CN103030761A - New member in cucurbituril family, namely hinged cucurbit (14) uril and synthesis and separation method thereof - Google Patents
New member in cucurbituril family, namely hinged cucurbit (14) uril and synthesis and separation method thereof Download PDFInfo
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- CN103030761A CN103030761A CN2012105516987A CN201210551698A CN103030761A CN 103030761 A CN103030761 A CN 103030761A CN 2012105516987 A CN2012105516987 A CN 2012105516987A CN 201210551698 A CN201210551698 A CN 201210551698A CN 103030761 A CN103030761 A CN 103030761A
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Abstract
The invention relates to a new member in a cucurbituril family, namely hinged cucurbit (14) uril and a synthesis and separation method thereof, belonging to an organic novel macrocyclic compound and the synthesis and separation method thereof. The compound is of a folded 8-shaped cage-like compound formed by bridging 14 glycoluril monomers (C4H6N4O2) by 28 methylene groups (-CH2-), the general formula of the chemical composition is C84H84N56O28, and the molecular weight is 2324; and the compound is of a white crystal and is easy to dissolve in water and a polar organic solvent, the compound, namely the hinged cucurbit (14) uril (tQ(14)) is accurately confirmed through analysis and the like of (fluorine spectrum and carbon spectrum), mass spectrum and single-crystal mechanisms, the compound is synthesized through a traditional cucurbituril synthesis method, and then column chromatography separation is performed for preparation.
Description
Technical field
The invention relates to a novel macrocylc compound and synthetic, separation method.The newcomer in the melon ring family-hinge joint ten quaternary melon rings and synthetic separation method thereof specifically.
Background technology:
Mock study group in 1981 utilizes the Advances in crystal X-ray diffraction method to characterize first member of melon ring family-hexa-atomic melon ring (Q[6]), and Day study group in 2000 and Kim study group are in the homologue-five yuan melon ring of having reported simultaneously three kinds of hexa-atomic melon rings (Q[5]), seven yuan of melon rings (Q[7]) and eight yuan of melon rings (Q[8]); Day study group in 2002 has reported again inclusion ten yuan of melon rings of five yuan of melon rings (Q[5]@Q[10]); American scholar Isaacs study group is at the synthetic special novel melon ring of a series of structures of isolating, as reporting trans hexa-atomic melon ring (Q[6] *) and trans seven yuan of melon rings (Q[7] *) in 2005; 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; Reported vacant hexa-atomic melon ring in 2011.Make people recognize that the melon ring is to be formed by n glycosides urea unit and 2n methylene-bridged to have the large ring cage compound that one or several hydrophobicity cavitys and opening port are covered with the polar carbonyl Sauerstoffatom.But utilize the not only nonpolar organic molecule of inclusion of melon annular space chamber, also can utilize the positively charged ion generation coordinations such as its port polar carbonyl oxygen and metal, thereby formed distinctive melon cyclisation, and because of its novelty and relate to the concern that research field extensively enjoys (comprising host-guest chemistry, supramolecular chemistry, biological chemistry, pharmaceutical chemistry, polymkeric substance, material, catalysis etc.) the various countries scholar.
Although the common melon ring existing many members of family are such as five, six, seven, eight and ten yuan of melon rings and above mentioned trans six, seven melon rings, dislocation bridging six and ten yuan of melon rings etc.Up to the present, go back both at home and abroad that neither one study group separates and characterize the polymerization degree greater than any report of 10 melon ring.For existing five, six, seven, eight and ten yuan of melon rings, the melon ring that generally has an odd number polymerization degree has water-soluble preferably, as five yuan of melon rings (Q[5]: solubleness
20Be about 5.6g), seven yuan of melon rings (Q[7]: solubleness
20Be about 1.7g); The melon ring that generally the has an even number polymerization degree then utmost point is insoluble in water, such as Q[6], Q[8] and Q[10], when carrying out host-guest chemistry, often be subject to the deliquescent puzzlement of melon ring.In addition, the oil soluble of these melon rings is all bad, and research is restricted to the host-guest chemistry of oil soluble object, has affected the development of melon cyclisation.At present, the host-guest chemistry in the solution, supramolecular chemistry, biological chemistry, pharmaceutical chemistry are mainly take water-soluble preferably seven yuan of melon rings as main.Therefore, the various countries investigator is striving to find always not only to have wetting ability and simultaneously has again oil-soluble melon ring, makes melon ring host-guest chemistry content more rich and varied.
