Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2002-11-12
2004-04-13
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C502S162000, C502S167000, C203S032000, C568S881000, C568S885000, C556S021000
Reexamination Certificate
active
06720439
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention concerns new ruthenium hydride complexes, procedures of preparing alcohol compounds using these new complexes, and methods of separating racemic carbonyl compounds using these new complexes.
2. Description of the Prior Art
Since priorly, various methods have been known for preparing alcohol compounds by reduction of carbonyl compounds using ruthenium complexes as homogeneous catalysts. For example, in Japanese Unexamined Patent Publication No. Hei 11-189600, a ruthenium dichloride complex, having 2,2′-bis-(diphenylphosphino)-1,1′-binaphthyl, which has a C2 axis of symmetry and high chemical stability, as a phosphine ligand, is used as a chiral catalyst to reduce acetophenone under the presence of a strong base to obtain a corresponding alcohol at high enantiomeric excess and high yield.
However, since the reduction reaction using the abovementioned ruthenium dichloride complex as a chiral catalyst is carried out under the presence of a strong base, when a base-sensitive carbonyl compound having an ester group or &bgr;-amino group, etc., is reduced, side reactions occur and an alcohol compound cannot be obtained efficiently.
SUMMARY OF THE INVENTION
An object of this invention is to provide ruthenium hydride complexes that enable efficient reduction of base-sensitive carbonyl compounds. Another object of this invention is to provide procedures of preparing alcohol compounds and methods of separating racemic carbonyl compounds using these ruthenium hydride complexes.
As a result of diligent research, the present inventors have found compounds of general formula (1) to be ruthenium hydride complexes that function as catalysts that enable reduction of carbonyl compounds without the presence of a strong base. In the present specification, a compound of general formula (1) is not restricted to a single diastereomer and may be a cis form or a trans form.
(wherein for R
1
R
2
P—W—PR
3
R
4
, W is a binaphthyl group, which is bonded to phosphorus atoms at positions 2 and 2′ and may have one or more substituents at any of the other positions, each of R
1
to R
4
is the same or different hydrocarbon group that may or may not have one or more substituents, R
1
and R
2
may together form a carbon chain ring that may have one or more substituents, R
3
and R
4
may together form a carbon chain ring that may have one or more substituents,
each of R
5
to R
8
is the same or different hydrocarbon group that may or may not have one or more substituents,
Z is a hydrocarbon group that may or may not have one or more substituents, and
each of the ligands of Ru may be positioned in any manner).
Unlike prior-art ruthenium dihalide complexes, ruthenium hydride complexes of general formula (1) enable carbonyl compounds to be reduced without the presence of a strong base and thus enable alcohol compounds to be prepared by efficient reduction of base-sensitive carbonyl compounds.
Each of the hydrocarbon groups at R
1
to R
4
of general formula (1) may have a substituent and may be an aliphatic or alicyclic hydrocarbon group that is saturated or unsaturated, amonocyclic or polycyclic aromatic or fatty aromatic hydrocarbon group, or any of various such hydrocarbon groups having substituents. Such a hydrocarbon group may be selected from the group consisting of such hydrocarbon groups as alkyl, alkenyl, cycloalkyl, cycloalkenyl, phenyl, tolyl, xylyl, naphthyl, phenylalkyl, etc., and hydrocarbon groups with any of various allowable substituents, such as alkyl, alkenyl, cycloalkyl, aryl, alkoxy, ester, acyloxy, halogen atom, nitro, and cyano groups, etc. Also, when a ring is formed by R
1
and R
2
or by R
3
and R
4
, R
1
and R
2
or R
3
and R
4
may be bonded to form a carbon chain and may be selected to have any of various allowable substituents, such as alkyl, alkenyl, cycloalkyl, aryl, alkoxy, ester, acyloxy, halogen atom, nitro, and cyano groups, etc., on the carbon chain.
Examples of the amine ligand (see,general formula (2)) in general formula (1) include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,2-cyclopentanediamine, 1,2-cyclohexanediamine, N-methylethylenediamine, N,N′-dimethylethylenediamine, N,N,N′-trimethylethylenediamine, N,N,N′,N′-tetramethylethylenediamine, o-phenylenediamine, p-phenylenediamine,etc. An optically active diamine compound may also be used. Examples include such optically active diamine compounds as optically active 1,2-diphenylethylenediamine, 1,2-cyclohexanediamine, 1,2-cycloheptanediamine, 2,3-dimethylbutanediamine, 1-methyl-2,2-diphenylethylenediamine, 1-isobutyl-2,2-diphenylethylenediamine, 1-isopropyl-2,2-diphenylethylenediamine, 1-methyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-isobutyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-isopropyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-benzyl-2,2-di(p-methoxyphenyl)ethylenediamine, 1-methyl-2,2-dinaphtylethylenediamine, 1-isobutyl-2,2-dinaphthlethylenediamine, 1-isopropyl-2,2-dinaphtylethylenediamine, etc. Furthermore, the optically active diamine compounds that may be used are not limited to optically active ethylenediamine derivatives, and optically active propanediamine derivatives, butanediamine derivatives, etc., may also be used.
As a ruthenium complex that is to be the starting material for complex synthesis, a complex of valence, 0, 1, 2, 3 or higher valence may be used. When a zero-valent or univalent ruthenium complex is used, oxidation of ruthenium must be carried out by the final stage. When a divalent complex is used, the ruthenium complex and phosphine ligand and then the amine ligand may be reacted successively or in reverse order or simultaneously for synthesis. When a ruthenium complex with a valence of 3, 4, or greater is used as the starting material, reduction of ruthenium atom must be carried out by the final stage. A ruthenium complex indicated for example in Japanese Unexamined Patent Publication No. Hei 11-189600 may be used as the ruthenium complex that is to be the starting material, and specific examples include inorganic ruthenium compounds, such as ruthenium (III) chloride hydrate, ruthenium (III) bromide hydrate, ruthenium (III) iodide hydrate, etc., diene-liganded ruthenium compounds, such as [ruthenium dichloride(norbornadiene)] polynuclear complex, [ruthenium dichloride(cyclooctadiene)] polynuclear complex, etc., aromatic-compound-liganded ruthenium compounds, such as [ruthenium dichloride(benzene)] dinuclear complex, [ruthenium dichloride(p-cimene)] dinuclear complex, [ruthenium dichloride(trimethylbenzene)] dinuclear complex, [ruthenium dichloride(hexamethylbenzene)] dinuclear complex, etc., and phosphine-liganded complexes, such as dichlorotris(triphenylphosphine)ruthenium, etc.
The reaction of the ruthenium complex that is the starting material and a phosphine ligand is carried out in toluene, xylene, or other aromatic hydrocarbon solvent; pentane, hexane, or other aliphatic hydrocarbon solvent; methylene chloride or other halogen-containing hydrocarbon solvent; ether, tetrahydrofuran, or other ether solvent; methanol, ethanol, 2-propanol, butanol, benzyl alcohol, or other alcohol solvent; or acetonitrile, N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), N-methylpyrrolidone, dimethyl sulfoxide (DMSO) or other organic solvent containing a heteroatom; at a reaction temperature between −100° C. and 200° C. to obtain a phosphine-ruthenium halide complex.
The reaction of the diamine-phosphine-ruthenium halide complex obtained and an amino ligand is carried out in toluene, xylene, or other aromatic hydrocarbon solvent; pentane, hexane, or other aliphatic hydrocarbon solvent; methylene chloride or other halogen-containing hydrocarbon solvent; ether, tetrahydrofuran, or other ether solvent; methanol, ethanol, 2-propanol, butanol, benzyl alcohol, or other alcohol solvent; or acetonitrile, DMA, DMF, N-methylpyrrolidone, DMSO or other organic solvent contai
Koizumi Masatoshi
Muñiz Kilian
Noyori Ryoji
Ohkuma Takeshi
Nagoya Industrial Science Research Institute
Nazario-Gonzalez Porfirio
LandOfFree
Synthesis of ruthenium-hydride complexes and preparation... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Synthesis of ruthenium-hydride complexes and preparation..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Synthesis of ruthenium-hydride complexes and preparation... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3255270