Organic Chemistry

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CH3-CH2-CH3

CH3-CH2-CH2-CH3

Ethane [ C2H6] Propane [C3H8]

Butane [C4H10]

Methane [CH4]

CH3-CH2-CH2-CH2-CH3

Pentane

C

H

H

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H C

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Iso butane[C4H10] Iso pentane [ C5H12] Neo pentane [C5H12]

C8R CH C8R

C8R

C8R CH CH@ C8R

C8RC8R C C8R

C8R

C8R

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R-CH=CH2 H2Ni or Pt

R-CH2-CH3

Alkene Alkane

R-C=CH + 2H2

Ni or Pt R-CH2-CH3

Alkane

O

Alkyne !

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R-I +HIP

150o; pressure

RH + I2

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R-OH 2HI red PR-H H2O I2

R-CHO 4HI R-CH3 2I2

R-CO-R R-CH2R

R-COOH 6HI 2H2O 3I2

red P

red P

red P

4HI

R-CH3

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H2O 2I2O

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R-CH2R H2OZn-Hg/HCl

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!!!! ! !!!!!!R-X 2Na X-R R-R 2NaX

dry ether

alkaneO O O

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CH3-I 2Na I-C2H5 CH3-C2H5 2NaIO O O

Propane !

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CH3-I 2Na I-CH3 CH3-CH3 2NaIO O O

Ethane !

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C2H5-I 2Na I-C2H5 C2H5-C2H5 2NaIO O O

Butane !

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R-X + 2Li RLi +LiX

2RLi +CuI +LiI

+R'X R-R' +RCu +LiX

Li(R)2Cu

R2CuLi

Alkane !

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RX +Mg ether RMgX

RMgX +HOH R-H +MgX(OH) Alkane

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R-COONa +NaOH CaO

R-H + Na2CO3

CH3COONa +NaOH

CaOCH

4 + Na2CO3

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AT ANODE

2NaOH +H2

AT CATHODE

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CH4

Cl2

-HClCH3Cl

methyl chloride

Cl2

-HClCH2Cl2

Cl2

-HClCHCl3 CCl4

dichloromethane

Cl2

-HClchloroform carbon tetra choride !

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CH4I2 CH3I+ HI+

5HI HIO3 3I2 3H2O + +!

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R-H HO-NO2 + 400-500oC R-NO2 H2O +!

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CH3CH2CH3HNO3

CH3CH2CH2NO2 CH3-CH-CH3 C2H5NO2 CH3NO2

NO2

+ + + 400oC

!

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R-H R-SO3H H2O

alkane fuming sulphuric acid alkane sulphonic acid

HO-SO3HO O!

](;%+!#6G#&%1!9(!&(,!M0L%!,/01!+%#4,0(&C!

!

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CH3CH3CH3

400-600oC

CH2=CH-CH3

CH2=CH2 CH4

CH4

400-600oC

O

O!

^&! *+%1%&4%! (-! 4#,#621,! *2+(62101! 4#&! I%! 4#++0%9! (5,! #,! 6%11! /0M/%+! ,%$*%+#,5+%C! K/01! 01! 4#66%9!

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CH3-CH2-CH2-CH3

AlCl3/HCl

25oCCH3-CH-CH3

CH3

n-Butane Iso butane !

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/($(6(M(51!#,!/0M/!,%$*%+#,5+%!#&9!0&!,/%!*+%1%&4%!(-!4#,#621,C!

3(+!%J#$*6%a!!

Cr2O3-Al2O3

600oC

4H2

n-Hexane Benzene

CH3

CH2

CH2

CH2

H2C

H2C

CH3

CH

CH

C

CH

HC

HC

CH3

CH3

CH2

CH3

CH2

CH2

CH2

n-Heptane Toluene

Cr2O3-Al2O3

600oC

CH

CH

CH

CH

HC

HC

4H2O

O

!

^K! F@781>7;2Z';O<C4>7;2[J! b/%&! I5+&,! ! 0&! %J4%11! (-! #0+! (+! (J2M%&! #6G#&%1! -(+$! 4#+I(&!

90(J09%!#&9!;#,%+!;0,/!,/%!%L(65,0(&!(-!/%#,C!!!

! D

3(+!QJ#$*6%a!

CH4 2O2 CO2 2H2O heat + + +

2C2H6 7O2 4CO2 6H2O + + heat +!

^&!M%&%+#6H!

n 2n + 2C H 3n+1

2O2 nCO2 + + (n+1) H2O + heat

!K/%!%L(65,0(&!(-!/%#,!0&!,/01!+%#4,0(&!-(+$1!,/%!I#101!(-!,/%!51%!(-!,/%1%!/29+(4#+I(&1!#1!1(5+4%!

(-!/%#,!#&9!*(;%+C!

!

$/03234!;:!F/3H724!

F6G%&%1! #+%! 5&1#,5+#,%9! /29+(4#+I(&1! 4(&,#0&0&M! 4#+I(&<4#+I(&! 9(5I6%! I(&9! A.f.E! 0&! ,/%0+!

$(6%456%1C!g%&%+#6! -(+$56#!(-!#6G%&%! 01!.&8@&C!K/%2!#+%!4($$(&62!G&(;&!#1!(6%-0&1!I%4#51%!

6(;%+!$%$I%+1!-(+$!(06!*+(954,1!;0,/!4/6(+0&%!(+!I+($0&%!A]#,0&!c6%5$fc06[!-04#&%!f!,(!$#G%EC!

Q,/26%&%!#&9!*+(*26%&%!#+%!,/%!-0+1,!#&9!1%4(&9!$%$I%+1!(-!,/01!1%+0%1!+%1*%4,0L%62C!

C C

HH

H H

C C

HH

CH3 H

or or

CH2=CH2CH3CH=CH2

Ethylene ( C2H4)Propylene (C3H6)

!!

)(5I6%!I(&9%9!4#+I(&!0&!#6G%&%1!01!1*@!/2I+0901%9C!K/%!.#+I(&<.#+I(&!9(5I6%!I(&9!0&!#6G%&%!

4(&101,1! (-! (&%! 10M$#! A!E! #&9! (&%! *0! A"E! I(&9C! "0M$#! I(&9! 01! -(+$%9! I2! (L%+6#**0&M! (-! 1*@!

/2I+09!(+I0,#6!(-!%#4/!4#+I(&!#&9!"!I(&9! 01! -(+$%9!I2!(L%+6#**0&M!(-!5&/2I+0901%9!*<(+I0,#61C!

K/%!,;(!4#+I(&!#,($1!;/04/!#+%!9(5I6%!I(&9%9!0&!!#6G#&%1!#+%!/%69!$(+%!,0M/,62!,(M%,/%+!,/#&!0&!

#6G#&%! ;0,/! ,/%! +%156,! ! .f.! I(&9! 6%&M,/! 0&! #6G%&%! 01! 6%11! A=CRBF(E! ,/#&! .<.! I(&9! 6%&M,/! 0&!

#6G#&%1C!

3(+!%J#$*6%[!

!

c+I0,#6!",+54,5+%!(-!Q,/#&%!

! h

F6G#&%1! #+%! $(+%! +%#4,0L%! ,/#&! #6G#&%1! ,/01! 01! 95%! ,(! ,/%! #L#06#I060,2! (-! $(+%! %J*(1%9! "<

%6%4,+(&1C!

!

&3>=;84!;H!":3?1:1>7;24J!

SK! D3=68:1>7;2! ;H! $/9;=;/4J!b/%&! #&! #64(/(6! 01! /%#,%9! ;0,/! 4(&4%&,+#,%9! 156*/5+04! #409! #,!

=>>(.!(+!;0,/! */(1*/(+04! #409! #,! @>>

(.!(+! I2!*#110&M! #64(/(6!L#*(5+! (L%+! #65$0&#H!N@cV

!! (+!

#&/29+(51!S0&4!4/6(+09%!#,!RV><B>>(.!#!$(6%456%!(-!;#,%+!01!%60$0&#,%9!#&9!#6G%&%!01!-(+$%9C!

R CH CH2

H OHR-CH=CH2 H2OO

!

K/%!%#1%!(-!9%/29+#,0(&!-(66(;1!,/%!-(66(;0&M!(+9%+C!

R(!#64(/(6!i@

!(!#64(/(6!i=

!(!#64(/(6!

)%/29+#,0(&!(-!5&12$$%,+04#6!@(!(+!!=

!(!#64(/(6!4#&!*+(4%%9!0&!,;(!;#21!#&9!$0J,5+%!(-!#6G%&%!

01!-(+$%9!-(+!%J#$*6%!9%/29+#,0(&!(-!@<I5,#&(6!20%691!$0J,5+%!(-!@<I5,%&%CA$#j(+!*+(954,E!#&9!

=<I5,%&%!A$0&(+!*+(954,EC!

CH3 CH CH CH

HH OH

H2SO4

H2SO4

CH2-CH=CH-CH3

CH3-CH2-CH=CH2

2-Butene; 80%

1-Butene ; 20%!

^&!154/!4#1%1!$#j(+!*+(954,1!4#&!I%!*+%904,%9!I2!-16>N3HHR4!:C/3C!b/04/!1,#,%1!,/#,!k829+(M%&!01!

*+%-%+%&,0#662!%60$0&#,%9!-+($!,/%!4#+I(&!#,($!;0,/!-%;%+!&5$I%+!(-!/29+(M%&!#,($1Cl!K/51!@<

I5,%&%!01!,/%!$#j(+!*+(954,!0&!#I(L%!%J#$*6%C!^&!(,/%+!;(+91!"#2,S%--Y1!+56%!1,#,%1!,/#,!kg+%#,%+!

,/%!&5$I%+!(-!#6G26!M+(5*1!#,,#4/%9!,(!,/%!9(5I6%!I(&9%9!4#+I(&!#,($1H!,/%!$(+%!1,#I6%!01!,/%!

F6G%&%Cl! 8%&4%! $(+%! 15I1,0,5,%9! #6G%&%! 01! *+%-%+%&,0#662! -(+$%9C! K/%! %#1%! (-! -(+$#,0(&! (-!

#6G%&%!01!H!

!

[email protected]@[email protected][email protected]@!i!Z.8f.8Z!i!Z.8f.8@!!K/01!4#&!I%!%J*6#0&%9!(&!,/%!I#101!(-!$(+%!1,#I060,2!(-!$(+%!15I1,0,5,%9!4#+I(&05$!0(&!-(+$%9C!

77K!T6!83=68:;L321>7;2!;H!$/06/!=1/7834J!;/%&!#&!#6G26!/#609%!01!/%#,%9!;0,/!#64(/(604!:#c8!

(+!mc8H!(&%!$(6%456%!(-!/29+(M%&!/#609%!A8_E!01!%60$0&#,%9!,(!M0L%!#6G%&%C!

R-CH2-CH2Xalc.KOH

R-CH=CH2 + HX!

K/%!%#1%!(-!9%/29+(M%&#,0(&!(-!#6G26!/#609%!01!!

R(!#6G26!/#609%i@

!(!!#6G26!/#609%!i=

!(!#6G26!/#609%!

^&! 4#1%! (-! 9%/29+(M%&#,0(&! (-! @! (! #&9! R

(! #6G26! /#609%1! ,/%! $#j(+! *+(954,! 4#&! I%! *+%904,%9!

#44(+90&M!,(!"#2,S%--Y1!+56%C!QCMC!

!

! U

CH3 CH CH2 CH3

Br

alc. KOH CH2=CH-CH2-CH3 CH3-CH=CH-H3+

1-Butene

(minor)

2-Butene

(major) !!

777K! T6! D3=68:;! #1/;L321>7;2! ;H! V79721/! D7=1/783J! ;/%&! L040&#6! 90/#609%1! A4(&,#0&0&M! ,;(!

/#6(M%&!#,($1!#,!#9j#4%&,!4#+I(&E!#+%!/%#,%9!;0,/!S0&4!951,!0&!#64(/(6!#6G%&%1!#+%!*+(954%9C!

!

!!!!!!!!!!!!!!

CH3 CH CH2

Br Br

alcoholR-CH=CH 2 ZnBr 2

Zn OO!

7EK!T6!A;/<3R4! 3/39>:;/6>79!O3>=;8J! %6%4,+(62101! (-! #d5%(51! 1(65,0(&! (-! 1(905$!(+! *(,#1105$!

1#6,!(-!1#,5+#,%9!904#+I(J2604!#4091!20%691!#6G%&%C!

!

CH

CH

COONa

COONa

R

R

2H2O +electrolysis

CH

CH

R

R

CO2 2NaOH H2 + + +

At CathodeAt anode

!

!

EK!T6!9;2>:;//38!#68:;L321>7;2!;H!$/0623J!F6G2&%!01!*+%1%&4%!(-!]0&96#+!.#,#621,!+%#4,!;0,/!

829+(M%&!0&!4(&,+(66%9!$#&&%+1!,(!M0L%!#6G%&%C!^&!]096#+!4#,#621,!N9!01!9%#4,0L#,%9!;0,/!.#.cR!

#&9!d50&(60&%C!

!!!!!!!!!!!!!!!!!!!!!!!!!

R C C R + H2

Pd-CaCO3

quinoline

R-CH=CH2

Alkene !

E7K!!':19072L!;H!$/01234J!N#+#--0&1!(&!/%#,0&M!#,!V>><h>>!.!0&!#I1%&4%!(-!#0+!M%,!9%4($*(1%9!

,(!6(;%+!$(6%456#+!;%0M/,!#6G%&%H!#6G#&%1!#&9!/29+(M%&C!

CH4 + CH

3-CH

3 C

2H

4 + H

2

?>>!n.

!":;?3:>734!;H!$/03234J!

"=64791/!?:;?3:>734J!!

=E K/%! -0+1,! ,/+%%!$%$I%+1! #+%! M#1%1! #,! (+90&#+2! ,%$*%+#,5+%H! &%J,! =B! #+%! 60d5091! #&9! ,/%!/0M/%+!(&%1!#+%!1(6091C!QJ4%*,!%,/26%&%!#66!$%$I%+1!#+%!4(6(5+6%11!#&9!(9(+6%11C!Q,/26%&%!

01!*6%#1#&,!1$%660&M!M#1C!

@E F6G%&%1!#+%!(&62!160M/,62!1(65I6%!0&!;#,%+!I5,!1(65I6%!0&!&(&!*(6#+!1(6L%&,1C!RE g%&%+#662H!,/%0+!I(060&M!*(0&,1H!$%6,0&M!*(0&,1!#&9!1*%40-04!M+#L0,0%1!+01%!;0,/!0&4+%#1%!(-!$(6%456#+!;%0M/,1C!35+,/%+! 60G%!#6G#&%1H! ,/%!I+#&4/%9!4/#0&!#6G%&%1!/#L%! 6(;%+!I(060&M!

*(0&,1!,/#&!,/%!4(++%1*(&90&M!&<#6G%&%1C!

BE ]0G%! #6G#&%1H! #6G%&%1! #+%! M%&%+#662! &(&! *(6#+H! I5,! 4%+,#0&! #6G%&%1! 95%! ,(! ,/%0+!5&12$$%,+04#6!1,+54,5+%!#+%!;%#G62!*(6#+C!K+#&1!#6G%&%!/#1!#!1$#66%+!90*(6%!$($%&,!,/#&!

401<01($%+!I%4#51%! ,+#&1! 01($%+! 01! +%6#,0L%62!$(+%! 12$$%,+04#6! ,/#&!401<#6G%&%C!)5%! ,(!

! =>

*((+%+!12$$%,+2!$(6%456%1!(-!401<#6G%&%1!9(!&(,!-0,!0&,(!,/%!4+21,#6!6#,,04%!1(!;%66!#1!0&!

,/%!,+#&1<01($%+!;0,/!,/%!+%156,!401!#G%&%1!/#L%!M%&%+#662!6(;%+!$%6,0&M!*(0&,1! ,/#&!,/%!

,+#&1C!

!

'=3O791/!?:;?3:>734J!F6G%&%1! #+%!$(+%! +%#4,0L%! ,/#&!#6G#&%1! 95%! ,(! ,/%! *+%1%&4%! (-!"<I(&9C!

K/%!"! %6%4,+(&1! 4(&1,0,5,0&M!"! I(&9! #+%! 6(4#,%9!$54/! -#+,/%+! ,/%! 4#+I(&!&546%0! #&9! #+%! %#1062!

#L#06#I6%! -(+! +%#4,0(&! ;/%&! &%%9%9C! K/%! (L%+6#*! (-! #,($04! (+I0,#6! -(+$0&M! "<I(&9! 01! &(,! #1!

%--%4,0L%!#1!,/#,!0&!!!I(&91C!K/51!"!I(&9!01!;%#G%+!,/#&!!!I(&9!#&9!4#&!I%!%#1062!I+(G%&C!

!

$887>7;2! :319>7;24! #+%! ,/%! $(1,! 0$*(+,#&,! +%#4,0(&1! (-! ,/%! 4#+I(&<4#+I(&! 9(5I6%! I(&9C! "!

%6%4,+(&1!(-!9(5I6%!I(&9!#+%!%#1062!#L#06#I6%! ,(! ,/%! +%#M%&,C! !K/51!4#+I(&<4#+I(&!9(5I6%!I(&9!

#4,1! #1! #! 1(5+4%! (-! %6%4,+(&1! -(+! %6%4,+(*/0604! +%#M%&,1! #&9! 5&9%+M(%1! %6%4,+(*/0604! #990,0(&!

+%#4,0(&C!

!!!!

C C

H

H H

H"! -bond

!! -bond

E-Nu CH3 C C CH3

E Nu

CH3 CH3

New - -bond!

O

!!!!!!!!!!

&39=1274O!;H!3/39>:;?=7//79!1887>7;2!>;!'1:<;2P'1:<;2!8;C</3!<;28J!

->3?!SJ!^(&01#,0(&!!(-!AQ<:5E!+%#M%&,!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!Q<:5!! !!!!!!!!QO!!!!!!!!!!!!

O!!!!!!!!!J:5<!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!Q6%4,+(*/06%!!!!!!!!!:546%(*/06%!

!

->3?!UJ!F,,#4G!(-!%6%4,+(*/06%!AQOE!,(!.#+I(&<!.#+I(&!9(5I6%!I(&9C!

C C

CH3

CH3

CH3

CH3

E+

CH3

C

E

CH3

CH3

CH3

alkene

+O

!

K/%!#990,0(&!(-!%6%4,+(*/06604!+%#M%&,1!+%60%L%1!,/%!1,+#0&!(-!.f.!AI(&9!#&M6%!=@>(E!I2!4(&L%+,0&M!

0,!,(!.<.!AI(&9!#&M6%!=>UCV(E!

->3?PXJ!K/%!&546%*/06%!A E!#,,#4G!,/%!4#+I(&05$!0(&!,(!M0L%!,/%!#990,0(&!*+(954,C!Nu-

:

CH3

C C

E

CH3

CH3

CH3

+ :Nu+

-

CH3

C C

E

CH3

CH3

CH3

Nu

Carbonium ion Addition product !

'%4#51%!,/%!#990,0(&!+%#4,0(&1!#+%!0&0,0#,%9!I2!%6%4,+(*/06%1H!,/%2!#+%!+%-%++%9!,(!#1!%6%4,+(*/0604!#990,0(&!

+%#4,0(&1C!

! ==

!!!!QO!01!515#662!8OH!'+!O!(+!.6O!

Nu-

: 01!515#662!'+!PH!.6!PH!Pc8!!(+!Pc"cR8!

-;O3!;H!>=3!7O?;:>12>!:319>7;24!;H!1/03234!1:3!H;//;I72LJ!

7K!$887>7;2!;H!#68:;L32a!F990,0(&!(-!/29+(M%&!,(!#6G%&%1!,#G%1!*6#4%!5&9%+!*+%115+%!#&9!0&!,/%!

*+%1%&4%!(-!4#,#621,!60G%!:0H!N,!(+!N9!,(!*+(954%!1#,5+#,%9!/29+(4#+I(&1C!K/01!01!4#66%9!4#,#62,04!

/29+(M%&#,0(&C!

R-CH=CH2 H2

NiR-CH2-CH3

Alkene Alkane

+

!

77K!$887>7;2!;H!#1/;L32J!F6G%&%1!+%#4,1!,(!/#6(M%&!0&!*+%1%&4%!(-!0&%+,!1(6L%&,!,(!M0L%!90/#6(M%&!

9%+0L#,0L%!-(+!%J#$*6%C!

!!!!!

R-CH=CH 2

inert solvent

Alkene

+ Br2 R CH CH

Br Br

Dibromo alkane !

777K$887>7;2! ;H! #68:;L32! #1/783P_#68:;! =1/;L321>7;2K! J! F990,0(&! (-! 829+(M%&! /#609%! ,(!

#6G%&%!*+(954%!#6G26!/#609%1C!^&!4#1%!(-!12$$%,+04#6!#6G%&%!(&62!(&%!#6G26!/#609%!01!-(+$%9!I5,!

;/%&!,/%!(6%-0&!01!5&12$$%,+04#6!,;(!*+(954,1!#+%!*(110I6%C!

3(+!QJ#$*6%a!

RCH=CHR HBr R CH2 CH

Br

symmetricalalkene

alkyl halide

RCH=CH2HBr R CH CH3

Br

R CH2 CH2 Br

2-Bromoalkane1-Bromoalkane

CH3-CH=CH2 HBr CH3 CH CH3

Br

CH3CH2CH2Br

Iso propyl bromide Propyl bromide

symmetricalalkene

O

O O

O O

!

^,!/#1!I%%&!-(5&9!,/#,!01(*+(*26!I+($09%!01!,/%!$#j(+!*+(954,C!^&!154/!4#1%1!#990,0(&!01!M(L%+&%9!

I2!T#+G(&0G(LY1!+56%!;/04/!1,#,%1!,/#,H!

“When an unsymmetrical reagent(such as HX, H2SO4,HOCl etc) adds to an unsymmetrical

alkene, then the negative part of the reagent is added to that carbon atom of the double bond

which bears the least number of hydrogen atoms i.e which bears more substituents and positive

part of the reagent is added to that carbon atoms which bears greatest number of hydrogen

atoms i.e. which bears less substituents.”

!

K/%!+%#4,0(&!,#G%!*6#4%!,/+(5M/!0(&04!$%4/#&01$C!T#+G(&0G(LY1!+56%!4#&!I%!%J*6#0&%9!;0,/!,/%!

/%6*!(-!$%4/#&01$C!

!

! =@

->3?!+J!^1($%+01#,0(&!(-!+%#M%&,!,(!M0L%!%6%4,+(*/06%!A8OE!#&9!&564%(*/06%CA'+

<E!

HBr H+

Br-

Proton Bromide ionO

!

->3?!++J!F,,#4G!(-!%6%4,+(*/06%!A8OE!,(!9(5I6%!I(&9!,(!-(+$!$(+%!1,#I6%!4#+I(4#,0(&C!

CH3CH=CH2 H+

CH3-CH-CH3

CH3-CH2-CH2

+

^

^^

2o carbonium ion (more stable)

1o carbonium ion (less stable)

+

+

!

^

^^

T(+%!1,#I6%!4#+I(4#,0(&!01!*+%-%+%&,0#662!-(+$%9C!

->3?!+++J!F,,#4G!(-!&546%(*/06%!A'+<E!,(!4#+I(&05$!0(&!A$(+%!1,#I6%E!,(!M0L%!$#j(+!*+(954,C!

CH3-CH-CH3 :Br+ -

CH3 CH CH3

Br

isopropyl bromide

O

!

"3:;@783! (HH39>! P! $2>7! O1:0;E270;E! 1887>7;2J!m/#+#14/! #&9! T#2(! =URRE! 9014(L%+%9! ,/#,!

#990,0(&!(-!8'+!,(!*+(*#&%!(+!(,/%+!5&12$$%+,+04#6!#6G%&%!0&!*+%1%&4%!(-!(+M#&04!*%+(J09%!AZ<

c<cZE! 20%691! $#0&62! &<#6G26! I+($09%A#&,0! $#+G(&0G(LY1! *+(954,EC! K/01! %--%4,! 01! G&(;&! #1!

*%+(J09%!%--%4,!(+!A=1:149=!3HH39>C!'5,!0,!9(%1!&(,!#**62!,(!#990,0(&!0&L(6L0&M!8.6H!8^!(+!83!

CH3CH=CH2 HBr

CH3CH2CH2Br

CH3 CH CH3

Br

peroxide

no peroxide

Propyl bromide

(Anti markonikov's product)

Iso propyl bromide

(markonikov's product)

O

!

^&!*+%1%&4%!(! -!*%+(J09%! ,/%! #990,0(&! ,#G%1!*6#4%!L0#! #! -+%%! +#904#6!$%4/#&01$! +#,/%+! ,/#&! ,/%!

0(&04! $%4/#&01$C! K/01! #990,0(&! (-! -+%%! +#904#6! ,(! 9(5I6%! I(&9! 0&L(6L%1! ,/%! 0&,%+$%90#,%!

-(+$#,0(&!(-!$(+%!1,#I6%!-+%%!+#904#6C!

!

7EK!$887>7;2!;H!#6?;=1/;C4!1978J!^&!/2*(/#6(51!#409A8c_E!!Pc8!01!$(+%!&%M#,0L%!*#+,C!K/%2!

#99! ,(! #6G%&%! ,(! M0L%! /#6(/29+0&C! ^&! 4#1%! (-! 5&12$$%,+04#6! #6G%&%! T#+G(&0G(LY1! +56%! 01!

-(66(;%9C!

! =R

CH2 CH2 HOCl H2C CH2

OH Cl

Ethylene Ethylene chlorohydrin

CH3CH=CH2 HOCl CH3 CH CH2 Cl

OH

PropylenePropylene chlorohydrin

O

O

!!

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156*/#,%1!;/04/!(&!/29+(62101!20%69!#64(/(61C!

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A:#:8@E!

R-C C-H +Naliquid NH3

H2

- +

H-C C-H + Naliquid NH3 - +

H2

R-C C:Na +1/2

R-C C:Na +1/2

Copper acetylides

Silver acetylides

!

IE!3(+$#,0(&!(-!.(**%+!#&9!106L%+!#4%,2609%1!;0,/!#$$(&04#6!1(65,0(&!(-!45*+(51!4/6(+09%!#&9!

106L%+!&0,+#,%C!

H-C C-H + 2AgNO + 2NH OH

2

3 4 AgC CAg +2NH NO +2H O+ +- -

4 3 2

H-C C-H + CuCl + 2NH OH2 4

+ +- -Cu C C Cu +2NH Cl +2H O

4Copper acetylides

Silver acetylides !

SSK!+4;O3:741>7;2J!F6G2&%1!;/%&!,+%#,%9!;0,/!,+#4%1!(-!#6G#60!60G%!#64Cmc8!#&9!:#:8@!5&9%+M(!

01($%+01#,0(&H!-(+!%J#$*6%!=<#6G2&%1!(&!,+%#,$%&,!;0,/!#6G#60!01($%+01%1!,(!@<#6G2&%C!KOH

AlcoholC8R CH@ C C H C8R C C C8R!

c&!,/%!(,/%+!/#&9!@<#6G2&%!;0,/!:#:8@!!0&!0&%+,!1(6L%&,!M0L%1!=<#6G2&%C!

C8R C C C8RNaNH2 H

+/H2O

2-Butyne 1-Butyne

C8R CH@ C CNa C8R CH@ C CH

!

SUK! ";/6O3:7N1>7;2J! F6G2&%1H! ;/%&! *#11%9! ,/+(5M/! #! +%9! /(,! 0+(&! ,5I%H! 5&9%+M(! 424604!

*(62$%+0S#,0(&! ,(! -(+$! #+($#,04! /29+(4#+I(&1C! 3(+! %J#$*6%H! ,/+%%! $(6%456%1! (-! #4%,26%&%!

4($I0&%!,(!M0L%!I%&S%&%!5&9%+!,/%1%!4(&90,0(&1C!

CH

CH

CH

CH

CH

CH

Red hot tube

BenzeneAcetylene ( 3 molecules ) !!

! @=

`&9%+!10$06#+!4(&90,0(&!,/+%%!$(6%456%1!(-!*+(*26%&%!*(62$%+0S%1!,(!M0L%!$%10,26%&%C!

!!!!!!!!!

CH

CH

CH

CH

CH

CH

CH3

CH3CH3

Red hot tube

CH3

3CHCH

3 mesitylenemesitylene( )

Propylene( 3 molecules)

mesitylene

( 1, 3, 5 -Trimethyl benzene)!

F4%,26%&%!;0,/!&04G%6!42#&09%!5&9%+!*+%115+%!M0L%1!4246(<(4,#!,%,+#%&%C!

!!!!!!!!!!!!!!!!!!!!!!!

CH CH4Ni(CN)2

Pressure

cycloocta-1,3,5,7-tetraene

Acetylene

cycloocta-1,3,5,7-tetraene!

$/06/!#1/7834!

F6G26!/#609%1!#+%!,/%!4($*(5&91!9%+0L%9!-+($!,/%!1#,5+#,%9!/29+(4#+I(&1!I2!+%*6#4%$%&,!(-!(&%!

(-!,/%!/29+(M%&!#,($!I2!/#6(M%&!#,($C!

R H-H R-X

Saturated hydrocarbon Alkyl halide.!

K/51!,/%2!4#&!I%!+%*+%1%&,%9!I2!M%&%+#6!-(+$56#!Z<_!;/%+%!Zf!#6G26!M+(5*[!_f!.6H!'+H!^!(+!3C!

8#6(M%&!#,($!$#2!I%!#,,#4/%9!,(!=(H!@(!(+!R

(!.#+I(&!#,($!(-!#6G26!M+(5*C!K/51!#6G26!/#609%!4#&!

I%!46#110-0%9!#1!*+0$#+2!A=(EH!1%4(&9#+2A@

(E!(+!,%+,0#+2!AR

(E!9%*%&90&M!5*(&!;/%,/%+!,/%!/#6(M%&!

01!#,,#4/%9!,(!*+0$#+2H!1%4(&9#+2!(-!,%+,0#+2!4#+I(&!#,($C!!

R-C-X R-C-X R-C-X

H

H H

R' R'

R"!

!!!!!!!!!!!!!!!!!!!!!!!!!!=(!P!#6G26!/#609%!!!!!!!!!!@

(P!#6G26!/#609%!!!!!!!!!!!!!!!!!!!R

(!P!#6G26!/#609%!!!!!!!!!!

F6G26!/#609%1!#+%!L%+2!51%-56!(+M#&04!4($*(5&91C!!!

&3>=;84!;H!?:3?1:1>7;2J!!SK!T6!87:39>!#1/;L321>7;2!;H!$/01234J!!!F6G#&%1!;/%&!,+%#,%9!;0,/!4/6(+0&%!(+!I+($0&%!0&!,/%!

*+%1%&4%!(-!`Ce!60M/,!(+!#,!/0M/!,%$*%+#,5+%!AB>>(.E!M0L%1!#6G26!4/6(+09%!(+!#6G26!I+($09%!#6(&M!

;0,/!*(62!/#6(M%&!9%+0L#,0L%1C!3(+!%J#$*6%H!

! @@

CH4

Cl2

UV lightCH3Cl CH3Cl2 CHCl3 CCl4O O O

!

'5,! 0(9(#6G#&%1!4#&!I%!*+%*#+%9!(&62! 0&!,/%!*+%1%&4%!(-!(J090S0&M!#M%&,1! 60G%!8^cRH!8^cBC!c+!

.(&4C!8:cR!%,4C!I%4#51%!8^!-(+$%9!95+0&M!,/%!+%#4,0(&!+%954%1!I#4G!#6G26!0(909%!,(!#6G#&%C!'5,!

,/%!*+(954,1!#+%!90--0456,!,(!1%*#+#,%C!

!

UK! T6! 1887>7;2! ;H! #68:;L32! #1/783! >;! $/0323J! ! b/%&! #6G%&%1! #+%! ,+%#,%9! ;0,/! /29+(M%&!

/#609%1H!#990,0(&!(-!/29+(M%&!/#609%!,#G%1!*6#4%!0&!#44(+9#&4%!;0,/!T#+G(&0G(LY1!+56%!%J4%*,!,/%!

#990,0(&!(-!8'+!0&!*+%1%&4%!(-!(+M#&04!*%+(J09%!WZ<c<c<ZXC!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

HC CH2R HX R-CH-CH3

X

Alkyl Halide

R-CH -CH-R2

X

Alkyl Halide

+

R-CH=CH-RO HX

!F990,0(&!(-!!8'+!,(!5&12$$%,+04#6!#6G%&%!

#E!^&!#I1%&4%!(-!*%+(J09%a!

!!!!!!!!!!!!!!!!!!!!!!!!! 2CH -CH=CH +HBr CH -CH-CH

3 3 3

Br

!

IE!^&!*+%1%&4%!(-!*%+(J09%a!

PeroxideC8R CH C8@ C8R CH@ CH@BrO HBr!

XK!T6!>:31>O32>!;H!$/9;=;/!I7>=!#1/;L32!$978J!F64(/(61!+%#4,!;0,/!8'+!(+!8^!,(!M0L%!#6G26!

I+($09%!(+!#6G26!0(909%C!K/%2!+%#4,!;0,/!8.6!0&!*+%1%&4%!(-!S0&4!4/6(+09%!4#,#621,C!

R-OH HBr RBr H2OO O!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!R-OH +HCl R-Cl H2O

ZnCl2

(dry)O

!

YK! T6! >:31>O32>! ;H! $/9;=;/! I7>=! "=;4?=;:;C4! #1/7834J! F64(/(61! +%#4,! ;0,/! */(1*/(+(51!!

/#609%1!AN_V!(+!N_RE!,(!M0L%!#6G26!/#609%1C!

!!!!!!!!!!!!!!!!!!!!!!!!!Z<c8!O!N_V!A(+!N_RE !Z<_!

!!!!!!!Z<c8!O!!N.6V !Z<.6!ONc.6R!O!8@c!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!R!Z<c8!O!N'+R! !R!Z<'+!O8RNcR!

! @R

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!R!Z<c8O!N R̂! !RZ<^!O!8RNcR!

N'+R!(+!N^R!#+%!*+(954%9!in situ!I2!,/%!+%#4,0(&!(-!I+($0&%!(+!0(90&%!;0,/!+%9!*/(1*/(+51!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!@NO@'+@! !@N'+R!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!@N!OR^@!!! !@!N^R!

\K! T6! >:31>O32>! ;H! $/9;=;/! I7>=! *=7;26/! '=/;:783J! F64(/(61! ;/%&! ,+%#,%9! ;0,/! ,/0(&26!

4/6(+09%! 0&! ,/%! *+%1%&4%! (-! *2+090&%! M0L%! #6G26! 4/6(+09%C! N2+090&%! #4,1! #1! 14#L%&M%+! -(+! 8.6!

-(+$%9C!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!Z<c8!O"c.6@!!!!!*2+090&%!!!!!!!!Z<.6!O"c@!!O!8.6!

]K! T6! #1/;L32! (@9=12L3! %319>7;2! ZB7203/4>372! :319>7;2[J! K/01! $%,/(9! 01! 150,#I6%! -(+! ,/%!

*+%*#+#,0(&! (-! #6G26! 0(909%1! #&9! -65(+09%1C! K/01! 0&L(6L%1! ,/%! ,+%#,$%&,! (-! #6G26! I+($09%! (+!

4/6(+09%!;0,/!4(&4%&,+#,%9!1(65,0(&!(-!1(905$!0(909%!0&!#4%,(&%C!

CH3CH2Br NaIacetone

CH3CH2I NaBrO O!

3(+! ,/%! *+%*#+#,0(&! (-! #6G26! -65(+09%! #6G26! I+($09%1! (+! 4/6(+09%1! #+%! /%#,%9! ;0,/! 0&(+M#&04!

-65(+09%1C!

2CH3-Cl Hg2F2 2CH3-F Hg2Cl2O O!

":;?3:>734!;H!$/06/!=1/7834J!

SK!"=64791/!":;?3:>734J!

0E! T%,/26! 4/6(+09%H! T%,/26! I+($09%H! T%,/26! -65(+09%! #&9! Q,/26! 4/6(+09%! #+%! M#1%1! #,! +(($!

,%$*%+#,5+%C!c,/%+! #6G26! /#609%1!5*! ,(!.=h! #+%! 4(6(5+6%11! 60d5091! #&9!I%2(&9!.=h! #+%! 4(6(+6%11!

M#1%1C!

00E! F6,/(5M/! #6G26! /#609%1! #+%! *(6#+! 0&! &#,5+%! I5,! ,/%2! #+%! 0&1(65I6%! 0&! ;#,%+! I5,! 1(65I6%! 0&!

(+M#&04! 1(6L%&,1C! ^&1(65I060,2! 0&! ;#,%+! 01! 95%! ,(! ,/%! 0&#I060,2! ,(! -(+$! /29+(M%&! I(&90&M! ;0,/!

;#,%+!#&9!,(!I+%#G!#6+%#92!%J01,0&M!/29+(M%&!I(&90&M!0&!;#,%+!$(6%456%C!

000E!K/%0+!9%&10,0%1!9%4+%#1%!0&!,/%!-(66(;0&M!(+9%+[!^(909%i!I+($09%i./6(+09%!i!-65(+09%C!F6G26!

I+($09%1!#&9!0(909%1!#+%!9%&1%+!,/#&!;#,%+!;/06%!#6G26!4/6(+09%1!#&9!-65(+09%1!#+%!60M/,%+! ,/#&!

;#,%+C!

0LE!!3(+!#!M0L%&!#6G26!M+(5*!I(060&M!*(0&,1!(-!#6G26!/#609%1!-(66(;!,/%!-(66(;0&M!(+9%+C!

F6G26!0(909%i!F6G26!I+($09%i!F6G26!./6(+09%i!F6G26!-65(+09%C!

!

3(+!#!M0L%&!/#6(M%&!#,($H!,/%!I(060&M!*(0&,1!(-!#6G26!/#609%1!0&4+%#1%!;0,/!,/%!0&4+%#1%!0&!,/%!10S%!

(-!,/%!#6G26!M+(5*C!

!

'=3O791/! ":;?3:>734J! ^&! #6G26! /#609%1! A.<_E! I(&9! 01! /0M/62! *(6#+! I%4#51%! (-! ,/%! /0M/!

%6%4,+(&%M#,0L0,2! (-! ,/%! /#6(M%&! #,($C! K/51! #6G26! /#609%1! #+%! L%+2! +%#4,0L%! 4($*(5&91! #6G26!

/#609%1! 4#&! I%! &%#+62! #66! ,2*%1! (-! (+M#&04! 4($*(5&91! #&9! ,/51! 12&,/%,04#662! ,/%2! #+%! L%+2!

0$*(+,#&,C!K/%2!5&9%+M(!4C<4>7>C>7;2H!3/7O721>7;2H!#&9!:38C9>7;2!+%#4,0(&1C!

-C<4>7>C>7;2! %319>7;2J! K/%! A.<_E! I(&9! 01! 1,+(&M62! *(6#+0S%9! 4(L#6%&,! I(&9! 95%! ,(! ,/%! /0M/!

%6%4,+(&%M#,0L0,2!(-!/#6(M%&!#,($C!

! @B

C X$ $

+ -

!

K/51!4#+I(&!#,($!(-!.<_!I(&9!01!,/%+%-(+%!#!M((9!10,%!-(+!,/%!#,,#4G!(-!&546%(*/06%1!A%6%4,+(&!

+04/!1*%40%1E!#&9!,/%!&546%(*/0604!15I1,0,5,0(&!+%#4,0(&1!#+%!$(1,!4($$(&!+%#4,0(&1!(-!,/%!#6G26!

/#609%1C!

C X$ $

+ -

Nu:- C Nu X:

-

nucleophile alkyl halide substitution product

OO

!

K/%!4($$(&!&546%(*/06%!#+%!Pc8H!

<.:H!

<"8H!:c@

<H!<:8@!#&9!cZ

<C!

:546%(*/0604!15I1,0,5,0(&!0&!#6G26!/#609%1!,#G%1!*6#4%!0&!,;(!;#21C!

SK!-GS!&39=1274O_!C27O;/39C/1:!2C9/3;?=7/79!4C<4>7>C>7;2!KJ!^&!,/01!$%4/#&01$!15I1,0,5,0(&!

,#G%1!*6#4%!0&!,;(!1,%*1C!]%,!51!4(&109%+!,/%!/29+(62101!(-!I+($09%!I2!#d5%(51!:#c8C!

->3?P+a!K/01!0&L(6L%1!,/%!0(&0S#,0(&!(-!#6G26!/#609%!,(!M0L%!#!*6#&#+!4#+I(&0$!0(&!0&!;/04/!4%&,+#6!

*(10,0L%62!4/#+M%9!4#+I(&05$!0(&!01!"N@!/2I+0901%9C!

Br

R

R

RSlow

C+

R

R

R

+ :Br-

tert-alkyl bromide!

->3?P++J!K/01! 0&L(6L%1! ,/%!#,,#4G!(-!&546%(*/06%!(&!4#+I(&05$!0(&!-+($!%0,/%+!109%! ,(!M0L%! ,/%!

15I1,0,5,0(&!*+(954,C!

C+

RR

R

R

OH

RR

fast

3o Alkyl alcoholOH

-

!!

Z%$%$I%+! ,/#,! 0-! #6G26! /#609%! 01! (*,04#662! #4,0L%! ,/%&!;%!;066! M%,! ,/%! +%4%$04!$0J,5+%!(-! ,;(!

%&#,0($%+1C! K%+,0#+2! #6G26! /#609%1! 5&9%+M(! 15I1,0,5,0(&! I2! ":=! $%4/#&01$! L0#! -(+$#,0(&! (-!

4#+I(&0$! 0(&! I%4#51%! ,/%! #,,#4G! (-! ,/%! &546%(*/06%! (&! ,/%! 4+(;9%9! ,%+,0#+2! #6G26! /#609%! 0C%C!

1,%+04#662!/0&9%+%9!4%&,+#6!4#+I(&!#,($!01!90--0456,C!K/%!+%#4,0L0,2!(+9%+!-(+!":=!$%4/#&01$!01!!

R(!#6G26!/#609%!i@

(!#6G26!/#609%!i=

(!#6G26!/#609%!

=(!#6G26!/#609%!5&9%+M(%1! 15I1,0,5,0(&!I2!":

@!$%4/#&01$!#&9! ,/%!@

(!#6G26!/#609%!$#2!5&9%+M(!

15I1,0,5,0(&!I2!%0,/%+!":@!(+!":

=!$%4/#&01$!9%*%&90&M!5*(&!,/%!1(6L%&,C!

UK! -GU!&39=1274O! ZT7O;/39C/1:!2C9/3;?=7/79! 4C<4>7>C>7;2[J!=

(!#6G26! /#609%! /#609%1! 5&9%+M(!

15I1,0,5,0(&!I2!":@!$%4/#&01$C!K/01!01!(&%!1,%*!*+(4%11!0&!;/04/!,/%!#,,#4G!(-!,/%!&546%(*/06%!

! @V

#&9! ,/%! %j%4,0(&! (-! ,/%! /#609%! 0(&! ,#G%1! *6#4%! 10$56,#&%(5162C! =(!#6G26! /#609%! 5&9%+M(%1!

15I1,0,5,0(&!I2!":=!$%4/#&01$!L0#!-(+$#,0(&!(-!,+#&10,0(&!1,#,%C!]%,!51!4(&109%+!,/%!/29+(62101!

(-!$%,/26I+($09%!I2!#d5%(51!!:#c8C!

!'56G0%+!,/%!#6G26!M+(5*H!$(+%!01!,/%!1,%+04!/0&9+#&4%!0&!,/%!-(+$#,0(&!(-!,+#&10,0(&!1,#,%!#&9!,/51!

01!,/%!+%#4,0L0,2!(-!#6G26!/#609%C!

!

K/%!+%#4,0L0,2!(+9%+!-(+!":@!$%4/#&01$!01H!

=(!#6G26!/#609%i@

(!#6G26!/#609%iR

(!#6G26!/#609%!

"($%!0$*(+,#&,!15I1,0,5,0(&!+%#4,0(&1!(-!#6G26!/#609%1!#+%!M0L%&!I%6(;a!

7K!%319>7;2!I7>=!1bC3;C4!AF#J!b/%&!#6G26!/#609%1!+%#4,!;0,/!#dCmc8H!/#6(M%&!01!15I1,0,5,%9!

I2!Pc8!M+(5*!,(!M0L%!#64(/(61C!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

H2OR-X + KOH R-OH +HX

alkylhalide

alcohol

!!

3(+!%J#$*6%[!

C2H5Br KOHH2O

C2H5OH KBr

ethyl alcohol

O O!

77K!%319>7;2!I7>=!O;74>!-7/E3:!F@783J!F6G26!/#609%1!(&!,+%#,$%&,!;0,/!$(01,!106L%+!(J09%!#61(!

M0L%1!#64(/(61C!

Z<_!OFMc8! Z<c8O!FM_!

QJ#$*6%a!!!!!!!!!!!!!!!!!!!!!!.@8V'+!OFMc8! .@8V!c8O!FM'+!

777K! %319>7;2! I7>=! 4;87CO! $/0;@783J! F6G26! /#609%1! (&! ,+%#,$%&,! ;0,/! 1(905$! #6G(J09%! M0L%!

%,/%+1C!K/01!+%#4,0(&!01!G&(;&!#1!M7//71O4;2!3>=3:!-62>=3474C!

R-X-

RONa+

R-OR NaX

Ether

C2H5Br NaOC2H5

+C2H5-O-C2H5 NaBr

Ethyl bromide Dethyl etherSodium ethoxide

-

O O

OO!

! @?

7EK!!%319>7;2!I7>=!D:6!-7/E3:!F@783J!F6G26!/#609%1!(&!/%#,0&M!;0,/!9+2!106L%+!(J09%!M0L%!%,/%+1C!

[email protected]^!OFM@c!!!.8R<c<.8R!

EK!%319>7;2!I7>=!-;87CO!;:!";>1447CO!'612783J!F6G26!/#609%1!+%#4,!;0,/!1(905$!(+!*(,#1105$!

42#&09%! ,(! M0L%! #6G26! 42#&09%1!;/04/! #+%! L%+2! 0$*(+,#&,! 12&,/%,04! 0&,%+$%90#,%1C!K/%2! 4#&!I%!

%#1062!4(&L%+,%9!,(!4#+I(J2604!#4091!#&9!*+0$#+2!#$0&%1C!

R-CN

RCOOH

RCH2NH2

LiAlH4

hydrolysis

H2OH+/

or Na-alcohol

(reduction) !

aqueous alcoholR-X + NaCN R-CN +NaX

!

F6G26!/#609%1!;/%&!+%#4,!;0,/!FM.:H!01(42#&09%1!#+%!-(+$%9C!!

!!!!!!!!!!!!!!!!!!!!!!!!!Z<_!!!O!!!FM.:! !!!Z<:#.!!O!!!FM_!

01(42#&09%!

E7K!%319>7;2!I7>=!$LGFUJ!F6G26!/#609%1!+%#4,!;0,/!106L%+!&0,+0,%!-(+$!&0,+(!#6G#&%C!"($%!F6G26!

&0,+0,%1!#+%!#61(!-(+$%9C!

!!!!!!!!!!!!!!!!!!!!!Z_!!!!!O!!!!FM:c@!!! !!Z:c@!!!!O!!!!Zc:c!!O!!!!FM_!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!&0,+(!#6G#&%!!!!#6G26!&0,+0,%!

%CMC!!!!!!!!!!!!!!!!!!!!.@8V'+!O!FM:c@! !.@8V!:c@!O!.@8Vc:c!O!FM'+!

!!!!!!!!!!!!!!!!!!!!!Q,/26!'+($09%!!!!!!!!!!!!!!!!!!!!!!!!!!!!!:0,+(!%,/#&%!!!Q,/26!&0,+0,%!

E777K!%319>7;2!I7>=!A-#J!c&!,+%#,$%&,!;0,/!#64(/(604!*(,#1105$!/29+(156*/09%H!!#6G26!/#609%1!

20%69!,/0(61C!

!!!!!!!!!!!!!!!!!!!!!!!

RX KSH alcohol R-SH KX

Ethanethiol

C2H5I KSH alcohol C2H5SH K X

Ethane thiol

e.g.

O O

O O!

!

! @D

E777K!%319>7;2!I7>=!AU-J!F64(/(61!+%#4,!;0,/!*(,#1105$!156*/09%!,(!-(+$!#6G26!156*/09%!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!@Z<_Om@"! !Z<"<Z!O@m_!

%CMC!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!@.@8V^!Om@" !.@8V<"<.@8V!O!@m^!

7@K!%319>7;2!I7>=!%P'FF$LJ!!b/%&!#6G26!/#609%!+%#4,1!;0,/!#64(/(604!1(65,0(&!(-!106L%+!1#6,!(-!

4#+I(J2604!#409!#&!%1,%+!01!-(+$%9C!

e.g

R C OAg

O

O X-R' R C OR'

O

O AgBr

CH3 C OAg

O

O BrC2H5 CH3 C OC2H5

O

O AgBr!

@K!%319>7;2!I7>=!$93>6/7834J!F6G26!/#609%1!;0,/!1(905$!#4%,2609%1!M0L%!/0M/%+!#6G2&%C!

RX + NaC C-H R-C C-H + NaX- +

RX + NaC C-R R-C C-R + NaX!

@7K!%319>7;2!I7>=!$OO;271J!8%#,0&M!(-!#6G26!/#609%1!;0,/!#64(/(604!1(65,0(&!(-!#$$(&0#!!0&!#!

1%#6%9!,5I%!+%156,1!#!$0J,5+%!(-!90--%+%&,!46#11%1!(-!#$0&%1C!

!

RX NH3 RNH2 BrH

RNH2

1o amine

RX R2NH HBr

2o amine

R2NH RX R3NH HBr

3o amine

R3NH RX R4NX+-

4o amine

O

O

O

O

O

O

O

!@77K! %319>7;2! I7>=! 1/9;=;/79! AF#J! b/%&! #6G26! /#609%1! #+%! ,+%#,%9! ;0,/! #64Cmc8H!

9%/29+(/#6(M%&#,0(&!,#G%1!*6#4%!#&9!#6G%&%1!#+%!*+(954%9C!

! @h

R-CH2-CH2X KOH,alcohol R-CH=CH2 K X H2OO O!

^&!#64(/(6H!,/%+%!01!#&!%d5060I+05$!I%,;%%&!,/%!1(6L%&,!#&9!mc8!

C2H5OH KOH C2H5OK H2O- +OO

Sod.EthoxideEthanol!

"(905$! %,/(J09%! 01! #! 1,+(&M! I#1%C! ^,! -#L(5+1! %60$0&#,0(&! $(+%! ,/#&! 15I1,0,5,0(&C! K/%! +#,%! (-!

%60$0&#,0(&!,(!15I1,0,5,0(&!*+(954,!9%*%&91!(&!,/%!1,+54,5+%!(-! ,/%!#6G26!/#609%!#&9!%J*%+0$%&,!

4(&90,0(&C!3(+!%J#$*6%!0&!4#1%!(-!=(!#64(/(6!15I1,0,5,0(&!*+(954,!01!#61(!-(+$%9!I5,!0&!4#1%!(-!@(

!

#&9! R(! #64(/(6! %60$0&#,0(&! *+(954,! *+%9($0&#,%1C! =

(!#&9! @

(! #6G26! /#609%1! 5&9%+M(!

9%/29+(/#6(M%&#,0(&!I2!Q@!$%4/#&01$!#&9!R(!#6G26!/#609%1!9(!1(!I2!Q=!$%4/#&01$C!

!

-16>N3HHR4!%C/3J! In case of unsymmetrical alkyl halide dehydro halogenation yield more than

one alkene. One of them, the most highly substituted alkene, is the major productC!^&!154/!4#1%1!

%60$0&#,0(&!(-!8_!01!M(L%+&%9!I2!"#2,S%--Y1! +56%C!F44(+90&M! ,(!;/04/! ,/%!$#0&!*+(954,! 01! ,/%!

$(1,!/0M/62!15I1,0,5,%9!#6G%&%C!c+!0&!(,/%+!;(+91!829+(M%&!01!%60$0&#,%9!-+($!,/%!.#+I(&!#,($!

(-!#6G26!/#609%!;/04/!I%#+1!,/%!6%#1,!&5$I%+!(-!/29+(M%&!#,($1C!

!

3(+!%J#$*6%H!;/%&!@<I+($(I5,#&%!5&9%+M(!%60$0&#,0(&!;0,/!#64C!mc8H!,;(!#6G%&%1!#+%!*(110I6%!

#&9!$#j(+!(&%!01!$(+%!15I1,0,5,%9!#6G%&%C!A^&!#44(+9#&4%!;0,/!"#2,S%--Y1!+56%EC!

!

CH3CH=CH-CH3

CH2=CH-CH2CH3

2-Butene

1-Butene

(80%)

(20%)

alc.KOH

-HBr

-HBr

alc.KOH

H C C C

H

H

Br

H

C

H

H

H

H

H

!

@777K!%38C9>7;2J!F6G26!/#609%1!#+%!+%954%9!,(!#6G#&%1!I2!90--%+%&,!+%9540&M!#M%&,1!60G%!]0F68BH!

\&o8.6!#&9!8@o:0!(+!N9!%,4C!!

R-XLiAlH4

H2/Ni or Pd

Or Zn/HClRH + HX

e.g.

C2H5Br H2Ni or Pd C2H6 HBr

CH3CH2CH2I 2[H]Zn/HCl CH3CH2CH3

HI

O O

O O!

! @U

@7EK!MC:>N!%319>7;2J!b/%&!#6G26!/#609%1!+%#4,!;0,/!$%,#6604!1(905$!0&!9+2!%,/%+!,;(!$(6%456%1!

j(0&!,(M%,/%+!,(!M0L%!#6G#&%!;0,/!9(5I6%!&5$I%+!(-!4#+I(&!#,($1C!

C2H5Br 2Na Br-C2H5 C2H5 - C2H5 2NaBrether

Butane

O O O!

@EK!%19>7;2!I7>=!&L!128!,7J!F6G26!/#609%1! +%#4,!;0,/!T#M&%105$! 0&!9+2! %,/%+! ,(!M0L%! #6G26!

$#M&%105$!/#609%H!,/%!g+0M&#+9!+%#M%&,C!

R-X Mg RMgXether

alkyl mag.halide.

(Grignard reagent)

O

!'5,!;0,/!]0,/05$!0&!9+2!%,/%+!#6G26!/#609%1!M0L%!#6G26!]0,/05$C!

R-X etherLi R-Li + LiXO!

g+0M&#+9!+%#M%&,!01!#&!0$*(+,#&,!M+(5*!(-!(+M#&($%,#6604!4($*6%J!;/04/!/#1!,/%!M+%#,!12&,/%,04!

5,060,2!0&!(+M#&04!4/%$01,+2C!F6G26!]0,/05$!I%/#L%1!0&!,/%!1#$%!;#2!#1!g+0M&#+9!+%#M%&,!I5,!;0,/!

0&4+%#1%!+%#4,0L0,2C!

!

_@E7K!B:7383/!':1H>4!%319>7;2J!F6G26!/#609%1! +%#4,!;0,/!F+%&%1! 0&! ,/%!*+%1%&4%!(-! !#&/29+(51!

F6.6R!,(!-(+$!#6G26!I%&S%&%C!

RXamhydrous AlCl3

R

HX

Bnzene

Alkyl benzene

O O

!

$/7969/79!#68:;91:<;24!;:!'69/;!$/01234!

F60424604!829+(4#+I(&1!#+%! ,/(1%!4#+I(J2604!4($*(5&91! 0&!;/04/! ,/%!4#+I(&!#,($1!#+%! j(0&%9!

,(M%,/%+! ,(! -(+$!#! +0&MC! ^&! ,/01! 4#+I(&! #,($1! #+%! j(0&%9! ,(M%,/%+! ,(! -(+$! #! +0&MC! ! ^&! 1#,5+#,%9!

#60424604!/29+(4#+I(&1!$%,/26%&%!M+(5*1!j(0&%9!,(M%,/%+!,(!-(+$!!#!424604!1,+54,5+%H!/%&4%!,/%2!

#+%!#61(!G&(;&!#1!*(62$%,/26%&%C!F44(+90&M!,(!^`NF.!121,%$H!,/%2!#+%!&#$%9!#1!4246(#6G#&%1!

(+!4246(*#+#--0&1C!K/%2!+%1%$I6%!;0,/!,/%!#60*/#,04!4($*(5&9!0&!,/%0+!*+(*%+,0%1C!"($%!%J#$*6%!

(-!4246(!#6G#&%1!#+%H!

CH2

CH2H2C

H2C

CH2

CH2

CH2

CH2

H2C

CH2

CH2

H2C

CH2

CH2

CH2

CH2

H2C

H2C

cyclo propanecyclopentane

cyclohexanecyclobutane

!

!

!

! R>

&3>=;84!;H!?:3?1:1>7;2J!

SK!B:;O!D7=1/7834J!K/%!+%#4,0(&!01!#&!%J,%&10(&!(-!b5+,S!+%#4,0(&!0&!;/04/!,%+$0&#6!90/#609%1!

#+%!,+%#,%9!;0,/!1(905$!(+!S0&4!,(!M0L%!4246(#6G#&%1C!K/+%%!,(!10J!$%$I%+%9!4246(#6G#&%1!4#&!I%!

*+%*#+%9!I2!,/01!+%#4,0(&!I2!510&M!#**+(*+0#,%!90/#609%a!

%CMa!

H2C

CH2Cl

CH2Cl

2Na

CH2

CH2H2C2NaCl

Cyclopropane

H2C

CH2Br

CH2Br

H2C

2Zn

H2C

CH2

CH2

H2C

ZnBr2

cyclobutane

O

O

O

O

!

UK!B:;O!'1/97CO!41/>4!;H!D791:<;@7/79!$9784J!b/%&!,/%!4#6405$!1#6,1!(-!)04#+I(J2604!#4091!#+%!

/%#,%9! (&%! 4#+I(&! 6%11! 424604! G%,(&%1! #+%! -(+$%9H! ;/04/! 4#&! I%! +%#9062! 4(&L%+,%9! 0&,(! ,/%!

4(++%1*(&90&M!4246(#(G#&%1!I2!.6%$$%&1%&!+%954,0(&C!

3(+!QJ#$*6%a!

H2C

H2C CH2

CH2 C

C

O

O

Ca2

+

O

O

-CaCO3

CH2

CH2C

CH2CH2

OZn/Hg

HCl

CH2

CH2

H2C

CH2CH2

Calcium Adipate Cyclopentanone Cyclopentane!

XK!B:;O!>=3!(4>3:4!;H!D791:<;@6/79!19784!ZD7390O122!%319>7;2[J!b/%&!%1,%+!(-!)04#+I(J2604!

#4091!#+%!6%#G%9!;0,/!1(905$!0&,%+$(6%456#+!4(&9%&1#,0(&!,#G%1!*6#4%!,(!M0L%!%<G%,(!%1,%+1C!%p

G%,(!%1,%+1!#+%!-0+1,!/29+(621%9!,(!M0L%!%<G%,(!#409!#&9!,/%&!9%4#+I(J26#,%9!,(!M0L%!424604!G%(&%C!

.24604!G%,(&%1!(&!.6%$$%&1%&!+%954,0(&!M0L%!4246(!#6G#&%1C!

3(+!%J#$*6%a!

!!!!!!!!!!

H2C

H2C

CH2 C

CH H

COOC2H5

O

OC@HVNa

-C2H5OH

C

HC

CH2

H2C

H2C

O

COOC2H5

H2O

H+

C

HC

CH2

H2C

H2C

O

COOH

!!!!!

!

! R=

C

CH2

CH2

H2C

H2C

OZn/Hg

HCl

CH2

CH2

CH2

H2C

H2C

Cyclopentane !

!

C

CH2

CH2

H2C

H2C

OZn/Hg

HCl

CH2

CH2

CH2

H2C

H2C

Cyclopentane !!

7EK! ! B:;O! $:;O1>79! #68:;91:<;24J! '%&S%&%! #&9! 0,1! 9%+0L#,0L%1! (&! 4#,#62,04! +%954,0(&! #+%!

4(&L%+,%9!,(!10J!$%$I%+%9!4246(#6G#&%1C!

QCMC!!

3H2Ni,

pressure

cyclohexane

O

!

EK! B:;O! $/03234a! W*+%*#+#,0(&! (-! 4246(*+(*#+&%! 9%+0L#,0L%1XJ! F6G%&%! ;/%&! ,+%#,%9! ;0,/!

$%,/26%&%! 0(909%! 0&! *+%1%&4%! (-! \&<.5! 4(5*6%! 0&! %,/%+H! M0L%! 4246(*+(*#&%! 9%+0L#,0L%1CA!

-7OO;24P-O7>=!%319>7;2!E!

!!

R HC CH R CH2I2Zn-Cu

etherR HC CH R

CH2

Dialkyl cyclo propane

O

!!

":;?3:>734J!

"=64791/!":;?3:>734J!

=E!.246(#6G#&%1!#+%!60d5091!#,!+(($!,%$*%+#,5+%!%J4%*,!4246(*+(*#&%!#&9!4246(I5,#&%!;/04/!#+%!

M#1%1!#,!+(($!,%$*%+#,5+%C!

@E!K/%0+!$%6,0&M!#&9!I(060&M!*(0&,1!#+%!M+#95#662!0&4+%#1%!;0,/!0&4+%#1%!0&!$(6%456#+!;%0M/,1C!

!

';O?;C28! ! <?;'! ! O?

;'!

.246(*+(*#&%! ! <R@Ch! ! <=@DCB!

.246(I5,#&%! ! =@CV! ! <U>CD!

.246(*%&,#&%! ! BUCR! ! <=RCU!

.246(/%J#&%! ! h>CD! ! !!!!?C?!

RE!.246(#6G#&%1!#+%!0&1(65I6%!0&!;#,%+!I5,!1(65I6%!0&!%,/#&(6!#&9!%,/%+C!

! R@

'=3O791/!":;?3:>734J!.246(#6G#&%1!+%1%$I6%!;0,/!#6G#&%1! 0&!1%L%+#6!4/%$04#6!*+(*%+,0%1C!'5,!

,/%! 6(;%+! $%$I%+1H! 4246(*+(*%&%! #&9! 4246(I5,%&%! #+%! ,/%! %J4%*,0(&1C! K/%2! -(+$! #990,0(&!

4($*(5&91!;0,/!,/%!+0&M!-510(&C!K/51!4246(#6G#&%1!I%/#L%!I(,/!60G%!#6G#&%1!#1!;%66!#1!#6G%&%1C!

!

+O?;:>12>!%319>7;24!;H!'69/;1/01234!1:3!8349:7<38!<3/;IJ!SK!-C<4>7>C>7;2!I7>=!'/U!128!T:UJ!^&!*+%1%&4%!(-!)V!/7L=>!4246(#6G#&%!+%#4,!;0,/!.6@!!(+!'+@!,(!

M0L%!15I1,0,5,0(&!*+(954,1C!

3(+!%J#$*6%a!

Cl2UV light

Cl

ClH

cyclohexane chlorocyclohexane

O O

!

UK! $887>7;2! ;H! '/U! 128! T:UJ! .246(*+(*#&%! +%#4,1! ;0,/! .6@! (+! '+@! 7281:0! 128! 72!''/Y! #1! #!

1(6L%&,!,(!M0L%!#990,0(&!*+(954,!;0,/!,/%!(*%&0&M!(-!+0&MC!

Br2

CCl4

darkH2C

CH2

CH2

Br

Br

1,3-dibromopropane

```` O

!.246(!I5,#&%!#&9!(,/%+!/0M/%+!$%$I%+1!9(!&(,!M0L%!,/01!+%#4,0(&C!

XK!$887>7;2!;H!#68:;L32J!.246(*+(*#&%!#&9!.246(I5,#&%!+%#4,!;0,/!829+(M%&!0&!,/%!*+%1%&4%!

(-!!:0!.#,#621,!,(!M0L%!4(++%1*(&90&M!&(+$#6!#6G#&%1!C0C%C!*+(*#&%!#&9!&<I5,#&%C!Ni

```` H2 80oCCH3 CH2 CH3

propane

````H2

Ni

200oC

CH3 CH2 CH2 CH3

butanen-

O

O

!YK!$887>7;2!;H!#T:!128!#+J!.246(*+(*#&%!M0L%1!(*%&!4/#0&!#990,0(&!*+(954,!;0,/!4(&4%&,+#,%9!!

8'+!#&9!8^C!

```` CH3 CH2 CH2 BrBrH

1-bromopropane

O

!80M/%+!$%$I%+1!9(!&(,!M0L%!,/01!+%#4,0(&C!

\K!F@781>7;2J!.246(!#6G#&%1!;/%&!,+%#,%9!;0,/!/(,!#6G#60&%!mT&cB!20%69!904#+I(J2604!#409!;0,/!

,/%!46%#L#M%!(-!+0&MC!

%CMC!

! RR

``

``

[O] KMnO4

COOH

COOH

pentanedioic acid 1,5-

O

!

$/9;=;/4!

F64(/(61!#+%!,/%!/29+(J26!9%+0L#,0L%1!(-!1#,5+#,%9!/29+(4#+I(&!0&!;/04/!/29+(J26A<c8E!M+(5*!01!

#,,#4/%9!,(!1#,5+#,%9!4#+I(&!#,($C!F66!,/%!4/%$04#6!*+(*%+,0%1!(-!#64(/(61!#+%!95%!,(!,/%!*+%1%&4%!

(-! Pc8! M+(5*! ,/51! /29+(J26! M+(5*! 01! ,/%! -5&4,0(&#6! M+(5*! (-! #64(/(61C! F64(/(61! 4#&! I%!

+%*+%1%&,%9!I2!,/%!M%&%+#6!-(+$56#!Z<c8C!

!

F64(/(61!4#&!I%!46#110-0%9!#1!$(&(H!90H!,+0!#&9!*(62/29+04!#64(/(61!9%*%&90&M!(&!,/%!&5$I%+!(-!

/29+(J26!M+(5*1!A=H!@H!R!(+!$(+%E!*+%1%&,!0&!#!$(6%456%C!3(+!%J#$*6%!

CH3 CH2 OHCH2OH

CH2OH

CH2OH

CHOH

CH2OH

CH3

(CHOH)4

CH3

ethanol

ethylene glycol(Mono hydric)

(Dihidric) glycerol[[Trihydric]

Sorbitol[Poly hydric]

!

T(&(/29+04!#64(/(61!WZ<c8X!#+%!-5+,/%+!15I90L09%9!0&,(!=(H!@

(!#&9!R

(!#64(/(61!9%*%&90&M!5*(&!

,/%!&#,5+%!(-!4#+I(&!#,($!,(!;/04/!Pc8!M+(5*!01!#,,#4/%9C!

C OH

H

R

H

C OH

H

R

R'

C OH

R"

R

R' 1oCarbon

2oCarbon 3oCarbon

Primary Alcohol secondary Alcohol Tertiary Alcohol!

Q323:1/!&3>=;84!;H!?:3?1:1>7;2J!

SK!T6!>=3!#68:;/6474!;H!!1/06/!=1/7834J!F6G26!/#609%1!+%#4,!;0,/!#dC!mc8!(+!$(01,!106L%+!(J09%!

,(!M0L%!#64(/(61C!

R-X + KOH(aq)

R-X + AgOH

R-OH +KX

R-OH + AgX!

UK! T6! =68:1>7;2! ;H! ;/3H724J!F6G%&%1! +%#4,! ;0,/! "56*/5+04! #409! AUhqE! ,(! M0L%! -0+1,! #990,0(&!

*+(954,H!#6G26!/29+(M%&!156*/#,%1!;/04/!(&!/29+(62101!M0L%!#64(/(61C!

!

^&!4#1%!(&!5&12$$%,+04#6!#6G%&%1!-(+!#990,0(&H!T#+G(&0G(LY1!+56%!01!-(66(;%9C!

! RB

R CH CH2 HOSO3H R CH CH3

OSO3H

R CH CH3

OSO3H

O H

HR CH CH3

OH

H2SO4

Alkyl hydrogen sulhate

2o alcohol

O

O O

!

QJ4%*,!%,/26!#64(/(61!*+0$#+2!#64(/(61!4#&&(,!I%!*+%*#+%9!I2! ,/01!$%,/(9C!cL%+#66! +%#4,0(&! 01!

,/%!T#+G(&0G(LY1!#990,0(&!(-!;#,%+!,(!#!9(5I6%!I(&9C!%CMC!

CH3 CH CH2 OH2H

+

CH3 CH CH3

OH

OPropylene

Iso propyl alcohol!

XK#68:;<;:1>7;2PF@781>7;2! ;H! $/03234J! b/%&! #6G%&%1! #+%! ,+%#,%9! ;0,/! 90I(+#&%H! ,+0#6G26!

I(+#&%1!#+%!-(+$%9C!^&!,/01!+%#4,0(&!90I(+#&%!#991!#1!I(+#&%!A'8REC!K/%!*(10,0L%!*#+,!(-!'8R!01!

I(+(&!#&9!&%M#,0L%!*#+,!01!/29+(M%&C!%CMC!

R C CH21/2 B2H6 (RCH2CH2)3B3 O

!K+0#6G26! I(+#&%! (&! ,+%#,$%&,! ;0,/! #6G#60&%! #d5%(51! 1(65,0(&! (-! /29+(M%&! *%+(J09%! M0L%1!

=(#64(/(61C!

(RCH2CH2)3B H2O2-OH

3RCH2CH2OH H3BO3

1o Alcohol

O O

!K/%!(L%+#66!+%#4,0(&!(-!/29+(I(+#,0(&<(J09#,0(&!+%156,1!#&,0<!T#+G(&0G(LY1!#990,0(&!(-!;#,%+!,(!

9(5I6%!I(&9C!%CMC!

CH3CH=CH2

I)B2H6

II) H2O/-OHCH3CH2CH2OH

Propylenen-propylalcohol

!YK!#68:;/6474!;H!(4>3:4J!F409!/29+(62101!(-!%1,%+1!20%69!#64(/(61C!%CM!

CH3 C CH3

O

OH2

H+

RCOOH R'OHO O!

\KT6!91>1/6>79!%38C9>7;2!;H!'1:<;26/!';O?;C284J!F69%/29%1!(&!+%954,0(&!M0L%!=(!#64(/(61!

#&9!G%,(&%1!M0L%!@(!#64(/(61C!R

(!F64(/(61!4#&Y,!I%!*+%*#+%9!I2!,/01!$%,/(9C!

7K!%38C9>7;2!<6!C472L!1/9;=;/79!4;87COZT;CE3;C/>PT/129!:38C9>7;2[J!

!

R C H

ONa/C2H5OH

R-CH2OH

R C R'

ONa/C2H5OH

R CH R'

OH

1o alcohol

Ketone

Aldehyde

2o alcohol!

! RV

77K!%38C9>7;2!<6!C472L!,7$/#Y!;:!G1T#Y

!J!

R C H

O

R-CH2OH

R C R'

O

R CH R'

OH

1o alcohol

Ketone

Aldehyde

Li AlH4

or

NaBH4

Li AlH4

orNaBH4

2o alcohol!

&H%<5&1#,5+#,%9! 4#+I(&26! 4($*(5&91! $#2! #61(! I%! +%954%9! I2! ]0F68B! (+! :#'8B! ,(! M0L%!

4(++%1*(&90&M!#64(/(61C!

!

777K%38C9>7;2!I7>=!#UcG7J!

R C H

O

R-CH2OH

R C R'

O

R CH R'

OH

1o alcohol

Ketone

Aldehyde

H2 /Ni

H2 /Ni

2o alcohol!

?K!B:;O!Q:7L21:8!%31L32>J!g+0M&#+9!Z%#M%&,!AZTM_E!-0+1,!+%#4,!;0,/!4#+I(&26!4($*(5&9!,(!

M0L%!,/%!#990,0(&!*+(954,!;/04/!(&!#409</29+(62101!M0L%1!4(++%1*(&90&M!#64(/(6C!

!

CH3 C CH3

O

R-MgX CH3 C CH3

OMgX

R

H+/H2O

CH3 C CH3

OH

R

$! $! +-

O

Addition product Unstable !

g+0M&#+9! +%#M%&,!;0,/! -(+$#69%/29%H! #69%/29%1! (,/%+! ,/#&! -(+$#69%/29%! #&9!G%,(&%1! 6%#91! ,(!

,/%!-(+$#,0(&!(-!=(H!@(!#&9!R

(!#64(/(61!+%1*%4,0L%62C!3(+!%J#$*6%H!

H C H

O

RMgX H C H

OMgX

R

H+/H2O

R-CH2OH

1o alcohol

R' C H

O

RMgXR' C H

OMgX

R

H+/H2O

R' C H

OH

R

2o alcohol

R' C R'

O

RMgX R' C R'

OMgX

R

H+/H2O

R' C R'

OH

R

3o alcohol

O

O

O

!

! R?

^K!T6! >=3! :319>7;2!;H! 1/7?=1>79!?:7O1:6!1O723!I7>=!27>:;C4!1978J! N+0$#+2! #60*/#,04! #$0&%1!

+%#4,!;0,/!&0,+(51!#409!,(!M0L%!#64(/(61C!

RCH2NH2 HONO RCH2OH N2H2OO O O

!

`K!T6!B3:O32>1>7;2J!3%+$%&,#,0(&! 01! ,/%!16(;!9%4($*(10,0(&!(-!4($*6%J!(+M#&04!4($*(5&91!

0&,(!10$*6%!4($*(5&9!0&!,/%!*+%1%&4%!(-!%&S2$%1!(I,#0&%9!-+($!$04+((+M#&01$C!3%+$%&,#,0(&!

(-!1,#+4/!#&9!15M#+1!5&9%+!,/%!0&-65%&4%!(-!150,#I6%!$04+((+M#&01$!M0L%1!#64(/(61C!

3(+!%J#$*6%a!

!!!!!!!!!!!!!!!!!!!!

C6H12O6 2C2H5OH 2CO2

Glucose Ethyl alcohol

Zymase

yeast

(C6H10O5)nFermentationCH3CH2CH2CH2OH CH3 C CH3

O

Starch n-Butyl alocohol

O

O!

":;?3:>734J!

"=64791/!?:;?3:>734J!

=E! ](;%+! #64(/(61! #+%! 4(6(5+6%11H! ,(J04! 60d5091! ;/06%! /0M/%+! /#L0&M!$(+%! ,/#&! =@! 4#+I(&! #+%!

1(6091C!K/%2!/#L%!4/#+#4,%+01,04!1;%%,!#64(/(604!(9(5+!#&9!I5+&0&M!,#1,%C!

@E!](;%+!#64(/(61!#+%!%#1062!1(65I6%!0&!;#,%+!I5,!1(65I060,2!9%4+%#1%1!;0,/!0&4+%#1%!0&!$(6%456#+!

;%0M/,C!

"(65I060,2!(-!6(;%+!#64(/(61!0&!;#,%+!01!95%!,(!,/%!829+(M%&!I(&90&M!I%,;%%&!/0M/62!*(6#+0S%9!P

c8!M+(5*1!*+%1%&,!I(,/!0&!;#,%+!#&9!#64(/(61C!

!

!!!!!!!!!!!!!!!!!!!!!!!!

H O

H

H O

R

H O

H

$ | | || || | | | | | | | | | |

$ $ $ $$!+

- + - + -

!!

30M5+%<Va!829+(M%&!I(&90&M!I%,;%%&!#64(/(6!#&9!;#,%+!$(6%456%1C!

!

'5,!80M/%+!#6(4(/(61!/#L%!6%11!,%&9%&42!,(!-(+$!/29+(M%&!I(&91!;0,/!;#,%+!$(6%456%!I%4#51%!

(-!,/%!*+%1%&4%!(-!&(&!*(6#+!6(&M!/29+(4#+I(&!4/#0&!#&9!/%&4%!,/%!1(65I060,2!0&!;#,%+!9%4+%#1%1C!

RE! '(060&M! *(0&,1! (-! #64(/(6! 0&4+%#1%! ;0,/! ,/%! 0&4+%#1%! 0&! &5$I%+! (-! 4#+I(&! #,($1! I5,! ,/%0+!

I(060&M!*(0&,1!#+%!$54/!/0M/%+!,/#&!,/(1%!(-!,/%!4(++%1*(&90&M!#6G&#%1C!K/01!01!#M#0&!I%4#51%!(-!

0&,%+$(6%456#+!/29+(M%&!I(&90&MC!80M/62!*(6#+!Pc8!M+(5*1!(-!90--%+%&,! #64(/(6!$(6%456%!#&9!

*#+,0#662!&%M#,0L%!(J2M%&!0&!#&(,/%+!#64(/(6!$(6%456%C!

H O

H

H O

R

H O

H

$ | | || || | | | | | | | | | |

$ $! $ $$!+

- + - + -

!

BE!F$(&M!01($%+04!#64(/(61!I(060&M!#&9!$%6,0&M!*(0&,1!9%4+%#1%1!;0,/!I+#&4/0&MC!

N+0$#+2i!"%4(&9#+2iK%+,0#+2C!

! RD

'=3O791/!":;?3:>734J!!F64(/(61! #+%! 4/%$04#662! +%#4,0L%! 4($*(5&91! ,/01! 01! 95%! ,(! ,/%!*+%1%&4%!(-! +%#4,0L%! -5&4,0(&#6!

