CN106633048B - A kind of carbene aminated compounds and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of organic chemistry, a kind of carbene aminated compounds and preparation method thereof is disclosed.The method, comprising the following steps: (1) under inert gas protection, in catalyst system and organic solvent, binary alkynes halogen compound and binary sulfonamide compounds are mixed, reacted, it is cooling, obtain reaction mother liquor；(2) reaction mother liquor is added in precipitating reagent and is precipitated, collected sediment and dry to constant weight, obtain carbene amine compounds.Preparation method of the invention is simple, reaction is efficient, and group tolerance is stronger, and several functions group can be introduced in monomer；Prepared carbene amine compounds contain triple carbon-carbon bonds, have important application as intermediate aspect for further reacting；And the compound facile hydrolysis, the great application prospect in terms of the environmentally friendly chemistries such as degradation material and Green Chemistry.
Description
Technical field
The invention belongs to the technical fields of organic chemistry, are 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 technique
Develop new polymerization reaction to be 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 concerns of scientists.The coupling polymerization reaction of ynamine has that reaction condition is mild, reaction efficiency is high, atom economy etc.
Feature meets the definition of green chemical reaction, is a kind of novel polymerization reaction.It is wide currently based on the small molecule of ynamine
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 application value synthetic intermediate it
One.
However, the coupling polymerization reaction of ynamine is but studied and reports yet in organic field, it can thus be anticipated that exploitation
Simply, efficiently carbene amine route of synthesis will be with important scientific meaning and application value.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of carbene amine compounds, this method belongs to easy to operate, anti-
It should efficient, atom economy green chemical reaction.
Another kind of the invention, which is designed to provide, utilizes carbene amine compounds obtained by the above method, the compound structure
Inside there are three keys, will also have important application as intermediate aspect for further reacting.Meanwhile the compound facile hydrolysis,
Develop degradation material etc. it is environmental-friendly with Green Chemistry in terms of also great potential.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of carbene amine compounds, comprising the following steps:
(1) under inert gas protection, in catalyst system and organic solvent, by binary alkynes halogen compound and binary sulphonyl
Amine compounds mixing, reacts, cooling, obtains reaction mother liquor；
(2) reaction mother liquor is added in precipitating reagent and is precipitated, collected sediment and dry to constant weight, obtain carbene amination
Close object.
Binary alkynes halogen compound described in step (1) and the molar ratio of binary sulfonamide compounds reaction are 1:1, binary alkynes
The concentration of halogen compound in organic solvent is 0.1-0.2mol/L.
Catalyst system described in step (1) is to contain CuSO4·5H2O, K2CO3With the system of 1,10- Phen；
The CuSO45H2The dosage of O is the 10-20mol% of binary alkynes halogen compound dosage, 1,10- Phen
Dosage is the 20-40mol%, K of binary alkynes halogen compound dosage2CO3Concentration in organic solvent is 0.2-0.4mol/L.
The organic solvent is one of dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF).
The temperature of reaction described in step (1) is 50-100 DEG C, and the time of reaction is 24-48h；
Precipitating reagent is methanol in step (2).
The mode that reaction mother liquor described in step (2) is added in precipitating reagent is that (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, dilution is filtered later.
The structural formula of binary alkynes halogen compound described in step (1) are as follows:Wherein X is that chlorine is former
Son or bromine atom；Any one of R in following 16-26, and it is not limited to following 16-26 kind；Wherein R1With R2It is identical or
Difference, R1For alkylidene (- CnH2n, n is integer), alkylene oxide group (- CnH2nO-, n are integer), oxygen (O), phenylene, alkylidene
Middle one or more C be substituted by phenyl (substituted carbon number be less than alkylidene in carbon number), in 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 is substituted by phenyl that (substituted carbon number is less than Asia in alkylidene
Carbon number in alkyl), one or more C is 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 the binary sulfonamide compounds in 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 be substituted by phenyl (substituted carbon number be less than alkylidene in carbon number), in 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, alkoxy, phenyl, alkyl-substituted phenyl,
Phenyl that alkoxy replaces, one or more C is substituted by phenyl (substituted carbon number is less than carbon number in alkyl), alkoxy in alkyl
Middle one or more C replaces (substituted carbon number is less than carbon number in alkylidene) by phenyl and/or oxygen；
The present invention also provides a kind of carbene amine compounds, are prepared by the above method.
