Chemical reactions

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A free review of chemical reactions in organic chemistry provided by Examville

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Chemical reactions

  1. 1. Unit One Part 6: analysing chemical reactions at last...chemical reactions!
  2. 2. 6 Unit One Part reactions (pg69-70) Balanced Reaction types (pg71-72) Reagents (pg72-77)
  3. 3. Chemistry... NUCLEOPHILE ELECTROPHILE electron rich electron poor high electron low electron density density this slide sums up the majority of chemical reactions (even the funkier ones follow these ...it’s that simple principles)
  4. 4. Chemistry... NUCLEOPHILE ELECTROPHILE electron rich electron poor high electron low electron density density ...so that was a quick lecture... ...it’s that simple
  5. 5. lets look at a simple reaction... lets just show its that simple (we do have 50 minutes to kill after all)
  6. 6. the Lucas test H3C H3C ZnCl2 (aq) H3C OH + HCl H3C Cl + H2O H3C H3C the Lucas test is simple...you’ll do it lab this week...two water soluble compounds react... water soluble water soluble water insoluble H-bond ion-dipole two layers
  7. 7. the Lucas test H3C H3C ZnCl2 (aq) H3C OH + HCl H3C Cl + H2O H3C H3C to give an insoluble compound. Why insoluble? (no longer able to H-bond) water soluble water soluble water insoluble H-bond ion-dipole two layers
  8. 8. the Lucas test H3C H3C ZnCl2 (aq) H3C OH + HCl H3C Cl + H2O H3C H3C } } reactants products stoichiometry 1 : 1 : simple definitions 1 : 1
  9. 9. the Lucas test H3C H3C ZnCl2 (aq) H3C OH + HCl H3C Cl + H2O H3C H3C ratio of } } compounds in reaction reactants products stoichiometry 1 : 1 : 1 : 1
  10. 10. ...simply count atoms (or electrons)... sorting out the stoichiometry is easy...just make sure you have the same number of atoms on both sides of the equation and remember...
  11. 11. NO atoms (or electrons) we only move them (or change the bonds) created or destroyed
  12. 12. unfortunately, chemists are lazy... a quick word of warning...organic chemists are a little lazy and often miss side products off their reaction schemes!
  13. 13. depiction of a standard reaction OMe OMe H2SO4 HO3S ...so, here is a standard reaction as shown in many text books...
  14. 14. depiction of a standard reaction OMe OMe H2SO4 HO3S ...problem is, it doesn’t show everything...so lets have a closer look...
  15. 15. so what bonds are broken?
  16. 16. depiction of a standard reaction redraw sulfuric acid and it becomes clear that we will loose an OH... OMe OMe HO SO3H HO3S obviously lost OH
  17. 17. depiction of a standard reaction OMe OMe HO SO3H HO3S ...we can’t just add it to the aryl ring or one C would have too many electrons... obviously lost OH
  18. 18. depiction of a standard reaction OMe OMe HO SO3H H HO3S remember we don’t always draw H
  19. 19. depiction of a standard reaction OMe OMe HO SO3H O H H H HO3S ...overall we have lost H from aromatic and OH from acid...or water which means we ‘forgot’ to add HOH
  20. 20. depiction of a standard reaction OMe OMe HO SO3H O H H H HO3S which means we ‘forgot’ to add HOH
  21. 21. depiction of a standard reaction OH HO Me Br O O Me HO O OMe O O OMe
  22. 22. depiction of a standard reaction H O HO Me Br O O Me HO O OMe ...break O–H bonds... O O OMe all the bonds broken & formed
  23. 23. depiction of a standard reaction H O HO Me Br O O Me HO O OMe O O ...break C–Br bond... OMe all the bonds broken & formed
  24. 24. depiction of a standard reaction ...form C–O bond AND H–Br H O HO Me Br O H Br O Me HO O OMe O O OMe ...and the ‘mystery’ product
  25. 25. depiction of a standard reaction H O HO Me Br O H Br O Me HO O OMe O O OMe 1 3 1 3 don’t forget the stoichiometry
  26. 26. what is happening in a reaction?
  27. 27. it is the movement of electrons
  28. 28. Lewis structures here is the Lucas reaction again... H3C H3C H3C OH + + H3C Cl + O Cl H H H H3C H3C as each bond is two electrons we have just moved electrons...
  29. 29. Lewis structures H H H C H H C H H H H Cl H C C O H H C C Cl O H HH H HH C H C H H H H3C H3C H3C OH + + H3C Cl + O Cl H H H ...and here is the H3C H3C Lewis structures as each bond is two electrons we have just moved electrons...
  30. 30. Lewis structures ...we take O with its complete octet of electrons and share H two of them with H H to... H C H H C H H H H Cl H C C O H H C C Cl O H HH H HH C H C H H H H3C H3C H3C OH + + H3C Cl + O Cl H H H H3C H3C as each bond is two electrons we have just moved electrons...
  31. 31. Lewis structures H H ...form water... H C H H C H H H H Cl H C C O H H C C Cl O H HH H HH C H C H H H H3C H3C H3C OH + + H3C Cl + O Cl H H H H3C H3C as each bond is two electrons we have just moved electrons...
  32. 32. Lewis structures ...then we share the electrons of the chloride octet to make sure the original C is still an a happy octet... H H H C H H C H H H H Cl H C C O H H C C Cl O H HH H HH C H C H H H H3C H3C H3C OH + + H3C Cl + O Cl H H H H3C H3C as each bond is two electrons we have just moved electrons...
  33. 33. Lewis structures H H H C H H C H H H H Cl H C C O H H C C Cl O H HH H HH C H C H H H H3C H3C H3C OH + + H3C Cl + O Cl H H H so just swapped H3C H3C electrons around... as each bond is two electrons we have just moved electrons...
  34. 34. what types of reaction are there?
  35. 35. 3 basic reactions
  36. 36. substitution reactions A B + C A C + B does what it says...the reagent swaps with a functional group in our molecule...
  37. 37. substitution reactions OH OH Br CH3NH2 NHCH3 H Br here’s an example from the synthesis of prozac® where an amine substitutes / displaces / exchanges with a bromide...
  38. 38. substitution reactions Na O Cl O NHCH3 NaCl NHCH3 F3C F3C fluoxetine here is another example finishing the Prozac® synthesis of prozac®; an alkoxide (alcohol derivative) substitutes a chloride...
  39. 39. A + Y A Y two molecules add together or combine...all atoms in both starting addition materials are found in the product reactions
  40. 40. CH3 CH3 H Br Br H here hydrogen bromide adds across an alkene to give us a addition new bromide reactions
  41. 41. at some point you’ll have to learn why it adds the bromide to the more hindered end of the CH3 CH3alkene...but that’s someone else’s job! Br H Br H addition reactions
  42. 42. O H3C O MgBr H3C MgBr CH3 CH3 Ph Ph here a Grignard reagent is adding to a ketone to give (eventually) an addition alcohol reactions
  43. 43. elimination reactions A X A + X elimination is the opposite of addition...we rip a bit of the molecule off.
  44. 44. elimination reactions OH CH3 CH3 O H H H this example shows the elimination of water (dehydration) to form an alkene
  45. 45. elimination reactions CH3 Br H3C CH3 H3C H3C H Br H3C H or the elimination of hydrogen bromide (hydrobromic acid) to form an alkene
  46. 46. what reagents are involved in these reactions? now we know what reactions we can perform...what reagents can we use?
