Documente Academic
Documente Profesional
Documente Cultură
Organic Chemistry II
Student Manual
Athabasca University
Course Team
Course Professor: Lawton Shaw
Course Authors: Arthur Last and Dietmar Kennepohl
Revisions: Dietmar Kennpohl (1996-2004); Lois Browne (2010)
Reviewer, 2004: David Law
Editor: Gilda Sanders
Visual Presentation: Athabasca University Digital Media Technology Unit
Cover Design: Jingfen Zhang
Every effort has been taken to ensure that these materials comply with the
requirements of copyright clearances and appropriate credits. Athabasca
University will attempt to incorporate in future printings any corrections
which are communicated to it.
The inclusion of any material in this publication is strictly in accord with the
consents obtained and Athabasca University does not authorize or license
any further reproduction or use without the consent of the copyright holder.
c Athabasca University 1998, 2003, 2004, 2010
Contents
The Course . . . . . . . . . . . . . . . . . . . . . . .
The MyAU Portal . . . . . . . . . . . . . . . . . . .
Your Student ID Number . . . . . . . . . . . . . . .
Freedom of Information and Protection of Privacy
The Athabasca University Calendar . . . . . . . .
Course Materials . . . . . . . . . . . . . . . . . . .
Other Items . . . . . . . . . . . . . . . . . . . . . .
Forms . . . . . . . . . . . . . . . . . . . . . . . . . .
Course Design . . . . . . . . . . . . . . . . . . . . .
Laboratories . . . . . . . . . . . . . . . . . . . . . .
Your Tutor . . . . . . . . . . . . . . . . . . . . . . .
The Course Professor . . . . . . . . . . . . . . . . .
Services to Students . . . . . . . . . . . . . . . . . .
Library Services . . . . . . . . . . . . . . . . . . . .
Study Strategies . . . . . . . . . . . . . . . . . . . .
How to Use the Study Guide . . . . . . . . . . . .
Course Outline and Study Schedule . . . . . . . .
Assessment . . . . . . . . . . . . . . . . . . . . . .
Applying for and Writing Examinations . . . . . .
Student Conduct and Appeals . . . . . . . . . . . .
Intellectual Indebtedness . . . . . . . . . . . . . . .
Transcripts . . . . . . . . . . . . . . . . . . . . . . .
Transferring Credit . . . . . . . . . . . . . . . . . .
Applying for Extensions . . . . . . . . . . . . . . .
Sample Examinations . . . . . . . . . . . . . . . . .
Sample Examination Answer Keys . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
1
2
2
2
3
4
4
4
6
7
8
9
10
12
12
14
17
18
20
20
21
21
21
23
55
The Course
Welcome to Chemistry 360: Organic Chemistry II, a three-credit, senior-level,
laboratory science course. We assume that all students registering in this
course will have completed Athabasca Universitys Chemistry 350: Organic
Chemistry I, or an equivalent university-level course in organic chemistry. If
you have not done so, you should contact the course professor immediately.
Organic Chemistry II deals with the chemistry of carbon compounds through
a study of the characteristic reactions of the common functional groups.
Particular emphasis is placed on the study of reaction mechanisms, in an
attempt to show similarities between apparently unrelated reactions. The
importance of stereochemistry is stressed throughout the course. The
compulsory laboratory component of Chemistry 360 introduces the student
to the basic techniques employed in modern organic chemistry laboratories.
Experiments have been selected to illustrate many of the principles
encountered in the theoretical part of the course. The course outline
provided in this manual gives a more detailed description of the course
contents.
This Student Manual provides you with some essential information about
the design of the course, the course materials, and the procedures you
should follow to obtain the maximum benefit from your studies. Please read
it carefully and keep it in a safe place.
Note: These course materials have been designed for students who are
taking the individualized-study version of this course. Students who are in
a grouped-study environment should follow the course outline, study
schedule and learning activities provided by their instructor.
Organic Chemistry II
Course Materials
The package you received should include each of the items listed below. If
anything is missing from your package, please contact the Course Materials
division of Athabasca University as soon as possible. If you live in Canada
or the United States, you can use email to contact Course Materials:
cmat@athabascau.ca
You can also call 1-800-788-9041, choose option 3 from the menu, and enter
extension 6366 when prompted.
Students who live outside of Canada or the United States can contact
Course Materials by email.
You can also write in care of Course Materials, Tim Byrne Centre, 400 Hwy 2
South, Athabasca, AB T9S 1A4.
Textbooks
McMurry, John. Organic Chemistry, 7th ed. Pacific Grove, CA: Brooks/Cole
Publishing Co., 2008.
McMurry, Susan. Study Guide and Student Solutions Manual for McMurrys
Organic Chemistry, 7th ed. Pacific Grove, CA: Brooks/Cole Publishing
Co., 2008.
Organic Chemistry II
Other Items
The items listed below are not supplied; you should purchase them before
you begin to work on the course. You will need
an electronic calculator capable of handling logarithms and exponentials.
ruler, etc.
Forms
The forms you need to submit assignments, request examinations or inform
the University of a change in your status as a student are available through
your myAU home page, or for download from the Office of the Registrars
Online Services (OROS) website:
http://www.athabascau.ca/registrar/forms.php
If you do not have access to the Internet or are unable to obtain the forms
online, please contact the Athabasca University Information Centre, toll
free, at 1.800.788.9041 to request that printed copies be sent to you. For
Chemistry 360, you will need at least two tutor-marked exercise forms and
two examination request forms.
