Process for producing aziridine compounds

Details Process for producing aziridine compounds Process for producing aziridine compounds

2000-03-09

2001-11-27

Solola, T. A. (Department: 1626)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C548S967000, C548S968000, C558S434000

Reexamination Certificate

active

06323346

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for producing aziridine compounds which are useful as, for example, precursors of amino acids and &bgr;-lactam antibiotics and as intermediates in organic synthetic reactions.
2. Description of the Related Art
Processes are known for producing aziridine compounds. For example, such aziridine compounds can be obtained by (i) a process of allowing a halogenating agent such as phosphorus chloride or thionyl chloride to act on a &bgr;-amino-alcohol to form a &bgr;-halogenoamine and treating the &bgr;-halogenoamine with potassium hydroxide or another base for cyclization (Gabriel method), (ii) a process of allowing sulfuric acid to act on a&bgr;-amino-alcohol to form a &bgr;-amino-sulfuricester and reacting the &bgr;-amino-sulfuric ester with sodium hydroxide or another base for cyclization (Wenker method), or (iii) a process of reacting a ketoxime with a Grignard reagent in excess to form aziridine via azirine. These processes, however, require large amounts of phosphorus compounds or other reagents and are inevitably accompanied with complicated aftertreatments. In addition, the processes by-produce large amounts of salts, which are disadvantageous from viewpoints of resources and environment.
SUMMARY OF THE INVENTION
Accordingly, an object of the invention is to provide a process for easily and efficiently producing an aziridine compound.
After intensive investigations, the present inventors found that a reaction of an imine with a diazoacetic acid derivative in the presence of an iridium compound can produce a corresponding aziridine compound in good yield. The present invention has been accomplished on the basis of these findings.
Specifically, the invention provides, in an aspect, a process for producing an aziridine compound. The process includes the step of reacting an imine with a diazoacetic acid derivative in the presence of an iridium compound to yield an aziridine compound, and the imine is of the following formula (1):
wherein R
1
, R
2
and R
3
are each, identical to or different from one another, a hydrogen atom or a non-reactive organic group, where R
1
and R
2
may be combined to form a ring together with the adjacent carbon atom, the diazoacetic acid derivative is of the following formula (2):
N
2
CHR
4
  (2)
wherein R
4
is a cyano group or a group of the following formula (3) or (4):
—COOR
5
  (3)
—CONR
6
R
7
  (4)
wherein R
5
is a hydrocarbon group or a heterocyclic group, and R
6
and R
7
are each, identical to or different from each other, a hydrogen atom, a hydrocarbon group or a heterocyclic group, where R
6
and R
7
may be combined to form a ring together with the adjacent nitrogen atom, and the aziridine compound is of the following formula (5):
wherein R
1
, R
2
, R
3
and R
4
have the same meanings as defined above.
In another aspect, the invention provides another process for producing an aziridine compound. This process includes the step of reacting a carbonyl compound with an amino-group-containing compound and a diazoacetic acid derivative in the presence of an iridium compound to yield an aziridine compound of the formula (5). In this process, the carbonyl compound is of the following formula (6):
wherein R
1
and R
2
are each, identical to or different from each other, a hydrogen atom or a non-reactive organic group, where R
1
and R
2
may be combined to form a ring together with the adjacent carbon atom, the amino-group-containing compound is of the following formula (7):
R
3
NH
2
  (7)
wherein R
3
is a hydrogen atom or a non-reactive organic group, and the diazoacetic acid derivative is of the following formula (2):
N
2
CHR
4
  (2)
wherein R
4
is a cyano group or a group of the following formula (3) or (4):
—COOR
5
  (3)
—CONR
6
R
7
(4)
wherein R
5
is a hydrocarbon group or a heterocyclic group, and R
6
and R
7
are each, identical to or different from each other, a hydrogen atom, a hydrocarbon group or a heterocyclic group, where R
6
and R
7
may be combined to form a ring together with the adjacent nitrogen atom.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[Iridium Compound]
Iridium compounds (including elementary iridium) are employed as catalysts in the invention. Such iridium compounds include, but are not limited to, metallic iridium, iridium oxide, iridium sulfide, iridium hydroxide, iridium fluoride, iridium chloride, iridium bromide, iridium iodide, iridium sulfate, iridic acid or its salts (e.g., potassium iridate), inorganic iridium complexes [e.g., hexaammineiridium(III) salts, and pentaamminechloroiridium(III) salts], and other inorganic compounds; iridium cyanide, organic iridium complexes [e.g., tris(acetylacetonato)iridium, dodecacarbonyltetrairidium(0), chlorotricarbonyliridium(I), di-,&mgr;-chlorotetrakis(cyclooctene)diiridium(I), di-&mgr;-chlorotetrakis(ethylene)diiridium(I), di-[-chlorobis(1,5-cyclooctadiene)diiridium(I), di-,&mgr;-chlorodichlorobis(pentamethylcyclopentadienyl)diiridium(III), trichlorotris(triethylphosphine)iridium(III), pentahydridobis(trimethylphosphine)iridium(V), chlorocarbonylbis(triphenylphosphine)iridium(I), chloroethylenebis(triphenylphosphine)iridium(I), (pentamethylcyclopentadienyl)dicarbonyliridium(I), bis{1,2-bis(diphenylphosphino)ethane}iridium(I) chloride, pentamethylcyclopentadienylbis(ethylene)iridium(I), and carbonylmethylbis(triphenylphosphine)iridium(I)], and other organic compounds.
The iridium may have any valency ranging from 0 to 6, preferably from 0 to 3, and especially 1 or 3.
Preferred iridium compounds include iridium complexes, particularly organic iridium complexes. Among them, organic iridium complexes each having an unsaturated hydrocarbon ligand such as cyclooctene, 1,5-cyclooctadiene, ethylene, or pentamethylcyclopentadiene are typically preferred. Such organic iridium complexes include, but are not limited to, di-&mgr;-chlorotetrakis(cyclooctene)diiridium(I), di -&mgr;-chlorotetrakis(ethylene)diiridium(I), and di-&mgr;-chlorobis(1,5-cyclooctadiene)diiridium(I). Each of these iridium compounds can be used alone or in combination.
The iridium compound can be employed as such or as being supported by a carrier. Such carriers include, for example, silica, alumina, silica-alumina, zeolite, titania, magnesia, and other inorganic metallic oxides, and activated carbon, and other conventional carriers for supporting catalysts. When the iridium compound is supported by a carrier, the proportion of the iridium compound is, for example, about 0.1 to 50% by weight, and preferably about 1 to 20% by weight relative to the weight of the carrier. The catalyst can be supported by the carrier in a conventional manner such as impregnation, precipitation, ion exchange, or another technique.
The amount of the iridium compound is, for example, about 0.001 to 1 mole, preferably about 0.005 to 0.3 mole, and more preferably about 0.01 to 0.1 mole relative to 1 mole of the substrate imine (or amino-group-containing compound).
[Imine]
The imines of the formula (1) for use as a reactant (substrate) include aldimines derived from aldehydes and ketimines derived from ketones. The term “imine” used herein also includes hydrazones, oximes, oxime ethers, oxime esters, and other compounds, as far as they each have a carbon-nitrogen double bond.
The non-reactive organic groups in R
1
, R
2
and R
3
of the formula (1) have only to be non-reactive in the present reaction. The substituents R
1
and R
2
include, for example, hydrocarbon groups, heterocyclic groups, ester groups, amido groups, and a cyano group. Examples of R
3
include, in addition to these groups, a hydroxyl group, substituted oxy groups, and unsubstituted or N-substituted amino groups.
The hydrocarbon groups include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups comprising these groups bonded with one another. Such aliphatic hydrocarbon groups include, but are not limited

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