M+(5*H! <c8! M+(5*H!;/04/! 01! *(6#+! 0&! &#,5+%C! '%4#51%! (-! ,/%! /0M/! %6%4,+(&%M#,0L0,2! (-! (J2M%&!

#,($!I(,/!! !#&9!$!$! + -

-C-O$!$! + -

-O-H I(&91!0&!#64(/(61!#+%!*(6#+!I(&91C!!

F64(/(61!5&9%+M(!-(66(;0&M!+%#4,0(&1C!

SK!%319>7;24!72E;/E72L!;2/6!>=3!=68:;L32!1>;O!;H!>=3!dF#!L:;C?J!

K/%1%!+%#4,0(&1!0&L(6L%!46%#L#M%!(-!(J2M%&!#&9!/29+(M%&!I(&9C!

7K!%319>7;2!I7>=!1/01/7!O3>1/4J!F64(/(61!+%#4,!;0,/!1(905$!(+!*(,#1105$!,(!-(+$!#6G(J09%1!;0,/!

,/%!60I%+#,0(&!(-!/29+(M%&!M#1C!

2ROH + 2Na 2RONa + H 2

Sod.alkoxide !

K/%0+! +%#4,0(&! 1/(;1! ,/%! #40904! &#,5+%! (-! #64(/(61C! N+0$#+2! #64(/(61! #+%! $(+%! #40904! ,/#&!

1%4(&9#+2H!;/04/!0&!,5+&!01!$(+%!#40904!,/#&!,%+,0#+2!,/51!(+9%+!(-!#40904!&#,5+%!01!#1!-(66(;1C!

=(#64(/(61i@

(#6(/(61iR

(#64(/(61!

K/01! 01!I%4#51%!(-! ,/%!O^!%--%4,!(-! ,/%!#6G26!M+(5*1!#,,#4/%9C! ^,!;(569!I%!$#J0$5$!0&! ,%+,0#+2!

#64(/(61C!

!

UK%319>7;2! I7>=! 91:<;@6/79! $9784J! F64(/(61! +%#4,! ;0,/! 4#+I(J2604! #4091! 0&! *+%1%&4%! (-!

4(&4%&,+#,%9!156*/5+04!#409!#1!#!4#,#621,!,(!M0L%!%1,%+C!K/%!*+(4%11!01!G&(;&!#1!%1,%+0-04#,0(&C!

K/%!+%#4,0(&!01!+%L%+10I6%C!

OH C R'

OH

+

R'O C R

O

H2OEster

Alcohol Carboxylic acid

C2H5OH OH C CH3

OH

+

H5C2-O C CH3

O

H2O

Ethyl alcohol Acetic acid Ethyl acetate

O

OO

R'OH O

!!

XK!%319>7;2!I7>=!$978!=1/7834!128!$978!12=68:7834J!F64(/(61!4#&!$(+%!%#1062!%1,%+0-0%9!I2!

,/%!#4,0(&!(-!#409!./6(+09%!(+!#409!#&/29+09%C!

R C Cl

O

R C OR'

O

HCl

R C O

O

RC

O

R C OR'

O

RCOOH

Ester Carboxylic acidAcid anhydride

O O

O OHOR'

HOR'

Ester

!

! Rh

YK! !%319>7;2!I7>=!Q:7L21:8!%31L32>J!F64(/(61! +%#4,!;0,/!g+0M&#+9! +%#M%&,! ,(! M0L%! #6G#&%1C!

K/01!+%#4,0(&!01!51%9!-(+!,/%!%1,0$#,0(&!(-!#64(/(604!M+(5*!We3:3I7>2;HH!:319>7;2X!

R'OH RMgX RH R'OMgX

Alcoholsalkyl magnesium

halidesAlkane Alkoxy mag.halide

C2H5OH CH3MgICH4

C2H5OMgBr

methaneEthoxy mag.bromide

O

O

O

O!

A'E! Z%#4,0(&! 0&L(6L0&M! Pc8! M+(5*a!K/%1%! +%#4,0(&! 0&L(6L%! 46%#L#M%! (-! .#+I(&<(J2M%&! I(&9!

-C--OH

`̀`̀`̀

!!!

!

\K! %319>7;2! I7>=! ?=;4?=;:;C4! #1/7834J! b/%&! #64(/(61! +%#4,! ;0,/! */(1*/(+(51! *%&,#!

/#609%WN_VX!(+!*/(1*/(+(51!/#609%!WN_RXH!+%*6#4%$%&,!(-!Pc8!M+(5*!I2!/#6(M%&!#,($!,#G%!*6#4%!

#&9!#6G26!/#609%1!#+%!-(+$%9C!

R-OH PX5 R-X POX3 HX

C2H5OH PCl5 C2H5Cl POCl3 HCl

O

O

O

OO

O

!

3-R-OH PX3 3-R-X H3PO3

3C2H5OH PX3 3C2H5Br H3PO3

O O

OO!

N'+R!#&9!N^R!#+%!515#662!*+%*#+%9!0&!10,5C!

]K!%319>7;2!I7>=!>=7;26/!9=/;:783J!K/01!0&L(6L%1!+%*6#4%$%&,!(-!Pc8!M+(5*!I2!4/6(+0&%!#,($C!!

R CH3R Cl

C2H5 CH3 C2H5 Cl

SOCl2 SO2 HCl

SO2 HCl

O O

O OSOCl2

O

O!

^K!%319>7;2!I7>=!=1/;L32!19784J!F64(/(61!+%#4,!;0,/!/#6(M%&!#409!,(!M0L%!4(++%1*(&90&M!#6G26!

/#609%1C!

R OH R X OO HX OH2!

K/%!+%#4,0L0,2!(-!/#6(M%&!#4091!!#+%!0&!,/%!(+9%+H!

8^!i8'+!i8.6!

:(! 4#,#621,! 01! +%d50+%9! 0&! 4#1%!(-!8^! #&9!8'+! I5,!8.6! +%#4,1!(&62! 0&! *+%1%&4%! (-! #&/29+(51!

\&.6@!4#,#621,C!

! RU

C2H5 OH H5C2 Cl OO OH2ClHanhydrous ZnCl2

!&39=1274OJ! N+0$#+2! #64(/(61! -(66(;! ":

=! $%4/#&01$! -(+! ,/%! 15I1,0,5,0(&! (-! Pc8! M+(5*! I2!

/#6(M%&!#,($C!

->3?!SJ!N+(,(&#,0(&!(-!F64(/(6!

H3CH2C O H O H+

..

..H3CH2C O

+H

H

..

!->3?!UJ!F,,#4/!(-!&546%(*/06%!W_

<X!

H3CH2C O+

H

H

O X

..- CH3-CH2-X O OH2

!@(!#&9!R

(!#64(/(61!-(66(;!":

@!$%4/#&01$C!

`K!%319>7;2!I7>=!4C/?=C:79!1978J!K/%!#4,0(&!(-!4(&4%&,+#,%9!156*/5+04!#409!01!(-!M+%#,!0&,%+%1,!

#1!0,!M0L%1!90--%+%&,!*+(954,1!5&9%+!90--%+%&,!4(&90,0(&1C!

0E! F,! +(($! ,%$*%+#,5+%H! %,/26! #64(/(6! +%#4,1! ;0,/! 4(&4%&,+#,%9! 156*/5+04! #409! ,(! M0L%! %,/26!

/29+(M%&!156*/#,%C!

H5C2 OH HOSO3H Room TemperatureC2H5OSO3HOEthyl hydrogen sulphate!

00E!b/%&!#64(/(61!/%#,%9!;0,/!4(&4%&,+#,%9!8@"cBH!9%/29+#,0(&!,#G%1!*6#4%!,(!M0L%!#6G%&%1C!3(+!

%J#$*6%!

H5C2 OH

H2SO4

170oCCH2 CH2 O OH2

Ethyl alcohol Ethylene!

&39=1274OJ!T%4/#&01$!0&L(6L%!-(+$#,0(&!(-!4#+I(4#,0(&C!

->3?!SJ!N+(,(&#,0(&!(-!#64(/(6C!

CH3 CH2 O H O H+

CH3 CH2 O+

H

H !->3?!UJ!Q60$0&#,0(&!(-!;#,%+!$(6%456%!,(!M0L%!4#+I(4#,0(&C!

CH3 CH2 O+

H

H

CH3 CH2

+

O OH2

..

!

->3?!XJ!Z%$(L#6!(-!*+(,(&!-+($!4#+I(4#,0(&a!

! B>

C C

H

H

H

H

H

+CH2 CH2

Ethylene !

K/%!%#1%!(-!9%/29+#,0(&!(-!#64(/(61!-(66(;!,/%!-(66(;0&M!(+9%+!

R(i@

(i=

(

K/01!01!#61(!,/%!(+9%+!(-!1,#I060,2!(-!4#+I(4#,0(&C!

b0,/!1%4(&9#+2!#&9!,%+,0#+2!#64(/(61H!9%/29+#,0(&!$#2!(445+!0&!,;(!;#21H!%CMCa!

CH3 CH2 CH CH3

OH-H2O

CH3CH2CH=CH2

1-Butene

CH3CH=CHCH3

2-Butene !F44(+90&M!,(!"#2,S%--Y1!+56%!$(+%!15I1,0,5,%9!#6G%&%!01!,/%!$#j(+!*+(954,C!

000E!b/%&! %J4%11!(-! %,/26! #64(/(6! 01! /%#,%9!;0,/! 4(&4%&,+#,%9! 156*/5+04! #409! #,! =B>(.H! 90%,/26!

%,/%+!01!-(+$%9C!

C2H5OH O OHC2H5

con H2SO4 C2H5-O-C2H5

Diethyl ether140oC!

&39=1274OJ!T%4/#&01$!0&L(6L%1!,/%!-(66(;0&M!1,%*1C!

->3?!SJ!N+(,(&#,0(&!(-!(&%!T(6%456%C!

!!!!!!!!!!!!!!!!!!!!!!

H3CH2C O H O H+

..

..H3CH2C O

+H

H

..

!->3?!UJ!Q60$0&#,0(&!(-!;#,%+!$(6%456%a!

CH3 CH2 O+

H

H

CH3 CH2

+

O OH2

..

!->3?!XJ!F,,#4/!(-!4#+I(4#,0(&!,(!#&(,/%+!$(6%456%!(-!#64(/(6C!

!!!!!!!!!

CH3 CH2

+CH2CH3OH ..

..

..O C2H5-O-C2H5

H

+

Oxonium ion !

! B=

->3?!YJ!Z%$(L#6!(-!*+(,(&!-+($!cJ(&05$!0(&!6%#91!,(!,/%!-(+$#,0(&!(-!%,/%+C!

H5C2 O+

C2H5

H

..

-H+

H5C2 O C2H5

..

..

Diethyl ether !!

F64(/(61!4#&!#61(!I%!9%/29+#,%9!I2!*#110&M!,/%!L#*(5+1!(-!#64(/(6!(L%+!/%#,%9!#65$0&0#!,(!M0L%!

%,/%+1!(+!#6G%&%1!%CMC!

2C2H5OHAl2O3

200oCH5C2 O C2H5 O OH2

diethyl ether..

..

!

fK!%38C9>7;2!;H!$/9;=;/4J!

F64(/(61!#+%!+%954%9!,(!#6G#&%1!I2!4(&4%&,+#,%9!8^!#&9!+%9!*/(1*/(+(51!

ROH 2HI RH I2 H2Ored P

O O Oalcohol Alkane

C2H5OH 2HIred P

O C2H6I2 H2OO O

Ethane !

SaK!F@781>7;2J!:#,5+%! (-! (J09#,0(&! *+(954,1! (-! #64(/(61! 9%*%&9! 5*(&! ,/%! &#,5+%! (-! #64(/(61H!

(J090S0&M!#M%&,!51%9!#&9!+%#4,0(&!4(&90,0(&1C!T(1,!4($$(&62!51%9!(J090S0&M!#M%&,1!#+%!#40904!

mT&cB!#&9!#40904!:#@.+@cDC!

!

N+0$#+2! #64(/(61! #+%! %#1062! (J090S%9! ,(! #69%/29%1! #&9! ,/%&! ,(! 4#+I(J2604! #4091! I(,/!;0,/! ,/%!

1#$%!&5$I%+!(-!4#+I(&!#,($1!#1!,/%!*#+%&,!#64(/(6C!QCMCa!!

CH3CH2OH[O]

K2Cr2O7/H+

CH3 C H

O

[O]

K2Cr2O7/H+ CH3COOH

Acetic acidAcetaldehyeEthyl alcohol !

"%4(&9#+2! #64(/(61! (J090S%9! ,(! G%,(&%!;0,/! 1#$%! &5$I%+! (-! 4#+I(&! #,($1H! I5,! ,/%1%! G%,(&%1!

4#&Y,!I%!%#1062!(J090S%9H!,/%1%!5&9%+M(!(J09#,0(&!5&9%+!L%+2!9+#1,04!4(&90,0(&1!,(!M0L%!$0J,5+%!(-!

4#+I(J2604!#409!;0,/!!6%11%+!&5$I%+!(-!4#+I(&!#,($%1!,/#&!*#+%&,!#64(/(6C!QMa!

CH3 HC CH3

OH[O]

K2Cr2o7 /H+

CH3 C CH3

O

Isopropyl alcohol

CH3 CH CH3

OH [O]

KMnO4 /H+

CH3COOH O HCOOH

Acetic acid Formic acid

Acetone

!

! B@

K%+,0#+2!#64(/(61!#+%!+%101,#&,!,(!(J09#,0(&!5&9%+!&(+$#6!4(&90,0(&1!I5,!5&9%+!9+#1,04!4(&90,0(&1!

,/%2!(J090S%9!,(!-0+1,!-(+$!G%,(&%1!#&9!,/%&!4#+I(J2604!#409!I(,/!/#L0&M!6%11%+!&5$I%+!(-!!4#+I(&!

#,($1C!

CH3 C OH

CH3

CH3

[O]CH3 C CH3

O

t-Butyl alcohol(one carbon less)

[O]

KMnO4 /H+ KMnO4 /H

+CH3COOH O HCOOH

Acetic acid Formic acid

Acetone

!

)-(J!!*=3!;@781>7;2!:319>7;2!O16!1/4;!<3!C438!>;!874>72LC74=!<3>I332!?:7O1:65!439;281:6!

128!>3:>71:6!1/9;=;/4C!

!

SSK! %319>7;2! I7>=! =;>! ';??3:J! N+0$#+2! #&9! 1%4(&9#+2! #64(/(61! 9%/29+(M%&#,%9! ,(! -(+$!

#69%/29%!#&9!G%,(&%1!+%1*%4,0L%62H!K%+,0#+2!#64(/(61!#+%!&(,!9%/29+(M%&#,%9!I5,!,/%2!9%/29+#,%9!

,(!M0L%!#6G#&%1C!%CMC!

CH3 CH2 OHCu

300oC

CH3 C H

O

acetaldehydeethanol

CH3 CH CH3

OH

iso propyl alcohol

Cu

300oCCH3 C CH3

O

acetone

CH3 C OH

CH3

CH3

Cu

300oC

CH3 C CH2

CH3

O OH2

t-Butyl alcoholIsobutene

!

)-(J! *=3! 83=68:;L321>7;2! I7>=! =;>! 9;??3:! O16! 1/4;! <3! C438! >;! 874>72LC74=! <3>I332!

?:7O1:6!128!439;281:6!1/9;=;/4W!

!

(>=3:4!!

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-5&4,0(&#6!M+(5*!01!W.<c<.XC!^-!1#$%!#6G26!M+(5*1!#+%!#,,#4/%9!,(!4%&,+#6!(J2M%&!#,($!%,/%+1!#+%!

46#110-0%9! #1! 12$$%,+04#6! %,/%+1C!b/06%! %,/%+1! 4(&,#0&0&M! 90--%+%&,! #6G26! M+(5*1! #,,#4/%9!;0,/!

4%&,+#6!(J2M%&!#,($!#+%!46#110-0%9!#1!5&12$$%,+04#6!%,/%+1C!

R O R..

..

R O R'..

..

symmetrical ethers unsymmetrical ethers!

! BR

Q,/%+1!$#2!I%!4(&109%+%9!#1!9%+0L#,0L%1!(-!#64(/(6!(+!;#,%+!0&!;/04/!/29+(M%&!#,($!o#,($1!/#L%!

I%%&!+%*6#4%9!I2!#6G26!M+(5*!(+!M+(5*1C!

H O H..

..R O H

..

..

R O R..

..

water alcohol ether !

"($%!4($$(&!%J#$*6%1!(-!%,/%+1!#+%!!

H5C2 O CH3..

..H5C2 O C2H5

..

..

ethyl methyl ether diethyl ether

[methoxy ethane] ethoxy ethane!

^&! %,/%+1! 4%&,+#6! (J2M%&! #,($! 01! 1*R! /2I+090S%9! CK/51! ,;(! .<cH!!<I(&9! #+%! -(+$%9! ! I2! ,/%!

(L%+6#*! (-! ,;(! /#6-! -066%9! 1*R! /2I+09! (+I0,#61! (-! (J2M%&! #,($!;0,/! ,/%! /#6-! -066%9! 1*

R! !/2I+09!

(+I0,#61!(-!,;(!4#+I(&!#,($1!(-!,;(!#6G26!M+(5*1C!Z%$#0&0&M!,;(!1*R!/2I+09!(+I0,#61!(-!(J2M%&!

#,($1!#+%!(445*0%9!I2!,/%!,;(!5&1/#+%9!*#0+1!(-!%6%4,+(&1C!8%+%!,/%!.<c<.!I(&9!#&M6%!01!#I(5,!

==>(!;/04/!01!d50,%!46(1%!,(!,%,+#/%9+#6!#&M6%!W=>UCV

(X!

R RR R

110o

unshared pair of electrons

SP

3 -SP

3 SP 3

-SP 3

!! !

!!!!!!!!!!!!!!!!!!!!!",+54,5+%!(-!Q,/%+!

&3>=;84!;H!?:3?1:1>7;2J!

7K!D3=68:1>7;2!;H!1/9;=;/4J!'2!/%#,0&M!%J4%11!(-! !#64(/(6!;0,/!4(&4%&,+#,%9!156*/5+04!#409!#,!!

=B>(.!

R-OH HO-ROCon.H2SO4

140oCR-O-RO OH2

C2H5OHO HO-C2H5

Con.H2SO4C2H5-O-C2H5O OH2

!77K!T6!?14472L!1/9;=;/!E1?;:4!;E3:!$/UFX!1>!U\a

;'J!

R-OH HO-R R-O-R H2OAl2O3

O O!

UK!T6!=31>72L!1/06/!=1/7834!I7>=!47/E3:!;@783J!Q,/%+1!#+%!(I,#0&%9!I2!/%#,0&M!#6G26!/#609%1!;0,/!

9+2!106L%+!(J09%C!

C2H5I Ag2O IC2H5O O C2H5-O-C2H5

Diethyl ether!

! BB

K/01!$%,/(9!01!51%-56!-(+!,/%!*+%*#+#,0(&!(-!10$*6%!%,/%+1!(&62C!

XK!M7//71O4;2!(>=3:!-62>=3474J!K/01!01!,/%!$(1,!0$*(+,#&,!0&951,+0#6!#&9!6#I(+#,(+2!$%,/(9!(-!

*+%*#+#,0(&! (-! %,/%+1C! ^,! 0&L(6L%1! ,/%! ,+%#,$%&,! (-! 1(905$! #6G(J09%!;0,/! #&! #6G26! /#609%C!'(,/!

12$$%,+04#6!5&12$$%,+04#6!%,/%+1!4#&!I%!*+%*#+%9!I2!,/01!$%,/(9C!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

!

R-ONa NaXO O+-

Alkyl halideSod. alkoxide Symmetrical ether

R-O-RX-R

!

R-ONa R-O-R' NaXO Ounsymmetrical ether

+-X-R'

Sod. alkoxide Alkyl halide

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

O O+-

C2H5ONa Br-C2H5 C2H5-O-C2H5 NaBr

Diethyl ether !

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

O O+-

CH3ONa Br-C2H5 CH3-O-C2H5 NaBr

Ethyl methyl ether !

K%+,0#+2!#&9!"%4(&9#+2!#6G26!/#609%1!5&9%+M(!%60$0&#,0(&!+%#4,0(&!;0,/!1(905$!#6G(J09%!W1,+(&M!

I#1%XC!K/51! ,(! 0&,+(954%!#! ,%+,0#+2!M+(5*! 0,!;066!I%!I%,,%+! ,(! ,#G%! ,/01!M+(5*!#1!#!I#1%H!&(,!#1!#!

,%+,0#+2!/#609%C!3(+!%J#$*6%!

R-ONaCH3

CH3

CH3

Cl CH3 C CH2

CH3

O ClH

!

K/51!-(+!*+%*#+0&M!A.8RER.<c<.@8V!H!;%!1/(569!1,#+,!;0,/!(CH3)3C-ONa+-!!#&9!.@8V'+C!

!

&39=1274OJ!^,!-(66(;1!":@!$%4/#&01$C!)01*6#4%$%&,!(-!/#609%!!0(&!I2!#6G(J09%!0(&C!

R-ONa R XSN

2

R-O-R NaBrOO+-

!\K$9>7;2! ;H! D71N;O3>=123! ;2!$/9;=;/4J! Q,/%+1! 4#&! I%! *+%*#+%9! I2! ,+%#,$%&,! (-! *+0$#+2! (+!

1%4(&9#+2!#64(/(61!;0,/!90#S($%,/#&%!0&!*+%1%&4%!(-!-6(5+(I(+04!#409!#1!#!4#,#621,C!

R-OH CH2N2

HBF4R-O-CH3 N2OO

C2H5-OH CH2N2OHBF4

C2H5-O-CH3N2O!

'5,!,/01!$%,/(9!01!(&62!51%-56!-(+!,/%!*+%*#+#,0(&!(-!$%,/26!%,/%+1C!

! BV

":;?3:>734J!

"=64791/!?:;?3:>734J!

=E Q,/%+1!#+%!/0M/62!L(6#,06%!#&9!0&-6#$$#I6%!15I1,#&4%1C!@E QJ4%*,! 90$%,/26! %,/%+! #&9! %,/26!$%,/26! %,/%+H! ;/04/! #+%! M#1%1! #66! #+%! *6%#1#&,!1$%660&M!4(6(5+6%11!60d5091C!

RE K/%0+!I(060&M!*(0&,1!M+#95#662!0&4+%#1%!;0,/!,/%!0&4+%#1%!0&!$(6%456#+!;%0M/,C!'5,!%,/%+1! /#L%! 6(;%+! I(060&M! *(0&,1! ,/#&! 01($%+04! #64(/(61! I%4#51%! ,/%2! #+%!

0&4#*#I6%!(-!-(+$0&M!0&,%+!$(6%456#+!/29+(M%&!I(&91!95%!,(!,/%!#I1%&4%!(-!Pc8!

M+(5*1C!

!

Q,/%+1!#+%!1*#+0&M62!1(65I6%!0&!;#,%+!10&4%!,/%0+!(J2M%&!#,($!01!&(,!4#*#I6%!(-!-(+$0&M!8<I(&9!

;0,/!/29+(M%&!;0,/!/29+(M%&!#,($!(-!;#,%+!$(6%456%C!

!

'=3O791/!":;?3:>734J!

Q,/%+1!#+%!$54/!6%11!+%#4,0L%!4($*(5&91!I%4#51%!,/%2!#+%!d50,%!1,#I6%C!K/%2!9(!&(,!+%#4,!;0,/!

#4,0L%!$%,#61H!1,+(&M!I#1%1!60G%!:#c8H!+%9540&M!#&9!(J090S0&M!#M%&,1C!

SK!#1/;L321>7;24J!b/%&!%,/%+1!+%#4,!;0,/!4/6(+0&%!(+!I+($0&%!15I1,0,5,0(&!*+%-%+%&,0#662!#,!&<

.#+I(&!,#G%1!*6#4%C!!

3(+!%J#$*6%a!

CH3-CH2-O-CH2-CH3

Cl2

dark

CH3-CH-O-CH2-CH3 CH3-CH-O-CH-CH3

Cl2

dark

Cl Cl Cl

!!!!!!!!! ! ! ! ! !&<!./6(+(!90%,/26!%,/%+!!!!!!!!!!!&H&

=<!)04/6(+(90%,/26!%,/%+C!

!

K/%!%J,%&,!(-!15I1,0,5,0(&!9%*%&91!(&!+%#4,0(&!4(&90,0(&1C!

UK!T1479!G1>C:3J!Q,/%+1!+%#4,!;0,/!4(69!4(&4%&,+#,%9!156*/5+04!#409!(+!8.6!,(!M0L%!(J(&05$!1#6,C!

K/%0+!I#104!&#,5+%!01!95%!,(!,/%!*+%1%&4%!(-!,;(!6(&%!*#0+1!(&!(J2M%&!#,($C!

ClR O R..

..

O ClH R O+

R

H

..

-

oxonium ion

4(69

!

K/01! *+(*%+,2! 01! 51%9! ,(! 1%*#+#,%! %,/%+1! -+($! %,/26! I+($09%! #&9! ,(! 901,0&M501/! -+($! #6G#&%1C!

"0&4%!#6G#&%1!9(!&(,!+%#4,!;0,/!#4091C!

!

XK!B;:O1>7;2!;H!?3:;@7834! _$C>;!;@781>7;2KJ!c&!1,#&90&M! 0&!4(&,#4,!;0,/!#0+!%,/%+1!4($I0&%!

;0,/!(J2M%&!,(!-(+$!*%+(J09%!;/04/!01!/0M/62!%J*6(10L%C!

H2CH3C O CH2CH3OO2long

contact(CH3CH(OOH).OC2H5

!

K/%1%! *%+(J09%1! 9%4($*(1%! L0(6%&,62! #,! /0M/! ,%$*%+#,5+%C! K/51! %,/%+1! 1/(569! I%! #6;#21! I%!

