CN106633048A - Polyacetylenic compound and preparation method thereof - Google Patents
Polyacetylenic compound and preparation method thereof Download PDFInfo
- Publication number
- CN106633048A CN106633048A CN201611086123.7A CN201611086123A CN106633048A CN 106633048 A CN106633048 A CN 106633048A CN 201611086123 A CN201611086123 A CN 201611086123A CN 106633048 A CN106633048 A CN 106633048A
- Authority
- CN
- China
- Prior art keywords
- carbene
- preparation
- phenyl
- reaction
- binary
- 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
- 0 *c1ccccc1 Chemical compound *c1ccccc1 0.000 description 2
Classifications
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0246—Polyamines containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/0253—Polyamines containing sulfur in the main chain
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
Abstract
The invention belongs to the technical field of organic chemistry, and discloses a polyacetylenic compound and a preparation method thereof. The method comprises the following steps: (1) under the protection of an inert gas, mixing a diacetylene halide compound and a binary sulphonamide compound in a catalytic system and an organic solvent, reacting, and cooling to obtain a reaction mother liquid; (2) adding the reaction mother liquid into a precipitator for precipitating, collecting a precipitated, and drying to constant weight to obtain a polyacetylenic compound. The preparation method disclosed by the invention is simple; the reaction is efficient; the group tolerance is high; a plurality of functional groups can be intruded into monomers; the prepared polyacetylenic compound contains a carbon-carbon triple bond, and has important application to serving as an intermediate in a further reaction; moreover, the compound is easy to hydrolyze, and has a very promising prospect in the aspects of environmentally friendly chemistry, green chemistry and the like, such as a degradable material.
Description
Technical field
The invention belongs to vitochemical technical field, is related to the synthesis of carbene aminated compounds, and in particular to Yi Zhongju
Alkynes aminated compounds and the method that the carbene aminated compounds is prepared by alkynes halogen and sulfuryl amine reaction.
Background technology
The new polymerisation of development is very important for polymer material science.Alkynes is to be easy to get or be easily-synthesized
One of chemical raw material, there is important academic significance and technical meaning using alkynes constructing function macromolecule, attracted
The extensive concern of scientists.The coupling polymerization reaction of ynamine has that reaction condition is gentle, reaction efficiency is high, atom economy etc.
Feature, meets the definition of green chemical reaction, is the new polymerisation of a class.The small molecule for being currently based on ynamine is wide
General report, and the intermediate as organic products, organic functional material and bioactive compound is widely used, and due to
Ynamine with carboxyl groups have higher stability, alkynyl amide molecule become more have using value synthetic intermediate it
One.
However, the coupling polymerization reaction of ynamine is not but studied yet in organic field and reports, it can thus be anticipated that exploitation
Simply, efficient carbene amine route of synthesis is by with important scientific meaning and using value.
The content of the invention
It is an object of the invention to provide a kind of preparation method of carbene amines, the method belongs to easy to operate, anti-
Should the efficient, green chemical reaction of atom economy.
Another kind of purpose of the present invention is to provide the carbene amines obtained using said method, the compound structure
Inside there are three keys, for further reaction will also have important application as intermediate aspect.Meanwhile, the compound facile hydrolysis,
The environmental friendliness such as development degradation material and Green Chemistry aspect also great potential.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of carbene amines, comprises the following steps：
(1) under inert gas shielding, in catalyst system and catalyzing and organic solvent, by binary alkynes halogen compound and binary sulphonyl
Amines mixes, reaction, and cooling obtains reaction mother liquor；
(2) reaction mother liquor is added and is precipitated in precipitating reagent, collected sediment and be dried to constant weight, obtain carbene amination
Compound.
Binary alkynes halogen compound described in step (1) and the mol ratio of binary sulfonamide compounds reaction are 1:1, binary alkynes
Halogen compound concentration in organic solvent is 0.1-0.2mol/L.
