CN103524405B - 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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- CN103524405B CN103524405B CN201310480269.XA CN201310480269A CN103524405B CN 103524405 B CN103524405 B CN 103524405B CN 201310480269 A CN201310480269 A CN 201310480269A CN 103524405 B CN103524405 B CN 103524405B
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- C07D213/00—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
- 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
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
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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-dimethylaminostyryl) picoline benzene sulfonate and preparation method thereof.
Background technology:
The non-linear effect of organic nonlinear optical crystal causes rapidly the very big attention of people after 1964 find, and found the organic nonlinear optical crystal of many excellent propertys successively, the advantage that organic non linear optical material has inorganic materials incomparable, as raw material is extensive, be easy to design molecular structure, non-linear electric susceptibility is large, and these advantages make, and organic non linear optical material becomes irreplaceable photonic material of new generation after inorganic materials.At present, have been found that a lot of organic nonlinear optical crystal, typical second-order non-linear optical crystal comprises urea and derivative thereof, organic pyridinium salt class and formiate, find in the research of organic non linear optical material, organic pyridinium salt and derivative thereof are that a quasi-nonlinear is active large, assemble various informative molecular material, wherein styryl pyridinium, organic pyridinium salt is a class organic non linear optical material of current most study, 4-(4-dimethylaminostyryl) picoline tosilate is the one that at present research is more, it is a kind of organic salt crystal formed 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-dimethylaminostyryl) picoline tosilate shown good two-stage non-linear optical property.Therefore, by changing the functional group in anionic group, design and synthesis prepares a kind of novel organic optical crystalline material one hydration 4-(4-dimethylaminostyryl) picoline benzene sulfonate and preparation method thereof, there is potential using value and practical significance.
Summary of the invention:
The object of the invention is to the shortcoming overcoming prior art existence, seek a kind of novel organic optical crystalline material one hydration 4-(4-dimethylaminostyryl 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-dimethylaminostyryl that the present invention relates to) picoline benzene sulfonate is the organic pyridinium salt formed by zwitterion key, there is larger π-electron conjugated system in its molecular structure, 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-dimethylaminostyryl that the present invention relates to) preparation method of picoline benzene sulfonate comprises building-up reactions, condensation reaction, ion exchange reaction and filtration and to purify four steps, and its specific embodiment is:
(1) building-up reactions: the purity of getting identical mole specific concentration be 98% 4-picoline and the purity methyl iodide that is not less than 98% be mixed to get mixing solutions, and mixing solutions is placed in the dehydrated alcohol that purity is 99.7%, wherein the volume ratio of mixing solutions and dehydrated alcohol is 3:2, leave standstill after stirring and at room temperature spontaneously carry out building-up reactions, react and generate white needles after 10-20 minute, 4-picoline salt compounded of iodine is obtained, then by for subsequent use for 4-picoline salt compounded of iodine oven dry sealed storage through filtration; The silver suboxide being 99.7% with purity after the Phenylsulfonic acid again purity being not less than 98% is dissolved in deionized water at room temperature carries out building-up reactions 1 minute, and 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 benzene sulfonic acid solution, then uses conventional evaporation drying device by benzene sulfonic acid solution evaporate to dryness, obtains dry Phenylsulfonic acid silvery white solid, and by for subsequent use for Phenylsulfonic acid silver sealed storage;
(2) condensation reaction: get the 4-picoline salt compounded of iodine of identical mol ratio and analytical pure paradimethy laminobenzaldehyde and be dissolved in purity respectively and be not less than in the anhydrous methanol of 99.5%, 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 anhydrous methanol respectively to be completely placed in three hole flasks, stirring is warming up to 65-70 DEG C, carry out condensing reflux simultaneously, add 15-20 to drip piperidines and gradually become scarlet as catalyst solution by light yellow, condensation reaction obtains 4-(4-dimethylaminostyryl) methyl pyridinium iodide,
(3) ion exchange reaction: after 18-24h is carried out in the condensation reaction of step (2), add the Phenylsulfonic acid silver prepared by step (1), the Phenylsulfonic acid silver and the 4-picoline salt compounded of iodine equimolar ratio in step (2) that added, continue to carry out ion exchange reaction at 65-70 DEG C, condensing reflux simultaneously, Silver iodide precipitation and a hydration 4-(4-dimethylaminostyryl is generated after reaction 18-24h) picoline benzene sulfonate, the solution obtained is dark red solution;
(4) filtration is purified: dark red solution filtered while hot step (3) be obtained by reacting, and by filtering the solution of Silver iodide precipitation through leaving standstill, cooling and recrystallization, prepares a hydration 4-(4-dimethylaminostyryl) picoline benzene sulfonate.
A hydration 4-(4-dimethylaminostyryl prepared by the present invention) picoline benzenesulfonate crystalline do not decompose before 238 DEG C, and thermal stability is good; In its molecular structure, the kind of hydrogen atom and number and nucleus magnetic resonance 1H represent that the number at the peak of hydrogen atom displacement and the integral area at each peak match in composing; Carbon atom kind and nucleus magnetic resonance 13C compose 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, and purity is high, and raw material is easy to get in the present invention, and preparation method is simple, and reaction conditions is gentle, and potential implementary value is high.
