CN104151327A - Synthesis and separation method of trans-seven-membered-cucurbituril - Google Patents
Synthesis and separation method of trans-seven-membered-cucurbituril Download PDFInfo
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- CN104151327A CN104151327A CN201410420394.6A CN201410420394A CN104151327A CN 104151327 A CN104151327 A CN 104151327A CN 201410420394 A CN201410420394 A CN 201410420394A CN 104151327 A CN104151327 A CN 104151327A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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Abstract
The invention provides a synthesis and separation method of trans-seven-membered-cucurbituril iQ[7] and belongs to the technical field of organic polymers. The method includes following steps: employing glycoluril and paraformaldehyde with concentrated hydrochloric acid as a medium; performing heating reflux for 5-8 hours; performing a cooling process; performing a dilution process with water being added step-by-step to separate eight-membered-cucurbituril Q[8], six-membered-cucurbituril Q[6], little trans-six-membered-cucurbituril iQ[6] and little ten-membered-cucurbituril with five-membered-cucurbituril Q[5] being included Q[5]@Q[10] which are poor in water dissolvability; concentrating a mother liquid containing five-membered-cucurbituril Q[5], seven-membered-cucurbituril Q[7], little trans-seven-membered-cucurbituril iQ[7] and little hinged fourteen-membered-cucurbituril tQ[14]; carrying the mother liquid onto a chromatographic colum with Dowex cationic exchange resin as an stationary phase; performing a leaching process with a solution composed of water, acetic acid and concentrated hydrochloric acid, wherein a volume ratio of the water, the acetic acid and the concentrated hydrochloric acid is 1:1:(0.01-0.3) to obtain a purified production of the trans-seven-membered-cucurbituril iQ[7]. The method is simple and quick.
Description
Technical field
The invention belongs to organic high molecular compound technical field, specifically trans seven yuan of melon ring iQ[7] synthetic, separation method.
Background technology
Mock study group in 1981 utilize Advances in crystal X-ray diffraction method to characterize first member-hexa-atomic melon ring Q[6 of Liao Guahuan family], 2000 HeKim study group of NianDay study group have reported the homologue-five yuan melon ring Q[5 of three kinds of hexa-atomic melon rings in simultaneously], seven yuan of melon ring Q[7] and eight yuan of melon ring Q[8]; 2002 NianDay study group have reported again inclusion ten yuan of melon ring Q[5 of five yuan of melon rings] Q[10]; American scholar Isaacs study group is at the synthetic special novel melon ring of a series of structures of isolating, as within 2005, reported trans hexa-atomic melon ring iQ[6] and trans seven yuan of melon ring iQ[7]; Ten yuan of melon rings of the synthetic bridging that obtains misplacing again in 2006; The hexa-atomic melon ring of the synthetic bridging that obtains misplacing again in 2007; Within 2011, reported vacant hexa-atomic melon ring; Guizhou Province's macrocyclic chemistry in 2013 and supramolecular chemistry key lab have synthesized again, have isolated maximum hinge joint ten quaternary melon ring tQ[14 in current Gua Huan family].Utilize the different melon ring of these sizes and constitutional features not only can the nonpolar organic molecule of inclusion, also can utilize the positively charged ion generation coordinations such as its port polar carbonyl oxygen and metal, thereby form and to comprise melon ring host-guest chemistry and the peculiar melon of melon ring coordination chemistry cyclisation, and because of its novelty and relate to the concern that research field popularity enjoys (comprising host-guest chemistry, supramolecular chemistry, biological chemistry, pharmaceutical chemistry, polymkeric substance, material, catalysis etc.) various countries scholar.
Although the existing many members of common Gua Huan family, for those special-shaped melon rings, as trans hexa-atomic melon ring iQ[6], trans seven yuan of melon ring iQ[7], the further research of the hexa-atomic melon ring of dislocation bridging, ten yuan of melon rings etc. is extremely rare.Topmost reason is that these melon rings are kinetic products in building-up process, and content seldom.Also do not find at present the simple and rapid separation method of these special-shaped melon rings.As up to the present, except report is found trans seven yuan of melon ring iQ[7] document (J. Am. Chem. Soc. 2005,127 18000-18001), goes back neither one study group both at home and abroad it is carried out to the research of further experiment.
Summary of the invention
The present invention seeks to utilize simple and quick synthetic, separation method to obtain pure trans seven yuan of melon ring iQ[7], and utilize nuclear-magnetism (hydrogen spectrum) analysis and characterization to resulting iQ[7] carried out confirming accurately.
The iQ[7 that the present invention is synthetic, separated] be a known member in the Gua Huan family having reported at present.IQ[7] be by 7 glycosides urea monomer C
4h
6n
4o
2by 14 methylene radical-CH
2the cage compound that-bridging forms, the mode of connection of one of them glycosides urea monomer is more special, and two of glycosides urea monomer protons point to melon ring inside, and its chemical constitution general formula is: C
42h
42n
28o
14.
The synthetic separation method of the trans seven yuan of melon rings of the present invention, be by glycosides urea and paraformaldehyde in concentrated hydrochloric acid medium, 100 ℃ of reflux 5 ~ 8 hours, the weight proportion of glycosides urea and paraformaldehyde is 2 ~ 2.5:1, cooling, obtain the mixed solution of multiple melon ring, it is characterized in that following these steps to successively carry out separation:
(1) mixed solution of the above-mentioned multiple melon ring of thin up progressively, reduction along with mixed solution concentration of hydrochloric acid, water-soluble eight yuan of the poorest melon ring Q[8] with ten yuan of melon ring Q[5 of a small amount of five yuan of melon rings of inclusion]@Q[10] mixture separates out at first, continue thin up, water-soluble poor hexa-atomic melon ring Q[6] with a small amount of trans hexa-atomic melon ring iQ[6] mixture separates out in succession, continues thin up, until no longer include precipitation in solution, produce, filter, get filtrate;
(2) filtrate after dilution is concentrated into 1/3rd to 1/4th of original volume, concentrated solution is containing the melon ring mixture of solubility: five yuan of melon ring Q[5], seven yuan of melon ring Q[7], a small amount of trans seven yuan of melon ring iQ[7] and a small amount of hinged ten quaternary melon ring tQ[14];
(3) chromatography column that is stationary phase by the upper cationic exchange resin of Dowex of this concentrated solution filling;
(4) use volume ratio water: acetic acid: concentrated hydrochloric acid=1:1:0.01 ~ 0.3 solution drip washing, first isolate trans seven yuan of melon ring iQ[7] sterling, as iQ[7] after drip washing is complete, strengthen gradually the volume ratio of concentrated hydrochloric acid in leacheate, isolate successively five yuan of melon ring Q[5], seven yuan of melon ring Q[7] and hinged ten quaternary melon ring tQ[14] sterling.
In the mixed solution of above-mentioned synthetic multiple melon ring, the multiple melon ring of gained is eight yuan of melon ring Q[8], ten yuan of melon ring Q[5 of five yuan of melon rings of inclusion]@Q[10], hexa-atomic melon ring Q[6], trans hexa-atomic melon ring iQ[6], five yuan of melon ring Q[5], seven yuan of melon ring Q[7], a small amount of trans seven yuan of melon ring iQ[7] and a small amount of hinged ten quaternary melon ring tQ[14].
The trans seven yuan of melon ring sterling iQ[7 of the present invention] synthetic separation method, it is the mixed solution of multiple melon ring in concentrated hydrochloric acid medium, first through progressively adding water separation, remove water-soluble eight yuan of the poorest melon ring Q[8] with ten yuan of melon ring Q[5 of a small amount of five yuan of melon rings of inclusion] Q[10], water-soluble poor hexa-atomic melon ring Q[6] with a small amount of trans hexa-atomic melon ring iQ[6], then pass through the cationic exchange resin column chromatography of Dowex and five yuan of melon ring Q[5], seven yuan of melon ring Q[7] and hinged ten quaternary melon ring tQ[14 on a small quantity] be isolated trans seven yuan of melon ring iQ[7].
In building-up process, when the weight proportion of glycosides urea and paraformaldehyde changes, and when reflux temperature and time changes, the content that obtains multiple each composition of melon ring mixed solution also can correspondingly change.
Patent of the present invention is to utilize hydrogen nuclear magnetic resonance spectrum analysis and characterization to resulting iQ[7] carried out confirming accurately.
The synthetic separated pure trans seven yuan of melon ring iQ[7 of the present invention] method is simple and quick, is to propose first from melon ring mixture, to isolate trans seven yuan of melon ring iQ[7] simple and quick method.
Accompanying drawing explanation
The trans seven yuan of melon ring iQ[7 of Fig. 1] at deuterated water
1h nmr spectrum.
Seven yuan of melon ring Q[7 of Fig. 2] and trans seven yuan of melon ring iQ[7] position on silica-gel plate, its mid point 1 is seven yuan of melon ring Q[7], selecting 2 is trans seven yuan of melon ring iQ[7].
specific implementation method
Embodiment: trans seven yuan of melon ring iQ[7] synthetic implementation method:
Take 50 grams of glycosides ureas, 20 grams of paraformaldehydes, concentrated hydrochloric acid 200mL, back flow reaction 6 hours, cooling, substep be diluted with water to without precipitation produce (be precipitated as water-soluble eight yuan of poor melon ring Q[8], hexa-atomic melon ring Q[6] etc. poorly soluble melon ring, approximately 40 grams).To contain five yuan of melon ring Q[5], seven yuan of melon ring Q[7], link ten quaternary melon ring tQ[14 on a small quantity], trans seven yuan of melon ring iQ[7] mother liquor be concentrated into certain volume (thickness too, in order to avoid affect sample upper prop, get every milliliter of concentrated solution 25 mL(and contain solid 0.9-1.1 gram).Concentrated solution is loaded into the chromatography column (diameter: 40mm that silica gel G is stationary phase; Highly: 800mm), take 1:1:0.01 ~ 0.3 water: acetic acid: concentrated hydrochloric acid is leacheate.First isolate according to drip washing and go out trans seven yuan of melon ring iQ[7] sterling, as iQ[7] after drip washing is complete, strengthen gradually the volume ratio of concentrated hydrochloric acid in leacheate, increase the polarity of leacheate, isolate successively five yuan of melon ring Q[5], seven yuan of melon ring Q[7] and hinged ten quaternary melon ring tQ[14] sterling.Trans seven yuan of melon ring iQ[7] yield account for 1% of theoretical yield.
Claims (4)
1. the synthetic separation method of trans seven yuan of melon rings, be by glycosides urea and paraformaldehyde in concentrated hydrochloric acid medium, 100 ℃ of reflux 5 ~ 8 hours, the weight proportion of glycosides urea and paraformaldehyde is 2 ~ 2.5:1, cooling, obtain the mixed solution of multiple melon ring, it is characterized in that following these steps to successively carry out separation:
(1) mixed solution of the above-mentioned multiple melon ring of thin up progressively, reduction along with mixed solution concentration of hydrochloric acid, water-soluble eight yuan of the poorest melon ring Q[8] with ten yuan of melon ring Q[5 of a small amount of five yuan of melon rings of inclusion]@Q[10] mixture separates out at first, continue thin up, water-soluble poor hexa-atomic melon ring Q[6] with a small amount of trans hexa-atomic melon ring iQ[6] mixture separates out in succession, continues thin up, until no longer include precipitation in solution, produce, filter, get filtrate;
(2) filtrate after dilution is concentrated into 1/3rd to 1/4th of original volume, concentrated solution is containing the melon ring mixture of solubility: five yuan of melon ring Q[5], seven yuan of melon ring Q[7], a small amount of trans seven yuan of melon ring iQ[7] and a small amount of hinged ten quaternary melon ring tQ[14];
(3) chromatography column that is stationary phase by the upper cationic exchange resin of Dowex of this concentrated solution filling;
(4) use volume ratio water: acetic acid: concentrated hydrochloric acid=1:1:0.01 ~ 0.3 solution drip washing, first isolate trans seven yuan of melon ring iQ[7] sterling, as iQ[7] after drip washing is complete, strengthen gradually the volume ratio of concentrated hydrochloric acid in leacheate, isolate successively five yuan of melon ring Q[5], seven yuan of melon ring Q[7] and hinged ten quaternary melon ring tQ[14] sterling.
2. the separation method of trans seven yuan of melon rings according to claim 1, the multiple melon ring that it is characterized in that gained in the mixed solution of the multiple melon ring that synthesizes is eight yuan of melon ring Q[8], ten yuan of melon ring Q[5 of five yuan of melon rings of inclusion]@Q[10], hexa-atomic melon ring Q[6], trans hexa-atomic melon ring iQ[6], five yuan of melon ring Q[5], seven yuan of melon ring Q[7], a small amount of trans seven yuan of melon ring iQ[7] and a small amount of hinged ten quaternary melon ring tQ[14].
3. trans seven yuan of melon ring sterling iQ[7 according to claim 1 and 2] synthetic separation method, the mixed solution that it is characterized in that multiple melon ring in concentrated hydrochloric acid medium, first through progressively adding water separation, remove water-soluble eight yuan of the poorest melon ring Q[8] with ten yuan of melon ring Q[5 of a small amount of five yuan of melon rings of inclusion] Q[10], water-soluble poor hexa-atomic melon ring Q[6] and a small amount of trans hexa-atomic melon ring iQ[6], pass through again the cationic exchange resin column chromatography of Dowex and five yuan of melon ring Q[5], seven yuan of melon ring Q[7] and a small amount of hinged ten quaternary melon ring tQ[14] be isolated trans seven yuan of melon ring iQ[7].
4. the synthetic separation method of trans seven yuan of melon rings according to claim 1 is characterized in that when the weight proportion of glycosides urea and paraformaldehyde changes, and when reflux temperature and time changes, the content that obtains multiple each composition of melon ring mixed solution also can correspondingly change.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557951A (en) * | 2014-12-19 | 2015-04-29 | 武汉科技大学 | Method for preparing high-purity cucurbit[10]uril |
| CN104860952A (en) * | 2015-04-17 | 2015-08-26 | 贵州大学 | Extraction separation method of high-purity cucurbituril Q[7] |
| CN105153171A (en) * | 2015-06-26 | 2015-12-16 | 贵州大学 | Heptamethyl-substituted cucurbit[7]uril, and synthetic method and separation thereof |
| CN106905958A (en) * | 2017-03-21 | 2017-06-30 | 贵州大学 | A kind of fluorescence probe based on trans cucurbit(7)uril, preparation method and application |
| CN106932425A (en) * | 2017-01-23 | 2017-07-07 | 贵州大学 | A kind of application of trans cucurbit(7)uril iQ [7] and preparation method |
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| WO2007014214A2 (en) * | 2005-07-22 | 2007-02-01 | University Of Maryland | Introverted cucurbituril compounds |
| CN103030761A (en) * | 2012-12-18 | 2013-04-10 | 贵州大学 | New member in cucurbituril family, namely hinged cucurbit (14) uril and synthesis and separation method thereof |
| CN103351399A (en) * | 2013-07-30 | 2013-10-16 | 贵州大学 | Synthesis and separation method for trans cucurbit[6]uril |
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2014
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Patent Citations (3)
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| WO2007014214A2 (en) * | 2005-07-22 | 2007-02-01 | University Of Maryland | Introverted cucurbituril compounds |
| CN103030761A (en) * | 2012-12-18 | 2013-04-10 | 贵州大学 | New member in cucurbituril family, namely hinged cucurbit (14) uril and synthesis and separation method thereof |
| CN103351399A (en) * | 2013-07-30 | 2013-10-16 | 贵州大学 | Synthesis and separation method for trans cucurbit[6]uril |
Non-Patent Citations (3)
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|---|
| LYLE ISAACS，等: "The Inverted Cucurbit[n]uril Family", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| RAHUL V. PINJARI，等: "Inverted Cucurbit[n]urils: Density Functional Investigations on the Electronic Structure, Electrostatic Potential, and NMR Chemical Shifts", 《JOURNAL OF PHYSICAL CHEMISTRY A》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557951A (en) * | 2014-12-19 | 2015-04-29 | 武汉科技大学 | Method for preparing high-purity cucurbit[10]uril |
| CN104860952A (en) * | 2015-04-17 | 2015-08-26 | 贵州大学 | Extraction separation method of high-purity cucurbituril Q[7] |
| CN105153171A (en) * | 2015-06-26 | 2015-12-16 | 贵州大学 | Heptamethyl-substituted cucurbit[7]uril, and synthetic method and separation thereof |
| CN106932425A (en) * | 2017-01-23 | 2017-07-07 | 贵州大学 | A kind of application of trans cucurbit(7)uril iQ [7] and preparation method |
| CN106932425B (en) * | 2017-01-23 | 2018-07-31 | 贵州大学 | A kind of application of trans- cucurbit(7)uril iQ [7] |
| CN106905958A (en) * | 2017-03-21 | 2017-06-30 | 贵州大学 | A kind of fluorescence probe based on trans cucurbit(7)uril, preparation method and application |
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Application publication date: 20141119 |