Catalyst system and catalyzing is containing CuSO described in step (1)4·5H2O, K2CO3With the system of 1,10- Phens；
The CuSO45H2The consumption of O is the 10-20mol% of binary alkynes halogen compound consumption, 1,10- Phen
Consumption is the 20-40mol%, K of binary alkynes halogen compound consumption2CO3Concentration in organic solvent is 0.2-0.4mol/L.
The organic solvent is dimethyl sulfoxide (DMSO) (DMSO) or the one kind in N,N-dimethylformamide (DMF).
The temperature reacted described in step (1) is 50-100 DEG C, and the time of reaction is 24-48h；
Precipitating reagent is methyl alcohol in step (2).
Reaction mother liquor described in step (2) adds the mode in precipitating reagent for (speed of dropwise addition is 1～3 drop/sec) is added dropwise,
And be first diluted with tetrahydrofuran before reaction mother liquor is added in precipitating reagent, filtered after dilution.
The structural formula of the binary alkynes halogen compound described in step (1) is：Wherein X is that chlorine is former
Son or bromine atoms；Any one of R in following 16-26, and it is not limited to following 16-26 kinds；Wherein R1With R2It is identical or
Difference, R1For alkylidene (- CnH2n-, n is integer), alkylene oxide group (- CnH2nO-, n are integer), oxygen (O), phenylene, alkylidene
In one or more C be substituted by phenyl in (substituted carbon number less than alkylidene in carbon number), alkylene oxide group one or more C by benzene
Base and/or oxygen replace (substituted carbon number is less than carbon number in alkylidene)；R2For alkylidene (- CnH2n-, n is integer), alkylene oxide group
(-CnH2nO-, n are integer), oxygen (O), phenylene, one or more C are substituted by phenyl that (substituted carbon number is less than Asia in alkylidene
Carbon number in alkyl), one or more C are replaced that (substituted carbon number is less than carbon in alkylidene by phenyl and/or oxygen in alkylene oxide group
Number)；* it is junction；
Any one of described binary sulfonamide compounds in the following 1-15, and it is not limited to following 15 kinds：Its
Middle R1For alkylidene (- CnH2n-, n is integer), alkylene oxide group (- CnH2nO-, n are integer), oxygen (O), phenylene, in alkylidene
One or more C are substituted by phenyl in (substituted carbon number less than alkylidene in carbon number), alkylene oxide group one or more C by phenyl
And/or oxygen replaces (substituted carbon number is less than carbon number in alkylidene)；R2For alkyl, alkoxyl, phenyl, alkyl-substituted phenyl,
One or more C are substituted by phenyl (substituted carbon number is less than carbon number in alkyl), alkoxyl in phenyl, alkyl that alkoxyl replaces
In one or more C replaced (substituted carbon number is less than carbon number in alkylidene) by phenyl and/or oxygen；
Present invention also offers a kind of carbene amines, is prepared by said method.
The structure of the carbene amines isWherein, R1、R1′With R2It is
By corresponding group in original structure after above-mentioned binary alkynes halogen compound and binary sulfonamide compounds reaction removing hydrogen halides, n is
Integer between 2-200.
Three keys are still left in the carbene amines structure, for further reaction will also have important as intermediate aspect
Using.Meanwhile, the compound facile hydrolysis, the also great potential in terms of development degradation material etc. environmental friendliness with Green Chemistry.
Compared with prior art, the invention has the advantages that：
1st, the present invention is polymerized using alkynes halogen and sulfonamide and obtains carbene amine, as far as we know, the type of polymerization never by
Report, therefore with very high scientific research value, using value and good development prospect；
2nd, preparation method process is simple of the invention, the catalyst and raw material for using is easy to get, can be by purchase or simple
Experimental implementation is obtained；
3rd, preparation method reaction condition of the invention it is gentle, efficiently, energy saving, and no coupling product generates, with original
The characteristics of subeconomy；
4th, preparation method group tolerance of the invention is stronger, and several functions group can be introduced in monomer；
5th, the carbene amines facile hydrolysis obtained by the preparation method of the present invention, in environmental friendliness such as degradation materials
Chemistry and the great application prospect of Green Chemistry aspect.
