CN114591136A - Synthetic method of 2-phenylanthracene - Google Patents
Synthetic method of 2-phenylanthracene Download PDFInfo
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- CN114591136A CN114591136A CN202210282110.6A CN202210282110A CN114591136A CN 114591136 A CN114591136 A CN 114591136A CN 202210282110 A CN202210282110 A CN 202210282110A CN 114591136 A CN114591136 A CN 114591136A
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- aldehyde
- phenylanthracene
- ratio
- bromonaphthalene
- styrylnaphthalene
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- GPOMKCKAJSZACG-UHFFFAOYSA-N 2-phenylanthracene Chemical compound C1=CC=CC=C1C1=CC=C(C=C2C(C=CC=C2)=C2)C2=C1 GPOMKCKAJSZACG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000010189 synthetic method Methods 0.000 title abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 20
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 2-methoxy vinyl-3-styryl naphthalene Chemical compound 0.000 claims abstract description 18
- GTILXPRQNNYDHT-UHFFFAOYSA-N 2,3-dibromonaphthalene Chemical compound C1=CC=C2C=C(Br)C(Br)=CC2=C1 GTILXPRQNNYDHT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 10
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims abstract description 10
- WNJSZOGOYJDJMP-UHFFFAOYSA-N ClCOCCl.C1=CC=C(C=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound ClCOCCl.C1=CC=C(C=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 WNJSZOGOYJDJMP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007239 Wittig reaction Methods 0.000 claims abstract description 5
- 238000006798 ring closing metathesis reaction Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 81
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 238000009776 industrial production Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000001308 synthesis method Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000012071 phase Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- SRDBPCUMFBSYFK-UHFFFAOYSA-N 2-[(4-phenylphenyl)methyl]benzaldehyde Chemical compound C1(=CC=C(C=C1)CC1=C(C=O)C=CC=C1)C1=CC=CC=C1 SRDBPCUMFBSYFK-UHFFFAOYSA-N 0.000 description 2
- UKPQBXOGKHHBMK-UHFFFAOYSA-N 2-[(4-phenylphenyl)methyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CC1=CC=C(C=2C=CC=CC=2)C=C1 UKPQBXOGKHHBMK-UHFFFAOYSA-N 0.000 description 2
- PYXBCVWIECUMDW-UHFFFAOYSA-N 2-bromoanthracene Chemical compound C1=CC=CC2=CC3=CC(Br)=CC=C3C=C21 PYXBCVWIECUMDW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- MENYRYNFSIBDQN-UHFFFAOYSA-N 5,5-dibromoimidazolidine-2,4-dione Chemical compound BrC1(Br)NC(=O)NC1=O MENYRYNFSIBDQN-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000007125 Buchwald synthesis reaction Methods 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/004—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with organometalhalides
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a synthetic method of 2-phenylanthracene, which comprises the following steps: reacting 2, 3-dibromonaphthalene with N-butyllithium and N, N-dimethylformamide to generate 2-aldehyde-3-bromonaphthalene; the 2-aldehyde-3-bromonaphthalene and styrene react through Heck to generate 2-aldehyde-3-styrylnaphthalene; 2-aldehyde-3-styryl naphthalene, chloromethyl ether triphenylphosphine salt and potassium tert-butoxide are subjected to a Wittig reaction to generate 2-methoxy vinyl-3-styryl naphthalene; 2-methoxy vinyl-3-styryl naphthalene is subjected to ring closure by methanesulfonic acid to prepare 2-phenylanthracene. The synthesis method of the 2-phenylanthracene provided by the invention adopts cheap raw materials, has simple reaction process and post-treatment, has small harm to the environment, reduces the production cost, has high yield and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a synthetic method of 2-phenylanthracene.
Background
The 2-phenylanthracene contains a plurality of strong active sites and can react with N-chlorosuccinimide, N-bromosuccinimide, dibromohydantoin, bromine and the like. Corresponding halides are introduced into the 10-position and the 5-position of the 2-phenylanthracene, and other molecular fragments are introduced through Suzuki reaction, Buchwald reaction, Heck reaction, Ullmann reaction and the like, so that the expansion of the molecular structure can be realized. Based on the above characteristics, 2-phenylanthracene is widely used for synthesis of materials having a conjugated structure as a derivative synthesized as an intermediate, and has wide applications in the fields of field effect transistors, organic light emitting diodes, and the like.
