CN100361990C - Second order non-linear optical chromophore containing indolyl radical and its prepn and application - Google Patents
Second order non-linear optical chromophore containing indolyl radical and its prepn and application Download PDFInfo
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- CN100361990C CN100361990C CNB2005100193965A CN200510019396A CN100361990C CN 100361990 C CN100361990 C CN 100361990C CN B2005100193965 A CNB2005100193965 A CN B2005100193965A CN 200510019396 A CN200510019396 A CN 200510019396A CN 100361990 C CN100361990 C CN 100361990C
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Abstract
The present invention relates to second order non-linear optical chromophore containing indolyl groups, which has a general formula of *, wherein the R is various alkyl, aryl groups or other heterocyclic compound functional groups. The X is oxygen or sulfur atoms, the A is various electron-drawing acceptors, such as malononitrile, thiobarbituric acid, 3-isoxazolone, 2-dicyanomethylene-3-cyano-4, 5, 5-trimethyl-2, 5-dihydrofuran, etc. The present invention comprises a series of chemical reactions, indole, halogenated hydrocarbon, various electron acceptors, brom furylmethyl triphenylphosphine or 2-methylthiophene and other agents are used as raw material, and the second order non-linear optical chromophore containing indolyl groups is prepared. The second order non-linear optical chromophore containing indolyl groups can be used as a second order non-linear optical material and can be used in remote communication, data storage, phase conjugation, etc.
Description
Technical field
The present invention relates to second-order nonlinear optical chromophore that contains indolyl radical and preparation method thereof.
Background technology
Information technology is to rely on electronics and microtronics technical development, but because the physics limit of electronics itself---comprises the DENSITY LIMIT that electronics forms owing to the mutual interference mutually of elementary charge as the transmission speed limit (maximum value of electric transmission speed is 600km/s) of information carrier and element (functional unit)---, and " Moore's Law " can not be grown and exist in the youth, the carrier magnitude of electronic information technology can only be lucky position (Gb, promptly 10
9Bits).On the other hand, the speed of photon is fast more than electronics, the frequency of its frequency ratio wireless (as microwave) is much higher, replace electronics to come transmission information with photon, can accelerate information processing speed greatly, increase the capacity of process information, can overcome the bottleneck of microelectronics, more accurate, more efficient, long-distance transmissions information more.Development for full optical information technology, nonlinear optics (NLO) is indispensable crucial subject, it has very important effect in practical fields such as high-speed light communication, optical information processing and photoelectronics, and nonlinear optical material obtains more and more widely attention in these Application for Field prospects.
Compare with inorganic materials, the organic polymer nonlinear optical material is paid attention to widely with advantage such as its super fast response speed, bigger nonlinear optical response, high light injury threshold values, excellent workability and low-k.In order to reach the requirement of practicability, these materials not only will have big nonlinear optical response, and to satisfy device simultaneously to its transparency, thermostability with can process and the aspect requirement such as give birth to, because the nonlinear optical properties of nonlinear optical active group (often claiming chromophoric group) molecule is wherein all at first depended in the nonlinear optical response of macromolecular material, so the synthetic second-order nonlinear optical chromophore molecule that has the big molecule single order hyperpolarizability (β) and the good optical transparency concurrently of design is one of challenging problem of tool for a long time always.
Below be reference related to the present invention: Moemer, W.E.; Jepsen, A.G.; Thompson, C.L.Annu.Rev.Mater.Sci.1997,32,585./leaf becomes; " nonlinear optical properties of organic solid ", " organic solid " chapter 5, chief editor: primary track basis, Wang Fosong, Shanghai Science Press, 1999; P.181./Hua, J.; Luo, J.; Qin, J.; Shen, Y.; Zhang, Y.; Lu, Z.J. Mater.Chem.2002,12,863.
Summary of the invention
Purpose of the present invention just is to provide second-order nonlinear optical chromophore and the method for making thereof that contains indolyl radical.Such chromophoric group has big molecule single order hyperpolarizability (β), the good optical transparency and high thermostability concurrently, can be used as novel second-order non-linear optical materials and obtains practical application at aspects such as telecommunication, data storage, phase conjugations.
Technical scheme provided by the invention is: a class contains the second-order nonlinear optical chromophore of indolyl radical, has following general formula:
R is various alkyl, aromatic group or other heterogeneous ring compound functional group in the formula.X is oxygen or sulphur atom, and A is the various acceptors that draw electronics, as propane dinitrile, thiobarbituricacid, 3-phenyl-isoxazolidinones, 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, electron-withdrawing groups such as 5-dihydrofuran.
Above-mentioned R is C
1-C
9Alkyl or C
7-C
11Aromatic group.
