Herbicide compositions of extended soil life

Abstract

The soil life of herbicidally active thiolcarbamates is extended by employing in combination therewith certain organophosphorus compounds having the formula 3 ##STR1## in which R.sup.4 is selected from the group consisting of C.sub.1 -C.sub.4 alkyl and C.sub.1 -C.sub.4 alkoxy; R.sup.5 is selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.2 -C.sub.4 alkenylthio and C.sub.2 -C.sub.4 alkynylthio; R.sup.6 is selected from the group consisting of hydrogen , C.sub.1 -C.sub.10 alkyl, C.sub.5 -C.sub.7 cycloalkyl and phenyl; and R.sup.7 is selected from the group consisting of C.sub.2 -C.sub.4 alkenyl, C.sub.1 -C.sub.10 alkoxy, C.sub.1 -C.sub.10 alkylthio, C.sub.2 -C.sub.6 alkynoxy, C.sub.2 -C.sub.5 carbalkoxy, phenyl, phenoxy, (C.sub.1 -C.sub.3 alkoxy)phenyl, benzyl and benzyloxy, all optionally substituted with up to two halogen atoms.

Description

BACKGROUND OF THE INVENTION

This invention relates to herbicidal compositions and methods of use. In particular, this invention relates to herbicidal compositions comprising an herbicidally active thiocarbamate in combination with certain organophosphorus compounds, the latter serving to prolong the effectiveness of a single application of the thiocarbamate in controlling undesired plant growth.

Thiocarbamates are well known in the agricultural art as herbicides useful for weed control in crops such as corn, potatoes, beans, beets, spinach, tobacco, tomatoes, alfalfa, rice and others. Thiocarbamates are primarily used in pre-emergence application, and are particularly effective when incorporated into the soil prior to the planting of the crop. The concentration of the thiocarbamate in the soil is greatest immediately after application of the compound. How long thereafter the initial concentration is retained depends in large part on the particular soil used. The rate at which the thiocarbamate concentration declines following its application varies from one type of soil to the next. This is evident both in the observable extent of weed control and in the detectable presence of undegraded thiocarbamate remaining in the soil after considerable time has elapsed.

It is therefore an object of this invention to increase the soil persistence of thiocarbamate herbicides and thus improve their herbicidal effectiveness.

BRIEF DESCRIPTION OF THE INVENTION

It has now been discovered that the soil persistence of certain herbicidally active thiocarbamates is significantly extended by the further addition to the soil of certain extender compounds in the form of organophosphorus compounds, which have little or no herbicidal activity of their own and do not decrease the herbicidal activity of the thiocarbamate. This improvement in the soil persistence of thiocarbamates manifests itself in a variety of ways. It can be shown, for example, by soil analyses taken at regular intervals, that the rate of decrease of the thiocarbamate content of the soil is substantially lessened. Improved soil persistence can also be shown by improvements in herbicidal efficacy, as evidenced by a higher degree of weed injury brought about when the extender compound increases the soil persistence of the thiocarbamate, prolonging its effective life.

Examples 1 and 2 below illustrate two different methods of proving the extending activity of the organophosphorus compounds of the instant invention. Example 1 provides chemical assay data whereas Example 2 provides bioassay data. The soil in both examples is pre-treated with a thiocarbamate herbicide to simulate field conditions wherein a field has been repeatedly treated with a thiocarbamate herbicide. However, instead of a year inbetween treatments as in the case of seasonally cultivated fields, the soil in the experiments herein was retreated with the herbicide within weeks of the first treatment. Such a short retreatment period provides a soil which is conditioned to degrade thiocarbamates rapidly for experimental purposes.

The chemical assay data of Example 1 shows by chromatographic analysis that the thiocarbamate herbicide's soil life is extended over time by evidencing that the parts per million of the herbicide is much greater when an organophosphorus extender is present than when it is absent.

The bioassay data of Example 2 shows the soil life extension of thiocarbamate herbicides by the extension of their herbicidal activity in soil also conditioned for rapid degradation of thiocarbamate herbicides.

In particular, this invention relates to a novel herbicidal composition comprising

(a) an herbicidally effective amount of a thiocarbamate having the formula ##STR2## in which R.sup.1, R.sup.2, and R.sup.3 are independently C.sub.2 -C.sub.4 alkyl; and

(b) an amount of an organophosphorus compound sufficient to extend the soil life of said thiocarbamate, said organophosphorus compound having the formula ##STR3## in which

R.sup.4 is selected from the group consisting of C.sub.1 -C.sub.4 alkyl and C.sub.1 -C.sub.4 alkoxy, R.sup.5 is selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.2 -C.sub.4 alkenylthio and C.sub.2 -C.sub.4 alkynylthio, R.sup.6 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.10 alkyl, C.sub.5 -C.sub.7 cycloalkyl and phenyl, and R.sup.7 is selected from the group consisting of C.sub.2 -C.sub.4 alkenyl, C.sub.1 -C.sub.10 alkoxy, C.sub.1 -C.sub.10 alkylthio, C.sub.2 -C.sub.6 alknyoxy, C.sub.2 -C.sub.5 carbalkoxy, phenyl, phenoxy, (C.sub.1 -C.sub.3 alkoxy)phenyl, benzyl and benzyloxy, all optionally substituted with up to two halogen atoms.

