Chem 41c Quiz 1

Stoltz, Spring 2011 April 8, 2011 Due April 11, 2011 9:00 AM You have 30 min to take this quiz. It is closed note, closed book, and no collaboration is allowed. Please do not discuss the quiz with anyone until you receive it back graded. Place a box around your answers. There is no partial credit.

Name______________________________________

Chem 41c Quiz 1

Quiz Grade_________
Stoltz, Spring 2011 April 8, 2011 Due April 11, 2011 9:00 AM You have 30 min to take this quiz. It is closed note, closed book, and no collaboration is allowed. Please do not discuss the quiz with anyone until you receive it back graded. Place a box around your answers. There is no partial credit. The quiz is worth 25 out of 20 points. 1. Provide a reagent or reagents to accomplish the following transformation (5 points)
O O O OH O O O OCH3

Predict the products of each reaction. (5 points each) 2.

OH HCl (1 mol%) Et2O

CO2H

3.
O MeO MeO H H2C=PPh3 THF

4.
Br 1. Mg, Et2O 2. CO2 (s) 3. H3O+/H2O

5.
O O O H H O H 1. HS H3O+ Cl 2. Raney Nickel SH

Chem 41c Quiz 3

Stoltz, Spring 2011 April 22, 2011 Due April 25, 2011 9:00 AM You have 30 min to take this quiz. It is closed note, closed book, and no collaboration is allowed. Please do not discuss the quiz with anyone until you receive it back graded. Place a box around your answers. There is no partial credit. The quiz is worth 25 out of 20 points.

Name______________________________________

Chem 41c Quiz 3

Quiz Grade_________
Stoltz, Spring 2011 April 22, 2011 Due April 25, 2011 9:00 AM You have 30 min to take this quiz. It is closed note, closed book, and no collaboration is allowed. Please do not discuss the quiz with anyone until you receive it back graded. Place a box around your answers. There is no partial credit. The quiz is worth 25 out of 20 points.

Predict the products of each reaction. (5 points each) 1.

Et2NH pyridine

Cl

2.
1. Mg, Et2O 2. O Br N OMe

3. H3O+/H2O

3.
O MeN 1. LiAlH4 2. HCl 3. KOH

4. Provide a reagent or reagents to accomplish the following transformation (5 points)

O O O OH O O O Cl

5. Provide a mechanism and all of the reasonable organic products having a molecular weight of at least 100 g/mol (hint: there are three!). (TAs will give partial credit).

O O O H H O H 1. MeMgBr (>3 equiv) THF, 0 C 2. H3O+, H2O

Chem 41c Quiz 4

Stoltz, Spring 2011 May 6, 2011 Due May 6, 2011 10:00 AM You have 30 min to take this quiz. It is closed note, closed book, and no collaboration is allowed. Please do not discuss the quiz with anyone until you receive it back graded. Place a box around your answers. There is no partial credit. The quiz is worth 25 out of 20 points.

Name______________________________________

Chem 41c Quiz 4

Quiz Grade_________
Stoltz, Spring 2011 May 6, 2011 Due May 6, 2011 10:00 AM You have 30 min to take this quiz. It is closed note, closed book, and no collaboration is allowed. Please do not discuss the quiz with anyone until you receive it back graded. Place a box around your answers. There is no partial credit. The quiz is worth 25 out of 20 points. Predict the products of each reaction. (5 points each) 1.
O EtO O N O OEt 1. NaOEt, EtOH PhH, 80 C, 6 h 2. mild acid work-up 0 C

2.
O 1. LDA, THF 2. then 1 O O H

1
3. mild H3O+ work-up

3.
1. LDA, THF 2. O Br N 3. H3O+

4. Circle the compound with the most acidic proton.

O O O O O N CN

5. Provide a plausible mechanism for the following transformation (TAs will give partial credit).
OH LiOt-Bu, t-BuOH O O

Name__________________________

February 11 2009

Please write your name on all pages

Ch 41b Midterm
Instructions: You have 1.5 hours to complete the exam. The exam is closed book and closed notes. No collaboration is allowed. Calculators are permitted.

