CN1738811A - 1-acetoxy-3-(substituted phenyl) propen compounds preparation method - Google Patents
1-acetoxy-3-(substituted phenyl) propen compounds preparation method Download PDFInfo
- Publication number
- CN1738811A CN1738811A CN 200380108657 CN200380108657A CN1738811A CN 1738811 A CN1738811 A CN 1738811A CN 200380108657 CN200380108657 CN 200380108657 CN 200380108657 A CN200380108657 A CN 200380108657A CN 1738811 A CN1738811 A CN 1738811A
- Authority
- CN
- China
- Prior art keywords
- phenyl
- compound
- acetoxy
- substituted
- mentioned
- 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
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- -1 1-acetoxy-3-(substituted phenyl) propen compounds Chemical class 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 29
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 65
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 55
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 55
- 229960003328 benzoyl peroxide Drugs 0.000 claims description 54
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 23
- KZDCMKVLEYCGQX-UDPGNSCCSA-N 2-(diethylamino)ethyl 4-aminobenzoate;(2s,5r,6r)-3,3-dimethyl-7-oxo-6-[(2-phenylacetyl)amino]-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid;hydrate Chemical class O.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 KZDCMKVLEYCGQX-UDPGNSCCSA-N 0.000 claims description 21
- 125000002947 alkylene group Chemical group 0.000 claims description 17
- 150000002366 halogen compounds Chemical class 0.000 claims description 16
- 150000005529 1,3-benzodioxoles Chemical group 0.000 claims description 14
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- 229910015900 BF3 Inorganic materials 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 claims description 10
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- LKUDPHPHKOZXCD-UHFFFAOYSA-N 1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=CC(OC)=C1 LKUDPHPHKOZXCD-UHFFFAOYSA-N 0.000 claims description 6
- 108091074834 12 family Proteins 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 claims description 6
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 6
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 230000026030 halogenation Effects 0.000 claims description 6
- 238000005658 halogenation reaction Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 6
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical group F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 6
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 5
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- LVZGQWKTUCVPBQ-UHFFFAOYSA-N acetic acid;trifluoroborane Chemical compound CC(O)=O.FB(F)F LVZGQWKTUCVPBQ-UHFFFAOYSA-N 0.000 claims description 4
- BNBQRQQYDMDJAH-UHFFFAOYSA-N benzodioxan Chemical group C1=CC=C2OCCOC2=C1 BNBQRQQYDMDJAH-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 4
- TXECTBGVEUDNSL-UHFFFAOYSA-N 1-acetyloxyprop-2-enyl acetate Chemical group CC(=O)OC(C=C)OC(C)=O TXECTBGVEUDNSL-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 claims description 3
- 229940075417 cadmium iodide Drugs 0.000 claims description 3
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 claims description 3
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 claims description 3
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 claims description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 3
- 150000005217 methyl ethers Chemical class 0.000 claims description 3
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 3
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- MJCYPBSRKLJZTB-UHFFFAOYSA-N trifluoroborane;dihydrate Chemical compound O.O.FB(F)F MJCYPBSRKLJZTB-UHFFFAOYSA-N 0.000 claims description 3
- 229940102001 zinc bromide Drugs 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 125000002070 alkenylidene group Chemical group 0.000 abstract 1
- 229910001849 group 12 element Inorganic materials 0.000 abstract 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 abstract 1
- 150000008648 triflates Chemical class 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 41
- 239000012300 argon atmosphere Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 238000004128 high performance liquid chromatography Methods 0.000 description 22
- 238000002156 mixing Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 16
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical class C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 15
- 239000011541 reaction mixture Substances 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 238000010790 dilution Methods 0.000 description 12
- 239000012895 dilution Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- FECRNHPJGAZUKO-UHFFFAOYSA-N erbium;trifluoromethanesulfonic acid Chemical compound [Er].OS(=O)(=O)C(F)(F)F FECRNHPJGAZUKO-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- YQEULRPIKNJWNO-UHFFFAOYSA-N lutetium;trifluoromethanesulfonic acid Chemical compound [Lu].OS(=O)(=O)C(F)(F)F YQEULRPIKNJWNO-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CZAJIUCBZHQHDS-UHFFFAOYSA-N thulium;trifluoromethanesulfonic acid Chemical compound [Tm].OS(=O)(=O)C(F)(F)F CZAJIUCBZHQHDS-UHFFFAOYSA-N 0.000 description 3
- CKUBWOWGEBSNBJ-UHFFFAOYSA-N tin;trifluoromethanesulfonic acid Chemical compound [Sn].OS(=O)(=O)C(F)(F)F CKUBWOWGEBSNBJ-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- SPLWDHARILMLDE-UHFFFAOYSA-N cerium;trifluoromethanesulfonic acid Chemical compound [Ce].OS(=O)(=O)C(F)(F)F SPLWDHARILMLDE-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- CDYCKNMKRGFHPW-UHFFFAOYSA-N dysprosium;trifluoromethanesulfonic acid Chemical compound [Dy].OS(=O)(=O)C(F)(F)F CDYCKNMKRGFHPW-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- BDSLFDHCFJHMLI-UHFFFAOYSA-N fluoro methanesulfonate Chemical compound CS(=O)(=O)OF BDSLFDHCFJHMLI-UHFFFAOYSA-N 0.000 description 2
- BGVUVBIFPBJZEI-UHFFFAOYSA-N holmium;trifluoromethanesulfonic acid Chemical compound [Ho].OS(=O)(=O)C(F)(F)F BGVUVBIFPBJZEI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- QYQKMQWPSIIZCG-UHFFFAOYSA-N 2-cyclohexylprop-2-enal Chemical compound O=CC(=C)C1CCCCC1 QYQKMQWPSIIZCG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- OKOSPWNNXVDXKZ-UHFFFAOYSA-N but-3-enoyl chloride Chemical compound ClC(=O)CC=C OKOSPWNNXVDXKZ-UHFFFAOYSA-N 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- ZEDZJUDTPVFRNB-UHFFFAOYSA-K cerium(3+);triiodide Chemical compound I[Ce](I)I ZEDZJUDTPVFRNB-UHFFFAOYSA-K 0.000 description 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FMSYTQMJOCCCQS-UHFFFAOYSA-L difluoromercury Chemical compound F[Hg]F FMSYTQMJOCCCQS-UHFFFAOYSA-L 0.000 description 1
- GBLDKMKYYYAAKD-UHFFFAOYSA-K dysprosium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Dy+3] GBLDKMKYYYAAKD-UHFFFAOYSA-K 0.000 description 1
- ASAMDJHOONJZTG-UHFFFAOYSA-K dysprosium(3+);triiodate Chemical compound [Dy+3].[O-]I(=O)=O.[O-]I(=O)=O.[O-]I(=O)=O ASAMDJHOONJZTG-UHFFFAOYSA-K 0.000 description 1
- BOXVSFHSLKQLNZ-UHFFFAOYSA-K dysprosium(iii) chloride Chemical compound Cl[Dy](Cl)Cl BOXVSFHSLKQLNZ-UHFFFAOYSA-K 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GZTUDAKVGXUNIM-UHFFFAOYSA-K erbium(3+);tribromide Chemical compound Br[Er](Br)Br GZTUDAKVGXUNIM-UHFFFAOYSA-K 0.000 description 1
