CN104341428A - Pentamethyl pentacarbonyl cucurbit[5]uril and preparation method thereof - Google Patents
Pentamethyl pentacarbonyl cucurbit[5]uril and preparation method thereof Download PDFInfo
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- CN104341428A CN104341428A CN201410512568.1A CN201410512568A CN104341428A CN 104341428 A CN104341428 A CN 104341428A CN 201410512568 A CN201410512568 A CN 201410512568A CN 104341428 A CN104341428 A CN 104341428A
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- pentamethyl
- yuan
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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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Abstract
The invention provides pentamethyl pentacarbonyl cucurbit[5]uril and a preparation method thereof and particularly relates to PPQ[5] (pentamethyl pentacarbonyl cucurbit[5]uril), belonging to the technical field of modified cucurbit[n]urils. According to the pentamethyl pentacarbonyl cucurbit[5]uril and a preparation method thereof, SPMeQ[5] is used as raw material and reacts with sodium persulfate in an aqueous solution under a heating condition and the reaction product is separated to obtain PPQ[5] which has a chemical formula of {[(C35H40N20O15)].10 (H2O)}. The invention discloses process steps and process conditions of PPQ[5]. The invention has the following advantages: 1, the synthetic method is simple to operate and high in yield; 2, based on the special structure of cucurbit[n]urils, pentamethyl pentacarbonyl cucurbit[5]uril can be applied to research on coordination chemistry, supramolecular self-assembly and the like of cucurbit[n]urils.
Description
Technical field
A kind of pentamethyl-penta hydroxy group of the present invention five yuan of melon rings and preparation method thereof, specifically pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] and preparation method thereof.Belong to modification melon loop technique field.
Background technology
Melon ring (Cucurbit [
n] urils, Q [
n] s) there is the large ring cage compound linked up by n glycosides urea unit and 2n methylene bridge, two opening end edge " is inlayed " and a circle carbonylic oxygen atom, thus there is the ability with metallic ion coordination, and then form melon cyclic group title complex and the ligand polymer of various structures feature.Hydroxyl melon ring (perhydroxycucurbit [
n] uril, (HO)
2nq [
n] s), because its outer wall also has multiple hydroxyl reactive group, hydroxyl substituted cucurbituril is made not only to maintain the feature such as structure and character of common melon ring, the reactive behavior of its outer wall hydroxyl and the coordination with metal ion, make hydroxyl substituted cucurbituril have better development prospect in the practical applications such as front line science and investigation of materials such as multidimensional and multiple-level time self-assembly, molecular recognition, molecular device, host-guest chemistry and supramolecular chemistry.The synthesis of current hydroxyl substituted cucurbituril general all with common melon ring for raw material, but normal yield is not high, the productive rate being the hydroxyl melon ring that raw material obtains as common five yuan of melon rings or hexa-atomic melon ring is no more than 45%, and seven yuan of melon rings or eight yuan of melon rings are productive rate not even (the Jon S. Y. more than 5% of the hydroxyl melon ring that raw material obtains, Selvapalam N., Oh D. H., et al
j. Am. Chem. Soc .
2003, 125,10186).This hinders the development of melon cyclisation in above-mentioned field greatly.Because the common oxidable position of melon ring is more, not only may produce too much hydroxylation position, make further derivatize restive, be also the major cause causing the decomposition of melon epoxidation, low yield simultaneously.Therefore we attempt utilizing alkyl substituted cucurbituril to replace common melon ring, can reduce hydroxylation position like this, also likely provide the hydroxyl melon ring that more structure is special simultaneously.In the present invention, the monosubstituted pentamethyl-that we select five yuan of melon ring SPMeQ [5], its waist have the position of half by can not hydroxylated methyl substituted, therefore, can obtain novel hydroxyl melon ring PPQ [5] only having five hydroxyls.This not only limit oxidable position, also may reduce the polyoxygenated decomposition to melon ring simultaneously and destroy, and can improve the productive rate of hydroxyl melon ring.
Summary of the invention
The object of the invention is to the hydroxyl melon ring preparing a kind of high yield, i.e. pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5].
A kind of pentamethyl-penta hydroxy group of the present invention five yuan of melon rings, be raw material by pentamethyl-five yuan of melon ring SPMeQ [5], with Sodium Persulfate reacting by heating in aqueous, a kind of pentamethyl-penta hydroxy group of resultant through being isolated five yuan of melon ring PPQ [5], pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] chemical formulas of indication are:
{[(C
35H
40N
20O
15)]·10(H
2O)}
The structural formula of pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] is:
Pentamethyl-five yuan of melon ring SPMeQ [5] molecular formula of indication are: { [(C
35h
40n
20o
10)] 10 (H
2o) }
Structural formula is
The preparation method of a kind of pentamethyl-penta hydroxy group of the present invention five yuan of melon rings, follows these steps to carry out:
(1) pentamethyl-five yuan of melon ring SPMeQ [5] and Sodium Persulfate are weighed 1:5 ~ 7 in molar ratio, pour into after mixing in there-necked flask;
(2) ratio adding 45-50ml distilled water according to every gram of pentamethyl-five yuan of melon rings in said mixture adds distilled water;
(3) the emulsion reacting by heating 7-8 hour under 75 DEG C of conditions will obtained in step (2), obtains the mixture of pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5];
(4) the mixture evaporate to dryness of PPQ [5] will obtained, obtains mixture solid;
(5) add dimethyl sulfoxide (DMSO) DMSO to mixture solid to dissolve, decompress filter removes insolubles filter residue, retains DMSO filtrate;
(6) in DMSO solution, add dehydrated alcohol, produce precipitation, and continue to add ethanol and make precipitation complete;
(7) by the precipitation decompress filter of step (6), and precipitate 3-4 time with absolute ethanol washing, obtain pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] crude products;
(8) by PPQ [5] crude product, through hydrogen ion type Dowex column chromatography for separation, pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] sterlings are obtained.
Experiment proves the preparation method of a kind of pentamethyl-penta hydroxy group five yuan of melon rings, as pentamethyl-five yuan of melon ring SPMeQ [5], Sodium Persulfate Na
2s
2o
8in molar ratio 1: 6 time, pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] productive rates are the highest.
Above-mentioned column chromatography stationary phase used is Dowex50W × 2 hydrogen ion types; Leacheate is the mixing solutions of glacial acetic acid, water and hydrochloric acid, and wherein concentration of hydrochloric acid is 0.1 ~ 0.5mol/L, and the volume ratio of Glacial acetic acid and water is 1:1, and the volume ratio of Glacial acetic acid, water and concentrated hydrochloric acid is 500:500:8.5 ~ 42.5.
The preparation of a kind of pentamethyl-penta hydroxy group of the present invention five yuan of melon rings, utilizes SPMeQ [5] and Sodium Persulfate in aqueous under heating condition, obtains the hydroxyl melon ring product be oxidized.In view of its advantage in solvability and active group, also provide favourable condition for the five yuan of melon ring researchs in other respects of pentamethyl-penta hydroxy group.
The present invention is by carrying out structural characterization and character research to PPQ [5], can draw to draw a conclusion: the solvability of PPQ [5] in water and in part organic solvent is greatly improved, PPQ [5] is containing multiple hydroxyl, and this improves in formation at metal-complexing, Supramolecular self assembly body etc.
In the present invention to synthesized melon ring and title complex adopt X-ray single crystal diffraction,
1the analysis means such as H-NMR carry out the sign such as structure, character.
Patent 1 of the present invention) synthetic method that uses has simple to operate, productive rate high.2) utilize the special construction of energy melon ring, can be used for the research of the aspects such as melon ring coordination chemistry and Supramolecular self assembly.
Accompanying drawing explanation
Fig. 1 SPMeQ [5] is oxidized to the crystalline structure schematic diagram of PPQ [5];
Fig. 2 SPMeQ [5] (on) and PPQ [5] (under)
1h-NMR schemes.
Embodiment
Embodiment 1:
(1) pentamethyl-five yuan of melon ring SPMeQ [5] 10.0g(9.26 mmol are taken respectively), Na
2s
2o
813.23g(55.56mmol), mol ratio is SPMeQ [5]: Na
2s
2o
8=1:6, pours in 1000ml there-necked flask after mixing;
(2) in said mixture, 500ml distilled water is added;
(3) be positioned in magnetic stirring apparatus and react, temperature is 75 DEG C, 8 hours reaction times, obtains PPQ [5] mixture after having reacted;
(4) the mixture evaporate to dryness of PPQ [5] will obtained, obtains mixture solid;
(5) add dimethyl sulfoxide (DMSO) DMSO to mixture solid to dissolve, decompress filter removes insolubles filter residue, retains DMSO filtrate;
(6) in DMSO solution, add dehydrated alcohol, produce precipitation, and continue to add ethanol and make precipitation complete;
(7) by the precipitation decompress filter of step (6), and precipitate 4 times with absolute ethanol washing, obtain pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] crude products;
(8) by PPQ [5] crude product, through hydrogen ion type Dowex column chromatography for separation, pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] sterlings are obtained.
Column chromatography stationary phase used is Dowex50W 2 hydrogen ion type, with leacheate by PPQ [5] crude product furnishing pasty state, transfer upper prop, leacheate is glacial acetic acid, the mixing solutions of water and hydrochloric acid, wherein concentration of hydrochloric acid is 0.2mol/L, the volume ratio of glacial acetic acid and water is 1:1, the volume being specifically formulated as glacial acetic acid is 500ml, the volume of water is 500ml, the volume of concentrated hydrochloric acid is 17.0ml, with leacheate drip washing repeatedly after sample upper prop, and the leacheate oozed is collected successively and evaporate to dryness after, solid is detected by nuclear-magnetism, judge whether isolated sample is PPQ [5].Isolated sampfe order is ammonium salt, glycosides urea fragment, the melon ring (seldom) of partial oxidation, PPQ [5] successively.Continue to be separated, finally sterling PPQ [5] is separated completely, and obtain the productive rate of 90%.
Embodiment 2:
Operation steps is with embodiment 1, and difference is step 1, takes pentamethyl-five yuan of melon ring SPMeQ [5] 10.0g(9.26mmol respectively), Na
2s
2o
811.02g(46.30mmol), mol ratio is SPMeQ [5]: Na
2s
2o
8=1:5, the thick product that step (7), (8) obtain is detected by nuclear-magnetism, and hydroxyl characteristic peak is compared with embodiment 1, and effect is obvious not, PPQ [5] productive rate 80%.
Embodiment 3:
Operation steps is with embodiment 1, and difference is step 1, takes pentamethyl-five yuan of melon ring SPMeQ [5] 10.0g(9.26mmol respectively), Na
2s
2o
815.44g(64.82mmol), mol ratio is SPMeQ [5]: Na
2s
2o
8the sterling productive rate 70% that=1:7 step (8) obtains.
Claims (4)
1. a pentamethyl-penta hydroxy group five yuan of melon rings, it is characterized in that by pentamethyl-five yuan of melon ring SPMeQ [5] be raw material, with Sodium Persulfate reacting by heating in aqueous, a kind of pentamethyl-penta hydroxy group of resultant through being isolated five yuan of melon ring PPQ [5], pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] chemical formulas of indication are:
{[(C
35H
40N
20O
15)]·10(H
2O)}
The structural formula of pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] is:
。
2. the preparation method of a kind of pentamethyl-as claimed in claim 1 five yuan of melon rings, is characterized in that following these steps to carry out:
(1) pentamethyl-five yuan of melon ring SPMeQ [5] and Sodium Persulfate are weighed 1:5 ~ 7 in molar ratio, pour into after mixing in there-necked flask;
(2) ratio adding 45-50ml distilled water according to every gram of pentamethyl-five yuan of melon rings in said mixture adds distilled water;
(3) the emulsion reacting by heating 7-8 hour under 75 DEG C of conditions will obtained in step (2), obtains the mixture of pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5];
(4) the mixture evaporate to dryness of PPQ [5] will obtained, obtains mixture solid;
(5) add dimethyl sulfoxide (DMSO) DMSO to mixture solid to dissolve, decompress filter removes insolubles filter residue, retains DMSO filtrate;
(6) in DMSO solution, add dehydrated alcohol, produce precipitation, and continue to add ethanol and make precipitation complete;
(7) by the precipitation decompress filter of step (6), and precipitate 3-4 time with absolute ethanol washing, obtain pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] crude products;
(8) by PPQ [5] crude product, through hydrogen ion type Dowex column chromatography for separation, pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] sterlings are obtained.
3. the preparation method of a kind of pentamethyl-according to claim 2 five yuan of melon rings, is characterized in that: as pentamethyl-five yuan of melon ring SPMeQ [5], Sodium Persulfate Na
2s
2o
8in molar ratio 1: 6 time, pentamethyl-penta hydroxy group five yuan of melon ring PPQ [5] productive rates are the highest.
4. the preparation method of a kind of pentamethyl-according to claim 2 five yuan of melon rings, is characterized in that: column chromatography stationary phase used is Dowex50W × 2 hydrogen ion types; Leacheate is the mixing solutions of glacial acetic acid, water and hydrochloric acid, and wherein concentration of hydrochloric acid is 0.1 ~ 0.5mol/L, and the volume ratio of Glacial acetic acid and water is 1:1, and the volume ratio of Glacial acetic acid and water and concentrated hydrochloric acid is 500:500:8.5 ~ 42.5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860079A (en) * | 2016-06-08 | 2016-08-17 | 贵州大学 | Sol-gel coating based on single-hydroxyl cucurbit (7) uril and preparing method and application thereof |
| CN106065019A (en) * | 2016-06-08 | 2016-11-02 | 贵州大学 | A kind of preparation method of monohydroxy cucurbit(7)uril |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1604899A (en) * | 2002-01-03 | 2005-04-06 | 学校法人浦项工科大学校 | Hydroxycucurbituril derivatives, their preparation methods and uses |
| WO2006005727A1 (en) * | 2004-07-08 | 2006-01-19 | International University Bremen Gmbh | Photostabilisation of fluorescent dyes |
| CN103157453A (en) * | 2013-04-03 | 2013-06-19 | 贵州大学 | Solid phase microextraction coating of hydroxyl cucurbituril as well as preparation method and application thereof |
-
2014
- 2014-09-29 CN CN201410512568.1A patent/CN104341428A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1604899A (en) * | 2002-01-03 | 2005-04-06 | 学校法人浦项工科大学校 | Hydroxycucurbituril derivatives, their preparation methods and uses |
| WO2006005727A1 (en) * | 2004-07-08 | 2006-01-19 | International University Bremen Gmbh | Photostabilisation of fluorescent dyes |
| CN103157453A (en) * | 2013-04-03 | 2013-06-19 | 贵州大学 | Solid phase microextraction coating of hydroxyl cucurbituril as well as preparation method and application thereof |
Non-Patent Citations (2)
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| 孙津鸽 等: "十羟基五元瓜环与镉离子配合物的合成及晶体结构", 《贵州大学学报(自然科学版)》, vol. 30, no. 1, 28 February 2013 (2013-02-28), pages 19 - 22 * |
| 尉震 等: "甲基取代瓜环的羟基化及其高聚物的合成", 《贵州大学学报(自然科学版)》, vol. 24, no. 3, 31 May 2007 (2007-05-31) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860079A (en) * | 2016-06-08 | 2016-08-17 | 贵州大学 | Sol-gel coating based on single-hydroxyl cucurbit (7) uril and preparing method and application thereof |
| CN106065019A (en) * | 2016-06-08 | 2016-11-02 | 贵州大学 | A kind of preparation method of monohydroxy cucurbit(7)uril |
| CN106065019B (en) * | 2016-06-08 | 2018-10-23 | 贵州大学 | A kind of preparation method of monohydroxy cucurbit(7)uril |
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Application publication date: 20150211 |