13. Alcohols and Carbonyl Compounds

Predict the products formed by periodic acid cleavage of the following diols.

(c)

(d)

Predict the major products of the following reactions, including stereochemistry where appropriate.

(c) cyclooctanol + NaOCl/HOAC

(d) cyclopentylmethanol + CrO₃·pyridine·HCl

Give the structure of the principal product(s) when each of the following alcohols reacts with (1) Na₂Cr₂O₇/H₂SO₄, (2) PCC

c. 4-hydroxydecanal

Give the structure of the principal product(s) when each of the following alcohols reacts with (3) DMP, and (4) 1 equiv NaOCl-TEMPO.

c. 4-hydroxydecanal

Predict the major products of the following reactions, including stereochemistry where appropriate.

(e) cyclopentylmethanol + Na₂Cr₂O₇/H₂SO₄

(f) cyclopentanol + HCl/ZnCl₂

(g) n-butanol + HBr

Predict the major products of the following reactions.

(a)

Predict the products of the reactions of the following compounds with:

1. chromic acid or excess sodium hypochlorite with acetic acid.

2. PCC or NaOCl (1 equivalent) with TEMPO.

d. cyclohexanone

Predict the products of the reactions of the following compounds with:

1. chromic acid or excess sodium hypochlorite with acetic acid.

2. PCC or NaOCl (1 equivalent) with TEMPO.

e. cyclohexane

Predict the products of the reactions of the following compounds with:

1. chromic acid or excess sodium hypochlorite with acetic acid.

2. PCC or NaOCl (1 equivalent) with TEMPO.

f. 1-phenylpropan-1-ol

Give the structure of the principal product(s) when each of the following alcohols reacts with (1) Na₂Cr₂O₇/H₂SO₄, (2) PCC

d. 1-methylcyclohexan-1,4-diol

Give the structure of the principal product(s) when each of the following alcohols reacts with (3) DMP and (4) 1 equiv NaOCl-TEMPO.

d. 1-methylcyclohexan-1,4-diol

Under normal circumstances, tertiary alcohols are not oxidized. However, when the tertiary alcohol is allylic, it can undergo a migration of the double bond (called an allylic shift) and subsequent oxidation of the alcohol. A particularly effective reagent for this reaction is Bobbitt's reagent, similar to TEMPO used in many oxidations. (M. Shibuya et al., J. Org. Chem., 2008, 73, 4750.)

Show the expected product when each of these 3° allylic alcohols is oxidized by Bobbitt’s reagent

(c)

(d)

Predict the products you expect when the following starting material undergoes oxidation with an excess of each of the reagents shown below.

d. DMSO and oxalyl chloride

e. DMP (periodinane) reagent

A chronic alcoholic requires a much larger dose of ethanol as an antidote to methanol poisoning than does a nonalcoholic patient. Suggest a reason why a larger dose of the competitive inhibitor is required for an alcoholic.

Show how you would convert 2-methylcyclopentanol to the following products. Any of these products may be used as the reactant in any subsequent part of this problem.

a. 1-methylcyclopentene

b. 2-methylcyclopentyl tosylate

c. 2-methylcyclopentanone