CH310N Spring 2010 Anslyn May 12,2010 Final Examanslyn.cm.utexas.edu/courses/ch320n/Exams_files/... · CH310N Spring 2010 Anslyn May 12,2010 Final Exam Please PRINT the first three

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CH310N Spring 2010

Anslyn

May 12,2010

Final Exam

Please PRINT the first three letters ofyour last name in the boxes below.

K E YI

PRINT Full Name UT-EID _

1) (9pts)

2) ( 6 pts)

3) ( 12 pts )

4) ( 6 pts )

5) (35pts)

6) ( 8 pts)

7) ( 10 pts )

8) ( 10 pts )

9) ( 10 pts )

10) ( 12 pts )

11) ( 10 pts )

12) (10pts)

13) ( 12 pts )

Bonus) ( 3 pts )

Total Score (150 pts)

1. a) Give either the common names or the IUPAC names for the following molecules. (From notes, 2 points)

o

~OH

OH

L......---....L__i 1 _

b) Give the IUPAC name for the following molecule. (2 point)

o

CI

c) Draw the chemical structures for the following molecules. (From notes and HW, 2 points)

o ""~~J/(!.l_)

H

N-methy1-(2E)-pentenamide N, N-Dimethy laniline

d) Draw the following projections of D-ribose. For each Haworth projection, circle the anomeric carbon. (3 points)

Fischer projection of t)-riboseHaworth projection of Haworth projection of

a- D-furanoribose 13- 0-furanoribose

o \-l---Ot'\ o H OH

r{--t--OK

0\' /1-)

0\-1VI20'1r,

Ot}

2. Below are the structure and the IH-NMR of the amino acid, phenylalanine. Circle the protons that correspond to the peaks at 3.17 ppm and 3.42 ppm, and explain the.splitting pattern observed for these peaks. (6 points)

Explanation:

-rhe'S2.. V(0 to (1 <; 0 c e-IH IH

3.42 3.17 d; a') teJ<_oto ~ l c . AY'" \(, 0

0.. (\ 0') hClve. 0... Clor (c. \

C<. t \9_C lV\e"'-f\ \1"\ J l~ c, t

5H

IH, triplet

IH

IH

I I I I I I I I I I I 11 10 9 8 7 6 5 4 3 2 o

ppm

3. a) Provided are the I H-NMR spectra and chemical formula of three aldehydes (Hint: A and B react to give C, shown in 3b). Please give the structures for all three compounds (12 points)

Compound A, CSHIOO:

~M

lH, s

2H, t

1H,m

llili.

6H, d

10 1

9 I

8 I

7 I

6 I

5 1

4 I

3 I

2 1 I

o I

lH, s

2H

2H 1H

I I I I I I I I I I I 10 9 8 7 6 5 4 3 2 1 o

~

6H, d

IH, s 0

5H~H ,--A---,

IH, s / IH,m

1 I I I I I I I I I I

10 9 6 5 4 3 2 1 08

b) Given that A and B are the starting materials of a reaction which makes product C, provide the name of the reaction.

NaOEt, EtOH

Compound A + Compound B Compound C

Reaction Name:

I

4. During the last class day, Dr. Sessler introduced us to the chemical method known as the Edman degradation. Please briefly explain how this process works. What is the name of the reagent used for this process? Where in the molecule does this reagent work? What information is gained from performing this analysis? (6 points)

fei'!;x er,Jt , . \

I\ r

I "TIe- \Xl,' i ex'? - ! ' ~ rec,d~J W\\~ r; ?rU I \ 1 $(Jfh/o(t':nl.-:t~. ( (0 t: (l ))(,.1

,

bJ) r J)

} ~{\~ '{ t·) ~\lV"t(! o.c . d Or, t~r.v- N-h.i n··' flUS \ .,.)I

('~o/~,)"""

T lr, j <, eroU- >5 \ ~ (r; p(~Il"\ +e.r\

," h I tl, .·tt a.JC(VV,./'u et(,Js d,.",..J t~ lY~o(e , JT f . l '

5. Fill in the box with the appropriate reactant, reagent, or product. Some boxes require more than one step. (35 points)

a) From homework, problem 19.53d

NaOEt

+ EtOH

b) From homework, problem 24.33

<: 1. Heat

o

c) From class notes

Ao 2.

CI

-

o 0

U~

d)

o ~CN~H ~.o ----­

Heat ~011 OH OH

e) From homework, problem 16.24a

<±) Ph3P~

e

f)

o 1. c>­

~CI

-

2

g)

1) Ntx.N 1

2) L.; A(r1 ~

2) L: AI\iIf )

\4."'\0 ' 3) H'O'O er-.

