DE102004029697B4 - 2-Amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives, process for the preparation of these derivatives and use of the derivatives for the preparation of 2-amino or 2-hydroxyphosphinoalkanoate nickel derivatives - Google Patents

Abstract

wobei
A gleich -⁺NHR⁴R⁵ (Typ 1)
oder -OH (mit ⁺NH₂R⁴R⁵ als Gegenion: Typ 2) ist,
X aus der Gruppe
-C((COO^–)(OH)R¹) (Typ 3, wenn A = -OH ist und mit ⁺NH₂R⁴R⁵ als Gegenion),
freies Elektronenpaar (kein Substituent) und einer Borverbindung
ausgewählt ist,
wobei die Borverbindung aus der Gruppe von BH₃, B(Alkyl)₃, B(Aryl)₃ und B(Perfluoraryl)₃ ausgewählt ist,
R¹ ein Wasserstoffatom oder
einen C₁-C₁₂-Alkylrest oder
einen C₆-C₁₄-Arylrest bedeutet,
R², R³, R⁴ und R⁵ unabhängig voneinander für
Wasserstoff,
C₁-C₁₂-n-Alkylgruppen,
C₁-C₁₂-verzweigte Alkylgruppen,
C₃-C₁₂-Cycloalkylgruppen,
C₁-C₁₂-Alkoxygruppen,
C₁-C₁₂-Alkenylgruppen,
C₇-C₂₀-Arylalkylgruppen,
C₆-C₁₄-Arylgruppen,
C₆-C₁₄-Arylgruppen, die gleich oder unterschiedlich substituiert sind durch eine oder mehrere
C₁-C₁₂-Alkylgruppen, C₁-C₁₂-Alkoxygruppen oder Halogene oder
OR⁶ oder
NR⁶R⁷
stehen,
wobei zwei der Reste R² und R³ oder R⁴ und R⁵ gegebenenfalls miteinander...2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of general formula I,

in which
A equals - ⁺ NHR ⁴ R ⁵ (Type 1)
or -OH (with ⁺ NH ₂ R ⁴ R ⁵ as counterion: type 2),
X from the group
-C ((COO ^- ) (OH) R ¹ ) (Type 3, when A = -OH and with ⁺ NH ₂ R ⁴ R ⁵ as counterion),
free electron pair (no substituent) and a boron compound
is selected,
wherein the boron compound is selected from the group of BH ₃ , B (alkyl) ₃ , B (aryl) ₃ and B (perfluoroaryl) ₃ ,
R ^{1 is} a hydrogen atom or
a C ₁ -C ₁₂ alkyl radical or
a C ₆ -C ₁₄ -aryl radical,
R ² , R ³ , R ⁴ and R ⁵ are each independently
Hydrogen,
C ₁ -C ₁₂ -n-alkyl groups,
C ₁ -C ₁₂ branched alkyl groups,
C ₃ -C ₁₂ cycloalkyl groups,
C ₁ -C ₁₂ alkoxy groups,
C ₁ -C ₁₂ alkenyl groups,
C ₇ -C ₂₀ arylalkyl groups,
C ₆ -C ₁₄ aryl groups,
C ₆ -C ₁₄ aryl groups which are the same or different substituted by one or more
C ₁ -C ₁₂ alkyl groups, C ₁ -C ₁₂ alkoxy groups or halogens or
OR ⁶ or
NR ⁶ R ⁷
stand,
where two of the radicals R ² and R ³ or R ⁴ and R ⁵ optionally together ...

Description

The The invention relates to 2-amino and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives, a method for preparing these compounds and the use of these compounds for the preparation of 2-amino or 2-hydroxyphosphinoalkanoate nickel derivatives.

Synthetic α-amino acids and their derivatives often show itself or as a component of compounds made therefrom biological Effects and are for biochemical, biomedical, pharmacological and other life sciences Research and applications of general importance.

The phosphonic acid H ₂ O ₃ P-CH (NH ₂ ) -COOH, (X = O, R ² = R ³ = OH), which has herbicidal activity (M. Kuwahara M. Mutsukado, H. Takahashi, Y. Kawamura, T. Oya, T. Ikai, Jpn. Kok, Tok Koho 79.89027, Chem. Abstr., 1979, 91, 15276r).

Also, 2-hydroxy-2-phosphinoylalkanoic acid derivatives of type 2 with X = O, biological activity is known. Thus, Me ₂ P (O) -CH (OH) -COOR with R = H (Hoe704) is a potent herbicide which inhibits acetolactate reducto-isomerases (A. Schulz, P. Spoenemann, H. Koecher, F. Wengenmayer ( Hoechst A.-G.) FEBS Lett 1988, 238, 375-378; R. Dumas, C. Cornilon-Bertrand, P. Guigue-Talet, P. Genix, R. Douce, D. Job, Biochem Aubert, R. Bligny, DA Day, J. Whelan, R. Douce, Plant J. 1997, 11, 649-657, 1994. 301, 813-820, R = alkyl, haloalkyl, hydroxyalkyl, alkoxy, Alkoxycarbonyl is also indicated as having herbicidal activity (K. Bauer, H. Bieringer, E. Hacker, (Hoechst A.-G.) DE 34 16 201 ; HJ Loeher, K. Bauer, H. Bieringer (Hoechst A.-G.) DE 35 11 198 A1 ).

Other noteworthy substances are a phosphinoglycine ester iPr ₂ PCH (NEt ₂ ) COOMe, as well as phosphinoyl and phosphonoglycine derivatives with pentavalent phosphorus, in which the phosphorus is not nucleophilic but electrophilic. In the latter compounds, for example, a P-metal coordination is not possible.

Furthermore, α-phosphonio or phosphoranylidene-α-amino acid derivatives (R ₃ P =CH (NHR ₂ ⁺ ) COO ^- , R ₃ P =C (NHR ₂ ⁺ ) COO ^- ) may be mentioned (R. Mazurkiewicz, M. Grymel, AW Pierwocha, Monatsh. Chem. 1999, 130, 597-604; LA Tamm, UN Chistokletov, AA Petrov, Zh. Obshch. Khim. 1972, 42, 1926-30). These contain a firmly covalently bound organic radical X on the phosphorus and are not nucleophilic on the pentavalent P atom.

The Phosphinoylglykolsäure derivatives with pentavalent Phosphorus, in which the phosphorus is not nucleophilic, but electrophilic is completely own other material properties than compounds with trivalent phosphorus.

The preparation of the ester iPr ₂ PCH (NEt ₂ ) COOMe is based on the reaction of chlorodiisopropylphosphine with the sodium enolate of N, N-diethylglycine methyl ester (ZS Novikova, SN Zdorova, IF Lutsenko, Zh. Obshch., Khim., 1976, 46, 433 -434). Individual P-oxidized phosphinoylglycine derivatives with double-bonded oxygen on the phosphorus were prepared by complex multistage processes. Thus, a diphenylphosphinoyl nosarcosine derivative, Ph ₂ P (O) -CH (NHMe) -C (O) NHBz, and phosphonosarcosine derivatives (RO) ₂ P (O) -CH (NHMe) -C (O) Y (R = Me, H; Y = NHBz, OH) by Michaelis-Arbuzov reaction of Ph ₂ POMe, PhP (OEt) ₂ or P (OR) ₃ with cyclic acetalically O, N-protected bromosarcosine derivatives and subsequent hydrolysis (K Burger, E. Heistracher, R. Simmerl, M. Eggersdorfer, Z. Naturforsch., 1992, 47B, 424-433).

Phosphonoglycine esters [(O-alkyl) ₂ P (O) -CH ( ⁺ NHR'R '') - COO-alkyl], which are required for the preparation of various β-lactam antibiotics as well as dehydroamino acids, were prepared by Michaelis-Arbuzov reaction of Triethyl phosphite with N-protected α-haloglycine esters (Gross, J. Freiberg, Angew Chem 1965, 77, 1022, H. Gross, G. Engelhardt, J. Freiberg, W. Buerger, B. Costisella, Liebigs Ann Chem., 1967, 707, 35-43, R. Kober, W. Steglich, Liebigs Ann. Chem., 1983, 599-609, B. Ku, DY Oh, Tetrahedron Lett., 1988, 29, 4465-4466) direct amination of 2- (diethoxyphosphono) acetates (H. Tadashi (Kyowa Hakko Kogyo Co. Ltd.)) JP 56 034 693 (06.04.1981), Chem. Abstr. 1981, 95, 169435t; EW Colvin, GW Kirby, AC Wilson, Tetrahedron Lett. 1982, 23, 3835-3836), by reduction of diazophosphonoacetates with zinc and acetic acid (Kyowa Hakko Kogyo Co. Ltd., JP 58 10 595 (21.01.1983), Chem. Abstr. 1983, 99, 38633r) or by diazotization of phosphonoacetates with tosyl azide and subsequent catalytic hydrogenation in the presence of Pd / C (H. Tadashi (Kyowa Hakko Kogyo Co. Ltd.)), JP 57 200 396 (08.12.1982), Chem. Abstr. 1983, 99, 38636u; C. Shiraki, H. Saito, K. Takahashi, C. Urakawa, T. Hirata, Synthesis 1988, 399-401).

Alternatively, by reaction of oxalyl carbamates with triethyiphosphite, ethoxyphosphoranes of the type BzOOC-N (Bz) -C (COOR) = P (OEt) ₃ with Me ₃ SiBr or HBr in acetic acid were prepared in phosphonoglycine derivatives (EtO) ₂ P (O) - CH (COOR) -N (Bz) COOBz (R = Et, tBu) (M. Seki, K. Matsumoto, Synthesis 1996, 580-582).

Other multi-step processes for the synthesis of phosphonoglycine derivatives (EtO) ₂ P (O) -CH (NHR) COOR '(R = acyl, H; R' = Me, H) involve the addition of diethyl phosphite to by fumarate ozonolysis and reaction benzylimino-glyoxylic acid esters obtainable with benzylamine (GH Hakimelahi, G. Just, Synth. Commun. 1980, 10, 429-435) and the reaction of benzyl carbamate with methyl glyoxylate or glyoxylic acid / MeOH to form N-benzyloxycarbonyl-α-alkoxyglycine esters, which are subsequently obtained successively reacted with PCl ₃ and triethyl phosphite to (EtO) ₂ P (O) -CH (NHAcyl) COOMe (U. Schmidt, A. Lieberknecht, J. Wild, Synthesis 1984, 53-60) and then with an aqueous piperidine solution (EtO) ₂ P (O) -CH (NHAcyl) COOH (R. Shankar, AI Scott, Tetrahedron Lett. 1993, 34, 231-233).

The synthesis of phosphonoglycine corrosion inhibitors (R ¹ O) ₂ P (O) -CR ² (NR ³ R ⁴ ) -COOH (R ¹ = H, alkyl, R ² = H, alkyl, aryl; R ³ , R ⁴ = H, alkyl, alkylene) is possible only by prolonged heating of amine hydrochloride with glyoxylic acid and H ₃ PO ₄ in the presence of concentrated hydrochloric acid (B. Cook, Ciba-Geigy AG, EP 118395 A2 , 09.12.1984).

One other synthesis route to phosphonoglycine starts from isocyanomethylphosphonic acid diethyl ester, after metallation with potassium tert-butoxide with methyl isocyanate or carbamoyl chlorides is converted to oxazolylphosphonic diesters, then with hydrochloric acid be hydrolyzed (J. Rachon, U. Schöllkopf, Liebigs Ann. Chem. 1981, 1693-1698).

The reactions of ω-aminoalkyl or o-aminoarylphosphines of the type R ² HP⌢NHR ⁴ with aldehydes or ketones to PCN heterocycles (eg K. Issleib, H. Oehme, R. Kümmel, E. Leissring, Chem. Ber. 1968 , 101, 3619-3622; K. Issleib, H. Oehme, E. Leissring, Chem. Ber., 1968, 101, 4032-4035; K. Issleib, H. -U. Brünner, H. Oehme, Organomet. Chem. Synth. 1970/71, 1, 161-168, H. Oehme, R. Thamm, J. Prakt. Chem., 1973, 315, 526-538) represent two-component reactions and are particularly favored by intramolecular ring formation.

Individual representatives of P-oxidized ammonium 2-hydroxy-2-phosphinoylalkanoaten with pentavalent phosphorus, which carries a double bonded oxygen or sulfur atom, were prepared by reacting compounds of the type R ¹ R ² P (O) H with glyoxylic acid, isolation of Reaction product and separate reaction with amines in aqueous solution, followed by a complicated azeotropic removal of the water (K. Bauer, H. Bieringer, H. Burstell, J. Kocur, (Hoechst AG) DE 32 38 958 A1 ; H. Bieringer, K. Albrecht, R. Heinrich, J. Kocur, P. Langelueddeke (Hoechst A.-G.) DE 39 31 051 A1 , The formation of the free 2-hydroxy-2-phosphinoylalkanoic acids R ¹ R ² P (X) CR '(OH) COOH from R ¹ R ² P (X) H and α-ketocarboxylic acids is also possible under mild conditions (X = O: AN Pudovik, IV Gur'yanova, MG Zimin, OE Raevskaya, MA Shakirova, A. Kh. Miftakhova, VF Toropova, Zh. Obshch. Khim. 1971, 41, 1222-1227; X = S: JR Goerlich, R. Schmutzler, Phosphorus, Sulfur, Silicon and Rel. El. 1995, 101, 213-220), but stoichiometric reactions with amines or the synthesis of the ammonium salts are not known.

Saponification of P-oxidized 2-hydroxy-2-phosphinoalkyl esters of R ¹ R ² P (O) H and α-ketocarboxylic acid esters to R ¹ R ² P (O) CR '(OH) COOH (JA Mikroyannidis, Phosphorus, Sulfur 1987, 32, 113-118) is complicated, but allows the kinetic separation of enantiomers by means of lipases (D. Wullbrandt, R. Keller, M. Schlingmann, W. Holla, M. Schneider (Hoechst A.-G.), DE 37 27 243 A1 ). For the extraction of ammonium salts, the method was not used.

Three-component reactions of compounds of the type R ² R ³ P (O) H with aldehydes or ketones and amines (Kabachnik-Fields reaction) to PCN compounds have been known since 1952 (MI Kabachnik, TY Medved, Dokl. Akad. Nauk SSSR 1952, 83, 689-92; EK Fields, J. Am. Chem. Soc 1952, 74, 1528-31; for recent review, see BVP Kuhkar, HR Hudson (Eds.), Aminophosphonic and Aminophosphinic Acids, Wiley 2000 (monograph); RA Cherkasov, VI Galkin, Russ. Chem. Rev. 1998, 67, 857-882).

For phosphines of the type R ² R ³ PH, however, such three-component reactions are hitherto restricted to formaldehyde (for review, see, for example, BA Arbuzov, GN Nikonov, Adv. Heterocycl Chem, 1994, 61, 59-140, K. Kellner, A. Tzschach, Z. Chem., 1984, 24, 365-375; D. Redmore, Topics in Phosphorus Chemistry 1976, 8, 515-585; recent work, for example, DE Berning, KV Katty, CL Barnes, WA Volkert, J. Am. Chem. Soc., 1999 . 121, 1658-1664; JGE Krauter, M. Beller, Tetrahedron 2000, 56, 771-774; AA Karasik, I. 0. Georgiev, OG Sinyashin, E. Hey-Hawkins, Polyhedron 2000, 19, 1455-1459; AA Karasik, IO Georgiev, EI Musina, OG Sinyashin, J. Heinicke, Polyhedron, 2001, 20, 3321-3331). Obviously, aldehydes and ketones are not sufficiently reactive or the products are not sufficiently stable under the required condensation conditions. Metal catalysts with P, O-hybrid ligands can, for example, allow the oligo- and polymerization of ethylene and α-olefins or the Cooligo- or copolymerization of their mixtures.

Diphenylphosphinoacetic acid nickel catalysts A (RS Bauer, H. Chung, PW Glockner, W. Keim, H. van Zwet (Shell), US 3,635,937 (01.18.1972), US 3,644,563 , (22.02.1972); RS Bauer, PW Glockner, W. Keim, RF Mason (Shell), US 3,647,915 (07.03.1972); RF Mason (Shell), US 3,686,351 (08.22.1972); Reviews: W. Keim, J. Mol. Catal. 1989, 52, 19-25; W. germ, vysokomol. Soedin., Ser. A 1994, 36, 1644-1652) and related catalysts B prepared in situ from acyl-P-ylides and nickel compounds (R. Bauer, H. Chung, KW Barnett, PW Glockner, W. Keim (Shell) US 3,686,159 (22.08.1972) or one-component phosphinoenolate nickel catalysts C with R ¹ ₂ P-CHR ² -C (O) R ³ ligands (W.Keim, FH Kowaldt, R. Goddard, C. Krüger, Angew. Chem., 1978, 90, 493; W. Keim, A. Behr, B. Gruber, B. Hoffmann, FH Kowaldt, U. Kürschner, B. Limbäcker, FP Sistig, Organometallics 1986, 5, 2356-2359; Reviews: W Chem., 1990, 102, 251-260; KA Ostoja-Starzewski, J. Witte, Angew. Chem., 1985, 97, 610-612; KA Ostoja-Starzewski, J. Witte, Angew. Chem., 1987 99, 76-77; GA Nesterov, VA Zakharov, G. Fink, W. Fenzl, J. Mol. Catal. 1991, 69, 129-136, J. Pietsch, P. Braunstein, Y. Chauvin, New J. Chem., 1998, 467-472, VC Gibson, A. Tomov, Chem., Commun., 2001, 1964-1965, W. Liu, JM Malinoski, M. Brookhart, Organometallics 2002, 21, 2836-2838, and cit. ) were or are used industrially for the production of ethylene oligomers. In order to achieve water solubility and oligomerization or polymerization even in polar solvents, an SO ₃ ^- group has been introduced for R ² or R ³ (DL Beach, JJ Harrison (Gulf Res. Dev.), US 4,293,502 (06.10.1981), US 4,293,727 (06.10.1981), US 4,310,716 (12.01.1982), US 4,382,153 (03.05.1983), US 4,507,247 (26.03.1985); YV Kissin, DL Beach, J. Polym. Sci., Polym. Chem. Ed. 1984, 22, 333; U. Klabunde, SD Ittel, J. Mol. Catal. 1987, 41, 123-134; U. Klabunde, R. Muelhaupt, T. Herskovitz, AH Janowicz, J. Calabrese, SD Ittel, J. Polym. Sci. Part A: Polym. Chem. 1987, 25, 1989-2003; YV Kissin, J. Polym. Sci. Part A: Polym. Chem. 1989, 27, 147; S. Mecking, Chem. Commun. 2000, 301-302).

Emulsion polymerizations of ethene with the catalysts C, R ² or R ³ = SO ₃ ^- Na ⁺ , SO ₃ ^- C ₁₆ H ₃₃ NMe ₃ ⁺ , in toluene-water, prepared from B and Ni (COD) ₂ , have recently been reported ( A. Tomov, R. Spitz, T. Saudemont, X. Drujon (Elf Atochem) FR Appl 12 476 (06.10.1988), R. Soula, C. Novat, A. Tomov, R. Spitz, J. Claverie , X. Drujon, J. Malinge, Macromolecules 2001, 34, 2022-2026; MO Kristen, L. Manders, S. Mecking, FM Bauer, DE 199 61 340 A1 (17.12.1999); S. Mecking, Chem. Commun. 2000, 301-302; FM Bauer, S. Mecking, Macromolecules 2001, 34, 1165-1171).

Claims for the use of one-component type C catalysts with NR _n H _4-n ⁺ groups have also been filed (U. Klabunde, (DuPont) US 4,698,403 (06.10.1987), US 4,716,025 (29.12.1987); MO Kristen, L. Manders, S. Mecking, FM Bauer, DE 199 61 340 A1 , 17.12. 1999). The copolymerization of ethylene with norbornene-like monomers, as also in the DE 199 61 340 A1 is also mentioned in the WO 03/031485 A2 addressed. In the context of this international patent application, P, O-chelate complexes are used as catalysts, with phosphinocarboxylates or phosphionecarboxylic esters being mentioned as special compounds.

It However, there was a need for further catalysts based on of 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives or 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives. These should catalytically consider the previously known compounds and above Be easier to produce.

The invention therefore an object of the invention, 2-amino or 2-hydroxy-2-phosphinoalkansäure derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives and a process for preparing these compounds, which allows a simple and direct synthesis and be carried out as a one-pot reaction can provide, as well as the corresponding nickel complexes.

wobei
A gleich -⁺NHR⁴R⁵ (Typ 1)
oder -OH (mit ⁺NH₂R⁴R⁵ als Gegenion: Typ 2) ist,
X aus der Gruppe
-C((COO^–)(OH)R¹) (Typ 3, wenn A = -OH ist und mit ⁺NH₂R⁴R⁵ als Gegenion),
freies Elektronenpaar (kein Substituent) und Borverbindung BR₃
ausgewählt ist, wobei die Borverbindung aus der Gruppe von BH₃, B(Alkyl)₃, B(Aryl)₃ und B(Perfluoraryl)₃ ausgewählt ist,
R¹ ein Wasserstoffatom oder
einen C₁-C₁₂-Alkylrest oder
einen C₆-C₁₄-Arylrest bedeutet,
R², R³, R⁴ und R⁵ unabhängig voneinander für
Wasserstoff,
C₁-C₁₂-n-Alkylgruppen,
C₁-C₁₂-verzweigte Alkylgruppen,
C₃-C₁₂-Cycloalkylgruppen,
C₁-C₁₂-Alkoxygruppen,
C₁-C₁₂-Alkenylgruppen,
C₇-C₂₀-Arylalkylgruppen,
C₆-C₁₄-Arylgruppen,
C₆-C₁₄-Arylgruppen, die gleich oder unterschiedlich substituiert sind durch eine oder mehrere
C₁-C₁₂-Alkylgruppen, C₁-C₁₂-Alkoxygruppen oder Halogene,
oder
OR⁶ oder
NR⁶R⁷
stehen,
wobei zwei der Reste R² und R³ oder R⁴ und R⁵ gegebenenfalls miteinander einen gesättigten oder ungesättigten Ring bilden,
R⁶ und R⁷ unabhängig voneinander aus
Wasserstoff,
C₁-C₁₂-Alkylgruppen,
C₆-C₁₄-Arylgruppen,
C₇-C₂₀-Arylalkylgruppen ausgewählt werden,
und gegebenenfalls miteinander einen gesättigten
oder ungesättigten Ring bilden.According to the invention, the object is achieved by the preparation of 2-amino- or 2-hydroxy-2-phosphinoalkanoic acid derivatives (X = no substituent, BR ₃ ) or 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of the general formulas I,

in which
A equals - ⁺ NHR ⁴ R ⁵ (Type 1)
or -OH (with ⁺ NH ₂ R ⁴ R ⁵ as counterion: type 2),
X from the group
-C ((COO ^- ) (OH) R ¹ ) (Type 3, when A = -OH and with ⁺ NH ₂ R ⁴ R ⁵ as counterion),
free electron pair (no substituent) and boron compound BR ₃
wherein the boron compound is selected from the group of BH ₃ , B (alkyl) ₃ , B (aryl) ₃ and B (perfluoroaryl) ₃ ,
R ^{1 is} a hydrogen atom or
a C ₁ -C ₁₂ alkyl radical or
a C ₆ -C ₁₄ -aryl radical,
R ² , R ³ , R ⁴ and R ⁵ are each independently
Hydrogen,
C ₁ -C ₁₂ -n-alkyl groups,
C ₁ -C ₁₂ branched alkyl groups,
C ₃ -C ₁₂ cycloalkyl groups,
C ₁ -C ₁₂ alkoxy groups,
C ₁ -C ₁₂ alkenyl groups,
C ₇ -C ₂₀ arylalkyl groups,
C ₆ -C ₁₄ aryl groups,
C ₆ -C ₁₄ aryl groups which are the same or different substituted by one or more
C ₁ -C ₁₂ -alkyl groups, C ₁ -C ₁₂ -alkoxy groups or halogens,
or
OR ⁶ or
NR ⁶ R ⁷
stand,
where two of the radicals R ² and R ³ or R ⁴ and R ⁵ optionally together form a saturated or unsaturated ring,
R ⁶ and R ^{7 are} independent of each other
Hydrogen,
C ₁ -C ₁₂ -alkyl groups,
C ₆ -C ₁₄ aryl groups,
C ₇ -C ₂₀ -arylalkyl groups are selected,
and optionally a saturated one another
or form unsaturated ring.

