Organic Chemistry I.- Alkanes and derivatives

To know the properties and the reactivity of the more representative organic compounds, in particular alkanes and derivatives with a carbon-heteroatom single bond.

CHAPTER 1. Structure and reactivity of organic compounds. Alkanes. Functional groups as sites of reactivity. Lineal and branched alkanes. Nomenclature of alkanes. Structure and physical properties of alkanes. Rotation around single bonds: conformational analysis.

CHAPTER 2. Reactions of alkanes
Bond-dissociation energies: radicals. Structure of alkyl radicals: hyperconjugation. Petroleum chemistry: pyrolysis. Chlorination of methane. Other radical halogenations of methane. Chlorination of higher alkanes: relative reactivities and selectivity. Selectivity in radical halogenation with fluorine and bromine. Synthetic processes based on radical halogenation. Chloroalkanes and ozone layer. Combustion and relative stability of alkanes.

CHAPTER 3. Cycloalkanes
Nomenclature and physical properties of cycloalkanes. Ring strain and structure of cycloalkanes. Cyclohexane: an unstrained cyclic alkane. Substituted cycloalkanes. Polycyclic alkanes. Carbocyclic products in nature.

CHAPTER 4. Steoisomers
Chiral molecules. Optical activity. Absolute configuration: the R-S rules. Fischer projection. Molecules with more than one stereocenter: diasteroisomers. Meso compounds. Stereochemistry of organic reactions. Chiral resolution: separation of enantiomers.

CHAPTER 5. Haloalkanes: bimolecular nucleophilic substitution.
Physical properties of haloalkanes. Nucleophilic substitution. Reaction mechanisms in molecules with polar functional groups. Analysis of the nucleophilic substitution mechanism: kinetics. Stereochemical outcome of SN2 reaction. Inversion in SN2 reactions. Structure and reactivity in SN2 reactions: leaving group, nucleophile and substrate.

CHAPTER 6. Haloalkanes: unimolecular nucleophilic substitution. Elimination (uni- and bimolecular).
Secondary and tertiary haloalkane solvolysis. Unimolecular and bimolecular elimination. Stereochemical outcome of SN1 reactions: stability of carbocations. Effects of solvent, leaving group and nucleophile. Effect of alkyl group in SN1. Unimolecular elimination: E1 mechanism. Unimolecular elimination: E1 mechanism. Bimolecular elimination: E2 mechanism. Competition between substitution and elimination.

CHAPTER 7. Alcohols: preparation and strategy of synthesis.
Nomenclature of alcohols. Structure and physical properties of alcohols. Alcohols as acids and bases. Industrial sources of alcohols: carbon monoxide and ethene. Synthesis of alcohols by nucleophilic substitution. Synthesis of alcohols: redox reactions between alcohols and carbonyl compounds. Organometallic reagents: sources of nucleophilic carbon. Complex alcohols: introduction to synthetic strategy.

CHAPTER 8. Further reactions of alcohols and chemistry of ethers.
Reaction of alcohols with bases: preparation of alkoxides. Reaction of alcohols with strong acids: substitution and elimination through alkyloxonium ions. Carbocation transpositions. Ethers from alcohols. Nomenclature and physical properties of ethers. Williamson synthesis of ethers. Synthesis of ethers from alcohols and mineral acids. Reactions of ethers. Reactions of oxacyclopropanes (epoxides). Physiological properties and applications of alcohols and ethers.

Laboratory :
EXPERIMENT 1 – Acid-base extraction
In this experiment the student will separate three different organic substrates attending to their acid-base properties, by means of liquid-liquid extraction. Once separated, two of the substances will be purified by common techniques for the purification of solids, such as crystallization and sublimation.
Specific literature: M. A. M. Grau and A. G. Csáky, “Técnicas Experimentales en Síntesis Orgánica” 1998, Ed. Síntesis. Chapters: 6.2, 6.3, 6.5 and 9.3.
Activities: Separation of organic substances attending to acid-base properties. Precipitation, filtration, crystallization, sublimation. Use of rotary evaporator. Melting point.

