JP7494164B2 - シクロペンテノンの合成 - Google Patents
シクロペンテノンの合成 Download PDFInfo
- Publication number
- JP7494164B2 JP7494164B2 JP2021512422A JP2021512422A JP7494164B2 JP 7494164 B2 JP7494164 B2 JP 7494164B2 JP 2021512422 A JP2021512422 A JP 2021512422A JP 2021512422 A JP2021512422 A JP 2021512422A JP 7494164 B2 JP7494164 B2 JP 7494164B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- methyl
- reagent
- alkyl
- acid
- 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.)
- Active
Links
- 238000003786 synthesis reaction Methods 0.000 title description 16
- 230000015572 biosynthetic process Effects 0.000 title description 15
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims description 142
- 239000003153 chemical reaction reagent Substances 0.000 claims description 55
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 44
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 43
- -1 cyclopentenone compound Chemical class 0.000 claims description 39
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 27
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 25
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- XAIDJKMHAGUWQN-UHFFFAOYSA-N 3-methyl-2,3,4,5,6,7-hexahydroinden-1-one Chemical compound C1CCCC2=C1C(C)CC2=O XAIDJKMHAGUWQN-UHFFFAOYSA-N 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 37
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 29
- 239000000203 mixture Substances 0.000 description 23
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 15
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 14
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229940098779 methanesulfonic acid Drugs 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 10
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 239000003880 polar aprotic solvent Substances 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 150000001925 cycloalkenes Chemical class 0.000 description 5
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 5
- ZUMGBVSYIVKLDH-QHHAFSJGSA-N cyclohexyl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC1CCCCC1 ZUMGBVSYIVKLDH-QHHAFSJGSA-N 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 239000003517 fume Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000007363 ring formation reaction Methods 0.000 description 5
- JHNLZOVBAQWGQU-UHFFFAOYSA-N 380814_sial Chemical compound CS(O)(=O)=O.O=P(=O)OP(=O)=O JHNLZOVBAQWGQU-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 3
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 description 2
- RUADGOLRFXTMCY-UHFFFAOYSA-N 2,5-dimethylcyclohexan-1-ol Chemical compound CC1CCC(C)C(O)C1 RUADGOLRFXTMCY-UHFFFAOYSA-N 0.000 description 2
- QKFKROULLRFXMV-UHFFFAOYSA-N 3,3-dimethylcyclopentan-1-ol Chemical compound CC1(C)CCC(O)C1 QKFKROULLRFXMV-UHFFFAOYSA-N 0.000 description 2
- GWIIZARHBAHTIX-UHFFFAOYSA-N 3,5,7-trimethylcyclooctan-1-ol Chemical compound CC1CC(C)CC(O)CC(C)C1 GWIIZARHBAHTIX-UHFFFAOYSA-N 0.000 description 2
- VEALHWXMCIRWGC-UHFFFAOYSA-N 3-methylcyclopentan-1-ol Chemical compound CC1CCC(O)C1 VEALHWXMCIRWGC-UHFFFAOYSA-N 0.000 description 2
- AHTKROFORNYYSL-UHFFFAOYSA-N 4,4-dimethylcycloheptan-1-ol Chemical compound CC1(C)CCCC(O)CC1 AHTKROFORNYYSL-UHFFFAOYSA-N 0.000 description 2
- GNOXBYBSCDZVMJ-UHFFFAOYSA-N 4-methylcycloheptan-1-ol Chemical compound CC1CCCC(O)CC1 GNOXBYBSCDZVMJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 2
