JP2005501841A - 複素環式ペンタレン誘導体の製造方法 - Google Patents
複素環式ペンタレン誘導体の製造方法 Download PDFInfo
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- JP2005501841A JP2005501841A JP2003519057A JP2003519057A JP2005501841A JP 2005501841 A JP2005501841 A JP 2005501841A JP 2003519057 A JP2003519057 A JP 2003519057A JP 2003519057 A JP2003519057 A JP 2003519057A JP 2005501841 A JP2005501841 A JP 2005501841A
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- phenyl
- acid
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- -1 heterocyclic pentalene derivative Chemical class 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 239000011630 iodine Substances 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 125000003226 pyrazolyl group Chemical group 0.000 claims abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 16
- 238000000746 purification Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910010082 LiAlH Inorganic materials 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000007848 Bronsted acid Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 150000002900 organolithium compounds Chemical class 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 58
- 239000000203 mixture Substances 0.000 description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- 239000012074 organic phase Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 229930192474 thiophene Natural products 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- WEJRYKSUUFKMBC-UHFFFAOYSA-N 1-(4-chlorophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(Cl)C=C1 WEJRYKSUUFKMBC-UHFFFAOYSA-N 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 5
- CVTQOTOILXATBU-UHFFFAOYSA-N N,N-dimethyl-4,5-diphenylthiophene-3-carboxamide Chemical compound CN(C)C(=O)C1=CSC(=C1C2=CC=CC=C2)C3=CC=CC=C3 CVTQOTOILXATBU-UHFFFAOYSA-N 0.000 description 4
- 229910006124 SOCl2 Inorganic materials 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- SRXJYTZCORKVNA-UHFFFAOYSA-N 1-bromoethenylbenzene Chemical compound BrC(=C)C1=CC=CC=C1 SRXJYTZCORKVNA-UHFFFAOYSA-N 0.000 description 3
- PHMRPWPDDRGGGF-UHFFFAOYSA-N 2-bromoprop-1-ene Chemical compound CC(Br)=C PHMRPWPDDRGGGF-UHFFFAOYSA-N 0.000 description 3
- QSKPIOLLBIHNAC-UHFFFAOYSA-N 2-chloro-acetaldehyde Chemical compound ClCC=O QSKPIOLLBIHNAC-UHFFFAOYSA-N 0.000 description 3
- YFUBCYGZFQQWQT-UHFFFAOYSA-N 3-chloro-2-phenylbut-2-enal Chemical compound CC(Cl)=C(C=O)C1=CC=CC=C1 YFUBCYGZFQQWQT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NHVZTTGAHYAYQE-UHFFFAOYSA-N N,N,5-trimethyl-4-phenylthiophene-3-carboxamide Chemical compound CC1=C(C(=CS1)C(=O)N(C)C)C2=CC=CC=C2 NHVZTTGAHYAYQE-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- SYAHQELCLODWRY-UHFFFAOYSA-N ethyl 5-methyl-4-phenylthiophene-2-carboxylate Chemical compound S1C(C(=O)OCC)=CC(C=2C=CC=CC=2)=C1C SYAHQELCLODWRY-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ONDVHGBTZRMBNW-UHFFFAOYSA-N 2,3,5-triphenyl-4,5-dihydrocyclopenta[b]thiophen-6-one Chemical compound O=C1C(C=2C=CC=CC=2)CC2=C1SC(C=1C=CC=CC=1)=C2C1=CC=CC=C1 ONDVHGBTZRMBNW-UHFFFAOYSA-N 0.000 description 2
- LWFNACCNVXLARG-UHFFFAOYSA-N 2-methyl-3,5-diphenyl-4,5-dihydrocyclopenta[b]thiophen-6-one Chemical compound CC=1SC=2C(=O)C(C=3C=CC=CC=3)CC=2C=1C1=CC=CC=C1 LWFNACCNVXLARG-UHFFFAOYSA-N 0.000 description 2
- ICHPKWCNDGFKTI-UHFFFAOYSA-N 3-(4-chlorophenyl)-2,5-dimethyl-4,5-dihydrocyclopenta[b]thiophen-6-one Chemical compound O=C1C(C)CC2=C1SC(C)=C2C1=CC=C(Cl)C=C1 ICHPKWCNDGFKTI-UHFFFAOYSA-N 0.000 description 2
- VOPVQXKEEYQCRV-UHFFFAOYSA-N 5-methyl-2,3-diphenyl-4,5-dihydrocyclopenta[b]thiophen-6-one Chemical compound O=C1C(C)CC2=C1SC(C=1C=CC=CC=1)=C2C1=CC=CC=C1 VOPVQXKEEYQCRV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 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 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- YFKBXYGUSOXJGS-UHFFFAOYSA-N 1,3-Diphenyl-2-propanone Chemical compound C=1C=CC=CC=1CC(=O)CC1=CC=CC=C1 YFKBXYGUSOXJGS-UHFFFAOYSA-N 0.000 description 1
- ZTVINOQSFPDNID-UHFFFAOYSA-N 1-(4,5-diphenylthiophen-2-yl)-2-methylprop-2-en-1-one Chemical compound S1C(C(=O)C(=C)C)=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 ZTVINOQSFPDNID-UHFFFAOYSA-N 0.000 description 1
- XCKQTYQHVQDQIF-UHFFFAOYSA-N 1-(4,5-diphenylthiophen-2-yl)-2-phenylprop-2-en-1-one Chemical compound C=1C=CC=CC=1C(=C)C(=O)C(S1)=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 XCKQTYQHVQDQIF-UHFFFAOYSA-N 0.000 description 1
- DHWJOBJKOYQFHY-UHFFFAOYSA-N 1-(5-methyl-4-phenylthiophen-2-yl)-2-phenylprop-2-en-1-one Chemical compound CC=1SC(C(=O)C(=C)C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 DHWJOBJKOYQFHY-UHFFFAOYSA-N 0.000 description 1
- MVSZNRZKWZWURI-UHFFFAOYSA-N 1-[4-(4-chlorophenyl)-5-methylthiophen-2-yl]-2-methylprop-2-en-1-one Chemical compound S1C(C(=O)C(=C)C)=CC(C=2C=CC(Cl)=CC=2)=C1C MVSZNRZKWZWURI-UHFFFAOYSA-N 0.000 description 1
- MLHGKKBLBNMFMY-UHFFFAOYSA-N 2,3,5-triphenyl-4h-cyclopenta[b]thiophene Chemical compound C1=2CC(C=3C=CC=CC=3)=CC=2SC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MLHGKKBLBNMFMY-UHFFFAOYSA-N 0.000 description 1
- IWKVRARLLPOLQV-UHFFFAOYSA-N 2,3,5-triphenyl-6h-cyclopenta[b]thiophene Chemical compound C1C(C=2C=CC=CC=2)=CC2=C1SC(C=1C=CC=CC=1)=C2C1=CC=CC=C1 IWKVRARLLPOLQV-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- ZNYVLXVPKPEZLG-UHFFFAOYSA-N 2-(4-chlorophenyl)benzonitrile Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1C#N ZNYVLXVPKPEZLG-UHFFFAOYSA-N 0.000 description 1
- SAICOLLHSSNWSP-UHFFFAOYSA-N 2-methyl-3,5-diphenyl-4h-cyclopenta[b]thiophene Chemical compound CC=1SC=2C=C(C=3C=CC=CC=3)CC=2C=1C1=CC=CC=C1 SAICOLLHSSNWSP-UHFFFAOYSA-N 0.000 description 1
- HMAPKTMQOBZWCM-UHFFFAOYSA-N 3-(4-chlorophenyl)-2,5-dimethyl-6h-cyclopenta[b]thiophene Chemical compound C1C(C)=CC2=C1SC(C)=C2C1=CC=C(Cl)C=C1 HMAPKTMQOBZWCM-UHFFFAOYSA-N 0.000 description 1
- MLMYPFYUGJOXPR-UHFFFAOYSA-N 4,5-diphenylthiophene-3-carboxylic acid Chemical compound OC(=O)C1=CSC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MLMYPFYUGJOXPR-UHFFFAOYSA-N 0.000 description 1
