CN104926674B - A kind of (Z)-3-dimethylamino-2-phenoxy group-α, beta-unsaturated acyl amine and preparation method thereof - Google Patents
A kind of (Z)-3-dimethylamino-2-phenoxy group-α, beta-unsaturated acyl amine and preparation method thereof Download PDFInfo
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- CN104926674B CN104926674B CN201510267937.XA CN201510267937A CN104926674B CN 104926674 B CN104926674 B CN 104926674B CN 201510267937 A CN201510267937 A CN 201510267937A CN 104926674 B CN104926674 B CN 104926674B
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- dimethylamino
- phenoxy group
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- unsaturated acyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- -1 beta-unsaturated acyl amine Chemical class 0.000 title claims description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000001409 amidines Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 150000001448 anilines Chemical class 0.000 claims abstract description 9
- 229940126214 compound 3 Drugs 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 150000001408 amides Chemical class 0.000 claims abstract 5
- REPVNSJSTLRQEQ-UHFFFAOYSA-N n,n-dimethylacetamide;n,n-dimethylformamide Chemical compound CN(C)C=O.CN(C)C(C)=O REPVNSJSTLRQEQ-UHFFFAOYSA-N 0.000 claims abstract 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 3
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical class CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000006260 ethylaminocarbonyl group Chemical group [H]N(C(*)=O)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 235000003642 hunger Nutrition 0.000 claims description 2
- 125000004458 methylaminocarbonyl group Chemical group [H]N(C(*)=O)C([H])([H])[H] 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004440 column chromatography Methods 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- ZSXGLVDWWRXATF-UHFFFAOYSA-N N,N-dimethylformamide dimethyl acetal Chemical compound COC(OC)N(C)C ZSXGLVDWWRXATF-UHFFFAOYSA-N 0.000 abstract description 9
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 abstract 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 abstract 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- 239000012074 organic phase Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- IMPPGHMHELILKG-UHFFFAOYSA-N 4-ethoxyaniline Chemical compound CCOC1=CC=C(N)C=C1 IMPPGHMHELILKG-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000000376 reactant Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ZYMLBOINJTXUAK-UHFFFAOYSA-N dimethoxymethanamine Chemical compound COC(N)OC ZYMLBOINJTXUAK-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 150000002240 furans Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 2
- CMVQGHJVMKWGDH-UHFFFAOYSA-N ClCC(=O)Cl.[O] Chemical compound ClCC(=O)Cl.[O] CMVQGHJVMKWGDH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 150000003857 carboxamides Chemical class 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- WINDXPMAARBVOY-UHFFFAOYSA-N 1-butyltellanylbutane Chemical compound CCCC[Te]CCCC WINDXPMAARBVOY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JUIKUQOUMZUFQT-UHFFFAOYSA-N 2-bromoacetamide Chemical compound NC(=O)CBr JUIKUQOUMZUFQT-UHFFFAOYSA-N 0.000 description 1
- PKUPAJQAJXVUEK-UHFFFAOYSA-N 2-phenoxyacetyl chloride Chemical compound ClC(=O)COC1=CC=CC=C1 PKUPAJQAJXVUEK-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- YKLZQTOZWPEVHV-NYAKATHWSA-N CN(\C=C(\C(=O)NC1=CC=C(C=C1)OCC)/OC1=CC=CC=C1)C.C(C=C)(=O)N Chemical compound CN(\C=C(\C(=O)NC1=CC=C(C=C1)OCC)/OC1=CC=CC=C1)C.C(C=C)(=O)N YKLZQTOZWPEVHV-NYAKATHWSA-N 0.000 description 1
- KYMRXTOEFJZXOB-AAKIMCHBSA-N ClC1=CC=C(O\C(\C(=O)NC2=CC=C(C=C2)OCC)=C/N(C)C)C=C1.C(C=C)(=O)N Chemical compound ClC1=CC=C(O\C(\C(=O)NC2=CC=C(C=C2)OCC)=C/N(C)C)C=C1.C(C=C)(=O)N KYMRXTOEFJZXOB-AAKIMCHBSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000002082 anti-convulsion Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005447 aza-Wittig reaction Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XFDJMIHUAHSGKG-UHFFFAOYSA-N chlorethoxyfos Chemical compound CCOP(=S)(OCC)OC(Cl)C(Cl)(Cl)Cl XFDJMIHUAHSGKG-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- IJCCOEGCVILSMZ-UHFFFAOYSA-L copper;dichlorate Chemical compound [Cu+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O IJCCOEGCVILSMZ-UHFFFAOYSA-L 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical class O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 229930185107 quinolinone Natural products 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses one (Z) 3 dimethylamino 2 phenoxy group α, β unsaturated amides and preparation method thereof, the reaction first step, in proper temperature and coordinative solvent, with amino benzenes compounds 1 and DMF DMA(N, N Dimethylformamide dimethyl acetal) react and purified rear generation corresponding virtue amidine 2；Reaction second step, generates compound 4, i.e. (Z) 3 dimethylamino 2 phenoxy group α, β unsaturated amides after being reacted with compound 3 and be purified by generation corresponding virtue amidine 2 in proper temperature, appropriate solvent and in the presence of alkali.The invention provides a kind of high selective reaction and prepare a class (Z) 3 dimethylamino 2 phenoxy group α, the method for β unsaturated amides, course of reaction are simple, and expense is low, and safe and environment-friendly.
