CN107056678A - A kind of organic nonlinear optical crystal material PBSB and its preparation technology - Google Patents
A kind of organic nonlinear optical crystal material PBSB and its preparation technology Download PDFInfo
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
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- C07D209/60—Naphtho [b] pyrroles; Hydrogenated naphtho [b] pyrroles
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Abstract
The invention belongs to technical field of function materials, specifically related to a kind of organic nonlinear optical crystal material and its preparation technology, particularly a kind of (E) 2 (4 (dimethylamino) styryl) 1, 1, benzene sulfonate of 3 trimethyl 1H benzos [e] indoles 3 and preparation method thereof, its preparation method includes synthetic reaction, condensation reaction, ion-exchange reactions, the step of filtration and recrystallization four, crystal prepared by the present invention, the cation and benzene sulfonate anion of benzindole ring are carried in structure, form larger pi-electron conjugated system, non-centrosymmetry is significantly improved, be conducive to producing larger nonlinear optical coefficients；Meanwhile, the crystal is not decomposed before 250 DEG C, and thermal stability is good, and purity is high, and preparation method is simple, and raw material is easy to get, and prepared by crystal and growth conditions is gentle, it is not necessary to strictly control the water content of each process；It is a kind of new non-linear optical crystal material, with higher potential practical value.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of organic nonlinear optical crystal material PBSB and its
Preparation technology, particularly one kind (E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e] indoles -
3- benzene sulfonates (PBSB) and preparation method thereof.
Background technology
Terahertz (THz) ripple refers to frequency in 0.1-10THz scopes, wavelength in the electromagnetic wave of 0.03-3mm scopes, terahertz
Hereby wave technology is in the basic research subject such as physics, chemistry, life science, and medical imaging, safety inspection, Product checking, sky
Between the application branch of learning such as communication, weapon guidance all there is important researching value and application prospect.And utilize non-linear optical methods
The THz ripples of the continuously adjustable of generation have higher power output and operating efficiency, and nonlinear optical crystal is to realize this skill
The key of art, while nonlinear optical crystal can be utilized for laser frequency conversion, realize laser signal storage etc., it is important
One of photoelectric information functional material, is indispensable critical material in new high-tech industry.
Organic nonlinear optical crystal because with isomers species is more, synthetic route flexibly, electron donor and acceptor relatively by force,
The characteristic such as conjugated bonds are extensible and planes of molecules is strong, the research focus as optical crystal material, and 4- (4- dimethylaminos
Base styryl) picoline tosilate (DAST) be nonlinear optical organic field a kind of significant material, because
Its cation is, with the organic structure for being conjugated big pi bond, to cause molecule that non-centrosymmetry is presented, and then it is shown preferably
Second-order nonlinear optical property.But research finds that DAST materials still suffer from some shortcomings：First, the crystal growth of DAST materials
And preservation condition is more harsh, each process need to be removed water strictly, and the crystal otherwise obtained is due to the presentation center with the crystallization water
Symmetrical structure, causes crystal without non-linear；Secondly, its molecular structure arranges not being optimal, its non-centrosymmetry
The space that property also improves a lot.Therefore, using the difference of molecular configuration activity, changing distinctive functional group in molecule makes molecule
Properties change, design prepare with bigger non-linear and crystal growth condition loosely new non-linear optical crystal
Body material has important research and application value.
The content of the invention
It is an object of the invention to overcome prior art to there is shortcoming, there is provided a kind of new organic nonlinear optical crystal material
Expect (E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e] indoles -3- benzene sulfonates, and provide
It designs preparation method.
To achieve these goals, one kind (E) -2- (4- (dimethylamino) styryl) -1,1,3- of the present invention
Trimethyl -1H- benzos [e] indoles -3- benzene sulfonates, its skeleton symbol is as follows：
Carried in the crystal structure on the cation and benzene sulfonate anion of benzindole ring, benzindole ring with excellent
Pi-electron conjugated system, make to form larger pi-electron conjugated system in whole crystal molecular structure, crystal structure it is non-central
Symmetry is significantly improved, and is conducive to producing larger nonlinear optical coefficients；Meanwhile, the crystal structure is stable, before 250 DEG C
Do not decompose, thermal stability is good.
