403221 ???????????? ????????????????????????? (amines and nitrogen compounds)

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403221 ?????????????????????????????????????
(amines and nitrogen compounds)

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

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?????????

• Amine ???????????????????????? NH3 ????????
• 1o amine RNH2
• 2o amine R2NH
• 3o amine R3N
• ???????????? N ???? trigonal pyramid

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• Nitrogen inversion (pyramid inversion)
• ??????? R ??? amine ???????????? amine ??????????
  chiral molecule ?????? 2 enantiomers
• ??????????????????????????????? enantiomers
  ????????????
• ??????? enantiomers ??????????????????????????????
  ????????? transition state ??? sp2-N ????????
  Nitrogen inversion

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????????????????? (Amine)

• ?????????
• ???????????????????????????? N ????????
  ?????????? amine

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• ???? IUPAC
• ???????????????????????? -NH2 ???????????????????
  ? alkanamine
• ??????? -NH2 ????????????????????
  ???????????????????

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• ?????????????????? N ???? N-alkyl ????
  N,N-dialkyl ???????????? alkanamine

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• aniline ??????????????? benzene ????????? -NH2
  ??????

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• ??????????????????????????????????? ?????????
  -NH2 ????????????????? amino

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???????????????

• ????????
• MW ???????? (oC)
• (CH3)3N 59 3
• CH3OCH2CH3 60 8
• CH3NHCH2CH3 59 37
• CH3CH2CH2NH2 59 48
• CH3CH2CH2OH 60 97

3o amine bp. ???????????? ether
1o 2o amine bp. ??????? alcohol
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• ????????
• 1o, 2o amine ?????????????????????????????
  ?????????????????????? 3o amine
  ??????????????????????

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• ????????
• amine C1-C6 ??????????? ?????????
  ???????????????????
• amine ?????????????????????????????????
• ?????
• CH3NH2 , CH3CH2NH2 ?????????? ammonia
• amine ??????????????????

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• ?????????? amine
• aliphatic amine ?????????????? ammonia ?????
  inductive effect ????? cation ?????????????????

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• aromatic amine ??????????????? aliphatic amine
  ????? resonance effect
• elecctron ??????? N ??????????????? aromatic
  ??????????????????? electron ????
  ?????????????????? H ???????????

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????????? amine

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

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• 1.2 reduction ????????? nitro

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• 2. ????????? alkylation ??? ammonia ???? amine

?????????? 1o amine ??????? NH3 ?????????
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• 3. Grabriel synthesis (?????????? 1o amine)

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• 4. ???????????????????????????????????
• 4.1 Hofmann degradation

OBr- ?????? NaOH Br2
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• 4.2 Curtius reaction

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• 4.3 Schmidt reaction

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???????????? amine

• 1. ???????????

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• 2. Alkylation

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• 3. Hofmann elimination

?????????????
????????????????? alkene ?????????????????????????
???????????
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• 4. ??????? amide

??????????????????????????? amine
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• 5. ???????????? ????????? (HONO lt-- NaNO2 HCl)

??????????????????????????? amine
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• 6. ???????????? diazonium salt
• 6.1 ??????????????????? N2

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• 6.2 ????????? coupling

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• ?????????????????????????????? diazonium salt