CN114835674A - Preparation method of aromatic thioether - Google Patents
Preparation method of aromatic thioether Download PDFInfo
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- CN114835674A CN114835674A CN202210617990.8A CN202210617990A CN114835674A CN 114835674 A CN114835674 A CN 114835674A CN 202210617990 A CN202210617990 A CN 202210617990A CN 114835674 A CN114835674 A CN 114835674A
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- -1 aromatic thioether Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 7
- 238000005286 illumination Methods 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 239000007806 chemical reaction intermediate Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 claims description 2
- YCBWLMWEQURJHX-UHFFFAOYSA-N 4-(trifluoromethyl)cyclohexan-1-amine Chemical compound NC1CCC(C(F)(F)F)CC1 YCBWLMWEQURJHX-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- WHELTKFSBJNBMQ-UHFFFAOYSA-L dichlororuthenium;2-pyridin-2-ylpyridine;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ru+2].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 WHELTKFSBJNBMQ-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000000543 intermediate Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000004832 aryl thioethers Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000002924 anti-infective effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/34—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/04—Thiosulfonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides symmetrical and asymmetrical aromatic thioether with pharmaceutical activity, a preparation method and application thereof, belonging to the field of organic synthesis and functional materials. The aromatic thioether of the invention has the structure
Wherein R is 1 、R 2 Independently selected from alkyl, substituted or unsubstituted aromatic group, substituted or unsubstituted heterocyclic group. The preparation method comprises the following steps: under the action of catalyst and additive
And
mixed illumination reaction to obtain reaction intermediate
After that
And
mixing and carrying out illumination reaction to obtain the aromatic thioether. The method has the advantages of simple and easily obtained raw materials, mild reaction conditions and environmental friendliness; and the operation steps are simple and convenient, the yield is high, the reaction conditions are suitable for amplification reaction, and a foundation is laid for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic compounds, and particularly relates to a preparation method of aromatic thioether.
Background
In the field of organic synthesis, thioethers are an important class of organic sulfur compounds, and are important intermediates for the synthesis of many biologically and pharmaceutically active molecules. In fact, many kinds of aromatic thioether compounds show potential clinical application properties, especially asymmetric aromatic thioether with pharmaceutical activity, which has been widely used in various therapeutic fields as a pharmaceutical intermediate, such as diabetes, anti-infective drugs, immunity, alzheimer disease, parkinson disease, and the like.
Researchers have been focusing on developing various synthetic strategies for constructing carbon-sulfur and per-sulfur bonds. In recent years, with the concern of society on environmental problems, research personnel pay more attention to finding a more environment-friendly, sustainable and high-atom-economy synthesis method. It is therefore of great importance to develop new efficient and versatile strategies for the preparation of asymmetric thioethers.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of aromatic thioether.
The first purpose of the invention is to provide an aromatic thioether with a structure
Wherein R is 1 、R 2 Independently selected from alkyl, substituted or unsubstituted aromatic group, substituted or unsubstituted heterocyclic group.
In one embodiment of the present invention, the substituent group in the substituted aromatic group is one or more of alkyl, halogen and alkoxy.
In one embodiment of the invention, the heterocyclic group is selected from substituted phenyl, naphthyl or thiophene.
In one embodiment of the present invention, the substituted group in the substituted or unsubstituted heterocyclic group is one or more of alkyl, halogen and alkoxy.
The second purpose of the invention is to provide a preparation method of the aromatic thioether, which comprises the following steps: under the action of catalyst and additive
And
mixed illumination reaction to obtain reaction intermediate
After that
Mixing and carrying out illumination reaction to obtain the aromatic thioether.
In one embodiment of the invention, the catalyst is selected from one or more of tris (2,2' -bipyridyl) ruthenium (ii) chloride hexahydrate, tris (2-phenylpyridine) iridium, acridine hydrochloride and 2,4,5, 6-tetrakis (9-carbazolyl) -isophthalonitrile.
In one embodiment of the invention, the additive is selected from one or more of potassium phosphate, cesium carbonate and sodium hydrogen phosphate.
In one embodiment of the invention, the solvent of the reaction is selected from one or more of acetonitrile, ethanol and ethyl acetate.
In one embodiment of the invention, the reaction conditions are: the reaction time is 12-24h at room temperature.
In one embodiment of the invention, the light source for the light reaction is selected from ultraviolet light having a wavelength of 400nm to 10 nm.
In one embodiment of the present invention,
in a molar ratio of 1:1 to 1: 2.
In one embodiment of the invention, the catalyst is in combination with
In a molar ratio of 1:25 to 1: 18.
In one embodiment of the invention, the additive is in combination with
In a molar ratio of 1:25 to 1: 18.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the technical scheme of the invention takes the commercialized aryl diazonium salt as a raw material, is cheap and easy to obtain, greatly widens the substrate range of aryl thioether, and can synthesize the aryl thioether compounds which are difficult to obtain in the past.
The mechanism of the invention is as follows:
firstly, under the action of an excited state photosensitive catalyst, diazonium salt forms aryl free radical and releases nitrogen through single electron transfer process, and the aryl free radical reacts with thiosulfonic acid ester to generate aryl thioether product.
Drawings
In order that the present disclosure may be more readily understood, a more particular description of the disclosure will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of Compound 01 of example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of Compound 01 of example 2 of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of Compound 01 of example 3 of the present invention.
Detailed Description
The present invention is further described in conjunction with table 1 and the following examples, which are not intended to limit the invention, so that those skilled in the art may better understand the present invention and can practice it.
Table 1 Structure of Compounds and methods of use thereof 1 HNMR data
Example 1
This example illustrates a specific synthetic method for the compounds in table 1. The compound can be synthesized by the following reaction steps:
(1): synthesis of intermediate (a-1) and intermediate (a-2)
In a 50mL round-bottom flask, heterocyclic amine (10.6mmol) was dissolved in absolute ethanol (8mL) and HBF 4 (50%, 4mL, 32mmol) of the mixed solution, t-BuONO (6.5mL,48mmol) was slowly added dropwise at 0 ℃. Diethyl ether (4mL) was added without the diazonium salt precipitating. The mixture was filtered, washed with diethyl ether (10mL) and petroleum ether (10mL) and dried to give the desired heterocyclic diazonium salts (a-1) and (a-2).
(2): synthesis of intermediate (a-3) and intermediate (a-4)
Aniline (10mmol) was dissolved in 4mL of distilled water and 3.4mL of 50% HBF 4 After cooling to 0 deg.C, sodium nitrite (0.69g in 1.5mL distilled water) was slowly added dropwise over 5min, stirred for 30min, filtered, the precipitate collected, and redissolved with acetone. Ether was added until the tetrafluoroboric acid diazonium salt precipitated, filtered, washed three times with 3X 10mL of ether, and dried under vacuum to afford the corresponding intermediate (a-3) and intermediate (a-4).
(3): synthesis of intermediate (a-5)
Sodium benzenesulfinate (10g, 61mmol) and sulfur (1.95g, 61mmol) were dissolved in anhydrous pyridine (60mL) to give a yellow solution. The reaction was stirred under argon and after 1 hour a white suspension was obtained. Ether was added to the suspension and the reaction was filtered and washed with anhydrous ether to give PhSO 2 SNa, white crystalline solid.
1.97g (10mmol) PhSO were added 2 SNa was dissolved in chloroform (10mL), and 0.5mL of acetyl chloride (7.2mmol) was slowly added thereto, followed by stirring at room temperature for 12 hours. After the reaction is finished, extracting by using ethyl acetate and water, removing a water layer, drying by using anhydrous sodium sulfate, removing an organic solvent by rotary evaporation, and purifying by column chromatography to obtain a light yellow solid, namely the corresponding intermediate (a-5).
(4): synthesis of Compounds
a) Synthesis of Compound 01
In a glove box, 0.2mmol of the compound (a-1), 0.4mmol of the compound (a-5), Ru (bpy) 3 Cl 2 ·6H 2 O (5 mol%) and K 3 PO 4 (1eq.) to a dry 8mL reaction vial, 2mL of MeCN solvent was added, the reaction vial was capped, and the reaction was allowed to proceed for 12 hours at room temperature under light. After the reaction, 0.2mmol of the compound (a-4) was weighed in a glove box, the reaction bottle cap was closed, and the reaction was continued at room temperature under light for 12 hours until the reaction was completed. Removing the organic solvent by rotary evaporation, and purifying by column chromatography to obtain the product, i.e. compound 01 1 The H NMR data are shown in Table 1.
b) Synthesis of Compound 02
In a glove box, 0.2mmol of the compound (a-2), 0.4mmol of the compound (a-5), Ru (bpy) 3 Cl 2 ·6H 2 O (5 mol%) and K 3 PO 4 (1eq.) to a dry 8mL reaction vial, 2mL of MeCN solvent was added, the reaction vial was capped, and the reaction was allowed to proceed for 12 hours at room temperature under light. After the reaction, 0.2mmol of the compound (a-4) was weighed in a glove box, the reaction bottle cap was closed, and the reaction was continued at room temperature under light for 12 hours until the reaction was completed. Removing the organic solvent by rotary evaporation, and purifying by column chromatography to obtain the product, i.e. the compound 02 which is 1 The H NMR data are shown in Table 1.
c) Synthesis of Compound 03
In a glove box, 0.2mmol of the compound (a-3), 0.4mmol of the compound (a-5), Ru (bpy) 3 Cl 2 ·6H 2 O (5 mol%) and K 3 PO 4 (1eq.) to a dry 8mL reaction vial, 2mL of MeCN solvent was added, the reaction vial was capped, and the reaction was allowed to proceed for 12 hours at room temperature under light. After the reaction, 0.2mmol of the compound (a-4) is weighed in a glove box, a reaction bottle cap is covered, and the reaction is continued for 12 hours at room temperature under illumination until the reaction is finished. And (4) removing the organic solvent by rotary evaporation, and purifying by column chromatography to obtain the product. I.e. compound 03, which 1 The H NMR data are shown in Table 1.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. An aromatic thioether, characterized in that the aromatic thioether has the structure
Wherein R is 1 、R 2 Independently selected from alkyl, substituted or unsubstituted aromatic group, substituted or unsubstituted heterocyclic group.
2. The aromatic thioether according to claim 1, wherein the substituent group in the substituted aromatic group is one or more of an alkyl group, a halogen group and an alkoxy group.
3. The aromatic thioether according to claim 1, wherein the heterocyclic group is selected from the group consisting of substituted phenyl, naphthyl, or thiophene.
4. The aromatic thioether according to claim 1, wherein the substituent in the substituted or unsubstituted heterocyclic group is one or more of an alkyl group, a halogen group and an alkoxy group.
5. The process for the preparation of aromatic thioethers according to any one of claims 1 to 4, characterized in that it comprises the following steps: under the action of catalyst and additive
And
mixed illumination reaction to obtain reaction intermediate
After that
Mixing and carrying out illumination reaction to obtain the aromatic thioether.
6. The method according to claim 5, wherein the catalyst is one or more selected from the group consisting of tris (2,2' -bipyridyl) ruthenium (II) chloride hexahydrate, tris (2-phenylpyridine) iridium, acridine hydrochloride and 2,4,5, 6-tetrakis (9-carbazolyl) -isophthalonitrile.
7. The method of claim 5, wherein the additive is selected from one or more of potassium phosphate, cesium carbonate and sodium hydrogen phosphate.
8. The method according to claim 5, wherein the light source for the photoreaction is selected from ultraviolet light having a wavelength of 400nm to 10 nm.
9. The production method according to claim 5,
in a molar ratio of 1:1 to 1: 2.
10. The method of claim 5, wherein the catalyst is mixed with
In a molar ratio of 1:25 to 1: 18; said additives and
in a molar ratio of 1:25 to 1: 18.
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- 2022-06-01 CN CN202210617990.8A patent/CN114835674A/en not_active Withdrawn
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