Course Design
The course materials are designed for self-instruction and individualizedstudy. What you should learn and how you should learn it are described in
the Study Guide. This book contains 16 units, each of which corresponds to
one of the chapters in Organic Chemistry, 7th ed., by John McMurry. Each
unit in the Study Guide contains a preview, a list of learning objectives, a
series of subsections corresponding to chapter subsections, and some hints
on how to work through the unit. Let us look at exactly what you can expect
to find under each of these headings.
Unit Preview
The Unit Preview is a brief discussion that outlines the overall approach
taken by the author in the relevant chapter of Organic Chemistry.
Unit Objectives
In this section, we inform you of the overall objectives that we expect you to
be able to fulfill when you have finished studying the unit.
Sections
The sections form the bulk of each unit. Each section in the Study Guide
normally contains the following features:
1. a list of objectives which are more detailed than those provided under
the heading Unit Objectives, and which may be one of the most
valuable features of the Study Guide, because they tell you explicitly what
you need to understand and to be able to do for each unit of the course.
Questions on the examinations and tutor-marked assignments are based
only on the unit objectives. However, you should be aware that many
questions will require you to demonstrate mastery of a number of related
objectives, and that you should not place too narrow an interpretation on
each objective.
2. a list of key terms introduced in the section. Unless we have indicated
otherwise, definitions of these key terms are provided in Appendix
CGlossary, beginning on page A10 of Organic Chemistry, 7th ed.
3. study notes, which may include hints on how to study the material
effectively, additional information, and details of any errors that occur in
the textbook.
4. a list of suggested exercises. These exercises are designed to improve
your understanding of the material you have just studied and to develop
your problem-solving skills. Refer to your notes and to the textbook
when you attempt the exercises. The answers to all the exercises are
provided in the Solutions Manual or in Appendix DAnswers to In-text
Problems, beginning on page A30 of the textbook. Do not spend a large
amount of time on any one exercise. If you are unable to make any
progress after a few minutes of concentrated work, use the answers
to help.
For further information, see the section of this manual titled How to Use
Your Study Guide.
Self tests are given at the end of Units 18, 20, 22 and 24, and after each of the
optional units. These tests are designed to allow you to measure your
progress in the coursethey are not a comprehensive overview of the
material, nor are they at the same level of difficulty that you will encounter
in the midterm and final examinations. [Sample examinations are given in
Organic Chemistry II
this manual.] If you have difficulty with any self test, you should go back
and review the material before going on.
The textbook by McMurry contains most of the information you will need
to pass this course. It is a standard textbook used in many universities and
colleges throughout North America. It was chosen because it offers clear
explanations and interesting discussions of the material we wished this
course to cover. In addition, we felt that this textbook has an advantage in
that it includes some discussion of a number of advances made in organic
chemistry during the last decade. The chapters are relatively short, and the
textbook contains problems, exercises and some review chapters.
Each chapter of the textbook concludes with a useful summary, and where
appropriate, a list of the reactions introduced in the chapter. These reviews
are excellent for quick reference and will help you to prepare for
examinations.
You should use a set of molecular models to assist you in understanding the
stereochemical aspects of the course. If you cannot obtain a set of molecular
models elsewhere, you may order one from the Athabasca University
Library (see the section of this manual titled Library Services). You may
use molecular models during examinations.
Laboratories
You must complete about 32 hours of laboratory work to obtain credit in
this course. Labs are typically held for week-long sessions during the
summer in Athabasca, or for full-day sessions on weekends in Edmonton at
selected times during the rest of the year. The Lab Coordinator will be able
to provide up-to-date information, or you may go to our Lab Information
website at:
http://science.pc.athabascau.ca/labinfo.nsf
You must contact the Lab Coordinator to book into a scheduled laboratory
session. Students in Canada and the United States can reach the Lab
Coordinator by calling 1-800-788-9041 (the extension is 6276). All students
can use electronic mail to contact the Lab Coordinator at
sciencelab@athabascau.ca
Information about the laboratory program and the experiments to be
carried out is included in the Laboratory Manual. Note that your lab work
accounts for 20 per cent of your overall course mark. You must satisfactorily
complete and write up a specified minimum number of experiments to
obtain credit for this course.
Your Tutor
Athabasca University provides each student in each course with a tutor
whose responsibility is to help the student complete the course successfully.
A letter containing your tutors name, address, telephone number and
tutoring hours was mailed to you shortly before your official start date. If
you have not yet received your tutor letter, please contact Learning
ServicesTutorial at Athabasca University as soon as possible. Students in
Canada or the United States can call 1-800-788-9041 (extension 6196); all
students can send electronic mail to
tutserv@athabascau.ca
Note: If you have chosen to receive communications from Athabasca
University in electronic form, be sure to check your myAU portal for your
tutor letter.
Your tutor has excellent academic qualifications, and is committed to
helping students learning at a distance. He or she is available to answer
your questions about course content or how to approach a problem or an
assignment, and can direct you to the right person or department to help
you with other problems that may be hindering your progress in your
course or program. In addition, your tutor will be responsible for marking
your assignments. In general, you should call your tutor first with any
queries about Athabasca University.
The tutor letter will help you become acquainted with your tutor and will
provide information about your tutors schedule. If you have not yet
received a call from your tutor, do not hesitate to make the first call yourself.
If you live in Canada or the United States, you can call your tutor, toll free,
during his or her tutoring hours, using the information provided in the
tutor letter. If you live outside of Canada or the United States, please refer to
the tutor letter and the current Athabasca University Calendar for information
about calling your tutor.
