CN101279939A - Synthetic method of 8,8'-2- phenylamino-5,5'2-naphthyl-1,1'-2-sulphonate - Google Patents
Synthetic method of 8,8'-2- phenylamino-5,5'2-naphthyl-1,1'-2-sulphonate Download PDFInfo
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- CN101279939A CN101279939A CNA2008100381972A CN200810038197A CN101279939A CN 101279939 A CN101279939 A CN 101279939A CN A2008100381972 A CNA2008100381972 A CN A2008100381972A CN 200810038197 A CN200810038197 A CN 200810038197A CN 101279939 A CN101279939 A CN 101279939A
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Abstract
The invention relates to a method to synthesize 8,8`-2-phenylamino-5,5`-2- naphthyl-1,1`2- sulfonate(bis-ANS) which is used as protein fluorescent probe in biological engineering field. The method takes alkyl-imidazole and alkyl halide as material and 1,1,1-trichloroethane as solvent; the phegma is stirred for reaction to get corresponding imidazole cation solution; after that 8-anilino-1-naphthalenesulfonic acid(ANS), as material, reacts with potassium hydroxide to produce 8-anilino-1-naphthalenesulfonic potassium; under the catalysis of hydrochloric acid and sodium nitrite, the imidazole cation solution is mixed with acetone to be used as solvent and the reaction begins under reflux temperature; after the reaction, the products are separated through silica gel column, obtaining 8,8`-2-phenylamino-5,5`-2- naphthyl-1,1`2- sulfonate(bis-ANS), with a yield up to 26%.
Description
Technical field
The present invention relates to a kind of synthetic method of protein fluorescence probe of technical field of bioengineering, be specifically related to a kind of 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate synthetic method.
Background technology
Fluorescent probe technique is to utilize the optical physics and the photochemical properties of material, protein high-sensitivity analysis method in the research solution on molecular level.The protein molecule fluorescent probe can be divided into fluorescent probe and the near infrared fluorescent probe that is transmitted in the UV, visible light district by wavelength of fluorescence.
8-anilino-1-naphthalene sulfonic acid salt (ANS) is most widely used in the protein molecule UV, visible light region probe always.Studies show that, ANS combines with protein is non-covalent at human hemoglobin center cavity 2DPG2 binding site, the hydrophobic interaction mechanism that its combination is based on protein molecule is attached in the apolar regions of protein molecule with non covalent bond, make protein fluorescence intensity greatly strengthen, within the specific limits, fluorescence intensity and proteinic concentration are linear.Discovered the dicyclic compound of ANS afterwards: 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate (bis-ANS) and protein molecule bonded be firm stable more, and binding substances has more wide in range fluorescent absorption spectrum.Therefore, use in the research in protein molecule fluorescent probe field for bis-ANS is the focus of biology and organic chemistry filed always.
Since the eighties in 20th century, that reported in the document is a lot of about the bis-ANS synthetic method.More early stage aluminum chloride, cupric chloride catalytic coupling method are arranged, nitric acid, hydrochloric acid/Sodium Nitrite catalysis synthesis process, thallium metal catalytic oxidation dehydrogenation coupling method, and the electrochemical oxidation process of development on this basis etc.Mechanism that it is generally acknowledged this reaction is the reaction of coupling certainly (self-couple reaction) of aromatic cycle compound, relates to radical reaction mechanism.
Find through literature search prior art, the article " Preparation; Crystalline Structure; andSpectral Properties of the Fluorescent Probe4; 4 '-Bis-1-phenylamino-8-naphthalenesulfonate " that F J Farris etc. delivers on " Journal of the AmericanChemical Society ", (JACS, the 4469th page of 1978 the 100th phases the 14th volume, " fluorescent probe 4; preparation of 4 '-two-1-phenylamino-8-naphthalenesulfonate, crystalline structure and spectral quality ").Propose in this article with the synthetic fluorescent probe 4 of hydrochloric acid/Sodium Nitrite catalysis, the method for 4 '-two-1-phenylamino-8-naphthalene sulfonic acid potassium), concrete grammar is: 8-anilino-1-naphthalene sulfonic acid (ANS) is that raw material and potassium hydroxide reaction make 8-anilino-1-naphthalene sulfonic acid potassium; Under concentrated hydrochloric acid and Sodium Nitrite catalysis,, to react under sour environment as reaction solvent with hydrochloric acid, separation obtained product 8 through silicagel column after reaction finished, 8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate, productive rate is up to 10%.Its deficiency is: the solvability of this reaction raw materials 8-anilino-1-naphthalene sulfonic acid salt is very poor in common organic solvents, so productive rate is very low.
