y
Benzyne>
Be
ek
\l5 CeHu
(1,2) -didehydavbenzene
— Also called = fryhe.
Ny IS NQutval Reaction Tntermediate -
i +, Fromatic in nature
o
aan TeacHve Intermediate. because af the
> Presence Shrain-
g) ———
eee
eee
Pee co — Benzyne Se illic in Nodure 80, tt is_abbickel
I 7 by Nucleophile ives Nucleophillic addition Rx
[ewe See .
1: From Halo benzene —>
A) “In Polar protic Solvent :- ae
ire. 720, Nig NHa-R ,R-oW etc
x Nant, Hens or”. a i
eee eee ea
og on al
‘ >
re
Tn Polay protic . .
| ees °
> RDS. —> Releasing o nr and Deawiieg OPC
eee Here 4. anism takes place . Cc
} feng CF,cl, Br,
ra Reactivity —>
Br > TP a>
. °C
| B)* Th polar Aprotic solvent 3+ °
| be. (DMSO, Acetone. Acetonitile , oO
Cc
j So
| Here Step wise mechanism -takes pigce- ©
°
oY > oF-O
> GC Po” re
Cea) Ge) E,C-B mechanism © &
Slows 7 ROS ‘ ©
Unimolecular Conjugate Base
Elimination.
o
©
| c
°
SaOeHOHOM HPF ePHeORHOPheHKPLlOe PRE LLLx CFcl B4/E)
Cle, i eyes
Relative Reackvily :~
From Substituted Halobenzene —
Conly EL efect of Subshiyen
4
Para -Isomey
z
Zz
cor?
x, w nl
T
Dee
re Cc
Pr ©
1°
1s
mo
3°
We
We
We
ae
aor on
2 ; NaNtta.
d,¢ = oH eeau @ iI
: ~
H,° (+1) oy
ae ‘vets 3
E:
a
a
abe CHL) NP PUD
°
{ GN _, more ncidic) 1"
6. NaNis .
| wl cc) 9
i <)
uw
CLL LS
SHEPPRPPP EP ETP SD HP OREO HM EO HM HOH HRHOLCOK HL LO LL
\ NaNho >
of ©
S .
a : U2 ©
| c
i i °
| ) di Halobenzene — °
°
if He ae c
| Oe br | sfinetatiasion Se, m® © -
os
io
4 jn
Relative Reactivity oj Metal :~
(X= Fl, By, L) were
eeooooooogoas
ots
© tw Y
a. BI’
Rui
15
TBRF
veeee4
‘
CECEE
CeCe eee Oeee e.¢€
escceoccecs
Je
pe eet ee a ee ee
eeeeev ev vn
om
=
-
|e
<=
ece
From aAnthranilic Acid:
_— Nia NaNo Hel
pt
2) oN or
f HNO2
3
i
S))
cl, By, 1 eke YL
Naon cag
a
et o®
iy 4
—Cor
=a A
NN O°.
Ge ~
\ No
cg ="
as So Sn
\es Stabe cpa
Form ak lone em’
Pb (OAC, 2
“ORS Tee S)
ie
uP
Diazonivm Salk Stable af 0° to Sc as-Tempy es to S°C
Na Rekase Autvmeticably.oT
4 )
é
©0900 600 0 OG © 0 Oo Oo ole
+t. ®
=
a
Q
_
o
A
vecoce WS
Ove 0e 06 6 6 ———_ gxz__—_—_ —ZF___— | |__|; 7
FiSD 3 Pee eee ee
Ba,
Ny Na i © Suit 0 wy,
Ny \s mr ( u ty te Tis Coon Coon o°%
Ray ee Novy Ty Ho, ‘Hitve ‘at
se : Wt ro i" 6 non,
ee ome nt}
: Fone opm ] i it
-
, ane N ’ % ( ) |
iD (Hf wv © ( 7
: “J WM) N A
€
Le Dimerisation and
_ Dimerta a5 e
ei oy
/. ¢ Y gemane}
|
PAC
GO
SSSsSsssSHUHPwUUtUUuceLectse cles
¢
Timer ay Lf
a. ;
7 be self heaves os the dienophile. _(clectronicany
: Agliciond Species) fn, ur valll Reged with here ( wn ralhy
r ich Spe iven, 5 q
Rich 9p-) and gives Delon Aldon. Reaction C444 (yelu adn)
co
vu
Yv
Den
8[x '
oo ee
ae BA y om ao
t
|
Gg eas OM
] sy
: A
1
an A
— > \
Ss
3: Nucleophillic Addition Rx PS
Since Benzyne js electrophillic ae Sy Tt ip attacked
by Nucleophile and gives — Nucleophilly? Hon Rxn-
Ey + ew
mechanism —
eo é 5e
CIR + ~ CM if
| Nucieopnillic Addition in Substituted Benzyne>
oS
G
: °e
C#t) ©
“ea
Co
G
Cc
i oe
WW
OO COCECCCOSOGMOCGOC OOSmojor
ome.
