MXPA96003616A - Cylopentadienile derivatives and processes to supreparate - Google Patents
Cylopentadienile derivatives and processes to supreparateInfo
- Publication number
- MXPA96003616A MXPA96003616A MXPA/A/1996/003616A MX9603616A MXPA96003616A MX PA96003616 A MXPA96003616 A MX PA96003616A MX 9603616 A MX9603616 A MX 9603616A MX PA96003616 A MXPA96003616 A MX PA96003616A
- Authority
- MX
- Mexico
- Prior art keywords
- general formula
- carried out
- compound
- give
- process according
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 230000007717 exclusion Effects 0.000 claims abstract description 3
- 150000002576 ketones Chemical class 0.000 claims description 29
- -1 alkylaryl radicals Chemical class 0.000 claims description 27
- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 7
- 239000001384 succinic acid Substances 0.000 claims description 7
- 238000006114 decarboxylation reaction Methods 0.000 claims description 6
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 6
- 229910010084 LiAlH4 Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- IZVGQRDTRJXDCF-UHFFFAOYSA-N 2,4,5,6,7,8-hexahydroazulene Chemical compound C1CCCCC2=CCC=C21 IZVGQRDTRJXDCF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- FSRUXSXQCDMZSI-UHFFFAOYSA-N 4,5,6,7,8,9,10,11,12,13-decahydro-2h-cyclopenta[12]annulene Chemical compound C1CCCCCCCCCC2=CCC=C21 FSRUXSXQCDMZSI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000002897 diene group Chemical group 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 77
- 239000000047 product Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 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 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000012259 ether extract Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 3
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 2
- 101150041968 CDC13 gene Proteins 0.000 description 2
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000006600 Stobbe condensation reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- BIEBZGCKLFWMCR-UHFFFAOYSA-N 2,3,3a,4-tetrahydro-1h-indene Chemical class C1C=CC=C2CCCC21 BIEBZGCKLFWMCR-UHFFFAOYSA-N 0.000 description 1
- CUYLPYBYCYQGCE-UHFFFAOYSA-N 2-benzylcyclohexan-1-one Chemical compound O=C1CCCCC1CC1=CC=CC=C1 CUYLPYBYCYQGCE-UHFFFAOYSA-N 0.000 description 1
- DRLVMOAWNVOSPE-UHFFFAOYSA-N 2-phenylcyclohexan-1-one Chemical compound O=C1CCCCC1C1=CC=CC=C1 DRLVMOAWNVOSPE-UHFFFAOYSA-N 0.000 description 1
- YOKZDALFYWMEHH-UHFFFAOYSA-N 3,4,5,6,7,8-hexahydro-2h-azulen-1-one Chemical compound C1CCCCC2=C1C(=O)CC2 YOKZDALFYWMEHH-UHFFFAOYSA-N 0.000 description 1
- GEVMEMAOWFMWAD-UHFFFAOYSA-N 3-methyl-4,5,6,7,8,9,10,11,12,13-decahydro-2h-cyclopenta[12]annulene Chemical compound C1CCCCCCCCCC2=CCC(C)=C21 GEVMEMAOWFMWAD-UHFFFAOYSA-N 0.000 description 1
- USBCYHSCQDWZJS-UHFFFAOYSA-N 4,5,6,7,8,9-hexahydro-2h-cyclopenta[8]annulene Chemical compound C1CCCCCC2=CCC=C21 USBCYHSCQDWZJS-UHFFFAOYSA-N 0.000 description 1
- QXAIDADUIMVTPS-UHFFFAOYSA-N 9-(9h-fluoren-9-yl)-9h-fluorene Chemical group C12=CC=CC=C2C2=CC=CC=C2C1C1C2=CC=CC=C2C2=CC=CC=C21 QXAIDADUIMVTPS-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 241000349731 Afzelia bipindensis Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical compound O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000010348 incorporation Methods 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
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012047 saturated solution Substances 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
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003900 succinic acid esters Chemical class 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
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Abstract
The present invention relates to cyclopentadienyl derivatives having the general formula (I): wherein R, R1, R2, R4, equivalents to or different from each other, are selected from: -H, alkyl radicals having a number of carbon atoms from 1 to 5, cycloalkyl radicals having a carbon number of 5 to 8, aryl and alkylaryl radicals having a carbon number of 6 to 8, aralkyl radicals having a carbon number of from 7 to 9; is an integer from 2 to 18, with the proviso that the number of R different from H does not exceed 2, with the exclusion of the compound that has n3, R = R1 = R2 = R4 = H. The invention also describes the process for the preparation of the cyclopentadienyl derivatives mentioned above.
