Diphosphoramidite ligands for isoselective hydroformylation reactions

Abstract

Disclosed is a catalyst composition comprising: (a) a transition metal; and (b) a diphosphoramidite ligand having the structure of formulas (I), (II), or (III): The catalyst composition is particularly useful for the hydroformylation of olefins to form aldehydes.

Description

DIPHOSPHORAMIDITE LIGANDS FOR ISOSELECTIVEHYDROFORMYLATION REACTIONSCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Patent Application No.63 / 683,072 filed on August 14, 2024; the entire content of which is hereby incorporatedby reference.FIELD OF TECHNOLOGY

[0002] The invention generally relates to catalyst compositions, catalyst solutions, andprocesses for preparing aldehydes using the catalyst solutions.BACKGROUND

[0003] The hydroformylation reaction, also known as the oxo reaction, is usedextensively in commercial processes for the preparation of aldehydes by reacting onemole of an olefin with one mole each of hydrogen and carbon monoxide. The mostextensive use of the reaction is in the preparation of normal- and iso-butyraldehyde frompropylene. The ratio of the amount of the normal-aldehyde product to the amount of theiso-aldehyde product is typically referred to as the normal-to-iso (N:I) or the normal-to-branched (N:B) ratio.

[0004] In the case of propylene, both products (the normal- and the iso-butyraldehydes) are key building blocks for the synthesis of many chemicalintermediates. For example, these aldehydes may be used to make solvents (such asalcohols, carboxylic acids, and esters), plasticizers, glycols, essential amino acids,flavorings, fragrances, polymers, insecticides, hydraulic fluids, and lubricants.

[0005] The hydroformylation of higher a-olefins (such as 1-hexene, 1-octene, and 1-tetradecene) yield aldehyde products that are useful feedstocks for the preparation ofdetergent alcohols and plasticizer alcohols.

[0006] A few rhodium-based catalyst systems are employed industrially. However, inpropylene hydroformylation, these systems provide higher normal-butyraldehydeselectivity. Iso-selectivity remains challenging. There is no known industrial processthat provides greater than 50% yield of iso-butyraldehyde from propylenehydroformylation.

[0007] Recently, ligand systems capable of producing 64.7% of iso-butyraldehyde at90°C have been disclosed (see, e.g., US 10,144,751; US 10,183,961; US 10,351,583;and Angew Chem. Int. Ed. 2019, 58, 2120). This is a significant advance.Unfortunately, the new ligand systems show thermal degradation at highertemperatures.

[0008] Despite the substantial progress that has been made in this area, there stillexists a need for more thermally stable and more iso-selective hydroformylation catalystsystems.

[0009] The present invention addresses this need as well as others, which willbecome apparent from the following description and the appended claims.SUMMARY

[0010] The invention is as set forth in the appended claims.

[0011] Briefly, in one aspect, the present invention provides a catalyst compositioncomprising:(a) a transition metal; and(b)a ligand having the structure of formulas (I), (II), or (III):R4R3R4R3R1R5R5O-P-NPNR5R5R2R4R3R3R4(1)R4R3R7R6R8RR1R5R5N-2-0N-P-O-R9R2R6R8R4R3R7(II)R7R7R8-R6R6-R8R1R9P-NN-P-O-R9R2R8-R6R6-R8R7R7(III)whereinR1 and R2 are each independently selected from H, and alkyl and cycloalkylgroups containing from 1 to 15 carbon atoms; andR3, R4, R5, R6, R7, R8, and R9 are each independently selected from H, F, CI, Br,and alkyl, cycloalkyl, aryl, alkoxy, trialkylsilyl, triarylsilyl, aryldialkylsilyl, anddiarylalkylsilyl groups containing from 1 to 20 carbon atoms, wherein the silicon atom ofthe alkylsilyl or triarylsilyl is directly bonded to the position of substitution.

[0012] In a second aspect, the invention provides a catalyst solution, which comprisesthe catalyst composition according to the invention and a solvent.

[0013] In a third aspect, the invention provides a process for preparing an aldehyde.The process comprises the step of contacting an olefin with hydrogen and carbonmonoxide in the catalyst solution according to the invention at conditions effective toform the aldehyde.

[0014] A particularly preferred transition metal for use in the catalyst composition ofthe invention is rhodium.

[0015] In a fourth aspect, the invention provides for a compound having the structureof formula (II):R4-R5R5R4R3R1-N-O-P-1R3NR2(II)R6-P-O-R6R7-R8-R9R7-R8whereinR1 and R2 are each independently selected from H, and alkyl and cycloalkylgroups containing from 1 to 15 carbon atoms; andR3, R4, R5, R6, R7, R8, and R9 are each independently selected from H, F, CI, Br,and alkyl, cycloalkyl, aryl, alkoxy, trialkylsilyl, triarylsilyl, aryldialkylsilyl, anddiarylalkylsilyl groups containing from 1 to 20 carbon atoms, wherein the silicon atom ofthe alkylsilyl or triarylsilyl is directly bonded to the position of substitution.DETAILED DESCRIPTION

[0016] Surprisingly, a highly iso-selective and thermally stable hydroformylationcatalyst has been discovered.Catalyst Composition

[0017] Thus, in a first aspect, the present invention provides a catalyst compositioncomprising (a) a transition metal and (b) a ligand having the structure of formulas (I),(II), or (III):R4R5R5R3R1O-P-NR3R4N-P-OR5R5R2R3R4R4R3(1)R7R4R3R6R8R1R5R5-O-P-O-P-NN-P-O--R9R2R6R8R4R3R7(II)R7R7R8-R6R6R8R1RgCP-NN-P-O--R9R2R8-R6R6-R8R7R7(III)whereinR1 and R2 are each independently selected from H, and alkyl and cycloalkylgroups containing from 1 to 15 carbon atoms; andR3, R4, R5, R6, R7, R8, and R9 are each independently selected from H, F, CI, Br,and alkyl, aryl, alkoxy, trialkylsilyl, triarylsilyl, aryldialkylsilyl, diarylalkylsilyl, andcycloalkyl groups containing from 1 to 20 carbon atoms, wherein the silicon atom of thealkylsilyl or triarylsilyl is directly bonded to the position of substitution.

[0018] The alkyl groups represented by R₁ and R2 may be the same or different,separate or combined, and contain from 1 to 15 carbon atoms. In variousembodiments, the alkyl groups may contain from 1 to 10 carbon atoms, from 1 to 8carbon atoms, from 1 to 6 carbon atoms, or from 1 to 4 carbon atoms.

[0019] Examples of the alkyl groups that R₁ and R2 can individually represent includemethyl, ethyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decyl, dodecyl, octadecyl, andvarious isomers thereof.

[0020] In various embodiments, R₁ and R2 are each methyl or linear alkyl containingup to 15 carbon atoms.

[0021] In various embodiments, R₁ and R2 are each methyl.

[0022] The cycloalkyl groups represented by R1 and R2 may be the same or different,and contain from 3 to 15 carbon atoms. In various embodiments, the cycloalkyl groupsmay contain from 3 to 12 carbon atoms, from 3 to 10 carbon atoms, from 3 to 8 carbonatoms, from 3 to 7 carbon atoms, from 3 to 6 carbon atoms, or from 3 to 5 carbonatoms.

[0023] Examples of the cycloalkyl groups that R₁ and R2 can individually representinclude cyclopentyl, cyclohexyl, and cycloheptyl.

[0024] The alkyl groups represented by R3, R4, R5, R6, R7, R8, and R9 may be thesame or different, separate or combined, and contain from 1 to 20 carbon atoms. Invarious embodiments, the alkyl groups may contain from 1 to 15 carbon atoms, from 1to 10 carbon atoms, from 1 to 8 carbon atoms, from 1 to 6 carbon atoms, or from 1 to 4carbon atoms.

[0025] Examples of the alkyl groups that R3, R4, R5, R6, R7, R8, and R9 can individuallyrepresent include methyl, ethyl, butyl, pentyl, hexyl, 2-ethylhexyl, octyl, decyl, dodecyl,octadecyl, and various isomers thereof.

