Nasiri CHE118B Midterm 2 Study Guide 

Spring 2019 || S. Ly ​sdly@ucdavis.edu  

CH 14: Extended Pi Systems 

→ ​ALLYLIC CARBONS 
R​2​C=CH-​C​H​3 
● Adjacent to a pi bond 
● Allylic system consists of 3 interacting p orbitals 
● Allylic carbon can be positively charged, negatively charged, or a radical--they are all stable 
** Find the number of pi electrons in each system and fill out the chart in order to explain their stability.  

 
● Allylic systems are also stable due to resonance 
** Draw the resonance structures for each allylic system above: 
 
 
 
 
 
 
 
 
 
 
 
● The stability of these allow allylic systems to react ​faster​ than other systems 
○ SN1/SN2 Rate: ​allylic ​> alkyl >>>> vinyl/alkynol 
○ Acidity: ​allylic ​> vinyl > alkyl 
○ Bond dissociation energy: vinyl > alkyl > ​allylic 
 
→ ​ALLYLIC CARBON SOLVOLYSIS (SN1) 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

 
● Two possible products can be formed: 
○ Kinetic product: ​major product with lower temperature and shorter reaction times 
■ Forms more quickly due to lower activation barrier 
■ Features the less substituted double bond (less stable alkene) 
○ Thermodynamic product: ​major product with higher temperature and long reaction time 
■ Has higher activation barrier but is overall more stable 
■ More substituted double bond (more stable alkene) 
** Fill in the mechanism for the reaction above. Make sure you show how each product gets formed. 
Hint: all the arrows should be reversible, since it’s an SN1 reaction. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
● SN2 reactions are also possible.  

 
 
→ FREE RADICAL HALOGENATION 
● Recall: FRH was achieved using X2, light, and heat.  
○ If we try using these reagents with our allylic system--then we get a competing reaction: 
halogenation of the double bond. 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

To prevent this, we need low concentrations of our halogen. This is achieved 

■
through using special reagents: 
● Adding Br: NBS 
● Adding Cl: NCS 
● Can have product mixtures if your starting material is not symmetrical 

 
** Fill in the mechanism for this reaction, and show how NBS is able to form low concentrations of Br.  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
→ ALLYLIC ANIONS 
● Remember: anions are mores table when they are less substituted (less electron pushers around 
them to make the negative charge even less stable) 

 
● Useful reaction to use in synthesis when you want to make longer C chains (these are applicable to 
any organometallics, not just allylic): 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

 
→ CONJUGATED DIENES 

 
● Conjugated dienes are particularly stable do to their extended pi system & resonance abilities 
● Can switch between two conformers w/o much energy (~3 kcal), but s-trans is more stable. 

 
● Synthesis: 
○ Review alkene synthesis reactions from MT1 material 
○ ​Heck reaction 

 
** Fill in mechanism below: 
 
 
 
 
 
 
 
 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

→ ELECTROPHILIC ADDITION OF CONJUGATED DIENES 

 
** Fill in the mechanism below. Make sure you show how each product gets formed: 
 
 
 
 
 
 
 
● 2 products are possible: kinetic (less subbed alkene) and thermodynamic (more subbed alkene). 
○ Again, determined by temperature and time. 
● Recall Markovnikov addition… H (electrophile) always bonds to a terminal carbon of the conjugated 
diene system. 
○ What if the two terminal carbons are not the same? >> electrophilic attack occurs on the 
end that makes the more stable allylic cation: 

 
 
→ DIELS-ALDER REACTION  

 
** Draw in the electron pushing arrows in the above reaction, and label the diene and dienophile. 
● D-A reaction is most successful when you have an ​electron rich diene​ + an ​electron poor 
dienophile 
○ Rich dienes have electron donating groups 
○ Poor dienophiles have electron withdrawing groups 

 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

● D-A rxn requires​ s-cis conformer 

○ Open chains can easily convert to s-cis and react, but cyclic dienes are “stuck” and cannot 
rotate its bonds to form an s-cis conformation 

 
STEREOCHEMISTRY: 
● Think of the groups on the diene as “outside” or “inside” groups: 
○ Outside and inside groups will remain trans to each other 
● You should view the dienophile simply as an alkene that may be cis or trans. 

