CN103739535B - A kind of S-replaces the synthetic method of aromatic sulfonic acid ester - Google Patents
A kind of S-replaces the synthetic method of aromatic sulfonic acid ester Download PDFInfo
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 37
- -1 aromatic sulfonic acid ester Chemical class 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000005864 Sulphur Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 91
- 150000001875 compounds Chemical class 0.000 claims description 52
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000741 silica gel Substances 0.000 claims description 26
- 229910002027 silica gel Inorganic materials 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 16
- 238000004440 column chromatography Methods 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 13
- 230000006837 decompression Effects 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 13
- 238000010898 silica gel chromatography Methods 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 46
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 19
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- 150000008111 thiosulfinates Chemical class 0.000 description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- DKENIBCTMGZSNM-UHFFFAOYSA-N benzenesulfinyl chloride Chemical compound ClS(=O)C1=CC=CC=C1 DKENIBCTMGZSNM-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- GWIKYPMLNBTJHR-UHFFFAOYSA-M thiosulfonate group Chemical group S(=S)(=O)[O-] GWIKYPMLNBTJHR-UHFFFAOYSA-M 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 description 1
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- MMGDBCUESCDKMW-UHFFFAOYSA-N C=[O]CCCCOCNS Chemical compound C=[O]CCCCOCNS MMGDBCUESCDKMW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ORYJPXCJDNXCTQ-UHFFFAOYSA-N O=Nc1ccc(CI)cc1 Chemical compound O=Nc1ccc(CI)cc1 ORYJPXCJDNXCTQ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- KFZUDNZQQCWGKF-UHFFFAOYSA-M sodium;4-methylbenzenesulfinate Chemical compound [Na+].CC1=CC=C(S([O-])=O)C=C1 KFZUDNZQQCWGKF-UHFFFAOYSA-M 0.000 description 1
- SRJQTHAZUNRMPR-UYQKXTDMSA-N spinosyn A Chemical compound O([C@H]1CCC[C@@H](OC(=O)C[C@H]2[C@@H]3C=C[C@@H]4C[C@H](C[C@H]4[C@@H]3C=C2C(=O)[C@@H]1C)O[C@H]1[C@@H]([C@H](OC)[C@@H](OC)[C@H](C)O1)OC)CC)[C@H]1CC[C@H](N(C)C)[C@@H](C)O1 SRJQTHAZUNRMPR-UYQKXTDMSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 230000006103 sulfonylation Effects 0.000 description 1
- 238000005694 sulfonylation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical compound N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the synthetic method that a kind of S-replaces aromatic sulfonic acid ester, described synthetic method taking aryl-sulfinate and N-sulphur for succimide as reaction raw materials, under condition of no solvent and as under the solid abrasive medium existence of catalyzer, reacted by grinding, just can high yield and high purity and obtain object product. The catalyzer used in the method for the invention cheap is easy to get, reaction conditions temperature and to be easy to control, the three wastes few, is a kind of green, environmental protection, safe brand-new synthetic method, has good social value and industrial prospect.
Description
Technical field
The present invention provides the synthetic method of a kind of sulfocompound, more specifically, it provides a kind of S-replaces the synthetic method of aromatic sulfonic acid ester, belongs to organic chemical synthesis field.
Background technology
At chemical industry and field of medicaments, sulphur is a kind of well hydrocarbon sulfuration reagent for sulphonate. Its activity is higher than alkyl sulphur chlorine, and stability and operability are better than alkyl sulphur chlorine, therefore]They can be used as the blocker of mercapto groups in protein chemistry. In addition, this compounds]Also can be used to synthesize the compound with biological activity and the production for polymeric material.
Based on its excellent properties and above-mentioned using value, therefore it is the important source material of medicine, material etc., in industrially, has important application.
Through research for many years and exploration, synthesis sulphur has much for the method for sulphonate at present. Wherein, the most frequently used synthetic method has two kinds: (1) reacts containing the direct oxidation of S--S compound; (2) by the vulcanization reaction of aryl, alkyl sulfinic acid and derivative thereof and sulfonylation agent. In addition, it is also possible to adopt thiosulfonate and the permutoid reaction of sulfinyl amine or the oxidative synthesis sulphur of thiosulfinate for sulphonate.
Such as, for symmetry classes or asymmetric class sulphur for the synthetic method of sulphonate, there is following existing document.
Takata, T. people (SelectiveoxidationofunsymmetricalthiosulfinicS-esterstot hecorrespondingthiosulfonicS-esterswithsodiumperiodate [J] .Bull.Chem.Soc.Jpn. is waited, 1981,54,1443-1447) disclose thiosulfinate under the effect of sodium periodate and acid or halogen simple substance, almost quantitatively generate sulphur for the reaction of sulphonate.But this reaction thiosulfinate used but obtains by raw material of thiophenol or two thioethers, and therefore, in fact this reaction is a stepwise reaction.
The people such as Mizhiritskii (Synthesisoforganosulfurcompoundsviasilicon-containingrea gents [J] .Zh.Obshch.Khim., 1986,56,1547-1558) report benzene sulfonyl chloride and organosilicon reagent obtains the reaction of sulphur for sulphonate under trimethylchlorosilane effect. This system organosilicon reagent used is expensive, is unfavorable for suitability for industrialized production, and its reaction formula is as follows:
The people such as Harpp (Preparationofthiosulfonatesfromsulfinylchloridesandlithi umorganotins:detectionofvic-disulfoxides [J] .SulfurLett., 1988,7,73-80) report and make solvent with tetrahydrofuran (THF), utilizing lithium reagent and phenylsulfinyl chlorine effect, the sulphur obtaining moderate yield is for sulphonate. But, lithium reagent is not only expensive, and the same with phenylsulfinyl chlorine be all very responsive to water, this will be subject to bigger restriction when being applied to suitability for industrialized production, and its reaction formula is as follows:
The people such as Freeman (PreparationandspectralpropertiesofsymmetricalS-arylarene sulfonothioates (thiosulfonates) [J] .Phosphorus, SulfurSiliconRelat.Elem., 1988,35,375-386) report and synthesize sulphur for the method for sulphonate by phenylsulfinyl chlorine. This reaction take benzene as solvent, and active zinc makes catalyzer. The toxicity of benzene is well-known, as a kind of strong carcinogen, it suffices to say that use benzene to be a kind of way that environment is extremely unfriendly as solvent. The metallic zinc used in reaction in addition needs activation, and therefore experimental implementation comparatively bothers, and its reaction formula is as follows:
The people such as Billard (ANewRoutetoThio-andSelenosulfonatesfromDisulfidesandDise lenides.ApplicationtotheSynthesisofNewThio-andSelenoeste rsofTriflicAcid [J] .J.Org.Chem., 1996,61,7545-7550) then report at room temperature, simple substance bromine/CH2Cl2Under system, sulphur obtains the reaction of sulphur for sulphonate for-sulfinic acid sodium and two thioether effects, and product rate is by the time outstanding in being. The method also exists the shortcoming that the reaction times grows excessively equally. And the simple substance bromine used in reacting has extremely strong corrodibility, not only that environment is unfriendly, and makes experimental implementation become very difficult, and its reaction formula is as follows:
The people such as Arterbum (Rhenium-CatalyzedOxidationofThiolsandDisulfideswithSulfo xides [J] .J.Am.Chem.Soc., 1997,119,9309-9310) report the synthesis of sulphur for sulphonate of rhenium metal catalysis, this reaction conditions is gentle, and product yield is higher. Although Re (O) Cl3(PPh3)2Only needing 5mol%, but another catalyzer diphenyl sulfoxide but needs 2.2 times of equivalents, Atom economy is not good, and its reaction formula is as follows:
The people such as Iranpoor (Dinitrogentetroxideimpregnatedactivatedcharcoal (N2O4/ charcoal) .Selectiveoxidationofsulfidestosulfoxidesanddisulfidesto thiosulfonates [J] .Synlett, 2004,347-349) disclose to pour into N2O4Charcoal system carry out catalysis two sulfide oxidation and generate sulphur for the method for sulphonate, compared to some synthetic methods reported before also exist problems such as easily generating the by product such as thiosulfinate, sulfonic acid, this system avoids over oxidation and scission reaction preferably, optionally being oxidized two thioethers thus obtain single sulphur for sulphonate product, its reaction formula is as follows:
The people such as Bandgar (DirectsynthesisofthiosulfonicS-estersfromsulfo-nicacidsu singcyanuricchlorideundermildconditions [J] .J.SulfurChem.2004,25,347-350) report under triphosphazene and N-methylmorpholine co-catalysis, use CH2Cl2Make solvent, taking sulfonic acid and thiophenol (alcohol) as Material synthesis sulphur is for sulphonate.This method can be used for synthesizing asymmetric sulphur for sulphonate, but reaction yield needs to be improved further, and its reaction formula is as follows:
CN102558004A discloses the chemical synthesis process of a kind of S-(4-tolyl) benzene sulfonate, described method is taking benzene sulfinic acid sodium salt and two (4-tolyl) two thioethers as raw material, under the effect of N-halogenated succinimide imide, react at-40��100 DEG C in organic solvent, obtaining S-(4-tolyl) benzene sulfonate, its reaction formula is as follows:
CN102531983A discloses the synthetic method of a kind of S-phenyl-4-tosylate, described method is taking SPTS and N-benzene sulfydryl succimide as raw material, reacting at 0-100 DEG C in organic solvent, obtain described S-phenyl-4-tosylate, its reaction formula is as follows:
Although multiple preparing the method for sulphur for sulphonate class as mentioned above, it is necessary, prior art has disclosed, but the reaction process of these methods all existing one or more following defects: 1. adopt the raw material being difficult to obtain as reactant; 2. it is used as sulfuration reagent by generating poisonous aryl sulphur halogen; 3. employ the organic solvent of poisonous and harmful, indirectly increase work difficulty; 4. reagent expensive, to water or to air-sensitive. These defects, result in operation loaded down with trivial details, cause environmental pollution, and the scope of substrate is very narrow.
Therefore, developing a kind of more convenient and efficient, the method for the more friendly synthesis sulphur of environment for sulphonate be still necessary, this not only meets the developing direction of Green Chemistry, also for environment protection, reduce the three wastes etc. and have extremely important realistic meaning. And these, the power place that also the present invention is accomplished just.
Summary of the invention
In order to overcome above-mentioned pointed many defects, seek to synthesize sulphur for the environmental protection of sulphonate, green, simple method, present inventor has performed deep research, after having paid a large amount of creative works, thus complete the present invention.
Specifically, the technical scheme of the present invention and content relate to the synthetic method that the S-shown in following formula (I) replaces aromatic sulfonic acid ester, it is specially: the present invention provides the synthetic method that S-shown in a kind of formula (I) replaces aromatic sulfonic acid ester, described synthetic method taking formula (II) aryl-sulfinate and formula (III) N-sulphur for succimide as reaction raw materials, under condition of no solvent and as under the solid abrasive medium existence of catalyzer, reacted by grinding, and obtain described formula (I) compound
Wherein R1��R2It is selected from H, C independently of one another1-C6Alkyl, C2-C6Alkene base, C1-C6Alkoxyl group, halogen, halogen are for C1-C6Alkyl or halogen are for C1-C6Alkoxyl group;
M is alkali metal.
In the described synthetic method of the present invention, unless otherwise prescribed, from start to finish, C1-C6The implication of alkyl refers to the straight or branched alkyl with 1-6 carbon atom, that includes C1Alkyl, C2Alkyl, C3Alkyl, C4Alkyl, C5Alkyl or C6Alkyl, such as can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl or just own base etc. in non-limiting manner.
In the described synthetic method of the present invention, unless otherwise prescribed, from start to finish, C2-C6The implication of alkene base refers to the straight or branched alkene base with 2-6 carbon atom, such as vinyl, 1-propenyl, 2-propenyl, 1-butylene base, crotyl, 1-pentenyl, 1-hexenyl etc.
In the described synthetic method of the present invention, unless otherwise prescribed, from start to finish, C1-C6Alkoxyl group refers to " C defined above1-C6Alkyl " be connected with O atom after group.
In the described synthetic method of the present invention, unless otherwise prescribed, from start to finish, the implication of halogen refers to haloid element, non-exclusively such as can be F, Cl, Br or I.
In the described synthetic method of the present invention, unless otherwise prescribed, from start to finish, halogen is for C1-C6The implication of alkyl refers to the " C defined above being optionally substituted by halogen1-C6Alkyl ", it is such as trifluoromethyl, pentafluoroethyl group, difluoromethyl, chloromethyl etc. in non-limiting manner.
In the described synthetic method of the present invention, unless otherwise prescribed, from start to finish, halogen is for C1-C6The implication of alkoxyl group refers to the " C defined above being optionally substituted by halogen1-C6Alkoxyl group ", it is such as trifluoromethoxy, five fluorine oxyethyl groups, difluoro-methoxy, chlorine methoxyl group etc. in non-limiting manner.
In the described synthetic method of the present invention, M is alkali metal, such as, be Li, Na, K, Rb etc., it is preferable to Li, Na or K.
In the described synthetic method of the present invention, described solid abrasive medium is selected from one or more the mixture any in neutral alumina, acidic alumina, alkali alumina, silica gel.
Wherein, it is preferable to silica gel. The granularity of described silica gel is not particularly limited, such as, can be 200-300 order silica gel, 300-400 order silica gel or 400-500 order silica gel.
In the described synthetic method of the present invention, the mol ratio of formula (II) compound and formula (III) compound is 1-2: 1, such as can be 1: 1,1.2: 1,1.4: 1,1.5: 1,1.7: 1,1.9: 1 or 2: 1 in non-limiting manner.
In the described synthetic method of the present invention, the g/mmol of silica gel and formula (III) compound is 1: 0.5-1.5, such as, can be 1: 0.5,1: 0.7,1: 0.9,1: 1,1: 1.2,1: 1.4 or 1: 1.5. Namely silica gel is with quality gram (g), and the ratio range of (III) compound taking the ratio between two of mmol timing as above-mentioned 1: 0.5-1.5.
In the described synthetic method of the present invention, temperature of reaction is 15-35 DEG C, such as, be 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C or 35 DEG C.
In the described synthetic method of the present invention, the reaction times, there is no particular limitation, such as, follow the tracks of by liquid chromatography or TLC and determine the suitable reaction times, it typically is 5-20min, such as, can be 5min, 10min, 15min or 20min.
In the described synthetic method of the present invention, as R1��R2The selection mode of group is enumerated, and enumerates as one is exemplary, R1��R2Can independently selected from H, phenyl, p-methylphenyl, p-methoxyphenyl, to fluorophenyl, rubigan or to bromophenyl.
In the described synthetic method of the present invention, described method can be specific as follows: adds formula (II) compound, formula (III) compound and grinding medium in grinding container, abundant griding reaction 5-20min at 15-35 DEG C; After completion of the reaction, by reaction system acetic acid ethyl dissolution, filtering, filtrate decompression concentrates, then post in dry method, with the separation of 300-400 order silica gel column chromatography, obtains formula (I) compound.
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 50-150.
In sum, the present invention taking aryl-sulfinate and N-sulphur for succimide as reaction raw materials, under condition of no solvent and under existing as the solid abrasive medium of catalyzer, reacted by grinding, just a step can obtain object product. Owing to not using expensive catalyzer and reagent, and do not use poisonous or harmful organic solvent, thus for this compounds green, environmental protection synthesis provide new synthetic route, there is good researching value and prospects for commercial application.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary enforcement modes and object are only used for enumerating the present invention; not the real protection scope of the present invention is formed any type of any restriction, more non-protection scope of the present invention is confined to this.
Embodiment 1
Mortar adds formula 10mmol (II) compound, 10mmol formula (III) compound and 7g200-300 order silica gel, abundant griding reaction 20min at 15 DEG C; After completion of the reaction, by reaction system acetic acid ethyl dissolution, filtering, filtrate decompression concentrates, then post in dry method, with the separation of 300-400 order silica gel column chromatography, obtains the target product for solid, and product rate is 92.8%, and purity is 98.1% (HPLC).
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 50.
Product fusing point: 69-70 DEG C.
Product nucleus magnetic resonance:1HNMR (300MHz, CDCl3): �� 2.35 (s, 3H), 2.42 (s, 3H), 7.12-7.21 (m, 6H), 7.41-7.45 (m, 2H);
13CNMR (125MHz, CDCl3): �� 21.3,21.6,124.2 (2C), 127.4 (2C), 129.1 (2C), 130.1,136.3 (2C), 140.2,142.1,144.7.
Embodiment 2
Mortar adds formula 15mmol (II) compound, 10mmol formula (III) compound and 10g300-400 order silica gel, abundant griding reaction 15min at 20 DEG C; After completion of the reaction, by reaction system acetic acid ethyl dissolution, filter, filtrate decompression concentrates, and then post in dry method, is separated with 300-400 order silica gel column chromatography, obtaining the formula for solid (I) compound, product rate is 91.5%, and purity is 98.2% (HPLC).
