CN116478031A - 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and preparation method and application thereof - Google Patents

1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and preparation method and application thereof Download PDF

Info

Publication number
CN116478031A
CN116478031A CN202310302002.5A CN202310302002A CN116478031A CN 116478031 A CN116478031 A CN 116478031A CN 202310302002 A CN202310302002 A CN 202310302002A CN 116478031 A CN116478031 A CN 116478031A
Authority
CN
China
Prior art keywords
dihydroxynaphthalene
derivative
dichalcone
compound
group
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
CN202310302002.5A
Other languages
Chinese (zh)
Inventor
廖良生
王雪东
闫长存
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.)
Suzhou University
Original Assignee
Suzhou 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 Suzhou University filed Critical Suzhou University
Priority to CN202310302002.5A priority Critical patent/CN116478031A/en
Publication of CN116478031A publication Critical patent/CN116478031A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
    • H01S3/16—Solid materials
    • H01S3/163—Solid materials characterised by a crystal matrix
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
    • C07C49/835—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups having unsaturation outside an aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/333—Radicals substituted by oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/66—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/80—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/36—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/56—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D455/00—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
    • C07D455/03—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
    • C07D455/04—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing a quinolizine ring system condensed with only one six-membered carbocyclic ring, e.g. julolidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic 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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • 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
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative, and a preparation method and application thereof, and belongs to the technical field of chalcone derivatives. The structural formula of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative isWherein Ar is selected from substituted or unsubstituted aryl; the unsubstituted aryl is selected from benzene, biphenyl, a condensed aromatic ring or an aromatic heterocyclic ring; the substituent group of the substituted aromatic group is selected from alkyl, alkoxy, amino, alkylthio or carbazole. The 1, 5-dihydroxynaphthalene-2, 6-dichalchalcone derivative can establish two pairs of excited intramolecular proton transfer centers, realize excited intramolecular double proton transfer, bring more possibility for the regulation and control of laser performance, and improve the laser performance.

