1 / 34

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.

beau-hull
Download Presentation

Chapter 10

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  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

More Related