CN103351392B - The product of the symmetrical hexa-atomic melon ring synthetic method of prestox and synthesis - Google Patents
The product of the symmetrical hexa-atomic melon ring synthetic method of prestox and synthesis Download PDFInfo
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- CN103351392B CN103351392B CN201310326523.0A CN201310326523A CN103351392B CN 103351392 B CN103351392 B CN 103351392B CN 201310326523 A CN201310326523 A CN 201310326523A CN 103351392 B CN103351392 B CN 103351392B
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Abstract
The product of the hexa-atomic melon ring synthetic method of symmetry prestox of the present invention and synthesis, it it is the hexa-atomic melon ring of symmetrical prestox of the synthetic method of a kind of organic chemistry macrocyclic compound symmetry prestox hexa-atomic melon ring and synthesis, it is replace glycoluril dimer with dimethyl, common glycoluril and paraformaldehyde are raw material, dimethyl is made to replace glycoluril dimer symmetrical prestox hexa-atomic melon ring selectively formed with common glycosides urea condensation by formaldehyde, the invention discloses synthetic method and concrete technology condition, product is adopted nuclear magnetic resonance, NMR, Advances in crystal X-ray diffraction, mass spectrum, IR, the analysis means such as DSC-TG carry out sufficient structural characterization.
Description
Technical field
The invention discloses a kind of new organic chemistry macrocyclic compound and synthesis separation method thereof, specifically, be the one synthesis separation method that is named as the compound of the symmetrical hexa-atomic melon ring of prestox (OMeQ [6]).
Background technology
Melon ring or claim calabash [n] ring connection urea (Cucurbit [n] urils), because of its Fructus Cucurbitae moschatae [Latin Cucurbit] and name melon ring seemingly. Generally, melon ring is a kind of class macrocyclic compound formed by the methylene-bridged that formaldehyde provides by glycosides urea (structure is Fig. 1 a such as), and reaction equation is as shown in Figure 1. The architectural feature of the hydrophobic cavity of melon ring hollow defines distinctive melon ring host-guest chemistry, relates to the subjects such as catalysis, polymer chemistry, pharmaceutical chemistry, biochemistry, life sciences, material, and becomes the mainstream research content of melon cyclisation; And two, melon ring opens wide and is covered with the architectural feature of polar carbonyl oxygen port, define distinctive melon ring Coordinative Chemistry, research contents expands to, to the coordination compound of metal ion, the research that other melon rings (such as Q [5] ~ Q [8]) are constructed with many kinds of metal ions and coordination compound, race's compound interaction and corresponding Supramolecular self assembly entity from simple Q [6], becomes melon ring chemical developer new growth point.But due to common melon ring, particularly hexa-atomic melon ring, the dissolubility in aqueous medium and organic media such as eight yuan of melon rings is bad, is an impediment to the development of melon cyclisation. Modified melon ring not only can improve the dissolubility of melon ring, melon ring also can be made to possess modifiability, be the research direction of the melon great development prospect of ring chemical field, but research report relevant so far is also few. Methyl substituted melon ring is the class in modified melon ring, is replaced, by dimethyl, the class Novel macrocyclic compound that glycosides urea (structure is Fig. 2 a such as) is formed by methylene-bridged, and reaction equation is as shown in Figure 2. The preparation of methyl substituted melon ring is adopt dimethyl to replace glycosides urea and polyformaldehyde reaction and obtain mostly, and the present inventor is in the research process of methyl substituted melon ring, adopting dimethyl glycoluril dimer is that raw material is (referring to patent application, application number: 201310278915.4), controllably synthesize a kind of novel modified melon hexa-atomic melon ring of ring symmetry prestox (OMeQ [6]) containing methyl substituents.
Summary of the invention
The purpose of the present invention, it is in that the synthetic method of the openly hexa-atomic melon ring of a kind of prestox, because prestox hexa-atomic melon ring (OMeQ [6]) is a kind of novel modified melon ring, its special architectural feature is conducive to synthesizing special melon ring derivatives and special polymer, make the host-guest chemistry of melon ring, supramolecular chemistry, biochemistry, pharmaceutical chemistry content more rich and varied, and the integrity of melon ring chemical research, novelty are made significant contribution. And the preparation method of prestox hexa-atomic melon ring (OMeQ [6]) was never published on any publication magazine.
