Phosphites

Details Phosphites Phosphites

2002-04-25

2004-08-03

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S150000, C558S332000, C558S335000, C585S671000

Reexamination Certificate

active

06770770

ABSTRACT:

The present invention relates to novel phosphites, a process for preparing them, their use as ligand in transition metal complexes, novel transition metal complexes, a process for preparing them, their use as catalyst and processes carried out in the presence of such transition metal complexes as catalyst.
Triaryl phosphites, nickel complexes containing such phosphites as ligands and the use of such complexes as catalysts are known.
DE-A 2 237 703, U.S. Pat. No. 3,850,973 and U.S. Pat. No. 3,903,120 describe a process for the hydrocyanation of unsaturated organic compounds and the isomerization of nitriles in the presence of nickel(0) complexes containing tri-o-tolyl phosphite as ligand. A disadvantage of this process is that the stability of such nickel complexes is unsatisfactory. This low stability is reflected in a very low content of Ni(0), which is the active species for the hydrocyanation, in the reaction solution.
U.S. Pat. No. 3,766,237 and U.S. Pat. No. 3,903,120 describe a process for the hydrocyanation of unsaturated organic compounds and the isomerization of nitriles in the presence of nickel(0) complexes containing tri-m/p-tolyl phosphite as ligand. A disadvantage of this process is that the reactivity of such nickel complexes is unsatisfactory.
It is an object of the present invention to provide a process which makes possible the hydrocyanation of unsaturated organic compounds in a technically simple and economical manner using a catalyst which has high stability and high reactivity.
We have found that this object is achieved by phosphites of the formula I
P(O—R
1
)
x
(O—R
2
)
y
(O—R
3
)
z
(O—R
4
)
p
  I
where
R
1
: aromatic radical having a C
1
-C
18
-alkyl substituent in the o position relative to the oxygen atom which connects the phosphorus atom to the aromatic system, or having an aromatic substituent in the o position relative to the oxygen atom which connects the phosphorus atom to the aromatic system, or having an aromatic system fused on in the o position relative to the oxygen atom which connects the phosphorus atom to the aromatic system,
R
2
: aromatic radical having a C
1
-C
18
-alkyl substituent in the m position relative to the oxygen atom which connects the phosphorus atom to the aromatic system, or having an aromatic substituent in the m position relative to the oxygen atom which connects the phosphorus atom to the aromatic system, or having an aromatic system fused on in the m position relative to the oxygen atom which connects the phosphorus atom to the aromatic system, where the aromatic radical bears a hydrogen atom in the o position relative to the oxygen atom which connects the phosphorus atom to the aromatic system,
R
3
: aromatic radical having a C
1
-C
18
-alkyl substituent in the p position relative to the oxygen atom which connects the phosphorus atom to the aromatic system, or having an aromatic substituent in the p position relative to the oxygen atom which connects the phosphorus atom to the aromatic system, where the aromatic radical bears a hydrogen atom in the o position relative to the oxygen atom which connects the phosphorus atom to the aromatic system,
R
4
: aromatic radical which bears substituents other than those defined for R
1
, R
2
and R
3
in the o, m and p positions relative to the oxygen atom which connects the phosphorus atom to the aromatic system, where the aromatic radical bears a hydrogen atom in the o position relative to the oxygen atom which connects the phosphorus atom to the aromatic system,
x: 1 or 2,
y, z, p: independently of one another, 0, 1 or 2, with the proviso that x+y+z+p=3,
and by a process for preparing them, their use as ligand in transition metal complexes, novel transition metal complexes, a process for preparing them, their use as catalyst and processes carried out in the presence of such transition metal complexes as catalyst.
According to the present invention, the radical R
1
is an aromatic radical having a C
1
-C
18
-alkyl substituent in the o position relative to the oxygen atom which connects the phosphorus atom to the aromatic system, or having an aromatic substituent in the o position relative to the oxygen atom which connects the phosphorus atom to the aromatic system, or having an aromatic system fused on in the o position relative to the oxygen atom which connects the phosphorus atom to the aromatic system.
Suitable aromatic radicals are heterocycles and preferably homocycles such as the phenyl radical.
The aromatic radical may bear further functional groups such as alkoxy groups or halogens, for example chlorine or bromine; the aromatic radical preferably bears no functional groups.
According to the present invention, the aromatic radical bears a C
1
-C
18
-alkyl substituent in the o position relative to the oxygen atom which connects the phosphorus atom to the aromatic system or has an aromatic system fused on in the o position relative to the oxygen atom which connects the phosphorus atom to the aromatic system. Alkyl radicals which may be present are linear or cyclic C
1
-C
18
radicals, preferably C
1
-C
9
radicals such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, n-pentyl and its isomers, n-hexyl and its isomers, cyclopentyl or cyclohexyl radicals, where the cyclic alkyl radicals may bear linear or further cyclic alkyl radicals or aromatic radicals as substituents and the alkyl radicals may bear cyclic alkyl radicals or aromatic radicals as substituents. Preferred alkyl radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and s-butyl.
These alkyl radicals may bear further functional groups such as alkoxy groups, amino groups such as unsubstituted, monosubstituted or disubstituted amino groups, mercapto groups such as substituted mercapto groups, where the substitution may be by the abovementioned alkyl groups or aromatic radicals. The alkyl radicals preferably bear no functional groups.
In the alkyl radicals, carbon atoms may be replaced by other atoms such as oxygen, nitrogen or sulfur; the alkyl radicals preferably have none of their carbon atoms replaced.
Suitable aromatic substituents are heterocycles and preferably homocycles such as the phenyl radical.
The aromatic substituent may bear further functional groups such as alkoxy groups or halogens, for example chlorine or bromine; the aromatic substituent preferably bears no functional groups.
The aromatic substituent may bear one or more C
1
-C
18
alkyl substituents or one or more fused-on aromatic systems or be free of further substituents.
Alkyl radicals which may be present are linear or cyclic C
1
-C
18
radicals, preferably C
1
-C
9
radicals such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, n-pentyl and its isomers, n-hexyl and its isomers, cyclopentyl or cyclohexyl radicals, where the cyclic alkyl radicals may bear linear or further cyclic alkyl radicals or aromatic radicals as substituents and the alkyl radicals may bear cyclic alkyl radicals or aromatic radicals as substituents. Preferred alkyl radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and s-butyl.
These alkyl radicals may bear further functional groups such as alkoxy groups, amino groups such as unsubstituted, monosubstituted or disubstituted amino groups, mercapto groups such as substituted mercapto groups, where the substitution may be by the abovementioned alkyl groups or aromatic radicals. The alkyl radicals preferably bear no functional groups.
In the alkyl radicals, carbon atoms may be replaced by other atoms such as oxygen, nitrogen or sulfur; the alkyl radicals preferably have none of their carbon atoms replaced.
The radical R
1
is advantageously o-tolyl, o-ethylphenyl, o-n-propylphenyl, o-isopropylphenyl, o-n-butylphenyl, o-sec-butylphenyl, o-tert-butylphenyl, (o-phenyl)phenyl or 1-naphthyl.
According to the present invention, R
2
is an aromatic radical having a C
1
-C
18
-alkyl substituent in the m position relative to the oxygen atom which connects the phosphorus atom to the aromatic system, or having an aromatic substituent in the m posi

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