CN113416138A - 一种铁介导醛与溴代硝基甲烷的Henry型反应方法及产物 - Google Patents
一种铁介导醛与溴代硝基甲烷的Henry型反应方法及产物 Download PDFInfo
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- CN113416138A CN113416138A CN202110825956.5A CN202110825956A CN113416138A CN 113416138 A CN113416138 A CN 113416138A CN 202110825956 A CN202110825956 A CN 202110825956A CN 113416138 A CN113416138 A CN 113416138A
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- Prior art keywords
- bromonitromethane
- iron
- henry
- type reaction
- mediated
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 54
- DNPRVXJGNANVCZ-UHFFFAOYSA-N bromo(nitro)methane Chemical compound [O-][N+](=O)CBr DNPRVXJGNANVCZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 30
- 230000001404 mediated effect Effects 0.000 title claims abstract description 29
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 23
- -1 aldehyde compound Chemical class 0.000 claims abstract description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012043 crude product Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims abstract description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 6
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 16
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 5
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 4
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 4
- 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 3
- UZQDUXAJFTWMDT-UHFFFAOYSA-N 4-(2-trimethylsilylethynyl)benzaldehyde Chemical compound C[Si](C)(C)C#CC1=CC=C(C=O)C=C1 UZQDUXAJFTWMDT-UHFFFAOYSA-N 0.000 claims description 3
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 claims description 3
- 229940107816 ammonium iodide Drugs 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 229960000359 chromic chloride Drugs 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 2
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 claims description 2
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001431 2-methylbenzaldehyde Substances 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 claims description 2
- XQNVDQZWOBPLQZ-UHFFFAOYSA-N 4-(trifluoromethoxy)benzaldehyde Chemical compound FC(F)(F)OC1=CC=C(C=O)C=C1 XQNVDQZWOBPLQZ-UHFFFAOYSA-N 0.000 claims description 2
- BEOBZEOPTQQELP-UHFFFAOYSA-N 4-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=C(C=O)C=C1 BEOBZEOPTQQELP-UHFFFAOYSA-N 0.000 claims description 2
