Chemistry 350 - Athabasca University

Chemistry 350

Organic Chemistry I

Student Manual

Athabasca University

Course Team

Course Professor: Lawton ShawCourse Authors: Arthur Last and Dietmar KennepohlRevisions: Dietmar Kennpohl (1996-2004); Ross Witherell (2010)Reviewer, 2004: David LawEditor: Gilda SandersVisual Presentation: Athabasca University Digital Media Technology UnitCover Design: Jingfen Zhang

Cover Image: Alchymist, in Search of the Philosopher’s Stone, DiscoversPhosphorus, and prays for the successful Conclusion of his operation, as was thecustom of the Ancient Chymical Astrologers, by Joseph Wright of Derby(1734-1797). This painting, created in 1771, is now held by the DerbyMuseum and Art Gallery, Derby UK. Public Domain.

Note: This course is a revision of a part of Chemistry 345: Organic Chemistryby Arthur Last, copyright © 1991 by Athabasca University.

Every effort has been taken to ensure that these materials comply with therequirements of copyright clearances and appropriate credits. AthabascaUniversity will attempt to incorporate in future printings any correctionswhich are communicated to it.

The inclusion of any material in this publication is strictly in accord with theconsents obtained and Athabasca University does not authorize or licenseany further reproduction or use without the consent of the copyright holder.

© Athabasca University 2010All rights reservedPrinted in Canada

CMID 552838Revision 6

Contents

Course Information 1

The Course . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

The MyAU Portal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

Your Student ID Number . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

Freedom of Information and Protection of Privacy . . . . . . . . . . . . . 4

The Athabasca University Calendar . . . . . . . . . . . . . . . . . . . . . . 4

Course Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

Other Items . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Course Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Laboratories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

Your Tutor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

The Course Professor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

Services to Students . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Library Services . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

Study Strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

How to Use the Study Guide . . . . . . . . . . . . . . . . . . . . . . . . . . 15

Course Outline and Study Schedules . . . . . . . . . . . . . . . . . . . . . 16

Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

Applying for and Writing Examinations . . . . . . . . . . . . . . . . . . . 20

Student Conduct and Appeals . . . . . . . . . . . . . . . . . . . . . . . . . 22

Intellectual Indebtedness . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

Transcripts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

Transferring Credit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

Applying for Extensions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

Sample Examinations 25

Sample Midterm Examination . . . . . . . . . . . . . . . . . . . . . . . . . 27

Sample Midterm Examination—Answer Key . . . . . . . . . . . . . . . . 43

Sample Final Examination . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

Sample Final Examination—Answer Key . . . . . . . . . . . . . . . . . . 67

Course Information

Organic Chemistry I 1

2 Chemistry 350 / Student Manual

The Course

Welcome to Chemistry 350: Organic Chemistry I, a three-credit, senior-level,laboratory science course. We assume that all students registering in thiscourse will have completed a university-level course in general chemistryequivalent to Athabasca University’s Chemistry 217/218 (formerly Chemistry209). If this is not the case, you should contact the course professorimmediately.

Organic Chemistry I deals with the chemistry of carbon compounds througha study of the characteristic reactions of the common functional groups.Particular emphasis is placed on the study of reaction mechanisms, in anattempt to show similarities between apparently unrelated reactions. Theimportance of stereochemistry is stressed throughout the course. Thecompulsory laboratory component of Chemistry 350 introduces the basictechniques employed in modern organic chemistry laboratories.Experiments have been selected to illustrate many of the principlesencountered in the theoretical part of the course. The course outline onpage 17 of this manual gives a more detailed description of the coursecontents.

This Student Manual provides you with some essential information aboutthe design of the course, the course materials, and the procedures youshould follow to obtain the maximum benefit from your studies. Please readit carefully and keep it in a safe place.

Note: These course materials have been designed for students who aretaking the individualized-study version of this course. Students who are ina grouped-study environment should follow the course outline, studyschedule and learning activities provided by their instructor.

The MyAU Portal

MyAU is a personalized portal to the University where you can quicklyaccess information that is relevant to you. Through myAU, you can viewpersonal information, such as library accounts and assignment marks andcourse grades, and take care of administrative matters, such as bookingexaminations, submitting assignments, applying for extensions, registeringfor courses, and so on. Athabasca University will also communicate directlywith you through myAU. Check the Message Centre on your myAU homepage for general information and for mail addressed specifically to you.

To login at

http://my.athabascau.ca/

enter your student ID number and password where requested. If you arehaving browser difficulties or you need help, refer to myAU Help at

http://www.athabascau.ca/uportal/help/index.php


Your Student ID Number

In contacts with your tutor, on assignments, or in any correspondence orother contact with the University, you are asked to provide your student ID

number. Record this number in the space below. Having your student ID

number will help University personnel to process requests, grades andadministrative matters more quickly.

Student ID number:

Note: It is important that we receive notification of any change of address ortelephone number. Please inform the Office of the Registrar whenever sucha change occurs. You can do so through your myAU portal, or you can use astudent change of information form (see the section of this manual titled“Forms”). In addition, you should send change-of-address cards to yourtutor and to the course professor, so that your student files can be keptup-to-date.

Freedom of Information and Protection of Privacy

The personal information and records collected and maintained by theUniversity as a result of a student’s registration in this course, such ascompleted assignments and examinations, electronic communications andcorrespondence, are subject to University policies and the privacy andaccess provisions of the Alberta Freedom of Information and Protection ofPrivacy Act.

The Athabasca University Calendar

Because Athabasca University’s policies, practices, and procedures changeover time, some of the information in this Student Manual may lose itscurrency between course revisions. Students are therefore advised to referto the current Athabasca University Calendar on important issues concerningUniversity policies, procedures and practices. In the event of anydiscrepancy between the printed version of the Calendar and the officialweb-based Calendar, the web-based version will be binding.


Course Materials

The package you received should include each of the items listed below. Ifanything is missing from your package, please contact the Course Materialsdivision of Athabasca University as soon as possible. If you live in Canadaor the United States, you can use email to contact Course Materials:

[email protected]

You can also call 1-800-788-9041, choose option 3 from the menu, and enterextension 6366 when prompted.

Students who live outside of Canada or the United States can contactCourse Materials by email.

You can also write in care of Course Materials, Tim Byrne Centre, 400 Hwy 2South, Athabasca, AB T9S 1A4.

Textbooks

McMurry, John. Organic Chemistry, 7th ed. Pacific Grove, CA: Brooks/ColePublishing Co., 2008.

McMurry, Susan. Study Guide and Student Solutions Manual for McMurry’sOrganic Chemistry, 7th ed. Pacific Grove, CA: Brooks/Cole PublishingCo., 2008.

