Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-11-17
2002-09-03
Pryor, Alton N (Department: 1616)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Heterocyclic carbon compounds containing a hetero ring...
C514S245000, C514S341000, C514S342000, C514S357000, C514S365000, C514S461000
Reexamination Certificate
active
06444667
ABSTRACT:
The invention relates to synergistic insecticidal mixtures of one or more spinosyns and agonists or antagonists of nicotinic acetylcholine receptors and to their use for controlling animal pests.
It is already known that spinosyns can be used for controlling insects (WO 97/00265, WO 93/09126, WO 94/20518, U.S. Pat. Nos. 5,362,634, 5,202,242, 5,670,364, 5,227,295, see also DowElanco trade magazine Down to Earth, Vol. 52, No. 1, 1997).
However, spinosyns on their own do not always exhibit satisfactory insecticidal activity.
Furthermore, it is known that agonists and antagonists of nicotinic acetylcholine receptors can be used for controlling insects.
It has now been found that mixtures of spinosyns and at least one agonist or antagonist of acetylcholine receptors of the formula (III) are synergistically effective and suitable for controlling animal pests. Owing to this synergism, it is possible to employ considerably lower amounts of active compounds, i.e. the activity of the mixture is greater than the activity of the individual components.
The spinosyns are known compounds. The fermentation product (A 83543) described in U.S. Pat. No. 5,362,634 comprises various compounds which are referred to as spinosyn A, B, C etc. (cf. WO 97/00265, WO 93/09126 and WO 94/20518). The spinosyns can be represented by the formulae (I) and (II) below.
Compound
R
1′
R
2′
R
3′
R
4′
R
5′
R
6′
R
7′
(I)
spinosyn A
H
CH
3
C
2
H
5
CH
3
CH
3
CH
3
spinosyn B
H
CH
3
C
2
H
5
CH
3
CH
3
CH
3
spinosyn C
H
CH
3
C
2
H
5
CH
3
CH
3
CH
3
spinosyn D
CH
3
CH
3
C
2
H
5
CH
3
CH
3
CH
3
spinosyn E
H
CH
3
CH
3
CH
3
CH
3
CH
3
spinosyn F
H
H
C
2
H
5
CH
3
CH
3
CH
3
spinosyn G
H
CH
3
C
2
H
5
CH
3
CH
3
CH
3
spinosyn H
H
CH
3
C
2
H
5
H
CH
3
CH
3
spinosyn J
H
CH
3
C
2
H
5
CH
3
H
CH
3
spinosyn K
H
CH
3
C
2
H
5
CH
3
CH
3
H
spinosyn L
CH
3
CH
3
C
2
H
5
CH
3
H
CH
3
spinosyn M
H
CH
3
C
2
H
5
CH
3
H
CH
3
spinosyn N
CH
3
CH
3
C
2
H
5
CH
3
H
CH
3
spinosyn O
CH
3
CH
3
C
2
H
5
CH
3
CH
3
H
spinosyn P
H
CH
3
C
2
H
5
CH
3
H
H
spinosyn Q
CH
3
CH
3
C
2
H
5
H
CH
3
CH
3
spinosyn R
H
CH
3
C
2
H
5
H
CH
3
CH
3
spinosyn S
H
CH
3
CH
3
H
CH
3
CH
3
spinosyn T
H
CH
3
C
2
H
5
H
H
CH
3
spinosyn U
H
CH
3
C
2
H
5
H
CH
3
H
spinosyn V
CH
3
CH
3
C
2
H
5
H
CH
3
H
spinosyn W
CH
3
CH
3
C
2
H
5
CH
3
H
H
spinosyn Y
H
CH
3
C
2
H
5
CH
3
CH
3
H
spinosyn A 17-Psa
H
CH
3
H
C
2
H
5
CH
3
CH
3
CH
3
spinosyn D 17-Psa
CH
3
CH
3
H
C
2
H
5
CH
3
CH
3
CH
3
spinosyn E 17-Psa
H
CH
3
H
C
2
H
5
CH
3
CH
3
CH
3
spinosyn F 17-Psa
H
H
H
C
2
H
5
CH
3
CH
3
CH
3
spinosyn H 17-Psa
H
CH
3
H
C
2
H
5
H
CH
3
CH
3
spinosyn J 17-Psa
H
CH
3
H
C
2
H
5
CH
3
H
CH
3
spinosyn L 17-Psa
CH
3
CH
3
H
C
2
H
5
CH
3
H
CH
3
and
(II)
spinosyn A 9-Psa
H
CH
3
C
2
H
5
H
spinosyn D 9-Psa
CH
3
CH
3
C
2
H
5
H
spinosyn A aglycone
H
CH
3
H
C
2
H
5
H
spinosyn D aglycone
CH
3
CH
3
H
C
2
H
5
H
Semisynthetic spinosyns of the formula (Ia)
in which
A and B each represent a single bond, a double bond or an epoxide unit,
R represents
R
1
represents hydrogen or methyl,
R
2
, R
3
and R
4
independently of one another each represent C
1
-C
4
-alkyl, C
1
-C
4
-halogenoalkyl, C
1
-C
4
-alkylcarbonyl or protected hydroxyl,
R
5
represents hydrogen, C
1
-C
4
-alkyl, C
1
-C
4
-alkylamino or represents alkylhydroxylamino of the formula
in which
R
10
and R
11
independently of one another each represent hydrogen, C
1
-C
4
-alkyl or C
1
-C
5
-alkylcarbonyl,
R
6
represents hydrogen or methyl,
R
7
, R
8
and R
8′
independently of one another each represent C
1
-C
4
-alkyl, C
1
-C
4
-halogenoalkyl or C
1
-C
4
-alkylcarbonyl or represent protected amino and
R
9
represents methyl or ethyl
are also known (WO 97/00 265).
The compounds disclosed in WO 97/00 265 are expressly incorporated into the present application by way of reference.
The mixtures according to the invention comprise at least one spinosyn of the formula (I), (Ia) or (II).
Preference is given to synergistic mixtures with at least one spinosyn of the formula (I) or (II).
Particular preference is given to synergistic mixtures which comprise a mixture of spinosyn A and spinosyn D, where the ratio of spinosyn A to spinosyn D is generally between approximately 80:20 and approximately 98:2, and where preference is given to a value of approximately 85:15.
Very particular preference is given to using Spinosad (see, for example, DowElanco trade magazine Down to Earth, vol. 52, No. 1, 1997 and literature cited therein) which essentially consists of a mixture of spinosyn A and spinosyn D in a ratio of approximately 85:15.
Use is made, in particular, of the fermentation product A 83543 known from U.S. Pat. No. 5,362,634 which comprises approximately 85 to 90% of spinosyn A, approximately 10 to 15% of spinosyn D and smaller amounts of the spinosyns B, C, E,F,G,H and J.
It is also possible to use the acid addition salts described therein.
The agonists and antagonists of the nicotinic acetylcholine receptors are known compounds which are known from the following publications:
European Published Specifications Nos. 464 830, 428 941, 425 978, 386 565, 383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600, 192 060, 163 855, 154 178, 136 636, 136 686, 303 570X 302 833, 306 696, 189 972, 455 000, 135 956, 471 372, 302 389, 428 941, 376 279, 493 369, 580 553, 649 845, 685 477, 483 055, 580 553;
German Offenlegungsschriften Nos. 3 639 877, 3 712 307;
Japanese Published Specifications Nos. 03 220 176, 02 207 083, 63 307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255 072, 05 178 833, 07 173 157, 08291 171;
U.S. Pat. Nos. 5,034,524, 4,948,798, 4,918,086, 5,039,686, 5,034,404, 5,532,365, 4,849,432;
PCT Applications Nos. WO 91/17 659, 91/4965;
French Application No. 2 611 114;
Brazilian Application No. 88 03 621.
All the generic formulae and definitions described in these publications, and also the individual compounds described therein, are expressly incorporated herein by reference.
Some of these compounds are summarized under the term nitromethylenes, nitro-imines and related compounds.
Preferably, these compounds can be summarized under the formula (III)
in which
R represents hydrogen or represents optionally substituted radicals selected from the group consisting of acyl, alkyl, aryl, aralkyl, heterocyclyl, heteroaryl or heteroarylalkyl;
A represents a monofunctional group selected from the group consisting of hydrogen, acyl, alkyl, aryl or represents a bifunctional group which is linked to the radical Z;
E represents an electron-withdrawing radical;
X represents the radicals —CH═ or ═N—, where the radical —CH═ may be linked to the radical Z instead of an H atom;
Z represents a monofunctional group selected from the group consisting of alkyl, —O—R, —S—R,
where the radicals R are identical or different and are as defined above,
or represents a bifunctional group which is linked to the radical A or the radical X.
Particular preference is given to compounds of the formula (III) in which the radicals have the following meaning:
R represents hydrogen and represents optionally substituted radicals selected from the group consisting of acyl, alkyl, aryl, aralkyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl.
Examples of acyl radicals are formyl, alkylcarbonyl, arylcarbonyl, alkyl-sulphonyl, arylsulphonyl, (alkyl-)-(aryl-)-phosphoryl, which may themselves be substituted.
Examples of alkyl are C
1
-C
10
-alkyl, in particular C
1
-C
4
-alkyl, specifically methyl, ethyl, i-propyl, sec- or t-butyl, which may themselves be substituted.
Examples of aryl are phenyl, naphthyl, in particular phenyl.
Examples of aralkyl are phenylmethyl, phenethyl.
An example of heterocyclylalkyl is the radical
Examples of heteroaryl are heteroaryl having up to 10 ring atoms and N, O, S, in particular N, as heteroatoms. Specific examples are thienyl, furyl, thiazolyl, imidazolyl, pyridyl, benzothiazolyl, pyridazinyl.
Examples of heteroarylalkyl are heteroarylmethyl, heteroarylethyl having up to 6 ring atoms and N, O, S, in particular N, as heteroatoms, in particula
Andersch Wolfram
Schnorbach Hans-Jürgen
Wollweber Detlef
Bayer Aktiengesellschaft
Gil Joseph C.
Mrozinski, Jr. John E.
Pryor Alton N
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