CN108530329A - 一种制备三级烷基三氟甲基硫醚的方法 - Google Patents
一种制备三级烷基三氟甲基硫醚的方法 Download PDFInfo
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- -1 alkyl trifluoromethyl thioether Chemical compound 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 claims abstract description 25
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 55
- 238000002360 preparation method Methods 0.000 claims description 12
- OVVURKRTLZQGJM-UHFFFAOYSA-N 1-iodo-2-[2-(trifluoromethylsulfanyloxy)propan-2-yl]benzene Chemical compound CC(C)(OSC(F)(F)F)c1ccccc1I OVVURKRTLZQGJM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910007161 Si(CH3)3 Inorganic materials 0.000 claims 1
- 125000003107 substituted aryl group Chemical group 0.000 claims 1
- OFHCXWMZXQBQMH-UHFFFAOYSA-N trifluoro(trifluoromethylsulfanyl)methane Chemical group FC(F)(F)SC(F)(F)F OFHCXWMZXQBQMH-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- WQXUWWUDOMNMMM-UHFFFAOYSA-N cyclohept-3-ene-1,2-dione Chemical compound O=C1CCCC=CC1=O WQXUWWUDOMNMMM-UHFFFAOYSA-N 0.000 abstract description 2
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 168
- 238000005160 1H NMR spectroscopy Methods 0.000 description 34
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000004440 column chromatography Methods 0.000 description 18
- 238000004293 19F NMR spectroscopy Methods 0.000 description 17
- 239000012300 argon atmosphere Substances 0.000 description 16
- 238000011068 loading method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 13
- 0 *N(C(c1ccccc11)=O)C1=O Chemical compound *N(C(c1ccccc11)=O)C1=O 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000000741 silica gel Substances 0.000 description 10
- 229910002027 silica gel Inorganic materials 0.000 description 10
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- 229940093499 ethyl acetate Drugs 0.000 description 5
- 235000019439 ethyl acetate Nutrition 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 2
- YJIYBOWAUVDENV-UHFFFAOYSA-N 1-(methoxymethoxy)-1-methylcyclododecane Chemical compound COCOC1(C)CCCCCCCCCCC1 YJIYBOWAUVDENV-UHFFFAOYSA-N 0.000 description 1
- RNWOROBMHREGJM-UHFFFAOYSA-N 1-[2-(methoxymethoxy)-2-methylpropyl]-4-(2-methylpropyl)benzene Chemical compound C(C(C)C)C1=CC=C(C=C1)CC(C)(C)OCOC RNWOROBMHREGJM-UHFFFAOYSA-N 0.000 description 1
- MGEIBHHLPGBPBM-UHFFFAOYSA-N 1-[2-(methoxymethoxy)-2-methylpropyl]-4-phenylbenzene Chemical group COCOC(CC1=CC=C(C=C1)C1=CC=CC=C1)(C)C MGEIBHHLPGBPBM-UHFFFAOYSA-N 0.000 description 1
- NUNGMRFQSZHOIL-UHFFFAOYSA-N 1-bromo-7-(methoxymethoxy)-7-methyloctane Chemical compound BrCCCCCCC(C)(C)OCOC NUNGMRFQSZHOIL-UHFFFAOYSA-N 0.000 description 1
- HGJBETDGLGADNH-UHFFFAOYSA-N 13-hydroxy-13-sulfanylidene-12,14-dioxa-13lambda5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene Chemical compound O1P(O)(=S)OC2=CC=C(C=CC=C3)C3=C2C2=C1C=CC1=CC=CC=C21 HGJBETDGLGADNH-UHFFFAOYSA-N 0.000 description 1
