EP0946573A1

EP0946573A1 - Catalysts made from transition metal compounds and 4,5-diphosphinoacridine-ligands

Info

Publication number: EP0946573A1
Application number: EP97953764A
Authority: EP
Inventors: Matthias Walter Haenel; Stefan Hillebrand
Original assignee: Studiengesellschaft Kohle gGmbH
Current assignee: Studiengesellschaft Kohle gGmbH
Priority date: 1996-12-17
Filing date: 1997-12-09
Publication date: 1999-10-06
Also published as: JP2001506644A; US6290926B1; CA2275309A1; DE19652350A1; WO1998027101A1

Abstract

The present invention relates to the production of novel catalysts made from transition metal compounds and 'three-toothed' 4,5-diphosphinoacridine-ligands ('Acriphos'). The ligands used to this effect are diphosphine compounds of 4,5-disubstituted acridine, which tri-coordinate the transition metals with both phosphor atoms and with the acridine nitrogen atom. The invention also relates to the use of the novel catalysts for catalysis of carbon monoxide conversion by water gas equilibrium (WGSR:CO+H2O=CO2+H2) and catalysis of the following reactions: hydroformylation, carbonylation, carboxylation, hydration, hydrocyanation, hydrosilylation, polymerization, isomerization, cross-coupling and metathesis. The invention also relates to the syntheses of the 4,5-diphosphinoacridines by reacting 4,5-difluoroacridine with alkali metal phosphides R2P?- M+ (M+ = Li+, Na+, K+, Rb+, Cs+¿, preferably K+) or by reacting 4,5-dibromacridine with chlorophosphines (R¿2?PCl) and magnesium, as well as to the production of 4,5-difluoroacridine and 4,5-dibromacridine, which were previously unknown.

Description

New catalysts made from transition metal compounds and 4,5-diphosphinoacridine ligands

The present invention relates to the production of new catalysts from transition metal compounds and 4,5-diphosphinoacridine ligands ("acriphos"). The new ligands used for this are diphosphine compounds of 4,5-disubstituted acridine with the general formula (I), which coordinate transition metals with the two phosphorus atoms and the acridine nitrogen atom to form transition metal complexes of the general formula (II):

i π la: R ¹ = R ² = R3 = R6 = R7 = R8 _{= R} 9 _{= H}

Rl l = Rl2 ₌ Rl3 _{= R} 14 ₌ p _henyl

The transition metal complexes (II) are novel catalyst systems that can be used to catalyze numerous chemical reactions.

Catalyst systems consisting of transition metal compounds and phosphine ligands are known in homogeneous catalysis. A variety of monophosphine and "bidentate" diphosphine compounds have been synthesized in the past and their application in homogeneous catalysis has been investigated [FR Hartley and S. Patai, ed., The Chemistry of Organophosphorus Compounds, Vol. 1, Wiley, New York , 1990; LH Pignolet, Ed., Homogeneous Catalysis with Metal Phosphine Complexes, Plenum Press, New York, 1983]. Monophosphine and also diphosphine ligands in divalent nickel, palladium and platinum compounds as well as in complex compounds with other transition metals have the disadvantage of being oxidized to phoshin oxides in a redox reaction with the transition metal in the presence of water [P. Giannoccaro, E. Panncciulli and G. Vasapallo, Inorg. Chim. Acta 96 (1985) 179; P. Giannoccaro and G. Vasapallo, Inorg. Chim. Acta 72 (1983) 51]. Since the phosphine ligand is consumed irreversibly, in such cases the catalysis either comes to a complete standstill or, in the best case, can be maintained by using the ligands in large excess in advance or replacing them again and again in the course of the catalysis. With "tridentate" triphosphine or "tridentate" diphosphine ligands with a third coordination site of another donor atom, a further strengthening of the transition metal-ligand bond can be achieved, so that their phosphorus centers are less vulnerable to chemical changes. However, in contrast to mono- and diphosphines, "tridentate" ligands have so far found little use for catalysts. In a new review article on polyphosphine ligands [HA Mayer and WC Kaska, Chem. Rev. 94 (1994) 1239-1272] the authors write: "Thus the idea to use polyphosphine-stabilized metal complexes as catalysts has emerged early. However, the non-dissociative character of the chelating polyphosphines is a disadvantage in catalytic processes which require open sites at the metal center. This seems to limit the application of polyphosphines in catalysis to processes which do not need many available positions at the metal center "(quote on page 1266).

The "tridentate" ligand 2,6-bis (diphenphylhosphinomethyl) pyridine (! _, R = Ph) has long been known [WV Dahlhoff and SM Nelson, J. Chem. Soc. A 1971, 2184; G. Vasapollo, P. Giannoccaro, CF Nobile and A.Sacco, Inorg. Chim. Acta 48 (1981) 125; A. Sacco, P. Giannoccaro and G. Vasapollo, Inorg. Chim. Acta 83 (1984) 125; G. Vasapollo, CF Nobile and A. Sacco ,. J. Organomet. Chem. 296 (1985) 435; Q. Jiang, D. Van Plew, S. Murtuza, and X. Zhang, Tetrahedron Lett. 37 (1996) 797]. The properties of the ligand (HI) differ from that of the ligands (I) and have some of them Disadvantage. In addition to metal complexes of structure (IV) with triple coordination in a "T" -shaped planar arrangement similar to (II), complexes of structure (V) are also known in which the diphosphine compounds (__) only function as "bidentate""Exercise ligands without additional metal-nitrogen coordination [P. Giannoccaro, G. Vasapollo and A.Sacco, J. Chem. Soc. Chem. Commun. 1980, 1 136]. A serious disadvantage of the ligand (__) is that that basic reagents such as alcoholates in transition metal complexes (IV) split off one of the reactive benzylic hydrogen atoms as a proton and lead to the formation of "phosphinomethanide" structures (VI) with a CP double bond character. Catalyst systems with (HI) as ligands can thus in the presence of basic and strong nucleophilic reagents are not used in principle, and the ligand (HI) as benzylic phosphine is extremely sensitive to oxygen [A. Sacco, G. Vasapollo, CF Nobile, A. Piergiovanni, MA Pell inghelli and M. Lafranchi ,. J. Organomet. Chem. 356 (1988) 435].

in IV V VI

It has now surprisingly been found that new transition metal complex compounds (II) which are prepared from the new 4,5-diphosphinoacridine ligands (I, "Acriphos") and transition metal compounds with different oxidation levels, in which R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} hydrogen atoms or, preferably R ⁹ or R ² and R ⁷ , one to two alkyl or alkoxy groups each having 1 to 12 C atoms or aryl, NH ₂ , NR ₂ , NR ₃ ⁺ Y ^" (R = alkyl with d to C ₄ , Y ^" = anions such as halides), OH, COOH, SO H, halogens or CF ₃ or where R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ⁹ = H or, preferably R ⁹ or R ² and R ⁷ , one to two alkyl, alkoxy or aryl groups with groups such as NH ₂ , NR ₂ , NR ₃ ⁺ Y ^" (R = alkyl with Ci to C ₄ , Y ^" = anions such as halides), OH, COOH, SO ₃ H, halogens or CF ₃ , where R ^u , R ¹² , R ¹³ and R ¹⁴ aryl, aralkyl, alkaryl, alkyl cycloalkyl groups, or with groups such as NH ₂ , NR ₂ , NR ₃ ⁺ Y ^" (R = alkyl with d to C ₄ , Y ^" = Anions such as halides), OH, COOH, SO ₃ H, halogens or CF ₃ substituted phenyl or alkyl groups in which R ¹¹ , R ¹² , R ¹³ and R ^{14 are} either identical or different, in which R ¹¹ and R ¹² and R ¹³ and R ¹⁴ each have two alkyl substituents which are linked to form phosphacycloalkanes, M transition metals Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf , Ta, W, Re, Os, Ir, Pt, Au in different oxidation states, X up to three anions or ligands (n = 0, 1, 2, 3) such as halides (F, Cl ^" , Br \ I ^" ) , Cyanide, acetate, propionate, trifluoroacetate, acetylacetonate, hexafluoroacetylacetonate, sulfate, alkyl sulfonate, aryl sulfonate, trifluorom ethanesulfonate, hydride, alkyl, aryl, carbon monoxide, nitrosyl, trialkylphosphine, triarylphosphine, trialkylphosphite, triarylphosphite, ethylene, olefins, acetylenes, cyclopentadienyl, benzene, which are bound to the transition metal M, are very active catalysts and are therefore very useful for catalysis numerous reactions can be applied.

The novel phosphine ligands (I), wherein R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} hydrogen atoms or, preferably R ⁹ or R ² and R ⁷ , one or two alkyl or Alkoxy groups each with 1 to 12 carbon atoms or aryl, NH ₂ , NR ₂ , NR ₃ ⁺ Y ^" (R = alkyl with Ci to C ₄ , Y ^" = anions such as halides), OH, COOH, SO ₃ H , Halogens or CF ₃ or in which R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ⁹ = H or,

0 1 preferably R or R and R, one to two alkyl, alkoxy or aryl groups which are linked to groups such as NH ₂ , NR ₂ , NR ₃ ⁺ Y ^" (R = alkyl with Q to C ₄ , Y ^" = Anions such as halides), OH, COOH, SO H, halogens or CF _{3 are} substituted, wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ aryl, aralkyl, alkaryl, alkyl-cycloalkyl groups, or with groups such as NH ₂ , NR ₂ , NR ₃ ⁺ X ^" (R = alkyl with C ₁ -C ₄ , Y ^" = anions such as halides), OH, COOH, SO H, halogens or CF ₃ substituted phenyl or alkyl groups in which R ¹¹ , R ¹² , R ¹³ and R ^{14 are} either the same or are different, in which R and R and R and R each represent two alkyl substituents which are linked to one another to form phosphacycloalkanes, are very tightly coordinated to the metal centers, and thus make undesired reactions irreversible under the conditions of catalysis at the phosphorus centers difficult. The ligands (I) differ from the previously known diphosphine ligands in a number of properties. The condensed, tricyclic, completely aromatic skeleton of the acridine, to which the phosphorus substituents are attached, ensures a flat and particularly rigid structure of the ligands. The acridine nitrogen atom located between the two phosphorus atoms represents a third coordination point, so that the diphosphine compounds (I) act as tridentate ligands for transition metals and therefore have the property of particularly strong metal-ligand coordination. In contrast to the pyridine ligand (__J, R = phenyl), the acridine ligands (I) in the case (R ^u to R ¹⁴ = phenyl or aryl) are triarylphosphines which have good oxygen resistance compared to the very oxygen-sensitive phosphines distinguishes one or more aliphatic phosphorus substituents.