Problem 1 Problem 2 Problem 3 Problem 4 Problem 5 Problem 6 Problem 7 Problem 8 Problem 9

(4 points) (4 points) (5 points) (6 points) (8 points) (5 points) (6 points) (6 points) (8 points)

____________________ ____________________ ____________________ ____________________ ____________________ ____________________ ____________________ ____________________ ____________________ ____________________

Problem 10 (8 points) TOTAL

(60 points) ____________________

Due 9:00 am Friday, February 13, 2009

Good luck!

Name__________________________

1) Arrange the following molecules in order of increasing max seen in their UV-vis spectra. (4 points)

Lowest max

Highest max

2) Molecule C, shown above, has a of 36,500 M-1 cm-1. A dilute solution is measured by UVvis spectrometry using a cuvette with path length of 1 cm resulting in an absorption of 0.65. What is the concentration of this solution? (4 points)

Name__________________________

3) Provide the products of each of the following reactions. (5 points)

Name__________________________

4) Propose a mechanism for the following transformation. (6 points)

Name__________________________

5) You are given a compound A which has the following spectroscopic data:
1

H NMR (A in CDCl3, TMS = 0.0 ppm)

1.34 (6H, s) 2.19 (1H, s) 2.30 (3H, s) = 2100 cm-1 (moderate, sharp) 1722 cm-1 (strong, sharp) C7H10O

IR (pure A on NaCl) molecular formula of A

When compound A is hydrogenated with H2 and catalytic Pd / C, a new compound B is formed, which has the following spectroscopic data:
1

H NMR (B in CDCl3, TMS = 0.0 ppm)

0.85 (3H, t, J = 7.4 Hz) 1.10 (2H, q, J = 7.4 Hz) 1.32 (6H, s) 2.28 (3H, s) = 1717 cm-1 (strong, sharp) C7H14O

IR (pure B on NaCl) molecular formula of B

Based on the data above, give the structures of both A and B in the boxes below. (8 points)

Name__________________________

6) The mass spectrum of 2,2-dimethylpropanal contains a small peak at m/z= 86 and a base peak at m/z= 57.

a) Draw the structure of the molecular ion of 2,2-dimethylpropanal: (2 points)

b) Write an equation for the fragmentation of the molecular ion shown in part a that leads to the formation of the ion that gives rise to the base peak (3 points)

Name__________________________ 7) Design a synthetic scheme for compound B starting from the alkyl halide A. Show synthetic intermediates and reagents. (6 points)

Name__________________________

8) The molecular formula of compound A is C4H9Br. Given the spectroscopic data below, provide the structure of compound A. (6 points)
1

H NMR: 3.3 (2H, d, J = 6.0 Hz), 1.95 (1H, multiplet(9), J = 6.8 Hz), 1.0 (6H, d, J=6.8 Hz),

Name__________________________

9) The molecular formula of compound B is C6H12O. Given the spectroscopic data below, provide the structure of compound B. (8 points) IR: strong peak at 1713 cm-1
1

H NMR: 2.63 (1H, multiplet(7), J = 6.9 Hz), 2.48 (2H, q, J = 7.3 Hz), 1.10 (6H, d, J=6.9 Hz), 1.05 (3H, t, J=7.3 Hz)

Name__________________________

10. For the hydroboration of an alkyne followed by oxidative workup, product A is preferred over B.

a) For the hydroboration of the alkyne, provide an energy diagram that explains this regioselectivity. (Draw the transition state structure with relative energies). (4 points)

b) Assume that G is 4.2 kcal/mol. What would be the expected ratio of products A/B at room temperature? (4 points)

Name ________________________________ Please write your name on all pages

February 10, 2010

Ch 41b Midterm
Instructions: You have 1 hour to complete the exam. The exam is closed book and closed notes. Calculators are permitted. Good luck!

Problem 1 Problem 2 Problem 3 Problem 4 Problem 5 Problem 6 Problem 7 Problem 8 Problem 9

(4 points) (6 points) (8 points) (8 points) (8 points) (8 points) (3 points) (3 points) (4 points)

____________________ ____________________ ____________________ ____________________ ____________________ ____________________ ____________________ ____________________ ____________________ ____________________

Problem 10 (8 points) TOTAL

(60 points) ____________________

Name ________________________________ 1. Rank the following molecules in order of decreasing pKa (increasing acidity). (4 points)

R H H

R R

H H

O R

pKa

>

>

>

Name ________________________________

2a. Provide the reagents necessary for the following transformation (2 points):

H O

2b. Draw the structure of the major organic product of the following reaction (2 points):

H2 Pd/C Pyridine

2c. Draw the structure of the major organic product of the following reaction (2 points):

Na/NH3

Name ________________________________

3. Propose a mechanism for the following transformation. (8 points)

Br2 H2O

O Br

Name ________________________________

4. Design a synthetic scheme for epoxide B starting from the alkyl halide A. Show synthetic intermediates and reagents (Organic molecules with 4 carbons or less may be used as reagents). (8 points)

H O Br
H

Name ________________________________

5. Design a synthetic scheme for diol B starting from acetylene A. Show synthetic intermediates and reagents. (Organic molecules with 4 carbons or less may be used as reagents). (8 points)

H A

HO H

OH H

Name ________________________________

6. Suppose you were able to cool a sample of 1-bromo-1,1,2-trichloroethane enough that rotation about the carbon-carbon bond becomes slow on the NMR time scale. What changes in the NMR spectrum would you anticipate? Be explicit. (8 points) (Hint: Draw Newman projections)

H H Cl

Cl Cl Br

1-bromo-1,1,2-trichloroethane

Name ________________________________

7. In the 1H NMR spectrum of propylbenzene (CDCl3, 300 MHz, in ppm), the twoproton triplet consists of the following peaks: 2.60, 2.57, 2.54. Express the coupling constant (J) for this splitting pattern in Hz. (3 points)

propylbenzene

8. A solution of 4-methyl-3-penten-2-one in ethanol shows an absorbance of 0.52 at 236 nm in a cell with a 1-cm light path. Its molar absorptivity in ethanol at that wavelength is 12,600 M-1 cm-1. What is the concentration of the compound? (3 points)

4-methyl-3-penten-2-one

Name ________________________________ 9. The 1H NMR spectrum of bromocyclohexane shows a downfield peak (1H) at 4.16. This signal is a single peak at room temperature, but at -75C separates into two peaks at 3.97 and 4.64. Explain this observation. (4 points)

10. Determine the structures of the stereoisomeric 1,3-dibromo-1,3-dimethylcyclobutanes A and B from the spectroscopic data below. (8 points) Isomer A: Isomer B:
1 1

H NMR peaks: 2.13 (6H, s), 3.21 (4H, s) H NMR peaks: 1.88 (6H, s), 2.84 (2H, d), 3.54 (2H, d) (Hint: doublets have equal spacing)

Stoltz Ch 41c Midterm 1

Chem 41c Midterm Exam

Stoltz, Spring 2011, April 29, 2011 The exam begins when you turn to page 2. You have 55 minutes to complete the exam. This is a closed note and closed book exam with no collaboration. You may use the periodic table at the front of the room or the one on the last page of this packet. You may also use a model kit if you like. You may not use any other materials. The exam has a total of 60 points. Good luck. There are 8 pages in this exam packet. Be sure to write your name on every page!

Name:_________________________________________

Stoltz Ch 41c Midterm 2

Chem 41c Midterm Exam

Stoltz, Spring 2011, April 29, 2011 The exam begins now. You have 55 minutes to complete the exam. This is a closed note and closed book exam with no collaboration. You may use the periodic table at the front of the room or the one on the last page of this packet. You may also use a model kit if you like. You may not use any other materials. The exam has a total of 60 points. Good luck. There are 8 pages in this exam packet. Be sure to write your name on every page!

THERE ARE 5 PROBLEMS WORTH 10-15 POINTS EACH ON THIS EXAM. 1. (10 points) 2. (10 points) 3. (15 points) 4. (10 points) 5. (15 points) TOTAL

PLEASE WRITE ALL ANSWERS IN SPACES PROVIDED; USE BACKS IF NECESSARY. ONLY THESE WILL BE GRADED GOOD LUCK!

Stoltz Ch 41c Midterm 3

1. Predict the major organic products of the following reactions or sequences. (2 points each) a.
O OEt 1. CH3MgBr (2 equiv), THF 2. H3O+, H2O

b.
O OH H 1. H+, HS 2. Raney-Ni SH

c.
O O Cl OH i-Pr2NEt, CH2Cl2 O

d.
O O H OCH3 H O O PhCH3 150 C O O

1. LiAlH4, Et2O 2. PDC, CH2Cl2 3. THF, 0 C P(Ph)3

H H3CO H CH3

HINT: heating the product in PhCH3 at 150 C leads to this compound

e.
O EtO O OEt NaOEt, HOEt

Stoltz Ch 41c Midterm 4

Stoltz Ch 41c Midterm 5

2. Propose a mechanism for the following reactions. (5 points each) a.

O Br O O KOH H2O, THF HO2C O O

b.
H O OH
Ph3P C O

O O

Stoltz Ch 41c Midterm 6

3. Provide the missing products in this multi-step synthesis scheme (15 points).

HBr

1. Mg, Ether 2. CO2 3. H2O, H3O+

A C6H11Br

B C7H12O2 1. SOCl2 2. HOCH3, DMAP, Et3N

O Cl Et3N 1. LiAlH4 2. H2O, H3O+

E C9H16O2

D C7H14O

C C8H14O2

Hint: Below is the 1H NMR spectrum of compound E acquired in CDCl3.

3H

2H 1H

10H

4 PPM

Stoltz Ch 41c Midterm 7

4. Glycoside derivatives of the terpene steviol (1) are naturally occurring molecules that have an extremely sweet taste and are used in a variety of soft drinks and other products as low calorie sweeteners. The conversion of steviol (1) to its methyl ester 2 is a slow reaction under acid catalyzed esterification reaction conditions. Why would you expect this to be so? Under what conditions would you expect a rapid reaction to occur? Provide reagents and draw a mechanism for the successful reaction. (10 points)
OH CH3OH, HCl slow reaction H O OH

H HO O H

H O H3C

Steviol (1)

Stoltz Ch 41c Midterm 8

5. We have discussed the so-called Weinreb amide a number of times this term. Show how you could use such an approach to prepare aldehyde 4 from carboxylic acid 3. Explain mechanistically how the Weinreb amide functions and how the chemistry observed differs from what would occur using a standard amide. Finally, propose a synthesis of hydroxyester 5 (15 points).

O OH

O H

OH

O OEt

Ph

Stoltz Ch 41c Midterm 9

The End

Name ________________________________ Please write your name on all pages

March 13, 2009

Ch 41b Final Exam

Instructions: You have 2 hours to complete the exam. The exam is closed book and closed notes. There is no collaboration allowed. Calculators are permitted. Please return the completed exam to 351 Crellin on Tuesday, March 17 by 1:00 PM.

Problem 1 Problem 2 Problem 3 Problem 4 Problem 5 Problem 6 Problem 7 Problem 8 Problem 9

( 2 points) ( 4 points) ( 4 points) ( 2 points) ( 4 points)

________________ ________________ ________________ ________________ ________________

( 4 points) ________________ ( 4 points) ________________ ( 6 points) ________________ ( 6 points) ________________ ________________ ________________

Problem 10 ( 6 points) Problem 11 (6 points)

Problem 12 ( 6 points) ________________ Problem 13 ( 6 points) TOTAL ________________

(60 points) ________________

Good luck!

Name ________________________________

1. Rank the molecules below in order of decreasing pKa (increasing acidity) of the indicated H: (2 points)

H H 3C H H

pKa
least acidic

>

>

>
most acidic

2.

Circle the compounds that are aromatic: (4 points)

O O A B

N N C

H N

Name ________________________________ 3. Provide the structures of the products of each of the following reactions. Show stereochemistry where appropriate: (4 points)

a)

b)

O OEt

c)

CN d) O

Name ________________________________

4. Circle the isoprene units in the following terpenes: (2 points)

OH H H O

menthol

camphor

COOH H

cedrene

abietic acid

Name ________________________________

5. Treatment of nerol with aqueous acid gives rise to terpin. Write a mechanism for its formation. (4 points)

OH H +, H2 O OH

OH nerol terpin

Name ________________________________

6. The following transformation occurs at high temperatures. Provide a mechanism and propose a structure for by-product A: (4 points)

CO2 Et O

+
CO2 Et

? EtO 2C

+
CO 2Et

7. The following transformation occurs at high temperature and pressure. Propose a structure for the intermediate of this reaction: (4 points)

Cl

O O NaOH

Name ________________________________

8. The Friedel-Crafts alkylation of benzene with 1-chloropropane yields two products, A and B, with molecular formula C9H12:

Cl

A
AlCl3

+
B

a) Product A has the following 1H NMR spectrum (CDCl3, 300 MHz, in ppm): 7.15-7.35 (m, 5H), 2.94 (septet, 1H), 1.29 (d, 6H). Identify the chemical structure of A and provide a mechanism for its formation: (4 points)

b) The one-proton septet in the 1H NMR spectrum of A (CDCl3, 300 MHz, in ppm) consists of the following peaks: 3.01, 2.99, 2.97, 2.95, 2.93, 2.91, 2.89, 2.87. Express the coupling constant (J) for this splitting pattern in Hz: (2 points)

Name ________________________________ 9. Compounds A and B are isomers with molecular formula C8H10O. Based on the following spectroscopic data, assign structures to compounds A and B: (6 points) Compound A: IR: 3329, 1046 cm-1 1 H NMR: 7.07-7.41 (m, 5H), 3.77 (t, 2H, J=7Hz), 2.82 (t, 2H, J=7), 2.01 (s, 1H, peak disappears in D2O)

Compound B: IR: 1245 and 1049 cm-1 1 H NMR: 6.8-7.22 (m, 5H), 3.96 (q, 2H, J=7Hz), 1.37 (t, 3H, J=7)

Name ________________________________ 10. Design a synthesis of the molecule below using benzene and starting materials with 3 carbons or less. (6 points)

O H

NO2

Name ________________________________ 11. For each of the following products, design a synthesis starting from benzene. (6 points) a)

COOH

Br

b)

Cl

SO 3H

10

Name ________________________________ 12. Two reaction mechanisms have been suggested to explain the 2+4 cycloaddition reaction. One is a concerted reaction affording cyclohexane product. The second mechanism involves the allylic radical intermediate, which could result in two products, as shown below. However, only cyclohexene is observed. Draw a reaction energy diagram and provide an explanation for why the lack of vinylcyclobutane product in the ring-closing step does not rule out the two-step mechanism. (6 points)

NOT OBSERVED

ONLY PRODUCT

11

Name ________________________________ 13. Please provide a mechanism that explains formation of products A and B, obtained through reaction of the starting material with HCl. (6 points) (Hint: Product B requires a 1,2 alkyl shift.)

HCl Cl A Cl B

12

Name ________________________________ Please write your name on all pages

March 12, 2010

Ch 41b Final Exam

Instructions: You have 2 hours to complete the exam. The exam is closed book and closed notes. There is no collaboration allowed. Calculators are permitted. Please return the completed exam to 351 Crellin on Monday, March 15 by 5:00 PM. Problem 1 Problem 2 Problem 3 Problem 4 Problem 5 Problem 6 Problem 7 Problem 8 Problem 9 ( 4 points) ( 4 points) ( 5 points) ( 8 points) ( 6 points) ____________________ ____________________ ____________________ ____________________ ____________________

( 5 points) ____________________ ( 5 points) ____________________ ( 6 points) ____________________ ( 4 points) ____________________ ____________________

Problem 10 ( 6 points)

Problem 11 ( 3 points) ____________________ Problem 12 ( 4 points) ____________________ TOTAL (60 points) ____________________ ____________________

Extra Credit ( 6 points)

Good luck!

Name ________________________________

1a. Rank the molecules below in order of decreasing pKa (increasing acidity) of the indicated H: (2 points)

H H H H B C D

pKa
least acidic

>

>

>
most acidic

1b. Rank the following in order of reactivity with Br2 in the presence of FeBr3. (2 points)

Br

>
most reactive

>

>
least reactive

Name ________________________________

2a. Rank the following species by carbocation stability: (2 points)

least stable

2b. Rank the following species by carbocation stability: (2 points)

H H 3C A H H 3C

CH3 CH3 B H 3C

OH CH3 C H3C

least stable

>

>
most stable

>

>
>

H CH3 D

most stable

Name ________________________________

3. Provide a mechanistic pathway for the biosynthesis of -terpineol from geranyl pyrophosphate. (5 points)

Name ________________________________

4. Predict the products of the following Diels-Alder reactions. Show stereochemistry when appropriate. (8 points)
O Heat a. O

b.

Heat

N c.

C H

H Heat O

d.

Heat

Name ________________________________

5. Over the arrows below, write in the reagents needed to produce the following reactions in good yield. If more than one step is needed, number each step 1), 2), etc. (6 points)

H3C H

CH3 H

a.

HO H H 3C

OH H CH3

b. CH3CH2C CCH3

H CH3CH2

H CH3

c.

H3C O H3C

d.

H3C CH3 OH O

e. H3C O H3C O H 3C OH CH3

Name ________________________________

6. A compound with molecular formula C4H6O has the following 1H NMR spectrum. Its infrared spectrum (IR) shows a strong, sharp band at 1636 cm-1. From this information deduce its structure and draw it in the box below. (5 points) 1.96 (2 H, m, J=6.9 Hz), 3.03 (4H, t , J=6.9 Hz)

ANSWER:

Name ________________________________ 7. A compound with molecular formula C9H20O2 has the following 1H NMR spectrum. From this information deduce its structure and draw it in the box below. (5 points) 0.90 (6 H, triplet, J=7.0 Hz), 1.31 (4H, m, J=7.0 Hz), 1.55 (4H, t, J=7.0 Hz), 3.30 (6H, s)

ANSWER:

Name ________________________________

8. For each of the following products, design a synthesis starting from benzene. (6 points) a.

SO3H

b.

Br COOH O2N

Name ________________________________ 9. Design a synthesis of compound A from benzoyl chloride and benzene. You may use any other reagents containing four carbons or less. (4 points)

O Cl

10

Name ________________________________

10. Design a synthesis for the following compound using starting materials of six carbons or less. (6 points)

CO2H CO2H

11

Name ________________________________ 11. Provide a mechanism for the transformation below. (3 points)

12

Name ________________________________ 12. Compounds A and B were synthesized by a graduate student in lab. When characterizing the compound, the graduate student discovered both A and B have the exact same melting point, boiling point, refractive index, density, and dipole moment. Provide an explanation for these observations. ( 4 points)

13

Name ________________________________ Extra Credit: Styrene reacts with aqueous sulfuric acid according to the following equation. Propose a reasonable mechanism for this transformation. (6 points)

14