Deck 21: Phenols and Aryl Halides: Nucleophilic Aromatic Substitution

Question 1

What is the common name for

A) m-Hydroxyphenol
B) m-Dihydroxybenzene
C) Resorcinol
D) 1,3-dihydroxybenzene
E) 1,3-Benzenediol

Answer 1

Resorcinol

Question 2

What would be the major product of the following reaction?

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

Answer 2

IV

Question 3

Which of the following phenols would have the largest pK_a?

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

Answer 3

III

Question 4

What is the IUPAC name for

A) p-Hydroxyphenol
B) p-Dihydroxybenzene
C) Resorcinol
D) 1,4-dihydroxybenzene
E) 4-methylphenol

Question 5

Which products would be formed in the following reaction?

A) Methoxybenzene + methyl bromide
B) 2-Methylphenol + methyl bromide
C) 2-Bromotoluene + methanol
D) 2-Bromotoluene + methyl bromide
E) Bromobenzene + methyl bromide

Question 6

Which of these is an acceptable synthesis of phenetole (ethyl phenyl ether)?

A)

B)

C)

D)

E) A and C

Question 7

Which of the following would be the strongest acid?

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

Question 8

When sodium phenoxide is heated to 125 $\degree$ C with carbon dioxide under pressure and the product mixture acidified,which of these is produced?

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

Question 9

What are the products of the reaction of phenol with propanoic anhydride in the presence of base?

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

Question 10

The common name for 1,2-benzenediol is which of these?

A) Catechol
B) m -Cresol
C) Resorcinol
D) Hydroquinone
E) o-Xylenol

Question 11

What is the IUPAC name for

A) m-Hydroxy-p-nitrotoluene
B) 3-Hydroxy-4-nitrotoluene
C) 5-methyl-2-nitrophenol
D) 3-methyl-2-nitrophenol
E) 2-Hydroxy-4methylnitrobenzene

Question 12

The common name for 3-methylphenol is which of these?

A) Catechol
B) m -Cresol
C) m-tolylol
D) Hydroquinone
E) p-Xylenol

Question 13

Refluxing anisole,CH₃OC₆H₅,with excess concentrated HBr would yield which of these product mixtures?

A) C₆H₅Br + CH₃OH
B) C₆H₅OH + CH₄
C) C₆H₅OH + CH₃OH
D) C₆H₅Br + CH₃Br
E) C₆H₅OH + CH₃Br

Question 14

Which compound would be most acidic?

A) Cyclohexanol
B) 1-Hexanol
C) Phenol
D) 4-Methylphenol
E) 4-Chlorophenol

Question 15

Indicate the correct product,if any,of the following reaction.

A) I
B) II
C) III
D) IV
E) There is no net reaction.

Question 16

Which of these species is the strongest base?

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

Question 17

Which of the following compounds would you expect to be the strongest acid?

A) CH₃OH
B) C₆H₅CH₂OH
C) p-CH₃C₆H₄OH
D) C₆H₅OH
E) p-NO₂C₆H₄OH

Question 18

What is the product of the reaction of phenol and chloroacetic acid in basic solution,followed by acidification?

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

Question 19

Which method could be used for preparing methoxybenzene from phenol?

A) NaOH,then CH₃I
B) NaOH,then CH₃OSO₃CH₃
C) NaOH,then CH₃OCH₃
D) A and B
E) All of these

Question 20

The common name for 4-methylphenol is which of these?

A) Catechol
B) p-Cresol
C) Resorcinol
D) Hydroquinone
E) p-Xylenol

Question 21

What is the product of the following synthesis?

A) 2,3-Dibromophenol
B) 2,4-Dibromophenol
C) 2,6-Dibromophenol
D) 2-Hydroxy-3,5-dibromobenzenesulfonic acid
E) 2,4,6-Tribromophenol

Question 22

What product is likely to be obtained by the action of Ag⁺ or Fe⁺³ on the following substance?

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

Question 23

Predict the product of this Cope rearrangement:

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

Question 24

Which of the following would provide a synthesis of aspirin, o-CH₃COOC₆H₄COOH?

A) C₆H₅COOH,CH₃COOH,AlCl₃,heat;then H₂O
B) CH₃COOC₆H₅,CO₂,heat;then H₃O⁺
C) CH₃COOC₆H₅,HCOOC₂H₅,C₂H₅O^-;then H₃O⁺;then OH^-
D) C₆H₅OH,CO₂,H₃O⁺;separate isomers;then CH₃COOH,AlCl₃
E) C₆H₅OH,OH^-,CO₂,heat,pressure;then H₃O⁺;then (CH₃CO)₂O

Question 25

Which of these reactions does not produce phenol? I think this question is ok

A)

B)

C)

D)

E)

Question 26

What is the product of the reaction of 1 mol of p-benzoquinone with 1 mol of isoprene (2-methyl-1,3-butadiene)?

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

Question 27

Thymol,isolated from thyme,has the following structure: Which of the following types of signal is NOT expected to be observed in its NMR spectrum?

A) singlet
B) doublet
C) triplet
D) septet
E) all of the above types of signals are expected to be observed

Question 28

What products(s)would you expect from the following reaction?

A) I
B) II
C) III
D) Products I and II
E) All of the above

Question 29

What product should be obtained if benzyne is generated in the presence of 1,3-butadiene?

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

Question 30

In terms of reactivity towards nucleophiles,bromobenzene is most similar to which of these?

A) Allyl bromide
B) Vinyl bromide
C) tert-Butyl bromide
D) Propyl bromide
E) Methyl bromide

Question 31

What is the final product?

A) 1-tert-Butyl-4-ethoxybenzene
B) 1-tert-Butyl-4-ethylbenzene
C) 1-tert-Butoxy-4-ethoxybenzene
D) tert-Butyl ethyl ether
E) 1-tert-Butoxy-3-ethylbenzene

Question 32

Which is the leaving group when the following substance reacts with sodium cyanide in DMSO solution?

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

Question 33

Which position is predicted to be the chief site of substitution when the following substance reacts with bromine in carbon disulfide at 10 $\degree$ C ?

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

Question 34

Which of the following would be most likely to undergo a nucleophilic substitution reaction with aqueous sodium hydroxide by an addition-elimination mechanism?

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

Question 35

Which of the following reactions would yield p-tert-butylphenol?

A)

B)

C)

D) All of these
E) None of these

Question 36

The formation of equal amounts of m-toluidine (m-aminotoluene)and p-toluidine in the reaction of p-bromotoluene with sodium amide in liquid ammonia at -33 $\degree$ C suggests this species as the reaction intermediate:

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

Question 37

Which product is likely to be obtained during the following reaction of the isotope-labeled allyl ether (14C-isotopic site marked with an asterisk)?

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

Question 38

What is the major product of the following reaction?

A) p-Hydroxybenzenesulfonic acid
B) p-Nitrophenol
C) o-Nitrophenol
D) B and C
E) A and B

Question 39

Which of these resonance structures makes the greatest contribution to the hybrid for the intermediate in the S_NAr reaction of o-chloronitrobenzene with methoxide ion?

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

Question 40

What product(s)would you expect from the following reaction?

A) I
B) II
C) III
D) Substantial amounts of I and II
E) Substantial amounts of I,II,and III

Question 41

Most of the worldwide industrial preparation of phenol is now based on the ___________.

Question 42

The cumene hydroperoxide synthesis of phenol is industrially very satisfying,because it takes two inexpensive starting materials,___________ and ___________,and converts them into two valuable products,phenol and __________.

Question 43

The industrial synthesis of phenol from cumene involves the acid hydrolysis of the key intermediate,cumene hydroperoxide (formed from cumene via oxidation).Outline the mechanistic steps that lead to this oxidation product.Which other industrially important substance is produced as a by-product in this reaction?

Question 44

Outline the steps involved in the synthesis of 3-nitrophenol from 1,3-dinitrobenzene

Question 45

Outline the steps involved in the synthesis of 3-nitrophenol from benzoic acid

Question 46

Methyl salicylate,commonly found in topical muscle relaxants,has the following structure: Which of the following signals is NOT expected to be observed in its NMR spectrum?

A) Singlet at ~4 ppm (3H)
B) Doublet at ~7 ppm (1H)
C) Quartet at about 7 ppm (4H)
D) Singlet at ~ 6 ppm (1H)
E) Two of the above types of signals are not expected to be observed

Question 47

Draw the structure corresponding to the following IUPAC name:
4-benzyl-3,5-diiodophenol

Question 48

Draw the structure corresponding to the following IUPAC name:
(2E,4S)-4-(3-hydroxyphenyl)-2-pentenoic acid

Question 49

What is the effect of electron releasing and withdrawing group on ring acidity?