N H 2 ~"::: CI ~NHI ......f-------- -------___ I~MeO .0 MeO .0 MeO .0

h) ,-----------,

o oHO~ AICI3---"~r

i) From homework, problem 20.14b Kinetic product Thermodynamic product

co +

j)

o 0r: 1. NaOEt, EtOH o ~O~V0

k)

1) From class notes

~ ~1. NaN02 ,

Hel

m) From homework, 15.12d

o°

n) From class notes

CI

¢ +

0)

~N/

I

~ ~------

a 1. ~MgBr1. LiAIH4 .. ~o~2.Hp

1. LOA Df6IH... -;f 2. Vel

-) 0 r ( ~. ,

o ~H

6. For each of the following cases, circle the side of the equilibrium which will be favored and provide a brief explanation. (8 points)

......~'__ ' __ ~_~'7""'_'.""""".";." __' __ """

o//'

+ +

H

//

17'f1Jtvr:~,in,.. of aYl!lI(\t '!c<Lt<, "lw/, 'f'~ rJ~;.'l t, 7 of ' r';l7;'i'

10"'" r " to be. cO"jv)"'kJ "ii~ I ~J rt.r., 1 '''j' 71, IC"

Spt' ( ,c (.. s s~}.. hP'h' d ,L.t.d J lJJ· rL, t ~( \ [),,~ ;)t " {:, r,I

()fbi {t; l (<,.3 ICii,>t',J fi {"{~"'\< (v('."/y:.lo,,). 'V.r7 ( J ,{ etc (\ '" I\ ,,' "i " (," J" t:» "" "r, a v' j ",: r,;, (, (Ji ~","I fW ';":: ;, if", 'k," (I,'.~.i·. 1 -, s, • ',. ",' a- ...~ t- ~nu 1 ,

J •

,t. (~, "" r- J1 , ), " \ I "":.:" ,~.;" ( \ ( ..I U-I, ,J,r·c,;l ""If.' "'''\ , '\ \ c {. ,,'y. \! " ;" ,

.. + oN

c,

r 0\

0

7. Please draw the mechanism for the formation of an enamine from the ketone and 2 amine, as shown below. This mechanism is neither acid nor base catalyzed, and proceeds with only the reagents shown. Your mechanism should include all participating lone pairs, applicable formal charges, and required arrow pushing to indicate flow of electrons. (10 points)

6 o Q

.. 6 ~ ~I~-._~ (0"

6 /C)XD~jJ? IXL/ (_. \ IL-)

\ \ /'----1­

-r,.\ : , /

,

~ .. _,.. ..,.. ,IT'"' !}

[J' '' >J (17 N., ,"'.' i

c--.__...,.....__.... ­--_.'~

u ot)

r ~

,>.,-:

,

/i

8. Using only benzene as a source of carbon, show how you would synthesize the following compound. You may use any reagent, as long as it contributes no carbon atoms to the final product. Note: you do not need to provide a mechanism for the transformations. (10 points)

o

( ,., c.J . I -.. Hw 3 ---~ > )

.A Ie! i, '.3

N;~J)·J.

Hu ' '-'--"'~ -~~ Fee

).

rl t s •. .......

! n,)

\l . YC j

i'

9. Please draw the mechanism for the hydrolysis of an amide in basic conditions, as shown below. Your mechanism should include all participating lone pairs, applicable formal charges, and required arrow pushing to indicate flow of electrons. (10 points)

(~)

,'c::.- G 0' O-f1~:O\{V "J -----)/""JJH") -(

( \ /

10. (From homework, problem 23.57) Show how you would synthesize the product, an antihistimine Histapyrrodine, using only the given starting materials as sources of carbon. You may use any reagent, as long as it contributes no carbon atoms to the final product. Note: you do not need to provide a mechanism for the transformations. (12 points)

CNH+ [::0 + 0 6,H+ • O~N:O

6 1b 1

0 r

Histapyrrodine ,~

I';' , '" .._--~, '";

(\J

, I .. /'/I)L'A",,­, if...J

\O~B{ \",i

/""\

U~ L tJ -----~_,

11. When formaldehyde is left in acidic water, it forms the dimerized product that is shown below. Please draw the mechanism for this transformation. Your mechanism should include all participating lone pairs, applicable formal charges, and required arrow pushing to indicate flow of electrons. (10 points)

•

')~H-() -\

I',.a· U ..

II . -­H-'\.f1 ~

{~,.) ,/ ''-../ ..•-­ i

U

H(} 0: -~\ \

<: \ ----~ \ '\ t­

\ I' \\., /?f

/ --~-,-~-

12. Show the steps needed to convert ethanol into the following product. You must only use ethanol as your sources of carbon atoms. You may use any other reagent needed as long as it contributes no carbon atoms to the final product. Note: you do not need to provide a mechanism for the transformations. (10 points)

o 0

./"OH A(O~

c (j \ 1

~O'\( ~~OH

o

)

~Oll >

I) ( f t j.J" on )

13. The Henry reaction, shown below, is one that we have did not explicitly cover in class, However, the mechanistic steps are similar to the ones we have seen previously for carbonyl addition. Given this information, please draw the mechanism for this reaction. Your mechanism should include all participating lone pairs, applicable formal charges, and required arrow pushing to indicate flow of electrons. (12 points)

C! fu): . 6-~­

~

NaOEt EtOH

BONUS: While gardening this last weekend, Dr. Anslyn was bitten by ants. What is the chemical compound that causes ant bites to hurt?