Description

1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and preparation method and application thereof
Technical Field
The invention belongs to the technical field of chalcone derivatives, and particularly relates to a 1, 5-dihydroxynaphthalene-2, 6-dichlorlone derivative, and a preparation method and application thereof.
Background
The laser mainly consists of three parts: pump source, resonant cavity and gain medium. Organic materials can be used as ideal gain media (chem. Rev.2016,116, 12823) due to their large stimulated emission cross section, tunable emission wavelength, and good processability. For most organic laser active molecules, however, stimulated emission is based primarily on a quasi-four energy level system consisting of vibrational energy levels. The stokes shift caused by the quasi-four energy level process is small, resulting in severe self-absorption loss and thus high lasing threshold.
2' -hydroxy chalcone compounds are receiving extensive attention because they can build a true four-level system by excited state intramolecular proton transfer. CN103242180 discloses 2' -hydroxy chalcone derivative crystals and their use in amplifying spontaneous emissions. There have also been recent reports of organic solid lasers based on 1 '-hydroxy-2' -naphthalene chalcone derivatives (J.Am. Chem. Soc.2015,137, 9289). However, there is no document report on derivatization and laser performance of centrosymmetric naphthalene chalcone. The centrally symmetrical naphthalene chalcone derivative has two pairs of excited state intramolecular proton transfer structural units, and can theoretically generate twice excited state intramolecular proton transfer, thereby providing more possibility for regulating and controlling the laser performance, and therefore, the derivatization of the centrally symmetrical 1, 5-dihydroxynaphthalene-2, 6-dichalcanone has important significance for developing high-performance organic laser active materials.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems that the laser threshold of the organic laser active material is high, near infrared laser is difficult to realize and the like in the prior art.
In order to solve the technical problems, the invention provides a 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative, and a preparation method and application thereof.
The first object of the invention is to provide a 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative, the structure of which is shown as the formula (I):
wherein Ar is selected from substituted or unsubstituted aryl; the unsubstituted aryl is selected from benzene, biphenyl, a condensed aromatic ring or an aromatic heterocyclic ring; the substituent group of the substituted aromatic group is selected from alkyl, alkoxy, amino, alkylthio or carbazole.
In one embodiment of the invention, the unsubstituted aryl is selected from benzene, biphenyl, naphthalene, pyridine, furan, pyrrole, thiophene, benzofuran, benzothiophene, indole, or carbazole; the substituent of the substituted aryl group is selected from C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 dialkyl amino, diphenylamino or carbazole.
In one embodiment of the invention, the C1-C20 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or n-hexyl; the C1-C20 alkoxy is selected from methoxy or ethoxy; the C1-C20 alkylthio is selected from methylthio or ethylthio; the C1-C20 dialkyl amino is selected from dimethylamino or diethylamino.
In one embodiment of the invention, the 1, 5-dihydroxynaphthalene-2, 6-dicarboxyl chalcone derivative is selected from the following compounds:
the second object of the present invention is to provide a process for the preparation of said 1, 5-dihydroxynaphthalene-2, 6-dicarboxyl chalcone derivative comprising the steps of,
s1, carrying out substitution reaction and oxidation reaction on a compound with a structure shown in a formula (II) to obtain a compound with a structure shown in a formula (III);
s2, connecting the compound with the structure shown in the formula (III) in the S1 through claisen-Schmidt reaction, and then deprotecting the compound to obtain the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative shown in the structure shown in the formula (I);
wherein the structures of the general formulae (I) - (III) are as follows:
wherein X is selected from halogen;
r is selected from C1-C20 alkyl;
ar is selected from substituted or unsubstituted aryl; the unsubstituted aryl is selected from benzene, biphenyl, a condensed aromatic ring or an aromatic heterocyclic ring; the substituent group of the substituted aromatic group is selected from alkyl, alkoxy, amino, alkylthio or carbazole.
The third object of the invention is to provide the application of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative in organic solid laser and luminescence.
A fourth object of the present invention is to provide a polystyrene microsphere comprising the 1, 5-dihydroxynaphthalene-2, 6-dicarboxyl chalcone derivative.
In one embodiment of the invention, the doping concentration of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative is greater than 0.1wt%.
Further, the doping concentration of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative is 0.1wt% to 10wt%.
A fifth object of the present invention is to provide an application of the polystyrene microsphere in organic solid laser.
In one embodiment of the invention, the polystyrene microsphere has a laser or luminescence wavelength of 650nm-2500nm.
