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More reactive than sigma bond. Bond dissociation energies: C=C BDE 146 kcal/mol C-C BDE -83 kcal/mol Pi bond 63 kcal/mol =>\ZZfZ    f& fC"    Orbital Description   FSigma bonds around C are sp2 hybridized. Angles are approximately 120 degrees. No nonbonding electrons. Molecule is planar around the double bond. Pi bond is formed by the sideways overlap of parallel p orbitals perpendicular to the plane of the molecule. =>GZf f&f/fff z &    t  Bond Lengths and Angles   zHybrid orbitals have more s character. Pi overlap brings carbon atoms closer. Bond angle with pi orbitals increases. Angle C=C-H is 121.7 Angle H-C-H is 116. 6 =>juIZ @    R    U  Pi Bond   Sideways overlap of parallel p orbitals. No rotation is possible without breaking the pi bond (63 kcal/mole). Cis isomer cannot become trans without a chemical reaction occurring. R* ft @     G    D  Elements of Unsaturation   A saturated hydrocarbon: CnH2n+2 Each pi bond (and each ring) decreases the number of H s by two. Each of these is an element of unsaturation. To calculate: find number of H s if it were saturated, subtract the actual number of H s, then divide by 2. =>DZ ff ff fff  D   Propose a Structure:   First calculate the number of elements of unsaturation. Remember: A double bond is one element of unsaturation. A ring is one element of unsaturation. A triple bond is two elements of unsaturation. =>BZZ* f   f#  f#  f   "      Heteroatoms     Halogens take the place of hydrogens, so add their number to the number of H s. Oxygen doesn t change the C:H ratio, so ignore oxygen in the formula. Nitrogen is trivalent, so it acts like half a carbon.lZ$f$ $f,$$f@$$f.$&        Structure for C6H7N?6   <Since nitrogen counts as half a carbon, the number of H s if saturated is 2(6.5) + 2 = 15. Number of missing H s is 15  7 = 8. Elements of unsaturation is 8 2 = 4. =>4 {      IUPAC Nomenclature   3Parent is longest chain containing the double bond. -ane changes to -ene. (or -diene, -triene) Number the chain so that the double bond has the lowest possible number. In a ring, the double bond is assumed to be between carbon 1 and carbon 2. =>4 ff 4    t5                     Name These Alkenes    Alkene Substituents    8+ 5*  Common Names   +Usually used for small molecules. Examples: ,   Cis-trans Isomerism    )Similar groups on same side of double bond, alkene is cis. Similar groups on opposite sides of double bond, alkene is trans. Cycloalkenes are assumed to be cis. Trans cycloalkenes are not stable unless the ring has at least 8 carbons. =>\*Z6=& ,        3                   w   Name these:   E-Z Nomenclature.   CUse the Cahn-Ingold-Prelog rules to assign priorities to groups attached to each carbon in the double bond. If high priority groups are on the same side, the name is Z (for zusammen). If high priority groups are on opposite sides, the name is E (for entgegen). =>zD>? Z        E    B   Example, E-Z.    Commercial Uses: Ethylene   Commercial Uses: Propylene   Other Polymers   Stability of Alkenes   Measured by heat of hydrogenation: Alkene + H2 Alkane + energy More heat released, higher energy alkene.8s1$=Z'         ,      Substituent Effects   More substituted alkenes are more stable. H2C=CH2 < R-CH=CH2 < R-CH=CH-R < R-CH=CR2 < R2C=CR2 unsub. < monosub. < disub. < trisub. < tetra sub. Alkyl group stabilizes the double bond. Alkene less sterically hindered.Z*       :I_                 8      Disubstituted Isomers      }Stability: cis < geminal < trans isomer Less stable isomer is higher in energy, has a more exothermic heat of hydrogenation.@         e  Cycloalkene Stability      Cis isomer more stable than trans. Small rings have additional ring strain. Must have at least 8 carbons to form a stable trans double bond. For cyclodecene (and larger) trans double bond is almost as stable as the cis. => Z N       ;    @  ,#Bredt s Rule    A bridged bicyclic compound cannot have a double bond at a bridgehead position unless one of the rings contains at least eight carbon atoms. Examples::9 f4 f&       Physical Properties   kLow boiling points, increasing with mass. Branched alkenes have lower boiling points. Less dense than water. Slightly polar Pi bond is polarizable, so instantaneous dipole-dipole interactions occur. Alkyl groups are electron-donating toward the pi bond, so may have a small dipole moment. =>:|ZZ| " &        Polarity Examples   !Alkene Synthesis Overview    E2 dehydrohalogenation (-HX) E1 dehydrohalogenation (-HX) Dehalogenation of vicinal dibromides (-X2) Dehydration of alcohols (-H2O) => LbB t                   i  "Removing HX via E2    Strong base abstracts H+ as X- leaves from the adjacent carbon. Tertiary and hindered secondary alkyl halides give good yields. Use a bulky base if the alkyl halide usually forms substitution products. => B     %Some Bulky Bases   &Hofmann Product   UBulky bases abstract the least hindered H+ Least substituted alkene is major product.$V),&=      .%E2: Diastereomers&       VStereospecific reaction: (S, R) produces only trans product, (R, R) produces only cis.rW! 4  D      /'E2: Cyclohexanes&       )Leaving groups must be trans diaxial. =>**!