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Syllabus 2018-19 - 10312015 - Organic Chemistry 2 (Química orgánica II)

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  • Level 1: Tutorial support sessions, materials and exams in this language
  • Level 2: Tutorial support sessions, materials, exams and seminars in this language
  • Level 3: Tutorial support sessions, materials, exams, seminars and regular lectures in this language
DEGREE: Grado en Químicas
FACULTY: FACULTY OF EXPERIMENTAL SCIENCES

ACADEMIC YEAR: 2018-19
SYLLABUS
1. COURSE BASIC INFORMATION
NAME: Organic Chemistry 2
CODE: 10312015 ACADEMIC YEAR: 2018-19
LANGUAGE: English LEVEL: 1
ECTS CREDITS: 6.0 YEAR: 3 SEMESTER: PC
 
2. LECTURER BASIC INFORMATION
NAME: MELGUIZO GUIJARRO, MANUEL
DEPARTMENT: U128 - QUÍMICA INORGÁNICA Y ORGÁNICA
FIELD OF STUDY: 765 - QUÍMICA ORGÁNICA
OFFICE NO.: B3 - 451 E-MAIL: mmelgui@ujaen.es P: 953212742
WEBSITE: -
LANGUAGE: English LEVEL: 1
 
3. CONTENT DESCRIPTION

Lesson 1. Acidity and basicity in organic compounds. Proton transfer. (2h)

Proton transfer in organic molecules. Relative acidity and basicity: the pK a tables. Structural factors that influence acidity and basicity in organic molecules. Acidity of hydrogen atoms bonded to carbon. Proton transfer in reaction mechanisms.

Lesson 2. Lewis acids and bases. Electrophiles and nucleophiles. (2h).

Lewis acids and bases and its classification. Nucleophilic groups in organic molecules: classification and reactivity. Electrophilic groups in organic structures: classification and reactivity.

Lesson 3. Structure of the aromatic compounds. (2h).

The structure of benzene as the archetype of aromatic compounds. The distinct properties of benzene due to its aromatic nature. Aromatic and anti-aromatic systems: Hückel's rule. Mononuclear aromatic systems different from benzene. Polynuclear aromatic systems. Heteroaromatic fused compounds. Nomenclature of benzene derivatives.

Lesson 4. Reactivity of aromatic compounds. (3h).

The classical electrophilic aromatic substitution (Ar-SE), thermodynamic aspects: Wheland complexes, energy profile and reversibility. Kinetic aspects of the Ar-SE: effects of substituents on the reactivity of the aromatic positions. Orientation of Ar-SE in polysubstituted benzene derivatives. Synthetically useful reactions of the Ar-SE type: halogenation, sulfonation, nitration, Friedel-Crafts alkylation, reactions with aldehydes and ketones, Friedel-Crafts acylation, formilation, preparation of diazoderivatives. Electrophilic substitution on organometallics. Ar-SN via Meisenheimer complexes. Monomolecular nucleophilic substitution (Ar-SN1) on aromatic diazonium salts. Ar-SN via arines. Transformation of groups bonded to aromatic rings: reduction of nitro to amino; reduction of aromatic ketones; oxidation of lateral chains; chemical behavior of phenols; behavior of anilines.

Lesson 5. Review of the main polar reaction mechanisms. Structural, kinetic and stereochemical effects. (4h).

Nucleophilic aliphatic substitution. beta-Elimination. Addition to double bonds. Nucleophilic substitution at planar trigonal centers. Rearrangements around electrophilic carbon atoms.

Lesson 6. Pericyclic reactions. (4 h)

What's a pericyclic reaction? Types of concerted pericyclic reactions. Building FMO diagrams in delocalized "pi" systems. Cycloadditions. Electrocyclic reactions. Sigmatropic rearrangements. "Ene" reactions.

Lesson 7. Sulfur, silicon and phosphorus in organic chemistry. (2h)

Sulfur functional groups. Anions stilized by sulfur groups. Sulfonium ylids and sufoxonium ylids. Carbon and silicon compared. Synthetically useful silicon derivatives. Phosphorus functional groups. Phosphorus ylids.

Lesson 8. Carbon-carbon bond formation (I). Reactions affording new C-C bonds under basic conditions. (4h).

Enols and enolates. Preparation of alkaline earth metal enolates. Regioselectivity in enolate formation: kinetic and thermodynamic enolates. Stereoselectivity in enolate formation. An overview of enolate reactivity: ambidoselectivity. Aldol addition. Aldol condensation (synthesis of Michael acceptors). Enolate acylation. Variations of the reaction between enolates and carbonyl compounds (Reformatzky, Perkin, Darzens, Henry and Knoevenagel reactions). Alkylation of enolates and azaenolates. Malonic ester synthesis. Acetoacetic ester synthesis. Formation of C=C via phosphorus ylides and stabilized carbanions.

Lesson 9. Carbon-carbon bond formation (II). Formation of C-C bonds via enols and their synthetic equivalents. (2h).

