CN105153385A - New members of cucurbit(13)uril and cucurbit(15)uril in cucurbit uril family and synthesis and separation method thereof - Google Patents
New members of cucurbit(13)uril and cucurbit(15)uril in cucurbit uril family and synthesis and separation method thereof Download PDFInfo
- Publication number
- CN105153385A CN105153385A CN201510636580.8A CN201510636580A CN105153385A CN 105153385 A CN105153385 A CN 105153385A CN 201510636580 A CN201510636580 A CN 201510636580A CN 105153385 A CN105153385 A CN 105153385A
- Authority
- CN
- China
- Prior art keywords
- melon
- yuan
- melon ring
- uril
- cucurbit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention provides new members of cucurbit(13)uril and cucurbit(15)uril in a cucurbit uril family and a synthesis and separation method thereof, and belongs to the technical field of novel macrocyclic compounds and a synthesis and separation method thereof. In the new members of cucurbit(13)uril Q[13] and cucurbit(15)uril Q[15] in the cucurbit uril family, Q[13] is a cage compound formed by bridging 13 glycoluril monomers C14H16O2 through 26 methylene-CH2-, the chemical component general formula is C78H78N52O26, and the molecular weight is 2158. Q[15] is a cage compound formed by bridging 15 glycoluril monomers C14H16O2 through 30 methylene-CH2-, the chemical component general formula is C90H90N60O30, and the molecular weight is 2490. The two compounds are both white solid, can be dissolved in water easily, and can be dissolved in organic solvents of dimethylsulfoxide, formic acid and acetic acid. Product composition is determined accurately and correctly through mass spectrum and nuclear magnetism. The invention discloses the synthesis and separation method of Q[13] and Q[15].
Description
Technical field
The invention relates to Novel macrocyclic compound and synthesis separation method thereof.13,15 yuan of melon rings and synthesis thereof specifically, separation method.
Background technology
Within 1981, Mock study group utilizes Advances in crystal X-ray diffraction method to characterize first member-hexa-atomic melon ring (Q [6]) of Gua Huan family, and Day study group in 2000 and Kim study group are in reporting homologue-five yuan of melon rings (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; Within 2002, Day study group reports again ten yuan of melon rings (Q [5] Q [10]) of inclusion five yuan of melon rings; The synthesis in 2006 of American scholar Isaacs study group obtains ten yuan of melon rings of dislocation bridging; Synthesis in 2007 obtains the hexa-atomic melon ring of bridging of misplacing, and within 2011, reports vacant hexa-atomic melon ring, and these melon rings are all be the melon ring substantially constructing module generation with C-type polymer.Within 2005, American scholar Isaacs study group cooperates to report trans hexa-atomic melon ring (Q [6] *) and trans seven yuan of melon rings (Q [7] *) with scholar Kim study group of Korea S, and these melon rings are all be the melon ring substantially constructing module generation with S-type polymer.So the mechanism appearing as the formation of melon ring of these melon rings is set up and established important foundation: namely glycosides urea and formaldehyde reaction form C-type polymer and S-type polymer, then C-type polymer forms serial common melon ring further and not exclusively closes melon ring etc.; And S-type polymer forms serial trans melon ring further.Within 2013, our laboratory reports the maximum melon ring of the polymerization degree at that time, hinged ten quaternary melon rings (tQ [14]), show in melon ring forming process, glycosides urea and formaldehyde reaction also may form the polymer (T-type polymer) of spirane structure, therefore enrich further and improve melon ring formation mechenism.Meanwhile, the discovery of the melon ring of this spline structure, enjoys the concern of scholars because of its novelty and the popularity (comprising host-guest chemistry, supramolecular chemistry, biological chemistry, pharmaceutical chemistry, polymkeric substance, material, catalysis etc.) that may relate to research field.
Inventor isolates hinge joint ten quaternary melon ring tQ [14] synthesis in 2012 and applies for a patent, the patent No.: ZL201210551698.7, and denomination of invention is " newcomer in Gua Huan family-link ten quaternary melon rings and synthesis separation method thereof ".The present invention is that isolated 13,15 yuan of melon rings are synthesized in research further on this basis.
Summary of the invention
The object of the invention is to synthesize and be separated the melon cyclic cpds that makes new advances and study.
The ten ternary melon rings (Q [13]) of the present invention's report and 15 yuan of melon rings (Q [15]) are two newcomers in the current Gua Huan family reported.
Newcomer-ten ternary melon ring Q [13], 15 yuan of melon ring Q [15] in Gua Huan family of the present invention,
Q [13] is by 13 glycosides urea monomer C
14h
16o
2by 26 methylene radical-CH
2the cage compound that-bridging is formed, chemical constitution general formula is: C
78h
78n
52o
26, molecular weight is: 2158;
Q [15] is by 15 glycosides urea monomer C
14h
16o
2by 30 methylene radical-CH
2the cage compound that-bridging is formed, chemical constitution general formula is: C
90h
90n
60o
30, molecular weight is: 2490; Two compound proterties are all white solid, soluble in water, are dissolved in organic solvent methyl-sulphoxide, formic acid, acetic acid; Show special lypohydrophilic character, product forms through mass spectrum, the accurate confirmation of nuclear-magnetism.
Newcomer in Gua Huan family of the present invention---the synthesis separation method of ten ternary melon rings Q [13], 15 yuan of melon ring Q [15], comprise the synthetic method of the mixture of Q [13], the first melon ring of Q [15] and other melon ring, be by glycosides urea and paraformaldehyde in concentrated hydrochloric acid medium, reflux 4 ~ 5 hours, the weight proportion of glycosides urea and paraformaldehyde is 2 ~ 2.5:1, cooling, obtains the mixed solution of multiple melon ring, and follows these steps to successively be separated:
(1) under vigorous stirring, slowly poured in methyl alcohol by mixed solution, the volume ratio of mixed solution and methyl alcohol is 1:8 ~ 12, obtains pale yellow precipitate, and filter, obtain filter residue, filter residue is the mixture of multiple melon ring;
(2) by filter residue Air drying, pale yellow powder is obtained;
(3) with the neutral boiling water leaching yellow powder of 2 ~ 3 times amount, ultrasonic oscillation 3 ~ 5 minutes, repeatedly lixiviate 5 ~ 8 times;
(4) vat liquor is concentrated, and constantly filters removing white crystals thing (white crystals thing is the poor melon rings of other solvabilities, as hexa-atomic melon ring or a small amount of eight yuan of melon rings and polymer), until concentrated solution concentration be every milliliter containing solid 1.0-1.1 gram;
(5) by upper for the concentrated solution filling 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 Q [5] successively, Q [7], and the mixture of Q [13], tQ [14] and Q [15]; It is characterized in that the synthetic method of the mixture of Q [13], Q [15] and other melon rings be by glycosides urea and paraformaldehyde in concentrated hydrochloric acid medium, heat 79 DEG C-82 DEG C backflows 4 ~ 4.5 hours, the weight proportion of glycosides urea and paraformaldehyde is 2 ~ 2.2:1, cooling, the mixed solution of multiple melon ring, and increase step (7) in separating step again;
(7) utilize large silica-gel plate (40cm × 40cm) chromatographic separating process by Q [13], the mixture separation of tQ [14] and Q [15], get the silica gel formic acid wash-out containing Q [13] and Q [15] respectively, elutriant is spin-dried for, and namely obtains product.
Above-mentioned separating step (4) by leaching liquid concentration process, when the white crystals thing if any the less melon ring of other solvability occurs, carry out step (5) after should first being filtered by white crystals thing again.
Column chromatography stationary phase is the cationic exchange resin of Dowex.
According to the material that drip washing goes out, gradient increases the polarity of leacheate, namely increases acetic acid and hydrochloric acid proportioning.When drip washing ten ternary melon ring Q [13], 15 yuan of melon ring Q [15], acetic acid and hydrochloric acid proportioning reach maximum value.
Ten ternary melon rings (Q [13]) and 15 yuan of melon rings (Q [15]) of patent indication of the present invention characterize the most strong means of new compound by mass spectroscopy, nuclear-magnetism (hydrogen spectrum) etc. to have carried out confirming accurately to obtained ten ternary melon rings (Q [13]) and 15 yuan of melon rings (Q [15]).
Accompanying drawing explanation
Fig. 1 ten ternary melon ring is respectively in deuterated water (upper figure) and deuterated dimethyl sulfoxide (figure below)
1h nmr spectrum.
The mass spectral results of Fig. 2 ten ternary melon ring.
Fig. 3 15 yuan of melon rings are respectively in deuterated water (upper figure) and deuterated dimethyl sulfoxide (figure below)
1h nmr spectrum.
The mass spectral results that Fig. 4 15 yuan of melon rings divide.
Fig. 5 ten ternary melon ring, link the compound of ten quaternary melon rings (tQ [14]) and 15 yuan of melon rings in large silica-gel plate (40cm × 40cm) chromatographic separation structure.
specific implementation method
The synthesis separation method of embodiment 1: ten ternary melon ring (Q [13]) and 15 yuan of melon rings (Q [15]):
Take glycosides urea 500 grams, paraformaldehyde 200 grams, concentrated hydrochloric acid 2000mL, 80 DEG C of back flow reaction 4 hours, cooling.Under vigorous stirring, slowly poured in methyl alcohol by reaction solution, the volume ratio of mixed solution and methyl alcohol is 1:8, obtains pale yellow precipitate, and filter, obtain filter residue, filter residue is the mixture of multiple melon ring.With the neutral boiling water leaching yellow powder of 2 ~ 3 times amount, ultrasonic oscillation 3 ~ 5 minutes, repeatedly lixiviate 5 ~ 8 times.To be concentrated into certain volume containing five yuan of melon rings (Q [5]), seven yuan of melon rings (Q [7]), a small amount of hinge joint ten quaternary melon rings (tQ [14]), ten ternary melon rings, 15 yuan of melon rings and a small amount of polymeric filtrate of glycosides urea (can not too thickness, in order to avoid affect sample upper prop, get concentrated solution 150mL(every milliliter containing solid 1.0-1.1 gram).Concentrated solution being loaded into the cationic exchange resin of Dowex is on the chromatography column of stationary phase, with 1:1 ~ 4:0.01 ~ 1 water: acetic acid: concentrated hydrochloric acid is leacheate.According to the polarity of the substance gradients increase leacheate that drip washing goes out, i.e. the amount of acetic acid and hydrochloric acid.Obtain five yuan of melon rings (Q [5]) according to this, seven yuan of melon rings (Q [7]), and ten ternary melon rings, link the mixture of ten quaternary melon rings (tQ [14]) and 15 yuan of melon rings.By the ten ternary melon rings obtained, mixture large silica-gel plate (40cm × 40cm) chromatographic separation linking ten quaternary melon rings (tQ [14]) and 15 yuan of melon rings, get the silica gel formic acid wash-out containing Q [13] and Q [15] respectively, elutriant is spin-dried for, and namely obtains product.Yield accounts for 0.5% of theoretical yield.
The synthesis separation method of embodiment 2: ten ternary melon ring (Q [13]) and 15 yuan of melon rings (Q [15]):
Take glycosides urea 500 grams, paraformaldehyde 200 grams, concentrated hydrochloric acid 2000mL, 82 DEG C of back flow reaction 4.5 hours, cooling.Under vigorous stirring, slowly poured in methyl alcohol by reaction solution, the volume ratio of mixed solution and methyl alcohol is 1:12, obtains pale yellow precipitate, and filter, obtain filter residue, filter residue is the mixture of multiple melon ring.With the neutral boiling water leaching yellow powder of 2 ~ 3 times amount, ultrasonic oscillation 3 ~ 5 minutes, repeatedly lixiviate 5 ~ 8 times.To be concentrated into certain volume containing five yuan of melon rings (Q [5]), seven yuan of melon rings (Q [7]), a small amount of hinge joint ten quaternary melon rings (tQ [14]), ten ternary melon rings, 15 yuan of melon rings and a small amount of polymeric filtrate of glycosides urea (can not too thickness, in order to avoid affect sample upper prop, get concentrated solution 150mL(every milliliter containing solid 1.0-1.1 gram).Concentrated solution being loaded into the cationic exchange resin of Dowex is on the chromatography column of stationary phase, according to the polarity of the substance gradients increase leacheate that drip washing goes out, i.e. and the amount of acetic acid and hydrochloric acid.With 1:1 ~ 4:0.01 ~ 1 water: acetic acid: concentrated hydrochloric acid is that leacheate obtains five yuan of melon rings (Q [5]), seven yuan of melon rings (Q [7]) and ten ternary melon rings, link the mixture of ten quaternary melon rings (tQ [14]) and 15 yuan of melon rings.By the ten ternary melon rings obtained, mixture large silica-gel plate (40cm × 40cm) chromatographic separation linking ten quaternary melon rings (tQ [14]) and 15 yuan of melon rings, get the silica gel formic acid wash-out containing Q [13] and Q [15] respectively, elutriant is spin-dried for, and namely obtains product.Yield accounts for 0.5% of theoretical yield.
Claims (6)
1. newcomer-ten ternary melon ring Q [13], 15 yuan of melon ring Q [15] in Gua Huan family, Q [13] is by 13 glycosides urea monomer C
14h
16o
2by 26 methylene radical-CH
2the cage compound that-bridging is formed, chemical constitution general formula is: C
78h
78n
52o
26, molecular weight is: 2158;
Q [15] is by 15 glycosides urea monomer C
14h
16o
2by 30 methylene radical-CH
2the cage compound that-bridging is formed, chemical constitution general formula is: C
90h
90n
60o
30, molecular weight is: 2490; Two compound proterties are all white solid, soluble in water, are dissolved in organic solvent methyl-sulphoxide, formic acid, acetic acid; Product forms through mass spectrum, the accurate confirmation of nuclear-magnetism.
2. according to newcomer in Gua Huan family according to claim 1---the synthesis separation method of ten ternary melon rings Q [13], 15 yuan of melon ring Q [15], comprise the synthetic method of the mixture of Q [13], Q [15] and other melon ring, be by glycosides urea and paraformaldehyde in concentrated hydrochloric acid medium, reflux 4 ~ 4.5 hours, the weight proportion of glycosides urea and paraformaldehyde is 2 ~ 2.5:1, cooling, obtains the mixed solution of multiple melon ring, and follows these steps to successively be separated:
(1) under vigorous stirring, slowly poured in methyl alcohol by mixed solution, the volume ratio of mixed solution and methyl alcohol is 1:8 ~ 12, obtains pale yellow precipitate, and filter, obtain filter residue, filter residue is the mixture of multiple melon ring;
(2) by filter residue Air drying, pale yellow powder is obtained;
(3) with the neutral boiling water leaching yellow powder of 2 ~ 3 times amount, ultrasonic oscillation 3 ~ 5 minutes, repeatedly lixiviate 5 ~ 8 times;
(4) concentrated by vat liquor, and constantly filter removing white crystals thing, white crystals thing is the poor melon rings of other solvabilities, as hexa-atomic melon ring or a small amount of eight yuan of melon rings and polymer, until concentrated solution concentration be every milliliter containing solid 1.0-1.1 gram;
(5) by upper for the concentrated solution filling 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, Q [5] is isolated successively, Q [7], and the mixture of Q [13], tQ [14] and Q [15]; It is characterized in that the synthetic method of the mixture of Q [13], Q [15] and other melon rings be by glycosides urea and paraformaldehyde in concentrated hydrochloric acid medium, heat 79 DEG C-82 DEG C backflows 4 ~ 4.5 hours, the weight proportion of glycosides urea and paraformaldehyde is 2 ~ 2.2:1, cooling, obtain the mixed solution of multiple melon ring, and in separating step, increase step (7);
(7) utilize large silica-gel plate (40cm × 40cm) chromatographic separating process by Q [13], the mixture separation of tQ [14] and Q [15], get the silica gel formic acid wash-out containing Q [13] and Q [15] respectively, elutriant is spin-dried for, and namely obtains product.
3. the synthesis separation method of newcomer-ten ternary melon ring, 15 yuan of melon rings in Gua Huan family according to claim 2, it is characterized in that separating step (4) is by leaching liquid concentration process, when white crystals thing if any the less melon ring of other solvability occurs, after should first being filtered by white crystals thing, carry out step (5) again.
4. the synthesis separation method of newcomer-ten ternary melon ring Q [13], 15 yuan of melon ring Q [15] in Gua Huan family according to claim 2, is characterized in that column chromatography stationary phase is the cationic exchange resin of Dowex.
5. the synthesis separation method of newcomer-ten ternary melon ring Q [13], 15 yuan of melon ring Q [15] in Gua Huan family according to claim 2, it is characterized in that the material gone out according to drip washing, gradient increases the polarity that leacheate is, namely increases acetic acid and hydrochloric acid proportioning.