Within the scope of the present invention, certain embodiments are preferred, namely:

In the thiocarbamate formula, R.sup.1 is preferably ethyl or n-propyl, and R.sup.2 and R.sup.3 are each preferably n-propyl or each isobutyl.

Concerning the organophosphorus compounds, it is preferred that:

R.sup.4 is selected from the group consisting of C.sub.1 -C.sub.4 alkyl, R.sup.5 is selected from the group consisting of C.sub.1 -C.sub.4 alkylthio, C.sub.2 -C.sub.4 alkenylthio and C.sub.2 -C.sub.4 alkynylthio, R.sup.6 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.10 alkyl, cyclohexyl, and phenyl, and R.sup.7 is selected from the group consisting of C.sub.2 -C.sub.4 alkenyl, C.sub.1 -C.sub.10 alkoxy, phenyl, and phenoxy, all optionally substituted with up to two halogen atoms.

This invention further relates to a method of controlling undesirable vegetation comprising applying the above composition to the locus where control is desired.

The terms "alkyl," "alkenyl", "alkynyl", etc. are intended to include both straight-chain and branched-chain groups. All carbon atoms ranges recited in this specification and the appended claims are intended to be inclusive of their upper or lower limits.

The term "herbicide", as used herein, means a compound or composition which controls or modifies the growth of plants. By the term "herbicidally effective amount" is meant any amount of such compound or composition which causes a modifying effect upon the growth of plants. By "plants" is meant germinant seeds, emerging seedlings and established vegetation, including roots and above-ground portions. Such controlling or modifying effects include all deviations from natural development, such as killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, leaf burn, dwarfing and the like.

The phrase "to extend the soil life of said thiocarbamate" as used herein means to retard the rate at which molecules of thiocarbamate are broken down into decomposition products when in contact with soil and/or to prolong the period of time following application in which herbicidal effects can be observed. This applies both to field sites where repeated applications of thiocarbamates have resulted in decreasing herbicidal effectiveness, and to field sites where a decline in activity is detected over time regardless of the prior history of herbicidal applications. An extended soil life can be manifest in a slower rate of decline of weed-killing activity, or an increased half-life of thiocarbamate concentration in the soil. Other techniques of determining soil life are readily apparent to one skilled in the art.

DETAILED DESCRIPTION OF THE INVENTION

The thiocarbamates within the scope of the present invention can be prepared by the process described in U.S. Pat. No. 2,913,327 (Tilles et al., Nov. 17, 1959). The organophosphorus compounds can be prepared by the process described in U.S. Pat. No. 4,001,404 (Hoffmann et al., Jan. 4, 1977) and USSR Pat. No. 464,592 (Moscow Mendeleev Chem., Apr. 12, 1973).

The objects of the present invention are achieved by applying the organophosphorus extender compound to the soil at an agricultural field site in conjunction with the thiocarbamate herbicide. The two compounds can be applied simultaneously in a single mixture or in separate formulations, or they can be applied in succession, with either one following the other. In successive application, it is preferable to add the compounds as close in time as possible.

The herbicide extending effect is operable over a wide range of ratios of the two compounds. It is most convenient, however, to apply the compounds at a ratio of about 1:1 to about 20:1 (herbicide/extender) on a weight basis, preferably about 1:1 to about 10:1, and most preferably about 1:1 to about 5:1.

Thiocarbamate herbicides useful in the present invention include S-ethyl di-n-propylthiocarbamate, S-ethyl diisobutylthiocarbamate, S-n-propyl di-n-propylthiocarbamate, and S-n-propyl ethyl-n-butylthiocarbamate.

The variety of crops on which the present composition is useful can be significantly broadened by the use of an antidote to protect the crop from injury and render the composition more selective against weeds.

For antidote descriptions and methods of use, reference is made to U.S. Pat. No. 3,959,304, issued to E. G. Teach on May 25, 1976; U.S. Pat. No. 3,989,503, issued to F. M. Pallos et al. on Nov. 2, 1976; U.S. Pat. No. 4,021,224, issued to F. M. Pallos et al. on May 3, 1977; U.S. Pat. No. 3,131,509 issued to O. L. Hoffman on May 5, 1964; and U.S. Pat. No. 3,564,768, issued to O. L. Hoffman on Feb. 3, 1971.

Examples of useful antidotes include acetamides such as N,N-diallyl-2,2-dichloroacetamide and N,N-diallyl-2-chloroacetamide, oxazolidines such as 2,2,5-trimethyl-N-dichloroacetyl oxazolidine and 2,2-spirocyclohexyl-N-dichloroacetyl oxazolidine, and 1,8-naphthalic anhydride. For maximum effect, the antidote is present in the composition in a non-phytotoxic, antidotally effective amount. By "non-phytotoxic" is meant an amount which causes at most minor injury to the crop. By "antidotally effective" is meant an amount which substantially decreases the extent of injury caused by the herbicide to the crop. The preferred weight ratio of herbicide to antidote is about 0.1:1 to about 30:1. The most preferred range for this ratio is about 3:1 to about 20:1.

