of the reaction conditions shown?

A)
B)
C)
D)
E)

Question 12

Which is the correct name for the ketone shown here?

A) 4-ethyl-5-methyl-3-hexanone
B) 3 -ethyl-2-methyl-4-hexanone
C) 3 -isopropyl-4-hexanone
D) 4-ethyl-5,5-dimethyl-3-pentanone
E) 2-ethyl-1,1-dimethyl-3-pentanone

Question 13

What is the major product generated on removal of the protecting groups in this molecule using the conditions shown?

A)
B)
C)
D)
E)

Question 14

Which carbonyl compounds below has the IUPAC name: (2 R, 3 S)-2,3 -dibromo-4-methylpentanal?

A)
B)
C)
D)
E)

Question 15

Which of the following statements correctly describes the major product of this reaction?

A) The major product is an enamine; imines form only when the amine is secondary.
B) The major product is a carbinolamine.
C) The major product is an enamine; to form an imine, the nitrogen-containing nucleophile must be ammonia.
D) The major product is an imine; imines are more stable than enamines.
E) The major product is an enamine because the carbonyl starting material is a ketone.

Question 16

Which of the following reagents is used to install a protecting group for an alcohol?

A)trimethylsiyl chloride
B)dihydropyran
C)ethylene glycol
D)both a and b
E)a, b, and c

Question 17

Which of the following compounds, when placed in water, do you expect to have the least amount of hydrate present at equilibrium?

A)
B)
C)
D)
E) All these compounds will have about the same amounts of hydrate at equilibrium.

Question 18

Which of the following is the major product of the reaction conditions shown?

A)
B)
C)
D)
E)

Question 19

What sequence of reagents could be used for the following synthetic transformation?

A)
B)
C)
D)
E)

Question 20

Rank the following compounds in order of increasing equilibrium constant for conversion to the hydrate.

A) II < IV < III < I
B) III < I < II < IV
C) IV < III < I < II
D) IV < II < I < III
E) I < IV < III < II

Question 21

What is the product of the following reaction?

A)
B)
C)
D)
E)

Question 22

Rank these carbonyl compounds in order of increasing C=O dipole moment.

Question 23

The following compound
was treated with the following sequence of reagents
1. HBr, H₂O₂
2. Li, ether
3. Formaldehyde, followed by H₃O⁺
4. CrO₃, pyridine
5. Ph₃P=CH₂
Which of the following absorptions would you not expect to see in the IR spectrum of the final product of this multistep synthesis?

A) C=O stretch
B) C-O stretch
C) C=C stretch
D) C-H stretch
E) a and b

Question 24

In the multistep synthesis shown here, what would be the first step?

A) Mg, ether
B) CO₂
C) H₃O⁺
D) KMnO₄
E)

Question 25

Which is a mechanistic intermediate in the following transformation?

A)
B)
C)
D)
E)

Question 26

Draw the following compounds with correct stereochemistry.

A) (Z)-4-oxo-2-pentenal
B) (R)-2-\mathrm{hydroxy}-4 -heptanone
C) (S)-4 -bromocyclopent-2-en-1-one

Question 27

What is the product of this reaction?

A)
B)
C)
D)
E) No reaction occurs.

Question 28

Which of the following statements about the biological oxidation of alcohols is false?

A) Alcohol dehydrogenase is an enzyme that binds both ethyl alcohol and nicotinamide adenine dinucleotide NAD⁺
B) NAD⁺ is a pyridinium ion and a strong Lewis acid.
C) In the reaction catalyzed by alcohol dehydrogenase, ethyl alcohol is reduced and NAD⁺ is oxidized.
D) Alcohol dehydrogenase catalyzes a hydride transfer.
E) One of the products of the reaction catalyzed by alcohol dehydrogenase is an aldehyde.

Question 29

Which statement about this reaction is correct?

A)The products are enantiomers, formed in a racemic mixture.
B)The products are diastereomers, formed in equal amounts.
C)The products are enantiomers, formed in unequal amounts.
D)The products are diastereomers, formed in unequal amounts.
E)Not enough information is given to predict the products.

Question 30

Provide a name for the following compound.

Question 31

What is the product of the following reaction?

A)
B)
C)
D)
E)

Question 32

What is the final product of this reaction?

A)
B)
C)
D)
E)

Question 33

Which of the following compounds will not react with CrO₃/pyridine to give a carbonyl compound?

A)
B)
C)
D)
E)

Question 34

Which reagent would you use to effect this transformation?

