CN114478449B - Polysubstituted selenium-containing dihydroisobenzofuran derivative and preparation method thereof - Google Patents
Polysubstituted selenium-containing dihydroisobenzofuran derivative and preparation method thereof Download PDFInfo
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- SFLGSKRGOWRGBR-UHFFFAOYSA-N phthalane Chemical class C1=CC=C2COCC2=C1 SFLGSKRGOWRGBR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 125000003748 selenium group Chemical class *[Se]* 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group 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 30
- 150000003342 selenium Chemical class 0.000 claims description 22
- -1 diaryl diselenide compound Chemical class 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 18
- 239000003208 petroleum Substances 0.000 claims description 15
- 238000010898 silica gel chromatography Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 125000005257 alkyl acyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 230000004071 biological effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 24
- 239000007810 chemical reaction solvent Substances 0.000 description 22
- 239000011669 selenium Substances 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 12
- 239000003570 air Substances 0.000 description 11
- YWWZCHLUQSHMCL-UHFFFAOYSA-N diphenyl diselenide Chemical compound C=1C=CC=CC=1[Se][Se]C1=CC=CC=C1 YWWZCHLUQSHMCL-UHFFFAOYSA-N 0.000 description 11
- 239000003480 eluent Substances 0.000 description 11
- 238000001819 mass spectrum Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 238000000746 purification Methods 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000036039 immunity Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
-
- 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
- C25B3/05—Heterocyclic 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
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- 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)
Abstract
The invention belongs to the field of organic synthesis, and particularly relates to a polysubstituted selenium-containing dihydro-isobenzofuran derivative and a preparation method thereof. The polysubstituted selenium-containing dihydroisobenzofuran derivative has more biological activity and great application value, the preparation method can be carried out at normal temperature and normal pressure, the reaction condition is mild, transition metal catalysis is not needed, and the method has the advantages of simplicity in operation, no pollution, safety, environmental protection, low cost, high yield and the like.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a polysubstituted selenium-containing dihydroisobenzofuran derivative and a preparation method thereof.
Background
Selenium is one of trace elements essential for human and animal life, and has the effects of resisting oxidation, regulating immunity, promoting animal growth, removing toxic substances, relieving stress, etc., and plays a vital role in maintaining body health and regulating diseases. The biomedical value of selenium is more important, and researches show that organic selenium has great potential in the aspects of antioxidation, anti-aging, anticancer, immunity enhancement, cardiovascular disease prevention, antiviral and the like. In addition, dihydroisobenzofurans are widely found in natural products and have numerous biological activities. Therefore, the synthesis of the polysubstituted selenium-containing dihydroisobenzofuran derivative is very important, few reports are made on the current synthesis method of the polysubstituted selenium-containing dihydroisobenzofuran derivative, a transition metal catalytic system is mostly adopted for constructing the dihydroisobenzofuran skeleton, the steps are complicated, and the application of noble metals can cause certain pollution to the environment. Therefore, the invention provides the polysubstituted selenium-containing dihydroisobenzofuran derivative which is environment-friendly, simple in method, few in steps and high in yield, and the synthesis method thereof.
Disclosure of Invention
The first object of the invention is to provide a polysubstituted selenium-containing dihydroisobenzofuran derivative having the following structure I or structure V:
wherein R is 1 、R 2 Selected from ester groups or acyl groups, R 1 、R 2 The same or different;
R 3 selected from hydrogen, halo, C1-C5 alkyl;
R 4 selected from aryl groups;
R 5 and R is 6 Selected from alkoxy groups having 1 to 5 carbon atoms or halogen radicals, R 5 And R is 6 The same or different.
Preferably, the ester group is selected fromCOOR 7 The R is 7 Selected from C1-C5 alkyl, aryl or benzyl; the acyl is selected from the group consisting of alkanoyl, and the alkyl of the alkanoyl is selected from the group consisting of C1-C5 alkyl.
Preferably, the formula I or formula V is selected from the following structures:
the invention also provides a preparation method of the polysubstituted selenium-containing dihydroisobenzofuran derivative, which is shown as follows:
and (3) carrying out electrifying reaction on the o-phthalene compound shown in the formula II or the formula IV, the diaryl diselenide compound shown in the formula III and water in a solvent containing electrolyte at the temperature of 0-35 ℃ under the atmosphere of air, nitrogen or inert gas.
