CN111960993A - Preparation method of 4- (3, 4-dimethoxystyryl) methylpyridine p-toluenesulfonate - Google Patents
Preparation method of 4- (3, 4-dimethoxystyryl) methylpyridine p-toluenesulfonate Download PDFInfo
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- CN111960993A CN111960993A CN202010883258.6A CN202010883258A CN111960993A CN 111960993 A CN111960993 A CN 111960993A CN 202010883258 A CN202010883258 A CN 202010883258A CN 111960993 A CN111960993 A CN 111960993A
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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
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
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Abstract
The invention belongs to the technical field of functional material preparation, and relates to a preparation method of 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate, wherein the chemical formula of the prepared 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystal is C23H27N2O5S, the purity is high, the raw materials are easy to obtain, the preparation method is simple, the reaction conditions are mild, the growth period is short, and the grown crystal has a highly polarizable pi electron conjugated system and is beneficial to generating a larger second-order nonlinear coefficient.
Description
The technical field is as follows:
the invention belongs to the technical field of functional material preparation, relates to a preparation method of an organic nonlinear crystal material, and particularly relates to a preparation method of 4- (3, 4-dimethoxystyryl) methylpyridine p-toluenesulfonate.
Background art:
the terahertz wave refers to an electromagnetic wave band between 0.1 and 10THz, and the frequency range of the terahertz wave enables the terahertz wave to have great application prospects in the application fields of basic subjects such as physics, chemistry and life science, drug identification, explosive detection, safety inspection and the like. The technology for generating terahertz waves based on the organic nonlinear optical crystal can cover the output range of the THz waves to the whole THz wave band, has the advantages of higher conversion efficiency, simple phase matching condition and the like, and has increasingly important position in the terahertz radiation generation technology. Currently, organic crystals used for generating THz waves are classified into ionic and molecular types. In 1970, R.Lemke et al reported for the first time that OH1(2- (3- (4-hydroxystyryl) -5, 5-dimethylcyclohex-2-enylidene) malononitrile) organic molecular crystal was synthesized, the crystal had a large second-order nonlinear coefficient, small absorption in low-frequency THz wave band, and wide application in photoelectric modulation, generation and detection of THz light wave, but most of molecular crystals had a central symmetric structure and could not exhibit nonlinear effect, and molecular crystal molecules had serious vibration and narrow THz wave output range. The ionic crystal is connected by ionic bonds between anions and cations, can inhibit intermolecular vibration, and has a high melting point. In 1989, S R Marker et al reported the nonlinear optical effect of DAST (4- (4-dimethylaminostyryl) methylpyridine p-toluenesulfonate) for the first time, the nonlinear crystal molecules of the pyridinium not only have very large first-order hyperpolarizability, but also the spatial arrangement of the molecules in the crystal is beneficial to generating large nonlinear optical effect, and the terahertz has important application value in the aspect of terahertz technology. While research on DAST crystal growth and THz performance is widely carried out, further development of DAST derivative crystals with excellent performance is expected, in 2005, crystals such as DSMOS, DSAS and DSMAS are synthesized by Yangtze and the like through replacing anions of the DAST crystals, but the solubility of the crystals in a solvent is too low, and large-size high-quality crystals are difficult to grow.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and provides a preparation method of a novel organic nonlinear crystal material 4- (3, 4-dimethoxystyryl) methylpyridine p-toluenesulfonate, wherein the prepared crystal has strong SHG strength and short growth cycle.
In order to achieve the above purpose, the method for preparing 4- (3, 4-dimethoxystyryl) methylpyridine p-toluenesulfonate according to the invention specifically comprises the following steps:
(1) respectively weighing 4-methylpyridine and methyl p-toluenesulfonate according to a molar ratio of 1: 0.5-1: 3, dissolving in 20-50 ml of methanol, pouring into a three-hole flask, magnetically stirring at 25-45 ℃, and carrying out condensation reflux for 18-24 hours;
(2) weighing 3, 4-dimethoxybenzaldehyde with the molar ratio of 1: 1-1: 4 to the product in the step (1), dissolving the 3, 4-dimethoxybenzaldehyde in 30-50 ml of methanol, pouring the dissolved solution into the three-hole flask in the step (1), dropwise adding 1-5 ml of piperidine as a catalyst, adjusting the temperature to 60-80 ℃, and reacting until a yellow precipitate is generated at the bottom of the flask;
(3) pouring the solution and the precipitate which are reacted in the step (2) into a beaker, cooling, pouring out the supernatant, and drying the residual precipitate in the beaker to obtain a 4- (3, 4-dimethoxystyryl) methylpyridine p-toluenesulfonate raw material;
(4) completely dissolving the dried 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate raw material in the step (3) in methanol, recrystallizing for 1-4 times, then carrying out suction filtration on the 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate solution, and filtering out insoluble impurities to obtain a high-purity 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystal growth raw material;
(5) the method comprises the steps of adopting a spontaneous nucleation method in the prior art to grow 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystals, using methanol as a solvent, preparing a solution of 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate with the concentration of 3-4 g/100ml, pouring the solution into a crystal growing bottle, keeping the solution at 45 ℃, stabilizing the solution for 24 hours, cooling the solution at the speed of 0.3-1 ℃/day, and obtaining the 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystals with the sizes of (1-5) mmx (1-5) x (0.2-1) mm after 10-30 days.
The chemical formula of the 4- (3, 4-dimethoxystyryl) methylpyridine p-toluenesulfonic acid salt crystal prepared by the invention is as follows: c23H27N2O5S, the structural formula is as follows:
compared with the prior art, the prepared novel organic optical crystal material 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate has high purity, easily obtained raw materials, simple preparation method, mild reaction conditions and short growth period, and the grown crystal has a highly polarizable pi electron conjugated system and is beneficial to generating larger second-order nonlinear coefficients.
