KR20060129489A - Process for the carbonylation of ethylenically or acetylenically unsaturated compounds - Google Patents

Abstract

A process for the carbonylation of unsaturated compounds by contacting the unsaturated compound with carbon monoxide in the presence of a catalyst system comprising: (a) a source of palladium and/or platinum; and (e) an unsymmetrical bidentate diphosphine ligand of formula (I), R1R2 > P1 - R3 - P2 < R4R5 (I) wherein P1 andp P2 represent phosphorus atoms; R3 represents a divalent organic bridging group; and R1, R2, R4 and R5 each individually, or Rl and R2 jointly, and/or R4 and R5 jointly represent organic groups that are covalently linked to the phosphorus; and wherein R1, R2, R 4 and R5 are chosen in such way, that the phosphino group R1R2 > P1 differs from the phosphino group P2 < R4R5.

Description

PROCESS FOR THE CARBONYLATION OF ETHYLENICALLY OR ACETYLENICALLY UNSATURATED COMPOUNDS

The present invention provides a method for carbonylating ethylenic or acetylene unsaturated compounds.

As used herein, the terms carbonylation refer to, for example, EP-A-0,495,548 and EP-A-0,565,199, WO-A-96 / 19434, WO-A-98 / 42717, WO-A-01 / 68583 and WO-A. As described in -01/72697, co-reactants containing carbon monoxide and mobile hydrogen atoms of alkenes or alkynes, ie ethylene or acetylene non-conjugated unsaturated compounds, are catalyzed by transition metal complexes. React with reactant). The result of this process is a carboxylic acid product or carboxylic acid derivative, such as an ester, amide or anhydride, depending on the nature of the co-reactant.

EP-A-0,495,548 is a catalyst system containing a diphosphine bidentate ligand containing a palladium cation and a di-alkyl-substituted phosphino group such as 1,3-bis (di-tertiary butyl phosphino) propane and The use of such catalysts in various carbonylation reactions is disclosed.

Although the disclosed catalyst system exhibits good activity in the carbonylation reaction, further improvements in catalyst activity and selectivity for the desired product are required to apply the process on an industrial scale.

Summary of the Invention

Catalyst systems based on metal cations and asymmetric diphosphine ligands selected from Groups 8, 9 or 10 on the Periodic Table of the Elements show improved catalytic activity in the carbonylation of ethylenic or acetylenically unsaturated compounds, thereby significantly improving It has been found that a method of carbonylation, as a result, is possible.

Thus the invention:

(a) palladium and / or platinum sources; And

(b) asymmetric diphosphine of formula (I)

R ¹ R ² > P ¹ -R ³ -P ² <R ⁴ R ⁵

Wherein P ¹ and P ² represent a person group; R ³ represents a divalent organic bridging group; R ¹ , R ² , R ⁴ and R ⁵ are each individually or R ¹ and R ² are bonded, And / or an organic substituent wherein R ⁴ and R ⁵ are bonded and covalently bound to a person, provided that R ¹ , R ² , R ⁴ and R ⁵ are phosphino groups R ¹ R ² > P ¹ Ethylenic or acetylene-unsaturated by contacting an unsaturated compound with a co-reactant having carbon monoxide and mobile hydrogen atoms in the presence of a catalyst system containing a pino group P ² <R ⁴ R ⁵ ) It relates to a carbonylation method of a compound.

Detailed description of the invention

The process utilizes a catalyst system that can be obtained by combining (a) a metal cation source of palladium or platinum with a diphosphine ligand as defined above. One or more sources of such metal cations can be used in various carbonylation reactions. Among these metal cations, palladium (Pd) is particularly preferred for carbonylation reactions on olefinically unsaturated substrates, while platinum (Pt) is very preferred for acetylenically unsaturated substrates, and ethylene-based if desired branched products Preferred for unsaturated compounds.

Examples of suitable metal sources include Pd and / or Pt and salts of nitric acid, sulfuric acid or sulfonic acids, Pd and Pt and / or salts of carboxylic acids having up to 12 carbon atoms, Pd and / or Pt complexes such as carbon monoxide and / or acetyl aceto Rapid compounds such as Pd and / or Pt in combination with solid materials such as nates or ion exchangers. Pd and / or Pt acetate and acetyl acetonate are examples of preferred metal sources.

The catalyst system additionally contains as a component (b) an asymmetric diphosphine of formula (I)

Formula (I)]

R ¹ R ² > P ¹ -R ³ -P ² <R ⁴ R ⁵

Wherein P ¹ and P ² represent a person; R ³ represents a divalent organic bridging group; R ¹ , R ² , R ⁴ and R ⁵ each independently represent an organic substituent which R ¹ and R ² are bonded to, and / or R ⁴ and R ⁵ are bonded to and covalently bound to a person; With the proviso that R ¹ , R ² , R ⁴ and R ⁵ are selected such that the phosphino group R ¹ R ² > P ¹ is different from the phosphino group P ² <R ⁴ R ⁵ .

The advantageous effect of the asymmetric diphosphine in comparison to the corresponding symmetric diphosphine is expressed even when the substituents R ¹ and R ² linked to P ¹ are very similar to R ⁴ and R ⁵ linked to P ² . While there is no intention to adhere to any particular theory, it is believed that the differences in substituents result in differences in electron density in the valence. The presence of two binding occupant sites with different electron densities in the ligands has been shown to have a beneficial effect on the reaction rate. Differences in the electron donating ability of the phosphino fragments P ¹ R ¹ R ² and P ² R ⁴ R ⁵ of this ligand are described in Chemical Reviews, 1977, Vol. 77, pages 313-348 for C. phosphine ligands as described. It can be easily measured by the method developed by C. Tolman. In this method, the electron donating ability of the phosphine ligand reacts with one equivalent of (single) phosphine and Ni (CO) ₄ to make P ¹ R ¹ R ² into a Ni (CO) ₃ (phosphine) complex, This is then measured by measuring the carbonyl nCO IR stretching vibration (very sharp in high energy mode) of the Ni (CO) ₃ (phosphine) complex. The more the phosphine ligand provides more electron density to the metal center, and thus the stronger the electron donating ability, the lower the measured nCO IR stretching vibration. In diphosphine (b), even if only one substituent of R ¹ , R ² , R ⁴ or R ⁵ is different from the other substituents, the two persons will have different electron densities.

As such, the substituents R ¹ to R ⁴ are selected in such a way that one of the groups P ¹ or P ² has a lower electron density than the other groups, which can be measured for the transition metal carbonyl complex of ligand (b). Which is separated and exemplified by lower IR stretching vibrations. Number characters P ^1, or in the electron density between P ² difference is how to have the substituent R ¹ and / or R ² of the electronic more donor than the one of the personnel character P ¹ or P ² is R ⁴ and R ⁵ Or vice versa, by selecting R ¹ , R ² , R ⁴ and R ⁵ .

Particularly high catalytic activity in ligands in which R ¹ and R ² together or each individually represent an electron donor compared to the PPh ₂ -group, while R ⁴ and R ⁵ together or each individually represent an electron acceptor compared to the PPh ₂ -group This was found.

Within the context of this specification, the term "organic group" is an unsubstituted or substituted, aliphatic or arylaliphatic radical having 1 to 30 carbon atoms, which is covalently bound to a person by a carbon atom.

The organic groups R ¹ , R ² , R ⁴ and R ⁵ may each independently be a monovalent group, or R ¹ may be together with R ² or R ⁴ together with R ⁵ to be a divalent group. These groups may additionally contain one or more heteroatoms such as oxygen, nitrogen, sulfur or phosphorus and / or for example oxygen, nitrogen, sulfur and / or halogen atoms such as fluorine, chlorine, bromine, iodine and / or cyano It may be substituted by one or more functional groups containing groups.

Although increased catalytic activity compared to each similar symmetric ligand is shown by all asymmetric bidentate ligands tested, at least one of R ¹ and R ² , or at least one of R ⁴ and R ⁵ comprises tertiary carbon atoms and This revealed a particularly high increase in catalytic activity in ligands which represent organic groups linked to personnel.

Higher activity was found when both R ¹ and R ² , or both R ⁴ and R ⁵ contain tertiary carbon atoms and through which each group represents an organic group linked to a person atom, R ¹ , R ² It has been found that both R ⁴ and R ⁵ exhibit tertiary carbon atoms and thus exhibit much higher and unparalleled activity when they represent organic groups linked to personnel.

Thus, most preferably the invention also relates to a carbonylation process where all of R ¹ , R ² , R ⁴ and R ⁵ contain tertiary carbon atoms and whereby each group represents an organic group linked to a person It is about.

Tertiary carbon atoms in which at least ^one of R ¹ , R ² , R ⁴ or R ⁵ is preferably linked to a tertiary carbon atom, in which the carbon atom is covalently bonded to three substituents other than hydrogen and hydrogen, are aliphatic, alicyclic It may be substituted with a group or an aromatic substituent, or may form part of a substituted saturated or unsaturated aliphatic ring structure, all of which may contain heteroatoms.

Preferably, the tertiary carbon atoms of R ¹ and R ² , or R ⁴ and R ⁵ may be substituted with alkyl groups, thereby making the tertiary carbon atoms part of the tertiary alkyl groups, or the tertiary Carbon atoms may be substituted with ether groups. Examples of suitable organic groups include tertiary-butyl, 2- (2-methyl) butyl, 2- (2-ethyl) butyl, 2- (2-phenyl) butyl, 2- (2-methyl) Pentyl, 2- (2-ethyl) pentyl, 2- (2-methyl-4-phenyl) pentyl, 1- (1-methyl) cyclohexyl group and 1-adamantyl-group (where 1 or 2 adamantyl Or trioxa-adamantyl group associates with a person via a tertiary bridging head atom). Although R ¹ and R ² , or R ⁴ and R ⁵ groups are each individually different organic groups, R ¹ and R ² , or R ⁴ and R ⁵ , Preferably the same tertiary organic group. Accordingly, the present invention also encompasses a process wherein both R ¹ and R ² , or both R ⁴ and R ⁵ , represent tertiary butyl groups.

Preferably a substituent of the second person, ie, R ¹ and R ² are bonded, or R ⁴ and R ⁵ are bonded to represent a divalent group directly connected to the person via two tertiary carbon atoms. Such divalent groups may be monocyclic or multicyclic structures.

Thus, R ¹ and R ² may combine or R ⁴ and R ⁵ may combine to represent an optionally substituted divalent alicyclic group, where the alicyclic group is bonded to a person via two tertiary carbons. do. Examples of preferred divalent groups are unsubstituted or substituted C ₄ -C ₃₀ -alkylene groups wherein the CH ₂ -group can be replaced by ether bonds via oxygen atoms or by other hetero groups. Suitable divalent groups include 1,1,4,4-tetramethyl-buta-1,4-diyl-, 1,4-dimethyl-1,4-dimethoxy-buta-1,4-diyl-, 1,1 , 5,5-tetramethyl-penta-1,5-diyl, 1,5-dimethyl-1,5-dimethoxy-penta-1,5-diyl-, 3-oxa-1,5-dimethoxy-penta -1,5-diyl, 3-oxa-1,1,5,5-tetramethyl-penta-1,5-diyl-, 3-oxa-1,5-dimethyl-1,5-dimethoxy-penta- 1,5-diyl and similar divalent radicals are included.

Particularly preferred monocyclic structures containing R ¹ and R ² together or R ⁴ and R ⁵ together include 2,2,6,6-tetrasubstituted phosphin-4-one or 2,2,6,6-tetra Substituted phosphinan-4-thione structures are included. Ligands containing such structures are described in Welcher and Day, Journal of Organic Chemistry, J. Am. Chem. Soc., 27 (1962) 1824-1827. Under mild conditions, for example, secondary phosphine can be converted to 2,6-dimethyl-2,5-heptadien-4-one (also diisopropyl). Easily known as lidene acetone, or poron).

Particularly preferred multicyclic structures comprising R ¹ and R ² together, or R ⁴ and R ⁵ together, are for example substituted at positions 1, 3 and 5 (thus providing tertiary carbon atoms which are linked to the person). ) 2-phospha-tricyclo [3.3.1.1 {3,7}] decyl groups, or derivatives thereof in which at least one of the carbon atoms is replaced by a heteroatom.

Tricyclo [3.3.1.1 {3,7}] decane is the systematic name for a compound, more commonly known as adamantan. 1,3,5-trisubstituted 2-phospha-tricyclo [3.3.1.1 {3,7} decyl groups or derivatives thereof are thus referred to herein as "2-PA" groups (2-phosphaadamantyl groups). Will be mentioned. This 2-PA group has 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms in at least one of positions 1, 3 and 5, optionally also in position 7 Monovalent organic group R ⁷ is substituted. Examples of R ⁷ include methyl, ethyl, propyl and phenyl.

More preferably, the 2-PA group is substituted at each of the 1, 3, 5 and 7 positions, suitably the same R ⁷ , even more preferably a methyl group. Preferably the 2-PA group contains additional heteroatoms in addition to the 2-membered atom in its backbone. Suitable heteroatoms are oxygen and sulfur atoms. More suitably such heteroatoms are found at positions 6, 9 and 10. Most preferred divalent radicals are 2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxadamantyl (2-phospha-1,3,5,7-tertamethyl-6, 9,10-trioxadamantyl) group.

R ¹ and R ² are each independently an organic group linked together only via a person atom, while R ⁵ and R ⁶ combine to represent a divalent organic group bonded to a second person through two tertiary carbon atoms, 2 Very good results have been obtained in the carbonylation of ethylenically unsaturated compounds by means of a catalyst system containing a site diphosphine ligand.

Thus, a particularly preferred diphosphine ligands for the catalyst system according to the invention (b) is a compound according to formula II, wherein R ¹ together with R ^2, or R ⁴ together with R ⁵ each person characters P ^1, or In combination with P ² , 2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxadamantyl group or 2,2,6,6-tetramethyl phosphinan-4- Form on, and the other substituents R ¹ and R ² , or R ⁴ and R ⁵ each individually represent a tertiary butyl group.

Within this application, a "bivalent organic bridging group" R ³ should be understood as a group connecting the person P ¹ to P ² via the shortest link in the ligand. The bridging group R ³ may preferably have a structure as represented by formula (III) below,

-R ^a _m -R ^b -R ^c _n-

Wherein R ^a and R ^b independently represent the same or different, optionally substituted methylene group; R ^b is an organic group containing a divalent bridging group C ¹ -C ² , wherein R ^b is linked to R ^a and R ^c ; m and n independently represent a natural number in the range of 0 to 3, where the rotation for the bond between the carbon atoms of the bridging groups C ¹ and C ² at a temperature in the range of 0 ° C. to 250 ° C. is limited and C ¹ , C ² and P ¹ 2 dihedral between direction C filled with 3 atomic sequence consisting atom directly bonded to the ^first plane, and C ^1, C ² and P ² direction in plan filled with 3 atomic sequence consisting atoms directly bonded to C ² of the ( dihedral angle) ranges from 0 to 120 degrees. The terms binding and rotation are as defined in Hendrickson, Cram and Hammond, Organic Chemistry, 3rd Edition, 1970, pages 175-201. Rotation according to the instant invention means that the atoms are individually attached to C ¹ and C ² with respect to the rotation axis passing through the center of the bond between C ¹ and C ^2. Rotation for binding is called "free" when the rotation barrier is so low that different conformations cannot be perceived as different species at experimental scale time. The suppression of rotation of a group for binding due to the presence of sufficiently large rotation barriers to create observable phenomena at an experimental scale can be described as "hindered rotation" or "restricted rotation" (IUPAC Compendium of Chemical). Terminology 2nd Edtion (1997), 68, 2209). Suitable experiments are described, for example, in Hendrickson, Cram and Hammond, Organic Chemistry, 3rd Edition, 1970, pages 265-281 and in FA Bovey, Nuclear Magnetic Resonance Spectroscopy, (New York, Academic Press, 1969), p. ¹ H-NMR-experiment as defined in 1-20], if a hydrogen atom is present in the ligand, an appropriate shift will be influenced by the bond between C ¹ and C ² .

Preferably, there is no free rotation for the bond between C ¹ and C ² in the temperature range in which the method is carried out. This temperature range can easily be from 0 ° C. to 250 ° C., but preferably the method can be carried out in the range from 10 ° C. to 200 ° C., even more preferably in the range from 15 ° C. to 150 ° C. and even more preferably. It may be carried out in the range of 18 ℃ to 130 ℃. When measured in liquid or solution, ie neat conditions, or in a solution of a suitable solvent, rotations to bonds in the temperature range where the ligand is liquid are considered to be suppressed if there is no measurable rotation. Thus, rotation of the bidentate ligand to C ¹ -C ² bonds is inhibited or limited in the solution or liquid state of the ligand. Preferably the rotation of the bidentate ligand relative to binding C ¹ -C ² is preferably inhibited or limited within the temperature range of the method.

The bridging group R ^b contains a chain of two carbon atoms C ¹ and C ² which are optionally substituted. These carbon atoms C ¹ and C ² form a direct bridge between R ¹ R ² P ¹ -R ^a _m -and -R ^c _n -P ² R ⁵ R ⁶ , whereby personnel P ¹ and P ² , and optionally substituted methylene groups R ^a _m and R ^c _n, are linked through a bridging group C ¹ -C ² to form a diphosphine ligand (b).

Although many different restricted loci are possible for the ligand in question, it has been found that certain dihedral angles are of great importance for the activity of the catalyst system. Biface angle is generally defined as an angle formed by two intersecting planes. 4 at the dihedral sequence (atom directly bonded to C ¹ in the direction of P ¹⁾ in the method -C ¹ -C ² - in (a direction atom directly bonded to C ² and the P ^2), three atomic C ² , By a plane filled with a triatomic sequence composed of atoms directly bonded to C ¹ in the directions of C ¹ and P ¹ , and a plane filled with a triatomic sequence composed of atoms directly bonded to C ^{2 in} the directions of C ¹ , C ² and P ² Angle formed and ranges from 0 ° to 120 °. As used herein, the term "in the direction of P ¹ or in the direction of P ² " means that the relevant atoms are located individually on a portion of the ligand chain linked to C ¹ and P ¹ , or C ² and P ² .

For example, when m and n are 1, the dihedral angle is the 3-membered sequence R ^a -C ¹ -C ² and the 4-membered sequence R ^a -C of the 4-membered sequence R ^a -C ¹ -C ² -R ^c . ¹ -C ² -R ^c Angle between planes filled by the other three-atomic sequence C ¹ -C ² -R ^c . It is to be understood that each plane passes through the center point of each atom. If m and n in formula (III) should be 0, the four-atom sequence would therefore be P ¹ -C ¹ -C ² -P ² , and the two planes would be P ¹ -C ¹ -C ² and C ¹ -C Will be defined as ² -P ² .

In ligands according to the method, the dihedral angle as defined above is in the range of 0 ° to 120 °. Since a higher catalytic activity of the catalyst system is thus obtained, the dihedral angle is preferably in the range of 0 ° to 70 °, more preferably in the range of 0 ° to 15 °, and most preferably in the range of 0 ° to 5 °. .

While not intending to adhere to a particular theory, it is believed that ligands that enable rotation about binding C ¹ -C ² are difficult to form morphologically stable bidentate complexes with palladium centers.

The bond formed between C ¹ and C ² may be a saturated or unsaturated bond as occurs in an ethylenically unsaturated compound or an aromatic compound compound. When a saturation bond connects C ¹ and C ² , R ^b can be represented by C ¹ R'R "-C ² R"'R"", so that the bidentate diphosphine ligand according to the invention is suitably It can be represented by the following formula (IV):

R ¹ R ² P ¹ -R ^a _m -C ¹ R'R "-C ² R"'R""-R ^c _n -P ² R ⁴ R ⁵ .

In this embodiment, if only one of R 'and R "and only one of R"' and R "" are hydrogen, then R 'and R "and R"' and R "" are hydrogen or the same or Different, optionally substituted organic groups are indicated. If C ¹ and C ² are connected by ethylenically unsaturated double bonds, C ¹ and C ² also cannot be freely rotated. In this case, R may be represented by C ¹ R ′ = C ² R ″, and the bidentate diphosphine ligand according to the present invention may suitably be represented by the following formula (V):

R ¹ R ² P ¹ -R ^a _m C ¹ R '= C ² R "-R ^c _n -P ² R ⁵ R ⁶ .

If the bond between C ¹ and C ² is an ethylenically unsaturated bond, the ligand chain connecting P ¹ and P ² through C ¹ and C ² may exist mainly in two isomers, trans- and cis-forms. have. As defined above, the dihedral angle in the trans-array is about 180 °, while in the cis-array the bifacial angle is about 0 °.

Substituents R ′ to R ″ ″ in formula IV or V may themselves be independent substituents, and thus are linked to each other only via carbon atoms C ¹ and C ² , or preferably have one or more additional linkages. Substituents may additionally contain carbon atoms and / or heteroatoms.

The limitation of free rotation is crosslinking group C of molecular structure which inhibits rotation with respect to bond C ¹ -C ² at room temperature, preferably at a temperature in the range from 0 to 250 ° C., more preferably at a temperature in the range from 15 to 150 ° C. It can also be easily achieved by the ¹ -C ² forming part. Preferably, this molecular structure is for example a) ethylenically unsaturated double bonds (where rotation is inhibited by the overlapping of energetically beneficial π-bonds) and / or b) aromatic or nonaromatic ring structures. The same cyclic hydrocarbon structure, wherein the rotation is due to a steric interaction of substituents R 'to R "" or to a steric hindrance caused by a cyclic structure in which R' to R "" form together or May be limited by a combination of factors). Morphological stability and thus rigidity are also determined by c) binding C ¹ , for example by strong steric interactions, even if R ′ and R ″ and / or R ″ ′ and R ″ ″ of the substituents are not linked to ^{one another.} It can be achieved if it has the property of inhibiting rotation about -C ² . For this purpose, even more preferably none of R ′ to R ″ ″ in Formula IV or Formula V represent hydrogen.

R ^b is preferably a cyclic hydrocarbon structure optionally substituted by a heteroatom, even more preferably an aliphatic or aromatic hydrocarbon structure. Such structures may be part of an optional additionally substituted saturated or unsaturated polycyclic structure, which may also optionally contain heteroatoms such as nitrogen, sulfur, silicon or oxygen atoms.