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 description 2
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 0.000 description 1
- 125000006526 (C1-C2) alkyl group Chemical group 0.000 description 1
- 125000004814 1,1-dimethylethylene group Chemical group [H]C([H])([H])C([*:1])(C([H])([H])[H])C([H])([H])[*:2] 0.000 description 1
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004809 1-methylpropylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- NDVWOBYBJYUSMF-UHFFFAOYSA-N 2-methylcyclohexan-1-ol Chemical compound CC1CCCCC1O NDVWOBYBJYUSMF-UHFFFAOYSA-N 0.000 description 1
- 125000004810 2-methylpropylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])[*:1] 0.000 description 1
- UMJCOSIPVBOCGS-UHFFFAOYSA-N 3,4-dimethylcyclopentan-1-ol Chemical compound CC1CC(O)CC1C UMJCOSIPVBOCGS-UHFFFAOYSA-N 0.000 description 1
- KWNIUTKCMLCEBU-UHFFFAOYSA-N 3-methyl-3a,4,5,6,7,7a-hexahydroinden-1-one Chemical compound C1CCCC2C(C)=CC(=O)C21 KWNIUTKCMLCEBU-UHFFFAOYSA-N 0.000 description 1
- QSVDFJNXDKTKTJ-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1h-indene Chemical class C1CCCC2=C1CC=C2 QSVDFJNXDKTKTJ-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RIVYHPGDAMWJDR-UHFFFAOYSA-N C1C=CC=2CC(CCC1=2)[Ru] Chemical class C1C=CC=2CC(CCC1=2)[Ru] RIVYHPGDAMWJDR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NIONDZDPPYHYKY-UHFFFAOYSA-N Z-hexenoic acid Natural products CCCC=CC(O)=O NIONDZDPPYHYKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 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
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N iso-butene Natural products CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 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
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/86—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
- C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/623—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
- C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/623—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
- C07C49/633—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having two rings the condensed ring system containing eight or nine carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Uemichi,Yoshio;Kanoh,Hisao.Kenkyu Hokoku-Asahi Garasu Kogyo Gijutsu Shoreikai,Volume 49,Pages 225-30,1986.CODEN:AGKGAA.ISSN:0365-2599によれば、白金は、特にポリエチレン分解の強力な原料であると報告されている。Uemichi,Yoshio;Makino,Yutaka;Kanazuka,Takaji,Degradation of polyethylene to aromatic hydrocarbons over metal-supported activated carbon catalysts,Journal of Analytical and Applied Pyrolysis(1989),14(4),331-44。
(式中、R4は、脱水条件下で、化合物(1)に対して定義されたとおりである)と反応させることによって容易に合成することができる。好適な脱水条件としては、還流トルエン、パラトルエンスルホン酸(pTsOH)などのプロトン酸、および生成される水を除去するためのディーンスタークトラップ、または分離するための乾燥剤が挙げられる。乾燥剤の例は、3オングストロームのモレキュラーシーブおよび無水硫酸ナトリウムである。対応するアルコールおよびカルボン酸からカルボン酸のエステルを合成するための方法ならびに条件はよく知られており、有用である。化合物(1)はまた、式(a)のシクロアルカノールを、対応するα、β-不飽和カルボン酸無水物と反応させることによって合成することができ、2モル等量の化合物(b)を脱水することによって作製することができる。
ドラフト内で、撹拌棒を備えた100mL丸底フラスコ内の窒素雰囲気下で、調製3の化合物(1c)(2E)-2-ブテン酸、シクロペンチルエステル(0.5g、3.24mmol)を添加した。フラスコ内のエステルを0℃に冷却した。次いで、P2O5/H3CSO3H試薬(0.1/1))(1.5mL、9.73mmol)を0℃で滴下した。得られた反応混合物を周囲温度(23℃)まで撹拌しながら温め、72時間撹拌を続けた。得られた粗生成物を5mLの水で希釈し、次いで、発泡がおさまるまで固体NaHCO3を少しずつ加えて、pH8~pH9を有するクエンチした混合物を得た。分液漏斗で、クエンチした混合物の水層と有機層を分離した。水層をジエチルエーテル(3×8mL)で3回抽出した。有機層を3つの抽出物と混ぜ合わせ、その混合を食塩水(15mL)で洗浄し、硫酸マグネシウム上で乾燥させ、ろ過した。真空中で溶媒を除去して、0.42g(95%収率)の化合物(2c)をオレンジ色の油として得た。1H NMR(400MHz、クロロホルム-d)δ3.05~2.89(m、1H)、2.81(dt、1H)、2.66~2.47(m、1H)、2.47~2.26(m、6H)、1.19(d、3H)は、化合物(2c)と一致した。
本願は以下の態様にも関する。
(1) 置換シクロペンテノン化合物を合成する方法であって、(A)式(1)の化合物(「化合物(1)」):
(2) 前記P 2 O 5 /H 3 CSO 3 H試薬を作製するために使用されるP 2 O 5 対H 3 CSO 3 Hの比は、0.05/1~1/1(重量/重量)である、前記(1)に記載の方法。
(3) 前記P 2 O 5 /H 3 CSO 3 H試薬を作製するために使用されるP 2 O 5 対H 3 CSO 3 Hの比は、0.1/1(重量/重量)である、前記(1)または(2)に記載の方法。
(4) 制限(i)~(xxi):(i)R 1 ~R 3 のうちの少なくとも1つが(C 1 ~C 4 )アルキルであるか、またはR4がHであること、(ii)R1~R4のそれぞれがHであること、(iii)R1~R3のそれぞれがHであり、R4がメチルであること、(iv)R1およびR2のそれぞれがHであり、R3およびR4のそれぞれがメチルであること、(v)R1および/またはR2がメチルであり、R3がHであること、(vi)R1がメチルであり、R2が1-メチルエチルであり、R3がHであること、(vii)R1が1-メチルエチルであり、R2がメチルであり、R3がHであること、(viii)R1およびR2が独立して、(C 1 ~C 4 )アルキルであり、R3がHであり、R1に結合した炭素原子の立体化学が(R)であり、R2に結合した炭素原子の立体化学が(S)であること、(ix)R1およびR2が独立して、(C 1 ~C 4 )アルキルであり、R3がHであり、R1に結合した炭素原子の立体化学が(S)であり、R2に結合した炭素原子の立体化学が(R)であること、(x)(vi)および(viii)の両方、(xi)(vi)および(ix)の両方、(xii)(vii)および(viii)の両方、(xiii)(vii)および(ix)の両方、(xiv)R5がHであること、(xv)R5がメチルであること、(xvi)(i)および(xiv)または(xv)の両方、(xvii)(ii)および(xiv)または(xv)の両方、(xviii)(iii)および(xiv)または(xv)の両方、(xix)(iv)および(xiv)または(xv)の両方、(xx)(v)および(xiv)または(xv)の両方、ならびに(xxi)任意の2つの隣接したR1~R3基が、一緒に結合して(C 1 ~C 4 )アルキレンを形成し、R1~R3のうちの残りの基が、Hまたは(C 1 ~C 4 )アルキルであること、のうちのいずれか1つを特徴とする、前記(1)~(3)のいずれか一項に記載の方法。
(5) 前記化合物(2)は、化合物(2a)~(2e):
構造(2a)を有する、化合物(2a)2,3,4,5,6,7-ヘキサヒドロ-3-メチル-1H-インデン-1-オン、
化合物(2e)2,4,6,11-テトラメチル-ビシクロ[6.3.0]-1(8)-ウンデセン-9-オン、のいずれか1つからなる群から選択される、前記(1)~(4)のいずれか一項に記載の方法。
Claims (5)
- 置換シクロペンテノン化合物を合成する方法であって、
(A)式(1)の化合物(「化合物(1)」):
(式中、下付き文字nは、1、2、3または4であり、基R1、R2、R3、およびR4のそれぞれが独立して、Hもしくは(C1~C4)アルキルであるか、または任意の2つの隣接したR1~R3基が、一緒に結合して(C1~C4)アルキレンを形成し、R1~R3のうちの残りの基が、Hもしくは(C1~C4)アルキルである)を、
有効量の五酸化リン/メタンスルホン酸試薬(P2O5/H3CSO3H試薬)と、
式(2)の化合物(「化合物(2)」):
(式中、下付き文字nおよび基R1~R4は先に定義されたとおりである)を作製するのに十分な反応条件下で接触させることを含み、但し、前記接触工程(A)は添加されたポリリン酸(PPA)を含まない、方法。 - 前記P2O5/H3CSO3H試薬を作製するために使用されるP2O5対H3CSO3Hの比は、0.05/1~1/1(重量/重量)である、請求項1に記載の方法。
- 前記P2O5/H3CSO3H試薬を作製するために使用されるP2O5対H3CSO3Hの比は、0.1/1(重量/重量)である、請求項1または2に記載の方法。
- 制限(i)~(xiii)、および(xxi):
(i)R 1 ~R 3 のうちの少なくとも1つが(C1~C4)アルキルであるか、またはR 4 がHであること、
(ii)R 1 ~R 4 のそれぞれがHであること、
(iii)R 1 ~R 3 のそれぞれがHであり、R 4 がメチルであること、
(iv)R 1 およびR 2 のそれぞれがHであり、R 3 およびR 4 のそれぞれがメチルであること、
(v)R 1 および/またはR 2 がメチルであり、R 3 がHであること、
(vi)R 1 がメチルであり、R 2 が1-メチルエチルであり、R 3 がHであること、
(vii)R 1 が1-メチルエチルであり、R 2 がメチルであり、R 3 がHであること、
(viii)R 1 およびR 2 が独立して、(C1~C4)アルキルであり、R 3 がHであり、R 1 に結合した炭素原子の立体化学が(R)であり、R 2 に結合した炭素原子の立体化学が(S)であること、
(ix)R 1 およびR 2 が独立して、(C1~C4)アルキルであり、R 3 がHであり、R 1 に結合した炭素原子の立体化学が(S)であり、R 2 に結合した炭素原子の立体化学が(R)であること、
(x)(vi)および(viii)の両方、
(xi)(vi)および(ix)の両方、
(xii)(vii)および(viii)の両方、
(xiii)(vii)および(ix)の両方、
ならびに
(xxi)任意の2つの隣接したR 1 ~R 3 基が、一緒に結合して(C1~C4)アルキレンを形成し、R 1 ~R 3 のうちの残りの基が、Hまたは(C1~C4)アルキルであること、
のうちのいずれか1つを特徴とする、請求項1~3のいずれか一項に記載の方法。 - 前記化合物(2)は、化合物(2a)~(2e):
構造(2a)を有する、化合物(2a)2,3,4,5,6,7-ヘキサヒドロ-3-メチル-1H-インデン-1-オン、
化合物(2e)2,4,6,11-テトラメチル-ビシクロ[6.3.0]-1(8)-ウンデセン-9-オン、のいずれか1つからなる群から選択される、請求項1~4のいずれか一項に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201862737969P | 2018-09-28 | 2018-09-28 | |
US62/737,969 | 2018-09-28 | ||
PCT/US2019/050544 WO2020068419A1 (en) | 2018-09-28 | 2019-09-11 | Synthesis of cyclopentenones |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2022501323A JP2022501323A (ja) | 2022-01-06 |
JP7494164B2 true JP7494164B2 (ja) | 2024-06-03 |
Family
ID=68051987
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2021512422A Active JP7494164B2 (ja) | 2018-09-28 | 2019-09-11 | シクロペンテノンの合成 |
Country Status (9)
Country | Link |
---|---|
US (1) | US11292757B2 (ja) |
EP (1) | EP3856709B1 (ja) |
JP (1) | JP7494164B2 (ja) |
KR (1) | KR20210068482A (ja) |
CN (1) | CN112601731B (ja) |
BR (1) | BR112021003385B1 (ja) |
CA (1) | CA3112919A1 (ja) |
SG (1) | SG11202102215WA (ja) |
WO (1) | WO2020068419A1 (ja) |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5492947A (en) * | 1977-12-28 | 1979-07-23 | Mitsui Petrochem Ind Ltd | Production of bicyclo10.3.0pentadeca-1(12)-ene-13-one |
US5721185A (en) | 1991-06-24 | 1998-02-24 | The Dow Chemical Company | Homogeneous olefin polymerization catalyst by abstraction with lewis acids |
JPH06287150A (ja) * | 1993-04-01 | 1994-10-11 | Nippon Fine Chem Kk | ジエン化合物の製造方法 |
IT1273662B (it) | 1994-07-20 | 1997-07-09 | Spherilene Srl | Procedimento per la preparazione di polimeri amorfi del propiline' |
IT1277696B1 (it) | 1995-12-22 | 1997-11-11 | Enichem Spa | Catalizzatori per la polimerizzazione di alfa-olefine |
JPH10316694A (ja) | 1997-03-18 | 1998-12-02 | Idemitsu Petrochem Co Ltd | 遷移金属化合物、それを用いた重合用触媒及び該重合 用触媒を用いた重合体の製造方法 |
US6911508B2 (en) | 2003-06-05 | 2005-06-28 | Univation Technologies, Llc | Class of metallocenes and method of producing polyethylene |
US8785677B1 (en) | 2013-02-25 | 2014-07-22 | International Flavors & Fragrances Inc. | Organoleptic compound |
CN111132989B (zh) | 2017-09-28 | 2023-12-15 | 尤尼威蒂恩技术有限责任公司 | 环状有机化合物和茂金属的合成 |
SG10202012871WA (en) | 2017-09-28 | 2021-01-28 | Univation Tech Llc | Synthesis of cyclic organic compounds and metallocenes |
CA3076590A1 (en) | 2017-09-28 | 2019-04-04 | Univation Technologies, Llc | Synthesis of cyclic organic compounds and metallocenes |
-
2019
- 2019-09-11 WO PCT/US2019/050544 patent/WO2020068419A1/en active Application Filing
- 2019-09-11 JP JP2021512422A patent/JP7494164B2/ja active Active
- 2019-09-11 SG SG11202102215WA patent/SG11202102215WA/en unknown
- 2019-09-11 EP EP19773680.4A patent/EP3856709B1/en active Active
- 2019-09-11 CN CN201980055816.5A patent/CN112601731B/zh active Active
- 2019-09-11 US US17/263,183 patent/US11292757B2/en active Active
- 2019-09-11 KR KR1020217012159A patent/KR20210068482A/ko active Search and Examination
- 2019-09-11 BR BR112021003385-8A patent/BR112021003385B1/pt active IP Right Grant
- 2019-09-11 CA CA3112919A patent/CA3112919A1/en active Pending
Non-Patent Citations (4)
Title |
---|
CONIA, J. M. et al.,"No. 515. - Sur la preparation de cyclopentenones par action de l'acide polyphosphorique sur les esters d'acides alpha-ethyleniques. 1re Partie: Aspects pratiques",BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE,1970年,No. 8-9,pp. 2981-2991,ISSN: 0037-8968 |
CONIA, J. M. et al.,"Sur un mode de preparation simple des cyclopentenones par action de l'acide polyphosphorique sur les esters d'acides αβ-ethyleniques",Tetrahedron Letters,1968年,Vol. 9、No. 17,pp. 2101-2104,DOI: 10.1016/S0040-4039(00)89752-X |
EATON, P. E. et al.,"Phosphorus pentoxide-methanesulfonic acid. Convenient alternative to polyphosphoric acid",The Journal of Organic Chemistry,1973年,Vol. 38, No. 23,pp. 4071-4073,DOI: 10.1021/jo00987a028 |
