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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 PDF

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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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Prior art keywords
hydrocarbyl
process according
substituted hydrocarbyl
heteroatom connected
general formula
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Ceased
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PCT/US2001/042976
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English (en)
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WO2002036585A3 (fr
Inventor
James Allen Ponasik, Jr.
Leslie Shane Moody
Peter Borden Mackenzie
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Eastman Chemical Co
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Eastman Chemical Co
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Priority to EP01992707A priority Critical patent/EP1334097A2/fr
Publication of WO2002036585A2 publication Critical patent/WO2002036585A2/fr
Publication of WO2002036585A3 publication Critical patent/WO2002036585A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

L'invention concerne des procédés de préparation de 4,5-bisimino-[1,3]dithiolanes et de 2,3-bisimino-[1,4]dithianes. Lesdits procédés consistent à convertir un oxalamide en dithiooxalamide, puis à convertir le dithiooxalamide soit en 4,5-bisimino-[1,3]dithiolane, soit en 2,3-bisimino-[1,4]dithiane.
PCT/US2001/042976 2000-11-06 2001-11-06 Procede de preparation de ligands pour catalyseurs de polymerisation des olefines Ceased WO2002036585A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01992707A EP1334097A2 (fr) 2000-11-06 2001-11-06 Procede de preparation de ligands pour catalyseurs de polymerisation des olefines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US24617800P 2000-11-06 2000-11-06
US60/246,178 2000-11-06

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WO2002036585A2 true WO2002036585A2 (fr) 2002-05-10
WO2002036585A3 WO2002036585A3 (fr) 2002-12-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2368607C2 (ru) * 2007-09-11 2009-09-27 Институт нефтехимии и катализа РАН Способ получения 1-(5-бензоил-1,3-дитиан-5-ил)-1-этанона

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
EP1192189B1 (fr) * 1999-02-22 2004-09-29 Eastman Chemical Company Catalyseurs contenant des donneurs d'azote substitues par n-pyrrolyle

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2368607C2 (ru) * 2007-09-11 2009-09-27 Институт нефтехимии и катализа РАН Способ получения 1-(5-бензоил-1,3-дитиан-5-ил)-1-этанона

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WO2002036585A3 (fr) 2002-12-27

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