Download CHEM 263 (AS 40) Organic Chemistry II Winter 2017 Instructor: Dr

CHEM 263 (AS 40) Organic Chemistry II
Winter 2017
Instructor: Dr. ManzarSaberi
Office: 5- 138 G, City Center Campus
Phone: (780) 497-4634
Email: [email protected]
Lectures: Monday, Wednesday, Friday 1:00-1:50 CCC Room 6-252
Office Hours: Office Hours: Monday, Wednesday, 9:00-10:30, and Friday 9:00-10:00
Total Course Hours: Lecture 45 hours, Laboratory 36 hours
Web address:http://academic.macewan.ca/saberim
Textbook: Organic Chemistry by T. W. Graham Solomons and Craig B. Fryhle,12thedition
Laboratory Manual: Organic Chemistry 263 Laboratory Manual edition 2016
Optional Materials: Study Guide and Solution manualand molecular model kit.
Grade Distribution:
Term I Exam- Friday, January 27
(50 min)  15 %
Term II Exam- Friday, February 17 (50 min  15 %
Term III Exam-Friday, March17
(50 min  15 %
Final Examination
(3.0 Hours) 30 %
Laboratory Component
 25%
Laboratory Examination, Monday, April 3, 6:00-7:30 PM
Note: Students are responsible for verifying the date of the final exam (see here).
Course Description: (3 credits). The nomenclature, structure, physical properties, synthesis and selected reactions of the basic
functional groups in organic chemistry are discussed. Functional groups covered include alkenes, alkynes, aromatic compounds,
alcohols, phenols, ethers, aldehydes, ketones, amines, carboxylic acids and carboxylic acid derivatives. The presence of these
functional groups in natural products is emphasized. The application of spectroscopic methods for structure determination in simple
organic molecules is discussed.
Prerequisite: Minimum grade of C- in CHEM 164 or 261
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.
To obtain a minimum grade of C- in CHEM 263, a score of 50% or higher must be obtained for the laboratory component and, at least
70% of the experiments, must be completed.
Upon completion of this course the student will be able to:
• Apply chemical concepts learned in the lecture to laboratory situations and vice versa.
• Identify and name a variety of organic functional groups (alkenes, alkynes, alcohols, phenols, ethers, aromatic compounds,
aldehydes, ketones, amines, carboxylic acids and carboxylic acid derivatives). Draw structural formulas of organic compounds
fromtheir names and vice versa.
• Summarize and predict the chemical and spectroscopic properties of an organic compound based on the functional group(s)
present in the molecule.
• Summarize the theory and application of infrared (IR), nuclear magnetic resonance (NMR), and ultraviolet (UV) spectroscopy as
applied to organic compounds.
• Determine the structural formula of a simple organic compound using information provided by spectroscopic methods (IR, NMR,
and UV spectroscopy).
University Information
Grading: MacEwan University adheres to the Alberta Common Grading Scheme, which is a 12 point letter grade system. While
faculty may use percentages to aid in their grade development, only the letter grade will appear on transcripts.
A+
95 - 100%
A
90 – 94%
A-
85 – 89%
B+
Excellent
80 – 84%
B
75 – 79%
B-
70 – 74%
C+
Good
65 – 69%
C
60 - 64%
C-
55 – 59%
Satisfactory
D+
50 - 54%
D
45 - 49%
F
below
45%
Minimum
Pass
Fail
Official grades will be provided by the Office of the University Registrar through myStudentSystem. A minimum grade of C– is
required to receive transfer credit or to satisfy a prerequisite for a higher level course.
Important Dates:
Jan 4
Jan 9
Jan 13
Feb 21-24
April 3
April 7
April-11-22
First day of classes
Laboratories begin
Last day for program changes (drop/add courses)
Reading week (no classes or laboratories)
Laboratory examination
Last day of classes, Last day to withdraw from courses(without academic penalty)
Final examination period
Student Responsibilities:
Students are expected to be aware of their academic responsibilities as outlined in MacEwan University Policy E3101: Student
Rights and Responsibilities (found here).
1.
Academic Integrity: All forms of student dishonesty are considered unacceptable. MacEwan University Policy C1000:
Academic Integrity (found here) promotes honesty, fairness, respect, trust, and responsibility in all academic work. According to
the policy, “Academic dishonesty involves participating in acts by which a person fraudulently gains or intentionally attempts to
gain an unfair academic advantage thereby compromising the integrity of the academic process”. All incidents of academic
dishonesty are reported and recorded by the Academic Integrity Office. The penalties and sanctions for academic dishonesty can
include the following: a mark reduction up to zero on a piece of academic work, a grade reduction up to an F in the course, and
suspension or expulsion (with transcript notation) from the University. Please see the academic integrity policy for more details.
You are responsible for understanding what constitutes academic dishonesty.
2.
Registration Status: You are responsible for your registration status at the University. Academic advisors (Rm 6-211) 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 myStudentSystem. You should check
your official registration status before the last date to officially withdraw from the course.
3.
Course prerequisites: Students are responsible for having all prerequisites required for a given course. Prerequisite checks are
periodically carried out and any students who do not have the appropriate prerequisite may be removed from the course. If you
are removed from the course, you may be responsible for any tuition costs up to the date of removal. Any courses from another
post-secondary institute cannot be used as a prerequisite until assessed and approved for transfer credit.
4.
Withdrawing From The Course: If you stop attending class you must complete a Course Drop Form, have it signed by a
Academic Advisor (Rm 6-211), and submit it to the Office of the University Registrar by the last day to withdraw as provided in
the Academic Schedule in the Academic Calendar. Failure to officially withdraw will result in a grade being assigned based on
course work completed. Late withdrawals are only allowed in exceptional circumstances.
5.
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. Only calculators approved for use by the instructor may be used during examinations, which include any
laboratory and lecture quizzes. Any devices capable of external communication, such as cell phones, iPods and blue tooth enabled
devices, cannot be used for exams of any type. Permission to use the washroom during exams is at the discretion of the instructor
and may require accompaniment.
6.
Missed Term Exams: If you miss a term examination you must provide the instructor with an explanation within 24 hours or a
mark 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 examination was missed will be needed to assess whether your absence will be excused or not. If
your absence is excused the weight of this examination will be added to the weight of the final examination in the course. 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 examination are
generally not accepted. A mark of zero will be given if the instructor considers the excuse inappropriate or inadequately
substantiated.
7.
Final Exams: You are responsible for accessing and confirming the official date, time, duration and location of the final exam.
The Office of the University Registrar releases the official schedule no later than half-way through the term. This schedule is
available here . Students are required to be available for the entire exam period. For further information, see MacEwan
University Policy C2005: Final Assessment (found here).
8.
Deferred Final Exam: University policy allows for the deferral of exams for extenuating circumstances, such as illness or
catastrophic events. To apply for a deferral, see Program Services (Rm 6-211). Applications must be received by Program
Services within two business days of the missed exam. A fee of $50 per exam, up to a maximum of $100, will be charged to your
account. Note that a vacation, even if paid for and/or documented, is not grounds for an exam deferral. Application forms are
available from the Program Services office, and must be submitted with appropriate documentation. Students should advise their
instructor prior to the examination if they know beforehand that they will be unable to attend the scheduled examination time. If
you have any questions about the process please contact Program Services (780 497 4520 or [email protected]). For further
information please refer to MacEwan University Policy C2005: Final Assessment (found here) and Policy C2020: Grading (found
here).
9.
Late Assignments (including laboratory assignments): As due dates for assignments are known well in advance, medical and
other excuses are generally not accepted as a reason for submitting late assignments.
10. Cell Phones: All cell phones are to be turned off during class and exam periods (except under exceptional circumstances in which
approval has been given by the instructor).
11. 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 Life office. You should advise the course
instructor(s) of any special needs that are identified. See Policy E3400 Students with Disabilities (found here).
12. Student Appeals: The University has a policy regarding Student Appeals (E3103, found here). You should access this policy to
become aware of the deadlines and guidelines that need to be followed if you are appealing a grade or other University
assessment. Assistance with the appeals process is available through counsellors in the Student Life office. Please call 780 497
5064 to make an appointment.
13. MyMacEwan.ca Email: All students are given a <name>@mymacewan.ca email address. This email address is available to the
course instructor who may distribute relevant course information or announcements via email. The Faculty of Arts and Science
regularly communicate with students via email. Check your mymacewan.ca email regularly or forward it to an email address you
check regularly. If you use email to communicate with your instructor, you must use your mymacewan.ca account. This is to
protect your privacy; if a non-mymacewan.ca account is used, there is no way for an instructor to verify the identity of the sender.
Disclaimer: 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
Chapter7. Hydrogenation of Alkenes
The Function of the Catalyst
- Syn and anti- addition
Hydrogenation of Alkynes
- Syn- addition of hydrogen: Synthesis of cis-Alkenes
-Anti addition of hydrogen: Synthesis of trans-Alkenes
Text Sections:7.15-7.17.
Chapter8. Alkenes and Alkynes II: Addition reactions
Addition reactions of alkenes
- Why Addition Reactions Occur?
- Electrophilic Addition To an Alkene
Electrophilic addition of hydrogen halides to alkenes: Mechanism and Markovnikov’s Rule
Theoretical Explanation of Markovnikov’s Rule
- General statement of Markovnikov’s Rule
Regioselective reactions
Anti-Markovnikov Addition of HBr in the presence of Peroxides
Stereochemistry of the ionic addition to an alkene
Addition of water to alkenes: Acid-catalyzed hydration
- Mechanism
- Rearrangements
Alcohols from alkenes through oxymercuration-demercuration: Markovnikov’s addition
- Regioselectivity of oxymercuration-demercuration
- Rearrangement Seldom Occur in 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
Mechanism for the reaction
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: 8.1- 8.9, 8.11- 8.13, 8-15-8.20
Chapter9. Nuclear Magnetic Resonance Spectroscopy
Nuclear Magnetic Resonance (NMR) spectroscopy
- Chemical shift
- Integration of signal area
- Coupling (signal splitting)
How to interpret proton NMR spectra
Shielding and Deshielding of Protons: More about Chemical Shift
Chemical Sift Equivalent and Nonequivalent Protons
- Homotopic and Heterotopic Atoms
- Enantiotopic and Diastereotopic Hydrogen Atoms
Spin-Spin Coupling: More about Signal Splitting and Nonequivalent or Equivalent protons
- Vicinal Coupling
- Coupling Constant-Recognizing Splitting Patterns
Proton NMR Spectra and Rate Processes
Carbon-13 NMR
- Interpretation of 13C NMR Spectra
- One Peak for Each Magnetically Distinct Carbon Atom
- 13C Chemical Shifts
- DEPT 13C Spectra
Text Sections: 9.1-9.18.
Chapter10. 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: 10.1-10.7,10-10.
Chapter11: Alcohols and Ethers: Synthesis and Reactions
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
- Phenols in the Williamson Ether Synthesis
- Synthesis of ethers by Alkoxymercuration-demercuration.
Reactions of Ethers
Cleavage of Ethers
- Cleavage of Alkyl Aryl Ethers
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 to use alkenes in synthesis
Text Sections: 11.1 –11.2, 11.4-11.15. (11.11A- D No 11.11E- F& 11.14 A)
Chapter12. 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
Alcohols by Reduction of Carbonyl Compounds
- lithium aluminum hydride
- Sodium borohydride
- Overall summary of LiAlH4 and NABH4 reactivity
Oxidation of alcohols
- A Common Mechanistic Theme
- Chromic Acid (H2CrO4) Oxidation
- PyridiniumChlorochromate (PCC)
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 Synthesis Using a Grignard Reaction
Restrictions on the use of Grignard reagents
The use of lithium reagents
The use of sodium alkynides
Text Sections: 12.1 – 12.3(No 12.3D), 12.4(No 12.4B), 12.5- 12.8.
Chapter14. Aromatic Compounds
Nomenclature of Benzene Derivatives
Text Sections: 14.2
Chapter15. 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 Benzene ring Carbon Side Chains:
- Benzylic Halogenation of the Side Chain
- Conjugation is Favored when Alkenylbenzenes are Formed by Elimination Reactions
- Addition to the Double Bond of Alkenylbenzenes
- Oxidation of the Side Chain
Synthetic Strategies
- Choosing the Order of Reactions
- Use Protecting and Blocking Groups
Text Sections: 15.1- 15.12 (No 15.7B).
Chapter 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: Mechanistic Theme
- 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
Imines
- Enamines
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: 1H NMR, IR spectroscopy
Summary of aldehyde and ketone addition reactions
Text Sections: 16.1-16.7 (no 16.7 D), 16.8 (no 16.8 B & C), 16.9-16.10(no 16.10 B), 16.11, 16.13-16.14.
Chapter 17: Carboxylic Acids and their Derivatives: Nucleophilic Addition-Elimination at the Acyl Carbon
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 spectra
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 – 17.5, (no 17.3 (4),& 17.7A.
Chapter20: 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 acids
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, F), 20.4, 20.11
Organic Chemistry by T. W. Graham Solomons and Craig B. Fryhle, and Scott A. Synder 12th edition