CN109134333A - 一种硒硫醚化合物的制备方法 - Google Patents
一种硒硫醚化合物的制备方法 Download PDFInfo
- Publication number
- CN109134333A CN109134333A CN201810964631.3A CN201810964631A CN109134333A CN 109134333 A CN109134333 A CN 109134333A CN 201810964631 A CN201810964631 A CN 201810964631A CN 109134333 A CN109134333 A CN 109134333A
- Authority
- CN
- China
- Prior art keywords
- compound
- acid
- solvent
- selenium sulfide
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 selenium sulfide compound Chemical class 0.000 title claims abstract description 58
- 229960005265 selenium sulfide Drugs 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 28
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Chemical compound CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 17
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims description 14
- 150000002466 imines Chemical class 0.000 claims description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- VVWRJUBEIPHGQF-MDZDMXLPSA-N propan-2-yl (ne)-n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)\N=N\C(=O)OC(C)C VVWRJUBEIPHGQF-MDZDMXLPSA-N 0.000 claims description 8
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 4
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000011669 selenium Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 229910052711 selenium Inorganic materials 0.000 abstract description 8
- 239000005864 Sulphur Substances 0.000 abstract description 7
- 238000010504 bond cleavage reaction Methods 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 230000007017 scission Effects 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical class [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 3
- 150000002081 enamines Chemical class 0.000 abstract description 3
- 150000002085 enols Chemical class 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 239000004327 boric acid Substances 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- 238000002114 high-resolution electrospray ionisation mass spectrometry Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- PSCXFXNEYIHJST-QPJJXVBHSA-N (e)-4-phenylbut-3-enoic acid Chemical compound OC(=O)C\C=C\C1=CC=CC=C1 PSCXFXNEYIHJST-QPJJXVBHSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003958 selenols Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- PSCXFXNEYIHJST-UHFFFAOYSA-N trans-styrilacetic acid Natural products OC(=O)CC=CC1=CC=CC=C1 PSCXFXNEYIHJST-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C391/00—Compounds containing selenium
