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Chapter 11. Alcohols & Ethers. Structure & Nomenclature. Alcohols have a hydroxyl (–OH) group bonded to a saturated carbon atom (sp 3 hybridized). 1 o. 2 o. 3 o. Ethanol. 2-Propanol (isopropyl alcohol). 2-Methyl- 2-propanol ( tert -butyl alcohol). Phenols

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Chapter 11

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Chapter 11
Chapter 11

Alcohols & Ethers


Chapter 11

Structure & Nomenclature

  • Alcohols have a hydroxyl (–OH) group bonded to a saturated carbon atom (sp3 hybridized)

1o

2o

3o

Ethanol

2-Propanol

(isopropyl

alcohol)

2-Methyl-

2-propanol

(tert-butyl alcohol)


Chapter 11

  • Phenols

    • Compounds that have a hydroxyl group attached directly to a benzene ring


Chapter 11

  • Ethers

    • The oxygen atom of an ether is bonded to two carbon atoms


1a nomenclature of alcohols
1A.Nomenclature of Alcohols

  • Rules of naming alcohols

    • Identify the longest carbon chain that includes the carbon to which the –OH group is attached

    • Use the lowest number for the carbon to which the –OH group is attached

    • Alcohol as parent (suffix)

      • ending with “ol”



Chapter 11

3-Propyl-2-heptanol


1b nomenclature of ethers
1B.Nomenclature of Ethers

  • Rules of naming ethers

    • Similar to those with alkyl halides

      • CH3O–Methoxy

      • CH3CH2O–Ethoxy

  • Example



Chapter 11

Physical Properties ofAlcohols and Ethers


Chapter 11

  • Water solubility of ethers and alcohols

    • Both ethers and alcohols are able to form hydrogen bonds with water

    • Ethers have solubilities in water that are similar to those of alcohols of the same molecular weight and that are very different from those of hydrocarbons

    • The solubility of alcohols in water gradually decreases as the hydrocarbon portion of the molecule lengthens; long-chain alcohols are more “alkane-like” and are, therefore, less like water


Chapter 11

Name

Formula

mp

(oC)

bp (oC)

(1 atm)


Chapter 11

Name

Formula

mp

(oC)

bp (oC)

(1 atm)

*

* Water solubility (g/100 mL H2O)


Chapter 11

4. Synthesis of Alcohols from Alkenes

  • Acid-catalyzed Hydration of Alkenes



Chapter 11

H+, H2O or

1. Hg(OAc)2, H2O, THF

2. NaBH4, NaOH

Markovnikov regioselectivity

1. BH3• THF

2. H2O2, NaOH

Anti-Markovnikov regioselectivity


Chapter 11

Reactions of Alcohols

  • The reactions of alcohols have mainly to do with the following

    • The oxygen atom of the –OH group is nucleophilic and weakly basic

    • The hydrogen atom of the –OH group is weakly acidic

    • The –OH group can be converted to a leaving group so as to allow substitution or elimination reactions


Chapter 11

C–O & O–H bonds of an

alcohol are polarized

  • Protonation of the alcohol converts a poor leaving group (OH⊖) into a good one (H2O)


Chapter 11

The protonated –OH

group is a good leaving

group (H2O)


Chapter 11

Alcohols as Acids possible

  • Alcohols have acidities similar to that of water


Chapter 11

H2O & alcohols are the

strongest acids in this series

Increasing acidity

  • Relative Basicity

OH⊖ is the weakest

acid in this series

Increasing basicity


Chapter 11

Conversion of Alcohols into possibleAlkyl Halides

  • HX (X = Cl, Br, I)

  • PBr3

  • SOCl2


Chapter 11


Chapter 11

Alkyl Halides from the Reaction of possibleAlcohols with Hydrogen Halides

  • The order of reactivity of alcohols

    • 3o

  • The order of reactivity of the hydrogen halides

    • HI > HBr > HCl (HF is generally unreactive)

> 2o

> 1o

< methyl


Chapter 11

OH possible⊖ is a poor

leaving group

H3O⊕ is a good

leaving group


Chapter 11

Alkyl Halides from the Reaction possibleof Alcohols with PBr3 or SOCl2

  • Reaction of alcohols with PBr3

  • The reaction does not involve the formation of a carbocation and usually occurs without rearrangement of the carbon skeleton (especially if the temperature is kept below 0°C)


Chapter 11


Chapter 11

  • Reaction of alcohols with SOCl possible2

    • SOCl2 converts 1o and 2o alcohols to alkyl chlorides

    • As with PBr3, the reaction does not involve the formation of a carbocation and usually occurs without rearrangement of the carbon skeleton (especially if the temperature is kept below 0°C)

    • Pyridine (C5H5N) is often included to promote the reaction


Chapter 11


Chapter 11

Cl⊖


Chapter 11

Tosylates, Mesylates, & Triflates: possibleLeaving Group Derivatives of Alcohols


Chapter 11

  • Thus we need to convert the OH⊖ to a better leaving group first


Chapter 11

(methane sulfonyl chloride)


Chapter 11

(p-toluene sulfonyl chloride)


Chapter 11

  • S and they can be prepared easily from an alcoholN2 displacement of the mesylate or tosylate with a nucleophile is possible


Chapter 11

  • Example and they can be prepared easily from an alcohol

Retention of

configuration

Inversion of

configuration


Chapter 11

  • Example and they can be prepared easily from an alcohol

Retention of

configuration

Inversion of

configuration


Chapter 11

Synthesis of Ethers and they can be prepared easily from an alcohol

11A. Ethers by IntermolecularDehydration of Alcohols


Chapter 11

  • Mechanism and they can be prepared easily from an alcohol

  • This method is only good for synthesis of symmetrical ethers


Chapter 11

1o alcohols

Mixture

of ethers


Chapter 11

  • Exception and they can be prepared easily from an alcohol


Chapter 11

11B. and they can be prepared easily from an alcoholThe Williamson Synthesis of Ethers

  • Via SN2 reaction, thus R is limited to 1o (but R' can be 1o, 2o or 3o)


Chapter 11

  • Example 1 and they can be prepared easily from an alcohol


Chapter 11

  • Example 2 and they can be prepared easily from an alcohol


Chapter 11

  • Example 3 and they can be prepared easily from an alcohol

  • However


Chapter 11

11C. and they can be prepared easily from an alcoholSynthesis of Ethers by Alkoxy-mercuration–Demercuration

Markovnikov regioselectivity


Chapter 11

  • Example and they can be prepared easily from an alcohol


Chapter 11

11D. and they can be prepared easily from an alcoholtert-Butyl Ethers by Alkylationof Alcohols:Protecting Groups

  • A tert-butyl ether can be used to “protect” the hydroxyl group of a 1o alcohol while another reaction is carried out on some other part of the molecule

  • A tert-butyl protecting group can be removed easily by treating the ether with dilute aqueous acid


Chapter 11

  • Example and they can be prepared easily from an alcohol


Chapter 11

(Not Formed)

  • Since Grignard reagents are basic and alcohols contain acidic proton


Chapter 11

tert-butyl protected alcohol

deprotonation


Chapter 11

Reactions of Ethers and they can be prepared easily from an alcohol

  • Dialkyl ethers react with very few reagents other than acids


Chapter 11

12A. and they can be prepared easily from an alcoholCleavage of Ethers

  • Heating dialkyl ethers with very strong acids (HI, HBr, and H2SO4) causes them to undergo reactions in which the carbon–oxygen bond breaks

Cleavage of an ether


Chapter 11

  • Mechanism and they can be prepared easily from an alcohol


Chapter 11

Epoxides and they can be prepared easily from an alcohol

  • Epoxide (oxirane)

    • A 3-membered ring containing an oxygen


Chapter 11

13A. and they can be prepared easily from an alcoholSynthesis of Epoxides:Epoxidation

  • Electrophilic epoxidation


Chapter 11

  • Common peracids


Chapter 11

13B. and they can be prepared easily from an alcoholStereochemistry of Epoxidation

  • Addition of peroxy acid across a C=C bond

  • A stereospecific syn (cis) addition


Chapter 11

Reactions of Epoxides and they can be prepared easily from an alcohol

  • The highly strained three-membered ring of epoxides makes them much more reactive toward nucleophilic substitution than other ethers


Chapter 11


Chapter 11


Chapter 11

1o carbon atom is

less hindered


Chapter 11

  • In the and they can be prepared easily from an alcoholacid-catalyzed ring opening of an unsymmetrical epoxide the nucleophile attacks primarily at the more substituted carbon atom

This carbon resembles a 3o carbocation


Chapter 11

Anti 1,2-Dihydroxylation of and they can be prepared easily from an alcoholAlkenes via Epoxides

  • Synthesis of 1,2-diols


Chapter 11

  • Anti and they can be prepared easily from an alcohol-Dihydroxylation

    • A 2-step procedure via ring-opening of epoxides


Chapter 11

Crown Ethers and they can be prepared easily from an alcohol

  • Crown ethers are heterocycles containing many oxygens

  • They are able to transport ionic compounds in organic solvents – phase transfer agent


Chapter 11

  • Crown ether names: and they can be prepared easily from an alcoholx-crown-y

    • x = ring size

    • y = number of oxygen


Chapter 11



Chapter 11

Summary of Reactions of transportAlkenes, Alcohols, and Ethers

  • Synthesis of alcohols





Chapter 11

  • Cleavage reaction of ethers


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