Amido phosphorothiolate pesticide

Abstract

Pesticidal compositions containing, as active ingredient, a compound of the formula ##STR1## wherein R.sub.1 is lower alkyl, lower alkenyl, lower alkynyl or a radical of the formula ##STR2## IN WHICH X is lower alkyl, halogen or hydrogen and n is zero or an integer of 1 to 5,R.sub.2 is lower alkyl, lower alkenyl or lower alkynyl,R.sub.3 is a radical of the formula ##STR3## or a radical of the formula ##STR4## and Y is oxygen or sulfur.

Description

The present invention relates to new compounds, herbicidal, insecticidal, acaricidal and nematocidal compositions 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 ##STR5## wherein R.sub.1 is lower alkyl, lower alkenyl, lower alkynyl or a group ##STR6## (IN WHICH X is lower alkyl, halogen or hydrogen, n is an integer of 0 to 5); R.sub.2 is lower alkyl, lower alkenyl or lower alkynyl; R.sub.3 is a radical of the formula, ##STR7## or a radical of the formula, ##STR8## and Y is oxygen or sulfur,

(2) THE PREPARATION OF THE COMPOUND OF THE FORMULA (I) characterized in condensing a salt of thiophosphate of the formula; ##STR9## wherein R.sub.1, R.sub.2 and Y are the same as defined above, and M is an alkali metal atom, with a halogenated acetoamide compound of the formula: ##STR10## wherein R.sub.3 is 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: ##STR11## wherein R'.sub.1 is straight or branched chain C.sub.1 -C.sub.6 alkyl, allyl, phenyl, C.sub.1 -C.sub.2 alkyl-substituted phenyl or chloro-substituted phenyl, R'.sub.2 is C.sub.1 -C.sub.4 alkyl; Y is oxygen or sulfur; and R'.sub.3 is a radical of the formula, ##STR12##

And a preferred compound as a herbicide is as follows: ##STR13## wherein R".sub.1 is a lower alkyl, lower alkenyl or lower alkynyl; R".sub.2 is an alkyl group; R".sub.3 is a radical of the formula, ##STR14##

Especially a compound of the formula, ##STR15## 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; R.sub.3 is a radical of the formula, ##STR16## has the most excellent herbicidal activity of the compounds represented by the formula (I - b) without phytotoxity and toxicity to warm-blood animals.

The new active ingredients 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 grass (Echinochloa Crus-galli), 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 fields such as false pimpernel (Lindernia pyxidaria), monochoria (Monochoria vaginalis Presl.) and toothcup (Rotala indica Koehue); sedge weeds such as nutsedge sp. (Cyperus difformis) and slender spikerush (Eleocharis acicularis).

One of the most important properties of herbicides is that they be able to 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, stem-borers and armyworms and cutworms; insects injurious to sanitation such as cockroaches, and houseflies; insects injurious to stored cereals; mites; and nematodes. Consequently they can be effectively used as a herbicide, insecticide, acaricide and nematocide.

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

Belgian Pat. No. 767,132 indicates that phosphorodithiolate compounds having an unsubstituted piperidine moiety have insecticidal, acaricidal and nematocidal activity, but the present inventors have found that azepine compounds and tetrahydro quinoline compounds have unexpected excellent herbicidal activity. This is unobvious from the prior art.

The present invention (1) relates to a compound having herbicidal, insecticidal, acaricidal and nematocidal activity based on the above-mentioned information.

The present invention (3) relates to a herbicidal, insecticidal, acaricidal and nematocidal composition 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; ##STR17## wherein R.sub.1, R.sub.2, R.sub.3 and Y are the same as defined above, is obtained by condensing a salt of thiophosphate of the formula, ##STR18## wherein R.sub.1, R.sub.2, Y and M are the same as defined above, with a halogenated acetoamide compound of the formula, ##STR19## wherein Hal and R.sub.3 are the same as defined above.

