Schaum's Outline of Organic Chemistry

George Hademenos, George Hademenos

Chapter 18 AMINES - all with Video Answers

Educators

Chapter Questions

01:07

Problem 1

Name and classify the following amines:

Ronald Prasad

Numerade Educator

02:30

A rearrangement of $\mathrm{R}$, from $\mathrm{C}$ to an electron-deficient $\mathrm{N}$, occurs in the following reactions. The substrates and conditions are given. Indicate how the intermediate is formed and give the structure of each product.

Alkendra Singh

Numerade Educator

01:05

Problem 2

Give names for
CAN'T COPY

Narayan Hari

Numerade Educator

07:31

Problem 3

Using $\mathrm{C}_6 \mathrm{H}_6, \mathrm{C}_6 \mathrm{H}_5 \mathrm{CH}_3$, via diazonium salts and other needed reagents, prepare $(a) o$-chlorotoluene, (b) $m$-chlorotoluene, $(c)$ 1,3,5-tribromobenzene, $(d) m$-bromochlorobenzene, $(e) p$-iodotoluene, $(f) p$-dinitrobenzene and $(g) p$-cyanobenzoic acid. Do not repeat the synthesis of intermediate products.

Lottie Adams

Numerade Educator

02:49

Problem 3

Predict the orders of $(a)$ boiling points, and $(b)$ solubilities in water, for $1^{\circ}, 2^{\circ}$, and $3^{\circ}$ amines of identical molecular weights.

Rabia Shuaib

Numerade Educator

02:26

Problem 4

Does $n$-propylamine or 1-propanol have the higher boiling point?

Dr. Satish Ingale

Numerade Educator

03:05

Problem 5

Draw a flow sheet to show the separation and recovery in almost quantitative yield of a mixture of the water-insoluble compounds benzaldehyde (A), $N, N$-dimethylaniline (B), chlorobenzene (C), $p$-cresol (D), benzoic acid (E).

Adriano Chikande

Numerade Educator

01:12

Problem 5

(a) What complication arises in the synthesis of a $1^{\circ}$ amine from the reaction of $\mathrm{RX}_{\text {and }} \mathrm{NH}_3$ ? (b) How is this complication avoided? (c) Which halides cannot be used in this synthesis?

Narayan Hari

Numerade Educator

02:20

Problem 6

Describe an efficient industrial preparation of allylamine, $\mathrm{H}_2 \mathrm{C}=\mathrm{CHCH}_2 \mathrm{NH}_2$, from propene, chlorine, and ammonia.

Matthew Lueckheide

Numerade Educator

01:01

Problem 7

Synthesize 2-phenylethanamine, $\mathrm{PhCH}_2 \mathrm{CH}_2 \mathrm{NH}_2$, from styrene, $\mathrm{PhCH}=\mathrm{CH}_2$, by the azide reduction method.

Narayan Hari

Numerade Educator

01:41

Problem 8

Prepare ethylamine by (a) Gabriel synthesis, (b) alkyl halide amination, (c) nitrile reduction, (d) reductive amination, $(e)$ Hofmann degradation.

Lottie Adams

Numerade Educator

01:45

Problem 9

Prepare $p$-toluidine from toluene.

Grigoriy Sereda

Numerade Educator

03:47

Problem 10

Synthesize the following compounds from $n-\mathrm{C}_{12} \mathrm{H}_{25} \mathrm{COOH}$ and inorganic reagents:
(a) $\mathrm{C}_{14} \mathrm{H}_{29} \mathrm{NH}_2$
(b) $\mathrm{C}_{13} \mathrm{H}_{27} \mathrm{NH}_2$
(c) $\mathrm{C}_{12} \mathrm{H}_{25} \mathrm{NH}_2$
$(d)$
(e) $\mathrm{C}_{12} \mathrm{H}_{25} \mathrm{NHC}_{13} \mathrm{H}_{27}$
(f) $\left(\mathrm{C}_{13} \mathrm{H}_{27}\right)_2 \mathrm{NH}$

Do not repeat preparation of any needed compound.
First, note the change, if any, in carbon content.

Ian Kaigh

Numerade Educator

09:24

Problem 11

There is no change in the configuration of the chiral $\mathrm{C}$ in sec-butylamine formed from the Hofmann degradation of $(S)$-2-methylbutanamide. Explain.

Anupa Sharad Medhekar

Numerade Educator

01:20

Problem 13

Which of the following compounds are (i) chiral, (ii) resolvable? Give reasons in each case.

Dr. Satish Ingale

Numerade Educator

03:34

Problem 14

Explain why 1,2,2-trimethylaziridine has isolable enantiomers.

