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Mid-Term Test

DALHOUSIE
yrglYFs$lT_y

Chemistry

2402

,2014

12 February

{rt *ft i t"i.trg &4i nd-s

D. J. Burnell
(50 minutes)

Read the questions completely and carefully. Answer all the questions on these sheets. This test
marked out of 40.

will

be

explain why the major

IIZ marksl. Draw the complete mechanism for the nitration of anisole, and
products are the ortho- andpara-products.

euestion

OCH.

ocH

l"
,,\

HN03, H2SOa

Noz

Generation of tre electrophile:

P)?

H_O-Nlt
o

Hra

ocH3

HO

,5.1qi
Ho

HO

u_---+

ffi:

NO2

(b*r,
)A._ -,,to,
[..-)-H

<'->

tertiary
ocH3

tu;

X: is any species with a lone pair

that can assist with the removal of
H*. 1n tnis case it would be wata.)

CgcH, t?t"

ocH3

,\

I )*o,

nitonium ion
O

,,\
*
[,\-H
@ NOz

>aY

<...._>

t"

H NOz

tertiary

charge on

?t*'

ocH"

oba
H

NO2

Noz

?""

Noz

para

X:

?c"

?cH,

q).I":*,OX*

o*o'

charge on O

gcH.

gcH. I

'd,*-#r,
NOz

NOz

_l

are much favored over meta since the intermediates are lower energy / more stable, i.e., the
intermediates for para and ortho form more quickly than for meta. The intermediates for the para and ortho
reactions are stabilized by four resonance structures, including a tertiary carbocation and a cation on oxygen. ln
contrast, the meta reaction's intermediate is stabilized by three resonance structures that are all just secondary
carbocations.

Para and ortho

Question 2 [6 marks]. Here are two infrared specta. These are labelled A and B. These belong to two of
six structures drawn below. Which structure belongs to spectrum A and which structure belongs to spectrum B?
(Make sure your answers are clear.)

A: ,o? 11 7. 7s + zJ ?ll

a'c?

{t5

$cioLs

tl

I T

tl tl t6 r0 rr rrf,2J,?,r0,

li

/_\

_.0

v,,-\./^__\
"

\_0,
\\

,t

loe

-[t

-0r

-0.E

-0.t
-0.7

-0J
-m

{
0ll

aro {.o0

-t,

a3!o ro0o rao aas lam

ril s

2t00 2t00 e.00

tll
1a00 ln6
glHgltm

2200 &

l.00

ta

!0@

l:

tm

It

310

,a4 T T \s41'2fT?

lt

ir

l5 16 tt rale

2.0

2s
ttI I al
I tlm

/1'*
| -0-t

I
1

-02

no C=O

-0:
-Ort

-o.t

-0t
,

0!l

.a0 aa6 ar6 .n6

so ao 3.0 tpo

300

e0 80

il00

22m

e0

r&o

lt00
YAYEXT'SIBS

ro

ltl

t20o

lm

i!

-eo

a6

Table of typical IR absorptions

Wavenumber (cm-l)

Bond

Typical intensity

37s0 - 3500
3500 - 3200
3500 - 3200
3300 - 2800
33s0 -32s0
3200 - 3000
3000 - 27s0
2900 -2700
2300 -2200

O-H (alcohol)
G-H (alcohol)
N_H
O-H (acid)
C-H (sp-carbon)
C-H (sp2-carbon)
C-H (sp3-carbon)
C-H (aldehyde)
C=N

strong, sharp for free OH

strong, broad for H-bonded OH
medium, broad, one or two peaks

2250 -2100

C=C
C=O
C=C

weak

- 1660
- 1600
- 1580
r6t0 - 1600
1570 - 1540
1300 - 10s0

1780
1680
1650

750
630

650
550

C=N
C=C (aromatic)

N=O (nifto)

strong extremely broad

medium, sharp
medium
medium
medium, two peaks
weak

stong
medium
medium
weak
medium

c{l

c-o

stong
stong

C-Br

strong

-0.t
-0t
-oJ
-tJ

uestion

[6 marks]. What is the mechanism of this reaction?

'ilo

-l

OH

l,-n

1. LiAlHa, ether

-"-ocH3

2. H*, H2O
A

of
-.llr

o')-

o")

11*i-ocH3

llc- 'H

lJr

c.!ocH3 --+

--+

\H

H
'lo

'lo

H*AI-H

HocH3

H*.

H,

'o

wca'
IH

H- Al-

oocH,

"tt-t

It.,

*ro

OH

c(H

(by-product)

(More than one

[6 marks]. Devise synthetic sequences to carry out the following tansformations.
that have
intermediates
of
all
the
structures
and
draw
on
rurows,
i"p * requirea. Indicate reagents and conditiorrs
significant lifetimes. Mechanisms are not required!)

euestion

CH"-OH

(/"'",,
racemic

m-CPBA
...........-_.....--..*

X,,"* "
(,

O
O

------>

2. H.,

Hrfo*

*,"D-to"

cHel'Alclg
(Friedel-Crafts

cftMsBr'

(Sp2 attack to open epoxide)

(epoxidation)

B'

1'

' *."O

alkylationl
(ortho-para directoQ

conc, H2SOa

(sulfonylation)

,r"''0to"

Question 5 [10 marks]. Provide the missing starting compounds, reagents/conditions and products.

A.

B.

(cHgcHz)zcu\i,

Oa-t'

Jo

(C-C bond formation with organocuprate)

1. excess CH3MgBr,
H.C CH"

^x";

ether
3. H*, H20

(double addition of organomagnesium to acid chloride)

c.

D.

Noz

o
E

1. NaBHa, CH3OH

-^-^*

AtoH

2. H*, H2O
(reduction of aldehyde)

rOH
F.

G.

NaOCl, CH3CO2H

-l-=,l-.

-?
(oxidation
of alcohol)
\, H242,

HzSO+

,D

?
(iodination - electroRh$c
aromatic substitution)
1.

CH3CH2-C-Cl , AlCl3

Z.HzO

H,

3. Zn(Hg), HCI

(Friedel-Crafts acylation then reduction)

Br
Br2,
t.

(benzylic

J.

,OH
t:
t-

hv

To

\A.Z

bromination)

PBr3, pyridine
(Sr'r2)

,Br

-1--\