# Patent

## Title
Control of plant fungi with S-p-methoxyphenyl

## Abstract

Disclosed are S-p-methoxyphenyl N,N-diallylthiolcarbamate and S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate. The latter compound possesses systemic nematocidal properties particularly against Meloidogyne species.

## Background
1. Field of the Invention

This invention concerns S-substituted phenyl, N,N-alkenyl and halogen substituted alkyl thiolcarbamates, in particular, S-p-methoxyphenyl, N,N-diallylthiolcarbamate and S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate. This invention also concerns the method of controlling the deleterious effects of nematodes upon plants, particularly by systemic control.

2. Description of the Prior Art

Nematodes (nemas) attack plants (trees, shrubs, etc.) and plant parts such as stems, roots, and bulbs causing deleterious effects by weakening the plant, decreasing the yield of fruit, stunting its growth, or causing lesions through which other parasitic organisms enter and harm the plant.

One method of combatting nematodes living in the soil, or upon decaying vegetation is to rotate the crops, but this is ineffective when the plants are maturing. Another methd is to use soil fungicides which kill nematodes, particularly those living in the soil, so as to rid the soil of these nematodes prior to crop planting. Examples of soil fungicides are methyl bromide, and chloropicrin. Soil fungicides are expensive, and in many cases are phytotoxic to plants. Another method is to apply nematocides to soil or to the bulbs to kill the nematodes prior to their entering the plant. Many nematodes, however, attack plants or become embedded within plants prior to application of the nematocide, or after the effective life of the nematocide, and these nematodes are not affected by such applications of nematocides. Another method is to apply systemic nematocides, which are applied to the plant; e.g., the foliage of the plant, to systemically control the deleterious effect of nematodes on the plant. This systemic control may result either from one or several different mechanisms. It may result from a translocation of the compound (or a metabolite thereof) from its application site (e.g., the foliage) to the area deleteriously affected by nematodes (the roots) where it controls the deleterious effect, e.g., by killing the nematodes or repelling them from the area, or by inducing rapid healing of the plant wound caused by the nematode. It may result from a translocation of the compound (or a metabolite thereof) from the application site (foliage) through the plant to outside the area deleteriously affected by nematodes (e.g., the roots), where it provides a protective shield against nematodes, such as a root coating which repels or kills nematodes feeding upon this area of the plant. It may result from the translocation of the compound or a metabolite thereof from its application site into the enzyme system of the plant where it stimulates formation of chemicals which repel or kill the nematodes attacking the plant or which rapidly heal the wounds caused by the nematodes.

Many thiolcarbamates are known as herbicides, fungicides, or nematocides, but very few are systemic nematocides. U.S. Pat. Nos. 2,977,209 and 3,265,563 disclose S-phenyl N-alkyl thiolcarbamates, S-chlorophenyl N-alkyl thiolcarbamates, S-ethoxy N-allylthiolcarbamate, and S-ethoxy N-alkyl thiol carbamates as herbicides and fungicides. U.S. Pat. Nos. 2,992,091 and 3,144,475 disclose S-substituted benzyl N,N-dialkylthiocarbamates and dithiocarbamates and defoliants and herbicides. U.S. Pat. No. 3,632,332 discloses S-4-methylbenzyl-N,N-diethylthiocarbamate as a herbicide for rice fields. U.S. Pat. No. 3,301,885 discloses S-substituted phenyl N-alkyl, N-alkoxy thiolcarbamates as herbicides, miticides, and insecticides. U.S. Pat. No. 3,687,653 discloses trifluoromethylbenzyl N-alkyl thiolcarbamates as herbicides. U.S. Pat. No. 3,046,189 and Canadian Pat. No. 789,575 discloses S-alkyl N-alkylthiocarbamates as nematocides.

S-p-methoxyphenyl N,N-diallylthiolcarbamate is an intermediate for the formation of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate which systemically controls nematodes; that is, when the compound is applied to a plant part, e.g., the foliage, either the compound, or a metabolite thereof translocates through the plant to the affected area, e.g., the roots, to control the deleterious effect of the nematode upon the plant. The compound S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate is effective against the Meloidogyne species, especially Meloidogyne incognita.

S-p-methoxyphenyl N,N-diallylthiolcarbamate is sometimes referred to as

S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate is sometimes referred to as

The following examples illustrate one method of synthesizing these compounds.