- YOGVODJHAOWJKG-UHFFFAOYSA-K erbium(3+);triiodate Chemical compound [Er+3].[O-]I(=O)=O.[O-]I(=O)=O.[O-]I(=O)=O YOGVODJHAOWJKG-UHFFFAOYSA-K 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- MZNSYJWLQLXLHE-UHFFFAOYSA-K holmium(3+);tribromide Chemical compound Br[Ho](Br)Br MZNSYJWLQLXLHE-UHFFFAOYSA-K 0.000 description 1
- KXCRAPCRWWGWIW-UHFFFAOYSA-K holmium(3+);triiodide Chemical compound I[Ho](I)I KXCRAPCRWWGWIW-UHFFFAOYSA-K 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- AWQUKXBZSLEACN-UHFFFAOYSA-K lutetium(3+);triiodate Chemical compound [Lu+3].[O-]I(=O)=O.[O-]I(=O)=O.[O-]I(=O)=O AWQUKXBZSLEACN-UHFFFAOYSA-K 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BSUUCDACXQTNMW-UHFFFAOYSA-K thulium(3+);triiodate Chemical compound [Tm+3].[O-]I(=O)=O.[O-]I(=O)=O.[O-]I(=O)=O BSUUCDACXQTNMW-UHFFFAOYSA-K 0.000 description 1
- ILOTUXNTERMOJL-UHFFFAOYSA-K thulium(iii) chloride Chemical compound Cl[Tm](Cl)Cl ILOTUXNTERMOJL-UHFFFAOYSA-K 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 description 1
- FWQVINSGEXZQHB-UHFFFAOYSA-K trifluorodysprosium Chemical compound F[Dy](F)F FWQVINSGEXZQHB-UHFFFAOYSA-K 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- LLMQNIXRCPRHGZ-UHFFFAOYSA-K ytterbium(3+);triiodate Chemical compound [Yb+3].[O-]I(=O)=O.[O-]I(=O)=O.[O-]I(=O)=O LLMQNIXRCPRHGZ-UHFFFAOYSA-K 0.000 description 1
- QNLXXQBCQYDKHD-UHFFFAOYSA-K ytterbium(iii) bromide Chemical compound Br[Yb](Br)Br QNLXXQBCQYDKHD-UHFFFAOYSA-K 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
The compounds represented by the formula (I) are produced by reacting benzene compound of the formula (IV) or (V) with alkenylidene diacetate of the formula (VI) in the presence of a catalyst comprising one or more members selected from (a) halogenated boron compounds, (b) triflate compounds of Group 11 elements, (c) halogenated compounds of Group 12 elements, and (d) triflate and halogenated compounds of tin and atomic numbers 58 and 66 to 71 elements. R<1>, R<2> = H or C1 - C10 alkyl group A = Substituted phenyl group corresponding to a compound of formula (IV) or (V), R<3>, R<4> = H or C1 - C4 alkyl group, m = 0 or 1 - 4, n = 1 to 5, k = 1 or 2.
Description
Technical field
The present invention relates to the preparation method of 1-acetoxy-3-(substituted-phenyl) propen compounds.If more particularly, the present invention relates on 3, to have the preparation method of 1-acetoxy-3-(substituted-phenyl) propen compounds of the phenyl that replaces with substituting groups such as alkoxyl group or alkane dioxy bases.
According to the prepared 1-acetoxy-3 of the inventive method-(substituted-phenyl) propen compounds,, be useful as spices, pharmaceuticals, agricultural chemicals goods, and the intermediate of other organic synthesis medicine.
Background technology
Synthetic method as 1-acetoxy-3-(substituted-phenyl) propen compounds, at Bull, Soc, Chim, France, 1961, disclose among the P1194-1198 in the presence of, made 1,2-dimethoxy benzene and the reaction of alkylene group diacetate esters by boron trifluoride ether coordination compound activatory titanium tetrachloride, the method of synthetic 1-acetoxy-3-(3, the 4-Dimethoxyphenyl) propylene.But the yield of the purpose compound that obtains by this method it is reported it is 62%, is unsafty.The present inventor etc. have repeated above-mentioned synthetic method, and confirm: the yield of purpose compound only is 12%, in addition, generates a large amount of by products, and reaction mixture is brown (comparative example 3 of REFERENCE TO RELATED).In addition, employed titanium tetrachloride is the unstable compound that can be decomposed by airborne moisture in this synthetic method, essential numerous and diverse attention in its operation.
In addition, the inventor etc., above-mentioned synthetic method is used for 3, the reaction of 4-MDB and alkylene group diacetate esters, owing to, carry out 3, the decomposition reaction of 4-MDB by boron trifluoride ether coordination compound activatory titanium tetrachloride, the yield of purpose compound is 43.1%, is unsafty (REFERENCE TO RELATED comparative example 1).And then in order to suppress or to prevent 3, the decomposition of 4-MDB with respect to 1 mole of alkylene group diacetate esters, is used 0.1 mole titanium tetrachloride, trial response, but the yield of purpose compound drops to 9.8% (REFERENCE TO RELATED comparative example 2).
Open the spy and to disclose in the clear 55-141437 communique in the presence of chemical theory amount lewis acidic, make t-butylbenzene, methacrylaldehyde and excess acetyl chloride synthesize the method for 1-acetoxyl group-2-methyl-3-(4-t-butyl phenyl) propylene.In the method, when using titanium tetrachloride as Lewis acid, the yield of purpose compound is 46.2%, when using boron trifluoride ether coordination compound, the yield of purpose compound is 2.3%, no matter in any situation, the yield of purpose compound is all low, is unsafty.
Summary of the invention
The object of the present invention is to provide a kind of can be with high yield, easily prepare as the useful 1-acetoxy-3 of the intermediate of spices, pharmaceuticals, agricultural chemicals goods and other organic synthesis medicine-(substituted-phenyl) propen compounds.
Above-mentioned purpose can reach according to the preparation method of 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds.
Preparation method of the present invention, it is characterized in that: in order to prepare 1-acetoxy-3-(substituted-phenyl) propen compounds with following general formula (I) expression, be to contain by (a) halogenation boron compound, (b) the trifluoromethanesulfonic acid salt compound of 11 family's elements in the periodic table of elements, (c) halogen compounds of 12 family's elements in the periodic table of elements, (d) tin or ordination number are 58, under the existence of the catalyzer of at least a compound of selecting in the group that the trifluoromethanesulfonic acid salt compound of 66～71 lanthanon and halogen compounds constitute, make from following general formula (IV) and reach one and the represented alkylene group diacetate esters compound reaction of selecting 1 group of (V) represented benzene compound of following general formula (VI);
(in following formula (I), R
1And R
2Represent from hydrogen atom independently of one another and have one that selects the group that alkyl constituted of 1～10 carbon atom, wherein R
1And R
2Also can interconnect and 2 of propenyl and 3 carbon atom form cyclic group jointly, A represents it is from following formula (II) and of (III) selecting represented 1 group the substituted-phenyl,
R
3And R
4Expression independently of one another has the alkyl of 1～4 carbon atom, and m represents 0 or 1～4 integer, and n represents 1～5 integer, and k represents 1 or 2 integer);
And
(at following formula (IV) and (V), R
3And R
4And n, m and k are as previously mentioned);
(in following formula (VI), R
1And R
2As previously mentioned).
In the preparation method of 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds, the represented benzene compound of above-mentioned general formula (IV) preferably from methyl-phenoxide, veratrole, hydroquinone dimethyl ether, phloroglucinol trimethyl ether, and hydroxyl Resorcinol three methyl ethers select.
