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MacEwan University Winter 2013 CHEM 263 (42) -Organic Chemistry II Instructor: Office: Dr. Manzar Saberi 5- 138 G, City Center Campus Phone: 497-4634 Lectures: Tuesday, Thursday 8:00-9:30 CCC Room 7-325 Office Hours: Tuesday, Thursday, 9:30-11:30 Web address: http://academic.macewan.ca/saberim Textbook: Organic Chemistry by T. W. Graham Solomons and Craig B. Fryhle, 10th edition Grade Distribution: 22.5 % 1st Midterm- Thursday, January 31 (80 min) 22.5% 2nd Midterm- Thursday, February28 (80 min) Final Examination- April 16, AM (3.0 hours) 30 % Laboratory Examination- April 5 (6:00-7:30 PM) 25% Description: This is the second course in organic chemistry. The topics covered include structural and chemical properties of alkenes, alkynes, alcohols, phenols, ethers, aromatic compounds. Aldehyde, ketones, amines, carboxylic acids, and carboxylic acid derivatives. Illustration of these functional groups in natural products is provided. The application of spectroscopic methods for structural determination in simple molecules is discussed. Prerequisite: Minimum grade of C- in CHEM 161 or 261 The Faculty of Arts and Science strictly adheres to the notion of prerequisites, and University staff conduct prerequisite checks throughout the term. If it is discovered that you do not have the appropriate prerequisite for this course, you will be withdrawn by the Registrar’s Office. Deciding to remain in the course without the prerequisite may result in a significant financial penalty because you will be responsible for any tuition costs associated with the course up to the date of the withdrawal. Courses transferred to Grant MacEwan University from another post-secondary institution will not be applied to your student record until a transfer credit assessment has been completed. If you believe you have the proper external prerequisite please consult with an advisor in the program office (6-211). Laboratory: Laboratory classes begin the second week of the term. The laboratory component is compulsory for credit in CHEM 263; attendance is mandatory and no make-up labs are available. If you know that you will be unable to attend a scheduled laboratory period, it is your responsibility to inform your laboratory instructor at least one week prior so that you can complete the experiment in another laboratory session. If a laboratory period is missed for a valid reason, the experiment may not be counted towards the final laboratory grade. In all other cases, a mark of zero will be assigned. Students who miss more than two labs will not receive credit for the laboratory component. Students must pass the laboratory component (minimum 50 %) and at least 70% of the experiments in order to pass the course. College Information Grading: Grant MacEwan College adheres to the Alberta Common Grading Scheme, which is a letter grade system. While instructors may use percentages to aid in their grade development, only the letter grade will appear on transcript. A+ A A– B+ 100 > 95 95 > 90 90 > 85 85 > 80 B B– C+ C 80 > 75 > 70 > 65 > 75 70 65 60 C– D+ D F 60 > 55 55 > 50 50 > 45 45 > Unofficial FINAL grades (lecture and laboratory) will be posted on my website approximately one week after each respective final exam at http://academic.macewan.ca/saberim A minimum grade of C- is required to receive transfer credit or to satisfy a prerequisite for higher-level course. Important Dates: 02 Jan 07 Jan 09 Jan 18 – 22 Feb 08- March 10 – 19 Apr First day of classes Laboratory classes begin Last day for program changes (drop/add courses) Reading Week (no classes or laboratories) Last day to withdraw from courses (without academic penalty) Examination period Student Responsibilities Students are expected to be aware of their academic responsibilities as outlined in the Students’ Rights and Responsibilities section in the College Calendar. ACADEMIC INTEGRITY: Academic Integrity: The Academic Integrity policy (C1000) promotes honesty, fairness, respect, trust, and responsibility in all academic work. You are responsible for understanding what constitutes academic dishonesty and acting accordingly. In chemistry, a grade of zero is the minimum penalty for any act of academic dishonesty. Cheating on final exams will generally result in a final grade of F for the course. All offenses will be reported to the college Academic Integrity Officer who may take additional disciplinary action. Registration Status: You are responsible for your registration status at the College. Program Advisors may assist you with the process of registration, including adding or dropping of courses, but it is your responsibility to verify that these changes have been officially completed. This verification can be done at any time using Web Advisor. You should check your official registration status before the last date to officially withdraw from the course. WITHDRAWING FROM THE COURSE: Students who stop attending class must officially withdraw from the course. This must be done by the official withdrawal deadline for the course, which can be determined from the Academic Schedule in the College Calendar. Failure to withdraw properly will result in a grade, based on completed course work, being assigned. EXAMS: Your student photo I.D. is required at exams. It is at the discretion of the instructor whether you will be allowed to write the exam if you arrive over 15 minutes after the exam has begun. You must remain in the exam room for at least 20 minutes from the time it commenced. Permission to use the washroom during exams is at the discretion of the instructor and may require accompaniment. MISSED TERM EXAMS: If you miss a term exam you must provide the instructor with an explanation within 24 hours or a grade of zero may be given. Notification may be provided through email, voice mail, or direct contact with the instructor. Official documentation as to why the exam was missed will be needed to assess whether pro-rating of the course grade will be allowed. Medical excuses must include the date you were examined, the specific dates for the period of the illness, a clear statement indicating that the severity of the illness prevented you from attending school or work, and the signature of the examining physician (a signature by office staff on behalf of the physician is not acceptable). Medical notes obtained subsequent to the date of the exam are generally not accepted. A grade of zero will be given if the instructor considers the excuse inappropriate or inadequately substantiated. DEFERRED FINAL EXAM: A deferred exam will be granted if you miss the final lecture exam for reasons considered by the Science Department to be unavoidable (deferred exams do not apply to term or lab exams). Advise your instructor within 24 hours of your absence and intent to apply for a deferred exam. Application forms are available from the Science Department Office. Completed applications and supporting documentation must be submitted to the Science Department within 48 hours from the date of the missed final exam or a grade of zero will be given on the final exam. You should advise the instructor prior to the exam if you know beforehand that you will be unable to attend the scheduled exam time. Deferred exams are granted by the Science Department, not by the course instructor. STUDENTS WITH DISABILITIES: Students with disabilities who may have special requirements in this course are advised to discuss their needs with Services to Students with Disabilities located in the Student Resource Centre. The course instructor(s) should be advised of any special needs that are identified. See Policy E3400 — Students with Disabilities. MYMAIL.MACEWAN EMAIL: All students are given a <name>@MyMail.MacEwan.ca email address. ISCLAIMER: The information in this Course Outline is subject to change. Any changes will be announced in class or, if applicable, in the laboratory. Chemistry 263 Course Outline 7. Alkenes and Alkynes: Hydrogenation of Alkenes and Alkynes An Introduction to Organic Synthesis 5. Alkenes and Alkynes II: Addition reactions Addition reactions of alkenes How to undersatand additios to alkenes Electrophilic addition of hydrogen halides to alkenes: Mechanism and Markovnikov’s Rule - theoretical explanation of Markovnikov’s rule - modern statement of Markovnikov’s rule - regioselective reactions - exception to Markovnikov’s rule Stereochemistry of the ionic addition to an alkene Addition of water to alkenes: Acid-catalyzed hydration - mechanism - rearrangements Alkohols from alkenes through oxymercuration-demercuration: Markovnikov’s addition - Regioselectivity of oxymercuration-demercuration - Mechanism of oxymercuration Alcohols from alkenes through hydroboration-oxidation:Anti-Markovnikov syn hydration Hydroboration: Synthesis of alkylboranes - mechanism of hydroboration - stereochemistry of hydroboration Oxidation and hydrolysis of alkylboranes - regiochemistry and stereochemistry of alkylborane oxidation and hydrolysis Summary of alkene hydration methods Electrophilic addition of bromine and chlorine to alkenes - mechanism of halogen addition - stereospecific reactions Halohydrin formation Oxidation of alkenes: Syn 1,2-dihydroxylation - mechanism for syn dihydroxylation of alkenes Oxidative cleavage of alkenes - cleavage with hot basic potassium permanganate - cleavage with ozone Electrophilic addition of bromine and chlorine to alkynes Addition of hydrogen halides to alkynes Oxidative cleavage of aklynes How to plan a synthesis: some approach and examples - retrosynthetic analysis - disconnections, synthons, and synthetic equivalents - stereochemical considerations Text Sections: 7.13-7.15, 7-16; 8.1- 8-3, 8.5-8.10, 8.12-8.14, 8-16-8.21 9. Nuclear Magnetic Resonance Spectroscopy Nuclear Magnetic Reonance (NMR) spectroscopy - chemical shift - integration of signal area - coupling (signal splitting) How to interpret proton NMR spectra Nuclear Spin: The origin of the signal Detecting the signal: Fourier transform NMR spectrometers Shielding and deshielding of protons The chemical shift - PPM and the δ scale Chemical shift equivalent and nonequivalent protons - Homotopic and heterotopic atoms - Enantiotopic and diastereotopic hydrogen atoms Signal slitting: Spin-spin coupling - Vicinal coupling - Splitting tree diagrams and the origin of signal splitting - Coupling constants-recognizing splitting patterns - The dependence of coupling constants on dihedral angle - Complicating features - Analysis of complex integrations Proton NMR spectra and rate processes Text Sections: 9.1-9. 10. Radical Reactions Introduction: How radicals forms and how they react - Production of radicals - Reactions of radicals Homolytic bond dissociation energy (∆Ho) - How to use hemolytic bond dissociation energies to calculate heat of reaction - How to use hemolytic bond dissociation energies to determine the relative stabilities of radical Reactions of alkenes with halogens - Multiple halogen substitution - Lake of chlorine selectivity Chlorination of methane: Mechanism of reaction - Activation energies - Reaction of methane with other halogens Halogenation of higher alkanes - Selectivity of bromine The geometry of alkyl radicals Reactions that generate tetrahedral chirality centers - Generation of a second chirality center in a radical halogenations Radical addition to alkenes: The anti-Markovnikov addition of hydrogen bromide - Summary of Markovnikov versus anti-Markovnikov addition of HBr to alkenes. Text Sections: 10.1-10.9. 11. Alcohols and Ethers Structure and Nomenclature - nomenclature of alcohols - nomenclature of ethers Physical Properties of Alcohols and Ethers Synthesis of Alcohols from Alkenes Reactions of Alcohols Alcohols as Acids Conversion of Alcohols into Alkyl Halides Alkyl Halides from the Reaction of Alcohols with Hydrogen Halides - mechanism of the reactions of alcohols with HX Alkyl halides from the reaction of alcohols with PBr3 or SOCl2 Tosylate, mesylates, and triflates: Leaving group derivatives of alcohols Synthesis of Ethers - ethers by intermolecular dehydration of alcohols - the Williamson Ether Synthesis of ethers - synthesis of ethers by Alkoxymercuration-demercuration. Reactions of Ethers - ether cleavage Epoxides - synthesis of epoxides: epoxidation - stereochemistry of epoxidation Reactions of epoxides - acid-catalyzed ring opening of an epoxide - base-catalyzed ring opening of an epoxide Anti 1,2-dihydoxylation of Alkenes via Epoxides Summary of reactions of alkenes, alcohols, and ethers - how alkenes can be used in synthesis Text Sections: 11.1 –11.2, 11.4-11.15. (no 11.11 D, E and 11.14 A) . 12. Alcohols from Carbonyl Compounds. Oxidation-reduction and Organometallic compounds Structure of the Carbonyl group - reactions of Carbonyl Compounds with Nucleophiles Oxidation-reduction Reactions in Organic Chemistry - oxidation states in organic chemistry Alcohols by Reduction of Carbonyl Compounds - lithium aluminum hydride - sodium borohydride - overall summary of LiAlH4 and NABH4 reactivity Oxidation of alcohols - oxidation of primary alcohols to aldehyde - oxidation of primary alcohols to carboxylic acids - oxidation of secondary alcohols to ketones - mechanism of chromate oxidations - a chemical test for primary and secondary alcohols - spectroscopic evidence for alcohols Organometallic Compounds Preparation of organolithium and organomagnesium compounds - organolithium compounds - Grignard reagents Reactions of organolithium and organomagnesium compounds - reactions with compounds containing acidic hydrogen atoms - reactions of Grignard reagents with epoxides - reactions of Grignard reagents with carbonyl compounds Alcohols from Grignard Reagents How to plan a Grignard synthesis Restrictions on the use of Grignard reagents The use of lithium reagents The use of sodium alkynides Text Sections: 12.1 – 12.8. 14. Aromatic Compounds Nomenclature of Benzene Derivatives Text Sections: 14.2 15. Reactions of aromatic Compounds Electrophilic Aromatic Substitution Reactions A General Mechanism for Electrophilic aromatic substitution Reactions of Benzenes - halogenation - nitration - sulfonation - Fridel-Crafts alkylation - Friedel-Crafts Acylation - Limitation of Friedel-Craft reactions Synthetic Applications of Friedel-Crafts Acylations: The Clemmensen Reduction Substituents can affect both the reactivity of the ring and the orientation of the incoming group - how do substituents affect reactivity? - ortho-para directing groups and meta-directing groups - electron-donating and electron-withdrawing substituents - ortho-para directors - deactivating groups: Meta directors - halo substituents: Deactivating ortho-para directors - classification of substituents How substituents affect electrophilic aromatic substitution: A closer look - reactivity: The effect of electron-releasing and electron-withdrawing groups - inductive and resonance effects: Theory of orientation - meta-directing groups - ortho-para-directing groups - ortho-para direction and reactivity of alkylbenzene Reactions of the Side Chain of Alkylbenzenes: - benzylic radicals and cations - halogenations of the side chain: Benzylic radicals - oxidation of the side chain Alkenylbenzenes: - stability of conjugated alkenylbenzenes - addition reaction to the double bond of alkenylbenzenes Synthetic Applications - use of protecting and blocking groups - orientation in disubstituted benzenes Allylic and Benzylic Halides in Nucleophilic Substitution Reactions Text Sections: 15.1- 15.15. 16. Aldehydes and Ketones. Nucleophilic Addition to the Carbonyl Group Nomenclature of Aldehydes and Ketones Physical Properties Synthesis of aldehydes: - aldehyde by oxidation of 1o alcohols - aldehydes by ozonolysis of alkene - aldehydes by reduction of acyl chlorides, esters, and nitriles Synthesis of ketones: - ketones from alkenes, arenes, and 2o alcohols - ketones from nitriles Nucleophilic Addition to the Carbon-oxygen Double Bond - relative reactivity of aldehydes vesus ketones - reversibility of nucleophilic addition to the carbon-oxygen double bond - addition products can undergo further reactions The addition of alcohols: Hemiacetals and acetals - hemiacetals - acetals - acetals are used as protecting groups The addition of primary and secondary amines - oximes and hydrazones The addition of hydrogen cyanide: Cyanohydrins The addition of Ylides: The Wittig reaction - how to plan a Wittig synthesis Oxidation of aldehydes Tollen’s test (silver mirror test) Spectroscopic properties of aldehydes and ketones. Summary of aldehyde and ketone addition reactions Text Sections: 16.1-16.10, 16.12-16.14 17. Carboxylic Acids and their Derivatives Introduction Nomenclature and physical Properties - carboxylic acids - carboxylate salts - acidity of carboxylic acids - dicarboxylic acids Carboxylic acid Derivatives: - esters - carboxylic anhydrides - acyl chlorides - amides - nitriles Spectroscopic Properties of Acyl Compounds - 1H NMR - IR specra Preparation of Carboxylic acids by: oxidation of alkenes oxidation of aldehydes and primary alcohols oxidation of alkylbenzene - hydrolysis of cyanohydrins and other nitriles - carbonation of Grignard reagents Acyl substitution: Nucleophilic Addition – Elimination at the Acyl carbon - relative reactivity of acyl compounds Acyl chlorides - synthesis of acyl chloride using thionyl chloride Synthesis of esters: Fischer esterification - mechanism of the esterification reaction Text Sections: 17.1 – 17.7. (no17.3 (4), and 17.5B, 17.6) 20. Amines Nomenclature of Amines - arlyamines Physical Properties and structure of amines - basicity of amine : Amine salts - basicity of arlyamines - amines versus amides - solubility of amines in aqueous acid Preparation of amines - through nucleophilic substitution reactions - the Gabriel synthesis - preparation of aromatic amines through reduction of nitro compounds - preparation of primary, secondary, and tertiary amines through reductive amination - preparation of primary, secondary, or tertiary amines through reduction of nitriles, oximes, and amides Spectroscopic analysis of Amines Text Sections: 20.1(A) –20.3(A-E, no B), 20.4, 20.11 22. Carbohydrates Classification of Carbohydrates Classification of Monosaccharides D and L Designations of Monosaccharides Structural Formulas for Monosaccharides Mutarotation Glycoside Formation Oxidation reactions of monosaccharides - Benedict’s or Tollens’ reagents: Reducing sugars Disaccharides: maltose cellobiose sucrose lactose Polysaccharides starch cellulose Text Sections: 22.1 A, 22.2 – 22. 4, 22. 6 A, 22.10, 22.12, 22.13 A, C. Organic Chemistry by T. W. Graham Solomons and Craig B. Fryhle, 10th edition Learning and studying guide 1. Read the text before class. Don’t expect to understand it, just read it. When reading novels, plays, or poetry in English, do you read the text before or after the class discussion? In which would you participate more and learn more in the process? Studies have shown that individuals remember about 10 % of material the first time they are introduced to it and up to 50 % the second time. By reading the textbook before class, you acquaint yourself with the information so that the classroom is where you see the material for the second time. You will find yourself saying, “Oh, so that’s what the textbook means!” Studies also show that reviewing your notes within 24 hours of taking them also improves retention. 2. Rewrite your notes at midterm and again at the end of term. Writing is a form of active learning. Rewriting your notes forces you to critically review the information, follow the ‘train-of-thought’ of the instructor, and say it in your own words. Importantly, you end up with a smaller set of notes from which to study for the final! Cue cards are great study tool and convenient when traveling. 3. When studying, don’t just read, write! Rewrite your notes, solve problems, and redo derivations. Prepare a ‘super-summary’ of your notes that contains only the important concepts. When you review the summary, fill in the details in your mind. 4. Don’t pull ‘all nighters’. Your ability to lean when fatigued is very low. Furthermore, your minds’ ability to recall information and dynamically formulate answers is faster if you get a good nights’ sleep rather than if you live off caffeine, etc. 5. Don’t study right up to the exam. Take at least a four-hour break before the exam. Get active: go for a walk, to the gym, etc. Your mind can better consolidate what you have learned if you aren’t cramming more in. Your mind will be refreshed for the exam and you will be able to recall information faster.