CN106554304A - The synthesis of 4- (4- dimethylaminostyryls) picoline 3-carboxyl -4- phenolsulfonates and crystal preparation method - Google Patents

The synthesis of 4- (4- dimethylaminostyryls) picoline 3-carboxyl -4- phenolsulfonates and crystal preparation method Download PDF

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CN106554304A
CN106554304A CN201510616636.3A CN201510616636A CN106554304A CN 106554304 A CN106554304 A CN 106554304A CN 201510616636 A CN201510616636 A CN 201510616636A CN 106554304 A CN106554304 A CN 106554304A
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dimethylaminostyryls
carboxyl
crystal
picoline
slow cooling
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周在国
杨洲
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Ji'nan Lehua Biotechnology Co Ltd
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Ji'nan Lehua Biotechnology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/54—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
    • C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The present invention discloses a kind of synthesis and the crystal preparation method of 4- (4- dimethylaminostyryls) picoline 3-carboxyl -4- phenolsulfonates.Wherein, DSCHS second-order non-linear optical crystals are grown using the method that slow cooling and slow evaporation are used in mixed way, first in the method for slow cooling, the nucleus that spontaneous nucleation is formed is used as crystal seed, the various impacts of plus seed initiation can be excluded, while the method that the later stage is combined using slow cooling and slow evaporation, shortens the test period, the bulky crystal for meeting application requirement is have successfully been obtained finally, size is 18 × 10 × 4mm3。

