Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
1998-08-31
2001-08-21
Solola, T. A. (Department: 1626)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C514S456000, C548S376100, C546S272400, C549S365000, C549S445000, C568S660000, C568S681000
Reexamination Certificate
active
06277867
ABSTRACT:
This application is the national phase under 35 U.S.C. §371 of prior PCT International Application No. PCT/HU96/00069 which has an International filing date of Nov. 19, 1996 which designated the United States of America, the entire contents of which are hereby incorporated by reference.
This invention relates to alkynyl pesticide compounds of the general formula I., pesticide compositions containing the active ingredients of general formula I., furthermore the pesticide synergists of general formula I., and synergized pesticide compositions with known pesticide active ingredients, and the process for the preparation thereof.
In general formula I the substituents have the following meanings:
Ar=an alicyclic-, aromatic-, or one or more heteroatom containing heterocyclic moiety, optionally substituted by one or more alkoxy, methylenedioxy, alkyl, halogen, haloalkyl or nitro group, and/or condensed with a benzene ring,
R
1
, R
2
=independently hydrogen, alkyl, alkenyl, haloalkyl, phenyl, substituted phenyl, cycloalkyl,
R
3
, R
4
=independently hydrogen, alkyl, alkenyl, haloalkyl, phenyl, substituted phenyl, cycloalkyl, or
R
3
, R
4
are together=O;
Y=C,=PO, or
YR
3
R
4
form together a
group;
X=—O—; —NR
10
—;
R
9
=hydrogen, alkyl, phenyl, substituted phenyl;
R
10
=hydrogen, alkyl;
R
5
, R
6
, R
7
, R
8
are independently hydrogen, alkyl, alkenyl, haloalkyl, or Ar—(CR
1
R
2
)
m
—(YR
3
R
4
)
n
—X— form together a carboximide group;
E=hydrogen, halogen, methyl;
m=0, 1, 2;
n=0, 1;
o=0, 1, 2;
p=0, 1, 2,
with the proviso that the sum of the atoms or groups of the bridge —(CR1R
2
)
m
—(CR
3
R
4
)
n
—X—(CR
5
R
6
)
o
—(CR
7
R
8
)
p
is 3 and the —C═C—E skeleton with the atoms of the bridge forms a linear chain, consisting of 6 atoms ending favorably in a methyl group,
furthermore with the proviso that if Ar is naphthyl group. Y means C-atom. X means O-atom. R
3
and R
4
together can not mean ═O.
The invention includes furthermore the salts and the optically active isomers of the compounds of general formula I.
Narrower groups within compounds of general formula I. are representated by the compounds of general formula IA, IB, IC, ID, IE, IF, their salts and optically active isomers, where the meanings of the substituents are the same as defined above.
Favourable representatives of the compounds of general formula I. are:
1-naphthyl-methyl 2-butynyl ether,
2-propynyl-1,3-benzodioxol-5-carboxylate,
1-[(2-butynyloxy)-ethyl]-3,4-dimethoxybenzene,
2,6-dichloro-1-(2-butynyloxymethyl)benzene,
1-[1-(2-butynyloxy)propyl]naphthalene,
R-(+)-2-[1-(2-butynyloxy)ethyl]naphthalene,
5-[(but-2-ynyloxy)methyl]-1,3-benzodioxole,
5-[2-methyl-1-(2-butynyloxy)propyl]-1,3-benzodioxole,
5-[(but-2-ynyloxy)phenylmethyl]-1,3-benzodioxole,
2-[(2-butynyloxy)methyl]-1,4-benzodioxane,
2,3-dihydro-2,2-dimethyl-7-(3-pentyloxy)benzofuran.
In the term Ar the aromatic group is preferably phenyl or naphthyl group, Ar as a heterocyclic moiety may contain one or more O, S, N heteroatoms, it may favourably represent benzodioxole-, benzodioxane-, 2-benzofuran-, 7-benzofuran-moieties.
The alicyclic group may favourably be condensed with a benzene ring, thus for instance may represent indane group, or 1,2,3,4-tetrahydronaphthyl group. The carboximide group may favourably represent phthalimide moiety. The aromatic, heterocyclic and alicyclic Ar groups are optionally substituted by C
1-4
alkoxy-, methylenedioxy-,C
1-4
alkyl-, halogen-, C
1-4
haloalkyl- or nitro group.
Compounds which are non-toxic, or only slightly toxic alone, but given together with a pesticide, preferably arthropodicide agent they enhance markedly the potency of the latter, are called synergists. These materials may in principle act in several ways, however they exert their effect decisively by blocking the metabolism of the active substance. Metabolism may proceed via oxidative, hydrolytic, conjugative and absorption reactions and by the variations thereof. At present there is no unambiguous example for a synergist acting at the receptor level, neither do they play an important role in the praxis.
The synergistic potency e.g. in the case of insecticides is characterized by the so-called SR synergist ratio which is given as follows:
SR
50
=
LD
50
insecticide
LD
50
insecticide
+
synergist
The more the SR
50
value differs from 1, the higher is the synergistic potency. The use of synergists in arthropodicidal preparations is very attractive since they afford a possibility to produce new preparations with practically all representatives of the area. These new preparations, compared to the previous ones, promise to be less expensive, less toxic, more selective, encountering less environmental hazard, suppressing the evolution of resistance, and being active also on strains which already evolved resistance.
Following the discovery of synergists and the reveal of their mode of action, a wide-range research and development work started from the mid 60's till the late 70's to work out new synergists. This research, however resulted only a few molecules which really attained application (at present the number of the registered insecticide synergists is less than 10). These compounds are of basic scientific importance in the research of resistance (K. F. Raffa and T. M. Priester.
J. Agric. Entomol.,
2(1), 27-45, (1985)), however, there are only 2-3 molecules listed as products in the Pesticide Manual, and only two materials (PBO, MGK264) which are actually on the market. The field application has been restricted by several factors: it is not easy to find a chemical tool which can be used selectively and safely, and the cost/effectiveness ratio of which is competitive with that of the active ingredient. To apply a synergist economically, it must be highly potent, it must act at small doses (not exceeding the original dose of the active ingredient).
On the basis of their chemical structures the presently known arthropodicide synergistic compounds may be divided into the following groups:
1,3-methylenedioxyphenyl (MDP) derivatives
O-2-propynyl and propynyl-homologues and their derivatives (ethers, oximethers, esters)
N-alkyl derivatives
phosphor esters
other derivatives e.g. thiocyanates, polyhalo ethers etc.
The compounds may also be divided into groups on the basis of their target of attack [K. F. Raffa and T. M. Priester,
J. Agric. Entomol.,
2(1), 27-45, (1985)], but this grouping is rather theoretical and less exact, because the actual metabolic processes are not fully known. The metabolism of most of the compounds proceeds consecutively, but may also proceed simultaneously, and may follow several mechanisms. Thus the division is less informative, even if we consider the first step of the cascade degradation as the decisive step.
For the metabolic degradation of most arthropodicides first of all the oxygenase system is responsible. It is agreed in the literature that the compounds of this group exert their activity basically by blocking the cytochrome P450 enzyme of the microsomal oxidation system [John E. Cassida,
J. Agr. Food Chem.,
18(5), 753-772, (1970), R. M. Sacher. R. L. Metcalf and T. R. Fukuto.
J. Agr. Food Chem.,
16(5), 779-786, (1968)]. The enzymes forming the structurally analogous group of so-called isoenzymes constitute the major part of the detoxificaton system of the organisms [Ortiz de Montellano. P. R. Ed.
Cytochrome P
-450.
Structure Mech. and Biochem
., Plenum New York, (1986)]. They perform detoxification via mono-oxygenation of the substrate, producing a more polar product, which possibly after further transformations can be eliminated by the organism. The system degrades very different structures by the same way. Therefore they are also designated as Mixed Function Oxygenases (MFO) and Polysubstrate Monooxygenases (PSMO).
On that basis one could expect that the surface of the enzyme is aspecifi
Arvai Geza
Bakonyvari Ildiko
Bertok Bela
Csiz Laszlo
Czudor Iren
Birch & Stewart Kolasch & Birch, LLP
Chinoin Gyogyszer es Vegyeszeti
Solola T. A.
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