?rergt,u 9€r # 3
Name:
Chem 252Week4
TA (circle): Matt DeMatteo
David Hilmey
ChrisMcDaniel
SandeepApte
Matt Bedore
Carrie Hayes
1. Write a mechanismfor each of the followingreactions.
cl
a)
\?v
Feclg
ct2
+
rm
'i,,,.s
i
l
t
U,
u,- Feuf,
-
+ FeQg
+ HCI
l
\?'-/
.rt7
[>-5]t"----->
9{
\
b)
^
+
Alcl3
r\r
+
/'t\--/'wl
/---,--- aL, -r->+/
)ra'
+ HCI
{+
l+
€-
-Y<g
e3 4>
42U3 -->
/-l-
+ -6--/
c)
o
--o.
v
A
SnC14
c)
A
c { + gclv E:=
+
I
6
@
\_
UJ
' c l
+
e)
C43'c=o
-
J
t Ftc't3f u q
fr
+t+
t 42at rrz?tc< ,6t -
a1><
+
HCI
@
C l f 3 e= s
+
@
SnCll
tuE7
d)
+
Atct3
CHzClz
d-
4/ A3
(J-dLq 49s (xR.
t+ ,l+
-;:
AM,?->+
GW)
2. The followinggroupsare ortho-para
directors
^
a) -oH b)
c)-N(cH3)2 d)
_o-E-cH,
O
-u;;,
t q;='
e)-O
-il-8-.r,
Draw the contributingstructurefor the resonancestabilizedcationformedduringelectrophilic
aromatic
subsitutionthat showsthe role of each groupin stabilizingthe intermediateby furtherdelocalizingits
t"nrt".;"*""'€ql
4,,/*y e i#+U**#(r!
p) i$g,*'t!_rrr
&1U'
_G^."F&-r./_,7
c")
,,.azt<' qn J,-.
(ol)
CrU
&z a)L\/<
&z
^'lr'< *a
*fl_^_
-zaA*L'
-24,1-LLt
G)
e*F'-
^,i
?hr*'*'
(>'F
( _fb
ef\
#
't
3. Drawtheexpecfed
majorproduct
reactions.
of iFlefottowing
1>
!- ,l+
#:
+ 4/"*<
;;.f:#
e
-GDryr' 4
a;9f.t
c2 o{z
*>B_?rU,
&
b) 9H. 'Y,
rA llJoo
V
oH
lx,
,A
\l_
oX
T',*::ef
v''
Do_
pD-
To,
c)
.,\l
l
l
%"t.
----I
cl2, Fecl3
+
N o .'
|
O
t
-'\--\
+
i l I
lneHj
e!
NDu
u_zLa4
L
v0/2 vr?iuN
.yuotj/
n
d)
so3, H2so4
x
[=r""r
| ( - ( +
1ryil
e)
l
.rrt tV(N
nhout/
?otH
,,\.
- L -- q
t- lU r H
I3
+
lott(
Br2, FeBr3
l
l
:g"r,
+
r^,
o"*^r,",
o
D
4. Following
are the finalstepsin the synthesisof trifluralin
B, a pre-emergent
herbicide.
c r
CI
a\
l t l
o2Nv.\s/,No2
HN03
Y
ll I
Y'
(1)
CFa
l l
-^N
-
H
+
ozN
(2)
cFa
CFs
a) Accountfor the orientation
of the nitration
in step1.
//-'k
"a*"-#'u^17
,, f/ro - |/4 /a /t? "tT
U
,
/4-'t
c4
*-t/
4( b 4/4
K
z-r)€t-t)o-
+ tL y*",b"t
I
ctr3
",T'TP:""
reactioniastep 2
b) Proposea mechanism
for the substitution
t'(
o'i,u-u$i
ao"-4.-P-'i
t+/t"'--,
<. ipr - Y
cF,
c'Fg
LuA
"'t.,,;"0'
qDI( )r
L4 D2,
a,DjiA-Dou
)=
cF3
cFt
^ry^t-rr'*l
$trv++z
J
nqc'&"YtrlL.
a,4,wra-fi? ,
C"jsilirti,^^
5. Providethe reagentsto synthesizethe following(note: the orderof reactionsis criticalto obtainingthe
correctproduct).
o
/rI
a)
r,Ar
u
b)
?r.
r\/
c)
?t.
,A
w
d)
?'
r\7
-
?
t')-&
\
2
t) kunoy
z) 9r.,ft$rj
z) 50dz
u) (cueU z ), eq Lt
ozN
l\ Htsot-
>/sltro'
\z\co,H
Hzey
z-)Kmnly
t) t+lsct,fta3
?o,'
r^
Y
z) K Mn |y
co2H
OMe
t) Hp?, t!,sa6.\.r.roz
*z+
\)
2 ) Daotuz
ilo,
6. Both of the following syntheseswill fail. Explain what is wrong with each one.
"/h^ 'k
#t '
Po-
6t
"r,loli'^ "-'-(- g
fr,e'L u'y'F
oboeh'v.rb/
to
^oth
ci
O tL
a'r-
at*
' 'f
)L
d"d'.frt
/24r'4e
O J.
,K
# /
ttt # z
-.'-(
l. NBS, CCla,light
2. NaOEt.EtOH. heal
3. Br2,FeBr3
Art^stg,*2,
*prrtut
(.i,4
l +
/a'n
7L utoqclt'c
u
t
l I
'teA'Y'"'1
ei rzn-t-{L
'
.,-o )4{ "'/4:'?*
/
ab , , n t
y'n't
^r// /-'^-t
fuil 4 k'*(
4"-'1
e)-",
phenylbenzoate
7.
/. One
One flng
ringot
of phenyl
benzoateundergoes
undergoes
electrophilic
el
aromaticsubstitution
muchmorereadilvthanthe
other. Which one is it? Explainyour answer.
n/6
,, ij
e-i-v
f.r u_
^./-,"-t"4
fin4
ry side
d
/saL LL
4/)Al rp&- l*/-'
1^/.
au,rtta,lh/
l/-.Lf
fA"
i*
@
ad_
-t- or<
5'l-
8 .Heating1,1,1-triphenylmethanol
with ethanolcontaining
a traceof a strongacidcausesthe formationof 1-ethoxy1,1,1-triphenylmethane.
Writea plausiblemechanism
thafaccountsfor the formationof this product.
n
v
H', EIOH
o*o'
A
\,/
,,tr1f
4
P
r Lr e N
@ Ju -