CN105203517A - 2, 8-di (4-vinylpyridine) -dibenzothiophene cation derivative and preparation method and application thereof - Google Patents
2, 8-di (4-vinylpyridine) -dibenzothiophene cation derivative and preparation method and application thereof Download PDFInfo
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- -1 (4-vinylpyridine) -dibenzothiophene cation Chemical class 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 20
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- FWBHETKCLVMNFS-UHFFFAOYSA-N 4',6-Diamino-2-phenylindol Chemical compound C1=CC(C(=N)N)=CC=C1C1=CC2=CC=C(C(N)=N)C=C2N1 FWBHETKCLVMNFS-UHFFFAOYSA-N 0.000 description 5
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Abstract
The invention relates to a 2, 8-di (4-vinylpyridine) -dibenzothiophene cationic derivative, which has the following structural formula:wherein R is CH3, C2H5, C4H9 or C6H 13. The invention provides a preparation method and application of the derivative, and the derivative is a fluorescent probe material which can solve the problems of complex synthesis process, low efficiency, poor selective labeling capability and the like commonly existing in the conventional two-photon fluorescent probe and has a practical value.
Description
Technical field
The present invention relates to probe material field, particularly 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives and its preparation method and application.
Background technology
Two-photon absorption has good three-dimensional space selectivity, the high-penetration degree of depth and long wave and excites the advantages such as short wavelength emissions.Therefore, two-photon absorbing material has important application prospect as fluorescence probe in high-resolution bioluminescence imaging field.
Since Goppert-Mayer in 1931 have studied the existence of two-photon absorption phenomenon first theoretically, people just start to have carried out deeply studying widely to two-photon absorbing material.The two-photon absorbing material of early stage people's research is mainly inorganic mineral crystal, but inorganic material also exists many defects in absorption efficiency and response speed etc., and therefore, the concern of people to Oragnic Two-photon Absorption Materials is constantly deepened.Improve the method for Oragnic Two-photon Absorption Materials mainly contain following some: (1) improves planar rigidity and the size of center conjugated bridge; (2) molecular chain length of Pi-conjugated systems is increased; (3) symmetry connection in molecule two ends has to electronics or electrophilic group, strengthens Intramolecular electron transfer efficiency, thus promotes fluorescence quantum yield; (4) the pi-conjugated delocalization plane that System forming is larger, thus improve two photon absorption cross section value.
Dibenzothiophene has rigid plane biphenyl structural, at parent 2,8 symmetrical connection vinylpyridine groups, the planar conjugate system of dibenzothiophene derivatives can be increased further, improve cyclic voltammetry method efficiency, increase molecular chain length, and then increase macromolecular two photon absorption cross section and fluorescence quantum yield.Meanwhile, carry out RI salinization reaction to the product of synthesis, the dibenzothiophene cationic derivative of formation can interact with the base-pair of cell amplifying nucleic acid DNA, enhances the biocompatibility of fluorescence probe, reaches selected marker and visits the effect shown.Most two-photon fluorescence probes of report are loaded down with trivial details owing to there is synthesis technique, and the defects such as efficiency is low, and selected marker ability is not good, limit the application of material in high-resolution fluorescence imaging field.
Can avoid so a kind of above-mentioned shortcoming, to solve the ubiquitous synthesis technique of existing two-photon fluorescence probe loaded down with trivial details, fluorescence probe material and the preparation method of the problems such as efficiency is low, and selected marker ability is not good extremely have practical value.
Summary of the invention
The object of the invention is to overcome above-mentioned shortcoming of the prior art, there is provided a kind of can avoid above-mentioned shortcoming, to solve the ubiquitous synthesis technique of existing two-photon fluorescence probe loaded down with trivial details, efficiency is low, problem 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives such as selected marker ability is not good and its preparation method and application.
To achieve these goals, one aspect of the present invention provides a kind of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, and it is characterized in that, the structural formula of described derivant is as follows:
Wherein, R is CH3, C2H5, C4H9 or C6H13.
