Carbonyls and Amines

Question 1

carbonyl

Answer 1

carbon double bonded to an oxygen

Question 2

functional groups that contain carbonyls

Answer 2

aldehydes, ketones, carboxylic acids, amides, esters

Question 3

2 things to think when see carbonyl….

Answer 3

planar stereochemistry, partial + charge on C/partial - charge on O

Question 4

aldehydes and ketones are more ___ and have higher _____ than alkanes and alkenes of similar weight

Answer 4

more polar, higher boiling points (lower boiling points than corresponding alcohols - cant H bond with each other)

Question 5

a carbon that is attached to a carbonyl carbon is in the ____ ____ and is called an ____ ____

Answer 5

alpha position, alpha carbon

Question 6

aldehyde and ketone commonly donate one of their….

Answer 6

alpha hydrogens

Question 7

enolate ion

Answer 7

alpha carbon anions, stabilized by resonance

Question 8

dicarbonyl

Answer 8

when beta carbon is also carbonyl, increases acidity of alpha hydrogen between carbonyl, making it more acidic than water or alcochol
enol from becomes more stable due to internal hydrogen bonding and resonance

Question 9

aldehydes are slightly more ____ than ketones

Answer 9

acidic and reactive

Question 10

keto-enol tautomerization

Answer 10

ketones and aldehydes exist at room temp as enol tautomers

proton shift, reaction at equilibrium not a resonance

Question 11

aldehydes and ketones react with alcohols to form…

Answer 11

hemiacetals and hemiketals

hemiacetal –> acetal and hemiketal –> ketal if second molar eqiv. of alcohol added

Question 12

because acetals and ketals are unreactive toward ____, they are often used as blocking groups

Answer 12

bases

Question 13

when aldehydes and ketones are dissolved in aq. solution they establish an equilibrium with their _____

Answer 13

hydrate, a geminal diol

Question 14

Aldol condensation

Answer 14

when one aldehyde reacts with another, when one ketone reacts with another, or when an aldehyde reacts with a ketone
catalyzed by acid or base
1. base takes alpha H leaving enolate ion
2. enoalte ion acts as nucleophile, attacks carbonyl C to from aloxide ion
3. removes proton from water to aldol
4. aldol is unstable, dehydrated by heat/base to become an enal

Question 15

halogenation of a ketone

Answer 15

halogens add to ketones at the alpha carbon in the presence of a base or an acid

Question 16

haloform reaction

Answer 16

when base used with methyl ketone in halogenation of ketone reaction, alpha carbon becomes completely halogenated
trihalo product reacts further with the base —> carobxylic acid and a halofrom (HCX3)

Question 17

Wittig reaction

Answer 17

converts a ketone to an alkene

phosphorus ylid is used

Question 18

ylid

Answer 18

neutral molecule with a negatively charged carbanion

Question 19

alpha-beta unsaturated carbonyl

Answer 19

carbocation at carbonyl carbon is stabilized by resonance

enol-keto tautomers

Question 20

formic acid/methanoic acid

Answer 20

H-C=O(-OH)

Question 21

acetic acid/ethanoic acid

Answer 21

H3C-C=O(-OH)

Question 22

benzoic acid

Answer 22

benzene-C=O(-OH)

Question 23

carboxylic acids are able to make strong double ____ to form a dimer

Answer 23

hydrogen bonds

Question 24

decarboxylation

Answer 24

when a carboxylic acid loses CO2

activation energy high

Question 25

acyl group

Answer 25

R-C=O

Question 26

____ ____ are the most reactive of the carboxylic acid derivatives because of the ____

Answer 26

acid chlorides [ R-C=O(-Cl) ] because of the stability of the Cl- leaving group acid chlorides love nucleophiles

Question 27

hydrolysis of carboxylic acid derivatives -->

Answer 27

carboxylic acid

Question 28

alcohols react with carboxylic acids through nucleophilic substitution to form ____

Answer 28

esters

Question 29

transesterification

Answer 29

trading alkoxy groups on an ester

Question 30

acetoacetic ester synthesis

Answer 30

production of a ketone from acetoacetic ester due to the strongly acidic properties of the alpha hydrogen

Question 31

amides are formed when an _____ acting as a nucleophile substitutes at the carbonyl of a carboxylic acid or one of its derivatives

Answer 31

amine

Question 32

in all of the reactions with carboxylic acid derivatives, the carbonyl carbon is acting as the ____ in _____ ____

Answer 32

acting as the substrate in acyl substitution

Question 33

carboxylic acids and their derivatives undergo ____ ____, while aldehydes and ketones prefer ____ ____

Answer 33

carboxylic acids: acyl substitution | aldehydes and ketones: nucleophilic addition

Question 34

amines

Answer 34

derivatives of ammonia

Question 35

ammonia

Answer 35

NH3

Question 36

primary amine

Answer 36

RNH2

Question 37

secondary amine

Answer 37

R2NH

Question 38

tertiary amine

Answer 38

R3N

Question 39

quaternay amine

Answer 39

R4N+

Question 40

nitrogen can take ____ bond

Answer 40

3 or 4

Question 41

3 considerations for nitrogen containing compounds

Answer 41

- may act as Lewis base donating their lone pair of e-'s - may act as nucleophile where the lone pair of e-s attacks a positive charge - nitrogen can take on a fourth bond becoming + charged

Question 42

ammonia and amines act as ___ bases by donating their lone pair of e-s

Answer 42

weak bases

Question 43

general trend of amine basicity from highest to lowest when the functional groups are e- donating

Answer 43

secondary, primary, ammonia, aromatic amines

Question 44

ammonia and amines ___ ___ which raises boiling point and increase solubility

Answer 44

hydrogen bond

Question 45

amines react with aldehydes and ketones losing water to produce ___ and ___

Answer 45

imines and enamines

Question 46

Wolff-Kishner Reduction

Answer 46

reduce a ketone or aldehyde by removing the oxygen and replacing it with two hydrogens (can do same by adding hot acid, but some cant survive it)

Question 47

amine alkylation

Answer 47

NH3 + RX --> RNH2 + HX | nucleophilic substitution, amine acting as nucleophile

Question 48

Hofmann elimination

Answer 48

heating the quarternary ammonium hydroxide, to form an alkene least stable alkene is major product

Question 49

primary amines react with nitrous acid to form____

Answer 49

diazonium salts, only aromatic amines work

Question 50

acetamide

Answer 50

H3C-C=O(-NH2)

Question 51

N-ethylacetamide

Answer 51

H3C-C=O(-NHC2H5)

Question 52

amides can behave as...

Answer 52

weak acids or weak bases

Question 53

amides are ____ than amine due to the e- withdrawing properties of the carbonyl

Answer 53

less basic than amines

Question 54

cyclic amides are called

Answer 54

lactams

Question 55

beta-lactams

Answer 55

4 membered rings, cyclic amides, highly reactive due to ring strain

Question 56

Hofmann degradation

Answer 56

primary amides react with strongly basic solutions of chlorine or bromine to form primary amines with carbon dioxide as byproduct -can produce amines with primary, secondary, or tertiary alkyl position (other methods rely on SN2 and prevent production of amines on tertiary carbons)

Question 57

phosphoric acid

Answer 57

P(OH)3=O

Question 58

when heated phosphoric acid forms_____

Answer 58

phosphoric anhydrides