CN104193666B - A kind of 1,3 disubstituted maleimides compound and its application as critical micelle concentration of surfactant fluorescence probe - Google Patents

A kind of 1,3 disubstituted maleimides compound and its application as critical micelle concentration of surfactant fluorescence probe Download PDF

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CN104193666B
CN104193666B CN201410368738.3A CN201410368738A CN104193666B CN 104193666 B CN104193666 B CN 104193666B CN 201410368738 A CN201410368738 A CN 201410368738A CN 104193666 B CN104193666 B CN 104193666B
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surfactant
compound
cmc
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朱秋华
刘叔文
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Southern Medical University
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    • C07—ORGANIC CHEMISTRY
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    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
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    • C07D207/456—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07—ORGANIC CHEMISTRY
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
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    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"

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Abstract

The present invention discloses application of the 1,3 disubstituted maleimides compounds in as critical micelle concentration of surfactant fluorescence probe.Described 1,3 disubstituted maleimides compounds have aggregation-induced emission characteristic, can enrich and light the classes of compounds that sonde method detects CMC of surfactant for fluorescence；Of the present invention 1,3 disubstituted maleimides compound test CMC sensitivity are high, and preferably suitable for the detection of anionic surfactant CMC the suitable application area that fluorescence lights sonde method can have been expanded than the known compound with similar performance；A kind of method of the present invention simple, sensitive, quick measure CMC approximations method for practical application is provided, method of the method similar to pH approximations are determined with pH test paper, but there is sensitivity higher than pH test paper method, detection method of the invention with physical method --- electrical conductivity method measure come CMC value closely.

Description

A kind of 1,3- disubstituted maleimides compound and its critical as surfactant The application of micellar concentration fluorescence probe
Technical field
The present invention relates to Surfactants Analysis technical field, and in particular to one kind 1,3- disubstituted maleimides chemical combination Thing and its application as critical micelle concentration of surfactant fluorescence probe.
Background technology
Surfactant has multifrequency nature, such as wetting, emulsification, foaming, dissolving, dispersion, washing, it is corrosion-resistant, antistatic Deng being widely used in multiple fields, such as pharmaceutical chemistry, synthesis chemistry, material science, biology.Under certain concentration, That is critical micelle concentration（critical micelle concentration, CMC）Under, surfactant initially forms heating power The micella of stabilization is learned, meanwhile, there is significant change in various properties.Therefore, the measure of CMC has weigh very much in actual applications The meaning wanted, it is a focus of physical chemistry and analytical chemistry research.The CMC assay methods of development are to utilize concentration at present The mutation of surfactant solution physical property determines CMC value when reaching CMC.By fluorescence probe when concentration reaches CMC The mutation of its photoluminescent property has that simple to operate, sensitivity is high, low cost and other advantages determining the method for CMC value, therefore enjoys The concern of various research fields.
CMC fluorimetries are more than in the surfactant solution of CMC and dense in concentration based on organic fluorescence probe What degree in the surfactant solution less than CMC there is visibly different photoluminescent property to determine.When concentration is less than CMC, table Face activating agent usually exists with monomer；When concentration is equal to CMC, the monomer of surfactant initially forms micella, the glue of formation There is dynamic equilibrium between beam and monomer.Have in the presence of micella, organic fluorescence probe is intended to preferentially dissolve or be included in these The inner hydrophobic area of micella, and show with surfactant low concentration（Concentration is less than CMC）It is visibly different in solution Photoluminescent property, such as fluorescence intensity, launch wavelength, emission spectrum vibrational structure property.It is prominent based on different photoluminescent properties at these In the probe of change, only the fluorescence probe based on fluorescence intensity mutation has intuitive, can develop into quick detection CMC value Indicator, the similar pH of its measuring principle detects the principle of pH, but sensitiveer than pH value, because change in fluorescence is cleverer It is quick, with more specificity.
But the existing fluorescence probe based on fluorescence intensity change only has a small amount of report, inventor synthesizes and reports recently Five substituted-tetrahydro pyrimidines can be used for quick detection CMC value（Chinese invention patent CN103411961 A； RSC Chem. Comm. 2013,50: 1107-1109;The A1 of United States Patent (USP) US 2,014 0051855）, and the probe of other reports Cannot be used for quick detection CMC value.Because, the CMC probes based on fluorescence intensity change before we study are CMC value is determined by the most weak catastrophe point of fluorescence intensity, belongs to fluorescence closing（fluorescence turn-off）Measure side Method, and the five substituted-tetrahydro pyrimidines that we report are to determine CMC value by the most strong catastrophe point of fluorescence intensity, category The assay method of (fluorescence turn-on) is lighted in fluorescence, the assay method that fluorescence is lighted is than method that fluorescence is closed It is sensitive.But due to the various structures of surfactant, the five substituted-tetrahydro pyrimidines that we synthesize are only applicable to part The measure of CMC of surfactant value, therefore also need to the more probes for being suitable for quick detection CMC value of development.
The content of the invention
The invention aims to overcome the deficiencies in the prior art, there is provided one kind can be as the critical glue of surfactant The 1,3- disubstituted maleimides compounds of beam concentration fluorescence probe.
Present invention simultaneously discloses the 1,3- disubstituted maleimides compounds of some new constructions.
Above-mentioned purpose of the invention is achieved by following technical solution：
1,3- disubstituted maleimides compound answering in as critical micelle concentration of surfactant fluorescence probe With 1, the 3- disubstituted maleimides compound has such as formula（Ⅰ）Shown structure：
（Ⅰ）
Wherein, R1Selected from the C of meta or para position substitution5~6Aromatic radical or non-substituted C9~18Polycyclic aromatic base；R1In, take Dai Jiwei C1~3Alkyl, C1~3Alkoxy, halogen, cyano group or trifluoromethyl；
R2Selected from C1~8Chain fatty base, C6~8Ring-shaped fat base or with C5~6Aromatic rings or C5~6Aromatic heterocycle replaces The C of base1~4Chain fatty base.
