CN104370838A - Preparation method and application of p-phenyl-4-substituted-bitriazole compound - Google Patents

Preparation method and application of p-phenyl-4-substituted-bitriazole compound Download PDF

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Publication number
CN104370838A
CN104370838A CN201410623860.0A CN201410623860A CN104370838A CN 104370838 A CN104370838 A CN 104370838A CN 201410623860 A CN201410623860 A CN 201410623860A CN 104370838 A CN104370838 A CN 104370838A
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Prior art keywords
triazole
phenyl
preparation
compound
ursol
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CN201410623860.0A
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Chinese (zh)
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王英
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Tianjin Normal University
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Tianjin Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method and application of a p-phenyl-4-substituted-bitriazole compound, and particularly discloses a preparation method of 4-(4-(4H-1, 2, 4-triazole-4-yl)phenyl)-4H-1, 2, 4-triazole. The organic compound is prepared by using a one-pot method, namely heating phenylenediamine and diformylhydrazine. The preparation method disclosed by the invention has the characteristics of simple technological operation, low production cost and little environmental pollution and is suitable for large-scale industrial production. The 4-(4-(4H-1, 2, 4-triazole-4-yl)phenyl)-4H-1, 2, 4-triazole prepared by using the preparation method can be applied to the aspects of photoelectric materials and luminescent agents.

Description

Two triazole compounds and preparation method thereof and application are replaced to benzene-4-
The present invention obtains state natural sciences fund general project (21471113), and Tianjin Education Commission funded projects (20140506) and Tianjin innovation team of institution of higher education training plan subsidize (TD12-5038).
Technical field
The invention belongs to technical field of organic synthesis, relate to 4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole compounds and its preparation method, 4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1, the application of 2,4-triazole in luminous agent.
Background technology
4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole has two dimensional structure.1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridgingligands that coordination ability is stronger, have synthesized at present and have characterized a large amount of monokaryons, multinuclear and multidimensional compound.These parts can with 1, nitrogen-atoms on 2 and metallic ion coordination form N1, N2-bridging pattern, for 4 unsubstituted 1,2,4-triazole derivative is by 2, nitrogen-atoms on 4 forms N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, and N3-bridging mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
In the dye sensitizing agent reported, the ruthenium base sensitizing agent performance containing precious metal is best, but its cost is higher.The two pure organic dye sensitizing agents not containing precious metal have structure diversity, are easy to design, with low cost and molar extinction coefficient advantages of higher.So the pure organic dye sensitizing agent that design and synthesis is used for substituting ruthenium radical dye has become a very important job.Based on this, the present invention mainly studies efficiently, the Design and synthesis of organic dye sensitized dose of low cost.Namely the present invention selects Ursol D, two formyl hydrazine in a heated condition, design and synthesis novel two triazole species organism is replaced to benzene one.
Summary of the invention
One object of the present invention is to provide a kind of 4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole compounds and preparation method thereof.
Another object of the present invention is provide 4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole and preparing the application in photoelectric material.
The present inventor is surprised to find in test: with Ursol D, and two formyl hydrazine reacts preparation in a heated condition; This reaction is that solid phase and solid phase are reacted under melting condition.Control temperature, 160 DEG C time, can obtain the high 4-of yield (4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole.
Current inventor provides following technical scheme for this reason:
4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole compounds has following structure:
The preferred Ursol D of the present invention, the mol ratio of two formyl hydrazine is 1:2; Temperature of reaction 160 DEG C, 12 hours reaction times.
 
The more detailed preparation method of the present invention is as follows:
A kind of 4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1, the preparation method of 2,4-triazole is characterized in that, in polar solvent, adopt " one kettle way ", by Ursol D, two formyl hydrazine prepares this organic compound in a heated condition; This reaction is that solid phase and solid phase are reacted under melting condition, wherein Ursol D, and the mol ratio of two formyl hydrazine is 1:2;
The advantage and disadvantage that 4-disclosed by the invention (4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole compounds has is:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) 4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2, the 4-triazole prepared by the present invention may be used for luminous agent, and its production cost is low, and profit margin is large, is more suitable for large-scale industrial production.
Accompanying drawing explanation
The nuclear magnetic spectrogram of Fig. 1: 4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole.
Embodiment
Below in conjunction with embodiment, the present invention is described further, and embodiment is only indicative, never means that it limits the scope of the invention by any way.All raw materials are all buy from chemical reagents corporation both domestic and external, through continuation purify but directly use.The fusing point of product is X in model 4the melting point apparatus of Micro carries out measure.Described Ursol D, two formyl hydrazine are by commercially available.
Embodiment 1
Ursol D, the mol ratio of two formyl hydrazine is 1:2.
In 50 mL, tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, add Ursol D (1 mmol) respectively, two formyl hydrazine (2 mmol), starts and is stirred in 160 DEG C, reacts 12 hours.After reaction terminates, reaction solution is down to room temperature, separates out and precipitate in a large number, by precipitation water and ethyl alcohol recrystallization, yield 86%.Ultimate analysis C 10h 8n 6theoretical value: C, 56.60; H, 3.80; N, 39.60.Experimental value: C, 56.49; H, 3.84; N, 39.63.
Preparation method:
Ursol D, the mol ratio of two formyl hydrazine is 1:2.
In 50 mL, tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, add Ursol D (1 mmol) respectively, two formyl hydrazine (2 mmol), starts and is stirred in 160 DEG C, reacts 12 hours.After reaction terminates, reaction solution is down to room temperature, separates out and precipitate in a large number, by precipitation water and ethyl alcohol recrystallization, yield 86%.Ultimate analysis C 10h 8n 6theoretical value: C, 56.60; H, 3.80; N, 39.60.Experimental value: C, 56.49; H, 3.84; N, 39.63.
Embodiment 3
Luminous agent, has photoluminescent property; Concrete method steps is as follows:
By spectrophotofluorometer, carry out the excitation wavelength of this compound (embodiment 1) and the scanning of emission wavelength respectively, select and determine optimal wavelength.
Conclusion: the excitation wavelength of this compound and emission wavelength are respectively 375 nm and 550 nm.
After the preferred embodiment described in detail, be familiar with this technology personage can be well understood to, do not departing under above-mentioned claim and spirit and can carry out various change and amendment, all above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all belong to the scope of technical solution of the present invention.And the present invention is not also by the restriction of example embodiment in specification sheets.

Claims (3)

1.4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole compounds has following structure:
There is 4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole nuclear magnetic data.
2. 4-described in claim 1 (4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1, the preparation method of 2,4-triazole compounds, is characterized in that adopting " one kettle way " at polar solvent, by Ursol D, two formyl hydrazine reacts preparation in a heated condition; Wherein Ursol D, the mol ratio of two formyl hydrazine is 1:2; Temperature of reaction 160 oc, 12 hours reaction times;
(Ⅰ) (Ⅱ) 。
3.4-(4-(4H-1,2,4-triazole-4-yl) phenyl)-4H-1,2,4-triazole is preparing the application in dye well luminous agent.
CN201410623860.0A 2014-11-10 2014-11-10 Preparation method and application of p-phenyl-4-substituted-bitriazole compound Pending CN104370838A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105418523A (en) * 2016-01-05 2016-03-23 天津师范大学 1,4-dimethyl-2,5-dimethylene bis(triazole)terephthalic acid single crystal and application
CN105524003A (en) * 2016-01-05 2016-04-27 天津师范大学 4-(4-(4-(4H-1,2,4-triazol-4-yl) phenoxy) phenyl)-4H-1,2,4-triazol-single crystal and application thereof
CN105646381A (en) * 2016-01-05 2016-06-08 天津师范大学 4-(4-(4H-1,2,4-triazole-4-yl)phenoxyl)phenyl)-4H-1,2,4-triazole mono-crystal

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103086988A (en) * 2013-02-21 2013-05-08 天津师范大学 Phenyl bistriazole compound, and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103086988A (en) * 2013-02-21 2013-05-08 天津师范大学 Phenyl bistriazole compound, and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
RICHARD H等: "REACTION OF DIFORMYLHYDRAZINE WITH AMINOHETEROCYCLES", 《J. ORG. CHEM.》 *
SHAO-BIN MIAO 等: "Synthesis，Crystal Structure，and Properties of a 3D Cu(I) Coordination Polymer Based on Cu3(CN)2 Clusters and 1,3-Di-(1,2,4-Triazole-4-yl)Benzene", 《J CLUST SCI》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105418523A (en) * 2016-01-05 2016-03-23 天津师范大学 1,4-dimethyl-2,5-dimethylene bis(triazole)terephthalic acid single crystal and application
CN105524003A (en) * 2016-01-05 2016-04-27 天津师范大学 4-(4-(4-(4H-1,2,4-triazol-4-yl) phenoxy) phenyl)-4H-1,2,4-triazol-single crystal and application thereof
CN105646381A (en) * 2016-01-05 2016-06-08 天津师范大学 4-(4-(4H-1,2,4-triazole-4-yl)phenoxyl)phenyl)-4H-1,2,4-triazole mono-crystal

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Application publication date: 20150225