The present process 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 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 1 to several hours. On completion of the reaction, the objective 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, which are used in the practice of the present invention will be shown as follows:

potassium O-ethyl-S-n-propylphosphorodithioate potassium O-ethyl-S-iso-propylphosphorodithioate phosphate 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-allylphosphorodithioate potassium O-ethyl-S-propargylphosphorodithioate potassium O-ethyl-S-methallylphosphorodithioate 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-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

Next, some representative examples of the organo phosphoric acid ester of the present invention will concretely be shown as follows. ##STR20##

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. 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 plants, radish, soy bean, pea, tomato, wheat and corn. The present compounds are also useful as herbicide for use in rice paddy fields, cereal fields, vegetable fields, 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 both when applied by spraying or dusting and in 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 combination 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 insecticides, prethroide 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 (1), 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

30 parts of the compound (2), 20 parts of a surfactant of polyethylene glycolester type and 50 parts of cyclohexanone were thoroughly mixed together to obtain an emulsifiable concentrate.

Preparation 4

5 parts of the compound (17), 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 5

5 parts of the compound (32), 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.

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 compounds 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. 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__________________________________________________________________________Com- Amount Barn- Large Common Commonpound applied yard crab- Redroot purs- lambs-No. (g/a.) grass grass Radish pigweed lane quarter__________________________________________________________________________ 40 5 5 0 5 5 51 20 5 5 0 4 4 4 10 5 5 0 3 3 4 40 5 5 0 5 5 52 20 5 5 0 4 4 4 10 5 5 0 4 4 4 40 5 5 0 5 4 43 20 5 5 0 4 3 4 10 4 5 0 3 3 3 40 5 5 0 4 4 34 20 4 5 0 4 3 3 10 4 4 0 3 3 3 40 5 5 1 5 5 55 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 0 5 5 56 20 5 5 0 4 4 4 10 5 5 0 4 3 4 40 5 5 0 5 5 57 20 5 5 0 4 4 4 10 5 5 0 4 4 4 40 5 5 0 5 5 58 20 5 5 0 4 4 4 10 5 5 0 4 3 4 40 5 5 0 5 5 59 20 5 5 0 4 4 4 10 5 5 0 4 4 3 40 5 5 0 5 4 410 20 5 5 0 4 4 4 10 4 5 0 3 3 3 40 5 5 0 4 4 411 20 4 4 0 4 3 3 10 4 4 0 3 3 3 40 5 5 0 5 4 412 20 5 5 0 4 4 4 10 4 4 0 4 3 3 40 5 5 0 5 5 513 20 5 5 0 5 5 5 10 5 5 0 5 4 5 40 5 5 1 5 5 514 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 1 5 5 515 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 0 5 5 516 20 5 5 0 5 5 5 10 5 5 0 5 5 4 40 5 5 0 5 5 517 20 5 5 0 5 5 5 10 5 5 0 5 4 4 40 5 5 0 5 5 518 20 5 5 0 5 5 5 10 5 5 0 5 4 5 40 5 5 0 5 5 519 20 5 5 0 4 4 5 10 4 5 0 4 4 4 40 5 5 0 4 4 420 20 4 4 0 4 4 4 10 3 4 0 3 4 3 40 5 5 0 4 4 421 20 4 5 0 4 4 4 10 4 4 0 3 3 3 40 5 5 0 4 4 422 20 4 5 0 4 4 4 10 4 4 0 3 3 3 40 5 5 1 5 5 523 20 5 5 0 5 5 5 10 5 5 0 5 5 5 40 5 5 0 4 4 424 20 5 5 0 4 4 4 10 5 5 0 3 3 3 40 5 5 0 5 5 525 20 5 5 0 4 4 4 10 5 5 0 4 4 4 40 5 5 0 5 5 526 20 5 5 0 5 5 5 10 5 5 0 4 4 4 40 5 5 0 4 4 327 20 5 5 0 4 3 3 10 4 5 0 3 3 3 40 5 5 1 4 4 428 20 5 5 0 4 4 3 10 4 5 0 3 3 3 40 5 5 0 5 5 529 20 5 5 0 4 4 4 10 5 5 0 3 3 4 40 5 5 0 5 5 530 20 5 5 0 5 4 4 10 5 5 0 4 4 4 40 5 5 0 4 4 431 20 5 5 0 4 4 4 10 5 5 0 4 3 3 40 5 5 0 5 5 532 20 5 5 0 4 4 4 10 5 5 0 4 4 3 40 5 5 0 5 5 533 20 5 5 0 4 4 4 10 5 5 0 3 3 3PCP.sup.1 100 3 4 4 4 4 4(control) 50 2 2 1 2 2 2Zytron.sup.2 40 4 3 0 1 2 2(control) 20 3 1 0 0 1 0__________________________________________________________________________ Note: ##STR21## ##STR22##?