[0026] The cycloalkyl groups represented by R3, R4, R5, R6, R7, R8, and R9 may be thesame or different, and contain from 3 to 20 carbon atoms. In various embodiments, thecycloalkyl groups may contain from 3 to 18 carbon atoms, from 3 to 15 carbon atoms,from 3 to 12 carbon atoms, from 3 to 10 carbon atoms, from 3 to 8 carbon atoms, from 3to 7 carbon atoms, from 3 to 6 carbon atoms, or from 3 to 5 carbon atoms.

[0027] Examples of the cycloalkyl groups that R3, R4, R5, R6, R7, R8, and R9 canindividually represent include cyclopentyl, cyclohexyl, and cycloheptyl.

[0028] Examples of the aryl groups that R3, R4, R5, R6, R7, R8, and R9 can individuallyrepresent include phenyl, naphthyl, anthracenyl, and substituted derivatives thereof.

[0029] Examples of the alkoxy groups that R3, R4, R5, R6, R7, R8, and R9 canindividually represent include methoxy, ethoxy, butoxy, pentoxy, hexoxy, 2-ethylhexoxy,octoxy, decoxy, dodecoxy, and octadecoxy.

[0030] Examples of the trialkylsilyl groups that R3, R4, R5, R6, R7, R8, and R9 canindividually represent include trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, andisomers thereof.

[0031] Examples of the triarylsilyl groups that R3, R4, R5, R6, R7, R8, and R9 canindividually represent include triphenylsilyl, tri(methoxyphenyl)silyl, tri(ethoxyphenly)silyl,and isomers thereof.

[0032] Examples of the aryldialkylsilyl groups that R3, R4, R5, R6, R7, R8, and R9 canindividually represent include dimethylphenylsilyl, diethylphenylsilyl, dipropylphenylsilyl,dibutylphenylsilyl, and isomers thereof.

[0033] Examples of the diarylalkylsilyl groups that R3, R4, R5, R6, R7, R8, and R9 canindividually represent include diphenylmethylsilyl, diphenylethylsilyl, diphenylpropylsilyl,and isomers thereof.

[0034] In various embodiments, R3, R4, R5, R6, R7, R8, and R9 are each independentlyselected from H, F, Cl, Br, trimethylsilyl, and alkyl, alkoxy, and cycloalkyl groupscontaining from 1 to 20 carbon atoms, wherein the silicon atom of the trimethylsilyl isdirectly bonded to the position of substitution.

[0035] In various embodiments, R3, R4, R5, R6, R7, R8, and R9 are each independentlyselected from F, Cl, Br, methyl, tert-butyl, (2-phenylpropan-2-yl), adamantyl,trimethylsilyl, and methoxy.

[0036] In various embodiments, R3 is tert-butyl or (2-phenylpropan-2-yl).

[0037] In various embodiments, R4 is methoxy or (2-phenylpropan-2-yl).

[0038] In various embodiments, R5 is hydrogen.

[0039] In various embodiments, R6 and R7 are each methyl, tert-butyl, or (2-phenylpropan-2-yl).

[0040] In various embodiments, R8 is hydrogen.

[0041] In various embodiments, R9 is hydrogen, tert-butyl, or cyclohexyl.

[0042] In various embodiments, the catalyst composition comprises a ligand havingthe structure of formula (I).

[0043] In various embodiments, the catalyst composition comprises a ligand havingthe structure of formula (II).

[0044] In various embodiments, the catalyst composition comprises a ligand havingthe structure of formula (III).

[0045] In various embodiments, the catalyst composition comprises two or moreligands having the structure of formulas (I), (II), or (III).

[0046] In various embodiments, the ligand has the structure of formulas (A), (B), (C),(D), (E), or (F):MeOtButBuOMePhPhtBuOMeMeP-NN-PMeMeP-NNMeMeOtButBuOMetBuOMePh(A)Ph(B)PhPhMeO.tBuMeO.tBuMeMeNNPPtBuPPNMeNMeMeOtBuMeOtBuPhPh(C)(D)tButBuMeOtBuMeO.tButButBuMeMePN-PO-d.tBuPN-PNNMeMeMeOtButBuMeOtButButButBu(E)(F)

[0047] Ligand (A) may be referred to as 1,2-bis(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethylhydrazine.

[0048] Ligand (B) may be referred to as 1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethyl-2-(2,4,8,10-tetrakis(2-phenylpropan-2-yl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)hydrazine.

[0049] Ligand (C) may be referred to as 1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethyl-2-(2,4,8,10-tetramethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-yl)hydrazine.

[0050] Ligand (D) may be referred to as 1-(12-(tert-butyl)-2,4,8,10-tetrakis(2-phenylpropan-2-yl)-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-yl)-2-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethylhydrazine.

[0051] Ligand (E) may be referred to as 1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethyl-2-(2,4,8,10,12-penta-tert-butyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-yl)hydrazine.

[0052] Ligand (F) may be referred to as 1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethyl-2-(2,4,8,10-tetra-tbutyl-12-cyclohexyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-yl)hydrazine.

[0053] In various embodiments, the catalyst composition comprises Ligand (A),Ligand (B), Ligand (C), Ligand (D), Ligand (E), Ligand (F), or combinations thereof.

[0054] The ligands may be prepared using the procedures described in the Examplessection hereinbelow.

[0055] The catalyst composition of the invention further includes a transition metal.

[0056] Among the transition metals, Group VIIIB metals (such as Fe, Co, Ni, Ru, Rh,Pd, Pt, etc.) are particularly useful. A preferred transition metal is rhodium.

[0057] The transition metal may be provided in the form of various metal compounds,such as carboxylate salts of the transition metal. For example, rhodium compounds thatmay be used as a source of rhodium for the active catalyst include rhodium (II) orrhodium (III) salts of carboxylic acids. Examples of such salts include di-rhodiumtetraacetate dihydrate, rhodium(II) acetate, rhodium(II) isobutyrate, rhodium(II) 2-ethylhexanoate, rhodium(II) benzoate, and rhodium(II) octanoate. Also, rhodiumcarbonyl species, such as Rh4(CO)12, Rh6(CO)16, and rhodium(I) acetylacetonatedicarbonyl, may be suitable rhodium feeds. Additionally, rhodium organophosphinecomplexes, such as tris(triphenylphosphine) rhodium carbonyl hydride, may be usedwhen the phosphine moieties of the complex feed are easily displaced by thediphosphoramidite ligands of the present invention. Less desirable rhodium sources arerhodium salts of strong mineral acids, such as chlorides, bromides, nitrates, sulfates,phosphates, and the like.

[0058] In various embodiments, the catalyst composition may be formed in situ from atransition metal compound (such as [Rh(acac)(CO)2]) and a ligand. It is appreciated bythose skilled in the art that a wide variety of Rh species may form the same activecatalyst when contacted with ligand, hydrogen, and carbon monoxide; thus, there is nolimitation on the choice of the Rh pre-catalyst.

[0059] The molar ratio of the diphosphoramidite ligand to the transition metal can varyover a wide range, e.g., from 1:1 to 300:1. For rhodium-containing catalyst systems, themolar ratio of the diphosphoramidite ligand to rhodium can range from 1:1 to 200:1 orfrom 1:1 to 75:1.

[0060] In various embodiments, the molar ratio of the ligand to the transition metal isat least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, atleast 8:1, at least 9:1, or at least 10:1.

[0061] In various embodiments, the catalyst composition of the invention provides aniso-selectivity of at least 50%, at least 55%, or at least 60% in a hydroformylationreaction at a temperature of 80°C to 110°C.

[0062] In various embodiments, the catalyst composition of the invention is thermallystable. For example, the catalyst composition can be effective for converting an olefinto an aldehyde in the presence of hydrogen and carbon monoxide for at least 5 hours at50°C, for at least 1 hour at 80°C, for at least 1 hour at 95°C, or for at least 1 hour at110°C.Catalyst Solution

[0063] In a second aspect, the invention provides a catalyst solution. The catalystsolution comprises the catalyst composition according to the invention and a solvent.

[0064] The catalyst compositions and solutions of the invention may be used in a widevariety of transition metal-catalyzed processes, such as hydroformylation. The catalystcompositions / solutions comprising rhodium as the transition metal are especially usefulfor the hydroformylation of olefins to produce aldehydes.