ZEWGE, D. et al.,"A Mild and Efficient Synthesis of 4-Quinolones and Quinolone Heterocycles",The Journal of Organic Chemistry,2007年,Vol. 72, No. 11,pp. 4276-4279,DOI: 10.1021/jo070181o |
Also Published As
Publication number | Publication date |
---|---|
WO2020068419A1 (en) | 2020-04-02 |
US11292757B2 (en) | 2022-04-05 |
CN112601731A (zh) | 2021-04-02 |
CA3112919A1 (en) | 2020-04-02 |
US20210206709A1 (en) | 2021-07-08 |
JP2022501323A (ja) | 2022-01-06 |
KR20210068482A (ko) | 2021-06-09 |
CN112601731B (zh) | 2023-10-03 |
SG11202102215WA (en) | 2021-04-29 |
BR112021003385B1 (pt) | 2024-02-15 |
EP3856709B1 (en) | 2024-06-26 |
EP3856709A1 (en) | 2021-08-04 |
BR112021003385A2 (pt) | 2021-05-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2008538352A (ja) | Ru/二座配位子の錯体を用いたエステルの水素化 | |
ES2912167T3 (es) | Síntesis de compuestos orgánicos cíclicos y metalocenos | |
Leforestier et al. | Synthesis and group 9 complexes of macrocyclic PCP and POCOP pincer ligands | |
JP7405839B2 (ja) | 置換シクロペンタジエン化合物およびメタロセンの合成 | |
JP7494164B2 (ja) | シクロペンテノンの合成 | |
US8278449B2 (en) | Thermally switchable ruthenium initiators | |
Söhner et al. | Halogen-free water-stable aluminates as replacement for persistent fluorinated weakly-coordinating anions | |
Knorr et al. | Reactivity of silyl-substituted heterobimetallic iron–platinum hydride complexes towards unsaturated molecules: Part II. Insertion of trifluoropropyne and hexafluorobutyne into the platinum–hydride bond | |
US10975012B2 (en) | Synthesis of cyclic organic compounds | |
Shao et al. | Synthesis and structural characterization of zirconium complexes containing aminodiolate ligands and their use as Lewis acid catalysts | |
Al‐Majid et al. | Synthesis of Some C2‐Symmetric Bidentate Ligands and Their Complexes Derived from Feist's Acid | |
Pavun et al. | A mesoionic carbene stabilized nickel (ii) hydroxide complex: a facile precursor for C–H activation chemistry | |
Esarte Palomero | Synthesis and characterization of 1, 1’-dicarbodiimidoferrocenes: heteroallylic ligand precursors for early transition metal guanidinate complexes and boramidinate frustrated Lewis pairs | |
JPS638959B2 (ja) | ||
Berenguer et al. | Preparation and characterisation of neutral double-and mono-alkynyl bridged diplatinum complexes | |
Burt et al. | Reaction of hexafluorobut-2-yne with carbonyl complexes of iron, ruthenium, and osmium | |
Schwarz et al. | Synthesis, crystal structure, and NMR investigation of methyl α, α-dimethyl acetate-substituted π-allylpalladium complexes | |
JPH02231484A (ja) | トリオール誘導体とその製造法 | |
JPS61151146A (ja) | 1(又は2あるいは3)−ホルミルプロポキシメチルベンゼンの製造法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20210309 |
|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20210701 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220829 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230718 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230725 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20231025 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20231219 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240229 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20240514 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240522 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7494164 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |