1. Following the IUPAC rules of nomenclature, provide either the correct name for the given structure or draw the correct structure for the given name. (12 points)

a) propanenitrile

This molecule has a three carbon chain including a nitrile: CH₃-CH₂-CN

b) 4-methanoylbenzoic acid

This molecule has an aldehyde (methanoyl) group and a carboxylic acid group at the 1 and 4 positions of a benzene ring.

c)

succinic anhydride

d)

N,N-dimethylbutanamide

2. Complete nine of the following reactions with either products, reactants, or reagents. (36 points)

a) from Chapter 18

Acid chloride and two equivalents of amine give an amide and the hydrochloride salt of the amine.

b) from Chapter 11

Reduction of a carboxylic acid with lithium aluminum hydride gives an alcohol.

c) from Chapter 19

Treatment of an ethyl ester with ethoxide gives the b-keto ester by the Claisen condensation.

d) from Chapter 17

Iodoform and a carboxylic acid result from treatment of methyl ketones with iodine and base; therefore the starting material was acetophenone (also ethanoylbenzene or acetylbenzene)

e) from Chapter 18

Basic hydrolysis of an amide gives the carboxylate anion and ammonia. (the carboxylic acid and ammonium cation were acceptable although they are typically found for acid hydrolysis)

f) from Chapter 16

The Wittig reaction of aldehydes and ketones gives an alkene and triphenylphosphine oxide.

g) from chapter 17

Nucleophilic reaction of Grignard reagents with a,b-unsaturated carbonyls gives both 1,2 and 1,4 products although the 1,2 products are generally favored.

h) from Chapter 18

Reaction of an alcohol with an anhydride in the presence of the carboxylate anion gives an ester, in this case cyclohexyl ethanoate, and the carboxylic acid, in this case ethanoic acid.

i) from Chapter 16

Reaction of a ketone with hydroxylamine with acid catalysis gives an oxime.

j) from Chapter 18

The reagents for conversion of carboxylic acids to acid chlorides are either thionyl chloride (SOCl₂) or phosphorus pentachloride (PCl₅)

k) from Chapter 16

The starting materials for the synthesis of an acetal are the aldehyde (here benzaldehyde) and two equivalents of the alchol (here ethanol).

l) from Chapter 17 (see page 778)

This is a Robinson annulation, a conjugate aldol addition (or Michael addition) followed by a simple aldol condensation to form the second six membered ring.

m) from Chapter 19

This is a Malonic Ester Synthesis. The appropriate reagents are: 1. sodium ethoxide in ethanol to make the enolate anion of diethyl malonate; 2. benzyl bromide as an alkylating agent; 3. sodium hydroxide and heat to hydrolyze the esters and decarboxylate.

3. Provide a detailed, step-by-step mechanism for the following reaction. (16 points)

The reaction shown is the formation of a cyanohydrin. This follows the direct mechanism. The first step is nucleophilic attack by the cyanide anion to form the anionic tetrahedral intermediate (formally an alkoxide). The second step is protonation of the alkoxide to give the cyanohydrin.

4. Provide a detailed, step-by step mechanism for the following reaction. (16 points)

The reaction shown is an acid catalyzed trans-esterification. The mechanism consists of the following steps: 1. Protonation of the carbonyl. 2. Nucleophilic attack by cyclohexanol. 3. Deprotonation of the cylohexyl ether. 4. Protonation of the ethyl ether. 5. Loss of ethanol. 6. Deprotonation to give the final product.

5. For the folowing compounds, consider the acidity of the highlighted protons. Order these compounds from most acidic to least acidic. (8 points)

(Most acidic) trifluoroacetic acid>acetic acid>dimethyl malonate>ethanal (Least acidic)

6. Provide a synthesis of methyl 4-phenyl-2-hydroxy-3-butenoate (shown below) from benzyl alcohol, ethanal, and any other necessary organic or inorganic reagents. You will need to use chemistry from several chapters! (12 points)

The synthesis begins with oxidation of benzyl alcohol (NOT to be confused with phenol!!) to benzaldehyde. Benzaldehyde and ethanal react by a crossed aldol condensation followed by spontaneous elimination to give cinnamaldehyde (3-phenyl-2-propenal). Formation of a cyanohydrin with HCN. (Note that there will be considerable competition with conjugate addition!) Hydrolysis of the nitrile to the carboxylic acid via the amide. Fischer esterification of the acid to give the methyl ester.