A 250 milliliter, three-necked flask was equipped with a power driven Trubore glass stirrer having a Teflon blade, an addition funnel and a Claisen type adapter fitted with a reflux condenser and thermometer. A heating mantle was placed around the flask. A solution of 1.50  grams (0.0154 moles) of diallylamine, an 1.30 grams (0.0128 mole) of triethylamine in 50 milliliters of benzene were placed in the flask. A solution of 2.60 grams (0.0128 mole) of p-methoxyphenylthiolchloroformate (also called 4-methoxyphenylthiolchloroformate) in 25 milliliters of benzene was placed in the addition funnel. This solution of p-methoxyphenylthiolchloroformate was slowly added (dropwise over a 15 minute period) to the vigorously stirred diallylamine solution. During the addition, the temperature rose from ambient to 37.degree. Centigrade. After the addition, the reaction mixture was refluxed at 80.degree. Centigrade for one hour, cooled to ambient temperature and then filtered to remove the white crystalline triethylamine hydrochloride salt. This filtrate of the benzene reaction mixture was washed with 100 milliliters of 2 weight percent aqueous hydrochloric acid solution, and then with 150 milliliters of water. It was then dehydrated with anhydrous magnesium sulfate (MgSO.sub.4) and refiltered. The filtrate was topped (that is volatiles were removed) under reduced pressure in a rotovac, to yield 3.5 grams of a pale yellow liquid (S-p-methoxyphenyl N,N-diallylthiolcarbamate). It had an infra-red spectrum with the carbonyl band (C.dbd.O) at 1650 cm.sup.-1.

Liquid bromine (4.1 grams, 0.0256 moles) was slowly added dropwise over a 20 minute period to a vigorously stirred, cooled (-5.degree. to 0.degree. Centigrade) solution containing p-methoxyphenyl N,N-diallylthiolcarbamate (3.4 grams, 0.0128 moles from Example I) in 75 milliliters of carbon tetrachloride. The reaction mixture was stirred and maintained at -5.degree. to 0.degree. Centigrade for two hours and then at ambient temperature for one hour. Afterwards the reaction solvent was removed by evaporating the mixture under reduced pressure in a rotovac. This left a thick, viscous product (7.2 grams) of p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate.

Infrared spectrum had a C.dbd.O band at 1650 cm.sup.-1,

NMR (CDCl.sub.3) had a singlet at 3.75 ppm (methoxy protons),

AA'xx' distorted doublet at 7.1 ppm (phenyl protons), and a

Complex multiplet at 3.35-4.8 ppm (N-bromoalkyl protons).

In lieu of triethylamine, for the synthesis of S-p-methoxyphenyl N,N-diallylthiolcarbamate, other tertiary amines may be used as the proton acceptor, such as trimethylamine, dimethylaniline, tributylamine, or N-methylmorpholine.

In the synthesis of the intermediate S-p-methoxyphenyl N,N-diallylthiolcarbamate, other inert solvents which dissolve the reactants and products, and which are easily removed from the products by evaporation, drying, filtering, or washing, and which have a boiling point appropriate to the reaction temperatures may be used in lieu of benzene. Examples are ethylether, methylethylether, methylpropylether, hexane, and chloroform. The reaction temperature may vary from 0.degree. C. to the boiling point of the refluxing mixture. Preferably the reaction temperature range is from 0.degree. C. to 80.degree. C.

Bromination may also be accomplished by bubbling bromine gas into a solution containing the intermediate S-p-methoxyphenyl N,N-diallylthiolcarbamate. The bromination reaction solvent is one which is readily removed from the product, dissolves the bromine, reactant or product, and has a boiling point appropriate to the bromination reaction temperature. Examples of such solvents are: carbon tetrachloride, chloroform, methylene chloride, CCl.sub.3 Br, and CCl.sub.2 Br.sub.2. The bromination reaction temperature may vary from -10.degree. C. to +50.degree. C.

As an alternative synthesis of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate, diallylamine may first be brominated to form bis(2,3-dibromopropyl)amine which could then be reacted with S-p-methoxyphenylthiolchloroformate.

Removal of the solvents, and reactants or other impurities from the S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate or S-p-methoxyphenyl N,N-diallylthiolcarbamate is not necessary except in so far as they interfere with the intended use of the compounds; such as the use of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate for systemic nematocidal control. All conventional purification techniques; such as recrystallization from solvents, fractional crystallization, washing with one or more solvents, followed by evaporation of the solvents, or filtration from the solvents, or their equivalents may be used.

