FERROCENE BASED COMPOUNDS AND PALLADIUM CATALYST BASED THEREON FOR THE ALCOHXICARBONYLATION OF ETHYL

专利摘要:
compounds based on ferrocene and palladium catalysts based thereon for the alkoxycarbonylation of ethylenically unsaturated compounds The invention relates to a compound of formula (i) (i) wherein: each of r1, r2, r3 and r4 is a group independently selected from -alkyl(C1-C12), -cycloalkyl(C3-C12), -heterocycloalkyl(C3-C12), -aryl(C6-C20), -heteroaryl(C3-C20); at least one of the radicals r1, r2, r3, r4 represents a -heteroaryl(c6-c20) radical having at least six ring atoms and the symbols r1, r2, r3, r4, if they are -(c1-c12)alkyl , -cycloalkyl(c3-c12), -heterocycloalkyl(c3-c12), -aryl(c6-c20), -heteroaryl(c3-c20), or -heteroaryl(c6-c20), may each be independently substituted with one or more substituents selected from -alkyl(c1-c12), -cycloalkyl(c3-c12), -heterocycloalkyl(c3-c12), -oalkyl(c1-c12), -o-alkyl(c1-c12)- aryl(c6-c20), -o-cycloalkyl(c3-c12), -salkyl(c1-c12), -s-cycloalkyl(c3-c12), -coo-alkyl(c1-c12), -coocycloalkyl(c3- c12), -conh-alkyl(c1-c12), -conh-cycloalkyl(c3-c12), -co-alkyl(c1-c12), -co-cycloalkyl(c3-c12), -n-[alkyl(c1-c12) )]2, -aryl(c6-c20), -aryl(c6-c20)-alkyl(c1-c12), -aryl(c6-c20)-o-alkyl(c1-c12), -heteroaryl(c3-c20) ),-heteroaryl(c3-c20)-alkyl(c1-c12), -heteroaryl(c3-c20)-o-alkyl(c1-c12), -cooh, -oh, -so3h, -nh2, halogen. the invention further concerns precursors for the preparation of the compound according to the invention, pd complexes comprising the compound according to the invention and their use in alkoxycarbonylation.
公开号:BR102016016724B1
申请号:R102016016724-8
申请日:2016-07-19
公开日:2021-06-29
发明作者:Kaiwu DONG；Helfried Neumann；Ralf Jackstell；Matthias Beller；Robert Franke；Dieter Hess；Katrin Marie Dyballa；Dirk Fridag；Frank Geilen
申请人:Evonik Operations Gmbh；
IPC主号:

专利说明:

[001] The present invention relates to new compounds based on ferrocene and their use in alkoxy-carbonylation.
[002] The alkoxy-carbonylation of ethylenically unsaturated compounds constitutes a process with increasing significance. An alkoxycarbonylation is intended to refer to the reaction of ethylenically unsaturated compounds, such as olefins, with carbon monoxide and alcohols in the presence of a metal or a metal complex and a binder to obtain the corresponding esters.

[003] Scheme 1: General equation of the alkoxy-carbonylation reaction of an ethylenically-instituted compound.
[004] Among the alkoxy-carbonylation reactions, methoxy-carbonylation of ethene to obtain 3-methylpropionate is important as an intermediate step for the preparation of methyl methacrylate (SG Khokarale, EJ García-Suárez, J. Xiong, UV Mentzel, R. Fehrmann, A. Riisager, Catalysis Communications 2014, 44, 73-75). The methoxy-carbonylation of ethene is carried out in methanol as a solvent under mild conditions with a palladium catalyst modified with phosphine binders.
[005] A very good catalytic system was developed by Lucite - now Mitsubishi Rayon - and in it is using a binder based on 1,2-bis-(di-tert-butyl-phosphino-methyl)-benzene (DTBPMB) (W Clegg, GR Eastham, MRJ Elsegood, RP Tooze, XL Wang, K. Whiston, Chem. Commun. 1999, 18771878).
[006] Applications of methoxy-carbonylation to longer-chain substrates are described, for example, in EP 0 662 467. The patent specification describes a process for the preparation of dimethyl adipate from methyl 3-pentanoate. The Pd source used is Pd(II) acetate. Examples of suitable bidentate phosphine binders which are cited include 1,1'-bis-(diphenyl-phosphino)-ferrocene, 1-(diphenyl-phosphino)-1'-(di-isopropyl-phosphino)-ferrocene and 1,1'-bis(isopropyl-phenyl-phosphino)-ferrocene. However, binders achieve only unsatisfactory yields in the methoxy-carbonylation of olefins, in particular of long-chain olefins such as 2-octene and di-n-butene.
[007] The technical problem on which the present invention was based is to provide new compounds based on ferrocene as binders for alkoxy-carbonylation reactions. These compounds aim to achieve improved yields, in particular, in the conversion of long-chain olefins such as 2-octene or di-n-butene. More particularly, the space-time yield should be increased in the alkoxy-carbonylation reaction.
[008] This problem is solved by diphosphine compounds of structural formula (I)

[009] in which:
[010] each of the symbols R1, R2, R3, R4 independently represents a group selected from -alkyl (C1-C12), -cycloalkyl (C3-C12), -hetero-cycloalkyl (C3-C12), -aryl (C6 -C20), -heteroaryl (C3-C20);
[011] at least one of the radicals R1, R2, R3, R4 represents a -heteroaryl (C6-C20) radical having at least six atoms in the ring; and
[012] the symbols R1, R2, R3, R4, if they represent -alkyl (C1-C12), - cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6-C20), - heteroaryl (C3-C20), or -heteroaryl (C6-C20),
[013] may each be replaced with one or more substituents selected from:
[014] -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -O-alkyl (C1-C12), -O-alkyl (C1-C12)-aryl (C6 -C20), -O-cycloalkyl (C3-C12), -S-alkyl (C1-C12), -S-cycloalkyl (C3-C12), -COO-alkyl (C1-C12), -COO- cycloalkyl (C3 -C12), -CONH-alkyl (C1-C12), -CONH-cycloalkyl (C3-C12), -CO-alkyl (C1-C12), -CO-cycloalkyl (C3-C12), -N-[alkyl ( C1-C12)]2, -aryl(C6-C20), -aryl(C6-C20)-alkyl(C1-C12), -aryl(C6-C20)-O-alkyl(C1-C12), -heteroaryl ( C3C20), -heteroaryl(C3-C20)-alkyl(C1-C12), -heteroaryl(C3-C20)-O-alkyl(C1-C12), -COOH, -OH, -SO3H, -NH2, halogen.
[015] The compounds according to the invention are suitable as bidentate phosphine ligands for complexes with Pd, with which it is possible to achieve high yields in the alkoxy-carbonylation of various ethylenically unsaturated compounds. More particularly, the compounds according to the invention are suitable for the alkoxy-carbonylation of long-chain olefins such as 1-octene or di-n-butene.
[016] The expression (C1-C12) alkyl comprises straight or branched chain alkyl groups that have between 1 and 12 carbon atoms. Preferably these are (C1-C8) alkyl groups, more preferably (C1-C6) alkyl and even more preferably (C1-C4) alkyl.
Suitable (C1-C12) alkyl groups include, in particular, methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl , 2-methyl-butyl, 3-methylbutyl, 1,2-dimethyl-propyl, 1,1-dimethyl-propyl, 2,2-dimethyl-propyl, 1-ethyl-propyl, n-hexyl, 2-hexyl, 2 -methyl-pentyl, 3-methyl-pentyl, 4-methyl-pentyl, 1,1-dimethyl-butyl, 1,2-dimethyl-butyl, 2,2-dimethyl-butyl, 1,3-dimethylbutyl, 2,3 -dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethyl-propyl, 1-ethyl-butyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3 - heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, decyl.
[018] The explanations regarding the expression alkyl (C1-C12) also correspondingly apply to the alkyl groups in -O-alkyl (C1C12), -S-alkyl (C1-C12), -COO-alkyl (C1-C12), -CONH-alkyl(C1-C12), -CO-alkyl(C1-C12) and -N-[alkyl(C1-C12)]2.
[019] The expression cycloalkyl (C3-C12) comprises monocyclic, bicyclic or tricyclic hydrocarbyl groups that have between 3 and 12 carbon atoms. Preferably, these groups are (C5-C12) cycloalkyl groups.
[020] Preferably, the cycloalkyl groups (C3-C12) have between 3 and 8 and more preferably, 5 or 6 atoms in the ring.
Suitable (C3-C12)cycloalkyl groups include, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl, norbornyl, adamantyl.
[022] The explanations regarding the expression cycloalkyl (C3-C12) also correspondingly apply to cycloalkyl groups in -O-cycloalkyl (C3-C12), -S-cycloalkyl (C3-C12), -COO -cycloalkyl (C3-C12), -CONH-cycloalkyl (C3-C12), -CO-cycloalkyl (C3-C12).
[023] The expression heterocycloalkyl (C3-C12) comprises non-aromatic, saturated or partially unsaturated cycloaliphatic groups having between 3 and 12 carbon atoms, in which one or more of the ring carbon atoms are replaced by heteroatoms. Heterocycloalkyl (C3-C12) groups preferably have 3 to 8 and more preferably 5 or 6 ring atoms and are optionally substituted with aliphatic side chains. In heterocycloalkyl groups, unlike cycloalkyl groups, one or more of the ring carbon atoms are replaced by heteroatoms or groups containing heteroatoms. Heteroatoms or groups containing heteroatoms are preferably selected from O, S, N, N(=O), C(=O), S(=O). In the context of the present invention, a heterocycloalkyl group (C3-C12) is thus also ethylene oxide.
Suitable heterocycloalkyl (C3-C12) groups include, in particular, tetrahydrothiophenyl, tetrahydrofuryl, tetrahydropyranyl and dioxanyl.
[025] The expression aryl (C6-C20) comprises monocyclic or polycyclic aromatic hydrocarbyl radicals that have between 6 and 20 carbon atoms. Preferably these represent aryl (C6-C14) and more preferably aryl (C6-C10).
Suitable aryl groups (C6-C20) include, in particular, phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl. Preferred aryl (C6-C20) groups include phenyl, naphthyl and anthracenyl.
[027] The expression heteroaryl (C3-C20) comprises monocyclic or polycyclic aromatic hydrocarbyl radicals having between 3 and 20 carbon atoms, in which one or more of the carbon atoms are replaced by heteroatoms. Preferred heteroatoms include N, O and S. Heteroaryl groups (C3-C20) have 3 to 20, preferably 6 to 14 and more preferably 6 to 10 ring atoms. Thus, for example, the pyridyl group, in the context of the present invention, represents a C6 heteroaryl radical; furyl represents a C5 heteroaryl radical.
Suitable heteroaryl groups (C3-C20) include, in particular, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, furazanyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl , indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.
[029] The term heteroaryl (C3-C20) also comprises heteroaryl radicals (C6-C20) that have at least six atoms in the ring.
[030] The expression heteroaryl (C6-C20) having at least six atoms in the ring comprises monocyclic or polycyclic aromatic hydrocarbyl radicals with 6 to 20 carbon atoms, in which one or more carbon atoms are replaced by heteroatoms. Preferred heteroatoms include N, O and S. Heteroaryl groups (C6-C20) have 6 to 14 and more preferably 6 to 10 ring atoms.
[031] Heteroaryl groups (C6-C20) having at least six suitable ring atoms include, in particular, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.
[032] The expression halogen includes, in particular, fluorine, chlorine, bromine and iodine. Fluorine and chlorine are particularly preferred.
[033] According to a variant, the radicals R1, R2, R3, R4, if they represent -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6- C20), -heteroaryl(C3-C20) or -heteroaryl(C6-C20), can each be independently substituted with one or more substituents selected from -alkyl(C1-C12), -cycloalkyl(C3- C12), -heterocycloalkyl (C3-C12), -O-alkyl (C1-C12), -O-alkyl (C1-C12)-aryl (C6-C20), -O-cycloalkyl (C3C12), -S-alkyl (C1-C12), -S-cycloalkyl (C3-C12), -aryl (C6-C20), -aryl (C6-C20)-alkyl (C1-C12), -aryl (C6-C20)-O-alkyl (C1-C12), -heteroaryl (C3-C20), - heteroaryl (C3-C20)-alkyl (C1-C12), -heteroaryl (C3-C20)-O-alkyl (C1-C12), - COOH , -OH, -SO3H, -NH2, halogen.
[034] According to a variant, the radicals R1, R2, R3, R4, if they represent -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6- C20), -heteroaryl(C3-C20) or -heteroaryl(C6-C20), can each be independently substituted with one or more substituents selected from -alkyl(C1-C12), -cycloalkyl(C3-C12) , -O-alkyl(C1-C12), -O-alkyl(C1-C12)-aryl(C6-C20), -O-cycloalkyl(C3-C12), -aryl(C6-C20), -aryl(C6 - C20)-alkyl (C1-C12), -aryl (C6-C20)-O-alkyl (C1-C12), -heteroaryl (C3-C20), - heteroaryl (C3-C20)-alkyl (C1-C12) , -heteroaryl(C3-C20)-O-alkyl(C1-C12).
[035] According to a variant, the radicals R1, R2, R3, R4, if they represent -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6- C20), -heteroaryl(C3-C20) or -heteroaryl(C6-C20), can each be independently substituted with one or more substituents selected from -alkyl(C1-C12), -O-alkyl(C1-C1- C12)-aryl(C6-C20), -heteroaryl(C3-C20), -heteroaryl(C3-C20)-alkyl(C1-C12), -heteroaryl(C3-C20)-O-alkyl (C1-C12) ).
[036] According to a variant, the radicals R1, R2, R3, R4, if they represent -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6- C20), -heteroaryl (C3-C20) or -heteroaryl (C6-C20), can each be independently substituted with one or more substituents selected from -alkyl (C1-C12) and -heteroaryl (C3-C20) .
[037] According to a variant, the radicals R1, R2, R3, R4 are unsubstituted if they represent -alkyl (C1-C12), -cycloalkyl (C3-C12) or heterocycloalkyl (C3-C12) and may be substituted such as It is described if they represent -aryl (C6-C20), -heteroaryl (C3-C20) or -heteroaryl (C6-C20).
[038] According to a variant, the radicals R1, R2, R3, R4 are unsubstituted if they represent -alkyl (C1-C12), -cycloalkyl (C3-C12), -hetero-cycloalkyl (C3-C12), -aryl (C6-C20), -heteroaryl (C3-C20) or -heteroaryl (C6C20).
[039] In one embodiment, each of R1, R2, R3, R4 is independently selected from -alkyl(C1-C12), -aryl(C6-C20), -heteroaryl(C3-C20);
[040] wherein at least one of the radicals R1, R2, R3, R4 represents a -heteroaryl radical (C6-C20) having at least six atoms in the ring;
[041] and the radicals R1, R2, R3, R4, if they represent -alkyl (C1-C12), -aryl (C6-C20), -heteroaryl (C3-C20) or -heteroaryl (C6-C20), can be substituted with one or more of the above-described substituents.
[042] According to a variant, at least two of the radicals R1, R2, R3, R4 represent a -heteroaryl radical (C6-C20) having at least six atoms in the ring.
[043] In one embodiment, each of the radicals R1 and R3 represents a -heteroaryl radical (C6-C20) having at least six ring atoms and each of which may be substituted with one or more of the described substituents. Preferably, R2 is here a -heteroaryl(C6-C20) radical having at least six ring atoms or is a group selected from -alkyl(C1-C12), -cycloalkyl(C3-C12), -heterocycloalkyl ( -C3-C12), -aryl(C6-C20), more preferably among -alkyl(C1-C12), -cycloalkyl(C3-C12), -aryl(C6-C20). In this case, R4 is preferably a group selected from -alkyl(C1-C12), -cycloalkyl(C3-C12), -heterocycloalkyl(C3-C12), -aryl(C6-C20) and more preferably , between -alkyl(C1-C12), -cycloalkyl(C3-C12), -aryl(C6-C20).
[044] According to a variant, each of the radicals R1 and R3 represents a -heteroaryl (C6-C20) radical having at least six atoms in the ring and the radicals R2 and R4 represent a group selected from -alkyl (C1-C1- C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6-C20). In this case, each of the radicals R 1 , R 2 , R 3 , R 4 can be independently substituted with one or more of the substituents described above.
[045] More preferably, each of the radicals R1 and R3 represents a -heteroaryl (C6-C20) radical having at least six atoms in the ring and the radicals R2 and R4 represent -alkyl (C1-C12). In this case, each of the radicals R 1 , R 2 , R 3 , R 4 can be independently substituted with one or more of the substituents described above.
[046] According to a variant, each of the radicals R1, R2, R3 represents a -heteroaryl radical (C6-C20) having at least six ring atoms and each of which may be independently substituted with one or more of the substituents described before. In this case, preferably, the radical R4 does not represent a -heteroaryl (C3-C20) radical. In this case, more preferably, the radical R4 represents a group selected from -alkyl(C1-C12), -cycloalkyl(C3-C12), -heterocycloalkyl(C3-C12), -aryl(C6-C20) and, more preferably, between -alkyl(C1-C12), -cycloalkyl(C3-C12), -aryl(C6C20).
[047] According to a variant, each of the radicals R1, R2, R3 and R4 represents a -heteroaryl (C6-C20) radical having at least six ring atoms and each of which can be independently substituted with one or more of the substituents described above.
[048] According to a variant, each of the radicals R1, R2, R3 and R4, if they represent a heteroaryl radical, represents a group independently selected from heteroaryl radicals having six to ten atoms in the ring.
[049] According to a variant, the radicals R1, R2, R3 and R4, if they represent a heteroaryl radical, represent a heteroaryl radical having six atoms in the ring.
[050] Preferably, each of the radicals R1, R2, R3 and R4, if they represent a heteroaryl radical, represents a group independently selected from pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl, wherein the mentioned heteroaryl radicals may be substituted as described above.
[051] According to a variant, each of the radicals R1, R2, R3 and R4, if they represent a heteroaryl radical, represents a group independently selected from pyridyl, pyrimidyl, indolyl, in which the mentioned heteroaryl radicals may be substituted such as described before.
[052] Preferably, each of the radicals R1, R2, R3 and R4, if they represent a heteroaryl radical, represents a group independently selected from 2-pyridyl, 2-pyrimidyl, 2-indolyl, wherein the heteroaryl radicals mentioned may be replaced as described above.
[053] Preferably, each of the radicals R1, R2, R3 and R4, if they represent a heteroaryl radical, represents a group independently selected from 2-pyridyl, 2-pyrimidyl, N-phenyl-2-indolyl, 2-indolyl, wherein the mentioned heteroaryl radicals have no further substitutions.
[054] According to a variant, each of the radicals R1 and R3 represents a heteroaryl radical selected from pyridyl and pyrimidyl and, in particular, 2-pyridyl and 2-pyrimidyl,
[055] wherein each of the radicals R2 and R4 represents a group independently selected from -alkyl (C1-C12), -cycloalkyl (C3-C12), - hetero-cycloalkyl (C3-C12), -aryl (C6-C20 ); and
[056] the radicals R1 and R3 and R2 and R4, if they represent -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12) or -aryl (C6-C20), may be, each independently substituted with one or more of the above-described substituents.
[057] In one embodiment, each of the radicals R1 and R3 represents a heteroaryl radical having six ring atoms and each of the radicals R2 and R4 represents -(C1-C12)alkyl;
[058] where
[059] each of the radicals R1, R3 may independently be substituted with one or more of the substituents described above.
[060] According to a variant, the compound has a structure according to one of structural formulas (8), (14) and (15):


[061] Diphosphine compounds according to the invention can be obtained, for example, by reacting ferrocene with butyl lithium and a chlorophosphine compound.
[062] Therefore, the invention also concerns new chlorophosphine compounds that can be used as precursors for the synthesis of the diphosphine compounds according to the invention. The diphosphine compounds according to the invention have the structural formula (II)

[063] wherein R5 is a -heteroaryl (C6-C20) radical having at least six ring atoms;
[064] R6 represents a group selected from -alkyl (C1C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6-C20), -heteroaryl (C3-C20); and
[065] each of the symbols R5 and R6, if they represent a radical -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6-C20), - heteroaryl ( C3-C20) or -heteroaryl (C6-C20),
[066] may be independently replaced with one or more substituents selected from:
[067] -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -O-alkyl (C1-C12), -O-alkyl (C1-C12)-aryl (C6 -C20), -O-cycloalkyl (C3-C12), -S-alkyl (C1-C12), -S-cycloalkyl (C3-C12), -COO-alkyl (C1-C12), -COO- cycloalkyl (C3 -C12), -CONH-alkyl (C1-C12), -CONH-cycloalkyl (C3-C12), -CO-alkyl (C1-C12), -CO-cycloalkyl (C3-C12), -N-[alkyl ( C1-C12)]2, -aryl(C6-C20), -aryl(C6-C20)-alkyl(C1-C12), -aryl(C6-C20)-O-alkyl(C1-C12), -heteroaryl ( C3C20), -heteroaryl(C3-C20)-alkyl(C1-C12), -heteroaryl(C3-C20)-O-alkyl(C1-C12), -COOH, -OH, -SO3H, -NH2, halogen.
[068] According to a variant, each of the radicals R5 and R6, if they represent -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6-C20) , -heteroaryl(C3-C20) or -heteroaryl(C6-C20), may be independently substituted with one or more substituents selected from -alkyl(C1-C12), -cycloalkyl(C3-C12), -heterocycloalkyl(C3-C12 ), -O-alkyl (C1-C12), -O-alkyl (C1-C12)-aryl (C6-C20), -O-cycloalkyl (C3-C12), -S-alkyl (C1-C12), - S-cycloalkyl(C3-C12), -aryl(C6-C20), -aryl(C6-C20)-alkyl(C1-C12), -aryl(C6-C20)-O-alkyl(C1-C12), - heteroaryl (C3-C20), -heteroaryl (C3-C20) alkyl (C1-C12), -heteroaryl (C3-C20)-O-alkyl (C1-C12), -COOH, -OH, -SO3H, -NH2, halogen
[069] According to a variant, each of the radicals R5 and R6, if they represent -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6-C20) , -heteroaryl(C3-C20) or -heteroaryl(C6-C20), may be independently substituted with one or more substituents selected from -alkyl(C1-C12), -cycloalkyl(C3-C12), -O-alkyl(C1 -C12), -O-alkyl(C1-C12)-aryl(C6-C20), -O-cycloalkyl(C3-C12), -aryl(C6-C20), -aryl(C6-C20)-alkyl(C1 -C12), -aryl(C6-C20)-O-alkyl(C1-C12), -heteroaryl(C3-C20), -heteroaryl(C3-C20)-alkyl(C1-C12), -heteroaryl(C3-C20) )-O-alkyl (C1-C12).
[070] According to a variant, each of the radicals R5 and R6, if they represent -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6-C20) , -heteroaryl(C3-C20) or -heteroaryl(C6-C20), can be independently substituted with one or more substituents selected from -alkyl(C1-C12), -O-alkyl(C1-C12)-aryl(C6- C20), -heteroaryl(C3-C20), -heteroaryl(C3-C20)-alkyl(C1-C12), -heteroaryl(C3-C20) -O-alkyl(C1-C12).
[071] According to a variant, each of the radicals R5 and R6, if they represent -alkyl (C1-C12), -cycloalkyl (C3-C12), -heterocycloalkyl (C3-C12), -aryl (C6-C20) , -heteroaryl(C3-C20) or -heteroaryl(C6-C20), can be independently substituted with one or more substituents selected from -alkyl(C1-C12) and -heteroaryl(C3-C20).
[072] In one variant, the radical R6 is unsubstituted if it represents -alkyl(C1-C12), -cycloalkyl(C3-C12) or -heterocycloalkyl(C3-C12) and may be substituted as described, if so radical R6 represents -aryl(C6C20), -heteroaryl(C3-C20) or -heteroaryl(C6-C20).
[073] In one embodiment, the radicals R5 and R6 are unsubstituted.
[074] In one embodiment, the radical R6 represents a group selected from -alkyl (C1-C12), -aryl (C6-C20), -heteroaryl (C3-C20). More preferably, the radical R6 represents a group selected from -(C1-C12)alkyl, the radical R6 may be substituted as described above.
[075] In one embodiment, the radical R5 represents a heteroaryl radical having six to ten ring atoms. Preferably, the radical R5 represents a heteroaryl radical having six ring atoms.
[076] According to a variant, the radical R5 represents a group selected from pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl, in which the mentioned heteroaryl radicals can also be substituted as described above . Preferably, the radical R5 represents a group selected from 2-pyridyl, 2-pyrimidyl, 2-indolyl, wherein the heteroaryl radicals mentioned can also be substituted as described above. More preferably, the radical R5 represents a group selected from 2-pyridyl, 2-pyrimidyl, N-phenyl-2-indolyl, 2-indolyl, in which the mentioned heteroaryl radicals have no further substitutions. Even more preferably, the radical R5 represents a group selected from pyridyl and pyrimidyl and, in particular, 2-pyridyl and 2-pyrimidyl.
[077] In one embodiment, the chlorophosphine compound is chloro-2-pyridyl-tert-butylphosphine.
[078] The invention further relates to complexes comprising Pd and a diphosphine compound according to the invention. In these complexes, the diphosphine compound according to the invention serves as a bidentate ligand for the metal atom. Complexes serve, for example, as catalysts for alkoxycarbonylation. With the complexes according to the invention, it is possible to achieve high yields in the alkoxy-carbonylation of a wide range of different ethylenically unsaturated compounds.
[079] The complexes according to the invention can also further comprise ligands that are coordinated with the metal atom. These are, for example, ethylenically unsaturated compounds or anions. Suitable additional binders include, for example, styrene, acetate anions, maleimides (e.g. N-methyl maleimide), 1,4-naphthoquinone, trifluoroacetate anions or chloride anions.
[080] The invention further relates to the use of a diphosphine compound according to the invention for the catalysis of an alkoxy-carbonylation reaction. The compound according to the invention can in particular be used as a metal complex according to the invention.
[081] The invention also relates to a process comprising the process steps consisting of: a) initially loading an ethylenically unsaturated compound; b) adding a diphosphine compound according to the invention and a compound comprising Pd;
[082] or adding a complex according to the invention comprising Pd and a diphosphine compound according to the invention;
[083] c) adding an alcohol;
[084] d) feed CO;
[085] e) heating the reaction mixture, with conversion of the ethylenically unsaturated compound into an ester.
[086] In this process, the process steps a), b), c) and d) can be performed in any desired sequence. However, typically, the addition of CO is carried out after the coreactants have been initially loaded in steps a) to c). Steps d) and e) can be carried out simultaneously or successively. Furthermore, the CO can also be fed in two or more steps, in such a way that, for example, a portion of the CO is fed at first switching on, then the mixture is heated and then another portion of CO is fed.
[087] The ethylenically unsaturated compounds used as reagent in the process according to the invention contain one or more carbon-carbon double bonds. These compounds are also hereinafter referred to as olefins for the sake of simplicity. Double bonds can be terminal or internal.
[088] Preferred are ethylenically unsaturated compounds having 2 to 30 carbon atoms, preferably 2 to 22 carbon atoms and more preferably 2 to 12 carbon atoms.
[089] According to a variant, the ethylenically unsaturated compound comprises 4 to 30 carbon atoms, preferably 6 to 22 carbon atoms, more preferably 8 to 12 carbon atoms and even more preferably 8 carbon atoms .
[090] The ethylenically unsaturated compounds may, in addition to one or more double bonds, contain other functional groups. Preferably, the ethylenically unsaturated compound comprises one or more functional groups selected from carboxyl, thiocarboxyl, sulfa, sulfinyl, carboxylic anhydride, imide, carboxylic ester, sulfonic ester, carbamoyl, sulfamoyl, cyano, carbonyl, carbonthioyl, hydroxyl, sulfhydryl, amino groups , ether, thioether, aryl, heteroaryl or silyl and/or halogen substituents. Simultaneously, the ethylenically unsaturated compound preferably comprises a total of 2 to 30 carbon atoms, preferably 2 to 22 carbon atoms and more preferably 2 to 12 carbon atoms.
[091] In one embodiment, the ethylenically unsaturated compound does not comprise any functional groups other than carbon-carbon double bonds.
[092] In a particularly preferred embodiment, the ethylenically unsaturated compound is a non-functionalized alkene having at least one double bond and 2 to 30 carbon atoms, preferably 6 to 22 carbon atoms, more preferably 8 to 12 carbon atoms and even more preferably 8 carbon atoms.
[093] Suitable ethylenically unsaturated compounds include, for example:
[094] ethene;
[095] propene;
[096] C4 olefins such as 1-butene, cis-2-butene, trans-2-butene, mixture of cis- and trans-2-butene, isobutene, 1,3-butadiene; refined I to III, crack-C4;
[097] C5 olefins, 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene;
[098] C6 olefins such as tetramethylethylene, 1,3-hexadiene, 1,3-cyclohexadiene;
[099] C7 olefins such as 1-methyl-cyclohexene, 2,4-heptadiene, norbornadiene;
[100] C8 olefins such as 1-octene, 2-octene, cyclooctene, di-n-butene, diisobutene, 1,5-cyclooctadiene, 1,7-octadiene;
[101] C9 olefins such as tripropene;
[102] C10 olefins such as dicyclopentadiene;
[103] undecenes;
[104] dodecenes;
[105] internal C14 olefins;
[106] internal C15 to C18 olefins;
[107] C15 to C30 internal, linear or branched, cyclic, acyclic or partially cyclic olefins;
[108] tri-isobutene, tri-n-butene;
[109] terpenes such as limonene, geraniol, farnesol, pinene, myrcene, carvone, 3-carene;
[110] polyunsaturated compounds having 18 carbon atoms, such as linoleic acid or linolenic acid;
[111] esters of unsaturated carboxylic acids, such as vinyl esters of acetic or propionic acid, alkyl esters of unsaturated carboxylic acids, methyl or ethyl esters of acrylic acid and methacrylic acid, oleic esters, methyl or ethyl oleate, linoleic acid esters or linolenic;
[112] vinyl compounds such as vinyl acetate, vinyl-cyclohexene, styrene, alpha-methyl-styrene, 2-isopropenylnaphthalene;
[113] 2-methyl-2-pentenal, methyl 3-pentenoate, methacrylic anhydride.
[114] In a process variant, the ethylenically unsaturated compound is selected from propene, 1-butene, cis- and/or trans-2-butene, or mixtures thereof.
[115] According to a process variant, the ethylenically unsaturated compound is selected from 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3- methyl-1-butene, or mixtures thereof.
[116] In a preferred embodiment, the ethylenically unsaturated compound is selected from ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethyl-ethylene, heptene, n-octene, 1-octene, 2 -octene, or mixtures thereof.
[117] In one embodiment, a mixture of ethylenically unsaturated compounds is used. In the context of the present invention, a mixture refers to a composition comprising at least two ethylenically unsaturated compounds, wherein the proportion of each ethylenically unsaturated compound is preferably at least 5% by weight, based on the total weight of the Mix.
[118] It is preferred to use a mixture of ethylenically unsaturated compounds, each of which has 2 to 30 carbon atoms, preferably 4 to 22 carbon atoms, more preferably 6 to 12 carbon atoms, and furthermore more preferably 8 to 10 carbon atoms.
[119] Suitable mixtures of ethylenically unsaturated compounds are those designated as raffinates I to III. Raffinate I comprises 40% to 50% isobutene, 20% to 30% 1-butene, 10% to 20% cis- and trans-2-butene, up to 1% 1,3-butadiene and 10% to 20% n-butane and isobutane. Raffinate II is a portion of the C4 fraction that is obtained by fracturing naphtha and consists essentially of isomeric n-butenes, isobutane and n-butane, after removal of isobutene from raffinate I. Raffinate III is a portion of the fraction C4 which is obtained from the fracture of naphtha and which consists essentially of isomeric n-butenes and n-butane.
[120] Another suitable mixture is di-n-butene, also referred to as dibutene, DNB or DnB. Di-n-butene is a mixture of C8 olefin isomers that is obtained from the dimerization of mixtures of 1-butene, cis-2-butene and trans-2-butene. In industry, raffinate II or raffinate III streams are normally subjected to a catalytic oligomerization, in which the butanes present (n/iso) appear unchanged and the olefins present are totally or partially converted. As well as dimeric di-n-butene, higher oligomers (C12 tributene, C16 tetrabutene) are normally also formed, which need to be removed by distillation after the reaction. These can also be used as reagents.
[121] In a preferred embodiment, a mixture comprising isobutene, 1-butene, cis- and trans-2-butene is used. Preferably, the mixture comprises 1-butene, cis- and trans-2-butene.
[122] The alkoxy carbonylation according to the invention is catalyzed by the Pd complex according to the invention. The Pd complex can be added in process step b) in the form of a preformed complex comprising Pd and the phosphine linkers according to the invention or it can be formed in situ from a compound comprising Pd and the free phosphine ligand. In this context, the compound comprising Pd is also referred to as catalyst precursor.
[123] In case the catalyst is formed in situ, then the binder can be added in excess, in such a way that the unbound binder is also present in the reaction mixture.
[124] In the case of the complex being added early on, it is also possible to add more ligand, in such a way that unbound ligand is present in the reaction mixture.
[125] In one embodiment, the compound comprising Pd is selected from palladium dichloride (PdCl2), palladium(II) acetylacetonate [Pd(acac)2], palladium(II) acetate [Pd(OAc) )2], dichloro-(1,5-cyclooctadiene)-palladium(II) [Pd(cod)2Cl2], bis(dibenzylidene-acetone)-palladium [Pd(dba)2], bis-(acetonitrile) -dichloropalladium(II) [Pd(CH3CN)2Cl2], palladium(cinnamyl) dichloride [Pd(cinnamyl)Cl2].
[126] Preferably, the compound comprising Pd is PdCl2, Pd(acac)2 or Pd(OAc)2. PdCl2 is particularly suitable.
[127] The alcohol in process step c) can be branched or linear, cyclic, alicyclic, partially cyclic or aliphatic and is, in particular, a C1 to C30 alkanol. It is possible to use monoalcohols or polyalcohols.
[128] The alcohol in process step c) preferably comprises 1 to 30 carbon atoms, more preferably 1 to 22 carbon atoms and even more preferably 1 to 12 carbon atoms. It can be a monoalcohol or a polyalcohol.
[129] Alcohol may contain, in addition to the hydroxyl group or more hydroxyl groups, other functional groups. Preferably, the alcohol may further comprise one or more functional groups selected from carboxyl, thiocarboxyl, sulfo, sulfinyl, carboxylic anhydride, imide, carboxylic ester, sulfenic ester, carbamoyl, sulfamoyl, cyano, carbonyl, carbonthioyl, sulfhydryl, amino, ether, thioether, aryl, heteroaryl or silyl and/or halogen substituents.
[130] In one embodiment, the alcohol does not comprise any functional groups other than hydroxyl groups.
[131] Alcohol may contain unsaturated and aromatic groups. However, an aliphatic alcohol is preferred.
[132] In the context of the present invention, an aliphatic alcohol designates an alcohol that does not comprise any aromatic groups, i.e., for example, an alkanol, alkenol or alkynol.
[133] In one embodiment, the alcohol is an alkanol having one or more hydroxyl groups and 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms, more preferably 1 to 12 carbon atoms, and, even more preferably, 1 to 6 carbon atoms.
[134] According to a process variant, the alcohol in process step c) is selected from the group of monoalcohols.
[135] According to a process variant, the alcohol in process step c) is selected from: methanol, ethanol, 1-propanol, isopropanol, isobutanol, tert-butanol, 1-butanol, 2-butanol, 1-pentanol , 2-pentanol, 3-pentanol, 1-hexanol, cyclohexanol, phenol, 2-ethylhexanol, isononanol, 2-propylheptanol.
[136] In a preferred embodiment, the alcohol in process step c) is selected from methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3 -pentanol, cyclohexanol, phenol and mixtures thereof.
[137] According to a process variant, the alcohol in process step c) is selected from the group of polyalcohols.
[138] According to a process variant, the alcohol in process step c) is selected from diols, triols, tetraols.
[139] According to a process variant, the alcohol in process step c) is selected from cyclohexane-1,2-diol, ethane-1,2-diol, propane-1,3-diol, glycerol, butane-1,2,4-triol, 2-hydroxymethylpropane-1,3-diol, 1,2,6-trihydroxyhexane, pentaerythritol, 1,1,1-tri(hydroxy-methyl)-ethane, catechol, resorcinol and hydroxyhydroquinone.
[140] According to a process variant, the alcohol in process step c) is selected from sucrose, fructose, mannose, sorbose, galactose and glucose.
[141] According to a preferred process variant, the alcohol in process step c) is selected from methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol.
[142] According to a particularly preferred variant of the process, the alcohol in process step c) is selected from methanol, ethanol.
[143] According to a process variant, the alcohol in process step c) is methanol.
[144] According to a process variant, the alcohol in process step c) is used in excess.
[145] According to a process variant, the alcohol in process step c) is used simultaneously as a solvent.
[146] According to a variant of the process, another solvent is used, which is selected from toluene, xylene, tetrahydrofuran (THF) and methylene chloride (CH2Cl2).
[147] The CO is fed in step d) preferably at a partial pressure of CO of between 0.1 and 10 MPa (1 to 100 bar), preferably between 1 and 8 MPa (10 to 80 bar) and more preferably between 2 and 4 MPa (20 to 40 bar).
[148] Preferably, the reaction mixture is heated in step e) of the process according to the invention to a temperature comprised between 10°C and 180°C, preferably between 20°C and 160°C and more preferably between 40°C and 120°C, to convert the ethylenically unsaturated compound to an ester.
[149] The molar ratio between ethylenically unsaturated compound initially loaded in step a) and the alcohol added in step c) is preferably comprised between 1:1 and 1:20, more preferably between 1:2 and 1:10, and further more preferably, between 1:3 and 1:4.
[150] The mass ratio between Pd and the ethylenically unsaturated compound initially loaded in step a) is preferably comprised between 0.001% and 0.5% by weight, preferably between 0.01% and 0.1% by weight and more preferably between 0.01% and 0.05% by weight.
[151] The molar ratio between the diphosphine compound according to the invention and the Pd is preferably comprised between 0.1:1 and 400:1, preferably between 0.5:1 and 400:1, more preferably between 1 :1 and 100:1 and even more preferably between 2:1 and 50:1.
[152] Preferably, the process is conducted with the addition of an acid. Therefore, according to a variant, the process further comprises a step c'): adding an acid to the reaction mixture. Preferably this may be a BrOnsted or Lewis acid.
[153] Suitable Br0nsted acids preferably have a pKa < 5 and preferably an acid strength of pKa < 3. The acid strength pKa described is based on the pKa value determined under standard conditions (25°C). 1.01325 bar). In the case of a polyprotic acid, the acid pKa strength, in the context of the present invention, refers to the pKa value of the first protolysis step.
[154] Preferably, the acid is not a carboxylic acid.
[155] Suitable Br0nsted acids include, for example, perchloric acid, sulfuric acid, phosphoric acid, methylphosphonic acid and sulfonic acids. Preferably, the acid is sulfuric acid or a sulfonic acid. Suitable sulfonic acids include, for example, methanesulfonic acid, trifluoromethanesulfonic acid, tert-butanesulfonic acid, p-toluenesulfonic acid (PTSA), 2-hydroxypropane-2-sulfonic acid, acid 2,4,6-trimethylbenzenesulfonic acid and dodecylsulfonic acid. Particularly preferred acids include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid.
[156] A Lewis acid used can be, for example, aluminum triflate.
[157] According to a variant, the amount of acid added in step c') is between 0.3% and 40% mol, preferably 0.4% and 15% mol, more preferably between 0.5 % and 5 mol%, and even more preferably 0.6% and 3 mol%, based on the molar amount of the ethylenically unsaturated compound used in step a).
[158] Description of figures
[159] Figure 1: methoxy-carbonylation of ethylene with 3 and 8 at 80°C and 40 bar CO.
[160] Figure 2: methoxy-carbonylation of ethylene with 3 and 8 at 60°C and 20 bar CO (constant pressure).
[161] Figure 3: Alcohol variation in the methoxy-carbonylation of ethene with binder 8 at 80°C and CO pressure of 30 bar.
[162] Figure 4: methoxy-carbonylation experiments on propene, 1-butene and 2-butene, at 100°C and 40 bar, with binder 8.
[163] Figure 5: Methoxy-carbonylation of raffinate 1 with binder 8 at 100°C and 60 bar CO pressure.
[164] Figure 6: Methoxy-carbonylation of raffinate 1, at 100°C and 50 bar, with binder 8.
[165] Figure 7: Methoxy-carbonylation of a mixture of propene, 1-butene and 2-butene, at 100°C and 60 bar, with binder 8.
[166] Figure 8: Methoxy-carbonylation of a mixture of C5 olefins, at 100°C and 50 bar CO pressure, with binder 8.
[167] Figure 9: Methoxy-carbonylation of di-n-butene with binder 8, at 120°C and 20 bar, with constant CO pressure.
[168] Figure 10: Methoxy-carbonylation of di-n-butene with 3 and 8 at 120°C and 40 bar CO.
[169] Figure 11: Performance curve for the methoxy-carbonylation of di-n-butene with 8 as the binder, at a total constant pressure of 20 bar and 120°C.
[170] Figure 12: gas consumption curves for reactions with 3 and 8.
[171] Examples
[172] The invention is hereafter described in more detail by means of working examples.
[173] General Procedures
[174] All of the following preparations were carried out under a protective gas using standard Schlenk techniques. Solvents were dried over suitable desiccants prior to use (Purification of Laboratory Chemicals, W.L.F. Armarego (Author), Christina Chai (Author), Butterworth Heinemann (Elsevier), 6th edition, Oxford 2009).
[175] Phosphorus trichloride (Aldrich) was distilled under argon prior to use. All preparatory operations were carried out in containers subjected to an oven. The products were characterized by means of NMR spectroscopy. Chemical shifts (δ) are given in p.p.m. The 31P NMR signals were referenced as follows: SR31P = SR1H * (BF31P / BF1H) = SR1H * 0.4048. (Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Robin Goodfellow and Pierre Granger, Pure Appl. Chem., 2001, 73, 1795-1818; Robin K. Harris, Edwin D. Becker, Sonia M Cabral de Menezes, Pierre Granger, Roy E. Hoffman and Kurt W. Zilm, Pure Appl. Chem., 2008, 80, 59-84).
[176] The recording of nuclear resonance spectra were performed on a Bruker Avance 300 or Bruker Avance 400, gas chromatography analysis on Agilent GC 7890A, elemental analysis on Leco TruSpec CHNS and Varian ICP-OES 715, and spectrometry of ESI-TOF putty in Thermo Electron Finnigan MAT 95-XP and Agilent 6890 N/5973.
[177] Preparation of precursor E
[178] Preparation of chloro-2-pyridyl-tert-butylphosphine
[179] Grignard reagent for the synthesis of chloro-2-pyridyl-t-butylphosphine is prepared by the “Knochel method” with isopropyl-magnesium chloride (Angew. Chem. 2004, 43, 2222-2226). Processing is carried out according to the method of Budzelaar (Organometallics 1990, 9, 1222-1227).

[180] Scheme 2: synthesis of precursor E
[181] Under an argon atmosphere, an amount of 8.07 mL of a 1.3 M isopropyl-magnesium chloride solution (Knochel's reagent) is introduced into a 50 mL round bottom flask with a magnetic stirrer and a partition and cooled to -15°C. Next, 953.5 µL (10 mmol) of 2-bromopyridine is quickly added dropwise. The solution immediately turns yellow. Allow to warm to -10°C. The reaction conversion is determined as follows: about 100 µl of solution is taken out and introduced into 1 ml of a saturated ammonium chloride solution. If the solution “bubbles” then not much Grignard reagent has formed. The aqueous solution is extracted with an ether pipette and the organic phase is dried over Na2SO4. The GC of the ethereal solution is recorded. When a large amount of pyridine is formed compared to 2-bromopyridine, conversions are high. At -10°C, little conversion is observed. After warming to room temperature and stirring for 1-2 hours, the reaction solution turns brown-yellow in color. A GC test shows a complete conversion. At this point, the Grignard solution can be slowly added, dropwise and with the aid of a syringe pump, to a solution of 1.748 g (11 mmol) of dichloro-tert-butyl-phosphine in 10 mL of THF, to which was previously cooled to -15°C. It is important that the dichloro-tert-butyl-phosphine solution is cooled. At room temperature, considerable amounts of dipyridyl-tert-butyl-phosphine would be obtained. A clear yellow solution initially forms, which then becomes cloudy. Allow the mixture to warm to room temperature and stir overnight. The solvent is removed under high vacuum and an off-white solid is obtained which is brown in places. The solid is suspended with 20 ml of heptane and the solid is subjected to comminution in an ultrasonic bath. After allowing the white solid to settle, the solution is decanted. The operation is repeated twice with 10-20 ml of heptane each time. After concentrating the heptane solution under high vacuum, it is distilled under reduced pressure. At 4.6 mbar, 120°C oil bath and 98°C distillation temperature, the product can be distilled. 1.08 g of a colorless oil are obtained. (50%).
[182] Analytical data: 1H NMR (300 MHz, C6D6): δ 8.36 (m, 1H, Py), 7.67 (m, 1H, Py), 7.03-6.93 (m, 1H, Py), 6.55-6.46 (m, 1H, Py), 1.07 (d, J = 13.3 Hz, 9H, t-Bu).
[183] 13C NMR (75 MHz, C6D6): δ 162.9, 162.6, 148.8, 135.5, 125.8, 125.7, 183.8, 35.3, 34.8, 25.9 and 25.8.
[184] 31P NMR (121 MHz, C6D6) δ 97.9.
[185] MS (EI) m:z (relative intensity) 201 (M+.2), 147 (32), 145 (100), 109 (17), 78 (8), 57.1 (17).
[186] Preparation of compound 8
[187] Preparation of 1,1'-bis-(tert-butyl-2-pyridylphosphino)-ferrocene

[188] Scheme 3: Synthesis of Compound 8
[189] Variant A
[190] 474.4 mg (2.55 mmol) of sublimated ferrocene is weighed into a 50 mL round bottom flask with a magnetic stirrer and a septum, and the flask is purged. After adding 15 ml of heptane, the ferrocene is completely dissolved. Next, 841 µL of tetramethyl-ethylene-diamine (1.1 eq, 5.61 mmol) is added all at once and 2.04 mL of BuLi (2.5 M in hexane, 2.0 eq., 5.1 mmol). After 2-3 hours, an orange solid precipitates. The mixture is stirred overnight, the heptane solution is decanted and the orange solid is washed twice with heptane. Then an additional 10 ml of heptane is added and the suspension is cooled to -70°C. 1.08 g (2.1 eq., 5.36 mmol) of chloro-2-pyridyl-tert-butylphosphine are dissolved in 7 mL of heptane. The solution is cloudy and must be filtered through Celite. A small amount of an insoluble white solid forms. This solution is added dropwise to the dilithium ferrocene solution. While warming to room temperature, the color of the orange suspension lightens. To complete the reaction, the reaction solution is heated under reflux for about 1 hour. A clear orange solution and a white precipitate form.
[191] 7 mL of argon-saturated water is added to the suspension. The white precipitate dissolves. After removing the aqueous phase, the operation is repeated twice. This causes the heptane phase to become cloudy. After complete removal of the organic phase under high vacuum, an orange oily residue remains. This residue is taken up in 10 ml of ether and dried over Na2SO4. (crude yield 913 mg). At -28°C, no precipitate or crystal formation is observed overnight. Nor does a mixture of diethyl ether and heptane give rise to crystallization at -28°C. 31P NMR analysis of the solution again shows the product peak, now at 7.39 p.p.m., and a signal at 40.4 p.p.m. The product can be purified by column chromatography. The ether solution is applied to a short column, which is eluted with diethyl ether under argon. The orange product comes out at the front and can be picked up easily. After removing the ether, 241 mg (16%) of an orange viscous oil with a purity of about 95% are obtained.
[192] Variant B
[193] Batch size: 650.17 mg (3.495 mol) ferrocene (sublimated), 2.8 mL (2 eq., 6.99 mmol) 2.5 M BuLi (n-butyllithium), 1.1 mL (2.1 eq., 7.3 mmol) of tetramethyl-ethylene-diamine and 1.48 g (2.1 eq., 7.34 mmol) of chloro-2-pyridyl-tert-butylphosphine.
[194] The dilithium ferrocene salt is again prepared in 15 mL of heptane. Dissolve chloro-2-pyridyl-tert-butylphosphine in 10 mL of THF instead of heptane, as chlorophosphine dissolves better in THF. Work-up is also optimised: after heating to boiling under reflux, the reaction mixture is quenched with just 1 ml of H2O and the solvent (heptane and THF) is completely removed under high vacuum. The dark yellow/orange fibrous solid is taken up in 8 ml of H2O and 15 ml of dimethyl ether and stirred for 1 minute. After phase separation, the aqueous phase is removed with the aid of a syringe and the organic phase is washed three times with H2O. The organic phase is dried over Na2SO4 and filtered. The Na 2 SO 4 product is washed 3 times with 10 ml of diethyl ether each time until an almost colorless solution is obtained. The dark orange solution is concentrated to a volume of 10 ml and passed through a column comprising silica gel 60 under argon. The eluent used is again diethyl ether. The filtrate is much brighter and more orange. After removing the solid, 1.16 g of an orange fibrous solid is obtained. (64%).
[195] Preparation of compound 10 (comparison compound)
[196] Starting from 1,1'-(ferrocenediyl)-phenyl-phosphine, the isolated phosphine ring is opened with PhLi and the resulting intermediate is quenched with chlorophosphine.

[197] Scheme 4: Synthesis of a ferrocenyl ligand:

[198] Scheme 5: Synthesis of Compound 10
[199] A 50 mL round bottom flask, with a magnetic stir bar and nitrogen bond, is initially charged with 1.13 mmol (565 µL) of phenyllithium (PhLi) and slowly added, drop by drop, a solution of 1.03 mmol (300 mg) of cyclic phosphine in 20 ml of heptane, with the aid of a syringe pump. The Li salt is washed twice with heptane and mixed with 6 ml of heptane. A heptane solution of 0.8 eq (0.824 mmol, 131 µL) of ClPiPr2 in 7 mL of heptane is added dropwise to the suspension at room temperature. The red-brown suspension hardly changes color. After stirring for 20 minutes, the suspension is heated under reflux for 1.5 hours. The solid is slightly lighter in color. The solvent is completely removed and the red-brown residue is taken up in H2O and ether. The organic phase is washed twice with H2O and dried over Na2SO4. A 31P spectrum of the ether phase is recorded. The spectrum shows 2 singlets. Chlorophosphine was completely consumed. The ether phase is dried and 300 mg (yield: 61%) of a brown-yellow oil are obtained, which is dissolved in MeOH in a water bath at 65°C. The solution is placed in a freezer (-78°C) overnight. 76 mg of a brown-yellow oil precipitated and analyzed by NMR spectroscopy.
[200] 1H NMR (300 MHz, CDCl3) δ 7.46-7.23 (m, 10H, Ph), 4.36 (m, 2H, Cp), 4.21 (m, 2H, Cp), 34 .24 (m, 4H, Cp), 1.88 (m, 2H, iPr), 1.15-0.96 (m, 12H, iPr).
[201] 13C NMR (75 MHz, CDCl3) δ 139.9 (J = 9.8 Hz, Ph), 133.4 (J = 19.2 Hz, Ph), 128.4, 128.1, 128, 0 (Ph), 77.1, 76.8, 76.2, 76.1 (Cp), 73.5 (J = 14.5 Hz, Cp), 72.8 (J = 2.9 Hz, Cp ), 71.9 (J = 10.5 Hz, Cp), 72.1 (Cp), 23.3 (J = 11.0 Hz, iPr), 20.1, 20.0, 19.9, 19 .8 (iPr).
[202] 31P NMR (121 MHz, C6D6) δ = 0.88 and -16.62.
[203] Preparation of compound 14
[204] Preparation of bis-(2-pyridyl-n-butylphosphino)-ferrocene

[205] Scheme 6: Synthesis of Compound 14
[206] In a 25 mL round bottom flask with a magnetic stir bar and a cap, cool 1.45 mL (2.33 mmol) of 1.6 M BuLi BuLi to -78°C (melting ice /EtOH). To this solution, 208 µL (2.18 mmol) of 2-bromopyridine dissolved in 2 mL of ether is added dropwise. The reaction mixture turns yellow first and then changes color to orange but remains clear. After stirring for 15 minutes, a sample is taken (100 µL) and quenched with NH4CI/H2O. According to GC, in addition to pyridine, several other compounds were formed. Then, at this temperature, 1,1'-bis-(dichlorophosphine)-ferrocene dissolved in 2 ml of ether is added dropwise and the reaction mixture is allowed to heat up overnight. A pale orange suspension forms, which is filtered through a frit (G4). A clear orange ether solution is obtained. After removing the solvent under reduced pressure, 173 mg of an orange solid are obtained and this is subjected to chromatography under argon. The mixture is first introduced into a column with pure diethyl ether (column parameters: diameter 4 cm, silica gel 60), and 50 mg of a yellow fibrous solid are obtained. Column the solid again with 2:1 heptane/diethyl ether, and obtain 31 mg of bis-(2-pyridyl-n-butylphosphino)ferrocene (18%).
[207] 1H NMR (300 MHz, C6D6): δ 8.54 (d, J = 4.6 Hz, 2H, py), 7.43-7.32 (m, 2H, py), 6.94- 6.88 (m, 2H, py), 6.58-6.49 (m, 2H, py), 4.47 (m, 1H, ferrocenyl), 4.37 (m, 1H, ferrocenyl), 4. 33 (m, 1H, ferrocenyl), 4.23-4.14 (m, 5H, ferrocenyl), 2.56-2.44 (m,2H, CH2), 2.23 (m, 2H, CH2), 1.80-1.65 (m, 4H, CH2), 1.57-1.39 (m, 4H, CH2), 0.93-0.85 (m, 6H, CH3).
[208] 13C NMR (75 MHz, C6D6): δ 166.5, 166.2, 166.1, 150.1, 134.8 and 122.1 (py), 78.7, 78.6, 78, 5, 74.9, 74.7, 74.3, 74.1, 72.8, 72.6, 72.1 and 71.7 (ferrocenyl), 29.7, 29.6, 29.5, 29 0.4, 28.2, 28.1, 27.9, 27.8, 24.8, 24.7, 24.6 and 14.1 (CH2), 14.1 (CH3).
[209] 31P NMR (121 MHz, C6D6) δ -24.7 and -24.9.
[210] HRMS (ESI) m/z+ calculated for C28H34FeN2P2 (M+H)+ 517.16197; found: 517,16238.
[211] Preparation of compound 15
[212] Preparation of bis-(2-pyridyl-n-butylphosphino)-ferrocene

[213] Scheme 7: Synthesis of Compound 15
[214] In a 25 mL round bottom flask with a magnetic stirrer, cool to -20°C 5.3 mL (1.1 eq) of a 1.3 M isopropyl-magnesium chloride solution (reagent Knochel) and added in one portion to 603 µL (6.32 mmol) of 2-bromopyridine. The mixture is stirred at -20°C for one hour and then at room temperature for 2 hours to achieve complete conversion. In a second 50 mL round flask, weigh 490.7 mg (1.26 mmol) of 1,1'-bis(dichlorophosphono)-ferrocene into a glove box and, after removal through a small chamber, dissolve in 10 mL of THF. After cooling to -20°C, the Grignard compound prepared above is added dropwise to the orange-yellow solution via a syringe pump. After dropwise addition, the solution is warmed to 0°C and a brown/black solution forms. To complete the reaction, the mixture is refluxed for a further 20 minutes. The next day, 0.5 ml of water is added to the black reaction solution and the solution clears in terms of color to become a dark red/brown suspension. The solvent is removed under high vacuum and the residue is taken up in 15 ml of ether and 10 ml of H2O. The suspension is filtered through Celite and an orange organic phase and a green aqueous phase are obtained. The organic phase is dried over Na2SO4 and, after removing the ether, 410 mg of a green/black solid are obtained. The almost black dark green solid is columned in pure diethyl ether. After removing the ether, 112 mg of yellow product 15 are obtained.
[215] 1H NMR (300 MHz, C6D6): δ 8.56 (m, 1H, py), 8.48-8.38 (m, 2H, py), 7.58 (m, 1H, py), 7.39-7.27 (m, 2H, py), 7.00-6.84 (m, 3H, py), 6.65-6.56 (m, 1H, py), 6.55-6 .44 (m, 2H, py), 4.50-4.39 (m, 3H, ferrokenyl), 4.26-4.18 (m, 2H, ferrokenyl), 4.18-4.12 (m, 1H, ferrocenyl), 4.12-4.04 (m, 2H, ferrocenyl), 2.69 (oct, J = 7.0 Hz, 1H ipr), 1.14-0.94 (m, 6H, ipr ).
[216] 13C NMR (75 MHz, C6D6): δ 165.4, 163.7, 150.2, 150.0, 149.9, 134.9, 216.8, 134.7, 131.1, 130.6 , 129.1, 128.8, 128.6, 122.7, 122.2, and 122.0 (py), 77.5, 77.3, 76.9, 76.5, 75.4, 75 .2, 74.8, 74.6, 74.4, 72.8, 72.7, 72.5, 72.0 and 71.9 (ferrocenyl), 32.2, 28.3, 28.2, 23.0, 20.6, 20.3, 19.7, 19.5 and 14.3 (ipr).
[217] 31P NMR (121 MHz, C6D6) δ -6.2 and -12.9.
[218] HRMS (ESI) m/z+ calculated for C28H27FeN3P2 (M+H)+ 524.11027; found: 524,11022.
[219] Preparation of compound 19 (comparison compound)

[220] Scheme 8: synthesis of compound 19
[221] 0.93 g of ferrocene is dissolved in 50 mL of absolute heptane in a three-way flask equipped with a thermometer, a magnetic stirrer, and a reflux condenser. 1.3 g of TMEDA (1.6 ml) and 7.5 ml of n-BuLi/hexane 1.6 M are added via syringe at room temperature. The solution is left to stand for 5 hours. The orange/brown crystals of the dilithium ferrocene precipitate. The supernatant solution is removed by syringe. And 20 ml of absolute heptane are added. Subsequently, the chlorophosphine dissolved in 10 ml of heptane is added dropwise. The mixture is heated under reflux for one hour. After cooling, the organic phase is washed three times with 10 ml each time of degassed water. Concentrate the mixture to dryness and add 10 ml of diethyl ether. The solution is filtered through 10 cm of silica gel 60 under argon with diethyl ether as solvent, concentrated to dryness and allowed to crystallize from a small amount of hot methanol to obtain the desired product with a 50% yield not optimized.
[222] Analysis
[223] 31P (121MHz, CDCl3), - 7.8 s, - 8.15 s.
[224]13C (75 MHz, CDCl3); 137.77, (d, J = 12 Hz), 137.4 (d, J = 11.3 Hz), 134.2 (d, J = 20.3 Hz), 129.1 s, 128.1 ( d, J = 7.5 Hz), 77.4 (d, J = 11.3 Hz), 75.0 (d, J = 26.2 Hz), 74.0 (d, J = 22.3 Hz) ), 72.1 s br, 71.9-71.5 m, 71.1 s, 69.0 s, 27.6 (d, J = 10 Hz), 27.55 8d, J = 10 Hz), 20.3-19.9 m.
[225] 1H (300 MHz, CDCl3): 7.52-7.44 (m, 4H), 7.33-7.23 (m, 6H), 4.23 (sept., J = 1.2 Hz , 1H), 4.1-4.0 (m, 4H), 3.93-3.9 (m, 1H), 3.87-3.84 (m, 1H), 3.58-3, 54 (m, 1H), 2.1-1.9 (m, 2H), 0.99 (d, J = 7 Hz, 3H), 0.94 (d, J = 7 Hz, 3H), 0.83-0.7 (m, 6H).
[226] Preparation of palladium complexes
[227] Experiment 52: Preparation of the K4 complex
[228] Preparation of n2-N-methylmaleimide from [Pd(Cp2Fe)1,1'-(P(2-pyridyl)-(t-butyl))2]] K4

[229] Scheme 9: K4 complex synthesis
[230] In each case, 172.9 mg (0.816 mmol) of palladium precursor (see scheme 9) and 90.64 mg (0.816 mmol) of sublimated N-methyl-maleimide (see experiment 51) are weighed into one. 50 mL Schlenk container in a glove box. 446.6 mg (0.866 mmol) of the viscous orange ferrocene binder 8 is dissolved in 15 mL of heptane and added to the N-methyl maleimide. The solution is heated to 60°C in a water bath until everything dissolves. To obtain a clear orange solution, filter the solution through Celite. Also dissolve the palladium precursor in 10 ml of heptane and filter through Celite. At room temperature, the pale orange solution of binder/N-methyl maleimide to the dark red palladium precursor is added dropwise. The dark red solution lightens in color and a pale yellow solid precipitates. The mixture is kept under stirring overnight and the supernatant solution is decanted after the solids have settled. After washing with heptane twice, the solid is dried under high vacuum and 541 mg (86%) of product is obtained.
[231] Elemental analysis calculated for: C33H39FeN3O2P2Pd: C, 54.01; H, 5.36; N, 5.73; P, 8.44, found: C, 53.44; H, 5.48; N, 5.72; P,8.48.
[232] Experiments with high pressure
[233] Raw materials
[234] Methanol (MeOH)
[235] Ethene (also referred to as ethylene)
[236] The C4 fraction designates a side stream from the so-called steam fractionation process for the production of ethylene and is generally constituted by an extension greater than 95% of a mixture of various linear and branched hydrocarbons that contain four carbon atoms and which can be saturated, monounsaturated or polyunsaturated. The main components of a C4 fraction stream are n-butane, isobutane, isobutene, n-butenes, butadienes.
[237] Raffinate 1 is obtained from the C4 fraction after removal (usually extractive) of butadienes. Raffinate 1 is made up of about 42% isobutene, 26% 1-butene, 17% cis- and trans-2-butene and also 0.3% 1,3-butadiene and 15% n-butane and isobutane. The exact composition may vary due to the source as well as seasonal factors. The values presented are, therefore, merely typical examples, but not limiting.
[238] Raffinate II is a portion of the C4 fraction that occurs during naphtha fractionation and consists essentially of the isomeric n-butenes, isobutane and n-butane, after removal of isobutene from raffinate 1.
[239] Raffinate III is a portion of the C4 fraction that is obtained during the fractionation of naphtha and consists essentially of isomeric n-butenes and n-butane.
[240] 99+% 2-Butene, mixture of cis and trans, Sigma Aldrich, catalog number 36335-9, LOT No. 14205MS.
[241] The isobutene used has a minimum purity of 99.9% (m/m). The manufacturer is Evonik Industries AG, Performance Materials.
[242] Di-n-butene has also been referred to as: dibutene, DNB or DnB.
[243] Di-n-butene is an isomeric mixture of C8 olefins derived from the dimerization of mixtures of 1-butene, cis-2-butene and trans-2-butene. In industry, raffinate II or raffinate III streams are normally subjected to a catalytic oligomerization, in which the butanes present (n/iso) remain unchanged and the olefins present are totally or partially converted. As well as dimeric di-n-butene, higher oligomers (C12 tributene, C16 tetrabutene) are normally also formed, which have to be removed by distillation after the reaction.
[244] A process practiced in the industry for the oligomerization of C4 olefins is called the “OCTOL process”.
[245] In the patent literature, in document DE102008007081A1, for example, an oligomerization based on the OCTOL process is described. EP1029839A1 concerns the fractionation of C8 olefins formed in the OCTOL process.
[246] In general, technical di-n-butene is constituted by an amount of 5% to 30% of n-octenes, 45% to 75% of 3-methyl-heptenes and an amount of 10% to 35 % of 3,4-dimethylhexenes. Preferred streams contain 10% to 20% n-octenes, 55% to 65% 3-methylheptenes and 15% to 25% 3,4-dimethylhexenes.
[247] Para-toluenesulfonic acid has been abbreviated as follows: pTSA, PTSA or p-TSA. In this text, PTSA always refers to para-toluenesulfonic acid monohydrate.
[248] General method for conducting experiments under high pressure
[249] Description of general experiment for batch mode reactions.
[250] Appropriate amounts of substrate, palladium salt, acid and alcohol are mixed under an argon atmosphere in a 50 mL Schlenk vessel, under stirring with a magnetic stirrer.
[251] A 100 mL Parr steel autoclave equipped with a gas inlet valve and gas outlet valve, a digital pressure transducer, a temperature sensor and a ball valve, and a capillary installed for sampling , is liberated from oxygen through a vacuum and argon purge three times. Subsequently, the reaction solution from the Schlenk vessel is introduced through a capillary into the autoclave with an argon countercurrent through the ball valve. Subsequently, the appropriate amount of CO is injected at room temperature and then the autoclave is heated to room reaction temperature (reactions that are not carried out under constant pressure) or the autoclave is heated first to the reaction temperature and then CO is injected through a burette connected to the autoclave through a pressure reducer. This burette is then charged with CO to about 100 bar and, during the reaction, supplies the necessary CO at a constant pressure. This burette has a dead volume of about 30 mL and is provided with a digital pressure transducer. Then, the reaction is carried out at the required temperature for the required time, under stirring. During this operation, through a computer application (Specview by SpecView Corporation) and a Parr 4870 process control and a 4875 power controller, the data for the pressure variation in the autoclave and the gas burette are recorded. This data is used to generate Excel tables, which are used in a later step to create diagrams that show gas consumptions and thus conversions over time. If necessary, through the capillary, samples for GC are collected and analyzed. For this purpose, an exact suitable amount (2-10 ml) of isooctane as an internal standard is also added to the Schlenk vessel. It also gives information regarding the course of the reaction. At the end of the reaction, the autoclave is cooled to room temperature, the pressure is carefully released, isooctane is added, if necessary, as an internal standard, and a GC analysis or, in the case of new products, an analysis by GC-MS is also performed.
[252] General Experimental Method for Autoclave Experiments in Glass Bottles
[253] A 300 mL Parr reactor is used. Coupled to this is an aluminum block of corresponding dimensions which has been produced around it and which is suitable for heating by means of a conventional magnetic stirrer, for example from Heidolph. For the interior of the autoclave, a round metal plate of about 1.5 cm thick was produced, which contains 6 holes corresponding to the outer diameter of the glass vials. Correspondingly to these glass flasks, they are equipped with small magnetic stirrers. These glass vials are supplied with suitable screw caps and caps and are loaded, using a special apparatus produced by glass blowers, under an argon atmosphere with the appropriate reagents, solvents, catalysts and additives. For this purpose, 6 containers are loaded at the same time; this allows 6 reactions to be carried out at the same temperature and pressure in one experiment. These glass containers are then closed with screw caps and septa and an appropriately sized small syringe cannula is used to pierce each of the septa. This allows for gas exchange at a later stage of the reaction. These vials are then placed on the metal plate and this is transferred to the autoclave under an argon atmosphere. The autoclave is purged with CO and charged at room temperature with the desired CO pressure. Then, by means of the magnetic stirrer, under magnetic stirring, the autoclave is heated to the reaction temperature and the reaction is carried out for the appropriate period of time. Subsequently, the autoclave is cooled to room temperature and pressure is slowly released. Subsequently, the autoclave is purged with nitrogen. Vials are removed from the autoclave and a defined amount of a suitable standard is added. An analysis is performed by GC, whose results are used to determine yields and selectivities.
[254] General method for experiments in 12-vial autoclaves (600 ml Parr autoclave)
[255] Glass vials heated in an oven are initially charged with di-n-butene (DNB) and methanol, and a solution of Pd(acac)2 (0.5 mg, 0.0016 mmol) and binder ( 0.0064 mmol) in 0.2 ml methanol, as well as H2SO4 (solution: 1 ml H2SO4 in 50 ml MeOH). In the autoclave, the mixtures are purged twice with 10 bar of CO, CO is injected to the desired pressure and the mixtures are stirred at the desired temperature for 20 hours. After completion of the reaction, isooctane (internal standard) and 1 mL of EtOAc are added in each case. The organic phase is analyzed by GC.
[256] Reaction yields are determined using GC (iso octane internal standard).
[257] Analysis
[258] GC analysis of ethylene-derived products: for GC analysis, an Agilent 7890A gas chromatograph with a 30 m HP column is used. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1. Methyl propionate retention time: 6.158 minutes.
[259] GC analysis of 2-butene products: for GC analysis, an Agilent 7890A gas chromatograph with a 30 m HP column is used. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1.
[260] Retention time for iso-C5 esters: 12.118 minutes.
[261] Retention time for n-C5 esters: 13.807 minutes.
[262] GC analysis of products from raffinate 1: for GC analysis, an Agilent 7890A gas chromatograph with a 30 m HP column is used. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1.
[263] Retention time for MTBE: 5.067 minutes.
[264] Retention time for iso-C5 esters: 12.118 minutes.
[265] Retention time for n-C5 esters: 13.807 minutes.
[266] GC analysis of products from the C4 fraction: for GC analysis, an Agilent 7890A gas chromatograph with a 30 m HP5 column is used. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1.
[267] Retention time of para methyl pentanoate: 13.842 minutes.
[268] Retention time for methyl pente-3-enoate: 14.344 minutes, 14.533 minutes.
[269] Retention time for dimethyl adipate: 21.404 minutes.
[270] GC analysis of products from isobutene: for GC analysis, an Agilent 7890A gas chromatograph with a 30 m HP5 column is used. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1.
[271] Retention time for MTBE: 5.045 minutes.
[272] Retention time for C5 esters: 12.105 minutes.
[273] GC analysis of products from tetramethyl-ethene: for GC analysis, an Agilent 7890A gas chromatograph with a 30 m HP column is used. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1.
[274] Retention time for tetramethyl-ethylene and products: 7,436 minutes.
[275] Retention time for ether: 11.391 minutes.
[276] Retention time for methyl 3,4-dimethylpentanoate: 17.269 minutes.
[277] GC analysis of C-5 mixture and products: For GC analysis, an Agilent 7890A gas chromatograph with a 30 m HP column is used. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1.
[278] Retention time for C5 olefins: 4.498, 4.437, 4.533, 4.533, 5.465, 5.793 minutes.
[279] Retention time for C6 methyl esters and their isomers: 14.547-16.362 minutes (main peak: 16,362 minutes).
[280] GC analysis of di-n-butene: For GC analysis, an Agilent 7890A gas chromatograph with a 30 m HP5 column is used. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1.
[281] Retention time for di-n-butene and products: 10.784-13.502 minutes.
[282] Esters formed from di-n-butene are hereinafter referred to as MINO (methyl isononanoate).
[283] Retention times for ether products of unknown isomeric distribution: 15.312, 17.042, 17.244, 17.417 minutes.
[284] Retention time for iso-C9 esters: 19.502-20.439 minutes (major peak: 19.990 minutes).
[285] Retention time for n-C9 esters: 20.669, 20.730, 20.884, 21.266 minutes.
[286] GC analysis for 1,3-butadiene products: for GC analysis, an Agilent 7890A gas chromatograph with a 30 m HP column is used. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1. Retention time for methyl pent-3-enoate: 14,430 minutes, retention time for dimethyl adipate: 21.404 minutes.
[287] GC analysis for methyl tert-butyl ether (MTBE) and products: Agilent 7890A gas chromatograph with a 30 m HP5 column. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1.
[288] Retention time of methyl 3-methylbutanoate: 12,070 minutes.
[289] MTBE retention time: 5.067 minutes.
[290] GC analysis for aromatic alcohols and products: Agilent 7890A gas chromatograph with a 30 m HP5 column. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1. GC analysis for the
[291] Retention time: 21.197 minutes.

[292] Retention time: 21,988 minutes.

[293] Secondary alcohols and products: Agilent 7890A gas chromatograph with a 30 m HP5 column. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1.
[294] Retention time for 3,3-dimethylbutan-2-ol: 10.975 minutes.
[295] Retention time for methyl 2,3,3-trimethylbutanoate: 15.312 minutes.
[296] Retention time for methyl 4,4-dimethylpentanoate: 17.482 minutes.
[297] GC analysis for tert-butanol and products: Agilent 7890A gas chromatograph with a 30 m HP5 column. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1.
[298] Retention time of tert-butanol: 4.631 minutes.
[299] Retention time of methyl 3-methylbutanoate: 12.063 minutes.
[300] GC analysis for methyl oleate and products: For GC analysis, an Agilent 7890A gas chromatograph with a 30 m HP column is used. Temperature profile: 50°C, 0 minutes; 8°C/minutes to 260°C, 15 minutes; the injection volume is 1 µL with a ratio of 50:1. Retention time for methyl oleate: 23.823 minutes, retention time for dimethyl nonadecan-1.19-dioate: 28.807 minutes, retention time for dimethyl nonadecan-1,X-dioate: 27.058 minutes; major peak, 27.058 minutes, 27.206 minutes, 27.906 minutes, 28.831 minutes (minor peaks). Position X is analytically indeterminate.
[301] Methanol analysis
[302] Methanol was pre-treated in a solvent drying system: PureSolv MD Solvent Purification System, from Innovative Technology Inc. One Industrial Way, Amesbury MA 01013
[303] Water Values
[304] Determined by Karl Fischer titration: TitraLab 580-TIM580, from Radiometer Analytical SAS (Karl Fischer titration), water content: measuring ranges, 0.1%-100% w/w, measured water content: 0 .13889%.
[305] The following were used:
[306] Applichem technical grade methanol: No. A2954.5000, lot number: LOT: 3L005446 maximum water content of 1%.
[307] Methanol from Acros Organics (on a molecular sieve): water content 0.005%, code number: 364390010, lot number: LOT 1370321.
[308] TON: number of results, defined as moles of product per mole of metal catalyst.
[309] TOF: frequency of results, defined as TON per unit of time to achieve a particular conversion, e.g., 50%.
[310] The n/iso ratio indicates the ratio of olefins terminally converted to esters to olefins internally converted to esters.
[311] The n selectivities described hereinafter refer to the ratio of terminal methoxy-carbonylation based on the overall yield in methoxy-carbonylation products.
[312] Methoxy-carbonylation of ethene with binders 3 and 8, at 80°C and 40 bar
[313] Binder 8 was tested against binder DTBPMB 3 at 80°C and 40 bar CO. The results are shown in figure 1 (figure 1: methoxy-carbonylation of ethene with 3 and 8 at 80°C and 40 bar CO).

[314] From figure 1 it can be clearly seen that the catalyst comprising binder 8 is much more active at 80°C than that comprising DTBPMB (binder 3), by about a factor of 5-6. Whereas the system comprising 8 is ready after just 10 minutes, with 3 it takes about 60-70 minutes. Both achieve the highest possible chemoselectivity (100%) for methyl propionate. Thus, the binder according to the invention presents a distinct improvement over the prior art system.
[315] Therefore, the system comprising 8 was studied in more detail and reactions were carried out at 60°C and 20 bar (important pressure level at industrial level) of CO, with the pressure of 20 bar kept constant.
[316] Methoxy-carbonylation of ethene with binders 3 and 8 at 60°C and 20 bar
[317] 3 (comparison example): Under an argon atmosphere, charge a 100 steel autoclave with [Pd(acac)2] (6.53 mg, 0.04 mol%) and the appropriate binder 3 (33 mg, 0.16% mol) and p-toluenesulfonic acid (PTSA, 61 mg, 0.6% mol). Subsequently, MeOH (20 mL) and ethene of purity 3.0 (1.5 g, 53 mmol) are added. The autoclave is heated to 60°C and then CO is injected up to a total pressure of 20 bar. This pressure is kept constant at 20 bar by introducing CO from a pressurized reservoir. The reaction is conducted for one hour and the gas consumption in the pressurized reservoir is measured. Subsequently, the autoclave is cooled and the pressure slowly released. The contents of the autoclave are transferred to a Schlenk container and 5 ml of isooctane is added as an internal standard. Yield is determined by GC analysis (100% yield). The TOF at 50% yield is 758 h-1.
[318] 8 : Under an argon atmosphere, charge a 100 mL steel autoclave with [Pd(acac)2] (6.53 mg, 0.04 mol%) and the appropriate binder 8 (44 mg, 0.16% mol) and p-toluenesulfonic acid (PTSA, 61 mg, 0.6% mol). Subsequently, MeOH (20 mL) and ethene of purity 3.0 (1.5 g, 53 mmol) are added. The autoclave is heated to 60°C and then CO is injected up to a total pressure of 20 bar. This pressure is kept constant at 20 bar by introducing CO from a pressurized reservoir. The reaction is conducted for one hour and the gas consumption in the pressurized reservoir is measured. Subsequently, the autoclave is cooled and the pressure slowly released. The contents of the autoclave are transferred to a Schlenk container and 5 ml of isooctane is added as an internal standard. Yield is determined by GC analysis (100% yield). The TOF at 50% yield is 3213 h-1.
[319] Figure 2 shows the consumption of gas from a pressurized reservoir. The reaction started with the injection of CO at 60°C (figure 2: methoxy-carbonylation of ethene with 3 and 8 at 60°C and 20 bar of CO (constant pressure)).
[320] Also in this case, it was concluded that 8 conducts the reaction much faster and without a preformation phase. As such, it is a much faster and more selective catalyst system with clear advantages over the prior art (binder 3).
[321] Alkoxy-carbonylation (comparison experiment)

[322] Scheme 10: Alkoxy-carbonylation of Ethene with Binder 59
[323] Linker 59
[324] Linker 59, 1,1'-bis-(diphenyl-phosphino)-ferrocene, is commercially available.
[325] Charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%) and 59 binder (47.9 mg, 0.16% mol) and PTSA (61 0.1 mg, 0.6% mol) and methanol (20 mL) under argon. Then, 1.5 g (53.6 mmol) of ethylene (3.5 from Linde AG) is transferred to the autoclave. (Monitoring the autoclave mass). After heating the autoclave to a reaction temperature of 80°C (pressure about 10 bar), CO (30 bar) is injected at this temperature. At this temperature, the reaction is carried out for 20 hours. Then, the autoclave is cooled to room temperature and subjected to decompression. The contents are transferred to a 50 mL Schlenk beaker and isooctane (internal standard, 5.0 mL) added. Yield and selectivity were determined by GC analysis. (Yield: 54%).
[326] Alkoxy-Carbonylation of Ethene with Various Alcohols
[327] General procedure: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0, 16% mol) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of the appropriate alcohol. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (mass monitoring). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected at 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer and Parr Instruments' Specview software application and correlated to plot the yield versus time graph. Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis.
[328] GC analysis: For GC analysis, an Agilent 7890A gas chromatograph is used which has a 30 m HP column. Temperature profile: 35°C, 10 minutes; 10°C/minute to 200°C, 16.5 minutes; injection volume of 1 μl with a ratio of 50:1.

[329] Scheme 11: Alkoxy-Carbonylation of Ethene with Various Alcohols
[330] Methanol: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0.16 mol%) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of methanol. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (monitoring by mass). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected up to 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer in the autoclave and Parr Instruments' Specview computer application and correlated to plot the yield versus time graph.
[331] Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis. At the end of the reaction, this is 100% methyl propionate. Retention time: 6,148 minutes.
[332] Ethanol: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0.16 mol%) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of ethanol. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (monitoring by mass). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected up to 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer in the autoclave and Parr Instruments' Specview computer application and correlated to plot the yield versus time graph. Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis. At the end of the reaction, this is 100% ethyl propionate. Retention time: 8.896 minutes.
[333] 1-Propanol: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0 .16 mol%) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of 1-propanol. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (monitoring by mass). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected up to 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer in the autoclave and Parr Instruments' Specview computer application and correlated to plot the yield versus time graph. Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis. At the end of the reaction, this is 100% 1-propyl propionate. Retention time: 13.342 minutes.
[334] 1-Butanol: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0 .16 mol%) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of 1-butanol. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (monitoring by mass). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected up to 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer in the autoclave and Parr Instruments' Specview computer application and correlated to plot the yield versus time graph. Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis. At the end of the reaction, this is 100% 1-butyl propionate. Retention time: 16.043 minutes.
[335] 1-Pentanol: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0 .16 mol%) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of 1-pentanol. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (monitoring by mass). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected up to 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer in the autoclave and Parr Instruments' Specview computer application and correlated to plot the yield versus time graph. Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis. At the end of the reaction, this is 100% 1-pentyl propionate. Retention time: 17.949 minutes.
[336] 1-Hexanol: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0 .16 mol%) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of 1-hexanol. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (monitoring by mass). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected up to 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer in the autoclave and Parr Instruments' Specview computer application and correlated to plot the yield versus time graph. Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis. At the end of the reaction, this is 100% 1-hexyl propionate. Retention time: 19.486 minutes.
[337] 2-Propanol: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0 .16 mol%) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of 2-propanol. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (monitoring by mass). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected up to 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer in the autoclave and Parr Instruments' Specview computer application and correlated to plot the yield versus time graph. Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis. At the end of the reaction, this is 100% 2-propyl propionate. Retention time: 11.212 minutes.
[338] t-Butanol: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0 .16 mol%) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of t-propanol. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (monitoring by mass). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected up to 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer in the autoclave and Parr Instruments' Specview computer application and correlated to plot the yield versus time graph. Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis. At the end of the reaction, this is 100% t-butyl propionate. Retention time: 13.342 minutes.
[339] 3-Pentanol: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0 .16 mol%) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of 3-pentanol. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (monitoring by mass). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected up to 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer in the autoclave and Parr Instruments' Specview computer application and correlated to plot the yield versus time graph. Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis. At the end of the reaction, this is 100% 3-pentyl propionate. Retention time: 16,648 minutes.
[340] Cyclohexanol: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0 .16 mol%) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of cyclohexanol. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (monitoring by mass). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected up to 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer in the autoclave and Parr Instruments' Specview computer application and correlated to plot the yield versus time graph. Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis. At the end of the reaction, this is 100% cyclohexyl propionate. Retention time: 19.938 minutes.
[341] Phenol: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (6.52 mg, 0.04 mol%), 8 (44.3 mg, 0.16 mol%) and PTSA (61.1 mg, 0.6% mol). Under an argon atmosphere, add 20 mL of phenol. The phenol was added as a solid without solvent. The melting point of phenol is 40.5°C. Therefore, all components must be dissolved at 80°C. Then, 1.5 g of ethene (53.6 mmol) is transferred to the autoclave (monitoring by mass). The autoclave is heated to 80°C (pressure is now around 10 bar). At this temperature, CO is injected up to 30 bar and the reaction is carried out for 20 hours, under stirring. Gas consumption is measured with a pressure transducer in the autoclave and Parr Instruments' Specview computer application and correlated to plot the yield versus time graph. Cool the autoclave to room temperature and slowly release residual pressure. The contents are transferred to a 50 ml Schlenk container, 5 ml of isooctane is added as an internal standard and the yield is determined by GC analysis. At the end of the reaction, this is 100% phenyl propionate. Retention time: 20.260 minutes.
[342] The results are shown in Figure 3.
[343] Figure 3: Variation of alcohol in the methoxy-carbonylation of ethene with binder 8 at 80°C and CO pressure of 30 bar.
[344] Of course, it is possible to use not only methanol in the alkoxylation, it is also possible to use multiple different alcohols. The corresponding products can be obtained in good to very good yields (in some cases quantitatively).
[345] Conversion of 8 with propylene

[346] Scheme 12: Propene conversion with 8
[347] Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (17.5 mg, 0.04 mol%), 8 (119 mg, 0.16% mol), MeOH (15 mL) and [98% H2SO4] (38 µL, 0.5 mol%). The autoclave is then cooled with melting ice. Condense propene (6.06 g, 144 mmol) into a separate cylinder (75 mL, mass monitor). This quantity defined in the autoclave is then condensed. Next, CO is injected into the autoclave up to 40 bar at room temperature. The reaction is carried out at 100°C for 30 minutes. After the reaction, the autoclave is cooled to room temperature and the pressure is released. 8.5 ml of isooctane is added to the solution as an internal standard. Yield and selectivity are determined by GC analysis. (Yield: >99%, n/iso: 77:23).
[348] Conversion of 1-butene with 8

[349] Scheme 13: conversion of 1-butene with 8
[350] Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (17.5 mg, 0.04 mol%), 8 (119 mg, 0.16% mol), MeOH (15 mL) and [98% H2SO4] (38 µL, 0.5 mol%). The autoclave is then cooled with melting ice. Condense 1-butene (8.04 g, 144 mmol) into a separate cylinder (75 mL, mass monitoring). This quantity defined in the autoclave is then condensed. Next, CO is injected into the autoclave up to 40 bar at room temperature. The reaction is carried out at 100°C for 60 minutes. After the reaction, the autoclave is cooled to room temperature and the pressure is released. 8.5 ml of isooctane is added to the solution as an internal standard. Yield and selectivity are determined by GC analysis. (Yield: >99%, n/iso: 80:20).
[351] Conversion of 2-butene with 8


[352] Scheme 14: Conversion of 2-butene with 8
[353] Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (17.5 mg, 0.04 mol%), 8 (119 mg, 0.16% mol), MeOH (15 mL) and [98% H2SO4] (38 µL, 0.5 mol%). The autoclave is then cooled with melting ice. Condense 2-butene (8.04 g, 144 mmol) in a separate cylinder (75 mL, mass monitor). This quantity defined in the autoclave is then condensed. Next, CO is injected into the autoclave up to 40 bar at room temperature. The reaction is carried out at 100°C for 60 minutes. After the reaction, the autoclave is cooled to room temperature and the pressure is released. 8.5 ml of isooctane is added to the solution as an internal standard. Yield and selectivity are determined by GC analysis. (Yield: >99%, n/iso: 75:25).
[354] The results are shown in figure 4. This figure shows the efficiency profile of the aforementioned reactions, which was calculated by conversion from the gas consumption curve. The curve was fitted using the yield determined by gas chromatography upon completion of the reaction.
[355] Figure 4: Methoxy-carbonylation experiments with propene, 1-butene and 2-butene, at 100°C and 40 bar, with binder 8.
[356] As can be seen from Figure 4, the conversion rates of olefins decrease with increasing chain length. The conversion rate is higher for terminal olefins than for olefins with an internal double bond. Whereas the propene was completely converted after less than 10 minutes, it takes about 40 minutes for 1-butene and almost 60 minutes for 2-butene to obtain a complete conversion (100% yield).
[357] Conversion of raffinate 1 to compound 8
[358] Technical mixtures were also tested, including the one referred to as raffinate 1. Raffinate 1 consists of 42% isobutene, 26% 1-butene, 17% cis- and trans-2-butene and also 0.3 % 1,3-butadiene and 15% n-butane and isobutane.
[359] Method
[360] Under an argon atmosphere, charge a 100 mL steel autoclave with [Pd(acac)2] (17.4 mg), 8 (118.9 mg) and H2SO4 (70.6 mg). Under an atmosphere of Ar, methanol (15 mL) is added. Cool the autoclave with melting ice. Next, 8.2 g raffinate 1 is condensed into a separate cylinder (75 ml, monitoring by mass) and this defined amount of substrate is condensed in the cooled autoclave. Then pressurize the autoclave with 60 bar of CO at room temperature. The reaction is carried out at 100°C for 20 hours. Then transfer the contents to a 50 mL Schlenk container and add isooctane as an internal standard. Yield and selectivity are determined by GC analysis.
[361] Result: C5 ester: 9.7 g, n/iso 37/63, MTBE: 2.0 g.


[362] Scheme 15: Reaction of raffinate 1 with linker 8
[363] The results are also shown in Figure 5.
[364] Figure 5: Methoxy-carbonylation of raffinate 1 with binder 8 at 100°C and 60 bar CO pressure.
[365] It was thus shown that also industrially relevant mixtures, such as the case here of raffinate 1, can be converted with binder 8 according to the invention.
[366] Refined 1 with sampling
[367] In addition, raffinate 1 was converted to binder 8.

[368] Scheme 16: methoxy-carbonylation of raffinate 1
[369] General procedure: Under an argon atmosphere, a 100 mL steel autoclave was charged with [Pd(acac)2] (17.4 mg), 8 (118.9 mg) and H2SO4 (70.6 mg). Then 15 ml of MeOH and 10 ml of isooctane were added as an internal standard. The autoclave is then cooled to -78°C with ice-water. Condense raffinate 1 (8.1 g) into a separate 75 mL pressurized cylinder (monitoring by mass). This defined mass is then condensed in the autoclave. Charge the autoclave with 50 bar of CO at room temperature. The autoclave is heated to 100°C and stirred at this temperature for 20 hours. During this period, 16 samples are collected from the autoclave via an HPLC valve and an internal capillary. Yield and selectivity are determined by GC analysis. GC analysis: For GC analysis, an Agilent 7890A gas chromatograph with a 30 m HP column is used. Temperature profile: 35°C, 10 minutes; 10°C/minute to 200°C, 16.5 minutes; the injection volume is 1 µL with a ratio of 50:1.
[370] Retention time for MTBE: 5.067 minutes.
[371] Retention time for iso-C5 esters: 12.118 minutes.
[372] Retention time for n-C5 esters: 13.807 minutes.
[373] The results are shown in Figure 6.
[374] Figure 6: Methoxy-carbonylation of raffinate 1 at 100°C and 50 bar with linker 8. At the end of the reaction, 80% of C5 ester and 20% of methyl-tert-butyl ester are present, based on amount of olefins used.
[375] Thus, binder 8 presents a good suitability for the conversion of a stream of industrial relevance, refined 1.
[376] Figure 5 shows the gas absorption curve for the no-sampling experiment with a 20 hour cycle and which provided 9.7 g of C5 ester with an n/iso ratio of 37/63 and a MTBE content of 2.0 g. The experiment conducted in Figure 6 provides 32% n-C5 ester and 48% iso-C5 ester. This corresponds to an n/iso ratio of 33/67. The mass ratio of methyl tert-butyl ether is 20%. Figure 5 shows a mass ratio of 17%. Thus, the two experiments provide similar results. From Figure 5 it is apparent that most of the reaction is over after about 1 hour. This is also in line with the experience with sampling in figure 6.
[377] Methoxy-carbonylation of isobutene with binders 3 and 8

[378] Scheme 17: methoxy-carbonylation of isobutene with binders 3 and 8
[379] Ligand 3 (comparison example): Under an argon atmosphere, a 100 mL steel autoclave is charged with Pd(acac)2 (4.9 mg), DTBPMB (25.3 mg), PTSA ( 45.6 mg) and MeOH (20 ml). Subsequently, the autoclave is cooled with melting ice. In a separate pressurized vessel, 2.5 g of isobutene is condensed (mass monitoring). This defined mass is condensed in the autoclave. Then charge the autoclave with CO to 40 bar at room temperature. The reaction is carried out at 120°C for 20 hours. Subsequently, the autoclave is cooled to room temperature and decompressed, the contents transferred to a 50 ml Schlenk container and isooctane (5 ml as internal standard) added. A GC analysis is performed. (GC analysis (50% yield on methyl 3-methylbutanoate, 37% yield on MTBE).
[380] Ligand 8: Under an argon atmosphere, charge a 100 mL steel autoclave with Pd(acac)2 (4.9 mg), 8 (33.1 mg), PTSA (45.6 mg) and MeOH (20 ml). Subsequently, the autoclave is cooled with melting ice. In a separate pressurized vessel, 2.5 g of isobutene is condensed (mass monitoring). This defined mass is condensed in the autoclave. Then charge the autoclave with CO to 40 bar at room temperature. The reaction is carried out at 120°C for 20 hours. Subsequently, the autoclave is cooled to room temperature and decompressed, the contents transferred to a 50 ml Schlenk container and isooctane (5 ml as internal standard) added. A GC analysis is performed. (GC analysis (99% yield in methyl 3-methylbutanoate).
[381] Test of a mixture of propene, 1-butene and 2-butene
[382] In addition, mixtures of reagents, that is, mixtures comprising different unsaturated compounds, were also tested.
[383] Method: Under an argon atmosphere, charge a 100 mL steel autoclave with [Pd(acac)2] (17.4 mg), 8 (118.9 mg) and H2SO4 (70.6 mg) ). Under an argon atmosphere, add methanol (15 mL). Cool the autoclave with melting ice. Next, condense 2.83 g of 2-butene, 4.85 mg and propene (2.2 g) in three separate cylinders (75 mL, monitoring by mass) and condense these defined amounts of gaseous substrate in the cooled autoclave. Then pressurize the autoclave with 60 bar of CO at room temperature. The reaction is carried out at 100°C for 20 hours. Then transfer the contents to a 50 mL Schlenk container and add isooctane as an internal standard. Yield and selectivity are determined by GC analysis. (Yield: 100%, C4 esters: n/iso 79/21, C5 esters: n/iso: 75/25).

[384] Scheme 18: Mixture of propene, 1-butene and 2-butene in methoxycarbonylation with binder 8
[385] The results are shown in Figure 7.
[386] Figure 7: Methoxy-carbonylation of a mixture of propene, 1-butene and 2-butene at 100°C and 60 bar with binder 8.
[387] As can be seen in figure 7, an almost complete yield of the methoxy-carbonylation products is achieved with the mixture of propene, 1-butene and 2-butene, after a reaction time period of about 1 hour .
[388] Conversion of tetramethyl-ethylene with various binders at various temperatures

[389] Scheme 19: conversion of tetramethyl-ethylene with various ligands at various temperatures
[390] Reaction temperature: 100°C
[391] 3 (comparison example): A 25 mL Schlenk flask was charged with [Pd(acac)2] (4.87 mg, 0.1 mol%), p-toluenesulfonic acid (PTSA) (24.32 mg, 0.8 mol%) and MeOH (8 ml). A 4 ml vial was charged with 3 (6.3 mg, 0.4 mol%) and a magnetic stir bar was added. Next, 2 ml of the clear yellow solution and tetramethyl-ethylene (478 µL, 4 mmol) were added with the aid of a syringe. The vial was placed in a sample holder, which was in turn inserted into a 300 mL Parr autoclave under an argon atmosphere. After purging the autoclave three times with nitrogen, the CO pressure was adjusted to 40 bar. The reaction proceeded at 100°C for 20 hours. After completion of the reaction, the autoclave was cooled to room temperature and carefully decompressed. Iso-octane (200 µL) was added as an internal standard for GC. Yield and regioselectivity were determined using GC. (Conversion: 40%, no yield to ester product; yield to ether product 38%).
[392] 8: Charge a 25 mL Schlenk flask with [Pd(acac)2] (4.87 mg, 0.1 mol%), p-toluenesulfonic acid (PTSA) (24.32 mg) , 0.8 mol%) and MeOH (8 ml). A 4 ml vial was charged with 8 (8.3 mg, 0.4 mol%) and a magnetic stir bar was added. Next, 2 mL of the clear yellow solution and tetramethyl-ethylene (478 µL, 4 mmol) were added with the aid of a syringe. The vial was placed in a sample holder, which was in turn inserted into a 300 mL Parr autoclave under an argon atmosphere. After purging the autoclave three times with nitrogen, the CO pressure was adjusted to 40 bar. The reaction proceeded at 100°C for 20 hours. After completion of the reaction, the autoclave was cooled to room temperature and carefully decompressed. Isooctane (200 µL) was added as an internal standard for GC. Yield and regioselectivity were determined using GC. (Conversion: 65%, yield to ester product: 37%; yield to product ether 27%).
[393] Reaction temperature: 120°C
[394] 3 (comparison example): A 25 mL Schlenk flask was charged with [Pd(acac)2] (4.87 mg, 0.1 mol%), p-toluenesulfonic acid (PTSA) (24.32 mg, 0.8 mol%) and MeOH (8 ml). A 4 ml vial was charged with 3 (6.3 mg, 0.4 mol%) and a magnetic stir bar was added. Next, 2 ml of the clear yellow solution and tetramethyl-ethylene (478 µL, 4 mmol) were added with the aid of a syringe. The vial was placed in a sample holder, which was in turn inserted into a 300 mL Parr autoclave under an argon atmosphere. After purging the autoclave three times with nitrogen, the CO pressure was adjusted to 40 bar. The reaction proceeded at 120°C for 20 hours. After completion of the reaction, the autoclave was cooled to room temperature and carefully decompressed. Iso-octane (200 µL) was added as an internal standard for GC. Yield and regioselectivity were determined using GC. (Conversion: 54%, no yield to ester product; yield to ether product 52%).
[395] 8: Charge a 25 mL Schlenk flask with [Pd(acac)2] (4.87 mg, 0.1 mol%), p-toluenesulfonic acid (PTSA) (24.32 mg) , 0.8 mol%) and MeOH (8 ml). A 4 ml vial was charged with 8 (8.3 mg, 0.4 mol%) and a magnetic stir bar was added. Next, 2 mL of the clear yellow solution and tetramethyl-ethylene (478 µL, 4 mmol) were added with the aid of a syringe. The vial was placed in a sample holder, which was in turn inserted into a 300 mL Parr autoclave under an argon atmosphere. After purging the autoclave three times with nitrogen, the CO pressure was adjusted to 40 bar. The reaction proceeded at 120°C for 20 hours. After completion of the reaction, the autoclave was cooled to room temperature and carefully decompressed. Isooctane (200 µL) was added as an internal standard for GC. Yield and regioselectivity were determined using GC. (Conversion: 90%, yield to ester product: 60%; yield to product ether 28%).
[396] Methoxy-Carbonylation of C5 Olefins
[397] Procedure: Under an argon atmosphere, a 100 mL steel autoclave was charged with [Pd(acac)2] (10.95 mg, 0.04 mol%), 8 (74.31 mg, 0 .16 mol%) and H2SO4 (44.1 mg, 0.5 mol%). Subsequently, under an argon atmosphere, 10 mL of MeOH, 1-pentene (0.5 g), 2-pentene (2.21 g), 2-methyl-1-butene (1.27 g) and 2-methyl-2-butene (1.3 g). The autoclave is then cooled to -78°C with ice-water. 1.1 g of 3-methyl-1-butene (1.1 g) are condensed into a separate pressurized container (monitoring by mass) and this defined amount is condensed in the autoclave. Subsequently, charge the autoclave with CO to 50 bar at room temperature. Under stirring, the reaction is carried out at 100°C for 20 hours. Then, the autoclave is cooled to room temperature and the residual pressure is slowly released. The contents are transferred to a 50 ml Schlenk beaker and 5 ml of isooctane is added as an internal standard. Yield is determined by GC analysis. At the end of the reaction, this is 76% in C6 methyl esters.
[398] GC analysis: For GC analysis, an Agilent 7890A gas chromatograph with a HP 30 choline is used. Temperature profile: 35°C, 10 minutes; 10°C/minutes to 200°C, 16.5 minutes; the injection volume is 1 μl with a ratio of 50:1.
[399] Retention times for C6 methyl esters and their isomers: 14.547-16.362 minutes (major peak: 16,362 minutes).

[400] Scheme 20: Mixing various C5 olefins in methoxy-carbonylation
[401] The results are shown in Figure 8.
[402] Figure 8: Methoxy-carbonylation of a mixture of C5 olefins at 100°C and 50 bar CO pressure with binder 8.
[403] As is evident, the corresponding C6 esters can be obtained as a mixture in good yields (distinctly > 50%).
[404] Conversion of di-n-butene with binder 8

[405] In addition, an experiment with constant pressure and gas consumption measurement was conducted with binder 8 at a total pressure of 20 bar.
[406] Experimental example: Under an argon atmosphere, a 100 mL steel autoclave is charged with [Pd(acac)2] (5.85 mg, 0.04 mol%) and the appropriate binder 8 (39 0.6 mg, 0.16% mol) and p-toluenesulfonic acid (PTSA, 54.7 mg, 0.6% mol). Subsequently, MeOH (30 mL) and di-n-butene (7.54 mL, 48 mmol) are added. The autoclave is heated to 120°C and then CO is injected to a total pressure of 20 bar. This pressure is kept constant at 20 bar by introducing CO from a pressurized container. The reaction is conducted for 20 hours and the gas consumption in the pressurized reservoir is measured. Subsequently, the autoclave is cooled and the pressure slowly released. The contents of the autoclave are transferred to a Schlenk container and 5 ml of isooctane is added as an internal standard. Yield is determined by GC analysis (86% yield, n:iso = 75:25).
[407] The results are shown in Figure 9.
[408] Figure 9: Methoxy-carbonylation of di-n-butene with the binder 8 at 120°C and 20 bar with constant CO pressure
[409] After just 5 hours, like linker 8, a yield of iso-methyl-nonanoate (MINO) of greater than 80% is achieved; the yield and the n:iso ratio after 20 hours corresponds to that of the experiment with binder 8 at 120°C and 40 bar under variable CO pressure (see above). A CO pressure of less than 20 bar during the reaction can thus be used without loss of yield and selectivity.
[410] Methoxy-carbonylation of di-n-butene with binders 3 and 8
[411] To have a good comparison of binders in the methoxycarbonylation of di-n-butene, experiments with gas consumption measurements were conducted.

[412] Scheme 21: Test of various binders in the methoxy-carbonylation of di-n-butene
[413] 3 (comparison example): Under an argon atmosphere, a 100 mL steel autoclave was charged with [Pd(acac)2] (5.85 mg, 0.04 mol%) and 3 (30 .3mg, 0.16% mol). Subsequently, MeOH (30 mL) and di-n-butene (7.54 mL, 48 mmol) and PTSA (54.7 mg, 0.6% mol) are added. The autoclave is charged at room temperature with CO purity 4.7 to 40 bar and the reaction is carried out at 120°C for 20 hours. Subsequently, the autoclave is cooled and the pressure slowly released. The contents of the autoclave are transferred to a Schlenk container. 5 ml of isooctane is added as an internal standard and the yield and selectivity is determined by GC analysis (60% yield in MINO, n/iso: 93/7).
[414] 8: Under an argon atmosphere, a 100 mL steel autoclave was charged with [Pd(acac)2] (5.85 mg, 0.04 mol%) and 8 (39.6 mg, 0 .16 mol%). Subsequently, MeOH (30 mL) and di-n-butene (7.54 mL, 48 mmol) and PTSA (54.7 mg, 0.6% mol) are added. The autoclave is charged at room temperature with CO purity 4.7 to 40 bar and the reaction is carried out at 120°C for 20 hours. Subsequently, the autoclave is cooled and the pressure slowly released. The contents of the autoclave are transferred to a Schlenk container. 5 ml of isooctane is added as an internal standard and the yield and selectivity is determined by GC analysis (86% yield in MINO, n/iso: 75/25).
[415] Figure 10 shows the gas consumption curves (or graphical representation of efficiency as a function of time) for the systems tested.
[416] Figure 10: Methoxy-carbonylation of di-n-butene as 3 and 8 at 120°C and 40 bar CO.
[417] It is quite evident from the gas consumption measurements and the experimental examples that binder 8 is faster than binder 3. Although the selectivity at 75% is lower compared to 3 as a binder, preference is given to binder 8 with regard to a possible industrial implementation and very high space-time yield.
[418] In addition, an experiment with constant pressure and gas consumption measurement with 8 at a total pressure of 20 bar was conducted.
[419] Experimental example: Under an argon atmosphere, a 100 mL steel autoclave is charged with [Pd(acac)2] (5.85 mg, 0.04 mol%) and the appropriate binder 8 (39, 6 mg, 0.16% mol) and p-toluenesulfonic acid (PTSA, 54.7 mg, 0.6% mol). Subsequently, MeOH (30 mL) and di-n-butene (7.54 mL, 48 mmol) are added. The autoclave is heated to 120°C and then CO is injected to a total pressure of 20 bar. This pressure is kept constant at 20 bar by introducing CO from a pressurized reservoir. The reaction is conducted for one hour and the gas consumption in the pressurized reservoir is measured. Subsequently, the autoclave is cooled and the pressure slowly released. The contents of the autoclave are transferred to a Schlenk container and 5 ml of isooctane is added as an internal standard. Yield is determined by GC analysis (86% yield, n:iso = 75:25).
[420] The results are shown in Figure 11.
[421] Figure 11: Performance curve for the methoxy-carbonylation of di-n-butene with 8 as a binder at a constant total pressure of 20 bar and 120°C.
[422] A performance equal to that of the experiment with 40 bar of non-constant CO is found. This means that the methoxy-carbonylation of di-n-butene as 8 as a binder is independent of the CO pressure above a certain CO pressure range, lower pressures below 20 bar being industrially favorable are achievable.
[423] Conversion of di-n-butene with other binders (comparison experiments in a 12-well autoclave)
[424] The conversion of di-n-butene with the aid of various binders was carried out by the following method.
[425] Method: Charge a 50 mL Schlenk container with [Pd(acac)2] (3.9 mg, 0.04 mol%), MeSO3H (methanesulfonic acid) (13 µL, 0.6 mol%) and MeOH (20 mL). Charge a 4 ml vial with the linker X (0.16% mol) and add a magnetic stir bar. Next, 1.25 mL of the clear yellow stock solution and di-n-butene (315 µL, 2 mmol) are added with the aid of a syringe. The vial is placed in a sample holder, which is in turn inserted into a 600 mL Parr autoclave under an argon atmosphere. After purging the autoclave three times with nitrogen, the CO pressure is adjusted to 40 bar. The reaction is carried out at 120°C for 20 hours. After completion of the reaction, the autoclave is cooled to room temperature and decompressed carefully. Iso-octane is added as an internal GC standard. The yield and regioselectivity are determined by means of GC.
[426] The results are summarized in scheme 22 below.

[427] Scheme 22: Catalyst results with a selection of ferrocenyl binders.
[428] Determination of STY space-time yield
[429] The space-time yield (STY) is intended to designate the production of a specific product (amount of product forming in a reactor) from a reaction vessel (reactor) per unit of space and time, for example, t (tonnes) of product per cubic meter and unit of time or kg per liter and second.
[430] Method: In each case, a Schlenk container, heated in an oven, is initially charged with 1.6% mol% PTSA (180 mg), 0.04 mol% Pd(acac)2 (7, 5 mg) and 0.16% molar binder 3 or 8. Then add 6.26 ml (150 mmol) methanol (technical grade) and 9.39 ml (60 mmol) di-n-butene and transfer the mixture to a 100 ml autoclave. The autoclave is then purged twice with CO at 10 bar, charged with CO to 6 bar and heated to 100°C. Then, charge the autoclave with CO to 12 bar by means of a gas burette and stir at 100°C under a constant pressure of CO (12 bar) for 20 hours. After the reaction is complete, isooctane (internal standard) and 10 mL of EtOAc are added. The organic phase is analyzed by GC.

[431] MINO: methyl iso-nonanoate
[432] Scheme 23: MINO Synthesis
[433] The results are shown in Figure 12.
[434] Figure 12: Gas consumption curves for reactions with 3 and 8.
[435] C-18 Olefins
[436] Methyl oleate (Alfa Aesar, H311358, LOT:10164632)
[437] Conversion of methyl oleate with linkers 3 and 8

[438] Scheme 24: Conversion of methyl oleate with linkers 3 and 8
[439] 3 (comparison example): Charge a 25 mL Schlenk container with [Pd(acac)2] (4.57 mg, 0.05 mol%), H2SO4 (22.05 mg, 7, 5 mol%) and MeOH (6 mL). Charge a 4 mL vial with 3 (7.9 mg, 2.0 mol%) and add a magnetic stir bar. Next, 2 mL of the clear yellow solution and methyl oleate (339 μL, 1 mmol) are added with the aid of a syringe. The vial is placed in a sample holder, which in turn is inserted into a 300 mL Parr autoclave under an argon atmosphere. After purging the autoclave three times with nitrogen, the CO pressure is adjusted to 40 bar. The reaction is carried out at 100°C for 20 hours. After completion of the reaction, the autoclave is cooled to room temperature and decompressed carefully. Iso-octane (100 µL) is added as an internal GC standard. The yield and regioselectivity are determined by means of GC. Yield on linear ester: 54%, no branched ester.
[440] 8: Charge a 25 mL Schlenk container with [Pd(acac)2] (4.57 mg, 0.05 mol%), H2SO4 (22.05 mg, 7.5% mol) and MeOH (6 mL). Charge a 4 mL vial with 8 (10.3 mg, 2.0 mol%) and add a magnetic stir bar. Next, 2 mL of the clear yellow solution and methyl oleate (339 μL, 1 mmol) are added with the aid of a syringe. The vial is placed in a sample holder, which in turn is inserted into a 300 mL Parr autoclave under an argon atmosphere. After purging the autoclave three times with nitrogen, the CO pressure is adjusted to 40 bar. The reaction is carried out at 100°C for 20 hours. After completion of the reaction, the autoclave is cooled to room temperature and decompressed carefully. Iso-octane (100 µL) is added as an internal GC standard. Yield and regioselectivity are determined using GC. Linear ester yield: 98%, no branched ester.
[441] From the results it is evident that binder 8 of the invention is more suitable for the conversion of methyl oleate than binder 3 of the prior art.
[442] Conversion of various olefins under optimized conditions
[443] The conditions for the methoxy-carbonylation of di-n-butene have been optimized as follows:

[444] Scheme 25: optimized conditions
[445] The optimized conditions were applied to a set of alkenes (Table 1).

[446] Method: First load glass vials, heated in an oven, each with 1 mg (0.04 mol%) of Pd(acac)2 and 7.2 mg (0.16% mol) of binder 8 and in each case 812 µL (20 mmol) of methanol (technical grade) and 8 mmol of alkene are added. Then add 2 μL (0.5 mol%) of H2SO4 (98%) (100 μL of a solution of sulfuric acid in methanol contains 2 μL of sulfuric acid).
[447] The reaction mixtures are purged in the autoclave twice with CO at 10 bar, charged with CO at 15 bar and stirred at 100°C for 20 hours. After the reaction is complete, isooctane (internal standard) and 1 mL of EtOAc are added in each case. The organic phase is analyzed by GC.
[448] The results are grouped in table 1. Table 1: substrate test with multiple alkenes

[449] The n selectivity in Table 1 is defined as the proportion of terminal methoxycarbonylation based on the total yield of the methoxycarbonylation products.
[450] Terminal linear olefins, such as 1-octene, 1-decene, 1-hexene, and 2-octene, have been found to provide quantitative ester yields. Also, good yields are provided by methyl 3-pentenoate, methyl oleate and methyl undecenoate. In the case of vinyl-cyclohexene, there is 52% monomethoxy-carbonylation and also partial methoxy-carbonylation of the internal double bond (35%). Octadiene is single methoxy carbonyl to an extent of 55% and doubly methoxy carbonyl to an extent of 26%.
[451] The experiments described show that the compounds according to the invention are suitable as catalyst binders for the alkoxycarbonylation of multiple ethylenically unsaturated compounds. More particularly, with the compounds according to the invention, superior results are achieved than with the bidentate phosphine binders known from the prior art, such as 1,2-bis-(di-tert-butyl-phosphinomethyl)-benzene ( DTBPMB, linker 3), 1,1'-bis-(diphenyl-phosphine)-ferrocene (linker 59), 1-(diphenyl-phosphine)-1'-(diisopropyl-phosphine)-ferrocene (linker 10) and 1,1'-bis(isopropyl-phenyl-phosphine)-ferrocene (linker 19). Furthermore, the compounds according to the invention also allow the alkoxy-carbonylation of industrially important long-chain olefins, such as di-n-butene and 2-octene, as well as of olefin mixtures, such as the raffinate 1 described. .

权利要求:
Claims (14)
[0001]
1. Compound characterized by having the structural formula (I):
[0002]
Compound according to claim 1, characterized in that at least two of the radicals R 1 , R 2 , R 3 , R 4 represent a -heteroaryl radical (C 6 -C 20 ) having at least six atoms in the ring.
[0003]
Compound according to claim 1 or 2, characterized in that both the radicals R 1 and R 2 represent a -heteroaryl radical (C 6 -C 20 ) having at least six atoms in the ring.
[0004]
Compound according to any one of claims 1 to 3, characterized in that each of the radicals R1 and R3 represents a -heteroaryl (C6-C20) radical having at least six atoms in the ring; the radical R2 represents -heteroaryl(C6-C20) having at least six atoms in the ring or is selected from -alkyl(C1-C12), -cycloalkyl(C3C12), -heterocycloalkyl(C3-C12), -aryl(C6- C20); and the radical R4 is selected from -alkyl(C1-C12), -cycloalkyl(C3C12), -heterocycloalkyl(C3-C12), -aryl(C6-C20).
[0005]
Compound according to any one of claims 1 to 4, characterized in that each of the radicals R1 and R3 represents a -heteroaryl (C6-C20) radical having at least six atoms in the ring; and each of the radicals R2 and R4 represents a group selected from -alkyl(C1-C12), -cycloalkyl(C3-C12), -heterocycloalkyl(C3-C12), -aryl(C6-C20).
[0006]
Compound according to any one of claims 1 to 5, characterized in that both the radicals R1 and R3 represent a -heteroaryl (C6-C20) radical having at least six atoms in the ring; and each of the radicals R2 and R4 represents -(C1-C12)alkyl.
[0007]
Compound according to any one of claims 1 to 6, characterized in that the radicals R 1 , R 2 , R 3 , R 4 , if they represent a heteroaryl radical, each represent a group independently selected from pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.
[0008]
Compound according to any one of claims 1 to 7, characterized in that it has one of the structural formulas (8), (14) and (15):
[0009]
A complex characterized in that it comprises Pd and a compound as defined in any one of claims 1 to 8.
[0010]
10. Process characterized by comprising the following process steps: a) initially loading an ethylenically unsaturated compound; b) adding a compound according to any one of claims 1 to 8 and a compound comprising Pd; or adding a complex as defined in claim 10; c) adding an alcohol; d) feed the CO; e) heating the reaction mixture, converting the ethylenically unsaturated compound to an ester.
[0011]
Process according to claim 10, characterized in that the ethylenically unsaturated compound is selected from ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis - and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethyl-ethylene, heptene, 1-octene, 2-octene, di-n-butene and mixtures thereof.
[0012]
Process according to claim 10 or 11, characterized in that the compound comprising Pd in process step b) is selected from palladium dichloride, palladium(II) acetylacetonate, palladium(II) acetate, dichloro- (1,5-cyclooctadiene)-palladium(II), bis(dibenzylidene-acetone)-palladium, bis-(acetonitrile)-dichloro-palladium(II), palladium(cinnamyl) dichloride.
[0013]
Process according to any one of claims 10 to 12, characterized in that the alcohol in process step c) is selected from methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, cyclohexanol, phenol and mixtures thereof.
[0014]
Use of a compound as defined in any one of claims 1 to 8 or a complex as defined in claim 9 characterized in that it is for catalysis of an alkoxy-carbonylation reaction.

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法律状态:
2017-02-14| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|

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2020-07-28| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-11-10| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |

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2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/07/2016, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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DE102015213918|2015-07-23|

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DE102015213918.2|2015-07-23|

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