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 Vaginalis Presl.). false pimpernel (Lindernia 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 effect.1 Very slightly affected.2 Slightly affected.3 Moderately affected.4 Considerably affected.5 Completely killed.______________________________________ Table 2______________________________________Amount Herbicidal effects Phytoto-Compound applied Barnyard Broad-leaved xicityNo. (g/a.) grass weeds on rice______________________________________ 20 5 5 01 10 5 5 0 5 5 4 0 20 5 5 02 10 5 4 0 5 5 4 0 20 5 5 03 10 5 4 0 5 4 4 0 20 5 5 04 10 4 4 0 5 4 3 0 20 5 5 15 10 5 5 0 5 5 5 0 20 5 5 06 10 5 5 0 5 5 4 0 20 5 5 07 10 5 5 0 5 5 4 0 20 5 5 08 10 5 5 0 5 5 4 0 20 5 5 09 10 5 5 0 5 5 4 0 20 5 5 010 10 5 4 0 5 4 4 0 20 4 4 011 10 4 4 0 5 4 3 0 20 5 5 012 10 4 4 0 5 4 4 0 20 5 5 013 10 5 5 0 5 5 5 0 20 5 5 114 10 5 5 0 5 5 5 0 20 5 5 115 10 5 5 0 5 5 5 0 20 5 5 016 10 5 5 0 5 5 5 0 20 5 5 017 10 5 5 0 5 5 5 0 20 5 5 018 10 5 5 0 5 5 5 0 20 5 5 019 10 5 4 0 5 4 4 0 20 5 4 020 10 4 4 0 5 4 3 0 20 5 5 021 10 4 4 0 5 4 3 0 20 5 5 022 10 4 4 0 5 4 3 0 20 5 5 023 10 5 5 0 5 5 5 0 20 5 5 024 10 5 5 0 5 5 5 0 20 5 5 025 10 5 5 0 5 5 5 0 20 5 5 026 10 5 5 0 5 5 5 0 20 5 5 027 10 5 5 0 5 5 4 0 20 5 5 028 10 5 5 0 5 5 4 0 20 5 5 029 10 5 5 0 5 5 4 0 20 5 5 030 10 5 5 0 5 5 5 0 20 5 5 031 10 5 5 0 5 5 5 0 20 5 5 032 10 5 5 0 5 5 5 0 20 5 5 033 10 5 5 0 5 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: ##STR23##

Test Example 3

Lethal effect on carmine mite (Tetranychus telarius)

A large number of carmine mite adults were made parasitic on leaves of potted kidney beans at a 2-leave 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 so as not to kill them, and after 48 hours the number of dead and live mites 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 (ppm)______________________________________2 9.18 13.59 52.615 16.117 50.818 36.7Smite .sup.1 102.0(control)______________________________________ Note: .sup.1 Chemical structure: ##STR24##

Test Example 4

Lethal effect on tobacco cut worm (Spodoptera litura)

The present compounds of an emulsifiable concentrate type were applied to leaves of chinese cabbage in the form of a 1,000 fold dilute solution. After air-drying, third to fourth instar larvae of tobacco cut worm were released and after 48 hours the number of dead and live were observed. The results are as shown in Table 4.

Table 4______________________________________Compound No. Mortality (%)______________________________________1 83.52 707 85.08 10015 84.217 70.018 93.1EPN.sup.1 70.0(control)______________________________________ Note: ##STR25##

Test Example 5

Lethal effect on rice stem borer (Chilo suppressalis)

Eggs, just before hatching, 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 1/50000 a Wagner's pot. After eggs were hatched and the larvae entered into stems of rice plants, a 1,000 fold dilute solution of each 50% emulsifiable concentrate of the present compounds was applied by means of a turn table. The number dead and live were observed to calculate the mortality 4 days after application. The results are as shown in Table 5.

Table 5______________________________________Compound No. Mortality (%)______________________________________15 85.617 98.7Malathion .sup.1 41.3(control)______________________________________ Note: ##STR26##

Test Example 6

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 concentrate of the present compounds. The concentration of the active ingredient in the mixture was adjusted to 500 p.p.m. After 24 hours, the number of dead and live were observed microscopically to calculate the mortality. The results are as shown in Table 6.

Table 6______________________________________Compound No. Mortality (%)______________________________________1 1002 1006 1007 1008 1009 10013 10014 85.715 10016 10017 10018 100Dichloropropane .sup.1 79.3(control)______________________________________ Note: .sup.1 Chemical structure: ClCH=CH--CH.sub.2 Cl

Test Example 7

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./10a, 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 7.

Table 7______________________________________ Number of insects tobacco diamond-backCompound No. cut worm moth______________________________________15 13 1818 9 36No treatment 47 158Bipterex.sup.1 19 49(control)______________________________________ ##STR27##

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. 5)

To a solution of 7.84 g. of potassium O,S-diethylphosphorodithioate in 50 ml. of acetone, were added 6.29 g. of N-chloroacetyltetrahydroquinoline. The mixture was heated under reflux at 60.degree. C. for 3 hours, and cooled to room temperature to separate potassium chloride which was then filtered off. Acetone was distilled off from the filtrate and then the residual oily matter was dissolved in 50 ml. of benzene, washed with a 5% sodium bicarbonate solution and then water, and dried over anhydrous calcium chloride. Thereafter benzene was distilled off under reduced pressure to obtain 10.1 g. of N-(O,S-diethyldithiolphosphorylacetyl)tetrahydroquinoline (n.sub.D.sup.28 1.5796). The yield was 94.5% based on N-chloroacetyltetrahydroquinoline.

______________________________________Elemental analysis: Calculated (%) (as C.sub.15 H.sub.22 NO.sub.3 PS.sub.2) Found (%)C 50.14 50.19H 6.13 6.23N 3.90 3.84P 8.64 8.66______________________________________

EXAMPLE 2

(Compound No. 8)

To a solution of 6.60 g. of potassium O-ethyl-S-i-butylphosphorodithioate in 50 ml. of ethanol, were added 5.40 g. of N-chloroacetyltetrahydroquinoline. The mixture was heated under reflux at 80.degree. C. for 2 hours, and cooled to room temperature to separate potassium chloride which was then filtered off. Ethanol was distilled off from the filtrate and then the residual oily matter was dissolved in 50 ml. of benzene, washed with a 5% sodium bicarbonate solution and then water, and dried over anhydrous calcium chloride. Thereafter benzene was distilled off under reduced pressure to obtain 9.6 g. of N-(O-ethyl-S-i-butyldithiolphosphorylacetyl)-tetrahydroquinoline (n.sub.D.sup.28 1.5700).

______________________________________Elemental analysis: Calculated (%) (as C.sub.17 H.sub.26 NO.sub.3 PS.sub.2) Found (%)C 52.71 52.82H 6.72 6.74N 3.62 3.57P 8.01 8.13______________________________________

EXAMPLE 3

(Compound No. 14)

To a solution of 7.84 g. of potassium O,S-diethylphosphorodithioate in 50 ml. of acetone, were added 5.44 g. of N-chloroacetylhexamethylene imine. The mixture was heated under reflux at 60.degree. C. for 3 hours, and cooled to room temperature to separate potassium chloride which was then filtered off. Acetone was distilled off from the filtrate and then the residual oily matter was dissolved in 50 ml. of benzene, washed with a 5% sodium bicarbonate solution and then water, and dried over anhydrous calcium chloride. Thereafter benzene was distilled off under reduced pressure to obtain 9.50 g. of oily N-(O,S-diethyldithiolphosphorylacetyl)-hexamethylene imine (n.sub.D.sup.29 1.5349). The yield was 94% based on N-chloroacetylhexamethylene imine.

______________________________________Elemental analysis: Calculated (%) (as C.sub.12 H.sub.24 NO.sub.3 PS.sub.2) Found (%)C 44.31 44.10H 7.38 7.31N 4.31 4.39P 9.54 9.22______________________________________

EXAMPLE 4

(Compound No. 18)

To a solution of 7.08 g. of potassium O-ethyl-S-sec-butylphosphorodithioate in 50 ml. of ethanol, were added 4.91 g. of N-chloroacetylhexamethylene imine. The mixture was heated under reflux at 80.degree. C. for 2 hours, and cooled to room temperature to separate potassium chloride which was then filtered off. Ethanol was distilled off from the filtrate and then the residual oily matter was dissolved in 50 ml. of benzene, washed with a 5% sodium bicarbonate solution and then water, and dried over anhydrous calcium chloride. Thereafter benzene was distilled off under reduced pressure to obtain 8.90 g. of N-(O-ethyl-S-sec-butyldithiolphosphorylacetyl)-hexamethylene imine (n.sub.D.sup.23 1.5299). The yield was 90% based on N-chloroacetylhexamethylene imine.

______________________________________Elemental analysis: Calculated (%) (as C.sub.14 H.sub.28 NO.sub.3 PS.sub.2) Found (%)C 47.59 47.32H 7.93 8.08N 3.97 4.01P 8.78 8.47______________________________________

EXAMPLE 5

(Compound No. 25)

In 50 ml. of acetone were dissolved 5.24 g. (0.025 mol) of N-chloroacetyl-1,2,3,4-tetrahydroquinoline and 7.0 g. (0.026 mol) of potassium o-ethyl-O-metatolyl-phosphorothioate. The mixture was heated under reflux for 2 hours, cooled to room temperature, and then the resulting solid matter was removed by filtration. After removal of the solvent under reduced pressure, the residual oily matter was dissolved in 100 ml. of benzene, washed twice with water, dried over anhydrous calcium chloride and distilled to remove benzene. The residual oily matter was allowed to stand at 90.degree. C. for 1 hour under reduced pressure (0.1 mmHg) to obtain 6.0 g. of an analytically pure objective product (n.sub.D.sup.21 1.5804).

______________________________________Elemental analysis: Calculated (%) (as C.sub.20 H.sub.24 O.sub.4 SPS) Found (%)C 59.24 59.07H 5.97 6.09N 3.46 3.56P 7.64 7.64S 7.91 8.01______________________________________

EXAMPLE 6

(Compound No. 24)

In 50 ml. of acetone were dissolved 5.45 g. (0.026 mol) of N-chloroacetyl-1,2,3,4-tetrahydroquinoline and 7.2 g. (0.03 mol) of sodium O-ethyl-O-phenyl-phosphorothioate. The solution was treated in the same manner as described in Example 5 to obtain 5.7 g. of an objective product (n.sub.D.sup.28 1.5819).

______________________________________Elemental analysis: Calculated (%) (as C.sub.19 H.sub.22 NO.sub.4 PS) Found (%)C 58.21 58.37H 5.63 5.56N 3.58 3.55P 7.93 7.81S 8.18 8.23______________________________________

According to the process of the present invention, there are produced such phosphorothiolates as shown in the following table.

______________________________________ Elemental analysisExample Compound Yield Refractive Calculated FoundNo. No. (%) index (%) d(%)______________________________________ C 50.14 49.917 1 78.1 n.sub.D.sup.24 1.5832 H 6.13 6.14 N 3.90 3.98 P 8.64 8.35 C 51.41 51.398 2 79.2 n.sub.D.sup.28 1.5775 H 6.43 6.39 N 3.75 3.87 P 8.31 8.06 C 52.71 52.48 H 6.72 6.749 3 80.5 n.sub.D.sup.24 1.5751 N 3.62 3.65 P 8.01 7.98 C 53.87 53.74 H 6.98 6.9110 4 82.1 n.sub.D.sup.24 1.5656 N 3.49 3.39 P 7.73 7.99 C 51.47 51.65 H 6.43 6.4911 6 82.2 n.sub.D.sup.24 1.5771 N 3.75 3.70 P 8.31 8.55 C 52.71 52.47 H 6.72 6.6812 7 83.5 n.sub.D.sup.24 1.5745 N 3.62 3.67 P 8.01 7.91 C 53.87 53.86 H 6.98 6.9313 9 84.3 n.sub.D.sup.24 1.5669 N 3.49 3.47 P 7.73 7.54 C 53.87 54.00 H 6.98 7.1014 10 85.2 n.sub.D.sup.25 1.5708 N 3.49 3.73 F 7.73 7.61 C 54.94 55.13 H 7.23 7.0415 11 80.4 n.sub.D.sup.25 1.5680 N 3.37 3.57 P 7.47 7.59 C 52.71 57.55 H 6.72 6.6816 12 81.3 n.sub.D.sup.28 1.5733 N 3.62 3.68 P 8.01 8.13 C 46.02 45.62 H 7.67 7.5717 13 77.9 n.sub.D.sup.24 1.5285 N 4.13 4.17 P 9.14 8.73 C 46.02 46.06 H 7.67 7.9318 15 85.7 n.sub.D.sup.30 1.5469 N 4.13 4.10 P/ 9.14 9.30 C 47.59 47.67 H 7.93 7.9819 16 82.3 n.sub.D.sup.24 1.5291 N 3.97 3.89 P 8.78 8.40 C 47.59 47.48 H 7.93 7.6920 17 80.1 n.sub.D.sup.30 1.5302 N 3.97 3.90 P 8.78 8.72 C 49.05 49.20 H 8.17 8.2021 19 81.5 n.sub.D.sup.25 1.5290 N 3.81 3.87 P 8.45 8.50 C 50.39 50.20 H 8.40 8.4922 20 81.6 n.sub.D.sup.24 1.5260 N 3.67 3.73 P 8.14 7.84 C 47.59 47.60 H 7.93 7.9723 21 82.1 n.sub.D.sup.25 1.5284 N 3.97 4.07 P 8.78 8.51 C 46.27 46.55 H 7.17 7.3824 22 79.5 n.sub.D.sup.23 1.5439 N 4.15 4.23 P/ 9.18 9.31 C 42.44 42.62 H 7.07 7.0125 23 83.1 n.sub.D.sup.25 1.5422 N 4.50 4.59 P 9.97 9.85 C 59.24 59.20 H 5.97 6.0526 20 82.7 n.sub.D.sup.23 1.5816 N 3.46 3.45 P C 60.13 60.28 H 6.25 6.1927 27 83.5 n.sub.D.sup.22 1.5803 N 3.34 3.34 P C 53.58 53.54 H 4.94 4.9728 28 81.4 n.sub.D.sup.21 1.5898 N 3.29 3.31 P______________________________________

Claims

1. A herbicidal composition comprising an inert carrier and a herbicidally effective amount of at least one phosphorothiolate compound of the formula ##STR28## wherein R.sub.1 is a radical of the formula ##STR29## in which X is methyl, ethyl or chlorine and n is zero, 1 or 2, R.sub.2 is ethyl, propyl or butyl, and R.sub.3 is a radical of the formula ##STR30##

2. A composition according to claim 1, wherein the composition is in the form of granules, dust, wettable powder or emulsifiable concentrate.

3. A composition according to claim 2, wherein the composition further contains a fertilizer, a fungicide, an insecticide, a nematocide, a herbicide or a combination thereof.

4. A herbicidal composition comprising an inert carrier and a herbicidally effective amount of at least one compound selected from the group consisting of

(1) N-(O-methyl-S-n-propyldithiolphosphorylacetyl)-tetrahydroquinoline,

(2) N-(O-methyl-S-n-butyldithiolphosphorylacetyl)-tetrahydroquinoline,

(3) N-(O-methyl-S-n-pentyldithiolphosphorylacetyl)-tetrahydroquinoline,

(4) N-(O-methyl-S-n-hexyldithiolphosphorylacetyl)-tetrahydroquinoline,

(5) N-(O,S-diethyldithiolphosphorylacetyl)-tetrahydroquinoline,

(6) N-(O-ethyl-S-n-propyldithiolphosphorylacetyl)-tetrahydroquinoline,

(7) N-(O-ethyl-S-n-butyldithiolphosphorylacetyl)-tetrahydroquinoline,

(8) N-(O-ethyl-S-iso-butyldithiolphosphorylacetyl)-tetrahydroquinoline,

(9) N-(O-ethyl-S-iso-pentyldithiolphosphorylacetyl)-tetrahydroquinoline,

(10) N-(O-ethyl-S-n-pentyldithiolphosphorylacetyl)-tetrahydroquinoline,

(11) N-(O-ethyl-S-n-hexyldithiolphosphorylacetyl)-tetrahydroquinoline,

(12) N-(O-n-butyl-S-ethyldithiolphosphorylacetyl)-tetrahydroquinoline,

(13) N-(O-methyl-S-n-butyldithiolphosphorylacetyl)-hexamethylene imine,

(14) N-(O,S-diethyldithiolphosphorylacetyl)-hexamethylene imine,

(15) N-(O-ethyl-S-n-propyldithiolphosphorylacetyl)-hexamethylene imine,

(16) N-(O-ethyl-S-n-butyldithiolphosphorylacetyl)-hexamethylene imine,

(17) N-(O-ethyl-S-iso-butyldithiolphosphorylacetyl)-hexamethylene imine,

(18) N-(O-ethyl-S-sec-butyldithiolphosphorylacetyl)-hexamethylene imine,

(19) N-(O-ethyl-S-n-pentyldithiolphosphorylacetyl)-hexamethylene imine,

(20) N-(O-ethyl-S-n-hexyldithiolphosphorylacetyl)-hexamethylene imine,

(21) N-(O-n-butyl-S-ethyldithiolphosphorylacetyl)-hexamethylene imine,

(22) N-(O-ethyl-S-allyldithiolphosphorylacetyl)-hexamethylene imine,

(23) N-(O-ethyl-S-methyldithiolphosphorylacetyl)-hexamethylene imine,

(24) N-(O-ethyl-O-phenylthiolphosphorylacetyl)-tetrahydroquinoline,

(25) N-(O-ethyl-O-metatolylthiolphosphorylacetyl)-tetrahydroquinoline,

(26) N-(O-ethyl-O-orthotolylthiolphosphorylacetyl)-tetrahydroquinoline,

(27) N-(O-ethyl-O-3,5-xylenylthiolphosphorylacetyl)-tetrahydroquinoline,

(28) N-(O-ethyl-O-parachlorophenylthiolphosphorylacetyl)-tetrahydroquinoline,

(29) N-(O-n-propyl-O-phenylthiolphosphorylacetyl)-tetrahydroquinoline,

(30) N-(O-n-propyl-O-orthotolylthiolphosphorylacetyl)-tetrahydroquinoline,

(31) N-(O-n-butyl-O-phenylthiolphosphorylacetyl)-tetrahydroquinoline,

(32) N-(O-n-butyl-O-metatolylthiolphosphorylacetyl)-tetrahydroquinoline, and

(33) N-(O-butyl-O-paraethylphenylthiolphosphorylacetyl)-tetrahydroquinoline,

(34) a compound of the formula ##STR31## (35) a compound of the formula ##STR32##

5. A composition according to claim 4, wherein the composition is in the form of granules, dust, wettable powder or emulsifiable concentrate.

6. A composition according to claim 5, wherein the composition further contains a fertilizer, a fungicide, an insecticide, a nematocide, a herbicide or a combination thereof.

7. A method for killing undesirable weeds, which comprises applying to said weeds an effective amount of a phosphorothiolate compound of the formula ##STR33## wherein R.sub.1 is a radical of the formula ##STR34## in which X is methyl, ethyl or chlorine and n is zero, 1 or 2, R.sub.2 is ethyl, propyl or butyl, and R.sub.3 is a radical of the formula ##STR35##

8. A method for killing undesirable weeds, which comprises applying to said weeds an effective amount of at least one compound selected from the group consisting of

(1) N-(O-methyl-S-n-propyldithiolphosphorylacetyl)-tetrahydroquinoline,

(2) N-(O-methyl-S-n-butyldithiolphosphorylacetyl)-tetrahydroquinoline,

(3) N-(O-methyl-S-n-pentyldithiolphosphorylacetyl)-tetrahydroquinoline,

(4) N-(O-methyl-S-n-hexyldithiolphosphorylacetyl)-tetrahydroquinoline,

(5) N-(O,S-diethyldithiolphosphorylacetyl)-tetrahydroquinoline,

(6) N-(O-ethyl-S-n-propyldithiolphosphorylacetyl)-tetrahydroquinoline,

(7) N-(O-ethyl-S-n-butyldithiolphosphorylacetyl)-tetrahydroquinoline,

(8) N-(O-ethyl-S-iso-butyldithiolphosphorylacetyl)-tetrahydroquinoline,

(9) N-(O-ethyl-S-iso-pentyldithiolphosphorylacetyl)-tetrahydroquinoline,

(10) N-(O-ethyl-S-n-pentyldithiolphosphorylacetyl)-tetrahydroquinoline,

(11) N-(O-ethyl-S-n-hexyldithiolphosphorylacetyl)-tetrahydroquinoline,

(12) N-(O-n-butyl-S-ethyldithiolphosphorylacetyl)-tetrahydroquinoline,

(13) N-(O-methyl-S-n-butyldithiolphosphorylacetyl)-hexamethylene imine,

(14) N-(O,S-diethyldithiolphosphorylacetyl)-hexamethylene imine,

(15) N-(O-ethyl-S-n-propyldithiolphosphorylacetyl)-hexamethylene imine,

(16) N-(O-ethyl-S-n-butyldithiolphosphorylacetyl)-hexamethylene imine,

(17) N-(O-ethyl-S-iso-butyldithiolphosphorylacetyl)-hexamethylene imine,

(18) N-(O-ethyl-S-sec-butyldithiolphosphorylacetyl)-hexamethylene imine,

(19) N-(O-ethyl-S-n-pentyldithiolphosphorylacetyl)-hexamethylene imine,

(20) N-(O-ethyl-S-n-hexyldithiolphosphorylacetyl)-hexamethylene imine,

(21) N-(O-n-butyl-S-ethyldithiolphosphorylacetyl)-hexamethylene imine,

(22) N-(O-ethyl-S-allyldithiolphosphorylacetyl)-hexamethylene imine,

(23) N-(O-ethyl-S-methyldithiolphosphorylacetyl)-hexamethylene imine,

(24) N-(O-ethyl-O-phenylthiolphosphorylacetyl)-tetrahydroquinoline,

(25) N-(O-ethyl-O-metatolylthiolphosphorylacetyl)-tetrahydroquinoline,

(26) N-(O-ethyl-O-orthotolylthiolphosphorylacetyl)-tetrahydroquinoline,

(27) N-(O-ethyl-O-3,5-xylenylthiolphosphorylacetyl)-tetrahydroquinoline,

(28) N-(O-ethyl-O-parachlorophenylthiolphosphorylacetyl)-tetrahydroquinoline,

(29) N-(O-n-propyl-O-phenylthiolphosphorylacetyl)-tetrahydroquinoline,

(30) N-(O-n-propyl-O-orthotolylthiolphosphorylacetyl)-tetrahydroquinoline,

(31) N-(O-n-butyl-O-phenylthiolphosphorylacetyl)-tetrahydroquinoline,

(32) N-(O-n-butyl-O-metatolylthiolphosphorylacetyl)-tetrahydroquinoline, and

(33) N-(O-butyl-O-paraethylphenylthiolphosphorylacetyl)-tetrahydroquinoline,

(34) a compound of the formula ##STR36## (35) a compound of the formula ##STR37##