Description
Technical field
The invention belongs to the synthesis technical field of amide-type organic compound, be specifically related to one (Z)-3-dimethylamino-
2-phenoxy group-α, beta-unsaturated acyl amine and preparation method thereof.
Background technology
Containing α, beta-unsaturated acyl amine in many medicines and agricultural chemicals.The most anticonvulsion, antidepression, anti-female hormone, pain relieving
And antibiotic property etc., α, beta-unsaturated acyl amine is also widely used in the key areas such as agricultural, materials industry.α, β-no
Saturated amide compounds is with its multi-functional design feature, it has also become the intermediate that in organic synthesis, a class is important, permissible
For preparing the multiple heterocycles compounds such as quinoline, quinolinone, furans, piperidones, pyridine, pyridone, pyrroles.In general, α,
The reaction of beta-unsaturated acyl aminated compounds mainly has: with the reaction of electrophilic reagent, with the reaction of nucleopilic reagent, electrocyclization is anti-
Should, reduction and oxidation reaction.From structure, this α, the existing nucleophilicity of beta-unsaturated acyl amine also has electrophilicity, both can be with parent
Core reagent reacting can react with electrophilic reagent again.
α, the preparation method of beta-unsaturated acyl aminated compounds, patent 1 (U.S. Patent No. 2,451, No. 436), 2
(Japanese Unexamined Patent Publication 4-208258 publication) and 3 (Japanese Unexamined Patent Publication 6-199752 publications) disclose and use acrylate
The method of N,N-DMAA.But, in this method, not only need to be esterified acrylic acid, but also need institute
The ester group obtaining ester compounds is converted into the step of amide groups.Generally, by ester group in the conversion of amide groups, need glycerine etc.
Polyol compound, as solvent, needs the step separated from solvent by product the most after the completion of reaction.Therefore, receiving
There is too high problem in rate, expense aspect.
In prior art, other prepares α, and the method for beta-unsaturated acyl amine is: first unsaturated acids is made acyl chlorides, then
Product is obtained again with secondary amine amidation process.Produced acyl chlorides by unsaturated acids it is generally required to use oxalyl chloride, phosphorus trichloride, three
The chemicals that chlorethoxyfos or thionyl chloride etc. are volatile, excitant and corrosivity strong, toxicity is bigger, not only produces environment
Pollute, and too increase the difficulty of the separation in production process and purifying.Saturated amide compound can be at α, and β position is dehydrated
Prepare α, beta-unsaturated acyl amines, such as, and patent CN1826314 A(2006) disclose a kind of α, β-insatiable hunger
With the preparation method of amide compound, first blocking group is introduced saturated amide compound, at dehydrogenation and applicable oxygen
It is dehydrated in the presence of agent, reacts formation double bond, finally remove blocking group and obtain end product, but whole course of reaction
Required chemical reagent is many, and the reaction time is long, complicated condition.
