DE19647640A1 - Mono-bridged porphyrin derivatives - Google Patents

Abstract

Mono-bridged porphyrin derivatives of formula (I) and their salts are new. R<1> - R<6> = independently alkyl, cycloalkyl, optionally substituted aryl or optionally substituted heteroaryl; R<7>, R<8> = independently H, halo, alkyl, NO2, SO3H, substituted phenyl or CN; Y = R<9>-A-R<10>; R<9>, R<10> = independently optionally substituted arylene, optionally substituted heteroarylene or optionally substituted cycloalkylene which is optionally interrupted by one or more O, N or S heteroatoms; A = a divalent linear or branched group. Also claimed are metal complexes of formula (II). Z, Z' = independently M, ML<1> or ML<1>L<2>, where M is a group IV, V, VI, VII, VIII, I or II transition metal cation and L<1> and L<2> are independent axial ligands.

Description

The present invention relates to mono-bridged porphyrin di mers and their metal complexes, processes for their production as well as catalytic processes using the metal porphy complexes.

Metal porphyrins are found in nature as prosthetic Group in the active centers of a variety of proteins. she take part in a wide variety of metabolic processes. In addition to the classic example of oxygen transport through Hemo- or myoglobin mainly include redox reactions and especially oxidation reactions in which certain metal pores phyrine both the transfer of electrons and the ge catalyze any oxygen transfer that may occur. In in this connection are particularly those in plants and animals to name richly widespread cytochrome P-450 systems.

It is therefore not surprising that numerous attempts have been made under synthetic biomimetic metal porphyrins to develop with which certain reactions in the of the Allow nature to perform in a manner that does not affect the having to resort to entire protein. A success of this Undertaking, however, presupposes that in this case the syn Theoretical metal porphyrin also takes on the functions that im Protein from the surrounding, often very specifically arranged Amino acids are perceived. For example, it is on the formation of bags of a certain size, shape or pola rity for receiving a specific substrate to which ready position of certain amino acids coordinating to the metal as so-called axial ligands or to steric influences to think of the porphyry scaffold. Directed porphyrin porphyrin interactions also count.

Iron, manganese or ruthenium porphyrins have been described many times Examples of catalysts for the oxidation of hydrocarbons substances, such as the hydroxylation of alkanes or epoxidation of Alkenes.  

US 4,822,899 describes, for example, that niobium, rhenium, Ruthenium, osmium, rhodium or iridium porphyrins for aerobic use catalytic oxidation of olefins in the absence of Coreduk are useful.

Conjectures about the oxygen-transmitting species have led to Postulation of porphyrins with a more or less reactive Metal oxo or metal dioxo grouping performed. In a ver publication by Groves J. T. et al. in Journal of the American Chemical Society 1985, 107, 5790-5792, for example 5,10,15,20-tetramesitylporphyrinato-trans-dioxo-ruthenium (VI) be wrote which is an olefin with transfer of an oxo group epoxidized and then with another oxo-ruthenium (IV) species to a trans-dioxo-ruthenium (VI) and a ruthenium (II) por phyrin disproportionate. This ruthenium (II) complex reacts then with molecular oxygen to form oxo-ruthe nium (IV), which closes the catalytic cycle.

DE 43 43 268 also makes reference to the reaction described above Use. The ruthenium porphyrin described there is steric sophisticated meso substituents in the form of optionally sub substituted anthryl groups and is suitable for catalytic epo Oxidation of olefins with oxygen.

Nevertheless, these porphyrins often meet those of Kataly unsatisfactory requirements. The reactions are often of a noticeable decomposition of the Accompanied catalyst, the yields are low or Product purity is not satisfactory. In the synthesis optically active products could generate enantiomeric excesses in the The past is rarely preserved.

The efforts of the professional community to create more complex porphyrin systems create to meet the specific requirements of catalytic reaction For example, a recent published publication by Collman J.P. et al. in journal or Organic Chemistry, 1995, 60, 1926-1931. The authors be write here the synthesis of porphyrin dimers, over a rigid aromatic bridge are linked together so that the the two, almost planar macrocycles face each other. This rigid arrangement was chosen to make the two porphyrin bound metal atoms are arranged so that they together on can act on a small substrate molecule. This rigid arrangement particularly in the reduction of oxygen to water, from protons to hydrogen or for mutual conversion of molecular nitrogen and nitrogen hydrides important. However, it is not suitable for processes where more or  less bulky organic molecules are involved as substrates, such as hydroxylations of alkanes or epoxidations of alkenes.

Surprisingly, it has been found that certain monovers bridged metal porphyrin dimers effective catalysts, in particular represent those for the oxidation of hydrocarbons. Here the two macrocycles are linked so that one on the one hand, sufficient flexibility via a kind of moving share nier is given, but on the other hand ver from the advantages bridged porphyrin dimers for intramolecular exchange reactions can be benefited between the two metal centers.

The present invention therefore relates to mono-bridged porphyrin dimers of the formula I.

wherein
R ¹ to R ⁶ , which may be the same or different, represent alkyl, cycloalkyl, aryl, substituted aryl, heteroaryl or substituted heteroaryl,
R ⁷ and R ⁸ , which may be the same or different, represent hydrogen, halogen, alkyl, nitro, SO ₃ H, phenyl, substituted phenyl or cyano,
Y stands for -R ⁹ -AR ¹⁰ -
wherein
R ⁹ and R ¹⁰ , which may be the same or different, represent arylene, substituted arylene, heteroarylene, substituted heteroarylene, optionally cycloalkylene or substituted cycloalkylene which is interrupted by one or more heteroatoms selected from O, N or S and
A represents a bivalent, linear or branched radical,
and salts thereof.

The terms "alkyl, alkoxy, alkylthio or alkylsulfonyl" encompass straight-chain or branched alkyl groups such as methyl, ethyl, n- and i-propyl, n, i- or t-butyl, n-pentyl, neopentyl, n-hexyl etc. Unless otherwise stated, "alkyl" in the radicals mentioned above, preferably for C ₁ -C ₁₀ alkyl, in particular for C ₁ -C ₆ alkyl and particularly preferably for C ₁ -C ₃ alkyl. "Cycloalkyl" includes cyclic alkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or polycyclic radicals, such as norbonyl, camphyl, indanyl or deca hydronaphthyl, where the mono- or polycyclic radicals can be substituted by one or more alkyl groups.

The term "halogen" includes fluorine, chlorine, bromine or iodine atom and in particular a fluorine or chlorine atom.

The term "haloalkyl" includes alkyl radicals, preferably Methyl radicals created by one or more halogen atoms, the same or can be different, are substituted and stands out preferably for trifluoroalkyl.

The terms "aryl, aryloxy, arylthio or arylsulfonyl" included aromatic residues, preferably naphthyl, anthryl, diphenyl and especially phenyl.

The term "heteroaryl" encompasses aromatic residues that have little contain at least one heteroatom selected from O, N or S. It is preferably a 5- or 6-membered hete rocyclic ring containing one, two or three heteroatoms. Preferred examples are thienyl, pyrroyl, imidazolyl, diazolyl, Isothiazolyl, thiadiazolyl, furyl, oxazolyl, isoxazolyl, pyridyl, Pyrimidyl, benzofuryl, benzodiazolyl, quinolyl, isoquinolyl, Indolyl or isoindolyl.

The terms "aralkyl, aralkoxy, aralkylthio or aralkylsulfonyl" encompass aryl radicals bonded via an alkylene chain, this alkylene radical in turn being able to be bonded to the basic structure via an oxygen or sulfur atom or an SO ₂ group. "Aralkyl" preferably stands for benzyl.

