北大有机醚环氧化物药学

1、1会计学北大有机醚环氧化物药学北大有机醚环氧化物药学2021-12-4一、结构二、分类和命名三、物理性质四、形成yang盐五、CO 键的断裂六、醚的自动氧化七、1,2-环氧化合物的开环反应1、酸性开环2、碱性开环八、环醚和冠醚的作用九、醚的制备2021-12-4一、结构OHH.OH3CH.OH3CCH3.2021-12-4通式：ROR(R)、ArOR 或 ArOAr分类：醚直链醚环醚单醚 R=R混醚 R=R环氧化合物冠醚CH3CH2OCH2CH3CH3CH2OCH3OHCCH2H3COOOOOO2021-12-4二、命名1、直链醚普通命名法CH3CH2-0-CH2CH3 二乙基醚（乙醚）(di

2、ethyl ether or Ethyl ether)O二苯基醚(苯醚)(diphenyl ether)CH3CH2CH3 甲基乙基醚（甲乙醚） (ethyl methyl ether)OOCH2CH3苯基乙基醚（苯乙醚）(ethyl phenyl ether)2021-12-42、环醚系统命名法环氧化合物CH3OCHCH2CH3CH3 2-甲氧基丁烷（2-methoxy butane)CH3OCH2CH2OCH3 1,2-二甲氧基乙烷（1,2-dimethoxy ethane)H2COCH2 环氧乙烷epoxyethaneHCOCHH3CCH3HCOCH2H3C 1,2-环氧丙烷1,2-ep

3、oxypropane2,3-环氧丁烷2,3-epoxybutaneOOOO 1,3-环氧丙烷1,3-epoxypropane 1,4-环氧丁烷 四氢呋喃tetrahydrofuran (THF)1,4-二氧六环1,4-dioxane2021-12-4冠醚OOOOOO 18-冠-618-crown-6 18-C-6OOOO 12-冠-4（12-crown-4)三、物理性质CH3CH2OCH2CH3 CH3CH2CH2CH2OH CH3CH2CH2CH2CH3分子量 74 74 72沸点 34.6 11835溶解度 7.5g 7.9不溶2021-12-4沸点：醚 烷烃 烷烃化学性质ROR KMnO

4、4NaNaOH稀酸强氧化剂强还原剂强碱不反应稳定性仅次于烷烃2021-12-4四、形成yang盐ROR + HClROR + ClH_+.ROR + H2SO4ROR + HSO4H_+.ROR + BF3.ORRBF3_+五、CO 键的断裂CH3OCH3 + HICH3OH + CH3ICH3OH + HICH3I + H2O亲核取代SN2 机理适于伯烷基醚CH3OCH3 + HICH3OCH3 + ICH3I +_H+质子化CH3OCH3 + I_H+H3CH3.OHCI+CH3OH2021-12-4SN1 机理适于叔烷基醚CH3CH2I +H+_CH3CH2CH2OHHICH3CH2OC

5、H2CH2CH3ICH3CH2OCH2CH2CH3CH3CH2OCH2CH2CH3 + HICH3CH2I + CH3CH2CH2OH(1mol)(CH3)3COCH3 + HI(1mol)H+(CH3)3COCH3+ I_H+(CH3)3COCH3(CH3)3C+ + CH3OH(CH3)3C+ + I_(CH3)3CI(CH3)3COCH3 + HI(CH3)3CI + CH3OH(1mol)2021-12-4苯基醚OCH2CH357%H120 130OHCH3CH2+问题：如何区别醚、烷烃？2021-12-4判断反应发生在a位还是b位？H3C O CH2CH3HabIa)b)HCOCCH

6、3CH3CH3CH3H3CabIc)O RIab位阻碳正离子稳定性2021-12-4六、醚的自动氧化2021-12-4七、1,2-环氧化合物的开环反应1、酸性开环HCOCH2H3C+ CH3OHHCH3CHOCH3CH2OHHCOCH2H3C+ HClCH3CHClCH2OHHCOCH2H3C+ HCNCH3CHCNCH2OHHCOCH2H3C+ H2OHCH3CHOHCH2OH2021-12-4机理HCOCH2H3C+ CH3OH +HCH3CHOCH3CH2OHHCOCH2H3CH+HCOCH2H3CH+HCOCH2H3CH+orHCOCH2H3CH+( I ) ( II )which o

7、ne ?HCOCH2H3CH+( I )H+CH3CHOCH3CH2OH2021-12-4机理HCOCH2H3C + CH3O_CH3CHOCH2OCH3_CH3OHCH3CHOHCH2OCH32、碱性开环HCOCH2H3C+ RMgXCH3CHOMgXCH2RH2OCH3CHOHCH2RHCOCH2H3C+ NH3CH3CHOHCH2NH2HCOCH2H3C+ CH3OCH3CHOHCH2OCH3_CH3OHHCOCH2H3C+ OHCH3CHOHCH2OH_2021-12-4思考题：COCH2+ CH3O_CH3OHHH3CH2C+ CH3OHH+COCH2HH3CH2C( S )?202

8、1-12-4答案：COCH2+ CH3O_CH3OHHH3CH2C CH3OHH+COCH2HH3CH2C( S )COCH2HH3CH2CH+CCH2OHHH3CH2CH3COH+H+_CCH2OHHH3CH2CH3CO( R )COCH2OCH3HH3CH2C_CHOCH2OCH3HH3CH2C( S )( S )2021-12-4四、环氧化合物的开环反应H2C CH2ONaOHH2OHXRMgXH2C CH2HOOHH2C CH2HOClRCH2CH2O MgXH2OH+RCH2CH2OHB：OH-,RO-,NH3特点：1)能形成含有两个官能团的化合物；2)和RMgX反应，制备比RMgX

9、多2个碳的伯醇2021-12-4问题：反应发生在哪个部位？HC CH2OCH3BabHX2021-12-4酸催化：亲核试剂优先进攻取代多的碳； SN2反应(具有SN1部分特征)HC CH2OCH3HClH3C CHClCH2OH2)HCCH2OCH3NaOC2H5C2H5OHHCCH2OC2H5OHCH31)碱催化：a)进攻取代少的C，为SN2反应；背面进攻b)开环需要强碱(强亲核试剂)2021-12-4五、冠醚(crown ether)含有 -O-CH2CH2- 重复单元的大环多醚OOOOOO1818-Crown-6相转移催化剂2021-12-42021-12-4一、结构二、分类和命名三、物

10、理性质四、形成yang盐五、CO 键的断裂六、醚的自动氧化七、1,2-环氧化合物的开环反应1、酸性开环2、碱性开环八、环醚和冠醚的作用九、醚的制备2021-12-4四、形成yang盐ROR + HClROR + ClH_+.ROR + H2SO4ROR + HSO4H_+.ROR + BF3.ORRBF3_+五、CO 键的断裂CH3OCH3 + HICH3OH + CH3ICH3OH + HICH3I + H2O亲核取代SN2 机理适于伯烷基醚CH3OCH3 + HICH3OCH3 + ICH3I +_H+质子化CH3OCH3 + I_H+H3CH3.OHCI+CH3OH2021-12-4苯基醚OCH2CH357%H120 130OHCH3CH2+问题：如何区别醚、烷烃？2021-12-4机理HCOCH2H3C + CH3O_CH3CHOCH2OCH3_CH3OHCH3CHOHCH2OCH32、碱性开环HCOCH2H3C+ RMgXCH3CHOMgXCH2RH