Diels-Alder Reaction

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

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• ??????????
• 1,4-??
• ????
• ?????????
• Diels-Alder Reaction

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??? ??????

• ????(????) ??CnH2n-2
• ??? ??
• ???????
• ??????
• C SP??

????835kJ/mol
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???????
????

?????
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Bond Properties vs. Hybridization

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???????

• Nomenclature of Alkynes
• 1. Naming of alkynes is very similar to the
  naming of alkenes, using the root name of the
  longest carbon chain. The ending, however, is
  changed from -ene to -yne, and a number is given
  to show the location of the triple bond for
  molecules of more than three base carbons.

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• 2. ???????????????????????????????????,??????????
  ??????????

1,3-???-5-? 3-??-1-?
(not 2-??-4-?)
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Ethyne
Propyne
Acetylene
2-Butyne
1-Butyne
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4-Chloro-4-methyl-2-pentyne
5-Bromo-2-methyl-3-heptyne
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5-???-1,3,6-???

4-???-1-??-5-?
3. ??
??? 3-???
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?????????

• ????
• ????????????FeCl3?HgCl2??????
• ?????????,???????????

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2. ??(Kucherov Reaction)
Hydration of an Alkyne
?????????,????????????
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Mechanism of Alkyne Hydration
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Keto-Enol Tautomerism

• Tautomers Two compounds with different
  structures but which exist in equilibrium.
• Most often, the two structures differ by the
  position of a proton.
• NOTE CAREFULLY This is equilibrium, not
  resonance!

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3. ??

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1). ?KMnO4??
?????????,??????
2). ?????
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4. ??????

• ?????????????
• 1). ???????
• ?NaNH2?????,?????
• (-33?C)????

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????,??????????
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2). ??????????

• ???????????????,??????????

?????????????????????????!???????
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5. ????
Why? ???????????
?????????H2CCH-gtCH3CH2-
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6. ?????

• 1)????

???????????,?????????Pd-CaCO3 /Pb (OAc) 2/ ??
(??Lindlar???)??????????????????????
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?????????
2)Na/NH3(l)??
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???????
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?? ?????

• 1)??????HX
• 2)??????????

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??? ???

• ????????????????
• ???????????
• 1. ??
• 1) ?????(??????1??????),??
  ?????????????????????
• 2)????? (?????1?????),??
  ???????
• ??????????1,3-????

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3) ????? ?????????????????,??
????????1,4-????

• 2. ??
• 1)???????????????,??????????????
• 2)?????????Z,E???

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????????

• ??????
• ???????????C-1?C-3SP2C-2SP?

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2. 1,3-???
C-1?C-2?C-3?C-4 SP2
??????
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1,3-Butadiene

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Bonding Molecular Orbitals of 1,3-Butadiene
Y1
Y2
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Antibonding Molecular Orbitals of 1,3-Butadiene
Y3
Y4
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3. ????

• 1. ?? ????????????????,????????,?????,??????
• 2. ??
• ?-???? CH2CH-CHCH2
• CH2CH-CHO
• p- ? ??? CH2CHCl
• CH2CHCH2
• CH2CHCH2-
• CH2CHCH2.

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?-???? CH3-CHCH2 ?-p??? (CH3)3C
(CH3)3C- (CH3)3C.
3. ?? ?????? ?????,???????????
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4. ??

• P-? C
• ?-p, ?-? ???C
• ??????????????? C-H?????-CH3gt-CH2RgtCHR2gtCR3
• ??????
• ??????

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4. ?????????????????

• 1)1,4-??

???????????1,2-??1,4-???
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2) ??(???)??????????????????????????????(???)???
???????????????
????(2)?(1)???
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??1
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??2
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??

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???????????
???(2)gt(1)
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Question
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3) Diels-Alder Reaction

????????????????????
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3) Diels-Alder Reaction

• ??a. ??????????
• b. ????????

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????
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Homework Assignment

• P97 2(1,3,5) 3467891114151619

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????
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