Chapter 23 Flashcards
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
alcohols
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 ..
N-substituted; larger; smaller; N
common names for amines are derived by listing the … bonded to the nitrogen in … order followed by the suffix amine
alkyl groups; alphabetical
quarternary ammonium ions are named by replacing the amine suffix with … and the name of the …
ammonium; anion
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
pyramidal inversion; quarternary ammonium salts
the pka values of conjugate acids of aliphatic amines are in the … to … range
10; 11
alkyl grouops make amines slightly more basic because … alkyl groups stabilize the alkylammonium ion
electron-releasing
aromatic amines are less basic because the nitrogen lone pair takes part in … with the aromatic pi system, a stabilizing interaction that is …
resonance; lost upon protonation
the basicity of N atoms within heterocyclic aromatic amines depends on whether the N lone pair is part of the
aromatic pi system
amines react with strong acids to give …, allowing the separation of amines from water-insoluble molecules
water-soluble salts
amines can be prepared using reactions including …, addition of nitrogen nucleophiles to … followed by …, … of amides, …. of nitriles, and … of arenes followed by reduction
epoxide ring opening; carbonyls; reduction; reduction; reduction; nitration
aklylation of amines generally results in
overalkylation
primary amines can be prepared in high yield by reacting a haloalkane with the strong nucleophile … or … followed by reduction with …
sodium; potassium azide (NaN3/ KN3); LiAlH4
tertiary aromatic amines can undergo … with nitrous acid, not a useful rxn
electrophilic aromatic substitution
secondary amines react with nitrous acid to give
N-nitrosamines
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.
diazonium ion; N2; substiution; elimination
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 …
Tiffeneau-Demjanov; one carbon ring expansion; cyclic ketone
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
aryl diazonium ions
reaction of aryl diazonium ions with water gives
phenols
reaction of aryl diazonium ions with HBF4 gives … in a reaction known as the … reaction
aryl fluorides; Schiemann
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
Cl; Br; CN; Sandmeyer
reaction of aryl diazonium ions with KI gives
aryl iodides
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
H
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 …
alkene; hofmann elimination
hofmann elimination rxns are stereoselective for .. eliminations and give predominantly the … alkene, counter to Zaitsev’s rule
anti; least substituted
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
steric bulk
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 …
amine oxide; alkene; Cope elimination
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
syn