The present invention also provides the method for making of above-mentioned second-order nonlinear optical chromophore, with indoles and C
1-C
9Halogenated alkane or C
7-C
11Halogenated aryl hydrocarbon be feedstock production substituted indole A, wherein indoles and C
1-C
9Halogenated alkane or C
7-C
11The molar ratio of halogenated aryl hydrocarbon be 1: 1.0～2.0, substituted indole A is connected with C on the N atom
1-C
9Alkyl or C
7-C
11The indoles of aromatic group; Substituted indole A and N, dinethylformamide and phosphorus oxychloride reaction, preparation indolal B, wherein substituted indole A, N, the mol ratio of dinethylformamide, phosphorus oxychloride is 1: 1.1～1.9: 1.1～1.9; Indolal B and bromo furan methyl triphenyl phosphine or bromo thiophene methyl triphenyl phosphine reaction then, preparation vinyl indoles furans C or vinyl indoles thiophene D, wherein the mol ratio of indolal B and bromo furan methyl triphenyl phosphine or bromo thiophene methyl triphenyl phosphine is 1: 1.0～2.0; Vinyl indoles furans C and N, dinethylformamide and phosphorus oxychloride reaction, preparation vinyl indoles Furan Aldehydes E, therein ethylene base indoles furans C, N, the mol ratio of dinethylformamide, phosphorus oxychloride is 1: 1.1～1.9: 2.0～3.7; Perhaps vinyl indoles thiophene D and n-Butyl Lithium and N, dinethylformamide prepared in reaction vinyl indoles thiophene aldehyde F, therein ethylene base indoles thiophene D and n-Butyl Lithium and N, the mol ratio of dinethylformamide is 1: 1.1～1.5: 1.0～1.4; Be raw material with vinyl indoles Furan Aldehydes E or vinyl indoles thiophene aldehyde F at last, with propane dinitrile, thiobarbituricacid, 3-phenyl-isoxazolidinones or 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the reaction of 5-dihydrofuran, make the second-order nonlinear optical chromophore that contains indolyl radical, the mol ratio between therein ethylene base indoles Furan Aldehydes E or vinyl indoles thiophene aldehyde F and the various drawing electron group is 1: 1～1.3.。
The second-order nonlinear optical chromophore that contains indolyl radical of the present invention can be used as the practical application of second-order non-linear optical materials at aspects such as telecommunication, data storage, phase conjugations.
The invention has the advantages that:
1. the present invention's second-order nonlinear optical chromophore of containing indolyl radical has extraordinary optical transparence, compare with the aniline analogue, its maximum absorption wavelength violet shift the 20-30 nanometer, this phenomenon is very rare.
2. the present invention's second-order nonlinear optical chromophore of containing indolyl radical has very high second-order nonlinear optical property (eight chromophoric single order hyperpolarizabilities is followed successively by 1162,1540,412,615,1068,1108,685,597 * 10 in example 1 and the example 2
-30Esu).
3. the invention describes the preparation of the second-order nonlinear optical chromophore that contains indolyl radical, enriched the content of second-order nonlinear optical chromophore research, expanded second-order nonlinear optical chromophore to a certain extent and become chemical method and mentality of designing.
Embodiment
Embodiment 1:
R is a n-hexyl, and when X was Sauerstoffatom, synthetic route was as follows:
A=in above-mentioned Ia, Ib, Ic, the Id compound is respectively
Synthetic method is:
Synthesizing of N-hexyl indoles (compound 1)
In the 250mL round-bottomed flask, put into potassium hydroxide solid and N, the dinethylformamide 3-10 of potassium hydroxide quality (be doubly) stirs and adds indoles after 20 minutes, stirs 40 minutes.Add 1-bromo-normal hexane at N with constant pressure funnel, the solution in the dinethylformamide (mass percent concentration is between the 20%-50%).Be warming up to 50 ℃ then, stirring reaction 2-20 hour.Reaction solution is poured in the suitable quantity of water, and chloroform extraction revolves except that behind the chloroform, uses the oil pump underpressure distillation, gets light yellow liquid, is product N-hexyl indoles.Wherein, the mol ratio of potassium hydroxide, indoles, 1-bromo-normal hexane is 5: 1: 1.2.
Synthesizing of 3-formyl radical-N-hexyl indoles (compound 2)
Take by weighing compound 1, with 1, the 2-ethylene dichloride is dissolved in (mass percent concentration is between the 3%-10%) in the 100mL flask, and ice bath is chilled to 0 ℃, stirs.Add N, dinethylformamide adds phosphorus oxychloride then.Heating reflux reaction 2 hours is poured reaction solution in the water into after the cooling, uses chloroform extraction.Revolving and remove chloroform, is that eluent carries out column chromatography with the chloroform, obtains reddish-brown product liquid 3-formyl radical-N-hexyl indoles.Compound 1, N, the mol ratio of dinethylformamide, phosphorus oxychloride is 1: 1.3: 1.3.
Synthesizing of 2-(N-n-hexyl-3-vinyl indoles) furans (compound 3)
Take by weighing bromo furan methyl triphenyl phosphine and place the Schlenk pipe, under the nitrogen protection, add the anhydrous tetrahydro furan 5-10 of bromo furan methyl triphenyl phosphine quality (be doubly), the adding potassium tert.-butoxide adds 3-formyl radical-N-hexyl indoles (compound 2) again.Reacted 20-30 hour.Reaction solution is poured in the distilled water, and chloroform extraction revolves except that chloroform, is that the chloroform and the sherwood oil of 1: 1 (volume ratio) is that eluent carries out column chromatography with proportioning, obtains bright orange green liquid 2-(N-n-hexyl-3-vinyl indoles) furans.Wherein, the mol ratio of bromo furan methyl triphenyl phosphine, potassium tert.-butoxide and 3-formyl radical-N-hexyl indoles is 1: 1.5: 1.
