CN116354781A - Synthesis method of organic thioether compound - Google Patents
Synthesis method of organic thioether compound Download PDFInfo
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- CN116354781A CN116354781A CN202310008895.2A CN202310008895A CN116354781A CN 116354781 A CN116354781 A CN 116354781A CN 202310008895 A CN202310008895 A CN 202310008895A CN 116354781 A CN116354781 A CN 116354781A
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- 150000003568 thioethers Chemical class 0.000 title claims abstract description 41
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- 239000003570 air Substances 0.000 claims description 23
- -1 alkenyl sulfonium salt Chemical class 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LOTBYPQQWICYBB-UHFFFAOYSA-N methyl n-hexyl-n-[2-(hexylamino)ethyl]carbamate Chemical compound CCCCCCNCCN(C(=O)OC)CCCCCC LOTBYPQQWICYBB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 150000008125 alkenyl sulfides Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 47
- 239000000047 product Substances 0.000 description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 43
- 150000001875 compounds Chemical class 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 23
- 239000003480 eluent Substances 0.000 description 22
- 238000001704 evaporation Methods 0.000 description 21
- 238000010898 silica gel chromatography Methods 0.000 description 21
- 238000012512 characterization method Methods 0.000 description 20
- 239000012043 crude product Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- 239000003208 petroleum Substances 0.000 description 20
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 20
- 238000004809 thin layer chromatography Methods 0.000 description 20
- 238000001514 detection method Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- 230000008020 evaporation Effects 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 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
- 238000010189 synthetic method Methods 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001430 anti-depressive effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 229940005513 antidepressants Drugs 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- QDXBVEACAWKSFL-UHFFFAOYSA-N ethenethiol Chemical class SC=C QDXBVEACAWKSFL-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- 150000003572 thiolanes Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B45/00—Formation or introduction of functional groups containing sulfur
- C07B45/06—Formation or introduction of functional groups containing sulfur of mercapto or sulfide groups
-
- 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
- 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
- C07D333/06—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
-
- 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
- C07D333/06—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of an organic thioether compound, belonging to the field of organic synthesis. The invention uses the alkenyl sulfide shown in formula I as a raw material, and does not need metal catalysis, and the organic thioether compound shown in formula II is obtained through reaction. Raw materials for the method of the inventionThe method is cheap and easy to obtain, does not need to use a metal catalyst, is environment-friendly and pollution-free, and has the advantages of wide substrate range, higher yield, simple operation, easy separation and purification of products and the like.
Description
Technical Field
The invention belongs to the field of organic synthesis, and in particular relates to a method for synthesizing an organic thioether compound.
Background
Organic thioether compounds are widely used in foods, medicines, pesticides, natural products and functional materials, are closely related to our lives and production, and are particularly important in the research and development of various new drugs. It is reported that compounds containing various organic thioethers have a broad spectrum of biological activities such as antibacterial, insecticidal (compound a), herbicidal, antiviral, antidepressant (compound B), antitumor, etc. In addition, tetrahydrothiophene is used as a special sulfur-containing five-membered heterocyclic compound, and the derivative thereof has various biological activities and pharmacological activities, and is widely used in alkaloids or medicines, such as certain antagonists (compound C), oxidation inhibiting enzymes, antioxidative active substances, plant growth regulators and the like. These above all fall into the category of application of organic thioether compounds. Although these compounds are important, the preparation of these high value compounds remains very challenging, and thus development of a gentle and efficient synthetic method remains of great interest.
The existing method for synthesizing the organic thioether compound mainly has the following defects: most require transition metal catalysis or use of toxic sulfur reagents, are costly and create serious environmental pollution.
Disclosure of Invention
Aiming at the situation that the existing synthetic route needs excessive metal participation and has higher cost, the invention aims to provide a method for synthesizing the organic thioether compound, which is low in cost and environment-friendly, has the advantages of no catalyst, wide applicable substrate range, higher yield, simple operation, easy separation of products and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for synthesizing organic thioether compounds without metal catalysis takes alkenyl sulfonium salt shown in formula I as a raw material, and the organic thioether compounds shown in formula II are obtained by reaction under the action of alkali;
wherein R is 1 Selected from substituted or unsubstituted aryl, substituted with one to three substituents, the substituents being: halogen (F, cl, br, I), C1-C4 alkyl, C1-C4 alkoxy, aryl; r is R 2 、R 3 Selected from hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl, phenyl, or
Is->
"- -" means covalent or non-covalent;
selected from->
Or->
Z 1 For CHR 4 ，Z 2 Is C1-C4 alkyl, phenyl; r is R 4 H, C1 is C4 alkyl.
In one embodiment of the invention, the aryl group is a benzene ring or a naphthalene ring.
In one embodiment of the invention, R 1 Specifically selected from:
in one embodiment of the inventionWherein R is 2 、R 3 Independently selected from hydrogen, methyl, phenyl, isopropyl, or
Is->
In one embodiment of the present invention,
specifically selected from: />
In one embodiment of the present invention,
specifically selected from: />
In one embodiment of the invention, the reaction is carried out in an organic solvent, in particular any one or more of dichloromethane, 1, 4-dioxane, tetrahydrofuran, toluene.
In one embodiment of the invention, the base comprises sodium hydride, sodium tert-butoxide, sodium hydroxide or potassium tert-butoxide.
In one embodiment of the present invention, the reaction temperature is 0℃to 60℃and the reaction time is 3 to 12 hours.
In one embodiment of the present invention, the temperature of the reaction is further preferably 0 to 30 ℃.
In one embodiment of the invention, the reaction time is specifically selected to be 4 hours.
In one embodiment of the present invention, the ratio of the amount of the alkenyl sulfonium salt represented by formula i to the amount of the base substance is 1.0:1.0 to 2.0. Specifically 1.0:1.5.
In one embodiment of the invention, the amount of the organic solvent added is 2-10 mL/mmol based on the amount of the substance of the alkenyl sulfonium salt shown in formula I. Specifically, the concentration of the catalyst is 2-5mL/mmol.
In one embodiment of the invention, the atmosphere of the reaction is air, oxygen or nitrogen.
In one embodiment of the invention, the product is purified after the reaction using silica gel column chromatography separation.
The purification method comprises the following steps: and after the reaction is finished, adding column chromatography silica gel, distilling under reduced pressure to remove the solvent, spin-drying until the silica gel adsorption product is in a powder form, loading the powder into a column, eluting with petroleum ether, collecting, evaporating and concentrating to obtain the organic thioether compound.
The beneficial effects are that:
compared with the prior art, the method has the advantages that no catalyst is needed, raw materials are easy to obtain, the catalytic efficiency is high, and products are easy to separate and purify compared with the prior reported synthesis of the organic thioether compounds. Therefore, the development of a synthetic method of the organic thioether compound has important significance.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to specific embodiments.
The vinylsulfonium salts according to the invention can be prepared by themselves according to the prior art, for example, document F.Berger, E.M.Alvarez, T.Ritter, et al, cine-Substitutions at Five-Membered Hetarenes Enabled by Sulfonium salts. The invention provides a synthesis method which comprises the following steps:
tetramethylene sulfoxide (5.5 mmol,572 mg) was dissolved in 25mL of dichloromethane under argon or nitrogen, the above mixture was stirred at-40 ℃, then α -substituted aryl alkene (5.0 mmol) and trifluoromethanesulfonic anhydride (5.5 mmol,1.55 g) were added dropwise to the reaction, the reaction was continued at-40 ℃ for 30 minutes, the reaction was further allowed to continue at 0 ℃ for 3 hours, tlc plate detection followed by reaction, and after the completion of the reaction, the solvent was removed under reduced pressure in vacuo. Recrystallizing with dichloromethane and diethyl ether to obtain white solid, which is the corresponding sulfonium salt.
The synthetic route of the sulfonium salt is as follows:
wherein R is 1 The method comprises the following steps:
wherein, the liquid crystal display device comprises a liquid crystal display device,
the method comprises the following steps: />
The synthesis route of the target product is as follows:
example 1
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: under air conditions, an alpha-methylstyrene-based tetrahydrothiosulfonium salt (1.0 mmol,354.1 mg), t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in 93% yield (189.8 mg). The material is colorless oilA liquid.
