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110 Cards in this Set
- Front
- Back
Aldehydes are named with suffix ___
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-al
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Aldehydes occupy what position?
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the terminal position
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Common names for the first five aldehydes are:
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*formaldehyde
*acetaldehyde propionaldehyde butyraldehyde valeraldehyde |
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t or f
A ketone can be a terminal functional group |
f
it can NEVER be a terminal functional group |
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If the aldehyde is attached to a ring, we use the suffix ___
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carbaldehyde
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We name an aldehyde as a substituent with the prefix -formly if....
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the aldehyde does not hold priority in the molecule
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Ketones are named with the suffix ___
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-one
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When ketones are named as a substituent we use the prefix __.
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-oxo
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Physical properties of aldehydes and ketones are goverened by the presence of...
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the carbonyl group
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The dipole of a carbonyl is ___ than the dipole of an alcohol because the carbonyl lacks a ____.
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greater, hydrogen
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The B.P. of aldehydes and ketones is ___ than that in alcohols because....
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less, because no hydrogen bonding is involved
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aldehydes or ketones
Which is more reactive towards nucleophiles |
aldehydes
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An aldehyde can be obtained from the ___ of a ____.
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partial oxidation, primary alcohol
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A ketone can be obtained from the ____ of a ____.
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oxidation, secondary alcohol
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The only reagent that can oxidize a primary alcohol to and aldehyde is ___.
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PCC
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What is PCC?
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A dry, nonhydrating oxidizing reagent
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Oxidizing reagents for ketones include....
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Sodium or potassium dichromate
chromium trioxide PCC |
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What is Jones Reagent?
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Chromium trioxide
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t or f
Can double bonds be cleaved to form aldehydes and ketones? |
t
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Define Ozonolysis?
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Breaks down double bonds using ozone
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What does Friedel-Crafts Acylation produce?
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It produces aromatic ketones in the form of R-CO-Ar
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Aldehydes and ketones exist in the ___ form.
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keto (C=O)
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Acidic are basic
alpha protons |
acidic
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Which two isomers can aldehyes and ketones exist in?
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keto and enol
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Define enol
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unsaturated alcohol
ene= double bond ol= alcohol |
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Define tautomers
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Two isomers which only differ in the placement of a proton
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The equilibrium between the tautomrs lies far to the ___ side, so there will be more ___ isomers in solution.
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keto, keto
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Define enolization
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the process of interconverting from the keto to the enol tautomer
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Enols are important ___ in many reactions of aldehydes and ketones
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intermediates
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Tautomers are not resonance structures because...
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they have different connectivity of atoms
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ENOLIZATION AND REACTIONS OF ENOLS
The enolate carbanion acts as a ____. |
nucleophile
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ENOLIZATION AND REACTIONS OF ENOLS
The enolate carbanion can be created with a _____. |
strong base
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Strong bases include....
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lithium diisopropyl amide (LDA)
Potassium hydride (KH) |
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ENOLIZATION AND REACTIONS OF ENOLS
A 1,3-dicarbonyl is extra acidic because... |
there are 2 carbonyls to delocalize negative charge
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ENOLIZATION AND REACTIONS OF ENOLS
Describe Michael additions |
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.
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Aldehyde and ketone addition reaction trend: _____ addition to a ____!
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nucleophilic, carbonyl
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ADDITION REACTIONS
C=O is polarized with a partial ____ charge on C and a partial ___ charge on O. This makes the carbon an ___. |
positive, negative
electrophile |
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ADDITION REACTIONS
When a nucleophile attacks, it forms a ___ bond to the carbon, breaking the ___ bond in the C=O. |
covalent, pi
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ADDITION REACTIONS
The electrons from the pi bond are pushed on the ___, generating a ____. |
oxygen atom, tetrahedral intermediate
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ADDITION REACTIONS
if no good leaving group is present will the carbonyl re form? |
no, the final product will be nearly identical to the intermediate
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ADDITION REACTIONS
If a good leaving group is present what happens? |
the carbonyl double bond can re-form and pulls off the leaving group
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In the presence of water, ketones and aldehydes react to form ___.
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gem-diols
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HYDRATION REACTION
the ___ oxygen in water attacks the ____ carbonyl carbon |
nucleophilic, electrophilic
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The hydration reaction normally proceeds ____.
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slowly
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How can we increase hydration reaction rate?
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Addition of acid or base
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When one equivalent of alcohol is added to an aldehyde or ketone, the product is
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a hemiacetal or hemiketal
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We can always recognize a hemiacetal or hemiketal because..
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it will still only contain one hydroxyl group
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B/c the reaction with only one equiv. of -OH have proceeded 1/2way the product is termed...
In ___ the reaction would stop here |
hemi, base
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When 2 equiv. of -OH are added, the reaction proceeds all the way and the product is...
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and acetal or ketal
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B/c aldehydes contain a ___ on the carbonyl, both hemiacetals and acetals will still contain a ____ as a distinguishing characteristic.
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hydrogen, hydrogen
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Acetal and ketal formation reaction proceeds via the same mechanism as....
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hydration
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Acetal and ketal formation reactions are catalyzed by...
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anhydrous acid
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Acetals and ketals are comparatively ___, and used as ____ for carbonyl funtionalities
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inert, protecting groups
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What is a popular protecting group?
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Ethylene glycol
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What is ethylene glycol?
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A diol and both alcohol groups come from the same molecule
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Molecules with protecting groups can easily be converted back to carbonyls with _____ and ____.
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aqueous acid and heat
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Hydrogen cyanide is a classic ___.
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nucleophile
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Alkynes are fairly acidic b/c of...
