WO2021078217A1 - Tetracene derivative, preparation method therefor, and use thereof - Google Patents

Tetracene derivative, preparation method therefor, and use thereof Download PDF

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WO2021078217A1
WO2021078217A1 PCT/CN2020/123012 CN2020123012W WO2021078217A1 WO 2021078217 A1 WO2021078217 A1 WO 2021078217A1 CN 2020123012 W CN2020123012 W CN 2020123012W WO 2021078217 A1 WO2021078217 A1 WO 2021078217A1
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acid
compound
reaction
alkyl
membered heteroaryl
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胡文平
舒志斌
董焕丽
王普
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中国科学院化学研究所
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Definitions

  • the invention belongs to the field of organic optoelectronics and semiconductor devices, and specifically relates to a naphthacene derivative and a preparation method and application thereof.
  • Naphthacene is composed of 4 benzene rings and its melting point is about 320°C. It has high thermal and light stability. It is less affected by external conditions such as water vapor and oxygen, and it is easy to form needles.
  • the crystals show a very regular fishbone arrangement. From the structural point of view, the field-effect mobility of crystals and films with fishbone-like arrangements of organic small molecules is often the highest. Therefore, tetracene should be an ideal field effect material.
  • Batlogg et al. of Bell Laboratory used naphthacene single crystal as the active layer and used the dual field effect to make an organic electric injection laser. The carrier mobility of the device reached 2cm 2 /V ⁇ s at room temperature.
  • topological conjugated benzene ring structure data materials such as pentacene and hexacene have also been synthesized and applied to the research of organic optoelectronic devices (Nat.Chem.,2020,12,63; Adv.Mater.,2007 ,5,688; Nat.Chem.,2017,9,Nat.Chem.,2012,4,574,etc.), but this type of material has serious problems such as poor light stability, which also limits its application research. Therefore, how to achieve a multi-fused ring conjugated molecular structure with good stability and film-forming properties is of vital importance to scientific research and device application research.
  • the lateral derivatization of the conjugated ring skeleton is of great significance for realizing the further expansion of the conjugation system and obtaining application materials with better performance, and provides an effective way to solve the above problems.
  • anthracene and pentacene have obtained considerable development and sufficient reports in the side modification and derivatization and their device applications, which are attributed to the ease of organic synthesis and the maturity of device preparation.
  • device research still remains on a few materials modified at fixed sites, especially those derived from both the 2- and 8-positions of naphthacene.
  • the present invention provides a 2,8-disubstituted naphthacene derivative represented by the following formula (I),
  • R are the same or different, and are independently selected from halogen, the following groups optionally substituted by one, two or more RS: C 6-20 aryl, 5-20 membered hetero Aryl, 5-20 membered heteroaryl and 5-20 membered heteroaryl, 5-20 membered heteroaryl and 5-20 membered heteroaryl and 5-20 membered heteroaryl, even two (C 6-20 Aryl and C 3-20 cycloalkyl and C 6-20 aryl) group, C 1-40 alkyl, C 3-20 cycloalkyl, 5-20 membered heterocyclic group, C 1-40 alkoxy , C 1-40 alkylthio;
  • the RS is selected from halogen, CN, C 1-40 alkyl, halogenated C 1-40 alkyl, -N (C 6-20 aryl) 2 , C 3-20 cycloalkyl, 3-20 membered hetero cycloalkyl group, -N (C 1- 40 alkyl) 2; optionally substituted by one, two or more C 1-40 alkyl substituted with halo radicals as follows: C 6-20 aryl group, 5- 20-membered heteroaryl.
  • R is selected from halogen, and the following groups optionally substituted by one, two or more RS: C 6-14 aryl, 5-14 membered heteroaryl Group, 5-14 membered heteroaryl and 5-14 membered heteroaryl, 5-14 membered heteroaryl and 5-14 membered heteroaryl and 5-14 membered heteroaryl, even two (C 6-14 aryl C 3-12 cycloalkyl and C 6-14 aryl) group, C 1-12 alkyl, C 1-12 alkoxy, C 1-12 alkylthio;
  • the RS is selected from halogen, CN, C 1-10 alkyl, halogenated C 1-10 alkyl, -N (C 6-14 aryl) 2 , C 3-10 cycloalkyl, 3-10 membered hetero Cyclic group, -N(C 1- 10 alkyl) 2 ; the following groups optionally substituted by one, two or more substituted halogenated C 1-10 alkyl groups: C 6-14 aryl, 5- 14-membered heteroaryl.
  • R is selected from Br, phenyl, 1-naphthyl, 2-naphthyl, thienyl, furyl, 2-anthryl, 5-anthryl, 2-fluorenyl, 3-fluorene Group, 1-dibenzofuranyl, 3-dibenzofuranyl, 3-dibenzopyrrolyl, N-dibenzopyrrolyl, 1-dibenzothienyl, 3-dibenzothienyl, 1-pyrazinyl, 1-thiazolyl, 2-phenazinyl, 1-quinoxalinyl, 9-fluorenone-2-yl, 7-quinolinyl,
  • RS is selected from fluorine, chlorine, bromine, CN, methyl, ethyl, n-hexyl, perfluoro-n-hexyl, phenyl, 3,4,5-tris(trifluoromethyl)-phenyl, 3,5- Bis(trifluoromethyl)-phenyl, 1-furyl, 1-thienyl, 4-trifluoromethyl-furyl, 4-trifluoromethyl-thienyl, N-carbazolyl, -N( Phenyl) 2 , trifluoromethyl.
  • the compound of formula (I) is selected from the following structures,
  • the present invention also provides a method for preparing the 2,8-dibromotetracene, which includes the following steps:
  • step S2 The compound 6-bromo-1,4-epoxy-1,4-dihydronaphthalene, 4-bromobenzocyclobutane and additive 1 prepared in step S1) are reacted in solvent 3 to obtain products 2,8 -Dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene;
  • step S3 Put the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and acid 2 prepared in step S2) in solvent 4 and heat to reflux In the reaction, the resulting product and the additive 2 are heated and refluxed in the solvent 5 to obtain 2,8-dibromotetracene;
  • step S1) the acid 1 is selected from inorganic acids
  • the nitrous acid compound is selected from at least one of tert-butyl nitrite, isoamyl nitrite, sodium nitrite, and potassium nitrite;
  • step S2) the additive 1 is selected from inorganic bases
  • step S3) the acid 2 is selected from inorganic acid or organic acid;
  • step S3) the additive 2 is selected from oxidizing agents.
  • the acid 1 is at least one of inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, boron trifluoride, phosphorus pentafluoride, etc., specifically hydrochloric acid or boron trifluoride;
  • the solvent 1 is an alcohol solvent such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol monomethyl ether, etc., specifically ethanol or ethylene glycol.
  • Alcohol solvent such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol monomethyl ether, etc., specifically ethanol or ethylene glycol.
  • Monomethyl ether such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol monomethyl ether, etc., specifically ethanol or ethylene glycol.
  • Monomethyl ether such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol monomethyl ether, etc., specifically ethanol or ethylene glycol.
  • Monomethyl ether solvent such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol monomethyl ether, etc
  • the solvent 2 is ethers such as diethyl ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc.
  • Solvents or aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or chloroform, methylene chloride, dichloroethane, trichloroethane, dibromoethane, Alkane solvents such as dodecane and hexadecane, specifically tetrahydrofuran or chlorobenzene or dichloroethane;
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or chloroform, methylene chloride, dichloroethane, trichloroethane, dibromoethane, Alkane solvents such as dodecane and hexadecane, specifically tetrahydrofuran or chlorobenzene
  • the molar ratio of the compound 2-amino-5-bromobenzoic acid, acid 1 and nitrous acid compound is 1:(0.01-100):(0.01-100), Preferably, it is 1:(1 ⁇ 5):(1 ⁇ 5), and specifically can be 1:1:1 or 1:2:3;
  • the molar ratio of the furan to the starting material 2-amino-5-bromobenzoic acid is 1:(0.01-100), preferably 1:(0.1-1), Specifically 1:1 or 1:0.2;
  • the low-temperature reaction temperature is -200-10°C, preferably -78-10°C; the heating reflux temperature range may be 30-300°C.
  • the additive 1 is potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, potassium acetate, sodium acetate, sodium citrate, specifically sodium carbonate or potassium acetate;
  • the solvent 3 is ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and other ethers Solvents, or aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or chloroform, methylene chloride, dichloroethane, trichloroethane, dibromoethane, Alkane solvents such as dodecane and hexadecane, specifically isoamyl ether, dichlorobenzene or dodecane;
  • step S2 the molar ratio of the compound 6-bromo-1,4-epoxy-1,4-dihydronaphthalene, 4-bromobenzocyclobutane and additive 1 is 1. :(0.01-100):(0.01-100), preferably 1:(0.5-3):(0.01-1), specifically 1:0.9:0.3 or 1:1.1:0.2;
  • the heating and reflux temperature range is 30-300°C.
  • the acid 2 is an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid or its hydrate, pyridine Organic acids such as p-toluenesulfonate, specifically hydrochloric acid or p-toluenesulfonic acid monohydrate;
  • the solvent 4 is ethers such as ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc.
  • Solvents or aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or chloroform, methylene chloride, dichloroethane, trichloroethane, dibromoethane, Alkane solvents such as dodecane and hexadecane, or acid anhydride solvents such as acetic anhydride, trifluoromethanesulfonic anhydride, or trifluoroacetic anhydride, specifically dioxane or toluene or dichloroethane or acetic anhydride;
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or chloroform, methylene chloride, dichloroethane, trichloroethan
  • the additive 2 is oxygen, benzoquinone, tetrachlorobenzoquinone, dichlorodicyanobenzoquinone (DDQ), trichlorourea cyanide, bromine, iodine, bromosuccinate Oxidizers such as imide and iodosuccinimide, or catalysts such as activated carbon and palladium on carbon, specifically DDQ or palladium on carbon;
  • the solvent 5 may be ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and other ethers.
  • Solvents can be aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or can be chloroform, dichloromethane, dichloroethane, trichloroethane, dibromide Alkane solvents such as ethane, dodecane, hexadecane, etc., specifically ethylene glycol dimethyl ether, benzene or carbon tetrachloride;
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or can be chloroform, dichloromethane, dichloroethane, trichloroethane, dibromide Alkane solvents such as ethane, dodecane, hexadecane, etc., specifically
  • step S3) the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and acid 2
  • the molar ratio is 1:(0.01-100), preferably 1:(0.5-25), and specifically may be 1:25 or 1:0.5;
  • step S3 the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and additive 2
  • the molar ratio is 1:(0.01-100), preferably 1:(0.02-5), specifically 1:0.5 or 1:2;
  • the heating and reflux temperature range may be 30-320°C.
  • the present invention also provides the application of the 2,8-dibromotetracene described above in the preparation of the 2,8-disubstituted naphthacene derivatives represented by formula (I).
  • the present invention also provides a preparation method of 2,8-disubstituted naphthacene derivatives represented by formula (I), which comprises the following steps:
  • 2,8-Dibromotetracene reacts with compound X-R to obtain 2,8-disubstituted tetracene derivatives represented by formula (I),
  • R has the above-mentioned definition
  • X is selected from a leaving group
  • 2,8-dibromotetracene is preferably prepared by the above method.
  • X is selected from halogen, boric acid, boric acid ester, alkyl tin, alkyl silicon, magnesium, zinc, and the like.
  • the reaction is the following reactions: Suzuki reaction, Stille reaction, Heck reaction, Sonogashira reaction, Hiyama reaction, Kumada reaction, Negishi reaction, Glaser-Eglinton reaction, Claisen-Schmidt reaction, Buchwald-Hartwig reaction.
  • the reaction is carried out in the presence of a catalytic system composed of a palladium complex or a palladium salt and a phosphine ligand;
  • the palladium complex refers to tetrakis (triphenylphosphine) palladium, dichlorodi (triphenylphosphine) palladium, dichlorodi (allyl) palladium, tris (dibenzylidene acetone) palladium, 1 ,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex or others Palladium complexes suitable for Suzuki reaction;
  • the palladium salt refers to palladium metal salts suitable for Suzuki reaction such as palladium acetate, palladium trifluoroacetate, palladium chloride, palladium acetylacetonate, etc.;
  • the phosphine ligand refers to triphenylphosphine, tricyclohexylphosphine, AmPhos, MePhos, TrippyPhos, SPhos, tBuXPhos, XPhos, QPhos, RuPhos, DPEPhos, XantPhos, BINAP, DPPF, DPPP, DTBPF, DPPBZ, vBRIDP, cBRIDP Such as phosphine ligands suitable for Suzuki reaction.
  • the preparation method of the 2,8-disubstituted naphthacene derivative represented by formula (I) further includes the preparation method of 2,8-dibromotetracene as described above.
  • the present invention also provides the use of 2,8-disubstituted naphthacene derivatives represented by formula (I), which are used to prepare organic semiconductor devices, electronic devices, electroluminescence devices, biosensor devices, and photonic devices Or organic spin devices and related fields.
  • formula (I) 2,8-disubstituted naphthacene derivatives represented by formula (I), which are used to prepare organic semiconductor devices, electronic devices, electroluminescence devices, biosensor devices, and photonic devices Or organic spin devices and related fields.
  • the organic semiconductor device is selected from organic field effect transistor OFETs and optoelectronic devices based on organic field effect transistors.
  • the organic semiconductor layer of the organic semiconductor device includes a 2,8-disubstituted naphthacene derivative represented by formula (I).
  • the present invention provides a class of 2,8-disubstituted naphthacene derivatives.
  • This class of compounds has 6 or more condensed ring conjugated structure features, but due to the free carbon-carbon single bond in its conjugated structure Rotational characteristics make this type of material have many unique characteristics: On the one hand, this type of compound can avoid the problem of poor stability of traditional planar conjugated fused ring polyacene materials (such as pentacene and hexacene) and perform well.
  • this type of compound can avoid the serious fluorescence quenching characteristics of traditional tetracene, pentacene, hexacene and rubrene and other condensed ring material systems, and show more excellent emission spectra. , Even in the crystal state, it can still exhibit strong and bright fluorescence emission characteristics.
  • the compound material also exhibits excellent film-forming characteristics. Through the modification of different substrates, the crystalline properties of the film can be effectively mentioned, and it has excellent molecular arrangement, which is very conducive to high Obtaining performance optoelectronic devices.
  • the preparation route adopted by the present invention is simple, and it is easy to synthesize and obtain various types of substituted naphthacene derivatives.
  • the post-processing steps of intermediates are reduced.
  • Improve the synthesis efficiency, shorten the preparation time, and the cost is relatively low.
  • the total yield of the synthesis route reaches ⁇ 50%, which is very suitable for the laboratory's high-volume preparation.
  • halogen refers to F, Cl, Br, and I. In other words, F, Cl, Br, and I can be described as “halogen" in this specification.
  • C 1-40 alkyl should be understood to mean a linear or branched saturated monovalent hydrocarbon group having 1 to 40 carbon atoms, preferably a C 1-10 alkyl group.
  • C 1-10 alkyl should be understood to preferably mean a linear or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.
  • the alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl Group, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2-dimethylbutyl, etc.
  • the group has 1, 2, 3, 4, 5, 6, carbon atoms ("C 1-6 alkyl”), such as methyl, ethyl, propyl, butyl, isopropyl , Isobutyl, sec-butyl, tert-butyl, more specifically, the group has 1, 2 or 3 carbon atoms ("C 1-3 alkyl”), such as methyl, ethyl, n-propyl ⁇ or isopropyl.
  • C 1-3 alkyl such as methyl, ethyl, n-propyl ⁇ or isopropyl.
  • C 1-40 alkyl refers to C 1-40 alkyl-O-, where C 1-40 alkyl has the definition as described above.
  • C 3-20 cycloalkyl used in the present invention means a saturated hydrocarbon ring, which may include a fused or bridged polycyclic ring system.
  • the cycloalkyl group preferably has 3 to 12 carbon atoms in its ring structure.
  • the cycloalkyl group has 3, 4, 5 or 6 carbon atoms in its ring structure.
  • C 3-6 cycloalkyl means a group such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
  • 3-20 membered heterocyclic group means a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O and S, preferably “3-10 membered heterocyclic group” ".
  • the term “3-10 membered heterocyclic group” means a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5, preferably 1-3 heteroatoms selected from N, O and S.
  • the heterocyclic group may be connected to the rest of the molecule through any of the carbon atoms or the nitrogen atom (if present).
  • the heterocyclic group may include but is not limited to: 4-membered ring, such as azetidinyl, oxetanyl; 5-membered ring, such as tetrahydrofuranyl, dioxolyl, pyrrole Alkyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or 6-membered ring, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithiaalkyl, thiomorpholinyl, piperazinyl Or trithiaalkyl; or 7-membered ring, such as diazeppanyl.
  • 4-membered ring such as azetidinyl, oxetanyl
  • 5-membered ring such as tetrahydrofuranyl, dioxolyl, pyrrole Alkyl, imidazolidinyl, pyrazolidinyl, pyrrol
  • the heterocyclic group may be benzo-fused.
  • the heterocyclic group may be bicyclic, such as but not limited to a 5, 5-membered ring, such as hexahydrocyclopenta[c]pyrrole-2(1H)-yl ring, or a 5, 6-membered bicyclic ring, such as hexahydropyrrole And [1,2-a]pyrazine-2(1H)-yl ring.
  • the ring containing the nitrogen atom may be partially unsaturated, that is, it may contain one or more double bonds, such as but not limited to 2,5-dihydro-1H-pyrrolyl, 4H-[1,3,4]thiadi Azinyl, 4,5-dihydrooxazolyl or 4H-[1,4]thiazinyl, or it may be benzo-fused, such as but not limited to dihydroisoquinolinyl.
  • the heterocyclic group is non-aromatic.
  • C 6-20 aryl should be understood to mean a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring with 6 to 20 carbon atoms, preferably “C 6-14 aryl”.
  • the term “C 6-14 aryl” should be understood as preferably meaning a monocyclic, bicyclic or partially aromatic monocyclic or partially aromatic monocyclic or partially aromatic having 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms
  • a tricyclic hydrocarbon ring (“C 6-14 aryl"), especially a ring having 6 carbon atoms (“C 6 aryl”), such as phenyl; or biphenyl, or one having 9 carbon atoms Ring (“C 9 aryl”), such as indanyl or indenyl, or a ring with 10 carbon atoms (“C 10 aryl”), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, Either a ring having 13 carbon atoms ("
  • 5-20 membered heteroaryl should be understood to include such a monovalent monocyclic, bicyclic or tricyclic aromatic ring system which has 5-20 ring atoms and contains 1-5 independently selected from N, O And S heteroatoms, for example "5-14 membered heteroaryl".
  • the term “5-14 membered heteroaryl” should be understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, especially 5 or 6 or 9 or 10 carbon atoms, and it contains 1-5, preferably 1-3 heteroatoms each independently selected from N, O and S and, additionally in each case The bottom can be benzo-fused.
  • the heteroaryl group is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiol Diazolyl, thio-4H-pyrazolyl, etc.
  • heterocyclic group, heteroaryl group or heteroarylene group includes all possible isomeric forms thereof, such as positional isomers thereof. Therefore, for some illustrative non-limiting examples, pyridinyl or pyridinylene includes pyridin-2-yl, pyridin-2-yl, pyridin-3-yl, pyridin-3-yl, pyridin-4-yl And pyridin-4-yl; thienyl or thienylene includes thiophen-2-yl, thiophen-2-yl, thiophen-3-yl, and thiophen-3-yl.
  • Figure 1 shows the equipment used in physical vapor transport to purify compounds, where A is the evaporation section; B is the deposition zone;
  • Figure 2 is a structural diagram of the devices prepared in Examples 4 and 5;
  • FIG. 3 is a diagram of a thin film device of the benzene derivative of naphthacene shown in formula 2;
  • Fig. 5 is a graph showing the transfer and output of the thiophene derivative of naphthacene shown in formula 5;
  • Fig. 6 is an AFM spectrum of the thin film device of the thiophene derivative of naphthacene shown in formula 5;
  • Fig. 7 is a transfer diagram of the naphthacene furan derivative thin film device shown in formula 6;
  • Fig. 8 is an output curve of the naphthacene furan derivative thin film device shown in formula 6;
  • the left picture in FIG. 9 is the ultraviolet absorption spectrum of the furan derivative of naphthacene shown in formula 6; the right picture is the ultraviolet absorption spectrum of the furan derivative of naphthacene shown in formula 5;
  • FIG. 10 is a transfer curve of a single crystal device of a naphthacene derivative represented by formula 2;
  • FIG. 11 is an output curve of a single crystal device of a naphthacene derivative shown in formula 2;
  • FIG. 12 is an atomic force scanning microscope image of a tetracene derivative (DPT) thin film device shown in formula 2;
  • Figure 13 is an X-ray diffraction diagram of the benzene derivative of naphthacene represented by formula 2;
  • Fig. 14 is an ultraviolet photoelectron spectrogram of the benzene derivative of naphthacene shown in formula 2;
  • FIG. 15 is an ultraviolet and fluorescence spectrum diagram of the benzene derivative of naphthacene shown in formula 2;
  • 16 is a real microscope photograph of a single crystal device prepared by the benzene derivative of naphthacene shown in formula 2;
  • Figure 17 is a single crystal transfer diagram of the furan derivative of naphthacene represented by formula 6;
  • FIG. 19 is a diagram of a single crystal device of the benzene derivative of naphthacene represented by Formula 2.
  • FIG. 21 is the stability data of continuous operation of the single crystal transistor device of naphthacene derivative represented by formula 2.
  • FIG. 22 is a study on the film-forming characteristics of the benzene derivative material of naphthacene represented by Formula 2.
  • Figure 23 shows the film-forming characteristics of the benzene derivative materials of naphthacene represented by formulas 4 (left) and 5 (right)
  • Figure 24 shows the structure data of the benzene derivative of naphthacene shown in formula 2 (a) single crystal simulated XRD diffraction data (bottom) and XRD experimental data from the obtained crystalline state, (b) single crystal packing mode data graph , Indicating that the material exhibits a typical herringbone accumulation pattern.
  • Fig. 25 is a bright-field photograph and ultraviolet fluorescence photograph of the benzene derivative material of naphthacene shown in Formula 2 in PMMA.
  • FIG. 26 is a data diagram of the luminescence performance of the benzene derivative material of naphthacene shown in formula 2 (emission of brown yellow (excitation wavelength 425nm), bright yellow (excitation wavelength 515nm) and red (excitation wavelength 590nm) light at different excitation wavelengths, respectively ).
  • FIG. 27 is a performance test diagram of a photoelectric device of a benzene derivative of naphthacene shown in formula 2.
  • the invention provides a synthetic route for efficiently preparing 2,8-dibromotetracene.
  • the compound represented by formula (I) is prepared by reacting 2,8-dibromotetracene with compound R-X.
  • Suitable compounds R-X are commercially available in many cases, and the starting compounds detailed in the examples can be obtained by known methods, so this information can be referred to.
  • X is a leaving group, for example, X is selected from D, NMe 2 , halogen, boric acid, boric acid ester, alkyl tin, silicon alkyl, magnesium, zinc and the like.
  • the compound 2,8-dibromotetracene, the preparation method includes the following steps:
  • the acid 1 can be an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, boron trifluoride, phosphorus pentafluoride, etc., specifically it can be hydrochloric acid or boron trifluoride;
  • the nitrous acid compound can be Compounds such as tert-butyl nitrate, isoamyl nitrite, sodium nitrite, potassium nitrite, etc., specifically may be isoamyl nitrite;
  • the solvent 1 may be methanol, ethanol, propanol, isopropanol, butanol, Alcoholic solvents such as ethylene glycol monomethyl ether, specifically ethanol or ethylene glycol monomethyl ether;
  • the solvent 2 can be ethyl ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol Ether solvents such as dimethyl ether, tetrahydrofuran,
  • Alkane solvents such as chloroethane, trichloroethane, dibromoethane, dodecane, hexadecane, etc., considering the three solvents, specifically tetrahydrofuran or chlorobenzene or dichloroethane; the compound 2-
  • the molar ratio of amino-5-bromobenzoic acid, acid 1 and nitrous acid compound is 1:(0.01-100):(0.01-100), specifically it can be 1:1:1 or 1:2:3;
  • the molar ratio of furan to the starting material 2-amino-5-bromobenzoic acid is 1: (0.01-100), specifically 1:1 or 1:0.2;
  • the low temperature range is -200-10°C, specifically It can be -10°C or 1°C;
  • the heating reflux means that the heating temperature is close to or higher than the boiling point of the reaction solvent under normal pressure, and the temperature range can be 30-1000°C, and in addition to the autoclave, the reaction vessel may
  • the additive 1 can be a weak base such as potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, potassium acetate, sodium acetate, sodium citrate, etc., specifically sodium carbonate or potassium acetate;
  • Solvent 3 can be ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and other ether solvents, or it can be benzene, toluene, xylene, chlorine Aromatic solvents such as benzene, fluorobenzene, bromobenzene, and chloronaphthalene, or alkane solvents such as chloroform, dichloromethane, dichloroethane, trichloroethane, dibromoethane, dodecane, hexadecane, etc.
  • the acid 2 can be an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or an organic acid such as acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and pyridine p-toluenesulfonate.
  • the solvent 4 may be ethers such as ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc.
  • the solvent may be aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or it may be chloroform, methylene chloride, dichloroethane, trichloroethane, dibromoethane Alkane, dodecane, hexadecane and other alkane solvents, or acetic anhydride, trifluoromethanesulfonic anhydride, trifluoroacetic anhydride and other acid anhydride solvents, considering the four solvents, specifically dioxane or toluene or Dichloroethane or acetic anhydride; the additive 2 can be oxygen, benzoquinone, tetrachlorobenzoquinone, dichlorodicyanobenzoquinone DDQ, trichlorourea cyanide, bromine, iodine, bromosuccin
  • Alkane solvents such as methyl chloride, dichloroethane, trichloroethane, dibromoethane, dodecane, hexadecane, etc., considering the three solvents, specifically it can be ethylene glycol dimethyl ether or benzene or tetrachloride
  • the molar ratio of the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and acid 2 is 1:(0.01 ⁇ 100 ), specifically 1:25 or 1:0.5; the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and additive 2
  • the molar ratio of is 1:(0.01-100), specifically it can be 1:0.5 or 1:2; the heating reflux and post-treatment are as described in step 1).
  • the compound of the present invention can also be mixed with a polymer, and it is even possible to be covalently bound to the molecular backbone of the polymer.
  • a polymer for example, using reactive leaving groups (for example, fluorine, chlorine, bromine, iodine, boric acid, borate, stannane, silicon ester, silane, etc.) or reactive polymerizable groups (for example, alkene, alkyne, etc.) Hydrocarbon, propylene oxide, oxetane and other groups) are particularly feasible methods to replace these compounds. Therefore, these compounds substituted by reactive groups can be used to prepare corresponding oligomers and dendrimers.
  • the oligomerization or polymerization is preferably achieved via a halogen functional group, a boric acid functional group, a tin-based functional group or a silicon-based functional group, or via a reactive polymerizable group.
  • crosslinking of the polymer can also be achieved via these reactive groups.
  • Solvents and reagents can be purchased from commercial sources, for example, chemical reagent companies such as Sinopharm, J&K, Acros, Innochem, Alfa-aesar, Adamas-beta.
  • chemical reagent companies such as Sinopharm, J&K, Acros, Innochem, Alfa-aesar, Adamas-beta.
  • the corresponding literature source and CAS number are also reported as appropriate in each case.
  • the bright red transparent liquid is high-purity 6-bromo-1,4-epoxy-1 ,4-Dihydronaphthalene.
  • the organic solvent was removed under reduced pressure to obtain a brown-red liquid.
  • the crude product is purified by 200-400 mesh silica gel column chromatography (the eluent is petroleum ether and dichloromethane), and finally a reddish brown liquid product (59 g, yield 80%) can be obtained.
  • the reddish-brown liquid is high-purity 2,8-dibromo-5,12-epoxy -5,5a,6,11,11a,12-hexahydrotetracene.
  • the purification method in this embodiment uses an electric tube furnace of Bruke Company, equipped with a quartz tube that can be evacuated and filled with gas.
  • the electric tube furnace is divided into evaporation section A and deposition section B.
  • the purification and sublimation operation is as follows: first the system pressure is pumped by a mechanical pump to 1x10 -1 pa, and then pumped to 1x10 -3 pa by a molecular pump, and then heated and purified.
  • the evaporation section is heated by resistance wire, and the temperature control is completed by the tube furnace's own system.
  • the compounds prepared in the foregoing Examples 2 and 3 were placed in a quartz boat and placed in the evaporation area, heated at 350° C. for 4 days, and deposited on B naturally.
  • the material obtained by sublimation deposition in B is the required material.
  • the furnace temperature drops below 50°C, turn off the pump, then vent the air and scrape off the required materials.
  • the source and drain of the source and drain electrodes are both composed of gold electrodes, and the thickness of the thin film device electrodes is about 20 nm. Operate in a vapor deposition machine, place the compound purified in Example 3 above in a quartz boat, heat it with 1.3 ampere current, and vaporize 50 nm at a rate of 0.1 A/S.
  • the substrate is a 300nm-thick silicon dioxide sheet modified by hexamethyltrichlorosilane. After taking it out, a different specification mask is used.
  • the gold is also evaporated in an evaporation machine, and 20-25nm is evaporated at a rate of 0.1A/s. .
  • the electrical test method is: at room temperature in the atmospheric environment, the widely used OFET test method (electrode vapor deposition or sticking to the organic layer, test on the probe station.
  • the source pin and the missing pin Poke on the gold electrode respectively, and then poke the gate pin on the bottom gate (copper sheet), keep the source gate voltage unchanged, change the source and drain voltage to test and observe the current) on the Micromanipulator 6150 manual probe station Use Keithley 4200SCS semiconductor electrical test system for testing.
  • the device structure is shown in Figure 2.
  • the source and drain electrodes are gold electrodes with a thickness of 20-25 nm
  • the organic semiconductor layer is the compound purified in Example 4
  • the insulating layer is a silicon dioxide layer modified with hexamethyltrichlorosilane (ots)
  • the gate is silicon.
  • the channel length in the following table is the channel length of the copper mesh.
  • the average value in the above table is the average value obtained by preparing 20 devices and measuring under the same conditions.
  • This example also tested the ultraviolet fluorescence spectra of the following compounds.
  • the test process was as follows: Dissolve 1 mg of the test compound in a tetrahydrofuran solution, and filter the residue with a filter due to the extremely poor solubility of the compound, and then the ultraviolet-visible spectrum and the fluorescence spectrum were respectively It was carried out on Hitachi U-3010 ultraviolet-visible spectrometer and J ⁇ S.CO FP-6600 spectrofluorometer. The operation is normal operation.
  • the test result is shown in Figure 9. It can be seen from Figure 9 that the band gaps of the thiophene and furan benzene derivatives of naphthacene are both around 2 eV, which is a narrow band gap material, which is prone to high mobility materials.
  • the source and drain electrodes are all composed of gold electrodes, and single crystals are prepared by physical vapor deposition.
  • the test is carried out.
  • the test method is to pierce the needle on the electrode and at the same time pierce the grid needle on the bottom grid electrode.
  • the gate uses a copper sheet
  • the gate uses a copper sheet
  • the gate voltage unchanged (the voltage between the source and the gate, the source is 0V)
  • the test is performed by changing the source and drain voltage.
  • the device uses bottom-gate top contact (gate at the bottom, top source and drain), and its structure is shown in Figure 2.
  • the source and drain electrodes are 25nm thick gold electrodes
  • the organic semiconductor layer is the compound purified in Example 4 above
  • the insulating layer is A silicon dioxide layer modified by hexamethyltrichlorosilane (ots)
  • the gate is silicon.
  • the average value in the above table is the average value obtained by preparing 20 devices and measuring under the same conditions.
  • an atomic force scanning microscope was used to test the tetracene derivative (DPT) thin film device shown in formula 2.
  • the result is shown in FIG. 12, which shows that the thin film is regular and large. Lump-shaped crystals reduce the grain boundaries, and the mobility of the device should be higher.
  • This example also tested the UV Photoelectron Spectroscopy (UPS) of the benzene derivative of naphthacene shown in Formula 2, and the result is shown in FIG. 14. From FIG. 14, the HOMO and LUMO can be known, so that the band gap can be calculated. After calculation, it is similar to the band gap calculated by ultraviolet, and it is expected to be a narrow band gap material.
  • UPS UV Photoelectron Spectroscopy
  • the stability data of the continuous operation of the tetracene benzene derivative single crystal transistor device shown in formula 2 (silicon and silicon dioxide are used as the gate and insulating layer, and gold is used as the source and drain electrodes.
  • the device does not undergo any special protection and packaging. Processing, atmospheric test conditions, test voltage range: grid voltage 20V--40V, source-drain voltage: -40V; test step: 2V) as shown in Figure 21. It can be seen from Figure 21 that the electronic device constructed based on this molecule has excellent working stability. During the continuous tracking test for 40 hours, the performance orientation of the device is basically the same, and with the extension of the test time, the curve of the device shows More standard, showing its excellent optoelectronic working characteristics.
  • FIG. 25 The bright field (left) and fluorescence (right) photographs of the benzene derivative of naphthacene shown in formula 2 doped (doping amount is 1-10%) in PMMA are shown in FIG. 25.
  • the figure shows that this type of material has obvious luminescence characteristics and can be used in the application research of electroluminescent devices, biosensing devices, photonics devices and related functional devices.
  • FIG. 26 The bright field (left one) of the single crystal of the benzene derivative of naphthacene shown in Formula 2 and the fluorescence photos at different excitation wavelengths are shown in FIG. 26.
  • the figure shows that this type of material also has good luminescence properties in the single crystal state, which is better than the traditional fused-ring acene material system, indicating its potential important applications in organic micro-nano electro-optical devices and biosensing.
  • the electrical performance test data of the benzene derivative photoelectric device of naphthacene shown in Formula 2 is shown in FIG. 27. It can be seen from Fig. 27 that under the condition of applying light, the photocurrent increases with the increase of the irradiated light intensity, showing an excellent photoresponse. Without optimization of the system device structure and interface conditions, the best light sensitivity (P) of the obtained device can be as high as 10 6 ; in addition, this type of device also exhibits a certain magnetic field response characteristic, indicating that this type of compound Potential applications in multifunctional optoelectronic devices and organic spin.
  • P light sensitivity

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Abstract

Disclosed are a 2,8-disubstituted tetracene derivative represented by formula (I), a preparation method therefor, and the use thereof. The compound can be used for preparing an organic semiconductor device, particularly an organic field-effect transistor (OFET). A single crystal and a thin-film device, as prepared from the above-mentioned tetracene derivative, have a higher mobility, threshold voltage and switch ratio. The preparation method is simple, can greatly increase the yield of 2,8-dibromotetracene, reduces the number of post-treatment steps of intermediates, increases the synthetic efficiency, reduces the preparation time, and has a relatively low cost. The total yield of the synthesis route reaches approximately 50%. The present invention is very suitable for scaled-up preparation in a laboratory, and can provide sufficient raw materials for the preparation of a photoelectronic device containing the tetracene derivative.

Description

一种并四苯类衍生物及其制备方法与应用A naphthacene derivative and its preparation method and application
本申请要求2019年10月22日向中国国家知识产权局提交的，专利申请号为201911008241.X，发明名称为“一种并四苯类衍生物及其制备方法与应用”在先申请的优先权。该申请的全文通过引用的方式结合于本申请中。This application claims the priority of the prior application filed with the State Intellectual Property Office of China on October 22, 2019. The patent application number is 201911008241.X and the title of the invention is "A naphthacene derivative and its preparation method and application". . The full text of this application is incorporated into this application by reference.
技术领域Technical field
本发明属于有机光电子学和半导体器件领域，具体涉及一种并四苯类衍生物及其制备方法与应用。The invention belongs to the field of organic optoelectronics and semiconductor devices, and specifically relates to a naphthacene derivative and a preparation method and application thereof.