- C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B45/00—Formation or introduction of functional groups containing sulfur
- C07B45/06—Formation or introduction of functional groups containing sulfur of mercapto or sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
- C07D207/48—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种硒硫醚化合物的制备方法,本发明通过在催化量的三氟甲磺酸和偶氮二甲酸二乙酯的作用下,可以有效的氧化断裂S‑S(Se‑Se)键,产生硫正离子或者硒正离子,该正离子接受不同亲核试剂的进攻可以得到多种类型的硒硫醚化合物。当采用烯酸、烯醇或者烯胺为底物时,通过该方法分别能高效的得到环化的烷基硒硫醚化合物。当采用芳基硼酸或芳环为底物时,通过该方法能合成不对称的芳基硒硫醚化合物。本发明简单易于操作,不含金属参与,快捷方便条件温和,反应底物适用范围广,区域选择性好,收率高,可高效的合成多种类型的硒硫醚化合物。
Description
技术领域:
本发明涉及一种硒硫醚化合物的制备方法。
背景技术:
有机硒硫化合物普遍存在于天然产物、药物和生物活性分子中((a)Dunbar,K.L.;Scharf,D.H.;Litomska,A.;Hertweck,C.Chem.Rev.2017,117,5521.(b)Chauhan,P.;Mahajan,S.;Enders,D.Chem.Rev.2014,114,8807.(c)Reich,H.J.;Hondal,R.J.;ACSChem.Biol.2016,11,821.)。通过直接C-S(C-Se)键的形成来构建有机硒硫化合物是一种重要的途径((a)Liu,H.;Jiang,X.Chem.Asian J.2013,8,2546.(b)Shen,C.;Zhang,P.;Sun,Q.;Bai,S.;Hor,T.S.A.;Liu,X.Chem.Soc.Rev.2015,44,291.(c)Yu,J.-S.;Huang,H.-M.;Ding,P.-G.;Hu,X.-S.;Zhou,F.;Zhou,J.ACS Catal.2016,6,5319.)。过去几十年来,由硫正离子(硒正离子)的亲电官能化来形成C-S(C-Se)键受到研究者的重视。通常有三种途径产生硫正离子(硒正离子):(1)直接活化亲电性硫(硒)正离子试剂((a)Denmark,S.E.;Hartmann,E.;Kornfilt,D.J.P.;Wang,H.Nat.Chem.2014,6,1056.(b)Zhu,D.;Gu,Y.;Lu,L.;Shen,Q.J.Am.Chem.Soc.2015,137,10547.(c)Liu,X.;An,R.;Zhang,X.;Luo,J.;Zhao,X.Angew.Chem.Int.Ed.2016,55,5846.);(2)氧化低价硒硫化合物((a)Vieira,A.A.;Azeredo,J.B.;Godoi,M.;Santi,C.;Junior,E.N.da S.;Braga,A.L.J.Org.Chem.2015,80,2120.(b)Zheng,Y.;He,Y.;Rong,G.;Zhang,X.;Weng,Y.;Dong,K.;Xu,X.;Mao,J.Org.Lett.2015,17,5444.(c)Huang,D.;Chen,J.;Dan,W.;Ding,J.;Liu,M.;Wu,H.Adv.Synth.Catal.2012,354,2123.);(3)还原高价硒硫化合物((a)F.-L.;Yang,S.-K.Tian,Angew.Chem.Int.Ed.2013,52,4929.(b)Wu,Z.;Li,Y.-C.;Ding,W.-Z.;Zhu,T.;Liu,S.-Z.;Ren,X.;Zou,L.-H.Asian J.Org.Chem.2016,5,625.(c)Fernández-Salas,J.A.;Pulis,A.P.;Procter,D.J.Chem.Commun.2016,52,12364.)。在众多方法当中,氧化二硫醚(二硒醚)产生硫正离子(硒正离子)被认为是一种理想的途径。一方面,二硫醚(二硒醚)在空气中稳定且易于保存((a)Wang,M.;Ren,K.;Wang,L.Adv.Synth.Catal.2009,351,1586.(b)Ren,K.;Wang,M.;Wang,L.Org.Biomol.Chem.2009,7,4858.)。另一方面,可以避免使用恶臭味的硫、硒醇和预制备高价硒硫醚化合物(Roy,S.;Chatterjee,T.;Islam,Sk.M.Tetrahedron Lett.2015,56,779.)。通常,氧化裂解S-S(Se-Se)键需要强氧化剂、毒性溶剂、高温和长的反应时间。这些苛刻的条件使得反应类型和官能团兼容性受到限制。所以,迫切需要发展通用的氧化体系来断裂S-S(Se-Se)键,快速构建多样的有机硒硫醚化合物。
偶氮类化合物是一类重要的有机试剂,广泛应用于染料((a)Bafana,A.;Devi,S.S.;Chakrabarti,T.Environ.Rev.2011,19,350.(b)Chung,K.-T.J.Environ.Sci.HealthC,2016,34,233.)、自由基引发剂((a)Inui,T.;Yamanishi,K.;Sato,E.;Matsumoto,A.Macromolecules 2013,46,8111.(b)Zenati,A.;Han,Y.-K.Macromolecules 2018,51,101.)和脱氢试剂((a)But,T.Y.S.;Toy,P.H.Chem.Asian J.2007,2,1340.(b)Swamy,K.C.K.;Kumar,N.N.B.;Balaraman,E.;Kumar,K.V.P.P.Chem.Rev.2009,109,2551.(c)Fletcher,S.Org.Chem.Front.2015,2,739.)。特别的,带有强吸电子基团的偶氮类化合物因其N-N键的缺电性被认为是强的电子受体((a)Yoneda,F.;Suzuki,K.;Nitta,Y.J.Am.Chem.Soc.1966,88,2328.(b)Axen,R.;Chaykovsky,M.;Witkop,B.J.Org.Chem.1967,32,4117.(c)Jung,D.;Kim,M.H.;Kim,J.Org.Lett.2016,18,6300.)。最近,这些亲电性的偶氮物种因其好的官能团容忍性、温和的反应条件和操作简易,在一些氧化反应中扮演着氧化剂的角色。比如醇、胺脱氢转化为羰基化合物和亚胺,氧化硫醇为二硫醚和氧化硫化物为亚砜类化合物等等((a)Koichi,N.;Anri,M.;Kazuhiko,S.;Teruaki,M.B.Chem.Soc.Jpn.1977,50,2773.(b)Wang,G.;Piva de Silva,G.;Wiebe,N.E.;Fehra,G.M.;Davis,R.L.RSC Adv.2017,7,48848.)。尽管已经有这些研究工作,但是通过偶氮类化合物氧化断裂二硫(硒)醚中的S-S(Se-Se)键还没有人报道过。
因此,我们发展了一种酸催化DEAD促进的氧化断裂S-S(Se-Se)键的新方法,具体为在催化量三氟甲磺酸和偶氮二甲酸二乙酯的作用下实现S-S(Se-Se)键的断裂及其在制备多种类型的硒硫醚化合物中的应用。
发明内容:
本发明的目的是克服现有技术的不足,提供一种酸催化DEAD促进的氧化断裂S-S(Se-Se)键的制备硒硫醚化合物的方法。
为了实现上述目的,本发明采用如下技术方案:
本发明公开了一种酸催化下DEAD促进的氧化断裂S-S(Se-Se)键的新方法,本发明通过在催化量的三氟甲磺酸和偶氮二甲酸二乙酯的作用下,可以有效的氧化断裂S-S(Se-Se)键,产生硫正离子或者硒正离子,该正离子接受不同亲核试剂的进攻可以得到多种类型的硒硫醚化合物。当采用烯酸、烯醇或者烯胺为底物时,通过该方法分别能高效的得到环化的烷基硒硫醚化合物。当采用芳基硼酸或芳环为底物时,通过该方法能合成不对称的芳基硒硫醚化合物。
一种硒硫醚化合物的制备方法,其表达式为:
式1化合物与R4EER4在溶剂中进行反应,催化剂为强酸和偶氮类化合物的混合物,所述强酸为三氟甲磺酸、三氟甲磺酸三甲基硅酯、三氟化硼—乙醚络合物或者双(三氟甲烷磺酰基)亚胺;所述偶氮类化合物为偶氮二甲酸二乙酯、偶氮二甲酸二异丙酯或偶氮二甲酸二苄酯;基团R1、R2、R3、R4为芳基或者烷基;E为S或者Se原子;n为1或2;所述溶剂为二氯甲烷、三氯甲烷或1,2-二氯乙烷。
一种硒硫醚化合物的制备方法,其表达式为:
式3化合物与二苯基二硫醚或二芳基二硒醚或二芳基二硫醚在溶剂中进行反应,催化剂为强酸和偶氮类化合物的混合物,所述强酸为三氟甲磺酸、三氟甲磺酸三甲基硅酯、三氟化硼—乙醚络合物或者双(三氟甲烷磺酰基)亚胺;所述偶氮类化合物为偶氮二甲酸二乙酯、偶氮二甲酸二异丙酯或偶氮二甲酸二苄酯;所述溶剂为二氯甲烷、三氯甲烷或1,2-二氯乙烷;基团R1、R2为芳基或者烷基。
一种硒硫醚化合物的制备方法,其表达式为:
式5化合物与二苯基二硫醚或二芳基二硒醚或二芳基二硫醚在溶剂中进行反应,催化剂为强酸和偶氮类化合物的混合物,所述强酸为三氟甲磺酸、三氟甲磺酸三甲基硅酯、三氟化硼—乙醚络合物或者双(三氟甲烷磺酰基)亚胺;所述偶氮类化合物为偶氮二甲酸二乙酯、偶氮二甲酸二异丙酯或偶氮二甲酸二苄酯;所述溶剂为二氯甲烷、三氯甲烷或1,2-二氯乙烷;基团R1、R2为芳基或者烷基。
一种硒硫醚化合物的制备方法,其表达式为:
式7化合物与R4EER4在溶剂中进行反应,催化剂为强酸和偶氮类化合物的混合物,所述强酸为三氟化硼—乙醚络合物、三氟甲磺酸、三氟甲磺酸三甲基硅酯或双(三氟甲烷磺酰基)亚胺;所述偶氮类化合物为偶氮二甲酸二乙酯、偶氮二甲酸二异丙酯或偶氮二甲酸二苄酯;所述溶剂为二氯甲烷、三氯甲烷或1,2-二氯乙烷;基团Ar为芳基;基团R4为芳基或者烷基;E为S或者Se原子。
与现有技术相比,本发明具有如下有益效果:本发明的硒硫醚化合物制备方法,简单易于操作,不含金属参与,快捷方便条件温和,反应底物适用范围广,区域选择性好,收率高,可高效的合成多种类型的硒硫醚化合物,在天然产物和药物制备方面具有广阔的应用前景。本发明所使用的试剂廉价易得,避免了使用硫酚等有恶臭味的试剂,改善了反应的环境友好性,绿色环保。
具体实施方式:
以下结合实施例对本发明作进一步说明。
实施例1:
将25.2mg(0.15mmol)4-苯基-3-丁烯酸、19.8mg(0.09mmol)二苯基二硫醚置于20ml带有搅拌子的反应瓶中,于室温加入3mL二氯甲烷后,再分别加入14.4uL(0.09mmol)偶氮二甲酸二乙酯和0.7uL(0.0075mmol)TfOH,在室温搅拌12小时,旋干后快速柱层析得到目标产物,99%产率。
1H NMR(400MHz,CDCl3)δ7.56–6.98(m,10H),5.31(d,J=5.8Hz,10H),3.80(dd,J=13.9,7.0Hz,1H),2.99(dd,J=18.0,8.2Hz,1H),2.62(dd,J=18.0,7.0Hz,1H).
13C NMR(101MHz,CDCl3)δ174.25,137.40,133.37,133.30,131.80,129.44,128.87,128.83,128.57,125.50,85.17,76.84,49.91,35.45.
HR-ESI-MS m/z calcd.for C16H15O2S[M+H]+:271.0787;found:271.0786。
实施例2:
将22.2mg(0.15mmol)如下所示烯醇、19.8mg(0.09mmol)二苯基二硫醚置于20ml带有搅拌子的反应瓶中,于室温加入3mL二氯甲烷后,再分别加入14.4uL(0.09mmol)偶氮二甲酸二乙酯和1.3uL(0.015mmol)TfOH,在室温搅拌12小时,旋干后快速柱层析得到目标产物,88%产率。
1H NMR(400MHz,CDCl3)δ7.36–7.28(m,6H),7.22(dt,J=14.5,6.4Hz,4H),4.77(d,J=5.7Hz,1H),4.25–4.16(m,1H),4.08(q,J=7.8Hz,1H),3.61(dd,J=12.7,5.7Hz,1H),2.45(dq,J=15.4,7.7Hz,1H),2.07(td,J=12.0,5.0Hz,1H).
13C NMR(101MHz,CDCl3)δ141.41,134.87,131.61,129.08,128.49,127.83,127.13,125.91,85.73,68.00,53.71,33.9.
HR-ESI-MS m/z calcd.for C16H17OS[M+H]+:257.0994;found:257.0994。
实施例3:
将45.2mg(0.15mmol)如下所示烯胺、19.8mg(0.09mmol)二苯基二硫醚置于20ml带有搅拌子的反应瓶中,于室温加入3mL二氯甲烷后,再分别加入14.4uL(0.09mmol)偶氮二甲酸二乙酯和0.7uL(0.0075mmol)TfOH,在室温搅拌12小时,旋干后快速柱层析得到目标产物,95%产率。
1H NMR(400MHz,CDCl3)δ7.70(d,J=7.8Hz,2H),7.41–7.01(m,12H),4.64(s,1H),3.78(t,J=7.9Hz,1H),3.60(dd,J=17.9,7.8Hz,2H),2.45(s,3H),2.36–2.21(m,1H),1.83–1.70(m,1H).
13C NMR(101MHz,CDCl3)δ143.51,141.68,134.56,133.58,132.30,129.58,129.13,128.51,127.86,127.71,127.52,126.04,68.75,55.55,47.93,29.26,21.65.
HR-ESI-MS m/z calcd.for C23H24O2NS2[M+H]+:410.1243;found:410.1239。
实施例4:
将25.2mg(0.15mmol)苯硼酸、28.2mg(0.09mmol)二苯基二硒醚置于20ml带有搅拌子的反应瓶中,于室温加入3mL二氯甲烷后,再分别加入14.4uL(0.09mmol)偶氮二甲酸二乙酯和3.7uL(0.03mmol)三氟化硼—乙醚络合物,在室温搅拌12小时,旋干后快速柱层析得到目标产物,94%产率。
1H NMR(400MHz,CDCl3)δ7.51–7.42(m,4H),7.32–7.21(m,6H).
