LU86313A1 - S, S-DITERTIOBUTYL ETHYLPHOSPHONODITHIOATE - Google Patents

Description

*; \> The invention relates to 4 S ethylphosphonodithioate, S-ditertiobutyle, pesticidal compositions containing it as active material and its use as an insecticide and nematicide.

The compound of the invention has the formula CHj CH2 - P (= 0) [-SC (CH3) 3] 2 (formula 1) and has a broad spectrum of insecticide and nematicide activity and has excellent stability and long afterglow, especially in the ground.

The compound can be used, in particular, in agriculture, against adults, larvae and eggs of Lepidoptera (butterflies and mites), for example Heliothis spp such as Heliothis virescens (tobacco budworm),

Heliothis armiqera and Heliothis zea, from spodoptera such as S. exempta, S. littoralis (cotton caterpillar), S. eridania (southern armyworm), Mamestra configurata (bertha :: armyworm); Earias spp, for example E. insulana (thorny caterpillar of cotton plant), Pectinophora spp. for example Pectinophora gossypiella (pink cotton worm), Ostrinia 20 spp. such as 0. nubilalis (European corn borer), Trichoplusia ni (cruciferous looper), Pieris spp (cabbage pieride), Laphygma spp. (armyworms), Agrotis and Amathes spp. cutworms), Wiseana spp. (porina mothe), Chilo spp. (rusty rice moth), Tryporyza spp and Diatraea spp. (white rice moths and sugar cane borers), Sparganothis pillerinia (grape borer), Cydia pomonella (codling moth), Archips spp. (fruit tree tortrix moths), Plutella xylostella (cruciferous moth), against adults and beetle larvae, for example Hypothenemus hampei 30 (coffee berry borer), Hylesinus spp. (bark beetles),

Anthonomus grandis (cotton beetle), Acalymma spp. (cucumber beetles), Lema spp., Psylliodes spp.,

Leptinotarsa decemlineata (Colorado potato beetle), Diabrotica spp. (corn rootworms), Gonocephalum spp. (false 35 wire worm), Agriotes spp. (wireworms), Dermolepida, Lepidiota and Heteronychus spp. (white worms), Phaedon cochleariae "2". (watercress beetle), Lissorhoptrus oryzophilus (aquatic rice weevil), Meligethes spp. (meligeths. cruciferous), Ceuto rhynchus spp., Rynchophorus and

Cosmopolites spp. (root weevils) Sitona spp (pea and bean 5 weevils); against Hemiptera, for example Psylla spp., Bemisia spp., Aphis spp., Myzus, Megoura viciae. Phylloxera spp, Adelges spp. Phorodon humuli (hop aphid), Aeneolamia spp., Nephotettix spp. (leafhoppers), Empoasca spp., Nilaparvata spp., Perkinsiella spp., Pyrilla spp., 10 Aonidiella spp (for California red), Coccus spp., Pseudococcus spp, Helopeltis spp. (mosquito bugs), Lygus spp. Dysdercus spp., Oxycarenus spp., Nezara spp. ; Hymenoptera, for example Athalia spp. and Cephus spp. (cephs), Atta spp. (leaf cutter ant); Diptera, for example Hylemyia spp. (root flies), Atherigona spp. and Chlorops spp. (shoot flies), Phytomyza spp. (leafminers), Ceratitis spp. (fruit fly); Thynasopters such as Thrips tabaci; Orthoptera such as Locusta and Schistocerca spp. (locusts) and locusts, for example Gryllus spp. and Acheta spp. and gryllotalpidaes (mole crickets); Collembola for example Sminthurus spp. and Onychiurus spp. (springtails), Isoptera for example Odontotermes spp. (termites), Dermaptera for example Forficula spp. (earwigs) and also other arthropods of agricultural importance such as mites, for example Tetranychus spp., Panonychus spp. and Bryobia spp. (spiders), Eriophyes spp. (phytoptes), Polyphagotarsonemus spp. ; Blaniulus (millipede), Scutiqerella spp. (symphilids), Oniscus spp. (woodlice) and 30 Triops (crustaceans) and also plant parasitic nematodes, infesting both roots and stems, such as root nematodes (Heterodera spp, Globodera spp), (Meloidogyne spp) "nematode lesion" ( Xiphinema spp) and "stem and bulb eelworms" (Ditylenchus 35 spp).

"* 3

Because of its good activity against corn rootworm (Diabrotica sp.) And its great persistence in the soil, the compound according to the invention is particularly advantageous for the fight against corn rootworm. The duration of the residual activity of the compound in the soil against corn rootworm is unexpectedly greater than that of the compounds of neighboring chemical structures, as shown by the following experiment described in Example 1:

Example 1: 10 Experience

The compounds tested have the formula: R (X) P (rX1) (X2R1) (X3R) 15

Compound R (X) X1 X2 R1 X3 A Et - 0 S t-butyl S t-butyl B Et - 0 S n-propyl S t-butyl 20 C Et - 0 S iso-propyl S t-butyl D Et - 0 S iso-butyl S t-butyl E Et - 0 S n-butyl S t-butyl F Me - 0 S n-propyl S t-butyl G Et - SS t-butyl 0 iso-propyl 25 H Et - SS t- butyl 0 t-butyl I And 0 0 S t-butyl S t-butyl J Et 0 0 S t-butyl S sec-butyl 4

Compound A is the compound according to the invention B is the compound n ° 2 of the American patent n ° 4 472 390 5 C is the compound n ° 7 of the American patent n ° 4 472 390 D is the compound n ° 9 of the American patent No. 4,472,390 E is Compound No. 10 of U.S. Patent No. 4,472,390 F is Compound No. 12 of United States Patent No. 4,472,390 G is Compound No. 8 of U.S. Patent No. 4,268,508 10 H is a congener of compound A included in American patent n ° 4,268,508 I is compound n ° 11 of PCT application n ° WO 83/000870 J is compound n ° 10 of PCT application n ° WO 83 / 000870 15 Residual activity and persistence test against corn rootworm (Diabrotica spp.) - Method:

A soil-clay mixture having a water content of approximately 23% of the weight dried in an oven (determined by drying a sample for 24 hours at 110 ° C.) is used as soil. All the doses of product tested for treatments are expressed in parts per million (ppm) of the weight of soil dried in the oven. Before treatment with the test compound, the soil is sieved with a 3.5 mm sieve. The product to be tested is dissolved in dimethyl ketone so as to provide concentrations such that the addition of quantities of 1 ml of solution to soil samples corresponding to 100 g of soil dried in the oven, gives concentrations of 0 , 05, 0.1 and 0.5 ppm and in some cases, 0.05 ppm of the product to be tested.

Soil samples corresponding to 500 g of oven-dried soil are placed in polyethylene bags to which are added 5 ml of solution, in dimethyl ketone, of the test product, at the desired concentration. The contents of the bags are then thoroughly mixed. The bags are then opened for one hour to allow 5 days for the dimethylketone vapor to disperse.

Soil samples taken from the bags are immediately tested for activity against Diabrotica 1 undecimpunctata (day 0). The remaining soil is then stored at 5 to 24 ° C in sealed browned glass jars and other examples are taken and tested on the 7th, 14th, 21st, 28th, 42nd, 56th, 70th and 84th day after treatment with the product. to be tested (days 7, 14, 21, 28, 42, 56, 70 and 84), the soil being remixed before taking each sample.

Activity against Diabrotica is determined as follows:

Diabrotica larvae are raised at 25 ° C on corn seeds.

About 20 g of treated soil is placed in a 25 x 75 mm glass flask containing 2.5 ml of distilled water and a germinated corn seed with well developed roots. Five 5-day-old Diabrotica larvae are placed on the ground and any larvae which do not sink into the ground after a few minutes are replaced until all the larvae have sunk into the ground. The tube is covered with a mesh cover and kept at 25 ° C for four days. Each treatment is subjected to four repetitions, up to and including day 42, and two repetitions for days 56, 70 and 84. After four days, the samples are examined, the number of dead and living larvae counted and the average larval mortality calculated as a percentage for the four replicates in comparison with untreated controls.

An average percentage mortality of at least 90 indicates a satisfactory level of efficacy against Diabrotica larvae.

The results obtained are recorded in the following 35 tables I and II

ύ 3 6 TABLE (I) 5 __ 1 I Concentration moyenne Average percentage mortality Γ i Compound I of the compound with Diabrotica larvae_

there testerl tester (ppm) I DAY

I_I_I Ö | 1 | 14 | 21 128 142 156 170 84 10 I I 0.5 | loo | loo | 100 | 100 | 100 | 100 | 100I100I100 I A I 0.1 110011001100i 901 95 | 90 \ 301 20 | ~ Ô ~ I_I 0.05 ~ ("901 95 | 100 | 351 401 161 101 0 ΊΓ IB | Ö75 f'ÏÔÔ'l10011001 9511001 0 * | | I_I 0.1 I 95 | 301 0 1 0 * 1 ....... 1 ..... 1 "| 15 1 I 0.5 | 100 | 100 | 100 | 100 | 100U00 | 50 * | 70 * | ~ I c 1 Ô7Ï I1001 85 | 601 15 | 10 | 0 * | | I_I 0.05 1 30i 251 ο I "Ό * Γ" 'Γ I' "T ......" I ~~ IDI 075 f100I100I1001100I 751 5 | 0 * |

I_I 0.1 I 301 201 5 i law 5 | 0 * | T ...... I

20 I Ë I Ö75 I100I 70 | 30 | 5 | 0 * | | | I I 0.1 1 0 1 101 0 i 0 * 1 1 1 -j- 1 - I F 1 075 I100I 951 10 | 0 * 1 | | |

I_I 0.1 I 351 5 I 0 I 0 * 1 I I I

I G I Ö75 Γ 30 | 0 * | I I I I I

25 I I Ö7I I 5 I 0 * | I I | I | 1 — R-, σ; · 5 · -Τ-35Γ j} "| 1 ........ 1! - | ....... [.......- | - I_I 0.1 Ί 0 I 0 * 1 I I I I I ~ I ï I 0.5 I100I100I100110011001 901 0 * 1 I_I 0.1 I 201 0 1 0 1 0 * 1 1 1 1 1 30 I J I Ö75 Γ100I 90I 80 | 50 | 75 | 16 | 10 | 0 *

J_1 0.1 1 0 I 5 1 0 1 0 * 1 I I I

* end of test 35 7 TABLE (II) Ί I Persistence of average mortality in Γ I Compound I percentage of at least 90 against larvae of | I to test I _Diabrotica (days) _ |

I I Concentration of the product to be tested (ppm) I

5 I_1 Û, 5 1 0.1 I 0.05 1 I A | gt 84 | 42-56 | 14-21 |

II I I I

! I-1-1-1 I B | 28-42 10-71 - |

I _I_I_I_I

10 I C | 56-70 10-71 + I

II I I I

! I I I I

I D | 21-28 | + | - | I E | 0-7 | + I - | 15 d-111_j I F I 7-14 I + I - |

II I I I

I-1-1-1-1

I G I + I + I - I

II I I I

I I I I I

20 I H | + | + I - | i _! _! _ I_i

I I I I I

I I I 42-56 I + I - I

II I I I

I I I I I

I J I 7-14 I + I - I

25 I _! _! _! _ I

"gt" means "greater than" "-" means "not tested" "+" means that the average percentage mortality did not reach 90 on day 0

A range for example "42-56" means that the average percentage mortality has fallen below 90 between these days.

V

8

From the above results, it appears that: 1) At the concentration of 0.1 (ppm), compound A has satisfactory efficacy against the larvae of Diabrotica for more than six times longer than compound B, the efficacy of compound A being satisfactory until day 42, while compound B no longer satisfactory efficacy on day 7. Even at a concentration five times higher (0.5 ppm), compound B no longer of satisfactory efficacy between day 28 and 10 day 42. In addition, compound A still has satisfactory efficacy on day 14 at the low concentration of 0.05 ppm, while, as indicated above, compound n has more satisfactory efficacy on day 7 even at a double concentration (0.1 ppm).

2) At the concentration of 0.1 ppm, compound A has satisfactory efficacy against Diabrotica larvae for more than six times longer than compound C, the efficacy of compound A being satisfactory until day 42 , while compound C no longer gives an average percentage mortality of 90% on day 7. At the half dose (0.05 ppm), compound A has satisfactory activity until day 14 while compound C does not reach this level of efficiency even on day 0.

3) Even at a concentration of 0.5 ppm, compound 25 D does not give satisfactory activity against Diabrotica larvae on day 28, while, on the contrary, compound A has satisfactory efficacy twice as long until on day 42, at a concentration five times lower (0.1 ppm). At a concentration of 0.1 ppm, compound D does not have satisfactory efficacy even on day 0, while compound A has satisfactory efficacy at this concentration until day 42 and even at a concentration of five times lower (0.05 ppm), has satisfactory efficacy until day 14.

4) At the concentration of 0.5 ppm, compound E no longer has satisfactory efficacy against the larvae of

V

9

Diabrotica on day 7, while even at a concentration five times lower (0.1 ppm) compound A has satisfactory efficacy for more than six times longer, until day 42. Even at a concentration ten times 5 lower (0.05 ppm) compound A has an efficiency twice as long, on day 14, than compound E at 0.05 ppm.

At a concentration of 0.1 ppm, compound E is little or not effective even on day 0, while at this concentration compound A has satisfactory efficacy until day 42 10 and, even at a concentration half (0 , 05 ppm), has satisfactory efficacy until day 14.

5) At a concentration of 0.5 ppm, compound F no longer has satisfactory efficacy against the larvae of Diabrotica on day 14, while at a concentration five 15 times lower (0.1 ppm) compound A has satisfactory efficacy for at least three times longer, until day 42 and even at a concentration ten times lower (0.05 ppm) compound A has an efficacy which lasts twice as long, until day 14. At a concentration of 0.1 ppm, compound F does not have satisfactory efficacy even on day 0, while at this concentration compound A has satisfactory efficacy until day 42 and even at half the concentration (0.05 ppm) has satisfactory efficacy until day 14.

6) Neither compound G nor compound H has satisfactory activity against Diabrotica larvae even on day 0 at concentrations of 0.5 ppm and 0.1 ppm, while compound A has satisfactory activity up to days 42 and 14 respectively, at concentrations of only one fifth or one tenth of the highest concentration (0.05 ppm) of compound G and compound H tested.

7) At a concentration of 0.1 ppm, compound I does not have satisfactory efficacy against Diabrotica larvae even on day 0, while, at this concentration, compound A has satisfactory efficacy until 10 day 42 and, even at a concentration five times lower (0.05 ppm), compound A has satisfactory efficacy until day 14. At a concentration of 0.5 ppm, compound I has no more Satisfactory efficacy 5 at day 56, while at this concentration compound A has satisfactory efficacy until day 84 and even at a concentration five times lower (0.1 ppm) has satisfactory efficacy for a period comparable to that obtained with compound I at a concentration five times 10 times (0.5 ppm).

8) At a concentration of 0.5 ppm, compound 3 no longer has satisfactory efficacy against the larvae of Diabrotica on day 14, while compound A, at one, concentration five times lower (0.1 ppm ) has an efficacy at least three times longer, on day 42 and at a concentration ten times lower (0.05 ppm) compound A has a satisfactory efficacy twice as long, until day 14. At a concentration from 0.1 ppm compound 3 no longer has satisfactory efficacy even on day 20 0, while at this concentration, compound A has satisfactory efficacy until day 42 and even at a concentration five times lower (0.05 ppm) has satisfactory efficacy until day 14.

9) At a concentration of 0.1 ppm, compound A has a satisfactory efficacy on Diabrotica larvae six times more persistent, ie at least until day 42, than the most persistent of the comparison compounds at 0.1 ppm (compound B and compound C), which at this concentration no longer has satisfactory efficacy on Diabrotica on day 7, while none of the other seven comparison compounds has satisfactory efficacy on Diabrotica even on day 0.

10) Expressed as average mortality as a percentage of Diabrotica on days 21, 28 and 42, at a concentration of 35 0.1 ppm, the results recorded in table (I) show that on day 21, compound A is six times more c 11 active than compound C and nine times more active than compound D and on day 28, compound A is nine and a half times more active than compound C and nineteen times more active than compound D, seven remaining comparison compounds 5 are no longer active at these days while at day 42, compound A gives an average percentage mortality of 90% of Diabrotica, while none of the nine comparison products is active at day 42.

The results recorded in Tables (I) and 10 (II) clearly demonstrate the essential and unexpected advantage of compound A compared to the nine comparison compounds both from the point of view of the persistence of a satisfactory level of efficacy. on Diabrotica and activity against Diabrotica at given times after application of the test compounds. This appears particularly well when examining the results obtained at a concentration of 0.1 ppm of product to be tested, for which one obtains with compound A a satisfactory efficacy on Diabrotica at least until day 42, while a compound of comparison at this concentration (compound C)) no longer has satisfactory efficacy on day 14 a comparison product, compound B has no longer satisfactory efficacy on day 7 and the other seven comparison compounds have no Satisfactory efficacy on day 0. Even at a concentration five times higher (0.5 ppm), only two of the comparison compounds (compound C and compound I) have a satisfactory efficacy as long or slightly longer than that of the compound A at a concentration five times lower (0.1 ppm) and even there compound C and compound I no longer have satisfactory efficacy respectively on day 56, while compound A has satisfactory activity beyond day 84 at a concentration 0.5 ppm.

EXAMPLE 2 Control of Diabrotica on Corn in the Field 35 Compound A, formulated as 10% granules, is applied in a strip, at the time of sowing, on the soil of a 12 ♦ 'i. '*' · * "'*'. · I. · 1 - it plots a field of maize infested with Dlabrotica larvae. Maize plans were then uprooted and their roots observed to assess the damage caused by Dlabrotica spp using a standard rating scale 5, in which 6.0 represents maximum attack by the parasite and 1.0 represents no visible damage.

The application rates indicated below are those of compound A in kilograms per hectare (kg / ha). The following results are obtained: 10

I Doses I Root notation I

Application ID I_I

1 (kg / ha) _I repeat plots_I average I

I Compound A | A B C D I I

15 I 0.84 i I 2.1 2.2 2.1 1.8 I 2.05 | I 0.56 il 2.6 2.1 2.4 1.9 | 2.25 | I 0.28_I 2.8 2.8 2.9 2.3_I 2.70 |

I witness no I II

I treated I 5.9 5.9 4.9 3.6 | 5.08 |

20 I_ | _! _ I

The low root ratings obtained with compound A in comparison with those of the untreated controls demonstrate the high efficacy of this compound against Diabrotica spp.

Example 3: Control of Hylemyia platura on corn in the field

Compound A, formulated as a 20% granule, is applied in a band or in the seed line, on the soil of a plot of corn in the open field infested with gray flies, at a rate of 1.12 kh / ha of compound A, the two treatments being carried out at the time of sowing.

13 The effectiveness of the treatment against the gray fly (Hylemia platura) is then determined by counting the fly pupae on the given lengths of the seed stripe.

The following results are obtained: 5

Compound A pupae found, in percentage at 1.12 kg / ha of those in the control

Band treatment 15 10 Sowing line treatment 30

The reduction of the pupae by 85¾ and 70¾ 15 respectively proves the high activity of compound A against the gray fly.

Example 4: Fighting mole crickets in the lawn

Compound A, formulated in granules at 20¾ and applied to turf infested with mole crickets (gryllotalpid species) 20 at doses equivalent to 5.56 and 11.2 kg / ha of compound A.

Mounds of earth produced by insects are observed before and after treatment. The following results are obtained: 25 I I Compound A I |

I number of I (kg / ha) I control I

I mounds I 5,6_11,2_1 untreated | washing treatment I 13,8 | 7.3 | 30 after treatment I 2.8 I 8.3 |

II II

washing treatment I 10.3 I 15.0 | after treatment I 1.5 I 17.0 | . .. ··. · “. * · / "'". · * '. > * ·; j. .14.

The significant reduction in the number of mounds between counts before and after treatment proves the usefulness of compound A in the fight against mole crickets.

5 Example 5: Control of pea and bean weevil (Sitona spp) larvae in bean fields

Compound A, formulated as a 10% granule, is applied, in two experiments, to the soil surrounding the emergence of beans sown in spring, in the open field, in a plot infested with pea and bean weevils, at doses of 1 kg / ha of compound A. The plots are subjected to four repetitions in experiment 1 and three repetitions in experiment 2. About seven weeks later, the plants are uprooted and the larvae of weevil counted on the roots. The results are expressed as an average percentage reduction in the number of larvae compared to the plants, untreated controls.

The following results are obtained. :

20 | Compound A I_% reduction in the number of larvae_I

1 (kg / ha) 1 Experience 1_j_Experience 2_I

I '2 I 90.2 I 92 |

I 1 I 53.3 I 93.75 I

25 | _j_j_ | The significant reduction in larval populations obtained with compound A, in particular at the dose of 2 30 kg / ha in experiment 1 and experiment 2 and of 1 kg / ha in experiment 2, proves the effectiveness of this compound against pea and bean weevil larvae.

».,» '* · * ‘T-.

* 15.

Example 6 is a measure of effectiveness against Lepidiota frenchi

Compound A is dissolved in acetone and this solution is used to process 5 t soil samples to have a scale of known concentrations of the compound in the soil. After evaporation of the solvent, the treated earth is placed in glass jars (approximately 110 g of earth per jar). Twenty jars are prepared for each concentration. Each jar then receives a larva 10 at the third stage of Lepidiota frenchi (cane white grub).

The mortality of the larvae is evaluated twenty eight days later.

The following results are obtained:

I Application rate of I% of corrected mortality I 15 I compound A in mg / kg I of dead larvae I

1 of earth I_in the witnesses I

I 0.5 I 47 I

I 1.0 | 89 | 20 | 2.0 | 95 |

I 4.0 .1 100 I

J_BjO_ | _100_I

25

The results obtained prove the high insecticidal activity of compound A against Lepidiota frenchi • I.

, · Ν. »·. · · I * -! • · - A .'-? '·· * *' · ’'î ·' i * 16.

· * I * * î »

Example 7: nematlcid activity weights a) Ditylenchus dispsaci (stem and bulb ellworm)

Nematodes are raised on alfalfa plants (cv du Puits) in the greenhouse. Two or three months after initial infection, the plants are harvested, washed and the eggs and larvae of the nematodes are removed by soaking the torn stems and leaves in water. After sieving, an inoculum suspension containing approximately 150 larvae per milliliter is prepared in distilled water. Equal parts of contaminated soil, sieved to a particle size of 1 to 2 mm, and river sand are mixed. To the lots of this earth is added the compound A to be tested, previously dispersed in distilled water with Tween 80, to obtain the necessary range of dilutions of chemical in the earth.

Plastic pots for plants, 200 ml capacity are partially filled with coarse untreated sand on which are sown 100 seeds of alfalfa per pot. The pots are then filled with chemically treated soil, except in the case of untreated controls where untreated soil is present. Each pot is watered from above with 5 ml of nematode suspension, so that each pot receives about 750 larvae. The pots are kept at an optimum moisture content for seed germination and plant growth.

Twelve to fourteen days later, the alfalfa seedlings are harvested and examined. The effectiveness of each treatment is determined by the percentage reduction in attack compared to the untreated controls.

i i don't 17

The following results are obtained:

I Dose I ¾ attack reduction I

Id'application J_ compared to witnesses_I

5 I of compound A | | I

I (kg / ha) _I Experiment 1 I Experience 2_I

III I

I 100 I 100 | - I

I 50 I 100 | 100 I

10 I 25 I 80 I 100 I

I 10 I 50 | 70 I

I 5 I 50 | 80 I

I 1 I | 60 |

I _! _! _ I

15 (h _ "means not tested at this dose in this experiment) b) Meloidogyme incognita (root nematode)

The culture is maintained on tomato plants in the greenhouse. A suspension of standard root nematode inoculum, of about 1,500 eggs per milliliter of distilled water is prepared from washed macerated and sieved roots. At least 10-15% of the eggs are in the embryonic larval stage.

25 The soil for the experiments is composed of a mixture of equal parts of river sand, peat and uncontaminated soil prepared by manual mixing. This soil is inoculated with enough suspension of eggs to yield approximately, 30,000 eggs per liter of soil. Compound 30 A is dissolved in acetone and absorbed on a small amount of attapulgite, the acetone then being removed by evaporation. Except for the untreated control soil, the soil lots are then manually mixed with the treated attapulgite to provide the necessary range of 35 dilutions of the chemical to be tested in the final soil lots.

18

With each batch of soil we fill two repetitions of pots. These are then watered and kept in a humid atmosphere for two weeks. Two small tomato plants (Marmande variety) are then transplanted each into a pot, these being kept in the greenhouse again for 4 weeks.

The plants are then harvested, washed and counted root galls. The effectiveness of each treatment is determined on the percentage of reduction of the galls in comparison with the untreated controls. The following results are obtained in the two experiments:

I Dose I% attack reduction I

Id'application J_in comparison with cookies_I

15 I of compound AI I I

I (kg / ha) _I Experiment 1 | _Experience 2_I

III I

I 100 I 100 I - I

I 50 I 100 I 100 I

20 | 25 I 100 I 100 I

I 10 I 100 I 90 I

I 5 | 50 | 0 I

I 1 I - I 0 I

l _! _! _ I

25 means not tested at this application dose in this experiment)

The above results demonstrate the high level of activity against Ditylenchus dipsaci and the very high level of activity against Meloidogyne incognita, of compound A.

The compound according to the invention can be prepared according to methods known per se (by the term "process known per se, the present description means the processes used up to now or described in the chemical literature). the compound according to 'i 19 r._ the invention is prepared from a starting product which is an ethylphosphonic acid halide, this ethylphosphonic acid halide is reacted with methyl 2 propane thiol-2 in the presence of a base for obtaining the compound according to the invention.

According to a characteristic of the invention, the compound of formula I is prepared according to the process consisting in reacting an ethylphosphonic acid halide of general formula CH3CH2 - P ^ OM-XJ-Xj ^ (general formula II), in which X represents a halogen atom, preferably chlorine, and X ^ represents a halogen atom, preferably chlorine, or a tert-butyl group [SC (CH ^) 3), with, when Xj ^ represents a atom halogen, generally two molar equivalents or, when X ^^ represents a tert-butyl group, generally a molar equivalent 2-methyl-propane thiol-2, in the presence of a base.

The process is carried out according to the following reaction schemes A and B: Reaction scheme A: (X- ^ represents a halogen atom) CHjCH ^ P ^ OM-XJ-Xj ^ + 2CH3C (SH) (CH3) CH3 (HA ) ^ 2 bases CH, CH0 -P (= 0) [SC (CH,),] o + 2 base HX / ΗΧΊ 25 / ^ dd 5 2. 552 1

Reaction scheme B: (X ^ represents S-C (CH3) 3) ch3ch2-p (= o) (- x) -sc (ch3) 3 + ch3c (sh) (ch3) ch3 (IIB)

30 base x CH, CH0 - P (= 0) [- SC (CH,),] o + base HX

1) qj 5 2 5 5 2 in which X and X1 are as defined above. The reaction according to reaction scheme A is preferred to prepare the compound of formula I.

The process is advantageously carried out at a temperature of about 0 ° C to 100 ° C in an organic solvent with an alkali thiolate, prepared from thiol and an alkali metal, for example sodium, or a hydroxide of

HO

/ Ί *. *.

alkali metal, for example sodium hydroxide. As suitable organic solvents, there may be mentioned, for example, benzene, toluene, cyclohexanone, tetrahydrofuran, dimethylformamide, 2-butanone and acetone (dimethyl ketone).

The compounds of general formula II can be prepared according to methods known per se. For example, the compounds of general formula IIA can be prepared according to the methods described by Morita et al, Tetra hedron 10 Letters 28, 2522-6 (1978), Morita et al, Chemistry Letters (1980), 435-8, English patent 1,374,757 and Pianfetti and Quin, 3. Amer Chem. Soc., 84,851 (1962) and the compounds of general formula IIB can be prepared according to the method described under published British patent application No. 2,087,891 A. 2-methyl-propane thiol-2 can be prepared according to process described by Dobbin, J. Chem.

Soc., 57,641.

The compound according to the invention is effective as an insecticide and / or nematicide at low concentrations. Due to the low doses to achieve satisfactory efficacy, it is generally practically impossible to apply the compound as is. This is why it is desirable that the compound is applied in the form of insecticide or nematicide compositions comprising S, S ditertiobutyl ethylphosphonodithioate in association with, and preferably homogeneously dispersed, at least one diluent or carrier and / or surfactant acceptable in agriculture and compatible (i.e. diluents or carriers and / or surfactants known in the art as suitable for use in insecticide and nematicide compositions and which are compatible with the material active.

The compositions intended to be applied comprising the active material according to the invention can be liquid dispersions or emulsions, containing from 0.001% to about 1% w / v (weight / volume) of active material. As i X- '' 21 the active ingredient is essentially insoluble in water,. it is desirable to add an inert non-phytotoxic organic solvent to obtain a concentrate which preferably comprises about 2 to 75% by weight by volume of active material and which can be easily dispersed in an aqueous medium to obtain a uniform dispersion of the active ingredient for application. The compositions usually include a surfactant. For example, an effective liquid composition can be prepared with the active ingredient, acetone or ethanol, water, and a surfactant such as Tween-20 (polyoxyethylene sorbitan monolaurate) or each of the other surfactants. well-known assets.

The compositions containing the active ingredient 15 can be in solid form, for example in powder or granular form. For example, the active compound may be mixed with a suitable solid support such as kentonite bentonite, talc or the like, or incorporated into granules for example, mineral clays, for example attapulgite, montmorillonite, diatomite or sepiolite. Preferably, the powder compositions comprise from about 0.5% to 25% w / w (w / w) and the granular compositions preferably from about 1% to 25% w / w of the active material.

Compositions containing the active ingredient may also include other agrochemicals, e.g. insecticides, nematicides and fungicides, e.g. thiofanox, carbofuran, aldicarb and benomyl.

For the control of insects and nematodes, the active ingredient is generally applied to the place where the infestation must be combated, at a dose of approximately 0.1 to 25 kg of active ingredient per hectare treated. Under ideal conditions, depending on the parasite to be controlled, the lower dose can provide adequate protection. On the other hand, adverse climatic conditions, resistance of the parasite and other factors may require, r ..

22 that the active ingredient be used in higher proportions.

When dealing with a soil pest, the formulation containing the active ingredient is evenly distributed over the surface to be treated by any suitable means. The application can be made, if necessary, on the ground or the surface of culture generally on or in a way very close to the seed or the plant to protect. The active ingredient can be washed in the soil by field spraying with water or the natural action of rain can be allowed to take place. During or after application, the formulation can, if necessary, be distributed mechanically in the soil, for example by plowing or passing discs. The application can be made before sowing, at sowing, after sowing but before emergence or after emergence.

The following example illustrates the preparation of the compound according to the present invention.

Example 8 Preparation of S, S-ditertiobutyl ethylphosphonodithioate.

Sodium hydride (3.0 g; 0.125 mole) is suspended in tetrahydrofuran (70 ml) at 0 ° C. 2-methyl-propane-thiol-2 (14.1 ml; 0.125 mole) was then added dropwise over 15 minutes, keeping the temperature below 5 ° C. The mixture is then stirred at room temperature overnight, and ethylphosphonic acid dichloride (7.35 g; 0.05 mole) in tetrahydrofuran (10 ml) is added for 30 minutes with cooling below 35 ° C in a water bath. The mixture is stirred at room temperature for 5 hours and then left to stand overnight.

After adding toluene (200 ml), then water (200 ml) the layers separate. The toluene layer is washed with a 2N sodium hydroxide solution (100 ml), 23 and water (100 ml) then dried, filtered and evaporated to give the S, S ditertiobutyl ethylphosphonodithioate oil (8.72 g; yield 69%).

The structure of the compound is confirmed by its phosphorus NMR (nuclear magnetic resonance) spectrum (a single peak at 65.0 ppm corresponding to 85% of phosphonic acid), and by its proton NMR (with tetramethylsilane as internal reference) : singlet at 1.6 ppm [SC (CH ^) 3 J »two triplets at 1.1 ppm and 1.3 ppm 10 (P-CI- ^ CH ^) and a multiplet at 2.2 ppm (P-CH2CH5 ).

The integration of the proton magnetic spectrum is consistent with the structure indicated.

The following example illustrates compositions according to the present invention: Example 9

A composition is prepared containing: ethylphosphonodithioate of S, S-ditertiobutyle ---- 10% w / w (weight / weight) propylene glycol ..................... ............ 5 ¾ w / w 20 attapulgite 24/48 mesh granules .................. 85% w / w by mixture of ethylphosphonodithioate of S, S-ditertiobutyle and propylene glycol and by spraying the mixture with a flat jet nozzle at a pressure of 2 bars on the attapulgite granules, the mixing being carried out in a horizontal drum. After the spraying on the granules is finished, mixing is continued for about 10 minutes until the liquid has been completely absorbed and the granules are homogeneous. The granules thus obtained can be applied at a dose of 3 kg per hectare to a place infested with Diabrotica sp.

Claims (5)

1. Ethylphosphonodithioate of S, S-ditertiobutyle. 2. Method for controlling insects and nematodes which consists in applying to themselves or their habitat an effective pesticidal amount of 5.5-ditertiobutyl ethylphosphonodithioate. 3. A method of controlling Corn rootworm (Diabrotica sp.) Which consists in introducing into the soil an effective pesticidal amount of 5.5-ditertiobutyl ethylphosphonodithioate. 4. A composition comprising 5.5-ditertiobutyl ethylphosphonodithioate in an amount effective as an insecticide or nematicide and an inert, non-phytotoxic organic solvent or a solid support. 5. Process for the preparation of 5.5-ditertiobutyl ethylphosphonodithioate which consists in reacting an ethylphophonic acid halide of general formula: ch3 ch2 - PUOHX) ^ in which: - X represents a halogen atom, - X · ^ represents a halogen atom or a tert-butyl group with, when X ^ represents a halogen atom, two molar equivalents or, when Xi represents the tert-butyl group, a molar equivalent of 2-methyl propane thiol 2, in the presence of 'a base. Drawings S ίΰπ-j »3 __ £ L ... page3 of which ...... J ...... cover page ....... 23 ..... description pagss ... ..... a ..... of claim 'λ descriptive abbreviation Luxembourg, la 2 0 FEV. 1986 The representative: Me Aîai "‘ “'••' 'avina