CN113957461A - Electrochemical synthesis method of 1,1' -binaphthyl compound - Google Patents
Electrochemical synthesis method of 1,1' -binaphthyl compound Download PDFInfo
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- -1 1,1' -binaphthyl compound Chemical class 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012074 organic phase Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 11
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 150000002790 naphthalenes Chemical class 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000012544 monitoring process Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 238000003818 flash chromatography Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- YSHGRWZEZYZZNB-UHFFFAOYSA-N 1-methyl-4-(4-methylnaphthalen-1-yl)naphthalene Chemical group C12=CC=CC=C2C(C)=CC=C1C1=CC=C(C)C2=CC=CC=C12 YSHGRWZEZYZZNB-UHFFFAOYSA-N 0.000 description 4
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 4
- CXDKRSFSUNPIDB-UHFFFAOYSA-N 1-(2,4-dimethylnaphthalen-1-yl)-2,4-dimethylnaphthalene Chemical group C1=CC=C2C(C3=C4C=CC=CC4=C(C)C=C3C)=C(C)C=C(C)C2=C1 CXDKRSFSUNPIDB-UHFFFAOYSA-N 0.000 description 3
- IGFVWCOWHFAJPA-UHFFFAOYSA-N 1-(4,5-dimethylnaphthalen-1-yl)-4,5-dimethylnaphthalene Chemical group C1=CC=C2C(C3=C4C=CC=C(C4=C(C)C=C3)C)=CC=C(C)C2=C1C IGFVWCOWHFAJPA-UHFFFAOYSA-N 0.000 description 3
- UELAEJHMIAUAPB-UHFFFAOYSA-N 1-ethyl-4-(4-ethylnaphthalen-1-yl)naphthalene Chemical group C12=CC=CC=C2C(CC)=CC=C1C1=CC=C(CC)C2=CC=CC=C12 UELAEJHMIAUAPB-UHFFFAOYSA-N 0.000 description 3
- MQYAATDATFXREH-UHFFFAOYSA-N 1-propan-2-yl-4-(4-propan-2-ylnaphthalen-1-yl)naphthalene Chemical group C12=CC=CC=C2C(C(C)C)=CC=C1C1=CC=C(C(C)C)C2=CC=CC=C12 MQYAATDATFXREH-UHFFFAOYSA-N 0.000 description 3
- VHMHKCGULUBCIU-UHFFFAOYSA-N 2-methoxy-1-(2-methoxy-6-methylnaphthalen-1-yl)-6-methylnaphthalene Chemical group CC1=CC=C2C(C3=C4C=CC(C)=CC4=CC=C3OC)=C(OC)C=CC2=C1 VHMHKCGULUBCIU-UHFFFAOYSA-N 0.000 description 3
- NUBNNORVNZUBFG-UHFFFAOYSA-N 4-(3,4-dimethylnaphthalen-1-yl)-1,2-dimethylnaphthalene Chemical group C1=CC=CC2=C(C)C(C)=CC(C=3C4=CC=CC=C4C(C)=C(C)C=3)=C21 NUBNNORVNZUBFG-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- QHJMFSMPSZREIF-UHFFFAOYSA-N 1,3-dimethylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC(C)=C21 QHJMFSMPSZREIF-UHFFFAOYSA-N 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XAABPYINPXYOLM-UHFFFAOYSA-N 1,8-dimethylnaphthalene Chemical compound C1=CC(C)=C2C(C)=CC=CC2=C1 XAABPYINPXYOLM-UHFFFAOYSA-N 0.000 description 1
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- PMPBFICDXLLSRM-UHFFFAOYSA-N 1-propan-2-ylnaphthalene Chemical compound C1=CC=C2C(C(C)C)=CC=CC2=C1 PMPBFICDXLLSRM-UHFFFAOYSA-N 0.000 description 1
- JWXYEXKKOMBZBH-UHFFFAOYSA-N 2-methoxy-6-methylnaphthalene Chemical compound C1=C(C)C=CC2=CC(OC)=CC=C21 JWXYEXKKOMBZBH-UHFFFAOYSA-N 0.000 description 1
- KDHFKMDVFWYSPT-UHFFFAOYSA-N 2-methyl-1-(2-methylnaphthalen-1-yl)naphthalene Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3C)=C(C)C=CC2=C1 KDHFKMDVFWYSPT-UHFFFAOYSA-N 0.000 description 1
- BBSSUOFNQSXDCO-UHFFFAOYSA-N 2-methyl-1-(7-methylnaphthalen-1-yl)naphthalene Chemical group C1=CC=C2C(C3=CC=CC4=CC=C(C=C43)C)=C(C)C=CC2=C1 BBSSUOFNQSXDCO-UHFFFAOYSA-N 0.000 description 1
- 238000003692 Hiyama coupling reaction Methods 0.000 description 1
- 238000005577 Kumada cross-coupling reaction Methods 0.000 description 1