According to the present invention, the new 4,5-diphosphinoacridines (I, "Acriphos") and transition metal compounds can be used to produce new catalysts which have significantly improved properties compared to previous catalysts made from transition metal compounds and phosphine ligands. For example, with the (l: l) complex of palladium (LT) chloride and "Acriphos" (I, R ¹ to R ⁹ = H, R ¹¹ to R ¹⁴ = phenyl), the carbon monoxide conversion via the water gas balance (WGSR ) catalyzed without the formation of phosphine oxide on the ligand in the presence of water - as stated above - and thus the catalyst system very quickly loses its activity. The strong metal-ligand bond of the "acriphos" ligands (I) is advantageous for the stability of catalysts. For example, the nickel (II) catalysts previously used for hydrocyanation often lose theirs very quickly Activity due to competing nickel (U) cyanide formation [M. Kranenburg, PCJ Kamer, PWNM van Leeuwen, D. Vogt, and W. Keim, J. Chem. Soc. Chem. Commun. 1995, 2177].

In the formulas (I) for the ligands and (II) for the transition metal complexes, the substituents R ¹¹ to R ¹⁴ on the phosphorus atoms represent aryl, aralkyl, alkaryl, alkyl or cycloalkyl groups. They can either be the same or different. Two alkyl substituents of a phosphorus atom can also be linked, so that they form ring-shaped phosphacycloalkanes with the phosphorus atom as substituents of the 4,5-substituted acridine. The acridine substituents R ¹ , R ² , R ³ , R, R ⁷ , R ⁸ and R ⁹ are either hydrogen atoms or at least one or two of these substituents, preferably R ⁹ or R ² and R ⁷ , are groups which increases the solubility of the ligands (I) and the transition metal complexes (Η) in certain solvents or reaction media. Such groups are, for example, alkyl and alkoxy groups with 1 to 12 carbon atoms, groups such as NH ₂ , NR ₂ and NR ₃ ⁺ X ^" (R = alkyl with C to C ₄ , X ^" = anions such as halides), OH, COOH, SO ₃ H, halogens or CF ₃ as well as alkyl or aryl groups, which in turn with groups such as NH ₂ , NR and NR ₃ ⁺ X ^" (R = alkyl with Ci to C ₄ , X ^" = anions such as Halides), OH, COOH, SO ₃ H, halogens or CF _{3 are} substituted. Such groups can also be attached to the phosphorus substituents R ¹¹ to R ¹⁴ , for example in such a way that R ¹¹ , R ¹² , R ¹³ and R ^{14 represent} one to four phenyl or alkyl radicals with such groups as substituents.

The transition metal compounds which are used together with the diphosphine ligands (I) for the new catalyst systems (II) can be compounds of the following transition metals in different oxidation states: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au. In the complex compounds (II), depending on the type of metal and the oxidation state, up to three anions or ligands (X _n , n = 0, 1, 2, 3) be bound. Such anions or ligands are, for example, halides (F ^" , Cl ^" , Br ^" , I ^" ), cyanide, acetate, propionate, trifluoacetate, acetylacetonate, hexafluoroacetyl acetonate, sulfate, alkyl sulfonate, aryl sulfonate, trifluoromethanesulfonate, hydride, alkyl, aryl, carbon monoxide , Nitrosyl, trialkylphosphine, triarylphosphine, trialkylphosphite, triarylphosphite, ethylene, olefins, acetylenes, cyclopentadienyl, benzene. The compounds (II) can be neutral, cationic or anionic complex compounds.

The catalyst systems can either be stoichiometric ligand-transition metal complexes, such as, for example, the complex compounds VIJI-XII listed below, or can also be formed from mixtures of ligands (I) and transition metal compounds in situ. In the latter case, the ligand / metal ratio is generally between 0.1 and 100 and preferably between 0.5 and 10. It may also be advantageous to additionally use a cocatalyst in order to increase the reactivity of the catalyst system. The cocatalyst can be, for example, a Lewis acid (for example A1C1 ₃ , BF ₃ , SnCl ₂ , ZnCl ₂ , SbF, SbF ₅ ) or a soluble silver (I) compound which is present in amounts of 1 to 10 equivalents of the transition metal compound is added.

The catalysts of the invention can be used for carbon monoxide conversion via the water gas equilibrium (WGSR: CO + H ₂ O = CO + H ₂ ) and for the catalysis of reactions such as hydroformylation, carbonylation, carboxylation, hydrogenation, hydrocyanation, hydrosilylation, polymerization, isomerization , Cross couplings and metathesis are used.

The present invention preferably relates to the preparation of complex compounds (II) by reacting 4,5-bis (diphenylphosphino) acridine (Ia) with transition metal compounds with various oxidation states. With this ligand, reactions with bis (benzonitrile) palladium (π) chloride, nickel (H) chloride hexahydrate, platinum (II) chloride, carbonylhydridotis (triphenyl- phosphine) rhodium (I) and 2,5-norbornadiene-molybdenum (0) tetracarbonyl in organic solvents such as hydrocarbons, preferably benzene and toluene, ether, preferably diethyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, carbon tetrachloride, chlorinated hydrocarbons, preferably Dichloromethane and chloroform, alcohols, preferably butanol, acetone, acetonitrile, dimethylformamide at temperatures between -100 ° C and +200 ° C, preferably between 0 ° C and 100 ° C, for example at room temperature to 30 ° C, the following transition metal -Complexes shown: 4,5-bis (diphenylphosphino) acridine-palladium (II) chloride (VIQ), 4,5-bis (diphenylphosphino) acridine-nickel (LT) chloride (LX), bis [4,5- bis (diphenylphosphino) acridine-chloroplatin (LI)] - tetrachloroplatinate (LI) (X), 4,5-bis (diphenylphosphino) acridine-carbonylhydrido-rhodium (I) (XI) and 4,5-bis (diphenylphosphino) acridine- molybdenum (0) ricarbonyl {___) ■

xπ It can be deduced from the spectroscopic data that in all cases the 4,5-bis (diphenylphosphino) acridine (la) ligand is coordinated to the transition metals both via its two phosphorus atoms and via its acridine nitrogen atom. In the case of the molybdenum tricarbonyl complex (XII), the triple, approximately "T" -shaped planar ligand-metal coordination was also confirmed by a single-crystal X-ray structure analysis (Fig. 1, distances P - P: 4,732 Å; Mo-P: 2,405 Ä and 2.426 Ä; Mo-N: 2.290 Ä). The mass spectra with the molecular ions of the complex cations and conductivity measurements indicate the ionic structure of the complexes (____), (IX) and (X).

Fig. 1: Single-crystal X-ray structure analysis of 4,5-bis (diphenylphosphino) acridine-molybdenum (0) tricarbonyl (XII). Left: Top view of the acridine unit. Right: Front view of the molybdenum tricarbonyl unit.

According to the invention, the described transition metal complexes (II), preferably the described metal complexes (VIII) - (XU), can be used as catalysts. For example, 4,5-bis (diphenylphosphino) acridine-palladium (LI) chloride (VLΩ) in solution of n-ButanolAV water 9: 1 can already convert carbon monoxide over WGSR under neutral conditions (ie without adding base or acid) to be catalyzed at the relatively low temperature of 130 ° C [Overview of homogeneous catalysis of WGSR: RM Laine and EJ Crawford, J. Mol. Catal. 44 (1988) 357]. The catalyst remains active even after the reaction has been interrupted (cooling, gas withdrawal, repressurization of carbon monoxide and reheating). The above-mentioned oxidation of the diphosphine ligand (I) by divalent transition metals in the presence of water is completely avoided or at least very slowed down. The example of WGSR catalysis by the palladium complex (VIII) in neutral solution has made great strides and has clear advantages when the comparison is made with WGSR catalysts which are described in the literature with catalyst systems composed of transition metal compounds and phosphine ligands are. This is e.g. B. clearly in comparison with that of Zudin et al. Catalyst system described from palladium (II) acetate and triphenylphosphine, the phosphine ligand in a very large excess (metal / ligand ratio of 1:50 to 1: 100) and the strongly acidic and thus also very corrosive reaction medium of trifluoroacetic acid / water 4 : 1 required [VN Zudin, VA Likholobov, Yu.I. Yermakov and NK Yeremenko, Kinet. Catal. (Transl. Of Kinet. Katl) 18 (1977) 440; VN Zudin, VD Chinakov, VM Nekipelov, VA Rogov, VA Likholobov and Yu. I. Yermakov, J. Mol. Catal. 52 (1989) 27-48].

The present invention also relates to the synthesis of 4,5-diphosphinoacridines (I). These ligands (I) can be obtained by the reaction of previously unknown 4,5-dihaloacridines (halogen = F, Cl, Br, J) with alkali metal phosphides [R ₂ P ^~ M ⁺ (R = alkyl, phenyl or aryl; M ⁺ = Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ )] in aprotic organic solvents such as hydrocarbons, preferably toluene, ether, preferably diethyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, oligomeric ethylene glycol dimethyl ether, hexamethylphosphoric triamide, N-methyl 2- pyrrolidinone, preferably in 1,4-dioxane, at temperatures between -100 ° C and +200 ° C, preferably between 0 ° C and +150 ° C, or by the reaction of 4,5-dihaloacridines (halogen = F , Cl, Br, J) with chlorophosphines [R ₂ PC1 (R = alkyl, phenyl or aryl)] and magnesium in aprotic organic Solvents such as hydrocarbons, preferably toluene, ether, preferably diethyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, oligomeric ethylene glycol dimethyl ether, hexamethylphosphoric acid triamide, N-methyl-2-pyrrolidinone, preferably in tetrahydrofuran, at temperatures between -100 ° C. and + 100 ° C, preferably between 0 ° C and +100 ° C, are produced. The ligands (I) are preferably obtained by reacting 4,5-difluoroacridine (Xm) with potassium phosphides [R ₂ P ^~ K ⁺ (R = alkyl, phenyl or aryl)] or by reacting 4,5-dibromoacridine (XIX) Chlorophosphines [R ₂ PC1 (R = alkyl, phenyl or aryl)] and magnesium are produced in these aprotic organic solvents. For example, 4,5-bis (diphenylphosphino) acridine (la) was obtained by the reaction of 4,5-difluoroacridine (XHI) with two equivalents of potassium diphenylphosphide (Ph ₂ PK ⁺ ) in 1,4-dioxane at temperatures between 0 ° C and

Get 100 ° C:

The previously unknown 4,5-difluoroacridine (XTfl) required for this can be prepared in a four-step synthesis from 2-amino-3-fluorobenzoic acid (XIV) and 2-fluoroiodobenzene (XV): (XIV) and (XV) can in a copper-catalyzed coupling reaction in the presence of potassium carbonate in solvents such as alcohols, ethylene glycols, ethers, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, preferably in cyclohexanol, at temperatures between 20 ° C and 200 ° C, preferably at 100 ° C to 160 ° C are converted to 3-fluoro-2- (2-fluorophenylamino) benzoic acid (XVI):

XVI can then be cyclized in phosphoryl chloride at temperatures between 50 ° C and 150 ° C to 9-chloro-4,5-difluoroacridine (XVII). To obtain the 4-, 5-fluoro substituents, the 9-chloro substituent can be removed from (XVU) by (XVII) with p-toluenesulfonic acid hydrazide in hydrocarbons or chlorinated hydrocarbons, preferably in chloroform, at temperatures between 0 ° C. and 100 ° C to 9 - (/? - toluenesulfonic acid hydrazido) -4,5-difluoroacridinium hydrochloride (XVIJT) and (XVLTI) then with sodium hydroxide solution in ethylene glycol at temperatures between 50 ° C and 200 ° C to 4,5-difluoroacridine (XHJ ) is decomposed:

4,5-bis (diphenylphosphino) acridine (la) was, for example, also by the reaction of 4,5-dibromoacridine (_____) with two equivalents of chlorodiphenylphosphine (Ph PCl) and two equivalents of magnesium in tetrahydrofuran at temperatures between 20 ° C and Get 70 ° C:

.

XIX

The previously unknown 4,5-dibromoacridine (XIX) required for this can be obtained in a four-step synthesis from 3-bromo-2-iodobenzoic acid (XX) and 2-bromoaniline (XXI). can be prepared: (XX) and (XXI) can be converted into their respective sodium compounds with sodium hydride and this presence of copper powder in solvents such as ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, preferably in tetrahydrofuran, at temperatures between 20 ° C. and 150 ° C, to 3-bromo-2- (2-bromophenylamino) benzoic acid (XXII):

Then (XXII) can be cyclized in phosphoryl chloride at temperatures between 50 ° C and 150 ° C to 9-chloro-4,5-dibromoacridine (XXHD). Obtaining the 4-, 5-fluoro substituents from (XXHI) the 9th Chlorine substituent are removed by (XU) with p-toluenesulfonic acid hydrazide in hydrocarbons or chlorinated hydrocarbons, preferably in chloroform, at temperatures between 0 ° C and 100 ° C to 9- (-Toluenesulfonic acid hydrazido) - 4,5-dibromoacridinium hydrochloride (XXPV) is reacted and (XXTV) is subsequently decomposed to sodium 4,5-dibromoacridine (XIX) with sodium hydroxide solution in ethylene glycol at temperatures between 50 ° C and 200 ° C:

XXII xxm XEX

With the syntheses of 4,5-difluoroacridine (____) and 4,5-dibromoacridine (XIX) according to the invention, intermediates are available for further syntheses of 4,5-disubstituted acridines which have hitherto been difficult to access. Examples of transition metal complexes of 4,5-bis (diphenylphosphino) acridine (I, R = phenyl) Example 1:

4,5-bis (diphenylphosphino) acridine-palladium (II) chloride (VIII): A solution of 0.15 g (0.27 mmol) of 4,5-bis (diphenylphosphino) acridine (la) in 30 ml of anhydrous dichloromethane was added at room temperature Solution of 0.10 g (0.26 mmol) of bis (benzonitrile) palladium (II) chloride in 8 ml of anhydrous dichloromethane was added dropwise. The resulting red solution was stirred at room temperature for 16 hours. After concentrating the mixture to a volume of 2 ml, 10 ml of tetrahydrofuran and 10 ml of “pentane” were added. The precipitate formed was filtered off, washed twice with rc-pentane and dried under high vacuum. 0.16 g (81% of theory) of 4,5-bis (diphenylphosphino) acridine-palladium (H) chloride (VIII) was obtained as a light brown solid which decomposes at 185 ° C. (DSC). C ₃₇ H ₂₇ NP ₂ PdCl ₂ (724.90 g mor ¹ ): calc. 61.31% C, 3.75% H, 1.93% N, 8.55% P, 9.78% Cl, 14.68% Pd found. 61.15% C, 3.94% H, 1.85% N, 8.52% P, 9.98% Cl, 14.65% Pd

MS (ESI, CH ₂ C1 ₂ , pos. Ions): m / z = 688 ([M - Cl] ^θ with ³⁵ C1 and ¹⁰⁶ Pd, isotope mother as calculated). - IR (KBr): v = 3047 cm ^"1 (w, v [CH]; 1518 (m), 1435 (s) and 1418 (m, v [C = C]); 1096 (s); 746 (s ) and 691 (s, γ [CH]); 519 (vs). - ³¹ P-NMR (81 MHz, CDC1 ₃ , external standard 85 percent phosphoric acid): δ = 32.7 (s). - 'H-NMR ( 400 MHz, CD ₂ C1 ₂ ): δ = 10.97 (s br., 1 H, 9-H); 9.18 (d br.), 8.36 ("q" br.) And 8.00 ("t" br.) ABCXX 'spin system with X = X' = ³¹ P, ⁴ 7 _AB nb, ³ J _AC - 8 Hz, ³ 7 _BC - 7 Hz, Σ ' _ß xpo «10 Hz, 2 H each for 1-, 8-H (A), 3-, 6-H (B), 2-, 7-H (C) ]; 7.89-7.76 (m, 8 H, phenyl- _ortho ), 7.66-7.56 (m, 12 H, phenyl-H). - ¹³ C-NMR (50 MHz, CDC1 ₃ ): δ (multiplicity with respect to ^] J _CH , apparent "multiplicity" by coupling with ³¹ P) = 153.7 (s, "t" with ∑ ⁿ J _CP = 24.4 Hz, C- 4a, -10a), 148.2 (d, s, C-9), 144.1 (d, s, C-1, -8 or C-3, -6), 136.8 (d, s, C-1, -8 or C-3, -6), 133.7 (d, "t" with ∑ ⁿ / _CP = 14.2 Hz, phenyl-C _ortΛo ), 132.7 (d, s, phenyl-C _pαra ), 130.6 (s, "t" with ∑ ⁿ 7 _CP = 40.7 Hz, C-4, -5), 129.7 (d, "t" with ∑ ⁿ 7 _CP = 10.2 Hz, phenyl-C _meto ), 129.4 (s, "t" with ∑ ⁿ 7 _CP = 8.1 Hz, C-8a, -9a), 128.1 (d, "m" with ∑ ⁿ J _CP = 8.5 Hz, C-2, -7), 126.8 (s, "t" with ∑ ⁿ 7 _CP = 52.9 Hz, phenyl-C ₍₀ ).

Example 2:

4,5-bis (diphenylphosphino) acridine-nickel (II) chloride (IX):

A solution of 0.10 g (0.42 mmol) of nickel (U) chloride hexahydrate in 10 was added to a suspension of 0.22 g (0.40 mmol) of 4,5-bis (diphenylphosphino) acridine (la) in 60 ml of «butanol at room temperature ml of n-butanol added dropwise. The mixture was then stirred at room temperature for 30 h. The resulting red solution was concentrated to a volume of 5 ml and 15 ml of pentane was added. The precipitate formed was filtered off, washed twice with “pentane and dried under high vacuum. This gave 0.18 g (63% of theory) of 4,5-bis (diphenylphosphino) acridine-nickel (II) chloride (IX) with two molecules of water of crystallization as a rust-red powder which decomposes at 150 ° C.

C ₃₇ H ₂₇ NP ₂ NiCl ₂ ^• 2 H ₂ O (713.20 g mol ^"1 ): calc. 62.31% C, 4.38% H, 1.96% N, 8.69% P, 9.94% Cl, 8.23% Ni found. 61.79% C, 4.31% H, 1.96% N, 8.74% P, 10.42% Cl, 8.67% Ni

MS (ESI, CH ₂ C1 ₂ , positive ions): m / z = 640 ([M - Cl] ^® with ³⁵ C1 and ⁵⁸ Ni,

Isotope pattern as calculated - IR (KBr): v = 3400 cm ^-1 (w, br., V [OH]); 3051 (w, v [CH]); 1517 (m), 1436 (s) and 1418 (m, v [C = C]); 1098 (m); 745 (s) and 692 (s, γ [CH]); 521 (vs). - ³¹ P-NMR (81 MHz, CDC1 ₃ , external standard 85 percent phosphoric acid): δ = 25.6 (s). - • H-NMR (400 MHz, CD ₂ C1 ₂ ): 6 = 1 1.9 (s br., 1 H,

9-H); 9.8 (s br., 2 H, 1-, 8-H), 8.3 (s br., 2 H, 3-, 6-H), 8.1 (s br., 2 H, 2-, 7-H) , 7.9 (d br., 8 H, phenyl-H _ortho ), 7.6-7.5 (m, 12 H, phenyl-H).

Example 3:

Bis [4,5-bis (diphenylphosphino) acridine chloroplatin (II) 1tetrachloroplatinate (II) (X): To a solution of 150 mg (0.27 mmol) 4,5-bis (diphenylphosphino) acridine (la) in 30 ml anhydrous dichloromethane a suspension of 73 mg (0.27 mmol) of platinum (π) chloride in 8 ml of anhydrous dichloromethane was added dropwise at room temperature. The resulting red solution was stirred for 4 d at room temperature. After the mixture was concentrated to a volume of 2 ml, 10 ml of tetrahydrofuran and 10 ml of pentane were added. The precipitate formed was filtered off, washed twice with “pentane and dried under high vacuum. 1 10 mg (65% of theory) of bis [4,5-bis (diphenylphosphino) acridine chloroplatinum (II)] tetrachloroplatinate (π) (X) were obtained as a light brown solid which decomposes at 200 ° C. C ₇₄ H ₅₄ N ₂ P ₄ Pt ₃ Cl ₆ (1893.1 1 g mol ^"1 ): calc. 46.95% C, 2.88% H, 1.48% N, 6.54% P, 1 1.74% Cl, 30.91% Pt found. 45.50 % C, 3.00% H, 1.51% N, 6.24% P, 1 1.45% Cl, 30.46% Pt MS (ESI, CH ₂ C1 ₂ , positive ions): m / z = 777 ([C ₃₇ H ₂₇ NP ₂ PtCl] ^θ with ³⁵ C1 and ¹⁹⁵ Pt,

Isotope pattern as calculated.). - IR (KBr): v = 3050 cm ^-1 (m, v [CH]; 1604 (m), 1520 (m) and 1436 (s), v [C = C]); 1099 (m); 747 (m) and 691 (s, γ [CH]); 523 (vs). - ³¹ P-NMR (81 MHz, CDC1 ₃ , external standard 85 percent phosphoric acid): δ = 27.2

("t", ^l J 9s _{? tP} = 2620 Hz). - 1H-NMR (400 MHz, CD ₂ C1 ₂ ): δ = 10.90 (s br., 1 H, 9-H); 9.04 (d br.), 8.54 ("q" br.) And 8.01 ("t" br.) [ABCXX 'spin system with X = X' = ³¹ P> ⁴ JAB ⁿ - ^b - _' ³ ^ AC = ⁷ - ^{8 Hz} > ³ BC = ^{7 Hz} > ∑ ^ B ^ X) ^Ä 10 Hz, 2 H each for 1-, 8-H (A), 3-, 6-H (B), 2-, 7-H (C)]; 7.95-7.82 (m, 8H, phenyl-H _{or [ho} ), 7.61-7.48 (m, 12H, phenyl-H). ¹³ C-NMR (50 MHz, CD ₂ C1 ₂ ): δ (multiplicity with respect to ¹ J _cu , apparent "multiplicity" by coupling with ³¹ P) = 154.4 (s, "t" with ∑ ⁿ 7 _CP = 22.0 Hz, C-4a, -10a), 146.8 (d, s br., C-9), 144.8 (d, s br., C-1, -8 or C-3, -6), 136.4 (d, s br ., C-1, -8 or C-3, -6), 134.1 (d, "t" with ∑ ⁿ 7 _CP = 14.0 Hz, phenyl-C _ortAo ), 133.0 (d, s, phenyl-C ^) , 131.5 (s, ^* 't "with ∑ ⁿ 7 _CP = 51.0 Hz, C-4, -5), 129.7 (d," t "with ∑ ⁿ 7 _CP = 10.2 Hz, phenyl-C _me , 128.9 (d , "m" with ∑ ⁿ / _CP = 8.0 Hz, C-2, -7), 128.9 (s, C-8a, -9a), 127.3 (s, "t" with ∑ ⁿ 7 _CP = 61.5 Hz, Pheny \ -C _1pso ).

Example 4:

4 ₁ 5-bis (diphenylphosphino) acridine-carbonylhydridorhodium (I) (XI):

To a suspension of 200 mg (365 μmol) 4,5-bis (diphenylphosphino) acridine

(Yes) in 30 ml of anhydrous toluene, a solution of 335 mg (365 μmol)

Carbonylhydridotri (triphenylphosphine) rhodium (I) in 25 ml of anhydrous toluene was added. The resulting mixture was stirred at 30 ° C for 4 h. Subsequently the solvent was distilled off in vacuo and the residue was suspended in 5 ml of tetrahydrofuran. After the addition of 10 ml of "pentane, the precipitate was filtered off, washed with" pentane and dried under high vacuum. This gave 120 mg of an orange-yellow solid which, according to mass spectrometric and IR spectroscopic analysis, consists of 4,5-bis (diphenylphosphino) acridine-carbonylhydridorhodium (I) (XI). C ₃₈ H ₂₈ NP ₂ ORh (679.50g mor ¹ ): calc. 679.069417 u found. 679.064144 u (high-resolution MS)

XI

MS (EI, 70 eV, VT 330 ° C): m / z (%) = 679 (100, M ^{θ *} ), 651 (72, [M - CO] ^{θ #} ),

570 (24), 494 (53, [M - PPh ₂ ] ^® ), 388 (28), 254 (18), 78 (20th - IR (KBr): v = 3053 cm ^"1 (w, v [CH ]); 1953 (vs, v [C = O]); 1573 (m), 1434 (s) and 1413 (vs, v [C = C]); 1097 (m); 742 (s) and 693 (s , γ [CH]); 515 (s).

Example 5:

4,5-bis (diphenylphosphino) acridine-molybdenum (0) tricarbonyl (XII): A suspension of 150 mg (0.274 mmol) of 4,5-bis (diphenylphosphino) acridine (la) in 25 ml of toluene was added at room temperature Solution of 82 mg (0.273 mmol) of 2,5-norbornadiene-molybdenum (0) tetracarbonyl in 10 ml of toluene was added dropwise. The mixture was stirred at room temperature for 17 h. The solvent was then distilled off and the residue was dissolved in 10 ml of methylene chloride. 20 ml of "pentane was added to the dark green solution. The resulting precipitate was filtered off and dried in a high vacuum. 30 mg (15% of theory) of 4,5-bis (diphenylphosphino) acridine-molybdenum (0) tricarbonyl (XU) were obtained as a dark green powder which decomposes at 345 ° C. (DSC). C ₄₀ H ₂₇ NP ₂ MoO ₃ (727.55 g mor ¹ ): calc. 66.04% C, 3.74% H, 1.93% N, 8.51% P, 13.19% Mo found. 65.87% C, 3.71% H, 2.03% N, 8.58% P, 13.31% Mo

MS (EI, 70 eV, VT 240 ° C): m / z (%) = 729 (<1, M ^{® *} with ⁹⁸ Mo, isotope pattern

as calc.), 701 (9, [M - CO] ^® 'with ⁹⁸ Mo), 645 (10, [M - 3CO] ^® ' with ⁹⁸ Mo), 547

(8, [M -Mo - 3CO] ^{® *} ), 154 (10), 78 (88), 77 (21), 51 (17), 39 (13), 28 (100). - IR

(KBr): v = 3054 cm ^"1 (w, v [CH]); 1957 (s), 1850 (vs), 1810 (vs) and 1801 (vs, v [C = O]); 1603 (m) , 1507 (m) and 1433 (m, v0 [C = C]); 1088 (m); 743 (m) and 694 (s, γ [CH]); 513 (s). - ³¹ P-NMR (81 MHz, CD ₂ C1 ₂ , external standard 85 percent phosphoric acid): δ = 58.6 (s). - H-NMR (200 MHz, CD ₂ C1 ₂ ): δ = 9.00 (s br., 1 H, 9-H ); 8.19 (d br., 2 H), 8.07 (m, 2 H) [AB part of an ABCXX 'spin system with X = X' = ³¹ P, ⁴ 7 _AB - 1 Hz., ³ 7 _AC = 8.0 Hz, ³ 7 _BC - 7 Hz, Σ ⁿ J _{BX (χ} . ₎ - 7 Hz, 2 H each for 1-, 8-H (A), 3-, 6-H (B); 7.72-7.57 [m , 10 H, 2-, 7-H (C part of the ABCXX 'spin system) and phenyl-U _ortho ], 7.44-7.35 (m, 12 H, phenyl-H). - ¹³ C-NMR (50 MHz, CD ₂ C1 ₂ ): δ (multiplicity regarding ^ J _Q H _* multiplicity or apparent "multiplicity" by coupling with ³¹ P) = 215.9 (s, t with ² 7 _CP = 30 Hz, C = O), 155.0 (s , "t" with ∑ ⁿ 7 _CP = 27 Hz, C-4a, -10a), 141.5 (d, s, C-3.-6), 140.0 (s, "t" with ∑ ⁿ 7 _CP = 24 Hz , C-4, -5), 139.6 (s, "t" with ∑ ⁿ 7 _CP = 35 Hz, phenyl-C ^ ₀ ), 139.2 (d, t with ⁶ 7 _CP = 3 Hz, C-9), 132.8 (d, "t" with ∑ ⁿ 7 _CP = 13 Hz, phenyl-C _ortΛo ), 132.1 (d, s, C-1, - 8), 129.4 (d, s, phenyl-C ^), 128.6 (d, "t" with ∑ ⁿ 7 _CP = 10 Hz, phenyl- C _meta ), 128.3 (s, "t" with ∑ ⁿ 7 _CP = 8 Hz, C-8a, -9a), 126.4 (d, "t" with ∑ ⁿ 7 _CP = 5 Hz, C-2, -7 ).

A single-crystal X-ray structure analysis of the compound (Xu) was able to be carried out with crystals obtained from a solution in dichloromethane / n-pentane (Fig. 1).

Example 6:

Catalysis of the water gas shift reaction (CO + H ₂ O =

CO ₂ + Ho):

A steel autoclave (V4A steel, 100 ml volume, equipped with a manometer, valve, magnetic stirrer and heating device) was exposed to 50.0 mg (0.07 mmol) of 4,5-bis (diphenylphosphino) acridine-palladium (II) chloride under an atmosphere of argon (VII), 18 ml of n-butanol and 2 ml of distilled water filled and sealed. The autoclave was first rinsed by injecting carbon monoxide and then relaxing. After 30 bar of carbon monoxide had been injected (pressure at room temperature), the autoclave was heated to 130 ° C. with stirring for 15.5 h. After cooling to room temperature, a pressure of 34 bar was read. A gas sample was taken via a valve and analyzed by mass spectrometry: 74.8 mol% CO, 18.1 mol% H, 7.1 mol% CO ₂ . According to the formula mol% H ₂

Degree of conversion = ^■ mol% H ₂ + mol% CO, a degree of conversion of 19.5% was calculated. From the volume of the autoclave and the partial pressures of the gases, the absolute amount of hydrogen formed was calculated to be 20 mmol according to the general gas equation. Based on the amount of catalyst used, a number of the catalyzed cycles (turn over number) of 285 is obtained. The autoclave, which still contained the catalyst in n-butanol / water, was then rinsed with carbon monoxide, a second time with 30 bar carbon monoxide charged and heated to 130 ° C. with stirring for 16 h. After cooling to room temperature, the pressure was 33 bar. From the gas analysis (87.1 mol% CO,

7.1 mol% H ₂ , 5.8 mol% CO ₂ ), as stated above, a degree of conversion of 7.5% and a number of catalytic cycles (turn over number) of 110 were calculated.

Example 7:

Synthesis of 4,5-bis (diphenylphosphino) acridine da)

To a solution of 0.51 g (2.37 mmol) 4,5-difluoroacridine Q___) in 50 ml

At room temperature, 1,4-dioxane became 9.3 ml (4.65 mmol) of a 0.5 molar

Solution of potassium diphenylphosphide (Ph ₂ P ^~ K ⁺ ) dropped in tetrahydrofuran.

When the addition was complete, the mixture was heated under reflux for one hour.

After cooling, the brown reaction solution was distilled with 30 ml. Water added. The precipitate formed was filtered off, thoroughly with distilled water. Water,

Washed ethanol and pentane and dried in a high vacuum. You got

1.02 g (79% of theory) 4,5-bis (diphenylphosphino) acridine (la) as a yellow powder that decomposes from 255 ° C.

C ₃₇ H ₂₇ NP ₂ (547.58 g mor ¹ ): calc. 81.16% C, 4.97% H, 2.56% N, 1 1.31% P found 80.67% C, 5.26% H, 2.44% N, 10.53% P

MS (EI, 70 eV, VT 190 ° C): m / z (%) = 547 (100, ^M® "), 360 (13), 284 (12), 283

(15). - IR (KBr): v = 3060 cm ^"1 (m, v [CH]); 1610 (m), 1510 (m) and 1435 (s, v [C = C]); 745 (s) and 695 ( s, γ [CH])]. - ³¹ P-NMR (81 MHz, CDC1 ₃ , external

Standard 85 percent Phosphoric acid): δ = -14.7 (s). - Η NMR (400 MHz, CD ₂ C1 ₂ ):

E = 8.82 (s, 1H, 9-H); 8.00 (dd), 7.40 (dd) and 7.15 (ddd) [ABCXX 'spin system with X = X '= ³¹ P, ³ 7 _AB = 8.5 Hz, ⁴ 7 _AC = 1.5 Hz, ³ 7 _BC = 6.8 Hz, Σ ⁿ 7 _{CX (χ} . ₎ = 3.6 Hz, 2 H each for 1-, 8 -H (A), 2-, 7-H (B), 3-, 6-H (C)]; 7.30-7.20 (m, 20H, phenyl-H). - ¹³ C-NMR (75 MHz, CD ₂ C1 ₂ ): δ (multiplicity with respect to ^, apparent "multiplicity" by coupling with ³¹ P) = 149.5 (s, "t", C-4a, -10a), 138.7 ( s, "t", C, -5 or phenyl-C, ^), 138.6 (s, "t", C-4, -5 or phenyl-C ^), 137.0 (d, s, C-9), 135.8 (d, s,

C-3, -6), 134.6 (d, "d" with ∑ ⁿ 7 _CP = 22.4 Hz, phenyl-C _or , _to ), 129.2 (d, s, C-1, -8), 128.6 (d, "d" with ∑ ⁿ 7 _CP = 12.2 Hz, phenyl-C _weω ), 128.5 (s, "d" with ∑ ⁿ 7 _CP = 3.0 Hz, phenyl-C _pαra ), 126.9 (s, s, C-8a, -9a), 126.3 (d, s, C-2, -7).

A single-crystal X-ray structure analysis of the compound (I, R ¹ = R ² = R ³ = R ⁴ = phenyl) was able to be carried out using crystals obtained from a solution in dichloromethane.

Example 8:

Synthesis of 4,5-bis (diphenylphosphino) acridine (la):

A solution of 337 mg (mmol) of 4,5-dibromoacridine (XD) and 440 mg (2 mmol) of chlorodiphenylphosphine (Ph PCl) in 40 ml of tetrahydrofuran was added dropwise to a boiling suspension of 72 mg (3 mmol) of magnesium powder in 20 ml of tetrahydrofuran . The mixture was then stirred at room temperature for 20 h. Hydrolysis with water and dilute hydrochloric acid, extraction with diethyl ether, drying the ether phase over sodium sulfate and distilling off the solvent gave a brown crude product from which 72 mg (15% of theory) was obtained by repeated recrystallization from dichloromethane and dichloromethane / hexane. Bis (diphenylphosphino) acridine (la) were obtained as a yellow powder.

Example 9:

Synthesis of 4,5-difluoroacridine (XIII): a) 3-fluoro-2- (2-fluorohenylamino) benzoic acid (XVI):

2-Amino-3-fluorobenzoic acid (XIV) was prepared as described in: B.

McKittrick, A. Failli, RJ Steffan, RM Soll, P. Hughes, J. Schmid, CC Shaw, AA Asselin, R. Noureldin, and G. Gavin, J. Heterocyclic Chem. 27 (1990) 2151; F. Clemence, O. Le Martret and F. Delevallee, U.S. Patent 4,596,875 (June 24, 1986).

A mixture of 14.0 g (90.2 mmol) of 2-amino-3-fluorobenzoic acid (XIV), 12.5 g (90.4 mmol) of potassium carbonate, 21.0 g (94.6 mmol) of 2-fluoroiodobenzene (XV) and a spatula tip of copper powder in 85 ml of cyclohexanol became 12 Heated to reflux for hours. The solvent was then removed by steam distillation and the aqueous residue obtained was centrifuged. The soluble centrifugate was acidified with dilute hydrochloric acid and the precipitate formed was filtered off and dried. Fractional sublimation of the solid in a high vacuum gave 16.0 g (71% of theory) of 3-fluoro-2- (2-fluorophenylamino) benzoic acid (XVI) as a yellow powder, mp. 176 ° C. C ₁₃ H ₉ F ₂ NO ₂ (249.22 g mor ¹ ): calc. 62.65% C, 3.64% H, 15.25% F, 5.62% N found 62.38% C, 3.72% H, 15.15% F, 5.66% N

MS (EI, 70 eV, VT 90 ° C): m / z (%) = 249 (50, M ^{® *} ), 232 (15), 231 (100,

[M - H ₂ O] ^® '), 203 (15), 202 (12), 183 (15), 182 (13). - IR (KBr): v = 3360 cm ^"1