Description of the drawings
Fig. 1 is carbene amines (P1) prepared by the embodiment of the present invention 1 and its corresponding monomer (M1, M2) and modelling
Compound proton nmr spectra comparison diagram in deuterated DMSO；
Fig. 2 is carbene amines (P1) prepared by the embodiment of the present invention 1 and its corresponding monomer (M1, M2) and modelling
Compound carbon-13 nmr spectra comparison diagram in deuterated DMSO；
Fig. 3 is carbene amines (P1) prepared by the embodiment of the present invention 1 and its corresponding monomer (M1, M2) and modelling
The infrared absorpting light spectra of compound；
Fig. 4 is fluorescence emission spectrums of the carbene aminated compounds P2 of the preparation of the embodiment of the present invention 4 under different water contents；
Fig. 5 is quantum yield figures of the carbene aminated compounds P2 of the preparation of the embodiment of the present invention 4 under different water contents.
Specific embodiment
The present invention is specifically described with reference to embodiment and accompanying drawing, but protection scope of the present invention be not limited to
Lower embodiment.
Embodiment 1
A kind of carbene amines P1, its structural formula is as follows：
The carbene amines is prepared by alkynes halogen with sulfamide monomer reaction, its concrete reaction equation such as formula
(1)：
(1) synthetic method of monomer M1 is：At 0 DEG C, 9.0mmol (3.29g) sulphonyl is added toward 250mL two-mouth bottles
Chlorine, vacuumizes and changes N2150mL dichloromethane and 36.9mmol (4.03mL) benzylamine are added afterwards, and reaction system is stirred at normal temperatures
After 2 hours, extracted three times, be spin-dried for dichloromethane and water, crude product purified by silica gel chromatographic column is isolated and purified and in 40 DEG C of temperature
The lower vacuum drying of degree, obtains 7.7mmol (3.90g) product (monomer M1), and yield is 85%；M1 monomers in the nuclear-magnetism figure of Fig. 1
8.20 is-NH peaks, and 4.04 is-CH2Peak, wherein, 3.32 is water peak, and 2.50 is DMSO-d6 peaks；Monomer M1 presence-NH in Fig. 3
Peak；
(2) synthetic method of monomer M2 is：10.0mmol (1.26g) 1,4- diacetylenes are added in 250mL single port bottles
Benzene, 22.0mmol (3.89g) NBS, 2.0mmol (0.34g) silver nitrate, after adding 100mL acetone, system are stirred at normal temperatures
Mix 3 hours, subsequently filter, be spin-dried for, crude product purified by silica gel chromatographic column is isolated and purified, after being vacuum dried at a temperature of 40 DEG C,
7.8mmol (2.20g) product (monomer M2) is obtained, yield is 78%；For on phenyl ring at the 7.48 of M2 monomers in the nuclear-magnetism figure of Fig. 1
H peaks, wherein, 3.32 is water peak, and 2.50 is DMSO-d6 peaks；There is triple carbon-carbon bonds peak in Fig. 3；
(3) preparation process of the carbene aminated compounds described in is：0.2mmol is sequentially added in 10mL polymerization pipes
(0.11g) monomer M1,0.2mmol (0.06g) monomer M2,0.03mmol (0.005g) CuSO4·5H2O、0.06mmol
(0.01g), 1,10- Phens, 0.6mmol (0.08g) K2CO3, vacuumize and change N22mL DMSO are added afterwards, and system is heated up
Stirred 24 hours with 400 rpms of speed to after 65 DEG C；Reaction uses 2mL tetrahydrofuran diluting reaction systems after terminating, and makes
System to be filtered out be added drop-wise to after copper sulphate and settled in precipitating reagent absolute methanol, stand 12 hours, filter, vacuum drying after
It is vacuum dried at a temperature of 40 DEG C, obtains 0.12g polymer Ps 1, yield is 86%, and molecular weight reaches 18000g/mol；The core of Fig. 1
P1 figures in magnetic chart can see that-NH the peaks of monomer M1 have disappeared, and-CH24.65 are displaced to from 4.04, wherein, 3.32 are
Water peak, 2.50 is DMSO-d6 peaks；After the reaction that can observe in Fig. 3 in P1-NH disappearance, the presence at triple carbon-carbon bonds peak；
(4) the concrete reaction equation of model compound is as follows：
The preparation process of the model compound is：Sequentially add in 50mL bottle with two necks 2.0mmol (0.57g) substrate 1,
4.2mmol (1.10g) substrate 2,0.4mmol (0.10g) CuSO4·5H2O, 0.8mmol (0.14), 1,10- Phens,
8.0mmol(1.11g)K2CO3, vacuumize and change N210mL DMSO are added afterwards, with 400 rpms after system is warming up to into 65 DEG C
Speed stir 36 hours, reaction is extracted three times, is spin-dried for after terminating with dichloromethane and water, and crude product purified by silica gel chromatographic column is carried out
Isolate and purify and be vacuum dried at a temperature of 40 DEG C, obtain 1.8mmol (1.16g) product, yield is 90%.
Carbene amines (P1) manufactured in the present embodiment and its corresponding monomer (M1, M2) and model compound are deuterated
Proton nmr spectra in DMSO is as shown in figure 1, carbon-13 nmr spectra is as shown in Fig. 2 infrared absorpting light spectra in deuterated DMSO
As shown in Figure 3.
Embodiment 2
Reaction time in embodiment 1 is changed to 80 DEG C by the present embodiment, the preparation method phase of other preparation conditions and embodiment 1
Together, polymer 0.13g is obtained, yield is 90%, and molecular weight reaches 17000g/mol.
Embodiment 3
The present embodiment is by the CuSO in embodiment 14·5H2O feeds intake and is changed to 0.04mmol (0.007g), 1,10- Phen
Feed intake and be changed to 0.08mmol (0.02g), K2CO3Feed intake and be changed to 0.80mmol (0.11g), the system of other preparation conditions and embodiment 1
Preparation Method is identical, obtains polymer 0.12g, and yield is 81%, and molecular weight reaches 18000g/mol.
Embodiment 4
A kind of carbene amines P2, shown in its structural formula：
The carbene amines is prepared by alkynes halogen with sulfamide monomer reaction, its concrete reaction equation such as formula
(2)：
(1) synthetic method of monomer M1 is with described in example 1；
(2) synthetic method of monomer M3 is as described below：3.0mmol (1.14g) diacetylene is added in 250mL single port bottles
Tetraphenylethylene, 6.6mmol (1.17g) NBS, 0.6mmol (0.10g) silver nitrate, after adding 60mL acetone, by system normal
The lower stirring of temperature 3 hours, subsequently filters, is spin-dried for, and crude product purified by silica gel chromatographic column is isolated and purified, and vacuum is done at a temperature of 40 DEG C
2.7mmol (1.45g) product is obtained after dry, yield is 90%；
Diacetylene tetraphenylethylene in this step is according to document [Hu, R.；Lam,J.W.Y.；Liu,J.；Sung,
H.H.Y.；Williams,I.D.；Yue,Z.；Wong,K.S.；Yuen,M.M.F.；Tang,B.Z.,Hyperbranched
conjugated poly(tetraphenylethene):synthesis,aggregation-induced emission,
fluorescent photopatterning,optical limiting and explosive detection.Polymer
Chemistry 2012,3 (6), 1481-1489.] disclosed in method prepare；
(3) preparation process of the carbene aminated compounds described in is as follows：0.2mmol is sequentially added in 10mL polymerization pipes
(0.10g) monomer M1,0.2mmol (0.11g) monomer M3,0.03mmol (0.005g) CuSO4·5H2O、0.06mmol
(0.01g), 1,10- Phens, 0.6mmol (0.08g) K2CO3, vacuumize and change N22mL DMSO are added afterwards, and system is heated up
Stirred 24 hours with 400 rpms of speed to after 65 DEG C；Reaction uses 2mL tetrahydrofuran diluting reaction systems after terminating, and makes
System to be filtered out be added drop-wise to after copper sulphate and settled in precipitating reagent absolute methanol, stand 12 hours, filter, vacuum drying after
It is vacuum dried at a temperature of 40 DEG C, obtains 0.15g polymer Ps 2, yield is 86%, and molecular weight reaches 11000g/mol.