*5+0-0%9! I%-(+%! 901,066#,0(&C! b/%&! %,/%+1! ,/#,! 4(&,#0&1! *%+(J09%! 01! 901,066%9H! #,! ,/%! %&9! (-!

! B?

901,066#,0(&!+%1095#6!*%+(J09%!$#2!%J*6(9%C!'%4#51%!(-!,/01!%,/%+!1/(569!&%L%+!I%!%L#*(+#,%9!,(!

9+2&%11C!

!

YK!#68:;/6474J!Q,/%+1!;/%&!,+%#,%9!;0,/!9065,%!156*/5+04!#409!5&9%+!*+%115+%H!,/%2!/29+(621%!,(!

M0L%!#64(/(61C!

R O R Odil H2SO4 2 ROHOH2

under pressure

H5C2 O C2H5dil H2SO4 2 C2H5OHOH2

under pressureO

Diethyl ether Ethyl alcohol!

\K!%319>7;2!I7>=!"=;4?=;:C4!"32>1P9=/;:783J!b0,/!N.6V!%,/%+!46%#L%!,(!M0L%!#6G26!4/6(+09%1!

R O R O

R O R' O

PCl5 2 R-Cl POCl3O

PCl5 R-Cl R'Cl POCl3O O!

]K!%319>7;2!I7>=!#+!128!#T:J!Q,/%+1!+%#4,!;0,/!/(,!4(&4%&,+#,%9!8^!(+!8'+!,(!M0L%!#&!#64(/(6!

#&9!#6G26!/#609%C!

R O R' O R'BrOBrH R-OH!

^&!4#1%!(-!$0J%9!%,/%+1!,/%!/#6(M%&!#,($!#,,#4G1!,(!,/%!1$#66%+!#6G26!M+(5*1H!95%!,(!,/%!1,%++04!

%--%4,C!%CMC!

H5C6 O C2H5 O OC6H5-OHHI C2H5I!

K/%!(+9%+!(-!+%#4,0L0,2!(-!/#6(M%&!#409!01!!

8^i8'+i8.6!

b0,/!,/%!%J4%11!(-!#409H!,/%!#64(/(6!0&0,0#662!*+(954%9!01!#61(!4(&L%+,%9!,(!#6G26!/#609%C!%CMC!

H5C2 O C2H5 O O2HI 2C2H5I OH2(excess) !

^K! %319>7;2!I7>=! 193>6/! ! 9=/;:783J! Q,/%+1! +%#4,! ;0,/! #409! 4/6(+09%! ,(! M0L%! #6G26! /#609%1! #&9!

%1,%+1C!3(+!%J#$*6%!

H5C2 O C2H5O CH3 C Cl

O

C2H5Cl O CH3 C C2H5

O

Ethyl actateEthyl chlorideDiethyl ether Acetyl chloride

\&.6@

!

! BD

(?;@783!

Q*(J09%1!#+%! ,/%!4264604!%,/%+1! 0&!;/04/!%,/%+%#6!(J2M%&!01! 60&G%9!;0,/! ,;(!#9j#4%&,!4#+I(&!,(!

-(+$! ,/+%%! $%$I%+%9! +0&MC! 0C%C! (J0+#&! A(J0+#&%E! +0&MC! Q*(J2! 4($*(5&9! 4(&,#0&! (J0+#&%! +0&MC!

cJ0+#&!4($*(5&91!#+%!#61(!+%-%++%9!,(!#1!424604!%,/%+1!(+!#6G%&%!(J09%1C!

C C CH3CH3

O

OHOH

H2C CH2

O

HC CH2

O

R

epoxide

Ethyleneoxide[ 1, 2 -Epoxyethane][ 1, 2 -epoxyalkane]

!

Q*(J2!%,/#&%!(+!%,/26%&%!(J09%!A(J0+#&E!01!,/%!$(1,!0$*(+,#&,!$%$I%+!(-!,/01!M+(5*C!

&3>=;8!;H!?:3?1:1>7;2J!Q*(J09%1!$#2H!0&!M%&%+#6H!I%!*+%*#+%9!I2!%*(J09#,0(&!(-!#6G%&%1!;0,/!

*%+(J2!#4091C!N%+I%&S(04!#409!.?8V.cc@8H!$(&(*%+*/,/#604!#409H!8cc..?8B.cc@8!#&9!N<

&0,+(!I%&S(04!#409!/#L%!I%%&!51%9C!

R-CH=CHR'per acid

R R

O

'

Epoxide

CH2 CH2per acid

H2C CH2

O

Ethylene oxide !!

(>=6/323!;@783!O16!<3!;<>17238J!

7K!T6!%319>7;2!;H!'=/;:;=68:72!I7>=!<143J!

HO-CH2-CH2-ClO KOH H2C CH2

O

O KCl H2OO!

!

!

! Bh

N(110I62!,/%!$%4/#&01$!01a!!

H O CH2 CH2 Clfast

-H2O

O-

H2C CH2 ClCH2H2C

O-HO

-

-Cl

!77K!T6!;@781>7;2!;H!3>=6/323!I7>=!;@6L32!72!>=3!?:343293!;H!47/E3:!91>1/64>W!

2CH2=CH2O O2

Ag

2500C

H2C C 2

O

H2

!":;?3:>734J!

Q,/26%&%! (J09%! 01! ,(J04H! -6#$$#I6%! M#1! /#L0&M! IC*! =>CD(.CM%&%+#662! %*(J09%1! #+%! +%#4,0L%!

4($*(5&9H!,/01!01!I%4#51%!,(!+%6%#1%!,/%0+!1,+#0&!,/%2!/#L%!,/%!,%&9%&42!,(!(*%&!,/%0+!+0&MC!K/%1%!

(J2M%&!#,($1!4($I0&%!;0,/!,/%!+%#4,0L%!/29+(M%&!#,($!(-!L#+0(51!4($*(5&91!,(!-(+$!/29+(J26!

M+(5*C!!

H2C CH2

OH AO HO-CH2-CH2-A

!%319>7;2!I7>=!#F#!

!!!!!!!!!!!!!!!!!!

H2C CH2

O O OH2

H+ H2C C 2

OH OH

H

Ethylene glycol!%319>7;2!I7>=!1/9;=;/4!

H2C CH2

O O

H2C CH2

OH

OR

H-O-R

Alkoxy ethane !%319>7;2!I7>=!$OO;271!

H2C CH2

O O

H2C CH2

OH

NH2

2-Aminoethonal

HNH2

!%319>7;2!I7>=!=1/;L321>385!#T:J!

H2C CH2

O O

H2C CH2

OH

Br

BrH!

! BU

%319>7;2!I7>=!,7$/#Y!

H2C CH2

OO LiAlH4 CH3CH2OH

Ethyl alcohol!

`&12$$%,+04#6!%*(J09%1!M0L%!,/%!$(+%!/0M/62!15I1,0,5,%9!#64(/(6!;0,/!$#0&!*+(954,C!

H2C CH2

O

R LiAlH4R-CH-CH3 RCH2CH2OHO

OH

main product !

!

%319>7;2!I7>=!#'GJ!

H2C CH2

OO HCN HO-CH2-CH2-CN

ethylene cyanohydrin!

!

%319>7;2!I7>=!Q:7L21:8!%31L32>J!

Q,/26%&%!(J09%!+%#4,1!;0,/!g+0M&#+9!Z%#M%&,!,(!M0L%!#990,0(&!*+(954,!;/04/!(&!/29+(62101!20%69!

*+0$#+2!#64(/(6C!

H2C CH2

OO R-MgX CH2-CH2-R

OMgX

H+ / H2O

HO-CH2-CH2-R

!

F@781>7;2a!

Q*(J09%1!#+%!(J090S%9!;0,/!90$%,/26!156*/(J09%!,(!&</29+(J2!G%,(&%1C!

HC CH

O

R R

O Me2SOH

+

R CH C R

O SMe2

OH H

+ -

R CH C

OH O

R-Me2S

!

$/83=6834!128!A3>;234!

F69%/29%1! #&9! G%,(&%1! I(,/! 4(&,#0&! (J(! (+! 4#+I(&26! M+(5*! A! ifc! EC! ^&! #69%/29%1! 4#+I(&26!

4#+I(&!(&!(&%!109%!#,,#4/%9!,(!/29+(M%&!#,($!#&9!,(!4#+I(&!#,($!(&!(,/%+!109%H!,/51!-5&4,0(&#6!

M+(5*! (-! #69%/29%1! 01! P.8cC! K/01! M+(5*! (445+1! #,! ,/%! %&9! (-! #! 4/#0&C! ^&! G%,(&%1! 4#+I(&26!

4#+I(&H!(&!I(,/!109%1!#,,#4G!,(!4#+I(&!#,($1H!,/51!,/%!-5&4,0(&#6!M+(5*!0&!G%,(&%1!(445+1!;0,/0&!#!

4/#0&C!A!c c c

O

E!

! V>

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! !!

F69%/29%!#&9!G%,(&%1!#+%!4(66%4,0L%62!4#66%9!4#+I(&26!4($*(5&91C!

!!!!!!!!!!!!!!!!!!!!!! !!

]0G%!4#+I(&<4#+I(&!9(5I6%!I(&9H!9(5I6%!I(&9!I%,;%%&!4#+I(&!#&9!(J2M%&!0&!4#+I(&26!M+(5*!01!

4($*(1%9!(-! (&%!!! ! #&9!(&%!"! I(&9C!.#+I(&26! 4#+I(&! 01! 0&! #! 1,#,%! (-! ! 1*@! /2I+090S#,0(&C!K/%!

4#+I(&! P(J2M%&!!! I(&9! 01! -(+$%9! I2! ,/%! (L%+6#*! (-! 1*@! (+I0,#6! (-! 4#+I(&!;0,/! 1*

@<! (+I0,#6! (-!

(J2M%&!#,($C!c&! ,/%!(,/%+!/#&9! ,/%!4#+I(&!(J2M%&!"!I(&9! 01! -(+$%9!I2!109%!;01%!(L%+6#*!(-!

5&/2I+0901%9! *<(+I0,#6! ! (-! I(,/! #,($1C! K;(! 5&1/#+%9! *#0+1! (-! %6%4,+(&! (445*2! ,/%! 1*</2I+09!

(+I0,#61! (-! (J2M%&C! 10&4%! ,/+%%!!<I(&9! (-! 4#+I(&26! 4#+I(&! 5,060S%! 1*@! (+I0,#61H! ,/%2! 60%! 0&! (&%!

*6#&%C!K/%!I(&9!#&M6%1!I%,;%%&!,/%!#,,#4/%9!#,($1!#+%!#**+(J0$#,%62!=@>>C!

!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! !'5,!/%+%!"!%6%4,+(&1!#+%!&(,!%d5#662!1/#+%9!I2!I(,/!4#+I(&!#&9!(J2M%&!#,($1C!K/01!01!I%4#51%!(-!

,/%!%6%4,+(&%M#,0L0,2!C!)5%!,(!,/%!/0M/!%6%4,+(&%M#,0L0,2!(-!(J2M%&!#,($H!,/%!"!%6%4,+(&!46(59!01!

*566%9! $(+%! -(+;#+9! ,/%! (J2M%&! #,($C! F1! +%156,! I(&9! 01! *(6#+0S%9H! (J2M%&! #,,#0&1! #! *#+,0#6!

&%M#,0L%!4/#+M%!#&9!4#+I(&!#!*#+,0#6!*(10,0L%!4/#+M%C!

! V=

.

C

.

O$ $+ -

polarity due to inductive effect!

8(;%L%+!,/%!/0M/!L#65%1!(-!90*(6%!$($%&,1!(-!#69%/29%1!#&9!G%,(&%1!4#&Y,!I%!#44(5&,%9!(&62!

I2!0&954,0L%!%--%4,!I5,!#61(!I2!,/%!+%1(&#&4%!%--%4,C!3(66(;0&M!+%1(&#&4%!1,+54,5+%1!#+%!*(110I6%C!

.

C

.

O

.

C

.

O-+

!.#+I(J26!M+(5*!01!+%1(&#&4%!/2I+09!(-!#I(L%!,;(!1,+54,5+%1C!

&3>=;84!;H!":3?1:1>7;2J!

'(,/!F69%/29%1!#&9!G%,(&%1!$#2!I%!*+%*#+%9!I2!,/%!-(66(;0&M!$%,/(91C!

SK!F@781>7;2!;H!1/9;=;/4J!F69%/29%1!#+%!-(+$%9!I2!,/%!(J09#,0(&!(-!*+0$#+2!#64(/(61C!

RCH2OHK2Cr2O7 / H

+

RCHOControlled Oxidation

Aldehyde

CH3CH2OH CH3CHOControlled Oxidation

1o alcohol

+ H2O

+ H2O

Ethyl alcohol Acetaldehyde!

.(&,+(66%9!(J09#,0(&!4#&!#61(!I%!4#++0%9!(5,!I2!510&M!.+cR<!*2+090&%!W';//72!:31L32>X!m%,(&%1!

#+%!!*+%*#+%9!I2!,/%!(J09#,0(&!(-!1%4(&9#+2!#64(/(61C!

K2Cr2O7 / H+

R-C-R'

Ketone

2o alcohol

R-CHOH

R'

O

CH3 C CH3

O

K2Cr2O7 / H+

CH3 CH CH3

OH

+ H2O

2-Propanol Acetone

+ H2O

!m%,(&%1!#+%!&(,!%#1062!(J090S%9!-5+,/%+C!m%,(&%1!4#&!#61(!I%!(I,#0&%9!I2!F??321C3:!;@781>7;2!

(-!1%4(&9#+2!#64(/(61H!;/04/!0&L(6L%1!+%-65J0&M!(-!1%4(&9!#64(/(6!;0,/!#4%,(&%!0&!,/%!*+%1%&4%!

(-!#65$0&05$!,%+,0#+2!I5,(J09%H!F6c.A.8RERH!4#,#621,C!

! V@

R

CHOH

R'

C

CH3

CH3

O

AlOC(CH3)3C

R

R'

O CHOH

CH3

CH3

O O

AcetoneKetone Iso propyl alcohol2o Alcohol

!

UK!D3=68:;L321>7;2!;H!1/9;=;/4J!'2!*#110&M!,/%!#64(/(6!L#*(5+1!(L%+!#!4(**%+!4#,#621,!/%#,%9!

,(!#I(5,!R>>(.H!#69%/29%1!#&9!G%,(&%1!#+%!*+%*#+%9C!=

(! #64(/(61!M0L%!#69%/29%1!;/06%!@

(!M0L%!

G%,(&%1C!!

RCH2OHCu

300 oC R C H

O

O H2

!

CH3CH2OHCu

300 oC CH3 C H

O

O H2

Ethylalcohol Acetaldehyde

R-CHOH-R' R C R'

O

O H2

2o alcohol

Cu

300 oCKetone

CH3 CH CH3

OHCu

300 oCCH3 CH CH3

O

O H2

Iso propyl alcohol Acetone !

XW!D:6!874>7//1>7;2!;H!91/97CO!41/>4!;H!$9784J!F69%/29%1!#+%!*+%*#+%9!I2!*2+(62101!(-!4#6405$!

1#6,! (-! -#,,2! #409! ;0,/! .#6405$! -(+$#,%C! b/06%! 4#6405$! -(+$#,%! #6(&%! (&! /%#,0&M! M0L%1!

-(+$#69%/29%C!

!!!!!!!!!!!!!!!! !

! VR

!!!!!!!!!!!!!! !

m%,(&%1!#+%!(I,#0&%9!I2!/%#,0&M!4#6405$!1#6,!(-!-#,,2!#409!(,/%+!,/#&!4#6405$!-(+$#,%C!

!!!!!!!!!!! !

YK!#68:1>7;2!;H!1/06234J!F69%/29%1!#&9!G%,(&%1!4#&!I%!*+%*#+%9!I2!+%#4,0(&1!(-!#6G2&%1!;0,/!

,/%!;#,%+!0&!*+%1%&4%!(-!$%+45+04!156*/#,%!#&9!156*/5+04!#409C!

CH3 C C CH3 O H OHHgSO4

H2SO4

R C C H

H

O H

R C CH3

OPropyneAcetone

Unstable!

F4%,26%&%!M0L%!#69%/29%!5&9%+!,/%1%!4(&90,0(&1C!

H C C H O H OHHgSO4

H2SO4

CH3 C H

O

!\K!#68:;/6474! ;H! L3OPD7=1/7834J!F69%/29%1! #+%! *+%*#+%9! I2! ,/%!/29+(62101! (-! M%$! 90/#609%1!

4(&,#0&0&M!I(,/!/#6(M%&!#,($!(&!,%+$0&#6!4#+I(&!#,($C!

R CH Cl

Cl H2O

NaOH R CH OH

OHH2O

R C

O

H

-

!!

! VB

m%,(&%1!#+%!*+%*#+%9!I2!,/%!/29(62101!(-!M%$<90/#609%1!4(&,#0&0&M!I(,/!/#6(M%&!#,($1!(&!&(&!

,%+$0&#6!4#+I(&!#,($C!

R C R'

C l

C l

H 2 O

NaOHR C

O

R'

!

3(+!%J#$*6%!

CH3 CH Cl

ClH2O

NaOHCH3CHO

Acetaldehyde

CH3 C CH3

Cl

Cl

H2O

NaOHCH3 C CH3

O

!

]K!'1>1/6>79!839;O?;47>7;2!;H! !19784J!F69%/29%1!4#&&(,!I%!*+%*#+%9!I2!,/01!$%,/(9C!m%,(&%1!

#+%!*+%*#+%9!I2!*#110&M!L#*(5+1!(-!4#+I(J2604!#409!(L%+!/%#,%9!T&c!(+!K/c@C!3(+!%J#$*6%H!

CH3 C OH

O

2MnO

300oCCH3 C CH3

O

O OH2 O CO2

2 molecules of acetic acid Acetone!

^K!%38C9>7;2!;H!$978!'=/;:7834J!Z%;432OC28!%38C9>7;2[J!F69%/29%1!4#&!I%!*+%*#+%9!I2!,/%!

+%954,0(&!(-!#409!4/6(+09%!0&!,/%!*+%1%&4%!(-!*#66#905$!15**(+,%9!(L%+!I#+05$!156*/#,%C!

R C Cl

O

R C H

O

OO H2Pd / BaSO4

S or quinolineClH

!F69%/29%1! 4#&! #61(! I%! %#1062! +%954%9! ,(! *+0$#+2! #64(/(6! I5,! ,/%! 4#,#621,! 01! *(01(&%9! I2! ,/%!

156*/5+!#&9!,/51!#69%/29%1!#+%!,/%!-0&#6!*+(954,C!

m%,(&%1!4#&&(,!I%!*+%*#+%9!I2!,/01!$%,/(9C!

`K!B:;O!Q:7L21:8!%31L32>J!F69%/29%1!4#&! !I%!*+%*#+%9! -+($!g+0M&#+9!Z%#M%&,! AZTM_E! 0&!

,;(!;#21C!

7K!B:;O!=68:;L32!9612783J!

RMgX H C NO R C NMgX

H

Additin product

H+ / H2O

R C CH3

O

MgX(NH2)

O!

! VV

77K!B:;O!1/06/!H;:O1>34J!

H C OR'

O

O RMgX H C

O-MgX

R

OR'H2O

H C OH

R

OH

-H2O

R C H

O

!

m%,(&%1!4#&!#61(!I%!*+%*#+%9!-+($!g+0M&#+9!+%#M%&,!0&!,;(!;#21H!

7K!B:;O!1/06/!9612783J!

R'-MgXO R C N R C

R

NMgBrH

+ / H2O

R C R'

O

OMgX

!

77K!B:;O!1978!'=/;:7834J!

CH3 C Cl

O

O R'MgX R C Cl

OMgX

R'

R C R'

O

O MgXCl

!

F69%/29%!(+!G%,(&%1!1(!-(+$%9H!$#2!-5+,/%+!+%#4,!;0,/!%J4%11!(-!,/%!g+0M&#+9!+%#M%&,1!,(!M0L%!

#64(/(61C!

!

fK! F@;! ?:;9344J! K/01! $%,/(9! 01! 0&951,+0#662! 0$*(+,#&,! -(+! ,/%! *+%*#+#,0(&! (-! #69%/29%1C! ! ^,!

0&L(6L%1! ,/%! ,+%#,$%&,! (-! #&! #6G%&%! ;0,/! 4#+I(&! $(&(J09%! #&9! /29+(M%&! 0&! ,/%! *+%1%&4%! (-!

4(I#6,!4#+I(&26!4#,#621,!#,!/0M/!,%$*%+#,5+%!#&9!*+%115+%C!

R CH CH2 O CO O H2

[Co(CO)4R CH2 CH2 C CH3

O

AldehydeAlkene !

m%,(&%1!4#&&(,!I%!*+%*#+%9!I2!,/01!$%,/(9C!

!

SaK! M1903:! ?:;9344J! K/01! $%,/(9! 0&L(6L%1! ,/%! ,+%#,$%&,! (-! #6G%&%! ;0,/! #4090-0%9! #d5%(51!

1(65,0(&!(-!*#66#905$!4/6(+09%H!!N9.6@!#&9!45*+04!4/6(+09%H!.5.6@C!

! V?

CH2 CH2O OCuCl2

CH3 C H

O

Alkene

PdCl2 OH2 O Pd O 2HCl

R CH CH2O OPdCl2 OH2 R C CH3

O

O Pd O 2HCl

Ketone

Acetaldehyde

!

":;?3:>734J!=E 3(+$#69%/29%!01!M#1!#,!+(($!,%$*%+#,5+%!#&9!(,/%+!#69%/29%1!#&9!G%,(&%1!#+%!4(6(5+6%11!60d5091C!

@E ](;%+!#69%/29%1!#&9!G%,(&%1!#+%!1(65I6%!0&!;#,%+!95%!,(!4#*#I060,2!(-!-(+$0&M!/29+(M%&!I(&91! ;0,/! ;#,%+! $(6%456%1C! '5,! /0M/%+! $%$I%+1! 4(&,#0&0&M! $(+%! ,/#&! -0L%! 4#+I(&!

#,($1!#+%!0&1(65I6%!0&!;#,%+!#&9!1(65I6%!0&!(+M#&04!1(6L%&,C!

RE "0&4%!#69%/29%1!#&9!G%,(&%1!#+%!*(6#+!4($*(5&91C!K/%0+!I(060&M!*(0&,1!#+%!/0M/%+! ,/#&!4(++%1*(&90&M! &(&! *(6#+! 4($*(5&91C! '5,! ,/%1%!$(6%456%1! #+%! &(,! 4#*#I6%! (-! -(+$0&M!

0&,%+$(6%456#+! /29+(M%&! I(&91C! K/%0+! I(060&M! *(0&,1! #+%! 6(;%+! ,/#&! 4(++%1*(&90&M!

#64(/(61C!

BE )%&10,2!(-!#69%/29%1!#&9!G%,(&%1!#+%!6%11%+!,/#&!,/#,!(-!;#,%+C!!

'=3O791/!?:;?3:>734J!'(,/!#69%/29%1!#&9!G%,(&%1!4(&,#0&!/0M/62!*(6#+!4#+I(&26!M+(5*C!

.

C

.

O

.

C+

.

O- $ $.

C

.

O

+ -

!

.#+I(&26!4#+I(&!01!%6%4,+(&!9%-040%&,!#&9!4#+I(&26!(J2M%&!01!%6%4,+(&!+04/C!K/%!%6%4,+(&!9%-040%&,!

4#+I(&!01!+%#9062!#,,#4G%9!I2!%6%4,+(&!+04/!&546%(*/06%1!#&9!%6%4,+(&!+04/!(J2M%&!01!#,,#4G%9!I2!

%6%4,+(&! 9%-040%&,! %6%4,+(*/06%1C! K/%! ,2*04#6! +%#4,0(&! (-! #69%/29%1! #&9! G%,(&%1! 01! &546%(*/0604!

#990,0(&C!K/%2!5&9%+M(!&546%(*/0604!#990,0(&!+%#4,0(&!I2!-(66(;0&M!M%&%+#6!$%4/#&01$C!!

Nu-H B Nu: B-HO O-

Neutral weak nucleophile Strong nucleophile

!

!

$J!T143!'1>1/6438!$887>7;2J!'#1%!4(&L%+,!;%#G!&546%(*/06%!,(!1,+(&M!(&%!

->3?!SJ!!F,,#4G!(-!&546%(*/06%!#,!4#+I(&26!!4#+I(&!,(!-(+$!&%;!!<I(&9C!

.

.

O

Nu

.

O-

Nu:

..

: :..

..

!

",%*!@a!F,,#4G!(-!%6%4,+(*/06%!A!%CMCH!<8OE!#,!&%M#,0L%62!4/#+M%9!(J2M%&!,(!M0L%!#990,0(&!*+(954,C!

! VD

Nu

.

O:..

..

+ H+

Nu

.

OH..

..

Addition product

-

!!

TK!$978!'1>1/6438!$887>7;2J!!

->3?!SJ!N+(,(&#,0(&!(-!4#+I(&26!M+(5*C!

.

.

O:..

..

+ H+

.

.

O+

H..

.

.

O H..

.. +

Resonance stabilised protonated carbonylgroup!

->3?!UJ!F,,#4G!(-!&546%(*/06%!(&!*+(,(&#,%9!4#+I(&26!4#+I(&!,(!M0L%!#990,0(&!*+(954,C!

.

C

.

O H..

Nu

.

O H..

..

Nu : -

..

+ O

Addition product. !

F990,0(&!*+(954,1!+%$#0&1!1#$%!0&!I(,/!#409!#&9!I#1%!4#,#621%9!+%#4,0(&C!

!

K/%! +%#4,0L0,2!(-! ,/%!4#+I(&26!M+(5*! ,(;#+91! ,/%!&546%(*/0604!#990,0(&! +%#4,0(&1!9%*%&91!5*(&!

,/%!$#M&0,59%!(-! ,/%!*(10,0L%!4/#+M%!(&! ,/%!4#+I(&26!4#+I(&!#&9!#61(!(&!4+(;90&M!#+(5&9! ,/%!

4#+I(&26! 4#+I(&C! A",%+04! -#4,(+EC! F6G26! M+(5*1! (-! (,/%+! %6%4,+(&! 9(&#,0&M! ,/#,! 9%4+%#1%1! ,/%!

*(10,0L%! 4/#+M%! (&! ,/%! 4#+I(&26! 4#+I(&! ;066! 9%4+%#1%! 0,1! +%#4,0L0,2! ,(;#+91! ,/%! &546%(*/0604!

#990,0(&!-(66(;1!,/%!-(66(;0&M!(+9%+C!

H C H

O

R C H

O

R C

O

R> >Formaldehyde Aldehyde Ketone !

$9787>6!;H!!P#68:;L324J!F!4#+I(&!#,($!&%J,!,(!4#+I(&26!M+(5*!01!&<4#+I(&!#,($!#&9!/29+(M%&1!

#,,#4/%9!,(!,/01!4#+I(&!#+%!G&(;&!#1!&!P!/29+(M%&1C!&<!/29+(M%&1!0&!#69%/29%1!#&9!G%,(&%1!#+%!

#I1,+#4,#I6%!I2!I#1%!0C%[!#40904!0&!&#,5+%C!,/01!01!95%!,(!,/%!-#4,!,/#,!4#+I(&0(&!-(+$%9!,/%!&(+$#6!

(-!/29+(M%&!#,($!01!1,#I060S%9!I2!+%1(&#&4%C!,/01!0(&!01!4#66%9!(2;/1>3!7;2C!

! Vh

CH3 C

O

C CH3

H

CH3

B

CH3 C

O

C CH3

CH3

CH3 C

O

C CH3

CH3

:

..

-

:

..

:

..

:

..

-

-

Resonance StabilizedEnolate ion.

!

K/%! &%M#,0L%62! 4/#+M%9! 4#+I(&! (-! %&(6#,%! 0(&! #4,! #1! #! &546%(*/06%C! F66! 4(&9%&1#,0(&! +%#4,0(&!

0&L(6L%9!-(+$#,0(&!(-!!%&(6#,%!0(&!#&9!0,1!#990,0(&!,(!4#+I(&26!M+(5*C!

!

_$K!GC9/3;?=7/79!$887>7;2!%319>7;24!;H!$/83=6834!g!A3>;234!

_SK! $887>7;2! ;H! #68:;L32! '612783J! F69%/29%1! #&9! m%,(&%1! (&! #990,0(&! (-! 8.:! M0L%!

9612;=68:724C!Z%#4,0(&!01!4#++0%9!(5,!0&!,/%!*+%1%&4%!(-!I#104!4#,#621,C!8.:!01!*+(954%9!in situ!

I2!,/%!#4,0(&!(-!9065,%!8@"cB!(&!m.:C!

!!!!!!!!!!!!!!!!!!!!

O HCN CH3 C CH3

CN

OH

Cyanohydrin

c

.8R .8R

!

!!!!!!!!!!!!!!!!!!!!

CH3 C H

O

O HCN CH3 C H

OH

CN

Acetaldehyde cyanohydrinAcetaldehyde !!

!!!!

! !

!!!!!!!!!!!!!!!

CH3 C CH3

O

HCN CH3 C CH3

OH

CN

O

Acetone Acetone cyanohydrin.!

!_UK!$887>7;2!;H!Q:7L21:8!:31L32>J!F69%/29%1!#&9!m%,(&%1!;0,/!g+0M&#+9!+%#M%&,!-0+1,!M0L%!,/%!

#990,0(&!*+(954,!;/04/!4#&!I%!/29+(621%9!;0,/!9065,%!#409!,(!20%69!#64(/(6C!c&62!-(+$#69%/29%!

M0L%1!=>!#64(/(61H!(,/%+!#69%/29%1!M0L%!@

>!#64(/(6!#&9!G%,(&%1!M0L%!R

(!#64(/(61C!3(+!%J#$*6%!

!!

H C H

ORMgX

H C H

OMgX

R

H+ / H2O

RCH2OH

1o alcoholFormaldehyde!

! VU

R C H

OR'MgX

R C H

OMgX

R'

H+ / H2O

R CH

OH

R'

Aldehyde 2o alcohol!

!!

R C R

OR'MgX

R C R

OMgX

R'

H+ / H2O

R C

OH

R'

R

Ketone

3o alcohol!

!_XK! $887>7;2! ;H! -;87CO! <74C/?=1>3J! F6%9%/29%1! #&9! $%,/26! G%,(&%1! ;/%&! ,+%#,%9! ;0,/!

1#,5+#,%9!#d5%(51!1(65,0(&!(-!1(905$!I0156*/#,%H!#!1(609!#990,0(&!4($*(5&9!01!-(+$%9C!

H C H

O

O NaHSO4 CH3 CH3

SO3Na

OH

Bisulphite addition compound!

CH3 C H

O

O NaHSO4CH3 H

SO3Na

OH

Acetaldehyde bisulphite

CH3 C CH3

O

O NaHSO4CH3 H

SO3Na

OH

Acetone bisulphite !

K/%1%! I0156*/0,%1! 4#&! I%! 9%4($*(1%9! ;0,/! 9065,%! #4091! (+! I#1%1! ,(! +%M%&%+#,%! ,/%! 4#+I(&26!

4($*(5&9H! ,/%+%-(+%! ,/01!*+(4%11!(-! -(+$#,0(&!#&9!9%4($*(10,0(&!(-!I0156*/0,%! 01!51%9! -(+! ,/%!

*5+0-04#,0(&!#&9!1%*#+#,0(&!(-!4#+I(&26!4($*(5&91!-+($!$0J,5+%1C!

!

_YK! $887>7;2! ;H! $OO;271J! F69%/29%1! A%J4%*,! -(+$#69%/29%E! -(+$! 1(609! #990,0(&! *+(954,H!

#69%/29%!#$$(&0#!

R C H

O

O NH3 R C H

NH2

OH

Aldehyde ammonia!

F69%/29%1! 4#&! #61(!I%! +%M%&%+#,%9!I2!/%#,0&M! #69%/29%! #$$(&0#1!;0,/!9065,%! #4091C!K/51! ,/%!

*+(4%11!(-!-(+$#,0(&!#&9!9%4($*(10,0(&!(-!,/%1%!4($*(5&91!4#&!I%!51%9!(+!,/%!1%*#+#,0(&!#&9!

*5+0-04#,0(&!(-!#69%/29%1C!

3(+$#69%/29%! #&9! G%,(&%1! 9(! &(,! -(+$! #990,0(&! *+(954,! ;0,/! #$$(&0#C! K/%2! 20%69! 4($*6%J!

4(&9%&1#,0(&!*+(954,!;0,/!#$$(&0#C!3(+!%J#$*6%!

! ?>

H C H

O

O NH36 4 CH2

CH2

CH2

N

Hexamethylene tetramine. (Urotropine)

N

N N

!

`+(,+(*0&%!01!51%9!#1!5+0&#+2!#&,01%*,04C!

CH3 C CH3

O

2 O NH3 CH3 C CH2 C CH3

NH2

CH3 O

Diacetone amine.F4%,(&%!

TK!%319>7;24!+2E;/E72L!1887>7;2!H;//;I38!<6!:3O;E1/!;H!I1>3:J!

\K!%319>7;2!I7>=!$OO;271!D3:7E1>7E34J!Z%#4,0(&1! (-!F69%/29%! #&9!m%,(&%1!;0,/! #$$(&0#!

9%+0L#,0L%1! #+%! L%+2! 0$*(+,#&,!#&9! 4/#+#4,%+01,04! +%#4,0(&1!(-! 4#+I(&26! 4($*(5&91C!K/%2! +%#4,!

;0,/!#$$(&0#!9%+0L#,0L%1!A8@:<rE!,(!-(+$!4($*(5&91!4(&,#0&0&M!4#+I(&<&0,+(M%&!9(5I6%!I(&9!

A.f:<EH!;0,/!,/%!%60$0&#,0(&!(-!;#,%+C!

CH3

CH3

O NH2 Y

CH3

C

CH3

N Y OH2OO

!g%&%+#6!$%4/#&01$!(-!,/%!+%#4,0(&!0&L(6L%!-(66(;0&M!1,%*1C!

->3?!SJ!F,,#4G!(-!&546%(*/06%!(&!4#+I(&26!4#+I(&!,(!M0L%!5&1,#I6%!#990,0(&!*+(954,C!

CH3

CH3

O NH2 Y

CH3

C

CH3

NH+

Y

O-

H

O.. H

+ transfer

CH3

C

CH3

N Y

OH

H

[ unstable]

$! $!+ -

!->3?!UJ!Z%$(L#6!(-!;#,%+!,(!M0L%!,/%!-0&#6!*+(954,C!

CH3

C

CH3

N Y

OH

H

-H2O CH3

C

CH3

N Y

!

! ?=

F66! ,/%! #$$(&0#! 9%+0L#,0L%1! -(66(;! ,/%! 1#$%! $%4/#&01$C! K/%! #$$(&0#! 9%+0L#,0L%1! #+%!

/29+#S0&%H!*/%&26!/29+#S0&%H!@HB<90&0,+(*/%&26!/29+#S0&%H!/29+(J26#$0&%H!#&9!1%$04#+I#S09%C!

!

1K! %319>7;2! I7>=! #68:1N723J! F69%/29%1! #&9! G%,(&%1! -(+$! /29+#S(&%1! ;0,/! /29+#S0&%!

A:8@:8@E!

CH3 C O

H

O NH2 NH2 CH3CH=N-NH2

Acetaldehyde hydrazoneacetaldehyde!

CH3 C O

CH3

O H2NNH2 CH3 C

CH3

N NH2

Acetone hydrazoneF4%,(&% !<K! %319>7;2! I7>=! ?=326/! =68:1N723J! F69%/29%1! #&9! G%,(&%1! -(+$! */%&26! /29+#S(&%! ;0,/!

*/%&26!/29+#S0&%C!!

!9K! %319>7;2! I7>=! U5YPD727>:;! ?=326/! =68:1N723J! F69%/29%1! #&9! G%,(&%1! +%#4,! ;0,/! @HB<

90&0,+(*/%&26!/29+#S0&%!,(!-(+$!@HB<90&0,+(*/%&26!/29+#S(&%C!

!!

8K! %319>7;2! I7>=! #68:;@6/1O723J! F69%/29%1! #&9! G%,(&%1! -(+$! (J0$%! ;0,/!

/29+(J26#$0&%A:8@c8EC!

!

! ?@

3K! %319>7;2! I7>=! -3O791:<1N783J! F69%/29%1! #&9! G%,(&%1! M0L%! "%$04#+I#S(&%! ;0,/!

1%$04#+I#S09%!

CH3 C

H

O O H2N NH C NH2

O

CH3 C

H

NH NH C NH2

O

O OH2

Acetaldehyde oxime.

CH3 C

CH3

O O H2N NH C NH2

O

CH3 C

CH3

NH NH C NH2

O

O OH2

Acetone Semicarbazone.

Acetaldehyde

Acetone!

]K!%319>7;2!I7>=!1/9;=;/4J!F69%/29%!+%#4,!;0,/!#64(/(6!0&!,/%!*+%1%&4%!(-!9+2!8.6!M#1!,(!-(+$!

F4%,#61!%CMa!

R

C

H

O O R'OHdry HCl

C

R OH

H OR'

R'OH

HClC

R OR'

H OR'

Hemi acetal Acetal !

F4%,#61!#+%!+%#9062!46%#L%9!I2!#4091!,(!M0L%!#4%,#69%/29%1H!#&9!#+%!1,#I6%!,(;#+91!I#1%C!m%,(&%1!

/(;%L%+H!9(!&(,!-(+$!G%,#61!;0,/!$(&(/29+04!#64(/(61H!,/%2!+%#4,!;0,/!90/29+04!#64(/(61!,(!M0L%!

424604!G%,#61C!%CM!

!

_'K!';283241>7;2!%319>7;24J!K/%1%!+%#4,0(&1!0&L(6L%!!-(+$#,0(&!(-!%&(6#,%!0(&!;/04/!#,,#4G!(&!

4#+I(&26!4#+I(&!(-!#&(,/%+!$(6%456%!,(!M0L%!4(&9%&1#,0(&!*+(954,C!

!

^K!$/8;/!9;283241>7;2J!F69%/29%1!4(&,#0&0&M!#,!6%#1,!(&%!&<!/29+(M%&!#,($C!b/%&!,+%#,%9!;0,/!

9065,%! I#1%! 60G%! :#c8! 5&9%+M(! 4(&9%&1#,0(&! +%#4,0(&! ,(! M0L%! *+(954,1! 4#66%9! $/8;/4C! K/%!

+%#4,0(&! 01!G&(;&!#1! #69(6! 4(&9%&1#,0(&C!F69(61! #+%! ,/%! 4($*(5&91! 4(&,#0&0&M!I(,/! #69%/2904!

#&9! F64(/(604! -5&4,0(&#6! M+(5*1C! 3(+! %J#$*6%! ,;(! $(6%456%1! (-! #4%,#69%/29%! 4($I0&%! 0&!

*+%1%&4%!(-!9065,%!:#c8!!,(!-(+$!R</29+(J2!I5,#&#6C!

CH3 C

O

H O H2C CHO

H

CH3 CH CH 2 CHO

OH

2-hydroxy butanal (Aldol) !

&39=1274OJ!

3(66(;0&M!1,%*1!#+%!0&L(6L%9!0&!,/%!$%4/#&01$!(-!#69(6!4(&9%&1#,0(&!+%#4,0(&C!

->3?!SJ!3(+$#,0(&!(-!%&(6#,%!0(&!

! ?R

H CH2 C H

O

OH-

CH2 C H

O

O OH2:-

Enolate ionAcetaldehyde!

->3?! UJ! F,,#4G! (-! %&(6#,%! 0(&! A&546%(*/06%E! (&! 4#+I(&26! 4#+I(&! (-! #&(,/%+! $(6%456%! (-!

#4%,#69%/29%C!

CH3 C H

O

CH2 C H

O

:-

O CH3 CH CH2 C H

OO-$!

$!

-

+!

->3?!XJ!FI1,+#4,0(&!(-!*+(,(&!-+($!;#,%+!$(6%456%!,(!M0L%!-0&#6!*+(954,!F69(6C!

CH3 CH CH2 C H

OO-OH H

CH3 CH CH2 C H

OOH

O

Aldol

c8-

!

F69(6! ;/%&! /%#,%9! %#1062! 6(1%1! #! $(6%456%! (-! ;#,%+! ,(! -(+$! &H%<5&1#,5+#,%9! 4($*(5&9C! 3(+!

%J#$*6%!

CH3 CH CH C H

OOH H-H2O

CH3 CH CH C H

O

Crotonaldehyde !m%,(&%1! 4(&,#0&0&M!&</29+(M%&1! #61(! 5&9%+M(! 4(&9%&1#,0(&! ,(! M0L%! G%,(61C! 3(+! %J#$*6%1H! ,;(!

$(6%456%!(-!#4%,(&%!4(&9%&1%! ,(M%,/%+! 0&! ,/%!*+%1%&4%!(-!I#+05$!/29+(J09%! ,(! -(+$!90#4%,(&%!

#64(/(6!A!m%,(6E!

CH3 C CH3

O

O H2C C CH3

OHBa(OH)2

CH3 C CH2 C CH3

CH3

OH O

!

)0#4%,(&%!#64(/(6!(&!/%#,0&M!6(1%1!(&%!$(6%456%!(-!;#,%+!,(!-(+$!$%10,26!(J09%C!

!

&7@38!$/8;/!';283241>7;2J!.(&9%&1#,0(&!,/#,!,#G%!*6#4%!I%,;%%&!,;(!90--%+%&,!$(6%456%1H!(&%!

(-! ;/04/! $51,! /#L%! #&! &</29+(M%&H! 0&! ,/%! *+%1%&4%! (-! I#1%! 01! G&(;&! #1! $0J%9! #69(6!

4(&9%&1#,0(&C!3(+!%J#$*6%!4(&9%&1#,0(&!(-!#4%,#69%/29%!;0,/!I%&S#69%/29%C!

! ?B

C H

O

O H2C C

CH3

CH3

H

OH-

CH

OH

CH2 C H

O

H+ or

CH CH C H

O

O OH2

Cinnamaldehyde !

_DK!%38C9>7;2!%319>7;24J!

`K!%38C9>7;2! >;!$/9;=;/4J!F69%/29%1! #&9! G%,(&%1! #+%! +%954%9! ,(! ,/%! *+0$#+2! #&9! 1%4(&9#+2!

#64(/(61! +%1*%4,0L%62! I2! 4#,#62,04! /29+(M%&#,0(&! A8@o! :0! (+! N,EH! &#14%&,! /29+(M%&! A:#<8M! (+!

:#o.@8@c8EH!]0F68B!(+!:#'8B!

RCHOO H2 or 2[H] RCH2OH

1o alcohol

R C

O

R O H2 or 2[H] R CH

OH

R

Ketone

Aldehyde

2o alcohol!

Z%954,0(&! (-! I(,/! #69%/29%1! #&9!G%,(&%1! ,(! #64(/(61!$#2! I%! %--%4,%9! I2!$%#&1! (-!T%+;%0&<

N(&&9+(-<e%+6%2!Z%954,0(&!;/04/!0&L(6L%1!,/%!+%954,0(&!I2!$%#&1!(-!#65$0&5$!01(!*+(*(J09%!

0&!01(*+(*#&(6C!

RCHOO RCH2OH

R C

O

R O

(CH3)2CHOH[CH3CH-O]2Al

(CH3)2CHOH [CH3CH-O]2Al

O CH3 C CH3

O

R CH

OH

RO CH3 C CH3

O

!K/%! +%954,0(&! (445+1! I2! /29+09%! 0(&! ,+#&1-%+! -+($! #65$0&05$! 01(*+(*(J09%! ,(! ,/%! 4#+I(&26!

4($*(5&9!L0#!#!424604!,+#&10,0(&!1,#,%C!

!

! ?V

fK! %38C9>7;2! >;! $/01234J! F69%/29%1! #&9! G%,(&%1! #+%! +%954%9! ,(! 4(++%1*(&90&M! #6G#&%1! I2!

$%#&1! (-! S0&4! #$#6M#$! #&9! /29+(4/6(+04! #409! W!.6%$%&1%&! +%954,0(&X! (+! #6G#60&%! 1(65,0(&! (-!

/29+#S0&%CWb(6-!m01/&%+!Z%954,0(&X!!

'/3OO32432!%38C9>7;2J!K/01!0&L(6L%1!,/%!51%!(-!S0&4<!$%+45+2!!#$#6M#$!0&!/29+(4/6(+04!#409!

#1!,/%!+%9540&M!#M%&,C!

!

R C

O

HZn-Hg

HClR-CH3

R C

O

RZn-Hg

HClR-CH2-R

!!

M;/H!A74=23:!%38C9>7;2!J!K/01!0&L(6L%1!,/%!51%!(-!I#104!1(65,0(&!(-!/29+#S0&%!#1!,/%!+%9540&M!!

#M%&,!

R C

O

H R-CH3

R C

O

R'NaOH

R-CH2-R'

:8@<:8@

NaOH

:8@<:8@

!

_(K!F@781>7;2!%319>7;24J!

SaK!$/83=6834!1:3!3147/6!;@787N38!>;!91:<;@7/9!1978!<6!197879!G1U':UF^!;:!AU':UF^!;:!197879!

A&2FYW!

R-CHOO [O]

K2Cr2O7 / H+

RCOOH

!F69%/29%1!4#&!#61(!I%!(J090S%9!I2!#&(,/%+!(J090S0&M!#M%&,1!154/!#1!K(66%&Y1!+%#M%&,H!3%/60&MY1!

1(65,0(&!#&9!'%&%904,1!1(65,0(&!#&9!,/51!#4,!#1!#!1,+(&M!+%9540&M!#M%&,1C!

!

*;//32R4! %31L32>JZ$OO;2791/! -7/E3:! 27>:1>3! -;/C>7;2[! J!b/%&! K(66%&Y1! +%#M%&,! 01! 51%9! ,(!

(J090S%!#&!#69%/29%H!,/%!"06L%+!0(&!01!+%954%9!,(!$%,#6604!-(+$!#&9!9%*(10,1!#1!#!$0++(+!(&!46%#&!

,%1,!,5I%C!K/01!+%#4,0(&!01!51%9!#1!#!,%1,!(-!#69%/29%!#&9!G&(;&!#1!-7/E3:!O7::;:!>34>C!

R C H

O

O Ag(NH3)2OH R C

O

ONH4O 2Ag O OH2

+-

O NH33silver mirror !

B3=/72L!4;/C>7;2J!'65%!4(6(5+%9!#6G#60&%!1(65,0(&!(-!45*+04!0(&!W3%/60&M!"(65,0(&!FX!4($*6%J%9!

;0,/! 1(905$! *(,#1105$! ,#+,%+#,%! A3%/60&M! "(65,0(&! 'E! 01! #61(! +%954%9! I2! F69%/29%C! K/%!

4($*6%J%9!45*+04!0(&!A9%%*!I65%E!01!+%954%9!,(!.5*+(51!(J09%C!

! ??

'%&%904,!1(65,0(&!A#6G#60&%!1(65,0(&!(-!45*+04!0(&!4($*6%J%9!;0,/!40,+#,%!0(&1E!+%#4,1!0&!,/%!1#$%!

;#2!#1!3%/60&M!"(65,0(&C!

!

m%,(&%1!#+%!&(,!(J090S%9!I2!$069%+!(J090S0&M!#M%&,1! ,/51! ,/%2!9(!&(,! +%954%!K(66%&Y1! +%#M%&,H!

3%/60&M! 1(65,0(&! #&9! '%&%904,1! 1(65,0(&1C! 8(;%L%+H! G%,(&%1! 4#&! I%! (J090S%9! I2! 1,+(&M%+!

(J090S0&M! #M%&,1! 154/! #1! #409! 904/+($#,%H! #6G#60&%! mT&cB! #&9! /(,! 4(&C! 8:cR! ,(! -(+$!

4#+I(J2604!#4091!;0,/!-%;%+!4#+I(&!#,($1!,/#,!,/%!(+0M0&#6!G%,(&%1C!3(+!%J#$*6%!

CH3 C CH3

O

K2Cr2O7 / H+

CH3COOH O HCOOH

CH3 CH2 C CH3

O

HNO3CH3CH2COOH HCOOHO

!

A3K!F>=3:!7O?;:>12>!%319>7;24!;H!$/83=6834!128!A3>;234W!

_SSK!'1227NN1:;!:319>7;2J!F69%/29%1!;/04/!9(!&(,!/#L%!&</29+(M%&!#,($H!;/%&!,+%#,%9!;0,/!

4(&4%&,+#,%9!1(65,0(&!(-!:#c8!5&9%+M(!901!*+(*(+,0(&#,0(&!+%#4,0(&C!c&%!/#6-!(-!,/%!#69%/29%1!

#+%!(J090S%9!,(!4#+I(J2604!#409!#&9!(,/%+!/#6-!#+%!+%954%9!,(!#64(/(6C!K/01!+%#4,0(&!01!G&(;&!#1!

'1227NN1:;!:319>7;2C!

2HCHO NaOH HCOONa CH3OHOOFormaldehyde Sodium formate Methyl alcohol

!

&39=1274OJ!3(66(;0&M!1,%*1!#+%!0&L(6L%9!

->3?!SJ!F,,#4G!(-!,/%!Pc8!(&!,/%!4#+I(&26!M+(5*C!

H C

O

H O OH-

H C H

OH

O-

$!

$!

+

-

!

->3?!UJ!829+09%!,+#&1-%+a!

H C H

O-

OH

H

H

O+ -

H C

O

OHO CH3O

- H+ transfer

H C O

O

O CH3OH$!$!

-

!

m%,(&%1!9(!&(,!M0L%!,/01!+%#4,0(&C!

SUK! %3H;:O1>406! %319>7;2J! Z%#4,0(&! (-! ! #69%/29%1! #&9! G%,(&%1! ;0,/! &<I+($(%1,%+! 0&! ,/%!

*+%1%&4%!(-!$%,#6604!S0&4!#&9!%,/%+! ,(!M0L%!%</29+(J2!%1,%+! 01!G&(;&!#1!Z%-(+$#,1G2!+%#4,0(&C!

%CMC!

! ?D

CH3 C

O

H O Br-CH2COOC2H5i) Zn.ether

ii) H2O / H+ CH3 C CH2

OH

H

COOC2H5

CH3 C

O

CH3 O Br-CH2COOC2H5i) Zn.ether

ii) H2O / H+

CH3 C CH2

OH

CH3

COOC2H5

!

&39=1274OJ!K/+%%!1,%*1!#+%!0&L(6L%9C!

->3?!SJ!3(+$#,0(&!(-!S0&4!1#6,!(-!%&(6!(-!,/%!%1,%+C!

Br CH2 C

O

OC2H5 H2C C

OZnBr

OC2H5!

->3?!UJ!K/%!S0&4!1#6,!+%#4,1!;0,/!,/%!4#+I(&26!4($*(5&9C!

CH3 C

O

CH3

O CH2 C

O

OC2H5

ZnBr

CH3 C

OZnBr

CH2

H

C

O

OC2H5+

-

!

->3?!XJ!F409!/29+(62101!

CH3 C

OZnBr

CH2

H

C

O

OC2H5

H+ / H2O

CH3 C

OH

CH2

H

C

O

OC2H5

!!

SXK!#1/;H;:O!%319>7;2J!F4%,#69%/29%!#&9!$%,/26!G%,(&%1!+%#4,!+#*0962!;0,/!/#6(M%&A.6@H'+@!(+!

^@E!0&!,/%!*+%1%&4%!(-!#6G#60!,(!M0L%!/#6(-(+$C!K/01!+%#4,0(&!01!G&(;&!#1!8#6(-(+$!+%#4,0(&C!

R C

O

CH3 O Br2 4NaOH CHBr3 3H2O 3NaBrO O OR

O

ONa O+-

Methyl ketoneBromoform

!!

K/%!+%#4,0(&!,#G%1!*6#4%!0&!,;(!1,%*1C!

1. R C CH3

O

O 3Br2 3NaOHO R C CBr3

O

O3H2O O 3NaBr

R C CBr3

O

NaOHO R C ONa

O

O 2. CHBr3Bromoform !

! ?h

8#6(-(+$!+%#4,0(&!01!51%9!#1!#!90#M&(1,04!,%1,!-(+!9%,%4,0&M!,/%!*+%1%&4%!(-!P.c.8R!M+(5*!0&!#!

4($*(5&9C!K/01!+%#4,0(&!4#&!#61(!I%!51%9!,(!901,0&M501/!$%,/26!G%,(&%1C!m%,(&%!&(,!4(&,#0&0&M!

A<.c<.8RE!9(!&(,!M0L%!,/01!+%#4,0(&C!

!

SYK! M7>>7L! %319>7;2J! Z%#4,0(&! I%,;%%&! #69%/29%1! #&9! G%,(&%1! ;0,/! ,+0*/%&26! */(1*/0&%!

#6G2609%&%1!(+!*/(1(*(5+(51!2609%!AN/RNf.Z@E!,(!-(+$!#6G%&%!01!G&(;&!#1!b0,,0M!+%#4,0(&C!

Alkene

CH3

CH3

O O R2C-PPh3

+-

ylide

CH3

CH3

CR2 O=PPh3O

!&39=1274OJ!F,,#4G!(-!&%M#,0L%!4#+I(&!(-!2609%!(&!4#+I(&26!4#+I(&!,(!-(+$!<3>1723H!

C

O

CH3 CH3

C

PPh3

R R

O-

PPh3

CH3 CH3R

R

O

+ +

+

-

:-

!'%,#0&%!5&9%+M(!%60$0&#,0(&!,(!M0L%!,/%!#6G%&%C!

O-

PPh3

CH3 CH3CH3CH3

+ O PPh3

CH3 CH3RR

CH3

CH3

CR2 O O=PPh3

Betaine !QJ#$*6%a!

CH3 C

CH3

O CH2

-PPh3

+

CH3 C

CH3

CH2 OO O=P-Ph3

2-methyl propene !!

S\K%319>7;2!I7>=!"'/\J!F69%/29%1!#&9!G%,(&%1!+%#4,!;0,/!N.6V!,(!M0L%!M%$<90/#609%1C%CMC!

R C H

O

PCl5 R C H

Cl

Cl

O O POCl3

R C R

O

PCl5 R C R

Cl

Cl

O O POCl3

Gem.dihalide !

! ?U

S]K! *749=320;! %319>7;2J!F69%/29%1! /#L0&M! &</29+(M%&! #,($! 4#&! #61(! I%! $#9%! ,(! 5&9%+M(!

4#&&0SS#+(!,2*%!+%#4,0(&H!0-!+%#4,0(&!01!4#++0%9!(5,!0&!*+%1%&4%!(-!#65$0&5$!%,/(J09%C!'5,!0&!154/!

4#1%H!#409!#&9!#64(/(6!+%#4,!,(M%,/%+!,(!-(+$!%1,%+!#1!,/%!-0&#6!*+(954,C!

2CH3CHOAl(OC2H5)3

CH3COOH CH3CH2OH CH3COOC2H5OEthyl acetate !

S^K!";/6O3:7N1>7;2J!](;%+!#69%/29%1!5&9%+M(!*(62$%+0S#,0(&!,(!-(+$!90--%+%&,!*+(954,1!5&9%+!

90--%+%&,!4(&90,0(&1C!m%,(&%1!/(;%L%+H!#+%!&(,!$54/!1514%*,0I6%!,(!*(62$%+0S#,0(&C!

!

'1:<;@6/79!$9784!128!*=37:!BC29>7;21/!D3:7E1>7E34!

c+M#&04!4($*(5&91!4(&,#0&0&M!4#+I(J26!M+(5*!A<.cc8E!#+%!G&(;&!#1!4#+I(J2604!#4091C!K/%2!

4#&!I%!+%*+%1%&,%9!I2!,/%!M%&%+#6!-(+$56#C!

R COOH Or CH3 C

O

OH!

K/%2! #+%! -5+,/%+! 46#110-0%9! #1!$(&(H! 90H! ,+0! %,4CH! 4#+I(J2604! #4091H! #44(+90&M! ,(! ,/%! &5$I%+! (-!

4#+I(J2604! M+(5*1! *+%1%&,! 0&! ,/%0+! $(6%456%1C! K/%! 6(&M! 4/#0&! $(&(4#+I(J2604! #4091! #+%! #61(!

4#66%9!-#,,2!#4091!I%4#51%!$#&2!(-!,/%$!#+%!(I,#0&%9!-+($!-#,1C!

!

&3>=;84!;H!":3?1:1>7;2!

SK! T6! >=3! ;@781>7;2! ;H! ?:7O1:6! 1/9;=;/4! ;:! $/83=6834J! N+0$#+2! #64(/(61! (+! #69%/29%1! #+%!

(J090S%9!I2!#40904!m@.+@cD!(+!:#@.+@cD!,(!M0L%!4#+I(J2604!#4091C!

RCH2OHK2Cr2O7 / H

+

RCHO RCOOHK2Cr2O7 / H

+

1oalcohol Aldehyde Carboxylic acid

CH3CH2OH[O]

CH3CHO[O]

CH3COOH

Ethyl alcohol Acetaldehyde Acetic acid !

UK! T6! >=3! =68:;/6474! ;H! 1/06/! 96127834! ;:! 27>:7/34J! !F6G26! 42#&09%! (&! #409! /29+(62101! M0L%!

4#+I(J2604!#4091C!

R C NH

+ / H2O

RCOOH NH3OAlkyl cyanide

carboxylic acid

CH3CN CH3COOH NH3OH

+ / H2O

Methyl cyanide Acetic acid !

XK!T6!>=3!#68:;/6474!;H!(4>3:J!b/%&!%1,%+1!#+%!/29+(621%9!I2!#6G#60!:#c8!(+!mc8H!1(905$!(+!

*(,#1105$! 1#6,! (-! 4#+I(J2604! #4091! #+%! -(+$%9! ;/04/! (&! ,+%#,$%&,! ;0,/! 906! 8.6! M0L%1! ,/%!

4(++%1*(&90&M!4#+I(J2604!#4091C!

! D>

CH3 C OC2H5

O

NaOHO CH3 C ONa

O

O C2H5OH

Sodium acetate Ethyl alcoholethyl acetate

- +

CH3 C ONa

O

- +

O ClH CH3 C OH

O

O NaCl

!

YK! T6! >=3!%319>7;2! ;H!Q:7L21:8!%31L32>4!I7>=!'FUJ! g+0M&#+9! +%#M%&,!;0,/! .c@! -0+1,! M0L%!

#990,0(&!*+(954,!;/04/!(&!/29+(62101!20%69!4#+I(J2604!#409C!

R-MgXO C O

O

R C

O

OMgXH

+ / H2O

RCOOH

carboxylic acidAlkyl

Magnesium halide

C2H5MgBr O C O

O

C2H 5 C

O

OMgXH

+ / H2O

C2H5-COOH

Ethyl

Magnesium bromidePropionic acid.

!

c+M#&(!60,/05$!4($*(5&91!4#&!#61(!I%!51%9!0&!*6#4%!(-!g+0M&#+9!Z%#M%&,C!

!

\K!T6!&1/;279!(4>3:!-62>=3474J!F6G26!/#609%!+%#4,!;0,/!1(905$!9%+0L#,0L%!(-!90%,/26!$#6(&#,%!

,(!M0L%!15I1,0,5,%9!$#6(&04!%1,%+C!K/01!01!/29+(621%9!#&9!9%4#+I(J26#,%9!,(!20%69!#&!#409C!

R X O NaHC

COOC2H5

COOC2H5-NaX

HC

COOC2H5

COOC2H5

RH

+ / H2O

HC

COOH

COOH

R -CO2

RCH2COOH

Carboxylic acid!

^&!,/01!$%,/(9!,;(!$(+%!4#+I(&1!#+%!#99%9!,(!#6G26!M+(5*!(-!1,#+,0&M!#6G26!/#609%C!

!

]K!T6!'1:<;@6/1>7;2!;H!$/03234J!K/01!01!#!+%4%&,!0&951,+0#6!$%,/(9!(-!*+%*#+#,0(&!(-!4#+I(J2604!

#4091!#&9!01!4#66%9!A;9=!%319>7;2C!K/01!0&L(6L%1!,+%#,$%&,!(-!#6G%&%!;0,/!4#+I(&!$(&(J09%!#&9!

1,%#$!5&9%+!*+%115+%!;0,/!*/(1*/(+04!#409H!8RNcR!#,!B>>(.C!!

! D=

!!!!!!!!!!!!!!!

CH2 CH2 O COO OH2

H3PO4

400oCCH3CH2COOH

Propionic acid!

":;?3:>734J!

=E! K/%! 6(;%+! 4#+I(J2604! #4091! A! .=! ,(! .=>E! #+%! 4(6(5+6%11! *5&M%&,! 1$%660&M! 60d5091C! 80M/%+!

$%$I%+1!#+%!;#J!60G%!1(6091!#&9!#6$(1,!4(6(5+6%11C!!

@E!30+1,!-(5+!$%$I%+1!#+%!-+%%62!1(65I6%!0&!;#,%+!95%!,(!/29+(M%&!I(&90&M!;0,/!;#,%+!$(6%456%C!

IIIIIII IIIIIIIIH O C O

R

H O

H

H O C O

R

H O

H

IIIIIII IIIIIII

!'5,!,/%!1(65I060,2!(-!/0M/%+!$%$I%+1!9%4+%#1%1!+#*0962!;0,/!,/%!0&4+%#1%!0&!,/%!10S%!(-!,/%!#6G26!

M+(5*!95%!,(!0&4+%#1%9!0&-65%&4%!(-!,/%!&(&<*(6#+!#&9!/29+(*/(I04!/29+(4#+I(&!4/#0&C!

!

RET%6,0&M!*(0&,1!(-!4#+I(J2604!#4091!0&4+%#1%!0++%M56#+62!;0,/!0&4+%#1%!0&!,/%!$(6%456#+!;%0M/,C!

K/%!%L%&!$%$I%+1!/#L%!$#+G%962!/0M/%+!I(060&M!*(0&,1!,/#&!,/%!(99!$%$I%+1C!

!

BE!'(060&M!*(0&,1!(-!,/%!4#+I(J2604!#4091H!*#+,0456#+62!6(;%+!$%$I%+1!/0M/%+!,/#&!,/%!#64(/(61!(-!

1#$%!$(6%456#+!;%0M/,C!%CMC!

F4%,04!#409!A.8R.cc8E!!!!!!!!!!!!!!!!!!!!!Tb!f!?>!!!!!!!!!!!!!!!!IC*C!f!==h(.!

=<N+(*#&([email protected]@c8E!!!!!!!!!!!!!!Tb!f!?>!!!!!!!!!!!!!!!!IC*!f!!UD(.!

!

K/01!01!95%!,(!!,/%!1,+(&M!/29+(M%&!I(&90&M!0&!4#+I(J2604!#4091!,/#&!,/(1%!0&!#64(/(61C!

R C

O

O H

RC

O

OH IIIIIII

IIIIIIII!

\K!$9787>6!;H!'1:<;@6/79!$9784J!.#+I(J2604!#409!#+%!#40904!0&!&#,5+%!I5,!,/%2!#+%!;%#G!#4091!#1!

4($*#+%9!,(!0&(+M#&04!#4091!A%CMC!8.6!(+!8@"cBEC!K/%2!4#&!9(&#,%!#!*+(,(&!#&9!-(+$!1#6,1!;0,/!

1,+(&M!I#1%1!#&9!,/%2!#+%!(&62!*#+,0#662!0(&0S%9!0&!#d5%(51!1(65,0(&C!

R C

O

OH O OH2 R C

O

O-O OH3

+

!K/%! #40904! 4/#+#4,%+! (-! 4#+I(J2604! #4091! 9%4+%#1%1!;0,/! 0&4+%#1%! 0&!$(6%456#+!;%0M/,C! 3(+$04!

#409!01!1,+(&M%1,!(-!#66!-#,,2!#4091C!

!

K/%! #40904! 4/#+#4,%+! (-! 4#+I(J2604! #409! 01! 95%! ,(! ,/%! +%1(&#&4%C! K/%! 4#+I(J2604! 0(&! -(+$! I2!

0(&0S#,0(&!01!1,#I060S%9!I2!+%1(&#&4%C!

!

! D@

8%&4%!4#+I(J2604!0(&!01!$(+%!1,#I060S%9!,/#&!,/%!#409!0,1%6-C!K/%!%d5060I+05$!(-!,/%!0(&0S#,0(&!(-!

#4091!1/0-,1!,(!,/%!+0M/,!/#&9!109%C!_<+#2!1,590%1!#61(!15**(+,!,/%!%J01,%&4%!(-!4#+I(J26#,%!0(&!#1!

+%1(&#&4%!/2I+09!-(+!%J#$*6%!I(&9!6%&M,/1!(-!4#+I(J2!(J2M%&!/#L%!90--%+%&,!L#65%1!0&!-(+$04!

#409C!b/%+%!#1!0&!1(905$!-(+$#,%!,/%!,;(!4#+I(&<(J2M%&!I(&9!6%&M,/1!#+%!09%&,04#6C!

!

K/%! 1,#I060,2! (-! 4#+I(J26#,%! 0(&! 4#&! #61(! I%! %J*6#0&%9! (&! ,/%! I#101! (-! 0,1! $(6%456#+! (+I0,#6!

1,+54,5+%C! K/%! 4#+I(&! #,($! (-! 4#+I(J26! M+(5*! 0&! 1*@! /2I+0901%9C! ^&! 4#+I(J26#,%! 0(&! ,/%!

5&/2I+0901%9! ! N! (+I0,#6! (-! 4#+I(&!(L%+6#*1!;0,/!N!(+I0,#6! (-! I(,/! (J2M%&! #,($! ,(! -(+$! 1,#I6%!

9%6(4#60S%9!$(6%456#+!(+I0,#6C!

!

(HH39>!;H!4C<4>7>C32>4!;2!$9787>6J!F40904!4/#+#4,%+!(-!4#+I(J2604!#409!!01!95%!,(!,/%!1,#I060S#,0(&!

(-! 4#+I(J26#,%! 0(&C! "(! #&2! ! -#4,(+!;/04/! 4#&! %&/#&4%! ,/%! 901*%+1#6! (-! &%M#,0L%! 4/#+M%! (-! ,/%!

4#+I(J26#,%!0(&!;066!0&4+%#1%!,/%!#4090,2!#&9!L01%!L%+1#C!^&954,0L%!%--%4,!(-!,/%!15I1,0,5%&,!(&!,/%!

&<4#+I(&!*6#2!L%+2!0$*(+,#&,!+(6%C!Q6%4,+(&!;0,/9+#;0&M!15I1,0,5,%&,1!60G%!.6H!'+H!3H!:c@H!c8H!

.:!%,4C!;(569!901*%+1%!,/%!&%M#,0L%!4/#+M%!#&9!/%&4%!1,#I060S%!,/%!4#+I(J2604!0(&C!c&!,/%!(,/%+!

/#&9! %6%4,+(&! +%6%#10&M! 15I1,0,5%&,1! ;(569! 0&4+%#1%! ,/%! &%M#,0L%! 4/#+M%! 9%1,#I060S%1! ,/%!

4#+I(J26#,%!0(&!#&9!,/51!9%4+%#1%!#4090,2!(-!,/%!#409C!

!

! DR

F6G26!M+(5*1!#+%!%6%4,+(&!+%6%#10&M!M+(5*!,/51!,/%0+!*+%1%&4%!0&!,/%!$(6%456%!;066!9%4+%#1%!,/%!

#4090,2!C!](&M%+!,/%!6%&M,/1!(-!#6G26!4/#0&H!6(;%+!;066!,/%!#4090,2!(-!,/%!#409C!"0&4%!-(+$04!#409!

/#1!&(!#6G26!M+(5*H!0,!01!,/%!1,+(&M%1,!(-!#66!-#,,2!#4091C!^,!01!,%&!,0$%1!1,+(&M%+!,/#&!#4%,04!#409C!

[email protected]!

"0$06#+62!./6(+(#4%,04! #409! 01! /5&9+%9! ,0$%1! 1,+(&M%+! ,/#&! #4%,04! #409! I%4#51%! (-! ,/%! %6%4,+(&!

;0,/9+#;0&M!&#,5+%!(-!.6!M+(5*!-(66(;0&M!(+9%+!01!(I1%+L%9!0&!./6(+(!#4%,04!#409C!

.6R<.<.cc8!i!.6@<.8<.cc8!i.6<[email protected]!.8R.cc8!

K+04/6(+(#4%,04!#409!01!#6$(1,!#1!1,+(&M!#1!#!$0&%+#6!#409C!

'=3O791/!":;?3:>734J!

$K!%319>7;24!72E;/E72L!=68:;L32!1>;O!;H!>=3!d'FF#!L:;C?!

SK!%319>7;2!I7>=!O3>1/4!128!1/01/734J!.#+I(J2604!#4091!+%#4,!;0,/!1,+(&M62!*(10,0L%!$%,#61!;0,/!

,/%!60I%+#,0(&!(-!/29+(M%&!#&9!-(+$!1#6,C!

RCOOH Na RCOONa 1/2 H2O O- +

!.#+I(J2604! #4091! #61(! -+($! 1#6,1! ;0,/! $%,#6! /29+(J09%1H! 4#+I(&#,%1! #&9! I04#+I(&#,%1C! 3(+!

%J#$*6%!

!

UK!%319>7;2!I7>=!$/9;=;/4J!T(&(4#+I(J2604!#4091!+%#4,!;0,/!#64(/(61!0&!,/%!*+%1%&4%!(-!1,+(&M!

#409!4#,#621,!60G%!156*/5+04!#409!,(!-(+$!%1,%+1C!K/%!+%#4,0(&!01!G&(;&!#1!(4>3:7H791>7;2C!

R C

O

OH O R C

O

OROH RH

+

H2OOcarboxylic acid

CH3 C

O

OH CH3 C

O

OC2H5OH C2H5

H+

H2OO OEthyl acetate

EthanolAcetic acid !

3(66(;0&M!$%4/#&01$!01!15MM%1,%9!-(+!,/%!%1,%+0-04#,0(&!

->3?!SJ!N+(,(&#,0(&!(-!4#+I(J2604!#409C!

CH3 C

O

OH O H+

CH3 C+

OH

OH

$!

$!

-

+

!

!

!

! DB

CH3 C+

OH

OH O

H

O C2H5: .. CH3

OH

OH

O+

H

C2H5

!

->3?!+++J!829+(M%&!0(&!,+#&1-%+!

CH3 O-C2H5

O

OH2

+

H

CH3

O

OH

H

O+

C2H5

H

!

->3?!+VJ!Q60$0&#,0(&!(-!;#,%+!#&9!*+(,(&C!

!!!!!!!!!!!!!!!!!!!!

CH3 O-C2H5

O

OH2

+

H

CH3 C O-C2H5

O

O OH2 O H+

!

TK!%319>7;2!72E;/E72L!dF#!?1:>!;H!>=3!d'FF#!L:;C?!

XK!%319>7;2!I7>=!"=;4?=;:;C4!#1/7834! 128!*=+;26/!'=/;:783J!.#+I(J2604! #4091! +%#4,!;0,/!

*/(1*/(+(51!/#609%1!#&9!,/0(&26!4/6(+09%!,(!-(+$!#409!/#609%1C!3(+!%J#$*6%C!

R C OH

O

O3 PCl3 3 RCOCl H3PO3O!

R C OH

O

O PCl5 RCOCl POCl3 HClO O!

R C OH

O

O SOCl2 RCOCl SO2 HClO O!

YK%319>7;2!I7>=!1OO;271J!.#+I(J2604!#409!+%#4,!;0,/!#$$(&0#!,(!-(+$!#$$(&05$!1#6,!;/04/!

(&!1,+(&M!/%#,0&M!M0L%!#409!#$09%1!;0,/!,/%!%60$0&#,0(&!(-!;#,%+C!

R C OH

O

O NH3R C ONH4

O

R C NH2

O

-H2O

Carboxylic acid Ammonium salt Acid amide

- +

!

! DV

CH3 C OH

O

ONH3CH3 C ONH4

O

CH3 C NH2

O

-H2O

- +

F4%,#$09%F$$(&05$!#4%,#,%F4%,04!#409 !

\K! D3=68:1>7;2J! .#+I(J2604! #409! (&! 9%/29+#,0(&! ;0,/! N@cV! A9%/29+#,0&M! #M%&,1E! M0L%! #409!

#&/29+09%C!

!

!!!!!!!!

CH3 C OH

O CH3 C

O

CCH3

O

O

O H2O

Acetic anhydride

P2O5

2

Acetic acid

!

F409!#&/29+09%1!4#&!#61(!I%!*+%*#+%9!I2!/%#,0&M!1(905$!1#6,!(-!#4091!;0,/!/#609%1C!

R C ONa

O

Cl C CH3

O CH3 C

O

CCH3

O

O

O NaCl

+-O

!'K!-;O3!F>=3:!%319>7;24J!

]K!%38C9>7;2J! Z%954,0(&! (-! 4#+I(J2604! #4091! 9%*%&91! (&! ,/%! &#,5+%! (-! +%9540&M! ! ! #M%&,1C!c&!

+%954,0(&!;0,/!]0F68BH!4#+I(J2604!#409!M0L%1!*+0$#+2!#64(/(6C!

RCOOH R CH2OH

Carboxylic acid alcohol

LiAlH4

1o

!

8%#,0&M!;0,/!8^!o!+%9!N/(1*/(+(51H!5&9%+!*+%115+%H!(+!;0,/!/29+(M%&!5&9%+!*+%115+%!#,!%6%L#,%9!

,%$*%+#,5+%!0&!,/%!*+%1%&4%!(-!#!&04G%6!4#,#621,H!*+(954%1!#&!#6G#&%C!

! D?

RCOOHH2 / Ni

orHI / red P

R CH3

Carboxylic acid Alkane !

^K! F@781>7;2J! F66! ,/%! #4091H! %J4%*,! -(+$04! #409! H! #+%! %J,+%$%62! +%101,#&,! ,(! (J09#,0(&H! I5,!

*+(6(&M%9!/%#,0&M!;0,/!(J090S0&M!#M%&,1!*+(954%1!4#+I(&!90(J09%!#&9!;#,%+C!

!

_DK!%319>7;24!+2E;/E72L!1/06/!L:;C?!;H!>=3!1978J!

_`K!!P#1/;L321>7;2J!.#+I(J2604!#4091!4(&,#0&0&M!&</29+(M%&!#,($1C!b/%&! ,+%#,%9!;0,/!.6@!(+!

'+@!0&!,/%!*+%1%&4%!(-!*/(1*/(+(51!#1!#!4#,#621,H!15I1,0,5,0(&!(-!&</#6(M%&#,%9!#4091!#+%!-(+$%9C!

K/%!+%#4,0(&!01!G&(;&!#1!,/%!#3//<V;/=1:8!e3/72406!_#VeK!+%#4,0(&C!

R CH2 COOH O Cl2P

R CH COOH

Cl

O ClH

Carboxylic acid halogenated acid&! -!

CH3 COOH O Cl2P

Cl CH2 COOHO ClH

Chloro acetic acidAcetic acid !

CH2 COOHCH3 O Br2P

Cl CH COOH

Br

OAcetic acid 2-Bromo propionic acid.

BrH

!

!_(K!%3191>7;24!;H!41/>4!;H!91:<;@6/79!19784J!

_fK!#31>72L! ;H! -;87CO! 41/>J!b/%&! 1(905$! 1#6,! (-! 4#+I(J2604! #409! #+%! /%#,%9!;0,/! 1(9#! 60$%!

W:#c8!O!.#cX!#6G#&%1!#+%!-(+$%9C!

CH3 C ONa

O

+-

O NaOHCaO

CH4 O Na2CO3

Sod. acetate Methane!

SaK!#31>72L!;H!$OO;27CO!41/>J!b/%&!#$$(&05$!1#6,1!#+%!/%#,%9H!#$09%1!#+%!-(+$%9C!

CH3 C ONH4

O

Ammonium acetate

+-CH3CONH2 H2OOAcetamide

!b/%&!#$$(&05$!1#6,1!#+%!/%#,%9!;0,/!N@cVH!#6G26!&0,+06%1!#+%!-(+$%9C!

CH3 C ONH4

O

P2O5

CH3 C N O 2 H2O

methyl cyanideAmmonium acetate !

! DD

SSK!#31>72L!;H!'1/97CO!41/>J!.#6405$!1#6,1!(-!4#+I(J2604!#4091!(&!/%#,0&M!M0L%!#69%/29%1!#&9!

G%,(&%1C!

1K!'1/97CO!H;:O1>3!L7E34!H;:O1/83=683W!

!

<K'1/97CO!41/>!;H!126!91:<;@6/79!1978!;>=3:!>=12!H;:O79!1978!L7E34!03>;234W!

(R-COO)2Ca 2CaCO3O

(CH3-COO)2Ca

R C R

O

2CaCO3CH3 C CH3

O

O!

9K!'1/97CO!41/>!;H!126!91:<;@6/79!1978W!I=32!=31>38!I7>=!91/97CO!H;:O1>3!L7E34!1/83=683W!

(R-COO)2CaO (HCOO)2Ca 2R-CHO 2CaCO3O

(CH3-COO)2Ca O (HCOO)2Ca 2CH3CHO 2CaCO3O!