Athabasca University Materials

Chemistry 350: Organic Chemistry I. Student Manual. Athabasca, AB:Athabasca University, 2010.

You are now reading the Student Manual.

Chemistry 350: Organic Chemistry I. Study Guide. Athabasca, AB: AthabascaUniversity, 2010.

The Study Guide, as its name implies, is designed to guide your study ofthe course textbook.

Chemistry 350: Organic Chemistry I. Assignment Manual. Athabasca, AB:Athabasca University, 2010.

The Assignment Manual contains the self tests and answers to the selftests, as well as the two “tutor-marked assignments.”

Chemistry 350: Organic Chemistry I. Laboratory Manual. Athabasca, AB:Athabasca University, 2010.


Other Items

The items listed below are not supplied; you should purchase them beforeyou begin to work on the course. You will need

● an electronic calculator capable of handling logarithms and exponentials.

Remember: Take your calculator with you whenever you write anexamination or attend a laboratory session.

● a lab coat. You will not be allowed to attend lab sessions without one.

● a laboratory notebook.

● other stationery, including paper for assignments, pens, pencils, aruler, etc.

Forms

The forms you need to submit assignments, request examinations or informthe University of a change in your status as a student are available throughyour myAU home page, or for download from the Office of the Registrar’sOnline 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 formsonline, please contact the Athabasca University Information Centre, tollfree, at 1.800.788.9041 to request that printed copies be sent to you. ForChemistry 350, you will need at least two tutor-marked exercise forms andtwo examination request forms.

Course Design

The course materials are designed for self-instruction and individualized-study. What you should learn and how you should learn it are described inthe Study Guide. This book contains 16 units, each of which corresponds toone of the chapters in Organic Chemistry, 7th ed., by John McMurry. Eachunit in the Study Guide contains a preview, a list of learning objectives, aseries of subsections corresponding to chapter subsections, and some hintson how to work through the unit. Let us look at exactly what you can expectto find under each of these headings.


Unit Preview

The “Unit Preview” is a brief discussion that outlines the overall approachtaken 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 tobe able to fulfill when you have finished studying the unit.

Sections

The sections form the bulk of each unit. Each section in the Study Guidenormally contains the following features:

1. a list of objectives which are more detailed than those provided underthe heading “Unit Objectives,” and which may be one of the mostvaluable features of the Study Guide, because they tell you explicitly whatyou need to understand and to be able to do for each unit of the course.Questions on the examinations and tutor-marked assignments are basedonly on the unit objectives. However, you should be aware that manyquestions will require you to demonstrate mastery of a number of relatedobjectives, and that you should not place too narrow an interpretation oneach objective.

2. a list of key terms introduced in the section. Unless we have indicatedotherwise, definitions of these key terms are provided in “AppendixC—Glossary,” beginning on page A10 of Organic Chemistry, 7th ed.

3. study notes, which may include hints on how to study the materialeffectively, additional information, and details of any errors that occur inthe textbook.

4. a list of suggested exercises. These exercises are designed to improveyour understanding of the material you have just studied and to developyour problem-solving skills. Refer to your notes and to the textbookwhen you attempt the exercises. The answers to all the exercises areprovided in the Solutions Manual or in “Appendix D—Answers to In-textProblems,” beginning on page A30 of the textbook. Do not spend a largeamount of time on any one exercise. If you are unable to make anyprogress after a few minutes of concentrated work, use the answersto help.

For further information, see the section of this manual titled “How to UseYour Study Guide.” There are two (2) tutor-marked assignments (TMAs) inthis course. These assignments contribute to the overall mark that you willobtain for the course (see the “Assessment” section of this manual).

Units 1 and 2 have entry-level tests designed to determine your mastery ofthe fundamentals. If you obtain a high score on the test in one of these units,you may proceed immediately to the next unit.


Self tests are given at the end of Units 5, 7, 9, 11, 14 and 16. These tests aredesigned to allow you to measure your progress in the course—they are nota comprehensive overview of the material, nor are they at the same level ofdifficulty that you will encounter in the midterm and final examinations.[Sample examinations are given in this manual.] If you have difficulty withany self test, you should go back and review the material before going on.

The textbook by McMurry contains most of the information you will needto pass this course. It is a standard textbook used in many universities andcolleges throughout North America. It was chosen because it offers clearexplanations and interesting discussions of the material we wished thiscourse to cover. In addition, we felt that this textbook has an advantage inthat it includes some discussion of a number of advances made in organicchemistry during the last decade. The chapters are relatively short, and thetextbook contains problems, exercises and some review chapters.

Each chapter of the textbook concludes with a useful summary, and whereappropriate, a list of the reactions introduced in the chapter. These reviewsare excellent for quick reference and will help you to prepare forexaminations.

You should use a set of molecular models to assist you in understanding thestereochemical aspects of the course. If you cannot obtain a set of molecularmodels elsewhere, you may order one from the Athabasca UniversityLibrary (see the section of this manual titled “Library Services”). You mayuse molecular models during examinations.

Laboratories

You must complete about 32 hours of laboratory work to obtain credit inthis course. Labs are typically held for week-long sessions during thesummer in Athabasca, or for full-day sessions on weekends in Edmonton inthe rest of the year. The Lab Coordinator will be able to provide up-to-dateinformation, 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 laboratorysession. Students in Canada and the United States can reach the LabCoordinator by calling 1-800-788-9041 (the extension is 6276). All studentscan use electronic mail to contact the Lab Coordinator at

[email protected]

Information about the laboratory program and the experiments to becarried out is included in the Laboratory Manual. Note that your lab workaccounts for 20 per cent of your overall course mark. You must satisfactorilycomplete and write up a specified minimum number of experiments toobtain credit for this course.


Your Tutor

Athabasca University provides each student in each course with a tutorwhose responsibility is to help the student complete the course successfully.A letter containing your tutor’s name, address, telephone number andtutoring hours was mailed to you shortly before your official start date. Ifyou have not yet received your tutor letter, please contact LearningServices—Tutorial at Athabasca University as soon as possible. Students inCanada or the United States can call 1-800-788-9041 (extension 6196); allstudents can send electronic mail to

[email protected]

Note: If you have chosen to receive communications from AthabascaUniversity in electronic form, be sure to check your myAU portal for yourtutor letter.

Your tutor has excellent academic qualifications, and is committed tohelping students learning at a distance. He or she is available to answeryour questions about course content or how to approach a problem or anassignment, and can direct you to the right person or department to helpyou with other problems that may be hindering your progress in yourcourse or program. In addition, your tutor will be responsible for markingyour assignments. In general, you should call your tutor first with anyqueries about Athabasca University.

The tutor letter will help you become acquainted with your tutor and willprovide information about your tutor’s schedule. If you have not yetreceived 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 thetutor letter. If you live outside of Canada or the United States, please refer tothe tutor letter and the current Athabasca University Calendar for informationabout calling your tutor.

We suggest that you contact your tutor as soon as you receive the coursematerials, and then get into the habit of communicating regularly, when youcomplete a unit or when you run into any special problem. We have foundthat students who maintain regular contact with their tutors are most likelyto be successful in completing their courses, so do keep in touch. You mayfind it useful to schedule a regular study period when your tutor isavailable so that you can contact him or her when questions arise. If you areunable to take advantage of the regular tutoring hours, contact your tutor orthe course professor to determine whether alternative arrangements can bemade.

If you use postal mail to send an assignment to your tutor, be sure to attacha tutor-marked exercise form, and to keep a copy, at least a rough draft, incase the original goes astray in the mail. If you take this course through theMoodle course management system, you may be instructed to use the“Assignment Drop Box” to submit your assignments. If you wish to submityour assignments electronically outside of the Moodle system, contact your


tutor to discuss appropriate formats. An electronic version of thetutor-marked exercise form is available online through your “myAU” portal.

In any case, allow several working days, in addition to mailing time eachway if applicable, before you expect to receive the graded assignment. Yourtutor will be pleased to provide additional feedback. Be sure to mention anyquestions you have about the assignment or the grade.

Keep your tutor’s letter of introduction with your course materials, and usethe space below to record information about your tutor.

Tutor’s name:

Address:

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 ortelephone number. Please inform the Office of the Registrar whenever sucha change occurs.

The Course Professor

The course professor is the member of Athabasca University’s academicstaff who is in charge of a given course. The professor works directly withtutors on both academic and administrative matters. If you have difficultiesyou cannot resolve with your tutor, you may wish to speak with theprofessor directly. You should also address any questions about creditrecords or centrally marked examinations to the professor. The professorcan also provide general information about program planning andcurriculum development. The course professor welcomes students’comments on the course.


Services to Students

Athabasca University offers a wide range of services to its students. TheAthabasca University Information Centre (1.800.788.9041) can help you findthe answer to most administrative questions. The Centre is staffed onregular business days from 7:00 a.m. to 5:30 p.m., Mountain Time.

Advisors are available to assist students in planning their programs andselecting appropriate courses. Counselors assist students in improving theirstudy skills and clarifying their educational goals. You may reach anadvisor or counselor in several ways: by dialling 1.800.788.9041 and askingto speak with an advisor or counselor; by visiting Athabasca University’sCentral Office in Athabasca, or the Athabasca University sites in Edmontonor Calgary; or by directing your query to

http://www.askau.ca

Students who are looking for information about student awards and adviceabout obtaining financial assistance are asked to contact the Office of theRegistrar. You may do so by dialling 1.800.788.9041 and asking for the Officeof the Registrar, or by inquiring through

http://www.askau.ca

Note: Students may write examinations at the Athabasca University sites inAthabasca, 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 variousadministrative matters, such as course registration and arrangements forextensions.

Indigenous Services at Athabasca University

If you are a student of Indigenous ancestry (Aboriginal, First Nations,Indian, Inuit, Native, Métis), or a non-Indigenous student who is interestedin identifying culturally appropriate services designed for Aboriginalstudents or counseling that is sensitive to the challenges Aboriginalstudents face, please contact the Centre for World Indigenous Knowledgeand Research, by telephone at 1.800.788.9041, extension 2064, or byelectronic mail at

[email protected]


Library Services

The Athabasca University Library collection contains more than 140,000books, many periodical titles and a range of audio-visual resources. TheLibrary subscribes to over 100 online databases, providing full text access toselected articles from more than 20,000 journals.

Athabasca University Library’s collection primarily supports AthabascaUniversity courses and programs. Materials found in the print andelectronic collections are available for use by our students, faculty and stafffor reference and research purposes. Requests for library materials orservices can be made, by email, phone, fax or mail, 24 hours a day (contactinformation is provided below). Responses to most requests are handledwithin 24 hours, or by the next business day. Borrowed materials arenormally mailed to the student’s home address, along with a return-mail card.

Core Services to Students

Athabasca University students registered in a course may

● borrow library materials.

● search the Library’s online catalogue (AUCAT).

● access resources through the Library’s website.

● receive library instruction and research assistance.

● request interlibrary loan (ILL) services for journal articles andbook chapters.

Digital Resources

Access to online journal databases, the Digital Reference Centre (DRC), andthe Digital Reading Room (DRR) is available from Athabasca UniversityLibrary’s main web page

http://library.athabascau.ca

Tips on searching the journal databases and help with researching, writingand 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 beyondthe contents of the course materials package. Some Athabasca Universitycourse Study Guides list “Supplementary Materials,” including books,


journal articles or audio-visual materials, which students may find usefulwhen completing assignments and course projects. The supplementarymaterials referenced in your course materials package are usually availablefrom the Athabasca University Library or your local library. Contact theAthabasca University Library to request materials.

How the Library Gateway Works

The Library website contains the Library’s online catalogue (AUCAT), and itis also the gateway to other online information. The website provides linksto journal databases and other subscribed online resources, as well as toselected, publicly accessible Internet sites. Subscribed resources areavailable to Athabasca University students, faculty and staff. You will berequired to enter your first and last names as your username and yourstudent ID number as your password.

The Library website also provides access to selected library catalogues fromCanadian public and academic libraries.

Interlibrary Loans

An interlibrary loan (ILL) involves one library borrowing materials fromanother on behalf of a library user. Athabasca University Library willrequest photocopies of journal articles and book chapters throughInterlibrary Loans, if you provide the Library staff with a completebibliographic citation (author, title of article, name of journal, volume andissue number, year of publication, and page numbers) for the requesteditem. You are not required to return these items to us. Allow sufficient timefor the material to be ordered and received. More information on theInterlibrary Loan process is available on the Library website at

http://aupac.lib.athabascau.ca/screens/ill.html

Contacts

Athabasca University Library1 University DriveAthabasca, AB Canada T9S 3A3

Library website: http://library.athabascau.caE-mail: [email protected]

Phone: 1.800.788.9041 (ext. 6254) Canada/US

Fax: 780.675.6477


Study Strategies

Chemistry 350 is a three-credit course and must be completed within the sixmonths of your official start date. This may seem like a long time, butprocrastination can rapidly put you in a difficult position. We suggest youstart right away and that you establish a study schedule. Your tutor canhelp you.

How fast you proceed through the first few units will depend on yourbackground in general chemistry. Most of the material covered in Units 1and 2 is a review of the topics covered in a typical university-level generalchemistry course, and you should be able to complete these units in lessthan a week. If your background is weak, you may have to put in extratime, and this may affect your chances of completing the course within thenormal six-month contract period. If you find that you really have troublewith Units 1 and 2, you should discuss the situation with your tutor andconsider withdrawing from the course or taking some action to improveyour understanding of basic chemistry.

At a traditional university, this course would normally be spread over onesemester and take about 12-13 weeks to complete. If you wish to attain thisrate, follow the 13-week study schedule shown in the “Course Outline andStudy Schedules” section of this Student Manual. If you wish to proceed atsomewhat slower rate, refer to the 18- and 24-week schedules when youplan your own personal study schedule. Should unforeseen circumstancesput you in a position where you find that you cannot complete the coursewithin the six-month contract period, check the Athabasca UniversityCalendar for current regulations about extensions. Be certain to check wellbefore the end of your course contract, to ensure that you meet anynecessary deadlines.

Although the amount of time that a student will need to spend on thecourse will depend on a variety of factors, students intending to completethe course in 13 weeks should be prepared to spend at least nine (9) hoursper week on the course. You may need additional time when you havelaboratory reports to write, or when you are reviewing for an examination.We suggest that you start in on Unit 1 now. As you work through it, make anote 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 thesequestions. Remember that regular study habits can be a major contributingfactor to ultimate success in this course.


How to Use the Study Guide

As you study each unit in Chemistry 350, follow the procedure outlinedbelow.

1. Read the preview and the list of unit objectives at the beginning of theunit. At this stage, some students find it beneficial to obtain an overallpicture of the unit by quickly reading through the whole chapter in thetextbook.

2. Study each lesson in the unit by

a. reading the objectives and study notes (if any). These notes maycontain study hints or additional information, and will also identifyany errors that occur in the relevant section of the textbook.

b. reading the required pages in the textbook, and using the objectivesand key terms to guide you in making your own notes.

c. completing the assigned exercises, and checking your answers in theStudy Guide, the Solutions Manual and the textbook. Note that yourproblem-solving ability will largely determine the overall grade thatyou receive in this course.

3. Review the unit by

a. making sure that you understand each of the unit objectives and cando what they require.

b. making sure that you can define and use the key terms.

c. reading the summary and the summary of reactions (whereappropriate) given at the end of the chapter in the textbook.

d. completing a selection of the recommended exercises listed in theStudy Guide.

4. Do the tutor-marked assignment (if there is one) and send it to yourtutor, or do the self test (if there is one) and check your own progress.

Warning: One of the problems with distance education is that,occasionally, lab reports, assignments, etc., get lost in the mail. As we canonly give credit for work that is actually received, we strongly advisethat you keep a rough copy of all of the work that you submit to yourtutor for marking. Also, please make certain that you attach a“Tutor-marked Exercise” form, from the course package, to any workyou submit for grading.


Course Outline and Study Schedules

The table below gives a brief course outline and suggests the amount oftime students should spend on each unit for 13-, 18- and 24-week schedules.

Note: Students who are receiving financial assistance may face special timeconstraints. Please check your course registration for any restrictions on thelength of registration, and be prepared to adjust your schedule.

13-week 18-week 24-weekUnit number and title schedule schedule schedule

1 Structure and Bonding Week 1 Week 1 Week 1

2 Polar Covalent Bonds: Acids andBases

Week 1 Week 1 Week 1

3 Organic Compounds: Alkanes andTheir Stereochemistry


4 Organic Compounds: Cycloalkanesand Their Stereochemistry


5 An Overview of Organic Reactions Week 2 Week 3 Week 4

6 Alkenes: Structure and Reactivity Week 3 Week 4 Week 5

7 Alkenes: Reactions and Synthesis Week 3 Week 5 Week 6

8 Alkynes: An Introduction to OrganicSynthesis


9 Stereochemistry Week 5 Week 7 Weeks 8/9

1-9 Review for Midterm Examination Week 6 Week 8 Week 10

10 Organohalides Week 7 Week 9 Week 11

11 Reactions of Alkyl Halides:Nucleophilic Substitutions andEliminations


12 Structure Determination: MS and IRS Week 8 Week 11 Weeks 13/14

13 Structure Determination: NMRS Week 9 Weeks 12/13 Weeks 15/16

14 Conjugated Compounds and UV

SpectroscopyWeek 10 Week 14 Weeks 17/18

15 Benzene and Aromaticity Week 11 Week 15 Weeks 19/20

16 Chemistry of Benzene ElectrophilicAromatic Substitution

Week 12 Week 16 Weeks 21/22

A Brief Review of Organic Reactions Week 13 Week 17 Week 23

1-16 Review for Final Examination Week 13 Week 18 Week 24


The table below allows you (with the help of your tutor) to plan apersonalized study schedule. Begin by filling in the first few units, and keeptrack of how long each unit is taking you. Once you have done the first fewunits, you (and your tutor) should be able to come up with a realisticschedule for the rest of the course. You may wish to remove the page anddisplay it in a prominent place, to help you keep track of your progress.

Planned Actual Time

Unit completion completion required Action

or event date date (hours) needed

Unit 1 Contact tutor re lab schedule;complete entry-level test

Unit 2 Complete entry-level test

Unit 3 See below, “Note 1.”

Unit 4

Unit 5 Complete first self test

Unit 6

Unit 7 Complete second self test

Unit 8 Complete TMA 1

Unit 9 Complete third self test

Midterm

Unit 10 See below, “Note 2.”

Unit 11 Complete fourth self test

Unit 12

Unit 13

Unit 14 Complete fifth self test

Unit 15

Unit 16 Complete TMA 2

Review Complete sixth self test

Final

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.



Assessment

The assessment of students in this course is based on examinations,tutor-marked assignments and laboratory work. Details are given in thetable below. To obtain credit for Chemistry 350, 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

Component Material covered of total mark

Midterm examination Units 3-9 20%

(2 hours)

Final examination Entire Course 50%

(3 hours)

Tutor-marked assignments following Unit 8 and Unit 16 10%

Laboratory work 20%

All examinations are supervised and “closed-book.” However, you will besupplied with a periodic table and a list of appropriate data (constants,spectral data, etc.).

Remember: You must be sure to have your own electronic calculator andmolecular models with you when you write an examination.

Note that while the emphasis of the final examination is on Units 10-16, youare still responsible for the material covered in Units 3-9.

If you are not satisfied with the mark you obtain on your first attempt at anexamination, you may rewrite that examination. There is a fee for thisservice. The supplemental examination will be similar in format to the firstone, and the higher of the two marks will be used when your overall coursemark is determined. You must write a supplemental if you obtain less than45% on an examination.

The following hints may help you to write examinations successfully.

Write only when you and your tutor feel that you are adequately prepared,and when you have successfully completed the relevant tutor-markedassignments.

Remember that the examination is based on the objectives outlined in theStudy Guide. Many of the questions will be similar in format to those givenin the tutor-marked assignments.