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 2
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 claims description 2
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 claims description 2
- NIEBHDXUIJSHSL-UHFFFAOYSA-N 4-iodobenzaldehyde Chemical compound IC1=CC=C(C=O)C=C1 NIEBHDXUIJSHSL-UHFFFAOYSA-N 0.000 claims description 2
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004799 bromophenyl group Chemical group 0.000 claims description 2
- 125000000068 chlorophenyl group Chemical group 0.000 claims description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 claims description 2
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 2
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims description 2
- 125000006303 iodophenyl group Chemical group 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 229920006395 saturated elastomer Polymers 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WNUQITFXWFDBIZ-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-nitroethanol Chemical compound [O-][N+](=O)CC(O)C1=CC=C(Cl)C=C1 WNUQITFXWFDBIZ-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000005526 G1 to G0 transition Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WSFMNWXMJBFYQT-UHFFFAOYSA-N 4-(4-acetylphenyl)benzaldehyde Chemical compound C1=CC(C(=O)C)=CC=C1C1=CC=C(C=O)C=C1 WSFMNWXMJBFYQT-UHFFFAOYSA-N 0.000 description 1
- 238000006842 Henry reaction Methods 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QDYBCIWLGJMJGO-UHFFFAOYSA-N dinitromethanone Chemical class [O-][N+](=O)C(=O)[N+]([O-])=O QDYBCIWLGJMJGO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
- C07C205/14—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to acyclic carbon atoms
- C07C205/15—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
- C07C205/14—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to acyclic carbon atoms
- C07C205/16—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to acyclic carbon atoms of a carbon skeleton containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
- C07C205/26—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups and being further substituted by halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/45—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
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Abstract