At present, the first common synthetic method of 2-phenylanthracene is to use 2-bromoanthracene or 2-Otf anthracene and phenylboronic acid as raw Materials (WO 2020149666A 1; WO 2021172664A 1; US 20170250346A 1; Journal of Materials Chemistry C: Materials for Optical and Electronic Devices (2020),8(18),6006-6012) to prepare 2-phenylanthracene (method one), in the synthetic route, the 2-bromoanthracene or 2-Otf anthracene cannot be purchased in large batches in the market, the self-made route is long, the cost is high, three wastes are large, and the method is not suitable for industrial production; secondly, biphenyl and phthalic anhydride are used as raw materials (European Journal of Organic Chemistry (2015),2015(23), 5099-5114; Organic & biological Chemistry (2016),14(12), 3256-3263; Dyes and Pigments (2011),89(3), 313-318; WO 2010114253A 2; WO 2010114263A 2) to prepare 2-phenylanthracene (method II), in the synthetic route, the preparation route is long, particularly when carbonyl is reduced in the third step, the reaction end point is difficult to control, impurities are more, three wastes are large, and the industrial production is not suitable; thirdly, 2- ([1,1 '-biphenyl ] -4-ylmethyl) benzaldehyde or 2- ([1,1' -biphenyl ] -4-ylmethyl) benzoic acid is used as a raw material (European Journal of Organic Chemistry (2015),2015(23), 5099-42-5114) to prepare 2-phenylanthracene (method III), the raw materials are not supplied in the market, the self-preparation in a laboratory is difficult, and acid used in the reaction can generate a large amount of waste water, so that the method is not environment-friendly. The first, second and third synthetic routes are as follows:
the synthesis process of the 2-phenylanthracene has the problems of difficult acquisition of raw materials, high preparation cost, large three wastes, more impurities, difficult control of reaction end point and the like, is only suitable for small-scale preparation, and is difficult to realize industrial production.
Disclosure of Invention
The invention aims to solve the problems that the existing 2-phenylanthracene synthesis process has the defects of difficult acquisition of raw materials, high preparation cost, large three wastes, more impurities, difficult control of reaction end point, suitability for small-scale preparation and difficult realization of industrial production.
In view of the above, the present application addresses this need in the art by providing an industrial process for the production of 2-phenylanthracene. According to the industrial production method of the 2-phenylanthracene, provided by the invention, the reaction route is changed, and the raw materials with low price are adopted in each reaction step, so that the reaction process and the post-treatment are simple, the environmental hazard is small, the production cost is low, the yield is high, and the industrial production is suitable.
In one aspect, the invention relates to a method for synthesizing 2-phenylanthracene, comprising: reacting 2, 3-dibromonaphthalene with N-butyllithium and N, N-dimethylformamide to generate 2-aldehyde-3-bromonaphthalene; the 2-aldehyde-3-bromonaphthalene and styrene react through Heck to generate 2-aldehyde-3-styrylnaphthalene; 2-aldehyde-3-styryl naphthalene, chloromethyl ether triphenylphosphine salt and potassium tert-butoxide are subjected to a Wittig reaction to generate 2-methoxy vinyl-3-styryl naphthalene; 2-methoxy vinyl-3-styryl naphthalene is subjected to ring closure by methanesulfonic acid to prepare 2-phenylanthracene.
Further, the synthesis method of the 2-phenylanthracene provided by the invention comprises the following steps: mixing 2, 3-dibromonaphthalene and tetrahydrofuran, cooling to-80-70 ℃, and then carrying out lithium substitution reaction with N-butyl lithium and N, N-dimethylformamide.
Further, in the synthesis method of the 2-phenylanthracene, the ratio of the 2, 3-dibromonaphthalene to the N-butyllithium to the N, N-dimethylformamide is 1: 1-2: 1.5-3 by molar mass; the ratio of the 2, 3-dibromonaphthalene to the tetrahydrofuran is 1: 10-15 in g: mL.
Further, in the method for synthesizing 2-phenylanthracene provided by the present invention, the step of generating 2-aldehyde-3-styrylnaphthalene comprises: mixing and dissolving 2-aldehyde-3-bromonaphthalene, styrene and triethylamine in toluene, heating to 40-50 ℃, adding palladium tetratriphenylphosphine, continuously heating to reflux, reacting for 1-2 h, washing the toluene phase to be neutral, dissolving methylcyclohexane, separating out solids, and filtering to obtain the 2-aldehyde-3-styrylnaphthalene.