“Alkylene” means linear or branched, divalent alkyl radicals, such as methylene, 1,1- and 1,2-ethylene, 1,1-, 1,2-, 1,3- and 2,2-propylene, 2- Methyl-1,1-propylene etc. Unless otherwise stated, "alkylene" preferably represents C ₁ -C ₆ alkylene and in particular C ₁ -C ₄ alkylene.

"Arylene" means divalent aromatic radicals, such as 1,2-, 1,3- and 1,4-phenylene.

"Acyl" stands for RCO, where R preferably the above for "alkyl" and "aryl" has the meanings given. Acetyl is special prefers.

"Alkoxycarbonyl" stands for ROC (O), where R is preferably the above has meanings given for "alkyl". Is acetoxycarbonyl particularly preferred.

"Acyloxy" stands for RC (O) O, where R is preferably the above for "Alkyl" and "aryl" has the meanings given. Is acetyloxy particularly preferred.

The radicals mentioned above and in particular the aromatic radicals can be substituted once or more, the maximum number of substituents depending on the size of the radical, in particular the ring size of aromatic groups. The possible substitution patterns also include substituent numbers that are between one and the maximum number, and their distribution in all possible positions. For example, a phenyl ring can carry one, two, three, four or five substituents, which are the same or different, and each of these possibilities includes further isomers by different arrangement of the substituents on non-equivalent positions of the phenyl ring. If it is a heteroaryl radical, in particular the hetero atom can also be substituted, which often results in ionic radicals, such as nitrogen-alkylated heterocycles. The substituents are preferably selected from alkyl, alkoxy, alkylthio, alkylsulfonyl, aryl, aryloxy, arylthio, arylsulfonyl, aralkyl, aralkoxy, aralkylthio, aralkylsulfonyl, halo, cyano, nitro, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, COOH, alkoxycarbon , Acyloxy, SO ₃ H, sulfamoyl, dialkylsulfamoyl, carbamoyl, dialkylcarbamoyl, hydroxyl, thiolyl, optionally alkylated amines and ammonium radicals, in particular alkyl, alkoxy, cyano, nitro, CF ₃ , COOH and SO ₃ H.

The porphyrin dimers of the formula I according to the invention comprise two porphyrin macrocycles, in each of which one meso position is bonded to a divalent radical Y. Each of the two macrocycles therefore has three further meso positions R ¹ to R ⁶ , which, identically or differently, preferably represent phenyl, substituted phenyl, pyridyl, substituted pyridyl, naphthyl, substituted naphthyl, anthryl or substituted anthryl. If R ⁹ and R ^{10 also represent} aromatic radicals, for example arylene, substituted arylene, heteroarylene or substituted heteroarylene, one speaks of mono-bridged mesotetra (hetero) aryl porphyrin dimers. This class of compounds according to the invention is particularly preferred since they are relatively easy to synthesize, offer diverse substitution options for the aromatic substituents and, moreover, have application-technical advantages, in particular when carrying out oxidative catalysis.

Preferred substituents of aromatic radicals R ¹ to R ⁶ are alkyl, halogen, CN, NO ₂ , CF _{3 '} , SO ₃ H, COOH, acyloxy, alkoxycarbonyl, OH, SH, NH ₂ , NHC (O) alkyl, alkoxy, alkylthio or Phenyl, in particular alkyl, preferably methyl, alkoxy, preferably methoxy, and halogen, preferably chlorine, according to the invention.

If the substituents are salt-forming groups, such as SO ₃ H, COOH, OH, SH, NH ₂ or NHC (O) alkyl, or at least one of the radicals R ¹ to R ⁶ comprises a heterocycle, such as pyridine the compounds according to the invention also their salts, for example alkali metal, alkaline earth metal or ammonium salts of deprotonable groups and acid addition salts of basic substituents. The number of possible substituents depends on the type of aromatic radicals R ¹ to R ⁶ . A phenyl radical can, for example, carry one, two, three, four or five substituents, which can be the same or different, which can result in multiple isomer possibilities for a given selection of substituents due to different arrangement options on the aromatic radical.

If R ¹ to R ^{6 are} phenyl radicals, these are preferably substituted twice or three times, in particular in the two ortho and / or the para position. Two identical ortho substituents are very particularly preferred. R ¹ to R ^{6 are} in particular 2,4,6-trimethylphenyl, 2,4,6-trichlorophenyl, 2,4,6-trimethoxyphenyl, 2,6-dimethylphenyl, 2,6-dichlorophenyl or 2,6- Dimethoxy phenyl.

A preferred embodiment comprises mono-bridged porphyrin dimers of the formula I in which a porphyrin macrocycle bears the same substituents at the non-bridging meso positions, that is to say R ¹ , R ² and R ³ are the same but, if appropriate, of R ⁴ , R ⁵ and R ^{6 are} different, with R ⁴ R ⁵ and R ^{6 being} identical to one another. Compounds in which R ¹ to R ^{6 have the} same meaning are particularly preferred.

The porphyrin dimers according to the invention at the so-called β-pyrrole positions offer further possibilities for the targeted introduction of certain substituents. R ⁷ and R ⁸ , which may be the same or different, are preferably hydrogen, halogen, alkyl, SO ₃ H, CN or NO ₂ . Compounds of the formula I in which R ⁷ and R ^{8 have the} same meaning are particularly preferred.

The function of the Y residue is to macro the two porphyrins To connect cyclen in such a way that their levels face each other can. It is neither necessary that both macrocycles are congruent come to lie immediately on top of each other, nor must their levels be parallel. X-ray structure analysis is usually found an arrangement in which the π-π interactions between the aro matic macrocycles are optimized. The ring distances are in usually between three and four angstroms, the distance between between the centers of both porphyrins due to lateral displacements can be bigger. The two centers can preferably be located in the compounds of the formula I according to the invention to 10 angstroms, in particular to 7 angstroms and particularly preferably to 5 angstroms approach stream. A particular advantage of the Di according to the invention mere is that the connection between the macrocycles is not rigid is, so that a variety of geometries with varying distances that is possible between the centers.

The chain length and the flexibility of the radical y result from the type of the radicals R ⁹ , R ¹⁰ and A. As mentioned above, R ⁹ and R ¹⁰ preferably represent aromatic divalent radicals which can optionally carry further substituents and include in particular the substituents of aromatic radicals R ¹ to R ⁶ . Before given R ⁹ and R ¹⁰ , which may be the same or different, represent phenylene or substituted phenylene. In this case, substituents are preferably in the ortho position. Especially before given R ⁹ and R ^{10 are} 1,3- and / or 1,4-phenylene. In particular, R ⁹ and R ^{10 have the} same meaning.

The divalent radical A links the radicals R ⁹ and R ¹⁰ . The preferred chain length of A depends, among other things, on the nature of the substituents R ⁹ and R ¹⁰ .

In this context, chain length means the number of successive atoms between the two binding sites this chain.  