本发明公开了一种铁介导醛与溴代硝基甲烷的Henry型反应方法及产物,包括,依次加入铁粉、超干MeCN,随后依次加入1,2‑二溴乙烷和三甲基氯硅烷对铁粉进行活化;加入催化剂、添加剂、溴代硝基甲烷和醛基化合物,搅拌;用饱和NH4Cl溶液淬灭,用乙酸乙酯进行萃取;萃取液用饱和食盐水洗涤、无水硫酸钠干燥后,通过旋蒸除去萃取液,获得粗产物;粗产物通过硅胶柱层析法提纯,得到目标产物。本发明反应条件温和,以良好的区域选择性进行,易于操作且经济实惠,无需提前制备对水敏感的有机金属试剂。
Description
技术领域
本发明属于有机化合物合成技术领域,具体涉及到一种铁介导醛与溴代硝基甲烷的Henry型反应方法及产物。
背景技术
2-硝基-1-醇被证明是有机合成化学中一个重要的合成子,它可以实现各种有机转化,快速构建各种类型的目标产物(例如氨基醇、硝基烯烃、硝基酮等)。通常情况下,该化合物是通过羰基化合物和硝基甲烷在碱性条件下反应得到的。
金属介导的羰基化合物与溴代硝基甲烷的Henry型反应吸引了很多研究人员的关注。与传统的Henry反应相比,其避免了使用强碱性的反应条件,这就使得其底物的普适性大大增强。目前,多种金属介导Henry型反应相继被报道出来,包括使用SmI2,In,Zn,和SnCl2。但是这些方法大多需要使用空气敏感的或者有毒的试剂,这就限制了它的实际应用,同时也与当今时代倡导的绿色化学的理念不一致。因此开发一种金属便宜易得的、环境友好的Henry型反应体系是一个值得进一步探索的课题。
发明内容
本部分的目的在于概述本发明的实施例的一些方面以及简要介绍一些较佳实施例。在本部分以及本申请的说明书摘要和发明名称中可能会做些简化或省略以避免使本部分、说明书摘要和发明名称的目的模糊,而这种简化或省略不能用于限制本发明的范围。
鉴于上述和/或现有技术中存在的问题,提出了本发明。
本发明的其中一个目的是提供一种铁介导醛与溴代硝基甲烷的Henry型反应新方法,并提供一系列2-硝基-1-醇类化合物。该反应的化学方程式如下所示:
为解决上述技术问题,本发明提供了如下技术方案:一种铁介导醛与溴代硝基甲烷的Henry型反应方法,包括,
依次加入金属还原剂、溶剂,随后依次加入1,2-二溴乙烷和三甲基氯硅烷对铁粉进行活化;
加入催化剂、添加剂、溴代硝基甲烷和醛基化合物,搅拌;
用饱和NH4Cl溶液淬灭,用乙酸乙酯进行萃取;
萃取液用饱和食盐水洗涤、无水硫酸钠干燥后,通过旋蒸除去萃取液,获得粗产物;
粗产物通过硅胶柱层析法提纯,得到目标产物。
作为本发明铁介导醛与溴代硝基甲烷的Henry型反应方法的一种优选方案,其中:所述醛基化合物包括4-氯苯甲醛,4-硝基苯甲醛,4-甲酰基苯甲酸甲酯,4-三氟甲基苯甲醛,4-三氟甲氧基苯甲醛,4-甲酰基苯甲腈,4-氟苯甲醛,4-溴苯甲醛,2-溴苯甲醛,3-溴苯甲醛,4-碘苯甲醛,4-甲基苯甲醛,4-甲氧基苯甲醛,4-((三甲基硅基)乙炔基)苯甲醛,噻吩-2-甲醛,1-萘醛,肉桂醛,3-苯丙醛,3,7-二甲基辛-6-烯醛中的一种。
作为本发明铁介导醛与溴代硝基甲烷的Henry型反应方法的一种优选方案,其中:所述催化剂包括二氯化铅、二溴化铅、二碘化铅、三氯化铟、三氯化铋、二氯化锰、三氯化铬、二氯化锌、三氯化铁、二氯化铁、三溴化铁、二溴化铁、溴化亚铜、碘化亚铜、碘化钠、碘化铵、碘化锂中的一种。
作为本发明铁介导醛与溴代硝基甲烷的Henry型反应方法的一种优选方案,其中:所述催化剂为二氯化铅。
作为本发明铁介导醛与溴代硝基甲烷的Henry型反应方法的一种优选方案,其中:所述金属还原剂包括铁、锰、铝、铅、镓、铋中的一种。
作为本发明铁介导醛与溴代硝基甲烷的Henry型反应方法的一种优选方案,其中:所述金属还原剂为铁。
作为本发明铁介导醛与溴代硝基甲烷的Henry型反应方法的一种优选方案,其中:所述溶剂包括乙腈、四氢呋喃、N-甲基甲酰胺、二甲基亚砜、甲醇、1,2-二氯乙烷、乙二醇二甲醚中的一种。
作为本发明铁介导醛与溴代硝基甲烷的Henry型反应方法的一种优选方案,其中:所述溶剂为乙腈。
作为本发明铁介导醛与溴代硝基甲烷的Henry型反应方法的一种优选方案,其中:所述添加剂包括四丁基溴化铵、四丁基碘化铵、四丁基硫酸氢铵、十六烷基三甲基溴化铵中的一种。
作为本发明铁介导醛与溴代硝基甲烷的Henry型反应方法的一种优选方案,其中:所述添加剂为四丁基硫酸氢铵。
作为本发明铁介导醛与溴代硝基甲烷的Henry型反应方法的一种优选方案,其中:所述醛基化合物和溴代硝基甲烷的摩尔比为1:2~3。
作为本发明铁介导醛与溴代硝基甲烷的Henry型反应方法的一种优选方案,其中:所述搅拌,温度为60℃,时间为24h。
本发明的另一个目的是提供一种所述的铁介导醛与溴代硝基甲烷的Henry型反应方法得到的2-硝基-1-醇类化合物,所述2-硝基-1-醇类化合物的通式为:
其中,R包括卤素取代苯基、氰基取代苯基、三氟甲基取代苯基、三氟甲氧基取代苯基、酯基取代苯基、硝基取代苯基、甲基取代苯基、甲氧基取代苯基、2-萘基、苯乙烯基、4-((三甲基硅基)乙炔基)苯基、苯乙基、2,6-二甲基-2-庚烯基种的一种。
作为本发明2-硝基-1-醇类化合物的一种优选方案,其中:所述卤素取代的苯基包括氟苯基、氯苯基、溴苯基、碘苯基中的一种。
与现有技术相比,本发明具有如下有益效果:
本发明提供了一种使用PbCl2为催化剂,Fe粉为促进剂,TBAHS为添加剂,在MeCN中实现了醛与溴代硝基甲烷反应简单高效地合成了一系列2-硝基-1-醇类化合物;该反应条件温和,以良好的区域选择性进行,并且得到一系列具有广泛的官能团兼容性的加成产物;本发明使用廉价易得的铁粉,通过“一锅法”反应,易于操作且经济实惠,无需提前制备对水敏感的有机金属试剂。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其它的附图。其中:
图1为本发明实施例1的目标产物1-(4-氯苯基)-2-硝基乙醇的氢谱;