We suggest that you contact your tutor as soon as you receive the course
materials, and then get into the habit of communicating regularly, when you
complete a unit or when you run into any special problem. We have found
that students who maintain regular contact with their tutors are most likely
to be successful in completing their courses, so do keep in touch. You may
find it useful to schedule a regular study period when your tutor is
available so that you can contact him or her when questions arise. If you are
unable to take advantage of the regular tutoring hours, contact your tutor or
the course professor to determine whether alternative arrangements can be
made.
If you use postal mail to send an assignment to your tutor, be sure to attach
a tutor-marked exercise form, and to keep a copy, at least a rough draft, in
case the original goes astray in the mail. If you take this course through the
Moodle course management system, you may be instructed to use the
Assignment Drop Box to submit your assignments. If you wish to submit
your assignments electronically outside of the Moodle system, contact your
Organic Chemistry II
Telephone number:
Electronic mail address:
Tutoring hours:
Note: If we are to keep you informed of upcoming laboratory sessions, etc.,
it is important that we receive notification of any change of address or
telephone number. Please inform the Office of the Registrar whenever such
a change occurs.
Services to Students
Athabasca University offers a wide range of services to its students. The
Athabasca University Information Centre (1.800.788.9041) can help you find
the answer to most administrative questions. The Centre is staffed on
regular business days from 7:00 a.m. to 5:30 p.m., Mountain Time.
Advisors are available to assist students in planning their programs and
selecting appropriate courses. Counselors assist students in improving their
study skills and clarifying their educational goals. You may reach an
advisor or counselor in several ways: by dialling 1.800.788.9041 and asking
to speak with an advisor or counselor; by visiting Athabasca Universitys
Central Office in Athabasca, or the Athabasca University sites in Edmonton
or Calgary; or by directing your query to
http://www.askau.ca
Students who are looking for information about student awards and advice
about obtaining financial assistance are asked to contact the Office of the
Registrar. You may do so by dialling 1.800.788.9041 and asking for the Office
of the Registrar, or by inquiring through
http://www.askau.ca
Note: Students may write examinations at the Athabasca University sites in
Athabasca, Edmonton or Calgary, or at the other locations listed online at
http://www.athabascau.ca/registrar/invignet.php
At the Athabasca University sites in Athabasca, Edmonton or Calgary,
students can also order materials from the Library, and take care of various
administrative matters, such as course registration and arrangements for
extensions.
Organic Chemistry II
Library Services
The Athabasca University Library collection contains more than 140,000
books, many periodical titles and a range of audio-visual resources. The
Library subscribes to over 100 online databases, providing full text access to
selected articles from more than 20,000 journals.
Athabasca University Librarys collection primarily supports Athabasca
University courses and programs. Materials found in the print and
electronic collections are available for use by our students, faculty and staff
for reference and research purposes. Requests for library materials or
services can be made, by email, phone, fax or mail, 24 hours a day (contact
information is provided below). Responses to most requests are handled
within 24 hours, or by the next business day. Borrowed materials are
normally mailed to the students home address, along with a returnmail card.
book chapters.
Digital Resources
Access to online journal databases, the Digital Reference Centre (DRC), and
the Digital Reading Room (DRR) is available from Athabasca University
Librarys main web page
http://library.athabascau.ca
Tips on searching the journal databases and help with researching, writing
and citing (referencing) can be found in the Help Centre
http://library.athabascau.ca/help.php
Supplementary Materials
University courses often require that students investigate material beyond
the contents of the course materials package. Some Athabasca University
course Study Guides list Supplementary Materials, including books,
10
Interlibrary Loans
An interlibrary loan (ILL) involves one library borrowing materials from
another on behalf of a library user. Athabasca University Library will
request photocopies of journal articles and book chapters through
Interlibrary Loans, if you provide the Library staff with a complete
bibliographic citation (author, title of article, name of journal, volume and
issue number, year of publication, and page numbers) for the requested
item. You are not required to return these items to us. Allow sufficient time
for the material to be ordered and received. More information on the
Interlibrary Loan process is available on the Library website at
http://aupac.lib.athabascau.ca/screens/ill.html
Contacts
Athabasca University Library
1 University Drive
Athabasca, AB Canada T9S 3A3
Library website: http://library.athabascau.ca
E-mail: library@athabascau.ca
Phone: 1.800.788.9041 (ext. 6254) Canada/US
Fax: 780.675.6477
Organic Chemistry II
11
Study Strategies
Chemistry 360 is a three-credit course and must be completed within the six
months of your contract period. This may seem like a long time, but
procrastination can rapidly put you in a difficult position. We suggest you
start right away and that you establish a study schedule. Your tutor can
help you.
How fast you proceed through the first few units will depend on your
background in organic chemistry from Chemistry 350. If your background is
weak, you may have to put in extra time, and this may affect your chances
of completing the course within the normal six-month contract period. If
you find that you really have trouble with Units 17 and 18, you should
discuss the situation with your tutor and consider withdrawing from the
course or taking some action to improve your understanding of
fundamental organic chemistry.
At a traditional university, this course would normally be spread over one
semester and take about 12-13 weeks to complete. If you wish to attain this
rate, follow the 13-week study schedule shown in the Course Outline and
Study Schedules section of this Student Manual. If you wish to proceed at
somewhat slower rate, refer to the 18- and 24-week schedules when you
plan your own personal study schedule. Remember that regular study
habits can be a major contributing factor to ultimate success in this course.
Should unforeseen circumstances put you in a position where you find that
you cannot complete the course within six months, check the Athabasca
University Calendar for current regulations about extensions.
Although the amount of time that a student will need to spend on the
course will depend on a variety of factors, students intending to complete
the course in 13 weeks should be prepared to spend at least nine (9) hours
per week on the course. You may need additional time when you have
laboratory reports to write, or when you are reviewing for an examination.