EXPERIMENT 2 Williamson ether synthesis: Synthesis of 2-buthoxynaphthalene.
In this experiment, 2-buthoxynaphthalene will be synthesized by a SN2 nucleophilic substitution. An alkyl halide will be reacted with an alkoxyde. The product is isolated by filtration, after aqueous work-up. The reaction is monitored by thin-layer chromatography.
Specific literature: M. A. M. Grau and A. G. Csáky, “Técnicas Experimentales en Síntesis Orgánica” 1998, Ed. Síntesis. Chapters: 5.1, 5.2.1, 7.1.4, 7.3.2, 9.2. J. Chem. Ed. 2009, 86, 850.
Activities: Preparation of an ether by SN2 reaction (Williamson Synthesis). Stoichiometric calculations. Reflux set-up. Vacuum filtration. Melting point. Thin layer chromatography.

EXPERIMENT 3. Oxidation of secondary alcohols to ketones: oxidation of cyclohexanol to cyclohexanone.
In this experiment, the oxidation of a secondary alcohol with hypochlorite will be carried out. The reaction will be performed at low temperature. Extraction and washing of organic solutions to remove inorganic byproducts. Use of rotary evaporator to concentrate the solutions.
Specific literature: M. A. M. Grau y A. G. Csáky, “Técnicas Experimentales en Síntesis Orgánica” 1998, Ed. Síntesis. Chapters: 5.1, 5.2.1, 6.2, 6.3, 6.4, 7.1.3. J. Org. Chem. 1980, 45, 2030.
Activities: Oxidation of alcohols. Stoichiometric calculations. Thin layer chromatography. Liquid-liquid extraction. Use of rotary evaporator.

EXPERIMENT 4. Synthesis of a chiral compound: preparation of (2S)-2-hydroxy-3-phenylpropanoic acid.
In this experiment the effect of SN2 reactions on chirality will be analysed. Activation of the amino functionality as leaving group: formation of a diazonium salt. Determination of the optical rotation.
Specific literature: M. A. M. Grau y A. G. Csáky, “Técnicas Experimentales en Síntesis Orgánica” 1998, Ed. Síntesis. Cap.: 5.1, 5.2.1, 7.1.4, 7.3.2, 9.2, 12.6. J. Chem. Ed. 2010, 87, 623.
Activities: SN2 Reaction: inversion of configuration. Stoichiometric calculations. Vacuum filtration. Melting point determination. Optical rotation measurement.

EXPERIMENT 5 Nucleophilic substitution reaction: synthesis of 2-chloro-2-methylpropane.
In this experiment, an SN1 reaction will be studied, by transformation of a tertiary alcohol into an alkyl chloride. The liquid product will be isolated by distillation.
Specific literature: R. Brewster, C.A. Vanderwert y W.E. McEwen “Curso Práctico de Química Orgánica" 1965, Ed. Alhambra, Madrid.
Activities: SN1 Reaction. Stoichiometric calculation. Elaboration, isolation and purification of the reaction product. Drying of solvents and organic solutions. Distillation.

Organic Chemistry.
K. P. C. Vollhardt; N. E. Schore
7º Ed in English (previous editions in English are also acceptable)
MacMillan Publishers, 2015

Workbooks
“Cuestiones y Ejercicios de Química Orgánica”
E. Quiñoá, R. Riguera
Ed. McGraw Hill, 1994.
“Nomenclatura y representación de los compuestos orgánicos”
E. Quiñoá, R. Riguera
Ed. McGraw-Hill, 1996

Experimental
“Técnicas experimentales en síntesis orgánica”
M. A. Martínez Grau, A. G. Csákÿ
Ed. Síntesis, 1998

On-line resources
Organic Chemistry Portal: https://www.organic-chemistry.org/

BASIC AND GENERAL SKILLS
CB1- Students should have demonstrated knowledge and understanding in a field of study that is built on the basis of general secondary education, and this is typically at a level which, although it is supported by advanced textbooks, also includes some aspects that will imply knowledge in the forefront of their field of study.
CG1- Graduates should possess and understand the concepts, methods and most important results of the various branches of chemistry, with an historical perspective of its development
CG2- They should be able to gather and understand data, information and relevant results, draw conclusions and issue reasoned reports in scientific, technological or other fields that require the use of knowledge of chemistry problems.
CG3- They should be able to apply both theoretical and practical knowledge acquired as the capacity of analysis and abstraction in the definition and approach to problems and in the search for solutions in both contexts, academic and as professionals
CG4- They should be able to able to communicate, both in writing and orally, knowledge, procedures, results and ideas in chemistry to both a specialist and non-specialist audiences.
CG5- They should be able to able to study and learn independently, with new organization of time and knowledge resources and techniques, in any scientific or technological discipline.

TRANSVERSAL SKILLS
CT1- Capacity for analysis and synthesis
CT2- Ability of organization and planning.
CT3- Knowledge of a foreign language.
CT4- Problem solving
CT5- Decission making

SPECIFIC SKILLS
CE7- Knowledge of properties of organic, inorganic and organometallic compounds.
CE13- Ability to demonstrate knowledge and understanding of essential facts, concepts, principles and theories related to the different areas of chemistry.
CE18- Conduct standard laboratory procedures involved in synthetic and analytical work, in relation to organic and inorganic systems.
CE20- Ability to understand experimental data derived from observation, in terms of their significance and on the base of the theory behind them.
CE25- Ability to relate chemistry to other disciplines.

REGULAR ATTENDANCE TO INTERACTIVE CLASSES (SEMINARS, LABORATORY, and BLACKBOARD TUTORIAL) IS MANDATORY.

a) LECTURES in large group: Lecture provided by the teacher in different formats (theory, problems and/or general examples, general guidelines for the subject...). Normally, these classes will follow the contents of the reference manual proposed in the Teaching Guide of the subject.

b) INTERACTIVE CLASSES (seminars/workshops) in small group: Practical-theoretical class in which applications of the theory and problems are solved. The student participates actively in this classes in different ways: handing over of exercises to the professor (some of those proposed in the worksheets provided in advance); solving problems in the classroom, etc. The students are recommended to use molecular models. Assessment tests may be included and counted upon for the mark in the continuous evaluation. Regular attendance to these classes is mandatory.

c) LABORATORY PRACTICAL CLASSES: The student acquires the skills corresponding to a chemistry laboratory and strengthens the knowledge acquired in the classes of theory. For theses practical classes, the student will get a Laboratory Practice Manual, that includes generalities over the laboratory work, as well as, a guide for each of the experiments, consisting in a brief presentation of the principles, methodology and indications about the calculations and results. The student must read carefully the content of the this Manual before attending each practical exercise. At the beginning of each exercise, the students will show the preliminary questions that will be evaluated and considered for the mark of the practical classes. After an explanation of the teacher, the student will perform individually, or in couples, the experiences and calculations necessary to finish the experiment. After finishing the experiment, the student will answer during 5-10 minutes a few subsequent questions related to the experimente that the teacher will qualify and will consider for the mark for the practical classes. A laboratory notebook must be kept up-to-date according to the Laboratory Practice Manual and it must include the procedures and the results of the experiments. It is an added requirement for the evaluation and it will be evaluated by the teacher at the end of each experiment. The attendance to these classes is compulsory. The lack of attendance must be documentary justified, being accepted exam and health reasons as well as those cases included in the current academic regulations. The experiments not done will be made up following guidelines from the teacher fitting the scheduled time for the subject. Lack of attendance without justification results in a FAIL mark in practical classes in the laboratory.

d) Blackboard TUTORIAL CLASSES in a very small group: Tutorials scheduled by the teacher and coordinated by the Faculty. In general, each student will receive 2 hours of tutorials per four-month period. The following activities will be proposed: supervised works, clarification of concepts regarding theory and experiments, problems, exercises, lectures, etc. In many cases, the teacher will demand the student to hand over exercises before the tutorial. These deliveries will be indicated in the calendar of student activities along the course included in the Teaching Guide of the subject. The attendance to these classes is compulsory. Assessment tests may be included and counted upon for the mark in the continuous evaluation.

1. The assessment of this subject consists in two parts:
1.1 Continuous evaluation, weighing 30%, divided in:
. Work in seminars and workshops (15 %)
. Work in tutorial classes (5 %)
. Laboratory classes (10 %)
1.2. Final exam (70%)

2. The assessment of seminars and tutorials is based on the oral, on-line and written evaluation tests and questions done during the teaching period, in seminars/workshops and tutorial classes. The non attendance to some of these classes results in a zero grade in the tests carried out in the corresponding class.

3. The following items are considered for the evaluation of the practical classes:
. Previous test
. Behaviour in the laboratory
. Order and cleanliness in the laboratory
. Implementation of the practical work
. Laboratory notebook
. Final test
The students must obtain a PASS mark in the continuous evaluation of practical classes to pass the whole subject, so they have to attend to all the sessions. Failing to carry out any of the practical classes results in a FAIL mark in the practical classes.

4. The final exam will consist in a number of questions regarding theory and practice that will verify the student's competence.
The final examination will include an eliminatory question about the basic contents that all students must know to pass. Should the student fail this question with basic contents, a qualification of 0 will be assigned to the remaining questions. The basic contents consist in:
• Identifying and naming the funcional groups in an organic molecule.
• Identifying and assigning the (R) or (S) configuration of the stereocenters in an organic molecule.
• Assigning the stereochemistry of alkenes in an organic moleculea.
• Identify stereoisomeric relationships.
• Fundamentals of conformational analysis
The final examination might include questions about practical classes.

5. The student's final mark will not be lower than the final examination's mark nor the mark obtained weighing the continuous evaluation with the final examination. The weighed average of the continuous evaluation mark with the final examination mark will be calculated according to the following formula:

Final mark= maximum (0,3 x N1 + 0,7 x N2, N2)

N1= mark corresponding to the continuous evaluation (0-10)
N2= mark corresponding to the final examination (0-10)

6. Students who have passed the laboratory practices in previous years will keep the corresponding mark during a maximum of two academic years. Therefore, they will not need to repeat the laboratory practices, but they will have to answer the questions on practicals that may appear in the final exam. In addition, these students will have to attend the remaining interactive classes (seminars and tutorials) under the same conditions than the remaining students.

7. Repeaters who have not achieved a pass mark in the laboratory practicals must take them again.

8. Skill will be evaluated in the different kind of classes as follow:
Seminars: CG2, CG3, CG4, CG5, CT1, CT4, CT5, CE7, CE13
Tutorial classes: CG1, CG2, CG3, CG4, CG5, CT2, CT4, CT5, CE25
Laboratory classes: CG2, CG3, CG4, CG5, CT2, CT4, CT5, CE18, CE20
Final exam: CB1, CT1, CT7, CE7, CE13

Presencial classroom activities:
Lectures in large group (23 h)
Interactive lessons in small group (seminars/workshops, 9 h)
Laboratory classes (20 h)
Tutorial classes (2 h)
Total number of hours of classroom and laboratory work (54 h)

Student's personal work:
Autonomous study, individual or in a group: (46 h)
Problem solving: (28 h)
Literature/Library work (10 h)
Preparation of laboratory work (12 h)
Total number of hours of student's individual work (96 h)

TOTAL NUMBER OF WORKING HOURS: 54 h + 96 h = 150 hours

i) Attend lectures
ii) It is very important the regular study of the subject along the semester, keeping an updated revision of concepts, problem solving, study of the class notes and textbook and doing self-assesment exercises and tests.
iii) Deep understanding of concepts and reaction mechanisms
iv) Problem solving is essential to learn this subject.

In case of exercises or test realized by dishonest means, the "Evaluation rules of students’ academic performance and qualifications" will be of application.