- SQWFCYUPGCKXIY-UHFFFAOYSA-N 2-(methoxymethoxy)-2-methyladamantane Chemical compound C1C(C2)CC3CC1C(OCOC)(C)C2C3 SQWFCYUPGCKXIY-UHFFFAOYSA-N 0.000 description 1
- URNQKMAWORRSRV-UHFFFAOYSA-N 2-(methoxymethoxy)-2-methylundecane Chemical compound CCCCCCCCCC(C)(C)OCOC URNQKMAWORRSRV-UHFFFAOYSA-N 0.000 description 1
- CFNSRIIHFLPQCE-UHFFFAOYSA-N 2-(trifluoromethylsulfanyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(SC(F)(F)F)C(=O)C2=C1 CFNSRIIHFLPQCE-UHFFFAOYSA-N 0.000 description 1
- ODAUJGHRIQMYKB-UHFFFAOYSA-N 2-[2-(methoxymethoxy)-2-methylpropyl]thiophene Chemical compound COCOC(CC=1SC=CC1)(C)C ODAUJGHRIQMYKB-UHFFFAOYSA-N 0.000 description 1
- WDWTXRMXRNEUBZ-UHFFFAOYSA-N 2-[3-(methoxymethoxy)-3-methylbutyl]-4,5-diphenyl-1,3-oxazole Chemical compound COCOC(CCC=1OC(=C(N1)C1=CC=CC=C1)C1=CC=CC=C1)(C)C WDWTXRMXRNEUBZ-UHFFFAOYSA-N 0.000 description 1
- CMFAQBDINVJDNP-UHFFFAOYSA-N 3-sulfanylidene-2-(trifluoromethyl)isoindol-1-one Chemical class C1=CC=C2C(=S)N(C(F)(F)F)C(=O)C2=C1 CMFAQBDINVJDNP-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- HIMYNEGZHIILCH-UHFFFAOYSA-N 6-(methoxymethoxy)-6-methylundecane Chemical compound COCOC(CCCCC)(CCCCC)C HIMYNEGZHIILCH-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- LSRGXLRLWFDKNR-UHFFFAOYSA-N FC(F)(F)[S] Chemical compound FC(F)(F)[S] LSRGXLRLWFDKNR-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- MQTUAKUTSFBGDS-UHFFFAOYSA-N [2-(methoxymethoxy)-2-methyl-4-phenylbutyl]-trimethylsilane Chemical compound CC(CCC1=CC=CC=C1)(C[Si](C)(C)C)OCOC MQTUAKUTSFBGDS-UHFFFAOYSA-N 0.000 description 1
- QQMMSRHZCHPAOT-UHFFFAOYSA-N [7-(methoxymethoxy)-7-methyloctyl] furan-2-carboxylate Chemical compound O1C(=CC=C1)C(=O)OCCCCCCC(C)(C)OCOC QQMMSRHZCHPAOT-UHFFFAOYSA-N 0.000 description 1
- 150000003838 adenosines Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- HGXLJRWXCXSEJO-GMSGAONNSA-N cefazaflur Chemical compound CN1N=NN=C1SCC1=C(C(O)=O)N2C(=O)[C@@H](NC(=O)CSC(F)(F)F)[C@H]2SC1 HGXLJRWXCXSEJO-GMSGAONNSA-N 0.000 description 1
- 229950004359 cefazaflur Drugs 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- SVPQZGWGYCARGG-UHFFFAOYSA-N silver;trifluoromethanethiol Chemical compound [Ag].FC(F)(F)S SVPQZGWGYCARGG-UHFFFAOYSA-N 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229940094989 trimethylsilane Drugs 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three 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
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
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Abstract
一种制备三级烷基三氟甲基硫醚的方法,它是以三级烷氧醚为原料,在蓝光灯照射下,在溶液中,氩气气氛下,在少量碳酸钾存在下,以光催化剂4CzIPN和有机硫醇催化剂4‑巯基萘并[2,1‑d:1′,2′‑f][1,3,2]二氧代环庚烯‑4‑氧化物协同催化,与2‑((三氟甲基)硫基)异二氢吲哚‑1,3‑二酮在室温下反应,得到三级烷基三氟甲基硫醚所述的光催化剂4CzIPN与有机硫醇催化剂有如下结构:
