Chapter 23

Question 1

in iupac names, aliphatic amines are named like …, except the suffix amine is used and a number is used to locate the position of the amine group

Answer 1

alcohols

Question 2

Secondary and tertiary amines are named as … primary amines and the … group is taken as the parent amine; then the … groups are named, given the prefix ..

Answer 2

N-substituted; larger; smaller; N

Question 3

common names for amines are derived by listing the … bonded to the nitrogen in … order followed by the suffix amine

Answer 3

alkyl groups; alphabetical

Question 4

quarternary ammonium ions are named by replacing the amine suffix with … and the name of the …

Answer 4

ammonium; anion

Question 5

secondary or tertiary amines with three different groups bonded to nitrogen are chiral, but they cannot usually be resolved because, at room temp, the undergo a process called … that rapidly interconverts the two enantiomers. … cannot undergo pyramidal inversion, so they can be resolved

Answer 5

pyramidal inversion; quarternary ammonium salts

Question 6

the pka values of conjugate acids of aliphatic amines are in the … to … range

Answer 6

10; 11

Question 7

alkyl grouops make amines slightly more basic because … alkyl groups stabilize the alkylammonium ion

Answer 7

electron-releasing

Question 8

aromatic amines are less basic because the nitrogen lone pair takes part in … with the aromatic pi system, a stabilizing interaction that is …

Answer 8

resonance; lost upon protonation

Question 9

the basicity of N atoms within heterocyclic aromatic amines depends on whether the N lone pair is part of the

Answer 9

aromatic pi system

Question 10

amines react with strong acids to give …, allowing the separation of amines from water-insoluble molecules

Answer 10

water-soluble salts

Question 11

amines can be prepared using reactions including …, addition of nitrogen nucleophiles to … followed by …, … of amides, …. of nitriles, and … of arenes followed by reduction

Answer 11

epoxide ring opening; carbonyls; reduction; reduction; reduction; nitration

Question 12

aklylation of amines generally results in

Answer 12

overalkylation

Question 13

primary amines can be prepared in high yield by reacting a haloalkane with the strong nucleophile … or … followed by reduction with …

Answer 13

sodium; potassium azide (NaN3/ KN3); LiAlH4

Question 14

tertiary aromatic amines can undergo … with nitrous acid, not a useful rxn

Answer 14

electrophilic aromatic substitution

Question 15

secondary amines react with nitrous acid to give

Answer 15

N-nitrosamines

Question 16

primary amines react with nitrous acid to give … intermediates that … and give a variety of … and … products, so the reaction is not generally synthetically useful.

Answer 16

diazonium ion; N2; substiution; elimination

Question 17

a synthetically useful version of primary amines with nitrous acid is the … reaction, which gives a … of a cyclic beta-amino alcohol and produces a …

Answer 17

Tiffeneau-Demjanov; one carbon ring expansion; cyclic ketone

Question 18

primary aromatic amines react with nitrous acid to give … which are very versatile and useful synthetic intermediates in the synthesis of a variety of substituted aromatic rings

Answer 18

aryl diazonium ions

Question 19

reaction of aryl diazonium ions with water gives

Answer 19

phenols

Question 20

reaction of aryl diazonium ions with HBF4 gives … in a reaction known as the … reaction

Answer 20

aryl fluorides; Schiemann

Question 21

reaction of aryl diazonium ions with HCl/CuCl, HBr/CuBr, or KCN/CuCN replaces the diazonium group with a …, …, or … group, respectively, in a reaction known as the … reaction

Answer 21

Cl; Br; CN; Sandmeyer

Question 22

reaction of aryl diazonium ions with KI gives

Answer 22

aryl iodides

Question 23

raction of aryl diazonium ions with hypophosphorous acid (H3PO2) replaces the diazonium group with an …. atom so that the reaction sequence of reacting an aniline with nitrous acid followed by hypophosphorous acid will remove the aryl NH2 group

Answer 23

H

Question 24

reaction of a quarternary ammonium halide with moist silver oxide to produce a quarternary ammonium hydroxide followed by heating to give an …. is a reaction known as the …

Answer 24

alkene; hofmann elimination

Question 25

hofmann elimination rxns are stereoselective for .. eliminations and give predominantly the … alkene, counter to Zaitsev’s rule

Answer 25

anti; least substituted

Question 26

hofmann elimination regiochem is thought to derive from the … of the ammonium group that directs deprotonation by base to the least hindered site leading to formation of the less substituted alkene

Answer 26

steric bulk

Question 27

treatment of a tertiary amine with hydrogen peroxide gives an …, which when heated gives an … and an N,N-dialkylhydroxyamine in a reaction known as a …

Answer 27

amine oxide; alkene; Cope elimination

Question 28

the cope elimination is … stereoselective and gives little preference for regiochemistry unless a conjugated double bond can be created, in which case the conjugated product predominates

Answer 28

syn