DE1768623B - Thioformimidate compounds and their preparation and use - Google Patents

Description

SR ₁

, R ₄

¹ R ₅

in which: R _{1 is} a. Alkyl radical with,], up to 4: carbon atoms or an allyl group, R ₂ .and R ₃ , which can be identical or different, a hydrogen atom, an alkyl radical with 1 to 4th carbon atoms, an allyl radical, a methoxy group or a cycloalkyl radical with 3 to 5 carbon atoms, with the proviso that R ₂ and R ₃ together do not have more than 7 carbon atoms and that not both are methoxy or cycloalkyl, or R ₂ and R _{s are combined} to form an alkylene radical having 4 to 6 carbon atoms, R _{4 is} an alkyl radical having 1 to 3 carbon atoms or a allyl radical and R _{5 is} a hydrogen atom or a methyl group.

2. Methyl -1 - carbamoy 1 - N - (methylcarbamoy 1 oxyVthioformimidat. _;;

3. Methyl 1-methylcarbamoyiyN-Cmethylcarbamoyloxy) thioformimidate.

4. Methyl 1 - methylcarbamoyl - N - (methylcarb amoyloxy) thioformimidate.

5. Methyl 1- (diethylcarbamoyl) -N- (methylcarbamoyloxy) thioformimidate.

6. A process for the preparation of the Veroindungen according to claim 1, characterized in that for the preparation of compounds in which R _{5 of} the general formula of claim 1 is a hydrogen atom, in a known manner a l-carbamoyl-N-hydroxythioformimidate of the general formula

: ν - c - c {

R,

SR ₁

in which Ri, R ₂ and R _{3 have} the meanings according to claim 1, in an inert solvent with a substituted isocyanate of the general formula R ₄ NCO, in which R _{4 has} the meanings according to claim 1, or that one for the preparation of compounds , in which R _{5 of} the general formula of claim 1 denotes a methyl radical, in a manner known per se a thioformimidate of the general formula

N - C - C

NOH

SR ₁

in which R ₁ , R ₂ and R _{11 have} the meanings according to claim 1, -reacts in an inert solvent with sodium hydride and. the resulting substituted sodium salt of the general formula

R ₂

with a substituted carbamoyl chloride in general formula

CH ₃

implements, in which R _{1 has} the meaning according to claim 1.

7. Use of the compounds according to claims 1 to 5 as pest control od <_ Pesticides.

From the documents of Belgian patent 674 792

are effective as insecticides and pesticides

. sameO-carbamylhydroxamate ester and O- (methylcarb-

amylj-hydroxamate ester known. The O-carbamyl hydroxamate esters can be prepared by treating a thiol hydroxamate ester with sodium hydride, the sodium salt obtained is added to a solution of phosgene and the chloroformate intermediate with

Treated 2 equivalents of ammonia. The O- (Methyi-

carbamyl) hydroxamate esters are made by

the above-mentioned thiol hydroxamate ester is reacted with methyl isocyanate. ....

The invention relates to thioformimidate

bonds, which are characterized by the general formula

R,

R ₂ '

χ Il '■ - /

^N _N - C - C = NO - CN _x
/ 'ι \

SR ₁

in which: R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an allyl radical, R ₂ and R ₃ , which can be identical or different, a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms, an allyl radical, .eine..Metboxygruppe or , a Cycloa) kyl radical with 3 to 5 carbon atoms, with the proviso that R ₂ and R ₃ together have no more than 7 carbon atoms, and that not both methoxy or cycloalkyl, or R ₂ and R ₃ to an alkylene radical with 4 to 6 carbon atoms are joined together, R _{4 is} an alkyl radical having 1 to 3 carbon atoms or an allyl group and R _{5 is} a hydrogen atom or a methyl group.

As from the general formula of the proper Compounds as can be seen, there are two stereoisomeric forms of these compounds, namely the syn and the anti isomers.

The compounds according to the invention can be used as pest control agents and crop protection agents. Thus, the founding methods are suitable

binding p. for ... fighting ticks, mites,., insects,, and Nematodes; they .protect .the.plants in especially effective against plant-destroying Pests. They show an extraordinary activity against the fruit capsule beetle Anthonomus grandis and the southern army worm Prodeniaeridania ,. where you instruct a good safety margin for the host plants. In addition to their high degree of harmlessness for seeds, fruits and leaves, those according to the invention have Compounds have physical properties by virtue of which they can easily and without disturbance have existing plants used at the location of the nematode infestation. In addition, the invention Connections a good security network for mammals and an exceptional residual activity.

of the erfidnungsgemäßen particularly preferred compounds are those in which the radicals R 'and R ₃ are both hydrogen atoms or both Methylrestc. Methyll-carbamoyl-N- (methylcarbamoyloxy) -thioformimidate, methyl-1- (dimethylcarbamoyl) -N- (methylcarbamoyloxy ¹ ) -thioformimidate, methyl - are particularly preferred because of their high effectiveness against pests and because of the high safety limit for crops. 1 -metliylcarbampyl-N - '(: methylcarbamoyloxy) -thioformimidate and methyl-1 - (diethylcarbLtnoyl) - N - (methylcarbamoyloxy) -thio formimidate. . · _: ·. ·, ■ _: ,. .