The preferred reaction temperature is 20-30 ℃, more preferably 20 ℃.
Preferably, the electrolyte is selected from lithium chloride, lithium bromide, lithium tetrafluoroborate, lithium perchlorate, sodium tetrafluoroborate or potassium tetrafluoroborate.
Preferably, the current is applied by direct current, the direct current is controlled to be 1-15mA, and the electrode is an inert electrode, such as a platinum electrode, a carbon electrode or other inert electrodes.
The direct current is more preferably 5-7mA.
Preferably, the molar ratio of the o-phthalene compound shown in the formula II or the formula IV to the diaryl diselenide compound shown in the formula III is 1:1-1:3.
Preferably, the solvent is selected from acetonitrile, tetrahydrofuran, benzene, toluene, acetone, methanol or dimethyl sulfoxide.
Preferably, the ratio of the feeding volume of the solvent to the amount of the o-phthalene compound represented by formula II or formula IV is 3-100 mL/mmol. More preferably 10 to 20mL/mmol.
Preferably, the product obtained by the reaction is obtained by separating and purifying through silica gel column chromatography, wherein the solvent used for separating and purifying through silica gel column chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is 4-30:1.
Advantageous effects
1. The invention provides a polysubstituted selenium-containing dihydroisobenzofuran derivative, which has more potential bioactivity, huge research value and application value according to the structure-activity relationship, and can be used as a screening of a drug lead compound, or as a drug research and development intermediate, or as a synthetic raw material of some complex drug molecules.
2. The invention provides a simple one-step synthesis method of a polysubstituted selenium-containing dihydroisobenzofuran derivative, which solves the problems of complex synthesis steps, low yield and poor environmental protection of the existing polysubstituted selenium-containing dihydroisobenzofuran derivative. The method can react at normal temperature and normal pressure, has mild reaction conditions, no need of transition metal catalysis, simple operation, no pollution, safety, environmental protection, low cost and the like.
Drawings
FIG. 1 shows the hydrogen spectrum of the product obtained in example 1.
FIG. 2 is a graph of the carbon spectrum of the product obtained in example 1.
FIG. 3 shows the hydrogen spectrum of the product obtained in example 5.
FIG. 4 carbon spectrum of the product obtained in example 5.
FIG. 5 is a hydrogen spectrum of the product obtained in example 7.
FIG. 6 is a graph of the carbon spectrum of the product obtained in example 7.
Detailed Description
In order to make the technical scheme and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The terms referred to in the present invention have the following meanings:
ester group: refers to-COOR 8 Wherein R is 8 Are non-hydrogen groups such as alkyl groups, aryl-containing alkyl groups, heteroatom-containing alkyl groups, and the like.
An acyl group: the radical remaining after removal of one or more hydroxyl groups of the organic or inorganic oxyacid, referred to herein as carbonyl, of the formula R 9 -C (O) -, wherein R 9 Is a non-hydrogen group.
Aryl: refers to any functional group or substituent derived from a simple aromatic ring, such as phenyl, naphthyl, tolyl, and the like.
C1-C5 alkyl: refers to saturated alkyl groups containing 1 to 5 carbon atoms such as methyl, ethyl, isopropyl, n-propyl, butyl, and the like.
Alkyl acyl: the general formula is R 10 -C (O) -, wherein R 10 Is alkyl.
Inert electrode: inert electrodes refer to electrodes that are not electron-donating and generally do not react with the electrolyte. Such as a platinum electrode, a carbon electrode, a silver electrode, or a gold electrode, etc. As long as the electrode that does not react with the electrolyte according to the present invention is an inert electrode according to the present invention.
Example 1
49.2mg (0.2 mmol) of disubstituted o-phenyldiene (2 a), 81.15mg (0.26 mmol) of diphenyl diselenide, 18.75mg (0.2 mmol) of lithium tetrafluoroborate and 3mL of acetonitrile are added into a 10mL electrolytic cell/reaction bottle, 3.6mg of water is added, the mixture is stirred uniformly, direct current is introduced under the condition of air atmosphere at room temperature of 25 ℃, the cathode and anode of the electrode are both platinum electrodes, the current of a reaction system is 6mA, the reaction lasts for about 4.5 hours, and after the reaction is finished, the reaction solvent is concentrated by a rotary evaporator, and the volume ratio of the reaction solvent is 20: petroleum ether of 1: the mixed solution of ethyl acetate is used as an eluent to carry out silica gel column chromatography purification and separation, and the reaction formula of the polysubstituted selenium-containing dihydroisobenzofuran derivative (3 aa) is as follows:
the product mass was 94.9mg with a yield of 82%. The hydrogen spectrum and the carbon spectrum are shown in figures 1-2, and the nuclear magnetic data and the mass spectrum data are analyzed as follows:
Major: 1 H NMR(600MHz,CDCl 3 )δ7.83(dd,J＝5.6,3.2Hz,2H),7.59–7.47(m,4H),7.35(dd,J＝5.7,3.2Hz,2H),7.31–7.19(m,6H),5.60(d,J＝8.1Hz,2H),3.98(d,J＝8.2Hz,2H),3.65(s,6H). 13 C NMR(150MHz,CDCl 3 )δ171.6,139.5,135.1,129.1,128.5,128.3,127.9,123.7,82.0,52.1,50.0.Minor: 1 H NMR(600MHz,CDCl 3 )δ7.67(dd,J＝5.6,3.2Hz,2H),7.57–7.50(m,4H),7.33(dd,J＝5.7,3.1Hz,2H),7.30–7.21(m,6H),5.80(d,J＝5.9Hz,2H),3.93(d,J＝6.1Hz,2H),3.63(s,6H). 13 C NMR(150MHz,CDCl 3 )δ171.4,139.9,134.8,129.1,128.6,128.4,128.3,123.1,82.4,52.1,50.1.HRMS(ESI)calculated for C 26 H 24 NaO 5 Se 2 [M+Na]+:598.9846；found:598.9832.
the above Major refers to the product of the main configuration, and Minor refers to the isomer thereof.
Example 2
To a 10mL electrolytic cell/reaction flask, 54.8mg (0.2 mmol) of disubstituted o-phenyldiene (2 b), 81.15mg (0.26 mmol) of diphenyl diselenide, 18.75mg (0.2 mmol) of lithium tetrafluoroborate as electrolyte and 3mL of acetonitrile were added, 36 mg of water was added, and after stirring uniformly, direct current was introduced under the condition of air atmosphere at room temperature of 25 ℃, the anode and the cathode of the electrode were both platinum electrodes, the current of the reaction system was 6mA, and the reaction time was 4-6 hours. After the reaction is finished, concentrating and spin-drying the reaction solvent by a rotary evaporator, and then mixing the reaction solvent with the solvent according to the volume ratio of 20: petroleum ether of 1: the mixed solution of ethyl acetate is used as an eluent to carry out silica gel column chromatography purification and separation, and the reaction formula of the polysubstituted selenium-containing dihydroisobenzofuran derivative (3 ab) is as follows:
product quality103.9mg, yield 86%. The nuclear magnetic data and mass spectrum data are analyzed as follows: major: 1 H NMR(600MHz,CDCl 3 )δ7.86(dd,J＝5.6,3.2Hz,2H),7.61–7.55(m,4H),7.40–7.35(m,2H),7.31(ddd,J＝6.5,3.7,1.2Hz,2H),7.29–7.22(m,4H),5.65(d,J＝7.8Hz,2H),4.21–4.08(m,4H),4.04(d,J＝7.8Hz,2H),1.19(t,J＝7.1Hz,6H). 13 C NMR(150MHz,CDCl 3 )δ171.3,139.6,135.1,129.0,128.4,128.3,128.1,123.7,82.0,61.1,50.18,14.0.Minor: 1 H NMR(600MHz,CDCl 3 )δ7.66(dd,J＝5.6,3.2Hz,2H),7.59–7.51(m,4H),7.32(dd,J＝5.7,3.1Hz,2H),7.30–7.26(m,2H),7.26–7.23(m,4H),5.80(d,J＝5.9Hz,2H),4.27–4.01(m,4H),3.92(d,J＝6.0Hz,2H),1.13(t,J＝7.1Hz,6H). 13 C NMR(150MHz,CDCl 3 )δ171.0,139.9,134.8,129.0,128.7,128.3,128.2,123.0,82.5,61.1,50.3,13.9.HRMS(ESI)calculated for C 28 H 28 NaO 5 Se 2 [M+Na]+:627.0159；found:627.0161
example 3
To a 10mL electrolytic cell/reaction flask, 79.6mg (0.2 mmol) of disubstituted o-phenyldiene (2 c), 81.15mg (0.26 mmol) of diphenyl diselenide, 18.75mg (0.2 mmol) of lithium tetrafluoroborate and 3mL of acetonitrile were added, 3.6mg of water was added, and after stirring uniformly, direct current was introduced under the condition of air atmosphere at room temperature of 25 ℃, the anode and the cathode of the electrode were both platinum electrodes, the current of the reaction system was 6mA, and the reaction time was 4-6 hours. After the reaction is finished, concentrating and spin-drying the reaction solvent by a rotary evaporator, and then mixing the reaction solvent with the solvent according to the volume ratio of 20: petroleum ether of 1: the mixed solution of ethyl acetate is used as an eluent to carry out silica gel column chromatography purification and separation, and the reaction formula of the polysubstituted selenium-containing dihydroisobenzofuran derivative (3 ac) is as follows:
the product mass was 107mg and the yield was 74%. The nuclear magnetic data and mass spectrum data are analyzed as follows: 1 H NMR(600MHz,CDCl 3 )δ7.81(dd,J＝5.6,3.2Hz,2H),7.47–7.43(m,4H),7.31(m,8H),7.25–7.16(m,6H),7.10(m,4H),5.65(d,J＝7.5Hz,2H),5.13(d,J＝12.4Hz,2H),5.01(d,J＝12.4Hz,2H),4.09(d,J＝7.6Hz,2H). 13 C NMR(150MHz,CDCl 3 )δ171.1,139.5,135.6,135.2,129.0,128.4,128.4,128.3,128.1,128.1,127.9,123.6,82.0,66.7,49.9.HRMS(ESI)calculated for C 38 H 32 NaO 5 Se 2 [M+Na]+:751.0472；found:751.0405
example 4
To a 10mL electrolytic cell/reaction flask, 43.6mg (0.2 mmol) of disubstituted o-phenyldiene (2 d), 81.15mg (0.26 mmol) of diphenyl diselenide, 18.75mg (0.2 mmol) of lithium tetrafluoroborate and 3mL of acetonitrile were added, 3.6mg of water was added, and after stirring uniformly, direct current was introduced under the condition of air atmosphere at room temperature of 25 ℃, the anode and the cathode of the electrode were both platinum electrodes, the current of the reaction system was 6mA, and the reaction time was 4-6 hours. After the reaction is finished, concentrating and spin-drying the reaction solvent by a rotary evaporator, and then mixing the reaction solvent with the solvent according to the volume ratio of 15: petroleum ether of 1: the mixed solution of ethyl acetate is used as an eluent to carry out silica gel column chromatography purification and separation, and the reaction formula of the polysubstituted selenium-containing dihydroisobenzofuran derivative (3 ad) is as follows:
the product mass was 65mg and the yield was 59.63%. The nuclear magnetic data and mass spectrum data are analyzed as follows: 1 H NMR(500MHz,CDCl 3 )δ7.63(dd,J＝5.6,3.4Hz,2H),7.53–7.33(m,4H),7.33–7.11(m,8H),5.69(ddt,J＝13.5,9.8,5.0Hz,2H),3.98–3.71(m,2H),2.67–2.28(m,4H),1.05–0.86(m,6H). 13 C NMR(150MHz,CDCl 3 )δ206.35,206.32,140.59,140.37,135.93,134.50,134.43,129.3,129.13,128.55,128.2,123.7,123.4,121.66,82.32,82.0,57.9,57.7,34.6,34.0,8.2,8.18.HRMS(ESI)calculated for C 28 H 28 NaO 3 Se 2 [M+Na]+:595.0261；found:595.0262.
example 5
To a 10mL electrolytic cell/reaction flask, 52mg (0.2 mmol) of disubstituted o-phenyldiene (2 e), 81.15mg (0.26 mmol) of diphenyl diselenide, 18.75mg (0.2 mmol) of lithium tetrafluoroborate and 3mL of acetonitrile were added, 3.6mg of water was added, and after stirring uniformly, direct current was introduced under the condition of air atmosphere at room temperature of 25 ℃, the anode and the cathode of the electrode were both platinum electrodes, the current of the reaction system was 6mA, and the reaction time was 4-6 hours. After the reaction is finished, concentrating and spin-drying the reaction solvent by a rotary evaporator, and then mixing the reaction solvent with the solvent according to the volume ratio of 20: petroleum ether of 1: the mixed solution of ethyl acetate is used as an eluent to carry out silica gel column chromatography purification and separation, and the reaction formula of the polysubstituted selenium-containing dihydroisobenzofuran derivative (3 ae) is as follows:
the product mass was 103mg with a yield of 87%. The hydrogen spectrogram and the carbon spectrogram are shown in figures 3-4, and the nuclear magnetic data and the mass spectrum data are analyzed as follows: major: 1 H NMR(400MHz,CDCl 3 )δ7.91–7.83(m,2H),7.63–7.55(m,4H),7.33–7.24(m,8H),5.66(d,J＝4.2Hz,2H),4.20–4.12(d,2H),4.01(d,J＝7.9Hz,2H),3.68(s,3H),1.20(t,J＝7.1Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ171.6,171.3,139.61,139.56,135.22,135.17,129.15,129.11,128.54,128.44,128.41,128.39,123.7,82.10,82.0,61.15,52.12,50.28,49.95,14.04.Minor: 1 H NMR(400MHz,CDCl 3 )δ7.73–7.68(m,2H),7.61–7.59(m,4H),7.40–7.33(m,8H),5.84(d,J＝5.9Hz,2H),4.12–4.07(d,2H),3.96(d,J＝6.0,3.7Hz,2H),3.66(s,3H),1.16(t,J＝7.1Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ171.50,171.04,139.98,139.94,134.86,134.83,128.74,128.62,128.36,128.26,128.17,127.95,123.16,123.09,82.51,82.46,61.13,52.19,50.31,50.19,13.99.HRMS(ESI)calculated for C 27 H 26 NaO 5 Se 2 [M+Na]+:613.0003；found:612.9992
example 6
To a 10mL electrolytic cell/reaction flask, 58.4mg (0.2 mmol) of substituted o-phenyldiene (2 f), 81.15mg (0.26 mmol) of diphenyl diselenide, 18.75mg (0.2 mmol) of lithium tetrafluoroborate and 3mL of acetonitrile were added, 3.6mg of water was added, and after stirring uniformly, direct current was introduced under the condition of air atmosphere at room temperature of 25 ℃, the anode and the cathode of the electrode were both platinum electrodes, the current of the reaction system was 6mA, and the reaction time was 4-6 hours. After the reaction is finished, concentrating and spin-drying the reaction solvent by a rotary evaporator, and then mixing the reaction solvent with the solvent according to the volume ratio of 15: petroleum ether of 1: the mixed solution of ethyl acetate is used as an eluent to carry out silica gel column chromatography purification and separation, and the reaction formula of the polysubstituted selenium-containing dihydroisobenzofuran derivative (3 af) is as follows:
the product mass was 82mg, yield 66.23%. The nuclear magnetic data and mass spectrum data are analyzed as follows: 1 H NMR(400MHz,CDCl 3 )δ7.79(dd,J＝8.5,5.0Hz,1H),7.56(ddd,J＝8.8,4.1,2.5Hz,5H),7.35–7.14(m,6H),7.02(td,J＝8.6,2.4Hz,1H),5.58(d,J＝7.6Hz,2H),4.22–4.06(m,4H),4.02(dd,J＝7.7,3.4Hz,2H),1.18(td,J＝7.1,5.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ171.34,171.21,162.87(d,J＝246.2Hz),141.87(d,J＝8.7Hz),135.2,135.16,135.14,135.09,129.16,129.14,128.57,128.45,128.02(d,J＝13.6Hz),125.05(d,J＝8.9Hz),115.56(d,J＝22.8Hz),111.09(d,J＝24.8Hz),81.70,81.67,61.23,61.18,50.18,49.80,14.03.HRMS(ESI)calculated for C 28 H 27 FNaO 5 Se 2 [M+Na] + :645.0065；found:645.0065
example 7
To a 10mL electrolytic cell/reaction flask, 66.8mg (0.2 mmol) of substituted o-benzodiene (2 g), 81.15mg (0.26 mmol) of diphenyl diselenide, 18.75mg (0.2 mmol) of lithium tetrafluoroborate and 3mL of acetonitrile were added, 3.6mg of water was added, and after stirring uniformly, direct current was introduced under the condition of air atmosphere at room temperature of 25 ℃, the anode and the cathode of the electrode were both platinum electrodes, the current of the reaction system was 6mA, and the reaction time was 4-6 hours. After the reaction is finished, concentrating and spin-drying the reaction solvent by a rotary evaporator, and then mixing the reaction solvent with the solvent according to the volume ratio of 6: petroleum ether of 1: the mixed solution of ethyl acetate is used as an eluent to carry out silica gel column chromatography purification and separation, and the reaction formula of the polysubstituted selenium-containing dihydroisobenzofuran derivative (3 ag) is as follows:
the product mass was 83mg, yield 61.92%. The hydrogen spectrogram and the carbon spectrogram are shown in fig. 5-6, and the nuclear magnetic data and the mass spectrum data are analyzed as follows: minor: 1 H NMR(400MHz,CDCl 3 )δ7.57–7.50(m,4H),7.32–7.20(m,8H),5.77(d,J＝5.6Hz,2H),4.13(ddd,J＝7.9,6.4,4.3Hz,4H),3.93(d,J＝5.7Hz,2H),3.85(s,6H),1.17(t,J＝4.7Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ171.29,149.26(s),134.58,131.87,129.08,128.88,128.46,105.74,82.68,61.11,56.01,50.77,14.03.Major: 1 H NMR(400MHz,CDCl 3 )δ7.61-7.46(m,4H),7.33–7.13(m,8H),5.58(d,J＝7.4Hz,2H),4.22-4.10(m,4H),4.07(d,J＝7.4Hz,2H),3.85(s,6H),1.18(m,6H). 13 C NMR(100MHz,CDCl 3 )δ171.56,149.26,134.67,131.42,129.11,128.30,128.18,106.26,82.24,61.13,56.01,50.45,14.06.HRMS(ESI)calculated for C 30 H 33 O 7 Se 2 [M+H]+:665.0551；found:665.0539.
example 8
To a 10mL electrolytic cell/reaction flask, 57.6mg (0.2 mmol) of substituted o-benzodiene (2 h), 81.15mg (0.26 mmol) of diphenyl diselenide, 18.75mg (0.2 mmol) of lithium tetrafluoroborate and 3mL of acetonitrile were added, 3.6mg of water was added, and after stirring uniformly, direct current was introduced under the condition of air atmosphere at room temperature of 25 ℃ for reaction, the anode and the cathode of the electrode were both platinum electrodes, the current of the reaction system was 6mA, and the reaction time was 4-6 hours. After the reaction is finished, concentrating and spin-drying the reaction solvent by a rotary evaporator, and then mixing the reaction solvent with the solvent according to the volume ratio of 20: petroleum ether of 1: the mixed solution of ethyl acetate is used as an eluent to carry out silica gel column chromatography purification and separation, and the reaction formula of the polysubstituted selenium-containing dihydroisobenzofuran derivative (3 ah) is as follows:
the product mass was 83mg with a yield of 67%. The nuclear magnetic data and mass spectrum data are analyzed as follows: major: 1 H NMR(400MHz,CDCl 3 )δ7.70(d,J＝7.9Hz,1H),7.56(tt,J＝7.5,4.0Hz,5H),7.31–7.16(m,7H),5.59(dd,J＝7.4,4.6Hz,2H),4.16–4.06(m,4H),4.01(dd,J＝7.9,5.6Hz,2H),2.38(s,3H),1.16(td,J＝7.1,1.5Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ171.40,171.34,139.84,138.26,136.8,135.20,129.21,129.07,128.39,128.20,124.15,123.40,82.04,81.93,61.10,50.35,50.30,21.50,14.04.Minor: 1 H NMR(400MHz,CDCl 3 )δ7.75–7.43(m,6H),7.32–7.00(m,7H),5.77(d,J＝6.0Hz,2H),4.20–4.06(m,4H),3.91(dd,J＝5.8,4.3Hz,2H),2.36(s,3H),1.15–1.10(m,6H). 13 C NMR(100MHz,CDCl 3 )δ171.14,171.06,140.22,138.19,137.19,135.15,134.79,128.88,128.33,128.23,123.54,122.76,82.49,82.38,61.07,50.57,50.45,21.50,13.98.HRMS(ESI)calculated for C 29 H 30 NaO 5 Se 2 [M+Na]+:641.0316；found:.641.0305
example 9
To a 10mL electrolytic cell/reaction flask, 61.7mg (0.2 mmol) of substituted o-phenyldiene (2 i), 81.15mg (0.26 mmol) of diphenyl diselenide, 18.75mg (0.2 mmol) of lithium tetrafluoroborate and 3mL of acetonitrile were added, 3.6mg of water was added, and after stirring uniformly, direct current was introduced under the condition of air atmosphere at room temperature of 25℃for reaction, the anode and the cathode of the electrode were both platinum electrodes, the current of the reaction system was 6mA, and the reaction time was 4-6 hours. After the reaction is finished, concentrating and spin-drying the reaction solvent by a rotary evaporator, and then mixing the reaction solvent with the solvent according to the volume ratio of 15: petroleum ether of 1: the mixed solution of ethyl acetate is used as an eluent to carry out silica gel column chromatography purification and separation to obtain the light polysubstituted selenium-containing dihydroisobenzofuran derivative (3 ai) with the reaction formula:
the product mass (3 ai) was 92mg with a yield of 71.64%. The nuclear magnetic data and mass spectrum data are analyzed as follows: major: 1 H NMR(400MHz,CDCl 3 )δ7.89–7.50(m,6H),7.42–7.08(m,7H),5.58(d,J＝7.7Hz,2H),4.23–4.04(m,4H),4.01(dd,J＝7.7,1.5Hz,2H),1.29–1.02(m,6H). 13 C NMR(100MHz,CDCl 3 )δ171.30,171.17,141.55,138.12,135.29,135.12,134.33,129.17,128.62,128.46,128.00,124.84,124.07,81.77,81.72,61.27,49.94,49.83,14.0.Minor: 1 H NMR(400MHz,CDCl 3 )δ7.84–7.52(m,6H),7.36–7.16(m,7H),5.88–5.71(m,2H),4.16–4.09(m,4H),3.89(dd,J＝5.7,2.5Hz,2H),1.26–1.10(m,6H). 13 C NMR(100MHz,CDCl 3 )δ171.02,170.88,142.00,138.57,135.29,134.83,134.27,128.55,128.46,128.39,127.91,124.30,123.58,82.20,81.72,61.23,50.15,50.02,13.99.HRMS(ESI)calculated for C 28 H 27 ClNaO 5 Se 2 [M+Na]+:660.9770；found:660.9779
example 10
To a 10mL electrolytic cell/reaction flask, 48.8mg (0.2 mmol) of substituted o-phenyldiene (2 j), 81.15mg (0.26 mmol) of diphenyl diselenide, 18.75mg (0.2 mmol) of lithium tetrafluoroborate and 3mL of acetonitrile were added, 3.6mg of water was added, and after stirring uniformly, direct current was introduced under the condition of air atmosphere at room temperature of 25 ℃, the anode and the cathode of the electrode were both platinum electrodes, the current of the reaction system was 6mA, and the reaction time was 4-6 hours. After the reaction is finished, concentrating and spin-drying the reaction solvent by a rotary evaporator, and then mixing the reaction solvent with the solvent according to the volume ratio of 15: petroleum ether of 1: the mixed solution of ethyl acetate is used as an eluent to carry out silica gel column chromatography purification and separation to obtain the light polysubstituted selenium-containing dihydroisobenzofuran derivative (3 aj) with the reaction formula:
the product mass was 55mg and the yield was 53.92%. The nuclear magnetic data and mass spectrum data are analyzed as follows: 1 H NMR(400MHz,CDCl 3 )δ8.02–7.61(m,2H),7.58–6.98(m,12H),5.91–5.41(m,2H),4.23–3.81(m,4H),2.47–2.20(m,3H),1.24–1.06(m,3H). 13 C NMR(100MHz,CDCl 3 )δ203.50,171.1,140.6,139.9,136.54,135.0,134.9,129.5,128.6,128.4,123.6,123.1,121.8 82.9,81.5,61.4,58.8,50.1,28.4,14.0.HRMS(ESI)calculated for C 27 H 26 NaO 3 Se 2 [M+Na]+:581.0105；found:581.0105.
example 11
To a 10mL electrolytic cell/reaction flask, 67mg (0.2 mmol) of substituted o-phthalene (2 n), 81.15mg (0.26 mmol) of diphenyl diselenide, 23.0mg (0.2 mmol) of sodium tetrafluoroborate and 3mL of methanol were added, 3.6mg of water was added, and after stirring uniformly, a direct current was introduced at 20℃for 4.5 hours, both of which were carbon electrodes, and the current of the direct current was 6mA. After the reaction is finished, concentrating and drying the reaction solvent by a rotary evaporator, and then mixing the reaction solvent with the solvent according to the volume ratio of 20: petroleum ether of 1: the mixed solution of ethyl acetate was used as an eluent, and purification and separation by silica gel column chromatography were carried out to obtain 47mg of a colorless oily product (3 an) in a yield of 33.33%.
The nuclear magnetic data and mass spectrum data are analyzed as follows: 1 H NMR(400MHz,CDCl 3 )δ7.67(td,J＝8.7,5.5Hz,2H),7.51(dt,J＝8.3,1.8Hz,2H),7.47–7.39(m,2H),7.36–7.14(m,11H),5.57(t,J＝6.2Hz,2H),5.13(dd,J＝50.3,12.3Hz,2H),4.31–3.92(m,4H),1.18(t,J＝7.1Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ171.26,171.07,150.46(dd,J＝251.0,15.3Hz),135.53(dd,J＝11.1,5.5Hz),135.44,135.22,135.14,129.22,129.19,128.67,128.63,128.53,128.29,128.26,127.76,127.63,112.79(dd,J＝13.7,7.0Hz),81.70,81.58,66.96,61.31,49.68,14.03.HRMS(ESI)calculated for C 28 H 26 F 2 NaO 5 Se 2 [M+Na]+:662.9971；found:662.9979
Claims (5)
1. a preparation method of a polysubstituted selenium-containing dihydro-isobenzofuran derivative, wherein the structure of the polysubstituted selenium-containing dihydro-isobenzofuran derivative is shown as a formula I or a formula V:
wherein R is 1 、R 2 Selected from ester groups or acyl groups, R 1 、R 2 The same or different;
the ester group is selected from-COOR 7 The R is 7 Selected from C1-C5 alkyl, phenyl, naphthyl or benzyl; the acyl is selected from alkyl acyl, and the alkyl of the alkyl acyl is selected from C1-C5 alkyl;
R 3 selected from hydrogen, halo, C1-C5 alkyl;
R 4 selected from phenyl, naphthyl, tolyl;
R 5 and R is 6 Selected from alkoxy groups having 1 to 5 carbon atoms or halogen radicals, R 5 And R is 6 The same or different;
the preparation method is as follows:
the o-phthalene compound shown in the formula II or the formula IV, the diaryl diselenide compound shown in the formula III and water are electrified to react in a solvent containing electrolyte at the temperature of 0-35 ℃ in the air or inert gas atmosphere; the electrolyte is selected from lithium chloride, lithium bromide, lithium tetrafluoroborate, lithium perchlorate, sodium tetrafluoroborate or potassium tetrafluoroborate; the electrifying is to electrify direct current, the direct current is controlled to be 1-15mA, and the electrode used for electrifying is an inert electrode; the solvent is selected from acetonitrile, tetrahydrofuran, benzene, toluene, acetone, methanol or dimethyl sulfoxide.
2. The method of claim 1, wherein formula I or formula V is selected from the following structures:
3. the preparation method according to claim 1, wherein the molar ratio of the o-benzodiene compound represented by formula II or formula IV to the diaryl diselenide compound represented by formula III is 1:1-1:3.
4. The process according to claim 1, wherein the ratio of the volume of the solvent to the amount of the o-dienic compound represented by formula II or IV is 3 to 100mL/mmol.
5. The preparation method according to claim 1, wherein the product obtained by the reaction is obtained by separating and purifying through silica gel column chromatography, the solvent used for separating and purifying through silica gel column chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is 4-30:1.
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