CN108484925A - A kind of advanced rotaxane and its synthetic method - Google Patents
A kind of advanced rotaxane and its synthetic method Download PDFInfo
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- CN108484925A CN108484925A CN201810283146.XA CN201810283146A CN108484925A CN 108484925 A CN108484925 A CN 108484925A CN 201810283146 A CN201810283146 A CN 201810283146A CN 108484925 A CN108484925 A CN 108484925A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/007—Polyrotaxanes; Polycatenanes
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Abstract
The present invention relates to a kind of synthetic methods of organic compound, more particularly to a kind of advanced rotaxane and its synthetic method, crown ether and ammonium salt are dissolved in organic solvent, it is stirred at room temperature 24 hours, trifluoromethanesulfonic acid is added, it is stirred at room temperature overnight, reaction solution is quenched with ice water, organic solvent extracts, washing, isolate organic layer, anhydrous sodium sulfate is dried, decompression rotation goes solvent to obtain branched rotaxane, the present invention carries out synthesis of such reaction in advanced rotaxane, molecule machine, the area researches such as supermolecule polymer, a completely new thinking is provided for the development of supramolecular chemistry, play certain impetus.
Description
Technical field
The present invention relates to a kind of synthetic method of organic compound, more particularly to a kind of advanced rotaxane and its synthetic method.
Background technology
Rotaxane（Rotaxane）It is one or more ring molecules and the molecule that one or more chain molecules are axis composition
Set, chain molecule make the cavity that axis passes through toroidal molecule, and both ends are combined with volume bigger molecule to prevent skidding off for molecular shaft, from
And the inner-lock-type supramolecular system formed（Fig. 1）.2016 annual Nobel chemistry Prizes authorize the allowing of Strasbourg, FRA university-
Pi Aiersuowa（Jean-Pierre Sauvage）, Northwestern Univ USA James frazier Situ Ta Te（Sir
J.Fraser Stoddart）And the bernard Fei Lingge of Groningen ,Holland university（Bernard L.Feringa）, with
Reward the contribution in terms of their " in the designs and synthesis of molecule machine ".
The report of first case rotaxane will trace back to the sixties in last century, but in nearly 20 year later, due to not having
The correlative study of the synthetic method of effect, rotaxane is constantly in opposite dead state.The beginning of the nineties, the hairs such as Stoddart, Gibson
It has opened up threading-sealing end, templated synthesis and has slid into method to construct rotaxane.Rotaxane has just obtained in fields such as molecule machines more next later
More it is widely applied.With the development to rotaxane application study, supermolecular scholars generally require to construct with labyrinth
Advanced rotaxane or inner-lock-type supermolecule polymer.Previously reported such advanced assembly is all by threading-sealing end, slide-in
Or templated synthesis these three conventional methods are constructed, general yield is relatively low or reaction is very slow.In order to solve this problem, supermolecule
Chemists are also exploring always the novel method for constructing rotaxane.2004 and 2010, Asakawa and Chiu were utilized respectively
The method of " threading-contracting ring " has constructed rotaxane, and a new thinking is provided for the preparation of this kind of inner-lock-type molecule.But this
The example yield of two rotaxanes synthesis is no more than 30%, and exists and need equivalent noble metal, discharge sulfur dioxide pollution, reaction
Condition is harsh, needs special installation, the deficiencies of reaction rate is slower, therefore this method is not yet in the synthesis of advanced rotaxane, supermolecule
The fields such as polymer are applied.
S-triazine molecule has special fragrant ring skeleton, they are because extensive with good physical and chemical properties
Applied to functional material, medicine and other fields.Lewis acid can be used as the poly- catalyst of nitrile compounds ring, the use such as Xu in 2002
Samarium (II) salt forms catalyst system and catalyzing with n-hexylamine, and under the conditions of 80 DEG C, it is anti-to be catalyzed fragrant cyanides initial ring polycondensation
It answers, obtains aryl class Striazine derivative, reaction yield is all higher, is the good method for synthesizing aromatics Striazine derivative.
The reports such as Ren in 2011 are using trifluoromethanesulfonic acid as catalyst, and chloroform is as solvent, in anhydrous and oxygen-free and room temperature condition
It is lower to have synthesized a series of s-triazines with electron transfer efficiency in larger conjugated system and higher molecular.Fragrance equal three
Piperazine molecule due to its have many advantages, such as big fragrant ring skeleton, it is multiple can derivatization reaction site, be easily-synthesized and can be used as wheel
The end-capping group of alkane synthesis, has in fields such as advanced rotaxane synthesis, molecule machine, supermolecule polymers and potentially applies valence
Value.
