Mcat Aldehydes And Ketones

Front 1

Aldehydes are named with suffix ___

Back 1

-al

Front 2

Aldehydes occupy what position?

Back 2

the terminal position

Front 3

Common names for the first five aldehydes are:

Back 3

*formaldehyde
*acetaldehyde
propionaldehyde
butyraldehyde
valeraldehyde

Front 4

t or f
A ketone can be a terminal functional group

Back 4

f
it can NEVER be a terminal functional group

Front 5

If the aldehyde is attached to a ring, we use the suffix ___

Back 5

carbaldehyde

Front 6

We name an aldehyde as a substituent with the prefix -formly if....

Back 6

the aldehyde does not hold priority in the molecule

Front 7

Ketones are named with the suffix ___

Back 7

-one

Front 8

When ketones are named as a substituent we use the prefix __.

Back 8

-oxo

Front 9

Physical properties of aldehydes and ketones are goverened by the presence of...

Back 9

the carbonyl group

Front 10

The dipole of a carbonyl is ___ than the dipole of an alcohol because the carbonyl lacks a ____.

Back 10

greater, hydrogen

Front 11

The B.P. of aldehydes and ketones is ___ than that in alcohols because....

Back 11

less, because no hydrogen bonding is involved

Front 12

aldehydes or ketones
Which is more reactive towards nucleophiles

Back 12

aldehydes

Front 13

An aldehyde can be obtained from the ___ of a ____.

Back 13

partial oxidation, primary alcohol

Front 14

A ketone can be obtained from the ____ of a ____.

Back 14

oxidation, secondary alcohol

Front 15

The only reagent that can oxidize a primary alcohol to and aldehyde is ___.

Back 15

PCC

Front 16

What is PCC?

Back 16

A dry, nonhydrating oxidizing reagent

Front 17

Oxidizing reagents for ketones include....

Back 17

Sodium or potassium dichromate
chromium trioxide
PCC

Front 18

What is Jones Reagent?

Back 18

Chromium trioxide

Front 19

t or f
Can double bonds be cleaved to form aldehydes and ketones?

Back 19

t

Front 20

Define Ozonolysis?

Back 20

Breaks down double bonds using ozone

Front 21

What does Friedel-Crafts Acylation produce?

Back 21

It produces aromatic ketones in the form of R-CO-Ar

Front 22

Aldehydes and ketones exist in the ___ form.

Back 22

keto (C=O)

Front 23

Acidic are basic
alpha protons

Back 23

acidic

Front 24

Which two isomers can aldehyes and ketones exist in?

Back 24

keto and enol

Front 25

Define enol

Back 25

unsaturated alcohol
ene= double bond
ol= alcohol

Front 26

Define tautomers

Back 26

Two isomers which only differ in the placement of a proton

Front 27

The equilibrium between the tautomrs lies far to the ___ side, so there will be more ___ isomers in solution.

Back 27

keto, keto

Front 28

Define enolization

Back 28

the process of interconverting from the keto to the enol tautomer

Front 29

Enols are important ___ in many reactions of aldehydes and ketones

Back 29

intermediates

Front 30

Tautomers are not resonance structures because...

Back 30

they have different connectivity of atoms

Front 31

ENOLIZATION AND REACTIONS OF ENOLS
The enolate carbanion acts as a ____.

Back 31

nucleophile

Front 32

ENOLIZATION AND REACTIONS OF ENOLS
The enolate carbanion can be created with a _____.

Back 32

strong base

Front 33

Strong bases include....

Back 33

lithium diisopropyl amide (LDA)
Potassium hydride (KH)

Front 34

ENOLIZATION AND REACTIONS OF ENOLS
A 1,3-dicarbonyl is extra acidic because...

Back 34

there are 2 carbonyls to delocalize negative charge

Front 35

ENOLIZATION AND REACTIONS OF ENOLS
Describe Michael additions

Back 35

The nucleophilic carbanion reacts via SN2 with alkyl halides or α, β- unsaturated carbonyl compounds. The carbanion attaches to the unsaturated carbonyl at the β-position.

Front 36

Aldehyde and ketone addition reaction trend: _____ addition to a ____!

Back 36

nucleophilic, carbonyl

Front 37

ADDITION REACTIONS
C=O is polarized with a partial ____ charge on C and a partial ___ charge on O.

This makes the carbon an ___.

Back 37

positive, negative

electrophile

Front 38

ADDITION REACTIONS
When a nucleophile attacks, it forms a ___ bond to the carbon, breaking the ___ bond in the C=O.

Back 38

covalent, pi

Front 39

ADDITION REACTIONS
The electrons from the pi bond are pushed on the ___, generating a ____.

Back 39

oxygen atom, tetrahedral intermediate

Front 40

ADDITION REACTIONS
if no good leaving group is present will the carbonyl re form?

Back 40

no, the final product will be nearly identical to the intermediate

Front 41

ADDITION REACTIONS
If a good leaving group is present what happens?

Back 41

the carbonyl double bond can re-form and pulls off the leaving group

Front 42

In the presence of water, ketones and aldehydes react to form ___.

Back 42

gem-diols

Front 43

HYDRATION REACTION
the ___ oxygen in water attacks the ____ carbonyl carbon

Back 43

nucleophilic, electrophilic

Front 44

The hydration reaction normally proceeds ____.

Back 44

slowly

Front 45

How can we increase hydration reaction rate?

Back 45

Addition of acid or base

Front 46

When one equivalent of alcohol is added to an aldehyde or ketone, the product is

Back 46

a hemiacetal or hemiketal

Front 47

We can always recognize a hemiacetal or hemiketal because..

Back 47

it will still only contain one hydroxyl group

Front 48

B/c the reaction with only one equiv. of -OH have proceeded 1/2way the product is termed...
In ___ the reaction would stop here

Back 48

hemi, base

Front 49

When 2 equiv. of -OH are added, the reaction proceeds all the way and the product is...

Back 49

and acetal or ketal

Front 50

B/c aldehydes contain a ___ on the carbonyl, both hemiacetals and acetals will still contain a ____ as a distinguishing characteristic.

Back 50

hydrogen, hydrogen

Front 51

Acetal and ketal formation reaction proceeds via the same mechanism as....

Back 51

hydration

Front 52

Acetal and ketal formation reactions are catalyzed by...

Back 52

anhydrous acid

Front 53

Acetals and ketals are comparatively ___, and used as ____ for carbonyl funtionalities

Back 53

inert, protecting groups

Front 54

What is a popular protecting group?

Back 54

Ethylene glycol

Front 55

What is ethylene glycol?

Back 55

A diol and both alcohol groups come from the same molecule

Front 56

Molecules with protecting groups can easily be converted back to carbonyls with _____ and ____.

Back 56

aqueous acid and heat

Front 57

Hydrogen cyanide is a classic ___.

Back 57

nucleophile

Front 58

Alkynes are fairly acidic b/c of...

Back 58

their triple bonds

Front 59

REACTIONS WITH HYDROGEN CYANIDE
after the ___ dissociates, the nucleophilic cyanide ____ can attack the carbonyl carbon atom.

Back 59

hydrogen, anion

Front 60

REACTIONS WITH HYDROGEN CYANIDE
Reactions with aldehydes and ketones produce stable compounds called

Back 60

cyanohydrins

Front 61

REACTIONS WITH HYDROGEN CYANIDE
The cyanohydrin gains its stability from the newly formed ____ bond.

Back 61

C-C

Front 62

REACTIONS WITH HYDROGEN CYANIDE
When a carbonyl reacts with HCl what happens?

Back 62

A weak C-Cl bond is formed, and the resulting chlorohydrin isnt very stable

Front 63

When you see a carbonyl carbon, think ____ first!!!

Back 63

electrophile

Front 64

Because they make good ___, ammonia derivatives react with carbonyls

Back 64

nucleophiles

Front 65

How are imines produced?

Back 65

Ammonia adds to the carbon atom and water is lost

Front 66

What is an imine?

Back 66

Compound with a nitrogen atom double bonded to a carbon atom

Front 67

A reaction in which water is lost between two atoms is termed...

Back 67

condensation reaction

Front 68

CONDENSATION WITH AMMONIA DERIVATIVES
The 1st part of the reaction follows ____ addition

Back 68

nucleophilic

Front 69

CONDENSATION WITH AMMONIA DERIVATIVES
Reactions forms ____ intermediate

Back 69

tetrahedral

Front 70

CONDENSATION WITH AMMONIA DERIVATIVES
A ___ bond forms b/w C and N and a leaving group (___) is kicked off.

Back 70

double, water

Front 71

CONDENSATION WITH AMMONIA DERIVATIVES
A leaving group is usually kicked off by the re-formation of the....

Back 71

C=O bond

Front 72

Common ammonia derivatives that react with aldehydes and ketones are:

Back 72

H2NOH- forms oximes
H2NNH2- forms hydrazones
H2NNHCONH2- forms semicarbazones

Front 73

Describe Adol Condensation.

Back 73

An aldehyde acts both as an electrophile and a nucleophile

Front 74

ADOL CONDENSATION
The enolate is more ____ than the enol because....

Back 74

nucleophilic, negatively charged

Front 75

ADOL CONDENSATION
The nucelophilic enolate ion can react with the carbonyl group of another ____ molecule

Back 75

acetaldehyde

Front 76

ADOL CONDENSATION
The product is ____, which contains both ____ and ____ functional groups

Back 76

3-hydroxybutanal, alcohol and aldehyde

Front 77

What is an adol?

Back 77

Aldehyde + alcohol

Front 78

ADOL CONDENSATION
With a ____ base and ___ temperatures condensation occurs

Back 78

strong, high

Front 79

ADOL CONDENSATION
We kick off a ___ molecule and form a double bond, producing an _____.

Back 79

water, α,β- unsaturated aldehyde

Front 80

ADOL CONDENSATION
The ____ acts as an electrophile, and the ____ acts as a nucleophile (in the form of an ___ ion)

Back 80

carbonyl, aldehyde, enolate

Front 81

The Witting reaction swaps out a __ for a ___.

Back 81

C=O, C=C

Front 82

The Witting reaction forms carbon-carbon double bonds by converting aldehydes and ketones into ____.

Back 82

alkenes

Front 83

WITTING REACTION
First step involves formation of a ___ from the SN2 reaction of an alky halide with the nucleophilic ____.

Back 83

Phosphonium salt, triphenylphosphine

Front 84

What is triphenylphosphine?

Back 84

Phosphorous atom that has 3 aromatic phenyl groups attached to it

Front 85

WITTING REACTION
The phosphonium salt is deprotonated with a ___ base, yielding a neutral compound called an ___ or ___.

Back 85

strong, ylide or phsphorane

Front 86

WITTING REACTION
The ylide form is a...

Back 86

zwitterion

Front 87

what is a zwitterion?

Back 87

a molecule with both positive and negative charges

Front 88

WITTING REACTION
The phosphorane form has ___ bond between ___ and ___.

Back 88

double, carbon an phosphorus

Front 89

WITTING REACTION
Is an ylide a type of carbanion?

Back 89

yes

Front 90

What kind of properties does an ylide have?

Back 90

nucleophilic

Front 91

WITTING REACTION
When combined with an aldehyde or ketone, and ylide attacks the carbonyl atom giving....

Back 91

an intermediate called a betaine

Front 92

WITTING REACTION
A betaine forms...

Back 92

a four membered ring with an ionic bond b/w the oxygen and phosphorous

Front 93

WITTING REACTION
What is an oxaphosphetane?

Back 93

a ringed intermediate which decomposes to yield and alkene and triphenylphosphine oxide

Front 94

Aldehydes are ___ oxidized than alcohols but ___ oxidized than carboxylic acids

Back 94

more, less

Front 95

Ketones are as oxidized as ___ carbons can get

Back 95

secondary

Front 96

Pretty much any oxidizing agent (except __) can oxidize aldehydes into ___.

Back 96

PCC, carboxylic acids

Front 97

Oxidizing agents include:

Back 97

PCC, KMnO4, CrO3, Ag2O, and H2O2

Front 98

The most common reagents used to reduce aldehydes and ketones to alcohols are...

Back 98

LAH and NaBH4

Front 99

What are 2 ways to reduce aldehydes and ketones all the way to alkanes?

Back 99

Wolff-Kishner reduction
Clemmensen reduction

Front 100

In the Wolff Kishner reduction, the carbonyl is first converted to ____

Back 100

hydrazone

Front 101

In the Wolff Kishner reduction hydrazone releases molecular ___ when it is heated with a ___, forming an ___

Back 101

nitrogen, base (KOH), alkane

Front 102

Wolff Kisher reaction is only useful when the product is __ under ___ conditions

Back 102

stable, basic

Front 103

In the Clemmensen reduction and aldehyde or ketone is heated with ___ in ___.

Back 103

amalgamated zinc, HCl

Front 104

What is ethylene glycol

Back 104

a high boiling solvent

Front 105

In a carbonyl, the carbon is ___ and the oxygen is ___.

Back 105

positive, negative

Front 106

Aldehydes can be synthesized from ____ with ___.

Back 106

primary alcohols, PCC

Front 107

Aldehydes can be oxidized to ___ or reduced to ____.

Back 107

carboxylic acids, primary alcohols

Front 108

Ketones cannot be further ___, but they can be reduced to ____.

Back 108

oxidized, secondary alcohols

Front 109

The enol form is significant because it can act as a ___, but is not prevalent in ____.

Back 109

nucleophile, solution

Front 110

Ammonia deriviatives often add in ___ reactions.

Back 110

condensation