Other routes may be used to synthesize S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate. For example, S-p-methoxyphenylthiol (also called S-p-methoxybenzenethiol) may be reacted with allylisocyanate in an inert solvent mentioned herein in the presence of a proton acceptor at temperatures from 15.degree. to 80.degree. C., to form the S-p-methoxyphenyl N-allylthiolcarbamate which is then brominated. Alternatively, 2,3-dibromopropylisocyanate may be substituted for allylisocyanate, and the reaction products from the isocyanate - thiol reaction may then be reacted with 1-bromo-2-propene, followed by bromination to form S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate.

In another method, p-methoxyphenylthiol may be reacted according to the process set forth in U.S. Pat. No. 3,165,544, with phosgene to form p-methoxyphenyl thiochloroformate which is then reacted with diallylamine or bis(2,3-dibromopropyl)amine as mentioned herein. The S-p-methoxyphenyl N,N-diallylthiolcarbamate is then brominated to form S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate.

Alternatively, diallylamine or bis(2,3-dibromopropyl)amine could be reacted with phosgene to form diallylcarbamoyl chloride, or bis(2,3-dibromopropyl)carbamoyl chloride. These carbamoyl chlorides are then reacted with p-methoxyphenylthiol in an inert solvent, mentioned herein, containing a proton acceptor, mentioned herein, to form the desired thiolcarbamate. The S-p-methoxyphenyl N,N-diallylthiolcarbamate is then brominated to form S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl) thiolcarbamate.

These examples illustrate systemic control of the deleterious effects of nematodes upon plants, particularly, those growing in soil infested with nematodes.

The examples illustrate the ability of the compound to control the adverse effect of nematodes on plants by application to the foliage of a plant. It achieves this without harm to the plant; e.g., without phytotoxic, or herbicidal effects upon the plant.

The test procedure for this example used a stock acetone solution consisting of 99.75 weight percent of acetone, 0.20 percent sorbitan trioleate (Span 85) and 0.05 percent sorbitan monooleate polyoxyalkene derivative (Tween 80). The test compound was dissolved in an aliquot of the stock solution, and deionized water was added to form the desired concentration for spraying. For example, 1200 mg. of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate was dissolved in 80 grams of the stock acetone solution, and this solution was diluted to 1000 grams, to form a spray solution containing 1200 ppm of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate.

Bonny Best tomato plants were grown from seedlings for four or five weeks in sterile soil until their height was 6 to 8 inches, and the plants had at least three fully expanded leaves (usually more).

The growing tomato plants were separated into two groups, those for spraying (treated) and control. The treated plants were passed through a spraying machine which sprayed them with the previously prepared test solution. The control group was not sprayed.

The solution containing S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate was applied as a spray by passing a tray of pots containing tomato plants, under a sprayer equipped with a Tee-Jet 8001 E spray nozzle tip and operating in the range of 35-40 pounds per square inch of pressure. The pot containing the plant was loaded within a tray which was placed on a conveyor belt moving at about 0.0625 mph (5.49 feet per minute). When the tray passed under the spray head, it tripped a microswitch which operated the sprayer. The spray was applied to the dripping point. The amount of compound within the solvent was adjusted to give the required application rate expressed as parts per million (ppm) per 30 milliliters of solution, or as pounds of active ingredient per 200 gallons per surface acre (lbs. ai/200 gal/acre) of soil. In these examples the sprayer sprayed 30 milliliters of solution per replicate. The sprayed plants were dried; then they and the control plants were transferred into soil infested with root-knot nematodes (Meloidogyne incognita), and grown under greenhouse conditions.

Both the sprayed (treated) and control plants were uprooted four (4) weeks after being transferred to the infested soil, and their roots were examined for root-knots which were counted in accordance with the method of W. M. Zeck. Pflanzenschutz - Nachrichten, Vol. 24, pages 141-144 (1971). The control is also rated according to the Zeck index. The root-knot counts were related to percent control by the following formula: treated)/(No. of root-knots in control)

Vydate (Dupont 1410 - methyl N',N'-dimethyl-N-[(methylcarbamoyl)oxy]-1-thiooxamimidate) a systemic nematocide known to be effective against the root-knot nematodes was also tested at the same concentration as the test compound and under the same conditions, as in internal check in some examples. Treated plants were also observed for evidence of damage by the applied test compound. This is reported on a scale of zero (0) to ten (10), with zero indicating no effect and ten indicating complete kill.

