ORGANIC CHEMISTRY 2 AND LABORATORY - MOD.1

Chimica Organica II falls within the training activities that characterize the three-year laurea degree in Chemistry and Sustainable Technologies. The course aims to allow the student to face a chemical problem in its various articulations and with a consistent use of the current technical-scientific language. The educational goal of the course is to provide knowledge of organic chemistry, especially regarding the mechanistic aspects and the relationships between structure and reactivity of the main functional groups of organic substances. Students should be enabled to design and check a basic sequence of organic synthesis. The theoretical course of Organic Chemistry II (module 1) is therefore intended to complete and integrate some of the fundamental notions examined in the course of Organic Chemistry I (1st part), and to provide students with modern methodological tools, also through the introduction of the principles of retrosynthetic analysis, for the preparation of organic molecules.

Expected learning outcomes
1. Knowledge and understanding
i) Knowledge of the relationships between structure and reactivity of the main classes of organic compounds.
ii) Knowledge of the basic notions for the elaboration of an organic synthesis also through the main notions of retrosynthetic analysis.
2. Ability to apply knowledge and understanding
i) Knowledge of the use the learned concepts to foresee and discuss the mechanism of an organic reactions.
ii) Ability to propose a coherent sequence of reactions to solve an organic synthesis problem, possibly recognizing the most direct, economic and/or environmental impact experimental procedures.
3. Judgment capacity
In accordance to the degree of knowledge of subjects during the course:
i) Capability to evaluate comparatively the effectiveness of different synthetic strategies in terms of choice of reagents and reaction conditions
ii) Knowledge of a preliminary critical capacity on the dangerousness of some classes of organic compounds for human health and the environment
4. Communication skills
i) Knowledge of the appropriate scientific-technical terminology and symbolism for the discussion of reaction mechanisms and the solution of synthesis problems.
ii) Ability to interact constructively with the teacher and classmates, to formulate coherent questions and argue alternative hypotheses of reaction mechanisms and solutions to synthetic problems
5. Learning skills
i) Ability to take class notes by identifying autonomously the salient aspects of scientific reasoning and notions expressed in class

Prerequisites
Before the course of organic chemistry part II, the student should have achieved the educational objectives of the course in Organic Chemistry I and Laboratory. The student should know and be familiar with the structure and properties of the main classes of organic substances, including aromatic compounds, carboxylic acids and their derivatives (halides, anhydrides, esters and amides), alcohols and ethers, alkenes, alkyl halides, carbonyl compounds and amines. Moreover, the knowledge of the nomenclature of these compounds is recommended, at least pertinent to the general families to which these molecules belong. It is recommended that the student has passed the exam of Organic Chemistry I and Laboratory.

Contents
- Introduction.
Program description, examination methods and bibliography.
- Reactivity of aromatic compounds.
Aromatic electrophilic substitutions: halogenations, nitrations, sulfonations, alkylations and Friedel-Crafts acylations. Structure / reactivity comparison. Halogenation and oxidation of alkylbenzene side chains. Reduction of aromatic derivatives. Aromatic nucleophilic substitution. Retrosynthetic analysis.
- Carboxylic acids and their derivatives.
Carboxylic acids and derivatives: order of reactivity of halides, anhydrides, esters, and amides. Nucleophilic acyl substitution with water, alcohols and amines. Reductions of acids and derivatives with saline hydrides. Retrosynthetic analysis.
- Carbonyl chemistry
Reduction and oxidation of the carbonyl with saline hydrides, chromic acid, and the Tollens reagent. Nucleophilic addition of organometallic compounds: Grignard reaction, with organolithium, and Na acetylides. Retrosynthetic analysis. Protection via silyl ethers. Alpha,beta unsaturated carbonyls: nucleophilic additions 1,2 and 1,4.
- Aldehydes and Ketones.
Synthesis via oxidative hydroboration and acid-catalyzed with HgSO4. Nucleophilic addition to aldehydes and ketones: i) Wittig reaction; ii) formation of imines and enamines, hydrates and acetals. Use of acetals as protecting groups.
- Substitution reactions in alpha of carbonyl compounds.
The alpha acidity of carbonyl compounds. The keto-enolic balance. Generation of enols and enolates: kinetic and thermodynamic control. Halogenations in alpha: acid catalysis and basic promotion (aloform reaction). Alpha-alkylations of enolates. Malonic and acetacetic synthesis. Use of enamines as analogues of enolates. Retrosynthetic analysis
- Condensations of carbonyl compounds
Aldol condensation in basic and acid conditions: symmetrical, cross-linked, and intramolecular reaction. Retrosynthetic analysis. Claisen condensation in basic conditions: symmetric, crossed, and intramolecular reaction. Michael reaction of alpha, beta-unsaturated carbonyls: study on the addition of 1,2 and 1,4, and retrosynthetic analysis. Conjugated addition of enamines. Robinson cyclization.
- Amines
Amine synthesis via alkylation, reduction, and reductive amination. Comparison of structure and basic properties. Reactions of Hofmann elimination and diazotization.

Reference texts/books
Study of the theory:
1. Chimica Organica, Janice G. Smith, McGraw-Hill, 2007.
2. Chimica Organica, John McMurry, 7th Edition, Piccin, 2008.
3. Chimica Organica, W. H. Brown, C. S. Foote, B. L. Iverson, E. V. Anslyn, 4th Edition, EdiSES, 2010
4. Chimica Organica, K. Peter, C. Vollhardt, N.E. Schore, 4th Edition, Zanichelli, 2016
5. Lecture notes.
Study and analysis of synthesis and retrosynthesis:
1. Guida ragionata allo svolgimento di esercizi di chimica organica, M. Valeria D'Auria, O. Taglialatela Scafati, A. Zampella, Loghìa Editore, 2nd Ed., 2009.
2. Esercizi di Chimica Organica, Cacchi S., Nicotra F., CEA - Casa Editrice Ambrosiana, 2001
3. Organic Synthesis: The Disconnection Approach, 2nd Edition, S. Warren, P. Wyatt, Wiley, 2009 (Text available only in English).

Learning test
The assessment of learning takes place through a written and an oral test. Before accessing the oral test, the student must have passed the written test and he/she must have received a positive evaluation of written reports related to the laboratory part of the Organic Chemistry II course. According to the schedule provided by the University, the student may decide to take the oral exam one week after the written one. The written test consists of a series of exercises on the entire program carried out (see contents section), aimed at ascertaining the skills acquired in solving problems of synthesis and organic synthesis and in proposing logical mechanisms of reactions. During the written test, lasting about 2 hours, the use of books, electronic or handwritten notes, electronic media is not permitted. The oral test consists of a series of questions to which the student must answer by demonstrating knowledge and ability to expose the topics of the entire program (see contents section) with knowledge of both the language and the use of scientific chemical symbology. The oral test lasts from 15 to 30 minutes depending to the clarity and consistency of the answers to the asked questions. The final score of the exam is predominantly evaluated (80-85%) based on the outcome of the written test, while the evaluation of the oral test and of the laboratory reports integrate (positively or negatively) the mark of the written test.

Classroom lectures are organized through the discussion of theoretical topics followed by the resolution of exercises of both synthesis and retrosynthesis problems, and mechanistic interpretations. In the "moodle" platform of the University, the content of classroom lectures can be downloaded as well as model exercises for the written exam.

Italian

written and oral

This subject deals with topics related to the macro-area "Climate change and energy" and contributes to the achievement of one or more goals of U. N. Agenda for Sustainable Development