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:i;i- r,t iilj,i i;1,,,\li

j.:r:i:ii,i,: I : i)Tr I,i,i.l I

NAME KY

DO NOT REMOVE THE STAPLE OR REMOVE

ANY SHEETS FROM THIS PACKET
Chemistry 0350
Exam 2 - April 13, 2016
Only answers written on the front of sheets in this packet will be
graded. Answers on the backs of sheets will not be examined,
Graded exams will be scanned and returned via email.

1. (20 points)

2.(12 points)
3. (B points)

4. (10 points)

5. (18 points)

6. (24 points)

7. (8 points)

Total (100 points)

NAME:

1. (20 points) For each reaction, fill in the box with the missing starting
material, reagents, or major product. ln cases where the product is
missing, if no reaction takes place for the given starting materials and
reag ents, write N.R. in the box. lndicate product stereochemistry where
relevant.
Zp* (h box

o l<o
Y'f srl o
0
o
Lq
f-1i = hali"e, P7"

-Br fs nof arr.|

[Jc - ^A tg{nce.
do chafr
+i ru s"f t Br,
b ec6Vtatt /V, R.
,rrrrtSf NaOEt

OH

A
Br 5 n,
( ,.^tl rearn35ye1+
*if*t-fiN.iI?'t A,
d, )

Na
NH (l)
-l-r-crng nqdv.c4j
o e*q,ad\{^
nn\f E ranS

2
NAME

I
lont inued
\\^sl ' tnat.{rif
+ o 3etcl a rltl
c,f ELrrrl ..r vtsf stn yDbtltr<.L
H
trSe hindr ., be e< basV
+ onet Pdr^c+ rndic*tedr
cl LB u-o1rLl A
unhinelr (d.
-fo

H
3
t o4..,) Hu o

4 Na t \1

L?+ ir HsLlft z- pNv\eQ

r.'
1
z pl i. ,(lt ncagrnfs g vi de t- in srhgte
HO
stt p

0Kqy r'{ s' e.

oH o
Le{
{-q =hattcl OT
o
r) o-e

.?.) Meas
t P+ f o n\ I
3 Pr *\. d
a r-f cl, r f\ e vr'de r| oo
^

3
NAME:
z pt eac. bo f
2. (12 points) For the following reactions
a) lf the reaction is 100% correct as written, write GORRECT in the box.
b) lf a reaction does occur but the product shown is incorrect, draw the
correct major product in the box. lndicate product stereochemistry
where relevant.
c) lf no reaction occurs, write N.R. in the box.
H
1. TsCl, pyri dine

2. NaOMe, MeOH CIrr ac-+

OMe nrcafe
c
,,,,rOTS M"9!
A
o srrar*+
OMe
\*Jt
Br
NaOMe
MeOH

r^ E+ a,r CiS

H2 co r f qc+
Lindlar

A
MeY
H ---__----+ H
DMSO c rf eC,
HCt H SMe

H3PO4

4
 .Pt I all correr{
lp+ r{ l l 3 cdrr<c!
NAME

3. (B points)
A. Consider the reactions of the molecules below with ethyl bromide in
acetone. Rank the reactions from fastest to slowest (1 is fastest and 3 is
slowest)
e {ocnrrbt\ar-
lhan wlrcrl
n
SO
eh p.ovrtg res, SH
Sta-U. an. rr\ll<l 6
Le-Es Nu.u\o f h\\\ c
a. 3
B. Consider the reactions of the molecules below with methyl iodide in
DMSO. Rank the reactions from fastest to slowest (1 is fastest and 3 is

?
rQg,

'g,t'o
slowest).
rDrC\S
gv N N
not N r.-

\,-
o e
C. Consider the reactions of the molecules below with sodium acetate in
DMF. Rank the reactions from fastest to slowest (1 is fastest and 3 is
slowest).

Acetate =
Br nr r Jcco"\ V
Br ll
=
; hn"ra[ I
\
S*2 Br
* rgtL
\-) I .
D. Consider the reactions of the molecules below with HzO as solvent &
reagent. Rank the reactions from fastest to slowest (1 is fastest and 3 is
slowest)'
pr'or. T'''"
pr.'or,
oMe

Xor,
lo,

e- \
?
5*,t I
rs
o, des. \iltzqs c<rrbot*1. b3n *;h**"'3 - -t,rsu
Ols st"\\"\te C.alho tat" t,l yl.t
 NAME:

4. (10 points) Compound A is a methyl,bromo cyclohexane of unknown

regio- and stereochemistry. The four possible regiosomers of A are shown
below. Some regioisomers can also have stereoisomers.
HC Br cHs CH
Br
Br H3

Br
Shown below is a seres of reactions that A undergoes, along with
information about whether the products of those reactions are chiral or
achiral. Provide structures for A - E in the boxes below. The correct
diastereomer must be shown where relevant.
E chiral

1. NaOMe

2. BH3
3. H2O2, NaOH

'l . NaOMe
1. NaOMe

2. Hg(OAc)2, H20
A 2'os B
ac iral 3. NaBH4 3. Me2S
achiral
1. NaOtBu
2os
3. Me2S

. eo.ch c
p* loo X
chiral

A Man r N\US! b.i B c

r .lt' ?t
f-
0
r ri ) H
H (
Itf
_j
ltte ca". 6e dash,w{r Q
1p* i{ Slrairht lines ,o1 iirz.df,t
llr\e
D E t'4 ant 0 u nnu* bz*a
:
oH
0 l.l
lrrr\
- c)\
o+
"oH
Me, o l4 ta r.,bc- ata, oKaSi Uotxf r^ru, p'^'v il"q d"
4 ^l : t , rr

\e t r 5l':'.ht line_
r'.Q
p+i{ M e {i4 otl crS
br 6
r{ 1,, A ca.nftl p\n\sf_
U,-,E
 NAME:

5. (18 points) Provide a detailed mechanism for the following reactions.

Your mechanisms must:
1) Show the individual chemical steps and all intermediates formed in the
process of converting starting material to product;
2) Correctly use curved arrows to show changes of bonding and lone pair
electrons;
3) Show all formal charges;
4) Employ only the starting material and reagents listed.

a)
B(OH)2 o
AmM]
NaOH, H2O2
l

o o+l lv IP
H - oog ----->
a
/^1
0F{ \p* 0
)o H I on
lP arrl
.-,o \-\ -- ,- l-
B B-* H B
\uH - I
0+l l{
kt | +o+a9

b)
S Mel
scH3
pl t a+d-t
acetone
H 3C .___-,-..--1
Itll@onSl
m^, \
.t l--l

I al, s
t1
I
-.r --) p +

lr YY^)

? * *nes
2 a rrtt

7
 NAME

5 continued...
b r'f c)
+
^e MeOH

A lP-f f
-k I gl arnvrJ o+h
"-
I I
o
Arnr,t,g

(1
ff*,
H O'n
oH Fl
o+l t{

MO H

e r{- ege &arrrrrtjs

,1,

:ff&Jl"".-*n
n t%'t'r sa rn
me8z

6. (24 points) Propose a series of reactions that convert the starting

material on the left into the final product on the right. Partial credit will only
be awarded if the product of each synthetic step is shown. Do not provide
mechanisms for each reaction.
Structure your answer as follows:
etc.
Starting Reagents-'l Product 1 Reagents-2 Product 2 ----* ---- Final Product
Materit(s) (with correct
--+ stereochemistry)

a)
+o+
---+
----+
tri
c,
// .::-3-+ /^--{ l-l e

8r -+>
Lr'n larr ra
I
P
!

" f"l' 2 o'r

' 2t t'{ s*orf ,;1 8rz- bwb t ( inr ovrec{

f rylainlnj sk ls
a Zff 'r'r $ ru ot I st< p as h-*f Ll,l l,rr
I
 pl tof,,- +o e\irn utl ht'nde,rc ilbase.
convc-\ alFa.n -> pod+not
o D
NAME:

1,13..*06
8,, ,(p
6) continued,..
- 0 ftA M0f, r"-
Br- 0 Me.
b)
o
.
o

.y
D
Me 0 4e
Buoo B",.(u.' 0
,/\4 )'r o" o

--+ /.pr\ J\ _ryjts3'

or LDA B {' ,,s cl
9( H r' oFl a
s"
6 QIV\I ''iJ
c'anbc- Azt l't\ 0l's
6 d. s""
t Bu-o
4
uuA lv llru.
*"'
Br --->Meo H
l\
o

oa

Br Bf r
o
co.A
r Qnav,
b r|wm
M - o vt4-
""",^^oJrluovWSg/
pl ( o. e.r t^ave.s &
+ ur,-tc

I c* r/+g t gr
---------->
-------->
HBT
t{Bv" ?---
lI r LB,04
rr Lh r/sg* (tr'u.n. \
r^ gtt IkA I
nN 3+ia,1 /
SPt+orts 3p{ {ar elim pl t'.in 'trel,-bas
-36
'q qa 0f\ 3 o- 3
o fi Tsct Ts
-_>
PYT
2.9+ Hz-D
k { ofng Br OH

---.-.---> + enantiomer
+
B OH

Bc luafit oH
__> = t'f
fv a-
H ) oro,1
gHr (.r --_-}
z) rua llsor, Hr
r otl
tfan
os og,

P+
tttl
t,u:ll,tr
L
9
orrw t,u boH

X
[ x
11 ot,
BlJ' /Isc t+-.^
 NAME:

7). (8 points) Provide a synthesis of octane starting from 1-butyne as the

only source of all the carbon atoms in the product. You may use 1-butyne
as a starting material more than once.

---------->

1- butyne
N orN He
-.--..-=
or a\
,'.G
-\,
rL bA
^J &P+ {orna
loL
f\r luln/la,*. ) n Bez Tscl
e) i?o.r/vaoH
- \ ---> oTs
W PUT
No./ruH

zytl*o
3pt to mo'"Y I 'oH
Co*ple As.*o
l"L+,r/alkYue
' anl4^

\
o
r *\kgnt 1, ^*, ,,

10