Description
技术领域
本发明涉及一种制备三级烷基三氟甲基硫醚的方法。
背景技术
三氟甲硫基官能团是一类重要的官能团[参见:Xu,X.H.;Matsuzaki,K.;Shibata,N. Chem.Rev.2015,115,731.],同时也广泛存在于许多药物分子(Adenosine analogue,cefazaflur,等)和生物活性分子结构中[参见:(a)Counts,G.W.;Gregory,D.;Zeleznik,D.;Turck,M.Antimicrobial Agents and Chemotherapy 1977,11,708.(b)Houston,M.E.;Vander Jagt,D.L.;Honek,J.F.Bioorganic&Medicinal Chemistry Letters 1991,1,623.]。尽管有少数几类通过三氟甲硫基金属试剂来构建一级或二级烷基三氟甲基硫醚,但是在无过渡金属条件下对三级烷基三氟甲基硫醚的定点合成仍然是一大挑战。反应的原料是三级烷氧醚(OCH2OCH3,-MOM),非常容易大规模制备[参见:Han,J.H.;Kwon,Y.E.;Sohn,J.-H.; Ryu,D.H.Tetrahedron 2010,66,1673.]。采用一种光催化与有机协同催化的,三级烷基 -MOM醚的直接定点三氟甲硫基化可以高效实现各类三级烷基三氟甲基硫醚的制备,在精细化工、材料科学和制药领域都有较好应用。
发明内容
本发明要解决的技术问题是提供一种制备三级烷基三氟甲基硫醚以及其应用。
本发明的合成路线如下:
一种制备三级烷基三氟甲基硫醚的方法,它是以三级烷氧醚(OCH2OCH3,-MOM)为原料,在蓝光灯照射下,在溶液中,氩气气氛下,在少量碳酸钾存在下,以光催化剂4CzIPN和有机硫醇催化剂4-巯基萘并[2,1-d:1′,2′-f][1,3,2]二氧代环庚烯-4-氧化物(4-mercaptodinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide)协同催化,与2-((trifluoromethyl)thio)isoindoline-1,3-dione(2-[(三氟甲基)硫基]异二氢吲哚-1,3- 二酮)在室温下反应,得到三级烷基三氟甲基硫醚
所述的光催化剂4CzIPN与有机硫醇催化剂有如下结构:
上述的制备方法,所述的三级烷基三氟甲基硫醚中的R1基团可以是各种取代的芳基、杂芳基或烷基等,R2基团可以是甲基、乙基或CH2TMS等。
上述的制备方法,所述的在溶液中是在二氯甲烷(dichloromethane)中。
上述的制备方法,所述的三级烷氧醚1与沈试剂2a的物质的量之比是1∶1-1∶2,优选的是1∶1.5。
上述的制备方法,所述的光催化剂4CzIPN与硫醇催化剂的用量是三级烷氧醚1摩尔数的2%的摩尔量。
上述的制备方法,所述的碳酸钾是三级烷氧醚1摩尔数的10%的摩尔量。
典型反应如下:
本发明的方法反应条件温和,不需要氧化剂以及高温条件,同时避免了过渡金属的残留,从稳定易制备的各种三级烷氧醚与三氟甲基硫试剂直接得到三级烷基三氟甲基硫醚。
具体实施方式
光催化剂4CzIPN由北京华威锐科化工有限公司提供。
有机硫醇催化剂合成:
根据文献(Kato,S.;Saga,Y.;Kojima,M.;Fuse,H.;Matsunaga,S.;Fukatsu,A.;Kondo,M.; Masaoka,S.;Kanai,M.J.Am.Chem.Soc.2017,139,2204.)进行合成,具体操作如下:取联萘酚2.9g(10mmol)加入到60mL吡啶中,于室温在搅拌状态下滴加PSCl34.3mL(42mmol),然后与85℃下反应3h,冷却至室温,然后加入15mL水,再与90℃反应2h,反应结束后冷却至室温,以饱和碳酸氢钠溶液淬灭,用乙酸乙酯萃取,合并有机相,以无水硫酸钠干燥,干法拌样,柱色谱纯化,得到白色固体粉末。
1H NMR(400MHz,CDCl3)δ8.02(d,J=8.7Hz,1H),7.91(d,J=8.1Hz,1H),7.79(s,2H), 7.62(t,J=8.8Hz,2H),7.40(t,J=7.3Hz,1H),7.24(dq,J=20.4,11.6,10.1Hz,4H),7.15- 7.08(m,1H),6.48(s,1H);31P NMR(162MHz,CDCl3)δ67.40.
原料合成:
原料N-三氟甲硫基邻苯二甲酰亚胺的合成
根据文献(Kang,K.;Xu,C.;Shen,Q.Organic Chemistry Frontiers 2014,7,294.),用 AgSCF3(三氟甲硫醇银)和N-溴邻苯二甲酰亚胺(N-Bromophthalimide)在无水乙腈中,氩气条件下反应3h,然后通过旋转蒸发仪,蒸掉多余的乙腈,用15mL二氯甲烷溶解,过滤,去滤液,移除二氯甲烷,即可得到白色固体(N-三氟甲硫基邻苯二甲酰亚胺)。N-溴邻苯二甲酰亚胺2a,1H NMR(400MHz,CDC13)δ8.03(dd,J=5.4,3.1Hz,2H),7.89(dd,J=5.4,3.1Hz,2H);19F NMR(376MHz,CDCl3)δ-48.93;13C NMR(101MHz,CDCl3)δ165.7,135.4,131.4,127.9(q,J=314.9Hz),124.7.
原料烷基醚的合成
通用步骤:
根据文献(Han,J.H.;Kwon,Y.E.;Sohn,J.-H.;Ryu,D.H.Tetrahedron 2010,66,1673)进行合成,具体操作如下,首先取一个100mL的圆底烧瓶,称取10mmol的烷基三级醇,然后加入20mL二氯甲烷溶解,搅拌均匀,再加入约4mL的二异丙基乙胺(4.4mmol),然后置于冰浴中,搅拌条件下,小心加入氯甲基甲醚(MOMCl)约1.2mL,约5min后,置于60摄氏度的加热搅拌器中反应,过夜,待反应结束后,在冰浴条件下,加入饱和氯化铵溶液,然后用乙酸乙酯萃取,合并有机相,无水硫酸钠干燥,然后旋干拌样,柱色谱纯化,即可得到相应的烷基醚。
(2-(methoxymethoxy)-2-methylpropyl)benzene,1H NMR(400MHz, CDCl3)δ7.23-7.17(m,2H),7.16-7.11(m,3H),4.68(s,2H),3.26(s,3H),2.74(s,2H),1.14(s,6H);13C NMR(101MHz,CDCl3)δ138.1,130.6,127.8,126.1,91.0,76.6,55.0,48.5, 26.0.
