Beckmann Rearrangement

Professor Dave Explains
20 Mar 202009:05
EducationalLearning
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TLDRThe script introduces the Beckmann rearrangement, a chemical reaction that converts ketones into amides, developed by Ernst Beckmann in 1886. It explains the mechanism involving the initial formation of an oxime, followed by a rearrangement that inserts nitrogen into a carbonyl carbon-alkyl bond. The summary also touches on the preference for more substituted groups to migrate during the rearrangement and the potential for Beckmann fragmentation with tertiary carbons, highlighting the reaction's utility in forming seven-membered lactams.

Takeaways
  • 📚 The Beckmann rearrangement is a chemical reaction that converts a ketone into an amide, developed by Ernst Beckmann in 1886.
  • 🔍 The reaction involves the insertion of a nitrogen atom into the carbonyl carbon-alkyl group bond of a ketone, resulting in the migration of an R group.
  • ⚗️ The mechanism begins with the reaction of a ketone with NH2OH, where the nitrogen atom attacks the carbonyl carbon.
  • 💧 A proton transfer occurs, leading to the loss of water and the formation of an oxime intermediate.
  • 🔄 The key rearrangement step involves the migration of an R group and the formation of a carbon-nitrogen bond, facilitated by the departure of water.
  • 🔬 Two resonance structures are possible for the product, with one being more contributing due to the positive charge on carbon being more favorable.
  • 🌐 The migration of the R group in the rearrangement is influenced by the degree of substitution, with more substituted groups being more favorable.
  • 🔬 In the case of asymmetric ketones, the R group that migrates is typically the more substituted one, due to partial positivity during the transition state.
  • 💠 When a cyclic substrate is used, the Beckmann rearrangement can result in the formation of a seven-membered ring, known as a lactam.
  • ⚠️ A limitation of the Beckmann rearrangement is the potential for Beckmann fragmentation, especially with tertiary carbons, which can lead to the formation of a nitrile and an alkene.
  • 🧪 The reaction is carried out under acidic conditions, and the mechanism involves protonation and the formation of a leaving group, such as water.
Q & A

  • What is the Beckmann rearrangement?

    -The Beckmann rearrangement is a chemical reaction that transforms a ketone into an amide. It was developed in 1886 by Ernst Beckmann and involves the insertion of a nitrogen atom into one of the carbonyl carbon-alkyl group bonds.

  • What is the purpose of the Beckmann rearrangement?

    -The purpose of the Beckmann rearrangement is to convert a ketone into an amide, which involves the migration of an alkyl group to the nitrogen atom in the presence of NH2OH.

  • What is the initial step in the Beckmann rearrangement mechanism?

    -The initial step in the Beckmann rearrangement mechanism involves the reaction of a ketone with NH2OH, where the nitrogen atom attacks the carbonyl carbon.

  • What functional group is formed after the first nitrogen attack in the Beckmann rearrangement?

    -After the first nitrogen attack, an oxime functional group is formed, which has a C=N bond with a hydroxyl group attached to the nitrogen.

  • How does the rearrangement step in the Beckmann rearrangement occur?

    -The rearrangement step occurs when a carbon-carbon bond breaks, kicking off water, and the nitrogen atom forms a bond with the alkyl group, resulting in a change of the bond structure and the formation of a carbon-nitrogen bond.

  • What are the two resonance structures formed after the rearrangement in the Beckmann rearrangement?

    -The two resonance structures formed after the rearrangement have either a double bond between the carbon and nitrogen with a positive charge on nitrogen or a single bond with the positive charge on the carbon and a pi bond between the carbon and oxygen.

  • What is a cyclic substrate in the context of the Beckmann rearrangement?

    -A cyclic substrate in the context of the Beckmann rearrangement refers to a cyclic ketone that undergoes the rearrangement to form a cyclic amide, also known as a lactam.

  • What is a lactam?

    -A lactam is a cyclic amide, similar to how a cyclic ester is called a lactone. It is formed when a nitrogen atom is inserted into a ring during the Beckmann rearrangement of a cyclic ketone.

  • What is Beckmann fragmentation and when does it occur?

    -Beckmann fragmentation is a limitation of the Beckmann rearrangement that occurs when a tertiary carbon is involved. Instead of forming the expected nitrogen-carbon bond, the reaction results in the cleavage of the carbon-carbon bond, leaving a nitrile and a tertiary carbocation that can lose a proton to form an alkene.

  • Why is the more substituted alkyl group more favorable to migrate in the Beckmann rearrangement?

    -The more substituted alkyl group is more favorable to migrate in the Beckmann rearrangement because it can better sustain the slight partial positivity that occurs during the migration and coordination to the nitrogen atom in the transition state.

  • Can the Beckmann rearrangement result in a mixture of products?

    -Yes, the Beckmann rearrangement can result in a mixture of products if there is an asymmetric ketone with two different R groups. Each R group can migrate in different circumstances, leading to multiple products.

Outlines
00:00
🧪 Introduction to the Beckmann Rearrangement

Professor Dave introduces the Beckmann rearrangement, a chemical reaction that converts a ketone into an amide. The reaction was first developed in 1886 by Ernst Beckmann. The process involves the insertion of a nitrogen atom into the carbonyl carbon-alkyl group bond, shifting the R2 group and replacing it with nitrogen. The mechanism begins with the reaction of a ketone with NH2OH, leading to the formation of an oxime intermediate. The rearrangement then occurs under acidic conditions, where water is eliminated, and the nitrogen atom forms a new bond with the alkyl group, resulting in an amide. The summary also touches on the resonance structures formed and the preference for migration of a more substituted R group due to partial positivity during the transition state.

05:05
🔬 Cyclic Substrates and Beckmann Fragmentation

This section delves into the application of the Beckmann rearrangement with cyclic substrates, such as cyclohexanone, resulting in the formation of a lactam, a cyclic amide. The process is similar to the rearrangement with acyclic ketones but leads to the creation of a seven-membered ring, which is less common and more challenging to form. The summary also discusses a potential limitation known as Beckmann fragmentation, which can occur with tertiary carbons. Instead of forming the expected nitrogen-carbon bond, the rearrangement may result in the fragmentation of the molecule, leaving behind a nitrile and an alkene product. This phenomenon is important to consider when dealing with highly branched substrates in Beckmann rearrangements.

Mindmap
Keywords
💡Beckmann rearrangement
The Beckmann rearrangement is an organic chemical reaction that converts a ketone to an amide. It was first developed by Ernst Beckmann in 1886. In the video, this reaction is the central theme, with the professor explaining how a nitrogen atom is inserted into the carbonyl group of a ketone, resulting in the formation of an amide. The process involves the initial formation of an oxime, followed by a rearrangement step that leads to the amide product.
💡Ketone
A ketone is an organic compound featuring a carbonyl group (C=O) bonded to two other carbon atoms. In the context of the Beckmann rearrangement, the ketone serves as the starting material, with two alkyl groups (R1 and R2) attached to the carbonyl carbon. The script mentions the transformation of a ketone into an amide as the primary objective of the reaction.
💡Amide
An amide is an organic compound containing a carbonyl group linked to a nitrogen atom (C=O-N). In the video, the formation of an amide is the end goal of the Beckmann rearrangement. The amide is formed through the insertion of a nitrogen atom into the carbonyl group of a ketone, which is a key step in the reaction mechanism.
💡Oxime
An oxime is an organic compound with a hydroxyl group (-OH) attached to a nitrogen atom that is double-bonded to a carbon atom (C=N-OH). In the script, the formation of an oxime is an intermediate step in the Beckmann rearrangement, where the nitrogen atom initially attacks the carbonyl carbon of the ketone.
💡Acidic conditions
Acidic conditions refer to an environment with a high concentration of hydrogen ions (H+). In the context of the Beckmann rearrangement, the script mentions that the reaction can be carried out under acidic conditions, which facilitates the protonation of the hydroxyl group in the oxime, leading to the departure of water and the subsequent rearrangement.
💡Migration
In organic chemistry, migration refers to the movement of an atom or group of atoms from one position to another during a reaction. In the Beckmann rearrangement, the script describes how the R2 group migrates from its original position to bond with the nitrogen atom, resulting in the formation of the amide.
💡Resonance structures
Resonance structures are different ways of representing the distribution of electrons in a molecule, which can help explain the stability and properties of a molecule. The script discusses two resonance structures for the intermediate formed during the Beckmann rearrangement, illustrating how the positive charge can be distributed between carbon and nitrogen.
💡Cyclic substrate
A cyclic substrate is a compound that contains a ring structure. The script explains that the Beckmann rearrangement can also occur with cyclic ketones, such as cyclohexanone, resulting in the formation of a cyclic amide, or lactam, which is a seven-membered ring in this case.
💡Lactam
A lactam is a cyclic amide, where the nitrogen atom is part of a ring structure. The script mentions lactams as products of the Beckmann rearrangement when a cyclic ketone is used as the substrate, highlighting the formation of a seven-membered ring lactam as an example.
💡Beckmann fragmentation
Beckmann fragmentation is a side reaction that can occur during the Beckmann rearrangement, especially with tertiary carbons. The script warns about this limitation, explaining that instead of forming the desired nitrogen-carbon bond, the reaction may lead to the formation of a nitrile and an alkene due to the stability of the tertiary carbocation.
Highlights

Introduction to the Beckmann rearrangement, a reaction developed in 1886 by Ernst Beckmann to transform ketones into amides.

The reaction involves the insertion of a nitrogen atom into a carbonyl carbon alkyl group bond.

Mechanism overview begins with the ketone reacting with NH2OH, where the nitrogen atom attacks the carbonyl carbon.

Protonation and loss of water leads to the formation of an oxime intermediate.

The key rearrangement step involves a carbon-carbon bond breaking and nitrogen coordinating with the alkyl group.

Two resonance structures are formed after the rearrangement, with the nitrogen now bound to R2.

The more substituted R group is generally favored to migrate during the rearrangement due to partial positivity.

Beckmann rearrangement can lead to a mixture of products if the ketone is asymmetric.

Cyclic substrates can undergo Beckmann rearrangement to form lactams, with seven-membered rings being notably difficult to form.

The formation of a seven-membered lactam is highlighted as a significant application of the Beckmann rearrangement.

Beckmann fragmentation is a limitation where a tertiary carbon does not form a bond with nitrogen, leading to a nitrile and alkene product instead.

The importance of the Beckmann rearrangement in forming challenging seven-membered rings is emphasized.

The reaction conditions, such as acidic conditions, are briefly mentioned for simplicity.

The potential for product mixtures depending on the migrating R group in asymmetric ketones is discussed.

The rearrangement is described as thermodynamically driven, with bond energies playing a key role.

The use of cyclic substrates to specifically form seven-membered lactams is highlighted as a strategic application.

The concept of resonance structures contributing to the stability of the rearranged product is explained.

The potential for Beckmann fragmentation in the case of tertiary carbons is warned, impacting the outcome of the reaction.

Transcripts

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Related Tags
Beckmann RearrangementOrganic ChemistryKetonesAmidesChemical ReactionErnst BeckmanOxime FormationAcidic ConditionsLactam ChemistryCyclic SubstratesBeckman Fragmentation