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Grant MacEwan University
Fall 2010
CHEM 362 (270) Advanced Organic Chemistry
Instructor: Dr. Manzar Saberi
Office:
5- 172 K, City Center Campus
Phone: 497-4634
Lectures: Tuesday, Thursday, 12:30-2:00 CCC Room 5-141
Office Hours: Monday, Wednesday, Friday 9:30-11:00.
Web address: http://academic.macewan.ca/saberim
Textbook:
Organic Chemistry by Clayden, Greeves, Warren and Wothers
Grade Distribution:
1st Midterm- Thursday, October 7 (80 min)
2nd Midterm- Thursday, November 9 (80 min)
Positive Class Participation
Final Examination- December 9, PM (3.0 hours)
Laboratory





20 %
20%
5%
30 %
25%
(Note: Students are responsible for verifying the date of the final examination when the final
examination schedule is posted later in the term.)
Description: This course is designed to build upon the concepts introduced in Chemistry 261 and
Chemistry 263, offering a more advanced and sophisticated insight into the physical properties and
chemical reactions of organic compounds. A focal point is the chemistry of carbonyl compounds.
Mechanistic and multistep synthesis approaches are emphasized.
Prerequisite: Minimum grade of C- in CHEM 263.
Laboratory: Laboratory classes begin the second week of the term. The laboratory component is
compulsory for credit in CHEM 362; 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 %) 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 transcripts.
A+
A
A–
B+
> 95 %
90 % – 94 %
85 % – 89 %
80 % – 84 %
B
B–
C+
C
75 % – 79 %
70 % – 74 %
65 % – 69 %
60 % – 64 %
C–
D+
D
F
55 % – 59 %
53 % – 54 %
45 % – 52 %
< 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
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Important
Dates:
Sept. 7
Sept. 13
Sept. 14
Oct. 11
Nov.12
Nov. 11
Dec. 7
Dec. 8 - 17
st
1 First day of classes
Laboratories begin
Last day for program changes (drop/add courses)
Thanksgiving day; College closed
Last day to withdraw without academic penalty
Remembrance Day; College closed
Last day of instruction
Final 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: All forms of student dishonesty are considered unacceptable. MacEwan’s
Academic Integrity policy (C1000) 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 Office of Academic Integrity. 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 College. Please see the
academic policy at www.macewan.ca/academicintegrity for more details. You are responsible for
understanding what constitutes academic dishonesty.
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.
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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.
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.
ELECTRONICS: All electronic equipment (cell phones, pagers, walkmans, A/V recorders, etc., except
calculators approved by the instructor) are to be turned off during class and exam periods (except with
written approval of the 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 362 Course Outline
Fall 2010
5. Organic Reactions
Charge attraction bring molecules together
Orbital overlap bring molecules together
Electron flow is the key to reactivity
Nucleophiles donate high-energy electrons to electrophiles
Electrophiles have a low energy vacant orbital
Interaction between HOMO and LUMO leads to reaction
Use of curly arrows to represent reaction mechanisms
Charge is conserved in each step of a reaction
The decomposition of molecules
Drawing your own mechanisms with curly arrows
Decide on a “push” or a “pull” mechanism
Guidelines for writing your own mechanism
Assigned Chapter 5 problems: 1,2,3,4,5,6,7.
6. Nucleophilic Addition to the Carbonyl Group
Molecular orbitals explain the reactivity of the carbonyl group
Cyanohydrins from the attack of cyanide on aldehydes and ketones
The Burgi-Dunitz angle
Nucleophilic attack by “hydride” on aldehydes and ketones
Addition of organometallic reagents to aldehydes and ketones
Addition of water to aldehydes and ketones
Hemiacetals from reaction of alcohols with aldehydes and ketones
Acid and base catalysis of hemiacetal and hydrate formation
Bisulfate addition compounds
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Assigned Chapter 6 problems: 1, 2, 3, 4, 6,7,10.
8. Acidity, Basicity, and pKa
Acidity
Water can behave as an acid or base
Constructing a pKa scale
The choice of solvent
Highly conjugated carbon acid
Nitrogen acids
Basicity
Neutral nitrogen bases
Factor affecting the acidity and basicity
Neutral Oxygen Bases
Amides basicity
Assigned Chapter 8 problems: 3, 4, 5, 6, 7, 8, 9, 12, 14.
10. Conjugate Addition
Conjugation changes the reactivity of carbonyl groups.
Alkenes conjugated with carbonyl groups are polarized.
Polarization is detectable spectroscopically.
Ammonia and amines undergo conjugate addition.
Conjugate addition of alcohols can be catalyzed by acid or base.
Conjugate addition or direct addition to the carbonyl group.
- reaction conditions
- kinetic or thermodynamic control
- structural factors
- the nature of nucleophile: Hard and soft.
Reactivity of hard and soft nucleophiles on conjugate addition.
Copper (I) salts have a remarkable effect on organometallic reagents.
Organocopper reagents undergo conjugate addition.
Assigned Chapter 10 problems: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.
12. Nucleophilic Substitution at the Carbonyl group
The product of nucleophilic addition to a carbonyl group is not always a stable compound
Carboxylic acid derivatives
How do we know that the tetrahedral intermediate exist
Why are tetrahedral intermediate unstable?
pKaH is a useful guide to leaving group ability.
Amines react with acyl chloride to give amides.
Using pKaH to predict the outcome of substitution reactions of carboxylic acid derivatives
Factors other than leaving group ability can be important.
Guide to nucleophilicity.
Reactivity of carboxylic acid derivatives
Carboxylic acids do not undergo substitution reactions under basic conditions
Acid-catalyzed substitution reactions of carboxylic acids
Acid-catalyzed ester hydrolysis and transesterification
Acid-base catalyzed hydrolysis of esters amides, and nitriles
Synthesis of acid chloride using SOCl2, PCl5, and oxalyl chloride
Synthesis of alcohols, ketones, by substitution reactions of acid derivatives
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Assigned Chapter 12 problems: 1, 2, 3, 4, 6, 7, 8, 9, 10, 11.
21. Formation and Reactions of Enols and Enolates
Tautomerism: Formation of enols by proton transfer.
Why don’t simple aldehydes and ketones exist as enols?
Evidence for equilibration of carbonyl compounds with enols
Acid-base catalyzed enolization
The intermediate in the base-catalyzed is the enolate ion.
Summery of types of enol and enolate
Kinetically stable enols
Thermodynamically stable enols; Enols of 1,3-dicarbonyl compounds.
Consequences of enolization
Reaction with enols or enolates as intermediates
Acid-base catalyzed halogenation of carbonyl compounds
Stable enolate equivalents
Assigned Chapter 21 problems: 1, 2, 4, 5, 7, 8, 9, 10.
24. Chemoselectivity: Selective reactions and protection
Selectivity
Reducing agents
Reduction of carbonyl groups
Catalytic hydrogenation
How to reduce unsaturated carbonyl group
Dissolving metal reductions
How to react the less reactive group: protecting groups
Assigned Chapter 24 problems: 1, 2, 3, 4, 5, 6, 7, 9, 11.
27. Reactions of Enolates with Aldehydes and Ketones: The Aldol Reaction
Introduction: The aldol reaction
Aldol reactions of unsymmetrical ketones
Cross-condensations
Compounds that can enolize but that are not electrophilic
Lithium enolates in aldol reactions
Silyl enol ether in aldol reactions
Specific enol equivalents for carboxylic acids
Specific enoate equivalent for esters: Reformatsky reagent
Specific enol equivalens for aldehydes and ketones
Making the less substituted enolate equivalent: Kinetic enolates
Making the more substituted enolate equivalent: Thermodynamic enolates
The Mannich reaction
The Cannizzaro reaction
Intramolecular aldol reactions
Assigned Chapter 27 problems: 1, 2, 3, 4, 6, 8, 9, 10, 11, 12.
28. Alkylation at Carbon
The Claisen ester condenasation compared to the aldol reaction
Problem with acylation at carbon.
Acylation of enolates by ester
The claisen ester condensation and other self-condensation
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How do we know that deprotonation drives the reaction?
Intramolecular acylation: The Dieckmann reaction
Crossed ester condensations
Reactive esters that cannot enolize
Cross Claisen ester condensation between two different esters
Claisen condensations between ketones and esters
Preparation of keto-esters by the Claisen reaction
Intramolecular crossed Claisen ester condensations
Assigned Chapter 28 problems: 1, 2, 3, 4.
30. Retrosynthetic Analysis
Creative chemistry
Synthesis backwards: Retrosynthetic analysis
Disconnection methods
Synthons
Choosing a disconnection
Chemoselectivity problems
Functional group interconversion
Two-group disconnections rather than one
1,3-Disconnections
Donor and acceptor synthons
Two group C-C disconnections
Functional group relationships may be masked by protection
Aldol-style disconnections with Nitrogen and Oxygen in a 1,3 relationship: The Mannich reaction
35 . Pericyclic Reactions: Cycloadditions
A new sort of reaction
General description of the Diels-Alder reaction
-the diene
-the dieophile
-the product
Stereochemistry of the diene
Stereochemistry of dieophile
The endo rule for the Diels-Alder reaction
The frontier orbital description of cycloaddition
Dimerizations of dienes by cycloaddition reactions
The Diels-Alder reaction in more detail
The solvent in the Diels-Alder reaction
Intramolecular Diels-Alder reactions
Summary of regioselectivity in Diels-Alder reactions
Lewis acid catalysis in Diels-Alder reactions
Regioselectivity in intramolecular Diels-Alder reactions
Clayden, Greeves, Warren and Wothers, Organic Chemistry.