CN114805289A - 一种1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法 - Google Patents
一种1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法 Download PDFInfo
- Publication number
- CN114805289A CN114805289A CN202210385120.2A CN202210385120A CN114805289A CN 114805289 A CN114805289 A CN 114805289A CN 202210385120 A CN202210385120 A CN 202210385120A CN 114805289 A CN114805289 A CN 114805289A
- Authority
- CN
- China
- Prior art keywords
- compound
- nmr
- mhz
- oxathia
- melting point
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexediene Natural products C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 130
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000012074 organic phase Substances 0.000 claims abstract description 12
- 229940125904 compound 1 Drugs 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229940125782 compound 2 Drugs 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000004809 thin layer chromatography Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229940126214 compound 3 Drugs 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 15
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- -1 diiodo, tetrabutylammonium iodide Chemical compound 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 5
- 235000009518 sodium iodide Nutrition 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- STBUWXYTSVWZIS-UHFFFAOYSA-N morpholine;2,2,2-trifluoroacetic acid Chemical compound C1COCCN1.OC(=O)C(F)(F)F STBUWXYTSVWZIS-UHFFFAOYSA-N 0.000 claims description 3
- RGGPDHHEMZDRQW-UHFFFAOYSA-N n-benzyl-1-phenylmethanamine;2,2,2-trifluoroacetic acid Chemical compound [O-]C(=O)C(F)(F)F.C=1C=CC=CC=1C[NH2+]CC1=CC=CC=C1 RGGPDHHEMZDRQW-UHFFFAOYSA-N 0.000 claims description 3
- LJZHQOFHXBAAAE-UHFFFAOYSA-N n-ethylethanamine;2,2,2-trifluoroacetic acid Chemical compound CC[NH2+]CC.[O-]C(=O)C(F)(F)F LJZHQOFHXBAAAE-UHFFFAOYSA-N 0.000 claims description 3
- KKXBFPVAQSRGAR-UHFFFAOYSA-N n-propan-2-ylpropan-2-amine;sulfuric acid Chemical compound OS(O)(=O)=O.CC(C)NC(C)C KKXBFPVAQSRGAR-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229940107816 ammonium iodide Drugs 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- RTLCITOIBQXPPP-UHFFFAOYSA-N di(propan-2-yl)azanium;2,2,2-trifluoroacetate Chemical group CC(C)[NH2+]C(C)C.[O-]C(=O)C(F)(F)F RTLCITOIBQXPPP-UHFFFAOYSA-N 0.000 claims description 2
- URAZVWXGWMBUGJ-UHFFFAOYSA-N di(propan-2-yl)azanium;chloride Chemical compound [Cl-].CC(C)[NH2+]C(C)C URAZVWXGWMBUGJ-UHFFFAOYSA-N 0.000 claims description 2
- KEEBIZOZZGQJHM-UHFFFAOYSA-N di(propan-2-yl)azanium;trifluoromethanesulfonate Chemical compound CC(C)[NH2+]C(C)C.[O-]S(=O)(=O)C(F)(F)F KEEBIZOZZGQJHM-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- RNTRKRXLUUYBHE-UHFFFAOYSA-N dicyclohexylazanium;2,2,2-trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F.C1CCCCC1[NH2+]C1CCCCC1 RNTRKRXLUUYBHE-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- BPPJEMLBERXGOK-UHFFFAOYSA-N n-butylbutan-1-amine;2,2,2-trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.CCCCNCCCC BPPJEMLBERXGOK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims 1
- CQUAMQGHXKKJRD-UHFFFAOYSA-N OCl(=O)(=O)=O.CC(C)NC(C)C Chemical compound OCl(=O)(=O)=O.CC(C)NC(C)C CQUAMQGHXKKJRD-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- XIHZEQVDTJKXOC-UHFFFAOYSA-N n-methylmethanamine;2,2,2-trifluoroacetic acid Chemical compound CNC.OC(=O)C(F)(F)F XIHZEQVDTJKXOC-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 76
- 238000002844 melting Methods 0.000 description 69
- 230000008018 melting Effects 0.000 description 69
- 239000003208 petroleum Substances 0.000 description 38
- 239000000047 product Substances 0.000 description 38
- 239000007787 solid Substances 0.000 description 37
- 230000005311 nuclear magnetism Effects 0.000 description 32
- 238000004896 high resolution mass spectrometry Methods 0.000 description 18
- 238000001819 mass spectrum Methods 0.000 description 15
- 238000004440 column chromatography Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 4