- VMOAISGZRQXRMI-UHFFFAOYSA-N 4-(4-chlorophenyl)-5-methylthiophene-2-carboxylic acid Chemical compound S1C(C(O)=O)=CC(C=2C=CC(Cl)=CC=2)=C1C VMOAISGZRQXRMI-UHFFFAOYSA-N 0.000 description 1
- KZPBMAZSIITGBK-UHFFFAOYSA-N 5-methyl-2,3-diphenyl-4h-cyclopenta[b]thiophene Chemical compound C1=2CC(C)=CC=2SC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 KZPBMAZSIITGBK-UHFFFAOYSA-N 0.000 description 1
- QRIRUPDZWDDHQE-UHFFFAOYSA-N 5-methyl-4-phenylthiophene-2-carboxylic acid Chemical compound S1C(C(O)=O)=CC(C=2C=CC=CC=2)=C1C QRIRUPDZWDDHQE-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- YEDVUDDWJVRKIS-UHFFFAOYSA-N cyclopenta[b]pyrrole Chemical class C1=C[C]2[N]C=CC2=C1 YEDVUDDWJVRKIS-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HLSBISFVXMCFBQ-UHFFFAOYSA-N ethyl 4,5-diphenylthiophene-2-carboxylate Chemical compound S1C(C(=O)OCC)=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 HLSBISFVXMCFBQ-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Chemical group 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- OKCBEPHXQAIBDY-UHFFFAOYSA-N lithium;thiophene Chemical compound [Li].C=1C=CSC=1 OKCBEPHXQAIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- DQEUYIQDSMINEY-UHFFFAOYSA-M magnesium;prop-1-ene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C=C DQEUYIQDSMINEY-UHFFFAOYSA-M 0.000 description 1
- WQMNNHNWITXOAH-UHFFFAOYSA-M magnesium;prop-1-ene;bromide Chemical compound [Mg+2].[Br-].CC=[CH-] WQMNNHNWITXOAH-UHFFFAOYSA-M 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01202930 | 2001-08-01 | ||
| PCT/EP2002/007680 WO2003014107A1 (en) | 2001-08-01 | 2002-07-10 | Process for the preparation of heterocyclic pentalene derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005501841A true JP2005501841A (ja) | 2005-01-20 |
| JP2005501841A5 JP2005501841A5 (enExample) | 2006-01-05 |
Family
ID=8180742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003519057A Ceased JP2005501841A (ja) | 2001-08-01 | 2002-07-10 | 複素環式ペンタレン誘導体の製造方法 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6930190B2 (enExample) |
| EP (1) | EP1412347B1 (enExample) |
| JP (1) | JP2005501841A (enExample) |
| AT (1) | ATE315559T1 (enExample) |
| DE (1) | DE60208683T2 (enExample) |
| WO (1) | WO2003014107A1 (enExample) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006511609A (ja) * | 2002-12-19 | 2006-04-06 | バーゼル、ポリオレフィン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング | 複素環ケトンの製造方法 |
| JP2007505992A (ja) * | 2003-09-19 | 2007-03-15 | エスアールアイ インターナショナル | 金属ハロゲン化物の還元によって金属組成物を製造するための方法および装置 |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002100909A1 (en) * | 2001-06-12 | 2002-12-19 | Basell Polyolefine Gmbh | Process for the polymerization of 1-butene |
| DE10145453A1 (de) | 2001-09-14 | 2003-06-05 | Basell Polyolefine Gmbh | Monocyclopentadienylkomplexe mit einem kondensierten Heterocyclus |
| US7834112B2 (en) | 2001-09-14 | 2010-11-16 | Basell Polyolefine Gmbh | Method of polymerization of olefins |
| ES2268126T3 (es) | 2001-11-30 | 2007-03-16 | Basell Polyolefine Gmbh | Compuestos de metaloceno y procedimiento para la preparacion de polimeros de propileno. |
| EP1539843B1 (en) * | 2002-09-06 | 2009-10-14 | Basell Polyolefine GmbH | Process for the copolymerization of ethylene |
| EP1549688A2 (en) | 2002-10-10 | 2005-07-06 | Basell Polyolefine GmbH | Process for the copolymerization of ethylene |
| FR2860792B1 (fr) * | 2003-10-10 | 2006-02-24 | Sanofi Synthelabo | Derives de thiophene-2-carboxamide, leur preparation et leur application en therapeutique |
| EP1765886A1 (en) | 2004-07-13 | 2007-03-28 | Basell Polyolefine GmbH | Metallocene compounds, ligands used in their preparation, preparation of 1-butene polymers and 1-butene polymers therefrom |
| DE602005005334T2 (de) | 2004-07-22 | 2009-03-26 | Basell Polyolefine Gmbh | 1-butenpolymerzusammensetzung |
| KR20070043798A (ko) | 2004-07-22 | 2007-04-25 | 바젤 폴리올레핀 게엠베하 | 분획가능한 1-부텐 중합체의 제조방법 |
| WO2006010379A1 (en) | 2004-07-29 | 2006-02-02 | Actelion Pharmaceuticals Ltd. | Novel thiophene derivatives as immunosuppressive agents |
| CA2584395A1 (en) * | 2004-10-18 | 2006-04-27 | Basell Poliolefine Italia S.R.L. | Butene-1 (co)polymers having low isotacticity |
| WO2006045687A1 (en) * | 2004-10-21 | 2006-05-04 | Basell Polyolefine Gmbh | 1-butene polymer and process for the preparation thereof |
| US8051611B2 (en) * | 2005-06-24 | 2011-11-08 | Dryvit Systems, Inc. | Exterior insulation and finish system and method and tool for installing same |
| EP1896446A1 (en) | 2005-06-24 | 2008-03-12 | Actelion Pharmaceuticals Ltd. | Novel thiophene derivatives |
| DE102005061326A1 (de) * | 2005-12-20 | 2007-06-21 | Basell Polyolefine Gmbh | Verfahren zur Herstellung von Metallocenen aus recycelten, substituierten Cyclopentadienylderivaten |
| CN101370805B (zh) | 2006-01-24 | 2011-04-27 | 埃科特莱茵药品有限公司 | 吡啶衍生物 |
| JP5580590B2 (ja) | 2006-08-30 | 2014-08-27 | バーゼル・ポリオレフィン・ゲーエムベーハー | １−ブテンプロピレンコポリマー組成物 |
| US8097681B2 (en) | 2006-08-30 | 2012-01-17 | Basell Polyolefine Gmbh | 1-butene propylene copolymer compositions |
| DE102008015032A1 (de) | 2008-03-17 | 2009-09-24 | Aicuris Gmbh & Co. Kg | Substituierte Pyrazolamide und ihre Verwendung |
| DE102008015033A1 (de) | 2008-03-17 | 2009-09-24 | Aicuris Gmbh & Co. Kg | Substituierte (Pyrazolyl-carbonyl)imidazolidinone und ihre Verwendung |
| KR20100133987A (ko) * | 2008-03-20 | 2010-12-22 | 바셀 폴리올레핀 이탈리아 에스.알.엘 | 1-부텐 삼원중합체 |
| JP2011515518A (ja) * | 2008-03-20 | 2011-05-19 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | １−ブテン系ポリマー類の組成物類 |
| EP2254919A1 (en) * | 2008-03-20 | 2010-12-01 | Basell Poliolefine Italia S.R.L. | 1-butene copolymers |
| BRPI0910237A2 (pt) * | 2008-03-20 | 2015-09-29 | Basell Poliolefine Srl | copolímeros de 1-buteno |
| DE102008062878A1 (de) | 2008-12-17 | 2010-06-24 | Aicuris Gmbh & Co. Kg | Substituierte Furancarboxamide und ihre Verwendung |
| DE102008062863A1 (de) | 2008-12-17 | 2010-06-24 | Aicuris Gmbh & Co. Kg | Substituierte (Thiophenyl-carbonyl)imidazolidinone und ihre Verwendung |
| CN110372662B (zh) * | 2019-08-07 | 2021-12-21 | 西安近代化学研究所 | 基于环戊烷并噻吩骨架的液晶化合物及其合成方法 |
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| US4496742A (en) * | 1981-10-13 | 1985-01-29 | The Upjohn Company | Analogs of 5,6-dihydro PGI2 |
| DE3147714A1 (de) * | 1981-11-27 | 1983-06-01 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Neue prostacycline und verfahren zu ihrer herstellung |
| JPS63122669A (ja) * | 1986-10-25 | 1988-05-26 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | 複素環状液晶化合物 |
| CA1333612C (en) * | 1988-09-23 | 1994-12-20 | Paul Howard Briner | Process for the preparation of cyclopentene, cyclopentane, and cyclohexane derivatives |
| IL103106A (en) * | 1991-09-25 | 1998-06-15 | Sanofi Elf | Ethers of thienocyclopentanone oximes, their preparation and pharmaceutical compositions containing them |
| ES2116630T3 (es) * | 1994-02-17 | 1998-07-16 | Asahi Glass Co Ltd | Difluorprostaciclinas; productos intermediarios y procedimientos para su preparacion. |
| FR2773798B1 (fr) * | 1998-01-16 | 2001-02-02 | Adir | Nouveaux composes tricycliques, leur procede de preparation et les compositions pharmaceutiques qui les contiennent |
| US6057316A (en) * | 1998-05-12 | 2000-05-02 | American Home Products Corporation | 4-aryl-1-oxa-9-thia-cyclopenta[b]fluorenes |
| US6762316B1 (en) * | 1999-06-28 | 2004-07-13 | Biocryst Pharmaceuticals, Inc. | Preparation of substituted cyclopentane and cyclopentene compounds and certain intermediates |
| US6444833B1 (en) | 1999-12-15 | 2002-09-03 | Basell Technology Company Bv | Metallocene compounds, process for their preparation and their use in catalytic systems for the polymerization of olefins |
-
2002
- 2002-07-10 US US10/485,497 patent/US6930190B2/en not_active Expired - Fee Related
- 2002-07-10 EP EP02748851A patent/EP1412347B1/en not_active Expired - Lifetime
- 2002-07-10 WO PCT/EP2002/007680 patent/WO2003014107A1/en not_active Ceased
- 2002-07-10 AT AT02748851T patent/ATE315559T1/de not_active IP Right Cessation
- 2002-07-10 JP JP2003519057A patent/JP2005501841A/ja not_active Ceased
- 2002-07-10 DE DE60208683T patent/DE60208683T2/de not_active Expired - Lifetime
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| ISHIKURA, M., ET AL., HETEROCYCLES, vol. 53(10), JPN5003023813, pages 2201 - 2220, ISSN: 0001478217 * |
| MAXIM, N., ET AL., BULL. SOC. CHIM. FR., vol. 6, JPN6009006002, pages 1339 - 1347, ISSN: 0001478218 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006511609A (ja) * | 2002-12-19 | 2006-04-06 | バーゼル、ポリオレフィン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング | 複素環ケトンの製造方法 |
| JP2007505992A (ja) * | 2003-09-19 | 2007-03-15 | エスアールアイ インターナショナル | 金属ハロゲン化物の還元によって金属組成物を製造するための方法および装置 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003014107A1 (en) | 2003-02-20 |
| EP1412347A1 (en) | 2004-04-28 |
| US20040192931A1 (en) | 2004-09-30 |
| ATE315559T1 (de) | 2006-02-15 |
| DE60208683T2 (de) | 2006-11-02 |
| DE60208683D1 (de) | 2006-04-06 |
| EP1412347B1 (en) | 2006-01-11 |
| US6930190B2 (en) | 2005-08-16 |
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