Develop syntheses for the following compounds. As starting materials, you may use cyclopentanol, alcohols containing no more than four carbon atoms, and any common reagents and solvents.

(f)

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

(a) (R)-butan-2-ol + TsCl in pyridine

(b) (S)-2-butyl tosylate + NaBr

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

(c) cyclooctanol + NaOCl/HOAC

(d) cyclopentylmethanol + CrO₃·pyridine·HCl

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, including stereochemistry where appropriate.

(h) cyclooctylmethanol + CH₃CH₂MgBr

(i) potassium tert-butoxide + methyl iodide

(j) sodium methoxide + tert-butyl iodide

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

(k) cyclopentanol + H₂SO₄/heat

(l) product from (k) + OsO₄/H₂O₂, then HIO₄

(m) sodium ethoxide + 1-bromobutane

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

(n) sodium ethoxide + 2-methyl-2-bromobutane

(o) octan-1-ol + DMSO + oxalyl chloride

(p) 4-cyclopentylhexan-1-ol + DMP reagent

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

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.

d. 1-methylcyclopentanol

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.

(g) 2-methylcyclopentyl acetate

(h) 1-bromo-1-methylcyclopentane

In each case, show how you would synthesize the chloride, bromide, and iodide from the corresponding alcohol.

(a) 1-halobutane (halo = chloro, bromo, iodo)

(b) halocyclopentane

Show how you would accomplish the following synthetic conversions.

(a)

(b)

Show how you would accomplish the following synthetic conversions.

(c)

Show how you would accomplish the following synthetic conversions.

(d)

Predict the major products of dehydration catalyzed by sulfuric acid.

(a) hexan-1-ol

(b) hexan-2-ol

(c) pentan-3-ol

Predict the esterification products of the following acid/alcohol pairs.

(a) CH₃CH₂CH₂COOH + CH₃OH

(b) CH₃OH + HNO₃

(c) 2 CH₃CH₂OH + H₃PO₄

Predict the esterification products of the following acid/alcohol pairs.

(d)

(e)

Both cis- and trans-2-methylcyclohexanol undergo dehydration in warm sulfuric acid to give 1-methylcyclohexene as the major alkene product. These alcohols can also be converted to alkenes by tosylation using TsCl and pyridine, followed by elimination using KOC(CH₃)₃ as a strong base. Under these basic conditions, the tosylate of cis-2-methylcyclohexanol eliminates to give mostly 1-methylcyclohexene, but the tosylate of trans-2-methylcyclohexanol eliminates to give only 3-methylcyclohexene. Explain how this stereochemical difference in reactants controls a regiochemical difference in the products of the basic elimination, but not in the acid-catalyzed elimination.

Show how you would convert (S)-hexan-2-ol to

(a) (S)-2-chlorohexane.

(b) (R)-2-bromohexane.

(c) (R)-hexan-2-ol.

Show how you would make each compound, beginning with an alcohol of your choice.

(d)

(e)

(f)

Show how you would make each compound, beginning with an alcohol of your choice.

(g)

(h)

Predict the major products (including stereochemistry) when cis-3-methylcyclohexanol reacts with the following reagents.

(a) PBr₃

(b) SOCl₂ 

(c) Lucas reagent

Predict the major products (including stereochemistry) when cis-3-methylcyclohexanol reacts with the following reagents.

(d) concentrated HBr

(e) TsCl/pyridine, then NaBr

The compound shown below has three different types of OH groups, all with different acidities. Show the structure produced after this compound is treated with different amounts of NaH followed by a methylating reagent. Add a brief explanation.

(a) 1 equivalent of NaH, followed by 1 equivalent of CH₃I and heat

(b) 2 equivalents of NaH, followed by 2 equivalents of CH₃I and heat

(c) 3 equivalents of NaH, followed by 3 equivalents of CH₃I and heat

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.

Give the structures of the intermediates and products V through Z.

Under acid catalysis, tetrahydrofurfuryl alcohol reacts to give surprisingly good yields of dihydropyran. Propose a mechanism to explain this useful synthesis.

Propose mechanisms for the following reactions. In most cases, more products are formed than are shown here. You only need to explain the formation of the products shown, however.

(a)

Propose mechanisms for the following reactions. In most cases, more products are formed than are shown here. You only need to explain the formation of the products shown, however.

(b)

Propose mechanisms for the following reactions. In most cases, more products are formed than are shown here. You only need to explain the formation of the products shown, however.

(c)