ITMI990427A1 - PROCEDURE FOR THE SELECTIVE SYNTHESIS OF OLEFINS HAVING 6 DICARBONIUM ATOMS - Google Patents
PROCEDURE FOR THE SELECTIVE SYNTHESIS OF OLEFINS HAVING 6 DICARBONIUM ATOMSInfo
- Publication number
- ITMI990427A1 ITMI990427A1 IT1999MI000427A ITMI990427A ITMI990427A1 IT MI990427 A1 ITMI990427 A1 IT MI990427A1 IT 1999MI000427 A IT1999MI000427 A IT 1999MI000427A IT MI990427 A ITMI990427 A IT MI990427A IT MI990427 A1 ITMI990427 A1 IT MI990427A1
- Authority
- IT
- Italy
- Prior art keywords
- phenyl
- halogen
- borate
- alkyl
- tetrakis
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 16
- 230000015572 biosynthetic process Effects 0.000 title claims description 11
- 238000003786 synthesis reaction Methods 0.000 title claims description 11
- 150000001336 alkenes Chemical class 0.000 title claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- -1 chlorine Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 238000006384 oligomerization reaction Methods 0.000 claims description 8
- 150000001450 anions Chemical group 0.000 claims description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- HFKJQIJFRMRSKM-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenoxy]boronic acid Chemical compound OB(O)OC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 HFKJQIJFRMRSKM-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 4
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 3
- GBSQTQRZHMQHGH-UHFFFAOYSA-N 2-pyridin-2-yl-4,5-dihydro-1,3-oxazole Chemical class O1CCN=C1C1=CC=CC=N1 GBSQTQRZHMQHGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 2
- FGWZWSGZIWCUFZ-UHFFFAOYSA-N 4-phenyl-2-pyridin-2-yl-4,5-dihydro-1,3-oxazole Chemical compound C1OC(C=2N=CC=CC=2)=NC1C1=CC=CC=C1 FGWZWSGZIWCUFZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001544 silver hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
Titolo: Procedimento per la sintesi selettiva di olefine aventi 6 atomi di carbonio Title: Process for the selective synthesis of olefins having 6 carbon atoms
La presente invenzione riguarda un procedimento per la sintesi selettiva di olefine aventi 6 atomi di carbonio. The present invention relates to a process for the selective synthesis of olefins having 6 carbon atoms.
Più in particolare la presente invenzione riguarda un procedimento per l'oligomerizzazione dell’etilene a pressione ambiente, in presenza di complessi di palladio con 2-(2-piridinil)-2-ossazoline. More specifically, the present invention relates to a process for the oligomerization of ethylene at ambient pressure, in the presence of palladium complexes with 2- (2-pyridinyl) -2-oxazolines.
Le reazioni di oligomerizzazione dell’etilene rivestono un significativo interesse industriale, in quanto portano alla produzione di α-olefine che vengono utilizzate come comonomeri per la sintesi di polietilene e di polimeri elastomerici. Ethylene oligomerization reactions are of significant industrial interest, as they lead to the production of α-olefins which are used as comonomers for the synthesis of polyethylene and elastomeric polymers.
E’ stato ora trovato dalla Richiedente un nuovo procedimento che permette, operando a pressione ambiente ed utilizzando come catalizzatori palladio piridinil-ossazoline , di ottenere selettivamente eseni avendo, come sottoprodotti di reazione, quasi esclusivamente buteni. A new process has now been found by the Applicant which allows, by operating at ambient pressure and using palladium pyridinyl-oxazolines as catalysts, to selectively obtain hexenes having, as reaction by-products, almost exclusively butenes.
Costituisce, pertanto, oggetto della presente invenzione un procedimento per la sintesi selettiva di olefine aventi 6 atomi di carbonio che comprende l’oligomerizzazione dell’etilene a pressione ambiente in presenza di un sistema catalitico costituito essenzialmente da un complesso di palladio di formula generale (I): Therefore, the object of the present invention is a process for the selective synthesis of olefins having 6 carbon atoms which comprises the oligomerization of ethylene at ambient pressure in the presence of a catalytic system consisting essentially of a palladium complex of general formula (I ):
dove che rappresenta un’unità chelante di formula: where representing a chelating unit of formula:
in cui uguali o diversi tra di loro, rappresentano ciascuno: in which the same or different from each other, each represent:
un atomo di idrogeno, un alogeno, come cloro, un radicale alchilico C1-C10, eventualmente recante un gruppo con R radicale alchilico ovvero a hydrogen atom, a halogen, such as chlorine, a C1-C10 alkyl radical, possibly bearing a group with R alkyl radical or
un gruppo a group
un radicale aromatico eventualmente sostituito con un radicale alchilico od alcossilico an aromatic radical optionally substituted with an alkyl or alkoxy radical
ovvero possono essere uniti tramite una catena alchilica a formare un anello aromatico eventualmente sostituito con un radicale alchilico or they can be joined by means of an alkyl chain to form an aromatic ring possibly substituted with an alkyl radical
R' rappresenta un atomo di idrogeno, un gruppo alchilico, alcossilico, carbossilico, alcossicarbossil ico, arilico, alchilarilico, arilalchilico. R 'represents a hydrogen atom, an alkyl, alkoxy, carboxylic, alkoxycarboxylic, aryl, alkylaryl, arylalkyl group.
o un alogeno come cloro; or a halogen such as chlorine;
X è un anione del tipo: X is an anion of the type:
tetraki s(pentafluorofenil) borato, tetrakis [3,5-bis(trifluorometil )fenil]borato (BAF), tetrafluoroborato, un alogeno come cloro; tetraki s (pentafluorophenyl) borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (BAF), tetrafluoroborate, a halogen such as chlorine;
n è uguale a 1 o 2; n is equal to 1 or 2;
con la clausola che, quando R' e X sono, uno od entrambi, un alogeno, il sistema catalitico comprende un cocatalizzatore contenente alluminio scelto fra MAO (metil alluminossano) o fra quelli di formula generale (II): with the proviso that, when R 'and X are, either or both, a halogen, the catalytic system comprises a cocatalyst containing aluminum selected from MAO (methyl aluminoxane) or from those of general formula (II):
dove R” rappresenta un radicale alchile contenente da 1 a 25 atomi di carbonio e con l'ulteriore clausola che, quando il cocatalizzatore è scelto fra quelli di formula generale (II) è presente anche un sale od un acido di un anione scelto fra where R "represents an alkyl radical containing from 1 to 25 carbon atoms and with the further clause that, when the cocatalyst is selected from among those of general formula (II), a salt or an acid of an anion selected from among
tetrakis(pentafl uorofenil) borato, tetrakis [3,5-bis(trifl uorometil)fenil]borato (BAF), tetrafluoroborato . tetrakis (pentafl uorophenyl) borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (BAF), tetrafluoroborate.
I leganti utilizzati nel procedimento oggetto della presente invenzione possono essere preparati a partire da 2-cianopiridina e da un animino alcol con una metodologia di sintesi già nota in letteratura e descritta in Brunner et al, Chemie Berische, 122, 1998, 499 e in Bremberg et al, Tetrahedron Asymmetry 9, 1998, 3437. The binders used in the process object of the present invention can be prepared starting from 2-cyanopyridine and an amino alcohol with a synthesis methodology already known in the literature and described in Brunner et al, Chemie Berische, 122, 1998, 499 and in Bremberg et al, Tetrahedron Asymmetry 9, 1998, 3437.
Esempi di leganti sono: 2-(2-piridinil)-2-ossazolina, 4-metìl-2-(2-piridìnil)-2-ossazolina, 4-fenil-2-(2-piridinil )-2-ossazolina. Examples of ligands are: 2- (2-pyridinyl) -2-oxazoline, 4-methyl-2- (2-pyridinyl) -2-oxazoline, 4-phenyl-2- (2-pyridinyl) -2-oxazoline.
Legante preferito per la presente invenzione è 4-fenil-2-(2-piridini l)-2-ossazolina, gli anioni preferiti sono SbF6 e BAF mentre il gruppo R’ preferito è il metile. Preferred binder for the present invention is 4-phenyl-2- (2-pyridini 1) -2-oxazoline, the preferred anions are SbF6 and BAF while the preferred R 'group is methyl.