- JXVJRVGTQNVIAU-UHFFFAOYSA-N pent-3-enethial Chemical class CC=CCC=S JXVJRVGTQNVIAU-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- ZSXGLVDWWRXATF-UHFFFAOYSA-N N,N-dimethylformamide dimethyl acetal Chemical compound COC(OC)N(C)C ZSXGLVDWWRXATF-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- AIUOUEPKBRDPLG-UHFFFAOYSA-N 1,3-benzoxathiole Chemical class C1=CC=C2SCOC2=C1 AIUOUEPKBRDPLG-UHFFFAOYSA-N 0.000 description 1
- FZTLLUYFWAOGGB-UHFFFAOYSA-N 1,4-dioxane dioxane Chemical group C1COCCO1.C1COCCO1 FZTLLUYFWAOGGB-UHFFFAOYSA-N 0.000 description 1
- BTBFCBQZFMQBNT-UHFFFAOYSA-N 3,4-difluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1F BTBFCBQZFMQBNT-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 230000036436 anti-hiv Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Substances CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/06—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
- C07D411/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J33/00—Normal steroids having a sulfur-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
- C07J33/002—Normal steroids having a sulfur-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton not condensed
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种1,4‑氧硫杂‑3,5‑二醛基环己二烯化合物的制备方法，本发明在密封耐压反应器中加入化合物1、化合物2、溶剂、催化剂、氧化剂、添加剂，在搅拌、55‑65℃的油浴锅中反应2.0 h，薄层色谱监测反应进程，直至反应完全；然后加入饱和硫代硫酸钠溶液混匀后加入乙酸乙酯萃取2‑4次，收集合并有机相并用饱和食盐水洗涤，收集有机相后用无水硫酸钠干燥，减压蒸出溶剂，残渣用硅胶柱层析分离纯化得到化合物3；本发明反应条件温和，合成路线短，操作安全，反应对空气不敏感等特点，具有极大的工业化应用价值；
。
Description
技术领域
本发明属于有机合成技术领域，具体涉及一种1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法。
背景技术
1,4-氧硫杂环己二烯类化合物是一类重要的多杂原子杂环化合物，如2-氯-5-(5,6-二氢-2-甲基-1,4-氧硫杂环己二烯-3-甲酰胺基)苯甲酸异丙酯(UC84)具有抗HIV活性。目前，1,4-氧硫杂环己二烯衍生物类化合物的合成报道并不多。例如，2013年Hu课题组报道的邻羟基硫酚与3,4-二氟苯甲腈在无金属催化的条件下较好产率合成苯并1,4-氧硫杂环己二烯化合物，但需要使用气味难闻的硫酚。（Hu F.D., Zhao X., Li Y.Q., Feng L., MaC.. Synthesis,2013, 45, 966–970.）
再有，2017年Saidalimu研究团队报道了以α-亚甲基酮和C6F5-DAST为起始物，在异丙醚的促进作用下成功的合成了全氟苯并1,4-氧硫杂环化合物，该方法只适用于合成全氟苯1,4-氧硫杂环化合物。（Saidalimu I., Suzuki S. G., Wang J. D., Tokunaga E.,Shibata N.Org. Lett. 2017, 19, 1012−1015.）
就目前而言，1,4-氧硫杂环己二烯类化合物的合成仍然存在着需通过繁琐操作预制备起始物、使用气味比较难闻的硫醇、底物适用范围不够广泛，构建1,4-氧硫杂环己二烯需要通过与苯环形成并环，难以制备单环的1,4-氧硫杂环己二烯衍生物。
发明内容
为了解决现有技术不足，本发明提供了一种简单高效的1,4-氧硫杂-3,5-二醛基环己二烯化合物制备方法。
为解决上述技术问题，本发明采用的技术方案是：在密封耐压反应器中加入化合物1、化合物2、溶剂、催化剂、氧化剂、添加剂，在搅拌、55-65℃的油浴锅中反应2.0 h，薄层色谱监测反应进程，直至反应完全；然后加入饱和硫代硫酸钠溶液混匀后加入乙酸乙酯萃取2-4次，收集合并有机相并用饱和食盐水洗涤，收集有机相后用无水硫酸钠干燥，减压蒸出溶剂，残渣用硅胶柱层析分离纯化得到化合物3；
其中R选自芳基、烷基；化合物1与化合物2的摩尔比为1:1~3。
所述催化剂选自五氧化二碘、四丁基碘化铵、碘化钾、碘化钠、碘化铵、碘化锂、碘化亚铜、N-碘代琥珀酰亚胺；化合物1与催化剂的摩尔比为1:0.1~1.0；
所述氧化剂选自叔丁基过氧化氢(TBHP)、过氧化苯甲酰、过氧化氢异丙苯、二叔丁基过氧化物、3-氯过氧化苯甲酸、过氧化苯甲酸叔丁酯、过硫酸钾、过硫酸钠、过硫酸铵、过氧硫酸氢钾复合盐，化合物1与氧化剂的摩尔比为1:0.5~1。
所述溶剂选自1,4-二氧六环(1,4-dioxane)、二氯甲烷、甲醇、二甲基亚砜、N,N-二甲基甲酰胺、乙腈、甲苯、丙酮、四氢呋喃、二甲苯、碳酸二甲酯。
所述添加剂选自二异丙基胺三氟醋酸盐（ i- Pr2N-TFA）、二甲基胺三氟醋酸盐（Me2N-TFA）、二乙基胺三氟醋酸盐（Et2N-TFA）、二丁基胺三氟醋酸盐（ n-Bu2N-TFA）、二环己基胺三氟醋酸盐（hexyl2N-TFA）、二苄基胺三氟醋酸盐（Bz2N-TFA）、吗啡啉三氟醋酸盐（Morpholine -TFA）、二异丙基胺盐酸盐（ i- Pr2N-HCl）、二异丙基胺硫酸盐（ i- Pr2N-H2SO4）、二异丙基胺四氟硼酸盐（ i- Pr2N-HBF4）、二异丙基胺高氯酸盐（ i- Pr2N-HclO4）、二异丙基胺三氟甲磺酸盐（ i- Pr2N-HSO3CF3）。化合物1与添加剂的摩尔比为1:1~2。
上述1,4-氧硫杂-3,5-二醛基环己二烯的制备是在催化条件下两分子烯胺酮先在α位构建硫桥键，然后发生分子内环化，一分子烯胺酮的羰基被另一分子烯胺酮的羰基氧进攻，两分子水再进攻N,N-二甲基亚胺双键，脱去两分子的N,N-二甲胺得到最终产物。
本发明与现有技术相比，具有以下优点：
1、本发明合成的1,4-氧硫杂-3,5-二醛基环己二烯化合物是一种全新的杂环化合物；
2、本发明利用简单易得的原料：N,N-二甲基烯胺酮（1）是通过广泛存在的α-甲基酮类化合物在N,N-二甲基甲酰胺二甲基缩醛（DMF-DMA）中加热过夜即可较好产率获得；
3、本发明的合成方法简洁高效，一步反应构建目标产物，在空气环境中反应，操作简便，环境友好，产率高等特点，十分有利工业生产；
4、所得目标产物化合物结构多样性丰富，对特殊结构的底物也能够适用；
5、本发明不需要昂贵的催化剂且操作安全。
附图说明
图1为化合物3b的单晶结构图。
具体实施方式
下面通过实施例对本发明作进一步详细说明，但本发明保护范围不局限于所述内容，实施例中试剂如无特殊说明，均为常规市售试剂或按常规方法制得的试剂。
实施例1：
在15mL厚壁耐压管中加入N,N-二甲基烯胺酮1a(0.5mmol)、NaI(0.35mmol)、 i- Pr2N-TFA(0.5 mmol)，加入1,4-dioxane (5mL)后加入化合物2(1mmol)，最后加入TBHP(1mmol)，在磁力搅拌下加热至60℃下反应2h；TLC监测反应，待原料点完全消失后，然后加入饱和硫代硫酸钠溶液混匀后加入乙酸乙酯萃取3次，收集合并有机相并用饱和食盐水洗涤，收集有机相后有机相用无水Na2SO4进行干燥，将经过干燥的液体浓缩蒸干，之后对浓缩蒸干物进行柱层析分离，柱色谱分离采用的溶剂为石油醚/乙酸乙酯的混合溶剂，收集洗脱液干燥，得红色固体3a，收率86 %，反应方程式如下：
产品3a的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1，R f = 0.15, 红色固体:66 mg, 产率 86%; 熔点 = 227-228oC; 1H NMR (600 MHz, CDCl3): δ = 9.51 (s, 2H, CHO), 7.60–7.50 (m, 10H, ArH);13C NMR (150 MHz, CDCl3): δ= 186.5, 186.5, 163.7, 163.7, 132.0, 132.0, 130.2,130.2, 129.5, 129.5, 129.5, 129.5, 129.0, 129.0, 129.0, 129.0, 114.3, 114.3;HRMS (TOF ES+): m/z calcd for C18H13O3S [(M+H)+], 309.0580, found, 309.0580.