背景技术Background technique
并四苯由4个苯环并环而成，其熔点在320℃左右，具有较高的热稳定性和光稳定性，受水蒸汽和氧气等外界条件的影响较小，并且很容易形成针状晶体，呈现出非常规则的鱼骨状排列。从结构上看，有机小分子呈鱼骨状排列的晶体及薄膜的场效应迁移率往往是最高的。因此，并四苯应该是一种理想的场效应材料。2000年，Bell实验室的Batlogg等人利用并四苯单晶作有源层，利用双场效应制成有机电注入激光器，在室温下器件的载流子迁移率达到2cm 2/V·s，低温下可达到1×10 3～1×10 5cm 2/V·s，开辟了新的有机器件的研究领域(Science,2000,289,599-601)。作为重要的并四苯类衍生物材料的明星分子——红荧烯(Rubrene)，由于其在发光效率、激子扩散长度、载流子迁移率等方面较之其他的有机材料有较大的优势，在近年来被广泛地应用于有机放光二极管(organic light-emitting diodes,OLEDs)、有机场效应晶体管(organic field-effect transistors,OFETs)及有机太阳能电池(organic photovoltaic cells,OPVCs)等领域。而且，作为荧光客体材料，它还可以应用在有机发光的显示与照明方面(Appl.Phys.Lett.2005,86,073510)。然而红荧烯存在成膜性差等缺点，使得其应用受到限制。为了克服这一问题，在保证多稠环共轭结构和优势光电的基础上，通过进一步延长结构的共轭性来改善材料的成膜性以提高材料的器件应用性方面研究者也开展了许多相应的研究。譬如，通过进一步拓扑共轭苯环结构数据，并五苯，并六苯等材料也被陆续合成和应用于有机光电器件研究(Nat.Chem.,2020,12,63；Adv.Mater.,2007,5,688；Nat.Chem.,2017,9,Nat.Chem.,2012,4,574,etc.)，但是该类材料存在严重的光稳定性差等方面的问题，同样限制了其应用研究。因此，如何实现稳定性和成膜性好的多稠环共轭分子结构，对于科学研究和器件应用研究来讲具有至关重要的意义。 Naphthacene is composed of 4 benzene rings and its melting point is about 320℃. It has high thermal and light stability. It is less affected by external conditions such as water vapor and oxygen, and it is easy to form needles. The crystals show a very regular fishbone arrangement. From the structural point of view, the field-effect mobility of crystals and films with fishbone-like arrangements of organic small molecules is often the highest. Therefore, tetracene should be an ideal field effect material. In 2000, Batlogg et al. of Bell Laboratory used naphthacene single crystal as the active layer and used the dual field effect to make an organic electric injection laser. The carrier mobility of the device reached 2cm 2 /V·s at room temperature. It can reach 1×10 3 ～1×10 5 cm 2 /V·s at low temperature, opening up a new field of organic device research (Science, 2000, 289, 599-601). As an important star molecule of naphthacene derivative materials, Rubrene (Rubrene), due to its luminous efficiency, exciton diffusion length, carrier mobility, etc. has greater than other organic materials Advantages, in recent years have been widely used in organic light-emitting diodes (organic light-emitting diodes, OLEDs), organic field-effect transistors (organic field-effect transistors, OFETs) and organic photovoltaic cells (organic photovoltaic cells, OPVCs) and other fields . Moreover, as a fluorescent guest material, it can also be applied to the display and lighting of organic luminescence (Appl. Phys. Lett. 2005, 86, 073510). However, rubrene has disadvantages such as poor film-forming properties, which limits its application. In order to overcome this problem, on the basis of ensuring the multi-fused ring conjugation structure and superior optoelectronics, the conjugation of the structure is further extended to improve the film-forming properties of the material to improve the applicability of the material device. Corresponding research. For example, through further topological conjugated benzene ring structure data, materials such as pentacene and hexacene have also been synthesized and applied to the research of organic optoelectronic devices (Nat.Chem.,2020,12,63; Adv.Mater.,2007 ,5,688; Nat.Chem.,2017,9,Nat.Chem.,2012,4,574,etc.), but this type of material has serious problems such as poor light stability, which also limits its application research. Therefore, how to achieve a multi-fused ring conjugated molecular structure with good stability and film-forming properties is of vital importance to scientific research and device application research.
通过共轭并环骨架的侧位衍生对于实现共轭体系的进一步拓展和获得性能更优良的应用材料具有非常重要的意义，为解决上述问题提供了一种有效途径。目前，蒽和并五苯在侧位修饰衍生及其器件应用上都获得了长足的发展和充分的报道，这归功于有机合成的简便和器件制备的成熟。但是，对于并四苯骨架的侧位衍生物，器件研究依然还停留在固定位点修饰后的少数材料上，尤其是在并四苯的2位和8位两个位点同时进行修饰衍生的材料几乎没有，主要原因是偶数并环化合物(并四苯和并六苯等)的合成以及选择性修饰较奇数并环化合物(蒽和并五苯等)更加困难。因此，2,8-双取代并四苯类衍生物，不仅是并四苯类衍生物材料中的一大空缺，也是有机半导体器件研究领域中的一个方向。The lateral derivatization of the conjugated ring skeleton is of great significance for realizing the further expansion of the conjugation system and obtaining application materials with better performance, and provides an effective way to solve the above problems. At present, anthracene and pentacene have obtained considerable development and sufficient reports in the side modification and derivatization and their device applications, which are attributed to the ease of organic synthesis and the maturity of device preparation. However, for the pendant derivatives of the naphthacene skeleton, device research still remains on a few materials modified at fixed sites, especially those derived from both the 2- and 8-positions of naphthacene. There are almost no materials, mainly because the synthesis and selective modification of even-numbered cyclic compounds (such as tetracene and hexacene) are more difficult than odd-numbered cyclic compounds (anthracene, pentacene, etc.). Therefore, 2,8-disubstituted naphthacene derivatives are not only a big gap in naphthacene derivative materials, but also a direction in the field of organic semiconductor device research.
发明内容Summary of the invention
为解决上述技术问题，本发明提供如下式(I)所示的2,8-双取代的并四苯类衍生物，In order to solve the above technical problems, the present invention provides a 2,8-disubstituted naphthacene derivative represented by the following formula (I),
Figure PCTCN2020123012-appb-000001
Figure PCTCN2020123012-appb-000001
其中，式(I)中，R相同或不同，彼此独立地选自卤素、任选被一个、两个或更多个RS取代的如下基团：C 6-20芳基、5-20元杂芳基、5-20元杂芳基并5-20元杂芳基、5-20元杂芳基并5-20元杂芳基并5-20元杂芳基、连二(C 6-20芳基并C 3-20环烷基并C 6-20芳基)基、C 1-40烷基、C 3-20环烷基、5-20元杂环基、C 1-40烷氧基、C 1-40烷硫基； Wherein, in formula (I), R are the same or different, and are independently selected from halogen, the following groups optionally substituted by one, two or more RS: C 6-20 aryl, 5-20 membered hetero Aryl, 5-20 membered heteroaryl and 5-20 membered heteroaryl, 5-20 membered heteroaryl and 5-20 membered heteroaryl and 5-20 membered heteroaryl, even two (C 6-20 Aryl and C 3-20 cycloalkyl and C 6-20 aryl) group, C 1-40 alkyl, C 3-20 cycloalkyl, 5-20 membered heterocyclic group, C 1-40 alkoxy , C 1-40 alkylthio;
所述RS选自卤素、CN、C 1-40烷基、卤代C 1-40烷基、-N(C 6-20芳基) 2、C 3-20环烷基、3-20元杂环基、-N(C 1- 40烷基) 2；任选被一个、两个或更多个取代卤代C 1-40烷基取代的如下基团：C 6-20芳基、5-20元杂芳基。 The RS is selected from halogen, CN, C 1-40 alkyl, halogenated C 1-40 alkyl, -N (C 6-20 aryl) 2 , C 3-20 cycloalkyl, 3-20 membered hetero cycloalkyl group, -N (C 1- 40 alkyl) 2; optionally substituted by one, two or more C 1-40 alkyl substituted with halo radicals as follows: C 6-20 aryl group, 5- 20-membered heteroaryl.
根据本发明的实施方式，式(I)化合物中，R选自卤素、任选被一个、两个或更多个RS取代的如下基团：C 6-14芳基、5-14元杂芳基、5-14元杂芳基并5-14元杂芳基、5-14元杂芳基并5-14元杂芳基并5-14元杂芳基、连二(C 6-14芳基并C 3-12环烷基并C 6-14芳基)基、C 1-12烷基、C 1-12烷氧基、C 1-12烷硫基； According to an embodiment of the present invention, in the compound of formula (I), R is selected from halogen, and the following groups optionally substituted by one, two or more RS: C 6-14 aryl, 5-14 membered heteroaryl Group, 5-14 membered heteroaryl and 5-14 membered heteroaryl, 5-14 membered heteroaryl and 5-14 membered heteroaryl and 5-14 membered heteroaryl, even two (C 6-14 aryl C 3-12 cycloalkyl and C 6-14 aryl) group, C 1-12 alkyl, C 1-12 alkoxy, C 1-12 alkylthio;
所述RS选自卤素、CN、C 1-10烷基、卤代C 1-10烷基、-N(C 6-14芳基) 2、C 3-10环烷基、3-10元杂环基、-N(C 1- 10烷基) 2；任选被一个、两个或更多个取代卤代C 1-10烷基取代的如下基团：C 6-14芳基、5-14元杂芳基。 The RS is selected from halogen, CN, C 1-10 alkyl, halogenated C 1-10 alkyl, -N (C 6-14 aryl) 2 , C 3-10 cycloalkyl, 3-10 membered hetero Cyclic group, -N(C 1- 10 alkyl) 2 ; the following groups optionally substituted by one, two or more substituted halogenated C 1-10 alkyl groups: C 6-14 aryl, 5- 14-membered heteroaryl.
根据本发明优选的实施方案，R选自Br、苯基、1-萘基、2-萘基、噻吩基、呋喃基、2-蒽基、5-蒽基、2-芴基、3-芴基、1-二苯并呋喃基、3-二苯并呋喃基、3-二苯并吡咯基、N-二苯并吡咯基、1-二苯并噻吩基、3-二苯并噻吩基、1-吡嗪基、1-噻唑基、2-吩嗪基、1-喹喔啉基、9-芴酮-2-基、7-喹啉基、According to a preferred embodiment of the present invention, R is selected from Br, phenyl, 1-naphthyl, 2-naphthyl, thienyl, furyl, 2-anthryl, 5-anthryl, 2-fluorenyl, 3-fluorene Group, 1-dibenzofuranyl, 3-dibenzofuranyl, 3-dibenzopyrrolyl, N-dibenzopyrrolyl, 1-dibenzothienyl, 3-dibenzothienyl, 1-pyrazinyl, 1-thiazolyl, 2-phenazinyl, 1-quinoxalinyl, 9-fluorenone-2-yl, 7-quinolinyl,
或如下基团：Or the following groups:
Figure PCTCN2020123012-appb-000002
Figure PCTCN2020123012-appb-000002
其中，“*”处表示连接位点；Among them, "*" represents the connection site;
RS选自氟、氯、溴、CN、甲基、乙基、正己基、全氟代正己基、苯基、3,4,5-三(三氟甲基)-苯基、3,5-二(三氟甲基)-苯基、1-呋喃基、1-噻吩基、4-三氟甲基-呋喃基、4-三氟甲基-噻吩基、N-咔唑基、-N(苯基) 2、三氟甲基。 RS is selected from fluorine, chlorine, bromine, CN, methyl, ethyl, n-hexyl, perfluoro-n-hexyl, phenyl, 3,4,5-tris(trifluoromethyl)-phenyl, 3,5- Bis(trifluoromethyl)-phenyl, 1-furyl, 1-thienyl, 4-trifluoromethyl-furyl, 4-trifluoromethyl-thienyl, N-carbazolyl, -N( Phenyl) 2 , trifluoromethyl.
作为实例，式(I)化合物选自如下结构，As an example, the compound of formula (I) is selected from the following structures,
Figure PCTCN2020123012-appb-000003
Figure PCTCN2020123012-appb-000003
Figure PCTCN2020123012-appb-000004
Figure PCTCN2020123012-appb-000004
Figure PCTCN2020123012-appb-000005
Figure PCTCN2020123012-appb-000005
Figure PCTCN2020123012-appb-000006
Figure PCTCN2020123012-appb-000006
Figure PCTCN2020123012-appb-000007
Figure PCTCN2020123012-appb-000007
本发明还提供一种所述2,8-二溴并四苯的制备方法，包括如下步骤：The present invention also provides a method for preparing the 2,8-dibromotetracene, which includes the following steps:
Figure PCTCN2020123012-appb-000008
Figure PCTCN2020123012-appb-000008
S1)将化合物2-氨基-5-溴苯甲酸，酸1和亚硝酸类化合物置于溶剂1中，在低温下进行反应；反应完成后与呋喃共同置于另一种溶剂2中，加热回流反应得到6-溴-1,4-环氧-1,4-二氢萘；S1) Put the compound 2-amino-5-bromobenzoic acid, acid 1 and nitrous acid compound in solvent 1 and react at low temperature; after the reaction is completed, put it in another solvent 2 together with furan, and heat to reflux The reaction obtains 6-bromo-1,4-epoxy-1,4-dihydronaphthalene;
S2)将步骤S1)制备的化合物6-溴-1,4-环氧-1,4-二氢萘，4-溴苯并环丁烷以及添加剂1置于溶剂3中反应得到产物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯；S2) The compound 6-bromo-1,4-epoxy-1,4-dihydronaphthalene, 4-bromobenzocyclobutane and additive 1 prepared in step S1) are reacted in solvent 3 to obtain products 2,8 -Dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene;
S3)将步骤S2)制备的化合物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯和酸2置于溶剂4中加热回流反应，将所得产物与添加剂2在溶剂5中加热回流反应得到2,8-二溴并四苯；S3) Put the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and acid 2 prepared in step S2) in solvent 4 and heat to reflux In the reaction, the resulting product and the additive 2 are heated and refluxed in the solvent 5 to obtain 2,8-dibromotetracene;
其中，步骤S1)中，所述酸1选自无机酸；Wherein, in step S1), the acid 1 is selected from inorganic acids;
步骤S1)中，所述亚硝酸类化合物选自亚硝酸叔丁酯、亚硝酸异戊酯、亚硝酸钠、亚硝酸钾中的至少一种；In step S1), the nitrous acid compound is selected from at least one of tert-butyl nitrite, isoamyl nitrite, sodium nitrite, and potassium nitrite;
步骤S2)中，所述添加剂1选自无机碱；In step S2), the additive 1 is selected from inorganic bases;
步骤S3)中，所述酸2选自无机酸或有机酸；In step S3), the acid 2 is selected from inorganic acid or organic acid;
步骤S3)中，所述添加剂2选自氧化剂。In step S3), the additive 2 is selected from oxidizing agents.
根据本发明的实施方案，步骤S1)中，所述酸1为盐酸、硫酸、磷酸、三氟化硼、五氟化磷等无机酸中的至少一种，具体为盐酸或三氟化硼；According to an embodiment of the present invention, in step S1), the acid 1 is at least one of inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, boron trifluoride, phosphorus pentafluoride, etc., specifically hydrochloric acid or boron trifluoride;
根据本发明的实施方案，步骤S1)中，所述溶剂1为甲醇、乙醇、丙醇、异丙醇、丁醇、乙二醇单甲醚等醇类溶剂，具体可为乙醇或乙二醇单甲醚；According to an embodiment of the present invention, in step S1), the solvent 1 is an alcohol solvent such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol monomethyl ether, etc., specifically ethanol or ethylene glycol. Monomethyl ether
根据本发明的实施方案，步骤S1)中，所述溶剂2为***、甲基异丙基醚、二异丙基醚、丁醚、乙二醇二甲醚、四氢呋喃、二噁烷等醚类溶剂，或者为苯、甲苯、二甲苯、氯苯、氟苯、溴苯、氯萘等芳烃类溶剂，或者为氯仿、二氯甲烷、二氯乙烷、三氯乙烷、二溴乙烷、十二烷、十六烷等烷烃类溶剂，具体为四氢呋喃或氯苯或二氯乙烷；According to an embodiment of the present invention, in step S1), the solvent 2 is ethers such as diethyl ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc. Solvents, or aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or chloroform, methylene chloride, dichloroethane, trichloroethane, dibromoethane, Alkane solvents such as dodecane and hexadecane, specifically tetrahydrofuran or chlorobenzene or dichloroethane;
根据本发明的实施方案，步骤S1)中，所述化合物2-氨基-5-溴苯甲酸，酸1和亚硝酸类化合物的摩尔比为1:(0.01～100):(0.01～100)，优选为1:(1～5):(1～5)，具体可为1:1:1或1:2:3；According to an embodiment of the present invention, in step S1), the molar ratio of the compound 2-amino-5-bromobenzoic acid, acid 1 and nitrous acid compound is 1:(0.01-100):(0.01-100), Preferably, it is 1:(1～5):(1～5), and specifically can be 1:1:1 or 1:2:3;
根据本发明的实施方案，步骤S1)中，所述呋喃和起始原料2-氨基-5-溴苯甲酸的摩尔比为1:(0.01～100)，优选为1:(0.1～1)，具体为1:1或1:0.2；According to an embodiment of the present invention, in step S1), the molar ratio of the furan to the starting material 2-amino-5-bromobenzoic acid is 1:(0.01-100), preferably 1:(0.1-1), Specifically 1:1 or 1:0.2;
根据本发明的实施方案，步骤S1)中，所述低温反应的温度是-200～10℃，优选-78～-10℃；所述加热回流温度范围可以是30～300℃。According to an embodiment of the present invention, in step S1), the low-temperature reaction temperature is -200-10°C, preferably -78-10°C; the heating reflux temperature range may be 30-300°C.
根据本发明的实施方案，步骤S2)中，所述添加剂1为碳酸钾、碳酸氢钾、碳酸钠、碳酸氢钠、醋酸钾、醋酸钠、柠檬酸钠，具体为碳酸钠或醋酸钾；According to an embodiment of the present invention, in step S2), the additive 1 is potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, potassium acetate, sodium acetate, sodium citrate, specifically sodium carbonate or potassium acetate;
根据本发明的实施方案，步骤S2)中，所述溶剂3为***、甲基异丙基醚、二异丙基醚、丁醚、乙二醇二甲醚、四氢呋喃、二噁烷等醚类溶剂，或者为苯、甲苯、二甲苯、氯苯、氟苯、溴苯、氯萘等芳烃类溶剂，或者为氯仿、二氯甲烷、二氯乙烷、三氯乙烷、二溴乙烷、十二烷、十六烷等烷烃类溶剂，具体为异戊醚或二氯苯或十二烷；According to an embodiment of the present invention, in step S2), the solvent 3 is ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and other ethers Solvents, or aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or chloroform, methylene chloride, dichloroethane, trichloroethane, dibromoethane, Alkane solvents such as dodecane and hexadecane, specifically isoamyl ether, dichlorobenzene or dodecane;
根据本发明的实施方案，步骤S2)中，所述化合物6-溴-1,4-环氧-1,4-二氢萘，4-溴苯并环丁烷和添加剂1的摩尔比为1:(0.01～100):(0.01～100)，优选为1:(0.5～3):(0.01～1)，具体为1:0.9:0.3或1:1.1:0.2；According to an embodiment of the present invention, in step S2), the molar ratio of the compound 6-bromo-1,4-epoxy-1,4-dihydronaphthalene, 4-bromobenzocyclobutane and additive 1 is 1. :(0.01-100):(0.01-100), preferably 1:(0.5-3):(0.01-1), specifically 1:0.9:0.3 or 1:1.1:0.2;
根据本发明的实施方案，步骤S2)中，所述加热回流温度范围是30～300℃。According to an embodiment of the present invention, in step S2), the heating and reflux temperature range is 30-300°C.
根据本发明的实施方案，步骤S3)中，所述酸2为盐酸、硫酸、磷酸等无机酸，或者为醋酸、三氟醋酸、三氟甲磺酸、对甲苯磺酸或其水合物、吡啶对甲苯磺酸盐等有机酸，具体为盐酸或一水合对甲苯磺酸；According to an embodiment of the present invention, in step S3), the acid 2 is an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid or its hydrate, pyridine Organic acids such as p-toluenesulfonate, specifically hydrochloric acid or p-toluenesulfonic acid monohydrate;
根据本发明的实施方案，步骤S3)中，所述溶剂4为***、甲基异丙基醚、二异丙基醚、丁醚、乙二醇二甲醚、四氢呋喃、二噁烷等醚类溶剂，或者为苯、甲苯、二甲苯、氯苯、氟苯、溴苯、氯萘等芳烃类溶剂，或者为氯仿、二氯甲烷、二氯乙烷、三氯乙烷、二溴乙烷、十二烷、十六烷等烷烃类溶剂，或者为醋酸酐、三氟甲磺酸酐、三氟醋酸酐等酸酐类溶剂，具体为二噁烷或甲苯或二氯乙烷或醋酸酐；According to an embodiment of the present invention, in step S3), the solvent 4 is ethers such as ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc. Solvents, or aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or chloroform, methylene chloride, dichloroethane, trichloroethane, dibromoethane, Alkane solvents such as dodecane and hexadecane, or acid anhydride solvents such as acetic anhydride, trifluoromethanesulfonic anhydride, or trifluoroacetic anhydride, specifically dioxane or toluene or dichloroethane or acetic anhydride;
根据本发明的实施方案，步骤S3)中，所述添加剂2为氧气、苯醌、四氯苯醌、二氯二氰基苯醌(DDQ)、三氯脲氰、溴、碘、溴代琥珀酰亚胺、碘代琥珀酰亚胺等氧化剂，或者为活性碳、钯碳等催化剂，具体为DDQ或钯碳；According to an embodiment of the present invention, in step S3), the additive 2 is oxygen, benzoquinone, tetrachlorobenzoquinone, dichlorodicyanobenzoquinone (DDQ), trichlorourea cyanide, bromine, iodine, bromosuccinate Oxidizers such as imide and iodosuccinimide, or catalysts such as activated carbon and palladium on carbon, specifically DDQ or palladium on carbon;
根据本发明的实施方案，步骤S3)中，所述溶剂5可以为***、甲基异丙基醚、二异丙基醚、丁醚、乙二醇二甲醚、四氢呋喃、二噁烷等醚类溶剂，或者可以为苯、甲苯、二甲苯、氯苯、氟苯、溴苯、氯萘等芳烃类溶剂，或者可以为氯仿、二氯甲烷、二氯乙烷、三氯乙烷、二溴乙烷、十二烷、十六烷等烷烃类溶剂，具体可为乙二醇二甲醚或苯或四氯化碳；According to an embodiment of the present invention, in step S3), the solvent 5 may be ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and other ethers. Solvents, or can be aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or can be chloroform, dichloromethane, dichloroethane, trichloroethane, dibromide Alkane solvents such as ethane, dodecane, hexadecane, etc., specifically ethylene glycol dimethyl ether, benzene or carbon tetrachloride;
根据本发明的实施方案，步骤S3)中，所述化合物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯和酸2的摩尔比为1:(0.01～100)，优选为1:(0.5～25)，具体可为1:25或1:0.5；According to an embodiment of the present invention, in step S3), the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and acid 2 The molar ratio is 1:(0.01-100), preferably 1:(0.5-25), and specifically may be 1:25 or 1:0.5;
根据本发明的实施方案，步骤S3)中，所述化合物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯和添加剂2的摩尔比为1:(0.01～100)，优选为1:(0.02～5)，具体为1:0.5或1:2；According to an embodiment of the present invention, in step S3), the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and additive 2 The molar ratio is 1:(0.01-100), preferably 1:(0.02-5), specifically 1:0.5 or 1:2;
根据本发明的实施方案，步骤S3)中，所述加热回流温度范围可以是30～320℃。According to an embodiment of the present invention, in step S3), the heating and reflux temperature range may be 30-320°C.
本发明还提供了如上所述2,8-二溴并四苯在制备式(I)所示2,8-双取代的并四苯类衍生物中的应用。The present invention also provides the application of the 2,8-dibromotetracene described above in the preparation of the 2,8-disubstituted naphthacene derivatives represented by formula (I).
本发明还提供式(I)所示2,8-双取代的并四苯类衍生物的制备方法，包括如下步骤：The present invention also provides a preparation method of 2,8-disubstituted naphthacene derivatives represented by formula (I), which comprises the following steps:
2,8-二溴并四苯与化合物X-R反应得到式(I)所示2,8-双取代的并四苯类衍生物，2,8-Dibromotetracene reacts with compound X-R to obtain 2,8-disubstituted tetracene derivatives represented by formula (I),
Figure PCTCN2020123012-appb-000009
Figure PCTCN2020123012-appb-000009
其中，R具有如上所述的定义，X选自离去基团，2,8-二溴并四苯优选采用如上方法制备。Wherein, R has the above-mentioned definition, X is selected from a leaving group, and 2,8-dibromotetracene is preferably prepared by the above method.
根据本发明的实施方案，X选自卤素、硼酸、硼酸酯、烷基锡、烷基硅、镁、锌等。According to an embodiment of the present invention, X is selected from halogen, boric acid, boric acid ester, alkyl tin, alkyl silicon, magnesium, zinc, and the like.
根据本发明的实施方案，所述反应为下列反应：Suzuki反应、Stille反应、Heck反应、Sonogashira反应、Hiyama反应、Kumada反应、Negishi反应、Glaser-Eglinton反应、Claisen-Schmidt反应、Buchwald-Hartwig反应。According to an embodiment of the present invention, the reaction is the following reactions: Suzuki reaction, Stille reaction, Heck reaction, Sonogashira reaction, Hiyama reaction, Kumada reaction, Negishi reaction, Glaser-Eglinton reaction, Claisen-Schmidt reaction, Buchwald-Hartwig reaction.
根据本发明的实施方案，所述反应在钯络合物或者钯盐和膦配体组成的催化体系存在下进行；According to an embodiment of the present invention, the reaction is carried out in the presence of a catalytic system composed of a palladium complex or a palladium salt and a phosphine ligand;
所述钯络合物是指四(三苯基膦)钯、二氯二(三苯基膦)钯、二氯二(烯丙基)钯、三(二亚苄基丙酮)二钯、1,1'-双(二苯基膦基)二茂铁]二氯化钯、1,1'-双(二苯基膦基)二茂铁]二氯化钯二氯甲烷络合物或其他等适用于Suzuki反应的钯络合物；The palladium complex refers to tetrakis (triphenylphosphine) palladium, dichlorodi (triphenylphosphine) palladium, dichlorodi (allyl) palladium, tris (dibenzylidene acetone) palladium, 1 ,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex or others Palladium complexes suitable for Suzuki reaction;
所述钯盐是指醋酸钯、三氟醋酸钯、氯化钯、乙酰丙酮钯等适用于Suzuki反应的钯金属盐；The palladium salt refers to palladium metal salts suitable for Suzuki reaction such as palladium acetate, palladium trifluoroacetate, palladium chloride, palladium acetylacetonate, etc.;
所述膦配体是指三苯基膦、三环己基膦、AmPhos、MePhos、TrippyPhos、SPhos、tBuXPhos、XPhos、QPhos、RuPhos、DPEPhos、XantPhos、BINAP、DPPF、DPPP、DTBPF、DPPBZ、vBRIDP、cBRIDP等适用于Suzuki反应的膦配体。The phosphine ligand refers to triphenylphosphine, tricyclohexylphosphine, AmPhos, MePhos, TrippyPhos, SPhos, tBuXPhos, XPhos, QPhos, RuPhos, DPEPhos, XantPhos, BINAP, DPPF, DPPP, DTBPF, DPPBZ, vBRIDP, cBRIDP Such as phosphine ligands suitable for Suzuki reaction.
根据本发明的实施方案，式(I)所示2,8-双取代的并四苯类衍生物的制备方法进一步包括如上所述2,8-二溴并四苯的制备方法。According to an embodiment of the present invention, the preparation method of the 2,8-disubstituted naphthacene derivative represented by formula (I) further includes the preparation method of 2,8-dibromotetracene as described above.
本发明还提供式(I)所示2,8-双取代的并四苯类衍生物的用途，其用于制备有机半导体器件，电子学器件、电致发光器件、生物传感器件、光子学器件或有机自旋器件等方面及其相关领域。The present invention also provides the use of 2,8-disubstituted naphthacene derivatives represented by formula (I), which are used to prepare organic semiconductor devices, electronic devices, electroluminescence devices, biosensor devices, and photonic devices Or organic spin devices and related fields.
根据本发明的实施方案，所述有机半导体器件选自有机场效应晶体管OFETs和基于有机场效应晶体管的光电器件。According to an embodiment of the present invention, the organic semiconductor device is selected from organic field effect transistor OFETs and optoelectronic devices based on organic field effect transistors.
根据本发明的实施方案，所述有机半导体器件的有机半导体层中包括式(I)所示2,8-双取代的并四苯类衍生物。According to an embodiment of the present invention, the organic semiconductor layer of the organic semiconductor device includes a 2,8-disubstituted naphthacene derivative represented by formula (I).
有益效果Beneficial effect
本发明提供了一类2,8-双取代的并四苯类衍生物，该类化合物具有6个及以上的稠环共轭结构特征，但是由于其共轭结构中碳-碳单键的自由旋转特性，使得该类材料具有许多独特特性：一方面该类化合物可避免传统平面共轭稠环多并苯类材料(如并五苯，并六苯)稳定性极差的问题，表现出良好的光稳定性和器件稳定性，常规条件下2,8-蒽衍生并四苯在稀溶液中的光稳定性超过2天(预测可以更长，相关的稳定性测试还在继续跟踪测试中)2小时，远超过并五苯的和并六苯的等稠环体系的稳定性；另一方面这种高度稠环的共轭结构特征为获得更为优异光电性能提供了可能，譬如该类材料具有更为优异的载流子传输性能，更长波段的光谱吸收及发射特性，其发射光谱在550nm以上，通过共轭体系调整，有望实现更长波段红光和近红外光的发射，预示在更多领域的应用前景；同时该类化合物还可避免传统并四苯、并五苯、并六苯和红荧烯等并稠环材料体系荧光猝灭严重的特性，表现了更为优异发射光谱，即便在晶体状态下，仍能展现强和亮的荧光发射特性。此外，从加工工艺方面来讲，该化合物材料还表现出来了优异的成膜特性，通过不同基底的修饰，其薄膜的结晶性能可有效提到，且具有优异的分子排列方式，非常有利于高性能光电器件的获得。这些优异的光电性能预示该类材料可用于电子学器件、电致发光器件，生物传感器件、光子学器件等方面。由上述并四苯类衍生物制备的单晶和薄膜展现了明显的发光特性，基于该类材料构筑的晶体管器件的迁移率、阈值电压和开关比均较高，同时器件还展现了优异的光电响应特性，具有高的响应比以及磁场的响应特性，预示其在有机自旋器件方面也具有很好的应用价值。The present invention provides a class of 2,8-disubstituted naphthacene derivatives. This class of compounds has 6 or more condensed ring conjugated structure features, but due to the free carbon-carbon single bond in its conjugated structure Rotational characteristics make this type of material have many unique characteristics: On the one hand, this type of compound can avoid the problem of poor stability of traditional planar conjugated fused ring polyacene materials (such as pentacene and hexacene) and perform well. Light stability and device stability, the light stability of 2,8-anthracene-derived naphthacene in dilute solution under normal conditions is more than 2 days (prediction can be longer, the related stability test is still continuing to follow up the test) 2 hours, far exceeding the stability of pentacene and hexacene fused ring systems; on the other hand, this highly fused ring conjugated structure feature provides the possibility to obtain more excellent photoelectric properties, such as this type of material It has more excellent carrier transmission performance, longer-band spectral absorption and emission characteristics, and its emission spectrum is above 550nm. Through the adjustment of the conjugate system, it is expected to achieve longer-band red light and near-infrared light emission. Application prospects in more fields; at the same time, this type of compound can avoid the serious fluorescence quenching characteristics of traditional tetracene, pentacene, hexacene and rubrene and other condensed ring material systems, and show more excellent emission spectra. , Even in the crystal state, it can still exhibit strong and bright fluorescence emission characteristics. In addition, from the aspect of processing technology, the compound material also exhibits excellent film-forming characteristics. Through the modification of different substrates, the crystalline properties of the film can be effectively mentioned, and it has excellent molecular arrangement, which is very conducive to high Obtaining performance optoelectronic devices. These excellent photoelectric properties indicate that such materials can be used in electronic devices, electroluminescent devices, biosensing devices, photonics devices and so on. Single crystals and thin films prepared from the above-mentioned naphthacene derivatives exhibit obvious light-emitting characteristics. Transistor devices constructed based on such materials have high mobility, threshold voltage, and switching ratio. At the same time, the devices also exhibit excellent photoelectric properties. The response characteristics, high response ratio and magnetic field response characteristics indicate that it also has good application value in organic spin devices.
此外，本发明采用的制备路线简单，易于合成得到多种不同类型取代的并四苯类衍生物，通过大幅度提高2,8-二溴并四苯的收率，减少中间体的后处理步骤，提高合成效率，缩短制备时间，成本相对较低，合成路线的总收率达到了～50％，非常适合实验室的放量制备。In addition, the preparation route adopted by the present invention is simple, and it is easy to synthesize and obtain various types of substituted naphthacene derivatives. By greatly improving the yield of 2,8-dibromotetracene, the post-processing steps of intermediates are reduced. , Improve the synthesis efficiency, shorten the preparation time, and the cost is relatively low. The total yield of the synthesis route reaches ~50%, which is very suitable for the laboratory's high-volume preparation.
术语定义和说明Definition and description of terms
本申请说明书和权利要求书记载“更多个”表示三个或三个以上。The description of "more" in the specification and claims of this application means three or more.
术语“卤素”指F、Cl、Br和I。换言之，F、Cl、Br和I在本说明书中可描述为“卤素”。The term "halogen" refers to F, Cl, Br, and I. In other words, F, Cl, Br, and I can be described as "halogen" in this specification.
术语“C 1-40烷基”应理解为表示具有1～40个碳原子的直链或支链饱和一价烃基，优选为C 1-10烷基。“C 1-10烷基”应理解为优选表示具有1、2、3、4、5、6、7、8、9或10个碳原子的直链或支链饱和一价烃基。所述烷基是例如甲基、乙基、丙基、丁基、戊基、己基、异丙基、异丁基、仲丁基、叔丁基、异戊基、2-甲基丁基、1-甲基丁基、1-乙基丙基、1,2-二甲基丙基、新戊基、1,1-二甲基丙基、4-甲基戊基、3-甲基戊基、2-甲基戊基、1-甲基戊基、2-乙基丁基、1-乙基丁基、3,3-二甲基丁基、2,2-二甲基丁基、1,1-二甲基丁基、2,3-二甲基丁基、1,3-二甲基丁基或1,2-二甲基丁基等或它们的异构体。特别地，所述基团具有1、2、3、4、5、6、个碳原子(“C 1-6烷基”)，例如甲基、乙基、丙基、丁基、异丙基、异丁基、仲丁基、叔丁基，更特别地，所述基团具有1、2或3个碳原子(“C 1-3烷基”)，例如甲基、乙基、正丙基或异丙基。 The term "C 1-40 alkyl" should be understood to mean a linear or branched saturated monovalent hydrocarbon group having 1 to 40 carbon atoms, preferably a C 1-10 alkyl group. "C 1-10 alkyl" should be understood to preferably mean a linear or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl Group, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2-dimethylbutyl, etc. or their isomers. In particular, the group has 1, 2, 3, 4, 5, 6, carbon atoms ("C 1-6 alkyl"), such as methyl, ethyl, propyl, butyl, isopropyl , Isobutyl, sec-butyl, tert-butyl, more specifically, the group has 1, 2 or 3 carbon atoms ("C 1-3 alkyl"), such as methyl, ethyl, n-propyl基 or isopropyl.
术语“C 1-40烷基”指C 1-40烷基-O-，其中C 1-40烷基具有如上所述的定义。 The term "C 1-40 alkyl" refers to C 1-40 alkyl-O-, where C 1-40 alkyl has the definition as described above.
本发明使用的术语“C 3-20环烷基”意指饱和的烃环，其可包括稠合或桥接的多环***。环烷基在其环结构中优选具有3至12个碳原子。优选地，环烷基在其环结构中具有3、4、5或6个碳原子。例如，“C 3-6环烷基”表 示例如环丙基、环丁基、环戊基或环己基的基团。 The term "C 3-20 cycloalkyl" used in the present invention means a saturated hydrocarbon ring, which may include a fused or bridged polycyclic ring system. The cycloalkyl group preferably has 3 to 12 carbon atoms in its ring structure. Preferably, the cycloalkyl group has 3, 4, 5 or 6 carbon atoms in its ring structure. For example, "C 3-6 cycloalkyl" means a group such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
术语“3-20元杂环基”意指饱和的一价单环或双环烃环，其包含1-5个独立选自N、O和S的杂原子，优选“3-10元杂环基”。术语“3-10元杂环基”意指饱和的一价单环或双环烃环，其包含1-5个，优选1-3个选自N、O和S的杂原子。所述杂环基可以通过所述碳原子中的任一个或氮原子(如果存在的话)与分子的其余部分连接。特别地，所述杂环基可以包括但不限于：4元环，如氮杂环丁烷基、氧杂环丁烷基；5元环，如四氢呋喃基、二氧杂环戊烯基、吡咯烷基、咪唑烷基、吡唑烷基、吡咯啉基；或6元环，如四氢吡喃基、哌啶基、吗啉基、二噻烷基、硫代吗啉基、哌嗪基或三噻烷基；或7元环，如二氮杂环庚烷基。任选地，所述杂环基可以是苯并稠合的。所述杂环基可以是双环的，例如但不限于5,5元环，如六氢环戊并[c]吡咯-2(1H)-基环，或者5,6元双环，如六氢吡咯并[1,2-a]吡嗪-2(1H)-基环。含氮原子的环可以是部分不饱和的，即它可以包含一个或多个双键，例如但不限于2,5-二氢-1H-吡咯基、4H-[1,3,4]噻二嗪基、4,5-二氢噁唑基或4H-[1,4]噻嗪基，或者，它可以是苯并稠合的，例如但不限于二氢异喹啉基。根据本发明，所述杂环基是无芳香性的。The term "3-20 membered heterocyclic group" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O and S, preferably "3-10 membered heterocyclic group" ". The term "3-10 membered heterocyclic group" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclic group may be connected to the rest of the molecule through any of the carbon atoms or the nitrogen atom (if present). In particular, the heterocyclic group may include but is not limited to: 4-membered ring, such as azetidinyl, oxetanyl; 5-membered ring, such as tetrahydrofuranyl, dioxolyl, pyrrole Alkyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or 6-membered ring, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithiaalkyl, thiomorpholinyl, piperazinyl Or trithiaalkyl; or 7-membered ring, such as diazeppanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, such as but not limited to a 5, 5-membered ring, such as hexahydrocyclopenta[c]pyrrole-2(1H)-yl ring, or a 5, 6-membered bicyclic ring, such as hexahydropyrrole And [1,2-a]pyrazine-2(1H)-yl ring. The ring containing the nitrogen atom may be partially unsaturated, that is, it may contain one or more double bonds, such as but not limited to 2,5-dihydro-1H-pyrrolyl, 4H-[1,3,4]thiadi Azinyl, 4,5-dihydrooxazolyl or 4H-[1,4]thiazinyl, or it may be benzo-fused, such as but not limited to dihydroisoquinolinyl. According to the present invention, the heterocyclic group is non-aromatic.
