columbia大学有机化学课件 （二十七）.pptVIP

6.18Epoxidation of Alkenes Epoxides are examples of heterocyclic compounds three-membered rings that contain oxygen ethylene oxide propylene oxide Epoxide Nomenclature Substitutive nomenclature: named as  epoxy-substituted alkanes. “epoxy” precedes name of alkane 1,2-epoxypropane 2-methyl-2,3-epoxybutane Problem 6.17 Give the IUPAC name, including stereochemistry, for disparlure. cis-2-Methyl-7,8-epoxyoctadecane Epoxidation of Alkenes Example Stereochemistry of Epoxidation Problem 6.18 Give the structure of the alkene,including stereochemistry, that you wouldchoose as the starting material in a preparationof synthetic disparlure. Problem 6.18 Give the structure of the alkene,including stereochemistry, that you wouldchoose as the starting material in a preparationof synthetic disparlure. Relative Rates of Epoxidation ethylene H2C=CH2 1 propene CH3CH=CH2 22 2-methylpropene (CH3)2C=CH2 484 2-methyl-2-butene (CH3)2C=CHCH3 6526 More highly substituted double bonds react faster.Alkyl groups on the double bond make itmore “electron rich.” Mechanism of Epoxidation 6.19Ozonolysis of Alkenes Ozonolysis has both synthetic and analytical applications. synthesis of aldehydes and ketones identification of substituents on the  double bond of an alkene Ozonolysis of Alkenes First step is the reaction of the alkene with ozone.The product is an ozonide. Ozonolysis of Alkenes Second step is hydrolysis of the ozonide. Two aldehydes, two ketones, or an aldehyde and a ketone are formed. Ozonolysis of Alkenes As an alternative to hydrolysis, the ozonide canbe treated with dimethyl sulfide. Example H2C CH2 O H2C CHCH3 O H2C CHCH3 O CHCH3 O C H3C H3C 1 2 3 4 O H H peroxy acid C C + O RCOOH C C O + O RCOH + CH3COOH O (52%) + CH3COH O O C C + O RCOOH C C O + O RCOH syn addition O H H peroxy acid O H H H H + O3 C C O O O C C + O3 C C O O O C C C O C O + H2O, Zn + O3 C C O O O C C C O C O + (CH3)2S 1. O3 2. H2O, Zn (38%) (57%) CH3 CH2CH3 H