Description
CYLOPENTADIENILE DERIVATIVES AND PROCESSES FOR PREPARATION
DESCRIPTION OF THE INVENTION
The present invention relates to novel cyclopentadienyl derivatives and the process for their preparation. It is known that the most usable soluble catalysts for the homo- and co-polymerization of α-olefins consists of complexes of zirconium or titanium carrying ligands of the bis-indenyl type, the bis-fluorenyl type or the mixed fluorenyl-cyclopentadienyl type (PC Mohring, NJ Coville, J. Organomet, Chem. 479, 1, 1994). It is also known that the corresponding tetrahydroindene derivatives, which also have a high activity, are more effective in the incorporation of co- and ter-monomers and therefore, are among the preferred catalysts. Indene or fluorene derivatives are readily available, but the corresponding tetrahydroindenyl derivatives are obtained by direct hydrogenation of the zirconium complex, since it is difficult to chemoselectively hydrogenate the initial ligands.
The hydrogenation processes of the complex show, however, some inconveniences. In fact, as reported by some experts (see E. Samuel, Bull, Soc Chi, Fr., 3548, 1966 and S. Collins et al., In Organometallic Chem., 342, 21, 1988), in effecting hydrogenation, there are difficulties due to low yields and / or drastic conditions. Now, new cyclopentadienyl derivatives have been found, which overcome the disadvantages mentioned in the foregoing, due to their structure, they do not need the hydrogenation step mentioned above of the complex with zirconium. Accordingly, the present invention relates to cyclopentadienyl derivatives having the general formula (I)
wherein: R, R- ^, R2, R4, equivalents to or different from each other, are selected from: - H, - alkyl radicals having a number of carbon atoms of 1 to 5, - cycloalkyl radicals having a number of carbon atoms of 5 to 8, aryl and alkylaryl radicals having a number of carbon atoms of 6 to 8, aralkyl radicals having a number of carbon atoms of 7 to 9; n is an integer from 2 to 18; with the proviso that the number of R different from H does not exceed 2; with the exclusion of the compound having n = 3, R = R1 = R2 = R = H. Typical examples of alkyl radicals of Cl to C5 are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl. Typical examples of cycloalkyl radicals having a carbon atom number of 5 to 8 are cyclopentyl, cyclohexyl, methylcyclopentyl, methylcyclohexyl. Typical examples of aryl and alkylaryl radicals having a carbon atom number of 6 to 8 are phenyl, methylphenyl, ethylphenyl, dimethylphenyl. Typical examples of aralkyl radicals having a number of carbon atoms of 7 to 9 are benzyl, methylbenzyl, ethylbenzyl, propylbenzyl.
In a preferred embodiment formed of R, R.,, R2 and R4 are selected from H and alkyl radicals from Cl to C3. In an even more preferred embodiment formed of n, selected from 3, 5, 6, 10, R = R2 = R1 = H, R4 is selected from H and alkyl radicals from Cl to C3. Typical examples of compounds having the general formula (I) are: - 2, 4, 5, 6, 7, 8-hexahydroazulene (compound in scheme 1, where R = R1 = R2 = H, n = 5); - 4, 5, 6, 7, 8, 9-hexahydro-2H-cyclopentacyclohexate (compound in scheme 1, where R = R1 = R2 = H, n = 6); - 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 -decahydro-2H-cyclopentacyclododecene (compound la in scheme 1, where R = R1 = R2 = H, n = 10); - l-methyl-4, 5, 6, 7, 8, 9, 10, 11, 12, 13-decahydro-2H-cyclopentacyclododecene (compound Ib in scheme 1, where R = R1 = R2 = H, R4 = CH3 , n = 10). The compounds having the general formula (I) are useful as ligands in the preparation of the complexes with transition metals, in particular Zirconium, components of typical catalysts in the (co) polymerization of α-olefins. A process for the preparation of chemical compounds having the general formula (I), constitute a further object of the present invention.
This process is represented schematically in scheme 1, where the compounds having the general formula
(I) are subdivided into compounds (la) and (Ib), if R4 is equivalent to or different from H, foreseeing some common stages and a different final stage as a function of R4. The process of the present invention, simple and original, is schematized in Scheme 1.