The present invention provides a kind of method preparing 2,8-bis-above-mentioned (4-vinylpridine)-dibenzothiophene cationic derivatives on the other hand, it is characterized in that, comprises the following steps:
Step (1): take 1 ~ 2% 2 by mass percentage, 8-dibromo dibenzothiophene, the 4-vinylpridine of 1 ~ 2%, the tri-o-tolyl phosphine of 0.2 ~ 0.6%, the palladium of 0.02 ~ 0.06%, the N of 37 ~ 40%, dinethylformamide and 56 ~ 59% triethylamine, mix, obtain the first potpourri;
Step (2): the first described potpourri is added in autoclave chamber, autoclave chamber described in sealing, chamber air is displaced with High Purity Nitrogen air-flow, regulate pressure to 3 ~ 4MPa in still, be warming up to 110 ~ 120 DEG C, stirring reaction 39 ~ 40h, obtains second potpourri of separating out containing a large amount of intermediate product;
Step (3): after the second described potpourri suction filtration, obtain filter cake, the filter cake by methanol wash and described in drying, obtains dry cake;
Step (4): take the described dry cake of 46 ~ 49% by mass percentage, the acetone of 34 ~ 37% and the RI reaction of 16 ~ 18%, condensing reflux 34 ~ 36h under temperature of reaction is 75 ~ 85 DEG C of conditions; By reactant liquor vacuum filtration after reaction terminates, collect upper strata filter cake, obtain 2,8-bis-described (4-vinylpridine)-dibenzothiophene cationic derivatives.
Preferably, in step (4), described RI is CH3I, C2H5I, C4H9I or C6H13I.
Preferably, in step (1), 1.5% 2 are taken by mass percentage, 8-dibromo dibenzothiophene, the 4-vinylpridine of 1.5%, the tri-o-tolyl phosphine of 0.5%, the palladium of 0.05%, the DMF of 38.5% and the triethylamine of 57.95%.
Preferably, in step (2), in adjustment still, pressure is to 3.5MPa.
Preferably, in step (2), 115 DEG C are warming up to, stirring reaction 39.5h.
Preferably, in step (4), take the filter cake of 47% by mass percentage, the acetone of 36% and the RI of 17%.
Preferably, in step (4), temperature of reaction is 80 DEG C.
Preferably, in step (4), condensing reflux 35h.
Third aspect present invention provides a kind of 2,8-bis-above-mentioned (4-vinylpridine)-dibenzothiophene cationic derivatives as the application of two-photon fluorescence probe material in high-resolution bioluminescence imaging field.
The present invention comprises following beneficial effect:
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives of the present invention, are soluble in the multiple organic solvents such as acetone, acetonitrile, DMF, ethanol, chloroform.Sample solution, under wavelength is the ultraviolet excitation within the scope of 390-410nm, all can produce strong and stable fluorescence.Under different capacity condition, use near infrared 800nm femtosecond laser to carry out excited sample solution, stronger two-photon fluorescence effect can be produced, embody obvious thermal stability, photochemical stability and good Photophysics.
Of the present invention 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, selective kernel dyeing can be carried out to mouse fibrocyte, and compared with commercial fluorescence probe DAPI, there is higher two-photon fluorescence intensity, embody the advantage of two-photon fluorescence probe.And they are first on 2,8-dibromo dibenzothiophene the both sides first symmetrical basis connecting 4-vinylpridine, then carry out one-sided RI (I=CH3, C2H5, C4H9 or C6H13) salinization reaction, form the one-sided cationic derivative of dibenzothiophene class.Synthesized derivant has good conjugation delocalization plane, the carbochain of molecular end can form D-π-A type structure with center conjugated bridge, utilize the electron-withdrawing power of N position and the electron donation of end carbon chain on center parent and pyridine, by the bridge channels of ethylene double bond, in the large pi-conjugated system of molecule, form good charge migration efficiency, thus put forward high molecular two photon absorption cross section and fluorescence quantum efficiency.
Of the present invention 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, in the closed environment of autoclave, adopt He Ke to react (heckreaction) by the mode of High Temperature High Pressure and first synthesize intermediate product 2,8-bis-(4-vinylpridine)-dibenzothiophene, then mode one step by directly adding acetone and RI (I=CH3, C2H5, C4H9 or C6H13) produces final product 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative.Mutually synthetic method has the following advantages than ever: the synthesis of intermediate product is eliminated to the tedious steps such as extraction in the past, column chromatography for separation and decompression distillation, the a small amount of impurity contained in intermediate product can be removed in the lump in salinization reaction, achieve the technological process that salinization and removal of impurities are carried out simultaneously, and reaction can obtain highly purified target product by means of only vacuum filtration one step after terminating.Whole preparation process had both saved the purification of products time, turn improved experimental work efficiency.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that specific embodiment 1 obtains;
Fig. 2 is the infrared spectrogram of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that specific embodiment 2 obtains;
Fig. 3 is the infrared spectrogram of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that specific embodiment 3 obtains;
Fig. 4 is the infrared spectrogram of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that specific embodiment 4 obtains;
Fig. 5 is the mass spectrogram of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that specific embodiment 1 obtains;
Fig. 6 is the mass spectrogram of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that specific embodiment 2 obtains;
Fig. 7 is the mass spectrogram of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that specific embodiment 3 obtains;
Fig. 8 is the mass spectrogram of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that specific embodiment 4 obtains.