Five replicates per concentration of the test compound are made and an average percent control is determined based on these five replicates. Each replicate is based on 2 plants. An average value of 10 or higher indicates systemic control.

The test results are given in Table 1. Column 1 gives the example number; column 2 gives the concentration (conc.) of compound used expressed as parts per million (ppm); column 3 gives the individual percent control per replicate for the S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate from Example II; column 4 gives the average percent control for S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate and the plant injury; column 5 gives individual percent control per replicate of Vydate; column 6 gives the average percent control obtained with Vydate, and the plant injury; and column 7 gives the average Zeck index rating of the control plants.

The test results indicate that S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate systemically controls the deleterious effects of root-knot nematodes upon plants. __________________________________________________________________________ SYSTEMIC CONTROL OF ROOT-KNOT NEMATODE, (Meloidogyne incognita) UPON TOMATO PLANTS Compound S-p-methoxyphenyl N,N-bis(2,3-di- Applied bromopropyl)thiolcarbamate (Example II) Vydate Zeck Example Conc. Percent Control-Replicate Average Percent Percent Control-Replicate Average Percent Index No.  ppm (1) 1  2 3  4 5  Control: Plant Injury 1  2 3  4 5  Control: Plant Rating __________________________________________________________________________ III  500  51 67 67 51 67 61:0       59 59 73 86 86 73:0        * 7.4 IV   50   67 67 51 67 51 61:0       59 59 59 73 59 62:0       * 7.4 V     5   51 51 67 67 51 57:0       46 59 59 59 46 54:0       * __________________________________________________________________________ 7.4 Control plants had an average of 266 surface knots per plant based on 12 replicates. At high Zeck index ratings, only the knots on the outer roots (surface knots) are counted.

The deleterious effects of other Meloidogyne species may be systemically controlled by S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate. The species Meloidogyne exigua (Coffee Root-knot Nematode), Meloidogyne arenaria (Peanut Root-knot Nematode), Meloidogyne hapla (Northern Root-knot Nematode), and Citrus root Nematode are examples of other Meloidogyne species which may be controlled. Ditylonchus destructor (Potato Rot Nematode) is another nematode which may be controlled by this compound. The Meloidogyne incognita namatode in particular is systemically controlled by the compound.

Other species of nematodes may be controlled by applications other than systemic foliage contact, for example, by supplying the compound to the soil, by dipping the bulbs in solutions. Some examples of these other nematodes are: Aphelenchoides species Bud and Leaf Nematodes Anguina tritici  Wheat Nematode Anguina agrostis Grass Nematode Belonlainus species Sting Nematodes Criconemoides species Ring Nematodes Ditylonchus dipsaci Stem and Bulb Nematode Ditylonchus angustus Rice Nematode Dolichodorus heterocephalus Awl Nematode Helicotylenchus species Spiral Nematodes Heterodera rostochiensis Golden Nematode Heterodera tabacum Tobacco Cyst Nematode Heterodera schachtii Sugar Beet Nematode Heterodera carotae Carrot Root Nematode Heterodera gottingiana Pea Root Nematode Heterodera glycines Soybeam Cyst Nematode Hoplolaimus species Lance Nematodes Pratylenchus brachyurus Smooth-headed Lesion Nematode Pratylenchus species Meadow Nematodes Pratylenchus musicola Banana Nematode Pratylenchus zeae Corn Nematode Radopholus similis Burrowing Nematode Rotylenchus reniformis Kidney-shaped Nematode Trichodorus species Stubby-root Nematodes Tylenchorhynchus claytoni Tobacco Stunt Nematode Xiphinema species Dagger Nematodes ______________________________________

S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate itself may also be applied directly to the area where the deleterious effects of the nematodes are to be controlled, particularly against Meloidogyne species, especially Meloidogyne incognita species. It is, however, preferable to use suitable agricultural formulations which contain other ingredients which enhance application of this compound. These agricultural formulations will generally comprise from 5% to 95% by weight of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate, and either from 1% to 95% by weight of an agricultural diluent, or from 1% to 20% by weight of a surface active agent and other ingredients required to produce wettable powders, dusts, solutions, emulsifiable concentrates, granules, and the like, or both.

