Ch 23 Amines

Question 1

Amine classification (1,2,3)

Answer 1

based on how many substituents on the NITROGEN

Question 2

Amines (undergo inversion/cannot invert)

Answer 2

undergo inversion

Question 3

Amines (undergo inversion/cannot invert)

Answer 3

undergo inversion

Question 4

Rank salt–> tertiary amines in terms of pKa

Answer 4

salt

Question 5

pKa of amines determined by two effects

Answer 5

inductive effects (more substituents make the nitrogen less acidic, and solvent effects( hydrogen bonding more favorable for less substituted amines.

Question 6

pKa of amines determined by two effects

Answer 6

inductive effects (more substituents make the nitrogen less acidic, and solvent effects( hydrogen bonding more favorable for less substituted amines.

Question 7

Amines can easily (protonate/deprotonate) in acid conditions

Answer 7

protonate.

Question 8

The protonated version of an amine is called

Answer 8

the ammonium salt

Question 9

The protonated version of an amine is called

Answer 9

the ammonium salt

Question 10

Nitrile dipole

Answer 10

carbon is more positive than the nitrogen

Question 11

How do polar effects change basicity/acidity of amine compounds?

Answer 11

the closer the positive carbon (from nitrile) is to the amine, the more acidic the protons, because they do not want to be near a positive charge and want to deprotonate.

Question 12

How do polar effects change basicity/acidity of amine compounds?

Answer 12

the closer the positive carbon (from nitrile) is to the amine, the more acidic the protons, because they do not want to be near a positive charge and want to deprotonate.

Question 13

aromatic rings (in/de/crease ) basicity of amines

Answer 13

decreases basicity

Question 14

Cl groups (in/de/crease) basicity of amines

Answer 14

decrease basicity

Question 15

LAH (2 functions)

Answer 15

(LiAlH4) reduction that removes carbonyl, or reduces nitriles to amines

Question 16

LAH (2 functions)

Answer 16

(LiAlH4) reduction that removes carbonyl, or reduces nitriles to amines

Question 17

Quarternary Ammonium salts

Answer 17

All four hydrogens of NH4 are replaced with groups

Question 18

Alkylation (Normal) amine + ____ =____

Answer 18

amine + alkyl halide (MeBr) = quarternization (R-N-Me3)

Question 19

How can you avoid quarternization if you want a primary amine or secondary amine?

Answer 19

Gabriel synthesis

Question 20

How can you avoid quarternization if you want a primary amine or secondary amine?

Answer 20

Gabriel synthesis (protects the amine nitrogen)

Question 21

Gabriel Synthesis

Answer 21

Using phthalimide which has only one acidic hydrogen. By creating its conjugate base anion by KOH/EtOH, doing SN2 to gain the alkyl chain, then doing amide hydrolysis (H2O, HBr/HOAc) you can gain the primary amine

Question 22

Gabriel Synthesis

Answer 22

Using phthalimide which has only one acidic hydrogen. By creating its conjugate base anion by KOH/EtOH, doing SN2 to gain the alkyl chain, then doing amide hydrolysis (H2O, HBr/HOAc) you can gain the primary amine

Question 23

When primary and secondary amines react with aldehydes or ketones, they form:

Answer 23

imines and enamines (C=NH-R)

Question 24

What are two reagents for reductive amination?

Answer 24

Sodium triacetoxyborohydride (NaBH(OAc)3) and Sodium cyanoborohydride (NaBH3CN)

Question 25

Reductive Amination Step 1: When primary and secondary amines react with aldehydes or ketones, they form:

Answer 25

imines and enamines (C=NH-R)

Question 26

What are two reagents for reductive amination?

Answer 26

Sodium triacetoxyborohydride (NaBH(OAc)3) and Sodium cyanoborohydride (NaBH3CN)

Question 27

What is an imine?

Answer 27

C=N

Question 28

What is an enamine?

Answer 28

C=C-N

Question 29

Borch rxn

Answer 29

simply a reductive amination using NaBH3CN

Question 30

What other reagent must be a part of the Borch rxn?

Answer 30

HCl one equivalent

Question 31

What other reagent must be a part of the Borch rxn?

Answer 31

HCl one equivalent

Question 32

Amination Cyclization Rxn

Answer 32

When there are two carbonyls, you can aminate the first one, then the second to create a ring.

Question 33

Pd Catalyzed Amination consists of three steps

Answer 33

Ligand Substitution, Reductive Elimination, Oxidative Addition

Question 34

Pd Catalyzed Amination: What it can do

Answer 34

Adds an amine to an aryl halide

Question 35

Pd Catalyzed Amination: What it can do

Answer 35

Adds an amine to an aryl halide

Question 36

Acylation of Amines: Can use (3)

Answer 36

Acid chlorides, anhydrides, and esters

Question 37

Diazotization of Anilines _____ + ____ = ____

Answer 37

Ar-NH2 + --(NaNO2/HCl/H2O)--> Ar-NtripleN

Question 38

Sandmeyer Combo CuCl

Answer 38

Ar-Cl

Question 39

Sandmeyer Combo CuBr

Answer 39

Ar-Br

Question 40

Sandmeyer Combo CuBr

Answer 40

Ar-Br

Question 41

Sandmeyer Combo CuCN

Answer 41

Ar-CN

Question 42

Sandmeyer Combo Cu2O

Answer 42

Ar-OH

Question 43

Sandmeyer ComboH3PO2

Answer 43

Ar-H

Question 44

Hofmann Rearrangements

Answer 44

Takes Amide--> R-NH2

Question 45

Hofmann Rearrangements

Answer 45

Takes Amide--> R-NH2

Question 46

Curtius Rearrangements

Answer 46

Takes Acid chloride--> R-NH2

Question 47

Curtius Rearrangements

Answer 47

Takes Acid chloride--> R-NH2

Question 48

Curtius Rearrangements: Extension + R'MgBr

Answer 48

R-N=C=O --(R'MgBr)--> amide with R' group on other end

Question 49

Curtius Rearrangements: Extension + R'NH2

Answer 49

R-N=C=O --(R'NH2)--> urea (double amide)

Question 50

Curtius Rearrangements: Extension +MeOH

Answer 50

r-N=C=O --(MeOH)--> ester with Me group