The designated. Compounds of the above general formula in which R ₅ denotes a hydrogen atom are prepared according to the invention in a manner known per se) by adding a 1-carbamoyl-N-hydroxy-thioformimidate of the general formula

R ₀ , NOH

N - C - C '

in an inert. Reacts solvent with a substituted isocyanate of the general formula R ₄ NCO. For some thioformimidates, a trace of a catalyst, such as triethylamine or dibutyltin dilaurate, can be added in this reaction. , .- ., _}

The compounds according to the invention of the above general formula, in which R ₅ denotes a methyl radical, are prepared according to the invention in a manner known per se by adding a thioformimidate of the general formula

- c -

NOH

R ₂

Reacts in an inert solvent with sodium hydride and the resulting substituted sodium salt of the general formula

ν - c - c:

, NO ³ Na =

3 °

35

with a substituted carbamoyl chloride of the general formula

^x N_ c - Cl

CH ₃

implements. . ..........

_{If the radicals R 2} and R _{3 are} both hydrogen atoms in the general formula of the starting materials, the thioformimidate used as the starting material is prepared by reacting l-carbamoylformhydroxamyl chloride with a mercaptan in the presence of a base. This implementation proceeds according to the equation

H ₂ N - C - C Γ

, NOH || , NOH

■ „■ NaOH _{TT XT nn}
+ R ₁ SH > H ₂ NCC.

C!

SR _x

The l-caibamoylformhydroxamyl chloride can according to Reports, 46: 2832 (1913). . . ,:

Another process for the production of the raw materials Serving thioformimidate is the implementation of Metlioxycarbonylfornihydroxamylchlorid with a mercaptan in the presence of a base and the further implementation of the product with the appropriate Amine to form the desired 1-carbamoyl-N-hydroxy thioformimidats.

Typical insects, ticks, mites and nematodes that can be combated with the compounds according to the invention are the following:

Aphids:

Aphis fabae, Brcvicoryne brassicae, Aphis niaidis. Anuraphis maidiradieis, Aphis gossypii, Myzus pcrsk'uc. Macrosinhum solanifolii, Eriosoma lanitierum; Army worms:
Laphygma f rugiperda, Prodenia eridania;

Beetle:

55 Autoscrica castanea, Cerotoma trifurcata, Lasioderma scrricorne, Leptinotarsa dccemlineata, Popil-Ha japonica, Epilachna varivestis, Epilachna borealis, Euetheola regiceps, Graphognathus leucolama, Anthonomus grandis, Heliothis zea;

Beetle larvae:

Pyrausta nubilalis. Sanninoidea exitiosa, Melittia cucurbitae, Diatraca saccharalis;

Butterflies:

Colins philodice, Pieris rapae;

Caterpillars:

Colias eurytheme. Malacosoma americanum;

fio

ana, Meloidogyne arenaria, Paratylenchus spp.,

Plum weevil: Ditylenchus destructor, Rotylenchulus reniformus,

Conotrachelus nenuphar Dithylenchus angustus, Criconemoides spp., P ^ aty-

lenchus brachyurus, Meloidogyne incognita, hetero-

Corn earworm: _{5 dera} gi _yc i _ne s, Helicotylenchus spp., Ditylenchus

Heliothis zea; dipsaci, Belonolaimus spp., Trichodorus spp., Hete

rodera schachtii, Heterodera tabacum, Tylenchor-

Flea beetles: hynchus claytoni, Anguina tritici;

Epitrix cucumeris, Epitrix _{Roga fear capsule worm:}

_iq

Srtipennis _iq

"" "'_. Pectinophora gossypiella;

Cotton flea buyers:

Psallus seriatus; Root worms:

Diabrotica longicornis, Diabrotica undecimpunctata

^Flie 8 ^en: i ₅ howardi, Diabrotica vigifera;

Aleurocanthus woglumi, Phytophaga destructor,. , .. "
Siphona irritans, Musca domestica, Stomoxys calci- blasen u r.
trans; Thrips tabaci, Frankliniella fusca;

_Fruit flies: 2o ticks:

Ceratitis capitata, Anastrepha ludens, Dacus dorsa- Dermacentor variabilis, Argas persicus, Dermacen-

Hs; torandersoni;

Cockroach: tobacco budworm:

Blattella germanica; as Heliothis virescens;

Leaf moth: weevils:

Archips argyrospila, Argyrotaenia velutinana; Hypera postica, Sitophilus granarius, Sitophilus

_D. oryzae, Cylas formicarius elegantulus.

Leaf caterpillars: ο

Liriomyza brassicae; As a pesticide one uses

. ... one or more compounds according to the invention

öiattnupler: possibly in a mixture with other pest-infected

Circulifer tenellus, Empoasca fabae, Perkinsiella pesticides, furthermore the approaches can

saccharicida; 35 surface-active agents, solid or liquid diluents

_D .... contain agents and other substances in order to

Cotton _{leafworm: ver>suspensions>} emulsifiable concentrates, dusts,

Alabama argillacea; Get solutions, grains or pills.

“Surfactants become anionic

baatnornmade: _{4o and not ionogenic in} pest control

Hylemya platura; average preferred. The amount of surface active

"...... _ agent in the pesticides

^{1 ause} up _to 15 percent by weight, based on the total

Pseudococcus citri, Pseudococcus brevipes; weight of the pesticide.

