Description
SOU
St
CHAR 10
) Study Sous
(onwards
Grigrard reagent R-x + mg
-
+
k-ng-x7.
up
Study
irbons attached to metals behave like Rosty
Study Sap
Both more conbons
nucleophilic
Study Soup
Organo lithiums R-X + 2 Li R-Li & Loxo7 R behomes like R:0
Grignard reactions The basic grignard reaction with a carbonyl is shown below!
Ric-oi → R-¢-030 R-¢-00 HO - R-C-GH We also discuss several other topics like Where does christian religion come from?
ALCOI
YNTHESIS BY NUCLEOPHILIC ADDITIONS TO CARBONYI
GIROURS
IR
with
a
0
Ketone
Aldehyde
Formaldehyde
C
formaldehyde
Hot
O: Aldehyde
+ R .
Ketone
+ R
de
ESTER If you want to learn more check out What is the conjunctive normal form?
OH
R
+R-mgx
est R-mgx
ACIP CHLORIDO
one mol of Rmgx
nol gives alcohol.
gives ketones If you want to learn more check out Which hormones have nuclear receptors?
Mg x
/B-c-OH
R - B-c-of (B-mg x +
+ B-Max
,
D
P-o-o:
& CAPSHOT R-¢-B- Ba mg Don't forget about the age old question of What is the musical example used for theme and variation?
R-C-R
3° aleahal,
20 alaho
o alcohol
1
2
-0
70-r
D-O-01
R
1
H-O
IKETONE
s adysou
SESO
H-O-HR-C-R
cao.
H-0-4
IR-C-H
Too
Н
-С If you want to learn more check out What is the difference between arthritis and rheumatism?
and 2nd
-n-op-no
OH
-
Н
Study
Studio We also discuss several other topics like What do you mean by capital budgeting?
Sour
a) St
Soup
Addition to
Ethylone
Oxich
OH
C
H307
R- CH2 - CH2
R-mg x
R-CH2 - CH2
CH2 - CH2
Sup
Study Cup
Epoxide
REDUCTION
OF CARBONYL compoUNDS
Ř
OH (OR) (e)
-
-
-&-oh 1024
☆ H (R) Grignard's reagent
StudySoull
- NaBiL
Ketons
Aldenyde
2
10
Study Soup
o
converts comboxylic acids
to lo alcohols
LiAIHL
Alkanest
Alkenes.
brings it to 1° alwhols
Study
Raney Ni (works on any
kind of
double bond)
Soudy sou
THIOL PREPARATION -SH this group Named by adding this to alkane name
CHz-SH CH3 CH2 CH2 CH2 -SH methane thiol butanethiol
• Thiob are moll audic than alcohols
to because weakce bond in beth s-t cor of s is bigger than o 48 has moll bigger é- cloud for delicatization
Stud
& SYNTHESIS OF THIOLS
Thiols oxidation disulfide
reduction bonds
Sour
Stussy Soup S
Study Soup
Study
SOU
SE
se dySoup
CHAP
D
; loss of 2
up
Oxidation addition of Oor O2 ; X2 ; loss of H2 Reduction - addition of H2 (or H-) ; LOSS OF OXYGEN Neither - add or loss of H+ OH, H2O, HX
Studi
Study Soup
top 33cn
) Study Soup
H2sou
Nazir207 -
R-C-OM
soup
Naou
PCC
30 DONT
Sween/ome/
OXIDIZE
aldehya Ketone
an
I bettee for sensitive
becomes
Stu
and 20
ma
OXIDATION OF ALCOHOLS 1. Na2Cr2O7 2 Ketones.
1 Carboxylic acids 2) m nou in
kalboxylic acids
Aldedyces canboxylic 3) Na ou jo - Carboxylit auds.
Ketones 4) PCC
aldehydes 5) Sween H 20 Ketones 6) DMP Iso 30 cannot be oxidized ALLOHOL AS A NULIDOPHILE
weak nucleophile CROH)
• Al koxides (R-0-) strong nucleophile ALCOHOL AS A ELECTROPHILE
• weak eleemophile
• Protonation of Ho- makes it a good learning group,
can be done on & Substitution and Celimination
using tosylates (good leaving group) Dehydration of Allohals
Stud
Carboxylic
muona
I Rez 25 OH, OR, CY
OV
alcohol by
HOH
ALCOHOL -> AKKYL HALIDES y so
2002
R-ce
Pu2 Zn42
R-OHJ
- isol,
SOU
StudySoap
2) Puridine
R-Br
Bral
e
l
/ HI
R-I
Hor
) Stua, Soup
Stud
ALCOHOL - ETHER * Williamson Ether Synthesis
OOH + Nath Do Not Han You H2C - CH2 - Br o -CH2-C013
NaT
+ NaH
up
Study
Study Sou
auso Ether
StudySoup
peso. R-E-GR
StudySoup
R-o-c-R
& H2O
ALCOHOL ESTER * Fischee Esterification,
R-O-H & H-o-c-R
Aluchal Coubraglic and with acid chloride
R-O-H & a-c-R
Ester
C-c-
R
R
-0-C-R' Estes usou
Acid
Chloride
Alcohol
R H Acid chloride?