Further, in the synthesis method of 2-phenylanthracene provided by the invention, the ratio of 2-aldehyde-3-bromonaphthalene to styrene to triethylamine is 1: 1-1.2: 1.5-2.5 by molar mass, and the molar ratio of 2-aldehyde-3-bromonaphthalene to tetratriphenylphosphine palladium is 1: 0.01-0.02; the volume ratio of the 2-aldehyde-3-bromonaphthalene to the toluene is 1: 10-20.
Further, the synthesis method of the 2-phenylanthracene provided by the invention comprises the following steps: mixing chloromethyl ether triphenyl phosphonium salt with tetrahydrofuran, cooling to-10-0 ℃, and carrying out Wittig reaction with 2-aldehyde-3-styryl naphthalene and potassium tert-butoxide.
Further, in the synthetic method of the 2-phenylanthracene, the ratio of the 2-aldehyde-3-styrylnaphthalene to the tetrahydrofuran is 1: 10-15 in terms of g: mL; the ratio of the 2-aldehyde-3-styryl naphthalene to the chloromethyl ether triphenyl phosphonium salt to the potassium tert-butoxide is 1: 1.3-1.7: 1.5-1.9 by mol mass.
Further, in the synthesis method of 2-phenylanthracene provided by the invention, the preparation of 2-phenylanthracene by ring closure comprises the following steps: mixing 2-methoxy vinyl-3-styryl naphthalene and toluene, adding methanesulfonic acid, reacting for 1-2 h at 40-50 ℃, washing with water, concentrating, and recrystallizing to obtain the 2-phenylanthracene.
Further, in the synthetic method of the 2-phenylanthracene, the ratio of the 2-methoxyvinyl-3-styrylnaphthalene to the toluene is 1: 10-15 in terms of g: mL; the ratio of the 2-methoxy vinyl-3-styryl naphthalene to the methanesulfonic acid is 1: 1.5-2.5 by molar mass.
Specifically, the synthesis method of the 2-phenylanthracene provided by the invention comprises the following steps: mixing 2, 3-dibromonaphthalene and tetrahydrofuran, cooling to-80-70 ℃, adding N-butyllithium, reacting at-80-70 ℃ for 0.5-1 h, adding N, N-dimethylformamide, reacting at-80-70 ℃ for 3-5 h, heating to-50-40 ℃, adding water to quench, adjusting the pH value of a water phase to 7-8, and concentrating to obtain 2-aldehyde-3-bromonaphthalene; mixing and dissolving 2-aldehyde-3-bromonaphthalene, styrene and triethylamine in toluene, heating to 40-50 ℃, adding palladium tetratriphenylphosphine, continuously heating to reflux, reacting for 1-2 h, washing the toluene phase to be neutral, dissolving methylcyclohexane, separating out solids, and filtering to obtain 2-aldehyde-3-styrylnaphthalene; mixing chloromethyl ether triphenyl phosphonium salt and tetrahydrofuran, cooling to-10-0 ℃, adding potassium tert-butoxide, keeping the temperature at-10-0 ℃ for reaction for 1-2 h, adding 2-aldehyde-3-styryl naphthalene, keeping the temperature at-10-0 ℃ for reaction for 1-2 h, quenching, extracting and concentrating to obtain 2-methoxy vinyl-3-styryl naphthalene; mixing 2-methoxy vinyl-3-styryl naphthalene and toluene, adding methanesulfonic acid, reacting for 1-2 h at 40-50 ℃, washing with water, concentrating, and recrystallizing to obtain 2-phenylanthracene.
Compared with the prior art, the invention has the following beneficial effects or advantages:
the invention provides a synthesis method of 2-phenylanthracene, which adopts 4 steps to prepare the 2-phenylanthracene. The synthesis method changes the reaction route, adopts cheap raw materials in each reaction step, greatly reduces the production cost on the basis of simple reaction process and post-treatment, avoids the problem of generating a large amount of wastewater, has small harm to the environment and high yield, and is suitable for industrial production.
Drawings
FIG. 1 is a liquid phase spectrum of 2-phenylanthracene obtained in example 1.
