Processes for production of oxadiazoline derivatives

Details Processes for production of oxadiazoline derivatives Processes for production of oxadiazoline derivatives

2002-05-29

2003-10-07

Rotman, Alan L. (Department: 1625)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C514S340000, C514S364000, C546S269100, C548S131000

Reexamination Certificate

active

06630592

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a process for producing oxadiazoline derivatives (for example, compounds [IX], [IX
a
] and the like described hereinafter), intermediates for synthesis of the oxadiazoline derivatives, and a process for producing the intermediates. The oxadiazoline derivatives are useful as insecticides and acaricides.
BACKGROUND ART
So far, known processes for producing &Dgr;
2
-1,2,4-oxadiazoline derivatives having a pyrazol substituent at the 3-position thereof include e.g. a process for producing the derivatives from cyanopyrazol derivatives (JP-A 10-152476).
However, a process for synthesizing 3-pyrazolyl-&Dgr;
2
-1,2,4-oxadiazoline derivatives having various kinds of substituents on the nitrogen atom at the 4-position of the oxadiazoline ring is still not known, and at present, there is no satisfactory process as a general or industrial process for synthesis of &Dgr;
2
-1,2,4-oxadiazoline derivatives useful as insecticides and acaricides.
OBJECT OF THE INVENTION
An object of the present invention is to provide a satisfactory process as a general or industrial process for synthesizing &Dgr;
2
-1,2,4-oxadiazoline derivatives useful as insecticides and acaricides.
SUMMARY OF THE INVENTION
The present inventors extensively studied for solving the problem described above, and unexpectedly found that 3-pyrazolyl-&Dgr;
2
-1,2,4-oxadiazoline derivatives can be synthesized in high yield by the ring transformation reaction of 3-isoxazolyl-&Dgr;
2
-1,2,4-oxadiazoline derivatives, and the present invention was thereby completed.
That is, the present invention relates to:
1. A process for producing isoxazole-5-carboxamide oxime represented by formula [I]:
or a salt thereof, which comprises reacting 5-cyanoisoxazole with hydroxylamine or a salt thereof;
2. A process for producing 3-(5-isoxazolyl)-&Dgr;
2
-1,2,4-oxadiazoline represented by formula [II]:
or a salt thereof, which comprises reacting isoxazole-5-carboxamide oxime represented by formula [I]:
or a salt thereof with formaldehyde or an equivalent thereof;
3. A process for producing a compound represented by formula [IV]:
wherein R
1
represents an optionally substituted alkyl group, an optionally substituted acyl group or chlorocarbonyl group (ClCO), or a salt thereof, which comprises reacting 3-(5-isoxazolyl)-&Dgr;
2
-1,2,4-oxadiazoline represented by formula [II]:
or a salt thereof with a compound represented by formula [III]:
R
1
X
1
  [III]
wherein X
1
represents a halogen atom, and R
1
is as defined above, or an equivalent thereof or a salt thereof;
4. A process for producing a compound represented by formula [V]:
wherein R
1
is as defined in the above 3, or a salt thereof, which comprises subjecting a compound represented by formula [IV]:
wherein R
1
is as defined in the above item 3, or a salt thereof to the ring-opening reaction of the isoxazole ring;
5. A process for producing a compound represented by formula [VII]:
wherein R
1
is as defined in the above item 3, and R
2
represents (1) halogen, (2) C
1-6
haloalkyl group, (3) C
1-6
haloalkoxy group or (4) phenyl group optionally substituted with a C
1-6
haloalkyl group] or a salt thereof, which comprises reacting a compound represented by formula [V]:
wherein R
1
is as defined in the above item 3, or a salt thereof with a compound represented by formula [VI]:
wherein A represents a nitrogen atom or
(wherein R
3
represents chlorine atom or cyano group, and the other symbol is as defined above, or a salt thereof;
6. A process for producing a compound represented by formula [IX]:
wherein R
1
is as defined in the above item 3, R
2
and A are as defined in the above item 5, and R
4
represents a C
1-6
alkyl group or C
1-6
haloalkyl group, or a salt thereof, which comprises reacting a compound represented by formula [VII]:
wherein R
1
is as defined in the above item 3, and R
2
and A are as defined in the above item 5, or a salt thereof with a compound represented by the formula [VIII]:
R
4
SO
n
X
2
  [VIII]
wherein R
4
is as defined above, n is 0, 1 or 2, and X
2
represents a halogen atom;
7. A process for producing a compound represented by formula [IV
b
]:
wherein R
5
and R
6
each represent a C
1-6
alkyl group, or R
5
and R
6
, together with their adjacent nitrogen atom, represent a cyclic amino group, or a salt thereof, which comprises reacting a compound represented by formula [IV
a
]:
wherein X represents a chlorine atom, 1-chloroethoxy group, chloromethoxy group or phenoxy group, or a salt thereof with an amine represented by formula [X]:
R
5
R
6
NH  [X]
wherein the symbols are as defined above, or a salt thereof;
8. A process for producing a compound represented by formula [V
a
]:
wherein R
5
and R
6
are as defined in the above item 7, or a salt thereof, which comprises subjecting a compound represented by formula [IV
b
]:
wherein R
5
and R
6
are as defined in the above item 7, or a salt thereof to the ring-opening reaction of the isoxazole ring;
9. A process for producing a compound represented by formula [VII
a
]:
wherein R
2
and A are as defined in the above item 5, and R
5
and R
6
are as defined in the above item 7, or a salt thereof, which comprises reacting a compound represented by formula [V
a
]:
wherein R
5
and R
6
are as defined in the above item 7, or a salt thereof with a compound represented by formula [VI]:
wherein R
2
and A are as defined in the above item 5, or a salt thereof;
10. A process for producing a compound represented by formula [IX
a
]:
wherein R
2
and A are as defined in the above item 5, R
4
and n are as defined in the above item 6, and R
5
and R
6
are as defined in the above item 7, or a salt thereof, which comprises reacting a compound represented by formula [VII
a
]:
wherein R
2
and A are as defined in the above item 5, and R
5
and R
6
are as defined in the above item 7, or a salt thereof with a compound represented by formula [VIII]:
R
4
SO
n
X
2
  [VIII]
wherein R
4
, n and X
2
are as defined in the above item 6;
11. 3-(5-Isoxazolyl)-&Dgr;
2
-1,2,4-oxadiazoline represented by formula [II]:
or a salt thereof;
12. A compound represented by formula [IV]:
wherein R
1
is as defined in the above item 3, or a salt thereof;
13. A compound represented by formula [V]:
wherein R
1
is as defined in the above item 3, or a salt thereof;
14. A compound represented by formula [VII]:
wherein R
1
is as defined in the above item 3, and R
2
and A are as defined in the above item 5, or a salt thereof;
15. A compound represented by formula [IV
a
]:
wherein X is as defined in the above item 7, or a salt thereof;
16. A compound represented by formula [IV
b
]:
wherein R
5
and R
6
are as defined in the above item 7, or a salt thereof;
17. A compound represented by formula [V
a
]:
wherein R
5
and R
6
are as defined in the above item 7, or a salt thereof; and
18. A compound represented by formula [VII
a
]:
wherein R
2
and A are as defined in the above item 5, and R
5
and R
6
are as defined in the above item 7, or a salt thereof.
DETAILED DESCRIPTION OF THE INVENTION
In the formulae above, the alkyl group in the optionally substituted alkyl group represented by R
1
includes e.g. C
1-6
alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
The substituent on the alkyl group include hydroxyl group, amino group, mono- or di-C
1-6
alkylamino group (e.g., methylamino, ethylamino, propylamino, dimethylamino, diethylamino and the like), C
1-6
alkoxy group (e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy and the like), C
1-6
alkylthio group (e.g., methylthio, ethylthio, n-

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