Nasiri CHE118B Final Study Guide 

Spring 2019 || S. Ly ​[email protected] 

CH 17: Aldehydes and Ketones 

 
→ ​NAMING KETONES 
● Alkan​one 
● In cyclic form: cyclo​alkanone 
● Priority: aldehydes > ketones > alcohols 
○ As a substituent:​ oxo- 

 
→ ​SYNTHESIS OF ALDEHYDES AND KETONES  
Recall previous reactions… 

 
New reactions: 
● Oxidation of allylic alcohol​: only the allylic alcohol gets oxidized. 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

 
→ ​NUCLEOPHILIC ADDITION REACTIONS 
● C=O bond is polar and susceptible to reaction. 
○ Acid acts as a catalyst by protonating the carbonyl O 

 
● Aldehydes are​ more reactive​ than ketones. 
○ Less steric hindrance 
○ More electron deficient carbon (only one alkyl group attached--recall alkyl groups are 
electron donating) 
 
→ ​ADDITION OF WATER/ALCOHOL 

 
● Hemiacetals and geminal diols CANNOT be isolated; Carbon is too electron deficient 
○ You will get a mixture of your original carbonyl + the geminal diol/acetal 
○ Equilibrium usually lies to the left with certain exceptions: 

 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

 
● Unlike hemiacetals and geminal diols, acetals can be isolated! 

 
** Fill in mechanism below (all steps should be reversible) 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
● Intramolecular acetal formation is possible.  

 
● Recall 5 and 6 membered rings are the most stable. 
● If you have two carbonyls on one molecule, acetals are a good way to protect one of those groups 
from reacting with your reagents.  

 
● Thioacetals can be formed similarly. 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

○ can also do reactions that acetals cannot, like reduction with hydrogen. 

 
→ ​REACTIONS WITH AMINES 
● Ideal pH for these reactions is 4.5 - 5.5 (need acidic medium as a catalyst). Reactions are 
reversible. 
● Primary amine: forms an imine 

 
** Fill in mechanism below 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
● Secondary amine: forms an enamine 

 
** Fill in the mechanism below: 
 
 
 
 
 
 
 
 
 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

 
 
● Tertiary amine: NR 
→ ​WOLFF KISHNER REDUCTION 
● Past methods of deoxygenation included H2, Raney Ni and Clemmensens reduction 
○ Both are in acidic medium 
● Wolff Kishner red. Occurs in ​basic m
​ edium 

 
** Fill in the mechanism below: 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
→ ​HCN ADDITION 
● HCN can be synthesized using NaCN and an acid (HCl, H2SO4, etc..) 

 
** Fill in the mechanism (for both addition and removal of CN) 
 
 
 
 
 
 
 
 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

 
→ ​YLIDE ADDITION 

 
** Fill in mechanism below, including ylide synthesis: 
 
 
 
 
 
 
 
 
 
 
 
→ ​OXIDATION TESTS FOR ALDEHYDES 
● Tollen’s reagent​ = [Ag(NH3)2]OH 
○ Forms a silver mirror precipitate 
○ Reacts only with aldehydes, not ketones 
● Fehling’s test​ =​ Cu2+, -OH, H2O  
○ Forms a brick red solid precipitate 
○ Reacts only with aldehydes, not ketones 
 
→ ​BAEYER WILLIGER OXIDATION 
● Basically inserting an oxygen next to your carbonyl 
● Migratory aptitude:​ H > tertiary > secondary > phenyl > primary > methyl 
○ Better migratory aptitude means the oxygen is more likely to stick itself in that position 

 
** Fill in the mechanism below: 
 
 
 
 
 
 
 
 
 
 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

* ​PRACTICE 

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Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

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Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

CH 18: Enols/Enolates 
→ ​ALPHA HYDROGENS 

 
● The alpha hydrogen is very acidic. This is due to resonance stability and inductive effects. 
○ The alpha H in aldehydes is more acidic than ketones (more electron deficient) 
● Removal forms a special ion called an ​enolate ion: 

 
● An optically active aldehyde or ketone will lose it's optical activity in the presence of acid or base, 
proving that the alpha H is acidic: 

