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

" h0 H/ D1 T) B

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 carbon will show a downfield shift while the belta carbon will show a : j: L5 p& a4 s+ H3 b- t% t( B, Iupfield shif.

See the following article how to revise a structure reported before just using the above rule!

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.
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( _! S( l9 ~& R' J( ^Another compound with one OH group acetylated: it could be C-6 OAc, C-7 OH (compound I in the article) or could be C-6 OH, C-7OAc (compound II # R, @3 n) [! U/ jin 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?

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The auhors resovled the problem:

/ X# P/ ^' H5 }2 E/ {If C-6 (80.5) and C-7 (78.5) were right, meaning both the chemical 7 h4 K0 Q5 S0 {0 d; X8 e3 jshifts of C-6 (79.3 to 80.5) and C-7 (76.2 to 78.5) were increased. That assupmtion violates the above rule.

# K. ?( K; G' t3 TSo chemical shift of C-6 was not 80.5 but 78.5, chemical shift of C-7 was not 78.5 but 80.5.
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+ K7 J1 y# o1 }* {& H3 XC-6 (78.5) and C-7 (80.5) meaned that C-6 shifted to highfield (from , u4 }9 U4 s0 i h" ^. z79.3 to 78.5), C-7 shifted to lowfield (from 76.2 to 80.5). Logically, ( t7 h2 b3 T. h( w: T" }it was the C-7 with the OAC group (compound II), not the C-6 with the 8 G, P- t' j$ G) z$ _) M4 tOAC group (compound I).
* L% x' U' | {" ^& @
) ?6 s. ~( @# e$ JSimple, logic structural revision published in 1981!

; }+ b! J/ l% e$ x* O: }5 [' s

  . i1 M0 s! R" C: n1 m) g

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]
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[此贴子已经被作者于2009-5-28 23:48:20编辑过]

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