Present patent application is synthetic exactly, separation has obtained hinge joint ten quaternary melon rings (tQ[14]), and utilize the most strong means of sign new compound such as nuclear-magnetism (hydrogen spectrum, carbon spectrum), mass spectrum, ray crystallographic analysis that resulting nine yuan of melon rings have been carried out confirming accurately.Utilize glycosides urea and Paraformaldehyde 96 under the concentrated hydrochloric acid ambient condition, reflux temperature 5 ~ 8 hours, cooling, the substep thin up with eight yuan of relatively poor melon rings of separating water-soluble (Q[8]), hexa-atomic melon ring (Q[6]) and a small amount of inclusion without ten yuan of melon rings of first melon ring (Q[5]@Q[10]) after.To contain five yuan of melon rings (Q[5]), seven yuan of melon rings (Q[7]), to link ten quaternary melon rings (tQ[14]) and a small amount of polymeric mother liquor of glycosides urea on a small quantity concentrated, being loaded into the cationic exchange resin of Dowex is the chromatography column of stationary phase, take 1:(1 ~ 4): (0.01 ~ 1) water: acetic acid: concentrated hydrochloric acid is leacheate, obtain according to this five yuan of melon rings (Q[5]), seven yuan of melon rings (Q[7]) etc., obtain at last pure hinge joint ten quaternary melon rings (tQ[14]).Property research shows, links ten quaternary melon rings (tQ[14]) and has well water-solublely, and can be dissolved in methyl-sulphoxide, dimethyl formamide isopolarity organic solvent, shown its special hydrophilic and oil-wet behavior.
Summary of the invention: the object of the invention is to synthesize, separate the melon cyclic cpds that makes new advances and study,The hinge joint ten quaternary melon rings of the present invention's report (tQ[14]) be a newcomer in the melon ring family that has reported at present.This compound is by 14 glycosides urea monomer (C
4H
6N
4O
2) by 28 methylene radical (CH
2-) bridging forms the cage compound of the folding figure of eight, its chemical constitution general formula is: C
84H
84N
56O
28
Structure is referring to accompanying drawing 1; Molecular weight is 2324; Be white crystal, soluble in water and polar organic solvent is such as methyl-sulphoxide.
The synthetic separation method of newcomer-hinge joint ten quaternary melon rings in the melon ring of the present invention family (tQ[14]) comprises the synthetic method of the mixture of hinge joint ten quaternary melon rings and other melon ring.Be with glycosides urea and Paraformaldehyde 96 in the concentrated hydrochloric acid medium, 100 ℃ of reflux 5 ~ 8 hours, the weight proportion of glycosides urea and Paraformaldehyde 96 is 2 ~ 2.5:1, cooling gets the mixed solution of multiple melon ring, then follows these steps to successively separate:
(1) under violent stirring, mixed solution slowly to be poured in the methyl alcohol, the volume ratio of mixed solution and methyl alcohol is 1:8 ~ 12, gets faint yellow precipitation, filters, and gets filter residue, filter residue is the mixture of multiple melon ring;
(2) with the filter residue Air drying, get pale yellow powder;
(3) the neutral boiling water with 2 ~ 3 times of amounts leaches yellow powder, ultrasonic oscillation 3 ~ 5 minutes, and lixiviate is 5 ~ 8 times repeatedly;
(4) vat liquor is concentrated, until being every milliliter, concentrated solution concentration contains solid 1.0-1.1 gram.
(5) with the upper silica gel G of concentrated solution filling or the cationic exchange resin column of Dowex.
(6) with volume ratio 1:(1 ~ 4): (0.01 ~ 1) water: acetic acid: concentrated hydrochloric acid solution drip washing, isolate successively Q[5], Q[7], and tQ[14].
Separating step (4) when occurring if any the white crystals thing of the less melon ring of other solvability, carry out step (5) after should be first will the white crystals thing filtering again in the leaching liquid concentration process.
Step (5) column chromatography stationary phase is silica gel G or the cationic exchange resin of Dowex.
Step (6) is the material that goes out according to drip washing, and the polarity of step increase leacheate namely increases acetic acid and hydrochloric acid proportioning, as drip washing tQ[14] time, acetic acid and hydrochloric acid proportioning reach maximum value.
The hinge joint ten quaternary melon rings of patent indication of the present invention (tQ[14]) are by the most strong means of signs new compound such as nuclear-magnetism (hydrogen spectrum, carbon spectrum), mass spectrum, ray crystallographic analysis resulting hinge joint ten quaternary melon rings (tQ[14]) to have been carried out accurately affirmation.
Description of drawings:
Fig. 1 links the crystalline structure synoptic diagram (left figure) of ten quaternary melon rings (tQ[14]): overlook; (right figure): side-looking.
Fig. 2 link ten quaternary melon rings (tQ[14]) respectively at deuterium in water (upper figure) and the deuterated dimethyl sulfoxide (figure below)
1The H nmr spectrum.
Fig. 3 link ten quaternary melon rings (tQ[14]) respectively at deuterium in water (upper figure) and the deuterated dimethyl sulfoxide (figure below)
13The C nmr spectrum.
Fig. 4 links the ground substance assistant laser desorption ionization flight time mass spectrum spectrogram (MALDI-TOFMS) of ten quaternary melon rings (tQ[14]).
The infrared spectrum that Fig. 5 links ten quaternary melon rings (tQ[14]) and links the title complex that ten quaternary melon rings (tQ[14]) and rare earth ion Eu form.
The differential thermal analysis spectrogram (left figure) that Fig. 6 links ten quaternary melon rings (tQ[14]) and links the title complex that ten quaternary melon rings (tQ[14]) and rare earth ion Eu form; Thermogravimetric analysis spectrogram (right figure).
Specific implementation method:
Embodiment 1: the synthetic implementation method that links ten quaternary melon rings (tQ[14]):
Take by weighing glycosides urea 50 grams, Paraformaldehyde 96 20 grams, concentrated hydrochloric acid 200mL, back flow reaction 6 hours, cooling.Under violent stirring, reaction solution slowly to be poured in the methyl alcohol, the volume ratio of mixed solution and methyl alcohol is 1:8 ~ 12, gets faint yellow precipitation, filters, and gets filter residue, filter residue is the mixture of multiple melon ring.With the neutral boiling water leaching yellow powder of 2 ~ 3 times of amounts, ultrasonic oscillation 3 ~ 5 minutes, lixiviate is 5 ~ 8 times repeatedly.To contain five yuan of melon rings (Q[5]), seven yuan of melon rings (Q[7]), link ten quaternary melon rings (tQ[14]) and a small amount of polymeric filtrate of glycosides urea on a small quantity and be concentrated into certain volume (thickness too, in order to avoid affect the sample upper prop, get every milliliter of concentrated solution 15 mL(and contain solid 1.0-1.1 gram).Concentrated solution is loaded into the chromatography column that silica gel G is stationary phase (40mm 800mm), take 1:(1 ~ 4): (0.01 ~ 1) water: acetic acid: concentrated hydrochloric acid is leacheate.The polarity of the material step increase leacheate that goes out according to drip washing, the i.e. amount of acetic acid and hydrochloric acid.Obtaining according to this five yuan of melon rings (Q[5]), seven yuan of melon rings (Q[7]) obtains at last sterling and links ten quaternary melon rings (tQ[14]).Yield accounts for 1% of theoretical yield.
Embodiment 2: the synthetic implementation method that links ten quaternary melon rings (tQ[14]):
Take by weighing glycosides urea 50 grams, Paraformaldehyde 96 20 grams, concentrated hydrochloric acid 200mL, back flow reaction 6 hours, cooling.Under violent stirring, reaction solution slowly to be poured in the methyl alcohol, the volume ratio of mixed solution and methyl alcohol is 1:8 ~ 12, gets faint yellow precipitation, filters, and gets filter residue, filter residue is the mixture of multiple melon ring.With the neutral boiling water leaching yellow powder of 2 ~ 3 times of amounts, ultrasonic oscillation 3 ~ 5 minutes, lixiviate is 5 ~ 8 times repeatedly.To contain five yuan of melon rings (Q[5]), seven yuan of melon rings (Q[7]), link ten quaternary melon rings (tQ[14]) and a small amount of polymeric filtrate of glycosides urea on a small quantity and be concentrated into certain volume (thickness too, in order to avoid affect the sample upper prop, get every milliliter of concentrated solution 15 mL(and contain solid 1.0-1.1 gram).Concentrated solution is loaded into the chromatography column that the cationic exchange resin of Dowex is stationary phase (40mm 800mm), take 1:(1 ~ 4): (0.01 ~ 1) water: acetic acid: concentrated hydrochloric acid is leacheate.The polarity of the material step increase leacheate that goes out according to drip washing, the i.e. amount of acetic acid and hydrochloric acid.Obtain according to this five yuan of melon rings (Q[5]), seven yuan of melon rings (Q[7]), obtain at last sterling and link ten quaternary melon rings (tQ[14]).Yield accounts for 1% of theoretical yield.
Claims (5)
1. newcomer in the melon ring family-hinge joint ten quaternary melon rings (tQ[14]), this compound is by 14 glycosides urea monomer (C
4H
6N
4O
2) by 28 methylene radical (CH
2-) bridging forms the cage compound of the folding figure of eight, its chemical constitution general formula is: C
84H
84N
56O
28, structure is referring to accompanying drawing 1; Molecular weight is 2324; Be white crystal, soluble in water and polar organic solvent is such as methyl-sulphoxide.
2. according to the synthetic separation method of newcomer-hinge joint ten quaternary melon rings in the melon ring claimed in claim 1 family (tQ[14]), the synthetic method that comprises the mixture of hinge joint ten quaternary melon rings and other melon ring, be with glycosides urea and Paraformaldehyde 96 in the concentrated hydrochloric acid medium, 100 ℃ of reflux 5 ~ 8 hours, the weight proportion of glycosides urea and Paraformaldehyde 96 is 2 ~ 2.5:1, cool off, get the mixed solution of multiple melon ring, it is characterized in that following these steps to successively separate:
(1) under violent stirring, mixed solution slowly to be poured in the methyl alcohol, the volume ratio of mixed solution and methyl alcohol is 1:8 ~ 12, gets faint yellow precipitation, filters, and gets filter residue, filter residue is the mixture of multiple melon ring;
(2) with the filter residue Air drying, get pale yellow powder;
(3) the neutral boiling water with 2 ~ 3 times of amounts leaches yellow powder, ultrasonic oscillation 3 ~ 5 minutes, and lixiviate is 5 ~ 8 times repeatedly;
(4) vat liquor is concentrated, until being every milliliter, concentrated solution concentration contains solid 1.0-1.1 gram;
(5) with the upper silica gel G of concentrated solution filling or the cationic exchange resin column of Dowex;
(6) with volume ratio 1:(1 ~ 4): (0.01 ~ 1) water: acetic acid: concentrated hydrochloric acid solution drip washing, isolate successively Q[5], Q[7], and tQ[14].
3. the synthetic separation method of newcomer-hinge joint ten quaternary melon rings in the melon ring according to claim 2 family (tQ[14]), it is characterized in that separating step (4) is in the leaching liquid concentration process, when occurring if any the white crystals thing of the less melon ring of other solvability, carry out again step (5) after should be first will the white crystals thing filtering.
4. the synthetic separation method of newcomer-hinge joint ten quaternary melon rings in the melon ring according to claim 2 family (tQ[14]) is characterized in that the column chromatography stationary phase is silica gel G or the cationic exchange resin of Dowex.
5. the synthetic separation method of newcomer-hinge joint ten quaternary melon rings in the melon ring according to claim 2 family (tQ[14]), it is characterized in that the material that goes out according to drip washing, the polarity of step increase leacheate, namely increase acetic acid and hydrochloric acid proportioning, as drip washing tQ[14] time, acetic acid and hydrochloric acid proportioning reach maximum value.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151327A (en) * | 2014-08-25 | 2014-11-19 | 贵州大学 | Synthesis and separation method of trans-seven-membered-cucurbituril |
| CN106117219A (en) * | 2016-06-24 | 2016-11-16 | 贵州大学 | The application of a kind of ten quaternarys melon ring tQ [14] and preparation method |
| CN106645056A (en) * | 2016-11-16 | 2017-05-10 | 贵州大学 | Method for detecting barium ions in drinking water |
| CN107446570A (en) * | 2017-07-12 | 2017-12-08 | 贵州大学 | It is a kind of to pass through fluorescent organic solid material of Supramolecular Assembling and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1950373A (en) * | 2004-04-26 | 2007-04-18 | 浦项工科大学校产学协力团 | Processes of preparing glycolurils and cucurbiturils using microwave |
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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1950373A (en) * | 2004-04-26 | 2007-04-18 | 浦项工科大学校产学协力团 | Processes of preparing glycolurils and cucurbiturils using microwave |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151327A (en) * | 2014-08-25 | 2014-11-19 | 贵州大学 | Synthesis and separation method of trans-seven-membered-cucurbituril |
| CN106117219A (en) * | 2016-06-24 | 2016-11-16 | 贵州大学 | The application of a kind of ten quaternarys melon ring tQ [14] and preparation method |
| CN106117219B (en) * | 2016-06-24 | 2018-11-09 | 贵州大学 | The application of ten quaternary melon ring tQ [14] of one kind |
| CN106645056A (en) * | 2016-11-16 | 2017-05-10 | 贵州大学 | Method for detecting barium ions in drinking water |
| CN106645056B (en) * | 2016-11-16 | 2019-05-03 | 贵州大学 | A kind of detection method of barium in drinking water ion |
| CN107446570A (en) * | 2017-07-12 | 2017-12-08 | 贵州大学 | It is a kind of to pass through fluorescent organic solid material of Supramolecular Assembling and preparation method thereof |
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