Download Grant MacEwan College - Faculty Web Pages

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prerequisite for this course, you will be withdrawn by the Registrar’s Office.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.