In these derivatives, it is preferable that the group R ^{1 is} selected from the group of hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl. It is particularly preferred if the radical R ^{1 represents} a hydrogen atom or a methyl radical.

wobei die Reste X und R¹ bis R⁵ und R⁶, R⁷ die in der allgemeinen Formel I und im weiterführenden Text angegebene Bedeutung haben.For the substituents 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, ethylpropyl, cyclohexyl, methoxy, ethoxy, propoxy, tert-butoxy, phenyl, and benzyl radical, said aryl radicals may also be further substituted. In the case that the radicals R ² to R ^{5 represent} substituted aryl groups, methyl, ethyl, tert-butyl, methoxy or ethoxy radicals are preferred for the further substituents. For halogens as substituents, fluorine, chlorine and bromine are preferred. Particularly preferred radicals on the substi 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 radicals. In this sense, R ⁶ and R ⁷ radicals from the group of hydrogen atom, methyl, ethyl, propyl, tert-butyl, cyclohexyl, phenyl, benzyl or tolyl are preferred. Particularly preferred as the radical R ⁶ , R ⁷ is a hydrogen atom or a methyl, ethyl or tert-butyl radical. In the following, the 2-amino- or 2-hydroxy-2-phosphinoalkanoic acid derivatives (X = no substituent, BR ₃ ) of the type 1 and 2 or 2-phos- phoniobis (2-hydroxyalkanoic acid) derivatives of the type 3 are once again individually displayed,

where the radicals X and R ¹ to R ⁵ and R ⁶ , R ^{7 have} the meaning given in the general formula I and in the continuative text.

According to the invention it is preferred if the boron compound BR _{3 is selected} from the group of BH ₃ and boron triphenyl.

The 2-amino and 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1 and 2 with X = no substituent and X = BR ₃ and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of type 3 are not yet known and extend the range and thus the application potential of the synthetic α-amino acids or α-hydroxyalkanoic acids. They naturally have completely different properties than the compounds mentioned in the introductory text.

The Compounds of the invention have no double-bonded radical X on the phosphorus. Therefore owns the phosphorus in these compounds as opposed to the compounds, which have a double-bonded radical on the phosphorus, directly or after cleavage of the radical X is a lone pair of electrons and nucleophilic.

The presence of trivalent phosphorus in 2-amino and 2-hydroxy-2-phosphinoalkanoic acid derivatives of types 1 and 2 (X = no substituent, BR ₃ ) or the facile formation of type 2 (X = no substituent, BR ₃ ) from the phosphonium salts of type 3 allows on the one hand simple oxidation reactions with H ₂ O ₂ to 2-hydroxy-2-phosphinoylalkanoic acid derivatives 2 (X = O), which could be of interest by biocidal effects (see above). On the other hand, a comparatively stable binding of "soft" transition metals directly on the phosphorus is possible. Outside the scope of the valid claims, it would be conceivable to trigger biocidal effects by influencing transition-metal-dependent enzymes, for example. Furthermore, it would be conceivable that the comparatively stable bond could be used specifically for the transport of metals in biosystems and potentially with radioactive metals for radiodiagnostic or therapeutic purposes, but also for the preparation of novel water-soluble catalysts with chiral P- or P, O-hybrid ligands. The water solubility of the ligands and catalysts, wherein only the nickel complexes are within the scope of the current claims with respect to the catalysts, is effected by the ammonium or hydroxyl and carboxylate groups. In addition, the NH- or the OH function, for example via amide or ester formation, offers the possibility of binding to radicals which further increase the water solubility or allow the recovery of heterogenized catalysts.

Another object of the present invention is a process for the preparation of the inventive 2-amino and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of general formula I, wherein the radicals A, X and R ¹ to R ^{7 have} the meaning given in the text below, by reaction of an α-ketocarboxylic acid R ¹ C (O) -COOH or its hydrate or its acetal with a phosphine 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 is BR ₃ - reaction of the product obtained with B ₂ H ₆ , a BH ₃ adduct or an organoborane.

The processes for preparing the compounds of the invention of types 1, 2 and 3 are fundamentally different from the processes for the preparation of the compounds listed closest thereto. Remotely related syntheses according to the invention have significant differences in conditions and (multistage) reaction regime. The inventive reactions of R ² R ³ PH and amines or silylamines with α-ketocarboxylic acids at room temperature to isolable 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1 or 2 (X = no substituent, BR ₃ ) or 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of type 3 were therefore surprising.

to execution the synthesis of the 2-amino and 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1 or 2 (X = no substituent) or 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives 3 of three components is preferably first prepared a solution of two components and with a solution implemented the third component.

A solution or mixture of the phosphine component R ² R ³ PH with an amine component R ⁴ R ⁵ NH or R ⁴ R ⁵ NSiAlkyl ₃ with an α-ketocarboxylic acid R ¹ C (O) -COOH or its hydrate or its acetal for the preparation of 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1 or 2 (X = no substituent) or reacted 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of the type 3.

It is likewise preferred to use a phosphine component R ² R ³ PH with a solution or mixture of an amine component R ⁴ R ⁵ NH or R ⁴ R ⁵ NSiAlkyl ₃ and an α-ketocarboxylic acid R ¹ C (O) -COOH or its hydrate or its acetal or an ammonium salt or condensation product formed from the amine component and the α-ketocarboxylic acid for the preparation of 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives of the type 1 or 2 (X = no substituent) or 2-phosphoniobis (2) hydroxyalkanoic acid) type 3 derivatives.

Another preferred variant for the preparation of 2-amino or 2-hydroxy-2-phosphinoalkansäu Type I or 2 (X = no substituent) derivatives or type 2 2-phosphoniobis (2-hydroxyalkanoic) derivates include the reaction of an amine component R ⁴ R ⁵ NH or R ⁴ R ⁵ NSiAlkyl ₃ with a solution or Mixture of a phosphine component R ² R ³ PH and an α-ketocarboxylic acid R ¹ C (O) -COOH or its hydrate or its acetal or a phosphonium salt or condensation product formed from the phosphine component and the α-ketocarboxylic acid.

The reaction takes place at a temperature between 0 ° C and the boiling point of the solvent, preferably at room temperature. The solvents used are polar solvents, preferably dialkyl ethers, alkylaryl ethers, alcohols, esters of carboxylic acids, phosphoric 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 or unsaturated hydrocarbons , Particularly preferred are di-n-alkyl ethers. 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, more preferred are secondary amines and bulky substituted primary amines. Instead of the NH components corresponding silylamines can be used. Preferred α-ketocarboxylic acid derivatives are derivatives of glyoxylic acid, pyruvic acid, phenylglyoxylic acid or oxomalonic acid, particularly preferred is glyoxylic acid hydrate. Optionally, a water-binding aid is used. Preferably activated molecular sieve A3 or A4 or in the respective solvent insoluble water-binding salts of main group metals such as Mg (ClO ₄ ) ₂ , MgSO ₄ or CaCl ₂ , wherein the desiccant is eg in a filter candle, which dips into the solution. Alternatively, water of reaction is dragged by boiling solvent into an extraction vessel filled with the desiccant (eg, Soxhlett apparatus, etc.) or azeotropically removed.

If X is BR ₃ , further reaction of the product obtained is carried out with B ₂ H ₆ , a BH ₃ adduct or an organoborane. The BH ₃ adduct is preferably of the BH ₃ donor type (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 selected from the group of B (alkyl) ₃ , B (aryl) ₃ and B (perfluoroaryl) ₃ , more preferably boron triphenyl.

The Reaction may be before or after isolation of 1 or 2 (X = no substituent) or 3 take place from the reaction mixture of the three-component reaction. Preferably, the reactions are carried out immediately after separation and Washing the precipitate of 1 or 2 or 3 from the three-component reaction, before purification tests by recrystallization. As a solvent serve polar aprotic solvents, preferably dialkyl ethers or arylalkyl ethers, particularly preferred cyclic dialkyl ethers such as THF or dioxane. The reactions will be in the temperature range from -80 ° C to Boiling point of the solvent performed, preferably between 0 and 80 ° C, especially preferred at 15-25 ° C.

The 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives of the invention of type 1 or 2 (X = no substituent, BR ₃ ) or phosphoniobis (2-hydroxyalkanoic acid) derivatives of the type 3 can be used for the preparation of 2-hydroxy 2-phosphinoylalkanoic acid derivatives of type 2 (X = O) can be used. These are the 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1 or 2 (X = no substituent, BR ₃ ) or 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of the type 3, as a crude product or in pure form, reacted with aqueous H ₂ O ₂ solution.

• – dass 2-Amino- oder 2-Hydroxy-2-phosphinoalkansäure-Derivate der allgemeinen Formeln I des Typs 1 oder 2 (X = kein Substituent, BR₃) bzw. 2-Phosphoniobis(2-hydroxyalkansäure)-Derivate des Typs 3 durch Reaktion einer α-Ketocarbonsäure R¹C(O)-COOH oder deren Hydrat oder deren Acetal mit einer Phosphinkomponente R²R³PH und einer Aminkomponente R⁴R⁵NH bzw. R⁴R⁵NSiAlkyl₃ in einem geeigneten Lösungsmittel erhalten werden,
• – dass in Abhängigkeit von den Substituenten und Reaktionsbedingungen meist eine der genannten Verbindungen stark bevorzugt gebildet wird,
• – dass 2-Amino- oder 2-Hydroxy-2-phosphinoalkansäure-Derivate vom Typ 1 oder 2 mit X = BR₃ aus vorstehenden Rohprodukten des Typs 1 oder 2 (X = kein Substituent) bzw. 2-Phosphoniobis(2-hydroxyalkansäure)-Derivaten des Typs 3, vor (Eintopfreaktion) oder nach deren Isolierung, durch Zugabe von BR₃ oder BR₃-Addukten (mit Alk₂S oder THF oder R₃N oder N-Heterocyclen) erhalten werden,
• – dass die zwitterionischen Verbindungen des Typs 1 und 3 aufgrund ihrer geringen Löslichkeit in geeigneten aprotischen Lösungsmitteln wie z.B. Diethylether direkt ausfallen und leicht von nicht umgesetzten Ausgangsstoffen oder Nebenprodukten abgetrennt werden können,
• – dass die Ammonium-2-hydroxy-2-phosphinoalkanoate vom Typ 2 (X = BR₃) durch die Salzform im Gegensatz zu eventuell in Abwesenheit von Aminen gebildeten freien 2-Hydroxy-2-phosphinoalkansäuren aus dem Reaktionsgemisch direkt ausfallen und leicht abtrennbar sind,
• – dass 2-Amino- und 2-Hydroxy-2-phosphinoalkansäure-Derivate vom Typ 1 und 2 (X = kein Substituent) in isolierter Form unter Luft- und Wasserausschluss für Lagerung und Anwendungen ausreichend stabil sind,
• – dass Ammonium-2-phosphoniobis-2-hydroxyalkanoate des Typs 3 in isolierter Form unter Wasserausschluss für Lagerung und Anwendungen ausreichend stabil sind,
• – dass die zwitterionischen Verbindungen des Typs 1 (X = kein Substituent) sich beim mäßigen Erhitzen ( > 70–100°C) sowie in aprotisch-polaren (z.B. THF) und besonders in leicht polarisierbaren halogenhaltigen Lösungsmitteln (z.B. CHCl₃) schon bei Raumtemperatur zersetzen können,
• – dass die zwitterionischen Verbindungen vom Typ 1 (X = kein Substituent) und 3 in Wasser und Alkoholen Protolyse bzw. Alkoholyse zu Organoammoniumsalzen von 2-Hydroxy- oder 2-Alkoxy-phosphinoalkansäuren eingehen können,
• – dass 2-Amino- und 2-Hydroxy-2-phosphinoalkansäure-Derivate vom Typ 1 oder 2 mit X = BR₃, insbesondere BH₃ und BPh₃, an Luft und in Lösungsmitteln wie CHCl₃ stabil sind,
• – dass die 2-Amino- oder 2-Hydroxy-2-phosphinoalkansäure-Derivate des Typs 1 oder 2 (X = kein Substituent, BR₃) bzw. Phosphoniobis(2-hydroxyalkansäure)-Derivaten des Typs 3 als Rohprodukt oder in reiner Form, mit H₂O₂- zu 2-Hydroxy-2-phosphinoylalkansäure-Derivaten des Typs 2 (X = O) umgesetzt werden können.

It was found,

• - That 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives of the general formulas I type 1 or 2 (X = no substituent, BR ₃ ) or 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of the type 3 by Reaction of an α-ketocarboxylic acid R ¹ C (O) -COOH 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 are obtained} in a suitable solvent,
• That, depending on the substituents and reaction conditions, one of the compounds mentioned is usually formed with great preference,
• That 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1 or 2 with X = BR ₃ from above crude products of type 1 or 2 (X = no substituent) or 2-phosphoniobis (2-hydroxyalkanoic acid) Type 3 derivatives, before (one-pot reaction) or after their isolation, by the addition of BR ₃ or BR ₃ adducts (with Alk ₂ S or THF or R ₃ N or N-heterocycles),
• That the zwitterionic compounds of type 1 and 3, due to their low solubility in suitable aprotic solvents such as diethyl ether, precipitate directly and can easily be separated from unreacted starting materials or by-products,
• - That the ammonium 2-hydroxy-2-phosphinoalkanoate type 2 (X = BR ₃ ) by the salt form in contrast to possibly formed in the absence of amines free 2-hydroxy-2-phosphinoalkansäuren precipitate directly from the reaction mixture and are easily separated .
• - that 2-amino and 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1 and 2 (X = no substituent) are sufficiently stable in isolated form with exclusion of air and water for storage and applications,
• That ammonium-2-phosphoniobis-2-hydroxyalkanoates of type 3 in isolated form are sufficiently stable with exclusion of water for storage and applications,
• - That the zwitterionic compounds of type 1 (X = no substituent) at moderate heating (> 70-100 ° C) and in aprotic polar (eg THF) and especially in easily polarizable halogenated solvents (eg CHCl ₃ ) even at room temperature can decompose,
• That the zwitterionic compounds of type 1 (X = no substituent) and 3 in water and alcohols can undergo protolysis or alcoholysis to give organoammonium salts of 2-hydroxy- or 2-alkoxy-phosphinoalkanoic acids,
• That 2-amino and 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1 or 2 with X = BR ₃ , in particular BH ₃ and BPh ₃ , are stable in air and in solvents such as CHCl ₃ ,
• - That the 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1 or 2 (X = no substituent, BR ₃ ) or phosphoniobis (2-hydroxyalkanoic acid) derivatives of type 3 as a crude product or in pure form , with H ₂ O ₂ - to 2-hydroxy-2-phosphinoylalkansäure derivatives of type 2 (X = O) can be implemented.

• – Verbindungen liefern, die biocide Eigenschaften besitzen können,
• – Verbindungen liefern, die als Vorstufen für die Synthese biocid wirksamer Verbindungen dienen könnten,
• – Verbindungen liefern, die mit wässrigem H₂O₂ zu 2-Hydroxy-2-phosphinoylalkansäure-Derivaten 2 mit fünfwertigem Phosphor (X = O) umgesetzt werden,
• – Verbindungen liefern, die wasserlösliche Übergangsmetallkomplexe für biochemische oder medizinische Anwendungen bilden, wobei dies außerhalb des Schutzbereichs der geltenden Ansprüche liegt,
• – Verbindungen liefern, die zusammen mit einer Verbindung eines Metalls der Gruppen 6–10 als Katalysatoren auch in polaren Lösungsmitteln oder in wässrig-organischen Zweiphasen-Systemen angewendet werden könnten, wobei im Schutzbereich der geltenden Ansprüche nur die Nickelverbindungen liegen.

The inventive method can

• - provide compounds that can possess biocidal properties,
• Provide compounds which could serve as precursors for the synthesis of biocidally active compounds,
• Provide compounds which are reacted with aqueous H ₂ O ₂ to form 2-hydroxy-2-phosphinoylalkanoic acid derivatives 2 with pentavalent phosphorus (X = O),
• Provide compounds which form water-soluble transition metal complexes for biochemical or medical applications, which is beyond the scope of the present claims,
• - Provide compounds which could be used together with a compound of a metal of groups 6-10 as catalysts in polar solvents or in aqueous-organic two-phase systems, with the scope of the current claims are only the nickel compounds.

From 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1, 2 (X = no substituent, BR ₃ ) or 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of type 3 with metals of groups 6 Catalysts formed by the periodic table could, for example, allow the oligo- and polymerization of ethylene and α-olefins or the cooligo or copolymerization of their mixtures, which is not within the scope of the valid claims. Oligomers of ethylene or α-olefins are industrially important intermediates which are used, for example, for the production of detergents, branched polymers, solvents, paint finishes, and adhesive raw materials.

The Type of catalysts has a significant influence on the choice of process and design as well as the structure of the products and thus their properties. As a result, new catalysts are of great economic importance.

-postulierte Struktur- wobei Y für ein Komplexfragment M, 1/2 M, ML_n oder 1/2 ML_n steht, M Nickel ist, L ein Ligand und n eine ganze Zahl von 1 bis 6 ist und
wobei
A gleich -⁺NHR⁴R⁵ (Typ 1)
oder -OH (mit ⁺NH₂R⁴R⁵ als Gegenion: Typ 2) ist,
R¹ ein Wasserstoffatom oder
einen C₁-C₁₂-Alkylrest oder
einen C₆-C₁₄-Arylrest bedeutet,
R², R³, R⁴ und R⁵ unabhängig voneinander für
Wasserstoff,
C₁-C₁₂-n-Alkylgruppen,
C₁-C₁₂-verzweigte Alkylgruppen,
C₃-C₁₂-Cycloalkylgruppen,
C₁-C₁₂-Alkoxygruppen,
C₁-C₁₂-Alkenylgruppen,
C₇-C₂₀-Arylalkylgruppen,
C₆-C₁₄-Arylgruppen,
C₆-C₁₄-Arylgruppen, die gleich oder unterschiedlich substituiert sind durch eine oder mehrere
C₁-C₁₂-Alkylgruppen, C₁-C₁₂-Alkoxygruppen oder Halogene,
oder
OR⁶ oder
NR⁶R⁷
stehen,
wobei zwei der Reste R² und R³ oder R⁴ und R⁵ gegebenenfalls miteinander einen gesättigten oder ungesättigten Ring bilden,
R⁶ und R⁷ unabhängig voneinander aus
Wasserstoff,
C₁-C₁₂-Alkylgruppen,
C₆-C₁₄-Arylgruppen,
C₇-C₂₀-Arylalkylgruppen ausgewählt werden,
und gegebenenfalls miteinander einen gesättigten oder ungesättigten Ring bilden.A further subject of the present invention is therefore the use of the 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives according to the invention and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of the general formula I as crude product or in pure form for the preparation of nickel-containing 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives (2-amino and 2-hydroxy-2-phosphinoalkanoate nickel derivatives). The structure of these 2-amino or 2-hydroxy-2-phosphinoalkanoate nickel derivatives probably corresponds to the postulated general formula II,

-postulated structure-where Y is a complex fragment M, 1/2 M, ML _n or 1/2 ML _n , M is nickel, L is a ligand and n is an integer from 1 to 6 and
in which
A equals - ⁺ NHR ⁴ R ⁵ (Type 1)
or -OH (with ⁺ NH ₂ R ⁴ R ⁵ as counterion: type 2),
R ^{1 is} a hydrogen atom or
a C ₁ -C ₁₂ alkyl radical or
a C ₆ -C ₁₄ -aryl radical,
R ² , R ³ , R ⁴ and R ⁵ are each independently
Hydrogen,
C ₁ -C ₁₂ -n-alkyl groups,
C ₁ -C ₁₂ branched alkyl groups,
C ₃ -C ₁₂ cycloalkyl groups,
C ₁ -C ₁₂ alkoxy groups,
C ₁ -C ₁₂ alkenyl groups,
C ₇ -C ₂₀ arylalkyl groups,
C ₆ -C ₁₄ aryl groups,
C ₆ -C ₁₄ aryl groups which are the same or different substituted by one or more
C ₁ -C ₁₂ -alkyl groups, C ₁ -C ₁₂ -alkoxy groups or halogens,
or
OR ⁶ or
NR ⁶ R ⁷
stand,
where two of the radicals R ² and R ³ or R ⁴ and R ⁵ optionally together form a saturated or unsaturated ring,
R ⁶ and R ^{7 are} independent of each other
Hydrogen,
C ₁ -C ₁₂ -alkyl groups,
C ₆ -C ₁₄ aryl groups,
C ₇ -C ₂₀ -arylalkyl groups are selected,
and optionally together form a saturated or unsaturated ring.

The Formula II represents a pure postulate, since the structure of the 2-amino or 2-hydroxy-2-phosphiono-alkanoate-nickel derivatives not yet with sufficient Safety could be determined.

In these nickel complexes, it is preferable that the group R ^{1 is} selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl. It is particularly preferred if the radical R ^{1 represents} a hydrogen atom or a methyl radical. For the 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, ethylpropyl, cyclohexyl, methoxy, ethoxy, propoxy, tert-butoxy, phenyl, and benzyl radical, said aryl radicals may also be further substituted. In the case that the radicals R ² to R ^{5 represent} substituted aryl groups, methyl, ethyl, tert-butyl, methoxy or ethoxy radicals are preferred for the further substituents. For halogens as substituents, 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 radicals. In this sense, R ⁶ and R ⁷ radicals from the group of hydrogen atom, methyl, ethyl, propyl, tert-butyl, cyclohexyl, phenyl, benzyl or tolyl are preferred. Particularly preferred as the radical R ⁶ , R ⁷ is a hydrogen atom or a methyl, ethyl or tert-butyl radical.

As metals, metals from the 6th-10th group of the periodic table are conceivable, whereby above all Ei sen, cobalt, nickel or palladium. The scope of the claims, however, includes only nickel. In the case of iron and cobalt, the oxidation states would be 0, +2 and +3, and for nickel and palladium the oxidation states 0 and +2 would be conceivable. However, the scope of the claims includes only nickel in the oxidation states 0 and +2.

Preferably, n is 1 or 2, and the ligands L are preferably independently selected from the group of
ethylenically unsaturated double bond systems,
CO,
nitrites,
halide
Hydrogen atom,
C ₁ -C ₁₂ -alkyl anions,
Allyl or meta-alanions,
benzyl anions,
C ₆ -C ₁₄ aryl anions,
Phosphines R _x PH _3-x or
Amines R _x NH _{3 -x} ,
where R is a C ₁ -C ₆ -alkyl radical or a C ₆ -C ₁₄ -aryl radical with x = 0, 1, 2, 3,
selected.

The conversion of the metal-free compounds of type 1 or 2 (X = no substituent, BR ₃ ) or of 3, as a crude product or in pure form, in nickel complexes of type 1 or 2 (Y = complex fragment) by reaction with a Nickel compound or a combination of a nickel salt with a reducing or alkylating agent.

Conceivable, but not covered by the scope of the claims would be the selection of compounds of a metal of the group iron, cobalt or palladium. In the case of iron and cobalt, it would be conceivable to use compounds containing the metal in the oxidation state 0, +2 or +3. at Nickel or palladium would be the use of compounds in which the metal is the oxidation state 0 or +2 has, possible. The scope of the claims includes nickel compounds in the oxidation states 0 and +2.

• – Nickel(0)-Verbindungen, ausgewählt aus der Gruppe von Ni(COD)₂ und NiL₄, wobei L für PMe₃, PPh₃, P(OEt)₃, CO) steht.
• – Besondert bevorzugt ist Ni(COD)₂.
• – Bevorzugte Nickelverbindungen sind ebenso ungesättigte Organonickel(II)verbindungen ausgewählt aus der Gruppe von Allylnickelverbindungen, Metallylnickelverbindungen, Nickel-β-diketonate, Diphenylnickel(PMe₃)₂.
• – Bevorzugt sind ebenso Nickelsalze, zusammen mit einem Reduktions- oder Alkylierungsmittel wie z.B. Natriumhydrid (NaH), Kaliumhydrid (KH), Natriumborhydrid (NaBH₄), Zinkborhydrid (Zn(BH₄)₂) oder Triethylsilan (Et₃SiH), Methyllithium (MeLi), Butyllithium (BuLi), Triethylaluminium (AlEt₃) oder Methylaluminoxan (MAO) etc..

Preferred nickel compounds are

• Nickel (0) compounds selected from the group consisting of Ni (COD) ₂ and NiL ₄ , where L is PMe ₃ , PPh ₃ , P (OEt) ₃ , CO).
• - Especially preferred is Ni (COD) ₂ .
• - Preferred nickel compounds are also unsaturated organonickel (II) compounds selected from the group of allyl nickel compounds, Metallylnickelverbindungen, nickel-β-diketonate, diphenylnickel (PMe ₃ ) ₂ .
• Also preferred are 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), methyllithium ( MeLi), butyllithium (BuLi), triethylaluminum (AlEt ₃ ) or methylaluminoxane (MAO) etc.

The Implementation takes place - if necessary excluding 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 Borane or nickel compound.

The conversion of 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives of type 1 or 2 (X - no substituent, BR ₃ ) or 2-phosphoniobis (2-hydroxyalkanoic acid) - derivatives of type 3 in nickel complexes succeed with compounds of nickel in a suitable solvent, optionally in the presence of ethylene or α-olefins, or mixtures thereof.

The molar ratio of the metal-free compound of the type 1, 2 or 3 to the nickel compound may vary from about 1.5: 1 to 1:50, preferably 1.2: 1 to 1: 5, for Ni (0) compounds 1: 1 particularly preferred. Suitable solvents are cyclic ethers such as THF or dioxane, acyclic ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether or dimethoxyethane, ketones such as acetone, amides such as dimethylformamide or dimethylacetamide, aromatic solvents such as toluene or xylenes, olefins such as Hexenes or olefin mixtures, as they arise in the oligomerization. Conditionally suitable are alcohols, for example n-butanol or butynediol, and water and mixtures thereof with the abovementioned organic solvents convey.

It has been found that the metal-free compounds of type 1 or 2 (X = no substituent, BR ₃ ) or 3 form nickel complexes with suitable nickel compounds with color change, for example with solutions of light yellow Ni (1,5-COD) ₂ (COD = Cyclooctadiene) in THF deep yellow complex solutions, which are more stable than the solutions of the ligands 1 (X = no substituent) or the Ni (1,5-COD) ₂ .

More detailed description the properties of the compounds of the invention

The 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives of the types 1 or 2 (X = no substituent) or 2-phosphoniobis (2-X) produced by the process according to the invention from a phosphine component, an amine component and an α-ketocarboxylic acid (2 Hydroxyalkansäure) derivatives of type 3 are suitable for derivatization by adduct or complex formation (X = BR ₃ , Y = M or 1/2 M, ML _n or 1/2 ML _n ) and by oxidation with H ₂ O ₂ to Preparation of 2-hydroxy-2-phosphinoylalkanoic acid derivatives of type 2 (X = O), the derivatives with X = BR ₃ are suitable for the preparation of complexes.

in the Comparison to 2-phosphinoalkanoic acids causes the Aminobzw. the OH group in 2-amino or 2-hydroxy-2-phosphinoalkanoic acid derivatives Type 1 or 2 or 3 significant property changes. Especially is the solubility of ligands and catalysts in polar solvents or water essential higher and could in hydrolysis resistance the catalyst complexes applications in aqueous-organic solvent systems or two-phase catalytic processes. The amino or the OH group can over it addition in addition to the phosphino and carboxylate group or competitively to transition metals coordinate and thus changes in activity and selectivity the nickel catalysts formed here compared to phosphinoacetic acid metal catalysts cause.

The amino group also has considerable influence on the stability and the spectroscopic properties of the compounds. In the crystalline state, the 2-amino-2-phosphinoalkanoic acid derivatives of type 1 (X = no substituent, BR ₃ ) are stable under normal conditions. Crystallization from methanol yields, as observed for monocrystalline Ph ₂ P-CH (NtBuH ₂ ⁺ ) COO ^- · MeOH, a monosolvate with H-bonding to the carboxylate group. On heating, removal of the solvent and at higher temperature, in the case of Ph ₂ P-CH (NtBuH ₂ ⁺ ) COO ^- MeOH between 90 and 140 ° C, thermal decarboxylation (TG / DTA, 5 K / min, peak maximum at 95 ° C. , exothermic). In THF [D ₈ ], slow decomposition occurs with CO ₂ splitting (after 1d at room temperature about 40%, after 7d about 14% residual content). In CDCl ₃ , which can not take over protons, strong decomposition already takes place during the preparation of an NMR sample at room temperature. For the decarboxylation of the compounds under these conditions, similar to phosphinoacetic acids (JA van Doorn, N. Meijboom, J. Chem. Soc. Perkin Trans. II 1989, 1309-1313) could be responsible for the formation of phosphonium structures which compete with the Protonation of the amino group. In the methanolic solution of Ph ₂ P-CH (NtBuH ₂ ⁺ ) COO ^- the alcoholysis product Ph ₂ P-CH (OCD ₃ ) COO ^- tBuNH ₃ ^{+ is} present at equilibrium predominantly (about 70%) at room temperature (and exclusion of air) , In D ₂ O is Ph ₂ solves P-CH (NtBuH ₂ ⁺⁾ COO ^- 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 Air exclusion is stable for a long time. Upon addition of base (NaOD), Ph ₂ P-CH (NtBuH) COO ^- Na ⁺ (about 30-40%) is formed in equilibrium and a small amount of Ph ₂ PD is temporarily formed. On addition of excess tert-butylamine, a mixture is formed Solution of Ph ₂ P-CH (NtBuH) COO ^- tBuNH ₃ ⁺ .

Consisting of Ph ₂ P-CH (NtBuH ₂ ⁺⁾ COO ^- and BH ₃ -THF formed borane adduct Ph ₂ P (BH ₃₎ -CH (NtBuH ₂ ⁺⁾ COO ^- is air-stable and dissolves in _CDCl3 without decomposition. Nevertheless, it is suitable as a procatalyst, probably by displacing the BH ₃ by transition metal fragments from the phosphorus. Transition-metal salts, which have not previously been isolated in pure form, are believed to be stabilized by intramolecular, five-membered chelate complexation and allow catalytic reactions even at elevated temperatures (100 ° C).

following the invention should be explained in more detail by examples, without them limit.

Examples of the preparation of the 2-amino-2-phosphinoalkanoic acid derivatives of type 1

example 1

N-tert-butyl-diphenylphosphinoglycine: To a solution of 1.89 g (10.2 mmol) of diphenylphosphine and 1.07 mL (10.2 mmol) of tert-butylamine in 20 mL of diethyl ether is prepared in an ultrasonic bath solution of Glyoxylic acid hydrate (939 mg, 10.2 mmol) in diethyl ether (10 mL). Immediately a colorless low falls precipitate, 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-butyl-diphenylphosphinoglycine-methanol solvate (characterized by crystal structure analysis). Elemental analysis found: C, 64.86, H, 7.77, N, 3.95; for C ₁₈ H ₂₂ NO ₂ P · CH ₃ OH (347.40) Calc .: C 65.69, H 7.54, N 4.03%. - MS (EI, 70 eV, T = 260 ° C): m / z (%) = 315 (7) [M ⁺ ], 270 (0.5) [M ⁺ -COOH], 187 (43), 186 (68) [Ph ₂ PH ⁺ ], 185 (44), 183 (53), 108 (38), 107 (81), 106 (71), 84 (25), 75 (100). TG / DTG / DTA (15-250 ° C, 5 K / min): mass loss of 95-140 ° C with maximum at 120 ° C and shoulder at 100 ° C, Δm at 140 ° C 22.3% (- MeOH, CO ₂ calc. 21.9%), exothermic peaks 114 ° C (m) and 132 ° C (w) [-CO ₂ ], endothermic peak 125 ° C (st) [-MeOH]. ¹ H NMR (D ₈ -THF, CH-COZY, ref THF δ = 1.72): δ = 0.96 (s, 9H, CMe ₃ ), 3.26 (s, 3H, MeOH), 4 , 12 (d, ² J _PH = 2.7 Hz, 1H, CH), 7.20-7.30 (m, 6H, Ph), 7.50-7.65 (2m, 4H, Ph). ¹³ C NMR (D ₈ -THF, CH-COZY, DEPT 135): δ = 29.40 (CMe ₃ ), 49.8 (MeOH), 52.49 (d, ³ J _PC = 9.4 Hz, CMe ₃ ), 58.26 (d, ¹ J _PC = 12.2 Hz, CH), 128.35 (d, ³ J _PC = 6.3 Hz, m-CH),
128.52 (d, ³ J _PC = 7.3 Hz, m-CH '), 128.89 (or 129, 07, p-CH), 134.37 (d, ² J _PC = 17.8 Hz, o-CH), 135.60 (d, ² J _PC = 21.3 Hz, o-CH), 136.88 (d, ¹ J _PC = 16.5 Hz, iC), 138.13 (d, ¹ J _PC = 18.0 Hz, iC), 176.06 (d, ² J _PC = 13.8 Hz, COO ^- ).
³¹ P { ¹ H} NMR (D ₈ -THF): δ = 3.4. Upon standing, the THF-D ₈ solution decomposes slowly at room temperature with decarboxylation (δ ³¹ P = -15.7).

Example 2

N-tert-butyl-diphenyl-phosphinoglycine · 2-butane: A solution of BH ₃ -SEt ₂ in THF (1.5 mL, 1.5 mmol) at 0 ° C to give N-tert-butyl-diphenylphosphinoglycine (200 mg, 0.576 mmol) dissolved in 10 mL THF. This is followed by strong gas evolution. The mixture is stirred for 1 h at 40 ° C. and overnight at room temperature. The solvent is removed and the residue is washed with hexane. There are 190 mg of white powder (yield 96%), mp 116-118 ° C. - Elemental analysis found: C 63.21, H 8.23, N 4.35; for C ₁₈ H ₂₂ NO ₂ P · 2BH ₃ (343.02) calc .: C 63.03, H 8.23, N 4.08%. ¹ H NMR (CDCl ₃ , ref. CHCl ₃ δ = 7.27): δ = 0.5-3.5 (s br, BH ₃ ), 1.33 (s, 9H, CMe ₃ ), 4, 33 (dd, ² J _PH = 8.2, J = 1.2 Hz, 1H, CH), 5.61 (d, J = 10.5 Hz, 1H, NH or OH), 7.38-7, 55 (m, 4H, Ph), 7.58-7.74 (m, 5H, Ph, OH or NH), 8.19-8.28 (m, 2H, Ph). ¹³ C NMR (CDCl ₃ ):
δ = 25.42 (CMe ₃ ), 56.58 (d, ¹ J _PC = 24.4 Hz, CH), 60.40 (d, ³ J _PC = 3.6 Hz, CMe ₃ ), 123.61 (d, ¹ J _PC = 55.9 Hz, iC _q ), 125.28 ( ¹ J _PC = 63.2 Hz, iC _q '), 128.74 ( ³ J _PC = 11.3 Hz, m-CH ), 129.50 ( ³ J _PC = 11.0 Hz, m-CH '), 132.62 ( ⁴ J _PC = 2.6 Hz, p-CH), 132.71 ( ⁴ J _PC = 2.7 Hz, p-CH '), 133.46 ( ² J _PC = 10.0 Hz, o-CH), 133.84 ( ² J _PC = 10.9 Hz, o-CH'), 169.23 ( ² J _PC = 4.2 Hz, COO). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ = 25.8 (br).

Example of preparation of an ammonium 2-hydroxy-2-phosphinoalkanoate derivative of type 2

Example 3

tert-Butylammonium diphenylphosphinoglycolate: The compound forms upon dissolution of N-tert-butyl-diphenylphosphinoglycine (methanol solvate) in water by hydrolysis. ¹ H NMR (D ₂ O): δ = 1.35 (s, 9H, CMe ₃ ), 3.34 (s, 3H, MeOH), 5.09 (d, ² J _PH = 3.3 Hz, 1H, CH), 7.38-7.45 (m, 6H, Ph), 7.45-7.60 (m, 4H, Ph). ¹³ C NMR (D ₂ O): δ = 24.15, 24.20 (2s, CMe ₃ ), 46.45, 46.47 (2d, J _{P C} = 2.0 Hz, CMe ₃ ), 71 , 07 (d, ¹ J _PC = 23 Hz, CHOH), 126.09 (d, ³ J _PC ≈ 8 Hz, m-CH), 126.18 (d, ³ J _PC = 6.3 Hz, CH '), 126.37, 127.37 (2s, p-CH), 130.23 (d, ² J _{P C} = 17.1 Hz, o-CH), 131.96 (d, ² J _PC = 19.3 Hz, o-CH), 130.72 (d, ¹ J _PC = 10.9 Hz, iC), 132.99 (d, ¹ J _PC = 11.2 Hz, iC), 175.13 ( d, ² J _PC = 8.0 Hz, COO). ³¹ P NMR (D ₂ O): δ = 6.7.

Examples of preparation of the ammonium 2-phosphoniobis (2-hydroxyalkanoate) derivatives of type 3

Example 4

• – Elementaranalyse gef.: C 58,91 (58,71), H 7,14 (6,72), N 3,01 (3,28); für C₂₀H₂₆NO₆P (407,40) ber.: C 58,96, H 6,43, N 3,44.
• – ¹H-NMR (D₂O, CH-COSY): δ = 1,19 (t, ³J_HH = 7,3 Hz, 6H, CH₃), 2,99 (q, ³J_HH = 7,3 Hz, 6H, N⁺CH₂), 5,84 (d, ²J_PH = 7,3 Hz, 1 H, CH_A), 6,00 (d, ²J_PH = 7,7 Hz, 1 H, CH_B), 7,53–7,65 (m, 4H, m-H), 7,68–7,82 (m, 5H, 3 o-H, 2 p-H), 7,85–7,94 (m, 1 H, o-H), N⁺H überlagert durch OH von Solvenz (4,72).
• – ¹³C NMR (D₂O, CH-COSY, DEPT): δ = 10,27, 41,98, 42,08 (N⁺Et), 68,99 (¹J_PC = 56,6 Hz, PCH_A), 69,70 (¹J_PC = 51,3 Hz, PCH_B), 114,93 (¹J_PC = 78,9 Hz, 2 i-C_q), 115,13 (¹J_PC = 77,8 Hz, i-Cq'), 115,51 (¹J_PC = 79,2 Hz, i-Cq'), 129,01 (³J_PC = 12,0 Hz, 2 m-CH'), 129,11 (³J_PC = 11,9 Hz, 4 m-CH), 129,21 (³J_PC = 12,1 Hz, 2 m-CH'), 133,89 (²J_PC = 8,4 Hz, 2 o-CH'), 134,00 (²J_PC = 8,3 Hz, 2 o-CH'), 134,26 (²J_PC = 8,2 Hz, 4 O-CH), 134,39 (⁴J_PC = 3,0 Hz, 2 p-CH), 134,46 (⁴J_PC = 3 Hz, p-CH), 170,74 (COO^–). – ³¹P{¹H}-NMR (D₂O): δ = 27,68, 27,53; Spur 22,87 (Ph₂PHO).

Diethylammonium diphenylphosphonium bis (glycolate): To a solution of 1.00 g (5.37 mmol) of diphenylphosphine and 0.56 mL (5.44 mmol) of diethylamine in 20 mL of diethyl ether is added a solution of glyoxylic acid hydrate (494 mg, 5.37 mmol) in diethyl ether (10 mL). After a few minutes, a colorless precipitate falls out. After standing overnight, it is filtered, washed with a little ether and dried, yield 0.80 g (47%), mp 121-122 ° C. The compound is soluble in methanol, in water, slightly soluble in THF and in CH ₂ Cl ₂ .

• Elemental analysis found: C, 58.91 (58.71), H, 7.14 (6.72), N, 3.01 (3.28); for C ₂₀ H ₂₆ NO ₆ P (407.40) calc .: C, 58.96, H, 6.43, N, 3.44.
• ¹ H-NMR (D ₂ O, CH-COZY): δ = 1.19 (t, ³ J _HH = 7.3 Hz, 6H, CH ₃ ), 2.99 (q, ³ J _HH = 7, 3 Hz, 6H, N ⁺ CH _2), 5.84 (d, ² J _PH = 7.3 Hz, 1 H, CH _A), 6.00 (d, ² J _PH = 7.7 Hz, 1 H , CH _B ), 7.53-7.65 (m, 4H, mH), 7.68-7.82 (m, 5H, 3 oH, 2 pH), 7.85-7.94 (m, 1 H, oH), N ⁺ H overlaid by OH of solvency (4.72).
• ¹³ C NMR (D ₂ O, CH-COZY, DEPT): δ = 10.27, 41.98, 42.08 (N ⁺ Et), 68.99 ( ¹ J _PC = 56.6 Hz, PCH _A ), 69.70 ( ¹ J _PC = 51.3 Hz, PCH _B ), 114.93 ( ¹ J _PC = 78.9 Hz, 2 iC _q ), 115.13 ( ¹ J _PC = 77.8 Hz, i-Cq ') , 115.51 ( ¹ J _PC = 79.2 Hz, i-Cq '), 129.01 ( ³ J _PC = 12.0 Hz, 2 m-CH'), 129.11 ( ³ J _PC = 11, 9 Hz, 4-CH m), 129.21 ⁽³ J _PC = 12.1 Hz, 2 m-CH '), 133.89 ⁽² J _PC = 8.4 Hz, 2 o-CH'), 134 , 00 ( ² J _PC = 8.3 Hz, 2 o -CH '), 134.26 ( ² J _PC = 8.2 Hz, 4 O-CH), 134.39 ( ⁴ J _PC = 3.0 Hz 2 p-CH), 134.46 ⁽⁴ J _PC = 3 Hz, p-CH), 170.74 (COO ^{-). 31} P { ¹ H} -NMR (D ₂ O): δ = 27.68, 27.53; Lane 22,87 (Ph ₂ PHO).

Example 5

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). After a few minutes, a colorless precipitate falls out. After 24 h, filtered, washed with a little ether and dried. Yield: 0.85 g (69%). Elemental analysis found: C 57.45, H 9.23, N 3.20; for C ₂₀ H ₃₈ NO ₆ P (419.50) calc .: C, 57.26, H, 9.13, N, 3.34. ¹ H NMR (D ₂ O + D ₈ -THF): δ = 1.30 (t, ³ J = 7.3 Hz, 6H, CH ₃ ), 1.15-2.10 (m, 20 H, Cy), 2.50-2.80 (m, 2H, Cy), 2.99 (q, ³ J = 7.3 Hz, 4H, NCH ₂ ), 5.14 (d, ¹ J = 8.9 Hz, 1 H, PCH), 5.17 (d, ¹ J = 9.5 Hz, 1 H, PCH). ¹³ C NMR (D ₂ O + D ₈ -THF): δ = 12.23 (CH ₃ ), 26.83 (C-δ), 27.29-28.12 (m, C-γ, C-) β), 31.78 (d, ¹ J = 36.2 Hz, C-α), 32.67 (d, ¹ J = 30.8 Hz, C-α), 43.90, 43.99 (NCH ₂ ), 65.85 (d, ¹ J = 33.5 Hz, PCH), 66.49 (d, ¹ J = 33.7 Hz, PCH), 173.58 (COO ^- ). In D ₂ O 2 signal sets: ¹ H NMR (D ₂ O): δ = 1.20 (t, ³ J = 7.3 Hz, 6H, CH ₃ ), 1.15-2.10 (m, 20 H, Cy), 2.50-2.80 (m, 2H, Cy), 2.99 (q, ³ J = 7.3 Hz, 4H, NCH ₂ ), 5.17 (d, ¹ J = 9 , 3 Hz, 1 H, PCH _A ), 5.19 (d, ¹ J = 9.9 Hz, 1 H, PCH _B ). ³¹ P NMR (D ₂ O): δ = 33.19 (A), 34.04 (B) (A> B, A ca. 2B).

Example 6

Diethylammonium di-tert-butylphosphonium bis (glycolate): To a solution of 1.77 g (12.11 mmol) of di-tert-butylphosphine and 1.25 mL (12.11 mmol) of diethylamine in 20 mL of diethyl ether Add a solution of glyoxylic acid hydrate (1.114 g, 12.11 mmol) in diethyl ether (10 mL) prepared in an ultrasonic bath. After a few minutes, a colorless, sticky precipitate falls out. After 24 h, it is filtered, washed with a little ether and n-hexane and dried, yield 2.5 g (75%), soluble in H ₂ O (D ₂ O), THF, CDCl ₃ .

Elemental analysis found: C, 48.44 (48.25), H, 9.04 (8.50), N, 2.95 (2.94); for mixture C ₁₆ H ₃₄ NO ₆ P · H ₂ O (80%) + tBu ₂ P (CH ₃ COO) ₂ H · H ₂ O (20%) calc .: C, 49.12, H, 9.14, N 2.90. - tBu ₂ P ⁺ [CH (OH) -COO ^- ] ₂ Et ₂ NH ₂ ⁺ : ¹ H NMR (CDCl ₃ ): δ = 1.28 (t, ³ J = 7.2 Hz, 6H, CH ₃ ) , 1.63 (d, ³ J _PH = 14.6 Hz, 18 H, CMe ₃ ), 3.03 (br, 4H, NCH ₂ ), 5.63 (d, ² J _PH = 6.8 Hz, 2H, CH), 5.85 (br, 2H, OH), 9.21 (br, 2H, NH ₂ ⁺ ). ¹³ C NMR (CDCl ₃ ): δ = 11.23 (CH ₃ ), 28.61 (CMe ₃ ), 37.70 (d, ¹ J = 26.6 Hz, CMe ₃ ), 42.20 (NCH ₂ ), 67.43 (d, ¹ J = 39.0 Hz, CH), 170.33 (COO ^- ). ³¹ P NMR (CDCl ₃ ): δ = 30.74.

Examples of Oxidation of Type 2 2-Amino-2-Phosphinoalkanoic Acid Derivatives and Type 2 Ammonium 2-Phosphoniobis (2-Hydroxyalkanoate) Derivatives with H ₂ O ₂ to Type 2 2-Hydroxy-2-Phosphinoylalkanoic Acid Derivatives (X = O)

Example 7

tert-Butylammonium diphenylphosphinoyl glycolate: To a solution of 0.379 g (1.203 mmol) of 2-tert-N-tert-butyl-diphenylphosphinoglycine (from Example 1) in 20 mL of a mixture of H ₂ O and THF (2: 1) at 0 ° C 0.122 ml H ₂ O ₂ (30%) added. 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. Elemental analysis found: C, 61.43, H, 6.62, N, 4.06; for C ₁₈ H ₂₄ NO ₄ P (349.37) Calc .: C 61.88, H 6.92, N 4.01. ¹ H NMR (CDCl ₃ ): δ = 1.18 (s, 9H, CMe ₃ ), 4.79 (d, ² J _PH = 4.1 Hz, 1 H, CH), 7.34-7, 50 (m, 6H, Ph), 7.80-7.90 (m, 4H, Ph), 8.2 (vbr, 3H, OH, NH ₂ ⁺ ); ¹ H NMR (D ₂ O): δ = 1.22 (s, 9H, CMe ₃ ), 4.96 (d, ² J _PH = 6.1 Hz, 1 H, CH), 7.35-7, 45 (m, 4H, Ph), 7.45-7.53 (m, 2H, Hp), 7.60-7.72 (m, 4H, Ph). ¹³ C NMR (D ₂ O, THF): δ = 28.34 (CMe ₃ ), 53.58 (d, ³ J = 6.1 Hz, CMe ₃ ), 73.34 (d, ¹ J = 79 , 2 Hz, CH), 130.49 (d, ³ J = 11.7 Hz, 2 mC), 130.79 (d, ¹ J = 100.9 Hz, iC), 133.04 (d, ² J = 9.3 Hz, oC), 133.14 (d, ² J = 8.9 Hz, oC '), 134.45 (d, ⁴ J = 2.2 Hz, PC), 134.57 ( d, ⁴ J = 2.2 Hz, p-C '), 174.33 (COO). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ = 31.96.

