MindMap Gallery Natural Medicinal Chemistry Spectral Resonance Properties of Sugars
This is a mind map about the spectral resonance properties of sugar in natural medicinal chemistry. By analyzing the spectral properties of sugar, you can further understand its structure and properties, as well as its interactions with other compounds.
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This is a mind map about bacteria, and its main contents include: overview, morphology, types, structure, reproduction, distribution, application, and expansion. The summary is comprehensive and meticulous, suitable as review materials.
This is a mind map about plant asexual reproduction, and its main contents include: concept, spore reproduction, vegetative reproduction, tissue culture, and buds. The summary is comprehensive and meticulous, suitable as review materials.
This is a mind map about the reproductive development of animals, and its main contents include: insects, frogs, birds, sexual reproduction, and asexual reproduction. The summary is comprehensive and meticulous, suitable as review materials.
Spectral resonance properties of sugar
IR
α-glucoside has strong absorption peaks at 770 and 780 cm-1
MS
Glucoside acetate 331 fragment peak intensity: α > β
1H-NMR
non-signal peak
solvent peak
D2O is the solvent: residual H, ~4.8
water peak
~4.8
Impurity peak
Look at the points ratio
chemical shift
Terminal proton: δ4.3~6.0
Flavonoid 3-β-D-Glc: 5.3~6.0
β-D-Glc in other positions of flavonoids: 4.8~5.2
Glycosides: <4.8
Methyl 5C sugar
δ~1.0 (-CH3)
Other protons
δ 3.2~4.2
ortho coupling constant
When the dihedral angle is 90°, the coupling constant is 0; when the dihedral angle is 90°~180°, the coupling constant becomes larger as the angle increases; when the dihedral angle is 0°~90°, the coupling constant becomes larger as the angle increases. Increasing the coupling constant becomes smaller. In the pyran ring, when two adjacent protons are both a bonds, the dihedral angle is 180°, and the coupling constant is 6~8Hz; when one is an a bond and the other is an e bond, the dihedral angle is 60°, and the coupling constant is 60°. The constant is 2~4Hz
When the glycoside bond is of the β-D or α-L type, its terminal protons and H-2 are both a bonds, and the coupling constant is 6~8Hz; when the glycoside bond is of the β-L or α-D type, its terminal protons The matrix proton is an e bond and H-2 is an a bond. The coupling constant is 2~4Hz.
2-H sugar in the e bond: rhamnose, mannose, lyxose
a-e, e-e dihedral angles are 60° or 120°, the J values are similar and cannot be judged
13C-NMR
Chemical shifts and coupling constants
-CH3: ~18; CH2OH: ~62; CHOH: 68~85; Terminal C: 95~105
The chemical shift of the terminal carbon is greater than 100: β-D, α-L of the C1 formula; α-D, β-L of the 1C formula; the chemical shift of the terminal carbon is less than 100: α-D, β-L of the C1 formula ; β-D, α-L of formula 1C
Coupling constants and glycoside bond configuration
Pyranose C1 formula
β-D, α-L: <164 (160~165) Hz
α-D, β-L: >165 (170~175) Hz
Pyranose 1C formula: rhamnose
α-L: 160~170 Hz
β-L: 150~160 Hz
Glycosylation shift (important!)
concept
After sugar and aglycon form glycosides, the chemical shift values of α-C, β-C of aglycon and the terminal carbon of sugar all change. This change is called glycosification shift.
Change rules
terminal carbon
Many move to the lower field, and ester glycosides move to the higher field.
aglycone
α-C: Move downfield
β-C: Multi-directional high field movement
Phenol, ester aglycone
α-C: Move upfield
β-C: Move slightly downfield
Glycoside shifts of different types of alcohol glycosides
β-C: Similar to small but different in size
α-C: Same as 5 different as 10 and the remaining 7
Common 13C-NMR substituent displacement effects
-OH methylation shift
Regardless of alcohol or phenol-OH
α-C low field displacement
β-C high field displacement
-OH acylation shift
Alcohol-OH
α-C low field displacement, β-C high field displacement
Phenol-OH
α-C high field displacement, β-C low field displacement