1. 13.8 Preparation of Phenols
2 million tons of phenol is produced industrially yearly
Acetone is a useful byproduct
Phenol is a precursor in many chemical syntheses
Pharmaceuticals
Polymers
Adhesives
Food preservatives, etc.
Copyright 2012 John Wiley & Sons, Inc.

2. 13.9 Reactions of Alcohols Recall this SN1 reaction from section 7.5
For primary alcohols, the reaction occurs by an SN2
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3. 13.9 Reactions of Alcohols
The SN2 reaction also occurs with ZnCl2 as the reagent
Recall from section 7.8 that the –OH group can be converted into a better leaving groups such as a tosyl group
Copyright 2012 John Wiley & Sons, Inc.

4. 13.9 Reactions of Alcohols
SOCl2 can also be used to convert an alcohol to an alkyl chloride
Copyright 2012 John Wiley & Sons, Inc.

5. 13.9 Reactions of Alcohols
PBr3 can also be used to convert an alcohol to an alkyl bromide
Note that the last step of the SOCl2 and PBr3 mechanisms are SN2
Practice with SkillBuilder 13.6
Copyright 2012 John Wiley & Sons, Inc.

6. 13.9 Reactions of Alcohols
Fill in the necessary reagents for the conversions below
Copyright 2012 John Wiley & Sons, Inc.

7. 13.9 E1 and E2 Reactions of Alcohols
In section 8.9, we saw that an acid (with a non-nucleophilic conjugate base) can promote E1
Why is E2 unlikely?
Recall that the reaction generally produces the more substituted alkene product
Copyright 2012 John Wiley & Sons, Inc.

8. 13.9 E1 and E2 Reactions of Alcohols
If the alcohol is converted into a better leaving group, then a strong base can be used to promote E2
E2 reactions do not involve rearrangements. WHY?
When applicable, E2 reactions also produce the more substituted product
Practice with conceptual checkpoint 13.21
Copyright 2012 John Wiley & Sons, Inc.

9. 13.10 Oxidation of Alcohols
We saw how alcohols can be formed by the reduction of a carbonyl
The reverse process is also possible with the right reagents
Copyright 2012 John Wiley & Sons, Inc.

10. 13.10 Oxidation of Alcohols
Oxidation of primary alcohols proceed to an aldehyde and subsequently to the carboxylic acid
Very few oxidizing reagents will stop at the aldehyde
Oxidation of secondary alcohols produces a ketone
Very few agents are capable of oxidizing the ketone
Copyright 2012 John Wiley & Sons, Inc.

11. 13.10 Oxidation of Alcohols
Tertiary alcohols generally do not undergo oxidation. WHY?
There are two main methods to produce the most common oxidizing agent, chromic acid
Copyright 2012 John Wiley & Sons, Inc.

12. 13.10 Oxidation of Alcohols
When chromic acid reacts with an alcohol, there are two main steps
Copyright 2012 John Wiley & Sons, Inc.

13. 13.10 Oxidation of Alcohols
Chromic acid will generally oxidize a primary alcohol to a carboxylic acid
PCC (pyridinium chlorochromate) can be used to stop at the aldehyde
Copyright 2012 John Wiley & Sons, Inc.

14. 13.10 Oxidation of Alcohols
PCC (pyridinium chlorochromate) is generally used with methylene chloride as the solvent
Both oxidizing agents will work with secondary alcohols
Practice with SkillBuilder 13.7
Copyright 2012 John Wiley & Sons, Inc.

15. 13.10 Oxidation of Alcohols
Predict the product for the following reaction
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16. 13.11 Biological Redox Reactions
Nature employs reducing and oxidizing agents
They are generally complex and selective. WHY?
NADH is one such reducing agent
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17. 13.11 Biological Redox Reactions
The reactive site of NADH acts as a hydride delivery agent
This is one way nature
converts carbonyls into
alcohols
Why is an enzyme required?
Copyright 2012 John Wiley & Sons, Inc.

18. 13.11 Biological Redox Reactions
NAD+ can undergo the reverse process
The NADH / NAD+
interconversion plays a
big role in metabolism
Copyright 2012 John Wiley & Sons, Inc.

19. 13.12 Oxidation of Phenol
Recall that tertiary alcohols do not undergo oxidation, because they lack an alpha proton
You might expect phenol to be similarly unreactive
Yet, phenol is even more readily oxidized than primary or secondary alcohols
Copyright 2012 John Wiley & Sons, Inc.

20. 13.12 Oxidation of Phenol
Phenol oxidizes to form benzoquinone, which in turn can be reduced to hydroquinone
Quinones are found everywhere in nature
They are ubiquitous
Copyright 2012 John Wiley & Sons, Inc.

21. 13.13 Synthetic Strategies
Recall some functional group conversions we learned
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22. 13.13 Synthetic Strategies
Classify the functional groups based on oxidation state
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23. 13.13 Synthetic Strategies
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24. 13.13 Synthetic Strategies
Give necessary reagents for the following conversions
Practice with SkillBuilder 13.8
Copyright 2012 John Wiley & Sons, Inc.

25. 13.13 Synthetic Strategies
Recall the C-C bond forming reactions we learned
Copyright 2012 John Wiley & Sons, Inc.

26. 13.13 Synthetic Strategies
What if you want to convert an aldehyde into a ketone?
What reagents are needed for the following conversion?
Practice with conceptual checkpoint and SkillBuilder 13.9
Copyright 2012 John Wiley & Sons, Inc.

27. Study Guide for Sections 13.8-13.13
DAY 6, Terms to know:
Sections PCC, benzoquinone, hydroquinone,
DAY 6, Specific outcomes and skills that may be tested on exam 1:
Sections
Given products and reactant(s), be able to choose appropriate reagents for any of the reactions discussed that alcohols undergo
Given a specific alcohol and specific reagents, be able to predict the products of the reaction and draw a complete mechanism for any of the reaction we discussed
Be able to solve 1, 2, or 3 step syntheses involving any of the reactions discussed up to this point
Given some reagents and/or intermediates, be able to solve syntheses longer than 3 steps
Be able to explain regio- and stereo- outcomes predicted in syntheses
Be able to perform a retrosynthetic analysis to design a synthesis for a specific product

28. Extra Practice Problems for Sections 13.8-13.13
Complete these problems outside of class until you are confident you have learned the SKILLS in this section outlined on the study guide and we will review some of them next class period a, b, c, and e b, d-f

29. Day 7: EXAM 1 Prep for Day 8 Must Watch videos: Other helpful videos:
(naming ethers, Khan)
(ethers, FLC)
(epoxides, FLC)
(properties of ethers, Khan)
(cleavage of ethers, Khan)
(naming cyclic ethers and epoxides, Khan)
Other helpful videos:
(ether synthesis, moballer12)
(naming ethers, Leah)
(ethers, UC-Irvine) start 20 minutes in.
(alcohols, UC-Irvine) start 12 minutes in.
(alcohols, UC-Irvine) start 14 minutes in.
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