Chapter 11: Q30P (page 572)
Predict the products formed by periodic acid cleavage of the following diols
(a) 
(b) 
(c) 
(d) 
Short Answer
(a) 
(b)
(c)
(d) 
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Chapter 11: Q30P (page 572)
Predict the products formed by periodic acid cleavage of the following diols
(a) 
(b) 
(c) 
(d) 
(a) 
(b)
(c)
(d) 
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Compound A is an optically active alcohol. Treatment with chromic acid converts A into a ketone, B. In a separate reaction, A is treated with PBr3, converting A into compound C. Compound C is purified, and then it is allowed to react with magnesium in ether to give a Grignard reagent, D. Compound B is added to the resulting solution of the Grignard reagent. After hydrolysis of the initial product (E), this solution is found to contain 3,4 dimethylhexan-3-ol. Propose structures for compounds A, B, C, D, and E.

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.
(a)

(b)

(c)

(d)

The Williamson ether synthesis involves the displacement of an alkyl halide or tosylate by an alkoxide ion. Would the synthesis shown be possible by making a tosylate and displacing it? If so, show the sequence of reactions. If not, explain why not and show an alternative synthesis that would be more likely to work.

When 1-cyclohexylethanol is treated with concentrated aqueous, the major product is 1-bromo-1-ethylcyclohexane.

(a)Propose a mechanism for this reaction.
(b) How would you convert 1-cyclohexylethanol to (1-bromoethyl)cyclohexane in good yield?

Predict the esterification products of the following acid/alcohol pairs.
(a) CH3CH2COOH + CH3OH
(b) CH3CH2OH + HNO3
(c) 2CH3CH2CH2OH + H3PO4
(d)

(e)

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