 
** Fill in the mechanism for an acidic medium: 
 
 
 
 
 
 
 
 
 
 
 
 
** Fill in the mechanism for a basic medium: 
 
 
 
 
 
 
 
 
 
 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

→ ​ALPHA HALOGENATION 
● In ​acidic medium -> monohalogenation 

 
** Fill in the mechanism below: 
 
 
 
 
 
 
 
 
 
 
 
● In ​basic medium -> polyhalogenation 
○ All alpha H’s get replaced by the halogen 
● Iodoform test: 
○ Used to test for presence of methyl ketones. Positive test yields a yellow precipitate. 
○ Can use other halogens besides iodine too (except F) 

 
** Fill in the mechanism below: 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
→ ​ALPHA ALKYLATION 
● The enolate ion can be used to do an alkylation reaction. 
○ Problems:  
■ Must be a methyl halide or a primary haloalkane; otherwise E2 reaction may occur 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

■ With aldehydes, there is a competing reaction: aldol condensation 

 
● To avoid these problems, enamines can be used as a type of protecting group, since they have 
enolate ion characteristic. 
○ Halide can be methyl, primary, or secondary 
○ No polyalkylation 

 
→ ​ALDOL CONDENSATION 

 
 
● Yield is lower for ketones than aldehydes 
● Requires at least two alpha hydrogens 
● ALWAYS count your carbons to check your answer. (i.e. adding an ald with 3 C + ald with 4 C -> 
product should have 7 C) 
** Fill in the mechanism below: 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

● Intramolecular aldol condensation is possible. Recall, 5 and 6 membered rings are the most 
favorable. 

 
● When a reaction has two different aldehydes, mixed condensation occurs. 

 
● To prevent this from happening, make sure one of the reagents does not have 2 alpha Hs. 
● Using a ketone can also be effective because ketones are less reactive than aldehydes. 
 
→ ​CONJUGATED ALPHA-BETA UNSATURATED ALDEHYDES AND KETONES 
● Aldol condensation leads to an important product: ​conjugated​ ​α-β-unsaturated 
aldehydes/ketones 

 
● Can be synthesized in other ways too: 

 
● Nucleophilic addition goes through two routes: 1,2 and 1,4 addition 
1,2 ADDITION: 
● Involves only one double bond and not both 
● Favored by RMgX, RLi, NaBH4, LiAlH4, X2 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

 
1,4 ADDITION 
● Involves both double bonds 
● Favored by water, alcohols, enolates, enamines, amines, HCN, organocuprates (R2CuLi) 

 
** Fill in the mechanism below: 
 
 
 
 
 
 
 
 
Organocuprates: 

 
 
 
 
 
 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

Michael addition (addition of enolate ion): 

 
● There should be three carbons between the two carbonyls 
● Again, count your carbons to make sure they are all accounted for. 
** Fill in mechanism: 
 
 
 
 
 
 
 
 
 
 
 
 
 
→ ​MICHAEL ADDITION 
● Michael addition followed by an intramolecular aldol condensation 

 
** Fill in the mechanism: 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

* ​PRACTICE​: 

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Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

* ​KEY 
Refer to lecture notes for mechanisms. If you need help or have found any mistakes, e-mail me or come to my office 
hours​ (MON: 9 - 10:45 AM CHEM159 // TUES: 4:30 - 6:00 PM CHEM163K) 
CH 17 
1. 4-hydroxy-2-pentanone 
2. 4-oxo-2-cyclohexene-1-carbaldehyde 

3.  
4. H2O, H2SO4, HgSO4 or hydroboration-oxidation 
5. 1) O3 2) S(CH3)2 3) HS(CH2)3SH, H+, ZnCl2, heat 4) H2, Raney-Ni 

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10. 1) PCC or Jones 2) NH2NH2, H2O, OH-, heat 
 
CH 18 

1.  
Nasiri CHE118B Final Study Guide 
Spring 2019 || S. Ly ​[email protected] 

2.  
3. 1) PCC or Jones 2) Br2, CH3COOH 3) NaHCO3 4) (CH3)2CuLi 5) CH3CH2Br 6) H2NCH3, H+ 

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