The following examples are offered to illustrate the utility of the present invention, and are intended neither to limit nor define the invention in any manner.

EXAMPLE 1

These examples show, by soil analysis, the effectiveness of the compounds of the present invention in extending the soil life of the thiocarbamate herbicides. The herbicide used in these tests was S-ethyl di-n-propylthiocarbamate, commonly known as EPTC. The soil was a sandy loam soil obtained from Sunol, Calif., containing approximately (on a weight basis) 64% sand, 29% silt, and 7% clay, determined by mechanical means. The total organic content of the soil was approximately 4% by weight and the pH was 6.8, both determined by chemical analysis.

The test procedure involved an initial pre-treatment of the soil to simulate field conditions where the soil had been previously treated with EPTC, followed by a soil persistence test, as described below.

A. Soil Pre-Treatment

An emulsion was prepared by diluting an emulsifiable liquid concentrate containing 6 lb/gal (0.72 kg/l) of the thiocarbamate in 100 ml of water, such that the concentration of thiocarbamate in the resulting emulsion was 4000 mg/l. Five ml of this emulsion was then added to 10 lb (4.54 kg) of soil and the mixture was mixed in a rotary mixer for 10-20 seconds.

Round plastic containers, 9 inches (22.9 cm) in diameter by 9 inches (22.9 cm) deep, were then filled with the sandy loam soil, which was tamped and leveled with a row marker to impress three rows across the width of each container. Two rows were seeded with DeKalb XL-45A corn Zea mays (L.), and one row was seeded with barnyardgrass Echinochloa crusgalli (L.). Sufficient seeds were planted to produce several seedlings per row. The containers were then placed in a greenhouse maintained at 20.degree. C. to 30.degree. C. and watered daily by sprinkler.

Five weeks after treatment, the soil was allowed to dry out and the plant foliage was removed. The soil was then passed through a 0.25 inch (0.64 cm) screen, followed by a 2 millimeter (mm) screen, to remove plant roots and clods.

B. Soil Persistence Test

A 100-gram quantity (air-dry basis) of the pre-treated soil was placed in an 8-ounce (0.25 liter) wide-mouth glass bottle. The same emulsifiable concentrate described in Part A above was appropriately diluted in water such that a 5-ml portion added to the soil would produce a herbicide concentration of 6 ppm (weight) in the soil. This is equivalent to an application rate of 6 pounds per acre (6.7 kilograms per hectare) in a field where the herbicide is incorporated into the soil through a depth of about 2 inches (5.08 cm) soon after application. A selected extender compound in technical (nonformulated) form was then diluted in an acetone-water mixture such that a one-ml portion added to the soil would produce a concentration of 4 ppm by weight, equivalent to 4 pounds per acre (4.5 kilograms per hectare). On these bases, the herbicide and extender were added to the bottle containing the soil. The bottle was then sealed with a lid and shaken manually for approximately 15 minutes.

Following such treatment, the soil was moistened with 20 ml deionized water. The bottle was then covered with a watch glass to maintain aerobic conditions and to prevent rapid soil drying, and placed in a controlled environmental chamber in darkness, where the temperature was maintained constant at 25.degree. C.

Two days later, the bottle was removed from the environmental chamber and 50 ml of water and 100 ml of toluene were added. The bottle was then tightly sealed with a lid containing a cellophane liner, and vigorously shaken on a variable speed, reciprocating shaker (Eberbach Corp. Model 6000) set at approximately 200 excursions per minute for one hour. After shaking, the bottle contents were allowed to settle, and a 10 ml aliquot of toluene was transferred by pipette into a glass vial and sealed with a polyseal cap. The toluene extract was analyzed for herbidal content by gas chromatography. The chromatogram data was then converted to equivalent soil concentrations in parts per million (ppm) by weight of the herbicide.

The results are shown in Table 1 below, where a variety of compounds were tested in two separately treated batches of soil. A control run without an extender compound was conducted for each soil batch, to show how the drop in herbicide concentration was affected by the extender compound. In each case, the quantity of herbicide remaining in the soil after two days was dramatically increased when the extender compound was added.

TABLE 1______________________________________2-DAY SOIL PERSISTENCE DATAHerbicide: SEthyl di-n-propylthiolcarbamate (EPTC) at 6 lb/A(6 ppm in soil)Extender: As shown at 4 lb/A (4 ppm in soil) EPTC Residue After 2 DaysEx- (ppm)tender With-Com- With outpound Ex- Ex-No. Structural Formula tender tender______________________________________ Soil Batch A: 1 ##STR4## 4.32 1.32 2 ##STR5## 3.04 1.32 3 ##STR6## 2.37 1.32 4 ##STR7## 3.04 1.32 5 ##STR8## 2.77 1.32 6 ##STR9## 2.81 1.32 7 ##STR10## 3.28 1.32 8 ##STR11## 2.54 1.32 9 ##STR12## 2.40 1.3210 ##STR13## 3.92 1.3211 ##STR14## 3.55 1.3212 ##STR15## 3.94 1.3213 ##STR16## 2.64 1.3214 ##STR17## 2.85 1.3215 ##STR18## 3.08 1.32 Soil Batch B:16 ##STR19## 0.53 0.4217 ##STR20## 0.52 0.4218 ##STR21## 0.56 0.4219 ##STR22## 0.51 0.42 Soil Batch C:20 ##STR23## 0.71 0.4421 ##STR24## 0.59 0.4422 ##STR25## 0.62 0.4423 ##STR26## 0.91 0.4424 ##STR27## 0.49 0.4425 ##STR28## 0.60 0.44______________________________________

