CN103030761B - 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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- CN103030761B CN103030761B CN201210551698.7A CN201210551698A CN103030761B CN 103030761 B CN103030761 B CN 103030761B CN 201210551698 A CN201210551698 A CN 201210551698A CN 103030761 B CN103030761 B CN 103030761B
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- melon ring
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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.Newcomer-hinge joint ten quaternary melon rings and synthetic separation method thereof in Gua Huan family specifically.
background technology:
Mock study group in 1981 utilizes Advances in crystal X-ray diffraction method to characterize first member-hexa-atomic melon ring (Q[6]) of Liao Guahuan family, and Day study group in 2000 and Kim study group are in reported the homologue-five yuan melon ring (Q[5]) of three kinds of hexa-atomic melon rings, seven yuan of melon rings (Q[7]) and eight yuan of melon rings (Q[8]) simultaneously; 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 within 2005, reported trans hexa-atomic melon ring (Q[6] *) and trans seven yuan of melon rings (Q[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, report vacant hexa-atomic melon ring.Make people recognize that melon ring is to be formed and had the large ring cage compound that one or several hydrophobicity cavitys and opening port are covered with polar carbonyl Sauerstoffatom by n glycosides urea unit and 2n methylene-bridged.Utilize the melon annular space chamber 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 formed distinctive melon cyclisation, and because of its novelty and relate to research field and extensively enjoy (comprising host-guest chemistry, supramolecular chemistry, biological chemistry, pharmaceutical chemistry, polymkeric substance, material, catalysis etc.) various countries scholar's concern.
Although the existing many members of common Gua Huan family, as five, six, seven, eight and ten yuan of melon rings and above mentioned trans six, seven melon rings, six and ten yuan of melon rings of dislocation bridging etc.Up to the present, go back neither one study group both at home and abroad and separate and characterize any report that the polymerization degree is greater than 10 melon ring.For existing five, six, seven, eight and ten yuan of melon rings, the melon ring generally with the 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 generally with the even number polymerization degree utmost point is insoluble in water, as Q[6], Q[8] and Q[10], in the time carrying out host-guest chemistry, be often subject to the deliquescent puzzlement of melon ring.In addition, the oil soluble of these melon rings is all bad, and the host-guest chemistry research of oil soluble object is restricted, and has affected the development of melon cyclisation.At present, the host-guest chemistry in solution, supramolecular chemistry, biological chemistry, pharmaceutical chemistry are mainly taking water-soluble good seven yuan of melon rings as main.Therefore, various countries investigator is striving to find always not only to be had 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 to carry out confirming accurately to nine yuan of obtained melon rings.Utilize glycosides urea and paraformaldehyde under concentrated hydrochloric acid ambient condition, reflux temperature 5 ~ 8 hours, cooling, substep thin up with eight yuan of 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, be loaded into the chromatography column that the cationic exchange resin of Dowex is stationary phase, taking 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., finally obtain pure hinge joint ten quaternary melon rings (tQ[14]).Property research shows, hinge joint ten quaternary melon rings (tQ[14]) have well water-soluble, and can be dissolved in methyl-sulphoxide, dimethyl formamide isopolarity organic solvent, have 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 making new advances and study,the hinge joint ten quaternary melon rings of the present invention report (tQ[14]) be a newcomer in the Gua Huan family having 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; For white crystal, soluble in water and polar organic solvent, as methyl-sulphoxide.
The synthetic separation method of newcomer-hinge joint ten quaternary melon rings in Gua Huan 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 by glycosides urea and paraformaldehyde in concentrated hydrochloric acid medium, 100 DEG C of reflux 5 ~ 8 hours, the weight proportion of glycosides urea and paraformaldehyde is 2 ~ 2.5:1, cooling, obtains 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 methyl alcohol, the volume ratio of mixed solution and methyl alcohol is 1:8 ~ 12, obtains faint yellow precipitation, filters, and obtains filter residue, filter residue is the mixture of multiple melon ring;
(2) by filter residue Air drying, obtain pale yellow powder;
(3) leach yellow powder, ultrasonic oscillation 3 ~ 5 minutes, repeatedly lixiviate 5 ~ 8 times with the neutral boiling water of 2 ~ 3 times of amounts;
(4) vat liquor is concentrated, until being every milliliter, concentrated solution concentration contains solid 1.0-1.1 gram.
(5) by upper concentrated solution filling silica gel G 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), by leaching liquid concentration process, while appearance, carries out step (5) after should first white crystals thing being filtered again if any the white crystals thing of the less melon ring of other solvability.
Step (5) column chromatography stationary phase is silica gel G or the cationic exchange resin of Dowex.
Step (6) is the material going out according to drip washing, and the polarity of step increase leacheate increase 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, obtained hinge joint ten quaternary melon rings (tQ[14]) have been carried out to confirmation accurately.
brief description of the drawings:
Fig. 1 links the crystalline structure schematic diagram (left figure) of ten quaternary melon rings (tQ[14]): overlook; (right figure): side-looking.
Fig. 2 links ten quaternary melon rings (tQ[14]) respectively in deuterated water (upper figure) and deuterated dimethyl sulfoxide (figure below)
1h nmr spectrum.
Fig. 3 links ten quaternary melon rings (tQ[14]) respectively in deuterated water (upper figure) and deuterated dimethyl sulfoxide (figure below)
13c 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]).
Fig. 5 links the infrared spectrum of the title complex that ten quaternary melon rings (tQ[14]) and hinge joint ten quaternary melon rings (tQ[14]) and rare earth ion Eu form.
Fig. 6 links the differential thermal analysis spectrogram (left figure) of the title complex that ten quaternary melon rings (tQ[14]) and hinge joint 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 of hinge joint ten quaternary melon rings (tQ[14]):
Take 50 grams of glycosides ureas, 20 grams of paraformaldehydes, concentrated hydrochloric acid 200mL, back flow reaction 6 hours, cooling.Under violent stirring, reaction solution slowly to be poured in methyl alcohol, the volume ratio of mixed solution and methyl alcohol is 1:8 ~ 12, obtains faint yellow precipitation, filters, and obtains 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, repeatedly lixiviate 5 ~ 8 times.To contain five yuan of melon rings (Q[5]), seven yuan of melon rings (Q[7]), and 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 (too thickness, in order to avoid affect 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), taking 1:(1 ~ 4): (0.01 ~ 1) water: acetic acid: concentrated hydrochloric acid is leacheate.The polarity of the material step increase leacheate going out according to drip washing, i.e. the 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]) finally obtains sterling and links ten quaternary melon rings (tQ[14]).Yield accounts for 1% of theoretical yield.
Embodiment 2: the synthetic implementation method of hinge joint ten quaternary melon rings (tQ[14]):
Take 50 grams of glycosides ureas, 20 grams of paraformaldehydes, concentrated hydrochloric acid 200mL, back flow reaction 6 hours, cooling.Under violent stirring, reaction solution slowly to be poured in methyl alcohol, the volume ratio of mixed solution and methyl alcohol is 1:8 ~ 12, obtains faint yellow precipitation, filters, and obtains 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, repeatedly lixiviate 5 ~ 8 times.To contain five yuan of melon rings (Q[5]), seven yuan of melon rings (Q[7]), and 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 (too thickness, in order to avoid affect 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), taking 1:(1 ~ 4): (0.01 ~ 1) water: acetic acid: concentrated hydrochloric acid is leacheate.The polarity of the material step increase leacheate going out according to drip washing, i.e. the 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]), finally obtain sterling and link ten quaternary melon rings (tQ[14]).Yield accounts for 1% of theoretical yield.
Claims (4)
1. another member-hinge joint ten quaternary melon ring tQ[14 in Gua Huan family], it is characterized in that this compound is by 14 glycoluril monomer C
4h
6n
4o
2by 28 methylene radical-CH
2-bridging forms the cage compound of the folding figure of eight, and its chemical constitution general formula is: C
84h
84n
56o
28; Molecular weight is 2324; For white crystal, soluble in water and polar organic solvent methyl-sulphoxide, its structure is:
。
2. according to another member-hinge joint ten quaternary melon ring tQ[14 in Gua Huan claimed in claim 1 family] synthetic separation method, comprise the synthetic method of the mixture of hinge joint ten quaternary melon rings and other melon ring, be by glycoluril and paraformaldehyde in concentrated hydrochloric acid medium, 100 DEG C of reflux 5～8 hours, the weight proportion of glycoluril 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 separate:
(1) under violent stirring, mixed solution slowly to be poured in methyl alcohol, the volume ratio of mixed solution and methyl alcohol is 1:8～12, obtains faint yellow precipitation, filters, and obtains filter residue, filter residue is the mixture of multiple melon ring;
(2) by filter residue Air drying, obtain pale yellow powder;
(3) leach yellow powder, ultrasonic oscillation 3～5 minutes, repeatedly lixiviate 5～8 times with the neutral boiling water of 2～3 times of amounts;
(4) vat liquor is concentrated, until being every milliliter, concentrated solution concentration contains solid 1.0-1.1 gram;
(5) by upper concentrated solution filling silica gel G 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 five yuan of melon ring Q[5], seven yuan of melon ring Q[7], and hinged ten quaternary melon ring tQ[14].
3. another member-hinge joint ten quaternary melon ring tQ[14 in Gua Huan according to claim 2 family] synthetic separation method, it is characterized in that separating step (4) is by leaching liquid concentration process, while appearance if any the white crystals thing of the less melon ring of other solvability, after should first white crystals thing being filtered, carry out again step (5).
4. another member-hinge joint ten quaternary melon ring tQ[14 in Gua Huan according to claim 2 family] synthetic separation method, it is characterized in that the material going out according to drip washing, the polarity of step increase leacheate, increase acetic acid and hydrochloric acid proportioning, when drip washing links ten quaternary melon ring tQ[14] time, acetic acid and hydrochloric acid proportioning reach maximum value.
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| CN104151327A (en) * | 2014-08-25 | 2014-11-19 | 贵州大学 | Synthesis and separation method of trans-seven-membered-cucurbituril |
| CN106117219B (en) * | 2016-06-24 | 2018-11-09 | 贵州大学 | The application of ten quaternary melon ring tQ [14] of one kind |
| CN106645056B (en) * | 2016-11-16 | 2019-05-03 | 贵州大学 | A kind of detection method of barium in drinking water ion |
| CN107446570B (en) * | 2017-07-12 | 2019-06-28 | 贵州大学 | A kind of fluorescent organic solid material and preparation method thereof by Supramolecular Assembling |
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