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Chapter 10

Chapter 10. Alkyl Halides. Alkyl Halides. Naming Synthesis - from alkene, alkane, & alcohol Reactions - Organometallic. Naming. 1,3-Dichloro-3-methylbutane. Naming. *. *. 2-Bromo-5-chlorohexane. (R or S)-2-Bromo-(R or S )-5-chlorohexane ( if 3-dimension structure is given ). Naming.

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Chapter 10

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  1. Chapter 10 Alkyl Halides Chapter 10 - Alkyl Halides

  2. Alkyl Halides • Naming • Synthesis - from alkene, alkane, & alcohol • Reactions - Organometallic Chapter 10 - Alkyl Halides

  3. Naming 1,3-Dichloro-3-methylbutane Chapter 10 - Alkyl Halides

  4. Naming * * 2-Bromo-5-chlorohexane (R or S)-2-Bromo-(R or S )-5-chlorohexane (if 3-dimension structure is given) Chapter 10 - Alkyl Halides

  5. Naming * * * 4-sec-Butyl-2-chlorononane Chapter 10 - Alkyl Halides

  6. Naming 1,1-Dibromo-4-tert-butylcyclohexane Chapter 10 - Alkyl Halides

  7. Naming * 5-Iodo-2-hexene Chapter 10 - Alkyl Halides

  8. Naming 1-Bromo-6-chloro-2-hexyne Chapter 10 - Alkyl Halides

  9. Naming * * cis-1-Bromo-2-ethylcyclopentane cis-(R)-1-Bromo-(S)-2-ethylcyclopentane Chapter 10 - Alkyl Halides

  10. Alkyl Halides • Naming • Synthesis - from alkene, alkane, & alcohol • Reactions - Organometallic Chapter 10 - Alkyl Halides

  11. Synthesis • Alkene + HX(X=Cl, Br, or I) or X2 (X=Cl or Br ) • Radical Halogenation of Alkanes • Allylic Halogenation of Alkenes • From Alcohol Chapter 10 - Alkyl Halides

  12. M HX ether X2 CH2Cl2 KMnO4, H3O+ X2 O3 H2O(xs) Zn/H3O+ HgAc2, H2O/THF CH2I2 NaBH4 Zn(Cu) ether BH3, THF CHCl3 H2O2, OH- KOH H2 OsO4 NaHSO4, H2O Pd or Pt halogenation anti halohydrination oxidation M anti oxymercuration M oxidation Alkene hydroboration non-M syn Simmons-Smith syn hydrogenation syn carbenation syn syn hydroxylation Chapter 10 - Alkyl Halides

  13. Synthesis • Alkene + HX(X=Cl, Br, or I) or X2 (X=Cl or Br ) • Radical Halogenation of Alkanes • Allylic Halogenation of Alkenes • From Alcohol Chapter 10 - Alkyl Halides

  14. Radical Chlorination of Methane h or heat h or heat h or heat Chapter 10 - Alkyl Halides

  15. h or heat Chlorination of alkanes Monochloro- Chiral, racemic * achiral achiral * + others... chiral, racemic * chiral, racemic achiral Chapter 10 - Alkyl Halides

  16. h or heat Chlorination of alkanes Monochloro- 1o 3o and others... 2o 2o Yields are different, with 3o > 2o > 1o (see p. 361) 1o Chapter 10 - Alkyl Halides

  17. relative reactivity(rr) expected yield #H  rr # H 6 1.0 6.0 21% 1 5.0 5.0 18% 2 3.5 7.0 25% 2 3.5 7.0 25% 3 1.0 3.0 11%  = 28.0 see p. 361 Chapter 10 - Alkyl Halides

  18. Reactivity Stability • • • Radical Chlorination of Alkane Yields 3o > 2o > 1o implies that ... Hammond Postulate Chapter 10 - Alkyl Halides

  19. Synthesis • Alkene + HX(X=Cl, Br, or I) or X2 (X=Cl or Br ) • Radical Halogenation of Alkanes • Allylic Halogenation of Alkenes • From Alcohol Chapter 10 - Alkyl Halides

  20. allylic 361 kJ/mol Vinylic C—H 444 kJ/mol alkyl 401 kJ/mol Allylic p 172, Table 5.3 1. Radical reactions take place at the allylic position. 2. Allylic hydrogen is more acidic than alkyl and vinylic hydrogen. Chapter 10 - Alkyl Halides

  21. • • • • • vinylic allylic 1o 2o 3o Radical Chlorination of Alkane Stability Chapter 10 - Alkyl Halides

  22. allylic • • vinylic Allylic vs. vinylic Stability Resonance • more stable No resonance less stable Chapter 10 - Alkyl Halides

  23. Allylic position Allylic position p 237 trans-2-Bromo-1-cyclohexynol * p 364 3-Bromocyclohexene * * Chapter 10 - Alkyl Halides

  24. Synthesis • Alkene + HX(X=Cl, Br, or I) or X2 (X=Cl or Br ) • Radical Halogenation of Alkanes • Allylic Halogenationof Alkenes • From Alcohol Chapter 10 - Alkyl Halides

  25. Alcohol  Alkyl Halides ROH + HX  RX + H2O Chapter 10 - Alkyl Halides

  26. ROH + HX  RX + H2O Ethers, carbonyl, and aromatic rings do not interfere. High yield Chapter 10 - Alkyl Halides

  27. Synthesis • Alkene + HX(X=Cl, Br, or I) or X2 (X=Cl or Br ) • Radical Halogenation of Alkanes • Allylic Halogenation of Alkenes • From Alcohol Chapter 10 - Alkyl Halides

  28. Alkyl Halides • Naming • Synthesis - from alkene, alkane, & alcohol • Reactions - Organometallic Chapter 10 - Alkyl Halides

  29. ether R — X + Mg R — Mg — X or THF Organometallic Reactions Organomagnesium halides, RMgX, - Grignard Reagents. R = 1o, 2o, 3o, alkyl, alkenyl (vinyl), or aryl. X = Cl, Br, or I Chapter 10 - Alkyl Halides

  30. Organometallic Reactions Organolithium reagent, RLi. Chapter 10 - Alkyl Halides

  31. Organometallic Compound 1. Although RMgX and Rli are polar covalent, they are still soluble in nonpolar pentane. 2. RMgX and RLi are strong bases. Chapter 10 - Alkyl Halides

  32. 25 16-18 15.7 9-10 8-9 4-5 51 38-40 pKa: pKa: 1. RMgX is a strong base. 2. CH3CH2MgBr will react with all the listed compounds. Chapter 10 - Alkyl Halides

  33. Organometallic Reactions Lengthen small molecules. Chapter 10 - Alkyl Halides

  34. Alkyl Halides • Naming • Synthesis - from alkene, alkane, & alcohol • Reactions - Organometallic Chapter 10 - Alkyl Halides

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