????????????????????? (alcohol)

1
403221 ????????????????????? ??????????

• ??. ??. ??????? ???????
• ??????????? ??????????????
• ??????????????????????

2
?????????
3
????????????????????? (alcohol)

• ?????????
• ?????????????????? ??????? alcohol

4

• ???? IUPAC
• ???????????????????????????????????? -OH
  ?????????????????? alkanol
• ??????????? -OH ????????????? -OH ??????????????

5
(No Transcript)
6

• ?????????????????? -OH 2 ???? ???????? diol ????
  glycol

7
??????????????????? (ether)

• ?????????
• ?????????????????? 2 ????????????? O
  ????????????????????????? ether

8

• ????IUPAC
• ???? -OR ?????????????????????? alkane
  ???????????? alkoxy

9

• Cyclic ether
• ??? cycloalkane ????????????
• ?????????? O ????????????? -CH2- ??? oxa

10
???????????????-?????????

• ????????
• ????????????????????????????????
  ?????????????????????????????????????
• MW ???????? (oC)
• CH3CH2OH 46 78
• CH3CH2CH3 44 -42
• CH3OCH3 46 -25
• ????? ????????? ?????????????????????????????

11

• ????????
• ??????????????????????????????????????
• ?????????????????????????????????????????????
• ??????????????????????????????????????????????????
  ?????
• ????????()
• CH3CH2CH2CH2OH 8
• CH3CH2CHOH 26
• CH3
• (CH3)3COH 100

12

• ??????????????????????????????????????????????????
  ????????????????

13
???????????????-???????

• ????????
• ??????????????????????????????????????????????????
  ????????????
• MW ???????? (oC)
• CH3CH2OCH2CH3 74 35
• CH3CH2CH2CH2CH3 72 36
• tetrahydrofuran 72 66
• (THF)
• cyclic ether ????????????????? non-cyclic ?????
  cyclic ether ?????????????????????????????????????
  ????????????????

14

• ????????
• tetrahydrofuran ?????????????? diethyl ether
  ?????????????????????????????????????
• non-cyclic ether ???????????????????

15
??????????????????

• 1. ???????????????????????????
• 1.1 reduction

??? NaBH4 ??? LiAlH4 ???
16

• 1.2 ???????????? Grignard reagent (RMgX)

17
????? C ????????????????????????????
18

• RMgX ?????????????????????????????????????

19

• ???????????????????????????????????????????
  Grignard reagent

20

• 2. ?????????????????????????????? alkene
• 2.1 hydration

21

• 2.2 hydroboration-oxidation

22

• 3. ?????????????????????????????? R-X
• ????????? hydrolysis

23
?????????????????????
24
?????????????????????

• 1. ???????????

????????????????????????????????????????????????
Na
25
??????????? CH3OH gt 1o gt2o gt3o ?????????

• pKa ???????????
• CH3OH 15.5
• H2O 15.7
• CH3CH2OH 15.9
• (CH3)3COH 18.0

26

• ??????????????????????????????????????? alkoxide
  ion

Inductive effect ???? alkyl R ???????????????????
?? ????? alkoxide ion ???????????????????????????
??
27

• 2. ???????????

28

• 3. dehydration

29
E1
E2

• ????? b-H ???????????
• ????????? alkene ????????
• alkene ???????????????????????????????????

30

• 4. ??????? alkyl halide R-X

31
SN2
SN1
32

• Lucas test -reagent ??? HCl ZnCl2
• -???????????? SN1
• -????????????????????????? 1o, 2o ???? 3o

3o ROH ?????????????????? 2o ROH
??????????????????? 5-10 ???? 1o ROH
?????????????? 15 ????????????????????
33

• reagent ???????????? RX ??? ROH

34

• 5. esterification

35

• 6. oxidation

?? H ???/???? ????? O
1o alcohol
36
1o alcohol

• Strong oxidizing agent
• KMnO4/OH-
• Na2Cr2O7/H H2CrO4 (chromic acid
• oxidise 1o alcohol ???? carboxylic acid
• Mild oxidizing agent
• pyridinium chlorochromate, PCC
• CuO, ???????????
• oxidise 1o alcohol ???? aldehyde

37
2o alcohol
3o alcohol ??????? oxidation
38
????????????????

• 1. Williamson synthesis

R-X ??????? 1o alkyl halide -X ??????? Br, I
???????????????????? symmetric ??? asymmetric
ether
39

• 2. Dehydration of alcohol

• ROH ??????? 1o alcohol
• ?????? symmetric ether
• ???????????

40

• Mechanism SN2

41
???????????????????

• 1. ??????????????????

?????? HX HI gt HBr gt HCl
42

• Mechanism

SN2 ????? R ?????? 3o alkyl
43

• Mechanism

SN1 ??????? R ???? 3o alkyl
44

• 2. ????????? autooxidation

45

• ???????????????????
• ??????????????????????? CnH2n2O
• ????????????????????????????????

46
Epoxide

• 3-membered cyclic ether

47
????????? epoxide

• 1. ?????????????????
• 2. ????????? bromohydrin

48

• 3. ??? peroxyacid

49
???????????? epoxide

• 1. ?????????????????????? (acid-catalysed ring
  opening)

Nucleophile ??????? H2O, ROH ?????
50

• mechanism

CH3OH ???? nucleophile ?????????????????? more
substituted carbon ??????????????????????????????
51

• 2. ?????????????????????? (base-catalysed ring
  opening)

Base (Nucleophile) ??????? OH-, RO-, H-, R-MgX
?????
d-
d
52

• mechanism

OH-, RO-, H-, R-MgX ???? nucleophile
?????????????????? less substituted carbon
??????????????????????????????
53
Thiol (Mercaptan) R-SH
????????????????? (thiol)

• ????????? -?????????????????? ??????? mercaptan
• ???? IUPAC -?????????????? alkanethiol
  ??????????? -SH ????

54
????????? thiol ??? ????????????

• 1. ????????? NaSH ???? KSH

55

• 2. ????????? thiourea

56
???????????? thiol

• 1. oxidation

2. ???????????
57
Thioether R-S-R
??????????????????????? (thioether)

• ????????? -??????????????????????????? S ???????
  sulfide
• ???? IUPAC -???? -SR ??????????????????????????
  alkane ???????????? alkylthio

58
????????? thioether
59
???????????? thioether

• oxidation