Accompanying drawing illustrates:
Fig. 1 is the hydration 4-(4-dimethylaminostyryl that the present invention relates to) molecular structure of picoline benzene sulfonate.
Fig. 2 is the hydration 4-(4-dimethylaminostyryl that the present invention relates to) crystallogram of picoline benzene sulfonate.
Fig. 3 is the hydration 4-(4-dimethylaminostyryl that the present invention relates to) nucleus magnetic resonance of picoline benzene sulfonate
1h composes.
Fig. 4 is the hydration 4-(4-dimethylaminostyryl that the present invention relates to) nucleus magnetic resonance of picoline benzene sulfonate
13c composes.
Embodiment:
Also by reference to the accompanying drawings the present invention is elaborated below by embodiment.
Embodiment:
The present embodiment prepares a hydration 4-(4-dimethylaminostyryl) concrete steps of picoline benzene sulfonate comprise building-up reactions, condensation reaction, ion exchange reaction and filtration and to purify four steps:
(1) building-up reactions: it is in the dehydrated alcohol of 99.7% that methyl iodide (purity the is not less than 98%) mixing of the 4-picoline (purity is 98%) and 0.1mol of getting 0.1mol is placed on 10-12ml purity, stir, after 10-15 minute, reaction generates white needles, be the dehydrated alcohol washing and filtering of 99.7% by 8-10ml purity and obtain 4-picoline salt compounded of iodine 17.6g with vacuum drying oven oven dry, productive rate is 74.9%, then by for subsequent use for 4-picoline salt compounded of iodine sealed storage; Then the Phenylsulfonic acid (purity is not less than 98%) of 0.1mol and the silver suboxide (purity is 99.7%) of 0.05mol is got, Phenylsulfonic acid (purity is not less than 98%) to be dissolved in 50-60ml deionized water and to react with silver suboxide (purity is 99.7%), the dilution of 50-60ml deionized water is added again after reaction, filtration obtains benzene sulfonic acid solution, use evaporation drying device rotatory evaporator by solution evaporate to dryness again, obtain dry Phenylsulfonic acid silvery white solid 23.5g, productive rate is 85.8%, by for subsequent use for Phenylsulfonic acid silver sealed storage;
(2) condensation reaction: the paradimethy laminobenzaldehyde (analytical pure) of the 4-picoline salt compounded of iodine and 0.03mol of getting 0.03mol is dissolved in 40ml and 60ml anhydrous methanol (purity is not less than 99.5%) respectively, heated and stirred makes it dissolve completely to be placed in the three hole flasks of 250ml, stirring is warming up to 65-70 DEG C, carry out condensing reflux simultaneously, add 15-20 and drip piperidines as catalyzer, solution gradually becomes scarlet by light yellow, obtains 4-(4-dimethylaminostyryl after condensation reaction 18-24h) methyl pyridinium iodide;
(3) ion exchange reaction: after 18-24h is carried out in the condensation reaction of step (2), add the Phenylsulfonic acid silver prepared by 0.03mol step (1), with 4-(4-dimethylaminostyryl) at 65-70 DEG C, there is ion exchange reaction in methyl pyridinium iodide, Silver iodide precipitation and a hydration 4-(4-dimethylaminostyryl is generated after condensing reflux 12-18h) picoline benzene sulfonate, the solution obtained is dark red solution;
(4) purification is filtered: by the dark red solution filtered while hot of about the 100ml that step (3) is obtained by reacting, filter the solution of Silver iodide precipitation through leaving standstill, cool and light green needle-like or a block hydration 4-(4-dimethylaminostyryl can being obtained at the middle recrystallization of 100-150ml anhydrous methanol (purity is not less than 99.5%)) picoline benzenesulfonate crystalline, productive rate is 43.8%.
The hydration 4-(4-dimethylaminostyryl that 5mg is prepared by the present embodiment) 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
1integral area ratio (1.94:2.02:1:4.04:2.99:1.04:1.95:2.97:6.1) and a hydration 4-(4-dimethylaminostyryl at each peak (containing displacement at the water peak of about 3.3 and the solvent peak of about 2.5) representing H atom displacement in collection of illustrative plates can be found out in H collection of illustrative plates (Fig. 3)) position of H atom (containing the H atom in crystal water) and number ratio (2:2:1:4:3:1:2:3:6) match in picoline benzene sulfonate molecular structural formula, and assorted peak occurs; From NMR
13can find out in C collection of illustrative plates (Fig. 4) that the spectral line of C knocking out in collection of illustrative plates has at 15 (not solvent-laden peaks), with a hydration 4-(4-dimethylaminostyryl) 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-dimethylaminostyryl) picoline benzene sulfonate.
Claims (1)
1. hydration 4-(4-dimethylaminostyryl) picoline benzene sulfonate, it is characterized in that a hydration 4-(4-dimethylaminostyryl) picoline benzene sulfonate is the organic pyridinium salt formed by zwitterion key, there is π-electron conjugated system in its molecular structure, 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:
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| 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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