CN117088893A - Synthetic method of chalcogen heterobowl-shaped molecular graphene - Google Patents
Synthetic method of chalcogen heterobowl-shaped molecular graphene Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 23
- 229910052798 chalcogen Inorganic materials 0.000 title claims abstract description 21
- 150000001787 chalcogens Chemical class 0.000 title claims abstract description 21
- 238000010189 synthetic method Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 19
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- -1 tetrabutylammonium tetrafluoroborate Chemical compound 0.000 claims description 14
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 229940125904 compound 1 Drugs 0.000 claims description 11
- 229940125782 compound 2 Drugs 0.000 claims description 11
- 229940126214 compound 3 Drugs 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229940125898 compound 5 Drugs 0.000 claims description 9
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- 229940071870 hydroiodic acid Drugs 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 7
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N dihydroxy-phenylborane Natural products OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- 239000011669 selenium Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 229910052763 palladium Inorganic materials 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 125000003748 selenium group Chemical group *[Se]* 0.000 abstract 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- 239000003480 eluent Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- IVJZBYVRLJZOOQ-UHFFFAOYSA-N hexabenzo[bc,ef,hi,kl,no,qr]coronene Chemical compound C12=C(C(C(=C34)C(=C56)C7=C89)=C%10%11)C7=C7C%12=C2C=CC=C1C%11=CC=CC%10=C4C=CC=C3C6=CC=CC5=C9C=CC=C8C7=CC=C%12 IVJZBYVRLJZOOQ-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000007302 alkyne metathesis reaction Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BGXZJSLTGNPDDH-UHFFFAOYSA-N benzenethiol;sodium Chemical compound [Na].SC1=CC=CC=C1 BGXZJSLTGNPDDH-UHFFFAOYSA-N 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XHJPOZDMDBETDO-UHFFFAOYSA-N hexabenzo[a,d,g,j,m,p]coronene Chemical compound C1=CC=CC2=C(C3=C45)C6=CC=CC=C6C4=C(C=CC=C4)C4=C(C=4C6=CC=CC=4)C5=C4C6=C(C=CC=C5)C5=C(C=5C6=CC=CC=5)C4=C3C6=C21 XHJPOZDMDBETDO-UHFFFAOYSA-N 0.000 description 1
- QBHWPVJPWQGYDS-UHFFFAOYSA-N hexaphenylbenzene Chemical class C1=CC=CC=C1C(C(=C(C=1C=CC=CC=1)C(C=1C=CC=CC=1)=C1C=2C=CC=CC=2)C=2C=CC=CC=2)=C1C1=CC=CC=C1 QBHWPVJPWQGYDS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- NVSDADJBGGUCLP-UHFFFAOYSA-N trisulfur Chemical compound S=S=S NVSDADJBGGUCLP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/16—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
- C07D517/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains three hetero rings
- C07D517/16—Peri-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of chalcogen heterobowl-shaped molecular graphene, which takes cheap and easily available 2-bromo-5-chloroacetophenone as a raw material, obtains a ternary product under the catalysis of trifluoromethanesulfonic acid, and finally introduces sulfur or selenium atoms to obtain the chalcogen heterobowl-shaped molecular graphene through Suzuki coupling, friedel-crafts acylation and Shore reaction. Besides the advantages of short synthesis steps, mild reaction conditions, simple operation and the like, the method mainly adopts no prior palladium catalysis mode when introducing sulfur or selenium atoms, but introduces sulfur or selenium atoms under the condition of no metal catalysis, and has higher yield. The compound shows excellent electrical properties and has great application value in the aspects of organic light-emitting diodes and semiconductor materials.
Description
Technical Field
The invention belongs to the technical field of synthesis of polycyclic aromatic hydrocarbon compounds, and particularly relates to a synthesis method of chalcogen heterobowl-shaped molecular graphene.
Background
Polycyclic Aromatic Hydrocarbons (PAHs), also known as nano graphene molecules, are closely related to basic theoretical research and organic light electromagnetic functional materials due to their clear molecular structure, good photoelectric properties and accurate self-assembly properties. Research into polycyclic aromatic hydrocarbons has become an important discipline area that intersects chemistry, physics, materials science, and biology. Since the discovery of graphene, polycyclic aromatic hydrocarbons have attracted increasing attention, known as the "odd" materials of the twenty-first century.
