CN104370837A - Thioether bitriazole compound as well as preparation method and application of thioether bitriazole compound - Google Patents

Thioether bitriazole compound as well as preparation method and application of thioether bitriazole compound Download PDF

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Publication number
CN104370837A
CN104370837A CN201410623855.XA CN201410623855A CN104370837A CN 104370837 A CN104370837 A CN 104370837A CN 201410623855 A CN201410623855 A CN 201410623855A CN 104370837 A CN104370837 A CN 104370837A
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Prior art keywords
thioether
compound
triazole
preparation
phenyl
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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
    • C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • 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 thioether bitriazole compound as well as a preparation method and application of the thioether bitriazole compound, and particularly discloses a bi(4-(4H-1, 2, 4-triazole-4-yl)phenyl)thioether compound and a preparation method of the bi(4-(4H-1, 2, 4-triazole-4-yl)phenyl)thioether compound. The organic compound is prepared by using a one-pot method, namely heating 4, 4'-biamino diphenyl sulfide 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 bi(4-(4H-1, 2, 4-triazole-4-yl)phenyl)thioether compound prepared by using the preparation method can be applied to the aspects of photoelectric materials and luminescent agents.

Description

Two triazole compounds of thioether 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 two (4-(4H-1,2,4-triazole-4-yl) phenyl) sulfide compound and its preparation method, two (4-(4H-1,2,4-triazole-4-yl) phenyl) thioether application in luminous agent.
Background technology
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 two (4-(4H-1,2,4-triazole-4-yl) phenyl) sulfide compound and preparation method thereof.
Another object of the present invention is provide two (4-(4H-1,2,4-triazole-4-yl) phenyl) thioethers and preparing the application in photoelectric material.
The present inventor is surprised to find in test: with 4,4 '-diaminodiphenyl sulfide, 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 two (4-(4H-1,2,4-triazole-4-yl) phenyl) thioether that yield is high.
Current inventor provides following technical scheme for this reason:
Two (4-(4H-1,2,4-triazole-4-yl) phenyl) sulfide compound has following structure:
The present invention preferably 4,4 '-diaminodiphenyl sulfide, and 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 preparation method of two (4-(4H-1,2,4-triazole-4-yl) phenyl) thioether is characterized in that, in polar solvent, adopt " one kettle way ", by 4,4 '-diaminodiphenyl sulfide, 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, and 4 '-diaminodiphenyl sulfide, the mol ratio of two formyl hydrazine is 1:2;
The advantage and disadvantage that two (4-(4H-1,2,4-triazole-4-yl) phenyl) disclosed by the invention sulfide compound 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) two prepared by the present invention (4-(4H-1,2,4-triazole-4-yl) phenyl) thioether 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: two (4-(4H-1,2,4-triazole-4-yl) phenyl) thioether.
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 wherein 4,4 '-diaminodiphenyl sulfide, two formyl hydrazine has commercially available.
Embodiment 1
4,4 '-diaminodiphenyl sulfide, 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 4 respectively, 4 '-diaminodiphenyl sulfide (1 mmol), 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 16h 12n 6s theoretical value: C, 59.98; H, 3.78; N, 26.23.Experimental value: C, 60.09; H, 3.74; N, 26.13.
Embodiment 2
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. two (4-(4H-1,2,4-triazole-4-yl) phenyl) sulfide compound has following structure:
There is two (4-(4H-1,2,4-triazole-4-yl) phenyl) thioether nuclear magnetic data.
2. the preparation method of two (4-(4H-1,2,4-triazole-4-yl) phenyl) sulfide compound described in claim 1, it is characterized in that adopting " one kettle way " at polar solvent, by 4,4 '-diaminodiphenyl sulfide, two formyl hydrazine reacts preparation in a heated condition; Wherein 4,4 '-diaminodiphenyl sulfide, the mol ratio of two formyl hydrazine is 1:2; 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. two (4-(4H-1,2,4-triazole-4-yl) phenyl) thioether is preparing the application in dye well luminous agent.
CN201410623855.XA 2014-11-10 2014-11-10 Thioether bitriazole compound as well as preparation method and application of thioether bitriazole compound Pending CN104370837A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104961694A (en) * 2015-06-23 2015-10-07 天津师范大学 Diphenyl sulfide compound displaced with double triazole and preparing method and application thereof
CN105294743A (en) * 2015-12-03 2016-02-03 天津师范大学 4H sulfide double triazole terephthalic acid zinc complex single crystal and preparation method as well as application thereof
CN105348307A (en) * 2015-12-03 2016-02-24 天津师范大学 4H thioether bis-triazole zinc acetate complex single crystal as well as preparation method and application thereof
CN105418649A (en) * 2015-12-03 2016-03-23 天津师范大学 Two-dimensional zinc 4H thioether bis(triazole) complex single crystal as well as preparation method and application thereof
CN105418522A (en) * 2016-01-05 2016-03-23 天津师范大学 1,4-bis(4-(1H-1,2,4-triazole-1-yl)phenyl)piperazine single crystal and application
CN105418648A (en) * 2015-12-03 2016-03-23 天津师范大学 Silver 4H thioether bis(triazole) complex single crystal as well as preparation method and application thereof
CN105418521A (en) * 2015-12-03 2016-03-23 天津师范大学 Di(4-(4H-1,2,4-triazole-4-yl)phenyl) sulfur compound and application thereof
CN105440060A (en) * 2015-12-03 2016-03-30 天津师范大学 4H thioether bis-triazole copper complex single crystal as well as preparation method and application thereof
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
CN106187925A (en) * 2016-07-28 2016-12-07 天津师范大学 The double triazole terephthalic acid compounds monocrystalline of 4H thioether and application
CN106243156A (en) * 2016-07-28 2016-12-21 天津师范大学 The double triazole ferrous perchlorate's complex monocrystal of 4H thioether and application

Citations (4)

* 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
CN102186813A (en) * 2008-08-13 2011-09-14 宇部兴产株式会社 Organosulfur compound, process for producing the same, and organic electroluminescence element using the same
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 (4)

* 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
CN102186813A (en) * 2008-08-13 2011-09-14 宇部兴产株式会社 Organosulfur compound, process for producing the same, and organic electroluminescence element using the same
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
BING LIU, ET AL.: "Four novel linear trinuclear assemblies containing bridging triazole ligands. Crystal structure, magnetic, semiconducting and fluorescent properties", 《JOURNAL OF MOLECULAR STRUCTURE》, no. 825, 31 December 2006 (2006-12-31), pages 79 - 86 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104961694A (en) * 2015-06-23 2015-10-07 天津师范大学 Diphenyl sulfide compound displaced with double triazole and preparing method and application thereof
CN105294743A (en) * 2015-12-03 2016-02-03 天津师范大学 4H sulfide double triazole terephthalic acid zinc complex single crystal and preparation method as well as application thereof
CN105348307A (en) * 2015-12-03 2016-02-24 天津师范大学 4H thioether bis-triazole zinc acetate complex single crystal as well as preparation method and application thereof
CN105418649A (en) * 2015-12-03 2016-03-23 天津师范大学 Two-dimensional zinc 4H thioether bis(triazole) complex single crystal as well as preparation method and application thereof
CN105418648A (en) * 2015-12-03 2016-03-23 天津师范大学 Silver 4H thioether bis(triazole) complex single crystal as well as preparation method and application thereof
CN105418521A (en) * 2015-12-03 2016-03-23 天津师范大学 Di(4-(4H-1,2,4-triazole-4-yl)phenyl) sulfur compound and application thereof
CN105440060A (en) * 2015-12-03 2016-03-30 天津师范大学 4H thioether bis-triazole copper complex single crystal as well as preparation method and application thereof
CN105418522A (en) * 2016-01-05 2016-03-23 天津师范大学 1,4-bis(4-(1H-1,2,4-triazole-1-yl)phenyl)piperazine 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
CN106187925A (en) * 2016-07-28 2016-12-07 天津师范大学 The double triazole terephthalic acid compounds monocrystalline of 4H thioether and application
CN106243156A (en) * 2016-07-28 2016-12-21 天津师范大学 The double triazole ferrous perchlorate's complex monocrystal of 4H thioether and application

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Application publication date: 20150225