加州大学伯克利分校有机化学课件11.pptVIP

? University of California ? Univesity of California Structure of Double Bond How Weak is the ? Bond? Bond Strengths (kcal/mol) Acidity: Coupling Constants Vibrations in Molecules: Infrared (IR) Spectroscopy Infrared Modes The Infrared Spectrometer Degrees of Unsaturation Relative Stability of Alkenes Synthesis of Alkenes Acid-Mediated Dehydration of Alcohols Dehydration with Rearrangement Most useful: υC H ~ - 1. Alkyl = 2900cm-1 υCsp2 H ~ - = 3080 cm-1, υC C ~ - - = 1640 cm-1, C C H R R H trans υ = 970 cm-1 ~ R O H 2. Alkenes 3. H H Trans-2-hexene 4. O C 1740 cm-1 3350 cm-1 (broad) Molecular formula tells us how many rings and/or ? bonds are present in a molecule. Reference is a saturated acyclic hydrocarbon: CnH2n+2. Simple examples: We need to determine the deviation of the molecular formula from CnH2n+2 (in increments of 2H). Every ring or double bond takes away 2H, triple bond 4H from CnH2n+2. C6H12, not C6H14. C6H10, not C6H14. Halogen: -1; C H C X Nitrogen: +1; C H C N R H Effect of Presence of Heteroatoms on CnH2n+2 C H C O H S, O no effect on count (still CnH2n+2 + Sx or Oy) Depends on valency of element: Steps: 1. Calculate Hsat = 2n C + 2 – nX + nN n = “number of” 2. Count Hactual in given molecular formula. 3. Degree of Unsaturation: (Hsat – Hactual)/2 C5H5N Examples: C10H16 1. Hsat = (2x10) + 2 = 22 2. Degree of unsaturation: (22-16)/2 = 3 etc. or Hsat= 10 + 2 + 1 = 13 2. (13 - 5)/2 = 4 degrees of unsaturation: N Pyridine C N Or? Or Problem C3HN: How many degrees of unsaturation? Hsat = 2n C + 2 – nX + nN Degree of Unsaturation: (Hsat – Hactual)/2 A. 2 B. 3 C. 4 Measure heat of hydrogenation ΔHH2 of isomers, e.g., butene + H2 + H2 + H2 ΔHH2 (kcal mol-1) -28.6 -27.6 -30.3 Internal terminal trans cis Stability: , cat. cat. cat. Why? 1. Hyperconjugation: 2. Steric hindrance (strain) C H C C : Cis is less stable than trans because of steric hindrance General order of stability: CH2 CH2 RCH CH2 RCH