The polymer that the method is obtained has special photoelectric property, and Fig. 4 is the polymer P 2 under different water contents
Fluorescence emission spectrum.With the rising of water content, the luminous of the polymer solution gradually strengthens, wherein, when water content is 95%
When, the polymer has highest luminous efficiency under the solution.Fig. 5 is quantum yield of the polymer P 2 under different water contents
Figure (excitation wavelength is 340nm), when water content is 95%, there is highest quantum yield 24.7%.
Embodiment 5
A kind of carbene amines P3, shown in its structural formula：
The carbene amines is prepared by alkynes halogen with sulfamide monomer reaction, its concrete reaction equation such as formula
(3)：
(1) synthetic method of monomer M4 is：At 0 DEG C, 9.0mmol (3.29g) sulphonyl is added toward 250mL two-mouth bottles
Chlorine, vacuumizes and changes N2150mL dichloromethane and 36.9mmol (2.05mL) ethamine are added afterwards, and reaction system is stirred at normal temperatures
After 2 hours, extracted three times, be spin-dried for dichloromethane and water, crude product purified by silica gel chromatographic column is isolated and purified and in 40 DEG C of temperature
The lower vacuum drying of degree, obtains 8.1mmol (3.11g) product (monomer M4), and yield is 90%；
(2) synthetic method of monomer M5 is：
(2-1) in 250mL two-mouth bottles add 15.0mmol (3.43g) bisphenol-A, 45mmol (6.22g) potassium carbonate and
33.0mmol (8.25g) then adds 100mL acetone to bromine bromobenzyl toward reaction system, and heating reflux reaction is cold after 12 hours
But, deionized water cleans white depositions repeatedly, and after being dried 7.64g white solid products 1 are obtained, and yield is 90%；
(2-2) the double triphens of 10.0mmol (5.66g) white solid 1,0.5mmol (0.35g) are added in 250mL two-mouth bottles
Base phosphorus palladium chloride, 0.5mmol (0.10g) cuprous iodide, 0.5mmol (0.13g) triphenylphosphine, and vacuum nitrogen gas three
Secondary, the triethylamine and 20mL for then processing through nitrogen bubble to reaction system addition 100mL weighs steamed tetrahydrofuran, then past
In system add 4mL (30.0mmol) trimethylsilyl acetylene, be heated to 90 DEG C reaction 24 hours after, cooling, with 100mL saturation chlorine
Change ammonium salt solution and reaction is quenched, filter, filtrate is extracted three times with dichloromethane, organic phase is merged and is concentrated, the crude product for obtaining is used
Silica gel chromatographic column is separated, and eluent is petroleum ether, obtains 5.40g white solid products 2, and yield is 90%；
(2-3) 5.0mmol (3.00g) white solid 2 and 25.0mmol (1.40g) hydrogen-oxygen are added in 250mL single port bottles
Change potassium, then add 25mL methyl alcohol, 25mL tetrahydrofurans, 5mL deionized waters inward, after stirring 12 hours under room temperature, reaction mixing
Liquid is extracted three times with dichloromethane, organic phase is merged and is concentrated, and the crude product purified by silica gel chromatographic column for obtaining is separated, eluent
For petroleum ether, 2.17g white solid products 3 are obtained, yield is 95%；
(2-4) in 250mL single port bottles add 2.5mmol (1.14g) white solid 3,5.5mmol (0.98g) NBS,
0.5mmol (0.08g) silver nitrate, after adding 60mL acetone, system is stirred at normal temperatures 3 hours, is subsequently filtered, is spin-dried for,
Crude product purified by silica gel chromatographic column is isolated and purified, and after being vacuum dried at a temperature of 40 DEG C 1.38g products, as monomer are obtained
M5, yield is 90%；
(3) preparation process of the carbene aminated compounds described in is：0.2mmol is sequentially added in 10mL polymerization pipes
(0.08g) monomer M4,0.2mmol (0.12g) monomer M5,0.03mmol (0.005g) CuSO4·5H2O、0.06mmol
(0.01g), 1,10- Phens, 0.6mmol (0.08g) K2CO3, vacuumize and change N22mL DMSO are added afterwards, and system is heated up
Stirred 24 hours with 400 rpms of speed to after 65 DEG C；Reaction uses 2mL tetrahydrofuran diluting reaction systems after terminating, and makes
System to be filtered out be added drop-wise to after copper sulphate and settled in precipitating reagent absolute methanol, stand 12 hours, filter, at a temperature of 40 DEG C
0.13g polymer Ps 3 are obtained after vacuum drying, yield is 78%.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Embodiment restriction.For those of ordinary skill in the field, can also make on the basis of the above description
The change or variation of other multi-forms.There is no need to be exhaustive to all of embodiment.It is all the present invention
Any modification, equivalent and improvement made within spirit and principle etc., should be included in the protection of the claims in the present invention
Within the scope of.