Suitable radicals according to the invention with chain length 1 are, for example, alkylene radicals C (R ¹⁴ R ¹⁵ ), where R ¹⁴ and R ^{15 can be the} same or different and represent hydrogen, alkyl or halogen, such as methylene, 1,1-ethylene, 1, 1- and 2,2-propylene, 1,1- and 2,2-butylene, 1,1- (2-methyl) propylene, 1,1-, 2,2- and 3,3-pentylene, 1, 1-, 2,2- (3-methyl) butylene, 1,1- (2-methyl) butylene, 1,1-, 2,2- and 3,3-hexylene, 1,1- and 2,2- (4-methyl) pentylene, 1,1- and 3,3- (2-methyl) pentylene, 1,1- and 2,2- (3-methyl) pentylene, 3,3- (2,4-dimethyl) pentylene, etc., difluoromethylene or dichloromethylene, alkylene radicals of the aforementioned type which comprise one or more heteroatoms selected from O or S, for example those in which R ¹⁴ and / or R ^{15 are} alkoxy or alkylthio, the abovementioned Alkylene radicals can also be substituted, O, S, S (O), S (O) ₂ , C (O), C (S), Si (R ¹¹ R ¹² ) or N (R ¹³ ), the radicals R ^11, R ^12, R ¹³ may be the same or different and R is hydrogen, alkyl, halogen or alkoxy.

Divalent radicals A with chain length 2 are, for example, linear or branched alkylene units C (R ¹⁶ R ¹⁷ ) C (R ¹⁸ R ¹⁹ ), in which R ¹⁶ to R ^{17 can be the} same or different and represent hydrogen, alkyl or halogen, such as 1,2-ethylene, 1,2-propylene, 1,2- and 2,3-butylene, 1,2- (2-methyl) propylene, 1,2- and 2,3-pentylene, 1,2- and 2,3- (2-methylbutylene, 1,2- (3-methyl) butylene, 1,2-, 2,3- and 3,4-hexylene, etc., tetrafluoro-1,2-ethylene or tetra chloro-1,2-ethylene, alkylene radicals of the aforementioned type which comprise one or more heteroatoms selected from O or S, for example those in which at least one of the radicals R ¹⁶ to R ^{19 is} alkoxy or alkylthio, or those which are bonded to R ⁹ or R ¹⁰ via O or S, alkenylene radicals C (R ²⁰ ) C (R ²¹ ) in which R ²⁰ and R ^{21 may be the} same or different and represent hydrogen, alkyl, halogen or alkoxy, such as 1, 2-ethenylene, prop-1,2-en-1,2-ylene or but-2,3-en-2,3-ylene, difluoroeth-1,2-en-1,2-ylene or he dichloro-1,2-ene-1,2-ylene, where the abovementioned alkylene and alkenylene radicals can also be substituted, 1,2-ethynylene, S (O) ₂ -O, C (O) -O or C (O) -N (R ¹³ ), where R ¹³ can have the meanings given above.

Examples of a divalent radical A with chain lengths of greater than two are alkylene units in which the two bond atoms are separated by at least one further atom, such as linear alkylene radicals (CH ₂ ) _n with n = 3 to 10 and in particular 3 to 5 , branched alkylene radicals, in which one or more (CH ₂ ) units of a linear alkylene radical (CH ₂ ) _{n can be} replaced by one or more, identical or different groups C (R ¹⁴ R ¹⁵ ), in which R ¹⁴ and R ¹⁵ can have the meanings given above and are preferably hydrogen and / or alkyl, alkylene radicals of the aforementioned type which one or more, of O, S, S (O), S (O) ₂ , C (O), C (S), Si (R ¹¹ R ¹² ), N (R ¹³ ), C (O) -O or C (O) -N (R ¹³ ) include selected groups, for example those that have one or two of these groups R ⁹ and R ^{10 are} bonded, where R ¹¹ , R ¹² and R ^{13 may have} the meanings given above, substituted alkylene units of the above Chneten types, as well as unsaturated radicals, wherein the above-mentioned alkylene residues have one or more double and / or triple bonds.

Preferred radicals A are selected from C (R ¹⁴ R ¹⁵ ), O, S, C (O), C (S), S (O) S (O) ₂ , Si (R ¹¹ R ¹² ), N (R ¹³ ) C (R ¹⁶ R ¹⁷ ) C (R ¹⁸ R ¹⁹ ) or (CH ₂ ) _n with n = 3 or 4, where R ¹¹ to R ^{19 can have} the meanings given above and preferably for hydrogen and / or alkyl, especially methyl.

If R ⁹ and R ^{10 are} 1,3-phenylene or substituted 1,3-phenylene, A is preferably selected from the above-mentioned substituents with the chain length of at least 1 or 2, preferably 1. In this context, the methylene group is very particularly preferred.

If R ⁹ and R ^{10 are} 1,4-phenylene or substituted 1,4-phenylene, A is preferably selected from the radicals A which have a chain length of at least 3 or 4 and in particular 4. 1,3-propylene and 1,4-butylene are particularly preferred here.

Preferred compounds of the formula I according to the invention are
Bis- (3- [10,15,20-tris (2,4,6-trimethylphenyl) porphyrin-5-yl] phenyl) methane,
Bis- (3- [10,15,20-tris (2,6-dichlorophenyl) porphyrin-5-yl] phenyl) methane and
Bis- (3- [10,15,20-tris (2,6-dimethylphenyl) porphyrin-5-yl] phenyl) methane.

The compounds of formula I can also be different isomers include. For example, it is formed by the four pyrrole sticks fabric layer no mirror plane if at least one of the meso substituents are not 2-fold, due to the bond to Porphyrin placed axis. In this case there are several Arrangements of such substituents possible that are distinguishable Lead porphyrins. In the case of meso substituents Open isomerism is called atropisomerism and is called two possible settings of a meso substituent with α  or β. According to the invention, all atropoisomers of Verbin of formula I, as well as diastereomers or enantiomers if the corresponding asymmetry centers are available. In In this context, it should be pointed out that the Rest y and especially group A for the introduction of a chira center are suitable. Even through the hike of the Possible tautomers of pyrrole are the subject of this he finding.

Another object of the present invention is a ver drive to the preparation of compounds of formula I. The inventions The method according to the invention is based on known production methods for the synthesis of porphyrins. Here are primarily those Porphyrin synthesis according to Rothemund (Rothemund, P .; J. Am. Chem. Soc. 1936, 58, 625-627 and Rothemund, P.J .; J. Am. Chem. Soc. 1939, 61, 2912-2915) and those introduced by Lindsey in this regard modifications (Lindsey, J.S .; et al. J. Org. Chem. 1987, 52, 827-836 and Lindsey, J.S .; et al .; J. Org. Chem. 1989, 54, 828-836).

The compounds of formula I according to the invention can be prepared, for example, by the aldehydes

R ^{1 '} -CHO, R ^2' -CHO, R ^{3 '} -CHO, R ^4' -CHO, R ^{5 '} -CHO and R ^6' -CHO,

in which R ^{1 '} to R ^6' can have the meanings given above for R ¹ to R ⁶ ,
with pyrroles

in which R ^{7 '} and R ^8' can have the meanings given above for R ⁷ and R ⁸ ,
and the aldehydes

OHC-Y'-CHO,

in which Y 'can have the meanings given above for Y, condensed under acid catalysis, then oxidized and the compounds of the formula I isolated, where appropriate the radicals R ^1' to R ^{8 '} and Y' which do not correspond to the desired radicals R ¹ until R ⁸ and Y match, transferred to them at a suitable point in time.

The process described above can advantageously be used for the synthesis of porphyrin dimers of the formula I according to the invention, in which R ¹ to R ⁶ on the one hand and R ⁷ and R ^{8 on the} other hand have the same meaning.

