CN113845445A - （1-乙烯基）氨磺酰氟衍生物及其制备方法和应用 - Google Patents
（1-乙烯基）氨磺酰氟衍生物及其制备方法和应用 Download PDFInfo
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- USPTVMVRNZEXCP-UHFFFAOYSA-N sulfamoyl fluoride Chemical class NS(F)(=O)=O USPTVMVRNZEXCP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 8
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims abstract description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- -1 di-substituted methyl Chemical group 0.000 claims description 11
- 125000001246 bromo group Chemical group Br* 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001345 alkine derivatives Chemical class 0.000 claims description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- QZJMONDPQWPMGI-UHFFFAOYSA-N lithium;azane Chemical compound [Li+].N QZJMONDPQWPMGI-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229940124530 sulfonamide Drugs 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 150000003456 sulfonamides Chemical class 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 239000012025 fluorinating agent Substances 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000000163 radioactive labelling Methods 0.000 claims description 3
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000007876 drug discovery Methods 0.000 abstract description 3
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- 125000004429 atom Chemical group 0.000 abstract description 2
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- 238000001308 synthesis method Methods 0.000 abstract description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Chemical group 0.000 abstract 1
- XMSZANIMCDLNKA-UHFFFAOYSA-N methyl hypofluorite Chemical group COF XMSZANIMCDLNKA-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 229960000909 sulfur hexafluoride Drugs 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- XGCDHPDIERKJPT-UHFFFAOYSA-N [F].[S] Chemical group [F].[S] XGCDHPDIERKJPT-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000487 histidyl group Chemical group [H]N([H])C(C(=O)O*)C([H])([H])C1=C([H])N([H])C([H])=N1 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QAGYXMQZSHPCMY-UHFFFAOYSA-N n-diazosulfamoyl fluoride Chemical compound FS(=O)(=O)N=[N+]=[N-] QAGYXMQZSHPCMY-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical group FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- DUGWRBKBGKTKOX-UHFFFAOYSA-N tetrafluoro(oxo)-$l^{6}-sulfane Chemical compound FS(F)(F)(F)=O DUGWRBKBGKTKOX-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C307/00—Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C307/02—Monoamides of sulfuric acids or esters thereof, e.g. sulfamic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/42—Radicals substituted by singly-bound nitrogen atoms having hetero atoms attached to the substituent nitrogen atom
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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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
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- 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
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
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- C07C2601/00—Systems containing only non-condensed rings
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Abstract
本发明公开了(1‑乙烯基)氨磺酰氟衍生物及其制备方法和应用，属于有机合成化学领域。该衍生物具有如式
所示的通式结构，R独立地选自芳香族或杂芳族或脂肪烃的单取代或二取代邻位、间位或对位上的苯基、甲基、乙基、丁基、戊基、甲氧基、氟、氯、溴、硝基或氰基。本发明中(1‑乙烯基)氨磺酰氟衍生物含有磺酰氟官能团(RSO2F)，具有独特的稳定性和活性，可作为中间体或氟交换试剂用于合成含氟化合物或含磺酰化合物，合成方法简便，产率和原子经济性高，在有机合成、材料科学、化学生物学和药物发现等方面具有广阔的应用前景。
Description
技术领域
本发明涉及有机合成化学领域，具体涉及一种(1-乙烯基)氨磺酰氟衍生物及其制备方法和应用。
背景技术
六价硫氟交换化学是最新和最强大的点击化学反应之一，其核心是基于硫氟键的相对稳定性及其在特定条件下能被亲核取代发生脱氟反应。在有机合成中，磺酰氟代替磺酰氯被长期认为是通用的前体用于合成含磺酰化合物，包括磺酰胺、磺酸酯和砜。此外，磺酰氟已被用作一类新的选择性氟化试剂，用于脱氧氟化和18F放射性标记，最近氟磺酰叠氮化物(FSO2N3)已被证明是用于从伯胺合成叠氮化物的极好的重氮转移试剂。在材料科学中，磺酰氟已被用于合成带有独特-SO2-键的聚合物，这是对具有碳-碳或碳-杂原子键的经典合成聚合物的重要补充。此外，由于SuFExable团的正交反应性，-SO2F部分已被用作侧链中的反应性手柄，可以顺利地预组装到单体上，用于聚合物的聚合后改性。在生物学科中，磺酰氟已被用作化学生物学中特权共价探针和抑制剂和药物发现，他们被证明能够共价修饰酶结合位点的各种氨基酸残基，包括上下文特定的丝氨酸、苏氨酸、赖氨酸、酪氨酸、半胱氨酸和组氨酸残基。相对于广泛采用铜催化的炔烃-叠氮化物环加成(CuAAC)，SuFEx反应具有独特的特性。首先，SuFEx反应通常在无金属条件下进行对应用程序具有特殊意义的生物系统中点击化学的研究。其次，SuFEx反应产生与各种不同的联系亲核试剂，从甲硅烷基醚、醇、胺到碳亲核试剂，通过S-F创建不同的功能分子交换。第三，与定义的末端炔烃和叠氮化物官能团需要多个步骤才能安装到基材中以进行CuAAC反应，SuFExable手柄是通常更灵活容易通过联合引入通过离散连接词的共同本机官能团集线器，例如SO2F2和SOF4。SuFEx反应的这些特点将使其在化学生物学和药物领域得到更广泛的应用发现。
发明内容
本发明的第一目的在于提供一种通式(I)所示的(1-乙烯基)氨磺酰氟衍生物。
本发明的另一目的在于提供上述通式(I)所示(1-乙烯基)氨磺酰氟衍生物的制备方法。
本发明的又一目的在于提供上述通式(I)所示(1-乙烯基)氨磺酰氟衍生物在合成含氟化合物或含磺酰化合物中的应用。
本发明的上述目的通过以下技术方案实现：
本发明提供的一种(1-乙烯基)氨磺酰氟衍生物，其通式如(I)所示：
R独立地选自芳香族或杂芳族或脂肪烃的单取代或二取代邻位、间位或对位上的苯基、甲基、乙基、丁基、戊基、甲氧基、氟、氯、溴、硝基或氰基。
优选地，所述(1-乙烯基)氨磺酰氟衍生物选自如(Ⅱ)任一个所示的通式结构：
R1独立地选自芳香族或杂芳族芳环上的单取代或二取代的甲基、乙基、甲氧基、氟、氯、溴、硝基、氰基或烷烃基；
m选自0-12的整数，n选自1-8的整数。
优选地，所述(1-乙烯基)氨磺酰氟衍生物选自以下2a至2b’任一结构的化合物：
本发明提供通式(I)所示(1-乙烯基)氨磺酰氟衍生物的制备方法，合成路线如下式(III)所示：
其中，R独立地选自芳香族或杂芳族或脂肪烃的单取代或二取代邻位、间位或对位上的苯基、甲基、乙基、丁基、戊基、甲氧基、氟、氯、溴、硝基或氰基；
该制备方法包括将炔、锂铵盐和季铵盐溶解在溶剂中，在20～100℃下搅拌2～24h。
优选地，所述季铵盐选自苄基三乙基氯化铵(TEBA)、四丁基溴化铵、四丁基氯化铵、四丁基硫酸氢铵(TBAB)、三辛基甲基氯化铵、十二烷基三甲基氯化铵、十四烷基三甲基氯化铵或四丁基四氟硼酸铵中的一种或两种以上组合。
优选地，所述溶剂选自二氯甲烷、氯仿、1，2-二氯乙烷、四氢呋喃、乙腈、甲苯或氯苯中的一种或两种以上组合。
优选地，通式(Ⅱ)所示(1-乙烯基)氨磺酰氟衍生物的制备方法，合成路线如下式(Ⅳ)所示：
其中，R1独立地选自芳香族或杂芳族芳环上的单取代或二取代的甲基、乙基、甲氧基、氟、氯、溴、硝基、氰基或烷烃基，m选自0-12的整数，n选自1-8的整数；
该制备方法包括将炔、锂铵盐和四丁基四氟硼酸铵溶解在溶剂中，在20～100℃下搅拌2～24h。
本发明提供任一所述(1-乙烯基)氨磺酰氟衍生物在合成含氟化合物或含磺酰化合物中的应用。
优选地，所述含氟化合物包括氟硫酸盐和氨磺酰氟化物，所述含磺酰化合物包括磺酰胺、磺酸酯和砜。
优选地，所述(1-乙烯基)氨磺酰氟衍生物作为中间体或氟交换试剂。
本发明提供任一所述(1-乙烯基)氨磺酰氟衍生物作为选择性氟化试剂在脱氧氟化和18F放射性标记中的应用。
与现有技术相比，本发明的有益效果在于：
一、本发明利用简单的加成反应合成(1-乙烯基)氨磺酰氟衍生物，合成方法简便，产率高，原子经济性高，在有机合成和药物化学领域为合成氟硫交换化合物提供新的途径。
二、本发明的(1-乙烯基)氨磺酰氟衍生物含有磺酰氟官能团(RSO2F)，其具有独特的稳定性和活性，可作为中间体或氟交换试剂用于合成含氟化合物如氟硫酸盐、氨磺酰氟化物或含磺酰化合物如磺酰胺、磺酸酯砜，在有机合成、材料科学、化学生物学和药物发现等方面具有广阔的应用前景。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点会变得更显著：
图1是实施例1中2a的核磁1H NMR。
图2是实施例1中2b的核磁1H NMR。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面结合本发明实施例的附图，对本发明实施例的技术方案进行清楚、完整地描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于所描述的本发明的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其它实施例，都属于本发明保护的范围。
实施例1
式III的合成制备反应式如下：
按如下步骤制备：将炔(10mmol)和锂铵盐(1.5equiv)溶于30ml溶剂中，加入四丁基四氟硼酸按(0.5equiv)，在20～100℃下于反应瓶中搅拌12h，冷却到室温后，用乙酸乙酯萃取分液，有机相用无水硫酸钠干燥，过滤，旋干，柱层析分离，得到淡黄色粘稠产物。
实施例1中，按照上述方法制备如式(2a-2b’)所示的(1-乙烯基)氨磺酰氟衍生物，其取代基选择、收率和核磁1H NMR数据如表1所示。
表1
Claims (10)
1.一种(1-乙烯基)氨磺酰氟衍生物，其通式如(I)所示：
R独立地选自芳香族或杂芳族或脂肪烃的单取代或二取代邻位、间位或对位上的苯基、甲基、乙基、丁基、戊基、甲氧基、氟、氯、溴、硝基或氰基。
2.根据权利要求1所述的(1-乙烯基)氨磺酰氟衍生物，其特征在于，选自如(Ⅱ)任一个所示的通式结构：
R1独立地选自芳香族或杂芳族芳环上的单取代或二取代的甲基、乙基、甲氧基、氟、氯、溴、硝基、氰基或烷烃基；
m选自0-12的整数，n选自1-8的整数。
3.根据权利要求1或2所述的(1-乙烯基)氨磺酰氟衍生物，其特征在于，选自以下2a至2b’任一结构的化合物：
4.权利要求1至3任一项所述(1-乙烯基)氨磺酰氟衍生物的制备方法，其特征在于，合成路线如式(III)所示：
其中，R独立地选自芳香族或杂芳族或脂肪烃的单取代或二取代邻位、间位或对位上的苯基、甲基、乙基、丁基、戊基、甲氧基、氟、氯、溴、硝基或氰基；
包括将炔、锂铵盐和季铵盐溶解在溶剂中后在20～100℃下搅拌2～24h的步骤。
5.根据权利要求4所述(1-乙烯基)氨磺酰氟衍生物的制备方法，其特征在于，所述季铵盐选自苄基三乙基氯化铵、四丁基溴化铵、四丁基氯化铵、四丁基硫酸氢铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵、十四烷基三甲基氯化铵或四丁基四氟硼酸铵中的一种或两种以上组合。
6.根据权利要求4所述(1-乙烯基)氨磺酰氟衍生物的制备方法，其特征在于，所述溶剂选自二氯甲烷、氯仿、1，2-二氯乙烷、四氢呋喃、乙腈、甲苯或氯苯中的一种或两种以上组合。
7.根据权利要求4至6任一项所述(1-乙烯基)氨磺酰氟衍生物的制备方法，其特征在于，合成路线如式(Ⅳ)所示：
其中，R1独立地选自芳香族或杂芳族芳环上的单取代或二取代的甲基、乙基、甲氧基、氟、氯、溴、硝基、氰基或烷烃基，m选自0-12的整数，n选自1-8的整数；
包括将炔、锂铵盐和四丁基四氟硼酸铵溶解在溶剂中后在20～100℃下搅拌2～24h的步骤。
8.权利要求1至3任一项所述(1-乙烯基)氨磺酰氟衍生物在合成含氟化合物或含磺酰化合物中的应用。
9.根据权利要求8所述的应用，其特征在于，所述含氟化合物包括氟硫酸盐和氨磺酰氟化物，和/或所述含磺酰化合物包括磺酰胺、磺酸酯和砜；
所述(1-乙烯基)氨磺酰氟衍生物作为中间体或氟交换试剂。
10.权利要求1至3任一项所述(1-乙烯基)氨磺酰氟衍生物作为选择性氟化试剂在脱氧氟化和18F放射性标记中的应用。
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