2-(methoxymethoxy)-2-methyladamantane
1H NMR(400MHz,CDCl3)δ4.75(s,2H),3.40(s,3H),2.21(d,J=10.9Hz,2H),1.90-1.76(m,6H),1.76-1.65(m,4H),1.49(d,J=12.4Hz,2H),1.35(s,3H);13C NMR(101 MHz,CDCl3)δ90.1,79.1,55.5,38.5,36.8,34.7,32.8,27.6,27.1,22.8.
1-chloro-4-(2-(methoxymethoxy)-2-methylpropyl)benzene,1H NMR (400MHz,Chloroform-d)δ7.23(d,J=8.4Hz,2H),7.14(d,J=8.4Hz,2H),4.72(s,2H), 3.32(s,3H),2.76(s,2H),1.19(s,6H);13C NMR(101MHz,CDCl3)δ136.6,132.0,131.9, 127.9,91.0,76.3,55.0,47.9,25.9.
1-methoxy-4-(2-(methoxymethoxy)-2-methylpropyl)benzene,1H NMR(400MHz,CDCl3)δ7.04(d,J=8.6Hz,2H),6.74(d,J=8.7Hz,2H),4.67(s,2H), 3.71(s,3H),3.26(s,3H),2.67(s,2H),1.12(s,6H);13C NMR(101 MHz,CDCl3)δ158.0,131.5,130.2,113.2,91.0,76.7,55.1,55.0,47.5,25.9.
1-bromo-2-(2-(methoxymethoxy)-2-methylpropyl)benzene,1g,10mmol scale,colorless oil,(1.51g,55%),Rf=0.8(petroleum ether/ethylacetate 20∶1);1H NMR(400 MHz,CDCl3)δ7.53(dd,J=8,0.8Hz,1H),7.38(dd,J=7.7,1.6Hz,1H),7.21(dt,J=7.6, 1.2Hz,1H),7.05(td,J=7.7,1.6Hz,1H),4.74(s,2H),3.33(s,3H),3.05(s,2H),1.27(s, 6H);13C NMR(101 MHz,CDCl3)δ137.7,132.6,132.6,127.6,126.5,90.8,77.0,54.9,46.5, 25.8.
(2-(methoxymethoxy)-2-methyl-4-phenylbutyl)trimethylsilane
1H NMR(500MHz,CDCl3)δ7.31(t,J=7.5Hz,2H),7.25-7.18(m,3H),4.80-4.74(m,2H),3.43(s,3H),2.75-2.68(m,2H),1.92-1.84(m,2H),1.35(s,3H),1.23-1.08(m,2H),0.12(s,9H);13C NMR(126MHz,CDCl3)δ142.8,128.3,128.3,125.6,90.8,78.9,55.4,44.1,30.5,29.4,27.0,0.6.
2-(methoxymethoxy)-2-methylundecane
1H NMR(500MHz,CDCl3)δ4.70(s,2H),3.36(s,3H),1.51-1.46(m,2H),1.34-1.24(m,14H),1.21(s,6H),0.88(t,J=6.9Hz,3H);13C NMR(126MHz,CDCl3)δ91.0,76.3,55.0,41.9,31.9,30.2,29.7,29.6,29.3,26.3,24.0,22.7,14.1.
1-bromo-7-(methoxymethoxy)-7-methyloctane
1H NMR(500MHz,CDCl3)δ4.70(s,2H),3.53(t,J=6.8Hz,2H),3.36(s,3H),1.81-1.73 (m,2H),1.52-1.41(m,4H),1.40-1.28(m,4H),1.23(s,6H);13C NMR(126MHz,CDCl3) δ90.9,76.2,55.0,45.1,41.8,32.6,29.4,26.9,26.3,23.8.
6-(methoxymethoxy)-6-methylundecane
1H NMR(500MHz,CDCl3)δ4.68(s,2H),3.37(s,3H),1.50-1.44(m,4H),1.35-1.24(m, 12H),1.17(s,3H),0.89(t,J=7.1Hz,6H);13C NMR(126MHz,CDCl3)δ90.7,78.5,55.3,39.1,32.5,23.9,23.4,22.7,14.1.
1-(methoxymethoxy)-1-methylcyclododecane
1H NMR(400MHz,CDCl3)δ4.71(s,2H),3.36(s,3H),1.63(td,J=13.3,11.5,4.4Hz,2H), 1.49-1.23(m,20H),1.18(s,3H);13C NMR(101MHz,CDCl3)δ90.5,79.2,55.1,34.0,26.5, 26.1,25.1,22.6,22.1,19.7.
