Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2002-11-07
2004-12-28
Richter, Johann (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S452000, C568S457000, C556S020000
Reexamination Certificate
active
06835855
ABSTRACT:
The present invention relates to a process for the hydroformylation of ethylenically unsaturated compounds, in which at least one ethylenically unsaturated compound is reacted with carbon monoxide and hydrogen in the presence of a ligand-metal complex of ruthenium, rhodium, palladium, iridium and/or platinum, and to a ligand-metal complex suitable for the process.
Hydroformylation or the oxo process is an important industrial process and is used for preparing aldehydes by reaction of ethylenically unsaturated compounds with carbon monoxide and hydrogen. The reaction itself is strongly exothermic and generally proceeds under superatmospheric pressure and elevated temperatures in the presence of catalysts. In industrial practice, cobalt catalysts were first employed, but rhodium catalysts now predominate. To stabilize the rhodium-containing catalyst during the reaction and to avoid decomposition of the catalyst with precipitation of metallic rhodium during the work-up, phosphorus-containing ligands are generally used as cocatalysts. In the case of lower &agr;-olefins, the use of triphenylphosphine and other triarylphosphines, in particular, as cocatalysts has proven useful (cf., for example, J. Falbe, New Synthesis with Carbonmonoxide, Springer, Berlin, 1980, p. 55ff). Although lower &agr;-olefins can be hydroformylated very well using triarylphosphine-modified rhodium catalysts, this catalyst system is not very suitable for internal and internal branched olefins and for higher &agr;-olefins. Thus, internal and internal branched double bonds are hydroformylated only very slowly in the presence of such a catalyst. For this reason, the hydroformylation of substrates having internal and/or internal branched double bonds requires use of high pressures and/or temperatures.
WO 98/42717 describes carbonylation reactions in the presence of diphosphines in which at least one phosphorus atom is part of a 2-phosphatricyclo[3.3.1.1{3,7}]decyl group.
FR 118524 describes, inter alia, the hydroformylation of olefinic compounds in the presence of a cobalt carbonyl catalyst and a cocatalyst in the form of a trioxaphosphaadamantane.
It is an object of the present invention to provide a process for the hydroformylation of ethylenically unsaturated compounds in the presence of a ligand-metal complex of ruthenium, rhodium, palladium, iridium and/or platinum as catalyst, by means of which ethylenically unsaturated compounds, in particular ethylenically unsaturated compounds having internal and/or internal branched double bonds can be reacted under pressure and/or temperature conditions which are as mild as possible.
We have found that this object is achieved by a process for the hydroformylation of ethylenically unsaturated compounds, in which at least one ethylenically unsaturated compound is reacted with carbon monoxide and hydrogen in the presence of a ligand-metal complex of ruthenium, rhodium, palladium, iridium and/or platinum, where the ligand-metal complex comprises a monophosphine, monophosphinite or monophosphinamidite ligand of the formula I
where
A together with the phosphorus atom to which it is bound forms a 2-phosphatricyclo[3.3.1.1{3,7}]decyl radical in which one or more nonadjacent carbon atoms may be replaced by heteroatoms and which may be substituted, and
R′ is hydrogen or an organic radical having a molecular weight of up to 20 000 bound via a carbon atom or oxygen atom or nitrogen atom.
In addition, the invention provides a metal-ligand complex comprising a metal selected from among ruthenium, rhodium, palladium, iridium and/or platinum and at least one monophosphine or monophosphinite ligand as defined above.
It has been found that ethylenically unsaturated compounds, in particular those having internal branched double bonds, can be reacted by means of the process of the present invention at significantly lower temperatures and/or pressures than those required for the hydroformylation of the same substrates using the same catalytically active metal but other phosphorus-containing cocatalysts, e.g. triarylphosphines. In particular, the process of the present invention makes it possible to hydroformylate ethylenically unsaturated compounds, in particular those having internal branched double bonds, at pressures of less than 100 bar, preferably less than 80 bar.
Tricyclo[3.3.1.1{3,7}]decane is also known under the trivial name “adamantane”. In the 2-phosphatricyclo[3.3.1.1{3,7}]decyl radical of the ligand used according to the present invention, one or more nonadjacent carbon atoms, which are preferably not adjacent to the phosphorus atom, may be replaced by heteroatoms, preferably oxygen atoms and/or nitrogen atoms. Preference is given to the carbon atoms in the positions 6, 9 and 10 being replaced by heteroatoms, in particular oxygen atoms.
The 2-phosphatricyclo[3.3.1.1{3,7}]decyl radical may be substituted by, for example, from 1 to 8, preferably from 1 to 4, substituents. In particular, it may bear substituents on one or more of its carbon atoms. Preference is given to one or more carbon atoms in the positions 1, 3, 5 and/or 7, in particular all carbon atoms in positions 1, 3, 5 and 7, bearing substituents which are preferably identical. Suitable substituents are, for example, halogen, alkyl, cycloalkyl, haloalkyl, aryl and or aralkyl. The carbon atoms in the positions 4 and/or 8 may bear one or two substituents, e.g. C
1
-C
4
-alkyl or halogen atoms, in particular fluorine atoms.
The radical R′ is hydrogen or an organic radical having a molecular weight of up to 20 000, preferably up to 10 000, in particular up to 5 000, bound via a carbon atom, oxygen atom or nitrogen atom. The ligands used according to the present invention are monophosphines, monophosphinites or monophosphinamidites, i.e. the radical R′ does not include a phosphorus atom. Possible radicals R′ are, in particular, alkyl, e.g. alkyl having from 1 to 500 carbon atoms, which may be interrupted by nonadjacent heteroatoms, in particular oxygen atoms and/or nitrogen atoms; cycloalkyl, aryl, aralkyl, alkoxy, cycloalkoxy, aryloxy, aralkyloxy or acyl. Furthermore, R′ may be a polymeric chain, e.g. Z(CHR″CH
2
O)
x
R′″ or Z(CH
2
CH
2
NR″)
x
R′″, where Z is a bridge consisting of from 0 to 20 atoms of which adjacent atoms may be part of a saturated or unsaturated, carbocyclic or heterocyclic ring, and R″ and R′″ are each, independently of one another, hydrogen, alkyl, cycloalkyl, aryl, aralkyl or acyl and x is an integer from 1 to 240, preferably from 1 to 60. Examples of bridges Z are —CH
2
—CH
2
—O—, —CH
2
—CH
2
—N(R″)—, —CH
2
—CH
2
— and the like.
Preferred ligands have the formula II,
where
X are each, independently of one another, O or NR,
R are each, independently of one another, hydrogen, alkyl, cycloalkyl, haloalkyl, aryl or aralkyl and
R′ is hydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, cycloalkoxy, aryloxy, aralkyloxy, alkylamino, di(alkyl)amino, cycloalkylamino, N-cycloalkyl-N-alkylamino, di(cycloalkyl)amino, arylamino, N-aryl-N-alkylamino, di(aryl)amino, aralkylamino, N-aralkyl-N-alkylamino, N-aralkyl-N-arylamino, di(aralkyl)amino, acyl or carbamoyl.
For the purposes of the present invention, the expressions employed (including those in compound nouns such as alkylamino and the like) have the following meanings:
“Alkyl”: straight-chain or branched alkyl, preferably C
1
-C
20
-alkyl, in particular C
1
-C
8
-alkyl, particularly preferably C
1
-C
4
-alkyl; examples of alkyl groups are, in particular, methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, s-butyl, t-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylprop
BASF - Aktiengesellschaft
Keil & Weinkauf
Richter Johann
Witherspoon Sikarl A.
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