In the preparation method of 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds, the represented benzene compound of above-mentioned logical formula V is selected in 2-methylenedioxybenzenes and the ethylenedioxy benzene preferably from 1.
In the preparation method of 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds, the represented alkylene group diacetate esters of above-mentioned general formula (VI) is preferably from 3,3-diacetoxy-2-methacrylic, 3,3-diacetoxy propylene, 3,3-diethoxy-1-methacrylic, 3,3-diacetoxy-2-ethyl propylene, 3,3-diethoxy-1-ethyl propylene and 3 is selected in 3-diethoxy-1-ethyl-2-methacrylic.
In the preparation method of 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds, in above-mentioned reaction, the mol ratio of above-mentioned benzene compound and above-mentioned alkylene group diacetate esters compound preferably uses 1～50: 1.
In the preparation method of 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds, with respect to 1 mole of above-mentioned alkylene group diacetate esters compound, preferably 0.005～1 mole of the usage quantity of above-mentioned catalyzer.
In the preparation method of 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds, the employed halogenation boron compound of above-mentioned catalyzer (a) is preferably selected from the group that boron fluoride, boron trifluoride diethyl ether coordination compound, boron trifluoride tetrahydrofuran (THF) coordination compound, boron trifluoride acetic acid complex salt, boron trifluoride dihydrate and boron trifluoride-n-butyl ether coordination compound constitutes.
In the preparation method of 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds, the trifluoromethanesulfonic acid salt compound (b) of the employed 11 family's elements of above-mentioned catalyzer is preferably selected from copper trifluoromethanesulfcomposite and silver trifluoromethanesulfonate.
In the preparation method of 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds, the halogen compounds (c) of the employed 12 family's elements of above-mentioned catalyzer is preferably selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, cadmium fluoride, Cadmium chloride fine powder, cadmium bromide, cadmium iodide, hydrogen fluoride, mercury chloride, mercuric bromide and red mercury iodide.
In the preparation method of 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds, employed tin of above-mentioned catalyzer and ordination number are that the trifluoromethanesulfonic acid salt compound and the halogen compounds (d) of 58,66～71 lanthanon preferably selected from trifluoromethanesulfonic acid salt compound, fluorochemical, muriate, bromide and the iodide of tin, cerium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
In the preparation method of 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds, above-mentioned reaction is preferably carried out in the atmosphere that gas constituted that does not react with above-mentioned general formula (IV), (V) and (VI) compound, above-mentioned catalyzer and resultant of reaction.
In the preparation method of the 1-of the invention described above acetoxy-3-(substituted-phenyl) propen compounds, the compound of above-mentioned formula (I) is preferably selected from the represented compound of following general formula (VII);
(in above-mentioned formula (VII), R
1And R
2As previously mentioned, B is that expression reaches 1 that selects 1 group (IX) the represented substituted-phenyl from following formula (VIII),
During formula (VIII) reaches (IX), R
3, R
4And k as previously mentioned).
The represented compound of above-mentioned general formula (VII) is a novel cpd.
In the preparation method of the 1-of the invention described above acetoxy-3-(substituted-phenyl) propen compounds, the compound of above-mentioned general formula (I) preferably reaches (XI) from following formula (X):
And
Select in represented 1-acetoxy-3-(3, the alkylenedioxy group phenyl of 4-C1～C2) propylene.Above-mentioned formula (X) and compound (XI) are novel cpds.
In the preparation method of the 1-of the invention described above acetoxy-3-(substituted-phenyl) propen compounds, in above-mentioned formula (X) or (XI), preferred R
1The expression hydrogen atom, R
2The expression methyl.
In the preparation method of the 1-of the invention described above acetoxy-3-(substituted-phenyl) propen compounds, the compound of above-mentioned general formula (I) is preferably from 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene, 1-acetoxyl group-2-methyl-3-(3,4-ethylenedioxy phenyl) propylene, 1-acetoxyl group-2-methyl-3-(4-p-methoxy-phenyl) propylene, 1-acetoxyl group-2-methyl-3-(2, the 5-Dimethoxyphenyl) selects in propylene and 1-acetoxyl group-2-methyl-3-(3, the 4-Dimethoxyphenyl) propylene.In these compounds, 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene, 1-acetoxyl group-2-methyl-3-(3,4-ethylenedioxy phenyl) propylene, 1-acetoxyl group-2-methyl-3-(2, the 5-Dimethoxyphenyl) propylene are novel cpds.
Employed periodictable is based on 18 family's type periodic table of elements, IUPAC, inorganic chemistry nomenclature, nineteen ninety rule among the present invention.
In addition, " fluoroform sulphonate " is meant Tri (fluoro) methanesulphonate.
Embodiment
1-acetoxy-3-(substituted-phenyl) propen compounds of preparation in accordance with the present invention preparation based on contained unsymmetrical carbon and/or two key in the represented compound of above-mentioned general formula (I), comprises multiple steric isomer certainly.
For the inventive method for preparing 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds comprises: under the existence of the special catalyst of Xiang Shuing, make from above-mentioned general formula (IV) and reach 1 and the alkylene group diacetate esters reaction of selecting 1 group (V) the represented benzene compound of above-mentioned general formula (VI) expression in the back.Formula (IV) and (V) benzene compound and general formula (II) and (III) represented substituted-phenyl correspondence, the alkylene group diacetate esters of general formula (VI) expression in general formula (I) in conjunction with the A base.With 1-acetoxyl group propenyl correspondence.
In the inventive method employed special catalyst contain from
(a) halogenation boron compound
(b) the trifluoromethanesulfonic acid salt compound of 11 family's elements in the periodic table of elements
(c) halogen compounds of 12 family's elements in the periodic table of elements, and
(d) tin, and ordination number be the trifluoromethanesulfonic acid salt compound and the halogen compounds of 58 and 66～71 lanthanon
Select in the group that is constituted at least 1 in compound.
In the methods of the invention, the represented benzene compound of above-mentioned general formula (IV) preferably from methyl-phenoxide, veratrole, hydroquinone dimethyl ether, phloroglucinol trimethyl ether, and hydroxyl Resorcinol three methyl ethers select, especially preferably use methyl-phenoxide and veratrole.These also can use commercially available product.
In addition, the represented benzene compound of above-mentioned logical formula V is selected in 2-methylenedioxybenzenes and the ethylenedioxy benzene preferably from 1.
Moreover, the represented alkylene group diacetate esters of above-mentioned general formula (VI) is preferably from 3,3-diacetoxy-2-methacrylic, 3,3-diacetoxy propylene, 3,3-diethoxy-1-methacrylic, 3,3-diacetoxy-2-ethyl propylene, 3,3-diethoxy-1-ethyl propylene and 3 is selected in the group that the 3-diethoxy-the 1-ethyl-the 2-methacrylic is constituted.These compounds also can use other material of commercial grades, in case of necessity, also can be according to Bull, Soc, Chim, France, 1961, the method that P1194 to 1198 put down in writing, by α, beta-unsaturated aldehyde and Glacial acetic acid preparation.These compounds comprise isomer.
In the represented alkylene group diacetate esters of general formula (VI), R
1And R
2Also can interconnect and 2 of propenyl and 3 carbon atom form cyclic group jointly, ring penta ring, hexamethylene ring etc., preferably hexamethylene ring be arranged as such cyclic group.