Description

The synthesis of 4- (4- dimethylaminostyryls) picoline 3-carboxyl -4- phenolsulfonates and crystalline substance Preparation
Technical field
The present invention relates to non-linear optical field, more particularly to a kind of 4- (4- dimethylaminostyryls) first The new synthesis of yl pyridines 3- carboxyl -4- phenolsulfonates and crystal preparation method.
Background technology
In recent years, under the huge driving of information technology, quickly, new crystal layer goes out photoelectric functional crystal development Not poor, nonlinear optical crystal is exactly the Typical Representative of this class material.From technical field to research field, Nonlinear optical crystal suffers from being widely applied：Make electrooptical switching and realize the modulation of laser；By swashing The conversion of light frequency is obtained and is as short as ultraviolet, VUV, long to far various laser；Using Optical Parametric Amount vibration realizes that the tuning of laser frequency (is combined with frequency multiplication, frequency mixing technique at present and can realize therefrom The infrared tuning in VUV broad range)；Can also be using defeated in some nonlinear optical effects Go out the phase conjugate feature that light beam has, carry out optical Information Processing, improve image quality and beam quality Etc..
For the crystal growth of nonlinear optical material, the method for generally adopting has two kinds：Slow evaporation method and Slow cooling method.Slow evaporation method is easy to operate, and instrument is simple, is most common method, easily grows up to big Block, the crystal that has good uniformity, and have more complete profile；As a rule, directly can observe Crystal growing process, is easy to the research to crystal growth kinetics.But the method is easily affected by extraneous factor, Simultaneously to be easier to grow up to bulky crystal, it will usually introduce crystal seed in early growth period, but the preparation of crystal seed, Choose and add these factors, can all affect the growth of crystal, this considerably increases crystal growth successful It is uncertain.For slow evaporation method, crystal growth can be controlled by controlling temperature, eliminate extraneous temperature The impact of degree, but this kind of method instrument and equipment is more bothered compared to slow evaporation method, and need material The change of solubility with temperature have obvious difference.
Therefore, an important research target in non-linear optical field is to explore to obtain one kind more effectively Growing method.We once applied for 4- (4- dimethylaminostyryls) picoline 3-carboxyl -4- The preparation of phenolsulfonate and growing method, but original preparation method is comparatively laborious, and adopt Single growing method can not obtain big crystal, therefore our preparations and crystal growth side to this material Method is improved, and achieves important progress.
The content of the invention
It is an object of the present invention to provide a kind of 4- (4- dimethylaminostyryls) first as shown in following formula 1 Yl pyridines 3- carboxyl -4- phenolsulfonate (molecular formula C23H24N2O6S, abbreviation DSCHS) new preparation Method.
Formula 1
It is a further object to provide a kind of new growth of above-mentioned DSCHS second-order non-linear optical crystals Method.
The DSCHS and its second-order non-linear optical crystal of the present invention is prepared by following methods：Raw material 4- methyl pyrroles Pyridine generates Isosorbide-5-Nitrae-lutidines iodine salt by salt-forming reaction with iodomethane first；Then Isosorbide-5-Nitrae-lutidines iodine Salt and paradime thylaminobenzaldehyde generate 4- (4- dimethylaminostyryls) picoline iodine by coupled reaction Salt；Again will be 4- (4- dimethylaminostyryls) picoline iodine salt soluble in water, add excessive 3- carboxyls - 4- hydroxy benzenesulfonic acid saturated aqueous solution of sodium is replaced, and obtains 4- (4- dimethylaminostyryls) picoline 23- carboxyls -4- phenolsulfonates (DSCHS).Filter, the precipitation for obtaining is carried out into recrystallization, after purification 45～50 DEG C of saturated solution is produced in being dissolved in methanol aqueous solution, is made using slow cooling and slow evaporation mixing Method, obtains nucleus by the spontaneous nucleation reaction of slow cooling first, then with these nucleus as crystal seed, DSCHS second-order non-linear optical crystals are grown using slow evaporation method.
The method that this kind of growing method is used in mixed way using slow cooling and slow evaporation, by it is spontaneous into Core can exclude the various impacts of plus seed initiation, while the later stage is combined using slow cooling and slow evaporation Method, achieve and original be beyond one's reach effect using single method.
Description of the drawings
Fig. 1 is that slow cooling method and slow evaporation are used in mixed way the bulky crystal for growing.
Specific embodiment
In the present invention, raw material and reagent used are common commercially available reagent.
The system of 1 4- of embodiment (4- dimethylaminostyryls) picoline 3-carboxyl -4- phenolsulfonates It is standby.
DSCHS material synthesis processes shown in formula 1 are as follows, and which mainly includes two parts：
I.4- the synthesis of (4- dimethylaminostyryls) picoline iodine salt；
II. anion metathesis reaction.
1. iodomethane (CH3I)；2. paradime thylaminobenzaldehyde；3.3- carboxyl -4- phenolsulfonate sodium.
I.4- the synthesis of (4- dimethylaminostyryls) picoline iodine salt：
(1) 0.1mol 4- picolines and 0.1mol iodomethane are placed in and are filled in right amount without water beetle according to 1: 1 ratio In the twoport round-bottomed flask of alcohol, 12h is heated to reflux, room temperature is cooled to, be filtrated to get solid, again with methanol Recrystallization is carried out, the solid for obtaining is vacuum dried.
(2) product of step (1) and paradime thylaminobenzaldehyde are dissolved in into methanol solvate with 1: 1.1 mol ratio In, add catalyst piperidines, 85 DEG C of temperature setting after back flow reaction 24h, to be cooled to room temperature, filter Solid is obtained, again with methanol recrystallization three times filters gained solid vacuum drying, that is, obtains 4- (4- bis- Methylamino styryl) picoline iodine salt.
II. anion metathesis reaction：
(3) 800mL deionized waters are added in 1000mL beakers, adds excessive 4- (4- dimethylamino benzene second Thiazolinyl) picoline iodine salt, iodine salt is fully dissolved after prolonged stirring and ultrasonic vibration, filter To saturated solution.
(4) the above-mentioned saturated solutions of 400mL are taken, in molar ratio (anion sodium salt: Propidium iodide salt=5: 1) weigh 3- carboxyl -4- the DHBSs of respective quality make sulfonate sodium in being dissolved in minimum deionized water Solution, pours the 3- carboxyl -4- hydroxy benzenesulfonic acid saline solution for preparing into 4- (4- dimethylaminostyrenes Base) picoline iodine salt saturated aqueous solution in, sufficient standing is separated out to there is solid.
(5) sucking filtration removes filtrate, carries out recrystallization, drying to solid product, obtains 4- (4- dimethylamino benzene second Thiazolinyl) picoline 3-carboxyl -4- phenolsulfonates (DSCHS).
Nuclear-magnetism result：1HNMR (300MHz, DMSO-d6)：
δ=8.68 (d, 2H, J=6.1Hz, C5H4N), 8.04 (d, 3H, J=4.5Hz, C5H4N+C7H5O6S), 7.91 (d, 1H, J=16.0Hz, C2H2), 7.68 (d, 1H, J=8.5Hz, C7H5O6S), 7.60 (d, 2H, J=8.0, C6H4), 7.18 (d, 1H, J=16.1Hz, C2H2), 6.87 (d, 1H, J=8.5Hz, C7H5O6S), 6.79 (d, 2H, J=8.1, C6H4), 4.17 (s, 3H, NMe), 3.02 (s, 6H, NMe2).
The growth of 2 DSCHS crystal of embodiment
Research confirms that the polarity of solvent can affect the growth characteristics of pi-conjugated crystal.In this test, we Have selected highly polar methanol solvate to grow DSCHS crystal.In view of adopting single crystal growth side in the past Method cannot obtain big crystal, and we have creatively used the method that slow cooling and slow evaporation are used in mixed way Carry out crystal growth.Initially with slow cooling method, the saturated solution under higher temperature is lowered the temperature, During being somebody's turn to do, the phenomenon for having spontaneous nucleation occurs, i.e., in temperature-fall period, have some small crystal nucleus and formed, It is most small crystal nucleus dissolving to heat up again, only retains one or two therein as crystal seed, treats that temperature is down to After room temperature, continue crystal growth using the method for slow evaporation, finally give ideal bulky crystal.
Using slow cooling and slow evaporation mixed method growth crystal, both eliminated in slow evaporation method because drawing Enter various uncertain factors caused by external crystal seed, considerably increase the success rate of crystal growth, and because of certainly After sending out nucleation formation crystal seed, crystal growth pattern switchs to the method that slow cooling and slow evaporation combine, and takes Obtained original employing single method to be beyond one's reach effect.
The material DSCHS of present invention synthesis is carried out using the method that slow cooling and slow evaporation are used in mixed way Crystal growth, step are as follows：
1) under the conditions of 50 DEG C of oil bath, the methanol solution for measuring 500ml is placed in the round-bottomed flask of 1000ml, The dried 4- of 1.0g (4- dimethylaminostyryls) picoline 3-carboxyl -4- hydroxyls are weighed again During benzene sulfonate (DSCHS) adds flask, stirrer is added, 24h is molten to ensure methanol for stirring Liquid has reached saturation.
2) it is ensure solution absolute pure, under conditions of 50 DEG C, using the organic of syringe and 0.22 μm Microfilter is filtered to above-mentioned saturated solution.Then it is molten to saturation with daily 2-3 DEG C of condition Liquid carries out slow cooling, in the process, has the generation of spontaneous nucleation phenomenon, begins with nucleus life It is long, high-temperature is risen with daily 2-3 DEG C of condition still then, most nucleus dissolving is made, is only protected Wherein one or two is stayed as crystal seed.
Below solution insulation is transferred in the 1000ml beakers of absolute cleanliness, beaker is placed in oil bath, uses preservative film Closing beaker mouth, air-vent bundles on, and beaker is put to peace and quiet, volatilization at sunshade, during to keep away as far as possible Exempt from vibrations；Lowered the temperature with daily 1 DEG C of condition simultaneously, after being down to room temperature, be still allowed to be maintained at slow steaming Hair-like state carries out crystal growth.Observation growth state of crystal, finds to form redness in spontaneous nucleation daily After DSCHS nucleus, crystal is in plane growth along the edge of any direction of nucleus.Until solution is complete After volatilization, size is obtained and reaches 18 × 10 × 4mm3Bulky crystal.

Claims (2)

1.4- (4- dimethylaminostyryls) picoline 3-carboxyl -4- phenolsulfonates (structural formula such as formula 1 It is shown) new preparation method, specifically as shown in following steps：
1. iodomethane；2. paradime thylaminobenzaldehyde；3.3- carboxyl -4- DHBSs.
A) 4- picolines and iodomethane act on forming Isosorbide-5-Nitrae-lutidines iodine salt；
B) salt and paradime thylaminobenzaldehyde reaction generates 4- (4- dimethylaminostyryls) methyl pyrrole Pyridine iodine salt；
C) will be the 4- obtained in step b) (4- dimethylaminostyryls) picoline iodine salt soluble in water, Add excessive 3- carboxyl -4- hydroxy benzenesulfonic acid saturated aqueous solution of sodium to be replaced, it is heavy by what is obtained Shallow lake purification obtains final product 4- (4- dimethylaminostyryls) picoline 3-carboxyl -4- hydroxy benzenesulfonic acids Salt.
2. 4- (4- dimethylaminostyryls) picoline 3-carboxyl -4- hydroxy benzeness sulphurs as claimed in claim 1 The preparation method of the second-order non-linear optical crystal of hydrochlorate, the method is by two kinds of slow cooling and slow evaporation Method combines.First in the method for slow cooling, nucleus is obtained by spontaneous nucleation reaction；Then with These nucleus are crystal seed, and the method combined using slow cooling and slow evaporation grown size and reach 18 ×10×4mm3Bulky crystal.
CN201510616636.3A 2015-09-24 2015-09-24 The synthesis of 4- (4- dimethylaminostyryls) picoline 3-carboxyl -4- phenolsulfonates and crystal preparation method Pending CN106554304A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108997312B (en) * 2018-08-09 2020-09-29 济南大学 RNA fluorescent probe for positioning mitochondria

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101823995A (en) * 2010-03-31 2010-09-08 北京科技大学 4-(4-dimethylaminostyryl) picoline3-carboxyl-4-hydroxy benzene sulfonate, nonlinear optical crystal and preparation method thereof
CN104073880A (en) * 2014-07-16 2014-10-01 青岛大学 Growth method for 4-(4-dimethyl-amino-styryl) picoline 4-toluenesulfonate crystal

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101823995A (en) * 2010-03-31 2010-09-08 北京科技大学 4-(4-dimethylaminostyryl) picoline3-carboxyl-4-hydroxy benzene sulfonate, nonlinear optical crystal and preparation method thereof
CN104073880A (en) * 2014-07-16 2014-10-01 青岛大学 Growth method for 4-(4-dimethyl-amino-styryl) picoline 4-toluenesulfonate crystal

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JIANHONG YIN ET AL.: "A new stilbazolium salt with perfectly aligned chromophores for second-order nonlinear optics: 4-N,N-Dimethylamino-4′-N′-methyl-stilbazolium 3-carboxy-4- hydroxybenzenesulfonate", 《DYES AND PIGMENTS》 *
李长春编著: "《功能材料》", 30 June 2014, 哈尔滨工业大学出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108997312B (en) * 2018-08-09 2020-09-29 济南大学 RNA fluorescent probe for positioning mitochondria

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