Further, the laser wavelength of the polystyrene microsphere is 650nm-760nm.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative disclosed by the invention is based on a 1, 5-dihydroxynaphthalene-2, 6-dichalcone structure, has the activity of proton transfer in an excited state molecule, and can construct an effective four-level system, so that the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative has excellent laser performance, and the laser wavelength is in a red light to near infrared light region (650 nm-2500 nm).
(2) The 1, 5-dihydroxynaphthalene-2, 6-dichalchalcone derivative can establish two pairs of excited intramolecular proton transfer centers, realize excited intramolecular double proton transfer, bring more possibility for the regulation and control of laser performance, and improve the laser performance.
(3) The 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative can realize effective regulation and control of HOMO and LUMO energy levels by introducing different electron donating and accepting groups, so that the laser wavelength can be regulated and controlled by regulating intramolecular charge transfer.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a graph showing absorption and emission spectra of Compound 3 of the present invention.
FIG. 2 is a graph showing absorption and emission spectra of Compound 4 of the present invention.
FIG. 3 is a graph showing absorption and emission spectra of Compound 5 of the present invention.
FIG. 4 is a scanning electron micrograph of polystyrene microspheres of the present invention.
FIG. 5 is a laser spectrum of a polystyrene microsphere doped with the compound 3 according to the present invention.
FIG. 6 is a laser spectrum of a polystyrene microsphere doped with compound 4 according to the present invention.
FIG. 7 is a laser spectrum of a polystyrene microsphere doped with the compound 5 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
A1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and a preparation method thereof specifically comprise the following steps:
to a 500mL reaction flask was added intermediate 1 (10 g,62 mmol), acetic acid (300 mL), and then liquid bromine (7 mL,137 mmol) was added dropwise, and after the addition was completed, the mixture was heated to 80℃and stirred for 2 hours. After the reaction solution was filtered, the obtained solid was recrystallized from acetic acid to obtain colorless needle-like crystals (intermediate 2, 14.5 g), yield: 73%.
A500 mL reaction flask was charged with intermediate 2 (10 g,31 mmol), anhydrous potassium carbonate (26 g,189 mmol) and acetone (300 mL). Methyl iodide (4.4 g,31 mmol) was then added and the reaction was heated at reflux for 12h. The reaction solution was filtered, and the solid was washed with dichloromethane (3X 100 mL), and the filtrates were combined, desolventized under reduced pressure and diluted with dichloromethane (300 mL). The resulting solution was washed with water (3×10 mL), saturated sodium bicarbonate solution (20 mL), dried over anhydrous sodium sulfate, pressure desolventized, washed with n-hexane, and dried in vacuo to give a pale yellow solid (intermediate 3,9.5 g), yield: 87%.
To a 250mL reaction flask was added intermediate 3 (3.5 g,10 mmol), tetrahydrofuran (100 mL), and n-butyllithium solution (2.5M, 10mL,25 mmol) was slowly added dropwise at low temperature, followed by stirring at low temperature for 2 minutes, and then acetaldehyde in tetrahydrofuran (5.0M, 10mL,50 mmol) was added at once, and the mixture was naturally warmed to room temperature and stirred for 1 hour. The reaction mixture was quenched by careful addition of water (50 mL), then slowly diluted hydrochloric acid (pH paper monitor) and extracted with dichloromethane (3X 100 mL). The organic phases were combined, washed with water (3X 100 mL), washed with saturated brine (200 mL), dried over anhydrous sodium sulfate, filtered and desolventized under reduced pressure to give the crude product (intermediate 4) which was used directly in the next step.
A500 mL reaction flask was charged with the crude intermediate 4, methylene chloride (200 mL), and then with dess-Martin oxidant (11 g,25 mmol), and the reaction was stirred at room temperature for 10h. The reaction was quenched by the addition of saturated sodium bicarbonate solution (100 mL) and sodium thiosulfate solution (100 mL) and continued to stir at room temperature for 30min. The solution was separated and the aqueous phase was extracted with dichloromethane (3X 50 mL). The organic phases were combined, washed with water (3×100 mL), washed with saturated brine (100 mL), dried over anhydrous sodium sulfate, and subjected to atmospheric column chromatography (oil ether: ethyl acetate=20:1 elution) to give a pale yellow solid (intermediate 5,2.1 g), yield: 76%.
A250 mL reaction flask was charged with intermediate 5 (1.4 g,5 mmol), intermediate 6 (15 g,10 mmol), sodium hydroxide (2 g,50 mmol) and ethanol (100 mL), stirred at room temperature for 10h, orange-red precipitate formed, the reaction solution was diluted with water, filtered, and the resulting orange-red solid was washed with fresh water, and was truly obtainedCrude product of intermediate 7, which was empty dried. The crude product was further purified by normal pressure column chromatography (dichloromethane: ethyl acetate=10:1 elution) to give an orange-red solid (intermediate 7,2.2 g). Yield: 81% of a glass fiber; 1 H NMR(400MHz,CDCl 3 )δ8.07(d,J＝8.4Hz,2H),7.73(d,J＝8.4Hz,2H),7.68(d,J＝15.6Hz,2H),7.54(d,J＝8.8Hz,4H),7.34(d,J＝15.6Hz,2H),6.69(d,J＝8.8Hz,4H),3.97(s,6H),3.05(s,12H).