Synthesizing of 2-(N-n-hexyl-3-vinyl indoles)-5-formylfuran (compound 4)
In two mouthfuls of flasks of 100mL, add compound 3, with 1,2-ethylene dichloride dissolving (mass percent concentration is between the 3%-10%).With phosphorus oxychloride and N, the mixed solution of dinethylformamide is added in above-mentioned two mouthfuls of flasks.Behind the stirring at room 2h, reaction solution is poured in the saturated solution of sodium carbonate, with 1, the extraction of 2-ethylene dichloride.Revolve and remove 1, the 2-ethylene dichloride carries out column chromatography with the chloroform give eluent, obtains orange red solid 2-(N-n-hexyl-3-vinyl indoles)-5-formylfuran.Wherein, compound 3, phosphorus oxychloride and N, the mol ratio of dinethylformamide is 1: 1.4: 2.4.
Chromophoric group Ia's is synthetic
Take by weighing above-claimed cpd 4, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, add propane dinitrile, stir and make its dissolving with dehydrated alcohol.Room temperature reaction 2h removes ethanol with reaction solution on Rotary Evaporators, carry out column chromatography then, and eluent is the chloroform and the sherwood oil of 1: 1 (volume ratio), obtains red solid chromophoric group Ia.Wherein, the mol ratio of compound 4 and propane dinitrile is 1: 1.Fusing point: 95-96 ℃.IR：2218cm
-1(C≡N)。UV-Vis (chloroform, λ max): 526 nanometers.
Chromophoric group Ib's is synthetic
Take by weighing above-claimed cpd 4, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, add the sulfo-veronal, reflux 3 hours with dehydrated alcohol.Revolving and remove ethanol, is that the chloroform and the sherwood oil (60 ℃-90 ℃ of boiling points) of 1: 1 (volume ratio) for eluent carries out column chromatography, obtains bluish voilet solid chromophoric group Ib with proportioning.Wherein, the mol ratio of compound 4 and sulfo-veronal is 1: 1.Fusing point: 198-200 ℃.IR：1665cm
-1(C＝O)。UV-Vis (chloroform, λ max): 590 nanometers.
Chromophoric group Ic's is synthetic
Take by weighing above-claimed cpd 4, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, add 3-phenyl-isoxazolidinones, stir and make its dissolving with dehydrated alcohol.Stirring at room 2 hours is revolved except that ethanol, with chloroform give column chromatography eluent, obtains bluish voilet solid chromophoric group Ic.Wherein, the mol ratio of compound 4 and 3-phenyl-isoxazolidinones is 1: 1.3.Fusing point: 118-120 ℃.IR：1665cm
-1(C＝O)。UV-Vis (chloroform, λ max): 566 nanometers.
Chromophoric group Id's is synthetic
Take by weighing compound 4, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, to wherein adding 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2,5-dihydrofuran, reflux 3 hours with dehydrated alcohol.Stopped reaction revolves except that ethanol, and with chloroform: ethyl acetate=20: 3 (volume ratio) is that eluent carries out column chromatography, obtains dark blue purple pressed powder chromophoric group Id.Wherein, compound 4 and 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the mol ratio of 5-dihydrofuran is 1: 1.2.Fusing point: 202-204 ℃.IR：2223cm
-1(C≡N)。UV-Vis (chloroform, λ max): 650 nanometers.
Embodiment 2:
R is a n-hexyl, and when X was sulphur atom, synthetic route was as follows:
A=in above-mentioned IIa, IIb, IIc, the IId compound is respectively
Synthetic method is:
The preparation of bromo thiophene methyl triphenyl phosphine
(5.01g 50mmol), adds in the 250ml round-bottomed flask, adds tetracol phenixin 150ml then, and (10.7g, 60mmol), BPO powder 0.1g is heated to CCl to the NBS powder to take by weighing the 2-thiotolene
4Backflow 2h, reaction solution is gradually become than deep yellow by pale yellow solution.With reacting liquid filtering and use CCl
4The washing filter residue is collected gained CCl
4Solution revolves except that CCl
4Obtain yellow oily liquid, remove water-soluble impurity, use CHCl to wherein adding entry
3Extraction adds anhydrous Na
2SO
4Dried overnight.Elimination Na
2SO
4, the gained yellow solution is changed over to-the 250ml flask in, add PPh
3(10.7g, 50mmol) and CHCl
3100ml, heated and stirred is to CHCl
3Reflux, stop heating behind the reaction 2h.A large amount of white solids appear in the bottle wall in the reflux course, and solution colour shoals.Filter and use a small amount of CHCl
3Washed product obtains white solid powdery product bromo thiophene methyl triphenyl phosphine.
Synthesizing as described in example 1 above of 3-formyl radical-N-hexyl indoles (compound 2).
Synthesizing of 2-(N-n-hexyl-3-vinyl indoles) thiophene (compound 5)
In the Schlenk pipe, add n-hexyl indolal 2 and bromo thiophene methyl triphenyl phosphine.In the Schlek pipe, add anhydrous tetrahydro furan (n-hexyl indolal 2 quality 10 times) under the nitrogen protection, add potassium tert.-butoxide then, behind the stirring at room reaction 24h reaction solution is poured in the water, use CHCl
3For the extraction agent extraction, revolve except that CHCl
3, be that the chloroform and the sherwood oil of 1: 1 (volume ratio) is that eluent carries out column chromatography with proportioning, obtain orange red oily liquids product 2-(N-n-hexyl-3-vinyl indoles) thiophene.Wherein, the mol ratio of compound 2, bromo thiophene methyl triphenyl phosphine and potassium tert.-butoxide is 1: 1: 2.