SCHEME 1
Accordingly, the present invention relates to a process for the preparation of compounds having the general formula (la), wherein n is an integer from 2 to 18, preferably n is selected from 3, 5, 6 , 10 and R, R1 and R2 have the meaning mentioned in the above, preferably R = R1 = R2 = H, which comprise the following steps: a) condensation of the Stobbe type between a ketone having the general formula (II) (-CHR-) n + 1 C = 0 with an ester of succinic acid having the general formula (III) R3OOC-CHR2-CHR1-COOR3, where the R3 groups, equivalent or different from each other, are selected from monofunctional alkyl radicals of C ^ -C ^, preferably R3 is selected from CH3 and C2H5 to give the propionate of - (a'-cycloalkenyl) -β-hydroxycarbonylalkyl having the general formula (IV); b) intramolecular condensation of the compound (IV) obtained in step (a) to give the condensed rings of the compound having the general formula (V); c) hydrolysis and decarboxylation of the compound (V) obtained in step (b) to give the condensed α-β-unsaturated ketone rings having the general formula (VI); d) reducing the condensed ar-ß-unsaturated ketone rings (VI) obtained in step (c) to give the fused conjugated diene rings having the general formula (la), steps (b) and (c) are also capable of being carried out in inverted order when compared to one mentioned in the above or in a single step, preferably in sequence (a), (b), (c), (d). Step (a) of the present invention is a typical condensation between ketones and succinic acid esters, known as the Stobbe reaction. This reaction (see H. House, Modern Synthetic Reactions, pages 663-666, Organic Reactions, Vo VI, pages 2-58) consists of the condensation of a carbonyl derivative with a succinic acid diester. In the case that the carbonyl derivative is a cycloalkanone, as in the case mentioned in the above, the half ester of the succinic acid substituted with cycloalkenyl, having the general formula (IV) is formed. Step (a) is carried out in the presence of strong bases, such as sodium methoxide, sodium hydride, tertiary alcohol alcoholates, preferably potassium terbutylate, a strong non-nucleophilic base. As regards the other experimental details of the Stobbe reaction, please refer to the references mentioned in the above. Typical cyclic ketones having the general formula (II) are cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclododecanone, 2-, 3-, 4-methylcyclohexanone, phenyl-cyclohexanone, benzylcyclohexanone. One of the advantages of the process of the present invention consists in the fact that many ketones having the general formula (II) are commercially available products. The condensation stage (a) occurs with a diester of succinic acid having the general formula (III), preferably with a diethyl or dimethyl succinate, optionally monosubstituted or disubstituted. Step (b) of the process of the present invention consists of an intramolecular condensation, with the removal of water of the product having the general formula (IV) obtained in step (a) to give the condensed rings of the compound having the formula general (V). This step is carried out in the presence of conventional condensation agents, for example strong acids such as sulfuric acid, hydrofluoric acid, phosphoric acid, polyphosphoric acid, preferably in the presence of polyphosphoric acid. The acids mentioned in the above can be used as commercially available or prepared in itself by mixing phosphoric acid and P205. If polyphosphoric acid is used, it is preferable to carry out step (b) at a temperature between 70 and 110 ° C. Alternatively, step (b) can be carried out in the presence of ZnCl2 in acetic acid-acetic anhydride, as described in the Organic Reactions reference mentioned in the above.
Step (c) consists in the hydrolysis of the ester group and in the subsequent decarboxylation of the compound having the general formula (V) to give the condensed or unsaturated ketone rings having the general formula (VI). The reaction is preferably carried out in an acidic medium and at such temperatures to facilitate the removal and removal of CO 2, preferably in a mixture of acetic acid / hydrochloric acid at reflux temperature. The ketone unsaturated α-β (VI) formed in step (c) is then reduced (step d) to a cyclopentadienyl derivative having the general formula (la) in the presence of reducing agents such as sodium borohydride or lithium , sodium hydride, lithium hydride, lithium-aluminum hydride, preferably with LiAlH4. According to another form of embodiment of the process of the present invention, step (c), ie hydrolysis to carboxylic acid and subsequent decarboxylation, the intramolecular condensation step (b) or the two steps can then be carried out. they can be carried out in a single step by selecting the most appropriate reaction conditions. The process of the present invention does not necessarily require the isolation of the unique reaction products at the end of the individual steps.
In addition to the advantage to start from easily available cycloalkanones, the process foresees other individual chemical steps and have a satisfactory overall performance. The present invention also relates to a process for the preparation of the compounds having the general formula (Ib), wherein n is an integer from 2 to 18, preferably selected from 3, 5, 6, 10, R, R-, R2, R4, having the meaning mentioned in the foregoing but with the proviso that R4 is different from H, preferably R = R1 = R2 = H, which comprise the following steps: a) condensation of the type Stobbe between a ketone having the general formula (II) (-CHR-) n + 1 C = 0 with an ester of succinic acid having the general formula (III) R300C-CHR2-CHR1-C00R3, wherein the R3 groups, equivalent or different from each other, are selected from monofunctional alkyl radicals of C - ^ - C ^, preferably R3 is selected from CH3 and C2H5 to give the propionate of - (a1-cycloalkenyl) -β-hydroxycarbonylalkyl having the general formula ( IV); b) intramolecular condensation of the compound (IV) obtained in step (a) to give the condensed rings of the compound having the general formula (V), - c) hydrolysis and decarboxylation of the compound (V) obtained in step (b) to give the condensed ß-unsaturated ketone rings having the general formula (VI), - d) reaction of the condensed ß-unsaturated ketone rings (VI) obtained in step (c) with an alkyl, aralkyl derivative , alkylaryl, alkali metal cycloalkyl and hydrolyzation to give the fused conjugated diene rings having the general formula
(Ib), steps (b) and (c) are also capable of being carried out in inverted order when compared with one mentioned in the above or in a single step, preferably in sequence (a), (b), (c), (d). As far as steps (a) to (c) are related, they are carried out under the same conditions as mentioned in the above for the synthesis of the compounds (la). Step (d) is carried out by reacting the condensed ß-unsaturated ketone (VI) rings obtained in step (c) with an alkyl, aralkyl, alkylaryl, cycloalkyl derivative of an alkali metal, preferably lithium. The lithium hydrocarbon derivative is a function of the type of R4, which one is willing to introduce into the compound, which has the general formula (Ib). Thus, for example, in the case one is wishing to prepare a compound (Ib), where R 4 is equivalent to -CH 3, methyl lithium will be used; in the case where it is desired to prepare a compound (Ib), where R4 is equivalent to -C2H ?, ethyl lithium will be used.
Then step (d) providing a subsequent hydrolysis step, preferably is carried out in the presence of acid catalysts, and then a dehydration step, in the same way preferably it will be carried out in the presence of acid catalysts. In this way, the product (Ib) obtained can be isolated according to the techniques used. The following examples are referred to for a better illustration of the present invention.
EXAMPLE 1 - Synthesis of 2, 4, 5, 6, 7, 8-hexahydroazulene (compound of scheme 1, where R = R1 = R2 = H, n = 5).
To a solution of cycloheptanone, compound (II), where n = 5, (56 grams corresponding to 0.5 moles) and of diethyl succinate, compound (III), where both of R3 are equal to -C2Hr, are slowly added 110 grams (0.63 moles) in 500 ml of N, N-dimethylformamide (DMF), potassium terbutylate (75 grams, 0.67 moles), (in about 1 hour), maintaining the temperature between 20 and 30 ° C. At the end a yellow suspension is obtained which, afterwards, is dissolved again approximately one hour to give, then a complete solidification of the reaction product. Everything is emptied in approximately 2 liters of water, in this way a transparent solution is obtained.
The solution is extracted for some time with ethyl ether and the aqueous solution is then acidified to a pH of 2-3, using dilute HCl. In this way the aqueous solution is acidified, then extracted with ether and the organic extract, then washed with water until neutral and then dried, evaporated. 118 grams (99% yield) of a- (a1-cycloheptenyl) -β-hydroxycarbonyl-ethyl propionate (compound IV) are obtained pure in the NMR analysis. The half-ester (IV) is then added to a mixture consisting of 400 grams of 85% H3P04 and 650 grams of P205, maintaining the temperature between 90 and 92 ° C. Once the addition has been added, the temperature is maintained for an additional 4 hours, during which time they have an abundant development of foam. The mixture is then hydrolyzed with water and extracted with diethyl ether. The ether extract is neutralized and dried. After evaporation of the solvent, 35 grams of the initial residue are obtained (yield of 64% of product V), which are emptied into 100 ml of AcOH, 100 ml of water and 10 ml of concentrated HCl and then maintained at room temperature. Reflux temperature overnight. The reaction mass is diluted with water and extracted with petroleum ether. After neutralization, drying and evaporation of the solvent, 16 grams of 3, 4, 5, 6, 7, 8-hexahydro-2H-azulen-1-one are obtained (yield of 64% of product VI). Add 16 grams of the product (VI) dissolved in 200 ml of diethyl ether to a solution of 3.0 grams of LiAlH4 in 300 ml of diethyl ether, maintaining the temperature between 5 and 10 ° C. The reaction mixture is then hydrolysed, the ether layer is separated and the aqueous phase is extracted again with 100 ml of diethyl ether. The ether extracts, (800 ml) after the neutralization and anhydrification are treated with 1.0 grams of p-toluenesulfonic acid for 1.5 hours at room temperature. The organic phase is then neutralized with NaHCO 3 and evaporated. The residue obtained is purified by chromatography on a column on silica gel by elution with petroleum ether. 14 grams of 2, 4, 5, 6, 7, 8-hexahydroazulene are obtained (compound with n = 5) with a yield of 98% of the product (VI) and 40% of the initial cycloheptanone, the which has the following NMR spectrum: RMN-iH (CDC13, d ppm, TMS re): 5.96 (s, broad, 2H); 2.84 (t, 2H, J = 2Hz); 2.47 (m, 4H); 1.61 (m, 6H).
EXAMPLE 2 - Synthesis of 4, 5, G, 7, 8, 9-hexahydro-2H-cyclopentacyclooctene (compound of scheme 1, where R = R1 = R2 = H, n = 6).
A solution of 63 grams (0.5 moles) of cyclooctanone (II) and 110 grams (0.63) moles of diethyl succinate is prepared. 75 grams (0.67 moles) of potassium terbutylate are added to this solution in small portions. After the addition, the mixture is left under stirring for 4 hours. The orange mass is hydrolyzed with water and ice, one is acidified and one is extracted with diethyl ether. 140 grams of an unpurified semi-solid containing two products are obtained in a ratio of 84:16 to evaporation. 70 grams of the initial ester prepared in this form are added to the polyphosphoric acid (which consists of 300 grams, 85% of H3P04 and 450 grams of 2 ^ 5 ^ • The exothermic reaction is carried out and at 70 ° C the ester goes to a solution, the brown mass and the temperature go up to 92 ° C. The reaction mass is stirred for about 1/2 hour.The temperature decreases to 80 ° C. The reaction mixture is emptied into ice, extracted with diethyl ether, it is neutralized with an aqueous solution of NaHCO3, it is anhydrified and the solvent is evaporated, 35 grams of a brown oil are obtained.
A mixture containing 35 grams of the crude oil mentioned above is prepared, 100 ml of AcOH, 100 ml of water and 10 ml of concentrated HCl. This mixture is maintained at reflux temperature for 6 hours, at the end of which it is hydrolyzed and extracted with diethyl ether. Many spots are separated. The mixture is washed with NaOH (dissolve stains) and water, anhydrified and the solvent evaporated. 12 grams of the yellow oil are obtained. These 12 grams of yellow oil (corresponding to product VI), are dissolved in 100 ml of diethyl ether, are added to a solution of 3.0 grams LiAlH4 in 200 ml of diethyl ether, maintaining the temperature between 5 and 10 ° C. The reaction mixture is then hydrolyzed, the ether layer separated and the aqueous phase extracted, even with 100 ml of diethyl ether. The ether extracts (400 ml), after neutralization and anhydrification are treated with 1.0 grams of p-toluenesulfonic acid for 1.5 hours at room temperature. The organic phase is then neutralized with NaHCO 3 and evaporated. The residue obtained is purified by chromatography on a column on silica gel by elution with petroleum ether.
7 grams of the product are obtained, pure in the NMR and GC analysis. The yield as compared to the initial cyclooctanone (II) is 20%. The NMR spectrum of the 4, 5, 6, 7, 8, 9-hexahydro-2H-cyclopentacyclooctene thus obtained is as follows: R -! H (CDC13, d ppm re.TMS): 6.02 (t, 2H); 2.88 (broad s, 2H); 2.50 (t, 4H); 1.70-1.40 (m, 8H).
EXAMPLE 3 - Synthesis of 4, 5, 6, 7, 8, 9, 10, 11, 12, 13-decahydro-2H-cyclopentacyclododecene (compound of scheme 1, where R = R1 = R2 = H, n = 10) .
To a solution of 100 grams (0.549 moles) of cyclododecanone (compound II, n = 10) in 700 ml of THF, 70 grams of potassium terbutylate are added slowly
(approximately 1 hour). At the end a yellow suspension is obtained which is stirred for 1 hour. The total is emptied in approximately 2 liters of water, in this way a transparent solution is obtained. The aqueous solution is washed for some time with diethyl ether and then acidified to a pH of 2-3, using dilute HCl.
I1 »
Then the aqueous solution is extracted with ether and the organic extract, after it is washed with water until neutral and after it is dried it evaporates. 160 grams (yield 94%) of a product having a low boiling point are obtained (product IV in scheme 1, where n = 10, R = R1 = R2 = H, R3 = Et). The ester thus obtained (120 grams, 0.387 moles) is emptied in one hour in a flask, maintaining the temperature at about 93-95 ° C, which contains 2.5 kg of polyphosphoric acid having a P205 content of 84%. Once the addition has been added, the temperature is increased to 96-97 ° C and the mixture is left under stirring for 4 hours. The mixture is then hydrolyzed with water and extracted with diethyl ether. The ether extract is neutralized and dried. After evaporation of the solvent, 90 grams of the initial residue are obtained, pure in the GC analysis (product V in scheme 1, where n = 10, R1 = R2 = H,
R3 = Et). The solid is put into a solution consisting of
125 ml of AcOH, 125 ml of water and 10 ml of concentrated HCl and kept under reflux temperature for 20 hours. The reaction mass is diluted with water and extracted with petroleum ether. After neutralization, drying and evaporation of the solvent, the residue is distilled under vacuum and the fraction which passes at 125-130 ° C / 0.2 mmHg is collected. 43 grams (yield 51%) of the product VI are obtained in scheme 1 having n = 10, R = R1 = R2 = H. 24 grams (0.11 moles) of the product thus obtained are dissolved in 200 ml of diethyl ether and then added to a solution of 3.0 grams of LiAlH4 in 300 ml of diethyl ether, maintaining the temperature between 5 and 10 ° C. The reaction mixture is then hydrolyzed with slightly dilute HCl, the ether layer is separated and the aqueous phase is extracted with 200 ml of diethyl ether. The ethereal extracts, (800 ml) after neutralization and anhydrification are treated with 2.7 grams of p-toluenesulfonic acid for 1.5 hours at room temperature, then at 30-35 ° C for 5-6 hours until the alcohol (TLC) has disappeared. The organic phase is then neutralized with NaHCO 3 and evaporated. The residue obtained is purified by chromatography on a column on silica gel by elution with petroleum ether. You get 21 grams (99% yield) of a mixture consisting of two products in a ratio of
81:19, of which the main product is 4, 5, 6, 7, 8, 9,
, 11, 12, 13-decahydro-2H-cyclopentacyclododecene
(Composed in scheme 1, n = 10, R = R1 = R2 = H).
EXAMPLE 4 - Synthesis of 1-methyl-4, 5, 6, 7, 8, 9, 10, 11, 12, 13-decahydro-2H-cyclopentacyclododecene (compound Ib of scheme 1, where R = R1 = R2 = H, R4 = CH3, n = 10).
To a solution in 100 ml of diethyl ether, of 10 grams (0.045 moles) of the carbonyl derivative prepared in example 3 (product VI in scheme 1, n = 10, R = R1 = R2 = H), is maintained at - 70 ° C, 30 ml of a 1.6 M MeLi solution in diethyl ether are added. The mixture is left under stirring overnight, then hydrolyzed. The ether phase is separated, 1 gram of p-toluenesulfonic acid is added and the mixture is left stirring for 2 hours. The mixture is neutralized with a saturated solution of sodium bicarbonate, dried over Na 2 SO 4 and the solvent is evaporated. The product is eluted on a column in silica gel using petroleum ether and collecting the first fraction. 7 grams of a product consisting of two isomers in a ratio of 3: 1 are obtained from the chromatographic gas analysis. The main product of the mixture mentioned above consists of l-methyl-4,5,6,7,8,9,11,11,12,13-decahydro-2H-cyclopentacyclododecene. Having described the invention as above, property is claimed as contained in the following:
Claims (25)
- CLAIMS 1. Cyclopentadienyl derivatives, characterized in that they have the general formula (I) where R, R ^, R2, R4, equivalents to or different from each other, are selected from: - H, - alkyl radicals having a number of carbon atoms of 1 to 5, - cycloalkyl radicals having a number of carbon atoms from 5 to 8, aryl and alkylaryl radicals having a number of carbon atoms of 6 to 8, aralkyl radicals having a number of carbon atoms of from 7 to 9; n is an integer from 2 to 18; with the proviso that the number of R different from H does not exceed 2; with the exclusion of the compound having n = 3, R = R1 = R2 = R4 = H.
- 2. The cyclopentadienyl derivatives according to claim 1, characterized in that R, R1 # R2, R4, are selected from H and alkyl radicals from Cl to C3.
- 3. The cyclopentadienyl derivatives according to claim 1, characterized in that n is selected from 3, 5, 6, 10, R = R2 = R1 = H, R4 is selected from H and alkyl radicals from Cl to C34. 2, 4, 5, 6, 7, 8-hexahydroazulene. 5. 4, 5, 6, 7, 8, 9-hexahydro-2H-cyclopentacyclohexate. 6. 4, 5, 6, 7, 8, 9, 10, 11, 12, 13-decahydro-2H-cyclopentacyclododecene. 7. l-methyl-4, 5, 6, 7, 8, 9, 10, 11, 12, 13-decahydro-2H-cyclopentacyclododecene. 8. A process for the preparation of the compounds having the general formula (la), where n is an integer from 2 to 18, R, R- ^ and R2 have the meaning mentioned in the above, preferably R = R1 = R2 = H, which are characterized in that they comprise the following steps: a) condensation of the Stobbe type between a ketone having the general formula (II) (-CHR-) n + 1 C = 0 with an ester of succinic acid having the general formula (III) R3OOC-CHR2-CHR1-COOR3, where the R3 groups, equivalent or different from each other, are selected from C1-C5 monofunctional alkyl radicals, preferably R3 is selected from CH3 and C2H5 to give the propionate of ex - (ct '-cycloalkenyl) -β-hydroxycarbonylalkyl having the general formula (IV); b) intramolecular condensation of the compound (IV) obtained in step (a) to give the condensed rings of the compound having the general formula (V); c) hydrolysis and decarboxylation of the compound (V) obtained in step (b) to give the condensed α-β-unsaturated ketone rings having the general formula (VI); d) reduction of the condensed α-β-unsaturated ketone rings (VI) obtained in step (c) to give the fused conjugated diene rings having the general formula (la), steps (b) and (c) are also capable of being carried out in inverted order when compared with one mentioned in the previous or in a single stage. 9. The process according to claim 8, characterized in that R3 is selected from -CH3 and -C2H5. 10. The process in accordance with the claim 8, characterized in that it is R = R1 = R2 = H. 11. The process according to claim 8, characterized in that n is selected from 3, 5, 6, 10. 12. The process according to claim 8, characterized in that step (a) is carried out in the presence of potassium terbutylate. 13. The process in accordance with the claim 8, characterized in that step (b) is carried out in the presence of the polyphosphoric acid such as or prepared in itself. 14. The process in accordance with the claim 8, characterized in that step (c) is carried out at acidic pHs. 15. The process according to claim 8, characterized in that step (d) is carried out in the presence of LiAlH4. 16. The process in accordance with the claim 8, characterized in that this is carried out in the next stage of sequence: stage (a), stage (b), stage (c), stage (d). 17. A process for the preparation of the compounds having the general formula (Ib), where n is an integer from 2 to 18, R, R1 # R2, R4, which have the meaning mentioned in the foregoing but with the proviso that R4 is different from H, preferably R = R1 = R2 = H, which are characterized in that they comprise the following steps: a ) condensation of the Stobbe type between a ketone having the general formula (II) (-CHR-) n + 1 C = 0 with an ester of succinic acid having the general formula (III) R3OOC-CHR2 -CHR-j ^ - COOR3, where the R3 groups, equivalent or different from each other, are selected from monofunctional alkyl radicals of C- ^ -C ^, to give the propionate of - (Q -'-cycloalkenyl) -β-hydroxycarbonylalkyl having the general formula (IV); b) intramolecular condensation of the compound (IV) obtained in step (a) to give the condensed rings of the compound having the general formula (V); c) hydrolysis and decarboxylation of the compound (V) obtained in step (b) to give the condensed α-β-unsaturated ketone rings having the general formula (VI); d) reaction of the condensed α-β-unsaturated ketone (VI) rings obtained in step (c) with an alkyl, aralkyl, alkylaryl, alkali metal cycloalkyl derivative and hydrolyzation to give the fused conjugated diene rings having the general formula (Ib), stages (b) and (c) are also capable of being carried out in inverted order when compared with one mentioned in the previous or in a single stage. 18. The process according to claim 17, characterized in that R3 is selected from -CH3 and -C2H5. 19. The process according to claim 17, characterized in that it is R = R1 = R2 = H. 20. The process according to claim 17, characterized in that n is selected from 3, 5, 6, 10. 21. The process according to claim 17, characterized in that step (a) is carried out in the presence of potassium terbutylate. 22. The process in accordance with the claim 17, characterized in that step (b) is carried out in the presence of the polyphosphoric acid such as or prepared in itself. 23. The process in accordance with the claim 17, characterized in that step (c) is carried out at acidic pHs. 24. The process according to claim 17, characterized in that in step (d) the alkali metal is lithium and the hydrolysis is carried out with acid catalysts. 25. The process according to claim 8, characterized in that this is carried out in the following sequence stage: step (a), step (b), step (c), step (d).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MIMI95A001826 | 1995-08-30 | ||
| IT95MI001826 IT1277513B1 (en) | 1995-08-30 | 1995-08-30 | Cyclo-pentadienyl derivs. useful as ligands for olefin polymerisation catalysts - prepd. by Stobbe condensation of a cyclic ketone with a succinic acid ester, intramolecular condensation, hydrolysis, decarboxylation and then reduction |
| IT95MI002707 IT1277682B1 (en) | 1995-12-21 | 1995-12-21 | Cyclo-pentadienyl derivs. useful as ligands for olefin polymerisation catalysts - prepd. by Stobbe condensation of a cyclic ketone with a succinic acid ester, intramolecular condensation, hydrolysis, decarboxylation and then reduction |
| MIMI95A002707 | 1995-12-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MXPA96003616A true MXPA96003616A (en) | 1997-06-01 |
| MX9603616A MX9603616A (en) | 1997-06-28 |
Family
ID=26331308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9603616A MX9603616A (en) | 1995-08-30 | 1996-08-23 | Cyclopentadienyl derivatives and processes for the preparation thereof. |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5900517A (en) |
| EP (1) | EP0760355B1 (en) |
| JP (1) | JPH09132537A (en) |
| KR (1) | KR100242140B1 (en) |
| CN (1) | CN1069625C (en) |
| CA (1) | CA2183171C (en) |
| DE (1) | DE69604875T2 (en) |
| ES (1) | ES2137626T3 (en) |
| MX (1) | MX9603616A (en) |
| RO (1) | RO116392B1 (en) |
| RU (1) | RU2159758C2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6281306B1 (en) | 1999-12-16 | 2001-08-28 | Univation Technologies, Llc | Method of polymerization |
| JP4246871B2 (en) | 2000-02-03 | 2009-04-02 | 本州化学工業株式会社 | Bridged cyclic cyclopentadiene and dihalobismetal compound having it as a ligand |
| BR0205610B1 (en) | 2001-06-07 | 2012-08-07 | process for preparing alkylidene substituted succinic acid esters. | |
| BR0305725A (en) | 2002-08-05 | 2004-09-28 | Basell Poliolefine Spa | Process for preparing alkylidene-substituted 1,4-dione derivatives |
| AU2003250923A1 (en) | 2002-08-05 | 2004-02-25 | Basell Poliolefine Italia S.P.A. | Process for preparing alkylidene-substituted-1,4-dions derivatives |
| AU2003304716A1 (en) | 2002-10-15 | 2005-11-25 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
| US7223822B2 (en) | 2002-10-15 | 2007-05-29 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
| RU2479593C2 (en) | 2007-12-18 | 2013-04-20 | Юнивейшн Текнолоджиз, Ллк | Method of controlling bimodal catalyst activity during polymerisation |
| RU2365572C1 (en) * | 2008-02-01 | 2009-08-27 | Государственное образовательное учреждение высшего профессионального образования Иркутский государственный университет | Method of obtaining bicyclo-[3,3,0]-octane-(2) |
| SG11201703851UA (en) | 2014-11-25 | 2017-06-29 | Univation Tech Llc | Methods of controlling polyolefin melt index |
| CA3076591A1 (en) | 2017-09-28 | 2019-04-04 | Univation Technologies, Llc | Synthesis of cyclic organic compounds and metallocenes |
| SG11202102220PA (en) * | 2018-09-28 | 2021-04-29 | Dow Global Technologies Llc | Synthesis of substituted cyclopentadiene compounds and metallocenes |
-
1996
- 1996-08-12 US US08/695,400 patent/US5900517A/en not_active Expired - Lifetime
- 1996-08-12 CA CA002183171A patent/CA2183171C/en not_active Expired - Lifetime
- 1996-08-23 MX MX9603616A patent/MX9603616A/en not_active IP Right Cessation
- 1996-08-28 ES ES96202388T patent/ES2137626T3/en not_active Expired - Lifetime
- 1996-08-28 EP EP96202388A patent/EP0760355B1/en not_active Expired - Lifetime
- 1996-08-28 DE DE69604875T patent/DE69604875T2/en not_active Expired - Lifetime
- 1996-08-29 RU RU96116939/04A patent/RU2159758C2/en not_active IP Right Cessation
- 1996-08-29 CN CN96111685A patent/CN1069625C/en not_active Expired - Fee Related
- 1996-08-29 RO RO96-01727A patent/RO116392B1/en unknown
- 1996-08-30 JP JP8231026A patent/JPH09132537A/en active Pending
- 1996-08-30 KR KR1019960037188A patent/KR100242140B1/en not_active Expired - Fee Related
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ksander et al. | A method for the synthesis of unsaturated carbonyl compounds | |
| MXPA96003616A (en) | Cylopentadienile derivatives and processes to supreparate | |
| EP0760355B1 (en) | Process for the preparation of cyclopentadienyl derivatives | |
| Brown et al. | Hydroboration. 42. Cyclic hydroboration of representative acyclic. alpha.,. omega.-dienes with monochloroborane etherate | |
| US3247239A (en) | Avoidance of retro-ionylidene transposition by deacyloxylation of compounds of the vitamin a1, a2, beta-carotene and carotenoid series, with a nucleophilic compound in an anhydrous medium | |
| US3981920A (en) | Method for preparing cyclopentenone derivatives | |
| JP3998270B2 (en) | Method for producing cyclopentadienyl compound | |
| US3870753A (en) | Process for preparing indenyl acetic acids | |
| JPS5953903B2 (en) | Method for producing vitamin A from sulfone | |
| Mandelbaum et al. | Polycyclic Studies. I. Synthesis of Triphenylenes Through Diels-Alder Adducts1 | |
| Ranganathan et al. | The synthesis of PGF1α by re-structuring of castor oil | |
| US3518296A (en) | Process of preparation of alkyl cyclopentane diones and intermediates therefor | |
| Dreiding et al. | The Reformatsky Reaction with 2-Hydroxymethylenecyclohexanone. 5, 6, 7, 8-Tetrahydrocoumarin1 | |
| OHTA et al. | A total synthesis of grifolin | |
| US3401210A (en) | Process for the manufacture of multiple unsaturated aliphatic compounds | |
| ITMI952707A1 (en) | CYCLOPENTADIENYL DERIVATIVES AND PROCEDURE FOR THEIR PREPARATION | |
| US5929298A (en) | Process for preparing conjugated dienes using substituted rhenium trioxide | |
| US4021491A (en) | Manufacture of 2,6,6-trimethyl-cyclohex-2-en-1-one | |
| US5453525A (en) | Carboxylic esters for the preparation of a bicyclic decalin ketone | |
| Wilds et al. | Preparation and reactions of diazo ketones. V. Normal and abnormal products from thermal Wolff rearrangement of 9-phenylfluorene-9-carbonyldiazomethane | |
| Cardona et al. | Synthesis of two natural 8-oxo-β-cyperone derivatives from (−)-santonin. | |
| Ho | Short Syntheses of Dihydrojasmone | |
| Leonard | Antispasmodics. I. 2-Diethylaminoethyl Esters of α-Substituted 2-Thienylacetic and β-(2-Thienyl)-propionic Acids | |
| US2582252A (en) | 2-alkoxyphenethyl-6-carboxycyclohexene-1-one-3 esters and process for preparing same | |
| Joergensen et al. | Cyclopropylidene formation during lithium aluminum hydride reduction of some ethyl 2, 2-dibromocyclopropanecarboxylates and their corresponding acids |