EXAMPLE 2

Test Procedures

This example offers herbicidal activity test data for many representative extender compounds within the scope of this invention showing their effectiveness in improving the herbicidal activity of thiocarbamates. The effect is observed by comparing the extent of weed control in test flats treated with a thiocarbamate against that occurring in similar flats treated with both the thiocarbamate and the extender. The soil used in these tests was a sandy loam soil from Sunol, Calif., which was pre-treated with the herbicide to simulate a typical field which had received previous herbicide applications.

The compounds tested by the procedures below have the structures as follows:

TABLE OF COMPOUNDS______________________________________Ex-tenderCmpd.No. R.sup.4 R.sup.5 R.sup.6 R.sup.7______________________________________1 C.sub.2 H .sub.5 CH.sub.3 S H OC.sub.2 H.sub.52 C.sub.2 H .sub.5 C.sub.2 H.sub.5 S CH.sub.3 OC.sub.2 H.sub.53 C.sub.2 H .sub.5 CHCCH.sub.2 S H OC.sub.2 H.sub.54 C.sub.2 H .sub.5 CH.sub.3 S CH.sub.3 OC.sub.2 H.sub.55 C.sub.2 H .sub.5 CH.sub.2CHCH.sub.2 S CH.sub.3 OC.sub.2 H.sub.56 C.sub.2 H .sub.5 CHCCH.sub.3 S CH.sub.3 OC.sub.2 H.sub.57 C.sub.2 H .sub.5 CH.sub.3 S C.sub.2 H.sub.5 OC.sub.2 H.sub.58 C.sub.2 H .sub.5 CH.sub.3 S ##STR29## OC.sub.2 H.sub.59 C.sub.2 H .sub.5 CH.sub.3 S ##STR30## OC.sub.2 H.sub.510 C.sub.2 H.sub.5 CH.sub.3 S H CHCH.sub.211 C.sub.2 H.sub.5 CH.sub.3 S H C(CH .sub.3)CH.sub.213 C.sub.2 H .sub.5 CH.sub.3 S H ##STR31##14 C.sub.2 H .sub.5 CH.sub.3 S H ##STR32##______________________________________

A. Soil Pre-Treatment

The soil was pre-treated in each instance at 3 lb/A. Where the thiocarbamate testes was S-ethyl diisobutylthiocarbamate, a 6.7 lb/gal (85.2%) emulsifiable liquid concentrate in a 24:1 ratio with the antidote N,N-diallyl-2,2-dichloroacetamide was employed. Where the thiocarbamate was S-propyl N,N-dipropylthiocarbamate, the soil was pretreated with either an emulsifiable liquid concentrate in a 12:1 ratio with the antidote N,N-diallyl-2,2-dichloroacetamide or an emulsifiable liquid concentrate of the herbicide alone. In each instance, the emulsifiable liquid concentrates were diluted in 200 ml of water, such that the resulting concentration of herbicide in the solution was 2000 mg/l. Two hundred ml of this solution was then added to 200 lb (90.8 kg) of soil to which 17-17-17 fertilizer (N--P.sub.2 O.sub.5 --K.sub.2 O on a weight basis) had been previously added to a concentration of 50 ppm by weight with respect to the soil. The mixture was mixed in a rotary mixer for 10 to 30 minutes.

The soil was then placed in round plastic containers, 7.5 inches (19.0 cm) in diameter by 7.5 inches (19.0 cm) deep. The soil was tamped and leveled with a row marker to impress one row across the width of each container. This row was seeded with watergrass (Echinochloa crusgalli). Sufficient seeds were planted to produce several seedlings. The containers were then placed in a greenhouse maintained at 20.degree. C. to 30.degree. C. and watered daily by sprinkler.

Five weeks after treatment, the soil was allowed to dry out and the plant foliage was removed. The soil was then passed through a 0.25 inch (0.64 cm) screen to remove plant roots and clods. The soil was then treated according to the procedure of (B) below. When the pre-treatment was with S-propyl N,N-dipropyl thiocarbamate alone, the soil was not employed for one or more months, whereas the thiocarbamate plus antidote conditioned soil was used shortly after pre-treatment.

B. Herbicide Test

Solutions were prepared by diluting those emulsifiable liquid concentrates described above as containing the antidote N,N-diallyl-2,2-dichloroacetamide and thiocarbamate in 650 ml of water such that the resulting concentration of herbicide in the solution was 1.48 mg/ml. Five ml of this solution when added to three pounds of soil yielded a quantity in the soil equivalent to three pounds per acre.

The extender compounds were used in technical form. These materials were added to 5 ml acetone and 21 ml water such that the resulting concentration of the extender in the solution was 1.54 mg/ml. The acetone contained 1% of an emulsifier/surfactant. Five ml of this solution when added to three pounds of soil yielded a quantity in the soil equivalent to four pounds per acre.

