Production process of diphosphine oxide and diphosphonate

Details Production process of diphosphine oxide and diphosphonate Production process of diphosphine oxide and diphosphonate

2001-07-06

2002-10-29

Dentz, Bernard (Department: 1625)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

active

06472539

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a novel process for practically and conveniently producing a diphosphine oxide or diphosphonate. More specifically, the invention pertains to a novel process for practically and conveniently producing a diphosphine oxide or diphosphonate which is an intermediate for the synthesis of an optically active phosphine compound serving as an important component of an excellent catalyst for asymmetric synthesis reaction.
BACKGROUND ART
A number of reports have hitherto been made on transition metal complexes usable for asymmetric synthesis such as asymmetric hydrogenation reaction, asymmetric isomerization reaction or asymmetric hydrosilylation reaction. Among them, complexes of a transition metal such as ruthenium, rhodium, iridium or palladium each having an optically active tertiary phosphine compound as a ligand are known to have an excellent performance as a catalyst for asymmetric synthesis reaction.
In order to heighten the performance of these complexes as a catalyst for asymmetric synthesis reaction, phosphine compounds of various structures have so far been developed and reported (for example, The Chemical Society of Japan, ed., “Kagakusousetsu 32: Yuukikinzokusakutai no Kagaku”, 232-237 (1982); Ryoji Noyori, “Asymmetric Catalysis In Organic Synthesis”, A Wiley-Interscience Publications). Among these various optically active phosphine compounds so far reported, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (which will hereinafter be abbreviated to “BINAP”) is one of excellent ligands of metallic complexes. A rhodium complex (JP-B-55-61973) and a ruthenium complex (JP-B-61-6390) containing this BINAP as a ligand have already been reported.
A process for synthesizing the above-described BINAP by brominating a racemic binaphthol by using a triphenylphosphine-dibromide at a high temperature (240 to 320° C.), introducing it to the corresponding digrignard reagent, condensing the reagent with a diarylphosphinyl chloride compound to form the corresponding diphosphine oxide compound and, after optical resolution, reducing it into the corresponding tertiary diphosphine compound (a BINAP) by using a trichlorosilane as a reducing agent is known as an industrial process (H. Takaya, K. Mashima, K. Koyano, M. Yagi, H. Kumobayashi, T. Taketomi, S. Akutagawa, R. Noyori, “J. Org. Chem., 51, 629 (1986)).
As another known process for synthesizing a diphosphine compound is a process of reducing a substituted (2-nitrophenyl)diphenylphosphine oxide compound into the corresponding (2-aminophenyl)diphenylphosphine oxide compound, diazotizing and iodinating the resulting compound into the corresponding substituted (2-iodophenyl)diphenylphosphine oxide compound, dimerizing the resulting compound in the presence of copper into the corresponding diphosphine oxide compound, and after optical resolution, reducing it into the corresponding tertiary diphosphine compound by using trichlorosilane as a reducing agent (Japanese Language Laid-Open Publication (PCT) No. Hei 5-507503).
A process for obtaining a diphosphine oxide compound by reacting a phosphine oxide compound with a lithium or magnesium amide compound, and adding an oxidative metal salt to the resulting suspension is also known as a process for synthesizing a diphosphine oxide compound (JP-B-11-246576).
The conventionally known processes for producing a diphosphine compound are however accompanied with the drawbacks that a long production step is sometimes required depending on an intermediate used for its synthesis; this process includes a severe exothermic reaction; a yield of a desired optically active diphosphine compound is low; or this process is not utterly safe upon industrialization.
Synthesis of a diphosphine oxide or diphosphonate which is an intermediate for the production of a diphosphine compound also involves various problems upon industrialization such as long production step, low yield, and inclusion of a dangerous step generating severe heat.
For example, a process described in the above-described JP-B-11-246576 is dangerous because marked heat generation is recognized when an oxidative metal compound is added to a base-treated phosphine oxide. Addition of an oxidative metal compound, particularly, anhydrous ferrous chloride which is presumed to be particularly important, in portions for suppressing this heat generation is disadvantageous as an industrial operation, because this metal compound itself has high hygroscopicity.
There is accordingly a demand for the development of a practical and industrially-suited process for conveniently producing a diphosphine oxide or diphosphonate in a high yield, which process does not need a long preparation step, and is free of severe heat generation.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a novel, safe and practical process for producing, easily in a high yield without generating severe heat, a diphosphine oxide or diphosphonate compound which is useful as an intermediate for the synthesis of a diphosphine compound useful as a ligand constituting a metallic complex catalyst having excellent performances such as chemical selectivity, enantioselectivity and catalytic activity in asymmetric synthesis reaction, particularly asymmetric hydrogenation reaction.
In order to achieve the above objects, the present inventors made extensive studies. As a result, it has been found that a diphosphine oxide or diphosphonate such as ((5,6),(5′,6′)-bis(methylenedioxy)biphenyl-2,2′-diyl)bis(diphenylphosphine oxide) (which will hereinafter be abbreviated as “SEGPHOSO”) or ((5,6),(5′,6′)-bis(methylenedioxy)biphenyl-2,2′-diyl)bis(diphenylphosphonate) can be synthesized in a short step, safely and in a high yield while suppressing a marked heat generation reaction, for example, by suspending an oxidative metal compound such as ferric chloride in a nonpolar solvent such as toluene, adding thereto a reaction mixture obtained by treating a phosphine or phosphonate such as diphenyl(3,4-methylenedioxyphenyl)phosphine oxide or diphenyl(3,4-methylenedioxyphenyl)phosphonate with a base such as lithium diisopropylamide and reacting them, leading to the completion of the invention.
In a first aspect of the present invention, there is thus provided a process for producing a diphosphine oxide or diphosphonate represented by the following formula (1):
wherein, R
1
represents a C
1-4
alkyl group, a C
5-8
cycloalkyl group, a phenyl group, a substituted phenyl group substituted with 1 to 5 substituents which may be the same or different and each selected arbitrarily from the group consisting of C
1-4
alkyl groups, C
1-4
alkoxy groups and a phenyl group, a naphthyl group which may be substituted with a C
1-4
alkyl group or a C
1-4
alkoxy group, a C
1-4
alkoxy group, a phenoxy group, or a substituted phenoxy group substituted with 1 to 5 substituents which may be the same or different and each selected arbitrarily from the group consisting of C
1-4
alkyl groups, C
1-4
alkoxy groups and a phenyl group, which comprises treating, with a base, a phosphine oxide or phosphonate compound represented by the following formula (2):
wherein, R
1
has the same meaning as described above, and adding the thus-treated compound to a nonpolar solvent having an oxidative metal compound suspended therein so as to effect dimerization.
In a second aspect of the invention, there is also provided a process for producing a diphosphine oxide or diphosphonate represented by the formula (1), wherein in the above-described first invention, the base is selected from the group consisting of organolithium reagents, organomagnesium reagents such as Grignard reagents and magnesiumamides.
In a third aspect of the invention, there is also provided a process for producing a diphosphine oxide or diphosphonate represented by the formula (1), wherein in the above-described first invention, the oxidative metal compound is at least one selected from the group consisting of metal salts and metallic complex compounds each m

Affiliated with

Also associated with

Rating

Production process of diphosphine oxide and diphosphonate does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Production process of diphosphine oxide and diphosphonate, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Production process of diphosphine oxide and diphosphonate will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2978414