FIG. 2 is a liquid mass spectrum of 2-phenylanthracene obtained in example 2.
Detailed Description
The following examples are given to illustrate the technical aspects of the present invention, but the present invention is not limited to the following examples.
Example 1
This example provides an industrial production method of 2-phenylanthracene.
The synthesis process is as follows:
adding 286mL of tetrahydrofuran and 28.60g (0.1mol) of 2, 3-dibromonaphthalene into a 1L three-neck round-bottom flask in sequence, cooling to-80 to-70 ℃ under stirring, dropwise adding 60mL (2mol/L and 0.12mol) of N-butyllithium, stirring for 0.5h, adding 10.97g (0.15mol) of N, N-dimethylformamide, keeping the temperature at-85 to-70 ℃ and stirring for 3h after dropwise addition, naturally heating to-20 ℃, adding hydrochloric acid and acidifying to pH 7, naturally heating to room temperature, concentrating under reduced pressure until the internal temperature is equal to 45 ℃, adding 286mL of toluene for dilution, carrying out phase separation, concentrating the organic phase to the rest 30mL of the system under normal pressure, adding 143mL of N-heptane, putting into a refrigerator for 3h of cryocrystallization, filtering, and drying to constant weight to obtain 20.30g of the white-like solid (1), wherein the yield is 86.35%. LC-MS calcd for C11H7BrO (M +), 235; found, 235.
The synthetic route is as follows:
adding 235mL of toluene, 23.51g (0.1mol) of 2-aldehyde-3-bromonaphthalene, 11.46g (0.11mol) of styrene and 15.18g (0.15mol) of triethylamine into a 500mL three-neck round-bottom flask in sequence, heating to 40-50 ℃, adding 1.156g (0.001mol) of palladium tetratriphenylphosphine, continuing heating to reflux, reacting for 1-2 h, naturally cooling to room temperature, separating, washing a toluene phase with water to be neutral, concentrating the residual 25mL, cooling to 90 ℃, adding 118mL of methylcyclohexane, heating to reflux, dissolving and clearing, naturally cooling to room temperature, filtering, and drying to constant weight to obtain 18.08g of a white solid of formula (2), wherein the yield is 70.00%. LC-MS calcd for C19H14O (M +), 258; found,258.
The synthetic route is as follows:
adding 78mL of tetrahydrofuran and 44.56g (0.13mol) of chloromethyl ether triphenyl phosphonium salt into a 500mL three-neck round-bottom flask in sequence, cooling to-10-0 ℃, adding 16.83g (0.15mol) of potassium tert-butoxide, reacting at 10-0 ℃ for 2h, dropwise adding a tetrahydrofuran solution of 2-aldehyde-3-styrylnaphthalene [ containing 25.83g (0.1mol) of 2-aldehyde-3-styrylnaphthalene and 129mL of tetrahydrofuran ], reacting at-10-0 ℃ for 1h, adding 1mL of water to quench the reaction, naturally heating to room temperature, adding 129mL of toluene, washing the toluene phase to be neutral, concentrating under normal pressure to the residual 25mL of the system, adding 78mL of ethanol, naturally cooling to room temperature, filtering, and drying to constant weight to obtain 26.34g of white solid (3), wherein the yield is 91.97%. LC-MS calcd for C21H18O (M +), 286; found,286.
The synthetic route is as follows:
115mL of toluene and 11.45g (0.04mol) of 2-methoxyvinyl-3-styrylnaphthalene are sequentially added into a 250mL three-neck round-bottom flask, 5.77g (0.06mol) of methanesulfonic acid is added, the temperature is kept at 40-50 ℃ for reaction for 2h, water is added for washing until the mixture is neutral, the toluene phase is concentrated to the residual 10mL under normal pressure, the temperature is reduced to 70 ℃, 58mL of ethanol is added, the temperature is increased to be dissolved and clear, the temperature is reduced to room temperature for crystallization, the mixture is filtered, and the material is dried until the weight is constant to obtain 8.65g of yellow solid (4), and the yield is 85.03%. Its liquid phase spectrum is shown in FIG. 1, LC-MS: calcd for C20H14(M +), 254; found ([ M + CH3- ] -),254.
The synthetic route is as follows:
example 2
This example provides an industrial production method of 2-phenylanthracene.
The synthesis process is as follows:
adding 286mL of tetrahydrofuran and 28.60g (0.1mol) of 2, 3-dibromonaphthalene into a 1L three-neck round-bottom flask in sequence, cooling to-80 to-70 ℃ under stirring, dropwise adding 90mL (2mol/L and 0.18mol) of N-butyllithium, stirring for 0.5h, adding 18.26g (0.25mol) of N, N-dimethylformamide, keeping the temperature at-85 to-70 ℃ and stirring for 3h after dropwise addition, naturally heating to-20 ℃, adding hydrochloric acid and acidifying to pH 7, naturally heating to room temperature, concentrating under reduced pressure until the internal temperature is equal to 45 ℃, adding 286mL of toluene for dilution, carrying out phase separation, concentrating the organic phase to the rest 30mL of the system under normal pressure, adding 143mL of N-heptane, putting into a refrigerator for 3h of cryocrystallization, filtering, and drying to constant weight to obtain 19.88g of the white-like solid (1), wherein the yield is 84.56%. LC-MS calcd for C11H7BrO (M +), 235; found, 235.
Adding 235mL of toluene, 23.51g (0.1mol) of 2-aldehyde-3-bromonaphthalene, 12.50g (0.12mol) of styrene and 25.30g (0.25mol) of triethylamine into a 500mL three-neck round-bottom flask in sequence, heating to 40-50 ℃, adding 2.311g (0.002mol) of palladium tetratriphenylphosphine, continuing heating to reflux, reacting for 1-2 h, naturally cooling to room temperature, separating, washing a toluene phase with water to be neutral, concentrating the residual 25mL, cooling to 90 ℃, adding 118mL of methylcyclohexane, heating to reflux, dissolving and clearing, naturally cooling to room temperature, filtering, and drying to constant weight to obtain 19.20g of a white solid of formula (2) with yield of 74.33%. LC-MS calcd for C19H14O (M +), 258; found,258.
Adding 78mL of tetrahydrofuran and 51.42g (0.15mol) of chloromethyl ether triphenyl phosphate into a 500mL three-neck round-bottom flask in sequence, cooling to-10-0 ℃, adding 20.20g (0.18mol) of potassium tert-butoxide, reacting at 10-0 ℃ for 2h, dropwise adding a tetrahydrofuran solution of 2-aldehyde-3-styrylnaphthalene [ containing 25.83g (0.1mol) of 2-aldehyde-3-styrylnaphthalene and 129mL of tetrahydrofuran ], reacting at 10-0 ℃ for 1h, adding 1mL of water to quench the reaction, naturally heating to room temperature, adding 129mL of toluene, washing the toluene phase to be neutral, concentrating under normal pressure to the residual 25mL of the system, adding 78mL of ethanol, naturally cooling to room temperature, filtering, and drying to constant weight to obtain 25.96g of white solid (3), wherein the yield is 90.64%. LC-MS calcd for C21H18O (M +), 286; found,286.
286mL of toluene and 28.64g (0.1mol) of 2-methoxyvinyl-3-styrylnaphthalene are sequentially added into a 250mL three-neck round-bottom flask, 5.77g (0.2mol) of methanesulfonic acid is added, the temperature is kept at 40-50 ℃ for reaction for 2h, water is added for washing until the mixture is neutral, the toluene phase is concentrated to the residual 30mL under normal pressure, the temperature is reduced to 70 ℃, 143mL of ethanol is added, the temperature is increased to be dissolved and clear, the temperature is reduced to room temperature for crystallization, the filtration is carried out, the materials are dried until the weight is constant, 20.35g of yellow solid of formula (4) is obtained, and the yield is 80.02%. The liquid-mass spectrum is shown in figure 2, LC-MS is calcd for C20H14(M +), 254; found ([ M + CH3- ] -),254.
The same examples as those of the above white solid of formula (1), white solid of formula (2), white solid of formula (3) and yellow solid of formula (4) were repeated. As can be seen from the above synthetic processes, the synthetic method provided by the present invention uses tetrahydrofuran and 2, 3-dibromonaphthalene as raw materials in each reaction step, and has lower synthetic cost compared to the prior art (European Journal of Organic Chemistry (2015),2015(23),5099-5114) using 2- ([1,1 '-biphenyl ] -4-ylmethyl) benzaldehyde or 2- ([1,1' -biphenyl ] -4-ylmethyl) benzoic acid as raw materials. Different from other prior art for synthesizing 2-phenylanthracene (WO 2020149666A 1; WO 2021172664A 1; US 20170250346A 1; Journal of Materials Chemistry C: Materials for Optical and Electronic Devices (2020),8(18),6006 and 6012), the reaction process and the post-treatment provided by the embodiment of the invention greatly reduce the production cost, avoid the problem of generating a large amount of wastewater, have small harm to the environment and high yield, and are suitable for industrial production.
As described above, the present invention can be preferably implemented, and the above-mentioned embodiments only describe the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various changes and modifications of the technical solution of the present invention made by those skilled in the art without departing from the design spirit of the present invention shall fall within the protection scope defined by the present invention.
Claims (10)
1. A method for synthesizing 2-phenylanthracene is characterized by comprising the following steps: reacting 2, 3-dibromonaphthalene with N-butyllithium and N, N-dimethylformamide to generate 2-aldehyde-3-bromonaphthalene; the 2-aldehyde-3-bromonaphthalene and styrene react through Heck to generate 2-aldehyde-3-styrylnaphthalene; 2-aldehyde-3-styryl naphthalene, chloromethyl ether triphenylphosphine salt and potassium tert-butoxide are subjected to a Wittig reaction to generate 2-methoxy vinyl-3-styryl naphthalene; 2-methoxy vinyl-3-styryl naphthalene is subjected to ring closure by methanesulfonic acid to prepare 2-phenylanthracene.
2. The method of claim 1, comprising: mixing 2, 3-dibromonaphthalene and tetrahydrofuran, cooling to-80-70 ℃, and then carrying out lithium substitution reaction with N-butyl lithium and N, N-dimethylformamide.
3. The method according to claim 2, wherein the ratio of the 2, 3-dibromonaphthalene to the N-butyllithium to the N, N-dimethylformamide is 1:1 to 2:1.5 to 3 by molar mass; the ratio of the 2, 3-dibromonaphthalene to the tetrahydrofuran is 1: 10-15 in g: mL.
4. The method of claim 1, wherein the step of generating the 2-formyl-3-styrylnaphthalene comprises: mixing and dissolving 2-aldehyde-3-bromonaphthalene, styrene and triethylamine in toluene, heating to 40-50 ℃, adding palladium tetratriphenylphosphine, continuously heating to reflux, reacting for 1-2 h, washing the toluene phase to be neutral, dissolving methylcyclohexane, separating out solids, and filtering to obtain the 2-aldehyde-3-styrylnaphthalene.
5. The method according to claim 4, wherein the ratio of the 2-aldehyde-3-bromonaphthalene to the styrene to the triethylamine is 1:1 to 1.2:1.5 to 2.5, and the molar ratio of the 2-aldehyde-3-bromonaphthalene to the tetrakistriphenylphosphine palladium is 1:0.01 to 0.02; the volume ratio of the 2-aldehyde-3-bromonaphthalene to the toluene is 1: 10-20.
6. The method of claim 1, comprising: mixing chloromethyl ether triphenyl phosphonium salt with tetrahydrofuran, cooling to-10-0 ℃, and carrying out Wittig reaction with 2-aldehyde-3-styryl naphthalene and potassium tert-butoxide.
7. The method according to claim 6, wherein the ratio of the 2-aldehyde-3-styrylnaphthalene to the tetrahydrofuran is 1: 10-15 in g: mL; the ratio of the 2-aldehyde-3-styryl naphthalene to the chloromethyl ether triphenyl phosphonium salt to the potassium tert-butoxide is 1: 1.3-1.7: 1.5-1.9 by mol mass.
8. The method of claim 1, wherein said ring closing to produce 2-phenylanthracene comprises: mixing 2-methoxyvinyl-3-styrylnaphthalene with toluene, adding methanesulfonic acid, reacting for 1-2 h at 40-50 ℃, washing with water, concentrating, and recrystallizing to obtain the 2-phenylanthracene.
9. The method according to claim 8, wherein the ratio of the 2-methoxyvinyl-3-styrylnaphthalene to the toluene is 1: 10-15 in g: mL; the ratio of the 2-methoxy vinyl-3-styryl naphthalene to the methanesulfonic acid is 1: 1.5-2.5 by molar mass.
10. Use of the process of any one of claims 1 to 9 for the preparation of 2-phenylanthracene.
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