CN104402835A - Phenoxyl tritriazole compound, preparation method and applications thereof - Google Patents

Phenoxyl tritriazole compound, preparation method and applications thereof Download PDF

Info

Publication number
CN104402835A
CN104402835A CN201410623858.3A CN201410623858A CN104402835A CN 104402835 A CN104402835 A CN 104402835A CN 201410623858 A CN201410623858 A CN 201410623858A CN 104402835 A CN104402835 A CN 104402835A
Authority
CN
China
Prior art keywords
triazole
phenoxy group
bis
preparation
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410623858.3A
Other languages
Chinese (zh)
Inventor
王英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Normal University
Original Assignee
Tianjin Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin Normal University filed Critical Tianjin Normal University
Priority to CN201410623858.3A priority Critical patent/CN104402835A/en
Publication of CN104402835A publication Critical patent/CN104402835A/en
Pending legal-status Critical Current

Links

Classifications

    • 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

Landscapes

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

Abstract

The invention provides a phenoxyl tritriazole compound, a preparation method and applications thereof. The invention discloses a preparation method of 4-(4-(3,5-di(4-(4H-1,2,4-triazole-4-yl)phenoxyl)phenoxyl)phenyl)-4H-1,2,4-triazole. The compound is prepared by a one-pot method, namely heating 4-(3,5-di(4-aminophenoxyl)phenoxyl)aniline and diformyl hydrazine to prepare the compound. The preparation method has the characteristics of simple operation, low production cost, and little environment pollution, and is suitable for massive industrial production. The prepared 4-(4-(3,5-di(4-(4H-1,2,4-triazole-4-yl)phenoxyl)phenoxyl)phenyl)-4H-1,2,4-triazole can be applied to fields of photoelectric materials and luminescent agents.

Description

Phenoxy group three triazole compounds and preparation method thereof and application
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-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl)-4H-1,2,4-triazole compounds and its preparation method, 4-(4-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl)-4H-1, the application of 2,4-triazole in luminous agent.
Background technology
4-(4-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl)-4H-1,2,4-triazole has tripod 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-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl)-4H-1,2,4-triazole compounds and preparation method thereof.
Another object of the present invention is to provide 4-(4-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl)-4H-1,2,4-triazole and preparing the application in photoelectric material.
The present inventor is surprised to find in test: with 4-(3,5-bis-(4-amino-benzene oxygen) phenoxy group) aniline, 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-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl)-4H-1,2,4-triazole compounds has following structure:
The preferred 4-of the present invention (3,5-bis-(4-amino-benzene oxygen) phenoxy group) aniline, 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-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl)-4H-1,2, the preparation method of 4-triazole is characterized in that, in polar solvent, adopt " one kettle way ", by 4-(3,5-bis-(4-amino-benzene oxygen) phenoxy group) aniline, 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 4-(3,5-bis-(4-amino-benzene oxygen) phenoxy group) aniline, and the mol ratio of two formyl hydrazine is 1:3;
The advantage and disadvantage that 4-disclosed by the invention (4-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) 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-(3 prepared by the present invention, 5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl)-4H-1,2,4-triazole may be used for luminous agent, and its production cost is low, profit margin is large, is more suitable for large-scale industrial production.
Accompanying drawing explanation
The nuclear magnetic spectrogram of Fig. 1: 4-(4-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) 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.
Embodiment 1
The preparation of 4-(3,5-bis-(4-amino-benzene oxygen) phenoxy group) aniline (I)
Add Phloroglucinol 6 g 250 mL single port bottles are red, p-fluoronitrobenzene 10 mL, DMF 20 mL refluxes 3 hours, is cooled to room temperature, and add 100 mL water, suction filtration obtains brown crude product.Use a small amount of methanol wash, obtain yellow-brown solid III.
 
In 250 mL there-necked flasks, add 5 g compound III, 1 g iron powder and 100 mL ethanolic solns, add 10 mL ethanol under stirring, refluxes 10 hours.Stirring 5 hours is continued, suction filtration after cooling.Solid CHCl3 extracts.After extraction liquid drying, rotary evaporation obtains light yellow solid powder and is 4-(3,5-bis-(4-amino-benzene oxygen) phenoxy group) aniline (Compound I)
Embodiment 2
4-(3,5-bis-(4-amino-benzene oxygen) phenoxy group) aniline, the mol ratio of two formyl hydrazine is 1:3
4-(3 is added respectively in 50 mL, tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, 5-bis-(4-amino-benzene oxygen) phenoxy group) aniline (1 mmol), two formyl hydrazine (2 mmol), start and be stirred in 160 DEG C, react 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 24h 21n 3o 3theoretical value: C, 72.17; H, 5.30; N, 10.52.Experimental value: C, 72.19; H, 5.38; N, 10.53.
Preparation method:
4-(3,5-bis-(4-amino-benzene oxygen) phenoxy group) aniline, the mol ratio of two formyl hydrazine is 1:2.
4-(3 is added respectively in 50 mL, tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, 5-bis-(4-amino-benzene oxygen) phenoxy group) aniline (1 mmol), two formyl hydrazine (2 mmol), start and be stirred in 160 DEG C, react 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 24h 21n 3o 3theoretical value: C, 72.17; H, 5.30; N, 10.52.Experimental value: C, 72.19; H, 5.38; N, 10.53.
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 (4)

1.4-(4-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl)-4H-1,2,4-triazole compounds has following structure:
There is 4-(4-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl)-4H-1,2,4-triazole nuclear magnetic data.
2. (the 4-(3 of 4-described in claim 1,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl) preparation method of-4H-1,2,4-triazole compounds, it is characterized in that adopting " one kettle way " at polar solvent, by 4-(3,5-bis-(4-amino-benzene oxygen) phenoxy group) aniline, two formyl hydrazine reacts preparation in a heated condition; Wherein 4-(3,5-bis-(4-amino-benzene oxygen) phenoxy group) aniline (I), the mol ratio of two formyl hydrazine (II) is 1:3; Temperature of reaction 160 oc, 12 hours reaction times;
(Ⅰ) (Ⅱ) 。
3. preparation method according to claim 2 is solid phase and solid phase direct reaction under heating and melting condition.
4.4-(4-(3,5-bis-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenoxy group) phenyl)-4H-1,2,4-triazole is preparing the application in dye well luminous agent.
CN201410623858.3A 2014-11-10 2014-11-10 Phenoxyl tritriazole compound, preparation method and applications thereof Pending CN104402835A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410623858.3A CN104402835A (en) 2014-11-10 2014-11-10 Phenoxyl tritriazole compound, preparation method and applications thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410623858.3A CN104402835A (en) 2014-11-10 2014-11-10 Phenoxyl tritriazole compound, preparation method and applications thereof

Publications (1)

Publication Number Publication Date
CN104402835A true CN104402835A (en) 2015-03-11

Family

ID=52640515

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410623858.3A Pending CN104402835A (en) 2014-11-10 2014-11-10 Phenoxyl tritriazole compound, preparation method and applications thereof

Country Status (1)

Country Link
CN (1) CN104402835A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN113501763A (en) * 2021-06-29 2021-10-15 天津众泰材料科技有限公司 Method for preparing 1,3, 5-tri (4-aminophenoxy) benzene

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009129036A1 (en) * 2008-04-14 2009-10-22 Merck & Co., Inc. Substituted cyclopropyl compounds, compositions containing such compounds and methods of treatment
US20110105761A1 (en) * 2008-01-30 2011-05-05 Technische Universitaet Dresden Salts Comprising Aryl-Alkyl-Substituted Imidazolium and Triazolium Cations and the Use Thereof
CN103772305A (en) * 2014-01-14 2014-05-07 天津师范大学 Oxyether triazole compound, and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110105761A1 (en) * 2008-01-30 2011-05-05 Technische Universitaet Dresden Salts Comprising Aryl-Alkyl-Substituted Imidazolium and Triazolium Cations and the Use Thereof
WO2009129036A1 (en) * 2008-04-14 2009-10-22 Merck & Co., Inc. Substituted cyclopropyl compounds, compositions containing such compounds and methods of treatment
CN103772305A (en) * 2014-01-14 2014-05-07 天津师范大学 Oxyether triazole compound, and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HONGMING HE，ET AL.: "Tunable colors and white-light emission based on a microporous luminescent Zn(II)-MOF", 《DALTON TRANS.》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN113501763A (en) * 2021-06-29 2021-10-15 天津众泰材料科技有限公司 Method for preparing 1,3, 5-tri (4-aminophenoxy) benzene
CN113501763B (en) * 2021-06-29 2022-04-15 天津众泰材料科技有限公司 Method for preparing 1,3, 5-tri (4-aminophenoxy) benzene

Similar Documents

Publication Publication Date Title
CN104370837A (en) Thioether bitriazole compound as well as preparation method and application of thioether bitriazole compound
CN103772305A (en) Oxyether triazole compound, and preparation method and application thereof
Li et al. Ruthenium-catalyzed meta-selective C–H sulfonation of azoarenes with arylsulfonyl chlorides
CN103772303B (en) Anthracene ring triazole compound, and preparation method and application thereof
CN103772304A (en) Tetraphenyl ethylene compound, and preparation method and application thereof
CN104447804B (en) Double; two triazole Cu-trifluoromethanesulfonic acid coordination compound of isophthalic and preparation method thereof and application
He et al. Three novel zinc (II) metal–organic frameworks based on three tetrazolate ligands: synthesis, structures and photoluminescence
CN104402835A (en) Phenoxyl tritriazole compound, preparation method and applications thereof
CN104370839A (en) Oxygen ether-4-substituted bitriazole compound as well as preparation method and application of oxygen ether-4-substituted bitriazole compound
CN103483279B (en) Preparation method of 1,4-disubstituted triazole compound
CN104370838A (en) Preparation method and application of p-phenyl-4-substituted-bitriazole compound
Dong et al. Studies on mono-and dinuclear bisoxime copper complexes with different coordination geometries
Tsukada et al. Fine electronic state tuning of cobaltadithiolene complexes by substituent groups on the benzene ring
Feng et al. Construction of 1D to 3D cadmium (II) coordination polymers from 4-(imidazol-1-yl)-benzoic acid: Effect of bridging anions
CN104370840A (en) Preparation method and application of m-phenyl-4-substituted-bitriazole compound
CN104356148B (en) Two triazole Cu-nitric acid title complex of isophthalic and preparation method thereof and application
Dou et al. 3D Luminescent Copper (I) Iodide Coordination Polymer Based on Cu4I4 Clusters and an Ethyl‐bridging Bis (triazole) Ligand
CN104370965A (en) Tri(4-(1H-1, 2, 4-triazole-1-yl)phenyl) phosphorus compound as well as preparation method and application of tri(4-(1H-1, 2, 4-triazole-1-yl)phenyl) phosphorus compound
Sun et al. Four cadmium coordination polymers modulated by bis (triazol-1-yl) propane and inorganic anions: Syntheses, structures and properties
CN104356149A (en) M-benzene bi-triazole Cu-hypochlorite complex and preparation method and application thereof
CN104311497B (en) 1 [7 (1H 1,2,4 triazole 1 base) naphthalene 2 base] 1H 1,2,4 3-triazole compounds and preparation method thereof
CN104370944A (en) M-benzene ditriazole Cu-boric acid complex as well as preparation method and application thereof
CN104230829B (en) Two triazole compounds of biphenyl and preparation method thereof and application
Zhang et al. One-pot solvent-free synthesis of 1, 3, 5-trisubstituted 1 H-pyrazoles catalyzed by H3 [PW12O40]/SiO2 under microwave irradiation
CN104829546B (en) Ethoxybenzene compound that double triazoles replace and preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20150311