CN101602746B - Preparation and application of 3-substituted-N-hexyl phenothiazine derivative - Google Patents
Preparation and application of 3-substituted-N-hexyl phenothiazine derivative Download PDFInfo
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- CN101602746B CN101602746B CN200910062863A CN200910062863A CN101602746B CN 101602746 B CN101602746 B CN 101602746B CN 200910062863 A CN200910062863 A CN 200910062863A CN 200910062863 A CN200910062863 A CN 200910062863A CN 101602746 B CN101602746 B CN 101602746B
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- pyrimidine
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- 0 CCCCCCN1c(ccc(C=C(*)C#N)c2)c2Sc2c1cccc2 Chemical compound CCCCCCN1c(ccc(C=C(*)C#N)c2)c2Sc2c1cccc2 0.000 description 2
- DZCOHLCHTVMOJU-UHFFFAOYSA-N CN1c(ccc(C=O)c2)c2Sc2c1cccc2 Chemical compound CN1c(ccc(C=O)c2)c2Sc2c1cccc2 DZCOHLCHTVMOJU-UHFFFAOYSA-N 0.000 description 2
- QTUUBOZSGQFLRZ-UHFFFAOYSA-N CC(C)(CC(C)=C1)CC1=C(C#N)C#N Chemical compound CC(C)(CC(C)=C1)CC1=C(C#N)C#N QTUUBOZSGQFLRZ-UHFFFAOYSA-N 0.000 description 1
- OPHSIMXYBLOTLY-UHFFFAOYSA-N CCCCCCN(c(cccc1)c1S)N(CC)C(N(CC)C(C)=O)=S Chemical compound CCCCCCN(c(cccc1)c1S)N(CC)C(N(CC)C(C)=O)=S OPHSIMXYBLOTLY-UHFFFAOYSA-N 0.000 description 1
- VDBQLDBQXHLYDJ-UHFFFAOYSA-N CCCCCCNc(cccc1)c1S Chemical compound CCCCCCNc(cccc1)c1S VDBQLDBQXHLYDJ-UHFFFAOYSA-N 0.000 description 1
- SHBTUGJAKBRBBJ-UHFFFAOYSA-N CCN(C(CC(N1CC)=O)=O)C1=S Chemical compound CCN(C(CC(N1CC)=O)=O)C1=S SHBTUGJAKBRBBJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses preparation and application of a 3-substituted-N-hexyl phenothiazine derivative shown in a general formula (I). In the formula, R is malononitrile group, 1, 2, 4-triazolo [1, 5-a] pyrimidyl, spiropyranyl, 3-dicyanomethylene-1, 5, 5-trimethylcyclohexenyl, 1, 3-diethyl-2-thiobarbituric acidyl, N, N-dimethylaminophenyl, p-nitrobenzophenone or 2, 4, 6-trimethyl-3, 5-dicyanopyridyl. All the compounds have fine solubility and thermostability and can be applied to flat-panel displays as red electroluminescent materials.
Description
Technical field
The invention belongs to the electroluminescent technology field, be specifically related to one type of preparation and application thereof with 3-replacement-N-hexyl phenothiazine derivative of outstanding electronics injection and cavity transmission ability.This compounds has good solubility and thermostability, can be used as red electroluminescent materials, is applied in the flat-panel monitor.
Background technology
Thiodiphenylamine is claimed phenothiazine or sulphur naphthazin(e) again, is the three member ring heterocyclic compound with sulphur and nitrogen heteroatom, and since being synthesized first in 1883 [1], it has a wide range of applications in fields such as dyestuff chemistry, pharmaceutical chemistry, photoelectrochemistry.As the compounds such as thionine, Socryl Blue BRL, thiamines indigo plant that contain the thiodiphenylamine structural unit have visible light and absorb and be widely used as dyestuff by force; Thiodiphenylamine has lower ionizing potential; Lose an electronics easily and form corresponding radical cation; The biological activity closely related [2] that this and phenothiazines medicine are had; It is used as the medicine of malaria, urinary tract infections, tuberculosis and the sterilant of livestock at first aspect pharmaceutical chemistry, found afterwards that it had good antihistaminic characteristic, and the hypotoxicity stable curative effect can not produce dependency and be widely used as Tranqilliser.Hefnawy has summed up the relationship analysis [3] of the relevant property of medicine and structure in its summary about Tranqilliser and drug testing; The phenothiazines compound also is widely used as inhibitor [4] in the industry; Aspect photoelectrochemistry, mainly contain the generation that is used for studying single electron transfer, positron radical and character [5], molecule sign [6] and as luminescent material etc.
Aspect the research of luminescent material; The thiodiphenylamine intramolecularly shows good cavity transmission ability because of sulphur and the nitrogen-atoms that contains electron rich; The existence of sulphur, nitrogen-atoms simultaneously makes that the thiodiphenylamine molecule is not the big two dimensional structure of conjugated; But serve as the angled butterfly structure of axle with sulphur, nitrogen-atoms, the size of this interfacial angle not only with nitrogen-atoms on substituting group relevant, but also receive substituent influence the on the phenyl ring.The nonplanarity of its molecular structure can effectively stop the formation of gathering of compound π key and intermolecular exciplex, thereby influences the organic light-emitting device quantum yield; In addition the sulphur atom in the thiodiphenylamine easily control condition be oxidized to sulfoxide or sulfone, can obviously strengthen its electron transport ability like this.The chemical modifiability of the nonplanarity of structure, multidigit point and special photoelectronic property make thiodiphenylamine aspect organic electroluminescent, receive increasing attention and research.Like Jenekhe [7] group the electroluminescent properties of phenothiazine derivative has been carried out more research; Like them to gathering N-methyl thiodiphenylamine (PMP) and its verivate 3; Detailed research has been carried out in difference and contact on the transfer transport of 7-two (4-phenyl-2-quinolyl)-N-methyl thiodiphenylamine (DPQMP) and optical physics characteristic, the photoelectric properties, has confirmed that thiodiphenylamine has the sub-ability of stronger power supply (hole transport performance).
These work have all greatly promoted the development of luminescent device.Yet although generally can not meet the demands to the luminescent lifetime of finding material in the three primary colours investigation of materials that shows the field at present, blue, the life-span of green material is long slightly, and red material is the shortest.In addition, the size of luminous efficiency is decided by the rate of injection and the balanced degree of current carrier, and the carrier transport ability difference of material different is very big.Research shows that thiodiphenylamine is a kind of good hole mobile material, and its molecule itself has very low ionizing potential, is a kind of good material that glows, and can improve the luminescent lifetime and the luminous efficiency of material.
Under this research background, the present invention has developed the 3-substituted phenothiazine verivate that can be used as novel strong luminescent material just.It is the compound of the conjugated structure of donor with the thiodiphenylamine that the present invention has prepared a series of; Select triazolo pyrimidine, propane dinitrile, spiro-pyrans, 3-dicyano methene-1; 5; Compounds such as 5-trimethyl cyclohexene are conjugation acceptor (they have the good electron transmittability) and its reaction has obtained a series of conjugated compounds, and their structure is characterized.Absorb and the pl-fluorescence peak through testing its ultraviolet-visible, find the fluorescence that majority of compounds is red, the part of compounds fluorescence quantum yield is higher, and the result shows that these compounds are the organic electroluminescent novel materials with using value.
Reference:
1、Hefnawy，M.M.，J.Pharm.Biomed.Anal.，2002，27，661.
2、Massie，S.P.，Chem.Rev.，1954，54(5)，797.
3a、Ito，T.；Kondo，A.；Terada，S.J.Am.Chem.Soc.2006，128，10934.
3b、Zhu，F.J.；Hua，Y.L.；Wu，X.M.，Chinese?Journal?of?Luminescence，2006，27，5：715.
3c、Cho，D.W.；Fujitsuka，M.；Choi，K.H.，J.Phys.Chem.B?2006，110，4576.
3d、Serron，S.A.；Meyer，T.J.，J.Am.Chem.Soc.2004，126，14506.
4、Hashmi，S.A.N.；Hu，X.；Immoos，C.E.，Org.Lett.，2002，4，26，4571.
5a、Jenekhe，S.A.；Wellinghoff，S.T.；Reed，J.F.，Mol.Cryst.Liq.Cryst.1984，105，175.
5b、Jenekhe，S.A.；Lu，L.；Alam，M.M.，Macromolecules，2001，34，7315.
5c、Jenekhe，S.A.；Lu，L.；Alam，M.M.Macromolecules?2003，36，8992.
5d、Kulkarni，A.P.；Wu，P.T.；Kwon，T.W.；Jenekhe，S.A.，J.Phys.Chem.B，2005，109，19584.
5e、Kulkarni，A.P.；Kong，X.；Jenekhe，S.A.，Adv.Funct.Mater.，2006，16，1057.
5f、Kulkarni，A.P.；Kong，X.；Jenekhe，S.A.，Macromolecules?2006，39，8699.
6a、Liu，Y.；Li，J.；Gong，Q.；Cao，S.Polym.Adv.Technol.2006；1?7：468.
6b、Qu，B.；Chen，Z.；Cao，S.；Gong，Q.J.Phys.D：Appl.Phys.，2006，39，2680.
6c、Cao，H.；Chen，Z.；Cao，S.；Gong，Q.，Synth.Met?2007，157，427.
6d、Liu，Y.；Cao，H.；Li，J.；Gong，Q.，J.Polym.Sci.A.：Polym.Chem.2007，45，4867.
6e、Liu，Y.；Li，J.；Cao，S.；Gong，Q.，Polym.Adv.Technol.，2008，19，1584.
7a、Yin，S.；Wedel，A.；Janietz，S.；Krueger，H.，Janietz，A.，Synth.Met.，2003，137，1145.
7b、Xu，F.；Wang，C.；Yang，L.；Yin，S.，Janietz，A.，Synth.Met.2005，152，221.
Summary of the invention
The objective of the invention is to explore the compound of good electrical electroluminescent properties, the 3-replacement-N-with characteristics of luminescence is provided hexyl phenothiazine derivative.
The present invention proposes 3-replacement-N-hexyl phenothiazine derivative (I):
R is a malononitrile group, 1,2 in the formula (I), 4-triazolo [1; 5-a] pyrimidyl, spiro-pyrans base, 3-dicyano methene-1,5,5-3-methyl cyclohexanol thiazolinyl, 1; 3-diethylammonium-2-thiobarbituricacid base, N, TMSDMA N dimethylamine base phenyl, right-nitrophenyl or 2,4; 6-trimethylammonium-3,5-dicyanopyridine base.
The compound of above-mentioned formula provided by the invention (I) has good electroluminescent properties, and majority of compounds is a red electroluminescent materials, is applied to can be made into Organic Light Emitting Diode in the flat-panel monitor.
With the preparation of the represented 3-replacement-N-hexyl phenothiazine derivative of general formula (I), be to make the represented compound of general formula (II) through the gram Na Gaier of Novi condensation (Knoevenagel condensation) reaction or Wittig (Wittig) reaction (I) verivate of expressing that obtains having general formula;
Wherein, described acceptor compound is a propane dinitrile, 5,7-dimethyl--1,2,4-triazolo [1; 5-a] pyrimidine-2-methylsulfonic acid, 5,7-dimethyl--1,2,4-triazolo [1; 5-a] pyrimidine-2-thioacetic acid, 5,7-dimethyl--1,2,4-triazolo [1; 5-a] pyrimidine-2-ethyl thioacetate, 3-dicyano methene-1,5,5-trimethyl cyclohexene, 1,3-diethylammonium-2-thiobarbituricacid, 2; 4,6-trimethylammonium-3,5-dicyanopyridine, spiro-pyrans, bromination be right-N, TMSDMA N dimethylamine base phenyl triphenyl phosphorus or bromination p-nitrophenyl triphenyl microcosmic salt.
(1) propane dinitrile is 3-(2,2-dicyano vinyl)-N-hexyl phenothiazine synthetic of acceptor,
Pyridine: pyridine; Reflux: reflux.
(2) through 3-formyl radical-N-hexyl phenothiazine and compound 5,7-dimethyl--1,2, more synthetic D-π-A of the Na Gaier of the gram Novi condensation reaction of 4-triazolo [1,5-a] pyrimidine or spiro-pyrans and D-A-D type conjugate light-emitting compound,
Piperidine: piperidines; N-butanol: propyl carbinol; Reflux: reflux.
(3) through 3-formyl radical-N-hexyl phenothiazine and 3-dicyano methene-1,5,5-trimethyl cyclohexene, 1, two D-π-A type conjugate light-emitting compounds are synthesized in the Na Gaier of the gram Novi condensation reaction of 3-diethylammonium-2-thiobarbituricacid,
Piperidine: piperidines; N-butanol: propyl carbinol; Ethanol: ethanol; Reflux: reflux.
(4) the wittig reaction synthesis of conjugate compound of 3-formyl radical-N-hexyl phenothiazine and corresponding season phosphonium salt (bromination is right-N, TMSDMA N dimethylamine base phenyl triphenyl phosphorus or bromination p-nitrophenyl triphenyl microcosmic salt),
T-BuOK: trimethyl carbinol first; THF: THF; R.t.: room temperature.
(5) 3-formyl radical-N-hexyl phenothiazine and 2,4,6-trimethylammonium-3, the Na Gaier of the gram Novi condensation reaction of 5-dicyanopyridine,
Piperidine: piperidines; N-butanol: propyl carbinol; Reflux: reflux; 72h:72 hour.
In the above-mentioned reaction, the basic operational steps of the gram Na Gaier of Novi condensation reaction:
With 3-formyl radical-N-hexyl phenothiazine and propane dinitrile is that adding in 1: 1.1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio, adds pyridine again and makes solvent, refluxes 1 hour; The reaction mixture cooling is poured in the water, chloroform extraction, salt solution washing; Anhydrous magnesium sulfate drying filters, and the pressure reducing and steaming solvent obtains the thick product of sorrel; Thick product is purified with 300-400 silica gel order chromatographic column, and eluent: sherwood oil: acetone=15: 1 (volume ratio) obtains 3-(2; 2-dicyano vinyl)-and the N-hexyl phenothiazine, promptly compound 1.
With 3-formyl radical-N-hexyl phenothiazine and acceptor compound 5,7-dimethyl--1,2,4-triazolo [1; 5-a] pyrimidine-2-methylsulfonic acid is to add at 2.1: 1 to be equipped with in the round-bottomed flask of reflux condensing tube in molar ratio, adds the piperidines that propyl carbinol is made solvent and catalytic amount again, temperature rising reflux, 5; 7-dimethyl--1,2,4-triazolo [1,5-a] pyrimidine-2-methylsulfonic acid divides the adding reaction flask four times; Reinforced finishing, reacting reduced pressure after 72 hours steams propyl carbinol, adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio); Collect the second colour band material, obtain 3-(5-methyl isophthalic acid, 2; 4-triazolo [1,5-a] pyrimidine-2-methylsulfonic acid-3-vinyl)-and the N-hexyl phenothiazine, promptly compound 3.
With 3-formyl radical-N-hexyl phenothiazine and acceptor compound 5,7-dimethyl--1,2,4-triazolo [1; 5-a] pyrimidine-2-ethyl thioacetate is to add at 2.1: 1 to be equipped with in the round-bottomed flask of reflux condensing tube in molar ratio, adds the piperidines that propyl carbinol is made solvent and catalytic amount again, temperature rising reflux, 5; 7-dimethyl--1,2,4-triazolo [1,5-a] pyrimidine-2-ethyl thioacetate divides the adding reaction flask four times; Reinforced finishing, reacting reduced pressure after 12 hours steams propyl carbinol, adopts 300-400 order silica gel chromatographic column to purify eluent: acetone: sherwood oil=15: 1 (volume ratio); Collect the second colour band material, obtain 3-(5-methyl isophthalic acid, 2; 4-triazolo [1,5-a] pyrimidine-2-ethyl thioacetate-3-vinyl)-and the N-hexyl phenothiazine, promptly compound 5.
With 3-formyl radical-N-hexyl phenothiazine and acceptor compound 3-dicyano methene-1,5, the 5-trimethyl cyclohexene is that adding in 1: 1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio; Reenter ethanol and make solvent, drip the piperidines of catalytic amount, 3-formyl radical-N-hexyl phenothiazine divides four addings; Add and refluxed 3 hours, steam ethanol and obtain thick product, thick product adopts 300-400 order silica gel chromatographic column to purify; Eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio), collect the first colour band material, obtain 3-(3-dicyano methene-1; 5,5-trimethyl cyclohexene-6-vinyl)-the N-hexyl phenothiazine, promptly compound 7.
With 3-formyl radical-N-hexyl phenothiazine and acceptor compound 1,3-diethylammonium-2-thiobarbituricacid is that adding in 1: 1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio, reenters ethanol and makes solvent; Drip the piperidines of catalytic amount, 3-formyl radical-N-hexyl phenothiazine divides four addings, adds the back and refluxes 3 hours; Steam ethanol and obtain thick product, thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=8: 1 (volume ratio); Collect the first colour band material; Obtain 3-(1,3-diethylammonium-2-thiobarbituricacid-5-vinyl)-N-hexyl phenothiazine, promptly compound 8.
With 3-formyl radical-N-hexyl phenothiazine and acceptor compound 2,4,6-trimethylammonium-3,5-dicyanopyridine are that adding in 2.1: 1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio; Add propyl carbinol again and make solvent, drip the piperidines of catalytic amount, 3-formyl radical-N-hexyl phenothiazine gradation adds; Add and refluxed 2 days, decompression steams propyl carbinol and obtains thick product, and thick product adopts 300-400 order silica gel chromatographic column to purify; Eluent: sherwood oil: ETHYLE ACETATE=20: 1 (volume ratio), collect the first colour band material, obtain 3-(4; 6-dimethyl--3,5-dicyanopyridine-2-vinyl)-the N-hexyl phenothiazine, promptly compound 11.
With 3-formyl radical-N-hexyl phenothiazine and acceptor compound 5,7-dimethyl--1,2,4-triazolo [1; 5-a] pyrimidine-2-methylsulfonic acid is to add at 2.1: 1 to be equipped with in the round-bottomed flask of reflux condensing tube in molar ratio, adds propyl carbinol and makes solvent, drips the piperidines of catalytic amount, temperature rising reflux; 5,7-dimethyl--1,2,4-triazolo [1; 5-a] pyrimidine-2-methylsulfonic acid gradation adding reaction flask, reinforced finishing, reacting reduced pressure after 72 hours steams propyl carbinol, adopts 300-400 order silica gel chromatographic column to purify; Eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio), collect the first colour band material, obtain 3,7-two (5-methyl isophthalic acid; 2,4-triazolo [1,5-a] pyrimidine-2-methylsulfonic acid-3-vinyl)-the N-hexyl phenothiazine, promptly compound 2.