图2为本发明实施例1的目标产物1-(4-氯苯基)-2-硝基乙醇的碳谱;
图3为本发明实施例2的目标产物2-硝基-1-(4’-((三甲基硅基)乙炔基)苯基)乙醇的氢谱;
图4为本发明实施例2的目标产物2-硝基-1-(4’-((三甲基硅基)乙炔基)苯基)乙醇的碳谱;
图5为本发明实施例3的目标产物4-乙酰基-4’-(1-羟基-2-硝基)乙基联苯的氢谱;
图6为本发明实施例3的目标产物4-乙酰基-4’-(1-羟基-2-硝基)乙基联苯的碳谱。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合说明书实施例对本发明的具体实施方式做详细的说明。
在下面的描述中阐述了很多具体细节以便于充分理解本发明,但是本发明还可以采用其他不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似推广,因此本发明不受下面公开的具体实施例的限制。
其次,此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例,也不是单独的或选择性的与其他实施例互相排斥的实施例。
实施例1
(1)向10mL Schlenk管中依次加入铁粉(50.3mg,0.9mmol,3.0equiv.)和MeCN(1mL);加入1,2-二溴乙烷(8.5mg,0.05mmol)在320℃下用电加热枪加热35秒后冷却至室温;随后加入三甲基氯硅烷(7mg,0.05mmol),并使用320℃电加热枪加热35秒,再次冷却至室温完成铁粉的活化;搅拌5分钟后,依次向反应瓶中加PbCl2(17mg,0.06mmol,0.2equiv.),TBAHS(101mg,0.6mmol,2.0equiv.),溴代硝基甲烷(126mg,0.9mmol,3.0equiv.)和对氯苯甲醛(0.3mmol,1.0equiv.);将该反应混合物在60℃下搅拌24h。
(2)在步骤(1)反应结束后,用饱和NH4Cl溶液淬灭,并用乙酸乙酯(20mL×3)萃取;合并的有机相先后用饱和食盐水(20mL)洗涤、无水硫酸钠干燥、以及真空浓缩获得粗产物;该粗产物通过硅胶柱层析法提纯,柱层析分离条件:固定相为300~400目硅胶粉,流动相为乙酸乙酯(A)和石油醚(B),流动相变化程序(A:B)为1:20→1:4,最终得到44.6mg的目标产物1-(4-氯苯基)-2-硝基乙醇,该化合物结构式为:
对上述1-(4-氯苯基)-2-硝基乙醇进行表征,如图1和2所示,结果为:无色油状液体;1H NMR(400MHz,CDCl3):δ7.41–7.31(m,4H),5.44(dt,J=9.5,3.1Hz,1H),4.57(dd,J=13.5,9.5Hz,1H),4.48(dd,J=13.5,3.2Hz,1H),3.07(d,J=3.6Hz,1H)ppm.13C NMR(100MHz,CDCl3):δ136.5,134.8,129.2,127.3,80.9,70.2ppm.HRMS(m/z):calcd forC8H9ClNO3 +[M+H]+202.0265,found:202.0271.IR(KBr):ν=3447,1623,1595,1553,1380,1332,910cm-1.
根据表征数据可知,制得的反应产物1-(4-氯苯基)-2-硝基乙醇(纯度>98%);对产品产率进行计算,结果为74%。
实施例2
(1)向10mL Schlenk管中依次加入铁粉(50.3mg,0.9mmol,3.0equiv.)和MeCN(1mL);加入1,2-二溴乙烷(8.5mg,0.05mmol)在320℃下用电加热枪加热35秒后冷却至室温;随后加入三甲基氯硅烷(7mg,0.05mmol),并使用320℃电加热枪加热35秒,再次冷却至室温完成铁粉的活化;搅拌5分钟后,依次向反应瓶中加PbCl2(17mg,0.06mmol,0.2equiv.),TBAHS(101mg,0.6mmol,2.0equiv.),溴代硝基甲烷(126mg,0.9mmol,3.0equiv.)和4-((三甲基硅基)乙炔基)苯甲醛(0.3mmol,1.0equiv.);将该反应混合物在60℃下搅拌24h。
(2)在步骤(1)反应结束后,用饱和NH4Cl溶液淬灭,并用乙酸乙酯(20mL×3)萃取;合并的有机相先后用饱和食盐水(20mL)洗涤、无水硫酸钠干燥、以及真空浓缩获得粗产物;该粗产物通过硅胶柱层析法提纯,柱层析分离条件:固定相为300~400目硅胶粉,流动相为乙酸乙酯(A)和石油醚(B),流动相变化程序(A:B)为1:20→1:4,最终得到38.7mg的目标产物2-硝基-1-(4’-((三甲基硅基)乙炔基)苯基)乙醇,该化合物结构式为:
对上述2-硝基-1-(4’-((三甲基硅基)乙炔基)苯基)乙醇进行表征,如图3和4所示,结果为:无色油状液体;1H NMR(400MHz,CDCl3):δ7.49(d,J=8.5Hz,2H),7.34(d,J=8.1Hz,2H),5.46(dd,J=9.4,3.1Hz,1H),4.57(dd,J=13.4,9.5Hz,1H),4.49(dd,J=13.5,3.1Hz,1H),2.91(brs,1H),0.25(s,9H)ppm.13C NMR(100MHz,CDCl3):δ138.1,132.5,125.8,123.8,104.1,95.3,80.9,70.6,-0.1ppm.HRMS(m/z):calcd for C13H18NO3Si+[M+H]+264.1050,found:264.1056.IR(KBr):ν=3529,2958,2156,1553,1384,1076,867cm-1.
根据表征数据可知,制得的反应产物2-硝基-1-(4’-((三甲基硅基)乙炔基)苯基)乙醇(纯度>98%);对产品产率进行计算,结果为49%。
实施例3
(1)向10mL Schlenk管中依次加入铁粉(50.3mg,0.9mmol,3.0equiv.)和MeCN(1mL);加入1,2-二溴乙烷(8.5mg,0.05mmol)在320℃下用电加热枪加热35秒后冷却至室温;随后加入三甲基氯硅烷(7mg,0.05mmol),并使用320℃电加热枪加热35秒,再次冷却至室温完成铁粉的活化;搅拌5分钟后,依次向反应瓶中加PbCl2(17mg,0.06mmol,0.2equiv.),TBAHS(101mg,0.6mmol,2.0equiv.),溴代硝基甲烷(126mg,0.9mmol,3.0equiv.)和4’-乙酰基-联苯-4-甲醛(0.3mmol,1.0equiv.);将该反应混合物在60℃下搅拌24h。
(2)在步骤(1)反应结束后,用饱和NH4Cl溶液淬灭,并用乙酸乙酯(20mL×3)萃取;合并的有机相先后用饱和食盐水(20mL)洗涤、无水硫酸钠干燥、以及真空浓缩获得粗产物;该粗产物通过硅胶柱层析法提纯,柱层析分离条件:固定相为300~400目硅胶粉,流动相为乙酸乙酯(A)和石油醚(B),流动相变化程序(A:B)为1:20→1:4,最终得到52.2mg的目标产物4-乙酰基-4’-(1-羟基-2-硝基)乙基联苯,该化合物结构式为:
对上述4-乙酰基-4’-(1-羟基-2-硝基)乙基联苯进行表征,如图5和6所示,结果为:白色固体;1H NMR(400MHz,CDCl3):δ8.03(d,J=8.3Hz,2H),7.67(dd,J=8.4,2.4Hz,4H),7.52(d,J=8.2Hz,2H),5.55(dd,J=9.4,3.0Hz,1H),4.66(dd,J=13.4,9.5Hz,1H),4.57(dd,J=13.4,3.0Hz,1H),2.64(s,3H),1.68(brs,1H)ppm.13C NMR(100MHz,CDCl3):δ197.8,144.8,140.5,138.1,136.1,129.0,127.9,127.2,126.6,81.1,70.6,26.7ppm.IR(KBr):ν=3347,2918,1668,1549,1381,1274,819cm-1.HRMS(m/z):calcd for C16H16NO4 +[M+H]+286.1074,found:286.1079.
根据表征数据可知,制得的反应产物4-乙酰基-4’-(1-羟基-2-硝基)乙基联苯(纯度>98%);对产品产率进行计算,结果为61%。
实施例4
实施例4与实施例1基本相同,差别之处在于步骤(1)中,催化剂不同并且未使用添加剂,具体如下表2所示:
表2
从表2中可以看出,相同反应条件下,使用催化剂,如:二溴化铅、二碘化铅、三氯化铟、三氯化铋、二氯化锰、三氯化铬、二氯化锌、三氯化铁、二氯化铁、三溴化铁、二溴化铁、溴化亚铜、碘化亚铜、碘化钠、碘化铵或碘化锂合成1-(4-氯苯基)-2-硝基乙醇1,产率较低;当以二氯化铅作催化剂时,反应产率为53%。
实施例5
实施例5与实施例1基本相同,差别之处在于步骤(1)中,添加剂不同,具体如下表3所示:
表3
添加剂 | 产率(%) |
TBAB | 32 |
TBAI | <5 |
TBAHS | 78 |
CTMAB | 20 |
从表3中可以看出,相同反应条件下,使用催化剂,如:四丁基溴化铵、四丁基碘化铵、十六烷基三甲基溴化铵合成1-(4-氯苯基)-2-硝基乙醇,产率较低;当以四丁基硫酸氢铵作添加剂时,反应核磁产率为78%。
实施例6
实施例6与实施例1基本相同,差别之处在于步骤(1)中,金属还原剂不同,具体如下表4所示:
表4
从表4中可以看出,相同反应条件下,使用金属还原剂,如:锰、铝、铅、镓、铋,产率较低;当以铁作金属还原剂时,反应核磁产率为78%。
实施例7
实施例7与实施例1基本相同,差别之处在于步骤(1)中,金属还原剂不同,具体如下表5所示:
表5
溶剂 | 产率(%) |
MeCN | 78 |
THF | 22 |
DMF | 56 |
DMSO | 37 |
MeOH | 13 |
DCE | 13 |
DME | 38 |
从表5中可以看出,相同反应条件下,使用金属还原剂,如:四氢呋喃、N-甲基甲酰胺、二甲基亚砜、甲醇、1,2-二氯乙烷、乙二醇二甲醚,产率较低;当以乙腈作溶剂时,反应核磁产率为78%。
实施例8
实施例8与实施例1基本相同,差别之处在于步骤(1)中,醛基化合物不同,具体如下表6所示:
表6
本发明提供了一种使用PbCl2为催化剂,Fe粉为促进剂,TBAHS为添加剂,在MeCN中实现了醛与溴代硝基甲烷反应简单高效地合成了一系列2-硝基-1-醇类化合物;该反应条件温和,以良好的区域选择性进行,并且得到一系列具有广泛的官能团兼容性的加成产物;本发明使用廉价易得的铁粉,通过“一锅法”反应,易于操作且经济实惠,无需提前制备对水敏感的有机金属试剂。
应说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (10)
1.一种铁介导醛与溴代硝基甲烷的Henry型反应方法,其特征在于:包括,
依次加入铁粉、超干MeCN,随后依次加入1,2-二溴乙烷和三甲基氯硅烷对铁粉进行活化;
加入催化剂、添加剂、溴代硝基甲烷和醛基化合物,搅拌;
用饱和NH4Cl溶液淬灭,用乙酸乙酯进行萃取;
萃取液用饱和食盐水洗涤、无水硫酸钠干燥后,通过旋蒸除去萃取液,获得粗产物;
粗产物通过硅胶柱层析法提纯,得到目标产物。
2.如权利要求1所述的铁介导醛与溴代硝基甲烷的Henry型反应方法,其特征在于:所述醛基化合物包括4-氯苯甲醛,4-硝基苯甲醛,4-甲酰基苯甲酸甲酯,4-三氟甲基苯甲醛,4-三氟甲氧基苯甲醛,4-甲酰基苯甲腈,4-氟苯甲醛,4-溴苯甲醛,2-溴苯甲醛,3-溴苯甲醛,4-碘苯甲醛,4-甲基苯甲醛,4-甲氧基苯甲醛,4-((三甲基硅基)乙炔基)苯甲醛,噻吩-2-甲醛,1-萘醛,肉桂醛,3-苯丙醛,3,7-二甲基辛-6-烯醛中的一种。
3.如权利要求1或2所述的铁介导醛与溴代硝基甲烷的Henry型反应方法,其特征在于:所述催化剂包括二氯化铅、二溴化铅、二碘化铅、三氯化铟、三氯化铋、二氯化锰、三氯化铬、二氯化锌、三氯化铁、二氯化铁、三溴化铁、二溴化铁、溴化亚铜、碘化亚铜、碘化钠、碘化铵、碘化锂中的一种。
4.如权利要求3所述的铁介导醛与溴代硝基甲烷的Henry型反应方法,其特征在于:所述催化剂为二氯化铅。
5.如权利要求1、2或4任一所述的铁介导醛与溴代硝基甲烷的Henry型反应方法,其特征在于:所述添加剂包括四丁基溴化铵、四丁基碘化铵、四丁基硫酸氢铵、十六烷基三甲基溴化铵中的一种。
6.如权利要求5所述的铁介导醛与溴代硝基甲烷的Henry型反应方法,其特征在于:所述添加剂为四丁基硫酸氢铵。
7.如权利要求1、2、4或6任一所述的铁介导醛与溴代硝基甲烷的Henry型反应方法,其特征在于:所述醛基化合物和溴代硝基甲烷的摩尔比为1:2~3。
8.如权利要求7所述的铁介导醛与溴代硝基甲烷的Henry型反应方法,其特征在于:所述搅拌,温度为60℃,时间为24h。
10.如权利要求9所述的产物,其特征在于:所述卤素取代的苯基包括氟苯基、氯苯基、溴苯基、碘苯基中的一种。
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