# 24.E: Amines and Heterocycles (Exercises)

- Page ID
- 61707

These are the homework exercises to accompany the Textmap for McMurry's Organic Chemistry textbook.

## 24.3 Basicity of Amines

### 24.3 Exercises

#### Questions

**Q24.3.1**

Select the more basic amine from each of the following pairs of compounds.

(a)

(b)

(c)

**Q24.3.2**

The 4-methylbenzylammonium ion has a pKa of 9.51, and the butylammonium ion has a pKa of 10.59. Which is more basic? What's the pKb for each compound?

#### Solutions

**S24.3.1**

(a)

(b)

(c)

**S24.3.2**

The butylammonium is more basic. The pKb for butylammonium is 3.41, the pKb for 4-methylbenzylammonium is 4.49.

## 24.7 Reactions of Amines

### 24.7 Exercises

#### Questions

**Q24.7.1**

Draw the product for a Hoffman elimination for each of the following molecules.

(a)

(b)

(c)

(d)

**Q24.7.2**

Draw the product of a Hoffman elimination for the following molecule.

#### Solutions

**S24.7.1**

(a)

(b)

(c)

(d)

**S24.7.2**

## 24.8 Reactions of Arylamines

### 24.8 Exercises

#### Questions

**Q24.8.1**

Propose a synthesis for the following compound via benzene and any amine you may require.

**Q24.8.2**

Proposes synthesis for each of the following compounds via benzene.

(a) *N,**N*-Diethylaniline

(b) *p*-Bromoaniline

(c) *m*-Bromoaniline

(d) 2,4-Diethylaniline

**Q24.8.3**

Propose a synthesis for each of the following molecules from benzene via the diazonium ion.

(a) *p*-Chlorobenzoic acid

(b) *m*-Chlorobenzoic acid

(c) *m*-Dichlorobenzene

(d) *p*-Ethylbenzoic acid

(e) 1,2,4-Trichlorobenzene

#### Solutions

**S24.8.1**

**S24.8.2**

(a) 1. HNO_{3}, H_{2}SO_{4}; 2. Zn(Hg), HCl; 3. EtBr

(b) 1. HNO_{3}, H_{2}SO_{4}; 2. Zn(Hg), HCl; 3. (CH_{3}CO)O_{2}; 4. Br_{2}, FeBr_{3}; 5. H_{2}O, NaOH

(c) 1. HNO_{3}, H_{2}SO_{4}; 2. Br_{2}, FeBr_{3}; 3. Zn(Hg), HCl

(d) 1. HNO_{3}, H_{2}SO_{4}; 2. Zn(Hg), HCl; 3. (CH_{3}CO)O_{2}; 4. EtCl, AlCl_{3}; 5. H_{2}O, NaOH

**S24.8.3**

(a) 1. CH_{3}CH_{2}Cl, AlCl_{3}; 2. HNO_{3}, H_{2}SO_{4}; 3. SnCl_{2}; 4. NaNO_{2}, H_{2}SO_{4}; 5. CuBr; 6. KMnO_{4}, H_{2}O

(b) 1. HNO_{3}, H_{2}SO_{4}; 2. Cl_{2}, FeCl_{3}; 3. SnCl_{2}, H_{3}O^{+}; 4. NaNO_{2}, H_{2}SO_{4}; 5. CuCN; 6. H_{3}O^{+}

(c) 1. HNO_{3}, H_{2}SO_{4}; 2. Cl_{2}, FeCl_{3}; 3. SnCl_{2}; 4. NaNO_{2}, H_{2}SO_{4}; 5. CuCl

(d) 1. CH_{3}CH_{2}Cl, AlCl_{3:} 2. HNO_{3}, H_{2}SO_{4}; 3. SnCl_{2}; 4. NaNO_{2}, H_{2}SO_{4}; 5. CuCN; 6. H_{3}O^{+}

(e) 1. HNO_{3}, H_{2}SO_{4}; 2. H_{2}/PtO_{2}; 3. (CH_{3}CO)_{2}O; 4. 2 Cl_{2}; 5. H_{2}O, NaOH; 6. NaNO_{2}, H_{2}SO_{4}; 7. CuCl