With 3-formyl radical-N-hexyl phenothiazine and acceptor compound 5,7-dimethyl--1,2,4-triazolo [1; 5-a] pyrimidine-2-thioacetic acid is to add at 2.1: 1 to be equipped with in the round-bottomed flask of reflux condensing tube in molar ratio, adds propyl carbinol and makes solvent, drips the piperidines of catalytic amount, 5; 7-dimethyl--1,2,4-triazolo [1,5-a] pyrimidine-2-thioacetic acid gradation adds reaction flask; Reinforced finishing, temperature rising reflux, reacting reduced pressure after 48 hours steams propyl carbinol, adopts 300-400 order silica gel chromatographic column to purify; Eluent: acetone: sherwood oil=20: 1 (volume ratio), collect the first colour band material, obtain 3,7-two (5-methyl isophthalic acid; 2,4-triazolo [1,5-a] pyrimidine-2-thioacetic acid-3-vinyl)-the N-hexyl phenothiazine, promptly compound 4.
With 3-formyl radical-N-hexyl phenothiazine and acceptor compound 2,6-dimethyl--4-H-4-(methylene dicyanoethyl) pyrans is that adding in 2.1: 1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio, adds propyl carbinol and makes solvent; Drip the piperidines of catalytic amount, 3-formyl radical-N-hexyl phenothiazine gradation adds, and adding finishes keeps refluxing 11 hours; Decompression steams propyl carbinol and obtains thick product, and thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=10: 1 (volume ratio); Collect the first colour band material; Obtain 2,6-two (3-vinyl-N-hexyl phenothiazine)-spiro-pyrans, promptly compound 6.
The basic operational steps of described wittig reaction is: with 3-formyl radical-N-hexyl phenothiazine, bromination right-N, TMSDMA N dimethylamine base phenyl triphenyl phosphorus and potassium tert.-butoxide are to add in dry good three-necked flask at 0.9: 1.5: 2.0 in molar ratio, vacuumize and logical nitrogen protection; Under the ice-water bath cooling, inject THF slowly; Stirred 20 minutes, and injected the tetrahydrofuran solution of 3-formyl radical-N-hexyl phenothiazine more slowly, room temperature reaction 4 hours; Filter, filtrate water washing back adds MgSO
4Dry 12 hours, refilter afterwards, evaporated under reduced pressure filtrating adds a granule iodine and a toluene in the gained solid; Refluxed one hour, evaporated under reduced pressure toluene gets thick product; Thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio), collect the first colour band material; Obtain 3-(right-N, TMSDMA N dimethylamine base phenyl vinyl)-N-hexyl phenothiazine, promptly compound 9.
With 3-formyl radical-N-hexyl phenothiazine, bromination p-nitrophenyl triphenyl microcosmic salt and potassium tert.-butoxide are 1.0: 2.1: 2.3 in molar ratio, add in the dry good three-necked flask; Vacuumize and logical nitrogen protection, under the ice-water bath cooling, inject THF slowly, stirred 20 minutes; Slowly inject the tetrahydrofuran solution of 3-formyl radical-N-hexyl phenothiazine again; Room temperature reaction 5 hours filters, and filtrate water washing back adds MgSO
4Dry 12 hours, refilter evaporated under reduced pressure filtrating afterwards; In the gained solid, add a granule iodine and a toluene again, refluxed one hour, evaporated under reduced pressure toluene gets thick product; Thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=20: 1 (volume ratio), collect the first colour band material; Obtain 3-(p-nitrophenyl vinyl)-N-hexyl phenothiazine, promptly compound 10.
Description of drawings
The ultraviolet-visible of Fig. 1 compound 3,4 in chloroformic solution absorbs figure
The ultraviolet-visible of Fig. 2 compound 3,5,11 in chloroformic solution absorbs figure
The ultraviolet-visible of Fig. 3 compound 1,8,11 in chloroformic solution absorbs figure
The fluorescent emission figure of Fig. 4 compound 2,3,6 in chloroformic solution
The fluorescent emission figure of Fig. 5 compound 3,5,11 in chloroformic solution
The fluorescent emission figure of Fig. 6 compound 1,7,10 in chloroformic solution
Embodiment
Come more specifically to explain the preparation and the illumination effect of compound in (I) of the present invention formula below through instance.
With 3-formyl radical-N-hexyl phenothiazine (0.33g, 1.1mmol) and propane dinitrile (80.1mg 1.2mmol) adds round-bottomed flask and adds the 15mL pyridine again, refluxes 1 hour.The reaction mixture cooling is poured in the water, chloroform extraction, and the salt solution washing, anhydrous magnesium sulfate drying filters, and the pressure reducing and steaming solvent obtains the thick product of sorrel; Thick product is purified eluent: sherwood oil with 300-400 order silica gel chromatographic column: acetone=15: 1 (volume ratio) gets red product-compound 1 (0.34g, productive rate 87%).
Compound 1:
Ultimate analysis: measured value C% 73.31 H% 5.70 N% 12.03 S% 8.96;
Calculated value C% 73.54 H% 5.85 N% 11.70 S% 8.91
IR(cm
-1)2217(CN)，960(C＝C)。
1HNMR(CDCl
3，400MHz)δ：0.88(t，3H，CH
3)，1.32(d，4H，CH
2)，1.43(t，2H，CH
2)，1.80(t，2H，CH
2)，3.87(t，2H，NCH
2)，6.84-6.89(m，2H，Ar-H)，7.00(t，1H，Ar-H)，7.08(d，1H，Ar-H)，7.16(t，1H，Ar-H)，7.48(m，1H，Ar-H)，7.55(m，1H，Ar-H)，7.75(m，1H，Ar-H)。
MS?m/z(％)：359.3(M
+，100.00)，273.9(89.54)，288.2(76.76)，256.6(19.02)，296.0(9.62)。
Embodiment 2
Compound 2 preparations:
Be equipped with at 50mL and add 3-formyl radical-N-hexyl phenothiazine in the round-bottomed flask of reflux condensing tube (0.87g 2.8mmol), and adds the piperidines of propyl carbinol (27mL) and 3 catalytic amounts, temperature rising reflux; 5,7-dimethyl--1,2,4-triazolo [1; 5-a] (0.30g 1.3mmol) divides four adding reaction flasks to pyrimidine-2-methylsulfonic acid, reinforced finishing; Reacting reduced pressure after 72 hours steams propyl carbinol, adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio); Collect the first colour band material, get atropurpureus product-compound 2 (190.3mg, productive rate 19%).
Compound 2
Ultimate analysis: measured value C% 67.87 H% 5.72 N% 10.39 S% 12.21;
Calculated value C% 67.95 H% 5.95 N% 10.34 S%11.83.
IR(cm
-1)1660，937(C＝C)，1335，1165(SO
2)
1HNMR(CDCl
3，400MHz)δ：0.88(t，6H，CH
3)，1.25-1.54(m，12H，CH
2)，1.82(s，4H，CH
2)，3.47(s，3H，SO
2-CH
3)，3.87(s，4H，NCH
2)，6.86-7.24(m，12H，Ar-H)，7.29-7.47(m，6H，Ar-H)，7.87(m，1H，Ar-H)。
MS?m/z(％)：813.1(M
+，0.00)，103.7(100.00)，131.2(45.82)，168.7(25.89)，187.8(25.86)。
Be equipped with at 50mL and add 3-formyl radical-N-hexyl phenothiazine in the round-bottomed flask of reflux condensing tube (0.87g 2.8mmol), and adds the piperidines of propyl carbinol (27mL) and 4 catalytic amounts, temperature rising reflux; 5,7-dimethyl--1,2,4-triazolo [1; 5-a] (0.30g 1.3mmol) divides four adding reaction flasks to pyrimidine-2-methylsulfonic acid, reinforced finishing; Reacting reduced pressure after 72 hours steams propyl carbinol, adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio); Collect the second colour band material, get orange/yellow solid product-compound 3 (277.0mg, productive rate 42%).
Ultimate analysis: measured value C% 62.45 H% 5.67 N% 13.50 S% 12.16;
Calculated value C% 62.40 H% 5.62 N% 13.48 S% 12.34.
IR(cm
-1)936(C＝C)，1333，1163(SO
2)。
1HNMR(CDCl
3，400MHz)δ：0.95(t，3H，CH
3)，1.38(m，4H，CH
2)，1.56(t，2H，CH
2)，1.97(t，2H，CH
2)，2.78(s，3H，CH
3)，3.45(s，3H，SO
2-CH
3)，4.23(t，2H，NCH
2)，7.32(t，2H，Ar-H)，7.46(t，2H，Ar-H)，7.61-7.70(m，2H，Ar-H)，7.99(d，2H，Ar-H)，8.06(d，1H，Ar-H)，8.20(s，1H，Ar-H)。
MS?m/z(％)：519.0(M
+，100.00)，434.2(65.84)，448.3(49.16)，354.7(38.04)，416.3(21.86)，521.0(20.32)，222.0(27.96)。
Be equipped with at 50mL and add 3-formyl radical-N-hexyl phenothiazine in the round-bottomed flask of reflux condensing tube (1.10g 3.5mmol), and adds the piperidines of propyl carbinol (35mL) and four catalytic amounts, temperature rising reflux; 5,7-dimethyl--1,2,4-triazolo [1; 5-a] (0.38g 1.6mmol) divides four adding reaction flasks to pyrimidine-2-thioacetic acid, reinforced finishing; Reacting reduced pressure after 48 hours steams propyl carbinol, adopts 300-400 order silica gel chromatographic column to purify eluent: acetone: sherwood oil=20: 1 (volume ratio); Collect the first colour band material, get atropurpureus product-compound 4 (290.3mg, productive rate 22%).
Ultimate analysis: measured value C% 68.39 H% 5.97 N% 10.49 S% 11.30;
Calculated value C% 68.41 H% 5.86 N% 10.19 S% 11.66.
IR(cm
-1)3582(OH)，1612(CO)，958(C＝C)。
1HNMR(CDCl
3，400MHz)δ：0.88(t，3H，CH
3)，1.26-1.57(m，6H，CH
2)，1.80(d，2H，CH
2)，3.48(s，3H，O-CH
3)，3.79(m，2H，N-CH
2)，4.15(m，2H，S-CH
2)，6.75-7.40(m，29H，Ar-H)，7.90(s，1H，Ar-H)。
Be equipped with at 50mL and add 3-formyl radical-N-hexyl phenothiazine in the round-bottomed flask of reflux condensing tube (0.87g 2.8mmol), and adds the piperidines of propyl carbinol (27mL) and 3 catalytic amounts, temperature rising reflux; 5,7-dimethyl--1,2,4-triazolo [1; 5-a] (0.30g 1.3mmol) divides four adding reaction flasks to pyrimidine-2-ethyl thioacetate, reinforced finishing; Reacting reduced pressure after 12 hours steams propyl carbinol, adopts 300-400 order silica gel chromatographic column to purify eluent: acetone: sherwood oil=15: 1 (volume ratio); Collect the second colour band material, get red solid product-compound 5 (0.47g, productive rate 51%).
Ultimate analysis: measured value C% 65.86 H% 5.80 N% 12.87 S% 11.50;
Calculated value C% 65.83 H% 5.73 N% 12.83 S% 11.75.
IR(em
-1)1738(CO)，960(C＝C)。
1HNMR(CDCl
3，400MHz)δ：0.84(t，3H，CH
3)，1.26-1.45(m，6H，CH
2)，1.77(m，2H，CH
2)，2.60(s，3H，CH
3)，3.74(m，2H，O-CH
3)，3.82(m，2H，N-CH
2)，4.11(s，2H，S-CH
2)，6.71-7.40(m，29H，Ar-H)，7.94(s，1H，Ar-H)。
Embodiment 6
Compound 6 preparations:
In the round-bottomed flask of 50mL, add 2; (0.21g 1.2mmol) with the 20mL propyl carbinol, drips 4 piperidines catalysis to 6-dimethyl--4-H-4-(methylene dicyanoethyl) pyrans; Reaction is warming up to backflow then with 3-formyl radical-N-hexyl phenothiazine (0.82g; 2.6mmol) divide four addings, adding finishes keeps refluxing 11 hours, and decompression steams propyl carbinol and obtains thick product; Thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=10: 1 (volume ratio), collect the first colour band material, and get black solid product-compound 6 (0.57g, productive rate 63%).
Compound 6
Ultimate analysis: measured value C% 75.98 H% 6.58 N% 7.33 S% 8.10;
Calculated value C% 75.95 H% 6.11 N% 7.38 S% 8.45.
IR(cm
-1)2219(CN)，963(C＝C)。
1HNMR(CDCl
3，400MHz)δ：0.87(t，6H，CH
3)，1.32(d，8H，CH
2)，1.45(s，4H，CH
2)，1.82(m，4H，CH
2)，3.86(t，4H，N-CH
2)，6.57(m，2H，Ar-H)，6.86-6.96(m，6H，Ar-H)，7.13-7.27(m，4H，Ar-H)，7.27-7.39(m，8H，Ar-H)。
Embodiment 7
Compound 7 preparations:
In the round-bottomed flask of 50mL, add 3-dicyano methene-1,5,5-trimethyl cyclohexene (0.17g; 1.0mmol) and 20mL ethanol; Drip 4 piperidines catalysis, reaction is warming up to backflow, and (0.34g 1.1mmol) divides four times and adds with 3-formyl radical-N-hexyl phenothiazine then; Adding finishes keeps refluxing 3 hours, steams ethanol and obtains thick product; Thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio), collect the first colour band material, and get reddish-brown solid phase prod-compound 7 (0.27g, productive rate 57%).
Compound 7:
Ultimate analysis: measured value C% 75.98 H% 6.58 N% 7.33 S% 8.10;
Calculated value C% 75.95 H% 6.11 N% 7.38 S% 8.45.
IR(cm
-1)2223(CN)，955(C＝C)。
1HNMR(CDCl
3，400MHz)δ：0.95(s，3H，CH
3)，1.02(s，6H，CH
3)，1.26-1.63(m，6H，CH
2)，1.98(m，2H，CH
2)，4.22(t，2H，NCH
2)，6.86(s，2H，Ar-H)，6.97-7.12(m，2H，Ar-H)，7.27-7.37(t，4H，Ar-H)，7.66(t，2H，Ar-H)，7.70(d，1H，Ar-H)，7.82(t，2H，Ar-H)。
MS?m/z(％)：479.1(M
+，100.00)，394.0(47.23)，408.1(26.80)，376.2(14.51)。
Embodiment 8
Compound 8 preparations:
In the round-bottomed flask of 50mL, add 1; 3-diethylammonium-2-thiobarbituricacid (0.20g; 1.0mmol) and 20mL ethanol, drip 4 piperidines catalysis, reaction is warming up to backflow then with 3-formyl radical-N-hexyl phenothiazine (0.31g; 1.0mmol) divide four addings, adding finishes keeps refluxing 3 hours.Steam ethanol and obtain thick product; Thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=8: 1 (volume ratio), collect the first colour band material, and get reddish-brown solid phase prod-compound 8 (0.38g, productive rate 76%).
Compound 8:
Ultimate analysis: measured value C% 65.74 H% 6.35 N% 8.48 S% 12.63;
Calculated value C% 65.69 H% 6.33 N% 8.51 S% 12.99.
IR(cm
-1)1669，1701(CO)，959(C＝C)。
1HNMR(CDCl
3，400MHz)δ：0.88(s，3H，CH
3)，1.25-1.45(m，12H，CH
2&CH
3)，1.83(m，2H，CH
2)，3.87(t，2H，N-CH
2)，4.55(t，4H，N-CH
2)，6.84-7.10(m，7H，Ar-H)，8.18(d，2H，Ar-H)，8.35(s，1H，Alykene-H)。
Embodiment 9
The preparation of compound 9:
In the three-necked flask of 100mL, add 3-formyl radical-N-hexyl phenothiazine (0.29g, 0.9mmol), bromination is right-N; TMSDMA N dimethylamine base phenyl triphenyl phosphorus (0.71g, 1.5mmol) and potassium tert.-butoxide (0.23g, 2.0mmol); Vacuumize and logical nitrogen protection, and the THF of under the ice-water bath cooling, newly handling with the syringe injection (THF, 15mL); Stir the THF solution that injected the 5mL of corresponding aldehyde in about 20 minutes, room temperature reaction 4 hours filters; Filtrate water washing back several times adds a dry night of MgSO4, refilters evaporated under reduced pressure filtrating afterwards.In the gained solid, add granule iodine and 120mL toluene again, refluxed one hour, evaporated under reduced pressure toluene gets thick product; Thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio), collect the first colour band material, and get reddish-brown solid phase prod-compound 9 (0.26g, productive rate 67%).
Compound 9:
Ultimate analysis: measured value C% 78.50 H% 7.49 N% 6.47 S% 7.20;
Calculated value C% 78.46 H% 7.52 N% 6.54 S% 7.48.
IR(cm
-1)1638，949(C＝C)。
1HNMR(CDCl
3，400MHz)δ：0.86(t，3H，CH
3)，1.25-1.31(m，6H，CH
2)，1.42(t，2H，CH
2)，1.80(t，2H，CH
2)，2.95(d，6H，N-CH
3)，3.81(t，2H，CH
2)，6.71-6.91(m，7H，Ar-H)，7.12-7.26(m，4H，Ar-H)，7.37(d，2H，Ar-H)。
The preparation of compound 10:
Adding 3-formyl radical-N-hexyl phenothiazine in the three-necked flask of 100mL (0.32g, 1.0mmol), bromination p-nitrophenyl triphenyl microcosmic salt (0.91g; 2.1mmol) and potassium tert.-butoxide (0.26g 2.3mmol), vacuumizes and logical nitrogen protection; (THF 15mL), stirs the THF solution that injected the 5mL of corresponding aldehyde in about 20 minutes under the ice-water bath cooling, to inject the new THF of handling with syringe; Room temperature reaction 5 hours filters, and filtrate water washing back several times adds a dry night of MgSO4; Refilter evaporated under reduced pressure filtrating afterwards.In the gained solid, add granule iodine and 120mL toluene again, refluxed one hour, evaporated under reduced pressure toluene gets thick product; Thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=20: 1 (volume ratio), collect the first colour band material, and get yellow solid product-compound 10 (0.35g, productive rate 83%).
Compound 10:
Ultimate analysis: measured value C% 72.50 H% 6.25 N% 7.53 S% 7.23;
Calculated value C% 72.53 H% 6.09 N% 6.51 S% 7.45.
IR(cm
-1)1642，954(C＝C)。
1HNMR(CDCl
3，400MHz)δ：0.85(m，3H，CH
3)，1.26-1.44(m，6H，CH
2)，1.75(m，2H，CH
2)，3.80(m，6H，N-CH
3)，6.70-6.85(m，2H，Ar-H)，6.90-6.94(m，2H，Ar-H)，7.07-7.17(m，4H，Ar-H)，7.50(d，2H，Ar-H)，8.14(m，2H，Ar-H)。
The preparation of compound 11:
In the round-bottomed flask of 50mL, add 2,4,6-trimethylammonium-3; 5-dicyanopyridine (0.17g; 1mmol), drip 4 piperidines catalysis, reaction is warming up to backflow then with 3-formyl radical-N-hexyl phenothiazine (0.67g with the 15mL propyl carbinol; 2.1mmol) divide adding several times, adding finishes keeps refluxing 2 days.Decompression steams propyl carbinol and obtains thick product; Thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=20: 1 (volume ratio), collect the first colour band material, and get atropurpureus solid phase prod-compound 11 (0.26g, productive rate 57%).
Compound 11:
Ultimate analysis: measured value C% 74.75 H% 6.15 N% 12.24 S% 8.12;
Calculated value C% 74.97 H% 6.07 N% 12.06 S% 6.90.
IR(cm
-1)2221(CN)，956(C＝C)。
1HNMR(CDCl
3，400MHz)δ：0.86(t，3H，CH
3)，1.25-1.32(m，6H，CH
2)，1.79(t，2H，CH
2)，2.70(s，3H，CH
3)，2.80(s，3H，CH
3)，3.83(t，2H，CH
3)，6.82-6.95(m，4H，Ar-H)，7.13-7.15(m，3H，Ar-H)，7.26-7.43(m，2H，Ar-H)，7.99(d，2H，Vinyl-H)。
Can find out that from following experiment compound of the present invention has good luminescent characteristic in chloroformic solution, emission wavelength mainly concentrates on red area.
Embodiment 12
The photoluminescence experiment:
Uv-visible absorption spectra (the λ of compound 1-11
Abs Max), fluorescence emission spectrum (λ
Spf Max) (concentration in chloroformic solution is 1 * 10
-5Mol/L) data are seen table 2.
Table 2
Claims (12)
1. one type of 3-replacement-N-hexyl phenothiazine derivative, (I) expresses to it is characterized in that having general formula
Structure,
In the formula: R is malononitrile group, 3-dicyano methene-5,5-dimethyl-cyclohexenyl, 1,3-diethylammonium-2-thiobarbituricacid base, N; TMSDMA N dimethylamine base phenyl, right-nitrophenyl or 4,6-dimethyl--3,5-dicyanopyridine base, 7-methyl isophthalic acid; 2,4-triazolo [1,5-a] pyrimidine-2-methylsulfonic acid base, 7-(N-hexyl phenothiazine base) vinyl)-1; 2,4-triazolo [1,5-a] pyrimidine-2-methylsulfonic acid base, 7-(N-hexyl phenothiazine base) vinyl)-1; 2,4-triazolo [1,5-a] pyrimidine-2-thioacetic acid base, 7-methyl isophthalic acid; 2,4-triazolo [1,5-a] pyrimidine-2-ethyl thioacetate base, 6-(N-hexyl phenothiazine base) vinyl-4-(methylene dicyanoethyl) pyranyl.
2. the preparation method of the represented 3-replacement-N-hexyl phenothiazine derivative of the described general formula of claim 1 (I); It is characterized in that, make represented compound of general formula (II) and acceptor compound through the gram Na Gaier of Novi condensation reaction or wittig reaction (I) verivate of expressing that obtains having general formula;
Wherein, described acceptor compound is a propane dinitrile, 5,7-dimethyl--1,2,4-triazolo [1; 5-a] pyrimidine-2-methylsulfonic acid, 5,7-dimethyl--1,2,4-triazolo [1,5-a] pyrimidine-2-thioacetic acid, 5; 7-dimethyl--1,2,4-triazolo [1,5-a] pyrimidine-2-ethyl thioacetate, 3-dicyano methene-1; 5,5-trimethyl cyclohexene, 1,3-diethylammonium-2-thiobarbituricacid, 2,4; 6-trimethylammonium-3,5-dicyanopyridine, 2,6-dimethyl--4-(methylene dicyanoethyl) pyrans, bromination be right-N, TMSDMA N dimethylamine base phenyl triphenyl phosphorus or bromination p-nitrophenyl triphenyl microcosmic salt.
3. the preparation method of the verivate that general formula as claimed in claim 2 (I) is represented is characterized in that, by the elementary operation of the gram Na Gaier of Novi condensation reaction, 3-formyl radical-N-hexyl phenothiazine and propane dinitrile are that adding in 1: 1.1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio; Add pyridine again and make solvent, refluxed 1 hour, the reaction mixture cooling is poured in the water; Chloroform extraction, salt solution washing, anhydrous magnesium sulfate drying; Filter, the pressure reducing and steaming solvent obtains the thick product of sorrel, and thick product is purified with 300-400 silica gel order chromatographic column; Eluent: sherwood oil: acetone=15: 1 (volume ratio) obtains 3-(2,2-dicyano vinyl)-N-hexyl phenothiazine.
4. the preparation method of the verivate that general formula as claimed in claim 2 (I) is represented is characterized in that, by the elementary operation of the gram Na Gaier of Novi condensation reaction, with 3-formyl radical-N-hexyl phenothiazine and acceptor compound 5; 7-dimethyl--1,2,4-triazolo [1,5-a] pyrimidine-2-methylsulfonic acid are that adding in 2.1: 1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio; Add propyl carbinol and make solvent, add the piperidines of catalytic amount, temperature rising reflux, 5; 7-dimethyl--1,2,4-triazolo [1,5-a] pyrimidine-2-methylsulfonic acid gradation adds reaction flask; Reinforced finishing, reacting reduced pressure after 72 hours steams propyl carbinol, adopts 300-400 order silica gel chromatographic column to purify; Eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio), collect the second colour band material, obtain 3-(5-methyl isophthalic acid; 2,4-triazolo [1,5-a] pyrimidine-2-methylsulfonic acid-3-vinyl)-the N-hexyl phenothiazine.
5. the preparation method of the verivate that general formula as claimed in claim 2 (I) is represented is characterized in that, by the elementary operation of the gram Na Gaier of Novi condensation reaction; With 3-formyl radical-N-hexyl phenothiazine and acceptor compound 3-dicyano methene-1,5, the 5-trimethyl cyclohexene is that adding in 1: 1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio; Add ethanol and make solvent, drip the piperidines of catalytic amount, 3-formyl radical-N-hexyl phenothiazine gradation adds; Add and refluxed 3 hours, steam ethanol and obtain thick product, thick product adopts 300-400 order silica gel chromatographic column to purify; Eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio); Collect the first colour band material, obtain 3-(3-dicyano methene-5,5-dimethyl-tetrahydrobenzene-6-vinyl)-N-hexyl phenothiazine.
6. the preparation method of the verivate that general formula as claimed in claim 2 (I) is represented is characterized in that, by the elementary operation of the gram Na Gaier of Novi condensation reaction; With 3-formyl radical-N-hexyl phenothiazine and acceptor compound 1,3-diethylammonium-2-thiobarbituricacid is that adding in 1: 1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio, adds ethanol again and makes solvent; Drip the piperidines of catalytic amount, 3-formyl radical-N-hexyl phenothiazine gradation adds, and adds the back and refluxes 3 hours; Steam ethanol and obtain thick product; Thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=8: 1 (volume ratio), collect the first colour band material; Obtain 3-(1,3-diethylammonium-2-thiobarbituricacid-5-vinyl)-N-hexyl phenothiazine.
7. the preparation method of the verivate that general formula as claimed in claim 2 (I) is represented is characterized in that, by the elementary operation of the gram Na Gaier of Novi condensation reaction, with 3-formyl radical-N-hexyl phenothiazine and acceptor compound 5; 7-dimethyl--1,2,4-triazolo [1,5-a] pyrimidine-2-methylsulfonic acid are that adding in 2.1: 1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio; Add propyl carbinol and make solvent, drip the piperidines of catalytic amount, temperature rising reflux, 5; 7-dimethyl--1,2,4-triazolo [1,5-a] pyrimidine-2-methylsulfonic acid gradation adds reaction flask; Reinforced finishing, reacting reduced pressure after 72 hours steams propyl carbinol, adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio); Collect the first colour band material, obtain 5, two (3 '-vinyl-N-the hexyl phenothiazine)-2-methylsulfonyls-1 of 7-; 2,4-triazolo [1,5-a] pyrimidine.
8. the preparation method of the verivate that general formula as claimed in claim 2 (I) is represented is characterized in that, by the elementary operation of the gram Na Gaier of Novi condensation reaction, with 3-formyl radical-N-hexyl phenothiazine and acceptor compound 5; 7-dimethyl--1,2,4-triazolo [1,5-a] pyrimidine-2-thioacetic acid are that adding in 2.1: 1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio; Add propyl carbinol and make solvent, drip the piperidines of catalytic amount, 5,7-dimethyl--1; 2,4-triazolo [1,5-a] pyrimidine-2-thioacetic acid gradation adds reaction flask, reinforced finishing; Temperature rising reflux, reacting reduced pressure after 48 hours steams propyl carbinol, adopts 300-400 order silica gel chromatographic column to purify eluent: acetone: sherwood oil=20: 1 (volume ratio); Collect the first colour band material, get 5, two (the 3 '-vinyl-N-hexyl phenothiazine)-1 of 7-; 2,4-triazolo [1,5-a] pyrimidine-2-thioacetic acid.
9. the preparation method of the verivate that general formula as claimed in claim 2 (I) is represented is characterized in that, by the elementary operation of the gram Na Gaier of Novi condensation reaction; With 3-formyl radical-N-hexyl phenothiazine and acceptor compound 2,6-dimethyl--4-(methylene dicyanoethyl) pyrans is that adding in 2.1: 1 is equipped with in the round-bottomed flask of reflux condensing tube in molar ratio, adds propyl carbinol and makes solvent; Drip the piperidines of catalytic amount, 3-formyl radical-N-hexyl phenothiazine gradation adds, and adding finishes keeps refluxing 11 hours; Decompression steams n-propyl alcohol and obtains thick product; Thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=10: 1 (volume ratio), collect the first colour band material; Obtain 2, two (3 '-vinyl-N-hexyl phenothiazine)-4-(methylene dicyanoethyl) pyrans of 6-.
10. the preparation method of the verivate that general formula as claimed in claim 2 (I) is represented is characterized in that, presses the elementary operation of wittig reaction; With 3-formyl radical-N-hexyl phenothiazine, bromination right-N, TMSDMA N dimethylamine base phenyl triphenyl phosphorus and potassium tert.-butoxide are to join in dry three-necked flask at 0.9: 1.5: 2.0 in molar ratio, vacuumize and logical nitrogen protection; Under the ice-water bath cooling, inject THF slowly; Stirred 20 minutes, and injected the tetrahydrofuran solution of 3-formyl radical-N-hexyl phenothiazine more slowly, room temperature reaction 4 hours; Filter, filtrate water washing back adds MgSO
4Dry 12 hours, refilter evaporated under reduced pressure filtrating afterwards; In the gained solid, add a granule iodine and a toluene, refluxed evaporated under reduced pressure toluene one hour; Get thick product, thick product adopts 300-400 order silica gel chromatographic column to purify eluent: sherwood oil: ETHYLE ACETATE=15: 1 (volume ratio); Collect the first colour band material, obtain 3-(right-N, TMSDMA N dimethylamine base phenyl vinyl)-N-hexyl phenothiazine.
11. the preparation method of the verivate that general formula as claimed in claim 2 (I) is represented is characterized in that, presses the elementary operation of wittig reaction; With 3-formyl radical-N-hexyl phenothiazine, bromination p-nitrophenyl triphenyl microcosmic salt and potassium tert.-butoxide are 1.0: 2.1: 2.3 in molar ratio, join in the dry three-necked flask; Vacuumize and logical nitrogen protection, under the ice-water bath cooling, inject THF slowly, stirred 20 minutes; Slowly inject the tetrahydrofuran solution of 3-formyl radical-N-hexyl phenothiazine again; Room temperature reaction 5 hours filters, and filtrate water washing back adds MgSO
4Dry 12 hours, refilter evaporated under reduced pressure filtrating afterwards; In the gained solid, add a granule iodine and a toluene again, refluxed one hour, evaporated under reduced pressure toluene gets thick product; Thick product adopts 300-400 order silica gel chromatographic column to purify; Eluent: sherwood oil: ETHYLE ACETATE=20: 1 (volume ratio), collect the first colour band material, obtain 3-(p-nitrophenyl vinyl)-N-hexyl phenothiazine.
12. the application of the represented verivate of the described general formula of claim 1 (I) is characterized in that being applied in the flat-panel monitor as red electroluminescent materials.
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