Use LEFT and RIGHT arrow keys to navigate between flashcards;
Use UP and DOWN arrow keys to flip the card;
H to show hint;
A reads text to speech;
25 Cards in this Set
- Front
- Back
|
Phenols |
acidic due to resonane. Benzene with a alcohol group. highly acidic due to resonance EW increace acidity. ED decrease acidity pka ~ 10 |
|
|
alcohol properties |
more alcohol = higher bp related to hydrogen bonding pka ~ 15 |
|
|
Alcohol Oxidation to aldehyde and ketone |
primary alcohol with PCC to form aldeydel seocndary alcohol with PCC to ketone tertiary cannot be oxidized |
|
|
Alcohol oxidation to carboxyllic acids/ketones |
strong oxidizing agents Na2Cr2O7 K2Cr2O7 primary to carboxylic acid secondary to ketone |
|
|
Jones Oxidation |
CrO3 w/ H2SO4 Primary -->carboxyllic acid Seocndary --> ketone |
|
|
Alcohol as LG |
Poor LG made good by adding Tosylate/Methylate Tosylate/Mesylate = Protecting groups |
|
|
Alcohol to Protect |
React with a diol to a primary or secondary alcohol. Ketals and acetals cannot be reduced with LiAlH4 Carbonyl's can be reduced by LiAlH4 |
|
|
Quinones |
Phenol with ketone. resonance stabilized electrophile (acid) Alcohol with Na2Cr207 with H2So4 further oxidize by adding an -OH hydroxyquoione destabilized b/c of electron donor -OH |
|
|
aldehyde/ketone |
more polar than alcohol lower bp b/c no hydrogen bonds electrophiles |
|
|
Nucleophile Addition |
carbonyl will be attacked by Nu: The pi bond e will join the O The carbonyl will only reform if a good LG. |
|
|
Aldehyde/Ketone Hydration |
With water, form geminal dioles (same C) |
|
|
Ketone/Aldehyde to Acetal/hemiacetal |
-OR group fromed when alchol or diol added |
|
|
Imines and Enamines |
Nucleophile substitution N is a good nucleophile Condensation reaction Imines tautomerize to form enamines |
|
|
Cynohydrins |
CHN=aweseom nuclophile very acidic New C - C bonds Carbonyl become -0H |
|
|
Aldehyde/Ketone oxidation to carboxyllic acid |
Anything stronger than PCC KMNO4, CrO3, AG2O, H2O2 |
|
|
Reduction of Aldehyde/Ketone to alcohol |
LiAlH4 or NaBH4 |
|
|
Acidity of alpha carbon hydrogen on carbonyl aldehyde/ketones in base form... |
weak bonds makes it easy to deprotonate alpha carbon. Forms a carbanion resonace stability makes this bigger effect |
|
|
Aldehyde/Ketone Hinderance |
aldehydes more reactive b/c less hindered |
|
|
Tautomers |
differe in placement of a proton double bond. equillibria lies towards keto side enolization is the conversion from keto to enol |
|
|
carbanion |
is a nucleophile ready to react with electrophile |
|
|
Michael Addition |
Aldehyde/Ketone in base forms carbanion. Thisn ucleophile attacks double bond to form an addition. |
|
|
Kinetic and Thermodynamic Enolates |
Kinetic= fast/less stable: bound to less substitued thermodynamic=slow/stable: bound to more substitutd |
|
|
Imines --> Enamines |
tautomers imine c=n enamine c=c |
|
|
Aldol condensation |
loss of H2O nucleophile addition the ketone acts as both electrophile/nucleophile and substitues on itself dehydrated with a strong base useful when use same aldehyde/ketone |
|
|
Aldol retro-aldo reaction |
Add based and heat breaks bonds |