The structure of the carbene amine compounds 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.
Still there are three keys in the carbene amine compounds structure, important as will also have in terms of intermediate for further reacting
Using.Meanwhile the compound facile hydrolysis, develop degradation material etc. it is environmental-friendly with Green Chemistry in terms of also great potential.
Compared with prior art, the present invention has the advantage that
1, the present invention polymerize to obtain carbene amine using alkynes halogen and sulfonamide, as far as we know, the type of polymerization never by
Report, therefore there is very high scientific research value, application value and good development prospect；
2, preparation method simple process of the invention, the catalyst and raw material used are easy to get, can be by purchase or simple
Experimental implementation obtains；
3, preparation method reaction condition of the invention is mild, efficient, energy saving, and no coupling product generates, and has original
The characteristics of subeconomy；
4, preparation method group tolerance of the invention is stronger, and several functions group can be introduced in monomer；
5, the carbene amine compounds facile hydrolysis that preparation method through the invention obtains, it is environmental-friendly in degradation material etc.
Chemistry and the great application prospect of Green Chemistry aspect.
Detailed description of the invention
Fig. 1 is carbene amine compounds (P1) prepared by the embodiment of the present invention 1 and its corresponding monomer (M1, M2) and modelling
Close object nuclear magnetic resonance spectroscopy comparison diagram in deuterated DMSO；
Fig. 2 is carbene amine compounds (P1) prepared by the embodiment of the present invention 1 and its corresponding monomer (M1, M2) and modelling
Close object carbon-13 nmr spectra comparison diagram in deuterated DMSO；
Fig. 3 is carbene amine compounds (P1) prepared by the embodiment of the present invention 1 and its corresponding monomer (M1, M2) and modelling
Close the infrared absorpting light spectra of object；
Fig. 4 is fluorescence emission spectrum 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 figure 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 below with reference to embodiment and attached drawing, but protection scope of the present invention be not limited to
Lower embodiment.
Embodiment 1
A kind of carbene amine compounds P1, structural formula are as follows:
The carbene amine compounds, which are reacted by alkynes halogen with sulfamide monomer, to be prepared, specific reaction equation such as formula
(1):
(1) synthetic method of monomer M1 are as follows: at 0 DEG C, 9.0mmol (3.29g) sulphonyl is added into 250mL two-mouth bottle
Chlorine vacuumizes and changes N2150mL methylene chloride and 36.9mmol (4.03mL) benzylamine are added afterwards, reaction system is stirred at normal temperature
After 2 hours, with methylene chloride and water extraction three times, be spin-dried for, 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), yield 85%；M1 monomer in the nuclear-magnetism figure of Fig. 1
8.20 be the peak-NH, and 4.04 be-CH2Peak, wherein 3.32 be water peak, and 2.50 be the peak DMSO-d6；Monomer M1 presence-NH in Fig. 3
Peak；
(2) synthetic method of monomer M2 are as follows: 10.0mmol (1.26g) 1,4- diacetylene is added in 250mL single port bottle
Benzene, 22.0mmol (3.89g) NBS, 2.0mmol (0.34g) silver nitrate, after adding 100mL acetone, system is stirred at normal temperature
It mixes 3 hours, then filters, is spin-dried for, crude product purified by silica gel chromatographic column is isolated and purified, after being dried in vacuo at a temperature of 40 DEG C,
Obtain 7.8mmol (2.20g) product (monomer M2), yield 78%；For on phenyl ring at the 7.48 of M2 monomer in the nuclear-magnetism figure of Fig. 1
The peak H, wherein 3.32 be water peak, and 2.50 be the peak DMSO-d6；There are triple carbon-carbon bonds peaks in Fig. 3；
(3) preparation step of the carbene aminated compounds described in are as follows: sequentially add 0.2mmol in 10mL polymerization pipe
(0.11g) monomer M1,0.2mmol (0.06g) monomer M2,0.03mmol (0.005g) CuSO4·5H2O、0.06mmol
(0.01g), 1,10- Phen, 0.6mmol (0.08g) K2CO3, vacuumize and change N22mL DMSO is added afterwards, system is heated up
It is stirred 24 hours after to 65 DEG C with 400 rpms of rate；2mL tetrahydrofuran diluting reaction system is used after reaction, is made
System is filtered out to be added drop-wise in precipitating reagent anhydrous methanol after copper sulphate and be settled, stand 12 hours, filtering, after vacuum drying
It is dried in vacuo at a temperature of 40 DEG C, obtains 0.12g polymer P 1, yield 86%, molecular weight reaches 18000g/mol；The core of Fig. 1
P1 figure in magnetic chart can see, and the peak-NH of monomer M1 has disappeared, and-CH24.65 are displaced to from 4.04, wherein 3.32 are
Water peak, 2.50 be the peak DMSO-d6；After the reaction that can observe in Fig. 3 in P1-NH disappearance, the presence at triple carbon-carbon bonds peak；
(4) the specific reaction equation of model compound is as follows:
The preparation step of the model compound are as follows: sequentially added 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- Phen,
8.0mmol(1.11g)K2CO3, vacuumize and change N210mL DMSO is added afterwards, system is warming up to after 65 DEG C with 400 rpms
Rate stir 36 hours, after reaction with methylene chloride and water extraction three times, be spin-dried for, crude product purified by silica gel chromatographic column carry out
It isolates and purifies and is dried in vacuo at a temperature of 40 DEG C, obtain 1.8mmol (1.16g) product, yield 90%.
Carbene amine compounds (P1) manufactured in the present embodiment and its corresponding monomer (M1, M2) and model compound are deuterated
Nuclear magnetic resonance spectroscopy 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 90%, molecular weight reaches 17000g/mol.
Embodiment 3
The present embodiment is by the CuSO in embodiment 14·5H2O, which feeds intake, is changed to 0.04mmol (0.007g), 1,10- Phen
It feeds intake and is changed to 0.08mmol (0.02g), K2CO3It feeds intake and is changed to 0.80mmol (0.11g), the system of other preparation conditions and embodiment 1
Preparation Method is identical, obtains polymer 0.12g, yield 81%, molecular weight reaches 18000g/mol.
Embodiment 4
A kind of carbene amine compounds P2, shown in structural formula:
The carbene amine compounds, which are reacted by alkynes halogen with sulfamide monomer, to be prepared, specific reaction equation such as formula
(2):
(1) synthetic method of monomer M1 is the same as described in example 1；
(2) synthetic method of monomer M3 is as described below: 3.0mmol (1.14g) diacetylene being added in 250mL single port bottle
Tetraphenylethylene, 6.6mmol (1.17g) NBS, 0.6mmol (0.10g) silver nitrate, after adding 60mL acetone, by system normal
It temperature lower stirring 3 hours, then filters, be spin-dried for, crude product purified by silica gel chromatographic column is isolated and purified, and vacuum is dry at a temperature of 40 DEG C
2.7mmol (1.45g) product, yield 90% are obtained after dry；
Diethylacetylene 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 preparation；
(3) preparation step of the carbene aminated compounds described in is as follows: sequentially adding 0.2mmol in 10mL polymerization pipe
(0.10g) monomer M1,0.2mmol (0.11g) monomer M3,0.03mmol (0.005g) CuSO4·5H2O、0.06mmol
(0.01g), 1,10- Phen, 0.6mmol (0.08g) K2CO3, vacuumize and change N22mL DMSO is added afterwards, system is heated up
It is stirred 24 hours after to 65 DEG C with 400 rpms of rate；2mL tetrahydrofuran diluting reaction system is used after reaction, is made
System is filtered out to be added drop-wise in precipitating reagent anhydrous methanol after copper sulphate and be settled, stand 12 hours, filtering, after vacuum drying
It is dried in vacuo at a temperature of 40 DEG C, obtains 0.15g polymer P 2, yield 86%, molecular weight reaches 11000g/mol.
The polymer that this method obtains has special photoelectric property, and Fig. 4 is the polymer P 2 under different water contents
Fluorescence emission spectrum.With the raising of water content, the luminous of the polymer solution is gradually increased, wherein when water content is 95%
When, which has highest luminous efficiency under the solution.Fig. 5 is quantum yield of the polymer P 2 under different water contents
Scheme (excitation wavelength 340nm), when water content is 95%, there is highest quantum yield 24.7%.
Embodiment 5
A kind of carbene amine compounds P3, shown in structural formula:
The carbene amine compounds, which are reacted by alkynes halogen with sulfamide monomer, to be prepared, specific reaction equation such as formula
(3):
(1) synthetic method of monomer M4 are as follows: at 0 DEG C, 9.0mmol (3.29g) sulphonyl is added into 250mL two-mouth bottle
Chlorine vacuumizes and changes N2150mL methylene chloride and 36.9mmol (2.05mL) ethamine are added afterwards, reaction system is stirred at normal temperature
After 2 hours, with methylene chloride and water extraction three times, be spin-dried for, 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), yield 90%；
(2) synthetic method of monomer M5 are as follows:
(2-1) in 250mL two-mouth bottle be added 15.0mmol (3.43g) bisphenol-A, 45mmol (6.22g) potassium carbonate and
100mL acetone then is added toward reaction system to bromine bromobenzyl in 33.0mmol (8.25g), cold after heating reflux reaction 12 hours
But, white depositions are cleaned repeatedly with deionized water, obtain 7.64g white solid product 1, yield 90% after dry；
10.0mmol (5.66g) white solid 1,0.5mmol (0.35g) double triphens is added in (2-2) in 250mL two-mouth bottle
Base phosphorus palladium chloride, 0.5mmol (0.10g) cuprous iodide, 0.5mmol (0.13g) triphenylphosphine, and vacuum nitrogen gas three
It is secondary, 100mL then is added to reaction system and is bubbled the triethylamine handled and the heavy steamed tetrahydrofuran of 20mL by nitrogen, then is past
4mL (30.0mmol) trimethylsilyl acetylene is added in system, it is cooling after being heated to 90 DEG C of reactions 24 hours, chlorine is saturated with 100mL
Change ammonium salt solution quenching reaction, filtering, filtrate is extracted with dichloromethane three times, organic phase is merged and is concentrated, and obtained crude product is used
Silica gel chromatographic column is separated, and eluent is petroleum ether, obtains 5.40g white solid product 2, yield 90%；
5.0mmol (3.00g) white solid 2 and 25.0mmol (1.40g) hydrogen-oxygen is added in (2-3) in 250mL single port bottle
Change potassium, then 25mL methanol, 25mL tetrahydrofuran, 5mL deionized water are added inward, after stirring 12 hours at room temperature, reaction mixing
Liquid is extracted with dichloromethane three times, and organic phase is merged and is concentrated, and obtained crude product purified by silica gel chromatographic column is separated, eluent
For petroleum ether, 2.17g white solid product 3, yield 95% are obtained；
(2-4) in 250mL single port bottle be added 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 3 hours at normal temperature, then filters, is spin-dried for,
Crude product purified by silica gel chromatographic column is isolated and purified, and obtains 1.38g product, as monomer after being dried in vacuo at a temperature of 40 DEG C
M5, yield 90%；
(3) preparation step of the carbene aminated compounds described in are as follows: sequentially add 0.2mmol in 10mL polymerization pipe
(0.08g) monomer M4,0.2mmol (0.12g) monomer M5,0.03mmol (0.005g) CuSO4·5H2O、0.06mmol
(0.01g), 1,10- Phen, 0.6mmol (0.08g) K2CO3, vacuumize and change N22mL DMSO is added afterwards, system is heated up
It is stirred 24 hours after to 65 DEG C with 400 rpms of rate；2mL tetrahydrofuran diluting reaction system is used after reaction, is made
System is filtered out to be added drop-wise in precipitating reagent anhydrous methanol after copper sulphate and be settled, stand 12 hours, filtering, at a temperature of 40 DEG C
0.13g polymer P 3, yield 78% are obtained after vacuum drying.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (9)
1. a kind of preparation method of carbene amine compounds, it is characterised in that: the following steps are included:
(1) under inert gas protection, in catalyst system and organic solvent, by binary alkynes halogen compound and binary sulfuryl amine
Object mixing is closed, is reacted, it is cooling, obtain reaction mother liquor；
(2) reaction mother liquor is added in precipitating reagent and is precipitated, collected sediment and dry to constant weight, obtain carbene amine compounds
Object；
The structural formula of binary alkynes halogen compound described in step (1) are as follows:Wherein X is chlorine atom or bromine
Atom；Any one of R in following 16-26；Wherein R1With R2It is same or different, R1It is-C for alkylidenenH2n, alkylene
Oxygroup is-CnH2nO-, oxygen, phenylene, in alkylidene one or more C be substituted by phenyl, one or more C quilt in alkylene oxide group
Phenyl and/or oxygen replace；R2It is-C for alkylidenenH2n, alkylene oxide group be-CnH2nO-, oxygen, phenylene, in alkylidene one or
Multiple C are substituted by phenyl, one or more C is replaced by phenyl and/or oxygen in alkylene oxide group；It * is junction；
Any one of the binary sulfonamide compounds in following 1-15；Wherein R1It is-C for alkylidenenH2n, alkylene
Oxygroup is-CnH2nO-, oxygen, phenylene, in alkylidene one or more C be substituted by phenyl, one or more C quilt in alkylene oxide group
Phenyl and/or oxygen replace；R2It is in alkyl, alkoxy, phenyl, alkyl-substituted phenyl, the phenyl of alkoxy substitution, alkyl one
A or multiple C are substituted by phenyl, one or more C is replaced by phenyl and/or oxygen in alkoxy；
2. the preparation method of carbene amine compounds according to claim 1, it is characterised in that: binary alkynes described in step (1)
Halogen compound and the molar ratio of binary sulfonamide compounds reaction are 1:1, the concentration of binary alkynes halogen compound in organic solvent
For 0.1-0.2mol/L.
3. the preparation method of carbene amine compounds according to claim 1, it is characterised in that: catalytic body described in step (1)
System is to contain CuSO4·5H2O, K2CO3With the system of 1,10- Phen.
4. the preparation method of carbene amine compounds according to claim 3, it is characterised in that: the CuSO4·5H2The dosage of O
For the 10-20mol% of binary alkynes halogen compound dosage, the dosage of 1,10- Phen is the 20- of binary alkynes halogen compound dosage
40mol%, K2CO3Concentration in organic solvent is 0.2-0.4mol/L.
5. the preparation method of carbene amine compounds according to claim 1, it is characterised in that: the organic solvent is dimethyl
One of sulfoxide or N,N-dimethylformamide.
6. the preparation method of carbene amine compounds according to claim 1, it is characterised in that: reaction described in step (1)
Temperature is 50-100 DEG C, and the time of reaction is 24-48h.
7. the preparation method of carbene amine compounds according to claim 1, it is characterised in that: precipitating reagent described in step (2)
For methanol.
8. the preparation method of carbene amine compounds according to claim 1, it is characterised in that: reacted described in step (2) female
The mode that liquid is added in precipitating reagent is to be added dropwise, and be first diluted with tetrahydrofuran before reaction mother liquor is added in precipitating reagent,
Dilution is filtered later.
9. a kind of carbene amine compounds obtained by preparation method according to any one of claims 1 to 8.
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