SUK(/39>:;/6474J! Q6%4,+(62101! (-! 4(&4%&,+#,%9! #d5%(51! 1(65,0(&! (-! 1(905$! (+! *(,#1105$! 1#6,1!

M0L%1!#6G#&%1C!AA;/<3R4!3/39>:;/6474E!

2RCOONaO 2H2O R RO 2CO2 2NaOH H2O Oelectrolysis

At anode At cathode

2CH3COONaO 2H2O CH3 CH3 O 2CO2 2NaOH H2O Oelectrolysis

Sodium acetate Ethane!

SXK!%319>7;2!;H!47/E3:!41/>4!I7>=!=1/;L324J!b/%&!106L%+!1#6,!(-!4#+I(J2604!#4091!#+%!/%#,%9!;0,/!

4/6(+0&%!(+!I+($0&%H!#6G26!/#609%1!#+%!-(+$%9C!K/%!+%#4,0(&!01!G&(;&!#1!#C24873903:!%319>7;2C!

! Dh

CH3 C

O

OAg O Br2 CH3Br O 2AgBr O CO2

+-

!'1:<;@6/79!$978!D3:7E1>7E34!_$978!D3:7E1>7E34KJ!K/%!4($*(5&91!9%+0L%9!-+($!,/%!4#+I(J2604!

#4091!I2! ,/%! +%*6#4%$%&,!(-!Pc8!-5&4,0(&!(-!!.#+I(J26!M+(5*!I2!#&(,/%+!M+(5*!#+%!G&(;&!#1!

#409!9%+0L#,0L%1C!F66!154/!9%+0L#,0L%1!5*(&!/29+(62101!M%&%+#,%!,/%!*#+%&,!#409C!

!

)0--%+%&,!F409!9%+0L#,0L%1!#+%a!

R C O

O

RC

O

R C OR

O

Name Formula

i) F409!/#609%1CH3 C

O

CH3 X = Cl,Br or!^

!!00E!!!!!!!!!!!F409!#&/29+09%

!000E!!!!!!!!!Q1,%+

!!!0LE!!!!!!!!F$09% R C NH2

O

!SW!$978!#1/7834J!F409!/#609%1!#+%!,/%!9%+0L#,0L%1!(-!#4091!0&!;/04/!,/%!Pc8!-5&4,0(&!(-!4#+I(J26!

M+(5*!01!+%*6#4%9!I2!#!/#6(M%&!#,($C!F409!/#609%1!#+%!#61(!G&(;&!#1!196/!=1/7834C!F409!4/6(+09%1!

#+%!$(1,!0$*(+,#&,!(-!#66!,/%!#409!/#609%1C!

K/%2!#+%!+%*+%1%&,%9!#1!!R C

O

Cl!!H!1($%!%J#$*6%1!#+%H!

CH3 C

O

Cl<!F4%,26!./6(+09%AQ,/#&(26!4/6(+09%E

H5C2 C

O

Cl !<!N+(*0(&26!4/6(+09%!AN+(*#&(26!4/6(+09%E!

&3>=;84!;H!":3?3:1>7;2J!

=E!'2!,/%!+%#4,0(&!(-!4#+I(J2604!#4091!;0,/!*/(1*/(+(51!/#609%1!

R C OH

O

PCl3 R C Cl

O

H3PO3OO3!

R C OH

O

PCl5 R C Cl

O

POCl3OO HClO!

@E!'2!,/%!+%#4,0(&!(-!.#+I(J2604!#4091!;0,/!,/0(&26!4/6(+09%!

! DU

R C OH

O

SOCl2 R C Cl

O

SO2OO

CH3 C OH

O

SOCl2 CH3 C Cl

O

SO2OO!

":;?3:>734J!

"=64791/!":;?3:>734J!

0E!F66!10$*6%!#409!4/6(+09%1!#+%!*5&M%&,!1$%660&M!4(6(5+6%11!60d5091!(-!6(;%+!I(060&M!*(0&,1!,/#&!

,/%!4(++%1*(&90&M!#409C!K/%2!#61(!/#L%!,%#+!*+(9540&M!*+(*%+,2C!0C%!6#4/+2$#,(+1C!

00E!K/%2!#+%!0&1(65I6%!0&!;#,%+!I5,!16(;62!1,#+,!,(!9011(6L%!0&!0,!I%4#51%!(-!/29+(62101C!

!

'=3O791/! ?:;?3:>734J! F409! 4/6(+09%1! #+%! L%+2! +%#4,0L%! 4($*(5&91! #1! ,/%2! #+%! $(+%! +%#9062!

#,,#4G%9! I2! &546%(*/06%! I%4#51%! (-! ,/%! %6%4,+(&!;0,/9+#;0&M! %--%4,! (-! /0M/62! %6%4,+(&%M#,0L%H!

4/6(+0&%!#,($!#,,#4/%9! ,(!4#+I(&26!4#+I(&C!K/01! -5+,/%+!90$0&01/%1! ,/%!%6%4,+(&!9%&10,2!(&! ,/%!

4#+I(&26!4#+I(&C!.6!#,($!01!+%*6#4%9!I2!,/%!&546%(*/06%C!

R C Cl

O

R C Cl

O-

OR C Nu

O

O :Nu Cl:-

..

$!

$!

-

+

!

"($%!0$*(+,#&,!+%#4,0(&1!(-!#409!4/6(+09%!#+%!-(66(;0&MC!

SK#68:;/6474J!K/%!#426!4/6(+09%1!#+%!+%#9062!/29+(621%9!I2!;#,%+!,(!+%-(+$!,/%!(+0M0&#6!#409C!

R C Cl

O

R C OH

O

O ClH

Acid chloride

O OH2

CH3 C Cl

O

CH3 C OH

O

O ClHO OH2

Carboxylic acid

Acetyl chloride Acetic acid!

UK!$96/1>7;2J!F409! 4/6(+09%1! #+%! 0$*(+,#&,! #426#,0&M! +%#M%&,C! K/51! 515#662! +%#4,! +#*0962!;0,/!

4($*(5&91! 4(&,#0&0&M! #4,0L%! /29+(M%&! #,($1! 0C%C! /29+(M%&! #,,#4/%9! ,(! (J2M%&H! &0,+(M%&! (+!

156*/5+C!K/01!#4,0L%!/29+(M%&!01!+%*6#4%9!I2!#426!M+(5*!AR C .

O

!E!(-!#409!4/6(+09%C!

!

1K!%319>7;2!I7>=!1/9;=;/4!_$/9;=1/6474KJ!Q1,%+1!#+%!-(+$%9!

! h>

!

<K!%319>7;2!I7>=!$OO;271!_$OO;2;/6474KJ!F$09%1!#+%!-(+$%9C!

R C Cl

O

O R C NH2

O

O ClHH-NH2

Acid chloride!

9K!%319>7;2!I7>=!":7O1:6!128!-39;281:6!$O7234J!:<15I1,0,5,%9!#$09%1!#+%!-(+$%9C!

R C Cl

O

O R C NHR'

O

O

R C Cl

O

O R C NR'2

O

ON,N-dialkyl amide

ClH

ClH

HNHR'

Acid chloride Primary amine N-Alkyl amide

HNHR'2

!8K%319>7;2!I7>=!=68:1N723!128!=68:;@6/1O723J!829+#S09%1!#+%!-(+$%9C!

R C Cl

O

O R C NHNH2

O

O

R C Cl

O

O R C NHOH

O

OAcetic anhydride

NH2 NH2 ClH

NH2 OH ClH

!XK%319>7;2!I7>=!41/>!;H!91:<;@6/79!19784J!F&/29+09%1!#+%!-(+$%9C!

R C Cl

O

NaOOCR-+

O R C O C R

O O

NaClOAcid anhydride

CH3 C Cl

O

-+O NaO C

O

CH3CH3 C O C CH3

O O

O NaCl

Acetic anhydride !

! h=

YK!%38C9>7;2J!

#E!F426!4/6(+09%1!$#2!I%!+%954%9!4#,#62,04#662!,(!#69%/29%1!(+!,(!#64(/(61C!

R C Cl

O

R C H

O

H2

AldehydePd

H2

RCH2OH

Alcohol !

b/%&!+%954%9!0&!*+%1%&4%!(-!*(01(&%9!N#66#905$!.#,#621,H!,/%2!-(+$!#69%/29%C!K/01!+%#4,0(&!01!

4#66%9!%;432OC28!%38C9>7;2C!

R C Cl

O

R C OH

O

CH3 C Cl

O

CH3 C H

O

H2 / Pd

Aldehyde

H2 / Pd

BaSO4

BaSO4

Acetaldehyde!

IE!b/%&!+%954%9!;0,/!]0F68BH!,/%2!-(+$!*+0$#+2!#64(/(61C!

R C Cl

O

LiAlH4R CH2 OH

CH3 C Cl

O

LiAlH4CH3 CH2 OH

Ethanol

1o Alcohol

!

\KB:7383/P':1H>! $96/1>7;2J! F426! 4/6(+09%1! +%#4,! ;0,/! #+($#,04! /29+(4#+I(&! 0&! *+%1%&4%! (-!

F6.6R!4#,#621,C!K/%!+%#4,0(&!01!G&(;&!#1!3C.C#426#,0(&C!%CMC!

O CH3 Cl

O

AlCl3

CCH3O

HClO

Benzene Acetophenone !

UW!$978!$2=68:7834J!K/%!4($*(5&9!9%+0L%9!-+($!#&!#409!I2!,/%!+%$(L#6!(-!(&%!;#,%+!$(6%456%!

-+($!,;(!$(6%456%!(-!,/%!#409!#+%!4#66%9!#&/29+09%1C!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!2 R-COOH-H2O

R C O C

O

R

O

!

F&/29+09%1!9%+0L%9!-+($!,;(!$(6%456%!(-!90--%+%&,!#4091!#+%!4#66%9!$0J%9!#&/29+09%C!

R-CO-O-CO-R' !

! h@

&3>=;84!;H!?:3?1:1>7;2J!

$978!12=68:7834!O16!<3!?:3?1:38W!

=E!'2!+%#4,0(&!(-!#409!/#609%!;0,/!4#+I(J2604!#409!(+!0,1!"(905$!1#6,C!

R C OH

O

O Cl-CO-RPyridine

R-CO-O-CO-R HClO

R C ONa

O

O Cl-CO-RPyridine

R-CO-O-CO-RO NaCl

!@E!'2!9%/29+#,0(&!(-!.#+I(J2604!#4091!0&!*+%1%&4%!(-!N@cVC!

R C OH

O

2P2O5

R-CO-O-CO-R H2OO!

":;?3:>734J!

"=64791/!?:;?3:>734J!

0E!K/%!6(;%+!10$*6%!#&/29+09%1!#+%!4(6(5+6%11!60d5091!;0,/!#&!0++0,#,0&M!1$%66C!

00E!K/%2! #+%! 0&! 1(65I6%! 0&!;#,%+! I5,! 9011(6L%! 16(;62! I%4#51%! (-! ,/%! 16(;!/29+(62101C! K/%2! #+%!

1(65I6%!0&!%,/%+!#&9!I%&S%&%C!

000E! K/%2! /#L%! /0M/%+! I(060&M! *(0&,1! ,/#&! ,/%! 4(++%1*(&90&M! #4091! I%4#51%! (-! 6#+M%! 10S%! (-!

$(6%456%!#&9!%&/#&4%9!L#&!9%+!b##61!0&,%+#4,0(&1C!

!

'=3O791/! ":;?3:>734J! ^&! #&/29+09%1! Pc.cZ! M+(5*! 01! +%*6#4%9! I2! &546%(*/06%! 60G%! #409!

4/6(+09%1! I5,! ,/%2! #+%! 6%11! +%#4,0L%! ,/#&! #409! 4/6(+09%1! I%4#51%! Pc.cZ! M+(5*! 01! &(,! #1!

%6%4,+(&%M#,0L%!#1!.6!#,($C!

R C O C R

OO

O R C O

O-

Nu

C O

O

H:Nu-

R C Nu

O

R C O-

O

-!

K/%!#&/29+09%1!M0L%!#66! ,/%!&546%(*/0604! 15I1,0,5,0(&! +%#4,0(&!M0L%&!I2!#409!4/6(+09%1!I5,!;0,/!

6%11!L0M(5+C!

7K!#68:;/6474J!

! !!!!!!!!!!!!!!F4%,04!#&/29+09%!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!F4%,04!#409!

! hR

77K!%319>7;2!I7>=!$/9;=;/4J!

!

777K!%319>7;2!I7>=!$OO;271J!

Acetamide Acetic acid !

!

7EK!%319>7;2!I7>=!$O7234J!

!!!!!!!!

CHRCOOHON-Alkylacetamide Acetic acid

!

EK!B:7383/!':1H>4!%3191>7;2J!

O (CH3CO)2O AlCl3O CH3COOH

AcetophenoneAcetic AcidAcetic acid anhydrideBenzene

C C8R

O

!

XW$978! $O7834J! K/%1%! #+%! ,/%! 9%+0L#,0L%1! (-! 4#+I(J2604! #4091! 0&! ;/04/! ,/%! Pc8! -5&4,0(&! (-!

4#+I(J2604!M+(5*!01!+%*6#4%9!I2!P:8@!M+(5*C!

R C

O

OH R C NH2

O

Amide

-OH

NH2+Carboxylic acid

!

! hB

35&4,0(&#6!M+(5*!(-!#$09%1!01!P.c:8@C!

H C

O

NH2 CH3 C NH2

O

AcetamideFormamide !

&3>=;84!;H!":3?1:1>7;2J!F$09%1!#+%!*+%*#+%9<!

7K!T6!>=3!19>7;2!;H!$OO;271!;2!$978!'=/;:7834J!

CH3 C

O

Cl CH3 C NH2

O

OAcetamide

O 2NH3NH4Cl

!

77K!T6!=31>72L!;H!$OO;271!41/>4!;H!'1:<;@6/79!1978J!

CH3 C ONH4

O

+-

CH3 C NH2

O

O OH2

Ammonium acetateAcetamide !

777K!T6!>=3!19>7;2!;H!1OO;271!;2!$2=68:7834J!

(CH3CO)2O NH3O CH3 C NH2

O

O CH3COOH

Acetamide Acetic acid!

":;?3:>734J!

"=64791/!":;?3:>734J!

0E!F66!#$09%1!#+%!;/0,%H!(9(5+6%11H!4+21,#660&%!1(6091C!

00E!F$(&M!,/%!-(5+!9%+0L#,0L%1!(-!#4091H!(&62!#409!#$09%1!#+%!4#*#I6%!(-!-(+$0&M!0&,%+$(6%456#+!

/29+(M%&! I(&91! 95%! ,(! ;/04/! ,/%2! /#L%! 1/#+*! $%6,0&M! *(0&,1! ,/#,! #+%! /0M/%+! ,/#&! ,/(1%! (-!

4(++%1*(&90&M!#4091C!

000E!"0$*6%!#$09%1!A5*!,(!.?E!#+%!1(65I6%!0&!;#,%+!I5,!1(65I060,2!0&!;#,%+!9%4+%#1%1!#1!;%!#14%&9!

,/%!1%+0%1C!

!

'=3O791/!":;?3:>734J!F$09%1!#+%!1,#I060S%9!I2!+%1(&#&4%C!

R C NH2

O

R C NH2

+

O-

..

!

"0&4%!,/%!%6%4,+(&!*#0+!(&!:<#,($!01!&(,!+%#9062!#L#06#I6%!,(!#&!#409!#$09%1!#+%!6%11!I#104!,/#&!

#$0&%1C!F$09%1!#+%!6%#1,!+%#4,0L%!(-!,/%!#409!9%+0L#,0L%1C!^$*(+,#&,!+%#4,0(&1!(-!#$09%1!#+%!M0L%&!

I%6(;C!

!

! hV

7K!#68:;/6474J!F$09%1!#+%!/29+(62S%9!I2!#409!(+!#6G#60!(&!*+(6(&M%9!/%#,0&MC!

CH3 C NH2

O

O OH2 O ClH CH3 C OH

O

O NH4Cl+ -+ -

CH3 C NH2

O

O NaOH CH3 C ONa

O

+-O NH3

!77K!%319>7;2!I7>=!G7>:;C4!$978! _#FGFKJ!F$09%1!;/%&! /%#,%9!;0,/!:0,+(51! #409! A:#:c@!O!

8.6E!M0L%!4#+I(J2604!#4091C!

!

!777K!%38C9>7;2J!F$09%1!+%954%1!,(!#$0&%1!I2!]0F68BC!

R C NH2

O

LiAlH4 R-CH2-NH2

Amide 1o amine

!

7EK!D3=68:1>7;2J!b/%&!/%#,%9!;0,/! 1,+(&M!9%/29+#,0&M!#M%&,! 154/!#1!*/(1*/(+(51!*%&,(J09%H!

,/%2!-(+$!&0,+06%1C!

R C NH2

O

P2O5

-H2OR C N

Amide Alkane nitrile

(Alkyl cyanide)!EK!#;HO122R4!D3L:181>7;2J!F$09%1!;/%&! ,+%#,%9!;0,/! I+($0&%! #&9! 1(905$!/29+(J09%H! ,/%2!

*+(954%1!*+0$#+2!#$0&%H!;/04/!01!(&%!4#+I(&!6%11!,/#&!,/%!#$09%C!

R C NH2

O

O Br2 O 4NaOH RNH2 2NaBr Na2CO3 2H2OO O O 1o amine

CH3 C NH2

O

O Br2 O 4NaOH CH3NH2 2NaBr Na2CO3 2H2O

Methyl amineAcetamideO O O

!

K/01!+%#4,0(&!01!#61(!4#66%9!#;HHO122R4!:31::12L3O32>C!!

&39=1274OJ!K/%!8(-$#&&Y1!9%M+#9#,0(&!(-!#$09%1!0&L(6L%1!,/%!-(66(;0&M!1,%*1C!

! h?

2NaOH Br2 NaOBr NaBr H2OOOO+ -

!

R C

O

N

H

H.. O-

BrO ^

R C

O

N

H

Br

O OH-

!

^^

-H2O ,BrR C

O

N..

: ^^^

R-N=C=O

iso cyanate

NaOHR-NH2 Na2CO3O

1o amine!

YW!(4>3:4J!Q1,%+1!#+%!4#+I(J2604!#409!9%+0L#,0L%1!0&!;/04/!,/%!Pc8!M+(5*!/#1!I%%&!+%*6#4%9!I2!

#6G(J2!A<cZE!M+(5*C!K/%2!4#&!I%!+%*+%1%&,%9!#1H!

R C

O

OR' Or R-COOR'!K/%2!#+%!&#$%9!#1!,/%!#6G26!1#6,1!(-!,/%!#409!%CM!

8.cc.@8V!P!Q,/26!-(+$#,%!

.8R.cc!.@8V!P!Q,/26!#4%,#,%C!

F! 6#+M%! &5$I%+! (-! %1,%+1! (445+! 0&! -6(;%+1H! -+50,1! (-! ,/%! *6#&,1! #&9! *+(L09%! ,/%! -+#M+#&4%! ,(!

-6(;%+1!#&9!-+50,1C!

!

&3>=;8! ;H! ":3?1:1>7;2J! g%&%+#662! %1,%+1! #+%! *+%*#+%9! I2! 4#+I(J2604! #4091! #&9! ,/%0+! (,/%+!

9%+0L#,0L%1C!

7K! T6! >=3! :319>7;2! ;H! 91:<;@6/79! 1978! I7>=! 1/9;=;/4! 72! ?:343293! ;H! 1978!

_B749=3:R4(4>3:7H791>7;2!O3>=;8KW!

R C

O

OHO HOR' R C OR'

O

O H2O

H2SO4

CH3 C

O

OHO HOC2H5

H2SO4CH3 C

O

OC2H5O OH2

!77K!T6!>=3!:319>7;2!;H!!$978!'=/;:7834!I7>=!$/9;=;/4W!

!777K!T6!>=3!:319>7;2!;H!'1:<;@6/79!41/>4!I7>=!1/06/!=1/783W!!

! hD

R C ONa

O

O XR'- +

R C OR'

O

O NaX+ -

EsterSodium carboxylate !

7EK!!T6!>=3!:319>7;2!;H!91:<;@6/79!1978!I7>=!D71N;O3>=123W!

R C OH

O

O CH2N2 R C OCH3

O

O N2

!

'5,!(&62!$%,/26!%1,%+1!#+%!-(+$%9!I2!,/01!$%,/(9C!

EK!*:124H;:O1>7;2W!

R C

O

R' O R"OH R C OR"

O

OH

+

R'OHor OH

-!

E7K!T6!>=3!:319>7;2!;H!!1/06/!=1/783!I7>=!47/E3:!41/>!;H!91:<;@6/79!1978W!

R-COOAgO Br-R' RCOOR' O AgBr

!

":;?3:>734J!

"=64791/!":;?3:>734J!

=E K/%!4#+I(J2604!%1,%+1!#+%!*6%#1#&,!1$%660&M!60d5091!(+!1(6091C!@E K/%!I(060&M!*(0&,1!(-!,/%!1,+(&M%1,!4/#0&!01($%+1!#+%!/0M/%+!,/#&!,/(1%!(-!!I+#&4/%9!4/#0&!01($%+1C! K/%! I(060&M! *(0&,1! (-! $%,/26! #&9! %,/26! %1,%+1! #+%! 6(;%+! ,/#&! ,/(1%! (-!

4(++%1*(&90&M!#409H!,/01!01!95%!,(!,/%0+!0&#I060,2!,(!-(+$!0&,%+$(6%456#+!/29+(M%&!I(&91C!

RE K/%2!#+%!M%&%+#662!0&1(65I6%!0&!;#,%+!#&9!1(65I6%!0&!$(1,!(+M#&04!1(6L%&,1C!!

'=3O791/! ":;?3:>734J! Q1,%+1! M0L%! &546%(*/0604! 15I1,0,5,0(&! +%#4,0(&! 10$06#+! ,(! #4091! /#609%1!

I%4#51%!(-!!,/%!%6%4,+(&!;0,/9+#;0&M!%--%4,!(-!,/%!PcZs!!M+(5*C!

R C OR'

O

R C OR'

O-

Nu

O :Nu -

CH3 C N

O

u-OR'+

-

!

'5,! %1,%+1! #+%! #61(! 1,#I060S%9! I2! +%1(&#&4%! ,/51! ,/%2! 5&9%+M(! &546%(*/0604! 15I1,0,5,0(&! 6%11!

+%#9062!,/#&!9(!#409!/#609%1C!

! hh

R C OR'

O

R C O

O-

R

..

.. O OHH+

!

g%&%+#6!+%#4,0(&1!(-!%1,%+1!#+%!M0L%&!I%6(;C!

SK!#68:;/6474J!

1K!$978!=68:;/6474J!Q1,%+1!#+%!/29+(62S%9!0&!*+%1%&4%!!(-!#409!4#,#621,!A8@"cBE!(+!8.6E!,(!M0L%!

*#+%&,!4#+I(J2604!#409!#&9!#64(/(6C!

R C OR'

O

O R C OH

O

O R'OH

Ester Carboxylic acid Alcohol

OH2H

+

reflux!

<K!$/01/723!=68:;/6474J!K/%! #6G#60&%! /29+(62101! (-! %1,%+! ,(!-(+$! 1(905$!(+! *(,#1105$! 1#6,! (-!

4#+I(J2604!#409!#&9!#64(/(6!01!+%-%++%9!,(!#1!"#*(&0-04#,0(&C!

R C OR'

O

O R C ONa

O

O R'OH

CH3COOC2H5 O CH3 C ONa

O

O C2H5OH

NaOH

NaOH

Ester Sodium carboxylate Alcohol

Ethyl acetate Sodium acetate Ethyl alcohol

+-

- +

!!

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R C OR'

O

O NH2H R C NH2

O

O R'OH

CH3COOC2H5 O NH2H CH3 C NH2

O

O C2H5OH

Ester AmideAlcohol

Ethyl acetate Acetamide !!

XK!%38C9>7;2J!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

R C OR'

O

LiAlH4 / Ether

orNa / C2H5OH

R-CH2OH R'OHOAlcohols

!

! hU

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

CH3 C OCH3

OLiAlH4 / Ether

orNa / C2H5OH

CH3-CH2OH CH3OHOEthyl alcohol Methyl alcohol

!YK!%319>7;2!I7>=!Q:7L21:8!%31L32>J!!Q1,%+1!;0,/!g+0M&#+9!+%#M%&,!-0+1,!M0L%1!G%,(&%!;/04/!(&!

-5+,/%+!+%#4,0&M!;0,/!#&(,/%+!$(6%456%!(-!,/%!gCZ!M0L%1!,%+,0#+2!#64(/(6C!

R C OR'

O

R"-MgXR C OR'

OMgX

R"

-OR'R C R"

O

Ketone

R"MgXR C R"

OMgX

R"

H2OR C R"

OH

R"

3o alcohol

!\K!'/17432!';283241>7;2J!Q1,%+1!4(&,#0&0&M!&</29+(M%&!#,($!5&9%+M(!4(&9%&1#,0(&!+%#4,0(&1!,(!

-(+$!%<G%,(%1,%+1H!0&!,/%!*+%1%&4%!(-!1,+(&M!I#1%C!K/01!+%#4,0(&!01!G&(;&!#1!C!

CH3 C OC2H5

O

O H CH2 C OC2H5

O

C2H5ONa

-C2H5OHCH3 C

O

CH2 C OC2H5

O

Ethyl acetoacetate !&39=1274OJ!3(66(;0&M!1,%*1!#+%!0&L(6L%9C!

H CH2 C OC2H5

O

C2H5O-

H2C C OC2H5

O

-

CH3 C OC2H5

O

!

CH3 C

O-

CH2 C OC2H5

O

OC2H5Ethyl acetoacetate

-

CH3 C

O

CH2 C OC2H5

O

-C2H5O

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!A%<G%,(!%1,%+E!

!

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Organic Chemistry

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