E

É
E I E-E- a- oi
; §°i¥
5 S
S

É E- of
EYE jÉ◦=ñ
0 I
€
.

É
•

¥÷÷÷÷:÷¥÷
is
s ◦ o
£

§ -
•

%
¥ '
u I
§ ◦= s

É
É É±É◦=uÉ ÷:
so
SS

I 0

.ÉÉÉÉ÷÷÷÷
iÉÉ
¥
•
0=0 I
•

¥=É
=

.
1k SPECTRUM

triple double
OH /WHICH CCICN CC / ON / CO

2300-2100 1850-1550
3600 -2850

↓
CH bonds
} ≥
sp sp sp
3000-3150 3250-3350
2850-3000

DEGREES OF UNSATURATION

2C -12 -
H -1N

2
RESONANCE

significance
1. most filled octets
:
:-O
,

at
:O :
HE :

MAJOR

2. fewer formal
charges
:O : :-O ij :-O

Ito _ E- # ii. -

,
#2 #3
#I

atom
3. ⊖ on more electronegative
④ on least electronegative atom

:O:-O iii.
i
CH } C -
Hz
CHL
-

CH } - C =

v
MINOR
MAJOR

de localizing ⊕

i
" "
"

de localizing
⊖
②
Ñ¥¥o
:

OF A
[Link]?o.: ⊖
: !o
.
:

① ⊖ on electronegative ③
atom oxygen

.
.
'
.
E¥
 ACID -
BASE REACTIONS
neutral ]
ACID : Proton 11-1-11 donor [( t ) or

BASE : proton (1-1-1) acceptor [ f) or neutral ]

acid strength row)

atom ( atoms in same
⊖ is on more electronegative
1.
⊖
⊖
iv. OR ~

column)
( atoms in same
-
=
sci I
-

>
-

I >Br
site of atom :

will stabilize the base

larger ionic radius

to delocalize ⊖ charge
resonance : more stable
2.
through resonance charge
@ greater
delocalization
µÑ ◦
-
H ⊖ in µ
-0-140
conj
.

base #
via

2
resonance

base # 1
.

co !nj -

different [Link] bonded together

3. induction : charge stabilized by
)
( neighboring
a. F. Br
f- and ft
0

Cl o_0
Cl
Cl

base -0 acid conj acid . conj . base

¥
"
◦
⊖ na⊕ µPÉ = I
Noi
on
u
sodium 2. 2,2
-
tri fluoro ethanol
fluoro acetate
 base acid Coni acid.
conj .
base

tnd%µ
⊖

①
= tin
,
+ -1-1 + lit
④

conj base to base :-O on 0 better than N

compare .

STRONG BASE
%
0 0

first equiv second Mri"

-É%f
"
ya .tl .

⊖
s

yNaH
◦
of → s
,
Of ⊖

toy Jatt
→
⊖
-
H
,

CONFORMATIONAL ANALYSIS
lowest energy staggered highest energy eclipsed
Hoq' ,,

1-1-01
"
_
Cl
off - H

↓,
,
H H Hot H

"
3 5
pg Up
sax
.

'
down .

2 6
6
2

agpgffM ,
4 3
NHZ ≈ ,
z
≤

Éz
^'
NHZ
both eq .

both ax .

ax . Up
e. 9. down T butyl favored in e4 position
-
.
.

Axial conformation has too much

steric interactions .
MECHANISMS electrons
compound that 'll donate
nucleophile ion or :

radius will polarize itself better

-

RS
-

sulfur big ionic

⊖ HS
- -

HO IRO I
-
-

Br , , ,
,

that can be
attacked by nucleophile
electrophiles :
ion or compound
⊕
GOOD NUCLEOPHILE poor NUCLEOPHILE

NUCLEOPHILIC ATTACK + Boo DBU lbulky )

-

OH Choo
-

.
,

Br
STVOND major / EZ min Hoff

/
:sn2
'

1
. .
I : .

:-O
:&! major / 5h2min
base
= EZ
major
.
'

2 :
2- :
Ez only
g. ,, .my
Ñ / RC
,
}
"
"

nvc
'

halides sulfur compounds .CN

.

,
,
_
1-1,0 ,
H > COHIROH
1- 5h2 Only N}
unreactive
:

PROTON TRANSFER↑
ii.
weak [Link] , major
2
.
: Snl elimination
""& " '
'

3 :S " "
:&! :-O
joIÑ
-1 sign , minor
= -

, µ

R ALCOHOL
acid
base GOOD NVC . HCI , HBV POOR NUC .
1-12504 ,HzP04
i. unreactive .sn 2 slow unreactive Elstow
GROUP
1.
.

