N arne (Last, First, MI

):

Student ID Number:

Chern 30C, Fall 2005

Final Exam

Wednesday, December 14

Problem # Possible Points Points A warded
1 45
2 24
3 8
4 8
5 5
6 8
7 6
8 8
9 14
10 12
11 14
12 20
13 14
14 14
Total 200 ***Do not open this exam until instructed to do so*** ***Write all answers in the boxes provided***

-16 Pages Follow-

Problem 1. Draw the major product for the following reactions in the boxes provided. Show stereochemistry where relevant. For multi-step reactions give the final product only (i.e. no intermediates). Unless otherwise noted, assume 1 equivalent (1 eq.) of reagent. If the product is a polymer, draw the repeat unit and the end groups. Assume for Diels-Alder reactions that all rules and preferences are followed. (3 points each)

a.
1. Li
N
2. 0
U
3. H20 b.

2 eq. ~CN + NH3

c.

A1BN

nEq~y ,...

o

(Daw the product that results from temination I:Jy radical dlain ooupIing; be sure to include both erd groups)

d.

ethyl benzene

NBS

Problem 1 continues on the next page

1

e.

f.

H:3CO a

a

o

g.

h.

heat

(Hnt: Cope)

Problem 1 continues on the next page

2

1.

N~

1. ~,HCI, o-c

2. KI

a

heat

k.

l.

Problem 1 continues on the next page

3

m.

a

1.(~~2OJU, -78 "C

0 _

2.1-0, ~o

n.

NaBI-4

D-Galactose

o.

2. 1-10, ~O

4

Problem 2. Draw the reagent(s), intermediate or product in the box provided. (4 points each box)

a.
F
F
F
F
F
F
1 F
A1BN, heat (Draw only repeat unit; no end groups)

b.

heat

o

NaSCH2CH3 !

Problem 2 continues on the next page

5

c.

1 C12• FeCI,

6

Problem 3. In both drawings and words, explain how polyurethane foams for seat cushions, etc. are made. (8 points)

Problem 4. Two Diels-Alder adducts are drawn below. Circle the one that would undergo reverse Diels-Alder at a lower temperature. Briefly explain your answer in the box below. (Hint: Draw the diene and dienophile.) (8 points)

o

o

o

7

Problem 5. The following product was synthesized by Robinson annulation. In the box provided, draw the starting material(s) only (i.e. no intermediates) that would yield the given product. (5 points)

Problem 6. Explain why cyclobutadiene is an especially unstable molecule. Draw the molecular orbital diagram to help explain your answer. (8 points)

8

Problem 7. Which is most acidic and which is least acidic between p-chlorophenol, benzyl alcohol, and p-nitrophenol? Answer this question by drawing the structures in increasing order of least acidic (to left) to most acidic (to right) in box below. (6 points)

Problem 8. Classify the following molecules as aromatic, anti aromatic or nonaromatic. Assume all molecules are planar. For each molecule state the number of pi electrons. Write your answers on the lines provided. (8 points)

o

B H

classification:

classification:

pi electrons:

pi electrons:

9

Problem 9. The following product was synthesized using malonic ester synthesis, starting from diethyl malonate (malonic ester). Provide the synthesis. Do not show the mechanism. (14 points)

COCl-I

10

Problem 10. Provide a reasonable synthesis to carry out the following transformation. (12 points)

o

o

11

Problem 11. Starting from aniline, synthesize the following compound, using whatever reagents necessary. More points will be given for a synthesis that involve fewer steps that are higher yielding. (14 points)

CN

aniline

12

Problem 12. Below is the structure of D-Idose. Answer the following questions related to this monosaccharide. (20 points total)

CHO

H OH

a. You classify this monosaccharide as a:

HO H

HO H

H OH

b. Draw the Haworth projection and conformation representation of the a-anomer of the 6-membered ring and name the resulting structure.

Haworth projection

conformation representation

Name:

Problem 12 continues on the next page

13

c. Subject the hemiacetal above to butanol and HeI. Draw the resulting compound as and name it. Draw the a-anomer

Name: _

d. Subject D-Idose to NaB~ in water. Draw and name the resulting compound.

Name:

e. Subject the product formed in c above to periodic acid. Draw the resulting product(s).

14

Problem 13. Provide a synthesis of Ala-He starting from alanine (Ala) and isoleucine (He). Throughout the synthesis, abbreviate the amino acids as H2N-Ala-COOH and H2NHe-COOH rather than drawing out the structures. Do not show the mechanism.

(14 points)

15

Problem 14. Provide a synthesis for the following polymer starting from dicyclopentadiene and using any other necessary reagents. Make sure you account for the polymer end groups in your synthesis. (14 points)

neq.

dicyclopentadiene

16

Name (Last, First, MI): _

Student ID Number:

Chern 30C, Fall 2005 K ~ """ Final Exam

Wednesday, December 14

Problem # Possible Points Points A warded
1 45
2 24
3 8
4 8
5 5
6 8
7 6
8 8
9 14
10 12
11 14
12 20
13 14
14 14
Total 200 ***Do not open this exam until instructed to do so*** ***Write all answers in the boxes provided***

-16 Pages Follow-

Problem 1. Draw the major product for the following reactions in the boxes provided. Show stereochemistry where relevant. For multi-step reactions give the final product only (i.e. no intermediates). Unless otherwise noted, assume 1 equivalent (1 eq.) of reagent. If the product is a polymer, draw the repeat unit and the end groups. Assume for Diels-Alder reactions that all rules and preferences are followed. (3 points each)

a.

Li

1.N

2. L

b.

2 eq. ~CN + NH3

c.

A1BN

nEq~y .-

o

(Draw the product that results from temination by radical dlain CXll.4JIing; be sure to include both erd groups)

d.

ethyl benzene

NBS

Problem 1 continues on the next page

1

e.

HP04

f.

H.300 a

a

g.

o

h.

heat

(Hnt: Cope)

Problem 1 continues on the next page

2

1.

a

J.

o

k.

N~

1. ~,HCI, o-c

2. KI

heat

1.

~'C~Jl

C\

Problem 1 continues on the next page

3

m.

a

n.

NaBf4

D'Galaetose

o.

2.1-0, ~O

C Hz cH

(-t ,- ~----.-. n \-\

1\ ( --- ~---- I t

110-- H-

I I -\---- Cl~

( \17_ () t-t

2. 1-0, H;P

4

Problem 2. Draw the reagent(s), intermediate or product in the box provided. (4 points each box)

a.

F

F

(Draw only repeat unit; no end groups)

F

F

F

b.

o

F

o

heat

G

.>".

r \ ,tJ /'/

.~ I

II

o

NaSCH,CH, ~

l./ Ii

/ "'rV~/

I /

,----Ii

r> _S' ! Si

Problem 2 continues on the next page

5

c.

! CI,. FeCI3

{ L f (, lh (.) )

6

Problem 3. In both drawings and words, explain how polyurethane foams for seat cushions, etc. are made. (8 points)

;\

,Co, IV< C. i l

~' t_ •• >

. f1 L---f 4 }V1, /U. ~-! (() Z

cC( (C; tV') {-:' UJ ( :5 c)

~2 e \.,C Ct)C. C ~ (C L C_( (_1 sec:> rvv {U <I j--rl

_[1_2 _c _) ~:'V fl - F U H] . __ -} r<,l/ it2 + ( L)zl

{~{" br1t'V1' ( C: c,.C'{

Problem 4. Two Diels-Alder adducts are drawn below. Circle the one that would undergo reverse Diels-Alder at a lower temperature. Briefly explain your answer in the

box below. (Hint: Draw the diene and dienophile.) (8 points)_- -~_

/<f' -----

f

o

o

fv v r1 n ct n )

o

Q

7

Problem 5. The following product was synthesized by Robinson annulation. In the box provided, draw the starting material(s) only (i.e. no intermediates) that would yield the given product. (5 points)

-:

/ /

Problem 6. Explain why cyclobutadiene is an especially unstable molecule. Draw the molecular orbital diagram to help explain your answer. (8 points)

fh l {I IT pie, '\ (, v

I

? e

L l v' (.y\ \,..-?_ t'\.{ c)

TTl

(--. "(:' '" ~( .\ ,; i ~

I'VI. () ~> .

1/\

;) LA V-j f vI [v-r") V--fLr v; r-. S 'ie- J:-:> ~

8

Problem 7. Which is most acidic and which is least acidic between p-chlorophenol, benzyl alcohol, and p-nitrophenol? Answer this question by drawing the structures in increasing order of least acidic (to left) to most acidic (to right) in box below. (6 points)

<

Problem 8. Classify the following molecules as aromatic, anti aromatic or nonaromatic. Assume all molecules are planar. For each molecule state the number of pi electrons. Write your answers on the lines provided. (8 points)

o

B H

classification:

classification:

pi electrons:

pi electrons:

9

Problem 9. The following product was synthesized using malonic ester synthesis, starting from diethyl malonate (malonic ester). Provide the synthesis. Do not show the mechanism. (14 points)

o

I.~ '-LY <,

It

I Nc,(tf, f{ c:4

------~

J I

,,/'''' " / /' "L'

Dv'

z' /'v--/\

I ""(' <t: I I, I\.!(J..I{ t J I ' 'h

z. /~r)V

-----)

c II C I, H? D

----:3 f' 'i (~j c L/( C +

10

Problem 10. Provide a reasonable synthesis to carry out the following transformation. (12 points)

o

I. Koti --)

z. c

~:VJ~

11

Problem 11. Starting from aniline, synthesize the following compound, using whatever reagents necessary. More points will be given for a synthesis that involve fewer steps that are higher yielding. (14 points)

aniline

CN

Br

(. C C: Ll C+

11,,)°3 [----"

\t7 SD '-I

I

O'(_

12

Problem 12. Below is the structure of D-Idose. Answer the following questions related to this monosaccharide. (20 points total)

CHO

HO H

H OH

a. You classify this monosaccharide as a:

HO--f--H

H OH

b. Draw the Haworth projection and conformation representation of the a-anomer of the 6-membered ring and name the resulting structure.

conformation representation

Name: d __ ·_·- __ I~ - __ I _{_)u_'~(~)_~~J_,_r_{,_I_lr_7_~_)_~_<~ _

Haworth projection

Problem 12 continues on the next page

13

c. Subject the hemiacetal above to butanol and Hel. Draw the resulting compound as and name it. Draw the a-anomer

Name:

! :5 0 I(

y{- 0 n_. r).) f':j ./ .' -c; " d.R

IV, ''4'10>(''

d. Subject D-Idose to NaB~ in water. Draw and name the resulting compound.

Name:

(' (+1 cit

'_I (J ' I t-

t\. c) ,-4

l+c .-- 1\

II - (>H

c I~? <.: , t

e. Subject the product formed in c above to periodic acid. Draw the resulting product(s).

I)'

''Ie.

l' -c \1-2 (l1 {' ( d 7( tf 3

u

,', I, i.\ \

t \,1 J

o /'

'. Ii C ·-01+

14

Problem 13. Provide a synthesis of Ala-Ile starting from alanine (Ala) and isoleucine (lIe). Throughout the synthesis, abbreviate the amino acids as H2N-Ala-COOH and H2NIIe-COOH rather than drawing out the structures. Do not show the mechanism.

(14 points)

t.

/~ - II

L=_; (\12.-0- C·-C I

+ ~tJ - A-I (1 (DC It

I\..J -- A l(,' ( cc (1 /1

H 2 AJ -_ r l e. -- ( C (l \ 1 + C 113 c: H

c I'

- 11? i'') . r I ~ - C . ell 143

CG~-r'l\

_--

L, II

c : c. /0 - A I t\ -- C 00 H

c,

'f It- 7 {) -- r I (_ -/:l -c (( f-:> _)

Q-CHZ

11

o

\....t oJ

<:-L ( H-z - O __ ~l /,v - It I ci - ~l .-. A)- T Ie:. -t -- () ((--+"'3

L_.J {1 d

,\ I~ (3 y (1i1 (C (;, H

"

15

Problem 14. Provide a synthesis for the following polymer starting from dicyclopentadiene and using any other necessary reagents. Make sure you account for the polymer end groups in your synthesis. (14 points)

neq.

dicyclopentadiene

i1 O~' C ,____.;>

2n

+ =>.

ll'ho 0 (_ ( (~C ( 1+3

)

2" ~tt'c~

CLI.f, ,t P r\ c{o

16

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