Synthesizing of 2-(N-n-hexyl-3-vinyl indoles)-5-formyl radical thiophene (compound 6)
In an exsiccant Schlenk pipe, add 2-(N-n-hexyl-3-vinyl indoles) thiophene and dry tetrahydrofuran (2-(N-n-hexyl-3-vinyl indoles) thiophene quality 50 times), at N
2Protection adds n-butyllithium solution (solvent is a normal hexane, and concentration is 2.5mol/L) down in-78 ℃ of liquid nitrogen baths, stirred 1.5 hours.Then reaction solution is carried to air, added N, dinethylformamide, stirred overnight at room temperature.In reaction solution, add entry, use CHCl after the stirring
3Extraction.With CHCl
3For eluent carries out column chromatography, obtain thick brown solid 2-(N-n-hexyl-3-vinyl indoles)-5-formyl radical thiophene.Wherein, 2-(N-n-hexyl-3-vinyl indoles) thiophene, n-Butyl Lithium and N, the mol ratio of dinethylformamide is 1: 1.2: 1.1.
Chromophoric group IIa's is synthetic
In a 100ml round-bottomed flask, add compound 6, add dissolve with ethanol again.Take by weighing propane dinitrile and add reaction soln, be warming up to 80 ℃, stirred 4 hours.Revolve and remove ethanol, with CHCl
3For eluent carries out column chromatography, obtain atropurpureus crystallite chromophoric group IIa.Wherein, the mol ratio of compound 6 and propane dinitrile is 1: 1.Fusing point: 115-117 ℃.IR：2218cm
-1(C≡N)。UV-Vis (chloroform, λ max): 524 nanometers.
Chromophoric group IIb's is synthetic
In a 100ml round-bottomed flask, add compound 6, add dissolve with ethanol again.Take by weighing the sulfo-veronal and add reaction soln, be warming up to 80 ℃, stirred 4 hours.Revolve and remove ethanol, with CHCl
3For eluent carries out column chromatography, obtain bluish voilet crystallite chromophoric group IIb.Wherein, the mol ratio of compound 6 and sulfo-veronal is 1: 1.3.Fusing point: 191-193 ℃.IR：1653cm
-1(C＝O)。UV-Vis (chloroform, λ max): 586 nanometers.
Chromophoric group IIc's is synthetic
In a 100ml round-bottomed flask, add compound 6, add dissolve with ethanol again.Take by weighing 3-phenyl-isoxazole oxazolone and add reaction soln, be warming up to 80 ℃, stirred 4 hours.Revolve and remove ethanol, with CHCl
3For eluent carries out column chromatography, obtain black-and-blue crystallite chromophoric group IIc.Wherein, the mol ratio of compound 6 and 3-phenyl-isoxazole oxazolone is 1: 1.2.Fusing point: 139-140 ℃.IR：1733cm
-1(C＝O)。UV-Vis (chloroform, λ max): 561 nanometers.
Chromophoric group IId's is synthetic
In a 100ml round-bottomed flask, add compound 6, add dissolve with ethanol again.Take by weighing 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the 5-dihydrofuran adds reaction soln, is warming up to 80 ℃, stirs 4 hours.Revolve and remove ethanol, with CHCl3: the mixed solvent of ethyl acetate=20: 3 (volume ratio) is that eluent carries out column chromatography, obtains black-and-blue crystallite chromophoric group IId.Wherein, compound 6 and 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the mol ratio of 5-dihydrofuran is 1: 1.Fusing point: 178-180 ℃.IR：2225cm
-1(C＝N)。UV-Vis (chloroform, λ max): 638 nanometers.
Embodiment 3:
R is a normal-butyl, and when X was Sauerstoffatom, synthetic route was as follows:
A=in above-mentioned IIIa, IIIb, IIIc, the IIId compound is respectively
Synthetic method is:
Synthesizing of N-indole-butyl (compound 7)
In the 250mL round-bottomed flask, put into potassium hydroxide solid and N, the dinethylformamide 3-10 of potassium hydroxide quality (be doubly) stirs and adds indoles after 20 minutes, stirs 40 minutes.Add 1-bromo-normal butane solution (solvent is N, and dinethylformamide, mass percent concentration are between the 20%-50%) with constant pressure funnel.Be warming up to 50 ℃ then, stirring reaction 2-20 hour.Reaction solution is poured in the water, and chloroform extraction revolves except that behind the chloroform, uses the oil pump underpressure distillation, gets light yellow liquid, is product N-indole-butyl.Wherein, the mol ratio of potassium hydroxide, indoles, 1-bromo-normal butane is 2: 1: 1.2.
Synthesizing of 3-formyl radical-N-indole-butyl (compound 8)
Take by weighing compound 7, with 1, the 2-ethylene dichloride is dissolved in (mass percent concentration is between the 3%-10%) in the 100mL flask, and ice bath is chilled to 0 ℃, stirs.Add N, dinethylformamide adds phosphorus oxychloride then.Heating reflux reaction 2 hours after the cooling is poured reaction solution into and is filled in the water, uses chloroform extraction.Revolving and remove chloroform, is that eluent carries out column chromatography with the chloroform, obtains the reddish-brown product liquid.Compound 7, N, the mol ratio of dinethylformamide, phosphorus oxychloride is 1: 1.3: 1.5.Synthesizing of 2-(N-normal-butyl-3-vinyl indoles) furans (compound 9)
Take by weighing bromo furan methyl triphenyl phosphine, place the Schlenk pipe, under the nitrogen protection, add the anhydrous tetrahydro furan 5-10 of bromo furan methyl triphenyl phosphine quality (be doubly), add an amount of potassium tert.-butoxide, at adding 3-formyl radical-N-indole-butyl.Reacted 20-30 hour.Reaction solution is poured in the distilled water, and chloroform extraction revolves except that chloroform, is that the chloroform and the sherwood oil of 1: 1 (volume ratio) is that eluent carries out column chromatography with proportioning, obtains bright orange green liquid 2-(N-normal-butyl-3-vinyl indoles) furans.Wherein, the mol ratio of bromo furan methyl triphenyl phosphine, potassium tert.-butoxide and 3-formyl radical-N-indole-butyl is 1: 1.5: 1.
Synthesizing of 2-(N-normal-butyl-3-vinyl indoles)-5-formylfuran (compound 10)
In two mouthfuls of flasks of 100mL, add compound 9, with 1,2-ethylene dichloride dissolving (mass percent concentration is between the 3%-10%).With phosphorus oxychloride and N, the mixed solution of dinethylformamide is added in above-mentioned two mouthfuls of flasks.After the stirring at room 2 hours, reaction solution is poured in the saturated solution of sodium carbonate, with 1, the extraction of 2-ethylene dichloride.Revolve and remove 1, the 2-ethylene dichloride carries out column chromatography with the chloroform give eluent, obtains orange red solid 2-(N-normal-butyl-3-vinyl indoles)-5-formylfuran.Wherein, compound 9, phosphorus oxychloride and N, the mol ratio of dinethylformamide is 1: 1.4: 2.4.
Chromophoric group IIIa's is synthetic
Take by weighing compound 10, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, add propane dinitrile, stir and make its dissolving with dehydrated alcohol.Room temperature reaction 2 hours is removed ethanol with reaction solution on Rotary Evaporators, carry out column chromatography then, and eluent is the chloroform and the sherwood oil of 1: 1 (volume ratio), obtains red solid chromophoric group IIIa.Wherein, the mol ratio of compound 10 and propane dinitrile is 1: 1.IR：2219cm
-1(C≡N)。UV-Vis (chloroform, λ max): 527 nanometers.
Chromophoric group IIIb's is synthetic
Take by weighing compound 10, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, add the sulfo-veronal, reflux 3 hours with dehydrated alcohol.Revolve and remove ethanol, with proportioning be the chloroform of 1: 1 (volume ratio) and sherwood oil (boiling point 60-90 ℃) for eluent carries out column chromatography, obtain bluish voilet solid chromophoric group IIIb.Wherein, the mol ratio of compound 10 and sulfo-veronal is 1: 1.3.IR：1663cm
-1(C＝O)。UV-Vis (chloroform, λ max): 5910 nanometers.
Chromophoric group IIIc's is synthetic
Take by weighing compound 10, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, add 3-phenyl-isoxazolidinones, stir and make its dissolving with dehydrated alcohol.Stirring at room 2 hours is revolved except that ethanol, with chloroform give column chromatography eluent, obtains bluish voilet solid chromophoric group IIIc.Wherein, the mol ratio of compound 10 and 3-phenyl-isoxazolidinones is 1: 1.2.IR：1667cm
-1(C＝0)。UV-Vis (chloroform, λ max): 565 nanometers.
Chromophoric group IIId's is synthetic
Take by weighing compound 10, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, to wherein adding 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2,5-dihydrofuran, reflux 3 hours with dehydrated alcohol.Stopped reaction revolves except that ethanol, and with chloroform: ethyl acetate=20: 3 (volume ratio) is that eluent carries out column chromatography, obtains dark blue purple pressed powder chromophoric group IIId.Wherein, compound 10 and 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the mol ratio of 5-dihydrofuran is 1: 1.IR：2224cm
-1(C≡N)。UV-Vis (chloroform, λ max): 652 nanometers.
Embodiment 4:
R is a normal-butyl, and when X was sulphur atom, synthetic route was as follows:
A=in above-mentioned IVa, IVb, IVc, the IVd compound is respectively
Synthetic method is:
Synthesizing as described in example 3 above of 3-formyl radical-N-indole-butyl (compound 8).
Synthesizing of 2-(N-normal-butyl-3-vinyl indoles) thiophene (compound 11)
In the Schlenk pipe, add compound 8 and bromo thiophene methyl triphenyl phosphine.Add anhydrous tetrahydro furan (compound 8 quality 10 times) under the nitrogen protection in the Schlek pipe, add potassium tert.-butoxide then, the stirring at room reaction was poured reaction solution in the water into after 24 hours, used CHCl
3For the extraction agent collection, revolve except that CHCl
3, be that the chloroform and the sherwood oil of 1: 1 (volume ratio) is that eluent carries out column chromatography with proportioning, obtain orange red oily liquids product 2-(N-normal-butyl-3-vinyl indoles) thiophene.Wherein, the mol ratio of compound 8, bromo thiophene methyl triphenyl phosphine and potassium tert.-butoxide is 1: 1: 2.
Synthesizing of 2-(N-normal-butyl-3-vinyl indoles)-5-formyl radical thiophene (compound 12)
In an exsiccant Schlenk pipe, add 2-(N-normal-butyl-3-vinyl indoles) thiophene and dry tetrahydrofuran (2-(N-normal-butyl-3-vinyl indoles) thiophene quality 50 times), at N
2Protection adds n-Butyl Lithium down in-78 ℃ of liquid nitrogen baths (hexane solution 2.5mol/L), stirred 1.5 hours.Then reaction solution is carried to air, added N, dinethylformamide, stirred overnight at room temperature.In reaction solution, add entry, use CHCl after the stirring
3Extraction.With CHCl
3For eluent carries out column chromatography, obtain thick brown solid compound 12.Wherein, 2-(N-normal-butyl-3-vinyl indoles) thiophene, n-Butyl Lithium and N, the mol ratio of dinethylformamide is 1: 1.2: 1.1.
Chromophoric group IVa's is synthetic
In a 100ml round-bottomed flask, add compound 12, add dissolve with ethanol again.Take by weighing propane dinitrile and add reaction soln, be warming up to 80 ℃, stirred 4 hours.Revolve and remove ethanol, with CHCl
3For eluent carries out column chromatography, obtain atropurpureus crystallite chromophoric group IVa.Wherein, the mol ratio of compound 12 and propane dinitrile is 1: 1.IR：2217cm
-1(C≡N)。UV-Vis (chloroform, λ max): 523 nanometers.
Chromophoric group IVb's is synthetic
In a 100ml round-bottomed flask, add compound 12, add dissolve with ethanol again.Take by weighing the sulfo-veronal and add reaction soln, be warming up to 80 ℃, stirred 4 hours.Revolve and remove ethanol, with CHCl
3For eluent carries out column chromatography, obtain bluish voilet crystallite chromophoric group IVb.Wherein, the mol ratio of compound 12 and sulfo-veronal is 1: 1.3.IR：1651cm
-1(C＝O)。UV-Vis (chloroform, λ max): 585 nanometers
Chromophoric group IVc's is synthetic
In a 100ml round-bottomed flask, add compound 12, add dissolve with ethanol again.Take by weighing 3-phenyl-isoxazole oxazolone and add reaction soln, be warming up to 80 ℃, stirred 4 hours.Revolve and remove ethanol, with CHCl
3For eluent carries out column chromatography, obtain black-and-blue crystallite chromophoric group IVc.Wherein, the mol ratio of compound 12 and 3-phenyl-isoxazole oxazolone is 1: 1.1.IR：1731cm
-1(C＝O)。UV-Vis (chloroform, λ max): 560 nanometers.
Chromophoric group IVd's is synthetic
In-100ml round-bottomed flask, add compound 12, add dissolve with ethanol again.Take by weighing 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the 5-dihydrofuran adds reaction soln, is warming up to 80 ℃, stirs 4 hours.Revolve and remove ethanol, with CHCl
3: the mixed solvent of ethyl acetate=20: 3 (volume ratio) is that eluent carries out column chromatography, obtains black-and-blue crystallite chromophoric group IVd.Wherein, compound 12 and 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the mol ratio of 5-dihydrofuran is 1: 1.IR：2227cm
-1(C≡N)。UV-Vis (chloroform, λ max): 639 nanometers.
Embodiment 5:
R is a benzyl, and when X was Sauerstoffatom, synthetic route was as follows:
A=in above-mentioned Va, Vb, Vc, the Vd compound is respectively
Synthetic method is:
Synthesizing of N-benzylindole (compound 13)
In the 250mL round-bottomed flask, put into potassium hydroxide solid and N, the dinethylformamide 3-10 of potassium hydroxide quality (be doubly) stirs and adds indoles after 20 minutes, stirs 40 minutes.Add benzyl chlorine at N with constant pressure funnel, the solution in the dinethylformamide (mass percent concentration is between the 20%-50%).Be warming up to 50 ℃ then, stirring reaction 2-20 hour.Reaction solution is poured in the water, and chloroform extraction revolves except that behind the chloroform, uses the oil pump underpressure distillation, gets light yellow liquid, is product compound 13.Wherein, the mol ratio of potassium hydroxide, indoles, benzyl chlorine is 4: 1: 1.2.
Synthesizing of 3-formyl radical-N-benzylindole (compound 14)
Take by weighing compound 13, with 1, the 2-ethylene dichloride is dissolved in (mass percent concentration is between the 3%-10%) in the 100mL flask, and ice bath is chilled to 0 ℃, stirs.Add N, dinethylformamide adds phosphorus oxychloride then.Heating reflux reaction 2 hours after the cooling is poured reaction solution into and is filled in the water, uses chloroform extraction.Revolving and remove chloroform, is that eluent carries out column chromatography with the chloroform, obtains reddish-brown product liquid compound 14.Compound 13, N, the mol ratio of dinethylformamide, phosphorus oxychloride is 1: 13: 13.
