CN103524405A - Monohydrate-4-(4-dimethyl amino styryl) methylpyridine benzene sulfonate and preparation method thereof - Google Patents
Monohydrate-4-(4-dimethyl amino styryl) methylpyridine benzene sulfonate and preparation method thereof Download PDFInfo
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
The invention belongs to functional material and its preparation technical fields, it is related to one kind one and is hydrated 4-(4- dimethylaminostyryl) picoline benzene sulfonate and preparation method thereof, there are pi-electron conjugated systems in its molecular structure, single crystal diffraction test result shows that its chemical formula is C22H24N2O3SH2O, belong to anorthic system at room temperature, space group is P-1, and cell parameter is
α=106.1087 (12) °, β=91.3577 (12) °, γ=105.0583 (12) °,
Z=4; Preparation process includes synthetic reaction, condensation reaction, ion-exchange reactions and filtering four steps of purification; Its thermal stability is good, and purity is high, raw material is easy to get, and preparation method is simple, and reaction condition is mild, and potential implementary value is high.
Description
Technical field:
The invention belongs to functional materials and preparing technical field thereof, relate to a kind of organic optical crystalline material and preparation technology thereof, particularly an a kind of hydration 4-(4-dimethylamino styryl) picoline benzene sulfonate and preparation method thereof.
Background technology:
The non-linear effect of organic nonlinear optical crystal causes rapidly people's very big attention after 1964 find, and found successively the organic nonlinear optical crystal of many excellent propertys, organic non linear optical material has the incomparable advantage of inorganic materials, as extensive in raw material, be easy to design molecular structure, non-linear electric susceptibility is large, and these advantages make, and organic non linear optical material becomes irreplaceable photon material of new generation after inorganic materials.At present, a lot of organic nonlinear optical crystals have been had been found that, typical second-order non-linear optical crystal comprises urea and derivative thereof, organic pyridinium salt class and formiate, in the research of organic non linear optical material, find, organic pyridinium salt and derivative thereof are that a quasi-nonlinear is active large, assemble various informative molecular material, styryl pyridinium wherein, organic pyridinium salt is a class organic non linear optical material of current most study, 4-(4-dimethylamino styryl) picoline tosilate is more a kind of of at present research, it is a kind of organic salt crystal forming by strong Coulomb's force, its positively charged ion is a kind of organic molecule with the large π key of conjugation, due to its non-centrosymmetric feature, 4-(4-dimethylamino styryl) picoline tosilate has shown good two-stage non-linear optical property.Therefore, by changing the functional group in anionic group, design synthetic a kind of novel organic optical crystalline material one hydration 4-(4-dimethylamino styryl of preparing) picoline benzene sulfonate and preparation method thereof, potential using value and practical significance there is.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, seek a kind of novel organic optical crystalline material one hydration 4-(4-dimethylamino styryl of design preparation) picoline benzene sulfonate, preparation method is simple, reaction conditions is gentle, and the organic optical crystalline material thermal stability of preparation is high.
To achieve these goals, the hydration 4-(4-dimethylamino styryl the present invention relates to) organic pyridinium salt of picoline benzene sulfonate for being formed by zwitterion key, in its molecular structure, have larger π-electron conjugated system, single crystal diffraction test result shows that its chemical formula is C
22h
24n
2o
3sH
2o, at room temperature belongs to triclinic(crystalline)system, and spacer is P-1, and unit cell parameters is
α=106.1087 (12) °, β=91.3577 (12) °, γ=105.0583 (12) °,
z=4; Its skeleton symbol is as follows:
The hydration 4-(4-dimethylamino styryl the present invention relates to) preparation method of picoline benzene sulfonate comprises building-up reactions, condensation reaction, ion exchange reaction and four steps of filtration purification, and its specific embodiment is:
