Devise a synthesis for each compound, starting with methylenecyclohexane and any other reagents you need.

d. trans-2-methylcyclohexanol

Devise a synthesis for each compound, starting with methylenecyclohexane and any other reagents you need.

f. 1-(phenylmethyl)cyclohexanol

Compare the properties of propan-2-ol (I) and the hexafluoro analog (II).

(a) Compound II has almost triple the molecular weight of I, but II has a lower boiling point. Explain.

Compounds containing deuterium (D = ²H) are useful for kinetic studies and metabolic studies with new pharmaceuticals. One way to introduce deuterium is by using the reagent LiAlD₄, equivalent in reactivity to LiAlH₄. Show how to make these deuterium-labeled compounds, using LiAlD₄ and D₂O as your sources of deuterium, and any non-deuterated starting materials you wish.

a. CH₃CHDOH

Compounds containing deuterium (D = ²H) are useful for kinetic studies and metabolic studies with new pharmaceuticals. One way to introduce deuterium is by using the reagent LiAlD₄, equivalent in reactivity to LiAlH₄. Show how to make these deuterium-labeled compounds, using LiAlD₄ and D₂O as your sources of deuterium, and any non-deuterated starting materials you wish.

(b) CH₃CD₂OH

Compounds containing deuterium (D = ²H) are useful for kinetic studies and metabolic studies with new pharmaceuticals. One way to introduce deuterium is by using the reagent LiAlD₄, equivalent in reactivity to LiAlH₄. Show how to make these deuterium-labeled compounds, using LiAlD₄ and D₂O as your sources of deuterium, and any non-deuterated starting materials you wish.

(c) CH₃CD₂OD

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 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.

c. CD₃CH₂CH₂OH

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

Often, compounds can be synthesized by more than one method. Show how this 3° alcohol can be made from the following:

(a) two different ketones

Often, compounds can be synthesized by more than one method. Show how this 3° alcohol can be made from the following:

(b) two different alkenes

Often, compounds can be synthesized by more than one method. Show how this 3° alcohol can be made from the following:

(c) an ester

Often, compounds can be synthesized by more than one method. Show how this 3° alcohol can be made from the following:

(d) a 3° alkyl bromide

Show how this 1° alcohol can be made from the following:

(a) a 1° alkyl bromide

Show how this 1° alcohol can be made from the following:

(b) formaldehyde

Show how this 1° alcohol can be made from the following:

(c) a 7-carbon aldehyde

(d) a carboxylic acid

Show how this 1° alcohol can be made from the following:

(e) an alkene

(f) ethylene oxide

For each synthesis, start with bromocyclohexane and predict the products. Assume that an excess of each reactant is added so that all possible reactions that can happen will happen.

(a)

For each synthesis, start with bromocyclohexane and predict the products. Assume that an excess of each reactant is added so that all possible reactions that can happen will happen.

(b)

For each synthesis, start with bromocyclohexane and predict the products. Assume that an excess of each reactant is added so that all possible reactions that can happen will happen.

(c)

Problem 8-54 describes a new method to perform ozonolysis reactions that used pyridine (py) to generate the final aldehydes and ketones in a non-aqueous reaction medium. In a subsequent publication (J. Org. Chem., 2013, 78, 42), Professor Dussault (U. of Nebraska at Lincoln) described a “tandem” process in which two reactions are performed sequentially without having to isolate the intermediate aldehyde or ketone. Show the final product from each sequence. (Hint: The isolated products were from the larger part of the structure. Ignore stereochemistry.)

(a)

(b)

Problem 8-54 describes a new method to perform ozonolysis reactions that used pyridine (py) to generate the final aldehydes and ketones in a non-aqueous reaction medium. In a subsequent publication (J. Org. Chem., 2013, 78, 42), Professor Dussault (U. of Nebraska at Lincoln) described a “tandem” process in which two reactions are performed sequentially without having to isolate the intermediate aldehyde or ketone. Show the final product from each sequence. (Hint: The isolated products were from the larger part of the structure. Ignore stereochemistry.)

(c)

(d)