Suitable structures R ^b include, for example, substituted cyclohexyl, cyclohexenyl, cyclohexadienyl, substituted cyclopentane, cyclopentenyl or cyclopentadienyl structures, all of which are nitrogen, sulfur, silicone Or optionally contains a heteroatom such as oxygen, provided that the rotation about the bond C ¹ -C ² is limited, the dihedral angle ranges from 0 ° to 120 °, preferably 2,2-dimethyl-1, There is no rotation about the bonds formed by C ¹ and C ² , caused by coordination changes, as in highly rigid acetal structures such as 3-dioxolane (2,2-dimethyl-1,3-dioxolane). In a particularly preferred embodiment, R ^b represents a divalent polycyclic hydrocarbon ring structure. Such polycyclic groups are particularly preferred because of their high morphological stability and thus the free rotation for the bond between C ¹ and C ² is very limited. Examples of such particularly preferred hydrocarbon groups include norbornyl, norbornadienyl, isonobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indenemethanyl (octahydro-4,7-methano-1H-indenemethanyl), α- and β-pinyl, and 1,8-cineolyl (1,8-cineolyl), all of which may be optionally substituted, or It may contain heteroatoms as defined.

When the bidentate ligand has a chiral center, it may be any of R, R-form, S, S-form or R, S-meso form or a mixture thereof. If the dihedral angle ranges from 0 to 120 °, both meso forms and racemic mixtures can be used.

In the diphosphine of formula (II), R ^b preferably represents an optionally substituted divalent aromatic group, which is connected to the person via the groups R ^a and R ^c . Such aromatic ring structures are preferred in that the rigidity of the structure and, in general, the dihedral angle ranges from 0 to 5 degrees.

The aromatic group may be a monocyclic group such as, for example, a phenyl group, and may be a multicyclic group such as, for example, naphthyl, anthryl or indyl group. Preferably the aromatic group R contains only carbon atoms, but R ^b is also an aromatic group whose carbon chain is interrupted by one or more heteroatoms such as nitrogen, sulfur or oxygen atoms such as pyridine, pyrrole, furan, tee Or a group of openes, oxazoles or thiazoles. Most preferred aromatic group R ^b represents a phenyl group or a naphthylene group. Optionally, aromatic group R ^b is substituted. Suitable substituents include groups containing heteroatoms such as halogens, sulfur, phosphorus, oxygen and nitrogen. Examples of such groups include chloride, bromide, iodide and the general formulas -OH, -OX, -CO-X, -CO-OX, -SH, -SX, -CO-SX, -NH ₂ , -NHX,- NO ₂ , -CN, -CO-NH ₂ , -CO-NHX, -CO-NX ₂ , -CI ₃ or -CF ₃ group, wherein X is independently methyl, ethyl, propyl, isopropyl And alkyl groups having 1 to 4 carbon atoms such as n-butyl. When aromatic group R ^b is substituted, R ^b is preferably substituted with one or more aryl, alkyl or cycloalkyl groups, preferably having from 1 to 10 carbon atoms. Suitable groups include methyl, ethyl, trimethyl, isopropyl, tetramethyl and isobutyl, phenyl and cyclohexyl.

Most preferably, however, the aromatic group R ^b is unsubstituted and is bound only to groups R ^a and R ^c which link R ^b to the person. Even more preferably, R ^a and R ^c are alkylene groups and are therefore bonded at adjacent positions, for example at the 1 and 2 positions of the aromatic group.

The symbols m and n in formulas (III), (IV) and (V) independently represent natural numbers ranging from 0 to 3. If m and n are zero, the persons P ¹ and P ² are directly connected to the bridges formed by the carbon atoms C ¹ and C ² . If either m or n is 0, then either C ¹ or C ² will be directly connected to P ¹ or P ² . While not intending to adhere to a particular theory, the resulting effect that occurs in the particular arrangement of the central linkages formed by C ¹ and C ² on the occupant and thus on the catalyst complex is due to the presence of a larger number of groups R ^a and / or R ^c . It is thought to be diluted by the presence. It is also contemplated that when m and n are zero, the distance between the occupants becomes rather short so that the ligand binds less strongly to the palladium central atom of the catalyst complex. Thus, due to the generally good catalytic activity found in such ligands, preferably m is 0 or 1, while n is preferably in the range of 1 to 3, more preferably in the range of 1 to 2, most preferably of 1 to be.

If m and / or n have a value of 1 or more, some optionally substituted groups R ^a and R ^c link R ^b to P ¹ and P ² . R ^a and / or R ^c can be of different groups, identically or individually, with these differences. Thus R ^a and / or R ^c are preferably lower alkylene groups (lower alkylene groups are understood as alkylene groups containing 1 to 4 carbon atoms). Such alkylene groups may or may not be substituted, for example with alkyl groups or heteroatoms, such as may represent methylene, ethylene, trimethylene, isopropylene, tetramethylene, isobutylene and tert-butylene or methyl Oxy, ethyloxy and similar groups. Most preferably at least one of R ^a and / or R ^c is a methylene group.

Particularly suitable aromatic groups for R ^b include aryl groups such as disubstituted phenyl or naphthyl groups, and substituted alkyl phenyl groups such as tolyl and xylyl groups. Preferred because of the high stability of the ligands and catalysts obtained are tolyl and xylyl groups, where the methylene substituents or methylene substituents in the aromatic ring contribute as R ^a and / or R ^c groups. Most preferably, C ¹ and C ² are part of an aromatic ring, while at least one of R ^a and / or R ^c represents a methylene group attached to adjacent atoms C ¹ and C ² in the aromatic.

Thus, particularly preferred ligand families according to the invention are that C ¹ and C ² are part of a phenyl ring; m is 0 or 1; n is 1; R ^a and R ^c are ligand groups that are methylene groups. Another particularly preferred ligand group is preferred because of its easy synthesis potential, and m and n are one. Thus, ligands based on 1,2-di (phosphinomethyl) benzene or 1-phosphino-2- (phosphinomethyl) -benzene groups provide high rigidity of the aromatic backbone, ease of synthesis and catalyst systems derived from the ligands. It is particularly suitable for this process because of the very good results obtained. Such ligands are for example 1- (1,3,5,7-tetramethyl) -1,3,5-trimethyl-6,9,10-trioxa-2-phosphatricyclo [3.3.1.1 {3 , 7}] decyl-2- (di-tert-butylphosphinomethyl) benzene.

Very good results are also obtained by means of the asymmetric bidentate diphosphine ligand of formula VI

R ¹ R ² > P ¹ -CH ₂ -C (= X)-CH ₂ -P ² <R ⁴ R ⁵

Wherein X represents an oxygen atom, a sulfur atom, an amino group or an optionally substituted alkylene group, and P ¹ and P ² represent a person group; R ¹ , R ² , R ⁴ and R ⁵ each represent an organic group which is bonded individually or R ¹ and R ² are bonded and / or R ⁴ and R ⁵ are bonded covalently with a person; Wherein R ¹ to R ⁴ are selected such that the phosphino group R ¹ R ² > P ¹ is different from the phosphino group P ² <R ⁴ R ⁵ . In such ligands, R ^a is CH ₂ , m is 1, R ^b is C═CH ₂ , and R ^c is CH ₂ . In such ligands, the divalent organic crosslinking group R ³ represents a tertiary alkylene carbon atom C (= X). X is preferably an optionally substituted alkylene group, more preferably a methylene group, thus R ³ is equal to -C (= CH ₂ )-. In this ligand, since rigidity of the alkylene structure rotating with respect to the carbon atoms are very _{^{limited, P 1 -CH 2 -C (=}} CH 2) - , and the _{C (= CH 2) -CH 2} -P 2 The dihedral angle formed is in the range of 0 ° to 120 °.

Preferably such ligands have been used in catalyst compositions containing asymmetric bidentate diphosphine ligands and sources of palladium, platinum or rhodium. Sources of palladium, platinum or rhodium have been found to be particularly effective in hydroformulation reactions, ie carbonylation reactions in the presence of hydride sources such as molecular hydrogen, specifically anion sources.

The invention makes it possible to convert non-conjugated ethylenic and acetylenically unsaturated compounds into corresponding products with very high turnover numbers due to high catalytic activity. Suitable ethylenic or acetylenically unsaturated compounds are ethylenic or acetylenically unsaturated compounds having 2 to 50 carbon atoms per molecule or mixtures thereof. Suitable ethylenic and acetylenically unsaturated compounds may have one or more isolated unsaturated bonds per molecule. Preferred are compounds having 2 to 20 carbon atoms or mixtures thereof, more preferably 18 or less carbon atoms, still more preferably 16 or less carbon atoms, and even more preferably 10 or less carbon atoms. The ethylenic or acetylenically unsaturated compounds may additionally contain functional groups or heteroatoms such as nitrogen, sulfur or oxygen. Examples include nitric acid as carboxylic acid, ester or functional group. In a preferred embodiment, the ethylenic or acetylene unsaturated compounds are olefins or mixtures of olefins. Such olefins can be converted by reaction with co-reactants having high regioselectivity to carbon monoxide and straight chain carbonylation products. Suitable ethylenic or acetylenically unsaturated compounds include acetylene, methyl acetylene, propyl acetylene, ethylene, propylene, butylene, isobutylene, pentene, pentene nitrile, methyl 3-pentenoate, 2-pentenoic acid and 3-pentenoic acid do. Another preferred feedstock is a mixture of olefins or mixtures of olefins and saturated compounds, for example obtained in the Fischer-Tropsch synthesis step. In such a synthesis, a mixture of olefins and saturated hydrocarbons are generally obtained. The content of olefins in such mixtures can vary and the content can be increased by starting the synthesis with the synthesis product of the iron-catcher Fischer-Tropsch synthesis step. Much higher olefin content in the mixture can be obtained by catalytic dehydrogenation or pyrolysis in the presence of steam. Particularly suitable methods for reacting such mixtures are the selective reaction of olefinic or acetylene based non-conjugated compounds in such mixtures without affecting other saturated compounds, thus carbonylated products from saturated hydrocarbons Allows for easy separation. According to this method, ethylenic or acetylenically unsaturated compounds can be converted into a wide variety of chemical compounds, such as aldehydes, esters, acids or acid anhydrides, thioesters, amides, and alcohols or other compounds. The specific properties of the product depend on the nature of the co-reactant with mobile hydrogen atoms. The co-reactant according to the invention is thus any compound with mobile hydrogen, which can react as a nucleophile with diene in the presence of a catalyst. The nature of the co-reactant usually determines the form of the product formed. Suitable co-reactants are water, carboxylic acids, alcohols, ammonia or amines, thiols or combinations thereof. In other words, the catalyst system can be used for "hydroformylation reaction", "hydrocarboxylation reaction", "hydroesterification reaction" or "hydroamidation reaction".

As long as the co-reactant is water, the product obtained will be carboxylic acid. Anhydrides are obtained if the co-reactant is carboxylic acid. For alcohol co-reactants, the product of carbonylation is an ester. Similarly, using ammonia (NH ₃ ) or primary or secondary amines, ie, RNH ₂ or R'R "NH, will result in amides, while thiols, RSH will produce thioesters. In defined co-reactants, R, R 'and / or R "represent organic radicals, preferably alkyl, alkenyl or aryl radicals, optionally substituted with heteroatoms. If ammonia or amines are used, small amounts of these co-reactants will react with the acids present in the formation of the amide and water. Thus, water is always present in the case of ammonia or amine co-reactants. Preferred alcohol co-reactants are alkanols having 1 to 20 carbon atoms per molecule, more preferably 1 to 6 carbon atoms per molecule, and alkanediols having 2 to 20 carbon atoms per molecule and more preferably 2 to 6 carbon atoms per molecule. Alkanols may be aliphatic, cycloaliphatic or aromatic. Suitable alkanols for the process of the invention include methanol, ethanol, ethanediol, n-propanol, 1,3-propanediol, iso-propanol, 1-butanol, 2-butanol (sec-butanol), 2-methyl-1 -Propanol (isobutanol), 2-methyl-2-propanol (tert-butanol), 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol (Isoamyl alcohol), 2-methyl-2-butanol (tert-amyl alcohol), 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 3,3-dimethyl-2-butanol, 1 -Heptanol, 1-octanol, 1-nonanol, 1-decanol, 1,2-ethylene glycol and 1,3-propylene glycol, of which methanol has high conversion water reachability and Most preferred because of its unique utility. Preferred amines have 1 to 20 carbon atoms per molecule, more preferably 1 to 6 carbon atoms per molecule, and diamines have 2 to 20 carbon atoms per molecule, more preferably 2 to 6 carbon atoms per molecule. . The amines can be aliphatic alicyclic or aromatic. Ammonia and primary amines are more preferred because of high conversion yields.

Thiol co-reactants may be aliphatic, cycloaliphatic or aromatic. Preferred thiol co-reactants are aliphatic diols having 1 to 20 carbon atoms per molecule, more preferably 1 to 6 carbon atoms per molecule and aliphatic dithiols having 2 to 20 carbon atoms per molecule and more preferably 2 to 6 carbon atoms per molecule. .

This carbonylation reaction is also known as hydroformylation reaction when the co-reactant is a hydride such as molecular hydrogen. It feeds carbon monoxide and hydrogen into the reaction in an equimolar or non-equimolar ratio, such as in the range 5: 1 to 1: 5, preferably in the range 3: 1 to 1: 3. This can be achieved by. Preferably carbon monoxide and hydrogen are fed at a ratio in the range from 2: 1 to 1: 2, resulting in an alcohol mixture. In particular, when the Fischer-Tropsch product stream is used as feedstock, the resulting mixture can be suitably used for hygiene or other related applications.

Carbonylation may suitably be carried out under mild reaction conditions. A temperature in the range of 50 to 200 ° C. is therefore recommended, preferably in the range of 70 to 160 ° C. Reaction pressures in the range of 5 to 100 bar are preferred and lower or higher pressures may be selected, but are not considered to be particularly advantageous. In addition, higher pressures require the provision of special devices.

In the process of the invention, the products formed as well as the unsaturated starting materials and co-reactants can serve as reaction solvents. Thus, the use of individual solvents may be unnecessary. However, the carbonylation reaction can easily be carried out in the presence of an additional solvent, in particular a solvent can be added in the start-up phase of the reaction. Saturated hydrocarbons, ie paraffins and isoalkanes themselves are preferred and additionally alcohols are preferred, and saturated hydrocarbons and alcohols preferably have from 1 to 10 carbon atoms per molecule, including methanol, butanol, 2-ethylhexane- General alcohols which are formed as 1-ols, nonan-1-ols or carbonylation products; There are also ethers such as 2,5,8-trioxanonan (diglyme), diethyl ether and anisole, ketones such as methyl ethyl ketone. Also preferred are solvents containing or substantially consisting of sulfones. Sulfones are particularly preferred, for example dialkylsulfones such as dimethylsulfone and diethylsulfone and cyclic sulfones such as sulfolane, 2-methyl sulfolane and 2-methyl-4-ethyl-sulfolane .

The molar ratio of atoms of the palladium cation, i.e., bidentate diphosphine per mole of catalyst component (a), ie catalyst component (b), is from 0.5 to 10, preferably from 0.8 to 8, and even more preferably from 1 to 5. The molar ratio of palladium atoms, i.e., bidentate diphosphine per mole of catalyst component (a), ie catalyst component (b), is not critical. Preferably the molar ratio is in the range of 0.1 to 100, more preferably 0.5 to 10.

More preferred catalytically active species are based on equimolar amounts of bidentate diphosphine ligands per mole of palladium. Therefore, the molar amount of the bidentate diphosphine ligand per mole of palladium is preferably in the range of 1 to 3, more preferably in the range of 1 to 2, even more preferably in the range of 1 to 1.5. In the presence of oxygen, slightly higher amounts may be advantageous.

Preferably, the catalyst system or composition preferably further contains an anion source. Suitable anion sources may be strong or weak coordinating anions. Various anions can be used as counter-ions for the metal cations. Examples of these include anions which are base salts of acids having a pKa of less than 6, preferably less than 4 (measured in water at 18 ° C.). Anions derived from these acids do not coordinate with the metal cations or only coordinate very weakly, meaning that there is little or no covalent interaction between the anions and the cations. Catalysts based on these anions exhibit good activity.

Suitable anions include phosphoric acid and sulfuric acid, in particular Bronsted acid and trifluoroacetic acid such as sulfonic acid, 2,6-dichlorobenzoic acid and 2,6-bis (trifluoromethyl) benzoic acid or trifluoroacetic acid Anions derived from (halogenated) carboxylic acids, such as, and the like. Anions derived from sulfonic acids are particularly preferred, for example methanesulfonic acid, trifluoromethanesulfonic acid, tert-butanesulfonic acid, p-toluenesulfonic acid and 2,4,6-trimethylbenzenesulfonic acid. Also suitable are complex anions, such anions being preferably selected from Lewis acids such as BF ₃ , B (C ₆ F ₅ ) ₃ , AlCl ₃ , SnF ₂ , Sn (CF ₃ SO ₃ ) ₂ , SnCl ₂ or GeCl ₂ and preferably 5 Occurs in combination with a protic acid having a pKa of less than, for example, sulfonic acid (eg CF ₃ SO ₃ H or CH ₃ SO ₃ H) or hydrohalogenic acid (HF or HCl), or a combination of Lewis acid with an alcohol ( combination). Examples of such complex anions include ^{_{BF 2 -, SnCl 3 -,}} [SnCl 2 · CF 3 SO 3] - a ^- and PF _6. Preferably the source of the anion is carboxylic acid, which acts not only as an accelerator component but also as a solvent of the reaction. Even more preferably, the source of the anion is an acid having a pKa of less than or equal to 3.6 (measured in an 18 ° C. aqueous solution), even more preferably the catalyst component (c) has a pKa of 3.0 or less, even more preferably 2.0 or more pKa. It is a mountain to hold. Examples of suitable acids include acetic acid, propionic acid, butyric acid, pentanoic acid, pentenoic acid and nonanoic acid. Very easily the acid corresponding to the desired product in the reaction can be used as catalyst component (c). The catalyst component (c) may also be an ion exchange resin containing carboxylic acid groups. This advantageously simplifies the purification of the product mixture.

If the co-reactant is amine or ammonia and the anion source of the catalyst system is an acid, preferably the amount of ammonia or amine is less than the stoichiometric amount based on amine functionality. Unintentionally, even when the co-reactant is ammonia and even some primary amines, small amounts of the acids present will react with the amide in the absence of water. Thus, there is always a small amount of acid formed in conjugated dienes, carbon dioxide and water, which in turn replaces the acids which are converted to amides by the direct reaction described above.

The anion source and the molar ratio of palladium, platinum or rhodium are not critical. However, the molar ratio is 2: 1 to 10 ⁷ : 1, more preferably 10 ² : 1 to 10 ⁶ : 1, even more preferably 10 ² : 1 to 10 ⁵ : 1, due to the activity of the enhanced catalyst system. And most preferably in the range 10 ² : 1 to 10 ⁴ : 1. Thus, if the co-reactant reacts with an acid that serves as an anion source, the amount of acid versus the amount of co-reactant must be chosen so that an appropriate amount of free acid is present. Because of the increased reaction rate, excess excess acid is generally preferred for the co-reactant.

The amount in which the complete catalyst system is used is not critical and can vary within wide limits. Conventional palladium-olefin per one mole atom ^10-8 to ^10-1 molar range, preferably from 10 ^-7 to 10 ^-2 mole of the range is used, preferably used olefin ^110-5 to 10 ^-2 g atom per mol do. The process may optionally be carried out in the presence of a solvent, but preferably acids are used as solvents and promoters.

The carbonylation reaction according to the invention is carried out at mild temperatures and pressures. Suitable reaction temperatures are in the range of 0-250 ° C, more preferably 50-200 ° C, even more preferably 80-150 ° C.

The reaction pressure is usually above room temperature. Suitable pressures are 0.1 to 15 MPa (1 to 150 bar), preferably 0.5 to 8.5 MPa (5 to 85 bar). Carbon monoxide partial pressures in the range of 0.1 to 8 Mpa (1 to 80 bar) are preferred, and higher ranges of 4 to 8 MPa are more preferred. Higher pressures require the provision of special devices.

The carbonylation reaction is additionally easily carried out at a temperature in the range from 30 to 200 ° C., preferably at a temperature in the range from 50 to 180 ° C.

In the process according to the invention, carbon monoxide can be used in pure form or in an inert gas such as nitrogen, carbon dioxide, or in a dilution with a Group 0 gas such as argon, or a co-reactant gas such as ammonia.

The invention will be illustrated by the following non-limiting examples.

Example 1: Preparation of 9- (2-{[di (tert-butyl) phosphino] methyl} -2-propenyl) -9-phosphabicyclo [3.3.1] nonane

1: 9- (2-{[di (tert-butyl) phosphino] methyl} -2-propenyl) -9-phosphabicyclo [3.3.1] nonane

A mixture of di-tert-butylphosphine (5 g, 34.1 mmol) and 3-chloro-2-chloromethyl-1-propene (14.04 g, 69 mmol) was dissolved in degassed acetonitrile (70 ml) and 16 hours Heated to 60 ° C. This solvent was removed in vacuo and the product suspended in hexane (50 ml). After filtration, the product was washed with hexane (40 ml, twice). The white solid salt was neutralized with HNEt ₂ (5 ml) in a mixture of toluene (50 ml) and water (30 ml) under reflux conditions. The toluene layer was separated, washed with water (30 ml, twice) and removed in vacuo to yield 3.14 g (40%) of di (tert-butyl) [2- (chloromethyl) -2-propenyl] phosphine. did.

The product was confirmed by the clear resonance signal shown at δ = + 21.7 ppm in ³¹ P NMR.

2.82 g (20 mmol) of 9-phosphabicyclo [3.3.1] nonane was dissolved in THF (90 ml). To this solution, a 1.6M solution of n-BuLi in hexane (12.5 ml, 20 mmol) was added at -50 ° C. This mixture was warmed to 0 ° C. for 15 minutes, then cooled to −70 ° C., then di (tert-butyl) [2- (chloromethyl) -2- obtained as described above in 10 ml THF. A solution of 4.7 g (20 mmol) of propenyl] -phosphine was added. The mixture was allowed to warm to room temperature, which in turn was cooled with water (5 ml). The solvent was removed in vacuo and toluene (60 ml) was added. The mixture was washed twice with water (40 ml and 20 ml) and toluene was removed in vacuo to yield 6.71 g of red / orangesec oil. This product was crystallized twice in methanol (boiling) to give a white solid (2.83 g, 42%). This product was confirmed by two distinct resonance signals appearing at +22.1 ppm and -36.5 ppm in ³¹ P NMR.

Example  2: 8- (2-{[D ( tert Butyl) Phosphino ] methyl }-2- Propenyl ) -1,3,5,7- Tetramethyl Preparation of -2,4,6-trioxa-8-phosphatricyclo [3.3.1.1. {3,7}] decane

Figure 2: 8- (2-{[di (tert-butyl) phosphino] methyl} -2-propenyl) -1,3,5,7-tetramethyl-2,4,6-trioxa-8- Phosphatricyclo [3.3.1.1. {3,7}] decane

Solution of HPcage * BH ₃ in THF (20 ml) (1.34 g, 5.83 mmol; Pcage = 1,3,5,7-tetramethyl-2,4,6-trioxa-8-phospha-tricycle [3.3 .1.1. {3,7}] decane) was added a 1.6M solution of n-BuLi in hexane (3.64 ml, 5.83 mmol) at -78 ° C. The mixture was allowed to warm to 0 ° C. for 15 minutes and cooled back down to −78 ° C., followed by di (tert-butyl) [2- (chloromethyl) -2-propenyl] -phosphine as described below in THF. Solution was added. The reaction mixture was allowed to warm to room temperature. HNEt ₂ (10 ml) was added and the reaction mixture was refluxed for several hours until NMR-measurement showed that deprotection was complete. Subsequently, the solvent was removed in vacuo and gradual cooling was performed to recrystallize the solid product from methanol. The isolated yield was 1.5 g (62%) and the product was identified by two distinct resonance signals at +20.3 ppm (p-tert.Bu) and -34.3 ppm (P-Cage) for ³¹ P NMR. there was.

Example  3: 8- (2-{[D ( tert Butyl) Phosphino ] methyl } Phenyl ) -1,3,5,7- Tetramethyl -2,4,6- Trioxa -8-phosphatricyclo [3.3.1.1 {3,7}] decane

Reference figure 3: 8- (2-{[di (tert-butyl) phosphino] methyl} phenyl) -1,3,5,7-tetramethyl-2,4,6-trioxa-8-phosphatri Cyclo [3.3.1.1 {3,7}] decane

8.25 g (33 mmol) of 2-bromobenzylbromide and 5 g (34.2 mmol) of di-tert-butyl phosphine in 40 ml of degassed acetonitrile were measured and injected into a 100 ml glass reactor under inert atmosphere and stirred at room temperature for 12 hours. . The acetonitrile was then removed in vacuo and 30 ml of degassed toluene, 30 ml of degassed water and 7.5 ml of triethylamine were added. 10 ml of ethanol was added to the mixture to increase phase separation. Immediately after phase separation, the upper layer containing toluene was separated, evaporated to dryness. The residue was ⁹ g (28.6 mmol, 87%) of (2-bromobenzyl) (di-tert-butyl) phosphine as a pale yellow oil with a resonance peak at +34.16 ppm in ³¹ P NMR.

2.5 g (7.9 mmol) of 2-bromobenzyl (di-tert-butyl) phosphine thus obtained in 10 ml of toluene, 2.24 g (20 mmol) of DABCO, 1,3,5-trimethyl-4,6,9- 1.94 g (9 mmol) of trioxa-2-phosphatricyclo- [3.3.1.1 {3.7}] decane and 0.23 g (0.2 mmol) of Pd (PPh ₃ ) ₄ are added to a 250 ml glass vessel under an inert atmosphere, The contents of the vessel were heated to 140 ° C. with stirring for 12 hours. The mixture was then cooled to 100 ° C. and then filtered. After the filtrate was cooled to room temperature, 30 ml of methanol was added and the mixture was cooled to -35 [deg.] C. for 12 hours; 8- (2-{[di (tert-butyl) -phosphino] -methyl} phenyl) -1,3,5,7-tetramethyl-2,4,6-trioxa-8-phosphatricyclo [ 3.3.1.1 {3,7}]-decane was separated into yellow crystals (2.2 g, 4.9 mmol, 62%) and identified by two distinct resonance signals at +38.08 and -38.96 ppm in ³¹ P NMR. there was.

Example  4 to 6 and Comparative example  A, B and C: 1- by methanol Octene  transform

A catalyst solution containing 40 ml of methanol, 20 ml of 1-octene, and 0.5 mmol of methanesulfonic acid, and 0.1 mmol of palladium acetate and 10 ml of methanol in a 250 ml magnetic stirred autoclave manufactured by HATELLOY C (HASTELLOY C is a tradename). 0.2 mmol of each ligand in it was charged sequentially. This autoclave was closed, degassed and pressurized with 3 MPa carbon monoxide. The reactor was then heated to 70 ° C. and maintained at this temperature for 10 hours. Finally the autoclave was cooled, depressurized and the reaction mixture was analyzed by GLC. Conversion frequency is defined as the amount of product converted, given in mol of olefins per mole of Pd per hour for batch operation, as shown in Table I.

Examples 7 and 8: Conversion of Ethylene by Means of Methanol

A 250 ml magnetic stirred autoclave made by HASTELLOY C (trade name HASTELLOY C) was continuously charged with 45 ml of methanol and 0.5 mmol of methanesulfonic acid. The autoclave was closed, degassed and pressurized with 3 MPa of carbon monoxide and 20 MPa of ethanol. The reactor was then heated to 85 ° C. and 0.1 mmol of each ligand in 5 ml of methanol and a catalyst solution containing 0.05 mmol of palladium acetate was injected into the autoclave, thereby further raising the carbon monoxide pressure by 5 bar. This autoclave was kept at 85 ° C. for 10 hours. Finally the autoclave was cooled, depressurized and the reaction mixture was analyzed by GLC. The conversion frequency is defined as the amount of product converted, given in mol of olefins per mole of Pd per hour for batch operation, as shown in Table I.

In Example 4 according to the invention, the ligand is 9- (2-{[di (tert-butyl) phosphino] methyl} -2-propenyl) -9-phosphabicyclo [3.3. 1] It was nonan. In Examples 5 and 7, according to the present invention, the ligand is 8- (2-{[di (tert-butyl) phosphino] methyl} -2-propenyl) -1,3,5, prepared in Example 2 7-tetramethyl-2,4,6-trioxa-8-phosphatricyclo [3.3.1.1 {3,7}] decane. In Examples 6 and 8 according to the invention, the ligand is 8- (2-{[di (tert-butyl) phosphino] methyl} phenyl) -1,3,5,7-tetramethyl prepared in Example 3 -2,4,6-trioxa-8-phospha-tricyclo [3.3.1.1 {3,7}] decane.

In Comparative Example A, the ligand is a (9- [2- (9-phosphabicyclo [3.3.1] non-), which is a symmetric ligand with two 9-phosphabicyclo [3.3.1] nonane rings attached to the isobutane structure. 9-ylmethyl) -2-propenyl] -9-phosphabicyclo [3.3.1] nonane). In Comparative Example B, the ligand is symmetric bis-di-tert-butylphosphino-analog (di (tert-butyl) (2- {di (tert-butyl) phosphino] methyl} -2-propenyl) phosphine) to be. In Comparative Example C, the ligand is symmetric bis-trioxa-adamantyl-ligand (1,3,5,7-tetramethyl-8- {2- [1,3,5,7-tetramethyl-2,4 , 6-trioxa-8-phosphatricyclo [3.3.1.1 {3,7} deck-8-yl) methyl] -2-propenyl} -2,4,6-trioxa-8-phospha- Tricyclo [3.3.1.1. {3,7}] decane). In Comparative Example D, the ligand is symmetric bis-trioxadamantyl-ligand ([1,3,5,7-tetramethyl-8- {2- {1,3,5,7-tetramethyl-2,4 , 6-trioxa-8-phosphatricyclo [3.3.1.1. {3,7}] dec-8-yl) methyl] benzyl} -2,4,6-trioxa-8phosphatricyclo- [ 3.3.1.1 {3,7}] decane). In Comparative Example E, the ligand is symmetric 1,2-bis (di-tert-butylphosphinomethyl) benzene ([1,2-phenylenebis- (methylene)] bis (di-tert-butylphosphine)) .

The results are shown in Table I.

Example Ligand temperament Conversion Frequency [mol / mol Pd / hr] Selectivity for straight chain products, [%] Example 4 Example 1 1-octene 1500 83 Example 5 Example 2 1-octene 15000 87 Example 6 Example 3 1-octene 20,000 96 Comparative Example A See above 1-octene 150 76 Comparative Example B See above 1-octene 250 67 Comparative Example C See above 1-octene 500 83 Comparative Example D See above 1-octene 50 67 Comparative Example E See above 1-octene 100 97 Chemosel. Carbonylation product, [%] Example 7 Example 5 Eten 20,000 99.9 Example 8 Example 6 Eten 60,000 99.9

In the data, it is clear that the asymmetric ligand clearly outperforms the symmetric ligand in terms of catalytic activity and selectivity for the desired straight chain product. In addition, the use of two different substituents of R ¹ , R ² , R ⁴ and R ⁵ resulted in unexpected catalytic activity and selectivity for straight chain carbonylation products, where R ¹ and R ² are R ⁴ on P ² And has a different electron donating ability on P ¹ compared to R ⁵ , and all substituents R ¹ , R ² , R ⁴ and R ⁵ bind to the person via a tertiary carbon atom).

Claims (19)

(a) palladium and / or platinum sources; And (b) carbonylating unsaturated compounds by contacting the unsaturated compounds with carbon monoxide in the presence of a catalyst system containing an asymmetric bidentate diphosphine ligand of Formula I: [Formula I] R ¹ R ² > P ¹ -R ³ -P ² <R ⁴ R ⁵ Wherein P ¹ and P ² represent a person; R ³ represents a divalent organic bridging group; R ¹ , R ² , R ⁴ and R ⁵ each represent an organic group which is individually or in which R ¹ and R ² are bonded and / or R ⁴ and R ⁵ are bonded and covalently bound to a person; Where R ¹ , R ² , R ⁴ And R ⁵ is a phosphino group R ¹ R ² > P ¹ is a phosphino group P ² <R ^{4 is} selected to be different from R ⁵ . The method of claim 1, wherein R ¹ and R ² are P ¹ than R ⁴ and R ⁵ on P ² . A method of carbonylation, characterized by a higher ability to donate electrons to a phase. 3. The compound of claim ¹ , wherein R ¹ and R ² independently represent the same or different, optionally substituted organic groups, which groups are connected to each other only via the person P ¹ ; And wherein R ⁴ and R ⁵ together represent an organic divalent group bonded to the phosphorus P ² . The method according to any one of claims 1 to 3, wherein R ¹ , R ² , R ⁴ and R ⁵ each represent an organic radical covalently bonded to each person via a tertiary carbon atom. , Carbonylation method. The compound according to any one of claims 1 to 4, wherein R ¹ represents a 2-phospha-adamantane structure or a phosphin-4-one structure together with R ² or R ⁴ together with R ^5. Characterized in that the carbonylation method. 6. The method of carbonylation according to claim 1, wherein R ³ represents a group of formula III: 7. [Formula III] -R ^a _m -R ^b -R ^c _n- Wherein R ^a and R ^b independently represent the same or different, optionally substituted methylene group; R ^b is an organic group containing a divalent bridging group C ¹ -C ² , wherein R ^b is linked to R ^a and R ^c ; m and n independently represent a natural number in the range of 0 to 4, wherein the carbon atom C ¹ of the crosslinked group at a temperature in the range of 0 ° C to 250 ° C And rotation about the bond between C ² is restricted, C ^1, in the direction of C ² and P directions as C 3 filled with the atom sequence-planar surfaces configured atom directly bonded to the ¹ and C ^1, C ^{2 1,} and P ² C ^The dihedral angle between planes filled with triatomic sequences composed of atoms directly bonded to 2 ranges from 0 to 120 degrees. 8. The compound of claim 7 wherein R ^b represents an aryl group, wherein m is 0 or 1, n is 1 and the persons P ¹ and P ² are linked to R via each methylene group R ^a or R ^c , Characterized in that it is directly linked with R at an adjacent position of the aryl group. 8. A compound according to claim 6 or 7, wherein R ¹ and R ² represent tertiary butyl groups, and R ⁴ and R ⁵ together represent a 2-phospha-adamantane structure or a phosphin-4-one structure. Characterized in that the carbonylation method. 9. The method of carbonylation according to claim 1, wherein ethylene is converted to methyl propionate in the presence of methanol. 10. The carbonylation method according to any one of claims 1 to 8, characterized in that the pentenoic acid is converted to adipic acid. (a) palladium and / or platinum sources; And (b) a catalyst composition containing an asymmetric bidentate diphosphine ligand of formula (I) [Formula I] R ¹ R ² > P ¹ -R ³ -P ² <R ⁴ R ⁵ Wherein P ¹ and P ² represent a person; R ³ represents a divalent organic bridging group; R ¹ , R ² , R ⁴ and R ⁵ each represent an organic group which is individually or in which R ¹ and R ² are bonded and / or R ⁴ and R ⁵ are bonded and covalently bound to a person; Wherein R ¹ , R ² , R ⁴ and R ⁵ are phosphino groups R ¹ R ² > P ¹ is phosphino group P ² <R ^{4 is} selected to be different from R ⁵ . The method according to claim 11, wherein R ¹ and R ² represents a tertiary butyl group, R ⁴ together with R ⁵ characterized in that it represents a 2-phospha-adamantane structure or phosphin-4-one structure, Catalyst composition. The catalyst composition of claim 11 or 12, wherein R ³ represents a group of formula III: [Formula III] -R ^a _m -R ^b -R ^c _n- Wherein R ^a and R ^b independently represent the same or different, optionally substituted methylene group; R ^b is an organic group containing a divalent bridging group C ¹ -C ² , wherein R ^b is linked to R ^a and R ^c ; m and n independently represent a natural number ranging from 0 to 4, wherein the carbon atom C ¹ of the bridging group And rotation about the bond between C ² is limited at a temperature ranging from 0 ℃ to 250 ℃, C ^1, C ² and filled with 3 atomic sequence consisting atoms directly bonded to C ¹ in the direction of P ¹ plane, and C ^1, The dihedral angle between planes filled with triatomic sequences consisting of atoms directly bonded to C ² in the direction of C ² and P ² ranges from 0 to 120 °. 14. The compound of claim 13, wherein R ^b represents an aryl group, wherein m is 0 or 1, n is 1, and the persons P ¹ and P ² are linked to R via each methylene group R ^a or R ^c Or directly connected to R at an adjacent position of an aryl group. The catalyst composition according to any one of claims 11 to 14, which further contains an anion source. Asymmetric bidentate diphosphine ligand of formula VI: [Formula VI] R ¹ R ² > P ¹ -CH ₂ -C (= X)-CH ₂ -P ² <R ⁴ R ⁵ Wherein X represents an oxygen atom, a sulfur atom, an amino group or an optionally substituted alkylene group; P ¹ and P ² represent personnel; R ¹ , R ² , R ⁴ and R ⁵ each represent an organic group which is bonded individually or R ¹ and R ² are bonded and / or R ⁴ and R ⁵ are bonded covalently with a person; R ¹ to R ⁴ are selected such that the phosphino group R ¹ R ² > P ¹ is different from the phosphino group P ² <R ⁴ R ⁵ . 17. The asymmetric bidentate diphosphine ligand of claim 16, wherein X represents a methylene group. A catalyst composition containing the asymmetric bidentate diphosphine ligand according to claim 16 or 17 and a palladium, platinum or rhodium source. 19. The catalyst composition of claim 18, further comprising an anion source.