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Double and triple bonds are treated like bonds to duplicate atoms. => AZAA  `5}796 Stereoisomers  Geometric isomers: cis-trans isomers. Enantiomers: nonsuperimposable mirror images, different molecules. => FZ  $ SF        l   Chirality     , Handedness : right glove doesn t fit the left hand. Mirror-image object is different from the original object. => Z  Chiral Carbons  Tetrahedral carbons with 4 different attached groups are chiral. Its mirror image will be a different compound (enantiomer). => <Z K   A/Mirror Planes of Symmetry  vIf two groups are the same, carbon is achiral. (animation) A molecule with an internal mirror plane cannot be chiral.*Hw&7 *&    J  B0 (R), (S) Nomenclature6  Different molecules (enantiomers) must have different names. Usually only one enantiomer will be biologically active. Configuration around the chiral carbon is specified with (R) and (S). L=7>   Assign Priorities   'Absolute Conformation Assign (R) or (S)6((  Working in 3D, rotate molecule so that lowest priority group is in back. Draw an arrow from highest to lowest priority group. Clockwise = (R), Counterclockwise = (S) =>PIZ5PnFH  N1 Properties of Enantiomers  Same boiling point, melting point, density Same refractive index Different direction of rotation in polarimeter Different interaction with other chiral molecules Enzymes Taste buds, scent => *ZfZf*d         Optical Activity  7Rotation of plane-polarized light Enantiomers rotate light in opposite directions, but same number of degrees. => 8    Polarimetry     Use monochromatic light, usually sodium D Movable polarizing filter to measure angle Clockwise = dextrorotatory = d or (+) Counterclockwise = levorotatory = l or (-) Not related to (R) and (S) => lr) Fa             Specific Rotation  Observed rotation depends on the length of the cell and concentration, as well as the strength of optical activity, temperature, and wavelength of light.!   Calculate [a]D<   A 1.00-g sample is dissolved in 20.0 mL ethanol. 5.00 mL of this solution is placed in a 20.0-cm polarimeter tube at 25C. The observed rotation is 1.25 counterclockwise. => Fx!O*b       O23-Biological Discrimination  Racemic Mixtures  Equal quantities of d- and l- enantiomers. Notation: (d,l) or () No optical activity. The mixture may have different b.p. and m.p. from the enantiomers! => z  Racemic Products  mIf optically inactive reagents combine to form a chiral molecule, a racemic mixture of enantiomers is formed.n!nn  Optical Purity  $Also called enantiomeric excess. Amount of pure enantiomer in excess of the racemic mixture. If o.p. = 50%, then the observed rotation will be only 50% of the rotation of the pure enantiomer. Mixture composition would be 75-25. => %Z%*         Calculate % Composition  Chirality of Conformers     If equilibrium exists between two chiral conformers, molecule is not chiral. Judge chirality by looking at the most symmetrical conformer. Cyclohexane can be considered to be planar, on average. => VZ 3 $FS     /     o  Mobile Conformers  Nonmobile Conformers      EIf the conformer is sterically hindered, it may exist as enantiomers.F!FF  Allenes  Chiral compounds with no chiral carbon Contains sp hybridized carbon with adjacent double bonds: -C=C=C- End carbons must have different groups.2 _  Fischer Projections  Flat drawing that represents a 3D molecule A chiral carbon is at the intersection of horizontal and vertical lines. Horizontal lines are forward, out-of-plane. Vertical lines are behind the plane.  W3 Fischer Rules  `Carbon chain is on the vertical line. Highest oxidized carbon at top. Rotation of 180 in plane doesn t change molecule. Do not rotate 90! Do not turn over out of plane! => tU#!  Fischer Mirror Images  VEasy to draw, easy to find enantiomers, easy to find internal mirror planes. Examples:W  Fischer (R) and (S)6   Lowest priority (usually H) comes forward, so assignment rules are backwards! Clockwise 1-2-3 is (S) and counterclockwise 1-2-3 is (R). Example:l" !   ]4Draw (R)-2-butanol"   Diastereomers  Stereoisomers that are not mirror images. Geometric isomers (cis-trans) Molecules with 2 or more chiral carbons. => .8  /    {  Alkenes  DCis-trans isomers are not mirror images, so these are diastereomers.,E!6 8  3        Ring Compounds  \Cis-trans isomers possible. May also have enantiomers. Example: trans-1,3-dimethylcylohexane$]@8  G      !Two or More Chiral Carbons  Enantiomer? Diastereomer? Meso? Assign (R) or (S) to each chiral carbon. Enantiomers have opposite configurations at each corresponding chiral carbon. Diastereomers have some matching, some opposite configurations. Meso compounds have internal mirror plane. Maximum number is 2n, where n = the number of chiral carbons. => d) p~          z     3      "Examples   #$Fischer-Rosanoff Convention: D and L%%$*      Before 1951, only relative configurations could be known. Sugars and amino acids with same relative configuration as (+)-glyceraldehyde were assigned D and same as (-)-glyceraldehyde were assigned L. With X-ray crystallography, now know absolute configuration of : D is (R) and L is (S). No relationship to dextro- or levorotatory. => Z ZV p~y    !    |         L  $ D and L Assignments.((   %!Properties of Diastereomers    8Diastereomers have different physical properties: m.p., b.p. They can be separated easily. Enantiomers differ only in reaction with other chiral molecules and the direction in which polarized light is rotated. Enantiomers are difficult to separate. => 9Z5   ,  &"Resolution of Enantiomers  ]React a racemic mixture with a chiral compound to form diastereomers, which can be separated.^!^*7       4.)Chromatographic Resolution of Enantiomers*  2, ` ̙33` ` ff3333f` 333MMM` f` f` 3>?" dd@,|?" dd@   " @ ` n?" dd@   @@``PR    @ ` ` p>> (    6 0 @  T Click to edit Master title style! !  0  @   RClick to edit Master text styles Second level Third level Fourth level Fifth level!     S  0# ``  Z*  0( `   :Unit 4  0- `   \*H  0޽h ? ̙33 Default Design0 zr ( r@k@   0m P    P*    0G     R*  d  c $ ?    0V  @  RClick to edit Master text styles Second level Third level Fourth level Fifth level!     S  6\ `P   P*    6p `   R*  H  0޽h ? ̙33@ ( [99[[   0< P    X*   0     Z*   6p `P   X*   6L `   Z* H  0޽h ? ̙33l 0 (  r  S $qp    6(K` .Organic Chemistry, 5th Edition L. G. Wade, Jr.J/(2H  0޽h ? ̙33  ,D( /@X ,l , C EP     , C dF<$0  H , 0޽h ? ̙33 @H(  `  c $A8 ??P    <̪  ] cis or trans?     <+ 1,$D 0 RE and Z Based on Priority:   3k  <o ,$D 0 [Cahn- Ingold-Prelongo: 1. Atomic Number 2. Atomic weight 3. Atomic number of the next atom\ \ 6G  < F D,$D 0 F----------------    6@ P,$D 0 >     <` ],$D 0 835  3  <ñg ,$D 0 853  3  <Ʊ@D,$D 0 91 $f  <0ʱpd,$D 0 72    <ͱ',$D  0 817  3  <DѱD ,$D  0 79  3  <ӱ',$D  0 72    <|ױT,$D  0 91 $f  <ڱ F,$D  0 dHigher priority at the opposite side of pi bond (E) Higher priority at the same side of pi bond (Z)ve            <x0 ? ,$D 0 ? (E) ? ethane    6 ]d ,$D 0 +(E)-1-bromo-2-chloro- 2-fluoro-1-iodoethane, , !   S ` 0   %Geometric isomers: cis-trans isomers&& 4      H  0޽h ? ̙33 1)P (    <l,$D 0 ] cis or trans?     < + },$D 0 RE and Z Based on Priority:   3  c $AD ??q I 8 $D  0  <$0f*,$D  0 F----------------    6d p ,$D 0 >     <,\t,$D 0 71  3  < -,$D 0 812  3  <@D ,$D 0 91 $f  <T-,$D 0 72    < p,$D 0 812  3  <M ,$D 0 812  3  <\-,$D 0 72    < ,$D 0 91 $f  <x m ,$D 0 b(E) ? pentyne    6#c ,$D 0 (E)-3-ethyl-3-pentene-1-yne  ,  <AE ??@ N8 $D 0  <AF ??p  8 $D 0   <AG ?? 08 $D 0H  0޽h ? ̙33x ( `(  x  <AQ ??@9    <AR ??p 28 $D 0  <AS ?? 0@ 8 $D 0  <AT ?? 8 $D 0  <AU ??  8 $D 0  <AV ?? 8 $D 0  <AW ??0 8 $D 0H  0޽h ? ̙33 p (  x  <A; ??0 " x  <A< ??>     <A= ?? 8 $D 0  <A> ??~ 08 $D 0  <A? ??P5 8 $D 0  <A@ ?? 8 $D 0  <AA ?? 8 $D 0   <AB ?? 8 $D 0  c $80h<$D 0   ?Geometric IsomersH  0޽h ? ̙33u  % ( f3ff r  S 00 @     S  <$0    <ZFq z,$D 0 vcis-1,2-dichlorocyclopentane#   <@ `,$D 0 trans -1,2-dichlorocyclopentane&     s *Ap 3B,$D 0   s *A@ ,$D 0H  0޽h ? ̙33  \T( 6,' r  S 0 @     S ȥ @@<$0    c l.EAHD:\WADE\CHAP05\FIGURES\FG05_001.PCT?  