下述实施例制备方法同实施例1；
实施例2：所得产品3b的结构、形态、熔点、核磁、高分辨质谱数据如下，化合物3b的单晶结构图见图1；
V石油醚/V乙酸乙酯 = 10:1, R f = 0.25, 红色固体:72 mg, 产率 85%; 熔点 = 209-210oC; 1H NMR (600 MHz, CDCl3): δ = 9.51 (s, 2H, CHO), 7.43–7.42 (d, J = 8.1 Hz,2H,ArH), 7.31–7.30 (d, J = 7.9 Hz, 2H,ArH), 2.45 (s, 6H, CH3); 13C NMR (150MHz, CDCl3): δ = 186.6, 186.6, 164.0, 164.0, 142.7, 142.7, 129.6, 129.6,129.6, 129.6, 129.5, 129.5, 129.5, 129.5, 127.4, 127.4, 113.8, 113.8, 21.6,21.6; HRMS (TOF ES+): m/z calcd for C20H17O3S [(M+H)+], 337.0893, found,337.0893.
实施例3所得产品3c的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯= 10:1, R f = 0.1, 红色固体:75 mg, 产率 83%; 熔点 = 240-241oC; 1H NMR (600 MHz, CDCl3): δ = 9.46 (s, 2H, CHO), 7.83 (d, J = 8.3 Hz, 4H,ArH), 7.65 (d, J = 8.3 Hz, 4H, ArH); 13C NMR (150 MHz, CDCl3): δ = 184.9,184.9, 160.3, 160.3, 133.8, 133.8, 132.8, 132.8, 132.8, , 132.8, 130.0,130.0, 130.0, 130.0, 117.4, 117.4, 116.4, 116.4, 115.8, 115.8; HRMS (TOF ES+): m/z calcd for C20H10N2NaO3S [(M+H)+], 381.0304, found, 381.0304.
实施例4所得产品3d的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.1, 橘黄色固体:84 mg, 产率 84%; 熔点 = 226-227 oC; 1H NMR (600 MHz, CDCl3): δ = 9.41 (s, 2H, CHO), 8.36–8.34 (d, J = 8.8Hz, 4H, ArH), 8.06–8.04 (d, J = 8.8 Hz, 4H, ArH); 13C NMR (150 MHz, CDCl3): δ=186.9, 186.9, 160.9, 160.9, 149.5, 149.5, 136.1, 136.1, 131.8, 131.8, 131.8,131.8, 124.4, 124.4, 124.4, 124.4, 114.8, 114.8; HRMS (TOF ES+): m/z calcdfor C18H11N2O7S [(M+H)+], 399.0281, found, 399.0279.
实施例5所得产品3e的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.25, 红色固体:58 mg, 产率 62%; 熔点 = 185-186oC; 1H NMR (600 MHz, CDCl3): δ = 9.48 (s, 2H, CHO), 7.53–7.43 (m, 8H, ArH); 13CNMR (150 MHz, CDCl3): δ= 185.8, 185.8, 162.1, 162.1, 138.4, 138.4, 130.7,130.7, 130.7, 130.7, 129.4, 129.4, 129.4, 129.4, 128.4, 128.4, 114.8, 114.8;HRMS (TOF ES+): m/z calcd for C18H11Cl2O3S [(M+H)+], 376.9800, found, 376.9799.
实施例6所得产品3f的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.2, 红色固体:82 mg, 产率 71%; 熔点 = 181-182oC; 1H NMR (600 MHz, CDCl3): δ = 9.48 (s, 2H, CHO), 7.66 (d, J = 8.5 Hz, 4H,ArH) , 7.39 (d, J = 8.5 Hz, 4H, ArH); 13C NMR (150 MHz, CDCl3): δ= 185.7,185.7, 162.1, 162.1, 132.4, 132.4, 132.4, 132.4, 130.8, 130.8, 130.8, 130.8,128.8, 128.8, 126.8, 126.8, 114.9 114.9; HRMS (TOF ES+): m/z calcd forC18H11Br2O3S [(M+H)+], 464.8790, found, 464.8788.
实施例7所得产品3g的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.15, 红色固体:85 mg, 产率 83%; 熔点 = 150-151oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.50 (s, 2H, CHO) , 8.40 (d, J = 1.9 Hz,2H) , 8.12–7.99 (m, 6H) , 7.80 (dd, J = 8.5, 1.8 Hz, 2H), 7.69–7.62 (dddd, J= 21.4, 8.1, 6.9, 1.4 Hz, 4H, ArH); 13C NMR (150 MHz, DMSO-d 6): δ= 187.4,187.4, 164.0, 164.0, 134.6, 134.6, 132.5, 132.5, 131.6, 131.6, 129.4, 129.4,129.2, 129.2, 128.8, 128.8, 128.2, 128.2, 127.7, 127.7, 127.6, 127.6, 125.7,125.7, 113.5; HRMS (TOF ES+): m/z calcd for C26H17O3S [(M+H)+], 409.0893,found, 409.0895.
实施例8所得产品3h的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 8:1, R f = 0.15, 红色固体:81 mg, 产率 82%; 熔点 = 241-242oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.40 (s, 2H, CHO) , 7.33 (s, 2H, ArH),7.25–7.23 (dd, J = 8.1, 1.9 Hz, 2H), 7.07–7.05 (dd, J = 8.1, 1.7 Hz, 2H),6.15 (s, 4H, CH2); 13C NMR (150 MHz, DMSO-d 6): δ= 186.9, 186.9, 163.6, 163.6,150.9, 150.9, 148.2, 148.2, 126.1, 126.1, 123.8, 123.8, 112.3, 112.3, 109.6,109.6, 108.9, 108.9, 102.6, 102.6; HRMS (TOF ES+): m/z calcd for C20H13O7S [(M+H)+], 397.0376, found, 397.0375.
实施例9所得产品3i的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.25, 红色固体:68 mg, 产率 76%; 熔点 = 225-226oC; 1H NMR (600 MHz, DMSO-d 6): δ = 10.35 (s, 2H, CHO) , 7.95 – 7.81 (m, 6H,ArH and CH) , 7.57 (s, J = 15.5 Hz, 2H, CH), 7.50 – 7.38 (m, 6H, ArH); 13C NMR(150 MHz, DMSO-d 6): δ = 186.9, 186.9, 157.8, 157.8, 135. 9, 135. 9, 135.7,135.7, 130.4, 130.4, 129.3, 129.3, 129.3, 129.3, 129.0, 129.0, 129.0, 129.0,115.6, 115.6, 114.0, 114.0; HRMS (TOF ES+): m/z calcd for C22H17O3S [(M+H)+],361.0893, found, 361.0893.
实施例10所得产品3j的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 8:1, R f = 0.15, 红色固体:92 mg, 产率 80%; 熔点 = 136-137oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.50 (s, 1H, CHO), 7.87–7.83 (q, J = 8.4Hz, 8H, ArH), 7.77–7.75 (m, 4H, ArH), 7.53–7.59 (t, J = 7.6 Hz, 4H), 7.45–7.42 (m, 2H, ArH); 13C NMR (150 MHz, DMSO-d 6): δ = 187.0, 187.0, 163.6, 163.6,143.9, 143.9, 139.2, 139.2, 130.9, 130.9, 130.9, 130.9, 129.6, 129.6, 129.6,129.6, 129.2, 129.2, 128.9, 128.9, 127.5, 127.5, 127.5, 127.5, 127.4, 127.4,127.4, 127.4, 113.2, 113.2; HRMS (TOF ES+): m/z calcd for C30H21O3S [(M+H)+],461.1206, found, 461.1205.
实施例11所得产品3k的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.25, 红色固体:80 mg, 产率 87%; 熔点 = 204-205oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.38 (s, 2H, CHO), 7.65–7.64 (m, 4H, ArH),7.08 (s, 4H, ArH), 3.83 (s, 3H, CH3); 13C NMR (150 MHz, DMSO-d 6): δ = 186.9,186.9, 164.2, 164.2, 162.6, 162.6, 132.1, 132.1, 132.1, 132.1, 132.1, 122.4,122.4, 114.8, 114.8, 114.8, 114.8, 112.0, 112.0, 56.0, 56.0; HRMS (TOF ES+):m/z calcd for C20H17O5S [(M+H)+], 369.0791, found, 369.0791.
实施例12所得产品3l的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 3:1, R f = 0.2, 红色固体: 97 mg, 产率 84%; 熔点 = 226-227oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.41 (s, 2H, CHO), 8.08–8.02 (m, 8H, ArH),3.30 (s, 6H, CH3); 13C NMR (150 MHz, DMSO-d 6): δ = 187.0, 187.0, 161.5, 161.5,143.7, 143.7, 134.8, 134.8, 131.3, 131.3, 131.3, 131.3, 127.9, 127.9, 127.9,127.9, 114.4, 114.4, 43.6, 43.6; HRMS (TOF ES+): m/z calcd for C20H17O7S3 [(M+H)+], 465.0131, found, 465.0132.
实施例13所得产品3m的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.2, 红色固体: 75 mg, 产率 87%; 熔点 = 229-230oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.38 (s, 2H, CHO), 7.83–7.81 (m, 4H, ArH),7.41–7.38 (m, 4H, ArH); 13C NMR (150 MHz, DMSO-d 6): δ = 187.0, 187.0, 164.4(C–F, 1J C–F = 250.4 Hz), 164.4 (C–F, 1J C–F = 250.4 Hz), 162.8, 162.8, 133.0(C–F, 3J C–F = 9.2 Hz), 133.0 (C–F, 3J C–F = 9.2 Hz), 133.0 (C–F, 3J C–F =9.2 Hz), 133.0 (C–F, 3J C–F = 9.2 Hz), 126.8 (C–F, 4J C–F = 3.2 Hz), 126.8(C–F, 4J C–F = 3.2 Hz), 116. 6 (C–F, 2J C–F = 22.1 Hz), 116. 6 (C–F, 2J C–F =22.1 Hz), 116.6 (C–F, 2J C–F = 22.1 Hz), 116. 6 (C–F, 2J C–F = 22.1 Hz),113.0, 113.0; HRMS (TOF ES+): m/z calcd for C18H11F2O3S [(M+H)+], 345.0391,found, 345.0390.
实施例14所得产品3n的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 2:1, R f = 0.15, 红色固体: 75 mg, 产率 76%; 熔点 = 231-232oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.55 (s, 2H, CHO), 7.44–7.43 (d, J = 8.9Hz, 4H, ArH), 6.72–6.71 (d, J = 8.6 Hz, 4H, ArH), 3.08 (s, 12H, NCH3); 13C NMR(150 MHz, DMSO-d 6): δ = 186.7, 186.7, 165.5, 165.5, 152.6, 152.6, 131.2,131.2, 131.2, 131.2, 117.1, 117.1, 111.4, 111.4, 111.2, 111.2, 111.2, 111.2,40.1, 40.1, 40.1, 40.1; HRMS (TOF ES+): m/z calcd for C22H23N2O3S [(M+H)+],395.1424, found, 395.1425.
实施例15所得产品3o的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.15, 红色固体: 46 mg, 产率 41%; 熔点 = 192-193 oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.41 (s, 2H, CHO), 7.99–7.98 (d, J =8.1 Hz, 4H, ArH), 7.92–7.90 (d, J = 8.2 Hz, 4H, ArH); 13C NMR (150 MHz, DMSO-d 6): δ = 187.0, 187.0, 161.7, 161.7, 134.2, 134.2, 131.9 (q, J = 33.0 Hz),131.9 (q, J = 33.0 Hz), 131.2, 131.2, 131.2, 131.2, 126.3 (q, J = 4.5 Hz),126.3 (q, J = 4.5 Hz), 126.3 (q, J = 4.5 Hz), 126.3 (q, J = 4.5 Hz), 124.2(q, J = 272.6 Hz), 124.2 (q, J = 272.6 Hz), 114.3, 114.3; HRMS (TOF ES+): m/zcalcd for C20H11F6O3S [(M+H)+], 445.0328, found, 445.0328.
实施例16所得产品3p的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 20:1, R f = 0.25, 黄色固体: 51 mg, 产率 48%; 熔点 = 256-257 oC; 1H NMR (600 MHz, DMSO-d 6): δ = 10.26 (s, 2H, CHO), 2.10–2.05 (m, 18H,CH and CH2), 1.75–1.68 (m, 12H, CH and CH2); 13C NMR (150 MHz, DMSO-d 6): δ =186.5, 186.5, 172.9, 172.9, 113.8, 113.8, 43.4, 43.4, 41.2, 41.2, 41.2, 41.2,41.2, 41.2, 36.1, 36.1, 36.1, 36.1, 36.1, 36.1, 28.2, 28.2, 28.2, 28.2, 28.2,28.2, ; HRMS (TOF ES+): m/z calcd for C26H33O3S [(M+H)+], 425.2145, found,425.2144.
实施例17所得产品3q的结构、形态、熔点、红外、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 8:1, R f = 0.15, 红色固体: 57 mg, 产率 79%; 熔点 = 198-199oC; 1H NMR (600 MHz, DMSO-d 6): δ = 10.17 (s, 2H, CHO), 8.11 (d, 2H, CH), 7.41(d, 2H, CH), 8.84–8.83 (dd, J = 3.6, 1.8 Hz, 2H, CH); 13C NMR (150 MHz, DMSO-d 6): δ = 186.5, 186.5, 151.6, 151.6, 149.0, 149.0, 145.0, 145.0, 117.6,117.6, 113.7, 113.7, 113.3, 113.3; HRMS (TOF ES+): m/z calcd for C14H9O5S [(M+H)+], 289.0165, found, 289.0166.
