CN109851809A - A kind of column [5] aromatic monomer and its homopolymer and preparation method - Google Patents
A kind of column [5] aromatic monomer and its homopolymer and preparation method Download PDFInfo
- Publication number
- CN109851809A CN109851809A CN201910184998.8A CN201910184998A CN109851809A CN 109851809 A CN109851809 A CN 109851809A CN 201910184998 A CN201910184998 A CN 201910184998A CN 109851809 A CN109851809 A CN 109851809A
- Authority
- CN
- China
- Prior art keywords
- column
- compound
- aromatic hydrocarbons
- homopolymer
- formula
- 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
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses column [5] aromatic monomer and its homopolymer and preparation method of a kind of functional group containing diine, column [5] aromatic hydrocarbons of diine modified with functional group has formula (I) structure；Side group is that the homopolymer of column [5] aromatic hydrocarbons has formula (II) structure.This be first case by diine modified with functional group on column [5] aromatic hydrocarbons, and the column aromatic polymer obtained using metathesis cyclization polymerization.The main chain of this polymer is polyacetylene, has certain electric conductivity；Side group contains a large amount of column aromatic hydrocarbons host molecule, can further be complexed with guest molecule, for building the oversubscription sub-platform based on column aromatic polymer.Preparation method of the invention overcomes column aromatic monomer and is difficult to form the difficulty of homopolymer, and substantially reduces polymerization time, improves polymerization efficiency.
Description
Technical field
The invention belongs to technical field of polymer preparation, and in particular to a kind of column [5] aromatic hydrocarbons list of diine modified with functional group
Body and its homopolymer and synthetic method.
Background technique
Supramolecular chemistry is an emerging in recent years cross discipline, receives the pass of more and more research workers
Note.It is established on a variety of weak interaction forces, multiple molecules using the effect assemble it is complicated orderly, have it is special
The system of function.With the research that deepens continuously of supramolecular chemistry, scientists, which have successfully developed, a variety of possesses Optimality
The supermolecule main block molecule of energy, wherein what is be known has cyclodextrin, Cucurbituril, calixarenes and crown ether.Nowadays, a kind of novel
Host molecule --- column aromatic hydrocarbons has come into the sight of people.Column aromatic hydrocarbons is reported out by Japanese Scientists Ogoshi for the first time within 2008
Come.It is to pass through the cyclic compound that 2,5- methylene bridge links up by hydroquinone or Hydroquinone ether, wherein most often being ground
What is studied carefully is column [n] aromatic hydrocarbons (n=5,6).It has many advantages, such as high degree of symmetry, easily modifies and can be complexed with a variety of guest molecules,
It has been increasingly becoming host molecule of new generation.
It is embodied in modification and the small molecule column virtue to its synthetic method, functional group mostly for the research of column aromatic hydrocarbons at present
Subjective and Objective complexing behavior of hydrocarbon etc., the high molecular research report about the aromatic hydrocarbons containing column are also relatively fewer.This is because column
Aromatic hydrocarbons steric hindrance is very big, and common polymerization is difficult to realize its polymerization.Such as 2013 Nian Wangleyong seminar once reported
Synthesis column aromatic homopolymers are attempted, but since column aromatic hydrocarbons steric hindrance is excessive, after reacting 48h under the conditions of 80 DEG C, final major part column
Aromatic hydrocarbons does not also react.Therefore, the regular column aromatic homopolymers of composite structure are that face one of current scientific worker is important
Problem.
Metathesis polymerization develops into a kind of new coordination polymerization process effectively polymerizeing in recent years, it includes that ring-opening metathesis is poly-
It closes (ROMP), metathesis cyclization polymerize (MCP) and acyclic diene hydrocarbon metathesis polymerization (ADMET) three types.Metathesis polymerization reaction tool
The characteristics of active polymerization, especially has apparent effect to the biggish monomer of certain steric hindrances.By diyne knot in the present invention
Structure is introduced into column aromatic hydrocarbons, is the homopolymer of column aromatic hydrocarbons using the method synthesis side group that metathesis cyclization polymerize.
Summary of the invention
Column [5] aromatic monomer steric hindrance is larger, is difficult to form the technical problem of homopolymer in order to solve, and the present invention passes through in column
[5] modification has polymerizable diine functional group on aromatic hydrocarbons, and further using Ru-III as catalyst, poly- using metathesis cyclization
Conjunction method, synthesis side group are the homopolymer of column [5] aromatic hydrocarbons.The polymerization efficiency of this polymerization is high, and synthesized polymer can be with
Guest molecule is further complexed, for building the oversubscription sub-platform based on column aromatic polymer.
Technical solution provided by the invention is specific as follows:
A kind of column [5] aromatic hydrocarbons and its corresponding homopolymer of diine modified with functional group have shown in formula (I) or formula (II)
Structure:
In formula (II), n=38~65.
A kind of synthetic method of column [5] aromatic hydrocarbons of above-mentioned diine modified with functional group, comprising the following steps:
(1) under the conditions of nitrogen protection, p-hydroxyanisole and Isosorbide-5-Nitrae-dibromobutane are dissolved in acetone solvent, are added
Anhydrous K2CO3, reacted for 24 hours at 50 DEG C.To which after the reaction was completed, crude product obtains white solid through silica gel column chromatography separating purification
The compound A of shape, structural formula are
(2) compound A and 4- carboxymethyl -1,6- heptadiyne is dissolved in n,N-Dimethylformamide, is added anhydrous
K2CO3, reacted at 70 DEG C for 24 hours, to which after the reaction was completed, crude product obtains flaxen chemical combination through silica gel column chromatography separating purification
Object B, structural formula are
(3) compound B and terephthaldehyde's ether, metaformaldehyde, boron trifluoride ether are dissolved in 1,2- dichloro at 31 DEG C
In ethane, water extraction is added to go out when reaction solution becomes blackish green, by extraction, dried product exhibited through silica gel column chromatography separating purification,
The compound C of white powder is obtained, i.e. column [5] aromatic monomer of diine modified with functional group, structural formula is
In step (1), reaction carries out under nitrogen protection, p-hydroxyanisole, Isosorbide-5-Nitrae-dibromobutane and anhydrous K2CO3's
Molar ratio is 1:3:2.
In step (2), compound A, 4- carboxymethyl -1,6- heptadiyne and anhydrous K2CO3Molar ratio be 1.1:1:1.
In step (3), terephthaldehyde's ether, compound B, metaformaldehyde and boron trifluoride ether molar ratio be 4:1:5:
10, the solvent is 1,2- dichloroethanes.
A kind of side group is the synthetic method of column [5] aromatic homopolymers, comprising the following steps:
Compound C is dissolved in anhydrous methylene chloride, by freezing-vacuumizing-after inflated with nitrogen recycles three times, be added
Ru-III catalyst and 3,5- dichloropyridine react 3h under the conditions of 30 DEG C, and vinyl ethyl ether is added and terminates reaction, by precipitating,
After centrifugation, the compound D of purple powder shape is obtained, structural formula is
In this step, the concentration of compound C is 0.1M, and ligand used is 3,5- dichloropyridine, and reaction carries out at 30 DEG C
3h。
Above-mentioned column aromatic homopolymers can be complexed as host molecule polymer with guest molecule, be based on host and guest for building
The oversubscription sub-platform of body complexing.
The present invention has the following advantages that and good result:
(1) present invention reports the synthesis of the column aromatic monomer and its homopolymer of diine modified with functional group for the first time.This conjunction
It solves column aromatic hydrocarbons at method to be difficult to form the technical difficulty of homopolymer, the molecule according to the column aromatic polymer that the method obtains
Amount can reach 3.5 × 104~6.0 × 104g/mol。
(2) main chain of this homopolymer is polyacetylene, has certain electric conductivity；The column aromatic hydrocarbons of side group is as main body point simultaneously
Son can be complexed with a variety of guest molecules, realize building for column aromatic homopolymers oversubscription sub-platform.
Detailed description of the invention
Fig. 1 is the synthetic route chart of the compounds of this invention C；
Fig. 2 is the synthetic route chart of the compounds of this invention D；
Fig. 3 is the compounds of this invention D and the nuclear magnetic spectrogram of guest molecule complexing front and back.
Specific embodiment
In order to better understand the content of the present invention, the contents of the present invention are made furtherly combined with specific embodiments below
Bright but of the invention protection content is not limited to following embodiment.
Raw material used in the embodiment of the present invention can be bought by market, or can be synthesized with methods known in the art
It arrives.
Embodiment 1
The synthesis of compound A-D
(1) under nitrogen atmosphere, p-hydroxyanisole (6.20g, 50mmol) is added in 500mL three-necked flask, Isosorbide-5-Nitrae-two
Bromobutane (32.40g, 150mmol), 300mL acetone stirring and dissolving add Anhydrous potassium carbonate (13.8g, 100mmol), 50 DEG C
Reflux for 24 hours, is filtered to remove potassium carbonate, yellow mucus is obtained after collecting filtrate decompression distillation, through methylene chloride: petroleum ether=1:3
White solid 10.31g, yield 80% are obtained after crossing column processing.With1H NMR characterizes its structure, it was demonstrated that the white solid
For compound A, structural formula is 1H NMR(CDCl3,500MHz,298K)δ(ppm):6.83(s,4H),
3.95 (t, J=6.1Hz, 2H), 3.77 (s, 3H), 3.49 (t, J=6.7Hz, 2H), 2.11-2.02 (m, 2H), 1.92 (dq, J
=9.6,6.2Hz, 2H)
(2) at room temperature, 4- carboxymethyl -1,6- heptadiyne (4.08g, 30mmol) is added in 100mL round-bottomed flask, it is anhydrous
Potassium carbonate (4.14g, 30mmol), 40mLN, dinethylformamide are stirred to being completely dissolved, and compound A is then added
(8.54g, 33mmol) is heated to reflux for 24 hours at 70 DEG C, is filtered to remove potash solid, is obtained after collecting filtrate decompression distillation
Yellow mucus, through ethyl acetate: petroleum ether=1:10 obtains pale yellow transparent mucus 7.68g, yield 81% after crossing column processing.
With1H NMR characterizes its structure, it was demonstrated that the weak yellow liquid is compound B, and structural formula is 1H NMR(CDCl3,500MHz,298K)δ(ppm):6.83(s,4H),4.24–4.19(m,
2H), 3.96-3.91 (m, 2H), 3.77 (s, 3H), 2.80-2.72 (m, 1H), 2.69-2.57 (m, 4H), 2.01 (t, J=
2.6Hz,2H),1.88–1.81(m,4H).
It (3) will be to methoxybenzene (1.87g, 13.6mmol), compound B (1.06g, 3.4mmol), metaformaldehyde
(1.53g, 17mmol) is dissolved in 260mL1, and in 2- dichloroethanes, boron trifluoride ether is added after being completely dissolved to solid in stirring
Reaction is quenched with water when system becomes blackish green in (4.82g, 4.4mL, 34mmol).Liquid separation, water phase wash three with methylene chloride
Secondary (3 × 100mL), organic phase are washed with water (3 × 100mL) three times, collect organic phase, and anhydrous magnesium sulfate is added and stirs drying, mistake
Filter, obtains dark brown mucus, is then deposited in 25mL acetonitrile after filtrate decompression is distilled, there is white solid precipitation, and centrifugation is received
Collect supernatant liquor, vacuum distillation obtains yellow mucus, through methylene chloride: petroleum ether=2:1 obtains white powder after crossing column processing
393mg, yield 12.5%.With1H NMR characterizes its structure, it was demonstrated that the white powder is compound C, and structural formula is 1H NMR(500MHz,CDCl3,298K)δ(ppm):6.91–6.75(m,
10H), 4.25 (t, J=5.8Hz, 2H), 3.90 (d, J=17.2Hz, 2H), 3.83-3.66 (m, 37H), 2.82-2.73 (m,
1H),2.70–2.58(m,4H),2.05–1.98(m,2H),1.98–1.85(m,4H).
(4) column [5] aromatic homopolymers D that the compounding design degree of polymerization is 50.The additionization in 25mL Schlenk reaction tube
Object C (92.6mg, 0.1mmol) and anhydrous methylene chloride (0.6mL) are closed, cool down-is vacuumized-inflated with nitrogen circulation 3 times by liquid nitrogen
Afterwards, be added Ru-III catalyst (1.8mg, 2 × 10-3Mmol), 3,5- dichloropyridine (2.9mg, 2 × 10-2) and anhydrous two mmol
Chloromethane alkane solvents (0.4mL) again stir reaction tube after liquid nitrogen cool down-vacuumizes-inflated with nitrogen circulation 3 times at 30 DEG C
The termination reaction of 0.5mL vinyl ethyl ether solvent is added after mixing reaction 3h.Reaction solution is deposited in 50mL anhydrous ether solvent, is obtained
It is precipitated to darkviolet polymer.Precipitating is collected after centrifugation and is dried in vacuo, obtains violet solid, is compound D, structural formula isIt is analyzed through gel permeation chromatogram, absolute molecular weight is 3.8 × 104G/mol, molecule
Measuring Distribution Breadth Index PDI is 1.42.
Embodiment 2
Compound D can be complexed as host molecule with guest molecule, construct supramolecular system.
It selects the double trifluoromethanesulfonimide salt of ionic liquid pyridine as guest molecule, passes through compound D center pillar aromatic hydrocarbons
Ionic liquid and polymer are combined together by the Host guest complexation between guest molecule by non-covalent bond.Pass through Fig. 3
Curve a) and curve b) can be seen that matter after guest molecule is added in column aromatic homopolymers, on guest molecule pyridine ring
Sub- HcPeak disappears；Proton HaPeak is mobile to low field direction, shields this is because column aromatic hydrocarbons cavity has the exposed proton outside cavity
The effect of covering；Proton Hb-gPeak is mobile to high field direction, this is because the electron rich in cavity is to it inside proton drilling column aromatic hydrocarbons
There is shielding action.Pass through1H NMR spectra it can be concluded that, by guest molecule be added column aromatic homopolymers in, the two can pass through master
Object complexing combines.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, others are any not to violate made changes, modifications, substitutions, combinations, simplifications under spiritual essence and principle of the invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (5)
1. a kind of column [5] aromatic hydrocarbons of diine modified with functional group, which is characterized in that have structure shown in formula (I):
2. the homopolymer that a kind of side group is column [5] aromatic hydrocarbons, which is characterized in that the structure with formula (II):
In formula, n=38~65.
3. side group according to claim 2 be column [5] aromatic hydrocarbons homopolymer, which is characterized in that the homopolymer it is absolute
Molecular weight is 3.5 × 104~6.0 × 104G/mol, Breadth parameter of molecular weight distribution PDI are 1.37~1.85.
4. a kind of synthetic method of column [5] aromatic hydrocarbons of diine modified with functional group described in claim 1, which is characterized in that the party
Method comprising the following specific steps
(1) under the conditions of nitrogen protection, p-hydroxyanisole and Isosorbide-5-Nitrae-dibromobutane are dissolved in acetone solvent, are added anhydrous
K2CO3Catalyst reacts for 24 hours at 50 DEG C, to after the reaction was completed, by crude product through silica gel column chromatography separating purification, obtain white
The compound A of solid-like, structural formula are
(2) compound A and 4- carboxymethyl -1,6- heptadiyne is dissolved in n,N-Dimethylformamide, anhydrous K is added2CO3,
It is reacted at 70 DEG C for 24 hours, to which after the reaction was completed, crude product obtains the chemical combination of weak yellow liquid shape through silica gel column chromatography separating purification
Object B, structural formula are
(3) compound B and terephthaldehyde's ether, metaformaldehyde, boron trifluoride ether are dissolved in 1,2- dichloroethanes at 31 DEG C
In, add water extraction to go out when reaction solution becomes blackish green, by extraction, dried product exhibited through silica gel column chromatography separating purification, obtains
The compound C of white powder, i.e. column [5] aromatic monomer of diine modified with functional group, structural formula areWherein:
The p-hydroxyanisole, 1,4- dibromobutane and anhydrous K2CO3Molar ratio is 1:3:2；
Compound A, 4- carboxymethyl -1,6- heptadiyne and anhydrous K2CO3Molar ratio is 1.1:1:1；
Terephthaldehyde's ether, compound B, metaformaldehyde and boron trifluoride ether molar ratio be 4:1:5:10.
5. the synthetic method that a kind of side group as claimed in claim 2 is the homopolymer of column [5] aromatic hydrocarbons, which is characterized in that
Compound C is dissolved in anhydrous methylene chloride, through freezing-vacuumize-after inflated with nitrogen recycles three times, Ru-III is added
Catalyst and 3,5- dichloropyridine react 3h under the conditions of 30 DEG C, and vinyl ethyl ether is added and terminates reaction, after precipitating, being centrifuged,
The compound D of purple powder shape is obtained, structural formula isWherein,
The concentration of the compound C is 0.1M；
In formula, n=38~65.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910184998.8A CN109851809B (en) | 2019-03-12 | 2019-03-12 | A kind of column [5] aromatic monomer and its homopolymer and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910184998.8A CN109851809B (en) | 2019-03-12 | 2019-03-12 | A kind of column [5] aromatic monomer and its homopolymer and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109851809A true CN109851809A (en) | 2019-06-07 |
| CN109851809B CN109851809B (en) | 2019-09-17 |
Family
ID=66900634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910184998.8A Expired - Fee Related CN109851809B (en) | 2019-03-12 | 2019-03-12 | A kind of column [5] aromatic monomer and its homopolymer and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109851809B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423365A (en) * | 2020-04-03 | 2020-07-17 | 华东师范大学 | Bifunctional group pillar aromatic hydrocarbon derivative ligand, metal organic cage and preparation method |
| CN112795005A (en) * | 2021-02-24 | 2021-05-14 | 福州大学 | Polycyclic linear polymer and preparation method thereof |
| CN112812269A (en) * | 2021-02-08 | 2021-05-18 | 福州大学 | Epoxy oligomer and preparation method thereof |
| CN113385225A (en) * | 2021-06-18 | 2021-09-14 | 辽宁东科药业有限公司 | Supermolecule ionic liquid catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396298A (en) * | 2013-08-22 | 2013-11-20 | 吉林大学 | Preparation of functionalized pillar(n)arene derivatives |
| CN105130889A (en) * | 2015-09-06 | 2015-12-09 | 西北师范大学 | Quinoline-modified pillararene and preparation thereof and application thereof in performing fluorescence detection on CN<-> in water-containing system |
| CN105693655A (en) * | 2016-04-01 | 2016-06-22 | 西北师范大学 | Aminobenzothiazole-modified column aromatic hydrocarbons and synthesis thereof, and application of column aromatic hydrocarbons in continuous fluorescent recognition of Fe<3+> and F<-> in water phase |
| WO2017025951A1 (en) * | 2015-08-10 | 2017-02-16 | Ramot At Tel-Aviv University Ltd. | Pillararenes and uses thereof |
-
2019
- 2019-03-12 CN CN201910184998.8A patent/CN109851809B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396298A (en) * | 2013-08-22 | 2013-11-20 | 吉林大学 | Preparation of functionalized pillar(n)arene derivatives |
| WO2017025951A1 (en) * | 2015-08-10 | 2017-02-16 | Ramot At Tel-Aviv University Ltd. | Pillararenes and uses thereof |
| CN105130889A (en) * | 2015-09-06 | 2015-12-09 | 西北师范大学 | Quinoline-modified pillararene and preparation thereof and application thereof in performing fluorescence detection on CN<-> in water-containing system |
| CN105693655A (en) * | 2016-04-01 | 2016-06-22 | 西北师范大学 | Aminobenzothiazole-modified column aromatic hydrocarbons and synthesis thereof, and application of column aromatic hydrocarbons in continuous fluorescent recognition of Fe<3+> and F<-> in water phase |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423365A (en) * | 2020-04-03 | 2020-07-17 | 华东师范大学 | Bifunctional group pillar aromatic hydrocarbon derivative ligand, metal organic cage and preparation method |
| CN112812269A (en) * | 2021-02-08 | 2021-05-18 | 福州大学 | Epoxy oligomer and preparation method thereof |
| CN112812269B (en) * | 2021-02-08 | 2022-08-16 | 福州大学 | Epoxy oligomer and preparation method thereof |
| CN112795005A (en) * | 2021-02-24 | 2021-05-14 | 福州大学 | Polycyclic linear polymer and preparation method thereof |
| CN112795005B (en) * | 2021-02-24 | 2021-11-02 | 福州大学 | Polycyclic linear polymer and preparation method thereof |
| CN113385225A (en) * | 2021-06-18 | 2021-09-14 | 辽宁东科药业有限公司 | Supermolecule ionic liquid catalyst and preparation method and application thereof |
| CN113385225B (en) * | 2021-06-18 | 2022-11-18 | 抚顺东科新能源科技有限公司 | Supermolecule ionic liquid catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109851809B (en) | 2019-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109851809B (en) | A kind of column [5] aromatic monomer and its homopolymer and preparation method | |
| CN108752575B (en) | Preparation method of polyester material | |
| CN105622421B (en) | The preparation method and application of benzoic acid column [5] aromatic hydrocarbons ester derivant | |
| CN109988290B (en) | Preparation method of oligomeric metalloporphyrin complex and polycarbonate | |
| CN107602744B (en) | A kind of superhigh cross-linking microporous polymer and preparation method thereof | |
| Cao et al. | Synthesis of pillar [n] arenes (n= 5 and 6) with deep eutectic solvent choline chloride 2FeCl 3 | |
| Ye et al. | A novel method for the synthesis of regiospecifically sulfonated porphyrin monomers and dimers | |
| Parvez et al. | Molecular design of chiral quaternary ammonium polymers for asymmetric catalysis applications | |
| CN105622406B (en) | Functionalization column [5] aromatic hydrocarbons trimer preparation method and application | |
| CN106378109A (en) | Multihole polycarbazole polymer and preparation method and application thereof | |
| CN109942638A (en) | Asymmetric alpha-diimine nickel (II) complex that methylbenzyl is replaced containing ortho position two for vinyl polymerization | |
| CN105198892A (en) | Synthetic method for isosorbide acrylic ester and application of isosorbide acrylic ester in improving thermal performance of polymer | |
| CN110452365B (en) | Conjugated porous polymer, preparation method thereof and application of conjugated porous polymer in preparation of imine through oxidation of primary amine in photocatalysis | |
| CN110483483A (en) | A kind of multiple tooth nitrogen ligand compound of chirality and its preparation method and application | |
| CN104557847B (en) | Production method for depolymerising polycaprolactone by using cationic catalyzing method | |
| CN113061077B (en) | Alpha, alpha-dideuteroalcohol compounds, deuterated drugs and preparation method thereof | |
| Ibrahim et al. | Synthesis and characterization of original calix–salen type ligands | |
| CN107266283B (en) | A kind of preparation method of the compound containing non-end group double bond | |
| Strasser et al. | On the chloride lability in electron-rich second-generation ruthenium benzylidene complexes | |
| CN103648645B (en) | For preparing the dimeric method of palladium (I) tri-butyl phosphine bromide and the using method in isomerization reaction thereof | |
| CN111154498B (en) | Preparation method of liquid crystal compound containing 1, 5-indan and difluoromethoxy bridge | |
| CN110627628A (en) | Beta-iodo-difluoropropanone derivative and preparation method thereof | |
| CN113461643A (en) | Synthesis method of 4-methylbenzenesulfonic acid [ (3-fluoro-oxetan-3-yl) methyl ] ester | |
| Huang et al. | Synthesis and characterization of novel ionophores of double-armed penta-crown ethers | |
| Xie et al. | A base-promoted desalicyloylative dimerization of 3-(1-alkynyl) chromones: An unusual approach to 2-alkynyl xanthones |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190917 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |