CN117946101A - Aryl methyl sulfone compound and synthesis method thereof - Google Patents
Aryl methyl sulfone compound and synthesis method thereof Download PDFInfo
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- CN117946101A CN117946101A CN202410018654.0A CN202410018654A CN117946101A CN 117946101 A CN117946101 A CN 117946101A CN 202410018654 A CN202410018654 A CN 202410018654A CN 117946101 A CN117946101 A CN 117946101A
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- pyridine
- phenylimidazo
- methyl
- sodium
- sulfone compound
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 125000005002 aryl methyl group Chemical group 0.000 title claims abstract description 12
- 238000001308 synthesis method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 41
- -1 imidazopyridine compound Chemical class 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 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 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 10
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000010189 synthetic method Methods 0.000 claims abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 154
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 77
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 16
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 12
- UTCSSFWDNNEEBH-UHFFFAOYSA-N imidazo[1,2-a]pyridine Chemical compound C1=CC=CC2=NC=CN21 UTCSSFWDNNEEBH-UHFFFAOYSA-N 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 5
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 229940079593 drug Drugs 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 5
- 230000000975 bioactive effect Effects 0.000 abstract description 2
- 229930014626 natural product Natural products 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 230000006103 sulfonylation Effects 0.000 abstract 1
- 238000005694 sulfonylation reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 115
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 87
- 239000002904 solvent Substances 0.000 description 34
- 238000005160 1H NMR spectroscopy Methods 0.000 description 32
- KFZUDNZQQCWGKF-UHFFFAOYSA-M sodium;4-methylbenzenesulfinate Chemical compound [Na+].CC1=CC=C(S([O-])=O)C=C1 KFZUDNZQQCWGKF-UHFFFAOYSA-M 0.000 description 31
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 30
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 29
- 238000004440 column chromatography Methods 0.000 description 29
- 238000000605 extraction Methods 0.000 description 29
- 239000012074 organic phase Substances 0.000 description 29
- 239000007787 solid Substances 0.000 description 29
- 239000007858 starting material Substances 0.000 description 27
- MZQPNPAWQSLKAI-UHFFFAOYSA-M sodium (4-methylphenyl) sulfate Chemical compound [Na+].CC1=CC=C(OS([O-])(=O)=O)C=C1 MZQPNPAWQSLKAI-UHFFFAOYSA-M 0.000 description 12
- 150000003457 sulfones Chemical class 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 9
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- FJSOUHVHPWODGS-UHFFFAOYSA-M sodium;4-bromobenzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=C(Br)C=C1 FJSOUHVHPWODGS-UHFFFAOYSA-M 0.000 description 6
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 5
- CQSFZPDGBPHCHV-UHFFFAOYSA-M sodium;cyclopropanesulfinate Chemical compound [Na+].[O-]S(=O)C1CC1 CQSFZPDGBPHCHV-UHFFFAOYSA-M 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 3
- FMKMKBLHMONXJM-UHFFFAOYSA-N 5-methyl-2-phenylpyrazol-3-amine Chemical compound N1=C(C)C=C(N)N1C1=CC=CC=C1 FMKMKBLHMONXJM-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229930016911 cinnamic acid Natural products 0.000 description 3
- 235000013985 cinnamic acid Nutrition 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- JFXAUUFCZJYLJF-UHFFFAOYSA-M sodium;4-chlorobenzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=C(Cl)C=C1 JFXAUUFCZJYLJF-UHFFFAOYSA-M 0.000 description 3
- VDDUCRSPMBZLMH-UHFFFAOYSA-M sodium;4-fluorobenzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=C(F)C=C1 VDDUCRSPMBZLMH-UHFFFAOYSA-M 0.000 description 3
- JZEDOEPVMYKFAB-UHFFFAOYSA-M sodium;4-methoxybenzenesulfinate Chemical compound [Na+].COC1=CC=C(S([O-])=O)C=C1 JZEDOEPVMYKFAB-UHFFFAOYSA-M 0.000 description 3
- HQCGASCBCQJRDJ-UHFFFAOYSA-M sodium;pyridine-2-sulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=N1 HQCGASCBCQJRDJ-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- ISNKSXRJJVWFIL-UHFFFAOYSA-N (sulfonylamino)amine Chemical class NN=S(=O)=O ISNKSXRJJVWFIL-UHFFFAOYSA-N 0.000 description 2
- ZUSMDKHVRFBRNJ-UHFFFAOYSA-N 6-phenyl-2,3-dihydroimidazo[2,1-b][1,3]thiazole Chemical compound N1=C2SCCN2C=C1C1=CC=CC=C1 ZUSMDKHVRFBRNJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001345 alkine derivatives Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- UTTKMJVQWOVAIH-UHFFFAOYSA-M sodium;2-chlorobenzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1Cl UTTKMJVQWOVAIH-UHFFFAOYSA-M 0.000 description 2
- IRJVONHUBTUTAL-UHFFFAOYSA-M sodium;4-(trifluoromethyl)benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=C(C(F)(F)F)C=C1 IRJVONHUBTUTAL-UHFFFAOYSA-M 0.000 description 2
- LYPGDCWPTHTUDO-UHFFFAOYSA-M sodium;methanesulfinate Chemical compound [Na+].CS([O-])=O LYPGDCWPTHTUDO-UHFFFAOYSA-M 0.000 description 2
- RRLLXOFIOPVYOP-UHFFFAOYSA-M sodium;thiophene-2-sulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CS1 RRLLXOFIOPVYOP-UHFFFAOYSA-M 0.000 description 2
- DOLVFFGLNYMIPV-UHFFFAOYSA-N 2,4-ditert-butyl-6-[3-[(3,5-ditert-butyl-2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C=NCCCN=CC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O DOLVFFGLNYMIPV-UHFFFAOYSA-N 0.000 description 1
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000244206 Nematoda Species 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 201000004681 Psoriasis Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000607618 Vibrio harveyi Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 150000001503 aryl iodides Chemical class 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000018612 quorum sensing Effects 0.000 description 1
- 239000012363 selectfluor Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KDYDJCSCGCIOKM-UHFFFAOYSA-M sodium;thiophene-2-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CS1 KDYDJCSCGCIOKM-UHFFFAOYSA-M 0.000 description 1
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical group CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Abstract
The invention belongs to the technical field of synthetic chemistry, and relates to an aryl methyl sulfone compound and a synthetic method thereof. According to the invention, an imidazopyridine compound is used as a reaction substrate, sodium sulfinate is used as a sulfonylation reagent, DMA is used as a methylene source, and the arylmethyl sulfone compound is obtained through direct one-step reaction under the action of a catalyst and an oxidant. The synthesis method provided by the invention has the advantages of rapid reaction, low-cost and easily available raw materials, simple operation and high yield. The aryl methyl sulfone compound which is efficiently constructed in the invention is an important skeleton of a plurality of medicines, bioactive molecules and natural products, and the synthetic method provides a widely applicable preparation method for the synthesis of the compound.
