1
CHE-310 Organic Chemistry I
Instructor:
Office:
Phone:
Office Hours:
e-mail:
1.
Dr. James L. Lyle
NSM-D-323
(310) 243-3388; 243-3376
Will be announced in class; open door policy
jlyle@csudh.edu
Grading:
Daily exams
4 exams @ 100 pts
final exam
homework
=
100
=
400
=
100
required
600
Letter grades will be assigned on the following basis. Grades are
not curved.
A = 100-93%, A- = 92-90%, B+ = 89-87%, B = 86-83%, B- = 82-80%,
C+ = 79-77%, C = 76-73%, C- = 72-70%, D+ = 69-67%, D = 66-60%,
F = 59-0%
2.
Required Texts:
Organic Chemistry, 6th Ed., Morrison & Boyd.
Study Guide for ...
Molecular Model Kit
3. Exams.
Daily exams will be given at the beginning of most lectures. No
make up exams will be given, but the two lowest will be dropped.
Attendance is expected. If you miss a daily exam it will count
toward one of the two dropped exams. For scheduled hourly exams,
no make up exams will be given. You must take the exams on the
dates and times as scheduled.
4. Final exam.
The final exam will be comprehensive.
5. Homework.
Daily homework will be assigned. It is due at the beginning of
the following lecture period. Penalty points will be assigned for
missing or late homework.
6.
Prerequisites.
The prerequisite for this course is completion of both semesters
of General Chemistry. A co-requisite is enrolment in CHE-311.
2
7. Office Hours.
The instructor is available at any time outside of class for
questions, etc. Do not hesitate to seek help if you need it.
8. Cheating. Don't do it! At best you will receive a failing
grade and be put on academic probation, at worst you will be
expelled from the university.
Review the University Catalog
statement on Academic Integrity!
9. Course goals, objectives and requirements are covered in the
rest of this syllabus.
3
CHE-310
Meeting
1.
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44.
TENTATIVE SCHEDULE
Date
8/25
8/27
8/29
9/1
9/3
9/5
9/8
9/10
9/12
9/15
9/17
9/19
9/22
9/24
9/26
9/29
10/1
10/3
10/6
10/8
10/10
10/13
10/15
10/17
10/20
10/22
10/24
10/27
10/29
11/31
11/3
11/5
11/7
11/10
11/12
11/14
11/17
11/19
11/21
11/24
11/26
11/27
12/1
12/3
12/5
TBA
Chapt.
1
1
1
no class
2
2
2
3
3
3
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4
4
4
5
5
5/7
6
6
6
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8
8
9
9
9
9
10
11
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13
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no class,
16
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Fall '03
Topic
Introduction/Basic Principles
Basic Principles
Basic Prinicples
Methane
Methane
Methane/Alkanes
Alkanes
Alkanes
Alkanes
EXAM I ***
Stereochemistry
Stereochemistry
Stereochemistry
Alkyl Halides
Alkyl Halides
Alkyl Halides
Alcohols
Alcohols/Ethers
Ethers
EXAM II ***
Alkenes, synthesis
Alkenes, synthesis
Alkenes, reactions
Alkenes, reactions
Alkenes, reactions
Alkenes, reactions
Stereochemistry
Dienes
Dienes
Alkynes
EXAM III ***
Alicyclics
Alicyclics
Epoxides
Aromatic Hydrocarbons/Benzene
Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution
Arenes
Arenes
Thanksgiving holiday
Arenes
EXAM IV ***
TBA
FINAL EXAM ***
1
CHEM-310
Information re Exam I
In studying for your first exam in this course, you should first
go over all of the homework assignments and make sure that you
understand them.
In fact, you should be able to do any of the
assigned homework problems on the exam.
This is more difficult
than doing the homework when you have access to your notes, etc.
One way to prepare would be to redo all of your homework as if it
were an exam.
Then, pay particular attention to those problems
that you cannot do or do not understand. If you have questions
about any of the assigned material you should seek help
immediately.
- be able to define important terms.
- from atomic numbers be able to give the numbers of protons and
electrons in a neutral atom.
- be able to give spectral notations for neutral atoms.
- be able to identify ionic and covalent bonding.
- be able to draw Lewis dot structures for simple molecules.
- state the types of hybrid orbitals used in simple molecules and
give their angles.
- know the relative strengths of some simple acids and bases.
- for acid base reactions, be able to predict if a reaction takes
place, or if the reaction is given, label the stronger and weaker
acids and bases.
- be able to predict which compounds are polar.
- predict the important products of the reactions of methane.
- be able to name alkanes.
- know the mechanism for free radical halogenation of alkanes.
You may be asked to propose a similar mechanism for a reaction you
have not done!
- be able to calculate enthalpy changes, given bond dissociation
energies.
- be able to graph P.E. changes and label all parts of the graph.
2
- be able to estimate Energies of activation and predict which
step in a mechanism is rate determining. Know the importance of
Eact to the rates of chemical reactions.
- be able to draw hypothetical structures for transition states.
- understand the Hammond Postulate
- draw Newman projections for conformations in alkanes.
- be able to write equations to show how you would synthesize
alkanes in the laboratory, given the starting materials.
- be able to predict the organic products of the reactions of
alkanes.
3
CHE 310
Information about Exam II
Your second exam will cover the chapters on stereochemistry,
alkyl halides, alcohols and ethers. To study for this exam you
should go over your homework assignments. It will also help to
write your own version of the exam and trade with another
student. Try to boil the subject down to the basic principles.
This exam will have a section on stereochemistry. You must be
able to correctly specify R/S for stereoisomers (you may bring a
model to the exam). You must know the definitions of the terms
from this chapter, and understand what is important for each of
the types of reactions of chiral molecules that you might
encounter.
For alkyl halides, alcohols and ethers, be able to name compounds
correctly (nomenclature). Where necessay, be able to specify
congiguration in the name.
Know the two new mechanisms that we have learned in these
chapters: SN2, SN1. Know which mechanisms go with which
reactions under which conditions. Be able to write out all steps
in the mechanisms for given reactions and label the RDS.
Be able to predict the organic products of the reactions of alkyl
halides, alcohols and ethers. This is where you will be tested
on the particulars of a reaction such as rearrangements,
stereochemistry, and orientation.
Know how to synthesize any alkyl halide or ether from a given
starting material. Some of the methods used in syntheses may
also be covered in the part of the exam on reactions or
mechanisms.
Pay particular attention to those homework problems that are of
the above types. If you have any questions about the material,
please do not hesistate to come see me.
J. Lyle
4
CHE 310
Homework # 1
1. Read Chapter 1 of your text.
2. Define the following terms: Organic chemistry, Pauli
exclusion principle, Atomic orbital.
3. For each of the following, state how many protons are there
in the nucleus? how many eletrons are there in shells about the
nucleus? Give the spectral notation (1s22s2...): Na, Cl, Ne, Cl, Na+, O, O2-, Br, Ar, Br-, I, C.
5.
On page 5 of your text: 1.1 (a,b,c,d), 1.2 (a,b,c,d)
CHE 310
1.
Homework # 2
Define the following terms: Ionic bond, Covalent bond.
2. What kind of hybridization is used by the central atom in
each of the following compounds and what are the approximate bond
angles?
CH4
BF3
BeCl2
NH4+
CH3+
(CH3)3B
BF43. Draw Lewis dot structures to show the bonding in the
following covalent compounds:
NH3
H2O
H3O+
NH4+
CO2
5
CHE-310
1.
Homework # 3
In your text do problems: 1.6 on page 26, 1.9 on page 35,
1.11 (a) page 36, 5 (a thru f).
2. In the following reactions, label the acids and bases
involved, and label each as stronger or weaker.
H3O+
+
HCO3-
NaCN
+
H2O
NaCl
+
HI
CH3MgBr
+
---->
H2CO3
<------->
H2O
HCN
HCl
--->
+
+
H2O
NaOH
+
CH4
NaI
+
Mg(OH)Br
3. Define the following terms:Lewis acid, Lewis base,LowryBronsted acid,Lowry-Bronsted base,isomers.
CHE 310
1.
Homework # 4
Read Chapter 2
2. Predict the important products of the following reactions; if
no reaction takes place, write N.R.:
A)
CH4
B)
6CH4
C)
CH4
+
H2O, 850o,Ni---->
D)
CH4
+
Br2,hv ----->
E)
CH4
+
Cl2
F)
CH4
+
(xs)Cl2,heat ---->
3.
+
(xs)O2,flame
+
---->
O2, 1500o ---->
---->
Name the following compunds, giving two names for each:
CH3I
CH2Br2
CHCl3
CBr4
4. Write all steps in the free radical substitution mechanism
for the chlorination of methane. Label the initiating,
propagating, and terminating steps. Label the rate determining
step (RDS).
6
CHE 310
Homework # 5
1. Calculate the enthalpy change (delta H) for the following
reaction.
heat
CH4 + Br2 ------> HBr + CH3Br
2. Outline all steps in the mechanism for the above reaction,
and calculate the delta H for each step in the mechanism.
3. Draw a graph of the potential energy changes in the second
step of the above mechanism. (the graph can be free hand, but
should have all parts labeled.)
4. Draw a graph of the P.E. changes in the third step of the
mechanism.
5. An alternate mechanism for chlorination of methane was
proposed by a student and contained the following two propagating
steps:
(2)
(3)
Cl. + CH4 ----> CH3Cl + H.
H. + Cl2 ----> HCl + Cl.
Calculate the delta H for each of the above steps.
Why does the chlorination of methane proceed by the mechanism in
the text and not by this alternative route?
7
CHE 310
Homework # 6
The compound HOCl (hypochlorous acid) reacts with the compound
C6H5CH3 (toluene) under the influence of ultraviolet light as
shown in the following equation:
hv
C6H5CH3 + HOCl ------> C6H5CH2Cl + HOH
The bond dissociation energies pertinent to the above system are:
C6H5CH2-H
1.
85;
HO-Cl
60;
C6H5CH2-Cl
68;
H-OH
119 Kcal/mole
Calculate the enthalpy change for the reaction.
2. Write a stepwise mechanism for the above reaction and label
the initiating and propagating steps. (Take the bond
dissociation energy values into account when considering the most
likely mechanistic steps.) Write two possible terminating steps.
3. Calculate the enthalpy changes for the steps in your
mechanism, where possible.
4. Draw a graph of the potential energy changes for the third
step in your mechanism. Label all parts of the graph.
5. Estimate the Energies of Activation for each of the
propagating steps in the mechanism.
6. Which of the steps is the RDS (rate determining step)?
do you know?
How
7. Draw a hypothetical structure for the transition state for
step 2 of the mechanism.
8
CHE-310
1.
Homework # 7
Read Chapter 3.
2. Draw the Newman Projections for the following conformations
about the C2-C3 bond in n-butane: anti, gauche, CH3-H eclipsed,
and CH3-CH3 eclipsed. Which of these are stable conformations?
3.
Name the following structures:
CH
3
CH3CH2CH2CH2
CH3CH2CH2CH2CH3
CH3 CH3
CH3CHCH2CHCH2CH3
CH3
CH3CH2CCH3
CH3
CH3
CH2
CH3
CH CHCH CH CHCH
3
2 2
3
CH3
CH2
CH3
CH3
CH CH CHCH CHCHCH CH
3 2
2
2 2
CH2
CH2
CH3
4.
Draw all nine isomeric heptanes (C7H16) and name each one.
CHE-310
Homework # 8
page 99
3.9, 3.10,3.11
page 121
8, 9 (a,b,c)
9
CHE-310
Homework # 9
1. In your text: p. 103:3.12;3.14 (predict the products and
circle the major product. Do not predict the proportions.)
p. 121;10 (and circle the major product.)
2. Outline all steps in the mechanism for the bromination of
ethane. Label the RDS.
CHE 310
1.
Homework # 10
Read Chapter 4.
2. Define the following terms: stereochemistry, optical
acitivity, dextrorotatory, levorotatory, specific rotation,
chirality, chiral center, enantiomers, racemic
modification,configurations.
3.
4.3; 4.4; 4.5 (a-d); 4.8; 4.10 (a).
CHE-310
Homework # 11(a)
1. Define the following: diasteromers, meso compound,
resolution
2.
In your text: 4.12 (a,b,h); 4.13.
CHE-310
1.
Homework # 11(b)
In your text: 4.24.
2. For each of the following reaction types, write a sentence or
two to indicate the sterochemical importance of that type of
reaction, or the basic principle to keep in mind about that type
of reaction.
a) a reaction of achiral compounds in which a
chiral center is generated.
b) a reaction of a chiral compound in which no bonds to the
chiral center are broken.
c) a reaction as in c) where a new chiral center is formed.
d) a reaction of a chiral molecule with an optically active
reagent.
e) a reaction of a chiral molecule in which a bond to the
chiral center is broken.
10
CHE-310
Homework # 12
1.
Read Chapter 5.
2.
In your text:
3.
Outline all steps in a possible laboratory synthesis of:
p. 211: 2; 3; 4;
a) n-propyl bromide from n-propyl alcohol,
TWO WAYS.
b) isopropyl iodide from isopropyl alcohol, THREE WAYS.
CHE 310
Homework # 13
In your text:
5.2; p. 212: 5; 6(a).
Predict the product(s) of the following reaction.
the stereochemistry of the product(s).
CH3
¦
H ---+--- Br
¦
CH2CH3
+
NaOH
You must show
SN2
----->
Using "curved arrow formalism", outline all steps in the
mechanism for the following reaction and label the RDS.
CH3Br
+
NaOH
----->
CH3OH
+
NaBr
Draw a hypothetical structure for the transition state of the RDS
in the above mechanism. What is the name of this mechanism?
11
CHE 310
Homework # 14
Predict the product(s) of the following reaction.
stereochemistry of the product(s):
CH3
¦
H ---+--- Br
¦
CH2CH3
+
NaOH
Show the
SN1
----->
Using "curved arrow formalism", outline all steps in the
mechanism for the following reaction and label the RDS.
CH3
CH3C-Br
CH3
+ dilute NaOH
----->
CH3
CH3C-OH
CH3
+
NaBr + alkene
Draw a hypothetical structure for the transition state of the RDS
in the above mechanism. What is the name of this mechanism?
In your text:
p. 212
CHE 310
8 (a-h); p. 271
Homework # 15
page 245:1;6;
Complete the following reactions:
CH3
CH3CHCHCH3
+ HBr ----->
OH
CH3CH2CH2CH2OH + HI ----->
p. 247
read "About Syntheses"
17 (a,b,d,e,h).
4 (i,j);
12
CHE-310
Homework # 16
Outline all steps in the mechanism(s) for the reactions: Don;t
forget to use "curved arrows" to show the movement of electron
pairs. Label the RDS. Name each mechanism!
CH3CH2-OH
+
tert-butyl alcohol
HCl
+
H+
----->
HBr
CH3CH2-Cl
H+
----->
+
H2O
tert-butyl bromide
+
H2O
Give the structures of the organic products expected for the
following reactions:
1.
n-butyl alcohol with
a) sodium bromide, sulfuric acid
b) ethyl magnesium bromide (CH3CH2MgBr)
c) sodium bicarbonate (NaHCO3)
d)
f)
K2Cr2O7
C H NHCrO Cl
5 5
3
CH3SO2Cl,OH-
g)
acetic acid (CH3COOH),H+
e)
2.
sec-butyl alcohol with
a) P,I2
b)
c)
d)
e)
NaOH
Na
NaOCl (bleach)
CrO3
C6H5COOH,H+
tert-butyl alcohol with
a) HI
b) NaNH2
f)
3.
c)
d)
e)
K
product of c) + ethyl iodide
KMnO4
f)
Br2
13
CHE-310
Homework # 17
page 245: 2;3;7. Outline Williamson Syntheses for each of
the ethers in problem 3.
CHE-310
Homework # 18
In your text: 8.1 (a) and name each compound (use E/Z for
geometric isomers); 8.2; 8.5 and circle the major product if more
than one is formed; 8.6 ( note: you want the alkyl halide that
will give only one organic product from the dehydrohalogenation,
not a mixture!);
p. 316:6 (a,b,c,e); 7 (a,b,c,e).
Outline all steps in the mechanism for the following reaction.
Label the RDS.
CH3CH2Br + KOH(alc) -----> CH2=CH2 + H2O + KBr
CHE 310
Homework # 19
1. Predict the products of the following reactions. If more
than one organic product is produced, circle the major product.
a)
n-butyl bromide
+
KOH(alc) ---->
b)
n-butyl alcohol
+
H+
c)
neopentyl alcohol
d)
2,3-dibromopentane
+
+
---->
H+
Zn
---->
---->
2. Outline all steps in the mechanism for the following
reaction. Label the RDS.
isopropyl alcohol + H+ ----> propylene
3. Why is dehydrohalogenation of an alkyl halide often preferred
over dehydration of an alcohol in the synthesis of many alkenes?
4.
p. 316:
13.
14
CHE-310
Homework # 20
In your text: Page 363: 1 (a-j);
20 (a,b); 21 (a).
3 (a thru e);
Page 366:
Outline all steps in the mechanism for the following reaction:
Label the RDS. Name the mechanism.
CH2=CH2
CHE-310
In your text:
21 (b, c, d).
CHE-310
In your text:
+
HBr
----->
CH3CH2Br
Homework # 21
page 363: 1 (k thru n);
page 366: 20 (c, d, e);
Homework # 22
Page 363:1 (s,t);Page 363: 4.
Outline all steps in the mechanism of the following reaction:
Label the RDS. Name of the mechanism?
H+
CH2=CH2 + H2O -----> CH3CH2-OH
Outline all steps in the mechanism for the following reaction:
Label the RDS. Name of the mechanism?
perox.
CH2=CH2 + HBr ----->
CH3CH2Br
CHE-310
In your text:
(f);21 (e,f).
Homework # 23
page 363: 1 (o thru r);16;17 (a);page 366:20
15
CHE-310
Homework # 24
Define the following terms:stereospecific reaction,
stereoselective reaction.
In your text:
10.1;10.4.
CHE 310
1.
Homework # 25
Name the following compounds:
CH2=CH-CH=CH-CH=CH-CH3
CH3
CH2=CH-C=CH2
2.
CH3-CH=CH-CH2-CH=CH2
CH3-CH2
\
H
/
C = C
CH3
/
\
/
H
C = C
/
\
H
H
predict the product(s) of the following reactions:
CH3-CH=CH2
+
Br2
CH2=CH-CH3
+
Br2
----->
heat
----->
16
Homework # 26
1.. Give the structures of the organic products expected from
the reaction (if any) of 1,3-butadiene with:
a) H2, Ni
b) 2 moles H2, Ni
c) Br2
d) 2 moles Br2
e) HCl
f) HBr, peroxides
g) KMnO4
h) Br2, H2O
2. Give the structures of the organic products expected from the
reaction (if any) of 1,4-pentadiene with each of the reagents
shown above in problem 1.
3.
In your text:
page 422
CHE 310
In your text:
Homework # 27
p. 441: 1;2;4.
CHE 310
In your text:
5 (b,f).
Homework # 28
p. 488-489:1 (a,f,h);2 (a thru h); 3 (b,h,j,k).
CHE 310
Homework # 29
In your text: 13.1;p. 488-489:1 (b,c,d,e);2 (i thru cc);3 (a,c
thru f, i, j, k).
CHE 310
13.27; 13.25; p. 491: 16.
Homework # 29-2
17
CHE 310
Homework # 30
In your text: page 515-516:
theoretical; 9.
CHE 310
In your text:
CHE 310
In your text:
p. 548:
4 (a thru f)
note the word
Homework # 31
p. 515:
2 (d,e);
Homework # 32
p. 546: 2 (all);
15 (a - g);
p. 546:
1 (all).
(two days?)
3 (all);
5.
Outline all steps in the mechanisms of the following reactions.
Label the RDS.
a) nitration
b) sulfonation
c) halogenation
d) Friedel-Crafts alkylation
CHE 310
Homework # 33
In your text:
p. 581: 1 (all);
CHE 310
In your text:
p. 581:
Homework # 34
p. 581: 3 (all);p. 584: 18 (a,b,d,e);
4 (all).
CHE 310
2 (a-h);
16.2
Homework # 35
In your text:
p. 581:
problem 4 using phenylacetylene instead of
trans-phenylpropene:(a,b,c,e,f,k,m,H2SO4 + Hg++ + H2O); 5 (all);
18 (c,g).
18