Embodiment
In order to more clearly understand technology contents of the present invention, below specific embodiment of the invention method is described further.
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the structural formula of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives of present embodiment is as follows:
wherein, R is CH3, C2H5, C4H9 or C6H13.
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives of present embodiment, are soluble in the multiple organic solvents such as acetone, acetonitrile, DMF, ethanol, chloroform.Sample solution, under wavelength is the ultraviolet excitation within the scope of 390-410nm, all can produce strong and stable fluorescence.Under different capacity condition, use near infrared 800nm femtosecond laser to carry out excited sample solution, stronger two-photon fluorescence effect can be produced, embody obvious thermal stability, photochemical stability and good Photophysics.
2 of present embodiment, 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, selective kernel dyeing can be carried out to mouse fibrocyte, and compared with commercial fluorescence probe DAPI, there is higher two-photon fluorescence intensity, embody the advantage of two-photon fluorescence probe.
Embodiment two: the preparation method of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives of present embodiment, carry out according to following steps:
One, 1 ~ 2% 2 are taken by mass percentage, 8-dibromo dibenzothiophene, the 4-vinylpridine of 1 ~ 2%, the tri-o-tolyl phosphine of 0.2 ~ 0.6%, the palladium of 0.02 ~ 0.06%, the DMF of 37 ~ 40% and 56 ~ 59% triethylamine.Above-mentioned mixing of materials is even, join in autoclave chamber that volume is 50ml, after sealed reactor, with air in High Purity Nitrogen air-flow repeatedly 3 displacement cavitys to complete nitrogen environment.Regulate pressure to 3 ~ 4MPa in still, be warming up to 110 ~ 120 DEG C, stirring reaction 39 ~ 40h, obtain the potpourri of separating out containing a large amount of intermediate product.
Two, by after potpourri vacuum filtration, with methanol wash upper strata filter cake 2 ~ 3 times, vacuum drying 1 ~ 2h under 20 ~ 30 DEG C of conditions, collects filter cake.Take the filter cake of 46 ~ 49% by mass percentage, the acetone of 34 ~ 37% and the RI (I=CH3, C2H5, C4H9 or C6H13) of 16 ~ 18%, condensing reflux 34 ~ 36h under temperature of reaction is 75 ~ 85 DEG C of conditions.By reactant liquor vacuum filtration after reaction terminates, collect upper strata filter cake, obtain 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative.
2 of present embodiment, 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative is produced by following two-step reaction: (1) 2, there is He Ke reaction (heckreaction) and prepare 2,8-bis-(4-vinylpridine)-dibenzothiophene in 8-dibromo dibenzothiophene and 4-vinylpridine; (2) 2, there is salinization reaction generation 2 in 8-bis-(4-vinylpridine)-dibenzothiophene and RI (I=CH3, C2H5, C4H9 or C6H13), 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, its reaction equation is:
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives of present embodiment, are soluble in the multiple organic solvents such as acetone, acetonitrile, DMF, ethanol, chloroform.Sample solution, under wavelength is the ultraviolet excitation within the scope of 390-410nm, all can produce strong and stable fluorescence.Under different capacity condition, use near infrared 800nm femtosecond laser to carry out excited sample solution, stronger two-photon fluorescence effect can be produced, embody obvious thermal stability, photochemical stability and good Photophysics.
2 of present embodiment, 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, selective kernel dyeing can be carried out to mouse fibrocyte, and compared with commercial fluorescence probe DAPI, there is higher two-photon fluorescence intensity, embody the advantage of two-photon fluorescence probe.
