3. ???? (addition reaction)

1
3. ???? (addition reaction) ??? ????????????,?????
?,???????????????????????????????????????????????(
????,???????????)?????????????????????   (1)????
?Pt?Pd?Ni???????,?????????????,???????,?????,???
??(heat of hydrogenation,1mol????????????)?  
2
????????(??????,?????) ???????????????????????????
????????? ???????????
?? ?? 1??? ??2??? ??2??? ???/kJmol?1
-137.2 -125.9 -126.8 -119.7
-115.5 (1)??????????,?????,????? R2CCR2 gt
R2CCHR gt R2CCH2 gt RCHCH2 gt CH2CH2 (2)?????????
? (3)??????-313.8kJmol?1,??????(-274.4kJmol?1)?
,???????????
3
???????? ??????????,?????????????? ???????????
,???????? ???/?????????????????,?????(Lindlar)???
,???????????????????????????,???????
?????????? ???????????,??????????? ????
(??????????)??????????
4
????????? ????????????,???????,?????????????????
??????,??????????
5
(2)?????? (a)????????????? ?????????????????,????
????     ????????HI?HBr?HCl (b)??????????????
??????????????,?????????(?)??????
6
??????????(Markovnikovs rule) (????) ????????????
????????,????????????????????????????,????????????
?????????????????? ???????????????? R2CCR
2 gtR2C gt CHR gt R2CCH2 gt RCHCH2gtCH2CH2 ???????
????,????????????????????
7
(c)??????(electrophilic addition reaction)??
????????????????????? ?????????????,??????????
??????????????????E ?????????????????????????????
??????????? ???,H???????,?????,????????????H??,?
???????sp2?????sp3???????????????????????????,???
sp2??? ???,???????????????????????? ???   ???
8
(d)????? (inductive effect) ??? ?????????????(????
?????)??,????????????????????????,??I??? ?????????
??? ???????,??????I??,?????I???I????????????,????
?????   ??????????????(?????P315??) NR3gt NH3
gt NO2 gt CN gt COOH gt F gt Br gt Cl gt I gt OAr gt COR gt
OCH3 gt OH gt C6H5gt CH2CH gt H gt CH3 gt C2H5 gt
CH(CH3)2 gt C(CH3)3 gt CO2-gt O?
????I??,???I???
9
(e)??p????? (hyperconjugation effect) ??? ???????
?????,??????sp2?????sp3??,???????????sp2??,????,??
???p?????????p????????C?H?????,?p???C?H???????????
,???? ?p?????      ????????? ??????????????????,??
????????????????????????,???????,?????????????????
??????(3?R)gt?????(2?R)gt?????(1?R)gt??????(CH3)
?
10
(f)????????? ????HX???? ???????? ???I??,???????
?C1??,C1?C2????????????,????H????C1,??????2?????
  ???????? ????H??????????,????CH3CH2CH2?(CH3)2
CH?(CH3)2CH?????CH3CH2CH2(2?Rgt1?R),??????2???
??
11
(3)?????? ????? ?????,??????????,??????????????
??????????,??????????sp????????,???????     ???
????????????,??????????(?????)?  ?????
?gt?gt?gt?????????,??????? ??????? ?????????????
12
(4)?H2SO4??? ??? ?????????????(??????),????????
????????????,??????? ??? ??????????,?????
??????(????)??????????,???????? ??????????,????
?????(????????,????)? ???????,???????
13
(5)????? ???????? ??????,??????????????     ??
??????????????????????,???????????? ?????????,?
???????
14
?????????? ????????????,????????(????????????),???
??????,??       (??????????????,?????????????
??????(interconversion isomery),?????????????
???HgSO4-H2SO4??????????????Kucherov???
15
(6)??????? ?????????? ????,???????????????????
?????????????
?? ????HOCl???,???????? ?????????????????
16
(7)????? ??????(2.1)???(2.0),BH???????
????????? ?????????(???BH3?????)???,?????????????
?(??????????),????????????????H2O2??,????????-??
???????     ??? ??????????????????????????
????????????????,???????????
 
17
????????? ?????????????,????????
??CH3CCHB2H6?(CH3CHCH)3B?CH3CHCHOH
? CH3CH2CHO
18
(8)????????? ??? ?????????????????????,?????????
,????????? ???????,???????????????????,??????????
????????????????????? ??????????-???????????1-????
?? ?? P867??15.2 ??1?a,c,d,g,I
2?a,c,e??3?1,2,3 9?15?,7-8???
19
????? ??? ???   ???   ???(1)??????????????,?
?????????????????????????? (2)????????????????????
?????????  ???????????,????????????????
20
(9)????????? (nucleophilic addition
reaction) ??????? ????????????????????????????????
?????????? ???????? ???????????????,???????????(?R
OH?HCN?RCOOH?)??????????    

21
????? ?????????,?????????,?????????????????????,??
??????????????? ??? ?????????????????????,????????
??????????????????????????????,???????????,???????
??????