Among them, hexabenzocoronen (HBC) and its derivatives are an important class of organic molecules in polycyclic aromatic hydrocarbons, which have a long synthetic history and a thorough and thorough research background. Hexabenzocoronene can be divided into two types according to the positions of benzene rings at the periphery of hexabenzocoronene, namely hexabenzocoronene (hexa-peri-hexabenzocoronene, or p-HBC) at a plane sharing two groups of carbon-carbon bonds with coronene, and hexabenzocoronene (hexa-cata-hexabenzocoronene, or c-HBC) at a biconcave sharing one group of carbon-carbon bonds with coronene. By taking the two molecules as the parent, the variety of the polycyclic aromatic hydrocarbon is greatly expanded, and simultaneously, a trigger is provided for synthesizing bowl-shaped polycyclic aromatic hydrocarbon.
There is only one currently reported mainstream method of introducing sulfur atoms in the bay area. The Feng Xinliang subject group uses unsubstituted hexaphenyl benzene as a raw material, ferric trichloride is used for oxidation ring closure to obtain unsubstituted p-HBC, iodine chloride is used as a chlorinating reagent, perchlorinated p-HBC (PCHBC) is obtained under the catalysis of aluminum trichloride, and finally the p-HBC (tri-sulfur nula HBC, TSHBC) with twelve benzene mercapto groups on the periphery is obtained through reaction with excessive sodium thiophenol. The bowl-shaped molecules are synthesized mostly by overcoming huge tension, so that the corresponding sulfur source is introduced into sulfur atoms under the condition of palladium catalysis in the reported literature, and the molecules are synthesized by means of the traction force of metal palladium, but palladium metal has a certain influence on the bond formation of the sulfur atoms, so that the general yield of the finally obtained target molecules is not high, and therefore, the development of a reaction system without metal catalysis has important theoretical significance and application value.
Disclosure of Invention
The invention aims to provide a method for synthesizing chalcogen heterobowl-shaped molecular graphene without metal catalysis.
The synthetic route and the synthetic method adopted by the invention are as follows:
(1) Synthesizing 2-bromo-5-chloroacetophenone into a compound 1 under the catalysis of trifluoromethanesulfonic acid;
(2) Coupling the compound 1 with 4-fluoro-2-methyl formate phenylboronic acid through Suzuki to obtain a compound 2;
(3) Performing Friedel-crafts acylation on the compound 2 under the catalysis of methanesulfonic acid to obtain a compound 3;
(4) Reducing the compound 3 by hydroiodic acid in the presence of red phosphorus to obtain a compound 4;
(5) Reacting the compound 4 with bromobutane under the action of potassium tert-butoxide to obtain a compound 5;
(6) Under the catalysis of trifluoromethanesulfonic acid, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is used as an oxidant to synthesize a compound 6;
(7) When M represents S, the chalcogen heterobowl-shaped molecular graphene is obtained from the compound 6 under the action of tert-butyl mercaptan, potassium carbonate and tetrabutylammonium tetrafluoroborate; and when M represents Se, reacting the compound 6 with tert-butylselenyllithium to obtain the chalcogen heterobowl-shaped molecular graphene.
In the step (1), 2-bromo-5-chloroacetophenone is preferably reacted for 8 to 9 hours at 140 to 150 ℃ under the catalysis of trifluoromethanesulfonic acid; the molar ratio of the 2-bromo-5-chloroacetophenone to the trifluoromethanesulfonic acid is 1:0.10 to 0.15.
In the step (2), toluene is preferably used as a solvent, and under the protection of inert gas, the compound 1 and 4-fluoro-2-methyl formate phenylboronic acid, tris (dibenzylideneacetone) dipalladium, 2-dicyclohexylphosphine-2, 6-dimethoxy biphenyl and potassium phosphate are refluxed for 20 to 24 hours at the temperature of between 100 and 110 ℃ for Suzuki coupling; the molar ratio of the compound 1 to 4-fluoro-2-methyl formate phenylboronic acid, tris (dibenzylideneacetone) dipalladium, 2-dicyclohexylphosphine-2, 6-dimethoxy biphenyl and potassium phosphate is 1:4.50 to 5.00:0.15 to 0.20:0.45 to 0.50:9.00 to 9.10.