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their triple bonds
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REACTIONS WITH HYDROGEN CYANIDE
after the ___ dissociates, the nucleophilic cyanide ____ can attack the carbonyl carbon atom. |
hydrogen, anion
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REACTIONS WITH HYDROGEN CYANIDE
Reactions with aldehydes and ketones produce stable compounds called |
cyanohydrins
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REACTIONS WITH HYDROGEN CYANIDE
The cyanohydrin gains its stability from the newly formed ____ bond. |
C-C
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REACTIONS WITH HYDROGEN CYANIDE
When a carbonyl reacts with HCl what happens? |
A weak C-Cl bond is formed, and the resulting chlorohydrin isnt very stable
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When you see a carbonyl carbon, think ____ first!!!
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electrophile
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Because they make good ___, ammonia derivatives react with carbonyls
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nucleophiles
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How are imines produced?
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Ammonia adds to the carbon atom and water is lost
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What is an imine?
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Compound with a nitrogen atom double bonded to a carbon atom
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A reaction in which water is lost between two atoms is termed...
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condensation reaction
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CONDENSATION WITH AMMONIA DERIVATIVES
The 1st part of the reaction follows ____ addition |
nucleophilic
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CONDENSATION WITH AMMONIA DERIVATIVES
Reactions forms ____ intermediate |
tetrahedral
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CONDENSATION WITH AMMONIA DERIVATIVES
A ___ bond forms b/w C and N and a leaving group (___) is kicked off. |
double, water
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CONDENSATION WITH AMMONIA DERIVATIVES
A leaving group is usually kicked off by the re-formation of the.... |
C=O bond
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Common ammonia derivatives that react with aldehydes and ketones are:
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H2NOH- forms oximes
H2NNH2- forms hydrazones H2NNHCONH2- forms semicarbazones |
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Describe Adol Condensation.
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An aldehyde acts both as an electrophile and a nucleophile
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ADOL CONDENSATION
The enolate is more ____ than the enol because.... |
nucleophilic, negatively charged
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ADOL CONDENSATION
The nucelophilic enolate ion can react with the carbonyl group of another ____ molecule |
acetaldehyde
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ADOL CONDENSATION
The product is ____, which contains both ____ and ____ functional groups |
3-hydroxybutanal, alcohol and aldehyde
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What is an adol?
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Aldehyde + alcohol
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ADOL CONDENSATION
With a ____ base and ___ temperatures condensation occurs |
strong, high
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ADOL CONDENSATION
We kick off a ___ molecule and form a double bond, producing an _____. |
water, α,β- unsaturated aldehyde
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ADOL CONDENSATION
The ____ acts as an electrophile, and the ____ acts as a nucleophile (in the form of an ___ ion) |
carbonyl, aldehyde, enolate
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The Witting reaction swaps out a __ for a ___.
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C=O, C=C
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The Witting reaction forms carbon-carbon double bonds by converting aldehydes and ketones into ____.
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alkenes
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WITTING REACTION
First step involves formation of a ___ from the SN2 reaction of an alky halide with the nucleophilic ____. |
Phosphonium salt, triphenylphosphine
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What is triphenylphosphine?
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Phosphorous atom that has 3 aromatic phenyl groups attached to it
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WITTING REACTION
The phosphonium salt is deprotonated with a ___ base, yielding a neutral compound called an ___ or ___. |
strong, ylide or phsphorane
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WITTING REACTION
The ylide form is a... |
zwitterion
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what is a zwitterion?
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a molecule with both positive and negative charges
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WITTING REACTION
The phosphorane form has ___ bond between ___ and ___. |
double, carbon an phosphorus
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WITTING REACTION
Is an ylide a type of carbanion? |
yes
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What kind of properties does an ylide have?
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nucleophilic
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WITTING REACTION
When combined with an aldehyde or ketone, and ylide attacks the carbonyl atom giving.... |
an intermediate called a betaine
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WITTING REACTION
A betaine forms... |
a four membered ring with an ionic bond b/w the oxygen and phosphorous
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WITTING REACTION
What is an oxaphosphetane? |
a ringed intermediate which decomposes to yield and alkene and triphenylphosphine oxide
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Aldehydes are ___ oxidized than alcohols but ___ oxidized than carboxylic acids
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more, less
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Ketones are as oxidized as ___ carbons can get
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secondary
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Pretty much any oxidizing agent (except __) can oxidize aldehydes into ___.
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PCC, carboxylic acids
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Oxidizing agents include:
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PCC, KMnO4, CrO3, Ag2O, and H2O2
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The most common reagents used to reduce aldehydes and ketones to alcohols are...
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LAH and NaBH4
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What are 2 ways to reduce aldehydes and ketones all the way to alkanes?
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Wolff-Kishner reduction
Clemmensen reduction |
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In the Wolff Kishner reduction, the carbonyl is first converted to ____
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hydrazone
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In the Wolff Kishner reduction hydrazone releases molecular ___ when it is heated with a ___, forming an ___
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nitrogen, base (KOH), alkane
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Wolff Kisher reaction is only useful when the product is __ under ___ conditions
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stable, basic
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In the Clemmensen reduction and aldehyde or ketone is heated with ___ in ___.
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amalgamated zinc, HCl
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What is ethylene glycol
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a high boiling solvent
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In a carbonyl, the carbon is ___ and the oxygen is ___.
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positive, negative
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Aldehydes can be synthesized from ____ with ___.
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primary alcohols, PCC
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Aldehydes can be oxidized to ___ or reduced to ____.
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carboxylic acids, primary alcohols
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Ketones cannot be further ___, but they can be reduced to ____.
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oxidized, secondary alcohols
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The enol form is significant because it can act as a ___, but is not prevalent in ____.
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nucleophile, solution
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Ammonia deriviatives often add in ___ reactions.
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condensation
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