EP0000283B1 - Substituierte Carbamate, Verfahren zu deren Herstellung, diese enthaltende Zusammensetzungen sowie deren Verwendung als Insektizide. - Google Patents

Substituierte Carbamate, Verfahren zu deren Herstellung, diese enthaltende Zusammensetzungen sowie deren Verwendung als Insektizide. Download PDF

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Publication number
EP0000283B1
EP0000283B1 EP78300097A EP78300097A EP0000283B1 EP 0000283 B1 EP0000283 B1 EP 0000283B1 EP 78300097 A EP78300097 A EP 78300097A EP 78300097 A EP78300097 A EP 78300097A EP 0000283 B1 EP0000283 B1 EP 0000283B1
Authority
EP
European Patent Office
Prior art keywords
compound
compounds
insecticidal
methyl
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78300097A
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English (en)
French (fr)
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EP0000283A1 (de
Inventor
Richard Frank Sauers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Priority claimed from US05/885,251 external-priority patent/US4160034A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0000283A1 publication Critical patent/EP0000283A1/de
Application granted granted Critical
Publication of EP0000283B1 publication Critical patent/EP0000283B1/de
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/58—Derivatives of thiocarboxylic acids, the doubly-bound oxygen atoms being replaced by nitrogen atoms, e.g. imino-thio ethers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof

Definitions

  • This invention relates to substituted carbamates, preparation thereof and use thereof as insecticides for the control of pestiferous insects.
  • U.S. Patent 3,576,834 issued April 27, 1971, relates to insecticidal compounds having the structure: such as methomyl.
  • This invention relates to compounds of Formula I, their preparation, to insecticidal compositions containing them and to the method of using said compounds as insecticides.
  • Specifically preferred for its outstanding insecticidal activity is dimethyl N,N'[[1,2-ethanediylbis[thio(methylimino)carbonyloxy]]]bis(ethaneimidothiate).
  • the compounds of Formula I can be prepared, as shown in Equation A,by reacting preferably at least two moles of a substituted N-(aminocarbonyloxy)-alkanimidothioic acid ester of Formula II with one mole of an alkane disulfenyl halide of Formula III in the presence of a base: wherein R, R 1 , and R 2 are as previously defined and X is halogen.
  • the reaction can be carried out in any organic solvent which is inert to the reactants and the reaction products, e.g. methylene chloride, dioxane, tetrahydrofuran, chloroform, 1,2-dichloroethane, acetonitrile, benzene, toluene, the xylenes, acetone or methyl ethyl ketone. Mixtures of such solvents can also be used.
  • a base which will function as an acid acceptor can be used in synthesizing the compounds of this invention.
  • the process can be carried out at a temperature of between about -20° and 60°C, preferably between about -5° and 40°C. Pressure is not critical; for convenience, atmospheric pressure is preferred.
  • Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few litres to several thousand litres per hectare (from a few pints to several hundred gallons per acre). High strength compositions are primarily used as intermediates for further formulation.
  • the formulations broadly, contain e.g. about 1% to 99% by weight of active ingredient(s) and at least one of (a) e.g. about 0% to 20% surfactant(s) and (b) e.g. about 1% to 99% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
  • Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers," 2nd Edn., Dorland Books, Caldwell, N.J. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts.
  • Typical liquid diluents and solvents are described in Marsden, “Solvents Guide,” 2nd Edn., Interscience, New York, 1950. Solubility under 0.1 % is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C.
  • compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques.
  • the ingredients are thoroughly blended, passed through an air mill, to produce an average particle size under 15 ⁇ m, reblended, and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.
  • the ingredients are blended, coarsely hammer milled and then air milled to produce particles of active ingredient essentially all below 10 ⁇ m in diameter.
  • the product is reblended before packaging.
  • the ingredients are thoroughly blended.
  • the liquid surfactant is added by spraying upon the solid ingredients in the blender. After grinding in a hammer mill to produce particles essentially all below 100 ⁇ m, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
  • the ingredients are ground together in a ball or roller mill until the solid particles have been reduced to diameters under 10 ⁇ m.
  • the ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 ⁇ m.
  • the resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
  • a slurry of wettable powder containing 50% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
  • the ingredients are blended, hammer-milled and then moistened with about 12% water.
  • the mixture is extruded as cylinders about 5 mm diameter which are cut to produce pellets about 3 mm long. These may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm opening).
  • the granules held on a U.S.S. No. 40 sieve (0.42 mm opening) may be packaged for use and the fines recycled.
  • the ingredients are blended and ground in a hammer mill to produce a high-strength concentrate essentially all passing a U.S.S. No. 50 sieve (0.3 mm opening). This material may then be formulated in a variety of ways.
  • the ingredients are thoroughly blended and packaged for use.
  • the ingredients are combined and stirred to produce a solution which can be emulsified in water for application.
  • a fine screen filter is include in packaging operation to ensure the absence of any extraneous undissolved material in the product.
  • the compounds of this invention are useful for control of insects which are detrimental to agriculture.
  • insects controlled by the compounds of this invention include but are not limited to: cotton bollworm (Heliothis zeaJ, tobacco budworm (Heliothis virescens), southern armyworm (Spodoptera eridania), beet armyworm (Spodoptera exigua), soybean looper Pseudoplusia includensJ, Mexican bean beetle (Epilachna varivestis), and the house fly (Musca domestica).
  • insects are controlled by applying the compound to the locus of infestation, to the area to be protected, or to the pests themselves.
  • a compound of Formula I is generally applied to the foliage or other plant parts which are infested or which are to be protected. Effective amounts to be applied depend upon the species to be controlled, its life stage, its size and location, the amount of rainfall, the time of year, moisture, temperature, type of application, and other variables. In general, 0.1 to 10 kg/ha may be required for insect control in agriculture with rates of .2 to 4 kg/ha usually being sufficient in many situations. In large-scale field operations, rates in the range of 1/4 to 2 kg/ha are generally used.
  • the compounds of this invention will generally be used in formulation with a carrier that commonly will contain oil or water. Applications may be made with concentrated or dilute suspensions of the insecticide in the carrier. Low-volume applications utilizing dispersions containing about 20% of the active ingredient may be preferred by some applicators while others may prefer dilute suspensions containing only 25 ppm in high-volume applications.
  • the compounds of this invention possess significant advantages over prior art compounds, e.g. fewer applications are required to provide a given level of insect control due to this distinctly longer residual insecticidal action. Use of fewer applications results in greater economy to the grower and dissemination of less insecticide in the environment. An additional advantage is lower phytotoxicity to cotton.
  • the compounds will be incorporated into a formulation in a known manner with incorporation of other components such as (a) surfactants, (b) diluents, (c) additives to reduce foam or corrosion, or (d) preservatives to control microbiological growth.
  • other components such as (a) surfactants, (b) diluents, (c) additives to reduce foam or corrosion, or (d) preservatives to control microbiological growth.
  • the compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, other insecticides, or other biologically active compounds in order to achieve desired results with a minimum expenditure of time, effort and material. Amounts of these biologically active materials added for each part by weight of the composition of this invention may vary from 0.05 to 25 parts by weight. Suitable agents of this type are well-known to those skilled in the art. Some are listed below; the terms “Monocide”, “Morestan”, “Folbex”, “Kelthane”, “Pentac”, “Furadan”, “Pyridin” and “Ambush” are Trade Marks, at least in Great Britain.
  • the foliage only of red kidney bean plants in the two-leaf stage was sprayed to run-off with aqueous dispersions of dimethyl N,N'-[[1,2-ethanediylbis[thio(methylimino)carbonyloxy]]]bis(ethan- imidothioate) (I) at the dilutions indicated.
  • the sprays contained Duponol L-144-WDG (sulfonated oleyl acetate surfactant) at a concentration of 1:3000.
  • SAW southern armyworm
  • Example 2 The plants from the test described in Example 1 were kept in a growth room at 77 ⁇ 2°F and 53 ⁇ 5% relative humidity for 7 days. At the end of that period of time the remaining cotyledonary leaf from each bean plant was placed singly in a Petri dish with southern armyworms as previously described. Insect mortality was again read 2 days later and is set forth below:
  • Cotton plants approximately 22 cm in height having 3-4 true leaves were sprayed to run-off with an aqueous dispersion of dimethyl N,N'-[[1,2-ethanediylbis[thio(methylimino)carbonyl- oxy]]]bis(ethanimidothioate) (I) at a concentration of 0.05%.
  • the spray contained Duponol L-144-WDG at a concentration of 1:3000.
  • Another set of plants was similarly treated with methomyl. Plant injury was evaluated 6 days after treatment and is recorded below.

Claims (10)

1. Verbindung der Formel
Figure imgb0030
in der
R verzweigtes oder geradkettiges Alkyl mit 1 bis 3 Kohlenstoffatomen oder Methoxymethyl bedeutet,
R1 verzweigtes oder geradkettiges Alkyl mit 1 bis 3 Kohlenstoffatom bedeutet,
R2 -CH2CH2-,
Figure imgb0031
oder ―CH2CH2ZCH2CH2― bedeutet und
Z 0 oder S bedeutet.
2. Verbindung nach Anspruch 1, wobei R Methyl oder Äthyl und R1 Methyl bedeutet.
3. Verbindung nach Anspruch 1 oder 2, wobei R Methyl und R2 ―CH2CH2― bedeutet.
4. Verbindung nach Anspruch 1, wobei R2 -CH2CH2 oder
Figure imgb0032
5. Verbindung nach Anspruch 1, nämlich Dimethyl-N,N'[[1,2-äthandiylbis-[thio-(methylimino)-carbonyloxy]]]-bis-(äthanimidothioat der Formel
Figure imgb0033
6. Mittel zur Bekämpfung von Schadinsekten, enthaltend eine wirksame Menge einer insektiziden Verbindung und mindestens (a) ein inertes Verdünnungsmittel und (b) ein grenzflächenaktives Mittel, dadurch gekennzeichnet, dass es sich bei der insektiziden Verbindung um eine Verbindung nach einem der Ansprüche 1 bis 4 handelt.
7. Mittel nach Anspruch 6, enthaltend als insektizide Verbindung die Verbindung nach Anspruch 5.
8. Verfahren zur Bekämpfung von Schadinsekten durch Aufbringen einer wirksamen Menge einer insektiziden Verbindung auf die Stelle des Befalls, den zu schützenden Bereich oder auf die Schädlinge selbst, dadurch gekennzeichnet, dass man als insektizide Verbindung eine Verbindung nach einem der Ansprüche 1 bis 4 verwendet.
9. Verfahren nach Anspruch 8, bei dem man als insektizide Verbindung die Verbindung nach Anspruch 5 verwendet.
10. Verfahren zur Herstellung der Verbindungen nach Anspruch 1, dadurch gekennzeichnet, dass man Verbindungen der Formeln
Figure imgb0034
wobei
X ein Halogenatom bedeutet und
R, RI und R2 die gleiche Bedeutung wie in Anspruch 1 haben,
in einem inerten organischen Lösungsmittel in Gegenwart einer Base umsetzt.
EP78300097A 1977-07-01 1978-06-28 Substituierte Carbamate, Verfahren zu deren Herstellung, diese enthaltende Zusammensetzungen sowie deren Verwendung als Insektizide. Expired EP0000283B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US81231677A 1977-07-01 1977-07-01
US812316 1977-07-01
US885251 1978-03-10
US05/885,251 US4160034A (en) 1977-07-01 1978-03-10 Substituted carbamates

Publications (2)

Publication Number Publication Date
EP0000283A1 EP0000283A1 (de) 1979-01-10
EP0000283B1 true EP0000283B1 (de) 1981-10-14

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EP78300097A Expired EP0000283B1 (de) 1977-07-01 1978-06-28 Substituierte Carbamate, Verfahren zu deren Herstellung, diese enthaltende Zusammensetzungen sowie deren Verwendung als Insektizide.

Country Status (22)

Country Link
EP (1) EP0000283B1 (de)
JP (1) JPS5444614A (de)
AR (1) AR220138A1 (de)
AU (1) AU515983B2 (de)
BR (1) BR7804185A (de)
CA (1) CA1107292A (de)
CS (1) CS199213B2 (de)
DE (1) DE2861154D1 (de)
DK (1) DK254378A (de)
EG (1) EG13741A (de)
ES (1) ES471280A1 (de)
GB (1) GB2001628B (de)
GR (1) GR64548B (de)
IE (1) IE47205B1 (de)
IL (1) IL55050A (de)
IT (1) IT1158872B (de)
MX (1) MX5138E (de)
OA (1) OA05999A (de)
PH (1) PH13803A (de)
PL (1) PL114208B1 (de)
TR (1) TR19962A (de)
YU (1) YU154178A (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR8104086A (pt) * 1980-07-03 1982-03-16 Du Pont Processo para o controle de carrapatos

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856972A (en) * 1970-09-24 1974-12-24 M Hirano Carbamate pesticides

Also Published As

Publication number Publication date
TR19962A (tr) 1980-05-16
AU515983B2 (en) 1981-05-14
GR64548B (en) 1980-04-12
CS199213B2 (en) 1980-07-31
AR220138A1 (es) 1980-10-15
IL55050A (en) 1983-03-31
PL114208B1 (en) 1981-01-31
PH13803A (en) 1980-10-01
IT1158872B (it) 1987-02-25
JPS5444614A (en) 1979-04-09
GB2001628B (en) 1982-01-13
DK254378A (da) 1979-01-02
IE781324L (en) 1979-01-01
MX5138E (es) 1983-03-28
YU154178A (en) 1983-01-21
IT7825229A0 (it) 1978-06-30
ES471280A1 (es) 1979-10-01
PL208044A1 (de) 1979-12-03
OA05999A (fr) 1981-06-30
DE2861154D1 (en) 1981-12-24
EP0000283A1 (de) 1979-01-10
IE47205B1 (en) 1984-01-11
EG13741A (en) 1982-09-30
AU3752678A (en) 1980-01-03
CA1107292A (en) 1981-08-18
BR7804185A (pt) 1979-03-20
IL55050A0 (en) 1978-08-31
GB2001628A (en) 1979-02-07

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