Five ml of the extender solution and 5 ml of the herbicide solution were tank-mixed. The resultant mixture of 10 ml was then added to 3 lbs of soil and incorporated into the soil by a rotary mixer. Thus, 10 ml of the mixture and 3 pound of soil were placed in rotary mixter and incorporated.

The treated soil was then placed in aluminum flats which were approximately 2.5 inches deep, 3.5 inches wide, and 7.5 inches long. The soil was tamped and leveled with a row marker to impress six rows across the width of the flat. The test weeds were as follows:

______________________________________ ABBRE-COMMON NAME VIATION SCIENTIFIC NAME______________________________________watergrass WG Echinochloa crusgalli (L.)wild oats WO Avena fatua (L.)wild cane WC Sorghum bicolor (L.) Moench______________________________________

R-10 milo (Sorghum bicolor) was also used as a plant growth indicator. Two rows of watergrass were planted. One row of each of the other weeds and plant growth indicator were planted.

Sufficient seeds were planted to produce several seedlings per inch in each row. The flats were then placed in a greenhouse maintained at 70.degree. to 85.degree. F. (21.degree. to 30.degree. C.) and watered daily by sprinkler.

Sixteen days after treatment, the degree of weed control and corn injury were estimated and recorded as a percentage compared to the growth of the same species in a check flat of the same age which had been seeded in conditioned soil but not treated with either an herbicide or an extender. The rating scale ranges from 0 to 100%, where 0 equals no effect with plant growth equal to the untreated check, and 100 equals complete kill.

The results are recorded in Table 2 below. An asterisk in the Table indicates that the treatment was run in soil pre-treated with the thiocarbamate S-propyl N,N-dipropyl thiocarbamate, alone, that is, without an antidote.

The average percentage of weed control is the average for the above-identified weed species and plant growth indicator. Control experimens (herbicide alone with no extender present) were included in each batch for comparison. Substantial improvements in average percent weed control over the control experiments are evident. The herbicidal efficacy of the thiocarbamate three weeks after application was much improved by the use of the extender.

TABLE 2______________________________________HERBICIDAL ACTIVITY TESTSHerbicide A: S--propyl N,N--dipropyl thiocarbamate in a 12:1weight ratio with the antidote N,N--diallyl-2,2-dichloroacetamideHerbicide B: S--ethyl N,N--diisobutyl thiocarbamate in a 24:1weight ratio with the antidote N,N--diallyl-2,2-dichloroacetamideExtender: Indicated by Compound No. (see list above)Herbicide Application Rate: 3 lb/AcreExtender Application Rate: 4 lb/AcreTreatment Average % ControlHerbicide Extender of 4 Grass Species______________________________________A -- 19(average of3 trials)A 1 32A 2 37A 3 60A 4 47A 5 44A 6 61A 7 40A 8 41A 9 35A 10 26A 13 36A 14 58*B -- 6(average of3 trials)B 1 67B 2 58B 3 54B 4 56B 5 58B 6 66B 7 49B 8 36B 9 70B 10 37B 11 61B 14 77______________________________________

Without Antidotes

The same procedures were followed as stated above under procedure above with antidote except that no antidote is present in the emulsifiable liquid concentrates with the thiocarbamates--S-ethyl N,N-diisobutylthiocarbamate (77.3% active ingredient) and S-propyl N,N-dipropylthiocarbamate (89% active ingredient); and that the rating was taken 22 days after treatment.

TABLE 3______________________________________HERBICIDAL ACTIVlTY TESTSHerbicide A: S--propyl N,N--dipropyl thiocarbamateHerbicide B: S--ethyl N,N--diisobutyl thiocarbamateExtender: Indicated by Compound No. (see Table ofCompounds above)Herbicide Application Rate: 3 lb/AcreExtender Application Rate: 2 or 4 lb/Acre ExtenderTreatment Application Average % ControlHerbicide Extender Rate (lb/A) of 4 Grass Species______________________________________A -- -- 18(average of3 trials)A 9 2 79A 9 4 82A 14 2 79A 14 4 89B -- -- 31(average of3 trials)B 9 2 67B 9 4 70B 14 2 66B 14 4 60______________________________________

Methods of Application

The herbicidal compositions of the present invention are useful in controlling the growth of undesirable vegetation by pre-emergence or post-emergence applcation to the locus where control is desired, including pre-plant and post-plant soil incorporation as well as surface application. The compositions are generally embodied in formulations suitable for conventient application. Typical formulations contain additional ingredients or diluent carriers which are either inert or active. Examples of such ingredients or carriers are water, organic solvents, dust carriers, granular carriers, surface active agents, oil and water, water-oil emulsions, wetting agents, dispersing agents, and emulsifying agents. The herbicidal formulations generally take the form of dusts, emulsifiable concentrates, granules and pellets, or microcapsules.

A. Dusts

Dusts are dense powder compositions which are intended for application in dry form. Dusts are characterized by their free-flowing and rapid settling properties so that they are not readily to areas where their presence is not desired. They contain primarily an active material and a dense, free-flowing, solid carrier.

