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S  0 ``  X*  0 `   Z*  0D `   Z*z  bA޽h @ ?Parchment ̙33 Default Design 0 zr@ ( )   0L؇ P    P*    0h݇     R*  d  c $ ?    0  @  RClick to edit Master text styles Second level Third level Fourth level Fifth level!     S  6  `P   P*    6d `   R*  H  0޽h ? ̙3380___PPT10. 0X(   $+ X X 0@ P    X*  X 0<     Z*  X 6\ `P   X*  X 6, `   Z* H X 0޽h ? ̙3380___PPT10.1 0L0 P,_(    0 _ORGANIC SYNTHESIS2(20f<fJ  C "A KTRE: . " <̙? x @ 0 0 ( <̙? x @L 0 0 ) 00x m OKNOCKHARDY PUBLISHING(2 f + 0( "`>B 2008 SPECIFICATIONS>G$G   B  s *޽h ? ̙33y___PPT10Y+D=' = @B +  0L0 0 (  dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0@   0HT INTRODUCTION This Powerpoint show is one of several produced to help students understand selected topics at AS and A2 level Chemistry. It is based on the requirements of the AQA and OCR specifications but is suitable for other examination boards. Individual students may use the material at home for revision purposes or it may be used for classroom teaching with an interactive white board. Accompanying notes on this, and the full range of AS and A2 topics, are available from the KNOCKHARDY SCIENCE WEBSITE at... www.knockhardy.org.uk/sci.htm Navigation is achieved by... either clicking on the grey arrows at the foot of each page or using the left and right arrow keys on the keyboard (2 2(2 2  75, dB   <D?     0*{0P( OKNOCKHARDY PUBLISHING(2    0kX _ORGANIC SYNTHESIS2(2$f<fB  s *޽h ? ̙33y___PPT10Y+D=' = @B +  0L0 - % `  (    0tf{  n CONTENTS Introduction Functional groups Chiral synthesis - introduction Nucleophilic addition Nucleophilic substitution Synthetic methods f 2`2 y>=  $dB  <D)P0Q  0Pp@ 0 0dB  @ <D)PXP   0X0@ 0 0  0X _ORGANIC SYNTHESIS2(2$f<f  0C"?%h @ 0 0  6C"?= @ 0 0  6C"?% @ 0 0  6C"?% t@ 0 0  6C"?% @ 0 0  6C"? ' h @ 0 0B  s *޽h ? ̙33y___PPT10Y+D=' = @B +O 0 vn $(  $ $ 0 ]ORGANIC SYNTHESIS0(2f3 $ 0D0 9Involves the preparation of new compounds from others. :: : dB $ <D)P0Q $ 0Pp@ 0 0dB $@ <D)PXP $ 0X0@ 0 0H $ 0޽h ? ̙33y___PPT10Y+D=' = @B + 0  (    0< ]ORGANIC SYNTHESIS0(2f3o  0lnjD0 Involves the preparation of new compounds from others. Many industrial processes involve a multi stage process where functional groups are converted into other functional groups. *9}  dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' = @B +; 0 bZ  (      0 ]ORGANIC SYNTHESIS0(2f3   0D0  mInvolves the preparation of new compounds from others. Many industrial processes involve a multi stage process where functional groups are converted into other functional groups. When planning a synthetic route, chemists must consider... HxMMM@  dB   <D)P0Q   0Pp@ 0 0dB  @ <D)PXP   0X0@ 0 0H   0޽h ? ̙33y___PPT10Y+D=' = @B +^ 0 } (    0(Ҍ ]ORGANIC SYNTHESIS0(2f3  0ՌD0   Involves the preparation of new compounds from others. Many industrial processes involve a multi stage process where functional groups are converted into other functional groups. When planning a synthetic route, chemists must consider... " the reagents required to convert one functional group into another " the presence of other functional groups - in case also they react Vx<!  dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' = @B +  0   0 ((  ( ( 0ӌ ]ORGANIC SYNTHESIS0(2f3 ( 0`D0  *rInvolves the preparation of new compounds from others. Many industrial processes involve a multi stage process where functional groups are converted into other functional groups. When planning a synthetic route, chemists must consider... " the reagents required to convert one functional group into another " the presence of other functional groups - in case also they react " the conditions required - temperature, pressure, catalyst " the rate of the reaction " the yield - especially important for equilibrium reactions " atom economy Hx<MMM! : dB ( <D)P0Q ( 0Pp@ 0 0dB (@ <D)PXP ( 0X0@ 0 0H ( 0޽h ? ̙33y___PPT10Y+D=' = @B +d  0   P 0 (  0 0 0d ]ORGANIC SYNTHESIS0(2f3 0 0>D0Y  Involves the preparation of new compounds from others. Many industrial processes involve a multi stage process where functional groups are converted into other functional groups. When planning a synthetic route, chemists must consider... " the reagents required to convert one functional group into another " the presence of other functional groups - in case also they react " the conditions required - temperature, pressure, catalyst " the rate of the reaction " the yield - especially important for equilibrium reactions " atom economy " safety - toxicity and flammability of reactants and products " financial economy - cost of chemicals, demand for product " problems of purification " possibility of optically active productsZx>B!  dB 0 <D)P0Q 0 0Pp@ 0 0dB 0@ <D)PXP 0 0X0@ 0 0H 0 0޽h ? ̙33y___PPT10Y+D=' = @B +r  0   @ ,) (  , , 0> ]ORGANIC SYNTHESIS0(2f3 , 0>D0Y  Involves the preparation of new compounds from others. Many industrial processes involve a multi stage process where functional groups are converted into other functional groups. When planning a synthetic route, chemists must consider... " the reagents required to convert one functional group into another " the presence of other functional groups - in case also they react " the conditions required - temperature, pressure, catalyst " the rate of the reaction " the yield - especially important for equilibrium reactions " atom economy " safety - toxicity and flammability of reactants and products " financial economy - cost of chemicals, demand for product " problems of purification " possibility of optically active productshx<f!  dB , <D)P0Q , 0Pp@ 0 0dB ,@ <D)PXP , 0X0@ 0 0H , 0޽h ? ̙33y___PPT10Y+D=' = @B + 0   (    0+> ]ORGANIC SYNTHESIS0(2f3(  02>D0h Functional groups Common functional groups found in organic molecules include... alkene hydroxyl (alcohols) halogenoalkane carbonyl (aldehydes & ketones) amine nitrile carboxylic acid esterH3B{fT             dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0X   C 0A functgroupsW 5H  0޽h ? ̙33y___PPT10Y+D=' = @B + 0  <O(  < < 0 \CHIRAL SYNTHESIS0(2f3+ < 00H>D0 qRationale Pharmaceutical synthesis often requires the production of just one optical isomer. This is because... *r !h r dB < <D)P0Q < 0Pp@ 0 0dB <@ <D)PXP < 0X0@ 0 0H < 0޽h ? ̙33y___PPT10Y+D=' = @B +s 0  *(    0@y> \CHIRAL SYNTHESIS0(2f3  0<>D0  Rationale Pharmaceutical synthesis often requires the production of just one optical isomer. This is because... " one optical isomer usually works better than the other " the other optical isomer may cause dangerous side effects " laboratory reactions usually produce both optical isomers " naturally occurring reactions usually produce just one optical isomer | !h=!@f@!Lf | dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' = @B +  0   p 8R (  8 8 00> \CHIRAL SYNTHESIS0(2f3. 8 0>D0U TRationale Pharmaceutical synthesis often requires the production of just one optical isomer. This is because... " one optical isomer usually works better than the other " the other optical isomer may cause dangerous side effects " laboratory reactions usually produce both optical isomers " naturally occurring reactions usually produce just one optical isomer Example Aldehydes and ketones undergo nucleophilic addition with cyanide (nitrile) ions; CH3CHO + HCN   > CH3CH(OH)CN ethanal 2-hydroxypropanenitrile+ !q_ffff f"!           9   dB 8 <D)P0Q 8 0Pp@ 0 0dB 8@ <D)PXP 8 0X0@ 0 0H 8 0޽h ? ̙33y___PPT10Y+D=' = @B +_ 0 ~ D(  D D 0> \CHIRAL SYNTHESIS0(2f3 D 0ܱ>D0 DExample Aldehydes and ketones undergo nucleophilic addition with cyanide ions CH3CHO + HCN   > CH3CH(OH)CN ethanal 2-hydroxypropanenitrile !Iffff f#!t          K   dB D <D)P0Q D 0Pp@ 0 0dB D@ <D)PXP D 0X0@ 0 0H D 0޽h ? ̙33y___PPT10Y+D=' = @B +  0 0 B(    0X> \CHIRAL SYNTHESIS0(2f3  0>D0  @Example Aldehydes and ketones undergo nucleophilic addition with cyanide ions CH3CHO + HCN   > CH3CH(OH)CN ethanal 2-hydroxypropanenitrile Problem - the C=O bond is planar - the nucleophile can attack from above and below - there is an equal chance of each possibility - a mixture of optically active isomers is produced - only occurs if different groups are attached to the C=O x@!Iffff f#!          K  G    dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' = @B +?  0 f ^ @(  @ @ 0x> \CHIRAL SYNTHESIS0(2f3p @ 0>D0  nExample Aldehydes and ketones undergo nucleophilic addition with cyanide ions CH3CHO + HCN   > CH3CH(OH)CN ethanal 2-hydroxypropanenitrile Problem - the C=O bond is planar - the nucleophile can attack from above and below - there is an equal chance of each possibility - a mixture of optically active isomers is produced - only occurs if different groups are attached to the C=O CN attacks from abovexW!Iffff f#! !          K  G    dB @ <D)P0Q @ 0Pp@ 0 0dB @@ <D)PXP @ 0X0@ 0 0Z @ C $A nuad1"` RH @ 0޽h ? ̙33y___PPT10Y+D=' = @B +?  