The keto-enol tautomerism in carbonyl and carboxyl derivatives. Formation of C-C bonds via enols. Enamines, enol ethers, silyl enol ethers and ketene silyl acetals as synthetic equivalents of enols.

Lesson 10. Carbon-carbon bond formation (III). Formation of C-C bonds through organometallic reagents and transition metal catalyzed reactions. (5h).

Organometallic compounds derived from the elements of the main groups: preparation and properties. Reaction affording new C-C bonds through organometallic reagents of magnesium, lithium and zinc. An introduction to the transition metal organometallic chemistry. Organometallic reagents derived from copper and its synthetic value. Reactions of C-C bond formation catalyzed by palladium. Alkylidene complexes and their synthetic applications.

Lesson 11. Carbon-nitrogen bond formation. (3h).

Nitrogenated organic functional groups. Nucleophilic and electrophilic nitrogen reagents. C-N bond formation through nucleophilic nitrogen reagents. Transition metal catalyzed C-N bond formation. C-N bond formation through electrophilic nitrogen reagents. Aminoacid synthesis. Peptide synthesis.

Lesson 12. An introduction to organic synthesis. (3h).

The concept of organic synthesis. Definitions of linear synthesis, convergent synthesis and combinatorial synthesis. Total and partial syntheses. The concept of stereoselective, stereospecific and asymmetric synthesis. An overview on synthesis design: retrosynthetic analysis.

4. COURSE DESCRIPTION AND TEACHING METHODOLOGY

A total of thirty six lectures (50 min duration each) developed with the whole group of students will be dedicated to present and explain the topics contained in the syllabus. Every lecture shall include explanatory presentations, exercises and discussion on the current topic.

Other twenty hours will be dedicated to seminars (50 min per session) for smaller groups of students. These seminars are of three types, as follows:

  • Fourteen seminars (one session each) will be dedicated to presenting and solving exercises dealing with the topics included in the lesson developed along the explanatory lectures.
  • Four seminars (one session each) will be dedicated to solve a collection of proposed problems that the students should previously solve as homework.
  • One monographic seminar of four hours dedicated to go in depth into stereochemical concepts.

Finally, two sessions of tutorials dedicated to review the studied topics and orient the students on how to study this course.

Students with special educational needs should contact the Student Attention Service (Servicio de Atención y Ayudas al Estudiante) in order to receive the appropriate academic support

5. ASSESSMENT METHODOLOGY

WRITTEN EXAM (70 %)

In the exam, the student must solve a collection of practical problems in relation with the course contents. The items to be evaluated are:

  • Using a proper language and suitable organic chemistry formalisms in his/her answers.
  • Ability to relate experimental kinetic and thermodynamic data with the mechanisms of a reaction, and viceversa.
  • Knowledge of the main procedures to transform organic functional groups and to generate new C-C and C-N bonds.
  • Integrating his/her knowledge on reactivity and reaction mechanisms to give a reasonable synthesis plan for molecules of medium-low complexity.

Competences to be evaluated: B1, B2, B9, C2, C8, C10, C13, Q2

MONITORING OF CONTINUOUS WORK (30 %)

To evaluate the work of the student during the course, he/she must solve four collections of exercises as homework at precise dates. The solutions shall be given to the lecturers prior to be publically solved in the corresponding seminar sessions. These solutions will be evaluated as a function of:

  • Completeness of the proposed exercises.
  • Degree of correctness of the given answer.
  • Participation of the student in de public discussion of the solutions.

Competences to be evaluated: B2, B5, B9, C10 y Q2

A MINIMUM OF 4 POINTS (OVER A TOTAL OF 10) MUST BE ACHIEVED IN THE WRITTEN EXAM TO CAN SUM UP THE POINTS ACHIEVED THROUGH THE CONTINUOUS WORK MONITORING TO THE FINAL MARK.

6. BOOKLIST
MAIN BOOKLIST:
  • Writing Reaction Mechanisms in Organic Chemistry. Edition: Tercera. Author: Kenneth A. Savin. Publisher: Academic Press  (Library)
  • Electron flow in organic chemistry [Recurso electrónico] : a decision-based guide to organic mechani. Edition: 2nd ed. Author: Scudder, Paul H. Publisher: Hoboken, N.J. : Wiley, 2013  (Library)
  • Organic Mechanisms [Recurso electrónico] : Reactions, Stereochemistry and Synthesis. Edition: -. Author: Bruckner, Reinhard. Publisher: Berlin, Heidelberg : Springer Berlin Heidelberg, 2010.  (Library)
  • Organic chemistry. Edition: 6th ed.. Author: Wade, L. G.. Publisher: Upper Saddle River, N.J. : Pearson Prentice Hall, c2006  (Library)
ADDITIONAL BOOKLIST:
  • Organic Chemistry (second edition). Edition: Segunda. Author: Clayden, Jonathan. Publisher: Oxford  (Library)