,, - ,,. 45 Fine-particle thinners can be concentrated in

Trations of 2 to 98 percent by weight, based on the

Paratetranychus citri, Bryobia praetiosa, Pannoy - total weight of the pesticide, chus ulmi, Tetranychus pacificus, Tetranychus urti- can be used. When solutions are used

cae; these contain 5 to 30 percent by weight of active

j ...,. 50 substance and 70 to 95 percent by weight solvent,

Suspensions contain 10 to 50 percent by weight

Anopheles quadrimaculatus, Aedes sollicitans, Culex active ingredient in dispersion in a nonsolvent as pipiens quinquefasciatus; Carrier. Aerosols usually contain an organic one

w ,, ,, c,, j. ,. · .., or aqueous liquid in quantities of 80 to 98 moths (the damage is caused by the moths ■ ,, ,, t λ r *. -Ij

, γ .. lani-ii ₅₅ percent by weight, based on the total weight of the

Pesticides. Grains or pills

Tineola biseUiella, Carpocapsa pomonella, Rhya- can produce 15 to 30 percent by weight of active ingredient

cionia buoliana, Polychrosis viteana, Porthetria dis- put; usually, however, the effective

par, Diaphania hyalinata, Grapholitha molcsta, substance concentration for the most favorable distribution 2 to

Diaphania nitidal "=; 60 20 percent by weight. Such granulated approaches are

N _cnn . ι. most favorable when they have grain sizes from 0.25 to

1.4 mm.

Dolichodorus defeated occphahis, Pratylchus musi- Although the inventive connections

eola, ΛρΙΐί-lcnchoidcs spp., Radopholus similus, can be quite stable under most conditions

llutcrodcra enrotae, Mcloidügyne exigua, Pratylcn- S ₅ it may be advisable to use üiiicn desiccants, buffers or substances,

chus zeac, Xiphincma spp., Heterodera rostochien- like ureas, add the catalytically active

sis, Anguina agrostis, Hoplolaimus spp., Pratylcn-Steilen au. the oil used as a diluent

chus spp., Meloidogyne hapla, Heterodera gottingi- just inactivate. Ai'ch additives that reduce corrosion

prevent foaming or caking can be added to reduce and increase flocculation. Besides, you can Bactericide, fungicide, bacleriostatic and fungistatic Agents and other Insecticides, Acaricides and Ncniatocides in amounts from 0.025 to 10 parts by weight depending on the type of compounds found to add.

When using the compounds according to the invention for pest control, the required quantities depend on the temperature, the season, humidity, method of application, type of pest and similar factors.

If one compares the effect of methyl-O- (methyl-carbamoyO-thiolacetohydroxamat (cf. documents of Belgian patent 674 792) with that of methyll-carbomoyl-N-imcthylcarbamoyloxyJ-thioformimidate, Methyl -1 - dimethylcarbamoyl - N - (methylcarbamoyl oxy) thioformimidate or ethyl-l-carbamoyl-N- (methylcarbamoyloxy) -thioformimidate against Colorado potato beetle, thus the three compounds according to the invention show a considerably better effect. Methyl-1-dimethylcarbamoyl-N- (methylcarbamoyloxy) thioformimidate also acts against alfalfa beetles considerably better than the known compound mentioned. This perfect connection also shows In contrast to the known compound, it has a good effect on nematodes, e.g. B. opposite the root nodule nematode Meloidogyne

In a further series of tests, 28 compounds according to the invention were tested with 1-naphthyl-N-methylcarbamate in their action against Aphis fabae Scop., house fly and Tetranychus binaculatus as well compared in their nematocidal effect. Here, too, the superiority of the invention was shown Links.

In the following examples, parts and percentages refer to, unless otherwise stated, on weight quantities.

Manufacturing

example 1
Preparation of the starting compound

A mixture of 12.3 parts of 1-carbamoylformhydroxamyl chloride, 79.2 parts of methanol and 10 parts of water is ^{cooled to 5 °} C. and 7 parts of methyl mercaptan are added. To this mixture ⁰ C 8 parts gradually at -5 to O to 50 ° / _o aqueous sodium hydroxide solution was added, the pH value rises on the eighth The sodium chloride formed is filtered off and the filtrate is concentrated until crystals form. The mixture is cooled well and filtered. Methyl-1-carbamoyl-N-hydroxythioformidate is obtained; M.p. 163 to 164 ° C.

Methyl 1-carbamoyl-N-imethylcarbamoyloxy I-thioformimidate

A trace of 1,4-diazabicyclo- [2,2,2] -octane is added to a suspension of 4.5 parts of methyl 1-carbamoyl-N-hydroxylthioformimidate and 2.2 parts of methyl isocyanate in 20 parts of acetone. The reaction temperature rises to 55 ° C and then falls again, forming a white solid. After several hours at room temperature, the mixture is filtered. Methyl-1-carbamoyl-Nf.methylcarbamoyloxy) thioformimidate is obtained; F. 162 to 164 ⁰ C.

The compounds listed in Table I are following the procedure of Example I using the mercaptans and isocyanates indicated in the table instead of methyl mercaptan or methyl isocyanate manufactured.

Table I.

Mercaptan Isocyanate compound according to the invention Physical
Key figures Ethyl mercaptan
Butyl mercaptan
Methyl mercaptan
Methyl mercaptan Methyl isocyanate
Methyl isocyanate
Ethyl isocyanate
Allyl isocyanate Ethyl-l-carbamoyl-N- (methylcarbamoyloxy) -
thioformimidate
Butyl-l-carbamoyl-N- (methylcarbamoyloxy) -
thioformimidate
Methyl-l-carbamoyl-N-Cäthylcarbamoyloxy) -
thioformimidate
Methy-l-carbamoyl-N- (aliylcarbamoyloxy) -
thioformimidate M.p. 145 to 149 ° C
M.p. 139 to 1 ^ 2 ° C
M.p. 121 to 122 ° C
F. 90 to 91 ⁰ C

Example 2
Output compound

A solution of 206 parts of methyl glyoxalate-oxime in 1500 parts of water is added in the course of 37 minutes at 0 to -5 ⁰ C with 145 parts of chlorine. It forms! - (MethoxycarbonyO-formhydroxamyl chloride in the form of an oil, which can be isolated by extraction with methylene chloride, evaporation of the methylene chloride and recrystallization from benzene; mp 63 to 65 ° C.

The suspension of l- (methoxycarbonyl) -formhydroxamylchlorid in water at 0 to -5 ⁰ C with 105 parts of methyl mercaptan and then with 130 parts of 50 ° / _o aqueous sodium hydroxide solution mixed with 330 parts of water, was added. The two-phase reaction mixture obtained in this way is extracted with methylene chloride. After evaporation of the solvent under reduced pressure, solid methyl 1-methoxycarbonyl-N-hydroxythioformimidate remains, which can be recrystallized from benzene; M.p. 63 to 64 ° C. This crude methyl 1-methoxycarbonyl-N-hydroxythioformimidate is dissolved in 250 parts of methanol, and 180 parts of anhydrous ditriethylamine are dissolved in this solution at a temperature below 30.degree. The solution is left to stand at room temperature overnight. After driving off the excess dimethylamine and the solvent under reduced

tem pressure hintcrbleiben 240 parts of methyl l- (dimcthylcarbamoyl) -N-hydroxyth ioforminiidiit: yield 74 ⁿ / ".

Metl'vl-MdimcthykarbamoyO-N-Oiiclhykarbamoyloxy) -lhioformimidal

A suspension \ l on 70 parts Methyl-l- (dimcthylcarbamoyl) -N-hydroxythioformimidat and 0.5 parts 4-Diazabicyelo- [2,2,2] octane in 350 parts of acetone is added slowly at 4O ⁰ C with 27 parts Methyl isocyanate is added. The temperature of the reaction mixture rises to 58.degree. After the temperature has dropped to 25 ° C, the solvent is reduced under

10

evaporated tem pressure and the residue recrystallized. Recrystallization from benzene gives one isomer of methyl - <- (dimethylearbamoyl> N- (melh> lcarhamoyloxy) thioformimidate: F. 109 to IK) ¹ C. Recrystallization from water gives the other!:; Omerc of methyl -1- (dimethylciirbamoyl) -N - (methylearbamoyloxy) -thioformimidates; F. 101 to 103 ⁰ C.

The compounds listed in Table II are

ίο according to Examples 1 and 2 from the in the table mentioned mercaptans, amines and isocyanates instead of methylmcrcaptan, dimethylamine or Methyl isocyanate produced.

Table II

Mercaptan Amine Isocyanate Krfind; ngsgcmällc connection Physical
Numbers Methyl mercaptan Methylamine Methyl isocyanate Methyl-l- (methylcarbamoyl) -N- (mc- F. 111.5 ethylcarbamoyloxy) thioformimidate up to 112.5 ¹ C Methyl mercaptan Butylamine Methyl isocyanate Methyl-l- (butylcarbamoyl) -N- (mc- F. 75 to 76 "C ethylcarbamoyloxy) thioformimidate Met. '. Yl mercaptan Diethylamine Methyl isocyanate Methyl-1- (diethylcarbamoyl) -N- (me- n? " 1.5230 ethylcarbamoyloxy) thioformimidate Methyl mercaptan Hexahydroa? E- Methyl isocyanate Methyl-l- (hexahydroazepinocarbonyl) - F. 93.5 pin code N- (methylcarbamoyloxy) -thioformi-
111 IUtLl up to 94.5 C Methyl mercaptan Pyrrolidine Methyl isocyanate Methyl-1- (pyrroüdinocarbonyl) - F. 124 N- (methylcarbamoyloxy) -thiofor-
JlJJllllUClL up to 125.5'C Methyl mercaptan N, O-dimethyl Methyl isocyanate Methyl-1- (N-methoxy-N-methyl- F. 99.5 hydroxylamine carbamoyl) -N- (methyIcarbamoyl- to 100,. · C oxy) thioformimidate

Example 3

Methyl 1-carbamoyl N- (dimethylcarbamoyloxy) thioformimidate

A suspension of 48 parts of a mixture of sodium hydride and mineral oil containing 50% sodium hydride in 648 parts of tetrahydrofuran is mixed with 114 parts of methyl 1-carbamoyl-N-hydroxythioformimidate, in portions over the course of one hour, while stirring. The temperature is kept at 20 to 30 ^° C. during this process. After the evolution of hydrogen has ceased, 107.5 parts of dimethylcarbamoyl chloride are added dropwise at 15 to 25 ° C. After this addition, the mixture is stirred for a further hour. The inorganic solids are filtered off and the methyl 1-carbamoyl-N- (dimethylcarbamoyloxy) thioformimidate is recovered by evaporating the solvent under reduced pressure. F. 166 to 167 ⁰ C.

In the same way is prepared from methyl-1-dimethylcarbamoyl-N-methyl-l-dimethylcarbamoyl hydroxythioformimidat - N- (dime thylcarbamoyloxy) - thioformimidate forth F. 103.5 to 104.5 ⁰ C.

Application example 4

Methyl-l-carbamoyl-N-Cmethylcarbamoyl-

oxy) thioformimidate 95%

Synthetic fine-particle silica 5%

A sieved fraction of the active ingredient with a particle size of less than 0.25 mm becomes fine Partial silica mixed to prevent agglomeration during storage. At the Ztisat; this crystalline form distributes itself to water in a satisfactory manner without the formation of lumps'.: n < goes into solution in a few minutes.

This approach is dissolved in water and in a concentrate with a conventional sprayer of 120 g of batch per 100 l of water in a spritzdiclit of 2.5 kg of active ingredient per hectare on wild fire beans brought by the Mexican bean k; 'ife Epilachna varivestis and the two-spotted mite Tctranv chus urticae are infested. The treated bean plants grow rapidly, have deep green leaves without the chewed areas characteristic of the bean beetle infestation and make a good egg wear firebeans. In a nearby plantation, the bean plants have withered

chlorotic and reticulate leaves and give a poor yield.

Methyl-1-tdimethylcarbamoyO-N-tmethylcarbamoy oxy) -thioformimidate can be used in the form of the same Ai rate in water for transplanting tobacco pear

zen in an amount of 15 mg of active ingredient per plant be used to protect the tobacco plants against NemaU denbefall and a rapid growth sow to achieve a good tobacco yield.

H c i s ρ i e I 5

Methyl-l-earbamoyl-N- (melhykarbamoyl-

oxyHliioformimidate 75 "/ ,,

Sodium salt /. an alkylnaphlhalinsulfone

! »• III I '. I / o

Partly cntsulfonicrles sodium ligninsil-

fonat 10%

Synthetic fine-particle silica 14 ⁿ / o

The above ingredients are mixed, finely powdered and ground in an air jet mill. To the simultaneous control of the root-knot nematode and the soil fungi Pythium spp. and Rhizoctonia • pp. the wettable powder is sprayed in an approach that also contains M-dichloro ^ S-dimethoxybcnzol contains. For this type of application, 2.4 kg of active ingredient according to the invention and 4.8 kg of 1,4-dichloro-2,5-dimethylbenzene are required added to 100 l of water. This mixture is in a 25 cm wide strip on the Row sprinkled in which cotton is to be planted. The spray density in the row of plants is 67.5kg Total active ingredient (22.5 kg of compound according to the invention and 45 kg of 1,4-dichloro-2,5-dimethoxybcnzene) each ha treated floor area. Immediately afterwards, the soil is mechanically dug up to remove the chemicals to mix thoroughly with the soil. The cottonseed is then plowed in the treated strip The developing cotton culture is against the nematodes Meloidogyne incognita and Rotylenchulus rcniformus and against the fungi Pythium spp. and Rhizoctonia spp. protected. To the At harvest time you get a healthy population of cotton plants and a high cotton yield. On In untreated areas, plant growth is poor and slow and the seed hair yield is reduced.

A similar approach is carried out with methyl l- (dimethylcarbamoylJ-N-Cmo'.hylcarbamoyloxyi-thioformimidate prepared and together with l, 4-dichloro-2,5-dimethoxybenzene in the manner described above before Planting cottonseed sprayed on the ground. The spray density in the row of plants is 6 kg of the compound according to the invention and 45 kg of 1,4-dichloro-2,5-dimethoxybenzene per hectare treated Surface. Immediately afterwards, the soil is mechanically dug up to thoroughly mix the chemicals with the soil to mix. The cottonseed is planted in the strips treated in this way. The cotton crops are against the nematodes Meloidogyne incognita and Rotylenchulus reniformus as well as against the fungi Pythium and Rhizoctonia protected. The plants develop extensive, deep roots and thrive fast.

The connections can be made without endangering the cotton plants can be used in much higher concentrations.

Example 6

The approach according to Example 5 is added to water in such an amount that the active ingredient konzenfation 45 g per 100 l spray mixture is. With this solution dispersion, apple trees become to drain sprayed with the help of a hydraulic high-pressure spraying device. By spraying once a week the apple trees are protected against the green apple aphid, the moth Carpocapsapomonella, the plum weevil and the leaf moth Argyrotaenia velutinana. When the treatment in larger Periods made to graze or air combat Other pests that are particularly difficult to control can result in the spray mixture the following insecticides are added in effective amounts: Dichlordiphcnyltrichloräthan, 1,1,1-Triehlor-2,2-bis- (p-methoxyphenyl) -ethane, o.o-Diniethyl-S- (1,2-dicarbethoxyethyl) dithiophosphate or Blciarscnat.

Example 7

ίο n-propyl-l-carbamoyl-N-fmethylcarba-

moyloxy) thioformimidate 50%

Sodium dioctyl sulfosuccinate Ί5%

Mcthylccllulosc of low viscosity 2.0%

Diatomaceous earthc 47.5%

The above ingredients are mixed and finely powdered until virtually all of the particles are smaller than 50 μ are. The wettable powder obtained in this way can be sprayed after addition to water or with heavy Diluents are diluted to form a pollinant; z. B.

above approach 20%,

ground pyrophyllite 80%.

In a ribbon or cone mixer, these ingredients are turned into a dust with an active ingredient content mixed by 10%.

The dust containing 10% active ingredient is applied to the dust using a hand crank Undersides and tops of the leaves of rose bushes, which are still wet from the morning dew, until they are thoroughly covered dusted up of leaves. Through this treatment, aphids, like the potato aphid, become Macrosiphum euphorbiae and the rose aphid Macrosiphum rosac, as well as adult specimens of the Japanese beetle Popillia japonica killed. The dust can also be composed that he has 5% "Manzatc" (active ingredient Manganäthylcn-bisdithiocarbamat) contains, to combat the black spot disease Diplocarpon rosae, of the Roses are often infested. Roses treated with this combination thrive well and have shiny, deep-colored ones Leaves and develop numerous buds. Adjacent untreated rose bushes do not thrive, lose numerous yellowed leaves and do not provide the expected flower yield.

Example 8

The wettable powder according to Example 7, but with methyl 1- (dimethylcarbamoyloxy) -N- (methyIcarbamoyloxy) thioformimidate as an active ingredient, is sprayed around young, fruit-bearing apple trees in Holland, that of the nematode Pratylenchus spp. are infested. The trees will be within the drainage line sprayed with the agent at a density of 2.25 to 4.5 kg of active ingredient per hectare of treated area. in the In contrast to neighboring, untreated trees, the treated trees thrive quickly.

B e i s ρ i e I 9

The wettable powder according to Example 7 is in J-orm of a 25 cm wide strip sprayed over the open furrow when planting cottonseed. for In this type of application, the spray density is 2.5 kg of active ingredient per 10,000 m of furrow length in 75 liters of water. As a result of the system's action, the active ingredient migrates from the soil into the cotton seedlings and makes the same toxic to suckling insects. This will make the

13 14

Infestation by aphids, bladder feet and plant sows in solution. With an injection preparation of lower

gendc insects suppressed. On the treated volume concentration, some active substance can

Plants flourish quickly and develop in areas where they remain loose:

full green foliage. Plants on a unbchandcltcn stalle prevented by the surface-active agent.

Soils thrive slowly and have 5 The cmulgicrbarc concentrate described above as a result of damage

silvery leaves thickened by bladder feet. is diluted with water and in one concentration

The pest rate described in this example of 17 kg of active ingredient in 11501 of water per hectare per hectare

Kämpfmittcl can without harm to the cotton of the sugar beet nematodc llclerodcra schachlii

Infested soil is also sprayed in much higher concentrations, whereupon the agent reaches up to

the. ίο is worked into the ground to a depth of 15 cm.

B e i s η i e 1 10 sugar beets, which are then grown on this field develop normally and show none

Isopropyl-i-carbamoyl-N-methylcarba nematode infestation. In a similar, of the same

moyloxy) -lhioformimidate 25.0% nematode-infested, but untreated area of the

Sodium salt of an alkylnaphthalene sulphate in the same field, the sugar beets are deformed

fonsäure 0.5% and give a poor yield.

Sodium N-methyl-N-palmitoyl taurate .. 2.0%

Attapulgite 72.5 ° /,

Example 13

The water-miscible batch according to Example 12 The above ingredients are mixed and finely dispersed in water, and powdered with this dispersion until practically all the particles are smaller than 50μ cotton seed at a concentration of. 750 g of active ingredient per 100 kg of seed treated. The bc-This approach is treated in water in a concentration of seeds yields cultures that disperse against the amount of 480 g per 10 l of water. This dispersants attacked are protected by insects and are sprayed the walls until the expiry of a time Sion, foot 25 room up to 3 weeks or more after planting soil, stalls and pens of barns, by the not the Kartoffelblatllaus Aphis gossypii , the house fly Musca domestica are infested. This pest is destroyed by the aphid Liriomyza brassicae or the tobacco blowing treatment. feet of Frankliniella fusca. The Lcbens-. 111 aer ability cotton is further veibessei i, when the seed Example 30 simultaneously with the above concentrate methyl-l-carbamoyl-N-idimcthylcarba- with l, 4-dichloro-2,5-dimethoxybenzene in an active

moyloxy) thioformimidate 80% substance concentration of 375 g per 100 kg of seeds bchan-

Glimmertalkum is 20% delt. The viability of the

Cotton can be improved when you are third

The above ingredients are mixed and finely 35 component bis- (m "thylmercuri) -si; ifat in one amount

powdered until practically all particles smaller than 200 ml per 100 kg of cottonseed are added. The

than 0.15 mm. The free flowing M-dichloro ^ S-dimethoxybenzene thus obtained in the mixture

Powder can be mixed with the same or different diluent by one or more of the following compounds

Renal extenders can be replaced by simply mixing them into a fertilizer: Pentachloronitro "> enzene, N-tri-

Dust with an active ingredient concentration of 2 to 40 chloromethylthiotetrahydrophthalimide, tetramethyllhi-

25% diluted. uram disulfide, l-chloro-2-nitropropane, 5-ethoxy-3-tri-

The dust concentrate is mixed with talc to form a chloromethyl-l, 2,4-thiadiazole or p-dimethylamino-

Active ingredient content diluted by 5%. When potato benzene diazo sodium sulfonate.

plants produced by the potato aphid Macrisiphum.

euphorbiae and the green peach aphid Myzus 45 B e 1 s ρ 1 e 1 14

persicas are infested with this dust with the help of allyl-l-carbamoyl-N-Cmethylcarbamoyl-

of a hand crank-operated pollinator green oxy) thioformimidate 25%

borrowed to be pollinated, one achieves an excellent dimethyl sulfoxide 75%

Suppression of pest infestation. When other

Insects such as the Colorado potato beetle Leptinotarsa decem- 50 When these ingredients are mixed together, one forms lineata, flea beetles, and leafhopper, are present, clear solution. When mixing this solution with you can add the pesticide to the water in a concentration of 0.6 g of active ingredient each To improve the effect, dichlorodiphenyltrichloroethane liter of water also gives a clear solution, or l, l, l-trichloro-2,2-bis (p-methoxyphenyl) ethane The solution described above is up to one to add. 55 Example of an active ingredient concentration of 0.2% with water 12 thins. By syringing with this agent with the help

of a mist atomizer, house flies become Musca

Methyl-l-carbamoyl-N-f-methylcarbamoyl domestica and other flies, such as stable flies Musca

oxy) thioformimidate 25% autumnalis, in agricultural buildings, shy

Sorbitan 60 modified with polyethylene oxide and outside buildings

Monotallölester 5% direction, such as pens and fences, destroy

Dimethylformamide 70% tet.

Example 15

By mixing these ingredients, an ethyl-l-carbamoyl-N- (äthylcarbamoyloxy) -

homosene solution produced. When added to water 65 thioformimidate 30%

the mixture becomes temporarily milky, as the polyethylene oxide lauryl ether 8%

Separates active ingredient; if the active ingredient concentration is white oil of low viscosity (Liteteck-

is low, but ultimately all of the active ingredient oil) 62%

The above ingredients are mixed and crushed in the sand mill to grain sizes below 10 μ. the Suspension can be emulsified in water and sprayed, or it can be mixed with a non-phytotoxic Paraffin oil can be diluted and then sprayed. For use in extremely small volumes, this can Concentrate can be sprayed as such.

This approach is brought to an active ingredient concentration with water of 2.2 kg per 230 l diluted and sprayed onto a maize plantation at a spray density of 230 l / ha, whereby the spray jet is directed onto the silky style of the developing ears. When used in this way at the time of pen development at intervals of 1 to 2 days the infestation by the corn worm Heliothis zea is suppressed.

Example 16

Allyl-l-carbamoyl-N-idimethylcarba-

moyloxy) thioformimidate 35%

Hydrocarbon polymer with several carboxyl groups (Carbopol 934) 0.4%

10% aqueous sodium hydroxide solution 1.00%

Na ₂ HPO ₄ 1.00%

Polyvinyl alcohol (»Elvanol 51-05«) 1.00%

Sulphated sebum as anti-foaming agent 0.1%

Water 61.5%

First, the hydrocarbon polymer and the polyvinyl alcohol are mixed with the active ingredient, to avoid clumping. The sodium hydroxide and the disodium phosphate are first dissolved in water. Then the solids and antifoam are added and the mixture is ground in the sand mill until the particle size of the active ingredient less than 10 μ. amounts to.

The aqueous dispersion is diluted with water and spread on selected plots in a strawberry plantation sprayed, which is heavily infested by the bud and leaf nematode Aphelenchoides besseyi. the Spray solution contains 120 g of active ingredient according to the invention per 100 liters of water. The spray density is 2.2 kg Active ingredient per hectare. All above-ground parts of the plant are thoroughly moistened. On the sprayed plots the strawberry plants thrive well and provide a rich yield. In the unsmashed parts of the When planted, the plants are yellow, slow-growing and have poor yields.

Example 17

Methyl-l-carbamoyl-N ^ methylcarbamoyl-

oxy) thioformimidate 2%

Dimethylformamide 4%

Granular attapulgite with particle sizes

from 0.25 to 0.6 mm 96%

First, the active ingredient is dissolved in the heat in the dimethylformamide and then this solution sprayed on the attapulgite while the latter is circulated. Due to the low volatility of the solvent, it remains in the grains for a longer period of time, however, slowly evaporates.

This granular preparation, the methyl-1-carbamoyl-N- (dimethylcarbamoyloxy) thioformimidate contains as active ingredient, is in a density of 3 kg of active ingredient per 10,000 m furrow length in the furrows of potato plants scattered. This increases the number of certain soil pests for potatoes, such as larvae of Graphognathus leueoloma, the mole locust and wireworm larvae, greatly diminished. As a result of the system movement of the connection according to the invention of the soil in the potato leaves, the potato plants are against the infestation by the potato aphid Macrosiphum iuphorbiae and the green peach aphid Myzus persicae.

Example 18

Methyl-l-carbamoyl-N-Cdimethylcarbamoyl-

oxy) thioformimidate 5%

Condensation product from polyethylene

oxide and trimethyl nonyl ether 5%

Granular vermiculite 89%

Fine-particle synthetic silica 1%

First, the active ingredient and the fine-grain silica are mixed and finely powdered. This Dust is then briefly mixed with the granular vermiculite and with the liquid surfactant Agent sprinkled.

The granular approach described above, the methyl-l-carbamoyl-N-CmethylcarbarnoyloxyVthioformi- Containing midat as an active ingredient, is used together with cottonseed when planted at a density of 2.5 kg Active ingredient sprinkled into the furrow for every 10,000 m furrow length. The developing cultures are owing the system movement of the compound according to the invention from the soil into the seedlings against attack protected by insects. The infestation by the cotton aphid Aphis gossypii, various bladder worms and the leaf caterpillar Liriomyza brassicae is suppressed for a period of up to 3 or 4 weeks.

Example 19

Allyl-1-carbamoyl-N-Onethylcarbamoyl-

oxy) thioformimidate 10%

Gypsum and ammonium sulfate 90%

The above ingredients are mixed and added according to the method of U.S. Patent 3,168,437 a product of rapidly disintegrating grains with particle sizes of 0.25 to 1 mm. the Active ingredient concentration can be in the range of 2 to without affecting the physical properties 50% can be changed.

The granulated product is spread with the fertilizer spreader at a density of 20 kg of active ingredient per hectare, then worked into the soil with the disc harrow. The one that was then grown on this field Tobacco is not attacked by the nematodes Pratylenchus braehyurus and Meloidogyne incognita. Soil insects such as mole locusts and wireworm larvae, which damage the tobacco, are also found killed. The tobacco plants in this field thrive quickly and give good yield, while tobacco only thrives slowly in a similar but untreated field and only a few marketable leaves supplies.

In the same way, methyl-l- (dimeth> lcarbamoyl) -N- (methylcarbamoyloxy) thioformimidate converted into a granulated product. This compound is supplied with a fertilizer distributor in a density of Spread 5 kg of active ingredient per hectare and then work it into the soil with the disc harrow.

The tobacco grown on this soil is resistant to infestation by the nematodes Pratylenchus spp. and Meloidogyne incognita protected. As a result, the plants will thrive quickly and produce good yields.

5 Example 20

The approach according to Example 19 with methyl 1- (dimethylcarbamoyl) -N- (methyIcarbamoyloxy) thioformimidate as an active ingredient, the fertilizer spreader is used at a density of 5 kg of active ingredient per ha on one the soybean nematode Heterodera glycines infested field. The grains are with the Disc harrow thoroughly mixed with the soil. Develop soybeans grown in this field vigorous green plants and give a good yield. Cultivated in a neighboring, untreated field Soybeans are small, have yellowish leaves, and have poor yields.

B e i s ρ i e 1 21

The approach according to Example 19 with methyl l- (dimethylcarbamoy!) - N- (methylcarbamoyloxy) -thi ( formimidate as an active ingredient is in a density of 5 to 12.5 kg of active ingredient per 10,000 m of furrow length on a through the Gold nematode Hecterodera rostochiensis infested potato field applied by removing the grains in front of the Scattered egg plants of the potato seeds in the open furrow will. The potato plants in this field have become dark green, vigorous at harvest time Plants develop and provide high potato yields. A habitable, untreated field provides small plants and poor yield at harvest time.

Example 22

35

The approach according to Example 19 with methyl l- (dimethylcarbamoyl) -N- (methylcarbamoyloxy) -th ^: oformimidat as active ingredient is used to treat a field in which vine cuttings are to be set and which is infested by the dagger nematode Xiphinema index. The treatment is carried out at a density of 4 to 8 kg of active ingredient per hectare with the fertilizer spreader and then worked into the soil with the disc harrow. The vines grown in this field are protected against the dagger nematode and the virus that it transmits, which causes fan leaf disease.

Example 23

The batch according to Example 19 with methyl l- (dimethylcarbamoyO-N ^ methylcarbamoyloxy ^ thioformimidate as the active ingredient is used in Hawaii for the treatment of a plantation infested by the nematodes Retylenchulus reniformis and Paratylenchus minutus. The treatment is carried out at a density of 3 to 8 kg of active ingredient per hectare using the fertilizer distributor and followed by incorporation into the soil with the disc harrow. in this field grown pineapple plants deep, extensive roots and thrive. in a ^ m adjacent untreated field Λ remain nanaspflanzen small and grow as a result of their poor roots slow.

Example 24

Methyl HdimethylcarbamoyO-N-imethylcarb ^ moyloxy) thioformimidate is dissolved in water, and with this solution, cucumber seeds are concentrated in a ionic concentration treated by 12.5 g of active ingredient per leg of seed. The seeds treated in this way produce a culture which can resist for a period of up to 1/2 weeks after planting the infestation is protected by the root nematode Meloidogyne incognita. A longer one Protection is obtained by treating the seeds with higher concentrations of active ingredients. That way Protected plants develop deep and dense roots, thrive quickly and provide an early and rich yield of marketable cucumbers.

The compound according to the invention is harmless to the seeds and can be used in concentrations of 10 g or more of active ingredient per kg of seed can be used without damaging the seedlings in any way. If the seeds are to be protected against fungus infestation after planting at the same time, the Compound according to the invention applied in combination with tetramethylthiuram disulfide.

Example 25

Methyl -1 - (dimethylcarbamoyl) - N - (methylcarbamoyloxy) thioformimidate is used to treat a young citrus plantation in Arizona infested by the citrus nematode Tylenchulus semipenetrans by dissolving the compound in the water used for irrigation. The treatment takes place at a concentration of 4 to 5 kg / ha in 2.5 cm of irrigation water. This will make the young Trees are protected against infestation by the citrus nematode, they thrive quickly and provide a marketable one Fruit yield. Shows a nearby citrus plantation not treated in this way poor growth, less strong trees and only a small yield of small ones Fruits.

Claims (1)

ί 768 623 claims: 1. Thiofon imidate compounds, labeled by the general formula : n - c - c = o - c - n: