CN107722025A - A kind of hexa-atomic melon ring of trans hexamethyl and preparation method and application - Google Patents
A kind of hexa-atomic melon ring of trans hexamethyl and preparation method and application Download PDFInfo
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- CN107722025A CN107722025A CN201711113438.0A CN201711113438A CN107722025A CN 107722025 A CN107722025 A CN 107722025A CN 201711113438 A CN201711113438 A CN 201711113438A CN 107722025 A CN107722025 A CN 107722025A
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- hexamethyl
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- melon ring
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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
- C07D487/22—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 four or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of hexa-atomic melon ring of trans hexamethyl and preparation method and application.The molecular formula of the hexa-atomic melon ring of described trans hexamethyl is { [(C42H48N24O12)]·10(H2O) }, molecular weight 1260, structural formula are：The present invention has good water solubility, the advantages of being dissolved in organic solvent and high yield.
Description
Technical field
The present invention relates to be related to supramolecular chemistry field, more particularly to a kind of hexa-atomic melon ring of trans hexamethyl and preparation method
And application.
Background technology
Mock seminar in 1981 characterizes first member-six of Gua Huan families using Advances in crystal X-ray diffraction method
First melon ring (Q [6]), Day seminar in 2000 and Kim seminar are in-five yuan of homologue for reporting three kinds of hexa-atomic melon rings simultaneously
Melon ring (Q [5]), cucurbit(7)uril (Q [7]) and eight yuan of melon rings (Q [8])；Day seminar in 2002 reports five yuan of inclusion again
Ten yuan of melon rings (Q [5]@Q [10]) of melon ring；The synthesis in 2006 of American scholar Isaacs seminar obtains ten yuan of melons of dislocation bridging
Ring；2007 synthesis obtain misplace bridging hexa-atomic melon ring, report within 2011 omission hexa-atomic melon ring, these melon rings be all with
C- types polymer is the melon ring for constructing module formation substantially.American scholar Isaacs seminar in 2005 grinds with South Korea scholar Kim
Study carefully combination to have made reports trans hexa-atomic melon ring (Q [6] *) and trans cucurbit(7)uril (Q [7] *), these melon rings are all with S- type polies
Body is the melon ring for constructing module formation substantially.Then the appearance of these melon rings is established for the mechanism that melon ring is formed and has established important base
Plinth：I.e. glycosides urea reacts to form C- types polymer and S- type polymers with formaldehyde, and then C- types polymer further forms series
Common melon ring and not completely closed melon ring etc.；And S- types polymer further forms the trans melon ring of series.
But trans hexa-atomic melon ring generally existing poorly water-soluble, and can not substantially dissolving in organic solvent at present, and
And its synthetic yield it is relatively low the shortcomings that.
The content of the invention
It is an object of the invention to provide a kind of hexa-atomic melon ring of trans hexamethyl and preparation method and application.The present invention has water
Dissolubility is good, the advantages of being dissolved in organic solvent and high yield.
What the present invention was realized in：A kind of hexa-atomic melon ring of trans hexamethyl, its molecular formula are { [(C42H48N24O12)]·
10(H2O) }, molecular weight 1260, structural formula are：
The preparation method of the hexa-atomic melon ring of foregoing trans hexamethyl, is prepared according to the following steps：
A. by methyl glycoluril diether and common glycoluril in molar ratio 1:1 mixing, obtains A product；
B. A product are put into the concentrated hydrochloric acid that mass fraction is 36%-38%, the amount of concentrated hydrochloric acid is corresponding by every gram of common glycoluril
11-12mL is counted, and when temperature is 90-100 DEG C, is heated to reflux 1.5-3 hours, is cooled down, and repeatedly plus water deacidifies to solution into neutrality,
Obtain B product；
C. formic acid 200-300mL is added into B product, concentration stands to obtain C product；
D. C product are loaded into the chromatographic column that Dowex cationics exchanger resin is stationary phase, and with 0.1~0.5M salt
Acid elution 1-2 days, obtains the hexa-atomic melon ring of trans hexamethyl.
The application of the hexa-atomic melon ring of foregoing trans hexamethyl：The trans hexa-atomic melon ring of hexamethyl is used for metal-complexing, oversubscription
The formation of sub- self-assembly or host-guest chemistry.
Beneficial effect：Compared with prior art, preparation method of the invention is simple to operate, and yield is high, can be efficient
It is quickly obtained melon ring.The dissolubility of the hexa-atomic melon ring of trans hexamethyl prepared by the present invention in water and in the organic solvent of part obtains
To large increase, using the special construction of the melon ring, melon ring Coordinative Chemistry, Supramolecular self assembly, host-guest chemistry etc. have been expanded
The research range of aspect.
In order to prove beneficial effects of the present invention, applicant carried out following experiment：
The hexa-atomic melon ring of trans hexamethyl that embodiment 1 is prepared carries out nuclear magnetic resonance in deuterated water, as a result such as Fig. 1
Shown, the hexa-atomic melon ring of trans hexamethyl that the present invention is prepared can be dissolved in water, and be pure melon ring.
The hexa-atomic melon ring of trans hexamethyl that embodiment 1 is prepared carries out nuclear magnetic resonance in deuterated dimethyl sulfoxide, knot
Fruit is as shown in Fig. 2 the hexa-atomic melon ring of trans hexamethyl that the present invention is prepared can be dissolved in DMSO, and be pure melon ring.
The hexa-atomic melon ring of trans hexamethyl that embodiment 1 is prepared carries out mass spectral analysis, as a result as shown in figure 3, mass spectrum
It is that 1080 (mass spectrum is not added with when calculating that analysis, which obtains the relative molecular mass of the hexa-atomic melon ring of trans hexamethyl that the present invention is prepared,
Crystalline water molecules amount).
The present invention is by common glycoluril and methyl glycoluril diether in molar ratio 1:1 mixing, the reaction time at 90~100 DEG C
1.5~3 hours, obtained trans hexamethyl substituted the yield of hexa-atomic melon ring to be higher than 1%, and its yield is high.
Brief description of the drawings
Fig. 1 is the hexa-atomic melon ring of trans hexamethyl in deuterated water1H nmr spectrums；
Fig. 2 is the hexa-atomic melon ring of trans hexamethyl in deuterated dimethyl sulfoxide1H nmr spectrums；
Fig. 3 is the mass spectral results of the hexa-atomic melon ring of trans hexamethyl；
Fig. 4 is the structural formula of the hexa-atomic melon ring of trans hexamethyl prepared by the present invention.
Embodiment
Embodiment 1.A kind of hexa-atomic melon ring of trans hexamethyl, its molecular formula are { [(C42H48N24O12)]·10(H2O) }, divide
Son amount is 1260, and structural formula is：
The preparation method of the hexa-atomic melon ring of foregoing trans hexamethyl, is prepared according to the following steps：
A. 42 grams of methyl glycoluril diether and 23 grams of common glycolurils are mixed, obtains A product；
B. by A product be put into 260mL mass fraction be 36%-38% concentrated hydrochloric acid in, temperature be 90-100 DEG C when, add
Heat backflow 2 hours, cooling, repeatedly plus water deacidifies to solution into neutrality, obtains B product；
C. formic acid 200-300mL is added into B product, concentration stands to obtain C product；
D. C product are loaded into the chromatographic column that Dowex cationics exchanger resin is stationary phase, and with 0.1~0.5M salt
Acid elution, during elution, increase the polarity of leacheate according to the substance gradients eluted, elution obtains trans hexamethyl six in 1-2 days
First melon ring.
The hexa-atomic melon ring of foregoing trans hexamethyl is used for for metal-complexing, Supramolecular self assembly body or host-guest chemistry
Formed；The research range of melon ring Coordinative Chemistry, Supramolecular self assembly, host-guest chemistry etc. is expanded.
Embodiment 2.A kind of hexa-atomic melon ring of trans hexamethyl, it is characterised in that：The hexa-atomic melon ring of described trans hexamethyl
Molecular formula is { [(C42H48N24O12)]·10(H2O) }, molecular weight 1260, structural formula are：
The hexa-atomic melon ring of foregoing trans hexamethyl is prepared according to the following steps：
A. by methyl glycoluril diether and common glycoluril in molar ratio 1:1 mixing, obtains A product；
B. A product are put into the concentrated hydrochloric acid that mass fraction is 36%-38%, the amount of concentrated hydrochloric acid is corresponding by every gram of common glycoluril
11-12mL is counted, and when temperature is 90-100 DEG C, is heated to reflux 1.5-3 hours, is cooled down, and repeatedly plus water deacidifies to solution into neutrality,
Obtain B product；
C. formic acid 200-300mL is added into B product, concentration stands to obtain C product；
D. C product are loaded into the chromatographic column that Dowex cationics exchanger resin is stationary phase, and with 0.1~0.5M salt
Acid elution 1-2 days, obtains the hexa-atomic melon ring of trans hexamethyl.
The hexa-atomic melon ring of foregoing trans hexamethyl is used for the shape of metal-complexing, Supramolecular self assembly body or host-guest chemistry
Into.
Claims (3)
- A kind of 1. hexa-atomic melon ring of trans hexamethyl, it is characterised in that：The molecular formula of the hexa-atomic melon ring of described trans hexamethyl is {[(C42H48N24O12)]·10(H2O) }, molecular weight 1260, structural formula are：
- 2. a kind of preparation method of the trans hexa-atomic melon ring of hexamethyl as claimed in claim 1, it is characterised in that in the steps below Prepare：A. by methyl glycoluril diether and common glycoluril in molar ratio 1:1 mixing, obtains A product；B. A product are put into the concentrated hydrochloric acid that mass fraction is 36%-38%, the amount of concentrated hydrochloric acid corresponds to 11- by every gram of common glycoluril 12mL is counted, and when temperature is 90-100 DEG C, is heated to reflux 1.5-3 hours, is cooled down, repeatedly plus water deacidifies to solution into neutrality, obtains B Product；C. formic acid 200-300mL is added into B product, concentration stands to obtain C product；D. C product are loaded into the chromatographic column that Dowex cationics exchanger resin is stationary phase, and drenched with 0.1~0.5M hydrochloric acid Wash 1-2 days, obtain the hexa-atomic melon ring of trans hexamethyl.
- A kind of 3. application of the trans hexa-atomic melon ring of hexamethyl as claimed in claim 1, it is characterised in that：The trans hexamethyl six First melon ring is used for the formation of metal-complexing, Supramolecular self assembly body or host-guest chemistry.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232587A (en) * | 2018-08-23 | 2019-01-18 | 南京信息工程大学 | A kind of melon ring and its preparation method and application with highly-water-soluble |
| CN113583009A (en) * | 2021-07-23 | 2021-11-02 | 贵州大学 | Novel dibromomethyl substituted six-membered cucurbituril with high active site and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040167328A1 (en) * | 2003-02-25 | 2004-08-26 | Geckeler Kurt E | Cucurbituril-fullerene complex |
| CN101157053A (en) * | 2007-10-17 | 2008-04-09 | 贵州大学 | Catalyst and use thereof new type solid catalyst as well as its preparing method and usage |
| CN102205242A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院福建物质结构研究所 | Method for preparing dispersed palladium nanoparticle catalyst with controllable appearance by using cucurbit[6]uril (CB[6]) |
| CN103351399A (en) * | 2013-07-30 | 2013-10-16 | 贵州大学 | Synthesis and separation method for trans cucurbit[6]uril |
-
2017
- 2017-11-13 CN CN201711113438.0A patent/CN107722025A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040167328A1 (en) * | 2003-02-25 | 2004-08-26 | Geckeler Kurt E | Cucurbituril-fullerene complex |
| CN101157053A (en) * | 2007-10-17 | 2008-04-09 | 贵州大学 | Catalyst and use thereof new type solid catalyst as well as its preparing method and usage |
| CN102205242A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院福建物质结构研究所 | Method for preparing dispersed palladium nanoparticle catalyst with controllable appearance by using cucurbit[6]uril (CB[6]) |
| 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 |
|---|
| 余大海: ""部分甲基取代改性瓜环的合成、表征及其性质研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232587A (en) * | 2018-08-23 | 2019-01-18 | 南京信息工程大学 | A kind of melon ring and its preparation method and application with highly-water-soluble |
| CN113583009A (en) * | 2021-07-23 | 2021-11-02 | 贵州大学 | Novel dibromomethyl substituted six-membered cucurbituril with high active site and preparation method thereof |
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