H  0޽h ? ̙33  nf ( ӭ r  S 0 @     S p<$0    C ~AfC:\Jo\Wade ed5 PPT\Graphics\Chapter 05\FG05_06.JPG/ PH  0޽h ? ̙33f (  x  <A ??[   6@ 0 p bStereoisomerisms,x  <A ??`P    0I < r@Chiral: An object that cannot be superposed on its mirror image A A   <xM p  X Chiral Carbon atom Chiral center! ! x  <A ?? P x  <A" ?? :@ H  0޽h ? ̙33  QI0 (   r  S      c l.kAHD:\WADE\CHAP05\FIGURES\FG05_006.PCT@ `+   0H/ `,$D0 {Caution! If there is no plane of symmetry, molecule may be chiral or achiral. See if mirror image can be superimposed. => $|x*E    0     s ,C0e0e   <$0  H  0޽h ? ̙33H  (  x  <A$ ??P   <A% ??  8 $D 0  <A& ??@  8 $D 0x  0W ,$D 0 nThese mirror images are not the same, even after rotation! These are two distinct 3-methylhexane enantiomers8a  c T H  0޽h ? ̙33  LD@(( $4 (r ( S 0 @    ( S L @ <$0  l `  (` ,$D0Z ( s *A` Pp ( <vf  2=>H ( 0޽h ? ̙33  IAP0( 5<5 0r 0 S 0 @   R 0 s *A  0 <,$D0 ;1 0 <(,$D0 ;2 0 <(,$D0 ;3 0 <d,$D0 ;4 0 s *A` 8 ,$D0  0 <P$0 ,$D0 ;1  0 < @,$D0 ;2  0 <(d,$D0 ;3  0 <H@,$D 0 ;4 0 < |P@,$D 0 ;1 0 < pD,$D 0 ;2 0 <  t ,$D 0 ;3l   0 ,$D0 0 BL  ,$D0 ;4 0 <  => rl   0 `,$D 0@t   0 ,$D 0Z  0 s *A 0 Z 0 s *A   0 <pY y  : expands to H 0 0޽h ? ̙33z  *"`4( $0  4r 4 S 0 @    4 C  <$0  h 4 C @A (A:\REV FG05_024.pct hH 4 0޽h ? ̙33t $  (  x  <A' ?? x  <A( ?? x  <A) ??@ = x  <A* ??p  x  <A+ ??P  x  <A, ?? `  c $A- ?? W   <8h ,   91  3  <k    92  3  <Zl   93  3`   c $A. ?? 0 0   <8r P  9R (3H  0޽h ? ̙33  p<D( _P <l < C %     < C &<$0  H < 0޽h ? ̙33  VN8( `T 8r 8 S *0 @    8 C /<$0   8 c l.)\A HD:\WADE\CHAP05\FIGURES\FG05_011.PCTpq1H 8 0޽h ? ̙33  h`@(  @r @ S F0 @    @ C > <$0   @ C ~A fC:\Jo\Wade ed5 PPT\Graphics\Chapter 05\FG05_13.JPG H @ 0޽h ? ̙33   D^(  Dr D S ,0 @    D S - @<$0  l p0  Dp0,$D0@ `    Dpp  D 0 -  b [a] = : 2     D < *    D 0P`  a (observed) J 2     fB D 6D1  D 0TV6 @   p c lJ       D <\ 0 |c is concentration in g/mL l is length of path in decimeters. => b} ?>:H D 0޽h ? ̙33  H(  Hr H S \h0 @   l H C i   H H 0޽h ? ̙33  _ W  (    c $A/ ??T)8 $D 0  <ph`Md,$D 0 9= -----    <kT,$D 0 pa lc.      c $A/ ??T )8 $D 0  0Lr0 ,$D 0 \$Specific rotation Na line D at 20C% %   <sqD,$D 0  observed rotation at 20C = 1.25 l the cell length in dm (1 dm = 10 cm)= 20 cm = 2.0dm c concentration g/mL = 1.00g/20.0 mLX& a` a&   $7 a$  < F4  7[a] = LB  c $D    <0 F  I1.25 2.0 dm(1g/20 mL) x  <A0 ?? k    <    3= H  0޽h ? ̙33  VN( 0o l  C `m @P     c lr&#A#HD:\WADE\CHAP05\FIGURES\FG05_014.PCT`  <lp Z 2=>H  0޽h ? ̙33  LP( x Lr L S t0 @    L S u @ <$0  H L 0޽h ? ̙33   PV(  Pr P S z0 @   r P S | @   P C ~A fC:\Jo\Wade ed5 PPT\Graphics\Chapter 05\FG05_16.JPG|  P 6<@` =>H P 0޽h ? ̙33  TP( L  Tr T S $0 @    T S  @ <$0  H T 0޽h ? ̙33>      X~ (  Xl X C 蒸` @0    X 0|  8dThe specific rotation of (S)-2-iodobutane is +15.90. Determine the % composition of a mixture of (R)- and (S)-2-iodobutane if the specific rotation of the mixture is -3.18.    1    C  , J 6 X <`P ,$D 0 BOptical Purity = B X c $D 0 ,$D 0& X <@; ,$D 0 ,Observed Rotation Rotation of pure enatiomer-- #  X <4  ,$D 0 3= B X c $D0  0 ,$D 0  X < R ,$D 0 F-3.18 x 100 -15.90   X < 0 ,$D 0 ;X 100   X <z   ,$D 0 3=   X <A1 ??@ "< 8 $D  0  X <Z v ,$D  0 7= 23% H X 0޽h ? ̙33  \P( ' ' \r \ S 0 @    \ S p @ <$0  H \ 0޽h ? ̙33    `Z(  `r ` S ø0 @   l @  `` ,$D0Z ` s *A` 5 ` <0Ǹ @  GNonsuperimposable mirror images, but equal energy and interconvertible.2H6   $$9l  p  ` ,$D0Z ` s *A0   ` <ϸ @   [Use planar approximation.&  ` 6H޸P p =>LB  ` c $D   H ` 0޽h ? ̙33  0dP(  dl d C `   r d S گ @  | d 600 => d C ~AfC:\Jo\Wade ed5 PPT\Graphics\Chapter 05\FG05_17.JPG  H d 0޽h ? ̙33  @ h=(   hr h S 0 @    h C  <$0  l  @  h T W,$D0 h s rH'+AHD:\WADE\CHAP05\FIGURES\FG05_018.PCT @ "  h <@  jAllene is achiral." l @ ` {  h` @ {,$D0 h s r)\AHD:\WADE\CHAP05\FIGURES\FG05_018.PCT@ ` {,$D0 h 6  => H h 0޽h ? ̙33  |Pl( /@ lr l S 00 @    l S  0 <$0   l C A |C:\Jo\Wade ed5 PPT\Graphics\Chapter 05\Reduced\FG05_20-01.jpg H l 0޽h ? ̙33  | t  (    0d0` UAbsolute conformation: the order of arrangement of four groups around the carbon atom&V  3A   0Еpf,$D 0 (+)-glyceraldehyde: the  OH group to the right ( a molecular structure)L L :  c $A6 (??G 8 ($D 0t  0욷 `,$D 0 nFisher Projection Regular projection Clockwise, S Clockwise, R Counterclockwise, R Counterclockwise, SVo M        c $A3 ??`  8 $D 0  < 6*y,$D 0 91  3  <),$D 0 92  3  <I ,$D 0 93  3  <<VJ,$D 0 94  3  <&I ,$D  0 91  3  <,z,$D  0 92  3  < 9 ,$D  0 93  3  c $A5 +??i@l 8 +$D  0  c $A2 &??p =) 8 &$D 0XB  0DԔ  H  0޽h ? ̙33  `pP(   pr p S t0 @    p S T @ <$0  H p 0޽h ? ̙33  p t[(  tr t S 0 @   r t S  @P   t s *A@G ,$D0Dl @   t@ ,$D0Z t s *A@ fB t 6Dp Ul 0 ppP   tp0 pP ,$D0Lt 0 pP   t0 pP ,$D0Z t s *AP pP fB  t 6D0    t 6, p p  => H t 0޽h ? ̙33   x9(  xr x S T0 @    x S 4 @` <$0   x s *A L p,$D0l    x 0 Tp ,$D0fB xB 6D  x < @  C(S)$l A   x A,$D0t 1 ``  xA p ,$D0fB x 6D` ` x < 1@` ;(S)  x 6|  => H x 0޽h ? ̙33y  )! (  r  S DP$     <A4 ,?? 8 ,$D 0  <* t u,$D 0 \$ 2 3 4 1% % f   c $A7 -??^Qp8 -$D 0  < . @ ,$D 0 91  3  <( 6* ,$D 0 92  3  <=  ,$D 0 93  3   c $A: 5?? 8 5$D 0  c $A9 1??P 8 1$D 0H  0޽h ? ̙33  |P( @ 4 |r | S 0 @    | S d  <$0  H | 0޽h ? ̙33  sk(  r  S `B0 @   r  S C @  R  s *Ap p }  6TFP p  => H  0޽h ? ̙33m  (   r  S K0 @     S L @<$0  Ul `` `G ` ``G,$D0Lt `` wG `` wG,$D0Z  s *A`` wGfB  6D@ @ @  68@ ``  => H  0޽h ? ̙33  D( $A   l  C S     C T`<$0  H  0޽h ? ̙33  1) ( ۬- r  S [0 @     0A?`P ,$D0ol b    b,$D0  <0hP p => `  0A!?b H  0޽h ? ̙33  D(  l  C g0`     C te`<$0  H  0޽h ? ̙33  LD (   l  C n   R  s *A00 p  <u 1*l 0 PG  P0 G,$D0Z  s *A0 PG  <HyLI 0  ;*l ` p L  ` p L,$D0t ` P L  ` p L,$D0Z  s *A` P L  <@@ `  9*   6؄ p  => H  0޽h ? ̙33  D( \ l  C P     C ĉ<$0  H  0޽h ? ̙33    `( `@ l  C    l  C `   |  60 =>  C A|C:\Jo\Wade ed5 PPT\Graphics\Chapter 05\Reduced\FG05_21-01.jpg0 H  0޽h ? ̙33  x0(  l  C ԠPpP     <@` 2=>  C A~C:\Jo\Wade ed5 PPT\Graphics\Chapter 05\Reduced\FG05_22-01X.jpgUH  0޽h ? ̙33 VN(    6÷   HEnd of Chapter 5,H  0޽h ? ̙33`xMlEnu>i)PQB I\[GMP$#說q#@%[.K/H EB=\sFc9{;ڳBG5;7ofvgݵ=׾JoA8;gs `]Ƙwi(,цQ'::ѺкzЎ<qN=vShϢF{y3h/΢hC{m5h !ʫպ7m|U=4IHJ{>~rƔ1PL:4xS0> ?| !Y>,MQq|fa)!l]nZO >QG?Zg`Ĵuد4_>~/Ԝi*ޯ踦Bы#r1mGhneD|+ߊ~}/\v4#ߍl9w07,7pˠA90}88orB{w ipkv.3EGŚiH)[UL)ؽ4\Q: 7x81-Ĵ>18Ppڰކʬǵ@;5$q*xƓu0Un_!yM\{RS蹪s$; SslO0q< ta?g_MsdkWM1$Jp"$ @aLBrlDn`DG|yU1V55ʔjd_Sq\/¸Dd8AHp6jQbH`ٍL6䀺:0]˜gՈe)va1q*XB4Qhk g)^oXFKe]^*xH⻿sGIoA̬XGUv: 皣999999999ZZOi4Gs4Gs"_6kNHaw5~Pqqs񛖖#lxKlTUǿ{{ӧS€(V%&nd@|t†8`B! ܕ B¢f &5ȦXcXX6m0=vn;3138}̹νˣ ~s~5f= e:LuEC8#U 7?a[nPJ{qR"+_ߦM>*~8᳾۾a/ڟQ&^?Ȑ5>m1<߽ҷya%g%Z 8.i=Mib;f~#Lm77Ti\\y`}0i8i4LڧȤV-i2(%*f<Δ1t8g~t`귏<Կ_S_tUM*9yhpL7a;`/QTnDj\#Zib'_,ұ?dVTbꥨ[5Oeۭwaw]#dw@ԎlgG066.]3g'رc088cH dj.cf&M&̇3 #]x-GÈ9͈$g?95ѣ,C%9%C'ж zo.0 F/s{;;X3̰hcT,!_CeHҪAms;s,;Χg`9o|ʹIxNl֋%*rV I%B~;vaߎݝ>~{C9`]0{^I>&~·_O-l?Czj#Wސ;o#^ 0/gt* XVSQpc~3roC^IBF|J#1 Di 3j$"5l N !Uk|duNnSmEoFy_0rcDaquc*?-* f>p*,?n ]./|-w/ᇫ2L ȷ|r+CյÏexE~6Ԕކԁ/gJ*$U8ea!YD>o6/+\X@o_dDIi?9ɟO s4~98KwKJk=s2(J熪onмWtOyNM9oOP%~`SC$M%_!R7Su * <[LԂ():X Jkxkǃjjih}Az@WO< |\_0S;<D_at]ꥏx;U&pO+ UjZR̗SҤ|UͯpoW'UJo2퇉 P# va]jdO 淫n&݇gD<U2P?97mbV23|f[xy3YxIAN!sVUu*ſY]o[c h+9ƏÅXN||xo2⵴ tX:xMlUE{n"qDPLY7Ȣ%( čqAjBtHX5QѰ#FBDIܘ\&M73wsW,wړyw|9}}۪ ? ܆ %.hYJ-ydSN.n+Q u5jj?kPעC]:Ahɣ%q9`|-ZYFηX)ۯ< W-ՔQxnh1G?F4!S4~zݦW0m\Οz]WFm!{sLJ%UJб`JG-Rܧ3d|_ W`K3F4 ?Վ:rn8vP3eOV)v/MeՑϻ=L ,egN1:<@.l!vE<%וhl6I+ ʥ ڑ;`gyIr}zJ[o>3eo( uOulǪ3xs[Iݗ҄C[=E뇱G }XU.䵿ҌWpv{QiԧQO ;nM=Zu5`ǁ3_ׯ_)v\r~ &''ԗpY8p@3N(vg犲+/YSơ6 Of^:*۞[}" V}v:w|Zײ{sd{'{Y,־DHvga bet_@v"q [H:(Yll3{wT[3{S7s3رqz{w#Z'Va;xSV@3 jAѭw`clv)6m \~(M)k4]ˊf7I-UoY,Ke$i,/6EƜly^֮ظ,mSYhYmS%\vX˒X`eˀEu t6aVSk,eĢiĆҚ76Tcm|l83$N+j\HNIXU*g4ŶM_\RZ}MsVgӏcCgxN65êzeHG߱,,(^BYp5b8˰<܏'bRcs&XQֳ<: 6ԂhIϢX9=Ku3ȺM,Ҳrqxky3LT2Q3b-"Dݎ}K| BcS;מm]F&l#ݼi,]Ҧ= X7*չ9bz>0d@BlEY,?k7j6)K꫻u񋲬 v֒2YYۚLV2˨`ɚ+kA{,G[-BxEIVE=\sZb Qqؘ@xME_~1 ?-D.^L,vI0@( D1& MT0H=H4NxcW5_U3y_߫WՓa /܁{ (%ƘumE}CyBmoj5kчCF_}OoDu۫pM 109_c(_>~Evvϝf+>2A6U뇂ƣ{ûmln=}Aƿ3VG#4~7ց?&tiEpE\>^Ή) GLs!{w{|Om [J8fK`'+^?<GcוpubVq$ ɗ'ws1Y8;_"X嵟>37ByĶ.a wU\% gb5*Y3x&6-@BXWB`{iʤZ`NYk܅%)d~&{y:oIz<\ï-Anl b㰦6_Yz^f~Q;4y'џB'㍵SLsUp].3 ܸqfffp_LÙ3g`߾}iչ[0{|Y6ޫ+>{Voa❱vɨ\3jơCqǘ>boȨ.2h@ŀq,7dTx,ujX1@_-omGX\WhL.0RXG`䃛}ˇjQɨif,1ֵukb:ڦ0G1 !"qLáQAJeĤx]6 90RS! #! !00dPP&$MJ(Ѥ3)$#$#$=914dd L &FvJyP`r`4FzBd 47Fj0THB SiB!4>0H[{ef5>g0SJSDlj= 92L#'v`Uf%IPФ`$1 q֘x! $ X!@ me Y|Y4;h17_4yF! caJ`4 cI0|pZ;7!!_Fx|j1R FO$vh Xʕ-1Q&<79,l0\00)sdd0`˻1eF 2h 8v[̕1Iiٗj1(_]ej20H;7gUbꘐ! y2S?F JqmgS3}/`ύ ·4ax1PQ0-8 & v/@%xKBC$.X@}O4̩,[(& vT92az4i*n[ |ڎa(1)6M͓;e_cL:{^VJ|dC3L7*GM6jhG!:j3i?qݹ=B[׊{Y,xYoUȆn*D+DO6^()QpD$@*qaE q#dzJ~NB;ُı?Ajy?kog{3Ɗ~ߠ@b4I%B#bF \\8,$$ Hl'-X&Y!ydƣq`ޡPmz^[/$RL۩޹\m\`k,X{Qםst.Uxsl+䟏whT~+ZgULq1k6.\ps߾߯9d?엽Az}@grBSlņÀw!?ycy+}~4uuxހkc80z㹯98F޷>. |&¸giLypq35H"y8;s'~S ߅t܄{w #Zpu܀OèΞpŠ;R)`h<ƧcPG^klD];nV}*͓SsZDbώ<-K9-lbIE_'"9CaNCAdV΀r:]2rbڑsPUtA?Dr#ߧt@DTgZ]qn}qΣ<=0f4O)T љ*vQc q09C,Ke8&b+حG.FADEdNq D[}B WC"ՒO%N:)ZHЉZ*N?x5ιPu/W*9et}=_vgz{Hr9G&4 Ni5И=]\sjNͩ95ԜSs+(4[j$QS3(D;]='-M|7[Ή]y7iG^ֶHI9G4QERKRd4ro˖ᑇ>4mWnQZ{Tt y*)x:H0M$ g VI(TRVAZ5bU544T x&xoE߮Ȇډ ZDH94rD" JJܸ!$C"rDđ9YޅR]]R.zY/g潙yތӊEQT du0{<, b e5 2c1wnmyx*H`qpUW ~|')CEsL4fԖAUd E;8W͉_:CYǧg{U߁KPa?(&xuh5>ʴʳUտWޏ}곳Ѵ<ͻjcCҨ ChlnϗDzMla@u=6LS##e匜>>Ĭ 7py||?jQ8bsxt(ʬlgmyٗj\8: DFw]߾߲?p1wG~8B nr[iը"0oE靦Q^TnۡRCzYa@G:0:N [+BX~VJ< 嗊8WW T T騪FSC~ Oینifsۨ.gt>%R}ǪcT_4 RT3 > -k5lA>WO*+M0  T*Cc/|/i v L R:l QG]U0H4]3cL:^G;˽~X7?b/Iߎ0Fҙ0I[zt ,b ;i^ wxF) pթ9$,j A;3isˬ\Q}JB9#f ln^F(ps&Ɉ?Щ9ԅ F;/U1TAf. 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R$JGw4@b$#§ϑPl E4@b$gK)2%P.J^MC?2$5 D" /^.ct2$tk7v-W!TsZ2$*Ÿ`Ve s2$c#hY67=i2$.li%z&2$|!|) >b$4 fov! R$*&V6{R$wi}ibJ8.#tO3b$Kj`1Xj6!2$CE6>ʱٴ%2$nkӧW[$yS=.<<L2$v`d zcg3 b2$F XmAJ2$zHc͢~Bx2$*pV rXaR2$+p b$$(7c5W( b$2E̷d;< b$7l` gAaD7Y  b$u@ytİuG E b$kK.3) b$:=U9 b$SkφC8ք5 b$Uo28 b$B,!{Ksi. 2$2`VF%y$dF p 2$> Y #!׵W>6g 2$$B^&릈68Jb[ "$,k8IQ%5 "$ |fD8 2$(waE* 2$bw8KZ[ b$ܭ)UM 2$¿5k& 2$d&4^8UVtA 2$}~ܭ9VWFXJ 2$=y HՊ5;?k 2$ӅrݮK W;<  2$^fO^XϤ b$VrPTުkrn7 b$ɿq!#q\/l\ b$z=VXx b$vkY: RGժx b$֔Gz!s> b$)BѰf b$^.(e+M b$U "@7y}.65 $2$(U<>,HVC b$52'ǨI u b$vHdZKɨa b$:~-m $$$$$$$$$b$d;֮ug-X=k b$Lٮ8#H  b$_p&ˆ1" b$RHc9<| 9& b$kF֏(%>>* b$*u;ف" a- b$QKU యJo96 c $@g4+d+dv 0pppp@  <4!d!d 0,<4BdBd 0,uʚ;2Nʚ;<4dddd{ 0:2___PPT9/ 0?&, Chapter 5O =9Chapter 5 Stereochemistry     Cahn-Ingold-Prelog RulesN            @Assign a priority number to each group attached to the chiral carbon. Atom with highest atomic number assigned the highest priority #1. In case of ties, look at the next atoms along the chain. Double and triple bonds are treated like bonds to duplicate atoms. => AZA A  `5}796 Stereoisomers  Geometric isomers: cis-trans isomers. Enantiomers: nonsuperimposable mirror images, different molecules. => FZ  $ SF        l   Chirality     , Handedness : right glove doesn t fit the left hand. Mirror-image object is different from the original object. => Z  Chiral Carbons  Tetrahedral carbons with 4 different attached groups are chiral. Its mirror image will be a different compound (enantiomer). => <Z K   A/Mirror Planes of Symmetry  vIf two groups are the same, carbon is achiral. (animation) A molecule with an internal mirror plane cannot be chiral.*Hw&7 *&    J  B0 (R), (S) Nomenclature6  Different molecules (enantiomers) must have different names. Usually only one enantiomer will be biologically active. Configuration around the chiral carbon is specified with (R) and (S). L=7>   Assign Priorities   'Absolute Conformation Assign (R) or (S)6((  Working in 3D, rotate molecule so that lowest priority group is in back. Draw an arrow from highest to lowest priority group. Clockwise = (R), Counterclockwise = (S) =>PIZ5PnFH  N1 Properties of Enantiomers  Same boiling point, melting point, density Same refractive index Different direction of rotation in polarimeter Different interaction with other chiral molecules Enzymes Taste buds, scent => *ZfZf*d         Optical Activity  7Rotation of plane-polarized light Enantiomers rotate light in opposite directions, but same number of degrees. => 8    Polarimetry     Use monochromatic light, usually sodium D Movable polarizing filter to measure angle Clockwise = dextrorotatory = d or (+) Counterclockwise = levorotatory = l or (-) Not related to (R) and (S) => lr) Fa             Specific Rotation  Observed rotation depends on the length of the cell and concentration, as well as the strength of optical activity, temperature, and wavelength of light.!   Calculate [a]D<   A 1.00-g sample is dissolved in 20.0 mL ethanol. 5.00 mL of this solution is placed in a 20.0-cm polarimeter tube at 25C. The observed rotation is 1.25 counterclockwise. => Fx!O*b       O23-Biological Discrimination  Racemic Mixtures  Equal quantities of d- and l- enantiomers. Notation: (d,l) or () No optical activity. The mixture may have different b.p. and m.p. from the enantiomers! => z  Racemic Products  mIf optically inactive reagents combine to form a chiral molecule, a racemic mixture of enantiomers is formed.n!nn  Optical Purity  $Also called enantiomeric excess. Amount of pure enantiomer in excess of the racemic mixture. If o.p. = 50%, then the observed rotation will be only 50% of the rotation of the pure enantiomer. Mixture composition would be 75-25. => %Z%*         Calculate % Composition  Chirality of Conformers     If equilibrium exists between two chiral conformers, molecule is not chiral. Judge chirality by looking at the most symmetrical conformer. Cyclohexane can be considered to be planar, on average. => VZ 3 $FS     /     o  Mobile Conformers  Nonmobile Conformers      EIf the conformer is sterically hindered, it may exist as enantiomers.F!FF  Allenes  Chiral compounds with no chiral carbon Contains sp hybridized carbon with adjacent double bonds: -C=C=C- End carbons must have different groups.2 _  Fischer Projections  Flat drawing that represents a 3D molecule A chiral carbon is at the intersection of horizontal and vertical lines. Horizontal lines are forward, out-of-plane. Vertical lines are behind the plane.  W3 Fischer Rules  `Carbon chain is on the vertical line. Highest oxidized carbon at top. Rotation of 180 in plane doesn t change molecule. Do not rotate 90! Do not turn over out of plane! => tU#!  Fischer Mirror Images  VEasy to draw, easy to find enantiomers, easy to find internal mirror planes. Examples:W  Fischer (R) and (S)6   Lowest priority (usually H) comes forward, so assignment rules are backwards! Clockwise 1-2-3 is (S) and counterclockwise 1-2-3 is (R). Example:l" !   ]4Draw (R)-2-butanol"   Diastereomers  Stereoisomers that are not mirror images. Geometric isomers (cis-trans) Molecules with 2 or more chiral carbons. => .8  /    {  Alkenes  DCis-trans isomers are not mirror images, so these are diastereomers.,E!6 8  3        Ring Compounds  \Cis-trans isomers possible. May also have enantiomers. Example: trans-1,3-dimethylcylohexane$]@8  G      !Two or More Chiral Carbons  Enantiomer? Diastereomer? Meso? Assign (R) or (S) to each chiral carbon. Enantiomers have opposite configurations at each corresponding chiral carbon. Diastereomers have some matching, some opposite configurations. Meso compounds have internal mirror plane. Maximum number is 2n, where n = the number of chiral carbons. => d) p~          z     3      "Examples   #$Fischer-Rosanoff Convention: D and L%%$*      Before 1951, only relative configurations could be known. Sugars and amino acids with same relative configuration as (+)-glyceraldehyde were assigned D and same as (-)-glyceraldehyde were assigned L. With X-ray crystallography, now know absolute configuration of : D is (R) and L is (S). No relationship to dextro- or levorotatory. => Z ZV p~y    !    |         L  $ D and L Assignments.((   %!Properties of Diastereomers    8Diastereomers have different physical properties: m.p., b.p. They can be separated easily. Enantiomers differ only in reaction with other chiral molecules and the direction in which polarized light is rotated. Enantiomers are difficult to separate. => 9Z5   ,  &"Resolution of Enantiomers  ]React a racemic mixture with a chiral compound to form diastereomers, which can be separated.^!^*7       4.)Chromatographic Resolution of Enantiomers*  2, @B(  `  c $A8 ??P    <pћ  ] cis or trans?     <x՛+ 1,$D 0 RE and Z Based on Priority:   3k  <ٛo ,$D 0 [Cahn- Ingold-Prelongo: 1. Atomic Number 2. Atomic weight 3. Atomic number of the next atom\ \ 6G  <DޛF D,$D 0 F----------------    6, P,$D 0 >     <@` ],$D 0 835  3  <g ,$D 0 853  3  <@@D,$D 0 91 $f  <pd,$D 0 72    <',$D  0 817  3  <<D ,$D  0 79  3  <`',$D  0 72    <lT,$D  0 91 $f  < F,$D  0 dHigher priority at the opposite side of pi bond (E) Higher priority at the same side of pi bond (Z)ve            <0 ? ,$D 0 ? (E) ? ethane    6Ĵ ]d ,$D 0 +(E)-1-bromo-2-chloro- 2-fluoro-1-iodoethene, , !   S ` 0   %Geometric isomers: cis-trans isomers&& .      H  0޽h ? ̙33r`5 ots( 0  !#$%&'()*+,-./0123456789:;<=>O+'0< hp   Stereochemistry Jo BlackburnryHamidik113Microsoft PowerPointP@I@&~@SR@`QG g  !& &&#TNPP,2OMi & TNPP &&TNPP    --- !-----iyH--j}w@> KQwZw0- @"Arialw@ ;QwZw0- 33.2 _ Chapter 5+! !!!. 33.2 e Stereochemistry'!! ! 1 .--!7-- 33@"Arialw@> TQwZw0- .!2 `Organic Chemistry   .@"Arialw@ =QwZw0- . 2 `, 5T .@"Arialw@> VQwZw0- . 2 U>th.@"Arialw@ ?QwZw0- .2 `^Edition . .2 [L. G. 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Double and triple bonds are treated like bonds to duplicate atoms. => AZAA  `5}796 Stereoisomers  Geometric isomers: cis-trans isomers. Enantiomers: nonsuperimposable mirror images, different molecules. => FZ  $ SF        l   Chirality     , Handedness : right glove doesn t fit the left hand. Mirror-image object is different from the original object. => Z  Chiral Carbons  Tetrahedral carbons with 4 different attached groups are chiral. Its mirror image will be a different compound (enantiomer). => <Z K   A/Mirror Planes of Symmetry  vIf two groups are the same, carbon is achiral. (animation) A molecule with an internal mirror plane cannot be chiral.*Hw&7 *&    J  B0 (R), (S) Nomenclature6  Different molecules (enantiomers) must have different names. Usually only one enantiomer will be biologically active. Configuration around the chiral carbon is specified with (R) and (S). L=7>   Assign Priorities   'Absolute Conformation Assign (R) or (S)6((  Working in 3D, rotate molecule so that lowest priority group is in back. Draw an arrow from highest to lowest priority group. Clockwise = (R), Counterclockwise = (S) =>PIZ5PnFH  N1 Properties of Enantiomers  Same boiling point, melting point, density Same refractive index Different direction of rotation in polarimeter Different interaction with other chiral molecules Enzymes Taste buds, scent => *ZfZf*d         Optical Activity  7Rotation of plane-polarized light Enantiomers rotate light in opposite directions, but same number of degrees. => 8    Polarimetry     Use monochromatic light, usually sodium D Movable polarizing filter to measure angle Clockwise = dextrorotatory = d or (+) Counterclockwise = levorotatory = l or (-) Not related to (R) and (S) => lr) Fa             Specific Rotation  Observed rotation depends on the length of the cell and concentration, as well as the strength of optical activity, temperature, and wavelength of light.!   Calculate [a]D<   A 1.00-g sample is dissolved in 20.0 mL ethanol. 5.00 mL of this solution is placed in a 20.0-cm polarimeter tube at 25C. The observed rotation is 1.25 counterclockwise. => Fx!O*b       O23-Biological Discrimination  Racemic Mixtures  Equal quantities of d- and l- enantiomers. Notation: (d,l) or () No optical activity. The mixture may have different b.p. and m.p. from the enantiomers! => z  Racemic Products  mIf optically inactive reagents combine to form a chiral molecule, a racemic mixture of enantiomers is formed.n!nn  Optical Purity  $Also called enantiomeric excess. Amount of pure enantiomer in excess of the racemic mixture. If o.p. = 50%, then the observed rotation will be only 50% of the rotation of the pure enantiomer. Mixture composition would be 75-25. => %Z%*         Calculate % Composition  Chirality of Conformers     If equilibrium exists between two chiral conformers, molecule is not chiral. Judge chirality by looking at the most symmetrical conformer. Cyclohexane can be considered to be planar, on average. => VZ 3 $FS     /     o  Mobile Conformers  Nonmobile Conformers      EIf the conformer is sterically hindered, it may exist as enantiomers.F!FF  Allenes  Chiral compounds with no chiral carbon Contains sp hybridized carbon with adjacent double bonds: -C=C=C- End carbons must have different groups.2 _  Fischer Projections  Flat drawing that represents a 3D molecule A chiral carbon is at the intersection of horizontal and vertical lines. Horizontal lines are forward, out-of-plane. Vertical lines are behind the plane.  W3 Fischer Rules  `Carbon chain is on the vertical line. Highest oxidized carbon at top. Rotation of 180 in plane doesn t change molecule. Do not rotate 90! Do not turn over out of plane! => tU#!  Fischer Mirror Images  VEasy to draw, easy to find enantiomers, easy to find internal mirror planes. Examples:W  Fischer (R) and (S)6   Lowest priority (usually H) comes forward, so assignment rules are backwards! Clockwise 1-2-3 is (S) and counterclockwise 1-2-3 is (R). Example:l" !   ]4Draw (R)-2-butanol"   Diastereomers  Stereoisomers that are not mirror images. Geometric isomers (cis-trans) Molecules with 2 or more chiral carbons. => .8  /    {  Alkenes  DCis-trans isomers are not mirror images, so these are diastereomers.,E!6 8  3        Ring Compounds  \Cis-trans isomers possible. May also have enantiomers. Example: trans-1,3-dimethylcylohexane$]@8  G      !Two or More Chiral Carbons  Enantiomer? Diastereomer? Meso? Assign (R) or (S) to each chiral carbon. Enantiomers have opposite configurations at each corresponding chiral carbon. Diastereomers have some matching, some opposite configurations. Meso compounds have internal mirror plane. Maximum number is 2n, where n = the number of chiral carbons. => d) p~          z     3      "Examples   #$Fischer-Rosanoff Convention: D and L%%$*      Before 1951, only relative configurations could be known. Sugars and amino acids with same relative configuration as (+)-glyceraldehyde were assigned D and same as (-)-glyceraldehyde were assigned L. With X-ray crystallography, now know absolute configuration of : D is (R) and L is (S). No relationship to dextro- or levorotatory. => Z ZV p~y    !    |         L  $ D and L Assignments.((   %!Properties of Diastereomers    8Diastereomers have different physical properties: m.p., b.p. They can be separated easily. Enantiomers differ only in reaction with other chiral molecules and the direction in which polarized light is rotated. Enantiomers are difficult to separate. => 9Z5   ,  &"Resolution of Enantiomers  ]React a racemic mixture with a chiral compound to form diastereomers, which can be separated.^!^*7       4.)Chromatographic Resolution of Enantiomers*  2, 1)@ (    <6hl,$D 0 ] cis or trans?     <:h+ },$D 0 RE and Z Based on Priority:   3  c $AD ??q I 8 $D  0  <?h0f*,$D  0 F----------------    6     <Gh\t,$D 0 71  3  <Jh-,$D 0 812  3  <Mh@D ,$D 0 91 $f  <Qh-,$D 0 72    <Uh p,$D 0 812  3  <WhM ,$D 0 812  3  <`[h-,$D 0 72    <@h ,$D 0 91 $f  <,bh m ,$D 0 b(E) ? pentyne    6ehc ,$D 0 (E)-3-ethyl-2-pentene-4-yne  ,  <AE ??@ N8 $D 0  <AF ??p  8 $D 0   <AG ?? 08 $D 0H  0޽h ? ̙33r}Ӆ7 \Root EntrydO) Pictures9 Current User?/SummaryInformation(lfc  !#$%&'()*+,-./0123456789:;<=>Ring CompoundsTwo or More Chiral Carbons Examples%Fischer-Rosanoff Convention: D and LD and L AssignmentsProperties of DiastereomersResolution of Enantiomers*Chromatographic Resolution of EnantiomersPowerPoint Presentation  Fonts UsedDesign TemplateEmbedded OLE Servers Slide Titles0@"Arialw@ QwZw0-_tGCCCDGCCCDi2 `,       !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abd ghijklmnopqrstuvwxyz