Symmetrical prestox hexa-atomic melon ring (OMeQ [6]) is to replace glycoluril dimer (A) with common glycoluril (B) for raw material with dimethyl, with paraformaldehyde (H2CO)n(C)nCoordinating by a certain percentage, in acid medium, heated and stirred reaction certain time can obtain the symmetrical hexa-atomic melon ring (D) of prestox, and its reaction equation is:
Formula is known from the reactions above: the ratio of raw material and the amount of substance of formaldehyde is 114.
Glycoluril dimer is replaced with dimethyl, common glycosides urea and paraformaldehyde are raw material, dimethyl is made to replace glycoluril dimer symmetrical prestox hexa-atomic melon ring selectively formed with common glycosides urea condensation by formaldehyde, glycoluril dimer is replaced by dimethyl, the ratio of common glycoluril and paraformaldehyde amount of substance is 114 dispensings, reaction hydrochloric acid content replaces glycoluril dimer with every 10 grams of dimethyl and is dissolved in 50��60mL concentration 12mol/L hydrochloric acid note, when 60 ~ 70 �� of C, stirring reaction 5 ~ 10 hours, cooling, rotary evaporation adds water to reduce system acidity to white powder solid occur repeatedly, stand and filter, precipitate and wash through frozen water, namely the hexa-atomic melon ring of target product symmetry prestox (OMeQ [6]) is obtained after drying.
In above-mentioned reaction in the raw material of indication, it is dimethyl replacement glycoluril dimer (referring to patent application, application number: 201310278915.4) being replaced glycosides urea and paraformaldehyde synthesis by dimethyl that the dimethyl of use replaces glycoluril dimer. In the process producing the symmetrical hexa-atomic melon ring of prestox (OMeQ [6]), temperature has very big impact, is generally not more than 70 �� of C, to avoid the formation of other products.
The synthesized hexa-atomic melon ring of symmetrical prestox (OMeQ [6]) is adopted by the present invention analysis means such as nuclear magnetic resonance, NMR, Advances in crystal X-ray diffraction, mass spectrum, IR, DSC-TG carry out sufficient structural characterization.
Accompanying drawing explanation
Fig. 1, common glycosides urea structure (Fig. 1 a) and common melon cyclization become reaction equation figure;
Fig. 2, dimethyl replace glycosides urea structure (Fig. 2 a) and methyl substituted melon cyclization becomes reaction equation figure;
Fig. 3, dimethyl replace glycoluril dimer structure and synthetic reaction formula figure thereof;
Fig. 4, the symmetrical hexa-atomic melon ring of prestox hydrogen nuclear magnetic spectrogram;
Fig. 5, the symmetrical hexa-atomic melon ring of prestox carbon nuclear magnetic spectrogram:
Fig. 6, the symmetrical hexa-atomic melon ring of prestox dept spectrogram:
Fig. 7, symmetrical prestox hexa-atomic melon ring two-dimentional spectrogram: H-H space correlation spectrum (Noe), H-H Correlated Spectroscopy, long-range C-H and C-H Correlated Spectroscopy;
Fig. 8, the symmetrical hexa-atomic melon ring of prestox mass spectrum;
Fig. 9, the symmetrical hexa-atomic melon ring of prestox crystal structure;
Figure 10, the symmetrical hexa-atomic melon ring of prestox infrared spectrum;
Figure 11, the symmetrical hexa-atomic melon ring of prestox Thermal Chart.
Detailed description of the invention
Embodiment 1: weigh 9.1 grams of dimethyl glycoluril dimers and 3.6 grams of common glycolurils, join (60mL) in the concentrated hydrochloric acid of 12mol/L, after stirring is completely dissolved, add 3 grams of paraformaldehydes, be warming up to 60 �� of C, reflux 7 hours, cooling, rotary evaporation adds water to reduce system acidity to white powder solid occur repeatedly, stands and filters, and precipitates and namely obtains the hexa-atomic melon ring of target product symmetry prestox after frozen water washing, drying.
Embodiment 2: weigh 9.1 grams of dimethyl glycoluril dimers and 3.6 grams of common glycolurils, join (60mL) in the concentrated hydrochloric acid of 12mol/L, after stirring is completely dissolved, add 3 grams of paraformaldehydes, be warming up to 70 �� of C, reflux 7 hours, cooling, rotary evaporation adds water to reduce system acidity to white powder solid occur repeatedly, stands and filters, and precipitates and namely obtains the hexa-atomic melon ring of target product symmetry prestox after frozen water washing, drying.
This white solid is dissolved in the hydrochloric acid of 6mol/L, adds the addition of C dCl2(crystallization induction agent), obtains the symmetrical hexa-atomic melon ring of prestox and [Cd2Cl7]3-The Supramolecular self assembly body constructed. Thus the symmetrical hexa-atomic melon ring crystal structure of prestox is characterized. Crystal parameters sees attached list 1.
The embodiment of the present invention is aided with explanation technical scheme, and the content of embodiment is not limited thereto.
Claims (2)
1. the hexa-atomic melon ring synthetic method of symmetrical prestox, it is characterized in that replacing glycoluril dimer with dimethyl, common glycosides urea and paraformaldehyde are raw material, dimethyl is made to replace glycoluril dimer symmetrical prestox hexa-atomic melon ring selectively formed with common glycosides urea condensation by formaldehyde, glycoluril dimer is replaced by dimethyl, the ratio of common glycoluril and paraformaldehyde amount of substance is 1:1:4 dispensing, reaction hydrochloric acid content replaces glycoluril dimer in every 10g dimethyl and is dissolved in 50��60mL concentration 12mol/L hydrochloric acid, under 60��70 DEG C of conditions, stirring reaction 5��10 hours, cooling, rotary evaporation adds water to reduce system acidity to white powder solid occur repeatedly, stand and filter, precipitate and wash through frozen water, namely target product symmetry prestox hexa-atomic melon ring OMeQ [6] is obtained after drying,
OMeQ [6] structural formula is:
��
2. the symmetrical hexa-atomic melon ring synthetic method of prestox according to claim 1, it is characterized in that dimethyl replaces glycoluril dimer is replaced glycosides urea by dimethyl to be synthetically derived with paraformaldehyde.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104151338A (en) * | 2014-08-12 | 2014-11-19 | 贵州大学 | Symmetric octamethyl cucurbituril Q[6]-rare earth adduct, and synthesis method and application thereof |
| CN105153171A (en) * | 2015-06-26 | 2015-12-16 | 贵州大学 | Heptamethyl-substituted cucurbit[7]uril, and synthetic method and separation thereof |
| CN106220637A (en) * | 2016-08-10 | 2016-12-14 | 贵州大学 | The control hydroxylating of a kind of symmetrical prestox hexa-atomic melon ring and the method for derivatization |
| CN108610347B (en) * | 2018-06-12 | 2021-08-03 | 贵州大学 | Compound with multi-carbonyl substituted six-membered semi-cucurbituril and preparation method thereof |
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| WO2005023816A2 (en) * | 2003-09-04 | 2005-03-17 | Technion Research & Development Foundation Ltd. | Synthetic binding pairs comprising cucurbituril derivatives and polyammonium compouds and uses thereof |
| DE102006011317A1 (en) * | 2006-03-09 | 2007-02-15 | Henkel Kgaa | Cosmetic agent, useful e.g. coloring and/or lightening the hair, comprises a component from e.g. oxidation dye precursor and oxidation agent and cucurbiturils compound and/or hemicucubiturils compound |
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| JP2003212877A (en) * | 2002-01-23 | 2003-07-30 | Sangaku Renkei Kiko Kyushu:Kk | Method for producing cucurbit derivative, gas scavenger and method for removing gas using the cucurbit derivative |
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Patent Citations (3)
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| WO2005023816A2 (en) * | 2003-09-04 | 2005-03-17 | Technion Research & Development Foundation Ltd. | Synthetic binding pairs comprising cucurbituril derivatives and polyammonium compouds and uses thereof |
| DE102006011317A1 (en) * | 2006-03-09 | 2007-02-15 | Henkel Kgaa | Cosmetic agent, useful e.g. coloring and/or lightening the hair, comprises a component from e.g. oxidation dye precursor and oxidation agent and cucurbiturils compound and/or hemicucubiturils compound |
| CN102875520A (en) * | 2012-09-25 | 2013-01-16 | 中国海洋石油总公司 | Synthetic method of fluoro carbonic ester |
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