Inventor has found, with such as formula（Ⅰ）The 1,3- disubstituted maleimides compounds of shown structure are lured with aggregation Lead the characteristics of luminescence.Such compound, completely without fluorescence, but sends very strong fluorescence in the solution in micella, is preferable CMC fluorescence lights probe, therefore can change the dismounting for indicating micella by such compound fluorescence signal in the solution Journey, so that determine CMC, i.e., by unstressed configuration（Probe is all included in micella）It is most strong to fluorescence（Micella is all transformed into Monomer, probe is all released in solution）Fluorescence intensity mutation process come indicate micella dismantle process, this process is glimmering Light is lighted（turn-on）Process, be detection sensitivity process very high, Fluorescence Mutation of A point of maximum intensity is CMC.Reported before us Lead and lighted probe for determining the fluorescence of CMC of surfactant：Five substituted-tetrahydro pyrimidines（Chinese invention patent CN103411961 A； RSC Chem. Comm. 2013 50: 1107-1109）, such compound although can be used for it is cloudy from The measure of son, cation and amphoteric ionic surfactant CMC, the CMC value of measure and the CMC of Fluorescent Probes pyrene measure Value is basically identical.But due to the structure diversity of surfactant, the five substituted-tetrahydro pyrimidines that we synthesize only are fitted For the measure of part surface activating agent CMC, such as five substituted-tetrahydro pyrimidines cannot be used for dodecyl sodium sulfate CMC Measure.
Maleimide compound synthesis disclosed in this invention are easy, yield is high, and synthesis cost is lower, also, horse Carry out imide analog compounds except the CMC value of lauryl sodium sulfate can be determined, can also quickly be surveyed under conditions of 40 DEG C Determine the CMC value of dodecyl sodium sulfate.In addition, with the CMC value of maleimide compound determination with use physics side Method --- electrical conductivity method measures the CMC value for coming closely, and the CMC value ratio determined with pyrene or five substituted-tetrahydro pyrimidine compounds Means of Electrical Conductivity value is lower slightly.This explanation, maleimide compound has little to no effect to the measure of CMC value in itself.Therefore, The fluorescence that maleimide compound can determine CMC of surfactant value as a new class lights probe.
The 1,3- disubstituted maleimides compound is in as critical micelle concentration of surfactant fluorescence probe The application method that is referred to existing five substituted-tetrahydros pyrimidine compound, it is preferable that the substitution Malaysia acyls of 1, the 3- bis- Group with imine moiety is configured to fluorescence indicator or kit.
When 1, the 3- disubstituted maleimides compound is configured to fluorescence indicator, following steps are preferably included Detected：
S1. the 1,3- disubstituted maleimides compound is configured to the storing solution that concentration is 2 ~ 5mM with solvent；
S2. by surfactant diluent preparing to be measured into the sample liquid that concentration is 1 ~ 20 mM；
S3. at 25 ~ 40 DEG C, the surfactant samples liquid prepared by step S2. of different volumes is added in difference Volumetric flask in, then the fluorescence indicator storing solution that is prepared by step S1. of same volume is added in each volumetric flask, so Constant volume is carried out using dilution afterwards, surfactant concentration is obtained for 0.1 ~ 19 mM, 1,3- disubstituted maleimides compounds Concentration is 2 ~ 50 μM of detection liquid；And in detection liquid, for dissolving the molten of 1, the 3- disubstituted maleimides compound The 2% of the detection liquid product that the volume of agent is less than；It is the ultraviolet of 200 ~ 400 nm in wavelength after detecting that liquid stands 5 ~ 25 minutes Fluorescence intensity is observed under lamp from unstressed configuration to the mutation process of most hyperfluorescence, the Singularity detection at correspondence fluorescence intensity point of maximum intensity Surfactant concentration contained by solution is the critical micelle concentration of surfactant.
Alternatively, in above-mentioned S3, can also be and take what 1 ~ 10 mL S2. were prepared at 25 ~ 40 DEG C Sample liquid, is separately added into 11 volumetric flasks of 10 mL, then the storing solution prepared by S1 is added in each volumetric flask, Shake up, add diluted to scale, obtain 11 dilute respectively 0 times, 1 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 Again, 8 times, 9 times, the 10 times detection liquid of diluted concentration gradient（The selection of diluted concentration can be by those skilled in the art according to need It is adjusted）, in detection liquid, fluorescent chemicals concentration is 2 ~ 50 μM, for dissolving 1, the 3- disubstituted maleimides The 2% of the detection liquid product that the volume of the solvent of compound is less than；It is 200 ~ 400 in wavelength after detecting that liquid stands 10 min Fluorescence intensity is observed under the uviol lamp of nm from unstressed configuration to the mutation process of most hyperfluorescence, it is ensured that the concentration range of Fluorescence Mutation of A is most It is small, if without mutation process, continuing to prepare detection liquid between two concentration, until the concentration range of Fluorescence Mutation of A is minimum Untill, now correspond to surfactant concentration contained by Singularity detection solution at fluorescence intensity point of maximum intensity and be surfactant Critical micelle concentration.
When 1, the 3- disubstituted maleimides compound is configured to kit, preferably including following steps is carried out Detection：
S1., 1, the 3- disubstituted maleimides compound is configured to detect the kit of CMC with solvent, it is Fluoresceinated Concentration of the compound in liquid is detected is 2 ~ 50 μM；
S2. by surfactant diluent preparing to be measured into the sample liquid that concentration is 1 ~ 20 mM；
S3. at 25 ~ 40 DEG C, in the kit as obtained in S1, the sample liquid for adding different volumes to be prepared by S2, Scale is diluted to diluent, is shaken up, prepare surfactant concentration for 0.1 ~ 19mM, 1,3- disubstituted maleimides During compound concentration is 2 ~ 50 μM of detection liquid, and detection liquid, for dissolving 1, the 3- disubstituted maleimides compound Solvent volume be less than detection liquid product 2%；It is 200 ~ 400 nm's in wavelength after detecting that liquid stands 5 ~ 25 minutes Fluorescence intensity is observed under uviol lamp from unstressed configuration to the mutation process of most hyperfluorescence, catastrophe point inspection at correspondence fluorescence intensity point of maximum intensity Surfactant concentration contained by surveying solution is the critical micelle concentration of surfactant.
Alternatively, 11 fluorescence indicators of 10 mL volumetric flasks are contained for what is prepared in above-mentioned S1 Kit.