6., when drip washing ten ternary melon ring Q [13], 15 yuan of melon ring Q [15], acetic acid and hydrochloric acid proportioning reach maximum value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510636580.8A CN105153385B (en) | 2015-09-30 | 2015-09-30 | Newcomer -13,15 yuan of melon rings and its synthesis separation method in Gua Huan families |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510636580.8A CN105153385B (en) | 2015-09-30 | 2015-09-30 | Newcomer -13,15 yuan of melon rings and its synthesis separation method in Gua Huan families |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105153385A true CN105153385A (en) | 2015-12-16 |
| CN105153385B CN105153385B (en) | 2018-07-10 |
Family
ID=54794458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510636580.8A Active CN105153385B (en) | 2015-09-30 | 2015-09-30 | Newcomer -13,15 yuan of melon rings and its synthesis separation method in Gua Huan families |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105153385B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103351399A (en) * | 2013-07-30 | 2013-10-16 | 贵州大学 | Synthesis and separation method for trans cucurbit[6]uril |
-
2015
- 2015-09-30 CN CN201510636580.8A patent/CN105153385B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103351399A (en) * | 2013-07-30 | 2013-10-16 | 贵州大学 | Synthesis and separation method for trans cucurbit[6]uril |
Non-Patent Citations (1)
| Title |
|---|
| SWARADAR.PEERANNAWAR ET AL.；: "MolecularelectrostaticpotentialsinCucurbit[n]uril(n =13–16)hosts", 《COMPUTATIONAL AND THEORETICAL CHEMISTRY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105153385B (en) | 2018-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103351399B (en) | The synthesis of trans hexa-atomic melon ring, separation method | |
| CN104209104B (en) | Cetirizine molecular engram integral column and preparation method thereof | |
| CN107245028B (en) | Biphenyl aromatic hydrocarbon, water-soluble biphenyl aromatic hydrocarbon and preparation method thereof | |
| Grajda et al. | Inherently chiral iminoresorcinarenes through regioselective unidirectional tautomerization | |
| CN103030761B (en) | New member in cucurbituril family, namely hinged cucurbit (14) uril and synthesis and separation method thereof | |
| CN101829201A (en) | Method for extracting alkaloid from monkshood medicinal material | |
| CN104151327A (en) | Synthesis and separation method of trans-seven-membered-cucurbituril | |
| CN110183338B (en) | Thiourea betaine eutectic crystal and preparation method and application thereof | |
| CN109705013A (en) | A kind of 1-(4- methylbenzyl) -3- amino -4- first seleno maleimide compound and preparation method | |
| CN109369430A (en) | A method of preparing 6-aminocaprolc acid | |
| CN102993206B (en) | Method for synthesising tetraphenylporphyrin metal complex via one-step process | |
| CN105153385A (en) | New members of cucurbit(13)uril and cucurbit(15)uril in cucurbit uril family and synthesis and separation method thereof | |
| CN102093226B (en) | Preparation method of diaminomethyl cyclobutane oxalate | |
| Arjunan et al. | Syntheses and a conformational study of certain selected 3-oxa-7-azabicyclo [3.3. 1] nonan-9-ones. Single crystal x-ray diffraction analysis of 6, 8-bis (2-chlorophenyl)-3-oxa-7-azabicyclo [3.3. 1] nonan-9-one | |
| CN106188560B (en) | The supermolecule polymer and preparation method and application that a kind of ten quaternarys melon ring and porphyrin are constructed | |
| CN111349121A (en) | Cobalt carbonyl complex and preparation method thereof | |
| CN107722025A (en) | A kind of hexa-atomic melon ring of trans hexamethyl and preparation method and application | |
| CN102775415B (en) | Synthetic method for porphyrin | |
| CN102718698B (en) | Aspartic acid amlodipine compound and synthesis method thereof | |
| CN109694723A (en) | The eutectic solvent and method of non basic nitrogen are extracted from analog gasoline | |
| LU505007B1 (en) | Synthesis method and application of 4',4''(5'')-di-tert-butyl dicyclohexylo-18-crown ether-6 | |
| CN111138243B (en) | Preparation method of (1S,2R) -2-phenylcyclohexanol | |
| Xiong et al. | Photo-controllable binding and release of HP 2 O 7 3− using an azobenzene based smart macrocycle | |
| ES2686136A1 (en) | SYNTHESIS PROCEDURE OF 9,10-BIS (CHLOROMETHYL) ANTHRACEN (Machine-translation by Google Translate, not legally binding) | |
| CN102936255B (en) | Separation method for Q[5]@Q[10] |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |