哥伦比亚大学有机化学课件03_04_08.ppt

3.4The Shapes of Cycloalkanes:Planar or Nonplanar? Adolf von Baeyer (19th century) assumed cycloalkanes are planar polygons distortion of bond angles from 109.5° givesangle strain to cycloalkanes with rings eithersmaller or larger than cyclopentane Baeyer deserves credit for advancing the ideaof angle strain as a destabilizing factor. But Baeyer was incorrect in his belief that cycloalkanes were planar. Types of Strain ? Torsional strain strain that results from eclipsed bonds ? van der Waals strain (steric strain) strain that results from atoms being too  close together ? angle strain strain that results from distortion of bond angles from normal values Measuring Strain in Cycloalkanes Heats of combustion can be used to comparestabilities of isomers. But cyclopropane, cyclobutane, etc. are not isomers. All heats of combustion increase as the numberof carbon atoms increase. Measuring Strain in Cycloalkanes Therefore, divide heats of combustion by number of carbons and compare heats of combustion on a per CH2 group basis. Heats of Combustion in Cycloalkanes Cycloalkane kJ/mol Per CH2 Cyclopropane 2,091 697 Cyclobutane 2,721 681 Cyclopentane 3,291 658 Cyclohexane 3,920 653 Cycloheptane 4,599 657 Cyclooctane 5,267 658 Cyclononane 5,933 659 Cyclodecane 6,587 659 Heats of Combustion in Cycloalkanes Cycloalkane kJ/mol Per CH2 According to Baeyer, cyclopentane should have less angle strain than cyclohexane. Cyclopentane 3,291 658 Cyclohexane 3,920 653 The heat of combustion per CH2 group is less for cyclohexane than for cyclopentane. Therefore, cyclohexane has less strain than cyclopentane. Adolf von Baeyer (19th century) assumed cycloalkanes are planar polygons distortion of bond angles from 109.5° givesangle strain to cycloalkanes with rings eithersmaller or larger than cyclopentane Baeyer deserves credit for advancing the ideaof angle strain as a destabilizing factor. But Baeyer was incorrect in his belief that cycloalkanes were planar. 3.5Conform