  47. 47. nucleophiles 2 electron rich molecules nucleophiles are electron rich compounds that donate two electrons to form a new bond... examples include... donateelectrons
  48. 48. anions H O ≡ H O Br ≡ Br 3 lone pairs 4 lone pairs H H3C ≡ Pr C H 1 lone pair
  49. 49. anions H O ≡ H O Br ≡ Br negatively charged compounds that possess a 3 lone pairs lone pair of electrons that 4 lone pairs can form a new bond H H3C ≡ Pr C H 1 lone pair
  50. 50. anions nucleophilic reaction O H O H H H
  51. 51. anions nucleophilic reaction hydroxide donates a pair of electrons to form a new bond to proton O H O H H H
  52. 52. anions nucleophilic reaction O H O H H H note: both sides of equation have same charge (both are neutral overall)
  53. 53. anions nucleophilic reaction O H O H H H note: both sides of equation have same charge (both are this is a good sign that you’ve neutral overall) got the reaction right!
  54. 54. lone pairs lone pairs as nucleophile O N S H H H H H3C CH3 H water ammonia dimethyl sulfide (DMS) lone pairs on neutral molecules are also good nucleophiles...
  55. 55. lone pairs nucleophilic reaction H N H Cl N Cl H H H H H H
  56. 56. lone pairs nucleophilic reaction ammonia donates a pair of electrons to form a new bond to hydrogen chloride H N H Cl N Cl H H H H H H
  57. 57. lone pairs nucleophilic reaction can’t have two bonds to H (4 electrons) so break H– Cl bond with electrons flowing towards most electronegative element H N H Cl N Cl H H H H H H
  58. 58. lone pairs nucleophilic reaction H overall its been a N H Cl substitution N Cl H H H H H H
  59. 59. lone pairs nucleophilic reaction H N H Cl N Cl H H H H H H note: overall both sides are neutral (have same charge)
  60. 60. bonds bonds can also be a source of electrons...and these cause confussion! δ– δ+ H C Y Y=Li, Mg B H H nucleophilic H site reactive σ bond H H C C H H R high electron density R = electron nucleophile donating group
  61. 61. electrophiles 2 electron poor molecules the other kind of reagents are...electrophiles are electron poor compounds that accept two electrons to form a new bond... examples include... acceptelectrons
  62. 62. proton H ≡ H empty 1s orbital no electrons! simplest electrophile...it has no electrons and desperately wants some!
  63. 63. proton electrophilic reagent H H H O H O H H
  64. 64. proton electrophilic reagent H H H O H O H H nucleophilic water donates two electrons to proton, which accepts them to form new bond
  65. 65. Group 13 F F Cl F B Cl Al F B F Cl F empty 2p empty 3p orbital orbital have 6 valence only electrons...need 8 to obey octet rule so happily accept a pair of electrons
  66. 66. bonds δ+ δ– Y = Cl, δ+ δ– C Y Y = O, Br, N, O C Y NR electrophilic electrophilic site site bonds can be electrophiles if they are polarised and have a δ+ centre
  67. 67. bonds electrophilic reagent H H O O H O O H H3C CH3 H3C CH3
  68. 68. is it that easy?
  69. 69. nucleophile + electrophile product yup, this equation sums up the majority of reactions...
  70. 70. yes!
  71. 71. ...and no...
  72. 72. H3C δ+ δ– H3C δ+ δ– H3C O H3C Cl H3C H H3C polarity in these two compounds looks the same...so do they behave in the same way??
  73. 73. H3C δ+ δ– H3C δ+ δ– H3C O H3C Cl H3C H H3C of course not! this is chemistry after all...
  74. 74. H3C δ+ δ– H3C δ+ δ– H3C O H3C C Cl alcohol uses lone H3C H H3C pair to act as a nucleophile nucleophile electrophile
  75. 75. H3C δ+ δ– H3C δ+ δ– H3C O H3C C Cl chloride isC H3 an H H3C electrophile nucleophile electrophile
  76. 76. ...you will learn to to identify which is which...
  77. 77. so what actually happens in a reaction?
  78. 78. H3C O H3C Cl H H + H Cl + O H3C H3C CH3 CH3 H so here’s the Lucas test again...overall it’s a substitution of hydroxyl for chlorine what order are the bonds made and broken?
  79. 79. H3C O H3C Cl H H + H Cl + O H3C H3C CH3 CH3 H what order are the bonds made and broken?
  80. 80. H H3C O H3C O H H H H3C H3C CH3 CH3 CH3 CH3 H H3C C O H H H3C C O H CH3 CH3 addition step step one
  81. 81. H H3C O H3C O H H H H3C H3C CH3 CH3 nucleophilic alcohol CH3 donates 2 electrons to CH3 H a proton from H–Cl in H3C C O H H anH3C Creaction addition O H CH3 CH3 addition step step one
  82. 82. H H3C O H3C O H H H H3C H3C CH3 CH3 note: octet rule is obeyed and the charge is the same CH3 on both sides CH3 H (positive) H3C C O H H H3C C O H CH3 CH3 addition step step one
  83. 83. H CH3 H H3C O H O H3C H3C CH3 CH3 H H H H C H H C H H H H H H C C O H H C C O H HH HH C H C H H H step two elimination
  84. 84. H CH3 H H3C O H O H3C H3C CH3 CH3 H H H elimination of H C H H water...molecule splits in C H H H H two...electrons go with H most electronegative H C C O H H C C atom O H HH HH C H C H H H step two elimination
  85. 85. H CH3 H H3C O H O H3C H3C CH3 CH3 H charge is the same H on both sides (positive)... H we now have a reactive H C H intermediate H C H H H H H (charged species with 6 H C C O H electrons) H C C O H HH HH C H C H H H step two elimination
  86. 86. CH3 H3C Cl Cl H3C H3C CH3 CH3 H H H C H H C H H H H C C Cl H C C Cl HH HH C H C H H H addition step step three
  87. 87. CH3 H3C Cl Cl H3C H3C CH3 CH3 H H H C H H C finally, second H H H addition step to H C C Cl H C complete octet C Cl HH HH C H C H H H addition step step three
  88. 88. CH3 H3C Cl Cl H3C H3C CH3 CH3 H H H C H H C H H H H C C Cl H C C Cl HH HH C H C H H H nucleophile donates two electrons to electrophile addition step that accepts them to step form new bond three
  89. 89. CH3 H3C Cl Cl H3C H3C CH3 CH3 H H H C H H C H H H H C C Cl H C C Cl HH note: the charge is HH C H the same on both C H sides (neutral) H H addition step step three
  90. 90. 3 steps 1 substitution reaction
  91. 91. another representation... we can follow the change of energy during a reaction...in a reaction profile
  92. 92. reaction profile energy Cl + H2O H O + Cl H OH + HCl reaction progress Cl + H2O
  93. 93. reaction profile each hill represents one step in our reaction energy Cl + H2O H O + Cl H OH + HCl reaction progress Cl + H2O
  94. 94. reaction profile each dip represents an intermediate we can see energy Cl + H2O H O + Cl H OH + HCl reaction progress Cl + H2O
  95. 95. reaction profile higher the hill, the harder the step energy Cl + H2O H O + Cl H OH + HCl reaction progress Cl + H2O
  96. 96. reaction profile the lower in energy any stage the more stable it is energy Cl + H2O H O + Cl H OH + HCl reaction progress Cl + H2O
  97. 97. just one hill, so just one step energy HO CH3Br Br reaction CH3OH progress
  98. 98. no dip so no intermediates energy HO CH3Br Br reaction CH3OH progress
  99. 99. direct energy substitution would look like this HO CH3Br Br reaction CH3OH progress HO + CH3Br CH3OH + Br
  100. 100. once again, you will learn energy more about this but not from me! Why don’t I get HO to teach the cool stuff? CH3Br Br reaction CH3OH progress H 1 H 1 H SLOW 2 δ– 2 δ– HO + Br HO Br Nu + Br H RDS H H H H H transition state
  101. 101. what have ....we learnt? • analyse reactions • classify reagents •r e a c t i o n t y p e s Picture: © Pittsburgh Supercomputing Center
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