&      (E2: Vicinal Dibromides&        pRemove Br2 from adjacent carbons. Bromines must be anti-coplanar (E2). Use NaI in acetone, or Zn in acetic acid.$q g&K    #  'Removing HX via E1   Secondary or tertiary halides Formation of carbocation intermediate Weak nucleophile Usually have substitution products too => @+          j  ) Dehydration of Alcohols   *Reversible reaction Use concentrated sulfuric or phosphoric acid, remove low-boiling alkene as it forms. Protonation of OH converts it to a good leaving group, HOH Carbocation intermediate, like E1 Protic solvent removes adjacent H+ =>:+!A tU         0         _  *!Dehydration Mechanism   -$Industrial Methods   |Catalytic cracking of petroleum Long-chain alkane is heated with a catalyst to produce an alkene and shorter alkane. Complex mixtures are produced. Dehydrogenation of alkanes Hydrogen (H2) is removed with heat, catalyst. Reaction is endothermic, but entropy-favored. Neither method is suitable for lab synthesis =>v t]q t Qqt+    )         4      +"/$  ` ̙33` ` ff3333f` 333MMM` f` f` 3>?" dd@,?" dd@  " @ ` n?" dd@   @@``PR    @ ` ` p>> =5(    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  0tc  ``   Z*  0f  `    oAlkenes Structure and Syn  0dY  `    \*H  0޽h ? ̙33 $Blank Presentation 0 zrP| (  | | 0C P   /  P*   | 0C     R*  d | c $ ?   | 0K  @  RClick to edit Master text styles Second level Third level Fourth level Fifth level!     S | 6C `P   P*   | 6tC `   R*  H | 0޽h ? ̙3380___PPT10.  0(  l  C A p      6A P` .Organic Chemistry, 5th Edition L. G. Wade, Jr.J/(2H  0޽h ? ̙33y___PPT10Y+D=' = @B +  80  (   r  S +#.<* !%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* !@%(D ' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* @\%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* \r%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* r%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* %(+8+0+ A  +   `J( wz kl r  S Է `0     C cA  <$ 0   H  0޽h ? ̙33  ___PPT10 .+} <Ds ' = @B D. ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*)%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*)O%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*Oh%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*h%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*G%(+8+0+A  +  0#*(  l  C 0/ 0  /    C / <$ 0 /  ` " C 8A FG07_00-03UN-01pv # s @/A%FG07_01-01"` H  0޽h ? ̙33  ___PPT10s .+} <D ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*'%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*'N%(Ds' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*Nu%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*u%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(+8+0+/  +A  D<(  l  C -/ P`  /    C -/  <$ 0 /  l  Jy  Jy,$D 0^  C .AFG07_02-01 0M  <// YJy 2=>H  0޽h ? ̙33  ___PPT10} .+fjD ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<**%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<**o%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*o%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(+8+0+/  +   pJ( 1P[ r  S l=/ ` 0  /    C T>/ ` <$ 0 /  H  0޽h ? ̙33  ___PPT10 .+} <D* ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*"%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*"c%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*c%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*D%(+8+0+/  +  ~ ( _t.  r  S Q/ `0  /    C M/  <$ 0 /    0Z/ Ps  dfor C5H8@      H  0޽h ? ̙33  ___PPT10 .+J\Ds ' = @B D. ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* 8%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* 8B%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* Bp%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* p%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* %(+8+0+ /  +  $( ff $r $ S PT/ `0  /   $ C g/  <$ 0 /   l p 0 $ p0,$D 0 t  P $p 0,$D 0 $ <lq/  0 C`B $ 0D``B $ 0D@`B  $ 0D @`B  $ 0D`  $ <u/   H  $ <x/ 0P H  $ <L|/ 0$0 C`B $ 0D`B $ 0D @`B $ 0D` $ <@/ !  H $ </ !0 P H $ <8/ PO0 N`B $ 0D $ <(/ ]Q 0 C`B $ 0D @`B $ 0D` $ <4/ a `  H $ <d/ a0` P H`B $ 0D0  `B $ 0D` $ <P/ A0@P H $ 6/ p   A =>"# H $ 0޽h ? ̙33  ___PPT10} .+$&&D ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*$P%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*$P%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*$%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*$%(+8+0+$/  +{   (J(  (r ( S ԰/ `0  /   ( C / <$ 0 /  H ( 0޽h ? ̙33ia___PPT10A.+} <D' = @B D' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*(\%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*(\%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*(%(+8+0+(/  +    ,J( r  ,r , S / `0  /   , C / 0<$ 0 /  H , 0޽h ? ̙33  ___PPT10 .+} <D* ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*,4%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*,4_%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*,_%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*,4%(+8+0+, ++  L D 0 0( r  0r 0 S / `0  /  h 0 # A@ ,$D 0h 0 # A@P ,$D 0h 0 # A 0U ,$D 0h 0 # A  p,$D 0h 0 # A 0 nZ ,$D  0  0 0/ P,$D 0 b1-butene    0 <|/   ,$D  0 k2-methyl-2-butene   0 </  B ,$D  0 n3-methylcyclopentenev  0 <x/ n t ,$D  0 B2-sec-butyl-1,3-cyclohexadiene 2(1-methylpropyl-1,3-cyclohexadiene2C=> U  0 <T/  V ,$D   0 ;3-propyl-1-heptene =>*<)!,.H 0 0޽h ? ̙33""___PPT10!