Their performance is sometimes aided by the inclusion of a wetting agent, and convenience in manufacture frequently demands the inclusion of an inert, absorptive grinding aid. For the dust compositions of this invention, the inert carrier may be either of vegetable or mineral origin, the wetting agent is preferably anionic or nonionic, and suitable absorptive grinding aids are of mineral origin.

Suitable classes of inert solid carriers for use in the dust composition are those organic or inorganic powders which possess high bulk density and are very free-flowing. They are also characterized by low surface area and poor liquid absorptivity. Suitable grinding aids are fillers derived from natural clays, diatomaceous earths, and synthetic mineral fillers derived from silica or silicate. Among ionic and nonionic wetting agents, the most suitable are the members of the group known to to the art as wetting agents and emulsifiers. Although solid agents are preferred because of ease in incorporation some liquid nonionic agents are also suitable in the dust formulations.

Preferred dust carriers are micaceous talcs, pyrophyllite, dense kailin clays, tobacco dust and ground calcium phosphate rock.

Preferred grinding aids are attapulgite clay, diatomaceous silica, synthetic fine silica and synthetic calcium and magnesium silicates.

Most preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, and ditertiary acetylenic glycols. Preferred dispersants are methyl cellulose, polyvinyl alcohol, lignin sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalenesulfonate, polymethylene bisnaphthalenesulfonate, and sodium-N-methyl-N-(long chain acid) taurates.

The inert solid carriers in the dusts of this invention are usually present in concentrations of from about 30 to 90 weight percent of the total composition. The grinding aid will usually constitute 5 to 50 weight percent of the compositions, and the wetting agent will constitute from about 0 to 1.0 weight percent of the composition. Dust compositions can also contain other surfactants such as dispersing agents in concentrations of up to about 0.5 weight percent, and minor amounts of anticaking and antistatic agents. The particle size of the carrier is usually in the range of 30 to 50 microns.

B. Emulsifiable Concentrates

Emulsifiable concentrates are usually solutions of the active materials in nonwater-miscible solvents together with an emulsifying agent. Prior to use, the concentrate is diluted with water to form a supended emulsion of solvent droplets.

Typical solvents for use in emulsifiable concentrates include weed oils, chlorinated hydrocarbons, and nonwater-miscible ethers, esters, and ketones.

Typical emulsifying agents are anionic or nonionic surfactants, or mixtures of the two. Examples include long-chain mercaptan polyethoxy alcohols, alkylaryl polyethoxy alcohols, sorbitan fatty acid esters, polyoxyethylene ethers with sorbitan fatty acid esters, polyoxyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, calcium and amine salts of fatty alcohol sulfates, oil soluble petroleum sulfonates, or preferably mixtures of these emulsifying agents. Such emulsifying agents will comprise from about 1 to 10 weight percent of the total composition.

Thus, emulsifiable concentrates of the present invention will consist of from about 15 to about 50 weight percent active material, about 40 to 82 weight percent solvent, and about 1 to 10 weight percent emulsifier. Other additives such as spreading agents and stickers can also be included.

C. Granules and Pellets

Granules and pellets are physically stable, particular compositions containing the active ingredients adhering to or distributed through a basic matrix of a coherent, inert carrier with macroscopic dimensions. A typical particle is about 1 to 2 millimeters in diameter. Surfactants are often present to aid in leaching of the active ingredient from the granule or pellet.

The carrier is preferably of mineral origin, and generally falls within one of two types. The first are porous, absorptive, preformed granules, such as preformed and screened granular attapulgite or heat expanded, granular, screened vermiculite. On either of these, a solution of the active agent can be sprayed and will be absorbed at concentrations up to 25 weight percent of the total weight. The second, which are also suitable for pellets, are initially powdered kaolin clays, hydrated attapulgite, or bentonite clays in the form of sodium, calcium, or magnesium bentonites. Water-soluble salts, such as sodium salts, may also be present to aid in the disintegration of granules or pellets in the presence of moisture. These ingredients are blended with the active components to give mixtures that are granulated or pelleted, followed by drying, to yield formulations with the active component distributed uniformly throughout the mass. Such granules and pellets can also be made with 25 to 30 weight percent active component, but more frequently a concentration of about 10 weight percent is desired for optimum distribution. The granular compositions of this invention are most useful in a size range of 15-30 mesh.

The surfactant is generally a common wetting agent of anionic or nonionic character. The most suitable wetting agents depend upon the type of granule used. When preformed granules are sprayed with active material in liquid form the most suitable wetting agents are nonionic, liquid wetters miscible with the solvent. These are compounds most generally known in the art as emulsifiers, and comprise alkylaryl polyether alcohols, alkyl polyether alcohols, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, oil solution petroleum or vegetable oil sulfonates, or mixtures of these. Such agents will usually comprise up to about 5 weight percent of the total combustion.

When the active ingredient is first mixed with a powdered carrier and subsequently granulated, or pelleted, liquid nonionic wetters can still be used, but it is usually preferable to incorporate at the mixing stage one of the solid, powdered anionic wetting agents such as those previously listed for the wettable powders. Such agents will comprise from about 0 to 2 weight percent of the total composition.

Thus, the preferred granular or pelleted formulations of this invention comprise about 5 to 30 percent by weight active material, about 0 to 5 weight percent wetting agent, and about 65 to 95 weight percent inert material carrier, as these terms are used herein.

D. Microcapsules

Microcapsules consist of fully enclosed droplets or granules containing the active materials, in which the enclosing material is an inert porous membrane, arranged to allow escape of the enclosed materials to the surrounding medium at controlled rates over a specified period. Encapsulated droplets are typically about 1 to 50 microns in diameter.

The enclosed liquid typically constitutes about 50 to 95% of the weight of the entire capsule, and may contain a small amount of solvent in addition to the active materials.

Encapsulated granules are characterized by porous membranes sealing the openings of the granule carrier pores, trapping the liquid containing the active components inside for controlled release. A typical granule size ranges from 1 millimeter to 1 centimeter in diameter. In agricultural usage, the granule size is generally about 1 to 2 millimeters in diameter. Granules formed by extrusion, agglomeration, or prilling are useful in the present invention as well as materials in their naturally occurring form. Examples of such carriers are vermiculite, sintered clay granules, kaolin, attapulgite clay, sawdust, and granular carbon.

Useful encapsulating materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyurethanes, and starch xanthates.

E. In General

Each of the above formulations can be prepared as a package containing both the herbicides and the exterior together with the other ingredients of the formulation (diluents, emulsifiers, surfactants, etc.). The formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site. The herbicide and extender may both be used in the same type of formulation or a different formulation may be used for each, e.g. the herbicide may be in microcapsule form while the extender may be an emulsifiable concentrate, or vice versa.

As a further alternative, the herbicide and extender can be applied sequentially, with either being applied first. This is a less preferred method, however, since more effective results are obtained with simultaneous application.

In general, any conventional method of application can be used. The locus of application can be soil, seeds, seedlings, or the actual plants, as well as flooded fields. Soil application is preferred. Dusts and liquid compositions can be applied by the use of powder dusters, boom and hand sprayers, and spray dusters. The compositions can also be applied from airplanes as dusts and sprays because they are effective in very low dosages. In order to modify or control the growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least one-half inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles. Instead, these compositions can be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition of irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surfce of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The herbicide/extender compositions can also be applied to the soil through irrigation systems. According to this technique, the compositions are added directly to irrigation water immediately prior to irrigation of the field. This technique is applicable in all geographical areas regardless of rainfall, since it permits supplementation of the natural rainfall at critical stages of plant growth. In a typical application, the concentration of the herbicide/extender composition in the irrigation water will range from about 10 to 150 parts per million by weight. The irrigation water can be applied by the use of sprinkler systems, surface furrows, or flooding. Such application is most effectively done before the weeds germinate, either early in the spring prior to germination or within two days after cultivation of the field.

The amount of the present composition which constitutes a herbicidally effective amount depends upon the nature of the seeds or plants to be controlled. The rate of application of active ingredient varies from about 0.01 to about 50 pounds per acre, preferably about 0.1 to about 25 pounds per acre with the actual amount depending on the overall cost and the desired results. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbicidal activity will require a higher dosage than more active compounds for the same degree of control.

Claims

1. An herbicidal composition comprising

(a) an herbicidally effective amount of a thiocarbamate having the formula ##STR33## in which R.sup.1, R.sup.2 and R.sup.3 are independently C.sub.1 -C.sub.4 alkyl with the proviso that wherein R.sup.1 is ethyl and R.sup.2 is propyl, R.sup.3 is other than propyl; and

(b) an amount of anorganophosphorus compound sufficient to extend the soil life of said thiocarbamate, said organophosphorus compound having the formula ##STR34## in which R.sup.4 is C.sub.1 -C.sub.4 alkyl;

R.sup.5 is selected from the group consisting of C.sub.1 -C.sub.4 alkylthio, C.sub.2 -C.sub.4 alkenylthiol, and C.sub.2 -C.sub.4 alkynylthio;

R.sup.6 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.5 -C.sub.7 cycloalkyl and phenyl; and

R.sup.7 is selected from the group consisting of C.sub.2 -C.sub.4 alkenyl, C.sub.1 -C.sub.4 alkoxy, phenoxy and phenyl optionally substituted with one halogen atom.

2. An herbicidal composition according to claim 1 wherein

R.sup.5 is selected from the group consisting of C.sub.1 -C.sub.2 alkylthio or C.sub.2 -C.sub.4 alkynylthio;

R.sup.6 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.4 alkyl and cyclohexyl; and

R.sup.7 is selected from the group consisting of C.sub.1 -C.sub.4 alkoxy and phenoxy.

3. An herbicidal composition according to claim 2 wherein R.sup.4 is ethyl, R.sup.5 is methylthio or propargylthio, R.sup.6 is hydrogen, methyl or cyclohexyl and R.sup.7 is ethoxy or phenoxy.

4. An herbicidal composition according to claim 1 wherein the thiocarbamate is either S-propyl N,N-dipropylthiocarbamate or S-ethyl N,N-diisobutylthiocarbamate.

5. An herbicidal composition according to claim 4 whereen the organophosphorus compound is selected from the group consisting of S-methyl, ethylphosphonoamido ethyl carbamate; S-propargyl, ethylphosphonamido ethyl carbamate; S-methyl, ethylphosphonoamido ethyl-N-cyclohexyl carbamate; S-methyl, ethylphosphonoamido phenyl carbamate; and S-propargyl, ethyl phosphonamido ethyl-N-methyl carbamate.

6. An herbicidal composition according to claim 5 wherein the organophosphorus compound is S-propargyl, ethylphosphonoamido ethyl-N-methyl carbamate; S-propargyl, ethylphosphonoamido; or S-methyl, ethyl phosphonoamido phenyl carbamate.

7. An herbicidal composition according to claim 5 wherein the thiocarbamate is S-ethyl diisobutylthiocarbamate and the organophosphorus compound is S-methyl, ethyl phosphonamido phenyl carbamate of S-methyl, ethyl phosphonamido ethyl-N-cyclohexyl carbamate.

8. An herbicidal composition according to claim 5 wherein the organophosphorus compound is S-methyl, ethyl phosphonamido phenyl carbamate.

9. An herbicidal composition according to claim 1 in which the weight ratio of thiocarbamate compound to organophosphorus compound is from about 1:1 to about 5:1.

10. An herbicidal composition according to claim 1 further comprising a non-phytotoxic antidotally effective amount of either N,N-diallyl dichloroacetamide or 2,2,5-trimethyl-N-dichloroacetyl oxazolidine.

11. An herbicidal composition according to claim 10 wherein the thiocarbamate herbicide is either S-ethyl N,N-diisobutylthiocarbamate or S-propyl N,N-dipropylthiocarbamate and the antidote is N,N-diallyl dichloroacetamide.

12. An herbicidal composition according to claim 10 wherein the weight ratio of said thiocarbamate herbicide to said antidote is from about 3:1 to about 25:1.

13. A method of extending the soil life of a thiocarbamate having the formula ##STR35## in which R.sup.1, R.sup.2 and R.sup.3 are independently C.sub.1 -C.sub.4 alkyl with the proviso that wherein R.sup.1 is ethyl and R.sup.2 is propyl, R.sup.3 is other than propyl; which comprises applying to the soil containing said thiocarbamate or to which said thiocarbamate is to be applied, an effective amount of an organophosphorus compound having the formula ##STR36## in which R.sup.4 is C.sub.1 -C.sub.4 alkyl;

R.sup.5 is selected from the group consisting of C.sub.1 -C.sub.4 alkylthio, C.sub.2 -C.sub.4 alkenylthiol, and C.sub.2 -C.sub.4 alkynylthio;

R.sup.6 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.5 -C.sub.7 cycloalkyl and phenyl; and

R.sup.7 is selected from the group consisting of C.sub.2 -C.sub.4 alkenyl, C.sub.1 -C.sub.4 alkoxy, phenoxy and phenyl optionally substituted with one halogen atom.

14. A method according to claim 13 wherein

R.sup.5 is selected from the group consisting of C.sub.1 -C.sub.2 alkylthio or C.sub.2 -C.sub.4 alkynylthio;

R.sup.6 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.4 alkyl and cyclohexyl; and

R.sup.7 is selected from the group consisting of C.sub.1 -C.sub.4 alkoxy and phenoxy.

15. A method according to claim 13 wherein R.sup.4 is ethyl, R.sup.5 is methylthio or propargylthio, R.sup.6 is hydrogen, methyl or cyclohexyl and R.sup.7 is ethoxy or phenoxy.

16. A method according to claim 13 wherein the thiocarbamate is either S-propyl N,N-dipropylthiocarbamate or S-ethyl N,N-diisobutylthiocarbamate.

17. A method according to claim 16 wherein the organophosphorus compound is selected from the group consisting of S-methyl, ethylphosphonamido ethyl carbamate; S-propargyl, ethylphosphonamido ethyl carbamate; S-methyl, ethylphosphonamido ethyl-N-cyclohexyl carbamate; S-methyl, ethylphosphonoamido phenyl carbamate; and S-propargyl, ethyl phosphonamido ethyl-N-methyl carbamate.

18. A method according to claim 17 wherein the organophosphorus compound is S-propargyl, ethylphosphonoamido ethyl-N-methyl carbamate; S-propargyl, ethylphosphonamido; or S-methyl, ethyl phosphonoamido phenyl carbamate.

19. A method according to claim 17 wherein the organophosphorus compound is S-methyl, ethyl phosphonamido phenyl carbamate.

20. A method according to claim 13 in which the weight ratio of thiocarbamate compound to organophosphorus compound is from about 1:1 to about 5:1.

21. A method according to claim 13 further comprising a non-phytotoxic antidotally effective amount of either N,N-diallyl dichloroacetamide or 2,2,5-trimethyl-N-dichloroacetyl oxazolidine.

22. A method according to claim 21 wherein the thiocarbamate herbicide is either S-ethyl N,N-diisobutylthiocarbamate or S-propyl N,N-dipropylthiocarbamate and the antidote is N,N-diallyl dichloroacetamide.

23. A method according to claim 21 wherein the weight ratio of said thiocarbamate herbicide to said antidote is from about 3:1 to about 25:1.