WO2002036585A2 - Procede de preparation de ligands pour catalyseurs de polymerisation des olefines - Google Patents
Procede de preparation de ligands pour catalyseurs de polymerisation des olefines Download PDFInfo
- Publication number
- WO2002036585A2 WO2002036585A2 PCT/US2001/042976 US0142976W WO0236585A2 WO 2002036585 A2 WO2002036585 A2 WO 2002036585A2 US 0142976 W US0142976 W US 0142976W WO 0236585 A2 WO0236585 A2 WO 0236585A2
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- WO
- WIPO (PCT)
- Prior art keywords
- hydrocarbyl
- process according
- substituted hydrocarbyl
- heteroatom connected
- general formula
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003446 ligand Substances 0.000 title description 8
- 150000001336 alkenes Chemical class 0.000 title description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 6
- 239000002685 polymerization catalyst Substances 0.000 title description 6
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 98
- 125000005842 heteroatom Chemical group 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical group S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- QLSWIGRIBOSFMV-UHFFFAOYSA-N 1h-pyrrol-2-amine Chemical compound NC1=CC=CN1 QLSWIGRIBOSFMV-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- CFHGBZLNZZVTAY-UHFFFAOYSA-N lawesson's reagent Chemical compound C1=CC(OC)=CC=C1P1(=S)SP(=S)(C=2C=CC(OC)=CC=2)S1 CFHGBZLNZZVTAY-UHFFFAOYSA-N 0.000 claims description 3
- YNZAFFFENDLJQG-UHFFFAOYSA-N pyrrol-1-amine Chemical compound NN1C=CC=C1 YNZAFFFENDLJQG-UHFFFAOYSA-N 0.000 claims description 3
- 230000001131 transforming effect Effects 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- OSWWFLDIIGGSJV-UHFFFAOYSA-N 1,4-diphenylbutane-1,4-dione Chemical compound C=1C=CC=CC=1C(=O)CCC(=O)C1=CC=CC=C1 OSWWFLDIIGGSJV-UHFFFAOYSA-N 0.000 claims 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- RNGWNLCPXATRHU-UHFFFAOYSA-N 1,3-dithiolane-4,5-diimine Chemical class N=C1SCSC1=N RNGWNLCPXATRHU-UHFFFAOYSA-N 0.000 abstract 2
- BIGAWNLJEGYSGL-UHFFFAOYSA-N 1,4-dithiane-2,3-diimine Chemical class N=C1SCCSC1=N BIGAWNLJEGYSGL-UHFFFAOYSA-N 0.000 abstract 2
- -1 4-tert-butyl phenyl Chemical group 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 239000012455 biphasic mixture Substances 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- CXWGKAYMVASWDQ-UHFFFAOYSA-N 1,2-dithiane Chemical compound C1CCSSC1 CXWGKAYMVASWDQ-UHFFFAOYSA-N 0.000 description 4
- IMLSAISZLJGWPP-UHFFFAOYSA-N 1,3-dithiolane Chemical compound C1CSCS1 IMLSAISZLJGWPP-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000005594 diketone group Chemical group 0.000 description 4
- LOZWAPSEEHRYPG-UHFFFAOYSA-N dithiane Natural products C1CSCCS1 LOZWAPSEEHRYPG-UHFFFAOYSA-N 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- ONGBXISBKSVVFS-UHFFFAOYSA-N 2-methyl-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(C)C(=O)C1=CC=CC=C1 ONGBXISBKSVVFS-UHFFFAOYSA-N 0.000 description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 0 *C(C(*)=N[n]1c(*)c(*=C)cc1*)=N[*@@]1C(*)=C(*)C=C1* Chemical compound *C(C(*)=N[n]1c(*)c(*=C)cc1*)=N[*@@]1C(*)=C(*)C=C1* 0.000 description 2
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 2
- KVFQMAZOBTXCAZ-UHFFFAOYSA-N 3,4-Hexanedione Chemical compound CCC(=O)C(=O)CC KVFQMAZOBTXCAZ-UHFFFAOYSA-N 0.000 description 2
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000004887 dithianes Chemical class 0.000 description 2
- 150000004863 dithiolanes Chemical class 0.000 description 2
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 239000008241 heterogeneous mixture Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- DKACXUFSLUYRFU-UHFFFAOYSA-N tert-butyl n-aminocarbamate Chemical compound CC(C)(C)OC(=O)NN DKACXUFSLUYRFU-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- CKORZISNPHDVIR-UHFFFAOYSA-N 2-trimethylsilylethyl n-aminocarbamate Chemical compound C[Si](C)(C)CCOC(=O)NN CKORZISNPHDVIR-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- PNMLOOBLEBXYGE-UHFFFAOYSA-N ethyl 2-benzoyl-4-oxo-4-phenylbutanoate Chemical compound C=1C=CC=CC=1C(=O)C(C(=O)OCC)CC(=O)C1=CC=CC=C1 PNMLOOBLEBXYGE-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- UKXWOVOPOCNSGO-UHFFFAOYSA-N n,n'-bis(2,5-diphenylpyrrol-1-yl)oxamide Chemical compound C=1C=CC=CC=1C1=CC=C(C=2C=CC=CC=2)N1NC(=O)C(=O)NN1C(C=2C=CC=CC=2)=CC=C1C1=CC=CC=C1 UKXWOVOPOCNSGO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
- C07D207/50—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/02—Five-membered rings
- C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/08—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Definitions
- the invention relates to processes for the preparation of 4,5-bisimino-
- Nickel and palladium complexes of bidentate N,N-donor ligands have recently been shown to be useful as olefin polymerization catalysts (Ittel et al., Chem. Reviews 2000, 100, 1169). There is a need therefore for efficient methods of synthesizing such ligands. In addition to the methods described in the literature reviewed by Ittel et al. (Chem. Reviews 2000, 100, 1169), Gonioukh et al. (WO 01/21586 Al) have recently described methods for this purpose. Notwithstanding these developments, there remains a need for further improvements in efficiency and scope to provide general and cost effective routes to such ligands.
- this invention provides a straightforward, efficient and cost effective process for the preparation of a 4,5-bisimino-[l,3]dithiolane or a 2,3- bis--mino-[l,4] ⁇ -ithiane of general formula I, useful as ligands for olefin polymerization catalysts;
- R and R 1 are each, independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl;
- Q is hydrocarbyl or substituted hydrocarbyl; and
- X and Y 1 are each, independently, a leaving group.
- this invention relates to a straightforward, efficient and cost effective process for the preparation of compounds of the general formula IV, useful as. ligands for olefin polymerization catalysts, in a single reactor, without isolation of any intermediates;
- a diketone of general formula V is reacted with a protected hydrazine in the ⁇ presence of an acid to form a protected amino pyrrole; the resultant protected amino pyrrole is then reacted with an ⁇ -diketone of general formula VI in the presence of an acid;
- R 5a a. nd R ,5b are each, independently, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl;
- R 6a is H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl;
- R 7a and R 70 are each hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl.
- this invention relates to a process for the preparation of a 4,5-bisimino-[l,3]dithiolane or a 2,3-bisimino-[l,4]dithiane of general formula I by reacting a substituted oxalamide of general formula II with a reagent capable of transforming an amide to a thioamide to form a dithiooxalamide compound.
- the second step of the process involves reaction of the dithiooxalamide compound with a compound of general formula HI to provide the 4,5-bisimino-[l,3]dithiolane or 2,3- bis-bnino-[l,4]dithiane of general formula I.
- the oxalamide may be any oxalamide of general formula II, which may be prepared by any number of methods known to those skilled in the art, including, but not limited to, reaction of oxalic dihydrazide with a 1 ,4-diketone and reaction of a primary amine with oxalyl chloride.
- Preferred R and R 1 groups in general formula II are chosen from the group consisting of
- R 2a'2c are each, independently, H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl;
- R 3a"3b are each, independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl;
- R 4a is H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl.
- R 2a and R 2c are each, independently, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl.
- R 2a and R 2c are each, independently, hydrocarbyl or substituted hydrocarbyl.
- suitable R 2a and R 2c groups include, but are not limited to, methyl, ethyl, isopropyl, isobutyl, tert-butyl, phenyl, 4-tert-butyl phenyl, 4-methyl phenyl, 4-methoxyphenyl, 4-trifluoromethyl phenyl, 4- nitro phenyl and 3,5-diphenyl phenyl.
- R 3a and R 3b are each, independently, hydrocarbyl or . substituted hydrocarbyl.
- suitable R 3a and R 3b groups include, but are not limited to, methyl, ethyl, isopropyl, isobutyl, tert-butyl, phenyl, 4-tert-butyl phenyl, 4- methyl phenyl, 4-methoxy phenyl, 4- nitro phenyl and 3,5-diphenyl phenyl.
- R 4a is H, hydrocarbyl or substituted hydrocarbyl. Examples
- R 4a groups include, but are not limited to, H, methyl, ethyl, isopropyl, tert- butyl, isobutyl, phenyl, -COOR 5 , -COR, -CONR 5 2 , -CONHR 5 , cyano and nitro; wherein R 5 is hydrocarbyl or substituted hydrocarbyl.
- suitable R 5 groups include, but are not limited to, methyl, ethyl, isopropyl, tert-butyl, isobutyl and phenyl.
- Examples of a reagent capable of tr -msform ng an amide to a thioamide include, but are not limited to, P 4 S ! o and 2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4- diphosphetane-2,4-disulfide.
- the first step of the process may be run in an inert solvent, preferably toluene or xylene.
- an inert solvent preferably toluene or xylene.
- the reaction may be conducted at temperatures ranging from about 25 to about 200 °C, preferably at temperatures ranging from about 75 to about 150 °C.
- the preferred temperature range will generally be similar but will best be detera-iined by routine experimentation. Pressures at or above about 1 atm are preferred.
- 2,3-bisimino-[l,4]dithiane of general formula I involves reaction of the dithiooxalamide formed in step (i) of the process with a compound of general formula III; wherein Q is hydrocarbyl or substituted hydrocarbyl; and X and Y 1 are each, independently, leaving groups.
- Q is -CH 2 CH 2 -, -CH2-, -CO- or -CS-; more preferably, Q is
- reaction may be conducted at temperatures ranging from about 0 to about 100 °C, preferably at temperatures ranging from about 25 to about 50 °C.
- temperatures ranging from about 25 to about 50 °C.
- the preferred temperature range will generally be similar but will best be determined by routine experimentation. Pressures at or above about 1 arm are preferred.
- a "leaving group” is any species that can be expelled by a nucleophile in an S N 2 reaction or is easily dissociated in an S N I reaction.
- suitable leaving groups include, but are not limited to, chloride, bromide, p-toluene sulfonate, methane sulfonate and trifluoromethane sulfonate.
- X and Y 1 are each, independently, bromide.
- Step (ii) of the process may further comprise a base to aid in the removal of the acidic dithiooxalamide proton.
- the base is an alkali metal hydroxide or ammonium hydroxide.
- Preferred alkali metal hydroxides are sodium hydroxide and potassium hydroxide.
- Step (ii) of the process may be run in neat compound III, as a solution in an inert organic solvent, in a biphasic mixture of compound III and water, or as a biphasic mixture of an inert organic solvent and water.
- a phase transfer catalyst may also be present.
- a non-limiting example of a phase transfer catalyst is tetrabutyl ammonium bromide.
- this invention relates to a process for the preparation of a compound of general formula IV in three steps, which may be carried out in a single reaction vessel without isolation of the intermediate products.
- the first step of the process of the second aspect involves the condensation of a protected hydrazine with a diketone of general formula V in the presence of an acid and an alcohol solvent to provide a protected 2,5-disubstituted, optionally 3-substituted, 1 -amino pyrrole.
- protected hydrazines include, but are not limited to, tert-butyl carbazate and hydrazine carboxylic acid 2- trimethylsilanyl-ethyl ester.
- Suitable diketones of general formula V include, but are not limited to, dibenzoyl ethane and 2-benzoyl-4-oxo-4-phenyl-butyric acid ethyl ester.
- suitable acids include, but are not limited to, acetic acid and para-toluene sulfonic acid.
- suitable alcohol solvents include, but are not limited to, methanol, ethanol and isopropanol.
- the reaction may be conducted at temperatures ranging from about 25 to about 150 °C, preferably at temperatures ranging from about 50 to about 115 °C. Pressures at or above about 1 atm are preferred.
- the second step of the process of the second aspect involves deprotection of the 1 -amino pyrrole prepared in the first step in the presence of an acid in an alcohol solvent.
- suitable acids include hydrochloric acid, trifluoroacteic acid, phosphoric acid and sulfuric acid.
- suitable alcohol solvents include methanol, ethanol and isopropanol.
- the reaction may be conducted at temperatures ranging from about 0 to about 200 °C, preferably at temperatures ranging from about 25 to about 115 °C. Pressures at or above about 1 atm are preferred.
- the third step of the process of the second aspect involves the condensation of the 1 -amino pyrrole prepared in the second step, with an ⁇ -diketone of general formula VI in the presence of an acid and alcohol solvent.
- suitable ⁇ -diketones include, but are not limited to, 2,3-butanedione, benzil and 3,4- hexanedione.
- suitable acids include, but are not limited to, hydrochloric acid, sulfuric acid and phosphoric acid.
- suitable alcohol solvents include, but are not limited to, methanol, ethanol and isopropanol.
- R 5a and R 5 " are each, independently, hydrocarbyl or substituted hydrocarbyl, more preferably phenyl, 4-trifluoromethylphenyl, 4-tert-butylpehnyl or 4- methylphenyl.
- R 6a is H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl.
- R 6 is H, methyl, hydroxymethyl, cyano, nitro or -COOR 8 , wherein R 8 is hydrocarbyl or substituted hydrocarbyl, preferably methyl or ethyl.
- R 7a and R 70 are each hydrocarbyl or substituted hydrocarbyl.
- R 7a and R 70 are each hydrocarbyl or substituted hydrocarbyl.
- R 7a and R 70 are each, independently, methyl, ethyl, phenyl, aryl, or isopropyl. Additionally, R 7a and R 715 may be finked to form a bridging group. Preferred bridging groups include, but are not limited to 1,2-phenylene and 1,8-na ⁇ hthylene. [0023]
- a "hydrocarbyl” group means a monovalent or divalent, linear, branched or cyclic group which contains only carbon and hydrogen atoms.
- Examples of monovalent hydrocarbyls include the following: C 1 -C 20 alkyl; C Cio alkyl substituted with one or more groups selected from -C 2 0 alkyl, C 3 -C 8 cycloalkyl, and aryl; C 3 -C 8 cycloalkyl; C 3 -C 8 cycloalkyl substituted with one or more groups selected from C ⁇ -C 2 o alkyl, C 3 -C 8 cycloalkyl, and aryl; C 6 -C 14 aryl; and C 6 -C 1 aryl substituted with one or more groups selected from -C 2 0 alkyl, C 3 -C 8 cycloalkyl, and aryl; where the term "aryl” preferably denotes a phenyl, napthyl, or anthracenyl group.
- Examples of divalent (bridging) hydrocarbyls include: -CH 2 - -CH 2 CH 2 - -CH 2
- a "substituted hydrocarbyl” refers to a monovalent or divalent hydrocarbyl substituted with one or more heteroatoms.
- monovalent substituted hydrocarbyls include: 2,6-dimethyl-4-methoxyphenyl, 2,6-diisopropyl-4- methoxyphenyl, 4-cy- o-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl, 2,6- difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 4-methoxycarbonyl-2,6- dimethylphenyl, 2-tert-butyl-6-chlorophenyl, 2,6-dimethyl-4-phenylsulfonylphenyl, 2,6- dimethyl-4-trifluoromethylphenyl, 2,6-dimethyl-4-trimethyl- ⁇ mmoniumphenyl (associated with a weakly coordinated anion), 2,6-di
- (bridging) substituted hydrocarbyls include: 4-methoxy- 1,2-phenylene, 1- methoxymethyl-l,2-ethanediyl, l,2-bis(benzyloxymethyl)-l,2-ethanediyl, and l-(4- methoxyphenyl)- 1 ,2-ethanediyl.
- a "heteroatom connected hydrocarbyl” refers to a group of the type
- E 1 (hydrocarbyl), E 2 H(hydrocarbyl), or E 2 (hydrocarbyl) 2 where E 1 is an atom selected from Group 16 and E 2 is an atom selected from Group 15.
- a "heteroatom connected substituted hydrocarbyl” refers to a group of the type E 1 (substituted hydrocarbyl), E 2 H(substituted hydrocarbyl), or E 2 (substituted hydrocarbyl , where E 1 is an atom selected from Group 16 and E 2 is an atom selected from Group 15.
- a "bridging group” refers to an atom or group which links two or more groups, which has an appropriate valency to satisfy its requirements as a bridging group. Suitable examples include divalent or trivalent hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, substituted silicon(IN), boron(m), ⁇ (III), P(m), andP(N), -C(O)-, -SO 2 -, -
- a suspension of aaal 3 (4.4 g, 4.78 mmol) in ⁇ rt r ⁇ -xylene (20 ml) was treated with phosphorus pentasulfide (1.1 g, 2.39 mmol).
- the flask was fitted with a reflux condenser, and immersed in a 180 °C oil bath.
- the resulting suspension was refluxed under nitrogen for ca. 3h, then cooled to 23 °C, then diluted with ca. 35 mL methylene chloride.
- the heterogeneous mixture was poured onto a column of silica (10" x 50 mm) and eluted with methylene chloride hexane, collecting only the forerunning orange band.
- aaal 4 crystallized from solution as orange needles (2 g), and was collected by filtration.
- the filtrate was concentrated to give more aaa!4 as an orange crystalline powder (1.8 g).
- a suspension of aaal 4 (2 g, 2.1 mmol) in 1,2-dibromoethat ⁇ e (7 ml) was treated with tetrabutylammomum bromide (15 mg) and 2 N aq NaOH (10 L).
- the biphasic mixture was stirred vigorously for 1.5 h.
- the color discharged markedly and a pale precipitate separated.
- the mixture was diluted with methylene chloride (200 mL) and water (200 mL).
- the layers were separated, and the organic layer was washed with water (2 x 50 mL).
- the organic layer was concentrated to 50 mL, the treated with methanol.
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Abstract
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WO1998040374A2 (fr) * | 1997-03-10 | 1998-09-17 | Eastman Chemical Company | Catalyseurs de polymerisation d'olefines contenant des metaux de transition des groupes 8-10, ligands bidentes, procedes utilisant de tels catalyseurs et polymeres obtenus a partir de ces procedes |
WO2000050470A2 (fr) * | 1999-02-22 | 2000-08-31 | Eastman Chemical Company | Catalyseurs contenant des donneurs d'azote substitues par n-pyrrolyle |
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US6103658A (en) * | 1997-03-10 | 2000-08-15 | Eastman Chemical Company | Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom |
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2001
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WO1998040374A2 (fr) * | 1997-03-10 | 1998-09-17 | Eastman Chemical Company | Catalyseurs de polymerisation d'olefines contenant des metaux de transition des groupes 8-10, ligands bidentes, procedes utilisant de tels catalyseurs et polymeres obtenus a partir de ces procedes |
WO2000050470A2 (fr) * | 1999-02-22 | 2000-08-31 | Eastman Chemical Company | Catalyseurs contenant des donneurs d'azote substitues par n-pyrrolyle |
Non-Patent Citations (2)
Title |
---|
CARPINO L A: "Alkaline Degradation of 1,1-Disubstituted 2-Arenesulfonhydrazides. Synthesis and Reactivity of 1-Amino-2,5-diphenyl- and -2,3,4,5-tetraphenylpyrrole" J.ORG.CHEM., vol. 30, 1965, pages 736-739, XP002200613 * |
ENDERS D ET AL: "DIASTEREO-AND ENANTIOSELECTIVE SYNTHESIS OF C2-SYMMETRIC, PROTECTED1,N-DIAMINES FROM DIALDEHYDES" ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, VERLAG CHEMIE. WEINHEIM, DE, vol. 35, no. 19, 1996, pages 2261-2263, XP000971190 ISSN: 0570-0833 * |
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