Name

ID#
TA
Chem

1128

F'inal Exam, 10:00

section

20 March 2013

This is a closed book, closed notes exam. Please write answers directly on the exam copy. Use of molecular models is encouraged. No calculators are allowed. Please print your name on all 8 pages ofthe exam. Please print the rurme of your lab TA and your ID # on page 1 only. Answers written on the backs of pases will not be accented. If you need more paper, raise your hand and a TA will bring you some.

I.

Draw the major organic product of each of the following Friedel-Crafts reactions. In each case, draw Ds at

the positions where the deuterium atoms

will

end up inthe products"

A.

OCH3 1 equivalent AlO3 + (cH3)2cDcH2cl '='-'"'- '"

Q
B.

cH3o^4nrcor8o ---+
II.
pyridine

il

lequivalentAlCg

H* Suppose you dissolve I mole of acrylic acid (CH2:CHCOOH, pKa: 4.25) and I mole of pyridine in a

Prridiniumion

litre of water. The pyridinium ion has a pKa of 5.25. Answer the following questions (please leave tlre answers
to parts A-C in exponent form):

A. what will be the numerical

value of the equilibrium constant [CHz:CHCoo. ][pyridinium] 9 [CH2:CHCOOFil hyridine] of the Brsnsted acid-base reaction, what will be the numerical value

B. Keeping in mind the stoichiometry l-ovridinium ionl ^ 4.1

of

lpyridine]

' at equilibrium?

C. What must be the hydrogen ion concentation

D. What is the pH of the solution?

III.

Use the frameworks printed below to draw 2 resonance structures for each of the following molecules. Show atl lone pairs and formal charges on the appropriate atoms and make sure that every atom has a complete

octet. All the hydrogens are already depicted in the frameworks below.

AB.

thiourea,

(HzN)2cs

*'!*
HzN

/\-

{=-*
HzN-N

H"N L\

/
HzN

>-s

The hydrazone of acetone

+------> HzN-\
cHs
CHs

cHs
c'
The enarnine formed by acetone & dimethylamine {with loss of HzO}

CH3*...N/ \
HzC'

<---*r{>

cHs-N/cHs
Hzc

,>CHs

A carbonyl groqp is often viewed as a hybrid oftrvo resonance structures, >C=O ++ >C*O tlrat have nearly equat weight. In a coqfugated ring, a carbonyl contibutes a vacantp-otbital (and

ry.

no electrons) to the ring's a-system. How many n-electrons does each of the following conjugated
systoms therefore possess

wi&in the ring ttrat is drawn? Draw a circle around the rings that should

have

aromatic character and cross out any strucfures tlrat should not have aromatic character.

-oA.# fu-electrons

of

deltic

acid

cycloperrtadienone cycloheptatrisnone

#*
oo

ooo

T-).*.fu
coni N?ffiN
H

phenazone teffazolone

uracil

in the ring

V.

Show how you would preparc 3-phenoxy'2-butanone from phenol and cis-2,3-dimethyloxirane below.

Draw the structure (including stereochemistry) of any isolable intermediate compound.

8{

fi

Fr-=qt>

ry"+'

Will yow method glve an opticalty active product? Would you expect a different final product if you ran the reaction using racemic trans-2,3'dimethyloxirane
instead?

Would the product fromthe racemic transbe optically active? Would the structure of the isolable intermediate from the trans be different? If so, draw its structure.

VII.
that

Draw the structure of Each of the following compounds has a tautome{ that ean be observed in the NMR. chirality center, draw a tautomer to the right of the equilibrium arrows. If the tautomerization creates a new

a chirality center, draw box around that center in the stucture you have drawn. Ifthe tautomerization desEoYq a

circle around it on the structure printed on the page' B.

C.
N=O
CHg
rrrrrrr;*-. {ffi

# -<ffi

VIII. The two most basic sites in isocytosine, the O and ooN, are indicated by the dashed axrows in the structure stable. Draw all the other to the left below. This problem asks you to deeide which conjugate apid ion is more Similarly, draw all the resonance stucflres for the O-protonated ion that have complete octets on evory atom. atom. Which ion has other resonance stnrctures for the J{-protonated ion trat have complete octets on every
therefore be the morc stable' more resonance structures? Circle the conjugate acid ion ptinted belou, that should

isocytosine

tr;f
H

o*'

A* It*ANHz
H

oHr

.L

o
or

-ANH+

(*ANHz
H

O-protonated

N-protonated

IX. SYNPT]ZZ
A.
*E--+--f> -#*r--{> s--s-{>,
OCH3

a) NatsHalmethanol b) Cr03/water & acetone c) (CHslsCCOCl, AlClg d) HOCH2CH2OH, acid catalyst e) PhPt* CHe-

ryoH
B.

f) Mglether
g) (GHslzC=O, then mild acid h) HNO3, H2SOa

+-,
C.

r--*-+!'-----+--*-{>

i) P0Cl3/pyridine

i) (HzN)2C=$, then HzO

k) H3o*

U OsOa
rn) Base, then CH3Br

OH
I

n) PBrr

X. According to the literature, the specifically deuterium labeled allyl phenyl ether A, has not yet been made.
However, both CD:I (deuterated iodomethane) and 2-phenoxyacetaldehyde are cofitmercially available.