to a 100mL reaction flask was added intermediate 7 (1.1 g,2.0 mmol), methylene chloride (20 mL), and then a methylene chloride solution of boron tribromide (1.0M, 5.0mL,5.0 mmol) was slowly added dropwise with stirring at room temperature, and after the addition was completed, the reaction was continued with stirring at room temperature for 1h. The reaction was quenched by the addition of saturated sodium bicarbonate solution (10 mL). The solution was separated and the aqueous phase was extracted with dichloromethane (3X 5 mL). The organic phases were combined, washed with water (3×10 mL), washed with saturated brine (20 mL), dried over anhydrous sodium sulfate, and subjected to atmospheric column chromatography (petroleum ether: dichloromethane=1:1 elution) to give a dark red solid (compound 1,0.57 g), yield: 56%. 1 H NMR(400MHz,CDCl 3 )δ14.94(s,2H),8.03(d,J＝15.2Hz,2H),7.96(d,J＝15.2Hz,2H),7.65(d,J＝8.8Hz,4H),7.60(d,J＝14.8Hz,2H),7.31(d,J＝14.8Hz,2H),6.75(d,J＝8.8Hz,4H),3.11(s,12H).
Example 2
A1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and a preparation method thereof specifically comprise the following steps:
substantially the same as in example 1, except that intermediate 6 was 9-aldehyde julolidine, was obtained in the form of a dark solid (compound 4,0.75 g), yield: 61%. 1 H NMR(400MHz,CDCl 3 )δ15.09(s,2H),7.99–7.90(m,6H),7.51(d,J＝15.2Hz,2H),7.21(s,4H),3.31(t,J＝5.6Hz,8H),2.82(t,J＝6.4Hz,8H),2.07–1.96(m,8H).
Example 3
A1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and a preparation method thereof specifically comprise the following steps:
substantially the same as in example 1, except that intermediate 6 was 4-diphenylaminobenzaldehyde, was obtained in the form of a dark red solid (compound 5,1.19 g), yield: 79%. 1 H NMR(400MHz,CDCl 3 )δ14.72(s,2H),7.97(d,J＝15.2Hz,2H),7.94(d,J＝8.4Hz,2H),7.91(d,J＝8.4Hz,2H),7.62(d,J＝15.2Hz,2H),7.56(d,J＝8.8Hz,4H),7.36–7.29(m,8H),7.20–7.11(m,12H),7.05(d,J＝8.8Hz,4H).
Test example 1
Absorption and emission spectroscopy test of 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative (Compound 3-5):
(1) Sample preparation: preparing dichloromethane solution of 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative with concentration of about 1×10 -5 mol/L，5mL。
(2) Ultraviolet-visible absorption spectroscopy test: the ultraviolet-visible absorption spectrum of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative solution was tested using an ultraviolet-visible spectrophotometer.
(3) Fluorescence spectrum test: the fluorescence emission spectrum of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative solution was measured by a fluorescence spectrometer, and the excitation light was 500nm xenon lamp light source, as shown in FIGS. 1-3.
As can be seen from fig. 1, the methylene chloride solution of compound 3 has a maximum absorption wavelength of 500nm and a maximum emission wavelength of 655nm.
As can be seen from fig. 2, the methylene chloride solution of compound 4 has a maximum absorption wavelength of 535nm and a maximum emission wavelength of 680nm.
As can be seen from fig. 3, the maximum absorption wavelength of the dichloromethane solution of the compound 5 was 500nm, and the maximum emission wavelength was 670nm.
Test example 2
Preparation of 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative doped (Compound 3-5) polystyrene microsphere and test of laser Performance:
(1) Preparing mother solution: 1, 5-dihydroxynaphthalene-2, 6-dicarboxyl chalcone derivative (1.0 mg), polystyrene powder (M W :260000 100 mg) was prepared into a 2mL dichloromethane solution, and the solution was completely dissolved by ultrasonic vibration, and the obtained solution was used as a mother solution.
(2) Preparation of CTAB solution: CTAB (14.6 mg) was accurately weighed, dissolved in 20mL of deionized water to prepare a 2mM aqueous solution, and sonicated until all was dissolved for use.
(3) Preparation of polystyrene microspheres: CTAB solution (2 mL) was added to the clean sample bottle, mother liquor (0.2 mL) was added under vigorous stirring, stirring was continued for 20min, stirring was stopped, and the mixture was allowed to stand for 12h. Filtering, washing the solid with deionized water, and obtaining the solid, namely the polystyrene microsphere. The doping concentration of the compound in the polystyrene was 1.0wt%.
(4) Characterization of polystyrene microspheres: dispersing the obtained polystyrene microsphere into absolute ethyl alcohol, taking a drop of dispersion liquid to be dripped on a clean glass sheet, a quartz sheet or a silicon wafer, and obtaining a sample for testing laser performance after the solvent is completely volatilized.
A Scanning Electron Microscope (SEM) image of the compound 3-doped polystyrene microsphere is shown in fig. 4, from which it can be seen that the 1, 5-dihydroxynaphthalene-2, 6-dicarboxyl chalcone derivative-doped polystyrene microsphere has a regular morphology and a smooth surface, and the polystyrene microsphere with a smooth surface can realize light reflection, thus being used as a resonant cavity.
(5) Laser performance test: the laser spectrum of the polystyrene microsphere doped with the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative can be obtained by utilizing a micro-region spectrum system under the excitation of 532nm pulse laser (pulse width: 10ns, frequency: 10 Hz), and is shown in figures 5-7.
As can be seen from FIG. 5, the compound 3-doped polystyrene microsphere can realize laser emission with the center wavelength of 720nm and the threshold value of 26.6 mu J/cm 2 。
As can be seen from FIG. 6, the compound 4-doped polystyrene microsphere can realize laser emission with the center wavelength of 720nm and the threshold value of 16.7 mu J/cm 2 。
As can be seen from FIG. 7, the compound 5-doped polystyrene microsphere can realize a laser with a center wavelength of 730nmEmission, threshold 18.4. Mu.J/cm 2 。
From the test results, the invention can effectively realize the laser emission with low threshold value, and can realize the laser from red light to near infrared.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (10)

1.1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative is characterized in that the structure is shown as a formula (I):
wherein Ar is selected from substituted or unsubstituted aryl; the unsubstituted aryl is selected from benzene, biphenyl, a condensed aromatic ring or an aromatic heterocyclic ring; the substituent group of the substituted aromatic group is selected from alkyl, alkoxy, amino, alkylthio or carbazole.
2. The 1, 5-dihydroxynaphthalene-2, 6-dicarboxyl chalcone derivative according to claim 1, wherein the unsubstituted aromatic group is selected from benzene, biphenyl, naphthalene, pyridine, furan, pyrrole, thiophene, benzofuran, benzothiophene, indole or carbazole; the substituent of the substituted aryl group is selected from C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C1-C20 dialkyl amino, diphenylamino or carbazole.
3. The 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative according to claim 2, wherein said C1-C20 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or n-hexyl; the C1-C20 alkoxy is selected from methoxy or ethoxy; the C1-C20 alkylthio is selected from methylthio or ethylthio; the C1-C20 dialkyl amino is selected from dimethylamino or diethylamino.
4. 1, 5-dihydroxynaphthalene-2, 6-dichalcanone derivative according to claim 1, wherein said 1, 5-dihydroxynaphthalene-2, 6-dichalcanone derivative is selected from the group consisting of:
5. a process for the preparation of a 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative according to any one of claims 1 to 4, comprising the steps of,
s1, carrying out substitution reaction and oxidation reaction on a compound with a structure shown in a formula (II) to obtain a compound with a structure shown in a formula (III);
s2, connecting the compound with the structure shown in the formula (III) in the S1 through claisen-Schmidt reaction, and then deprotecting the compound to obtain the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative shown in the structure shown in the formula (I);
wherein the structures of the general formulae (I) - (III) are as follows:
wherein X is selected from halogen;
r is selected from C1-C20 alkyl;
ar is selected from substituted or unsubstituted aryl; the unsubstituted aryl is selected from benzene, biphenyl, a condensed aromatic ring or an aromatic heterocyclic ring; the substituent group of the substituted aromatic group is selected from alkyl, alkoxy, amino, alkylthio or carbazole.
6. Use of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivatives according to any one of claims 1 to 4 for organic solid-state lasers and luminescence.
7. A polystyrene microsphere comprising the 1, 5-dihydroxynaphthalene-2, 6-dicarboxchalcone derivative of any one of claims 1-4.
8. The polystyrene microsphere of claim 7, wherein the doping concentration of the 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative is greater than 0.1wt%.
9. Use of the polystyrene microsphere of claim 7 or 8 in an organic solid laser.
10. The use according to claim 9, wherein the polystyrene microsphere has a wavelength of 650nm to 2500nm of laser light or luminescence.
CN202310302002.5A 2023-03-27 2023-03-27 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and preparation method and application thereof Pending CN116478031A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310302002.5A CN116478031A (en) 2023-03-27 2023-03-27 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310302002.5A CN116478031A (en) 2023-03-27 2023-03-27 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116478031A true CN116478031A (en) 2023-07-25