Dr. Satish Ingale

Numerade Educator

01:26

Problem 15

(a) Why does aqueous $\mathrm{CH}_3 \mathrm{NH}_2$ turn litmus blue? (b) Why does $\mathrm{C}_6 \mathrm{H}_5 \mathrm{NH}_2$ dissolve in aqueous $\mathrm{HCl}$ ?

Narayan Hari

Numerade Educator

08:29

Problem 16

Account for the following observations. $(a)$ In the gas phase the order of increasing basicity is $\mathrm{NH}_3<\mathrm{CH}_3 \mathrm{NH}_2<\left(\mathrm{CH}_3\right)_2 \mathrm{NH}<\left(\mathrm{CH}_3\right)_3 \mathrm{~N}$. (b) In water the order is $\mathrm{NH}_3<\mathrm{CH}_3 \mathrm{NH}_2 \approx\left(\mathrm{CH}_3\right)_3 \mathrm{~N}<\left(\mathrm{CH}_3\right)_2 \mathrm{NH}$.

Tom Rutherford

Numerade Educator

01:06

Problem 17

(a) Assign numbers from 1 for LEAST to 4 for MOST to indicate relative base strengths of (i) $\mathrm{C}_6 \mathrm{H}_5 \mathrm{NH}_2$ (ii) $\left(\mathrm{C}_6 \mathrm{H}_5\right)_2 \mathrm{NH}$, (iii) $\left(\mathrm{C}_6 \mathrm{H}_5\right)_3 \mathrm{~N}$, (iv) $\mathrm{NH}_3$. (b) Explain.

Ayushi Sambyal

Numerade Educator

01:08

Problem 18

Assign numbers from 1 for LEAST to 4 for MOST to indicate relative base strengths of the following:
(b) $\mathrm{C}_6 \mathrm{H}_5 \mathrm{NH}_2 \quad p-\mathrm{NO}_2 \mathrm{C}_6 \mathrm{H}_4 \mathrm{NH}_2 \quad m-\mathrm{NO}_2 \mathrm{C}_6 \mathrm{H}_4 \mathrm{NH}_2 \quad p-\mathrm{H}_3 \mathrm{COC}_6 \mathrm{H}_4 \mathrm{NH}_2$

Sima Sarker

Numerade Educator

01:15

Problem 19

Account for the following order of decreasing basicity:
$$
\mathrm{RNH}_2>\mathrm{R} \ddot{N}=\mathrm{CHR}^{\prime}>\mathrm{RC}=\mathrm{N}:
$$

Narayan Hari

Numerade Educator

04:40

Problem 20

(a) Outline the steps in the formation of a diazonium cation from nitrous acid and a $1^{\circ}$ amine.
(b) Why are diazonium ions of aromatic amines more stable than those of aliphatic amines?
(a) Initially a nitrosonium cation is formed from $\mathrm{HNO}_2$ in acid solution.

Zubair Abdulla

Numerade Educator

01:40

Problem 21

$$
\text { Prepare } p \cdot \mathrm{H}_2 \mathrm{NC}_6 \mathrm{H}_4 \mathrm{~N}\left(\mathrm{CH}_3\right)_2 \text { from } \mathrm{C}_6 \mathrm{H}_5 \mathrm{~N}\left(\mathrm{CH}_3\right)_2 \text {. }
$$

Rashmi Gondi

Numerade Educator

01:41

Problem 22

$$
\text { How can the Hinsberg test be used to distinguish among liquid } \mathrm{RNH}_2, \mathrm{R}_2 \mathrm{NH} \text {, and } \mathrm{R}_3 \mathrm{~N} \text { ? }
$$

Adriano Chikande

Numerade Educator

01:35

Problem 23

Outline two laboratory preparations of sym-diphenylurea.

Adriano Chikande

Numerade Educator

01:38

Problem 24

Condensation of $\mathrm{C}_6 \mathrm{H}_5 \mathrm{NH}_2$ with $\mathrm{C}_6 \mathrm{H}_5 \mathrm{CH}=\mathrm{O}$ yields compound (A), which is hydrogenated to compound (B). What are compounds (A) and (B)?

Farhana Sharmin

Numerade Educator

05:05

Problem 25

Compare and account for the products obtained from thermal decomposition of $(a)$ $\left[\left(\mathrm{CH}_3\right)_3 \mathrm{~N}^{+}\left(\mathrm{C}_2 \mathrm{H}_5\right)\right] \mathrm{OH}^{-},\left(\right.$b) $\left(\mathrm{CH}_3\right)_4 \mathrm{~N}^{+} \mathrm{OH}^{-}$.

Zubair Abdulla

Numerade Educator

02:46

Problem 26

Deduce the structures of the following amines from the products obtained from exhaustive methylation and Hofmann elimination. $(a) \mathrm{C}_5 \mathrm{H}_{13} \mathrm{~N}(\mathrm{~A})$ reacts with 1 mol of $\mathrm{CH}_3 \mathrm{I}$ and eventually yields propene. (b) $\mathrm{C}_5 \mathrm{H}_{13} \mathrm{~N}$ (B) reacts with $2 \mathrm{~mol}$ of $\mathrm{CH}_3 \mathrm{I}$ and give ethene and a $3^{\circ}$ amine. The latter reacts with $1 \mathrm{~mol}$ of $\mathrm{CH}_3 \mathrm{I}$ and eventually gives propene.

Ramesh Singh

Numerade Educator

04:12

Problem 27

Outline the reactions and reagents used to establish the structure of 4-methylpyridine by exhaustive methylation and Hofmann elimination.

Colton K

Numerade Educator

02:23

Problem 28

How does the dipolar ion structure of sulfanilic acid account for its $(a)$ high melting point, (b) insolubility in $\mathrm{H}_2 \mathrm{O}$ and organic solvents, (c) solubility in aqueous $\mathrm{NaOH},($ d $)$ insolubility in aqueous $\mathrm{HCl}$ ?

Adriano Chikande

Numerade Educator

01:44

Problem 29

$$
\mathrm{H}_3 \stackrel{+}{\mathrm{NCH}_2 \mathrm{COO}^{-}} \text {exists as a dipolar ion whereas } p-\mathrm{H}_2 \mathrm{NC}_6 \mathrm{H}_4 \mathrm{COOH} \text { does not. Explain. }
$$

Ahmed Ali

Numerade Educator

01:24

Problem 30

$$
\text { Distinguish among } 1^{\circ}, 2^{\circ} \text {, and } 3^{\circ} \text { amines by ir spectroscopy. }
$$

Lottie Adams

Numerade Educator

05:03

Problem 32

Explain the following conditions used in coupling reactions: (a) excess of mineral acid during diazotization of arylamines, (b) weakly acidic medium for coupling with $\mathrm{ArNH}_2,(c)$ weakly basic solution for coupling with ArOH.

Grigoriy Sereda

Numerade Educator

04:44

Problem 33

Deduce the structures of the azo compounds that yield the indicated aromatic amines on reduction with $\mathrm{SnCl}_2 ;(a) p$-toluidine and $p-\mathrm{NH}_2-N, N$-diMeaniline, (b) $1 \mathrm{~mol}$ of $4,4^{\prime}$-diaminobiphenyl and $2 \mathrm{~mol}$ of 2-hydroxy-5 aminobenzoic acid.

Shahina -

Numerade Educator

01:52

Problem 34

Write a structural formula for (a) $N, N^{\prime}$-di-p-tolylthiourea, (b) 2,4-xylidine, (c) $N$-methyl-pnitrosoaniline, $(d)$ 4-ethyl-3'-methylazobenzene.

Ronald Prasad

Numerade Educator

02:30

Problem 35

Name: (a) $\mathrm{C}_6 \mathrm{H}_5 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{NH}_2$, (b) $\mathrm{CH}_3 \mathrm{NHCH}_2 \mathrm{CH}_3$, (c) $\mathrm{NH}_2 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CH}\left(\mathrm{NH}_2\right) \mathrm{CH}_3$, (d) $\mathrm{NH}_2 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{OH},(e)\left(\mathrm{CH}_3\right)_3 \mathrm{CNHC}\left(\mathrm{CH}_3\right)_3,(f) \mathrm{NH}_2 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{NH}_2,(g) p-\mathrm{C}_6 \mathrm{H}_4\left(\mathrm{NH}_2\right)_2$

Sima Sarker

Numerade Educator

04:42

Problem 36

Give the structure of (a) 3-( $N$-methylamino)-1-propanol, (b) ethyl 3-( $N$-methylamino)-2-butenoate, (c) 2-N,N-dimethylaminobutane, (d) allylamine.

Grigoriy Sereda

Numerade Educator

01:22

Problem 37

Give the structures and names of 5 aromatic amines with the molecular formula $\mathrm{C}_7 \mathrm{H}_9 \mathrm{~N}$.

Chloe Schroeder

Numerade Educator

01:20

Problem 38

A compound $\mathrm{C}_3 \mathrm{H}_9 \mathrm{~N}$ is a $2^{\circ}$ amine. Deduce its structure.

Narayan Hari

Numerade Educator

04:32

Problem 39

Give the product of reaction in each case:

Keenan Mintz

University of Miami

04:58

Problem 40

What is the organic product when $n$-propylamine is treated with $(a) \mathrm{PhSO}_2 \mathrm{Cl}$ ? (b) excess $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{Cl}$ ? (c) chlorobenzene? (d) excess $\mathrm{CH}_3 \mathrm{I}$, then $\mathrm{Ag}_2 \mathrm{O}$ and heat?

Anand Kumar

Numerade Educator

03:00

Problem 41

What is the product of catalytic hydrogenation of $(a)$ acetone oxime, (b) propane-1,3-dinitrile, $(c)$ propanal and methylamine?

Niamat Khuda

Numerade Educator

07:30

Problem 42

Show the steps in the following syntheses:
(a) Ethylamine $\longrightarrow$ Methylethylamine
(b) Ethylamine $\longrightarrow$ Dimethylethylamine
(c) n-Propyl chloride $\longrightarrow$ Isopropylamine
(d) Aniline $\longrightarrow p$-Aminobenzenesulfonamide (sulfanilamide)

Anupa Sharad Medhekar

Numerade Educator

02:50

Problem 43

Outline the steps in the syntheses of the following compounds from $\mathrm{C}_6 \mathrm{H}_6, \mathrm{C}_6 \mathrm{H}_5 \mathrm{CH}_3$ and any readily available aliphatic compound: (a) $p$-aminobenzoic acid, (b) $m$-nitroacetanilide, (c) 1-amino-1-phenylpropane, (d) 4-amino-2-chlorotoluene.

Lottie Adams

Numerade Educator

View

Problem 44

Use the benzidine rearrangement to synthesize $2,2^{\prime}$-dichlorobiphenyl from benzene and inorganic reagents.

Kaden Bunch

Numerade Educator

06:58

Problem 45

Use $o$ - or $p$-nitroethylbenzene and any inorganic reagents to synthesize the six isomeric dichloroethylbenzenes. Do not repeat preparations of intermediate products.

Ian Kaigh

Numerade Educator

00:44

Problem 46

Deduce a possible structure for each of the following. (a) Compound (A), $\mathrm{C}_6 \mathrm{H}_4 \mathrm{~N}_2 \mathrm{O}_4$, is insoluble in both dilute acid and base and its dipole moment is zero. (b) Compound ( $B$ ), $\mathrm{C}_8 \mathrm{H}_9 \mathrm{NO}$, is insoluble in dilute acid and base. (B) is transformed by $\mathrm{KMnO}_4$ in $\mathrm{H}_2 \mathrm{SO}_4$ to compound (C), which is free of $\mathrm{N}$, soluble in aqueous $\mathrm{NaHCO}_3$ and gives only one mononitro substitution product. (c) Compound (D), $\mathrm{C}_7 \mathrm{H}_7 \mathrm{NO}_2$, undergoes vigorous oxidation to form compound $(\mathrm{E}), \mathrm{C}_7 \mathrm{H}_5 \mathrm{NO}_4$, which is soluble in dilute aqueous $\mathrm{NaHCO}_3$ and forms two isomeric monochloro substitution products.

Aadit Sharma

Numerade Educator

13:08

Problem 47

Using any aliphatic and inorganic reagents, outline the syntheses of $(a) m-\mathrm{HOC}_6 \mathrm{H}_4 \mathrm{CH}_3$ from toluene, (b) 4-bromo-4'-aminoazobenzene from aniline.

Shalini Tyagi

Numerade Educator

02:25

Problem 48

Synthesize novocaine, $p-\mathrm{H}_2 \mathrm{NC}_6 \mathrm{H}_4 \mathrm{COOCH}_2 \mathrm{CH}_2 \mathrm{NEt}_2$, from toluene and any aliphatic compound of four or fewer C's.

Raghvendra Singh

Numerade Educator

04:12

Problem 49

An optically active amine is subjected to exhaustive methylation and Hofmann elimination. The alkene obtained is ozonized and hydrolyzed to give an equimolar mixture of formaldehyde and butanal. What is the amine?

Colton K

Numerade Educator

01:52

Problem 51

Synthesize the following compounds from alcohols of four or fewer C's, cyclohexanol and any needed solvents and inorganic reagents. ( $a$ ) $n$-hexylamine, (b) triethylamine $\mathrm{N}$-oxide, (c) 4 -(N-methylamino)heptane, (d) cyclohexyldimethylamine, $(e)$ cyclopentylamine, $(f)$ 6-aminohexanoic acid.

Alexander Cheng

Numerade Educator

08:53

Problem 52

Use simple, rapid, test-tube reactions to distinguish between (a) $\mathrm{CH}_3 \mathrm{CONHC}_6 \mathrm{H}_5$ and $\mathrm{C}_6 \mathrm{H}_5 \mathrm{CONH}_2$, (b) $\mathrm{C}_6 \mathrm{H}_5 \mathrm{NH}_3^{+} \mathrm{Cl}^{-}$and $p-\mathrm{ClC}_6 \mathrm{H}_4 \mathrm{NH}_2, \quad(c) \quad\left(\mathrm{CH}_3\right)_4 \mathrm{~N}^{+} \mathrm{OH}^{-}$and $\left(\mathrm{CH}_3\right)_2 \mathrm{NCH}_2 \mathrm{OH}$, (d) $p-\mathrm{CH}_3 \mathrm{COC}_6 \mathrm{H}_4 \mathrm{NH}_2$ and $\mathrm{CH}_3 \mathrm{CONHC}_6 \mathrm{H}_5$.

Pronoy Sinha

Numerade Educator

06:30

Problem 53

Synthesize from benzene, toluene, naphthalene $(\mathrm{NpH})$, and any aliphatic or inorganic compounds (a) $\alpha$-(p-nitrophenyl)ethylamine, (b) $\beta$-(p-bromophenyl)ethylamine, $(c) 1-(\alpha$-aminomethyl)naphthalene, $(d) 2$-naphthylamine, (e) $\beta-\mathrm{NpCH}_2 \mathrm{NH}_2$.

Matthew Lueckheide

Numerade Educator

02:23

Problem 54

Synthesize from naphthalene and any other reagents: $(a)$ naphthionic acid (4-amino-1-naphthalenesulfonic acid), (b) 4-amino-1-naphthol, (c) 1,3-dinitrionaphthalene, $(d)$ 1,4-diaminonaphthalene, $(e)$ 1,2-dinitronaphthalene. Do not repeat the synthesis of any compound.

Susan Hallstrom

Numerade Educator

04:36

Problem 55

In the presence of $\mathrm{C}_6 \mathrm{H}_5 \mathrm{NO}_2, 2 \mathrm{~mol}$ of $\mathrm{C}_6 \mathrm{H}_5 \mathrm{NH}_2$ reacts with $1 \mathrm{~mol}$ of $p$-toluidine to give a triarylmethane that is converted to the dye pararosaniline (Basic Red 9) by reaction with $\mathrm{PbO}_2$ followed by acid. Show the steps, indicating the function of $(a)$ nitrobenzene, $(b) \mathrm{PbO}_2,(c) \mathrm{HCl}$.

Grigoriy Sereda

Numerade Educator

05:09

Problem 56

How can $N$-methylaniline and $o$-toluidine be distinguished by ir spectroscopy?

Tianyu Li

Numerade Educator

02:00

Problem 57

Amines A, B, D, and E each have their parent-ion peaks at $m / e=59$. The most prominent peaks for each are at $m / e$ values of 44 for $\mathrm{A}$ and $\mathrm{B}, 30$ for $\mathrm{D}$, and 58 for $\mathrm{E}$. Give the structure for each amine and for the ion giving rise to the most prominent peak for each.

Zubair Abdulla

Numerade Educator

06:00

Problem 58

What compound, $\mathrm{C}_3 \mathrm{H}_7 \mathrm{NO}$, has the following nmr spectrum: $\delta=6.5$, broad singlet (two H's); $\delta=2.2$, quartet (two H's): and $\delta=1.2$, triplet (three H's)?

Sharfa Farzandh

Numerade Educator

06:39

Problem 59

Determine the structure of a compound $\left(\mathrm{C}_9 \mathrm{H}_{11} \mathrm{NO}\right)$ which is soluble in dilute $\mathrm{HCl}$ and gives a positive Tollens' test. Its ir spectrum shows a strong band at $1695 \mathrm{~cm}^{-1}$ but no bands in the $3300-3500 \mathrm{~cm}^{-1}$ region. The proton-decoupled ${ }^{13} \mathrm{C}$ spectrum shows six signals which would display the following splitting pattern in the coupled ${ }^{13} \mathrm{C}$ spectrum: one quartet, two singlets, and three doublets, one doublet being very downfield.

Zubair Abdulla

Numerade Educator

01:01

Problem 60

What compound results from treating the diazonium salt of $p$-toluidine with copper bronze powder?

Narayan Hari

Numerade Educator