topic 13: i-clicker slides beauchamp 1 nomenclature...

Topic 13: i-Clicker Slides Beauchamp 1

a. 1,2-diamino-5,11-dioxo-6-isopropoxy-7-hydroxy-9-cyanoundec-3E-en-1-one

b. 3-cyano-5-hydroxy-6-isopropoxy-7,11-dioxo-10,11-diaminoundec-8E-enal

c. 2-amino-5,11-dioxo-6-(2-methylethoxy)-7-hydroxy-9-cyanoundec-3E-enamide

d. 2-(2-oxoethyl)-4-hydroxy-5-(1-methylethoxy)-6,10-dioxo-9,10-diaminodec-3E-enenitrile

e. No entirely correct answer is provided

H

O C

N

O

O

O O

NH2

NH2

H

Nomenclature Question

Q-1:What are the likely reactions of the following carbocation?

C

H3C

CH3

C

H

CH3

a. additionb. eliminationc. rearrangementd. a & b & ce. a & b

Notes: pp 1-5

H

C:\Documents and Settings\psbeauchamp.WIN\My Documents\classes\315\i-clicker questions\Topic 13 Carbonyl (C=O) i-Clicker Slides for pdf.doc


Q-2:What are the likely reactions of the following carbocation?

Notes: pp 1-5

C

H3C

CH3

C

H

O

a. additionb. eliminationc. rearrangementd. a & be. resonance

H

H

Q-3:What are sites of partial positive polarity?

C

H3C

CH3

C

C

C

C

O

H

H12

34

56

7

H H

H

Notes: pp 1-5

a. 2,3,5b. 2,4,6c. 1,3,5d. 1,2,4,5e. 1,2,4,6



Q-4:What is the best orbital to receive electronsin and the best orbital to donate electrons from?

Notes: pp 3

σ∗CH

σCH

n2n1

πCO

σCC

σCO

σ∗CC

σ∗CO

π∗CO

donate accept from intoa. πCO π*

CO b. n1 or n2 π*

CO

c. σCO σ*CH

d. σCH σ*CH

e. σCC σ*CH

C

H

HH

C

O

H

MO's of ethanal

Potential Energy

Nuclear Charges

Q5: How many different products can form inthe following reaction (include stereoisomers)?

Notes: p 5

ClD

a. 2b. 4c. 6d. 8e. 10

?



Q6: Which of the following are isomers, stereoisomers (diastereomers, enantiomers)?

ClD

a. (1,7) (1,2) (3,4)b. (4,5) (1,4) (6,7)c. (3,5) (1,7) (1,2)d. (3,7) (2,3) (7,8)e. There is no answer provided with all parts correct.

D

Cl

H

H

H

H

D

Cl

D

H

H

Cl

H

Cl

D

H

Cl

D

H

H

H

H

Cl

D

H

D

Cl

H

Cl

H

H

D

1 2 3 4

5 6 7 8

isomers (not stereoisomers) diastereomers enantiomers

Only selected answers are provided, not all possible answers.

Notes: pp 5



Q7: What is a reasonable sequence of steps for a carbonyl reaction in acid?

Notes: pp 4

C

O

CH OH CH3

C

O

CH

O CH3

H

C

O

C

H

C

O

CH

H

O

H3Celimination product

additionproduct

C

O

CH OH CH3

C

O

CH

O CH3

H

C

O

C

H

C

O

CH

H

O


additionproduct

C

O

CH O CH3

C

O

CC

O

C

H

C

O

CH

H

O


additionproduct

C

O

CH OH CH3

C

O

CH

H

C

O

C

H

C

O

CH

H

O

H3Celimination products

additionproduct

a

b

c

d

e. None of the above is a reasonable carbonyl reaction sequence in acid.

H

O CH3

H

H

O CH3

H

OH CH3

H

H



Q8: What is a reasonable sequence of steps for a carbonyl reaction in base?

C

O

CH OH CH3

C

O

CO CH3 C

O

C

H

C

O

CH

H

O


additionproduct

C

O

CH OH CH3

C

O

CH

H

C

O

C

H

C

O

CH

H

O


additionproduct

C

O

CH O CH3

C

O

C

C

O

C

H

C

O

CH

O


additionproduct

C

O

CH OH CH3

C

O

CH

H

C

O

C

H

C

O

CH

H

O

H3Celimination products

additionproduct

a

b

c

d

e. None of the above is a reasonable sequence of steps for a carbonyl reaction in base.

O CH3

H

H

O CH3

H

OH CH3

H

H

H

H

O CH3

O CH3

Notes: p 6



Q9: What is the expected order of reactivity with nucleophiles?

H3C

C

H

O

H3C

C

CH3

O

H3C

C

Cl

O

H3C

C

O

O

H3C

C

N

O

CH3CH3

CH3

1 2 3 4 5

a. 5 > 2 > 4 > 1 > 3

b. 3 > 4 > 1 > 5 > 2

c. 5 > 1 > 2 > 4 > 3

d. 3 > 4 > 2 > 1 > 5

e. The correct answer is not provided.

Notes: pp 7-8

Q10: Which are tautomers of the given structure?

N

O

H

OA 1 2 3

N

O

H

O

N

O

OH

N

O

O H

Possible TautomersComparison Structure

a. only 1

b. only 2

c. only 3

d. 1 and 2

e. 1, 2 and 3

Notes: p 8



Q11: What are the expected products in the following reaction?

a. only 1

b. only 2

c. only 3

d. only 4

e. only 2 and 3 (racemic mixture)

H3CC

O

H

1. LiAlH42. D3O+ / D2O

CH2

C

O

HD

H3CC

D

O

H

H

H3CC

H

O

D

H

H3CC

H

O

H

D

1 2 3 4

Notes: pp 9-11



Q12: How do the following reactions compare?

H3CC

O

H

H3CC

O

CH3

H3CC

O

OCH3

AlH3H

Li Na

BH3H

H3CC

O

H

H3CC

O

CH3

H3CC

O

OCH3

AlH3H

Li

AlH3H

Li

Na

BH3H

Na

BH3H

a. All of the reactions work and deliver 1 equivalent of hydride.b. All of the reactions work and reactions 1,2,5 and 6 deliver 1 equivalent of hydride and reactions 3,4,7,8 deliver 2 equivalents of hydride.c. All of the reactions work and reactions 1,2,4,5,6,8 deliver 1 equivalent of hydride and reactions 3 and 7 deliver 2 equivalents of hydride.d. Reactions 1,2,4,5,6 and 8 deliver 1 equivalent of hydride, reaction 3 delivers 2 equivalents of hydride and reaction 7 does not work.e. No answer above is completely correct.

O

AlH3H

Li ONa

BH3H

2. workup

2. workup

2. workup

2. workup2. workup

2. workup

2. workup

2. workup

1

2

3

4

5

6

7

8

Notes: p 12



Q13: What are the expected products in the following reaction?

a. only 1

b. only 2

c. only 3

d. only 4

e. The correct answer is not shown

1. LiAlD42. H3O+ / H2O

1 2 3 4

H3CC

CH2

O

H3CC

CH2

O

D

H3CC

CH2

O

H

H D

H3CC

CH2

O

D

D

HC

CH2

O

D

H

H HH3C H H

Notes: p 11

Q14: Which PE vs. POR diagram goes with each reaction?Energy Picture 1 Energy Picture 2 Energy Picture 3

A

A*

B

B*

A

A*

B

B*

A

A*

B

B*

Progress of Reaction

Potential Energy

Progress of Reaction Progress of Reaction

Potential Energy

Potential Energy

O

OH

H3O+

H2O

O

O

O

O

H2O

1

2

3

4

OH

H2O

O

H3O+

OH

H2O OH

O

OH

5

6

7

8

OH

H2O

O

HO O

HO OH2

OH

OH H2O

OH3O+

O

H2O

a. PE/POR diagram 1 = (1,2,3,4) / PE/POR diagram 2 = (5,6) / PE/POR diagram 3 = (7,8) b. PE/POR diagram 1 = (1,2,7,8) / PE/POR diagram 2 = (3,4) / PE/POR diagram 3 = (3,4) c. PE/POR diagram 1 = (1,2,5,6) / PE/POR diagram 2 = (3,4) / PE/POR diagram 3 = (7,8) d. PE/POR diagram 1 = (7,8) / PE/POR diagram 2 = (5,6) / PE/POR diagram 3 = (1,2,3,4)

Notes: pp 13-16



Q15: What is the order of reactivity (1=fastest)?O O

H

a. 3 > 2 > 4 > 1 because of resonance, inductive and steric effects

b. 1 > 3 > 2 > 4 because of resonance and inductive effects

c. 2 > 4 > 1 > 3 because of steric and inductive effects

d. 1 > 3 > 2 > 4 because of steric and resonance effects


1 2 3

1. NaCN2. slow addition of acid

O

4

O

Notes: pp 18-19

cyanohydrins

CR R

O C

NH

Q16: What atom reacts first when laetrile breaks down in acidto form cyanide?

O

O

O

HO

HO

HO

OH

HOHO

OH

O

C

N

a

b

cd

e H-X(acid)

O

H

CH Nlaetrile

hydrogen cyanide

benzaldehyde

sugarH2O

Notes: pp 19-20



Q17: Match the correct reaction conditions with itsproper reaction?

a. reaction 1 = viii, reaction 2 = v, reaction 3 = vi, reaction 4 = ii, reaction 5 = i

b. reaction 1 = ix, reaction 2 = vi, reaction 3 = v, reaction 4 = ii, reaction 5 = iv

c. reaction 1 = vii, reaction 2 = i, reaction 3 = vi, reaction 4 = iv, reaction 5 = iii

d. reaction 1 = ix, reaction 2 = ii, reaction 3 = v, reaction 4 = iii, reaction 5 = i


1

2

3

4

5OH

O

H

O

OH

1. NaNR22.

1. R2BH2. H2O2 / HO

H2SO4H2O / Hg+2

H2 / Pdquinoline

H2 / Pd Na / NH3

O

O

H

O O1. NaNR22.

1. NaNR22.

1. NaNR22.

i iiiii iv

v vi vii viii ix

3. workup 3. workup3. workup 3. workup

Notes: p 21



Q18: Identify any mechanistic steps where errors occur?

O

H

H O

H

H

H O H

1

O

HH

2

C

O

HH

C

4

H

H O

H

H

H2C CH

H

HH2C C

H

H

H

7

5

OH

H8

CH2

OH

H O H

H O

H

H

9

C

OH

H

H

H

C

OH

H

H

HC

O

H

H

H

11

H O H

H O

H

H

a. steps 3, 7, 9b. steps 2, 5, 11c. steps 4, 6, 10d. All steps are correcte. The correct answer is not shown

3

6

10

Notes: p 21



Q-19 How many errors are present in the following mechanism?

Li Li Li LiLi metal

BrR

hexane Li Li Li

BrRLi

BrR

Li

Li Li Li Li Li

Li Br

R

Li

a. 0-1 b. 2-3 c. 4-5 d. 6-7 e. >7

Q-20 How many different R-Br compounds can be made from the following alkanes (in one reaction)?

CH4

a. 6 b. 7 c. 8 d. 9 e. >9



Q-21 How many different R-Br compounds can be made from the following alkenes (in one reaction)?

a. 6 b. 7 c. 8 d. 9 e. ≥ 10

Q-22 How many different R-Br compounds can be made from the following alcohols (in one reaction)?

H3C OH OH

OH

OH

OHOH

OH

OH

OH

OH

OH

a. 6 b. 7 c. 8 d. 9 e. ≥ 10 C:\Documents and Settings\psbeauchamp.WIN\My Documents\classes\315\i-clicker questions\Topic 13 Carbonyl (C=O) i-Clicker Slides for pdf.doc


Q-23: How many different carbanions can potentially be made from the starting molecules (after an appropriate number of steps)? Include ALL different possibilities.

CH4

a. 9-10 b. 11-12 c. 13-14 d. 15-16 e. ≥ 17



Q-24: How many bonds represent a reasonable carbonyl (C=O) disconnection strategy?

HCH2C

H H

C

H

O

H

C

H

H2C

H

HC

CH3

CH2

H1

2

3

4

5

6 7

8

9

10

11

12

1314

a. 0 b. 1 c. 3 d. 4 e. ≥ 5

Q-25: How many bonds represent a reasonable epoxide disconnection strategy?

HCH2C

H H

C

H

O

H

C

H

H2C

H

HC

CH3

CH2

H1

2

3

4

5

6 7

8

9

10

11

12

1314

a. 0 b. 1 c. 3 d. 4 e. ≥ 5



Q-26: How many bonds represent a reasonable R-X / organolithium coupling strategy?

HCH2C

H H

C

H

O

H

C

H

H2C

H

HC

CH3

CH2

H1

2

3

4

5

6 7

8

9

10

11

12

1314

a. 0 b. 1 c. 3 d. 4 e. ≥ 5

Q-27: How many “fatal flaw” steps (wrong steps) are present in the following reaction sequences? Each arrow represents a different synthetic step.

Cl2 / hνCl

1. Li 2.H2C O

OH

CrO3H2O

H

O

Br2

Br

O1. Mg2.

3. workupOH

CrO3pyridine

OH

O

1. BH32. Br2/CH3O

Br1. Mg2. O

3. workup

OH

HBr

Br

1 2 3

4 5 6

78 9

a. 0-1 b. 2-3 c. 4-5 d. 6-7 e. ≥ 8



Q-28: How many reasonable strategies could be used to make the target molecule (TM)? More than one step can be used.

OH

TM

aldehyde +RBr / Mg

ketone +RBr / Li

ester +LiAlH4

ester +RBr / Mg

aldehyde + alkyne

ketone +alkyne

epoxide +RBr / Mg

epoxide +LiAlH4

SN1 SN2 alkene

?

a. 0-1 b. 2-3 c. 4-5 d. 6-7 e. ≥ 8



Q-29: How many nitriles below could be prepared using a SN strategy and RX compounds?

H3C C N CN C

N

CN

CN

CN

CN

CN

CN

CN

a. 0-1 b. 2-3 c. 4-5 d. 6-7 e. ≥ 8

Q-30: How many proton transfers are needed to workup the reaction to the indicated products?

CR R

N

OH

H

HC

R R

O

NH

H

H

H

2. workup

intermediate from reaction of nitrile + Grignard

OH H

a. 3 b. 4 c. 5 d. 6 e. ≥ 7



Q-31: How many errors are in the following mechanism?

H3CCH2

CN

CCH2

CH3

NOH

H

H

2. workupOH HCH3Li

H3CC

CH2

CH3

N

H3C

H

OH

H

H

CCH2

CH3

N

H3C

HH

OH H

CH2C

H3C NH2

CH3

OHHOH

H

CH2C

H3C NH2

CH3

OH

CH2C

H3C NH3

CH3

OH

CH2C

H3C

H3N

CH3

OH

OH2H

CH2C

H3C

CH3

OH

CCH2

CH3

O

H3C

O H

H

OH2H

H2O H

a. 0 b. 1 c. 2 d. 3 e. ≥ 4



Q-32: Use the same 1st step for all reactions = Mg, and same last step = H3O+/H2O. Only the 2nd step (electrophile) is different in each reaction (shown). How many answers are wrong?

Br

Br

1

2

1 2Possible Products

2. O

H

O

O

OCH3

O

C OO

CH3C N

Br

2.

2.

2.

2.

2.

2.

OH

OH

OH OH

OHHO

OH OH

OH

O

OH

O

OO

a. 3 b. 5 c. 7 d. 11 e. not given



Q-33: How many starting combinations could lead to a reasonably good yield of the product shown (within 2 steps)?

OH

BrO

Br

Br

O

H

O

O

OH

O

Br

H

O

Br

H2O

11 2 3 4Product

5 6 7

a. 2 b. 3 c. 4 d. 5 e. ≥ 6

Q-34: How many starting combinations could lead to a reasonably good yield of the product shown (within 3 steps)?

OH

Product

Br

and

Br OH

OO

H

O

O

One of these.

a. 3 b. 4 c. 5 d. 6 e. ≥ 7



Q-35: What would be the most straight forward approach to the following target molecule?

O

TM

*

Br

CH2

OBr

OHH3C OHH3C

*

*

*

aNaCN

bBr

Br

cBr

d. All are similar.e. None are workable.

Q-35: Which oxygen is most likely to react with thionyl chloride, in the mechanism to form an acid chloride?

O

OH S

O

Cl Cl

a

b

O

Cl

SO2 HCl



Q-37 How many of the following combinations will lead to the indicated target molecule within 2 synthetic steps?

O ? CN

H3C

CN

Br Br

O

H

Br

CH3Br

Br

O

H

Br

1 2 3 4

5 67 8 9

10

Target Molecule

CN

Br

Br

NaCN

a. 1-2 b. 3-4 c. 5-6 d. 7-8 e. 9-10

Q-38 Starting from the given molecules, which approaches could lead to the target molecule?

Target MoleculeOH

* *

a. 1C + 1C + 1C + 1C + 1Cb. 2C + 1C + 1C + 1C c. 3C + 1C + 1C d. 2C + 2C + 1C e. any of the above could work

Starting Molecules: CH4, CH3CH3, CH3CH2CH3, *CH4



Q-39 How many of the following molecules could be made using a 3C+1C+1Cstrategy?

OH

*

a. 1 b. 2 c. 3 d. 4 e. No correct answer


OH

*

OH

*OH

*

Target molecules1 2 3 4

Q-40 How many of the following molecules could be made using a 2C+2C+1Cstrategy?

OH

*



OH

*

OH

*OH

*




Q-41 How many of the following molecules could be made using a 3C+2Cstrategy?

OH

*



OH

*

OH

*OH

*




Q-42 How many errors are in the given ketalization mechanism, used to protect aldehydes and ketones?

OTsHO

H

HO

RO

H

OH

OH

O

OTs

ketoneOH

OH

HO

OH

O

HO

TsO HOH

O

HO

H

OH

O

HO

H

O

ethylene glycol

HO O

RO

H

O O

ketal

remove H2O

OH H

a. 2-3 b. 3-4 c. 5-6 d. 7-8 e. ≥ 9