Description
Technical Field
The invention relates to an aryl methyl sulfone compound and a synthesis method thereof, belongs to the technical field of synthetic chemistry, and is widely applied to synthesis research of natural products and medicines.
Background
Sulfone compounds are an important component of organic sulfides and are the core skeleton of many drugs. For example, aplestics containing a methylsulfone structure are drugs for the treatment of psoriasis; the heterocyclic polyfluoroalkyl sulfone is a novel nematicide and has good control effect on parasitic nematodes of various crops; some of the novel antagonists of bacterial quorum sensing in Vibrio harveyi also have structures containing sulfone backbones; the sulfone-based derivatives have also been found to be potent inhibitors of several enzymes, such as LpxC and MMP. Pharmaceutically active sulfones include, but are not limited to, the following:
A compound represented by DMF, due to its special structure, can insert a certain group into other molecules to form a new compound, wherein the available groups include NMe 2、Me2NCO、H、C、O、CO、CHO、HCO2, CN, etc., and the compounds specifically include the following compounds:
The synthesis of sulfones has been reported in the literature. The most common method is by direct oxidation of the thioether. Hydrogen peroxide is widely used in a plurality of oxidants because of the advantages of low cost, high atomic economy, no harmful by-products, safe operation and the like. In 2005, the Strukul group was prepared from sulfones by oxidation of sulfides using a Pt/BINAP/H 2O2/surfactant (SDS) system with water as solvent (Scarso A, strukul G. Advanced Synthesis & Catalysis,2005,347 (9): 1227-1234.). In 2007, katsuki et al (Egami H, katsuki T. Journal of THE AMERICAN CHEMICAL Society,2007 (10): 1066-1066.) prepared sulfone compounds with Fe (salan) complex as catalyst and hydrogen peroxide as oxidant, and the method has high yield, wide substrate application range and mild conditions. In 2010 Rahimizadeh et al converted sulfide to sulfone or sulfoxide compounds with pure or pregsler-type heteropolyacid modified nano titania as catalyst and hydrogen peroxide as oxidant. The reaction condition is mild, the catalyst can be recycled and reused, and the catalytic activity is basically unchanged (Rahimizadeh M,Rajabzadeh G,Khatami S M,et al.Journal of Molecular Catalysis A Chemical,2010,323(1-2):59-64.).
In 2014, wu et al synthesized diaryl sulfone at room temperature using Cu (OAc) 2 as a catalyst, aryl boric acid and sulfonyl hydrazides as raw materials, ethanol as a solvent, and at moderate reaction yields (Wu X M, wang Y. Synlett,2014,25 (08): 1163-1167.). In 2018, wu et al prepared diaryl sulfone at 100℃with Cu (OAc) 2·H2 O as a catalyst, arylsulfonyl hydrazine and aryl halide as raw materials, and PEG-400 as a solvent. Typically, electron withdrawing group substituted aryl iodides are produced in relatively high yields (e.g., F, cl, br), and electron donating group containing aryl iodides are produced in somewhat lower yields (e.g., me, OMe, SCH 3、NH2) (Wu X, yan W.New Journal of Chemistry,2018,42 (13): 10953-10957).
In 2014, jiang et al prepared vinyl sulfone (Li X, xu Y, wu W, et al chemistry-A European Journal,2014,20 (26): 7911-7915) at 100deg.C using CuCl as catalyst, sulfonyl hydrazide and aryl ethylene as raw materials, and DMSO as solvent. Vinyl sulfones (Tang S, wu Y, et al chemical Communications,2014,50 (34): 4496-4499) were synthesized by Lei et al in the same year under the combined action of iodine and TBHP. In 2017, lu et al prepared vinyl sulfone (Ding,Zong-Cang,Lu-Chuan,et al.Synthesis:International Journal of Methods in Synthetic Organic Chemistry,2017,49(7):1575-1582.). by reacting a terminal alkyne with an arylsulfonyl hydrazide with a copper salt as a catalyst, and two different vinyl sulfones, namely (E) -vinyl sulfone and (Z) - β -chlorovinyl sulfone, were obtained depending on the source of copper (II), and the addition of cyclohexanone was critical to the reaction. Huang et al used elemental iodine as a catalyst, TBHP as an oxidant, and sodium carbonate as an additive, and obtained the target compound under nitrogen at 90 ℃ (Zhan Z, ma H, wei D, et al tetrahedron Letters,2018,59 (14): 1446-1450).
In addition, in situ formation of olefins by decarboxylation can also participate in such reactions. In 2015 Zhang et al, iron and copper co-catalyzed, decarboxylated terminal alkyne derivatives reacted with sulfonyl hydrazines to give the target compounds in high yields (Rong G, mao J, yan H, et al, the Journal of Organic Chemistry,2015,80 (9): 4697-4703.). The same year Singh et al takes cinnamic acid and sulfonyl hydrazine as raw materials and reacts for 1h at room temperature under an iodine/TBHP/DBU system to obtain a target product. The mechanism by which cinnamic acid and sulfonyl hydrazides synthesize sulfones is generally thought to be that sulfonyl hydrazides leave a molecule of nitrogen under the action of an oxidizing agent to form sulfonyl radicals, and cinnamic acid is then added to the sulfonyl radicals and subsequently decarboxylated to form the target (Singh R, allam B K, singh N, et al, organic Letters,2015,17 (11): 2656-2659.).
In 2021, rode et al used 2-phenylimidazo [1,2, - α ] pyridine as the starting material, sodium sulfinate as the sulfone source, DMSO as the carbon source, and Selectfluor as the oxidant to produce sulfone compounds with an additional carbon atom. In 2022, tang et al used 2-phenylimidazo [1,2, -alpha ] pyridine as a raw material, sodium sulfinate as a sulfonyl source, CHOCOOH as a carbon source, and water as a solvent to produce a sulfone compound having one carbon atom inserted therein.
In summary, although there are various methods for preparing sulfone compounds, the current methods tend to have harsh reaction conditions, require inert gas protection, and have low yields.
Accordingly, those skilled in the art are constantly researching and exploring new methods for synthesizing sulfones more efficiently.
Disclosure of Invention
In a first aspect, the invention provides a method for synthesizing an aryl methyl sulfone compound, wherein the chemical reaction formula of the method is shown as the following formula I:
Ar is selected from the group consisting of 2-phenylimidazo [1,2- α ] pyridine, 2- (2-methyl) phenylimidazo [1,2- α ] pyridine, 2- (3-methyl) phenylimidazo [1,2- α ] pyridine, 2- (4-chlorophenyl) imidazo [1,2- α ] pyridine, 2- (4-bromophenyl) imidazo [1,2- α ] pyridine, 2- (4-nitrophenyl) imidazo [1,2- α ] pyridine, 6-methyl-2-phenylimidazo [1,2- α ] pyridine, 7-bromo-2-phenylimidazo [1,2- α ] pyridine, 8-methyl-2-phenylimidazo [1,2- α ] pyridine, 2- (2-thiophene) imidazo [1,2- α ] pyridine, 2- (2-furan) imidazo [1, 2-tert-butylimidazo [1,2- α ] pyridine, 6-phenyl-2, 3-dihydroimidazo [2,1- β, 6-phenylimidazo [1,2- α ] pyridine, 8-methyl-2-phenylimidazo [1,2- α ] thiazole, 1-methyl-5-amino-1H;
R is selected from one of methyl, phenyl, p-tolyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methoxyphenyl, 2-chlorophenyl, cyclopropyl, p-trifluoromethylphenyl, thienyl and pyridyl;
The synthetic method comprises the following reaction steps: adding a raw material aryl substrate Ar-H, sodium hydrocarbyl sulfinate RSO 2 Na, a catalyst FeCl 3 and an oxidant K 2S2O8 into a mixed system of DMA and water, reacting at 110-130 ℃ until the raw material disappears, and separating and purifying to obtain an aryl methyl sulfone compound; the DMA is N, N-dimethylacetamide.
Preferably, the molar ratio of the aryl substrate, the sodium hydrocarbyl sulfinate, the catalyst and the oxidant is 1 (1.1-2): 0.1:2.5.
Further, in the mixed system of the DMA and the water, the volume ratio of the DMA to the water is 2:1.
Further, the reaction temperature was 120 ℃.
Further, the concentration of the raw aryl substrate is 0.1 to 0.4mol/L.
In a second aspect, the invention provides an arylmethyl sulfone compound prepared by the synthesis method according to the first aspect.
Preferably, the aryl methyl sulfone compound specifically comprises the following compounds:
The invention has the beneficial effects that: according to the method, sodium sulfinate is used as a sulfur source, imidazopyridine is used as a reaction substrate, a catalyst (ferric trichloride) is added, and an oxidant (potassium persulfate) is used for efficiently synthesizing a sulfone compound inserted into one carbon atom, and compared with the prior art, the method has the following advantages:
(1) The sodium sulfinate is used as a sulfonyl source, so that the sodium sulfinate has stable property and is easy to store;
(2) The N, N-dimethylacetamide is used as a carbon source, and raw materials are easy to obtain;
(3) The synthesis method has high yield, simple operation and wide substrate application range;
(4) The synthesis method does not need inert gas protection and is insensitive to air moisture;
(5) Compared with the traditional method, the synthesis method can provide sulfonyl compounds with more than one carbon atom.
The sulfone compound inserted with one carbon atom is an important skeleton of many drugs and bioactive molecules, and the synthesis method provides a widely applicable preparation method for the synthesis of the compound.
Drawings
FIGS. 1 to 2 show the NMR spectra (a) 1H NMR(b)13 C NMR of the synthesized products of examples 1 to 2;
FIG. 3 is a synthetic product NMR spectrum (a) 1H NMR(b)13C NMR(c)19 F NMR of example 3;
FIGS. 4 to 29 show the NMR spectra (a) 1H NMR(b)13 C NMR of the synthesized products of examples 4 to 29.
Detailed Description
Example 1
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 a):
0.6mmol of 2-phenylimidazo [1,2, -alpha ] pyridine (1 a), 0.66mmol of sodium p-toluenesulfinate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added into a reaction flask, and reacted at 120 ℃ until the raw material disappears. Saturated saline and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 90 percent.
1H NMR(300MHz,CDCl3)δ8.45(d,J＝6.9Hz,1H),7.67(d,J＝9.1Hz,1H),7.38(d,J＝8.3Hz,2H),7.35–7.27(m,6H),7.09(d,J＝8.0Hz,2H),6.94(s,1H),4.88(s,2H),2.36(s,3H).13C NMR(75MHz,CDCl3)δ147.42,146.00,145.33,134.22,133.03,129.84,128.34,128.23,128.16,128.14,126.03,124.98,117.50,112.92,108.29,52.69,21.67.
Example 2
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium phenylsulfinate (2 b) are used as raw materials to synthesize (3 b):
0.6mmol of 2-phenylimidazo [1,2- α ] pyridine (1 a), 0.9mmol of sodium phenylsulfinate (2 b), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate, and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 88 percent.
1H NMR(300MHz,CDCl3)δ8.47(d,J＝7.0Hz,1H),7.71(d,J＝9.0Hz,1H),7.59–7.52(m,3H),7.39–7.29(m,8H),6.96(td,J＝6.9,1.2Hz,1H),4.91(s,2H).13C NMR(75MHz,CDCl3)δ147.67,146.04,137.51,134.26,132.99,129.28,128.55,128.28,128.25,128.19,126.08,124.96,117.57,112.97,108.03,52.74.
Example 3
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium p-fluorophenyl sulfinate (2 c) are used as raw materials to synthesize (3 c):
0.6mmol of 2-phenylimidazo [1,2- α ] pyridine (1 a), 1.2mmol of sodium p-fluorophenyl sulfinate (2 c), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and the reaction is carried out at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 78 percent.
1H NMR(300MHz,CDCl3))δ8.36(d,J＝6.9Hz,1H),7.64(d,J＝9.0Hz,1H),7.29–7.23(m,5H),7.22–7.10(m,5H),6.92(td,J＝6.9,1.2Hz,1H),4.87(s,2H).13C NMR(75MHz,CDCl3)δ167.79,164.38,147.38,146.08,132.95,131.07,130.93,128.52,128.26,128.06,126.11,124.84,117.60,116.57,116.27,112.99,107.91,52.35.19FNMR(282MHz,CDCl3)δ-102.63.
Example 4
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium p-chlorophenyl sulfinate (2 d) are used as raw materials to synthesize (3 d):
0.6mmol of 2-phenylimidazo [1,2- α ] pyridine (1 a), 1.2mmol of sodium p-chlorophenyl sulfinate (2 d), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to a reaction flask, and the reaction is carried out at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 80 percent.
1H NMR(300MHz,CDCl3)δ8.43(d,J＝6.8Hz,1H),7.77–7.67(m,1H),7.40–7.28(m,6H),7.25(s,2H),7.21–7.14(m,2H),6.97(d,J＝6.8Hz,1H),4.93(s,2H).13C NMR(75MHz,CDCl3)δ147.06,145.93,141.27,135.26,132.50,129.60,129.48,128.66,128.51,128.14,126.61,124.95,117.60,113.40,107.98,52.27.
Example 5
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium p-bromophenyl sulfinate (2 e) are used as raw materials to synthesize (3 e):
0.6mmol of 2-phenylimidazo [1,2- α ] pyridine (1 a), 1.2mmol of sodium p-bromophenyl sulfinate (2 e), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate, and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 82 percent.
1H NMR(300MHz,CDCl3)δ8.39(d,J＝6.9Hz,1H),7.65(d,J＝9.1Hz,1H),7.31(ddd,J＝7.8,4.0,2.3Hz,6H),7.26–7.15(m,4H),6.93(td,J＝6.8,1.2Hz,1H).13C NMR(75MHz,CDCl3)δ147.37,146.11,135.75,132.77,132.36,129.91,129.56,128.57,128.32,128.06,126.26,124.84,117.63,113.13,107.82,52.17.
Example 6
Synthesizing (3 f) by taking 2- (2-methyl) phenylimidazo [1, 2-alpha ] pyridine (1 b) and sodium p-tolylsulfinate (2 a) as raw materials:
0.6mmol of 2- (2-methyl) phenylimidazo [1, 2-alpha ] pyridine (1 b), 0.66mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 82 percent.
1H NMR(300MHz,CDCl3)δ8.44(d,J＝6.9Hz,1H),7.56(d,J＝9.1Hz,1H),7.22(dd,J＝9.0,7.1Hz,3H),7.12(td,J＝7.5,1.4Hz,1H),7.02(d,J＝7.6Hz,3H),6.94(t,J＝7.3Hz,1H),6.86(td,J＝6.9,1.2Hz,1H),6.62(dd,J＝7.5,1.3Hz,1H),4.64(s,2H),2.31(s,3H),1.91(s,3H).13C NMR(75MHz,CDCl3)δ147.69,145.66,145.06,137.38,134.49,131.82,130.30,129.87,128.43,128.05,125.82,125.29,125.15,117.48,112.86,109.31,52.29,21.67,20.00.
Example 7
2- (3-Methyl) phenylimidazo [1, 2-alpha ] pyridine (1 c) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 g):
0.6mmol of 2- (3-methyl) phenylimidazo [1, 2-alpha ] pyridine (1 c), 0.66mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 88 percent.
1H NMR(300MHz,CDCl3)δ8.38(d,J＝6.9Hz,1H),7.59(dd,J＝9.1,1.2Hz,1H),7.30(d,J＝8.3Hz,2H),7.25–7.20(m,1H),7.09(d,J＝1.3Hz,1H),7.02(d,J＝9.1Hz,5H),6.84(td,J＝6.9,1.2Hz,1H),4.79(s,2H),2.27(s,3H),2.23(s,3H).13C NMR(75MHz,CDCl3)δ147.50,145.92,145.26,138.09,134.39,132.84,129.84,128.95,128.26,128.21,126.06,125.22,125.04,117.46,112.93,108.27,52.81,21.70,21.47.
Example 8
2- (4-Chlorophenyl) imidazo [1, 2-alpha ] pyridine (1 d) and sodium p-methylsulfinate (2 a) are used as raw materials to synthesize (3 h):
0.6mmol of 2- (4-chloro) phenylimidazo [1,2- α ] pyridine (1 d), 0.66mmol of sodium p-methylphenyl sulfinate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate, and 3mL of solvent (DMA: H 2 O=2:1) were added to the reaction flask, and reacted at 120℃until the starting material disappeared. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 85 percent.
1H NMR(300MHz,CDCl3)δ8.33(d,J＝7.0Hz,1H),7.58(d,J＝9.1Hz,1H),7.33(d,J＝8.3Hz,2H),7.26–7.16(m,5H),7.04(d,J＝8.0Hz,2H),6.86(t,J＝7.3Hz,1H),4.75(s,2H),2.30(s,3H).13C NMR(75MHz,CDCl3)δ210.22,146.05,146.00,145.62,134.36,134.30,131.55,129.94,129.50,128.59,128.24,126.39,124.93,117.53,113.19,108.46,52.64,21.72.
Example 9
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium p-methoxyphenyl sulfinate (2 f) are used as raw materials to synthesize (3 i):
0.6mmol of 2-phenylimidazo [1,2- α ] pyridine (1 a), 1.2mmol of sodium p-methoxyphenyl sulfinate (2 f), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and the mixture is reacted at 120℃until the material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 90 percent.
1H NMR(300MHz,CDCl3)δ8.36(d,J＝7.0Hz,1H),7.59(d,J＝9.1Hz,1H),7.34–7.28(m,2H),7.26–7.18(m,6H),6.85(td,J＝6.8,1.2Hz,1H),6.69–6.58(m,2H),4.79(s,2H),3.72(s,3H).13C NMR(75MHz,CDCl3)δ164.10,147.20,145.90,132.99,130.30,128.37,128.15,128.10,125.99,124.92,117.47,114.34,112.90,108.47,55.63,52.68
Example 10
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium o-chlorophenyl sulfinate (2 g) are used as raw materials to synthesize (3 j):
0.6mmol of 2-phenylimidazo [1,2- α ] pyridine (1 a), 1.2mmol of sodium 2-chlorophenyl sulfinate (2 g), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and the reaction is carried out at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 74 percent.
1H NMR(300MHz,CDCl3)δ8.48(d,J＝7.0Hz,1H),7.73(dd,J＝7.9,1.7Hz,1H),7.66(d,J＝9.1Hz,1H),7.44(d,J＝3.8Hz,3H),7.35–7.27(m,5H),7.24(dd,J＝7.9,1.2Hz,1H),6.95(td,J＝6.9,1.2Hz,1H),5.14(s,2H).13C NMR(75MHz,CDCl3)δ148.07,146.22,135.41,135.27,133.08,132.91,132.04,132.01,128.67,128.52,128.41,127.37,126.24,125.10,117.59,113.07,107.48,50.37.
Example 11
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium cyclopropylsulfinate (2 h) are used as raw materials for synthesis (3 h):
0.6mmol of 2-phenylimidazo [1,2- α ] pyridine (1 a), 0.9mmol of sodium cyclopropylsulfate (2H), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate, and 3mL of solvent (DMA: H 2 O=2:1) are added to a reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 80 percent.
1H NMR(300MHz,CDCl3)δ8.40(d,J＝7.0Hz,1H),7.79(dd,J＝8.2,1.4Hz,2H),7.71(d,J＝9.1Hz,1H),7.52–7.38(m,3H),7.36–7.28(m,1H),6.93(dd,J＝6.9,1.1Hz,1H),4.86(s,2H),2.12(ddd,J＝12.8,8.0,4.8Hz,1H),1.00(dd,J＝4.7,2.1Hz,2H),0.68(dd,J＝7.9,2.2Hz,2H).13C NMR(75MHz,CDCl3)δ147.08,145.99,133.51,129.00,128.64,128.53,126.21,124.91,117.52,113.08,108.12,49.91,28.80,4.98.
Example 12
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium p-trifluoromethylphenyl sulfinate (2 i) are used as raw materials to synthesize (3 i):
0.6mmol of 2-phenylimidazo [1,2- α ] pyridine (1 a), 1.2mmol of sodium p-trifluoromethylphenyl sulfinate (2 i), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to a reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 75 percent.
1H NMR(300MHz,CDCl3)δ8.37(d,J＝6.9Hz,1H),7.66–7.60(m,1H),7.40(d,J＝1.0Hz,4H),7.33–7.26(m,1H),7.21–7.12(m,5H),6.92(d,J＝6.1Hz,1H),4.93(s,2H).13C NMR(75MHz,CDCl3)δ147.45,146.20,140.44,132.74,128.76,128.68,128.32,127.92,126.30,126.11,126.06,124.82,121.18,117.70,113.15,107.42,51.93.HRMS(ESI)m/z:[M+H]+Calcd for C21H16F3N2O2S+417.0880;Found 417.0881.
Example 13
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium 2-thiophene sulfinate (2 j) are used as raw materials to synthesize (3 j):
0.6mmol of 2-phenylimidazo [1,2- α ] pyridine (1 a), 1.2mmol of sodium 2-thiophenesulfonate (2 j), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate, and 3mL of solvent (DMA: H 2 O=2:1) were added to the reaction flask, and reacted at 120℃until the starting material disappeared. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 78 percent.
1H NMR(300MHz,CDCl3)δ8.41(d,J＝6.9Hz,1H),7.69(d,J＝9.1Hz,1H),7.57(dd,J＝5.0,1.3Hz,1H),7.45–7.37(m,2H),7.37–7.27(m,5H),6.98–6.90(m,2H),4.99(s,2H).13C NMR(75MHz,CDCl3)δ147.91,146.12,138.00,135.41,135.07,132.98,128.65,128.41,128.35,128.21,126.24,124.95,117.63,113.12,108.11,54.07.
Example 14
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium 2-pyridine sulfinate (2 k) are used as raw materials to synthesize (3 k):
0.6mmol of 2-phenylimidazo [1,2- α ] pyridine (1 a), 1.2mmol of sodium 2-pyridine sulfinate (2 k), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate, and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 70 percent.
1H NMR(300MHz,CDCl3)δ8.60–8.54(m,1H),8.45(dt,J＝4.6,1.4Hz,1H),7.90–7.78(m,3H),7.67–7.60(m,2H),7.48–7.35(m,5H),7.05(t,J＝6.9Hz,1H),5.23(s,2H).13C NMR(75MHz,CDCl3)δ156.10,150.38,147.67,146.20,137.96,133.05,128.72,128.59,128.37,127.81,126.25,125.00,122.90,117.57,113.07,107.15,48.81.
Example 15
2-Phenylimidazo [1, 2-alpha ] pyridine (1 a) and sodium methylsulfinate (2 l) are used as raw materials to synthesize (3 l):
0.6mmol of 2-phenylimidazo [1,2- α ] pyridine (1 a), 0.9mmol of sodium methylsulfinate (2 l), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate, and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 82 percent.
1H NMR(300MHz,CDCl3)δ8.39(d,J＝6.9Hz,1H),7.75(d,J＝6.8Hz,2H),7.70(d,J＝9.1Hz,1H),7.54–7.47(m,2H),7.47–7.41(m,1H),7.36–7.30(m,1H),6.94(td,J＝6.9,1.2Hz,1H),4.83(s,2H),2.63(s,3H).13CNMR(75MHz,CDCl3)δ147.44,146.46,133.54,129.29,128.87,128.53,126.30,124.94,117.82,113.19,108.02,50.95,39.61.
Example 16
2- (4-Bromophenyl) imidazo [1, 2-alpha ] pyridine (1 e) and sodium phenyl sulfinate (2 b) are used as raw materials to synthesize (3 m):
0.6mmol of 2- (4-bromophenyl) imidazo [1,2- α ] pyridine (1 e), 0.72mmol of sodium phenylsulfinate (2 b), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) were added to the reaction flask, and the reaction was carried out at 120℃until the starting material disappeared. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 82 percent.
1H NMR(300MHz,Chloroform-d)δ8.36(d,J＝7.0Hz,1H),7.63(d,J＝9.0Hz,1H),7.52(td,J＝7.0,1.4Hz,3H),7.34(qd,J＝7.5,6.7,2.0Hz,4H),7.23–7.12(m,3H),6.89(d,J＝6.9Hz,1H),4.77(s,2H).HRMS(ESI)m/z:[M+H]+Calcd for C20H16BrN2O2S+427.0111;Found 427.0111.
Example 17
2- (4-Bromophenyl) imidazo [1, 2-alpha ] pyridine (1 e) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 n):
0.6mmol of 2- (4-bromophenyl) imidazo [1,2- α ] pyridine (1 e), 0.9mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) were added to the reaction flask, and reacted at 120℃until the starting material disappeared. Saturated saline and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 84 percent.
1H NMR(300MHz,CDCl3)δ8.42(d,J＝7.0Hz,1H),7.68(d,J＝9.1Hz,1H),7.45–7.38(m,4H),7.37–7.31(m,1H),7.24(d,J＝8.5Hz,2H),7.12(d,J＝7.7Hz,2H),6.95(td,J＝6.9,1.2Hz,1H),4.82(s,2H),2.38(s,3H).13CNMR(75MHz,CDCl3)δ146.09,146.06,145.65,134.35,132.05,131.55,129.95,129.78,128.25,126.39,124.93,122.53,117.58,113.20,108.48,52.64,21.76.
Example 18
2- (4-Bromophenyl) imidazo [1, 2-alpha ] pyridine (1 e) and sodium p-bromophenyl sulfinate (2 e) are used as raw materials to synthesize (3 o):
0.6mmol of 2- (4-bromophenyl) imidazo [1,2- α ] pyridine (1 e), 1.2mmol of sodium p-bromophenyl sulfinate (2 e), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate, and 3mL of solvent (DMA: H 2 O=2:1) were added to the reaction flask, and reacted at 120℃until the starting material disappeared. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 75 percent.
1H NMR(300MHz,CDCl3)δ8.39(d,J＝7.0Hz,1H),7.70–7.66(m,1H),7.50–7.44(m,2H),7.44–7.38(m,2H),7.38–7.32(m,1H),7.30–7.26(m,2H),7.20(d,J＝8.5Hz,2H),6.98(td,J＝6.9,1.2Hz,1H),4.88(s,2H).13CNMR(75MHz,CDCl3)δ146.18,135.92,132.53,131.81,130.24,129.69,129.65,126.63,124.84,122.81,117.74,113.44,107.98,52.27.HRMS(ESI)m/z:[M+H]+Calcd for C20H15Br2N2O2S+506.9195;Found 506.9196.
Example 19
2- (4-Bromophenyl) imidazo [1, 2-alpha ] pyridine (1 e) and sodium cyclopropylsulfinate (2 h) are used as raw materials to synthesize (3 p):
0.6mmol of 2- (4-bromophenyl) imidazo [1,2- α ] pyridine (1 e), 0.9mmol of sodium cyclopropylsulfinate (2H), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 74 percent.
1H NMR(300MHz,CDCl3)δ8.37(d,J＝7.0Hz,1H),7.74–7.64(m,3H),7.64–7.57(m,2H),7.35–7.28(m,1H),6.93(td,J＝6.9,1.2Hz,1H),4.80(s,2H),2.24–2.17(m,1H),1.08(dt,J＝6.6,3.3Hz,2H),0.81(tt,J＝8.0,3.6Hz,2H).13C NMR(75MHz,CDCl3)δ146.19,146.09,132.56,132.11,130.06,126.32,124.87,122.94,117.58,113.17,108.01,50.00,29.11,5.12.HRMS(ESI)m/z:[M+H]+Calcd for C17H16BrN2O2S+391.0110,Found 391.0111.
Example 20
2- (4-Nitrophenyl) imidazo [1, 2-alpha ] pyridine (1 f) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 q):
0.6mmol of 2- (4-nitrophenyl) imidazo [1,2- α ] pyridine (1 f), 0.9mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 75 percent.
1H NMR(300MHz,CDCl3)δ8.44(d,J＝7.0Hz,1H),8.23–8.11(m,2H),7.74(d,J＝9.1Hz,1H),7.69–7.63(m,2H),7.48(d,J＝8.3Hz,2H),7.43–7.37(m,1H),7.16(d,J＝8.0Hz,2H),7.01(td,J＝6.9,1.1Hz,1H),4.85(s,2H),2.38(s,3H).13C NMR(75MHz,CDCl3)δ147.47,146.35,145.95,144.83,139.70,134.42,130.14,128.98,128.33,126.97,125.02,123.68,117.89,113.69,109.65,52.69,21.74.HRMS(ESI)m/z:[M+H]+Calcd for C21H18N3O4S+408.1013;Found 408.1013.
Example 21
6-Methyl-2-phenylimidazo [1, 2-alpha ] pyridine (1 g) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 r):
0.6mmol of 6-methyl-2-phenylimidazo [1,2- α ] pyridine (1 g), 0.9mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate, 3mL of solvent (DMA: H 2 O=2:1) are reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 90 percent.
1H NMR(300MHz,CDCl3)δ8.12(s,1H),7.57(d,J＝9.1Hz,1H),7.38(d,J＝8.3Hz,2H),7.34–7.25(m,5H),7.15(dd,J＝9.2,1.4Hz,1H),7.07(d,J＝8.1Hz,2H),4.86(s,2H),2.36(d,J＝6.8Hz,6H).13C NMR(75MHz,CDCl3)δ147.19,145.32,145.04,134.35,133.19,129.85,129.15,128.33,128.27,128.20,128.04,122.69,122.52,116.86,108.00,52.81,21.70,18.55.
Example 22
7-Bromo-2-phenylimidazo [1, 2-alpha ] pyridine (1 h) and sodium p-tolylsulfinate (2 a) are used as raw materials for synthesis (3 s):
0.6mmol of 7-bromo-2-phenylimidazo [1,2- α ] pyridine (1H), 0.9mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 80 percent.
1H NMR(300MHz,CDCl3)δ8.29(d,J＝7.3Hz,1H),7.56(d,J＝1.6Hz,1H),7.29–7.25(m,2H),7.19(s,5H),6.99(d,J＝8.1Hz,2H),6.79(dd,J＝7.4,2.1Hz,1H),4.75(s,2H),2.26(s,3H).13C NMR(75MHz,CDCl3)δ147.98,145.65,145.45,134.01,132.63,132.41,129.86,128.37,128.12,128.05,125.50,116.17,114.46,108.75,52.39,21.64.HRMS(ESI)m/z:[M+H]+Calcd for C21H18BrN2O2S+441.0267;Found 441.0267.
Example 23
8-Methyl-2-phenylimidazo [1, 2-alpha ] pyridine (1 i) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 t):
0.6mmol of 8-methyl-2-phenylimidazo [1,2- α ] pyridine (1 i), 0.9mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 93 percent.
1H NMR(300MHz,CDCl3)δ8.21(d,J＝6.8Hz,1H),7.30(d,J＝8.3Hz,2H),7.20(dt,J＝9.6,2.8Hz,5H),7.00(d,J＝7.9Hz,3H),6.74(t,J＝6.9Hz,1H),4.75(s,2H),2.56(s,3H),2.26(s,3H).13C NMR(75MHz,CDCl3)δ146.96,146.32,145.22,134.42,133.25,129.83,128.44,128.31,128.19,127.99,127.44,124.82,122.74,112.91,108.61,52.85,21.68,17.18.
Example 24
2- (2-Thiophene) imidazo [1, 2-alpha ] pyridine (1 j) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 u):
0.6mmol of 2- (2-thiophene) imidazo [1,2- α ] pyridine (1 j), 0.9mmol of sodium p-tolylsulfinate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 80 percent.
1H NMR(300MHz,CDCl3)δ8.72(d,J＝6.7Hz,1H),8.60(s,1H),7.48(d,J＝7.9Hz,2H),7.29(d,J＝5.2Hz,1H),7.15(d,J＝7.9Hz,2H),7.07(d,J＝3.2Hz,1H),6.94(s,2H),4.91(s,2H),2.33(s,3H).13C NMR(75MHz,CDCl3)δ151.32,148.80,145.86,142.92,135.04,134.03,132.76,130.04,128.37,127.58,127.18,126.24,109.20,106.21,52.67,21.71.
Example 25
2- (2-Furan) imidazo [1, 2-alpha ] pyridine (1 k) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 v):
0.6mmol of 2- (2-furo) imidazo [1, 2-a ] pyridine (1 k), 0.9mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to the reaction flask, and reacted at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 82 percent.
1H NMR(300MHz,CDCl3)δ8.38(d,J＝7.0Hz,1H),7.60(d,J＝9.2Hz,1H),7.37(d,J＝7.9Hz,2H),7.29(t,J＝8.2Hz,1H),7.12(s,1H),7.05(d,J＝8.0Hz,2H),6.92(d,J＝7.0Hz,1H),6.67(d,J＝3.0Hz,1H),6.35–6.24(m,1H),5.07(s,2H),2.26(s,3H).13C NMR(75MHz,CDCl3)δ148.92,146.24,145.13,142.10,137.51,133.82,129.22,128.31,126.45,124.67,117.09,112.98,111.08,108.44,107.95,52.55,21.50.
Example 26
2-Tert-butylimidazo [1, 2-alpha ] pyridine (1 l) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 w):
0.6mmol of 2-tert-butylimidazo [1,2- α ] pyridine (1 l), 0.9mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to a reaction flask, and the reaction is carried out at 120℃until the starting material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 86 percent.
1H NMR(300MHz,CDCl3)δ8.21(d,J＝6.9Hz,1H),7.60(d,J＝8.2Hz,3H),7.28(d,J＝8.0Hz,2H),7.20(t,J＝8.1Hz,1H),6.76(t,J＝6.9Hz,1H),4.89(s,2H),2.41(s,3H),1.30(d,J＝2.1Hz,9H).13C NMR(75MHz,CDCl3)δ155.80,145.49,144.90,135.55,130.04,128.52,125.27,124.20,116.92,112.12,106.12,53.60,34.18,30.84,21.68.
Example 27
6-Phenyl-2, 3-dihydroimidazo [2,1-b ] thiazole (1 m) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 x):
0.6mmol of 6-phenyl-2, 3-dihydroimidazo [2,1-b ] thiazole (1 m), 0.9mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to a reaction flask, and the mixture is reacted at 120℃until the material disappears. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 80 percent.
1H NMR(300MHz,CDCl3)δ7.40(d,J＝7.8Hz,1H),7.06(d,J＝8.1Hz,1H),4.45(s,1H),4.29(t,J＝7.4Hz,1H),3.78(t,J＝7.3Hz,1H).13C NMR(75MHz,CDCl3)δ151.08,147.55,145.20,133.87,133.20,129.67,128.06,128.03,127.10,126.68,113.96,53.18,46.11,34.77,21.55.
Example 28
6-Phenylimidazole [2,1-b ] thiazole (1 n) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 y):
0.6mmol of 6-phenylimidazole [2,1-b ] thiazole (1 n), 0.9mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) are added to a reaction flask, and reacted at 120℃until the starting material disappeared. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 78 percent.
1H NMR(300MHz,CDCl3)δ7.67(d,J＝4.5Hz,1H),7.43(d,J＝8.0Hz,2H),7.27–7.15(m,5H),7.12(d,J＝7.9Hz,2H),6.86(d,J＝4.4Hz,1H),4.69(s,2H),2.34(s,3H).13C NMR(75MHz,CDCl3)δ150.77,148.42,145.37,134.00,133.01,129.83,128.27,128.16,127.78,127.49,119.07,112.72,109.77,77.58,77.16,76.74,53.45,21.62.
Example 29
1-Phenyl-3-methyl-5-amino-1H-pyrazole (1 o) and sodium p-tolylsulfinate (2 a) are used as raw materials to synthesize (3 z):
0.6mmol of 1-phenyl-3-methyl-5-amino-1H-pyrazole (1O), 0.9mmol of sodium p-tolylsulfate (2 a), 0.06mmol of FeCl 3, 1.5mmol of potassium persulfate and 3mL of solvent (DMA: H 2 O=2:1) were added to the reaction flask and reacted at 120℃until the starting material disappeared. Saturated saline solution and ethyl acetate are added for extraction for 3 times, and the organic phases are combined, dried and separated by column chromatography to obtain white solid with the yield of 82 percent.
1H NMR(300MHz,CDCl3)δ7.65(d,J＝8.3Hz,2H),7.50–7.42(m,4H),7.37–7.28(m,3H),4.40(br s,2H),4.12(s,2H),2.43(s,3H),1.62(s,3H).13C NMR(75MHz,CDCl3)δ148.75,145.56,144.99,138.05,134.66,129.78,129.58,128.54,127.61,124.01,90.17,53.08,21.65,11.24.
Claims (7)
1. The method for synthesizing the aryl methyl sulfone compound is characterized by comprising the following chemical reaction formula I:
Ar is selected from the group consisting of 2-phenylimidazo [1,2- α ] pyridine, 2- (2-methyl) phenylimidazo [1,2- α ] pyridine, 2- (3-methyl) phenylimidazo [1,2- α ] pyridine, 2- (4-chlorophenyl) imidazo [1,2- α ] pyridine, 2- (4-bromophenyl) imidazo [1,2- α ] pyridine, 2- (4-nitrophenyl) imidazo [1,2- α ] pyridine, 6-methyl-2-phenylimidazo [1,2- α ] pyridine, 7-bromo-2-phenylimidazo [1,2- α ] pyridine, 8-methyl-2-phenylimidazo [1,2- α ] pyridine, 2- (2-thiophene) imidazo [1,2- α ] pyridine, 2- (2-furan) imidazo [1, 2-tert-butylimidazo [1,2- α ] pyridine, 6-phenyl-2, 3-dihydroimidazo [2,1- β, 6-phenylimidazo [1,2- α ] pyridine, 8-methyl-2-phenylimidazo [1,2- α ] thiazole, 1-methyl-5-amino-1H;
R is selected from one of methyl, phenyl, p-tolyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methoxyphenyl, 2-chlorophenyl, cyclopropyl, p-trifluoromethylphenyl, thienyl and pyridyl;
The synthetic method comprises the following reaction steps: adding a raw material aryl substrate Ar-H, sodium hydrocarbyl sulfinate RSO 2 Na, a catalyst FeCl 3 and an oxidant K 2S2O8 into a mixed system of DMA and water, reacting at 110-130 ℃ until the raw material disappears, and separating and purifying to obtain an aryl methyl sulfone compound; the DMA is N, N-dimethylacetamide.
2. The method for synthesizing an arylmethyl sulfone compound according to claim 1, wherein the molar ratio of the aryl substrate, the sodium hydrocarbylsulfinate, the catalyst and the oxidizing agent is 1 (1.1-2): 0.1:2.5.
3. The method for synthesizing the aryl methyl sulfone compound according to claim 2, wherein the volume ratio of the DMA to the water in the mixed system of the DMA and the water is 2:1.
4. The method for synthesizing an arylmethyl sulfone compound according to claim 3, wherein the reaction temperature is 120 ℃.
5. The method for synthesizing an arylmethyl sulfone compound according to claim 2, wherein the concentration of the raw aryl substrate is 0.1 to 0.4mol/L.
6. An arylmethyl sulfone compound prepared by the synthetic method according to any one of claims 1 to 5.
7. The aryl methyl sulfone compound according to claim 6, characterized in that it comprises the following specific compounds:
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