- 238000006411 Negishi coupling reaction Methods 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/03—Acyclic or carbocyclic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an electrochemical synthesis method of a 1,1' -binaphthyl compound, which comprises the following steps: sequentially adding a solvent, an electrolyte, a naphthalene compound and a positive electrode and a negative electrode into a diaphragm-free electrolytic cell, stirring at room temperature, and reacting under a constant current condition; after the reaction is finished, concentrating the reaction solution, and separating and purifying the organic phase to obtain the product 1,1' -binaphthyl compound. The method has the advantages of easily obtained raw materials, no transition metal and oxidant, no safety problem and heavy metal residue problem, simple operation, considerable yield, environmental friendliness and good application prospect. The electrode used in the invention is a common inert electrode, electrode modification is not needed, oxidant and toxic and expensive catalyst are not used, the reaction yield is high, and the reaction system is simple and safe.
Description
Technical Field
The invention belongs to the technical field of electrochemical organic synthesis, relates to a synthesis method of 1,1 '-binaphthyl, and particularly relates to an electrochemical preparation method of a 1,1' -binaphthyl compound.
Background
The 1,1' -binaphthyl is the core structure of various functional material molecules such as bioactive molecules, dyes, supermolecules, sensors and the like. The 1,1 '-binaphthyl compound has chiral axis characteristic, so that the 1,1' -binaphthyl compound can be widely applied to the field of organic asymmetric synthesis as a chiral ligand and a chiral catalyst.
The traditional method for preparing 1,1' -binaphthyl compounds comprises two main types of reduction coupling and oxidation coupling. The reduction coupling is mainly realized by Kumada, Negishi, Stille, Hiyama and Suzuki coupling reaction; the oxidative coupling is to directly construct a 1,1' -binaphthyl skeleton by dehydrogenation between two naphthalenes and derivatives thereof. It is noteworthy that transition metals and stoichiometrically strong oxidizers are critical to the above reaction, resulting in high cost, low atomic efficiency, environmental problems and limited industrial application. In 2018, Waldvogel et al [ B.Dahms, R.Franke and S.R.Waldvogel, ChemElectrochem,2018,5, 1249-. However, it should be noted that the substrates of such methods are limited to naphthalene compounds having a strong electron donating group attached thereto, so that the substrates are limited. Therefore, the method has important significance in finding a synthesis route which does not need an exogenous oxidant, does not participate in a transition metal catalyst and has a wide application range, further reducing the preparation cost and solving the environmental problem.
Furthermore, US5522982A discloses a process for electrochemically preparing 4,4 '-dimethyl-1, 1' -binaphthyl, which comprises electrochemically oxidatively dimerizing 1-methylnaphthalene in the presence of a mixture of acetonitrile, water, a conductive salt, and at least one additional component. However, such methods require an additional solvent immiscible or only partially miscible with water to be added to the reaction system, making the reaction system and operation complicated. Meanwhile, the substrate of the method is 1-methyl substituted naphthalene, does not contain a substrate containing a strong electron-donating group on a naphthalene ring, and has a narrow application range. Therefore, it is very important to develop a reaction system and a synthetic route for preparing 1,1' -binaphthyl, which is simple to operate and has a wide application range.
US5767333A discloses a process for the electrochemical preparation of 2,2 '-dimethyl-1, 1' -binaphthyl and 2,7 '-dimethyl-1, 1' -binaphthyl by electrochemical oxidation of dimerized 2-methylnaphthalene in the presence of an electrolyte. However, the system still needs to contain at least one other component which is immiscible or only partially miscible with water, and the products are mixtures, which makes it difficult to satisfy the specificity and precise synthesis of the reaction. Therefore, how to realize the precise synthesis of the 1,1' -binaphthyl by an electrochemical organic synthesis means has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, particularly the problems of high cost, complex reaction system and operation, narrow application range, low atomic efficiency, environmental friendliness, no friendliness and the like of the existing preparation method, the invention provides a method for synthesizing 1,1' -binaphthyl compounds, which is more green, environment-friendly and wide in application range. The invention adopts an electrochemical synthesis method, does not contain exogenous oxidant and transition metal to catalyze the activation of C-H bonds to synthesize various 1,1' -binaphthyl compounds, and provides a high-efficiency, green and environment-friendly synthesis route with atom economy, simple steps and wide application range for bioactive molecules, functional material molecules and organic catalytic micromolecules so as to meet the requirements of industrial application.
The technical scheme of the invention is as follows:
an electrochemical synthesis method of 1,1' -binaphthyl compounds comprises the following steps:
sequentially adding a solvent, an electrolyte, a naphthalene compound and a positive electrode and a negative electrode into a diaphragm-free electrolytic cell, stirring at room temperature, and reacting under a constant current condition; after the reaction is finished, concentrating the reaction solution, and separating and purifying the organic phase to obtain the product 1,1' -binaphthyl compound.
According to the present invention, preferably, the naphthalene compound has a structure represented by formula (I):
in the formula (I), R1Selected from alkyl, preferably methyl, 2-propanoate carbomethoxy, 2-propanoate; alkoxy, preferably methoxy; a hydrogen atom;
R2selected from alkyl, preferably methyl, ethyl; alkoxy, preferably methoxy; a hydroxyl group;
according to the present invention, preferably, the 1,1' -binaphthyl compound has a structure represented by formula (II):
in the formula (II), the compound is shown in the specification,R1、R2the meanings indicated are the same as in formula (I).
According to the present invention, it is preferable that the cathode is a platinum sheet electrode and the anode electrode is a carbon rod.
According to the invention, preferably, the solvent is one or any combination of acetonitrile and hexafluoroisopropanol.
According to the present invention, preferably, the electrolyte is one of lithium perchlorate, lithium fluoride, potassium hexafluorophosphate and tetrabutylammonium hexafluorophosphate.
According to the invention, the molar concentration of the electrolyte in the solvent is preferably 0.08-0.4 mol/L. Too large or too small a concentration will result in a decrease in yield.
According to the invention, the constant current is preferably 5-10 mA. Too much or too little current will result in reduced yield.
According to the invention, the reaction temperature is preferably 25 ℃. Too high a temperature will result in a reduced yield. Preferably, the reaction is carried out under air conditions.
According to the invention, the reaction time is preferably 4-12 h.
According to the present invention, preferably, the separation and purification method is as follows: the solvent was removed by rotary evaporation and the residue was purified by column chromatography over silica gel with ethyl acetate as eluent: petroleum ether is 1: 10.
according to the invention, the electrochemical synthesis method of the 1,1' -binaphthyl compound, a preferred embodiment, comprises the following steps:
(1) sequentially adding 0.4mmol of naphthalene compounds, 1.0mmol of lithium perchlorate and 5mL of acetonitrile into a 10mL three-necked flask, reacting for 5h at constant current of 5mA under the air condition and at 25 ℃ by using a carbon rod as an anode and a platinum sheet electrode as a cathode, and tracking and monitoring by TLC;
(2) after the reaction is finished, removing the solvent of the reaction solution by using a rotary evaporator, and purifying the residue by using a flash silica gel column chromatography to obtain a product, wherein an eluant adopted by the silica gel column chromatography is ethyl acetate: petroleum ether is 1: 3 to 50.
The principle of the invention is as follows:
the invention has the beneficial effects that:
1. the method for electrochemically synthesizing the 1,1' -binaphthyl compound has the advantages of easily obtained raw materials, no transition metal and oxidant, no safety problem and heavy metal residue problem, simple operation, considerable yield, environmental friendliness and good application prospect.
2. The electrode used in the invention is a common inert electrode, electrode modification is not needed, oxidant and toxic and expensive catalyst are not used, the reaction yield is high, and the reaction system is simple and safe.
3. Compared with the method for preparing the 1,1' -binaphthyl compound by reduction coupling, the method avoids the use of a metal catalyst, does not need to prepare halogenated naphthalene and analogues thereof in advance, greatly reduces the reaction cost, and has the advantage of simple and convenient operation;
compared with the conventional method for preparing the 1,1' -binaphthyl compound by oxidative coupling, the method avoids the use of equivalent chemical oxidant, saves the cost, and avoids the pollution of byproducts of the reduced chemical oxidant to the environment;
compared with an electrochemical synthesis method taking high-activity naphthylamine and naphthol as raw materials [ B.Dahms, R.Franke and S.R. Waldvogel, ChemElectrochem,2018,5,1249-1252], the method not only takes high-activity naphthalene as a raw material, but also takes weakly-activated naphthalene (such as alkyl naphthalene) as a substrate, and has wider application range and higher reaction yield;
compared with the reported 1,1' -binaphthyl compound prepared by coupling 1-methylnaphthalene or 2-methylnaphthalene (US5522982A, US5767333A), the method avoids the use of a multi-solvent system, thereby ensuring simple and convenient operation, and has the advantages of precise synthesis and wide substrate application range.
Drawings
FIG. 1 shows 4,4 '-diethyl-1, 1' -binaphthyl prepared in example 1 of the present invention1H NMR chart.
FIG. 2 shows 4,4 '-diethyl-1, 1' -binaphthyl prepared in example 1 of the present invention13C NMR chart.
FIG. 3 shows 4,4 '-dimethyl-1, 1' -binaphthyl prepared in example 2 of the present invention1H NMR chart.
FIG. 4 shows 4,4 '-dimethyl-1, 1' -binaphthyl prepared in example 2 of the present invention13C NMR chart.
FIG. 5 shows 4,4 '-diisopropyl-1, 1' -binaphthyl prepared in example 3 of the present invention1H NMR chart.
FIG. 6 shows 4,4 '-diisopropyl-1, 1' -binaphthyl prepared in example 3 of the present invention13C NMR chart.
FIG. 7 shows 3,3 ', 4,4 ' -tetramethyl-1, 1' -binaphthyl prepared in example 4 of the present invention1H NMR chart.
FIG. 8 shows 3,3 ', 4,4 ' -tetramethyl-1, 1' -binaphthyl prepared in example 4 of the present invention13C NMR chart.
FIG. 9 shows 2,2 ', 4,4 ' -tetramethyl-1, 1' -binaphthyl prepared in example 5 of the present invention1H NMR chart.
FIG. 10 shows 2,2 ', 4,4 ' -tetramethyl-1, 1' -binaphthyl prepared in example 5 of the present invention13C NMR chart.
FIG. 11 shows 4,4 ', 5,5 ' -tetramethyl-1, 1' -binaphthyl prepared in example 6 of the present invention1H NMR chart.
FIG. 12 shows 4,4 ', 5,5 ' -tetramethyl-1, 1' -binaphthyl prepared in example 6 of the present invention13C NMR chart.
FIG. 13 shows 2,2 ' -dimethoxy-6, 6 ' -dimethyl-1, 1' -binaphthyl prepared in example 7 of the present invention1H NMR chart.
FIG. 14 shows 2,2 ' -dimethoxy-6, 6 ' -dimethyl-1, 1' -binaphthyl prepared in example 7 of the present invention13C NMR chart.
FIG. 15 shows 2,2 ' -dimethoxy-6, 6 ' -di (methyl 2-propionate) -1, 1' -binaphthyl prepared in example 8 of the present invention1H NMR chart.
FIG. 16 shows 2,2 ' -dimethoxy-6, 6 ' -di (methyl 2-propionate) -1, 1' -binaphthyl prepared in example 8 of the present invention13C NMR chart.
Detailed Description
The present invention will be further described with reference to the following specific examples, which are not intended to limit the scope of the present invention.
The starting materials used in the examples are commercially available or can be prepared according to the prior art.
Example 1: preparation of 4,4 '-diethyl-1, 1' -binaphthyl
Sequentially adding 0.4mmol of 1-ethylnaphthalene, 0.2mmol of lithium perchlorate and 5mL of acetonitrile into a 10mL three-necked flask, reacting for 5h at 25 ℃ by using a carbon rod as an anode and a platinum sheet electrode as a cathode under constant current of 5mA, and tracking and monitoring by TLC; after the reaction was complete, the solvent was removed by rotary evaporator and the residue was purified by flash column chromatography on silica gel (petroleum ether as mobile phase) to give the product in 76% yield.
1H NMR(400MHz,Chloroform-d)δ8.19(d,J＝8.5Hz,2H),7.55-7.40(m,8H),7.30(t,J＝ 7.6Hz,2H),3.25(q,J＝7.5Hz,4H),1.52(t,J＝7.5Hz,6H)；
13C NMR(101MHz,Chloroform-d)δ139.9,137.1,133.3,131.8,127.8,127.6,125.5,125.4, 124.4,123.9,26.0,15.1；
MS for C24H22 calcd 310,found 310.
Example 2: preparation of 4,4 '-dimethyl-1, 1' -binaphthyl
Sequentially adding 0.4mmol of 1-methylnaphthalene, 0.2mmol of lithium perchlorate and 5mL of acetonitrile into a 10mL three-necked flask, reacting for 5h at 25 ℃ by using a carbon rod as an anode and a platinum sheet electrode as a cathode under constant current of 5mA, and tracking and monitoring by TLC; after the reaction was complete, the solvent was removed by rotary evaporator and the residue was purified by flash column chromatography on silica gel (petroleum ether as mobile phase) to give the product in 78% yield.
1H NMR(600MHz,Chloroform-d)δ8.11(d,J＝8.4Hz,2H),7.52(t,J＝7.6Hz,2H), 7.47-7.43(m,4H),7.40(d,J＝7.0Hz,2H),7.30(t,J＝7.4Hz,2H),2.81(s,6H)；
13C NMR(151MHz,Chloroform-d)δ137.0,133.9,133.0,132.5,127.6,127.3,126.1,125.5, 124.2,19.6；
MS for C22H18 calcd 282,found 282.
Example 3: preparation of 4,4 '-diisopropyl-1, 1' -binaphthyl
Sequentially adding 0.4mmol of 1-isopropylnaphthalene, 0.2mmol of lithium perchlorate and 5mL of acetonitrile into a 10mL three-necked bottle, reacting for 5h at 25 ℃ by using a carbon rod as an anode and a platinum sheet electrode as a cathode under constant current of 5mA, and tracking and monitoring by TLC; after the reaction was complete, the solvent was removed by rotary evaporator and the residue was purified by flash column chromatography on silica gel (petroleum ether as mobile phase) to give the product in 73% yield.
1H NMR(400MHz,Chloroform-d)δ8.22(dd,J＝8.6,1.1Hz,2H),7.54-7.42(m,8H),7.25 (td,J＝6.8,1.2Hz,2H),3.86(p,J＝6.8Hz,2H),1.49(dd,J＝9.3,6.9Hz,12H)；
13C NMR(151MHz,Chloroform-d)δ144.2,136.9,133.4,131.4,127.8,127.7,125.5,125.2, 123.4,121.3,28.7,23.8；
MS for C26H26 calcd 338,found 338.
Example 4: preparation of 3,3 ', 4,4 ' -tetramethyl-1, 1' -binaphthyl
Sequentially adding 0.4mmol of 1, 2-dimethylnaphthalene, 0.2mmol of lithium perchlorate and 5mL of acetonitrile into a 10mL three-necked bottle, reacting for 4h at 25 ℃ by using a carbon rod as an anode and a platinum sheet electrode as a cathode at constant current of 5mA, and tracking and monitoring by TLC; after the reaction was complete, the solvent was removed by rotary evaporator and the residue was purified by flash column chromatography on silica gel (petroleum ether as mobile phase) to give the product in 72% yield.
1H NMR(400MHz,Chloroform-d)δ8.19(d,J＝8.5Hz,2H),7.54(t,J＝7.5Hz,2H),7.46 (d,J＝8.2Hz,2H),7.39(s,2H),7.29(d,J＝7.8Hz,2H),2.77(s,6H),2.61(s,6H)；
13C NMR(101MHz,Chloroform-d)δ136.4,132.9,132.7,131.8,131.1,130.9,127.3,125.6, 124.5,123.9,20.9,14.7；
MS for C24H22 calcd 310,found 310.
Example 5: 2,2 ', 4,4 ' -tetramethyl-1, 1' -binaphthyl
Sequentially adding 0.4mmol of 1, 3-dimethylnaphthalene, 0.2mmol of lithium perchlorate and 5mL of acetonitrile into a 10mL three-necked bottle, reacting for 3h at 25 ℃ by using a carbon rod as an anode and a platinum sheet electrode as a cathode at constant current of 5mA, and tracking and monitoring by TLC; after the reaction was complete, the solvent was removed by rotary evaporator and the residue was purified by flash column chromatography on silica gel (petroleum ether as mobile phase) to give the product in 75% yield.
1H NMR(600MHz,Chloroform-d)δ8.06(d,J＝8.4Hz,2H),7.44(t,J＝7.5Hz,2H),7.38 (s,2H),7.22(t,J＝7.5Hz,2H),7.11(d,J＝8.4Hz,2H),2.80(s,6H),2.02(s,6H)；
13C NMR(151MHz,Chloroform-d)δ132.9,132.5,132.3,132.0,130.3,128.5,125.3,124.6, 123.6,123.0,19.0,18.4；
MS for C24H22 calcd 310,found 310.
Example 6: preparation of 4,4 ', 5,5 ' -tetramethyl-1, 1' -binaphthyl
Sequentially adding 0.4mmol of 1, 8-dimethylnaphthalene, 0.2mmol of lithium perchlorate and 5mL of acetonitrile into a 10mL three-necked bottle, reacting for 4h at 25 ℃ by using a carbon rod as an anode and a platinum sheet electrode as a cathode at constant current of 5mA, and tracking and monitoring by TLC; after the reaction was complete, the solvent was removed by rotary evaporator and the residue was purified by flash column chromatography on silica gel (petroleum ether as mobile phase) to give the product in 76% yield.
1H NMR(400MHz,Chloroform-d)δ7.34(d,J＝7.2Hz,2H),7.25(d,J＝7.2Hz,2H),7.21 (d,J＝8.3Hz,4H),7.05(dd,J＝8.5,6.8Hz,2H),3.09-2.90(m,12H)；
13C NMR(101MHz,Chloroform-d)δ138.6,135.6,135.1,134.8,133.1,129.4,129.0,127.1, 126.4,125.0,26.3；
MS for C24H22 calcd 310,found 310.
Example 7: preparation of 2,2 ' -dimethoxy-6, 6 ' -dimethyl-1, 1' -binaphthyl
Sequentially adding 0.4mmol of 2-methyl-6-methoxynaphthalene, 0.2mmol of lithium perchlorate and 5mL of acetonitrile into a 10mL three-necked bottle, reacting for 4h at 25 ℃ by using a carbon rod as an anode and a platinum sheet electrode as a cathode and under constant current of 5mA, and tracking and monitoring by TLC; after the reaction was complete, the solvent was removed by rotary evaporator and the residue was purified by flash column chromatography on silica gel (petroleum ether as mobile phase) to give the product in 90% yield.
1H NMR(400MHz,Chloroform-d)δ7.87(d,J＝9.0Hz,2H),7.62(s,2H),7.41(d,J＝9.0 Hz,2H),7.07-6.98(m,4H),3.73(s,6H),2.44(s,6H)；
13C NMR(101MHz,Chloroform-d)δ154.4,132.9,132.2,129.4,128.6,126.8,125.2,119.7, 114.5,57.0,21.4；
MS for C24H22O2 calcd 342,found 342.
Example 8: preparation of 2,2 ' -dimethoxy-6, 6 ' -di (2-methyl propionate) -1, 1' -binaphthyl
Sequentially adding 0.4mmol of 2-di (2-methyl propionate) -6-methoxynaphthalene, 0.2mmol of lithium perchlorate and 5mL of acetonitrile into a 10mL three-necked bottle, reacting for 6h at 25 ℃ by using a carbon rod as an anode and a platinum sheet electrode as a cathode and under constant current of 5mA, and tracking and monitoring by TLC; after completion of the reaction, the solvent was removed by rotary evaporator, and the residue was purified by flash silica gel column chromatography (ethyl acetate: petroleum ether ═ 10:1 as mobile phase) to give the product in 67% yield.
1H NMR(400MHz,Chloroform-d)δ7.94(d,J＝9.0Hz,2H),7.77(s,2H),7.45(d,J＝9.0 Hz,2H),7.17(d,J＝8.8Hz,2H),7.06(d,J＝8.8Hz,2H),3.83(q,J＝7.1Hz,2H),3.76(s,6H), 3.66(d,J＝2.0Hz,6H),1.56(d,J＝7.1Hz,6H)；
13C NMR(101MHz,Chloroform-d)δ175.1,155.0,135.4,133.1,129.3,129.2,126.3,126.1, 125.7,119.4,114.4,56.9,52.0,45.3,18.6；
HRMS(ESI)for C30H31O6[M+H]+calcd 487.2115,found 487.2116。
Claims (10)
1. An electrochemical synthesis method of 1,1' -binaphthyl compounds comprises the following steps:
sequentially adding a solvent, an electrolyte, a naphthalene compound and a positive electrode and a negative electrode into a diaphragm-free electrolytic cell, stirring at room temperature, and reacting under a constant current condition; after the reaction is finished, concentrating the reaction solution, and separating and purifying the organic phase to obtain the product 1,1' -binaphthyl compound.
2. The electrochemical synthesis method of 1,1' -binaphthyl compounds according to claim 1, wherein the naphthalene compounds have a structure represented by formula (I):
in the formula (I), R1Selected from alkyl, alkoxy or hydrogen atoms;
R2selected from alkyl, alkoxy or hydroxy.
3. The electrochemical synthesis method of 1,1' -binaphthyl compounds according to claim 2, wherein R is1Wherein the alkyl is methyl, methyl 2-propionate or 2-propionate, and the alkoxy is methoxy; r2Wherein the alkyl is methyl or ethyl, and the alkoxy is methoxy.
4. The electrochemical synthesis method of 1,1' -binaphthyl compounds according to claim 1, wherein the cathode is a platinum sheet electrode, and the anode is a carbon rod.
5. The electrochemical synthesis method of 1,1' -binaphthyl compounds according to claim 1, wherein the solvent is one or any combination of acetonitrile and hexafluoroisopropanol.
6. The electrochemical synthesis method of 1,1' -binaphthyl compounds according to claim 1, wherein the electrolyte is one of lithium perchlorate, lithium fluoride, potassium hexafluorophosphate, and tetrabutylammonium hexafluorophosphate.
7. The electrochemical synthesis method of the 1,1' -binaphthyl compound according to claim 1, wherein the molar concentration of the electrolyte in the solvent is 0.08-0.4 mol/L.
8. The electrochemical synthesis method of the 1,1' -binaphthyl compound according to claim 1, wherein the constant current is 5-10 mA.
9. The electrochemical synthesis method of 1,1' -binaphthyl compounds according to claim 1, wherein the reaction temperature is 25 ℃;
preferably, the reaction is carried out under air conditions;
preferably, the reaction time is 4-12 h.
10. The electrochemical synthesis method of 1,1' -binaphthyl compounds according to claim 1, wherein the separation and purification method comprises: the solvent was removed by rotary evaporation and the residue was purified by column chromatography over silica gel with ethyl acetate as eluent: petroleum ether is 1: 10.
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| US5522982A (en) * | 1994-03-30 | 1996-06-04 | Hoechst Aktiengesellschaft | Process for preparing 4,4'-dimethyl-1,1'-binaphthyl |
| US5767333A (en) * | 1993-12-11 | 1998-06-16 | Hoechst Ag | Process for preparing 2,2'-dimethyl-1,1'binaphthyl and 2,7'-dimethyl-1,1'-binaphthyl |
| CN110552018A (en) * | 2019-10-17 | 2019-12-10 | 广西师范大学 | Method for synthesizing 1-naphthol compound based on electrochemical intermolecular cyclization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5767333A (en) * | 1993-12-11 | 1998-06-16 | Hoechst Ag | Process for preparing 2,2'-dimethyl-1,1'binaphthyl and 2,7'-dimethyl-1,1'-binaphthyl |
| US5522982A (en) * | 1994-03-30 | 1996-06-04 | Hoechst Aktiengesellschaft | Process for preparing 4,4'-dimethyl-1,1'-binaphthyl |
| CN110552018A (en) * | 2019-10-17 | 2019-12-10 | 广西师范大学 | Method for synthesizing 1-naphthol compound based on electrochemical intermolecular cyclization |
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| CN114892188A (en) * | 2022-06-17 | 2022-08-12 | 江苏农牧科技职业学院 | Method for electrochemically synthesizing zolpidem |
| CN114892188B (en) * | 2022-06-17 | 2023-10-03 | 江苏农牧科技职业学院 | Electrochemical synthesis method of zolpidem |
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