13. Alcohols and Carbonyl Compounds

Point out the flaws in the following incorrect Grignard syntheses.

(b)

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.

Show how to make these deuterium-labeled compounds, using CD₃MgBr and D₂O as your sources of deuterium, and any non-deuterated starting materials you wish.

d. Ph(CD₃)₂COD

Show how to make these deuterium-labeled compounds, using CD₃MgBr and D₂O as your sources of deuterium, and any non-deuterated starting materials you wish.

b. CH₃C(OH)(CD₃)₂

Show how to make these deuterium-labeled compounds, using CD₃MgBr and D₂O as your sources of deuterium, and any non-deuterated starting materials you wish.

a. CH₃CH(OD)CD₃

Show how you would synthesize the following:

a. 2-phenylethanol by the addition of formaldehyde to a suitable Grignard reagent

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 alcohol by adding Grignard reagents to ethylene oxide.

(a) 2-phenylethanol

Show how you would add Grignard reagent to acid chloride or ester to synthesize the following alcohols.

a. Ph₃C–OH

Show how you would synthesize following tertiary alcohol by adding an appropriate Grignard reagent to a ketone.

b. Ph₃COH

Show two ways you could synthesize each of the following secondary alcohol by adding an appropriate Grignard reagent to an aldehyde.

(a)

Show how you would synthesize the following primary alcohol by adding an appropriate Grignard reagent to formaldehyde.

(a)

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.

(a) octane

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