A)
B)
C)
D)
E)

Question 35

Which of the following alcohols cannot be made through the reduction of a carbonyl compound using a nucleophilic hydride reagent?

A)
B)
C)
D)
E)

Question 36

Which of the following compounds would you use, with an acid catalyst, to convert the starting material to the product shown?

A)
B)
C)
D)
E)

Question 37

Which reagents would you use to accomplish the following transformation?

A) LiAlH₄, then H₃O⁺
B) NaBH₄ in methanol
C)1. CH3MgBr,
2. H₃O⁺
D)H₂,Pd /C
E) CH₃MgBr and H₃O⁺

Question 38

Which of the following products could be made from cyclohexanone plus other reagents?

A) I
B) II
C) III
D) I and II
E) II and IV

Question 39

Which of the following reagents could be used to effect the organic transformation shown here?

A) CH₃CH₂Li
B) CH₃CH₂MgBr
C) (CH₃)₂CuLi
D) CH₃Li
E) (CH₃CH₂)₂CuLi

Question 40

Which reagent would you use to accomplish the transformation shown?

A)
B)
C)
D)
E)

Question 41

Predict the product of the following reaction and draw an arrow-pushing mechanism to rationalize its formation.Include all necessary lone pairs, curved arrows, and nonzero formal charges.

Question 42

What product would be recovered from the following reaction?

Question 43

Draw a mechanism to illustrate the removal of the acetal under the conditions shown.Include all necessary lone pairs, curved arrows, and nonzero formal charges.

Question 44

Draw a mechanism for the following transformation.Include all necessary lone pairs, curved arrows, and nonzero formal charges.

Question 45

Draw a mechanism for the following transformation.Include all necessary lone pairs, curved arrows, and nonzero formal charges.

Question 46

Predict the product of the following reaction.

Question 47

For each structure, state whether it is an acetal, a hemiacetal, or neither.

Question 48

Draw the structure of the compound with molecular formula C₄H₆O that has the following ¹H NMR and IR spectra.

Question 49

Draw the product of the following reaction, showing stereochemistry.

Question 50

Propose a mechanism for the removal of the THP ether-protecting group in the following compound under the conditions shown.Include all necessary lone pairs, curved arrows, and nonzero formal charges.

Question 51

Predict the product of the following reaction and draw a mechanism to rationalize its formation. Include all necessary lone pairs, curved arrows, and nonzero formal charges.

Question 52

Draw a mechanism for the following transformation.Include all curved arrows, necessary lone pairs, and nonzero formal charges.

Question 53

Match each compound to the appropriate spectrum.

Question 54

Predict the product of the following reaction.

Question 55

Draw a mechanism to illustrate the following transformation.Include all necessary lone pairs, curved arrows, and nonzero formal charges.

Question 56

Draw a mechanism for the hydration of the compound shown here under acidic conditions. Include all lone pairs, curved arrows, and nonzero formal charges.

Question 57

Draw a mechanism for the hydration of the compound shown here under basic conditions.Include
all lone pairs, curved arrows, and nonzero formal charges.

Question 58

Draw a mechanism to illustrate the formation of an acetal (ketal) under the conditions shown. Include all necessary lone pairs, curved arrows, and nonzero formal charges.

Question 59

An acyclic compound was treated with trace acid to produce this structure. Draw the structure of the acyclic compound.

Question 60

For each of the carbonyl compounds shown, qualitatively show the relative free energies (ΔG) of the carbonyl and its hydrate based on K_eq for the hydration reaction.

Question 61

Write a multistep synthesis for the following transformation.

Question 62

Predict the product of the following reaction.

Question 63

Draw all combinations of carbonyl compounds and organometallic reagents that would give the alcohol shown.

Question 64

Predict the product of the following reaction.

Question 65

Which combination of carbonyl compound and organometallic reagent would give the compound shown?

Question 66

Design a multistep synthesis for the following transformation.You may use any organic or inorganic reagents.Show the reagents needed for each step and the product of each step.

Question 67

Use a retrosynthetic analysis to provide five possible precursors to this alcohol. Include the reagents needed to transform each of the precursors to the alcohol.

Question 68

Design a multistep synthesis for the transformation shown here.You may use any organic or inorganic reagents.Show the reagents needed for each step and the product of each step.

Question 69

Which reagent or reagents would you use to accomplish the following transformation?

Question 70

Predict the product of the following reaction.

Question 71

How would you accomplish the following oxidation reaction?

Question 72

Predict the product of the following reaction.

Question 73

Design a multistep synthesis for the following transformation.You may use any organic or inorganic reagents.Show the reagents needed for each step and the product of each step.