Employed α in the preparation as the alkylene group diacetate esters, beta-unsaturated aldehyde, can enumerate: propenal, methacrylaldehyde, crotonic aldehyde, α, beta-dimethyl-propenal, α-ethyl acrylic aldehyde, β-ethyl acrylic aldehyde, β-propyl group propenal, α-cyclohexyl propenal etc., preferably propenal, methacrylaldehyde, crotonic aldehyde are more preferably methacrylaldehyde.
Employed catalyzer for example can be enumerated with halogenation boron compound (a) in the inventive method: boron fluoride, boron trifluoride diethyl ether coordination compound, boron trifluoride tetrahydrofuran (THF) coordination compound, boron trifluoride acetic acid complex salt, boron trifluoride dihydrate and boron trifluoride-n-butyl ether coordination compound etc., preferably use boron trifluoride ether coordination compound, boron trifluoride acetic acid complex salt.These compounds can use the material of commercially available product grade.
In addition, catalyzer is preferably selected from copper trifluoromethanesulfcomposite and silver trifluoromethanesulfonate with the trifluoromethanesulfonic acid salt compound (b) of 11 family's elements.
Moreover, catalyzer comprises zinc fluoride, zinc chloride, zinc bromide, zinc iodide, cadmium fluoride, Cadmium chloride fine powder, cadmium bromide, cadmium iodide, Mercury difluoride, mercury chloride, mercuric bromide and red mercury iodide with the halogen compounds (c) of 12 family's elements, among these, the preferred halogen compounds of using zinc, comparative optimization uses zinc chloride.
In addition, catalyzer is 58 with tin and ordination number, the trifluoromethanesulfonic acid salt compound of 66～71 lanthanon and halogen compounds (d) comprise trifluoromethanesulfonic acid tin, Tin tetrafluoride., tin chloride, Tin tetrabromide, Tin tetraiodide, cerium fluoride, Cerium II Chloride, comprise cerium bromide, cerous iodide, the trifluoromethanesulfonic acid cerium, dysprosium fluoride, Dysprosium trichloride, dysprosium bromide, the iodate dysprosium, the trifluoromethanesulfonic acid dysprosium, holmium fluoride, Holmium trichloride, Holmium tribromide, Holmium triiodide, the trifluoromethanesulfonic acid holmium, fluoridize erbium, Erbium trichloride, Erbium tribromide, the iodate erbium, the trifluoromethanesulfonic acid erbium, fluoridize thulium, thulium chloride, the bromination thulium, the iodate thulium, the trifluoromethanesulfonic acid thulium, fluoridize ytterbium, Ytterbium trichloride, ytterbium bromide, the iodate ytterbium, Ytterbiumtriflate, fluoridize lutetium, lutecium chloride, the bromination lutetium, the iodate lutetium, the hydrate of trifluoromethanesulfonic acid lutetium etc. and these compounds etc.Among these, preferably use tin chloride, trifluoromethanesulfonic acid tin, trifluoromethanesulfonic acid erbium, trifluoromethanesulfonic acid thulium, Ytterbium trichloride, Ytterbiumtriflate or trifluoromethanesulfonic acid lutetium, more preferably use tin chloride or Ytterbium trichloride.
In the methods of the invention, catalyzer with respect to 1 mole of addition that uses below 0.005～1 mole of alkylene group diacetate esters, more preferably is 0.01～0.5 mole preferably, more preferably 0.01～0.2 mole.If the addition of catalyzer is above 1 mole, must react the recovery of the catalyzer after the end and decomposition, numerous and diverse operation such as discarded, exist and implement the unfavorable of the inventive method on the industrial application, in addition, if 0.005 mole of its addition less than, can not be in the time of practicality, for example with interior reaction was finished in 24 hours.
Reaction among the preparation method of the present invention also can be carried out in solvent, but preferably carries out under solvent-free.As solvent, can use aliphatics halogenated hydrocarbons of the aromatic hydrocarbons of benzene,toluene,xylene, chlorobenzene etc. and fragrant halogenated hydrocarbons or methylene dichloride, ethylene dichloride etc. etc.
Temperature of reaction in the inventive method can suitably be set according to the kind and the concentration of starting compound, catalyzer, but generally preferably-10～80 ℃, more preferably 0～60 ℃.Reaction times in the inventive method can suitably be set according to kind, concentration and the temperature of reaction of above-mentioned raw materials compound, catalyzer, but generally preferably 0.5～24 hour, be more preferably 0.5～12 hour.
There is no particular limitation for the reaction atmosphere in the inventive method, but general preferred and starting compound (general formula (I) and compound (II)), above-mentioned catalyzer and the nonreactive gas of reacting generating compound, for example: nitrogen, and the atmosphere that constituted more than a kind of the rare gas element of argon gas etc. in or carry out in the air-flow.In addition, reaction pressure can be carried out under common normal atmosphere, but is not to be defined in this.
According to the inventive method synthetic 1-acetoxy-3-(substituted-phenyl) propen compounds, the reaction mixture after reaction finishes with common Separation and Recovery operation, for example: extraction, concentrate, and the aftertreatment Separation and Recovery of filtration etc., in case of necessity, the refinement treatment that this regenerant is imposed distillation, recrystallization, various chromatography methods etc. is made with extra care.
In the general formula (I) of expression according to the inventive method synthetic 1-acetoxy-3-(substituted-phenyl) propen compounds, R
1And R
2Expression hydrogen atom or C
1～C
10Alkyl, preferred R
1And R
2At least one the expression C
1～C
10Alkyl.R
1And R
2Represented C
1～C
10Alkyl comprise methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and decyl, they comprise various isomer.R
1And R
2The alkyl of expression is methyl preferably.
In general formula (I), R
1And R
2The alkyl of expression also can interconnect (combination) and propyl group 1 and 2 carbon atom at its end and form cyclic group jointly, as this cyclic group ring penta ring, hexamethylene ring etc., preferably cyclohexyl is arranged.
In general formula that A in the compound of general formula (I) represents (II) and the substituted-phenyl (III), R
3And R
4Represent C independently of one another
1～C
4Alkyl, m represents 0 or 1～4 integer, n represents 1～5 integer, k represents 1 or 2 integer.R
3And R
4The C of expression
1～C
4Alkyl comprise methyl, ethyl, propyl group and butyl, comprise isomer respectively.C
1～C
4Alkyl preferably from methyl, ethyl, n-propyl group, sec.-propyl, n-butyl, isobutyl-and sec-butyl, select.
In the compound of general formula prepared according to the methods of the invention (I), 1-acetoxy-3-(substituted-phenyl) propen compounds of following general formula (VII) expression is a novel cpd;
(in above-mentioned formula (VII), R
1And R
2As previously mentioned, B represents to reach 1 that selects 1 group (IX) the represented substituted-phenyl from following formula (VIII),
During formula (VIII) reaches (IX), R
3, R
4And k as previously mentioned).
In 1-acetoxy-3-(substituted-phenyl) propen compounds of general formula of the present invention (I), when the A in the general formula (I) represents the substituted-phenyl of general formula (III), preferably from above-mentioned general formula (X) and (XI) expression the 1-acetoxy-3-(3,4-C
1～C
2The alkylenedioxy group phenyl) select in the propylene.At this moment, at general formula (X) and (XI), preferred R
1The expression hydrogen atom, R
2The compound of expression methyl.
In addition, in the general formula (I) of expression 1-acetoxy-3 of the present invention-(substituted-phenyl) propen compounds, when A represented the substituted-phenyl of general formula (II), this substituted-phenyl (II) is 4-p-methoxy-phenyl, 2 preferably, 5-Dimethoxyphenyl, and 3, the 4-Dimethoxyphenyl.
Thereby, the 1-acetoxy-3 of general formula of the present invention (I)-(substituted-phenyl) propen compounds is 1-acetoxyl group-2-methyl-3-(3 preferably, the 4-methylenedioxyphenyl) propylene, 1-acetoxyl group-2-methyl-3-(3,4-ethylenedioxy phenyl) propylene, 1-acetoxyl group-2-methyl-3-(4-p-methoxy-phenyl) propylene, 1-acetoxyl group-2-methyl-3-(2, the 5-Dimethoxyphenyl) propylene, 1-acetoxyl group-2-methyl-3-(3, the 4-Dimethoxyphenyl) propylene.
Embodiment
Further specify the present invention according to following embodiment, but scope of the present invention is not by these
Embodiment limits.
In addition, the yield of 1-acetoxyl group-2-methyl-3-(substituted-phenyl) propylene is with 3, and 3-diacetoxy-2-methacrylic is that benchmark is calculated.
Embodiment 1
In argon atmosphere, under 20 ℃, in the flask of 20ml, add 1,2-methylenedioxybenzenes (6.83g, 56.0mmol) and content are 3 of 91.8 quality %, the mixing solutions of 3-diacetoxy-2-methacrylic (1.05g, 5.6mmol) is to wherein mixing boron trifluoride diethyl ether coordination compound (74mg, 0.52mmol).Mixture was stirred 1 hour for 23 ℃ in temperature, mix ethyl acetate (50ml) in the reaction solution that obtains, separate accessing formed organic layer in the reaction solution, water (50ml) is used anhydrous sodium sulfate drying after washing three times, and distillation removes and desolvates.Residue is carried out silica gel column chromatography, make 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene 1.15g separate out collection as white crystals with ethyl acetate/n-hexane=1/13 (v/v).The separation yield of the purpose compound that obtains is 88%.
The physics value of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is expressed as follows:
1H-NMR(300MHz，CDCl
3)δ＝1.56(3H，d，J＝1.5Hz)，2.15(3H，s)，3.18(2H，s)，5.92(2H，s)，6.63(1H，dd，J＝7.8Hz，J＝1.5Hz)，6.67(1H，d，J＝1.5Hz)，6.72(1H，d，J＝7.8Hz)，7.02(1H，q，J＝1.5Hz)。
13C-NMR(75.5MHz，CDCl
3)δ＝13.43，20.78，40.05，100.86，108.10，109.10，121.31，121.70，131.24，132.79，146.08，147.69，168.26。
Ultimate analysis:
C(％)H(％)
C
13H
14O
4Calculated value 66.666.02
Measured value 66.716.16
Embodiment 2
In argon atmosphere, under 20 ℃, in the flask of 20ml, add 1,2-methylenedioxybenzenes (6.83g, 55.97mmol) and content are 3 of 88 quality %, the mixing solutions of 3-diacetoxy-2-methacrylic (0.96g, 4.88mmol) is to wherein mixing boron trifluoride diethyl ether coordination compound (77mg, 0.54mmol).This mixed solution was stirred 1 hour for 23 ℃ in temperature, in the reaction solution that obtains, mix acetonitrile (100ml), this mixture is supplied with high performance liquid chromatography, carry out the analysis of reaction solution with the absolute standard curve method.Consequently the yield of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 97.1%.In addition, contain the unreacted 1 of 5.86g in the reaction solution, the 2-methylenedioxybenzenes.
Embodiment 3～6
In each example of embodiment 3～6 and embodiment 2 similarly react and analyze.But, 1 of use, 2-methylenedioxybenzenes, 3,3-diacetoxy-2-methacrylic, and amount, temperature of reaction and reaction times of boron trifluoride ether coordination compound change to such as table 1 record.The results are shown in table 1.
Table 1
| Compound 1 (mmol) (*)1 | Compound 2 (mmol) (*)2 | BF 3·Et 2O (mmol) (*)4 | Temperature of reaction (℃) | Reaction times (h) | Compound 3 yields (%) (*)3 | |
| Embodiment 3 | 27.99 | 5.55 | 0.54 | 0 | 2 | 84.6 |
| Embodiment 4 | 27.94 | 5.55 | 0.56 | 23 | 1 | 89.3 |
| Embodiment 5 | 27.94 | 5.55 | 0.27 | 23 | 3 | 86.8 |
| Embodiment 6 | 55.95 | 5.61 | 5.58 | 23 | 0.5 | 93.8 |
[notes] (*)
1Compound 1:1, the 2-methylenedioxybenzenes
(*)
2Mixture 2:3,3-diacetoxy-2-methacrylic
(*)
3Compound 3:1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene
(*)
4BF
3Et
2O: boron trifluoride diethyl ether coordination compound
Comparative example 1
In argon atmosphere, in the there-necked flask of 25ml, add titanium tetrachloride (1.28g, 6.7mmol), to wherein mixing boron trifluoride diethyl ether coordination compound (0.017g, 0.12mmol).8～12 ℃ of interior temperature, dripped 1 with 60 minutes, 2-methylenedioxybenzenes (3.27g, 26.8mmol) mixes in said mixture, then, dripping content with 15 minutes is 3 of 100 quality %, 3-diacetoxy-2-methacrylic (1.05g, 6.1mmol) and 1, the mixture of 2-methylenedioxybenzenes (0.75g, 6.1mmol) mixes.The mixture that obtains was stirred 30 minutes for 8～10 ℃ in interior temperature,, stirred then 30 minutes to wherein mixing 6N-hydrochloric acid (10ml) and methylene dichloride (10ml).Filtering insolubles from the mixed solution that obtains mixes methylene dichloride and carry out extraction treatment in filtrate, separates the organic layer that obtains, water, saturated common salt water washing, anhydrous sodium sulfate drying.The liquid that obtains is filtered, concentrates, get crude product 3.16g.This is supplied with high performance liquid chromatography, analyze according to the absolute standard curve method.Consequently the yield of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 43.1%, in addition, contains the unreacted 1 of 1.40g in reaction solution, the 2-methylenedioxybenzenes.
Comparative example 2
In argon atmosphere, in the there-necked flask of 25ml, add titanium tetrachloride (0.10g, 0.5mmol).4～5 ℃ of interior temperature, be 3 of 91.7 quality % to wherein dripping content, 3-diacetoxy-2-methacrylic (0.94g, 5.0mmol) makes it to mix, and then, drips 1, and 2-methylenedioxybenzenes (6.11g, 50.0mmol) makes it to mix.The reaction mixture that obtains is warming up to 23 ℃, stirred 18 hours.In the reaction solution that obtains, add ethanol 20g, this is supplied with high performance liquid chromatography, carry out the analysis of resultant with the absolute standard curve method.Consequently the yield of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 9.8%.
Embodiment 7
In argon atmosphere, under 20 ℃, in the flask of 20ml, add 1, the mixing solutions of 2-methylenedioxybenzenes (6.83g, 56.0mmol) and zinc chloride (152mg, 1.12mmol), to mixture content wherein is 3 of 100 quality %, 3-diacetoxy-2-methacrylic (0.96g, 5.60mmol).This mixed solution after 23 ℃ of interior temperature stir 3 hours, is mixed acetonitrile (85ml) in the reaction solution that obtains, this mixed solution is supplied with high performance liquid chromatography, carry out the analysis of reaction solution with the absolute standard curve method.Consequently the yield of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 88.3%.In addition, in reaction solution, contain the unreacted 1 of 6.06g, the 2-methylenedioxybenzenes.
Embodiment 8
In argon atmosphere, under 20 ℃, in the flask of 25ml, add 1, the mixing solutions of 2-methylenedioxybenzenes (2.44g, 20.0mmol) and copper trifluoromethanesulfcomposite (72mg, 0.20mmol), to mixture content wherein is 3 of 100 quality %, 3-diacetoxy-2-methacrylic (0.38g, 2.0mmol).After 22 ℃ of interior temperature stirred 6 hours, mixed ethanol in the reaction solution that obtains (10ml) was supplied with high performance liquid chromatography with this, carries out the analysis of reaction solution with the absolute standard curve method with this mixed solution.Consequently the yield of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 84.0%.In addition, in reaction solution, contain the unreacted 1 of 2.17g, the 2-methylenedioxybenzenes.
Embodiment 9～11
In each example of embodiment 9～11, carry out the reaction same with embodiment 7.But, 1 of use, 2-methylenedioxybenzenes, 3, amount, the reaction times of 3-diacetoxy-2-methacrylic and zinc chloride change to such as table 2 record.The results are shown in table 2.
Table 2
| Compound 1 (mmol) (*)1 | Compound 2 (mmol) (*)2 | Zinc chloride (mmol) | Temperature of reaction (℃) | Reaction times (h) | Compound 3 yields (%) (*)3 | |
| Embodiment 9 | 55.97 | 5.95 | 0.54 | 23 | 6 | 82.1 |
| Embodiment 10 | 55.88 | 5.58 | 2.81 | 23 | 1 | 90.0 |
| Embodiment 11 | 27.96 | 5.62 | 1.16 | 23 | 2 | 81.9 |
[notes] (*)
1Compound 1:1, the 2-methylenedioxybenzenes
(*)
2Mixture 2:3,3-diacetoxy-2-methacrylic
(*)
3Compound 3:1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene
Embodiment 12
In argon atmosphere, adding content in 4 mouthfuls of flasks of 200ml volumetrical is 3 of 89.6 quality %, 3-diacetoxy-2-methacrylic (19.22g, 100mmol) and methyl-phenoxide (108.14g, 1.0mol).24 ℃ of interior temperature, wherein mix boron trifluoride diethyl ether coordination compound (1.42g, 10mol) with 2 fens clockwise, under 24～25 ℃ of interior temperature, stir this mixed solution and made it reaction in 1 hour.After reaction finishes, the reaction solution that obtains with the water washing of 20ml 2 times, is used the saturated common salt water washing of 20ml then.The organic layer underpressure distillation that separatory is obtained (20mmHg, 55～57 ℃), residue with silica gel column chromatography (eluting solvent: hexane/ethyl acetate=10/1) refining, obtain colourless liquid object 1-acetoxyl group-2-methyl-3-(4-p-methoxy-phenyl) propylene.Its yield is 93.4%, and its output is 20.58g.
Embodiment 13
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml volumetrical is 3 of 89.6 quality %, 3-diacetoxy-2-methacrylic (1.92g, 10mmol) and hydroquinone dimethyl ether (13.82g, 100mmol).54 ℃ of interior temperature, wherein mix boron trifluoride ether coordination compound (0.14g, 1mmol) with 1 fen clockwise, under 53～54 ℃ of interior temperature, stir and made it reaction in 1 hour.After reaction finishes, in reaction solution, add ethyl acetate 150ml, the saturated common salt water washing of usefulness 20ml 2 times.Behind this reaction solution of separatory, with the organic layer underpressure distillation that obtains (20mmHg, 55～57 ℃), residue silica gel column chromatography (eluting solvent: hexane/ethyl acetate=10/1) refining, obtain colorless solid object 1-acetoxyl group-2-methyl-3-(2, the 5-Dimethoxyphenyl) propylene (yield 77.4%, output 1.94g).
The physics value of 1-acetoxyl group-2-methyl-3-(2, the 5-Dimethoxyphenyl) propylene is expressed as follows:
1H NMR(300MHz，CDCl
3)δ＝1.63(3H，d，J＝1.5Hz)，2.13(3H，s)，3.26(2H，s)，3.75(3H，s)，3.77(3H，s)，6.70～6.74(2H，m)，6.78(1H，d，J＝9.6Hz)，6.99(1H，q，J＝1.5Hz)。
13C NMR(75.5MHz，CDCl
3)δ：13.75，20.76，33.73，55.66，56.06，111.57，120.58，128.67，131.58，151.98，153.55，168.17。
HRMS (EI) (M
+) C
14H
18O
4Calculated value: 250.1205, measured value: 250.1198
Embodiment 14
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml volumetrical is 3 of 89.6 quality %, 3-diacetoxy-2-methacrylic (1.92g, 10mmol) and hydroquinone dimethyl ether (13.82g, 100mmol).54 ℃ of interior temperature, wherein mix boron trifluoride ether coordination compound (0.14g, 1mmol) with 1 fen clockwise, under 53～54 ℃ of interior temperature, stir and made it reaction in 1 hour.After reaction finishes, to reaction solution, use high performance liquid chromatography to carry out quantitative analysis, the output of 1-acetoxyl group-2-methyl-3-(2, the 5-Dimethoxyphenyl) propylene is 2.16g (yield 86.0%).
Embodiment 15
In argon atmosphere, in 4 mouthfuls of flasks of 100ml volumetrical, add 1,2-dimethoxy benzene (69.2g, 500mmol), content are 3 of 89.6 quality %, 3-diacetoxy-2-methacrylic (9.61g, 50mmol), in 24～25 ℃ of interior temperature to mixed chlorinated zinc (1.36g, 10mmol) wherein.25～26 ℃ of interior temperature, after stirring this mixed solution and making it reaction in 1.5 hours, with saturated aqueous common salt 50ml washing reaction liquid 3 times.Separate organic layer for underpressure distillation (8～10mmHg, 80～84 ℃), with distillation residue silica gel column chromatography (eluting solvent: hexane/ethyl acetate=10/1) refining, obtain object 1-acetoxyl group-2-methyl-3-(3, the 4-Dimethoxyphenyl) propylene (yield 95.1%, output 11.9g) of colourless liquid.
Embodiment 16
In argon atmosphere, in 3 mouthfuls of flasks of 25ml volumetrical, add 1,2-dimethoxy benzene (13.82g, 100mmol), content are 3 of 92.0 quality %, 3-diacetoxy-2-methacrylic (1.87g, 10mmol), in 18～19 ℃ of interior temperature to wherein adding boron trifluoride ether coordination compound (0.142g, 1mmol).The mixed solution that obtains was stirred 2 hours for 22～23 ℃ in interior temperature, after reaction finishes, reaction solution is carried out quantitative analysis with high performance liquid chromatography, and the result is that the yield of object 1-acetoxyl group-2-methyl-3-(3, the 4-Dimethoxyphenyl) propylene is 94.4% (output 2.36g).
Comparative example 3
In argon atmosphere, in 3 mouthfuls of flasks of 25ml volumetrical, add titanium tetrachloride (1.18g, 6.2mmol), to wherein mixing boron trifluoride ether coordination compound (0.016g, 0.11mmol), 8～12 ℃ of interior temperature, wherein drip 1 with 30 fens clockwise, 2-dimethoxy benzene (3.40g, 24.6mmol), then, dripping content with 5 minutes is 3 of 100 quality %, 3-diacetoxy-2-methacrylic (0.96g, 5.6mmol) and 1, the mixture of 2-dimethoxy benzene (0.77g, 5.6mmol).The mixed solution that obtains was stirred 60 minutes for 8～10 ℃ in interior temperature, and the hydrochloric acid (10ml) and the methylene dichloride (10ml) that add 6N stirred 30 minutes.Insolubles in the reaction solution that filtering obtains is used dichloromethane extraction, organic layer water, saturated common salt water washing, Na
2SO
4Dry.Behind the reaction solution that filtration obtains, concentrated filtrate obtains crude product 4.54g.Carry out quantitative analysis with high performance liquid chromatography, the result is that the yield of object 1-acetoxyl group-2-methyl-3-(3, the 4-Dimethoxyphenyl) propylene is 12.0% (output 0.18g).
In addition, this reaction solution is a brown, according to the analysis confirmation of high performance liquid chromatography a large amount of by products.
Embodiment 17
In argon atmosphere, in 3 mouthfuls of flasks of 100ml, add Ytterbiumtriflate (ytterbium tri (fluoro) methanesulphonate) (1.86g, 3mmol), to wherein mixing 1,2-methylenedioxybenzenes (61.38g, 502.6mmol).38～40 ℃ of interior temperature, with 30 minutes in above-mentioned mixed solution mixture content be 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (19.30g, 100.0mmol) is 40～41 ℃ of interior temperature, stirred this mixed solution 3 hours.The reaction mixture that obtains carries out 3 washings with the water of 16ml, the water layer after each time washing is concentrated to do reclaim Ytterbiumtriflate admittedly.With the organic layer after the quantitative washing of high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 19.57g (yield 83.6%).
Embodiment 18
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.44g, 17.8mmol) and 1,2-methylenedioxybenzenes (12.2g, 100.0mmol).39 ℃ of interior temperature, to wherein adding ytterbium trichloride 6 hydrates (0.23g, 0.6mmol), the reaction solution that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 3.89g (yield 93.1%).
Embodiment 19
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.86g, 20.0mmol) and 1,2-methylenedioxybenzenes (12.212g, 100.0mmol), 38 ℃ of interior temperature, to wherein mixing Ytterbiumtriflate (recovery article of embodiment 17: 0.37g, 0.6mmol), the reaction solution that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 3.64g (yield 77.7%).
Embodiment 20
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.86g, 20.0mmol) and 1,2-methylenedioxybenzenes (12.21g, 100.0mmol), 38 ℃ of interior temperature, to wherein mixing trifluoromethanesulfonic acid tin (0.25g, 0.6mmol), the reaction mixture that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 4.10g (yield 87.6%).
Embodiment 21
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.86g, 20.0mmol) and 1,2-methylenedioxybenzenes (12.21g, 100.0mmol), 38 ℃ of interior temperature, to wherein mixing tin tetrachloride (0.16g, 0.6mmol), the reaction mixture that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 4.15g (yield 88.5%).
Embodiment 22
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.86g, 20.0mmol) and 1,2-methylenedioxybenzenes (12.21g, 100.0mmol) is 38 ℃ of interior temperature, to wherein mixing trifluoromethanesulfonic acid cerium (0.36g, 0.6mmol).The reaction mixture that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 3.64g (yield 77.7%).
Embodiment 23
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.86g, 20.0mmol) and 1,2-methylenedioxybenzenes (12.21g, 100.0mmol) is 38 ℃ of interior temperature, to wherein adding trifluoromethanesulfonic acid dysprosium (0.37g, 0.6mmol).The reaction mixture that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 3.26g (yield 69.6%).
Embodiment 24
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.86g, 20.0mmol) and 1,2-methylenedioxybenzenes (12.21g, 100.0mmol) is 38 ℃ of interior temperature, to wherein mixing trifluoromethanesulfonic acid holmium (0.37g, 0.6mmol).The reaction mixture that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 3.56g (yield 76.1%).
Embodiment 25
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.86g, 20.0mmol) and 1,2-methylenedioxybenzenes (12.21g, 100.0mmol) is 38 ℃ of interior temperature, to wherein mixing trifluoromethanesulfonic acid lutetium (0.37g, 0.6mmol).The reaction mixture that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 3.91g (yield 83.5%).
Embodiment 26
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.86g, 20.0mmol) and 1,2-methylenedioxybenzenes (12.21g, 100.0mmol) is 38 ℃ of interior temperature, to wherein mixing trifluoromethanesulfonic acid thulium (0.370g, 0.6mmol).The reaction mixture that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 3.89g (yield 82.9%).
Embodiment 27
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.86g, 20.0mmol) and 1,2-methylenedioxybenzenes (12.21g, 100.0mmol) is 38 ℃ of interior temperature, to wherein mixing trifluoromethanesulfonic acid erbium (0.37g, 0.6mmol).The reaction mixture that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene is 3.77g (yield 80.5%).
Embodiment 28
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.86g, 20.0mmol) and methyl-phenoxide (10.82g, 100.0mmol) are 38 ℃ of interior temperature, to wherein mixing copper trifluoromethanesulfcomposite (0.22g, 0.6mmol).The reaction mixture that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(4-p-methoxy-phenyl) propylene is 4.09g (yield 92.7%).
Embodiment 29
In argon atmosphere, adding content in 3 mouthfuls of flasks of 25ml is 3 of 89.2 quality %, 3-diacetoxy-2-methacrylic (3.86g, 20.0mmol) and methyl-phenoxide (11.0g, 101.8mmol) are 38 ℃ of interior temperature, to wherein mixing Ytterbiumtriflate (0.37g, 0.6mmol).The reaction mixture that obtains was stirred 3 hours for 39～40 ℃ in interior temperature.The reaction solution dilution in acetonitrile that obtains, quantitative with high performance liquid chromatography, the output of 1-acetoxyl group-2-methyl-3-(4-p-methoxy-phenyl) propylene is 4.15g (yield 94.2%).
Embodiment 30
Under argon atmosphere, 24 ℃, in 3 mouthfuls of flasks of 25ml 1, (content is 97 quality % to the 2-ethylenedioxybenzenes, 7.04g, 51.7mmol) and 3, add boron trifluoride ether coordination compound (71mg, 0.5mmol) in the mixing solutions of 3-diacetoxy-2-methacrylic (content is 89.2 quality %, 0.97g, 5.0mmol).After 24 ℃ of interior temperature stir 2 hours, in reaction solution, add ethyl acetate (50ml), after organic layer water (50ml) washing that obtains 2 times, use anhydrous sodium sulfate drying, distillation is except that desolvating.Residue carries out silica gel column chromatography, obtains oily matter 1-acetoxyl group-2-methyl-3-(3,4-ethylenedioxy phenyl) propylene 0.97g according to ethyl acetate/n-hexane=1/5 (v/v).Separation yield is 78.2%.
The physics value of 1-acetoxyl group-2-methyl-3-(3,4-ethylenedioxy phenyl) propylene is expressed as follows:
1H-NMR(300MHz，CDCl
3)δ＝1.59(3H，d，J＝1.5Hz)，2.14(3H，s)，3.15(2H，s)，4.23(4H，s)，6.64(1H，dd，J＝8.1Hz，J＝2.0Hz)，6.69(1H，d，J＝2.0Hz)，6.77(1H，d，J＝8.1Hz)，7.02(1H，q，J＝1.5Hz)。
HRMS (EI) (M
+) C
14H
16O
4Calculated value: 248.1049, measured value: 248.1051
Utilize possibility on the industry
The inventive method can and easily prepare the propen compounds as the useful 1-acetoxyl group-3-of the intermediate of spices, pharmaceuticals, agricultural chemicals product, other organic synthesis medicine (replacement phenyl) with high yield. Thereby the preparation method of 1-acetoxyl group-3-of the present invention (replacement phenyl) propen compounds has the high possibility of utilizing industrially. In addition, the 1-acetoxyl group-3-that obtains according to the inventive method (replacement phenyl) propen compounds comprises novel compound.
Claims (15)
1, the preparation method of 1-acetoxy-3-(substituted-phenyl) propen compounds, it is characterized in that, in order to prepare 1-acetoxy-3-(substituted-phenyl) propen compounds with following general formula (I) expression, be to contain by (a) halogenation boron compound, (b) the trifluoromethanesulfonic acid salt compound of 11 family's elements in the periodic table of elements, (c) halogen compounds of 12 family's elements in the periodic table of elements, (d) tin or ordination number are 58, under the existence of the catalyzer of at least a compound of selecting in the group that the trifluoromethanesulfonic acid salt compound of 66～71 lanthanon and halogen compounds constitute, make from following general formula (IV) and reach one and the represented alkylene group diacetate esters compound reaction of selecting 1 group of (V) represented benzene compound of following general formula (VI);
(in following formula (I), R
1And R
2Represent from hydrogen atom independently of one another and have one that selects the group that alkyl constituted of 1～10 carbon atom, wherein R
1And R
2Also can interconnect and 2 of propenyl and 3 carbon atom form cyclic group jointly, A represents from following formula (II) and of (III) selecting in the substituted-phenyl the represented group,
R
3And R
4Expression independently of one another has the alkyl of 1～4 carbon atom, and m represents 0 or 1～4 integer, and n represents 1～5 integer, and k represents 1 or 2 integer);
And
(at following formula (IV) and (V), R
3And R
4And n, m and k are as previously mentioned);
(in following formula (VI), R
1And R
2As previously mentioned).
2, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the represented benzene compound of above-mentioned general formula (IV) is selected from methyl-phenoxide, veratrole, hydroquinone dimethyl ether, reaches phloroglucinol trimethyl ether, reaches hydroxyl Resorcinol three methyl ethers.
3, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the represented benzene compound of above-mentioned logical formula V is selected from 1,2-methylenedioxybenzenes and ethylenedioxy benzene.
4, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the represented alkylene group diacetate esters of above-mentioned general formula (VI) is selected from 3,3-diacetoxy-2-methacrylic, 3,3-diacetoxy propylene, 3,3-diethoxy-1-methacrylic, 3,3-diacetoxy-2-ethyl propylene, 3,3-diethoxy-1-ethyl propylene and 3,3-diethoxy-1-ethyl-2-methacrylic.
5, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, in above-mentioned reaction, above-mentioned benzene compound and above-mentioned alkylene group diacetate esters use mol ratio 1～50: 1.
6, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, with respect to 1 mole of above-mentioned alkylene group diacetate esters, the usage quantity of above-mentioned catalyzer is 0.005～1 mole.
7, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the employed halogenation boron compound of above-mentioned catalyzer (a) is selected from the group that boron fluoride, boron trifluoride diethyl ether coordination compound, boron trifluoride tetrahydrofuran (THF) coordination compound, boron trifluoride acetic acid complex salt, boron trifluoride dihydrate and boron trifluoride-n-butyl ether coordination compound constitutes.
8, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the trifluoromethanesulfonic acid salt compound (b) of the employed 11 family's elements of above-mentioned catalyzer is selected from copper trifluoromethanesulfcomposite and silver trifluoromethanesulfonate.
9, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the halogen compounds (c) of the employed 12 family's elements of above-mentioned catalyzer is selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, cadmium fluoride, Cadmium chloride fine powder, cadmium bromide, cadmium iodide, hydrogen fluoride, mercury chloride, mercuric bromide and red mercury iodide.
10, the preparation method of the described 1-acetoxy-3 of claim 5-(substituted-phenyl) propen compounds, employed tin of above-mentioned catalyzer and ordination number are the fluoroform sulphonate of 58,66～71 lanthanon and trifluoromethanesulfonic acid salt compound, fluorochemical, muriate, bromide and the iodide that halogen compounds (d) is selected from tin, cerium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
11, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, above-mentioned being reflected in the atmosphere that gas constituted that does not react with above-mentioned general formula (IV), (V) and (VI) compound, above-mentioned catalyzer and resultant of reaction carried out.
12, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the compound of above-mentioned formula (I) is selected from the compound of following general formula (VII) expression;
(in above-mentioned formula (VII), R
1And R
2As previously mentioned, B is that expression is selected from following formula (VIII) and (IX) 1 in represented 1 group the substituted-phenyl,
During formula (VIII) reaches (IX), R
3And R
4And k as previously mentioned).
13, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the compound of above-mentioned general formula (I) is selected from following formula (X) and reaches (XI):
And
1-acetoxy-3-(3, the alkylenedioxy group phenyl of 4-C1～C2) propylene of expression.
14, the preparation method of the described 1-acetoxy-3 of claim 12-(substituted-phenyl) propen compounds, in above-mentioned formula (X) or (XI), R
1The expression hydrogen atom, R
2The expression methyl.
15, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the compound of above-mentioned general formula (I) is selected from 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene, 1-acetoxyl group-2-methyl-3-(3,4-ethylenedioxy phenyl) propylene, 1-acetoxyl group-2-methyl-3-(4-p-methoxy-phenyl) propylene, 1-acetoxyl group-2-methyl-3-(2, the 5-Dimethoxyphenyl) propylene and 1-acetoxyl group-2-methyl-3-(3, the 4-Dimethoxyphenyl) propylene.
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| JP2002367031 | 2002-12-18 | ||
| JP367031/2002 | 2002-12-18 | ||
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| JP316336/2003 | 2003-09-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI422581B (en) * | 2007-02-15 | 2014-01-11 | Ube Industries | 2-methyl-3-(3,4-methylenedioxyphenyl) propionaldehyde and a process for producing the same |
| CN113527077A (en) * | 2020-04-16 | 2021-10-22 | 成都三香汇香料有限公司 | Method for preparing anisyl propionaldehyde from anisole |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL230107A (en) * | 1957-08-01 | |||
| JPS55141437A (en) * | 1979-04-20 | 1980-11-05 | Toray Ind Inc | Preparation of alkenylcarboxylate derivative |
-
2003
- 2003-12-18 CN CNB200380108657XA patent/CN100336811C/en not_active Expired - Lifetime
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI422581B (en) * | 2007-02-15 | 2014-01-11 | Ube Industries | 2-methyl-3-(3,4-methylenedioxyphenyl) propionaldehyde and a process for producing the same |
| CN113527077A (en) * | 2020-04-16 | 2021-10-22 | 成都三香汇香料有限公司 | Method for preparing anisyl propionaldehyde from anisole |
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|---|---|
| CN100415734C (en) | 2008-09-03 |
| CN100336811C (en) | 2007-09-12 |
| CN1807423A (en) | 2006-07-26 |
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