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E(2)

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

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