: ~~,m~~¥Jlu , ~tt-~M~,ta , .tt.~~·~ ' •ti' 1t~ 0

~ PlT JJI #JI.Ji1] : !!.. ~t4* FfG ~f.JL

f4 El 1\ ~~ : 0502

:t ti\ f4 El : 1f fik1c*

1. -~W$.4(~)i~$~ff~,ff§~~k~~~ 0

2. ~$t~~*~~Mfy~~*,ff*+•~~AJA~,~~ff-t-*M ~M;t o

3. ~ 1- ftl--(f.$ #-4i;tJ "te,r rm il:f:.~ ¥o1f $ J(& F\J 1f $' ll-~ oJ"":f ~ :kl~ '

*~•~~~~$•Y~~~~~~#~ o

4. $ #- 4ffl tt~1l-t->"t/Ja ~ 0

5. $#-4oJ""ffl~M:f~i~~$,*A%~M4mffi, •• ;~m•~~ ~~:f~;$#-~~ffl2B~-•~;~•~~*C¼**~~•u) •~•Mtt••*fflffi$#-¼,~~*-#m~!i§ffi• 0

6. ~ ~ J.t ~ JJt ~ 11 , l!)Jt 4 J.f. 1l Jo )t % i( , -tt § 1t·ft M 1it ~ ff BA i r II .tL ~

•*•~••~a•••~•*J'•*~*~Mtt~~$a:t•~t * f 1J BA ITTJ ti* j;a ti} 0

~ JI.*•*~ 109 ~~&,t~ ±J)l~"t~A~t~~

* PIT JJI fli Ji1J : ±. -4r # * fil C:.. fli , T fli

~t;'(.f4 El ( 1t~~) : ;!f il1t.~(0502 , 0706)

#_1_1 _J , i_I_J Part 1 AA ~,11! (70%) 1. Show how the following compound can be prepared from the given starting

material. Draw the structure of the compound that is formed in each step of the synthesis. (5%)

H-==-H 0

fa-.,,,/ 2. Given the reaction coordinate diagram for the reaction of A to form G, answer the

following questions: (11 % )

>, O'l ... a, C: a, a, a, L.

u.. A

B

Progress of the reaction

a. How many intermediates are formed in the reaction? b. Which letters represent transition states? c. What is the fastest step in the reaction? d. Which is more stable: A or G? e. Does A or E form faster from C? f. Which is the more stable intermediate? g. What is the reactant of the rate-determining step? h. Is the first step of the reaction exergonic or endergonic? i. Is the overall reaction exergonic or endergonic? j. Which step in the forward direction has the largest rate constant? k. Which step in the reverse direction has the smallest rate constant?

3. Explain why 2,3-pentadiene is chiral. (4%)

4. Write the appropriate reagent over each arrow. (12%)

CXOH

OH

l show 2ways

G

CXOH cx·•'~OH

•-,,,,OH+ OH

~ _IL ~t * _k * 109 *-if-It_ ,z;~ ± J)I 3lf-t~A * t~~ * ?IT J)I i1U}1j : 1.. ~ # * flt. Z:. #JI. , T #Ji

;;ift~# El ( 1~i.~): :tf~1t.*(0502, 0706)

#_ll_]l • J_2_]l *tk-tf_ [ $*% ] 1"fc$

5. An unknown compound, L, has the formula CsH1002. Elucidate the structure of L . by scrutinizing its IR, 1H NMR and 13C NMR spectra, shown below. (6%)

I OC)

4000

3.5 3.0

N

"" __, 0

3000 W b ( I) 2000 · avenum ers cm·

2.5 2.0

I

L5

00 00

J-LO

I 11

ppm

"'''''I""" ·"I"' .... " I' """ "I ...... .. ;., .... "'"I"' ""' "I',.,; .. "I ' "' IH"I"" ' "' 'I' ..... ... , .. .. . "' T"'"" 'r' "'·' " ' I'"" .... I" ' " "" ' 1" """' I""""' I

170· 160 150 140 130 120 110 JOO 90 80 70 60 50 40 30 20 ppm

~SLm-.f-A* 109 *~,oci~±JJI~t~A*t~~ * PlT .f)I jJI. >31

] : 1.. -fp--ft * ~fc. 0 jJI. ' T jJI.

J;-tJ,fl- § C 1-t?;.!!i): :Jf ~l1t.~(oso2, 0706)

#_1_1 _J{ • J_3 _J{

6. Are the following pairs identical, enantiomers, diastereomers, or constitutional isomers? (12%)

a. p ,,,, Br Br

and ~ Br Br

e.

b A ___ and ... A

· B~~Br Bt~Br

r--------T'-cl f, c1--L---J and

g.

H CH3 \ I C=C and

I \ CH3 Br

h.

Br CH3 \ I C=C and

I \ H CH3

7. Indicate the reagents needed for the following multistep transformation. (5%)

OH

8. Starting with benzene, toluene, or aniline and any other required reagents, outline a synthesis of each of the following: (15%)

(a) CH3 (d) 0 0

H

~N (Eor Z)

(Eor Z)

(b)°' I . /? o/'-.........

(e) 0 vrDH (c) Br (E or Z )

c,-Q Br

~ SL ~W * ;k ~ 109 ~ _ff=-li_ i~ ± J)I~t~A ~ t~;;'J!

~ PJT J)I t1Uj1J : 1-~ft$ /I1f, 0 fli , T fli

~-t~ft El ( 1t~~) : ~ ;tl1t.$(0502 , 0706)

#_ll_Ji , J_4_ Ji

Part 2 -'l!:11 (30% , 1.5% each)

1. Which of the following resonance structures is not a significant contributor to the hybrid for the carbonyl group?

\ ·. \~ ~ C=O C-0

I ·· I ·· \ (±) ~ c-o:

I I II III

a) I b) II c) III d) Neither II nor III is important. e) All are significant contributors.

2. The following transformation would be considered a(n)?

Br

a) Reduction b) Oxidation c) Addition d) Elimination e) Rearrangement

3. Which of these molecules is not expected to arise as a product of the high temperature chlorination of methane?

a) CC14 b) HCCb c) CH2Ch d) CH3CH3 e) CH2=CH2

~SL5t*:k~ 109 ~iJ:-&i~±JJI~t~A.~t~~

im*•m=~• #~~~•,T• ~t~# El ( 1~~~) : 1f -1l1[:;~(0502 , 0706)

#_1_1 _Jf , J_5 _Jf

4. The IUPAC name for 1s:

a) 6-Ethyl-3,4-dimethylheptane b) 2-Ethyl-4,5-dimethylheptane c) 3,4,6-Trimethyloctane d) 3,5,6-Trimethyloctane e) 2-(1-Methylpropyl)-4-methylhexane

5. What is the name of this compound?

a) Bicyclo[2.2.2]octane b) Bicyclo[3.2.l]octane c) Bicyclo[ 4.1.1 ]octane d) Bicyclo[ 4.2.0]octane e) Bicyclo[3.3.0]octane

6. The most stable conformation of 2,3-dibromobutane, viewed through the C-2-C-3 bond:

Br*CH3 H

Br H CH3

I

a) I

II

b) II c) III d) IV e) V.

~iL5¼%A* 109 *_ff=-J.ii~±JJI~t~A*t~il! ~ PIT J)I fJi ] 1] : 1:. 4rfl-~ rfc. G fJi , T fJi

~ti(.t4 El ( 1~Z.~) : ~ ~1t.~(0502 , 0706)

#_ll_Ji: , ~_6_1i:

7. Which of the following compounds contains polar covalent bonds? a) CS2 b) LiF c) F2 d) CH3F e) None of these choices.

8. What functional group(s) is/are present in the following compound?

rNCH3

0~

a) ether and 2° amine b) ester and 3 ° amine c) 3° amine d) 3 ° amine and ether e) None of these choices.

9. Which compound would have the highest boiling point?

a) CH3CH2CH2CH2CH2CH3 b) CH3CfuOCH2CH2CH3 c) CH3CH2CH2CH2CH20H d) CH3CH20CH(CH3) 2 e) CH30CH2CH2CH2CH3

10. The IR spectrum of which of the following substances is likely to show a small, but sharp peak at 2200 cm-1 ?

OH

~

I

/'N/'-.../ H

II

.,,,,,o-...../'-../

III

~ IV

\,..__ ________

a) I b) II c) III

V d) IV e) V.

* f'tr J)l fJI. )i1J : !!.. 4f t4 ~ ~tf. l. fJI. , T fJI.

~t~f4 § ( 1\i.~) : ;Jr ~1G~(0502 , 0706)

¥--_ ll_Jf , J_7_Jf

11. What is the conjugate base of ethanol?

a) CH3CH20 -

b) CH3CH2-

c) CH3CH20H2+

d) CH3CH3

e) CH30CH3

. 12. What is/are the product(s) of the following acid-base mechanism?

0 ~~/ H I ---

H H

0

Liffi H + + (CH3)iNH

8CH3

a)

e) None of these choices.

~t~# El ( 1\i.~) : ;Jr il1G~(0502 , 0706)

# _ ll_ J , J _8_J 13 . In the molecular orbital model of the cyclobutadiene, how many pairs of degenerate

n-bonding molecular orbitals are there?

a) 1

b) 2

c) 3

d) 4

e) 0

14. What would be the major product of the following reaction?

CN

25°C

I II

III IV

a) I

b) II

c) III

d) IV

e) Equal amounts ofl and III.

~t~# El ( 1-~i.~) : if :¥~1t.~(0502 , 0706) #_ll_ ]i , J_9_1i

15. What would be the major product(s) of the following reaction?

~ ~Br

0 ,p

I II III

a) I

b) II

c) III

d) IV

e) None of these choices.

0 IV

16. Predict the splitting pattern you would observe for the proton at Cl of 2,3-

dimethyl-2-phenylbutane.

a) Doublet

b) Singlet

c) Quartet

d) Septet

e) Octet

#_1_1 _J , J_l _O _J

17. For the following compound how many different signals would you see in the

proton NMR? (Assume that you can see them all.)

a) 1

b) 2

c) 3

d) 4

e) 5

18. Which of the following structures contribute(s) to the resonance hybrid of the

intermediate formed when acetanilide undergoes para-bromination?

:NHCOCH3

¢ H Br

I

a) I

b) II

c) III

d) IV

e) All of these choices.

+¢COCH3

H Br

III

¢:OCH, H Br

IV

i PIT J)I #JI.]1] : ± 4(;f4 $ Fi£ 0 #JI. ' T #JI.

~t~f4 § C 1·t?;.~) : 1f :¥l1c$(0502 , 0706)

~ _ 11_1{ , J _ll_J{

19. The electrophilic bromination or chlorination of benzene requires, in addition to the

halogen:

a) a hydroxide ion.

b) a Lewis base.

c) a Lewis acid.

d) peroxide.

e) ultraviolet light.

20. Which of the following pairs of compounds could be used as the basis for a Diels­

Alder synthesis of the compound shown below?

0 II m

oy N

0 V

IV

a) I

b) II

c) III

d) IV

e) V