WO2005123753A1 - Derives d'acide 2-amino- et 2-hydroxy-2-phosphinoalcanoique et derives d'acide 2-phosphoniobis(2-hydroxyalcanoique), procede pour preparer ces derives, et utilisation de ces derives pour preparer des catalyseur metalliques - Google Patents

Derives d'acide 2-amino- et 2-hydroxy-2-phosphinoalcanoique et derives d'acide 2-phosphoniobis(2-hydroxyalcanoique), procede pour preparer ces derives, et utilisation de ces derives pour preparer des catalyseur metalliques Download PDF

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WO2005123753A1
WO2005123753A1 PCT/DE2005/000969 DE2005000969W WO2005123753A1 WO 2005123753 A1 WO2005123753 A1 WO 2005123753A1 DE 2005000969 W DE2005000969 W DE 2005000969W WO 2005123753 A1 WO2005123753 A1 WO 2005123753A1
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radicals
derivatives
butyl
methyl
groups
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PCT/DE2005/000969
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Joachim Heinicke
Normen Peulecke
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Ernst Moritz Arndt Universität Greifswald
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    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5004—Acyclic saturated phosphines
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5407—Acyclic saturated phosphonium compounds

Definitions

  • the invention relates to new 2-A ino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives, a process for the preparation of these compounds and the use of these compounds for the production of new metal catalysts.
  • Synthetic ⁇ -amino acids and their derivatives often show biological effects themselves or as a component of compounds produced therefrom and are of general importance for biochemical, biomedical, pharmacological and other life science research and applications.
  • R alkyl, haloalkyl, hydroxyalkyl, alkoxy, alkoxycarbonyl
  • phosphinoglycine ester iPr 2 PCH (NEt 2 ) COOMe phosphinoyl and phosphonoglycine derivatives with pentavalent phosphorus, in which the phosphorus is not nucleophilic but electrophilic.
  • P-metal coordination is not possible.
  • the phosphinoylglycolic acid derivatives with pentavalent phosphorus in which the phosphorus is not nucleophilic but electrophilic, have completely different properties than compounds with trivalent phosphorus.
  • ester iPr 2 PCH (NEt 2 ) COOMe is based on the reaction of chlorodiisopropylphosphine with the
  • Phosphonoglycine esters [(0-alkyl) 2 P (0) -CH ( + NHR 'R'') -C00- alkyl], which are required for the preparation of various ß-lactam antibiotics and dehydroamino acids, were obtained by Michaelis-Arbuzov reaction of triethyl phosphite with N-protected ⁇ -haloglycine esters (H. Gross,
  • Another synthetic route to phosphonoglycine is based on diethyl I-socyanomethylphosphonic acid, which after metalation with potassium tert. butylate is reacted with methyl isocyanate or carbamoyl chlorides to form oxazolylphosphonic diesters, which are then hydrolyzed with hydrochloric acid (J. Rachon, U. Schöllkopf, Liebigs Ann. Chem. 1981, 1693-1698).
  • Metal catalysts with P, O hybrid ligands can e.g. enable the oligo- and polymerization of ethylene and ⁇ -olefins or the cooligo- or copolymerization of their mixtures.
  • Emulsion polymerizations of ethene with the catalysts C, R 2 or R 3 S0 3 " Na + , S0 3 ⁇ -C 6 H 33 NMe 3 + , in toluene-water, made from B and Ni (COD), have recently been reported (A Tomov, R. Spitz, T. Saudemont, X. Drujon (Elf Atochem) FR Appl 12 476 (06.10.1998); R. Soula, C. Novat, A. Tomov, R. Spitz, J. Claverie, X. Drujon, J.
  • the invention was therefore based on the object of 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives and a process for the preparation of these compounds which is simple and direct synthesis enables and can be carried out as a one-pot reaction, and to provide the corresponding metal complexes.
  • A is - + NHR 4 R 5 (type 1) or -OH (with + NH 2 R 4 R B as counter ion: type 2)
  • R 1 is a hydrogen atom or a C ⁇ -C ⁇ 2 alkyl radical or a C 6 -C ⁇ 4 aryl radical,
  • R 2 , R 3 , R 4 and R 5 independently of one another for hydrogen, C 1 -C 2 -n-alkyl groups, C 1 -C 12 -branched alkyl groups, -CC 2 -cycloalkyl groups, -C- 2 alkoxy groups, -C -C ⁇ 2 alkenyl groups, CC 2 o-arylalkyl groups, C6 -C 4 aryl groups, C 6 -C aryl groups which are substituted identically or differently by one or more C 1 -C 2 alkyl groups, C 1 -C 2 alkoxy groups or halogens, or OR 6 or NR 6 R 7 , where two of the radicals R 2 and R 3 or R 4 and R 5 optionally form a saturated or unsaturated ring with one another,
  • R 6 and R 7 are selected independently of one another from hydrogen, C 1 -C 2 -alkyl groups, C 6 -C 4 -aryl groups, C-co-arylalkyl groups, and optionally form a saturated or unsaturated ring with one another.
  • radical R 1 is selected from the group of hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl radical. It is particularly preferred if the radical R 1 represents a hydrogen atom or a methyl radical.
  • R 2 , R 3 , R 4 and R 5 are radicals from the group of hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl, iso-propyl, iso-butyl, tert .- Butyl, ethyl propyl, cyclohexyl, methoxy, ethoxy, propyloxy, tert. -Butoxy-, phenyl- and benzyl radical are preferred, the aryl radicals mentioned also being substituted-
  • PV 1 73C Fa n ⁇ can be.
  • the other substituents are methyl, ethyl or tert. -Butyl, methoxy or ethoxy radicals are preferred.
  • fluorine, chlorine and bromine are preferred.
  • Particularly preferred radicals on the substituted aryl groups are methyl radicals or chlorine as a substituent.
  • Particularly preferred radicals for R 2 to R 5 are hydrogen atoms, ethyl, tert. -Butyl, cyclohexyl and phenyl residues.
  • R 6 and R 7 are radicals from the group of hydrogen atom, methyl, ethyl, propyl, tert. -Butyl, cyclohexyl, phenyl, benzyl or tolyl radical preferred.
  • a radical R 6 , R 7 is particularly preferably a hydrogen atom or a methyl, ethyl or tert. Butyl residue.
  • boron compound BR 3 from the group of BH 3 , B (alkyl) 3 B (aryl) 3
  • PVA-2173 fit and B (perfluoroaryl) 3 is selected.
  • BH and boron triphenyl are particularly preferred.
  • the compounds according to the invention have no double bonded radical X on the phosphorus. Therefore, in contrast to the compounds which have a double-bonded radical on the phosphorus, the phosphorus in these compounds has a lone pair of electrons directly or after the radical X has been split off and is nucleophilic.
  • the water solubility of the ligands and catalysts is brought about by the ammonium or hydroxyl and carboxylate groups.
  • the NH or OH function for example via amide or ester formation, offers the possibility of binding to residues which further increase water solubility or allow the production of heterogeneous catalysts.
  • Another object of the present invention is a process for the preparation of the 2-amino and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of the general formula I, wherein the radicals A, X and R 1 to R 7 have the meaning given below, by reaction of an ⁇ -ketocarboxylic acid R 1 C (0) -C00H or its hydrate or its acetal with a phosphine component R 2 R 3 PH and an amine component R 4 R 5 NH or R 4 R 5 NSiAlkyl 3 , optionally with a dehydrating auxiliary reagent, in a suitable solvent and optionally - if X stands for BR 3 - reaction of the product obtained with B 2 H 6 , a BH 3 adduct or an organoborane.
  • PVA- 1 'Tu Pa ⁇ w ⁇ g nem formed from the phosphine component and the ⁇ -ketocarboxylic acid phosphonium salt or condensation product.
  • R 'NH + amine component (or R "R 5 NSiAlkyl 3 )
  • the reaction takes place at a temperature between 0 ° C. and the boiling point of the solvent, preferably at room temperature.
  • Polar solvents preferably dialkyl ethers, alkylaryl ethers, alcohols, esters of carboxylic acids, phosphoric acid esters, amides of carboxylic acids, chlorinated hydrocarbons, aromatic hydrocarbons, mixtures of the abovementioned solvents, mixtures of the abovementioned solvents with water or mixtures of the abovementioned solvents with saturated solvents are used as solvents or unsaturated hydrocarbons.
