Organic compounds -- part of the class 532-570 series – Organic compounds – Phosphorus containing
Reexamination Certificate
1999-06-23
2001-05-01
Wilson, James O. (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Phosphorus containing
C568S016000, C568S017000, C536S004100, C536S018500, C536S055300
Reexamination Certificate
active
06225504
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to hydrophilic phosphanes, a process for their production, their use in metal complexes, these metal complexes and their use in catalytic conversions.
STATE OF THE ART
Many chemical conversions of organic compounds are carried out under conditions of homogeneous catalysis. A general problem of homogeneous catalysis is the simple and economical separation, following the conversion, of the catalyst system from the organic products. The catalysts should advantageously be simple to separate from the organic products and be recyclable into the conversion process. A solution to these problems represents the so-called two-phase catalysis in which the catalyst system and the organic products are present in different phases and can be separated one from the other by simple decanting. Such two phase-catalyzed conversions are described for example in W. A. Herrmann, C. W. Kohlpaintner, Angew. Chem. 1993, 105, 1588-1609 and in P. Kalck, F. Monteil, Adv. Organomet. Chem. 1992, 34, 219. In these conversions a hydrophilic aqueous phase is frequently used as the catalyst phase, however, it is also possible to use fluoridated hydrocarbons or polyethylene glycols. The prerequisite for an effective two-phase catalysis is high solubility of the catalyst system in the catalyst phase and low solubility in the product phase. For this purpose mainly hydrophilically modified ligands have been used in the past when using metal complex catalysts. A typical example of this are sulfonated triaryl phosphanes such as are described for example in W. A. Herrmann, C. W. Kohlpaintner, Angew. Chem. 1993, 105, 1588-1609 and in P. Kalck, F. Monteil, Adv. Organomet. Chem. 1992, 34, 219. They are used commercially for the hydroformylation of propene. Up to now ionic groups such as —SO
3
−
, —CO
2
−
, —NR
3
+
, —P(O)O
2
2−
have substantially been used to increase the hydrophilicity of phosphane ligands. This is described for example in M. Beller, B. Cornils, C. D. Frohning, C. W. Kohlpaintner, J. Mol. Catal. 1995, 104, 17-85. Ionic functionalities can be of disadvantage in various processes due to the salt concentrations present. Furthermore, no chiral ionic groups are accessible. To avoid these disadvantages, neutral substituents can be used. As neutral substituents in order to increase the hydrophilicity of phosphanes have previously been used for example polyethylene glycol groups. This is described for example in B. Cornils, Angew. Chem. 1995, 107, 1709-1711.
OBJECTS OF THE INVENTION
The task of the present invention is providing hydrophilic phosphane compounds which can be used as metal complex ligands for the production of catalysts and which make accessible a multiplicity of structural variants including chiral centers.
SUMMARY OF THE INVENTION
This task is solved through a process for the production of phosphanes having the general formula (I)
Ar
1
3−x
P(Ar
2
(OZ)
y
)
x
(I)
in which Ar
1
and Ar
2
independently are aromatic C
6-20
radicals or heteroaromatic C
4-9
radicals substituted, if appropriate, by halogen atoms, carboxyl groups, hydroxyl groups, C
1-6
alkyl groups, phenyl groups or naphthyl groups wherein Ar
1
has one and Ar
2
has y+1 free valences,
Z is a carbohydrate radical with a glycosidic bond,
x has the value 1, 2 or 3, and
y has the value 1 or 2, by
(1) the conversion of carbohydrate halogenoses having the general formula (II)
Z′—X (II)
in which Z′ is a radical Z as specified above, in which the hydroxyl groups are substituted by protective groups, and X represents Br, Cl or F,
with a phosphane having the general formula (III)
Ar
1
3−x
,P(Ar
2
(OH)
y
)
x
(III)
in which Ar
1
, Ar
2
, x and y have the above meaning
in a multiphase reaction medium in the presence of a base and of a phase transfer catalyst,
into a phosphane having the general formula (IV)
Ar
1
3−x
P(Ar
2
(OZ′)
y
)
x
(IV)
in which Ar
1
, Ar
2
, x, y and Z′ have the above specified meaning, and
(2) removal of the protective groups from Z′.
It was found according to the invention that the compounds having the general formulas (I) and (IV) are accessible through the phase transfer-catalyzed conversion of carbohydrate halogenoses.
Only O. Neunhoeffer, L. Lamza, Chem. Ber. 1961, 94, 2514-2521 have published the synthesis of a triphenyl phosphane in which one phenyl radical in the p-position is substituted by a glucosyl radical, in which the hydroxyl groups are protected by acetyl groups. The production takes place through the glycosylation in aqueous acetone with potassium hydroxide as a base. The yield was 8% and was thus substantially less than the yields obtainable in the process according to the invention.
The phosphanes produced according to the invention have the general formula (I)
Ar
1
3−x
P(Ar
2
(OZ)
y
)
x
(I)
In the formula (I) the radicals Ar
1
and Ar
2
are aromatic C
6-20
radicals or heteroaromatic C
4-9
radicals. As aromatic radicals they are therein preferably independently phenyl, naphthyl, biphenyl or binaphthyl radicals. If several Ar
1
or Ar
2
radicals are present, each individual radical can independently be one of the above radicals. At least one aromatic radical Ar
1
or Ar
2
is therein preferably a phenyl radical and, especially preferred, two of the aromatic radicals are phenyl radicals. In particular all of the aromatic radicals Ar
1
and Ar
2
are phenyl radicals.
The radicals Ar
1
and/or Ar
2
as the heteroaromatic radicals comprise preferably 1 or 2, especially preferably 1 hetero atom selected from oxygen, sulphur and nitrogen. Especially preferred are radicals based on pyridine, furan or thiophene. The aromatic radicals can, if appropriate, be substituted independently of one another, for example by halogen atoms, carboxyl groups, hydroxyl groups, C
1-6
, preferably C
1-2
alkyl groups, phenyl groups or naphthyl groups. These substituents can be present in addition to the substituent(s) OZ of the radical Ar
2
. The substituents are preferably hydroxyl groups, in particular maximally one hydroxyl group per benzene nucleus is present.
Ar
1
comprises one and Ar
2
comprises y+1 free valences. y has therein the value 1 or 2. If the radical Ar
2
is a radical based on a phenyl radical, at y=1 the free valences can be present in the o-, m- or p-position. The free valences are preferably present in the o- or p-, in particular in the p-position. In the case of biphenyl radicals or binaphthyl radicals as the radicals Ar
2
, the valences are preferably present in different benzene nuclei i.e. each phenyl or naphthyl radical preferably contains at least one of the free valences. y has preferably the value 1.
x can have the value 1, 2 or 3. x preferably has the value 1 or 2, in particular the value 1. y has preferably the value 1.
Preferred compounds of formula (I) are such in which y=1 and x=1 or 2. The radical Ar
1
is therein preferably a phenyl radical or a phenyl radical substituted by an hydroxyl in the p-position. The radical Ar
2
is preferably a p-phenylene radical or a binaphthyl radical, in particular a 1,1′-binaphthyl radical in which the free valences are in the 2,2′-position.
The radical Z is a carbohydrate radical with a glycosidic bond which is derived from a sugar radical. Z is preferably derived from glucose, mannose, galactose, fructose, cellobiose, saccharose, glucosamine, N-acetylglucosamine or their stereoisomers. Consequently, Z is preferably derived from a glycosidically linked 5 or 6-member carbohydrate. Corresponding amines or N-acetylamines of these compounds can also be used. Each radical Z independently has one of the above meanings.
Z is preferably derived from glucose, galactose or N-acetylglucosamine.
The phosphanes according to the invention having the general formula (I) are produced by the conversion of carbohydrate halogenoses having the general formula (II)
Z′—X (II)
Z′ is therein a radical Z as was described
Beller Matthias
Bogdanovic Sandra
Krauter Jurgen
Zapf Alexander
Bierman, Muserlian and Lucas
Celanese GmbH
Owens Howard
Wilson James O.
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