Example 8

Diethylammonium diphenylphosphinoylglycolate semihydrate: Hydrogen peroxide (0.10 mL, 30%, 0.88 mmol) is added dropwise at 20 ° C to a solution of Ph ₂ P ⁺ [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 residual oil is washed with hexane and a little diethyl ether. After drying result 130 mg (98%) of white solid, mp 149.5 ° C. - Elemental analysis found: C 59.7, H 7.16, N 3.88; for C ₁₈ H ₂₄ NO ₄ P · 0.5H ₂ O (358.37) calc .: C 60.33, H 7.03, N 3.91. ¹ H NMR (CDCl ₃ ): δ = 1.10 (br s, 6H, CH ₃ ), 2.85 (br s, 4H, NCH ₂ ), 4.87 (d, ² J _PH = 7.1 Hz, 1 H, CH), 7.35-7.55 (m, 6H, Ph), 7.75-7.80 (m, 4H, Ph), 8.40 (vbr, 5H, 2 H ₂ O , H ⁺ ). ¹³ C NMR (CDCl ₃ ): δ = 11.19 (CH ₃ ), 41.95 (NCH ₂ ), 71.58 (d, ¹ J = 83.8 Hz, CH), 128.19 (d, ³ J = 12.4 Hz, 2 mC), 128.34 (d, ³ J = 12.2 Hz, 2 m-C '), 129.95 (d, ¹ J = 98.2 Hz, iC), 131.66 (d, ² J = 9.3 Hz, oC), 131.71 (d, ² J = 8.9 Hz, o-C '), 131.91 (br, pC), 171.86 ( COOH). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ = 33.1.

Example 9

Diethylammonium dicyclohexylphosphinoylglykolat hydrate: Cy ₂ P ⁺ [CH (OH) -COO ^-] ₂ Et ₂ NH ₂ ⁺ from Example 5 (163 mg, 0.498 mmol) is dissolved in water (10 mL), and at 20 ° C
is added dropwise hydrogen peroxide (0.1 mL, 30%). After stirring for 2-15 hours, the solvent is removed in vacuo. The colorless liquid residue is washed with a little hexane and Et ₂ O and dried in vacuo. The zwitterionic viscous liquid slowly solidifies to 120 mg (70%) of white solid, mp 112-115 ° C. - Elementary analysis found: C 57.31, H 9.87, N 3.19; for C ₁₈ H ₃₆ NO ₄ P · H ₂ O (379.58) calc .: C, 56.96, H, 10.07, N, 3.68. ¹ H NMR (CDCl ₃ ): δ = 1.15-2.20 (m, 22H, cHex), 1.31 (t, ³ J = 7.2 Hz, 6H, CH ₃ ), 3.49 ( q, ³ J = 7.2 Hz, 4H, NCH ₂ ), 4.44 (d, ² J _PH = 8.5 Hz, 1 H, CH), 8.80 (vbr, 5H, H ₂ O, H ⁺ ). ¹³ C NMR (CDCl ₃ ): δ = 11.09 (CH ₃ ), 24.89 (d, J = 2.4 Hz), 25.03 (d, J = 2.4 Hz), 25.41 (d, J = 2.2 Hz), 25.63 (d, J ≈ 2 Hz), 25.80 and 25.87 (2 s) or 25.84 (d, J = 5.2 Hz) (γ- C and δ-C), 26.39 (d, ² J = 12.6 Hz, 2β-C), 26.60 (d, ² J = 12.6 Hz, β-C), 26.68 ( d, ² J = 12.6 Hz, β-C), 34.12 (d, ¹ J = 62.0 Hz, α-C), 34.73 (d, ¹ J = 60.7 Hz, α- C)], 42.18 (NCH ₂ ), 68.26 (d, ¹ J = 68.3 Hz, CH), 174.17 (COOH). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ = 55.2.

Example 10

Diethylammonium 2-di-tert-butylphosphinoylglykolat hydrate: tBu ₂ P ⁺ [CH (OH) -COO ^-] ₂ Et ₂ NH ₂ ⁺ from Example 6 (245 mg, 0.89 mmol) in water (10 mL ), oxidized with excess hydrogen peroxide (0.15 mL, 30%, 1.32 mmol) and worked up as described in the previous example. This results in 200 mg (77%) of white solid, mp 134-136 ° C. - Elementary analysis:
C, 50.46, H, 10.44, N, 4.53; for C ₁₄ H ₃₂ NO ₄ P · H ₂ O (327.40) calc .: C 51.36, H 10.47, N 4.28. ¹ H NMR (CDCl ₃ ): δ = 1.30 (t, ³ J = 7.3 Hz, 6H, CH ₃ ), 1.32 (d, ³ J _PH = 13.6 Hz, 9H, CMe ₃ ), 1.38 (d, ³ J _PH = 13.4 Hz, 9H, CMe ₃ ), 3.05 (q, ³ J = 7.3 Hz, 4H, NCH ₂ ), 4.47 (d, ² J _PH = 9.4Hz, 1H, CH), 8.75 (vbr, 5H, H ₂ O, OH, NH ₂ ⁺ ). ¹³ C NMR (CDCl ₃ ): δ = 11.22 (CH ₃ ), 26.78 (CMe ₃ ), 27.05 (CMe ₃ ), 36.26 (d, ¹ J = 55.5 Hz, CMe ₃ ), 36.86 (d, ¹ J = 53.7 Hz, CMe ₃ ), 41.98 (NCH ₂ ), 69.89 (d, ¹ J = 65.3 Hz, OH), 174.06 ( COOH). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ = 60.83. MS (70 eV, 130 ° C): m / z (%) = 246 (2.5) [M ⁺ -CO ₂ ], 244 (13), 200 (18), 199 (24), 198 (48) , 99 (41), 57 (100).

Examples of preparation the catalysts

Example 11

To a solution of Ni (COD) ₂ (34 mg, 124 μmol) in THF (10 mL) at 0 ° C is a solution of N-tert-butyl-diphenylphosphinoglycine from Example 1 (38 mg, 110 .mu.mol) in THF (10 mL). After stirring for 10 minutes at 0 ° C and 30 minutes at 20 ° C orange mixture is injected into a 75 mL autoclave. Ethylene (30 bar, 8.1 g) is pressurized and the mixture is heated to 100 ° C for 15 hrs. After cooling and check weighing unreacted ethylene is discharged (conversion 85%). Approximately 0.5 g of volatile components are separated by distillation (1.5 Torr, bath to about 150 ° C). The residue is stirred with methanol / hydrochloric acid (1: 1) at room temperature (1d), washed with water and methanol. From the waxy polymer (5.2 g) low molecular weight components are washed out with methylene chloride. After vacuum drying, 4.0 g of polyethylene wax are obtained, mp 113-117 ° C, d = 0.958 g · cm ^-3 . - 1H NMR (in C ₆ D ₅ Br at 100 ° C after swelling at 120 ° C / 15 h): α / internal olefins 93: 7:%, Me / olefin groups 1.5, Me / 1000C 17.5 , average molecular weight (similar to Mn) 1230 g · mol ^-1 .

Example 12

To a solution of Ni (COD) ₂ (32 mg, 135 .mu.mol) in THF (10 mL) at 0 ° C, a solution of N-tert-butyl-diphenylphosphinoglycin · 2Boran from Example 2 (38.5 mg, 112 μmol) 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 (29 bar, 7.6 g) is squeezed and heated to 100 ° C for 15 hrs. After cooling and check weighing unreacted ethylene is discharged (conversion 51%). Volatile constituents are removed by distillation, the residue is stirred with methanol / hydrochloric acid (1: 1) at room temperature (1d), washed with water, methanol and methylene chloride and dried. This gives 3.2 g of polyethylene wax, mp. 119-120 ° C, d = 0.958 g · cm ^-3 . 1H NMR (in C ₆ D ₅ Br at 100 ° C. after swelling at 120 ° C./15 h): α / internal olefins 96: 4:%, Me / olefin 1.5, Me / 1000 ° C 17.7, medium Molar mass 1250 g · mol ^-1 .

Example 13

To a solution of Ni (COD) ₂ (33 mg, 120 μmol) in THF (10 mL) at 0 ° C Et ₂ NH ₂ ⁺ Ph ₂ P ⁺ [CH (OH) -COO-] ₂ from Example 4 ( 38 mg, 120 μmol) in THF (10 mL, not completely dissolved). The mixture is stirred for 10 min. At 0 ° C and 30 min. 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 hrs. After cooling and check weighing unreacted ethylene is discharged (conversion 44%). Volatile components are separated by distillation (1.5 Torr, bath to about 150 ° C). In addition to THF, the distillate contains 3.7 g α-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 (1d), then washed with water and methanol and dried, 1.3 g of wax.

Example 14

To a solution of Ni (COD) ₂ (30 mg, 110 μmol) in THF (10 mL) at 0 ° C is a solution of Et ₂ NH ₂ ⁺ cHex ₂ P ⁺ [CH (OH) -COO-] ₂ from Example 5 (34 mg, 104 .mu.mol) in THF (10 mL) ge, 10 min. At 0 ° C and 30 min. At 20 ° C stirred. The mixture is injected into the autoclave, ethylene (30 bar, 7.3 g) is pressurized and heated to 100 ° C for 15 hrs. Work-up as in Example 11 gives a conversion of 59% and 4.3 g of polyethylene, mp 124-126 ° C, d = 0.961 g · cm ^-3 . 1H NMR (in C ₆ D ₅ Br at 100 ° C. after swelling at 120 ° C./15 h): α / internal olefins> 99: 1:%, Me / olefin 1.2, Me / 1000C 9.4, average molecular weight 1900 g · mol ^-1 .

Example 15

To a solution of Ni (COD) ₂ (29 mg, 106 μmol) in THF (10 mL) at 0 ° C is a solution of Et ₂ NH ₂ ⁺ tBu ₂ P ⁺ [CH (OH) -COO-] ₂ from Example 6 (28 mg, 102 .mu.mol) in THF (10 mL), 10 min. At 0 ° C and 30 min. At 20 ° C stirred. The mixture is injected into the autoclave, ethylene (50 bar, 12.6 g) is pressurized and heated to 100 ° C for 15 hrs. Work-up as in Example 11 gives a conversion of 75% and 9.3 g of polyethylene, mp 129-132 ° C, d = 0.960 g · cm ^-3 . - 1H NMR (in C ₆ D ₅ Br at 100 ° C after swelling at 120 ° C / 15 h): α / internal olefins 97: 3:%, Me / olefin 1.2, Me / 1000C 3.1, medium Molar mass 5350 g · mol ^-1 .

Example 16

To a solution of Ni (COD) ₂ (30 mg, 110 .mu.mol) in 1-hexene (10 mL) at 0 ° C a solution of N-tert-butyl-diphenylphosphinoglycin (38 mg, 110 .mu.mol) and nBu ₄ HCl (27.5 mg, 100 μmol) in H ₂ O (10 mL), stirred at 0 ° C for 10 min and at 20 ° C for 30 min. The mixture (2 phases) is injected into the autoclave, ethylene (50 bar, 10.8 g) is pressurized and heated to 100 ° C for 15 hrs. After cooling and check weighing unreacted ethylene is discharged. Despite poor mixing (magnetic stirrer) partial reaction took place. The white polymer foam on the surface is worked up with MeOH / HCl (3: 1) and yields 1.6 g of wax (15%) mp. 68-70 ° C.

Claims (35)

2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of general formula I,

where A is - ⁺ NHR ⁴ R ⁵ (type 1) or -OH (with ⁺ NH ₂ R ⁴ R ⁵ as counterion: type 2), X is selected from the group -C ((COO ^- ) (OH) R ¹ ) (type 3, when A = -OH and with ⁺ NH ₂ R ⁴ R ⁵ as counterion), lone pair of electrons (no substituent) and a boron compound where the boron compound is selected from the group of BH ₃ , B (alkyl) ₃ , B (aryl) ₃ and B (perfluoroaryl) ₃ , R ^{1 is} a hydrogen atom or a C ₁ -C ₁₂ -alkyl radical or a C ₆ - C ₁₄ aryl radical, R ² , R ³ , R ⁴ and R ⁵ independently of one another are hydrogen, C ₁ -C ₁₂ -n-alkyl groups, C ₁ -C ₁₂ -branched alkyl groups, C ₃ -C ₁₂ -cycloalkyl groups, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkenyl groups, C ₇ -C ₂₀ arylalkyl, C ₆ -C ₁₄ aryl groups, C ₆ -C ₁₄ aryl groups which are substituted identically or differently by one or more C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy groups or halogens or oR ⁶ or NR ⁶ R ^7, wherein two of the radicals R ² and R ³ or R ⁴ and R ⁵ optionally together form a saturated or unsaturated ring, R ⁶ and R ⁷ are independently separately of each other from hydrogen, C ₁ -C ₁₂ alkyl, C ₆ -C ₁₄ aryl groups, C ₇ -C ₂₀ arylalkyl groups are selected, and optionally together form a saturated or unsaturated ring. 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives according to claim 1, characterized in that the radical R ^{1 is} selected from the group of hydrogen atom, methyl, ethyl , Propyl, butyl, pentyl, hexyl and phenyl radicals. 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives according to one of claims 1 or 2, characterized in that the radical R ¹ denotes a hydrogen atom or a methyl radical. 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives according to one of claims 1 to 3, characterized in that the radicals R ² , R ³ , R ⁴ and R ⁵ from the group of hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl, iso-propyl, isobutyl, tert-butyl, ethylpropyl, cyclohexyl, methoxy, ethoxy , Propyloxy, tert-butoxy, phenyl and benzyl are selected, said aryl radicals are optionally further substituted. 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives according to any one of claims 1 to 4, characterized in that the substituted aryl radicals as further substituents methyl, ethyl, tert-butyl, methoxy or ethoxy radicals, or halogens from the group of fluorine, chlorine and bromine. 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives according to any one of claims 1 to 5, characterized in that the radicals on the substituted aryl radicals Methyl or chlorine. 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives according to any one of claims 1 to 6, characterized in that as radicals R ² to R ^{5 are} hydrogen atoms, ethyl, tert.-butyl, cyclohexyl or phenyl radicals are selected. 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives according to any one of claims 1 to 7, characterized in that for R ⁶ and R ⁷ radicals from the group of hydrogen atom, Methyl, ethyl, propyl, tert-butyl, cyclohexyl, phenyl, benzyl and tolyl are selected. 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives according to any one of claims 1 to 8, characterized in that the radicals R ⁶ , R ^{7 are} hydrogen atoms, methyl, ethyl - or tert-butyl radicals are. 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives according to any one of claims 1 to 9, characterized in that X is BH ₃ or borontriphenyl. A process for the preparation of 2-amino- and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of general formula I according to claim 1,

where A is - ⁺ NHR ⁴ R ⁵ (type 1) or -OH (with ⁺ NH ₂ R ⁴ R ⁵ as counterion: type 2), X from the group -C ((COO ^- ) (OH) R ¹ ) (Type 3, when A = -OH and with ⁺ NH ₂ R ⁴ R ⁵ as counterion), lone pair of electrons (no substituent) and a boron compound, wherein the boron compound is selected from the group of BH ₃ , B (alkyl) ₃ , B (aryl) ₃ and B (perfluoroaryl) ₃ , R ^{1 represents} a hydrogen atom or a C ₁ -C ₁₂ alkyl radical or a C ₆ -C ₁₄ aryl radical, R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen, C ₁ -C ₁₂ -n-alkyl groups, C ₁ -C ₁₂ -branched alkyl, C ₃ -C ₁₂ cycloalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkenyl, C ₇ -C ₂₀ -arylalkyl groups, C ₆ -C ₁₄ -aryl groups, C ₆ -C ₁₄ -aryl groups which are identical or different substituted by one or more C ₁ -C ₁₂ -alkyl groups, C ₁ -C ₁₂ -alkoxy groups or halogens, or OR ⁶ or NR ⁶ R ⁷ , wherein two of the radicals R ² and R ³ or R ⁴ and R ⁵ gege optionally together form a saturated or unsaturated ring, R ⁶ and R ^{7 are} independently selected from hydrogen, C ₁ -C ₁₂ alkyl groups, C ₆ -C ₁₄ aryl groups, C ₇ -C ₂₀ arylalkyl groups, and optionally with each other a saturated or unsaturated ring, characterized in that an α-ketocarboxylic acid R ¹ C (O) -COOH 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 _3rd and optionally reacted with a dehydrating auxiliary reagent in a suitable solvent and optionally - if X is BR ₃ - the product obtained is reacted with B ₂ H ₆ , a BH ₃ adduct or an organoborane

A method according to claim 11, characterized in that the radical R ^{1 is selected} from the group of hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl radical. Method according to one of claims 11 or 12, characterized in that the radical R ^{1 represents} a hydrogen atom or a methyl radical. Method according to one of claims 11 to 13, characterized in that the radicals R ² , R ³ , R ⁴ and R ⁵ from the group of hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl, iso Propyl, iso-butyl, tert-butyl, ethylpropyl, cyclohexyl, methoxy, ethoxy, propyloxy, tert-butoxy, phenyl and benzyl radicals, said aryl radicals optionally being further substituted. Method according to one of claims 11 to 14, characterized that the substituted aryl groups are methyl substituents as further substituents Ethyl, tert-butyl, methoxy or ethoxy, or halogens from the Wear group of fluorine, chlorine and bromine. Method according to one of claims 11 to 15, characterized the radicals on the substituted aryl groups are methyl or chlorine are. Method according to one of claims 11 to 16, characterized in that as radicals R ² to R ⁵ hydrogen atoms, ethyl, tert-butyl, cyclohexy or phenyl radicals are selected. Method according to one of claims 11 to 17, characterized in that for R ⁶ and R ⁷ radicals from the group of hydrogen atom, methyl, ethyl, propyl, tert-butyl, cyclohexyl, phenyl, benzyl or Tolylrest are selected. Method according to one of claims 11 to 18, characterized in that the radicals R ⁶ , R ^{7 are} hydrogen atoms, methyl, ethyl or tert-butyl radicals. Method according to one of claims 11 to 19, characterized in that are used as BH ₃ adducts BH ₃ -SEt ₂ , BH ₃ -NEt ₃ , BH ₃ -pyridine or BH ₃ -THF. Method according to one of claims 11 to 20, characterized in that BH ₃ or boron triphenyl are used. Method according to one of claims 11 to 21, characterized in that a solution or mixture of the phosphine component R ² R ³ PH and an amine component R ⁴ R ⁵ NH or R ⁴ R ⁵ NSiAlkyl ₃ with an α-ketocarboxylic acid R ¹ C (O ) -COOH or its hydrate or its acetal is reacted

Method according to one of claims 11 to 22, characterized in that a solution or mixture of an amine component R ⁴ R ⁵ NH or R ⁴ R ⁵ NSiAlkyl ₃ and an α-ketocarboxylic acid R ¹ C (O) -COOH or their hydrate or their Acetal or a formed from the amine component and the α-ketocarboxylic acid ammonium salt or condensation product with a phosphine R ² R ³ PH is reacted

Process according to one of Claims 11 to 23, characterized in that a solution or mixture of a phosphine component R ² R ³ PH and an α-ketocarboxylic acid R ¹ C (O) -COOH or its hydrate or its acetal or one of the phosphine component and the phosphonium salt or condensation product formed with the α-ketocarboxylic acid is reacted with an amine component R ⁴ R ⁵ NH or R ⁴ R ⁵ NSiAlkyl ₃

2-amino or 2-hydroxy-2-phosphinoalkanoate nickel derivatives obtainable by the reaction of 2-amino and 2-hydroxy-2-phosphinoalkanoic acid derivatives and 2-phosphoniobis (2-hydroxyalkanoic acid) derivatives of the general formula I

where A is - ⁺ NHR ⁴ R ⁵ (type 1) or -OH (with ⁺ NH ₂ R ⁴ R ⁵ as counterion: type 2), X from the group -C ((COO ^- ) (OH) R ¹ ) (Type 3, when A = -OH and with ⁺ NH ₂ R ⁴ R ⁵ as counterion), lone pair of electrons (no substituent) and a boron compound, wherein the boron compound is selected from the group of BH ₃ , B (alkyl) ₃ , B (aryl) ₃ and B (perfluoroaryl) ₃ , R ^{1 represents} a hydrogen atom or a C ₁ -C ₁₂ alkyl radical or a C ₆ -C ₁₄ aryl radical, R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen, C ₁ -C ₁₂ -n-alkyl groups, C ₁ -C ₁₂ -branched alkyl, C ₃ -C ₁₂ cycloalkyl, C ₁ -C ₁₂ alkoxy groups, C ₁ -C ₁₂ -alkenyl groups, C ₇ -C ₂₀ -arylalkyl groups, C ₆ -C ₁₄ -aryl groups, C ₆ -C ₁₄ -aryl groups which are identical or differently substituted by one or more C ₁ -C ₁₂ -alkyl groups, C ₁ -C ₁₂ 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 together form a saturated or unsaturated ring, R ⁶ and R ⁷ independently are selected from among hydrogen, C ₁ -C ₁₂ -alkyl groups, C ₆ -C ₁₄ -aryl groups, C ₇ -C ₂₀ -arylalkyl groups, and optionally together form a saturated or unsaturated ring, as crude product or in pure form, with a nickel A compound or a combination of a nickel salt with a reducing or alkylating agent, wherein the nickel compound from the group of Ni (COD) ₂ or NiL ₄ , wherein L is PMe ₃ , PPh ₃ , P (OEt) ₃ or CO, or from the group of allyl nickel compounds, methallyl nickel compounds, nickel diketonates or Diphenylnickel (PMe ₃₎ is selected. ₂ 2-amino or 2-hydroxy-2-phosphinoalkanoate nickel derivatives according to claim 25, characterized in that the radical R ^{1 is} selected from the group of hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, Hexyl and phenyl. 2-amino or 2-hydroxy-2-phosphinoalkanoate nickel derivatives according to one of claims 25 or 26, characterized in that the radical R ^{1 represents} a hydrogen atom or a methyl radical. 2-amino or 2-hydroxy-2-phosphinoalkanoate nickel derivatives according to any one of claims 25 to 27, characterized in that the radicals R ² , R ³ , R ⁴ and R ⁵ from the group of hydrogen atom, methyl, Ethyl, propyl, butyl, pentyl, hexyl, iso-propyl, isobutyl, tert-butyl, ethylpropyl, cyclohexyl, methoxy, ethoxy, propoxy, tert-butoxy , Phenyl and benzyl radical, wherein said aryl radicals are optionally further substituted. 2-amino or 2-hydroxy-2-phosphinoalkanoate nickel derivatives according to one the claims 25 to 28, characterized in that the substituted aryl radicals as further substituents methyl, ethyl, tert-butyl, methoxy or ethoxy radicals, or halogens from the group of fluorine, chlorine and carry bromine. 2-amino or 2-hydroxy-2-phosphinoalkanoate nickel derivatives according to one the claims 25 to 29, characterized in that the radicals on the substituted Aryl radicals are methyl or chlorine. 2-amino or 2-hydroxy-2-phosphinoalkanoate nickel derivatives according to any one of claims 25 to 30, characterized in that as radicals for R ² to R ⁵ hydrogen atoms, ethyl, tert-butyl, cyclohexyl or phenyl radicals are selected. 2-amino or ^2- hydroxy-2-phosphinoalkanoate nickel derivatives according to any one of claims 25 to 31, characterized in that R ⁶ and R ⁷ radicals from the group of hydrogen atom, methyl, ethyl, propyl, tert.-butyl, cyclohexyl, phenyl, benzyl or tolyl are selected. 2-amino or 2-hydroxy-2-phosphinoalkanoate nickel derivatives according to any one of claims 25 to 32, characterized in that the radicals R ⁶ , R ^{7 are} hydrogen atoms, methyl, ethyl or tert-butyl radicals. 2-amino or 2-hydroxy-2-phosphinoalkanoate nickel derivatives according to any one of claims 25 to 33, characterized in that the reducing agent is selected from the group of sodium hydride (NaH), potassium hydride (KH), sodium borohydride (NaBH ₄ ), Zinc borohydride (Zn (BH ₄ ) ₂ ) or triethylsilane (Et ₃ SiH). 2-Amino or 2-hydroxy-2-phosphinoalkanoate nickel derivatives according to any one of claims 25 to 34, characterized in that the alkylating agent is methyllithium (MeLi), butyllithium (BuLi), triethylaluminum minium (AlEt ₃ ) or methylaluminoxane (MAO).