A formate ester, such as ethyl formate, reacts with an excess of a Grignard reagent to give (after protonation) secondary alcohols with two identical alkyl groups.

(a) Propose a mechanism to show how the reaction of ethyl formate with an excess of allylmagnesium bromide gives, after protonation, hepta-1,6-dien-4-ol.

A formate ester, such as ethyl formate, reacts with an excess of a Grignard reagent to give (after protonation) secondary alcohols with two identical alkyl groups.

(b) Show how you would use reactions of Grignard reagents with ethyl formate to synthesize the following secondary alcohols.

(i) pentan-3-ol

(ii) diphenylmethanol

(iii) trans,trans-nona-2,7-dien-5-ol

Show how you would synthesize the following alcohol by adding Grignard reagents to ethylene oxide.

(a) 2-phenylethanol

Show how you would synthesize the following alcohol by adding Grignard reagents to ethylene oxide.

(c)

Acetylide ions also add to ethylene oxide much like Grignard and organolithium reagents. Predict the products obtained by adding the following acetylide ions to ethylene oxide, followed by a dilute acid workup.

(a) HC≡C:^–

(b) CH₃CH₂–C≡C:^–

Show how you would synthesize the following compound from alkyl halides, vinyl halides, and aryl halides containing no more than six carbon atoms.

(a) octane

Show how you would synthesize the following compound from alkyl halides, vinyl halides, and aryl halides containing no more than six carbon atoms.

(c) trans-oct-3-ene

Show how you would synthesize the following compound from alkyl halides, vinyl halides, and aryl halides containing no more than six carbon atoms.

(d) cyclopentyl propyl ketone

Predict the products of the following reactions.

(a) sec-butylmagnesium iodide + D₂O

(b) n-butyllithium + CH₃CH₂OH

(c) isobutylmagnesium bromide + but-1-yne

Predict the products of the following reactions.

(d)

(e)

Point out the flaws in the following incorrect Grignard syntheses.

(a)

Point out the flaws in the following incorrect Grignard syntheses.

(b)

Point out the flaws in the following incorrect Grignard syntheses.

(c)

(d)

Predict the products you would expect from the reaction of NaBH₄ with the following compounds. You may assume that these reactions take place in methanol as the solvent.

(a) CH₃–(CH₂)₈–CHO

Predict the products you would expect from the reaction of NaBH₄ with the following compounds. You may assume that these reactions take place in methanol as the solvent.

(c) Ph-COOH

Predict the products you would expect from the reaction of NaBH₄ with the following compounds. You may assume that these reactions take place in methanol as the solvent.

(d)

Predict the products you would expect from the reaction of NaBH₄ with the following compounds. You may assume that these reactions take place in methanol as the solvent.

(e)

Predict the products you would expect from the reaction of NaBH₄ with the following compounds. You may assume that these reactions take place in methanol as the solvent.

(f)

Predict the products you would expect from the reaction of LiAlH₄ followed by hydrolysis with the following compounds. You may assume that these reactions take place in methanol as the solvent.

(a) CH₃–(CH₂)₈–CHO

Predict the products you would expect from the reaction of LiALH₄ followed by hydrolysis with the following compounds. You may assume that these reactions take place in methanol as the solvent.

(c) Ph-COOH

Predict the products you would expect from the reaction of LiAlH₄ followed by hydrolysis with the following compounds. You may assume that these reactions take place in methanol as the solvent.

(d)

Predict the products you would expect from the reaction of LiAlH₄ followed by hydrolysis with the following compounds. You may assume that these reactions take place in methanol as the solvent.

(e)

Show how you would synthesize the following alcohol by reducing appropriate carbonyl compound.

a. heptan-1-ol

Show how you would synthesize the following alcohol by reducing appropriate carbonyl compound.

c. 2-methylhexan-3-ol

Show how you would synthesize the following alcohol by reducing appropriate carbonyl compound.

(d)

Arrange the following compounds in order of decreasing acidity.

CH₃COOH, CH₃OH, CH₃CH₃, CH₃SO₃H, CH₃NH₂, CH₃SH, CH₃C≡CH

Give IUPAC names for the following compounds.

Authentic skunk spray has become valuable for use in scent-masking products. Show how you would synthesize the major component of skunk spray (3-methylbutane-1-thiol and but-2-ene-1-thiol) from any of the readily available butene or from buta-1,3-diene.

Give a systematic (IUPAC) name for each alcohol. Classify each as primary, secondary, or tertiary.

(f)

(g)

Give systematic (IUPAC) names for the following diols and phenols.

(a)

(b)