In the step (3), the compound 2 is preferably subjected to heating reflux reaction at 110-180 ℃ for 8-10 hours under the catalysis of methanesulfonic acid, and friedel-crafts acylation is carried out; the molar ratio of the compound 2 to the methylsulfonic acid is 1: 200-250.
In the step (4), propionic acid is preferably used as a solvent, and the compound 3, red phosphorus and hydroiodic acid are refluxed at 145-155 ℃ for 48-50 hours to perform a reduction reaction, wherein the molar ratio of the compound 3 to the red phosphorus to the hydroiodic acid is 1: 35-40: 178-200.
In the step (5), preferably, dry tetrahydrofuran is used as a solvent, and the compound 4 is reacted with potassium tert-butoxide and bromobutane for 3 to 5 hours at the temperature of between 75 and 85 ℃ under the protection of inert gas; the molar ratio of the compound 4 to the potassium tert-butoxide to the bromobutane is 1: 14-16: 14-15.
In the step (6), preferably, the compound 5, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone and trifluoromethanesulfonic acid are heated to react for 2 hours at 35 ℃ under the protection of inert gas by using dry dichloromethane as a solvent; the molar ratio of the compound 5 to the 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is 1:8, the amount of the triflic acid is 3% of the volume of the solvent.
In the step (7), when M represents S, preferably dry N, N-dimethylformamide is used as a solvent, and the compound 6 and tert-butyl mercaptan, potassium carbonate and tetrabutylammonium tetrafluoroborate are heated and reacted for 48 to 50 hours at the temperature of between 120 and 130 ℃ under the protection of inert gas; the molar ratio of the compound 6 to the tert-butyl mercaptan, the potassium carbonate and the tetrabutylammonium tetrafluoroborate is 1:23 to 25: 14-16: 2 to 4. When M represents Se, preferably taking dry N, N-dimethylformamide as a solvent, and heating and reacting the compound 6 and tertiary butyl selenium lithium for 48-50 hours at 120-130 ℃ under the protection of inert gas; the molar ratio of the compound 6 to the tert-butylseleno lithium is 1:60 to 80 percent.
The beneficial effects of the invention are as follows:
the invention takes cheap and easily available 2-bromo-5-chloroacetophenone as a starting material, obtains a trimerization product through acid catalysis, and finally obtains chalcogen heterobowl-shaped molecular graphene by Suzuki coupling, friedel-crafts acylation and Shore reaction and introducing heteroatoms into a bay area. Besides the advantages of short synthesis steps, mild reaction conditions, simple operation and the like, the method mainly adopts no prior palladium catalysis mode when introducing sulfur atoms, but overcomes intermolecular tension by intermolecular vibration under the condition of no metal catalysis, and has the advantages of easy reaction and purification, no catalyst residue and higher yield. The chalcogen heterobowl-shaped molecular graphene provided by the invention has excellent electrical properties and has great application value in the aspects of organic light-emitting diodes and semiconductor materials.
Drawings
FIG. 1 is a compound 7-1 in dichloromethane (5X 10) -3 mol/L) at a scanning rate of 0.1V/s.
FIG. 2 is a chart of the reaction of Compound 7-1 in dichloromethane (5X 10) -3 mol/L).
FIG. 3 is a thermogravimetric analysis of compound 7-1.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
1. 10.00g (42.83 mmol) of 2-bromo-5-chloroacetophenone (synthesized according to the method in the literature "Hillenbrand J, leutzsch M, YIannakas E, et al," Canopy Catalysts "for Alkyne Metathesis: molybdenum Alkylidyne Complexes with a Tripodal Ligand Framework [ J ]. Journal of the American Chemical Society,2020,142 (25): 11279-11294 ]) are placed in a 25mL lock tube, 0.69g (4.63 mmol) of trifluoromethanesulfonic acid is added dropwise to the lock tube, the lock tube is then transferred into a microwave, and the reaction is carried out at 140℃for 9 hours after sealing. After the reaction was completed, the reaction solution was diluted with dichloromethane to prevent solidification after cooling, washed with aqueous sodium bicarbonate, dried over anhydrous sodium sulfate, and after concentrating the solvent, purified by column chromatography silica gel chromatography (with volume ratio DCM: pe=1:4 as eluent) to obtain a pure product of compound 1 in a yield of 51%.
