MXPA94007442A - Procedure and compound to prepare nitro-compounds and product obtain - Google Patents

Abstract

The present invention relates to the preparation for the nitro-compound of formula (I) wherein R 1 is C 1-4 alkyl and R 2 is hydrogen or C 1-4 alkyl, R 3 is -S-R 4 or R 5 wherein R 4 is C 1 alkyl -4, R5 and R6 are hydrogen or C1-4alkyl, Y is CH and Z is a 5-6 membered heterocyclic group having at least one nitrogen atom which may be substituted by halogen or C1-4alkyl, the process is characterized in that ) (in the case where R3 is -S-R4, R1 is then replaced by R7 where R7 is C1-4 alkyl), compounds of formula (II) wherein R4 is as defined above, are reacted with compounds of formula (III) wherein R7, R2 and Z are defined as above, in the presence of inert solvents, b) (in the case where R3 is R5 then R1 is replaced by R7), compounds of formula (Ia) are reacted wherein R7, R2, R4 and Z are defined as above, with compounds of formula (IV) wherein R5 and R6 are defined as subsequently, in the presence of inert solvents

Description

"PROCEDURE AND COMPOUND TO PREPARE NITRO-COMPOUNDS AND PRODUCT OBTAINED" Inventors: KOZO SHIOKAWA, Japanese, domiciled at 2-23-30, Shukugawara, Tama-ku, Kawasaki-shi, Kanagawa-ken, Japan; SHINICHI TSUBOI, Japanese, domiciled at 3-26-1, Hirayama, Hino-shi, Tokyo, Japan; KOICHI MORIYA, Japanese, domiciled at 1-7-3, Ueno, Taito-ku, Tokyo, Japan; YUMI HATTORI, Japanese domiciled in 598, Kobiki-machi, Hachioj i-shi, Tokyo, Japan; IKURO HONDA, Japanese, domiciled at 3-17-7, Minami-machi, Tanashi-shi, Tokyo, Japan and KATSUHIKO SHIBUYA, Japanese, domiciled at 39-15, Namiki-cho, Hachioj i-shi, Tokyo, Japan.

Causaire: NIHON BAYER AGROCHEM K.K., Japanese company; domiciled at 7-1, Nihonbashi Honcho 2-chome, Chuo-ku, Tokyo, Japan.

EXTRACT OF THE INVENTION New nitro compounds of formula (I) and the uao of the new compounds as insecticides.

DESCRIPTION OF THE INVENTION The present invention relates to new nitro-compounds, to processes for their preparation and to their use as insecticides. It has already been described that a certain group of 2-nitro-1, 1-etheno diamines is useful as drugs that influence the circulation, in particular, as hypotensive agents (see US Pat. No. 4,567,188), that a certain group of N-cyanoisothio-ureas is useful as medicaments for the treatment of ulcers (see Japanese Patent Application No. 234,064 / 1937), that the N-cyanoisothioureas described in the said Japanese patent application also have utility in the control of plant-destroying insects and nematodes (see Japanese Patent Application No. 233,903 and EP-A 303,570) and that a certain group of alpha-unsaturated amines have insecticidal / iticidal activity (see EP-A 0302,339). We have now found new nitro compounds of formula (I) R 1 R2 R 3 Z-C IH-NI-CI-Y-N02 w wherein R 1 and R 2 are hydrogen or C, C alkyl, R-37 is -S-R4 or R5 I fi - N-R6 wherein R 4 is C,., 5 'and 6'-alkyl are hydrogen or C,., alkyl, and is CH or N and Z is a 5- or 6-membered heterocyclic group having at least one nitrogen atom which can be to be substituted by halogen or C-lobule, with the proviso that when Y is CH, then it is C, alkyl. . The compounds of formula (I) can be obtained by a process in which: a): (in the case where it is -S- and Y is CH, R 1 is then replaced by R 7 where 7 is alkyl C, _. ), compounds of formula (II) are reacted R ^ -S C-CH-N02 (II) wherein R is defined as above, with compounds of formula (III) R7 Z-CH-NHR2 (III) wherein R7, R2 and Z are defined as above, in the presence of inert solvents; ^ 5 b): (in the case where 3 '' ~ is -N'-R6 and Y is CH, then R 1 is replaced by R7), compounds of formula (la) R7 R2 S-R1 are reacted » III Z-CH-NC-CH-N02 (la) 7 A wherein R, R, R and Z are defined as above, with compounds of formula (IV) where R iormente, in the presence of inert solvents; or c): (in the case where F. is -S-R and Y is N), compounds of formula (V) are reacted wherein R 2 and R 4 are defined as above, with compounds of formula (VI) R 1 Z-CH-Hal (VI where R and Z are defined as above and Hal represents a halogen atom, in the presence of inert solvents, and, if appropriate, in the presence of acid acceptors, or "d): (in the case where it is -N'-R6 and Y is N), compounds of formula (le) R1 R2 SR" III are reacted Z-CH-NCN-N02 (le) wherein R, R, R and Z are defined as above, with the above compounds of formula (IV) in the presence of inert solvents. The new nitro-compounds exhibit potent insecticidal properties. Surprisingly, the nitro-compounds according to the invention exhibit a substantially higher insecticidal activity than that shown by the compounds known from the prior art. In the previous formulas, the C, alkyl groups. represented by R 1, R 2, R 4, R "5 and R 6 are straight or branched chain, such as methyl, ethyl, n- and i-propyl and n-, i-, s- and t-butyl. In the above formulas, the 5- or 6-membered heterocyclic group represented by Z contains at least one nitrogen atom as a ring member.The 3-pyridyl, 4-pyridyl and 5-thiazole groups are preferred. zolyl, in particular 3-pyridyl and 5-thiazolyl Substituent halogen atoms on the 5- or 6-membered heterocyclic group Z are fluorine, chlorine, bromine and iodine The chlorine atom is preferred. substituents on the 5- or 6-membered heterocyclic group Z are straight or branched chain, such as methyl, ethyl, n- and i-pro-pyl and n-, i-, s- and t-butyl.The methyl group is preferred The substituent can be found in all possible positions of the 5- or 6-membered heterocyclic group R.suppressed by Z. Prefera it is in the 6-position of the anil 3-pyridyl and in the 2-position of the 5-thiazolyl ring. Among the nitro compounds according to the invention of formula (I), the preferred compounds are those in d is -S-R -NR wherein R is methyl, R and R are hydrogen or methyl, Y is CH or N and Z is 3-pyridyl, 4-pyridyl or 5-thiazolyl which may be substituted by chlorine or methyl, with the proviso that when And it's CH, so R is methyl. The most preferred nitro compounds of formula (I) are those wherein R 1 and R 2 are hydrogen or methyl, R is - -R 6 where R and R are hydrogen or methyl, Y is CH or N and Z is 2-chloro -5-pyridyl or 2-chloro-5-thiazolyl, with the proviso that when Y is CH, then R is methyl. Nitro-most preferred compounds of formula I (I) are those wherein R and R are hydrogen or methyl, R is hydrogen or methyl, Y is CH or N and Z is 2-chloro-5-pyridyl. or 2-chloro-5-thiazolyl, with the proviso that when Y is CH, 1 '2 3 then R is methyl, or when R is hydrogen and R is 6-N-R wherein either R or R is hydrogen and the other is methyl, then Y is N. Nitro-very particularly preferred compounds of formula (I) are those wherein R 1 and R 2 are hydro- R 5 fi * 5-methyl or methyl, R ^ is -NR where R3 and R are hydrogen or methyl, Y is N and Z is 2-chloro-5-pyridyl. Specifically, the following compounds can be mentioned: 3- (2-chloro-5-pyridylmethyl) -l-methyl-2-nitroguanidine, 3- (2-chloro-5-pyridylmethyl) -1, l-dimethyl-2-nitroguanidine, 3- (2-Chloro-5-pyridylmethyl) -1,3-dimethyl-2-nitroguanidine, 3- (2-chloro-5-pyridylmethyl) -l, .l, 3-trimethyl-2-nitroguani-dine, 3- (2-Chloro-5-pyridylmethyl) -3-methyl-2-nitroguanidine, 3- (2-chloro-5-thiazolylmethyl) -l-methyl-2-nitroguanidine, - a - l- "l- (2 -chloro-5-pyridyl) ethylamino __7-l-dl__ethylamino-2-nitroethylene, l-amino-l- "l- (2-chloro-5-pyridyl) ethylamino __7-2-nitro-ethylene, l-l - (2-chloro-5-pyridyl) ethylamino-7-l-methylamino-2-nitroethylene, and 1- (N- "1- (2-chloro-5-pyridyl) ethyl-7-N-methylamino-1-dimethylamino-2 -Nitroethylene For example, if in procedure a) above, 1, 1-bis-methylthio-2-nitroethylene and 1- (2-chloro-5-pyridyl) ethylamine are used as starting materials, the course of the reaction can be represented by the following equation: For example, if in procedure b) above, 1- "l- (2-chloro-5-pyridyl) ethylamino-7-l-methylthio-2-nitroethylene and methylamine are used as starting materials, the course of the reaction may be represented by the following equation: S - CH3 CH¬ Cl L- CH-NH - C - CH -N02 + CH3NH2 For example, if in procedure c) above 2-methyl-3-nitroisothiourea and 2-chloro-5-chlorome-tilpyridine are used as starting materials, the course of the reaction can be represented by the following equation: For example, if in procedure d) above, l- (2-chloro-5-pyridylmethyl) -3-nitro-2-methyliso-thiourea and dimethylamine are used as starting materials, the course of the reaction may be represented by The following equation: -N02 + (CH3) 2NH In process a), the compounds of formula (II) as starting material represent those based on the aforementioned definition of In formula (II), R4 preferably has the meanings indicated above. The compounds of formula (II) include known compounds (see, for example, Chem. Ber., Vol.100, pages 591-604, 1967) and, for example, compound 1, l-bis-methylthio-2 -nitroethylene. The compounds of formula (III) used as a starting material represent those based on the above-mentioned definitions of R 1, R 2 and Z. i 2 In formula (III), R, R and Z preferably have the meanings indicated above. The compounds of formula (III) include in part known compounds (see Nihon Kagaku Zasshi (Perio-dical of Japanese Chemistry), vol 83, pages 218-222, 1962, J. Chem. Soc. Perkin I, 1979, pages 2364 -2368). The compounds of formula (III), for example, can be prepared according to a method described in the above reference J. Chem. Soc. Perkin I, 1979. pages 2364-2368. The compounds of formula (III), in the case where R is hydrogen, they can be obtained when compounds of formula (VII) are hydrolyzed: 7 wherein R and Z are defined as above. The compounds of formula (VII) can be obtained when the Schiff bases of formula (VIII) wherein Z is defined as above, they are alkylated by reaction with compounds of formula (IX) R7-Hal (IX) 7 wherein R is defined as above and Hal is halogen, in the presence of a catalytic amount of bu-tyl-lithium and in the presence of an inert solvent, such as tetrahydrofuran. The compounds of formula (VIII) can be obtained when compounds of formula (X) are reacted Z - CH2 - NH2 (?) wherein Z is defined as above, with mesitaldehyde, in the presence of inert solvents. The compounds of formula (X) include the known compounds described in US Patent No. 4,499,097 and in the aforementioned reference Nihon agaku Zasshi. In process b), the compounds of formula (Ia) used as starting material correspond to a part of the compounds of formula (I) which can be prepared by process a) above. The compounds of formula (IV) used as starting material represent those based on the above defined definitions of R? and R. In the formula (IV);, R and R preferably have the meanings, already indicated above. Compounds ^ of formula (IV) are well known in the field of organic chemistry and, as examples, include: methylamine, diethylamine and the like. In process c), the compounds of formula (V) used as starting material represent those based on the aforementioned definitions of R2 and R4. __L In the formula (V), R and preferably have the meanings already indicated above. The compounds of formula (V) are known (see, for example, J. Am. Chem. Soc., Vol.76, pages 1877-1879, 1954) and, as examples, include: 3-nitro-2-methylisothiourea , 1, 2-dimethyl-3-nitroisothiourea, 1, 1, 2-trimethyl-3-nitroisothiourea and the like. The compounds of formula (VI) used as a starting material represent those based on the above-mentioned definitions of R, Z and Hal. In the formula (VI), R and Z preferably have the meanings already indicated above and Hal preferably represents chlorine or bromine. The compounds of formula (VI) are known (see Japanese patent applications Nos. 178981/1986, 173982/1986 or 183271/1986) and, as examples, include: 2-chloro-5-chloromethylpyridine, 2-chloro-5 -chloro-methylthiazole and the like. In process d) the compounds of formula (le) used as a starting material correspond to a part of the compounds of formula (I) which can be prepared by process c) above. The compounds of formula (IV) are the same as those used in process b) above. Suitable diluents are all inert solvents. These preferably include water; Aliphatic, cycloaliphatic and aromatic hydrocarbons, optionally chlorinated, such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichlorethylene, chlorobenzene and the like. -miles; ethers such as diethylether, methylethylether, diisopropylether, dibutylether, propylene oxide, dioxane, tetrahydrofuran and the like; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone; nitriles such as acetonitrile, pro-pionitrile, acrylonitrile and the like; alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol and the like; esters such as ethyl acetate, amyl acetate; acid amides such as dimethylformamide, dimethylacetamide and the like; and sulfones and sulfoxides such as dimethylsulfoxide, sulfolane and the like; and bases, for example, pyramid. In the above-mentioned process a), the reaction temperature can be varied within a wide range. In general, the reaction is carried out at a temperature of 0 to 150 ° C, preferably of 20 to 90 ° C., approximately . In general, the reaction is preferably carried out under normal pressure, but may also be verified under elevated or reduced pressure. In carrying out process a), for example, 0.9 mol to a slightly excess molar amount of the compounds of formula (III) may be used per mol of the compounds of formula (II) and the mixture is made react in the presence of inert solvents, under thermal reflux, until the mer-captan generation stops, so that the desired compounds of formula (I) can be obtained. In carrying out process b), suitable diluents include the same solvents exemplified for process a). In the aforementioned process b), the reaction temperature can vary within a wide range. For example, the reaction is carried out at a temperature of the order of 0 to 150 ° C, preferably 20 to 90 ° C, approximately. In general, the reaction is preferably carried out under normal pressure, but can also be carried out under elevated or reduced pressure. In the embodiment of process b), for example, an amount ranging from equimolar to slightly in excess of the compounds of formula (IV) may be used per mole of the compounds of formula (la), and the mixture is reacted in the presence of inert solvents, in order to obtain the desired compounds of formula (I). In carrying out process c), suitable diluents include the same solvents as exemplified above for process a). The aforementioned process c) can be carried out in the presence of acid acceptors such as, for example, the traditionally used hydroxides, hydrides, carbonates, bicarbonates and alcoholates of alkali metals, tertiary amines such as, for example, triethylamine, diethylamiline , pyridine, etc. In process c) mentioned above, the reaction temperature can vary within a wide range. In general, the reaction is carried out at temperatures ranging from 0 ° C to the boiling point of the reactant mixture, preferably from 0 to 80 ° C, approximately. In general, the reaction is preferably carried out under normal pressure, but can also be carried out under elevated or reduced pressure. In. the embodiment of process c) above, for example, an amount ranging from equimolar to about 1.2 moles, preferably an equimolar amount, per mole of the compounds of formula (V) can be employed and the mixture is reacted in the presence of of inert solvents such as, for example, dimethylsulfoxide, and in the presence of an acid acceptor such as, for example, sodium hydride, to thereby obtain the desired compounds of formula (I). In carrying out process d), suitable diluents include the same solvents mentioned as examples above for process a). In process d) mentioned above, the reaction temperature can vary within a wide range. In general, the reaction is carried out at a temperature of the order of 0 to 150 C, preferably 20 to 90 ° C, approximately. In general, the reaction is preferably carried out under normal pressure and can also be carried out under elevated or reduced pressure. In carrying out process d), for example, amounts ranging from equimolar to slightly higher molar amounts of the compounds of formula (IV) can be used per mole of the compounds of formula (le) and the mixture is reacted presence of inert solvents, in order to obtain the desired compounds of form (I). The active compounds are well tolerated by plants, have a favorable level of toxicity for warm-blooded animals and can be used to combat arthropod pests, especially insects found in agriculture, in forestry, in the protection of stored products and materials. and in the field of hygiene. The compounds are active against normally sensitive and resistant species and against all or some of the phases of their development. The aforementioned pests include: - of the genus Isopoda. for example Oniscus Asellus. Armadillidium vulgare and Porcellio scaber; - of the genus Diplopoda. for example, Blaniu-lus guttulafrus: - of the genus Chilopoda, for example, Geophilus-carpophagus and Scutigera spec; - of the genus Symphyla, for example, Scutige-relia immaculata; - of the genus Thysanura. for example, Lepisma saccharina; - of the genus Collembola, for example, Onychiurus armatus; - of the genus Orthoptera; for example, Blatta orientalis, American Periplapeta, Leucophae maderae, Blattella germanica, Acheta domesticus, Gryllotalp spp., Locusta migrato ria migratorioides, Melapoplu differentialis and Schistocerca gregaria; - of the genus Dermaptera, by. example, Forfícula auricularia; - of the genus Isoptera. for example, Reticulitermes spp .; - of the genus Anoplura. for example, Phylloxera vastatrix. Pemphiqus spp .. Pediculus Humanus corporis. Haematopinus spp. and Linognathus spp.; - of the genus Mallophaga. for example, Trichodect spp. and Damalinea spp.; - of the genus Thysanoptera. for example, Herculeopus femoralis and Thrips tabaci. of the genus Heteroptera. for example, Eurygaster spp.-, Dysdercus intermedius. Piesma guadrata, Cimex lectularius. Rhodnius prolixus and Triatoma spp.; - of the genus Homoptera. for example, Aleurodes brassicae. Semisia tabaci, Trialeurodes vaporarioru, Aph i s gossypii, Bre vi corvne brassicae, Crvptomyzus ribis, Aphis f abae, Doralis pomi, Eriosoma lanigerum ,. Hyalopterus arundinis, Macrosiphum avenae, Myzus. spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugeps, Aonidiella aurantii, Aspidiotus hederae, Pseudocsccus spp. and Psylla spp .; - of the genus Lepidoptera, for example, Pecfcipsphsra gsssypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blapcardella, Hvpopomeuta padella, Plutella maculipennis, Malacosoma neustria, Euprosctis. chrysorrhsea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella. Agrotis spp., Euxoa spp., Feltia spp., Earias insulana. Heliothis spp., Spodoptera exigua, Mamestra brassicae. Panolis flammea, Prodepia litura, Spsdoptera spp., Trichoplusia ni, Carpocapsa pomopella, Pieris SPP-. Chilo spp., Pyrausta pubilalis, Ephestia uehniella. Galleria mellonella. Cacoecia podapa, Capua reticulana. Choristopeura fumiferana. Clvsia ambiguella. Homona magnánima and Tortrix viridana; - of the genus Coleoptera, for example, Anobium punctatu, Rhizopertha dominica, Acanthos ce lides obtectus, Acapthoscelides obtectus, Hylotrupes bajulus, Ágelas tica alni, Leptipstarsa decemlipea.a, Phaedon cschleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varives tis, Atomaria spp ., Orvzaephilus surinamensis, Anthopomus spp., Si tophilus spp., Otiorhynchus sülcatus, Cos opolites sordidus, Ceuthorrhvnchus assimilis, Hypera psstica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lvctus spp., Meli. eth.es aeneus, Ptinus spp., Niptus hololeucus, Gibbiu Dsvlloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Meloloptha melolontha, Amphima-llon solsfcitialis and Csstelytra zealandica; - of the genus Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Msnomorium pharasnis Vespa spp .; - of the genus Diptera, for example Aedes spp., Anopheliss spp., Culex spp., Drosophila melanogas ter, Musca spp., Fannia spp., Calllphora ery throcephala, Lucili spp., Chrysomia spp., Cu terebra spp., Gas trophilus spp., Hyppobssca spp., Stsmoxys spp., Oes trus spp., Hypoderma spp., Tabapus spp., Tannia spp., Bibis hortulapus, Oscinella frit, Phorbid spp., Pegsmyia hvoscyarpi, Ceratitis-spitaba, Dacus oleae and- Tipula paludosa; - - of the genus Siphonaptera. for example, Xenopsylla cheopis and Ceratophyllus- spp.; - of the genus Arachnida, for example, Scorpio aurus and Latrodec us mactans: - of the genus Aranina, for example, Acarus siró, Argas spp., Ornithodoros spp., Dermanyssus gallinae Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp. / Rhipicephalus .spp. , A blyomma spp., Hvalomjna spp., Ixodes spp., Psoroptes spp. / Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Brysbia praetiosa, Pansnychus spp. Tetranychus. spp ..