Characterization data: 1 H NMR(400MHz,CDCl 3 )δ7.40–7.37(m,2H),7.34–7.28(m,2H),7.28–7.25(m,1H),5.30(d,J＝1.5Hz,1H),5.12(d,J＝1.3Hz,1H),3.48–3.39(m,1H),2.93–2.87(m,1H),2.85–2.76(m,3H),2.11–1.96(m,2H),1.89–1.80(m,1H),1.65–1.57(m,1H). 13 C NMR(101MHz,CDCl 3 )δ147.0,140.7,128.3,127.5,126.2,113.9,47.0,43.5,36.8,32.3,30.1.
example 2
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: alpha-methyl p-phenyl styrium salt (1.0 mmol,430.1 mg) was added under air, t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in 85% (238.1 mg). The material was a white solid.
Characterization data: 1 H NMR(400MHz,CDCl 3 )δ7.63–7.56(m,4H),7.50–7.43(m,4H),7.37–7.33(m,1H),5.39(s,1H),5.17(s,1H),3.52–3.48(m,1H),2.95–2.92(m,1H),2.86–2.82(m,3H),2.13–2.02(m,2H),1.91–1.84(m,1H),1.68–1.61(m,1H). 13 C NMR(101MHz,CDCl 3 )δ146.5,140.7,140.3,139.6,128.7,127.3,127.0,126.9,126.6,113.9,47.0,43.4,36.8,32.4,30.2.HRMS m/z(ESI)calcd for C 19 H 21 S(M+H) + 281.1358,found 281.1357.
example 3
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: alpha-methyl p-bromostyrol sulfonium salt (1.0 mmol,431.9 mg) was added under air, t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the formula (yield 80% (224.0 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.47–7.43(m,2H),7.27–7.24(m,2H),5.29(s,1H),5.15(s,1H),3.43–3.37(m,1H),2.93–2.88(m,1H),2.84–2.70(m,3H),2.11–1.97(m,2H),1.88–1.81(m,1H),1.64–1.56(m,1H). 13 C NMR(126MHz,CDCl 3 )δ146.0,139.7,131.4,127.9,121.4,114.5,46.9,43.3,36.8,32.3,30.1.HRMS m/z(ESI)calcd for C 13 H 14 BrSNa(M+Na) + 304.9970,found 304.9968.
example 4
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: alpha-methyl meta-chlorostyrosol (1.0 mmol,239.1 mg) was taken up in air, t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction is finished, the solvent is removed by reduced pressure distillation, the crude product is subjected to silica gel column chromatography separation, petroleum ether is used for eluting, TLC (thin layer chromatography) point plate tracking detection is carried out, eluent containing target products is collected, the target product eluent is combined, and evaporation concentration is carried out to obtain the shown nodeThe compound was structured in 54% yield (128.6 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(400MHz,CDCl 3 )δ7.34(s,1H),7.23(s,3H),5.29(s,1H),5.14(s,1H),3.42–3.35(m,1H),2.91–2.68(m,4H),2.07–1.98(m,2H),1.87–1.79(m,1H),1.62–1.52(m,1H). 13 C NMR(101MHz,CDCl 3 )δ145.9,142.7,134.2,129.6,127.5,126.4,124.4,115.1,46.8,43.3,36.8,32.4,30.2.HRMS m/z(ESI)calcd for C 13 H 16 ClS(M+H) + 239.0656,found 238.0655.
example 5
The structural formula of the tetrahydrothiophene derivative prepared in the embodiment is as follows:
the preparation method comprises the following steps: alpha-methyl 2, 4-dichlorostyryl sulfonium salt (1.0 mmol,422.0 mg) was added under air, t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the formula (yield: 78% (212.2 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(400MHz,CDCl 3 )δ7.37(d,J＝2.1Hz,1H),7.22–7.19(m,1H),7.15–7.13(m,1H),5.32(s,1H),5.03(s,1H),3.28–3.24(m,1H),2.90–2.81(m,3H),2.64–2.58(m,1H),2.08–2.02(m,2H),1.87–1.83(m,1H),1.62–1.56(m,1H). 13 C NMR(101MHz,CDCl 3 )δ145.9,139.5,133.5,132.8,131.4,129.3,126.9,117.8,46.9,44.5,37.0,32.4,30.2.HRMS m/z(ESI)calcd for C 13 H 14 Cl 2 NaS(M+Na) + 295.0085,found 295.0087.
example 6
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: under air conditions, 1-isopropenyl naphthalene sulfonium salt (1.0 mmol,404.1 mg), t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the following formula (yield: 87% (221.1 mg)). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ8.11–8.07(m,1H),7.88–7.85(m,1H),7.79(d,J＝8.3Hz,1H),7.52–7.32(m,3H),7.33(dd,J＝7.0,1.3Hz,1H),5.50(d,J＝1.6Hz,1H),5.17(d,J＝1.9Hz,1H),3.39–7.34(m,1H),2.95–2.88(m,2H),2.85–2.75(m,2H),2.11–2.01(m,2H),1.89–1.80(m,1H),1.66–1.59(m,1H). 13 C NMR(126MHz,CDCl 3 )δ147.1,140.4,133.7,131.2,128.3,127.4,125.8,125.7,125.7,125.3,125.2,117.0,47.0,46.7,37.0,32.3,30.3.HRMS m/z(ESI)calcd for C 17 H 19 S(M+H) + 255.1202,found 255.1203.
example 7
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: under air conditions, alpha-methyl 1, 2-methylenedioxystyrene sulfonium salt (1.0 mmol,398.0 mg), t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperatureAnd stirring for 4 hours. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in 89% yield (220.7 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ6.90–6.85(m,2H),6.76(d,J＝8.0Hz,1H),5.95(s,2H),5.20(d,J＝1.4Hz,1H),5.04(d,J＝1.4Hz,1H),3.46–3.40(m,1H),2.92–2.87(m,1H),2.84–2.80(m,1H),2.79–2.70(m,2H),2.10–1.98(m,2H),1.89–1.80(m,1H),1.63–1.57(m,1H). 13 C NMR(126MHz,CDCl 3 )δ147.7,147.0,146.5,135.0,119.7,113.0,108.0,106.8,101.0,47.0,43.7,36.7,32.3,30.1.HRMS m/z(ESI)calcd for C 14 H 17 O 2 S(M+H) + 249.0944,found249.0944.
example 8
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: under air conditions, an alpha-ethylstyrenesulfonium salt (1.0 mmol,368.1 mg), t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the formula (yield: 83% (180.9 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(400MHz,CDCl 3 )δ7.39–7.35(m,2H),7.34–7.24(m,3H),5.21(s,1H),5.13(s,1H),3.54–3.48(m,1H),2.88–2.80(m,2H),2.80–2.72(m,1H),2.21–2.13(m,2H),1.91–1.80(m,1H),1.53–1.49(m,1H),1.18(d,J＝6.9Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ154.3,142.6,128.1,127.2,127.0,112.6,53.7,45.9,34.8,32.3,31.3,19.2.HRMS m/z(ESI)calcd for C 14 H 19 S(M+H) + 219.1202,found 219.1201.
example 9
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: under air conditions, an alpha-cyclopentylstyryl sulfonium salt (1.0 mmol,408.1 mg), t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (2 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the following formula (185.8 mg) in a yield of 72%. The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.31–7.27(m,3H),7.25–7.22(m,2H),5.31(d,J＝1.4Hz,1H),5.03(d,J＝1.4Hz,1H),3.89(dd,J＝9.4,6.4Hz,1H),2.83–2.79(m,2H),2.16–2.11(m,1H),2.05–1.95(m,2H),1.94–1.85(m,2H),1.83–1.78(m,1H),1.74–1.65(m,4H),1.63–1.55(m,2H). 13 C NMR(126MHz,CDCl 3 )δ154.9,143.1,128.7,127.6,126.6,115.6,56.1,55.5,35.9,33.2,32.4,31.5,31.4,24.1,24.0.HRMS m/z(ESI)calcd for C 17 H 23 S(M+H) + 259.1515,found 259.1516.
example 10
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: alpha-methyl p-chlorostyrosol salt (1.0 mmol,424.0 mg) was taken under air, t BuOK (1.5 equiv,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and finally the reaction was stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the formula (yield 83% (227.4 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.39–7.35(m,2H),7.33–7.29(m,6H),7.24–7.21(m,H),5.37(d,J＝1.1Hz,1H),5.17(d,J＝1.3Hz,1H),3.04–3.01(m,2H),2.85–2.82(m,2H). 13 C NMR(126MHz,CDCl 3 )δ145.3,138.6,136.1,133.3,129.4,128.8,128.5,127.3,126.0,114.2,35.0,32.3.HRMS m/z(ESI)calcd for C 16 H 16 ClS(M+H) + 275.0656,found 275.0655.
example 11
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: alpha-methyl o-chlorostyrosol sulfonium salt (1.0 mmol,424.0 mg) was added under air, t BuOK (1.5 equiv,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and finally the reaction was stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the formula (yield 83% (221.9 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.42–7.37(m,1H),7.33–7.27(m,4H),7.25–7.22(m,3H),7.21–7.17(m,1H),5.33(d,J＝1.4Hz,1H),5.11(d,J＝1.4Hz,1H),3.00–2.97(m,2H),2.85–2.82(m,2H). 13 C NMR(126MHz,CDCl 3 )δ146.4,140.7,136.3,132.1,130.6,129.5,129.1,128.8,128.5,126.6,125.8,116.9,36.1,31.8.HRMS m/z(ESI)calcd for C 16 H 16 ClS(M+H) + 275.0656,found 275.0656.
example 12
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: 2-isopropenyl naphthalenesulfonium salt (1.0 mmol,404.1 mg) was reacted under air conditions, t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the following formula (208.9 mg) in 72% yield. The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.87–7.81(m,4H),7.59(dd,J＝8.5,1.9Hz,1H),7.54–7.48(m,2H),7.40–7.38(m,2H),7.34–7.31(m,2H),7.25–7.22(m,1H),5.54(d,J＝1.1Hz,1H),5.27(d,J＝1.2Hz,1H),3.12–3.09(m,2H),3.01–2.98(m,2H). 13 C NMR(126MHz,CDCl 3 )δ146.3,137.4,136.2,133.3,132.8,129.4,128.9,128.1,128.0,127.5,126.2,126.0,125.9,124.7,124.5,114.3,35.3,32.6.HRMS m/z(ESI)calcd for C 20 H 19 S(M+H) + 291.1202,found291.1202.
example 13
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: alpha-ethyl p-chlorostyrosol (1.0 mmol,438.0 mg) was taken under air, t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the specification in 84% (242.0 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.26–7.20(m,6H),7.17–7.14(m,3H),5.22(s,1H),5.12(s,1H),3.09(dd,J＝12.7,4.9Hz,1H),2.88–2.83(m,1H),2.74(dd,J＝12.7,8.4Hz,1H),1.26(d,J＝6.7Hz,3H). 13 C NMR(126MHz,CDCl 3 )δ151.6,140.3,136.6,133.2,129.5,128.8,128.4,128.0,126.0,112.9,40.1,37.7,19.0.HRMS m/z(ESI)calcd for C 17 H 18 ClS(M+H) + 289.0812,found 289.0812.
example 14
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: under air conditions, alpha-benzylstyrenesulfonium salt (1.0 mmol,466.1 mg), t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction is finished, the solvent is removed by reduced pressure distillation, the crude product is subjected to silica gel column chromatography separation, petroleum ether is used for eluting, TLC (thin layer chromatography) point plate tracking detection is carried out, eluent containing the target product is collected, the eluent containing the target product is combined, the compound with the structure shown is obtained by evaporation and concentration, and the yield is 82(259.1 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.37–7.32(m,8H),7.31–7.24(m,6H),7.23–7.19(m,1H),5.54(s,1H),5.29(s,1H),4.32–4.04(m,1H),3.55(dd,J＝12.8,7.1Hz,1H),3.39(dd,J＝12.8,8.0Hz,1H). 13 C NMR(126MHz,CDCl 3 )δ149.9,141.6,141.3,136.7,129.4,128.8,128.4,128.2,128.1,127.4,126.8,126.7,126.0,114.3,49.9,39.0.HRMS m/z(ESI)calcd for C 22 H 21 S(M+H) + 317.1358,found 317.1360.
example 15
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: alpha-ethyl p-chlorostyrosol (1.0 mmol,376.0 mg) was taken up in air, t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in 89% yield (201.1 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.28–7.23(m,4H),5.20(s,1H),5.09(s,1H),2.87–2.81(m,1H),2.64(dd,J＝12.7,5.1Hz,1H),2.39(dd,J＝12.7,8.3Hz,1H),2.04(s,3H),1.21(d,J＝6.8Hz,3H). 13 C NMR(126MHz,CDCl 3 )δ152.0,140.6,133.2,128.4,128.0,112.6,40.9,38.0,19.2,16.3.HRMS m/z(ESI)calcd for C 12 H 16 S(M+H) + 227.0656,found 227.0657.
example 16
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: alpha-ethyl p-fluorostyrylsulfonium salt (1.0 mmol,360.0 mg) was added under air, t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the following formula (yield 90% (189.7 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.33–7.29(m,2H),7.03–6.99(m,2H),5.20(s,1H),5.09(s,1H),2.90–2.85(m,1H),2.68(dd,J＝12.8,5.2Hz,1H),2.42(dd,J＝12.8,8.4Hz,1H),2.07(s,3H),1.24(d,J＝6.8Hz,3H). 13 C NMR(126MHz,CDCl 3 )δ162.2(d,J＝246.2Hz),152.1,138.1(d,J＝3.1Hz),128.3(d,J＝7.8Hz),115.0(d,J＝21.1Hz),112.2,40.9,38.2,19.2,16.3. 19 F NMR(471MHz,CDCl 3 )δ-115.38.HRMS m/z(ESI)calcd for C 12 H 16 FS(M+H) + 211.0951,found 211.0950.
example 17
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: under air conditions, an alpha-benzylstyrenesulfonium salt (1.0 mmol,404.1 mg), t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction is finished, the solvent is removed by reduced pressure distillation, and the crude product is subjected to silica gel column chromatography separation to obtain petroleumEther elution, TLC plate tracing, collecting the eluent containing the target product, combining the target product eluates, evaporating and concentrating to obtain the compound with the shown structure, yield 85% (216.0 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.33–7.27(m,6H),7.25–7.21(m,4H),5.48(d,J＝0.8Hz,1H),5.24(t,J＝1.0Hz,1H),4.10(t,J＝7.0Hz,1H),3.11(dd,J＝12.8,6.7Hz,1H),2.94(dd,J＝12.8,8.4Hz,1H),2.05(s,3H). 13 C NMR(126MHz,CDCl 3 )δ150.3,141.9,141.7,128.4,128.2,128.1,127.3,126.8,126.7,114.0,50.4,39.8,16.4.HRMS m/z(ESI)calcd for C 17 H 19 S(M+H) + 255.1202,found 255.1203.
example 18
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: alpha-isopropylstyrene sulfonium salt (1.0 mmol,356.1 mg) was isolated under air conditions, t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the following formula (yield 88% (181.4 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.31–7.25(m,3H),7.22–7.20(m,2H),5.23(d,J＝1.5Hz,1H),4.92(d,J＝1.5Hz,1H),2.58(s,2H),2.10(s,3H),1.22(s,6H). 13 C NMR(126MHz,CDCl 3 )δ156.4,142.6,128.9,127.4,126.5,114.1,47.1,40.7,27.2,17.6.HRMS m/z(ESI)calcd for C 13 H 19 S(M+H) + 207.1202,found 207.1204.
example 19
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: under air conditions, an alpha-cyclopentylstyryl sulfonium salt (1.0 mmol,382.1 mg), t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, eluting with petroleum ether, followed by detection by TLC plate, collecting the eluent containing the objective product, combining the eluates of the objective product, and concentrating by evaporation to give the compound of the structure shown in the following formula (yield: 63% (146.2 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.33–7.27(m,5H),5.26(d,J＝1.5Hz,1H),5.04(d,J＝1.5Hz,1H),2.65(s,2H),2.10(s,3H),1.92–1.88(m,2H),1.77–1.68(m,6H). 13 C NMR(126MHz,CDCl 3 )δ154.2,143.0,128.5,127.5,126.6,114.9,53.0,43.6,36.6,23.2,17.2.HRMS m/z(ESI)calcd for C 15 H 21 S(M+H) + 233.1358,found 233.1360.
example 20
The structural formula of the organic thioether compound prepared in the embodiment is as follows:
the preparation method comprises the following steps: under air conditions, an alpha-cyclohexylstyryl sulfonium salt (1.0 mmol,396.1 mg), t BuOK (1.5 mmol,168.3 mg) was added to a 25mL reaction tube equipped with a magnetic stirrer, then solvent THF (5 mL) was added, and the reaction was finally stirred at room temperature for 4h. After the reaction, the solvent is removed by reduced pressure distillation, the crude product is subjected to silica gel column chromatography and separated, petroleum ether is used for eluting, and TLC (thin layer chromatography) plate tracking is carried outDetecting, collecting eluent containing target products, combining the target product eluates, evaporating and concentrating to obtain a compound with the structure shown in the specification, and obtaining the compound with the yield of 62% (152.5 mg). The material was a colorless oily liquid.
Characterization data: 1 H NMR(500MHz,CDCl 3 )δ7.29–7.23(m,5H),5.23(d,J＝1.5Hz,1H),5.05(d,J＝1.5Hz,1H),2.63(s,2H),2.11(s,3H),1.76–1.72(m,2H),1.55–1.41(m,8H). 13 C NMR(126MHz,CDCl 3 )δ153.9,142.7,128.9,127.5,126.5,116.5,44.4,43.4,34.6,26.2,22.3,17.2.HRMS m/z(ESI)calcd for C 16 H 23 S(M+H) + 247.1515,found 247.1516.
example 21: influence of alkali
Referring to example 1, only potassium t-butoxide was replaced with other base shown in table 1, and the other was unchanged, and the results of the corresponding reaction are shown in table 1.
TABLE 1 Effect of base on the preparation of organic thioether compounds
Example 22: influence of solvent
Referring to example 1, only tetrahydrofuran was replaced with other solvents shown in table 2, and the other solvents were unchanged, and the results of the corresponding reactions are shown in table 2.
TABLE 2 Effect of solvent selection on the preparation of organic thioether compounds
| Solvent(s) | Yield of organic thioether compounds |
| Tetrahydrofuran (example 1) | 93％ |
| DCM | 85％ |
| 1, 4-Dioxahexacyclic ring | 89％ |
| Toluene | 76％ |
| DMSO | <5％ |
Example 23: expansion of reaction atmosphere
Referring to example 1, the atmosphere was replaced with oxygen and nitrogen, respectively, and the results of the corresponding reactions were shown in table 3.
TABLE 3 influence of the reaction atmosphere on organic thioether compounds
| Reaction atmosphere | Yield of organic thioether compounds |
| Air (example 1) | 93％ |
| Oxygen gas | 86％ |
| Nitrogen gas | 89％ |
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (10)
1. A method for synthesizing an organic thioether compound without metal catalysis is characterized in that an alkenyl sulfonium salt shown in a formula I is used as a raw material, and the organic thioether compound shown in a formula II is obtained through reaction under the action of alkali;
wherein R is 1 Selected from substituted or unsubstituted aryl, substituted with one to three substituents, the substituents being: halogen (F, cl, br, I), C1-C4 alkyl, C1-C4 alkoxy, aryl; r is R 2 、R 3 Selected from hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl, phenyl, or
Is->
"- -" means covalent or non-covalent;
selected from->
Or->
Z 1 For CHR 4 ，Z 2 Is C1-C4 alkyl, phenyl; r is R 4 H, C1 is C4 alkyl.
2. The method of claim 1, wherein the aryl group is a benzene ring or a naphthalene ring.
3. The method of claim 1, wherein R 1 Selected from:
4. the method of claim 1, wherein R 2 、R 3 Independently selected from hydrogen, methyl, phenyl, isopropyl, or
Is->
5. The process according to claim 1, wherein the reaction is carried out in an organic solvent, in particular any one or more of dichloromethane, 1, 4-dioxane, tetrahydrofuran, toluene.
6. The method of claim 1, wherein the base comprises sodium hydride, sodium t-butoxide, sodium hydroxide, or potassium t-butoxide.
7. The method according to claim 1, wherein the reaction temperature is 0 ℃ to 60 ℃ and the reaction time is 3 to 12 hours.
8. The method according to claim 1, wherein the ratio of the amount of the alkenyl sulfonium salt represented by formula i to the amount of the base substance is 1.0:1.0 to 2.0.
9. The method according to claim 1, wherein the amount of the organic solvent added is 2-10 mL/mmol based on the amount of the substance of the alkenyl sulfonium salt represented by formula i.
10. The method according to any one of claims 1 to 9, wherein the atmosphere of the reaction is air, oxygen or nitrogen.
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