Family

ID=87212862

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310302002.5A Pending CN116478031A (en) 2023-03-27 2023-03-27 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116478031A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070053021A (en) * 2005-11-18 2007-05-23 동우 화인켐 주식회사 Organic light emitting devices using compounds having excited-state intramolecular proton-transfer property
US20080179565A1 (en) * 2007-01-31 2008-07-31 Au Optronics Corp. Photosensitive monomer, liquid crystal material having the same, liquid crystal panel and method for manufacturing thereof by incorporating the same, and electro-optical device and method for manufacturing thereof by incorporating the same
CN114644564A (en) * 2022-04-06 2022-06-21 苏州大学 Cascade excited state proton transfer laser molecule single crystal material and preparation and application thereof
CN115466187A (en) * 2022-09-15 2022-12-13 苏州大学 1 '-hydroxy-2' -anthracene chalcone derivative and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070053021A (en) * 2005-11-18 2007-05-23 동우 화인켐 주식회사 Organic light emitting devices using compounds having excited-state intramolecular proton-transfer property
US20080179565A1 (en) * 2007-01-31 2008-07-31 Au Optronics Corp. Photosensitive monomer, liquid crystal material having the same, liquid crystal panel and method for manufacturing thereof by incorporating the same, and electro-optical device and method for manufacturing thereof by incorporating the same
CN114644564A (en) * 2022-04-06 2022-06-21 苏州大学 Cascade excited state proton transfer laser molecule single crystal material and preparation and application thereof
CN115466187A (en) * 2022-09-15 2022-12-13 苏州大学 1 '-hydroxy-2' -anthracene chalcone derivative and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YONG YANG等: "Investigation of ultrafast optical nonlinearities in novel bis-chalcone derivatives", 《OPTICS AND LASER TECHNOLOGY》, vol. 123, 30 October 2019 (2019-10-30), pages 105903, XP085932699, DOI: 10.1016/j.optlastec.2019.105903 *

Similar Documents

Publication Publication Date Title
CN111825634B (en) Novel compounds, process for their preparation and their use
JP6341923B2 (en) Strong fluorescent luminescent heterocyclic compound and method for producing the same
CN113999254B (en) Diazosulfide imidazole fluorescent dye and synthetic method thereof
CN111647140A (en) Novel polymeric carbazole derivative cadmium complex and preparation method and application thereof
CN115466187B (en) 1 '-Hydroxy-2' -anthracenechalcone derivative, and preparation method and application thereof
CN113416203B (en) Near-infrared-emitting thiadiazole quinoxaline fluorescent molecule with large Stokes shift and preparation method thereof
CN105505379A (en) Long-wavelength BODIPY fluorescent dye derivative and preparation method thereof
CN115819281B (en) Cyano-substituted p-phenylene ethylene derivative, preparation method and application
CN116478031A (en) 1, 5-dihydroxynaphthalene-2, 6-dichalcone derivative and preparation method and application thereof
CN115197260B (en) Alkynyl coupled double BODIPY near infrared fluorescent dye with J aggregation effect and preparation method thereof
CN108047278B (en) D-A-D type six-membered ring metal platinum (II) complex near-infrared luminescent material
CN114249758B (en) Dimer based on five-membered aromatic heterocyclic BODIPY and preparation method thereof
CN112209951B (en) Dye sensitizer of benzimidazole derivative and 8-hydroxyquinoline derivative cadmium complex, and preparation method and application thereof
CN110330511B (en) Synthesis method and biological detection application of imidazole ligand
CN111943965B (en) Pyridine imine derivative and 8-hydroxyquinoline derivative cadmium complex dye sensitizer (BDTT-im-Cd) and preparation method and application thereof
CN113501836A (en) Star BODIPY near-infrared fluorescent dye and preparation method thereof
CN110642830B (en) Dehydroabietic acid triarylamine D-pi-A type compound with thiophene derivative as pi bridge and synthesis method thereof
CN108558595B (en) P-phenylene ethylene bridged trimer indene derivative and preparation method thereof
CN111057008A (en) D-A type excited state proton transfer high-efficiency fluorescent material and preparation method and application thereof
Manav et al. Ferrocene and triphenylamine appended boranils
Yagi et al. Synthesis and light absorption/emission properties of novel bis-squaraine dyes with extensively conjugated π-electron systems
CN114957102B (en) Amide nitroxide free radical modified perylene molecule and preparation and application thereof
CN101270036B (en) Organic electroluminescence ethereal blue optical material, preparation method and application thereof
CN115850993B (en) Chiral amphiphilic near-infrared aza-BODIPY dye and preparation method thereof
RU2788650C2 (en) Asymmetrical luminescent donor-acceptor molecules based on triphenylamine-thiophene block with different electron-acceptor groups and their production method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination