Oxygenation catalyst and process for producing a ketone...

Details Oxygenation catalyst and process for producing a ketone... Oxygenation catalyst and process for producing a ketone...

1998-05-05

2001-05-15

Padmanabhan, Sreeni (Department: 1621)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C548S475000, C568S357000, C568S818000

Reexamination Certificate

active

06232258

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a catalyst useful for efficiently oxygenating (oxidizing) a substrate with oxygen and an oxygenation process (an oxo-producing process) using the catalyst, and a process for producing a ketone (e.g., a monoketone, a polyketone, a hydroxyketone).
BACKGROUND OF THE INVENTION
An adamantanol derivative compound is a useful material as an commercial material. Specifically, a ketone among the adamantanol derivative compound is chemically used with comparative ease as a novel material or a material for medicines or agricultural chemicals, and commercial values thereof are increasing.
As a laboratory-level process for producing adamantanone, some technical examples using a three-step reaction are reported. The reaction comprises cationizing a separately prepared tertiary adamantanol, generating a secondary adamantanol with maintaining an equilibrium via 1,2-sigmatropy and converting it to an irreversible ketone body in a further continuous oxidation.
Schlatmann, for example, has reported that 2-adamantanone can be obtained in 72% yield by heating to maintain 1-adamantanol in concentrated sulfuric acid for 12 hours at 30° C. [Tetrahedronn, 24, 5361 (1968)].
Further, Geluk has reported that 2-adamantanol can be obtained in 50% yield from adamantane and in 70% yield from 1-damantanol, respectively, by heating to maintain them in 120-fold eqiv. concentrated sulfuric acid for 5 hours at 70° C. [Tetrahedronn, 24, 5369 (1968)].
These producing process, however, is not commercially suitable process because of using a large quantity of concentrated sulfuric acid. Moreover, the reaction is conducted under severe condition. Further, it is reported in these literatures that a slight deterioration of the condition of super strong acid insures a decrease of the yield of the ketone body, thus controlling the acidic condition is highly difficult. On the other hand, any process for producing a commercially useful hydroxyketone, polyketone or the like has not been reported.
Incidentally, a compound substituted by a hydroxyl group at a tertiary carbon atom of the site connecting adjacent rings each other, is useful as a physiologically active substance and has high utility values as an antiviral drug (agent), an antibacterial drug (agent), a plant hormone, and so forth. A compound bound by a functional group at a carbon atom of the connecting site of the rings, is broadly utilized as a raw material of various perfumes, a fragrant compound. Thus, a tertiary alcohol body having a hydroxyl group at the connecting site of rings, is an important compound. Therefore, producing a hydroxyketone body, which is a tertiary alcohol body and ketone body having a hydroxyl group at the connecting site of rings, is exceedingly important.
Japanese Patent Application Laid-open No. 38909/1996 (JP-A-8-38909) proposes a process for generating adipic acid by oxidizing cyclohexanone or cyclohexanol with molecular oxygen in the presence of an oxidation catalyst comprising an imide compound. A process for generating isocoumarin by oxidizing isochroman with molecular oxygen in the presence of the oxidation catalyst comprising the imide compound is also proposed.
On the page 762 of the “Lecture Draft II” (1994) of 67th Spring Annual Meeting of Chemical Society of Japan, it is reported that oxidation of adamantane with oxygen by using N-hydroxyphthalimide provides a corresponding alcohol or ketone. However, producing a ketone body or a hydroxyketone body, effectively and efficiently, with controlling a generation of a polyol body of a polycyclic hydrocarbon such as adamantane, is difficult. Specifically, it is difficult to give the ketone body and the hydroxyketone body with high conversion and selectivity.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide a catalyst which insures efficient oxygenation of a substrate with oxygen and a oxygenation process using the catalyst.
It is another object of the invention to provide a catalyst which can oxygenate a substrate with oxygen even in a mild or moderate condition and a oxygenation process using the catalyst.
A further object of the invention is to provide a catalyst which can provide a ketone with high conversion and selectivity by using oxygen and a oxygenation process using the catalyst.
It is yet another object of the invention to provide a process for producing a ketone, efficiently, in a simple operation and less steps.
The present inventors did much investigation to accomplish the above objects, and as a result, found that a reaction of a substrate with oxygen in the presence of a catalyst comprising a specific imide compound and a strong acid, insures efficient oxygenation of the substrate. The present invention has been accomplished based on the above findings.
Thus, a catalyst of the present invention, which is used for contacting a substrate with oxygen to oxygenate (oxidize) the substrate, comprises comprising an imide compound shown by the following formula (I),
wherein R
1
and R
2
respectively represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group; or R
1
and R
2
may bond together to form a double bond, or an aromatic or non-aromatic ring; X represents an oxygen atom or a hydroxyl group; and n denotes an integer of 1 to 3,
and a strong acid. A pKa value of the strong acid at 25° C. is in the range of about −15 to 2.
The catalyst may comprise the imide compound shown by the formula (1), the strong acid and a co-catalyst. As such a co-catalyst, for instance, a compound containing at least one element selected from the group consisting of, for example, Group 2A elements of the Periodic Table of Elements, a transition metal element and Group 3B elements of the Periodic Table of Elements may be employed.
According to the present invention, a substrate is converted to a ketone by contacting the substrate with oxygen in the presence of the catalyst. The substrate comprises, for instance, (a) a compound having a methyl group or a methylene group at an adjacent site of an unsaturated bond, (b) a homo- or heterocyclic compound having a methylene group, (c) a compound having a methine carbon atom, (d) a compound having a methyl group or a methylene group at an adjacent site of an aromatic ring and (e) a compound having a methyl group or a methylene group at an adjacent site of a carbonyl group.
The present invention also comprises a process for producing a ketone corresponding to a substrate by using the oxygenation process.
DETAILED DESCRIPTION OF THE INVENTION
[Imide Compound]
In the imide compound shown by the formula (1), the halogen atom, as the substituents R
1
and R
2
, includes iodine, bromine, chlorine and fluorine atoms. The alkyl group includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, or other straight chain or branched chain alkyl groups each having about 1 to 10 carbon atoms. An illustrative preferred alkyl group includes alkyl groups having about 1 to 6 carbon atoms, in particular lower alkyl groups having about 1 to 4 carbon atoms.
As the aryl group, there may be mentioned, for instance, a phenyl group and a naphthyl group. Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and cyclooctyl groups.
The alkoxy group includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, and other alkoxy groups each having about 1 to 10 carbon atoms. Among them, alkoxy groups having about 1 to 6 carbon atoms, in particular lower alkoxy groups having about 1 to 4 carbon atoms are preferable. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, iso-propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, and other alkoxycarbonyl groups each having about 1 to 10 carbon atoms in the alkoxy

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