Synthesizing of 2-(N-benzyl-3-vinyl indoles) furans (compound 15)
Take by weighing bromo furan methyl triphenyl phosphine, place the Schlenk pipe, under the nitrogen protection, add the anhydrous tetrahydro furan 5-10 of bromo furan methyl triphenyl phosphine quality (be doubly), the adding potassium tert.-butoxide adds 3-formyl radical-N-benzylindole again.Reacted 20-30 hour.Reaction solution is poured in the distilled water, and chloroform extraction revolves except that chloroform, is that the chloroform and the sherwood oil of 1: 1 (volume ratio) is that eluent carries out column chromatography with proportioning, obtains bright orange green liquid compound 15.Wherein, the mol ratio of bromo furan methyl triphenyl phosphine, potassium tert.-butoxide and 3-formyl radical-N-benzylindole is 1: 1.5: 1.
Synthesizing of 2-(N-benzyl-3-vinyl indoles)-5-formylfuran (compound 16)
In two mouthfuls of flasks of 100mL, add compound 15, with 1,2-ethylene dichloride dissolving (mass percent concentration is between the 3%-10%).With phosphorus oxychloride and N, the mixed solution of dinethylformamide is added in above-mentioned two mouthfuls of flasks.After the stirring at room 2 hours, reaction solution is poured in the saturated solution of sodium carbonate, with 1, the extraction of 2-ethylene dichloride.Revolve and remove 1, the 2-ethylene dichloride carries out column chromatography with the chloroform give eluent, obtains orange red solid chemical compound 16.Wherein, compound 15, phosphorus oxychloride and N, the mol ratio of dinethylformamide is 1: 1.4: 2.4.
Chromophoric group Va's is synthetic
Take by weighing compound 16, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, add propane dinitrile, stir and make its dissolving with dehydrated alcohol.Room temperature reaction 2 hours is removed ethanol with reaction solution on Rotary Evaporators, carry out column chromatography then, and eluent is the chloroform and the sherwood oil of 1: 1 (volume ratio), obtains red solid chromophoric group Va.Wherein, the mol ratio of compound 16 and propane dinitrile is 1: 1.3.IR：2219cm
-1(C≡N)。UV-Vis (chloroform, λ max): 527 nanometers.Chromophoric group Vb's is synthetic
Take by weighing compound 16, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, add the sulfo-veronal, reflux 3 hours with dehydrated alcohol.Revolve and remove ethanol, with proportioning be the chloroform of 1: 1 (volume ratio) and sherwood oil (boiling point 60-90 ℃) for eluent carries out column chromatography, obtain bluish voilet solid chromophoric group Vb.Wherein, the mol ratio of compound 16 and sulfo-veronal is 1: 1.3.IR：1664cm
-1(C＝O)。UV-Vis (chloroform, λ max): 591 nanometers.
Chromophoric group Vc's is synthetic
Take by weighing compound 16, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, add 3-phenyl-isoxazolidinones, stir and make its dissolving with dehydrated alcohol.Stirring at room 2 hours is revolved except that ethanol, with chloroform give column chromatography eluent, obtains bluish voilet solid chromophoric group Vc.Wherein, the mol ratio of compound 16 and 3-phenyl-isoxazolidinones is 1: 1.IR：1665cm
-1(C＝O)。UV-Vis (chloroform, λ max): 566 nanometers.
Chromophoric group Vd's is synthetic
Take by weighing compound 16, be dissolved in (mass percent concentration is between the 0.1%-1%) in the 100mL flask, to wherein adding an amount of 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2,5-dihydrofuran, reflux 3 hours with dehydrated alcohol.Stopped reaction revolves except that ethanol, and with chloroform: ethyl acetate=20: 3 (volume ratio) is that eluent carries out column chromatography, obtains dark blue purple pressed powder chromophoric group Vd.Wherein, compound 16 and 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the mol ratio of 5-dihydrofuran is 1: 1.3.IR：2221cm
-1(C≡N)。UV-Vis (chloroform, λ max): 651 nanometers.
Embodiment 6:
R is a benzyl, and when X was sulphur atom, synthetic route was as follows:
A=in above-mentioned VIa, VIb, VIc, the VId compound is respectively
Synthetic method is:
Synthesizing as described in example 5 above of 3-formyl radical-N-benzylindole (compound 14).
Synthesizing of 2-(N-benzyl-3-vinyl indoles) thiophene (compound 17)
In the Schlenk pipe, add compound 14 and bromo thiophene methyl triphenyl phosphine.Add anhydrous tetrahydro furan (compound 14 quality 10 times) under the nitrogen protection in the Schlek pipe, add potassium tert.-butoxide then, the stirring at room reaction was poured reaction solution in the water into after 24 hours, used CHCl
3For the extraction agent collection, revolve except that CHCl
3, be that the chloroform and the sherwood oil of 1: 1 (volume ratio) is that eluent carries out column chromatography with proportioning, obtain orange red oily liquids product compound 17.Wherein, the mol ratio of compound 14, bromo thiophene methyl triphenyl phosphine and potassium tert.-butoxide is 1: 1: 2.
Synthesizing of 2-(N-benzyl-3-vinyl indoles)-5-formyl radical thiophene (compound 18)
In dry Schlenk pipe, add 2-(N-benzyl-3-vinyl indoles) thiophene and dry tetrahydrofuran (2-(N-benzyl-3-vinyl indoles) thiophene quality 50 times) to one, at N
2Protection adds n-Butyl Lithium down in-78 ℃ of liquid nitrogen baths (hexane solution 2.5mol/L), stirred 1.5 hours.Then reaction solution is carried to air, added N, dinethylformamide, stirred overnight at room temperature.In reaction solution, add entry, use CHCl after the stirring
3Extraction.With CHCl
3For eluent carries out column chromatography, obtain thick brown solid compound 18.Wherein, 2-(N-benzyl-3-vinyl indoles) thiophene, n-Butyl Lithium and N, the mol ratio of dinethylformamide is 1: 1.2: 1.1.
Chromophoric group VIa's is synthetic
In a 100ml round-bottomed flask, add compound 18, add dissolve with ethanol again.Take by weighing propane dinitrile and add reaction soln, be warming up to 80 ℃, stirred 4 hours.Revolve and remove ethanol, with CHCl
3For eluent carries out column chromatography, obtain atropurpureus crystallite chromophoric group VIa.Wherein, the mol ratio of compound 18 and propane dinitrile is 1: 1.IR：2220cm
-1(C≡N)。UV-Vis (chloroform, λ max): 524 nanometers.
Chromophoric group VIb's is synthetic
In a 100ml round-bottomed flask, add compound 18, add dissolve with ethanol again.Take by weighing the sulfo-veronal and add reaction soln, be warming up to 80 ℃, stirred 4 hours.Revolve and remove ethanol, with CHCl
3For eluent carries out column chromatography, obtain bluish voilet crystallite chromophoric group VIb.Wherein, the mol ratio of compound 18 and sulfo-veronal is 1: 1.3.IR：1655cm
-1(C＝O)。UV-Vis (chloroform, λ max): 586 nanometers
Chromophoric group VIc's is synthetic
In a 100ml round-bottomed flask, add compound 18, add dissolve with ethanol again.Take by weighing 3-phenyl-isoxazole oxazolone and add reaction soln, be warming up to 80 ℃, stirred 4 hours.Revolve and remove ethanol, with CHCl
3For eluent carries out column chromatography, obtain black-and-blue crystallite chromophoric group VIc.Wherein, the mol ratio of compound 18 and 3-phenyl-isoxazole oxazolone is 1: 1.IR：1730cm
-1(C＝O)。UV-Vis (chloroform, λ max): 562 nanometers.
Chromophoric group VId's is synthetic
In a 100ml round-bottomed flask, add compound 18, add dissolve with ethanol again.Take by weighing 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the 5-dihydrofuran adds reaction soln, is warming up to 80 ℃, stirs 4 hours.Revolve and remove ethanol, with CHCl
3: the mixed solvent of ethyl acetate=20: 3 (volume ratio) is that eluent carries out column chromatography, obtains black-and-blue crystallite chromophoric group VId.Wherein, compound 18 and 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the mol ratio of 5-dihydrofuran is 1: 1.2.IR：2222cm
-1(C≡N)。UV-Vis (chloroform, λ max): 636 nanometers.
Claims (2)
1. the second-order nonlinear optical chromophore that contains indolyl radical, its general structure is:
R is C in the formula
1-C
9Alkyl or C
7-C
11Aromatic group; X is oxygen or sulphur atom, and A is selected from following electron-withdrawing group: propane dinitrile, thiobarbituricacid, 3-phenyl-isoxazolidinones, 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2,5-dihydrofuran.
2. the described method for making that contains the second-order nonlinear optical chromophore of indolyl radical of claim 1 is characterized in that: with indoles and C
1-C
9Halogenated alkane or C
7-C
11Halogenated aryl hydrocarbon be feedstock production substituted indole A, wherein indoles and C
1-C
9Halogenated alkane or C
7-C
11The molar ratio of halogenated aryl hydrocarbon be 1: 1.0～2.0, substituted indole A is connected with C on the N atom
1-C
9Alkyl or C
7-C
11The indoles of aromatic group; Substituted indole A and N, dinethylformamide and phosphorus oxychloride reaction, preparation indolal B, wherein substituted indole A, N, the mol ratio of dinethylformamide, phosphorus oxychloride is 1: 1.1～1.9: 1.1～1.9; Indolal B and bromo furan methyl triphenyl phosphine or bromo thiophene methyl triphenyl phosphine reaction then, preparation vinyl indoles furans C or vinyl indoles thiophene D, wherein the mol ratio of indolal B and bromo furan methyl triphenyl phosphine or bromo thiophene methyl triphenyl phosphine is 1: 1.0～2.0; Vinyl indoles furans C and N, dinethylformamide and phosphorus oxychloride reaction, preparation vinyl indoles Furan Aldehydes E, therein ethylene base indoles furans C, N, the mol ratio of dinethylformamide, phosphorus oxychloride is 1: 1.1～1.9: 2.0～3.7; Perhaps vinyl indoles thiophene D and n-Butyl Lithium and N, dinethylformamide prepared in reaction vinyl indoles thiophene aldehyde F, therein ethylene base indoles thiophene D and n-Butyl Lithium and N, the mol ratio of dinethylformamide is 1: 1.1～1.5: 1.0～1.4; Be raw material with vinyl indoles Furan Aldehydes E or vinyl indoles thiophene aldehyde F at last, with propane dinitrile, thiobarbituricacid, 3-phenyl-isoxazolidinones or 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the reaction of 5-dihydrofuran, make the described second-order nonlinear optical chromophore that contains indolyl radical of claim 1, the mol ratio between therein ethylene base indoles Furan Aldehydes E or vinyl indoles thiophene aldehyde F and the various drawing electron group is 1: 1～1.3.
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