[0065] The solvent in the catalyst solution may be selected from a wide variety ofcompounds (or mixture of compounds). The main criteria for the solvent are that (1) it isa liquid under reaction conditions, (2) it can solubilize the catalyst and the reactantsunder reaction conditions, and (3) it is not a catalyst poison. General examples ofsolvents include alkanes, cycloalkanes, alkenes, cycloalkenes, carbocyclic aromaticcompounds, alcohols, esters, ketones, acetals, ethers, and water. Specific examples ofsolvents include alkane and cycloalkanes, such as dodecane, decalin, n-octane, iso-octane, cyclohexane, cyclooctane, cyclododecane, and methylcyclohexane; aromatichydrocarbons, such as benzene, toluene, xylene isomers, tetralin, and cumene; alkyl-substituted aromatic compounds, such as the isomers of diisopropylbenzene,triisopropylbenzene, and tert-butylbenzene; alkenes and cycloalkenes, such as 1,7-octadiene, dicyclopentadiene, 1,5-cyclooctadiene, octene-1, octene-2, 4-vinylcyclohexene, cyclohexene, 1,5,9-cyclododecatriene, and 1-pentene; crudehydrocarbon mixtures, such as naphtha, mineral oils, and kerosene; high-boiling esters,such as 2,2,4-trimethyl-1,3-pentanediol diisobutyrate; ethers, such as di-n-butyl ether;and ester-alcohols, such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.

[0066] The aldehyde product of a hydroformylation reaction may also be used as thesolvent. In various embodiments, the solvent includes the higher boiling by-productsthat are formed during the hydroformylation reaction, or during subsequent separationor purification steps. Suitable solvents for the production of volatile aldehydes (e.g.,propionaldehyde and butyraldehydes) include those that are sufficiently high boiling toremain, for the most part, in a gas-sparged reactor. Suitable solvents for the productionof less volatile or non-volatile aldehydes include 1-methyl-2-pyrrolidinone; dimethyl-formamide; perfluorinated solvents, such as perfluoro-kerosene; sulfolane; water; andhigh-boiling hydrocarbon liquids. Mixtures of solvents may also be used. Non-hydroxylic compounds, in general, and hydrocarbons and esters, in particular, may alsoadvantageously be used as the hydroformylation solvent, since their use can minimizedecomposition of the ligand.

[0067] The concentration of the transition metal (e.g., rhodium) and ligand in thesolvent or reaction mixture is not critical. As mentioned above, a molar ratio of ligand totransition metal of at least 1:1 in the reaction mixture is typically sufficient (e.g., from 1:1to 300:1, from 1:1 to 200:1, from 1:1 to 100:1, or from 1:1 to 10:1).

[0068] The absolute concentration of transition metal in the reaction mixture orsolution may vary from 1 mg / L up to 5000 mg / L or more. In various embodiments, theconcentration of transition metal in the reaction solution is in the range of 20 to 300mg / L. Concentrations lower than these ranges may not yield acceptable reaction rateswith most olefin reactants and / or would require temperatures that are so high as to bedetrimental to catalyst stability. Higher rhodium concentrations are less attractivebecause of the high cost of rhodium.

[0069] No special or unusual techniques are required to prepare the catalystcompositions or solutions of the present invention. Nonetheless, to obtain a catalystwith high activity, the transition metal and the ligand may be mixed in an inertatmosphere, e.g., nitrogen, argon, and the like. The desired quantities of a suitabletransition metal compound and ligand may be charged to the reactor in a suitablesolvent and thoroughly mixed. Typical mixing conditions include 10 to 150°C and 1 to150 bars absolute for 1 minute to 12 hours.

[0070] The catalyst compositions or solutions may be activated before use inhydroformylation. The activation can be accomplished by contacting the catalystcompositions or solutions with CO and hydrogen before introduction of the olefin. Thecontacting step may be carried out at hydroformylation reaction conditions or close to it,for, e.g., 1 minute to 12 hours.Hydroformylation Process

[0071] In a third aspect, the invention provides a process for preparing an aldehyde.The process comprises the step of contacting an olefin with hydrogen and carbonmonoxide in the catalyst solution according to the invention at conditions effective toform the aldehyde.

[0072] The process may be practiced with a wide range of olefin feeds, such asaliphatic (including ethylenically-unsaturated, low molecular weight polymers), alicyclic,aromatic, and heterocyclic mono-, di-, and tri-olefins containing 2 to 40 carbon atoms.

[0073] Examples of aliphatic, mono-olefins include straight- and branched-chain,unsubstituted and substituted, a-olefins containing 2 to 20 carbon atoms. Examples ofthe groups that may be present on the substituted a-olefins include hydroxyl; alkoxyincluding ethers and acetals; alkanoyloxy, such as acetoxy; amino including substitutedamino; carboxyl; alkoxycarbonyl; carboxamido; keto; cyano; and the like.

[0074] Specific examples of a-olefins include ethylene, propylene, 1-butene, 1-octene,vinyl acetate, vinyl isobutyl ether, allyl alcohol, and 3-acetoxy-1-propene.

[0075] Aliphatic, di-olefins may also be used in the inventive process, particularlythose containing up to 20 carbon atoms.

[0076] Cyclic olefins that may be used in the hydroformylation process includecycloalkenes (e.g., cyclohexene, 1,5-cyclooctadiene, and cyclodecatriene), vinyl-substituted cycloalkanes, heterocyclics, and aromatic compounds. Examples of suchcyclic olefins include 4-vinylcyclohexene, 1,4-cyclohexadiene, 4-cyclohexene-carboxylicacid, methyl 4-cyclohexene-carboxylic acid, 1,4-cyclooctadiene, and 1,5,9-cyclododecatriene.

[0077] In various embodiments, the olefin reactants include a-olefins with 2 to 10carbon atoms, especially propylene.

[0078] In various embodiments, the olefin comprises propylene, and the aldehydecomprises normal- and iso-butyaldehyde.

[0079] In various embodiments, the hydroformylation process has an iso-butyraldehyde selectivity of at least 50%, at least 55%, or at least 60%.

[0080] Mixtures of olefins can also be used in the practice of this invention. Themixtures may be of the same carbon number, such as mixtures of octene isomers, ormay represent refinery distillation cuts, which can contain a mixture of olefins with arange of carbon numbers.

[0081] The amount of olefin present in the reaction mixture is not critical. Forexample, relatively high-boiling olefins (such as 1-octene) may function both as theolefin reactant and the process solvent. In the hydroformylation of a gaseous olefinfeedstock (such as propylene), the olefin partial pressures in the reactor typically canrange from 0.07 to 35 bars absolute. In practice, the rate of reaction can be favored byhigher concentrations of olefin in the reactor. In the hydroformylation of propylene, forexample, the partial pressure of propylene can be at least 1.4 bars, e.g., from 1.4 to 10bars absolute. In the case of ethylene hydroformylation, the partial pressure of ethylenein the reactor can be at least 0.14 bars absolute.

[0082] The hydrogen to carbon monoxide molar ratio introduced into the reactor mayvary considerably, ranging from 10:1 to 1:10, and the sum of the absolute partialpressures of hydrogen and carbon monoxide may range from 0.3 to 36 bars absolute.The molar ratio of hydrogen to carbon monoxide can be varied widely within thesepartial pressure ranges.

[0083] In various embodiments, the partial pressures of hydrogen and carbonmonoxide in the reactor are in the range of 1.4 to 13.8 bars absolute (about 20 to 200psia) for each gas.

[0084] Synthesis gas (also known as syngas) may be a source of the hydrogen andcarbon monoxide. The molar ratio of hydrogen to carbon monoxide and the partialpressure of each in the syngas can be readily changed by adding either hydrogen orcarbon monoxide to the syngas stream.

[0085] The reaction conditions are not critical for the operation of the hydroformylationprocess. Conventional hydroformylation conditions can be used. The process may becarried out at temperatures in the range of 20 to 200°C, of 50 to 135°C, of 75 to 125°C,or of 80 to 110°C. Higher reaction temperatures can increase the rate of catalystdecomposition, while lower reaction temperatures may result in relatively slow reactionrates. The total reaction pressure may range from ambient or atmospheric to 70 barsabsolute (about 1000 psig), or from 8 to 40 bars absolute (about 100 to 600 psig).

[0086] Any of the known hydroformylation reactor designs or configurations may beused in carrying out the process of the present invention. In various embodiments, agas-sparged, vapor take-off reactor can be used. In this mode of operation, the catalystcomposition can be dissolved in a high-boiling organic solvent and may not leave thereaction zone with the aldehyde product, which is taken overhead by the unreactedgases. The overhead gases can then be chilled in a vapor / liquid separator to condensethe aldehyde product, and the gases can be recycled to the reactor. The liquid productcan be let down to atmospheric pressure for separation and purification by conventionaltechniques.

[0087] The process may also be practiced in a batchwise manner by contacting theolefin, hydrogen, and carbon monoxide with the catalyst composition or solution in anautoclave as illustrated in the working examples.

[0088] A reactor design where catalyst and feedstock are pumped into a reactor andallowed to overflow with product aldehyde (i.e., a liquid overflow reactor design) is alsosuitable. For example, high-boiling aldehyde products, such as nonyl aldehydes, maybe prepared in a continuous manner with the aldehyde product being removed from thereaction zone as a liquid in combination with the catalyst. The aldehyde product may beseparated from the catalyst by conventional means, such as by distillation or extraction,and the catalyst may be recycled back to the reactor. Water-soluble aldehyde productscan be separated from the catalyst by extraction techniques.

[0089] A trickle-bed reactor design also is suitable for this process. It will be apparentto those skilled in the art that other reactor schemes may be used with this invention.Compound

[0090] In a fourth aspect, the invention provides for a compound having the structureof formula (II):R4R5R5R4R3R1O-P-NR3R6N-P-O-R2(II)R6R7-R8-R9-R8R7whereinR1 and R2 are each independently selected from H, and alkyl and cycloalkylgroups containing from 1 to 15 carbon atoms; andR3, R4, R5, R6, R7, R8, and R9 are each independently selected from H, F, CI, Br,and alkyl, cycloalkyl, aryl, alkoxy, trialkylsilyl, triarylsilyl, aryldialkylsilyl, anddiarylalkylsilyl groups containing from 1 to 20 carbon atoms, wherein the silicon atom ofthe alkylsilyl or triarylsilyl is directly bonded to the position of substitution.

[0091] In various embodiments, R3, R4, R5, R6, R7, R8, and R9 are each independentlyselected from H, F, Cl, Br, trimethylsilyl, and alkyl, alkoxy, and cycloalkyl groupscontaining from 1 to 20 carbon atoms, wherein the silicon atom of the trimethylsilyl isdirectly bonded to the position of substitution.

[0092] In various embodiments, R3, R4, R5, R6, R7, R8, and R9 are each independentlyselected from F, Cl, Br, methyl, tert-butyl, (2-phenylpropan-2-yl), adamantyl,trimethylsilyl, and methoxy.

[0093] In various embodiments, R3 is tert-butyl or (2-phenylpropan-2-yl).

[0094] In various embodiments, R4 is methoxy or (2-phenylpropan-2-yl).

[0095] In various embodiments, R5 is hydrogen.

[0096] In various embodiments, R6 and R7 are each methyl, tert-butyl, or (2-phenylpropan-2-yl).

[0097] In various embodiments, R8 is hydrogen.

[0098] In various embodiments, R9 is hydrogen, tert-butyl, or cyclohexyl.

[0099] In various embodiments, the compound has the structure of formulas (C), (D),(E), or (F):MeO.tBuMeNPPNMeMeOtBu(C)PhPhMeO,tBuMePN-PtBuNMeMeOtBuPhPh(D)tButBuMeOtButBuMeNPPtBuNMeMeOtButBu*****MeOtButBuMeNPPNMeMeOtButButButBu(E)(F)

[0100] Ligand (C) may be referred to as 1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethyl-2-(2,4,8,10-tetramethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-yl)hydrazine.

[0101] Ligand (D) may be referred to as 1-(12-(tert-butyl)-2,4,8,10-tetrakis(2-phenylpropan-2-yl)-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-yl)-2-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethylhydrazine.

[0102] Ligand (E) may be referred to as 1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethyl-2-(2,4,8,10,12-penta-tert-butyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-yl)hydrazine.

[0103] Ligand (F) may be referred to as 1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethyl-2-(2,4,8,10-tetra-tert-butyl-12-cyclohexyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-yl)hydrazine.

[0104] The ligands may be prepared using the procedures described in the Examplessection hereinbelow.General Provisions

[0105] To remove any doubt, the present invention includes and expresslycontemplates and discloses any and all combinations of embodiments, features,characteristics, parameters, and / or ranges mentioned herein. That is, the subjectmatter of the present invention may be defined by any combination of embodiments,features, characteristics, parameters, and / or ranges mentioned herein.

[0106] It is contemplated that any ingredient, component, or step that is notspecifically named or identified as part of the present invention may be explicitlyexcluded.

[0107] Any process / method, apparatus, compound, composition, embodiment, orcomponent of the present invention may be modified by the transitional terms"comprising," "consisting essentially of," or "consisting of," or variations of those terms.

[0108] As used herein, the indefinite articles “a” and “an” mean one or more, unlessthe context clearly suggests otherwise. Similarly, the singular form of nouns includestheir plural form, and vice versa, unless the context clearly suggests otherwise.

[0109] As used herein, the term "and / or," when used in a list of two or more items,means that any one of the listed items can be employed by itself, or any combination oftwo or more of the listed items can be employed. For example, if a composition isdescribed as containing components A, B, and / or C, the composition can contain Aalone; B alone; C alone; A and B in combination; A and C in combination; B and C incombination; or A, B, and C in combination.

[0110] While attempts have been made to be precise, the numerical values andranges described herein should be considered to be approximations (even when notqualified by the term "about"). These values and ranges may vary from their statednumbers depending upon the desired properties sought to be obtained by the presentinvention as well as the variations resulting from the standard deviation found in themeasuring techniques. Moreover, the ranges described herein are intended andspecifically contemplated to include all sub-ranges and values within the stated ranges.For example, a range of 50 to 100 is intended to describe and include all values withinthe range including sub-ranges such as 60 to 90, 70 to 80, etc.

[0111] Any two numbers of the same property or parameter reported in the workingexamples may define a range. Those numbers may be rounded off to the nearestthousandth, hundredth, tenth, whole number, ten, hundred, or thousand to define therange.

[0112] The content of all documents cited herein, including patents as well as non-patent literature, is hereby incorporated by reference in their entirety. To the extent thatany incorporated subject matter contradicts or conflicts with any disclosure herein, thedisclosure herein shall take precedence over the incorporated content.

[0113] This invention can be further illustrated by the following examples, although itwill be understood that these examples are included merely for purposes of illustrationand are not intended to limit the scope of the invention.EXAMPLESGeneral Procedures

[0114] All reactions were performed under an inert atmosphere of nitrogen or argonusing standard Schlenk techniques, unless otherwise stated. All glassware used wereflame-dried. Dry and degassed solvents were obtained from a solvent still or SPSsolvent purification system.

[0115] Commercially purchased anhydrous solvents were degassed before use by thefreeze-pump-thaw method or purging with inert gas. Triethylamine was degassedbefore use. All chemicals, unless specified, were purchased commercially and used asreceived. CO / H2 (1:1) and propylene / CO / H2 (10 / 45 / 45%) were obtained pre-mixed fromBOC.Analytical Methods

[0116] Nuclear magnetic resonance (NMR) spectra were recorded on a BrukerAvance 300, 400, or 500 MHz instrument. Proton chemical shifts were referenced tointernal residual solvent protons. Carbon chemical shifts were referenced to the carbonsignal of the deuterated solvent. Signal multiplicities were given as s (singlet), d(doublet), t (triplet), q (quartet), m (multiplet), or a combination of the above, br (broad),vbr (very broad), ap (apparent). Where appropriate, coupling constants (J) were quotedin Hz and were reported to the nearest 0.1 Hz. All spectra were recorded at r.t. (unlessotherwise stated), and the solvent for a particular spectrum is given in parentheses.NMR of compounds containing phosphorus were recorded under an inert atmosphere indry and degassed solvent unless otherwise stated.

[0117] Gas chromatography was performed on an Agilent Technologies 7820Amachine.

[0118] Mass spectrometry was performed on a Micromass GCT spectrometer,Micromass LCT spectrometer, Waters ZQ4000, Thermofisher LTQ Orbitrap XL, orFinnigan MAT 900 XLT instruments.

[0119] Flash column chromatography was performed using Merck Geduran Si 60 (40-63 µm) silica gel.

[0120] Thin layer chromatographic (TLC) analyses were carried out usingPOLYGRAM SIL G / UV254 or POLYGRAM ALOX N / UV254 plastic plates. TLC plateswere visualized using a UV visualizer or stained using potassium permanganate dipfollowed by gentle heating.Example 1Preparation of Ligand (A): 1,2-bis(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethylhydrazine

[0121] The structural formula of Ligand (A) is shown below.MeO.tButBuOMeMeO-P-N-P-N-N-P-OMeMeOtButBuOMeLigand (A)

[0122] To a stirred solution of 1,2-bis(dichlorophosphaneyl)-1,2-dimethylhydrazine(0.166 g, 0.63 mmol) in THF (3 mL) at -78°C was added a solution of 3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'-diol (0.454 g, 1.27 mmol) in THF (5 mL) slowly viasyringe. This was followed by Et3N (0.386 mL, 2.77 mmol) addition also via syringe.The reaction mixture was then allowed to warm to -45°C while stirring for 1 h, then thesolution was taken out of the cold bath and stirred for another 90 minutes at roomtemperature. The reaction was filtered under an argon atmosphere and concentrated invacuo.

[0123] The resulting solid was purified under air by flash chromatography on silica gel(5:1 petrol (40-60°C):EtOAc), affording the desired product (0.386 g, 0.463 mmol, 74%)as a white solid.

[0124] The white solid product was analyzed by NMR spectroscopy and high-resolution mass spectroscopy (HRMS). The results are shown below.

[0125] 1H NMR (C6D6, 500 MHz) δ 7.20 (4H, br d, J = 2.6 Hz, ArCH), 6.74 (4H, br d, J= 2.6 Hz, ArCH), 3.36 (12H, s, 4 x OCH3), 2.76 (3H, s, 2 x NCH3), 1.62 (18H, s, 2 xC(CH3)3), 1.53 (18H, s, 2 x C(CH3)3).

[0126] 13C NMR (C6D6, 126 MHz) δ 155.75-155.69 (4 x ArC), 143.61 (2 x ArC),143.31 (2 x ArC), 142.74 (2 x ArC), 142.16 (2 x ArC), 134.06 (2 x ArC), 133.44 (2 xArC), 114.61 (4 x ArCH), 112.83 (4 x ArCH), 54.74 (4 x OCH3), 35.64 (2 x NCH3), 35.50(2 x C(CH3)3), 35.18 (2 x C(CH3)3), 30.76 (4 x C(CH3)3).

[0127] 31P{H} NMR (C6D6, 202 MHz) δ 144.0 (s).

[0128] HRMS (ES+) [MH]+ m / z: 833.4028 found; C46H63O8N2P2 requires 833.4054.Example 2Preparation of Ligand (B): 1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethyl-2-(2,4,8,10-tetrakis(2-phenylpropan-2-yl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)hydrazine

[0129] The structural formula of Ligand (B) is shown below.PhPhtBuOMeMe-NP-NMetBuPhPhLigand (B)OMe

[0130] To a stirred solution of 3,3',5,5'-tetrakis(2-phenylpropan-2-yl)-[1,1'-biphenyl]-2,2'-diol (0.405 g, 0.615 mmol) in THF (4 mL) at -78°C was added in one portion asolution of 1,2-bis(dichlorophosphaneyl)-1,2-dimethylhydrazine (0.161 g, 0.615 mmol) inTHF (3 mL). This was followed by Et3N (0.214 mL, 1.54 mmol) addition via syringe.The reaction mixture was then allowed to warm to -50°C while stirring for 1 h. Thesolution was taken out of the cold bath and stirred for a further 60 minutes at roomtemperature. The reaction mixture was cooled down again to -78°C and, using asyringe, a solution of the second diol 3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'-diol (0.220 g, 0.615 mmol) in THF (4 mL) was added in one portion, followed by Et3N(0.214 mL, 1.54 mmol). The reaction mixture was then allowed to warm up slowly for 1h and then stirred for 0.5 h at room temperature. The reaction was filtered under anargon atmosphere and concentrated in vacuo.

[0131] The resulting solid was purified under air by flash chromatography on silica gel(8:1 petrol (40-60°C):EtOAc), affording the desired product (0.417 g, 0.370 mmol, 60%)as a white solid.

[0132] The white solid product was analyzed by NMR spectroscopy and HRMS. Theresults are shown below.

[0133] 1H NMR (C6D6, 500 MHz) 8 7.41 (2H, br s, ArCH), 7.32 (2H, br d, J = 7.2 Hz,ArCH), 7.24-6.90 (22H, m, ArCH), 6.77 (2H, d, J = 3.0 Hz, ArCH), 3.37 (6H, s, 2 xOCH3), 2.59 (3H, s, NCH3), 2.49 (3H, s, NCH3), 2.00 (3H, s, CH3), 1.78 (3H, s, CH3),1.69 (3H, s, CH3), 1.63 (3H, s, CH3), 1.58-1.52 (30H, m, 4 x CH3, 2 x C(CH3)3).

[0134] 13C NMR (C6D6, 126 MHz) δ 155.70-143.36 (12 x ArC), 143.00 (ArC), 142.11(ArC), 140.83 (ArC), 140.07 (ArC), 133.99 (ArC), 133.65 (ArC), 132.53 (ArC), 131.72(ArC), 128.78-15.66 (24 x ArCH), 114.62 (2 x ArCH), 112.83 (2 x ArCH), 54.78 (2 xOCH3), 36.10 (d, J = 5.5 Hz, NCH3), 34.66 (d, J = 5.8 Hz, NCH3), 43.16 (CPH(CH3)2),42.79 (CPH(CH3)2), 42.67 (CPH(CH3)2), 42.58 (CPH(CH3)2), 35.54 (C(CH3)3), 35.18(C(CH3)3), 32.08-29.82 (4 x Ph(CH3)2, 2 x C(CH3)3).

[0135] 31P{1H} NMR (C6D6, 202 MHz) δ 146.2 (d, J = 32.0 Hz), 144.1 (d, J = 32.0 Hz).

[0136] HRMS (ES+) [MH]+ m / z: 1133.5692 found; C72H83O6N2P2 requires 1133.5721.Example 3Preparation of Ligand (C): 1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethyl-2-(2,4,8,10-tetramethyl-12H-dibenzo[d.g][1,3,2]dioxaphosphocin-6-yl)hydrazine

[0137] The structural formula of Ligand (C) is shown below.MeOtBuMeCP-NN-P-OMeMeOtBuLigand (C)

[0138] To a stirred solution of 3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'-diol(0.399 g, 1.110 mmol), in THF (4 mL) at -78°C was added in one portion a solution of1,2-bis(dichlorophosphaneyl)-1,2-dimethylhydrazine (0.292 g, 1.110 mmol) in THF (2mL). This was followed by Et3N (0.387 mL, 2.775 mmol) addition via syringe. Thereaction mixture was then allowed to warm to -50°C while stirring for 1 h. The solutionwas taken out of the cold bath and stirred for a further 60 minutes at room temperature.The reaction mixture was cooled down again to -78°C and, using a syringe, a solution ofthe second diol 6,6'-methylene bis(2,4-dimethylphenol) (0.378 g, 1.110 mmol) in THF (3mL) was added in one portion, followed by Et3N (0.387 mL, 2.775 mmol). The reactionmixture was then allowed to warm up slowly for 1 h and then stirred at r.t. for a further60 minutes. The reaction was filtered under an argon atmosphere and concentrated invacuo.

[0139] The resulting reaction crude was purified under air by flash chromatography onsilica gel (3:1 Hexane:Et2O), affording the desired product (0.436 g, 0.597 mmol,53.7%) as an off-white solid.

[0140] The off-white solid product was analyzed by NMR spectroscopy and HRMS.The results are shown below.

[0141] 1H NMR (C6D6, 400 MHz) δ 7.18 (2H, br s, ArCH), 6.90 (2H, br s, ArCH), 6.75(2H, d, J = 3.1 Hz, ArCH), 6.68 (2H, br s, ArCH), 4.60 (1H, dd, J = 12.4, 3.1 Hz, HCH),3.36 (6H, s, 2 x OCH3), 3.34-3.30 (4H, m, NCH3, HCH), 2.89 (3H, s, NCH3), 2.42 (3H, brs, CH3), 2.26 (3H, br s, CH3), 2.04 (6H, s, 2 x CH3), 1.56 (9H, s, C(CH3)3), 1.47 (9H, s,C(CH3)3).

[0142] 13C NMR (C6D6, 100 MHz) δ 155.72-133.37 (16 x ArC), 129.85 (2 x ArCH),128.00 (2 x ArCH), 114.57 (2 x ArCH), 112.88 (2 x ArCH), 54.75 (2 x OCH3), 35.49 (d, J= 5.4 Hz, NCH3), 35.30 (2 x C(CH3)3), 32.97 (NCH3), 30.70 (2 x C(CH3)3), 20.38 (2 xCH3), 17.63 (brs, CH3) 17.20 (br s, CH3).

[0143] 31P{H} NMR (C6D6, 162 MHz) & 145.9 (d, J = 20.3 Hz), 135.7 (d, J = 20.3 Hz).

[0144] HRMS (ES+) [MH]+ m / z: 731.370 found; C41H53O6N2P2 requires 731.3373.Example 4Preparation of Ligand (D): 1-(12-(tert-butyl)-2,4,8,10-tetrakis(2-phenylpropan-2-yl)-12H-dibenzo[dg][1,3,2]dioxaphosphocin-6-yl)-2-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethylhydrazine

[0145] The structural formula of Ligand (D) is shown below.PhPhMeO.tBuMeCP--N-N-PO-tBuMeMeOtBuPh-PhLigand (D)

[0146] Ligand (D) was prepared by following the method of Example 3, except with3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'-diol (0.428 g, 1.195 mmol), 1,2-bis(dichlorophosphaneyl)-1,2-dimethylhydrazine (0.313 g, 1.195 mmol), and 6,6'-(2,2-dimethylpropane-1,1-diyl)bis(2,4-bis(2-phenylpropan-2-yl)phenol) (0.871 g, 1.195mmol). The resulting reaction crude was purified under air by flash chromatography onsilica gel (10:1 Hexane:Et2O), affording the desired product (0.892 g, 0.741 mmol, 62.0%) as a white solid in 95% chemical purity (isomeric mixture in a 1:1.4 ratio by 31P{1H}NMR).

[0147] The white solid product was analyzed by NMR spectroscopy and HRMS. Theresults are shown below.

[0148] 1H NMR (C6D6, 400 MHz) δ 7.52 (2 x 2H, br s, ArCH), 7.34-6.96 (2 x 24H, brm, ArCH), 6.76 (2H, br d, J = 2.9 Hz, ArCH major isomer), 6.73 (2H, br d, J = 3.0 Hz,ArCH minor isomer), 5.10-4.95 (2 x 1H, m, CH), 3.36-3.34 (2 x 6H, m, 2 x OCH3), 2.56-2.52 (2 x 6H, m, 2 x NCH3), 1.90-1.07 (2 x 51H br m, 8 x CH3, 3 x C(CH3)3).

[0149] 13C NMR (CDCI3, 126 MHz) δ 155.02-130.91 (m, 2 x 20 x ArC), 128.92-112.15(m, 2 x 28 x ArCH), 55.62-55.60 (m, 2 x 2 x OCH3), 52.82-44.85 (m, 2 x CH), 42.89-35.33 (m, 2 x 3 x C(CH3)3, 2 x 4 x C(CH3)2Ph), 36.34-32.18 (m, 2 x 2 x NCH3), 31.01-28.64 (m, 2 x 3 x C(CH3)3, 2 x 4 x (CH3)2Ph).

[0150] 31P{1H} NMR (C6D6, 162 MHz) δ 144.85 (brs), 143.93 (d, J = 31.4 Hz), 139.90(br s), 131.08 (d, J = 31.4 Hz).

[0151] HRMS (ES+) [MH]+ m / z: 1203.6499 found; C77H93O6N2P2 requires 1203.6503.Example 5Preparation of Ligand (E): 1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethyl-2-(2,4,8,10,12-penta-tert-butyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-yl)hydrazine

[0152] The structural formula of Ligand (E) is shown below.tBuMeO.tButBuMeP-N-N-PN-P-OtBuMeMeOtButButBuLigand (E)

[0153] Ligand (E) was prepared by following the method of Example 3, except with3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'-diol (0.339 g, 0.946 mmol), 1,2-bis(dichlorophosphaneyl)-1,2-dimethylhydrazine (0.236 g, 0.901 mmol), and 6,6'-(2,2-dimethylpropane-1,1-diyl)bis(2,4-di-tert-butylphenol) (0.433 g, 0.901 mmol). Theresulting reaction crude (as an isomeric mixture in a 1:20 ratio) was purified by flashchromatography on silica gel (18:1 Hexane:Et2O), affording the major isomer (0.349 g,0.365 mmol, 40.5%) as a white solid.

[0154] The white solid product was analyzed by NMR spectroscopy and HRMS. Theresults are shown below.

[0155] 1H NMR (CDCI3, 400 MHz) δ 7.60 (2H, br s, ArCH), 7.14 (2H, br s, ArCH), 7.02(1H, br s, ArCH), 6.96 (1H, br s, ArCH), 6.72 (2H, br s, ArCH), 4.96 (1H, s, CH), 3.83(6H, s, 2 x OCH3), 3.34 (3H, s, NCH3), 2.74 (3H, s, NCH3), 1.56 (9H, br s, C(CH3)3),1.44 (9H, br s, C(CH3)3), 1.39 (9H, br s, C(CH3)3), 1.35 (9H, br s, C(CH3)3), 1.30 (18H, s,2 x C(CH3)3), 1.10 (9H, s, C(CH3)3).

[0156] 13C NMR (CDCI3, 100 MHz) δ 155.44-132.45 (16 x ArC), 122.36 (ArCH),122.14 (ArCH), 121.23 (2 x ArCH), 114.33 (2 x ArCH), 112.90 (ArCH), 112.50 (ArCH),55.56 (2 x OCH3), 45.07 (CH), 35.96 (2 x C(CH3)3), 35.39 (2 x C(CH3)3), 35.22(C(CH3)3), 35.07 (NCH3), 34.50 (2 x C(CH3)3), 32.79 (NCH3), 31.59 (C(CH3)3), 31.17(C(CH3)3), 31.12 (C(CH3)3), 30.88 (C(CH3)3), 30.83 (C(CH3)3), 30.72 (C(CH3)3), 30.70(C(CH3)3).

[0157] 31P{H} NMR (CDCI3, 161 MHz) δ 148.04 (s), 138.02 (s).

[0158] HRMS (ES+) [MH]+ m / z: 955.5854 found; C57H85O6N2P2 requires 955.5877.Example 6Preparation of Ligand (F): 1-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)-1,2-dimethyl-2-(2,4,8,10-tetra-tert-butyl-12-cyclohexyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-yl)hydrazine

[0159] The structural formula of Ligand (F) is shown below.tBuMeO.tButBuMeP-N-P-ONMeMeOtButButBuLigand (F)

[0160] Ligand (F) was prepared by following the method of Example 3, except with3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'-diol (0.333 g, 0.930 mmol), 1,2-bis(dichlorophosphaneyl)-1,2-dimethylhydrazine (0.232 g, 0.886 mmol) and 6,6'-(cyclohexylmethylene)bis(2,4-di-tert-butylphenol) (0.449 g, 0.886 mmol). The resultingreaction crude was purified under air by flash chromatography on silica gel (4:1Hexane:Et2O), affording the desired product (0.325 g, 0.331 mmol, 37.3%) as a whitesolid in 93% chemical purity (isomeric mixture in a 1:1.6 ratio as determined by 31P{1H}NMR).

[0161] The white solid product was analyzed by NMR spectroscopy and HRMS. Theresults are shown below.

[0162] 31P{1H} NMR (C6D6, 202 MHz) δ 147.71 (d, J = 6.4 Hz), 147.40 (s), 138.00 (d,J = 6.3 Hz), 137.01 (s).

[0163] HRMS (ES+) [MH]+ m / z: 981.6014 found; C59H87O6N2P2 requires 981.6034.Example 7Propylene Hydroformylation

[0164] Propylene hydroformylation reactions were conducted using [Rh(acac)(CO)2],as the Rh source, and Ligands (A) - (F).

[0165] The catalyst was preformed from [Rh(acac)(CO)2] (5.12 x 10-3 mmol) and eachligand (10.24 x 10-3 mmol (L:Rh 2:1)) by stirring under 20 bar of CO / H2 at the activationtemperature reported in Table 1 (Ligand (A) - 1.5 h; Ligand (B) - 1 h; Ligands (C) and(D) - 20 min; Ligand (E) - 50 min; and Ligand (F) - 60 min) in DOTP (90%) (18 mL + 2mL toluene).

[0166] The hydroformylation reactions of propene were performed in a Parr 4590Micro Reactor fitted with a gas entrainment stirrer, which contained holes to give bettergas dispersion throughout the reaction mixture. The vessel had a volume capacity of0.1 L, an overhead stirrer with gas entrainment head (set to 1000 r.p.m.), temperaturecontrols, a pressure gauge, and the ability to be connected to a gas cylinder.

[0167] Each ligand (10.24 µmol (Rh:L 1:2)) was added to a Schlenk tube, which wasthen purged with nitrogen (or argon). The internal standard 1-methylnaphthalene (0.1mL) was then added. The mixture was dissolved in a stock solution of [Rh(acac)(CO)2]in toluene (2 mg / mL, 0.65 mL, 5.12 µmol of [Rh(acac) (CO)2]), followed by the addition oftoluene (1.35 mL) and dioctyl terephthalate (DOTP) (18 mL). The solution wastransferred via syringe to the pressure vessel (which had been purged with CO / H2)through the injection port. A CO / H2 mixture (1:1) (20 bar) was added and the heatingsystem was set to the desired temperature while stirring. Once the desired temperaturewas reached, the reaction mixture was stirred for the required time to fully activate thecatalyst. Then, the pressure was slowly released and repressurized with a mixture ofpropene / CO / H2 in a 1:4.5:4.5 ratio. The reaction was then run for the time specified inTable 1. After this time, stirring was stopped and the reaction mixture was cooled byplacing the vessel in a basin of cold water. The pressure was released, and the crudesample was analysed immediately by GC (using toluene as eluent).

[0168] The GC method was run on a HP-5 Agilent column with a length of 30 m, adiameter of 0.250 mm, and a film thickness of 0.25 µm. The oven was initially held at25°C for 6 minutes, and then increased to 60°C at a rate of 10°C per minute. The rampwas then increased to 20°C per minute until the temperature reached 300°C. Theproducts could be identified with the following retention times: iso-butyraldehyde (1.02min); n-butyraldehyde (1.15 min); and 1-methylnaphthalene (13.50 min). The GC wascalibrated for propene hydroformylation using (1-methylnaphthalene) as an internalstandard. Both the linear (n-butyraldehyde) and branched (iso-butyraldehyde) productswere calibrated against the internal standard and against each other.

[0169] From the GC results, the amount of both products from each reaction wascalculated to give the iso-selectivity (which is the percentage of iso-butyraldehyde tototal butyraldehyde products), the n-to-iso ratio, and the productivity of the catalystbased on the turnover number (TON). ΤON refers to the relationship between the metalcatalyst loading and the amount of product formed using the equation: TON = (iso- + n-aldehyde) (mmol) / [Rh(acac)(CO)2] (mmol).

[0170] The results of the hydroformylation of propylene for each Ligand (A) - (F) arereported in Table 1.TABLE 1Effect of Ligand on Selectivity of Propylene HydroformylationRun; Ligand; L:Rh Ratio; Solvent; Total Pressure (bar); N2 Partial Pressure (bar); Catalyst Activation Temp. (°C); Reaction Temp. (°C); Reaction Time (hr); Catalyst TON; iso Selectivity (%); n:iso Ratio1; A; 2:1; DOTP (90%); 20; 0; 105; 80; 1; 711; 63.3; 0.58:12; A; 10:1; DOTP (90%); 20; 0; 105; 80; 1; 501; 63.8; 0.57:13; A; 2:1; DOTP (90%); 20; 10; 105; 80; 1; 447; 61.3; 0.63:14; A; 2:1; DOTP (90%); 20; 0; 105; 95; 1; 1085; 60.0; 0.67:15; A; 2:1; DOTP (90%); 20; 0; 105; 110; 0.5; 687; 57.7; 0.73:16; B; 2:1; DOTP (90%); 20; 0; 105; 80; 1; 543; 62.6; 0.60:17; B; 10:1; DOTP (90%); 20; 0; 105; 80; 1; 501; 63.2; 0.58:18; B; 2:1; DOTP (90%); 20; 10; 105; 80; 1; 274; 61.4; 0.63:19; B; 2:1; DOTP (90%); 20; 0; 105; 95; 1; 1034; 59.2; 0.69:110; B; 2:1; DOTP (90%); 20; 0; 105; 110; 0.5; 1042; 56.3; 0.77:111; C; 2:1; DOTP (90%); 20; 0; 105; 80; 1; 111; 52.9; 0.89:112; C; 10:1; DOTP (90%); 20; 0; 105; 80; 1; 147; 51.5; 0.94:113; C; 2:1; DOTP (90%); 20; 10; 105; 80; 1; 85; 54.0; 0.85:114; C; 2:1; DOTP (90%); 20; 0; 105; 95; 1; 374; 53.8; 0.86:115; C; 2:1; DOTP (90%); 20; 0; 105; 110; 1; 926; 55.4; 0.81:116; D; 2:1; DOTP (90%); 20; 0; 105; 80; 1; 580; 53.0; 0.88:117; D; 10:1; DOTP (90%); 20; 0; 105; 80; 1; 57; 49.7; 1.03:118; D; 2:1; DOTP (90%); 20; 10; 105; 80; 1; 305; 53.5; 0.87:119; D; 2:1; DOTP (90%); 20; 0; 105; 95; 1; 1081; 53.8; 0.86:120; D; 2:1; DOTP (90%); 20; 0; 105; 110; 1; 1046; 54.5; 0.83:121; E; 2:1; DOTP (90%); 20; 0; 80; 80; 1; 601; 52.8; 0.89:122; E; 10:1; DOTP (90%); 20; 0; 80; 80; 1; 1405; 49.4; 1.02:123; E; 2:1; DOTP (90%); 20; 10; 80; 80; 1; 76; 55.6; 0.80:124; E; 2:1; DOTP (90%); 20; 0; 80; 95; 1; 1190; 54.2; 0.85:125; E; 2:1; DOTP (90%); 20; 0; 80; 110; 1; 884; 54.5; 0.83:126; F; 2:1; DOTP (90%); 20; 0; 80; 80; 1; 14; 53.7; 0.86:127; F; 10:1; DOTP (90%); 20; 0; 80; 80; 1; 30; 47.7; 1.10:128; F; 2:1; DOTP (90%); 20; 10; 80; 80; 1; 22; 53.9; 0.85:129; F; 2:1; DOTP (90%); 20; 0; 80; 95; 1; 80; 50.8; 0.97:130; F; 2:1; DOTP (90%); 20; 0; 80; 110; 1; 887; 55.2; 0.81:1

[0171] As seen in Table 1, all the Ligands (A) - (F) can produce iso-butyraldehydeselectively and can operate at higher temperatures.

[0172] The invention has been described in detail with particular reference to specificembodiments thereof, but it will be understood that variations and modifications can bemade within the spirit and scope of the invention.

Claims

We claim:1.A catalyst composition comprising:(a)a transition metal; and(b)a ligand having the structure of formulas (I), (II), or (III):R4R3R3R4R1R5R5R5R5R2R3R4R3R4(1)R7R4R3R6-R8R1R5R5O-P-NN-P-O-R9R2R6-R8R4R3R7(II)R7R7R8-R6R6-R8R1R9P-N.N-P-O-R9R2R8-R6R6-R8R7R7(III)whereinR1 and R2 are each independently selected from H, and alkyl and cycloalkylgroups containing from 1 to 15 carbon atoms; andR3, R4, R5, R6, R7, R8, and R9 are each independently selected from H, F, CI, Br,and alkyl, cycloalkyl, aryl, alkoxy, trialkylsilyl, triarylsilyl, aryldialkylsilyl, anddiarylalkylsilyl groups containing from 1 to 20 carbon atoms, wherein the silicon atom ofthe alkylsilyl or triarylsilyl is directly bonded to the position of substitution.

2. The catalyst composition of claim 1, which comprises a ligand having thestructure of formula (I).

3. The catalyst composition of any one of claims 1-2, which comprises aligand having the structure of formula (II).4.The catalyst composition of any one of claims 1-3, which comprises aligand having the structure of formula (III).

5. The catalyst composition of any one of claims 1-4, wherein R₁ and R2 areeach methyl or linear alkyl containing 15 carbon atoms or less.6.The catalyst composition of any one of claims 1-5, wherein R₁ and R2 areeach methyl.7.The catalyst composition of any one of claims 1-6, wherein R3, R4, R5, R6,R7, R8, and R9 are each independently selected from H, F, CI, Br, trimethylsilyl, andalkyl, alkoxy, and cycloalkyl groups containing from 1 to 20 carbon atoms, andwherein the silicon atom of the trimethylsilyl is directly bonded to the position ofsubstitution.

8. The catalyst composition of any one of claims 1-7, wherein R3, R4, R5, R6,R7, R8, and R9 are each independently selected from F, CI, Br, methyl, tert-butyl, (2-phenylpropan-2-yl), adamantyl, trimethylsilyl, and methoxy.

9. The catalyst composition of any one of claims 1-8, wherein R3 is tert-butylor (2-phenylpropan-2-yl).

10. The catalyst composition of any one of claims 1-9, wherein R4 is methoxyor (2-phenylpropan-2-yl).

11. The catalyst composition of any one of claims 1-10, wherein R5 ishydrogen.

12. The catalyst composition of any one of claims 1-11, wherein R6 and R7 aremethyl, tert-butyl, or (2-phenylpropan-2-yl).13.The catalyst composition of any one of claims 1-12, wherein R8 ishydrogen.14.The catalyst composition of any one of claims 1-13, wherein R9 ishydrogen, tert-butyl, or cyclohexyl.

15. The catalyst composition of any one of claims 1-14, wherein the ligandhas the structure of formulas (A), (B), (C), (D), (E), or (F):MeO.tBuPhtBuOMePhMetBuOMeO-P-NN-P-OMeMeP-N.P-ONMeOtButBuMeOMe(A)PhtBuPhOMe(B)PhPhMeO.tBuMeOtBuMeNMeN-PPPtBuNMeNMeMeOtBuMeOtBuPh-Ph(C)(D)tButBuMeOtBuMeO.tButButBuMeMeNN-PPtBuPPNMeNMeMeOtButBuMeOtButButButBu(E)(F)16.The catalyst composition of any one of claims 1-15, wherein the transitionmetal is a Group VIIIB metal.17.The catalyst composition of any one of claims 1-16, wherein the transitionmetal comprises rhodium.

18. The catalyst composition of claim 17, wherein the rhodium is sourced fromdi-rhodium tetraacetate dihydrate, rhodium(II) acetate, rhodium(II) isobutyrate,rhodium(II) 2-ethylhexanoate, rhodium(II) benzoate, rhodium(II) octanoate, Rh4(CO)12,Rh6(CO)16, rhodium(I) acetylacetonate dicarbonyl, tris(triphenylphosphine) rhodiumcarbonyl hydride, or combinations thereof.

19. The catalyst composition of any one of claims 1-18, which provides an iso-selectivity of at least 50%, at least 55%, or at least 60% in a hydroformylation reactionat a temperature of 80°C to 110°C.

20. The catalyst composition of any one of claims 1-19, which is effective forconverting an olefin to an aldehyde in the presence of hydrogen and carbon monoxidefor at least 5 hours at 50°C.

21. The catalyst composition of any one of claims 1-20, wherein the molarratio of the ligand to the transition metal is at least 1:1, at least 2:1, at least 3:1, at least4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, or at least 10:1.22.A catalyst solution comprising:(a)the catalyst composition of any one of claims 1-21; and(b)a solvent.

23. The catalyst solution of claim 22, wherein the solvent comprisesdodecane, decalin, n-octane, iso-octane, cyclohexane, cyclooctane, cyclododecane,methylcyclohexane, 1,7-octadiene, dicyclopentadiene, 1,5-cyclooctadiene, octene-1,octene-2, 4-vinylcyclohexene, cyclohexene, 1,5,9-cyclododecatriene, 1-pentene,benzene, toluene, xylene isomers, tetralin, cumene, diisopropylbenzene,triisopropylbenzene, tert-butylbenzene, naphtha, mineral oils, kerosene, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, bis(2-ethylhexyl) terephthalate, octafluorotolulene, 1-methyl-2-pyrrolidinone, dimethyl-formamide, perfluoro-kerosene, sulfolane, higher boiling by-products formed during ahydroformylation reaction, water, or combinations thereof.

24. A process for preparing an aldehyde, the process comprising contactingan olefin with hydrogen and carbon monoxide in the catalyst solution of any one ofclaims 22-23, at conditions effective to form an aldehyde.25.The process of claim 24, wherein the olefin comprises ethylene,propylene, 1-butene, 1-octene, vinyl acetate, vinyl isobutyl ether, allyl alcohol, 3-acetoxy-1-propene, cyclohexene, 1,5-cyclooctadiene, cyclodecatriene, 4-vinylcyclohexene, 1,3-cyclohexadiene, 4-cyclohexene-carboxylic acid, methyl 4-cyclohexene-carboxylic acid, 1,4-cyclooctadiene, or 1,5,9-cyclododecatriene.

26. The process of claim 25, wherein the olefin comprises propylene, and thealdehyde comprises normal- and iso-butyraldehyde.

27. The process of claim 26, which has an iso-butyraldehyde selectivity of atleast 50%, at least 55%, or at least 60%.

28. The process of any one of claims 24-27, wherein the contacting step iscarried out at a temperature of 50 to 135°C, of 75 to 125°C, or of 80 to 110°C.

29. The process of any one of claims 24-28, wherein the contacting step iscarried out at a total pressure of 8 to 40 bars absolute.30.A compound having the structure of formula (II):R7R4R3R5R5R4R3(II)-P-N・ロードN-P-OR1R2R6R6R8-R9R8R7whereinR1 and R2 are each independently selected from H, and alkyl and cycloalkylgroups containing from 1 to 15 carbon atoms; andR3, R4, R5, R6, R7, R8, and R9 are each independently selected from H, F, CI, Br,and alkyl, cycloalkyl, aryl, alkoxy, trialkylsilyl, triarylsilyl, aryldialkylsilyl, anddiarylalkylsilyl groups containing from 1 to 20 carbon atoms, wherein the silicon atom ofthe alkylsilyl or triarylsilyl is directly bonded to the position of substitution.

31. The compound of claim 30, wherein R₁ and R2 are each methyl or linearalkyl containing 15 carbon atoms or less.32.The compound of any one of claims 30-31, wherein R₁ and R2 are eachmethyl.33.The compound of any one of claims 30-32, wherein R3, R4, R5, R6, R7, R8,and R9 are each independently selected from H, F, Cl, Br, trimethylsilyl, and alkyl,alkoxy, and cycloalkyl groups containing from 1 to 20 carbon atoms, andwherein the silicon atom of the trimethylsilyl is directly bonded to the position ofsubstitution.

34. The compound of any one of claims 30-33, wherein R3, R4, R5, R6, R7, R8,and R9 are each independently selected from F, Cl, Br, methyl, tert-butyl, (2-phenylpropan-2-yl), adamantyl, trimethylsilyl, and methoxy.

35. The compound of any one of claims 30-34, wherein R3 is tert-butyl or (2-phenylpropan-2-yl).

36. The compound of any one of claims 30-35, wherein R4 is methoxy or (2-phenylpropan-2-yl).

37. The compound of any one of claims 30-36, wherein R5 is hydrogen.

38. The compound of any one of claims 30-37, wherein R6 and R7 are methyl,tert-butyl, or (2-phenylpropan-2-yl).39.The compound of any one of claims 30-38, wherein R8 is hydrogen.40.The compound of any one of claims 30-39, wherein R9 is hydrogen, tert-butyl, or cyclohexyl.41.The compound of any one of claims 30-40, wherein the ligand has thestructure of formulas (C), (D), (E), or (F):MeOtBuPhPhMeO.tBu****MeNPPNMeMeOtBu(C)N-MePN-PtBuNMeMeOtBuPhPh(D)tButBuMeOtBuMeOtButButBuMeMeNPPPNNMeMeMeOtButBuMeOtButButButBu*****PtBu(E)(F)

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