CN114044730A - Synthesis method of sulfoxide compound - Google Patents
Synthesis method of sulfoxide compound Download PDFInfo
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- CN114044730A CN114044730A CN202111419804.1A CN202111419804A CN114044730A CN 114044730 A CN114044730 A CN 114044730A CN 202111419804 A CN202111419804 A CN 202111419804A CN 114044730 A CN114044730 A CN 114044730A
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- alkyl
- electron
- sulfoxide
- sulfoxide compounds
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- -1 sulfoxide compound Chemical class 0.000 title claims abstract description 66
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- DIIWSYPKAJVXBV-UHFFFAOYSA-N Hantzch dihydropyridine Natural products CCOC(=O)C1=CC(C(=O)OCC)=C(C)N=C1C DIIWSYPKAJVXBV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 239000011941 photocatalyst Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000005286 illumination Methods 0.000 claims abstract description 8
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 8
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 5
- 150000003455 sulfinic acids Chemical class 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical group C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 2
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical class C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical class C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000002346 iodo group Chemical group I* 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 abstract description 10
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 abstract description 7
- 150000003568 thioethers Chemical class 0.000 abstract description 7
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 5
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- FJPFWMYTFGJMAN-UHFFFAOYSA-N 2-sulfinylimidazole Chemical compound O=S=C1N=CC=N1 FJPFWMYTFGJMAN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000269 nucleophilic effect Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 2
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 8
- 229910000024 caesium carbonate Inorganic materials 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 7
- 238000009423 ventilation Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- DILXLMRYFWFBGR-UHFFFAOYSA-N 2-formylbenzene-1,4-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(S(O)(=O)=O)C(C=O)=C1 DILXLMRYFWFBGR-UHFFFAOYSA-N 0.000 description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- YDRYLMNFLKANKC-UHFFFAOYSA-N 1,3-dimethyl-1,2-dihydroimidazol-1-ium;iodide Chemical compound [I-].CN1C[NH+](C)C=C1 YDRYLMNFLKANKC-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IMFBMMNQDMTHGG-UHFFFAOYSA-M 1,4-dimethyl-1,2,4-triazol-4-ium;iodide Chemical compound [I-].CN1C=N[N+](C)=C1 IMFBMMNQDMTHGG-UHFFFAOYSA-M 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- XBWYYTURPBHPFJ-UHFFFAOYSA-M 3-ethyl-1,3-benzothiazol-3-ium;bromide Chemical compound [Br-].C1=CC=C2[N+](CC)=CSC2=C1 XBWYYTURPBHPFJ-UHFFFAOYSA-M 0.000 description 1
- JIUIHDUXMVJNKD-UHFFFAOYSA-N 4-(trifluoromethyl)benzenesulfinic acid Chemical compound OS(=O)C1=CC=C(C(F)(F)F)C=C1 JIUIHDUXMVJNKD-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHLIXXLINGXTDI-UHFFFAOYSA-N diethyl 2,6-dimethyl-4-(phenylmethoxymethyl)-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1COCC1=CC=CC=C1 QHLIXXLINGXTDI-UHFFFAOYSA-N 0.000 description 1
- GERWBKSVDHUVIT-UHFFFAOYSA-N diethyl 4-cyclohexyl-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1CCCCC1 GERWBKSVDHUVIT-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 description 1
- IILVFSMKWWTVRT-UHFFFAOYSA-M sodium;4-iodobenzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=C(I)C=C1 IILVFSMKWWTVRT-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- AUPDIWFBUOVUGO-UHFFFAOYSA-N thiophene-2-sulfinic acid Chemical compound OS(=O)C1=CC=CS1 AUPDIWFBUOVUGO-UHFFFAOYSA-N 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 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
- C07B45/04—Formation or introduction of functional groups containing sulfur of sulfonyl or sulfinyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of organic chemistry, and particularly relates to a synthesis method of a sulfoxide compound. The synthesis method comprises the steps of reacting sulfinic acid or sulfinate thereof, N '-carbonyl diimidazole and 4-alkyl Hantzsch ester in an organic solvent under the existence of a photocatalyst, a nitrogen heterocyclic carbene catalyst and alkali under the illumination condition under the simple and mild condition, firstly reacting the sulfinic acid and the N, N' -carbonyl diimidazole to generate corresponding sulfinylimidazole, then carrying out nucleophilic attack by the nitrogen heterocyclic carbene, carrying out single electron transfer under the photocatalysis to generate sulfinyl free radicals and alkyl free radicals in a system, and then carrying out free radical coupling to generate the target sulfoxide compound. The method provides a brand-new idea for synthesizing the sulfoxide compounds without oxidation reaction of mercaptan and thioether compounds, constructs a series of sulfoxide compounds which are difficult to synthesize by using a common method, and has good guiding significance and application prospect in the fields of scientific research and industry.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, and particularly relates to a synthesis method of a sulfoxide compound.
