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sp3 .
:
(ChemicalAbstracts).
,
.
:
,
.
,
().
( ).
:
E,,,
.
,
.
sp3
()
~6Kcal/mol.
.
.
:
(
).
:
.
(Lewis)
o.
.
:
Kb (pKb),.
.
(RNH2),
()RNH3+.
:
:
,Ka,pKa
()
:
: pKa
: pKa
.
(pKa 10)(pKa =15,7)
(pKa =45).
:
()
:
pKa :NH4+<CH3NH3+ <(CH3)2NH2+ <<(CH3)3NH+
.
.
O
C
N
H
O
C
N
H
H
N H
H
G,
.
(),()
()
().
.
(pKa 40)
(LDA)
LDA
()
1. :
2. :
. ,
,
Gabriel
pKa 8,3
O
R
LiAlH4
NH2
Et2O
O
R
H2N
AlH3
H
H
R
H
NH2
H
H
R
H
,.
,
,
..
.NaBH3CN.
,
85%
,,
2/NiNaBH3CN,
Hofmann
.
( )
Hofmann
Hofmann
1.
Hofmann
2.
Curtius
()
Hofmann
: ()
CH3I
().
To,Ag2O
,.
Saytzef.
Hofmann
:
,,..,
,.
SN2
:
.
.,
,.
:
().
.
.
2:
~33003400cm1
:~3350cm1
R2:3300 3500cm1
R4+: 22003000cm1
1HR
.
D2O
().
13CR
.
20ppm.
13CNMR
PapaverSomniferum:
N
N
,
,
1.
,,
,
.R S
.
2..
.
R C NH2
O
H2SO4
R C NH2
+O H
_
HSO4
3. ,
.
) ) ) )
4.
;.
) CH3CH2NHCH(CH3)2 ) N)
5.
Hofmann Curtius;
6.Hofmann
;,
.) CH3CH2CH2CH(NH2)CH2CH2CH2CH3 )
) CH3CH2CH2CH(NH2)CH2CH2CH3 )
7. Hofmann ,
;.
NH
1. CH3I, ()
2. Ag2O, H2O
3.
8. (..3C)
(..7C),;
9. 1;
) ) ) )
) ,)
10.;
) ) ) ) )
11. ;
) ) ) 1)) 1
)5)
12.,C8H17N,.
Hofmann,5(,)1.
,;
13.//.
,.
14.
,
.,Trger
..
15. :
16. ,,
(1,3,5).;
N
CH3
17. .
,
.
;.
18. .
.
CH3
CH2CHNHCH3
19.,1
;
20.Hofmann
;,
;
21. Gabriel
:
) 1 ) 3) )H2NCH2CO2H()
(:
.;),
,;
22..
23.
()().
24. C7H13N 13CNMR
=21,0,26,847,8ppm.,
CH(CH=CH2)3,Hofmann.
.
25. ,,.
.
.
26. ,Hofmann,
.
.
27.()
Hofmann;
) 3 ) 2 3) 1)1 2
28. Hofmann ,,
.
.
29. ,,
,
..
30. ,
. IR:3330cm1.
1R: =0,91(t,J =7Hz,3H),1,33(s,1H),1,52(m,10H),2,70(t,J =6Hz,2H)3,0
(m,1H)ppm.
MS:m/z ()=127(+,43),84(100)56(20).
31. IR 1715cm1
NaBH3CN,,C6H15N.IR 1HNMR
. ;
(s,9H)
(d,3H)
(q,1H)
McMurry:
124.5
224.9
324.12
424.13
524.16
624.17
724.18
824.23
924.24
1024.25
1124.28
1224.35
1324.31
1424.30
1524.32
1624.37
1724.38
1824.40
1924.45
2024.48
31 24.19