The present invention provides one kind (E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e] Yin
The preparation method of diindyl -3- benzene sulfonates, including synthetic reaction, condensation reaction, ion-exchange reactions, four steps of filtration and recrystallization
Suddenly, its specific embodiment is：
(1) synthetic reaction：It is 2 in molar ratio:1 ratio weighs silver oxide (purity respectively>99.7%) it is (pure with benzene sulfonic acid
Degree>99.8%), fully dissolved in deionized water at room temperature respectively, wherein the mass ratio of silver oxide and deionized water is 1:
4, the mass ratio of benzene sulfonic acid and deionized water is 1:4；Obtained silver oxide solution is mixed with benzene sulfonic acid solution, and in room temperature
Under the conditions of stirring reaction 2 minutes, reaction solution collects solution after multiple suction filtration；Conventional drying rotary evaporating device is used again by gained
Solution is evaporated, and obtains the silver-colored solid of white benzene sulfonic acid of drying；After finally obtained benzene sulfonic acid silver is dried in vacuum drying chamber
Sealing preserve；
Three hole flasks are taken, the 1 of identical mole specific concentration, 1,2- trimethyl -1H- benzos [e] indoles (purity is separately added into>
98%) with iodomethane (purity>98%), with absolute methanol (purity>99.8%) it is solvent, wherein, 1,1,2- trimethyl -1H-
The mass ratio of benzo [e] indoles and absolute methanol is 1:6, filemot 1,1,2,3- tetramethyl is generated by condensing reflux reaction
Base -1H- benzos [e] indoles -3- iodized salt solutions, reaction temperature is 50 DEG C；
(2) condensation reaction：Weigh paradime thylaminobenzaldehyde (purity>95%) it is dissolved in absolute methanol (purity>99.8%),
Wherein, the mol ratio of paradime thylaminobenzaldehyde and 1,1,2- trimethyl -1H- benzos [e] indoles in step (1) is 1:1, to two
The mass ratio of methylamino phenenyl formaldehyde and absolute methanol is 1:9；Resulting solution is added to and fills 1,1,2,3- tetramethyl -1H- benzene
And in the three hole flasks of [e] indoles -3- iodized salt solutions, 70 DEG C are warming up to, add 15~20 and drip piperidines as catalyst, condensation is anti-
Trimethyl -1H- benzos [e] indoles -3- salt compounded of iodine of (E) -2- (4- (dimethylamino) styryl) -1,1,3- should be obtained；This is produced
It is placed in vacuum drying chamber and dries after thing recrystallization, sealing preserve；
(3) ion-exchange reactions：Weigh (E) -2- (4- (dimethylamino) styryl) -1,1,3- tri- of identical mol ratio
Methyl isophthalic acid H- benzos [e] indoles -3- salt compounded of iodine is dissolved in absolute methanol respectively with benzene sulfonic acid silver, wherein (E) -2- (4- (dimethylamino)
Styryl) mass ratio of -1,1,3- trimethyl -1H- benzos [e] indoles -3- salt compounded of iodine and absolute methanol is 1:9, benzene sulfonic acid silver
Mass ratio with absolute methanol is 1:5；Obtain two kinds of solution are added in three hole flasks and mixed, are condensed back at 70~80 DEG C
Stream 15~30h of reaction, obtains darkviolet (E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e]
Indoles -3- benzene sulfonate solution；
(4) filtration and recrystallization：The deep purple solution that step (3) is obtained is filtered while hot, is filtered silver iodide precipitation, will be obtained
Purple solution be placed in and be capable of in the crystal nourishing jar of temperature control, obtained product is finally placed in vacuum by slow cooling, then cooled down
Dried in drying box, obtain purple needle-like and block (E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -
1H- benzos [e] indoles -3- benzene sulfonates.
The purity of silver oxide of the present invention>99.7%, the purity of benzene sulfonic acid>99.8%, 1,1,2- trimethyl -1H-
The purity of benzo [e] indoles>98%, the purity of iodomethane>98%, the purity of absolute methanol>99.8%, to Dimethylaminobenzene first
The purity of aldehyde>95%.
Beneficial effects of the present invention are：(E) -2- (4- (dimethylamino) styryl) -1,1,3- tri- prepared by the present invention
The benzindole ring of excellent pi-electron conjugated system is carried in methyl isophthalic acid H- benzos [e] indoles -3- benzenesulfonate crystallines, structure
Cation and benzene sulfonate anion, make to form larger pi-electron conjugated system in whole crystal molecular structure, crystal structure
Non-centrosymmetry is significantly improved, and is conducive to producing larger nonlinear optical coefficients；Zwitterion passes through the close shape of ionic bond
Into stable connection structure, do not decomposed before 250 DEG C, thermal stability is good；Obtained crystal purity is high, preparation method letter
Single, raw material is easy to get, and prepared by crystal and growth conditions is gentle, it is not necessary to strictly control the water content of each process；It is a kind of new non-thread
Property optical crystal material, with higher potential practical value.
Brief description of the drawings
Fig. 1 is (E) -2- of the present invention (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e]
The apparent figure of indoles -3- benzene sulfonates.
Fig. 2 is (E) -2- of the present invention (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e]
Indoles -3- benzenesulfonate crystallines.
Fig. 3 is (E) -2- of the present invention (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e]
Indoles -3- benzene sulfonate Powder XRD patterns.
Fig. 4 is (E) -2- of the present invention (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e]
Indoles -3- benzene sulfonates Fourier transformation-infrared spectrum (FT-IR).
Fig. 5 is (E) -2- of the present invention (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e]
Indoles -3- benzene sulfonate nuclear magnetic resonance 1H is composed.
Embodiment
Below by specific embodiment combination accompanying drawing, the invention will be further described：
Embodiment 1
Trimethyl -1H- benzo [e] indoles -3- of (E) -2- (4- (dimethylamino) styryl) -1,1,3- of the present embodiment
The preparation method of benzene sulfonate, including synthetic reaction, condensation reaction, ion-exchange reactions, four steps of filtration and recrystallization, it has
Body technology process is：
(1) synthetic reaction：Weigh 0.05moL silver oxide (purity>99.7%) 80mL deionized waters are dissolved at room temperature,
Weigh 0.1moL benzene sulfonic acid (purity>99.8%) 70mL deionized waters are dissolved at room temperature, are sufficiently stirred for filling with glass bar
Divide dissolving；Reaction 2 minutes is stirred at room temperature in obtained benzene sulfonic acid solution and silver oxide solution, reaction solution is after 3 suction filtrations
Collect solution；Resulting solution is evaporated with conventional drying rotary evaporating device, to remove the deionized water in solution, drying is obtained
The silver-colored solid of white benzene sulfonic acid；Obtained benzene sulfonic acid silver is placed in after being dried in vacuum drying chamber and claims to obtain product 22.5g, yield is
84.9%, by product sealing preserve；
Weigh 0.03moL1,1,2- trimethyl -1H- benzos [e] indoles (purity>98%) with 0.03moL iodomethane (purity
>98%) with 25mL absolute methanol (purity>99.8%) it is solvent, it is yellowish-brown by condensing reflux reaction generation in three hole flasks
The 1 of color, 1,2,3- tetramethyl -1H- benzos [e] indoles -3- iodized salt solutions, reaction temperature is 50 DEG C.
(2) condensation reaction：Weigh 0.03moL paradime thylaminobenzaldehyde (purity>95%) it is dissolved in 25mL absolute methanols (pure
Degree>99.8%), resulting solution is added to the three holes burning for filling 1,1,2,3- tetramethyl -1H- benzos [e] indoles -3- iodized salt solutions
Bottle, is warming up to 70 DEG C, adds 15~20 and drips piperidines as catalyst, condensation reaction obtains (E) -2- (4- (dimethylamino) benzene second
Alkenyl) -1,1,3- trimethyl -1H- benzos [e] indoles -3- salt compounded of iodine；It is placed in vacuum drying chamber and dries after product is recrystallized,
Sealing preserve；
(3) ion-exchange reactions：Weigh 0.02moL (E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -
1H- benzos [e] indoles -3- salt compounded of iodine is dissolved in 20mL absolute methanols respectively with benzene sulfonic acid silver, and obtain two kinds of mixed solutions are added
Three hole flasks, condensing reflux obtains darkviolet (E) -2- (4- (dimethylamino) styrene after reacting 15~30h at 70~80 DEG C
Base) -1,1,3- trimethyl -1H- benzos [e] indoles -3- benzene sulfonate solution；
(4) filtration and recrystallization：The deep purple solution that step (3) is obtained is filtered while hot, is filtered silver iodide precipitation, will be obtained
Purple solution be placed in and be capable of in the crystal nourishing jar of temperature control, obtained product is placed in vacuum drying by slow cooling, then cooled down
Purple needle-like and bulk (E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos are dried to obtain in case
[e] indoles -3- benzene sulfonates.
Trimethyl -1H- benzos [e] Yin of (E) -2- (4- (dimethylamino) styryl) -1,1,3- manufactured in the present embodiment
Diindyl -3- benzene sulfonates amount to 3.25g, and yield is 31.7%.
Embodiment 2
(E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e] indoles -3- benzene sulfonates
Crystalline structure performance test
Trimethyl -1H- benzos [e] indoles of (E) -2- (4- (dimethylamino) styryl) -1,1,3- prepared by 20mg -
3- benzene sulfonate raw materials clay into power progress powder X-ray RD tests, from collection of illustrative plates it can be seen that diffraction maximum be concentrated mainly on 10 ° to
Between 30 °, and miscellaneous peak is less, and main diffraction peak half-peak breadth is narrower and sharp, shows that prepared material purity is higher, crystallinity compared with
It is good.
Embodiment 3
(E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e] indoles -3- benzene sulfonates
Molecular structure FT-IR spectrum tests
By (E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e] indoles -3- benzene sulfonates
Powder carries out FT-IR tests, it can be seen that there is absworption peak at 1167.97cm-1 in FT-IR collection of illustrative plates, shows there are S=O bases
, there is absworption peak at 1601.06cm-1, show the presence compared with multi-aromatic ring in the presence of group's vibration.
Embodiment 4
(E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzos [e] indoles -3- benzene sulfonates
Molecular structure nuclear-magnetism is tested
Trimethyl -1H- benzos [e] indoles of (E) -2- (4- (dimethylamino) styryl) -1,1,3- prepared by 5mg -
3- benzene sulfonates are dissolved in the deuterated DMSO of 0.5mL, carry out nuclear magnetic resonance1H spectrum tests, from NMR1It can be seen that in H collection of illustrative plates
The integral area ratio at each peak (being free of solvent peak of the displacement at the water peak and 2.5 at 3.3) of H displacements is represented in collection of illustrative plates
(0.16:0.16:0.16:0.23:0.32:0.16:0.32:0.97:1.00) with (E) -2- (4- (dimethylamino) styryl) -
The position number ratio (2 of H atom in 1,1,3- trimethyl -1H- benzos [e] indoles -3- benzene sulfonate molecular structural formulas:2:2:2:
3:4:2:3:12:12) match, miscellaneous peak does not occur.Test result shows (E) -2- (4- (diformazans that product is high-purity
Amino) styryl) -1,1,3- trimethyl -1H- benzos [e] indoles -3- benzene sulfonates.
Claims (2)
1. a kind of organic nonlinear optical crystal material PBSB, i.e. (E) -2- (4- (dimethylamino) styryl) -1,1,3- tri-
Methyl isophthalic acid H- benzos [e] indoles -3- benzene sulfonates, it is characterised in that skeleton symbol is as follows：
2. a kind of method for preparing organic nonlinear optical crystal material PBSB as claimed in claim 1, it is characterised in that：Bag
Synthetic reaction, condensation reaction, ion-exchange reactions, four steps of filtration and recrystallization are included, its specific embodiment is：
(1) synthetic reaction：It is 2 in molar ratio:1 ratio weighs silver oxide (purity respectively>99.7%) with benzene sulfonic acid (purity>
99.8%), fully dissolved in deionized water at room temperature respectively, wherein the mass ratio of silver oxide and deionized water is 1:4, benzene
Sulfonic acid and the mass ratio of deionized water are 1:4；Obtained silver oxide solution is mixed with benzene sulfonic acid solution, and in room temperature condition
Lower stirring reaction 2 minutes, reaction solution collects solution after multiple suction filtration；Conventional drying rotary evaporating device is used again by resulting solution
It is evaporated, obtains the silver-colored solid of white benzene sulfonic acid of drying；Sealed after finally obtained benzene sulfonic acid silver is dried in vacuum drying chamber
Preserve；
Three hole flasks are taken, the 1 of identical mole specific concentration, 1,2- trimethyl -1H- benzos [e] indoles (purity is separately added into>98%)
With iodomethane (purity>98%), with absolute methanol (purity>99.8%) it is solvent, wherein, 1,1,2- trimethyl -1H- benzos
The mass ratio of [e] indoles and absolute methanol is 1:6, filemot 1,1,2,3- tetramethyl -1H- is generated by condensing reflux reaction
Benzo [e] indoles -3- iodized salt solutions, reaction temperature is 50 DEG C；
(2) condensation reaction：Weigh paradime thylaminobenzaldehyde (purity>95%) it is dissolved in absolute methanol (purity>99.8%), its
In, the mol ratio of paradime thylaminobenzaldehyde and 1,1,2- trimethyl -1H- benzos [e] indoles in step (1) is 1:1, to diformazan
The mass ratio of aminobenzaldehyde and absolute methanol is 1:9；Resulting solution is added to and fills 1,1,2,3- tetramethyl -1H- benzos
In the three hole flasks of [e] indoles -3- iodized salt solutions, 70 DEG C are warming up to, 15~20 drop piperidines is added and is used as catalyst, condensation reaction
Obtain trimethyl -1H- benzos [e] indoles -3- salt compounded of iodine of (E) -2- (4- (dimethylamino) styryl) -1,1,3-；By this product
It is placed in vacuum drying chamber and dries after recrystallization, sealing preserve；
(3) ion-exchange reactions：Weigh (E) -2- (4- (dimethylamino) styryl) -1,1,3- front three of identical mol ratio
Base -1H- benzos [e] indoles -3- salt compounded of iodine is dissolved in absolute methanol respectively with benzene sulfonic acid silver, wherein (E) -2- (4- (dimethylamino) benzene
Vinyl) mass ratio of -1,1,3- trimethyl -1H- benzos [e] indoles -3- salt compounded of iodine and absolute methanol is 1:9, benzene sulfonic acid silver with
The mass ratio of absolute methanol is 1:5；Obtain two kinds of solution are added in three hole flasks and mixed, the condensing reflux at 70~80 DEG C
15~30h is reacted, trimethyl -1H- benzos [e] Yin of darkviolet (E) -2- (4- (dimethylamino) styryl) -1,1,3- are obtained
Diindyl -3- benzene sulfonate solution；
(4) filtration and recrystallization：The deep purple solution that step (3) is obtained is filtered while hot, silver iodide precipitation is filtered, by obtained purple
Color solution, which is placed in, is capable of in the crystal nourishing jar of temperature control, slow cooling, then is cooled down, and obtained product finally is placed in into vacuum drying
Dried in case, obtain purple needle-like and block (E) -2- (4- (dimethylamino) styryl) -1,1,3- trimethyl -1H- benzene
And [e] indoles -3- benzene sulfonates.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112279818A (en) * | 2020-11-12 | 2021-01-29 | 青岛大学 | Preparation method of 2- (4-hydroxy) -styryl-5-chlorobenzothiazole p-toluenesulfonate |
| CN114016137A (en) * | 2021-10-13 | 2022-02-08 | 天津理工大学 | Benzoindole iodine nonlinear optical crystal and preparation method and application thereof |
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| CN104945307A (en) * | 2015-05-18 | 2015-09-30 | 北京科技大学 | Benzoindolyl salt material and nonlinear optical crystal thereof, and preparation method and application thereof |
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| CN104945307A (en) * | 2015-05-18 | 2015-09-30 | 北京科技大学 | Benzoindolyl salt material and nonlinear optical crystal thereof, and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112279818A (en) * | 2020-11-12 | 2021-01-29 | 青岛大学 | Preparation method of 2- (4-hydroxy) -styryl-5-chlorobenzothiazole p-toluenesulfonate |
| CN114016137A (en) * | 2021-10-13 | 2022-02-08 | 天津理工大学 | Benzoindole iodine nonlinear optical crystal and preparation method and application thereof |
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