A..Describe how you would prepaxe A from those two commercially availabte starting materials. B. Draw the product expected from a thermal Claisen reamangement of A, showing the specific position(s) where deuterium should be found.

C. Show how you would convert A

and the aforementioned starting materials to compor.ud

B. All

the cmbon

atoms must come from &e designated starting matedals.

xI.

Draw the structure of the major product of each of the 3 fotlowing reactions of phenylacetonitile. There are 4 IR spectra below. One corresponds to phenylacetonitrile, while the other 3 corrospond to the products. Matoh ths letter of the correspondiag IR spoctrum hlow to tlre starting material or t to the products you have drawrr Assign tlre bands in tlr IR spectra above 1?00 cm marked with an

to the appropriate functional groups.

CH3MgBr_
then HsO

Abase then H.O+

GCHzCN
phenylacetonitrile

{*'
LiAHN

Gas phase lR

?ilfiO r 3ftilS lrtffr*hrerturrt,t*er mt- 'L

{c

3***

ffi fi m Fft :S 'fiffi ?*** 3#*ff tffav#fiurrl*er {cm*13

Lfi**

ffitt,

,ffifuffi.&* t#&

3t)fiff

=*fi{} f c m* r l l*Hauerlurr'ther

f_

{},{3{}

XII.Thisprob1emdealswiththeregiochemistryoftheDie1s-A1de':":,Yl,^:'::'::"P in the following questrons'

il;il;;ntially?).

Do not worry about stereochemistry

r*o'
L_r

OR

Diels-Alder Product structure to be completed above, making certain that every r-alkoxybutadiene the for structures resonance A. Draw 2 other the specific atoms that carry them' sure to show formal charges on Be octet. complete a has atom printed above that the l-alkoxybutadiene sffucture of 4) position or 1 (position the carbon

B. circle

end' should correspond to the more nucleophilic (H2CdIII'{O', were to proceed by making with nitroothylene reaction Diels-Alder c. suppose the the neutrar structure in the middle of the page above, draw framework the using time. a at bond one between the alkoxy the + and * charges are disffibuted how indicating stable, most that would be the has a complete octet' please make certain that every atom Again, groups. nito the and should result when the draw the constitutionar isomer that above, right far the to D. using the framework completes the Diels-Alder reaction' formation of the second c-c bond drawn below. Draw another resonance 2-alkoxybutadiene the of reaction Diels-Alder E. consider the in which every atom has a complete octet' structure for the 2-alkoxybutadiene that should the 2-alkoxybutadiene structure below of 4) position or 1 (position F. Circle the carbon end' correspond to the more nucleophilic

G.SupposetheDiels.Alderreactionwithnitroethyleneweretoproceedbymakingonebondatatime. that would be the

sffueture of the page belowo draw the neutral Using the framework in the middle and the nitro groups' are distibuted betweenthe alkoxy charges + and the how most stable, indicating that should result when the below, draw the constitutionar isomer right ftr the to framework the H. using completes the Diels-Alder reaction' formation of the second c-c bond

r*o'
L-

----------d>

*o\
Diels-Alder Product structure to be compteted below' Neglect stereo2 intramolecurar Diels-Alder reactions the of each from product major I. Draw the chemistry
internal

W'

internal Dlels-Alder
-,4>'

t/

t-oR

VI.

EIMS, IR, and NMR of unknown molecule X are reproduced below. If one mole of this compound is

reduced with

LiAllI+ in ether,

one mole of each of two products, Y and Z, is recovered whose mass spectra

are also reproduced below.

A. Identiff X, Y, andZ. Assign the resonances in the proton NMR B. Draw structures for the base peak of each of t}e 3 EIMSs.

of X between 1 and 5 ppm.

f;[Imwexffi
!

o-l*---r--

1?* rftlr

1#*

3*il

{frsx

isg*xffiffir

tffi ffif }f,

3**{}
\fifm\ren
ff*rfu*rr HffiH ef 3t

3**{}
[,J ilYx

Lpsr {c ryr*

1fifi*
33

HilffiS of Y

Htil$S nf E

.,1.,,r1,,1

,ll,lt
ffilfr

,ll
4* rfift
5$

4*

.Efi

1?*

?*

3*