术语“C 6-20芳基”应理解为表示具有6～20个碳原子的一价芳香性或部分芳香性的单环、双环或三环烃环，优选“C 6-14芳基”。术语“C 6-14芳基”应理解为优选表示具有6、7、8、9、10、11、12、13或14个碳原子的一价芳香性或部分芳香性的单环、双环或三环烃环(“C 6-14芳基”)，特别是具有6个碳原子的环(“C 6芳基”)，例如苯基；或联苯基，或者是具有9个碳原子的环(“C 9芳基”)，例如茚满基或茚基，或者是具有10个碳原子的环(“C 10芳基”)，例如四氢化萘基、二氢萘基或萘基，或者是具有13个碳原子的环(“C 13芳基”)，例如芴基，或者是具有14个碳原子的环(“C 14芳基”)，例如蒽基。 The term "C 6-20 aryl" should be understood to mean a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring with 6 to 20 carbon atoms, preferably "C 6-14 aryl". The term "C 6-14 aryl" should be understood as preferably meaning a monocyclic, bicyclic or partially aromatic monocyclic or partially aromatic monocyclic or partially aromatic having 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms A tricyclic hydrocarbon ring ("C 6-14 aryl"), especially a ring having 6 carbon atoms ("C 6 aryl"), such as phenyl; or biphenyl, or one having 9 carbon atoms Ring ("C 9 aryl"), such as indanyl or indenyl, or a ring with 10 carbon atoms ("C 10 aryl"), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, Either a ring having 13 carbon atoms ("C 13 aryl"), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl"), such as anthracenyl.
术语“5-20元杂芳基”应理解为包括这样的一价单环、双环或三环芳族环系：其具有5～20个环原子且包含1-5个独立选自N、O和S的杂原子，例如“5-14元杂芳基”。术语“5-14元杂芳基”应理解为包括这样的一价单环、双环或三环芳族环系：其具有5、6、7、8、9、10、11、12、13或14个环原子，特别是5或6或9或10个碳原子，且其包含1-5个，优选1-3各独立选自N、O和S的杂原子并且，另外在每一种情况下可为苯并稠合的。特别地，杂芳基选自噻吩基、呋喃基、吡咯基、噁唑基、噻唑基、咪唑基、吡唑基、异噁唑基、异噻唑基、噁二唑基、***基、噻二唑基、噻-4H-吡唑基等以及它们的苯并衍生物，例如苯并呋喃基、苯并噻吩基、苯并噁唑基、苯并异噁唑基、苯并咪唑基、苯并***基、吲唑基、吲哚基、异吲哚基等；或吡啶基、哒嗪基、嘧啶基、吡嗪基、三嗪基等，以及它们的苯并衍生物，例如喹啉基、喹唑啉基、异喹啉基等；或吖辛因基、吲嗪基、嘌呤基等以及它们的苯并衍生物；或噌啉基、酞嗪基、喹唑啉基、喹喔啉基、萘啶基、蝶啶基、咔唑基、吖啶基、吩嗪基、吩噻嗪基、吩噁嗪基等。The term "5-20 membered heteroaryl" should be understood to include such a monovalent monocyclic, bicyclic or tricyclic aromatic ring system which has 5-20 ring atoms and contains 1-5 independently selected from N, O And S heteroatoms, for example "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" should be understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, especially 5 or 6 or 9 or 10 carbon atoms, and it contains 1-5, preferably 1-3 heteroatoms each independently selected from N, O and S and, additionally in each case The bottom can be benzo-fused. In particular, the heteroaryl group is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiol Diazolyl, thio-4H-pyrazolyl, etc. and their benzo derivatives, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzene O-triazolyl, indazolyl, indolyl, isoindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc., and their benzo derivatives, such as quinoline Group, quinazolinyl, isoquinolinyl, etc.; or azecinyl, indazinyl, purinyl, etc. and their benzo derivatives; or cinolinyl, phthalazinyl, quinazolinyl, quinoxa Linyl, naphthyridinyl, pterridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, etc.
除非另有说明，杂环基、杂芳基或亚杂芳基包括其所有可能的异构形式，例如其位置异构体。因此，对于一些说明性的非限制性实例，吡啶基或亚吡啶基包括吡啶-2-基、亚吡啶-2-基、吡啶-3-基、亚吡啶-3-基、吡啶-4-基和亚吡啶-4-基；噻吩基或亚噻吩基包括噻吩-2-基、亚噻吩-2-基、噻吩-3-基和亚噻吩-3-基。Unless otherwise specified, heterocyclic group, heteroaryl group or heteroarylene group includes all possible isomeric forms thereof, such as positional isomers thereof. Therefore, for some illustrative non-limiting examples, pyridinyl or pyridinylene includes pyridin-2-yl, pyridin-2-yl, pyridin-3-yl, pyridin-3-yl, pyridin-4-yl And pyridin-4-yl; thienyl or thienylene includes thiophen-2-yl, thiophen-2-yl, thiophen-3-yl, and thiophen-3-yl.
附图说明Description of the drawings
图1为物理气相传输提纯化合物时使用的设备，其中A为蒸发段；B为沉积区；Figure 1 shows the equipment used in physical vapor transport to purify compounds, where A is the evaporation section; B is the deposition zone;
图2为实施例4和5制备的器件的结构图；Figure 2 is a structural diagram of the devices prepared in Examples 4 and 5;
图3为式2所示的并四苯的苯衍生物的薄膜器件图；3 is a diagram of a thin film device of the benzene derivative of naphthacene shown in formula 2;
图4为式2所示的并四苯的苯衍生物的薄膜输出曲线图；4 is a graph showing the output curve of the film of the benzene derivative of naphthacene shown in formula 2;
图5为式5所示的并四苯的噻吩衍生物的转移和输出曲线图；Fig. 5 is a graph showing the transfer and output of the thiophene derivative of naphthacene shown in formula 5;
图6为式5所示的并四苯的噻吩衍生物的薄膜器件的AFM图谱；Fig. 6 is an AFM spectrum of the thin film device of the thiophene derivative of naphthacene shown in formula 5;
图7为式6所示的并四苯的呋喃衍生物薄膜器件的转移图；Fig. 7 is a transfer diagram of the naphthacene furan derivative thin film device shown in formula 6;
图8为式6所示的并四苯的呋喃衍生物薄膜器件的输出曲线；Fig. 8 is an output curve of the naphthacene furan derivative thin film device shown in formula 6;
图9中左图为式6所示的并四苯的呋喃衍生物的紫外吸收光谱图；右图为式5所示的并四苯的呋喃衍生物 的紫外吸收光谱图；The left picture in FIG. 9 is the ultraviolet absorption spectrum of the furan derivative of naphthacene shown in formula 6; the right picture is the ultraviolet absorption spectrum of the furan derivative of naphthacene shown in formula 5;
图10为式2所示的并四苯的苯衍生物单晶器件转移曲线；FIG. 10 is a transfer curve of a single crystal device of a naphthacene derivative represented by formula 2;
图11为式2所示的并四苯的苯衍生物单晶器件输出曲线；FIG. 11 is an output curve of a single crystal device of a naphthacene derivative shown in formula 2;
图12为式2所示的并四苯的苯衍生物(DPT)薄膜器件原子力扫描显微镜图；FIG. 12 is an atomic force scanning microscope image of a tetracene derivative (DPT) thin film device shown in formula 2;
图13为式2所示的并四苯的苯衍生物的X射线衍射图；Figure 13 is an X-ray diffraction diagram of the benzene derivative of naphthacene represented by formula 2;
图14为式2所示的并四苯的苯衍生物的紫外光电子能谱图；Fig. 14 is an ultraviolet photoelectron spectrogram of the benzene derivative of naphthacene shown in formula 2;
图15为式2所示的并四苯的苯衍生物的紫外和荧光光谱图；FIG. 15 is an ultraviolet and fluorescence spectrum diagram of the benzene derivative of naphthacene shown in formula 2;
图16为式2所示的并四苯的苯衍生物制备的单晶器件的显微镜实拍图；16 is a real microscope photograph of a single crystal device prepared by the benzene derivative of naphthacene shown in formula 2;
图17为式6所示的并四苯的呋喃衍生物的单晶转移图；Figure 17 is a single crystal transfer diagram of the furan derivative of naphthacene represented by formula 6;
图18为式6所示的并四苯的呋喃衍生物的输出曲线图；18 is a graph showing the output curve of the furan derivative of naphthacene shown in formula 6;
图19为式2所示的并四苯的苯衍生物的单晶器件图。FIG. 19 is a diagram of a single crystal device of the benzene derivative of naphthacene represented by Formula 2. FIG.
图20为式2所示的并四苯的苯衍生物溶液稳定性测试结果。20 is a test result of the stability of the solution of the benzene derivative of naphthacene represented by Formula 2.
图21为式2所示的并四苯的苯衍生物单晶晶体管器件连续工作的稳定性数据。FIG. 21 is the stability data of continuous operation of the single crystal transistor device of naphthacene derivative represented by formula 2. FIG.
图22为式2所示的并四苯的苯衍生物材料的成膜特性研究。FIG. 22 is a study on the film-forming characteristics of the benzene derivative material of naphthacene represented by Formula 2. FIG.
图23为式4(左)和5(右)所示的并四苯的苯衍生物材料的成膜特性研究Figure 23 shows the film-forming characteristics of the benzene derivative materials of naphthacene represented by formulas 4 (left) and 5 (right)
图24为式2所示的并四苯的苯衍生物材料结构数据(a)单晶模拟XRD衍射数据(下)和所得晶态才来的XRD实验数据，(b)单晶堆积模式数据图，表明该材料展现了典型的herringbone堆积模式。Figure 24 shows the structure data of the benzene derivative of naphthacene shown in formula 2 (a) single crystal simulated XRD diffraction data (bottom) and XRD experimental data from the obtained crystalline state, (b) single crystal packing mode data graph , Indicating that the material exhibits a typical herringbone accumulation pattern.
图25为式2所示的并四苯的苯衍生物材料在PMMA中的明场照片和紫外下荧光照片。Fig. 25 is a bright-field photograph and ultraviolet fluorescence photograph of the benzene derivative material of naphthacene shown in Formula 2 in PMMA.
图26为式2所示的并四苯的苯衍生物材料发光性能数据图(不同激发波长下分别发射棕黄(激发波长425nm)、亮黄(激发波长515nm)和红色(激发波长590nm)光)。图27为式2所示的并四苯的苯衍生物光电器件性能测试图。Figure 26 is a data diagram of the luminescence performance of the benzene derivative material of naphthacene shown in formula 2 (emission of brown yellow (excitation wavelength 425nm), bright yellow (excitation wavelength 515nm) and red (excitation wavelength 590nm) light at different excitation wavelengths, respectively ). FIG. 27 is a performance test diagram of a photoelectric device of a benzene derivative of naphthacene shown in formula 2. FIG.
具体实施方式Detailed ways
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The technical solution of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only illustrative and explanation of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the foregoing contents of the present invention are covered by the scope of the present invention.
本发明化合物的实施方式在实施例中具体详述，这些化合物可单独使用或与其它化合物组合用于本发明的所有目的。The embodiments of the compounds of the present invention are specifically detailed in the examples, and these compounds can be used alone or in combination with other compounds for all purposes of the present invention.
本发明提供了高效制备2,8-二溴并四苯的合成路线。式(I)所示的化合物使用2,8-二溴并四苯与化合物R-X反应制备。The invention provides a synthetic route for efficiently preparing 2,8-dibromotetracene. The compound represented by formula (I) is prepared by reacting 2,8-dibromotetracene with compound R-X.
合适的化合物R-X在许多情况下可以通过市场购得，并且实施例中详述的起始化合物可通过已知方法获得，因此可参考这些信息。Suitable compounds R-X are commercially available in many cases, and the starting compounds detailed in the examples can be obtained by known methods, so this information can be referred to.
这些化合物可以通过已知的偶联反应与其它芳基化合物反应，为此目的的必要条件是本领域技术人员已知的，并且实施例中的详细说明为本领域技术人员实施这些反应给予支持。These compounds can be reacted with other aryl compounds through known coupling reactions. The necessary conditions for this purpose are known to those skilled in the art, and the detailed description in the examples provides support for those skilled in the art to implement these reactions.
在所有后面的合成方案中，化合物用少量取代基显示以简化结构，但这并不排除在过程中存在任何所需的其它取代基。In all the following synthetic schemes, the compounds are shown with a small number of substituents to simplify the structure, but this does not exclude the presence of any other desired substituents in the process.
下面的方案给出了一个示例性的实施方案，而没有任何意图对这些方案施加限制。各个方案的组成步骤可以根据需要相互组合。The following schemes give an exemplary embodiment without any intention to impose restrictions on these schemes. The constituent steps of each scheme can be combined with each other as required.
用于合成本发明化合物的所示方法应该作为实例来理解。本领域技术人员将能够在本领域的普通知识范围内开发替代的合成路线。The shown methods for synthesizing the compounds of the present invention should be understood as examples. Those skilled in the art will be able to develop alternative synthetic routes within the scope of ordinary knowledge in the field.
Figure PCTCN2020123012-appb-000010
Figure PCTCN2020123012-appb-000010
其中，X是离去基团，例如X选自D、NMe 2、卤素、硼酸、硼酸酯、烷基锡、烷基硅、镁、锌等。 Wherein, X is a leaving group, for example, X is selected from D, NMe 2 , halogen, boric acid, boric acid ester, alkyl tin, silicon alkyl, magnesium, zinc and the like.
化合物2,8-二溴并四苯，制备方法包括下述步骤：The compound 2,8-dibromotetracene, the preparation method includes the following steps:
1)将化合物2-氨基-5-溴苯甲酸，一种酸1和亚硝酸类化合物置于溶剂1中，在低温下进行反应0.1～300h，待大量有机重氮盐析出，加入***后再搅拌0.1～300h后过滤。将滤出的有机重氮盐收集，与呋喃共同置于另一种溶剂2中，加热回流0.1～300h后，待溶液澄清结束反应。经后处理得到产物6-溴-1,4-环氧-1,4-二氢萘。1) Put the compound 2-amino-5-bromobenzoic acid, an acid 1 and nitrous acid compounds in solvent 1, and carry out the reaction at low temperature for 0.1～300h. After a large amount of organic diazonium salt is deposited, add ether and then After stirring for 0.1-300h, filter. Collect the filtered organic diazonium salt, put it in another solvent 2 together with furan, heat to reflux for 0.1-300h, wait until the solution is clear to complete the reaction. After post-treatment, the product 6-bromo-1,4-epoxy-1,4-dihydronaphthalene is obtained.
2)将化合物6-溴-1,4-环氧-1,4-二氢萘，4-溴苯并环丁烷以及一种添加剂1置于溶剂3中，加热回流0.1～300h后结束反应。经后处理得到产物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯，产率在1～99％。2) The compound 6-bromo-1,4-epoxy-1,4-dihydronaphthalene, 4-bromobenzocyclobutane and an additive 1 are placed in solvent 3, and the reaction is terminated after heating and refluxing for 0.1～300h . After post-treatment, the product 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene, is obtained, and the yield is 1-99%.
3)将化合物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯和一种酸2置于溶剂4中，加热回流0.1～300h后结束反应。将反应后的溶液依次经过去离子水清洗，萃取分液并在减压下除去溶剂，初步得到一种混合物。不需分离提纯，直接将该混合物与一种添加剂2在溶剂5中加热回流0.1～300h后结束反应。经后处理得到2,8-二溴并四苯。3) Put the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and an acid 2 in solvent 4, and heat to reflux for 0.1～ The reaction was terminated after 300h. The reacted solution was washed with deionized water successively, extracted and separated, and the solvent was removed under reduced pressure to initially obtain a mixture. Without separation and purification, the mixture and an additive 2 are directly heated and refluxed in the solvent 5 for 0.1 to 300 hours, and then the reaction is completed. After post-treatment, 2,8-dibromotetracene was obtained.
上述步骤1)中，所述酸1可以为盐酸、硫酸、磷酸、三氟化硼、五氟化磷等无机酸，具体可为盐酸或三氟化硼；所述亚硝酸类化合物可以为亚硝酸叔丁酯、亚硝酸异戊酯、亚硝酸钠、亚硝酸钾等化合物，具体可为亚硝酸异戊酯；所述溶剂1可以为甲醇、乙醇、丙醇、异丙醇、丁醇、乙二醇单甲醚等醇类溶剂，具体可为乙醇或乙二醇单甲醚；所述溶剂2可以为***、甲基异丙基醚、二异丙基醚、丁醚、乙二醇二甲醚、四氢呋喃、二噁烷等醚类溶剂，或者可以为苯、甲苯、二甲苯、氯苯、氟苯、溴苯、氯萘等芳烃类溶剂，或者可以为氯仿、二氯甲烷、二氯乙烷、三氯乙烷、二溴乙烷、十二烷、十六烷等烷烃类溶剂，综合考虑三种溶剂，具体可为四氢呋喃或氯苯或二氯乙烷；所述化合物2-氨基-5-溴苯甲酸，酸1和亚硝酸类化合物的摩尔比为1:(0.01～100):(0.01～100)，具体可为1:1:1或1:2:3；所述呋喃和起始原料2-氨基-5-溴苯甲酸的摩尔比为1:(0.01～100)，具体可为1:1或1:0.2；所述低温的范围是–200～10℃，具体可为–10℃或1℃；所述加热回流是指加热温度接近或高于该反应溶剂在常压下的沸点，温度范围可以是30～1000℃，并且除了高压反应釜以外，反应器具可能需要搭载回流装置；所述后处理是指包含过滤、水洗、中和、萃取、盐洗、分液、吸附柱、柱色谱、重结晶、升华等本领域技术人员熟知的基本有机实验操作。In the above step 1), the acid 1 can be an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, boron trifluoride, phosphorus pentafluoride, etc., specifically it can be hydrochloric acid or boron trifluoride; the nitrous acid compound can be Compounds such as tert-butyl nitrate, isoamyl nitrite, sodium nitrite, potassium nitrite, etc., specifically may be isoamyl nitrite; the solvent 1 may be methanol, ethanol, propanol, isopropanol, butanol, Alcoholic solvents such as ethylene glycol monomethyl ether, specifically ethanol or ethylene glycol monomethyl ether; the solvent 2 can be ethyl ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol Ether solvents such as dimethyl ether, tetrahydrofuran, dioxane, etc., or aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, etc., or chloroform, dichloromethane, dioxane, etc. Alkane solvents such as chloroethane, trichloroethane, dibromoethane, dodecane, hexadecane, etc., considering the three solvents, specifically tetrahydrofuran or chlorobenzene or dichloroethane; the compound 2- The molar ratio of amino-5-bromobenzoic acid, acid 1 and nitrous acid compound is 1:(0.01-100):(0.01-100), specifically it can be 1:1:1 or 1:2:3; The molar ratio of furan to the starting material 2-amino-5-bromobenzoic acid is 1: (0.01-100), specifically 1:1 or 1:0.2; the low temperature range is -200-10°C, specifically It can be -10°C or 1°C; the heating reflux means that the heating temperature is close to or higher than the boiling point of the reaction solvent under normal pressure, and the temperature range can be 30-1000°C, and in addition to the autoclave, the reaction vessel may It needs to be equipped with a reflux device; the post-treatment refers to basic organic experimental operations well-known to those skilled in the art, such as filtration, water washing, neutralization, extraction, salt washing, liquid separation, adsorption column, column chromatography, recrystallization, and sublimation.
上述步骤2)中，所述添加剂1可以为碳酸钾、碳酸氢钾、碳酸钠、碳酸氢钠、醋酸钾、醋酸钠、柠檬酸钠等弱碱，具体可为碳酸钠或醋酸钾；所述溶剂3可以为***、甲基异丙基醚、二异丙基醚、丁醚、乙二醇二甲醚、四氢呋喃、二噁烷等醚类溶剂，或者可以为苯、甲苯、二甲苯、氯苯、氟苯、溴苯、氯萘等芳烃类溶剂，或者可以为氯仿、二氯甲烷、二氯乙烷、三氯乙烷、二溴乙烷、十二烷、十六烷等烷烃类溶剂，综合考虑三种溶剂，具体可为异戊醚或二氯苯或十二烷；所述化合物6-溴-1,4-环氧-1,4-二氢萘，4-溴苯并环丁烷和添加剂1的摩尔比为1:(0.01～100):(0.01～100)，具体可为1:0.9:0.3或1:1.1:0.2；所述加热回流和后处理都如步骤1)中所述。In the above step 2), the additive 1 can be a weak base such as potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, potassium acetate, sodium acetate, sodium citrate, etc., specifically sodium carbonate or potassium acetate; Solvent 3 can be ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and other ether solvents, or it can be benzene, toluene, xylene, chlorine Aromatic solvents such as benzene, fluorobenzene, bromobenzene, and chloronaphthalene, or alkane solvents such as chloroform, dichloromethane, dichloroethane, trichloroethane, dibromoethane, dodecane, hexadecane, etc. , Comprehensive consideration of three solvents, specifically isoamyl ether or dichlorobenzene or dodecane; the compound 6-bromo-1,4-epoxy-1,4-dihydronaphthalene, 4-bromobenzo ring The molar ratio of butane to additive 1 is 1:(0.01-100):(0.01-100), specifically it can be 1:0.9:0.3 or 1:1.1:0.2; the heating reflux and post-treatment are as in step 1) As described in.
上述步骤3)中，所述酸2可以为盐酸、硫酸、磷酸等无机酸，也可以为醋酸、三氟醋酸、三氟甲磺酸、 对甲苯磺酸、吡啶对甲苯磺酸盐等有机酸，具体可为盐酸或对甲苯磺酸；所述溶剂4可以为***、甲基异丙基醚、二异丙基醚、丁醚、乙二醇二甲醚、四氢呋喃、二噁烷等醚类溶剂，或者可以为苯、甲苯、二甲苯、氯苯、氟苯、溴苯、氯萘等芳烃类溶剂，或者可以为氯仿、二氯甲烷、二氯乙烷、三氯乙烷、二溴乙烷、十二烷、十六烷等烷烃类溶剂，或者可以为醋酸酐、三氟甲磺酸酐、三氟醋酸酐等酸酐类溶剂，综合考虑四种溶剂，具体可为二噁烷或甲苯或二氯乙烷或醋酸酐；所述添加剂2可以为氧气、苯醌、四氯苯醌、二氯二氰基苯醌DDQ、三氯脲氰、溴、碘、溴代琥珀酰亚胺、碘代琥珀酰亚胺等氧化剂，也可以为活性碳、钯碳等催化剂，具体可为DDQ或钯碳；所述溶剂5可以为***、甲基异丙基醚、二异丙基醚、丁醚、乙二醇二甲醚、四氢呋喃、二噁烷等醚类溶剂，或者可以为苯、甲苯、二甲苯、氯苯、氟苯、溴苯、氯萘等芳烃类溶剂，或者可以为氯仿、二氯甲烷、二氯乙烷、三氯乙烷、二溴乙烷、十二烷、十六烷等烷烃类溶剂，综合考虑三种溶剂，具体可为乙二醇二甲醚或苯或四氯化碳；所述化合物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯和酸2的摩尔比为1:(0.01～100)，具体可为1:25或1:0.5；所述化合物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯和添加剂2的摩尔比为1:(0.01～100)，具体可为1:0.5或1:2；所述加热回流和后处理都如步骤1)中所述。In the above step 3), the acid 2 can be an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or an organic acid such as acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and pyridine p-toluenesulfonate. , Specifically may be hydrochloric acid or p-toluenesulfonic acid; the solvent 4 may be ethers such as ether, methyl isopropyl ether, diisopropyl ether, butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc. The solvent may be aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene, or it may be chloroform, methylene chloride, dichloroethane, trichloroethane, dibromoethane Alkane, dodecane, hexadecane and other alkane solvents, or acetic anhydride, trifluoromethanesulfonic anhydride, trifluoroacetic anhydride and other acid anhydride solvents, considering the four solvents, specifically dioxane or toluene or Dichloroethane or acetic anhydride; the additive 2 can be oxygen, benzoquinone, tetrachlorobenzoquinone, dichlorodicyanobenzoquinone DDQ, trichlorourea cyanide, bromine, iodine, bromosuccinimide, iodine The oxidant such as succinimide can also be activated carbon, palladium on carbon and other catalysts, specifically DDQ or palladium on carbon; the solvent 5 can be diethyl ether, methyl isopropyl ether, diisopropyl ether, butyl ether , Ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and other ether solvents, or can be benzene, toluene, xylene, chlorobenzene, fluorobenzene, bromobenzene, chloronaphthalene and other aromatic solvents, or can be chloroform, dioxane, etc. Alkane solvents such as methyl chloride, dichloroethane, trichloroethane, dibromoethane, dodecane, hexadecane, etc., considering the three solvents, specifically it can be ethylene glycol dimethyl ether or benzene or tetrachloride The molar ratio of the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and acid 2 is 1:(0.01～100 ), specifically 1:25 or 1:0.5; the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and additive 2 The molar ratio of is 1:(0.01-100), specifically it can be 1:0.5 or 1:2; the heating reflux and post-treatment are as described in step 1).
对于以上详述的制备方法的原理，原则上可以由相似化合物的参考文献所知，并且本领域技术人员可以容易地使所述方法用于本发明化合物的制备。更多信息可见于实施例中。The principle of the preparation method detailed above can in principle be known from the references of similar compounds, and those skilled in the art can easily apply the method to the preparation of the compound of the present invention. More information can be found in the examples.
如果需要，可以通过这些方法，接着进行纯化步骤(例如，重结晶或者升华)，可以获得高纯度、优选大于99％(通过核磁或元素分析测定)的包含结构通式(I)的本发明化合物。If necessary, these methods can be followed by purification steps (for example, recrystallization or sublimation) to obtain high purity, preferably greater than 99% (determined by nuclear magnetic or elemental analysis) of the compound of the present invention containing the general formula (I) .
本发明的化合物也可以与聚合物混合，甚至同样可能被共价结合到聚合物的分子骨架中。如利用反应性可离去基团(例如，氟、氯、溴、碘、硼酸、硼酸酯、锡烷、硅酯、硅烷等基团)或者反应性可聚合基团(例如，烯烃、炔烃、环氧丙烷、氧杂环丁烷等基团)来取代这些化合物，都是尤其可行的方法，所以，这些被反应性基团取代的化合物可以用作制备相应低聚物、树枝状大分子或聚合物的单体。低聚或聚合的优选经由卤素官能团、硼酸官能团、锡基官能团或硅基官能团，或者经由反应性可聚合基团来实现。另外也可以经由这些反应性基团来实现聚合物的交联。The compound of the present invention can also be mixed with a polymer, and it is even possible to be covalently bound to the molecular backbone of the polymer. For example, using reactive leaving groups (for example, fluorine, chlorine, bromine, iodine, boric acid, borate, stannane, silicon ester, silane, etc.) or reactive polymerizable groups (for example, alkene, alkyne, etc.) Hydrocarbon, propylene oxide, oxetane and other groups) are particularly feasible methods to replace these compounds. Therefore, these compounds substituted by reactive groups can be used to prepare corresponding oligomers and dendrimers. The monomer of a molecule or polymer. The oligomerization or polymerization is preferably achieved via a halogen functional group, a boric acid functional group, a tin-based functional group or a silicon-based functional group, or via a reactive polymerizable group. In addition, crosslinking of the polymer can also be achieved via these reactive groups.
除非另外说明，否则以下合成在保护性气体气氛和无水溶剂中进行。溶剂和试剂可从商业途径购自，例如，国药集团、J&K、Acros、Innochem、Alfa-aesar、Adamas-beta等化学试剂公司。对于文献已知的化合物，在每种情况下也酌情报道相应的文献出处和CAS号。Unless otherwise specified, the following synthesis was performed in a protective gas atmosphere and anhydrous solvent. Solvents and reagents can be purchased from commercial sources, for example, chemical reagent companies such as Sinopharm, J&K, Acros, Innochem, Alfa-aesar, Adamas-beta. For compounds known in the literature, the corresponding literature source and CAS number are also reported as appropriate in each case.
实施例1Example 1
a)6-溴-1,4-环氧-1,4-二氢萘a) 6-bromo-1,4-epoxy-1,4-dihydronaphthalene
Figure PCTCN2020123012-appb-000011
Figure PCTCN2020123012-appb-000011
在带有滴液漏斗的1000mL两口圆底烧瓶中，加入2-氨基-5-溴苯甲酸(63.5g，294mmol)和400mL乙醇，之后放进冷却浴中搅拌并降温至–10℃。往该两口圆底烧瓶中缓慢滴加盐酸(24.5mL，294mmol)并待固体完全溶解后，再缓慢往烧瓶中滴加亚硝酸异戊酯(35g，294mmol)。滴加过程中，溶液由黄色变为棕褐色并伴随少量气泡产生。反应一段时间后，溶液逐渐由澄清变为浑浊。此时加入500mL无水***，并继续在<10℃的温度下搅拌一段时间。反应结束，将圆底烧瓶小心超声后过滤，并用无水***(200mL)清洗固体三次，再将所得固体转移并投入到带有回流冷凝管的1000mL两口圆底烧瓶中。加入500mL无水二氯乙烷和重蒸后的新鲜呋喃(100g,1460mmol)后，将该两口圆底烧瓶加热到70℃并搅拌一段时间。待反应溶液澄清后，向该两口圆底烧瓶中加入100mL水和100mL二氯甲烷，萃取分液，保留有机相。用二氯甲烷(50mL)再清洗水相三次后，合并所有的有机相，并在减压下除去有机溶剂，得到棕红色液体。粗产品用200～400目硅胶柱色谱提纯(洗脱剂为石油醚和二氯甲烷)，最终可以得到亮红色透明液体产物(46g，产率69％)。经核磁数据和质谱 分析，与已知文献(J.Am.Chem.Soc.2011,133,19864)比对，该亮红色透明液体为高纯的6-溴-1,4-环氧-1,4-二氢萘。In a 1000 mL two-neck round bottom flask with a dropping funnel, add 2-amino-5-bromobenzoic acid (63.5 g, 294 mmol) and 400 mL ethanol, then put it in a cooling bath and stir and cool to -10°C. Slowly add hydrochloric acid (24.5 mL, 294 mmol) into the two-necked round bottom flask and slowly add isoamyl nitrite (35 g, 294 mmol) into the flask after the solid is completely dissolved. During the dripping process, the solution changed from yellow to brown with a small amount of air bubbles. After a period of reaction, the solution gradually changed from clear to turbid. Add 500 mL of anhydrous ether at this time, and continue to stir for a period of time at a temperature of <10°C. At the end of the reaction, the round bottom flask was carefully sonicated and filtered, and the solid was washed three times with anhydrous ether (200 mL), and then the obtained solid was transferred and put into a 1000 mL two-neck round bottom flask with a reflux condenser. After adding 500 mL of anhydrous dichloroethane and redistilled fresh furan (100 g, 1460 mmol), the two-neck round bottom flask was heated to 70° C. and stirred for a period of time. After the reaction solution was clarified, 100 mL of water and 100 mL of dichloromethane were added to the two-necked round bottom flask, and the extraction and liquid separation were performed, and the organic phase was retained. After washing the aqueous phase three more times with dichloromethane (50 mL), all the organic phases were combined, and the organic solvent was removed under reduced pressure to obtain a brown-red liquid. The crude product is purified by 200-400 mesh silica gel column chromatography (eluent is petroleum ether and dichloromethane), and finally a bright red transparent liquid product (46 g, yield 69%) can be obtained. After NMR data and mass spectrometry analysis, compared with known literature (J.Am.Chem.Soc.2011,133,19864), the bright red transparent liquid is high-purity 6-bromo-1,4-epoxy-1 ,4-Dihydronaphthalene.
b)2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯b) 2,8-Dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene
Figure PCTCN2020123012-appb-000012
Figure PCTCN2020123012-appb-000012
在带有回流冷凝管的250mL两口圆底烧瓶中，依次加入4-溴苯并环丁烷(33g，182mmol)，6-溴-1,4-环氧-1,4-二氢萘(46g，202mmol)、碳酸钠(6g，55mmol)和十二烷(100mL)后，搅拌并加热至温度220℃回流一段时间。待反应体系由亮红色变为深褐色后，停止加热并冷却至室温。用硅胶吸附柱减压分离固体，再用二氯甲烷(20mL)淋洗吸附柱三次。合并所有的有机相后，在减压下除去有机溶剂，得到棕红色液体。粗产品用200～400目硅胶柱色谱提纯(洗脱剂为石油醚和二氯甲烷)，最终可以得到红褐色液体产物(59g，产率80％)。经核磁数据和质谱分析，与已知文献(J.Am.Chem.Soc.2011,133,19864)比对，该红褐色液体为高纯的2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯。In a 250mL two-necked round bottom flask with a reflux condenser, add 4-bromobenzocyclobutane (33g, 182mmol), 6-bromo-1,4-epoxy-1,4-dihydronaphthalene (46g , 202mmol), sodium carbonate (6g, 55mmol) and dodecane (100mL), stir and heat to a temperature of 220°C and reflux for a period of time. After the reaction system changed from bright red to dark brown, the heating was stopped and cooled to room temperature. The solid was separated by a silica gel adsorption column under reduced pressure, and then the adsorption column was rinsed three times with dichloromethane (20 mL). After all the organic phases were combined, the organic solvent was removed under reduced pressure to obtain a brown-red liquid. The crude product is purified by 200-400 mesh silica gel column chromatography (the eluent is petroleum ether and dichloromethane), and finally a reddish brown liquid product (59 g, yield 80%) can be obtained. After nuclear magnetic data and mass spectrometry analysis, compared with known literature (J.Am.Chem.Soc.2011,133,19864), the reddish-brown liquid is high-purity 2,8-dibromo-5,12-epoxy -5,5a,6,11,11a,12-hexahydrotetracene.
c)2,8-二溴并四苯c) 2,8-Dibromotetracene
Figure PCTCN2020123012-appb-000013
Figure PCTCN2020123012-appb-000013
在带有回流冷凝管的500mL两口圆底烧瓶中，依次加入2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯(30g，74mmol)和甲苯(250mL)。在常温和持续搅拌下，缓慢往该两口圆底烧瓶中分批加入一水合对甲苯磺酸(7.1g，37mmol)。然后，将反应体系加热至120℃回流一段时间。待反应体系由红褐色变为深黑色后，停止加热并冷却至室温。向该两口圆底烧瓶中加入100mL水，分液，保留有机相。用氯仿(50mL)再清洗水相三次后，合并所有的有机相，并在减压下除去有机溶剂，得到灰黑色固体。再将所得固体转移并投入到带有回流冷凝管的250mL两口圆底烧瓶中，依次加入重结晶的DDQ(34g，150mmol)和四氯化碳(150mL)，并将反应体系升温至80℃回流一段时间。待反应体系由棕灰色变为红褐色后，停止加热并冷却至室温。向反应体系加入50mL甲醇并充分搅拌，再用抽滤漏斗过滤该混合物得到红褐色固体。粗品依次经100mL乙醇，50mL***和50mL二氯甲烷清洗，最终得到砖红色固体(23g，产率81％)。经核磁数据和质谱分析，与已知文献(Nat.Sci.Rep.2016,6,36310)比对，该砖红色固体为文献报道的2,8-二溴并四苯。质谱和元素分析数据如下：EI-MS Calcd.for C 18H 10Br 2:385.91.Found:386.00.Anal.Calcd for C 18H 10Br 2:C,56.00；H,2.61.Found:C,56.26；H,2.54. In a 500mL two-necked round bottom flask with a reflux condenser, add 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene (30g, 74 mmol) and toluene (250 mL). Under normal temperature and continuous stirring, slowly add p-toluenesulfonic acid monohydrate (7.1 g, 37 mmol) into the two-necked round bottom flask in batches. Then, the reaction system was heated to 120°C and refluxed for a period of time. After the reaction system changed from reddish brown to dark black, stop heating and cool to room temperature. Add 100 mL of water to the two-necked round bottom flask, separate the liquids, and retain the organic phase. After washing the aqueous phase three more times with chloroform (50 mL), all the organic phases were combined, and the organic solvent was removed under reduced pressure to obtain a gray-black solid. Then the obtained solid was transferred and put into a 250mL two-necked round bottom flask with reflux condenser, and recrystallized DDQ (34g, 150mmol) and carbon tetrachloride (150mL) were sequentially added, and the reaction system was heated to 80℃ for reflux a period of time. After the reaction system changed from brownish gray to reddish brown, the heating was stopped and cooled to room temperature. 50 mL of methanol was added to the reaction system and fully stirred, and then the mixture was filtered with a suction filter funnel to obtain a reddish brown solid. The crude product was washed successively with 100 mL ethanol, 50 mL ether and 50 mL dichloromethane, and finally a brick red solid (23 g, yield 81%) was obtained. After nuclear magnetic data and mass spectrometry analysis, compared with known literature (Nat.Sci.Rep.2016,6,36310), the brick-red solid is 2,8-dibromotetracene reported in the literature. The mass spectrum and elemental analysis data are as follows: EI-MS Calcd.for C 18 H 10 Br 2 :385.91.Found:386.00.Anal.Calcd for C 18 H 10 Br 2 :C,56.00; H,2.61.Found:C,56.26 ;H,2.54.
实施例2Example 2
Figure PCTCN2020123012-appb-000014
Figure PCTCN2020123012-appb-000014
在带有回流冷凝管的100mL两口圆底烧瓶中，依次加入上述实施例1制备的2,8-二溴并四苯(1.0g，2.6mmol)，苯硼酸(0.95g，7.8mmol)，磷酸钾一水合物(3.0g，13mmol)和甲苯(30mL)。向该悬浮液中加入12mg醋酸钯(0.05mmol)和41mg SPhos(0.1mmol)，并且将反应混合物加热回流16h以上。反应结束后，停止搅拌并冷却至常温，接着往该反应体系中加入50mL石油醚，并将该两口圆底烧瓶置于超声震荡仪中超声一段时间。用抽滤漏斗过滤圆底烧瓶中的混合物得到红褐色固体。粗品依次经50mL乙醇，100mL热水，50 mL甲醇，50mL***和50mL正己烷清洗，最终得到砖红色固体(0.98g，产率99％)。HRMS Calcd.for C 30H 20:380.1565.Found:380.1563.Anal.Calcd for C 30H 20:C,94.70；H,5.30.Found:C,93.07；H,5.32. In a 100mL two-necked round bottom flask with a reflux condenser, add 2,8-dibromotetracene (1.0g, 2.6mmol), phenylboronic acid (0.95g, 7.8mmol) and phosphoric acid prepared in Example 1 above in sequence. Potassium monohydrate (3.0 g, 13 mmol) and toluene (30 mL). To this suspension were added 12 mg of palladium acetate (0.05 mmol) and 41 mg of SPhos (0.1 mmol), and the reaction mixture was heated to reflux for more than 16 hours. After the reaction, the stirring was stopped and cooled to normal temperature, and then 50 mL of petroleum ether was added to the reaction system, and the two-neck round-bottomed flask was placed in an ultrasonic shaker and sonicated for a period of time. The mixture in the round bottom flask was filtered with a suction filter to obtain a reddish brown solid. The crude product was washed successively with 50 mL ethanol, 100 mL hot water, 50 mL methanol, 50 mL ether and 50 mL n-hexane, and finally a brick red solid (0.98 g, yield 99%) was obtained. HRMS Calcd.for C 30 H 20 : 380.1565. Found: 380.1563. Anal. Calcd for C 30 H 20 : C, 94.70; H, 5.30. Found: C, 93.07; H, 5.32.
实施例3Example 3
参考实施例2中的方法，将苯硼酸替换为不同的原料，可以获得下列化合物：With reference to the method in Example 2, replacing phenylboronic acid with different raw materials, the following compounds can be obtained:
Figure PCTCN2020123012-appb-000015
Figure PCTCN2020123012-appb-000015
Figure PCTCN2020123012-appb-000016
Figure PCTCN2020123012-appb-000016
实施例4物理气相传输提纯Example 4 Physical vapor transmission purification
上述实施例2和3制备的化合物均经提纯升华后用于制备器件。The compounds prepared in the foregoing Examples 2 and 3 were purified and sublimated and used to prepare devices.
本实施例提纯方法使用bruke公司的电管式炉，配备一根可抽真空和充入气体的石英管。电管式炉分蒸发段A和沉积区B。The purification method in this embodiment uses an electric tube furnace of Bruke Company, equipped with a quartz tube that can be evacuated and filled with gas. The electric tube furnace is divided into evaporation section A and deposition section B.
提纯升华操作为：首先由机械泵抽体系压力至1x10 -1pa，再由分子泵抽至1x10 -3pa，之后加热提纯。其中蒸发段由电阻丝加热，控温由管式炉自带***完成。将上述实施例2和3制备的化合物放入石英舟中放置于蒸发区域，在350℃下加热4天，由其自然沉积于B。在B升华沉积所得物质即为所需材料。在炉子温度降至50℃以下时，关泵，然后放气，刮下所需材料。 The purification and sublimation operation is as follows: first the system pressure is pumped by a mechanical pump to 1x10 -1 pa, and then pumped to 1x10 -3 pa by a molecular pump, and then heated and purified. The evaporation section is heated by resistance wire, and the temperature control is completed by the tube furnace's own system. The compounds prepared in the foregoing Examples 2 and 3 were placed in a quartz boat and placed in the evaporation area, heated at 350° C. for 4 days, and deposited on B naturally. The material obtained by sublimation deposition in B is the required material. When the furnace temperature drops below 50°C, turn off the pump, then vent the air and scrape off the required materials.
实施例5薄膜器件Example 5 Thin film device
源漏电极的源极和漏极均由金电极构成，薄膜器件电极厚度为20nm左右。在蒸镀机中操作，将上述实施例3纯化的化合物放在石英舟中，用1.3安培电流加热，用0.1A/S的速度蒸镀50nm。基底为由十六甲基三氯硅烷修饰的300nm厚的二氧化硅片，取出后，采用不同规格掩模版，同样在蒸镀机中蒸镀金，以0.1A/s的速度蒸 镀20-25nm。之后进行测试，电学测试方法为：在室温下大气环境中，以广泛使用的OFET测试方法(电极蒸镀或贴附在有机层以后，在探针台上测试。将源极针与漏记针分别戳在金电极上，之后将栅极针戳在底部栅极(铜片)上，通过保持源极栅极电压不变，改变源漏电压进行测试观察电流)在Micromanipulator 6150手动探针台上用keithley 4200SCS半导体电学测试***进行测试。器件结构如图2所示。The source and drain of the source and drain electrodes are both composed of gold electrodes, and the thickness of the thin film device electrodes is about 20 nm. Operate in a vapor deposition machine, place the compound purified in Example 3 above in a quartz boat, heat it with 1.3 ampere current, and vaporize 50 nm at a rate of 0.1 A/S. The substrate is a 300nm-thick silicon dioxide sheet modified by hexamethyltrichlorosilane. After taking it out, a different specification mask is used. The gold is also evaporated in an evaporation machine, and 20-25nm is evaporated at a rate of 0.1A/s. . Afterwards, the electrical test method is: at room temperature in the atmospheric environment, the widely used OFET test method (electrode vapor deposition or sticking to the organic layer, test on the probe station. The source pin and the missing pin Poke on the gold electrode respectively, and then poke the gate pin on the bottom gate (copper sheet), keep the source gate voltage unchanged, change the source and drain voltage to test and observe the current) on the Micromanipulator 6150 manual probe station Use Keithley 4200SCS semiconductor electrical test system for testing. The device structure is shown in Figure 2.
其中，源漏电极为20-25nm厚的金电极，有机半导体层为上述实施例4纯化的化合物，绝缘层为十六甲基三氯硅烷(ots)修饰的二氧化硅层，栅极为硅。Among them, the source and drain electrodes are gold electrodes with a thickness of 20-25 nm, the organic semiconductor layer is the compound purified in Example 4, the insulating layer is a silicon dioxide layer modified with hexamethyltrichlorosilane (ots), and the gate is silicon.
制备有机半导体层时使用的化合物与其对应的检测结果列于下表(如下表格中的沟道长度为铜网的道沟长度)。The compounds used in the preparation of the organic semiconductor layer and their corresponding test results are listed in the following table (the channel length in the following table is the channel length of the copper mesh).
Figure PCTCN2020123012-appb-000017
Figure PCTCN2020123012-appb-000017
如上表格中的平均值为制备20个器件在相同条件下测定获得的平均值。The average value in the above table is the average value obtained by preparing 20 devices and measuring under the same conditions.
本实施例还测试了如下化合物的紫外荧光光谱，测试过程为：将测试化合物取1mg溶解于四氢呋喃溶液中，因化合物溶解性极差故用滤头将残渣过滤，之后紫外可见光谱和荧光光谱分别在Hitachi U-3010紫外可见光谱仪和JΛS.CO FP-6600 spectrofluorometer荧光光谱仪上进行。操作为常规操作。测试结果如图9所示，由图9可知 并四苯的噻吩和呋喃苯衍生物的带隙均在2ev左右，是一种窄带隙材料，易出现高迁移率材料。This example also tested the ultraviolet fluorescence spectra of the following compounds. The test process was as follows: Dissolve 1 mg of the test compound in a tetrahydrofuran solution, and filter the residue with a filter due to the extremely poor solubility of the compound, and then the ultraviolet-visible spectrum and the fluorescence spectrum were respectively It was carried out on Hitachi U-3010 ultraviolet-visible spectrometer and JΛS.CO FP-6600 spectrofluorometer. The operation is normal operation. The test result is shown in Figure 9. It can be seen from Figure 9 that the band gaps of the thiophene and furan benzene derivatives of naphthacene are both around 2 eV, which is a narrow band gap material, which is prone to high mobility materials.
实施例6单晶器件Example 6 Single crystal device
源漏电极均由金电极构成，采用物理气相沉积的方式制备单晶。按照实施例5的方法使用管式炉，将上述实施例4纯化的化合物放置于石英舟中，放置在石英管的蒸发区域，之后在真空条件下，以200℃的温度蒸镀2h，在沉积区域放置由十六甲基三氯硅烷修饰的300nm厚的二氧化硅片，期间通氩气，保持压强大小为1.2pa。在温度降至30℃时取出二氧化硅片，在显微镜下找到规则形貌微纳晶，采用贴金膜的方式在晶体两端贴上金电极。之后进行测试，测试方法为将针扎在电极上，同时将栅极针扎在底部栅电极。(此处栅极采用铜片)保持栅电压不变(源极栅极间电压，源极为0V)通过改变源漏电压进行测试。器件采用底栅顶接触(栅极在底，顶部源漏)，其结构如图2所示，其中源漏电极为25nm厚的金电极，有机半导体层为上述实施例4纯化的化合物，绝缘层为十六甲基三氯硅烷(ots)修饰的二氧化硅层，栅极为硅。The source and drain electrodes are all composed of gold electrodes, and single crystals are prepared by physical vapor deposition. Using a tube furnace in accordance with the method of Example 5, place the compound purified in Example 4 above in a quartz boat and place it in the evaporation area of the quartz tube. Then, under vacuum conditions, it was vapor-deposited at a temperature of 200°C for 2 hours. A 300nm-thick silicon dioxide sheet modified by hexamethyltrichlorosilane was placed in the area, and argon gas was applied during the period to keep the pressure as low as 1.2pa. Take out the silicon dioxide sheet when the temperature drops to 30°C, find the micro-nano crystals with regular morphology under the microscope, and stick gold electrodes on both ends of the crystals by sticking gold films. Afterwards, the test is carried out. The test method is to pierce the needle on the electrode and at the same time pierce the grid needle on the bottom grid electrode. (Here, the gate uses a copper sheet) to keep the gate voltage unchanged (the voltage between the source and the gate, the source is 0V), and the test is performed by changing the source and drain voltage. The device uses bottom-gate top contact (gate at the bottom, top source and drain), and its structure is shown in Figure 2. The source and drain electrodes are 25nm thick gold electrodes, the organic semiconductor layer is the compound purified in Example 4 above, and the insulating layer is A silicon dioxide layer modified by hexamethyltrichlorosilane (ots), and the gate is silicon.
制备有机半导体层时使用的化合物与其对应的检测结果列于下表。The compounds used in the preparation of the organic semiconductor layer and their corresponding test results are listed in the table below.
Figure PCTCN2020123012-appb-000018
Figure PCTCN2020123012-appb-000018
如上表格中的平均值为制备20个器件在相同条件下测定获得的平均值。The average value in the above table is the average value obtained by preparing 20 devices and measuring under the same conditions.
本实施例还使用原子力扫描显微镜(AFM)对式2所示的并四苯的苯衍生物(DPT)薄膜器件进行了测试，结果如图12所示，由图12可知其薄膜存在规则且大块条状结晶，减少了晶界，器件的迁移率应较高。In this example, an atomic force scanning microscope (AFM) was used to test the tetracene derivative (DPT) thin film device shown in formula 2. The result is shown in FIG. 12, which shows that the thin film is regular and large. Lump-shaped crystals reduce the grain boundaries, and the mobility of the device should be higher.
本实施例还测试了式2所示的并四苯的苯衍生物的X射线衍射(XRD)，结果如图13所示，由图13可知其结晶峰很尖锐，说明其结晶性较好。In this example, the X-ray diffraction (XRD) of the benzene derivative of naphthacene represented by Formula 2 was also tested. The result is shown in FIG. 13. From FIG. 13, it can be seen that the crystalline peak is sharp, indicating that its crystallinity is better.
本实施例还测试了式2所示的并四苯的苯衍生物的紫外光电子能谱(UPS)，结果如图14所示，由图14可知其HOMO与LUMO，从而可以计算带隙。经计算，与由紫外计算的带隙数值相近，预期其为一种窄带隙材料。This example also tested the UV Photoelectron Spectroscopy (UPS) of the benzene derivative of naphthacene shown in Formula 2, and the result is shown in FIG. 14. From FIG. 14, the HOMO and LUMO can be known, so that the band gap can be calculated. After calculation, it is similar to the band gap calculated by ultraviolet, and it is expected to be a narrow band gap material.
本实施例还测试了式2所示的并四苯的苯衍生物的紫外荧光光谱，结果如图15所示，由图15可知其荧光为红色，同时由其紫外谱图可知其带隙为2ev左右。In this example, the ultraviolet fluorescence spectrum of the benzene derivative of naphthacene shown in formula 2 was also tested. The result is shown in Figure 15. It can be seen from Figure 15 that the fluorescence is red, and the ultraviolet spectrum shows that its band gap is Around 2ev.
本实施例还测试了式2所示并四苯的苯衍生物制备的单晶器件的显微镜实拍图，结果如图16所示。In this example, the actual microscope images of the single crystal device prepared by the benzene derivative of naphthacene shown in Formula 2 were also tested, and the result is shown in FIG. 16.
实施例7化合物稳定性测试Example 7 Compound stability test
在常规大气条件下测试式2所示的并四苯的苯衍生物和如下所示的并六苯的溶液稳定性(物质浓度为10 -5mol/L溶液，大气测试环境，样品不做任何特殊处理和封装保护，不避光，常规保存)，结果如图20所示。由图20可知，2h内式2所示的并四苯的苯衍生物的紫外光谱重叠性很好(图20a)，同时对比研究表明如果在氮气保护氛围下其光学稳定性可达18h以上(图20b)，预测可具有更长时间的稳定特性，进一步的稳定性跟踪实验在进一步开展中。这些研究数据表明该类化合物材料由于C-单晶自由旋转特性对于分子构象的调控，使其展示了良好的稳定性，这对于后面的器件应用具有非常重要的意义。 Under normal atmospheric conditions, test the solution stability of the tetracene derivatives shown in formula 2 and the hexacene shown below (substance concentration is 10 -5 mol/L solution, the atmospheric test environment, the sample does not do anything Special treatment and packaging protection, not protected from light, conventional storage), the result is shown in Figure 20. It can be seen from Figure 20 that the UV spectra of the benzene derivatives of naphthacene represented by Formula 2 in 2h have a good overlap (Figure 20a). At the same time, a comparative study shows that the optical stability can reach more than 18h under a nitrogen atmosphere ( Figure 20b), the prediction may have a longer-term stability characteristic, and further stability tracking experiments are in further development. These research data show that this type of compound material exhibits good stability due to the free rotation characteristic of C-single crystal on the regulation of molecular conformation, which is of great significance for the subsequent device applications.
实施例8单晶晶体管器件连续工作的稳定性测试Example 8 Stability Test of Continuous Operation of Single Crystal Transistor Device
式2所示的并四苯的苯衍生物单晶晶体管器件连续工作的稳定性数据(硅和二氧化硅作为栅极和绝缘层，金做源漏电极，器件不经过任何的特殊保护和封装处理，大气测试条件，测试电压范围栅压20V—-40V，源漏电压：-40V；测试步幅：2V)如图21所示。由图21可知，基于该分子所构筑的电子器件具有优异的工作稳定性，在连续跟踪40h小时的测试过程中，器件的性能取向基本一致，而且随着测试时间的延长，器件的曲线表现的更加标准，表明其优异的光电工作特性。The stability data of the continuous operation of the tetracene benzene derivative single crystal transistor device shown in formula 2 (silicon and silicon dioxide are used as the gate and insulating layer, and gold is used as the source and drain electrodes. The device does not undergo any special protection and packaging. Processing, atmospheric test conditions, test voltage range: grid voltage 20V--40V, source-drain voltage: -40V; test step: 2V) as shown in Figure 21. It can be seen from Figure 21 that the electronic device constructed based on this molecule has excellent working stability. During the continuous tracking test for 40 hours, the performance orientation of the device is basically the same, and with the extension of the test time, the curve of the device shows More standard, showing its excellent optoelectronic working characteristics.
实施例9化合物成膜特性的测试Example 9 Test of film-forming properties of compound
式2所示的并四苯的苯衍生物材料的成膜性能研究(真空热蒸发蒸镀条件，蒸镀速度：
Figure PCTCN2020123012-appb-000019
基板加热温度：室温RT-90℃；基板为二氧化硅和OTS修饰的二氧化硅)，如图22，23所示。由图22，23可知，该类化合物具有良好的成膜特性，在不同基板和不同蒸镀条件下，所形成薄膜均具有良好的连续性及结晶特性(图24)，这对于实现高性能光电性能器件来讲具有非常重要的意义，预示其重要的潜在应用。 Study on the film-forming performance of the benzene derivative material of naphthacene shown in formula 2 (vacuum thermal evaporation evaporation conditions, evaporation speed:
Figure PCTCN2020123012-appb-000019
Substrate heating temperature: room temperature RT-90°C; substrate is silica and OTS modified silica), as shown in Figures 22 and 23. It can be seen from Figures 22 and 23 that this type of compound has good film-forming properties. Under different substrates and different evaporation conditions, the formed films have good continuity and crystalline properties (Figure 24), which is useful for realizing high-performance photovoltaics. In terms of performance devices, it has a very important meaning and heralds important potential applications.
实施例10发光性能测试Example 10 Luminous Performance Test
式2所示的并四苯的苯衍生物掺杂(掺杂量为1-10％)在PMMA中样品的明场(左)和荧光(右)照片如图25所示。该图表明该类材料具有明显的发光特性，可用于电致发光器件、生物传感器件、光子学器件及其相关功能器件的应用研究。The bright field (left) and fluorescence (right) photographs of the benzene derivative of naphthacene shown in formula 2 doped (doping amount is 1-10%) in PMMA are shown in FIG. 25. The figure shows that this type of material has obvious luminescence characteristics and can be used in the application research of electroluminescent devices, biosensing devices, photonics devices and related functional devices.
实施例11单晶发光性能测试Example 11 Single crystal luminescence performance test
式2所示的并四苯的苯衍生物单晶的明场(左一)及不同激发波长下的荧光照片如图26所示。该图表明该类材料在单晶状态下同样也具有良好的发光特性，优于传统稠环并苯类材料体系，表明其在有机微纳电光器件和生物传感方面的潜在重要应用。The bright field (left one) of the single crystal of the benzene derivative of naphthacene shown in Formula 2 and the fluorescence photos at different excitation wavelengths are shown in FIG. 26. The figure shows that this type of material also has good luminescence properties in the single crystal state, which is better than the traditional fused-ring acene material system, indicating its potential important applications in organic micro-nano electro-optical devices and biosensing.
实施例12化合物光电器件性能测试数据Example 12 Compound photoelectric device performance test data
式2所示的并四苯的苯衍生物光电器件电性能测试数据，如图27所示。由图27可知，该器件在施加光的情况下，随着照射光强的增大，光电流增大，表现出优秀的光响应。在没有经过***器件结构及界面等条件优化的条件下，所获得器件的最优异光敏感度(P)可高达到10 6；此外，该类器件还展现了一定的磁场响应特性，表明该类化合物在多功能光电器件及有机自旋等领域的潜在应用。 The electrical performance test data of the benzene derivative photoelectric device of naphthacene shown in Formula 2 is shown in FIG. 27. It can be seen from Fig. 27 that under the condition of applying light, the photocurrent increases with the increase of the irradiated light intensity, showing an excellent photoresponse. Without optimization of the system device structure and interface conditions, the best light sensitivity (P) of the obtained device can be as high as 10 6 ; in addition, this type of device also exhibits a certain magnetic field response characteristic, indicating that this type of compound Potential applications in multifunctional optoelectronic devices and organic spin.
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。In the foregoing, the embodiments of the present invention have been described. However, the present invention is not limited to the above-mentioned embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (10)

  1. 2,8-二溴并四苯的制备方法，其特征在于，包括如下步骤：The preparation method of 2,8-dibromotetracene is characterized in that it comprises the following steps:
    Figure PCTCN2020123012-appb-100001
    Figure PCTCN2020123012-appb-100001
    S1)将化合物2-氨基-5-溴苯甲酸，酸1和亚硝酸类化合物置于溶剂1中，在低温下进行反应；反应完成后与呋喃共同置于另一种溶剂2中，加热回流反应得到6-溴-1,4-环氧-1,4-二氢萘；S1) Put the compound 2-amino-5-bromobenzoic acid, acid 1 and nitrous acid compound in solvent 1 and react at low temperature; after the reaction is completed, put it in another solvent 2 together with furan, and heat to reflux The reaction obtains 6-bromo-1,4-epoxy-1,4-dihydronaphthalene;
    S2)将步骤S1)制备的化合物6-溴-1,4-环氧-1,4-二氢萘，4-溴苯并环丁烷以及添加剂1置于溶剂3中反应得到产物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯；S2) The compound 6-bromo-1,4-epoxy-1,4-dihydronaphthalene, 4-bromobenzocyclobutane and additive 1 prepared in step S1) are reacted in solvent 3 to obtain products 2,8 -Dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene;
    S3)将步骤S2)制备的化合物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯和酸2置于溶剂4中加热回流反应，将所得产物与添加剂2在溶剂5中加热回流反应得到2,8-二溴并四苯；S3) Put the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and acid 2 prepared in step S2) in solvent 4 and heat to reflux In the reaction, the resulting product and the additive 2 are heated and refluxed in the solvent 5 to obtain 2,8-dibromotetracene;
    其中，步骤S1)中，所述酸1选自无机酸；Wherein, in step S1), the acid 1 is selected from inorganic acids;
    步骤S1)中，所述亚硝酸类化合物选自亚硝酸叔丁酯、亚硝酸异戊酯、亚硝酸钠、亚硝酸钾中的至少一种；In step S1), the nitrous acid compound is selected from at least one of tert-butyl nitrite, isoamyl nitrite, sodium nitrite, and potassium nitrite;
    步骤S2)中，所述添加剂1选自无机碱；In step S2), the additive 1 is selected from inorganic bases;
    步骤S3)中，所述酸2选自无机酸或有机酸；In step S3), the acid 2 is selected from inorganic acid or organic acid;
    步骤S3)中，所述添加剂2选自氧化剂。In step S3), the additive 2 is selected from oxidizing agents.
  2. 根据权利要求1所述的方法，其特征在于，步骤S1)中，所述酸1为盐酸、硫酸、磷酸、三氟化硼、五氟化磷等无机酸中的至少一种；The method according to claim 1, wherein in step S1), the acid 1 is at least one of inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, boron trifluoride, and phosphorus pentafluoride;
    优选地，步骤S1)中，所述化合物2-氨基-5-溴苯甲酸，酸1和亚硝酸类化合物的摩尔比为1:(0.01～100):(0.01～100)；Preferably, in step S1), the molar ratio of the compound 2-amino-5-bromobenzoic acid, acid 1 and nitrous acid compound is 1:(0.01-100):(0.01-100);
    优选地，步骤S1)中，所述呋喃和起始原料2-氨基-5-溴苯甲酸的摩尔比为1:(0.01～100)；Preferably, in step S1), the molar ratio of the furan to the starting material 2-amino-5-bromobenzoic acid is 1: (0.01-100);
    优选地，步骤S1)中，所述低温反应的温度是–200～10℃；Preferably, in step S1), the temperature of the low-temperature reaction is -200-10°C;
    优选地，步骤S2)中，所述添加剂1为碳酸钾、碳酸氢钾、碳酸钠、碳酸氢钠、醋酸钾、醋酸钠、柠檬酸钠；Preferably, in step S2), the additive 1 is potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, potassium acetate, sodium acetate, sodium citrate;
    优选地，步骤S2)中，所述化合物6-溴-1,4-环氧-1,4-二氢萘，4-溴苯并环丁烷和添加剂1的摩尔比为1:(0.01～100):(0.01～100)；Preferably, in step S2), the molar ratio of the compound 6-bromo-1,4-epoxy-1,4-dihydronaphthalene, 4-bromobenzocyclobutane and additive 1 is 1:(0.01～ 100): (0.01～100);
    优选地，步骤S3)中，所述酸2为盐酸、硫酸、磷酸、醋酸、三氟醋酸、三氟甲磺酸、对甲苯磺酸或其水合物、吡啶对甲苯磺酸盐；Preferably, in step S3), the acid 2 is hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid or its hydrate, pyridine p-toluenesulfonate;
    优选地，步骤S3)中，所述添加剂2为氧气、苯醌、四氯苯醌、二氯二氰基苯醌(DDQ)、三氯脲氰、溴、碘、溴代琥珀酰亚胺、碘代琥珀酰亚胺，或者为活性碳、钯碳；Preferably, in step S3), the additive 2 is oxygen, benzoquinone, tetrachlorobenzoquinone, dichlorodicyanobenzoquinone (DDQ), trichlorourea cyanide, bromine, iodine, bromosuccinimide, Iodosuccinimide, or activated carbon, palladium on carbon;
    优选地，步骤S3)中，所述化合物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯和酸2的摩尔比为1:(0.01～100)；Preferably, in step S3), the molar ratio of the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene to acid 2 is 1. :(0.01～100);
    优选地，步骤S3)中，所述化合物2,8-二溴-5,12-环氧-5,5a,6,11,11a,12-六氢并四苯和添加剂2的摩尔比为1:(0.01～100)。Preferably, in step S3), the molar ratio of the compound 2,8-dibromo-5,12-epoxy-5,5a,6,11,11a,12-hexahydrotetracene and additive 2 is 1. :(0.01～100).
  3. 式(I)所示的2,8-双取代的并四苯类衍生物，The 2,8-disubstituted naphthacene derivatives represented by formula (I),
    Figure PCTCN2020123012-appb-100002
    Figure PCTCN2020123012-appb-100002
    其中，式(I)中，R相同或不同，彼此独立地选自卤素、任选被一个、两个或更多个RS取代的如下基团：C 6-20芳基、5-20元杂芳基、5-20元杂芳基并5-20元杂芳基、5-20元杂芳基并5-20元杂芳基并5-20元杂芳基、连二(C 6-20芳基并C 3-20环烷基并C 6-20芳基)基、C 1-40烷基、C 3-20环烷基、5-20元杂环基、C 1-40烷氧基、C 1-40烷硫基； Wherein, in formula (I), R are the same or different, and are independently selected from halogen, the following groups optionally substituted by one, two or more RS: C 6-20 aryl, 5-20 membered hetero Aryl, 5-20 membered heteroaryl and 5-20 membered heteroaryl, 5-20 membered heteroaryl and 5-20 membered heteroaryl and 5-20 membered heteroaryl, even two (C 6-20 Aryl and C 3-20 cycloalkyl and C 6-20 aryl) group, C 1-40 alkyl, C 3-20 cycloalkyl, 5-20 membered heterocyclic group, C 1-40 alkoxy , C 1-40 alkylthio;
    所述RS选自卤素、CN、C 1-40烷基、卤代C 1-40烷基、-N(C 6-20芳基) 2、C 3-20环烷基、3-20元杂环基、-N(C 1- 40烷基) 2；任选被一个、两个或更多个取代卤代C 1-40烷基取代的如下基团：C 6-20芳基、5-20元杂芳基。 The RS is selected from halogen, CN, C 1-40 alkyl, halogenated C 1-40 alkyl, -N (C 6-20 aryl) 2 , C 3-20 cycloalkyl, 3-20 membered hetero cycloalkyl group, -N (C 1- 40 alkyl) 2; optionally substituted by one, two or more C 1-40 alkyl substituted with halo radicals as follows: C 6-20 aryl group, 5- 20-membered heteroaryl.
  4. 根据权利要求3所述的化合物，其特征在于，式(I)化合物中，R选自卤素、任选被一个、两个或更多个RS取代的如下基团：C 6-14芳基、5-14元杂芳基、5-14元杂芳基并5-14元杂芳基、5-14元杂芳基并5-14元杂芳基并5-14元杂芳基、连二(C 6-14芳基并C 3-12环烷基并C 6-14芳基)基、C 1-12烷基、C 1-12烷氧基、C 1-12烷硫基； The compound according to claim 3, wherein in the compound of formula (I), R is selected from halogen, the following groups optionally substituted by one, two or more RS: C 6-14 aryl, 5-14 membered heteroaryl group, 5-14 membered heteroaryl group and 5-14 membered heteroaryl group, 5-14 membered heteroaryl group and 5-14 membered heteroaryl group and 5-14 membered heteroaryl group, even two (C 6-14 aryl and C 3-12 cycloalkyl and C 6-14 aryl) group, C 1-12 alkyl, C 1-12 alkoxy, C 1-12 alkylthio;
    所述RS选自卤素、CN、C 1-10烷基、卤代C 1-10烷基、-N(C 6-14芳基) 2、C 3-10环烷基、3-10元杂环基、-N(C 1- 10烷基) 2；任选被一个、两个或更多个取代卤代C 1-10烷基取代的如下基团：C 6-14芳基、5-14元杂芳基。 The RS is selected from halogen, CN, C 1-10 alkyl, halogenated C 1-10 alkyl, -N (C 6-14 aryl) 2 , C 3-10 cycloalkyl, 3-10 membered hetero Cyclic group, -N(C 1- 10 alkyl) 2 ; the following groups optionally substituted by one, two or more substituted halogenated C 1-10 alkyl groups: C 6-14 aryl, 5- 14-membered heteroaryl.
  5. 根据权利要求3或4所述的化合物，其特征在于，R选自Br、苯基、1-萘基、2-萘基、噻吩基、呋喃基、2-蒽基、5-蒽基、2-芴基、3-芴基、1-二苯并呋喃基、3-二苯并呋喃基、3-二苯并吡咯基、N-二苯并吡咯基、1-二苯并噻吩基、3-二苯并噻吩基、1-吡嗪基、1-噻唑基、2-吩嗪基、1-喹喔啉基、9-芴酮-2-基、7-喹啉基，The compound according to claim 3 or 4, wherein R is selected from Br, phenyl, 1-naphthyl, 2-naphthyl, thienyl, furyl, 2-anthryl, 5-anthryl, 2 -Fluorenyl, 3-fluorenyl, 1-dibenzofuranyl, 3-dibenzofuranyl, 3-dibenzopyrrolyl, N-dibenzopyrrolyl, 1-dibenzothienyl, 3 -Dibenzothienyl, 1-pyrazinyl, 1-thiazolyl, 2-phenazinyl, 1-quinoxalinyl, 9-fluorenone-2-yl, 7-quinolinyl,
    或如下基团：Or the following groups:
    Figure PCTCN2020123012-appb-100003
    Figure PCTCN2020123012-appb-100003
    其中，“*”处表示连接位点；Among them, "*" represents the connection site;
    RS选自氟、氯、溴、CN、甲基、乙基、正己基、全氟代正己基、苯基、3,4,5-三(三氟甲基)-苯基、3,5-二(三氟甲基)-苯基、1-呋喃基、1-噻吩基、4-三氟甲基-呋喃基、4-三氟甲基-噻吩基、N-咔唑基、-N(苯基) 2、三氟甲基。 RS is selected from fluorine, chlorine, bromine, CN, methyl, ethyl, n-hexyl, perfluoro-n-hexyl, phenyl, 3,4,5-tris(trifluoromethyl)-phenyl, 3,5- Bis(trifluoromethyl)-phenyl, 1-furyl, 1-thienyl, 4-trifluoromethyl-furyl, 4-trifluoromethyl-thienyl, N-carbazolyl, -N( Phenyl) 2 , trifluoromethyl.
  6. 根据权利要求3-5任一项所述的化合物，其特征在于，式(I)化合物选自如下结构，The compound according to any one of claims 3-5, wherein the compound of formula (I) is selected from the following structures,
    Figure PCTCN2020123012-appb-100004
    Figure PCTCN2020123012-appb-100004
    Figure PCTCN2020123012-appb-100005
    Figure PCTCN2020123012-appb-100005
    Figure PCTCN2020123012-appb-100006
    Figure PCTCN2020123012-appb-100006
    Figure PCTCN2020123012-appb-100007
    Figure PCTCN2020123012-appb-100007
    Figure PCTCN2020123012-appb-100008
    Figure PCTCN2020123012-appb-100008
  7. 权利要求3-6任一项所述化合物的制备方法，其特征在于，包括如下步骤：The preparation method of the compound according to any one of claims 3-6, characterized in that it comprises the following steps:
    2,8-二溴并四苯与化合物X-R反应得到式(I)所示2,8-双取代的并四苯类衍生物，2,8-Dibromotetracene reacts with compound X-R to obtain 2,8-disubstituted tetracene derivatives represented by formula (I),
    Figure PCTCN2020123012-appb-100009
    Figure PCTCN2020123012-appb-100009
    其中，R具有权利要求1-4任一项的定义，X选自离去基团。Wherein, R has the definition of any one of claims 1 to 4, and X is selected from a leaving group.
  8. 权利要求7所述的制备方法，其特征在于，X选自卤素、硼酸、硼酸酯、烷基锡、烷基硅、镁、锌；The preparation method of claim 7, wherein X is selected from halogen, boric acid, boric acid ester, alkyl tin, alkyl silicon, magnesium, zinc;
    所述反应为下列反应：Suzuki反应、Stille反应、Heck反应、Sonogashira反应、Hiyama反应、Kumada反应、Negishi反应、Glaser-Eglinton反应、Claisen-Schmidt反应、Buchwald-Hartwig反应；The reactions are the following reactions: Suzuki reaction, Stille reaction, Heck reaction, Sonogashira reaction, Hiyama reaction, Kumada reaction, Negishi reaction, Glaser-Eglinton reaction, Claisen-Schmidt reaction, Buchwald-Hartwig reaction;
    优选地，2,8-二溴并四苯采用权利要求1或2的方法制备。Preferably, 2,8-dibromotetracene is prepared by the method of claim 1 or 2.
  9. 权利要求3-6任一项所述式(I)所示2,8-双取代的并四苯类衍生物的用途，其特征在于，用于制备有机半导体器件，电子学器件、电致发光器件、生物传感器件、光子学器件或有机自旋器件等及其相关器件。The use of 2,8-disubstituted naphthacene derivatives of formula (I) according to any one of claims 3-6, characterized in that they are used to prepare organic semiconductor devices, electronic devices, and electroluminescence Devices, biosensing devices, photonics devices or organic spin devices, etc. and related devices.
  10. 根据权利要求9所述的用途，其特征在于，所述有机半导体器件选自有机场效应晶体管OFETs；The use according to claim 9, wherein the organic semiconductor device is selected from OFETs;
    所述有机半导体器件的有机半导体层中包括权利要求1-4任一项所述式(I)所示2,8-双取代的并四苯类衍生物。The organic semiconductor layer of the organic semiconductor device includes the 2,8-disubstituted naphthacene derivative represented by the formula (I) of any one of claims 1-4.
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