The invention relates to a method for producing activated carbon provided and/or impregnated with a metal-organic framework substance (MOF material), the activated carbon being in particular in the form of discrete activated carbon particles, and preferably for producing an activated carbon with a reactive and/or catalytic action. The metal-organic framework substance is produced in situ in the pores and/or in the pore system of the activated carbon, starting from at least one metal precursor compound (MP) containing a metal and at least one ligand precursor (LP).

The present invention relates to the technical field of adsorptive materials based on activated carbon which have some reactive/catalytic activity as well as adsorptive properties.
More particularly, the present invention relates to a process for producing an activated carbon having reactive/catalytic activity additization by endowing/impregnating the activated carbon with at least one metal-organic framework substance (MOF material).
The present invention further relates to an activated carbon having reactive/catalytic activity additization, obtainable by the process of the present invention, and also to a corresponding activated carbon as such.
The present invention further relates to uses of the activated carbon having catalytic/reactive activity/additization in the manufacture of filters and filter materials of any kind and also in the manufacture of protective materials of any kind. The present invention further relates to uses of the activated carbon according to the invention as a sorption store, as a catalyst/catalyst carrier and also for chemical catalysis and as gas sensor or in fuel cells. The present invention further relates to the uses of the activated carbon of the present invention for sorptive applications and/or for gas cleaning and also for gas purification and/or for the removal of noxiants. The present invention finally relates to the use of the activated carbon according to the invention for reprocessing/providing cleanroom atmospheres.
The present invention further relates to protective materials as such, obtained by using the activated carbon according to the invention and/or including the activated carbon according to the invention. The present invention further relates to filters/filter materials as such, obtained by using the activated carbon according to the invention and/or including the activated carbon of the present invention.
Chemical and biological noxiants/poisons and thus toxic substances based on organic and inorganic compounds/chemistries may occur in various forms in the built and/or natural environment and are an immense potential hazard to human life and health. The underlying chemical and biological noxiants/poisons may differ widely in origin:
For example, harmful or even toxic compounds are often by-produced in industrial processes as undesired secondary/waste products which, if improperly handled and, more particularly, if freely released into the environment, are a source of high danger and/or high toxic potential.
Chemical/biological noxiants/poisons are also employed as chemical/biological warfare agents, interchangeably also known as chemical warfare agents (CWAs). Warfare agents of this type continue to be part of the arsenal of many countries. In addition, owing to their in-principle ease of production and simplicity of transportation, warfare agents of this type represent a constant risk that they will also come into the possession of terrorist groups, so there is a permanent danger of misuse for that reason as well. The best-known warfare agents are, in particular, mustard gas, also known by the synonym of "HD", soman, sarin, phosgene and also tabun.
There are numerous prior art methods reportedly offering a basis for ensuring some protection against the above-adduced noxiants/poisons, in particular against toxic substances of industrial origin and also warfare agents. These include, for example, the employment of liquid/gas-impervious barrier materials processable in an appropriate manner, for example into protective suits. However, the materials employed for this are sometimes deficient in wearing comfort, since they prevent not only air but also water vapor transfer.
Adsorption materials, particularly in the form of activated carbon, are a further possibility for ensuring some protective function against chemical/biological noxiants/poisons. The adsorption material, in particular the activated carbon, may in this context be employed in the form of filters, for example on the basis of filters for NBC protective masks or the like. Employing adsorption materials of this type in protective suits is a further possibility, in which case the adsorption materials employed for this purpose are often fixed on a supporting structure. This makes it possible in principle to also realize air and water vapor pervious materials, which serves in particular to increase the wearing comfort of the protective suits manufactured on this basis—and this without significantly reducing the protective function.
Activated carbon has highly non-specific adsorptive properties—which ensures a protective function with regard to numerous chemical/biological noxiants/poisons of various types/characteristics—and a high adsorption capacity and so is the most widely used adsorbent in this context. Statutory requirements as well as increasing environmental awareness are leading to an increasing demand for activated carbon.
Activated carbon is generally obtained by carbonization (also known as pyrolysis) and subsequent activation of carbonaceous starting compounds, the preference being for starting compounds which lead to economically viable yields. This is because the weight losses caused by detachment of volatile constituents during carbonization and by the subsequent burn-out during activation are appreciable. For further details regarding the production of activated carbon in general, reference may be made for example to H. v. Kienle and E. Bäder, "Aktivkohle and ihre industrielle Anwendung", Enke Verlag Stuttgart, 1980.
The constitution of the activated carbon produced—whether finely or coarsely porous, firm or brittle, etc.—is also dependent on the starting material. Customary starting materials are coconut shells, charcoal and wood (e.g., waste wood), peat, bituminous coal, pitches, but also particular plastics, which play a certain part in the production of activated carbon cloths inter alia.
Various forms of activated carbon are used: carbon powder, splint coal and/or granulocarbon, molded carbon and also, since the end of the 1970s, activated carbon in spherical form ("spherocarbon"). Spherical activated carbon has a number of advantages over other forms of activated carbon, such as carbon powder, splint coal, granulocarbon, molded carbon and the like, making it valuable or even indispensable for certain applications: it is free-flowing, abrasion resistant, i.e. dustless, and hard. Spherocarbon, for example, is very much in demand for particular uses because of its specific shape, but also because of its high abrasion resistance.
Spherocarbon is currently still mostly produced in multi-step processes which are very costly and inconvenient. The best-known process consists in spherules being produced from coal tar pitch and suitable asphaltic residues from the petrochemical industry and oxidized (to render them unmeltable), and then carbonized and activated. For instance, spherocarbon is also obtainable in a multi-step process proceeding from bitumen. These multi-step processes are very cost-intensive, and the associated high price of the spherocarbon thus obtainable is a bar to many uses where spherocarbon actually ought to be preferred on account of its properties.
WO 98/07655 A1 describes a process for producing activated carbon spherules wherein a mixture comprising a distillation residue from diisocyanate production, a carbonaceous processing aid and optionally one or more further added substances is first processed into flowable spherules and subsequently the spherules thus obtained are carbonized and then activated.
The prior art further discloses the production of spherocarbon by carbonization and subsequent activation of virgin or spent ion exchangers containing sulfonic acid groups, or by carbonization of ion exchanger precursors in the presence of sulfuric acid with subsequent activation, wherein the sulfonic acid groups and the sulfuric acid, respectively, have the function of a crosslinker. Processes of this type are described for example in DE 43 28 219 A1, DE 43 04 026 A1 and also DE 196 00 237 A1 including the DE 196 25 069 A1 application for a German patent of addition.
The prior art further discloses processes wherein the production of activated carbon, in particular spherocarbon, is effected by carbonization and subsequent activation of sulfonated divinylbenzene-crosslinked polystyrenes (i.e., sulfonated styrene-divinylbenzene copolymers), cf. for example DE 10 2007 050 971 A1.
There are specific uses, however, where it is not just the geometry and/or outer shape of the activated carbon which is of decisive importance, but also its porosity, in particular the total pore volume and the adsorption capacity on the one hand and the distribution of the pores, i.e., the fraction of micro-, meso- and macropores in relation to the total pore volume, on the other. Especially the porosity can be intentionally varied through the choice of starting materials and also through the processing conditions. In the context of the present invention, the term "micropores" refers to pores having pore diameters of less than 2 nm, whereas the term "mesopores" refers to pores having pore diameters in the range from 2 nm (i.e., 2 nm inclusive) to 50 nm and the term "macropores" refers to pores having pore diameters of more than 50 nm (i.e. >50 nm).
Its good adsorptive properties help activated carbon into employment for a multiplicity of uses. For instance, activated carbon is employed for example in medicine or pharmacy, but also in the food industry. Activated carbon is also widely used for filter applications (e.g., filtration of gases and liquids, removal of unwanted or harmful/toxic gases, etc.).
Activated carbon is employable in particular in adsorption filter materials, including in particular specifically in protective materials against poisons, such as chemical-biological warfare agents, for example NBC protective apparel.
Air and water vapor pervious protective suits against chemical warfare agents are known for this purpose in particular; these air and water vapor pervious protective suits often have an adsorption filter layer comprising activated carbon to adsorb the chemical poisons.
There are disadvantages entailed by the use of porous adsorbents in the form of activated carbon in that, in particular, the capacity for adsorbing the chemical/biological noxiants/poisons in question is limited. This is because a specifically durable attachment of the adsorbed substances in the porous system of the activated carbon employed leads to a certain degree of saturation/exhaustion, limiting the uptake/adsorption of further noxiants. There is also a risk that the adsorbed noxiants/poisons will desorb again from the noxiant/poison-laden adsorbents and so will be released again.
On the other hand, activated carbon as such does not always have the ideal adsorption spectrum/bandwidth for the particular application, in particular with regard to the adsorption of inorganic chemistries/compounds, such as ammonia, hydrogen sulfide and hydrogen cyanide, or the like. Gas treatment and/or purification in particular requires adsorption materials having optimum adsorption capacities for inorganics as well as organics.
The prior art in this context discloses an additization of activated carbon on the basis of so-called salt impregnations, in particular in the form of metal salts present as such in the activated carbon. More particularly, permeable adsorptive filtering systems, in particular permeable adsorptive filtering systems based on activated carbon, are often additized with a catalyst to enhance the adsorptive performance/spectrum, in that this is reported to not only provide a certain degree of regenerability to the activated carbon but also to broaden the adsorption spectrum with regard to inorganic substances in particular.
An example of a specific impregnation employed in this context is a so-called ABEK impregnation, which has a catalytic effect with regard to specific toxic substances. In this context, type A relates to certain organic gases and vapors having a boiling point>65° C., for example cyclohexane. Type B relates to certain inorganic gases and vapors, for example hydrogen cyanide. Type E relates to a degrading/protecting effect with regard to sulfur dioxide and other acidic gases and vapors. Type K finally relates to a protective function with regard to ammonia and organic derivatives of ammonia. For further information, see the relevant European standard EN 14387 (January 2004).
The disadvantage with conventional impregnations of activated carbon is the fact that some of the adsorption capacity of the activated carbon, in particular with regard to organic compounds, is lost by the impregnation, which thus also reduces the adsorption and hence neutralization of chemical noxiants. The performance capability of the activated carbon is thus at times adversely affected by the impregnation processes known from the prior art.
In addition, a conventional additization of activated carbon with a catalytic/reactive component does not always attain the desired efficacy. Particularly the problem of noxiants/poisons, in particular warfare agents, striking through at high concentrations is also not always solved by this principle; on the other hand, the desired efficiency is often not achieved at very low concentrations of to-be-removed noxiants or unwelcome gases (in the reprocessing of air for cleanroom conditions, for example), since effective adsorption only ensues at higher concentrations. Moreover, any conventional additization of activated carbon, in particular with metal salts, requires relatively large amounts of impregnant and, on the other hand, the desired homogeneous loading/additization of the adsorbents with the impregnating material is often not achieved in a satisfactory manner.
Against this background, approaches have been pursued in the prior art to provide adsorption materials having not only some reactive/catalytic activity but also improved adsorption properties with regard to inorganic toxic substances in particular.
EP 1 738 823 A2 in this context relates to a catalytically active unit comprising a supporting material, wherein the catalytically active unit or the supporting material comprises polymeric particles, wherein the polymeric particles include at least one catalytically active component, wherein organic-inorganic hybrid polymers in this regard, containing metals and/or heteroatoms in addition to silicon alkoxides and/or Si—O—Si units. The materials described, however, primarily act not as adsorbents but as catalytically active particles as such.
DE 10 2005 022 844 A1 describes a process for separating odorants from gases wherein a gas is said to be brought into contact with a filter which contains a porous metal-organic framework material, wherein the framework material includes at least one at least two-pronged organic compound bound coordinatively to a metal ion. Yet there are disadvantages in the occasionally costly and inconvenient production process and also the limited adsorption performance of the resulting adsorption material.
WO 2009/056184 A1 relates to a sorption filter material including an adsorbent based on a metal-organic framework substance and also, as a further adsorbent, a spatially separate sorbent based on activated carbon. The particles of the metal-organic framework substance on the one hand and also the particles based on activated carbon, on the other, may be fixed on a supporting material. The resulting sorption filter material, however, is not ideal with regard to its physical properties in particular, since particularly the particles based on the metal-organic framework material may have a lower stability and/or attritional hardness. In addition, the adsorption properties resulting from the separate arrangement of activated carbon on one side and of metal-organic framework substance on the other are not always ideal particularly under extremely high noxiant exposure in that adsorption properties across the area of the sorption filter material are sometimes not unitary with regard to organic and/or inorganic compounds.

Activated carbon with a special finishing, production and use thereof


The invention relates to novel substituted cyanophenyluracils of the general formula (I)

The invention relates to novel substituted cyanophenyluracils, to processes for their preparation and to their use as crop treatment agents, in particular as herbicides and insecticides.
Certain substituted phenyluracils are known to have herbicidal properties (cf. EP-408 382/U.S. Pat. Nos. 5,084,084/5,127,935/5,154,755, EP-563 384, EP-648 749, WO 91/00278, U.S. Pat. Nos. 4,979,982, 5,169,430). However, these compounds have hitherto not attained any major importance.
This invention provides the novel substituted cyanophenyluracils of the general formula (I)
in which
Q represents O, S, SO or SO2,
R1 represents hydrogen, cyano or halogen,
R2 represents hydrogen or represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl and heterocyclylalkyl,
R3 represents hydrogen, halogen or represents a respectively optionally substituted radical from the group consisting of alkyl and alkoxy,
R4 represents optionally substituted alkyl and
R5 represents hydrogen or represents a respectively optionally substituted radical from the group consisting of alkyl, alkoxy, alkenyl and alkinyl,
but excluding the known compounds 1-(4-cyano-2-fluoro-5-methylthio-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine, 1-(4-cyano-2-fluoro-5-methoxycarbonylmethylthio-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine and 1-[4-cyano-2-fluoro-5-(1-ethoxycarbonyl-ethylthio)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine (cf EP-408 382, p. 85 and U.S. Pat. No. 5,084,084, Col. 76) by disclaimer.
The novel substituted cyanophenyluracils of the general formula (I) are obtained when
(a) substituted halogenophenyluracils of the general formula (II)
xe2x80x83in which
R1, R3, R4 and R5 are each as defined above and
X represents halogen,
are reacted with nucleophilic compounds of the general formula (III)
Mxe2x80x94Qxe2x80x94R2xe2x80x83xe2x80x83(III)
in which
Q and R2 are each as defined above and
M represents hydrogen or an alkali metal,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or
(b) substituted cyanophenyluracils of the general formula (Ia)
xe2x80x83in which
Q, R1, R2, R3 and R4 are each as defined above
are reacted with an alkylating agent, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent.
The novel substituted cyanophenyluracils of the general formula (I) have strong herbicidal and insecticidal activity.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably flurorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula (I)
in which
Q represents O, S, SO or SO2,
R1 represents hydrogen, cyano, fluorine or chlorine,
R2 represents hydrogen, represents respectively optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl-, di-(C1-C4-alkyl)-amino-carbonyl- or Nxe2x80x94C1-C4-alkyl-N-phenyl-amino-carbonyl- (where the phenyl group is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl or methoxy) substituted alkyl, alkenyl or alkinyl having in each case up to 10 carbon atoms, represents. respectively optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, C1-C4-alkyl-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted cycloalkyl or cycloalkylalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety and optionally up to 4 carbon atoms in the alkyl moiety, represents respectively optionally cyano-, carboxyl-, nitro-, carbamoyl-, thiocarbomyl-, fluorine-, chlorine-, bromine-, or C1-C4-alkyl-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl-, C1-C4-alkyl-sulphonyl-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl- (each of which is optionally by fluorine and/or chlorine), or phenyl-, phenoxy- or phenylthio- (each of which is optionally substituted by fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl and/or trifluoromethoxy) substituted aryl or arylalkyl having 6 or 10 carbon atoms in the aryl moiety and optionally up to 4 carbon atoms in the alkyl moiety,
R2 furthermore represents respectively optionally cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, fluorine-, chlorine-, bromine-, or C1-C4-alkyl-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl- (each of which is optionally by fluorine and/or chlorine), or phenyl-, phenoxy- or phenylthio- (each of which is optionally substituted by fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl and/or trifluoromethoxy) substituted substituted furyl, tetrahydrofuryl, thienyl, tetrahydrothienyl, oxetanyl, thietanyl, oxazolyl, isoxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, triazinyl, indolyl, quinolinyl or quinoxalinyl,
R3 represents hydrogen, fluorine, chlorine, bromine or represents respectively optionally fluorine- and/or chlorine-substituted alkyl or alkoxy having in each case 1 to 4 carbon atoms,
R4 represents optionally fluorine- and/or chlorine-substituted alkyl having 1 to 4 carbon atoms and
R5 represents hydrogen or represents respectively optionally fluorine-, chlorine- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkenyl or alkinyl having in each case up to 6 carbon atoms,
but excluding the known compounds 1-(4-cyano-2-fluoro-5-methylthio-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine, 1-(4-cyano-2-fluoro-5-methoxycarbonylmethylthio-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine and 1-[4-cyano-2-fluoro-5-(1-ethoxycarbonyl-ethylthio)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine (cf. EP-408 382, p. 85 and U.S. Pat No. 5,084,084, Col. 76) by disclaimer.
The invention in particular provides compounds of the formula (I)
in which
Q represents O, S, SO or SO2,
R1 represents hydrogen, fluorine or chlorine,
R2 represents hydrogen, represents respectively optionally cyano-, carboxyl-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, n- or i-propoxycarbonyl-, dimethylaminocarbonyl- or diethylaminocarbonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, propenyl, butenyl, pentenyl, propinyl, butinyl or pentinyl,
R2 furthermore represents respectively optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, methoxy-, ethoxy-, n- or i-propoxy-, acetyl- or propionyl-, methoxycarbonyl-, ethoxycarbonyl-, n- or i-propoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl,
R2 furthermore represents respectively optionally cyano-, carboxyl-, nitro-, carbamoyl-, thiocarbamoyl-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, n- or i-propoxycarbonyl-substituted phenyl, benzyl or phenylethyl, or
R2 furthermore represents respectively optionally cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, n- or i-propoxycarbonyl-, or phenyl-, phenoxy- or phenylthio-substituted substituted furyl, tetrahydrofuryl, thienyl, tetrahydrothienyl, oxetanyl, thietanyl, oxazolyl, isoxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, triazinyl, indolyl, quinolinyl or quinoxalinyl,
R3 represents hydrogen, fluorine, chlorine, bromine or methyl,
R4 represents methyl, ethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, chloroethyl, fluoroethyl, dichloroethyl, dichloroethyl, chlorofluoroethyl, chlorodifluoroethyl, fluorodichloroethyl, trifluoroethyl, tetrafluoroethyl, chlorotrifluoroethyl or pentafluoroethyl and
R5 represents hydrogen or represents respectively optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, propenyl, butenyl, propinyl or butinyl,
but excluding the known compounds 1-(4-cyano-2-fluoro-5-methylthio-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine, 1-(4-cyano-2-fluoro-5-methoxycarbonylmethylthio-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine and 1-[4-cyano-2-fluoro-5-(1-ethoxycarbonyl-ethylthio)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine (cf. EP-408 382, p. 85 and U.S. Pat. No. 5,084,084, Col. 76) by disclaimer.
The general or preferred radical definitions listed above are valid both for the end products of the formula (I) and also, in a corresponding manner, for starting materials or intermediates which are required in each case for the preparation. These radical definitions can be combined with each other at will, i.e. combinations between the given preferred ranges are also possible.
Examples of the compounds of the formula (I) according to the invention are listed in the groups below.
Group 1
R2 has, for example, the meanings in the list below:
hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, fluoroethyl, chloroethyl, chlorofluoroethyl, difluoroethyl, dichloroethyl, trifluoroethyl, trichloroethyl, chlorodifluoroethyl, tetrafluoroethyl, chlorotrifluoroethyl, pentafluoroethyl, fluoropropyl, chloropropyl, difluoropropyl, dichloropropyl, trifluoropropyl, trichloropropyl, cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, methoxymethyl, ethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylethyl, propoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylpropyl, propoxycarbonylpropyl, 1-propen-3-yl (allyl), 3-methyl-1-propen-3-yl, 2-buten-4-yl (crotonyl), 1-propin-3-yl (propargyl), 3-methyl-1-propin-3-yl, 2-butin-4-yl, cyclopropyl, cyanocyclopropyl, carboxycyclopropyl, difluorocyclopropyl, dichlorocyclopropyl, methylcyclopropyl, methoxycarbonylcyclopropyl, ethoxycarbonylcyclopropyl, cyclobutyl, cyanocyclobutyl, carboxycyclobutyl, difluorocyclopropyl, trifluorocyclobutyl, tetrafluorocyclobutyl, chlorotrifluorocyclobutyl, methylcyclobutyl, cyclopentyl, cyanocyclopentyl, carboxycyclopentyl, fluorocyclopentyl, chlorocyclopentyl, difluorocyclopentyl, dichlorocyclopentyl, methylcyclopentyl, methoxycarbonylcyclopentyl, ethoxycarbonylcyclopentyl, cyclohexyl, cyanocyclohexyl, carboxycyclohexyl, fluorocyclohexyl, chlorocyclohexyl, difluorocyclohexyl, dichlorocyclohexyl, methylcyclohexyl, trifluoromethylcyclohexyl, methoxycarbonylcyclohexyl, ethoxycarbonylcyclohexyl, cyclopropylmethyl, difluorocyclopropylmethyl, dichlorocyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyanocyclohexylmethyl, carboxycyclohexylmethyl, fluorocyclohexylmethyl, chlorocyclo-hexylmethyl, methylcyclohexylmethyl, trifluoromethylcyclohexylmethyl, phenyl, cyanophenyl, carboxyphenyl, nitrophenyl, fluorophenyl, chlorophenyl, bromophenyl, methylphenyl, trifluoromethylphenyl, methoxyphenyl, difluoromethoxyphenyl, trifluoromethoxyphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, benzyl, cyanobenzyl, carboxybenzyl, fluorobenzyl, chlorobenzyl, methylbenzyl, trifluoromethylbenzyl, methoxybenzyl, difluoromethoxybenzyl, trifluoromethoxybenzyl, methoxycarbonylbenzyl, ethoxycarbonylbenzyl, phenylethyl, furyl, tetrahydrofuryl, thienyl, tetrahydrothienyl, oxetanyl, oxazolyl, isoxazolyl.
Group 2
R2 has, for example, the meanings listed above in Group 1.
Group 3
R2 has, for example, the meanings listed above in Group 1.
Group 4
R2 has, for example, the meanings listed above in Group 1.
Group 5
R2 has, for example, the meanings listed above in Group 1.
Group 6
R2 has, for example, the meanings listed above in Group 1.
Group 7
R2 has, for example, the meanings listed above in Group 1.
Group 8
R2 has, for example, the meanings listed above in Group 1.
Group 9
R2 has, for example, the meanings listed above in Group 1.
Group 10
R2 has, for example, the meanings listed above in Group 1.
Group 11
R2 has, for example, the meanings listed above in Group 1.
Group 12
R2 has, for example, the meanings listed above in Group 1.
Group 13
R2 has, for example, the meanings listed above in Group 1.
Group 14
R2 has, for example, the meanings listed above in Group 1.
Group 15
R2 has, for example, the meanings listed above in Group 1.
Group 16
R2 has, for example, the meanings listed above in Group 1.
Group 17
R2 has, for example, the meanings listed above in Group 1.
Group 18
R2 has, for example, the meanings listed above in Group 1.
Group 19
R2 has, for example, the meanings listed above in Group 1.
Group 20
R2 has, for example, the meanings listed above in Group 1.
Using, for example, 1-(4-cyano-2,5-difluoro-phenyl)-3,6-dihydro-2,6-dioxo-5-chloro-4-difluoromethyl-3-methyl-1(2H)-pyrimidine and potassium ethoxide as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following scheme:
Using, for example, 1-(2-chloro-4-cyano-5-methylthio-phenyl)-3,6-dihydro-2,6-dioxo-4-chlorodifluoromethyl-5-methyl-1(2H)-pyrimidine and bromomethane as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following scheme:
The formula (II) provides a general definition of the substituted halogenophenyluracils to be used as starting materials in the process according to the invention for preparing the compounds of the formula (I). In the formula (II), R1, R3, R4 and R5 each preferably or in particular have that meaning which has already been indicated above, in the description of the compounds of the formula (I) to be prepared according to the invention, as preferred or as particularly preferred for R1, R3, R4 and R5; X preferably represents fluorine, chlorine or bromine, in particular fluorine.
The starting materials of the formula (II) are known and/or can be prepared by processes known per se (EP 648749, Preparation Examples).
The formula (III) provides a general definition of the nucleophilic compounds further to be used as starting materials in the process according to the invention for preparing the compounds of the formula (I). In the formula (III), Q and R2 each preferably or in particular have that meaning which has already been indicated above,. in the description of the compounds of the formula (I) to be prepared according to the invention, as preferred or as particularly preferred for Q and R2; M preferably represents hydrogen, lithium,. sodium or potassium, in particular hydrogen, sodium or potassium.
The starting materials of the formula (III) are known chemicals for synthesis.
The process (a) according to the invention for preparing the compounds of the formula (I) is preferably carried out in the presence of a suitable reaction auxiliary. Suitable reaction auxiliaries are generally the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide, sodium ethoxide or potassium ethoxide, sodium n- or i-propoxide or potassium n- or i-propoxide, sodium n-, i-, s- or t-butoxide or potassium n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), and 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU).
The process (a) according to the invention for preparing the compounds of the formula (I) is preferably carried out in the presence of a diluent. Suitable diluents are generally the customary organic solvents. These preferably include aliphatic, alicyclic and aromatic, optionally halogenated hydrocarbons, such as, for example, pentane, hexane, heptane, petroleum ether, ligroin, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, methylcyclohexane, di-chloromethane (methylene chloride), trichloromethane (chloroform) or carbon tetrachloride, dialkyl ethers, such as, for example, diethyl ether, diisopropyl ether, methyl-t-butyl ether (MTBE), ethyl-t-butyl ether, methyl-t-pentyl ether (TAME), ethyl-t-pentyl ether, tetrahydrofuran (THF), 1,4-dioxane, ethylene glycol dimethyl ether or ethylene glycol diethyl ether, diethylene glycol dimethyl ether or diethylene glycol diethyl ether; dialkyl ketones, such as, for example, acetone, butanone (methyl ethyl ketone), methyl-i-propyl ketone or methyl-i-butyl ketone, nitriles, such as, for example acetonitrile, propionitrile, butyronitrile or benzonitrile; amides, such as, for example, N,N-dimethyl-formamide (DMF), N,N-dimethyl-acetamide, N-methyl-formamide, N-methyl-pyrrolidone or hexamethyl-phosphoric triamide; esters, such as, for example, methyl acetate, ethyl acetate, n- or i-propyl acetate, n-, i- or s-butyl acetate; sulphoxides, such as, for example, dimethyl sulphoxide; alcohols, such as, for example, methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; mixtures thereof with water or pure water.
When carrying out the process (a) according to the invention, the reaction temperatures can be varied over a relatively wide range. In general, temperatures of between 0xc2x0 C. and 200xc2x0 C., preferably between 10xc2x0 C. and 150xc2x0 C., are employed.
The process (a) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressurexe2x80x94in general between 0.1 bar and 10 bar.
To carry out the process (a) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use one of the components in a relatively large excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for several hours at the temperature required. Work-up is carried out according to customary methods (cf. the Preparation Examples).
The formula (Ia) provides a general definition of the substituted cyanophenyluracils to be used as starting materials in the process (b) according to the invention for preparing the compounds of the formula (I). In the formula (Ia), Q, R1, R2, R3 and R4 each preferably or in particular have that meaning which has already been indicated above, in the description of the compounds of the formula (I) to be prepared according to the invention, as preferred or as particularly preferred for Q, R1, R2, R3 and R4.
The starting materials of the formula (Ia) are novel compounds according to the invention; they can be prepared by the process (a) according to the invention.
The process (b) according to the invention is carried out using an alkylating agent. Alkylating agents in this context are preferably optionally fluorine-, chlorine- or C1-C4-alkoxy-substituted alkyl halides, alkenyl halides or alkinyl halides (in particular chlorides, bromides or iodides) having in each case up to 6 carbon atoms, or dialkyl sulphates having up to 6 carbon atoms in the alkyl groups. The compounds are known chemicals for synthesis.
The process (b) according to the invention for preparing the compounds of the formula (I) is preferably carried out in the presence of a suitable reaction auxiliary. Suitable reaction auxiliaries are generally the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide, sodium ethoxide or potassium ethoxide, sodium n- or i-propoxide or potassium n- or i-propoxide, sodium n-, i-, s- or t-butoxide or potassium n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethyl amine, tri ethyl amine, tripropylamine, tributyl amine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethylpyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methylpiperidine, 1,4-diazabicyclo[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), or 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU).
The process (b) according to the invention for preparing the compounds of the formula (I) is preferably carried out in the presence of a diluent. Suitable diluents are generally the customary organic solvents. These preferably include aliphatic, alicyclic and aromatic, optionally halogenated hydrocarbons, such as, for example, pentane, hexane, heptane, petroleum ether, ligroin, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, methylcyclohexane, dichloromethane (methylene chloride), trichloromethane (chloroform) or tetrachloromethane, dialkyl ethers, such as, for example, diethyl ether, diisopropyl ether, methyl t-butyl ether (MTBE), ethyl t-butyl ether, methyl t-pentyl ether (TAME), ethyl t-pentyl ether, tetrahydrofuran (THF), 1,4-dioxane, ethylene glycol dimethyl ether or ethylene glycol diethyl ether, diethylene glycol dimethyl ether or diethylene glycol diethyl ether; dialkyl ketones, such as, for example, acetone, butanone (methyl ethyl ketone), methyl i-propyl ketone or methyl i-butyl ketone, nitriles, such as, for example, acetonitrile, propionitrile, butyronitrile or benzonitrile; amides, such as, for example, N,N-dimethyl-formamide (DMF), N,N-dimethyl-acetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters, such as, for example, methyl acetate, ethyl acetate, n- or i-propyl acetate, n-, i- or s-butyl acetate; sulphoxides, such as, for example, dimethyl sulphoxide; alkanols, such as, for example, methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; mixtures thereof with water or pure water.
When carrying out the process (b) according to the invention, the reaction temperatures can be varied over a relatively wide range. In general, temperatures of between 0xc2x0 C. and 150xc2x0 C., preferably between 10xc2x0 C. and 120xc2x0 C., are employed.
The process (b) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressurexe2x80x94in general between 0.1 bar and 10 bar.
To carry out the process (b) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use one of the components in a relatively large excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for several hours at the temperature required. Work-up is carried out according to customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm-killers and, especially, as weed-killers. By weeds, in the broadest sense, are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cycnodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial cultures, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture-land, and for the selective control of weeds in annual crops.
The compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous or dicotyledenous crops by both the pre- and the post-emergence method.
Furthermore, the compounds of the formula (I) according to the invention also have strong insecticidal activity, especially against beetle larvae, such as, for example, Phaedon cochleariae, and against the caterpillars of butterflies, such as, for example, Plutella xylostella.
To a certain extent, the compounds of the formula (I) also exhibit fungidical activity, for example against Pyricularia oryzae in rice.
The active compounds, having good crop tolerance and homeotherm safety, are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene sector. They are preferably used as crop protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
From the order of Isopoda, for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus. From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec. From the order of the Symphyla, for example, Scutigerella immaculata.
From the order of the Thysanura, for example, Lepisma saccharina. From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica, Acheta domesticus, Gryllotalpa spp., Locusta-migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.
From the order of the Dermaptera, for example, Forficula auricularia. From the order of the Isoptera, for example, Reticulitermes spp. From the order of the Anoplura, for example, Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.
From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp. From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci. From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli; Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.
From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana.
From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon soistitialis, and Costelytra zealandica.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.
From the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp.
From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans.
From the order of the Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.
The phytoparasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.
Suitable compounds are, for example, those listed below:
Fungicides
2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2xe2x80x2,6xe2x80x2-dibromo-2-methyl-4xe2x80x2-trifluoromethoxy-4xe2x80x2-trifluoro-methyl-1,3-thiazole-5-carboxanilide; 2,6-dichloroN-(4-trifluoromethylbenzyl)-benzamide; (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide; 8-hydroxyquinoline sulphate; methyl (E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate; methyl (E)-methoximino-[alpha-(o-tolyloxy)-o-tolyl]-acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, calcium polysulphide, captafol, captan, carbendazim, carboxin, quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulphamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione, isoprothiolane, kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulphocarb, methfuroxam, metiram, metsulphovax, myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol; ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron; phosdrphen, phthalide, pimaricin, piperalin, polycarbamates, polyoxin, probenazole, prochloraz, proeymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanyl, pyroquilon, quintozene (PCNB), sulphur and sulphur preparations, tebucanozole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thio-phanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforin, triticonazole, validamycin A, vinclozolin, zineb, ziram.
Bactericides
bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
Insecticides/Acaricides/Nematicides
abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin. Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxin, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan, cartap, CGA 157 419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulphoton, edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivemectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mevinphos, mesulphenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, NI 25, nitenpyram, omethoate, oxamyl, oxydemethon M, oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozin, pyrachlophos, pyradaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, RH 5992, salithion, sebufos, silafluofen, sulphotep, sulprofos, tebufenozid, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.
A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators, is also possible.
The active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations, as a mixture with synergists. Synergists are compounds which increase the action of the active compounds without it being necessary for the synergist added to be active itself.
The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
The compounds are employed in a customary manner appropriate for the use forms.
When used against hygiene pests and pests of stored products, the active compound has an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
The active compounds according to the invention are not only active against plant, hygiene and stored-product pests, but also, in the veterinary medicine sector, against animal parasites (ectoparasites), such as ixodid ticks, argasid ticks, scab mites, trombiculid mites, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird lice and fleas. These parasites include:
From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
From the order of the Mallophagida and the sub-orders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
From the order Diptera and the sub-orders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.,
From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.
From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela germanical and Supella spp.
From the sub-class of the Acaria (Acarida) and the orders of the Meta- and Mesostigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp, Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Octodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which attack agricultural livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, honey bees, other domestic animals, such as, for example, dogs, cats, cage birds, aquarium fish, and so-called experimental animals such as, for example, hamsters, guinea-pigs, rats and mice. By controlling these arthropods, it is intended to reduce mortality and decreased performance (in meat, milk, wool, hides, eggs, honey and the like), so that more economical and simpler animal keeping is made possible by using the active compounds according to the invention.
In the veterinary sector, the active compounds according to the invention are used in a known manner by enteral administration, for example in the form of tablets, capsules, drinks, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, such as, for example, by means of injections (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal application, by dermal administration, for example in the form of dipping or bathing, spraying, pouring-on and spotting-on, washing, dusting, and with the aid of shaped articles which comprise active compound, such as collars, ear tags, tail marks, limb bands, halters, marking devices and the like.
When administered to livestock, poultry, domestic animals and the like, the active compounds of the formula (I) can be used as formulations (for example powders emulsions, flowables) which comprise the active compounds in an amount of 1 to 80% by weight, either directly or after dilution by a factor of 100 to 10,000, or they may be used in the form of a chemical bath.
Furthermore, it has been found that the compounds of the formula (I) according to the invention have a potent insecticidal action against insects which destroy industrial materials.
The following insects may be mentioned by way of example and as being preferred, but without any limitation.
Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis; Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus;
Dermapterans, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;
Termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus;
Bristletails, such as Lepisma saccharina.
Industrial materials are to be understood as meaning, in the present context, non-live materials such as, preferably, synthetic materials, glues, sizes, paper and board, leather, wood and timber products, and paint.
The materials to be very particularly protected against attack by insects are wood and timber products.
Wood and timber products which can be protected by the composition according to the invention or mixtures comprising such a composition are to be understood as meaning, for example, construction timber, wooden beams, railway sleepers, bridge components, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wood lagging, windows and doors made of wood, plywood, particle board, joiner""s articles, or wood products which, quite generally, are used in the construction of houses or in joinery.
The active compounds can be used as such, in the form of concentrates or generally customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes.
The formulations mentioned can be prepared in a manner known per se, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant and/or binder or fixative, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, colorants and pigments and other processing auxiliaries.
The insecticidal compositions or concentrates used for the protection of wood and wooden materials comprise the active compound according to the invention at a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
The amount of the compositions or concentrates employed depends on the species and the occurrence of the insects and on the medium. The optimum rate of application can be determined upon use in each case by test series. However, in general, it suffices to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
The solvent and/or diluent used is an organochemical solvent or solvent mixture and/or an oily or oil-type organochemical solvent or solvent mixture of low volatility and/the a polar organochemical solvent or solvent mixture and/or water and, if appropriate, an emulsifier and/or wetting agent.
Organochemical solvents which are preferably employed are oily or oil-type solvents having an evaporation number of above 35 and a flashpoint of above 30xc2x0 C., preferably above 45xc2x0 C. Substances which are used as such oily and oil-type solvents which have low volatility and are insoluble in water are suitable mineral oils or their aromatic fractions, or mineral-oil-containing solvent mixtures, preferably white spirit, petroleum and/or alkylbenzene.
Substances which are advantageously used are mineral oils with a boiling range of 170 to 220xc2x0 C., white spirit with a boiling range of 170 to 220xc2x0 C., spindle oil with a boiling range of 250 to 350xc2x0 C., petroleum or aromatics of boiling range 1-60 to 280xc2x0 C., essence of turpentine and the like.
In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range of 180 to 210xc2x0 C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 220xc2x0 C. and/or spindle oil and/or monochloro-naphthalene, preferably xcex1-monochloronaphthalene, are used.
The organic oily or oil-type solvents of low volatility having an evaporation number of above 35 and a flashpoint of above 30xc2x0 C., preferably above 45xc2x0 C., can be partially replaced by organochemical solvents of high or medium volatility, with the proviso that the solvent mixture also has an evaporation number of above 35 and a flashpoint of above 30xc2x0 C., preferably above 45xc2x0 C., and that the insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture.
In a preferred embodiment, part of the organochemical solvent or solvent mixture is replaced by an aliphatic polar organochemical solvent or solvent mixture. Substances which are preferably used are aliphatic organochemical solvents having hydroxyl and/or ester and/or ether groups, such as, for example, glycol ether, esters and the like.
The organochemical binders used within the scope of the present invention are the synthetic resins and/or binding drying oils which are known per se and can be diluted with water and/or are soluble or dispersible or emulsifiable in the organochemical solvents employed, in particular binders composed of, or comprising, an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, poly-condensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenol resin, hydrocarbon resin, such as indene/coumarone resin, silicone resin, drying vegetable and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.
The synthetic resin used as the binder can be employed in the form of an emulsion, dispersion or solution. Up to 10% by weight of bitumen or bituminous substances can also be used as binders. In addition, known colorants, pigments, water repellents, odour-masking substances and inhibitors or anticorrosives per se and the like can also be employed.
The composition or the concentrate preferably comprises, in accordance with the invention, at least one alkyd resin or modified alkyd resin and/or a drying vegetable oil as the organochemical binder. Preferably used according to the invention are alkyd resins with an oil content of over 45% by weight, preferably 50 to 68% by weight.
All or some of the abovementioned binder can be replaced by a fixative (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active compounds and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of binder employed.
The plasticizers are from the chemical classes of the phthalic esters, such as dibutyl phthalate, dioctyl phthalate or benzylbutyl phthalate, the phosphoric esters, such as tributyl phosphate, the adipic esters, such as di-(2-ethylhexyl) adipate, the stearates, such as butyl stearate or amyl stearate, the oleates, such as butyl oleate, the glycerol ethers or relatively high-molecular-weight glycol ethers, glycerol esters and p-toluene-sulphonic esters.
Fixatives are chemically based on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl ether, or ketones, such as benzophenone or ethylene benzophenone.
Particularly suitable as a solvent or diluent is also water, if appropriate as a mixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersants.
Particularly effective protection of wood is achieved by large-scale industrial impregnation processes, for example vacuum, double-vacuum or pressure processes.
If appropriate, the ready-to-use compositions can additionally comprise one or more other insecticides and, if appropriate, additionally one or more fungicides.
Suitable additional components which may be admixed are, preferably, the insecticides and fungicides mentioned in WO 94/29 268. The compounds mentioned in that document are expressly incorporated into the present application by reference.
Very particularly preferred components which may be admixed are insecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron, and fungicides, such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole; metconazole, imazalil, dichlorofluanide, tolyl-fluanide, 3-iodo-2-propinylbutyl carbamate, N-octyl-isothiazolin-3-one and 4,5-di-chloro-N-octylisothiazolin-3-one.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersing agents and/or foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite, OF diatomaceous earth, and ground synthetic minerals, such as highly disperse silica alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compounds according to the invention can be used as such or, in their formulations, as a mixture with known herbicides for the control of weeds, in which case ready-to-use formulations or tank mixes are possible.
Suitable co-components for the mixtures are known herbicides, for example anilides such as, for example, diflufenican and propanil; arylcarboxylic acids such as, for example, dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids such as, for example, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as, for example, chloridazon and norflurazon, carbamates such as, for example, chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines such as, for example, oryzalin, pendimethalin and trifluralin; diphenyl ethers such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas such as, for example, chlortoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines such as, for example, alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones such as, for example, imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles such as, for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides such as, for example, mefenacet; sulphonylureas such as, for example, amido-sulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiolcarbamates such as, for example, butylates, cycloates, di-allates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; triazines such as, for example, atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; triazinones such as, for example, hexazinone, metamitron and metribuzin; others such as, for example, aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the, nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and the use of the active compounds according to the invention can be seen from the examples below.

Abstract: in which

Abstract: R1, R2, R3, R4, R5 and Q are each as defined in the description,

Abstract: to processes for their preparation, to novel intermediates and to their use as herbicides and insecticides.


A camera module having a lens unit; an intermediate part a hollow part of which the lens unit is affixed to; and a base unit which is opened in one direction and is equipped with a mounting part to which the intermediate part is mounted in such a way as to be able to rotate freely; wherein a latching protrusion that latches with the base unit is provided on an outer periphery of the intermediate part; a sliding hole having a movable step is provided on a mounting part side of the base unit; and the intermediate part moves in a direction perpendicular to the rotating direction, as the latching protrusion of the intermediate part rotates along the sliding hole of the base unit.

FIG. 12 illustrates a typical small camera module 100 used on a cellular phone equipped with a camera and other similar electronic devices comprises a lens module 101 containing lenses, an intermediate part 102 provided on the outside of the lens module 101, and a base 103 on which the intermediate part 102 equipped with the lens module 101 is mounted.
The lens module 101 is formed in a cylindrical shape, and contains a lens L1 and a lens L2 inside. A screw thread 104 is formed on the cylindrical surface of the lens module 101.
The intermediate part 102 is a ring-like part and a screw thread 105 that fit with the lens module 101 is provided on its internal cylindrical surface. The engagement between this screw thread 105 and the screw thread 104 of the lens module 101 accomplishes the assembling of the lens module 101 into the intermediate part 102. Furthermore, a screw thread 106 is provided on the outer cylindrical surface of the intermediate part 102 as well.
The base 103 provides a cylindrical space, in which a screw thread 107 is provided to engage with a crew thread 106 of the intermediate part 102, and a light receiving unit 108 is affixed to the bottom of the cylindrical space. The intermediate part 102 carrying the lens module 101 is mounted on the base 103 as the screw 106 of the intermediate part 102 is engaged with the screw thread 107 of the base 103.
The camera module 100 is normally shipped out from the factory after adjusting the focus so that an image of the lens module 101 can be focused properly on the light receiving unit 108 by means of the screw threads 106 and 107 of the intermediate part 102 and the base unit 103 respectively.
In order to use the camera module 100 utilizing its macro function, it is necessary to adjust the engagement condition of the screw threads 104 and 105 that unite the intermediate part 102 and the lens module 101 while using the equipment the camera module 100 is attached to.
To activate the macro function of the camera module 100, it is necessary to change its focal distance by moving the lens module 101 inside the intermediate part 102. However, this causes the pitch of the screw threads 104 and 105 that unite the lens module 101 and the intermediate part 102 to be too fine as overall compacting of the camera module 100 is demanded, which forces the lens module 101 and the intermediate part 102 to be smaller, thus preventing the screw threads 104 and 105 from having a coarser pitch.
Consequently, a large rotary angle of the lens module 101 is required in order to relocate it relative to the intermediate part 102 for changing from the normal use condition to the macro use condition. This causes a problem in that it is difficult to provide the macro function of the micro camera module 100 when used on devices such as cellular phones. More specifically, the problem is that it is, practically speaking, impossible to switch from the normal to macro condition on a compact camera module 100 with as screw pitch of 0.3 mm or so as it requires a rotary angle of half a revolution (180°) to one revolution (360°) in order to achieve a switching distance of 0.15 mm to 0.3 mm. Any attempt to use a larger screw thread form to minimize the required rotary angle would end up in a problem that a larger pitch screw thread means a larger thread height, thus defeating the intention of minimizing the overall size of the camera module.


The present invention relates to a method and apparatus for transmitting channel parameter information. A method for transmitting a frame in consideration of a channel environment includes the steps of: receiving long training field (LTF) setting information from a station; creating a frame including an LTF, a plurality of divided data fields, and an additional LTF on the basis of the LTF setting information; and transmitting the frame, wherein the LTF positions are ahead of the plurality of divided data fields, the additional LTF positions are between or behind the plurality of divided data fields, and the LTF setting information can be created on the basis of the movement of the station. Therefore, channel estimation performance can be increased.

Field of the Invention
The present invention concerns wireless communications, and more specifically, to a method and apparatus of transmitting channel change information.
Related Art
Machine-to-machine (M2M) systems recently draw attention as next-generation communication technology and new standards for supporting the same are now being establishment in IEEE 802.11 WLAN. An M2M system means a network where not humans but machines perform communication to exchange information. Temperature sensors, moisture sensors, cameras, TVs or other home appliances, factory processing machines, vehicles, and other large-size machines may be M2M elements. Recently, as smart grid, e-Health, ubiquitous and other various communication services appear, M2M techniques are being utilized to support such services. The M2M system has the following features.
1) Many stations: M2M assumes a great number of stations unlike existing networks because not only an individual's machine but also sensors installed in home or business should be taken into account. Accordingly, a large number of stations may be linked to a single AP.
2) Low traffic load per station: since an M2M terminal collects and reports ambient information in its traffic pattern, it need not often send information and the amount of information to be sent is relatively small.
3) Uplink-centered: M2M has a structure of primarily receiving commands on downlink, taking an action, and then reporting resultant data on uplink. Major data is usually transmitted on uplink, and thus, M2M is uplink-centered.
4) Long life-span station: an M2M terminal is primarily battery-powered, and is in many cases difficult for a user to recharge often. Accordingly, battery consumption needs to be minimized, ensuring long lifespan.
5) Automatic restoring function: an M2M terminal is hard for a human to directly manipulate and thus it requires a self-restoring function,

Method and apparatus for transmitting channel parameter information


A basket hanger attached to a basket. The basket hanger having a hook with a plurality of spring steel wires strands extending from the hook, the spring steel wire strands having a substantially straight downwardly extending portion terminated at a distal end in a clip. Each clip positionable between an open position and a clipped position. In the clipped position, an upwardly extending leg of each of the clips extends through an opening in the peripheral flange of the basket such that the peripheral flange is received in an upward first bend of each of the clips, and a second bend of each of the clips engages a back side of the substantially straight downwardly extending portion such that a short dogleg partially wraps around the substantially straight downwardly extending portion.

Hangers for plant baskets are well known. A conventional basket hanger includes an upper hook, from which a plurality of strands (typically three or four) extend downwardly. The distal ends of the strands are configured to attach to the flange of a plastic basket. The strands of conventional hangers are comprised of either mild steel wire which are welded or otherwise secured to the upper hook or, alternatively, the strands and hook are molded entirely from plastic.
Steel wire hangers offer the advantage of strength and are typically considered more aesthetically appealing than plastic hangers, but if the mild steel wire strands become bent during shipping or use, the bent wire strands will detract from the smooth, clean lines typically desired for hanging baskets. Accordingly, finished hanging basket products with mild steel wire hangers are more costly to package and ship because the mild steel wire hangers cannot be bent over for shipping in a box or shipping cage without detracting from their appearance, thereby requiring longer packages or shipping cages, even if the wire hangers are detached from the hanging baskets. Additionally, to attach a mild steel wire hanger to a hanging basket, a worker or purchaser will typically have to insert the end of the mild steel wire strands through holes in the basket flange and then bend and either twist or squeeze the end of the wire by hand to secure it to the basket. Depending on the diameter of the mild steel wire strand, in order to properly secure the hanger to the basket, a pliers or tool may be required. With or without tools, but especially without tools, if a worker's job duty is to attach conventional mild steel wire strand hangers to hanging baskets throughout the day, repeating this task several times a day can cause considerable pain and injury to the hands of a worker. Additionally, if a conventional mild steel wire strand hanger is not properly secured, the bend created at the bottom of the mild steel wire strand will open up and the hanger will detach from the basket even under normal conditions, let alone under high wind conditions when the basket is twisting and swaying.
Plastic hangers offer the advantage of allowing the hangers to be coiled or bent to fit into shorter packages when shipping the hanging basket, but plastic stranded hangers are necessarily larger in diameter than steel wire strand hangers to achieve the same tensile strength and therefore plastic strands are typically considered less aesthetically appealing. Furthermore, plastic strands and conventional mild steel wire strands are more susceptible to breaking in high wind conditions which can cause a hanging plant to twist and swing.
Accordingly, there is a need for a basket hanger which offers the advantages of a hanger with steel wire strands but which provides the advantages of allowing the hanger to be coiled or bent like a plastic hanger, but which will hold up to twisting and swaying in high wind conditions common in many areas. There is also a need for an improved manner of attaching the hanger to the basket which is more quickly and efficiently attached and does not require the use of a pliers or other tools.