2013 European Journal of Organic Chemistry [(Eur.J.0rg.Chem., 2013 (7): 1218)] report use height
Copper chlorate catalysis benzoic acid and Carbox amide synthesis acid amide compounds.But this catalyst system and catalyzing is to substrate requirements height also
And reaction needs to carry out under the high temperature of 100 ° of C.
2014 Chinese patent CN103232357B have reported one and have prepared α, and the method for beta-unsaturated acyl amine, at indifferent gas
In atmosphere, with cinnamic acid compound and Carbox amide as reactant, with molysite and oxidant as catalyst system and catalyzing, pass through acyl
Aminating reaction prepares product α, beta-unsaturated acyl amine.The method not only use various molysite as catalyst, but also need
Want TBHP etc. for oxidant.
Huang Zhizhen, Wu Luling at Chin. J. Org. Chem., 1996,16 (4): 340-343 report (E)-
α, the Stereo-selective synthesis of beta-unsaturated acyl amine.The method is bromo acetamide and aldehyde under metal and dibutyl tellurid effect
Target compound is generated by azaWittig reaction.
Summary of the invention
It is an object of the invention to provide one (Z)-3-dimethylamino-2-phenoxy group-α, beta-unsaturated acyl amine and system thereof
Preparation Method, to solve above-mentioned technical problem.
For achieving the above object, the technical solution used in the present invention is:
A kind of (Z)-3-dimethylamino-2-phenoxy group-α, beta-unsaturated acyl amine, for compound 4 in following formula:
Wherein: in amino benzenes compounds 1, R1For independent-H ,-F ,-Cl ,-Br ,-I ,-CN ,-NO2, -OH,
-CO2Me, -CO2Et, -CONHMe, -CONHEt, C1-C6Alkyl; R2For independent-H ,-F ,-OH ,-CN; R3For
Independent-H ,-CN ,-NO2；
In compound 3: R4For-H ,-Cl.
A kind of (Z)-3-dimethylamino-2-phenoxy group-α, the preparation method of beta-unsaturated acyl amine, comprise the following steps:
The reaction first step, in proper temperature and coordinative solvent, with amino benzenes compounds 1 and DMF-DMA(N, dinethylformamide two
Dimethoxym ethane) react and purified rear generation corresponding virtue amidine 2；Reaction second step, will generate corresponding virtue amidine 2 proper temperature,
React in appropriate solvent and in the presence of alkali with compound 3 and purified after generate compound 4, i.e. (Z)-3-dimethylamino-
2-phenoxy group-α, beta-unsaturated acyl amine.
As the further scheme of the present invention: the proper temperature in the described reaction first step refers to 20 80 DEG C, accordingly
Solvent refer to dichloromethane, 1,2-dichloroethanes, carbon tetrachloride, chloroform, oxolane any one.
As the further scheme of the present invention: the proper temperature in described reaction second step is that room temperature is to 68oC；Suitably
Solvent be dichloromethane, 1,2-dichloroethanes, carbon tetrachloride, chloroform, oxolane any one.
As the further scheme of the present invention: the alkali in described reaction second step refers to sodium carbonate, sodium acid carbonate, carbonic acid
Potassium, saleratus, NaOH, potassium hydroxide, sodium phosphate, sodium hydride, potassium tert-butoxide, triethylamine, diisopropylethylamine, pyrrole
Pyridine, 3,5-lutidines, 4-N, N-lutidines, DBU any one.
As the further scheme of the present invention: described virtue amidine 2 is 1:1 3 with the mol ratio of compound 3.
As the further scheme of the present invention: amino benzenes compounds 1 and DMF-DMA(N, dinethylformamide diformazan contracts
Aldehyde) mol ratio be 1: 1～30.
As the further scheme of the present invention: in the described reaction first step, the purification process of virtue amidine 2 is that rotation is evaporated off DMF-
DMA(N, dinethylformamide dimethylacetal) solvent, recrystallization, silica gel column chromatography.
As the further scheme of the present invention: compound 4 in described reaction second step, i.e. (Z)-3-dimethylamino-2-
Phenoxy group-α, beta-unsaturated acyl amine purification process is for steaming solvent, recrystallization, silica gel column chromatography, decompression distillation.
As the further scheme of the present invention: the reaction first step, amino benzenes compounds 1 and DMF-DMA reaction time are 2-
24 hours；Reaction second step, is 6-36 hour by generation corresponding virtue amidine 2 and compound 3 reaction time.