We suggest that you start Unit 17 now. As you work through it, make a note
of any questions you have on content, study procedures, etc. Then, before
you go on to the next unit, contact your tutor to clear up these questions.
12
Organic Chemistry II
13
13-week
schedule
18-week
schedule
24-week
schedule
17
Week 1
Week 1
Weeks 1-2
18
Week 2
Week 2
Weeks 3-4
A Preview of Carbonyl
Compounds
Aldehydes and Ketones:
Nucleophilic Addition
Reactions
Carboxylic Acids and
Nitriles
Carboxylic Acid
Derivatives and
Nucleophilic Acyl
Substitution Reactions
Carbonyl
Alpha-Substitution
Reactions
Week 2
Week 2
Week 5
Week 3
Weeks 3-4
Weeks 6-7
Week 4
Week 5
Week 8
Week 5
Weeks 6-7
Weeks 9-10
Week 6
Week 8
Week 11
Week 7
Week 9
Week 12
Week 8
Weeks 10-11
Weeks 13-15
Week 10
Weeks 12-13
Weeks 16-18
19
20
21
22
23
24
14
25
Biomolecules:
Carbohydrates
Week 11
Weeks 14-15
Weeks 19-21
26
Week 12
Weeks 16-17
Weeks 22-23
27
Biomolecules: Amino
Acids, Peptides, and
Proteins
Biomolecules: Lipids
Week 12
Weeks 16-17
Weeks 22-23
28
Week 12
Weeks 16-17
Weeks 22-23
Week 13
Week 18
Week 24
The table below allows you to plan (with the help of your tutor) a
personalized study schedule. We suggest you begin by filling in the first few
units and keep track of how long each unit is taking you. After you have
done the first few units, you (and your tutor) should be able to come up
with a realistic schedule for the rest of the course.
Planned
completion
date
Unit
or event
Actual
completion
date
Time
required
(hours)
Action
needed
Unit 17
Contact tutor
re lab schedule.
Unit 18
Preview
Unit 19
Unit 20
Unit 21
Complete TMA 1
Unit 22
Midterm
Examination
Unit 23
Unit 24
Unit 25
Unit 26, 27 or 28
Complete
Self Test 5, 6 or 7
Review
Final
Examination
Note 1: Check Applying for and Writing Examinations, in this manual, and note,
on the schedule above, the date by which you must apply for the midterm exam.
Note 2: Check Applying for and Writing Examinations, in this manual, and note,
on the schedule above, the date by which you must apply for the final exam.
Organic Chemistry II
15
16
Assessment
The assessment of students in this course is based on examinations,
tutor-marked assignments and laboratory work. Details are given in the
table below. To obtain credit for Chemistry 360, you must
obtain an overall (composite) mark of at least 50%.
achieve at least 45% on each of the two examinations.
obtain an average of at least 60% on the tutor-marked assignments.
achieve an average of at least 55% on the laboratory work.
Percentage
of total mark
Component
Material covered
Midterm Examination
(2 hours)
Units 17-22
20%
Final Examination
(3 hours)
Entire Course
50%
Tutor-marked
Assignments
Following Unit 21
and Unit 25
10%
Laboratory Work
20%
Organic Chemistry II
17
3. For numerical problems, show your work! Part marks will be given for
correct methods even if your answer is incorrect. The answers to
numerical problems should be given to the correct number of significant
figures, and where appropriate, with the correct units. Marks may be
deducted if answers are given to an incorrect number of significant
figures or in the wrong (or no) units.
Procedures for applying to write examinations may be found in the section
of this Student Manual titled Applying for an Examination, below.
Supplemental Examinations
Students who are dissatisfied with their grade on any examination, or who
obtain less than the required passing grade, may write a supplemental
examination. Only one supplemental is permitted per examination. The
higher of the two grades received will be recorded as the official grade.
Note that there is a fee for each supplemental examination.
Appeals
Appeals to examination or assignment grades should be discussed first with
your tutor or instructor. For the correct procedure, see Student Code of
Conduct and Right to Appeal in the current Athabasca University Calendar
or available through your myAU portal.
Organic Chemistry II
19
Intellectual Indebtedness
Students enrolled in any Athabasca University course are considered to be
responsible scholars, and are therefore expected to adhere rigorously to the
principles of intellectual honesty.
Plagiarism is a form of intellectual dishonesty in which anothers work is
presented as ones own, and, as will any form of academic misconduct,
plagiarism will be severely penalized. Depending on the circumstances,
penalties may involve rejection of the submitted work; expulsion from the
examination, the course or the program; or legal action.
Students sometimes commit plagiarism inadvertently. To avoid doing so,
make certain that you acknowledge all your sourcesboth primary and
secondaryin a full and consistent manner. All direct quotes (quotations,
however short, from an original work), indirect quotes, paraphrased
passages, ideas, images, and tabular and statistical information that you use
from other sources (including electronic sources) must be documented
using an acceptable citation style. There are three conventional ways of
acknowledging your sources: in-text citations, footnotes or end-notes. We
prefer that you use in-text citations, combined with a full bibliography
presented at the end of the essay. The in-text citation must give the name of
the author, the date of publication, and the page on which the cited material
appears (Doe, 1997, p. 60). The bibliographic entry must provide at least the
authors last name, first name or initial, the date of publication, the title of
the work, the place of publication and the publisher.
20
Transcripts
A student can request an official transcript by completing a paper
Transcript Request form, by writing to the Office of the Registrar, by
appearing at the Office of the Registrar in person, or by using the secure
online request form. For instructions on making an online request, see
http://www.athabascau.ca/registrar/OROShelp.php?page=transcriptRequest
Only the student whose transcript is being issued may make the request,
and a paper request must bear the students signature.
No partial transcripts are issued. The students entire record is shown on
each transcript.
Most institutions and agencies require that official transcripts be sent
directly from Athabasca University. Please allow a minimum of ten working
days for the receipt of a transcript. Consult the current edition of the
Athabasca University Calendar for further information about transcripts.
Transferring Credit
If you wish to transfer credit to another institution, contact the Office of the
Registrar at Athabasca University. Remember, however, that transfer of
credit is determined by the receiving institution. If you plan to transfer credit
for this course to another institution, we suggest you get an agreement, in
writing, from that institution. This agreement is usually called a letter of
permission.
Organic Chemistry II
21
22
Sample Examinations
On the following pages you will find sample examinations that will help
you prepare for your midterm examination and your final examination. We
have included such questions in this manual to give you a better idea of the
length of a normal Athabasca University chemistry examination. Short
answers for the questions are given at the end of the sample examinations
(see the section of this manual titled Sample Examination Answer Keys).
Organic Chemistry II
23
24
a.
O
b.
SH
c.
Organic Chemistry II
25
b. N,N-dimethylacetamide
c. 5-hydroxy pentanenitrile
OH
OH
26
OH
O
SH
SH
Organic Chemistry II
H3 O+
EGGGGGGGGC
GGGGGGGG
HO
OH
27
O
GGGGGGGGA
(b)
OH
H
D GGGGGGGG
OH
GGGGGGGGA
(a)
(c)
ppm
28
9. What properties account for the fact that acetic acid is a stronger acid
than ethanol?
Intensity
Multiplicity
9.8
quartet
2.2
doublet
Organic Chemistry II
29
11. Identify the major product or products for seven (7) of the following
reactions, and show stereochemistry where appropriate.
Note: Only the first seven questions answered will be markedso
only give answers for those items you want marked.
O
a.
1. CH3 MgBr
GGGGGGGGGGGGGGGA , ether
2. H3 O+
HCN
GGGGGGGGA
b.
O
c.
30
NH2 OH
GGGGGGGGGGGGA
OH
d.
PCC
GGGGGGGGGGGA
CH2 Cl2
NH2
e.
SOCl2
GGGGGGGGGGA
H Br
GGGGGGGGA
f.
O
O
g.
OH
O
O
GGGGGGGGGGGGGGGGGGA
OH
N
Organic Chemistry II
31
h.
l2
GGGGGGGGGGGGGGGA
H2 O
SH
O
Cl
i.
OH
GGGGGGGGGGGGGGGGGGGA
1. O3
GGGGGGGGGGGGGGGGGGGGA
2. Zn, CH3 CO2 H
j.
k.
2 NH3
GGGGGGGGGGA
32
12 marks
12. Show by means of a series of chemical equations how three (3) of the
following conversions could be achieved.
Note: Only the first three questions answered will be markedso only
give answers for those items you want marked.
OH
a.
O
GGGGGGGGA
O
OH
b.
Organic Chemistry II
GGGGGGGGA
33
c.
GGGGGGGGA
OH
O
d.
8 marks
GGGGGGGGA
13. Write the complete stepwise mechanism for the reaction shown below.
Show all intermediate structures and mark electron flows with arrows.
NH2
O
34
OH
H3 O+
FGGGGGGGGB
GGGGGGGG
+ NH4+
O
6 marks
14. Give a brief definition for three (3) of the following terms. Use
examples where appropriate.
Note: Only the first three questions answered will be markedso only
give answers for those items you want marked.
a. mercapto group
b. carbinolamine
d. thioester
e. enolate ion
Organic Chemistry II
35
7 marks
6H
1H
ppm
END OF EXAMINATION
36
a.
N
H
O
b.
CN
O
Cl
c.
SH
d.
Br
e.
f.
Organic Chemistry II
Li Cu(CH3 )2
NH2
37
1 mark each
2. Draw the IUPAC the chemical structure for each of the compounds below.
a.
D-glyceraldehyde
b. N,N-dimethyl cyclopentylamine
c. (S) 4-bromo-2-hexanone
d. 2-ethylcyclohexane-1,3-dione
e. 2-butene-1-thiol
f. 3-chloropyridine
38
3. Rank the basicity of the amines below (1 = least basic, 3 = most basic)
NH2
H2 N
CH2 CH3
N
H
Organic Chemistry II
39
NH2
when prepared by the Curtius reaction?
b. Is the structure of this carboxylic acid the same as or different from the
structure of the carboxylic acid needed to prepare 3-methylaniline by
the Hofmann reaction?
40
+
+
CH2 OH
Cl
H
CH3
Cl
H3 C
CHO
HO
H
Br
Cl
OH
H
OH
CH2 OH
Organic Chemistry II
Chemical shift
(ppm)
Signal
multiplicity
2.1
singlet
(3 H)
2.4
quartet
(2 H)
1.1
triplet
(3 H)
41
9. State the major product or products for ten (10) of the reactions below.
Note: Only the first ten questions answered will be markedso only
give answers for those items you want marked.
a.
HO
O
H
HNO3
GGGGGGGGGGGGGGGGA
OH
CH2 OH
NO2
b.
1. SnCl2 , HCl
GGGGGGGGGGGGGGGGGGGGGA
2. HNO2 , H2 SO4
3. NaI
MgBr
1.
c.
42
CN GGGGGGGGGGGGGGGGGGGGGA
2. H3 O+
O
1. Br2 , PBr3
OH GGGGGGGGGGGGGGGGA
2. H2 O
d.
e.
+
O
1. SOCl2
GGGGGGGGGGGGGGGGGGGA
f.
2.
OH
g.
Organic Chemistry II
1. THF
GGGGGGGGGGGGGGGGA
2. H+
1. NaOCH3 , CH3 OH
GGGGGGGGGGGGGGGGGGGGGGGGGA
2. H3 O+
43
h.
O
i.
NH2 NH2
GGGGGGGGGGGGA
KOH
H
.
CrO3
GGGGGGGGGGGGGGGGA
H3 O+
OH
pyridine
1.
Cl
GGGGGGGGGGGGGGGGGGGGGGGA
O
2. CH3 OH, HCl
H
j.
44
O
NaOCH3 , CH3 OH
GGGGGGGGGGGGGGGGGGGGGGGA
k.
SH
l.
l2
GGGGGGGGGGGGGGA
H2 O
m.
+ (C6 H5 )3 P C H
CH3
GGGGGGGGGGGGGGA
OH
n.
Organic Chemistry II
PCC
OH GGGGGGGGGGGGGGA
CH2 Cl2
45
10 marks
10. In your own words, define five (5) of the terms given below.
Note: Only the first five questions answered will be markedso only
give answers for those items you want marked.
a. heterocyclic amine
b. mutarotation
c. chemical shift
d. parent peak
e. enol
f. anomers
h. mixed aldol
i. ,-unsaturated ester
46
10 marks
NH2
N HSO4
NH2
N
b.
O
H
Organic Chemistry II
GGGGGGGGA
NaOH
GGGGGGGGGGGGGG
AG
D GGGGGGGGGGGGG
ethanol
OH
O
H
47
10 marks
12. Propose and show the synthetic pathway for two of the
transformations below.
Note: Only the first two questions answered will be markedso only
give answers for those items you want marked.
CN
NH2
a.
GGGGGGGGA
b.
GGGGGGGGA
O
c.
48
HO
O
O
GGGGGGGGA
10 marks
Organic Chemistry II
49
Note: The remainder of this examination is based on the three optional units
in this course. You have studied one of the possible three units. Please
complete only one (1) of the following questions
Unit 26
10 marks
50
Biomolecules: Lipids
Unit 27
10 marks
16. a. Draw the major products you would expect from the reaction of
cholesterol and the following reagents
HO
Cholesterol
i.
CrO3
GGGGGGGGGGGGGGA
H+
ii.
O
GGGGGGGGGGGGGGGGGGGA
pyridine
iii.
Organic Chemistry II
Br2
GGGGGGGGGGGGGGA
CH2 Cl2
51
ii.
52
Unit 28
10 marks
END OF EXAMINATION
Organic Chemistry II
53
54
Organic Chemistry II
55
56
a.
cyclopentyl 2-methylpropanoate
O
b.
1-methoxycyclohexene
SH
c.
Organic Chemistry II
(R)3-heptanethiol
57
b. N,N-dimethylacetamide
O
N
c. 5-hydroxy pentanenitrile
HO
CN
OH
OH
58
OH
O
SH
SH
EGGGGGGC
GGGGGG
H2 O
HO
H3 O+
EGGGGGGGGC
GGGGGGGG
H2 O
OH
+ OH
FGGGB
GGG
OH
FGGGB
GGG
+
H
O+
+ H3 O+
OH
Organic Chemistry II
59
LiAlH4
GGGGGGGGGGGGA
ether
OH
OH
PCC
GGGGGGGGGA
CH2 Cl2
NH2 NH2
GGGGGGGGGGGGGGA
KOH
O
CH3C
3H
CH
3H
OCH2
2H
8
ppm
60
3
~3.5 ppm
2
1
~2.0 ppm ~1.0 ppm
9. What properties account for the fact that acetic acid is a stronger acid
than ethanol?
O
FGGGGGGB
GGGGGG
OH
GGGGGG
OH FGGGGGGB
Intensity
Multiplicity
9.8
quartet
2.2
doublet
1715 cm1
O
H3 C
d 2.2 ppm
Organic Chemistry II
H
q 9.8 ppm
61
1. CH3 MgBr
GGGGGGGGGGGGGGGA
either
2. H3 O+
HCN
GGGGGGGGGA
b.
62
OH
O
c.
NC
or
OH
NH2 OH
GGGGGGGGGGGGA
OH
O
OH
d.
PCC
GGGGGGGGGGGA
CH2 Cl2
NH2
e.
CN
SOCl2
GGGGGGGGGGA
OH
H Br
GGGGGGGGA
f.
Br
O
O
g.
OH
O
O
OH O
GGGGGGGGGGGGGGGGGGA
OH
N
Organic Chemistry II
63
h.
l2
GGGGGGGGGGGGGGGA
H2 O
SH
O
Cl
i.
OH
GGGGGGGGGGGGGGGGGGGA
1. O3
GGGGGGGGGGGGGGGGGGGGA
2. Zn, CH3 CO2 H
j.
k.
O
64
2 NH3
GGGGGGGGGGA
O+
O
O
NH4+
+
NH2
12. Show by means of a series of chemical equations how three (3) of the
following conversions could be achieved.
Note: Only the first three questions answered will be markedso only
give answers for those items you want marked.
a.
OH
CrO3
D GGGGGGGGG
pyridine
GGGGGGGGGGGGGA
D GGGGGGGGGGG
Br2 /PBr3
GGGGGGGGGGGGGGA
Br
O
OH
b.
H3 O+
GGGGGGGGGGA
CrO3
D GGGGGGGGGGGGGGG
H3 O+ , acetone
GGGGGGGGA
O
NaOH
GGGGGGGGGGGA
ethanol
HO
Organic Chemistry II
65
66
CH3 Cl
D GGGGGGGGGGG
AlCl3
c. Either
or
KMnO4
D GGGGGGGGGGGG
CH3 Cl
D GGGGGGGGGGG
AlCl3
GGGGGGGGGGGA
NBS
GGGGGGGGGGGA
CH2 Cl2
GGGGGGGGGGGA
CO2 H
LiAlH4
GGGGGGGGGGGA
ether
Br
OH
Na OCH3
GGGGGGGGGGGGGGGA
CH3 OH
1. NaOH
GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGA
2. CH3 Br
d.
OH
GGG
GGG
GGG BH
H GGGGG 3
2O
G
2 , O GGGG
H GGGA
PPh3
Br
D GGGGGGGGGGGGGGGGGGGGGG
GGGGGGGGGGGA
13. Write the complete stepwise mechanism for the reaction shown below.
Show all intermediate structures and mark electron flows with arrows.
NH2
O
FGGGGGGB
GGGGGG
HO+
Organic Chemistry II
NH2 FGGGGGGB
GGGGGG
OH
NH2
FGGGGGGGGB
GGGGGGGG
+H
+ NH4+
G GBGG
GGG
G GG G
G GG G
G GG G
G GG G
GFGG
OH
H3 O+
GGGGGGB
F GGGGGG
NH3
OH
67
14. Give a brief definition for three (3) of the following terms. Use
examples where appropriate.
Note: Only the first three questions answered will be markedso only
give answers for those items you want marked.
a. mercapto group
a thiol
SH
b. carbinolamine
C
OH
NH2
O
R
H+
OH + R OH FGGGGGGB
GGGGGG R
OR + H2 O
d. thioester
O
SR
e. enolate ion
O
68
6H
1H
ppm
degree of unsaturation = 1
1715 cm1
C=O
CH3
NMR
H
CH3
CH3
major fragment
CH
m/z 28
CH3
m/z 43
m/z 71
Compound A:
O
H3 C
H
H3 C
CH3
C
H
CH3
END OF EXAMINATION
Organic Chemistry II
69
70
a.
pyrrolidine
N
H
O
b.
3-cyano-2-cyclohexen-1-one
CN
O
Cl
c.
2-chlorocyclopentanone
SH
d.
4-bromobenzenethiol
Br
e.
f.
Organic Chemistry II
Li Cu(CH3 )2
NH2
lithium dimethylcuprate
aniline
71
2. Draw the IUPAC the chemical structure for each of the compounds below.
a.
D-glyceraldehyde
OH
CH2 OH
b. N,N-dimethyl cyclopentylamine
N
c. (S) 4-bromo-2-hexanone
H
O
Br
d. 2-ethylcyclohexane-1,3-dione
O
O
e. 2-butene-1-thiol
SH
f. 3-chloropyridine
Cl
72
3. Rank the basicity of the amines below (1 = least basic, 3 = most basic)
NH2
H2 N
CH2 CH3
N
H
Organic Chemistry II
73
CH2 (CO2 R )2
+
Br
O
OR
NH2
when prepared by the Curtius reaction?
CH3
CO2 H
b. Is the structure of this carboxylic acid the same as or different from the
structure of the carboxylic acid needed to prepare 3-methylaniline by
the Hofmann reaction?
It is the same.
74
+
+
2 , allylic
CH2 OH
Cl
H
CH3
Cl
H3 C
CHO
HO
H
Br
Cl
OH
H
OH
CH2 OH
Signal
multiplicity
2.1
singlet
(3 H)
2.4
quartet
(2 H)
1.1
triplet
(3 H)
Organic Chemistry II
75
HO
O
H
CO2 H
HO
HNO3
GGGGGGGGGGGGGGGGA
OH
OH
CO2 H
CH2 OH
NO2
b.
1. SnCl2 , HCl
GGGGGGGGGGGGGGGGGGGGGA
2. HNO2 , H2 SO4
3. Nal
HSO4
$ GGGA
"
MgBr
1.
c.
CN GGGGGGGGGGGGGGGGGGGGGA
2. H3 O+
76
d.
O
1. Br2 , PBr3
OH GGGGGGGGGGGGGGGA
2. H2 O
OH
Br
e.
+
O
1. THF
GGGGGGGGGGA
2. H+
1. SOCl2
GGGGGGGGGGGGGGGGGGGA
f.
2.
OH
g.
O
GGGGGGGGGGGA
1. NaOCH3 , CH3 OH
GGGGGGGGGGGGGGGGGGGGGGGGGA
2. H3 O+
OH
Organic Chemistry II
77
h.
O
i.
NH2 NH2
GGGGGGGGGGGGA
KOH
H
.
CrO3
GGGGGGGGGGGGGGGGA
H3 O+
1.
pyridine
Cl
GGGGGGGGGGGGGGGGGGGGGGGA
O
2. CH3 OH, HCl
H
j.
78
OH
OH
k.
O
OCH3
.
NaOCH3 , CH3 OH
GGGGGGGGGGGGGGGGGGGGGGGA
SH
l.
m.
l2
GGGGGGGGGGGGGGA
H2 O
(C6 H5 )3 P C H
CH3
GGGGGGGGGGA
CHCH3
OH
n.
O
PCC
OH GGGGGGGGGGGGA
CH2 Cl2
O
Organic Chemistry II
79
10. In your own words, define five (5) of the terms given below.
Note: Only the first five questions answered will be markedso only
give answers for those items you want marked.
a. heterocyclic amine
compounds in which the N atom occurs as part of ring; for
example, pyridine,
N
b. mutarotation
change in optical rotation observed when a pure anomer is
dissolved in water; it is caused by reversible opening and closing of
the hemiacetal, which gives a mixture of anomers
c. chemical shift
the position in a 1 H NMR spectrum where a nucleus absorbs
d. parent peak
the peak in the mass spectrum corresponding to the molecular
ion, M+
e. enol
a vinyl alcohol,
OH
f. anomers
cyclic stereoisomers of sugars that differ only in their configuration
at the hemiacetal (anomeric) carbon
g. Hell Volhard-Zelinskii reaction
formation of an -bromo carboxylic acid
1. Br2
RCH2 CO2 H GGGGGGGGGGA
RC HCO2 H
PBr3
Br
2. H2 O
h. mixed aldol
aldol reaction between one or more aldehydes and one or more
ketones, one of which has no H and thus cannot form an
enolate ion
i. ,-unsaturated ester
OR
80
N HSO4
NH2
NH2
N
GGGGGGGGA
GGG
GGG
G
G
GGG
GGG
G
G
GGG
NH2
OH
NaOH
GGGGGGGGGGGGGG
AG
D
GGGGGGGGGGGGG
H
ethanol
H2 SO4
O
H
!
H
EGGGGGGGGC
GGGGGGGG
OH
HSO4
b.
+ H2 O
H
H
H
O
H
Organic Chemistry II
+ OH
BG
FGGGGGGGGGG
GGGGGGGGG
O
81
12. Propose and show the synthetic pathway for two of the
transformations below.
Note: Only the first two questions answered will be markedso only
give answers for those items you want marked.
a. Either
CN
NH2
1. NaN3
GGGGGGGGGGGGGGGGA
2. H2 O/
1. NaOH
D GGGGGGGGGGGGGG
2. H3 O+
GGGGGGGGA
O
OH
SOCl2
GGGGGGGGGGGGGG
A
Cl
or
CN
NH2
1. NH3
GGGGGGGGGGGGGGGGGGGA
2. Br2 /NaOH
H2 O
1. NaOH
D GGGGGGGGGGGGGG
2. H3 O+
GGGGGGGGA
OH
82
SOCl2
GGGGGGGGGGGGGG
A
Cl
O
HO
1. HNO3 , H2 SO4
D GGGGGGGGGGGGGGGGGGGGGGG
GGGGGGGGGGGGGGGGA
HSO4
+
O2 N
c.
1. SnCl2 /HCl
GGGGGGGGGGGGGGGGGGGGA
2. HNO2 /H2 SO4
O
GGGGGGGGA
Br
product
2.
1. NaOEt/EtOH
D GGGGGGGGGGGGGGGGGGGGGGG
b.
O
1. H3 O+
GGGGGGGGGGGA
2. heat
O
Organic Chemistry II
OEt
83
B
C10 H16
degree of
unsaturation = 3
C
C10 H16
O3
D GGGGGGGGG
2n/HoAc
A
C10 H18 O
degree of
unsaturation = 2
B is
OH
A must be
and C should be
84
CHO
OH
OH
OH
Kiliani
GGGGGGA
Fischer
OH
OH
OH
OH
OH
CH2 OH
CH2 OH
HNO3
D GGGGGGGGGGG
HNO3
D GGGGGGGGGGG
OH
CH2 OH
CO2 H
CO2 H
OH
B
HO
OH
OH
CO2 H
HNO3
D GGGGGGGGGGG
OH
CHO
CO2 H
HO
E
OH
F
OH
OH
OH
OH
OH
OH
CO2 H
CO2 H
optically
active
optically
inactive
Therefore,
CHO
CO2 H
OH
OH
OH
D is
OH
OH
CH2 OH
Organic Chemistry II
OH
F is
OH
OH
CO2 H
85
CHO
CO2 H
HO
HO
OH
C is
OH
OH
E is
OH
OH
OH
CH2 OH
CO2 H
CO2 H
CHO
OH
A is
OH
OH
CH2 OH
86
OH
B is
OH
OH
CO2 H
Note: The remainder of this examination is based on the three optional units
in this course. You have studied one of the possible three units. Please
complete only one (1) of the following questions
Biomolecules: Amino Acids, Peptides and Protein
Unit 26
OH
CH3
b. Draw the predominant form of threonine in a pH 4.0 buffer solution.
The isoelectric point of threonine is 5.6.
H
HO
H2 N
C
HN
CO2 Et
C
CH3
1. NaOEt
GGGGGGGGGGGGA PhCH2
2. PhCH2 Br
CO2 Et
C
CO2 Et
HN
H3 O+
GGGGGGGA
heat
PhCH2
CH
CO2
+ NH
3
O
O
Organic Chemistry II
87
Unit 27
Biomolecules: Lipids
16. a. Draw the major products you would expect from the reaction of
cholesterol and the following reagents
HO
cholesterol
CrO3
i. GGGGGGGGGGGGGGA
H+
O
O
O
ii. GGGGGGGGGGGGGGGGGGGA
pyridine
O
O
Br2
iii. GGGGGGGGGGGGGGA
CH2 Cl2
.
HO
Br
Br
88
H
ii.
Organic Chemistry II
89
Unit 28
RNA
O
O
ribose
unique base
thymine
P OCH2
O
O
base
NH
N
HO
unique base
uracil
P OCH2
O
O
O
base
NH
O
OH OH
sugar
sugar
END OF EXAMINATION
90