I catalizzatori utilizzati nel procedimento oggetto della presente invenzione, in particolare i catalizzatori in cui X e R' non sono alogeni, possono essere preparati a partire da palladio dicloruro in analogia con una metodologia di sintesi già nota in letteratura e descritta in Brunner et al, Chemie Berische, 122, 1998. 499 o in Rulke et al. Inorg. Chem. 1993, 32, 5769 o nella domanda di brevetto internazionale WO 96/23010. The catalysts used in the process object of the present invention, in particular the catalysts in which X and R 'are not halogen, can be prepared starting from palladium dichloride in analogy with a synthesis methodology already known in the literature and described in Brunner et al, Chemie Berische, 122, 1998. 499 or in Rulke et al. Inorg. Chem. 1993, 32, 5769 or in the international patent application WO 96/23010.
La reazione di oligomerizzazione dell’etilene, secondo il procedimento oggetto della presente invenzione, viene condotta in fase omogenea in presenza di un solvente scelto tra i solventi idrocarburici , quali esano, eptano, cicloesano, toluene, xilene ecc, tra i solventi ossigenati, quali etere etilico, tetraidrofurano, diossano, acetato di etile, metanolo, etanolo, t-butanolo, ecc. tra i solventi clorurati come cloruro di metilene, dicloroetano ecc, tra i solventi florurati come esafluorobenzene , 1,1,1,3,3,3-esafluoro-Z-fenil-2-propanolo, ecc. The ethylene oligomerization reaction, according to the process object of the present invention, is carried out in the homogeneous phase in the presence of a solvent selected from the hydrocarbon solvents, such as hexane, heptane, cyclohexane, toluene, xylene, etc., among the oxygenated solvents, such as ethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methanol, ethanol, t-butanol, etc. among the chlorinated solvents such as methylene chloride, dichloroethane etc., among the fluorinated solvents such as hexafluorobenzene, 1,1,1,3,3,3-hexafluoro-Z-phenyl-2-propanol, etc.
Risultati vantaggiosi si ottengono operando con concentrazioni del catalizzatore comprese tra 1 M/litro e 0.001 mM/litro, preferibilmente tra 50 mM/litro e 0.01 mM/litro. Advantageous results are obtained by operating with catalyst concentrations ranging from 1 M / liter to 0.001 mM / liter, preferably between 50 mM / liter and 0.01 mM / liter.
La reazione di oligomerizzazione avviene ad una temperatura compresa tra 0 e 100°C. preferibilimente a 20°C. I tempi di reazione sono generalmente compresi tra 1 ora e 5 giorni, preferibilmente tra 5 e 24 ore. La reazione viene condotta a pressione atmosferica . The oligomerization reaction takes place at a temperature between 0 and 100 ° C. preferably at 20 ° C. The reaction times are generally comprised between 1 hour and 5 days, preferably between 5 and 24 hours. The reaction is carried out at atmospheric pressure.
Allo scopo di meglio comprendere la presente invenzione e per mettere in pratica la stessa, di seguito vengono forniti alcuni esempi illustrativi, ma non limitativi. In order to better understand the present invention and to put it into practice, some illustrative, but not limitative, examples are provided below.
ESEMPIO 1 EXAMPLE 1
In un pallone vengono caricati, in atmosfera di argon, 45 cc di metanolo anidro, 5 g (48 mmoli)di 2-cianopiridina e 4 cc di una soluzione al 10% di MeONa in MeOH. La miscela di reazione viene mantenuta in agitazione a temperatura ambiente per 24 ore. In an argon atmosphere, 45 cc of anhydrous methanol, 5 g (48 mmoles) of 2-cyanopyridine and 4 cc of a 10% solution of MeONa in MeOH are charged into a flask. The reaction mixture is kept under stirring at room temperature for 24 hours.
Si aggiungono, quindi. 1,6 cc di acido acetico e si evapora la soluzione . They are added, therefore. 1.6 cc of acetic acid and the solution is evaporated.
Al solido bianco ottenuto si aggiungono 48 mmoli dell’ammino alcol utilizzato e 4 gocce di acido cloridrico concentrato. Si mantiene in agitazione a 60°C per un giorno in flusso di azoto per allontanare l’ammoniaca ed il metanolo che si formano. 48 mmoles of the amino alcohol used and 4 drops of concentrated hydrochloric acid are added to the white solid obtained. It is kept stirred at 60 ° C for a day in a nitrogen flow to remove the ammonia and methanol that are formed.
Il prodotto ottenuto viene purificato per cromatografia su gel di silice utilizzando come eluente una miscela acetato di metile/MeOH 70/30. The product obtained is purified by chromatography on silica gel using a mixture of methyl acetate / MeOH 70/30 as eluent.
ESEMPIO 2 EXAMPLE 2
Sintesi 1 , 5 -cicloottadiene-palladio-dicloruro Synthesis 1,5 -cyclooctadiene-palladium-dichloride
In un pallone si caricano 4 g di PdCl2 in 10 cc di HC1 concentrato. Si scalda a 80°C fino a completa dissoluzione. Si raffredda e si aggiungono 300 cc di EtOH. 4 g of PdCl2 in 10 cc of concentrated HCl are loaded into a flask. It is heated to 80 ° C until complete dissolution. It is cooled and 300 cc of EtOH are added.
Si filtra e alla soluzione si aggiungono 60 cc di 1,5-cicloottadiene. Si forma immediatamente un precipitato giallo che viene filtrato e lavato con etere etilico: Si ottengono 6,3 g di prodotto. It is filtered and 60 cc of 1,5-cyclooctadiene are added to the solution. A yellow precipitate is immediately formed which is filtered and washed with ethyl ether: 6.3 g of product are obtained.
ESEMPIO 3 EXAMPLE 3
Sintesi 1,5-cicloottadiene-palladio-metil cloruro Synthesis 1,5-cyclooctadiene-palladium-methyl chloride
In un pallone vengono caricati, in atmosfera di argon, 2 g (7 mmoli) di In an argon atmosphere, 2 g (7 mmoles) of
anidro. anhydrous.
Alla sospensione si aggiungono 1,7 cc (10,5 mmoli) di e si mantiene in agitazione sino a che la soluzione gialla non si decolora. Si evapora il solvente mantenendo la soluzione a 0°C. 1.7 cc (10.5 mmoles) of are added to the suspension and the mixture is kept stirred until the yellow solution is discolored. The solvent is evaporated by keeping the solution at 0 ° C.
Il solido ottenuto viene lavato più volte con etere etilico. Si ottengono 1,5 g di prodotto. The solid obtained is washed several times with ethyl ether. 1.5 g of product are obtained.
ESEMPIO 4 EXAMPLE 4
Sintesi 1 , 5-cicloottadiene-palladio-metil-esafluoroantimoniato Synthesis 1,5-cyclooctadiene-palladium-methyl-hexafluoroantimoniate
In un pallone si introducono, in atmosfera di argon, 0,5 g (1,9 mmoli) di (COD)PdMeCl, 10 cc di CH2C12 e 0,8 cc di CH3CN e 0,65 g (1,9 mmoli) di AgSbF6. Si forma subito un precipitato bianco. Si lascia in agitazione per 30 minuti, si filtra e si concentra la soluzione. Si ottengono 0,74 g di prodotto con una resa dell'85%. In a flask, 0.5 g (1.9 mmoles) of (COD) PdMeCl, 10 cc of CH2C12 and 0.8 cc of CH3CN and 0.65 g (1.9 mmoles) of AgSbF6. A white precipitate is formed immediately. The mixture is left under stirring for 30 minutes, the solution is filtered and concentrated. 0.74 g of product are obtained with a yield of 85%.
Il solido viene analizzato via <1>H-NMR: The solid is analyzed via <1> H-NMR:
<1>H-NMR: 5,83 (m 2H); 5,23 (m 2H); 2,61 (m 4H): 1,13 (s 3H). <1> H-NMR: 5.83 (m 2H); 5.23 (m 2H); 2.61 (m 4H): 1.13 (s 3H).
ESEMPIO 5 EXAMPLE 5
In un pallone si introducono in atmosfera di argon, 0,2 g di (COD)PdMeSbF6 e 0,10 g di 4-metil-2-(2-piridinil )-2-ossazolina in 10 cc di CH2C12 e 1 cc di CH3CN. Si lascia sotto agitazione per 4 ore, si forma un precipitato giallo chiaro che viene filtrato e seccato. Si ottengono 0,25 g di una polvere bianca. ESEMPIO6 In a flask, 0.2 g of (COD) PdMeSbF6 and 0.10 g of 4-methyl-2- (2-pyridinyl) -2-oxazoline in 10 cc of CH2C12 and 1 cc of CH3CN are introduced into an argon atmosphere. . It is left under stirring for 4 hours, a pale yellow precipitate is formed which is filtered and dried. 0.25 g of a white powder are obtained. EXAMPLE 6
In un pallone si introducono in atmosfera di argon, 0,2 g di (C0D)PdMeSbF6 e 0,10 g di 2-(2-piridinil )-2-ossazolina in 10 cc di CH2C12 e 1 cc di CH3CN. Si lascia sotto agitazione per 4 ore, si forma un precipitato bianco che viene filtrato e seccato. Si ottengono 0,22 g di una polvere bianca. In a flask, 0.2 g of (C0D) PdMeSbF6 and 0.10 g of 2- (2-pyridinyl) -2-oxazoline in 10 cc of CH2C12 and 1 cc of CH3CN are introduced into an argon atmosphere. It is left under stirring for 4 hours, a white precipitate is formed which is filtered and dried. 0.22 g of a white powder are obtained.
ESEMPIO 7 EXAMPLE 7
In un pallone si introducono in atmosfera di argon, 0,2 g di (C0D)PdMeSbF6 e 0,12 g di 4-fenil-2-(2-piridinil)-2 -ossazolina in 10 cc di CH2C12 e 1 cc di CH3CN. Si lascia sotto agitazione per 4 ore, quindi si aggiunge esano sino a quando inizia a formarsi un precipitato. In a flask, 0.2 g of (C0D) PdMeSbF6 and 0.12 g of 4-phenyl-2- (2-pyridinyl) -2 -oxazoline in 10 cc of CH2C12 and 1 cc of CH3CN are introduced into an argon atmosphere. . It is left under stirring for 4 hours, then hexane is added until a precipitate begins to form.
Si raffredda a -20°C per 20 ore, quindi si filtra . Si ottengono 0,28 g di una polvere bianca. It is cooled at -20 ° C for 20 hours, then filtered. 0.28 g of a white powder are obtained.
ESEMPIO 8 EXAMPLE 8
In un pallone da 25 cc vengono introdotti 10 mg (0,02 mmoli) di 2-(2-piridinil)-2-ossazolina-metilpalladio esafluoroantimoniato e 5 cc di diclorometano . La miscela biene mantenuta sotto agitazione, degasata e messa in atmosfera di etilene. 10 mg (0.02 mmoles) of 2- (2-pyridinyl) -2-oxazoline-methylpalladium hexafluoroantimoniate and 5 cc of dichloromethane are introduced into a 25 cc flask. The mixture is kept under stirring, degassed and placed in an ethylene atmosphere.
Si mantiene a temperatura ambiente per 5 ore. Al termine si analizza la miscela di reazione tramite analisi gascromatografica utilizzando n-decano come standard interno. Sono state convertite 75 moli di etilene per mole di palladio, producendo esclusivamente buteni ed eseni in un rapporto molare di 23:1. It is kept at room temperature for 5 hours. At the end the reaction mixture is analyzed by gas chromatography analysis using n-decane as internal standard. 75 moles of ethylene per mole of palladium were converted, producing exclusively butenes and hexenes in a molar ratio of 23: 1.
ESEMPI 9-13 EXAMPLES 9-13
Nella tabella successiva sono riportati i risultati di alcune oligomerizzazioni dell’etilene con differenti catalizzatori. Il tipo di legante del palladio è riportato in tabella, il radicale R’ è il metile e l'anione X è SbF6 . The following table shows the results of some ethylene oligomerizations with different catalysts. The type of palladium ligand is shown in the table, the radical R 'is methyl and the anion X is SbF6.
TABELLA TABLE
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