Reactions of Alcohols

You may use these summaries and problems but you may NOT download them for use at another site, nor may you charge for access to them. Copyright Linda M. Sweeting 1997

The following example reactions are organized by type, with references to text chapters. Links within these summaries (which may show up as boxes around reagents) will provide further information about the reagents and their other reactions. Return to Graphical Reaction Summary menu for other functional group choices.

Reactions which break the OH bond

As weak acids

+ 1/2 H2
Other reagents: any base stronger than alkoxide, such as H-, NH2-, CH3MgBr, CH3Li (H2 not formed)
Reference McMurry 17.3, Fessenden 7.2, Schmid 11.15

As nucleophiles with Carboxylic Acids

+ H2O
Mechanism!
Reference: McMurry 21.3, Fessenden 7.7A, 14.6, Schmid 15.11
To other syntheses of esters

As nucleophiles with Carboxylic Acid Chlorides

+ HCl
Other reagents: sulfonic acid (sulfonyl) chlorides
Mechanism!
Reference McMurry 21.3, Fessenden 7.7B, 15.3, Schmid 16.5
To other syntheses of esters

Intermediate is ROSOCl, the half-ester; the reaction is stereospecific.
The reaction of PCl3 and PBr3 is similar; no rearrangements.
McMurry 11.16, 17.7, Fessenden 7.5, Schmid 11.17

As nucleophiles with Esters

+
Other reagents: any other alcohols
Mechanism!
Reference Fessenden 15.5C, Schmid 16.9

As nucleophiles with sp3 carbon


Mechanism!; SN2 reaction.
Note that more substituted halides will undergo the E2 elimination instead.
McMurry 11.15, 18.3, Fessenden 5.3, Schmid 13.8C

Reactions which break the CO bond

Nucleophilic Substitution


Mechanism!; SN2; other reagents HCl, HI, H2SO4
Reference McMurry 10.7, 17.7, Fessenden 7.4, Schmid 11.17, 12.9

Substitution and Elimination

+
Mechanism!; SN1 and E1; other reagents HCl, HI
Reference McMurry 10.7, 11.10, 17.7, Fessenden 7.4-7.6, Schmid 11.17, 12.10, 12.11, 12.16

Elimination

+ H2O
Mechanism!: E1; other reagents H3PO4 (acid must be very concentrated).
McMurry 17.3, 17.7, Fessenden 7.6

Oxidation


Other reagents: K2Cr2O7 + H2SO4 or CrO3 + H2SO4 or KMnO4 + OH- or KMnO4 + H3O+
Reference McMurry 17.8, Fessenden 7.8, Schmid 11.18

Note that all aqueous chromium reagents and permanganate oxidize primary aldehydes to carboxylic acids and cannot be used for this reaction; selective reagents are needed.
Reference McMurry 17.8, Fessenden 7.8, Schmid 11.18
+ MnO2
Other reagents: H2CrO4 or K2Cr2O7 + H2SO4 or CrO3 + H2SO4
Reference McMurry 17.8, Fessenden 7.8, Schmid 11.18, 15.5
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Last update Nov 1, 1998