Wettable powders will contain from 25 to 80 percent active ingredients, from 0.1 percent to 5.0 percent wetters and dispersants with the balance consisting of inorganic absorptive diluents.

Since the compound is a viscous material, it may be thinned by heating and then sprayed upon the absorptive diluents of attapulgite clay, synthetic fine silica, and synthetic calcium and sodium aluminosilicates, or other solid insecticides, or foliar fungicides mentioned herein. It can be dissolved in a solvent and sprayed upon these solid diluents, and then the solvent is evaporated off.

Emulsifiable oils will contain from 20 percent to 97 percent active ingredient, from 3.0 to 10.0 percent of an emulsifying agent, and may also contain from 1 percent to 77 percent water-immiscible solvent such as xylene or alkylated naphthalene.

Granules will contain from 5 percent to 25 percent active ingredient, and may also contain from 1 percent to 20 percent of a surfactant extended upon a granular base such as vermiculite or granular attapulgite. Granules produced by extrusion or tumbling will contain like amounts of active ingredient and surfactant.

For the control of a wider range of crop-pests and diseases it is sometimes desirable to combine S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate with from 0.05 to 4 parts by weight of insecticides and fungicides, etc., known to be effective against crop-pests and diseases in concentrated premix or during the application step for foliar applications. Examples of other pesticides are: granules containing stable metal azide-metal salt formulations disclosed in assignee's copending application, Serial No. 624,357, filed Oct. 21, 1975 Sevin (1-naphthyl-N-methylcarbamate), Chlorobenzilate (ethyl 4,4'-dichlorobenzilate), Guthion (0,0-diethyl-S-[4-oxo-1,2,3-benzotriazin-3(4H)-ylmethyl]phosphorodithioate ), Disyston (0,0-diethyl-S-[2-(ethylsulfinyl)ethyl]phosphorodithioate, Maneb (manganous ethylene bisdithiocarbamate), Karathane (mixture of 2,4-dinitro-6-octylphenylcrotonate, 2,6-dinitro-4-octylphenylcrotonate, nitrooctylphenols (principally dinitro), 4-(1-methylheptyl)2,6-dinitrophenylcrotonate, 4-(1-ethylhexyl)2,6-dinitrophenylcrotonate, 4-(1-propylpentyl)2,6-dinitrophenylcrotonate, 6-(1-methylheptyl)-2,4-dinitrophenylcrotonate, 6-(1-ethylhexyl)2,4-dinitrophenylcrotonate, and 6-(1-propylpentyl)2,4-dinitrophenylcrotonate, Blasticidin (blasticidin-S-benzylaminobenzensulfonate), Benlate (methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, or Plantvax (5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide-4,4-dioxide).

In some instances it is also desirable to include special purpose additives which will inhibit corrosion, reduce foaming, reduce caking, or increase flocculation.

S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate, when used to control the deleterious effects of nematodes upon plants and plant parts, is applied in an effective amount as a suitable agricultural formulation within the vicinity of the infested area where the deleterious effects of the nematodes are to be controlled.

The phrase "to control the deleterious effects of nematodes upon plants and plant parts" means that the adverse effects of the nematodes upon the plants are reduced in intensity. This control may be direct control or systemic control which results from one mechanism or combination of several mechanisms; such as (a) direct killing of the nematodes; (b) repelling of the nematodes; or (c) rapid healing of the plant attacked by the nematode. In systemic control, S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate is applied within the vicinity of the infested area, e.g., to the foliage of the plant which has its roots infested by root nematodes, rather than directly to the infested area, e.g., the plant roots itself. Systemic control may result from a single mechanism or from a combination of mechanisms. It may result from a translocation of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate, (or a metabolite thereof) from its application site (e.g., the foliage), or to the area deleteriously affected by the nematodes (e.g., the roots, or the center portion of the stem) where it controls the deleterious effect; by (a) killing the nematodes; (b) repelling the nematodes; or (c) by healing the plant; or from translocation into the plant enzyme system where it induces the enzyme system to produce chemicals which (a) kill the nematodes or (b) repel them, or (c) which promote rapid healing of the plant. Systemic control may also result from a translocation of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate (or a metabolite of it) from its application site (foliage) through the plant to outside of the area (the roots) deleteriously affected by nematodes where it provides a protective shield against the nematodes; such as a root coating which repels or kills nematodes feeding upon this area of the plant.

The effective amount varies with the particular nematode involved, the application method used, e.g., systemic, soil incorporation, or dusting with a powder, the type of formulation utilized, the plant species to be protected, and local conditions such as temperature, humidity, moisture content of the soil, nature of the soil and the like. Since many factors are involved, different rates of application are selected for best results depending upon these specific conditions.

The phrase "applied to the parts of the plant" refers to any method of application as by spraying or dusting the part of the plant which is above-ground, such as its foliage, bark or stem, or plant parts which are underground, such as bulbs, canes, tubers, or roots with S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate.

For systemic control, S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate is applied preferably as a spray to the foliage of plants, particularly plants growing in soil infested with root-knot nematodes of the Meloidogyne species, particularly Meloidogyne incognita.

For other nematodes, it is possible to apply the compound by dipping the canes, or tubers, or bulbs affected by nematodes which attack these parts of the plants into solutions containing S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate, or by dusting these parts with granules or powders containing the compound.

The effective amount of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate for systemic control of Meloidogyne species, particularly Meloidogyne incognita, is a solution containing from 5 ppm to the maximum amount tolerated by the plants applied as a spray to the dripping point. In general it is from 5 ppm to 4,000 ppm, normally from 5 ppm to 500 ppm, and preferably from 5 ppm to 200 ppm.

These same amounts of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate are applied when the compound is used in combination with insecticides such as Sevin, Chlorobenzilate, Guthion, Disyston, or foliar fungicides such as Maneb, Karathane, Blasticidin, Benlate, or Plantvax. The amount of these other insecticides or fungicides will be in accordance with the label instructions disclosed in technical literature given with these known commercial compounds. In some cases, better control of the deleterious effects of nematodes is obtained when S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate is used in combination with the aforementioned insecticides and foliar fungicides.

Other application methods may include spraying above-ground parts such as stems, leaves and buds of plants in which nematodes are already present or where later attack is expected. Examples of these other applications are: dipping or soaking the reproductive parts in an aqueous suspension, solution or emulsion of an active ingredient; dusting above-ground parts or reproductive parts with a dust composition of an active ingredient; or immersing the root system to disinfect the plant or to provide protection against subsequent nematode invasion. The reproductive parts may be seeds, cane pieces, and bulbs which are infested or are to be planted in infested soil.

The effective amount of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate for applying directly to the infested area in which nematodes are present, or directly to areas which may become infested with nematodes is from 40 to 100 lbs. of the compound per acre, and preferably from 50 to 75 lbs. per acre of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate, the same amount mentioned herein. Of course, higher rates may also be used.

For a more effective control of the deleterious effects of root-knot nematodes upon plants, particularly Meloidogyne species, especially Meloidogyne incognita, it is preferable to apply a control nematocide such as azide, heavy metal formulations of azides, Nemagon, or S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate to the soil before planting the crops so as to reduce the number of pathogenic nematodes contained therein, and then after planting the crop to maintain control of the deleterious effects of nematodes on the plants by applying an effective amount of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate to systemically control the deleterious effects of the nematodes.

It is best to remove as much of the pathogenic pests from the soil, by applying azide compounds mentioned herein, or Nemagon, Nemacur, or S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate as well as Nemagon (1,2-dibromo-3-chloropropane), Nemacur (0-phenyl N,N'-dimethylphosphorodiamidate), as well as soil fungicides and insecticides, such as: Captan (cis-N-((trichloromethyl)thio)-4-cyclohexene-1,2-dicarboximide), Dexon (p-dimethylaminobenzenediazo sodium sulfate), PCNB (pentachloronitrobenzene), Furadan (2,3-dihydro-2,2-dimethyl-7-benzofuranylmethylcarbamate), Mocap (0-ethyl S,S-dipropylphosphorodithioate), or Temik (2-methyl 2(methylthio)propionaldehyde 0-(methylcarbamoyl)oxime), prior to planting the crops followed by one or more applications of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate to the plant's foliage during plant growth to maintain better systemic control of the deleterious effects of nematodes.

S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate is effective to control the deleterious effect of nematodes particularly Meloidogyne species and in particular Meloidogyne incognita upon plants affected by these nematodes; especially plants such as ornamentals, banana, avocado, sugar cane, pineapple, tobacco, citrus, soybeans, coffee, peanuts, corn, cucumbers, or garden crops such as sweet potato, tomato, carrot, celery, sugar beets, potato, etc.

The following example illustrates a suitable emulsifiable concentrate formulation for dilution in water for spraying plants, particularly, plant foliage or for application to other plant parts as herein mentioned. In this emulsifiable concentrate formulation, the percentages are weight percent. EMULSIFIABLE CONCENTRATE FORMULATIONS ______________________________________ S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl) 13% thiolcarbamate Xylene                     41% Isophorone                 41% Atlox.sup.(R) 3404 *        1% Atlox.sup.(R) 3403 F *      4% ______________________________________ * Commercial emulsifier for agricultural pesticides manufactured by Atla Powder Co., Wilmington, Delaware, and registered with the U.S. Food and Drug Administration.

The concentration of S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate in the emulsifiable concentrate may vary from 5 to 15 weight percent, the xylene may vary from 35 to 45 weight percent, isophorone may vary from 38 to 45 weight percent, Atlox.RTM. 3404 may vary from 0.5 to 3.0 weight percent and Atlox.RTM. 3403 F may vary from 3 to 6 weight percent.

The resulting emulsifiable concentrate of Example VI is dispersed in water, and using conventional spraying equipment the resulting suspension is applied at the rate of 50 lbs/200 gal of the S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate per acre (55 kilograms per hectare) to the surface of the soil in a field infested with the southern root-knot nematode (Meloidogyne incognita), and then promptly mixed in the soil to a depth of 10 to 15 centimeters with a rotovator prior to planting of tomato plants. This gave an effective 60 percent control of the deleterious effects of the nematodes upon the tomato plants.

While the invention has been described with reference to specific details of certain illustrative embodiments, it is not intended that it shall be limited thereby except insofar as such details appear in the accompanying claims.

## Claims

1. S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate.

2. A method of controlling the deleterious effects of nematodes upon plants and plant parts which comprises: N,N-bis(2,3-dibromopropyl)thiolcarbamate to the area deleteriously affected by said nematode to control said deleterious effects of the nematode.

3. A method of systemically controlling the deleterious effects of nematodes upon plants which comprises: N,N-bis(2,3-dibromopropyl)thiolcarbamate to the above-ground parts of the plant to control the deleterious effects of said nematode upon the plant.

4. The method as recited in claim 3, wherein said nematode is a nematode causing root-knots.

5. The method as recited in claim 4, wherein the plant is selected from the group consisting of an ornamental, banana, avocado, sugar cane, pineapple, tobacco, citrus, soybean, coffee, peanut, corn, cucumber, sweet potato, potato, tomato, celery, and sugar beet.

6. The method as recited in claim 5, wherein the nematode is Meloidogyne species.

7. The method as recited in claim 6, wherein S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate is applied to the foliage of said plants.

8. The method as recited in claim 7, wherein the nematode is selected from the group consisting of Meloidogyne incognita and Meloidogyne hapla.

9. A method of controlling the deleterious effects of pathogenic nematodes upon plants to be grown in soil infested with nematodes, which comprises: planting said plants to reduce the number of pathogenic nematodes contained therein, planting said plant in the treated soil, and N,N-bis(2,3-dibromopropyl)thiolcarbamate to the upper parts of the plant to control said deleterious effects of pathogenic nematodes upon said plant.

10. The method of claim 9, wherein the plant is selected from the group consisting of ornamentals, banana, avocado, sugar cane, pineapple, tobacco, citrus, soybean, coffee, peanut, corn, cucumber, sweet potato, potato, tomato, carrot, celery, and sugar beet.

11. The method as recited in claim 10, wherein the pathogenic nematode is a nematode causing root-knots.

12. The method as recited in claim 11, wherein the upper parts of the plant is the foliage of the plant.

13. The method as recited in claim 12, wherein the pathogenic nematode is a species of the genera Meloidogyne.

14. The method as recited in claim 12, wherein the pathogenic nematode is selected from the group consisting of Meloidogyne incognita and Meloidogyne hapla.

15. The method as recited in claim 14, wherein the contact nematocide is S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate.

16. A method of controlling the deleterious effects of soil nematodes upon plants growing in soil infested with nematodes which comprises: N,N-bis(2,3-dibromopropyl)thiolcarbamate to the soil to reduce the deleterious effects of said nematode upon said plant.

17. The method of claim 16, wherein S-p-methoxyphenyl N,N-bis(2,3-dibromopropyl)thiolcarbamate is applied prior to planting said plants.