The spectrum data of the obtained compound 1 are as follows: 1 H NMR(600MHz,CDCl 3 )δ7.59(s,3H),7.43(s,3H),7.40(d,J＝2.5Hz,3H),7.18(dd,J＝8.5,2.6Hz,3H). 13 C NMR(151MHz,CDCl 3 )δ143.03(s),139.76(s),134.34(s),133.51(s),131.23(s),129.71(s),129.20(s),120.61(s)。
2. in a 250mL round bottom flask, 5.00g (7.73 mmol) of Compound 1 and 6.89g (34.81 mmol) of 4-fluoro-2-carboxylic acid methyl phenylboronic acid, 1.06g (1.16 mmol) of tris (dibenzylideneacetone) dipalladium, 1.43g (3.48 mmol) of 2-dicyclohexylphosphine-2, 6-dimethoxybiphenyl, 14.78g (69.61 mmol) of potassium phosphate were dissolved in 100mL of degassed toluene, refluxed at 100℃for 24 hours under nitrogen atmosphere, after the reaction was completed, the excess insoluble matter was filtered off through a silica gel bed, and after concentrating the solvent, the pure product of Compound 2 was obtained by column chromatography silica gel chromatography (with a volume ratio of DCM: PE=2:1 as eluent) in a yield of 63%.
The spectrum data for the resulting compound 2 are as follows: 1 H NMR(600MHz,CDCl 3 )δ7.47(dd,J＝8.6,6.7Hz,3H),7.21(dd,J＝8.1,1.9Hz,3H),7.08–6.96(m,6H),6.82–6.45(m,9H),3.44(t,J＝28.8Hz,9H). 13 C NMR(151MHz,CDCl 3 )δ166.34(s),162.27(s),141.07(s),139.38(d,J＝21.9Hz),139.28–138.37(m),137.33(s),133.67(d,J＝14.4Hz),132.92(s),131.00(s),129.99(s),129.64(s),129.42(s),127.34(s),52.29(s)。
3. 5.00g (5.77 mmol) of Compound 2 was placed in a 150mL round bottom flask, 80mL (1.24 mol) of methanesulfonic acid was added, the reaction was heated at 110℃for 8 hours under reflux, after the completion of the reaction, quenched with addition of sodium bicarbonate, extracted with dichloromethane, dried over anhydrous sodium sulfate, and after concentration of the solvent, purified by column chromatography silica gel chromatography (in a volume ratio DCM: PE=1:1 as eluent) to give pure product of Compound 3 in a yield of 41%.
The spectrum data for the resulting compound 3 are as follows: 1 H NMR(600MHz,CDCl 3 )δ7.70(s,3H),7.63(d,J＝2.0Hz,3H),7.38(d,J＝1.9Hz,3H),7.33(dd,J＝6.9,2.3Hz,5H),7.25–7.19(m,4H)。
4.3 g (3.90 mmol) of Compound 3 was placed in a 150mL round bottom flask, 4.34g (140.26 mmol) of red phosphorus and 89.71g (701.32 mmol) of hydroiodic acid were added, 50mL of propionic acid was added as a solvent, and reflux was carried out at 150℃for 48 hours, after the completion of the reaction, the reaction solution was diluted with methylene chloride, the organic phase was washed with saturated aqueous sodium bicarbonate solution, finally dried over anhydrous sodium sulfate, and after concentrating the solvent, purified by column chromatography silica gel chromatography (in a volume ratio DCM: PE=1:6 as eluent) to obtain a pure product of Compound 4 in a yield of 72%.
The spectrum data for the resulting compound 4 are as follows: 1 H NMR(600MHz,CDCl 3 )δ7.61(s,3H),7.42(s,3H),7.25(s,3H),7.11(t,J＝18.7Hz,6H),6.66(t,J＝122.4Hz,3H),3.84(s,6H). 13 CNMR(151MHz,CDCl 3 )δ144.71(d,J＝42.2Hz),144.55–144.11(m),139.81(s),135.70(d,J＝80.5Hz),130.90(s),128.65–128.37(m),128.22(d,J＝30.8Hz),127.78(d,J＝28.2Hz),123.53(s),122.17(s),35.83(s)。
5. 2g (2.75 mmol) of Compound 4 and 4.62g (41.21 mmol) of potassium tert-butoxide were added in a tube-sealed, 10mL of dry THF was added as a solvent, 5.65g (41.21 mmol) of bromobutane was added by syringe under nitrogen protection, the reaction was carried out in an oil bath at 80℃for 3 hours after sealing, after completion of the reaction, the reaction solution was diluted with methylene chloride, the organic phase was washed with aqueous solution, dried over anhydrous sodium sulfate, and after concentrating the solvent, purified by column chromatography silica gel chromatography (eluting with pure petroleum ether) to give pure product of Compound 5 in 83% yield.
The spectrum data for the resulting compound 5 are as follows: 1 H NMR(600MHz,CDCl 3 )δ7.60(s,3H),7.23(d,J＝5.0Hz,6H),7.09(dd,J＝6.9,5.1Hz,2H),6.93(d,J＝8.0Hz,4H),6.85–6.24(m,3H),1.95–1.77(m,12H),1.00(dd,J＝14.4,7.2Hz,12H),0.63–0.43(m,30H). 13 CNMR(151MHz,CDCl 3 )δ154.63–152.98(m),140.76(s),137.01(s),136.00(s),135.78(s),132.30(d,J＝12.7Hz),129.27(s),128.85(s),123.32(d,J＝8.5Hz),122.48(s),55.02(s),40.37(s),25.82(s),22.97(s),13.76(s)。
6. 0.20g (187.85. Mu. Mol) of Compound 5 and 0.34g (1.50 mmol) of DDQ were added to a 100 mL-tube, 30mL of dried methylene chloride was used as a solvent after argon was replaced, 0.9mL of trifluoromethanesulfonic acid was added under ice bath to catalyze the reaction, the reaction was heated at 35℃for 2 hours after the sealing, the reaction mixture was diluted with methylene chloride, insoluble impurities were filtered off by a silica gel bed, and after concentration of the solvent, the solvent was purified by column chromatography silica gel chromatography (using pure petroleum ether as an eluent) to obtain a pure product of Compound 6, the yield of which was 34%.
7. To a 10 mL-sealed tube were added 0.10g (95.00. Mu. Mol) of compound 6, 205.63mg (2.28 mmol) of t-butylmercaptan and 196.95mg (1.43 mmol) of potassium carbonate and 93.85mg (285.01. Mu. Mol) of tetrabutylammonium tetrafluoroborate, and after replacing argon, 2mL of dried N, N-dimethylformamide was added as a solvent, and after sealing, the reaction was heated at 120℃for 48 hours, and after completion of the reaction, the organic phase was washed with hydrochloric acid, extracted with dichloromethane, dried over anhydrous sodium sulfate, and after concentrating the solvent, purified by column chromatography silica gel chromatography (with pure petroleum ether as an eluent) to obtain a pure product of compound 7-1, the yield of which was 26%.
The spectrum data for the resulting compound 7-1 are as follows: 1 H NMR(600MHz,CDCl 3 )δ8.06(s,6H),2.70-2.66(m,6H),2.13-2.09(m,6H),2.05-2.00(m,6H),1.58-1.56(m,6H),1.05(t,J＝7.4Hz,9H),0.59(dd,J＝14.7,7.4Hz,6H),-0.02(t,J＝7.3Hz,9H),-1.01--1.07(m,6H). 13 C NMR(151MHz,CDCl 3 )δ153.00(s),142.88(s),139.79(s),134.76(s),130.82(s),128.59(s),119.60(s),77.26(s),77.04(s),76.83(s),64.38(s),42.14(s),35.83(s),28.65(s),26.06(s),23.62(s),22.46(s),14.30(s),13.16(s).
example 2
Steps 1 to 6 of this example 1 are the same as those of example 1. In step 7, 0.01g (9.50. Mu. Mol) of Compound 6, 81.52mg (570.03. Mu. Mol) of tert-butylseleno lithium (according to the literature "Guschlbauer J, vollgraff T, sundermeyer J. Systematic student' S reaction-cation interactions via doubly ionic H-bonds in1,3-dimethylimidazolium salts comprising chalcogenolate anions MMIm [ ER ] (E=S, se; R=H, tBu, siMe 3) [ J ]. Dalton Transactions,2019,48 (29): 10971-10978)", were added to a 10mL tube, after the replacement of argon, 2.5mL of dried N, N-dimethylformamide was added as a solvent, after the completion of the reaction, the reaction was quenched with diluted hydrochloric acid, extracted with methylene chloride, the organic phase was dried over anhydrous sodium sulfate, and after concentration of the solvent, the solvent was purified by column chromatography silica gel chromatography (using petroleum ether as eluent) to obtain pure product of Compound 7-2 in 17% yield.
