CN112979402A - Industrial production method of benzo [ a ] anthracene - Google Patents
Industrial production method of benzo [ a ] anthracene Download PDFInfo
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- CN112979402A CN112979402A CN202110271542.2A CN202110271542A CN112979402A CN 112979402 A CN112979402 A CN 112979402A CN 202110271542 A CN202110271542 A CN 202110271542A CN 112979402 A CN112979402 A CN 112979402A
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- phenylnaphthalene
- bromo
- benzo
- anthracene
- industrial production
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- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000009776 industrial production Methods 0.000 title claims abstract description 22
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 25
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 22
- GDQSRRFKYLCYMF-UHFFFAOYSA-N 2-bromo-3-phenylnaphthalene Chemical compound BrC1=CC2=CC=CC=C2C=C1C1=CC=CC=C1 GDQSRRFKYLCYMF-UHFFFAOYSA-N 0.000 claims abstract description 20
- XHWQSFJZSCVQOV-UHFFFAOYSA-N COC=CC1=CC(=CC2=CC=CC=C12)C1=CC=CC=C1 Chemical compound COC=CC1=CC(=CC2=CC=CC=C12)C1=CC=CC=C1 XHWQSFJZSCVQOV-UHFFFAOYSA-N 0.000 claims abstract description 18
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical class CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- APSMUYYLXZULMS-UHFFFAOYSA-N 2-bromonaphthalene Chemical compound C1=CC=CC2=CC(Br)=CC=C21 APSMUYYLXZULMS-UHFFFAOYSA-N 0.000 claims abstract description 15
- IYDMICQAKLQHLA-UHFFFAOYSA-N 1-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 IYDMICQAKLQHLA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 11
- 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 10
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims abstract description 10
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims abstract description 10
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical class CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims abstract description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004327 boric acid Substances 0.000 claims abstract description 8
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 6
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 238000006798 ring closing metathesis reaction Methods 0.000 claims abstract description 5
- MEZCZWDLMIBKID-UHFFFAOYSA-N (3-bromonaphthalen-2-yl)boronic acid Chemical compound C1=CC=C2C=C(Br)C(B(O)O)=CC2=C1 MEZCZWDLMIBKID-UHFFFAOYSA-N 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 52
- 238000001816 cooling Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- 238000007326 Weinreb synthesis reaction Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- CPDRCKWKDRDHPW-UHFFFAOYSA-N boric acid;naphthalene Chemical compound OB(O)O.C1=CC=CC2=CC=CC=C21 CPDRCKWKDRDHPW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- YVLMZDXROKVBHB-UHFFFAOYSA-N O=CC1=CC2=CC=CC=C2C=C1C1=CC=CC=C1 Chemical compound O=CC1=CC2=CC=CC=C2C=C1C1=CC=CC=C1 YVLMZDXROKVBHB-UHFFFAOYSA-N 0.000 claims 1
- 238000007865 diluting Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000005605 benzo group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- 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
-
- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
Abstract
The invention discloses an industrial production method of benzo [ a ] anthracene, belonging to the technical field of organic synthesis, comprising the following steps: carrying out boronization on 2-bromonaphthalene by lithium substitution of 2,2,6, 6-tetramethyl piperidine and triisopropyl borate, and acidifying to obtain 2-bromo-3-naphthalene boric acid; preparing 2-bromo-3 phenylnaphthalene by carrying out Suzuki reaction on 2-bromo-3 naphthylboronic acid and iodobenzene; preparing 2-aldehyde-3 phenylnaphthalene by substituting 2-bromo-3 phenylnaphthalene with n-butyllithium through DMF (dimethyl formamide); carrying out Witting reaction on 2-aldehyde-3-phenylnaphthalene, chloromethyl ether triphenylphosphine salt and sodium tert-butoxide to prepare 2-methoxyvinyl-3-phenylnaphthalene; preparing benzo [ a ] anthracene from 2-methoxyvinyl-3-phenylnaphthalene through ring closure by methanesulfonic acid; compared with the existing benzo [ a ] anthracene synthesis method, the method has the advantages of cheap and easily obtained raw materials, simple operation, less discharge of three wastes, environment-friendly preparation and convenient industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an industrial production method of benzo [ a ] anthracene.
