& Amine (-NH) > 10

-
: 2 peaks

s
↳ 20 =
1 peak

~
3 = x
peak
C = 0

& Amide
(1)
(N -
( = 0) >
-
10 =
2 peaks

↳
20 = 1
peak

>
30 =
x peak

alkane
*
>
- ((3000) Sp>
Stretch
-
alkene ( > 3000) sp2

IR
UV & Woodward -
Fieser Rule For Dienes

a -
CH3

1
L
-
(H3

I 3
-
Transoid = 1 =
214 nm I
CH3100
-

Exocyclic
-
double bond = 1 x 5nm = 5 nm
-

Cisoid =
1 =
253 M
I
Ring 5m
-

residue : 3 x = 15 m
- Double bond
extending
= 230 m =
60 m
. 234
:

nm (observed = 235 nm) Conjugation

~

cisoid =
1 =
253 nm Ring substituent = 5 x 3 m = 25 nm

CH300
-

= O
Ring residues
-

=
3 X 5 = 15 nm

Exocyclic double bond =

3
Exocyclic Sam 15 am
-
x =
double bond = 1 5M =
5 m

Alkyl Substituent = 1 x 5 = 5 m
: 353 nm /Observed =
355 nm (

: 278 nm
(Observed : 275 nm)
 & Woodward Fieser Rule For Enones
&
II
I ↓ L
- I
B C = - &
L

-
/ &

O
↓
-
a =

L I
-
B
33
Acytic Parent Enone = 215m
L -
Br

I
-
OCOCH3
Five-membered
-

X-CH3 ring
-

= 1 x 10 M = 10 M enone :
202 nm
B S
J -

B x - Br = 1x 25m
-
CH3 = 2 x 12 m = 24 m
=
25 M

Six-membered ring enone =

215 m -

: B -
CH3 = 2 X 12 M =
24 M
249 nm
(Observed = 249 nm)
Double
-
~

bond extending Exocyclic double band :

1 5m
= 30 m x 1 = 30 m = 5m

Conjugation
: 256 nm /Observed =
251 nm)
-Homocydic diene :
1x 39m = 39 nm

S-Ring
-

residue =
I x 18 =
18 nm

: 302 nm (observed = 300 nm)

Mass Spectroscopy

& Rule of Thirteen

>
-
M ↑
-
= n +
13 13

>
Base (nn +
-

formula =

n -
r + 2
>
-

DBE (double bond equivalent) = U = 2

& Rule
Nitrogen

-
MWodd ,
N = odd

MW
= even ,
N =
even
& Isotope Ratio Data

M
> MF common isotope (2H6 =
30
=
-
M
peak

MF heavy isotope (2H6 : =

31 M + Peak

Example=

181 183
~unitrile group

① + = n
+ & Base formula : (1325

=
r = 181 -
(13 x 13)

U =
12
Fragmentation

& Initial ionization [ Stevenson's Rule 1

>
-

-
& Y

-
>
I
-

&
!
+

>

i
-
-

&

+ I +

homolytic cleavage
si
&
<-ceavage /radical site initiated) > from
-
cleave at 2nd bond away radical atom

>
le radical site initiated
+. -Y
-

7 +
& - & &
 -
o
III
&

>
-

! >
-

+ -
O
&

B-cleavage
↳
& Inductive (B-cleavage) > cleave I pair by
beavage electronegative
-

heteroton

>
-

L
E
heterolytic
+ +
>
& O
beavage

o
+

S &
II &
III
*
>
t
C= 0 ?!

!
S
II
 >
-

+ -

HIN > Ha +

-
↑

> ↑
N - J

> vπe
&
McLafferty rearrangement
>
v
long chain (n)

-
vU -
M

& - osH
I - & C
& >
-

-
I- - H

d +, I
>
-

&

o
+

~
+
& ne
1. &
+ M
-
0
+

> Il I
-

>
-
& Il >

H U
H "n
↓
& Two Bonds Cleavage >
-
Cleave 2 bonds ,
eliminate small molecule

HJ
>
17 xl *H
> -
(
N
!

>
-

Hi >
- H - c) +
-

↳
C

>
- + +
R -

Vl RI >
R R
-
=

"n
* 2 Jab = 0 - 2Hz

ab
- : Jenen
4 Jab : 0 - 3 Hz

5 ab =
0 - 2 HZ
 * Ortho
~ 8H2

meta
~ 2Hz

para
~ 1 Hz

* EWG ~ downfield / deshielded

EDG
~ upfield / shielded

H + x -
N -
2
=> DBE Formula =
C-
2