CN101863875A - Triazole derivatives containing liquid crystal units and preparation method and application thereof - Google Patents
Triazole derivatives containing liquid crystal units and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a series of new triazole derivatives which contain liquid crystal units and have good liquid crystal character, and a preparation method and an application thereof. The synthetic method of the new triazole derivatives comprises the steps of synthesizing different chlorimide type compound intermediates and further being reacted with the corresponding hydrazide. The synthetic method of target products is simple, easy to operate and easy to control, the purity and the yield of the products are higher, and the type of compounds have great liquid crystal character, thereby being a type of novel organic electronic transmission materials.
Description
Technical field
The invention belongs to the preparing technical field of novel liquid crystal material, relate to the synthetic of a series of new triazole derivatives and liquid crystal property research thereof.Saying so more specifically, is intermediate with the different chlorimide compounds of synthetic, again with its synthetic method and liquid crystal property research thereof with the corresponding a series of new triazole derivatives of hydrazides prepared in reaction.
Background technology
Technique of display has been applied to all many-sides such as amusement, industry, military affairs, traffic, education, space flight and aviation, medical treatment as the platform of man-machine communication and information displaying, and the demonstration industry has become a big pillar of electronic information industry.Along with progress of science and technology, technique of display will constantly be expanded its Application Areas, be penetrated into human lives's every aspect.Technique of display is of a great variety, have their own characteristics each, but the flora development of novel flat-plate technique of display can be traced back to the last century sixties, and flat-panel display device is different from traditional vacuum display device fully on principle.At present, the flat panel display growth momentum is swift and violent and powerful, and liquid-crystal display (LCD) industry is fully matured, and its market share has accounted for about 85% of whole flat pannel display market.Yet because the LCD visual angle is little, response speed slow (ms level), temperature profile poor (can not use at low temperatures), LCD self can not be luminous in addition, and its demonstration depends on backlight or surround lighting.Therefore the monopoly position of LCD just is being subjected to the challenge of new technique of display organic light emitting display (Organic Lighting Emitting Display OLED).
The application prospect of OLED is very tempting, except that making indicating meter, can also be used for illumination.Optimum is applied to the indicating meter on the indicating meter of aerospacecraft, military open-air portable indicating meter and the operation battlebus etc., and civilian purposes is more extensive.OLED is the active illuminating device, can improve contrast gradient greatly, obtains better display quality, and this is that liquid-crystal display hardly matches.The OLED display screen can also be made flexible, is easy to realize crooked.Because the many application characteristics of OLED, make the research department of lot of domestic and foreign drop into huge fund one after another and great amount of manpower is carried out the OLED technical study.
Electron transport material is the chief component of charge transport layer in the organic photoconductor, the good and bad performance that directly influences organic photoconductor of its performance.The electron transport material of synthetic excellent property is one of focus of present OLED research.The organic materials that is used for electron transport material at present still relatively lacks, and scientists is actively being sought the organic electronic transport material with higher electron transport ability.
1,2,4-triazole species heterogeneous ring compound has bigger conjugate planes, shows good electronic transmission performance, is widely used as electron transport material in recent years.The present invention uses reaction conditions experimental technique simple, easy to control and that productive rate is higher relatively to synthesize 9 not see 1,2 of bibliographical information, the 4-triazole class compounds, it is characterized, and this compounds carried out the liquid crystal liquid crystal property test, the result shows that this compounds has good liquid crystal liquid crystal property.
Summary of the invention
The object of the present invention is to provide a series of the novel 1,2 of liquid crystal unit, 4-triazole derivatives of containing.
It is a kind of novel synthetic 1,2 that another object of the present invention is to provide, the method for 4-triazole derivative.
What the present invention adopted synthesizes 1,2, and the method for 4-triazole derivative has significantly different with the document of having reported, patent.The present invention selects for use different chlorimide compounds as intermediate, again itself and corresponding hydrazides reaction is obtained target product.The synthetic target product method of the present invention is simple, easy to operate, easy to control, and product purity and yield are higher.
The present invention is achieved by the following technical solutions:
The triazole derivative that contains liquid crystal unit, it is represented with following general structure:
Wherein, R
1, R
2, R
3For containing halogen, nitro, C
1-C
4Alkyl or C
1-C
4The phenyl of alkoxyl group or pyridyl.
The triazole derivative that contains liquid crystal unit of the present invention, its representative compound is as follows:
The preparation method who contains the triazole derivative of liquid crystal unit of the present invention is characterized in that being undertaken by following step:
(a) be raw material and sulfur oxychloride reaction with p-methylbenzoic acid, m-methyl benzoic acid or p-nitrobenzoic acid, synthetic acyl chloride compound;
(b) reaction by acyl chlorides and substituted aniline, synthesizing amide class intermediate; By amides intermediate and the synthetic chlorimide intermediate of sulfur oxychloride reaction.
(c) (b) synthetic chlorimide intermediate is reacted the preparation triazole class compounds with different hydrazides.
Chlorimide intermediate wherein is:
N-(4-chloro-phenyl-)-imines is to methyl benzoyl chloride;
N-(4-p-methoxyphenyl)-imines is to methyl benzoyl chloride;
N-(4-chloro-phenyl-)-imines m-methyl benzoyl formyl chloride;
N-(4-p-methoxyphenyl)-imines m-methyl benzoyl formyl chloride;
N-(4-chloro-phenyl-)-imines paranitrobenzoyl chloride.
The present invention further discloses the application of triazole derivative aspect preparation organic electronic transport material that contains liquid crystal unit.The particularly application aspect preparation liquid crystal unit or organic light emitting display material.Indicating meter on the indicating meter of aerospacecraft, military open-air portable indicating meter and the operation battlebus or the like for example.
The present invention has carried out following detection to the liquid crystal property of the new triazole derivative of institute's synthetic:
Be the measuring of new triazole derivative liquid crystal property below:
One, experimental principle
Second-order transition temperature (Tg) is a key property parameter of polymer materials, and people decide its purposes according to the height of the Tg of macromolecular material.Generally speaking, as the polymkeric substance of rigid structure material, it is use temperature that its Tg should be higher than, and as the macromolecular material of rubber use, its Tg should be lower than use temperature.From molecular structure, Tg is a kind of relaxation phenomenon of superpolymer pars amorpha from the frozen state to the thawed state.Polymkeric substance is when Tg, and except mechanical properties such as deformation and modulus changed, many other physical propertiess also all had a lot of variations as volume, the coefficient of expansion, specific heat, thermal conductivity, specific inductivity etc.Therefore, Tg has significance to the research of polymer materials.
The present invention takes the liquid crystal photograph of target compound down with polarizing microscope again by adopting the Tg of determine with dsc method target compound, and then the liquid crystal property of goal in research compound.
Two, experimental technique
1. the mensuration of liquid crystal texture: take a morsel synthetic sample on slide glass, build cover glass, observe the liquid crystal texture of its heating and cooling process under with the polarizing microscope of hot platform, carry out repeatedly repeatedly determining its texture, and take the texture photo.
2. the mensuration of characteristic temperature (DSC method): with about the accurate weighing sample of electronic balance 10mg; on DSC Q20 type differential scanning calorimeter, carry out the DSC test, to determine the fusing point and the clearing point temperature of sample, 10 ℃/min of heat-up rate; temperature range 50-350 ℃, nitrogen protection.
Three, experimental result
1. the DSC of compound 1a, 3a and 4a tests and polarized light microscope observing
Compound 4-(4-chloro-phenyl-)-3-p-methylphenyl-5-(4-pyridyl)-1,2, aminomethyl phenyl-5-(4-pyridyl)-1 between 4-triazole (1a), 4-(4-chloro-phenyl-)-3-, 2,4-triazole (3a) and 4-(4-p-methoxy-phenyl)-3-p-methylphenyl-5-(4-pyridyl)-1,2,4-triazole (4a) has similar intensification DSC curve, with 4-(4-chloro-phenyl-)-3-p-methylphenyl-5-(4-pyridyl)-1,2,4-triazole (1a) illustrates its thaw process for example.The mensuration process is observed kapillary bottom compound, and to be solid earlier opaque, is heated to the melting temperature interval, and slowly fusing is colored, continues to be heated to 210 ℃, and the liquid in the kapillary is bleach gradually.
With 4-(4-chloro-phenyl-)-3-p-methylphenyl-5-(4-pyridyl)-1,2, the DSC spectrogram of 4-triazole (1a) is an example, by we can observe among the figure, compound 1a has only an endotherm(ic)peak in the temperature-rise period, temperature changes corresponding to crystal form-isotropy attitude, and summit temperature is respectively 197.47 ℃.
