Textbook: Wade 7th Ed. (2009)

Chapter 19: Amines

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Individual Problems

Individual Problems

Problem # 755

The nitrosyl cation is shown below. Also shown are several proposed resonance arrows, only one of which is correct.

Draw the resonance forms that would follow from each set of arrows, and include formal charges. Which one is the correct resonance form? Explain your reasoning.

Solution

When evaluating possible Lewis structures the most important rule to follow is the octet rule: every atom must be surrounded by 8 and only 8 electrons (atoms in period 3 or below on the periodic table have d orbitals and so can contain more than 8 electrons, but that exception does not apply here).

Do any of the resonance forms drawn have atoms that break the octet rule? Yes- they all do! Except for resonance arrows in D. So D is the correct resonance form.

Problem Details

MendelSet practice problem # 755 submitted by Matt on July 27, 2011.

Subject: Organic Chemistry

Subject Topic(s): Lewis Structures, Formal Charges, and Resonance, Diazonium Chemistry (NaNO2, Sandmeyer, Nitrosyl)

Question Type: Concept (explain why this is so..)

Keyword(s): resonance, Lewis structures

Problem # 753

Rank the amines W through Z below in order of decreasing basicity (1 = most basic). Explain your reasoning.

Solution

Electron withdrawing groups (EWG) reduce electron density and reduce basicity. Resonance delocalizes electron density and so also decreases basicity (the electrons are less available to pick up a proton).

Electron donating groups (EDG) add electron density and increase basicity.

Alkyl groups are weakly EDG (induction), and hydrogen is neither EDG nor EWG. So cyclohexylamine (compound X) is a stronger base than ammonia (compound W).

Aniline (compound Y) has resonance, so it is less basic than compound X, which does not have resonance.

N-acyl aniline (compound Z) has more resonance forms than aniline, so it will be the least basic.

So the overall over is:

(most basic) X > W > Y > Z (least basic)

Problem Details

MendelSet practice problem # 753 submitted by Matt on July 27, 2011.

Subject: Organic Chemistry

Subject Topic(s): Amines (Basicity, Hoffman Elimination, Gabriel Amine Synthesis)

Question Type: Concept (explain why this is so..)

Keyword(s): base strength, amine bases, EDG and EWG

Problem # 754

Show how each amine can be prepared from a carbonyl and an amine via reductive amination.

Solution

Reductive amination is a two step process. First, an imine or enamine is formed from a carbonyl and an imine.

Then, a the imine (or enamine) is reduced to an amine (using reducing agents such as H₂, NaBH₄, NaBH₃(CN), NaBH(OAc)₃, etc.). For practice on forming imine and enamines, see problem 712).

Problem Details

MendelSet practice problem # 754 submitted by Matt on July 27, 2011.

Subject: Organic Chemistry

Subject Topic(s): Amines (Basicity, Hoffman Elimination, Gabriel Amine Synthesis)

Question Type: Concept (explain why this is so..)

Keyword(s): imines, enamines, reductive amination

Problem # 756

For each amine below, show all Hofmann elmination products.

If more than one product is formed, predict which one will be the major product.

Solution

The Hoffman elimination first turns an amine into a better leaving group by methylating it with excess methly iodide, and then eliminates the methylated amine using base (such as ^-OH fomed from Ag₂O in H₂O). The products are alkenes.

This reaction is similar to an E2 elimination in that a beta proton is ripped off, and the alkene forms between alpha and beta. One notable difference from the E2 is that the less substituted product is favored, so Hoffman products are usually anti-Zaitsev.

a) There are three different types of beta protons, so three possible products can form. Product A is the least substituted alkene, so it's the major product.

b) There is only one possible product. The Hoffman elimination can't be done on aryl hydrogens (benzene rings).

Problem Details

MendelSet practice problem # 756 submitted by Matt on July 27, 2011.

Subject: Organic Chemistry

Subject Topic(s): Amines (Basicity, Hoffman Elimination, Gabriel Amine Synthesis)

Question Type: Reactions (predict the product, show the starting material..)

Keyword(s): Zaitsev's rule, Hoffman elimination

Problem # 591

Pyrrole undergoes eletrophilic aromatic substitution at C-2. Let's compare the resonance forms of EAS carbocation intermediates to see why this is the case. What do you think? Why C-2 and not C-3?

Solution

Electrophilic substitution at C-2 leads to a carbocation intermediate with three resonance forms, while substitution at C-3 leads to a carbocation intermediate with only two resonance forms.

The C-2 intermediate has more resonance forms than the C-3 intermediate, and so is more stable. Therefore, EAS occurs at C-2.

Problem Details

MendelSet practice problem # 591 submitted by Matt on July 9, 2011.

Subject: Organic Chemistry

Subject Topic(s): Pyridine and Heteroaromatic EAS

Question Type: Concept (explain why this is so..)

Keyword(s): heteroaromatic compounds, EAS mechanism

Problem # 584

Imidazole (shown below) has two nitrogen atoms, N-1 and N-3. Which nitrogen is more basic?

To answer this problem, draw the product after each nitrogen protonates, and compare their stabilities. Explain your reasoning.

Solution

Imidazole is aromatic. When N-3 protonates, the product is still aromatic.