+ȺD ' = @B Dz ' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*0%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* 0%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*0%(D{' =%(D#' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* 0%(D' =+4 8?\CB#ppt_xBCB#ppt_xB*Y3>B ppt_x<* 0D' =+4 8?dCB1+#ppt_h/2BCB#ppt_yB*Y3>B ppt_y<* 0D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*0%(D{' =%(D#' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* 0%(D' =+4 8?\CB#ppt_xBCB#ppt_xB*Y3>B ppt_x<* 0D' =+4 8?dCB1+#ppt_h/2BCB#ppt_yB*Y3>B ppt_y<* 0D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*0%(D' =%(D?' =%(D' =A@BBBB0B@B%(D' =1:Bvisible*o3>+#.<* 0%(D' K=+4 8?\CB#ppt_xBCB#ppt_xB*Y3>B ppt_x<* 0D' K=+4 8?dCB1+#ppt_h/2BCB#ppt_yB*Y3>B ppt_y<* 0D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*0%(D' =%(D?' =%(D' =A@BBBB0B@B%(D' =1:Bvisible*o3>+#.<* 0%(D' K=+4 8?\CB#ppt_xBCB#ppt_xB*Y3>B ppt_x<* 0D' K=+4 8?dCB1+#ppt_h/2BCB#ppt_yB*Y3>B ppt_y<* 0++0+ 0A  ++0+ 0/  ++0+ 0/  ++0+ 0/  ++0+ 0/  +    @8 ( r  8r 8 S $ `0  $  l   8,$D 0 8 <$ & I= CH2( 8 < $  imethylene (methylidene) l    8 ,$D 0 8 <$   N - CH = CH2(  8 <`$ 2Z  avinyl (ethenyl)2l   8 ,$D 0 8 <\$   j- CH2 - CH = CH2>  8 <p$  \allyl (2-propenyl)Ol 0@ M 8@ 0 M,$D 0  8 <%$ 00 P  Name: <  8 # A@ Ml  > 8 >,$D 0v  8 3 A  >,$D 0 8 <($ P m  A =>"# < 8 <-$ : `0  0 methylenecyclohexane ethenylbenzeneP1     , H 8 0޽h ? ̙33v n ___PPT10N +:9D2 ' = @B D ' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<* 8%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<* 8%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*8%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*8%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*8%(+   <(   0 6A +?`@ +  $  0 NA) ,? ?` H ,$D 0 $  0 ZA, -?AA ? H -$D  0 $  0 ZA- .?AA ?@H .$D  0 $ H  0޽h ? ̙33  ___PPT10 . `4+WDd ' = @B D ' = @BA?%,( < +O%,( < +D' =%(D' =%(DG' =4@BBB B%(D' =1:Bvisible*o3>+#.<*%(D' =-6B'blinds(horizontal)*<3<*D' =%(D' =%(D1' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(D' =-m6Bbox(in)*<3<*Dn' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(D' =+4 8?\CB#ppt_xBCB#ppt_xB*Y3>B ppt_x<*D' =+4 8?dCB1+#ppt_h/2BCB#ppt_yB*Y3>B ppt_y<*+  @(    0$ 8H  JIn a ring, the double bond is assumed to be between carbon 1 and carbon 2.K 2K J    c $A+ #?? 8 #$D  0  c $A* !??@ 8 !$D  0A  <J$ 0  ,$D  0 )4-ethyl-3-methyl-7-brormo-cyclohept-1-ene** > H  0޽h ? ̙33C ; ___PPT10 +pD ' = @B D ' = @BA?%,( < +O%,( < +DR' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(D' =+4 8?RCBBCB#ppt_wB*Y3>B ppt_w<*D' =+4 8?RCBBCB#ppt_hB*Y3>B ppt_h<*D_' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(D' =+4 8?RCBBCB#ppt_wB*Y3>B ppt_w<*D' =+4 8?RCBBCB#ppt_hB*Y3>B ppt_h<*+8+0+$  +   `X<(   <r < S |T$ `0  $   < C dU$ <$ 0 $  l p`,  <p`, ,$D 0 < <A ??pP,   < 0W$  `@  2=> 2H < 0޽h ? ̙33\T___PPT104.+Pv@D' = @B D' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*<"%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*<",%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*<%(+8+0+<$  +   @J( @ @r @ S `0    @ C (<$ 0  H @ 0޽h ? ̙33  ___PPT10 .+} <D* ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*@;%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*@;}%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*@}%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*@*%(+8+0+@$  +  D(( `@ Dr D S s$ `0  $   D <A ??p 8 $D 0 D <A ?? 8 $D 0 D <v$   ,$D 0 otrans-2-pentene* Z D <|$ `  ,$D 0 @cis-1,2-dibromoethene =><A)# 6 D 6 $ `   ? "# H D 0޽h ? ̙33  ___PPT10 +D ' = @B D ' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*D%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*D%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*D%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*D%(+p+0+D$  ++0+D$  +{   HJ(   Hr H S $ `0  $   H C Ԕ$ <$ 0 $  H H 0޽h ? ̙33ia___PPT10A.+} <D' = @B D' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*Hl%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*Hl%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*HD%(+8+0+H$  +    PL0 Y ( ( Lr L S $ `0  $  x L <A ??P#:  l   L ,$D 0 L <$   31f L <`$    32fl 0   L0 ,$D 0 L B8$ 0P 31f  L B$ @   32f  L <X$  &z ,$D 0 J2Z,l `   L` ,$D 0  L B@$    32f L B$ ` 4  31fl 0   L0  ,$D 0 L B$ 0   31f L B$ 0   32f L <$  ? / ,$D 0 J5E, L <$  ,$D 0 s(2Z, 5E)-3,7-dichloro-2,5-octadiene =>TtP!, WH L 0޽h ? ̙33___PPT10+ GD' = @B D' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*L%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<* L%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* L%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*L%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*L%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*L%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*L%(++0+ L$  ++0+L  ++0+L  +L  `P(  Pl P C A ``   | P 6A P p =>\ P S 4HaA'FG07_03-010H P 0޽h ? ̙33L  pT( @ Tl T C   ``  $  | T 6#   =>\ T S 4)A'FG07_03-01k` H T 0޽h ? ̙33F  X( zy0 Xl X C ( `    | X 6+ P p =>V X C .A FG07_04-01H X 0޽h ? ̙33  IA \0 (  * \l \ C T0 P     \ C P1 @<$ 0   yl  \,$D 0   \# ,$D 0 \ <3 p} A =>"# d \ S 45AFG07_05-01<T @   \# @  Z  \ s * ~   \ B8    = 30.3 kcal   \ B= @   = 27.6 kcal H \ 0޽h ? ̙33\T___PPT104.+g&D' = @B D' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*\I%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*\Is%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*\%(+8+0+\  +   `L( _ `l ` C J P     ` C K  <$ 0   l    ` ,$D 0j  ` c :0AFG07_06-01 d  ` S 4õAFG07_06-01@   ` <@N 6  2=>H ` 0޽h ? ̙33  ___PPT10} .+BD ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*`%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*`%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*`%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<* `%(+8+0+`  +  +d(  dl d C a P     d C b `<$ 0   P l ` +d`,$D 0 d B l ?  O 27.6 kcal   @` d Bt ?0  P  @` d B} ? 0  Trans-2-butene  @`  d B$ ?P   O 28.0 kcal   @`  d Bh ?0 P    (CH3)2C=CH2N    @`  d B( ?P 0  Q Isobutylene   @`  d BL ?P  O 28.6 kcal   @`  d B ?0 P  P  @` d B ?0 P   Cis-2-butene  $ @`fB d 6o ?`B d 01 ?P P `B d 01 ?  fB d 6o ?fB d 6o ?`B d 01 ?0 0 `B d 01 ?fB d 6o ?` &d 0A? 0d ` (d 0A? 0 0 *d <  p@` 2=>H d 0޽h ? ̙33\T___PPT104.+J{D' = @B D' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*d)%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*d)~%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*+d%(+8+0+d  +   hJ(  hr h S  `0  A   h C  <$ 0   H h 0޽h ? ̙33  ___PPT10 .+} <D* ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*h#%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*h#L%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*hL%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*h%(+8+0+h  +   4( Unstable. Violates Bredt s rule  l  pR  p ,$D 0Z  s *A!p(   <  @ R NStable. Double bond in 8-membered ring. =>OO -H  0޽h ? ̙33  ___PPT10p .+D ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<* %(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<* %(+8+0+  +  lJ(  lr l S T `0     l C < 0 <$ 0   H l 0޽h ? ̙33  ___PPT10 .+} <D\ ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*l*%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*l*V%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*lVm%(Ds' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*lm|%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*l|%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*ll%(+8+0+l  +   p,(  pr p S  `0    dB p@ <DfjJ0PdB p <DfjJ0 p <o  P   \m = 0.33 D, f f p <u  p  J m = 0$ffdB  p <DfjJdB  p@ <DfjJ |  p 6Lq  0  =>X  p 0A&?0 X p 0A(?=  H p 0޽h ? ̙33   tJ( X tr t S e `0    t C f  @<$ 0   H t 0޽h ? ̙33  ___PPT10 .+} <D* ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*t%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*t:%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*t:e%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*te%(+8+0+t  +{    xJ(  xr x S 3 `0    x C 4 p<$ 0   H x 0޽h ? ̙33ia___PPT10A.+} <D' = @B D' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*x@%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*x@%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*x %(+8+0+x  +  0(  (  r  S @ `0     s *A` ,$D 0  <|B  T ,$D 0 O(CH3CH2)3N : triethylamine =>P   2! @  s *A@ K ,$D 0  s *A/ ,$D 0  6  `}  ? "# H  0޽h ? ̙33 w ___PPT10W +D ' = @B D ' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(+8+0+  +   0(    l  C \ P     C D  P <$ 0     s *APpp ,$D 0l  )  ),$D 0  s *A @),$D 0  6 p`   A =>"# H  0޽h ? ̙33  ___PPT10p .+rD ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*+%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*+V%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(+8+0+  ++!  @00e(  x  c $  `   x  c $H     R  s *A"    < 01m B$ 'z  Z     ,$D 0Z2  s *P``B  0Dpp`B  B 0Dp@`B   0Dp@   <Ш  * 9H   <\ J  2Ph   < Z ?CH3 `B  0Dpp  < p:  Br`B  0D``  << 0 Ph`B  0D0  < !* J Hz P 0   P 0 ,$D 0  <h Pp 9HN  0    0 ,$D 0Z2  s *0 @ `B  0D  0`B  0D@ 0`B  0D 0 @  <   0  :Ph  <    GCH3(`B  0D  @  <T v  0  Ph`B  0D@     <  @ ` H`B ! 0Dp0  " <h  BrZ # s *A#  Z $ s *A$@ Yz    %   ,$D 0 6P   &  D ,$D 0Z2 ' s * P 0` `B ( 0D@p  `B )B 0D0p @0  * <    ?CH3  + <0 6   2Ph , <L Fj   Ph - < p o  H`B . 0D0 Pp `B / 0D0@ p  0 B    5 => H  0޽h ? ̙33___PPT10+n˷D' = @B Du' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%%(+T  P(  ~  s *& `0   x  c $  0   V  C .AFG07_08-01 F H  0޽h ? ̙33    `a ( Dn0ȹ l  C  @P     C  ` <$ 0    l p p,$D 0 t p@ p@,$D 0     p:,$D 0Z  s *A40 p   p ,$D 0>N  :   p Z2  s * `B  0D`B  B 0D@`B   0D@   <  * :Br   <(P t  ICH3*  < 09 =H `B  0D  < p  Br`B  0D `  < {:0 CCH3$`B  0Dj*0  <(] *J HZ  s *AP  Z  s *AP`@lB  <DjJ0 0 Z  s *AP @   6]    A =>"# H  0޽h ? ̙33  ___PPT10} .+&D ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*"%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*"G%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*Gq%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(+8+0+ +r   h`p(  r  S `0     C  <$ 0    6GB p@ U 0U 0H  0޽h ? ̙33  ___PPT10 .+} <D* ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*D%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*DU%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*U%(+8+0+ +  D(   l  C DP     C ,<$ 0  H  0޽h ? ̙33  ___PPT10 .+} <Ds ' = @B D. ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*i%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*i%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*+%(+8+0+ +   } ( `@ r  S d*`0     s *APp,$D 0l       ,$D 0  s *A  ,$D 0   6,@ }  U =>"#    H  0޽h ? ̙33___PPT10+AD~' = @B D9' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<* %(+  D(  l  C P     C p9 <$ 0  H  0޽h ? ̙33___PPT10.+} <DE' = @B D' = @BA?%,( < +O%,( < +Ds' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* %(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* u%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*u%(Ds' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* %(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* }%(+8+0+ + xp@(    66   j2End of Chapter 7 Alkenes: Structure and synthesis.33,H  0޽h ? ̙33 0 x(  R  3 |   C~  C pC| @  C  H  0޽h ? ̙33xWKOQ>δ2Ţ D HDT  MhLk.\ Wݹ%K\NJ5QÙN{{9~7[;_ R9cr9eFfظSğnqza@+ ~8uX1gWVC5h, ւrz_yI~՞)`Գ:\ͭsָ*݋}k"sSG?6S6lia-Gwsl DZ &$SeI\v$k>JbQߟKtHݬ Jܢ0 '@͋ n[ߵПr Mswr&ߦ~+Bq0K@"N:++>?v l^(ܖ l ׵z$]TQ5Df5=( h|:,:Ib:.iz2h9 NA^Yl@CKԬ$%:mxu0OU'a&aV.2)gPAaV%ªjAzJDBsD->+oc'o lJcC5 ;S1iK'n.!Yt$:MD%TbaY 2Tc<",SW`;%;yLaK> ZL}`|xH-; m a_!P' x;Hc>'m?>vEh?#xWkA34ɶiڦպMEJ ]#-IQV#MV6ҞRKĪQL-/Oh$Z_ ,NΉHq*4< I-q Oqc]"LXqzz¶n~0gG @&?__|Ų h2W leAɘw,R>vc!̡w/x# !% UCE~-81HeV/kgjA:%hqx7`7pD' yL$=$ s06i"l oB }xW]hY>OdڴN4lJQtıRIaѦ#Ӭ * > TFT}X|>,}}ز/ s'SE& ܹ9s&+-7 _ejԕfݗYv䣒I˞ʔ?Tr%O3t`=gd;1fݖ򾞾'k^|V=wo`Fuim[% ܫ=ŵyWv/sgk`u<7qK;V{e/v"'G@c FHD@ B% 8Aȇ.ߐ &43'̾)+3 %eCh4_FssѴY#-6g0B䋤y"쎖2tSm ֨wEٗr0݇tsK@LoՉ:tZN46u2R_&"t DO+ i.qdxIQtZ+Ju00RkZ Tn[I pH?C™߄^ֱnxg!]wb7 a{8"*071Ny/JS!`h~iRFcP&b [R*! /mz{* , 1qEjl~V[a!K$9Gl*1i# |4}eZBd~:7;v+,QTčL@c,(&i,&RCqLka`kvnnYS"nq!^gwgw7c% %^ 40$PK@XxWMHTQ>IM'36&pX()2l!k&p&(BK+׵]0Rs{#c>ws=!N\63!%X,fciTb3w:٦SpQ(p Ǘ5#ZOmwTNfVM;ⴋ8^X^C;%O5|Rgnw> P%Rh9'[ynO5j?DlEd@lcOb` 7/v' Q(C#v# *{}=Z_0)6ڃG"`w8z $RÑp$#~x+[`/!&uHs"XRg['c8ކi7<xW_LgݡBRԃ1 1j$0^@sIm5"}J?oMB1(MF3.{ݝ77߷wJ|7Ȣ `!"i6t:mkr@ϡīB9_eA}]7W(/V,cؾ*Mz[w|M&%d.D^n gxڕ(>-ħH1'O='84m:O=z0r1z (r &*̱lFD~ yچ(r5r !"oGCkĬm U{kj=HE_$R~f `"8|X^K,ZWl4za%FA^eJ/߈|t4ͩ_2Cw2*. 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w:[( #  D$    YOn-screen Shown-sJ)A 1Times New RomanArial WingdingsSymbolBlank PresentationChemWindow DocumentISIS/Draw Sketch Bitmap Image8Alkenes: Chapter 7 Structure and Synthesis of AlkenesFunctional GroupOrbital DescriptionBond Lengths and AnglesPi BondElements of UnsaturationPropose a Structure: HeteroatomsStructure for C6H7N?IUPAC NomenclatureName These AlkenesAlkene Substituents Slide 13 Slide 14 Common NamesCis-trans Isomerism Name these:E-Z Nomenclature Example, E-ZCommercial Uses: EthyleneCommercial Uses: PropyleneOther PolymersStability of AlkenesSubstituent EffectsDisubstituted IsomersCycloalkene Stability Bredts RulePhysical PropertiesPolarity ExamplesAlkene Synthesis OverviewRemoving HX via E2Some Bulky BasesHofmann ProductE2: DiastereomersE2: CyclohexanesE2: Vicinal DibromidesRemoving HX via E1Dehydration of AlcoholsDehydration MechanismIndustrial Methods Slide 41  Fonts UsedDesign TemplateEmbedded OLE Servers Slide Titles) 8@ _PID_HLINKSA6F:\Instructor_Resources\Chapter_06\Animations\08A.MOV.-@Aria_&C  . 2 (L. 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More reactive than sigma bond. Bond dissociation energies: C=C BDE 146 kcal/mol C-C BDE -83 kcal/mol Pi bond 63 kcal/mol =>\ZZfZ    f& fC"    Orbital Description   FSigma bonds around C are sp2 hybridized. Angles are approximately 120 degrees. No nonbonding electrons. Molecule is planar around the double bond. Pi bond is formed by the sideways overlap of parallel p orbitals perpendicular to the plane of the molecule. =>GZf f&f/fff z &    t  Bond Lengths and Angles   zHybrid orbitals have more s character. Pi overlap brings carbon atoms closer. Bond angle with pi orbitals increases. Angle C=C-H is 121.7 Angle H-C-H is 116. 6 =>juIZ @    R    U  Pi Bond   Sideways overlap of parallel p orbitals. No rotation is possible without breaking the pi bond (63 kcal/mole). Cis isomer cannot become trans without a chemical reaction occurring. R* ft @     G    D  Elements of Unsaturation   A saturated hydrocarbon: CnH2n+2 Each pi bond (and each ring) decreases the number of H s by two. Each of these is an element of unsaturation. To calculate: find number of H s if it were saturated, subtract the actual number of H s, then divide by 2.   !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~JRoot EntrydO);o%"F@Pictures~Current User<#SummaryInformation(PowerPoint Document(JDocumentSummaryInformation8Document &ChemWindow.Document0&ChemWindow DocumentDocument &ChemWindow.Document0&ChemWindow DocumentDocument &ChemWindow.Document0&ChemWindow DocumentDocument &ChemWindow.Document0&ChemWindow Document08A.MOVjF:\Instructor_Resources\Chapter_06\Animations\08A.MOV#3 ISIS/Draw Sketch ISISServer0 ISIS/Draw Sketch!4 ISIS/Draw Sketch ISISServer0 ISIS/Draw Sketch+6Bitmap Image Paint.Picture0Bitmap Image,7Bitmap Image Paint.Picture0Bitmap Image-9Bitmap Image Paint.Picture0Bitmap Image.:Bitmap Image Paint.Picture0Bitmap Image/ 00DTimes New Roman<$0<z[ 04DArialNew Roman<$0<z[ 04 DWingdingsRoman<$0<z[ 040DSymbolgsRoman<$0<z[ 04 C  .  @n?" dd@  @@``_@,whoosh.wav.WAV 10103RIFFWAVEfmt ++data~~~~~~~~~~~~~~~~~~~~~~~~~~~|||~~~~~zvtvxz|~zvrnlrv||vtrpptz~|xvtv|~~zxvvvz|~xrlhntzzvrrpprrx~|j[QU_|bICCYn[ICY~zlnh]_r|]SUSSjz|x__l~v_]drnUb|nfd_]d]5=rrnj]jz~lMldrx[[_f|YQfWK_xh[zx[CIjzxxdSQz|_fI9WӹM;QnvK;OUx~xj]]YS~ɵlM?plM;CGpٵ[)Kh|% %;xtKQS]ɖbGr|lSnvz~nfS[nëx;Az=+AYݻ|=/1r_ ?|潄W5/Czãf)/pvbMQr|O=OtjdhjlG?G_ɊK3לdQCMppW;1SŷAMz/#?bx͖SAM[hvhYp~~zrvt[]ptWOUtxxd]v~vvxzd_xzh_nrSQltbdp~_lrQ_l][tf]W]~hWfp|fWhnhbU[hzlSCWbYbnxpdhjvjM9Ot]GQ[dpp~hhhdpx~xh]Yntnrp]dlvjQMb|vdjpzxzztljr||_[r~~jb_j|z|xpp~~v]Wh||zx|x|zzndhpxr]Yfntzjl|z||~vppnrzphrxz|~|xtrjjtv~~vz|z||xrrv~xrprtz|||vzxvx|xtx~~~~~~~zxxxx|zxz~~~rrz~|xz~~|vtx|zxz|~~~||zx|||~~zz|zz~~~~|~~||~~||zz|~||z~~~~zxzz|~~~~|~~~|~||~~~~~~~~~~~~~|||~~~~~~~~~~~~~||~~||~||~~~~|||~~~~||||~~~~~~||||~~~~~~~~~~~|~~~~|zz~~~~~~~||||~~||~~~~~|||~~~~~|||~|~|~~~~|z|~~~~~~~|||~~~~~~~~||~~~~~~~~    5a, 23$./ .   .  /,  "  '% *$1+%41  R$rC >oR$xU(&mc"$ ,yF.p4^t &"$Gzec_[v+,"$(P̯C8qO3"$04 {^5I9"$W5tc_l.B"$)y<܅ F $F"$M u2߯MJR$R< kxR;]!O2$ 9rWYDp2$Gy,Reeau2$":h;sPGY8y2$\1c$D%R$F9 a h1ΚʅR$zЀ4 te=b 2$eLķTlGՂ2$d+L+DvR$ a5Ŏ~$b$L lbc 2$d.}ՌU32$b\`<E.2$6dc"^g'Y }e s2$yZdV2Ƌ 2$'e1\y^X 2$KါI= Zz?Q $2$Z  uX#&T)22$nqY9J,62$ЯݜH(j;2$H,:wJApT2$"~ƌWZ9sQq2$1= ;imNF@u2$/9Hm|iy2$/C12X!˱\~2$p5-T&YHridnނR$kԆ}=}0n<ɐWjĆ2$I2XC^ fR$̙@Vp,2$ Ҟ0!?b$X|b@/732$٥A?")=4]_&o12$?D4g((\lQb$ 26QNJb$4B<\w"Jv#*T 0AAPff@ g4HdHdTz[ 08ppp@ g4&d&dTz[ 0p@ pp<4!d!d 0,uC<4BdBd 0,uCR ʚ;no8ʚ;<4dddd|- 0lh___PPT2001D<4XX0___PPT10 2___PPT9/ 0? -O ==7Alkenes: Chapter 7 Structure and Synthesis of Alkenes 8   Functional Group   Pi bond is the functional group. More reactive than sigma bond. Bond dissociation energies: C=C BDE 146 kcal/mol C-C BDE -83 kcal/mol Pi bond 63 kcal/mol =>\ZZfZ    f& fC"    Orbital De      !"#$%&'()*+,-./0123456789:;<=>?@ABCDGHIKLMNOPQRSTUVWXYZ[\]^_`abcscription   FSigma bonds around C are sp2 hybridized. Angles are approximately 120 degrees. No nonbonding electrons. Molecule is planar around the double bond. Pi bond is formed by the sideways overlap of parallel p orbitals perpendicular to the plane of the molecule. =>GZf f&f/fff z &    t  Bond Lengths and Angles   zHybrid orbitals have more s character. Pi overlap brings carbon atoms closer. Bond angle with pi orbitals increases. Angle C=C-H is 121.7 Angle H-C-H is 116. 6 =>juIZ @    R    U  Pi Bond   Sideways overlap of parallel p orbitals. No rotation is possible without breaking the pi bond (63 kcal/mole). Cis isomer cannot become trans without a chemical reaction occurring. R* ft @     G    D  Elements of Unsaturation   A saturated hydrocarbon: CnH2n+2 Each pi bond (and each ring) decreases the number of H s by two. Each of these is an element of unsaturation. To calculate: find number of H s if it were saturated, subtract the actual number of H s, then divide by 2. =>DZ ff ff fff  D   Propose a Structure:   First calculate the number of elements of unsaturation. Remember: A double bond is one element of unsaturation. A ring is one element of unsaturation. A triple bond is two elements of unsaturation. =>BZZ* f   f#  f#  f   "      Heteroatoms     Halogens take the place of hydrogens, so add their number to the number of H s. Oxygen doesn t change the C:H ratio, so ignore oxygen in the formula. Nitrogen is trivalent, so it acts like half a carbon.lZ$f$ $f,$$f@$$f.$&        Structure for C6H7N?6   <Since nitrogen counts as half a carbon, the number of H s if saturated is 2(6.5) + 2 = 15. Number of missing H s is 15  7 = 8. Elements of unsaturation is 8 2 = 4. =>4 {      IUPAC Nomenclature   3Parent is longest chain containing the double bond. -ane changes to -ene. (or -diene, -triene) Number the chain so that the double bond has the lowest possible number. In a ring, the double bond is assumed to be between carbon 1 and carbon 2. =>4 ff 4    t5                     Name These Alkenes    Alkene Substituents    8+ 5*  Common Names   +Usually used for small molecules. Examples: ,   Cis-trans Isomerism    )Similar groups on same side of double bond, alkene is cis. Similar groups on opposite sides of double bond, alkene is trans. Cycloalkenes are assumed to be cis. Trans cycloalkenes are not stable unless the ring has at least 8 carbons. =>\*Z6=& ,        3                   w   Name these:   E-Z Nomenclature.   CUse the Cahn-Ingold-Prelog rules to assign priorities to groups attached to each carbon in the double bond. If high priority groups are on the same side, the name is Z (for zusammen). If high priority groups are on opposite sides, the name is E (for entgegen). =>Du "? Z        E    B   Example, E-Z.    Commercial Uses: Ethylene   Commercial Uses: Propylene   Other Polymers   Stability of Alkenes   Measured by heat of hydrogenation: Alkene + H2 Alkane + energy More heat released, higher energy alkene.8s1$=Z'         ,      Substituent Effects   More substituted alkenes are more stable. H2C=CH2 < R-CH=CH2 < R-CH=CH-R < R-CH=CR2 < R2C=CR2 unsub. < monosub. < disub. < trisub. < tetra sub. Alkyl group stabilizes the double bond. Alkene less sterically hindered.Z*       :I_                 8      Disubstituted Isomers      }Stability: cis < geminal < trans isomer Less stable isomer is higher in energy, has a more exothermic heat of hydrogenation.@         e  Cycloalkene Stability      Cis isomer more stable than trans. Small rings have additional ring strain. Must have at least 8 carbons to form a stable trans double bond. For cyclodecene (and larger) trans double bond is almost as stable as the cis. =>HZ_   N       ;    @  ,#Bredt s Rule    A bridged bicyclic compound cannot have a double bond at a bridgehead position unless one of the rings contains at least eight carbon atoms. Examples:P ' f4 f&       Physical Properties   kLow boiling points, increasing with mass. Branched alkenes have lower boiling points. Less dense than water. Slightly polar Pi bond is polarizable, so instantaneous dipole-dipole interactions occur. Alkyl groups are electron-donating toward the pi bond, so may have a small dipole moment. =>V|ZZ|    " &        Polarity Examples   !Alkene Synthesis Overview    E2 dehydrohalogenation (-HX) E1 dehydrohalogenation (-HX) Dehalogenation of vicinal dibromides (-X2) Dehydration of alcohols (-H2O) => LbB t                   i  "Removing HX via E2    Strong base abstracts H+ as X- leaves from the adjacent carbon. Tertiary and hindered secondary alkyl halides give good yields. Use a bulky base if the alkyl halide usually forms substitution products. => B     %Some Bulky Bases   &Hofmann Product   UBulky bases abstract the least hindered H+ Least substituted alkene is major product.$V),&=      .%E2: Diastereomers&       VStereospecific reaction: (S, R) produces only trans product, (R, R) produces only cis.rW! 4  D      /'E2: Cyclohexanes&       )Leaving groups must be trans diaxial. =>**!&      (E2: Vicinal Dibromides&        pRemove Br2 from adjacent carbons. Bromines must be anti-coplanar (E2). Use NaI in acetone, or Zn in acetic acid.$q g&K    #  'Removing HX via E1   Secondary or tertiary halides Formation of carbocation intermediate Weak nucleophile Usually have substitution products too => @+          j  ) Dehydration of Alcohols   *Reversible reaction Use concentrated sulfuric or phosphoric acid, remove low-boiling alkene as it forms. Protonation of OH converts it to a good leaving group, HOH Carbocation intermediate, like E1 Protic solvent removes adjacent H+ =>:+!A tU         0         _  *!Dehydration Mechanism   -$Industrial Methods   |Catalytic cracking of petroleum Long-chain alkane is heated with a catalyst to produce an alkene and shorter alkane. Complex mixtures are produced. Dehydrogenation of alkanes Hydrogen (H2) is removed with heat, catalyst. Reaction is endothermic, but entropy-favored. Neither method is suitable for lab synthesis =>v t]q t Qqt+    )         4      +"/${   HJ(   Hr H S `0    H C <$ 0  H H 0޽h ? ̙33ia___PPT10A.+} <D' = @B D' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*Hl%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*Hl%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*HD%(+8+0+H +    PL0 5 ( ( Lr L S `0   x L <A ??P#:  l   L ,$D 0 L <p' 51f L <   52fl $   L$ ,$D 0 L BW 51f  L B@ $  52f  L <ಘ &z ,$D 0 J2Z,l `   L`  ,$D 0  L B  ' 52f L B` D  51fl 0   L0  ,$D 0 L BԿ0   51f L BØ0 p   52f L <`˜ ? / ,$D 0 J5E, L < ̘ ,$D 0 s(2Z, 5E)-3,7-dichloro-2,5-octadiene =>TtP!H L 0޽h ? ̙33___PPT10+ GD' = @B D' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*L%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<* L%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<* L%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*L%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<*L%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*L%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*L%(++0+ L ++0+L ++0+L +   hJ(  hr h S `0    h C <$ 0  H h 0޽h ? ̙33  ___PPT10 .+} <D* ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*h#%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*h#L%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*hL%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*h%(+8+0+h +r  z ( Unstable. Violates Bredt s rule  l  pR  p ,$D 0Z  s *A!p(   <T @ R NStable. Double bond in 8-membered ring. =>OOH  0޽h ? ̙33  ___PPT10p .+D ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<* %(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+#.<* %(+8+0+ +  lJ(  lr l S @`0    l C <0 <$ 0  H l 0޽h ? ̙33  ___PPT10 .+} <D\ ' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*l*%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*l*V%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*lVm%(Ds' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*lm|%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*l|%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+#.<*ll%(+8+0+l +r( Vcm ,{'? c:[( #  DDocument &ChemWindow.Document0&ChemWindow DocumentDocument &ChemWindow.Document0&ChemWindow Document  !"#$%&'()*+,-./0123456789:;Oh+'0h hp   ( 4@HAlkenes Jo BlackburnoCC:\Program Files\Microsoft Office\Templates\Blank Presentation.pot \P100Microsoft PowerPointoso@ `@=d@ K6o%"Gg  +  -- @ !--'@Arial-. 33$2 _Alkenes: Chapter 7Q=DDD="""XDED"D)"D."System-@Arial-. 33+2 _Structure and Synthesis Q")D="D)D"DDD"R<D#DD==".-@Arial-. 332  of AlkenesD""Q=DDD=.-@Arial-. !2 Organic Chemistryt=+++'8,+A''.-@Arial-.  2 V, 5+.-@Arial-.  2 th.-@Arial-. 2 Edition4+,+.-@Arial-. 2 (L. G. Wade, Jr.+<L+++'.-՜.+,D՜.+, =>DZ ff ff fff  D   Propose a Structure:   First calculate the number of elements of unsaturation. Remember: A double bond is one element of unsaturation. A ring is one element of unsaturation. A triple bond is two elements of unsaturation. =>BZZ* f   f#  f#  f   "      Heteroatoms     Halogens take the place of hydrogens, so add their number to the number of H s. Oxygen doesn t change the C:H ratio, so ignore oxygen in the formula. Nitrogen is trivalent, so it acts like half a carbon.lZ$f$ $f,$$f@$$f.$&        Structure for C6H7N?6   <Since nitrogen counts as half a carbon, the number of H s if saturated is 2(6.5) + 2 = 15. Number of missing H s is 15  7 = 8. Elements of unsaturation is 8 2 = 4. =>4 {      IUPAC Nomenclature   3Parent is longest chain containing the double bond. -ane changes to -ene. (or -diene, -triene) Number the chain so that the double bond has the lowest possible number. In a ring, the double bond is assumed to be between carbon 1 and carbon 2. =>4 ff 4    t5                     Name These Alkenes    Alkene Substituents    8+ 5*  Common Names   +Usually used for small molecules. Examples: ,   Cis-trans Isomerism    )Similar groups on same side of double bond, alkene is cis. Similar groups on opposite sides of double bond, alkene is trans. Cycloalkenes are assumed to be cis. Trans cycloalkenes are not stable unless the ring has at least 8 carbons. =>\*Z6=& ,        3                   w   Name these:   E-Z Nomenclature.   CUse the Cahn-Ingold-Prelog rules to assign priorities to groups attached to each carbon in the double bond. If high priority groups are on the same side, the name is Z (for zusammen). If high priority groups are on opposite sides, the name is E (for entgegen). =>Du "? Z        E    B   Example, E-Z.    Commercial Uses: Ethylene   Commercial Uses: Propylene   Other Polymers   Stability of Alkenes   Measured by heat of hydrogenation: Alkene + H2 Alkane + energy More heat released, higher energy alkene.8s1$=Z'         ,      Substituent Effects   More substituted alkenes are more stable. H2C=CH2 < R-CH=CH2 < R-CH=CH-R < R-CH=CR2 < R2C=CR2 unsub. < monosub. < disub. < trisub. < tetra sub. Alkyl group stabilizes the double bond. Alkene less sterically hindered.Z*       :I_                 8      Disubstituted Isomers      }Stability: cis < geminal < trans isomer Less stable isomer is higher in energy, has a more exothermic heat of hydrogenation.@         e  Cycloalkene Stability      Cis isomer more stable than trans. Small rings have additional ring strain. Must have at least 8 carbons to form a stable trans double bond. For cyclodecene (and larger) trans double bond is almost as stable as the cis. =>HZ_   N       ;    @  ,#Bredt s Rule    A bridged bicyclic compound cannot have a double bond at a bridgehead position unless one of the rings contains at least eight carbon atoms. Examples:P ' f4 f&       Physical Properties   kLow boiling points, increasing with mass. Branched alkenes have lower boiling points. Less dense than water. Slightly polar Pi bond is polarizable, so instantaneous dipole-dipole interactions occur. Alkyl groups are electron-donating toward the pi bond, so may have a small dipole moment. =>V|ZZ|    " &        Polarity Examples   !Alkene Synthesis Overview    E2 dehydrohalogenation (-HX) E1 dehydrohalogenation (-HX) Dehalogenation of vicinal dibromides (-X2) Dehydration of alcohols (-H2O) => LbB t                   i  "Removing HX via E2    Strong base abstracts H+ as X- leaves from the adjacent carbon. Tertiary and hindered secondary alkyl halides give good yields. Use a bulky base if the alkyl halide usually forms substitution products. => B     %Some Bulky Bases   &Hofmann Product   UBulky bases abstract the least hindered H+ Least substituted alkene is major product.$V),&=      .%E2: Diastereomers&       VStereospecific reaction: (S, R) produces only trans product, (R, R) produces only cis.rW! 4  D      /'E2: Cyclohexanes&       )Leaving groups must be trans diaxial. =>**!&      (E2: Vicinal Dibromides&        pRemove Br2 from adjacent carbons. Bromines must be anti-coplanar (E2). Use NaI in acetone, or Zn in acetic acid.$q g&K    #  'Removing HX via E1   Secondary or tertiary halides Formation of carbocation intermediate Weak nucleophile Usually have substitution products too => @+          j  ) Dehydration of Alcohols   *Reversible reaction Use concentrated sulfuric or phosphoric acid, remove low-boiling alkene as it forms. Protonation of OH converts it to a good leaving group, HOH Carbocation intermediate, like E1 Protic solvent removes adjacent H+ =>:+!A tU         0         _  *!Dehydration Mechanism   -$Industrial Methods   |Catalytic cracking of petroleum Long-chain alkane is heated with a catalyst to produce an alkene and shorter alkane. Complex mixtures are produced. Dehydrogenation of alkanes Hydrogen (H2) is removed with heat, catalyst. Reaction is endothermic, but entropy-favored. Neither method is suitable for lab synthesis =>v t]q t Qqt+    )         4      +"/$rG'? #:Root EntrydO)(kF@Pictures~Current User</SummaryInformation(      !"#$%&'()*+,-./0123456789:;<=>?@ABCDGHIKLMNOPQRSTUVWXYZ[\]^_`abchJ  !"#$%&'()*+,-./0123456789:;@ _PID_HLINKSA6F:\Instructor_Resources\Chapter_06\Animations\08A.MOV.-@Aria_&GCCCDGCCCD 2 (L. G. Wade, Jr.+<L+++'.-