For the preparation of compounds of formula I according to the invention which comprise two different porphyrin macrocycles, the process can be modified in such a way that the aldehydes

R ^{1 '} -CHO, R ^2' -CHO and R ^{3 '} -CHO,

in which R ¹ to R ³ may have the meanings given above for R ¹ to R ³ ,
with pyrroles

where R ^{7 '} can have the meaning given above for R ⁷ ,
and the semi-protected dialdehydes

OHC-Y'-CQ,

wherein Y 'can have the meaning given above for Y and Q represents an aldehyde protective group, condensed acid-catalyzed, then oxidized, the protective group is split off and the compound of the formula III thus obtained,

where R ^{1 ''} to R ^{3 ''} , R ^{7 ''} and Y '' can have the meanings given above for R ^{1 '} to R ^3' , R ^{7 '} and Y',
with the aldehydes

R ^{4 '} -CHO, R ^5' -CHO and R ^{6 '} -CHO,

in which R ^{4 '} to R ^{6' can have} the meaning given above for R ⁴ to R ⁶ ,
and the pyrroles

in which R ^{8 '} can have the meaning given above for R ⁸ ,
acid-catalyzed, oxidized and the compound of the formula I isolated, where appropriate the radicals R ^{1 '} to R ^3' , R ^{7 '} and Y' which do not correspond to the desired radicals R ^{1 '} to R ^3'' , R ^7'' and Y''agree, as well as the radicals R ^1'' to R ^3'' , R ^7'' , R ^4' to R ^{6 '} , R ^8' and Y '', which do not match the desired radicals R ¹ to R ⁶ , R ⁷ , R ⁸ and Y match, transferred to them at a suitable time.

Both of the methods described above can also be modified so that first dipyrrole units of the formula IVa,

wherein R ^{x "stands} for R ^1" , R ^{2 "} or R ^3" if R ^{y "} stands for R ^7" , and R ^{x "} stands for R ^4" , R ^{5 "} or R ^{6 ''} , if R ^{y '' stands} for R ^{8 ''} , dipyrrole units of the formula IVb,

wherein R ^{y "stands} for R ^7" or R ^{8 "} and Q stands for an aldehyde protecting group, and / or dipyrrole units of the formula IVc,

where in the formulas IVa-c R ^{1 "} to R ^8" and Y "may have the meanings given above for R ¹ to R ⁸ and Y, from the corresponding aldehydes, dialdehydes, semi-protected aldehydes and pyrroles by acid-catalyzed condensation produces, if appropriate isolated and then suitable dipyrrole units of the formulas IV a to c with the remaining aldehydes and, if appropriate, pyrroles to the compounds of the formula I acid-catalyzed, oxidized and isolated, where appropriate the radicals R ^{1 '} to R ^8' and Y ', which do not match the desired radicals R ^{1 "} to R ^8" and Y ", and the radicals R ^1" to R ^{8 "} and Y", which do not match the desired radicals R ¹ to R ⁸ and Y match, transferred to them at a suitable time.

For example, the aldehydes

R ^{1 '} -CHO and R ^3' -CHO,

in which R ^{1 '} and R ^3' can have the meanings given above for R ¹ and R ³ ,
with pyrroles

where R ^{7 '} can have the meaning given above for R ⁷ ,
as well as the aldehydes

R ^{4 '} -CHO and R ^6' -CHO,

in which R ^{4 '} and R ^6' may have the meanings given above for R ⁴ and R ⁶ ,
with the pyrroles

in which R ^{8 '} can have the meaning given above for R ⁸ ,
acid catalyzed to the corresponding dipyrroles of the formula IVa,

where R ^{x "stands} for R ^1" or R ^{3 "} if R ^{y "} stands for R ^{7 "} , and R ^x" stands for R ^{4 "} or R ^6" if R ^{y ''represents} R ⁸ ,
condense, isolate if necessary and then the compounds of formula IVa with the aldehydes

R ^{2 '} -CHO and R ^5' -CHO,

in which R ^{2 '} and R ^5' can have the meanings given above for R ² and R ⁵ ,
and the aldehydes

OHC-Y'-CHO,

where Y 'can have the meanings given above for Y,
implement to the compounds of formula I, where appropriate the radicals R ^{1 '} , R ^3' , R ^{4 '} , R ^6' , R ^{7 '} and R ^8' , which do not match the desired radicals R ^{1 ''} , R ^{3 ''} , R ^{4 ''} , R ^{6 ''} , R ^{7 ''} and R ^{8 ''} match, as well as the radicals R ^{1 ''} , R ^{2 '} , R ^3'' , R ^4'' , R ^{5 '} , R ^6'' , R ^7'' , R ^8'' and Y', which do not match the desired radicals R ¹ to R ⁸ and Y, are converted into these at a suitable point in time.

Another option is to start with the bridging Dialdehyde unit with the corresponding pyrroles to form a compound to implement the formula IVc, if necessary to isolate them and then with the pyrroles or the corresponding dipyrrole units  ten of the formula IVa and the remaining aldehydes to a compound dung of the formula I to condense and oxidize.

Furthermore, instead of a dialdehyde unit, this can be done half protected equivalent and use the first step by step and then build the second macrocycle.

The detailed design of individual measures of the above be Written methods can the specialist due to his general knowledge about porphyrin chemistry or, for example, under Carry out the publications mentioned above. in the the following are just a few preferred measures for synthesis of the porphyrin dimers according to the invention.

The procedures described above are usually in solution carried out. Organic solvents are preferably used uses, especially halogenated hydrocarbons, such as chloro form and dichloromethane.

For acid-catalyzed condensation of aldehydes with pyrroles are generally added catalytic amounts of acid. Lewis acids are preferably used, particularly in the Solvents used are soluble, such as boron trifluoride ethe advice. The reaction is generally carried out with the exclusion of acid fabric carried out. This is done using an inert gas such as nitrogen or argon, pass through the reaction solution before the start of the reaction tet. During the reaction, this protective gas atmosphere becomes keep and preferably the reaction mixture is exposed to light protected. Usually the reaction is at room temperature carried out. But it can also make sense, at least for a while wise to heat the mixture. Especially before following one the oxidation of a porphyrinogen can be advantageous.

After the condensation reaction is complete, the porphy formed rinogen oxidized to porphyrin. These are particularly suitable Electron transfer reagents, which the porphyrinogen by Auf can oxidize electrons. Examples are un ter the 1,4-benzoquinones, such as chloranil or 2,3-dichloro-5,6-di cyano-1,4-benzoquinone (DDQ). This oxidation reaction can normal or elevated temperature.

It can be useful for isolating the porphyrin dimer formed be new to the acid in a conventional way tralize. Organic bases are preferably used for this purpose, like triethylamine. The desired connection can then, for example  wise by chromatographic separation from the multiple porphy mixture containing rin isomers can be isolated.

When using the semi-protected dialdehydes OHC-Y'-CQ com Protective groups to apply, which under the selected Kon conditions are stable. In particular, in this Relationship to that of Collman, J.P .; et al. in J. Org. Chem. 1995, 60, 1926-1931 bridged synthesis methods ter porphyrin dimers, in which a dialdehyde with 1,3-propanedithiol to the corresponding semi-protected dialdehyde is implemented. The separation can be carried out according to conventional methods be carried out, preferably the one in the above Publication described reaction with DDQ and boron trifluoride-Ethe advice.

A particular embodiment of the invention comprises processes in which the radicals R ¹ to R ⁶ , R ⁷ , R ⁸ and Y correspond to their respective stages. This process variant is particularly advantageous when the residues used in the starting materials are stable under the chosen reaction conditions and they do not adversely affect the production process. If this is not the case for one or more of the radicals R ¹ to R ⁶ , R ⁷ , R ⁸ or Y, suitable precursors of these radicals are preferably selected, which are then converted into the desired radicals of a compound of the formula I or III in a later process step being transformed. For example, carboxyl or sulfonic acid groups in the form of the corresponding esters, a hydroxyl group as ethers or amines as amides can be used. The conversion of such precursors is preferably carried out during or after isolation of the porphyrin. Further examples of modifications that are carried out on the porphyrin are the salt formation and the quaternization of nitrogen.

