13.1 Structure and Properties of Alcohols!

Chapter 13. Alcohols and Phenols! ! "

Junha Jeon !
Department of Chemistry ! University of Texas at Arlington ! Arlington, Texas 76019 ! " ! Chem 2321, Fall 13 !

Nomenclature!
" Alcohols are named using the same procedure we used in Chapter 4 to name alkanes with minor modications:! 1." 2." 3." 4." 5." Identify the parent chain, which should include the carbon that the OH is attached to.! Identify and name the substituents.! Assign a locant to each substituent. Give the carbon that the OH is attached to the lowest number possible.! List the numbered substituents before the parent name in alphabetical order. Ignore prexes (except iso) when ordering alphabetically.! The OH locant is placed either just before the parent # name or just before the -ol sufx.!

Nomenclature!
" Alcohols are named using the same procedure we used in Chapter 4 to name alkanes with minor modications:! 1." 2." 3." 4." 5." Identify the parent chain, which should include the carbon that the OH is attached to! Identify and name the substituents.! Assign a locant to each substituent. Give the carbon that the OH is attached to the lowest number possible.! List the numbered substituents before the parent name in alphabetical order. Ignore prexes (except iso) when ordering alphabetically.! The OH locant is placed either just before the parent # name or just before the -ol sufx.!

Nomenclature!

Nomenclature!

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Nomenclature!

Nomenclature!

Nomenclature!
For cyclic alcohols, the OH group should be on carbon 1, so often the locant is assumed and omitted.! !

Nomenclature!

Nomenclature!
When an OH group is attached to a benzene ring, the parent name is PHENOL.! !

Physical Properties!

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Acidity of Alcohols and Phenols!

Reagents for Deprotonating an Alcohol!

1. A strong base!

2. Alkali metals!

Factors Affecting the Acidity of Alcohols and Phenols!

1. Resonance!

Factors Affecting the Acidity of Alcohols and Phenols!

1. Resonance!

Factors Affecting the Acidity of Alcohols and Phenols!

1. Resonance!

Factors Affecting the Acidity of Alcohols and Phenols!

2. Induction!

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Factors Affecting the Acidity of Alcohols and Phenols!

3. Solvation effects!

Factors Affecting the Acidity of Alcohols and Phenols!

3. Solvation effects!

13.3 Preparation of Alcohols via Substitution or Addition Reactions!

Substitution Reactions!

Preparation of Alcohols via Substitution or Addition Reactions!

Substitution Reactions!

Preparation of Alcohols via Substitution or Addition Reactions!

Addition Reactions!

13.4 Preparation of Alcohols via Reduction!

" A third method to prepare alcohols is by the reduction of a carbonyl (C=O). !

"

Reductions involve a change in oxidation state.!

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Oxidation states are a method of electron bookkeeping.!

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Preparation of Alcohols via Reduction!

" A third method to prepare alcohols is by the reduction of a carbonyl (C=O). !

Preparation of Alcohols via Reduction!

" Oxidation states are a method of electron bookkeeping: Two methods!

"

Reductions involve a change in oxidation state.!

"

Oxidation states are a method of electron bookkeeping.!

"

For oxidation states, we imagine the bonds breaking heterolytically, and the electrons go to the more electronegative atom.!

Preparation of Alcohols via Reduction!

" Oxidation states are a method of electron bookkeeping: Two methods!

Preparation of Alcohols via Reduction!

" Oxidation states are a method of electron bookkeeping: Two methods!

"

For oxidation states, we imagine the bonds breaking heterolytically, and the electrons go to the more electronegative atom.!

"

For oxidation states, we imagine the bonds breaking heterolytically, and the electrons go to the more electronegative atom.!

Preparation of Alcohols via Reduction!

" Oxidation states are a method of electron bookkeeping: Two methods!

Preparation of Alcohols via Reduction!

" Calculate oxidation states:!

vs.!

"

For oxidation states, we imagine the bonds breaking heterolytically, and the electrons go to the more electronegative atom.!

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Reducing Agents!

Catalytic Hydrogenation: Catalysts Pt, Pd, Ni Yes, IRONMAN!!!

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Calculate oxidation states of the carbonyl carbon.! Is the reducing agent oxidized or reduced?!

Reducing Agents for a C=O double bond!

There are three reducing agents you should know:! 1. We have already seen how catalyzed hydrogenation can reduce alkenes. It can also work for carbonyls.!

Reducing Agents!
There are three reducing agents you should know:! Reagents that can donate a HYDRIDE are generally good reducing agents:! 2. Sodium borohydride!

"

Forceful conditions (high temperature and/or high pressure)!

Reducing Agents!
There are three reducing agents you should know:! Reagents that can donate a HYDRIDE are generally good reducing agents:! 2. Sodium borohydride!

Reducing Agents!
There are three reducing agents you should know:! Reagents that can donate a HYDRIDE are generally good reducing agents:! 3. Lithium Aluminum Hydride (LAH)! : LAH is signicantly more reactive that NaBH4.! !

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Reducing Agents!
There are three reducing agents you should know:! Reagents that can donate a HYDRIDE are generally good reducing agents:! 3. Lithium Aluminum Hydride (LAH)! : LAH is signicantly more reactive that NaBH4.! ! !

Reducing Agents!
There are three reducing agents you should know:! Reagents that can donate a HYDRIDE are generally good reducing agents:! 3. Lithium Aluminum Hydride (LAH)! : LAH is signicantly more reactive that NaBH4.!

Reducing Agents!
" HYDRIDE delivery agents will somewhat selectively reduce carbonyl compounds.! !

Reducing Agents!
" LAH is significantly more reactive that NaBH4. As a result, LAH is less selective. " LAH is strong enough to also reduce esters and carboxylic acids, whereas NaBH4 is generally not. !

Reducing Agents!
" LAH is significantly more reactive that NaBH4. As a result, LAH is less selective. " LAH is strong enough to also reduce esters and carboxylic acids, whereas NaBH4 is generally not. !

Reducing Agents!
" Mechanism!

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Reducing Agents!
" Mechanism!

Reducing Agents!
" Mechanism!

13.5 Preparation of Diols!

" Diols are named using the same method as alcohols, except the sufx, diol is used.!

Preparation of Diols!
" Reducing Agents!

" Common diols!

Preparation of Diols!
" Oxidizing Agents!

13.6 Preparation of Alcohols via Grignard Reagents!

" To form a Grignard reagents, an alkyl halide is treated with Mg metal.!

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Preparation of Alcohols via Grignard Reagents!

" To form a Grignard reagents, an alkyl halide is treated with Mg metal.!

Preparation of Alcohols via Grignard Reagents!

" The electronegativity difference between C (2.5) and Mg (1.3) is great enough that the bond has signicant ionic character.!

" "

The carbon atom is not able to effectively stabilize the negative charge it carries.! It act as an nucleophile.!

Preparation of Alcohols via Grignard Reagents!

" The electronegativity difference between C (2.5) and Mg (1.3) is great enough that the bond has signicant ionic character.!

Preparation of Alcohols via Grignard Reagents!

" "

The carbon atom is not able to effectively stabilize the negative charge it carries.! It act as an nucleophile.!

Preparation of Alcohols via Grignard Reagents!

Preparation of Alcohols via Grignard Reagents!

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Preparation of Alcohols via Grignard Reagents!

Preparation of Alcohols via Grignard Reagents!

Preparation of Alcohols via Grignard Reagents!

Preparation of Alcohols via Grignard Reagents!

Preparation of Alcohols via Grignard Reagents!

Protection of Alcohols!

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Protection of Alcohols!

Protection of Alcohols!
" " Evidence suggests that substitution at the Si atom occurs by an SN2 mechanism.! Because Si is much larger than C, it is more open to backside attack.!

Protection of Alcohols!

Protection of Alcohols!

13.9 Reactions of Alcohols: Substitution and Elimination Reactions!

Reactions of Alcohols: Substitution and Elimination Reactions!

via SN1!

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Reactions of Alcohols: Substitution and Elimination Reactions!

" For primary alcohols, the reaction occurs by an SN2.!!

Reactions of Alcohols: Substitution and Elimination Reactions!

" For primary alcohols, the reaction occurs by an SN2.!!

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The SN2 reaction also occurs with ZnCl2 as the reagent.!

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The SN2 reaction also occurs with ZnCl2 as the reagent.!

Reactions of Alcohols: Substitution and Elimination Reactions!

" For primary alcohols, the reaction occurs by an SN2.!!

Reactions of Alcohols: Substitution and Elimination Reactions!

" Converted into a better leaving groups such as a tosyl group.!

"

The SN2 reaction also occurs with ZnCl2 as the reagent.!

Reactions of Alcohols: Substitution and Elimination Reactions!

" Converted into a better leaving groups such as a tosyl group.!

Reactions of Alcohols: Substitution and Elimination Reactions!

" SOCl2 can also be used to convert an alcohol to an alkyl chloride.!

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Reactions of Alcohols: Substitution and Elimination Reactions!

" SOCl2 can also be used to convert an alcohol to an alkyl chloride.!

Reactions of Alcohols: Substitution and Elimination Reactions!

" PBr3 can also be used to convert an alcohol to an alkyl bromide.!

13.10 Reactions of Alcohols: Oxidation!

" Oxidation states of the carbons of the carbinol and ketone?!

Reactions of Alcohols: Oxidation!

" Oxidation of primary alcohols proceeds to aldehydes and subsequently to carboxylic acids!

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Reactions of Alcohols: Oxidation!

" Oxidation of secondary alcohols produces a ketone.!

Reactions of Alcohols: Oxidation!

" Tertiary alcohols generally do not undergo oxidation. !

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Reactions of Alcohols: Oxidation!

" Tertiary alcohols generally do not undergo oxidation. !

Reactions of Alcohols: Oxidation!

" The most common oxidizing agent, chromic acid: !

Reactions of Alcohols: Oxidation!

" The most common oxidizing agent, chromic acid: !

Reactions of Alcohols: Oxidation!

" The most common oxidizing agent, chromic acid: !

Reactions of Alcohols: Oxidation!

" When chromic acid reacts with an alcohol, there are two main steps:! 1. Activation of alcohol!

Reactions of Alcohols: Oxidation!

" When chromic acid reacts with an alcohol, there are two main steps:! 1. Activation of alcohol!

2. Elimination of activator!

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Reactions of Alcohols: Oxidation!

" Chromic acid will generally oxidize a primary alcohol to a carboxylic acid.!

Reactions of Alcohols: Oxidation!

" Chromic acid will generally oxidize a primary alcohol to a carboxylic acid.!

" PCC (pyridinium chlorochromate) can be used to stop at the aldehyde. !

" PCC (pyridinium chlorochromate) can be used to stop at the aldehyde. !

Reactions of Alcohols: Oxidation!

" Chromic acid will generally oxidize a primary alcohol to a carboxylic acid.!

Reactions of Alcohols: Oxidation!

" Both oxidizing agents will work with secondary alcohols.!

" PCC (pyridinium chlorochromate) can be used to stop at the aldehyde. !

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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.!

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.!

! " Yet, phenol is even more readily oxidized than primary or secondary alcohols.!

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CarbonCarbon Bond Formation!

" Carboncarbon bond formation is important in organic synthesis:!

CarbonCarbon Bond Formation via Alkylation of Terminal Alkynes!

" What other methods have we learned? !

CarbonCarbon Bond Formation!

Sequential CC Bond Formation/Oxidation!

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