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NAME: .

~
ANSWER ANY FIVE OF THE FOLLOWING QUESTI S. ALL QUESTIONS CARRY

EQUAL POINTS. ANSWER IN THE SPACE PROVIDED.

CHEM 143 FIRST EXAM OCTOBER 20, 2009

1. (a) The heat of formation of cyclohexane, cyclohexene and benzene are, respectively, -29.S, ­
1.1, and +19.8 K. cal/mole. Estimate the resonance energy of benzene using this data. A

H.2. 4 U,.. - ~ N-f (JyDJ"1


...,J -
- L.11-1('RI,.,.a-*t1,
o cJ~ 0 ~U~J -= -~q. 5' - (-1./) -=:. - ~<g. 4- K· ~\Mu(..
r(;J W '1, /.j J..yo Y"".J.' t1VI ;1k• .J.J. ~ : - ;H? '4 >< 3 -:. - 'g., . J.
II • • : M ~<t1 l..d.yt)~"l-ld>l "l O!4: {d-J.J..J v.. I..)k.<.,
rr4W.c.v~ I (.; b "'-7) ~/ ~
l~
t.Jd .3 #2
c.J-~
.~
'--J !: -:2. ~. ~ -
Jel 8
t •
_ -lfr.3 k· ./~ -', \
(AG~ vc.Lw./

:. &<NI4MUl ~1 ~ :: -ft£·;} _(_'f1.3) = -"i;:~


(b) Arrange the following compounds, within each set, in the increasing order of their heats of

y( " I h~k k ~Dl.- ~do


T /.>ol"f-~ ~ ~. d.,...J,,~' Low.A
J.",J,!... 'o~kw.:t&- ~ C''''Jl.lr~et",J I A....t...J '1, ~tW0r-'.j.,'<lVI:::
h-o _,0-1 J,..c.. I L-fJ - d...o~ I t/~' }- "" w to. p .•-.-..... j .
b-~ ~d\1aMu....~f1JA"1 ~ ~ ~----
I'

b G1- J O'Y\ a

'0 <. ~
/..

~. ~t~~ <6
~ ~
U T ..V - I~o/J--I i-41..1.1,j",~1.t fV,'/t;. ,,£)(O-<:J""'<
PF - t;rb1'l~~ J bCVlJ .
bvi- (U\AJT .
2

2.
(a)

Df~';"'~
J;pfu.'
0·11 :D

,
3

3. The structure of (+)-Trienomycin A is shown below as 1. (a) what is the total count of
stereoisomers based on the variations possible at each stereogenic center? (b) What is the absolute
stereochemistry at carbon 2' based on the isolation of D-alanine as a degradation product? (c)
What is the absolute stereochemistry at carbon 3 based on the isolation of (+)-2 as a degradation
product? (d) Given 125 stereochemistry in 1 what stereochemsitry can be assigned to C-ll and C­
13 in 1 based on the isolation of 3 as a degradation product?

OH

o 0

~OMe O··'OMe
NH
4

4. (a) Give the product(s) of stereospecific anti addition of bromine to trans-cinnamic acid.
Specify all aspects of stereochemistry and show the stepwise mechanism of this reaction.

---
\.l BY
~IL~. 11 (.0 J. IJ.
> ~,'ll

13..,. H

(b) 1,2-Dimethyl-l-butanol may be prepared in either of two ways: 3


(i ) Lithium aluminum hydride reduction of 3-methyl-2~penpnone.'-.....:,.
~
(ii) Reaction of 2-methylbutanal with methyllithium. -::;y~U :,. J
. method woul d you c hoose to'prepare
Which ­ t he eryth
ro 'Isomer.
=t ? ExpI'
am. CJ.l:l.
J

- (!)/J.
\t M,c. t-4 111/" _ ~~.
j-J;rr~ ~ J~~~
tu.

I\, fW,.v 1\ l.!--s~


WA 'Y~vh'()'I/I ltJtlf 'r'~ ~ 0
5
~

5. (a) Free radical chlorination of (S)-(+)-1-chloro-2-methylbutane gave six fractions of formula


C sH ,oCI 2 • Four fractions were found to be optically active and two fractions optically inactive.
Draw structural formulae for compounds making up each fracti~ Account for optical activity or

G~h~~'irchC;':-h'v.L tr",cH(/W': ~U (~) cL~d ($)


r U.J cj (!) H lfl'li @

lA.
~ y.~~cJ. ~

:. J

~R,3R @ @

. L\.-,-v-J I "AJe. ~'~ bo;L'-nj po,~J-~

:J>'M'.e-u.a~4 ~ 0

OJ-h'~ IY,AC-h'u.t H~C.+'·qv.,,:


6

6. (a) Draw the stable conformations of all possible stereoisomers of 4-tert-butylcycJohexane-


l,3-dioJ. Which stereoisomer will fonn a stable ketal with acetone? Why?
0", fH- el+­
~ol}~
/;\ 6lf ~()~
0; @ 8; CA~ _ d.;. "X1'p,
Onl 1JdY.)(jl tt~~7l'I ::;l'it;.- ell.ttbl<.f.
wLm AL -fwD
[/<> ~.t- (J) J ~ W~ 'rA(AM-fw: ok - ~"'t4
I oM­

o"ft", )..'oA J-~w-L ¥'~ e.t.'c- K-of.Jp.


j~ ~ ~+;:(o ~ ~~C.U3
~o ~ --0 0 ~/~

)~

/j) ~
LY fTsA- CN
\-}-t
(b) Draw the two chair forms of sugar (a)-D-galactopyranose, one form of the sugar galactose.
Which of these two forms is the major conformer?

HO CH2 0H
HO --)d
~b (d)-D-Galactopyranose
.,. of '•
.:i 1-:..
HO OH
7

(i)a ,j\\ H I~'0


N0 (ii) Cf<J

: :

.:: .::

cD

ell.?>

7wo 1,3 ­ /.A""tA/


f
I''V1 ~ OI.{;A ',.."..

t'V J. ~ k·t-/
8

8. Which will be the major reaction product in the following reactions? Explain the basis of
your selection.
o
(a) H3CO-~-C-CH2-CH20H--~ r

~H2
9

(c)

(dJ(j + (j --.::H3~O+-....... Or
A A
J: J Mixture

-h
Bo!t ~ --10x,'k wN/ "'I~ f/Vi~ H2 0/1/1
J'/A.C ....
P4Ava, -klftll
?+ '£'DI.
~1Je ittii ~~o/I/a-\~~
n: UM--h'~ r-U~:r
G(
...
~y ~1\-h'vt1.

\-----,
-
:::

,,

J
: oJil

-
9 10
. (a) Construct a qualitative Huckel "
Frost's Circle. MO diagram for the following eye I"Ie polyenes using

Bre
0
o
(i) (f)
(i ii)

D (iv)

_ tJr,A'J, rnc1f~
"
( ii 0
l' l'
-C><

( 'IV)