CN104987346B - A kind of preparation method of the multiamide based compound with fluorescence - Google Patents
A kind of preparation method of the multiamide based compound with fluorescence Download PDFInfo
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- CN104987346B CN104987346B CN201510216058.4A CN201510216058A CN104987346B CN 104987346 B CN104987346 B CN 104987346B CN 201510216058 A CN201510216058 A CN 201510216058A CN 104987346 B CN104987346 B CN 104987346B
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Abstract
The present invention relates to one kind using thionyl chloride processing polyacid, then the method for preparing the multiamide based compound with fluorescence with amino-compound reaction.Including dissolving polyacid with tetrahydrofuran, the tetrahydrofuran solution of thionyl chloride is being instilled dropwise, thionyl chloride is removed after reaction and obtains mixture I；Amino-compound is added in mixture I and obtains mixtures II；After mixtures II is washed three times with petroleum ether, tetrahydrofuran layer is isolated with separatory funnel, decompression steams tetrahydrofuran and obtains crude product III；With the multiamide based compound in chloroform dissolving crude product III, chloroform decompression is steamed after centrifuging or filtering, finally obtains the multiamide based compound with fluorescence.It is to contain multiamide base in molecular structure that the compound that the inventive method obtains, which has the reason for fluorescence, and by changing different amino-compounds, the fluorescent quantum intensity of product, fluorescence color are different.The recyclable recycling of organic solvent used in preparation process.
Description
Technical field
The present invention relates to a kind of preparation method of the multiamide based compound with fluorescence, more particularly to it is anti-to use carboxylic acid
Substrate is answered, thionyl chloride is as acyl chlorides reagent, the side with multiamide based compound of the amino-compound reaction generation with fluorescence
Method.
Background technology
Organic molecule has fluorescent characteristic, is due to conjugation heterocycle and various chromophores in molecule, by drawing more
Enter the unsaturated groups such as ethylene linkage, phenyl ring and various chromophores to change its conjugate length, so that compound optoelectronic property occurs
Change.Wherein amido link is that conventional connection is conjugated heterocycle and functional group of chromophore, but yet there are no only generate multiamide both at home and abroad
Key and with photoluminescent property compound.
The content of the invention
In order to solve the above technical problems, the invention provides a kind of preparation side of the multiamide based compound with fluorescence
Method.The multiamide based compound can be used for ion concentration of mercury in test water.
Technical scheme is as follows：
A kind of preparation method of the multiamide based compound with fluorescence, step are as follows：
1）Under conditions of nitrogen is passed through, carboxylic acid is dissolved with tetrahydrofuran, the dichloro for instilling tetrahydrofuran dilution dropwise is sub-
After sulfolane solution, amino-compound is added after stirring（Primary amine or secondary amine）Reaction.Unnecessary thionyl chloride is steamed after the completion of reaction,
Obtain the mixture I that main component is polynary acyl chlorides；
2）With tetrahydrofuran dissolving mixt I, after adding amino-compound stirring, it is polynary amidatioon to obtain main component
The mixtures II of compound；
3）After mixtures II is washed three times with petroleum ether, tetrahydrofuran layer is isolated with separatory funnel, decompression steams mixed
Tetrahydrofuran in compound obtains crude product III；
4）Crude product III is dissolved with chloroform, chloroform decompression in chloroformic solution is steamed after filtering, finally obtained with fluorescence
Multiamide based compound.
Above-mentioned steps 1）In carboxylic acid select polyacid, preferable polyacid is citric acid, and the quantum yield of its product is general
All over higher；
Above-mentioned steps 1）In, preferable polyacid and tetrahydrofuran mass ratio are about 1:25~1:30, under this ratio,
Reaction is gentle and the usage amount of solvent is moderate；
Above-mentioned steps 1）In polyacid be about with thionyl chloride mol ratio（1:n）~（1:1.05n）；
Above-mentioned steps 1）In tetrahydrofuran be about with thionyl chloride volume ratio（5:1）~（50:1）；（Tetrahydrochysene is also needed to
Both quantity relative ratio relationships in the thionyl chloride solution of furans dilution）
Above-mentioned steps 1）In preferable range of reaction temperature be 0 DEG C ~ 30 DEG C, the reaction time is 1 ~ 4hr；
Above-mentioned steps 2）In amino-compound, preferably aminoethylaminopropyl dimethoxysilane, allylamine.When anti-
It is citric acid and N- to answer substrate（β-aminoethyl-γ-aminopropyl）During methyl dimethoxysilane, the quantum yield of its product is
10.7%, under 365nm ultra violet lamps, fluorescence color is blue and white, purple in 365nm when amino-compound is diethylamide
Under outer light irradiation, fluorescence color is yellow green.
Above-mentioned steps 2）In polyacid and amino-compound mol ratio, preferably（1：n） ~ （1:1.1n）, its
InnFor the number of-COOH in polyacid.
Above-mentioned steps 2）In, reaction temperature preferred scope is 30 ~ 50 DEG C, and the range of reaction temperature is easily controlled, and at this
Accessory substance is few in temperature range.Reaction time is preferably 30min ~ 1hr, and reaction efficiency is high in the reaction time.
Above-mentioned steps 3）In, the ratio between preferable mixtures II and petroleum ether cumulative volume are about（75~150）：750, the ratio
Under, petroleum ether dosage is moderate, and can clean up nonreactive amino-compound in reaction system.
Above-mentioned steps 4）In, the ratio between preferable crude product III and chloroform volume is 1：（25~35）, under the ratio, chloroform
Dosage is moderate, and the fluorescence multiamide compound that can be completely dissolved in crude product II.
Specific chemical reaction is as follows：
。
The good results effect of the inventive method is as follows：
1. preparation method operation of the present invention is easy.Only it can be obtained by by relatively low temperature and in the short period
With compared with high-fluorescence quantum yield, the multiamide based compound of a variety of fluorescence colors.
2. the multiamide based compound quantum yield that the present invention obtains is higher.Using the preparation method of the present invention, multiamide
The quantum yield of based compound is up to 40.7%.
3. preparation method economic effect of the present invention is obvious, the recyclable recycling of solvent in each preparation process.
Brief description of the drawings
Fig. 1 is the absorption spectrum, excitation spectrum and transmitting light of the multiamide based compound with fluorescence prepared by embodiment 1
Spectrum.
Fig. 2 is emission spectrum of the multiamide based compound with fluorescence of the preparation of embodiment 1 under different excitation wavelengths.
Fig. 3 is the Characterization of The Products figure of the multiamide based compound with fluorescence prepared by embodiment 2.
Embodiment
With reference to example, the present invention will be further described, but not limited to this.
Raw materials used anhydrous citric acid in embodiment, the third three acid, malic acid, diethylamide, ethylenediamine, diethylamine, propylene
Amine, N-（β-aminoethyl-γ-aminopropyl）Methyl dimethoxysilane, thionyl chloride, tetrahydrofuran, petroleum ether, chloroform（Trichlorine
Methane）It is commercially available.
Embodiment 1
The preparation of fluorescence citric mide, step are as follows：
1. taking 2g citric acids to add in three-necked flask, the dissolving of 30ml tetrahydrofurans is added, nitrogen is slowly introducing, takes 2.7ml
Thionyl chloride（Citric acid is 1 with thionyl chloride mol ratio:3.2）It is placed in constant pressure funnel, then is diluted with 2.3 ml tetrahydrofurans,
Then be added dropwise in the citric acid of dissolving, by this device as uniform stirring 12h at 40 DEG C after, it is sub- to steam unnecessary dichloro
Sulfone, transparency liquid I is produced,
2. taking 2ml tetrahydrofurans to dilute transparency liquid I, N- is added（β-aminoethyl-γ-aminopropyl）Methyl dimethoxy epoxide silicon
The ml of alkane 10, is stirred vigorously half an hour, obtains mixtures II；
3. mixtures II is cleaned three times with 35mL petroleum ethers respectively, separatory funnel isolates tetrahydrofuran layer, then subtracts
Pressure steams tetrahydrofuran, obtains crude product III about 2g；
4. with the product in 50mL chloroforms extraction crude product III, depressurized again after centrifugation or filtering and steam chloroform, obtained
To the multiamide based compound CA-Si with fluorescence.
Multiamide based compound obtained as above with fluorescence fluorometric investigation has been done into.Fig. 1 is the multiamide with fluorescence
Absorption spectrum, excitation spectrum and the emission spectrum of based compound.Insert pictures are fluorescent small molecule solution in natural light（It is left）And
Ultraviolet light（It is right）Under photo.Fig. 2 is its emission spectrum under different excitation wavelengths（Excitation wavelength difference is 20nm）.With sulfuric acid
Quinine is reference substance, and the fluorescence quantum yield for obtaining multiamide based compound is 40.7%.
Embodiment 2
The preparation of fluorescence citric mide, step are as follows：
1. taking 2g citric acids to add in three-necked flask, the dissolving of 30ml tetrahydrofurans is added, nitrogen is slowly introducing, takes
1.45ml thionyl chloride（Citric acid is 1 with thionyl chloride mol ratio:2）It is placed in constant pressure funnel, then with 1.55 ml tetrahydrofurans
Dilution, be then added dropwise in the citric acid of dissolving, by this device as uniform stirring 12h in 0 DEG C of environment after, add 20ml just
Hexane decompression filters three times, steams remaining thionyl chloride, produces transparency liquid I；
2. taking 2ml tetrahydrofurans to dilute transparency liquid, the ml of diethylamide 10 is added, half an hour is stirred vigorously, is mixed
Compound II；
3. mixtures II is cleaned three times with 35mL petroleum ethers respectively, separatory funnel isolates tetrahydrofuran layer, then subtracts
Pressure steams tetrahydrofuran, obtains crude product III about 1.25g.
4. with the product in 50mL tetrachloromethanes extraction crude product III, depressurized again after centrifugation or filtering and steam four
Chloromethanes, obtain the multiamide based compound CA with fluorescence；
The products therefrom phenogram such as ultraviolet absorptivity of Fig. 3 fluorescent small molecules CA solution, excite, launch collection of illustrative plates；It is and glimmering
Light small molecule is in natural light（It is right）And ultraviolet light（It is left）Photo.Using quinine sulfate as reference substance, multiamide based compound is obtained
Fluorescence quantum yield be 37.6%.
Embodiment 3
The preparation of the third three sour acid amides of fluorescence, step are as follows：
1. taking the acid of 2g the third three to add in three-necked flask, the dissolving of 30ml tetrahydrofurans is added, nitrogen is slowly introducing, takes 2.5ml
Thionyl chloride（Citric acid is 1 with thionyl chloride mol ratio:2）It is placed in constant pressure funnel, then is diluted with 1.5 ml tetrahydrofurans, so
Be added dropwise afterwards in the citric acid of dissolving, by this device as uniform stirring 12h in 0 DEG C of environment after, add 20ml n-hexanes subtract
Pressure filters three times, steams remaining thionyl chloride, produces transparency liquid I；
2. taking 2ml tetrahydrofurans to dilute transparency liquid, diethylamide and N- are added（β-aminoethyl-γ-aminopropyl）Methyl
The ml of dimethoxysilane 10, is stirred vigorously half an hour, obtains mixtures II；
3. mixtures II is cleaned three times with 35mL petroleum ethers respectively, separatory funnel isolates tetrahydrofuran layer, then subtracts
Pressure steams tetrahydrofuran, obtains crude product III about 0.7g；
4. with the product in 50mL chloroforms extraction crude product III, depressurized again after centrifugation or filtering and steam chloroform, obtained
To the multiamide based compound with fluorescence.
Products therefrom characterizes, fluorescence quantum yield 10.5% similar with example 1.
Embodiment 4
The preparation of the third three sour acid amides of fluorescence, step are as follows：
1. taking the acid of 2g the third three to add in three-necked flask, the dissolving of 30ml tetrahydrofurans is added, nitrogen is slowly introducing, takes 1.4ml
Thionyl chloride（Citric acid is 1 with thionyl chloride mol ratio:2.2）It is placed in constant pressure funnel, then is diluted with 2.6ml tetrahydrofurans,
Then be added dropwise in the citric acid of dissolving, by this device as uniform stirring 12h in 0 DEG C of environment after, add 20ml n-hexanes
Decompression filters three times, steams unnecessary thionyl chloride, produces transparency liquid I；
2. taking 2ml tetrahydrofurans to dilute transparency liquid, appropriate N- is added（β-aminoethyl-γ-aminopropyl）Methyl dimethoxy oxygen
The ml of base silane 10, is stirred vigorously half an hour, obtains mixtures II；
3. mixtures II is cleaned three times with 35mL petroleum ethers respectively, separatory funnel isolates tetrahydrofuran layer, then subtracts
Pressure steams tetrahydrofuran, obtains crude product III about 2.05g.
4. with the product in 50mL dichloromethane extraction crude product III, depressurized again after centrifugation or filtering and steam two
Chloromethanes, obtain the multiamide based compound with fluorescence.
Embodiment 5
The preparation of fluorescence citric mide, step are as follows：
1. taking 2g malic acid to add in three-necked flask, the dissolving of 30ml tetrahydrofurans is added, nitrogen is slowly introducing, takes 2.7ml
Thionyl chloride（Citric acid is 1 with thionyl chloride mol ratio:2.2）It is placed in constant pressure funnel, then is diluted with 2.3ml tetrahydrofurans,
Then be added dropwise in the citric acid of dissolving, by this device as uniform stirring 12h in 0 DEG C of environment after, add 20ml n-hexanes
Decompression filters three times, steams unnecessary thionyl chloride, produces transparency liquid I；
2. taking 2ml tetrahydrofurans to dilute transparency liquid, allylamine 10ml is added, half an hour is stirred vigorously, obtains mixture
II；
3. mixtures II is cleaned three times with 35mL petroleum ethers respectively, separatory funnel isolates tetrahydrofuran layer, then subtracts
Pressure steams tetrahydrofuran, obtains crude product III about 1.45g.
4. with the product in 50mL dichloromethane extraction crude product III, depressurized again after centrifugation or filtering and steam two
Chloromethanes, obtain the multiamide based compound with fluorescence.
Embodiment 6
The preparation of fluorescence citric mide, step are as follows：
1. taking 2g citric acids to add in three-necked flask, the dissolving of 30ml tetrahydrofurans is added, nitrogen is slowly introducing, takes 1.45ml
Thionyl chloride（Citric acid is 1 with thionyl chloride mol ratio:2.2）It is placed in constant pressure funnel, then is diluted with 1.55ml tetrahydrofurans,
Then be added dropwise in the citric acid of dissolving, by this device as uniform stirring 12h in 0 DEG C of environment after, add 20ml n-hexanes
Decompression filters three times, steams unnecessary thionyl chloride, produces transparency liquid I；
2. taking 2ml tetrahydrofurans to dilute transparency liquid, allylamine 10ml is added, half an hour is stirred vigorously, obtains mixture
II；
3. mixtures II is cleaned three times with 35mL petroleum ethers respectively, separatory funnel isolates tetrahydrofuran layer, then subtracts
Pressure steams tetrahydrofuran, obtains crude product III about 0.9g.
4. with the product in 50mL chloroforms extraction crude product III, depressurized again after centrifugation or filtering and steam chloroform, obtained
To the multiamide based compound with fluorescence.
Claims (1)
- A kind of 1. application of multiamide based compound as fluorescent material, it is characterized in that the structure of described multiamide based compound Formula is：。
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| CN107245332A (en) * | 2017-07-13 | 2017-10-13 | 济南大学 | A kind of organo-mineral complexing fluorescent microsphere preparation method |
| CN107952403A (en) * | 2017-12-04 | 2018-04-24 | 济南大学 | A kind of fluorescent silicon dioxide method for preparing microsphere of Quantitative detection iron ion |
| CN107892914A (en) * | 2017-12-08 | 2018-04-10 | 济南大学 | A kind of quick identification and the fluorescent microsphere preparation method for quantitatively detecting mercury ion |
| CN114133570B (en) * | 2021-11-16 | 2022-10-04 | 北京科技大学 | Self-repairing polysiloxane elastomer and preparation method thereof |
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