  • Di-n-alkyl ethers are particularly preferred.
  • Preferred phosphines are P-secondary representatives R 2 R 3 PH (R 2 , R 3 ⁇ H).
  • Preferred NH components are secondary and primary amines and ammonium salts, particularly preferred are secondary amines and bulky substituted primary amines. Corresponding silylamines can be used instead of the NH components.
  • Preferred ⁇ -ketocarboxylic acid derivatives are derivatives of glyoxylic acid, pyruvic acid, phenylglyoxylic acid or oxomalonic acid, and particularly preferred is glyoxyl acid hydrate.
  • a water-binding aid is optionally used.
  • Activated molecular sieves A3 or A4 or water-binding salts of main group metals such as Mg (C10 4 ) 2 which are insoluble in the respective solvent are preferred.
  • the desiccant is, for example, in a filter candle that is immersed in the solution.
  • water of reaction is dragged through boiling solvent into an extraction vessel filled with the desiccant (eg Soxhlett apparatus etc.) or removed azeotropically.
  • the product obtained is reacted further with BH 6 , a BH 3 adduct or an organoborane.
  • the BH 3 adduct is preferably of the type BH 3 donor (donor selected from dialkyl sulfide, THF, amine R 3 N or N heterocycle), preferably BH 3 -SEt 2 , BH 3 - NEt 3 , BH 3 -pyridine or BH 3 -THF used.
  • the organoborane is preferably selected from the group of B (alkyl) 3 , B (aryl) 3 and B (perfluoroaryl) 3 , boron triphenyl being particularly preferred.
  • the reactions are preferably carried out immediately after separation and washing of the precipitate of 1 or 2 or 3 from the three-component reaction, before cleaning attempts by recrystallization.
  • Polar aprotic solvents preferably dialkyl ethers or aryl alkyl ethers, particularly preferably cyclic dialkyl ethers such as THF or dioxane, serve as solvents.
  • the reactions are carried out in the temperature range from -80 ° C to the boiling point of the solvent, preferably between 0 and 80 ° C, particularly preferably at 15-25 ° C.
  • aprotic-polar e.g. THF
  • easily polarizable halogen-containing solvents e.g. CHC1 3
  • PVA I Tit. F-sr ⁇ n Form with which H 2 0 2 can be converted to 2-hydroxy-2-phosphinoylalkanoic acid derivatives of type 2 (X 0).
  • the method according to the invention can provide compounds which have biocidal properties,
  • Another object of the present invention is therefore the use of the 2-amino and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphonobis (2-hydroxyalkanoic acid) derivatives of the general formula I according to the invention as a crude product or in pure form Production of metal-containing 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives (2-amino and 2-hydroxy-2-phosphinoalkanoate transition metal derivatives) with metals of the 6th-10th Group of the periodic table, these metal complexes corresponding to the general formula II,
  • Y is a complex fragment M, 1 / 2M, ML n or 1/2 ML n
  • M is a metal of the 6th-10th Group of the Periodic Table of the Elements
  • L is a ligand and n is an integer from 1 to 6 and
  • A is - + NHRR 5 (type 1) or -OH (with + NH 2 R 4 R 5 as counter ion: type 2),
  • R 1 represents a hydrogen atom or a C 1 -C 2 alkyl radical or a C 6 -C 4 aryl radical
  • R 2, R 3, R 4 and R 5 independently of one another are hydrogen, C ⁇ 2 -n-alkyl, C ⁇ -C ⁇ 2-branched alkyl groups, C ⁇ -C ⁇ cycloalkyl, C ⁇ -C ⁇ 2 alkoxy, C ⁇ -C ⁇ 2 -Alkenyl groups, C -C 20 arylalkyl groups, C 6 -Ci 4 aryl groups, C 6 -C ⁇ 4 aryl groups, which are identical or differently substituted by one or more
  • C 1 -C 2 alkyl groups, C 6 -C 14 aryl groups, C -C 2 o arylalkyl groups are selected, and optionally together form a saturated or unsaturated ring.
  • the radical R 1 is selected from the group of hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl radical. It is particularly preferred if the radical R 1 represents a hydrogen atom or a methyl radical.
  • radicals R 2 , R 3 , R 4 and R 5 are radicals from the group of hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl, iso-propyl, iso-butyl, tert , - Butyl, ethyl propyl, cyclohexyl, methoxy, ethoxy, propyloxy, tert. -Butoxy, phenyl, and benzyl radical preferred, where the aryl radicals mentioned can also be further substituted.
  • the radicals R 2 to R 5 represent substituted aryl groups, the other substituents are methyl, ethyl or tert.
  • R 6 and R 7 are radicals from the group of hydrogen atom, methyl, ethyl, propyl, tert. - Butyl, cyclohexyl, phenyl, benzyl or tolyl radical preferred.
  • Particularly preferred as radical R 6 , R 7 is a hydrogen atom or a methyl, ethyl or tert. - Butyl residue.
  • Metals preferred according to the invention are iron, cobalt, nickel or palladium.
  • iron and cobalt the oxidation states 0, +2 and +3, with nickel and palladium the oxidation states 0 and +2 are preferred.
  • Preferred metal compounds are nickel (0) compounds, for example Ni (COD) 2 , NiL 4 (L for example PMe 3 , PPh 3 , P (OEt) 3 , CO), - Ni (COD) 2 is particularly preferred.
  • unsaturated organonickel (II) compounds eg allyl nickel compounds, metal nickel compounds, nickel ß-diketonates, diphenyl nickel (PMe 3 ) 2 or - soluble metal salts, preferably nickel salts, together with a reducing or alkylating agent such as sodium hydride (NaH ), Potassium hydride (KH), sodium borohydride (NaBH 4 ), zinc borohydride (Zn (BH 4 ) 2 ) or triethylsilane (Et 3 SiH), methyl lithium (MeLi), butyl lithium (BuLi), triethyl aluminum (AlEt 3 ) or methyl luminoxan (MAO) etc.
  • reaction takes place — optionally with the exclusion of water or alcohols as solvents — for example by combining freshly prepared solutions of the components in THF or adding the solid zwitterionic compound to a solution of the borane or metal compound.
  • PVA ⁇ 73s ⁇ a r ⁇ i suitable solvents, optionally in the presence of ethylene or ⁇ -olefins or mixtures thereof.
  • the molar ratio of the metal-free compound of type 1, 2 or 3 to the metal, preferably nickel compound can vary from approximately 1.5: 1 to 1:50, preferably it is 1.2: 1 to 1: 5, for Ni (0 ) Compounds is 1: 1 particularly preferred.
  • Cyclic ethers such as e.g. THF or dioxane, acyclic ethers such as e.g. Diethyl ether, diisopropyl ether, di-n-butyl ether or dimethoxyethane, ketones such as e.g. Acetone, amides such as e.g.
  • Dirnethylformamide or Dirnethylacetamid aromatic solvents such as toluene or xylenes, olefins such as e.g. Hexenes or olefin mixtures, such as those formed during oligomerization.
  • Alcohols are conditionally suitable, e.g. n-butanol or butynediol, and water and their mixtures with the aforementioned organic solvents.
  • the amino or OH group in 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1 or 2 or 3 brings about significant changes in properties.
  • the solubility of ligands and catalysts in polar solvents or water is considerably higher and, if the catalyst complexes are resistant to hydrolysis, favors applications in aqueous-organic solvent systems or two-phase catalytic processes.
  • the amino or the OH group can coordinate in addition to the phosphino and carboxylate group or competitively to transition metals and thus bring about changes in the activity and selectivity of the metal catalysts formed here in comparison to phosphinoacetic acid metal catalysts.
  • the amino group also has a significant influence on the stability and the spectroscopic properties of the compounds.
  • Ph 2 P-CH (NtBuH 2 + ) COO "dissolves to form a solution of the hydrolysis product Ph 2 P-CH (OH) COO " tBuNH 3 + (type 2, X no substituent), which at room temperature and Exclusion of air is stable over a long period of time.
  • base NaOD
  • Ph 2 P-CH (NtBuH) COO " Na + approximately a small amount of Ph 2 PD, with the addition of excess tert-butylamine a Solution of Ph 2 P-CH (NtBuH) COO " tBuNH 3 + .
  • the borane adduct Ph 2 P (BH 3 ) -CH (NtBuH 2 + ) COO " formed from Ph 2 P-CH (NtBuH 2 + ) COO " and BH 3 -THF is air-stable and dissolves in CDC1 3 without decomposition. Nevertheless, it is suitable as a procatalyst, probably by displacing the BH 3 with transition metal fragments from the phosphorus. Transition metal salts, not previously isolated in their pure form, are believed to be formed by intramolecular five-membered chelate complex formation.
  • FVA-21 '1 » bilises and enables catalytic reactions even at higher temperatures (100 ° C).
  • N- tert. -Butyl-diphenylphosphinoglycine To a solution of 1.89 g (10.2 mmol) of diphenylphosphine and 1.07 mL (10.2 mmol) of ter. -Butylamine in 20 mL diethyl ether is given a solution of glyoxylic acid hydrate (939 mg, 10.2 mmol) in diethyl ether (10 mL) prepared in an ultrasonic bath. A colorless precipitate immediately precipitates, which is filtered off after about 24 h, washed with a little ether and dried, yield 3.25 g, mp. 123-125 ° C. Rapid recrystallization from a little methanol gives N-tert.
  • N- tert. -Butyl-diphenylphosphinoglycin -2Boran A solution of BH 3 -SEt 2 in THF (1.5 mL, 1.5 mmol) is converted to N-tert at 0 ° C. -Butyl-diphenylphosphinoglycine (200 mg, 0.576 mmol), dissolved in 10 mL THF. This leads to strong gas development. The mixture is stirred at 40 ° C. for 1 hour and at room temperature overnight. The solvent is removed and the residue washed with hexane. 190 mg of white powder are formed (yield 96%), mp. 116-118 ° C.
  • Diethylammonium-diphenylphosphoniumbis (glycolate) A solution of glyoxylic acid hydrate (494 mg, 494 mg, 5.37 mmol) in diethyl ether (10 mL) was added. A colorless precipitate precipitates out after a few minutes. After standing overnight, it is filtered,
  • Diethylammonium dicyclohexylphosphonium bis (glycolate) To a solution of 0.743 g (3.75 mmol) dicyclohexylphosphine and 0.39 mL (3.75 mmol) diethylamine in 15 mL diethyl ether, a solution of glyoxylic acid hydrate (345 mg, 3.75 mmol) in diethyl ether (10 mL) was added. A colorless precipitate precipitates out after a few minutes. After 24 h, the mixture is filtered, washed with a little ether and dried. Yield: 0.85 g (69%).
  • Diethylammonium-di- er. -butylphosphonium-bis (glycolate) A solution prepared in an ultrasonic bath is added to a solution of 1.77 g (12.11 mmol) of diet. - butylphosphine and 1.25 mL (12.11 mmol) of diethylamine in 20 mL of diethyl ether - Solution of glyoxylic acid hydrate (1.114 g, 12.11 mmol) in diethyl ether (10 mL) added. A colorless, sticky precipitate precipitates out after a few minutes. After 24 h, the mixture is filtered, washed with a little ether and n-hexane and dried, yield 2.5 g (75%), soluble in H 2 0 (D 2 0), THF, CDC1 3 .
  • Example 7 ter. -Butylammonium-diphenylphosphinoyl glycolate: To a solution of 0.379 g (1.203 mmol) 2- ert N- tert. Butyl diphenylphosphinoglycine (from Example 1) in 20 mL of a mixture of H 2 0 and THF (2: 1) are added at 0 ° C 0.122 ml H 2 0 2 (30%). After stirring for 24 h at room temperature, the solvent is removed in vacuo, the sticky residue is washed with a little ether and dried. Yield: 0.35 g (88%), mp 177-179 ° C.
  • Diethylammonium diphenylphosphinoyl glycolate semihydrate Hydrogen peroxide (0.10 mL, 30%, 0.88 mmol) is added dropwise at 20 ° C. to a solution of PhP + [CH (OH) -COO " ] 2 Et 2 NH 2 + from Example 4 (150 mg, 0.368 mmol) in water (10 mL). After stirring overnight, the solvent is removed in vacuo and the remaining oil is washed with hexane and a little diethyl ether. After drying, 130 mg (98%) whiter Solid, mp 149.5 ° C.
  • Et 2 NH 2 + Ph 2 P + [CH (OH) -COO-] 2 from Example 4 is added to a solution of Ni (COD) 2 (33 mg, 120 ⁇ mol) in THF (10 mL) at 0 ° C. 38 mg, 120 ⁇ mol) in THF (10 mL, not completely dissolved).
  • the mixture is stirred for 10 minutes at 0 ° C. and 30 minutes at 20 ° C. (light yellow) and injected into the autoclave. After pressing on ethylene (30 bar, 10 g) the mixture is heated to 100 ° C. for 15 hours. After cooling and check weighing, unreacted ethylene is discharged (conversion 44%). Volatile constituents are separated off by distillation (1.5 torr, bath up to approx.
  • the distillate contains 3.7 g of ⁇ -olefins (C4 22%, C6 33.7%, C8 27.5%, C10 14.3%, C12 2.5%, isomers ⁇ 0.1% GC).
  • the residue is stirred with methanol / hydrochloric acid (1: 1) at room temperature (ID), then washed with water and methanol and dried, 1.3 g of wax.
  • a solution of Et 2 NH 2 + cHex 2 P + [CH (OH) - COO-] 2 is made from a solution of Ni (COD) 2 (30 mg, 110 ⁇ mol) in THF (10 mL) at 0 ° C
  • Example 5 34 mg, 104 ⁇ mol added to THF (10 mL), stirred at 0 ° C. for 10 minutes and at 20 ° C. for 30 minutes.
  • the mixture is injected into the autoclave, ethylene (30 bar, 7.3 g) is pressed in and heated to 100 ° C. for 15 hours.
  • Working up as in Example 11 gives a conversion of 59% and 4.3 g of polyethylene, mp.
  • Example 15 A solution of Et 2 NH + tBu 2 P + [CH (OH) - COO-] 2 is added to a solution of Ni (COD) 2 (29 mg, 106 ⁇ mol) in THF (10 mL) at 0 ° C from Example 6 (28 mg, 102 ⁇ mol) in THF (10 mL), stirred for 10 min at 0 ° C and 30 min. at 20 ° C. The mixture is injected into the autoclave, ethylene (50 bar, 12.6 g) is pressed in and the mixture is heated to 100 ° C. for 15 hours. Working up as in Example 11 gives a conversion of 75% and 9.3 g of polyethylene, mp.
  • PVA 2173t "E 10.8 g) is pressed on and heated to 100 ° C. for 15 hours. After cooling and check weighing, unreacted ethylene is drained off. Despite weak mixing (magnetic stirrer) there was a partial reaction. The white polymer foam on the surface is worked up with MeOH / HCl (3: 1) and gives 1.6g wax (15%) mp 68-70 ° C.

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Abstract

La présente invention concerne de nouveaux dérivés d'acide 2-amino- et 2-hydroxy-2-phosphinoalcanoïque (X = aucun substituant - paire d'électrons libres, BR3) et des dérivés d'acide 2-phosphoniobis(2-hydroxyalcanoïque) de formule générale I(A), dans laquelle A est -+NHR4R5 (type 1) ou -OH (avec +NH2R4R5 en tant qu'ion opposé: type 2), et X est choisi dans le groupe -C ( (COO-) (OH) R1) (type 3, lorsque A = -OH et avec +NH2R4R5 en tant qu'ion opposé), aucun substituant (paire d'électrons libres) et composé de bore BR3. L'invention a également pour objet un procédé pour préparer ces composés et l'utilisation de ces composés pour préparer de nouveaux catalyseurs métalliques. La préparation des dérivés d'acide 2-amino- et 2-hydroxy-2-phosphinoalcanoïque et des dérivés d'acide 2-phosphoniobis(2-hydroxyalcanoïque) fait intervenir une réaction à trois composantes qui - dans la mesure où X est BR3 - est suivie de la conversion du produit obtenu avec B2H6, un produit d'addition BH3 ou un organoborane. Les complexes métalliques sont obtenus par conversion avec des composés comprenant des métaux des groupes 6-10 du tableau périodique des éléments.
PCT/DE2005/000969 2004-06-15 2005-05-26 Derives d'acide 2-amino- et 2-hydroxy-2-phosphinoalcanoique et derives d'acide 2-phosphoniobis(2-hydroxyalcanoique), procede pour preparer ces derives, et utilisation de ces derives pour preparer des catalyseur metalliques WO2005123753A1 (fr)

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