0 f ^  (    0} \CHIRAL SYNTHESIS0(2f3p  0}D0  nExample Aldehydes and ketones undergo nucleophilic addition with cyanide ions CH3CHO + HCN   > CH3CH(OH)CN ethanal 2-hydroxypropanenitrile Problem - the C=O bond is planar - the nucleophile can attack from above and below - there is an equal chance of each possibility - a mixture of optically active isomers is produced - only occurs if different groups are attached to the C=O CN attacks from belowxW!Iffff f#!  !          K  G    dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0Z  C $A nuad2"`O qxH  0޽h ? ̙33y___PPT10Y+D=' = @B +  0 ;3P  (    0} \CHIRAL SYNTHESIS0(2f3  0!}D0  >Example CH3CHO + HCN   > CH3CH(OH)CN ethanal 2-hydroxypropanenitrile CN attacks from above CN attacks from below!ffff f#!  ! ff&6  Q dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0Z  C $A nuad1"`!#Z   C $A nuad2"`? 2h XB  @ 0Dff>v v    01}ffC"?=  ] MIRROR IMAGES (2ff  H  0޽h ? ̙33y___PPT10Y+D=' = @B + 0   (    088} \CHIRAL SYNTHESIS0(2f3  0=}D0  >Example CH3CHO + HCN   > CH3CH(OH)CN ethanal 2-hydroxypropanenitrile CN attacks from above CN attacks from below!ffff f#!  ! ff&6  Q dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0^   C (ACOopt1g"`@^   C (ACOopt2g"` n H  0޽h ? ̙33y___PPT10Y+D=' = @B +} 0   4(  x   0C"? "(   0P} \CHIRAL SYNTHESIS0(2f3$  0M}D0 Example CH3CHO + HCN   > CH3CH(OH)CN ethanal 2-hydroxypropanenitrile ANIMATIONY !ffff f#! &6  ' dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0d  C <A $nucaddanimwhite2x] H  0޽h ? ̙33y___PPT10Y+D=' = @B +_ 0 ~ L(  L L 0Ph} \CHIRAL SYNTHESIS0(2f3 L 0$n}D0 6Consequences " isomers have to be separated to obtain the effective one " separation can be expensive and complicated " non-separation leads to ,} !  dB L <D)P0Q L 0Pp@ 0 0dB L@ <D)PXP L 0X0@ 0 0H L 0޽h ? ̙33y___PPT10Y+D=' = @B +Q 0 xp P(  P P 0h{} \CHIRAL SYNTHESIS0(2f3 P 0H}}D0 Consequences " isomers have to be separated to obtain the effective one " separation can be expensive and complicated " non-separation leads to larger doses needed possible dangerous side effects possible legal action v} !m Pf  dB P <D)P0Q P 0Pp@ 0 0dB P@ <D)PXP P 0X0@ 0 0H P 0޽h ? ̙33y___PPT10Y+D=' = @B +  0   H(  H H 0L} \CHIRAL SYNTHESIS0(2f3r H 0}D0  Consequences " isomers have to be separated to obtain the effective one " separation can be expensive and complicated " non-separation leads to larger doses needed possible dangerous side effects possible legal action Solution " use natural chiral molecules as starting materials " use stereoselective reactions which give one isomer " use catalysts which give a specific isomer " use enzymes or bacteria which are stereoselective } } !f f  f'fZ   *  x   dB H <D)P0Q H 0Pp@ 0 0dB H@ <D)PXP H 0X0@ 0 0H H 0޽h ? ̙33y___PPT10Y+D=' = @B +  0   p  (    0l^} \CHIRAL SYNTHESIS0(2f3f  0|}D0O (Consequences " isomers have to be separated to obtain the effective one " separation can be expensive and complicated " non-separation leads to larger doses needed possible dangerous side effects possible legal action Solution " use natural chiral molecules as starting materials " use stereoselective reactions which give one isomer " use catalysts which give a specific isomer " use enzymes or bacteria which are stereoselective Other examples Nucleophilic substitution of halogenoalkanes,} }B !Pf !f f  f'f!2   *  x        dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' = @B + 0 ` Z(    0} eNUCLEOPHILIC SUBSTITUTION0(2f3  0}D0  iProblems There are two possible mechanisms SN2 This produces just one optical isomer with reversed optical activity Called SN2 because two species are involved in the rate determining step. r+}!' T C  dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0\  C 4ASN2animtranspaH  0޽h ? ̙33y___PPT10Y+D=' = @B + 0  a(  Z  C 2A SN1animtranssa  0} eNUCLEOPHILIC SUBSTITUTION0(2f3  0}D0k  rProblems There are two possible mechanisms SN1 This produces a racemic mixture of two optical isomers Called SN1 because one species is involved in the rate determining step.r+}!' F @&G  i dB  <D)P0Q  0Pp@ 0 0dB @ <D)PXP  0X0@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' = @B + 0    (    0 eNUCLEOPHILIC SUBSTITUTION0(2f3  0 D0- IQProblems There are two possible mechanisms SN2 This produces just one optical isomer with reversed optical activity Called SN2 because two species are involved in the rate determining step. SN1 This produces a racemic mixture of two optical isomers Called SN1 because one species is involved in the rate determining step.+}'!' 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