A class (Z)-3-diformazan ammonia is prepared in a kind of high selective reaction to have the invention have the benefit that what the present invention provided
Base-2-phenoxy group-α, the method for beta-unsaturated acyl amine, course of reaction are simple, and expense is low, and safe and environment-friendly.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1
4-phenetidine 27.4 grams (0.2 mole) and N, N-diformazan is added in 100 milliliters of single necked round bottom flask
Base formamide dimethylacetal 35.7 grams (0.3 mole).Addition dichloromethane (30 milliliters) is as solvent and a magneton, instead
Mixture is answered to be stirred at room temperature 5 hours.TLC analysis shows that 4-phenetidine disappears and has and newly puts generation.Rotation is evaporated off two
After the N,N-dimethylformamide dimethylacetal of chloromethanes, methyl alcohol and excess (recyclable and be used further in preparation reaction) one
Sticky oil thing is (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine, 37.6 grams, productivity 98%.1H NMR
(CDCl3), 300 MHz (δppm ): 7.93 (1H, s), 7.47 (2H, d), 7.01(2H, d), 3.76 (2H,
q),2.95 (3H, s), 2.98 (3H, s), 1.37(3H, t);MS:m/z(M+1) 193.01.
By (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine (3.84 grams, 0.02 mole), dichloromethane
(20 milliliters), triethylamine (4.17 milliliters, 3.03 grams, 0.03 mole) and magneton join the single neck round bottom of 50 milliliters
In flask, start magnetic stirring apparatus, be then slowly added dropwise 2-phenoxyacetyl chloride (5.12 grams, 0.03 mole) with syringe, whole
Dropping process the most about 15 minutes.After dripping, reactant mixture is at room temperature stirred overnight.Rotation is evaporated off solvent.Then
In reaction bulb, add ethyl acetate (20 milliliters) and water (20 milliliters) and stir 10 minutes, being transferred into a separatory leakage
In bucket, separate lower floor's inorganic phase.Inorganic phase ethyl acetate (10 milliliters) extracts.Merge organic phase and with saturated aqueous common salt (20
Milliliter) and water (20 milliliters) washing.Organic phase anhydrous sodium sulfate is dried.After recycling design is steamed in rotation, residue over silica gel post layer
Analysis (ethyl acetate/n-hexane: 1:5) obtains product (Z)-3-(dimethylamino)-N-(4-ethoxyphenyl)-2-phenoxy group acrylamide
[(Z)-3-(dimethylamino)-N-(4-ethoxyphenyl)-2-phenoxyacrylamide] 3.07 grams, productivity 47%
。1H NMR (CDCl3), 300 MHz (δppm ): 9.89 (1H, s), 7.49 (2H, m), 7.29(2H, m),
7.04(1H, m), 6.96(2H, m), 6.82 (2H, m), 6.49 (1H, s), 3.75 (2H, q),2.99 (3H,
s), 3.02 (3H, s), 1.36 (3H, t);MS:m/z(M+1) 327.10.
Embodiment 2
4-phenetidine 54.8 grams (0.4 mole) and N, N-diformazan is added in 250 milliliters of single necked round bottom flask
Base formamide dimethylacetal 86 grams (0.5 mole).Addition oxolane (100 milliliters) is as solvent and a magneton, instead
Mixture is answered to be stirred at room temperature overnight.TLC analysis shows that 4-phenetidine disappears and has and newly puts generation.Rotation is evaporated off tetrahydrochysene
After the N,N-dimethylformamide dimethylacetal of furans, methyl alcohol and excess (recyclable and be used further in preparation reaction) one glue
Thick grease.Shift after ethyl acetate (80 milliliters) and water (50 milliliters) are joined in above-mentioned reaction bulb and are stirred 10 minute
In a separatory funnel.Release lower floor's inorganic phase.Organic phase anhydrous sodium sulfate is dried.Rotation steam after product (E)-N '-
(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine, 71.3 grams, productivity 92%.
By (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine (38.4 grams, 0.2 mole), chloroform (250 millis
Rise), triethylamine (41.7 milliliters, 30.3 grams 0.3 mole) and magneton join the single necked round bottom flask of 500 milliliters
In, start magnetic stirring apparatus, be then slowly added dropwise 2-phenol oxygen chloroacetic chloride (51.2 grams, 0.3 mole), whole dropping with syringe
Process the most about 25 minutes.After dripping, reactant mixture is at room temperature stirred overnight.Rotation is evaporated off solvent.Then to instead
Answer and bottle add ethyl acetate (100 milliliters) and water (60 milliliters) and stirs 10 minutes, be transferred in a separatory funnel,
Separate lower floor's inorganic phase.Inorganic phase ethyl acetate (80 milliliters) extracts.Merge organic phase and with saturated aqueous common salt (80 milliliters)
Wash with water (80 milliliters).Organic phase anhydrous sodium sulfate is dried.After recycling design is steamed in rotation, residue over silica gel column chromatography (second
Acetoacetic ester/n-hexane: 1:5) obtain product (Z)-3-(dimethylamino)-N-(4-ethoxyphenyl)-2-phenoxy group acrylamide 27.2
Gram, productivity 42%.
Embodiment 3
4-phenetidine 27.4 grams (0.2 mole) and N, N-diformazan is added in 100 milliliters of single necked round bottom flask
Base formamide dimethylacetal 35.7 grams (0.3 mole).Addition dichloromethane (30 milliliters) is as solvent and a magneton, instead
Mixture is answered to be stirred at room temperature 5 hours.TLC analysis shows that 4-phenetidine disappears and has and newly puts generation.Rotation is evaporated off two
After the N,N-dimethylformamide dimethylacetal of chloromethanes, methyl alcohol and excess (recyclable and be used further in preparation reaction) one
Sticky oil thing is (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine, 37.6 grams, productivity 98%.1H NMR
(CDCl3), 300 MHz (δppm ): 7.93 (1H, s), 7.47 (2H, d), 7.01(2H, d), 3.76 (2H,
q),2.95 (3H, s), 2.98 (3H, s), 1.37(3H, t);MS:m/z(M+1) 193.01.
By (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine (38.4 grams, 0.2 mole), chloroform (250 millis
Rise), triethylamine (41.7 milliliters, 30.3 grams 0.3 mole) and magneton join the single necked round bottom flask of 500 milliliters
In, at 40 DEG C, start magnetic stirring apparatus, be then slowly added dropwise 2-phenol oxygen chloroacetic chloride (51.2 grams, 0.3 mole) with syringe, whole
Individual dropping process the most about 30 minutes.After dripping, reactant mixture is at room temperature stirred overnight.Rotation is evaporated off solvent.So
Backward reaction bulb add ethyl acetate (100 milliliters) and water (60 milliliters) and stirs 10 minutes, being transferred into a separatory
In funnel, separate lower floor's inorganic phase.Inorganic phase ethyl acetate (80 milliliters) extracts.Merge organic phase and use saturated aqueous common salt
(80 milliliters) and water (80 milliliters) wash.Organic phase anhydrous sodium sulfate is dried.After recycling design is steamed in rotation, residue over silica gel
Column chromatography (ethyl acetate/n-hexane: 1:5) obtains product (Z)-3-(dimethylamino)-N-(4-ethoxyphenyl)-2-phenoxy group propylene
Acid amides 29.8 grams, productivity 45.7%.
Embodiment 4
4-phenetidine 54.8 grams (0.4 mole) and N,N-dimethylformamide is added in 250 milliliters of single necked round bottom flask
Dimethylacetal 86 grams (0.5 mole).Add oxolane (100 milliliters) as solvent and a magneton, reactant mixture
It is stirred at room temperature overnight.TLC analysis shows that 4-phenetidine disappears and has and newly puts generation.Rotation is evaporated off oxolane, first
Alcohol and excess N,N-dimethylformamide dimethylacetal (recyclable and be used further to preparation reaction in) after a sticky oil
Thing.One is transferred to after ethyl acetate (80 milliliters) and water (50 milliliters) being joined in above-mentioned reaction bulb and be stirred 10 minutes
In separatory funnel.Release lower floor's inorganic phase.Organic phase anhydrous sodium sulfate is dried.Rotation obtains product (E)-N '-(4-ethoxy after steaming
Phenyl)-N, N-dimethylamino carbonamidine, 71.3 grams, productivity 92%.
By (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine (3.84 grams, 0.02 mole), dichloromethane
(20 milliliters), triethylamine (4.17 milliliters, 0.03 mole) and magneton join the single necked round bottom flask of 50 milliliters
In, start magnetic stirring apparatus, be then slowly added dropwise 2-(4 '-chlorobenzene oxygen) chloroacetic chloride (6.15,0.03 moles) with syringe, whole
Individual dropping process the most about 15 minutes.After dripping, reactant mixture is at room temperature stirred overnight.Rotation is evaporated off solvent.So
Backward reaction bulb add ethyl acetate (20 milliliters) and water (20 milliliters) and stirs 10 minutes, being transferred into a separatory
In funnel, separate lower floor's inorganic phase.Inorganic phase ethyl acetate (10 milliliters) extracts.Merge organic phase and use saturated aqueous common salt
(20 milliliters) and water (20 milliliters) wash.Organic phase anhydrous sodium sulfate is dried.After recycling design is steamed in rotation, residue over silica gel
Column chromatography (ethyl acetate/n-hexane: 1:5) product (Z)-2-(4 '-chlorophenoxy)-3-dimethylamino)-N-(4 '-ethoxy benzene
Base) acrylamide [(Z)-2-(4-chlorophenoxy)-3-(dimethylamino)-N-(4-ethoxyphenyl)
Acrylamide] 3.17 grams, productivity 44%.1H NMR (CDCl3), 300 MHz (δppm ): 9.91 (1H, s), 7.58
(2H, m), 7.49 (2H, m), 6.96 (2H, m), 6.82 (2H, m), 6.49 (1H, s), 3.75 (2H,
q),2.99 (3H, s), 3.02 (3H, s), 1.36 (3H, t);MS:m/z(M+1) 361.10.
Embodiment 5
4-phenetidine 54.8 grams (0.4 mole) and N, N-diformazan is added in 250 milliliters of single necked round bottom flask
Base formamide dimethylacetal 86 grams (0.5 mole).Addition oxolane (100 milliliters) is as solvent and a magneton, instead
Mixture is answered to be stirred at room temperature overnight.TLC analysis shows that 4-phenetidine disappears and has and newly puts generation.Rotation is evaporated off tetrahydrochysene
After the N,N-dimethylformamide dimethylacetal of furans, methyl alcohol and excess (recyclable and be used further in preparation reaction) one glue
Thick grease.Shift after ethyl acetate (80 milliliters) and water (50 milliliters) are joined in above-mentioned reaction bulb and are stirred 10 minute
In a separatory funnel.Release lower floor's inorganic phase.Organic phase anhydrous sodium sulfate is dried.Rotation steam after product (E)-N '-
(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine, 71.3 grams, productivity 92%.
By (E)-N '-(4-ethoxyphenyl)-N, N-dimethylamino carbonamidine (3.84 grams, 0.02 mole), dichloromethane
(20 milliliters), triethylamine (4.17 milliliters, 0.03 mole) and magneton join the single necked round bottom flask of 50 milliliters
In, start magnetic stirring apparatus, less than 35 DEG C, (6.15,0.03 rub to be slowly added dropwise 2-(4 '-chlorobenzene oxygen) chloroacetic chloride with syringe
You), whole dropping process the most about 30 minutes.Reactant mixture is at room temperature stirred overnight.Rotation is evaporated off solvent.Then to
Reaction bulb add ethyl acetate (20 milliliters) and water (20 milliliters) and stirs 10 minutes, being transferred into a separatory funnel
In, separate lower floor's inorganic phase.Inorganic phase ethyl acetate (10 milliliters) extracts.Merge organic phase and (20 in the least with saturated aqueous common salt
Rise) and water (20 milliliters) washing.Organic phase anhydrous sodium sulfate is dried.After recycling design is steamed in rotation, residue over silica gel column chromatography
(ethyl acetate/n-hexane: 1:5) obtains product (Z)-2-(-4 '-chlorobenzene oxygen)-3-(dimethylamino)-ethoxyphenyl) acrylamide
【(Z)-2-(4-chlorophenoxy)-3-(dimethylamino)-N-(4-ethoxyphenyl)acrylamide】4.97
Gram, productivity 69%.