Ionic liquid is meant in room temperature or near presenting salt liquid, that be made up of zwitterion fully under the room temperature, is also referred to as watery fusion salt.Ionic liquid at room temperature is owing to its unique physical and chemical properties obtains the extensive concern of countries in the world chemist, and it is considered to " new generation of green solvent " after supercritical co.Because ionic liquid has high resolution (reaction that is difficult to finish during especially suitable common organic liquid phase is synthetic); But special performances such as reuse, at present, ionic liquid has been applied in the broad variety reaction as reaction solvent.For example: hydrogenation; Fu-Ke reaction; The Heck reaction; Diels-Alder reaction or the like.
Summary of the invention
The objective of the invention is to the deficiency that exists at prior art, a kind of protein fluorescence probe bis-ANS synthetic method is provided, promptly 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1, the chemical synthesis process of 1 '-two-sulfonate (bis-ANS).The present invention utilizes ion liquid characteristic, adopt the solvent of several white capable synthetic glyoxaline cation class ionic liquids as reaction, solve reaction raw materials 8-anilino-1-naphthalene sulfonic acid salt poorly soluble problem in ordinary organic solvents, improved the bis-ANS productive rate.
The present invention is achieved by the following technical solutions, and the present invention is a raw material with alkyl imidazole, haloalkane, does reaction solvent with 1, and the stirring and refluxing reaction obtains corresponding glyoxaline cation class ionic liquid.Be that raw material and potassium hydroxide reaction make 8-anilino-1-naphthalene sulfonic acid potassium with 8-anilino-1-naphthalene sulfonic acid (ANS) then, under hydrochloric acid and Sodium Nitrite catalysis, mix as reaction solvent with acetone with synthetic glyoxaline cation class ionic liquid, react under the reflux temperature, separation obtained product 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1 through silicagel column after reaction finished, 1 '-two-sulfonate (bis-ANS), productive rate is up to 26%.
The present invention includes following synthesis step:
The first step, the ion liquid synthetic preparation of glyoxaline cation class:
To get alkyl imidazole and haloalkane is raw material, is solvent with the 1, and back flow reaction gets glyoxaline cation class ionic liquid product.
In the described the first step, concrete parameter is:
Alkyl imidazole and haloalkane are with 1: the 1.0-1.5 molar ratio mixes, and is dissolved in the 20-30 times of volume ratio 1 stirring and refluxing reaction 2-4 hour.With separating funnel product is separated while hot, use the 1 washed twice again, get product behind the rotary evaporation solvent.
Gained glyoxaline cation class ionic liquid product is respectively:
1, iodate 1,3-dimethyl-imidazoles (MMIMI
-), 2, bromination 1-ethyl-3-Methylimidazole (EMIMBr
-), 3, bromination 1-propyl group-3-Methylimidazole (PMIMBr
-), 4, chlorination 1-butyl-3-Methylimidazole (BMIMCl
-), 5, bromination 1,3-diethyl imidazoles (EEIMBr
-), 6, bromination 1-propyl group-3-ethyl imidazol(e) (PEIMBr
-), 7, chlorination 1-butyl-3-ethyl imidazol(e) (BEIMCl
-).
Second step, 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-potassium sulfonate synthetic:
With 8-anilino-1-naphthalene sulfonic acid (ANS) is the sylvite that raw material and potassium hydroxide reaction make ANS, with this sylvite under concentrated hydrochloric acid and Sodium Nitrite catalysis, mix the back with acetone as reaction solvent with synthetic glyoxaline cation class ionic liquid, react under the reflux temperature, separation obtained product through silicagel column after reaction finished.
In described second step, be implemented as follows:
Step 1,8-anilino-1-naphthalene sulfonic acid and potassium hydroxide molar ratio are 1: 1, are dissolved in the water to heat up and stirring, are cooled to room temperature afterwards and slowly separate out crystallization, collect also and obtain 8-anilino-1-naphthalene sulfonic acid sylvite behind the recrystallization;
Step 2, at room temperature, 8-anilino-1-naphthalene sulfonic acid sylvite is dissolved in the acetone of 20-30 times of mass ratio, add the first step synthetic glyoxaline cation class ionic liquid, add hydrochloric acid under vigorous stirring, the question response thing slowly drips sodium nitrite solution after being cooled to room temperature, heat up and the control solvent refluxing, stoichiometric number hour, reactant is cooled to room temperature, and top acetone layer is poured out;
Step 3, ionic liquid with acetone rinsing remnants, merge acetone soln and adjust the pH value with saturated sodium bicarbonate solution, concentrating under reduced pressure obtains blackish green pressed powder, be 8-anilino-1-naphthalene sulfonic acid potassium and 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1, the mixture of 1 '-two-potassium sulfonate and small amounts of inorganic salt;
Step 4, with said mixture by column chromatography, with acetone with make eluent after ethyl acetate is mixed according to volume ratio at 1: 1, separation obtaining product 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-potassium sulfonate (bis-ANS).
In the step 1, described intensification, its temperature is 40 ℃～60 ℃.
In the step 2, described hydrochloric acid is meant that volumetric concentration is 36% concentrated hydrochloric acid.
In the step 2, described sodium nitrite solution, its concentration is 0.2 mol sodium nitrite solution.
In the step 2, described intensification and control solvent refluxing, its temperature is 60 ℃～80 ℃.
In the step 3, described adjustment pH value is meant and regulates the pH value to 7-9.
The present invention is directed to 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1, the low problem of 1 '-two-potassium sulfonate (bis-ANS) synthetic yield, adopt voluntarily synthetic glyoxaline cation class ionic liquid as reaction solvent, compared with the prior art, solved the problem that causes productive rate low (productive rate＜3%) in the synthetic method in the past because of the reactant indissoluble, and productive rate has been brought up to more than 20%.Simultaneously, this synthetic method has been simplified reactions steps relatively and has been made aftertreatment easier; Ionic liquid as solvent can be reused, and has also embodied the Green Chemistry environmental protection ideas.This synthetic method has optimized 8 preferably, 8 '-two-phenylamino-5, and 5 '-two-naphthyl-1, the operational path of 1 '-two-potassium sulfonate (bis-ANS) is for suitability for industrialized production provides technical support.
Embodiment
Below embodiments of the invention are elaborated: present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.
The following embodiment of the present invention implements according to following steps:
The first step, the ion liquid synthetic preparation of glyoxaline cation class
Under the room temperature, alkyl imidazole is dissolved in the 1, the haloalkane after the new distillation of normal pressure adds in the reactant, is warming up to reflux temperature (70-80 ℃), keeps this temperature stirring reaction 2-4 hour.Reaction finishes, while hot with separating funnel with the product layering, collect the product part of lower floor; Use 1 20ml * 2 washed twice again, will get glyoxaline cation class ionic liquid product behind the evaporated under reduced pressure solvent under the product part room temperature.
Second step, 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-potassium sulfonate synthetic
(1) 8-anilino-1-naphthalene sulfonic acid potassium is synthetic
8-anilino-1-naphthalene sulfonic acid is dissolved in potassium hydroxide aqueous solution, be warming up to 40 ℃-60 ℃ and stirred 1 hour, be cooled to room temperature afterwards, leave standstill and see and slowly separate out crystallization in the reactant, collect the crystallization that this is separated out, and in water, obtain 8-anilino-1-naphthalene sulfonic acid sylvite behind the recrystallization.
(2) at room temperature, with 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-potassium sulfonate is dissolved in the acetone solvent, to wherein adding synthetic ionic liquid in the first step, is added dropwise to hydrochloric acid in vigorous stirring downhill reaction thing afterwards, the question response thing is chilled to after the room temperature to wherein slowly dripping sodium nitrite solution, is warming up to 60～80 ℃ of reactions 40 minutes～2 hours after dropwising.Reactant is cooled to room temperature, and top acetone layer is poured out.
(3) resistates is filtered with B, use the acetone rinsing resistates, merge acetone soln and adjust the pH value with saturated sodium bicarbonate solution, this solution decompression concentrated obtain blackish green pressed powder (this is raw material 8-anilino-1-naphthalene sulfonic acid potassium and product 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1, the mixture of 1 '-two-potassium sulfonate and sodium bicarbonate).
(4) with said mixture by column chromatography, with acetone with make eluent after ethyl acetate is mixed according to volume ratio at 1: 1, separation obtaining product 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-potassium sulfonate (bis-ANS).
Below provide the concrete implementation condition of embodiment 1-3:
The first step, as previously discussed, the glyoxaline cation class ion liquid synthetic in, the parameter condition is respectively:
Alkyl imidazole and haloalkane are respectively with 1: 1.0; 1: 1.2; Molar ratio mixed in 1: 1.5;
Alkyl imidazole and haloalkane are dissolved in 20; 25; In 30 times of volume ratio 1;
The reaction stirring and refluxing time is respectively 2; 2.5; 3 hours;
70 ℃ of temperature of reaction; 75 ℃; 80 ℃.
Gained glyoxaline cation class ionic liquid product is respectively:
1, iodate 1,3-dimethyl-imidazoles (MMIMI
-), 2, bromination 1-ethyl-3-Methylimidazole (EMIMBr
-), 3, bromination 1-propyl group-3-Methylimidazole (PMIMBr
-), 4, chlorination 1-butyl-3-Methylimidazole (BMIMCl
-), 5, bromination 1,3-diethyl imidazoles (EEIMBr
-), 6, bromination 1-propyl group-3-ethyl imidazol(e) (PEIMBr
-), 7, chlorination 1-butyl-3-ethyl imidazol(e) (BEIMCl
-).
Second step, as previously discussed, wherein:
In described 8-anilino-1-naphthalene sulfonic acid potassium synthetic, the parameter condition is:
8-anilino-1-naphthalene sulfonic acid 0.15mol is dissolved in potassium hydroxide aqueous solution 8.4g/150ml water;
Temperature of reaction is 60 ℃, 1 hour reaction times.
Described 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1, in 1 '-two-potassium sulfonate (bis-ANS) synthetic, the parameter condition is: at room temperature, and with 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-potassium sulfonate 5g are dissolved in the 50ml acetone solvent, afterwards to wherein adding synthetic ionic liquid 10g in the first step.
Be added dropwise to 36% concentrated hydrochloric acid 10ml in vigorous stirring downhill reaction thing, the question response thing is chilled to after the room temperature to wherein slowly dripping 0.2 mol sodium nitrite solution 10ml.
Dropwising the back heats up respectively to 60 ℃, 70 ℃, 80 ℃ reactions.
Reaction times was respectively 40 minutes, 1.5 hours, 2 hours.
Reactant is cooled to room temperature, and top acetone layer is poured out.Then, resistates is filtered with B, with 100ml acetone rinsing resistates, merge acetone soln and adjust pH value to 7.5 with saturated sodium bicarbonate solution, this solution decompression concentrated obtain blackish green pressed powder (this is raw material 8-anilino-1-naphthalene sulfonic acid potassium and product 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1, the mixture of 1 '-two-potassium sulfonate and sodium bicarbonate).
With said mixture by column chromatography for separation, with acetone with make eluent after ethyl acetate is mixed according to volume ratio at 1: 1, obtain product 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-potassium sulfonate (bis-ANS) 2.6g productive rate 26%.
Embodiment 4
8,8 '-two-phenylamino-5, in 5 '-two-naphthyl-1,1 '-two-potassium sulfonate synthetic, use seven kinds of ionic liquids of preparation to mix as reaction solvent respectively with acetone, (0.2M sodium nitrite solution 8ml under the identical situation of other reaction conditionss, 36% concentrated hydrochloric acid 10ml, 60 ℃ of temperature of reaction, 2 hours reaction times), investigate its productive rate separately respectively, the result is as follows.
1, iodate 1,3-dimethyl-imidazoles (MMIMI
-)-productive rate 14.8%, 2, bromination 1-ethyl-3-Methylimidazole (EMIMBr
-)-productive rate 12.5%, 3, bromination 1-propyl group-3-Methylimidazole (PMIMBr
-)-productive rate 9.6%, 4, chlorination 1-butyl-3-Methylimidazole (BMIMCl
-)-productive rate 19.2%, 5, bromination 1,3-diethyl imidazoles (EEIMBr
-)-productive rate 10.8%, 6, bromination 1-propyl group-3-ethyl imidazol(e) (PEIMBr
-)-productive rate 16.3%, 7, chlorination 1-butyl-3-ethyl imidazol(e) (BEIMCl
-)-productive rate 23.4%.
Embodiment 5
8,8 '-two-phenylamino-5,5 '-two-naphthyl-1, in 1 '-two-potassium sulfonate synthetic, for the influence of the consumption of investigating Sodium Nitrite to productive rate, according to the result of embodiment 4, the highest ionic liquid of productive rate---7 chlorination 1-butyl of wherein in embodiment 4, describing-3-ethyl imidazol(e) (BEIMCl have been selected for use
-) with acetone as mixed solvent, other reaction conditionss are consistent with describing among the embodiment 4, in these cases, investigated respectively and used the productive rate situation of 0.2M sodium nitrite solution under 8ml, 10ml, 15ml different amounts to be:
0.2M sodium nitrite solution is at 8ml-productive rate 23.1%, the 0.2M sodium nitrite solution is at 10ml-productive rate 26.0%, and the 0.2M sodium nitrite solution is at 12ml-productive rate 25.7%.