Question 50

Compound L has the molecular formula C₁₁H₁₆O.L is insoluble in water but dissolves in aqueous NaOH.The infrared spectrum of L shows a broad absorption band in the 3200-3600 cm^-1 region;its ¹H NMR spectrum consists of: triplet, δ 0.80 (3H)
Singlet, δ1.2 (6H)
Quartet,δ 1.5 (2H)
Singlet, δ4.5 (1H)
Multiplet,δ 7.0 (4H)
The most likely structure for compound L is:

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

Question 51

Propose three synthetic methods to outline the steps that could be used (showing all
reagents and reaction conditions)to carry out the transformation shown below.

Question 52

The spectra shown below are for the compound A.Explain each spectrum with labeling all
the peaks and Identify compounds A-C. IR Spectrum of Compound A ¹HNMR Spectrum of Compound A ¹³CNMR Spectrum of Compound A 9 different signals = 9 different protons

Question 53

Outline the steps involved in the synthesis of 3-bromo-4-methylphenol from 4-nitrotoluene

Question 54

Give the IUPAC name of the following substance:

Question 55

The most important laboratory synthesis of phenols is by _______________.

Question 56

Draw the structure corresponding to the following IUPAC name:
(R)-2-Bromo-5-(3-methylpentyl)phenol

Question 57

Eugenol,isolated from cloves,has the following structure: Which of the following signals is NOT expected to be observed in its NMR spectrum?

A) Singlet at ~4 ppm (3H)
B) Doublet at ~2.5 ppm (2H)
C) Singlet at ~ 7 ppm (1H)
D) Singlet at ~ 6 ppm (1H)
E) All of the above types of signals are expected to be observed

Question 58

The commonly used name for hydroxybenzene is __________.

Question 59

A key step in the industrial synthesis of phenol from cumene is the oxidation of cumene to cumene hydroperoxide with oxygen.Outline the mechanistic steps that lead to this oxidation product.

Question 60

Write the IUPAC name of aspirin and its use.

Question 61

Nitration of phenol gives only ortho and para products.What is the reason for this?

Question 62

Phenol is an enol.In water it will undergo an enol to keto tautomerization
1)Will this reaction likely go by a base or acid catalyzed mechanism? Show the
mechanism.
2)Which is more stable the enol or ketoform? Why?

Question 63

Identify the major products formed by the reaction of phenol with each of the following:
(a)HNO₃ / H₂SO₄ / heat
(b)CH₃CH₂Cl / AlCl₃ / heat
(c)H₂SO₄ / SO₃/ heat
(d)CH₃CH₂COCl / AlCl₃ / heat /H₂/Pd-C
(e)Na then add benzyl chloride
(f)HBr

Question 64

Explain why cleavage of phenyl alkyl ether with HBr always give phenol and alkyl bromide.

Question 65

Draw the structure of the product obtained when benzoquinone reacts with 2 molar equivalents of 1,3-butadiene via a Diels Alder reaction.

Question 66

When phenol is nitrated with dilute nitric acid,a mixture of o- and p- substituted products is obtained.These products can then be separated by the technique of steam distillation.However,analogous products from the nitration of methoxybenzene cannot be similarly separated by steam distillation.Explain.

Question 67

Draw the structure of the product obtained when the following substance is heated strongly:

Question 68

Draw the structure of the final product obtained when 3-methylphenol is subjected to the following reaction sequence:
i)NaOH;ii)CH₃CH₂CH₂OSO₂OCF₃

Question 69

Draw the structure of the ionic species obtained when the following substance is treated with NaOH:

Question 70

Discuss the less boiling point of o-nitrophenol compared to p-nitrophenol.

Question 71

Discuss the following reaction
(a)Williamson's synthesis (b)Kolbe's reaction

Question 72

Draw the structure of the final product obtained when 2-nitrophenol reacts with acetic anhydride in presence of base.

Question 73

Which is a stronger acid: Phenol or p-cresol?

Question 74

The Claisen and Cope rearrangements are two examples of a general class of reactions called ___________.

Question 75

Suggest a simple chemical test to distinguish between 4-methylphenol and 2,4,6-trinitrophenol,briefly explaining your rationale.

Question 76

Draw the structure of the final product obtained when 4-cyclopentylphenol is subjected to the following reaction sequence:
i)NaOH;ii)CH3I;iii)NBS;iv)CH3ONa/CH3OH,heat

Question 77

Arrange the following in increasing order of acidity.

Question 78

Suggest a reasonable synthetic strategy for the synthesis of 3-bromophenol from acetophenone

Question 79

Benzyne is a very unstable intermediate,because _____________.

Question 80

Outline the steps involved in the synthesis of p-methoxybenzoic acid from phenol.