Unit ORGANIC CHEMISTRY 2

Course
Chemistry
Study-unit Code
55055612
Curriculum
In all curricula
Teacher
Luigi Vaccaro
CFU
12
Course Regulation
Coorte 2020
Offered
2022/23
Type of study-unit
Obbligatorio (Required)
Type of learning activities
Attività formativa integrata

ORGANIC CHEMISTRY 2

Code 55044106
CFU 6
Teacher Luigi Vaccaro
Teachers
  • Luigi Vaccaro
Hours
  • 42 ore - Luigi Vaccaro
Learning activities Caratterizzante
Area Discipline chimiche organiche e biochimiche
Academic discipline CHIM/06
Type of study-unit Obbligatorio (Required)
Language of instruction Italian
Contents Summary of the fundamental concepts of the Organic Chemistry illustrated in the course of Organic Chemistry I
Acidity of the organic compounds and related reactivity
Rearrangment reactions
Synthesis and reactivity of ethers
Reactivity of carbonyl compounds
Introduction to the chemistry of sulfur, phosphorus and silicon chemistry
Heterocyclic compounds
Polymers
Spectroscopy in Organic Chemistry
Synthetic methodology
Reference texts Peter C Vollhardt, Neil E Schore, Organic Chemistry
7th American edition
2016
Educational objectives This course completes the teaching of Organic Chemistry program that is given to students of the degree course in Chemistry. It aims to complete the acquisition of the fundamental knowledge of the subject. In particular with this course the student is introduced to the chemistry of conjugated compounds, heterocyclic compounds, and deepens the stereochemical concepts affecting the organic chemistry.
Prerequisites Organic Chemistry I
Teaching methods This course completes the Organic Chemistry program that is given to the students in the Chemistry degree course. It aims to complete the acquisition of the basic arguments for a good knowledge of the subject. Particularly with this course, the student is introduced to the chemistry of conjugate compounds, transposition reactions, retrospectives, protection of functional groups and deepen the stereochemical notions affecting organic chemistry.

The course should allow the student to acquire the following basic knowledge:
Know the principles of reactivity that trigger a transposition process
Understand the basic protection / deprotection methods of a functional group
Understand the basic methods of using organic compounds containing sulfur
Understand the basic methods of using organic compounds containing Phosphorus
Know the fundamental chemistry that allows the synthesis of Wittig and its variants based on carbanions of different chemical nature
Other information
Learning verification modality The proof of profit includes the assessment of written reports on laboratory activities and an oral test, which will involve the formulation of 4-5 questions over a period of approximately 40 minutes. The test is aimed at assessing students' abilities and assessing the environmental impact of a chemical process and distinguishing the various factors that influence it.
The overall evaluation of the exam will take into account the following aspects: correctness and adequacy of responses, processing skills and conceptual connection, mastery and language skills, according to the following percentages: 60%, 20%, 20%.
Extended program Summary of the fundamental concepts of the Organic Chemistry illustrated in the course of Organic Chemistry I
Stereochemistry, Reactions and Mechanism, Addition and addition-elimination reactions, Functional group chemistry and classes of organic compounds.

Acidity of the organic compounds and related reactivity
Acidity of hydrogen atoms alpha to carbonyl, nitrile and nitro groups, keto-enol tautomerism, reactivity of enols, alpha halogenation of carbonyl compounds. Enolate ion formation and reactivity, alkylation of enolate ions, decarboxylation, the use of ethyl acetoacetate and malonic esters in synthesis. Enolate acylation, carbonyl condensation reactions, aldol reaction and analogues, the Claisen condensation and related reactions. The Cannizzaro reaction

Rearrangment reactions
Carbocation rearrangements (Wagner-Meerwein, pinacol), Beckmann, Baeyer-Villiger, Hofrnann and Curtius rearrangements.


Synthesis and reactivity of ethers
Williamson ether synthesis, acidic cleavage, cyc1ic ethers and crown ethers.
Synthesis and ring opening reactions of epoxides.

Reactivity of carbonyl compounds
Stereochemistry of addition reactions to carbonyls. Conjugate addition to unsaturated carbonyl systems (Michael addition).

Introduction to the chemistry of sulfur, phosphorus and silicon chemistry
Thiols and sulfides, sulfoxides and sulfones. Structure, nomenc1ature, preparation and reactions of simple organophosphorous and organosilicon compounds. The Wittig and Wadsworth-Emmons reactions, Peterson olefin.

Heterocyclic compounds
Pyrrole, furan, thiophen, pyridine, aromaticity in monocyclic heterocyclic compounds, electrophilic and nucleophilic attack, oxidation and reduction, acid/base properties.

Polymers
Free radical and ionic polymerisation of alkenes (addition or chain growth). Step-growth (condensation) polymerisation.

Spectroscopy in Organic Chemistry
Spectroscopy and mass spectrometry for structure determination Infrared (IR) spectroscopy, characteristic group frequencies. Ultraviolet (UV) and visible spectra, colour and conjugation.
Nuclear magnetic resonance (NM) spectroscopy, chemical equivalence, the delta scal chemical shift.
lH NMR spectra, integration, proton counting, spin-spin coupling, the n+ l rule. 13C NMR spectroscopy, multiplicity in off-resonance spectra.
Mass spectra, molecular ions, accurate mass, isotope signals, and simple fragmentations.

Synthetic methodology
Systematic approaches to the design of syntheses, utilisation of reactions of functional groups for synthesis, functional group interconversions and the formation of carbon-carbon and carbon-heteroatom bonds, application and removal of protecting groups, analysis and modification of synthetic sequences. Use of retrosynthetic analysis and the disconnection approach, synthons and corresponding reagents.

ORGANIC CHEMISTRY LABORATORY 2

Code 55044206
CFU 6
Teacher Stefano Santoro
Teachers
  • Francesco Ferlin (Codocenza)
Hours
  • 57 ore (Codocenza) - Francesco Ferlin
Learning activities Caratterizzante
Area Discipline chimiche organiche e biochimiche
Academic discipline CHIM/06
Type of study-unit Obbligatorio (Required)
Language of instruction Italian
Contents NMR spectroscopy: theoretical basis, chemical shift, splitting and coupling constants, factors influencing chemical shifts and coupling constants, first-order spectra. Laboratory experiences are dedicated to the synthesis, purification and characterization of organic molecules.
Mass spectrometry.
Reference texts "Identificazione Spettrometrica di Composti Organici", R. M. Silverstein, F. X. Webster, D. J. Kiemple, D. L. Bryce; Casa Editrice Ambrosiana (CEA), 2016.
"Guida Pratica alla Interpretazione di Spettri NMR", A. Randazzo; Loghia, 2018.
"Advanced Practical Organic Chemistry", J. Leonard, B. Lygo, G. Procter; CRC Press, 2013.
Educational objectives The course provides a part of lectures and an experimental part in the laboratory. The first part aims at introducing two spectroscopic techniques: nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry. The experimental part is focused on organic synthesis and on the application of spectroscopic knowledge to verify the structures of products and intermediates prepared in the laboratory.
The main aim of this course is to provide students with the fundamental knowledge to analyze and interpret mass and NMR spectra of simple organic compounds.
At the end of the course, the student should be able to identify the structure of an unknown organic compound on the basis of its spectra and limited chemical information.
Main knowledge acquired will be:
- Basic knowledge of nuclei that are able to give the phenomenon of nuclear magnetic resonance;
- Essential knowledge of the nuclear resonance phenomenon;
- Knowledge of the meaning of magnetic and chemical equivalence;
- Knowledge of chemical shift (d) and spin-spin coupling constant (J);
- Knowledge of factors that influence the value of the chemical shift and the value of the spin-spin coupling constant;
- Knowledge of the meaning of integration signal;
- Knowledge of first-order coupling patterns and ability to distinguish first-order couplings from higher-order couplings;
- Essential knowledge about multistep synthetic sequences, processing procedures of a reaction mixture, and methods for the characterization of the reaction products.
The main competence (i.e. the ability to apply acquired knowledge) will be:
- Recognize in a 1H-NMR spectrum the presence of magnetically different protons;
- Predict the chemical shifts of the various types of nuclei present in a molecule;
- Recognize the various spin coupling and discern a first order spin system from those of higher order;
- Apply the acquired knowledge to determine the complete structure of an organic molecule;
- Be able to design and implement a synthesis of an organic compound.
Prerequisites In order to be able to understand the topics of the course you must have successfully passed the Chimica Organica 1 and Chimica Generale ed Inorganica 1 exams.
Teaching methods The Laboratory module of Organic Chemistry 2 presents both a part of lectures and a practical part in the laboratory. The course is organized as follows:
- Lectures of two hours each, held in the classroom, aimed at introducing NMR spectroscopy and mass spectrometry. During the lectures exercises for the interpretation of spectra will be held. Attendance to these lessons is highly recommended.
- Laboratory activity is focused on the preparation of organic compounds in one or more synthetic steps, and on the subsequent purification and physico-chemical and spectroscopic characterization through the techniques mentioned above. The laboratory activity involves 8 sessions lasting 5 hours (14:30 to 19:30). Depending on the number of students, generally two groups of maximum of 24 students are necessary. The frequency to the laboratory is mandatory in view of the fact that many experiences are closely connected. In fact, the product of a reaction may be the reagent of a second reaction and some syntheses require more synthetic steps, which occupy more than one day.
Other information -
Learning verification modality The oral test consists in an interview of about 40 minutes aiming at the assessment of the level of knowledge and ability of understanding reached by the student on the theoretical and methodological contents as indicated in the program. The oral test will also test the student communication skills and his ability in organizing the exposure of the theoretical topics.
Extended program Proton Nuclear Magnetic Resonance Spectroscopy (1H NMR). Introduction. Magnetic properties of atomic nuclei. Physical principle of magnetic resonance. Instrumentation. The chemical shift and the shielding constant. Inductive, anisotropic, steric, solvent and hydrogen bonding effects on the chemical shift. Spin-spin coupling constant. First order spectra. AXn, AmXn and AMX spin systems. Spectra of non-first order. AB and ABX spin systems. Chemical and magnetic equivalence. Simplification of complex spectra using deuterium. The coupling constant: geminal, vicinal and long range coupling. Factors affecting the coupling constant. Examples of interpretation of 1H NMR spectra of organic molecules of medium structural complexity. Introduction to 13C-NMR. Introduction to mass spectrometry.
EXPERIMENTAL PART
Consists of 7-8 practical experiences involving the preparation of organic molecules in single or multistep syntheses and the characterization of the products through the above mentioned spectroscopic techniques.
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