Description of the drawings:
FIG. 1 is a crystal diagram of 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate prepared in the present invention.
FIG. 2 shows the NMR spectrum of 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystals prepared in the present invention.
FIG. 3 is an XRD pattern of crystals of 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate prepared in the present invention.
FIG. 4 shows the second harmonic efficiency of 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystals prepared by the present invention.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Example (b):
the preparation process of 4- (3, 4-dimethoxystyryl) methylpyridine p-toluenesulfonate according to this example includes the following steps:
(1) respectively weighing 4-methylpyridine and methyl p-toluenesulfonate according to a molar ratio of 1:1, dissolving in 50ml of methanol, pouring into a three-hole flask, magnetically stirring at 45 ℃, and condensing and refluxing for 24 hours;
(2) weighing 3, 4-dimethoxybenzaldehyde with the molar ratio of 1:1 to the product in the step (1), dissolving the 3, 4-dimethoxybenzaldehyde in 50ml of methanol, pouring the dissolved solution into the three-hole flask in the step (1), dropwise adding 3ml of piperidine serving as a catalyst, adjusting the temperature to 70 ℃, and reacting until a yellow precipitate is generated at the bottom of the flask;
(3) pouring the solution and the precipitate which are reacted in the step (2) into a beaker, cooling, pouring out the supernatant, and drying the residual precipitate in the beaker to obtain a 4- (3, 4-dimethoxystyryl) methylpyridine p-toluenesulfonate raw material;
(4) completely dissolving the dried 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate raw material in the step (3) in methanol, recrystallizing for 3 times, then carrying out suction filtration on the 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate solution, and filtering out insoluble impurities to obtain a high-purity 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystal growth raw material;
(5) the growth of 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystals is carried out by a spontaneous nucleation method, methanol is used as a solvent, a 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate solution with the concentration of 3.5g/100ml is prepared, the solution is poured into a crystal growing bottle, the temperature of the solution is kept at 45 ℃, the solution is stabilized for 24 hours, then the temperature is reduced at the speed of 0.5 ℃/day, and after 10 days, 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystals with the size of 2mm multiplied by 3 multiplied by 0.5mm are obtained, as shown in figure 1.
In this example, 5mg of 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate prepared was dissolved in 0.5ml of deuterated DMSO and subjected to NMR by a JNM ECP-600 type nuclear magnetic resonance spectrometer1H spectrum detection, the results are shown in FIG. 2, from NMR shown in FIG. 21The integral area ratio of each peak of the shifts of H atoms in the graph (1.95:0.94:1.25:1.92:1:1.19:0.64:0.68:1:0.89:3.63) to the H atom in the molecular structural formula of 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate can be seen in the H graphThe position and the number ratio (3:2:2:3:2:2:1:1:2:2:6) are matched.
Claims (2)
1. A preparation method of 4- (3, 4-dimethoxy styryl) methylpyridine p-toluenesulfonate is characterized by comprising the following steps:
(1) respectively weighing 4-methylpyridine and methyl p-toluenesulfonate according to a molar ratio of 1: 0.5-1: 3, dissolving in 20-50 ml of methanol, pouring into a three-hole flask, magnetically stirring at 25-45 ℃, and carrying out condensation reflux for 18-24 hours;
(2) weighing 3, 4-dimethoxybenzaldehyde with the molar ratio of 1: 1-1: 4 to the product in the step (1), dissolving the 3, 4-dimethoxybenzaldehyde in 30-50 ml of methanol, pouring the dissolved solution into the three-hole flask in the step (1), dropwise adding 1-5 ml of piperidine as a catalyst, adjusting the temperature to 60-80 ℃, and reacting until a yellow precipitate is generated at the bottom of the flask;
(3) pouring the solution and the precipitate which are reacted in the step (2) into a beaker, cooling, pouring out the supernatant, and drying the residual precipitate in the beaker to obtain a 4- (3, 4-dimethoxystyryl) methylpyridine p-toluenesulfonate raw material;
(4) completely dissolving the dried 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate raw material in the step (3) in methanol, recrystallizing for 1-4 times, then carrying out suction filtration on the 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate solution, and filtering out insoluble impurities to obtain a high-purity 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystal growth raw material;
(5) the method comprises the steps of adopting a spontaneous nucleation method in the prior art to grow 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystals, using methanol as a solvent, preparing a solution of 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate with the concentration of 3-4 g/100ml, pouring the solution into a crystal growing bottle, keeping the solution at 45 ℃, stabilizing the solution for 24 hours, cooling the solution at the speed of 0.3-1 ℃/day, and obtaining the 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate crystals with the sizes of (1-5) mmx (1-5) x (0.2-1) mm after 10-30 days.
2. The process for preparing 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate according to claim 1, wherein the crystal of 4- (3, 4-dimethoxystyryl) picoline p-toluenesulfonate produced has the formula: c23H27N2O5S, the structural formula is as follows:
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Cited By (2)
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| 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 |
| CN113293439A (en) * | 2021-04-22 | 2021-08-24 | 青岛大学 | Organic nonlinear optical crystal material DOBT and preparation method thereof |
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| CN105648519A (en) * | 2016-01-11 | 2016-06-08 | 青岛大学 | Square rectangular-pyramid-bottom DAST (diethylaminosulfurtrifluoride) crystal growth device |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN113293439A (en) * | 2021-04-22 | 2021-08-24 | 青岛大学 | Organic nonlinear optical crystal material DOBT and preparation method thereof |
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