The synthesis of rotaxane is presently mainly to pass through threading-sealing end, slide-in, templated synthesis or " threading-contracting ring " these types side
What method was constructed, general yield is relatively low or reaction is very slow, also has limitation in the synthesis of advanced rotaxane.
Invention content
One kind is provided and contains envelope by synthesizing one end it is an object of the invention to overcome the deficiencies in the prior art
End group group, the other end contain the pseudorotaxane of fragrant cyanides, and initial ring polycondensation reaction, is contained under Lewis acid catalysis
The advanced rotaxane and its synthetic method of the branched rotaxane of fragrant Striazine derivative.
A kind of rotaxane, molecular formula are shown in formula I：
Formulas I.
The synthetic method of above-mentioned rotaxane carries out in accordance with the following steps：
Step 1）, crown ether and ammonium salt be dissolved in organic solvent, stir 2-4 hours at room temperature；
Step 2）, be added trifluoromethanesulfonic acid, be stirred at room temperature overnight, reaction solution is quenched with ice water, organic solvent extraction, water
It washes, isolates organic layer, anhydrous sodium sulfate drying, decompression rotation goes solvent to obtain branched rotaxane.
In step 1）Described in organic solvent be dichloromethane.
Compared with prior art, the present invention has the advantages that：Carry out such reaction advanced rotaxane synthesis, point
The area researches such as handset device, supermolecule polymer provide a completely new thinking for the development of supramolecular chemistry, play certain
Impetus.Advanced rotaxane prepared by the present invention is suitable for constructing the supramolecular system of molecule machine, it is reversibly dissociated into
Free annular body and linear object, generate the motion mode similar to " screw-in/back-out ".
Friendship of the supermolecule science as subjects such as chemical science, life science, material science, molectronics, sensors
Fork and the recent studies on field merging and generate, in recent years obtained swift and violent development, achieve the achievement to attract people's attention.Pass through
The oversubscription fructifications such as rotaxane, the catenne that intermolecular interaction is formed are also novel to design and constructing in nanometer and molecular scale
Molecular device provide wide application prospect.The present invention has there is no equivalent noble metal is needed, and does not discharge titanium dioxide
Sulphur pollution, and the advantages that reaction condition is suitable, does not need special installation, and reaction rate is very fast, therefore the present invention is in high step cone
The fields such as alkane synthesis, supermolecule polymer are applied.
Description of the drawings
Fig. 1 is that chain molecule makees axis and has volume bigger molecule shape across toroidal molecule cavity and both ends in rotaxane elements collection
At inner-lock-type supramolecular system figure.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below, it is to be understood that protection scope of the present invention is not
It is restricted by specific implementation.
Embodiment 1：
Synthetic route is as follows：
By dibenzo -24- crown-s 8 (250 mg, 0.56 mmol) and N- (anthracene -9- ylmethyls) -3- (4- cyano-benzene oxygens)
Propyl- 1- ammoniums hexafluorophosphate (285 mg, 0.56 mmol) is dissolved in the dichloromethane of 10 ml, and it is small to be stirred at room temperature 3
When.Trifluoromethanesulfonic acid (85 mg, 0.56 mmol) is added into above-mentioned reaction solution, is stirred at room temperature overnight, reaction solution is used
Ice water is quenched, dichloromethane (2 × 50 ml) extraction, washing, isolates organic layer, anhydrous sodium sulfate drying, and decompression rotation is gone molten
Agent obtains branched rotaxane (465 mg), yield 87%.1H NMR (400MHz, CD3D) δ：1H NMR (400 MHz, CDCl3,
295 K): δ 8.64 (d, J = 8.8 Hz, 6H), 8.48 (s, 3H), 8.27-8.23 (m, 6H), 7.97 (d,J = 8.4 Hz, 6H), 7.90 (d, J = 8.0 Hz, 6H), 7.65-7.41 (m, 24H), 6.91-6.85 (m,
12H), 6.75-6.71 (m, 6H), 6.60 (d, J = 8.8 Hz, 6H), 6.48-6.46 (m, 6H), 5.58
(s, 4H), 5.19 (s, 4H), 4.14-4.16 (m, 18H), 4.07-4.03 (m, 45H), 3.93-3.84 (m,
15H), 3.77-3.70 (m, 5H), 3.55-3.51 (m, 5H), 3.11 (s, 4H), 2.22-2.19(m, 6H)。
Anthryl group containing electron rich in the branched rotaxane prepared, therefore using the shuttle of rotaxane, make macrocycle molecule
Relative position changes, and molecular computer is prepared to replace so as to cause the variation of the high conductance state and low conductance state of system
ON/OFF state in transistor.The branched rotaxane of preparation is dissolved in acetonitrile, by the way that triethylamine or trifluoroacetic acid are added into solution
The shuttle for realizing rotaxane, is detected by nucleus magnetic hydrogen spectrum and the variation of conductance state in system.
Advanced rotaxane prepared by the present invention is suitable for constructing the supramolecular system of molecule machine, it is reversibly dissociated into certainly
By annular body and linear object, generate the motion mode similar to " screw-in/back-out ".
The advanced rotaxane that the present invention is manipulated using outside stimulus is used for stablizing the non-covalent bond work of initial super molecular complex
Firmly, cooperation is given by N-HO and C-HO hydrogen bond actions or C-HO hydrogen bonds and π-electronics
The effect of be combineding with each other of body/acceptor, addition can enable the alkali of ammonium center deprotonation easily destroy N-H
The interaction of hydrogen bond of O, and the acid that amine can be made to protonate, which is added, to be recovered, and lean on interaction of hydrogen bond to combine so super
Mechanical movement can be generated in molecular complex by the variation (acid/base) of place chemical environment.
Disclosed above is only specific embodiments of the present invention, and still, the present invention is not limited to this, any this field
What technical staff can think variation should all fall into protection scope of the present invention.
Claims (3)
1. a kind of advanced rotaxane, which is characterized in that its molecular formula is shown in formula I：
Formulas I.
2. a kind of synthetic method of advanced rotaxane as described in claim 1, which is characterized in that carry out in accordance with the following steps：
Step 1）, crown ether and ammonium salt be dissolved in organic solvent, be stirred at room temperature 2-4 hours；
Step 2）, be added trifluoromethanesulfonic acid, be stirred at room temperature overnight, reaction solution is quenched with ice water, organic solvent extraction, water
It washes, isolates organic layer, dried using anhydrous sodium sulfate, decompression rotation goes solvent to obtain branched rotaxane.
3. the synthetic method of advanced rotaxane according to claim 2, which is characterized in that in step 1）Described in organic solvent
For dichloromethane.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6100329A (en) * | 1998-03-12 | 2000-08-08 | Virginia Tech Intellectual Properties, Inc. | Reversible, mechanically interlocked polymeric networks which self-assemble |
| JP2004083470A (en) * | 2002-08-27 | 2004-03-18 | National Institute Of Advanced Industrial & Technology | Noncovalently bonded aggregate, its production method, mechanically bonded aggregate obtained by direct conversion of former aggregate, and its direct conversion method |
| WO2014045921A1 (en) * | 2012-09-19 | 2014-03-27 | 住友精化株式会社 | Method for manufacturing polyrotaxane |
| CN104341385A (en) * | 2014-10-17 | 2015-02-11 | 南京理工大学 | Fluorescent [2] rotaxane based on pyrene and rhodamine B, and preparation and application thereof |
-
2018
- 2018-04-02 CN CN201810283146.XA patent/CN108484925A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6100329A (en) * | 1998-03-12 | 2000-08-08 | Virginia Tech Intellectual Properties, Inc. | Reversible, mechanically interlocked polymeric networks which self-assemble |
| JP2004083470A (en) * | 2002-08-27 | 2004-03-18 | National Institute Of Advanced Industrial & Technology | Noncovalently bonded aggregate, its production method, mechanically bonded aggregate obtained by direct conversion of former aggregate, and its direct conversion method |
| WO2014045921A1 (en) * | 2012-09-19 | 2014-03-27 | 住友精化株式会社 | Method for manufacturing polyrotaxane |
| CN104662066A (en) * | 2012-09-19 | 2015-05-27 | 住友精化株式会社 | Method for manufacturing polyrotaxane |
| CN104341385A (en) * | 2014-10-17 | 2015-02-11 | 南京理工大学 | Fluorescent [2] rotaxane based on pyrene and rhodamine B, and preparation and application thereof |
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