Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2002-09-13
2004-02-17
Vollano, Jean F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C564S015000, C560S129000, C560S182000, C568S013000
Reexamination Certificate
active
06693210
ABSTRACT:
TECHNICAL FIELD
This invention relates to a process for preparing a biaryl derivative useful as an intermediate for a medical or agricultural agent; a novel water-soluble ligand complex useful as a catalyst for the preparation process; as well as a novel triphenylphosphine derivative with which the complex can be prepared and a preparation process therefor.
BACKGROUND ART
Conventionally, a biaryl derivative has been typically prepared according to a process described in N. Miyaura, A. Suzuki, Synth. Commun., 11, 513 (1981), which has been extensively utilized not only in medical/agricultural applications but also organic synthesis.
The process, however, has drawbacks that a product is contaminated with palladium and phosphorous compounds requiring acid decomposition of a catalyst and then common purification such as column chromatography and recrystallization for removing them. Thus, application to a larger industrial scale requires especially easier separation of the product from a catalyst and a phosphorous compound and reduction of the amount of the catalyst.
For solving the problem of separation of the product from the catalyst, there have been known processes where a catalyst used is solubilized in water and at the end of the reaction a desired biaryl derivative is extracted with an organic layer, e.g., (A) synthesis of a biaryl derivative using a water-soluble palladium complex derived from a water-soluble phosphine ligand such as triphenylphosphino-3,3,3-trisulfonate trisodium salt (TPPTS) described in JP-A 8-59514; (B) synthesis of a biaryl derivative using a water-soluble palladium complex derived from a water-soluble phosphine ligand such as triphenylphosphino-3-sulfonate sodium salt (TPPMS) described in A. Casalnuovo, J. Am. Chem. Soc. 112, 4324 (1990), (C) using a water-soluble phosphine ligand prepared from diphenyl-4-hydroxyphenyl phosphine and a hexose to provide a water-soluble palladium complex, which is then used as a catalyst for preparing a biaryl derivative described in M. Beller, Angew. Chem. Int. Ed. Engl., 36, 772 (1997).
The process in (A) has drawbacks such as a longer reaction period and a lower yield because of a two-phase reaction. For the process in (B), an yield in a single-phase reaction is lower. The process in (C) has drawbacks such as an extremely lower yield of the ligand as the starting material for the catalyst.
DISCLOSURE OF THE INVENTION
There has been desired to develop a novel water-soluble phosphine ligand and its palladium or nickel complex which can be conveniently prepared in an improved yield, whereby in a reaction of, for example, an aryl halide with an arylboronic acid for preparing a biaryl derivative, the biaryl derivative as a product can be provided in a higher yield and the product can be easily separated from a catalyst and a phosphorous compound. Thus, objectives of this invention are to provide such a water-soluble phosphine ligand and a preparation process therefor, to provide such a complex and to provide a convenient process for preparing a biaryl derivative in a higher yield.
The inventors have intensely applied themselves to the above objectives and have finally developed a completely novel triphenylphosphine derivative and a palladium and a nickel complexes comprising the derivative as a ligand, and have established a very useful preparation process having the following features: (1) it can be used not only in an organic phase but also in an aqueous phase or a two-phase reaction system of an aqueous phase and an organic phase, (2) a catalyst and a phosphorous compound can be easily removed by post-treatment after the reaction such as water washing, and contamination with the complex or the phosphorous compound can be eliminated and (3) the biaryl derivative can be provided in a good yield using a very small amount of the catalyst.
Specifically, in the first aspect, this invention provides a triphenyl phosphine derivative represented by formula (I):
[in the formula (I), R
1
and R
2
, which may be the same or different, represent hydrogen atom, fluorine atom, alkyl with 1 to 6 carbon atoms, phenyl optionally having alkyl with 1 to 6 carbon atoms, alkenyl with 2 to 6 carbon atoms, alkynyl with 2 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkylthio with 1 to 6 carbon atoms, cyano, formyl, acyl with 2 to 7 carbon atoms, benzoyl optionally having alkyl with 1 to 6 carbon atoms, alkoxycarbonyl with 2 to 7 carbon atoms, phenoxycarbonyl optionally having alkyl with 1 to 6 carbon atoms, amino optionally having alkyl with 1 to 6 carbon atoms, amido optionally having alkyl with 1 to 6 carbon atoms, nitro, sulfonyl having alkyl with 1 to 6 carbon atoms or having phenyl optionally having alkyl with 1 to 6 carbon atoms, sulfonic ester group having alkyl with 1 to 6 carbon atoms or having phenyl optionally having alkyl with 1 to 6 carbon atoms, fluoroalkyl with 1 to 6 carbon atoms or aminoalkyl with 1 to 3 carbon atoms; m and n independently represent 1 or 2; v represents an integer of 0 to 3; z represents 1 or 2; and Q represents oxygen atom, sulfur atom or —NR— where R represents alkyl with 1 to 6 carbon atoms or hydrogen atom.]
In the second aspect, this invention provides the triphenyl phosphine derivative according to the first aspect of this invention represented by formula (II):
[in the formula (II), R
1
and R
2
, which may be the same or different, represent hydrogen atom, fluorine atom, alkyl with 1 to 6 carbon atoms, phenyl optionally having alkyl with 1 to 6 carbon atoms, alkenyl with 2 to 6 carbon atoms, alkynyl with 2 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkylthio with 1 to 6 carbon atoms, cyano, formyl, acyl with 2 to 7 carbon atoms, benzoyl optionally having alkyl with 1 to 6 carbon atoms, alkoxycarbonyl with 2 to 7 carbon atoms, phenoxycarbonyl optionally having alkyl with 1 to 6 carbon atoms, amino optionally having alkyl with 1 to 6 carbon atoms, amido optionally having alkyl with 1 to 6 carbon atoms, nitro, sulfonyl having alkyl with 1 to 6 carbon atoms or having phenyl optionally having alkyl with 1 to 6 carbon atoms, sulfonic ester group having alkyl with 1 to 6 carbon atoms or having phenyl optionally having alkyl with 1 to 6 carbon atoms, fluoroalkyl with 1 to 6 carbon atoms or aminoalkyl with 1 to 3 carbon atoms; m and n independently represent 1 or 2; v represents an integer of 0 to 3; and Q represents oxygen atom, sulfur atom or —NR— where R represents alkyl with 1 to 6 carbon atoms or hydrogen atom.]
In the third aspect, this invention provides the triphenyl phosphine derivative according to the second aspect of this invention wherein in the formula (II), R
1
and R
2
represent hydrogen; m, n and v represent 1; and Q represents —NR— where R represents alkyl or hydrogen.
In the fourth aspect, this invention provides a process for preparing the triphenyl phosphine derivative according to the first aspect of this invention by reacting a hydroxy-containing lactone with the compound represented by formula (III):
[in the formula (III), R
1
and R
2
, which may be the same or different, represent hydrogen atom, fluorine atom, alkyl with 1 to 6 carbon atoms, phenyl optionally having alkyl with 1 to 6 carbon atoms, alkenyl with 2 to 6 carbon atoms, alkynyl with 2 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkylthio with 1 to 6 carbon atoms, cyano, formyl, acyl with 2 to 7 carbon atoms, benzoyl optionally having alkyl with 1 to 6 carbon atoms, alkoxycarbonyl with 2 to 7 carbon atoms, phenoxycarbonyl optionally having alkyl with 1 to 6 carbon atoms, amino optionally having alkyl with 1 to 6 carbon atoms, amido optionally having alkyl with 1 to 6 carbon atoms, nitro, sulfonyl having alkyl with 1 to 6 carbon atoms or having phenyl optionally having alkyl with 1 to 6 carbon atoms, sulfonic ester group having alkyl with 1 to 6 carbon atoms or having phenyl optionally having alkyl with 1 to 6 carbon atoms, fluoroalkyl with 1 to 6 carbon atoms or aminoalkyl with 1 to 3 carbon atoms; m and n independently represent 1 or 2; v represents an integer of 0 to 3;
Mitsubishi Rayon Co. Ltd.
Vollano Jean F.
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