Aldehyde & Ketone Flashcards
Aldehyde & ketones both have a ________ group
Carbonyl
Aldehydes & ketones are named the same way as _________
Alkanes (same rules)
When choosing the parent of an aldehyde have to identify the longest chain that includes the carbon atom of the ____________ group
Aldehyde group
Aldehyde ends in _____
“al”
When numbering an aldehyde has ______ priority over any substituents even over an OH group
so should have the lowest #
Higher
Cyclic compounds with aldehydes group directly adjacent to the ring end in ____________
“Carbaldehyde” ex. Cylcohexanecarbaldehyde
What is the name of this simple aldehyde ?
Formaldehyde
What is the name of this simple aldehyde ?
Acetaldehyde
What is the name of this simple aldehyde ?
Benzaldehyde
Ketones end in what?
“one” ex. Butanone
What is the name of this simple ketone?
Acetone
What is the name of this simple ketone?
Acetophenone
What is the name of this simple ketone?
Benzophenone
What is the mechanism for nucleophilic addition under basic conditions for ketones & aldehydes?
- Nucleophilic attack
- Proton transfer
What is the mechanism for nucleophilic addition under acidic conditions?
- Proton transfer
- Nucleophilic attack
When an aldehyde or ketone is treated with water, the carbonyl groups can be converted into a _________
Hydrate
The position of equilibrium generally favors the _________ rather than the hydrate except when dealing with simple aldehydes like formaldehyde
Carbonyl
What is the mechanism for basic catalyzed hydration?
- Nucleophilic attack
- Proton transfer
What is mechanism for acid catalyzed hydration?
- Proton transfer
- Nucleophilic attack
- Proton transfer
Under _______ conditions a mechanism will only be reasonable if it avoids the use or formation of strong base (only weak bases can be employed)
Acidic
Under ______ condition a mechanism will only be reasonable if it avoids the use or formation of strong acid (only weak acids can be employed)
Basic
In ______ conditions an aldehyde or ketone will react with two molecules of alcohols to form an acetal
Acidic
What are the two common acids use for the reaction to convert a ketone or aldehyde into an acetal?
- p-Toluenesulfonic acid (TsOH)
- Sulfonic acid (H2SO4)
What is the mechanism for acetal formation?
- Proton transfer
- Nucleophilic attack
- Proton transfer
- Hemiacetal (intermediate)
- Proton transfer
- Loss of LG
- Nucleophilic attack
- Proton transfer
A _______ acetal can be formed with the same mechanism for acetal formation
Cyclic
_________ can be used to protect ketones or aldehydes
Acetals
When a compound contains both a _________ & ________ group the resulting cyclic hemiacetal can be formed (isolated)
Carbonyl & OH group
In mildly acidic condition an aldehyde or ketone will react with a primary amine to form an ______
Imine (Shiff base)
What mechanism for imine formation?
- Nucleophilic attack
- Proton transfer
- Carbinolamine (intermediate)
- Proton transfer
- Loss of LG
- Proton transfer
Many different compounds of the form RNH2 will react with aldehydes or ketones where the R group can be an _____ or ______
OH or NH2
When hydroxylamine (NH2OH) is used as a nucleophile then an ________ is formed
Oxime
When hydrazine (NH2NH2) is used as a nucleophile a ___________ is formed
Hydrazone
Both the formation of oxime & hydrazone have the same mechanism as the formation of an _______
Imine
In acidic conditions, an aldehyde or ketone will react with a secondary amine to form an _________
Enamine
What is the mechanism for the formation of enamine?
- Nucleophile attack
- Proton transfer
- Carbinolamine
- Proton transfer
- Loss of LG
- Proton transfer
Wolff-Kisher reduction
Reduces a hydrazone into an alkane with KOH/H2O & heat
What is the mechanism for the wolf-kishner reduction?
- Proton transfer
- Proton transfer
- Proton transfer
- Loss of LG
- Proton transfer
In a __________ reaction bonds are cleaved when treated with water
Hydrolysis
What is the mechanism for a hydrolysis of acetals?
- Proton transfer
- Loss of LG
- Proton transfer
- Hemiacetal
- Proton transfer
- Loss of LG
- Proton transfer
In acidic conditions an aldehyde or ketone will react with 2 equivalents of thiol to form a __________
Thioacetal
The formation of thioacetal has the same mechanism as the formation of _________
Acetal
If a compound with two SH group is used then a cyclic ___________ is formed
thioacetal
When treated with _________ thioacetals undergo desulfurization yielding an alkane
Raney Nickel
Can reduce ketones with _________ & __________ to form alkanes
Thioacetals & Raney Ni
Ketones & aldehydes can be reduced to alcohols by ________ reducing agents like LAH & NaBH4
Hydride
What is the mechanism for reduction of ketone or aldehydes with hydride reagents?
- Nucleophilic attack
- Proton transfer
When treated with __________ aldehydes or ketones care converted into alcohols
Grignard reagent
When treated with hydrogen cyanide (HCN) aldehydes or ketones are converted into ___________
Cyanohydrins
What is mechanism for cyanohydrin formation?
- Nucleophilic attack
- Proton Transfer
______________ can also be formed by treating a ketone or aldehyde with potassium cyanide & HCl (or another source of protons)
Cyanohydrins
Wittig Reaction
Converts a ketone into alkene
A ________________ is used to convert a ketone to an alkene
Phosphorus ylide (Wittig reagent)
What is the mechanism for the Wittig reaction?
- [2+2] cycloaddition
- Fragmentation
_____________ is prepared by treating triphenylphosphine with an alkyl halide followed by a strong base in an SN2 reaction followed by deprotonation with the strong base
Wittig Reagent
Baeyer Villiger reaction
When treated with peroxy acids ketones can be converted into ester by insertion of an oxygen atom
What is the mechanism for the Beayer Villiger oxidation?
- Nucleophilic attack
- Proton transfer
- Rearrangement
When a cyclic ketone is treated with peroxy acid the product is ___________
Cyclic ester (lactone)
When unsymmetrical ketone is treated with peroxy acid formation is ester is ____________
Regioselective
Migratory aptitude (migration rates) is what?
H>3o>20, Ph>10>methyl (increasing order so H migrates most rapidly)
What ae the 4 reaction that change the carbon skeleton?
- Grignard reaction
- Cyanohydrin formation
- Wittig reaction
- Baeyer Villiger oxidation
Carbonyl groups produces a strong signal in IR spectrum around ________ or ________
1715 or 1720cm-1
A ____________ carbonyl group will produce a signal at a lower wavenumber
conjugated
When you increase the ring strain then the wavenumber __________
Increases
Aldehydes usually have one or 2 signals between ______ & _____cm-1
2700 & 2850cm-1
Carbonyl groups adds ____ to the chemical shift of its neighbors
+1
Aldehydes proton usually produce signals around _____ ppm
10 ppm
In a 13C spectrum the carbonyl group of a ketone or aldehyde will have a weak signal near ________ ppm
200ppm
Can hydrolyze an acetal, imine, enime with acidic aqueous water to form a _________
Ketone
When Acetal is treated with Acidic water it can be converted back into a __________
Ketone
Can turn a ketone carbonyl group into an ___________ for protection
Acetal
A cyanohydrin can be reduced with LAH to produce ____________
A compound with OH & NH2
Cyanohydrins can be reduced with Acidic water & heat to produce ___________
OH & carboxylic acid