实施例18所得产品3r的结构、形态、熔点、红外、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 8:1, R f = 0.2, 红色固体: 53 mg, 产率 66%; 熔点 = 205-206oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.72 (s, 2H, CHO), 8.08–8.07 (dd, J = 5.0,1.2 Hz, 2H, CH), 7.88–7.87 (dd, J = 3.7, 1.2 Hz, 2H, CH), 7.29–7,28 (dd, J =5.1, 1.2 Hz, 2H, CH); 13C NMR (150 MHz, DMSO-d 6): δ = 186.2, 186.2, 157.5,157.5, 134.9, 134.9, 133.5, 133.5, 131.5, 131.5, 129.0, 129.0, 113.3, 113.3;HRMS (TOF ES+): m/z calcd for C14H9O3S3 [(M+H)+], 320.9708, found, 320.9706.
实施例19所得产品3s的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 5:1, R f = 0.2, 红色固体: 66 mg, 产率 85%; 熔点 = 156-157oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.44 (s, 2H, CHO), 8.78–8.77 (m, 4H, CH),8.77–8.75 (m, 4H, CH); 13C NMR (150 MHz, DMSO-d 6): δ = 186.8, 186.8, 160.6,160.6, 150.8, 150.8, 150.8, 150.8, 137.5, 137.5, 124.0, 124.0, 124.0, 124.0,114.9, 114.9; HRMS (TOF ES+): m/z calcd for C16H11N2O3S [(M+H)+], 311.0485,found, 311.0484.
实施例20所得产品3t的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.1, 红色固体: 86 mg, 产率 82%; 熔点 = 188-189oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.40 (s, 2H, CHO), 8.61–8.60 (t, J = 2.1Hz, 2H, ArH), 8.43–8.42 (dd, J = 7.9, 2.2 Hz, 2H, ArH), 8.21–8.19 (dt, J =7.7, 1.4 Hz, 2H, ArH), 7.85–7.82 (t, J = 8.0 Hz, 2H, ArH); 13C NMR (150 MHz,DMSO-d 6): δ = 187.2, 187.2, 160.9, 160.9, 148.4, 148.4, 136.5, 136.5, 131.7,131.7, 131.1, 131.1, 126.7, 126.7, 125.2, 125.2, 114.4, 114.4; HRMS (TOF ES+): m/z calcd for C18H10N2NaO7S [(M+H)+], 421.0101, found, 421.0101.
实施例21所得产品3u的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 3:1, R f = 0.15, 红色固体: 87 mg, 产率 82%; 熔点 = 216-217oC; 1H NMR (600 MHz, DMSO-d 6): δ = 10.72 (s, 2H, NH), 9.40 (s, 2H, CHO), 7.82–7.81 (d, J = 8.4 Hz, 4H, ArH), 7.65–7.64 (d, J = 8.3 Hz, 4H, ArH), 2.10 (s,6H, CH2); 13C NMR (150 MHz, DMSO-d 6): δ = 187.0, 187.0, 169.6, 169.6, 164.1,164.1, 143.3, 143.3, 131.2, 131.2, 131.2, 131.2, 124.2, 124.2, 119.0, 119.0,119.0, 119.0, 112.2, 112.2, 24.6, 24.6; HRMS (TOF ES+): m/z calcd forC22H19N2O5S [(M+H)+], 423.1009, found, 423.1010.
实施例22所得产品3v的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.25, 红色固体: 66 mg, 产率 73%; 熔点 = 142-143 oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.40 (s, 2H, CHO), 7.63–7.62 (d, J =8.2 Hz, 4H, ArH), 7.40–7.38 (d, J = 8.1 Hz, 4H, ArH), 2.70–2.66 (q, J = 7.6Hz, 4H, CH2), 1.22–1.19 (t, J = 7.6 Hz, 6H,CH3); 13C NMR (150 MHz, DMSO-d 6): δ= 187.0, 187.0, 164.1, 164.1, 148.7, 148.7, 130.3, 130.3, 130.3, 130.3,128.8, 128.8, 128.8, 128.8, 127.8, 127.8, 112.7, 112.7, 28.6, 28.6, 15.7,15.7; HRMS (TOF ES+): m/z calcd for C22H21O3S [(M+H)+], 365.1206, found,365.1205.
实施例23所得产品3w的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.15, 红色固体: 85 mg, 产率 83%; 熔点 = 244-245 oC; 1H NMR (600 MHz, CDCl3): δ = 9.25–9.23 (d, J = 13.2 Hz, 2H, CHO),8.26–8.25 (d, J = 8.3 Hz, 1H, ArH), 8.11–8.10(d, J = 8.4 Hz, 1H, ArH), 7.98–7.96 (t, J = 7.0 Hz, 2H, ArH), 7.88–7.86 (d, J = 8.1 Hz, 2H, ArH), 7.70–7.68(d, J = 7.0 Hz, 1H, ArH), 7.63–7.61 (d, J = 6.8 Hz, 1H, ArH), 7.59–7.49 (m,6H, ArH); 13C NMR (150 MHz, CDCl3): δ = 186.3, 186.2, 163.5, 163.0, 133.6,133.6, 132.0, 131.9, 131.4, 131.2, 129.5, 129.3, 128.8, 128.7, 127.8, 127.7,127.4, 127.3, 127.0, 127.0, 125.0, 124.9, 124.6, 124.6, 116.1, 115.7; HRMS(TOF ES+): m/z calcd for C26H17O3S [(M+H)+], 409.0893, found, 409.0893.
实施例24所得产品3x的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 8:1, R f = 0.25, 红色固体: 75 mg, 产率 77%; 熔点 = 194-195oC; 1H NMR (600 MHz, CDCl3): δ = 9.49 (s, 2H, CHO), 8.08–8.07 (d, J = 8.4 Hz,4H, ArH), 7.63–7.62 (d, J = 8.4 Hz, 4H, ArH), 2.66 (s, 6H, CH3); 13C NMR (150MHz, CDCl3): δ = 196.8, 196.8, 185.6, 185.6, 161.8, 161.8, 139.4, 139.4,133.9, 133.9, 129.7, 129.7, 129.7, 129.7, 128.8, 128.8, 115.7, 115.7, 26.8,26.8; HRMS (TOF ES+): m/z calcd for C22H17O5S [(M+H)+], 393.0791, found,393.0790.
实施例25所得产品3y的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 20:1, R f = 0.25, 橘黄色固体:19 mg, 产率 33%; 熔点 = 198-199 oC; 1H NMR (600 MHz, DMSO-d 6): δ = 10.00 (s, 2H, CHO), 2.74–2.69 (m, 2H,CH), 1.00–0.94 (m, 8H, CH2); 13C NMR (150 MHz, DMSO-d 6): δ = 186.2, 186.2,164.8, 164.8, 110.5, 110.5, 11.7, 11.7, 7.5, 7.5, 7.5, 7.5; HRMS (TOF ES+):m/z calcd for C12H13O3S [(M+H)+], 237.0580, found, 237.0580.
实施例26所得产品3z的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 15:1, R f = 0.1, 红色固体:51 mg, 产率 56%; 熔点 = 125-126oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.56 (s, 2H, CHO), 7.32–7.19 (m, 10H, ArH),2.98–2.88 (m, 8H, CH2); 13C NMR (150 MHz, DMSO-d 6): δ = 186.4, 186.4, 164.9,164.9, 140.0, 140.0, 129.1, 129.1, 129.1, 129.1, 128.9, 128.9, 128.9, 128.9,126.9, 126.9, 111.9, 111.9, 32.8, 32.8, 31.9, 31.9; HRMS (TOF ES+): m/z calcdfor C22H21O3S [(M+H)+], 365.1206, found, 365.1205.
实施例27所得产品3aa的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 25:1, R f = 0.15, 橘黄色液体: 37 mg, 产率 55%; 1H NMR (600MHz, DMSO-d 6): δ = 9.76 (s, 2H, CHO), 2.48–2.46 (d, J = 7.3 Hz, 4H, CH2),2.06–2.02 (dt, J = 13.6, 6.7 Hz, 2H, CH), 1.03–1.02 (d, J = 6.7 Hz, 12H,CH3); 13C NMR (150 MHz, DMSO-d 6): δ = 182.9, 182.9, 163.3, 163.3, 112.3,112.3, 38.1, 38.1, 25.8, 25.8, 21.0, 21.0, 21.0, 21.0; HRMS (TOF ES+): m/zcalcd for C14H21O3S [(M+H)+], 269.1206, found, 269.1206.
实施例28所得产品3bb的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 8:1, R f = 0.25, 红色固体:71 mg, 产率 84%; 熔点 = 247-248oC; 1H NMR (600 MHz, DMSO-d 6): δ = 10.42 (s, 2H, OH), 9.40 (s, 2H, CHO), 7.54(d, J = 8.3 Hz, 4H, ArH), 6.91–6.90 (d, J = 8.2 Hz, 4H, ArH); 13C NMR (150MHz, DMSO-d 6 ): δ = 186.9, 186.9, 164.9, 164.9, 161.5, 161.5, 132.3, 132.3,132.3, 132.3, 120.8, 120.8, 116.2, 116.2, 116.2, 116.2, 111.4, 111.4; HRMS(TOF ES+): m/z calcd for C18H13O5S [(M+H)+], 341.0478, found, 341.0479.
实施例29所得产品3cc的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.15, 橘黄色固体:47 mg, 产率 51%; 熔点 = 171-172 oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.17 (s, 2H, CHO), 7.57–7.52 (m, 4H,ArH), 7.20–7.18 (d, J = 8.4 Hz, 2H, ArH), 7.10–7.07 (m, 2H, ArH), 3.83 (s,6H, CH3); 13C NMR (150 MHz, DMSO-d 6 ): δ = 187.0, 187.0, 161.7, 161.7, 157.8,157.8, 133.7, 133.7, 131.8, 131.8, 121.1, 121.1, 119.0, 119.0, 113.3, 113.3,112.7, 112.7, 56.3, 56.3; HRMS (TOF ES+): m/z calcd for C20H17O5S [(M+H)+],369.0791, found, 369.0792.
实施例30所得产品3dd的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.15, 橘黄色固体:30 mg, 产率 35%; 熔点 = 145-146 oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.29–9.28 (d, J = 2.1 Hz, 2H, CHO),7.76–7.74 (m, 2H, ArH), 7.69–7.66 (dq, J = 5.1, 2.5 Hz, 2H, ArH), 7.45–7.42(t, J = 9.2 Hz, 2H, ArH), 7.40–7.38 (t, J = 7.6 Hz, 2H, ArH); 13C NMR (150MHz, DMSO-d 6 ): δ = 186.8, 186.8, 160.0 (C–F, 1J C–F = 250.5 Hz), 160.0 (C–F,1J C–F = 250.5 Hz), 158.1, 158.1, 134.7 (C–F, 3J C–F = 7.8 Hz), 134.7 (C–F,3J C–F = 7.8 Hz), 132.6, 132.6, 125.6, 125.6, 118.1 (C–F, 3J C–F = 13.1 Hz),118.1 (C–F, 3J C–F = 13.1 Hz), 117.0 (C–F, 2J C–F = 20.3 Hz), 117.0 (C–F, 2JC–F = 20.3 Hz), 114.6, 114.6; HRMS (TOF ES+): m/z calcd for C18H11F2O3S [(M+H)+], 345.0391, found, 345.0392.
实施例31所得产品3ee的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.15, 红色固体:79 mg, 产率 94%; 熔点 = 152-153oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.38 (s, 2H, CHO), 7.51–7.43 (m, 8H, ArH),2.37 (s, 6H, CH3); 13C NMR (150 MHz, DMSO-d 6 ): δ = 187.1, 187.1, 164.1, 164.1,138.9, 138.9, 133.1, 133.1, 130.5, 130.5, 130.2, 130.2, 129.3, 129.3, 127.3,127.3, 112.9, 112.9, 21.3, 21.3; HRMS (TOF ES+): m/z calcd for C20H17O3S [(M+H)+], 337.0893, found, 337.0894.
实施例32所得产品3ff的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 10:1, R f = 0.15, 红色固体:121 mg, 产率 86%; 熔点 = 152-153 oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.38 (s, 2H, CHO), 7.91 (d, J=8.0 Hz,4H, ArH), 7.49 (d, J=8.0 Hz, 4H, ArH); 13C NMR (150 MHz, DMSO-d 6 ): δ = 186.9,186.9, 162.8, 162.8, 138.2, 138.2, 138.2, 138.2, 131.9, 131.9, 131.9, 131.9,129.7, 129.7, 113.4, 113.4, 100.3, 100.3; HRMS (TOF ES+): m/z calcd forC18H11I2O3S [(M+H)+], 560.8513, found, 560.8513.
实施例33所得产品3gg的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 8:1, R f = 0.15, 黄色固体:142 mg, 产率 81%; 熔点 = 311-312oC; 1H NMR (600 MHz, CDCl3:DMSO-d 6 = 4:1): δ = 9.79 (d, J = 11.3 Hz, 2H, CHO),5.31 (m, 2H, OH), 3.42–3.39 (m, 2H), 3.19–3.14 (m, 2H), 2.61–2.59 (m, 2H),2.27–2.18 (dt, J = 30.5, 10.3 Hz, 6H), 2.03–1.99 (dt, J = 17.5, 5.9 Hz, 2H),1.82–1.77 (t, J = 14.4 Hz, 8H), 1.71–1.57 (m, 6H), 1.54–1.37 (ddtd, J = 43.5,23.6, 11.5, 10.9, 5.2 Hz, 8H), 1.25–1.12 (dtd, J = 41.5, 13.7, 12.4, 8.5 Hz,4H), 1.07–0.98 (q, J = 9.2, 6.6 Hz, 10H), 0.87–0.85 (d, J = 11.3 Hz, 6H); 13CNMR (150 MHz, CDCl3:DMSO-d 6 = 4:1): δ = 189.3, 189.3, 168.2, 168.2, 146.2,146.2, 125.4, 125.4, 118.2, 118.2, 75.4, 75.4, 60.5, 60.5, 55.3, 55.3, 54.7,54.7, 51.0, 51.0, 47.0, 47.0, 42.0, 42.0, 41.8, 41.8, 41.3, 41.3, 36.8, 36.8,36.5, 36.5, 36.3, 36.3, 29.3, 29.3, 27.7, 27.7, 25.5, 25.5, 24.2, 24.2, 18.7,18.7; HRMS (TOF ES+): m/z calcd for C44H61O5S [(M+H)+], 701.4234, found,701.4236.
实施例34：
在15 mL厚壁耐压管中加入N,N-二甲基烯胺酮1a (0.25mmol)、N,N-二甲基烯胺酮1l (0.25mmol)、NaI(0.35 mmol)、 i- Pr2N-TFA (0.5 mmol)，加入1,4-dioxane (5mL)后加入化合物2 (1mmol)，最后加入TBHP (1mmol)，在磁力搅拌下加热至60℃下反应2 h；TLC监测反应，待原料点完全消失后，反应物加入饱和硫代硫酸钠溶液，之后用有机溶剂乙酸乙酯对反应液进行萃取三次，收集合并有机层用饱和食盐水洗涤，有机相用无水Na2SO4进行干燥，将经过干燥的液体浓缩蒸干，之后对浓缩蒸干物进行柱层析分离，柱色谱分离采用的溶剂为石油醚/乙酸乙酯的混合溶剂，收集洗脱液干燥，得红色固体3a(20%)，3l(27%)和3gg(32%)，反应方程式如下：
所得产品3gg的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 8:1, R f = 0.15, 橘黄色固体:125 mg, 产率 32%; 熔点 = 101-102 oC; 1H NMR (600 MHz, CDCl3): δ = 9.48 (s, 1H, CHO), 9.47 (s, 1H, CHO),8.09 (d, J = 8.4 Hz, 2H, ArH), 7.75 (d, J = 8.4 Hz, 2H, ArH), 7.59 (tt, J =6.0, 3.0 Hz, 1H, ArH), 7.56–7.45 (m, 4H, ArH), 3.12 (s, 3H, CH3); 13C NMR (150MHz, CDCl3): δ = 186.2, 185.3, 163.4, 160.6, 143.3, 135.2, 132.3, 130.4,130.4, 129.7, 129.5, 129.5, 129.1, 129.1, 128.1, 128.1, 116.8, 113.9, 44.4;HRMS (TOF ES+): m/z calcd for C19H15O5S2 [(M+H)+], 387.0355, found, 387.0362.
实施例35:
在15 mL厚壁耐压管中加入N,N-二甲基烯胺酮1b (0.25mmol)、N,N-二甲基烯胺酮1l (0.25mmol)、NaI(0.35 mmol)、 i- Pr2N-TFA (0.5 mmol)，加入1,4-dioxane (5mL)后加入化合物2 (1mmol)，最后加入TBHP (1mmol)，在磁力搅拌下加热至60℃下反应2 h；TLC监测反应，待原料点完全消失后，反应物加入饱和硫代硫酸钠溶液，之后用有机溶剂乙酸乙酯对反应液进行萃取三次，收集合并有机层用饱和食盐水洗涤，收集有机相用无水Na2SO4进行干燥，将经过干燥的液体浓缩蒸干，之后对浓缩蒸干物进行柱层析分离，柱色谱分离采用的溶剂为石油醚/乙酸乙酯的混合溶剂，收集洗脱液干燥，得红色固体3b(26%)，3l(27%)和3hh(29%)，反应方程式如下：
所得产品3hh的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯 = 8:1, R f = 0.15, 红色固体:116 mg, 产率 29%; 熔点 = 107-108oC; 1H NMR (600 MHz, DMSO-d 6): δ = 9.40 (s, 1H, CHO), 9.38 (s, 1H, CHO), 8.12–7.80 (m, 4H, ArH), 7.60 (d, J = 7.8 Hz, 2H, ArH), 7.35 (d, J = 7.9 Hz, 2H,ArH), 3.29 (s, 3H, CH3), 2.38 (s, 3H, CH3); 13C NMR (150 MHz, DMSO-d 6): δ =187.0, 187.0, 164.2, 161.4, 143. 6, 142.8, 135.0, 131.2, 131.2, 130.7, 130.2,130.2, 129.9, 127.9, 127.8, 127.3, 115.0, 112.1, 43.6, 21.6; HRMS (TOF ES+):m/z calcd for C20H17O5S2 [(M+H)+], 401.0512, found, 401.0518.
Claims (7)
1.一种1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法，其特征在于：在密封耐压反应器中加入化合物1、化合物2、溶剂、催化剂、氧化剂、添加剂，在搅拌、55-65℃的油浴锅中反应2.0h，薄层色谱监测反应进程，直至反应完全；然后加入饱和硫代硫酸钠溶液混匀后加入乙酸乙酯萃取2-4次，收集合并有机相并用饱和食盐水洗涤，收集有机相后用无水硫酸钠干燥，减压蒸出溶剂，残渣用硅胶柱层析分离纯化得到化合物3；
其中R选自芳基、烷基。
2.根据权利要求1所述的1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法，其特征在于：催化剂选自五氧化二碘、四丁基碘化铵、碘化钾、碘化钠、碘化铵、碘化锂、碘化亚铜、N-碘代琥珀酰亚胺。
3.根据权利要求1所述的1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法，其特征在于：氧化剂选自叔丁基过氧化氢、过氧化苯甲酰、过氧化氢异丙苯、二叔丁基过氧化物、3-氯过氧化苯甲酸、过氧化苯甲酸叔丁酯、过硫酸钾、过硫酸钠、过硫酸铵、过氧硫酸氢钾复合盐。
4.根据权利要求1所述的1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法，其特征在于：溶剂选自1,4-二氧六环、二氯甲烷、甲醇、二甲基亚砜、N,N-二甲基甲酰胺、乙腈、甲苯、丙酮、四氢呋喃、二甲苯、碳酸二甲酯。
5.根据权利要求1所述的1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法，其特征在于：添加剂选自二异丙基胺三氟醋酸盐、二甲基胺三氟醋酸盐、二乙基胺三氟醋酸盐、二丁基胺三氟醋酸盐、二环己基胺三氟醋酸盐、二苄基胺三氟醋酸盐、吗啡啉三氟醋酸盐、二异丙基胺盐酸盐、二异丙基胺硫酸盐、二异丙基胺四氟硼酸盐、二异丙基胺高氯酸盐、二异丙基胺三氟甲磺酸盐。
6.根据权利要求1所述的1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法，其特征在于：化合物1与催化剂的摩尔比为1:0.1~1.0，化合物1与化合物2的摩尔比为1:1~3，化合物1与氧化剂的摩尔比为1:0.5~1，化合物1与添加剂的摩尔比为1:1~2。
7.根据权利要求1所述的1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法，其特征在于：反应温度为室温~100℃，反应时间为1~12h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210385120.2A CN114805289B (zh) | 2022-04-13 | 2022-04-13 | 一种1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210385120.2A CN114805289B (zh) | 2022-04-13 | 2022-04-13 | 一种1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114805289A true CN114805289A (zh) | 2022-07-29 |
| CN114805289B CN114805289B (zh) | 2024-05-28 |
Family
ID=82537480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210385120.2A Active CN114805289B (zh) | 2022-04-13 | 2022-04-13 | 一种1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114805289B (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947288A (zh) * | 2010-04-14 | 2013-02-27 | 拜耳知识产权有限责任公司 | 作为杀菌剂的二噻英衍生物 |
| CN105153123A (zh) * | 2015-09-29 | 2015-12-16 | 合肥师范学院 | 一种4-吡嗪基嘧啶-2-磺酸钠的合成方法 |
| CN106946843A (zh) * | 2017-03-03 | 2017-07-14 | 北京化工大学 | 一种3‑酰基‑1,4‑氧硫杂环己烯的制备方法 |
| CN110590734A (zh) * | 2019-09-20 | 2019-12-20 | 常州大学 | 一种合成2-甲基-4H-苯并[d][1,3]氧硫杂环己二烯-4-酮的方法 |
-
2022
- 2022-04-13 CN CN202210385120.2A patent/CN114805289B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947288A (zh) * | 2010-04-14 | 2013-02-27 | 拜耳知识产权有限责任公司 | 作为杀菌剂的二噻英衍生物 |
| CN105153123A (zh) * | 2015-09-29 | 2015-12-16 | 合肥师范学院 | 一种4-吡嗪基嘧啶-2-磺酸钠的合成方法 |
| CN106946843A (zh) * | 2017-03-03 | 2017-07-14 | 北京化工大学 | 一种3‑酰基‑1,4‑氧硫杂环己烯的制备方法 |
| CN110590734A (zh) * | 2019-09-20 | 2019-12-20 | 常州大学 | 一种合成2-甲基-4H-苯并[d][1,3]氧硫杂环己二烯-4-酮的方法 |
Non-Patent Citations (1)
| Title |
|---|
| SAMUEL I. ETKIND ET AL: "Electroactive Anion Receptor with High Affinity for Arsenate", J. ORG. CHEM., vol. 85, 27 July 2020 (2020-07-27), pages 10050 - 10061 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114805289B (zh) | 2024-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111646964B (zh) | 一种碱催化的合成2h-吡喃-2-酮衍生物新方法 | |
| CN110511193B (zh) | 一种α-酮硫代酰胺类化合物及其合成方法 | |
| CN114805289A (zh) | 一种1,4-氧硫杂-3,5-二醛基环己二烯化合物的制备方法 | |
| CN112679521B (zh) | 一种温和的氮杂螺三环骨架分子的合成方法 | |
| JPH01117898A (ja) | 新規な１４−アジドステロイド誘導体およびその製造方法 | |
| CN112457175B (zh) | 一种制备1,3-二苄氧基-2-丙酮的方法 | |
| Newkome et al. | Chemistry of heterocyclic compounds. 136. 1, 3, 5-Tri [2, 6] pyridacyclohexaphane-2, 4, 6-trione ketals: synthesis, structural analysis, and complexation | |
| Barluenga et al. | Regiospecific synthesis of isoxazoles by reaction of 1-azabutadiene derivatives with hydroxylamine hydrochloride | |
| US4421923A (en) | Ring substituted crown ethers and method of producing same | |
| CN107721917B (zh) | 一种多取代烟酸酯类化合物的绿色合成方法 | |
| Piacenza | Nucleophilic substitution with inversion of alcohol configuration with the reagent complex triphenylphosphine-diethyl azodicarboxylate-carboxylic acid. A convenient preparation of epicholesterol | |
| CN107445835B (zh) | 一种1,2-二氢环丁烯并[a]萘衍生物及其前体的合成方法 | |
| Bates et al. | Acid catalysis of the Claisen rearrangement. 1. Formation of 4, 4'-bis (2H-chromenyl) mercury derivatives from aryl 2-propynyl ethers | |
| CN113620795B (zh) | 苯并环庚烯酮类化合物的合成方法 | |
| CN115385850B (zh) | 一种1,4-二氢吡啶化合物的制备方法 | |
| CN113004235B (zh) | 一种(z)-3-烯基苯酞衍生物的立体选择性合成方法 | |
| Jonas | Configuration of sodium salt and preparation of sulphonates and carboxylates of (E)-and (Z)-3-(hydroxymethylene) dihydro-2 (3H)-furanone | |
| CN107325025A (zh) | 一种手性α‑氨基酸衍生物及其制备方法 | |
| Satoh et al. | Synthesis of Unsymmetrically Substituted Antimony (V) Tetraphenylporphyrins. | |
| CN111499524B (zh) | 一种利用卤代中间体制备氨基醇化合物的方法 | |
| Hu et al. | Formation of stable enols from 1, 4-dilithio-1, 3-dienes and acid chlorides by a de-aromatization/Michael addition/re-aromatization domino process | |
| KR100543172B1 (ko) | 테레인 화합물의 제조방법 | |
| AU2022403631A1 (en) | Catalytic tetrahydrocannabinol synthesis and precursors | |
| CN117486880A (zh) | 一种将吡咯和吡啶嵌入苝的稠环芳烃的制备方法及应用 | |
| Takekuma et al. | X-Ray Crystal Structure and Electrochemical Behavior of (5 R, 5′ S)-5, 5′-Biguaiazulene-3, 3′(5 H, 5′ H)-dione |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |