Structures in solid state and solution of dimethoxy curcuminoids: regioselective bromination and chlorination

Chemistry Central Journal

Petra Galer¹  Amalija Golobič¹  Jože Koller¹  Berta Košmrlj¹  Boris Šket¹ 

[1] Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, SI-1000, Ljubljana, Slovenia

关键词: α-halodiketones;    Halogenation;    Enols;    Regioselectivity;    Theoretical investigations;    NMR experiments of solids;    X-ray structures;    Dimethoxy curcuminoids;   

Others  :  787886
DOI  :  10.1186/1752-153X-7-107

 received in 2013-01-08, accepted in 2013-06-06,  发布年份 2013

【 摘 要 】

Background

Several papers described the structure of curcumin and some other derivatives in solid and in solution. In the crystal structure of curcumin, the enol H atom is located symmetrically between both oxygen atoms of the enolone fragment with an O···O distance of 2.455 Å, which is characteristic for symmetrical H-bonds. In the solution, the geometry of the enolone fragment is attributed to the inherent disorder of the local environment, which solvates one of the basic sites better than the other, stabilizing one tautomer over the other. In this paper, how the position of methoxy groups in dimethoxy curcuminoids influence the conformation of molecules and how the halogen atoms change it when they are bonded at α-position in keto-enol part of molecules is described.

Results

Six isomers of dimethoxy curcuminoids were prepared. Conformations in solid state, which were determined by X-ray single crystallography and ¹H MAS and ¹³C CPMAS NMR measurements, depend on the position of methoxy groups in curcuminoid molecules. In solution, a fast equilibrium between both keto-enol forms exists. A theoretical calculation finding shows that the position of methoxy groups changes the energy of HOMO and LUMO. An efficient protocol for the highly regioselective bromination and chlorination leading to α-halogenated product has been developed. All α-halogenated compounds are present mainly in cis keto-enol form.

Conclusions

The structures in solid state of dimethoxy curcuminoids depend on the position of methoxy groups. The NMR data of crystalline solid samples of 3,4-diOCH₃ derivative, XRD measurements and X-ray structures lead us to the conclusion that polymorphism exists in solids. The same conclusion can be done for 3,5-diOCH₃ derivative. In solution, dimethoxy curcuminoids are present in the forms that can be described as the coexistence of two equivalent tautomers being in fast equilibrium. The position of methoxy groups has a small influence on the enolic hydrogen bond. Theoretical calculations show that the energy gap between HOMO and LUMO depend on the position of methoxy groups and are lower in solution. Chlorination and bromination on α-position of 1,3-diketone moiety do not change the preferential form being cis keto-enol as in parent compounds.

【 授权许可】

   
2013 Galer et al.; licensee Chemistry Central Ltd.

【 图 表 】

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