Claims (10)
1. a kind of preparation method of carbene amines, it is characterised in that：Comprise the following steps：
(1) under inert gas shielding, in catalyst system and catalyzing and organic solvent, by binary alkynes halogen compound and binary sulfuryl amine
Compound mixes, reaction, and cooling obtains reaction mother liquor；
(2) reaction mother liquor is added and is precipitated in precipitating reagent, collected sediment and be dried to constant weight, obtain carbene amine compounds
Thing.
2. the preparation method of carbene amines according to claim 1, it is characterised in that：
The structural formula of the binary alkynes halogen compound described in step (1) is：Wherein X is chlorine atom or bromine
Atom；Any one of R in following 16-26, and it is not limited to following 16-26 kinds；Wherein R1With R2Identical or difference,
R1It is-C for alkylidenenH2n-, alkylene oxide group be-CnH2nIn O-, oxygen, phenylene, alkylidene one or more C be substituted by phenyl,
One or more C are replaced by phenyl and/or oxygen in alkylene oxide group；R2It is-C for alkylidenenH2n-, alkylene oxide group be-CnH2nO-、
One or more C are substituted by phenyl in oxygen, phenylene, alkylidene, one or more C are taken by phenyl and/or oxygen in alkylene oxide group
Generation；* it is junction；
Any one of described binary sulfonamide compounds in the following 1-15, and it is not limited to following 15 kinds：Wherein R1For
Alkylidene is-CnH2n-, alkylene oxide group be-CnH2nIn O-, oxygen, phenylene, alkylidene one or more C be substituted by phenyl, alkylene
One or more C are replaced by phenyl and/or oxygen in epoxide；R2For alkyl, alkoxyl, phenyl, alkyl-substituted phenyl, alkoxyl
One or more C are substituted by phenyl in substituted phenyl, alkyl, one or more C are replaced by phenyl and/or oxygen in alkoxyl；
3. the preparation method of carbene amines according to claim 1, it is characterised in that：Binary alkynes described in step (1)
Halogen compound and the mol ratio of binary sulfonamide compounds reaction are 1:1, binary alkynes halogen compound concentration in organic solvent
For 0.1-0.2mol/L.
4. the preparation method of carbene amines according to claim 1, it is characterised in that：Catalytic body described in step (1)
System is containing CuSO4·5H2O, K2CO3With the system of 1,10- Phens.
5. the preparation method of carbene amines according to claim 4, it is characterised in that：The CuSO45H2The consumption of O
For the 10-20mol% of binary alkynes halogen compound consumption, the consumption of 1,10- Phen is the 20- of binary alkynes halogen compound consumption
40mol%, K2CO3Concentration in organic solvent is 0.2-0.4mol/L.
6. the preparation method of carbene amines according to claim 1, it is characterised in that：The organic solvent is dimethyl
One kind in sulfoxide or N,N-dimethylformamide.
7. the preparation method of carbene amines according to claim 1, it is characterised in that：React described in step (1)
Temperature is 50-100 DEG C, and the time of reaction is 24-48h.
8. the preparation method of carbene amines according to claim 1, it is characterised in that：Precipitating reagent described in step (2)
For methyl alcohol.
9. the preparation method of carbene amines according to claim 1, it is characterised in that：React described in step (2) female
Liquid adds the mode in precipitating reagent to be added dropwise, and is first diluted with tetrahydrofuran before reaction mother liquor is added in precipitating reagent,
Filtered after dilution.
10. the carbene amines that a kind of preparation method by described in any one of claim 1～9 is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611086123.7A CN106633048B (en) | 2016-11-30 | 2016-11-30 | A kind of carbene aminated compounds and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611086123.7A CN106633048B (en) | 2016-11-30 | 2016-11-30 | A kind of carbene aminated compounds and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106633048A true CN106633048A (en) | 2017-05-10 |
| CN106633048B CN106633048B (en) | 2019-04-09 |
Family
ID=58813803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611086123.7A Active CN106633048B (en) | 2016-11-30 | 2016-11-30 | A kind of carbene aminated compounds and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106633048B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485814A (en) * | 2018-10-31 | 2019-03-19 | 华南理工大学 | A kind of method that alkynes, amine and aldehyde multicomponent polymerization prepare carbene propyl amine |
| CN114773605A (en) * | 2022-04-14 | 2022-07-22 | 湖北宜化新材料科技有限公司 | Preparation method of selenium-containing polymer taking carbamate bond as core |
| CN115819768A (en) * | 2023-02-23 | 2023-03-21 | 广东工业大学 | Reversible adhesive polysulfide and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772027A (en) * | 1972-02-04 | 1973-11-13 | Eastman Kodak Co | Photosensitive element containing a photosensitive crystalline polyacetylenic compound and a photoconductive inorganic metal salt |
| WO2010033771A2 (en) * | 2008-09-19 | 2010-03-25 | Trustees Of The University Of Pennsylvania | Modulators of hsp70/dnak function and methods of use thereof |
| CN104130177A (en) * | 2014-07-15 | 2014-11-05 | 四川大学 | Synthesis method of phthalonitrile and arylacetylene-terminated aromatic imide |
| TW201600091A (en) * | 2014-06-24 | 2016-01-01 | 國立清華大學 | Use of heat shock protein inhibitor in preparing pharmaceutical composition for treating hepatitis and hepatoma |
| CN105820335A (en) * | 2016-03-31 | 2016-08-03 | 华南理工大学 | Polyene amino compound and preparation method thereof |
-
2016
- 2016-11-30 CN CN201611086123.7A patent/CN106633048B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772027A (en) * | 1972-02-04 | 1973-11-13 | Eastman Kodak Co | Photosensitive element containing a photosensitive crystalline polyacetylenic compound and a photoconductive inorganic metal salt |
| WO2010033771A2 (en) * | 2008-09-19 | 2010-03-25 | Trustees Of The University Of Pennsylvania | Modulators of hsp70/dnak function and methods of use thereof |
| TW201600091A (en) * | 2014-06-24 | 2016-01-01 | 國立清華大學 | Use of heat shock protein inhibitor in preparing pharmaceutical composition for treating hepatitis and hepatoma |
| CN104130177A (en) * | 2014-07-15 | 2014-11-05 | 四川大学 | Synthesis method of phthalonitrile and arylacetylene-terminated aromatic imide |
| CN105820335A (en) * | 2016-03-31 | 2016-08-03 | 华南理工大学 | Polyene amino compound and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| CARRIE Y. K. CHAN,ET AL.: "Construction of functional macromolecules with well-defined structures by indium-catalyzed three-component polycoupling of alkynes, aldehydes, and amines", 《MACROMOLECULES》 * |
| IN-HWAN LEE,ET AL.: "Cu-catalyzed multicomponent polymerization to synthesize a library of poly (n-sulfonylamidines)", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| JINSONG PENG,ET AL.: "Nucleophilic addition of benzimidazoles to alkynyl bromides/palladium-catalyzed intramolecular C–H vinylation: synthesis of benzo [4, 5] imidazo [2, 1-a] isoquinolines", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| RYOHEI KAKUCHI,ET AL.: "Pendant structure governed anion sensing property for sulfonamide‐functionalized poly (phenylacetylene) s bearing various α‐amino acids", 《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485814A (en) * | 2018-10-31 | 2019-03-19 | 华南理工大学 | A kind of method that alkynes, amine and aldehyde multicomponent polymerization prepare carbene propyl amine |
| CN114773605A (en) * | 2022-04-14 | 2022-07-22 | 湖北宜化新材料科技有限公司 | Preparation method of selenium-containing polymer taking carbamate bond as core |
| CN115819768A (en) * | 2023-02-23 | 2023-03-21 | 广东工业大学 | Reversible adhesive polysulfide and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106633048B (en) | 2019-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104230953B (en) | Benzene-naphthalene diimide and derivant thereof containing 2-(1,3-bis-sulfur/selenium-2-subunit) second cyanogen conjugated structure unit | |
| CN101094718B (en) | Method for the production of polymers | |
| CN107200832B (en) | A kind of polymer and preparation method thereof with aggregation-induced emission effect, graphene composite material and preparation method thereof | |
| CN106633048B (en) | A kind of carbene aminated compounds and preparation method thereof | |
| CN107132207B (en) | It is a kind of for quickly detecting the fluorescent optical sensor and preparation method thereof of explosive, quickly detect explosive method | |
| CN103172650A (en) | Strong fluorescence fluoro-boron dipyrrole compound containing triphenylamine structure as well as preparation method and application thereof | |
| CN107501276B (en) | A kind of triangular prism shaped organic clathrate compound of fluorenyl and its preparation method and application | |
| CN109734736A (en) | Seven yuan of fluorine boron fluorescent dyes of one kind and its synthetic method | |
| CN108586318A (en) | A kind of hot activation delayed fluorescence material of solution processable and preparation method thereof | |
| CN108864137A (en) | A kind of acceptor compound, preparation method, purposes and the photovoltaic cell containing it | |
| CN104559286B (en) | A kind of triphenylamine-boron fluoride complexing dimethyl pyrrole methine derivative organic dyestuff and preparation method thereof | |
| CN103242312B (en) | A kind of efficient method preparing Bing bis-perylene diimides derivative | |
| CN104558541B (en) | Conjugated polymer polymer based on acetylenic ketone intermediate and preparation method and application | |
| CN105505379B (en) | A kind of long wavelength BODIPY fluorochrome derivatives and preparation method thereof | |
| CN1594314A (en) | Fluorene based water soluble conjugated polymer and process for preparing same | |
| CN108503669A (en) | A kind of efficient diarylethene light-operated switch molecule and preparation method thereof | |
| CN106146496A (en) | A kind of gulf district cyclization synthetic method of double imide derivative | |
| CN113788779B (en) | Acceptor-donating compound based on diphenyl sulfone and indole derivatives, and preparation method and application thereof | |
| CN111056987A (en) | Aggregation-induced emission compound and preparation method and application thereof | |
| Yang et al. | Novel AIE luminogen containing axially chiral BINOL and tetraphenylsilole | |
| CN113527708B (en) | Bridged tetraphenyl vinyl based supramolecular polymer light capture system, preparation and application | |
| CN104628753B (en) | Meso-triphenylamine-substituted 3,5-aryl-modified boron dipyrromethene fluorophore derivatives and preparation method thereof | |
| CN109320708A (en) | A kind of chiral liquid crystal polymer and preparation method thereof that shines | |
| CN106699784A (en) | Preparation method of europium complex containing thiophene groups and application thereof in mercury ion sensing material | |
| CN104387407A (en) | 6-methyl-6H-benzo[4, 5]thiophene[2, 3-b]indole and derivatives thereof as well as synthesis method of 6-methyl-6H-benzo[4, 5]thiophene[2, 3-b]indole and derivatives thereof |
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 |