 
● 2 possible products for D-A 
○ Heat -> ​kinetic (endo) 
○ Light (hv) -> ​thermodynamic (exo) 
● ENDO ADDITION: ​the outside groups on your diene will be cis to the bulky side of your 
dienophile. Equivalently, the inside groups on your diene will be trans to the bulky side of your 
dienophile. 
○ Exo addition is just the opposite of this; outside groups will be trans to bulky side 

 
 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

REGIOCHEMISTRY: 
● For regiochemistry, look at the ​2nd best resonance structure ​of the diene and dienophile 

 
● Then, align charges. 

 
● Some reactions are not regioselective! In that case, look out for product mixtures. 

 
 
 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

GENERAL STRATEGY: 
1. Determine regiochemistry using resonance structures and aligning the positive/negative charges. 
Not all rxns are regioselective. 
2. Draw your cyclohexene “base.”  
3. Add all the substituents from the diene, retaining stereochemistry.  
4. Look at your dienophile, determine the side that has more groups. Determine whether the rxn is 
exo or endo. Then add in your dienophile substituents according to the inside/outside trick.  
5. Make sure you have written “+ enantiomer” or “racemic” (unless the compound is meso) and also 
check that you have all the diastereomers, if there are any. 
 
● Intramolecular D-A: fill in the electron pushing arrows below 

 
● This reaction is able to proceed because sigma bonds are more stable than pi bonds. 
 
* ​PRACTICE 

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3.  
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

4.  

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Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

CH 15: Aromatic Compounds  

→ ​NAMING 
● As parent compound: ​benzene 
● As substituent: ​phenyl 
○ benzyl ​= C6H5CH2-  

 
● Naming priority: 
Benzoic acid > benzaldehyde > acetophenone > phenol > thiols > aniline > hydrocarbons 
** The above names are common names for benzene compounds. Draw them below: 
 
 
 
 
 
 
 
● Disubstituted benzenes: 
○ 1,2 - ​ortho 
○ 1,3 - ​meta 
○ 1,4 - ​para 
→ ​AROMATICITY 
● Criteria for aromaticity: 
○ Cyclic 
○ Conjugated pi system 
○ Every member of the ring has a p orbital 
○ Planar  
○ Huckel’s rule​: 4n + 2 = # pi electrons (n = integer 0, 1, 2…) 
■ If structure meets all the criteria except Huckel’s rule (n is not an integer), then it is 
anti-aromatic​. 

 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

● Aromatic systems are highly stable 

○ If possible, nonaromatic compounds will convert into aromatic compounds favorably 
○ Aromatic compounds are not very reactive 

 
Can you determine which side is more favorable? 
 
→ ​REACTIONS OF BENZENE 
● Benzene is very stable and doesn’t undergo the same reactions that alkenes would 
(dihalogenation, oxidation, etc…) 
● Benzene reactions all have similar mechs and undergo Electrophilic Aromatic Substitution (EAS) 
○ Adding electrophile, momentarily getting rid of aromaticity, and then undergoing 
elimination to regain aromaticity 

 
→ ​HALOGENATION 

 
** Fill in the mechanism for either reaction: 
 
 
 
 
 
 
 
 
 
 
 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

→ ​NITRATION 

 
** Fill in the mechanism: 
 
 
 
 
 
 
 
 
 
 
 
 
 

 
→ ​SULFONATION 

 
** Fill in the mechanism: 
 
 
 
 
 
 
 
 
 
 
 
 
 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

→ ​FRIEDEL-CRAFTS ALKYLATION 

 
** Fill in the mechanism: 
 
 
 
 
 
 
 
 
 
 
 
● Requires a base and acid to form an electrophile.  
● Electrophiles can be formed from.. RX, ROH, RCH=CH2 

 
● LIMITATIONS:  
○ Electrophiles can NOT be formed from C=CX, C​≡​CX, or halobenzenes 
○ Rearrangement 

 
○ Polysubstitution: adding alkyl groups makes the ring more electron rich and therefore 
more prone to further reactions 

 
○ Can not do reaction with benzenes containing meta-directing groups or NR2 (ch16) 
 
 
 
 
 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

→ ​FRIEDEL-CRAFTS ACYLATION 

 
● Prevents rearrangement 
● LIMITATIONS:​ can not do reaction with benzenes containing meta-directing groups or NR2 (ch16) 
** Fill in the mechanism for either route 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
→ ​DE-OXYGENATION (CLEMMENSENS REDUCTION) 

 
● Very often paired with FC-acylation to remove the oxygen. 
 
 
 
 
 
 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

CH 16: Substituent Effects  

→ ​ACTIVATING AND DEACTIVATING GROUPS 
● ACTIVATING GROUPS: ​ortho/para directing (+ halogens) 
○ Most activating:​ NR2, NHR, NH2, OH (have lone pairs; donate e- thru resonance) 
■ NH2 and OH are so activating that they often have to be ​protected ​to prevent 
polysubstitution  
○ Medium activating:​ NHCOR, OR 
○ Weak activating: ​CnHm (alkyl groups are weakly electron donating) 
● DEACTIVATING GROUPS:​ meta directing / ortho/para deactivating (except halogens) 
○ Most deactivating:​ NO2, RN4+ 
○ Very strong deactivating: ​CF3 
○ Strong deactivating: ​R2CO, SO3H, CN 
○ Weak deactivating:​ halogens 
● Why is this the case? 
○ Draw out all the resonance structures for aniline below: 
 
 
 
 
 
 
● You should have found that the lone pair of electrons is only on the ortho/para positions, making 
those positions more electron rich, more reactive, and therefore activated 
● Now draw out all the resonance structures for nitrobenzene: 
 
 
 
 
 
 
● You should have found that the positive charge is only on the ortho/para positions, making them 
more electron poor, less reactive, and therefore deactivated. The meta position is now the most 
reactive position. 
→ ​APPROACHING BENZENE RXNS 
1. Look at all the substituents on your ring. Circle the MOST activating group (or least 
deactivating)--that will be your directing group 
2. Now circle the possible positions where you can add your new substituent based on your directing 
group (does it direct o/p or m?) 
3. Check for steric hindrance. Adding a group between two substituents will result in a low yield.  
4. Draw all possible products. 
 
 
 
 
 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

Some examples: 

 
● Recall the limitations to F-C reactions: they don’t work with​ meta directing group​s--the ring 
becomes too deactivated.  
○ Also ineffective with NH2/NR2 groups: acid base reaction occurs. Prevent this by 
protecting your NH2 group 

 
→ ​PROTECTING GROUPS 
● In synthesis, you often will need to use protecting groups to block certain positions.  
● The most common one is using sulfonation to block para positions, since it can easily be removed 
(recall its mechanism has all reversible arrows).  
○ It’s a pretty big group so it prefers to add para over ortho. 

 
● With that being said, be aware that the order in which you add substituents to a benzene ring 
matters! Look over your synthesis when you’re done and make sure it makes sense while 
considering deactivating/activating effects, etc. 
 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

* ​PRACTICE 
 

1. Name ____________________________________ 

2. Name _______________________________________ 

3.  

4.  

5.  
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

6.  

7.  

8.  
9. Circle the aromatic compounds: 

 
 
 
 
 
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

* ​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 14 

1.  

2.  

3.  
4. NBS, hv 
5. 1) C4H9Li 2) CH3CHO 3) H3O+ 

6.  

7.  

8.  

9.  

10.  
Nasiri CHE118B Midterm 2 Study Guide 
Spring 2019 || S. Ly ​sdly@ucdavis.edu  

 
CH 15/16 
1. 3-ethyl-5-hydroxybenzoic acid 
2. (3R)-2-benzyl-3-chlorobutan-1-ol 
3. 1) Sn, Hcl 2) H2SO4, SO3, heat 3) MCPBA 

4.  

5.  

6.  
7. NR 

8.  

9.