Obviously, embodiments described above is only a part of embodiment of the present invention rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art obtained under not making creative work premise all its
His embodiment, broadly falls into the scope of protection of the invention.
Claims (9)
1. (Z)-3-dimethylamino-2-phenoxy group-α, the preparation method of beta-unsaturated acyl amine, it is characterised in that this insatiable hunger
It is compound 4 in following formula with acid amides:
Wherein: in amino benzenes compounds 1, R1For independent-H ,-F ,-Cl ,-Br ,-I ,-CN ,-NO2, -OH, -
CO2Me, -CO2Et, -CONHMe, -CONHEt, C1-C6Alkyl; R2For independent-H ,-F ,-OH ,-CN; R3For solely
-the H stood ,-CN ,-NO2；In compound 3: R4For-H ,-Cl；Preparation method comprises the following steps: the reaction first step, suitably
In temperature and coordinative solvent, after reacting with amino benzenes compounds 1 with DMF-DMA and be purified, generate corresponding virtue amidine 2；Reaction the
Two steps, react generation corresponding virtue amidine 2 and purified with compound 3 in proper temperature, appropriate solvent and in the presence of alkali
Rear generation compound 4, i.e. (Z)-3-dimethylamino-2-phenoxy group-α, beta-unsaturated acyl amine.
One the most according to claim 1 (Z)-3-dimethylamino-2-phenoxy group-α, the preparation side of beta-unsaturated acyl amine
Method, it is characterised in that: the proper temperature in the described reaction first step refers to 20 80 DEG C, coordinative solvent refer to dichloromethane,
1,2-dichloroethanes, carbon tetrachloride, chloroform, oxolane any one.
One the most according to claim 1 (Z)-3-dimethylamino-2-phenoxy group-α, the preparation side of beta-unsaturated acyl amine
Method, it is characterised in that: the proper temperature in described reaction second step is that room temperature is to 68oC；Appropriate solvent be dichloromethane, 1,
2-dichloroethanes, carbon tetrachloride, chloroform, oxolane any one.
One the most according to claim 1 (Z)-3-dimethylamino-2-phenoxy group-α, the preparation side of beta-unsaturated acyl amine
Method, it is characterised in that the alkali in described reaction second step refers to sodium carbonate, sodium acid carbonate, potassium carbonate, saleratus, hydroxide
Sodium, potassium hydroxide, sodium phosphate, sodium hydride, potassium tert-butoxide, triethylamine, diisopropylethylamine, pyridine, 3,5-lutidines, 4-
N, N-lutidines, DBU any one.
One the most according to claim 1 (Z)-3-dimethylamino-2-phenoxy group-α, the preparation side of beta-unsaturated acyl amine
Method, it is characterised in that described virtue amidine 2 is 1:1 3 with the mol ratio of compound 3.
One the most according to claim 1 (Z)-3-dimethylamino-2-phenoxy group-α, the preparation side of beta-unsaturated acyl amine
Method, it is characterised in that amino benzenes compounds 1 is 1: 1～30 with the mol ratio of DMF-DMA.
One the most according to claim 1 (Z)-3-dimethylamino-2-phenoxy group-α, the preparation side of beta-unsaturated acyl amine
Method, it is characterised in that in the described reaction first step, the purification process of virtue amidine 2 is that rotation is evaporated off DMF-DMA solvent, recrystallization, silicon
Plastic column chromatography.
One the most according to claim 1 (Z)-3-dimethylamino-2-phenoxy group-α, the preparation side of beta-unsaturated acyl amine
Method, it is characterised in that compound 4 in described reaction second step, i.e. (Z)-3-dimethylamino-2-phenoxy group-α, β-unsaturation
Acid amides purification process is for steaming solvent, recrystallization, silica gel column chromatography, decompression distillation.
One the most according to claim 1 (Z)-3-dimethylamino-2-phenoxy group-α, the preparation side of beta-unsaturated acyl amine
Method, it is characterised in that the reaction first step, amino benzenes compounds 1 and DMF-DMA reaction time are 2-24 hour；Reaction second step,
It it is 6-36 hour by generation corresponding virtue amidine 2 and compound 3 reaction time.
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