Claims (10)
1, a kind of 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate synthetic method is characterized in that, comprises following synthesis step:
The first step, the ion liquid synthetic preparation of several glyoxaline cation classes: to get alkyl imidazole and haloalkane is raw material, is solvent with the 1, back flow reaction gets glyoxaline cation class ionic liquid product;
Second step, 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1, synthesizing of 1 '-two-potassium sulfonate: is the sylvite that the reaction of raw material and potassium hydroxide makes 8-anilino-1-naphthalene sulfonic acid with the 8-anilino-1-naphthalene sulfonic acid, this sylvite under hydrochloric acid and sodium nitrite solution catalysis, is mixed the back as reaction solvent with synthetic glyoxaline cation class ionic liquid with acetone, react under the reflux temperature, separation obtained product through silicagel column after reaction finished.
2, according to claim 18,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate synthetic method is characterized in that, in the described the first step, concrete parameter is: alkyl imidazole and haloalkane are with 1: the 1.0-1.5 molar ratio mixes, and is dissolved in 20-30 times of volume ratio 1,1, in the 1-trichloroethane, stirring and refluxing reaction 2-4 hour separates product with separating funnel while hot, use 1 again, 1,1-trichloroethane washed twice gets product behind the rotary evaporation solvent.
3, according to claim 1 and 28,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate synthetic method is characterized in that, described back flow reaction, its reflux temperature is controlled at 70 ℃-80 ℃, 2 hours reaction times.
4, according to claim 18,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate synthetic method is characterized in that, the described the first step has prepared following seven serial glyoxaline cation class ionic liquids altogether, be respectively: iodate 1,3-dimethyl-imidazoles MMIMI
-, bromination 1-ethyl-3-Methylimidazole EMIMBr
-, bromination 1-propyl group-3-Methylimidazole PMIMBr
-, chlorination 1-butyl-3-Methylimidazole BMIMCl
-, bromination 1,3-diethyl imidazoles EEIMBr
-, bromination 1-propyl group-3-ethyl imidazol(e) PEIMBr
-), chlorination 1-butyl-3-ethyl imidazol(e) BEIMCl
-
5, according to claim 18,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate synthetic method is characterized in that, in described second step, is implemented as follows:
Step 1,8-anilino-1-naphthalene sulfonic acid and potassium hydroxide molar ratio are 1: 1, are dissolved in the water to heat up and stirring, are cooled to room temperature afterwards and slowly separate out crystallization, collect also and obtain 8-anilino-1-naphthalene sulfonic acid sylvite behind the recrystallization;
Step 2, at room temperature, 8-anilino-1-naphthalene sulfonic acid sylvite is dissolved in the acetone of 20-30 times of mass ratio, add the first step synthetic glyoxaline cation class ionic liquid, add hydrochloric acid under vigorous stirring, the question response thing slowly drips sodium nitrite solution after being cooled to room temperature, heat up and the control solvent refluxing, stoichiometric number hour, reactant is cooled to room temperature, and top acetone layer is poured out;
Step 3, ionic liquid with acetone rinsing remnants, merge acetone soln and adjust the pH value with saturated sodium bicarbonate solution, concentrating under reduced pressure obtains blackish green pressed powder, be 8-anilino-1-naphthalene sulfonic acid potassium and 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1, the mixture of 1 '-two-potassium sulfonate and small amounts of inorganic salt;
Step 4 by column chromatography, is made eluent with acetone/ethyl acetate with said mixture, separates obtaining product 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-potassium sulfonate.
6, according to claim 58,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate synthetic method is characterized in that, in the step 1, described intensification, its temperature is 40 ℃～60 ℃.
7, according to claim 58,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate synthetic method is characterized in that, in the step 2, described hydrochloric acid is meant that volumetric concentration is 36% concentrated hydrochloric acid.
8, according to claim 5 or 7 described 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate synthetic method is characterized in that, in the step 2, described sodium nitrite solution, its concentration is 0.2 mol sodium nitrite solution.
9, according to claim 5 or 7 described 8,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate synthetic method is characterized in that, and in the step 2, described intensification is the control solvent refluxing also, and its temperature is 60 ℃～80 ℃.
10, according to claim 58,8 '-two-phenylamino-5,5 '-two-naphthyl-1,1 '-two-sulfonate synthetic method is characterized in that, in the step 3, described adjustment pH value is meant and regulates the pH value to 7-9.
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| CN106896093A (en) * | 2017-03-01 | 2017-06-27 | 中南大学 | A kind of assay method of protein domain and linear interaction of biomacromolecules |
| CN106896093B (en) * | 2017-03-01 | 2019-12-17 | 中南大学 | Method for determining interaction between protein domain and linear biomacromolecule |
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