CN115974730A - 以过硫酸盐合成有机硫酸盐的方法 - Google Patents
以过硫酸盐合成有机硫酸盐的方法 Download PDFInfo
- Publication number
- CN115974730A CN115974730A CN202310019868.5A CN202310019868A CN115974730A CN 115974730 A CN115974730 A CN 115974730A CN 202310019868 A CN202310019868 A CN 202310019868A CN 115974730 A CN115974730 A CN 115974730A
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- China
- Prior art keywords
- nmr
- sulfate
- base
- sodium
- 400mhz
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 21
- 150000004028 organic sulfates Chemical class 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 134
- -1 sulfate radical Chemical class 0.000 claims abstract description 104
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 150000003254 radicals Chemical class 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 239000003446 ligand Substances 0.000 claims description 32
- 229910052796 boron Inorganic materials 0.000 claims description 29
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 29
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 28
- 125000003342 alkenyl group Chemical group 0.000 claims description 28
- 125000003545 alkoxy group Chemical group 0.000 claims description 28
- 125000004414 alkyl thio group Chemical group 0.000 claims description 28
- 125000000304 alkynyl group Chemical group 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 28
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 28
- 229910052710 silicon Inorganic materials 0.000 claims description 28
- 239000010703 silicon Substances 0.000 claims description 28
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 28
- 125000003172 aldehyde group Chemical group 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 23
- 125000003368 amide group Chemical group 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 23
- 125000001424 substituent group Chemical group 0.000 claims description 22
- 125000005843 halogen group Chemical group 0.000 claims description 17
- 238000004440 column chromatography Methods 0.000 claims description 14
- 238000010791 quenching Methods 0.000 claims description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 5
- YNLLTVQHFISWLO-UHFFFAOYSA-N B(O)(O)O.FC=1C(=C(C=CC1)F)F Chemical compound B(O)(O)O.FC=1C(=C(C=CC1)F)F YNLLTVQHFISWLO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 16
- 230000007246 mechanism Effects 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000007342 radical addition reaction Methods 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 253
- 238000005160 1H NMR spectroscopy Methods 0.000 description 106
- 238000002474 experimental method Methods 0.000 description 92
- 239000011734 sodium Substances 0.000 description 91
- 229910052708 sodium Inorganic materials 0.000 description 76
- 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 73
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 53
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 43
- 229910052938 sodium sulfate Inorganic materials 0.000 description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 239000012074 organic phase Substances 0.000 description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 22
- 239000010949 copper Substances 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 229910052786 argon Inorganic materials 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 235000011152 sodium sulphate Nutrition 0.000 description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 9
- 101710134784 Agnoprotein Proteins 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 229910021653 sulphate ion Inorganic materials 0.000 description 6
- ZXUCBXRTRRIBSO-UHFFFAOYSA-L tetrabutylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC ZXUCBXRTRRIBSO-UHFFFAOYSA-L 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 238000005670 sulfation reaction Methods 0.000 description 5
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 4
- CZNJCCVKDVCRKF-UHFFFAOYSA-N Benzyl sulfate Chemical compound OS(=O)(=O)OCC1=CC=CC=C1 CZNJCCVKDVCRKF-UHFFFAOYSA-N 0.000 description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 4
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 3
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001180 sulfating effect Effects 0.000 description 3
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical group C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 2
- NZFLWVDXYUGFAV-UHFFFAOYSA-N 1-methyl-2-acetylpyrrole Chemical compound CC(=O)C1=CC=CN1C NZFLWVDXYUGFAV-UHFFFAOYSA-N 0.000 description 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 2
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 2
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 2
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- MUXFZBHBYYYLTH-UHFFFAOYSA-N Zaltoprofen Chemical compound O=C1CC2=CC(C(C(O)=O)C)=CC=C2SC2=CC=CC=C21 MUXFZBHBYYYLTH-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical class CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- QGXBDMJGAMFCBF-LUJOEAJASA-N epiandrosterone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC[C@H]21 QGXBDMJGAMFCBF-LUJOEAJASA-N 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- CGIGDMFJXJATDK-UHFFFAOYSA-N indomethacin Chemical compound CC1=C(CC(O)=O)C2=CC(OC)=CC=C2N1C(=O)C1=CC=C(Cl)C=C1 CGIGDMFJXJATDK-UHFFFAOYSA-N 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 2
- BAZQYVYVKYOAGO-UHFFFAOYSA-M loxoprofen sodium hydrate Chemical class O.O.[Na+].C1=CC(C(C([O-])=O)C)=CC=C1CC1C(=O)CCC1 BAZQYVYVKYOAGO-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical group 0.000 description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 2
- SERHXTVXHNVDKA-UHFFFAOYSA-N pantolactone Chemical compound CC1(C)COC(=O)C1O SERHXTVXHNVDKA-UHFFFAOYSA-N 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- 229910001958 silver carbonate Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- KKKDGYXNGYJJRX-UHFFFAOYSA-M silver nitrite Chemical compound [Ag+].[O-]N=O KKKDGYXNGYJJRX-UHFFFAOYSA-M 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开了一种有机硫酸盐的制备方法，包括以下步骤:以过硫酸盐为硫酸根来源,通过所述硫酸根的自由基负离子实现自由基前体化合物官能团的转化，从而制备出所述有机硫酸盐。本发明以过硫酸盐为来源，通过自由基加成机制，作用于自由基前体底物，过硫酸盐作为一种硫酸根自由基负离子参与到有机的官能团转化中，高效的合成有机硫酸盐。
Description
技术领域
本发明涉及有机化学领域和自由基化学领域，公开了一类全新的自由基硫酸化反应。
背景技术
有机硫酸盐化合物在自然界广泛存在，包括核苷、多肽、蛋白质、类固醇、多糖和信息素，它们在信号转导、激素调节、分子识别和解毒等生物学功能中起着重要作用。同时，将天然药物分子进行后期硫酸化处理是非常普遍的药物改性手段，如肝素、软骨素进行硫酸化后可以得到硫酸肝素和硫酸软骨素，增强了其在分子间相互作用和蛋白质与受体的结合。值得关注的是第一种含有机硫酸盐的抗生素阿维巴坦钠的出现，已经促使了其他新型β-内酰胺酶抑制剂的逐步报道。由于有机硫酸盐化合物在各种重要的生物过程中发挥着重要作用，它的合成已成为人们相当感兴趣的焦点。
迄今为止，向化合物中引入硫酸根基团最为普遍的方法是化合物中的羟基或者胺基与三氧化硫(SO3)-有机胺的络合物发生亲核加成反应。此方法的具有很好的普适性，但是也有很大的局限性，即完全依赖底物中羟基和氨基官能团的亲核性(UmeshR.Desai.Tetrahedron,2010,66,2907-2918；Alan M.Jones.Chem.Commun.,2019,55,4319-4322)，并且三氧化硫毒性大，生物兼容性差。其他方法，如含羟基的化合物与硫酸发生酯化反应、浓硫酸与烯烃发生加成反应都是理论上可行的；硫酸根的弱亲核性，使其对底物有严格的要求、反应条件苛刻，这些方法并不具有太大的应用价值。因此，开发一种全新的反应机制，即不依赖底物亲核性或者SO3络合物的亲电性，反应条件温和的硫酸化方法具有很重要的意义。
发明内容
为解决传统硫酸化底物受限和硫酸化试剂毒性较大的问题，本发明公开了一种有机硫酸盐及其制备方法。
一种有机硫酸盐的制备方法，包括以下步骤:以过硫酸盐为硫酸根来源,通过所述硫酸根的自由基负离子实现有机化合物官能团的转化，从而制备出所述有机硫酸盐。
可选的，所述过硫酸盐具有如下分子通式：
其中，M为抗衡阳离子。
一种有机硫酸盐，所述有机硫酸盐具有如下分子通式：
其中R包括取代的烃基和取代的芳(杂)基，取代基包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基、叠氮基或卤素原子，取代基的数量为一个或多个。
本发明以过硫酸盐为来源，通过自由基加成机制，作用于自由基前体底物，过硫酸盐作为一种硫酸根自由基负离子参与到有机的官能团转化中，高效的合成有机硫酸盐。本发明使用的过硫酸盐为K2S2O8、Na2S2O8、Ag2S2O8、(NH4)2S2O8、(Et4N)2S2O8、(Bu4N)2S2O8、(PyH)2S2O8等，所适用的自由基前体化合物包含但不限于羧酸、苄位化合物、烯烃、卤素、烷基硼、烷基醇、1,3-二羰基化合物、芳(杂)环、环丙烷类等化合物。
具体实施方式
以下通过具体实施方式对本发明的技术方案作具体说明，下述实施例中的部件或设备如无特别说明，均为通用标准件或本领域技术人员知晓的部件，其结构和原理都为本技术人员均可通过技术手册得知或通过常规实验方法获知。
一般说明
实施实例中使用了缩写，其含义如下：Me是甲基，Ph是苯基，Bu是丁基，B2Pin2是联硼酸频哪醇酯，TMS是三甲基硅基。THF是四氢呋喃，DCM是二氯甲烷，Acetone是丙酮，DMF是N,N-二甲基甲酰胺，NMR是核磁共振。
本发明所涉及的无水无氧的实验条件均按照Schlenk(史兰克)技术标准执行。所用溶剂在使用前用标准方法提纯和干燥，所用化合物均为市售或按照已有文献方法合成得到，并在使用前提纯。特别的，烷基硼类化合物的制备方法参考文献(LeiLiu.Angew.Chem.Int.Ed.,2012,51,528-53)。
本发明是通过一种全新的自由基机制进行的，以往所有硫酸化反应的机理都是依赖于反应起始物的亲核性，对活性三氧化硫复合物(亲电性)进行加成反应；或者借助于硫酸根负离子的弱亲核性。本发明的核心在于过硫酸盐生成硫酸根自由基负离子，使其不仅只是一种氧化剂，而是一种重要的硫酸根官能团试剂。硫酸化反应的机理通式如下所示：
实施例一
该实施例重点介绍一种以羧酸类化合物为底物、过硫酸铵为硫酸根来源的有机硫酸盐化合物的制备方法，其通式如下：
其中R包括取代的烃基和取代的芳(杂)基。取代基包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基、叠氮基或卤素原子，取代基的数量为一个或多个。
Ag(I)为任何一价银盐，包括AgOAc、AgNO3、AgNO2、Ag2SO4、AgF、AgBr、AgI、AgOTf、AgBF4、AgPF6、AgClO4、Ag2CO3、AgTFA等。Ligand为配体，包括单齿、双齿、三齿和多齿配体。Base为有机碱或无机碱，包括LiHCO3、Li2CO3、Li3PO4、LiH2PO4、Li2HPO4、LiHC2O4、Li2C2O4、CH3COOLi、HCOOLi、LiOH、MeOLi、t-BuOLi、NaHCO3、Na2CO3、Na3PO4、NaH2PO4、Na2HPO4、NaHC2O4、Na2C2O4、CH3COONa、HCOONa、NaOH、MeONa、t-BuONa、KHCO3、K2CO3、K3PO4、KH2PO4、K2HPO4、KHC2O4、K2C2O4、CH3COOK、HCOOK、KOH、KOLi、t-BuOK、NH4HCO3、(NH4)2CO3、(NH4)3PO4、(NH4)H2PO4、(NH4)2HPO4、NH4HC2O4、(NH4)2C2O4、氨水、三乙胺、二异丙胺、三甲胺、哌啶、吡啶。RT为室温，Na+resin为钠离子型树脂。
实施例二
该实施例重点介绍一种以苄位碳氢类化合物为底物、过硫酸铵为硫酸根来源的有机硫酸盐化合物的制备方法，其通式如下：
其中R1包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基R1的数量为1～5；R2包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基；R3包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基。
Ag(I)、Ligand、Base、RT、Na+resin同实施例一。
实施例三
该实施例重点介绍一种以烯烃类化合物为底物、过硫酸钾为硫酸根来源，合成有机双硫酸盐化合物的制备方法，其通式如下：
其中R1包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基R1的数量为1～5；R2包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基；R3包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基。
Ag(I)、Ligand、Base、RT、Na+resin同实施例一。
实施例四
该实施例重点介绍一种以烯烃类化合物为底物、过硫酸钾为硫酸根来源的有机硫酸盐化合物的制备方法，其通式如下：
其中R1包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基R1的数量为1～5；R2包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基；R3包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基。[Nu-]包括氰基(CN)、羟基(OH)、氯(Cl)、叠氮(N3)。
Cu(I)为任何一价铜盐，包括CuI、CuCl、CuBr、Cu2O、CuSCN、Cu(MeCN)4BF4、Cu(MeCN)4OTf、Cu(MeCN)4PF6；Cu(II)为任何二价铜盐，包括CuI2、CuCl2、CuBr2、CuO、Cu(OAc)2、Cu(TFA)、CuSO4、Cu(OTf)2、Cu(BF4)2、Cu(PF6)2、CuCO3、Cu(NO3)2、Cu(NO2)2。Ligand为配体，包括单齿、双齿、三齿和多齿配体。RT为室温，Na+resin为钠离子型树脂。
实施例五
该实施例重点介绍一种卤代烃类化合物为底物、过硫酸四丁基铵为硫酸根来源的有机硫酸盐化合物的制备方法，其通式如下：
Y为卤素原子，包括：氯、溴、碘。[Cu]为任何一价或二价铜盐，包括CuOAc、CuNO3、CuNO2、Cu2SO4、CuF、CuBr、CuI、CuOTf、CuBF4、CuPF6、CuClO4、Cu2CO3、CuTFA、Cu(OAc)2、Cu(NO3)2、Cu(NO2)2、CuSO4、CuF2、CuBr2、CuI2、Cu(OTf)2、Cu(BF4)2、Cu(PF6)2、CuCO3、Cu(TFA)2等。Ligand为配体，包括单齿、双齿、三齿和多齿配体。Base为有机碱或无机碱，包括LiHCO3、Li2CO3、Li3PO4、LiH2PO4、Li2HPO4、LiHC2O4、Li2C2O4、CH3COOLi、HCOOLi、LiOH、MeOLi、t-BuOLi、NaHCO3、Na2CO3、Na3PO4、NaH2PO4、Na2HPO4、NaHC2O4、Na2C2O4、CH3COONa、HCOONa、NaOH、MeONa、t-BuONa、KHCO3、K2CO3、K3PO4、KH2PO4、K2HPO4、KHC2O4、K2C2O4、CH3COOK、HCOOK、KOH、KOLi、t-BuOK、NH4HCO3、(NH4)2CO3、(NH4)3PO4、(NH4)H2PO4、(NH4)2HPO4、NH4HC2O4、(NH4)2C2O4、氨水、三乙胺、二异丙胺、三甲胺、哌啶、吡啶。RT为室温，Na+resin为钠离子型树脂。
实施例六
该实施例重点介绍烷基硼类化合物为底物、过硫酸铵为硫酸根来源的有机硫酸盐化合物的制备方法，其通式如下：
R是取代的烃基。取代基包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基的数量为一个或多个。[B]为硼酸(B(OH)2)、三氟硼酸盐(-BF3)和双联嚬哪醇硼酸酯(Bpin)，RT为室温，Na+resin为钠离子型树脂。
实施例七
该实施例重点介绍羟基类化合物为底物、过硫酸钾为硫酸根来源的有机硫酸盐化合物的制备方法，其通式如下：
R同实施例六，Na+resin为钠离子型树脂。
实施例八
该实施例重点介绍一种以1,3-二羰基类化合物为底物、过硫酸钾为硫酸根来源的有机硫酸盐化合物的制备方法，其通式如下：
其中R1包括≥C1的芳基、烃基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基R1的数量为1～5；R2包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基；R3包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基。
Ag(I)为任何一价银盐，包括AgOAc、AgNO3、AgNO2、Ag2SO4、AgF、AgBr、AgI、AgOTf、AgBF4、AgPF6、AgClO4、Ag2CO3、AgTFA等。Ligand为配体，包括单齿、双齿、三齿和多齿配体。
实施例九
该实施例重点介绍一种(杂)芳烃为底物、过硫酸铵为硫酸根来源的芳基硫酸盐化合物的制备方法，其通式如下：
其中R1包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基R1的数量为1～5；
Ag(I)为任何一价银盐，包括AgOAc、AgNO3、AgNO2、Ag2SO4、AgF、AgBr、AgI、AgOTf、AgBF4、AgPF6、AgClO4、Ag2CO3、AgTFA等。Ligand为配体，包括单齿、双齿、三齿和多齿配体。Na+resin为钠离子型树脂。
实施例十
该实施例重点介绍一种以芳基环丙烷类化合物为底物、过硫酸铵为硫酸根来源的有机硫酸盐化合物的制备方法，其通式如下：
其中R1,R2,R3,R4,R5,R6的结构包括H、芳基、≥C1的烃基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基R1的数量为1～5。
Ag(I)为任何一价银盐，包括AgOAc、AgNO3、AgNO2、Ag2SO4、AgF、AgBr、AgI、AgOTf、AgBF4、AgPF6、AgClO4、Ag2CO3、AgTFA等。Ligand为配体，包括单齿、双齿、三齿和多齿配体。Na+resin为钠离子型树脂。
实验例一4-氯苄基硫酸钠的制备
向4mL的反应瓶中依次加入4-氯苯乙酸(0.2mmol)，亚硝酸银(0.01mmol)，配体(0.01mmol)，过硫酸铵(0.6mmol)，四丁基硫酸氢铵(0.24mmol)，磷酸二氢钾(0.24mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入1mL的二氯甲烷，并至于室温下反应11小时。待反应结束后，向体系中加入200mg碳酸氢钠淬灭反应，然后过滤收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出4-氯苄基硫酸四丁基铵，最后将其进行离子交换即可得到4-氯苄基硫酸钠(35.7mg,73％)。1H NMR(400MHz,CD3OD,298K,δ):7.40(d,J＝8.8Hz,2H),7.34(d,J＝8.8Hz,2H),4.99(s,2H)；13C NMR(101MHz,CD3OD,298K,δ):136.6,134.6,130.4,129.3,69.6.