ae
\
3 or
“ 4 ynojor
ie :
AO
a Oo 4 Nanos tHe) 4 >) Fy
x ais) @ HO Cv
r ° [ ye
~ o — S
7 2 @y
J ©
he oO Le
"7 6 &2 4
Mg-Hg- i
Mo er as
IS o a a
ye Ge ons
lo
yo “
2 i)
wg OOS
oo re we
> B
a : soy Gh DME
2g
ie . l2 +RLi —> Ce, ann
a
‘ uO AC ee
p iftimes \
e v cB
|TIFT FT eS es ae
cocoosc EES
cit
Work uP
®
Nhs
oo
2. ®
aH.
6
ao
CuNy
a |
AYO 7 |
ay ~@ | Nanha @ Nata
\? = Kc | = : CHgCN
~“ i W
wwe
Our— CLs. Ga
cHacn + NdNH2 ——> Br, —en
cho [Ht Pee
Hono [Ht cy
CHaCle =
P Pha +FBxy
Bali
Hao
Oo
F PRL /THR |
=
then.
Te",
VSO ov vv veer eve ce cece
v
Tv
,
yVIF FILS TT TS ee ETT TTT een
POOCOCOSLOOSCVODO0000& 0000000
773 :
2 °
$833 é ie
zg @ & i
= — = iy
S :
a
|
Ph
cmH
\
| PPhatcBry
Bub
Ho
P|
CG
SN
Ro
Pyridinium chloro
——O
Ss
‘NH
cy
Zz
To
8
2
chroma)
dd Loe S
ey
iy Pd-¢
>
a
—
as
A—o—
it
oe
pr
Ri
cD
Sy2
Y, 4 Mal onote ester
avy ~~ 7
© 5 abe
an il LL Naw, 9 LO 28!
; Ge + eto oet ome
& br " Cmatonate estes)
Gj solD- ome Doe ae 0b
uy ZT 4) | Wo Nei — a ee Ko
iy @ *~Ncooet 8 Ss
wv : we ome” Ke ome. o¢t
at { Cook
i) e
A a
9 ) cst qme ott
°
Ou: thane aes work uP
ay p « WU) Base
> mee) oo) oe oi oi ee i ee io i mei in io in ign fel llmn COUie rr rTheesrmeerawi Fs vee ri ee rs riers ae fan
VovvsyrxVv2xVUUUErtUlEeccececee
VV
ecPa
oe or
< b=) Ge : goo , :
[ OMe ®
Oo
Nome
ented
|
SS acho “ coat coo et
me
ey Por
eK a
Oe a :
Ne ne
é oe ;
i. ° ome.
| 2tlea 101g
1 oe pn
| —— omom <
i Los est gon’ — thu
Om Lg
| oe ome _
| — We vie [18°C ® — ®-—-
af “yee 0% :
Oy Pre Crm
©
S256 )
so
Qo0oao0
eooooo
Ite SSP PP LRT OLS LPOR TLL LES
veceee
i
°
°
a ee er ee ee eeil Qu
Nucleophillic Substitution iN Haloderivatives .- 2log}zo1g,
AY
S
q
Hatod erivedives
~
By
By Miphatc saturated Halide 1 frul Halide ag Hie
~
i
a ee 2 oe omnes
a — tou ir
XS v
2 “J Weak « bond —s
ze 4S, a
a
Re
a
Fe:
Pe:
bond charades ) ey > cee
(Partially core]
: . a i (Bond characte
‘ ‘ ~Nue
1 a ie aN x ’ A
ao Vacant ff 5 me
= ae Blechonic
tI 4 Repuision.
a2 -
1; Apo
L 2
vu
7
SETeNe TT
i
ees
\)
A
9FB yg — cH = C—— CH Hg
o b > CHa CH Ee cy —CHy
Lequi nue
Halngens! :
Halides gives Nucleophillic substitution Reaction. Via
og types Y mechanigm
Ya
Na
Substitution
Nu®
ArvSn>
Mecha nig rn +-
SCS Ba,
Tpso
Carbgn: Cy
es ine Slon- \
Roe
Ypso atteek—
Sp — Sp?
Addition Hep
ArSn2 Mechanism —> )r
Ny
a
Benzyne Mechanipr,
ow
Cine Subst huion
or
Elimination — Redition rechanipm
ee ny
G5
CS
5g
N
Woe)
co
Meisenheimey Complex
eo ec.
°
oageo
oco$o
oo
ecececosd
Wreceerererereeerrerereeearsrsr essere7. nin
a i aaa Rate & [eotio-e lJ LN)
tol
Jollow Second ardey
Kinelves
Te is also Kla Relivalal Complex Peebanisny
since Foleymediote Carbanion ts form in KDS+ Ho, dy nte
of Rlecben withdrawing hp. in Mayt. Hatide (Yes lve
We. 3 Pays Mechamsm:] Pes the Reachivily gy Subslrale
« ? PySpX mechaniypm
9 ‘ ' .
4 a nce Ss Bw o |p more efpective When Ut Vices dhe
w ortho «4 ~ fesi Hon cot to Leaving gap -
v
Se Th Mation takes place. in bl Carbon. and—~
mC Soom nue :
mo —
pa © Que Prrange the following ae order af Reactivity—
ye towards — ASN we
50 “1
a a i
Nop. ee
oO Qn Non,
ai
wee ee
eee
z
a
v
DE
f
SSovvvvvy v-
i.
*
Zz
z0 e
Te is also Kla Activatal Compley mechanism:
May SS
Ry :
“i cy Na ey
u a = a Rake & [colts-cl') (uuO}
x ce :
uy . Sp3 -sp2 ' wo Follour Second order
— ee
MI : elimination kineheg
ole-4 inte. Fnleymediote Carbanion 1s form in RDS- Go, Bw
of Blecton withdvavsing gop In Aaj Halide Ds toe,
“fi Prd mechanism: | @e tre Reachvily 9 Substrate
9
firGNR mechanrpm
Le,
3°
Th nce.g) EWG 1b more effective when i Ves Whe
to Leaving gep-
* Th RD-S Bon fien takes place. in bls Carbon and—~
Focoming Nue ,
Que Prange the following en order of Reactivity
La Wee eee eee es
OH OME EO EK
©
| Co towards — ArSN2_ mechanigfth +
j o cy
I G a u a
1° G cor™ fo}
Ml oc = BY
aly « Cy Nor = A
mgt el.
a, 2 Non, = (B>LY29495
qe es
DH * & jee i
Boe a °
Boe ye
Boe x Nu
Re
.
|
Ai; i
{ |
: Ex $40
. Noa, \
A ee + Lo \
equi .
Nu
3 Mo,
ine
&
L
°
&
&
&
(oye on 1D wor :
2 eo . —— ‘
: by Loy a)
F - =
° J q
Note-2 |
\
}
| As the Blectphiliaty ey Tpso nh
\
‘
{
Sor
Reach vity
towors — ArSN? J Rate oy freon
spl I 7 2.
Rate of Aesn® Dea
Reattinily a Subst towards fron? (Des
S
St o
| °
Kop) 5 9 ‘s3 “<
No, Now Now No, “]
SS ———_—_ CCG
| =I effect o Halege Ges
Blectrophillicty J Jpso Orban bes
|
i
i
|
ececcecce
eoecooeccaoons
>} Pr epee eer eereee pepe pe SP Pf eSW ,
|
|
id
eeu.
Bee
ee
uu
REET Eee e
oD 4)
Gat)
yy) chibebin Reacton >
a)
“
‘ul
also The example of eS? mechanem
US in pyeiding 4 Qyinolingt TaoQuindies-
: =
po ———_» |i & bi uy
cM i A wy" 3 Wo
Mechantorn .—
Ch ° AF ya i
2 cs
GH Ns Sp?—> oy yt @
err A [
Og, be
~ Aa ty
el)
Gem a Lal Hy
ice D
Vs
9p — op. = 4
Elininahan Pin
Rot. & Ca) Cru? J
(Filow IL order Kinetics)
|
|
g|
ead
Ca.
3
sequi Nu® eu
Se
Ry
JO. ts
“J a
ined) dequi Me
sy pote ee No Rin
— me
me
= VO
@ Men
1 N 4 fy 4.
. ,
3
e
©
c
e
©
| Co
i cy iv c
eB } N :
ca a .
| N PY co
| S8rn. cl a
— NuS 7 Cy ue
tS ae a C
°
©
Qu Arerarge the Following mn Usiy order 2 by a
towards Teenithibabin Ren °
°
ar
io a fel ee
j \> > Bou, :
fa =| ©
°
~ Oo a
Sy SH ma °
| p32 °
°
4
1
;
’
,
f
il
4
ba
il
4
‘I
Hi
il
i!
il
A]
il
il
dl
‘I
|
|P
vo
akk
1
oO _%86 Ps Lewei Nue o's
ae Tne > ooh
: J]
vo
G ~~ oui ue “ee
¢ ANAM
Rs
NS » Que Complete Pre Tollowaing Ri a
Im .
ee eget ~ il Fei Mu - 7
4 ‘ : i Neo we oH
7 e
3 4 | hy
a
Me
ay
id -
ad tow
1 "
Vy,
Ae
suet
r ) . 5 ls ae Nu
a
x oO /
a: ; ie Qe
i of ery. W Poke ray
>
>
4
2
2
a
a
wesee
¢ —
Y ge ow feu Nude AL
2 ors 4" OD
© SN SO
yo
syeeeeeeee mg Ir
Jd eayi ud : \ J \
1 y echantan Whe Wu) ned ape
| (Kou 4
' (ne Nagy.
Nig, R= ity) :
iy So
\
( Cine Substitution) S—~
\ * _satiita,_ a) OY
Mechanisya (kxee ‘hg
ececce
i }
: err nabs + a
omg l | _ Nana KN oe (OW Onin, :
i= on ‘p ° Car)
i ) (em) hennyne, Oo,
coy) .
( ; Z sy ered 6 7
Fm ce 4 (eo o
- Hi \ 4
} Nh + MMe _. 3 “NM \ JI G 4
(484 °,
—— rere!2
fF
€ ith fov_B
enayNe Mechanism —
LY EL
Presence Q ’ oY, ,
Presence g) ortho H adom wwrved leaving SOUP musty
Requirement 9) Ahong Bane: fe~ NaNla , Buti, LDA ce
iS alheence 4 (owe a tn the Pubsfrate
Presence BRO COR, Cy we) In the Bengene Reng fees
LER, tHd
iS
&
¥ CDy ~~ on, —or ele nee
|. Que. Set oC
a) ue AY, $y)
_ wo im sO étoNa
mw up Nog
Relative, lan, S
ws Ree conkeg is Ps. NO een
|
S re: Oe
Etoty
( Nani
2 ANH; aa
7 o _ Keke Kad ty
A) Ky> ka and kod ky Cepy QO wa
G@ Kook, and Kg ky bp) Koka
Nucteopil Substihution —>
nat 1 nge a RNa AL:
Sub aleale. ao '
ENatine a) 4) Substrate? a
{ ree ~—
Avomasic Nucleophillic Substitution Aliphatic Nucleophillic Sub"
oe at fl Ceca
NSW Bervaymne. cD) Sut ey? Sut NUPs
Mech| a Nog wee
or
Nano tke! Colazotisation Rxn)
O-49 6*c.
| Replacement gy Na from
|
sé ArSNE Cunimotecutar Fhromotic Nucleophillic Substitution) — —-
[
Benzene diageniome’ Saif
°
oO
PPrPrePrprnvenkeeaneeetnr
Q
Oo
ooo0oeos9d
Ren « C
> Cc
Presence @ ERG: In << >» the Rode}. “Diazotisation ©
eo f
o
by Nue
Poo ooo oO
eoooce oosg
aArSnt mechanipm —>
PAGS caer ie
. '
NEN cr®
al + NU® —__, fog. iN
Mechanipm ‘-
AvSn2 mechanigm-
Maolh COT
ROH/D OR,
5 [x ony CS"
On Kron or
foun, °F
kd ae.
aS
opt
ee
\ an =uel oy 6 so cot
om fluorit Acid: ET zene Diazonane 8 Ty a)
Bornftuarote oo(B) cod oy Here Free Radical
= oi eos) \ is form onthe
Guay bua Ran “Lnterm ed iccte
Gaby VBE {o \ &
e =
® J Ciro ¥ By ~ —
tae
act tle
or
Cua Cen), Fon
(Cur Powder PME
~>
qr:
~4eo °
G Cucla 225 cucl + 01
S40 OS yy
gre es"
Og th
vol
acy — (CW +
co SNS" Radical
aon
( Benzene Carbenshile /
0K)
Lecce OW
RIS; ! TT
|
~! © B Reduchve deamination —»
Mia,
a
> ic HaPo>
r oe Es @
se Qe Gromberg _ Reaction - _—
len GY Asomatic Substrade- by benzene diazoniven Salt
a Gromberg Rxn-
ee = oe
matic Substrode-
mechaniam ;-
plage.
Se 7 ,
a
7
co
nbd eA ted
i
c aeeeaeee:
7
Be K+ ere Onn
lo -
[> °°
t
|r
vo
oe
ce
van
Vo
Ls
f
|(FOReplacement by —NO, Group —
]
i
Mechanism —
ee! @ we .
ne No BFP cs Pode em 1G,
“hs Oy ane COS
HNO. 1 Nog
Sy Gigo:, Coy
Couftin: tion —>
DAMS sor
=NHe Sere.
< —Nme,
Bynen ye
Azodyes -
til
c Wo.
a Le
ae
a oad
ernreawrnre er
ao
Ln eRe ee
El echophile Nucleophite
| Slow
3 RDS
i ;
a 4
7: Fast oe
¢
| Oyn-N en