R-o-Neon
OsudySoup
Ront=0
0
OH
OH
OH
Study Soup
u
* INORGANIC
Intermediate ESTERS
Nitrate ester R-O-H)
[OH-P-OH
R-O-P-OM R-OH R-O-P-P-R OH Phosphate
ester, REACTION OF ALKOXID ES
Alloxides can be made using Na,K, NaH/THE
Important for Williamson Ether reaction.
R-0-H & Nath – R-ö & Nat +H2 t/
Alwheel
Williamson R-00 + R - C2 - - R-O-CH2 - RJ
Ethee
reaction Alkoxice Swo l' alkye halihe Ether sol
SUSQUE
Study Soup
Studio
SOU
St
CHAP-14
StudySoup
NamING ETHERS
IUPAC 1) The most complex 2) Name the small
3 CH2 Hiz- 82 C- CH2
CH2
alkyl group is the alkane name. group with o as alkoxy (Methoxy, ethoxy etc)
ro-CH2
Stud
Study Soup
Methoxycyclohexane
2-methyl-2-methoxypropane
1,2-epoxy-4-methylbyl cyclohexane
suas
NAMING EPOXIDES 1) detemine the longest chain. 2) Locate expoxy group 3) Arrange alphabetically.
Study Soup
MAKING EROXIDES ETHERS i) williamson Ether synthesis R-OH + NaH - R-6 +R-X Alcohol sinong
Study
R-O-R
Ether
Alxoxide
Alkyl Halide
base
) Sedy Soup
-
C-H
2) Alkoxymercuration - Demuuration reaction
-R NABHY
H.
7
ROH
-H
OR
x=CR & Hg (Ac), usou o Actig
OR
Ether
H
Alkene
Study Soup
REACTIONS OF ETHERS
• Cleavage of Ethers by HBr and HI
©
.
D
H
-Br
R-Bri
- Br
-
Goo + Bro
-
e
7 BY.
.
or + RO Ether
Alcohol
Alkyl
R-Br: +R-O-H. Alkyl halide
The process for phierols stops here!
hande
Soup
studySoup
12
Autoxidation
of Ethers.
SE
내국
CH3
CH3
OOH CH-o-c-CH3 +
CHE
ICH-o- of th3 excess O2
412 41
CH-o-o-c
CH3
CH3
Studio
SOUT
St
THIOETHERS R-S-R 1) syt Synthesized using williamson ethee by using a thiolate
ion as a nice instead of Alkoxide ion. 1. Sulfonium sults as Aly Alkylating agents.
Nuc & CSR
Studium
StudySOU
-
Nuc
-cu
Study Soup
-
& RAC R-C-0-4
C
COU
SYNTHESIS OF REPOXIDES
'c = c + R-d-o-0-H - Alkene peroxyacid
epoxide (MCPBA) * the most é rich double bond reacts of astee to
This is selective epoxiclation. 2) Halolydin cyclization (Inteenal SN 2)
carboxylic
acid form epoxides,
Studyso
OHS
-c-
OM
tix
epoxide.
a
in
polar solwent like
H2O.
Study
X @
Halchydin Base Ablahydrius ale fermed via addition of OPENING OF EPOXIDES 1) Via hydrohalic Acids. H
--- + HX - - -
HX
-
x-u
-X
#: 0
Study Sour
2) Via
ACID
AND BASES
H
H UN CH2 - C-Ć -
H -
CH2 - C - d
oup
Ole
Wy
05
ACID IS CATALYZE
TH3 -C- CH
JOH
4
vazh? te asto
он н
CH2-
c-c-H.
Sour
studySouz
-
OH
CH2-c-c-it
St
2
нон
H oH
The Grignaed and organolithium and attack a
reagents The regring
R to it
attack the least subs
opens up and form OH.
choose a
Studio
САР 15
av Soup
DIENES
Stud
CONJUGATED . one single bond
sepeating the double bonds
ISOLATED & two or more single bonds sepereativy
the double bonds stuar
CoMOLATED . No single bond.
seperating the double & bonds
StudySou
HEAT OR HYDROGENATION
Study Soup
tu
P STABILITY
& HEAT OF
HYDROGENATION
tudySoup
ZATIVE STABILITIES
hast stable
most stable Cumulated, taminal Internal Isoleta
diene
alkyne - Alkyne diene
tolated
diane
. Corrugated < diene
deceases
heat of hydrogenation POSITION
dy Soup
Theem
THE ALLYLIC
Kinetic
c=c
Allyric"
Position
Study Soup
Theino higher Ea
Kinetic lower Ea
THERMODYNAMIC AND KINETIC POSITIONS 1. 1,2 and 1,4 Additions.
+
H- Br
ud Cup
Bi.
no
H
a
(12) mono substituted
double bond 2° callocation
kinetic
ic
(least substituted &
results from most stable carbocation)
Sou
tudySoul
11,4)
disubstituted
double bond 1 carbocation
Theemodynamic
(most substitutos Cand results
furon least. stable cacbocation)
Study Soup
Studio
SOU
SE
StudySoup
A Allylic cations
Stability l ñ 2 carbocation
2 x 3 cacbocation 3° h most stable cacbocation.
Study up
StudySoup
*
ALLY LIC RADICE
Study Soup
RADICALS
> Study Soup
Ravlical stability i<2 <3 <l'allylic IA ALLYLIC BROMINATION
Low amount of Bre In the presence of light (hr)
Needs R-oo-R
Adds Br to the
rather than the
• NBS can be used to connel the amount of Brs
Br
allylic position double bond.
H-Br &
N-By
Bra &
CN-H.
low
concentration
) StudySoup
of Bra prevents the addition of HBr.
access the double bond. SN2 reaction of Allylic nalices are mou stable coz of
the resonance.
tudySoup
• SN2 reactions with organolithium Our selylic holiches and organelithin
of tesonce resonance.
wone stable becaen
Soup
StadySoup
SE
) Study Soup
Studio
CHAP -16
BENZENE
Study Soup
Studium
ANNULENES - hydrocarbous
with
alternating
double and single banels
[4] Annulene
[o Annulene
[8] cyclo
Annulene
AROMACZTY TEST:
dysou
Test
Aromatic
Antiaromatic
Non-Aromatic
Х
3) Planet
Planar
✓
2) Hybridization
sp/sp
sp3
sp2/sp.
Study Soup
UN
4N+2
3) Hikles rule
4) Example
4-4N
6=4N+ 2
L3) Annulene [io ] Annulene
is non aromatic coz Aromatic isomers
of no planar shape are non aromatic, Y & Non alomatic
Study Soup
CYCLOPENTADIENYL
IONS
+ B
-
Ter= AROMATIC
4 π e not SOUP aromatic CYCLOHEPTATRIENZL
udy Soup
FONS
1 Study Soup
& & sp2
HT
H2O
che, spa
-AROMATIC
St
Studio
SOU
SE
CYCLOOCTATETRAENE DI ANION
+ K
+ 2K
O
8 Ten
=4N Alo Anti Aromatic
10 Te - AROMATIC
Study up
Study Soap
HETEROATOMS
) StudySoup
To Get
involved
- 6 Te
oup - 6 Te
- 6 T e
- Spe - AROMATIC
- blue -sp?
-AROMATIC
make it
Aromatic
- sp2 - AROMATIC
- sp2 - AROMATIC
) StudySoup
BASIC OR
NOT?
IN ENTH
N
Not basic
Basic
Not basic
Basic
or the love
pair takes part
in aromanity
DISUBSTITUTED
DIENES
meta
ortho
para
PHENYL
VS
BENZYL
Study Soup
OCH2 {
Sour
sudy Soup
SE
(
Phenye
Beneye
Studys up
Stud
ISSOU
AROMATICO SUBSTITUTION
LCHAP
17
ELEC TROPHILIC STEPI
+
Step 2
[ext basei D E + base
STEP 2
Stup
StudySoup
Study Soup
Argarin
Aicle, ou
77 LHNO3/H THREE WATS TO FORM CARBO ATIBMS
NO 200
Ha
OH
, Bf3 iudy
Clemmensen
Reduction.
.
a
, H2SO4
, HE
lo- ortho m-meta P- para
(12) (1,3) 11,4)
, ALUZ
1.
2ND GROUP
ADDITIONS
) StudySoup
DIRECTING
GROUP
ACTIVATING/ DEACTIVATING
Activating
Deactivation
- NO2
Activating Deactivating
m. o
op!
m
Deactivating Deactivating Deactivating
1
Study Soul
op
lo:
Activating
op
-a:
Study Soup
Deactivating
op
Activating
EXCEPTIONS
NH2
Study Soup
-OH
Activating
- S-OH Deactivating me
During the signa complex (there is a completion of octet at o and
s
adySoup
ome
Activating
PO
Iss op
Stud
SOUT
St
ENERGY DIAGRAMS
RTO
Mz Nor
NO2
NUZ
NO2
VH
POSITION
Sup
Study Soup
СН3
PARA
Studys
loszTION
H NO2
H
No2
H NO2
Study Typ
o
CH3
13° CH3
сна
CH3
ansour
7 Never 30
3) StudySoup
МЕТІЯ
H
+
Noz
I POSITION
NO2
NO2
20
) StudySoup
or tho and mila para y 3 Carbocation but
more stable because there is a chance in mela there is herec a 3 callocation.
NO2
NO2
2 stud
ho ipara
ortho
benene
НЕ
NU
su
YCH
meta
boncen
I the and para
Energy
VOUR
least enefy
StudySoup
Dettet
Activating groups. Stur prefer op because lowee
Cheegy than meta.
Deactivating groeps.
prefer neta z lower energy than
Study Soup
Stud Soup
op
Study Soup