WO2016139245A1 - Protected selenodiphenols and method for the production thereof - Google Patents

Abstract

The invention relates to novel selenodiphenols which are protected at at least one hydroxyl group, to methods for producing same and to the use thereof as ligands in complexes.

Description

 Protected selenodiphenols and processes for their preparation Novel selenodiphenols protected at least one hydroxyl group, as well as processes for their preparation and their use as ligands in complexes.

The preparation of low-yielding selenodiphenols unprotected on the hydroxyl group is known from TK Paine et al., "Manganese complexes of mixed O, X, O donor ligands (X = S or Se): synthesis, characterization and catalytic reactivity", Dalton Trans., 2003, 15, 3136-3144.) TK Paine et al describes a synthesis of 2,2 ^" - selenobis (4,6-di-tert-butylphenol) using selenium dioxide. The preparation of 2,2 ^" -selenobis (4,6-di-tert-butylphenol) takes place here in an acidic medium with the addition of concentrated hydrochloric acid The product is obtained in a yield of only 25%.

A further multi-step synthetic route using Grignard reagent is disclosed in HM Lin et al., "A novel and efficient synthesis of selenides", ARKIVOC, 2012, viii, 146-156, which discloses a synthesis route for selenobiaryl ether in which bromine is first synthesized add the appropriate phenol to convert the product to a Grignard reagent with magnesium, and the Grignard reagent can then react with the added selenium before the actual coupling to the biaryl ether takes place:

+ Br + Mq + Se + Ph-R

Ph Ph Br-Ph-Mg-Br-Ph-Se-Mg-Br Ph-Se-Ph

The product could be obtained in a good yield, but this synthesis route is very expensive, which makes it unattractive for large-scale use. Here, a large number of synthesis steps are necessary, some of which are not uncritical in their implementation, especially when one thinks of an upscaling and uses standards that are common in the industry. Furthermore, large amounts of waste products and solvents which have to be disposed of in a complicated manner, inter alia due to the use of bromine, are obtained in this synthesis route.

A large-scale economical synthesis route for the preparation of selenodiphenols is described by EP 15168645.8 and US Pat. No. 14 / 720,063. In the hydroformylation mono- and bisphosphites are usually used, which are often composed of biphenol building blocks. The development of new ligands is often limited by the available biphenol, so ligand building blocks. Thus, 2,2'-selenobiaryl ethers represent a highly interesting class of compounds. The 2,2'-selenobiaryl ethers are currently used only in certain complexes, especially manganese-containing, but they have great potential for further applications.

The object of the invention was to produce a further completely new class of ligand building blocks in order to expand the field of available ligands for the respective specific complexes in catalysis. Furthermore, the task of producing ligands for rhodium hydroformylation catalysts. Therefore, it was also the object to provide new ligand building blocks, which serve as an intermediate for the preparation of ligands. The objects are achieved by simple and / or doubly protected on the two hydroxyl groups selenodiphenols. Thus, the objects are achieved by the selenobiaryls of the general structure Ia and the structures Ib and / or Ic, as well as mixtures containing Ia, Ib and Ic or two of said selenobiaryl. The invention relates to compounds of the selenodiaryl of the general structure Ia and compositions obtainable by the process according to the invention,

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ^{9 are} each independently selected from: -H, - (Ci-Ci ₂ ) -alkyl, -0- (ci Ci ₂₎ -alkyl, - (C ₆ -C ₂ o) aryl, -0- _(C6-C2o) -aryl, -halo, preferably -Cl, -F, -I optional -Br, -OC = 0- _(Ci-Ci2) alkyl, -N _[(Ci-Ci2) alkyl] _2,

-S-alkyl, -S-aryl, -COO- (Ci-Ci ₂ ) -alkyl, -CONH- (Ci-Ci ₂ ) -alkyl, -CO- (Ci-Ci ₂ ) -alkyl, -CO- ( C ₆ -C ₂₀ ) -aryl, -COOH, -SO ₃ H, -CN,

wherein each of the alkyl and aryl groups may be independently unsubstituted or substituted, optionally substituted - (Ci-Ci ₂ ) -alkyl groups and optionally substituted - (C6-C ₂ o) - Aryl groups may have one or more substituents depending on their chain length; optionally, the substituents may independently be selected from (C 3 -C 12) -cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluoro, chloro, cyano, formyl, acyl or alkoxycarbonyl, and wherein R is as defined above ⁵ and R ^{10 are} each independently selected from:

-H, - (Ci-Ci ₂₎ -alkyl, - _(C6-C2o) -aryl,

-C = O- (Ci-Ci2) -alkyl, wherein said alkyl and aryl groups may each be independently unsubstituted or substituted, optionally substituted - (Ci-Ci2) alkyl groups and optionally substituted - (C6-C2o) aryl groups depending on their chain length, have one or more substituents; the substituents can preferably be selected independently from - (C 3 -C 12) -cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, likewise R ⁵ and R ¹⁰ according to the invention are each independently selected from: -methylthioethyl, -trimethylsilyl, -triethylsilyl, -triisopropylsilyl, -ie / f.-butyldimethylsilyl, -ie / f.-butyldiphenylsilyl, -acetyl, -pivaloyl, - benzoic acid ester, -3 (2-nitrophenyl) acetyl, oxoacyl, trifluoromethanesulfonyl,

wherein R ⁵ and R ^{10 are} unequal when R ⁵ or R ¹⁰ is -H. In the structure of formula la, the situation R ⁵ and R ¹⁰ equal to -H are excluded from the invention.

Particular preference is given in formula la R ^1, R ^2, R ^3, R ^4, R ^6, R ^7, R ^8, R ⁹ are each independently selected from: -H, - (Ci-Ci2) alkyl, -0- (Ci-Ci2) alkyl, - (C6-C2o) aryl, -0- _(C6-C2o) -aryl, -Cl, -F, -I, -O-C = 0- (Ci-Ci ₂₎ -Alkyl, -N [(Ci-Ci ₂ ) -alkyl] ₂ .

The terms selenodiaryl, selenodiphenol, phenol and olefin are used in this application as a generic term and thus each include thus also substituted selenodiaryl, selenodiphenols, phenols and olefins. The abovementioned definitions for substituted - (C 1 -C 12) -alkyl groups and substituted - (C 6 -C 20) -aryl groups apply to all groups in which these alkyl or aryl groups are contained, ie in particular also for the following groups: -O- (Ci -Ci2) alkyl, - _(C6-C2o) aryl, -0- _(C6-C2o) -aryl, -OC = 0- (Ci-Ci ₂₎ -alkyl.

According to a particularly preferred embodiment, R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ^{9 are} each independently selected in the selenodiaryls of structures Ia, Ib, Ic and in the selenodiphenols of structure II from: -H, unsubstituted - (Ci-Ci2) -alkyl and / or unsubstituted -0- (Ci-Ci2) -alkyl groups, whereby the alkyl groups can be linear, branched or cyclisch.

 One or more substituents preferably comprise 1 to 10 substituents, in particular 1 to 3. In the context of the invention, the term - (C 1 -C 12) -alkyl comprises straight-chain and branched alkyl groups. These are preferably unsubstituted straight-chain or branched - (C 1 -C 5) -alkyl groups and, most preferably, - (C 1 -C 6) -alkyl groups. Examples of - (C 1 -C 12) -alkyl groups are, in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl,

2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1, 1-dimethylpropyl,

 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 2 , 2-dimethylbutyl,

 1, 3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1, 1, 2-trimethylpropyl,

1, 2,2-trimethylpropyl, 1-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl,

3-heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, decyl.

Halogen (shark) includes chlorine, bromine and iodine, with chlorine and fluorine being particularly preferred.

The explanations concerning the expression - (C 1 -C 12) -alkyl also apply to the alkyl groups in -O- (C 1 -C 12) -alkyl, ie in - (C 1 -C 12) -alkoxy. These are preferably unsubstituted straight-chain or branched - (C 1 -C 6) -alkoxy groups.

Substituted - (Ci-Ci2) alkyl groups and substituted - (Ci-Ci2) alkoxy groups can, depending on their chain length, have one or more substituents. The substituents are preferably selected independently of one another

- (C ₃ -C ₂₎ cycloalkyl, - (C ₃ -C ₂₎ -heterocycloalkyl, - _(C6-C2o) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl. This definition applies to all substituted alkyl or alkoxy groups of the present invention.

The term - (C 6 -C 20) -aryl and - (C 6 -C 20) -aryl- (C 6 -C 20) -aryl encompasses mono- or polycyclic aromatic hydrocarbon radicals for the purposes of the present invention. These have 6 to 20 ring atoms, particularly preferably 6 to 14 ring atoms, in particular 6 to 10 ring atoms, on. Aryl is preferably - (C 6 -C 10) -aryl and - (C 6 -C 10) -aryl- (C 6 -C 10) -arykyl is in particular phenyl, naphthyl, indenyl, Fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl. In particular, aryl is phenyl, naphthyl and antracenyl.

The term - (C 3 -C 12) -cycloalkyl in the context of the present invention comprises mono-, bi- or tricyclic hydrocarbon radicals having 3 to 12, in particular 5 to 12, carbon atoms. These include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl, norbonyl or adamantyl. An example of a substituted cycloalkyl would be menthyl.

The term - (C 3 -C 12) -heterocycloalkyl groups in the context of the present invention comprises non-aromatic, saturated or partially unsaturated cycloaliphatic groups having 3 to 12, in particular 5 to 12, carbon atoms. The - (C 3 -C 12) -heterocycloalkyl groups preferably have 3 to 8, more preferably 5 or 6, ring atoms. In the heterocycloalkyl groups, in contrast to the cycloalkyl groups 1, 2, 3 or 4, the ring carbon atoms are replaced by heteroatoms or heteroatom-containing groups. The heteroatoms or the heteroatom-containing groups are preferably selected from -O-, -S-, -N-, -N (= O) -, -C (= O) - or -S (= O) -. Examples of - (C 3 -C 12) -heterocycloalkyl groups include tetrahydrothiophenyl, tetrahydrofuryl, tetrahydropyranyl and dioxanyl.

Particularly preferred ethers protected Selenodiaryle are the following MeO (alkoxy, such as methoxy) protected selenodiphenols of the structure la (la 'with R ⁵ , R ¹⁰ = - (Ci-Ci ₂ ) alkyl, in particular -Me, -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ ,, optionally analogously as la "with R ⁵ , R ¹⁰ = - (C 6 -C 20) -aryl, preferably -phenyl, -9-anthryl).

Compounds according to the invention include mono- and / or diethers of selenodiphenols and mixtures thereof.

a) Particular preference is given to selenodiaryl of the structure Ia, where R ⁵ and R ¹⁰ are each independently selected from -H, - (C 1 -C 12) -alkyl, - (C 6 -C 20) -aryl, -trimethylsilyl, -acetyl, wherein R ⁵ and R ^{10 are} unequal when R ⁵ or R ¹⁰ is -H. b) Particular preference is given Selenodiaryle the structure la, where R ⁵ and R ¹⁰ are each independently selected from -H, -trimethylsilyl, acetyl, wherein R ⁵ and R ¹⁰ are unequal, when R ⁵ or R ¹⁰ -H is. c) Particular preference is given to selenodiaryl of the structure Ia, where R ⁵ and R ¹⁰ are each independently selected from -H, - (C 1 -C 12) -alkyl, -phenyl, where R ⁵ and R ^{10 are} different when R ⁵ or R ¹⁰ is -H. d) Particular preference is given to selenodiaryl of the structure Ia, where R ⁵ and R ¹⁰ are each independently selected from -H, methyl, ie / f.-butyl, where R ⁵ and R ^{10 are} different when R ⁵ or R ¹⁰ equals -H.

It is preferred in the abovementioned alternatives if in each case independently R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ in a), b), c) or d) are selected from H, - (Ci-Ci ₂ ) -alkyl, -0- (Ci-Ci ₂ ) -alkyl, - (C6-C ₂ o) -aryl, -0- (C6-C ₂ o) -aryl, -halogen , such as -Cl, -F, -I, and -OC = 0- (Ci-Ci2) -alkyl, are preferably selected from -H, - (Ci-Ci2) -alkyl,

-O- (Ci-Ci2) -alkyl, -halogen, particularly preferably are selected from -H, - (Ci-Ci2) -alkyl.

According to a further alternative of the invention, the compound is selected from

(I)

(Iii)

or mixtures containing at least two of the structures of Ia, Ib and Ic, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ^{9 are} each, in particular within the respective

Structures la, Ib and / or Ic, or for the structures la, Ib and Ic, are independently selected from: -H, - _(Ci-Ci2) alkyl, -0- (Ci-Ci ₂₎ -alkyl, - (C6-C ₂ o) aryl, -0- _(C6-C2o) -aryl, -halo, preferably -Cl, -F, -I optional -Br, -OC = 0- (Ci-Ci ₂₎ -Alkyl, -N [(Ci-Ci ₂ ) -alkyl] ₂ ; -S-alkyl, -S-aryl, -COO- (Ci-Ci ₂ ) -alkyl, -CONH- (Ci-Ci ₂ ) -alkyl, -CO- (Ci-Ci ₂ ) -alkyl,

-CO- (C ₆ -C ₂₀ ) aryl, -COOH, -SO ₃ H, -CN, wherein the alkyl and aryl groups may each be independently unsubstituted or substituted, optionally substituted - (Ci-Ci ₂ ) alkyl groups and optionally substituted - (C6-C ₂ o) - aryl groups may, depending on their chain length, have one or more substituents; the substituents are independently selected from - (C3-Ci ₂₎ cycloalkyl, - (C3-Ci ₂₎ -heterocycloalkyl, - _(C6-C2o) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, or wherein the respective radical R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ^9, although independently selected but is the same in the structures la, Ib and / or Ic, and

wherein R ⁵ and R ^{10 are the} same and are selected from:

- (Ci-Ci ₂ ) -alkyl, - (C ₆ -C ₂₀ ) -aryl, -C = 0- (Ci-Ci ₂ ) -alkyl, wherein said alkyl and aryl groups are each independently independently unsubstituted or substituted, optionally substituted - (Ci-Ci ₂ ) -alkyl groups and optionally substituted - (C6-C ₂ o) -aryl groups, depending on their chain length, one or more substituents exhibit; the substituents may optionally be independently selected from - (C3-Ci ₂₎ - cycloalkyl, - (C3-Ci ₂₎ -heterocycloalkyl, - _(C6-C2o) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl; also R ⁵ and R ¹⁰ according to the invention may each be independently selected from: methylthioethyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, -ie / f.-butyldimethylsilyl, -ie / f.-butyldiphenylsilyl, -acetyl, -pivaloyl , benzoate, -3 (2-nitrophenyl) acetyl, oxoacyl, trifluoromethanesulfonyl. a) According to one alternative, it is preferred if R ⁵ equal to R ¹⁰ is selected in structure la and R ⁵ and R ¹⁰ are selected from - (Ci-Ci ₂₎ -alkyl, - _(C6-C2o) -aryl, - C = O- (Ci-Ci ₂ ) -alkyl, wherein said alkyl and aryl groups may be substituted, optionally substituted - (Ci-Ci2) alkyl groups and optionally substituted - (C6-C2o) aryl groups depending on their Chain length, one or more substituents; the substituents may optionally be independently selected from - (C ₃ -C ₂₎ cycloalkyl, - (C ₃ -C ₂₎ -heterocycloalkyl, - _(C6-C2o) -aryl, fluorine, chlorine, cyano, formyl, Acyl or alkoxycarbonyl. b) According to an alternative, it is preferred that R ⁵ is R ¹⁰ in structure Ia and R ⁵ and R ^{10 are} selected from - (C 1 -C 12) -alkyl, where said alkyl groups may be substituted as defined above. R ⁵ is more preferably R ¹⁰ and is selected from methyl, -Me, -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , Fe / f.-Butyl c). In a further alternative, it is preferred that R ⁵ is R ¹⁰ in Structure Ia and R ⁵ and R ^{10 are} selected from methylthioethyl, -trimethylsilyl, -triethylsilyl, -triisopropylsilyl, -fe / f-butyldimethylsilyl, -fe / f-butyldiphenylsilyl, -acetyl, -pivaloyl, -benzoic acid ester, -3 - (2-nitrophenyl) acetyl, oxoacyl, trifluoromethanesulfonyl. d) According to another alternative, it is preferred that R ⁵ is R ¹⁰ in structure Ia and R ⁵ and R ^{10 are} selected from trimethylsilyl, acetyl.

According to a further alternative, the invention provides a compound of a selenodiaryl,

a) wherein in structure Ia R ⁵ is R ¹⁰ and is selected from -Me, -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , ie / f-butyl,

b) wherein in structure Ib R ^{5 is} selected from -Me, -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , ie / f-butyl, c) wherein in structure Ic R ^{10 is} selected from -Me, -CH ₂ CH ₃ , -CH 2 CH 2 CH 3, ie / f-butyl.

Particular preference is given to compounds of the structures Ia, Ib, Ic in which R ⁵ and R ^{10 are} methyl or R ⁵ and R ¹⁰ are identical to -CH ₂ CH ₃ or R ⁵ and R ¹⁰ are equal to -CH ₂ CH ₂ CH ₃ or R ⁵ and R ¹⁰ are equal to Fe / F-butyl. According to a particularly preferred embodiment, R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ in the structures Ia, Ib and / or Ic are each independently selected of: -H, - _(Ci-Ci2) alkyl, -0- (Ci-Ci ₂₎ -alkyl, - (C ₆ -C ₂ o) aryl, and -0- (C6-C ₂ o) - Aryl, wherein said alkyl groups may be unsubstituted or substituted as defined above, in particular in the alternatives a), b), c) and / or d). Particularly preferably, R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ in the structures Ia, Ib and / or Ic are each independently selected from -H, - (Ci-Ci2) -Alkyl, -0- (Ci-Ci2) -alkyl, preferably from -H and - (Ci-C ₆ ) -alkyl.

According to a further preferred embodiment, R ¹ , R ³ , R ⁶ , R ⁸ in the structures Ia, Ib and / or Ic are each independently selected from -H, - (Ci-Ci2) alkyl, in particular - (Ci-C4 ) Alkyl, wherein said alkyl groups may be unsubstituted or substituted. Particularly preferably, R ¹ , R ³ , R ⁶ , R ⁸ in the structures Ia, Ib and / or Ic are each independently methyl, ethyl, ie / f-butyl and / or isopentyl and R ² , R ⁴ , R ⁷ and R ^{9 are} equal to -H. Particularly preferably, the abovementioned selenodiarylics according to embodiments a), b), c) and d) are correspondingly substituted.

In one variant, R ¹ , R ³ , R ⁶ , R ⁸ in the structures Ia, Ib and / or Ic are methyl, preferably R ² , R ⁴ , R ⁷ , and R ⁹ are -H.

In one variant, R ¹ , R ³ , R ⁶ , R ⁸ in the structures Ia, Ib and / or Ic are tert-butyl, preferably R ² , R ⁴ , R ⁷ , and R ⁹ are -H.

In a variant, R ¹ , R ⁶ in the structures Ia, Ib and / or Ic are tert-butyl, wherein preferably R ² , R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ are -H. In one variant, R ³ , R ⁸ in the structures Ia, Ib and / or Ic are methyl, preferably R ¹ , R ² , R ⁴ , R ⁶ , R ⁷ and R ⁹ are -H.

 The invention likewise provides a process for the preparation of selenodiarylenes of the general structure Ia, in particular of the general structures Ia, Ib and Ic, and the compounds and compositions obtainable by the process, the process comprising the process steps,

(i) Reaction of a selenodiphenol of the general structure (II)

- with YR ⁵ formula IIIa and / or YR ¹⁰ formula IIIb for the connection of structure Ia, with Y as a leaving group, and R ⁵ and R ¹⁰ in formulas IIIa and IIIb are each independently selected from:

- (Ci-Ci ₂₎ -alkyl, - _(C6-C2o) -aryl,

-C = 0- (Ci-Ci2) -alkyl, wherein each independently the alkyl and aryl groups can be unsubstituted or substituted, optionally substituted - (Ci-Ci2) alkyl groups and optionally substituted - (C6-C2o) aryl groups can in Depending on their chain length, have one or more substituents; the substituents can be selected independently of one another from - (C 3 -C 12) -cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl, and / or alkoxycarbonyl, also R ⁵ and R ¹⁰ according to the invention may each be independently selected from: methylthioethyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, -ie / f.-butyldimethylsilyl, -ie / f.-butyldiphenylsilyl, -acetyl, -pivaloyl , benzoate, -3- (2-nitrophenyl) acetyl, oxoacyl, trifluoromethanesulfonyl,

- In particular, a reaction with a compound of formula III (purple = IIIb), so that YR ⁵ of the formula IIIa and YR ^{10 of} the formula IIIb are the same, or (ii) wherein at least one selenodiaryl of the structure Ia is obtained

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ in the structures II and la are each independently selected from: -H, - (Ci-Ci2) alkyl, - 0- (Ci-Ci2) -alkyl, - (C6-C2o) -aryl, -0- (C6-C2o) -aryl, -Halogen, such as -F, -Cl, -I, -OC = 0- (Ci -Ci ₂ ) -alkyl, -N [(Ci-Ci ₂ ) -alkyl] ₂ ;

-S-alkyl, -S-aryl, -COO- (Ci-Ci ₂ ) -alkyl, -CONH- (Ci-Ci ₂ ) -alkyl, -CO- (Ci-Ci ₂ ) -alkyl,

-CO- _(C6-C2o) aryl, -COOH, -S0 ₃ H, -CN, wherein said alkyl and aryl groups each independently may be unsubstituted or substituted, optionally substituted

- (Ci-Ci2) -alkyl groups and optionally substituted - (C6-C2o) -aryl groups can in

Depending on their chain length, have one or more substituents; the substituents can be independently selected from - (C 3 -C 12) -cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl or

Alkoxycarbonyl, in particular R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ^{9 are} each independently selected but identical in structures II and la,

wherein R ⁵ and R ¹⁰ in structure la are each independently selected from: -H, - (Ci-Ci ₂₎ -alkyl, - _(C6-C2o) -aryl,

-C = 0- (Ci-Ci2) -alkyl, wherein the alkyl and aryl groups are unsubstituted or substituted, optionally substituted - (Ci-Ci2) alkyl groups and optionally substituted - (C6-C2o) aryl groups depending on their Chain length, one or more substituents; the substituents can be independently selected from - (C 3 -C 12) -cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl; ⁵ and R ¹⁰ according to the invention are each independently selected from: -methylthioethyl, -trimethylsilyl, -triethylsilyl, -triisopropylsilyl, -ie / f.-butyldimethylsilyl, -ie / f.-butyldiphenylsilyl, -acetyl, -pivaloyl, -benzoic acid esters , -3- (2-nitrophenyl) acetyl, -oxoacyl, -trifluormethansulfonyl, wherein R ⁵ and R are not equal to ¹⁰ when R ⁵ or R is -H ^10th

Y in YR ^{5 of} the formula IIa and / or in YR ¹⁰ as the cleavable radical Y can correspond to one of the following cleavable radicals, without these radicals being limited to those listed. Y may include: shark, organyl, acyl, carboxy, carbonyl. In principle, all radicals known to the person skilled in the art in protecting group chemistry can be used as cleavable radicals Y. The choice of Y is known to the person skilled in the art, since the compound YR ⁵ of the formula IIIa and / or YR ^{10 of} the formula IIIb is used to introduce the group R ⁵ or R ¹⁰ and Y represents the counterpart. As an example, the introduction of R ⁵ or R ¹⁰ = Me called. The skilled person knows that he must use a methylating reagent. For example, methyl iodide or dimethyl sulfate in question, so that Y is iodide or sulfate. Y as a cleavable group thus also represents a counterion that is negatively charged or a negative one Partial charge carries. Accordingly, this counterion has a negative oxidation number.

In a preferred process variant, the compounds comprising the protecting groups R ⁵ and R ^{10 may be the} same, such that YR ^{5 may be} lilac and / or YR ¹⁰ lllb, where Y is halogen selected from chlorine, bromine and iodine, in particular Y is the same Chlorine, and R ⁵ and R ¹⁰ are the same and selected from - (Ci-Ci2) -alkyl and - (C ₆ -C ₂ o) -aryl. According to a process alternative, the selenodiphenol II can be reacted with YR ⁵ of the formula IIIa and / or YR ^{10 of} the formula IIIb in a molar ratio of 10: 1 to 1:10, preferably from 5: 1 to 1: 5. The selenodiphenol can be particularly preferred II with 0.8 to 1.2 eq (equimolar), in particular 0.9 to 1.1 eq, of the YR ⁵ formula IIIa and / or YR ^10, formula IIIb, where preferably formula IIIa is equal to IIIb. In this case, a reaction of about 1 mol of selenodiphenol with about greater than or equal to 2 moles of YR ⁵ formula IIIa and / or YR ¹⁰ formula IIIb each with +/- 0.2 mol for preparing the compound Ia with R ⁵ is R ¹⁰ , and wherein R ⁵ is R ^{10 is} not -H, preferred according to a process alternative. According to a preferred further alternative, a selenodiphenol of general structure II can be converted to selenodiaryls of structures Ia and / or Ib by reacting about 1 mol of selenodiphenol II with about 0.8 to 1.2 moles of YR ⁵ formula IIIa and / or YR ¹⁰ Formula IIIb is implemented.

According to a further preferred variant of the method, the reaction can be carried out by reacting the selenodiphenol of the general structure II in the presence of a strong base selected from metal hydrides sodium hydride, lithium hydride, lithium organyls such as n-butyllithium, alkylamines such as triethylamine, pyridine bases, in particular metal hydrides with YR ⁵ purple and YR ¹⁰ lllb where Y is halogen selected from chlorine, bromine and iodine, and R ⁵ and R ^{10 are} selected from - (C 1 -C 12) -alkyl, - (C 6 -C 20) -aryl, in particular YR ^{5 of} the formula IIIa and YR ¹⁰ of formula IIIb. More preferably X is chlorine and R ⁵ and R ¹⁰ are selected from - (Ci-Ci2) alkyl, - (C6-C2o) -aryl, particularly preferred are - (Ci-C4) alkyl, preferably methyl, ie /f.-Butyl-.

According to the process, it is also preferable to obtain the following compounds selected from selenodiaryls of the structures Ia, Ib and Ic or Mixtures comprising at least two of the structures Ia, Ib and Ic, such as Ia and Ic, Ia and Ib; Ib and Ic,

 (I)

where R ⁵ is R ¹⁰ in structure Ia,

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ^{9 are} each independently selected from: -H, - (Ci-Ci ₂ ) -alkyl, -0- (ci Ci ₂ ) -alkyl, - (C6-C ₂ o) -aryl, -O- (C6-C ₂ o) -aryl, -halogen,

-OC = 0- _(Ci-Ci2) alkyl, -N _[(Ci-Ci2) alkyl] _2, -S-alkyl, -S-aryl, -COO- (Ci-Ci ₂₎ -alkyl, -CONH- (Ci-Ci ₂₎ -alkyl, -CO- (Ci-Ci ₂₎ -alkyl, CO- _(C6-C2o) aryl, -COOH, -S0 ₃ H, -CN; wherein the alkyl and aryl groups may each independently be unsubstituted or substituted, optionally substituted - (C 1 -C 12) alkyl groups and optionally substituted - (C 6 -C 20) aryl groups may have one or more substituents depending on their chain length; the substituents can be selected independently its - (C 3 -C 12) -cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and

wherein R ⁵ and R ^{10 are the} same and are selected from: - (Ci-Ci2) alkyl, - (C6-C2o) -aryl, - C = 0- (Ci-Ci2) alkyl, wherein the alkyl and aryl groups each independently are unsubstituted or substituted, optionally substituted - (C 1 -C 12) -alkyl groups and optionally substituted - (C 6 -C 20) -aryl groups, depending on their chain length, have one or more substituents; the substituents can be independently selected from - (C 3 -C 12) -cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl; likewise, R ⁵ and R ¹⁰ according to the invention may each be independently selected from:

 -methylthioethyl, -trimethylsilyl, -triethylsilyl, -triisopropylsilyl, -ie / f -butyldimethylsilyl, -tert -butyldiphenylsilyl, -acetyl, -pivaloyl, -benzoic acid, -3- (2-nitrophenyl) -acetyl, -oxoacyl, -trifluoromethanesulfonyl.

It is preferred that R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ^{9 are} each independently selected and R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are the same in the respective structures Ia, Ib and Ic.

The invention further provides a complex comprising at least one compound of general structure Ia, Ib and / or Ic or of mixtures comprising at least two of said structures, and at least one metal atom selected from Rh, Ru, Co, Ir, in particular Rh, Ir, Ru, preferably Rh. The complexes may be present as simple complexes or dimers, etc. Preferred is a complex comprising at least one compound of the general structure Ia wherein R ⁵ and R ^{10 are} not -H, and R ⁵ and R ¹⁰ otherwise correspond to the abovementioned definitions, preferably with R ⁵ equal to R ¹⁰ .

The invention likewise provides for the use of at least one compound of the general structure Ia, Ib and / or Ic or of mixtures comprising at least two of said structures as ligand in a complex comprising at least one meta IIatom.

According to a further alternative, the invention provides the use of at least one compound of general structure Ia, Ib and / or Ic or of mixtures comprising at least two of the cited hydroformylation reaction structures, particularly preferred is the use of a compound the structure Ia, wherein R ⁵ and R ^{10 are} not -H and R ⁵ and R ¹⁰ otherwise correspond to the abovementioned definitions, preferably with R ⁵ equal to R ¹⁰ .

The invention likewise relates to the use of a compound of general structure Ia, in particular of structures Ib and / or Ic, as an intermediate for the preparation of ligands, such as phosphite-protected selenodiphenols in which R ⁵ or R ¹⁰ corresponds to an unsubstituted or substituted phosphite group which carries, for example, a phenol or biphenol unit. Furthermore, the subject matter of the invention is a method comprising the method steps

(i) presentation of at least one olefin,

(ii) adding a complex comprising at least one compound of general structure Ia, Ib and / or Ic or mixtures comprising at least two of said structures, and at least one metal atom selected from Rh, Ru, Co, Ir, or at least one compound of the general Structure Ia, Ib and / or Ic or of mixtures comprising at least two of said structures and at least one substance which has at least one metal atom selected from Rh, Ru, Co, Ir, more preferably compound Ia, wherein R ⁵ and R ¹⁰ are not -H and R ⁵ and R ¹⁰ correspond to the otherwise mentioned definitions above.

(iii) supplying H and CO,

 (iv) heating the reaction mixture,

wherein the olefin is reacted to an aldehyde. The process steps (i), (ii), (iii) and (iv) may alternatively be carried out in any order. In this case, a yield of greater than or equal to 85% and / or an n-regioselectivity of greater than 20% can preferably be achieved with the compounds according to the invention of the structures Ia, Ib and / or Ic in a hydroformylation according to the above use or the above process. The invention will be explained in more detail by way of examples, without limiting the invention to the exemplary embodiments. General methods

Solvents and reagents

 All reactions with moisture- and / or oxygen-sensitive substances were carried out in heated apparatus under an argon atmosphere. Solvents for extraction and column chromatography were used in the following purities: dichloromethane (99.9%, Walter, Art. No. BIE 073107033), ethyl acetate (99.5%, Walter, Art. No. BIE 003917025) and n-hexane ( 95%, Walter (Baker), Item No. 8669), n-heptane (95%, Walter (Baker), Item No. 8662). Other solvents for extraction and column chromatography were of technical grade and were used without further purification unless otherwise stated. Dry solvents (abs.) Were cleaned with a Pure Solv MD-7 system and stored under argon atmosphere. Benzyl bromide was freshly distilled before use (17 mbar / 82 ° C). Deuterated solvents were distilled from the indicated desiccants: dichloromethane-d2 (phosphorus pentoxide), toluene-ds (1st KOH, 2. sodium). Chemicals from Sigma Aldrich, Alfa Aesar, Acros Organics, Avantor Performance Materials B.V., Merck KGaA and ABCR GmbH & Co. KG were used for the syntheses. Unless otherwise stated, these were used without further purification.

Chromatographic methods

Column chromatography: Column chromatographic separations were carried out at elevated pressure (flash chromatography) on silica gel 60 230-400 mesh from Merck KGaA (particle size: 0.040-0.063 mm). The eluent mixtures used and the volume ratios v / v are given in the following instructions. For the eluents used, the following abbreviations apply: DCM (dichloromethane), EE (ethyl acetate), H (n-hexane), and Toi (toluene).

Filtration: Filtrations for the separation of resulting solids were carried out with a G4 frit (pore size: 10-16 μηη). analytics

 IR spectroscopy: The IR spectra were recorded using the Nicolet 6700 FT-IR spectrometer from Thermo Electron. The substances were measured by ATR method.

¹ H NMR spectroscopy: The ¹ H NMR spectra were recorded on the model AV 300 (300 MHz) and on the Bruker model Fourier 300 (300 MHz). The chemical shifts are given in units of the δ scale. The residual proton signals of the solvents (dichloromethane-d2: δ = 5.32 ppm, toluene-ds: δ = 7.09, 7.00, 6.98, 2.09 ppm) served as standard.

¹³ C NMR spectroscopy: The ¹³ C NMR spectra were recorded on Bruker's AV 300 (75 MHz) and Fourier 300 (75 MHz) models. The internal standard used was the solvent signal (dichloromethane-d2: δ = 54.0 ppm, toluene-ds: δ = 137.9, 129.2, 128.3, 125.5, 20.4 ppm) with the chemical shifts taken from the ¹ H broadband decoupled spectra.

⁷⁷ Se NMR spectroscopy: The ⁷⁷ Se NMR spectra were recorded on the Bruker AV 300 (57 MHz). The spectra were measured ¹ H broadband decoupled. The chemical shifts are indicated in ppm.

Mass spectrometry: El mass spectra were recorded on the Thermigan Electron Finnigan MAT 95-XP and Agilent Model 6210 Time-of-Flight LC / MS ESI-TOF mass spectra.

Autoclave experiments of rhodium-catalyzed hydroformylation

 The hydroformylation was carried out in a 200 mL autoclave from Premex Reactor AG, Lengau, Switzerland, equipped with pressure maintenance, gas flow measurement, gassing stirrer and pressure pipette. The toluene solvent was purified with a Pure Solv MD-7 system and stored under argon. The substrate 1-octene or n-octene used as substrate (EVONIK Industries AG, octene isomer mixture of 1-octene: 3.3%, cis + trans-2-octene: 48.5%, cis + trans-3-octene: 29.2%; cis + trans-octene-4: 16.4%, skeletally isomer octene: 2.6%) was refluxed for several hours over sodium and distilled under argon.

For the experiments, solutions of the catalyst precursor and of the ligand were mixed in an autoclave under an argon atmosphere. The catalyst precursor used was [(acac) Rh (COD)] (Umicore, acac = acetylacetonate anion, COD = 1,5-cyclooctadiene). For experiments with a concentration of 100 ppm-rhodium, 10 mL of a 4.31 mM solution were added to the autoclave. Subsequently, the ratio of L / Rh = 5: 1 (or 1: 1) corresponding mass of the ligand was dissolved in 10 mL of toluene and mixed. By adding more toluene, the initial volume of the catalyst solution was adjusted to 41.0 ml. In a pressure-resistant pipette was charged: 1-octene and n-octenes (10.70 g). The autoclave was at a total gas pressure (synthesis gas: Linde; H ₂ (99.999%): CO (99.997%) = 1: 1) of a) 42 bar for a final pressure of 50 bar and b) 12 bar for the final pressure of 20 bar with stirring (1500 rev / min) heated to the temperatures specified. After the reaction temperature had been reached, the synthesis gas pressure was increased to a) 48.5 bar for a final pressure of 50 bar or b) 19.5 bar for a final pressure of 20 bar and the educt was pressurized with an overpressure of about 3 bar set in the pressure pipette. The reaction was carried out at a constant pressure of 50 or 20 bar (post-pressure regulator from Bronkhorst, NL) for 4 h. The autoclave was cooled to room temperature at the end of the reaction time, expanded with stirring and purged with argon. In each case 1 .0 mL of the reaction mixtures were removed immediately after switching off the stirrer, diluted with 5.0 mL of pentane and analyzed by gas chromatography: HP 5890 Series II plus, PONA, 50 mx 0.2 mm x 0.5 μηι.

Abbreviations: calc. = Calculated; gef. = found; NCS = / V-chlorosuccimide; RT =

room temperature General procedure for the synthesis of precursors:

 General procedure AAV1 for the preparation of selenodiphenols (II).

 The corresponding unsubstituted and / or substituted phenols (1 equivalent) were added to a mixture of selenium dioxide (0.6 equivalent) in pyridine and stirred for 2-18 hours at 55-85 ° C. Subsequently, the reaction mixtures were diluted with ethyl acetate, filtered and the organic phases were washed with hydrochloric acid (10%) and water. After separation of the organic phase, it was dried over magnesium sulfate and the solvent was distilled off under reduced pressure. The crude product of II was purified by column chromatography. dimethyl-2-hydroxyphenyl) selen

In a 250 ml round bottom flask, 49.9 g of selenium dioxide (413 mmol) in 100 ml of pyridine were heated to 55 ° C. using an oil bath. Then, 25 ml of 2,4-dimethylphenol (206 mmol) was added and the temperature was held for seven and a half hours. After completion of the reaction, the mixture was diluted with 400 ml of ethyl acetate and filtered. The organic phase was washed with water and dried over magnesium sulfate. The pyridine was removed by distillation and the residue redissolved in ethyl acetate and washed with 10% hydrochloric acid and water to remove residues of pyridine. The organic phase was dried with magnesium sulfate and freed from the solvent under reduced pressure. The crude product thus obtained was heated under reflux in 400 ml of cyclohexane. After cooling to room temperature, the product crystallized. After one day, the product was filtered off, the filtrate was concentrated by half and recrystallized at 4 ° C. There were obtained 18.56 g, 58 mmol (56%) of fine, slightly yellow plates of the product m _p = 120.1 ° C (recrystallization from cyclohexane).

¹ H NMR (400 MHz, CDCl ₃ ) δ = 7.1 1 -7.12 (m, 2H), 6.90-6.92 (m, 2H), 5.95 (br, 2H, OH), 2.23 (s, 6H), 2.19 (s , 6H); ¹³ C NMR (100 MHz, CDC) δ = 152.04, 133.35, 133.30, 130.67, 124.42, 1 15.31, 20.45, 16.69; ⁷⁷ Se NMR (76 MHz, CDCb) δ = 164.91; HRMS for Ci ₆ Hi ₈ O 2 ⁸⁰ Se (ESI +) [M + Na ⁺ ]: Calcd: 345.0370, found: 445.0363; Elemental analysis for Ci6Hie02Se: calculated: C: 59.82%, H: 5.65%, found: C: 59.69%, H: 5.76%. - (3-ieri-butyl-2-hydroxy-5-methylphenyl) selen

As described in AAV1, 0.80 g of 4-he / f-butyl-2-methylphenol (4.9 mmol, 1 .0 eq) was added to a solution of 0.33 g of selenium dioxide (2.9 mmol, 0.6 eq.) In 6.7 mL of pyridine and 55 ° C stirred for 56 hours. The reaction mixture was diluted with 50 mL of ethyl acetate, filtered and washed three times with 50 mL hydrochloric acid (10%) and once with 50 mL brine. After drying over magnesium sulfate, the solvent was removed under reduced pressure and the residue obtained was purified by column chromatography (eluent cyclohexane / ethyl acetate 99: 1). Yield: 36%, 0.35 g, 0.9 mmol. m _p = 98.5 ° C; ¹ H NMR (400 MHz, CDCl ₃ ) δ = 7.30 (d, ⁴ J = 2.4 Hz, 2H), 7.1 1 (d, ⁴ J = 2.4 Hz, 2H), 5.92 (s, 2H, OH), 2.26 ( d, 6H), 1.23 (s, 18H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ = 151.78, 144.03, 129.83, 129.51, 123.89, 1 14.95, 34.18, 31 .56, 16.99; HRMS for C2 ₂ H ₃ oO 2 ⁸⁰ Se (ESI +) [M + Na ⁺ ]: calculated: 429.1309, found: 429.1250. -di-tert-butyl-2-hydroxyphenyl) selen

As described in AAV1, 0.80 g of 2,4-di-ie-f-butylphenol (3.8 mmol, 1 .0 eq.) Was added to a solution of 0.25 g of selenium dioxide (2.3 mmol, 0.6 eq.) In 5.4 mL of pyridine and 55 ° C stirred for 4 days. The reaction mixture was diluted with 50 mL of ethyl acetate, filtered and washed three times with 50 mL hydrochloric acid (10%) and once with 50 mL Washed saline. After drying over magnesium sulfate, the solvent was removed under reduced pressure and the residue obtained was purified by column chromatography (eluent cyclohexane / ethyl acetate 99: 1). The desired product was crystallized from n-heptane at 4 ° C. Yield: 25%, 0.24 g, 0.5 mmol. m _p = 141 .1 ° C (recrystallization from heptane); ¹ H NMR (400 MHz, CDCl ₃ ) δ = 7.31 (d, ⁴ J = 2.4 Hz, 2H), 7.29 (d, ⁴ J = 2.4 Hz, 2H), 6.29 (s, 2H, OH), 1.42 (s, 18H), 1.24 (s, 18H); ¹³ C NMR (100 MHz, CDCIs) δ = 151.7, 143.5, 135.8, 129.8, 125.6, 1 17.2, 35.4, 34.4, 31.6, 29.7; HRMS for C28H ₄₂ ⁸⁰ O2 Se (ESI +) [M + Na ^+]: Calculated: 513.2248, Found: 513.2152. -ferf-butyl-5-ethyl-2-hydroxyphenyl) selen

As described in AAV1, 2.00 g of 2-ie / f-butyl-4-ethylphenol (15.8 mmol, 1 .0 eq.) Was added to a solution of 1.06 g of selenium dioxide (9.5 mmol, 0.6 eq.) In 18 mL of pyridine and added Stirred 60 ° C for 4 days. The reaction mixture was diluted with 50 mL of ethyl acetate, filtered and washed three times with 50 mL hydrochloric acid (10%) and once with 50 mL brine. After drying over magnesium sulfate, the solvent was removed under reduced pressure and the residue obtained was purified by column chromatography (mobile phase: cyclohexane / ethyl acetate 99: 1). Yield: 27%, 0.659 g, 1 .5 mmol. m _p = 68.2 ° C; ¹ H NMR (400 MHz, CDCl ₃ ) δ = 7.18 (d, ⁴ J = 2.1 Hz, 2H), 7.07 (d, ⁴ J = 2.1 Hz, 2H), 6.32 (s, 2H, OH), 2.51 (q , ³ J = 7.6 Hz, 4H), 1 .40 (s, 18H), 1 .16 (t, ³ J = 7.6 Hz, 6H). ¹³ C NMR (100 MHz, CDC) δ = 152.00, 136.42, 136.32, 131.98, 128.22, 1 17.19, 35.09, 29.53, 28.12, 15.66; HRMS for C _{24 24} ⁸⁰ O2 Se (ESI +) [M + Na ^+] H: Calculated: 457.1622, Found: 457.1632; Elemental analysis for C ₂₄ H ₂₄ 0 ₂ Se: Calculated: C: 66.50%, H: 7:38%, found: C: 66.26%, H: 7:54%. -di (1, 1-dimethylpropyl) -2-hydroxyphenyl) selenium

As described in AAV1, 2.00 g of 2,4-ϋί- (Ί, 1-dimethylpropyl) phenol (13.6 mmol, 1 .0 eq.) Was added to a solution of 0.91 g of selenium dioxide (8.2 mmol, 0.6 eq.) In 19 mL of pyridine and stirred at 60 ° C for 4 days. The reaction mixture was diluted with 50 mL of ethyl acetate, filtered and washed three times with 50 mL hydrochloric acid (10%) and once with 50 mL brine. After drying over magnesium sulfate, the solvent was removed under reduced pressure and the residue obtained was purified by column chromatography (eluent: cyclohexane / ethyl acetate with a gradient of 100: 0 to 95: 5). Yield: 25%, 0.586 g, 1 .1 mmol. m _p = 1 19.7 ° C; ¹ H NMR (400 MHz, CDCl ₃ ) δ = 7.18 (d, ⁴ J = 2.3 Hz, 2H), 7.1 1 (d, ⁴ J = 2.3 Hz, 2H), 6.15 (s, 2H), 1 .82 ( q, ³ J = 7.5 Hz, 4 H), 1 .50 (q, ³ J = 7.4 Hz, 4 H), 1 .34 (s, 12H), 1 .16 (s, 12H), 0.58 (q, ³ J = 7.5 Hz, 12 H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ = 151.34, 142.32, 133.78, 130.15, 127.34, 1.16.99, 38.85, 37.45, 36.94, 33.1 1, 28.45, 27.72, 9.46, 9.01; HRMS for C2 ₂ H ₃ OO 2 ⁸⁰ Se (ESI +) [M + Na ⁺ ]: calcd: 569.2874, found: 569.2800. -trimethoxyphenyl) selenium

The reaction was carried out in accordance with AAV1 in a screw-test tube. To this was dissolved 1, 2,4-trimethoxyphenol (1 .30 g, 7.7 mmol) and selenium dioxide (0.51 g, 4.6 mmol) in acetic acid (1 mL, 8.2 m) and heated to 85 ° C for 5 h. Product 2 (0.72 g, 1.74 mmol, 45%) was obtained as a brown crystalline solid.

GC (hard, HP-5): t _R = 17.3 min. R _f = 0.6 (CH: EE 95: 5). ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 6.76 (s, 2H), 6.56 (s, 2H), 3.90 (s, 6H), 3.85 (s, 6H), 3.70 (s, 6H) ppm. ¹³ C-NMR (75 MHz, CDC): 153.19, 138.92, 123.14, 1 15.27, 1 1 1 .72, 109.98, 55.74, 35.28, 29.71, 29.49, 29.24 ppm. ⁷⁷ Se NMR (76 MHz, CDCl ₃ ): δ = 282.15 ppm; HRMS (ESI): m / z for Ci ₈ H220 ₆ NaSe: calculated 435.0479, found: 435. 1 171.

To 6-methyl-2,3,4-trimethoxyphenyl) selenium

 In a 25 mL round bottom flask, 0.80 g 3,4,5-trimethoxytoluene (4.3 mmol) was dissolved in 6 mL acetic acid, added with 0.27 g selenium dioxide (2.4 mmol) and heated in an oil bath at 85 ° C. After 12 days, the reaction mixture was filtered, the filtrate diluted with dichloromethane and washed with saturated sodium chloride solution. The organic phase was dried over magnesium sulfate and the solvent was distilled off under reduced pressure. The crude product was purified by column chromatography. The column length was 24 cm with a diameter of 3 cm. The eluent used was cyclohexane / ethyl acetate in the ratio 9: 1.

Yield: 0.399 g (0.9 mmol), 41%; GC: R (hard, HP-5) = 16,250 min; TLC: R _f (CH: EE, 2: 1) = 0.4; ¹ H-NMR: (400 MHz, CDCl 3) δ [ppm] = 2.37 (s, 6H), 3.59 (s, 6H), 3.78 (s, 6H), 3.82 (s, 6H), 6.54 (s, 2H) ; ¹³ C-NMR: (100 MHz, CDCl 3) δ [ppm] = 23.52 56.00, 60.60, 60.86, 109.17, 1 18.21, 137.07, 140.44, 153.06, 154.19.

HRMS (ESI, pos.mode): m / z for [M + Na +]: calculated: 465.0792 found: 465.0780

selenium-bis (4,5-dimethoxy-2-methyl-phenyl)

In a 25 mL round bottomed flask 1.00 g of 3,4-dimethoxytoluene (6.5 mmol) were dissolved in 9 mL of acetic acid, treated with 0.40 g of selenium dioxide (3.6 mmol) and heated in an oil bath at 85 ° C. After 12 days, the reaction mixture was filtered, the filtrate diluted with dichloromethane and washed with saturated sodium chloride solution. The organic phase was dried over magnesium sulfate and the solvent Distilled under reduced pressure. The crude product was purified by column chromatography. In this case, a column automat the company BUCHI-Labortechnik GmbH, Essen was used. The column length was 16 cm and the diameter 6 cm. The eluent used was cyclohexane / ethyl acetate using an ethyl acetate gradient: 0% (over 5 min), 1-5% (over 5 min), 5-10% (over 8 min), 10-20% (8 min), 20-40% (10 min), 40-100% (10 min). The pumping speed was 100 mL / min.

Yield: 0.637 g (1 .6 mmol), 51%; GC: R (hard, HP-5) = 15,968 min; ¹ H-NMR: (400 MHz, CDCl 3) δ [ppm] = 2.34 (s, 6H), 3.70 (s, 6H), 3.86 (s, 6H), 6.76 (s, 2H), 6.77 (s, 2H) ; ¹³ C-NMR: (100 MHz, CDCl 3) δ [ppm] = 21.96, 56.07, 56.16, 1 13.47, 1 16.51, 121 .55, 132.50, 147.54, 148.70; HRMS (ESI, pos.mode): m / z for [M + Na +]: calculated: 405.0581 found: 405.0484. Synthesis of the hydroxyl-protected selenodiphenols Ia and Ib / Ic

 (1.0 eq) R = Me: la '

Example 1: 2.0 eq of sodium hydride (60% in paraffin oil) in 3.0 mL of abs. H 2 O were added to a 25 mL Schlenk vessel under argon atmosphere. DMF suspended and cooled to 0 ° C. Subsequently, 1 .0 eq selenodiphenol II, dissolved in 2.0 mL abs. DMF, added dropwise. The resulting yellowish solution was stirred at 0 ° C for ten minutes and at RT for one hour. Subsequently, again at 0 ° C, 2.0 eq of the halide, here methyl iodide, added and stirred for 10 minutes at 0 ° C, with a turbidity of the reaction solution was observed. After a further 17 hours at RT, water (3.0 ml / 1.0 mmol) was added with ice-cooling and the resulting phases were separated. The aqueous phase was extracted with ethyl acetate (3 × per 5.0 mL / 1 .0 mmol). The combined organic phases were washed with water (2 × 10 ml / 1.0 mmol) and a saturated NaCl solution (2 × 10 ml / 1 .0 mmol) and dried over magnesium sulfate. The desiccant was filtered off and the solvent removed under reduced pressure. The resulting yellowish oil was dissolved in Acetonitrile (5.0 mL / 1.0 mmol) was added and treated with n-heptane (2.5 mL / 1 .0 mmol). The phases were separated and the solvent removed under reduced pressure. The crude product was dried in vacuo at 50 ° C for three hours. Example 2: Synthesis of bis (2- (methoxy) -3,5-dimethylphenyl) selane la '

According to Example 1, 81.0 mg (2.03 mmol, 2.0 eq, 60% in paraffin oil) of sodium hydride and 548 mg (1.70 mmol, 1.0 eq) of selenodiphenol II were reacted with 3.74 mmol of 2.0 eq) of methyl iodide. After extractive work-up, the title compound Ia 'was obtained.

Example 3: Synthesis of bis (2- (benzyloxy) -3,5-dimethylphenyl) selane la '"

 According to Example 1, 82.4 mg (2.06 mmol, 2.0 eq, 60% in paraffin oil) of sodium hydride and 331 mg (1.03 mmol, 1 .0 eq) of selenodiphenol II were reacted with 244 μM (352 mg, 2.06 mmol, 2.0 eq) of benzyl bromide. After extractive work-up, 407 mg (0.810 mmol, 79%) of the title compound Ia "were obtained as a pale yellow oil.

IR (ATR): * (cm ^"1 ) = 3088; 3063; 3029; 2917; 2859; 2730; 1598; 1566; 1497; 1465; 1453; 1370; 1308; 1270; 1209; 1 127; 1078; 978; 912 ; 848; 815; 776; 749; 725; 694; 601; 569; 513; 492; 466; ¹ H-NMR (300 MHz, dichloromethane-d ₂ ): δ (ppm) = 7.42-7.30 (m, 4H, Ar-CH); 7.30-7.09 (m, 6H, Ar-CH); 6.90-6.68 (m, 4H, Ar-CH); 4.78 (s, 4H, -OCH ₂ Ph); 2.19 (s, 6H, -; CH ₃ ); 2.10 (t, J = 0.7 Hz, 6H, -CH ₃ ); ¹³ C-NMR (75 MHz, dichloromethane-d ₂ ): δ (ppm) = 154.5, 138.0, 135.2, 132.6, 132.0, 131.9 ; 128.7; 128.5; 128.3; 125.1; 74.77; 20.86; 16.77; ⁷⁷ Se NMR (57 MHz, dichloromethane-d ₂ ): δ (ppm) = 299.2; ⁷⁷ Se NMR (57 MHz, toluene-ds): δ (ppm) = 302.6; MS (ESI-TOF): m / z = 525,130 ([M + Na] ⁺ ); 541 .124 ([M + K] ⁺ ); HR-MS (ESI-TOF): calcd for C3oH ₃ o0 ₂ SeNa ([M + Na] ^+): 525.13053, Found .: 525.12986;. C3oH ₃ o0 ₂ Se (502.14 g / mol).

Both bis (3,5-dimethyl-2-hydroxyphenyl) selenium, di (3-he / f-butyl-2-hydroxy-5-methylphenyl) selenium; Bis (3,5-di-IE / f-butyl-2-hydroxyphenyl) selenium; Di (3-ie / f-butyl-5-ethyl-2-hydroxyphenyl) selenium; Bis (3,5-di (1,1-dimethylpropyl) -2-hydroxyphenyl) selenium; Bis (3-he / f-butyl-5-methyl-2-hydroxyphenyl) selenium, bis (3,3 ', 5,5'-tetra-ie / f-butyl-2-hydroxyphenyl) selenium can be prepared analogously Examples 1 or to the corresponding bis (2- (methoxy) - or analogous derivatives of the substituted selenenes of the general structure Ia.

Mono-protection of selenodiphenol

Example 4: Synthesis of 2 - ((2- (methoxy) -3,5-dimethylphenyl) selanyl) -4,6-dimethylphenol la "

 (1.0 eq)

40.2 mg (1.01 mmol, 1.0 eq, 60% strength in paraffin oil) of sodium hydride in 3.0 mL abs. in a heated, under argon atmosphere 25 mL teapot. THF suspended and cooled to 0 ° C. Subsequently, 324 mg (1 .01 mmol, 1.0 eq) selenodiphenol II, dissolved in 2.0 mL abs. THF, added dropwise. The yellowish solution was stirred at 0 ° C for 15 minutes and at RT for two hours. Subsequently, at 0 ° C, 1 .01 mmol, 1 .0 eq) were added methyl iodide and stirred at 0 ° C for 30 minutes. After a further 16 hours at RT, the solvent was removed under reduced pressure. There were in the reaction mixture, 2 - ((2- (methoxy) -3,5-dimethylphenyl) selanyl) -4,6-dimethylphenol Ib ", lc" and bis (2- (methoxyoxy) -3,5-dimethylphenyl) selan la "((determined from crude ¹ H NMR spectrum) can be detected. atalyse - hydroformylation

 IV

 Schematic: Representation of the substances tested in rhodium-catalyzed hydroformylation. As compound IV, the commercially available Alkanox 240 was used.

Table 1: Representation of the catalysis experiments using

 Organoselenium.

Explanations to Table 1: p = pressure, T = temperature, t = time, A = yield; S = n regioselectivity. VG = Comparative Example The rhodium-catalyzed hydroformylation without addition of a trivalent phosphorus compound IV (entry 2) resulted in a yield of 9.5% (yield of 90.5% Restolefin) and an n-regioselectivity of 33.2%. An addition of component IV (entry 1), which is known to be active in the hydroformylation, also showed only a low yield of 20%. The use of unprotected selenodiphenols II, ie those having two free OH groups, in the hydroformylation thus leads to an inhibition. The use of the benzyl-protected selenodiphenol 1a '(entry 3) also resulted in a good yield of 85.8% with constant n-regioselectivity, meaning that the compounds according to the invention are suitable as ligands in the hydroformylation.

Claims

claims

1 . Compound of a selenodiaryl having a general structure (Ia)

- wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ^{9 are} each independently selected from: -H, - (Ci-Ci ₂ ) -alkyl, -0- (Ci -Ci ₂ ) -alkyl, - (C ₆ -C 20) -aryl, -O- (C ₆ -C 20) -aryl, -halo, -OC = O- (Ci-Ci ₂ ) -alkyl, -N [( Ci-Ci ₂₎ -alkyl] _2, -S-alkyl, -S-aryl, -COO- _(Ci-Ci2) alkyl, -CONH- (Ci-Ci ₂₎ -alkyl, -CO- (Ci Ci ₂ ) -alkyl, -CO- (C ₆ -C 2o) -aryl, -COOH, -SO ₃ H, -CN, wherein the alkyl and aryl groups are each independently independently substituted or substituted, optionally substituted - ( Ci2) alkyl groups and optionally substituted - (C6-C2o) aryl groups have at least one substituent and the at least one substituent is independently selected from - (C3-Ci2) -cycloalkyl, - (C3-Ci2) -Heterocycloalkyl, - (C6 -C 2o) aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and

wherein R ⁵ and R ^{10 are} each independently selected from:

-H, - (Ci-Ci ₂₎ -alkyl, - (C ₆ -C2o) -aryl, -C = 0- _(Ci-Ci2) alkyl, -methylthioethyl, -trimethylsilyl, -triethylsilyl, -triisopropylsilyl, - ie / f.-butyldimethylsilyl, -ie / f.-butyldiphenylsilyl, -acetyl, -pivaloyl, -benzoic acid ester, -3- (2-nitrophenyl) -acetyl, -oxoacyl, -trifluoromethanesulfonyl, wherein said alkyl and aryl groups each independently are unsubstituted or substituted, where optionally substituted - (Ci-Ci2) -alkyl groups and optionally substituted - (C6-C2o) -aryl groups have at least one substituent and the at least one substituent are each independently selected from - (C3-C12) - cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl;

wherein R ⁵ and R ^{10 are} unequal when R ⁵ or R ¹⁰ is -H.

2. A compound according to claim 1,

wherein R ⁵ and R ^{10 are} each independently selected from -H, methyl, ie / f.-butyl, wherein R ⁵ and R ^{10 are} unequal when R ⁵ or R ¹⁰ is -H.

3. A compound according to claim 1 or 2, characterized in that it is selected from

or mixtures containing at least two of the structures of (Ia), (Ib) and (Ic), - wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ^{9 are} each independently selected from: -H, - (Ci-Ci ₂ ) -alkyl, -0- (Ci -Ci ₂ ) -alkyl, - (C ₆ -C 20) -aryl, -O- (C ₆ -C 20) -aryl, -halo, -OC = O- (Ci-Ci ₂ ) -alkyl, -N [( Ci-Ci ₂₎ -alkyl] _2, -S-alkyl, -S-aryl, -COO- (Ci-Ci ₂₎ -alkyl, - CONH- (Ci-Ci ₂₎ -alkyl, -CO- (Ci Ci ₂ ) -alkyl, -CO- (C ₆ -C 20) -aryl, -COOH, -SO ₃ H, -CN; wherein each of the alkyl and aryl groups is independently unsubstituted or substituted, optionally substituted - (C 1 -C 12) -alkyl groups and optionally substituted - (C 6 -C 20) -aryl groups having at least one substituent and the at least one substituent each being independently selected from - (C 3 -C 12) -cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and

wherein R ⁵ and R ^{10 are the} same and are selected from:

- (Ci-Ci ₂₎ -alkyl, - _(C6-C2o) -aryl, -C = 0- _(Ci-Ci2) alkyl, -methylthioethyl, -trimethylsilyl, -triethylsilyl, -triisopropylsilyl, -fe / f.-butyldimethylsilyl, -fe / f-butyldiphenylsilyl, -acetyl, -pivaloyl, -benzoic acid ester, -3- (2-nitrophenyl) acetyl, -oxoacyl, -trifluoromethanesulfonyl wherein said alkyl and aryl groups are each independently independently substituted or substituted in which optionally substituted - (C 1 -C 12) -alkyl groups and optionally substituted - (C 6 -C 20) -aryl groups have at least one substituent and the at least one substituent is in each case independently selected from - (C 3 -C 12) -cycloalkyl,

 - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl.

A compound according to any one of claims 1 to 3, wherein

a) in structure (Ia) R ⁵ is R ¹⁰ and is selected from methyl, Fe / F-butyl, b) in structure (Ib) R ^{5 is} selected from methyl, ie f.-butyl,

c) in structure (Ic) R ^{10 is} selected from methyl, ie f.-butyl.

A compound according to any one of claims 1 to 4,

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ^{9 are} each independently selected from:

-H, - (Ci-Ci ₂ ) -alkyl, -0- (Ci-Ci ₂ ) -alkyl, - (C ₆ -C ₂ o) -aryl and -0- (C ₆ -C ₂ o) -aryl ,

6. A compound according to any one of claims 1 to 5,

wherein R ¹ , R ³ , R ⁶ , R ^{8 are} each independently selected from:

 -H, - (Ci-Ci2) -alkyl, wherein said alkyl groups are unsubstituted or substituted.

7. A compound according to any one of claims 1 to 6,

wherein R ¹ , R ³ , R ⁶ , R ^{8 are} each methyl or ie / f-butyl and R ² , R ⁴ , R ⁷ , R ⁹ are each -H. 8. A process for the preparation of a selenodiarylene of the general structure (Ia), comprising the process steps

 (i) Reaction of a Selenodihenol of the General Structure (II)

with YR ⁵ (IIIa) and / or YR ¹⁰ (IIIb) to give a compound of structure (Ia), with Y as a leaving group, and

- R ⁵ and R ¹⁰ in (IIIa) and (IIIb) are each independently selected from: - (Ci-Ci ₂₎ -alkyl, - _(C6-C2o) -aryl, -C = 0- (Ci- Ci ₂ ) -alkyl, -methylthioethyl, -trimethylsilyl, -triethylsilyl, -triisopropylsilyl, -ie / f.-butyldimethylsilyl, -ie / f.-butyldiphenylsilyl, -acetyl, -pivaloyl, -benzoic acid, -3- (2-nitrophenyl ) acetyl, oxoacyl, trifluoromethanesulfonyl, wherein each independently the alkyl and aryl groups are unsubstituted or substituted, wherein optionally substituted - (Ci-Ci2) alkyl groups and optionally substituted - (C6-C2o) aryl groups have at least one substituent and the at least one substituent is in each case independently selected from - (C 3 -C 12) -cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl,

- wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ in (II) and (la) are each independently selected from: -H, - (Ci-Ci ₂ ) -Alkyl, -O- (Ci-Ci ₂ ) -alkyl, - (C ₆ -C 2o) -aryl, -O- (C ₆ -C ₂₀ ) -aryl, -halo, -OC = 0- (Ci-Ci ₂₎ alkyl, -N _[(Ci-Ci2) alkyl] _2, -S-alkyl, -S-aryl, -COO- (Ci Ci ₂₎ -alkyl,

-CONH- (Ci-Ci ₂ ) -alkyl, -CO- (Ci-Ci ₂ ) -alkyl, -CO- (C ₆ -C ₂ o) -aryl, -COOH, -S0 ₃ H, -CN, wherein the alkyl and aryl groups are each independently unsubstituted or substituted, optionally substituted - (Ci-Ci ₂₎ -alkyl, and optionally substituted - (o -C 6 C ₂₎ aryl groups have at least a substituent, and at least one substituent is independently selected from - (C3-Ci ₂₎ cycloalkyl, - (C3-Ci ₂₎ -heterocycloalkyl, - _(C6-C2o) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl,

wherein R ⁵ and R ¹⁰ in (Ia) are each independently selected from:

-H, - (Ci-Ci ₂₎ -alkyl, - (C ₆ -C ₂₀₎ -aryl, -C = 0- _(Ci-Ci2) alkyl,

-methylthioethyl, -trimethylsilyl, -triethylsilyl, -triisopropylsilyl, -ie / f -butyldimethylsilyl, -ie / f -butyldiphenylsilyl, -acetyl, -pivaloyl, -benzoic acid, -3 (2-nitrophenyl) acetyl, -oxoacyl, - trifluoromethanesulfonyl, wherein the alkyl and aryl groups are unsubstituted or substituted, wherein optionally substituted - (Ci-Ci ₂ ) alkyl groups and optionally substituted - (C6-C ₂ o) aryl groups have at least one substituent and the at least one substituent each independently selected is from - (C ₃ -C 12) -cycloalkyl,

- (C3-Ci ₂₎ -heterocycloalkyl, - _(C6-C2o) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl,

- wherein R ⁵ and R ¹⁰ in (Ia) are unequal when R ⁵ or R ¹⁰ is -H.

9. The method according to claim 8,

wherein YR ⁵ (purple) and / or YR ¹⁰ (IIIb) are the same and

 Y is halogen selected from chlorine, bromine and iodine, and

R ⁵ and R ^{10 are} identical and are selected from - (C 1 -C 12) -alkyl,

and - (C ₆ -C ₂ o) -aryl.

10. The method according to claim 8 or 9,

 the reaction being carried out by reacting the selenodiphenol of general structure (II) in the presence of a strong base selected from metal hydrides, lithium organyls and pyridine bases

with YR ⁵ (purple) and YR ¹⁰ (IIIb), wherein YR ⁵ (purple) and YR ¹⁰ (IIIb) are the same and Y is halogen selected from chlorine, bromine and iodine, and R ⁵ and R ^{10 are} selected from - (Ci-Ci ₂ ) -alkyl, - (C ₆ -C 2o) -aryl. 1 1. A method according to any one of claims 8 to 10, wherein the selenodiaryl is selected from

 (I)

or mixtures containing at least two of the structures of (Ia), (Ib) and (Ic),

- wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ^{9 are} each independently selected from: -H, - (Ci-Ci ₂ ) -alkyl, -0- (Ci -Ci ₂ ) -alkyl, - (C ₆ -C 2o) -aryl, -O- (C ₆ -C 2o) -aryl, - halogen,

-OC = 0- _(Ci-Ci2) alkyl, -N _[(Ci-Ci2) alkyl] _2, -S-alkyl, -S-aryl, -COO- (Ci-Ci ₂₎ -alkyl, -CONH- (Ci-Ci ₂₎ -alkyl, -CO- (Ci-Ci ₂₎ -alkyl, CO- _(C6-C2o) aryl, -COOH, -S0 ₃ H, -CN; wherein the alkyl and aryl groups are each independently unsubstituted or substituted, with optionally substituted - (Ci-Ci2) alkyl groups and optionally substituted

(C 6 -C 20) -aryl groups have at least one substituent and the at least one substituent in each case is independently selected from - (C 3 -C 12) -cycloalkyl,

- (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and

wherein R ⁵ and R ^{10 are} identical and are selected from: (C 1 -C 12) -alkyl,

- _(C6-C2o) -aryl, -C = 0- _(Ci-Ci2) alkyl, -methylthioethyl, -trimethylsilyl, -triethylsilyl, -triisopropylsilyl, -ie / f.-butyldimethylsilyl, -ie / f. -butyldiphenylsilyl, -acetyl, -pivaloyl, -benzoic acid, -3 (2-nitrophenyl) -acetyl, -oxoacyl-trifluoromethanesulfonyl wherein the alkyl and aryl groups are each independently independently unsubstituted or substituted, with optionally substituted - (Ci-Ci2) alkyl groups and optionally substituted - (C 6 -C 20) -aryl groups have at least one substituent and the at least one substituent is in each case independently selected from - (C 3 -C 12) -cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) - Aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl.

12. Complex comprising

 at least one compound of the general structure (Ia), (Ib), (Ic) of claims 1 to 7 and

 at least one metal atom selected from Rh, Ru, Co, Ir.

13. Use of a compound according to any one of claims 1 to 7 as a ligand in a complex comprising at least one metal atom.

14. Use of a compound according to any one of claims 1 to 7 for the catalysis of a hydroformylation reaction or as an intermediate for the preparation of ligands.

15. Method comprising the method steps

 (i) presentation of at least one olefin,

 (ii) adding a complex according to claim 12,

 or a compound according to any one of claims 1 to 7 and a substance which has a metal atom selected from Rh, Ru, Co, Ir,

 (iii) supplying H and CO,

 (iv) heating the reaction mixture,

 wherein the olefin is reacted to an aldehyde.