1 : ,

LOSS OF LEAVING ⊖
2. i. [Link] minor z
.
: El only

. Ng , =
⊕ :& ! :
3. isnt only 3
'
:
El only

I. G.
SOLVENTS
DMSO DMS
aprotic acetone ,DMF 5h2 favored
as strong 'd
:
,

polar
REARRANGEMENT

\
won't coordinate
aaaa, a. pond , to the nucleophile

=
⊕
polar [Link] / favored
④ and
ROH .

¥ stability carbocation
✓ ,,
nucleophile

3
'

>
2- > 1
'

carbocation 2 common CCR

H
R

• r
>

r
1,
r
>

oµ ① rf
r

methyl shift ①

most
↑
substituted
CH }
µ CH }
1

2
'

3
'

more stable

¥ > ¥
tertiary
②
"
tertiary %
shift
H
allylic .
:| hydride
↓ ⊕

④ it
'

2 → 3
'
 NA
Snl : PT → TIG →
/ % ⊕

3- substrate
allylic
and benzylic
CCR and S)
mixture ( R stable carbocation through
racemic more
resonance stability

☆
alcohol
nut
] ☆ good
" 20
•
OH / 11101
ABC '
µ
And o
◦
HCl ⊕ l
'

•
☆ 2°
Snl
,
[ →
I

PT .
UGNA racemic mixture
racemic

01
concerted good I Br >

Snl :
NA -1116 1.6 : >

↑ so more
I
'

> 2
'

substrate bigger halogen

NO CCR stable anion
inverts stereochemistry

É5oodnw%vba
"

• • Naan
>
jN←inversion
☒H }
5h2 major
-
inversion ¥+1}

El :
LLG , PT
CCR
'

3- 2 1
.

> >

substituted ) + trans
major Zaitsev ( more
more stable
:

minor :( is
☆ weak
nut ⊕ PT
↓ LY
◦

☆
1-12504
,
≈ ⊕ methyl g
≈ //
El
s shift
OH T H H ← Base
•

OH ,
-

:
☆ "" 3
'
'

H .

all 2
hyperconjugation
.
 Base
Major
[Link]
i.

250 "
1¥
"
=
"
✓ % zaitsev
⊕
He : Base
g. ≈ minor
⊕ /

EZ : LLGTPT
I
_

2-
'

3 > >

if bulky base
Hofmann major
!
+ :
-0
Eto
. .

I >
/
Br>

"
otpu + of
,
☆ bulky base
* EZ
Hofmann
(di sub)
-

Maj Maj .

Hofmann
.

4 zaitsev
minor

(tri -
sub)

e?

[Link]
K

'

EZ major

Br
p H Br 4^3 H

→
/
H
gauche
H CH }
R k
midterm 2 # 12

n % Eka
¥, major minor

pushing mechanism major

for
arrow
-

← KOTBU

Tts"☒i "

≈ ,
major
¥9
☆ It wedge is
on

antiperiplanar to
substrate ( Br ) so
we react w/ that

products
explain why there's diff quantities .
of

in the Newmans ,

are
" f- "
anti +
→
Fr trans our sub groups
anti to each other ,
antiperiptanar major
Br ;µ
,
µ
leading to trans
r conformation ,
thus
it's
H, rotate to →
cis more stable hence
Gauche trans less
Br
'
H minor major .

hindered than cis

µ

coming from gauche

ALKENES
Regio chemistry
:

HYDRO HALOGENATION
"
Markovnikov addition
-

¥!¥m _
- Br
Bron more substituted carbon

Br
- H anti Mark - addition
substituted carbon
-

Bron less

^^ ↑ ⊖
:& " Mark
on anti -

\ ← =
①
⊖
a
:&.ir :

" BV
①
ftp.T +0% H
-

z
.
'

µ
Mark

> H'

pj! :
Br

÷iq1
⊕ anti Mark
-

""
=
+,

Br

syn
:
same side Fa
H stereochemistry
in Br
anti :
opposite sides
"/
H

OH °"
Et
it
\
01-1-01--1,04 H → Et H →

Mtg a. Et
anti OH
OH Me OH
Et

addition 1-1-04
1 ,
KB , ÉaH these are En
+
7- And
anti -
Mark so choose
" ' °"
gym tBoH write "

+ Eh
"
 OH OH
OH OH OH-

, > + En
_ syn AHH
¥
"

are
it products
Br
-
Br
☆Br meso ,
only draw

product
>

/ anti + En one

¥1Bn

HYDROGENATION
alkene
☆ adding Hz across

☆ metal catalyst
☆ syn

☆ no regio chemistry
'
"

1980$
"

H2 +
, '
""
Pt go

✓ [Link]
>
Égq

≤§
H