Chemistry 360 - Athabasca University

Chemistry 360

Organic Chemistry II

Student Manual

Note: The Student Manual was prepared primarily for individualized-studystudents. Students who are taking this course with seminar support orthrough a co-operating institution should be aware that some of theinformation will not apply in their situation. In case of doubt, please askyour tutor or seminar leader about any problems that might arise. Furtherclarification can be obtained from the course professor.

Athabasca University

Course Team

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

Note: This course is a revision of a part of Chemistry 345: Organic Chemistryby Arthur Last, copyright c© 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.

c© Athabasca University 1998, 2003, 2004, 2010All rights reservedPrinted in Canada

CMID 554275Revision 6

Contents

The Course . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

The MyAU Portal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Your Student ID Number . . . . . . . . . . . . . . . . . . . . . . . . . . 2

Freedom of Information and Protection of Privacy . . . . . . . . . . . 2

The Athabasca University Calendar . . . . . . . . . . . . . . . . . . . 2

Course Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

Other Items . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

Forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

Course Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

Laboratories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Your Tutor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

The Course Professor . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

Services to Students . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

Library Services . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

Study Strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

How to Use the Study Guide . . . . . . . . . . . . . . . . . . . . . . . 12

Course Outline and Study Schedule . . . . . . . . . . . . . . . . . . . 14

Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

Applying for and Writing Examinations . . . . . . . . . . . . . . . . . 18

Student Conduct and Appeals . . . . . . . . . . . . . . . . . . . . . . . 20

Intellectual Indebtedness . . . . . . . . . . . . . . . . . . . . . . . . . . 20

Transcripts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

Transferring Credit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

Applying for Extensions . . . . . . . . . . . . . . . . . . . . . . . . . . 21

Sample Examinations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

Sample Examination Answer Keys . . . . . . . . . . . . . . . . . . . . 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 thiscourse will have completed Athabasca University’s Chemistry 350: OrganicChemistry I, or an equivalent university-level course in organic chemistry. Ifyou have not done so, you should contact the course professor immediately.

Organic Chemistry II 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 360 introduces the studentto the basic techniques 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 outlineprovided in 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 Athabasca University where you canquickly access information that is relevant to you. Through myAU, you canview personal information, such as library accounts and assignment marksand course 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

Organic Chemistry II 1

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.

2 Chemistry 360 / Student Manual

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 360: Organic Chemistry II. Student Manual. Athabasca, AB:Athabasca University, 2010.

You are now reading the Student Manual.

Chemistry 360: Organic Chemistry II. Study Guide. Athabasca, AB: AthabascaUniversity, 2010.

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

Chemistry 360: Organic Chemistry II. 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 360: Organic Chemistry II. 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 360, 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.”

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 yourprogress in the course—they are not a comprehensive overview of thematerial, nor are they at the same level of difficulty that you will encounterin the midterm and final examinations. [Sample examinations are given in


this manual.] If you have difficulty with any self test, you should go backand 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 atselected times during the rest of the year. The Lab Coordinator will be ableto provide up-to-date information, or you may go to our Lab Informationwebsite 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 360 is a three-credit course and must be completed within the sixmonths of your contract period. 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 organic chemistry from Chemistry 350. If your background isweak, you may have to put in extra time, and this may affect your chancesof completing the course within the normal six-month contract period. Ifyou find that you really have trouble with Units 17 and 18, you shoulddiscuss the situation with your tutor and consider withdrawing from thecourse or taking some action to improve your understanding offundamental organic 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. Remember that regular studyhabits can be a major contributing factor to ultimate success in this course.Should unforeseen circumstances put you in a position where you find thatyou cannot complete the course within six months, check the AthabascaUniversity Calendar for current regulations about extensions.

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 Unit 17 now. As you work through it, make a noteof any questions you have on content, study procedures, etc. Then, beforeyou go on to the next unit, contact your tutor to clear up these questions.

How to Use the Study Guide

As you study each unit in Chemistry 360, 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 and the textbook. Note that your problem-solving abilitywill largely determine the overall grade that you 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 can only give creditfor work that is actually received, we strongly advise that you keep a roughcopy of all of the work that you submit to your tutor by mail. Also, pleasemake certain that you attach a “Tutor-marked Exercise” form to any workyou mail in for grading. Student using the Moodle Assignment Drop Boxshould follow the instructions given on the Moodle course website.


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.

Unit number and title

13-weekschedule

18-weekschedule

24-weekschedule

17 Alcohols and Phenols Week 1 Week 1 Weeks 1-2

18 Ethers and Epoxides;Thiols, and Sulphides

Week 2 Week 2 Weeks 3-4

A Preview of CarbonylCompounds

Week 2 Week 2 Week 5

19 Aldehydes and Ketones:Nucleophilic AdditionReactions

Week 3 Weeks 3-4 Weeks 6-7

20 Carboxylic Acids andNitriles


21 Carboxylic AcidDerivatives andNucleophilic AcylSubstitution Reactions


22 CarbonylAlpha-SubstitutionReactions


Review for MidtermExamination


23 Carbonyl CondensationReactions


24 Amines and Heterocycles Week 10 Weeks 12-13 Weeks 16-18

25 Biomolecules:Carbohydrates


26 Biomolecules: AminoAcids, Peptides, andProteins


27 Biomolecules: Lipids Week 12 Weeks 16-17 Weeks 22-23

28 Biomolecules: Nucleic Acids Week 12 Weeks 16-17 Weeks 22-23

Review for FinalExamination



The table below allows you to plan (with the help of your tutor) apersonalized study schedule. We suggest you begin by filling in the first fewunits and keep track of how long each unit is taking you. After you havedone the first few units, you (and your tutor) should be able to come upwith a realistic schedule for the rest of the course.

Planned Actual Time

Unit completion completion required Action

or event date date (hours) needed

Unit 17 Contact tutorre lab schedule.

Unit 18 Complete Self Test 1.

See below, “Note 1.”

Preview

Unit 19

Unit 20 Complete Self Test 2

Unit 21 Complete TMA 1


MidtermExamination

Unit 23 See below, “Note 2.”


Complete TMA 2

Unit 25

Unit 26, 27 or 28 CompleteSelf Test 5, 6 or 7

Review

FinalExamination

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 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.

Component Material coveredPercentageof total mark

Midterm Examination(2 hours)

Units 17-22 20%

Final Examination(3 hours)

Entire Course 50%

Tutor-markedAssignments

Following Unit 21and Unit 25

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 the materialcovered in Units 23-25 and the optional unit, you are still responsible for thematerial covered in Units 17-22. In addition, both midterm and finalexaminations assume you still have the skills and knowledge gained inyour previous organic chemistry course.

The hints given below may help you to write examinations successfully.

1. Write only when you and your tutor feel that you are adequatelyprepared, and when you have successfully completed the relevanttutor-marked assignments. Remember that the examination is based onthe objectives outlined in the Study Guide. Many of the questions will besimilar in format to those given in the tutor-marked assignments.

2. For short answer questions, do the ones that you find easiest first. Thisprocedure has two benefits. First, you can more quickly accumulateenough marks to pass the examination. Second, you gain confidence totackle the harder questions.


3. For numerical problems, show your work! Part marks will be given forcorrect methods even if your answer is incorrect. The answers tonumerical problems should be given to the correct number of significantfigures, and where appropriate, with the correct units. Marks may bededucted if answers are given to an incorrect number of significantfigures or in the wrong (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 website

http://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 Formyou 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 to give you a better idea of thelength of a normal Athabasca University chemistry examination. Shortanswers for the questions are given at the end of the sample examinations(see the section of this manual titled “Sample Examination Answer Keys”).



Sample Midterm Examination

The midterm examination is two (2) hours long. In the actual examination,you will not be allowed to consult your books or notes; however, you willbe permitted to use a calculator or slide rule. You will also be provided witha periodic table and a set of 1H NMR chemical shifts and infrared stretchingfrequencies.

Part A: Short Questions (3 marks each)

1. Provide the IUPAC name for each of the compounds below. Indicatestereochemistry as appropriate.

IUPAC name:

a. O

O

b.

O

SHH

.c.


2. Draw the appropriate structure for each of the compounds below.

a. 1, 2-epoxybutane

b. N,N-dimethylacetamide

c. 5-hydroxy pentanenitrile

3. Rank the acidity of the compounds below (1 = most acidic; 3 = leastacidic).

O

OHO

OH

O

OH


4. Draw all the resonance forms for the following species:

O−

O

5. Circle the secondary thiol

S

SHSH

6. Draw the mechanism showing the acid catalyzed hydration of acetone.

O H3O+

E GGGGGGGGGGGGGGGGC

HO OH


7. Identify regents (a)-(c) in the following scheme:

O

OH

GGGGGGGGA

OH

GGGGGGGGA

O

H

DGGGGGGGG

(a) (b)

(c)

8. Sketch the 1H NMR spectrum of ethyl acetate:

O

O .

For each signal, indicate intensity, multiplicity and chemical shift.

8ppm

7 6 5 4 3 2 1 0


9. What properties account for the fact that acetic acid is a stronger acidthan ethanol?

10. Compound A, C2H4O, shows an infrared absorption at 1715 cm−1 andan 1H NMR spectrum as detailed below.

Signal (ppm) Intensity Multiplicity

9.8 1 quartet

2.2 3 doublet

Propose a structure for Compound A, and justify your answer.


Part B: Longer Questions (marks indicated)

11. Identify the major product or products for seven (7) of the following14 marksreactions, and show stereochemistry where appropriate.

Note: Only the first seven questions answered will be marked—soonly give answers for those items you want marked.

a.O

GGGGGGGGGGGGGGGA , ether1. CH3MgBr

2. H3O+

b.O

GGGGGGGGA

HCN

c.

O

GGGGGGGGGGGGA

NH2OH


d.OH

GGGGGGGGGGGA

PCC

CH2Cl2

e.O

NH2

GGGGGGGGGGA

SOCl2

f.

O

GGGGGGGGA

H Br

g.

O

OH

OH

GGGGGGGGGGGGGGGGGGA

O

O

O

N


h.SH

GGGGGGGGGGGGGGGA

l2

H2O

i. GGGGGGGGGGGGGGGGGGGA

Cl

O

O OH

j. GGGGGGGGGGGGGGGGGGGGA

1. O3

2. Zn, CH3CO2H

k.

O

O

O

GGGGGGGGGGA

2 NH3


12. Show by means of a series of chemical equations how three (3) of the12 marksfollowing conversions could be achieved.

Note: Only the first three questions answered will be marked—so onlygive answers for those items you want marked.

a.

OH

GGGGGGGGA

O

b.

OH

GGGGGGGGA

O


c. GGGGGGGGA

O

d.O

GGGGGGGGA

OH

13. Write the complete stepwise mechanism for the reaction shown below.8 marksShow all intermediate structures and mark electron flows with arrows.

O

NH2

GGGGGGGGBF GGGGGGGG

H3O+

O

OH

+ NH+

4


14. Give a brief definition for three (3) of the following terms. Use6 marksexamples where appropriate.


a. mercapto group

b. carbinolamine

c. Fischer esterification reaction

d. thioester

e. enolate ion

f. α, β-unsaturated carbonyl compound


15. An unknown Compound A shows the molecular ion M+ at m/z 1147 marks(C7H14O), with a single major fragment at m/z 71.

The infrared spectrum of Compound A displays a strong absorptionband at 1715 cm−1, and its 1H NMR spectrum is shown below.

Derive the structure of Compound A. Justify your answer.[7 marks]

1H NMR

ppm7 6 5 4

1H

3 2 1

6H

0

— END OF EXAMINATION—


Sample Final Examination

The final examination is three (3) hours long. In the actual examination, youwill not be allowed to consult your books or notes; however, you will bepermitted to use a calculator or slide rule. You will also be provided with aperiodic table and a set of 1H NMR chemical shifts and infrared stretchingfrequencies.

Part A: Short Questions (3 marks each, unless otherwise noted)

1. Provide the IUPAC name for each of the compounds below.1 mark each

IUPAC name:

a.NH

b.

O

CN

c.

O

Cl

d.

SH

Br

e. Li Cu(CH3)2

f. NH2


2. Draw the IUPAC the chemical structure for each of the compounds below.1 mark each

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


3. Rank the basicity of the amines below (1 = least basic, 3 = most basic)

H2N CH2CH3NH

NH2

4. Write the resonance structures for the anion below.

O O

−


5. a. What alkyl halide would you use to prepare 4-phenylbutanoic acidusing the malonic ester synthesis?

b. What alkyl halide would you use to prepare 4-phenyl-2-butanoneusing the acetoacetic ester synthesis?

6. a. What is the structure of the carboxylic acid precursor to3-methylaniline

CH3

NH2

when prepared by the Curtius reaction?

b. Is the structure of this carboxylic acid the same as or different from thestructure of the carboxylic acid needed to prepare 3-methylaniline bythe Hofmann reaction?


7. a. Circle the most stable stable cation

+

+

+

b. Circle the optically active compound

Cl

Cl

Br

CH3 H3C

H

Cl

CHO

C

OHH

HHO

OHH

CH2OH

H2OH

8. Draw the structure of the carbonyl compound whose 1H NMR spectrumis summarized in the table below.

Chemical shiftδ (ppm)

Signalmultiplicity

2.1 singlet (3 H)

2.4 quartet (2 H)

1.1 triplet (3 H)


Part B: Longer Questions (marks indicated)

9. State the major product or products for ten (10) of the reactions below.20 marks

Note: Only the first ten questions answered will be marked—so onlygive answers for those items you want marked.

a. HC

HHO

OHH

CH2OH

O

GGGGGGGGGGGGGGGGA

HNO3

b.

NO2

GGGGGGGGGGGGGGGGGGGGGA

1. SnCl2, HCl

2. HNO2, H2SO4

3. NaI

c. CN GGGGGGGGGGGGGGGGGGGGGA

1.

MgBr

2. H3O+


d.

O

OH GGGGGGGGGGGGGGGGA

1. Br2, PBr3

2. H2O

e.N

+

O

GGGGGGGGGGGGGGGGA

1. THF

2. H+

f.

O

OH

GGGGGGGGGGGGGGGGGGGA

1. SOCl2

2. H N

g.O

O

GGGGGGGGGGGGGGGGGGGGGGGGGA

1. NaOCH3, CH3OH

2. H3O+


h.O

GGGGGGGGGGGGA

NH2NH2

KOH

i.

.

..

H

OHH

GGGGGGGGGGGGGGGGA

CrO3

H3O+

j.

OH

O

OH

GGGGGGGGGGGGGGGGGGGGGGGA

1.

O

Clpyridine

2. CH3OH, HCl


k.

O


NaOCH3, CH3OH

l.SH

GGGGGGGGGGGGGGA

l2

H2O

m. O + (C6H5)3P+

C−

H CH3 GGGGGGGGGGGGGGA

OO

n.

OH

OH GGGGGGGGGGGGGGA

PCC

CH2Cl2


10. In your own words, define five (5) of the terms given below.10 marks

Note: Only the first five questions answered will be marked—so onlygive answers for those items you want marked.

a. heterocyclic amine

b. mutarotation

c. chemical shift

d. parent peak

e. enol

f. anomers

g. Hell Volhard-Zelinskii reaction

h. mixed aldol

i. α,β-unsaturated ester


11. Propose the step-wise mechanism for each of the transformations10 marksbelow. Use arrows to show electron flow where appropriate.

a.

N N+

HSO−4

+

NH2

GGGGGGGGA

N N

NH2

b. O

H

GGGGGGGGGGGGGGAD GGGGGGGGGGGGGG

NaOH

ethanol

OH O

H


12. Propose and show the synthetic pathway for two of the10 markstransformations below.

Note: Only the first two questions answered will be marked—so onlygive answers for those items you want marked.

a.

CN

GGGGGGGGA

NH2

b.

O

GGGGGGGGA

HO

O

c.

O O

OGGGGGGGGA

O


13. a. Compound A, C10H18O undergoes reaction with dilute H2SO4 at10 marks25◦C to yield two alkenes, C10H16, B and C. The major alkeneproduct B gives only cyclopentanone after ozone treatmentfollowed by reduction with zinc in acetic acid.

Identify A, B and C.

b. Compound A is a D-aldopentose C5H10O5 that can be oxidized toan optically inactive aldaric acid B on treatment with HNO3.

On Kiliani-Fischer chain extension, Compound A is converted tocompounds C and D: Compound C can be oxidized to an opticallyactive aldaric acid E, where as Compound D is oxidized to anoptically inactive aldaric acid F.

What are the structures of A to F?


Note: The remainder of this examination is based on the three optional unitsin this course. You have studied one of the possible three units. Pleasecomplete only one (1) of the following questions

Unit 26 Biomolecules: Amino Acids, Peptides and Protein

15. Threonine, (2S, 3R)-2-amino-3-hydroxybutanoic acid, has two chirality10 markscentres.

a. Draw the Fischer projection of threonine

b. Draw the predominant form of threonine in a pH 4.0 buffer solution.The isoelectric point of threonine is 5.6.

c. Use the amidomalonate synthesis to prepare the amino acidphenylalanine beginning with diethyl acetamidomalonate.


Unit 27 Biomolecules: Lipids

16. a. Draw the major products you would expect from the reaction of10 markscholesterol and the following reagents

HOCholesterol

i.GGGGGGGGGGGGGGA

CrO3

H+

ii.


O

O

O

pyridine

iii.GGGGGGGGGGGGGGA

Br2

CH2Cl2


b. Draw the molecules below in chair conformations, and indicatewhether the bridgehead methyl is axial or equatorial.

i.

.

H

ii.

H


Unit 28 Biomolecules: Nucleic Acids

17. a. Describe, using chemical structures, two major structural differences10 marksbetween DNA and RNA.

b. Explain each of the following terms:

i. replication

ii. messenger RNA

iii. coding strand

c. What RNA base sequence is complementary to the DNA base sequencebelow?

(5′) G A T T A C C G T A(3′) end

— END OF EXAMINATION —



Sample Examination Answer Keys



Sample Midterm Examination

Part A:

1. Provide the IUPAC name for each of the compounds below. Indicatestereochemistry as appropriate.

IUPAC name:

a. O

O

cyclopentyl 2-methylpropanoate

b.

O

1-methoxycyclohexene

SHH

.c. (R)3-heptanethiol


2. Draw the appropriate structure for each of the compounds below.

a. 1, 2-epoxybutane

O

b. N,N-dimethylacetamide

O

N

c. 5-hydroxy pentanenitrile

HOCN

3. Rank the acidity of the compounds below (1 = most acidic; 3 = leastacidic).

O

OHO

OH

O

OH

3 2 1


4. Draw all the resonance forms for the following species:

−O O

O−

O

←→

←→

O O−

5. Circle the secondary thiol

S

SHSH

6. Draw the mechanism showing the acid catalyzed hydration of acetone.

OH

O

H

H••

+

E GGGGGGGGGGGGGGGGC

H3O+

H2O

HO OH

H2O +

EGGGGGG

GGGGGGC

••

+OHGGGBF GGG

O+

H H

OH

GGGBF GGG

OH

OH

+ H3O+

HO

H

• •


7. Identify regents (a)-(c) in the following scheme:

O

OH

LiAlH4GGGGGGGGGGGGA

ether OH

PCCGGGGGGGGGA

CH2Cl2

O

H

NH

2 NH

2GGGGGGGGGGGGGGA

KO

H

8. Sketch the 1H NMR spectrum of ethyl acetate:

O

O .

For each signal, indicate intensity, multiplicity and chemical shift.

8ppm

7 6 5 4 3 2 1 0

~3.5 ppm

OCH2

2H

CH3

3H

−

O

CH3C

3H

~2.0 ppm ~1.0 ppm


9. What properties account for the fact that acetic acid is a stronger acidthan ethanol?

O

OH

GGGGGGBF GGGGGG

O

O−

←→

O−

O

OH GGGGGGBF GGGGGG O−

Resonance stabilization of carboxylate anion accounts for increasedacidity of acetic acid compared to ethanol.

10. Compound A, C2H4O, shows an infrared absorption at 1715 cm−1 andan 1H NMR spectrum as detailed below.

Signal (ppm) Intensity Multiplicity

9.8 1 quartet

2.2 3 doublet

Propose a structure for Compound A, and justify your answer.

d 2.2 ppm

degrees of unsaturation = 1

∼1715 cm−1

H3CC

O

H

q 9.8 ppm


Part B: Longer Questions

11. Identify the major product or products for seven (7) of the followingreactions, and show stereochemistry where appropriate.

Note: Only the first seven questions answered will be marked—soonly give answers for those items you want marked.

a.O

GGGGGGGGGGGGGGGA either1. CH3MgBr

2. H3O+ OHor

b.O HCN

GGGGGGGGGA

NC OH

c.

O

GGGGGGGGGGGGA

NH2OH

NOH


d.OH

GGGGGGGGGGGA

PCC

CH2Cl2

O

H

e.O

NH2

GGGGGGGGGGA

SOCl2 CN

f.

O

GGGGGGGGA

H Br OH

Br

g.

O

OH

OH

GGGGGGGGGGGGGGGGGGA

O

O

O

N

O

OH

O

O


h.SH

GGGGGGGGGGGGGGGA

l2

H2O S S

i. GGGGGGGGGGGGGGGGGGGA

Cl

O

O OH

O

j. GGGGGGGGGGGGGGGGGGGGA

1. O3

2. Zn, CH3CO2HO +

H

O

k.

O

O

O

GGGGGGGGGGA

2 NH3O

NH2

+

O

O−

NH+

4


12. Show by means of a series of chemical equations how three (3) of thefollowing conversions could be achieved.


a. OH

CrO

3DGGGGGGGGG

D GGGGGGGGGGG

py

rid

ine

GGGGGGGGGGGGGA

O

OBr2/PBr3

GGGGGGGGGGGGGGA

OBr

b.

OH

GGGGGGGGA

O

O

GGGGGGGGGGGA

NaOH

ethanol

O

H O

H3O

+

GGGGGGGGGGA

CrO

3DGGGGGGGGGGGGGGG

H3O

+,a

ceto

ne


c.E

ithe

r

GGGGGGGGGGGA

O

CH3ClD GGGGGGGGGGG

AlCl3

GGGGGGGGGGGA

NB

S

CH

2 Cl2

Br

Na OCH3GGGGGGGGGGGGGGGA

CH3OH

+−

or

GGGGGGGGGGGA

O

CH3ClD GGGGGGGGGGG

AlCl3

KMnO4D GGGGGGGGGGGG

CO

2 H

GGGGGGGGGGGA

LiA

lH4

ether

OH

1. NaOHGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGA

2. CH3Br

66C

hem

istry360

/S

tud

en

tM

an

ual

d.O

GGGGGGGGGGGA

OH

Br

DGGGGGGGGGGGGGGGGGGGGGG

PP

h3

BH

3

GGGGGGGGGGGGGGGGGGGGGGA

H2O

2, O

H−

13. Write the complete stepwise mechanism for the reaction shown below.Show all intermediate structures and mark electron flows with arrows.

O

NH2

••

GGGGGGBF GGGGGG

H3O+

O

OH+ NH+

4

H O

H

H

+

GGGGGGGGB

FGGGGGGGG

+HO

H

• •

HO+

NH2

GGGGGGBF GGGGGG

OH

OHH

NH2

+

• •

GGGGGGBF GGGGGG

GGGGGGGGGGGGGGGGGGGGGGGGB

FGGGGGGGGGGGGGGGGGGGGGGGG

OH

OH

NH3

+

••


14. Give a brief definition for three (3) of the following terms. Useexamples where appropriate.


a. mercapto group

a thiol SH

b. carbinolamine

COH

NH2

c. Fischer esterification reaction

an acid catalyzed reaction between a carboxylic acid and an alcohol

R C

O

OH + R′OHH+

GGGGGGBF GGGGGG R C

O

OR′ + H2O

d. thioester

O

SR

e. enolate ion

O −

f. α, β-unsaturated carbonyl compound

O

αβ


15. An unknown Compound A shows the molecular ion M+ at m/z 114(C7H14O), with a single major fragment at m/z 71 in its mass spectrum.

The infrared spectrum of Compound A displays a strong absorptionband at 1715 cm−1, and its 1H NMR spectrum is shown below.

Derive the structure of Compound A. Justify your answer.

1H NMR

ppm7 6 5 4

1H

3 2 1

6H

0

degree of unsaturation = 1

1715 cm−1∴ C = O

NMR C

CH3

CH3

H

14H − 7H = 7H; therefore, the molecule is symmetrical.

MS C

O

CH

CH3

CH3

major fragment

m/z 28

m/z 43

m/z 71

Compound A:

H3C

CH

H3C

C

O

C H

CH3

CH3

— END OF EXAMINATION—



Sample Final Examination

The final examination is three (3) hours long. In the actual examination, youwill not be allowed to consult your books or notes; however, you will bepermitted to use a calculator or slide rule. You will also be provided with aperiodic table and a set of 1H NMR chemical shifts and infrared stretchingfrequencies.

Part A:

1. Provide the IUPAC name for each of the compounds below.

IUPAC name:

a.NH

pyrrolidine

b.

O

CN

3-cyano-2-cyclohexen-1-one

c.

O

Cl 2-chlorocyclopentanone

d.

SH

Br

4-bromobenzenethiol

e. Li Cu(CH3)2 lithium dimethylcuprate

f. NH2 aniline


2. Draw the IUPAC the chemical structure for each of the compounds below.

a. D-glyceraldehyde

CH O

H OH

CH2OH

b. N,N-dimethyl cyclopentylamine

N

c. (S) 4-bromo-2-hexanone

H

OBr

d. 2-ethylcyclohexane-1,3-dione

O

O

e. 2-butene-1-thiol

SH

f. 3-chloropyridine

Cl

N


3. Rank the basicity of the amines below (1 = least basic, 3 = most basic)

H2N CH2CH3NH

NH2

3 2 1

4. Write the resonance structures for the anion below.

O O

−

O O−

←→

O O

−

←→

O O−

There are three resonance structures.


5. a. What alkyl halide would you use to prepare 4-phenylbutanoic acidusing the malonic ester synthesis?

Br

+ CH2(CO2R′)2

b. What alkyl halide would you use to prepare 4-phenyl-2-butanoneusing the acetoacetic ester synthesis?

Br+

OR′C

O

O

6. a. What is the structure of the carboxylic acid precursor to3-methylaniline

CH3

NH2

when prepared by the Curtius reaction?

CH3

CO2H

b. Is the structure of this carboxylic acid the same as or different from thestructure of the carboxylic acid needed to prepare 3-methylaniline bythe Hofmann reaction?

It is the same.


7. a. Circle the most stable stable cation

+

+

+

1◦ 2◦ 2◦, allylic

b. Circle the optically active compound

Cl

Cl

Br

CH3 H3C

H

Cl

CHO

C

OHH

HHO

OHH

CH2OH

H2OH

8. Draw the structure of the carbonyl compound whose 1H NMR spectrumis summarized in the table below.

Chemical shiftδ (ppm)

Signalmultiplicity

2.1 singlet (3 H)

2.4 quartet (2 H)

1.1 triplet (3 H)

O


Part B: Longer Questions

9. State the major product or products for ten (10) of the reactions below.

Note: Only the first ten questions answered will be marked—so onlygive answers for those items you want marked.

a. HC

HHO

OHH

CH2OH

O

GGGGGGGGGGGGGGGGA

HNO3

CO2H

HHO

OHH

CO2H

b.

NO2

GGGGGGGGGGGGGGGGGGGGGA

1. SnCl2, HCl

2. HNO2, H2SO43. Nal

⌈

⌊

N N+

HSO−4

⌉

⌋

GGGA

I

c.CN GGGGGGGGGGGGGGGGGGGGGA

1.

MgBr

2. H3O+

O


d. O

OH GGGGGGGGGGGGGGGA

1. Br2, PBr3

2. H2O

Br

O

OH

e.N

+

O

GGGGGGGGGGA

1. THF

2. H+

O O

f.

O

OH


1. SOCl2

2. H N

O

N

g.

O

O

GGGGGGGGGGGGGGGGGGGGGGGGGA

1. NaOCH3, CH3OH

2. H3O+

O

OH

GGGGGGGGGGGA

O


h.O

GGGGGGGGGGGGA

NH2NH2

KOH

i.

.

..

H

OHH

GGGGGGGGGGGGGGGGA

CrO3

H3O+

O

.

.

H

H

j.

OH

O

OH


1.

O

Clpyridine

2. CH3OH, HCl

O

O

O

O


k.

O


NaOCH3, CH3OH .

OH

OCH3

l.SH

GGGGGGGGGGGGGGA

l2

H2OS S

m.O + (C6H5)3P

+

C−

H CH3

GGGGGGGGGGA OO

CHCH3

n.

OH

OH GGGGGGGGGGGGA

PCC

CH2Cl2

O

O

H


10. In your own words, define five (5) of the terms given below.

Note: Only the first five questions answered will be marked—so onlygive 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 isdissolved in water; it is caused by reversible opening and closing ofthe hemiacetal, which gives a mixture of anomers

c. chemical shift

the position in a 1H NMR spectrum where a nucleus absorbs

d. parent peak

the peak in the mass spectrum corresponding to the molecularion, M+

e. enol

a vinyl alcohol, OH

f. anomers

cyclic stereoisomers of sugars that differ only in their configurationat the hemiacetal (anomeric) carbon

g. Hell Volhard-Zelinskii reaction

formation of an α-bromo carboxylic acid

RCH2CO2H GGGGGGGGGGA

1. Br2

PBr3

2. H2O

RC

Br

HCO2H

h. mixed aldol

aldol reaction between one or more aldehydes and one or moreketones, one of which has no αH and thus cannot form anenolate ion

i. α,β-unsaturated ester

βα

O

OR


11. Propose the step-wise mechanism for each of the transformationsbelow. Use arrows to show electron flow where appropriate.

a.

N N+

HSO−4

+

NH2

• •

GGGGGGGGA

N N

NH2

DGGGGGGGGGGGGGGGGGGG

N N NH2+ H2SO4

+

H HSO−4

b.

OH−

H

O

H

x

GGGGGGGGGGGGGGAD GGGGGGGGGGGGGG

ethanol

NaOHOH O

H

O

H

HO

H

O−

H

EGGGGGGGG

GGGGGGGGC

+

GGGGGGGGGGBF GGGGGGGGGG

H2O

H

OH

O

H

+ OH−


12. Propose and show the synthetic pathway for two of thetransformations below.

Note: Only the first two questions answered will be marked—so onlygive answers for those items you want marked.

a. Either

CN

GGGGGGGGA

NH2

O

OH

1.

Na

OH

DGGGGGGGGGGGGGG

2.

H3O

+

GGGGGGGGGGGGGGA

SOCl2

O

Cl

1.

Na

N3

GGGGGGGGGGGGGGGGA

2.

H2O

/∆

or

CN

GGGGGGGGA

NH2

O

OH

1.

Na

OH

DGGGGGGGGGGGGGG

2.

H3O

+

GGGGGGGGGGGGGGA

SOCl2

O

Cl

1.

NH

3GGGGGGGGGGGGGGGGGGGA

2.

Br 2

/N

aO

H

H2O


b. O

GGGGGGGGGGGGGGGGA

HO

O

O2N

O

1.

HN

O3,

H2S

O4

DGGGGGGGGGGGGGGGGGGGGGGG

GGGGGGGGGGGGGGGGGGGGA

1. SnCl2/HCl

2. HNO2/H2SO4

N N

O+

Cu

2O

/C

u(N

O3) 2

/H

2O

GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGA

HSO4−

c.O O

OGGGGGGGGA

O

product

O

CO OEt

1.

Na

OE

t/E

tOH

DGGGGGGGGGGGGGGGGGGGGGGG

2.

Br

GGGGGGGGGGGA

1. H3O+

2. heatproduct + CO2 + EtOH


13. a. Compound A, C10H18O undergoes reaction with dilute H2SO4 at25◦C to yield two alkenes, C10H16, B and C. The major alkeneproduct B gives only cyclopentanone after ozone treatmentfollowed by reduction with zinc in acetic acid.

Identify A, B and C.

degree ofunsaturation = 2

C10H18OA GGGGGGGGGGGGA

dil H2SO4B

C10H16

degree ofunsaturation = 3

+ CC10H16

O3

DGGGGGGGGG

2n

/H

oA

c

O

∴ B is

A must be

OH

and C should be


b. Compound A is a D-aldopentose C5H10O5 that can be oxidized toan optically inactive aldaric acid B on treatment with HNO3.

On Kiliani-Fischer chain extension, Compound A is converted tocompounds C and D: Compound C can be oxidized to an opticallyactive aldaric acid E, where as Compound D is oxidized to anoptically inactive aldaric acid F.

What are the structures of A to F?

A

OH

OH

OH

CH2OH

CHO

GGGGGGA

Kiliani

FischerC

OH

OH

OH

OH

CH2OH

CHO

+ D

HO

OH

OH

OH

CH2OH

CHO

HN

O3

DGGGGGGGGGGG

HN

O3

DGGGGGGGGGGG

HN

O3

DGGGGGGGGGGG

B

OH

OH

OH

CO2H

CO2H

E

HO

OH

OH

OH

CO2H

CO2H

opticallyactive

F

OH

OH

OH

OH

CO2H

CO2H

opticallyinactive

Therefore,

D is

OH

OH

OH

OH

CH2OH

CHO

F is

OH

OH

OH

OH

CO2H

CO2H


C is

HO

OH

OH

OH

CH2OH

CHO

E is

HO

OH

OH

OH

CO2H

CO2H

A is

OH

OH

OH

CH2OH

CHO

B is

OH

OH

OH

CO2H

CO2H


Note: The remainder of this examination is based on the three optional unitsin this course. You have studied one of the possible three units. Pleasecomplete only one (1) of the following questions

Unit 26 Biomolecules: Amino Acids, Peptides and Protein

15. Threonine, (2S, 3R)-2-amino-3-hydroxybutanoic acid, has two chiralitycentres.

a. Draw the Fischer projection of threonine

SH2N

OHR

CH3

CO2H

b. Draw the predominant form of threonine in a pH 4.0 buffer solution.The isoelectric point of threonine is 5.6.

HO H

H2N H

O

O−

.

.

c. Use the amidomalonate synthesis to prepare the amino acidphenylalanine beginning with diethyl acetamido malonate.

O

CCH3HN

CH CO2Et

CO2Et

GGGGGGGGGGGGA

1. NaOEt

2. PhCH2BrPhCH2 C

CO2Et

HN

CO2Et

O

GGGGGGGA

H3O+

heatPhCH2 CH CO−2

+NH3


Unit 27 Biomolecules: Lipids

16. a. Draw the major products you would expect from the reaction ofcholesterol and the following reagents

HOcholesterol

i. GGGGGGGGGGGGGGA

CrO3

H+

O

ii. GGGGGGGGGGGGGGGGGGGA

O

O

O

pyridine

O

O

iii. GGGGGGGGGGGGGGA

Br2

CH2Cl2

HO

.

BrBr


b. Draw the molecules below in chair conformations, and indicatewhether the bridgehead methyl is axial or equatorial.

i.

.

H

H

axial CH3 group

ii.

H

H

axial CH3 group


Unit 28 Biomolecules: Nucleic Acids

17. a. Describe, using chemical structures, two major structural differencesbetween DNA and RNA.

O−

P−O

O

deoxyriboseDNA

OCH2O

HO

base

O

NH

ON

sugar

thymineunique base

−O P

O

O−

OCH2O

OH OH

base

riboseRNA

O

NH

ON

sugar

uracilunique base

b. Explain each of the following terms:

i. replication

process by which double-stranded DNA uncoils and is replicated toproduce two new copies

ii. messenger RNA

During transcription, a short segment of the DNA double helixrewinds and complementary RNA line up to produce mRNA, aform of RNA that carries genetic messages to ribosomes, the cellpart that manufactures proteins.

iii. coding strand

the strand of double-helical DNA that contains the gene

c. What RNA base sequence is complementary to the DNA base sequencebelow?

(5′) G A T T A C C G T A(3′) end

RNA (3′) C U A A U G G C A U(5′) end

— END OF EXAMINATION —


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Chemistry 360 - Athabasca University