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Helicene analogs and preparation method thereof

A technology of helicene and compound, applied in the field of helicene analogs and their preparation, can solve the problems of small type and quantity, and achieve the effects of simple method, easily available raw materials, and short synthetic route

Inactive Publication Date: 2012-11-21
SUZHOU UNIV
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Problems solved by technology

In 2008, Caronna reported that 2,2'-diamine-1,1'-dinaphthalene reacted under the effect of m-chloroperoxybenzoic acid to generate 7,8-diaza[5]helicene (Caronna, T.; Fontana , F.; Mele, A.; Sora, I.N.; Panzeri, W.; Vigano, L.Synthesis 2008, 413.), however, this method is accompanied by the generation of many by-products
[0007] It can be seen from the above reports that the structure, synthesis and application of helicene analogs have been reported to a certain extent, but the types and quantities of structures of helicene analogs containing heteroatoms are still relatively small.

Method used

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  • Helicene analogs and preparation method thereof
  • Helicene analogs and preparation method thereof
  • Helicene analogs and preparation method thereof

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preparation example Construction

[0038] The present invention also provides a preparation method of helicene analogs, comprising the following steps:

[0039] Refluxing solid phosgene and bisimine compound in anhydrous tetrahydrofuran under the action of low-valent titanium reagent;

[0040] The product obtained by the reflux reaction is mixed with hydrochloric acid, then extracted, washed with water, and dried to obtain the helicene analogue.

[0041] The solid phosgene chemical name described in the present invention is two (trichloromethyl) carbonates, and structure is as shown in formula (V),

[0042]

[0043] The bisimine compound has a structure shown in formula (III) or formula (IV),

[0044]

[0045] Formula (III), Formula (IV),

[0046] Among them, R 1 H, OCH 3 , Cl or Br; R 2 H, OCH 3 , Cl, Br or OCH 2 O; R 3 H, OCH 3 , Cl, Br or OCH 2 O; R 4 for H, CH 3 or cyclohexyl; R 5 Is H or cyclohexyl; X is OH or NO 2 ; 6 and R 7 are each independently H or cyclohexyl.

[0047] Accordin...

Embodiment 1

[0058] Add samarium powder (0.9g, 6mmol) and 10mL of anhydrous THF into a 100mL three-necked flask, slowly inject TiCl under nitrogen protection, room temperature and stirring 4 (0.66mL, 6mmol) to obtain the mixture, reflux for 2h, and cool to room temperature to obtain a low-valent titanium reagent in black paste;

[0059] At room temperature and under the protection of nitrogen, the o-hydroxybisimine (1mmol) of the structure of formula (III) and solid phosgene (2mmol) were dissolved in 10mL THF, wherein, X is OH, R 1 for H, R 2 for OCH 3 , R 3 for H, R 4 for H, R 5 H, to obtain a mixed solution, slowly drop the mixed solution into the low-valent titanium reagent, add, reflux for 2 hours, after the reaction, mix with 100mL of 3% hydrochloric acid, and extract with 50mL of chloroform for 3 Once, combine the organic layers, wash 3 times with 50mL water until neutral, dry the organic layer with anhydrous sodium sulfate, filter off the desiccant, evaporate the solvent under ...

Embodiment 2

[0062] With the o-hydroxyl bisimine (1mmol) and solid phosgene (2mmol) of formula (III) structure as raw materials, wherein, X is OH, R 1 for H, R 2 for H, R 3 for H, R 4 for H, R 5 For H, the same preparation method as in Example 1 was used to prepare 5,10-dioxa-6,9-dioxo-18,20-diazadecahydro[5]helicene with a yield of 88 %.

[0063] The NMR data of the 5,10-dioxa-6,9-dioxo-18,20-diazadecahydro[5]helicene prepared in this example are: 1 H NMR (400Hz, DMSO-d6 )δ: 7.39(t, J=7.6Hz, 2H, ArH), 7.14-7.16(m, 2H, ArH), 6.95(t, J=7.6Hz, 2H, ArH), 6.19-6.21(m, 2H, ArH), 5.02(s, 2H, 2×CH), 4.25-4.33(m, 2H, CH 2 ), 3.26-3.36 (m, 2H, CH 2 ).

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Abstract

The invention discloses a [5] helicene analog and a [7] helicene analog. The analogs enrich the kind of helicene analogs. The invention also provides a preparation method of the helicene analogs. According to the method, heterocyclic helicene analogs are prepared from a bisimine compound and solid phosgene under the action of a low-valent titanium reagent. The heterocyclic helicene analogs are prepared through utilizing the reduction coupling effect of the low-valent titanium reagent and using the bisimine compound and the solid phosgene as raw materials in the invention. The method has the advantages of easily available raw materials, simplicity, short synthetic route and the like. Additionally, the regulation of the number of rings of the prepared helicene analogs can be realized through controlling the number of aromatic rings in the raw materials in the invention.

Description

technical field [0001] The invention relates to the technical field of organic chemistry, more specifically, to a helicene analog and a preparation method thereof. Background technique [0002] Helicene compounds are a class of non-planar aromatic compounds with helical chirality and ortho-condensation, which have excellent optical and electrical properties, and are widely used in nonlinear optical materials (Verbiest, T.; Elshocht, S.V.; Kauranen, M.; Hellemans, L.; Snauwaert, J.; Nuckolls, C.; Katz, T.J.; Persoons, A. Science 1998, 282, 913.) (Verbiest, T.; Sioncke, S.; Persoons, A.; Vyklicky, L. .; Katz, T.J.Angew.Chem., Int.Ed.2002, 41, 3882.), liquid crystal materials (Nuckolls, C.; Katz, T.J.J.Am.Chem.Soc.1998, 120, 9541-9544.), hands (Feringa, B.L.; van Delden, R.A.; Koumura, N.; Geertsema, E.M.Chem.Rev.2000, 100, 1789.) and other aspects show good performance, therefore, for the synthesis and The study of properties has become one of the research hotspots in organi...

Claims

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Application Information

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IPC IPC(8): C07D498/14
Inventor 史达清窦国兰
Owner SUZHOU UNIV
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