????? Nitro Compunds

1
???? ???????
2
????? Nitro Compunds
?? Amides
? Nitriles
? Oximes
?????
? Amines
???????? Diazonium Salts Azo compounds
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????????
?.????????
RH,ArH ?H?-NO2??
RNO2(??)?ArNO2(??)
2?N-O????
P-p??
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?.????
??
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??????
(?)a-H????
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1.???????
??? ???? ??
(???) (??)
NO2???
a-H??????
????
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2.????????
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(?)???????
???????
????????????
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(?) ????
?
?????Fe,Sn,Zn HClSnCl2 HClH2/Ni
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(?) ?HNO2???
?
?
?
??
()
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??? ??-NH2
?.?????
RNH2?R2NH R3N?R4NX-
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1.??
???
CH3NH2
???
??N????????
???
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RNH2
1? (??) Primary Amines
R2NH
2? (??) Secondary Amines
??N????????
3? (??) Tertiary Amines
R3N
R4N
4? (???) Quaternary Ammonium Salt
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???
??????????
???
(CH3)3C-OH
(CH3)3C-NH2
3?
3o???
1?
???????????? !
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2.??

• ?????
• ???????

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(No Transcript)
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?????

• ??????????,?????????N?

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?????

• ???????????,??????

2-??-4-????
2-??-2-????
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???????????????????????
??????
????????
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?. ??
?(?)???Preparation by Nucleolic Substitution
1??????
1 ?
2?
3?
4?
??????
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2?????????
3.???????
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?(?)??Preparation by Reduction
1. ?????
2. ?
3. ??
4. ?
5. Alkyl Azide ???
1 ?
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6??????????? (Reductive Amination)
NH3
1 ?
2 ?
1 ?
2 ?
3 ?
1 ??????
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?.????
SP3
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SP3
SP2
SP3
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????????
???
N??????
????? ?
????,????,??????
??????,????
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????????
? ??N???,????
?????,????
Troger ?
???? ????????
????????????
S-
R-
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?.????
????? b.P?? ????????? ??
(????)
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?.????
SP3
Long electron pair
Basicity ??,??
Nucleophlicity ???,???
Resonance Activition to the Aromatic
ring Electophilic Substitution ??????????
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(?)??
Lewis Base
?????????
???????
??
??
pKb -lgKb
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???????pKb
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Basicity and Formation of Ammonium Salts
?????????
???? 2??1??3?
???? ??????gt??gt?????
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??N??????
??????
??????????
??N??????
? ??????
??????????????,??????, ??????
2o gt 1o gt3o
??(?????)??
3o gt 2o gt 1o
?????
1o gt 2o gt 3 o
????
1o gt 2o gt 3 o
pKb 3.01
pKb 2.73
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? ??????
?????
p-???
N????????
????????
? ??????????????
? ??????????????
?????
?????????????,?????

----?????????
????(-NH2, -OCH3, -CH3)
????(-NO2, -SO3H, -CO2H, -X, -NH3)
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? ???
?????
? ????
??? gt??? gt ? gt ???gt??gt ???? ???
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(?)?????
-
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?????? ????? ?????
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?????

• ??????gt??gt?(???????)

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Applications
?????????
???? (phenacetin)
???? (paraspen)
??? (???)
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Acylation and Sulfonylation
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?????
()
??????
???????
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(?)?HNO2??
NaNO2??
10
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20
??
??
30
??
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(?)?????
1.??
2.????????
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(?)???????
????
Schiffs base
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2.????(10?)
??(?)
??
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(?)?????

• ??? R4NX-
• ??? R4NOH-

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???

• ??????????,????,???????????
• ????????????,????????????????,????????????????????
  ????????????????,????TBA??

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?????

• ??????????????????????????????????????????????,???
  ???????????????????????
• ?????????????????????????
• ??????C12-C16????????????????????????

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?????

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

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2.????Hofmann??
a
ß
?ß-H
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?????????
??
???
?????????
????????
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Hofmann?? ??????C?????? ???
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????????
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(?)?????
1.??
2.????????
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(?)???????
????
Schiffs base
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2.????(10?)
??(?)
??
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(?)?????

• ??? R4NX-
• ??? R4NOH-

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???

• ??????????,????,???????????
• ????????????,????????????????,????????????????????
  ????????????????,????TBA??

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?????

• ??????????????????????????????????????????????,???
  ???????????????????????
• ?????????????????????????
• ??????C12-C16????????????????????????

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?????

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

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2.????Hofmann??
a
ß
?ß-H
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?????????
??
???
?????????
????????
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Hofmann?? ??????C?????? ???
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?? ??????
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(No Transcript)
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??? ???????
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????????
(?)????? (diazotization reaction)
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(?)????

• ??????????????,???05?,??????????????????,????????
  ?

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(?)????

• ?????,????????????,?????????????????,?????????????
  ?????

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?????????
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????????
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Transformations of Aryl Diazonium Salts
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Preparation of Phenols
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Preparation of Aryl Iodides
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(?)????
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(No Transcript)
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????????(Sandmeyer??)
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??
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(No Transcript)
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??????
?????????
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(No Transcript)
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(?)????

• 1.????

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2. ????(??)
?????????? ????? (?????)
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??????
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? ?????
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Azo compounds ?????
???
R,R??
??
????
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???
????????????
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??
??
???
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??? ???????

• ??????
• (?)???????

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(?)???????

• 1.?????????????

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2.??????
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????(??)
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?????