(1) building-up reactions: the 4-picoline that the purity of getting identical mol ratio concentration is 98% and purity are not less than 98% methyl iodide and are mixed to get mixing solutions, and mixing solutions is placed in to purity is 99.7% dehydrated alcohol, wherein the volume ratio of mixing solutions and dehydrated alcohol is 3:2, the standing at room temperature spontaneous building-up reactions of carrying out after stirring, react and generate white needles solid after 10-20 minute, through filtering, obtain 4-picoline salt compounded of iodine, then that 4-picoline salt compounded of iodine oven dry sealed storage is standby; Purity is not less than to 98% Phenylsulfonic acid again and is dissolved in the silver suboxide that is 99.7% with purity after deionized water and at room temperature carries out building-up reactions 1 minute, wherein, the mass ratio of Phenylsulfonic acid and deionized water is 1:5, and the mol ratio of Phenylsulfonic acid and silver suboxide is 2:1; Filtration obtains Phenylsulfonic acid solution, then uses conventional evaporation drying device by Phenylsulfonic acid solution evaporate to dryness, obtains dry Phenylsulfonic acid silvery white solid, and Phenylsulfonic acid silver sealed storage is standby;
(2) condensation reaction: get the 4-picoline salt compounded of iodine of identical mol ratio and analytical pure paradimethy laminobenzaldehyde and be dissolved in respectively purity and be not less than in 99.5% anhydrous methanol, wherein the mass ratio of 4-picoline salt compounded of iodine and anhydrous methanol is 1:6, the mass ratio of paradimethy laminobenzaldehyde and anhydrous methanol is 1:9, heated and stirred makes 4-picoline and paradimethy laminobenzaldehyde be dissolved in respectively anhydrous methanol to be completely placed in three hole flasks, stirring is warming up to 65-70 ℃, carry out condensing reflux simultaneously, add 15-20 drip piperidines as catalyst solution by the light yellow scarlet that gradually becomes, condensation reaction obtains 4-(4-dimethylamino styryl) picoline iodide,
(3) ion exchange reaction: carry out after 18-24h in the condensation reaction of step (2), add the prepared Phenylsulfonic acid silver of step (1), the Phenylsulfonic acid silver adding and the 4-picoline salt compounded of iodine equimolar ratio in step (2), ion exchange reaction is carried out in continuation at 65-70 ℃, while condensing reflux, after reaction 18-24h, generate Silver iodide precipitation and a hydration 4-(4-dimethylamino styryl) picoline benzene sulfonate, the solution obtaining is dark red solution;
(4) filter and purify: the dark red solution filtered while hot that step (3) reaction is obtained, through standing, cooling and recrystallization, prepares a hydration 4-(4-dimethylamino styryl by the solution that filters Silver iodide precipitation) picoline benzene sulfonate.
A hydration 4-(4-dimethylamino styryl prepared by the present invention) picoline benzene sulfonate crystal did not decompose before 238 ℃, and thermal stability is good; In its molecular structure, in the kind of hydrogen atom and number and nucleus magnetic resonance 1H spectrum, represent that the number at peak of hydrogen atom displacement and the integral area at each peak match; Carbon atom kind and nucleus magnetic resonance 13C spectrum in represent that the number at the peak of carbon atom displacement matches.
Compared with prior art, the organic optical crystalline material thermal stability of preparation is good in the present invention, and purity is high, and raw material is easy to get, and preparation method is simple, and reaction conditions is gentle, and potential implementary value is high.
Accompanying drawing explanation:
Fig. 1 is the hydration 4-(4-dimethylamino styryl the present invention relates to) molecular structure of picoline benzene sulfonate.
Fig. 2 is the hydration 4-(4-dimethylamino styryl the present invention relates to) crystallogram of picoline benzene sulfonate.
Fig. 3 is the hydration 4-(4-dimethylamino styryl the present invention relates to) nucleus magnetic resonance of picoline benzene sulfonate
1h spectrum.
Fig. 4 is the hydration 4-(4-dimethylamino styryl the present invention relates to) nucleus magnetic resonance of picoline benzene sulfonate
13c spectrum.
Embodiment:
Below by embodiment, also by reference to the accompanying drawings the present invention is elaborated.
Embodiment:
The present embodiment is prepared a hydration 4-(4-dimethylamino styryl) concrete steps of picoline benzene sulfonate comprise building-up reactions, condensation reaction, ion exchange reaction and filtration four steps of purifying:
(1) building-up reactions: get the 4-picoline (purity is 98%) of 0.1mol and the methyl iodide (purity is not less than 98%) of 0.1mol and mix that to be placed on 10-12ml purity be in 99.7% dehydrated alcohol, stir, after 10-15 minute, reaction generates white needles solid, the dehydrated alcohol washing and filtering that is 99.7% by 8-10ml purity is also dried and is obtained 4-picoline salt compounded of iodine 17.6g with vacuum drying oven, productive rate is 74.9%, then that 4-picoline salt compounded of iodine sealed storage is standby; Then get the Phenylsulfonic acid (purity is not less than 98%) of 0.1mol and the silver suboxide of 0.05mol (purity is 99.7%), Phenylsulfonic acid (purity is not less than 98%) is dissolved in 50-60ml deionized water and with silver suboxide (purity is 99.7%) and is reacted, after reaction, add again the dilution of 50-60ml deionized water, filtration obtains Phenylsulfonic acid solution, again with evaporation drying device rotatory evaporator by solution evaporate to dryness, obtain dry Phenylsulfonic acid silvery white solid 23.5g, productive rate is 85.8%, and Phenylsulfonic acid silver sealed storage is standby;
(2) condensation reaction: get the 4-picoline salt compounded of iodine of 0.03mol and the paradimethy laminobenzaldehyde (analytical pure) of 0.03mol and be dissolved in respectively in 40ml and 60ml anhydrous methanol (purity is not less than 99.5%), heated and stirred is dissolved in the three hole flasks that are placed on 250ml it completely, stirring is warming up to 65-70 ℃, carry out condensing reflux simultaneously, add 15-20 to drip piperidines as catalyzer, solution, by the light yellow scarlet that gradually becomes, obtains 4-(4-dimethylamino styryl after condensation reaction 18-24h) picoline iodide;
(3) ion exchange reaction: carry out after 18-24h in the condensation reaction of step (2), add the prepared Phenylsulfonic acid silver of 0.03mol step (1), with 4-(4-dimethylamino styryl) at 65-70 ℃, there is ion exchange reaction in picoline iodide, after condensing reflux 12-18h, generate Silver iodide precipitation and a hydration 4-(4-dimethylamino styryl) picoline benzene sulfonate, the solution obtaining is dark red solution;
(4) filter and purify: the dark red solution filtered while hot of the 100ml left and right that step (3) reaction is obtained, the solution that filters Silver iodide precipitations through standing, cooling and in 100-150ml anhydrous methanol (purity is not less than 99.5%) recrystallization can obtain light green needle-like or a block hydration 4-(4-dimethylamino styryl) picoline benzene sulfonate crystal, productive rate is 43.8%.
The hydration 4-(4-dimethylamino styryl that the present embodiment is prepared 5mg) picoline benzene sulfonate is dissolved in the deuterated DMSO of 0.5ml, utilizes JNM ECP-600 type nuclear magnetic resonance spectrometer to be NMR1H spectrum and NMR
13c composes detection, from NMR
1in H collection of illustrative plates (Fig. 3), can find out the integral area ratio (1.94:2.02:1:4.04:2.99:1.04:1.95:2.97:6.1) and a hydration 4-(4-dimethylamino styryl at each peak (containing displacement at the water peak of 3.3 left and right and the solvent peak of 2.5 left and right) that represents H knocking out in collection of illustrative plates) position and the number of H atom (containing the H atom in crystal water) matches than (2:2:1:4:3:1:2:3:6) in picoline benzene sulfonate molecular structural formula, and assorted peak occurs; From NMR
13the spectral line that can find out C knocking out in collection of illustrative plates in C collection of illustrative plates (Fig. 4) has 15 (not solvent-laden peaks), with a hydration 4-(4-dimethylamino styryl) kind (15 kinds) of C atom is consistent in picoline benzene sulfonate molecular structural formula, test result shows that product is a highly purified hydration 4-(4-dimethylamino styryl) picoline benzene sulfonate.
Claims (2)
1. a hydration 4-(4-dimethylamino styryl) picoline benzene sulfonate, it is characterized in that a hydration 4-(4-dimethylamino styryl) organic pyridinium salt of picoline benzene sulfonate for being formed by zwitterion key, in its molecular structure, have π-electron conjugated system, single crystal diffraction test result shows that its chemical formula is C
22h
24n
2o
3sH
2o, at room temperature belongs to triclinic(crystalline)system, and spacer is P-1, and unit cell parameters is
α=106.1087 (12) °, β=91.3577 (12) °, γ=105.0583 (12) °,
z=4; Its skeleton symbol is as follows:
2. prepare a hydration 4-(4-dimethylamino styryl as claimed in claim 1 for one kind) method of picoline benzene sulfonate, it is characterized in that comprising building-up reactions, condensation reaction, ion exchange reaction and four steps of filtration purification, its specific embodiment is:
(1) building-up reactions: the 4-picoline that the purity of getting identical mol ratio concentration is 98% and purity are not less than 98% methyl iodide and are mixed to get mixing solutions, and mixing solutions is placed in to purity is 99.7% dehydrated alcohol, wherein the volume ratio of mixing solutions and dehydrated alcohol is 3:2, the standing at room temperature spontaneous building-up reactions of carrying out after stirring, react and generate white needles solid after 10-20 minute, through filtering, obtain 4-picoline salt compounded of iodine, then that 4-picoline salt compounded of iodine oven dry sealed storage is standby; Purity is not less than to 98% Phenylsulfonic acid again and is dissolved in the silver suboxide that is 99.7% with purity after deionized water and at room temperature carries out building-up reactions 1 minute, wherein, the mass ratio of Phenylsulfonic acid and deionized water is 1:5, and the mol ratio of Phenylsulfonic acid and silver suboxide is 2:1; Filtration obtains Phenylsulfonic acid solution, then uses conventional evaporation drying device by Phenylsulfonic acid solution evaporate to dryness, obtains dry Phenylsulfonic acid silvery white solid, and Phenylsulfonic acid silver sealed storage is standby;
(2) condensation reaction: get the 4-picoline salt compounded of iodine of identical mol ratio and analytical pure paradimethy laminobenzaldehyde and be dissolved in respectively purity and be not less than in 99.5% anhydrous methanol, wherein the mass ratio of 4-picoline salt compounded of iodine and anhydrous methanol is 1:6, the mass ratio of paradimethy laminobenzaldehyde and anhydrous methanol is 1:9, heated and stirred makes 4-picoline and paradimethy laminobenzaldehyde be dissolved in respectively anhydrous methanol to be completely placed in three hole flasks, stirring is warming up to 65-70 ℃, carry out condensing reflux simultaneously, add 15-20 drip piperidines as catalyst solution by the light yellow scarlet that gradually becomes, condensation reaction obtains 4-(4-dimethylamino styryl) picoline iodide,
(3) ion exchange reaction: carry out after 18-24h in the condensation reaction of step (2), add the prepared Phenylsulfonic acid silver of step (1), the Phenylsulfonic acid silver adding and the 4-picoline salt compounded of iodine equimolar ratio in step (2), ion exchange reaction is carried out in continuation at 65-70 ℃, while condensing reflux, after reaction 18-24h, generate Silver iodide precipitation and a hydration 4-(4-dimethylamino styryl) picoline benzene sulfonate, the solution obtaining is dark red solution;
(4) filter and purify: the dark red solution filtered while hot that step (3) reaction is obtained, through standing, cooling and recrystallization, prepares a hydration 4-(4-dimethylamino styryl by the solution that filters Silver iodide precipitation) picoline benzene sulfonate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279818A (en) * | 2020-11-12 | 2021-01-29 | 青岛大学 | Preparation method of 2- (4-hydroxy) -styryl-5-chlorobenzothiazole p-toluenesulfonate |
| CN112679419A (en) * | 2020-12-28 | 2021-04-20 | 中国科学院福建物质结构研究所 | P-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate, preparation method and application |
| CN112939851A (en) * | 2021-01-29 | 2021-06-11 | 青岛大学 | 4- (4-hydroxy-3, 5-dimethyl styryl) methylpyridine p-aminobenzene sulfonate and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279818A (en) * | 2020-11-12 | 2021-01-29 | 青岛大学 | Preparation method of 2- (4-hydroxy) -styryl-5-chlorobenzothiazole p-toluenesulfonate |
| CN112679419A (en) * | 2020-12-28 | 2021-04-20 | 中国科学院福建物质结构研究所 | P-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate, preparation method and application |
| CN112939851A (en) * | 2021-01-29 | 2021-06-11 | 青岛大学 | 4- (4-hydroxy-3, 5-dimethyl styryl) methylpyridine p-aminobenzene sulfonate and preparation method thereof |
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