Background
The sulfoxide compounds have wide application in organic synthesis, pharmaceutical chemistry and agricultural chemistry. Traditional strategies for the synthesis of sulfoxides rely heavily on the catalytic oxidation of thioethers [ (a) k. -j.liu, z.wang, w. -m.he et al.green chem.,2021,23, 496; (b) l.zhao, h.zhang and y.wang, j.org.chem.,2016,81, 129; (c) r. H.Wu, J.Wu, M.X.Yu and L.G.Zhu, RSC adv, 2017,7,44259 ] easily generate sulfone byproducts, and are difficult to separate; and thioether compounds are usually prepared from malodorous mercaptan and thiophenol compounds, so that the application development of the thioether compounds is greatly limited.
Disclosure of Invention
The invention aims to provide a method for synthesizing sulfoxide compounds, which is simple, convenient, environment-friendly and efficient and does not need to pass through a mercaptan/thioether oxidation path. The synthesis method provided by the invention comprises the steps of taking sulfinic acid and salts thereof as reaction raw materials, generating sulfinyl free radicals under the co-catalysis of light and N-heterocyclic carbene, and obtaining the sulfoxide compounds through one-step coupling. The sulfinic acid and the salt thereof have the advantages of wide sources and easy preparation, simultaneously, the reaction process does not completely pass through odorous mercaptan and thioether compounds, the sulfone byproducts are not generated, the subsequent separation is simple, and the method has wide application prospect.
The invention creatively uses sulfinic acid and salts thereof as synthons to simply, efficiently and selectively generate the sulfoxide compounds. Sulfoxide groups exist in molecules of the compounds, and the molecular structural general formula of the compounds is as follows:
the technical scheme adopted by the invention for solving the technical problems is as follows:
a synthesis method of sulfoxide compounds comprises the steps of reacting sulfinic acid compounds, N '-carbonyl diimidazole and 4-alkyl Hantzsch ester compounds in an organic solvent under the existence of a photocatalyst, a nitrogen heterocyclic carbene catalyst and alkali under the illumination condition, reacting the sulfinic acid compounds and the N, N' -carbonyl diimidazole firstly to generate corresponding sulfinylimidazole, then carrying out nucleophilic attack by the nitrogen heterocyclic carbene, carrying out single electron transfer under photocatalysis to generate sulfinyl free radicals and alkyl free radicals in a system, and then carrying out free radical coupling to generate target sulfoxide compounds.
Preferably, the structure of the sulfoxide compound is as follows:
in the formula, R1Is phenyl substituted or not by substituent, heterocyclic group substituted or not by substituent, or C1-C14 alkyl, R2Is primary alkyl, secondary alkyl or tertiary alkyl; wherein, the substituent group is at least one of electron-withdrawing group and electron-donating group, the electron-withdrawing group is at least one of fluoro group, chloro group, bromo group, acyl group, ester group, cyano group and trifluoromethyl group, the electron-donating group is at least one of iodo group, C1-C14 alkyl group, C1-C14 alkoxy group and amino group, the heterocycle is a multi-membered ring compound containing at least one hetero element, the hetero element is at least one of N, O, S, and the multi-membered ring is a four-membered ring to a fourteen-membered ring; more preferably, the heterocyclic ring is pyridine, thiophene, pyrimidine, furan, or a (pyridine, thiophene, pyrimidine, furan) fused ring derivative thereof.
Preferably, the reaction formula of the synthesis method is as follows:
wherein R is an ester group or a cyano group, R1Is phenyl substituted or not by substituent, heterocyclic group substituted or not by substituent, or C1-C14 alkyl, R2Is primary alkyl, secondary alkyl or tertiary alkyl; wherein the substituent is at least one of electron-withdrawing group and electron-donating group, and the electron-withdrawing group is fluoro groupAt least one of chlorine, bromine, acyl, ester group, cyano and trifluoromethyl, wherein the electron-donating group is at least one of iodine, C1-C14 alkyl, C1-C14 alkoxy and amino, the heterocycle is a polycyclic compound containing at least one hetero element, the hetero element is at least one of N, O, S, and the polycyclic ring is a four-membered ring to a fourteen-membered ring; more preferably, the heterocyclic ring is pyridine, thiophene, pyrimidine, furan, or a (pyridine, thiophene, pyrimidine, furan) fused ring derivative thereof.
Preferably, when the sulfinic acid compound is unstable, the corresponding salt can be used for substitution, the salt is preferably sodium salt and lithium salt, and when the corresponding salt of the sulfinic acid compound is used for substitution, acid is added into a reaction system, so that the corresponding salt of the sulfinic acid compound is converted into the sulfinic acid compound to be reacted.
Preferably, the feeding amount of each material is 1.0 equivalent of 4-alkyl Hantzsch ester compound, and the dosage of the sulfinic acid compound and the N, N' -carbonyl diimidazole is 1.2-2.5 equivalents; the dosage of the photocatalyst is 0.005-0.02 equivalent; the dosage of the N-heterocyclic carbene catalyst is 0.05 to 0.2 equivalent; the dosage of the alkali is 0.05-0.4 equivalent; namely, the charging amount of each material is 4-alkyl Hantzsch ester compound according to molar ratio: sulfinic acid compounds: n, N' -carbonyldiimidazole: photocatalyst: n-heterocyclic carbene catalysts: the alkali is 1.0: (1.2-2.5): (1.2-2.5): (0.005-0.02): (0.05-0.2): (0.05-0.4).
Preferably, the reaction temperature is room temperature, which is 15-40 ℃.
Preferably, the organic solvent is at least one of acetonitrile, dichloromethane, dichloroethane and chloroform, and more preferably dichloromethane.
Preferably, the R group in the 4-alkyl Hantzsch ester compound is selected from COOMe, COOEt and COOtBu and CN when R2Preferred is COOEt, R when it is a primary alkyl group or a secondary alkyl group2CN is preferred as tertiary alkyl.
Preferably, the photocatalyst is Ir (ppy)3、Ir[dF(CF3)ppy]2(bpy)PF6、Ir[dF(CF3)ppy]2(dtbbpy)PF64CzIPNOne, more preferably Ir [ dF (CF)3)ppy]2(bpy)PF6Or 4 CzIPN.
Preferably, the azacyclo-carbene catalyst is at least one of N-alkyl derivative salts of imidazole, triazole, thiazole, oxazole, such as 1, 3-dimethylimidazole iodide, 1, 4-dimethyl-1, 2, 4-triazolium iodide, 1, 3-ditrimethylphenyl-1H-imidazol-3-ium tetrafluoroborate, 1, 3-di-tert-butyl-1H-imidazol-3-ium tetrafluoroborate, 2-phenyl-5, 6-dihydro-8H- [1,2,4] triazolo [3,4-c ] [1,4] oxazin-2-ium tetrafluoroborate, 3-ethylbenzo [ d ] thiazol-3-ium bromide; more preferably 1, 3-di-tert-butyl-1H-imidazol-3-ium tetrafluoroborate, CAS 263163-17-3.
Preferably, the base is at least one of a carbonate, a phosphate, and an acetate of sodium, potassium, cesium (alkali metal), and more preferably cesium carbonate.
Preferably, the organic solvent is used in an amount of 0.5-3 mL per 0.2mmol of the 4-alkyl Hantzsch ester compound. More preferably, 3mL of methylene chloride is used per 0.2mmol of 4-alkyl Hantzsch esters.
Preferably, the illumination condition is visible light illumination, and the visible light includes white light and blue light.
Preferably, the reaction time of the reaction is 4 to 20 hours, more preferably 4 to 12 hours.
Preferably, the synthesis method comprises the following specific steps:
adding a photocatalyst, a 4-alkyl Hantzsch ester compound, a nitrogen heterocyclic carbene catalyst, alkali, a sulfinic acid compound or corresponding salts thereof and N, N' -carbonyl diimidazole into a dry reaction tube in an inert atmosphere, adding an organic solvent after the system is in an anhydrous and anaerobic condition, and placing the system under a lighting condition for reaction to obtain the sulfoxide compound.
Preferably, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
Preferably, after the reaction is completed, the sulfoxide compound is obtained through post-treatment; the post-treatment comprises the following steps: and (3) concentrating the reaction liquid under reduced pressure, and performing column chromatography separation by using a mixed solution of petroleum ether and ethyl acetate as a mobile phase to obtain the corresponding sulfoxide compound.
The structure of the compound prepared by the invention is shown in the specification1H NMR、13C NMR, HRMS and the like.
Compared with the prior art, the invention has the beneficial effects that: under the simple and mild conditions, sulfinic acid, N '-carbonyl diimidazole and 4-alkyl Hantzsch ester react in an organic solvent in the presence of a photocatalyst, a N-heterocyclic carbene catalyst and alkali under the illumination condition, sulfinic acid and N, N' -carbonyl diimidazole firstly react to generate corresponding sulfinyl imidazole, then nitrogen-heterocyclic carbene nucleophilic attack is carried out, single electron transfer is carried out under photocatalysis, sulfinyl free radicals and alkyl free radicals are generated in a system, and then free radical coupling is carried out to generate the target sulfoxide compound. The method provides a brand-new idea for synthesizing the sulfoxide compounds without oxidation reaction of mercaptan and thioether compounds, constructs a series of sulfoxide compounds which are difficult to synthesize by using a common method, and has good guiding significance and application prospect in the fields of scientific research and industry.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. The room temperature in the invention is 15-40 ℃.
Example 1
0.002mmol of Ir [ dF (CF) was added to a dry tube reaction tube at room temperature3)ppy]2(bpy)PF60.2mmol of Hantzsch ester diethyl 4- ((1, 3-dioxoindolin-2-yl) methyl) -2,6-dimethyl-1,4-dihydropyridine-3,5-dica rbyloxylate, 0.04mmol of 1, 3-di-tert-butyl-1H-imidazole-3-onium tetrafluoroborate, 0.04mmol of cesium carbonate, 0.4mmol of p-toluenesulfinic acid and 0.4mmol of N, N' -carbonyldiimidazole, placing the mixture in a high-purity argon gas to carry out ventilation so that the system is in a water-free and oxygen-free condition, adding 3mL of dichloromethane, placing the mixture in a blue light illumination reaction device, and stirring until complete reaction, wherein the reaction time is 12 hours. Followed by TLC monitoring for completenessAfter the reaction, the reaction solution is decompressed and concentrated, and column chromatography separation is carried out by using a mixed solution (the volume ratio is preferably 6-1: 1) of petroleum ether and ethyl acetate as a mobile phase, so that the corresponding 2- ((p-Tolylsulfinyl) methyl) isoindolone-1, 3-dione example 1 can be obtained. The yield was 92%.
Structural characterization of compound example 1:
1H NMR(400MHz,Chloroform-d)δ7.88(dd,J＝5.4,3.1Hz,2H),7.76(dd,J＝5.5,3.1Hz,2H),7.60(d,J＝8.1Hz,2H),7.33(d,J＝8.0Hz,2H),4.85(d,J＝12.5Hz,1H),4.68(d,J＝12.5Hz,1H),2.42(s,3H).13C NMR(101MHz,Chloroform-d)δ166.76,142.69,138.56,134.68,131.74,130.32,124.63,124.01,60.37,21.67.HRMS(ESI)calc.for C16H13NNaO3S+(M+Na+):322.0508,found:322.0519.
example 2
0.003mmol of Ir [ dF (CF) was added to a dry tube reaction tube at room temperature3)ppy]2(bpy)PF60.2mmol Hantzsch ester diethyl 4- ((benzyloxy) methyl) -2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate, 0.03mmol 1, 3-di-tert-butyl-1H-imidazole-3-onium tetrafluoroborate, 0.03mmol cesium carbonate, 0.4mmol p-toluenesulfinic acid and 0.4mmol N, N' -carbonyldiimidazole, placing in high purity nitrogen for ventilation to make the system in anhydrous and anaerobic condition, adding 1mL dichloromethane, placing in blue light illumination reaction device, and stirring until complete reaction. After TLC monitoring complete reaction, the reaction liquid is decompressed and concentrated, and column chromatography separation is carried out by using mixed liquid of petroleum ether and ethyl acetate as a mobile phase, so as to obtain the corresponding 1- (((Benzyloxy) methyl) sulfinyl) -4-methyllbenzene example 2. The yield was 97%.
Structural characterization of compound example 2:
1H NMR(400MHz,Chloroform-d)δ7.52(d,J＝8.1Hz,2H),7.38–7.30(m,7H),4.92–4.83(m,2H),4.51–4.41(m,2H),2.41(s,3H).13C NMR(101MHz,Chloroform-d)δ142.03,137.86,136.44,130.14,128.72,128.45,128.26,124.61,91.49,74.96,21.58.HRMS(ESI)calc.for C15H16NaO2S+(M+Na+):283.0763,found:283.0774.
example 3
0.004mmol of Ir [ dF (CF) was added to a dry tube reaction tube at room temperature3)ppy]2(bpy)PF60.2mmol of Hantzsch ester diethyl 2,6-dimethyl-4- (5-methylhex-4-en-2-yl) -1,4-dihydropyridine-3,5-dicarboxylate, 0.04mmol of 1, 3-di-tert-butyl-1H-imidazole-3-onium tetrafluoroborate, 0.04mmol of cesium carbonate, 0.5mmol of p-toluenesulfinic acid and 0.4mmol of N, N' -carbonyldiimidazole, placing the mixture in a high-purity argon gas to carry out ventilation so that the system is in anhydrous and anaerobic conditions, adding 2.5mL of dichloromethane, placing the mixture in a blue light irradiation reaction device, and stirring until the reaction is completed. After TLC monitoring complete reaction, the reaction solution is decompressed and concentrated, and column chromatography separation is carried out by using mixed solution of petroleum ether and ethyl acetate as a mobile phase, so as to obtain the corresponding 1-Methyl-4- ((5-methylhex-4-en-2-yl) sulfenyl) bezene example 3. The yield was 81%.
Structural characterization of compound example 3:
1H NMR(400MHz,Chloroform-d)δ7.48(d,J＝8.0Hz,2H),7.44(d,J＝8.1Hz,2H),7.29(d,J＝7.4Hz,4H),5.14(t,J＝7.2Hz,1H),5.07(t,J＝7.3Hz,1H),2.71(dtd,J＝12.1,6.7,2.5Hz,1H),2.55(td,J＝14.0,7.3Hz,2H),2.40(s,6H),2.38–2.32(m,1H),2.12(td,J＝13.9,7.8Hz,2H),1.71(s,3H),1.68(s,3H),1.59(s,3H),1.55(s,3H),1.07(d,J＝6.9Hz,3H),1.02(d,J＝6.6Hz,3H).13C NMR(101MHz,Chloroform-d)δ141.60,141.12,138.99,138.47,135.21,135.11,129.70,125.41,124.82,120.05,119.63,60.10,60.03,29.45,27.58,25.93,21.54,21.50,18.06,18.01,12.61,10.52.HRMS(ESI)calc.for C14O20NaOS+(M+Na+):259.1127,found:259.1130.
example 4
At room temperature, 0.004mmol of 4CZIPN, 0.4mmol of Hantzsch ester 4- (adamantan-1-yl) -2,6-dimethyl-1,4-dihydropyridine-3,5-dicarbonitrile, 0.04mmol of 1, 3-di-tert-butyl-1H-imidazole-3-onium tetrafluoroborate, 0.05mmol of cesium carbonate, 0.8mmol of p-toluenesulfinic acid and 0.7mmol of N, N' -carbonyldiimidazole are added into a dry test tube reaction tube, placed in a high-purity argon atmosphere for ventilation, 4mL of dichloromethane is added after the system is in an anhydrous and anaerobic condition, and placed in a blue light reaction device for stirring until complete reaction. After TLC monitoring complete reaction, the reaction solution is decompressed and concentrated, and column chromatography separation is carried out by using mixed solution of petroleum ether and ethyl acetate as a mobile phase, so as to obtain the corresponding 1- (p-Tolylsulfinyl) alamantane example 4. The yield was 53%.
Structural characterization of compound example 4:
1H NMR(400MHz,Chloroform-d)δ7.42(d,J＝8.0Hz,2H),7.29(d,J＝8.0Hz,2H),2.42(s,3H),2.10(s,3H),1.75–1.67(m,9H),1.60(d,J＝12.0Hz,3H).13C NMR(101MHz,Chloroform-d)δ141.54,135.23,129.17,126.53,57.56,36.35,35.04,28.95,21.61.HRMS(ESI)calc.for C17H22NaOS+(M+Na+):297.1284,found:297.1292.
example 5
0.004mmol of Ir [ dF (CF) was added to a dry tube reaction tube at room temperature3)ppy]2(bpy)PF60.2mmol of Hantzsch ester diethyl 4-cyclohexenyl-2, 6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate, 0.04mmol of 1, 3-di-tert-butyl-1H-imidazole-3-onium tetrafluoroborate, 0.04mmol of cesium carbonate, 0.5mmol of sodium p-iodobenzene sulfinate and 0.5mmol of N, N' -carbonyldiimidazole are placed in a high-purity argon gas to be ventilated, and then the system is placed in an anhydrous and oxygen-free condition, added with4mL of dichloromethane and 0.5mmol of trifluoromethanesulfonic acid were placed in a blue light irradiation reaction apparatus and stirred until the reaction was completed. After TLC monitoring complete reaction, the reaction liquid is decompressed and concentrated, and column chromatography separation is carried out by using the mixed liquid of petroleum ether and ethyl acetate as a mobile phase, thus obtaining the corresponding 1- (Cyclohexylsulfinyl) -4-iodobenzene example 5. The yield was 89%.
Structural characterization of compound example 5:
1H NMR(400MHz,Chloroform-d)δ7.84(d,J＝8.2Hz,2H),7.31(d,J＝8.2Hz,2H),2.53(ddt,J＝11.7,8.3,3.4Hz,1H),1.88–1.81(m,3H),1.76(d,J＝13.0Hz,1H),1.65(d,J＝10.0Hz,1H),1.47–1.35(m,2H),1.27–1.15(m,3H).13C NMR(101MHz,Chloroform-d)δ142.01,138.12,126.71,97.42,63.34,26.38,25.74,25.52,25.44,23.95.HRMS(ESI)calc.for C12H15INaOS+(M+Na+):356.9780,found:356.9791.
example 6
At room temperature, 0.006mmol of 4CZIPN, 0.4mmol of Hantzsch ester diethyl 4-cyclohexyl-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate, 0.06mmol of 1, 3-di-tert-butyl-1H-imidazole-3-onium tetrafluoroborate, 0.06mmol of cesium carbonate, 0.8mmol of thiophene-2-sulfinic acid and 0.8mmol of N, N' -carbonyldiimidazole are added into a dry test tube reaction tube, placed in a high-purity argon gas for ventilation, 4mL of dichloromethane is added after the system is in an anhydrous and anaerobic condition, and placed in a blue light reaction device for stirring until complete reaction. After TLC monitoring complete reaction, the reaction liquid is decompressed and concentrated, and column chromatography separation is carried out by using the mixed liquid of petroleum ether and ethyl acetate as a mobile phase, thus obtaining the corresponding 2- (Cyclohexylsulfinyl) thiophene example 6. The yield was 56%.
Structural characterization of compound example 6:
1H NMR(400MHz,Chloroform-d)δ7.68–7.62(m,1H),7.45–7.41(m,1H),7.12(dd,J＝4.8,3.8Hz,1H),2.82(ddt,J＝11.2,7.4,3.8Hz,1H),2.21–2.16(m,1H),1.95–1.89(m,1H),1.83–1.78(m,1H),1.69–1.66(m,2H),1.54–1.46(m,1H),1.33–1.23(m,4H).13C NMR(101MHz,Chloroform-d)δ135.95,131.10,130.43,127.33,64.96,25.97,25.63,25.42,25.28.HRMS(ESI)calc.for C10H14NaOS2 +(M+Na+):237.0378,found:237.0388.
example 7
At room temperature, 0.004mmol of 4CZIPN, 0.2mmol of Hantzsch ester diethyl 4-cyclohexyl-2,6-dimethyl-1, 4-dipyridine-3, 5-dicaroxylate, 0.04mmol of 1, 3-di-tert-butyl-1H-imidazole-3-onium tetrafluoroborate, 0.04mmol of cesium carbonate and 0.4mmol of N, N' -carbonyldiimidazole are added into a dry test tube reaction tube, placed in a high-purity argon gas for ventilation, and after the system is in an anhydrous and anaerobic condition, a solution of 0.4mmol of p-trifluoromethylbenzenesulfinic acid in 4mL of dichloromethane is added, placed in a blue light irradiation reaction device and stirred until complete reaction. After TLC monitoring complete reaction, the reaction liquid is decompressed and concentrated, and column chromatography separation is carried out by using the mixed liquid of petroleum ether and ethyl acetate as a mobile phase, so as to obtain the corresponding 1- (Cyclohexylsulfinyl) -4-trifluoromethylbenzene example 7. The yield was 40%.
Structural characterization of compound example 7:
1H NMR(400MHz,Chloroform-d)δ7.78(d,J＝8.3Hz,2H),7.71(d,J＝8.3Hz,2H),2.58(tt,J＝11.9,3.6Hz,1H),1.96–1.83(m,3H),1.70–1.66(m,2H),1.51–1.41(m,2H),1.30–1.19(m,3H).13C NMR(101MHz,Chloroform-d)δ146.56(d,JF＝1.4Hz),133.03(q,J＝32.7Hz),126.02(q,J＝3.7Hz),125.53,123.71(q,J＝272.7Hz),63.40,26.57,25.78,25.46,25.43,23.65.19F NMR(376MHz,Chloroform-d)δ-62.79.
example 8
The sulfoxide compound of example 1 was obtained in 89% yield based on example 1 with the solvent replaced by acetonitrile.
Example 9
The sulfoxide compound of example 1 was obtained in 81% yield based on example 1, with the base replaced by sodium acetate.
Example 10
Based on example 1, replacing the N-heterocyclic carbene catalyst with 1, 3-dimethyl imidazole iodide, the yield of the sulfoxide compound in example 1 is 78%.
It will be appreciated by persons skilled in the art that the foregoing examples are illustrative of the present invention only, and are not to be construed as limiting the invention in any way, as variations and modifications of the described embodiments may be made within the spirit and scope of the invention as defined by the appended claims without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A synthesis method of sulfoxide compounds is characterized in that sulfinic acid compounds, N' -carbonyl diimidazole and 4-alkyl Hantzsch ester compounds react in an organic solvent under the condition of illumination in the presence of a photocatalyst, a nitrogen heterocyclic carbene catalyst and alkali to generate target sulfoxide compounds.
2. The method for synthesizing sulfoxide compounds according to claim 1, wherein the structure of sulfoxide compounds is as follows:
in the formula, R1Is phenyl substituted or not by substituent, heterocyclic group substituted or not by substituent, or C1-C14 alkyl, R2Is primary alkyl, secondary alkyl or tertiary alkyl; wherein, the substituent group is at least one of electron-withdrawing group and electron-donating group, the electron-withdrawing group is at least one of fluoro group, chloro group, bromo group, acyl group, ester group, cyano group and trifluoromethyl group, and the electron-donating group is iodine group, C1-C14 alkyl group, C1-C14 alkoxy group, C,At least one of the amino groups, the heterocycle is a polycyclic compound containing at least one hetero element which is at least one of N, O, S, and the polycyclic ring is a four-membered ring to a fourteen-membered ring.
3. The method for synthesizing sulfoxide compounds according to claim 1, wherein said organic solvent is at least one of acetonitrile, dichloromethane, dichloroethane, and chloroform.
4. The method for synthesizing sulfoxide compounds according to claim 1, wherein said photocatalyst is Ir (ppy)3、Ir[dF(CF3)ppy]2(bpy)PF6、Ir[dF(CF3)ppy]2(dtbbpy)PF6And 4 CzIPN.
5. The method for synthesizing sulfoxide compounds according to claim 1, wherein the N-heterocyclic carbene catalyst is at least one of N-alkyl derivative salts of imidazole, triazole, thiazole and oxazole.
6. The method for synthesizing sulfoxide compounds according to claim 1, wherein said base is at least one of carbonate, phosphate and acetate of sodium, potassium and cesium.
7. The method for synthesizing sulfoxide compounds according to claim 1, wherein the amount of said organic solvent is 0.5-3 mL/0.2 mmol of 4-alkyl Hantzsch ester compound.
8. The method for synthesizing sulfoxide compounds according to claim 1, wherein the feeding amount of each material is 4-alkyl Hantzsch ester compounds in terms of molar ratio: sulfinic acid compounds: n, N' -carbonyldiimidazole: photocatalyst: n-heterocyclic carbene catalysts: the alkali is 1.0: (1.2-2.5): (1.2-2.5): (0.005-0.02): (0.05-0.2): (0.05-0.4).
9. The method for synthesizing sulfoxide compounds according to claim 1, wherein the reaction formula of the method is as follows:
wherein R is an ester group or a cyano group, R1Is phenyl substituted or not by substituent, heterocyclic group substituted or not by substituent, or C1-C14 alkyl, R2Is primary alkyl, secondary alkyl or tertiary alkyl; the substituent group is at least one of an electron-withdrawing group and an electron-donating group, the electron-withdrawing group is at least one of fluoro, chloro, bromo, acyl, ester, cyano and trifluoromethyl, the electron-donating group is at least one of iodo, C1-C14 alkyl, C1-C14 alkoxy and amino, the heterocycle is a multi-membered ring compound containing at least one hetero element, the hetero element is at least one of N, O, S, and the multi-membered ring is a four-membered ring to a fourteen-membered ring.
10. The method for synthesizing sulfoxide compounds according to claim 1, wherein the method comprises the following steps: adding a photocatalyst, a 4-alkyl Hantzsch ester compound, a nitrogen heterocyclic carbene catalyst, alkali, a sulfinic acid compound or corresponding salts thereof and N, N' -carbonyl diimidazole into a dry reaction tube in an inert atmosphere, adding an organic solvent after the system is in an anhydrous and anaerobic condition, and placing the system under a lighting condition for reaction to obtain the sulfoxide compound.
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| WO2003095423A1 (en) * | 2002-05-10 | 2003-11-20 | Dipharma S.P.A. | A process for the preparation of modafinil |
| US20040038973A1 (en) * | 2002-08-13 | 2004-02-26 | Joe Nahra | Phthalimide derivatives as matrix metalloproteinase inhibitors |
| CN110683971A (en) * | 2019-09-29 | 2020-01-14 | 台州学院 | Method for synthesizing aryl acetylene alkyl sulfone compounds based on Hantzsch esters |
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| WO2003095423A1 (en) * | 2002-05-10 | 2003-11-20 | Dipharma S.P.A. | A process for the preparation of modafinil |
| US20040038973A1 (en) * | 2002-08-13 | 2004-02-26 | Joe Nahra | Phthalimide derivatives as matrix metalloproteinase inhibitors |
| CN110683971A (en) * | 2019-09-29 | 2020-01-14 | 台州学院 | Method for synthesizing aryl acetylene alkyl sulfone compounds based on Hantzsch esters |
Non-Patent Citations (2)
| Title |
|---|
| XUEFENG WANG ET AL.: "Access to Sulfoxides under NHC/Photocatalysis via a Radical Pathway", 《ORG. LETT.》, vol. 24, pages 2059 - 2063 * |
| 叶盛青等: "4-取代的汉斯酯(Hantzsch Esters)作为烷基化试剂参与的有机反应", 《化学学报》, vol. 77, pages 814 - 831 * |
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