Plant parasitic nematodes include Pratylenchus spp. , Radooholus similisf itylen-chus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longido-rus spp., Xiphinema spp., And Trichodorus spp. On the other hand, in the field of veterinary medicine, the new compounds of the present invention can be used effectively to combat a variety of parasitic pests harmful to animals (internal and external parasitic pests), for example, insects and parasitic nematodes. Said parasitic pests of the animals can be exemplified as follows: From the insect genus, for example, Gas rophi-lus spp.f Stomoxys spp., Tricodectes spp., Rhodius spp., Ctenocephalides canis and the like. The active compounds can be converted into customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with the active compound, very thin capsules in polymeric substances , coating compositions for use in seeds, and formulations used with combustion devices, such as fumigation cartridges, fumigation cans and fumigation streamers, as well as cold and hot ULV mist formulations. These formulations can be prepared in known manner, for example, by mixing the active compounds with diluents, ie diluents or liquid carriers, or liquefied or solid gases, optionally with the use of surface active agents, ie, emulsifying and / or dispersing agents. and / or foam formers. In the case of using water as a diluent, organic solvents can also be used as auxiliary solvents. Suitable diluents or liquid solvent vehicles are, in particular, aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such - >; - 24 - such as cyclohexane or paraffins, for example, fractions of mineral 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, or strongly polar solvents, such as dimethylformamide and dimethylsulfoxide, as well as water. By diluents or liquefied gaseous vehicles is meant liquids that will be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. As solid carriers, ground natural minerals such as kaolins, kaolin, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly dispersed silicic acid, alumina and the like, can be used. silicates. Solid crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours, and granules of organic material such as sawdust, can be used as solid vehicles for the granules. Coconut bark, corn cobs and tobacco stems.

Emulsifying and / or foaming agents which may be used are nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates, and albumin hydrolysis products. Dispersing agents include, for example, residual lignin-sulfite liquors and methylcellulose. In the formulation, adhesives such as carboxymethylcellulose and natural and synthetic polymers can be used in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate. It is possible to use dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and traces of nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. The formulations generally contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90% by weight. The active compounds according to the invention can They can be present in their commercially available formulations and in the forms of use, prepared from these formulations, as a mixture with other active compounds, such as insecticides, baits, sterilizing agents, acaricides, nematocides, fungicides, growth regulating substances or herbicides. Insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms. The active compounds according to the invention can also be present in their commercially available formulations and in the forms of use, prepared from these formulations, as a mixture with synergistic agents. The synergists are compounds that increase the action of the active compounds, without the incorporation of the synergistic agent in the active compound itself being necessary. The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The concentration of active compound of the forms of use can be from 0.0000001 to 100% by weight of active compound, preferably between 0.0001 and 1% by weight.

The compounds are used in the usual way, suitable for the forms of use. When used against unhygienic pests and pests of stored products, the active compounds are distinguished by their excellent residual action on wood and clay, as well as a good alkali stability on lime substrates. The preparation and use of the active compounds according to the invention can be seen from the following examples. Preparation examples Example 1 A mixture of l- (2-chloro-5-pyridyl) ethylamine (4.7 g), 1,1-bis-methylthio-2-nitroethylene (5 g) and ethanol (50 ml) was refluxed under heating until that the generation of mercaptan ceased. Then, the ethanol was distilled off from the mixture under reduced pressure and the resulting residue was purified on a chromatographic column (eluent mixture = ethanol + chloroform) to obtain 1- l- (2-chloro-5-pyridyl) desired ethylamino J-1-methylthio-2-nitro-ethylene (3.3 g) having a melting point on the order of 136 to 140 ° C. Example 2 To a solution comprising l- (1- (2-chloro-5-pyridyl) ethylamino) -l-methylthio-2-nitroethylene (2.7 g) in ethanol (50 ml) was added dropwise an aqueous solution of methylamine (40%, 3 g) at 50 ° C, followed by stirring for 2 hours at the same temperature. After cooling the solution to room temperature, the desired product was separated in the form of crystals, which were filtered and washed with ethanol to obtain l- (1- (2-chloro-5-pyridyl) ethyl-amino) -1 desired methylamino-2-nitroethylene (1.5 g) having a melting point on the order of 183 to 186 C. Example 3 N02 To a solution of 2-methyl-3-nitroisothiourea (15 g) in dimethyl sulfate (100 ml) was gradually added sodium hydride (oil free, 2.9 g) at 5 ° C, while stirring for 1 hour. Subsequently, 2-chloro-5-chloromethylpyridine (18 g) was added to the solution at a temperature of 5 to 10 ° C, followed by stirring overnight at room temperature. Once the dimethylsulfoxide in the solution was distilled off under reduced pressure, the resulting residue was purified on a chromatographic column (the eluent consisted of a mixture of ethanol and chloroform), to obtain the l- (2-chloro- 5-pyridylmethyl) -2-methyl-3-nitroisothiourea desired (2 g) with a melting point of 141 to 143 ° C. Example 4 L- (2-Chloro-5-pyridylmethyl) -2-methyl-3-nitroisothiourea (1.3 g) was dissolved in ethanol (20 mL) and an aqueous solution (50%) of dimethylamine (0%) was added to the solution. 5 g) at room temperature, followed by stirring for 1 day at 30 ° C. The ethanol in the solution was distilled off under reduced pressure and purified on a chromatographic column (the eluent consisted of a mixture of methanol and chloroform) to obtain the 3- (2-chloro-5-pyridylmethyl) -l, l- desired dimethyl-2-nitroguanidine (1.2 g) with a melting point of 158-160 ° C. Subordinate example 1 A mixture of 5-aminomethyl-2-chloropyridine (14.25 g), mesitaldehyde (14.3 g) and toluene (100 ml) was heated under reflux for 3 hours. The water formed during the reaction was trapped by a constant Dean-Stark water separator. The toluene was removed by styling the mixture under reduced pressure, in order to obtain N- (2,4,6-trimethylbenzylidene) -2-chloro-5-pyridylmethylamine (27 g), m.p. 47-48 ° C. Subordinate example 2 To a stirred solution of N- (2,4,6-trimethylbenzylidene) -2-chloro-5-pyridylmethylamine (10.9 g) in dry tetrahydrofuran (150 ml), cooled to -70 ° C, under one atmosphere of, butyllithium (10 p / v% in hexane, 26 ml) was added, an intense color immediately appearing. After 30 minutes of stirring at said temperature, methyl iodide (5.7 g) was added dropwise and the mixture was stirred for 3 hours without cooling. The solvent was removed under reduced pressure. To the residue were added ethanol (50 ml) and 2N hydrochloric acid (50 ml) and heated under reflux for 1 hour. The cooled solution was poured into water (100 ml) and extracted with methylene chloride (50 ml x 2). The aqueous fraction was neutralized with 2N sodium hydroxide and extracted with methylene chloride (50 ml x 2). The extract was dried over sodium sulfate and evaporated to obtain l- (2-chloro-5-pyridyl) ethylamine (4 g). n20 1.5440. In the following tables 1 and 2 there are compounds of formula (I) according to the invention, which can be prepared in the same manner as in the preceding examples 1 to 4. When Y is CH in the formula (I), the compounds of the formula (I) are illustrated "in table 1, and when n is N in the formula (I), the compounds are illustrated in table 2.

TABLE 1 1 R2 R3 Z - CH - N - C "CH - NO.

-. TABLE. 2 R1 R2 R3 Z - CH - N - C »N - NO.

Comp No. 41 2-chloro-5-thiazolylf H NHC3H7-n 42 2-chloro-5-pyridyl C2H5 NHC3H7-n p. 43 2-chloro-5-pyridyl NHC3H? -iso 16? - 165ßC 44 2-chloro-5-pyridyl CH, NHC3H7-iso p. 45 2-chloro-5-pyridyl H H N (CH3) 2 158 - 160 ° C 46 2-chloro-5-thiazolid H N (CH3) 2 47 2-chloro-5-thiazolyl CH. N (CH3) 2 p. F. 48 2-chloro-5-pyridyl CH, N (CH3), 96-99 ° C 49 2-chloro-5-pyridyl C2H5 N (CH3) 2 50 2-chloro-5-thiazolyl CH. H N (OI3) 2 51 2-chloro-5-pyridyl HH -C2H5 CH3 52 2-chloro-5-pyridyl CH3 -C2H5 CH3 53 2-chloro-5-thiazolyl HH N-C2H5 CH3 54 2-chloro-5-t-iazolylq H CH, N-C2H5 CH, Biological tests Comparative compound E-l Described in Japanese patent application n »233903/1988 Example 5 (biological test) Test on Nephotettix cincticeps which has resistance to organophosphorus agents: Preparation of the test chemical compound Solvent: 3 parts by weight of xylene; Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether. To form a suitable preparation, one part by weight of the active compound was mixed with said amount of the solvent containing said amount of the emulsifier. The mixture was diluted with water to a predetermined concentration. Test method On rice plants, approximately 10 cm in height, each in a pot with a diameter of 12 cm, were sprayed 10 ml per pot of water dilution of each active compound in a predetermined concentration. , prepared as previously described. The pulverized chemical compound was dried and on each pot a metal net having a diameter of 7 cm and a height of 14 cm was placed and 30 female insects of Nephotettix cincticeps showing resistance to the organophosphorus agents were released into the net. The sherds were placed in a constant temperature chamber and two days later the number of dead insects was examined, calculating the mortality of insects. The results are shown in table 3. TABLE 3 Example 6 (biological test) Test on plant-hopping insects: - or - Test method A dilution in water of a predetermined concentration of the active compound, prepared as in example 5, was sprayed on rice plants, approximately 10 cm in height, planted in pots with a diameter of 12 cm, in an amount of 10 mi per pot. The pulverized chemical compound was dried and a metal net of 7 cm in diameter and 14 cm in height was placed in each of the sherds. 30 female insects of Nilaparvata lugens Stal of a genus that showed resistance to organophosphorus chemicals were released into the net. The sherds were left in a constant temperature chamber and two days later the number of dead insects was examined. The death rate was then calculated. In the same way as above, the insect mortality was calculated on Sogatella fur-cifera Horvath and on Laodelphax striatellus Fallen. resistant to organophosphorus compounds. The results are shown in table 4.

Claims (9)

TABLE 4 Having described the invention as above, the content of the following is claimed as property CLAIMS

1. Process for the preparation of nitro-compound of formula (I) 1 2 wherein R is C 1-4 alkyl and R is hydrogen or C 1-4 alkyl R 3 is -S-R 4 or R 5 wherein R 4 is C 1-4 alkyl, R 5 and R 6 -N-R 6 are hydrogen or C 4 alkyl, and is CH and Z is a 5- or 6-membered heterocyclic group having at least one nitrogen atom which may be substituted by halogen or alkyl C. _4; the process is characterized in that: a) (in the case where R is -S-R, R is then replaced by R where R is C.sub.1 alkyl,) compounds of formula (II) are reacted wherein R is defined as above, with compounds of formula (III) I Z-CH-NHR2 (III) 7 2 wherein R, R and Z are defined as above, in the presence of inert solvents; b) (in the case where R is R I -N-R (then R 1 is replaced by R 7), compounds of formula (Ia) are reacted R R2 S.-R * I I I Z-C-I-Í.-C-CH-NO ?. (the) wherein R 7, R 2, R 4 and Z are defined as above, with compounds of formula (IV) 5 wherein R and R are defined as above, in the presence of inert solvents.

2. Method according to claim 1, characterized in that nitro-compounds of the formula (I) are obtained as a final product, wherein R is methyl and R5 and R2 are hydrogen or methyl, R3 is -S-R4 or - N-R6 wherein R4 is 5 6 methyl, R and R are hydrogen or methyl, Y is CH and Z is 3-pi -ridyl, 4-pyridyl or 5-thiazolyl which may be substituted by chloro or methyl.

3. Procedure in accordance with the claim 1, characterized in that 1 is obtained as a final product? compounds of formula (I), wherein R is methyl and R is R5 I 3 fi R f hydrogen or methyl, R is -NR where R and R are hydrogen or methyl, Y is CH and Z is 2-chloro-5 -pyridi lo or 2-chloro-5-t-yiazolyl.

4. Method according to claim 1, characterized in that 1 2 compounds of formula (I) are obtained as a final product, wherein R is methyl and R is 3 is hydrogen or methyl, R is -N-R wherein R and R are hydrogen or methyl, Y is CH and Z is 2-chloro-5-pyridyl or 2-chloro-5-thiazole.

5. Procedure in accordance with the claim 1, characterized in that compounds of formula (I) are obtained as a final product, wherein R 1 and R 2 are hydrogen or R 5 I or f. R-methyl, R is -N-R wherein R and R are hydrogen or methyl and Z is 2-chloro-5-pyridyl.

6. Process according to claim 1, characterized in that compounds of formula (I) are obtained as the final product, having the following individual structures: 1-Z * l- (2-chloro-5-pyridyl) ethylamino -7- 1-dimethylane-2-nitroethylene represented by the following formula l-amino-l- "l- (2-chloro-5-pyridyl) ethylamino-7-2-nitro-ethylene represented by the following formula l-Z "l- (2-Chloro-5-pyridyl) ethylamino-7-l-methylamino-2-nitroethylene represented by the following formula 1- (N-ZTl- (2-chloro-5-pyridyl) ethyl-7-N-methylamino) -l-dimethylamino-2-nitroethylene represented by the following formula '

7. N i tro-compounds of formula (I) R1 R2 R3 I I I Z - CH -N - C - Y -N02 (I) wherein R 1 is C.sub.4 alkyl and R.sub.2 is hydrogen or C.sub.4-4 alkyl is -SR.sub.R wherein R.sub.4 is C.sub.4 alkyl, R.sub.6 and R.sub.6 -N-R.sub.6 are hydrogen or C.sub.4 alkyl, Y is CH or N and Z is a 5-6 membered heterocyclic group having at least one nitrogen atom which may be substituted by halogen or C.sub.4 alkyl, when prepared in accordance with the process described in claim 1

8. Process for preparing insecticidal compositions, characterized in that the nitro-compounds of formula (I) are mixed with diluents and / or surface active agents. In testimony of which I sign the present in this City of Mexico, D.F., November 21, 1989. Attorney. GG * gch.