2 of present embodiment, 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, first 2,8-dibromo dibenzothiophene both sides first symmetry connect on the basis of 4-vinylpridine, carry out one-sided RI (I=CH3, C2H5, C4H9 or C6H13) salinization reaction again, form the one-sided cationic derivative of dibenzothiophene class.Synthesized derivant has good conjugation delocalization plane, the carbochain of molecular end can form D-π-A type structure with center conjugated bridge, utilize the electron-withdrawing power of N position and the electron donation of end carbon chain on center parent and pyridine, by the bridge channels of ethylene double bond, in the large pi-conjugated system of molecule, form good charge migration efficiency, thus put forward high molecular two photon absorption cross section and fluorescence quantum efficiency.
2 of present embodiment, 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, in the closed environment of autoclave, adopt He Ke to react (heckreaction) by the mode of High Temperature High Pressure and first synthesize intermediate product 2,8-bis-(4-vinylpridine)-dibenzothiophene, then mode one step by directly adding acetone and RI (I=CH3, C2H5, C4H9 or C6H13) produces final product 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative.Mutually synthetic method has the following advantages than ever: the synthesis of intermediate product is eliminated to the tedious steps such as extraction in the past, column chromatography for separation and decompression distillation, the a small amount of impurity contained in intermediate product can be removed in the lump in salinization reaction, achieve the technological process that salinization and removal of impurities are carried out simultaneously, and reaction can obtain highly purified target product by means of only vacuum filtration one step after terminating.Whole preparation process had both saved the purification of products time, turn improved experimental work efficiency.
Embodiment three: present embodiment and embodiment two unlike: described in step one take by mass percentage 1.5% 2,8-dibromo dibenzothiophene, the 4-vinylpridine of 1.5%, the tri-o-tolyl phosphine of 0.5%, the palladium of 0.05%, the DMF of 38.5% and the triethylamine of 57.95%.Other is identical with embodiment two.
Embodiment four: present embodiment and embodiment two or three unlike: in the adjustment still described in step one, pressure is to 3.5MPa.Other is identical with embodiment two or three.
Embodiment five: one of present embodiment and embodiment two to four unlike: be warming up to 115 DEG C described in step one.Other is identical with one of embodiment two to four.
Embodiment six: one of present embodiment and embodiment two to five are unlike stirring reaction 39.5h described in step one.Other is identical with one of embodiment two to five.
Embodiment seven: one of present embodiment and embodiment two to six unlike: described in step 2 take by mass percentage 47% filter cake, the acetone of 36% and the RI (CH3I, C2H5I, C4H9I or C6H13I) of 17%.Other is identical with one of embodiment two to six.
Embodiment eight: one of present embodiment and embodiment two to seven are unlike the temperature of reaction described in step 2 80 DEG C.Other is identical with one of embodiment two to seven.
Embodiment nine: one of present embodiment and embodiment two to eight are unlike condensing reflux 35h described in step 2.Other is identical with one of embodiment two to eight.
Embodiment ten: 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives of present embodiment as two-photon fluorescence probe materials application in high-resolution bioluminescence imaging field.
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives of present embodiment, are soluble in the multiple organic solvents such as acetone, acetonitrile, DMF, ethanol, chloroform.Sample solution, under wavelength is the ultraviolet excitation within the scope of 390-410nm, all can produce strong and stable fluorescence.Under different capacity condition, use near infrared 800nm femtosecond laser to carry out excited sample solution, stronger two-photon fluorescence effect can be produced, embody obvious thermal stability, photochemical stability and good Photophysics.
2 of present embodiment, 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, selective kernel dyeing can be carried out to mouse fibrocyte, and compared with commercial fluorescence probe DAPI, there is higher two-photon fluorescence intensity, embody the advantage of two-photon fluorescence probe.
2 of present embodiment, 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, first 2,8-dibromo dibenzothiophene both sides first symmetry connect on the basis of 4-vinylpridine, carry out one-sided RI (I=CH3, C2H5, C4H9 or C6H13) salinization reaction again, form the one-sided cationic derivative of dibenzothiophene class.Synthesized derivant has good conjugation delocalization plane, the carbochain of molecular end can form D-π-A type structure with center conjugated bridge, utilize the electron-withdrawing power of N position and the electron donation of end carbon chain on center parent and pyridine, by the bridge channels of ethylene double bond, in the large pi-conjugated system of molecule, form good charge migration efficiency, thus put forward high molecular two photon absorption cross section and fluorescence quantum efficiency.
2 of present embodiment, 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, in the closed environment of autoclave, adopt He Ke to react (heckreaction) by the mode of High Temperature High Pressure and first synthesize intermediate product 2,8-bis-(4-vinylpridine)-dibenzothiophene, then mode one step by directly adding acetone and RI (I=CH3, C2H5, C4H9 or C6H13) produces final product 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative.Mutually synthetic method has the following advantages than ever: the synthesis of intermediate product is eliminated to the tedious steps such as extraction in the past, column chromatography for separation and decompression distillation, the a small amount of impurity contained in intermediate product can be removed in the lump in salinization reaction, achieve the technological process that salinization and removal of impurities are carried out simultaneously, and reaction can obtain highly purified target product by means of only vacuum filtration one step after terminating.Whole preparation process had both saved the purification of products time, turn improved experimental work efficiency.
Beneficial effect of the present invention is verified by following examples:
Embodiment 1:
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative preparations of the present embodiment are carried out according to following steps:
Take 2, the 8-dibromo dibenzothiophene of 1.42% by mass percentage, the 4-vinylpridine of 1.2%, the tri-o-tolyl phosphine of 0.336%, the palladium of 0.044%, the DMF of 38% and 59% triethylamine.Above-mentioned mixing of materials is even, join in autoclave chamber that volume is 50ml, after sealed reactor, with air in High Purity Nitrogen air-flow repeatedly 3 displacement cavitys to complete nitrogen environment.Regulate pressure in still to 3.5MPa, to be warming up to 118 DEG C, stirring reaction 39.5h, obtain the potpourri of separating out containing a large amount of intermediate product.After potpourri vacuum filtration, with methanol wash upper strata filter cake 3 times, vacuum drying 1h under 25 DEG C of conditions, collects filter cake.Take the filter cake of 47% by mass percentage, the acetone of 36% and the CH3I of 17%, condensing reflux 36h under temperature of reaction is 80 DEG C of conditions.By reactant liquor vacuum filtration after reaction terminates, collect upper strata filter cake, obtain 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative.
The structural formula that the present embodiment obtains 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative is:
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative sterlings that the present embodiment obtains are yellow powdery solid.
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative productive rates 92.1% that the present embodiment obtains.The present embodiment obtain 2, the infrared spectrogram of 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative as shown in Figure 1, mass spectrogram as shown in Figure 5, as shown in Figure 1, the characteristic absorption peak of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that the present embodiment obtains is: 1618cm-1 is the stretching vibration of C=C double bond.As shown in Figure 5, the MALDI-TOF-MS:m/z of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that the present embodiment obtains, 405.223 (theoretical value is 405.14) [M].
Embodiment 2:
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative preparations of the present embodiment are carried out according to following steps:
Take 2, the 8-dibromo dibenzothiophene of 1.58% by mass percentage, the 4-vinylpridine of 1.69%, the tri-o-tolyl phosphine of 0.293%, the palladium of 0.037%, the DMF of 39.4% and 57% triethylamine.Above-mentioned mixing of materials is even, join in autoclave chamber that volume is 50ml, after sealed reactor, with air in High Purity Nitrogen air-flow repeatedly 3 displacement cavitys to complete nitrogen environment.Regulate pressure in still to 3.5MPa, to be warming up to 118 DEG C, stirring reaction 39.5h, obtain the potpourri of separating out containing a large amount of intermediate product.After potpourri vacuum filtration, with methanol wash upper strata filter cake 3 times, vacuum drying 1h under 25 DEG C of conditions, collects filter cake.Take the filter cake of 47% by mass percentage, the acetone of 35% and the C2H5I of 18%, condensing reflux 36h under temperature of reaction is 80 DEG C of conditions.By reactant liquor vacuum filtration after reaction terminates, collect upper strata filter cake, obtain 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative.
The structural formula that the present embodiment obtains 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative is:
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative sterlings that the present embodiment obtains are yellow powdery solid.
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative productive rates 91.9% that the present embodiment obtains.The present embodiment obtain 2, the infrared spectrogram of 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative as shown in Figure 2, mass spectrogram as shown in Figure 6, as shown in Figure 2, the characteristic absorption peak of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that the present embodiment obtains is: 1615cm-1 is the stretching vibration of C=C double bond.As shown in Figure 6, the MALDI-TOF-MS:m/z of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that the present embodiment obtains, 419.288 (theoretical value is 419.16) [M].
Embodiment 3:
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative preparations of the present embodiment are carried out according to following steps:
Take 2, the 8-dibromo dibenzothiophene of 1.68% by mass percentage, the 4-vinylpridine of 1.91%, the tri-o-tolyl phosphine of 0.358%, the palladium of 0.052%, the DMF of 38% and 58% triethylamine.Above-mentioned mixing of materials is even, join in autoclave chamber that volume is 50ml, after sealed reactor, with air in High Purity Nitrogen air-flow repeatedly 3 displacement cavitys to complete nitrogen environment.Regulate pressure in still to 3.5MPa, to be warming up to 118 DEG C, stirring reaction 39.5h, obtain the potpourri of separating out containing a large amount of intermediate product.After potpourri vacuum filtration, with methanol wash upper strata filter cake 3 times, vacuum drying 1h under 25 DEG C of conditions, collects filter cake.Take the filter cake of 48% by mass percentage, the acetone of 35.5% and the C4H9I of 16.5%, condensing reflux 36h under temperature of reaction is 80 DEG C of conditions.By reactant liquor vacuum filtration after reaction terminates, collect upper strata filter cake, obtain 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative.
The structural formula that the present embodiment obtains 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative is:
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative sterlings that the present embodiment obtains are yellow powdery solid.
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative productive rates 89.4% that the present embodiment obtains.The present embodiment obtain 2, the infrared spectrogram of 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative as shown in Figure 3, mass spectrogram as shown in Figure 7, as shown in Figure 3, the characteristic absorption peak of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that the present embodiment obtains is: 1616cm-1 is the stretching vibration of C=C double bond.As shown in Figure 7, the MALDI-TOF-MS:m/z of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that the present embodiment obtains, 447.333 (theoretical value is 447.19) [M].
Embodiment 4:
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative preparations of the present embodiment are carried out according to following steps:
Take 2, the 8-dibromo dibenzothiophene of 1.52% by mass percentage, the 4-vinylpridine of 1.89%, the tri-o-tolyl phosphine of 0.548%, the palladium of 0.042%, the DMF of 40% and 56% triethylamine.Above-mentioned mixing of materials is even, join in autoclave chamber that volume is 50ml, after sealed reactor, with air in High Purity Nitrogen air-flow repeatedly 3 displacement cavitys to complete nitrogen environment.Regulate pressure in still to 3.5MPa, to be warming up to 118 DEG C, stirring reaction 39.5h, obtain the potpourri of separating out containing a large amount of intermediate product.After potpourri vacuum filtration, with methanol wash upper strata filter cake 3 times, vacuum drying 1h under 25 DEG C of conditions, collects filter cake.Take the filter cake of 49% by mass percentage, the acetone of 34.5% and the C6H13I of 16.5%, condensing reflux 36h under temperature of reaction is 80 DEG C of conditions.By reactant liquor vacuum filtration after reaction terminates, collect upper strata filter cake, obtain 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative.
The structural formula that the present embodiment obtains 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative is:
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative sterlings that the present embodiment obtains are yellow powdery solid.
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative productive rates 90.5% that the present embodiment obtains.The present embodiment obtain 2, the infrared spectrogram of 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative as shown in Figure 4, mass spectrogram as shown in Figure 8, as shown in Figure 4, the characteristic absorption peak of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that the present embodiment obtains is: 1616cm-1 is the stretching vibration of C=C double bond.As shown in Figure 8, the MALDI-TOF-MS:m/z of 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives that the present embodiment obtains, 475.235 (theoretical value is 475.22) [M].
The present invention comprises following beneficial effect:
2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives of the present invention, are soluble in the multiple organic solvents such as acetone, acetonitrile, DMF, ethanol, chloroform.Sample solution, under wavelength is the ultraviolet excitation within the scope of 390-410nm, all can produce strong and stable fluorescence.Under different capacity condition, use near infrared 800nm femtosecond laser to carry out excited sample solution, stronger two-photon fluorescence effect can be produced, embody obvious thermal stability, photochemical stability and good Photophysics.
Of the present invention 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, selective kernel dyeing can be carried out to mouse fibrocyte, and compared with commercial fluorescence probe DAPI, there is higher two-photon fluorescence intensity, embody the advantage of two-photon fluorescence probe.And they are first on 2,8-dibromo dibenzothiophene the both sides first symmetrical basis connecting 4-vinylpridine, then carry out one-sided RI (I=CH3, C2H5, C4H9 or C6H13) salinization reaction, form the one-sided cationic derivative of dibenzothiophene class.Synthesized derivant has good conjugation delocalization plane, the carbochain of molecular end can form D-π-A type structure with center conjugated bridge, utilize the electron-withdrawing power of N position and the electron donation of end carbon chain on center parent and pyridine, by the bridge channels of ethylene double bond, in the large pi-conjugated system of molecule, form good charge migration efficiency, thus put forward high molecular two photon absorption cross section and fluorescence quantum efficiency.
Of the present invention 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, in the closed environment of autoclave, adopt He Ke to react (heckreaction) by the mode of High Temperature High Pressure and first synthesize intermediate product 2,8-bis-(4-vinylpridine)-dibenzothiophene, then mode one step by directly adding acetone and RI (I=CH3, C2H5, C4H9 or C6H13) produces final product 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative.Mutually synthetic method has the following advantages than ever: the synthesis of intermediate product is eliminated to the tedious steps such as extraction in the past, column chromatography for separation and decompression distillation, the a small amount of impurity contained in intermediate product can be removed in the lump in salinization reaction, achieve the technological process that salinization and removal of impurities are carried out simultaneously, and reaction can obtain highly purified target product by means of only vacuum filtration one step after terminating.Whole preparation process had both saved the purification of products time, turn improved experimental work efficiency.
In this description, the present invention is described with reference to its specific embodiment.But, still can make various amendment and conversion obviously and not deviate from the spirit and scope of the present invention.Therefore, instructions is regarded in an illustrative, rather than a restrictive.
Claims (10)
1. one kind 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, it is characterized in that, the structural formula of described derivant is as follows:
Wherein, R is CH3, C2H5, C4H9 or C6H13.
2. prepare the method for 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives according to claim 1 for one kind, it is characterized in that, comprise the following steps:
Step (1): take 1 ~ 2% 2 by mass percentage, 8-dibromo dibenzothiophene, the 4-vinylpridine of 1 ~ 2%, the tri-o-tolyl phosphine of 0.2 ~ 0.6%, the palladium of 0.02 ~ 0.06%, the N of 37 ~ 40%, dinethylformamide and 56 ~ 59% triethylamine, mix, obtain the first potpourri;
Step (2): the first described potpourri is added in autoclave chamber, autoclave chamber described in sealing, chamber air is displaced with High Purity Nitrogen air-flow, regulate pressure to 3 ~ 4MPa in still, be warming up to 110 ~ 120 DEG C, stirring reaction 39 ~ 40h, obtains second potpourri of separating out containing a large amount of intermediate product;
Step (3): after the second described potpourri suction filtration, obtain filter cake, the filter cake by methanol wash and described in drying, obtains dry cake;
Step (4): take the described dry cake of 46 ~ 49% by mass percentage, the acetone of 34 ~ 37% and the RI reaction of 16 ~ 18%, condensing reflux 34 ~ 36h under temperature of reaction is 75 ~ 85 DEG C of conditions; By reactant liquor vacuum filtration after reaction terminates, collect upper strata filter cake, obtain 2,8-bis-described (4-vinylpridine)-dibenzothiophene cationic derivatives.
3. the method for preparation 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative according to claim 2, it is characterized in that, in step (4), described RI is CH
3i, C
2h
5i, C
4h
9i or C
6h
13i.
4. preparation 2 according to claim 2, the method of 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, it is characterized in that, in step (1), take 1.5% 2 by mass percentage, 8-dibromo dibenzothiophene, the 4-vinylpridine of 1.5%, the tri-o-tolyl phosphine of 0.5%, the palladium of 0.05%, the DMF of 38.5% and the triethylamine of 57.95%.
5. the method for preparation 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative according to claim 2, is characterized in that, in step (2), in adjustment still, pressure is to 3.5MPa.
6. the method for preparation 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative according to claim 2, is characterized in that, in step (2), be warming up to 115 DEG C, stirring reaction 39.5h.
7. preparation 2 according to claim 2, the method of 8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative, is characterized in that, in step (4), take the filter cake of 47% by mass percentage, the acetone of 36% and the RI of 17%.
8. the method for preparation 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative according to claim 2, it is characterized in that, in step (4), temperature of reaction is 80 DEG C.
9. the method for preparation 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivative according to claim 2, is characterized in that, in step (4), and condensing reflux 35h.
10. 2,8-bis-(4-vinylpridine)-dibenzothiophene cationic derivatives according to claim 1 are as the application of two-photon fluorescence probe material in high-resolution bioluminescence imaging field.
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