But when N-1 protonates, the product is no longer aromatic (and therefore significantly less stable).

Because of this, N-3 is much more basic than N-1. Another way of thinking of this is that the lone pair on N-1 is involved in the aromatic circuit, and so is not available to pick up a proton.

Problem Details

MendelSet practice problem # 584 submitted by Matt on July 9, 2011.

Subject: Organic Chemistry

Subject Topic(s): Benzene and Aromaticity, Amines (Basicity, Hoffman Elimination, Gabriel Amine Synthesis), Pyridine and Heteroaromatic EAS

Question Type: Concept (explain why this is so..)

Keyword(s): base strength, aromaticity, amine bases

Problem # 728

The acyl group is a protecting group for amines. Amines can be acylated using acetic anhydride, and deacylated with base.

Propose a mechanism for each reaction.

Solution

These reactions are both nucleophilic acyl substitution under basic conditions. See problem 705 for the mechanism in detail.

Problem Details

MendelSet practice problem # 728 submitted by Matt on July 24, 2011.

Subject: Organic Chemistry

Subject Topic(s): Nucleophilic Acyl Substitution (Carboxylic Acid Derivatives), Amines (Basicity, Hoffman Elimination, Gabriel Amine Synthesis)

Question Type: Mechanism (show a mechanism using curved arrows..)

Keyword(s): nucleophilic acyl substitution

Problem # 752

Rank the amines A through D below in order of decreasing basicity (1 = most basic). Explain your reasoning.

Solution

sp² carbons are more electronegative (electron withdrawing) than sp³ carbons due to increased s-character. Electron withdrawing groups (EWG) make acids more acidic and bases less basic.

For this reason, piperidine (compound A) is the more basic than pyridine (compound B):

(more basic) A > B (less basic)

Nitro (-NO₂) is an EWG, so 4-nitropyridine (compound C) will be less basic than compound A.

Dimethylamine is an electron donating group (EDG), so it adds electron density to pyridine and increases basicity. So dimethylamino pyridine (DMAP, compound D) will be more basic than compound A:

(more basic) D > B > C (less basic)

So how does compound A compare with compound D? There is no way of predicting this based on EWG/EDG rules alone. After all, what should be more basic: piperidine, which has sp³ carbons (increases base strength), or DMAP, which has sp² carbons (decreases base strength) but also an EDG (increases base strength) ?

There's no way to tell. But it turns out that Piperidine is a little more basic than DMAP. So the overal order is:

(more basic) A > D > B > C (least basic)

Problem Details

MendelSet practice problem # 752 submitted by Matt on July 27, 2011.

Subject: Organic Chemistry

Subject Topic(s): Amines (Basicity, Hoffman Elimination, Gabriel Amine Synthesis)

Question Type: Concept (explain why this is so..)

Keyword(s): base strength, amine bases, EDG and EWG

Problem # 757

Propose a synthesis to accomplish each transformation. The only carbon sources allowed are alkenes and NaCN.

Solution

a) The starting alkene has 4 carbons, and the product has 5 carbons and a nitrogen. So you have to add 1C and 1N. This screams "add cyanide!"

Based on the location of the alcohol on the product, it looks like the way to go is to add NaCN to an epoxide. This puts the -CN and the -OH in the right positions.

b) The best way to prepare 2º and 3º amines is via reductive amination. Working backwards, the product can be prepared from a 4-carbon aldehyde (butyraldehyde) and a 3-carbon amine (propyl amine).

Performing hydroboration on the butene results in the anti-Markovnikov alcohol, which can be oxidized to the aldehyde using PCC.

To prepare propyl amine from an alkene, add HBr/peroxides to make the bromide (anti-Markovnikov), and then add NaN₃ follow by H₂/Pd.

Problem Details

MendelSet practice problem # 757 submitted by Matt on July 27, 2011.

Subject: Organic Chemistry

Subject Topic(s): Amines (Basicity, Hoffman Elimination, Gabriel Amine Synthesis)

Question Type: Synthesis (show how to prepare X from Y..)

Keyword(s): nitriles, reductive amination

Problem # 593

a) Rationalize the relative stabilities of the cation species below.

b) Pyridine undergoes eletrophilic substitution at C-3. Let's compare the resonance forms of EAS carbocation intermediates to see why this is the case. Consider part a) in your explanation.

Solution

a) The species on the left are much more stable than the species on the right because they have complete octets.

Nitrogen is less electronegative than oxygen, so a positive nitrogen (with a full octect) is more stable than a positive oxygen; oxygen is electronegative and so doesn't "like" being positive (have low electron density).

The carbocation and the "nitrocation" are both very unstable because they only have 6 valence electrons. Because nitrogen is more electronegative than carbon, the nitrocation is even less stable than the carbocation, because its worse at handling a positive charge.

b) The cation intermediates that result from substitution at C-3 only contain carbocations, while the intermdiates from C-2 or C-4 substitution contain a "nitrocation," which is less stable than a regular carbocation, and so are not favored. So pyridine undergoes EAS reactions at C-3.

One more note: For substitution at C-2 and C-4, it's tempting to draw a resonance form where the positive charge is on the nitrogen, which is flanked by two double bonds. But this cyclic compound is too strained to exist, and so doesn't contribute to this analysis.