The spectrum data for the resulting compound 7-1 are as follows: 1 H NMR(600MHz,CDCl 3 ):δ8.21(s,6H),2.71–2.66(m,6H),2.17–2.12(m,6H),2.02–1.98(m,6H),1.57–1.54(m,6H),1.04(t,J＝7.4Hz,9H),0.59(dd,J＝14.7,7.4Hz,6H),0.01(t,J＝7.3Hz,9H),-0.93–-0.98(m,6H). 13 C NMR(150MHz,CDCl 3 ):δ151.8,141.9,139.0,136.0,129.3,128.2,121.6,64.4,41.5,36.5,28.5,25.8,23.6,22.4,14.3,13.2。
the electrical performance of the compound 7-1 is tested, and the specific method is as follows: first using Al 2 O 3 After the working electrode is polished, the working electrode, the counter electrode and the reference electrode are soaked in absolute ethyl alcohol for 15 minutes. After drying, the electrode, the electrolytic cell, the tetrabutylammonium hexafluorophosphate and the sample to be tested are placed into a glove box, and the tetrabutylammonium hexafluorophosphate and the sample are prepared into a solution to be tested by using ultra-dry dichloromethane. As can be seen from the cyclic voltammogram 1, the compound has two reversible oxidation peaks and no reduction peak in the solvent measurement range, and the two half-wave potentials are respectively 0.93V and 1.37V (figure 2), according to the formula E HOMO ＝-(4.8+E onset ox ) eV and E LUMO ＝(E HOMO +E g opt ) The HOMO and LUMO orbital level values of the compound are respectively-5.65 eV and-3.07 eV. As can be seen from fig. 1 and 2, it is an electrochemically stable compound, due to the presence of two reversible peaks, which can be used as a good electronic device for applications in the semiconductor field.
And performing thermogravimetric analysis on the compound 7-1 under the protection of nitrogen, selecting an instrument Q1000-SDT, heating to 30-800 ℃, and processing the obtained data to obtain a thermogravimetric curve of the compound. As can be seen from fig. 3: the thermal decomposition temperature of the compound is near 410 ℃, and the thermal stability of the compound is similar to that of the traditional HBC derivative, so that the bowl-shaped structure of the compound has higher thermal stability. The compound synthesized by the invention has excellent thermal stability and photoelectric property, and the compound is expected to be applied to the fields of organic photoelectric devices, semiconductor materials, new energy batteries and the like.
Claims (9)
1. A synthesis method of chalcogen heterobowl-shaped molecular graphene comprises the following steps:
wherein M represents S or Se, characterized in that the synthesis method comprises the following steps:
(1) Synthesizing 2-bromo-5-chloroacetophenone into a compound 1 under the catalysis of trifluoromethanesulfonic acid;
(2) Coupling the compound 1 with 4-fluoro-2-methyl formate phenylboronic acid through Suzuki to obtain a compound 2;
(3) Performing Friedel-crafts acylation on the compound 2 under the catalysis of methanesulfonic acid to obtain a compound 3;
(4) Reducing the compound 3 by hydroiodic acid in the presence of red phosphorus to obtain a compound 4;
(5) Reacting the compound 4 with bromobutane under the action of potassium tert-butoxide to obtain a compound 5;
(6) Under the catalysis of trifluoromethanesulfonic acid, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is used as an oxidant to synthesize a compound 6;
(7) When M represents S, the chalcogen heterobowl-shaped molecular graphene is obtained from the compound 6 under the action of tert-butyl mercaptan, potassium carbonate and tetrabutylammonium tetrafluoroborate; and when M represents Se, reacting the compound 6 with tert-butylselenyllithium to obtain the chalcogen heterobowl-shaped molecular graphene.
2. The method for synthesizing chalcogen heterobowl-shaped molecular graphene according to claim 1, wherein the method comprises the following steps: in the step (1), 2-bromo-5-chloroacetophenone reacts for 8 to 9 hours at 140 to 150 ℃ under the catalysis of trifluoromethanesulfonic acid; the molar ratio of the 2-bromo-5-chloroacetophenone to the trifluoromethanesulfonic acid is 1:0.10 to 0.15.
3. The method for synthesizing chalcogen heterobowl-shaped molecular graphene according to claim 1, wherein the method comprises the following steps: in the step (2), toluene is taken as a solvent, and under the protection of inert gas, compound 1, 4-fluoro-2-methyl formate phenylboronic acid, tris (dibenzylideneacetone) dipalladium, 2-dicyclohexylphosphine-2, 6-dimethoxy biphenyl and potassium phosphate are refluxed for 20-24 hours at 100-110 ℃ for Suzuki coupling; the molar ratio of the compound 1 to 4-fluoro-2-methyl formate phenylboronic acid, tris (dibenzylideneacetone) dipalladium, 2-dicyclohexylphosphine-2, 6-dimethoxy biphenyl and potassium phosphate is 1:4.50 to 5.00:0.15 to 0.20:0.45 to 0.50:9.00 to 9.10.
4. The method for synthesizing chalcogen heterobowl-shaped molecular graphene according to claim 1, wherein the method comprises the following steps: in the step (3), the compound 2 is heated and refluxed for 8 to 10 hours at a temperature of between 110 and 180 ℃ under the catalysis of methanesulfonic acid, and is subjected to Friedel-crafts acylation; the molar ratio of the compound 2 to the methylsulfonic acid is 1: 200-250.
5. The method for synthesizing chalcogen heterobowl-shaped molecular graphene according to claim 1, wherein the method comprises the following steps: in the step (4), propionic acid is taken as a solvent, and compound 3, red phosphorus and hydroiodic acid are refluxed for 48-50 hours at 145-155 ℃ to carry out reduction reaction, wherein the molar ratio of the compound 3 to the red phosphorus to the hydroiodic acid is 1: 35-40: 178-200.
6. The method for synthesizing chalcogen heterobowl-shaped molecular graphene according to claim 1, wherein the method comprises the following steps: in the step (5), dry tetrahydrofuran is used as a solvent, and the compound 4 reacts with potassium tert-butoxide and bromobutane for 3 to 5 hours at the temperature of between 75 and 85 ℃ under the protection of inert gas; the molar ratio of the compound 4 to the potassium tert-butoxide to the bromobutane is 1: 14-16: 14-15.
7. The method for synthesizing chalcogen heterobowl-shaped molecular graphene according to claim 1, wherein the method comprises the following steps: in the step (6), dry dichloromethane is used as a solvent, and under the protection of inert gas, the compound 5, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone and trifluoromethanesulfonic acid are heated and reacted for 2 hours at 35 ℃; the molar ratio of the compound 5 to the 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is 1:8, the amount of the triflic acid is 3% of the volume of the solvent.
8. The method for synthesizing chalcogen heterobowl-shaped molecular graphene according to claim 1, wherein the method comprises the following steps: in the step (7), when M represents S, dry N, N-dimethylformamide is taken as a solvent, and under the protection of inert gas, the compound 6 and tert-butyl mercaptan, potassium carbonate and tetrabutylammonium tetrafluoroborate are heated and reacted for 48 to 50 hours at the temperature of 120 to 130 ℃; the molar ratio of the compound 6 to the tert-butyl mercaptan, the potassium carbonate and the tetrabutylammonium tetrafluoroborate is 1:23 to 25: 14-16: 2 to 4.
9. The method for synthesizing chalcogen heterobowl-shaped molecular graphene according to claim 1, wherein the method comprises the following steps: in the step (7), when M represents Se, dry N, N-dimethylformamide is taken as a solvent, and under the protection of inert gas, the compound 6 and tertiary butyl selenium lithium are heated and reacted for 48 to 50 hours at the temperature of 120 to 130 ℃; the molar ratio of the compound 6 to the tert-butylseleno lithium is 1:60 to 80 percent.
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