(m, V [NH]), 3060 (m, br., v [COO-H]), 1660 (s, v [C = O]), 1525 (s), 1260 (s, v [C- F ]), 740 (s, γ [CH]). - ¹⁹ F-NMR (188 MHz, [D ₆ ] acetone, external standard CFC1 ₃ ): δ = -1 18.0 (s), -131.0 (s). - ^! H-NMR (400 MHz, [D ₆ ] acetone): δ = 9.38 (s, br., 1 H, NH), 7.90 (dd, ³ 7 _5. _{H 6} H = ⁸ -l Hz, ⁴ 7 ₄ . _{H 6.} _H - 2 Hz. 6-H), 7.39 (ddd, ³ 7 ₃ _ _{F 4.} _H = 12.2 Hz, ³ 7 _4. _{H 5.} _H = 8.0 Hz, ⁴ 7 _4. _{H 6.} _H «2 Hz, 1 H, 4-H), 7.16-7.02 (m, 3H), 6.99- 6.88 (m, 2H). - ¹³ C-NMR (100 MHz, [D ₆ ] acetone): δ (multiplicity with respect to ^] 7 _CH , coupling with ¹⁹ F) = 169.6 (s, d with ⁴ 7 _CF = 4.0 Hz, COOH), 154.9, (s , d with ^ cp = 246.6 Hz, C-3), 153.3 (s, d with ^l J _CF = 241.7 Hz), 134.8 (s, m, ² 7 _CF = 11.2 Hz, C-2), 131.7 (s, m, ² 7 _CF = 11.2 Hz, C-1 '), 128.2 (d, d with ⁴ 7 _CF = 3.2 Hz, C-6), 124.8 (d, d with ⁴ 7 _CF = 3.2 Hz, C- 5 '), 123.0 (d, d with ³ 7 _CF = 7.2 Hz, C-5), 121.5 (d, d with ² 7 _CF = 20.1 Hz, C-4), 121.5 (d, d with ³ 7 _CF = 5.6 Hz, C-4 '), 120.4 (s, d with ³ 7 _CF = 4.0 Hz, Cl), 120.2 (d, d with ³ 7 _CF = 6.4 Hz, C-6'), 115.7 (d, d with ² 7 _CF = 19.3 Hz, C-3 '); Incremental calculations were carried out to help with the assignment.

b) 9-chloro-4,5-difluoroacridine (XVID:

A suspension of 31.1 g (125 mmol) of 3-fluoro-2- (2-fluorophenylamino) benzoic acid (XVD in 110 ml (1.19 mol) of phosphoryl chloride was heated to reflux for 3.5 hours. The excess phosphoryl chloride was then added to the resulting solution The remaining brown oil was dissolved in chloroform and the solution was dropped into ice-cooled dilute aqueous ammonia solution with stirring. After the mixture reached room temperature, the phases were separated. The aqueous phase was extracted twice with chloroform and the combined organic Phases were dried over sodium sulfate, the solvent was distilled off on a rotary evaporator and the residue was dried under high vacuum to give 29.8 g of a brown-yellow solid, fractionated sublimation under high vacuum gave 25.4 g (81% of theory) of 9-chloro-4, 5-difluoro-acridine (XVII) in analytically pure form as a yellow powder of mp. 183-186 ° C. C _{] 3} H ₆ F ₂ C1N (249.65 g mor ¹ ): calc. 62.55% C, 2.42% H, 15.22% F, 5.61% N, 14.20% Cl found 62.38% C, 2.51% H, 15.19% F, 5.69% N, 14.16% Cl

MS (EI, 70 eV, VT 60 ° C): m / z (%) = 249 (100, M ^® \ ³⁵ C1, isotope pattern as calculated), 213 (10). - IR (KBr): v = 3050 cm ^"1 (m, v [CH], 1630 s, 1550 (s, v [C = C]), 1330 (s), 1250 (s, v [CF]), 740 (s, γ [CH]). - ¹⁹ F-NMR (188 MHz, CDC1 ₃ , external standard CFC1 ₃ ): δ = -122.4 (s). - ^! H-NMR (400 MHz, CDC1 ₃ ): δ = 8.18 (d "t"), 7.58 (ddd), 7.51 (ddd) [ABCX spin system with X = ¹⁹ F, ³ 7 _cx = 10.1 Hz, ³ 7 _AB = 8.7 Hz, ³ 7 _BC = 7.4 Hz, ³ 7 _AC = 1.3 Hz, ⁴ 7 _AX = 1.3 Hz, ³ 7 _BX = 5.0 Hz, 2 H each for 1-, 8-H (A), 2-, 7-H (B), 3-, 6-H (C)].

c) 4.5-difluoroacridine (XU) i) Synthesis of 9- (p-toluenesulfonic acid hvdrazido) -4,5-difluoroacridinium ^ hvdrochloride (XVIII): A solution of 25.4 g (102 mmol) 9-chloro-4,5-difluoroacridine (XVID in 300 ml of anhydrous chloroform was added dropwise to a suspension of 20.7 g (111 mmol) of αra-toluenesulfonic acid hydrazide in 200 ml of anhydrous chloroform which had been stirred at 50 ° C. The suspension which had cooled to room temperature was then stirred for 2 d. The precipitate was filtered off, Washed with a little chloroform and dried under high vacuum to give 38.7 g (87% of theory) of 9- (p-toluenesulfonic acid hydrazido) -4,5-difluoroacridinium hydrochloride (XVUI) as a bright yellow solid. MS (EI, 70 eV, VT 80 ° C): m / z (%) = 399 (3, [M - HC1] ^{® *} ), 244 (100), 224 (13),

215 (23). - IR (KBr): v = 3410 cm ^"1 (w, v [NH]), 3230 (m, v [NH]), 3200-2000 (vs, br., V [N ^® -H]), 1345 (s, v [SO]), 1165 (s, v [SO]).

ii) Conversion to 4,5-difluoroacridine (XIII): 670 ml of 3.4 molar was added to a suspension of 37.7 g (86.3 mmol) of 9 - (/? - toluenesulfonic acid hydrazido) - 4,5-difluoroacridinium chloride (XVHI) in 1300 ml of ethylene glycol Sodium hydroxide solution was added and the mixture was heated under reflux with stirring for 2 hours. After cooling, the suspension was poured into 4 liters of water and the resulting precipitate was filtered off, washed thoroughly with water and dried under high vacuum. Sublimation in a high vacuum gave 11.6 g (62% of theory) of 4,5-difluoroacridine (X) as a yellow solid, mp. 193-195 ° C.

C ₁₃ H ₇ F ₂ N (215.20 g mol ^"1 ): calc. 72.56% C, 3.28% H, 17.66% F, 6.51% N found. 72.30% C, 3.51% H, 17.57% F, 6.45% N

MS (EI, 70 eV, VT 80 ° C): m / z (%) = 215 (100, ^{M® *} ), 214 (10). - IR (KBr): v =

3070 cm ^"1 (w, v [CH]), 1250 (s, v [CF]), 750 (s, γ [CH]). - ¹⁹ F-NMR (188 MHz, CDC1 ₃ , external standard CFC1 ₃ ) : δ = -123.7 (s). - H-NMR (400 MHz, CDC1 ₃ ): δ = 8.79 (t, ⁵ 7 _HF = 1.5 Hz, 1 H, 9-H), 7.80-7.74 (m, 2 H , 1-, 8-H), 7.51-743 (m, 4 H, 2-, 3-H and 6-, 7-H). - ¹³ C-NMR (50 MHz, CDC1 ₃ ): δ (multiplicity with respect to ^ CH, coupling with ¹⁹ F) = 157.8 (s, d with ^] J _CF = 259.8 Hz, C-4, -5), 139.7 (s, d with ² 7 _CF = 14.0 Hz, C-4a, -10a) , 135.7 (d, t with ⁴ 7 _CF = 6.1 Hz, C-9), 128.0 (s, s br., C-8a, -9a), 125.6 (d, d with ³ 7 _CF = 7.0 Hz, C- 2, -7), 123.8 (d, "t" with ∑ ⁿ 7 _CF = 6.1 Hz, C-1, -8), 113.3 (d, d with ² 7 _CF = 19.2 Hz, C-3, -6); Incremental calculations were carried out to help with the assignment.

Example 10:

Synthesis of 4,5-dibromoacridine (XIX): a) 3-bromo-2- (2-bromophenylamino) benzoic acid (XXII)

3-bromo-2-iodobenzoic acid (XX) was prepared as described in: D. Twiss and R.V. Heinzelmann, J. Org. Chem. \ 5 (1950) 496.

A mixture of 16.0 g (46 mmol) sodium 3-bromo-2-iodobenzoate [prepared from 15.0 g (46 mmol) 3-bromo-2-iodobenzoic acid (XX) and 1.1 g (46 mmol) sodium hydride], 19.5 g ( 100 mmol) of sodium 2-bromoanilide [prepared from 17.3 g (100 mmol) of 2-bromoaniline (XXI) and 2.4 g (100 mmol) of sodium hydride] and a spatula tip of copper powder in 100 ml of tetrahydrofuran were heated under reflux for 9 h. The solvent was distilled off, the residue was extracted with 0.5 molar sodium hydroxide solution and the suspension formed was centrifuged. The centrifugate was acidified with dilute hydrochloric acid, the precipitated solid was filtered off and dried in a high vacuum. Fractional sublimation in a high vacuum gave 6.3 g (37% of theory) of 3-bromo-2- (2-bromophenylamino) benzoic acid (XXII) as a yellow powder with a melting point of = 181-182 ° C.

C ₁₃ H ₉ Br ₂ NO ₂ (371.03 g mor ¹ ): calc. 42.08% C, 2.44% H, 43.07% Br, 3.78% N found 42.28% C, 2.41% H, 42.82% Br, 3.75% N

MS (EI, 70 eV, VT 120 ° C): m / z (%) = 369 (21, M ^{® *} with ⁷⁹ Br ₂ , isotope pattern as calculated), 290 (9, [M - Br] ^® with ⁷⁹ Br), 272 (100, [M - Br- H ₂ O] ^θ with ⁷⁹ Br), 244 (12), 193 (11), 165 (29). - 'H-NMR (200 MHz, [D ₆ ] acetone): δ = 8.70 (s, br., 1 H, NH), 8.10 (dd), 7.87 (dd), 7.19 ("t") [AMX- Spin system with ³ 7 _MX = 7.9 Hz, ³ 7 _AX = 7.3 Hz, ⁴ 7 _AM = 1.5 Hz, 1 H each for 6- (A), 4-H (M), 5-H (X)], 7.57 ( dd), 7.16 (ddd), 6.83 (d "t"), 6.54 (dd) [ABCD spin system with ³ 7 _AC = 7.9 Hz, ³ 7 _BD = 7.6 Hz, ³ 7 _BC = 7.2 Hz, ⁴ 7 _AB = 1.5 Hz, ⁴ 7 _CD = 1.5 Hz, 1 H each for 3'-H (A), 5'-H (B), 4'-H (C), 6'-H (D)]. ¹³ C-NMR (50 MHz, [D ₆ ] acetone): δ = 168.5 (s, COOH), 143.5 (s, C-2),

142.0 (s, C-l '), 139.5 (d, C-4) 133.4 (d, C-3'), 132.0, (d, C-6), 128.4 (d, C-5 '),

125.1 (C-5), 125.1 (s, Cl or C-3), 120.1 (s, Cl or C-3), 122.9 (d, C-4 'or C-6'), 118.6 (d, C- 4 'or C-6'), 1 14.0 (s, C-2 ') Incremental calculations were carried out to help with the assignment.

b) 4.5-dibromo-9-chloroacridine (XXIII.)

A suspension of 7.43 g (20.0 mmol) of 3-bromo-2- (2-bromophenylamino) benzoic acid (XXII) in 19.5 ml (213 mmol) of distilled phosphoryl chloride was heated under reflux for 2.5 h. The excess phosphoryl chloride was then distilled off in vacuo at room temperature. The resulting brown oil was dissolved in chloroform and the solution was added dropwise to ice-cooled, dilute aqueous ammonia solution while stirring. After the mixture reached room temperature, the phases were separated. The aqueous phase was extracted twice with chloroform and the combined organic phases were dried over sodium sulfate. The solvent was distilled off in vacuo and the residue was dried in a high vacuum. From 7.00 g of crude product, 5.5 g (74% of theory) of 4,5-dibromo-9-chloroacridine (XXIJJ) were obtained as a pure yellow solid of mp 195-196 ° C. by fractional sublimation in a high vacuum. C _{! 3} H ₆ Br ₂ ClN (371.46 g mor ¹ ): calc. 42.04% C, 1.63% H, 43.02% Br, 9.54% Cl, 3.77% N found. 41.97% C, 1.68% H, 43.10% Br, 9.54% Cl, 3.78% N

xxm

MS (EI, 70 eV, VT 100 ° C): m / z (%) = 369 (100, M ^{θ *} with 79ßr ₂ , ³⁵ C1, Isoto¬

pattern as calculated), 290 (1 1, [M -Br] ^® with ⁷⁹ Br, ³⁵ C1), 211 (25, [M - 2Br] ^® \

³⁵ C1), 176 (15, [M - 2Br-Cl] ^® ). - ER (KBr) v = 1615 cm ^"1 (m), 1550 (m, v [C = C]); 750 (s), 740 (s, γ [CH]). - ^] H-NMR (200 MHz , CDC1 ₃ ): δ = 8.42 (dd), 8.23 (dd), 7.51 (dd) [AMX spin system with ³ 7 _AX = 8.8 Hz, ³ 7 _MX = 7.2 Hz, ⁴ 7 _AM = 1.3 Hz, each 2 H for 1-, 8-H (A), 3-, 6-H (M), 2-, 7-H (X).

4,5-dibromoacridine (XIX): i) Synthesis of 9- (p-toluenesulfonic acid hydrazido) -4,5-dibromoacridinium chloride (XXIV): A solution of 5.2 g (14.0 mmol) of 4.5 dibromo-9-chloroacridine (XXHJ ) in 20 ml of anhydrous chloroform was added dropwise to a suspension of 2.9 g (15.6 mmol) of αra-toluenesulfonic acid hydrazide in 30 ml of anhydrous chloroform, which was stirred at 50 ° C. The resulting suspension was stirred for 24 hours at room temperature. The precipitate formed was filtered off, washed with water and dried under high vacuum. 7.1 g (91% of theory) of 9- (p-toluenesulfonic acid hydrazido) -4,5-dibromoacridinium chloride were obtained as a yellow solid. IR (KBr) v = 3370 cm ^"1 (w), 3290 (m, v [NH]]; 2920 (m, v [CH]); 2750 (m br, v [NH] ^® ); 1350 (m) , 1 170 (s, v [SO); 745 (m, γ [CH]).

ii) Conversion to 4,5-dibromoacridine (XIX): A solution of 13.5 g was added to a suspension of 7.1 g (12.7 mmol) of 9 (p-toluenesulfonic acid hydrazido) -4,5-dibromoacridinium chloride in 200 ml of ethylene glycol Sodium hydroxide in 100 ml of water was added and the mixture was refluxed with stirring for 3 hours. After cooling, the solution was poured into 600 ml of water. The precipitate was filtered off, washed with water and dried in a high vacuum. 3.9 g (91% of theory) of 4,5-dibromoacridine (XIX) were obtained as a yellow solid which was obtained by pure recrystallization from toluene / cyclohexane (mp. 205 ° C.). C ₁₃ H ₇ Br ₂ N (337.01 g or ¹ ): calc. 46.33% C, 2.09% H, 47.42% Br 4.16% N found 46.18% C, 2.19% H, 47.51% Br, 4.23% N

MS (EI, 70 eV, VT 120 ° C): m / z (%) = 335 (52, M ^{θ *} with ⁷⁹ Br ₂ , isotope pattern

as calc.), 246 (14, [M-Br] ^® with ⁷⁹ Br), 177 (38, [M-2Br] ^{® *} ), 150 (10), 75 (16).

- IR (KBr) v = 3050 cm ^'1 (w, v [CH]); 1620 (s, v [C = C)]); 740 (s, γ [CH)]). 'H-NMR (200 MHz, CDC1 ₃ ): δ = 8.78 (s, 1 H, 9-H), 8.18 (dd), 7.98 (dd), 7.40 (dd) [AMX spin system with ³ 7 _MX = 8.5 Hz, ³ 7 _AX = 7.2 Hz, ⁴ 7 _AM = 1.4 Hz, 2 H each for 3-, 6-H (A), 1-, 8-H (M), 2-, 7-H (X)] . - ¹³ C-NMR (50 MHz, CDC1 ₃ ): δ = 145.8

(s, C-4a, -10a), 137.4 (d, C-9), 134.0 (d, C-1, -8 or C-3, -6), 127.8 (d C-1, -8 or C -3, -6), 127.5 (s, C-8a, -9a), 126.5 (d, C-2, -7), 125.7 (s, C-4, -5). Incremental calculations were carried out to help with the assignment.

Claims

Expectations:

1. transition metal compounds of the general formula (II),

II

wherein R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} hydrogen atoms or, preferably R ⁹ or R ² and R ⁷ , one or two alkyl or alkoxy groups each having 1 to 12 C. -Atoms or aryl, NH ₂ , NR ₂ , NR ₃ ⁺ Y ^" (R = alkyl with C, to C ₄ , Y ^" = anions such as halides), OH, COOH, SO ₃ H, halogens or CF or in which R. ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ⁹ = H or, preferably R ⁹ or R ² and R ⁷ , one or two alkyl, alkoxy or aryl groups with groups such as NH ₂ , NR ₂ , NR ₃ ⁺ Y ^" (R = alkyl with Ci to C ₄ , Y ^" = anions such as halides), OH, COOH, SO ₃ H, halogens or CF ₃ , where R ¹¹ , R ¹² , R ¹³ and R ¹⁴ aryl, aralkyl, alkaryl, alkyl cycloalkyl groups, or with groups such as NH ₂ , NR ₂ , NR ₃ ⁺ Y ^" (R = alkyl with up to C ₄ , Y ^" = anions such as halides), OH, COOH, SO H, halogens or CF ₃ substituted phenyl or alkyl groups in which R ¹¹ , R ¹² , R ¹³ and R ^{14 are} either identical or different, in which R ¹¹ and R ¹² and R ¹³ and R ¹⁴ each have two alkyl substituents which are linked to form phosphacycloalkanes and M transition metals Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au in different oxidation levels, X up to three anions or ligands (n = 0, 1, 2, 3) such as halides (F ^" , Cl ^" , Br ^" , T), cyanide, acetate, propionate, trifluoacetate, acetylacetonate, hexafluoroacetylacetonate, sulfate, alkyl sulfonate, Aryl sulfonate, trifluoromethanesulfonate, hydride, alkyl, aryl, carbon monoxide, nitrosyl, trialkylphosphine, triarylphosphine, trialkylphosphite, triarylphosphite, ethylene, olefins, acetylenes, cyclopentadienyl, benzene, which are bonded to the transition metal M, mean.

1 1 14

2. Compounds according to claim 1, wherein R - R have the same meaning but are not substituted.

3. Compounds according to claim 1, wherein R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ⁹

Are hydrogen atoms.

4. Compounds according to claim 1, wherein R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} hydrogen atoms and R ^{1 1} , R ¹² , R ¹³ and R ¹⁴ aryl, aralkyl, alkaryl , Alkyl or cycloalkyl groups.

5. Compounds according to claim 1, wherein R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} hydrogen atoms and R ¹¹ , R ¹² , R ¹³ and R ^{14 are} phenyl.

6. Compounds of the general formula (I),

I.

wherein R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} hydrogen atoms or, preferably R ⁹ or R ² and R ⁷ , one to two alkyl or alkoxy groups each having 1 to 12 C atoms or aryl, NH ₂ , NR ₂ , NR ₃ ⁺ Y ^" (R = alkyl with C, to C ₄ , Y ^" = anions such as halides), OH, COOH, SO ₃ H, halogens or CF ₃ or wherein R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ⁹ = H or, preferably R ⁹ or R ² and R ⁷ , one to two alkyl, alkoxy or aryl groups which with groups such as NH ₂ , NR ₂ , NR ₃ ⁺ Y ^" (R = alkyl with C, to C ₄ , Y ^" = anions such as halides), OH, COOH, SO ₃ H, halogens or CF ₃ , where R ¹¹ , R ¹² , R ¹³ and R ¹⁴ aryl, aralkyl, alkaryl, alkylcycloalkyl groups, or with groups such as NH ₂ , NR ₂ , NR ₃ ⁺ X ^" (R = alkyl with Ci to C, Y ^" = Anions such as halides), OH, COOH, SO ₃ H, halogens or CF ₃ substituted phenyl or alkyl groups in which R ^{1 1} , R ¹² , R ¹³ and R ^{14 are} either identical or different, in which R ¹¹ and R ¹² and R ¹³ and R ¹⁴ each represent two alkyl substituents which are linked to one another to form phosphacycloalkanes.

11 14

7. Compounds according to claim 6, wherein R - R have the same meaning but are not substituted.

8. Compounds according to claim 6, wherein R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} hydrogen atoms.

9. Compounds according to claim 6, wherein R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} hydrogen atoms and R ¹¹ , R ¹² , R ¹³ and R ^{14 are} aryl, aralkyl, alkaryl, Mean alkyl or cycloalkyl groups.

10. A compound according to claim 6, wherein R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} hydrogen atoms and R ¹¹ , R ¹² , R ¹³ and R ^{14 are} phenyl.

1 1. Compounds consisting of mixtures of the compounds of general formula (I) according to claims 6-10 and transition metal compounds of the elements Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au in the ratio between 0.1 to 100, preferably between 0.5 and 10, which are formed in situ.

12. Compounds according to claims 1-5 and 11, to which Lewis acids such as A1C1 ₃ , BF ₃ , SnCl ₂ , ZnCl ₂ , SbF ₃ , SbF ₅ or soluble silver (I) salts in amounts of 1 to 10 equivalents of the transition metal Connections are added.

13. 4,5-dihaloacridines (halogen = F, Cl, Br, J).

14. 4,5-difluoroacridine (formula XIII)

XIII

and 4,5-dibromoacridine (Formula XIX).

XIX

15. A process for the preparation of catalysts of the general formula (II) according to Claims 1 to 5, which is characterized in that 4,5-diphosphinoacridine ligands of the general formula (I) according to Claims 6 to 10 and transition metal compounds of Elements Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au with different oxidation levels in organic solvents such as Hydrocarbons, preferably benzene and toluene, ethers, preferably diethyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, carbon tetrachloride, chlorinated hydrocarbons, preferably dichloromethane and chloroform, alcohols, preferably butanol, acetone, acetonitrile, dimethylformamide at temperatures between -100 ° C. and +200 ° C, preferably between 0 ° C and 100 ° C, are reacted.

16. A method for using catalysts according to claims 1 to 5, 11 and 12 for the carbon monoxide concentration via the water gas equilibrium (WGSR: CO + H ₂ O = CO ₂ + H ₂ ) and for the catalysis of reactions such as hydroformylation, Carbonylation, carboxylation, hydrogenation, hydrocyanation, hydrosilylation, polymerization, isomerization, cross-coupling and metathesis, which are characterized in that solid, liquid or gaseous reactants in the presence of these catalysts, in organic solvents, water or mixtures of various solvents with and without water are reacted at temperatures between -100 ° C and +300 ° C, preferably between 0 ° C and 200 ° C, and a pressure between 1 bar and 300 bar, preferably between 1 bar and 100 bar.

17. A process for producing hydrogen from carbon monoxide and water via the water gas equilibrium (WGSR: CO + H ₂ O = CO ₂ + H ₂ ), which is characterized in that carbon monoxide or gases containing carbon dioxide and water in the presence of catalysts according to claims 1 to 5, 11 and 12, using either a water-miscible organic solvent such as alcohols, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, glycol, glycol dialkyl ether, oligomeric glycols or their dialkyl ether, at temperatures between 0 ° C and 300 ° C, preferably between 100 ° C and 250 ° C, and a pressure between 1 bar and 300 bar, preferably between 1 bar and 100 bar.

18. The method according to claim 17 with 4,5-bis (diphenylphosphino) acridine-palladium (II) chloride (VIII) as a catalyst.

19. A process for the preparation of 4,5-diphosphinoacridine ligands of the general formula (I) according to claims 6 to 10, which is characterized in that 4,5-dihaloacridines (halogen = F, Cl, Br, J), preferably 4th , 5-difluoroacridine (XIII). with alkali metal phosphides [R ₂ P ^_ M ⁺ (R = alkyl, phenyl or aryl; M ⁺ = Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ )], preferably potassium phosphides [R ₂ P ^_ K ⁺ (R = Alkyl, phenyl or aryl)], in aprotic organic solvents such as hydrocarbons, preferably toluene, ether, preferably diethyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, oligomeric ethylene glycol dimethyl ether, hexamethylphosphoric acid triamide, N-methyl-2-pyrrolidinone, preferably in 1, 4-dioxane, at temperatures between -100 ° C and +200 ° C, preferably between 0 ° C and +150 ° C, are reacted.

20. A process for the preparation of 4,5-bis (diphenylphosphino) acridine (La) according to claim 10, which is characterized in that 4,5-dihaloacridines (halogen = F, Cl, Br, J), preferably 4.5- Difluoroacridine (XIII), with alkali metal diphenylphosphide [Ph ₂ P ^~ M ⁺ (M ⁺ = Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ )], preferably potassium diphenylphosphide (Ph ₂ P ^_ K ⁺ ) in aprotic organic solvents in aprotic organic solvents such as hydrocarbons, preferably toluene, ether, preferably diethyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, oligomeric ethylene glycol dimethyl ether, hexamethylphosphoric acid triamide, N-methyl-2-pyrrolidinone, preferably in 1,4-dioxane , at temperatures between -100 ° C and +200 ° C, preferably between 0 ° C and +150 ° C, are reacted.

21. A process for the preparation of 4,5-diphosphinoacridine ligands of the general formula (I) according to claims 6 to 10, which is characterized in that 4,5-dihaloacridines (halogen = F, Cl, Br, J), preferably 4th , 5-dibromoacridine (XIX), with chlorophosphines [R ₂ PC1 (R = alkyl, phenyl or Aryl)] and magnesium in aprotic organic solvents such as hydrocarbons, preferably toluene, ether, preferably diethyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, oligomeric ethylene glycol dimethyl ether, hexamethylphosphoric triamide, N-methyl-2-pyrrolidinone, preferably in tetrahydrofuran Temperatures between -100 ° C and +100 ° C, preferably between 0 ° C and +100 ° C, are reacted.

22. A process for the preparation of 4,5-bis (diphenylphosphino) acridine (La) according to claim 10, which is characterized in that 4,5-dihaloacridines (halogen = F, Cl, Br, J), preferably 4.5- Dibromoacridine (XIX), with chlorodiphenylphosphine (Ph ₂ PCl) and magnesium in aprotic organic solvents such as hydrocarbons, preferably toluene, ether, preferably diethyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, oligomeric ethylene glycol dimethyl ether, hexamethylphosphoric acid triamide, N-methyl methyl 2-pyrrolidinone, preferably in tetrahydrofuran, at temperatures between -100 ° C and +100 ° C, preferably between 0 ° C and +100 ° C, are reacted.

23. A process for the preparation of 4,5-difluoroacridine (XIII) according to claims 13 and 14 from 2-amino-3-fluorobenzoic acid (XIV) and 2-fluoroiodobenzene (XV), which is characterized in that. (XIV) and (XV) in the presence of copper powder and potassium carbonate in solvents such as alcohols, ethylene glycols, ethers, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, preferably in cyclohexanol, at temperatures between 20 ° C. and 200 ° C., preferably at 100 ° C to 160 ° C, converted to 3-fluoro-2- (2-fluorophenylamino) benzoic acid (XVI), (XVI) in phosphoryl chloride (POCl) at temperatures between 50 ° C and 150 ° C to 9-chlorine -4,5-difluoroacridine (XVII) is cyclized, (XVII) with / 7-toluenesulfonic acid hydrazide (TolSO ₂ NHNH ₂ ) in hydrocarbons or chlorinated hydrocarbons, preferably chloroform, at temperatures between 0 ° C and 100 ° C to 9- (-Toluenesulfone - acid hydrazido) -4,5-difluoroacridinium hydrochloride (XVIII) is reacted and (XVIII) with sodium hydroxide solution in ethylene glycol at temperatures between 50 ° C and 200 ° C to 4,5-difluoroacridine (XIII) is decomposed.

24. A process for the preparation of 4,5-dibromoacridine (XIX) according to claims 13 and 14 from 3-bromo-2-iodobenzoic acid (XX) and 2-bromoaniline (XXI), which is characterized in that (XX) and (XXI ) are converted with sodium hydride into their respective sodium compounds, this presence of copper powder in solvents such as ether, tetrahydrofuran, 1, 4-dioxane, dimethoxyethane, preferably in tetrahydrofuran, at temperatures between 20 ° C and 150 ° C, to 3-bromo -2- (2-bromophenylamino) benzoic acid (XXII) is reacted, (XXII) is cyclized in phosphoryl chloride (POCl ₃ ) at temperatures between 50 ° C and 150 ° C to 9-chloro-4,5-dibromoacridine (XXIII), (XXIII) with toluenesulfonic acid hydrazide (TolSO ₂ NHNH ₂ ) in hydrocarbons or chlorinated hydrocarbons, preferably chloroform, at temperatures between 0 ° C. and 100 ° C. to give 9- (p-toluenesulfonic acid hydrazido) -4,5-dibromoacridinium hydrochloride (XXIV) and (XXIV) with sodium hydroxide solution in ethylene glycol at temperature between 50 ° C and 200 ° C to 4,5-dibromoacridine (XIX) is decomposed.