Amido phosphorothiolates

Abstract

The present invention relates to compounds of the formula: ##STR1## wherein R.sub.1 is lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl, unsubstituted aralkyl, lower alkyl or halogen-substituted aralkyl or halogen-substituted alkenyl; R.sub.2 is lower alkyl; Y is hydrogen or methyl and X is lower alkyl; n is an integer of 1 to 5, and a method of producing these compounds. These compounds are eminently suited for killing weeds, injurious insects, nematodes and acaricides.

Description

The present invention relates to new compounds, herbicides, insecticides, acaricides and nematocides characterized by containing a new phosphorothiolate derivative as an active ingredient and the preparation thereof.

More particularly, the present invention provides

1. A NEW PHOSPHOROTHIOLATE DERIVATIVE OF THE FORMULA ##STR2## wherein R.sub.1 is lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl, unsubstituted aralkyl, lower alkyl or halogen-substituted aralkyl or halogen-substituted alkenyl; R.sub.2 is lower alkyl; Y is hydrogen or methyl; X is lower alkyl; n is an integer of 1 to 5,

2. THE PREPARATION OF THE COMPOUND OF THE FORMULA (I) characterized in condensing a salt of thiophosphate of the formula; ##STR3## wherein R.sub.1 and R.sub.2 are the same as defined above, and M is an alkali metal with a halogenated acetoamide compound of the formula; ##STR4## wherein Y, X and n are the same as defined above, and Hal is a halogen atom, and

3. A HERBICIDAL, INSECTICIDAL, ACARICIDAL AND NEMATOCIDAL COMPOSITION CONTAINING THE COMPOUND OF THE FORMULA (I) as an active ingredient.

A preferred range of the compound of the formula (I) is as follows: ##STR5## wherein R.sub.1 is C.sub.1 - C.sub.8 straight or branched chain alkyl, allyl, chloroallyl, methallyl, propargyl, cyclohexyl, benzyl, .alpha.-methylbenzyl, phenethyl, .beta.-methylphenethyl, chlorobenzyl, dichlorobenzyl, bromobenzyl or C.sub.1 - C.sub.4 alkyl substituted benzyl; R.sub.2 is C.sub.1 - C.sub.4 alkyl; Y is hydrogen or methyl; X is methyl or ethyl; n is an integer of 1 to 3.

And a preferred compound as a herbicide is as follows: ##STR6## wherein R.sub.2 is an alkyl group; R.sub.1 is lower alkyl, cycloalkyl, lower alkenyl, halogen-substituted alkenyl, lower alkynyl or phenyl lower alkyl group; Y is a hydrogen atom or methyl group; X is a lower alkyl group; and n is in integer of 1 to 3.

Especially a compound of the formula; ##STR7## wherein Alk.sub.1 is a C.sub.1 - C.sub.4 alkyl; Alk.sub.2 is a C.sub.1 - C.sub.5 alkyl; Alk.sub.3 is a C.sub.1 - C.sub.2 alkyl; has the most excellent herbicidal activity of the compound represented by the formula (I - b) without phytotoxity and toxity to warm-blood animals.

The new active ingredient of the present invention displays a strong herbicidal activity not only when used in both a pre-emergence treatment and a foliage treatment of weeds, but also on various kinds of weed including grassy weeds such as barnyard glass (Echinochloa crusgalli), large crabgrass (Digitaria sanguinalis), goose grass (Eleusine indica), water foxtail (Alopecurus aequalis) and annual bluegrass (Poa annua); broad-leaved weeds such as redroot pigweed (Amaranthus retroflexus), common purslane (Portulaca oleracea), smart weed sp. (Poligonum sp.), common lambsquarter (Chenopodium album), and weeds in paddy field such as false pimpernel (Linderna pyxidaria), monochoria (Monochoria viaginalis presl.) and toothcut (Rotala indica Koehue); sedge weeds such as nutsedge sp. (Cyperus difforuds) and slender spikerush (Eleocharis acicularis).

One of the most important properties of herbicides is that they can display a herbicidal activity on various kinds of weed, because, if they can control most kinds of weed but not a few other kinds of weed, the remaining weeds will often grow and do harm to crops.

Therefore, the compounds of the present invention, which can display a strong herbicidal activity on more kinds of weed, can be said most suitable for a herbicide.

As for the insecticidal effect of the present compounds, they have a strong controlling effect on insects injurious to agriculture such as aphids, stan-borers and armyworms and cutworms; insects injurious to sanitation such as cockroaches, and houseflies; insects injurious to stored cereals; mites; and nematodes. Consequently they are effectively used as a herbicide, insecticide, acaricide and nematocide.

The present invention (1) relates to a herbicide, insecticide, acaricide and nematocide completed based on the above-mentioned information which contain the compounds represented by the formula (I) as an active ingredient.

There were known as relating prior arts to the present invention Belg. Patent No. 767,132 and Swiss Patent No. 496,398. The Belg. patent sayd phosphorodithiolate compounds having unsubstituted piperizino moisty have insecticidal, acaricidal and nematocidal activity, but present inventors have found that alkyl-substituted on that piperidin ring compounds, azepine compounds and tetrahydro quinoline compounds have unexpected excellent herbicidal activity. And it is unobvious from the prior art.

The Swiss Patent No. 496,398 says Thionothiolate type compounds have herbicidal activity, but Dithiolate type compound and Thiolate type compound of the present invention have the different structure.

The present invention (1) and (3) relate to a herbicidal, insecticidal, acaricidal and nematocidal composition completed based on the above-mentioned information which contain the compound represented by the formula (I) as an active ingredient.

The present invention (2) relates to a method for producing a compound of the formula (I) with a herbicidal insecticidal, acaricidal and nematocidal activity characterized in that phosphorodithiolate of the formula: ##STR8## wherein R.sub.1, R.sub.2, Y, X and n are the same as defined above, is obtained by condensing a salt of dithiophosphate of the formula (II); ##STR9## wherein R.sub.1, R.sub.2 and M are the same as defined above, with a halogenated acetoamide compound of the formula (III); ##STR10## wherein Hal, Y, X and n are the same as defined above.

The present invention (2) can preferably be carried out by condensing a salt of dithiophosphate of the formula (II) with halogenated acetamide compound of the formula (III) in the presence of solvents such as water, alcohols, ketones and if possible solvents which can dissolve the both starting materials completely therein. The reaction temperatures and reaction times vary depending upon the kinds of solvent and starting material, and in general the reaction can satisfactorily proceed at 20.degree. to 100.degree. C. for one to several hours. On completion of the reaction, the aimed products can readily be obtained in a very high purity by conventional treatments, however, if necessary, can further be purified by column-chromatography.

Some examples of the starting materials, i.e. dithiophosphate salts and halogenated acetamides, which are used in the practice of the present invention will be shown as follows.

First, examples of dithiophosphate salt are as follows, which are only illustrative but not limitative thereto:

potassium O-ethyl-S-n-propylphosphorodithioate potassium O-ethyl-S-iso-propylphosphorodithioate potassium O-ethyl-S-butylphosphorodithioate potassium O-ethyl-S-sec-butylphosphorodithioate potassium O-ethyl-S-iso-butylphosphorodithioate potassium O-ethyl-S-ethylphosphorodithioate potassium O-ethyl-S-methylphosphorodithioate potassium O-ethyl-S-iso-amylphosphorodithioate potassium O-ethyl-S-n-octylphosphorodithioate potassium O-ethyl-S-cyclohexylphosphorodithioate potassium O-ethyl-S-cyclopentylphosphorodithioate potassium O-ethyl-S-allylphosphorodithioate potassium O-ethyl-S-propargylphosphorodithioate potassium O-ethyl-S-methallylphosphorodithioate potassium O-ethyl-S-2-chloropropenylphosphorodithioate potassium O-ethyl-S-benzylphosphorodithioate potassium O-ethyl-S-.beta.-phenylethylphosphorodithioate potassium O-n-propyl-S-n-propylphosphorodithioate potassium O-n-propyl-S-n-butylphosphorodithioate potassium O-n-propyl-S-allylphosphorodithioate potassium O-n-propyl-S-.beta.-phenylethylphosphorodithioate potassium O-n-propyl-S-iso-propylphosphorodithioate potassium O-n-propyl-S-sec-butylphosphorodithioate sodium O-n-butyl-S-ethylphosphorodithioate sodium O-n-butyl-S-n-propylphosphorodithioate sodium O-n-butyl-S-iso-propylphosphorodithioate sodium O-n-amyl-S-n-propylphosphorodithioate sodium O-methyl-S-n-propylphosphorodithioate sodium O-methyl-S-n-butylphosphorodithioate sodium O-methyl-S-iso-propylphosphorodithioate sodium O-ethyl-S-n-propylphosphorodithioate sodium O-ethyl-S-n-butylphosphorodithioate sodium O-ethyl-S-iso-propylphosphorodithioate sodium O-ethyl-S-sec-butylphosphorodithioate sodium O-n-propyl-S-n-propylphosphorodithioate sodium O-n-propyl-S-n-butylphosphorodithioate potassium o-ethyl-S-(4-chlorobenzyl)-phosphorodithioate potassium O-ethyl-S-(4-tert-butylbenzyl)-phosphorodithioate potassium O-ethyl-S-(4-methylbenzyl)-phosphorodithioate potassium O-ethyl-S-(4-ethylbenzyl)-phosphorodithioate potassium O-ethyl-S-(2-chlorobenzyl)-phosphorodithioate potassium O-methyl-S-(4-chlorobenzyl)-phosphorodithioate potassium O-methyl-S-(4-tert-butylbenzyl)-phosphorodithioate potassium O-n-propyl-S-(4-chlorobenzyl)-phosphorodithioate potassium O-n-propyl-S-(4-methylbenzyl)-phosphorodithioate potassium O-n-butyl-S-(4-methylbenzyl)-phosphorodithioate sodium O-ethyl-S-(3,4-dichlorobenzyl)-phosphorodithioate sodium O-ethyl-S-(4-methylbenzyl)-phosphorodithioate

Examples of halogenated acetamide compound are as follows, which are only illustrative but not limitative thereto:

2-methylpiperidine-.alpha.-chloroacetamide 3-methylpiperidine-.alpha.-chloroacetamide 4-methylpiperidine-.alpha.-chloroacetamide 2-ethylpiperidine-.alpha.-chloroacetamide 2-n-propylpiperidine-.alpha.-chloroacetamide 2,6-dimethylpiperidine-.alpha.-chloroactamide 2,4,6-trimethylpiperidine-.alpha.-chloroacetamide 2-methylpiperidine-.alpha.-bromoacetamide 3-methylpiperidine-.alpha.-bromoacetamide 4-methylpiperidine-.alpha.-bromoacetamide 2-methylpiperidine-.alpha.-iodoacetamide

Next, some representative examples of the organo phosphoric acid ester of the present invention will concretely be shown as follows. ##STR11##

The compounds of the present invention, as described above, display a strong herbicidal activity on various kinds of weed, however one of the most noticeable features thereof is their herbicidal activity on more kinds of weed in addition to their strong herbicidal activity.

Moreover, the compounds of the present invention have other excellent properties as a herbicide, for example, a long persistency, an activity on both a pre-emergence treatment and a foliage treatment of weeds, and a selectivity to many crops such as rice plant, radish, soy bean, pea, tomato, wheat and corn. The present compounds are also useful as a herbicide for, needless to say, paddy rice fields, and cereals, vegetables, orchards, turfs, pasture lands, woods and forests and non-crop lands.

The features of the present compounds as an insecticide, acaricide and nematocide are that they have a controlling effect on various kinds of insect, a wide insecticidal spectrum, a particularly strong lethal effect on insects of Lepidoptera such as stem-borers and armyworms and cutworms, a strong lethal effect in both a spraying or dusting and a soil treatment, and a long persistency.

The present compounds, in actual application thereof, may be used as they are or may be used in any preparation form of dusts, granules, fine granules, wettable powders and emulsifiable concentrates. In formulating those preparations, there are used solid carriers including talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite and calcium hydroxide; and liquid carriers including benzene, alcohols, acetone, xylene, methylnaphthalene, dioxane and cyclohexanone.

In actual application, the present compounds may be enhanced and ensured in effectiveness by using them in condition with surfactants such as spreaders for agriculture. It is also possible to use the present compounds in combination with agricultural chemicals such as fungicides, microbial insectides, prechroide type insecticides, other insecticides and other herbicides, or with fertilizers.

The compositions of the present invention will be illustrated with reference to the following preparation examples.

Preparation 1

25 parts of the compound (2), 5 parts of a surfactant of polyoxyethylene acetylallylester type and 70 parts of talc were thoroughly mixed together by pulverizing to obtain a wettable powder.

Preparation 2

30 parts of the compound (3), 20 parts of a surfactant of polyethylene glycolester type and 50 parts of cyclohexanone were thoroughly mixed together to obtain an emulsifiable concentrate.

Preparation 3

5 parts of the compound (5), 40 parts of bentonite, 50 parts of clay and 5 parts of sodium lignosulfonate were thoroughly mixed together by pulverizing, sufficiently kneaded with water, granulated and dried to obtain granules.

Preparation 4

3 parts of the compound (12) and 97 parts of clay were thoroughly mixed together by pulverizing to obtain dusts.

Preparation 5

5 parts of the compound (15), 4 parts of sodium lignosulfonate, 86 parts of clay and 5 parts of water were thoroughly kneaded in a ribbon mixer and dried to obtain fine granules.

Preparation 6

25 parts of the compound (50), 5 parts of a surfactant of polyoxyethylene acetylallylester type and 70 parts of talc were thoroughly mixed together by pulverizing to obtain a wettable powder.

The present invention will be illustrated in more details with reference to the following test examples, in which the names of compound are represented by the numbers of the compound exemplified above. Test Example 1: Pre-emergence application.

Seeds of barnyard grass (Echinochloa crus-galli) and large crabgrass (Digitaria sanguinalis) as representatives of grassy weeds and those of radish, redroot pigweed (Amaranthus retroflexus), common purslane (Portulaca oleracea) and common lambsquarter (Chenopodium album) as representatives of broad-leaved weeds were individually sowed in flower pots of about 10 cm. in diameter. After covering the seeds with soil, test compounds as shown in Table 1 were individually applied to the soil treatment. Thereafter the plants were grown in a green house and 20 days after application the herbicidal effects of the compounds were observed, the results of which are as shown in Table 1.

Herbicidal effects were evaluated by the numerals ranging from 0 (not damaged) to 5 (completely killed). All the test compounds were used in the form of wettable powder and diluted with water before application.

Table 1__________________________________________________________________________ Amount Large CommonComp. applied Barnyard crab- Redroot Common lambs-No. (g./a.) grass grass Radish pigweed purslane quarter__________________________________________________________________________ 40 5 5 0 5 5 5 1 20 5 5 0 5 4 4 10 5 5 0 4 4 4 40 5 5 1 5 5 5 2 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 0 5 5 5 3 20 5 5 0 5 5 5 10 5 5 0 4 5 5 40 5 5 0 4 5 5 4 20 5 5 0 4 4 4 10 4 5 0 4 4 4 40 5 5 0 5 5 5 5 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 0 5 5 5 7 20 5 5 0 5 5 5 10 5 5 0 4 5 5 40 5 5 0 4 4 4 8 20 4 4 0 4 4 4 10 4 4 0 3 4 3 40 5 5 0 5 5 5 9 20 5 5 0 5 5 5 10 5 5 0 4 5 4 40 5 5 0 4 4 410 20 4 4 0 4 4 4 10 4 4 0 3 3 3 40 5 5 0 5 5 511 20 5 5 0 5 4 4 10 4 4 0 4 4 4 40 5 5 0 5 5 512 20 5 5 0 5 5 5 10 5 5 0 4 5 5 40 5 5 0 5 5 513 20 5 5 0 5 5 5 10 5 5 0 4 4 4 40 5 5 0 5 5 514 20 5 5 0 5 5 5 10 5 5 0 4 5 4 40 5 5 0 5 5 515 20 5 5 0 5 5 5 10 5 5 0 4 5 4 40 5 5 0 4 4 516 20 4 5 0 4 4 4 10 4 5 0 4 4 4 40 5 5 0 4 4 517 20 4 5 0 4 4 4 10 4 4 0 3 3 4 40 5 5 0 5 5 518 20 5 5 0 4 4 5 10 4 5 0 4 4 4 40 5 5 0 4 4 419 20 4 4 0 4 4 4 10 4 4 0 4 4 3 40 5 5 0 5 4 522 20 5 5 0 4 4 4 10 4 4 0 3 4 4 40 5 5 0 4 4 424 20 5 5 0 4 4 4 10 4 4 0 3 4 3 40 5 5 0 4 4 426 20 5 5 0 4 4 4 10 4 4 0 4 4 3 40 5 5 0 5 4 527 20 5 5 0 4 4 4 10 4 5 0 3 4 4 40 5 5 0 4 4 536 20 4 4 0 4 4 4 10 4 4 0 3 3 4 40 5 5 0 5 5 549 20 5 5 0 4 4 4 10 5 5 0 3 3 4 40 5 5 2 5 5 550 20 5 5 1 5 5 5 10 5 5 0 5 5 5 40 5 5 0 5 5 552 20 5 5 0 4 4 4 10 5 5 0 4 3 3 40 5 5 0 5 5 453 20 5 5 0 4 3 3 10 4 5 0 3 3 3 40 5 5 0 5 4 556 20 5 5 0 3 3 4 10 5 4 0 3 3 3 40 5 5 0 5 5 458 20 5 5 0 4 4 4 10 4 5 0 3 3 3 40 5 5 0 5 5 562 20 5 5 0 4 4 4 10 4 4 0 3 3 4 40 5 5 0 5 5 563 20 5 5 0 5 5 4 10 5 4 0 4 4 4 40 5 5 0 4 4 464 20 5 5 0 3 3 4 10 4 4 0 3 3 3 40 5 5 0 5 5 565 20 5 5 0 4 4 4 10 5 5 0 4 4 4 40 5 5 1 5 5 566 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 0 5 5 567 20 5 5 0 4 4 4 10 4 4 0 4 4 3 40 5 5 0 5 5 568 20 4 4 0 4 4 4 10 4 4 0 4 3 4 40 5 5 0 5 5 569 20 5 5 0 5 5 5 10 4 5 0 4 4 4 40 5 5 0 5 5 570 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 2 5 5 571 20 5 5 1 5 5 4 10 5 5 0 4 4 4 40 5 5 0 5 5 572 20 5 5 0 4 4 4 10 4 5 0 3 3 4 40 5 5 0 5 5 573 20 5 5 0 4 4 4 10 5 5 0 4 4 4 40 5 5 2 5 5 574 20 5 5 1 5 5 5 10 5 5 0 5 5 5 40 5 5 2 5 5 575 20 5 5 1 5 5 5 10 5 5 0 5 5 5 40 5 5 2 5 5 576 20 5 5 1 5 5 5 10 5 5 0 5 5 5 40 5 5 0 5 5 577 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 0 5 5 578 20 5 5 0 4 4 4 10 5 5 0 4 4 3 40 5 5 1 5 5 579 20 5 5 0 5 5 5 10 5 5 0 4 5 5 40 5 5 0 5 5 580 20 5 5 0 4 4 4 10 4 5 0 3 3 3 40 5 5 1 5 5 581 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 1 5 5 582 20 5 5 0 4 4 4 10 5 5 0 4 3 4 40 5 5 2 5 5 583 20 5 5 1 5 5 5 10 5 5 0 5 5 5 40 5 5 2 5 5 584 20 5 5 1 5 5 5 10 5 5 0 4 5 4 40 5 5 0 5 5 585 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 0 5 5 586 20 5 5 0 5 5 5 10 5 5 0 4 5 5 40 5 5 0 5 5 587 20 5 5 0 4 4 3 10 5 5 0 3 3 3 40 5 5 0 4 4 488 20 5 5 0 3 3 3 10 5 5 0 3 3 3 40 5 5 0 5 5 589 20 5 5 0 4 4 4 10 4 4 0 3 3 3 40 5 5 0 5 5 590 20 5 5 0 4 4 3 10 5 5 0 3 3 3 40 5 5 0 4 4 491 20 5 5 0 3 4 3 10 4 5 0 3 3 3 40 5 5 0 5 5 592 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 0 5 5 593 20 5 5 0 5 4 5 10 5 5 0 4 4 4 40 5 5 0 5 5 594 20 5 5 0 4 4 4 10 5 5 0 3 3 4 40 5 5 0 3 3 495 20 5 5 0 3 3 3 10 4 4 0 2 2 2 40 5 5 0 5 5 596 20 5 5 0 4 4 4 10 4 5 0 3 3 3 40 5 5 0 5 5 597 20 5 5 0 4 4 4 10 4 4 0 3 4 3 40 5 5 0 5 5 598 20 5 5 0 5 5 5 10 5 5 0 4 4 5 40 5 5 0 5 5 599 20 5 5 0 5 5 5 10 4 5 0 4 5 5 40 5 5 1 5 5 5100 20 5 5 0 4 4 4 10 4 5 0 4 3 3 PCP.sup.1) 100 3 4 4 4 4 4(control) 50 2 2 1 2 2 2 Zytron.sup.2) 40 4 3 0 1 2 2(control) 20 3 1 0 0 1 0__________________________________________________________________________Note: .sup.1) Chemical structure .sup.2) Chemical structure ##STR13##__________________________________________________________________________ Test Example 2: Water application.

Wagner pots of 14 cm. in diameter, which had been packed with 1.5 kg. of paddy field soil, were brought into the state of paddy fields. To the pots were transplanted rice seedlings at the 3-leave stage. Further, seeds of barnyard grass (Echinochloa crus-galli) were sowed in the pots and required amounts of test compounds were applied to the soil under water lodged condition. 25 days after application, the degrees of herbicidal activity and phytotoxity were investigated on above-mentioned plants which had been transplanted and sowed, and on broad-leaved weeds, e.g., monochoria (Monochoria viaginalis Presl.), false pimpernel (Linderna pyxidaria) and toothcup (Rotala indica Koehue), which had been spontaneously germinated. The test compounds were used in the form of wettable powder. The results obtained are as shown in Table 2. The herbicidal effects and the phytotoxity were evaluated as follows by the numerals ranging from 0 to 5.

______________________________________ Effect on plants______________________________________0 no effect1 very slightly affected2 slightly affected3 moderately affected4 considerably affected5 completely killed______________________________________ Table 2______________________________________Amount Herbicidal effects______________________________________Compound applied Barnyard Broad-leaved PhytotoxicityNo. (g/a) grass weeds on rice______________________________________ 40 5 5 01 20 5 5 0 10 5 5 0 40 5 5 12 20 5 5 1 10 5 5 0 40 5 5 03 20 5 5 0 10 5 5 0 40 5 5 04 20 5 5 0 10 5 4 0 40 5 5 05 20 5 5 0 10 5 5 0 40 5 5 07 20 5 5 0 10 5 5 0 40 5 5 08 20 5 5 0 10 5 4 0 40 5 5 09 20 5 5 0 10 5 5 0 40 5 5 010 20 5 5 0 10 5 4 0 40 5 5 011 20 5 5 0 10 5 5 0 40 5 5 012 20 5 5 0 10 5 5 0 40 5 5 013 20 5 5 0 10 5 5 0 40 5 5 014 20 5 5 0 10 5 5 0 40 5 5 015 20 5 5 0 10 5 5 0 40 5 5 016 20 5 5 0 10 5 5 0 40 5 5 017 20 5 5 0 10 5 4 0 40 5 5 018 20 5 5 0 10 5 5 0 40 5 5 019 20 5 5 0 10 5 4 0 40 5 5 022 20 5 5 0 10 5 5 0 40 5 5 024 20 5 5 0 10 5 4 0 40 5 5 026 20 5 5 0 10 5 5 0 40 5 5 027 20 5 5 0 10 5 5 0 40 5 5 036 20 5 5 0 10 5 4 0 40 5 5 149 20 5 5 0 10 5 5 0 40 5 5 150 20 5 5 0 10 5 5 0 40 5 5 052 20 5 5 0 10 5 5 0 40 5 5 053 20 5 5 0 10 5 5 0 40 5 5 056 20 5 5 0 10 5 5 0 40 5 5 058 20 5 5 0 10 5 5 0 40 5 5 062 20 5 5 0 10 5 5 0 40 5 5 063 20 5 5 0 10 4 5 0 40 5 5 064 20 5 5 0 10 5 5 0 40 5 5 065 20 5 5 0 10 4 5 0 40 5 5 066 20 5 5 0 10 5 5 0 40 5 5 067 20 5 5 0 10 5 5 0 40 5 5 068 20 5 5 0 10 5 5 0 40 5 5 169 20 5 5 0 10 5 5 0 40 5 5 270 20 5 5 0 10 5 5 0 40 5 5 071 20 5 5 0 10 5 5 0 40 5 5 072 20 5 5 0 10 5 5 0 40 5 5 073 20 5 5 0 10 5 5 0 40 5 5 074 20 5 5 0 10 5 5 0 40 5 5 175 20 5 5 0 10 5 5 0 40 5 5 076 20 5 5 0 10 5 5 0 40 5 5 177 20 5 5 0 10 5 5 0 40 5 5 078 20 5 5 0 10 5 5 0 40 5 5 179 20 5 5 0 10 5 5 0 40 5 5 280 20 5 5 0 10 4 5 0 40 5 5 181 20 5 5 0 10 5 5 0 40 5 5 282 20 5 5 0 10 5 5 0 40 5 5 083 20 5 5 0 10 5 5 0 40 5 5 284 20 5 5 0 10 5 5 0 40 5 5 085 20 5 5 0 10 5 5 0 40 5 5 086 20 5 5 0 10 5 5 0 40 5 5 087 20 5 5 0 10 5 5 0 40 5 5 088 20 5 5 0 10 5 5 0 40 5 5 089 20 5 5 0 10 5 5 0 40 5 5 190 20 5 5 0 10 5 5 0 40 5 5 091 20 5 5 0 10 4 5 0 40 5 5 292 20 5 5 0 10 5 5 0 40 5 5 093 20 5 5 0 10 5 5 0 40 5 5 094 20 5 5 0 10 5 5 0 40 5 5 095 20 5 5 0 10 5 5 0 40 5 5 096 20 5 5 0 10 5 5 0 40 5 5 097 20 5 5 0 10 5 5 0 40 5 5 098 20 5 5 0 10 5 5 0 40 5 5 099 20 5 5 0 10 5 5 0 40 5 5 0100 20 5 5 0 10 5 5 0PCP 100 5 5 3(control) 50 4 5 2Zytron 40 3 3 0(control) 20 1 2 0NIP.sup. 1) 40 5 5 4(control) 20 5 5 2______________________________________Note:

Test Example 3

Lethal effect on carmine mite (Tetranychus telavius)

A large number of carmine mite adult were made parasitic on leaves of potted kidney beans at a 2-leaves stage which had elapsed 10 days after sowing. The leaves of kidney bean on which carmine mites had been made parasitic were dipped for 1 minute in each aqueous solution of the present compounds of wettable powder type. Water was given to the leaves not to kill them, and after 48 hours the death and alive were observed microscopically to calculate the mortality. Values of LC.sub.50 were obtained from the mortality. The results are as shown in Table 3.

Table 3______________________________________Compound No. LC.sub.50 (p.p.m.)______________________________________2 4.63 18.54 11.45 7.97 18.511 50.014 23.130 22.8Smite.sup.1) 102.0(control)______________________________________.sup.1) Chemical structure: ##STR15##______________________________________

Test Example 4

Lethal effect on carmine mite (Tetranychus telarius)

About 50 carmine mite adults were made parasitic on leaves of potted kidney beans at a 2-leaves stage which had elapsed 10 days after swing. After a week, the present compounds of a 25% wettable powder type were each applied in the form of a 200 fold dilute solution. After allowing to stand for another week the degree of damage was observed, the results of which are as shown in Table 4.

Table 4______________________________________Compound No. Degree of damage______________________________________49 -53 -.about.+60 -61 -No treatment +++______________________________________ Note: -: damage is hardly increased. +: damage is slightly increased. ++: damage is fairly increased. +++: damage is heavily increased.

Test Example 5

Lethal effect on tobacco cut work (Spondoptera litura)

The present compounds of an emulsifiable concentrate type were applied to leaves of chinese cabbage in the form of an 1000 fold dilute solution. After air-drying, third to fourth instar larvae of tobacco cut worm were released and after 48 hours the death and alive were observed. The results are as shown in Table 5.

Table 5______________________________________Compound No. Mortality (%)______________________________________ 2 100 3 83.3 5 70.013 73.349 75.050 81.258 72.0EPN.sup.1) 70.0(control)______________________________________.sup.1) Chemical structure:

Test Example 6

Lethal effect on rice stem borer (Chilo suppressalis)

Eggs just before hatch of the rice stem borer were applied in a ratio of 100/pot near the root of rice plants grown up into the tillering stage in an 1/1000000 Wagner's pot. After eggs were hatched and the larvae entered into stems of rice plants, an 1000 fold dilute solution of each 50 % emulsifiable concentrates of the present compounds was applied by means of a turn table. The death and alive were observed to calculate the mortality 4 days after application. The results are as shown in Table 6.

Table 6______________________________________Compound No. Mortality (%)______________________________________ 4 97.6 5 88.9 6 75.0 9 10018 76.424 83.031 69.535 95.0Malathion.sup.1) 41.3(control)______________________________________.sup.1) Chemical structure: ##STR17##______________________________________

Test Example 7

Effect on nematode

0.5 ml. of a nematode-containing aqueous solution separated from food according to Baermann's method was placed in a test tube with ground stopper containing 0.5 ml. of an aqueous dilute solution of each emulsifiable concentrates of the present compounds. The concentration of the active ingredient in the mixture was adjusted to 500 p.p.m. After 24 hours, the death and alive were observed microscopically to calculate the mortality. The results are as shown in Table 7.

Table 7______________________________________Compound No. Mortality (%)______________________________________2 1003 1004 1005 1007 1009 10010 10011 10012 10014 10028 10033 10049 10050 10052 85.753 83.657 91.0Dichloropropene.sup.1) 79.3(control)______________________________________ .sup.1) Chemical structure: ClCH= C-- CH.sub.2 Cl

Test Example 8

Lethal effect on tobacco cut worm (Spodoptera litura) and diamond-back moth (Plutella maculipennis)

A 3% dust of each compound of the present invention was applied, in a proportion of 5 kg./10 a., to the field of cabbage where a large number of tobacco cut worm and diamond-back moth were generated, After 7 days, 20 cabbages were pulled out and the number of insects thereon were checked. The results are as shown in Table 8.

Table 8______________________________________ Number of insectsCompound No. Tobacco cut worm Diamond-back moth______________________________________2 0 83 1 12No treatment 47 158Bipterex.sup.1) 19 49(control)______________________________________.sup.1) Chemical structure: ##STR18##______________________________________ The treated cabbages suffered only the same feeding damage as before dusting, however with the untreated cabbages only leaf veins were left.

The synthetic method according to the present invention will be illustrated with reference to the following examples which are only illustrative but not limitative thereto.

EXAMPLE 1

(Compound No. 2)

To a solution of 26.2 g. of potassium O-ethyl-S-n-propylphosphorodithioate in 100 ml. of ethylalcohol, were added 17.5 g of 2-methylpiperidino-.alpha.-chloroacetamide, and then the mixture was refluxed under stirring for 2 hours. After removal of ethylalcohol under reduced pressure, the remainder was dissolved in benzene. The resulting solution was washed with a 5% sodium carbonate solution and then water. Thereafter benzene was distilled off to obtain 29.7 g. of pale yellow and oily O-ethyl-S-n-propyl-S(2-methylpiperidinocarbomoylmethyl)phosphorodithiolate (n.sub.D.sup.23.0 1.5320).

______________________________________Elementary analysis:Calculated (%) (as C.sub.13 H.sub.26 NO.sub.3 PS.sub.2) Found (%)______________________________________P 9.12 8.97C 46.00 45.91H 7.72 7.81N 4.13 4.14______________________________________

EXAMPLE 2

(Compound No. 16)

To a solution of 26.0 g. of sodium O-n-propyl-S-n-propylphosphorodithioate in 100 ml. of acetone, were added 17.5 g. of 2-methylpiperidino-.alpha.-.alpha.-chloroacetoamide, and then the mixture was refluxed under stirring for 2 hours, and thereafter treated in the same manner as described in Example 1. 29.6 g. of pale yellow and oily O,S-di-n-propyl-S-(2-methylpiperidinocarbamoylmethyl)phosphorodithiolate (n.sub.D.sup.27.0 1.5224) were obtained.

______________________________________Elementary analysis:Calculated (%) (as C.sub.14 H.sub.28 NO.sub.3 PS.sub.2) Found (%)______________________________________P 8.76 8.81C 47.57 47.36H 7.98 7.87N 3.96 3.78______________________________________

EXAMPLE 3

(Compound No. 49)

To a solution of 35.0 g. of potassium O-ethyl-S-(4-chlorobenzyl)-phosphorodithioate in 100 ml. of ethanol, were added 17.5 g. of 2-methylpiperidino-.alpha.-chloroacetamide. The mixture was refluxed under stirring for 2 hours. After removal of ethanol under reduced pressure, the remainder was dissolved in benzene. The resulting solution was washed with a 5% sodium carbonate solution and then water. Thereafter benzene was distilled off to obtain 34.2 g. of yellow and oily O-ethyl-S-(4-chlorobenzyl)-S-(2-methylpiperidinocarbamoylmethyl)phosphorodithiolate (n.sub.D.sup.20.0 1.5680).

______________________________________Elementary analysis:Calculated (%) (as C.sub.17 H.sub.25 ClNO.sub.3 PS.sub.2) Found (%)______________________________________C 48.39 48.28H 5.97 5.98N 3.32 3.39P 7.34 7.25______________________________________ ______________________________________ Elementary analysisEx. Compound Yield Refractive Calculated FoundNo. No. (%) index (%) (%)______________________________________ C 44.29 44.51 H 7.43 7.29 4 1 86.2 n.sub.D.sup.26.5 1.5330 N 4.30 4.27 P 9.52 9.38 C 46.00 45.71 H 7.72 7.72 5 3 89.1 n.sub.D.sup.24.0 1.5309 N 4.13 4.25 P 9.12 9.07 C 47.57 47.34 H 7.98 8.15 6 4 84.2 n.sub.D.sup.24.0 1.5281 N 3.96 3.99 P 8.76 8.98 C 47.57 47.80 H 7.98 7.96 7 5 91.9 n.sub.D.sup.24.0 1.5287 N 3.96 3.97 P 8.76 8.81 C 47.57 47.35 H 7.98 8.07 8 6 87.7 n.sub.D.sup.25.0 1.5284 N 3.96 3.86 P 8.76 8.97 C 49.02 48.68 H 8.23 8.30 9 7 88.0 n.sub.D.sup.24.0 1.5242 N 3.81 3.82 P 8.43 8.73 C 52.78 52.51 H 8.86 8.9610 8 88.0 n.sub.D.sup.26.5 1.5160 N 3.42 3.41 P 7.56 7.85 C 41.99 42.23 H 6.23 6.5111 9 89.7 n.sub.D.sup.25.0 1.5412 N 3.71 4.00 P 8.33 8.71 C 50.64 50.32 H 7.97 7.7612 10 79.5 n.sub.D.sup.25.0 1.5395 N 3.69 3.77 P 8.16 8.41 C 52.69 52.87 H 6.76 6.8713 11 85.7 n.sub.D.sup.28.0 1.5652 N 3.61 3.53 P 7.99 8.13 C 45.99 45.71 H 7.72 7.8314 12 85.9 n.sub.D.sup.28.0 1.5270 N 4.13 4.01 P 9.12 8.87 C 45.99 46.23 H 7.72 7.5015 13 87.8 n.sub.D.sup.25.0 1.5287 N 4.13 4.11 P 9.12 9.41 C 47.57 47.63 H 7.98 7.8416 14 92.9 n.sub.D.sup.25.0 1.5266 N 3.96 3.83 P 8.76 8.78 C 47.57 47.36 H 7.98 7.8917 15 80.9 n.sub.D.sup.25.0 1.5270 N 3.96 3.88 P 8.76 9.03 C 49.02 49.37 H 8.23 8.2118 17 85.0 n.sub.D.sup.27.0 1.5211 N 3.81 3.76 P 8.43 8.10 C 44.02 44.31 H 8.00 7.8819 18 85.7 n.sub.D.sup.26.5 1.5301 N 4.28 4.21 P 9.46 9.62 C 55.92 56.13 H 7.51 7.2720 19 78.1 n.sub.D.sup.27.0 1.5541 N 3.26 3.24 P 7.21 7.53 C 47.57 47.39 H 7.98 7.8121 20 70.5 n.sub.D.sup.24.5 1.5220 N 3.96 3.92 P 8.76 8.95 C 47.57 47.86 H 7.98 8.1522 21 73.5 n.sub.D.sup.27.0 1.5245 N 3.96 3.82 P 8.76 8.51 C 46.00 45.71 H 7.72 7.9623 22 87.6 n.sub.D.sup.28.0 1.5255 N 4.13 4.07 P 9.12 9.37 C 47.57 47.28 H 7.98 8.1324 23 74.0 n.sub.D.sup.27.0 1.5249 N 3.96 3.87 P 8.76 9.01 C 47.57 47.29 H 7.98 8.0325 24 93.5 n.sub.D.sup.28.0 1.5216 N 3.96 4.11 P 8.76 8.68 C 47.57 47.87 H 7.98 7.7626 25 89.0 n.sub.D.sup.27.0 1.5248 N 3.96 3.88 P 8.76 8.56 C 46.00 46.25 H 7.72 7.8427 26 87.5 n.sub.D.sup.28.0 1.5240 N 4.13 4.21 P 9.12 9.03 C 47.57 47.73 H 7.98 8.1128 27 80.0 n.sub.D.sup.28.0 1.5205 N 3.96 4.11 P 8.76 8.52 C 47.57 47.54 H 7.98 8.0729 44 82.9 n.sub.D.sup.25.0 1.5272 N 3.96 3.89 P 8.76 8.86 C 49.02 49.31 H 8.23 8.4230 45 86.5 n.sub.D.sup. 27.0 1.5224 N 3.81 3.76 P 8.43 8.27 C 49.02 50.27 H 8.23 8.0031 46 83.6 n.sub.D.sup.25.0 1.5230 N 3.81 3.68 P 8.43 8.71 C 49.02 48.87 H 8.23 8.1532 47 82.1 n.sub.D.sup.27.0 1.5255 N 3.81 3.78 P 8.43 8.29 C 49.02 49.16 H 8.23 8.3533 48 75.0 n.sub.D.sup.25.0 1.5223 N 3.81 3.91 P 8.43 8.36 C 56.85 56.92 H 7.44 7.7134 50 81.3 n.sub.D.sup.22.0 1.5592 N 3.16 3.22 P 6.98 6.63 C 49.59 49.36 H 6.24 6.2935 51 82.4 n.sub.D.sup.21.0 1.5636 N 3.21 3.35 P 7.10 7.03 C 53.84 53.62 H 7.04 7.0036 52 80.5 n.sub.D.sup.23.0 1.5700 N 3.49 3.45 P 7.71 7.57 C 54.91 54.88 H 7.29 6.9137 53 80.9 n.sub.D.sup.23.0 1.5652 N 3.37 3.56 P 7.45 7.20 C 55.91 55.92 H 7.52 7.5138 56 81.2 n.sub.D.sup.18.0 1.5600 N 3.26 3.21 P 7.21 7.21 C 55.92 56.07 H 7.51 7.3739 58 83.1 n.sub.D.sup.21.0 1.5608 N 3.26 3.29 P 7.21 7.41 C 50.86 50.58 H 8.47 8.2540 62 82.7 n.sub.D.sup.18.0 1.5261 N 3.67 3.62 P 8.12 7.91 C 53.84 52.29 H 7.04 7.0641 63 83.4 n.sub.D.sup.20.0 1.5649 N 3.50 3.61 P 7.71 7.69 C 53.84 53.87 H 7.04 7.1042 64 84.1 n.sub.D.sup.20.0 1.5685 N 3.49 3.54 P 7.71 7.65 C 54.91 54.65 H 7.29 7.3143 65 81.9 n.sub.D.sup.22.5 1.5629 N 3.37 3.35 P 7.45 7.18 C 44.28 44.34 H 7.45 7.4644 66 82.2 n.sub.D.sup.21.0 1.5388 N 4.30 4.37 P 9.52 9.47 C 49.01 49.62 H 8.24 8.2645 67 82.4 n.sub.D.sup.21.5 1.5276 N 3.81 4.03 P 8.43 8.21 C 50.36 50.22 H 8.48 8.4946 68 79.8 n.sub.D.sup.21.0 1.5243 N 3.67 3.66 P 8.12 7.92 C 50.36 50.43 H 8.47 8.4847 69 81.2 n.sub.D.sup.28.0 1.5247 N 3.67 3.68 P 8.12 8.17 C 47.83 47.82 H 7.47 7.5448 70 80.5 n.sub.D.sup.23.5 1.5391 N 3.99 4.09 P 8.81 8.36 C 44.28 44.22 H 7.45 7.5649 71 82.1 n.sub.D.sup.28.0 1.5360 N 4.30 4.39 P 9.52 9.67 C 49.01 49.10 H 8.24 8.2850 72 83.4 n.sub.D.sup.22.5 1.5258 N 3.81 3.84 P 8.43 8.20 C 49.01 49.01 H 8.24 8.1851 73 82.5 n.sub.D.sup.20.5 1.5260 N 3.81 3.95 P 8.43 8.71 C 44.28 44.43 H 7.45 7.6752 74 82.9 n.sub.D.sup.23.0 1.5409 N 4.30 4.51 P 9.52 9.47 C 45.99 46.12 H 7.74 7.8953 75 82.7 n.sub.D.sup.22.0 1.5338 N 4.13 4.19 P 9.12 8.97 C 47.56 47.61 H 8.00 7.9554 76 82.5 n.sub.D.sup.22.5 1.5298 N 3.96 3.95 P 8.76 8.68 C 49.01 48.79 H 8.24 8.2655 77 83.1 n.sub.D.sup.20.0 1.5261 N 3.81 3.76 P 8.43 8.31 C 50.36 50.39 H 8.47 8.3856 78 82.6 n.sub.D.sup.20.0 1.5240 N 3.67 3.67 P 8.12 7.87 C 50.36 50.07 H 8.47 8.3757 79 80.9 n.sub.D.sup.22.5 1.5281 N 3.67 3.74 P 8.12 8.16 C 51.61 51.40 H 8.68 8.4558 80 80.5 n.sub. D.sup.18.0 1.5235 N 3.54 3.60 P 7.83 7.67 C 49.28 49.24 H 7.74 7.7659 81 85.1 n.sub.D.sup.22.0 1.5390 N 3.83 3.84 P 8.47 8.28 C 43.57 43.43 H 6.54 6.8860 82 81.1 n.sub.D.sup.22.0 1.5393 N 3.63 3.91 P 8.02 8.22 C 45.99 46.04 H 7.74 7.7261 83 80.8 n.sub.D.sup.21.0 1.5329 N 4.13 4.11 P 9.12 9.01 C 47.56 47.48 H 8.00 7.9862 84 81.9 n.sub.D.sup.22.5 1.5272 N 3.96 3.98 P 8.76 8.57 C 49.02 49.24 H 8.23 8.3963 85 81.5 n.sub.D.sup.22.0 1.5230 N 3.81 3.81 P 8.43 8.51 C 50.37 50.43 H 8.45 8.4264 86 82.2 n.sub.D.sup.22.0 1.5204 N 3.67 3.64 P 8.12 7.84 C 50.36 50.58 H 8.47 8.5865 87 82.7 n.sub.D.sup.23.0 1.5245 N 3.67 3.78 P 8.12 8.11 C 50.36 50.37 H 8.47 8.4966 88 83.1 n.sub.D.sup.22.5 1.5232 N 3.67 3.68 P 8.12 8.06 C 51.63 50.67 H 8.68 8.6667 89 82.7 n.sub.D.sup.23.0 1.5220 N 3.54 3.51 P 7.83 7.89 C 51.63 51.65 H 8.68 8.6668 90 85.4 n.sub.D.sup.19.5 1.5212 N 3.54 3.54 P 7.83 7.71 C 49.28 48.89 H 7.74 7.5769 91 84.6 n.sub.D.sup.22.0 1.5362 N 3.83 3.84 P 8.47 8.04 C 49.01 49.09 H 8.24 8.2670 92 84.2 n.sub.D.sup.22.5 1.5248 N 3.81 3.95 P 8.43 7.87 C 50.36 50.37 H 8.47 8.3771 93 83.5 n.sub.D.sup.22.5 1.5241 N 3.67 3.60 P 8.12 8.08 C 50.36 50.46 H 8.47 8.4972 94 81.6 n.sub.D.sup.22.5 1.5225 N 3.67 3.63 P 8.12 7.97 C 51.61 51.90 H 8.68 8.6173 95 82.1 n.sub. D.sup.21.5 1.5199 N 3.54 3.85 P 7.83 7.55 C 51.61 61.12 H 8.68 9.1274 96 80.1 n.sub.D.sup.21.5 1.5220 N 3.54 3.51 P 7.83 7.66 C 51.61 51.46 H 8.68 8.6775 97 81.8 n.sub.D.sup.21.5 1.5221 N 3.54 3.91 P 7.83 7.57 C 52.77 52.81 H 8.88 8.7276 98 81.5 n.sub.D.sup.21.0 1.5205 N 3.42 3.18 P 7.56 7.33 C 52.77 52.56 H 8.88 8.6177 99 82.3 n.sub.D.sup.22.5 1.5171 N 3.42 3.13 P 7.56 7.41 C 44.29 44.12 H 7.43 7.4678 100 84.1 n.sub.D.sup.25.5 1.5270 N 4.30 4.29 P 9.52 9.58______________________________________

Claims

1. A compound of the formula ##STR19## wherein R.sub.1 is lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl having up to 6 carbon atoms, phenyl C.sub.1 -C.sub.2 alkyl, and phenyl C.sub.1 -C.sub.2 alkyl substituted with halogen or lower alkyl or halogen substituted alkenyl having up to 3 carbon atoms; R.sub.2 is lower alkyl; Y is hydrogen or methyl, X is lower alkyl and n is an integer of 1 to 5.

2. A compound of the formula, ##STR20## wherein R.sub.1 is C.sub.1 - C.sub.8 straight or branched chain alkyl, allyl, chloroallyl, methallyl, propargyl, cyclohexyl, benzyl, .alpha.-methylbenzyl, phenethyl, .beta.-methylphenethyl, chlorobenzyl, dichlorobenzyl, bromobenzyl or C.sub.1 - C.sub.4 alkyl substituted benzyl; R.sub.2 is C.sub.1 - C.sub.4 alkyl; Y is hydrogen or methyl; X is methyl or ethyl; n is an integer of 1 to 3.

3. A compound of the formula, ##STR21## wherein R.sub.1 is lower alkyl, cycloalkyl, lower alkenyl, halogen-substituted alkenyl, lower alkynyl or phenyl lower alkyl group; R.sub.2 is lower alkyl; Y is hydrogen or methyl; X is lower alkyl; n is an integer of 1 to 3.

4. A compound of the formula, ##STR22##

5. A compound of the formula, ##STR23##

6. A compound of the formula, ##STR24##

7. A compound of the formula, ##STR25##

8. A compound of the formula, ##STR26##

9. A compound of the formula, ##STR27##

10. A pesticidal composition comprising an inert carrier and a pesticidal amount of at least one phosphorothiolate compound of the formula ##STR28## wherein R.sub.1 is lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl having up to 6 carbon atoms, phenyl C.sub.1 -C.sub.2 alkyl, and phenyl C.sub.1 -C.sub. 2 alkyl substituted with halogen or lower alkyl or halogen substituted alkenyl having up to 3 carbon atoms; R.sub.2 is lower alkyl; Y is hydrogen or methyl, X is lower alkyl and n is an integer of 1 to 5.

11. A pesticidal composition of claim 10, wherein the composition is in the form of granules, dusts, wettable powders, emulsifiable concentrates or fine granules.

12. A pesticidal composition of claim 11, wherein the composition further contains fertilizers, fungicides, insecticides, nematocides or herbicides or a combination thereof.

13. A method for killing bad weeds, injurious insects, nematodes and acarides, which comprises applying an effective amount of a compound embraced by formula (I) in claim 17.