Alternatively, in above-mentioned S3, can also be to select and contain 11 10 mL capacity by what S1 was prepared The fluorescent reporter reagents box of bottle, at 25 ~ 40 DEG C, adds 1 ~ 10 mL to be prepared into by S2. in each 10 mL volumetric flask The surfactant samples liquid for arriving, is shaken up, and scale is diluted to diluent, is shaken up, and obtains 11 surfactant concentration difference It is that 0 times of sample liquid concentration, 1 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times of detection liquid are prepared by S2. （The selection of diluted concentration can be as needed adjusted by those skilled in the art）, and fluorescent chemicals concentration in detection liquid It it is 2 ~ 50 μM, for dissolving the detection liquid product that the volume of solvent of 1, the 3- disubstituted maleimides compound is less than 2%, fluorescence intensity will be observed in the case where wavelength is for the uviol lamp of 200 ~ 400 nm from unstressed configuration to most strong after detection liquid stands 10min The mutation process of fluorescence, it is ensured that the concentration range of Fluorescence Mutation of A is minimum, if without mutation process, between two concentration after It is continuous to prepare detection liquid, untill the concentration range minimum of Fluorescence Mutation of A, now correspond to catastrophe point inspection at fluorescence intensity point of maximum intensity Surfactant concentration contained by surveying solution is the critical micelle concentration of surfactant.
Preferably, the diluent is water, salting liquid or cushioning liquid；The salting liquid is sodium chloride-containing, potassium chloride, carbon Any one or a few solution in sour sodium, potassium carbonate, sodium phosphate, potassium phosphate；
The cushioning liquid is phosphoric acid and its sylvite or sodium salt, citric acid and its sylvite or sodium salt, carbonic acid and its sylvite Or any one in sodium salt, acetic acid and its sylvite or sodium salt, barbiturates and its sylvite or sodium salt, trishydroxymethylaminomethane Or several solution.
Preferably, the solvent is methyl alcohol, ethanol, tetrahydrofuran, dimethyl sulfoxide, DMF, acetonitrile, water One or more.
Preferably, the surfactant is anionic surfactant.
Preferably, the anionic surfactant is dodecyl sodium sulfate or lauryl sodium sulfate.
One kind 1,3- disubstituted maleimides compounds, with such as formula（Ⅰ）Shown structure：
（Ⅰ）
Wherein, R1Selected from the C of meta or para position substitution5~6Aromatic radical or non-substituted C9~18Polycyclic aromatic base；R1In, take Dai Jiwei C1~3Alkyl, C1~3Alkoxy first, halogen, cyano group or trifluoromethyl；
R2Selected from C1~8Chain fatty base, C6~8Ring-shaped fat base or with C5~6Aromatic rings or C5~6Aromatic heterocycle replaces The C of base1~4Chain fatty base；
And work as R1During for p-methylphenyl, R2It is not normal-butyl.
Preferably, R1Selected from p-methylphenyl, o-methyl-phenyl, p-fluorophenyl, rubigan, p-bromophenyl, a trifluoro Aminomethyl phenyl, p-methoxyphenyl, to cyano-phenyl, quinolyl；
R2Selected from normal-butyl, cyclohexyl, ethylthiophene base.
The preparation method of 1, the 3- disubstituted maleimides compound, comprises the following steps：
Following material consumption is calculated by mM number：
（1）In the organic solvent of 1 ~ 10mL, 1 part of formula is added（Ⅱ）Compound and 1 part of formula（Ⅲ）Compound, at 0 ~ 60 DEG C Lower stirring 10 ~ 60 minutes；
（2）In step（1）Reaction solution in add 4 ~ 6 parts of formula（Ⅳ）Compound, at 20 ~ 100 DEG C stir 18 hours ~ 2 days, isolate and purify and obtain 1, the 3- disubstituted maleimides compound；
The organic solvent is alcohol, benzene, toluene, hexane, halogenated hydrocarbons, ether, N,N-dimethylformamide, dimethyl sulfoxide or second One or more in nitrile.
The present invention has the advantages that compared with prior art：
1,3- disubstituted maleimides compound disclosed by the invention has aggregation-induced emission, can enrich for glimmering Light lights the classes of compounds that sonde method detects CMC of surfactant；1,3- disubstituted maleimides chemical combination of the present invention Analyte detection CMC sensitivity is high, and anionic surface activity can be preferably applied to than the known compound with similar performance The detection of agent CMC, has expanded the suitable application area that fluorescence lights sonde method；Method of the present invention provides one for practical application The method for planting simple, sensitive, quick measure CMC approximations, method of the method similar to pH approximations are determined with pH test paper, but There is sensitivity higher than pH test paper method, detection method of the invention with physical method --- electrical conductivity method measure come CMC value is closely.
Brief description of the drawings
Fig. 1 determines the principle schematic of CMC for the CMC assay methods for providing of the invention；
Fig. 2 is the kit quick detection anion surfactant dodecyl sulphur prepared with compound 1 in embodiment 1 The fluorogram of sour sodium CMC approximations；
Fig. 3 is approximate with the quick detection anionic CMC of compound 2 in embodiment 5 The fluorogram of value；
Fig. 4 is approximate with the quick detection anionic CMC of compound 9 in embodiment 12 The fluorogram of value；
Fig. 5 is approximate with the quick detection anion surfactant dodecyl sodium sulfate CMC of compound 1 in embodiment 3 The fluorogram of value；
Fig. 6 is approximate with the quick detection anion surfactant dodecyl sodium sulfate CMC of compound 2 in embodiment 15 The fluorogram of value；
Fig. 7 is to use physical method --- electrical conductivity method determines the result figure of Surfactant SDS CMC value；
Fig. 8 is to use physical method --- electrical conductivity method determines surfactant sodium dodecyl base sodium sulfonate CMC value at 40 DEG C Result figure.
Fig. 9 is that compound 1 is observed by what is obtained after recrystallization under 365nm uviol lamps（It is left）Under fluorescent light It was observed that（It is right）Crystal picture.
Specific embodiment
The present invention is further explained with reference to specific embodiment, but specific embodiment is not to the present invention It is limited in any way.Unless stated otherwise, reagent involved in embodiment, method are reagent and method commonly used in the art.
