DE60208683T2 - Verfahren zur herstellung von heterocyclischen pentalen derivaten - Google Patents
Verfahren zur herstellung von heterocyclischen pentalen derivaten Download PDFInfo
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- DE60208683T2 DE60208683T2 DE60208683T DE60208683T DE60208683T2 DE 60208683 T2 DE60208683 T2 DE 60208683T2 DE 60208683 T DE60208683 T DE 60208683T DE 60208683 T DE60208683 T DE 60208683T DE 60208683 T2 DE60208683 T2 DE 60208683T2
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- 238000004519 manufacturing process Methods 0.000 title abstract 2
- QGMRQYFBGABWDR-UHFFFAOYSA-N sodium;5-ethyl-5-pentan-2-yl-1,3-diazinane-2,4,6-trione Chemical class [Na+].CCCC(C)C1(CC)C(=O)NC(=O)NC1=O QGMRQYFBGABWDR-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000460 chlorine Substances 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 9
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- -1 heterocyclic pentalene derivative Chemical class 0.000 claims abstract description 8
- 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 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007848 Bronsted acid Substances 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 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 18
- 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 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 229910010082 LiAlH Inorganic materials 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000011593 sulfur Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 125000003226 pyrazolyl group Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- 239000000203 mixture Substances 0.000 description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- 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
- 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
- 239000000047 product Substances 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- 239000012074 organic phase Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 238000010992 reflux Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 238000003756 stirring 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
- 238000004821 distillation Methods 0.000 description 5
- 239000001257 hydrogen Substances 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 238000002425 crystallisation Methods 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
- 239000002244 precipitate Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- PHMRPWPDDRGGGF-UHFFFAOYSA-N 2-bromoprop-1-ene Chemical compound CC(Br)=C PHMRPWPDDRGGGF-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 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
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SRXJYTZCORKVNA-UHFFFAOYSA-N 1-bromoethenylbenzene Chemical compound BrC(=C)C1=CC=CC=C1 SRXJYTZCORKVNA-UHFFFAOYSA-N 0.000 description 2
- 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
- QSKPIOLLBIHNAC-UHFFFAOYSA-N 2-chloro-acetaldehyde Chemical group ClCC=O QSKPIOLLBIHNAC-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
- 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 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
- 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 2
- 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 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 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
- 229930192474 thiophene Natural products 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
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 1
- 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
- NWQWQKUXRJYXFH-UHFFFAOYSA-N 2,2-Dichloroacetaldehyde Chemical compound ClC(Cl)C=O NWQWQKUXRJYXFH-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
- ROUCEOOZZLFMBL-UHFFFAOYSA-N 2-methyl-3,5-diphenyl-6h-cyclopenta[b]thiophene Chemical compound CC=1SC=2CC(C=3C=CC=CC=3)=CC=2C=1C1=CC=CC=C1 ROUCEOOZZLFMBL-UHFFFAOYSA-N 0.000 description 1
- AJXBRTSKJYLODR-UHFFFAOYSA-N 3-(4-chlorophenyl)-2,5-dimethyl-6h-cyclopenta[b]thiophene;lithium Chemical compound [Li].C1C(C)=CC2=C1SC(C)=C2C1=CC=C(Cl)C=C1 AJXBRTSKJYLODR-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
- 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
- RRRGXIXLWIYWJT-UHFFFAOYSA-N 5-methyl-2,3-diphenyl-6h-cyclopenta[b]thiophene Chemical compound C1C(C)=CC2=C1SC(C=1C=CC=CC=1)=C2C1=CC=CC=C1 RRRGXIXLWIYWJT-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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 238000004639 Schlenk technique Methods 0.000 description 1
- IUJDSEJGGMCXSG-UHFFFAOYSA-N Thiopental Chemical compound CCCC(C)C1(CC)C(=O)NC(=S)NC1=O IUJDSEJGGMCXSG-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
- HHNLJRLNDSEYOX-UHFFFAOYSA-M [Br-].CC=C[Mg+] Chemical compound [Br-].CC=C[Mg+] HHNLJRLNDSEYOX-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- FEMBXICCJNZMMC-UHFFFAOYSA-M allyl magnesium bromide Chemical compound [Br-].[Mg+]CC=C FEMBXICCJNZMMC-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 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
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000002803 fossil fuel Substances 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
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 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
- 239000000314 lubricant 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
- LRPCLTPZMUIPFK-UHFFFAOYSA-N methane;sulfuric acid Chemical compound C.OS(O)(=O)=O LRPCLTPZMUIPFK-UHFFFAOYSA-N 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GUVXZFRDPCKWEM-UHFFFAOYSA-N pentalene Chemical compound C1=CC2=CC=CC2=C1 GUVXZFRDPCKWEM-UHFFFAOYSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 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
- 239000004094 surface-active agent Substances 0.000 description 1
- 229960003279 thiopental Drugs 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 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)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01202930 | 2001-08-01 | ||
| 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 |
|---|---|
| DE60208683D1 DE60208683D1 (de) | 2006-04-06 |
| DE60208683T2 true DE60208683T2 (de) | 2006-11-02 |
Family
ID=8180742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE60208683T Expired - Lifetime DE60208683T2 (de) | 2001-08-01 | 2002-07-10 | Verfahren zur herstellung von heterocyclischen pentalen derivaten |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6930190B2 (https=) |
| EP (1) | EP1412347B1 (https=) |
| JP (1) | JP2005501841A (https=) |
| AT (1) | ATE315559T1 (https=) |
| DE (1) | DE60208683T2 (https=) |
| WO (1) | WO2003014107A1 (https=) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1446429B1 (en) * | 2001-06-12 | 2009-10-07 | 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 |
| ATE412016T1 (de) * | 2001-09-14 | 2008-11-15 | Basell Polyolefine Gmbh | Verfahren zur polymerisation von olefinen |
| WO2003045964A1 (en) | 2001-11-30 | 2003-06-05 | Basell Polyolefine Gmbh | Metallocene compounds and process for the preparation of propylene polymers |
| WO2004022613A1 (en) | 2002-09-06 | 2004-03-18 | Basell Polyolefine Gmbh | Process for the copolymerization of ethylene |
| JP2006502260A (ja) * | 2002-10-10 | 2006-01-19 | バセル ポリオレフィン ジーエムビーエイチ | エチレンの共重合方法 |
| DE10260095A1 (de) * | 2002-12-19 | 2004-07-01 | Basell Polyolefine Gmbh | Verfahren zur Herstellung von heterocyclischen Ketonen |
| AU2004280559A1 (en) * | 2003-09-19 | 2005-04-21 | Sri International | Methods and apparatuses for producing metallic compositions via reduction of metal halides |
| FR2860792B1 (fr) * | 2003-10-10 | 2006-02-24 | Sanofi Synthelabo | Derives de thiophene-2-carboxamide, leur preparation et leur application en therapeutique |
| WO2006005648A1 (en) | 2004-07-13 | 2006-01-19 | Basell Polyolefine Gmbh | Metallocene compounds, ligands used in their preparation, preparation of 1-butene polymers and 1-butene polymers therefrom |
| ATE388994T1 (de) | 2004-07-22 | 2008-03-15 | Basell Polyolefine Gmbh | 1-butenpolymerzusammensetzung |
| JP2008506825A (ja) | 2004-07-22 | 2008-03-06 | バーゼル・ポリオレフィン・ゲーエムベーハー | フラクション化可能な１−ブテンポリマー類の製造法 |
| WO2006010379A1 (en) | 2004-07-29 | 2006-02-02 | Actelion Pharmaceuticals Ltd. | Novel thiophene derivatives as immunosuppressive agents |
| PL1805231T3 (pl) | 2004-10-18 | 2010-08-31 | Basell Poliolefine Italia Srl | (Ko)polimery butenu-1 o niskiej izotaktyczności |
| EP1802669B1 (en) * | 2004-10-21 | 2011-03-09 | Basell Polyolefine GmbH | 1-butene polymer and process for the preparation thereof |
| US7951794B2 (en) | 2005-06-24 | 2011-05-31 | Actelion Pharmaceuticals Ltd. | Thiophene derivatives |
| US8051611B2 (en) * | 2005-06-24 | 2011-11-08 | Dryvit Systems, Inc. | Exterior insulation and finish system and method and tool for installing same |
| DE102005061326A1 (de) * | 2005-12-20 | 2007-06-21 | Basell Polyolefine Gmbh | Verfahren zur Herstellung von Metallocenen aus recycelten, substituierten Cyclopentadienylderivaten |
| AU2007209051A1 (en) | 2006-01-24 | 2007-08-02 | Actelion Pharmaceuticals Ltd | Novel pyridine derivatives |
| WO2008025710A1 (en) | 2006-08-30 | 2008-03-06 | Basell Polyolefine Gmbh | 1-butene propylene copolymer compositions |
| 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 |
| DE102008015033A1 (de) | 2008-03-17 | 2009-09-24 | Aicuris Gmbh & Co. Kg | Substituierte (Pyrazolyl-carbonyl)imidazolidinone und ihre Verwendung |
| DE102008015032A1 (de) | 2008-03-17 | 2009-09-24 | Aicuris Gmbh & Co. Kg | Substituierte Pyrazolamide und ihre Verwendung |
| EP2254918A1 (en) * | 2008-03-20 | 2010-12-01 | Basell Poliolefine Italia S.R.L. | 1-butene terpolymers |
| ATE543870T1 (de) * | 2008-03-20 | 2012-02-15 | Basell Poliolefine Srl | Zusammensetzungen aus polymeren auf 1-buten-basis |
| EP2254917A1 (en) * | 2008-03-20 | 2010-12-01 | Basell Poliolefine Italia S.R.L. | 1-butene copolymers |
| JP2011515517A (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−ブテンコポリマー |
| DE102008062863A1 (de) | 2008-12-17 | 2010-06-24 | Aicuris Gmbh & Co. Kg | Substituierte (Thiophenyl-carbonyl)imidazolidinone und ihre Verwendung |
| DE102008062878A1 (de) | 2008-12-17 | 2010-06-24 | Aicuris Gmbh & Co. Kg | Substituierte Furancarboxamide 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 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| DE69531110T2 (de) * | 1994-02-17 | 2004-05-19 | Asahi Glass Co., Ltd. | Difluoroprostacycline, Zwischenprodukte zu deren Herstellung und Herstellungsverfahren |
| 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 JP JP2003519057A patent/JP2005501841A/ja not_active Ceased
- 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 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 DE DE60208683T patent/DE60208683T2/de not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP1412347B1 (en) | 2006-01-11 |
| EP1412347A1 (en) | 2004-04-28 |
| US20040192931A1 (en) | 2004-09-30 |
| ATE315559T1 (de) | 2006-02-15 |
| JP2005501841A (ja) | 2005-01-20 |
| WO2003014107A1 (en) | 2003-02-20 |
| DE60208683D1 (de) | 2006-04-06 |
| US6930190B2 (en) | 2005-08-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8364 | No opposition during term of opposition |