4-(2-(methoxymethoxy)-2-methylpropyl)-1,1′-biphenyl
1H NMR(500MHz,CDCl3)δ7.58(d,J=8.5Hz,2H),7.50(d,J=8.1Hz,2H),7.41(t,J= 7.7Hz,2H),7.31(t,J=7.4Hz,1H),7.27(d,J=8.1Hz,2H),4.76(s,2H),3.34(s,3H),2.84 (s,2H),1.24(s,6H);13C NMR(126MHz,CDCl3)δ141.0,139.0,137.2,131.0,128.7,127.0, 126.9,126.5,91.0,76.6,55.0,48.1,26.0.
2-fluoro-4′-(3-(methoxymethoxy)-3-methylbutan-2-y1)-1,1′-biphenyl
1H NMR(400MHz,CDCl3)δ7.55(d,J=8.1Hz,2H),7.42(t,J=7.6Hz,2H),7.36-7.29(m,2H),7.12-7.06(m,2H),4.76-4.69(m,2H),3.34(s,3H),2.83(q,J=7.1Hz,1H),1.35(d,J=7.1Hz,3H),1.23(s,3H),1.17(s,3H);13C NMR(101 MHz,CDCl3)δ160.4,158.0,145.8(d,J=7.4Hz),135.8(d,J=1.1Hz),129.6(d,J=4.0Hz),128.9(d,J=2.9Hz),128.3, 127.4,126.6(d,J=13.5Hz),125.4(d,J=3.1Hz),116.8,116.6,91.0,77.9,55.1,49.9,24.7, 24.2.15.8.
1-isobutyl-4-(2-(methoxymethoxy)-2-methylpropyl)benzene
1H NMR(400MHz,CDCl3)δ7.15(d,J=8.1Hz,2H),7.03(d,J=8.1Hz,2H),4.73-4.67(m,2H),3.31(s,3H),2.81(q,J=7.2Hz,1H),2.43(d,J=7.2Hz,2H),1.83(dq,J=13.6,6.8Hz,1H),1.33(d,J=7.2Hz,3H),1.16(s,3H),1.14(s,3H),0.89(d,J=6.6Hz,6H);13CNMR(101MHz,CDCl3)δ139.4,128.9,128.3,90.9,78.3,55.0,49.6,45.0,30.2,24.9,23.6,22.4.15.7.
2-(3-(methoxymethoxy)-3-methylbutyl)-4,5-diphenyloxazole
1H NMR(400MHz,CDCl3)δ7.64(dd,J=8.2,1.4Hz,2H),7.58(dd,J=8.2,1.4Hz,2H), 7.38-7.26(m,6H),4.74(s,2H),3.39(s,3H),2.99-2.94(m,2H),2.12-2.06(m,2H),1.31 (s,6H);13C NMR(101MHz,CDCl3)δ163.7,145.0,135.0,132.6,129.1,128.5,128.5,128.2, 127.9,127.9,126.3,91.0,75.2,55.2,38.8,26.1,23.1.
2-(2-(methoxymethoxy)-2-methylpropyl)thiophene
1H NMR(400MHz,CDCl3)δ7.08(dd,J=5.1,1.2Hz,1H),6.86(dd,J=5.1,3.4Hz,1H), 6.77-6.73(m,1H),4.70(s,2H),3.31(s,3H),2.94(s,2H),1.19(s,6H);13C NMR(101MHz,CDCl3)δ139.8,126.8,126.2,124.3,91.2,76.0,55.3,42.8,25.9.
7-(methoxymethoxy)-7-methyloctyl furan-2-carboxylate
1H NMR(500MHz,CDCl3)δ7.58(s,1H),7.18(s,1H),6.51(s,1H),4.70(s,2H),4.30(t,J =6.7Hz,2H),3.36(s,3H),1.75(p,J=6.9Hz,2H),1.53-1.47(m,2H),1.46-1.40(m,2H), 1.38-1.31(m,4H),1.21(s,6H);13C NMR(126MHz,CDCl3)δ158.8,146.2,144.8,117.7,111.8,91.0,76.2,65.0,55.1,41.8,29.8,28.7,26.3,25.9,23.9.
利用下述实施例将有助于理解本发明,但并不限制本发明的内容。
实施例1
先称取(37.1mg,0.15mmol),4CzIPN(北京华威锐科化工有限公司提供,下同)(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(自己合成,下同)(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(2-(甲氧基甲氧基)-2-甲基丙基)苯(19.4mg,0.1mmol),然后置于两支45W蓝光灯照射下,室温反应 12h。干法上样,柱层析(300-400目层析硅胶)得到产物17.4mg(正己烷),产率74%,1H NMR(400MHz,CDCl3)δ7.34-7.27(m,3H),7.22-7.17(m,2H), 3.01(s,2H),1.45(s,6H);19F NMR(376MHz,CDCl3)δ-35.12;13C NMR(101MHz,CDCl3) δ136.2,131.1(q,J=308.05),130.9,128.0,127.0,51.9,49.2,28.8.MS(EI)m/z 234(M)+
实施例2
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入 (22.9mg,0.1mmol),然后置于两支45W蓝光灯照射下,室温反应12h。干法上样,柱层析(300-400目层析硅胶)得到产物22.8mg(正己烷),产率 76%,1H NMR(400MHz,CDCl3)δ7.28(d,J=8.4Hz,2H),7.13(d,J=8.4Hz,2H),2.98(s, 2H),1.43(s,6H);19F NMR(376MHz,CDCl3)δ-35.15;13C NMR(101 MHz,CDCl3)δ 134.6,133.0,132.2,131.0(q,J=309.06Hz),128.2,51.6,48.4,28.8.MS(EI)m/z 268(M+).
实施例3
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入22.5mg,0.1mmol),然后置于两支45W蓝光灯照射下,室温反应12h。干法上样,柱层析(300-400目层析硅胶,下同)得到产物22.8mg(正己烷),产率76%,1H NMR(400MHz,CDCl3)δ7.11(d, J=8.6Hz,2H),6.84(d,J=8.7Hz,2H),3.80(s,3H),2.95(s,2H),1.43(s,6H);19F NMR (376MHz,CDCl3)δ-35.08;13C NMR(101MHz,CDCl3)δ158.6,131.9,131.2(q,J=307.5 Hz),128.2,113.4,55.2,52.2,48.3,28.8.MS(EI)m/z264(M+).
实施例4
先称取(27.1mg.0.1mmol),(37.1mg,0.15 mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL 二氯甲烷,然后置于45W蓝光灯照射下,室温反应12h。干法上样,柱层析(300-400 目层析硅胶)得到产物18.9mg(正己烷),产率61%,1H NMR (500MHz,CDCl3)δ7.59(d,J=7.8Hz,2H),7.54(dd,J=8.1,1.6Hz,2H),7.46-7.40(m, 2H),7.36-7.31(m,1H),7.28-7.25(m,2H),3.05(s,2H),1.48(s,6H).19F NMR(471MHz, CDCl3)δ-35.05.13C NMR(126MHz,CDCl3)δ140.7,139.8,135.2,131.3,131.1(q,J= 308.3),128.8,127.3,127.0,126.7,52.0,48.8,28.9.MS(EI)m/z310(M+).
实施例5
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入 (27.1mg,0.1mmol),然后置于两支45W蓝光灯照射下,室温反应12h。干法上样,柱层析(300-400目层析硅胶)得到产物18.8mg(正己烷),产率60%,1H NMR(400MHz,CDCl3)δ7.58(dd,J=8.0,1.1Hz,1H),7.35(dd,J=7.7,1.7Hz,1H),7.27(td,J=7.5,1.2Hz,1H),7.12(td,J=7.8,1.7Hz,1H),3.30(s,2H),1.51(s,6H);19F NMR(376MHz,CDCl3)δ-35.19;13C NMR(101MHz,CDCl3)δ136.1,133.3,132.8,131.0 (q,J=309.06Hz),128.7,127.0,126.2,52.9,47.0,28.8.MS(EI)m/z233[(M-Br)+].
实施例6
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(27.1mg,0.1mmol),然后置于两支45W蓝光灯照射下,室温反应12h。干法上样,柱层析(300-400目层析硅胶,下同)得到产物17.5mg(石油醚60-90:乙酸乙酯=100∶1),产率51%,1H NMR (400MHz,CDCl3)δ7.58-7.52(m,2H),7.44(t,J=7.5Hz,2H),7.40-7.33(m,2H),7.10- 7.01(m,2H),3.13(q,J=7.1Hz,1H),1.48(dd,J=10.5,3.3Hz,9H);19F NMR(376MHz, CDCl3)δ-34.73;13C NMR(101 MHz,CDCl3)δ159.2(d,J=247.9Hz),143.2(d,J=7.2 Hz),135.5(d,J=1.2Hz),131.1(q,J=307.7Hz),130.0(d,J=4.0Hz),128.9(d,J=2.9 Hz),128.5,127.7,127.5,125.5(d,J=3.2Hz),116.8(d,J=23.2Hz),55.5,49.2,28.9,25.8, 16.5.MS(EI)m/z342(M+).
实施例7
先称取(49.4mg,0.2mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38 mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(26.5mg,0.1mmol),然后置于45W蓝光灯照射下,室温反应24h。干法上样,柱层析(300-400目层析硅胶,下同)得到产物18.0mg(正己烷),产率59%,1H NMR(400MHz,CDCl3)δ7.12(d,J=8.2Hz,2H),7.06(d,J=8.2Hz,2H), 3.04(q,J=7.2Hz,1H),2.45(d,J=7.2Hz,2H),1.85(dp,J=13.6,6.8Hz,1H),1.46-1.40 (m,9H),0.90(d,J=6.6Hz,6H);19F NMR(376MHz,CDCl3)δ-34.76;13C NMR(101MHz, CDCl3)δ140.4,138.7,129.0,128.6,128.0(q,J=191.9Hz),56.0,49.2(d,J=1.2Hz),45.0, 30.2,29.0(d,J=0.9Hz),25.7(d,J=1.3Hz),22.4(d,J=2.4Hz),16.5.MS(EI)m/z 304 (M+).
实施例8
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(35.2mg,0.1mmol),然后置于两支45W蓝光灯照射下,室温反应12h。干法上样,柱层析(300-400目层析硅胶)得到产物 16.4mg(石油醚60-90:乙酸乙酯=10:1),产率42%,1H NMR(500MHz,CDCl3)δ7.63 (d,J=8.2Hz,2H),7.58(d,J=8.2Hz,2H),7.39-7.32(m,6H),3.09-3.00(m,2H),2.33- 2.25(m,2H),1.54(s,6H);19F NMR(471MHz,CDCl3)δ-35.70;13C NMR(101MHz, CDCl3)δ162.5,145.4,135.2,132.5,130.8(q,J=309.06Hz),129.0,128.7,128.6,128.4, 128.1,128.0,126.4,51.3,39.8,29.3,24.1.MS(EI)m/z 391(M+).
实施例9
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入((2-(甲氧基甲氧基)-2-甲基-4-苯基丁基)三甲基硅烷)(28.1mg,0.1mmol),然后置于45W蓝光灯照射下,室温反应24h。干法上样,柱层析(300-400目层析硅胶,下同)得到产物17.0mg(正己烷),产率53%,1H NMR(400MHz,CDCl3)δ7.29 (t,J=7.4Hz,2H),7.19(t,J=6.9Hz,3H),2.86(td,J=12.8,5.0Hz,1H),2.74(td,J=12.9, 5.7Hz,1H),2.10-1.94(m,2H),1.61(s,3H),1.26(s,2H),0.14(s,9H);19F NMR(376MHz,CDCl3)δ-35.89;13C NMR(101MHz,CDCl3)δ141.6,130.9(q,J=308.4Hz),128.5,128.4, 126.0,56.8,45.5,31.5,31.3(d,J=0.1Hz),30.5(d,J=0.2Hz),0.9.MS(EI)m/z320(M+).
实施例10
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(23.1mg,0.1mmol),然后置于两支45W蓝光灯照射下,室温反应12h。干法上样,柱层析(300-400目层析硅胶)得到产物18.9mg(正己烷),产率70%,1HNMR(400MHz,CDCl3) δ1.67-1.60(m,2H),1.45(s,6H),1.41(dd,J=10.1,5.1Hz,2H),1.27(s,12H),0.88(t,J= 6.8Hz,3H);19F NMR(376MHz,CDCl3)δ-35.63;13C NMR(101 MHz,CDCl3)δ130.4(q, J=308.6Hz),52.2,43.3,31.9,29.8,29.6,29.5,29.4(d,J=1.4Hz),29.3,24.6,22.7,14.1. MS(EI)m/z 270(M+).
实施例11
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(26.8mg,0.1mmol),然后置于45W蓝光灯照射下,室温反应12h。干法上样,柱层析(300-400目层析硅胶)得到产物 17.9mg(正己烷),产率70%,1H NMR(400MHz,CDCl3)δ3.54(t,J=6.7Hz,2H),1.83 -1.73(m,2H),1.68-1.62(m,2H),1.51-1.39(m,10H),1.33(ddd,J=15.5,6.4,1.6Hz, 2H);19F NMR(376MHz,CDCl3)δ-35.65;13C NMR(101 MHz,CDCl3)δ131.1(q,J= 308.6Hz),52.1,45.1,43.1,32.5,29.4,29.4,29.0,26.7,24.5;MS(EI)m/z 306(M+).
实施例12
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(23.1 mg,0.1mmol),然后置于45W蓝光灯照射下,室温反应12h。干法上样,柱层析(300-400 目层析硅胶)得到产物20.3mg(正己烷),产率75%,1HNMR (400MHz,CDCl3)δ1.67-1.58(m,4H),1.42-1.24(m,15H),0.90(t,J=7.1Hz,6H);19F NMR(376MHz,CDCl3)δ-35.19;13C NMR(101MHz,CDCl3)δ131.2(q,J=307.5Hz), 56.3,40.6(d,J=1.1Hz),32.03,26.8(d,J=0.8Hz),23.8,22.5,14.0.MS(EI)m/z270(M+).
实施例13
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(21.1mg,0.1mmol),然后置于45W蓝光灯照射下,室温反应12h。干法上样,柱层析(300-400目层析硅胶)得到产物20.0mg(正己烷),产率80%,1H NMR(400MHz,CDCl3)δ2.46-2.38(m,2H),2.18-2.09(m,2H),2.00-1.83(m,4H),1.79(s,3H),1.75-1.63(m, 6H);19F NMR(376MHz,CDCl3)δ-34.25;13C NMR(101MHz,CDCl3)δ131.5(q,J= 307.8Hz),61.5,39.0,37.4,33.8,33.2,27.2,27.1,26.9.MS(EI)m/z250(M+).
实施例14
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(24.3mg,0.1 mmol),然后置于45W蓝光灯照射下,室温反应12h。干法上样,柱层析(300-400 目层析硅胶)得到产物27.0mg(正己烷),产率48%,1H NMR(400MHz, CDCl3)δ1.68-1.59(m,2H),1.51(s,3H),1.35(s,18H),0.88(q,J=8.3,6.7Hz,2H);19F NMR(376MHz,CDCl3)δ-34.84;13CNMR(101 MHz,CDCl3)δ131.2(q,J=308.9Hz), 56.0,35.1,28.4,26.3,26.0,22.7,22.2,19.8.MS(EI)m/z 282(M+).
实施例14
先称取(49.4mg,0.2mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38 mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(20.3mg,0.1mmol),然后置于45W蓝光灯照射下,室温反应24h。干法上样,柱层析(300-400目层析硅胶)得到产物13.0mg(正己烷),产率54%,1H NMR(500MHz,CDCl3) δ7.21(dd,J=5.2,1.1Hz,1H),6.97(dd,J=5.1,3.5Hz,1H),6.88(d,J=3.0Hz,1H),3.23 (s,2H),1.50(s,6H);19F NMR(471 MHz,CDCl3)δ-35.28;13C NMR(126MHz,CDCl3)δ 137.8,131.0(q,J=307.0Hz),128.1,126.7,124.8,51.5,43.2,28.9.MS(EI)m/z240(M+).
实施例16
先称取(49.4mg,0.2mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38 mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(30.0 mg,0.1mmol),然后置于45W蓝光灯照射下,室温反应24h。干法上样,柱层析(300-400 目层析硅胶,下同)得到产物21.2mg(石油醚60-90:乙酸乙酯=20∶1-10∶1),产率63%,1H NMR(400MHz,CDCl3)δ7.58(dd,J=1.7,0.8Hz,1H), 7.18(dd,J=3.5,0.7Hz,1H),6.51(dd,J=3.5,1.7Hz,1H),4.30(t,J=6.7Hz,2H),1.76(p, J=6.7Hz,2H),1.65(dd,J=10.5,5.6Hz,2H),1.50-1.40(m,10H),1.37(td,J=9.2,8.5, 3.0Hz,2H);19FNMR(376MHz,CDCl3)δ-35.65;13C NMR(101 MHz,CDCl3)δ158.8, 146.2,144.9,131.1(q,J=308.8Hz),117.7,111.8,64.9,52.1,43.1,29.4,28.6,25.8,24.5. MS(ESI)calcd forC15H22F3O3S+[M+H]+339.12,found 339.15。
Claims (7)
1.一种制备三级烷基三氟甲基硫醚的方法,其特征是:它是以三级烷氧醚(OCH2OCH3,-MOM)为原料,在蓝光灯照射下,在溶液中,氩气气氛下,在少量碳酸钾存在下,以光催化剂4CzIPN和有机硫醇催化剂4-巯基萘并[2,1-d:1′,2′-f][1,3,2]二氧代环庚烯-4-氧化物协同催化,与2-((三氟甲基)硫基)异二氢吲哚-1,3-二酮)2a在室温下反应,得到三级烷基三氟甲基硫醚
所述的光催化剂4CzIPN与有机硫醇催化剂有如下结构:
2.根据权利要求1所述的制备方法,其特征是:所述的三级烷基三氟甲基硫醚中的R1基团是各种取代的芳基、杂芳基或烷基,R2基团是甲基、乙基或CH2Si(CH3)3。
3.根据权利要求1所述的制备方法,其特征是:所述的在溶液中是在二氯甲烷中。
4.根据权利要求1所述的制备方法,其特征是:所述的三级烷氧醚1与沈试剂2a的物质的量之比是1∶1-1∶2。
5.根据权利要求4所述的制备方法,其特征是:所述的三级烷氧醚1与沈试剂2a的物质的量之比是1∶1.5。
6.根据权利要求1所述的制备方法,其特征是:所述的光催化剂4CzIPN与硫醇催化剂的用量是三级烷氧醚1摩尔数的2%的摩尔量。
7.根据权利要求1所述的制备方法,其特征是:所述的碳酸钾是三级烷氧醚1摩尔数的10%的摩尔量。
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