Embodiment 1
S1. by 1- butyl -3- para-totuidine base -2,5- diketone -1- hydrogen pyrroles（3-(p-tolylamino)-1-butyl- 1H-pyrrole-2,5-dione, compound 1）The storing solution that concentration is 2 mM is configured to ethanol.
Compound 1
S2. detection CMC kits are prepared.Concrete operations are：In 4 volumetric flasks of 10mL, it is separately added into by step S1 The μ L of storing solution 50 of preparation, it is 1,2,3, No. 4 bottles that 4 volumetric flasks containing fluorescence indicator are numbered respectively.
S3. in the volumetric flask of 100mL, 288 mg lauryl sodium sulfate are added（SDS）, plus distilled water is molten to sample Solution, carries out constant volume, so as to get concentration is the SDS sample liquids of 10 mM using distilled water.
S4. detected with the kit of the detection CMC prepared by step S2 and the SDS sample liquids for obtaining are prepared by step S3. Critical micelle concentration（critical micelle concentration, CMC）.Comprise the following steps that：
At 25 DEG C, the SDS sample liquids that S3. is prepared the step of take different volumes respectively by table 1 are in 4 prepared by step S2 In the kit of individual detection CMC, i.e., numbering is 4 containing the fluorescence indicator that 50 μ L concentration are 2mM 10 of 1,2,3 and No. 4 In mL volumetric flasks, shake up, then add distilled water to the graduation mark of each volumetric flask, 25min is stood after shaking up, be placed on 365 nm uviol lamps Lower observation fluorescence intensity, as shown in fig. 2, it can be seen that fluorescence intensity is mutated（From most hyperfluorescence to unstressed configuration）Corresponding SDS is dense Between 7.0 ~ 8.0mM, 7.0 to 7.5 fluorescence intensities substantially weaken degree scope, so the mM of fluorescence intensity catastrophe point 7.0 is The CMC value of SDS, close to the accurate CMC measured values determined with luminoscope（Table 5）And with physical method-electrical conductivity method survey it is accurate CMC value（Fig. 7）.
Table 1
Embodiment 2
S1. by 1- butyl -3- para-totuidine base -2,5- diketone -1- hydrogen pyrroles（3-(p-tolylamino)-1-butyl- 1H-pyrrole-2,5-dione, compound 1）The storing solution that concentration is 2 mM is configured to ethanol.
Compound 1
S2. in the volumetric flask of 100mL, 288 mg lauryl sodium sulfate are added（SDS）, plus distilled water is molten to sample Solution, carries out constant volume, so as to get concentration is the SDS sample liquids of 10 mM using distilled water.
S3. the fluorescence indicator storing solution and step S3. for being obtained with step S1. preparations are prepared the SDS sample liquids for obtaining and are matched somebody with somebody It is made for fluoroscopic examination SDS critical micelle concentrations（critical micelle concentration, CMC）Detection liquid. Comprise the following steps that：
At 25 DEG C, the SDS sample liquids that S2. is prepared the step of take different volumes respectively by table 2 are in 4 10 mL volumetric flasks In, then in each volumetric flask plus the μ L of fluorescence indicator storing solution 50 that prepare of step S1, plus distilled water is to the quarter of each volumetric flask Degree line, after standing 25min after shaking up, is placed under 365 nm uviol lamps and observes fluorescence intensity, as shown in fig. 2, it can be seen that fluorescence Intensity Abrupt（From most hyperfluorescence to unstressed configuration）Corresponding SDS concentration ranges are between 7.0 ~ 8.0 mM, and 7.0 to 7.5 fluorescence are strong Degree substantially weakens, so the mM of fluorescence intensity catastrophe point 7.0 is the CMC value of SDS, is surveyed close to the accurate CMC determined with luminoscope Definite value（Table 5）And the accurate CMC value surveyed with physical method-electrical conductivity method（Fig. 7）.
Table 2
Embodiment 3
S1. by 1- butyl -3- para-totuidine base -2,5- diketone -1- hydrogen pyrroles（3-(p-tolylamino)-1-butyl- 1H-pyrrole-2,5-dione, compound 1）The storing solution that concentration is 2mM is configured to ethanol.
Compound 1
S2. detection CMC kits are prepared.Concrete operations are：In 4 volumetric flasks of 10mL, it is separately added into by step S1 The μ L of storing solution 150 of preparation, it is 1,2,3, No. 4 bottles that 4 volumetric flasks containing fluorescence indicator are numbered respectively.
S3. in 40 DEG C of Water Tanks with Temp.-controlled, in the volumetric flask of 100mL, 544.7 mg dodecyl sodium sulfates are added （sodium dodecylsulfonate）, plus distilled water to sample dissolves, and carries out constant volume using distilled water, so as to get concentration is The dodecyl sodium sulfate sample liquid of 20 mM.
S4. detected with the kit of the detection CMC prepared by step S2 and the dodecyl sulphur for obtaining is prepared by step S3. The critical micelle concentration of sour sodium sample liquid（critical micelle concentration, CMC）.Comprise the following steps that：
In 40 DEG C of Water Tanks with Temp.-controlled, the dodecyl sodium sulfate sample that S3. is prepared the step of take different volumes respectively by table 3 In prepared by step S2 4 kits of detection CMC, i.e., numbering is 4 of 1,2,3 and No. 4 containing 150 μ L concentration to product liquid In for 10 mL volumetric flasks of the fluorescence indicator of 2mM, shake up, plus distilled water is to the graduation mark of each volumetric flask, shakes up standing 5min Afterwards, it is placed under 365 nm uviol lamps and observes fluorescence intensity, as shown in Figure 4, it can be seen that fluorescence intensity is mutated（From most hyperfluorescence To unstressed configuration）Corresponding dodecyl sodium sulfate concentration range is between 10.5 ~ 13.0 mM, and 10.5 to 11.0 fluorescence intensities are bright It is aobvious to weaken, so the mM of fluorescence intensity catastrophe point 10.5 is the CMC value of SDS, determined close to the accurate CMC determined with luminoscope Value（Table 6）And the accurate CMC value surveyed with physical method-electrical conductivity method（Fig. 8）.
Table 3
Embodiment 4
S1. by 1- butyl -3- para-totuidine base -2,5- diketone -1- hydrogen pyrroles（3-(p-tolylamino)-1-butyl- 1H-pyrrole-2,5-dione, compound 1）The storing solution that concentration is 2mM is configured to ethanol.
Compound 1
S3. in 40 DEG C of Water Tanks with Temp.-controlled, in the volumetric flask of 100mL, 544.7 mg dodecyl sodium sulfates are added （sodium dodecylsulfonate）, plus distilled water to sample dissolves, and carries out constant volume using distilled water, so as to get concentration is The dodecyl sodium sulfate sample liquid of 20 mM.
S3. the fluorescence indicator storing solution and step S3. for being obtained with step S1. preparations prepare the dodecyl sulphur for obtaining Sour sodium sample liquid is configured to for fluoroscopic examination dodecyl sodium sulfate critical micelle concentration（critical micelle concentration, CMC）Detection liquid.Comprise the following steps that：
In 40 DEG C of Water Tanks with Temp.-controlled, the dodecyl sodium sulfate sample that S2. is prepared the step of take different volumes respectively by table 4 Product liquid in 4 10 mL volumetric flasks, then in each volumetric flask plus step S1 prepare the μ L of fluorescence indicator storing solution 150, Plus distilled water is to the graduation mark of each volumetric flask, after shaking up standing 5min, it is placed under 365 nm uviol lamps and observes fluorescence intensity, such as schemes Shown in 4, it can be seen that fluorescence intensity is mutated（From most hyperfluorescence to unstressed configuration）The concentration range of corresponding dodecyl sodium sulfate Between 10.5 ~ 13.0mM, 10.5 to 11.0 fluorescence intensities substantially weaken, so fluorescence intensity catastrophe point 10.5mM is 12 The CMC value of sodium alkyl sulfonate, close to the accurate CMC measured values determined with luminoscope（Table 6）And surveyed with physical method-electrical conductivity method Accurate CMC value（Fig. 8）.
Table 4
Embodiment 5 ~ 14
Embodiment 5 ~ 14 determines anionic（SDS）Critical micelle concentration（CMC）'s Method only changes the compound 1 of aggregation-induced emission in embodiment 1 or 2 into corresponding formula with embodiment 1 or 2（Ⅰ）Its Its compound 2 ~ 11.Table 5 lists the structure of compound 1 ~ 11, anionic（SDS）'s Critical micelle concentration（CMC）Compound concentration, time of repose, temperature of the measurement etc. in accurate measured value, detection liquid.
Formula（Ⅰ）
Table 5
aThe CMC value accurately determined with luminoscope.
Embodiment 15 ~ 24
Embodiment 15 ~ 24 determines anion surfactant dodecyl sodium sulfate critical micelle concentration（CMC）Method With embodiment 3 or 4, only the compound 1 of aggregation-induced emission in embodiment 3 or 4 is changed into corresponding formula（Ⅰ）Other compounds 2~11.Table 7 lists the structure of compound 1 ~ 11, the critical micelle concentration of anion surfactant dodecyl sodium sulfate （CMC）Compound concentration, time of repose, temperature of the measurement etc. in accurate measured value, detection liquid.
Formula（Ⅰ）
Table 6
aThe CMC value accurately determined with luminoscope.
Embodiment 25
（1）The para-totuidine of the dimethyl butyn of 1mmol (142mg), 1mmol (107mg) is added sequentially to In 2mL ethanol, 20min is stirred under room.
（2）In step（1）Reaction solution in add 4mmol (292mg) n-butylamine, after being stirred at room temperature 18 hours, Saturated sodium-chloride water solution 20mL is added, is extracted with dichloromethane 20mL, in triplicate, the dichloromethane solution of merging, then use Saturated sodium-chloride water solution 20mL is extracted, and in triplicate, gained dichloromethane solution is dried with magnesium sulfate, and vacuum distillation is except molten Agent, then with thin chromatoplate purified product is prepared, solvent is n-hexane+ethyl acetate（10:1）, eluant, eluent is ethyl acetate, is used Vacuum revolving method removes solvent, finally gives the compound 1 of 194mg.Fig. 9 is compound by being obtained after recrystallization Observed under 365nm uviol lamps（It is left）Observe under fluorescent light（It is right）Crystal picture.
1- butyl -3- para-totuidine base -2,5- diketone -1- hydrogen pyrroles（3-(p-tolylamino)-1-butyl-1H- Pyrrole-2,5-dione, compound 1）；Yield 75%, yellow solid, fusing point=145.5-145.7 DEG C;IR (KBr):ν max = 3470,3102,3020,2972,1696,1646,1370,1061,770 CM-1; 1H NMR (400 MHz, CDCl3) δ = 7.14 (dd, J=62.6, 7.9, 4H), 5.45 (s, 1H), 3.55 (t, J=7.2, 2H), 2.37 (s, 3H), 1.61 (d, J=7.5, 2H), 1.36 (d, J=7.5, 2H), 0.96 (t, J=7.3, 3H) ppm;13C NMR (101 MHz, CDCl3) δ = 172.83, 168.24, 142.50, 135.84, 134.28, 130.19, 118.71, 88.21, 37.61, 30.69, 20.78, 19.96, 13.56 ppm; MS (ESI): m/z 259(M + H+, 17).
Embodiment 26
（1）The meta-aminotoluene of the dimethyl butyn of 1mmol (142mg), 1mmol (107mg) is added sequentially to In 1mL DMFs, 10min is stirred under room.
（2）In step（1）Reaction solution in add 5mmol (365mg) n-butylamine, after being stirred at room temperature 20 hours, Plus saturated sodium-chloride water solution 20mL, with dichloromethane 20mL extract, in triplicate, the dichloromethane solution of merging, then with satisfy With sodium-chloride water solution 20mL extractions, in triplicate, gained dichloromethane solution is dried with magnesium sulfate, and vacuum distillation removes solvent, Again with thin chromatoplate purified product is prepared, solvent is n-hexane+ethyl acetate（10:1）, eluant, eluent is ethyl acetate, with true Empty revolving method removes solvent, finally gives the compound 2 of 180mg.
1- butyl -3- meta-aminotoluenes base -2,5- diketone -1- hydrogen pyrroles（3-(m-tolylamino)-1-butyl-1H- Pyrrole-2,5-dione, compound 2）；Yield 70%, yellow solid, fusing point=129.6-129.8 DEG C;IR (KBr):ν max = 3445,3304,2962,1756,1692,1626,1438,1230,777,606 CM-1; 1H NMR (400 MHz, CDCl3) δ = 7.29 (d, J=6.2, 1H), 6.99 (d, J=4.8, 3H), 5.51 (s, 1H), 3.56 (t, J =7.2, 2H), 2.39 (s, 3H), 1.67 – 1.59 (m, 2H), 1.36 (dd, J=15.2, 7.5, 2H), 0.96 (t, J=7.4, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ = 172.71, 167.99, 142.35, 135.92, 134.17, 130.16, 130.02, 124.38, 118.69, 88.23, 44.88, 42.59, 38.61, 20.78, 19.18 ppm.MS (ESI): m/z 259 (M + H+,17).
Embodiment 27
（1）The para-bromoaniline of the dimethyl butyn of 1mmol (142mg), 1mmol (170mg) is added sequentially to In 3mL methyl alcohol, 1h is stirred under room.
（2）In step（1）Reaction solution in add 6mmol (438mg) n-butylamine, after being stirred at room temperature 19 hours, Plus saturated sodium-chloride water solution 20mL, with dichloromethane 20mL extract, in triplicate, the dichloromethane solution of merging, then with satisfy With sodium-chloride water solution 20mL extractions, in triplicate, gained dichloromethane solution is dried with magnesium sulfate, and vacuum distillation removes solvent, Again with thin chromatoplate purified product is prepared, solvent is n-hexane+ethyl acetate（10:1）, eluant, eluent is ethyl acetate, with true Empty revolving method removes solvent, finally gives the compound 3 of 225mg.
1- butyl -3- para-bromoaniline base -2,5- diketone -1- hydrogen pyrroles（3-(4-bromophenylamino)-1-butyl- 1H-pyrrole-2,5-dione, compound 3）；Yield 70%, yellow solid, fusing point=212.2-212.6 DEG C;IR (KBr):ν max =3306,3125,3062,2857,1756,1686,1638,1449,1377,846,704 CM-1; 1H NMR (400 MHz, CDCl3) δ = 7.53 (d, J=8.6, 2H), 7.05 (d, J=8.6, 2H), 5.49 (s, 1H), 3.56 (t, J=7.2, 2H), 1.61 (dd, J=14.7, 7.5, 3H), 1.44 – 1.25 (m, 2H), 0.96 (t, J= 7.3, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ = 172.43, 168.06, 141.86, 137.52, 132.72, 120.14, 117.10, 89.62, 37.72, 30.63, 19.94, 13.55 ppm.MS (ESI): m/z 322 (M + H+,100), 324 (100).
Embodiment 28
（1）The para-fluoroaniline of the dimethyl butyn of 1mmol (142mg), 1mmol (111mg) is added sequentially to In 3mL n-hexanes, 1h is stirred under room.
（2）In step（1）Reaction solution in add 6mmol (438mg) n-butylamine, after being stirred at room temperature 24 hours, Plus saturated sodium-chloride water solution 20mL, with dichloromethane 20mL extract, in triplicate, the dichloromethane solution of merging, then with satisfy With sodium-chloride water solution 20mL extractions, in triplicate, gained dichloromethane solution is dried with magnesium sulfate, and vacuum distillation removes solvent, Again with thin chromatoplate purified product is prepared, solvent is n-hexane+ethyl acetate（10:1）, eluant, eluent is ethyl acetate, with true Empty revolving method removes solvent, finally gives the compound 4 of 178mg.
1- butyl -3- para-fluoroaniline base -2,5- diketone -1- hydrogen pyrroles（3-(4-fluorophenylamino)-1- Butyl-1H-pyrrole-2,5-dione, compound 4）；Yield 68%, yellow solid, fusing point=174.6-174.7 DEG C;IR (KBr):ν max =3312,3144,3122,2965,1749,1686,1638,1445,1067,826,699 CM-1; 1H NMR (400 MHz, CDCl3) δ = 7.22 – 7.02 (m, 4H), 5.43 (s, 1H), 3.74 – 3.37 (m, 2H), 1.61 (dd, J=14.6, 6.9, 3H), 1.35 (dt, J=14.8, 7.3, 2H), 1.12 – 0.76 (m, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ = 172.61, 168.09, 160.60, 142.65, 134.53, 120.51, 116.67, 116.44, 88.41, 37.67, 30.65, 19.95, 13.55 ppm.MS (ESI): m/z 263 (M + H+,16).
The synthetic method of example 2 below 9-35 is identical with embodiment 27, and difference is that substituted for corresponding raw material.
Embodiment 29
1- butyl -3- parachloroanilinum base -2,5- diketone -1- hydrogen pyrroles（3-(4-chlorophenylamino)-1- Butyl-1H-pyrrole-2,5-dione, compound 5）；Yield 65%, yellow solid, fusing point=192.4-192.7 DEG C;IR (KBr):ν max =3307,3125,2972,1758,1686,1635,1448,1065,819,704,663 CM-1; 1H NMR (400 MHz, CDCl3) δ = 7.39 (d, J=7.9, 2H), 7.11 (d, J=8.0, 2H), 5.48 (s, 1H), 3.56 (t, J=7.1, 2H), 1.61 (dd, J=14.7, 7.2, 2H), 1.43 – 1.28 (m, 2H), 0.96 (t, J=7.3, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ = 172.45, 168.06, 137.02, 129.69, 119.84, 89.43, 37.71, 30.63, 19.94, 13.54 ppm.MS (ESI): m/z 279 (M + H+,15).
Embodiment 30
1- butyl -3- are to cyano-aniline base -2,5- diketone -1- hydrogen pyrroles（3-(4-cyanphenylamino)-1- Butyl-1H-pyrrole-2,5-dione, compound 6）；Yield 20%, faint yellow solid, fusing point=196.9-197.3 DEG C;IR (KBr):ν max =3445,3308,2956,2223,1765,1689,1635,1541,1444,1371,1170,685 CM-1;1H NMR (400 MHz, CDCl3) δ = 7.72 (d, J=8.1, 2H), 7.23 (d, J=8.2, 2H), 5.65 (s, 1H), 3.58 (t, J=7.0, 2H), 1.61 (d, J=11.1, 3H), 1.36 (dd, J=14.7, 7.3, 2H), 0.96 (t, J=7.2, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ = 142.33, 133.90, 118.29, 107.16, 92.33, 37.88, 30.56, 19.92, 13.52 ppm.MS (ESI): m/z 270 (M + H+,17).
Embodiment 31
1- butyl -3- m-benzotrifluorides amido -2,5- diketone -1- hydrogen pyrroles（3-(3-(trifluoromethyl) Phenylamino) -1-butyl-1H-pyrrole-2,5-dione, compound 7）；Yield 40%, yellow solid, fusing point= 137.3-137.6℃;IR (KBr):ν max =3418,3310,2965,1755,1688,1628,1553,1453,1334, 1126,1068,693 CM-1; 1H NMR (400 MHz, CDCl3) δ = 7.56 (t, J=7.9, 1H), 7.43 (d, J =6.9, 2H), 7.36 (s, 1H), 5.58 (s, 1H), 3.58 (t, J=7.2, 2H), 1.65 – 1.57 (m, 3H), 1.44 – 1.23 (m, 2H), 0.96 (t, J=7.3, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ = 141.65, 130.37, 121.52, 120.86, 115.27, 90.42, 37.79, 30.61, 19.93, 13.54 ppm. MS (ESI): m/z 313 (M + H+,18).
Embodiment 32
1- butyl -3- are to anisidino -2,5- diketone -1- hydrogen pyrroles（3-(4-methoxyphenylamino)-1- Butyl-1H-pyrrole-2,5-dione, compound 8）；Yield 50%, dark yellow solid, fusing point=153.5-153.7 DEG C;IR (KBr):ν max =3309,3159,3131,3071,2954,1748,4694,1639,1454,1374,1249,1069,812, 695 CM-1; 1H NMR (400 MHz, CDCl3) δ = 7.14 – 6.93 (m, 4H), 5.38 (s, 1H), 3.84 (s, 3H), 3.66 – 3.47 (m, 2H), 1.61 (dd, J=17.8, 10.4, 2H), 1.46 – 1.27 (m, 2H), 0.96 (t, J=7.3, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ = 120.48, 114.91, 87.23, , 55.51, 37.58, 30.70, 19.96, 13.57.MS (ESI): m/z 275 (M + H+,17).
Embodiment 33
1- butyl -3-（8- amido quinolyls）- 2,5- diketone -1- hydrogen pyrroles（1-butyl-3-(quinolin-8- ylamino)-1H-pyrrole-2,5-dione）, compound 9）；Yield 13%, yellow solid, fusing point=114.6-114.8 DEG C; IR (KBr):ν max=3297,3134,2951,1761,1699,1638,1530,1486,1377,1034,822,688,622 CM-1; 1H NMR (400 MHz, CDCl3) δ = 8.93 (s, 1H), 8.24 (d, J=8.3, 1H), 7.77 – 7.40 (m, 3H), 7.43 (d, J=6.8, 1H), 5.73 (s, 1H), 3.62 (t, J=7.1, 2H), 2.03 (s, 1H), 1.75 – 1.59 (m, 2H), 1.39 (dd, J=14.9, 7.5, 2H), 0.98 (t, J=7.3, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ = 172.97, 148.82, 141.03, 139.08, 136.15, 135.17, 128.28, 126.79, 122.31, 121.79, 113.14, 90.50, 37.64, 30.70, 19.96, 13.58.MS (ESI): m/z 296 (M + H+,19).
Embodiment 34
1- cyclohexyl -3- para-totuidine base -2,5- diketone -1- hydrogen pyrroles（3-(p-tolylamino)-1- cyclohexyl-1H-pyrrole-2,5-dione）, compound 10）；Yield 25%, yellow solid, fusing point=154.4-154.6 ℃;IR (KBr):ν max =3446,3109,3056,3040,2928,1758,1690,1628,1465,1453,1376,1164, 1101,772,714 CM-1; 1H NMR (400 MHz, CDCl3) δ = 7.21 (d, J=8.2, 2H), 7.05 (d, J =8.4, 2H), 5.42 (s, 1H), 3.95 (s, 1H), 2.37 (s, 3H), 2.09 (dd, J=12.4, 3.3, 2H), 1.86 (d, J=13.3, 2H), 1.72 (d, J=10.5, 3H), 1.43 – 1.13 (m, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ = 172.83, 168.01, 142.27, 135.91, 134.16, 130.17, 118.67, 99.93, 88.16, 50.41, 30.02, 25.91, 25.05, 20.77 ppm.MS (ESI): m/z 285 (M + H+,19).
Embodiment 35
1- (2 acetyl thiophene base) -3- para-totuidine base -2,5- diketone -1- hydrogen pyrroles（3-(p-tolylamino)-1- (2-(thiophen-2-yl)ethyl)-1H-pyrrole-2,5-dione）, compound 11）；Yield 40%, yellow solid melts Point=190.1-190.5 DEG C;IR (KBr):ν max =3319,3129,1756,1694,1632,1448,1379,780,700,620 CM-1; 1H NMR (400 MHz, CDCl3) δ = 7.23 – 7.15 (m, 4H), 7.06 (d, J=8.4, 2H), 6.95 (dd, J=5.1, 3.4, 1H), 6.88 (dd, J=3.4, 0.8, 1H), 5.46 (s, 1H), 3.91 – 3.74 (m, 2H), 3.19 (t, J=7.3, 2H), 2.37 (s, 3H), 1.61 (s, 1H) ppm. 13C NMR (101 MHz, CDCl3) δ = 172.37, 167.93, 142.53, 140.10, 135.74, 134.40, 130.21, 126.91, 125.52, 124.03, 118.75, 88.27, 39.20, 28.69, 20.79 ppm.MS (ESI): m/z 313 (M + H+,19).
With maleimide Surfactant SDS and dodecyl sodium sulfate are determined as fluorescence probe The result of CMC value, the result with the CMC value determined with physical method-electrical conductivity method is basically identical, represents probe in itself to CMC The measure of value does not influence, and than general organic fluorescence probe, including pyrene, the CMC value of measure is truer, accurate.
The CMC fluorescence probes that the present invention is provided are to determine CMC value by the catastrophe point of fluorescence most strength, are that fluorescence is lighted Probe, closing probe than fluorescence has sensitivity higher.Being at present can be by uviol lamp quick detection CMC and for preparing Detect that the Equations of The Second Kind fluorescence of CMC kits lights probe, compared with five substituted-tetrahydro pyrimidine compound probes were found before us, With the different surfactant scope of application, and measured value is closer to the CMC value of physics Means of Electrical Conductivity.

Claims (8)

  1. Application of 1.1, the 3- disubstituted maleimides compounds in as critical micelle concentration of surfactant fluorescence probe, Characterized in that, the surfactant is anion surfactant, 1, the 3- disubstituted maleimides compound tool Just like formula（Ⅰ）Shown structure：
    Wherein, R1Selected from the C of meta or para position substitution5~6Aromatic radical or non-substituted C9~18Polycyclic aromatic base；R1In, take Dai Jiwei C1~3Alkyl, C1~3Alkoxy, halogen, cyano group or trifluoromethyl；
    R2Selected from C1~8Chain fatty base, C6~8Ring-shaped fat base or 2 acetyl thiophene base.
  2. 2. applied according to claim 1, it is characterised in that 1, the 3- disubstituted maleimides compound is prepared Into fluorescence indicator or kit.
  3. 3. applied according to claim 2, it is characterised in that match somebody with somebody when 1, the 3- disubstituted maleimides compound When being made fluorescence indicator, comprise the following steps：
    S1. the 1,3- disubstituted maleimides compound is configured to the storing solution that concentration is 2 ~ 5mM with solvent；
    S2. by surfactant diluent preparing to be measured into the sample liquid that concentration is 1 ~ 20 mM；
    S3. at 25 ~ 40 DEG C, the surfactant samples liquid prepared by step S2. of different volumes is added in different appearances In measuring bottle, then the fluorescence indicator storing solution that addition same volume is prepared by step S1. in each volumetric flask, then adopt Constant volume is carried out with dilution, surfactant concentration is obtained for 0.1 ~ 19 mM, 1,3- disubstituted maleimides compound concentrations It is 2 ~ 50 μM of detection liquid；And in detection liquid, the solvent for dissolving 1, the 3- disubstituted maleimides compound The 2% of the detection liquid product that volume is less than, is the uviol lamp of 200 ~ 400 nm in wavelength after detection liquid is stood into 5 ~ 25 minutes , from unstressed configuration to the mutation process of most hyperfluorescence, correspondingly the Singularity detection at fluorescence intensity point of maximum intensity is molten for lower observation fluorescence intensity Surfactant concentration contained by liquid is the critical micelle concentration of surfactant.
  4. 4. applied according to claim 2, it is characterised in that match somebody with somebody when 1, the 3- disubstituted maleimides compound When being made kit, comprise the following steps：
    S1., 1, the 3- disubstituted maleimides compound is configured to detect the kit of CMC, fluorescence chemical combination with solvent Concentration of the thing in liquid is detected is 2 ~ 50 μM；
    S2. by surfactant diluent preparing to be measured into the sample liquid that concentration is 1 ~ 20 mM；
    S3. at 25 ~ 40 DEG C, in the kit for detecting CMC as obtained in S1, different volumes are added to be prepared by S2 Surfactant samples liquid, be diluted to scale with diluent, shake up, prepare surfactant concentration for 0.1 ~ 19mM, During 1,3- disubstituted maleimides compound concentration is 2 ~ 50 μM of detection liquid, and detection liquid, for dissolving described 1,3- The 2% of the detection liquid product that the volume of the solvent of disubstituted maleimides compound is less than, 5 ~ 25 minutes are stood by detection liquid Afterwards, fluorescence intensity is observed in the case where wavelength is for the uviol lamp of 200 ~ 400 nm from unstressed configuration to the mutation process of most hyperfluorescence, correspondence Surfactant concentration contained by Singularity detection solution is the critical micelle concentration of surfactant at fluorescence intensity point of maximum intensity.
  5. 5. applied according to claim 3 or 4, it is characterised in that the diluent is water, salting liquid or cushioning liquid；Institute It is any one or a few molten in sodium chloride-containing, potassium chloride, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate to state salting liquid Liquid；The cushioning liquid is phosphoric acid and its sylvite or sodium salt, citric acid and its sylvite or sodium salt, carbonic acid and its sylvite or sodium In salt, acetic acid and its sylvite or sodium salt, barbiturates and its sylvite or sodium salt, trishydroxymethylaminomethane any one or it is several The solution planted.
  6. 6. applied according to claim 3 or 4, it is characterised in that the solvent is methyl alcohol, ethanol, tetrahydrofuran, diformazan Asia One or more of sulfone, N,N-dimethylformamide, acetonitrile, water.
  7. 7. one kind 1,3- disubstituted maleimides compounds, it is characterised in that 1, the 3- disubstituted maleimides chemical combination Thing has claim 1 formula（1）Shown structure, R1Selected from p-methylphenyl, o-methyl-phenyl, p-fluorophenyl, rubigan, P-bromophenyl, m-trifluoromethylphenyl, p-methoxyphenyl, to cyano-phenyl, quinolyl；R2Selected from normal-butyl, cyclohexyl, Ethylthiophene base；And R1During for p-methylphenyl, R2It is not normal-butyl.
  8. 8. the preparation method of 1,3- disubstituted maleimides compound described in claim 7, it is characterised in that including as follows Step：Following material consumption is calculated by mM number：
    （1）In the organic solvent of 1 ~ 10mL, 1 part of formula is added（Ⅱ）Compound and 1 part of formula（Ⅲ）Compound, at 0 ~ 60 DEG C Lower stirring 10 ~ 60 minutes；
    （2）In step（1）Reaction solution in add 4 ~ 6 parts of formula（Ⅳ）Compound, stirs 18 hours ~ 2 at 20 ~ 100 DEG C My god, isolate and purify and obtain 1, the 3- disubstituted maleimides compound；
    The organic solvent is in alcohol, benzene, toluene, hexane, halogenated hydrocarbons, ether, N,N-dimethylformamide, dimethyl sulfoxide or acetonitrile One or more.
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