Ch:18 Aldehydes and ketones: Nucleophilic Addition Rxn Flashcards
The more R groups on the carbonyl C, the _______ reactive the compound. What effect is this due to? 
Less, steric effects 
Are Aldehydes or ketones more reactive?
Aldehydes 
According to IUPAC how do you name aldehydes?
- end in -al
- the -e in the corresponding alkane name is replace with suffix -al
- if the -CHO Group is bonded to a carbon in a ring, the aldehyde is named by using the name of the cycloalkane + the suffix carbaldehyde 
How do you name Unbranched aldehydes by their common name?
Root + aldehyde 
How do you name branched aldehydes by their common name?
-use Greek letters 
What are the rules for naming ketones according to IUPAC?
- end in -one
- parent chain = longest carbon chain that contains the C double bond O group
How do you name ketones by IUPAC if the double bond O is attached to a carbon in a ring?
Replace the e in the cycloalkane name with -one
How do you name ketones by their common name?
Name the two R groups alphabetically and add the word ketone. 
Ex:Diethylketone
In the group priorities, does ketones or aldehydes have a higher priority?
Aldehydes
Aldehydes and ketones do not contain ___ groups . 
OH
- as a result there’s no possibility of hydrogen bonding, They only have the VDW forces and dipole dipole interactions
Aldehydes and ketones have _______ MP and BP Then alcohols in carboxylic acids of comparable molar mass.
Lower
What ketones and aldehydes are soluble in organic solvents?
All sizes
Aldehydes and ketones with a number of carbons less than or equal to ____ Are soluble in water because of their ability to hydrogen bond with water.
5
For cyclic ketones, the -C=O Frequency ___________ As the number of carbon atoms decreases because of ring strain.
Increases
For conjugated systems IR:
Frequency __________ With increasing conjugation because the -C=O Any conjugate system has a partial single bond character due to resonance. 
Deceases
For H NMR, Alpha H is ______ and the H Double bonded to O is ______. 
2-2.5 delta
9-10 delta
Oxidation of primary alcohols is done with?
-produces an aldehyde
PCC
Reduction of Esters Is done with
-produces an aldehyde
DIBAL-H
Reduction of acid chloride is done with? 
-produces an aldehyde
LiAlH[OC(CH3)3]3
Hydroboration (Non-Markonikov) of Terminal alkynes is done with?
-produces an aldehyde
- BH3
2. H2O2,OH-
Ozonolysis: Oxidative cleavage of Alkenes is done with? 
-Produces an aldehyde
- O3
2. Zn, H2O or CH3SCH3
Oxidation of a secondary alcohol is done by?
Produces a ketone
K2Cr2O7
H3O+
O |
Reaction of Organocuprates with Acid Chlorides is done with? 
(produces a ketone)
- R’2 CuLi
- H2O
- (CH3)2CuLi
- H2O
Friedel-Crafts Acylation: Aromatic ketones is done with?
AlCl3
Mercury ration or hydration of an alkaline (Follows Markovnikov) Is done by?
(Produces a ketone) 
H2O, H2SO4
HgSO4
Ozonolysis: Oxidative cleavage of try and Tetrasubstituted Alkenes Is done by?
(produces ketones)
- O3
2. Zn, H2O or CH3SCH3
Non-Markonikov Hydroboration of internal alkynes is done by?
Produces two ketones
- BH3
2. H2O2, OH-
Reaction of nitriles with R’MgX 
(Produces a ketone)
- R’MgX
2. H2O
What are the two general kinds of reactions of aldehydes and ketones?
- nucleophilic addition reactions at the carbonyl carbon (unit 10)
- Reactions at the Alpha carbon. These reactions require a base (unit 14) 
See page 382
In reactions at the Alpha Carbon, what is produced as an intermediate?
an enolate ion
What are the organometalic reagents?
R’M = R’MgX, R’Li, HC triple bond C-Li
What is the grignard’s reagent?
MgX
What is needed for Addition of CN- In acidic media: Cyanohydrin formation?
NaCN
HCL
What is needed for the hydrolysis of a cyanohydrin To lead to alpha-hydroxy carboxylic acid? 
H2O
H+ or OH-
What is the Wittig reaction used to do?
Convert a ketone or aldehyde to an alkene
What is the Cannizzaro reaction of Aldehydes?
It occurs with aldehydes and ketones with no alpha hydrogens (Formaldehyde and benzaldehyde) in NaOH or KOH. The aldehyde is oxidized and reduced at the same time. 
What is disproportionation?
And what rxn is associated?
Oxidation and reduction at the same time
Cannizzaro reaction 
What is needed for the addition of a primary means to aldehydes and ketones:Imines?
R’NH2
Mild acid
Produces an imine
C=N
Replace oh with NR2 And put a double bond between C1 and alpha carbon
Addition of secondary a means to aldehydes and ketones. What is needed?
What is produced? 
R’2NH
Mild acid
An enamine
C=C
What is needed for the hydration of aldehydes in acidic or alkaline media? 
H2O
H+ or OH-
Produces a gem-diol (hydrate)
Thermodynamics of hydration: is the reaction reversible?
Yes, dose not reach equilibrium
Thermodynamics of hydration: More stable reactants give ______ yields.
Small
Thermodynamics of hydration:
Does having more alkyl groups Give a higher or lower yeild at equilibrium?
Lower
Alkyl groups (EDG) stabilize the carbonyl groups through inductive electron donation 
Thermodynamics of hydration:
The presence of EDG in a compound leads to _______ yields at equilibrium. 
Small
What is needed for the addition of alcohols to aldehydes and ketones:acetal products? 
Catalyzed by an acid such as p-toluenesulfonic acid (TsOH)
-Get OR groups instead of OH groups
Called a ketal when done with ketones and an acetal when with aldehydes
Acetals of ethylene glycol produce cyclic acetals by what reagent?
HOCH2CH2OH ——> ethylene glycol
(OH on both ends)
What is used to remove water to increase the yield? 
Dean-Stark trap
What can be used to protect aldehydes and ketones from Being reduced?
Ethylene glycol: HOCH2CH2OH
Hydroxy aldehydes exist mostly as
Cyclic hemiacetals = lactol 
A cyclic hemiacetal can or lactol can always be converted to ______.
Acetal
What reagent is needed for the hydrolysis of imines in acidic media? 
H2O/H+
Produces a ketone and a primary amine
What region is needed for the hydrolysis of enamines in acidic media?
H2O/H+
Alpha-D-glucose (hemiacetal) is ….
Beta-D-glucose (hemiacetal) is…..
Axial
Equatorial (major product)
Is sugar that has an aldehyde, a ketone, a hemiacetal, or a hemiketal is called a…
Reducing sugar. These can reduce an oxidizing agent such as Br2
What are some bon-reducing sugars?
Acetals, Ketals, alpha and beta glycosides
What test is used for aldehydes only? What kind of reaction is it?
The Tollen’s silver mirror test
Oxidation reaction
Tollens reagent is prepared by dissolving…..
Silver oxide in ammonia. Reacts with aldehyde to give a silver mirror 
what does the Fehlings test for?
For aldehydes.
Oxidizes aldehyde to a carboxylic acid
How is Fehling’s test prepared? 
Cu2+ -tartare complex in alkaline solution
Cu+ Combines with oxygen to give a Cu2O brick red precipitate. 
What is another test for aldehydes that is similar to Fehlings reagent? What does it use instead? 
Benedicts test for aldehydes
Citric acid instead of Tartaric acid
What kind of reaction is the bisulfate test?
What does it test for?
-An addition reaction
-aldehydes and ketones

Test where a small amount of 20% aqueous sodium bisulfite solution is added to an aldehyde or ketone
-A positive test produces white bisulfate compound crystals
Bisulfite Test
The Shiff’s Fuchsin-aldehyde test?
Is for what only?
What type of reaction is it?
Aldehydes
Complex addition reaction
And this test a Faintly pink dye is decolorized by sulfur dioxide this reagent turns purple in the presence of an aldehyde
The Schiff’s Fushin-Aldehyde Test
Treatment of an aldehyde or ketone with either _____ or ______ followed by protonation of Forms a Primary or secondary alcohol*
NaBH4, LiAlH4