实验例二4-氟苄基硫酸钠的制备
实验流程见实例一，4-氟苄基硫酸钠(34.7mg,76％)。1H NMR(400MHz,CD3OD,298K,δ):7.47-7.39(m,2H),7.13-7.02(m,2H),4.99(s,2H)；13C NMR(101MHz,CD3OD,298K,δ):164.0(d,J＝244.8Hz),134.0,131.2(d,J＝8.3Hz),116.0(d,J＝21.8Hz),70.0；19F NMR(376MHz,CD3OD,298K,δ):-116.67.
实验例三4-溴苄基硫酸钠的制备
实验流程见实例一，4-溴苄基硫酸钠(40.1mg,72％)。1H NMR(400MHz,CD3OD,298K,δ):7.50(d,J＝8.4Hz,2H),7.34(d,J＝8.4Hz,2H),4.97(s,2H)；13C NMR(101MHz,CD3OD,298K,δ):137.3,132.5,130.8,122.8,69.8.实验例四4-硝基苄基硫酸钠的制备
实验流程见实例一，4-硝基苄基硫酸钠(31.6mg,62％)。1H NMR(400MHz,CD3OD,298K,δ):7.50(d,J＝8.4Hz,2H),7.34(d,J＝8.4Hz,2H),4.97(s,2H)；13C NMR(101MHz,CD3OD,298K,δ):137.3,132.5,130.8,122.8,69.8.实验例五4-甲磺酰基苄基硫酸钠的制备
实验流程见实例一，4-甲磺酰基苄基硫酸钠(36.9mg,64％)。1H NMR(400MHz,CD3OD,298K,δ):7.95(d,J＝8.4Hz,2H),7.68(d,J＝8.4Hz,2H),5.13(s,2H),3.12(s,3H)；13C NMR(101MHz,CD3OD,298K,δ):144.7,141.3,129.3,128.5,69.4,44.4.
实验例六1,4-苯并二恶烷-2-硫酸钠的制备
实验流程见实例一，1,4-苯并二恶烷-2-硫酸钠(40.2mg,75％)。1H NMR(400MHz,CD3OD,298K,δ):6.93-6.81(m,4H),6.04(s,1H),4.20(ddd,J＝73.8,14.2,2Hz,2H)；13C NMR(101MHz,CD3OD,298K,δ):144.6,142.1,123.1,122.8,118.7,117.8,92.8,66.9.
实验例七4-甲氧基苄基硫酸钠的制备
实验流程见实例一，4-甲氧基苄基硫酸钠(20.2mg,42％)。1H NMR(400MHz,CD3OD,298K,δ):7.33(d,J＝8.8Hz,2H),6.89(d,J＝8.8Hz,2H),4.94(s,2H),3.79(s,3H)；13C NMR(101MHz,CD3OD,298K,δ):161.1,130.9,129.8,114.7,70.7,55.7.实验例八4-碘苄基硫酸钠的制备
实验流程见实例一，4-碘苄基硫酸钠(37.0mg,55％)。1H NMR(400MHz,CD3OD,298K,δ):7.70(d,J＝8Hz,2H),7.20(d,J＝8.4Hz,2H),4.96(s,2H)；13C NMR(101MHz,CD3OD,298K,δ):138.6,137.9,130.9,94.0,69.9.实验例九α-异丙基-4-氯苄基硫酸钠的制备
实验流程见实例一，α-异丙基-4-氯苄基硫酸钠(35.0mg,65％)。1H NMR(400MHz,CD3OD,298K,δ):7.34-7.27(m,4H),5.00(d,J＝6.5Hz,1H),2.04(dq,J＝13.5,6.7Hz,1H),0.96(d,J＝6.8Hz,3H),0.84(d,J＝6.8Hz,3H)；13C NMR(101MHz,CD3OD,298K,δ):140.9,133.9,129.8,128.8,85.8,35.8,18.9,18.5.
实验例十4-氰基苄基硫酸钠的制备
实验流程见实例一，4-氰基苄基硫酸钠(24.5mg,52％)。1H NMR(400MHz,CD3OD,298K,δ):7.72(d,J＝8.4Hz,2H),7.60(d,J＝8.8Hz,2H),5.09(s,2H)；13C NMR(101MHz,CD3OD,298K,δ):144.0,133.3,129.3,119.7,112.5,69.4.
实验例十一α-邻苯二甲酰亚胺苄基硫酸钠的制备
实验流程见实例一，α-邻苯二甲酰亚胺苄基硫酸钠(47.6mg,67％)。1H NMR(400MHz,CD3OD,298K,δ):7.90-7.78(m,4H),7.54(d,J＝7.6Hz,2H),7.40-7.30(m,3H),7.29(s,1H)；13C NMR(101MHz,CD3OD,298K,δ):168.3,137.8,135.7,133.1,129.4,129.2,127.1,124.5,78.7.
实验例十二α-烯丙基-4-氟苄基硫酸钠的制备
实验流程见实例一，α-烯丙基-4-氟苄基硫酸钠(25.8mg,48％)。1H NMR(400MHz,CD3OD,298K,δ):7.38(dd,J＝8.7,5.5Hz,2H),7.03(t,J＝8.8Hz,2H),5.72(ddt,J＝17.2,10.2,7.0Hz,1H),5.31(t,J＝6.6Hz,1H),5.04-4.95(m,2H),2.68(dtd,J＝28.4,14.2,6.8Hz,2H)；13C NMR(101MHz,CD3OD,298K,δ):163.6(d,J＝243.9Hz),138.3,134.7,129.7(d,J＝8.1Hz),118.1,115.6(d,J＝21.6Hz),80.5),42.7；19F NMR(376MHz,CD3OD,298K,δ):-117.54(tt,J＝8.9,5.4Hz).
实验例十三6-氯吡啶-3-甲基硫酸钠的制备
实验流程见实例一，6-氯吡啶-3-甲基硫酸钠(24.6mg,50％)。1H NMR(400MHz,CD3OD,298K,δ):8.41(d,J＝2.0Hz,1H),7.89(dd,J＝8,2.4Hz,1H),7.45(d,J＝8Hz,1H),5.05(s,2H)；13C NMR(101MHz,CD3OD,298K,δ):151.7,150.0,140.6,133.7,125.4,67.1.
实验例十四硫酸化的扎托布洛芬的制备
实验流程见实例一，扎托布洛芬硫酸钠(41.0mg,55％)。1H NMR(400MHz,CD3OD,298K,δ):8.13(dd,J＝8.0,1.2Hz,1H),7.66-7.61(m,2H),7.50(ddd,J＝15.2,9.2,1.6Hz,2H),7.39-7.29(m,2H),5.46(q,J＝6.8Hz,1H),4.36(s,2H),1.58(d,J＝6.4Hz,3H)；13C NMR(101MHz,CD3OD,298K,δ):193.1,146.8,141.7,138.9,137.2,134.6,133.9,132.3,132.1,131.9,128.0,126.2,77.1,51.7,23.7.
实验例十五硫酸化的洛索洛芬的制备
实验流程见实例一，硫酸化的洛索洛芬(34.6mg,54％)。1H NMR(400MHz,CD3OD,298K,δ):7.32(d,J＝8.0Hz,2H),7.14(d,J＝8.4Hz,2H),5.44(q,J＝6.8Hz,1H),3.05(dd,J＝14.0,4.4Hz,1H),2.53(dd,J＝13.7,9.3Hz,1H),2.45-2.25(m,2H),2.05(dddd,J＝10.2,8.1,7.1,5.3Hz,2H),1.98-1.70(m,2H),1.63-1.52(m,4H)；13C NMR(101MHz,CD3OD,298K,δ):222.8,141.9,140.5,129.8,127.2,77.8,52.0,39.0,36.1,30.0,23.5,21.4.
实验例十六α-甲基-4-苯基苄基硫酸钠的制备
向4mL的反应瓶中依次加入4-乙基联苯(0.2mmol)，亚硝酸银(0.02mmol)，配体(0.02mmol)，过硫酸铵(0.6mmol)，三乙胺(0.3mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入1mL的二氯甲烷，并至于室温下反应8小时。待反应结束后，向体系中加入200mg碳酸氢钠淬灭反应，然后过滤收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出α-甲基-4-苯基苄基硫酸四丁基铵，最后将其进行离子交换即可得到α-甲基-4-苯基苄基硫酸钠(48.0mg,80％)。1HNMR(400MHz,CD3OD,298K,δ):7.58(td,J＝6.9,6.4,1.9Hz,4H),7.49(d,J＝8.1Hz,2H),7.41(dd,J＝8.3,6.9Hz,2H),7.34–7.27(m,1H),5.52(q,J＝6.6Hz,1H),1.64(d,J＝6.5Hz,3H)；13C NMR(101MHz,MHz,CD3OD,298K,δ):143.1,142.1,141.6,129.8,128.2,127.9,127.8,127.6,77.7,23.6.
实验例十七α-甲基-4-邻苯二甲酰亚胺苄基硫酸钠的制备
实验流程见实例十六，α-甲基-4-邻苯二甲酰亚胺苄基硫酸钠(80％，1H-NMR产率)。1H NMR(400MHz,DMSO-d6,298K,δ):7.99–7.88(m,4H),7.48(d,J＝8.3Hz,2H),7.38(d,J＝8.3Hz,2H),5.30(q,J＝6.6Hz,1H),1.48(d,J＝6.6Hz,3H)；13C NMR(101MHz,DMSO-d6,298K,δ):167.1,144.0,134.8,131.6,130.4,126.9,126.3,123.4,73.2,23.5.
实验例十八α-丙基-4-(4-氰基苯)苄基硫酸四丁基铵的制备
实验流程见实例十六，α-丙基-4-(4-氰基苯)苄基硫酸四丁基铵(65％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.67–7.60(m,4H),7.50–7.44(m,4H),5.33(t,J＝6.7Hz,1H),3.24–3.11(m,8H),1.95(dddd,J＝13.6,10.5,6.9,5.3Hz,1H),1.74(ddt,J＝13.4,10.2,6.0Hz,1H),1.62–1.47(m,8H),1.35(h,10H),0.92(t,J＝7.3Hz,12H),0.85(t,J＝7.4Hz,3H)；13C NMR(101MHz,CDCl3,298K,δ):145.6,143.8,137.1,132.4,127.4,127.3,126.51,118.9,110.2,78.4,58.4,39.7,23.7,19.5,18.4,13.9,13.5.
实验例十九α-甲基-4-二氟甲氧基苄基硫酸钠的制备
实验流程见实例十六，α-甲基-4-二氟甲氧基苄基硫酸钠(60％，1H-NMR产率)。1HNMR(400MHz,CD3OD,298K,δ):7.44(d,J＝8.6Hz,2H),7.10(d,J＝8.7Hz,2H),6.79(t,J＝74.3Hz,1H),5.46(q,J＝6.6Hz,1H),1.59(d,J＝6.6Hz,3H)；13C NMR(101MHz,CD3OD,298K,δ):152.1,141.1,128.7,119.8,117.7(t,J＝257.4Hz),77.2,23.6；19F NMR(376MHz,CD3OD,298K,δ):-83.13.
实验例二十α-甲基-4-((4-乙基苯甲酰基)氧基)苄基硫酸钠的制备
实验流程见实例十六，α-甲基-4-((4-乙基苯甲酰基)氧基)苄基硫酸钠(45％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):8.08(d,J＝8.0Hz,2H),7.50(d,J＝8.4Hz,2H),7.38(d,J＝8.1Hz,2H),7.18(d,J＝8.4Hz,2H),5.51(q,J＝6.6Hz,1H),2.75(q,J＝7.6Hz,2H),1.63(d,J＝6.6Hz,3H),1.27(t,J＝7.6Hz,3H)；13C NMR(101MHz,CD3OD,298K,δ):166.7,152.2,151.7,141.8,131.2,129.3,128.3,128.1,122.5,77.4,29.9,23.7,15.7.
实验例二十一α-甲基-4-(1-硝基-4-甲基苯)苄基硫酸四丁基铵的制备
实验流程见实例十六，α-甲基-4-(1-硝基-4-甲基苯)苄基硫酸四丁基铵(72％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.59(s,1H),7.47(d,J＝7.9Hz,2H),7.38(d,J＝1.7Hz,1H),7.28(d,J＝7.8Hz,1H),7.19(d,J＝7.9Hz,2H),5.54(d,J＝6.5Hz,1H),3.30–2.93(m,8H),2.43(s,3H),1.64(d,J＝6.6Hz,3H),1.61–1.48(m,8H),1.35(h,J＝7.4Hz,8H),0.94(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3):149.0,143.8,138.44,135.8,133.3,133.0,131.8,127.5,126.6,124.1,74.7,58.6,23.8,23.1,20.8,19.6,13.5.
实验例二十二α-氰基-4-甲氧基苄基硫酸四丁基铵的制备
实验流程见实例十六，α-甲基-4-(1-硝基-4-甲基苯)苄基硫酸四丁基铵(89％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.41(d,J＝8.7Hz,2H),6.81(d,J＝8.8Hz,2H),5.92(s,1H),3.73(s,3H),3.14–3.07(m,8H),1.56–1.45(m,8H),1.30(h,J＝7.4Hz,8H),0.88(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):160.1,128.7,125.9,118.2,113.7,65.6,58.1,55.1,23.5,19.3,13.4.
实验例二十三α-甲基甲酸-2-甲氧基苄基硫酸四丁基铵的制备
实验流程见实例十六，α-甲基甲酸-2-甲氧基苄基硫酸四丁基铵(85％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.50(dd,J＝7.7,1.7Hz,1H),7.20(ddd,J＝8.3,7.4,1.7Hz,1H),6.85(td,J＝7.5,1.1Hz,1H),6.79(dd,J＝8.3,1.0Hz,1H),6.08(s,1H),3.74(s,3H),3.61(s,3H),3.20–3.11(m,8H),1.57–1.45(m,8H),1.32(h,J＝7.4Hz,8H),0.90(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):171.5,156.7,129.4,129.5,125.5,120.4,110.9,71.6,58.2,55.8,52.0,23.8,19.5,13.67.
实验例二十四α-二乙氧基磷酸-4-甲氧基苄基硫酸四丁基铵的制备
实验流程见实例十六，α-二乙氧基磷酸-4-甲氧基苄基硫酸四丁基铵(52％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.44(dd,J＝8.8,2.1Hz,2H),6.79(d,J＝8.5Hz,2H),5.67(d,J＝14.8Hz,1H),4.20–4.07(m,4H),3.74(s,3H),3.18–3.06(m,8H),1.53(p,J＝8.1,7.6Hz,8H),1.35(p,J＝7.4Hz,8H),1.22(t,6H),0.94(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):159.22,129.3(d,J＝6.0Hz),113.4(d,J＝2.2Hz),74.0(d,J＝168.0Hz),63.8,56.9(d,J＝327.0Hz),23.9,19.7,16.5,16.4,13.7；31P NMR(162MHz,CDCl3,298K,δ):18.34.
实验例二十五5-甲氧基-3-氧代-2,3-二氢-1H-茚-1-基硫酸钠的制备
实验流程见实例十六，5-甲氧基-3-氧代-2,3-二氢-1H-茚-1-基硫酸钠(90％，1H-NMR产率)。1H NMR(400MHz,DMSO-d6,298K,δ):7.70(d,J＝8.3Hz,1H),7.32(dd,J＝8.5,2.7Hz,1H),7.08(s,1H),5.69(dd,J＝6.5,2.4Hz,1H),3.82(s,3H),3.05(dd,J＝19.1,6.7Hz,1H),2.69(dd,J＝19.0,2.5Hz,1H)；13C NMR(101MHz,DMSO-d6,298K,δ):202.8,160.5,146.1,137.9,128.3,123.5,104.1,71.1,55.7,45.3.
实验例二十六硫酸化的吲哚美辛的制备
实验流程见实例十六，吲哚美辛硫酸四丁基铵(40％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.64(d,J＝8.5Hz,2H),7.39(d,J＝8.5Hz,2H),6.92(d,J＝2.5Hz,1H),6.74(d,J＝9.0Hz,1H),6.64(dd,J＝9.0,2.5Hz,1H),5.19(s,2H),3.91(s,2H),3.78(s,3H),3.64(s,3H),3.15–3.06(m,8H),1.56–1.43(m,8H),1.27(h,J＝7.3Hz,8H),0.88(t,J＝7.3Hz,12H)；13C NMR(400MHz,CDCl3,298K,δ):171.6,168.2,155.8,139.2,135.3,133.8,131.4,131.3,130.1,129.0,116.0,114.8,113.0,101.7,59.2,58.3,55.7,52.1,30.0,23.8,19.6,13.6.
实验例二十七α-苯基-4-氯苄基硫酸四丁基铵的制备
实验流程见实例十六，α-苯基-4-氯苄基硫酸四丁基铵(68％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.34–7.29(m,4H),7.24–7.15(m,5H),6.35(s,1H),3.07–2.96(m,8H),1.50–1.37(m,8H),1.26(h,J＝7.4Hz,8H),0.89(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):142.0,141.2,132.5,129.0,128.0,127.9,127.5,127.2,79.0,58.2,23.7,19.6,13.6.
实验例二十八1-(2-乙酰氧基苯基)羰基苯并呋喃丁基硫酸四丁基铵的制备
实验流程见实例十六，1-(2-乙酰氧基苯基)羰基苯并呋喃丁基硫酸四丁基铵(54％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.87(d,J＝8.4Hz,2H),7.44(d,J＝8.2Hz,1H),7.26–7.20(m,1H),7.14–7.07(m,4H),5.67(t,J＝7.2Hz,1H),3.14–3.02(m,8H),2.28(s,3H),2.15–2.03(m,1H),2.00–1.89(m,1H),1.54–1.39(m,9H),1.27(h,J＝7.4Hz,9H),0.87(t,J＝7.2Hz,15H)；13C NMR(101MHz,CDCl3,298K,δ):190.6,168.8,162.3,154.1,153.7,136.5,131.3,126.5,124.7,123.3,121.6,121.4,118.0,111.5,70.4,58.2,36.3,23.8,21.2,19.6,18.6,13.9,13.6.
实验例二十九α-甲基-4-(5-(乙氧基羰基)噻吩)苄基硫酸钠的制备
实验流程见实例十六，α-甲基-4-(5-(乙氧基羰基)噻吩)苄基硫酸钠(56％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.75(d,J＝3.9Hz,1H),7.66(d,J＝8.3Hz,2H),7.48(d,J＝8.3Hz,2H),7.42(d,J＝3.9Hz,1H),5.49(q,J＝6.6Hz,1H),4.34(q,J＝7.1Hz,2H),1.61(d,J＝6.6Hz,3H),1.37(t,J＝7.1Hz,3H)；13C NMR(101MHz,CD3OD,298K,δ):163.7,152.4,145.1,135.6,133.7,133.2,127.9,127.0,125.0,77.4,62.4,23.6,14.6.
实验例三十硫酸化的表雄酮的制备
实验流程见实例十六，硫酸化的表雄酮(93％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.35(d,J＝8.2Hz,2H),6.77(d,J＝8.3Hz,2H),5.63(s,1H),4.65(tt,J＝10.8,4.9Hz,1H),3.73(s,3H),3.23–3.11(m,8H),2.38(dd,J＝19.2,8.8Hz,1H),1.99(dd,J＝19.0,9.2Hz,1H),1.93–1.83(m,1H),1.71(dt,J＝26.1,10.7Hz,4H),1.51(tt,J＝17.5,9.8Hz,13H),1.33(h,J＝6.9Hz,10H),1.22(tt,J＝14.3,7.1Hz,5H),1.08(t,J＝7.3Hz,1H),0.91(t,J＝7.3Hz,14H),0.78(d,J＝13.8Hz,6H),0.64(dt,J＝11.1,5.4Hz,1H)；13CNMR(101MHz,CDCl3,298K,δ):170.43,170.41,159.4,129.0,128.7,128.7,113.5,76.2,73.9,58.3,55.2,54.3,51.4,47.8,44.8,44.7,36.7,36.6,35.9,35.6,35.0,33.7,33.5,31.5,30.8,28.3,28.2,27.3,27.1,23.8,21.8,20.4,19.6,13.8,13.7,12.3.
实验例三十一1-苯基乙烷-1,2-双硫酸钠的制备
向4mL的反应瓶中依次加入苯乙烯(0.2mmol)，碳酸银(0.01mmol)，配体(0.02mmol)，过硫酸钾(0.6mmol)，四丁基过硫酸钾(0.2mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入1mL的二氯甲烷，并至于室温下反应10小时。待反应结束后，向体系中加入200mg碳酸氢钠淬灭反应，然后过滤收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出1-苯基乙烷-1,2-双硫酸四丁基铵，最后将其进行离子交换即可得到1-苯基乙烷-1,2-双硫酸铵钠(80％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.58–7.40(m,5H),5.58(dd,J＝6.7,4.4Hz,1H),4.34(dd,J＝11.1,6.8Hz,1H),4.27(dd,J＝11.1,4.3Hz,1H)；13C NMR(101MHz,D2O,298K,δ):136.2,128.9,128.7,126.8,78.7,70.0.
实验例三十二1-(4-苯基)苯基乙烷-1,2-双硫酸钠的制备
实验流程见实例三十一，1-(4-苯基)苯基乙烷-1,2-双硫酸钠(80％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.69(d,J＝7.6Hz,1H),7.58–7.46(m,5H),7.42(d,J＝7.2Hz,2H),7.31(d,J＝6.8Hz,1H),5.66(dd,J＝6.4,4.8Hz,1H),4.19–4.10(m,2H)；13C NMR(101MHz,D2O,298K,δ):141.0,139.8,133.7,129.9,129.3,128.6,128.5,128.0,127.6,127.0,75.8,69.6.
实验例三十三1-(3-氯苯基)乙烷-1,2-双硫酸钠的制备
实验流程见实例三十一，1-(3-氯苯基)乙烷-1,2-双硫酸钠(58％，1H-NMR产率)。1HNMR(400MHz,D2O,298K,δ):7.56(s,1H),7.48–7.41(m,3H),5.59(dd,1H),4.38–4.26(m,2H)；13C NMR(101MHz,D2O,298K,δ):138.3,133.8,130.2,128.8,126.8,125.2,77.9,69.8.
实验例三十四1-(3-溴苯基)乙烷-1,2-双硫酸钠的制备
实验流程见实例三十一，1-(3-氯苯基)乙烷-1,2-双硫酸钠(66％，1H-NMR产率)。1HNMR(400MHz,D2O,298K,δ):7.64(d,J＝8.4Hz,2H),7.41(d,J＝8.4Hz,2H),5.56(dd,J＝4.4,2.0Hz,1H),4.29(qd,J＝11.1,5.5Hz,2H)；13C NMR(101MHz,D2O,298K,δ):135.5,131.6,128.7,122.2,78.0,69.7.
实验例三十五1-(4-(甲氧羰基)苯基)乙烷-1,2-双硫酸钠的制备
实验流程见实例三十一，1-(4-(甲氧羰基)苯基)乙烷-1,2-双硫酸钠(74％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):8.08(d,J＝8.4Hz,2H),7.64(d,J＝8.4Hz,2H),5.71-5.66(m,1H),4.40-4.31(m,2H),3.97(s,3H)；13C NMR(101MHz,D2O,298K,δ):169.0,141.9,129.7,129.7,78.0,69.8,52.7.
实验例三十六1-(4-氟苯基)乙烷-1,2-双硫酸钠的制备
实验流程见实例三十一，1-(4-氟苯基)乙烷-1,2-双硫酸钠(72％，1H-NMR产率)。1HNMR(400MHz,D2O,298K,δ):7.54–7.48(m,1H),7.20(t,J＝8.9Hz,1H),5.58(dd,J＝6.7,4.5Hz,1H),4.32(dd,J＝11.1,6.7Hz,1H),4.26(dd,J＝11.1,4.4Hz,1H)；13C NMR(101MHz,D2O,298K,δ):162.6(d,J＝244.5Hz),132.2(d,J＝3.2Hz),128.9(d,J＝8.6Hz),115.4(d,J＝21.8Hz),78.0,69.9；19F NMR(376MHz,D2O,298K,δ):-113.92.
实验例三十七2-苯基戊烷-1,2-二硫酸钠的制备
实验流程见实例三十一，2-苯基戊烷-1,2-二硫酸钠(58％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.47(d,J＝7.5Hz,2H),7.31(t,J＝7.6Hz,2H),7.21(t,J＝7.3Hz,1H),4.17–4.11(m,2H),1.86(dtd,J＝25.6,13.8,4.8Hz,2H),1.38–1.31(m,1H),1.04(dd,J＝12.1,6.9Hz,1H),0.84(t,J＝7.4Hz,3H)；13C NMR(101MHz,CD3OD,298K,δ):145.0,128.9,127.7,126.8,76.7,75.8,42.1,17.4,14.8.
实验例三十八1-萘乙烷-1,2-双硫酸钠的制备
实验流程见实例三十一，1-萘乙烷-1,2-双硫酸钠(53％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):8.05–7.88(m,4H),7.60(ddd,J＝9.9,7.4,2.4Hz,3H),5.79(dd,J＝6.9,4.3Hz,1H),4.46(dd,J＝11.2,6.9Hz,1H),4.39(dd,J＝11.1,4.3Hz,1H)；13C NMR(101MHz,D2O,298K,δ):133.8,133.0,132.7,128.4,128.1,127.7,126.7,126.7,126.6,126.3,124.24,78.8,70.0.
实验例三十九1-(4-氰基苯基)乙烷-1,2-双硫酸钠的制备
实验流程见实例三十一，1-(4-氰基苯基)乙烷-1,2-双硫酸钠(48％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.86(d,J＝8.4Hz,2H),7.68(d,J＝8.4Hz,2H),5.68(t,J＝5.2Hz,1H),4.40–4.30(m,2H)；13C NMR(101MHz,D2O,298K,δ):142.0,132.6,127.5,119.4,111.2,77.6,69.6.
实验例四十1-(4-硝基苯基)乙烷-1,2-双硫酸钠的制备
实验流程见实例三十一，1-(4-硝基苯基)乙烷-1,2-双硫酸钠(48％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):8.45(d,J＝8.6Hz,2H),7.88(d,J＝8.6Hz,2H),5.88(t,J＝4.8Hz,1H),4.56–4.46(m,2H)；13C NMR(101MHz,D2O,298K,δ):147.7,144.0,128.0,123.8,77.5,69.7.
实验例四十一1-(6-氯吡啶-3-)乙烷-1,2-双硫酸钠的制备
实验流程见实例三十一，1-(6-氯吡啶-3-)乙烷-1,2-双硫酸钠(48％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):8.46(d,J＝2.0Hz,1H),7.94(dd,J＝8.4,2.0Hz,1H),7.45(d,J＝8.4Hz,1H),5.61(t,J＝5.6Hz,1H),4.40(dd,J＝10.8,5.2Hz,1H),4.24(dd,J＝10.8,6.0Hz,1H)；13C NMR(101MHz,CD3OD,298K,δ):151.5,149.6,139.9,135.2,125.1,75.7,70.0.
实验例四十二2,3-二氢苯并呋喃-2,3-双硫酸钠的制备
实验流程见实例三十一，2,3-二氢苯并呋喃-2,3-双硫酸钠(82％，1H-NMR产率)。1HNMR(400MHz,D2O,298K,δ):7.65(d,J＝7.5Hz,1H),7.50(t,J＝7.8Hz,1H),7.19(t,J＝7.5Hz,1H),7.11(d,J＝8.2Hz,1H),6.48(s,1H),5.76(s,1H)；13C NMR(101MHz,D2O,298K,δ):158.9,132.4,127.0,123.0,121.8,111.2,105.1,81.6.
实验例四十三雌酮衍生物双硫酸钠的制备
实验流程见实例三十一，雌酮衍生物双硫酸钠(30％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.35(d,J＝8.1Hz,1H),7.24(d,J＝9.6Hz,2H),5.51(dd,J＝7.1,4.2Hz,1H),4.34–4.16(m,2H),2.86(t,J＝9.2Hz,2H),2.55(dd,J＝19.6,8.2Hz,1H),2.41–2.33(m,1H),2.20(dt,J＝19.2,8.3Hz,2H),2.11–1.92(m,2H),1.88–1.81(m,1H),1.71–1.50(m,3H),1.48–1.28(m,3H),0.87(s,3H)；13C NMR(101MHz,D2O,298K,δ):229.2,140.7,137.4,133.6,127.4,125.7,124.2,78.6,70.0,52.2,49.7,48.6,43.6,37.5,36.0,30.9,28.7,25.8,25.1,21.1,13.3.
实验例四十四1,1-二苯乙烷-1,2-二硫酸钠的制备
实验流程见实例三十一，1,1-二苯乙烷-1,2-二硫酸钠(50％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.45(d,J＝7.5Hz,4H),7.29(t,J＝7.6Hz,4H),7.21(t,J＝7.3Hz,2H),4.52(s,2H)；13C NMR(101MHz,CD3OD,298K,δ):145.8,128.9,128.1,127.9,78.2,74.3.
实验例四十五1,1,2-三苯乙烷-1,2-二硫酸钠的制备
实验流程见实例三十一，1,1,2-三苯乙烷-1,2-二硫酸钠(60％，1H-NMR产率)。1HNMR(400MHz,CD3OD,298K,δ):7.71(d,J＝7.7Hz,2H),7.31(t,J＝7.6Hz,2H),7.21(t,J＝7.3Hz,1H),7.14(dd,J＝7.6,1.8Hz,2H),7.10–6.97(m,8H),6.14(s,1H)；13C NMR(101MHz,CD3OD,298K,δ):146.7,145.6,138.4,130.4,128.9,128.5,128.2,128.0,127.9,127.6,127.3,127.3,84.9,81.5.
实验例四十六苯乙氰-3-硫酸钠的制备
向4mL的反应瓶中依次加入苯乙烯(0.2mmol)，氧化亚铜(0.02mmol)，配体(0.02mmol)，过硫酸钾(0.2mmol)，四丁基过硫酸钾(0.1mmol)和三甲基硅氰(0.5mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入0.85mL的二氯甲烷和0.15mL的水，并至于室温下反应6小时。待反应结束后，向体系中加入200mg碳酸氢钠淬灭反应，然后过滤收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出苯乙氰-3-硫酸四丁基铵，最后将其进行离子交换即可得到苯乙氰-3-硫酸钠(91％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.48–7.33(m,5H),4.49(dd,J＝8.2,5.7Hz,1H),4.28–4.18(m,2H)；13C NMR(101MHz,CD3OD,298K,δ):132.4,128.8,128.3,127.6,119.0,68.3,37.4.
实验例四十七1-(4-苯基)苯乙氰-3-硫酸钠的制备
实验流程见实例四十六，1-(4-苯基)苯乙氰-3-硫酸钠(92％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.67(d,J＝8.4Hz,2H),7.62(d,J＝8.3Hz,2H),7.53(d,J＝7.9Hz,2H),7.44(t,J＝7.6Hz,2H),7.38–7.31(m,1H),4.55(dd,J＝7.8,6.0Hz,1H),4.29–4.23(m,2H)；13C NMR(101MHz,CD3OD,298K,δ):141.5,140.1,131.4,128.5,128.2,127.3,127.3,126.6,118.8,68.2,37.0.
实验例四十八对氟苯乙腈-3-硫酸钠的制备
实验流程见实例四十六，对氟苯乙腈-3-硫酸钠(90％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.51(dd,J＝8.5,5.2Hz,2H),7.17(t,J＝8.6Hz,2H),4.53(dd,J＝6.7Hz,1H),4.29–4.20(m,2H)；13C NMR(101MHz,CD3OD,298K,δ):164.0,161.5,129.8,129.7,128.6,128.6,118.7,115.7,115.4,68.1,36.6.
实验例四十九对三氟甲基苯乙腈-3-硫酸钠的制备
实验流程见实例四十六，对三氟甲基苯乙腈-3-硫酸钠(79％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.66(d,J＝10.3Hz,2H),7.53(d,J＝10.2Hz,2H),4.56(dd,J＝5.5Hz,1H),4.32–4.26(m,2H)；13C NMR(101MHz,D2O,298K,δ):135.6,130.3,130.0,128.6,126.1,126.1,126.1,126.0,125.3,122.6,119.2,68.2,37.1；19F NMR(376MHz,D2O,298K,δ):-62.52.
实验例五十对乙酰氧基苯乙腈-3-硫酸钠的制备
实验流程见实例四十六，对乙酰氧基苯乙腈-3-硫酸钠(87％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.47(d,J＝8.1Hz,2H),7.16(d,J＝8.1Hz,2H),4.54(dd,J＝6.3Hz,1H),4.43–4.20(m,2H),2.31(s,3H)；13C NMR(101MHz,D2O,298K,δ):173.2,150.4,129.7,129.5,122.5,119.6,68.4,36.8,20.5.
实验例五十一对甲氧基苯乙腈-3-硫酸钠的制备
实验流程见实例四十六，对甲氧基苯乙腈-3-硫酸钠(45％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.41(d,J＝8.5Hz,2H),7.03(d,J＝8.5Hz,2H),4.49(dd,J＝6.3Hz,1H),4.36–4.28(m,2H),3.84(s,3H)；13CNMR(101MHz,D2O,298K,δ):159.1,129.4,123.8,120.0,114.7,68.6,55.4,36.5.
实验例五十二对叔丁基苯乙腈-3-硫酸钠的制备
实验流程见实例四十六，对叔丁基苯乙腈-3-硫酸钠(92％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.48(d,J＝8.1Hz,2H),7.38(d,J＝8.1Hz,2H),4.47(dd,J＝8.2,5.8Hz,1H),4.23(dd,J＝7.0,5.0Hz,2H),1.34(s,9H)；13C NMR(101MHz,CD3OD,298K,δ):151.5,129.3,127.3,125.8,119.0,68.3,37.0,34.1,30.3.实验例五十三对氯苯乙腈-3-硫酸钠的制备
实验流程见实例四十六，对氯苯乙腈-3-硫酸钠(82％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.51–7.36(m,4H),4.55(dd,J＝5.5Hz,1H),4.40–4.30(m,2H)；13CNMR(101MHz,D2O,298K,δ):134.2,130.1,129.5,129.2,119.5,68.3,36.7.
实验例五十四间氯苯乙腈-3-硫酸钠的制备
实验流程见实例四十六，间氯苯乙腈-3-硫酸钠(89％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.55–7.35(m,4H),4.56(dd,J＝7.1,5.2Hz,1H),4.41–4.32(m,2H)；13C NMR(101MHz,D2O,298K,δ):134.3,133.4,130.7,129.0,127.9,126.4,119.3,68.2,36.9.
实验例五十五α-甲基苯乙腈-3-硫酸钠的制备
实验流程见实例四十六，α-甲基苯乙腈-3-硫酸钠(88％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.62–7.42(m,5H),4.33(q,J＝9.9Hz,2H),1.79(s,3H)；13C NMR(101MHz,D2O,298K,δ):136.2,129.3,128.8,126.0,122.65,72.4,42.7,22.5.
实验例五十六α-氯联苯-β-硫酸四丁基铵的制备
向4mL的反应瓶中依次加入联苯乙烯(0.1mmol)，氯化亚铜(0.01mmol)，配体(0.01mmol)，过硫酸钾(0.1mmol)，四丁基过硫酸钾(0.05mmol)和氯化钾(0.3mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入1.0mL的二氯甲烷，并至于室温下反5小时。待反应结束后，向体系中加入200mg碳酸氢钠淬灭反应，然后过滤收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出α-氯联苯-β-硫酸四丁基铵(72％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.55(dd,J＝7.9,3.9Hz,5H),7.50(d,J＝8.2Hz,3H),7.42(t,J＝7.6Hz,2H),7.33(t,J＝7.3Hz,1H),5.29(dd,J＝8.2,5.8Hz,1H),4.43(dd,J＝2.7Hz,1H),4.41(dd,J＝1.8Hz,1H),1.64–1.58(m,8H),1.45–1.36(m,8H),0.97(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):141.2,140.5,137.6,128.7,128.1,127.4,127.2,127.0,70.6,60.7,58.6,23.9,19.6,13.6.
实验例五十七α-羟基联苯-β-硫酸四丁基铵的制备
向4mL的反应瓶中依次加入联苯乙烯(0.1mmol)，氧化亚铜(0.01mmol)，配体(0.01mmol)，过硫酸钾(0.1mmol)和四丁基过硫酸钾(0.05mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入0.9mL的乙腈和0.1mL的水，并至于室温下反4小时。待反应结束后，向体系中加入200mg碳酸氢钠淬灭反应，然后过滤收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出α-羟基联苯-β-硫酸四丁基铵(54％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.53(t,J＝8.1Hz,4H),7.45(d,J＝8.2Hz,2H),7.39(t,J＝7.6Hz,2H),7.29(dd,J＝14.6,7.3Hz,1H),5.03(dd,J＝8.7,2.6Hz,1H),4.24–4.08(m,2H),3.29–3.11(m,8H),1.62–1.55(m,8H),1.43–1.31(m,8H),0.96(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):140.7,140.1,139.6,128.6,127.0,126.8,126.8,126.7,73.1,58.4,23.7,19.5,13.5.
实验例五十八α-叠氮联苯-β-硫酸四丁基铵的制备
向4mL的反应瓶中依次加入联苯乙烯(0.2mmol)，水合三氟乙酸铜(0.02mmol)，配体(0.02mmol)，三甲基叠氮(0.5mmol)，过硫酸钾(0.6mmol)和四丁基过硫酸钾(0.1mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入1.0mL的乙腈，并至于室温下15小时。待反应结束后，向体系中加入200mg碳酸氢钠淬灭反应，然后过滤收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出α-叠氮联苯-β-硫酸四丁基铵(46％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.35–7.16(m,5H),4.89(dd,J＝9.1,4.2Hz,1H),4.17(dd,J＝11.1,4.2Hz,1H),4.04–3.98(m,1H),3.33–3.13(m,32H),1.60–1.52(m,32H),1.40–1.31(m,33H),0.91(t,J＝7.3Hz,49H)；13C NMR(101MHz,CDCl3,298K,δ):136.5,128.4,128.0,126.9,69.8,64.7,58.3,23.7,19.4,13.4.
实验例五十九3-苯基正丙基硫酸四丁基铵的制备
向4mL的反应瓶中依次加入(3-氯丙基)苯(0.2mmol)，溴化亚铜(0.02mmol)，配体(0.02mmol)，过硫酸四丁基铵(0.6mmol)，联硼酸频那醇酯(0.3mmol)，甲醇锂(0.6mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入2mL的丙酮，并至于60℃下反应18小时。待反应结束后，过滤收集有机相，将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出3-苯基正丙基硫酸四丁基铵(87％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.03(d,J＝7.4Hz,2H),6.91–6.97(m,3H),3.81(t,J＝6.6Hz,2H),3.02-3.06(m,8H),2.50(t,J＝7.8Hz,2H),1.71-1.78(m,2H),1.36-1.44(m,8H),1.15-1.24(m,8H),0.76(t,J＝7.4Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):141.3,127.8,127.6,125.1,65.7,57.8,31.7,30.9,23.2,19.0,13.1.
实验例六十4-炔基戊烷硫酸四丁基铵的制备
实验流程见实例五十九，4-炔基戊烷硫酸四丁基铵(84％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):3.78(t,J＝6.3Hz,2H),3.00–3.04(m,8H),3.78(td,J＝7.3,2.6Hz,2H),1.71(t,J＝2.6Hz,1H),1.57–1.64(m,2H),1.35-1.43(m,8H),1.13–1.22(m,8H),0.73(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):83.4,68.0,65.0,57.9,28.3,23.3,19.1,14.7,13.1.
实验例六十一萘-1-基甲基硫酸四丁基铵的制备
实验流程见实例五十九，萘-1-基甲基硫酸四丁基铵(84％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):8.07–8.09(m,1H),7.53–7.59(m,2H),7.28(d,J＝7.0Hz,1H),7.22–7.25(m,2H),7.15(t,J＝7.6Hz,1H),5.21(s,2H),2.70–2.74(m,8H),1.06-1.14(m,8H),0.94–1.03(m,8H),0.63(t,J＝7.2Hz,12H)；13CNMR(101MHz,CDCl3,298K,δ):132.9,132.5,131.3,128.1,127.7,126.3,125.6,125.2,124.6,124.0,66.5,57.2,22.8,18.8,13.0.
实验例六十二2-(4-氟苯基)乙基硫酸四丁基铵的制备
实验流程见实例五十九，2-(4-氟苯基)乙基硫酸四丁基铵(87％，1H-NMR产率)。1HNMR(400MHz,CDCl3,298K,δ):7.14-7.18(m,2H),6.88(t,J＝8.6Hz,2H),4.13(t,J＝7.4Hz,2H),3.16-3.21(m,8H),2.92(t,J＝7.3Hz,2H),1.52–1.60(m,8H),1.31–1.40(m,8H),0.93(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):161.4(d,J＝242.4Hz),134.5(d,J＝3.1Hz),130.4(d,J＝7.7Hz),114.8(d,J＝21Hz),67.4,58.6,35.2,23.9,19.7,13.7；19FNMR(376MHz,CDCl3,298K,δ):-117.6(m).
实验例六十三2-噻吩基乙基硫酸四丁基铵的制备
实验流程见实例五十九，2-噻吩基乙基硫酸四丁基铵(60％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.07(d,J＝5.0Hz,1H),6.84–6.88(m,2H),4.20(t,J＝7.4Hz,2H),3.16–3.23(m,10H),1.55–1.63(m,8H),1.34–1.43(m,8H),0.96(t,J＝7.3Hz,12H)；13CNMR(101MHz,CDCl3,298K,δ):140.8,126.7,125.2,123.3,67.2,58.6,30.3,23.9,19.7,13.7.
实验例六十四4-(1-环己基-1H-四唑-5-基)丁基硫酸四丁基铵的制备
实验流程见实例五十九，4-(1-环己基-1H-四唑-5-基)丁基硫酸四丁基铵(87％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):4.09–4.17(m,1H),3.94(t,J＝6.1Hz,2H),3.15–3.19(m,8H),2.78(t,J＝7.7Hz,2H),1.77-1.86(m,8H),1.62–1.68(m,3H),1.50–1.58(m,8H),1.36–1.45(m,2H),1.25-1.34(m,8H),1.14–1.23(m,1H),0.85(t,J＝7.4Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):153.3,64.9,57.7,56.3,32.2,27.8,24.2,24.1,23.2,23.0,21.7,18.8,12.8.
实验例六十五咖啡因衍生物硫酸四丁基铵的制备
实验流程见实例五十九，咖啡因衍生物硫酸四丁基铵(55％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.87–7.88(m,1H),4.64–4.66(m,2H),4.31–4.34(m,2H),3.54–3.55(m,3H),3.35–3.36(m,3H),3.18–3.23(m,8H),1.56–1.62(m,8H),1.36–1.42(m,8H),0.94–0.98(m,12H)；13C NMR(101MHz,CDCl3,298K,δ):155.4,151.9,148.9,143.4,106.5,65.6,58.8,46.7,29.8,27.9,24.0,19.8,13.7.
实验例六十六睾酮衍生物硫酸四丁基铵的制备
实验流程见实例五十九，睾酮衍生物衍生物硫酸四丁基铵(77％，1H-NMR产率)。1HNMR(400MHz,CDCl3,298K,δ):5.67(s,1H),4.53(t,J＝8.3Hz,2H),4.00(t,J＝6.1Hz,2H),3.22–3.26(m,8H),1.89–2.44(m,12H),1.71–1.82(m,2H),1.57–1.65(m,10H),1.50–1.53(m,2H),1.34–1.45(m,8H),1.21–1.35(m,3H),1.15(s,3H),0.96(t,J＝7.0Hz,12H),0.77(s,3H)；13C NMR(101MHz,CDCl3,298K,δ):199.5,173.6,171.2,123.9,82.3,66.1,58.7,53.8,50.3,42.5,38.7,36.7,35.7,35.4,34.0,32.8,31.6,31.3,27.6,25.2,24.0,23.5,20.6,19.8,17.4,13.7,12.1.
实验例六十七阿达帕林衍生物硫酸钠的制备
实验流程见实例五十九，咖啡因衍生物硫酸四丁基铵，最后将其进行离子交换即可得到阿达帕林衍生物硫酸钠(66％，1H-NMR产率)。1H NMR(400MHz,DMSO-d6,298K,δ):8.64(s,1H),8.23(s,1H),8.18(d,J＝8.6Hz,1H),8.10(d,J＝8.6Hz,1H),7.99(d,J＝8.6Hz,1H),7.90(d,J＝8.7Hz,1H),7.66(dd,J＝8.4,2.1Hz,1H),7.58(d,J＝2.2Hz,1H),7.11(d,J＝8.5Hz,1H),4.38(t,J＝6.4Hz,2H),3.93(t,J＝6.2Hz,2H),3.86(s,3H),2.13(s,6H),2.00–2.07(m,5H),1.75(s,6H)；13C NMR(101MHz,DMSO-d6,298K,δ):165.9,158.6,140.4,138.1,135.6,131.4,130.9,130.3,129.9,128.6,126.7,126.1,125.8,125.1,125.1,124.1,112.7,32.5,62.1,55.4,36.6,36.6,28.6,28.4.
实验例六十八非布索坦衍生物硫酸钠的制备
实验流程见实例五十九，非布索坦衍生物硫酸四丁基铵，最后将其进行离子交换即可得到非布索坦衍生物硫酸钠(86％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):8.21(d,J＝2.2Hz,1H),8.17(dd,J＝8.8,2.3Hz,1H),7.27(d,J＝8.8Hz,1H),4.42(t,J＝6.2Hz,2H),4.17(t,J＝6.1Hz,2H),3.99(d,J＝6.4,2H),2.72(s,3H),2.09-2.22(m,3H),1.10(d,J＝6.7,6H)；13C NMR(101MHz,CD3OD,298K,δ):169.0,164.0,163.1,162.1,134.3,132.9,127.1,123.0,116.4,114.5,103.5,76.9,65.5,63.2,29.8,29.4,19.3,17.5.
实验例六十九萘普生衍生物硫酸钠的制备
实验流程见实例五十九，萘普生衍生物硫酸四丁基铵，最后将其进行离子交换即可得到萘普生衍生物硫酸钠(97％，1H-NMR产率)。1H NMR(400MHz,DMSO-d6,298K,δ):7.81(d,J＝8.9Hz,1H),7.77(d,J＝8.5Hz,1H),7.72(s,1H),7.39(d,J＝8.4Hz,1H),7.28(d,J＝2.4Hz,1H),7.14(dd,J＝8.9,2.5Hz,1H),4.01-4.12(m,2H),3.91(q,J＝7.1Hz,1H),3.86(s,3H),3.73(d,J＝6.3Hz,2H),1.74-1.81(m,2H),1.47(d,J＝7.0Hz,3H)；13CNMR(101MHz,DMSO-d6,298K,δ):173.9,157.2,135.7,133.3,129.2,128.4,127.0,126.2,125.5,118.7,105.7,62.2,61.6,55.1,44.4,28.5,18.5.
实验例七十非诺贝特衍生物硫酸铵的制备
实验流程见实例五十九，非诺贝特衍生物硫酸四丁基铵(93％，1H-NMR产率)。1HNMR(400MHz,CDCl3,298K,δ):7.65(dd,J＝8.6,3.3Hz,4H),7.39(d,J＝8.2Hz,2H),6.79(d,J＝8.6Hz,2H),4.24(t,J＝6.5Hz,2H),3.97(t,J＝6.1Hz,2H),3.16-3.20(m,8H),1.89-1.96(m,2H),1.52-1.59(m,14H),1.30-1.39(m,8H),0.91(t,J＝7.2Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):194.3,173.5,159.6,138.2,136.3,132.0,131.2,130.2,128.5,117.4,79.4,63.3,63.0,58.6,28.8,25.4,23.9,19.6,13.6.
实验例七十一氟比洛芬衍生物硫酸铵的制备
实验流程见实例五十九，氟比洛芬衍生物硫酸四丁基铵(91％，1H-NMR产率)。1HNMR(400MHz,CDCl3,298K,δ):7.48(d,J＝8.0Hz,2H),7.26-7.39(m,4H),7.04-7.11(m,2H),4.00-4.12(m,2H),3.96(t,J＝6.1Hz,2H),3.68(q,J＝7.1Hz,1H),3.17-3.21(m,8H),1.53-1.74(m,12H),1.46(d,J＝7.1Hz,3H),1.32-1.41(m,8H),0.93(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):173.9,159.6(d,J＝248.9Hz),142.0(d,J＝7.7Hz),135.5,130.7(d,J＝4.0Hz),128.9(d,J＝3.0Hz),128.4,127.6(d,J＝13.6Hz),127.6,123.6(d,J＝3.3Hz),115.1(d,J＝23.7Hz),66.2,64.8,58.6,45.0,45.0,26.0,25.2,23.9,19.6,18.4,13.6.实验例七十二塞来昔布衍生物硫酸铵的制备
实验流程见实例五十九，昔布衍生物硫酸四丁基铵(88％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.71(d,J＝8.4Hz,2H),7.39(d,J＝8.4Hz,2H),7.10(d,J＝7.9Hz,2H),7.03(d,J＝7.9Hz,2H),6.66(s,1H),3.96(t,J＝5.8Hz,2H),3.18-3.22(m,8H),3.08(t,J＝6.6Hz,2H),3.02(t,J＝7.7Hz,2H),2.31(s,3H),1.54-1.62(m,12H),1.31-1.43(m,10H),1.30-1.22(m,2H),0.92(t,J＝7.4Hz,12H),0.80(t,J＝7.3Hz,3H)；13C NMR(101MHz,CDCl3,298K,δ):145.2,143.8(q,J＝38.6Hz),142.1,139.7,139.6,129.6,128.6,127.9,125.6,125.4,121.0(q,J＝270.1Hz),106.1,66.5,58.6,47.9,47.9,30.4,26.7,25.3,23.8,21.2,19.8,19.6,13.6.
实验例七十三伊索克酸衍生物硫酸铵的制备
实验流程见实例五十九，伊索克酸衍生物硫酸四丁基铵(79％，1H-NMR产率)。1HNMR(400MHz,CDCl3,298K,δ):7.96(d,J＝2.2Hz,1H),7.75(d,J＝6.9Hz,1H),7.45(td,J＝7.4,1.3Hz,1H),7.30–7.37(m,2H),7.26(t,J＝3.7Hz,1H),6.90(d,J＝8.4Hz,1H),5.06(s,2H),4.00(t,J＝6.2Hz,2H),3.91(t,J＝6.1Hz,2H),3.50(s,2H),3.14-3.18(m,8H),1.57–1.69(m,4H),1.49–1.55(m,8H),1.26–1.35(m,8H),0.87(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):190.5,171.2,160.2,140.1,136.2,135.5,132.7,132.1,129.1,129.0,127.7,127.7,124.9,120.9,73.4,66.0,64.6,58.4,40.0,25.9,25.0,23.7,19.5,13.5.
实验例七十四2-苯基-1-乙基硫酸钠的制备
向4mL的反应瓶中依次加入2-苯基-1-乙基硼酸频那醇酯(0.2mmol)，过硫酸铵(0.4mmol)，四丁基硫酸氢铵(0.24mmol)，氟化钠(0.2mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入1mL的四氢呋喃，并至于室温下反应12小时。待反应结束后，向体系中加入碳酸氢钠淬灭反应，然后收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出2-苯基-1-乙基硫酸四丁基铵，最后将其进行离子交换即可得到2-苯基-1-乙基硫酸钠(86％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.38(dq,J＝15.6,7.7Hz,5H),4.29(t,J＝6.6Hz,2H),3.03(t,J＝6.6Hz,2H)；13C NMR(101MHz,D2O,298K,δ):138.0,129.1,128.7,126.7,69.5,34.8.
实验例七十五2-(4-叔丁基苯)-1-乙基硫酸钠的制备
实验流程见实例七十四，2-(4-叔丁基苯)-1-乙基硫酸钠(72％，1H-NMR产率)。1HNMR(400MHz,CD3OD,298K,δ):7.30(d,J＝8.3Hz,2H),7.18(d,J＝8.3Hz,2H),4.18(t,J＝7.2Hz,2H),2.94(t,J＝7.2Hz,2H),1.29(s,9H)；13C NMR(101MHz,CD3OD,298K,δ):150.2,36.1,129.6,126.2,9.7,36.2,5.1,31.8
实验例七十六2-(4-甲氧羰基苯)-1-乙基硫酸钠的制备
实验流程见实例七十四，2-(4-甲氧羰基苯)-1-乙基硫酸钠(71％，1H-NMR产率)。1HNMR(400MHz,CD3OD,298K,δ):7.97–7.91(m,2H),7.43–7.38(m,2H),4.23(t,J＝6.8Hz,2H),3.89(s,3H),3.06(t,J＝6.8Hz,2H)；13C NMR(101MHz,CD3OD,298K,δ):168.4 145.4 130.4,130.1,129.2,68.7,52.3,36.4.
实验例七十七2-(4-氯苯)-1-乙基硫酸钠的制备
实验流程见实例七十四，2-(4-氯苯)-1-乙基硫酸钠(72％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.36(d,J＝8.2Hz,2H),7.28(d,J＝8.2Hz,2H),4.25(t,J＝6.5Hz,2H),2.98(t,J＝6.5Hz,2H)；13C NMR(101MHz,D2O,298K,δ):136.6,131.7,130.5,128.4,69.2,34.1.
实验例七十八2-(2-氯苯)-1-乙基硫酸钠的制备
实验流程见实例七十四，2-(2-氯苯)-1-乙基硫酸钠(80％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.44(d,J＝7.3Hz,1H),7.37(d,J＝7.3Hz,1H),7.28(p,J＝7.3Hz,2H),4.29(t,J＝6.6Hz,2H),3.14(t,J＝6.7Hz,2H)；13C NMR(101MHz,D2O,298K,δ):135.0,133.6,131.4,129.4,128.4,127.1,67.8,32.7.
实验例七十九2,2-二苯基-1-乙基硫酸钠的制备
实验流程见实例七十四，2,2-二苯基-1-乙基硫酸钠(27％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.38(d,J＝4.3Hz,8H),7.30(h,J＝4.3Hz,2H),4.61(d,J＝7.6Hz,2H),4.47(t,J＝7.6Hz,1H)；13C NMR(101MHz,D2O,298K,δ):141.0,128.9,128.1,127.1,70.4,49.8.
实验例八十4-(4-联苯氧基)-1-丁基硫酸钠的制备
实验流程见实例七十四，4-(4-联苯氧基)-1-丁基硫酸钠(80％，1H-NMR产率)。1HNMR(400MHz,DMSO-d6,298K,δ):7.64–7.55(m,4H),7.42(t,J＝7.7Hz,2H),7.30(t,J＝7.4Hz,1H),7.05–6.99(m,2H),4.02(t,J＝6.4Hz,2H),3.77(t,J＝6.4Hz,2H),1.81–1.72(m,2H),1.71–1.62(m,2H)；13C NMR(101MHz,DMSO-d6,298K,δ):158.3,139.9,132.4,128.8,127.8,126.6,126.2,114.9,67.2,65.1,25.7,25.5.
实验例八十一4-咔唑-1-丁基硫酸钠的制备
实验流程见实例七十四，4-咔唑-1-丁基硫酸钠(63％，85.8mg)。1H NMR(400MHz,CD3OD,298K,δ):8.04(d,J＝7.7Hz,2H),7.46(d,J＝8.2Hz,2H),7.43–7.37(m,2H),7.19–7.13(m,2H),4.35(t,J＝7.2Hz,2H),4.02(t,J＝6.3Hz,2H),1.94(p,J＝7.1Hz,2H),1.72–1.63(m,2H)；13C NMR(101MHz,CD3OD,298K,δ):141.6,126.6,124.0,121.0,119.7,109.9,68.7,43.1,27.8,26.5.
实验例八十二3-((噻吩-2-羰基)氧基)-1-丙基硫酸钠的制备
实验流程见实例七十四，3-((噻吩-2-羰基)氧基)-1-丙基硫酸钠(81％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.82(d,J＝3.7Hz,1H),7.75(d,J＝5.0Hz,1H),7.15(t,J＝4.4Hz,1H),4.40(t,J＝6.4Hz,2H),4.17(t,J＝6.2Hz,2H),2.11(p,J＝6.3Hz,2H)；13C NMR(101MHz,CD3OD,298K,δ):163.7,134.7,134.5,134.1,129.0,65.6,63.0,29.8.
实验例八十三3-((喹啉-2-羰基)氧基)丙基-1-硫酸四丁基铵的制备
实验流程见实例七十四，3-((喹啉-2-羰基)氧基)丙基-1-硫酸四丁基铵(57％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):8.25(d,J＝8.6Hz,2H),8.11(d,J＝8.5Hz,1H),7.83(d,J＝8.2Hz,1H),7.73(t,J＝7.8Hz,1H),7.59(t,J＝7.6Hz,1H),4.57(t,J＝6.7Hz,2H),4.21(t,J＝6.3Hz,2H),3.33–3.17(m,8H),2.20(p,J＝6.6Hz,2H),1.61(p,J＝7.7Hz,8H),1.39(h,J＝7.3Hz,8H),0.95(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):165.2,148.2,147.7,137.3,130.8,130.2,129.3,128.6,127.6,121.2,63.9,63.6,58.8,29.1,24.0,19.8,13.7.
实验例八十四4-(4-(甲基磺酰基)苯氧基)丁基-1-硫酸四丁基铵的制备
实验流程见实例七十四，4-(4-(甲基磺酰基)苯氧基)丁基-1-硫酸四丁基铵(83％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.81–7.72(m,2H),7.01–6.92(m,2H),4.03(t,J＝6.3Hz,4H),3.25–3.16(m,8H),2.97(s,3H),1.89(p,J＝6.7Hz,2H),1.79(h,J＝6.9Hz,2H),1.58(p,J＝7.8Hz,8H),1.37(h,J＝7.4Hz,9H),0.93(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):163.3,131.8,129.4,115.1,68.2,66.3,58.7,44.9,25.9,25.6,23.9,19.7,13.7.
实验例八十五4-甲基香豆素衍生物硫酸四丁基铵的制备
实验流程见实例七十四，4-甲基香豆素衍生物硫酸四丁基铵(67％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.42(d,J＝8.8Hz,1H),6.78(dd,J＝8.8,2.4Hz,1H),6.68(d,J＝2.4Hz,1H),6.01(s,1H),4.05–3.94(m,4H),3.27–3.17(m,8H),2.32(s,3H),1.87(dq,J＝11.7,6.6Hz,2H),1.82–1.72(m,2H),1.58(td,J＝11.6,10.1,6.0Hz,8H),1.37(h,J＝7.3Hz,8H),0.92(t,J＝7.3Hz,13H)；13C NMR(101MHz,CDCl3,298K,δ):162.2,161.3,155.1,152.8,125.6,113.3,112.4,111.5,101.4,68.2,66.3,58.6,26.0,25.6,23.9,19.6,18.6,13.6.
实验例八十六1-甲苯基哌啶-4-硫酸钠的制备
实验流程见实例七十四，1-甲苯基哌啶-4-硫酸钠(41％，58.3mg)。1H NMR(400MHz,CD3OD,298K,δ):7.65(d,J＝8.0Hz,2H),7.42(d,J＝7.9Hz,2H),4.41(td,J＝5.8,2.8Hz,1H),3.07(dtt,J＝19.8,7.9,4.8Hz,4H),2.45(s,3H),1.93(tt,J＝7.5,3.3Hz,4H)；13C NMR(101MHz,CD3OD,298K,δ):145.3,134.4,130.8,128.8,73.2,44.0,31.8,21.5.
实验例八十七萘普生衍生物硫酸钠的制备
实验流程见实例七十四，萘普生衍生物硫酸钠(67％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.73(dd,J＝8.7,3.4Hz,2H),7.69–7.64(m,1H),7.39(dd,J＝8.6,1.8Hz,1H),7.20(d,J＝2.5Hz,1H),7.11(dd,J＝9.0,2.5Hz,1H),4.20(dt,J＝9.0,6.2Hz,2H),4.02(t,J＝6.3Hz,2H),3.90(s,3H),1.94(td,J＝6.3,1.5Hz,2H),1.55(d,J＝7.2Hz,3H)；13C NMR(101MHz,CD3OD,298K,δ):176.4,159.1,137.0,135.2,130.4,130.2,128.2,127.1,126.9,119.9,106.6,65.5,62.6,55.7,46.6,29.7,18.9.
实验例八十八非布索坦衍生物硫酸铵的制备
实验流程见实例七十四，非布索坦衍生物硫酸四丁基铵(66％，1H-NMR产率)。1HNMR(400MHz,CDCl3,298K,δ):8.13(s,1H),8.03(d,J＝8.9Hz,1H),6.99(d,J＝8.9Hz,1H),4.38(t,J＝6.4Hz,2H),4.14(t,J＝6.2Hz,2H),3.86(d,J＝6.4Hz,2H),3.29–3.19(m,8H),2.69(s,3H),2.12(dp,J＝26.4,6.5Hz,3H),1.61(td,J＝12.0,10.2,6.0Hz,8H),1.40(h,J＝7.4Hz,8H),1.04(d,J＝6.7Hz,6H),0.96(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):167.2,162.5,162.0,161.0,132.7,131.9,126.1,122.0,115.5,112.8,102.8,75.7,63.5,62.7,58.7,29.1,28.2,24.0,19.7,19.0,17.5,13.7.
实验例八十九3-苯基丙基硫酸钠的制备
向4mL的反应瓶中依次加入3-苯基-1-丙醇(0.2mmol)，过硫酸钾(0.4mmol)，四丁基硫酸氢铵(0.24mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入1mL的N,N-二甲基甲酰胺，并至于80℃下反应12小时。待反应结束后，向体系中加入水和二氯甲烷淬灭反应，然后收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出3-苯基丙基硫酸四丁基铵，最后将其进行离子交换即可得到3-苯基丙基硫酸钠(97％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.27-7.20(m,4H),7.16-7.13(m,1H),4.01(t,J＝6.4Hz,2H),2.72(t,J＝7.7Hz,2H),1.99-1.90(m,2H)；13C NMR(101MHz,CD3OD,298K,δ):142.9,129.5,129.3,126.8,68.3,33.0,32.4.
实验例九十2-(4-羟基苯基)乙基硫酸钠的制备
实验流程见实例八十九，2-(4-羟基苯基)乙基硫酸钠(78％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.23(d,J＝8.5Hz,2H),6.89(d,J＝8.5Hz,2H),4.25(t,J＝6.7Hz,2H),2.95(t,J＝6.7Hz,2H)；13C NMR(101MHz,D2O,298K,δ):154.0,130.3,129.8,115.4,69.7,33.9.
实验例九十一4-戊烯-1-硫酸钠的制备
实验流程见实例八十九，4-戊烯-1-硫酸四丁基铵(82％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):5.90-5.80(m,1H),5.05(dd,J＝17.1,1.8Hz,1H),4.97(d,J＝10.3Hz,1H),3.99(t,J＝6.5Hz,2H),3.27-3.23(m,8H),2.19-2.14(m,2H),1.78-1.73(m,2H),1.71-1.63(m,8H),1.42(h,J＝7.4Hz,8H),1.02(t,J＝7.4Hz,12H)；13C NMR(101MHz,CD3OD,298K,δ):139.0,115.5,68.1,59.43,59.40,59.37,31.0,29.8,24.7,20.65,20.63,20.62,14.0.
实验例九十二(E)-3-苯基丙-2-烯-1-硫酸钠的制备
实验流程见实例八十九，(E)-3-苯基丙-2-烯-1-硫酸四丁基铵(30％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.42(d,J＝7.2Hz,2H),7.32(t,J＝7.5Hz,2H),7.24(t,J＝7.3Hz,1H),6.68(d,J＝15.9Hz,1H),6.39(dt,J＝15.9,6.2Hz,1H),4.65(d,J＝6.5Hz,2H),3.22-3.18(m,8H),1.65-1.59(m,8H),1.40(h,J＝7.4Hz,8H),1.00(t,J＝7.4Hz,12H)；13C NMR(101MHz,CD3OD,298K,δ):137.8,134.0,129.6,128.9,127.5,125.5,69.3,59.3,24.7,20.6,14.0.
实验例九十三4-戊炔-1-硫酸钠的制备
实验流程见实例八十九，4-戊炔-1-硫酸钠(79％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):4.21(t,J＝6.1Hz,2H),2.39(t,J＝7.0Hz,2H),1.95(p,J＝6.6Hz,2H)；13CNMR(101MHz,CD3OD,298K,δ):84.0,69.9,67.6,29.7,15.6.
实验例九十四3-苯基丙-2-炔-1-硫酸钠的制备
实验流程见实例八十九，3-苯基丙-2-炔-1-硫酸钠(47％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.60-7.58(m,2H),7.50-7.44(m,3H),4.96(s,2H)；13C NMR(101MHz,D2O,298K,δ):131.8,129.3,128.6,121.4,87.3,83.0,57.1.
实验例九十五环丙基甲基硫酸钠的制备
实验流程见实例八十九，环丙基甲基硫酸钠(69％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):3.82(d,J＝7.2Hz,2H),1.20-1.10(m,1H),0.58-0.53(m,2H),0.31-0.27(m,2H)；13C NMR(101MHz,CD3OD,298K,δ):74.0,11.1,3.6.
实验例九十六2-(噻吩-3-基)乙烷-1-硫酸钠的制备
实验流程见实例八十九，2-(噻吩-3-基)乙烷-1-硫酸钠(77％，1H-NMR产率)。1HNMR(400MHz,CD3OD,298K,δ):7.30(dd,J＝5.0,3.0Hz,1H),7.15(s,1H),7.03(d,J＝4.9Hz,1H),4.19(t,J＝7.0Hz,2H),3.01(t,J＝7.0Hz,2H)；13C NMR(101MHz,CD3OD,298K,δ):139.6,129.4,126.2,122.4,69.0,31.2.
实验例九十七2-(4-甲基噻唑-5-基)乙烷-1-硫酸钠的制备
实验流程见实例八十九，2-(4-甲基噻唑-5-基)乙烷-1-硫酸四丁基铵(77％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):8.76(s,1H),4.15(t,J＝6.5Hz,2H),3.26-3.22(m,8H),3.18(t,J＝6.5Hz,2H),2.40(s,3H),1.70-1.62(m,8H),1.41(h,J＝7.4Hz,8H),1.02(t,J＝7.4Hz,12H)；13C NMR(101MHz,CD3OD,298K,δ):152.3,150.4,129.3,68.5,59.5,27.4,24.8,20.7,14.6,14.0.
实验例九十八2-金刚烷硫酸钠的制备
实验流程见实例八十九，2-金刚烷硫酸钠(98％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):4.51(t,J＝3.2Hz,1H),2.15(d,J＝13.6Hz,4H),1.91-1.87(m,2H),1.78(d,J＝9.4Hz,6H),1.55(d,J＝13.1Hz,2H)；13C NMR(101MHz,CD3OD,298K,δ):83.1,38.6,37.6,34.0,32.4,28.6,28.4.
实验例九十九α-甲酸-4-氟苄基硫酸钠的制备
实验流程见实例八十九，α-甲酸-4-氟苄基硫酸钠(87％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.54(dd,J＝8.6,5.5Hz,2H),7.10(t,J＝8.7Hz,2H),5.67(s,1H),3.24-3.20(m,8H),1.67-1.59(m,8H),1.39(h,J＝7.4Hz,8H),0.98(t,J＝7.4Hz,12H)；13C NMR(101MHz,CD3OD,298K,δ):173.2,165.2,162.8,134.0,134.0,130.4,130.3,116.1,115.9,78.0,59.3,24.6,20.5,14.0；19F NMR(376MHz,CD3OD,298K,δ):-115.20.实验例一百DL-泛酰内酯硫酸钠的制备
实验流程见实例八十九，DL-泛酰内酯硫酸四丁基铵(73％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):4.84(s,1H),4.06-4.01(m,2H),3.28-3.24(m,8H),1.71-1.63(m,8H),1.42(h,J＝7.4Hz,8H),1.29(s,3H),1.10(s,3H),1.02(t,J＝7.4Hz,12H)；13C NMR(101MHz,CD3OD,298K,δ):175.4,80.6,77.1,59.4,41.5,24.8,23.1,20.6,19.8,14.0.
实验例一百零一埃卡瑞丁硫酸钠的制备
实验流程见实例八十九，埃卡瑞丁硫酸四丁基铵(43％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):4.69(h,J＝6.2Hz,1H),4.43-4.38(m,1H),4.02-3.95(m,3H),3.27-3.23(m,8H),2.96-2.88(m,1H),2.17-2.06(m,1H),1.96-1.86(m,1H),1.71-1.59(m,15H),1.42(h,J＝7.4Hz,9H),1.22(t,J＝6.8Hz,3H),1.02(t,J＝7.3Hz,12H),0.92(td,J＝7.5,3.8Hz,3H)；13C NMR(101MHz,CD3OD,298K,δ):157.14,157.11,74.7,66.6,59.5,49.6,49.6,40.1,40.0,30.6,30.04,30.01,29.4,26.7,26.6,24.8,20.70,20.68,20.66,20.1,19.9,14.0,10.14,10.07.
实验例一百零二羟丙茶碱硫酸钠的制备
实验流程见实例八十九，羟丙茶碱硫酸钠(80％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.93(s,1H),4.81-4.76(m,1H),4.57(dd,J＝14.2,3.0Hz,1H),4.37(dd,J＝14.2,7.7Hz,1H),3.53(s,3H),3.34(s,3H),1.34(d,J＝6.5Hz,3H)；13C NMR(101MHz,CD3OD,298K,δ):156.7,153.3,149.8,144.6,108.4,74.7,52.2,30.2,28.3,18.2.
实验例一百零三薯蓣皂素硫酸钠的制备
实验流程见实例八十九，薯蓣皂素硫酸钠(65％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):5.40-5.39(m,1H),4.43-4.37(m,1H),4.18-4.10(m,1H),3.47-3.42(m,1H),2.57-2.52(m,1H),2.38-2.31(m,1H),2.05-1.99(m,4H),1.92-1.87(m,3H),1.77-1.73(m,3H),1.68-1.54(m,9H),1.29(s,3H),1.05(s,4H),0.96(d,J＝6.9Hz,4H),0.82-0.78(m,5H)；13C NMR(101MHz,CD3OD,298K,δ):141.6,123.0,110.6,82.2,79.7,67.8,63.7,57.7,51.6,42.9,41.4,40.9,40.4,38.4,37.8,33.2,32.8,32.7,32.4,31.4,30.0,29.9,22.0,19.8,17.5,16.8,14.9.
实验例一百零四1-(4-联苯)-1,3-丁二酮-α-硫酸的制备
向4mL的反应瓶中依次加入1-(4-联苯)-1,3-丁二酮(0.2mmol)，硝酸银(0.01mmol)，配体(0.03mmol)，过硫酸钾(0.6mmol)，过硫酸四丁基铵(0.12mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入1.5mL的二氯甲烷，并至于50℃下反应18小时。待反应结束后，向体系中加入200mg碳酸氢钠淬灭反应，然后过滤收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出1-(4-联苯)-1,3-丁二酮-α-硫酸四丁基铵(88％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):15.48*(s,0.1H),8.32*(d,J＝8.3Hz,0.2H),8.19(d,J＝8.3Hz,2H),7.64(d,J＝8.5Hz,2H),7.58(d,J＝7.2Hz,2H),7.44(t,J＝7.4Hz,2H),7.37(t,J＝7.3Hz,1H),5.87(s,1H),3.19–3.15(m,9H),2.50*(s,0.3H),2.39(s,3H),1.61-1.53(m,9H),1.36(h,J＝7.3Hz,9H),0.93(t,J＝7.2Hz,13H)；13C NMR(101MHz,CDCl3,298K,δ):205.6,193.2,146.0,139.7,133.6,130.2,130.1*,128.9,128.8*,128.2,127.1,127.0,126.9*,126.2*,83.2,58.4,26.8,23.7,19.5,13.5.
实验例一百零五1-(4-溴苯)-1,3-丁二酮-α-硫酸的制备
实验流程见实例一百零四，1-(4-溴苯)-1,3-丁二酮-α-硫酸四丁基铵(93％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):15.30*(s,0.3H),8.07*(d,J＝8.3Hz,0.5H),7.99(d,J＝8.3Hz,2H),7.55(d,J＝8.2Hz,2H),7.46*(d,J＝8.4Hz,0.5H),5.75(s,1H),3.17-3.13(m,10H),2.47*(s,0.8H),2.36(s,3H),1.57(s,10H),1.36(q,J＝7.2Hz,10H),0.95(t,J＝6.8Hz,15H)；13C NMR(101MHz,CDCl3,298K,δ):205.3,196.0*,193,173.1*,133.7,131.7,131.2,131.1*,130.8*,130.2*,128.8,125.3*,83.2,58.4,26.8,23.8,23.6*,19.6,13.6.
实验例一百零六1-(4-甲氧基苯)-1,3-丁二酮-α-硫酸的制备
实验流程见实例一百零四，1-(4-甲氧基苯)-1,3-丁二酮-α-硫酸四丁基铵(74％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):15.67*(s,0.06H),8.26(d,J＝9.0Hz,0.1H),8.12(d,J＝8.9Hz,2H),6.89(d,J＝9.0Hz,2H),5.80(s,1H),3.83(s,3H),3.80*(s,0.2H),3.20–3.16(m,8H),2.44(s,0.2H),2.35(s,3H),1.62–1.54(m,8H),1.36(h,J＝7.3Hz,8H),0.94(t,J＝7.3Hz,13H)；13C NMR(101MHz,CDCl3,298K,δ):205.9,191.9,163.9,132.1,128.0,113.6,83.0,58.4,55.4,26.8,23.8,19.6,13.6.
实验例一百零七1-(4-乙基甲酸基苯)-1,3-丁二酮-α-硫酸的制备
实验流程见实例一百零四，1-(4-乙基甲酸基苯)-1,3-丁二酮-α-硫酸四丁基铵(90％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):15.19*(s,0.4H),8.22*(d,J＝8.2Hz,0.8H),8.16(d,J＝8.0Hz,2H),8.06(d,J＝8.1Hz,2H),7.99*(d,J＝8.1Hz,0.8H),5.82(s,1H),4.39-4.31(m,3H),3.16–3.13(m,11H),2.50*(s,1H),2.37(s,3H),1.56(s,11H),1.39-1.32(m,15H),0.94(t,J＝6.7Hz,17H)；13C NMR(101MHz,CDCl3,298K,δ):205.2,197.4*,193.6,171.9*,166.2*,165.7,138.8*,138.1,134.3,131.6*,130.5*,129.49,129.45,129.2*,128.7*,83.3,61.3,60.9*,58.5,26.9,24.0*,23.8,19.6,14.2*,13.5.
实验例一百零八1-(2-氯苯)-1,3-丁二酮-α-硫酸的制备
实验流程见实例一百零四，1-(2-氯苯)-1,3-丁二酮-α-硫酸四丁基铵(47％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):14.75*(s,0.8H),7.81(d,J＝7.4Hz,1H),7.62*(d,J＝6.7Hz,0.8H),7.39-7.36(m,2H),7.34–7.31(m,2H),7.25-7.21(m,1H),5.82(s,1H),3.18(s,14H),2.46*(s,2H),2.35(s,3H),1.58(s,14H),1.37(s,14H),0.96(t,J＝5.7Hz,22H)；13C NMR(101MHz,CDCl3,298K,δ):203.5,195.1,193.4*,178.2*,135.9*,134.7*,132.2,132.1*,132.0*,131.2*,130.9,130.6,130.2,129.3,126.6,125.9*,85.5,58.6,27.1,23.9,23.1*,19.7,13.6.
实验例一百零九1-(3-氯苯)-1,3-丁二酮-α-硫酸的制备
实验流程见实例一百零四，1-(3-氯苯)-1,3-丁二酮-α-硫酸四丁基铵(93％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):15.22*(s,0.3H),8.14*(dt,J＝7.3,1.6Hz,0.3H),8.08*(t,J＝1.9Hz,0.3H),8.05–8.01(m,2H),7.50-7.47(m,1H),7.36(t,J＝7.9Hz,1H),7.33–7.30*(m,0.3H),7.28*(s,0.3H),5.76(s,1H),3.17–3.13(m,10H),2.47*(s,0.8H),2.36(s,3H),1.61–1.53(m,10H),1.35(h,J＝7.3Hz,10H),0.94(t,J＝7.3Hz,16H)；13C NMR(101MHz,CDCl3,298K,δ):205.1,196.3*,192.7,172.4*,136.5,134.5,133.4*,133.3,130.4*,130.3*,129.8,129.2,128.99*,128.96*,128.1,128.0*,83.3,58.4,26.8,23.7,19.5,13.5.
实验例一百一十1-(3-甲氧基苯)-1,3-丁二酮-α-硫酸的制备
实验流程见实例一百零四，1-(3-甲氧基苯)-1,3-丁二酮-α-硫酸四丁基铵(89％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):15.43*(s,0.1H),7.85*(t,J＝2.1Hz,0.1H),7.79*(d,J＝7.9,0.1H),7.72(d,J＝7.7,1H),7.65(t,J＝2.1Hz,1H),7.31(t,J＝8.0Hz,1H),7.22*(d,J＝8.0Hz,0.1H),7.07(dd,J＝8.2,2.5,1H),6.91*(dd,J＝8.2,2.5,1H,0.1H),5.80(s,1H),3.81(s,3H),3.17–3.13(m,9H),2.48*(s,0.3H),2.35(s,3H),1.59-1.51(m,9H),1.34(h,J＝7.3Hz,9H),0.93(t,J＝7.3Hz,13H)；13C NMR(101MHz,CDCl3,298K,δ):205.6,195.9*,193.4,173.8*,159.6,158.9*,136.1,135.8*,129.4,128.5*,122.3,122.0*,120.5,117.7*,114.0*,113.5,83.0,58.3,55.5,26.8,23.7,19.5,13.5.
实验例一百一十一1-苯基-4,4-二甲基-1,3-戊二酮-α-硫酸的制备
实验流程见实例一百零四，1-苯基-4,4-二甲基-1,3-戊二酮-α-硫酸四丁基铵(58％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):8.22(d,J＝7.8Hz,2H),7.52(t,J＝7.4Hz,1H),7.43(t,J＝7.6Hz,2H),6.44(s,1H),3.26–3.21(m,8H),1.65–1.57(m,8H),1.36(h,J＝7.4Hz,8H),1.21(s,9H),0.94(t,J＝7.3Hz,12H)；13CNMR(101MHz,CDCl3,298K,δ):209.0,194.9,135.4,133.2,129.8,128.4,58.6,44.4,26.5,23.9,19.6,13.6.实验例一百一十二1-苯基-3-(2-噻吩)-1,3-丙二酮-α-硫酸的制备
实验流程见实例一百零四，1-苯基-3-(2-噻吩)-1,3-丁二酮-α-硫酸四丁基铵(62％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):8.29(d,J＝3.8Hz,1H),8.12(d,J＝7.3Hz,2H),7.62(d,J＝4.9Hz,1H),7.51(t,J＝7.4Hz,1H),7.40(t,J＝7.6Hz,2H),7.09(t,J＝4.4Hz,1H),6.48(s,1H),3.19–3.14(m,8H),1.60-1.52(m,8H),1.33(q,J＝7.3Hz,8H),0.92(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):193.9,187.4,141.5,135.7,135.2,134.4,133.2,129.6,128.5,128.3,82.1,58.4,23.8,19.6,13.6.
实验例一百一十三1-苯基-3-(4-溴苯)-1,3-丙二酮-α-硫酸的制备
实验流程见实例一百零四，1-苯基-3-(4-溴苯)-1,3-丁二酮-α-硫酸四丁基铵(80％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):8.09(d,J＝7.8Hz,2H),7.99(d,J＝8.2Hz,2H),7.85*(d,J＝8.2Hz,0.2H),7.51(d,J＝8.5Hz,3H),7.39(t,J=7.6Hz,2H),6.62(s,1H),3.18-3.15(m,9H),1.57(s,9H),1.38-1.31(m,9H),0.93(t,J＝6.9Hz,13H)；13C NMR(101MHz,CDCl3,298K,δ):194.3,194.0,135.2,134.1,133.4,132.2*,131.7,131.5*,131.3,130.8,129.6,129.3*,128.9*,128.5,81.6,58.6,23.9,19.7,13.7.
实验例一百一十四二-1,3-(4-甲氧基苯)-1,3-丙二酮-α-硫酸的制备
实验流程见实例一百零四，二-1,3-(4-甲氧基苯)-1,3-丁二酮-α-硫酸四丁基铵(50％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):8.13(d,J＝8.6Hz,4H),6.87(d,J＝8.7Hz,4H),6.64(s,1H),3.82(s,6H),3.23–3.19(m,8H),1.63-1.53(m,8H),1.36(h,J＝7.3Hz,8H),0.93(t,J＝7.3Hz,12H)；13C NMR(101MHz,CDCl3,298K,δ):192.8,163.6,132.0,128.4,113.6,81.3,58.5,55.4,23.9,19.6,13.6.
实验例一百一十五1-噻吩-1,3-丁二酮-α-硫酸的制备
实验流程见实例一百零四，1-噻吩-1,3-丁二酮-α-硫酸四丁基铵(72％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):15.35*(s,0.1H),8.33*(dd,J＝3.9,1.1Hz,0.1H),8.20(dd,J＝3.9,1.1Hz,1H),7.64(dd,J＝5.0,1.1Hz,1H),7.52*(dd,J＝5.0,1.2Hz,0.1H),7.09(dd,J＝4.9,3.9Hz,1H),7.06*(dd,J＝5.0,3.9Hz,0.1H),5.64(s,1H),3.20–3.15(m,9H),2.40*(s,0.3H),2.34(s,3H),1.61-1.53(m,9H),1.40–1.31(m,9H),0.93(t,J＝7.3Hz,13H)；13C NMR(101MHz,CDCl3,298K,δ):204.6,186.2,141.4,135.8,134.8,128.5,84.1,58.4,26.7,23.7,19.5,13.5.
实验例一百一十六1-甲基-5-乙酰基吡咯-2-硫酸的制备
向4mL的反应瓶中依次加入1-甲基-2-乙酰基吡咯(0.2mmol)，碳酸银(0.02mmol)，配体(0.02mmol)，过硫酸铵(0.6mmol)，过硫酸四丁基铵(0.1mmol)和碳酸锂(0.2mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入1.0mL的二氯甲烷，并至于室温下反应10小时。待反应结束后，向体系中加入200mg碳酸氢钠淬灭反应，然后过滤收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出1-甲基-5-乙酰基吡咯-2-硫酸四丁基铵(56％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.41(d,J＝6.0Hz,1H),6.20(d,J＝6.0Hz,1H),3.27–3.17(m,10H),2.89(s,3H),2.39(s,3H),1.72–1.55(m,10H),1.43(m,10H),1.01(t,J＝7.3Hz,14H).
实验例一百一十七5-甲基乙酸酯呋喃-2-硫酸的制备
实验流程见实例一百一十六，5-甲基乙酸酯呋喃-2-硫酸四丁基铵(45％，1H-NMR产率)。1H NMR(400MHz,CDCl3,298K,δ):7.64(d,J＝5.7Hz,1H),6.13(d,J＝5.7Hz,1H),4.47(d,J＝11.5Hz,1H),4.26(d,J＝11.5Hz,1H),3.24–3.14(m,10H),1.98(s,3H),1.60(m,10H),1.40(m,10H),0.97(t,J＝7.3Hz,15H)；13C NMR(101MHz,CDCl3,298K,δ):170.2,170.0,152.3,123.4,105.4,64.1,58.5,23.8,20.6,19.6,13.6.
实验例一百一十八1-苯基丙烷-1,3–二硫酸钠的制备
向4mL的反应瓶中依次加入苯基环丙烷(0.2mmol)，硝酸银(0.02mmol)，配体(0.02mmol)，过硫酸铵(0.6mmol)和四丁基硫酸氢铵(0.6mmol)。加完后将4mL的反应瓶密封抽真空，再充入氩气，反复操作3次。最后向瓶中加入1.0mL的二氯甲烷，并至于室温下反应10小时。待反应结束后，向体系中加入200mg碳酸氢钠淬灭反应，然后过滤收集有机相。将有机相浓缩后进行柱层析，用二氯甲烷与甲醇的体积比为20:1的洗脱剂分离出1-苯基丙烷-1,3-二硫酸四丁基铵,最后将其进行离子交换即可得到1-苯基丙烷-1,3-二硫酸钠(88％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):7.44–7.33(m,5H),5.40(t,J＝6.8,1H),4.12(m,1H),3.96(m,1H),2.34(dt,J＝13.9,7.0Hz,1H),2.17(dt,J＝14.3,6.5Hz,1H)；13C NMR(101MHz,D2O,298K,δ):139.6,128.7,128.5,126.6,78.7,65.4,36.4.
实验例一百一十九1-(4-溴苯)丙烷-1,3–二硫酸的制备
实验流程见实例一百一十八，1-(4-溴苯)丙烷-1,3-二硫酸四丁基铵(99％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.47(d,J＝8.5Hz,2H),7.38–7.32(m,2H),5.41(t,J＝6.7Hz,1H),4.08(m,1H),3.96(m,1H),3.27–3.18(m,16H),2.35(dt,J＝14.4,7.2Hz,1H),2.16(dt,J＝13.7,6.7Hz,1H),1.66(dd,J＝10.6,6.0Hz,16H),1.41(q,J＝7.4Hz,17H),1.02(t,J＝7.4Hz,24H)；13C NMR(101MHz,CD3OD,298K,δ):140.5,130.9,128.3,120.9,76.5,64.1,58.1,37.0,23.4,19.2,12.6.
实验例一百二十1-(4-氯苯)丙烷-1,3–二硫酸的制备
实验流程见实例一百一十八，1-(4-氯苯)丙烷-1,3-二硫酸四丁基铵(74％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.41(d,J＝8.4Hz,2H),7.32(d,J＝8.4Hz,2H),5.43(t,J＝6.8Hz,1H),4.09(dt,J＝10.2,6.5Hz,1H),3.96(dt,J＝10.2,7.1Hz,1H),3.27–3.20(m,16H),2.35(dd,J＝14.0,7.1Hz,1H),2.14(dd,J＝13.6,6.8Hz,1H),1.66(dd,J＝10.4,6.2Hz,17H),1.41(q,J＝7.4Hz,17H),1.02(t,J＝7.3Hz,25H)；13C NMR(101MHz,CD3OD,298K,δ):141.4,134.2,129.3,129.3,77.8,65.5,59.5,38.5,24.8,20.7,14.0.实验例一百二十一1-(4-叔丁基苯)丙烷-1,3–二硫酸的制备
实验流程见实例一百一十八，1-(4-叔丁基苯)丙烷-1,3-二硫酸四丁基铵(72％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.39–7.32(m,4H),5.42(t,J＝6.8Hz,1H),4.07(td,J＝9.1,8.7,5.6Hz,1H),3.97(dt,J＝10.1,7.4Hz,1H),3.28–3.15(m,16H),2.40(dq,J＝14.4,7.2Hz,1H),2.18(dq,J＝13.6,6.7Hz,1H),1.72–1.60(m,16H),1.42(q,J＝7.4Hz,17H),1.30(s,9H),1.02(t,J＝7.3Hz,24H)；13C NMR(101MHz,CD3OD,298K,δ):151.6,139.3,127.4,126.1,78.6,65.8,59.5,38.5,35.3,31.8,24.8,20.7,14.0.
实验例一百二十二1-(4-异丙基苯)丙烷-1,3–二硫酸的制备
实验流程见实例一百一十八，1-(4-异丙基苯)丙烷-1,3-二硫酸四丁基铵(78％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.33(d,J＝7.9Hz,2H),7.19(d,J＝8.0Hz,2H),5.41(t,J＝6.8Hz,1H),4.07(td,J＝9.1,8.4,5.6Hz,1H),3.97(dt,J＝10.0,7.3Hz,1H),3.27–3.20(m,16H),2.88(p,J＝6.9Hz,1H),2.39(dt,J＝14.4,7.1Hz,1H),2.22–2.13(m,1H),1.66(t,J＝8.3Hz,16H),1.42(q,J＝7.4Hz,16H),1.23(d,J＝6.9Hz,6H),1.02(t,J＝7.3Hz,24H)；13C NMR(101MHz,CD3OD,298K,δ):149.4,139.7,127.7,127.2,78.6,65.8,59.5,38.5,35.1,24.8,24.5,20.7,14.0.
实验例一百二十三1-(4-乙酰氧基苯)丙烷-1,3–二硫酸的制备
实验流程见实例一百一十八，1-(4-乙酰氧基苯)丙烷-1,3-二硫酸四丁基铵(93％，1H-NMR产率)。1H NMR(400MHz,CD3OD,298K,δ):7.48(d,J＝8.3Hz,2H),7.08(d,J＝8.3Hz,2H),5.47(t,J＝6.8Hz,1H),4.12(td,J＝9.1,8.3,5.7Hz,1H),4.01(dt,J＝10.3,7.3Hz,1H),3.29–3.20(m,16H),2.40(dt,J＝14.4,7.2Hz,1H),2.28(s,3H),2.21(dt,J＝13.6,6.8Hz,1H),1.66(d,J＝8.0Hz,16H),1.43(q,J＝7.4Hz,16H),1.07–1.01(m,24H)；13CNMR(101MHz,CD3OD,298K,δ):171.0,151.7,140.1,128.7,122.4,78.0,65.7,59.5,38.6,24.8,20.9,20.7,14.0.
实验例一百二十四1-(4-甲基甲酸基苯)丙烷-1,3–二硫酸钠的制备
实验流程见实例一百一十八，1-(4-基甲酸基苯)丙烷-1,3-二硫酸钠(49％，1H-NMR产率)。1H NMR(400MHz,D2O,298K,δ):8.02(dd,J＝8.3,2.0Hz,2H),7.55(d,J＝8.1Hz,2H),5.48(t,J＝6.8Hz,1H),4.16(dt,J＝12.4,6.1Hz,1H),4.01(dt,J＝11.2,6.1Hz,1H),3.91(s,3H),2.41–2.30(m,1H),2.20(dd,J＝14.2,6.7Hz,1H)；13C NMR(101MHz,D2O,298K,δ):169.2,145.4,129.7,129.4,126.7,77.9,65.1,52.7,36.2.
在以上的描述中阐述了很多具体细节以便于充分理解本发明。但是，以上描述仅是本发明的较佳实验例而已，本发明能够以很多不同于在此描述的其它方式来实施，因此本发明不受上面公开的具体实施的限制。同时任何熟悉本领域技术人员在不脱离本发明技术方案范围情况下，都可利用上述揭示的方法和技术内容对本发明技术方案做出许多可能的变动和修饰，或修改为等同变化的等效实验例。凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实验例所做的任何简单修改、等同变化及修饰，均仍属于本发明技术方案保护的范围内。
Claims (10)
1.一种有机硫酸盐的制备方法，其特征在于，包括以下步骤:以过硫酸盐为硫酸根来源,通过所述硫酸根的自由基负离子实现自由基前体化合物官能团的转化，从而制备出所述有机硫酸盐。
2.根据权利要求1所述的制备方法，其特征在于，所述过硫酸盐具有如下分子通式：
其中，M为抗衡阳离子。
3.根据权利要求2所述的制备方法，其特征在于，所述自由基前体化合物包括：R-COOH，其中R包括取代的烃基和取代的芳(杂)基，取代基包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基的数量为一个或多个。
4.根据权利要求2所述的制备方法，其特征在于，所述自由基前体化合物包括：
其中R1包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基R1的数量为1～5；R2包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基；R3包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基。
5.根据权利要求2所述的制备方法，其特征在于，所述自由基前体化合物包括：
R-Y R-[B] R-OH
其中，R包括取代的烃基，R中的取代基包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基的数量为一个或多个；Y包括氯、溴、碘；[B]为硼酸(B(OH)2)、三氟硼酸盐(-BF3)和双联嚬哪醇硼酸酯(Bpin)。
6.根据权利要求2所述的制备方法，其特征在于，所述自由基前体化合物包括：
其中，R1包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基R1的数量为1～5；R2包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基；R3包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基。
7.根据权利要求2所述的制备方法，其特征在于，所述自由基前体化合物包括：
其中R1包括包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基R1的数量为1～5；n为0或1；X为C,N,O,S。
8.根据权利要求2所述的制备方法，其特征在于，所述自由基前体化合物包括：
其中R1,R2,R3,R4,R5,R6的结构包括H、芳基、≥C1的烃基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基或卤素原子，取代基R1的数量为1～5。
9.根据权利要求1至8任一所述制备方法，其特征在于，包括以下步骤：按比例将所述自由基前体化合物、过硫酸盐、金属催化剂、配体和有机铵盐在反应容器中混合，反应容器抽真空，之后向反应瓶中加入有机溶剂，搅拌反应，反应结束后进行淬灭反应，然后进行柱层析，得到有机硫酸铵盐，将得到的有机硫酸铵盐进行离子交换得到有机硫酸钠盐。
10.一种根据权利要求1至9任一所述制备方法制备的有机硫酸盐，其特征在于，所述有机硫酸盐具有如下分子通式：
其中R包括取代的烃基和取代的芳(杂)基，取代基包括≥C1的烃基、芳基、烷氧基、烷硫基、硅基、硼基、酯基、酰胺基、氰基、三氟甲基、醛基、硝基、烯基、炔基、叠氮基或卤素原子，取代基的数量为一个或多个。
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