Chem 3 BPractice Exams 2011

1
EXAMINATION 1 Chemistry 3B
Name:__________________________ Print first name before second! Use capital letters!
SID #:______________________
Peter Vollhardt February 23, 2006 Please provide the following information if applicable. Making up an I Grade _____ (If you are, please indicate the semester during which you took previous Chem 3B: Semester Instructor Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 17 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Good Luck!
DO NOT WRITE IN THIS SPACE I. II. III. IV. V. VI. VII. Total: ______ ______ ______ ______ ______ ______ ______ (30) (30) (50) (50) (40) (30) (20) (250)
I.
[30 Points] Name or draw, as appropriate, the following molecules according to the IUPAC rules. Indicate stereochemistry where necessary (cis, trans, R, or S).
a.
CHO
I Br
b.
c. R-4-Methyl-2-cyclohexenone
d. Meta-(1-methylethyl)(methoxymethyl)benzene
e.
II. [30 Points] 1-Methylthio-4-nitrobenzene A undergoes preferential electrophilic attack by E+ to give only one of the two products shown.
SCH3
1 2 3 4 E
+
SCH3 E
-H+ or
SCH3
E NO2 NO2
NO2
A
a. b.
Which one? Mark the box below your choice with an X. Write the resonance forms of the intermediate formed on attack of E+ at:
C-2:
Four resonance forms
C-3:
Three resonance forms c. Circle (in your answers above):
a. the most strongly contributing resonance form of the attack at C-2 and b. the least contributing resonance form of the attack at C-3. III. [50 Points] Add the missing components (starting materials, reagents, or products) of the following reactions in the boxes provided. Aqueous work-up (when required) is assumed to be part of a step. It is not part of any answer.
a.
+ HCl
Thermodynamic product
OCH3
b.
H 3C
H 3C CH3
A cyclobutene
c.
CN + CN
d.
H
h
A hexatriene isomer of product. e.
CH3 CH3
K
+-
OC(CH3)3
13
C NMR: 7 lines
A salt; 13C NMR: 4 lines
f.
Cl SO3,H2SO4 OCH3 NO2
g.
OH + OH
O CH3CCH3
H+ -H2O
13
C NMR: 4 lines
h.
O
1.
Cl, AlCl3
2.
Zn(Hg), HCl,
i. 1. P(C6H5)3 2. CH3Li
O
3.
I
j. H2NNH2, , and
IR Spectrum of product :
A hydrocarbon
4000
3000
2000
1500
1000
500 cm-1
IV. [50 Points] Treatment of acetal A with conc. nitric acid and H2SO4 led to unknown B. The IR and NMR spectra of this product are shown below.
O HO
O H
1. HNO3, H2SO4 2. H2O, H+, B (unknown)
HO3S
a. After consideration of the spectral data, write the structure of the product in the box below.
Structure of unknown
b. Interpret the spectral data as requested in the spaces provided. 1. IR Spectrum
Confirm or rule out the presence or absence (circle one) of the following bonds. Enter an approximate expected stretching frequency in the box.
~
(Csp2H) is:
present
absent
at
cm-1
(OH) is:
present
absent
at
cm-1
(C=O) is:
present
absent
at
cm-1
2.
13
C NMR Spectrum (these are all single lines; ignore the seeming splitting of some).
A D
ppm
The proton-coupled spectrum leaves the singlets for B, C, and D unchanged.
10
Draw your suggestion for the unknown in the box below and label the types of carbon atoms A, B, C, and D, giving rise to the corresponding signals in the spectrum. For the assignment of B, C, and D, consider that the order of chemical shifts parallels roughly the order of electronegativity of the attached atom.
3. 1H NMR Spectrum (for expanded sections, see next two pages).
D E
ppm
11 The signal due to protons A disappears in D2O solvent.
ppm
12
ppm
ppm
Draw your suggestion for the unknown in the box and label the hydrogens A, B, C, D, and E giving rise to the corresponding signals in the spectrum.
13
V. [40 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have! Work from left to right in the following spaces. There is much more space than you will need. a.
NH2 N O H+ + H H
14
b.
O O H+ O CH3COCH3 + CH3COOH CH3CCH3 + CH3COOH
Work from left to right in the following spaces. There is much more space than you will need.
15
VI. [30 Points] Provide a reasonable synthetic route from starting material to product. Note: Several steps are required, and there may be more than one solution to the problem. Do not write mechanisms! a. Here, you may use any additional organic or organometallic reagents to effect your conversions.
OH
16
b.
Synthesize compound A using only the materials shown and no additional reagents.
O
N
,
O
H2NNH2
17
VII. [20 Points] Place an X mark in the box next to the most accurate statement. a. The equilibrium constant for hydration of 1, 2, and 3 increases in the order
O F 3C H H3C O CH3 CH3 O C H
1, 2, 3
3, 2, 1
2, 3, 1
3, 1, 2 b. Circle the compounds which are aromatic
The End
SID #:______________________
Peter Vollhardt September 28, 2006 Please provide the following information if applicable. Making up an I Grade _____ (If you are, please indicate the semester during which you took previous Chem 3B: Semester Instructor Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 20 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Good Luck!
I.
a.
Br
Cl
b.
F O
c. S-4-Methyl-2-cyclohexenone
d. 4-Methyl-3-nitrobenzenecarbaldehyde
e.
II. [30 Points] Compound A undergoes preferential electrophilic attack by E+ to give only one of the two products shown.
CH3 O2N 1 2 3 4 5 E A NO2 E+ -H+ O2N CH3 NO2 O2N or E CH3 NO2
a. b.
Which one? Mark the box below your choice with an X. Write the resonance forms of the intermediate formed on attack of E+ at:
C-4:
Three resonance forms
C-5:
Three resonance forms c. Circle (in your answers above):
a. the most strongly contributing resonance form of the attack at C-4 and b. the most strongly contributing resonance form of the attack at C-5. III. [50 Points] Add the missing components (starting materials, reagents, or products) of the following reactions in the boxes provided. Aqueous work-up (when required) is assumed to be part of a step. It is not part of any answer.
a.
O S O O
CH3OH Solvolysis
Thermodynamic product b.
C(CH3)3
h
C(CH3)3
c.
O
d.
CH3
CH3
An octatetraene isomer of product.
e.
+ NBr ROOR + NH
f.
H N CH3
SO3, H2SO4
g.
O OH H+, CH3OH
IR spectrum of product :
h.
CH3O Br2, FeBr3 CH3 Monobromination
i.
1.
2.
SO3H
3.
NH2
j.
1. O 2. HS
SH
Mass spectrum of product :
IV. [60 Points] Heating compound A with acetylene gas under pressure generated the unknown B. The complete spectral data for this product are shown below in the sequence : 1. 1H NMR , 2. 13C NMR , 3. Mass , 4. IR , 5. UV.
OCH3
+ H C C H
B (unknown)
Cl
OCH3
A a. After consideration of the spectral data, write the structure of the product in the box below.
10
1. 1H NMR Spectrum (for expanded section, see bottom spectrum).
A B
ppm
9 Hz
ppm
11
b. Draw again your suggestion for the unknown in the box and label the hydrogens A, B, and C giving rise to the corresponding signals in the spectrum. Consider resonance in your assignments of A and B.
2.
13
C NMR Spectrum (these are five single lines).
C D
ppm
12
The proton-coupled 13C NMR spectrum leaves the singlets for A and B unchanged, but shows that each of the carbons giving rise to signals C and D are attached to one hydrogen, while the carbon due to E bears three hydrogens. Draw again your suggestion for the unknown in the box below and label the types of carbon atoms AE giving rise to the corresponding signals in the spectrum. For the assignments of A versus B and C versus D, consider the effect of electronegativity of the attached atom and the effect of resonance, respectively.
13
3. Mass spectrum
a. Clearly mark on the spectrum the molecular ion as M+. b. In the box above the fragment ion m/z = 199, indicate the molecular piece that has fragmented from M+, e.g. Cl, or CH3O, or CH3CH2, or ?
14
4. IR Spectrum
~
(Csp2H) is:
present
absent
at
cm1
(CspH) is:
present
absent
at
cm1
(CC) is:
present
absent
at
cm1
15
5. UV spectrum
nm
Place an X mark into the box next to the most accurate statement. The spectrum depicts a nonconjugated compound.
The spectrum is that of a colored compound.
The unknown is aromatic.
The max is at 300 nm.
16 V. [30 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have! Work from left to right in the following spaces. There is much more space than you will need.
a.
O Catalytic H+
17
b.
O Cl3CCH + H2 O H+ Cl3C
OH C H OH
18
VI. 30 Points] Provide a reasonable synthetic route from starting material to product. Note: Several steps are required, and there may be more than one solution to the problem. Do not write mechanisms! a.
H 3C OCH3 CH3 H3C OCH3 CH3
NH2
19
b. Synthesize compound A from any materials containing six carbons or less.

CH3 CH2OH
CH3
A Work from left to right in the following spaces. There is much more space than you will need.
20
VII. [20 Points] Place an X mark in the box next to the most accurate statement. a. The electron donating power of benzene substituents 14 increases in the order
N CH3 CH3
CH3 1
OCH3 2
NO2 4
1, 2, 3, 4
4, 3, 2, 1
4, 2, 3, 1
4, 1, 2, 3 b. Circle the compounds which are aromatic
The End
SID #:______________________
GSI (if you are taking Chem 3BL): ______________________ Peter Vollhardt October 2, 2008 Please provide the following information if applicable. Making up an I Grade _____ (If you are, please indicate the semester during which you took previous Chem 3B: Semester Instructor Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 20 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Good Luck!
I.
a.
Br
b.
c. (S)-3-Methylcyclohexanone
d. trans-4-Bromo-2-oxo-3-butenal
e.
II.
[30 Points] Compound A undergoes preferential electrophilic attack by E+ to give only one of the three products shown.
OCH3 OCH3 NO2 E+ -H+ NO2 or E CH3 E CH3 CH3 OCH3 NO2 or E OCH3 NO2
4 CH3 A
a. b.
Which one? Mark the box below your choice with an X. Write the resonance forms of the intermediate formed on attack of E+ on A at:
C-3:
C-5:
C-6:
Four resonance forms c. d. Circle (in your answers above) the most strongly contributing resonance forms of the attack at C-3, C-5, and C-6. Considering all of the above most strongly contributing resonance forms, which one is the best overall? Redraw it in the box below.
III.
[50 Points] Add the missing components (starting materials, reagents, or products) of the following reactions in the boxes provided. Show stereochemistry when appropriate. Aqueous work-up (when required) is assumed to be part of a step. It is not part of any answer.
a.
O S O O
CH3OH (solvent)
b.
CH3
CH3
c.
O
d.
CH3
CH3
Product of ring opening

O O
e.
+ NBr
NH
f.
H N CH3
SO3, H2SO4
g.
O H+, HOCH2CH2OH
IR spectrum of product:
h.
CH3O Br2, FeBr3 Cl Monobromination
i.
1.
2.
SO3H
3.
NH2
CH3
CH3
j.
1.
2. O
IV. [60 Points] An attempt to effect allylic bromination of A generated the unknown B. The complete spectral data for this product are shown below in the sequence: 1. 1H NMR, 2. 13C NMR, 3. Mass, 4. IR, 5. UV.
O H + NBr B (Unknown)
H3CO A O
10
A
1H
B
2H
C
2H
D
3H
ppm
11
b. Draw again your suggestion for the unknown in the box and label the hydrogens A, B, C and D giving rise to the corresponding signals in the 1H NMR spectrum on p. 10. Consider resonance in your assignments of B and C.
2.
13
C NMR Spectrum (these are six single lines).
B D
ppm
12
DEPT spectra (dont worry if you dont remember what that is) shows that the carbons giving rise to signals A, C, and E are attached to one hydrogen each. Signal F is due to a carbon with 3 attached hydrogens. Signals B and D are associated with carbons without any bound hydrogens. Draw again your suggestion for the unknown in the box below and label the types of carbon atoms AF giving rise to the corresponding signals in the 13C NMR spectrum on p. 11. For the assignments of B versus D and C versus E, consider the effect of electronegativity of the attached atom and the effect of resonance, respectively.
13
3.
Mass spectrum Atomic weights of all the elements in the reaction on p. 9: H 1; C 12; N 14; O 16, Br 79 and 81 (1:1 isotope ratio). Caution: Not all of these elements are incorporated in the product.
136
a. Clearly mark on the spectrum the molecular ion as M+ and the base peak as B+. b. In the box above the fragment ion m/z = 135, indicate the structure of this fragment.
14
4.
IR Spectrum
Confirm the presence or absence (circle one) of the following bonds. Enter an approximate expected stretching frequency in the box.
~
(Csp2H) is:
present
absent
at
cm1
(Csp3H) is:
present
absent
at
cm1
(C=O) is:
present
absent
at
cm1
15
5. UV spectrum
nm
Place an X mark into the box next to the most accurate statement.
The spectrum depicts a nonconjugated compound.
The spectrum is that of a colored compound.
The unknown is aromatic.
The max is at 300 nm.
16 V. [30 Points] Write detailed stepwise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have! Work from left to right in the following spaces. There is much more space than you will need.
a.
NH2
Catalytic H+
17
b.
O O O H
O O
18
VI. [30 Points] Provide a reasonable synthetic route from starting material to product. Note: Several steps are required, and there may be more than one solution to the problem. Do not write mechanisms! Write out each step separately, including reagents and products. a.
CH2OH
Caution: You cannot introduce the CH2OH group directly. Hint: To do so, think alcohol synthesis. Work from left to right in the following spaces. There is much more space than you will need.
19
b. Synthesize compound A from any acyclic materials containing six carbons or less. Hint: Think Diels-Alder reaction. Caution: Work backwards. What compound must precede A for a retro-Diels-Alder step?
H H CN CN
A Work from left to right in the following spaces. There is much more space than you will need.
20
VII. [20 Points] Place an X mark in the box next to the most accurate statement. a. The electron withdrawing power of benzene substituents 14 decreases and their electron donating power increases in the order CH3 1 OCH3 2 F 3 NO2 4
1, 2, 3, 4
4, 3, 1, 2
4, 2, 3, 1
4, 1, 2, 3 b. Circle the compounds which are aromatic
:
The End
SID #:______________________
GSI (if you are taking Chem 3BL): ______________________ Peter Vollhardt October 1, 2009 Please provide the following information if applicable. Making up an I Grade _____ (If you are, please indicate the semester during which you took previous Chem 3B: Semester Instructor
Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 15 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Good Luck!
I.
[30 Points] Name or draw, as appropriate, the following molecules according to the IUPAC rules. Indicate stereochemistry where necessary (cis, trans, E, Z, R, or S).
a.
b.
c. (R)-2-Methylcyclohexanone
d. (E)-3-(p-Methylphenyl)but-2-en-1-ol
e.
II.
[30 Points] product.
Compound A undergoes preferential electrophilic nitration to give only one
CF3 HNO3, H2SO4
CF3 or NO2 CH3 O2N CH3
CF3 or
O2N
CF3
4 CH3 A
CH3
a. b.
Which one? Mark the box below your choice with an X, preferably after you have completed questions b.d. Write all the resonance forms of the intermediate formed by attack of E+ (= NO2+) on A at:
2 3
CF3
C-3:
5 4
CH 3
Note: A first stencil is provided for format. Leave out the numbering in any additional structures.
C-5:
6 5
2 3
CF3
CH 3
Note: A first stencil is provided for format. Leave out the numbering in any additional structures.
6 5
2 3
CF3
CH 3
C-6:
Note: A first stencil is provided for format. Leave out the numbering in any additional structures. c. d. Circle (in your answers above) the most strongly contributing resonance forms of the attack at C-3, C-5, and C-6. Considering all of the above most strongly contributing resonance forms, which one is the best overall? Redraw it in the box below.
6 5
2 3
CF3
CH 3
III.
OH a.
OH
OH
b.
CH3OH, H+
c. CH3 CN O CH3 CH3 O
+
CN
Use the stencil above and add all the groups missing from the hashed and wedged bonds.
d.
CH3
CH3
Product of ring opening
e.
f.
OCH3 H3C SO3, H2SO4 O2N F
g.
h.
CH3O Br2, FeBr3 Cl Monobromination
i.
1.
2.
3.
j.
CH 3 H
CH 3 CH 3 H
CH 3
Two diastereomers. Add the missing pieces. IV. [40 Points]
a. In the reaction shown, which product is the result of 1,4-addition, and which is the thermodynamic product, respectively? Circle the appropriate answer.
H3 C
HCl
Cl H3C +
H3C
Cl A
Product of 1,4-addition: A B Thermodynamic product: A B
b. Rank compounds 15 in order of increasing acidity. Mark the box next to the best answer below.
1, 2, 3, 4, 5
1, 4, 2, 3, 5
3, 1, 5, 4, 2
5, 3, 1, 4, 2
4, 1, 2, 5, 3 c. Circle the compounds which are aromatic:
CH3
CH3
10
d. Rank compounds 15 in order of increasing reactivity as dienes in the Diels-Alder reaction:
1, 2, 3, 4, 5
1, 4, 2, 3, 5
3, 1, 5, 4, 2
5, 3, 1, 4, 2
3, 1, 2, 4, 5
11 V. [40 Points] Write detailed stepwise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have!
a.
12
b. Intramolecular Friedel-Crafts alkylation of A provided the expected B, but also 10% of C, suggesting the operation of a competing pathway to the normal mechanism. Propose such a pathway to C. Caution: Do not propose a pathway to B, it will not be graded! Hint: While unusual in this case, what is the normally preferred position of electrophilic attack in naphthalene?
13
14
b. Synthesize compound A from any acyclic materials and any other reagent. Hint: Think Diels-Alder reaction. Caution: Work backwards.
A (racemate) Work from left to right in the following spaces. There is much more space than you will need.
15
VII. [20 Points] Place an X mark in the box next to the most accurate statement. a. Kinetic versus thermodynamic control is present when a racemate is formed in a reaction the (4N+2) rule overrides the Lewis octet rule of two isomeric products the less stable one is formed the reaction requires heat to go to completion everything happens all at once b. The reactivity of the carbonyl group increases with increasing electrophilic character of the carbonyl carbon with electron donating substituents on formation of acetals on reduction on going from aldehydes to ketones
The End
SID #:______________________ Laboratory GSI (if applicable):
Peter Vollhardt April 6, 2006 Please provide the following information if applicable.
Making up an I Grade _____ (If you are, please indicate the semester during which you took previous Chem 3B:
Semester
Instructor
Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 18 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Good Luck! DO NOT WRITE IN THIS SPACE I. II. III. IV. V. VI. ______ ______ ______ ______ ______ ______ (20) (50) (60) (40) (60) (20)
Total:
(250)
I.
[20 Points] Write a detailed mechanism of the following aldol condensation using arrow pushing techniques.
H
H + O CH3 O
NaOH, H2O O
II.
[50 Points] Add the missing components (starting materials, reagents, or products) of the following reactions in the boxes provided. Aqueous work-up (when required) is assumed to be part of a step. It is not part of any answer.
O
a.
H2O, H+
IR:
~ = 3350 (broad), 1720 cm1
b.
1. SOCl2 2. CH3OH OCH3
Mass spectrum of starting material:
c.
O O
Cl
d.
O NaOH, Br2 NH2
e.
1.
O 2. H
OH
COOH
f.
NH3, NaBH3CN
NH2
13
C NMR : = 208.9, 45.7, 29.8, 17.4, 13.7 ppm
g.
H N CH3
NO N CH3
h.
H3 C CH3 H3 C H H CH3
i.
+ O N H H+, THF
IR: No peaks >3010 cm1
j.
+ 2 CH3MgBr
III.
[60 Points] Subjecting acid A to the three step sequence shown below led to unknown B. The mass, IR, and NMR spectra of this product are shown on the following pages.
OH
1. PBr3 2. Br2 3. NH3 (excess) B (unknown)
b. Interpret the spectral data as requested in the spaces provided, starting on the following page.
1.
Mass Spectrum
Label the molecular ion as M+ and the base peak as BP. Using the partial periodic table on the previous page for atomic weights, draw the structures of the fragment ions at m/z = 148, 120, 91, and 77, respectively, in the boxes below. Draw a + charge at the point of the dangling valence in your line structure.
m/z = 148
m/z = 120
m/z = 91
m/z = 77
2.
IR Spectrum
~
(Csp3H) is:
present
absent
at
cm1
(Csp2H) is:
present
absent
at
cm1
(NH) is:
present
absent
at
cm1
(C=O) is:
present
absent
at
cm1
3.
13
C NMR Spectrum (these are all single lines; ignore the seeming splitting of some).
B C A D
ppm
Draw your suggestion for the unknown in the box below and label the types of carbon atoms A, B, C, and D, giving rise to the corresponding signals in the spectrum. Note that B is a group of four signals, which belong to a group of similar carbon atoms all of which should be labeled B.
10
1
4.
H NMR Spectrum (for expanded sections, see below and the next page).
A,B
D EF
ppm
A C
ppm
11
As indicated on the spectra, the signals due to protons A, C, and G disappear in D2O solvent (exchanges).
ppm
Draw your suggestion for the unknown in the box and label the hydrogens AG giving rise to the corresponding signals in the spectrum. Note: A and C can be assigned arbitrarily. B corresponds to a group of five hydrogens that can be assigned as such. E and F are due to hydrogens attached to the same carbon and can also be assigned arbitrarily.
12
IV. [40 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have! Work from left to right in the following spaces. There is much more space than you will need. a.
N C O H2, PdC, H N O O O
OH O
Note: Disregard the mechanism of catalytic hydrogenation.
13
b.
O Cl
Cl2
HCl
14
V. [60 Points] Provide a reasonable synthetic route from starting materials to product. Note: Several steps are required, and there may be more than one solution to the problem. You may use any additional organic or organometallic reagents to effect your conversions. Do not write mechanisms! a.
O
H2 N
OCH3
O O
15
b.
Na+-CN In 3 steps or less
16
c.
O P(C6H5)3 Br O
17
VI. [20 Points] a. Name the following molecule according to the IUPAC rules.
CH3 N H O O
b. The mass spectrum of 2-propylcyclohexanone is shown below. What is the origin of the large fragmentation peak at m/z = 98? Show your answer in the form of a scheme using epushing.
18
The End
Peter Vollhardt November 2, 2006 Please provide the following information if applicable.
______________________
Making up an I Grade _____ (If you are, please indicate the semester during which you took previous Chem 3B: Semester Instructor Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 21 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Good Luck!
DO NOT WRITE IN THIS SPACE I. II. III. IV. V. VI. ______ ______ ______ ______ ______ ______ (25) (50) (50) (45) (45) (35)
Total:
(250)
Chemistry 3B, Examination 2
Page
I.
[25 Points] Write the products of the following reactions of the starting material, methyl 3methylbutanoate.
CH3CH2OH, H+
CH3NH2,
1. CH3MgBr (2 equiv.) 2. H+, H2O work-up

OCH3
1. LiAlH4 2. H+, H2O work-up
1.
2
AlH
2. H+, H2O work-up
Page
II.
[50 Points] Add the missing components (starting materials, reagents, or products) of the following reactions in the boxes provided. Aqueous work-up (when required) is assumed to follow each step. It is not part of any answer.
a.
O
, H+ N H
Mass spectrum of product::
Page
b. 1. HCN 2. H+, H2O

HO COOH
13
C Spectrum of starting material:
c.
O
Page
d.
O CH3COOH
O
e.
O CH3 O
NaOH, H2O,
C11H10O
f.
COOH
Br COOH
Page
g.
O O CH3 O
H+, CH3OH
C6H12O2 IR spectrum of product :
h.
CN CH2NH2
Page
i.
Cl2, NaOH
NH2
IR spectrum of starting material :
j.
CH3
O
Page
III. [50 Points] Treatment of 2-bromopropanoic acid A with base gave, after work-up with aqueous HBr, mainly 2-propenoic acid, but, in addition, a small amount of a side product B. The spectral data for this product are shown below in the sequence : 1. 1H NMR , 2.
13
C NMR , 3. Mass , 4. IR.
Br OH
1. NaOH 2. HBr, H2O
OH
+ B (unknown)
O
2-Propenoic acid
Page
Page
10
b. Draw again your suggestion for the unknown in the box and label the hydrogens A, B, and C giving rise to the corresponding signals in the spectrum. Use the Table below, if necessary.
Page
11
2.
13
C NMR Spectrum.
Draw again your suggestion for the unknown in the box below and label the types of carbon atoms AC giving rise to the corresponding signals in the spectrum. Hint: The carbon giving rise to the signal labeled B above is attached to the hydrogens giving rise to signal B in the 1H NMR spectrum. Similarly, the carbon giving rise to the signal labeled C above is attached to the hydrogens giving rise to signal C in the 1H NMR spectrum.
Page
12
3. Mass spectrum. Hint: Atomic weights: C = 12; H = 1; O = 16; Br exists in nature as a 1:1 mixture of Br = 79 and Br = 81.
a. Clearly mark on the spectrum the molecular ion(s) as M+.
b. In the boxes above the respective fragment ions, indicate the molecular piece that has fragmented from M+, e.g. Cl, or CH3O, or CH3CH2, or ?
Page
13
4. IR Spectrum.
~
(Csp2H) is:
present
absent
at
cm1
(Csp3H) is:
present
absent
at
cm1
(OH) is:
present
absent
at
cm1
(C=O) is:
present
absent
at
cm1
Page
14
IV. [45 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have! a.
O Catalytic H
+
Work from left to right in the following spaces. There is more space than you will need.
Page
15
b.
O
H+
H2O
OH OH
Page
16
c.
O O
NaOH, H2O,
(Dont worry about stereochemistry). Work from left to right in the following spaces. Hint: Work backwards to unravel the product!
Page
17
V. [45 Points] Provide a reasonable synthetic route from starting material to product. Note: Several steps are required, and there may be more than one solution to the problem. Do not write mechanisms! O a.
N
+ any other material

H
Page
18
b. Synthesize (racemic) compound A from 2-butanone and any materials containing four carbons or less. O
O O
A Work from left to right in the following spaces. There is more space than you will need.
Page
19
c. One step in this sequence will not work. Circle the reaction arrow denoting this step. Note: Appropriate aqueous work-up (when required) follows each step and is not indicated.
OH H+ cat. COOCH3 O O H O
LiAlH4
OH MnO2
OH
O CrO3, H2O COOH H2, Pd
O COOH
O (CH3CH2)2CuLi
NaOH, H2O,
VI.
[35 Points] Place an X mark in the box next to the most accurate statement. a. The reactivity of 14 toward NH3 increases in the order
O CH3CCl
O CH3CNH2
O CH3COCH3
O O CH3COCCH3
1, 2, 3, 4
4, 3, 2, 1
2, 3, 4, 1
3, 2, 1, 4
Page
20
b. The acidity of 14 increases in the order

O
+
O CH3COCH3
O HCOH
NH4
CH3CCH3
1, 2, 3, 4
4, 3, 2, 1
2, 3, 4, 1
3, 2, 1, 4 c. A researcher finds two unlabeled bottles containing liquids in a cabinet. He knows that one of them is azacyclohexane A, the other is the ether analog B. A 13C NMR spectrum of the contents of bottle 1 shows = 25.5, 27.2, and 47.5 ppm, while that of bottle 2 shows = 23.6, 26.6, and 68.0 ppm. What is in bottle 1, A or B?
Bottle 1 contains
N H
Bottle 1 contains
O
Page
21
d. In problem c., give one (and only one) other spectral technique that would solve it and why or how. Place your respective answers into the boxes below.
Other spectral technique
How will this technique distinguish between A and B? (One sentence or expression only!)
"A little knowledge is a dangerous thing. But, then, so is a lot." A. Einstein
The End
Peter Vollhardt November 4, 2008 Please provide the following information if applicable.
______________________
DO NOT WRITE IN THIS SPACE I. II. III. IV. V. VI. ______ ______ ______ ______ ______ ______ (25) (50) (50) (45) (45) (35)
Total:
(250)
Page
I.
[25 Points] Write the organic products of the following reactions of the starting amide.
H2SO4, H2O
N:Li
(LDA)
:
1.
O
H Al
2. H+, H2O work-up

NH2
1. LiAlH4 2. H+, H2O work-up
Cl2, NaOH
Page
II.
a.
D2O, NaOD
Mass spectrum of product: m/z = 102
b.
O
1. HCN 2. H+, H2O,

H
13
C Spectrum of product:
Page
c.
O
d.
O CH3COOH
e.
O CH3 O
NaOH, H2O,
H3C
C6H8O
Page
f.
O
COOH
C Cl
g.
Cl
CH3
h.
MgBr
2 equiv.
OCH3
Page
i.
O
HCl, CH3CH2OH (solvent) +
Product after basic work-up Two additional neutral reagents
j.
H3C
H N H CH3
Two reagents
Page
III. [50 Points] In an attempt to hydrolyze lactone A with concentrated aqueous HBr, a student obtained compound B. The complete spectral data for this product are shown below in the sequence: 1. 1H NMR, 2.
13
C NMR, 3. Mass, 4. IR.
HBr, H2O
O
B (unknown)
Page
1. 1H NMR spectrum (for expanded section, see bottom spectrum).
B C D
ppm
B C D
ppm
Page
b. Draw again your suggestion for the unknown in the box and label the hydrogens A, B, C, and D giving rise to the corresponding signals in the spectrum. Use the Table below, if necessary.
Page
10
2.
13
C NMR spectrum.
ppm Draw again your suggestion for the unknown in the box below and label the types of carbon atoms A and B giving rise to the corresponding signals in the spectrum.
Page
11
a. Clearly mark on the spectrum the molecular ion(s) as M+.
b. In the boxes above the respective fragment ions, indicate the structure of the fragment.
Page
12
4. IR spectrum.
(Csp3H) is:
present
absent
at
cm1
(OH) is:
present
absent
at
cm1
(C=O) is:
present
absent
at
cm1
Page
13
IV. [45 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have! a.
O Catalytic HO
Page
14
b.
CH3CN
H+, H2O
O NH2
Page
15
c.
O H HO, H2O HO O H
Work from left to right in the following spaces.
Page
16
V. [45 Points] Provide a reasonable synthetic route from starting material to product. Note: Several steps are required, and there may be more than one solution to the problem. Do not write mechanisms! Write out each step separately, including reagents and products. You need to apply retrosynthesis!
O
a.
N
+ any other material
Page
17
b. O HO OH H CN Work from left to right in the following spaces. There is more space than you will need.
Page
18
c. Synthesize ketone A from starting materials containing one or two carbons only.
A
Page
19
VI.
[35 Points] Place an X mark in the box next to the most accurate statement. a. The reactivity of 14 toward H2O increases in the order
O CH3CCl
O CH3CNH2
O CH3COCH3
O O CH3COCCH3
1, 2, 3, 4
4, 3, 2, 1
2, 3, 4, 1
3, 2, 1, 4
b. The acidity of 14 increases in the order

O
CH3NH3+
O CH3COCH3
O HCOH
CH3CCH3
1, 2, 3, 4
4, 3, 2, 1
2, 3, 4, 1
3, 2, 1, 4
Page
20
c. Explain the following finding in one sentence. For the equilibria shown below, K1 = ~1, but K2 > 1
O
+
OH
CH3OH
H+
+
OCH3
H2O
K1
OH O H+
HO
O O
H2O
K2
Place your answer into the box below.
The End
SID #:______________________
GSI (if you are taking Chem 3BL): ______________________ Peter Vollhardt November 5, 2009 Please provide the following information if applicable. Making up an I Grade _____ If you are, please indicate the semester during which you took previous Chem 3B:
Semester
Instructor
Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 13 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Good Luck! DO NOT WRITE IN THIS SPACE I. II. III. IV. V. VI. (30) (30) (50) (60) (60) (20)
Total:
(250)
Page
I. a.
Cl
Br COOH
b.
c. (R)-trans-3-Penten-2-amine
d. 3-Methyl- N-bromo-N-ethylbutanamide
e.
Page
II.
[30 Points] bromide.
Write the organic products of the following reactions of the starting acyl
Br2, HBr
NH3
1.
Li+
H Al O O O
2. H+, H2O work-up
1. (CH3)2CuLi 2. H+, H2O work-up
CH3COOH
Page
III.
O
a.
(CH3)2NH, NaBH3CN
b. 1. LDA 2. CH3I 3. LiAlH4
c.
O
d.
Page
e.
1. 2.
One pot reaction
CH 3 O
f.
O
COOH
C Cl
g. 1. PCC 2. H+, H2O 3. NaOH, H2O,
C10H14O h.
MgBr
2 equiv.
C5H10O2
Page
i. 1. 2.
j.
Page
IV.
[60 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have!
a.
O
Na+-OCH
2CH 3,
O
CH 3CH2OH
OCH3
OCH2CH3
Page
b.
Page
c. The following atom-economical reaction occurs in a dry solvent (this means: no water!). Although it is new to you, you can apply the principles that you have learned to write a mechanism.
Page
10
V. [60 Points] Provide a reasonable synthetic route from starting material to product. Note: Several steps are required, and there may be more than one solution to the problem. Do not write mechanisms! Write out each step separately, including reagents and products. You need to apply retrosynthesis! a.
Page
11
b.
Page
12
c. Synthesize compound A from benzene.
Page
13
VI.
[20 Points]
Place an X mark in the box next to the most accurate statement.
a. The reactivity of 14 toward NH3 increases in the order

O CH3CCl
O CH3COCH3
1 1, 2, 3, 4 4, 3, 2, 1 2, 3, 4, 1 3, 2, 1, 4
b. The acidity of 14 (above) increases in the order 1, 2, 3, 4 4, 3, 2, 1 2, 3, 4, 1 3, 2, 1, 4 c. Circle the most likely product of the following reaction:
Br 2, O excess OH Br O or Br O or or OH O
The End
FINAL EXAMINATION Chemistry 3B
SID #:______________________
Peter Vollhardt May 17, 2006 Please provide the following information if applicable.
Making up an I Grade _____ (If you are, please indicate the semester during which you took previous Chem 3B: Semester Instructor
Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 25 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Grades will be posted on May 25, by 5 pm, outside 320 Latimer Hall. Good Luck!
DO NOT WRITE IN THIS SPACE I. II. III. IV. V. VI. VII. ______ ______ ______ ______ ______ ______ ______ (60) (175) (60) (40) (60) (60) (45)
Total:
(500)
I.
[60 Points] Provide the IUPAC name or draw the structure, as appropriate, of the following molecules. Remember the priority of functional groups in choosing names, indicate the correct stereochemistry (e.g., R, S, and E, Z), and do not forget about the alphabetical ordering of substituents!
(a)
COOH H2 N H
(b) Methyl cis-4-bromocyclohexanecarboxylate
(c)
S H
(d)
O N CCH2COCH2CH3
(e) (4R)-Bromo-N-ethyl-N-methylpentanamide
(f)
COOH H2 N H CH2CH2SCH3
(This is the amino acid methionine)
II. [175 Points; (a) - (j) 10 points each, (k) - (o) 15 points each] Add the missing components (starting materials, reagents, or products) of the following reactions in the boxes provided. Aqueous work-up (when required) is assumed to be part of a step. It is not part of any answer. (a)
O S O CH3
CH3OH -CH3SO3H
(b)
1.
O C H
2.
NH3 COO-
(c)
CH3
CH3
13
C NMR: = 23.4, 32.9, 137.2 ppm
(d)
O
H+, H2O
O
1
H NMR: = 6.20 (s, 2H), 2.01 (s, 6H) ppm
(e)
CH3
CH3
CI
(f)
CH3O OCH3
H+, CH3OH
(g)
CH3NH2, Na+ NCBH3
(h)
+
O
(i)
CH3
(CH3)2NH
HOOC O
13
N CH3
C NMR spectrum of starting material:
Mass spectrum of starting material:
(j)
Na+OH, H2O +
O O
(k) 1.
2.
NO2
CN
3.
(l)
1.
2.
O
3.
(m)
1. PBr3 2. NaCN 3.
MgBr
4. H+, H2O
OH
(n)
O
1. LiAlH4 2. CH3I (2 equiv) 3. Ag2O

NH
m/z = 99
(o)
O O
OCH3
CH3O
OCH3
+
H3 C N H CH3
III. [60 Points] Treatment of chloroacetic acid A with methoxybenzene B and AlCl3 led to unknown C. The mass, IR, and NMR spectra of this product are shown in the following pages.
AlCl3 ClCH2COOH A +
OCH3
C (Unknown)
(a) After consideration of the spectral data, write the structure of the product in the box below.
10
1.
Mass Spectrum
Label the molecular ion as M+ and the base peak as BP. Using the partial periodic table on the previous page for atomic weights, draw the structures of the fragment ions at m/z = 148, 135, and 121, respectively, in the boxes below. Draw a + charge at the point of the dangling valence in your line structure.
m/z = 148
m/z = 135
m/z = 121
11
2.
IR Spectrum
~
(Csp3H) is:
present
absent
at
cm1
(Csp2H) is:
present
absent
at
cm1
(OH) is:
present
absent
at
cm1
(C=O) is:
present
absent
at
cm1
12
13
3.
C NMR Spectrum (scale in ppm).
Draw your suggestion for the unknown in the box below and label the types of carbon atoms A, B, C, and D, giving rise to the corresponding signals in the spectrum. Note that B is a group of four signals, which belong to a group of similar carbon atoms, all of which should be labeled B.
13
4.
H NMR Spectrum (scale in ppm; for expanded sections, see below and the next page).
As indicated on the spectrum above, the signal due to proton A disappears in D2O solvent (exchanges).
14
Draw your suggestion for the unknown in the box and label the hydrogens AE giving rise to the corresponding signals in the spectrum. Note: For the assignment of B and C, consider the effect of close lying substituents.
15
IV. [40 Points] You are asked to assign the structures of the two pentoses D-arabinose and Dxylose. Ruff degradation of the former gives D-erythrose, that of the latter D-threose. KilianiFischer extension of D-arabinose furnishes D-glucose and D-mannose, that of D-xylose results in D-gulose and D-idose.
CHO H H OH OH CH2OH HO H CHO H OH CH2OH
D-(-)-Erythrose
D-(-)-Threose
D-Arabinose
D-Xylose
CHO H HO H H OH H OH OH CH2OH HO HO H H
CHO H H OH OH CH2OH
H H HO H
CHO OH OH H OH CH2OH HO H HO H
CHO H OH H OH CH2OH
D-(+)-Glucose
D-(+)-Mannose
D-(-)-Gulose
D-(-)-Idose
1. Draw your assignments in the respective boxes, using Fischer projections.
16
2. Specify the conditions of (a) the Ruff degradation
1.
2.
(b) the Kiliani-Fischer extension
1.
2.
17
V. [60 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have! Work from left to right in the following spaces. There is much more space than you will need. (a)
O
OH Br Br
NaOH, Br2
Br
18
(b)
O
1. LiAlH4 2. H+, H2O,
19
(c)
H
H+, CH3CH2OH + CH2=O + CH3NH2

H3C
N CH3 H
20
VI. [60 Points] Provide a reasonable synthetic route from starting materials to product. Note: Several steps are required, and there may be more than one solution to the problem. You may use any additional organic or organometallic reagents to effect your conversions. Do not write mechanisms! Br (a)
Br
21
(b)
CH(CH3)2 H2NCHCOOH and H2NCH2COOH
CH(CH3)2 H2NCHCNHCH2COOH O
Valine
Glycine
Val-Gly 1. Protection of valine
2. Protection of glycine
3. Dipeptide formation
22
(c)
23
VII. [45 Points] Place an X mark in the box next to the most accurate statement. (a) The longest wavelength band in the UV spectra of the hydrocarbons below moves to lower energy in the order
1, 2, 3
3, 2, 1
2, 3, 1
3, 1, 2
(b) Circle the compounds which are aromatic
24
(c) The pKa values of the following compounds decrease in the order
O
CH3OH
N + H N H
1, 2, 3, 4
4, 3, 2, 1
2, 3, 4, 1
3, 4, 2, 1
(d) The rates of electrophilic aromatic nitration of the following compounds increases in the order NO2 NO2
Cl
S
Cl
1, 2, 3
2, 1, 3,
3, 2, 1
2, 3, 1
25
(e) Oxidation of idose to idaric acid causes

CHO HO H HO H H OH H OH CH2OH
HNO3
COOH HO H HO H H OH H OH COOH
Idose
Idaric acid
the specific rotation to go to zero the 13C NMR spectrum to simplify to 3 lines
the sugar to become reducing
mutarotation
The End Have a great summer!
Peter Vollhardt December 15, 2006 Please provide the following information if applicable.
______________________
Making up an I Grade _____ (If you are, please indicate the semester during which you took previous Chem 3B: Semester Instructor Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 25 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Grades will be posted on Wednesday, December 20, by 5 pm, outside 320 Latimer Hall. Good Luck!
Total:
(500)
I.
[60 Points] Provide the IUPAC name or draw the structure, as appropriate, of the following molecules. Remember the priority of functional groups in choosing names, indicate the correct stereochemistry (e.g., R, S, and E, Z), and do not forget about the alphabetical ordering of substituents!
(a) (2S)-Amino-6-heptynoic acid
(b)
Cl Br
Cl
(c) (R)-2, 3-Dihydroxypropanal
(d)
O O
OCH2CH3
(e)
N-(2-Methylpropyl)ethanamide
(f)
O S O CH3
Na+-OCH3, CH3OH
(b) 1.
NH2
2.
CH3O OCH3
CH3O OCH3
(c)
(d)
P2S5
O
1
H NMR: =2.35 (s, 6H), 2.01 (s, 6H) ppm
(e)
CH3 HNO3, H+ N
(f)
H OH HO HO HO H H OH H H O CH3OH, H+
(g)
O
CH3NH2, Na+ NCBH3
(h)
+ CN
(i)
O CH3COOH
13
C NMR = 220.2, 38.3, 23.3 ppm
(j)
Na+OCH3, HCH3OH
OCH3
H NMR spectrum:
(k) 1.
O
2.
+
N
N N
3.
(l) 1.
2.
O CH3COCH3
OH O
CH3CHCH2COCH3
(m)
1. CH3OH, H+ 2. 2 CH3MgBr H+, CH3OH
OH
(n) 1. NaCN 2. CH3CH2CH2MgBr 3. CH2=P(C6H5)3
CH3I
Mass spectrum of product:
(o)
O O
OCH3
CH3O H3 C N H CH3
OCH3
III. [60 Points] In an attempt to effect electrophilic methoxylation, benzene carbaldehyde A was treated with methyl hydroperoxide B in the presence of acid. The mass, IR, and NMR spectra of this product are shown in the following pages. From the complex mixture of products, traces of unknown C were obtained.
O
H+ C (Unknown)
H
CH3OOH
(a) After consideration of the spectral data, write the structure of the product in the box below.
10
11
b. Draw again your suggestion for the unknown in the box and label the hydrogens A, B, C, and D giving rise to the corresponding signals in the spectrum. Use the Table below, if necessary.
2.
13
C NMR Spectrum.
12
Draw again your suggestion for the unknown in the box below and label the types of carbon atoms AE giving rise to the corresponding signals in the spectrum.
3. Mass spectrum.
13
a. Clearly mark on the spectrum the molecular ion as M+.
b. In the boxes above the respective fragment ions, indicate the molecular piece that has fragmented from M+, e.g. Cl, or CH3O, or CH3CH2, or ?
4. IR Spectrum.
14
~
(Csp2H) is:
present
absent
at
cm1
(Csp3H) is:
present
absent
at
cm1
(OH) is:
present
absent
at
cm1
(C=O) is:
present
absent
at
cm1
15
IV. [40 Points] You are asked to assign the structures of the two pentoses D-ribose and Dlyxose. Ruff degradation of the former gives D-erythrose, that of the latter D-threose. KilianiFischer extension of D-ribose furnishes D-allose and D-altrose, that of D-lyxose results in Dgalactose and D-talose ribose.
CHO H H OH OH CH2OH HO H CHO H OH CH2OH
D-(-)-Erythrose
D-(-)-Threose
D-Ribose
D-Lyxose
CHO H H H H OH OH OH OH CH2OH HO H H H
CHO H OH OH OH CH2OH
CHO H HO HO H OH H H OH CH2OH HO HO HO H
CHO H H H OH CH2OH
D-Allose
D-Altrose
D-Galactose
D-Talose
1. Draw your assignments in the respective boxes, using Fischer projections.
16
2. Specify the conditions of (a) the Ruff degradation
1.
2.
(b) the Kiliani-Fischer extension
1.
2.
17
OH
OH
NaOH,
18
(b)
O N O CH3
CH2D N CH3 OH
1. LiAlD4 2. H+, H2O (work up)
19
(c)
O H2N
NaBH3CN, CH3OH
H
N H
20
VI. [60 Points] Provide a reasonable synthetic route from starting materials to product. Note: Several steps are required, and there may be more than one solution to the problem. You may use any additional organic or organometallic reagents to effect your conversions. Do not write mechanisms! (a)
N H O
21
(b)
O
H 2N COOH
H 2N
CNH
COOH
22
(c) The only organic starting materials:

O
O O N N
OCH3 O O OCH3
23
VII. [45 Points] Place an X mark in the box next to the most accurate statement. (a) The longest wavelength band in the UV spectra of the hydrocarbons below moves to lower energy in the order
1, 2, 3
3, 2, 1
2, 1, 3
3, 1, 2
(b) Circle the compounds which are aromatic

N
O
O2N
N
N H
24
(c) In the collection below, circle the most abundant fragments formed during the mass spectral ionization of 2-pentanone.
O 70 eV H+ C O CH3+
C 3H 6O+
CH3CH2+
C 2H 4 +
CH 3CH 2CH2+
(d) The rates of electrophilic aromatic nitration of the following compounds increases in the order Cl
Cl
N CH3
1, 2, 3
2, 1, 3,
3, 2, 1
2, 3, 1
25
(e) Give the products and their molar amounts per mole of starting material of the complete periodic acid oxidation of D-erythrose and D-erythrulose.
CHO H H OH OH CH2OH
HIO4
D-Erythrose
CH2OH O H OH CH2OH
D-Erythrulose
The End Merry Christmas!
Peter Vollhardt December 17, 2008 Please provide the following information if applicable.
______________________
Total:
(500)
I.
[60 Points] Provide the IUPAC name or draw the structure, as appropriate, of the following molecules. Remember the priority of functional groups in choosing names and indicate the correct stereochemistry (cis, trans, E, Z, R, and S, as appropriate)! Trans-3-oxo-4-hexenal
(a)
(b)
1-Bromo-4-(2,2-dichloropropyl)benzene
(c)
(R)-2,3-Dihydroxypropanenitrile (Fischer projection)

1 2
The numbers refer to the main chain
(d)
H2N H O
OCH2CH3
(e)
N-Chloro-N-methyl-3-pentanamine
(f)
O S O CH3 +
O O CH3OH
Na+
O O
(b) 1.
H3CO
NH2
2.
H3CO
H3CO OCH3
CH3O OCH3
(c)
H
(d)
O NH3, H+ O
13
C NMR spectrum:
(e)
HNO3, H+ N H3C NH2
(f)
H OCH3 H3CO H3CO H3CO H O OCH3 H H H2O, H+ mildly acidic

O
(g)
O
H N CH3
Two reagents
(h)
H3CO CN + CN
(i)
+ NaOH
H2N O
NH2
(j)
OH
1. LiAlH4 2. H+, H2O
H3CO
IR spectrum of starting material:
13
C NMR spectrum of starting material:
(k) 1.
2.
O
H3C
OH
(l) 1.
2.
Br
OH
3.
NH2
NH2
(m) HIO4
2 HCOOH + 1 CH2=O
An aldose
(n) 1.
O N Br O
2.
CH3
Mass spectrum of product:
H NMR spectrum of product:
ppm (o) 1. MnO2 2. NH3 +
3.
NH2 COOH
OH
10
III. [60 Points] Diethyl malonate A was treated with bromine to give a product B. The mass, IR, and NMR spectra of B are shown in the following pages in the sequence : 1. 1H NMR , 2.
13
C NMR , 3. Mass , 4. IR.
Br2 O
A (a) After consideration of the spectral data, write the structure of B in the box below.
Structure of B
11
1. 1H NMR spectrum (for expanded sections, see bottom spectra).
C B A
ppm
B
(J = 8 Hz)
C (J = 8 Hz)
ppm
ppm
12
b. Draw again your suggestion for B in the box and label the hydrogens A, B, and C giving rise to the corresponding signals in the 1H NMR spectrum. Use the Table below, if necessary.
13
2.
13
C NMR spectrum.
D B
C A
14
Draw again your suggestion for B in the box below and label the types of carbon atoms AD giving rise to the corresponding signals in the spectrum.
a. Clearly mark on the spectrum the molecular ion(s) M+. b. In the boxes below, indicate the structure of the fragment ions with the m/z value given under the box.
m/z =
193/195
29
15
4. IR Spectrum.
~
(Csp2H) is:
present
absent
at
cm1
(Csp3H) is:
present
absent
at
cm1
(OH) is:
present
absent
at
cm1
(C=O) is:
present
absent
at
cm1
16
IV. [40 Points] (a) D-Ribulose is a non-reducing pentose. Treatment with NaBH4 gives two alditols. One of them is identical to the product of NaBH4 reduction of D-ribose, the other is identical to the product of NaBH4 reduction of D-arabinose. Fill in the blanks below and provide a structure for D-ribulose.
NaBH4
An alditol D-Ribulose NaBH4

CHO H H H OH OH OH CH2OH D-Ribose
An alditol NaBH4
CHO HO H H H OH OH CH2OH D-Arabinose
(b) D-Erythrose was treated with aqueous bromine to give the aldonic acid A, which was subsequently thermally dehydrated to B, and then treated with acidic acetone to give the final product C. Provide structures for A and B.
CHO H H OH OH CH2OH D-Erythrose A O H+, H3C CH3 B H2O O C Note: These "corners" are not atoms. H O H CH2 O O C CH3 CH3 Br2, H2O H2O
17
H3C + O CH3 O
CH3
NaOH, H2O,
18
(b)
Br O2N O
O O2N
2 NaOH, H2O
NO2
NO2
19
(c)
OH
H+, H2O
CH3
H3C
CH3
CH3
20
VI. [60 Points] Provide a reasonable synthetic route from starting material to product. Note: Several steps are required, and there may be more than one solution to the problem. Do not write mechanisms! Write out each step separately, including reagents and products. You need to apply retrosynthesis! You may use any additional organic or organometallic reagents to effect your conversions. (a)
NH2
Note:
HCCl, HCCl, H2NCCl, and ClCH2NH2 do not exist and are not allowed as reagents. O NH O
21
(b)
COOH
COOH
H2N
NH2
NH
22
(c) For this problem, use the materials given below as the only organic compounds:
O O I
O Starting material Additional organic reagents
23
VII. [45 Points] Place an X mark in the box next to the most accurate statement. (a) The acidity of 14 increases in the order
O
CH3NH3
H3NCH2COH
CH3C
1, 2, 3, 4
4, 3, 2, 1
4, 1, 2, 3
3, 2, 1, 4
(b) In the 1H NMR spectrum of the compund below circle the hydrogens that you expect to show peaks in the left half of the spectrum (that is > 5 ppm).
H Cl H
H H
O O N
O N O H H
24
(c) The following Diels-Alder reaction follows the endo rule. True or false? Circle the correct answer below
CH3 CH3 + CO2CH3 CO2CH3 H CO2CH3 H CO2CH3
True
False
(d) The mass spectrum of N,N-dipropylpropanamine (see below) shows only a relatively small molecular ion peak at m/z = 143. The base (100%) peak is a fragment at m/z = 114. In the box below the spectrum, draw the structure of this fragment (including charges).
N,N-dipropylpropanamine
25
(e) Aromatic heterocycles are frequently constructed in one step by a combination of aldol and imine condensations. With this statement in mind provide the most suitable retrosynthetic disconnection of A into two starting materials (boxes).
CH3
O CH3
CH3
SID #:______________________
GSI (if you are taking Chem 3BL): ______________________ Peter Vollhardt December 16, 2009 Please provide the following information if applicable. Making up an I Grade _____ (If you are, please indicate the semester during which you took previous Chem 3B: Semester Instructor
Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 19 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Good Luck! DO NOT WRITE IN THIS SPACE I. ______ II. ______ III. ______ IV. ______ V. ______ VI. ______ VII. ______ Total: (45) (500) (60) (60) (40) (60) (175) (60)
I.
[60 Points] Name or draw, as appropriate, the following molecules according to the IUPAC rules. Indicate stereochemistry where necessary (cis, trans, E, Z, R, or S). (R)-4-bromo-N-ethyl-N-methyl-pentanamide
(a)
(b)
1-Bromo-4-(2,2-dichloropropyl)benzene
(c)
(R)-2,3-Dihydroxypropanal (Fischer projection)
The numbers refer to the main chain
(d)
(e)
Methyl 3-oxo-butanoate
(f)
H2, PdC
(b) 1.
C6H8O
H3CO
NH2
2.
H3CO OCH3
(c) H
(d)
(e)
(f)
(g)
H N
H2C=O + NaBH3CN, CH3OH
CH3
(h)
OCH3
Complete the stencil above
(i)
H3C O
(j)
OH
H3CO
(k) 1.
2.
(l) 1.
2.
3.
(m) HIO4
2 HCOOH + 1 CH2=O
An aldose
(n)
(o)
OH
1. MnO2 2. NH4CN 3. H+, H2O,
III. [60 Points] The wavy lines in the following structure indicate four possible retrosynthetic disconnections of four bonds (numbered 1-4).
Show the respective four reactions that would lead to the generation of each of these strategic bonds in the four boxes below. Note: It is fine to use a protected or otherwise modified fragment to make the desired connection, as long as it can be elaborated later into the target structure. However, do not show such elaboration. Each box should contain only the reagents that you would use to make the bond in question. Bond 1:
Bond 2:
Bond 3:
Bond 4:
10
IV. [40 Points] (a) D-Ribulose is a pentaketose. Treatment with NaBH4 gives two alditols. One of them is identical to the product of NaBH4 reduction of D-ribose, the other is identical to the product of NaBH4 reduction of D-arabinose. Fill in the blanks below and provide a structure for D-ribulose.
NaBH4
D-Ribulose
An alditol NaBH4
CHO H H H OH OH OH CH2OH D-Ribose
An alditol NaBH4
CHO HO H H H OH OH CH2OH D-Arabinose
(b) D-Erythrose was treated with nitric acid to give the aldaric acid A, which was treated with acidic acetone to give B. On heating, B dehydrated to the final product C. Provide structures for A and B.
11
V. [60 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have! Work from left to right in the following spaces. There is more space than you will need. (a) H+, H2O, THF
12
(b) H+, H2O
13
(c) H+, H2O,
14
VI. [60 Points] Provide a reasonable synthetic route from starting material to product. Note: Several steps are required, and there may be more than one solution to the problem. Do not write mechanisms! Write out each step separately, including reagents and products. You need to apply retrosynthesis! You may use any additional organic or organometallic reagents to effect your conversions. (a)
15
(b)
NH2
HOOC
NH O Work from left to right in the following spaces. There is much more space than you will need.
16
(c)
17
VII. [45 Points] Place an X mark in the box next to the most accurate statement. (a) The acidity of 14 increases in the order:
O
CH3NH3
H3NCH2COH
CH3C
1, 2, 3, 4
4, 3, 2, 1
1, 4, 2, 3
3, 2, 1, 4 (b) The following two sugars are:
CHO H HO H H OH H OH OH CH2OH HO HO H HO
CH2OH H H OH H CHO
Identical Enantiomers Diastereomers Anomers
18
(c) The following heterocycle will undergo electrophilic bromination at position:
N
1 4
N 1 2 3 4 (d) The following reaction will give
O O
Na+ OCH2CH3, CH3CH 2 OH
O O O
O O
O O O
19
(e) Which of the following molecules are reduced by LiAlH4? Check all the boxes that apply.
OH O
Cl
N
SID #:______________________
GSI (if you are taking Chem 3BL): ______________________ Peter Vollhardt September 23, 2010 Please provide the following information if applicable. Making up an I Grade _____ (If you are, please indicate the semester during which you took previous Chem 3B: Semester Instructor
Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 15 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Good Luck!
I.
a. (S)-1-(2-Chlorobutyl)-2-nitrobenzene
b. cis-Hexa-1,3-diene
c.
CH3 O
CH3 Pure enantiomer d.
e. 4-Oxopentanal
II.
[30 Points] product.

CF3
Compound A undergoes preferential electrophilic nitration to give only one
CF3 2 NO2 HNO3, H2SO4 or O2N OH
CF3 O2N or
CF3
4 OH A
OH
OH
a. b.
Which one? Mark the box below your choice with an X, preferably after you have completed questions b.d. Write all the resonance forms of the intermediate formed by attack of NO2+ on A at:
CF3 6 1 2
C-2:
5 4 OH 3
Note: A first stencil is provided for format. Leave out the numbering in any additional structures. Write the nitro group as NO2 (no need for the Lewis structure).
CF3 6 1 2
C-5:
5 4 OH 3
Note: A first stencil is provided for format. Leave out the numbering in any additional structures. Write the nitro group as NO2 (no need for the Lewis structure).
CF3 6 1 2
C-6:
4 OH
Note: A first stencil is provided for format. Leave out the numbering in any additional structures. Write the nitro group as NO2 (no need for the Lewis structure). c. d. Circle (in your answers above) the most strongly contributing resonance forms of the attack at C-2, C-5, and C-6. Considering all of the above most strongly contributing resonance forms, which one is the best overall? Redraw it in the box below.
CF3 6 1 2
4 OH
III.
a.
Two isomers. Add the missing pieces.
b.
1
BrH2C
2 3 4
Br2
Kinetic product Hint: Electrophilic attack occurs preferentially at C-1.
c. CH3 CN O
+
CN
Complete the stencil above, showing clearly stereochemistry (hashed and wedged bonds).
d.
Product of ring opening e. OH MnO2
OH
f.
1. 2.
g. CH3 HO3S HNO3, H2SO4 O2N F
h.
O2N Br2, FeBr3 Cl Monobromination
i.
j.
1.
2.
H3C
H C
CH3
SO3, H2SO 4
3.
H+, H2O
H3C H2N
H C
CH3
IV.
[40 Points]
a. Rank the following arenes in order of reactivity (highest to lowest) toward electrophilic aromatic substitution. Mark the box next to the best answer below.
Cl
OCH3 NO2
Br
1 2 3 4
CF3
1, 2, 3, 4
3, 1, 2, 4
3, 2, 1, 4
3, 1, 4, 2
b. Among the compounds shown below, circle those that are stabilized by conjugation.
10
c. One of the compounds shown below is aromatic. Circle its structure.
CH3
CH3
d. Rank compounds 15 in order of increasing reactivity as dienes in the Diels-Alder reaction:
1, 2, 3, 4, 5
1, 4, 2, 3, 5
3, 1, 5, 4, 2
5, 3, 1, 4, 2
3, 5, 1, 2, 4
11 V. [40 Points] Write detailed stepwise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have!
a.
12
b. Hydrocarbon A is doubly deprotonated by methyllithium to give the aromatic dianion B. Treatment of B

with bromine at low temperatures gave C. Write a plausible mechanism that leads from B to C.
13
14
b. Synthesize compound A from any acyclic materials and any other reagent. Hint: Think Diels-Alder reaction. Caution: Work backwards.
CO2CH3 O
A (racemate) Work from left to right in the following spaces. There is much more space than you will need.
15
VII.
[20 Points]
a. The Diels-Alder reaction is made possible because a racemate is formed the (4N+2) rule overrides the Lewis octet rule of two isomeric products the less stable one is formed the reaction requires heat to go to completion an aromatic transition state b. The bromine substituent in bromobenzene directs electrophiles ortho/para because it is inductively donating it is inductively electron-withdrawing it stabilizes the cationic intermediates by resonance it is sterically hindered it is an electron acceptor by resonance
The End
SID #:______________________
GSI (if you are taking Chem 3BL): ______________________ Peter Vollhardt October 28, 2010 Please provide the following information if applicable. Making up an I Grade _____ If you are, please indicate the semester during which you took previous Chem 3B:
Semester
Instructor
Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 13 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Good Luck! DO NOT WRITE IN THIS SPACE I. II. III. IV. V. VI. (30) (30) (50) (60) (60) (20)
Total:
(250)
Page
I. a.
O HO H
b.
N-Methylpent-2-ynamide
c. H2N
COOH d. O O
Br
e.
(Z)-4-Hydroxybut-2-enal
Page
II.
[30 Points] Write the organic products of the following reactions of the starting ester. Neutralizing aqueous work up is assumed.
(CH3)2NH, 250 C
1.
N Li+
2.
Molecular formula = C 5H8O2
LiAlH4
CH3MgBr (2 equiv)
NaOH, H2O
Page
III.
a.
CH3CH2OH, CH3CH2ONa+
b. 1. LDA 2. CH3I 3. LiAlH4
c.
d.
Page
e.
Br
Br
O
O O
OH
f.
PCl5
g. 1.
2.
h.
MgBr
CH3CN
Page
i.
j.
NaCNBH3, CH3OH
Page
IV.
[60 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have!
a.
O
catalytic H2 SO4 , THF
O OH
HO
Page
b.
Page
c.
Page
10
V. [60 Points] Provide a reasonable synthetic route from starting material to product. Note: Several steps are required, and there may be more than one solution to the problem. Do not write mechanisms! Write out each step separately, including reagents and products. Apply retrosynthesis! It will help you obtain at least partial credit. a. You may use any additional simple reagents.
NHCH3 and
as starting materials
Page
11
b.
Page
12
c. Synthesize compound A from benzene.
Page
13
VI.
[20 Points]
a. The equilibrium constant K for the hydration of 14 increases in the order
1, 2, 3, 4 4, 3, 2, 1 2, 3, 4, 1 2, 3, 1, 4
b. The basicity of 14 increases in the order
1, 2, 3, 4 4, 3, 2, 1 2, 1, 4, 3 3, 2, 1, 4
They failed Chem 3B.
The End
SID #:______________________
GSI (if you are taking Chem 3BL): ______________________ Peter Vollhardt December 15, 2010 Please provide the following information if applicable. Making up an I Grade _____ (If you are, please indicate the semester during which you took previous Chem 3B: Semester Instructor
Please write the answer you wish to be graded in the spaces provided. Do scratch work on the back of the pages. This test should have 19 numbered pages. Check to make sure that you have received a complete exam. A good piece of advice: Read carefully over the questions (at least twice); make sure that you understand exactly what is being asked; avoid sloppy structures or phrases. It is better to be pedantic in accuracy now than sorry later! Good Luck! DO NOT WRITE IN THIS SPACE I. ______ II. ______ III. ______ IV. ______ V. ______ VI. ______ VII. ______ Total: (45) (500) (60) (60) (40) (60) (175) (60)
I. (a)
O N H
(b)
2-Chloro-1-methyl-4-(2-propenyl)benzene
(c)
(d)
(e) 4-Fluoro-2-iodopyrrole
(f) N-Ethyl-3-methylpent-4-ene-1-amine
II. [175 Points; (a)(j) 10 points each, (k)(o) 15 points each] Add the missing components (starting materials, reagents, or products) of the following reactions in the boxes provided. Aqueous work-up (when required) is assumed to be part of a step. It is not part of any answer. (a)
Cl2
(b) 1.
O
2.
Cl
NH2
OCH3
(c)
OCH3
(d)
1.
O
NH2 2.
H2N
O OH
O O O
(e)
(f)
(g)
NC
H2C=O + NH3 +
CN
N H
(h)
(i)
Na+OCH3, CH3OH,
OCH3
(j) 1. Li 2.
(k)
MgBr
OH H
(l) 1.
2.
3.
OH
4.
(m)
HIO4
1 HCOOH + 2 CH2=O + 1 CO2
A D-ketose
(n)
C6H13N (o)
1. MnO2 2. +NH4CN 3. H+, H2O,
III.
[60 Points] The wavy lines in the following structure indicate four possible retrosynthetic disconnections of four bonds (numbered 1-4).
O 1
4 N
Show the respective four reactions that would lead to the generation of each of these strategic bonds in the four boxes below. Note: It is fine to use a protected or otherwise modified fragment to make the desired connection, as long as it can be elaborated later into the target structure. However, do not show such elaboration. Each box should contain only the reagents that you would use to make the bond in question. Bond 1:
Bond 2:
Bond 3:
Bond 4:
10
IV. [40 Points] In water, ribose exists mainly in its cyclic furanose form (both structures are shown below). A researcher finds a bottle of ribose monomethyl ether and wants to know the position of the methoxy group. There are five options, indicated by boxes in the two structures given for ribose. NaBH4 reduction of ribose monomethyl ether gave an optically active compound A. HNO3 produced optically active dicarboxylic acid B. Ruff degradation of ribose monomethyl ether, followed by NaBH4 reduction led to optically active compound C. Fill in the blank boxes below with the structures of A, B, C, and ribose monomethyl ether.
NaBH4
Ribose monomethyl ether
1. Ruff degradation 2. NaBH4
11
V. [60 Points] Write detailed step-wise mechanisms for the following transformations. Use only structures and arrow-pushing techniques. Note: These are not synthetic problems. Do not add any reagents! What you see is what you have! (a)
12
(b)
13
(c)
Hint: There is no water. Work from left to right in the following spaces. There is much more space than you will need.
14
VI. [60 Points] Provide a reasonable synthetic route from starting material to product. Note: Several steps are required, and there may be more than one solution to the problem. Do not write mechanisms! Write out each step separately, including reagents and products. Apply retrosynthesis! It will help you obtain at least partial credit. (a)
15
(b)
16
(c)
You may use additional organic or organometallic reagents containing seven carbons or less to effect your conversions. Work from left to right in the following spaces. There is much more space than you will need.
17
VII. [45 Points] Place an X mark in the box next to the most accurate statement. (a) The product of the following Diels-Alder reaction is
O OCH3
+ O
OCH3
endo
exo
entropically favored
kinetically disfavored (b) Show by an arrow the most likely site of protonation of the following molecule:
O NH2
N
H2N
N H
18
(c) In the following molecule, circle all possible sites of reduction by excess LiAlH4:
O CN OCH3 O H
HN
(d) The following scheme describes part of an industrial synthesis of the drug Chantix. One step will not work. Circle which one.
1. O3 2. H2, Pt
CHO
C6H5CH2NH2, H+, H2, Pt
NCH2C6H5
H+, H2O
CHO O O NH CF3COCCF3 O NCCF3 O2N O2N O NCCF3
HNO3, H+
19
(e) Circle the most thermodynamically stable of the following isomers:
OH

Chem 3 BPractice Exams 2011

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Chem 3 BPractice Exams 2011

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1

Name:__________________________ Print first name before second! Use capital letters!

Four resonance forms

Three resonance forms c. Circle (in your answers above):

A hexatriene isomer of product. e.

A salt; 13C NMR: 4 lines

b. Interpret the spectral data as requested in the spaces provided. 1. IR Spectrum

The proton-coupled spectrum leaves the singlets for B, C, and D unchanged.

3. 1H NMR Spectrum (for expanded sections, see next two pages).

11 The signal due to protons A disappears in D2O solvent.

3, 1, 2 b. Circle the compounds which are aromatic

Name:__________________________ Print first name before second! Use capital letters!

Three resonance forms

Three resonance forms c. Circle (in your answers above):

An octatetraene isomer of product.

Mass spectrum of product :

1. 1H NMR Spectrum (for expanded section, see bottom spectrum).

C NMR Spectrum (these are five single lines).

The spectrum is that of a colored compound.

The unknown is aromatic.

The max is at 300 nm.

b. Synthesize compound A from any materials containing six carbons or less.

4, 1, 2, 3 b. Circle the compounds which are aromatic

Name:__________________________ Print first name before second! Use capital letters!

Three resonance forms

Three resonance forms

Product of ring opening

1. 1H NMR Spectrum (for expanded section, see bottom spectrum).

C NMR Spectrum (these are six single lines).

The spectrum depicts a nonconjugated compound.

The spectrum is that of a colored compound.

The unknown is aromatic.

The max is at 300 nm.

4, 1, 2, 3 b. Circle the compounds which are aromatic

Name:__________________________ Print first name before second! Use capital letters!

[30 Points] product.

Compound A undergoes preferential electrophilic nitration to give only one

CF3 HNO3, H2SO4

CF3 or NO2 CH3 O2N CH3

c. CH3 CN O CH3 CH3 O

Product of ring opening

OCH3 H3C SO3, H2SO4 O2N F

Two diastereomers. Add the missing pieces. IV. [40 Points]

4, 1, 2, 5, 3 c. Circle the compounds which are aromatic:

d. Rank compounds 15 in order of increasing reactivity as dienes in the Diels-Alder reaction:

Name:__________________________ Print first name before second! Use capital letters!

SID #:______________________ Laboratory GSI (if applicable):

~ = 3350 (broad), 1720 cm1

1. SOCl2 2. CH3OH OCH3

Mass spectrum of starting material:

C NMR : = 208.9, 45.7, 29.8, 17.4, 13.7 ppm

IR: No peaks >3010 cm1

1. PBr3 2. Br2 3. NH3 (excess) B (unknown)

Note: Disregard the mechanism of catalytic hydrogenation.

Name:__________________________ Print first name before second! Use capital letters!

SID #:______________________ Laboratory GSI (if applicable):

Chemistry 3B, Examination 2

1. CH3MgBr (2 equiv.) 2. H+, H2O work-up

1. LiAlH4 2. H+, H2O work-up

2. H+, H2O work-up

Chemistry 3B, Examination 2

Mass spectrum of product::