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 100.
Product fusing point: 38-40 DEG C.
Product nucleus magnetic resonance:1HNMR (300MHz, CDCl3): �� 7.33-7.46 (m, 7H), 7.53-7.58 (m, 3H);
13CNMR (125MHz, CDCl3): �� 127.5,127.8 (2C), 128.7 (2C), 129.6 (2C), 131.3 (2C), 133.6,136.7,143.1.
Embodiment 3
Mortar adds formula 20mmol (II) compound, 10mmol formula (III) compound and 15g400-500 order silica gel, abundant griding reaction 10min at 25 DEG C; After completion of the reaction, by reaction system acetic acid ethyl dissolution, filter, filtrate decompression concentrates, and then post in dry method, is separated with 300-400 order silica gel column chromatography, obtaining the formula for solid (I) compound, product rate is 88.9%, and purity is 99.1% (HPLC).
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 150.
Product fusing point: 84-85 DEG C.
Product nucleus magnetic resonance:1HNMR (300MHz, CDCl3): �� 3.82 (s, 3H), 3.86 (s, 3H), 6.80-6.89 (m, 4H), 7.21-7.25 (m, 2H), 7.44-7.48 (m, 2H);
13CNMR (125MHz, CDCl3): �� 55.6,55.8,113.7 (2C), 114.8 (2C), 118.7,129.7 (2C), 134.8 (2C), 138.4,162.1,163.5.
Embodiment 4
Mortar adds formula 12mmol (II) compound, 10mmol formula (III) compound and 20g200-300 order silica gel, abundant griding reaction 5min at 30 DEG C; After completion of the reaction, by reaction system acetic acid ethyl dissolution, filter, filtrate decompression concentrates, and then post in dry method, is separated with 300-400 order silica gel column chromatography, obtaining the formula for solid (I) compound, product rate is 93.6%, and purity is 98.3% (HPLC).
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 70.
Product fusing point: 130-131 DEG C.
Product nucleus magnetic resonance:1HNMR (300MHz, CDCl3): �� 7.29-7.37 (m, 4H), 7.40-7.43 (m, 2H), 7.48-7.53 (m, 2H);
13CNMR (125MHz, CDCl3): �� 125.2 (2C), 127.8 (2C), 128.4 (2C), 128.9 (2C), 136.8,137.4,139.5,140.4.
Embodiment 5
Mortar adds formula 14mmol (II) compound, 10mmol formula (III) compound and 8g300-400 order silica gel, abundant griding reaction 7min at 35 DEG C; After completion of the reaction, by reaction system acetic acid ethyl dissolution, filter, filtrate decompression concentrates, and then post in dry method, is separated with 300-400 order silica gel column chromatography, obtaining the formula for solid (I) compound, product rate is 88.7%, and purity is 98.4% (HPLC).
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 90.
Product fusing point: 150-152 DEG C.
Product nucleus magnetic resonance:1HNMR (300MHz, CDCl3): �� 7.19-7.23 (m, 2H), 7.41-7.86 (m, 6H);
13CNMR (125MHz, CDCl3): �� 126.5,127.0,129.1 (2C), 129.4,132.5 (2C), 133.2 (2C), 137.9 (2C), 142.0.
Embodiment 6
Mortar adds formula 18mmol (II) compound, 10mmol formula (III) compound and 12g400-500 order silica gel, abundant griding reaction 18min at 18 DEG C; After completion of the reaction, by reaction system acetic acid ethyl dissolution, filter, filtrate decompression concentrates, and then post in dry method, is separated with 300-400 order silica gel column chromatography, obtaining the formula for solid (I) compound, product rate is 90.9%, and purity is 98.0% (HPLC).
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 110.
Product fusing point: 53-54 DEG C.
Product nucleus magnetic resonance:1HNMR(CDCl3, 500MHz): �� 7.59-7.56 (m, 3H), 7.44-7.41 (m, 2H), 7.23-7.22 (m, 2H), 7.14-7.13 (m, 2H), 2.37 (s, 3H);
13CNMR(CDCl3, 125MHz): �� 143.1,142.1,136.5,133.5 (2C), 130.2,128.8 (2C), 127.6 (2C), 124.4 (2C), 21.4.
Embodiment 7
Mortar adds formula 16mmol (II) compound, 10mmol formula (III) compound and 16g200-300 order silica gel, abundant griding reaction 16min at 22 DEG C; After completion of the reaction, by reaction system acetic acid ethyl dissolution, filter, filtrate decompression concentrates, and then post in dry method, is separated with 300-400 order silica gel column chromatography, obtaining the formula for solid (I) compound, product rate is 84.6%, and purity is 98.6% (HPLC).
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 130.
Product fusing point: 72-73 DEG C.
Product nucleus magnetic resonance:1HNMR(CDCl3, 500MHz) and �� 7.55-7.52 (m, 3H), 7.40-7.37 (m, 2H), 7.24-7.20 (m, 4H);
13CNMR (125MHz, CDCl3): �� 142.9,138.3,137.7,133.8 (2C), 129.7,128.9 (2C), 127.6 (2C), 126.3 (2C).
Embodiment 8
Mortar adds formula 10mmol (II) compound, 10mmol formula (III) compound and 18g300-400 order silica gel, abundant griding reaction 14min at 26 DEG C;After completion of the reaction, by reaction system acetic acid ethyl dissolution, filter, filtrate decompression concentrates, and then post in dry method, is separated with 300-400 order silica gel column chromatography, obtaining the formula for solid (I) compound, product rate is 89.8%, and purity is 99.2% (HPLC).
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 140.
Product fusing point: 75-77 DEG C.
Product nucleus magnetic resonance:1HNMR(CDCl3, 500MHz) and �� 7.48-7.43 (m, 3H), 7.37-7.32 (m, 4H), 7.21-7.19 (m, 2H), 2.41 (s, 3H);
13CNMR (125MHz, CDCl3): �� 144.7,140.3,136.6,131.3 (2C), 129.4 (2C), 129.3 (2C), 128.0 (2C), 127.6,21.6.
Embodiment 9
Mortar adds formula 15mmol (II) compound, 10mmol formula (III) compound and 8g400-500 order silica gel, abundant griding reaction 15min at 25 DEG C; After completion of the reaction, by reaction system acetic acid ethyl dissolution, filter, filtrate decompression concentrates, and then post in dry method, is separated with 300-400 order silica gel column chromatography, obtaining the formula for solid (I) compound, product rate is 93.1%, and purity is 97.9% (HPLC).
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 60.
Product fusing point: 76-78 DEG C.
Product nucleus magnetic resonance:1HNMR(CDCl3, 500MHz) and �� 7.57-7.55 (m, 2H), 7.50-7.47 (m, 1H), 7.37-7.34 (m, 4H), 7.10-7.07 (m, 2H);
13CNMR (125MHz, CDCl3): �� 165.5 (1C, d,1J=255.1Hz), 138.9,136.6,131.6 (2C), 130.4 (2C, d,3J=9.6Hz), 129.5 (2C), 127.6,116.0 (2C, d,2J=22.8Hz).
Embodiment 10
Mortar adds formula 10mmol (II) compound, 10mmol formula (III) compound and 10g400-500 order silica gel, abundant griding reaction 12min at 30 DEG C; After completion of the reaction, by reaction system acetic acid ethyl dissolution, filter, filtrate decompression concentrates, and then post in dry method, is separated with 300-400 order silica gel column chromatography, obtaining the formula for solid (I) compound, product rate is 88.6%, and purity is 98.4% (HPLC).
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 80.
Product fusing point: 81-83 DEG C.
Product nucleus magnetic resonance:1HNMR(CDCl3, 500MHz) and �� 7.51-7.46 (m, 3H), 7.39-7.36 (m, 6H);
13CNMR (125MHz, CDCl3): �� 141.3,140.2,136.5,131.6 (2C), 129.6 (2C), 129.1 (2C), 128.9,127.5 (2C).
Embodiment 11
Mortar adds formula 15mmol (II) compound, 10mmol formula (III) compound and 14g200-300 order silica gel, abundant griding reaction 20min at 35 DEG C; After completion of the reaction, by reaction system acetic acid ethyl dissolution, filter, filtrate decompression concentrates, and then post in dry method, is separated with 300-400 order silica gel column chromatography, obtaining the formula for solid (I) compound, product rate is 88.9%, and purity is 98.2% (HPLC).
Wherein, described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 130.
Product fusing point: 66-68 DEG C.
Product nucleus magnetic resonance:1HNMR(CDCl3, 500MHz) and �� 7.55-7.57 (m, 2H), 7.47-7.53 (m, 1H), 7.34-7.43 (m, 6H);
13CNMR (125MHz, CDCl3): �� 142.0,136.6,132.1 (2C), 131.6 (2C), 129.6 (2C), 129.0 (2C), 128.9,127.6.
Can find out by above-described embodiment 1-11, when adopting the described method of the present invention, under condition of no solvent, using silica gel as catalyzer and grinding medium, formula (II) and (III) compound can be made at low temperature, react in the short period of time, but can obtain S-with high yield, high purity and replace aromatic sulfonic acid ester cpds.
Embodiment 12-22
Except being replaced by silica gel wherein as except neutral alumina, implementing embodiment 12-22 respectively in the way of identical with embodiment 1-11, the receipts rate of products therefrom sees the following form 1.
Embodiment 23-33
Except being replaced by silica gel wherein as except acidic alumina, implementing embodiment 23-33 respectively in the way of identical with embodiment 1-11, the receipts rate of products therefrom sees the following form 1.
Embodiment 34-44
Except being replaced by silica gel wherein as except alkali alumina, implementing embodiment 34-44 respectively in the way of identical with embodiment 1-11, the receipts rate of products therefrom sees the following form 1.
Embodiment 45-55
Except being replaced by silica gel wherein as except polynite, implementing embodiment 45-55 respectively in the way of identical with embodiment 1-11, the receipts rate of products therefrom sees the following form 1.
Table 1. uses product yield during aluminum oxide
By upper table 1 it can be seen that when using aluminum oxide and polynite, also can obtain corresponding product, but its product rate all significantly reduces, especially when using polynite, product rate is only up to 18%. This demonstrate that, silica gel has best catalysis and reaction effect for griding reaction.
It is to be understood that the purposes of these embodiments only is not intended to for illustration of the present invention limit the scope of the invention. In addition; also should understand; after the technology contents having read the present invention, the present invention can be made various change, amendment and/or modification by those skilled in the art, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (7)
1. S-shown in a formula (I) replaces the synthetic method of aromatic sulfonic acid ester, described synthetic method taking formula (II) aryl-sulfinate and formula (III) N-sulphur for succimide as reaction raw materials, under condition of no solvent and as under the solid abrasive medium existence of catalyzer, reacted by grinding, and obtain described formula (I) compound
Wherein R1��R2It is selected from H, C independently of one another1-C6Alkyl, C1-C6Alkoxy or halogen;
M is alkali metal;
Described solid abrasive medium is silica gel.
2. synthetic method as claimed in claim 1, it is characterised in that:
Described M is Li, Na or K.
3. synthetic method as described in item as arbitrary in claim 1-2, it is characterised in that:
The mol ratio of described formula (II) compound and formula (III) compound is 1-2: 1.
4. synthetic method as described in item as arbitrary in claim 1-2, it is characterised in that:
The g/mmol of described solid abrasive medium and formula (III) compound is 1: 0.5-1.5;
Temperature of reaction is 15-35 DEG C.
5. synthetic method as described in item as arbitrary in claim 1-2, it is characterised in that:
Reaction times is 5-20min.
6. synthetic method as described in item as arbitrary in claim 1-2, it is characterised in that:
Described synthetic method is specific as follows: add formula (II) compound, formula (III) compound and grinding medium in grinding container, abundant griding reaction 5-20min at 15-35 DEG C;After completion of the reaction, by reaction system acetic acid ethyl dissolution, filtering, filtrate decompression concentrates, then post in dry method, with the separation of 300-400 order silica gel column chromatography, obtains formula (I) compound.
7. synthetic method as claimed in claim 6, it is characterised in that:
Described column chromatography for separation leacheate used is ethyl acetate/petroleum ether mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 1: 50-150.
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| WO1997020855A2 (en) * | 1995-12-07 | 1997-06-12 | Genzyme Limited | Solid phase organic synthesis |
| CN102531983A (en) * | 2011-12-12 | 2012-07-04 | 温州大学 | Chemical synthesis method of S-phenyl-4-tosylate |
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