US 2004/0106512 A1 · Phosphacyclohexanes and the use thereof in the hydroformylation of olefins

Abstract

The invention relates to phosphacyclohexanes of general formulae I and II, wherein the following designations, among others, apply: R can represent hydrogen, C1-100-alkyl, C7-20-aralkyl, C7-20-alkaryl, and C6-12-aryl: R1 to R10 can independently represent hydrogen, C1-20-alkyl, C7-20-aralkyl, C7-20-alkaryl, and C6-12-aryl: W, W′ can independently represent single bonds or bridges comprising 1 to 20 carbon atoms, which can form part of a cyclic or aromatic group and can be interrupted by heteroatoms. Said phosphacyclohexanes are used as ligands in transition metal complexes of transition metals belonging to groups VIII to X of the periodic table. 1

Claims25

Dependent claims

The use of compounds having at least one unbridged phosphacyclohexane and/or phosphacyclohexene structural element as ligands in complexes of transition metals of transition group VIII of the Periodic Table of the Elements.

A process for preparing at least one phosphacyclohexene and/or phosphacyclohexane of the formulae V.a to V.c

30
where
R
is hydrogen, C1-100-alkyl, cycloalkyl, heterocycloalkyl, C7-20-aralkyl, C7-20-alkaryl, C6-12-aryl, hetaryl, W′COO−M+, W′SO3−M+, W′PO32−M+2, W′NR′3+X−, W′OR′, W′NR′2, W′COOR′, W′SR′, W′(CHR′CH2O)xR′, W′(CH2NR′)xR′, W′(CH2CH2NR′)xR′, W′((CH2)4O)xR′ or W′COR′,
where the radicals R or one of the radicals R11 to R15 in each of two identical or different units V.a, V.b or V.c may also together form a bridging group W which covalently joins these units to one another,
R11 to R15
are each, independently of one another, hydrogen, C1-20-alkyl, C7-20-aralkyl, C7-20-alkaryl, C6-12-aryl, where one or more carbon atoms may be replaced by heteroatoms, W′COO−M+, W′SO3−M+, W′PO32−M+2, W′NR′3+X−, W′OR′, W′NR′2, W′COOR′, W′SR′, W′(CHR′CH2O)xR′, W′(CH2NR′)xR′, W′(CH2CH2NR′)xR′, W′((CH2)4O)xR′, W′halogen, W′NO2, W′COR′ or W′CN,
where one or more hydrogen atoms in the radicals R and R11 to R15 may be replaced by fluorine,
W and W′
are, independently of one another, single bonds or bridges having from 1 to 20 carbon atoms which may be part of a cyclic or aromatic group and may be interrupted by heteroatoms, where W may also be a polyoxyalkylene or polyalkylenimine bridge having at least 21 carbon atoms,
R′ is hydrogen, C1-20-alkyl, carbonylalkyl, cycloalkyl or aryl,
M+ is a cation equivalent,
X− is an anion equivalent and
x is an integer from 1 to 240,
where one or more of the radicals R and R11 to R15 may bear an additional trivalent phosphorus or nitrogen group capable of coordination
where one of the radicals R or R11 to R15 or, if present, a group W in the compounds of the formulae V.a, V.b and V.c may also be a polymer radical having a number average molecular weight in the range from 500 to 50 000 and made up of repeating units derived from monomers selected from among monoolefins and diolefins, vinylaromatics, esters of α,β-ethylenically unsaturated monocarboxylic and dicarboxylic acids with C1-30-alkanols, N-vinyl amides, N-vinyl lactams, heterocyclic compounds which can be polymerized with the ring opening and mixtures thereof,
which comprises
a) hydrogenating at least one phosphabenzene of the formula IV
31
where R11, R12, R13, R14 and R15 are as defined above, by means of hydrogen in the presence of a hydrogenation catalyst to give at least one phosphacyclohexene and/or phosphacyclohexane of the formulae V.a to V.c in which the radical R is hydrogen, and, if desired,
b1) reacting the hydrogenation product(s) obtained in step a) with at least one ethylenically unsaturated compound
in the presence of at least one free-radical former, or
in the presence of at least one acid or at least one base or at least one transition metal compound, or
at an elevated temperature in the range from 100 to 250° C., or
b2) reacting the hydrogenation product(s) obtained in step a) with at least one compound of the formula R—X or X—W—Y, where X and Y are nucleophilically displaceable groups and R and W are as defined above, with the exception of R=hydrogen.

22 more elements

A process for preparing at least one phosphacyclohexane of the formulae VI.a and/or VI.b

33
where
R
is C1-100-alkyl, cycloalkyl, heterocycloalkyl, C7-20-aralkyl, C7-20-alkaryl, C6-12-aryl, hetaryl, W′COO−M+, W′SO3−M+, W′PO32−M+2, W′NR′3+X−, W′OR′, W′NR′2, W′COOR′, W′SR′, W′(CHR′CH2O)xR′, W′(CH2NR′)xR′, W′(CH2CH2NR′)xR′, W′((CH2)4O)nR′ or W′COR′,
where two radicals R may also together form a bridging group W which covalently joins two identical or different units VI.a or VI.b to one another,
R11 to R16
are each, independently of one another, hydrogen, C1-20-alkyl, C7-20-aralkyl, C7-20-alkaryl, C6-12-aryl, where one or more carbon atoms may be replaced by heteroatoms, W′COO−M+, W′SO3−M+, W′PO32−M+2, W′NR′3+X−, W′OR′, W′NR′2, W′COOR′, W′SR′, W′(CHR′CH2O)xR′, W′(CH2NR′)xR′, W′(CH2CH2NR′)xR′, W′((CH2)4O)xR′, W′halogen, W′NO2, W′COR′ or W′CN,
where one or more hydrogen atoms in the radicals R11 to R16 may be replaced by fluorine,
where two radicals R16 may also together form a bridging group W which covalently joins two identical or different units VI.a or VI.b to one another,
W and W′
are, independently of one another, single bonds or bridges having from 1 to 20 carbon atoms which may be part of a cyclic or aromatic group and may be interrupted by heteroatoms, where W may also be a polyoxyalkylene or polyalkylenimine bridge having at least 21 carbon atoms,
R′ is hydrogen, C1-20-alkyl, carbonylalkyl, cycloalkyl or aryl,
M+ is a cation equivalent,
X− is an anion equivalent and
x is an integer from 1 to 240,
where one or more of the radicals R11 to R16 may bear an additional trivalent phosphorus or nitrogen group capable of coordination,
where one of the radicals R or R11 to R16 or, if present, a group W in the compounds of the formula VI.a or VI.b may also be a polymer radical having a number average molecular weight in the range from 500 to 50 000, and made up of repeating units derived from monomers selected from among monoolefins and diolefins, vinylaromatics, esters of α,β-ethylenically unsaturated monocarboxylic and dicarboxylic acids with C1-C30-alkanols, N-vinyl amides, N-vinyllactams, heterocyclic compounds which can be polymerized with ring opening and mixtures thereof,
which comprises
A) reacting at least one phosphabenzene of the formula IV
34
where R11, R12, R13, R14 and R15 are as defined above, with an organometallic compound R-Me or Me-W-Me′, where R and W are as defined above and Me and Me′ are each a metal atom or a group containing a metal atom, and subsequently with at least one compound of the formula R16—X or X—W—Y, where X and Y are nucleophilically displaceable groups and R16 and W are as defined above, and
B) hydrogenating the reaction product(s) obtained in step A) by means of hydrogen in the presence of a hydrogenation catalyst.

19 more elements

A process for preparing at least one phosphacyclohexane of the formula V

36
in which
R
is hydrogen, C1-100-alkyl, cycloalkyl, heterocycloalkyl, C7-20-aralkyl, C7-20-alkaryl, C6-12-aryl, hetaryl, W′COO−M+, W′SO3−M+, W′PO32−M+2, W′NR′3+X−, W′OR′, W′NR′2, W′COOR′, W′SR′, W′(CHR′CH2O)xR′, W′(CH2NR′)xR′, W′(CH2CH2NR′)nR′, W′((CH2)4O)xR′ or W′COR′,
where the radicals R or one of the radicals R11 to R15 in each of two identical or different units V may together be a bridging group W which covalently joins these units to one another,
R11 to R15
are each, independently of one another, hydrogen, C1-20-alkyl, C7-20-aralkyl, C7-20-alkaryl, C6-12-aryl, where one or more carbon atoms may be replaced by heteroatoms, W′COO−M+, W′SO3−M+, W′PO32−M+2, W′NR′3+X−, W′OR′, W′NR12, W′COOR′, W′SR′, W′(CHR′CH2O)xR′, W′(CH2NR′)xR′, W′(CH2CH2NR′)xR′, W′((CH2)4O)xR′, W′halogen, W′NO2, W′COR′ or W′CN,
where one or more hydrogen atoms in the radicals R and R11 to R15 may be replaced by fluorine,
W and W′
are, independently of one another, single bonds or bridges having from 1 to 20 carbon atoms which may be part of a cyclic or aromatic group and may be interrupted by heteroatoms, where W may also be a polyoxyalkylene or polyalkylenimine bridge having at least 21 carbon atoms,
R′ is hydrogen, C1-20-alkyl, carbonylalkyl, cycloalkyl or aryl,
M+ is a cation equivalent,
X− is an anion equivalent and
x is an integer from 1 to 240,
where one or more of the radicals R and R11 to R15 may bear an additional trivalent phosphorus or nitrogen group capable of coordination,
where one of the radicals R or R11 to R15 or, if present, a group W in the compounds of the formula V may also be a polymer radical having a number average molecular weight in the range from 500 to 50 000 and made up of repeating units derived from monomers selected from among monoolefins and diolefins, vinylaromatics, esters of α,β-ethylenically unsaturated monocarboxylic and dicarboxylic acids with C1-30-alkanols, N-vinyl amides, N-vinyl lactams, heterocyclic compounds which can be polymerized with ring opening and mixtures thereof,
which comprises
α) reacting at least one pyrylium salt of the formula IX
37
where R11, R12, R13, R14 and R15 are as defined above and X− is an anion equivalent,
with a compound of the formula R-PH2 or H2P—W—PH2, where R and W are as defined above,
β) hydrogenating the reaction product(s) obtained in step α) by means of hydrogen in the presence of a hydrogenation catalyst, and
γ) reacting the hydrogenation product(s) from step β) with at least one reducing agent,
where the steps β) and γ) may be carried out in any order.

21 more elements

Dependencies are inferred from the claim text.

Phosphacyclohexanes and the use thereof in the hydroformylation of olefins

Life of this patent

Phosphacyclohexanes and the use thereof in the hydroformylation of olefins

Life of this patent

Abstract

Claims25