10.%20Alkyl%20Halides

1
??? ????????? ???????
2
????? ?????????

• ????? ?????? ?X? ???? ?????? ?? ????Sp3 ???
  ??? ??? .
• ????? X ?? ???? Sp2 ???? ??? ??? ???.
• ???? X?? ???? Sp2 ???? ???? ??? ??? ???.
• ????? ??

3
????? ? ????? ?????

• ???????? ?????????????? ?? ???? ????? .
• ????? ????- ?????? ???? ???? ?? ???? ???? ????
  ??? ???? ???? .
• ???? ?? ????? ?? ?? ????????? (???? ????) ????
  ???.
• ?????? ?? ????? ?? ??? ??????? ???? ???.

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

• ???? ??????? ??? ?? ???? ?????, CH3X
• ??? ??? ????? ?? X ?? ?? ????? C-C ??? ???
  ???? .
• ??? ??? ????? ?? X ?? ?? ????? ????C-C ???
  ??? ???? .
• ??? ??? ????? ?? X?? ?? ????? C-C ??? ???
  ???? .

6
??? ???
??? ???
??? ???
7
?? ???????

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

8
????????? ????? ???????

• ?? ????? ????
• ???? ???? ???? ???? ??????? ????
• ????? ????? CF3CHClBr ?? ??????? ??? .
• CHCl3 ?? ????? ???? ???? ??????? ?? ???.(???????
  ? ????? ????? ??? .)
• ??????? ? ??????????? ?????? ?? CFC ??
• ????? 12 CF2Cl2 ?? ????? 22 CF2CHCl ?? ????
  ???? ????? ??? ?????? ??????? ??? ???.
• ???? ??? ?? (DDT)Dichloro-Diphenyl-Trichloroethane
  ?? U.S. ????? ??? ???.

The decoding system for CFC-01234 0 Number of
double bonds (omitted if zero) 1 Carbon atoms
-1 (omitted if zero) 2 Hydrogen atoms 1 3
Fluorine atoms 4 Replaced by Bromine ("B"
prefix added) a Letter added to identify
isomers, the "normal" isomer in any number has
the smallest mass difference on each carbon, and
a, b, or c are added as the masses diverge from
normal.
9
??? ????
10
???????? ??????

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

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Naming with Multiple Halides

• If more than one of the same kind of halogen is
  present, use prefix di, tri, tetra
• If there are several different halogens, number
  them and list them in alphabetical order

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Naming if Two Halides or Alkyl Are Equally
Distant from Ends of Chain

• Begin at the end nearer the substituent whose
  name comes first in the alphabet

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Many Alkyl Halides That Are Widely Used Have
Common Names

• Chloroform CHCl3
• Carbon tetrachloride CCl4
• Methylene chloride CH2Cl2
• Methyl iodide CH3I

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

• m 4.8 x d x d ??d ?????? ( ?????? ?? DEN ) ?
  d ????? ( ??? ?????) ?? ???? ???????? ???.
• ??????????????? F gt Cl gt Br gt I
• ??? ????? C-F lt C-Cl lt C-Br lt C-I
• ????? ?? ???? C-Cl gt C-F gt C-Br gt C-I 1.56 D
  1.51 D 1.48 D 1.29 D
  
• ???? ???? ?? ??? ?????? ??? ?????? ???.

16
???? ???

• ??????? ??? ??????? ???? ????? ??? ?? ???? ??
  ????.
• ?????? ??????-?????? ????? ???? ?? ???????? ?????
  ??????.
• ??????? ????? ???? ?????? ?????? ????? ???.
• ??? ??????? ???? ??? ?? ?????? ?? ???.
• ??? ???? ???? ??? ?? ????? ?? ????.
• (CH3)3CBr CH3(CH2)3Br
  73?C 102?C

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Properties of the Halomethanes
18
????? ??

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

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Preparing Alkyl Halides

• Alkyl halide is formed by the addition of HCl,
  HBr, HI to alkenes to give the Markovnikov
  product (see Alkenes chapter)
• Alkyl geminal dihalide from anti addition of
  bromine or chlorine

20
??? ??? ???? ????? ??????

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

21
?????? ??? ???? ???????

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

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Multiple Substitution
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25
??? ???? ????? ???????
????????? ???????
?????? ???? ????????? ?? ?????? ???
1.0 3.5 5.0
????? ??????? ?????????
26
?????? ??????? ?????

• ??????? ????? ???? ??????? ?????? ?????.
• ??? ??????? ?? ?????? ????? ?? ????? ??? ?????
  ??????.(???? sp3 ??? ?? CC)
• ?? ??????? ?? N- ????????????? (NBS) ?? ????? ???
  ????? ??????? ?????.

27
??????? ?????

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

28
??? ???? ????? ???????
??? ??? ??? ????? ??????
lt ??????
?????? lt
29
???? ????? ??????? ?? ???? ?? HBr????? ??

• -OH ???? ?????? ??? ?? ???
• -OH2 ???? ??? ????? ???? ???
• ???? ??? 3 ? 2 ?? Br- ?? ???? SN1 ????? ?? ????
• ???? ??? 1 ?? ????SN2 ????? ?? ????

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HCl ????? ??

• ????? ???? ???? ???? ?? ?? ????? ???.
• ZnCl2 ?? ????? ?????? ?? -OH ?????? ?? ???
  ?????? ?? ????? ?????.
• ????? ????? ??? ??????? ???.
• ?????? ????? ZnCl2 ????? ?? HCl
• ??????? 1 ?? ?????? ????? ?? ???? ?? ??? ????.
• ??????? 2? ???? ??? ??? ????? ????? ?? ????.
• ???????3? ?? ???? ?? ?? ????? ????? ?? ????.

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?????????? ???????? HX

• HI ????? ??? ???
• ????? ??? ?? ???????? 1 ? 2 ?? ????.
• ???? ??? ???? ????? ????? ???? ???? ???.
• ?????????? ?????? ???? ??? ??????? ???.

32
??????? ?? ???????? ????

• ????? ???? ?? ???? ??? 1 ? 2 ?? ????.
• PCl3 ???? ????? ?????( ??? SOCl2 ???? ???)
• PBr3 ???? ????? ?????
• P ? I2 ???? ????? ????(PI3 ?????? ????)

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??????? ?? PBr3

• P ?? -OH ??? ??? ? Br- ???? ?? ???.
• Br- ?? ??? ???? ?? ???.(SN2)
• HOPBr2 ???? ?? ???.

34
????? ?? ?????? ?????

• ????? ?????? SO2 ? HCl ?? ???.
• S ?? -OH ?????? ? Cl- ???? ?? ???.
• Cl- ? H ?? ?? OH ??? ?? ???.
• ????? C-O ?? ???? ? Cl- ?? ??? C?????? ?? ????.

35
?????????? ??? ????

• ???? ?? ?? ??? ????? ????? ???(Mg ?? Li)
• ???? ?? ???? ???? ???(????? ???????)
• ?? ?? ????? ?? ???? ????? ???? ???? ???.
• C X
• C O
• ?? ????? ????-???? ???? ????? ?? ???.

36
Organometallic Coupling Reactions

• Alkyllithium (RLi) forms from RBr and Li metal
• RLi reacts with copper iodide to give lithium
  dialkylcopper (Gilman reagents)

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François Auguste Victor Grignard

• Born in Cherbourg, 1871
• PhD, University of Lyon, 1901
• Nobel Prize in Chemistry, 1912

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Reactions of Grignard Reagents

• Many useful reactions
• RMgX behaves as R- (adds to CO)
• RMgX H3O yields R-H

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Grignard Carbon as Nucleophile
40
?????????? ????????

• ????? R-Mg-X (??? R- MgX ????? ?? ???)
• ?? ??????? ?? ??? ?? ?? ?? ?? ?? ???? ?????? ??
  ?? ?????.
• ??????? ????? ????? ????
• ???? ??? ?? ????? ?? ??? ?????? ????? ???.
• ??? ???
• ??? ???
• ??? ???
• ?????
• ????

41
?????? ?? ?????????? ????????
42
??????? ??? ????????

• ?? ?? ???? ?????? ??? ????? ???? O-H, N-H, S-H
  ?? -CC-H ????? ???? ????? ????. ?? ???? ????
  ??? ????? ??????? ???????? ????? ??? ?????? ?? ??
  ????? ?? ???.
• ?????? ???????? ??????? ??????? ???? ???? ???
  CN, CN, SO ?? NO ????? ???? ????? ?????.

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Utility of Organometallic Coupling in Synthesis

• Coupling of two organometallic molecules produces
  larger molecules of defined structure
• Aryl and vinyl organometallics also effective

45
Lithium dialkylcopper reagents react with alkyl
halides to give alkanes
46
Problem
47
Problem Identify reagents
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Problem

• a BH3/THF followed by H2O2/OH-
• b PBr3/ether
• c (CH3)2CuLi/ether