Compound 1a under polarizing microscope presents more weak crystal refraction at 210 ℃, to 210 ℃ of visual field deepenings, shows the isotropic liquid state that enters.Along with the reduction of temperature, during to 98.6 ℃ become clear again in the visual field, and compound changes crystal (seeing Fig. 2 and Fig. 3) into.Along with the reduction of temperature, liquid crystal fluid presents brokenly ball-type texture gradually, presents to 67.8 ℃ and significantly breaks ball-type texture.This illustrates compound 4-(4-chloro-phenyl-)-3-p-methylphenyl-5-(4-pyridyl)-1,2, and the 4-triazole is a kind of change thermotropic liquid crystal.
2. the DSC of compound 2b tests and polarized light microscope observing
Compound 4-(4-p-methoxy-phenyl)-3-(4-nitrophenyl)-5-p-methylphenyl-1,2,4-triazole (2b) all has thermotropic liquid crystal through DSC test and polarized light microscope observing.The DSC curve of compound 2b as shown in Figure 4.As seen from the figure, in the compound 2b heating curve, located two endotherm(ic)peaks at 182.72 ℃ and 227.95 ℃, the 1st peak is the transformation peaks of solid phase-mesomorphic phase, i.e. the fusing point peak of sample; The 2nd peak is the transformation peaks of mesomorphic phase-each identical condition, i.e. the clearing point peak of sample.It between 182.72 ℃ and 227.95 ℃ the mesomorphic phase interval.
Under polarizing microscope, observe compound 4-(4-p-methoxy-phenyl)-3-(4-nitrophenyl)-5-p-methylphenyl-1,2,4-triazole (2b), in the time of near slowly being heated to 198 ℃, the sample fusion enters liquid crystal state, occurs a large amount of drops in the visual field, present typical schlieren texture, and be colored all around, liquid flows rapidly, shows that sample exists with nematic phase at present.During reheat to 241.5 ℃, schlieren texture reduces rapidly to disappear, and the visual field presents a slice black, shows that sample has been converted into isotropic liquid.During cooling, earlier at 120 ℃ of schlieren textures that yellow background occurs, become crystal again in about 67 ℃ of crystallizations again in the visual field.This illustrates compound 4-(4-p-methoxy-phenyl)-3-(4-nitrophenyl)-5-p-methylphenyl-1,2, and 4-triazole (2b) is a kind of change thermotropic liquid crystal (the polarizing microscope photo is seen Fig. 5,6).
3. the DSC of compound 1b and 4b tests and polarized light microscope observing
Compound 4-(4-chloro-phenyl-)-3-(4-nitrophenyl)-5-p-methylphenyl-1,2, aminomethyl phenyl-1 between 4-triazole (1b) and compound 4-(4-p-methoxy-phenyl)-3-(4-nitrophenyl)-5-, 2,4-triazole (4b) has similar intensification DSC curve, is that example illustrates its thaw process with 4b.As shown in Figure 7, in the compound 1b heating curve, located two endotherm(ic)peaks at 61.84 ℃ and 159.81 ℃, the 1st peak is the transformation peaks of solid phase-mesomorphic phase, i.e. the fusing point peak of sample; The 2nd peak is the transformation peaks of mesomorphic phase-each identical condition, i.e. the clearing point peak of sample.It between 61.84 ℃ and 159.81 ℃ the mesomorphic phase interval.Except two endotherm(ic)peaks are arranged, locate in addition exothermic peak in the DSC curve spectrogram of compound 4b at 161.76 ℃, this be because in heat-processed when energy reaches certain value the generation crystalline polamer, have a large amount of heat release.
By polarized light microscope observing compound 4b, at room temperature present optical anisotropy texture, in the time of near slowly being heated to 70 ℃, the sample fusion enters liquid crystal state, occur a large amount of drops in the visual field, during reheat to 170.2 ℃, schlieren texture disappears, the visual field presents a slice black, and sample has been converted into isotropic liquid.Be cooled to 72.5 ℃ gradually and begin to change into crystal (seeing Fig. 8,9).Aminomethyl phenyl-1,2 between this explanation compound 4-(4-p-methoxy-phenyl)-3-(4-nitrophenyl)-5-, the 4-triazole is a kind of change thermotropic liquid crystal.
Description of drawings:
The DSC curve of Fig. 1 compound 1a;
Texture pattern when Figure 21 a is warmed up to 202.8 ℃;
Texture pattern when Figure 31 a cools to 67.2 ℃;
The DSC curve of Fig. 4 compound 2b;
Figure 52 b is cooled to 120.5 ℃ texture pattern;
Texture pattern when Figure 62 b is cooled to 67.8 ℃;
The DSC curve of Fig. 7 compound 1b;
Texture pattern when Figure 84 b is warmed up to 162.5 ℃;
Texture pattern when Figure 94 b cools to 75.2 ℃.
Embodiment:
Below in conjunction with preferred embodiment, the present invention will be further described, to being described in detail as follows according to embodiment provided by the invention; Simultaneously for simple and purpose clearly, hereinafter appropriate omission the description of known technology, in order to avoid those unnecessary details influences are to the description of the technical program.
Embodiment 1:4-(4-chloro-phenyl-)-3-p-methylphenyl-5-(4-pyridyl)-1,2,4-triazole synthetic:
In 100mL single port flask, add N-(4-chloro-phenyl-)-imines to methyl benzoyl chloride 1.32g (5mmol), Isonicotinoylhydrazine 0.69g (5mmol), N, N-N,N-DIMETHYLACETAMIDE 15mL, reflux obtains white precipitate, suction filtration, drying, ethyl alcohol recrystallization gets white powder 1.21g, productive rate: 69.9%, fusing point: 206-207 ℃.
1H NMR (CDCl
3, δ/ppm): 8.599-8.588 (d, 2H, pyridine ring 3,5-H), 7.471-7.454 (d, 2H, pyridine ring 2,6-H), and 7.314-279 (m, 4H is to methyl phenyl ring 2,6-H reaches chlorobenzene ring 3,5-H), and 7.150-7.120 (m, 4H, to chlorobenzene ring 2,6-H reaches to methyl phenyl ring 3,5-H), 2.353 (s, 3H is to CH on the methyl phenyl ring
3).
IR (KBr, cm
-1): phenyl ring v C-H:3095cm
-1, 3031cm
-1, methyl/methoxyl group: 2913cm
-1, phenyl ring skeletal vibration: 1628cm
-1, 1600cm
-1, v C=N:1524cm
-1, v C-N:1231cm
-1, v N-N:1094cm
-1
Ultimate analysis: calculated value (%): C:69.26, H:4.36, N:16.15; Measured value (%): C:69.32, H:4.45, N:16.10.
Embodiment 2:4-(4-chloro-phenyl-)-3-(4-nitrophenyl)-5-p-methylphenyl-1,2,4-triazole synthetic:
In 100mL single port flask, add N-(4-chloro-phenyl-)-imines to methyl benzoyl chloride 2.89g (11.0mmol), p-nitrophenyl formyl hydrazine 1.97g (10.0mmol), N, N-N,N-DIMETHYLACETAMIDE 15mL, reflux obtains yellow mercury oxide, suction filtration, drying, re-crystallizing in ethyl acetate gets yellow solid 2.42g, productive rate: 62.1%, fusing point: 226-228 ℃.
1H NMR (CDCl
3, δ/ppm): 8.200-8.182 (d, 2H is to methyl phenyl ring, 2,6-H), and 7.624-7.606 (d, 2H, p-nitrophenyl ring 2,6-H), 7.469-7.452 (d, 2H, to chlorobenzene ring 3,5-H), 7.302-7.286 (d, 2H, to chlorobenzene ring 2,6-H), 7.160-7.113 (m, 4H, to the methyl phenyl ring, 3,5-H and p-nitrophenyl ring, 3,5-H), 2.360 (s, 3H is to CH3 on the methyl phenyl ring).
IR (KBr, cm
-1): phenyl ring v C-H:3064cm
-1, 3015cm
-1, methyl/methoxyl group: 2917cm
-1, phenyl ring skeletal vibration: 1601cm
-1, 1486cm
-1, v C=N:1511cm
-1, v C-N:1286cm
-1, v N-N:1094cm
-1
Ultimate analysis: calculated value (%): C:64.54, H:3.87, N:14.34; Measured value (%): C:64.46, H:3.76, N:14.22.
Embodiment 3:4-(4-p-methoxy-phenyl)-3-p-methylphenyl-5-(4-pyridyl)-1,2,4-triazole synthetic:
In 100mL single port flask, add N-(4-p-methoxy-phenyl)-imines to methyl benzoyl chloride 1.29g (5.0mmol), Isonicotinoylhydrazine 0.69g (5.0mmol), N,N-dimethylacetamide 10mL, reflux, obtain white precipitate, suction filtration, drying, separate with column chromatography method, developping agent is an ethyl acetate: sherwood oil=8: 1, isolate the component at Rf=0.30 place, and be spin-dried for the back and be white solid 1.32g, productive rate: 77.2%, fusing point: 185-187 ℃.
1H NMR (CDCl
3, δ/ppm): 8.857-8.566 (d, 2H, pyridine ring 3,5-H), and 7.355-7.333 (m, 4H is to methyl phenyl ring 2,6-H and pyridine ring 2,6-H), 7.134-7.103 (t, 4H, to methyl phenyl ring 3,5-H reaches the methoxyl group phenyl ring, and 2,6-H), 6.982-6.964 (d, 2H is to methoxyl group phenyl ring, 3,5-H), 3.884 (s, 3H is to OCH on the methoxyl group phenyl ring
3), 2.343 (s, 3H is to CH on the methyl phenyl ring
3).
IR (KBr, cm
-1): phenyl ring v C-H:3061cm
-1, 3031cm
-1, methyl/methoxyl group: 2932cm
-1, phenyl ring skeletal vibration: 1664cm
-1, 1599cm
-1, v C=N:1515cm
-1, v C-N:1350cm
-1, v N-N:1101cm
-1
Ultimate analysis: calculated value (%): C:73.67, H:5.30, N:16.36; Measured value (%): C:73.76, H:5.22, N:16.56.
Embodiment 4:4-(4-p-methoxy-phenyl)-3-(4-nitrophenyl)-5-p-methylphenyl-1,2,4-triazole synthetic:
In 100mL single port flask, add N-(4-p-methoxy-phenyl)-imines to methyl benzoyl chloride 2.50g (9.65mmol), p-nitrophenyl formyl hydrazine 1.67g (8.50mmol), N, N-N,N-DIMETHYLACETAMIDE 15mL, reflux obtains yellow mercury oxide, suction filtration, drying, re-crystallizing in ethyl acetate gets faint yellow solid 2.17g, productive rate: 66.2%, fusing point: 235-236 ℃.
1H NMR (CDCl
3, δ/ppm): 8.174-8.156 (d, 2H is to methyl phenyl ring, 2,6-H), and 7.657-7.639 (d, 2H, p-nitrophenyl ring 2,6-H), 7.350-7.334 (d, 2H, to methoxyl group phenyl ring 2,6-H), 7.140-.7.090 (m, 4H, to methyl phenyl ring 3,5-H and p-nitrophenyl ring, 3,5-H), 6.976-6.958 (d, 2H is to methoxyl group phenyl ring, 3,5-H), 3.879 (s, 3H is to OCH on the methoxyl group phenyl ring
3), 2.347 (s, 3H is to CH on the methyl phenyl ring
3).
IR (KBr, cm
-1): phenyl ring v C-H:3074cm
-1, 3025cm
-1, methyl/methoxyl group: 2927cm
-1, phenyl ring skeletal vibration: 1604cm
-1, 1461cm
-1, v C=N:1524cm
-1, v C-N:1259cm
-1, v N-N:1105cm
-1
Ultimate analysis: calculated value (%): C:68.38, H:4.70, N:14.50; Measured value (%): C:63.48, H:4.56, N:14.59.
Aminomethyl phenyl-5-(4-pyridyl)-1,2 between embodiment 5:4-(4-chloro-phenyl-)-3-, 4-triazole synthetic:
In 100mL single port flask, add N-(4-chloro-phenyl-)-imines m-methyl benzoyl formyl chloride 2.33g (9.50mmol), Isonicotinoylhydrazine 1.30g (9.50mmol), N,N-dimethylacetamide 20mL, reflux, obtain white precipitate, suction filtration, drying, separate with column chromatography method, developping agent is an ethyl acetate: sherwood oil=8: 1, isolate the component at Rf=0.30 place, and be spin-dried for the back and be white solid 1.87g, productive rate: 56.8%, fusing point: 185-187 ℃.
