FR2514007A1 - THIOPHOSPHORIC ACID AMIDATES, THEIR PREPARATION AND THEIR USE AS INSECTICIDES, ACARICIDES AND / OR NEMATOCIDES - Google Patents

Abstract

THIOPHOSPHORIC ACID AMIDATES OF FORMULA I, IN WHICH R IS AN N-PROPYL, ISOBUTYL OR SECONDARY BUTYL GROUP AND R IS A HYDROGEN ATOM OR A METHYL GROUP; PROCESS FOR THE PREPARATION OF THESE AMIDATES BY CONDENSATION OF A HALO

Description

The present invention relates to thio- acid amidates

phosphoric formula

CHO R

  in which R 1 is an n-propyl, isobixutyl or secondary butyl group and R 2 is a hydrogen atom or a methyl group,

  a process for their preparation and insecticidal compositions

  acaricides and / or nematocides containing them as

as an active ingredient.

  Among the compounds of the present invention, those which are

  particularly preferred for their insecticidal, acari-

  cide and / or nematocide are those which correspond to the formula (I) above in which R 1 is an n-propyl group and R 2 is a

hydrogen atom.

  It is stated in the patent memories of the United States

  States 3,883,556 and 3,968,206, that some sort of amidates

  thiophosphoric acid, for example l- (ethoxy-n-propylthio-

  phosphinyl) -3-pyrroline, have an insecticidal, acaricidal and / or nematocidal effect These patent briefs also indicate the

  1- (ethoxy-n-propylthiophosphinyl) -aziridine and l- (ethoxy-n-

  propylthiophosphinyl) -2-metbylaziridine But it cannot always be said that these compounds are satisfactory as an active ingredient in insecticides, acaricides and / or nematocides. The compounds of the present invention are used as active ingredient in insecticides, acaricides and / or nematocides for controlling parasites harmful to humans, domestic animals, grains, vegetables, fruits,

  grassland, trees, etc. in houses, farmhouses

  vage, cultivated fields, orchards, gardens, woods, etc. These harmful parasites include the following insects, mites and / or nematodes: Insects of the order Hemiptera, such as

  white back (Sogatella furcifera), brown rice jumper (Nilaiar-

  vata lugens), small brown jumper (Laodelphax striatellus), sau-

  Green rice seed (Ne Photettix cincticeps), gray sinphid aphid (M Vzus persicae), cotton aphid (Aphis gossy Dii), and gray cabbage aphid (Brevicoryne brassicae); insects of the Lepidoptera order, such as tea budworm (Caloptilia thoivora), apple adele (Phyllonorycter ringoneella), lemon adele (Phyllocnistis citrella), purple-backed moth (Plutella xylostella), summer fruit moth ( Adoxophyes orana), Oriental tea budworm (Homona mananima), chilo du

  rice (Chilo suppressalis), grain boring (Ostrinia furna-

  calis), rice moth (Cnaphalocrocis medinalis), agrotis

  common (Spodoptera litura) and leucania caterpillar (Pseuda-

  letia separata); insects of the order beetles, such as

  copper chafer (Anomala cuprea), soy beetle (Anomala rufô-

  cuprea), Japanese beetle (Popilla japonica), beetle

  squash leaf (Aulacophora femoralis), zebra flea beetle (Phvllo-

  treta striolata), rice plant weevil (chinocnemus squameus), corn weevil (Sitophilus zeamais) and wheat root worm (Diabrotica sp); insects of the order Diptera, such as common mosquito (Culexpiiens pallens), mosquito

  yellow fever (Aedes aegvpti), malaria mosquito (Anophe-

  lus stephans), housefly (Musca domestica) - and melon fly (Dacus cucurbitae); insects of the Diclyoptera order, such as cockroach (Periplaneta americana), brown cockroach

  ash (Periplaneta fuliginosa) and the German cockroach (Blattel-

  germanica); insects of the order mites, such as the mite-

  common spider (Tetranychus cinnabarinus), two-spotted mite (Tetranychus urticae), lemon moth (Pa nonychus citri), European spider mite (Panonvychus ulmi), cryptomeria red spider, tick bull (Boophilus microolus), the two-spined tick (Haemaphysalis longicornis); and nematodes (order of tylenchids), such as the potato eel (Ditylenchus destructor), the coffee root lesion eel (Pratylenchus coffeae), the cystic eel pommp (Globodera rostochiensis), soybean cystic eel (Heterodera glycines), peanut root node eel (Meloidogyne arenaria), root node eel

  North (Meloidogyne hapla), the eel of the radicular nodes-

  southern res (Meloidogyvne incognita) and the lemon eel

(Tylenchulus semipenetrans).

  The compounds of the present invention can be prepared by reacting a phosphoric acid halide of formula CH 3 O il ap _ x (II) in which R 1 has the meaning given above and X is a halogen atom, with an equivalent or a slight excess

  ethylene imine or propylene imine in the presence or absence of

  presence of a solvent, preferably in the presence of an appropriate solvent

  required, at a temperature of the order of -10 to 502 0, for about minutes to about 5 hours, in the presence of an agent fixing the

  acids Among the solvents, aromatic hydrocarbons will be mentioned

  ticks such as benzene, toluene and xylene; ethers

  such as diethyl ether, tetrahydrofuran and dioxan

  born; halogenated hydrocarbons such as chloroform and carbon tetrachloride; ketones such as acetone and methyl isobutyl ketone; other organic solvents such as acetonitrile, & dimethylformamide and dimethylsulfoxide; the water; and mixtures of these solvents. Among other acid-binding agents, there may be mentioned organic bases such as pyridine, triethylamine and N-methylmorpholine and inorganic bases such as sodium hydroxide, hydroxide.

  potassium, sodium carbonate and potassium carbonate.

  ethylene imine or propylene imine, one of the starting materials, can also be used in large excess. The compounds of the present invention are separated from the reaction mixtures by usual methods of subsequent treatment and, if necessary, they are purified. by rectification, chro-

  column matography or by similar methods.

  Examples of the preparation of the compounds of this

invention are given below.

Example 1

Preparation of compound N 2 (1)

  A mixture of 2.6 g of e # hyleneimine and 6.0 g of tri-

  thylamine was added dropwise to a solution of 9.5 g of methoxy-n-propylthiophosphinyl chloride in 50 ml of chloroform with stirring, while cooling the reaction mixture to maintain its temperature at 15-2000 The reaction mixture was stirred for 30 min still at temperature

  room, then water and the chloroform phase were added.

  that separated was isolated and dried over anhydrous sodium sulfate. Removal of the solvent by vacuum distillation gave 9.3 g of a brown oily substance which was purified by column chromatography on silica gel. 8.3 g of 1- (methoxy-npropylthiophosphinyl) -azfridine 21-

  in the form of a colorless oily substance; ID: 1.4888.

Example 2

Preparation of compound N 2 (3)

  A solution of O l g of dry methoxybutyl chloride -thio-

  phosphinyl in 20 ml of toluene was added dropwise, with stirring, to a mixture of 2.3 g of ethyleneimine and

  0.5 g of 20% aqueous sodium hydroxide, while cooling

  the reaction mixture to maintain its temperature at 0-

  520 The mixture was stirred for 30 min still at room temperature.

  ambient ture The aqueous phase which had separated off was removed and the tolu 4 nic phase was washed with water The solvent was removed by distillation under vacuum and 9.9 g of a brown oily substance were obtained which has been purified by

2.544007

  column chromatography on silica gel 9.1 g of 1 (dry methoxy-butyl-thiophosphinyl) -aziridine were thus obtained

  the form of a yellow oily substance; 23.5: 1.4855.

  The compounds of the present invention which can be obtained

  These preparation processes are indicated in the

table 1.

Board,

  Thiophosphoric acid amidates of formula (I) Starting substance, the phosphoric acid halide of formula (II), used in these preparation processes, can be obtained by the process or processes described in Jo Orgo Chem,

3., 3217 (1965).

  When used 4 S as an active ingredient in

  insecticides, acaricides and / or nematocides, the ingredients

  ses of the present invention are mixed, in proportions of 0.1 to 99.9% o, preferably 1 to 50% by weight, with suitable substances, chosen from solid excipients, liquid excipients, surfactants and other adjuvants, to be mls in the form of oily sprays, highly imulsifiable concentrates, wettable powders, suspensions,

granules or dry powders.

  These compositions contain fine powders or granules of kaolin, bentonite, talc, diatomaceous earth, calcite, hydrated synthetic silica, etc. serving as excipient Compound, R Refractive index n 2 2 2

(1) N 3 H 7 H N 21 1.4888

  (2) nC 3 22 1.4827 (3) Ca H sec H 23.5 1.4855 49 n (4) iso-04 HH 43 1.4848 (5) C 4 H 9 sec C 225 14800 (6) iso -C 4 H CE N 25 1.4773 49, l, 4 v D

  solid; xylene, methylnaptalene, benzene, ligrol-

  ne, petroleum ether, kerosene, cyclohexanone,

  isophorone, chlorobenzene, dichloroethane, dimethyl-

  sulfoxide, acetonitrile, Cellosolve, ethylene glycol, etc. as liquid carriers; non-ionic surfactants

  such as polyoxyethylene alkyl ethers, alkyl ethers,

  polyoxyethylene aryls, fatty acid and sorbent esters

  polyoxyethylene tene and oxyethylene-oxypropylene polymers, and anionic surfactants such as alkyl sulfate salts, alkyl sulfonate salts, dialkyl succinate salts and alkylaryl sulfonate salts, as active tensioning agents used for emulsification, dispersion, wetting or spraying purposes; as well as lignin, salts of sulfonic acids, salts of arginic acid, polyvinyl alcohol, carboxymethylcellulose, PAP (phosphate

  isopropyl acid), as other adjuvants.

  Examples of formulation of the compositions are given below, the numbers of the compounds referring to Table 1 and

  the term "parts" referring to weight.

  Formulation example 1 Compound n (1) (40 parts), an emulsifier, Sorpol

  SM-200 (trademark of Toho Chem Co; principal constituent

  pal: an alkyl-aryl ether of polyoxyethylene) (10 parts) and

  xylene (50 parts) are mixed well to give a concentration

very emulsifiable at 40%.

  Formulation example 2 Compound N 2 (2) (40 parts) and Sorpol SM-200 (the same

  above) (7.5 parts) are mixed, an exci-

  solid pient, Carplex # 80 (trademark of Shionogi and Co; main constituent: silica hydrate 4 e) (20 parts), then diatomaceous earth of 300 mesh (3.5 parts) and the mixture is stirred in a mixer to give a composition

40% wettable powder.

  Formulation example 3 Compound N 2 (3) (5 parts), Toyolignin CT (trademark of Toyobo Co; main constituent: lignin sulfonate salt) (5 parts) and GSM clay (coimmercial brand from Zieklite Kogyo Co; main constituents: kaolin and sericite) (90 parts) are mixed in a friction mill After the addition of 10% water, the mixture is further stirred using a granulator and dried in a stream

  air to give a 5% granule composition.

  Formulation example 4 Carplex # 80 (the same as before) (3 parts), PAP (0.3 parts) and 300 mesh talc (91.7 parts) are

  a Added to a solution of compound N 2 (4) (5 parts) in the acetate

  tone (20 parts), the mixture is stirred in a mixer and

  acetone is removed by distillation to give a compound

tion of dry powder at 5%.

  Formulation example 5 A mixture of compound N 2 (5) or (6) (20 parts) and kerosene (80 parts) is stirred vigorously to give a

  20% oily spray composition.

  When the compounds of the present invention are used in rice fields, other cultivated fields, orchards,

  meadows, lawns or woods as an insect composition

  cide, acaricide and / or nematocide, the amounts applied vary between 1 and 100 g / are and the concentrations vary between 0.01 and 30% when spreading emulsifiable concentrates or wettable powders after dilution with water. oily spray, dry powder and granules are used without dilution When used to control insects harmful to health or against parasites in livestock, their concentrations are the same the compounds of the present invention can also be used in mixed with other insecticides, acaricides and / or nematocides or with fungicides, seed disinfectants, fertilizers or soil modifiers, etc.

  The insecticide, acaricide and / or nematocide activity of the

  of the present invention will be demonstrated by the following experimental examples In the experimental examples, the compounds of the present invention are designated by the numbers which appear in Table 1 and the compounds serving as controls are designated by the compound numbers shown in Table 2.

Table 2

  compound I Chemical structure Observations O n-C 3 H 758 Z o C H O il

n-C 3 H 77 -

C 2 H 50

  aH O N. n-C 4 Hq Sle 2 5 n-C 4 H 9 P "o il 0 H 3 fCH 3

-0 CH 3

NHC O CH 3

  Br% -CE Br-0 H 201 Described in

US patents

  Unis n R 3 883 556 and 3 968 206 ti il, 'i il Il Commercial insecticide 11 cepbat ef Commercial nematocide DBCP (A) (B) (C) (D) (B) (Pè) (G) I r

'14007

  3 experimental example 1 Imulsifiable concentrates of experimental compounds,

  prepared according to the example of formulation i and diluted with the

  prescribed centers, have been sprayed individually on cabbage plants grown in plastic pots each measuring 9 cm in diameter and 6.5 cm in height on a turntable, at a dose of 30 ml / 2 pots After drying in air of

  sprayed compositions, ten tobacco agrotis larvae (S do-

  tera litura) at the 4th larval stage per pot were left to live on the plants, which were covered with a cage Four days later, we counted the number of larvae killed and

  examined the extent of plant damage caused by the larvae.

  The results are presented in Table 3 in terms of larval mortality and extent of damage, the symbols

  expressing the extent of the damage having the following meanings

  High: Symbol Extent of damage None + Slight + Moderate ++ Important +. + Very important

Table 3

  experimental component concentration of the active ingredient used (ppm) Larval mortality (%) Extent of damage

100

(1) 50 100

(1) * 25 90

100

(2) 50 100

90 +

100 +

(A) 50 60 1

(B) 100 70 +

(C) 100 70 +

(D) 100 65 +

(E) 100 O

100 +

(l?) 50 95 +

60 +

  S years O treatment H o C lj cz I il Experimental example 2 Emulsifiable concentrates of experimental compounds, prepared according to formulation example 1, were each diluted with water Up to a concentration of 100 ppm The diluted composition (20 ml) was mixed with 500 g of soil, half of the treated earth was placed in a 12 cm diameter and 8 cm high polyethylene box and three cut pieces of carrot, 3 cm in diameter and 0.5 cm thick, were placed on top and covered with the rest of the treated soil Four copper chafer larvae (Anomala

  cuprea) at the 3rd larval stage were released into the box.

  Seven days later, we measured the number of larvae killed and

  examined the extent of damage to the carrot by the larvae.

  The results of five repetitions of this test for each experimental compound are presented in Table 4, the extent of the damage being indicated by the same symbols as in

experimental example 1.

Table 4

  Compound Number of insects killed experimentally on 20 larvae used Extent of damage

(1) 18

(2) 16

(A) 6 ++

  Without t Without e O ++ treatment Experimental example 5 Emulsifiable concentrates of experimental compounds,

  prepared according to the example of formulation 1, were diluted each

  cun with water up to concentrations of 100, 50, 25 and 12.5 ppm Each diluted composition (0.7 ml) was adsorbed in a filter paper placed in a 5.5 cm polyethylene box of diameter and 3.5 cm in height, into which about 30 mg of sugar were introduced and 10 adults of house flies (Musca domestica) were released After 24 hours, the number of flies killed was measured and deduct the O CL 50

  (ppm) The results are presented in Table 5.

Table 5

Experimental compound LC 50 (ppm)

(1) <12.5

(2) 15.0

(B) 50.0

  Experimental example 4 Five carmine mites (Tetranychus cinnabarinus) adult females per leaf were allowed to parasitize four leaves

  of kidney beans which had grown for 5 Days after being-

  planted in plastic pots each measuring 9 cm in diameter

  tre and 6.5 cm in height Then the pots were kept at 262 C in a room at constant temperature Six days later, each emulsifiable concentrate of experimental compounds, prepared according to the example of formulation l and diluted with water to '' at a concentration of 500 ppm, was sprayed on potted plants, on a turntable, at the rate of 10 ml / pot After 10

  days, the number of adult females on the plants was counted.

  The results are presented in Table 6, a number of adult female mites between 0 and 9 per leaf being represented by (a), between 10 and 30 / leaf by (b) and more than

/ sheet by (c).

Table 6

  Compound Number of experimental adult females (1) (a) (2) (a) (A) (b) Without (experimental treatment xem Dle 5 Each emulsifiable concentrate of experimental compounds, prepared as in formulation example 1, was diluted with water -.1 to a concentration of. 0 r 'pp: lm-iu Gqr -o The rice plants were immersed in each of the 6 mutations for a minute, then air dried The shoots and ten rice chile larvae (Chilo su D Oressa 12 s) at the 3rd larval stage were placed in a plastic box 5.5 cm in diameter and 3.5 cm in height After 10 days, we have counted the number of insects

  killed The results are presented in Table 7.

Table 7

  Compound ju Mortality (% experimentalalrtalt ()

(1) 100

(2) 100

  Without treatment Experimental example 6

  Each of the dry powder compositions of the compounds

  rimentaux, prepared according to the example of frmttlation 4 e was sprayed on a rice plant which had grown in a pot of Wagner of 1/5000 ares, at a rate of 35 kg / 10 ares, and the plant was covered with a wire mesh cage Fifteen small adult brown female jumpers (Laodelph Qx striatellus) were released into the cage and the number of insects killed was counted at

  after 24 hours The results are presented in Table 8.

Table 8

  Experimental Mortality Compound (A)

(1) 100

(2) 100

  Without treatment Experimental example Each of the emulsified concentrates of experimental compounds prepared according to the example of formulation 1 was diluted with water to a concentration of 500 ppm and sprayed on a plant of

  rice which had grown for a month from its seed-

  in a 180 ml plastic box on a turntable

  nant, at a dose of 15 ml / 2 cans After air-drying the sprayed composition, the plant was covered with a wire mesh cage and 15 adult females were released from it.

  green rice jumper (Nephotettix cincticeps) resistant to insects

  carhamate series ticides; after 24 hours, the number of insects killed was counted The results are presented in table 9

0 l Table 9

  Compound ei Mortality (%) experimental I

(1) 100

(2) 100

  Without O treatment Experimental example 8 A mixture of 500 g of soil infested with root node eels (Meloidgvne sp) and 500 g of uninfested soil was loaded into each 1/5000 ares Wagner jar

  and we planted there Young tomato shoots at the age of the 3rd -

  4 th sheet Two days later, the soil was treated with emulsifiable concentrates of experimental compounds, prepared

  following the example of formulation 1 and diluted with water to the concentrations

  prescribed trations, at a dose of 80 ml / pot After 21 days,

  the formation of root nodes was assessed.

  By way of comparison, the same experiment was carried out on uninfested soil only and on infested soil only, without application of nematocidal compound. In this case, the formation of root nodes was evaluated after 30

  days from the planting of the tomato shoots The res l-

  states are presented in table 10, o the extent of training

  of root nodes was scored based on the following criteria.

  Note Extent of root node formation 0 Same result as in uninfested and untreated soil (i.e. no root node formation) 1 Slight root node formation, compared to uninfested and untreated soil 2 Clear knot formation, by comparison with uninfested and untreated soil 3 Strong knot formation, almost to the same extent as in infested land 4 Very strong knot formation, to the same extent or beyond, by comparison with infested land

Table 10

  Compound N Concentration of the ingredient Extent of active experimental formation used (ppm) of root nodes

500 0

(1) 250 O

(2) 250 o O

250 O

(A) 250 2

(G) 500 2

250 3

Experimental example 9

  A mixture of 500 g of soil infested with cystic eels

  only soybeans (Heterodera glycines) and 500 g of soil not

  infested was loaded into each 1/5000 ares Wagner jar.

  The soil was treated, at the rate of 80 ml / pot, with concen-

  highly emulsifiable from experimental compounds, prepared according to

  formulation example 1 and diluted to a concentration almost

  written, then mixed uniformly with the earth of the upper layer

  15 cm larger, and 10 soybeans were planted in each pot. After 30 days, the adhesion of the cysts to the plants was evaluated. For comparison purposes, the same experiments were carried out on uninfested soil. only and on 2 Ä 140 oi of infested soil only, without application of nematocidal compound The results are presented in Table 11, the extent of cyst formation being noted from

  criteria similar to those of experimental example 8.

Table ll

  Compound Concentration of ingredient Scope of forma-

  active experimental used (ppm) tion of cysts (1) loo o (2) 100 O o

(A) 100 2

(G) 500 2

  Experimental example 10 A mixture of 500 g of soil infested with root lesion eels (Pratylenchus sp) and 500 g of soil not

  infested was loaded into each 1/5000 ares Wagner jar.

  Dry powder compositions of experimental compounds, pre-

  trimmed according to the formulation example 4 were applied to the soil at the rate of 0.2 g / pot, and mixed with the latter up to a depth of 15 cm, then 15 carrot seeds were sown on the soil in each jar After 60 days, the development of pathological spots of root lesion was evaluated. For comparison purposes, the same tests were made

  on uninfested soil only and on infested soil

  only with no application of nematacid compound

  results are presented in table 12, the degree of development

* pement of pathogenic spots of radicular lesion being noted according to criteria similar to those of experimental example 8.

Table 12

  Compound Concentration of ingredient Degree of development-

  active experimental used (ppm) of root lesion spots

(1) 100 O

(2) 100 O

(A) 100 2

  (G) 500 1 z Exemplary experimental Ple 11 Adult cotton aphids (Ahis ossii) were released on cucumbers (two true leaves) which had each grown in a plastic box measuring 5.5 cm in diameter and 3.5 cm in height, at the rate of approximately 50 insects per cucumber Three days later, the number of aphids on the cucumber leaves was counted. The soil was treated, at the rate of 9 ml / box, with emulsifiable compounds concentrates experimental, prepared according to formulation example 1 and diluted with water to a concentration of 100 ppm After 2, 5 and 7 days, the number of aphids on the cucumber leaves was counted The results are presented in Table 13 in the form of a density index calculated according to the following formula: Number of aphids Number of aphids in the treated batch in the untreated batch after i days Index before treatment after treatment Index de_ _-x O = xxl OO density 8 O density Number re of aphids Number of aphids

  in the batch treated in the batch not processed

  before the treatment t after i Days after the treatment i represents 2, 5 or 7 and "treatment" means treatment

with an experimental compound.

  Talaul Density index 0 omitted experimental After 2 days After 5 days After 7 days (1) o o o

(2) 10 O O

(3) o o o (4) 5 o o

(5) 3 O O

(6) 6 O O

(a) 40 38 57

(D) 45 37 60

(.) 89 22 20 CD

  (i ') 80 50 53 Sansa treatment 100 100 100 at C>, CD

Claims (4)

  1 Thiophosphoric acid amidate of formula CHO It R R 1 SP -N i in which R is an n-propyl, isobutyl or secondary butyl group and R 2 is a hydrogen atom or a methyl group. 2 Thiophosphoric acid amidate according to claim 1, characterized in that R 1 is an n-propyl group and R 2 is a hydrogen atom.   3 Process for the preparation of a thiophos acid amidate   photic according to claim 1, characterized in that it comprises a condensation of a phosphoric acid halide of formula OH 30 CHO O l J 3. P X   Ri s in which R 1 has the meaning given in claim 1 and X is a halogen atom, with an ethylene-imine or propylene-imine of formula HNR 2   wherein R 2 has the meaning given in claim 1.   4 Insecticide, acaricide and / or nematocide composition, charac-   terized in that it contains an inert excipient and, as   active ingredient, an effective amount for an insecticidal effect   cide, acaricide and / or nematocide of thiophospho- acid amidate 2 o The risk of claim 1.   , Method for controlling an insect, a mite and / or a   ngmatode, characterized in that it consists in treating this insect   ticide, mite and / or nematode with an effective amount for an insecticidal, acaricidal and / or nematocidal effect of the thiophosphoric acid amidate according to claim 1 with a view to the destruction of the insect, mite and / or nematode, 6 Use of the thiophosphoric acid amidate according to claim 1 as an insecticide, acaricide and / or nemato-r cide.