Background
Benzo [ a ] anthracene contains a strong active site, can react with N-chlorosuccinimide, N-bromosuccinimide, dibromohydantoin, bromine and the like, can introduce corresponding halide at the 7 th site of benzo [ a ] anthracene, and then introduces other molecular fragments through Suzuki reaction, Buchwald reaction, Heck reaction, Ullmann reaction and the like to realize the expansion of a molecular structure. The benzo [ a ] anthracene is used as a derivative synthesized by an intermediate, is widely used for synthesizing materials with a conjugated structure, and has wide application in the fields of field effect transistors, organic light emitting diodes and the like.
At present, benzo [ a ] is common]The synthesis method of anthracene uses 1-bromonaphthalene (as shown in figure method 1) as raw material (J.Med.chem.2019,62,15, 7089-7110; J.chem.Soc.,1935,1367-1370) or naphthalene (as shown in figure method 2) as raw material (Beilsteine J.org.chem.2019,15, 1313-1320), and obtains product benzo [ a ] a through Friedel-crafts acylation reaction, strong acid dehydration ring closing, and finally hydrogenation reduction]And (b) anthracene. The main problem of this process is that the three reactions all result in large amounts of waste water. Each 1Kg of benzo [ a ] produced, as measured by method 2]Anthracene, 400Kg of waste water phase is generated. First step AlCl32.50eq is used to generate a large amount of high-salinity wastewater containing aluminum; in the second step, the reaction temperature is lower than 90 ℃, the conversion is incomplete, the temperature is higher than 120 ℃, a large amount of products are carbonized, at least 2 times of volume of methanesulfonic acid is needed to be used as a solvent for dehydration and ring closing in the reaction process, the methanesulfonic acid cannot be recovered, more high-salt wastewater is caused, the emulsification is serious during the post-treatment, and the poor phase separation needs to be carried out for standing at a long time. In the third step, 10 times volume of glacial acetic acid is taken as a solvent, at least 5eq of hydriodic acid and 2.5eq of hypophosphorous acid are used for preparing benzo [ a ] by hydrogenation]Anthracene, in particular, causes and produces a large amount of wastewater.
Generally, the water washing process of the preparation scheme often generates emulsification, the post-treatment operation is difficult, and further the cost of benzo [ a ] anthracene is difficult to reduce, and the operation is complex.
The route is as follows:
disclosure of Invention
In order to solve the problems, the invention provides an industrial production method of benzo [ a ] anthracene, compared with the method, benzo [ a ] anthracene is prepared by changing a reaction route (taking 2-bromonaphthalene as a raw material and sequentially carrying out lithium generation, boronization, acidification, Suzuki reaction, Weinreb reaction, Witting reaction and ring closure), and cheap raw materials 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 reduced, the yield is high, and the method is suitable for industrial production.
The invention provides an industrial production method of benzo [ a ] anthracene, which comprises the following steps:
s1, carrying out lithium substitution on 2,2,6, 6-tetramethyl lithium piperidine by 2-bromonaphthalene, carrying out boronization by triisopropyl borate, and then acidifying to prepare 2-bromo-3-naphthalene boric acid;
s2, preparing 2-bromo-3 phenylnaphthalene by carrying out Suzuki reaction on the 2-bromo-3 naphthylboronic acid prepared in the step S1 and iodobenzene;
s3, carrying out substitution on the 2-bromo-3 phenylnaphthalene prepared in the S2 and N-butyllithium, and then carrying out Weinreb reaction on N, N-dimethylformamide to prepare 2-aldehyde-3 phenylnaphthalene;
s4, carrying out Witting reaction on the 2-aldehyde-3-phenylnaphthalene prepared in the step S3, chloromethyl ether triphenylphosphine salt and potassium tert-butoxide to prepare 2-methoxyvinyl-3-phenylnaphthalene;
s5, preparing benzo [ a ] anthracene from the 2-methoxy vinyl-3-phenyl naphthalene prepared in the S4 through ring closure by methanesulfonic acid;
the synthetic route is as follows:
preferably, the S1 specifically includes the following steps:
s11, mixing 2,2,6, 6-tetramethylpiperidine and tetrahydrofuran, cooling to-20-0 ℃, adding n-butyllithium, and reacting at-20-0 ℃ for 0.5-1 h to obtain 2,2,6, 6-tetramethyllithium piperidine;
s12, cooling the 2,2,6, 6-tetramethyl lithium piperidine system prepared in the S11 to-80-70 ℃, adding triisopropyl borate, adding 2-bromonaphthalene, heating to-55-45 ℃, reacting for 3-5 h in a heat preservation manner, heating to-20-10 ℃, adjusting the pH to 5-6, washing to be neutral, and concentrating to obtain the 2-bromo-3 naphthalene boric acid.
Preferably, in S1, the molar ratio of n-butyllithium to 2,2,6, 6-tetramethylpiperidine is 1: 1-2, 2-bromonaphthalene to tetrahydrofuran is 1 g: 10-15 mL, wherein the molar ratio of 2-bromonaphthalene to n-butyllithium is 1: 2-2.5, and the molar ratio of n-butyllithium to tri-isopropyl borate is 1: 1-2.
Preferably, the S2 specifically includes the following steps:
mixing and dissolving 2-bromo-3-naphthalene boric acid, iodobenzene and potassium carbonate in a mixed solvent prepared from toluene, ethanol and water, heating to 40-50 ℃, adding palladium tetratriphenylphosphine, continuing heating to reflux, reacting for 1-2 h, washing a toluene phase to be neutral, dissolving methylcyclohexane, separating out a solid, and filtering to obtain 2-bromo-3-phenyl naphthalene.
Preferably, in S2, the molar ratio of 2-bromo-3-naphthalene boronic acid to iodobenzene is 1: 1-1.2, the mass ratio of 2-bromo-3 naphthalene boronic acid to palladium tetratriphenylphosphine is 43-44: 1, the mass ratio of 2-bromo-3 naphthalene boronic acid to potassium carbonate is 1.5:1, and the volume ratio of toluene, ethanol and water is 2:1: 1.
Preferably, the S3 specifically includes the following steps:
mixing 2-bromo-3 phenylnaphthalene with tetrahydrofuran, cooling to-90 to-80 ℃, adding n-butyllithium, keeping the temperature at-80 to-90 ℃ for reaction for 0.5 to 1 hour, then adding DMF, keeping the temperature at-80 to-90 ℃ for reaction for 1 to 2 hours, quenching, concentrating and extracting to obtain 2-aldehyde-3 phenylnaphthalene.
Preferably, in S3, the ratio of the 2-bromo-3-phenylnaphthalene to the tetrahydrofuran is 1 g: 10-15 mL of the aqueous solution, wherein the molar ratio of 2-bromo-3 phenylnaphthalene to n-butyllithium is 1: 1.1-1.5, and the molar ratio of 2-bromo-3 phenylnaphthalene to DMF is 1: 1.3-1.7.
Preferably, the S4 specifically includes the following steps:
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 phenyl naphthalene, keeping the temperature at-10-0 ℃ for reaction for 1-2 h, quenching, extracting and concentrating to obtain the 2-methoxy vinyl-3-phenyl naphthalene.
Preferably, in S4, the ratio of the 2-aldehyde-3-phenylnaphthalene to the tetrahydrofuran is 1 g: 10-15 mL, the molar ratio of 2-aldehyde-3-phenylnaphthalene to chloromethyl ether triphenyl phosphonium salt is 1: 1.3-1.7, and the molar ratio of 2-aldehyde-3-phenylnaphthalene to potassium tert-butoxide is 1: 1.5-1.9.
Preferably, the S5 specifically includes the following steps:
mixing 2-methoxy vinyl-3-phenyl naphthalene with toluene, adding methanesulfonic acid, reacting for 1-2 h at 40-50 ℃, washing with water, concentrating, and recrystallizing to obtain benzo [ a ] anthracene; the dosage ratio of the 2-methoxy vinyl-3-phenyl naphthalene to the toluene is 1 g: 10-15 mL, and the molar ratio of the 2-methoxyvinyl-3-phenylnaphthalene to the methanesulfonic acid is 1: 1.5-2.5.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides an industrial production method of benzo [ a ] anthracene, which comprises the following steps: the 2-bromonaphthalene is subjected to lithium substitution by 2,2,6, 6-tetramethylpiperidine, then boric esterification is carried out by triisopropyl borate, and then acidification is carried out to prepare 2-bromo-3-naphthalene boric acid; carrying out Suzuki reaction on 2-bromo-3-naphthalene boric acid and iodobenzene through a catalyst to prepare 2-bromo-3-phenyl naphthalene; substituting 2-bromo-3-phenylnaphthalene with n-butyllithium, and then preparing 2-aldehyde-3-phenylnaphthalene through DMF (dimethyl formamide); carrying out Witting reaction on 2-aldehyde-3-phenylnaphthalene, chloromethyl ether triphenylphosphine salt and sodium tert-butoxide to prepare 2-methoxyvinyl-3-phenylnaphthalene; 2-methoxy vinyl-3-phenyl naphthalene is subjected to ring closure under the action of acid to prepare a target product benzo [ a ] anthracene;
(2) compared with the method in the background art, the method has the advantages that the raw materials adopted in the steps are simple and easy to obtain, the cost is low, the post-treatment process of the steps is simple, the problem that the method in the background art generates a large amount of wastewater is solved, the method is low in environmental hazard, the yield is high, and the industrial production is facilitated.
Drawings
FIG. 1 is a liquid mass spectrum of benzo [ a ] anthracene obtained in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention. The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
An industrial production method of benzo [ a ] anthracene specifically comprises the following steps:
s1, adding 414mL of tetrahydrofuran and 56.50g of 2,2,6, 6-tetramethylpiperidine into a 1L three-neck round-bottom flask in sequence, cooling to-20-0 ℃ under stirring, dropwise adding 200mL of n-butyllithium, stirring for 0.5h, cooling to-80 ℃, adding 75.23g of triisopropylborate, and dropwise adding a tetrahydrofuran solution of 2-bromonaphthalene [ containing 41.41g of 2-bromonaphthalene and 83mL of tetrahydrofuran ] at the temperature of less than-70 DEG]After the dropwise addition, naturally heating to-55 ℃, keeping the temperature between-55 ℃ and-45 ℃, stirring for 3h, heating to-20 ℃, adding hydrochloric acid to acidify until the pH value is 5, naturally heating to room temperature, concentrating under reduced pressure until the internal temperature is 45 ℃, adding 1035mL of dichloroethane to dilute, washing with water until the pH value is 7, carrying out phase separation, concentrating the organic phase at normal pressure until the residual 248mL of the system is obtained, putting the system into a refrigerator to freeze and crystallize for 3h, filtering, and drying to constant weight to obtain 27.59g of light yellow solid of formula (I), wherein the yield is 54.98%. LC-MS calcd for C10H8BBrO2(M+),250；found,250.
The synthetic route is as follows:
s2, sequentially adding 151mL of toluene, 75mL of ethanol, 15.06g of 2-bromo-3-naphthalene boric acid, 14.69g of iodobenzene, 9.95g of potassium carbonate and 75mL of water into a 500mL three-neck round-bottom flask, heating to 40-50 ℃, adding 0.347g of palladium tetratriphenylphosphine, continuously heating to reflux, reacting for 1-2 h, naturally cooling to room temperature, separating liquid, washing the toluene phase with water to be neutral, concentrating the residual 20mL, cooling to 90 ℃, adding 151mL of methylcyclohexane, heating to reflux, dissolving, naturally cooling to room temperature, filtering, and drying to constant weight to obtain 13.68g of white solid of formula (II) with yield of 80.52%. LC-MS calcd for C16H11Br(M+),282；found,282.
The synthetic route is as follows:
s3, adding 142mL of tetrahydrofuran and 14.16g of 2-bromo-3-phenylnaphthalene into a 250mL three-neck round-bottom flask in sequence, cooling to-90 to-80 ℃, adding 32.5mL of n-butyllithium, reacting at-90 to-80 ℃ for 0.5h, adding 5.48g of DMF, reacting at-90 to-80 ℃ for 2h, heating to-20 ℃, and adding 1mL of water to quench the reaction. Naturally heating to room temperature, concentrating under reduced pressure until the internal temperature is equal to 50 ℃, adding 71ml of methylcyclohexane, washing with water to be neutral, concentrating the methylcyclohexane phase at normal pressure until the residual 30ml of the system, naturally cooling to room temperature, filtering, and drying the material to constant weight to obtain 9.49g of white solid shown in the formula (III), wherein the yield is 81.74%. LC-MS calcd for C17H12O(M+),232；found,232.
The synthetic route is as follows:
s4, adding 93mL of tetrahydrofuran and 20.57g of chloromethyl ether triphenylphosphine salt into a 500mL three-neck round-bottom flask in sequence, cooling to-10-0 ℃, adding 6.74g of potassium tert-butoxide (adding in 3 batches), keeping the temperature at 10-0 ℃ for reaction for 2h, and then dropwise adding a tetrahydrofuran solution of 2-aldehyde-3 phenylnaphthalene [ wherein 9.29g of 2-aldehyde-3 phenylnaphthalene is contained, and 46mL of tetrahydrofuran]And after the reaction is carried out for 1 hour at the temperature of between 10 and 0 ℃, adding 1ml of water for quenching reaction, naturally heating to room temperature, adding 93ml of toluene, washing the toluene phase to be neutral, concentrating to the residual 20ml of the system at normal pressure, naturally cooling to room temperature, filtering, and drying the material to constant weight to obtain 8.58g of white solid of the formula (IV), wherein the yield is 82.38%. LC-MS calcd for C20H18O(M+),274；found,274.
The synthetic route is as follows:
s5, adding 86mL of toluene, 8.58g of 2-methoxy vinyl-3-phenyl naphthalene and 7.69g of methanesulfonic acid into a 250mL three-neck round-bottom flask in sequence, keeping the temperature at 40-50 ℃ for reaction for 2h, adding water for washing to neutrality, concentrating the toluene phase to the residual 20mL at normal pressure, cooling to 70 ℃, adding 86mL of ethanol, heating to dissolve and clear, cooling to room temperature for crystallization, filtering, and drying to constant weight to obtain 6.70g of white solid of formula (V), wherein the yield is 89.07%. As shown in FIG. 1, LC-MS is calcd for C18H12(M+),228；found([M+CH3 -]-),242.
The synthetic route is as follows:
example 2
An industrial production method of benzo [ a ] anthracene specifically comprises the following steps:
s1, adding 994mL of tetrahydrofuran and 259.65g of 2,2,6, 6-tetramethyl piperidine into a 5L three-neck round-bottom flask in sequence, cooling to-20-0 ℃ under stirring, dropwise adding 750mL of n-butyl lithium, stirring for 0.5h, cooling to-80 ℃, adding 338.53g of boric acid tri-isopropyl ester, then dropwise adding a tetrahydrofuran solution of 2-bromonaphthalene [ containing 124.24g of 2-bromonaphthalene and 248mL of tetrahydrofuran at the temperature of less than-70 ℃]After the dropwise addition, naturally heating to-55 ℃, keeping the temperature between-55 ℃ and-45 ℃, stirring for 3h, heating to-20 ℃, adding hydrochloric acid to acidify until the pH value is 5, naturally heating to room temperature, concentrating under reduced pressure until the internal temperature is 45 ℃, adding 2485mL of dichloroethane for dilution, washing with water until the pH value is 7, carrying out phase separation, concentrating the organic phase at normal pressure until the rest 745mL of the system is obtained, putting the system into a refrigerator for freezing and crystallizing for 3h, filtering, and drying to constant weight to obtain 81.38g of light yellow solid with the yield of 54.06%. LC-MS calcd for C10H8BBrO2(M+),250；found,250.
S2, sequentially adding 755mL of toluene, 375mL of ethanol, 75.30g of 2-bromo-3-naphthalene boronic acid, 64.26g of iodobenzene, 49.75g of potassium carbonate and 375mL of water into a 2000mL three-neck round-bottom flask, heating to 40-50 ℃, adding 1.733g of palladium tetratriphenylphosphine, continuing to heat to reflux,reacting for 1-2 h, naturally cooling to room temperature, separating liquid, washing a toluene phase to be neutral, concentrating the residual 100ml, cooling to 90 ℃, adding 755ml of methylcyclohexane, heating to reflux, dissolving and cleaning, naturally cooling to room temperature, filtering, and drying to constant weight to obtain 67.53g of white solid with the yield of 79.49%. LC-MS calcd for C16H11Br(M+),282；found,282.
S3, adding 651mL of tetrahydrofuran and 65.13g of 2-bromo-3-phenylnaphthalene into a 1000mL three-neck round-bottom flask in sequence, cooling to-90 to-80 ℃, adding 126.5mL of n-butyllithium, reacting at-90 to-80 ℃ for 0.5h, adding 21.83g of DMF, reacting at-90 to-80 ℃ for 2h, heating to-20 ℃, and adding 5mL of water to quench the reaction. Naturally heating to room temperature, concentrating under reduced pressure until the internal temperature is equal to 50 ℃, adding 500ml of methylcyclohexane, washing with water to neutrality, concentrating the methylcyclohexane phase at normal pressure until the residual 200ml of the system, naturally cooling to room temperature, filtering, and drying the material to constant weight to obtain 43.98g of white solid with the yield of 82.33%. LC-MS calcd for C17H12O(M+),232；found,232.
S4, adding 430mL of tetrahydrofuran and 82.44g of chloromethyl ether triphenylphosphine salt into a 2000mL three-neck round-bottom flask in sequence, cooling to-10-0 ℃, adding 26.99g of potassium tert-butoxide (adding in 3 batches), keeping the temperature at 10-0 ℃ for reaction for 2h, and then dropwise adding a tetrahydrofuran solution of 2-aldehyde-3 phenylnaphthalene [ containing 42.97g of 2-aldehyde-3 phenylnaphthalene and 213mL of tetrahydrofuran]And after the reaction is carried out for 1 hour at the temperature of between 10 and 0 ℃, adding 1ml of water for quenching reaction, naturally heating to room temperature, adding 430ml of toluene, washing the toluene phase to be neutral, concentrating under normal pressure until the residual volume of the system is 85ml, naturally cooling to room temperature, filtering, and drying the material to constant weight to obtain 40.51g of white solid with the yield of 84.12 percent. LC-MS calcd for C20H18O(M+),274；found,274.
S5, sequentially adding 391mL of toluene, 39.05g of 2-methoxyvinyl-3-phenylnaphthalene and 21.62g of methanesulfonic acid into a 250mL three-neck round-bottom flask, reacting at 40-50 ℃ for 2h, adding water to wash the mixture to be neutral, concentrating the toluene phase to be 80mL at normal pressure, cooling to 70 ℃, adding 391mL of ethanol, heating to dissolve and clear, cooling to room temperature for crystallization, filtering, and drying to constant weight to obtain 30.45g of white solid with the yield of 88.92％。LC-MS:calcd forC18H12(M+),228；found([M+CH3 -]-),242.
The method can be used for successfully synthesizing benzo [ a ] anthracene through 5 steps, raw materials adopted in each step of reaction are simple and easy to obtain, the price is low, the treatment after the reaction is simple, a large amount of wastewater is not generated, the yield is high, and the method is suitable for industrial production and application.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (10)
1. An industrial production method of benzo [ a ] anthracene is characterized by comprising the following steps:
s1, carrying out lithium substitution on 2,2,6, 6-tetramethyl lithium piperidine by 2-bromonaphthalene, carrying out boronization by triisopropyl borate, and then acidifying to prepare 2-bromo-3-naphthalene boric acid;
s2, preparing 2-bromo-3 phenylnaphthalene by carrying out Suzuki reaction on the 2-bromo-3 naphthylboronic acid prepared in the step S1 and iodobenzene;
s3, carrying out substitution on the 2-bromo-3 phenylnaphthalene prepared in the S2 and N-butyllithium, and then carrying out Weinreb reaction on N, N-dimethylformamide to prepare 2-aldehyde-3 phenylnaphthalene;
s4, carrying out Witting reaction on the 2-aldehyde-3-phenylnaphthalene prepared in the step S3, chloromethyl ether triphenylphosphine salt and potassium tert-butoxide to prepare 2-methoxyvinyl-3-phenylnaphthalene;
s5, preparing benzo [ a ] anthracene from the 2-methoxy vinyl-3-phenyl naphthalene prepared in the S4 through ring closure by methanesulfonic acid;
the synthetic route is as follows:
2. the industrial production method of benzo [ a ] anthracene according to claim 1, wherein the S1 specifically includes the following steps:
s11, mixing 2,2,6, 6-tetramethylpiperidine and tetrahydrofuran, cooling to-20-0 ℃, adding n-butyllithium, and reacting at-20-0 ℃ for 0.5-1 h to obtain 2,2,6, 6-tetramethyllithium piperidine;
s12, cooling the 2,2,6, 6-tetramethyl lithium piperidine system prepared in the S11 to-80-70 ℃, adding triisopropyl borate, adding 2-bromonaphthalene, heating to-55-45 ℃, reacting for 3-5 h in a heat preservation manner, heating to-20-10 ℃, adjusting the pH to 5-6, diluting with dichloroethane, washing with water to be neutral, concentrating, and crystallizing to obtain the 2-bromo-3 naphthalene boric acid.
3. The industrial production method of benzo [ a ] anthracene according to claim 2, wherein in S1, the molar ratio of n-butyllithium to 2,2,6, 6-tetramethylpiperidine is 1:1 to 2, and the ratio of the amount of 2-bromonaphthalene to tetrahydrofuran is 1 g: 10-15 mL, wherein the molar ratio of 2-bromonaphthalene to n-butyllithium is 1: 2-2.5, and the molar ratio of n-butyllithium to tri-isopropyl borate is 1: 1-2.
4. The industrial production method of benzo [ a ] anthracene according to claim 1, wherein the S2 specifically includes the following steps:
mixing and dissolving 2-bromo-3-naphthalene boric acid, iodobenzene and potassium carbonate in a mixed solvent prepared from toluene, ethanol and water, heating to 40-50 ℃, adding palladium tetratriphenylphosphine, continuing heating to reflux, reacting for 1-2 h, washing a toluene phase to be neutral, and extracting to obtain 2-bromo-3-phenyl naphthalene.
5. The industrial production method of benzo [ a ] anthracene according to claim 4, wherein in S2, the molar ratio of 2-bromo-3-naphthalene boronic acid to iodobenzene is 1: 1-1.2, the mass ratio of 2-bromo-3 naphthalene boronic acid to palladium tetratriphenylphosphine is 43-44: 1, the mass ratio of 2-bromo-3 naphthalene boronic acid to potassium carbonate is 1.5:1, and the volume ratio of toluene, ethanol and water is 2:1: 1.
6. The industrial production method of benzo [ a ] anthracene according to claim 1, wherein the S3 specifically includes the following steps:
mixing 2-bromo-3 phenylnaphthalene with tetrahydrofuran, cooling to-90 to-80 ℃, adding N-butyllithium, reacting at-80 to-90 ℃ for 0.5 to 1 hour, adding N, N-dimethylformamide, reacting at-80 to-90 ℃ for 1 to 2 hours, quenching with water, concentrating, and extracting to obtain 2-aldehyde-3 phenylnaphthalene.
7. The method according to claim 6, wherein the ratio of 2-bromo-3-phenylnaphthalene to tetrahydrofuran in S3 is 1 g: 10-15 mL of the aqueous solution, wherein the molar ratio of 2-bromo-3 phenylnaphthalene to n-butyllithium is 1: 1.1-1.5, and the molar ratio of 2-bromo-3 phenylnaphthalene to DMF is 1: 1.3-1.7.
8. The industrial production method of benzo [ a ] anthracene according to claim 1, wherein the S4 specifically includes the following steps:
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 phenyl naphthalene, keeping the temperature at-10-0 ℃ for reaction for 1-2 h, quenching with water, extracting, and concentrating to obtain the 2-methoxy vinyl-3-phenyl naphthalene.
9. The industrial production method of benzo [ a ] anthracene according to claim 8, wherein the amount ratio of 2-formyl-3-phenylnaphthalene to tetrahydrofuran in S4 is 1 g: 10-15 mL, the molar ratio of 2-aldehyde-3-phenylnaphthalene to chloromethyl ether triphenyl phosphonium salt is 1: 1.3-1.7, and the molar ratio of 2-aldehyde-3-phenylnaphthalene to potassium tert-butoxide is 1: 1.5-1.9.
10. The industrial production method of benzo [ a ] anthracene according to claim 1, wherein the S5 specifically includes the following steps:
mixing 2-methoxy vinyl-3-phenyl naphthalene with toluene, adding methanesulfonic acid, reacting for 1-2 h at 40-50 ℃, washing with water, concentrating a toluene phase, and recrystallizing with ethanol to obtain benzo [ a ] anthracene; the dosage ratio of the 2-methoxy vinyl-3-phenyl naphthalene to the toluene is 1 g: 10-15 mL, and the molar ratio of the 2-methoxyvinyl-3-phenylnaphthalene to the methanesulfonic acid is 1: 1.5-2.5.
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