Sp2001 Final Organic II

200pts (Weighted as 300)

Name If you do not want your graded exam placed in the box outside my office, then please tick here Good luck (I believe in you, you can do it, etc.) and please read the questions! 1) Identify the class of compounds each of the following molecules belongs to (22.5pts).
C O O R O R R NH2

N H

R C O-H O

R C O-R O

R N C O

R C N

R C H O

R C R O

R C Cl O

R C O C R O O

R O H

R O R

R O O R

2) Circle the molecule which is most acidic (1.5pts) 3) Double circle the molecule which is most basic (1.5pts) 4) Underline the molecule, which has the most ring strain (1.5pts) 5) Put a cross through the molecule that contains the shortest carbonnitrogen bond (1.5pts)

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6) Provide one term for each reaction which describes each transformation (e.g. oxidation, electrophilic addition, elimination, etc) (16pts)
PCC (a) CH2OH (b) O R R NaBH4 CHO OH R R H

H (c)

OH

H2SO4

O (d) R Cl

OH

O R OH NO2

(e)

HNO3

O (f) R R

H2O
CH3O

OH R R OH

(g)

OCH3

(h)

O R R

HS-CH2CH2-SH S R S R

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7) The following reactions are named after their inventors - give the names of the following reactions (9pts).
(a) CH2CH2CH3

(b)

O (c)

(d) N2+ Cl

O (e) R NH2 R NH2

R' (f) R O C R R C C

R' R

8) Choose one example of an electrophilic aromatic substitution of benzene, and show mechanistically how the use of a Lewis acid helps promote the reaction (7pts).

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9) Give one advantage and one disadvantage of Molecular orbital theory (4pts).

10) State whether each of the following Molecular orbitals are overall bonding, antibonding or non-bonding (4.5pts).
(a)

(b)

(c)

11) Draw two Lewis resonance structures for an allylic cation, and show the electron movement which interconverts the two forms (5pts).

12) Indicate which one has the lowest energy (1pt).

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13) Indicate which of the following molecules are aromatic, non-aromatic or anti-aromatic. (Assume all the molecules are planar). (12pts)
+ O O

CH3 N

P N +

14) Pick one of the above antiaromatic molecules, and use the polygon rule to demonstrate its antiaromaticity. (8pts)

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15) Give the products in six of the following reactions, paying attention to regio/stereochemistry where applicable. (18pts)

OH

1) NaOH 2) CH3CH2I heat

NC

CN

Ph C CH2 Ph

mcpba

HCl

Excess HI O O

Br CO, HCl CuCl, AlCl3 NO2 1) Zn, HCl 2) NaNO2, HCl 3) CuCl, HCl CH3 Br2, FeBr3

OH

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16) The below heterocycle is 6 Hckel aromatic.

H N N

What is a heterocycle? (1pt) Explain why there are 6 electrons (3.5pts).

Would you expect this compound to undergo substitution or addition reactions? (1.5pts)

Suppose the nitrogen is deprotonated, draw the product, and state whether it is aromatic or not (4pts).

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17) Give reagents and conditions to accomplish five of the following transformations. (15pts)

A
CO2H CHO

O H

O H

CH3

CN CH2

Ph Ph H3C O H H3C

Ph Ph Ph HO H

O2N CN

O2N

CO2CH3

CO2CH2CH3

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18) Circle the stronger base in the following pairs, and in a sentence explain your choice. (6pts)
O C H2 C

(a)

F3C N H

CH3

H3C N H

CF3

(b)

O2N

NH2

NH2

19) Circle the stronger acid in the following pairs, and in a sentence explain your answer. (12pts)
(a) O H3C C OH CH3CH2 OH

CO2H (b)

CO2H

CF3

(c)

O Cl3C C OH

O Br3C C OH

CO2H (d) H3C

CO2H

CH3
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20) Name five of the following compounds in IUPAC form (14pts).

O H F O O O O Br

O O O HO

NH2 N

21) Fill in the blanks for two of the following reactions. (6pts)
NH2 1) excess CH3-Br (a) 2) Ag2O, H2O, heat O excess H3C C Cl

(b)

CH3CH2 NH2 O H3C C CH3

(c)

1) PhMgBr 2) H3O+

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22) Fill in the blanks for three of the following reactions. (9pts)

(a)

1) HNO3, H2SO4 2) Zn, HCl O C OH

1) NaNO2, HCl ? 2) H2O, Steam

O C SOCl2 ? ?

(b)

O NH2 (c) ? H3C NH ? H3C

O NH

Cl O H3C (d) CH2 ? H3C N-CH3 CH2 ? H3C NH-CH3 CH2

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23) Give the mechanism for two of the below conversions (16pts)
NH2 (a) 1) excess CH3Br 2) Ag2O, H2O, heat

(b)

CH3CH2CH2CH2Cl AlCl3 O

(c)

CH3CH2NH2 Ph H2SO4 Ph

NCH2CH3 Ph

Ph

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*Bonus question* (up to 3 points) Name 3 naturally occurring forms of pure carbon.

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