1H NMR (CDCl
3, δ/ppm): 8.610-8.598 (d, 2H, pyridine ring 3,5-H), 7.474-7.456 (d, 2H, pyridine ring 2,6-H), 7.404 (s, 1H, a methyl phenyl ring 2-H), 7.326-7.313 (d, 2H is to chlorobenzene ring 3,5-H), and 7.215-7.181 (m, 2H, a methyl phenyl ring 5,6-H), 7.139-7.122 (d, 2H, to chlorobenzene ring 2,6-H), 7.016-7.001 (s, 1H, a methyl phenyl ring 4-H), 2.324 (s, 3H, CH on the methyl phenyl ring
3).
IR (KBr, cm
-1): phenyl ring v C-H:3056cm
-1, 3028cm
-1, methyl/methoxyl group: 2910cm
-1, phenyl ring skeletal vibration: 1594cm
-1, 1599cm
-1, v C=N:1549cm
-1, v C-N:1217cm
-1, v N-N:1084cm
-1
Ultimate analysis: calculated value (%): C:69.26, H:4..36, N:16.15; Measured value (%): C:69.32, H:4.29, N:16.19.
Aminomethyl phenyl-1,2 between embodiment 6:4-(4-chloro-phenyl-)-3-(4-nitrophenyl)-5-, 4-triazole synthetic:
In 100mL single port flask, add N-(4-chloro-phenyl-)-imines m-methyl benzoyl formyl chloride 2.89g (11.0mmol), p-nitrophenyl formyl hydrazine 1.97g (10.0mmol), N, N-N,N-DIMETHYLACETAMIDE 15mL, reflux obtains yellow mercury oxide, suction filtration, drying, re-crystallizing in ethyl acetate gets faint yellow solid 2.13g, productive rate: 54.6%, fusing point: 183-184 ℃.
1H NMR (CDCl
3, δ/ppm): 8.201-8.183 (d, 2H, p-nitrophenyl ring 2,6-H), 7.629-7.611 (d, 2H, to chlorobenzene ring 3,5-H), 7.467-7.450 (d, 2H, to chlorobenzene ring 3,5-H), 7.406 (s, 1H, between methyl phenyl ring 2-H), 7.219-7.184 (m, 2H, a methyl phenyl ring 5,6-H), 7.131-7.113 (d, 2H, p-nitrophenyl ring 3,5-H), 7.016-7.001 (s, 1H, a methyl phenyl ring 4-H), 2.326 (s, 3H, CH on the methyl phenyl ring
3).
IR (KBr, cm
-1): phenyl ring v C-H:3080cm
-1, 3060cm
-1, methyl: 2921cm
-1, phenyl ring skeletal vibration: 1601cm
-1, 1486cm
-1, v C=N:1523cm
-1, v C-N:1348cm
-1, v N-N:1098cm
-1
Ultimate analysis: calculated value (%): C:64.54, H:3.87, N:14.34; Measured value (%): C:64.49, H:3.81, N:14.27.
Aminomethyl phenyl-5-(4-pyridyl)-1,2 between embodiment 7:4-(4-p-methoxy-phenyl)-3-, 4-triazole synthetic:
In 100mL single port flask, add N-(4-p-methoxy-phenyl)-imines m-methyl benzoyl formyl chloride 1.29g (5.mmol), Isonicotinoylhydrazine 0.69g (5.0mmol), N, N-N,N-DIMETHYLACETAMIDE 10mL, reflux obtains white precipitate, suction filtration, drying, ethyl alcohol recrystallization gets white solid 1.21g, productive rate: 70.8%, fusing point: 242-243 ℃.
1H NMR (CDCl
3, δ/ppm): 8.582-8.572 (d, 2H, pyridine ring 3,5-H), 7.665-7.647 (d, 2H, pyridine ring 2,6-H), 7.456 (s, 1H, a methyl phenyl ring 2-H), 7.214-7.153 (m, 2H, a methyl phenyl ring 5,6-H), and 7.109-7.059 (m, 3H, a methyl phenyl ring 4-H reach methoxyl group phenyl ring 2,6-H), and 6.697-6.958 (d, 2H is to methoxyl group phenyl ring 3,5-H), 3.881 (s, 3H is to OCH on the methoxyl group phenyl ring
3), 2.324 (s, 3H, CH on the methyl phenyl ring
3).
IR (KBr, cm
-1): phenyl ring v C-H:3064cm
-1, 3035cm
-1, methyl: 2953cm
-1, phenyl ring skeletal vibration: 1605cm
-1, 1454cm
-1, v C=N:1515cm
-1, v C-N:1258cm
-1, v N-N:1098cm
-1
Ultimate analysis: calculated value (%): C:73.67, H:5.30, N:16.36; Measured value (%): C:73.58, H:5.26, N:16.39.
Aminomethyl phenyl-1,2 between embodiment 8:4-(4-p-methoxy-phenyl)-3-(4-nitrophenyl)-5-, 4-triazole synthetic:
In 100mL single port flask, add N-(4-p-methoxy-phenyl)-imines m-methyl benzoyl formyl chloride 2.46g (9.50mmol), p-nitrophenyl formyl hydrazine 1.67g (8.50mmol), N, N-N,N-DIMETHYLACETAMIDE 15mL, reflux obtains white precipitate, suction filtration, drying, re-crystallizing in ethyl acetate gets faint yellow solid 2.04g, productive rate: 62.2%, fusing point: 186-188 ℃.
1H NMR (CDCl
3, δ/ppm): 8.181-8.164 (d, 2H, p-nitrophenyl ring 2,6-H), (7.453 s, 1H, a methyl phenyl ring 2-H), 7.366-7.354 (d, 2H, to methoxyl group phenyl ring 2,6-H), 7.205-7.145 (m, 2H, a methyl phenyl ring 5,6-H), and 7.121-7.103 (d, 2H is to methoxyl group phenyl ring 3,5-H), (7.070-7.055 d, 1H, a methyl phenyl ring 4-H), 6.975-6.958 (d, 2H, p-nitrophenyl ring 3,5-H), 3.818 (s, 3H is to OCH on the methoxyl group phenyl ring
3), 2.321 (s, 3H, CH on the methyl phenyl ring
3).
IR (KBr, cm
-1): phenyl ring v C-H:3064cm
-1, 3096cm
-1, methyl: 2998cm
-1, phenyl ring skeletal vibration: 1621cm
-1, 1482cm
-1, v C=N:1519cm
-1, v C-N:1249cm
-1, v N-N:1115cm
-1
Ultimate analysis: calculated value (%): C:68.38, H:4.70, N:14.50; Measured value (%): C:68.42, H:4.76, N:14.41.
Embodiment 9:4-(4-chloro-phenyl-)-3-p-nitrophenyl-5-(4-pyridyl)-1,2,4-triazole synthetic:
In 100mL single port flask, add N-(4-chloro-phenyl-)-imines paranitrobenzoyl chloride 2.95g (9.50mmol), Isonicotinoylhydrazine 1.71g (8.50mmol), N,N-dimethylacetamide 20mL, reflux 5h, the pressure reducing and steaming solvent adds 15mL concentrated hydrochloric acid and 30mL distilled water, back hydrolysis 1h, filter, filtrate is separated out solid with the unsaturated carbonate potassium solution PH=8-9 that neutralizes, suction filtration, drying, re-crystallizing in ethyl acetate, get yellow solid 1.69g, productive rate: 52.6%, fusing point: 262-264 ℃.
1H NMR (CDCl
3, δ/ppm): 8.649-8.638 (d, 2H, pyridine ring 3,5-H), 8.227-8.209 (d, 2H, p-nitrophenyl ring 3,5-H), 7.644-7.626 (d, 2H, p-nitrophenyl ring 2,6-H), 7.548-7.530 (d, 2H, pyridine ring 2,6-H), 7.334-7.322 (d, 2H is to chlorobenzene ring 3,5-H), 7.190-7.173 (d, 2H, p-nitrophenyl ring 2,6-H).
IR (KBr, cm
-1): phenyl ring v C-H:3057cm
-1, 3031cm
-1, phenyl ring skeletal vibration: 1597cm
-1, 1490cm
-1, v C=N:1519cm
-1, v C-N:1287cm
-1, v N-N:1091cm
-1
Ultimate analysis: calculated value (%): C:60.41, H:3.20, N:18.54; Measured value (%): C:60.36, H:3.16, N:18.51.
Embodiment 10: the example of practical application.
To prepare the prepared compound 1a of example, be made into 1 * 10
-5The mol/L dichloromethane solution accurately is deposited on this solution in the insulated column groove of ito glass substrate, forms nano thin-layer (thickness is about 100 nanometers) after the solvent evaporates, constitutes light emitting pixel, adopts specification technology to make display screen.
Measurement result:
Big, the response speed piece (ms level) in display screen visual angle, temperature profile good (can use at low temperatures) as a result, its demonstration does not rely on backlight or surround lighting just can be luminous.The characteristic of excellences such as the display screen that adopts The compounds of this invention to make has that the use temperature scope is wide, structure and processing procedure are simpler is considered to follow-on flat-panel screens.
Claims (7)
1. the triazole derivative that contains liquid crystal unit, it is represented with following general structure:
Wherein, R
1, R
2, R
3For containing halogen, nitro, C
1-C
4Alkyl or C
1-C
4The phenyl of alkoxyl group or pyridyl.
2. the described triazole derivative that contains liquid crystal unit of claim 1, the compound that it had is as follows:
3. claim 1 or the 2 described preparation methods that contain the triazole derivative of liquid crystal unit is characterized in that being undertaken by following step:
(a) be raw material and sulfur oxychloride reaction with p-methylbenzoic acid, m-methyl benzoic acid or p-nitrobenzoic acid, synthetic acyl chloride compound;
(b) reaction by acyl chlorides and substituted aniline, synthesizing amide class intermediate; By amides intermediate and the synthetic chlorimide intermediate of sulfur oxychloride reaction.
(c) (b) synthetic chlorimide intermediate is reacted the preparation triazole class compounds with different hydrazides.
4. the described preparation method of claim 3, chlorimide intermediate wherein is:
N-(4-chloro-phenyl-)-imines is to methyl benzoyl chloride;
N-(4-p-methoxyphenyl)-imines is to methyl benzoyl chloride;
N-(4-chloro-phenyl-)-imines m-methyl benzoyl formyl chloride;
N-(4-p-methoxyphenyl)-imines m-methyl benzoyl formyl chloride;
N-(4-chloro-phenyl-)-imines paranitrobenzoyl chloride.
5. claim 1 or the 2 described application of triazole derivative aspect preparation organic electronic transport material that contain liquid crystal unit.
6. claim 1 or the 2 described application of triazole derivative aspect preparation liquid crystal unit or organic light emitting display material that contain liquid crystal unit.
7. claim
Described organic light emitting display comprises the indicating meter on the indicating meter of aerospacecraft, military open-air portable indicating meter and the operation battlebus.
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| CN102633734A (en) * | 2012-03-23 | 2012-08-15 | 天津师范大学 | Tris(4-triazole phenyl) amine compound as well as preparation method and application thereof |
| CN102746853A (en) * | 2012-06-18 | 2012-10-24 | 北京科技大学 | Triazole bending rodlike liquid crystal compound and preparation method thereof |
| CN104072429A (en) * | 2014-07-01 | 2014-10-01 | 安徽师范大学 | Synthetic method of 1,2,4-triazole derivative |
| CN105585535A (en) * | 2016-01-05 | 2016-05-18 | 天津师范大学 | 4-(4-nitrophenyl)-4H-1,2,4-triazole single crystal and application |
| CN109096279A (en) * | 2018-09-28 | 2018-12-28 | 武汉天马微电子有限公司 | Nitrogen heterocyclic, display panel and display device |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633734A (en) * | 2012-03-23 | 2012-08-15 | 天津师范大学 | Tris(4-triazole phenyl) amine compound as well as preparation method and application thereof |
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| CN102746853A (en) * | 2012-06-18 | 2012-10-24 | 北京科技大学 | Triazole bending rodlike liquid crystal compound and preparation method thereof |
| CN104072429A (en) * | 2014-07-01 | 2014-10-01 | 安徽师范大学 | Synthetic method of 1,2,4-triazole derivative |
| CN104072429B (en) * | 2014-07-01 | 2016-05-18 | 安徽师范大学 | A kind of synthetic method of 1,2,4-triazole derivative |
| CN105585535A (en) * | 2016-01-05 | 2016-05-18 | 天津师范大学 | 4-(4-nitrophenyl)-4H-1,2,4-triazole single crystal and application |
| CN109096279A (en) * | 2018-09-28 | 2018-12-28 | 武汉天马微电子有限公司 | Nitrogen heterocyclic, display panel and display device |
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