For short-answer questions, do the ones that you find easiest first. Thisstrategy has two benefits. First, you can more quickly accumulate enough


marks to pass the examination. Second, you gain confidence to tackle theharder questions.

For numerical problems, show your work! Part marks will be given forcorrect methods even if your answer is incorrect. The answers to numericalproblems should be given to the correct number of significant figures andwhere appropriate, with the correct units. Marks may be deducted ifanswers are given to an incorrect number of significant figures or in thewrong (or no) units.

Procedures for applying to write examinations may be found in the sectionof this Student Manual titled “Applying for an Examination,” below.

Applying for and Writing Examinations

If you are requesting to write an examination at Athabasca University(Athabasca), Athabasca University (Edmonton), or Athabasca University(Calgary), you must request your examination 10 calendar days before yourrequested write date.

If you live within Canada or the United States and are requesting anexamination to be written at an established Athabasca University ApprovedInvigilation Centre, you must request your examination 20 calendar daysbefore your requested write date.

If you live outside of Canada and the United States and are requesting anexamination to be written at an established Athabasca University ApprovedInvigilation Centre, your request must be received 30 calendar days beforeyour requested write date.

If you are requesting to write your examination using an invigilator who isnot established as an Athabasca University Approved Invigilator, yourrequest must be received 60 calendar days before your requested write date.

To request an examination, follow the steps below.

1. Review the “Examinations and Grades” section of the current AthabascaUniversity Calendar.

2. Arrange for a time to write your examination with one of AthabascaUniversity’s Examination Centres or with an invigilator. For a list ofExamination Centres, see the websitehttp://www.athabascau.ca/registrar/invignet.php

If you would like to use an invigilator who has not been approved by theOffice of the Registrar, you may propose their approval by filling in theappropriate details on the online Examination Request Form. Keep inmind that invigilators may charge a fee, for which you will beresponsible.

3. Complete and submit the online Examination Request Form. If you donot have access to the Internet, fill out the Examination Request Form


you received from the Office of the Registrar, and submit it by fax(780.675.6174), or in person or by postal mail to Examination Services,Office of the Registrar, at Athabasca University, Athabasca.

Note: To minimize the time required to process your application, be surethat you provide all of the information requested on the form, and thatyou write legibly.

4. Confirm that your invigilator has received the examination packagebefore you arrive to write your examination. Take picture identificationand your student number with you when you go to the examination site.

After you have written an examination, please be patient while you wait forthe result. Examinations rarely reach our central offices in less than fivedays, and a ten-day lapse from when the examination is written to its arrivalin Athabasca is not unusual. Chemistry examinations are normally markedwithin twenty-four hours of receipt, and your tutor is informed of the markbefore your next tutor night. Writing an examination one day and calling thecourse professor a day or two later does not expedite the marking process.

For security reasons, examinations cannot be returned to students, nor canthe professor enter into detailed discussions of specific examinationquestions. After each of your examinations is corrected, some writtencomments will be sent to you. Your tutor will also receive a copy of thesecomments, and you should discuss the issues raised with your tutor on thefirst suitable occasion.

Supplemental Examinations

Students who are dissatisfied with their grade on any examination, or whoobtain less than the required passing grade, may write a supplementalexamination. Only one supplemental is permitted per examination. Thehigher 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 withyour tutor or instructor. For the correct procedure, see “Student Code ofConduct and Right to Appeal” in the current Athabasca University Calendaror available through your myAU portal.


Student Conduct and Appeals

Three policies in particular govern the conduct of students of AthabascaUniversity:

● the Non-Academic Misconduct Policy,

● the Academic Misconduct Policy, and

● the Student Academic Appeals Committee Policy, also known as theAcademic Appeals Policy.

You are responsible for reading these policies carefully, as they affect yourstudies and your role as an Athabasca University student.

Links to these policies are provided though your myAU portal. Click on the“Student Services” tab near the top of your myAU web page. Links to thepolicies affecting students are given in the “Policies and Standards” sectionat the bottom right-hand side of the Student Services page. We encourageyou to read all of the policies on this list.

Note: All of the assignments you submit for this course must be originalwork completed especially for the course. The use of assignmentscompleted for other courses, or assignments from other students, both areconsidered cheating, and will be penalized as such.

Intellectual Indebtedness

Students enrolled in any Athabasca University course are considered to beresponsible scholars, and are therefore expected to adhere rigorously to theprinciples of intellectual honesty.

Plagiarism is a form of intellectual dishonesty in which another’s work ispresented as one’s 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 theexamination, the course or the program; or legal action.

Students sometimes commit plagiarism inadvertently. To avoid doing so,make certain that you acknowledge all your sources—both primary andsecondary—in a full and consistent manner. All direct quotes (quotations,however short, from an original work), indirect quotes, paraphrasedpassages, ideas, images, and tabular and statistical information that you usefrom other sources (including electronic sources) must be documentedusing an acceptable citation style. There are three conventional ways ofacknowledging your sources: in-text citations, footnotes, or end-notes. Weprefer that you use in-text citations, combined with a full bibliographypresented at the end of the essay. The in-text citation must give the name ofthe author, the date of publication, and the page on which the cited materialappears (Doe, 1997, p. 60). The bibliographic entry must provide at least theauthor’s last name, first name or initial, the date of publication, the title ofthe work, the place of publication and the publisher.


Transcripts

A student can request an official transcript by completing a paper“Transcript Request” form, by writing to the Office of the Registrar, byappearing at the Office of the Registrar in person, or by using the secureonline 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 student’s signature.

No partial transcripts are issued. The student’s entire record is shown oneach transcript.

Most institutions and agencies require that official transcripts be sentdirectly from Athabasca University. Please allow a minimum of ten workingdays for the receipt of a transcript. Consult the current edition of theAthabasca University Calendar for further information about transcripts.

Transferring Credit

If you wish to transfer credit to another institution, contact the Office of theRegistrar at Athabasca University. Remember, however, that transfer ofcredit is determined by the receiving institution. If you plan to transfer creditfor this course to another institution, we suggest you get an agreement, inwriting, from that institution. This agreement is usually called a “letter ofpermission.”

Applying for Extensions

If you are unable to complete this course within the six-month coursecontract period, you may apply for and purchase up to three, two-monthextensions. Note that extension request forms must be received by theOffice of the Registrar a minimum of one month before the end of yourcourse contract. Requests for second and third extensions must be receivedby the Office of the Registrar a minimum of one month before the expiry ofthe previous extension. Consult the online Athabasca University Calendar formore information about obtaining extensions.



Sample Examinations

On the following pages you will find sample examinations that will helpyou prepare for your midterm examination and your final examination. Wehave included such questions in this manual so that you may obtain a betteridea of the length of a normal Athabasca University chemistry examination.Short answers for a majority of the questions are given at the end of thesample examinations.



Sample Midterm Examination

The midterm examination is two (2) hours long. In the actual examination,you may not consult your books or notes; however, you may use acalculator or slide rule. You will also be provided with a periodic table and aset of 1H NMR chemical shifts and infrared stretching frequencies, asneeded.

1. Provide the complete IUPAC name for each of the following compounds:

a.

b.

c.


2. Provide structures for each of the following compounds:

a. 3-ethyl-1-methyl-1,3-cycloheptadiene

b. 3,3,7-trimethyl-5-(2-methylpropyl)nonane

c. 3-cyclobutyl-1,5-hexadiene


3. For each of the compounds below, assign the appropriate R or Sconfiguration to each of the atoms labeled with an asterisk.

Me Et

N+*a.

b.

Cl H

*

MeH

*

c.

d.

D H

*

4. Provide concise definitions for any (four) of the following terms. Be sureto make it clear which four are to be considered for grading, otherwisethe first four for which answers are provided will be evaluated.

a. torsional strain

b. chirality center

c. conformation


d. activation energy

e. electrophile

f. polarizability

g. substitution reaction

5. For each of the following molecules, provide a structure that satisfies thespecified condition:

a. The enantiomer of this cycloalkene:

Me

Me


b. A stereoisomer of the following compound that has a differentmelting point:

2HO C 2CO H

c. An alkyne that yields the following compound on treatment with Limetal in liquid ammonia:

d. A constitutional isomer of the following compound that yields asingle product on treatment with hydrochloric acid in ether solvent:


6. For each of the following pairs of structures, circle the one that is moststable. Provide a brief justification for your decision.

a. and

b. ● and

●

c. and

d. and


7. Compound A is a clear colourless liquid with a molecular formula ofC8H8. On treatment with excess H2 gas in the presence of Lindlarcatalyst, Compound B (C8H12) was recovered as the only product.Treatment of Compound B with O3 followed by zinc dust furnished thetwo products shown below. Provide structures for compounds A and B,and briefly justify your answers.

H

O O O

H

and

H

O

H


8. Consider the hypothetical transformation of starting material C intoproduct D. The ∆G○ for the process is 20 KJ/mol and the ∆G‡ is30 KJ/mol.

a. Complete the potential energy diagram for the conversion of C to D inthe grid provided below. Note that the position of C is provided foryou, and that each division along the vertical axis corresponds to10 KJ/mol.

C

En

erg

yGGGGGGGGGGGGGGGA

C GGGGGGGGGGGGGGGGGGGGA D

} 10 KJ/mol

b. Is the forward reaction endergonic, exergonic, or neither? Justify yourdecision.

c. Calculate the ∆G‡ for the hypothetical reverse process.

d. Which species would you expect to most closely resemble thetransition state: C or D? Justify your decision.


9. Provide a complete “arrow-pushing” mechanism for the followingtransformation that includes any reactive intermediates. Account for thefact that only a single alkyl bromide is formed in the reaction.

HBr CH3 ether Br


10. Identify which of the following two chair conformers ofchlorocyclohexane is more stable, and support your argument with athorough discussion including an analysis (with drawings) of Newmanprojections along the C1—C2 and C1—C6 bonds of each conformer.

H

2

61

Cl6

2

Cl

H

1


11. Provide three additional reasonable resonance structures for each of thefollowing compounds:

a.

O

N● ●

O

b.

O

c.N

O

N


12. Complete five of the following chemical equations by providing themissing starting material, reagent(s) or product(s) as necessary. Be sure toindicate stereochemistry where appropriate. Remember to clearlyindicate which reaction you do not want graded, otherwise the first fiveequations for which answers are given will be graded.

a.

KMnO4, H3O+

GGGGGGGGGGGGGGGGGGGA and

Note: There are two organic products.

b.H2SO4, H2O

GGGGGGGGGGGGGGGGGA

HgSO4

O

Cl

c.1. OsO4

GGGGGGGGGGGGGGGGA

2. NaHSO3, H2O


d.

HBr(1 equivalent)

GGGGGGGGGGGGGGGGGGA

Ether

e.H2, Pd/C

GGGGGGGGGGGGGA

f. GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGA


13. Outline a synthetic strategy for the multi-step preparation of any two) ofthe following compounds from the indicated organic starting material.For each synthetic step, indicate the required reagent(s) as well as anyorganic intermediate. Be sure to indicate which problem you do not wantgraded: otherwise the first two problems for which an answer (correct orotherwise) is provided will be graded.

a. prepare

OH

OH from

Br

b. prepare

CO2H

from

Br


c. prepare from



Sample Midterm Examination—Answer Key

1. a. 3-methyl-1,4-cyclohexadiene

b. (4Z)-5-methyl-4-octen-1-yne or (4Z)-5-methyloct-4-en-1-yne

c. 1-cyclohexyl-3-ethynylcyclohexane

2. a.

b.

c.

3. a. S

b. S

c. S

d. S

4. Definitions of all terms are given in the textbook glossary.

5. a.

Me

Me

b. 2CO H2HO C

c.

d.


6. a.

More highly substituted.

b. ●

Tertiary alkyl radicals are more stable than secondary ones, owingto the ability of the alkyl substituents to stabilize electron-deficientcentres via induction.

c.

Less ring strain.

d.

The E isomer is more stable, primarily as a result of slightly highersteric repulsion in the Z isomer.

7. A.

B.

The ozonolysis products directly implicate B as having the abovestructure, since this is the only possible structure with the formulaC8H12 that could possibly furnish the indicated products.

The reaction with H2 in the presence of Lindlar catalyst is a classic testfor alkyne functionality: no other functionality (including alkene) willreact under these conditions. The fact the molecular formula increasesby 4 hydrogen atoms as A converts to B indicates that 2 equivalents ofH2 gas are being consumed and that therefore A is a diyne. Since thecentral carbon in the 7-carbon chain in compound B does not have ahydrogen atom attached to it, it must be the double bond in themolecule that was originally also a double bond in A: as a result, theother two double bonds (those at the ends of the 7-carbon chain) musthave arisen from triple bonds in A, which allows one to arrive at theabove structure for A.


8. a.

En

erg

yGGGGGGGGGGGGGGGA

C GGGGGGGGGGGGGGGGGGGGA D

C. ............ ........... ...........

.......................................

....................................................... ....... ...... ....... ........ .......... ........................... ........... ............ ............

D

} 10 KJ/mol

b. Endergonic: ∆G○ is positive (the product is higher in energy thanthe starting material).

c. From the graph, it is apparent that ∆G‡ for the reverse process isthe difference between ∆G‡ for the forward process and ∆G○.

30 KJ/mol − 20 KJ/mol = 10 KJ/mol.

d. D: According to the Hammond postulate, the transition state mostclosely resembles the species which is most similar in energy. In anendothermic process, this is the product.

9.

H—Br

CH3

Br+

Br_

: :

::

The reason that only a single alkyl bromide is formed lies in the natureof the carbocation formed in the first step: it is tertiary. The alternativecarbocation (shown below) would be primary, and thus would be toohigh in energy to form.

+


10.

H

2

61

Cl

6

2

Cl

H1

more stable

Newman projection: C1–C6

H

H

H

R

R Cl

H

H

HR

R

Cl!

Newman projection: C1–C2

H

H

H

R

R

Cl H

H

H

R

R

Cl !

The conformer on the left, with the Cl atom in an equatorial position,is the most stable. In the case of this conformer, the Newmanprojections (C1—C6 and C1—C2) reveal that, in each case, theR-groups are “gauche” with respect to one another, but the bulky Clatom (on C1) is “anti” to the R group on the other atom.

In the case of the less stable conformer, the Newman projections(C1—C6 and C1—C2) reveal that the R-groups are in each case still“gauche” with respect to one another, but now there exists a secondunfavourable “gauche” interaction between the Cl atom on C1 and theR group on the adjacent atom (C2 or C6).

11. Any of the following are acceptable:

a.

OO_

: :

:

N+

O O_

: :

:

N +

OO_

: :

:

N+

O O_

: :

:

N

+

O O_

: :

:N

+

O

_:N+

:::

O


b.

O_

: :

:

+

O_

: :

:

+

O_

: :

:

+

c.

O_

: :

:

N+

N

::

O_

: :

:

N+ N

:

O_

: :

:

N

:

N +

12. a.

CO2H

andO

b. Cl

c.

HO

HO

d.Br

e.

f. CH2I2, Zn/Cu


13. a.

ethanol

KOH 1. OsO4

2. NaHSO , H O3 2

OH

OH

b.

Br

KOHGGGGGGGGGA

ethanol

KMnO4, H3O+

GGGGGGGGGGGGGGGGGGGA

CO2H

+ CO2

c.

Br2GGGGGGA

CH2Cl2

BrBr 2 KOH

GGGGGGGGGGGA

ethanol

H2GGGGGGGGGGGGGGGA

Lindlar catalyst


Sample Final Examination

The final examination is three (3) hours long. In the actual examination youmay not consult your books or notes; however, you may use a calculator orslide rule. You will also be provided with a periodic table and a set of1H NMR chemical shifts and infrared stretching frequencies, as needed.

1. Provide the complete IUPAC name for each of the following compounds:

a. OH

b.

NO2

Cl

c.


2. Provide structures for each of the following compounds:

a. m-chloroacetophenone

b. 3,3-dibromocyclooctene

c. (R)-3-benzyldecane

3. Identify which of the two protons, Ha or Hb, will have the higherchemical shift, and explain why.

O

CH3

HbHa

H3CO


4. Draw the structure of an organic compound that satisfies the givenspectral data:

a. a compound with the formula C4H9Cl with only one signal in its1H NMR spectrum: a singlet at 1.62 ppm.

b. a compound with the formula C3H7Br with the following 1H NMR

signals: A septet at 3.79 ppm (integrating for 1H), and a doublet at1.31 ppm (integrating for 6H).

c. a compound with the formula C7H5N with the following IR signals:3066 cm−1 (medium, sharp), 2230 cm−1 (strong, sharp), 1572 cm−1

(medium, sharp), 1492 cm−1 (medium, sharp).

d. a compound with the formula C6H8 which gives rise to two signals(ignoring coupling/splitting) in its 1H NMR spectrum, and does notabsorb UV light in the 200-400 nm range.


5. Using any combination of words, diagrams and chemical equations,explain the following observations.

a. Although 2-butyne possesses a C—C triple bond, no signal isobserved between 2400 cm−1 and 2100 cm−1 in the IR spectrum of thiscompound.

2-butyne

b. Friedel-Crafts alkylation is a poor method for the preparation ofbutylbenzene.

butylbenzene

c. During the preparation of a Grignard reagent, it is important that theglassware and chemicals are completely dry.


6. a. Complete the molecular orbital diagram for the cyclopentadienylcation by placing the electrons in the appropriate orbitals.

+

cyclopentadienyl cation

En

erg

y

ψ4 ψ5

ψ2 ψ3

ψ1

b. Complete the molecular orbital diagram for the cyclopentadienylanion by placing electrons in the appropriate orbitals.

−

cyclopentadienyl anion

En

erg

y

ψ4 ψ5

ψ2 ψ3

ψ1

c. Identify which of the two compounds (the cation or the anion) is themore stable, and carefully explain why this is so. A complete answershould include a discussion of the two MO diagrams completed above.


7. Compound A (C8H10) is a clear colourless liquid with a boiling point of139○C. Compound A is unreactive towards Br2 in the absence of light,but slowly reacts when exposed to sunlight to form HBr as a by-product.As well, compound A is unreactive towards H2 in the presence of anumber of different catalysts, including Pd/C and Lindlar catalyst. Onthe other hand, Compound A reacts with KMnO4 to form Compound B(C8H6O4). The 1H NMR spectrum of B contains three signals, all havingthe same integration. Provide structures for A and B.


8. a. From the following assortment of dienes, circle the one which youwould expect to be the most suitable for use in a Diels-Alder reaction.Briefly justify your choice.

b. From the following group of dienophiles, circle the one that youwould expect to be most reactive in a Diels-Alder reaction. Brieflyjustify your choice.

H

CO2CH3H

CO2CH3 H

HH

H H

CH3H

CH3

c. Draw the product you would obtain from the Diels-Alder reactionbetween the diene and dienophile you selected above. Be sure toindicate any product stereochemistry where appropriate.


9. Provide complete arrow-pushing mechanisms for the followingtransformations.

a.Br2

GGGGGGA

H2O

Br

OH


b.CH3Cl

GGGGGGGGGGA

AlCl3


10. In each of the cases below, circle the most appropriate compound. Justifyyour choice.

a. Which of these solvents is better for promoting an SN2 reaction?Explain your decision.

H

O

N(CH3)2

or CH3OH

DMF Methanol

b. Which of these substrates will undergo SN1 substitution morerapidly?

Br

or

Br

c. Which of these anions is more likely to promote an eliminationreaction instead of a substitution reaction?

CH3CH2S− or CH3CH2O−

d. Which of these anions reacts more rapidly as a nucleophile in an SN2reaction, if all other conditions are identical?

Br− or I−


11. Provide concise definitions for any four of the following terms. Be sure tomake it clear which four are to be considered for grading, otherwise thefirst four for which answers are provided will be evaluated.

a. McLafferty rearrangement

b. prochiral

c. Grignard reagent

d. LUMO

e. heterocycle

f. downfield

g. exothermic


12. Identify the number of signals you would expect to observe in the1H NMR of each of the compounds below. Also, for each compound,sketch the 1H NMR signal arising from the proton labeled with anasterisk, taking care to estimate the chemical shift of the indicated protonand to represent clearly the expected splitting pattern.

a.

H

NO2

HH

H3C

∗H

b.

O H∗

O

O

c.

H∗

O

O


13. Complete ten of the following chemical equations by providing themissing starting material, reagent(s) or major organic product(s) asnecessary. Be sure to indicate stereochemistry where appropriate. Be sureto make it clear which reaction you do not want graded, otherwise thefirst ten equations for which answers are given will be graded.

a.

BrSO3

GGGGGGGA

H2SO4

b.NBS

GGGGGGGA

c.NaNH2

GGGGGGGGGGGA


d. OHH3PO4

GGGGGGGGGGA

120○C

e.

Br

Na+ −CNGGGGGGGGGGGGGA

DMSO

f.1. O3

GGGGGGGGGGGA

2. Zn/H3O+

g.2 Br2

GGGGGGGGA

CH2Cl2


h.O

GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGA

O

i.

BrNaNH2

GGGGGGGGGGGA

NH3

200○C

j.H2

GGGGGGA

Pd/C


k.

O

Cl2GGGGGGA

FeCl3

l.Br

MgGGGGGGGA

ether


14. Outline a synthetic strategy for the multi-step preparation of thefollowing compounds from the indicated organic starting material. Foreach synthetic step, indicate the required reagent(s) as well as anyorganic intermediate.

a. prepare

CO2H

NO2

from

b. prepare

D

from

OH



Sample Final Examination—Answer Key

1. a. 2,3,5-trimethylphenol

b. 1-chloro-2-nitrobenzene

c. 2-ethyl-5-methyl-1,5-hexadiene

2. a.

O

Cl

b.

BrBr

c.

H CH Ph2

3.

O

CH3

HbHa

H3CO

Hb has the higher chemical shift. It is ortho to the carbonyl group,which is electron-withdrawing both by induction and by resonance.These same effects which deactivate the ortho and para positions forelectrophilic aromatic substitution also deshield protons in thesepositions raising the chemical shift.

O

CH3

O

+

_

: :

:

CH3

H

H CO3H CO3

a H aH b H b


4. a. Cl

b.Br

c. N

d.

5. a. 2-butyne is a symmetrical alkyne: each of the triply-bondedcarbons bears a methyl group and, as a result, the C—C triple bondis completely non-polar. Stretching this bond (with IR radiation)will not therefore result in a change in the bond dipole (ormolecular dipole) and so will result in no absorption in theindicated region of the IR spectrum.

b. Friedel-Crafts alkylation is a poor method for the preparation ofbutylbenzene because it would require the use of a primary alkylhalide, such as 1-chlorobutane or 1-bromobutane. Such alkylhalides do not directly form stable carbocations and often undergocarbocation rearrangements, making them unsuitable for use inFriedel-Crafts chemistry.

c. Grignard reagents are extremely basic and reactive towards waterand any other compounds containing —OH groups. If theglassware or chemicals are wet, the Grignard reagent, if formed,will immediately be protonated (and thus destroyed) by the water.

6. a.

Ψ1

Ψ2 Ψ3

Ψ4 Ψ5+

cyclopentadienyl cation

b.

Ψ1

Ψ2 Ψ3

Ψ4 Ψ5_

cyclopentadienyl anion

ener

gy

c. The anion is considerably more stable than the cation. The sixvalence electrons completely fill the degenerate orbitals Ψ2 and ψ3,


imparting unusual stability on the anion: the anion is thusaromatic.

On the other hand, the cation has only four valence electrons,which result in partially filled degenerate orbitals ψ2 and ψ3. As aresult of this, the cation is said to be anti-aromatic and is extremelyunstable.

7. CO2H

CO2HA B

8. a.

This is the only one of the dienes that can attain the required s-cisconformation required for Diels-Alder chemistry. Furthermore, thethird diene is not conjugated, and is thus doubly unsuitable forDiels-Alder chemistry.

b. H

CO2CH3H

CO2CH3

This dienophile will work best in Diels-Alder chemistry as it is theone bearing the electron-withdrawing groups: such groupsenhance the reactivity of a dienophile.

c. H

H

CO CH2 3

CO CH2 3


9.

— Br:

::

Br:

::

B

+Br:

:

Br

O

HH

: :

+

OH:

:

OH

H

Br

a.

B

+

—::

::Cl

AlCl3

CH 3

—

:

:

Cl

H C3

H

: _

+

AlCl3b.


10. a. DMF is the better solvent for promoting SN2 reactivity. Althoughboth solvents are quite polar, DMF is aprotic whereas methanol isprotic. The protic solvent, methanol, stabilizes nucleophiles,rendering them less reactive and therefore slowing the rate of SN2reactions. On the other hand, the aprotic solvent does not sufferfrom this disadvantage.

H

O

N(CH3)2

or CH3OH

DMF Methanol

b. The rate of the SN1 substitution is determined by the rate of cationformation,which is in turn determined by cation stability. The alkylbromide on the left would form the more stable carbocation (it istertiary) and therefore is more rapid in SN1 substitution chemistry.

Br

or

Br

c. The anion on the right is the more basic and therefore the morelikely to induce an elimination reaction.

CH3CH2S− or CH3CH2O−

d. Although both anions are good nucleophiles, iodide is larger andmore polarizable, and is therefore the one which will react morerapidly in an SN2 process.

Br− or I−

11. Definitions for all of the terms are located in the glossary in the coursetextbook.


12. a.

H

NO2

HH

H3C

∗H

3 signals7.3 ppm

The indicated proton should appear as

a doublet near 7.3 ppm.

b.

O H∗

O

O

1 signal3.7 ppm


a singlet near 3.7 ppm.

c.H∗

O

O

4 signals4.1 ppm


a quartet near 4.1 ppm.

13. a.

Br

SO3H

and

Br

HO3S

b.

Br

c.C− +Na..


d.

e.

CN

f.

O

O

g.

BrBr

BrBr

h.

i.

NH2

j.

k.

O

Cl

l.MgBr


14. a.

CH3Cl,AlCl3

GGGGGGGGGGGA

KMnO4,

H3O+

GGGGGGGGGGGGA

CO2H

HNO3,H2SO4

GGGGGGGGGGGA

CO2H

NO2

b.

OH

H3PO4GGGGGGGGGGA

HBrGGGGGGGA

Ether Br

MgGGGGGGGA

Ether MgBr

D2OGGGGGGGGA

D


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Chemistry 350 - Athabasca University