请教这四种类似结构某个C化学位移的相对大小

zlfbaggio

4>3, 4>1

3>2,
1>2

3>1 (-OCO- alpha +56.5; belta +6.5; -OH alpha +49.0, belta +10.1) although 3 is close to 1

4>3>1>2

according to your conclusion，maybe 3 is the  lowest

北冥有鱼

 Why?
The conclusion is 4>3>1>2.

北冥有鱼

  On acetylation (OH group was changed to OCOCH3 group), the alpha ' H. T' `" A1 _9 i4 r0 zcarbon will show a downfield shift while the belta carbon will show a [/ d. `6 K2 L. Fupfield shif.
9 b/ a0 w# u# m* N# S- ~& _
See the following article how to revise a structure reported before just using the above rule!
$ O3 l' }5 m$ N
One compound with C-6 OH, C-7 OH (compound IV in the article):  chemical shift values of C-6 79.3 ppm, C-7 76.2 ppm were known.

# T8 ?' P5 n( {. xAnother compound with one OH group acetylated: it could be C-6 OAc, C-7 2 Z& h" ?4 }7 I4 |( KOH (compound I in the article) or could be C-6 OH, C-7OAc (compound II ! ?; B' F) U* P4 e4 vin the article). The chemical shifts of the two carbons are 78.1 and 80.5. How to determine which carbon (C-6 or C-7) has the OAC group?


The auhors resovled the problem:
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If C-6 (80.5) and C-7 (78.5) were right, meaning both the chemical 2 D2 R1 I& v" Y% ]shifts of C-6 (79.3 to 80.5) and C-7 (76.2 to 78.5) were increased. That assupmtion violates the above rule.

So chemical shift of C-6 was not 80.5 but 78.5, chemical shift of C-7 was not 78.5 but 80.5.
% V5 x0 U7 v; x: [$ \; i I! e- {5 Z
C-6 (78.5) and C-7 (80.5) meaned that C-6 shifted to highfield (from 79.3 to 78.5), C-7 shifted to lowfield (from 76.2 to 80.5). Logically, % O7 _4 `: _3 _" B; Mit was the C-7 with the OAC group (compound II), not the C-6 with the OAC group (compound I).

( q) S" S$ h- m0 {% SSimple, logic structural revision published in 1981!



  , ^# r8 S+ {( [8 H+ F5 s. @! b
* u1 b1 u8 s4 G% T5 i2 W7 ]' c+ O

北冥有鱼

 

北冥有鱼

More example:

CH3CH2OH  chemical shift values: 18 (CH3), 58 (CH2).
CH3CH2OAc chemical shifts values: 14 (CH3), 60 (CH2).

These data should be remembered to remind the above rule.

alpha carbon 60>58;

belta carbon 14<18.

[em79][em79]

[此贴子已经被作者于2009-5-28 23:48:20编辑过]

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