13C NMR(101MHz,CDCl3)δ133.11,131.26,129.46,127.46。
Claims (4)
1.一种硒硫醚化合物的制备方法,其特征在于:其表达式为:
式1化合物与R4EER4在溶剂中进行反应,催化剂为强酸和偶氮类化合物的混合物,所述强酸为三氟甲磺酸、三氟甲磺酸三甲基硅酯、三氟化硼—乙醚络合物或者双(三氟甲烷磺酰基)亚胺;所述偶氮类化合物为偶氮二甲酸二乙酯、偶氮二甲酸二异丙酯或偶氮二甲酸二苄酯;基团R1、R2、R3、R4为芳基或者烷基;E为S或者Se原子;n为1或2;所述溶剂为二氯甲烷、三氯甲烷或1,2-二氯乙烷。
2.一种硒硫醚化合物的制备方法,其特征在于:其表达式为:
式3化合物与二苯基二硫醚或二芳基二硒醚或二芳基二硫醚在溶剂中进行反应,催化剂为强酸和偶氮类化合物的混合物,所述强酸为三氟甲磺酸、三氟甲磺酸三甲基硅酯、三氟化硼—乙醚络合物或者双(三氟甲烷磺酰基)亚胺;所述偶氮类化合物为偶氮二甲酸二乙酯、偶氮二甲酸二异丙酯或偶氮二甲酸二苄酯;所述溶剂为二氯甲烷、三氯甲烷或1,2-二氯乙烷;基团R1、R2为芳基或者烷基。
3.一种硒硫醚化合物的制备方法,其特征在于:其表达式为:
式5化合物与二苯基二硫醚或二芳基二硒醚或二芳基二硫醚在溶剂中进行反应,催化剂为强酸和偶氮类化合物的混合物,所述强酸为三氟甲磺酸、三氟甲磺酸三甲基硅酯、三氟化硼—乙醚络合物或者双(三氟甲烷磺酰基)亚胺;所述偶氮类化合物为偶氮二甲酸二乙酯、偶氮二甲酸二异丙酯或偶氮二甲酸二苄酯;所述溶剂为二氯甲烷、三氯甲烷或1,2-二氯乙烷;基团R1、R2为芳基或者烷基。
4.一种硒硫醚化合物的制备方法,其特征在于:其表达式为:
式7化合物与R4EER4在溶剂中进行反应,催化剂为强酸和偶氮类化合物的混合物,所述强酸为三氟化硼—乙醚络合物、三氟甲磺酸、三氟甲磺酸三甲基硅酯或双(三氟甲烷磺酰基)亚胺;所述偶氮类化合物为偶氮二甲酸二乙酯、偶氮二甲酸二异丙酯或偶氮二甲酸二苄酯;所述溶剂为二氯甲烷、三氯甲烷或1,2-二氯乙烷;基团Ar为芳基;基团R4为芳基或者烷基;E为S或者Se原子。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810964631.3A CN109134333B (zh) | 2018-08-23 | 2018-08-23 | 一种硒硫醚化合物的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810964631.3A CN109134333B (zh) | 2018-08-23 | 2018-08-23 | 一种硒硫醚化合物的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109134333A true CN109134333A (zh) | 2019-01-04 |
CN109134333B CN109134333B (zh) | 2020-04-21 |
Family
ID=64791307
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810964631.3A Expired - Fee Related CN109134333B (zh) | 2018-08-23 | 2018-08-23 | 一种硒硫醚化合物的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109134333B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114805156A (zh) * | 2022-04-29 | 2022-07-29 | 浙江工业大学 | 一种在室温、水相条件下铜催化制备不对称芳基硒醚类化合物的方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104045589A (zh) * | 2014-05-07 | 2014-09-17 | 华东师范大学 | 一种芳基烷基硫醚化合物及其合成方法 |
CN105669503A (zh) * | 2016-01-12 | 2016-06-15 | 中山大学 | 三氟甲硫基试剂及其制备方法与在不对称三氟甲硫基化反应中的应用 |
-
2018
- 2018-08-23 CN CN201810964631.3A patent/CN109134333B/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104045589A (zh) * | 2014-05-07 | 2014-09-17 | 华东师范大学 | 一种芳基烷基硫醚化合物及其合成方法 |
CN105669503A (zh) * | 2016-01-12 | 2016-06-15 | 中山大学 | 三氟甲硫基试剂及其制备方法与在不对称三氟甲硫基化反应中的应用 |
Non-Patent Citations (3)
Title |
---|
M OF DIPHENYLA DISELENIDERCELLO TIECCO等: "Oxidation of Diphenyl Diselenide with 2,3-Dichloro-5,6-dicyanobenzoquinone (DDQ). A New Method for the Electrophilic Phenylselenenylation of Alkenes under Mild Conditions", 《SYNLETT》 * |
MARCELLO TIECCO等: "Preparation of a New Chiral Non-Racemic Sulfur-Containing Diselenide and Applications in Asymmetric Synthesis", 《CHEM.EUR.J.》 * |
STEFAN ORTGIES等: "Mechanistic and Synthetic Investigations on the Dual Selenium-π-Acid/Photoredox Catalysis in the Context of the Aerobic Dehydrogenative Lactonization of Alkenoic Acids", 《ACS CATAL.》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114805156A (zh) * | 2022-04-29 | 2022-07-29 | 浙江工业大学 | 一种在室温、水相条件下铜催化制备不对称芳基硒醚类化合物的方法 |
CN114805156B (zh) * | 2022-04-29 | 2024-03-26 | 浙江工业大学 | 一种在室温、水相条件下铜催化制备不对称芳基硒醚类化合物的方法 |
Also Published As
Publication number | Publication date |
---|---|
CN109134333B (zh) | 2020-04-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Shi et al. | 1, 3-Diyne chemistry: synthesis and derivations | |
Casola et al. | Iron-catalyzed cyclization of alkynols with diorganyl diselenides: synthesis of 2, 5-dihydrofuran, 3, 6-dihydro-2 H-pyran, and 2, 5-dihydro-1 H-pyrrole organoselanyl derivatives | |
Xu et al. | Synthesis of chalcones catalyzed by a novel solid sulfonic acid from bamboo | |
Jacubert et al. | p-Toluenesulfonic acid-promoted selective functionalization of unsymmetrical arylalkynes: a regioselective access to various arylketones and heterocycles | |
Luo et al. | An efficient electrochemical synthesis of vinyl sulfones from sodium sulfinates and olefins | |
Buzas et al. | Gold (I)-catalyzed isomerization of allenyl carbinol esters: an efficient access to functionalized 1, 3-butadien-2-ol esters | |
Teiber et al. | Rapid consecutive three-component coupling-Fiesselmann synthesis of luminescent 2, 4-disubstituted thiophenes and oligothiophenes | |
Hilt et al. | The First Broad Application of Alkynyl Sulfides as Dienophiles in Cobalt (I)-Catalyzed Diels− Alder Reactions | |
Reddy et al. | Phosphomolybdic acid: a highly efficient solid acid catalyst for the synthesis of trans-4, 5-disubstituted cyclopentenones | |
Coppi et al. | Exploiting the Lithiation‐Directing Ability of Oxetane for the Regioselective Preparation of Functionalized 2‐Aryloxetane Scaffolds under Mild Conditions | |
Gogoi et al. | Grafting of Ru (III) complex onto nanosilica and its implication as heterogeneous catalyst for aerobic oxidative hydroxylation of arylboronic acids | |
Xu et al. | The first ionic liquids promoted conjugate addition of azide ion to α, β-unsaturated carbonyl compounds | |
Rungtaweevoranit et al. | A facile two-step synthesis of thiophene end-capped aromatic systems | |
Wang et al. | Visible-light-induced 1, 2-alkylarylation of alkenes with aC (sp3)–H bonds of acetonitriles involving neophyl rearrangement under transition-metal-free conditions | |
Xin et al. | Copper-catalyzed sulfenylation, sulfonylation, and selenylation of 2, 3-allenoic acids with disulfides or diselenides | |
CN109134333A (zh) | 一种硒硫醚化合物的制备方法 | |
Nishino et al. | Indium-Catalyzed Reductive Dithioacetalization of Carboxylic Acids with Dithiols: Scope, Limitations, and Application to Oxidative Desulfurization | |
Kohrs et al. | Cycloparaphenylenes via [2+ 2+ 2] cycloaddition | |
Yang et al. | Stereoselective electrochemical carboxylation of α, β-unsaturated sulfones | |
Miao et al. | Iron (III)-Mediated Bicyclization of 1, 2-Allenyl Aryl Ketones: Assembly of Indanone-Fused Polycyclic Scaffolds and Dibenzo [a, e] pentalene Derivatives | |
Yan et al. | α-Arylchalcogenation of acetone with diaryl dichalcogenide via metal-free oxidative C (sp3)–H bond functionalization | |
Singh et al. | Synthesis of symmetrical 1, 3-diynes via homocoupling reaction of n-butyl alkynyltellurides | |
Chao et al. | Cerium ammonium nitrate-mediated access to biaryl lactones: substrate scopes and mechanism studies | |
Parumala et al. | S-Arylation of thiols with masked o-benzoquinones: synthesis of alkyl aryl/diaryl sulfides | |
Fang et al. | Enantioselective sulfenylation of α-nitroesters catalyzed by diarylprolinols |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200421 Termination date: 20200823 |