Furthermore, the radicals R ¹ to R ^{6 can} be derivatized in a known manner by electrophilic aromatic substitution. For example, the meso-phenyl groups can be nitrided, sulfonated or halogenated. Such reactions are usually carried out on the non-metalated free porphyrin base. In contrast, porphyrins metallized with iron, zinc or nickel are preferred for the electrophilic substitution of the β-pyrrole positions. This leads to an activation of the β-pyrrole positions with simultaneous deactivation of aromatic meso substituents in relation to the electrophilic substitution. For example, porphyrins according to the invention in which R ⁷ and / or R ^{8 represent} hydrogen can be nitrided, sulfonated or halogenated in a known manner. The metal can then be removed before, during or after isolation of the resulting pophyrin.

The properties of the compounds of the formula I according to the invention can thus be influenced in a targeted manner by the choice of the radicals R ¹ to R ⁶ , R ⁷ , R ⁸ and Y. For example, an essentially hydrophobic porphyrin can subsequently be converted into an essentially hydrophilic porphyrin, so that it can also be used in hydrophilic media, such as water or alcohols.

As described above, the porphyrin di mers of formula I comprise a number of isomers. In particular There is often the possibility with different atropisomers ability to convert them into each other, for example through treatment in a suitable solvent or solvent mixture elevated temperature. The method according to the invention thus comprises also measures for the enrichment of certain atropisomers.

Another object of the present invention are metal complexes of a compound of formula I according to one of the preceding claims of formula II

wherein R ¹ to R ⁸ and Y have the meanings given above, Z and Z ', which may be the same or different, represent M, ML ¹ or ML ¹ L ² , where M is a transition metal cation of the minor groups IV, V, VI, VII, VIII, I or II of the periodic table and L ¹ and L ² , which may be the same or different, stand for axial ligands, and salts thereof.

In these metal complexes according to the invention, a porphyrin macrocycle acts as a tidentate ligand. Depending on the type and electronic state of the bound metal cation, one or two further coordination sites for suitable ligands are available at this. If one defines the area formed by the four pyrrole nitrogen of a porphyrin as an equatorial plane, one can call each fifth and / or sixth binding partner L ¹ and / or L ^{2 of} the metal cation M an axial ligand. For stereochemical reasons, L ¹ and L ² , if both are present, are generally on opposite sides of the plane formed by the macrocycle, that is to say in the trans position. If only one axial ligand is present, the metal cation M is often shifted out of the porphyrin plane in the direction of the axial ligand. This is particularly evident when the axial ligand L ^{1 is} an anion.

As the transition metal cation M of the metal complexes according to the invention Formula II is particularly suitable for those with which oxidative catalysis can be carried out, i.e. such porphyrin Me talllexe whose redox potential is suitable to a be to convert the correct substrate into its oxidized form. To the For this purpose, Ti, V, Nb, Cr, Mo, W, Mn, Re are particularly suitable. Fe, Ru, Os, Co, Rh, Ir, Ni, and Cu. Are very particularly preferred Ti, V, Nb, Re, Ru, Os, Co, Rh, Ir, Ni, Fe and Mn. Especially M is preferably Ru.

"Axial ligand" means in the context of the present Er uncharged or charged, mono- or polyatomic groups L, which is attached to a certain metal cation M according to the invention can be stored. Due to the given by the porphyrin In stereochemistry, they usually act as a monodentate ligand. Examples of anionic ligands are fluoride, chloride, bromide, Iodide, hydroxide, oxo, peroxo, nitrito, cyanato, fulminato, thio cyanato, sulfido, disulfido, mercapto, acido, amido, imido, Nitrido, nitro, isocyano, isocyaanato, isothiocyanato, alkoxy, such as methoxy or ethoxy, aryloxy, such as phenoxy or substituted Phenoxy, carboxylates such as acetate, benzoate or substituted Benzoate, perchlorate, tetrafluoroborate, hexafluorophosphate, tri flat, imidazolate, substituted imidazolate, etc.

Examples of neutral ligands are aqua, tetrahydrofuran, di nitrogen, pyridine, substituted pyridines, imidazole, substi acted imidazoles, such as N-methylimidazole, carbonyl, dioxygen, Nitriles such as acetonitrile, isonitriles, ethers and in particular cyclic ethers, such as tetrahydrofuran, amines, such as triethylamine, Phosphines, such as triphenylphosphine, amine oxides, pyridine oxides, Phos phanoxides etc.

A particular embodiment of the invention comprises Metallkom plexes of formula II in which one or both axial ligands for Oxo stand, the metal cation coordinates four or five times or at least one of the two with six-fold coordination Axial ligands is unstable so that it is acidic by one  substance-transferring ligands can be displaced. Most notably preferred axial ligands are therefore selected from Oxo, Car bonyl and weakly coordinating ligands, such as acetonitrile, Tetrahydrofuran, chloride, bromide, perchlorate, triflate, hydroxide, Methanol or methanolate.

Some of the above ligands can also be bidentate koordi kidneys and in particular as a bridge ligand between the the metal cations of the compounds of the formula according to the invention II act. Examples of such ligands are oxygen, Nitrous oxide, oxo, nitrido or carboxylates. Of special Interest are Oxygen and Oxo, which lead to so-called µ-Peroxo- or µ-Oxo-bridged dimers. The invention Metal complexes of the formula II preferably form μ-peroxo-ver bridged porphyrin dimers, particularly the formation of µ-Oxo units is difficult or even impossible. Preferably this is achieved through suitable substituents at the meso positions the porphyrins reached. Suitable according to the invention are, for example as phenyl residues, which are substituents in both ortho positions wear whose size is that of a hydrogen or fluorine atom increases. The same can be said for the 2 position in 1-position bound naphthyl residue transferred while an in 9-position bound anthryl residue itself is already sufficient obstacle granted.

In addition to the steric function, the porphyrin substituents R ¹ to R ⁶ , R ⁷ , R ⁸ and Y also affect the electronic properties of the resulting metal complexes. In this context, the redox potentials for metal- or porphyrin-centered redox reactions should be mentioned in particular. Thus, the redox potentials of a given metal center Z or Z 'can be varied in a wide range by introducing electron-withdrawing or electron-donating substituents at the meso- and in particular β-pyrol positions of the porphyrins. For example, the redox potentials for metal complexes of the formula II in which R ⁷ and / or R ^{8 are} chlorine or bromine and / or one or more of the radicals R ¹ to R ^{6 are} 2,6-dichlorophenyl are relatively high.

In the metal complexes of the formula II according to the invention, Z and Z 'can be the same or different. Taking into account that the two porphyrin macrocycles can be the same or different, there are a number of possible types of metal complexes according to the invention. The present invention therefore includes in example
Homo-bis (metallo) -homo-diporphyrins, in which the axial ligands of both metal centers can be the same or different,
Hetero-bis (metallo) -homo-diporphyrins, in which the axial ligands of the two metal centers can be the same or different,
Homo-bis (metallo) hetero-diporphyrins in which the axial ligands of the two metal centers can be the same or different and
Hetero-bis (metallo) hetero-diporphyrins, in which the axial ligands of both metal centers can be the same or different.

Homo-bis (metallo) diporphyrins and in particular homo-bis (metallo) -homo-diporphyrins are particularly preferred. Homo-bis (metallo) -homo-diporphyrins of the formula II, in which Z and Z 'are identical, and in particular Compounds of formula II, which are selected from
Bis- (3- [10,15,20-tris (2,4,6-trimethylphenyl) porphyrin-5-yl ato-ruthenium carbonyl] phenyl) methane,
Bis- (3- [10,15,20-tris (2,6-dichlorophenyl) porphyrin-5-yl ato-ruthenium carbonyl] phenyl) methane,
Bis- (3- [10,15,20-tris (2,6-dimethylphenyl) porphyrin-5-yl ato-ruthenium carbonyl] phenyl) methane,
Bis- (3- [10,15,20-tris (2,4,6-trimethylphenyl) porphyrin-5-yl ato-trans-dioxo-ruthenium] phenyl) methane,
Bis- (3- [10,15,20-tris (2,6-dichlorophenyl) porphyrin-5-ylato-trans-di oxo-ruthenium] phenyl) methane and
Bis- (3- [10,15,20-tris (2,6-dimethylphenyl) porphyrin-5-ylato-trans-di oxo-ruthenium] phenyl) methane.

If the metal complexes of the formula II have a total charge, the present invention also includes their salts with conventional ones Anions or cations.

The present invention also includes isomers of compounds of Formula II, which is in addition to the above for the free Porphyrin bases shown options due to asymmetry different metal centers Z and Z '.  

Another object of the present invention is a process for the production of metal complexes of the formula II. The process according to the invention is carried out based on known techniques for the metalation of porphyrins. A compound of the formula I is usually reacted with a salt, oxide or complex of the metal M and, if appropriate, the axial ligand (s) L ¹ and / or L ^{2 is} introduced. This process is particularly suitable for the production of homo-bis (metallo) diporphyrins.

Metallization of hetero-bis (metallo) diporphyrins is carried out the procedure preferably in two steps. Here comes in particular the process for the synthesis of Heterodiporphyrins for use. A compound of the formula III or its protected equivalent is first in übli with a salt, oxide or complex of a metal M. set. Then the second porphyrin macrocycle, the in this case can be identical to the first, synthesized, so that the second metallization with another Metal can be made. The introduction of axial ligands can be made after the first and / or second metallization will.

As a rule, the metalation leads to metal complexes in which the metal center (s) have axial ligands. these can come from different sources. Examples are coordinating Solvents such as tetrahydrofuran, acetonitrile or methanol, Counterions from metal salt starting materials, such as chloride or bromide, Educt complex ligands, such as carbon monoxide, in the surrounding Atmosphere of existing oxygen or dinitrogen, or also result from the decarbonylation of an organic compound carbon monoxide.

Such primarily existing axial ligands can then be in a white step can be replaced. You can do it better Use processes such as metathetic reactions.

Within the scope of the present invention, the introduction of oxo ligands into the axial position of the metal complexes is of particular importance. For this purpose, a metal complex of the formula II is preferably reacted with an oxygen-transferring agent. These include, in particular, hydrogen peroxide, organic hydroperoxides, such as cumene hydroperoxide and t-butyl hydroperoxide, organic peracids, such as meta-chloroperbenzoic acid, performic acid, peracetic acid or para-nitroperbenzoic acid, alkali metal hypohalites, such as NaOCl or NaOBr, substituted or unsubstituted iodo- _4- ozone, disodium or ionosobenzone, Na. When these reagents are used, the metal porphyrins according to the invention are usually oxidized, the metal and / or the porphyrin macrocycle being able to change the oxidation state. Another way of introducing oxo ligands is to first oxidize the metal porphyry without simultaneous oxygen transfer, for example with the aid of pure electron transfer reagents or electrochemical methods, and then in a metha thetic reaction, for example with hydroxide ions in the axial oxo groups Introduce positions.

The oxo or dioxo metal di according to the invention thus produced porphyrins can either be isolated or generated in situ and be applied.

Another object of the present invention is Ver use of at least one compound of formula II for catalysis, preferably catalytic oxidation of hydrocarbons.

The present invention therefore also relates to a process for the catalytic oxidation of hydrocarbons, one or more compounds of the formula II being used as the catalyst. The compounds suitable according to the invention include both metal complexes of the formula II in which L ¹ and / or L ^{2 are} oxo, and metal complexes which have no axial oxo ligands, but which can be converted into those using the processes described above. The second alternative method is preferably used when the oxo-metal or dioxo-metal porphyrins are relatively unstable and therefore in situ generation is advantageous.

The catalysis process according to the invention is preferably carried out in one liquid medium. The catalyst can be dissolved, suspended or dispersed form. That too oxidie rende substrate is preferably soluble in the medium used Lich. The catalyst can also be in a bound form on a inorganic or organic insoluble in the reaction medium Carrier material can be used. As suitable carrier materials come in particular silicon dioxide, silica gels, silicas, Aluminum oxides, kaolins, aluminum silicates, and chemically fixed tes Hexamethylphosphorsäuretriamid on a polystyrene matrix in Consideration.

Various solvents or or can be used as the reaction medium multiphase solvent mixtures are used. Ge Suitable solvents are, for example, alkanes, aromatics, such as Benzene, haloalkanes, such as dichloromethane, chloroform or 1,2-dichloroethane, halogen aromatics, such as chlorobenzene, ethers, ketones, Esters, alcohols and water. Prerequisite for the suitability of a  The solvent is that it does not oxidize during catalysis or is decomposed. The choice continues to depend on the solves properties of the catalyst, substrate and / or pro dukt.

The catalytic oxidation according to the invention is preferably at Temperatures from 0 to 120 ° C and especially from 15 to 50 ° C carried out. It is preferable to work at room temperature.

It is preferable to work at normal air pressure. But it can also be advantageous, the reaction under a protective gas atmosphere sphere, for example nitrogen or argon. There against in the case of aerobic catalytic oxidations - dioxygen reacts here as a substrate - oxygen-containing atmospheres preferably pure oxygen used. The pressure is generally 0.2 to 10 bar, preferably at Nor color print.

A particular embodiment of the invention comprises methods for catalytic epoxidation of olefins.

In the context of the present invention, olefins are understood to be molecules which contain one or more carbon-carbon double bonds. Typical examples are ethene, propene, 1-butene, 2-butene, isobutene, 1,3-butadiene, 1-pentene, 2-pentene, isoprene, cyclopentene, 1-hexene, cyclohexene, C ₈ -C ₂₄ -α-monoolefins , Styrene, indene, norbornene, cyclopentadiene, dicyclopentadiene and also alkene oligomers, such as polypropene and polyisobutene. The olefins can also carry substituents on the olefinic double bond based on elements of the fourth to seventh main group. Examples include vinyl silicones, vinyl amines, vinyl phosphines, vinyl ethers, vinyl sulfides and halogenated alkenes, such as vinyl chloride, vinylidene chloride or trichlorethylene.

Often, several isomeric epoxides can be synthesized from one olefin be settled. In such cases, the reaction conditions are chosen gene, especially the catalyst, preferably so that an over Shot of the desired isomer can be obtained. In this To in connection, metal complexes of the formula II are particularly suitable net, which themselves have one or more chirality centers.

Another particular embodiment of the invention relates to a Process for the catalytic aerobic epoxidation of olefins. Here, the catalytic reaction, as described above, in An presence of oxygen. You choose as catalyst preferably metal complexes of the formula II, in which M is under niobium, Rhenium, ruthenium, osmium, rhodium or iridium is selected.  

In particular, ruthenium complexes according to the invention are used. The catalyst is ent based on the above description neither used as trans-dioxo-ruthenium complex or it comes a suitable precursor, especially a ruthenium carbonyl com plex of formula II, for use with the help of oxygen transmitting agents of the type described above in-situ for corresponding trans-dioxo-ruthenium complex are implemented can.

The following examples describe the invention without limiting it restrict.

example 1 Synthesis of bis- (3- [10,15,20-tris (2,4,6-trimethylphenyl) porphy rin-5-yl] phenyl) methane

162 mg (0.72 mmol, 1 eq.) Of bis (3-formylphenyl) methane were dissolved in 2300 ml of chloroform and the solution was flushed with nitrogen for 30 min. 2.55 ml (17.28 mmol, 24 eq.) Of mesityl aldehyde, 1.30 ml (18.72 mmol, 26 eq.) Of pyrrole and 0.95 ml (7.56 mmol) of boron trifluoride etherate were then added in the dark and stirred for 2 hours at room temperature. After the addition of 3.92 g (17.28 mmol, 24 eq.) DDQ (dichlorodicyanobenzoquinone, oxidizing agent), the mixture was stirred at room temperature for a further 4.5 h. After neutralization with 1.16 ml (8.36 mmol, 1.1 eq. With respect to BF ₃ ) triethylamine, the mixture was concentrated to approx. 50 ml on a rotary evaporator. Column filtration on neutral aluminum oxide, packed in n-hexane: dichloromethane 1: 1, eluted with pure dichloromethane, followed by column chromatography on silica gel (7 × 22 cm), gradient elution: n-hexane: dichloromethane 4: 1 to 2: 1, gave 19 mg (1.8%) metallic flaky violet product (purity approx. 95%, HPLC).
FAB-MS and MALDI-TOF: m / z: 1494 (100%), calc. For C ₁₀₇ H ₉₆ N ₈ : 1493.99
UV / VIS: λ _max : 412 nm (n-hexane: dichloromethane 60:40)
1H-NMR (300 MHz, CDCl ₃ ): δ = -2.54 (s, 4H, NH), 1.81-1.88 (m, 36H, o-CH ₃ ), 2.60-2.62 (m, 18H, p-CH ₃ ), 4.55 (s, 2H, CH ₂ ), 7.22 (s, 4H, aryl-H / pyrrole-H), 7.69-7.77 (m, 4H, aryl-H / pyrrole-H), 8.07-8.09 (m, 2H, aryl-H / pyrrole-H), 8.30 (s, 2H, aryl-H / pyrrole-H), 8 , 63 (s, 8H, aryl-H / pyrrole-H), 8.65-8.67 (m, 4H, aryl-H / pyrrole-H), 8.83-8.85 (m, 4H, aryl -H / pyrrole-H).

Example 2 Synthesis of bis-3 (- [10,15,20-tris (2,4,6-trimethylphenyl) porphy rin-5-ylato-ruthenium carbonyl] phenyl) methane

8 mg (5.35 µm, 1 eq.) Bis- (3- [10,15,20-tris (2,4,6-trimethylphenyl) porphyrin-5-yl] phenyl) methane were dissolved in 2 ml abs. Dissolved diethylene glycol monomethyl ether and heated to 160 ° C. At this temperature, 7.5 mg (11.78 µmol, 2.2 eq.) Of ruthenium dodecacarbonyl were added in several portions over a period of 45 minutes. The mixture was then stirred at the same temperature for 3 h (formation of a metal mirror). After cooling, it was poured onto 4 ml of concentrated sodium chloride solution and stirred one hour after. Filtration over Celite, drying the filter cake in an oil pump vacuum and subsequent extraction with dichloromethane gave 7 mg of crude product, which was purified by column chromatography on silica gel (2 × 25 cm), eluent: n-hexane-dichloromethane 1: 1. 4.5 mg of orange-colored, crystalline solid were isolated.
MALDI-TOF: m / z: 1720.3 (22%, M⁺-CO], 1691.8 (100%, M⁺-2CO); calculated for C ₁₀₇ H ₉₂ N ₈ Ru ₂ : 1692.1
FT-IR (KBr): ν: 1942 cm⁻ ¹ (Ru-CO)

Example 3 Synthesis of bis- (3- [10,15,20-tris (2,4,6-trimethylphenyl) porphy rin-5-ylato-trans-dioxo-ruthenium] phenyl) methane

To 10 mg (60 µmol, 52 eq.) M-chloroperbenzoic acid dissolved in 6 ml dichloromethane, 2 mg (1.14 µmol, 1 eq.) Bis- (3- [10,15,20-tris ( 2,4,6-trimethylphenyl) porphyrin-5-ylato ruthenium carbonyl) phenyl) methane, dissolved in 1 ml of dichloromethane. After stirring for 5 minutes at room temperature, the reaction mixture was filtered under argon over 6 g of basic aluminum oxide (activity level I) and rinsed with 6 ml of dichloromethane. The brown solution was then gently freed from the solvent on the rotary evaporator. 1.6 mg (80%) of a shiny metallic, violet powder were obtained.
FT-IR (KBr): ν: 820 cm⁻ ¹ (O = Ru = O)

Example 4 Catalytic epoxidation of norbornene with oxygen

1.6 mg (0.91 µmol) bis- (3- [10,15,20-tris (2,4,6-trimethylphenyl) por phyrin-5-ylato-trans-dioxo-ruthenium] phenyl) methane were found in 1.0 ml of benzene dissolved and after adding 39 mg (414 µmol) of norbor in an oxygen atmosphere under normal pressure at 25 ° C stirs. After 24 h was by means of gas chromatographic analysis (Addition of chlorobenzene as internal standard) sales of Norbornene to exo-2,3-epoxy norbornene found. A control experiment in the absence of the catalyst showed no a little turnover of the educt.

Claims (28)

1. Mono-bridged porphyrin dimers of the formula I
wherein
R ¹ to R ⁶ , which may be the same or different, represent alkyl, cycloalkyl, aryl, substituted aryl, heteroaryl or substituted heteroaryl,
R ⁷ and R ⁸ , which may be the same or different, represent hydrogen, halogen, alkyl, nitro, SO ₃ H, phenyl, substituted phenyl or cyano,
Y stands for -R ⁹ -AR ¹⁰ -
wherein
R ⁹ and R ¹⁰ , which may be the same or different, represent arylene, substituted arylene, heteroarylene, substituted heteroarylene, optionally cycloalkylene or substituted cycloalkylene which is interrupted by one or more heteroatoms selected from O, N or S and
A represents a bivalent, linear or branched radical,
and salts thereof. 2. Compounds according to claim 1 of formula I, wherein R ¹ to R ^{6 are} phenyl, substituted phenyl, pyridyl, substituted pyridyl, naphthyl, substituted naphthyl, anthryl or substituted anthryl. 3. Compounds according to claim 2 of formula I, wherein R ¹ to R ^{6 are} phenyl or monosubstituted, disubstituted, triple, quadruple or five-fold substituted phenyl, the substituents being selected from alkyl, halogen, cyano, nitro, SO ₃ H , COOH, acyloxy, alkoxycarbonyl, OH, SH, NH ₂ , NHC (O) alkyl, alkoxy, alkylthio or phenyl. 4. Compounds according to claim 3 of formula I, in which R ¹ to R ⁶ are phenyl which is substituted twice or three times, the substituents being selected from alkyl, alkoxy, halogen and in particular 2,4,6-trimethylphenyl, 2,4, 6-trichlorophenyl, 2,4,6-trimethoxyphenyl 2,6-timethylphenyl, 2,6-di chlorophenyl or 2,6-dimethoxyphenyl. 5. Compounds according to any one of claims 1 to 4 of formula I, wherein R ¹ = R ² = R ³ and R ⁴ = R ⁵ = R ⁶ . 6. Compounds according to any one of claims 1 to 4 of formula I, wherein R ¹ = R ² = R ³ = R ⁴ = R ⁵ = R ⁶ . 7. Compounds according to any one of claims 1 to 6 of formula I, wherein R ⁷ and R ⁸ , which may be the same or different, are hydrogen, alkyl, halogen, SO ₃ H, cyano or nitro. 8. Compounds according to any one of claims 1 to 7 of formula I, wherein R ⁹ = R ⁸ . 9. Compounds according to any one of claims 1 to 8 of formula I, wherein R ⁹ and R ¹⁰ , which may be the same or different, are phenylene or substituted phenylene. 10. Compounds according to claim 9 of formula I, wherein R ⁹ and R ¹⁰ , which may be the same or different, are 1,3- or 1,4-phenylene. 11. Compounds according to any one of claims 1 to 10 of formula I, wherein R ⁹ = R ¹⁰ . 12. Compounds according to any one of claims 1 to 11 of formula I, wherein the chain length of A is at least 1 when R ⁹ and R ^{10 are} 1,3-phenylene or substituted 1,3-phenylene, and the chain length of A at least 3 is when R ⁹ and R ^{10 are} 1,4-phenylene or substituted 1,4-phenylene. 13. Compounds according to claim 1 of formula I, which are selected from
Bis- (3- [10,15,20-tris (2,4,6-trimethylphenyl) porphyrin-5-yl] phenyl) methane
Bis- (3- [10,15,20-tris (2,6-dichlorophenyl) porphyrin-5-yl] phenyl) methane
Bis- (3- [10,15,20-tris (2,6-dimethyl) porphyrin-5-yl] phenyl) methane. 14. Metal complexes of a compound of formula I according to one of the preceding claims of formula II
wherein R ¹ to R ⁸ and Y have the meanings given above, Z and Z ', which may be the same or different, represent M, ML ¹ or ML ¹ L ² , where M is a transition metal cation of subgroups IV, V, VI , VII, VIII, I or II of the periodic table and L ¹ and L ² , which may be the same or different, stand for axial ligands, and salts thereof. 15. Compounds according to claim 14 of formula II, wherein M is Nb, Re, Ru, Os, Rh, Ir, Ti, V, Co, Ni, Fe or Mn. 16. Compounds according to claim 15 of formula II, wherein M represents Ru stands. 17. Compounds according to any one of claims 14 to 16 of formula II, wherein L ¹ and L ^{2 may be the} same or different and stand for oxo, carbonyl or weakly coordinating ligands. 18. Compounds according to any one of claims 14 to 17 of the formula II, where Z = Z '. 19. Compounds according to claim 14 of formula II, wherein Z and Z 'are RuCO or Ru (O) ₂ . 20. A process for the preparation of a compound of formula I according to any one of claims 1 to 13, wherein the aldehydes R ^{1 '} -CHO, R ^2' -CHO, R ^{3 '} -CHO, R ^4' -CHO, R ^{5 '} - CHO, and R ^{6 '} -CHO, in which R ^1' to R ^{6 '} can have the meanings given above for R ¹ to R ⁶ , with the pyrroles
wherein R ^{7 '} and R ^8' may have the meanings given above for R ¹ and R ⁶ , and the aldehydes
OHC-Y'-CHO,
wherein Y 'can have the meanings given above for Y, condensed acid-catalyzed, then oxidized and the compounds of the formula I isolated, where appropriate the radicals R ^1' to R ^{8 '} and Y', which do not correspond to the desired radicals R ¹ to R ⁸ and Y match, transferred to them at a suitable time. 21. The method according to claim 20, wherein the aldehydes
R ^{1 '} -CHO, R ^2' -CHO and R ^{3 '} -CHO,
wherein R ^{1 '} to R ^3' may have the meanings given above for R ¹ to R ³ , with the pyrroles
wherein R ^{7 '} can have the meaning given above for R ⁷ , and the semi-protected dialdehydes
OHC-Y'-CQ,
in which Y 'can have the meaning given above for Y and Q represents an aldehyde protective group, condensed under acid catalysis, then oxidized, the protective group split off and the compound of the formula III thus obtained,
wherein R ^{1 ''} to R ^{3 ',} R ^7''andY'^'the', R ^{7 'and} Y' may have the meanings given ^'above for R ¹ to R ^3,
with the aldehydes
R ^{4 '} -CHO, R ^5' -CHO and R ^{6 '} -CHO,
wherein R ^{4 '} to R ^6' may have the meaning given above for R ⁴ to R ⁶ , and the pyrroles
in which R ^{8 '} can have the meaning given above for R ⁸ ,
acid-catalyzed, oxidized and the compound of the formula I isolated, where appropriate the radicals R ¹ to R ^{3 '} , R ^7' and Y 'which do not contain the desired radicals R ^1'' to R ^3'' , R ^{7 ""} and Y "match, and the radicals R ^1" to R ^{3 "} , R ^7" , R ^{4 '} to R ^6' , R ^{8 '} and Y'', which do not correspond to the desired radicals R ¹ to R ⁶ , R ⁷ , R ⁸ and Y match, transferred to them at a suitable time. 22. The method according to any one of claims 20 or 21, wherein next dipyrrole units of the formula IVa,
wherein R ^{x "stands} for R ^1" , R ^{2 "} or R ^3" if R ^{y "} stands for R ^7" , and R ^{x "} stands for R ^4" , R ^{5 "} or R ^{6 ''} , if R ^{y '' stands} for R ^{8 ''} , dipyrrole units of the formula IVb,
wherein R ^{y "represents} R ^7" or R ^{8 "} and Q represents an aldehyde protecting group, and / or dipyrrole units of the formula IVc,
where in the formulas IVa-c R ^{1 ″} to R ^{8 ″} and Y ″ may have the meanings given above for R ¹ to R ⁸ and Y, from the corresponding aldehydes, dialdehydes, semi-protected aldehydes and pyrroles by acid-catalyzed condensation , optionally isolated and then suitable dipyrrole units of the formula IV are condensed, oxidized and isolated with the remaining aldehydes and optionally pyrroles to the compounds of the formula I acid-catalyzed, where appropriate the radicals R ^{1 '} to R ^8' and Y 'which are not compatible with the desired residues R ^{1 ″} to R ^{8 ″} and Y ″ agree, and the residues R ^{1 ″} to R ^{8 ″} and Y ″ which do not correspond to the desired residues R ¹ to R ⁸ and Y, transferred to it at a suitable point in time. 23. A process for the preparation of a compound of formula II according to one of claims 14 to 19, wherein the free porphyry bases are reacted with a salt, oxide or complex of a metal M and, if appropriate, the axial ligand (s) L ¹ and / or L ^{2 is} introduced. 24. The method according to claim 23, wherein the introduction of Oxo ligands in the axial position are oxygen-transferring Agent used. 25. Process for the catalytic oxidation of hydrocarbons fen, one or more compounds being used as the catalyst of formula II according to one of claims 14 to 19 used. 26. The method according to claim 25, wherein he produces a compound of formula II, wherein L ¹ and / or L ^{2 are} oxo, in situ. 27. The method according to any one of claims 25 or 26 for catalytic , especially aerobic, epoxidation of olefins. 28. The method according to any one of claims 25 to 27, wherein the Compound (s) of the formula II in bound form on an im Reaction medium insoluble carrier uses.