Alkylthiocinnamic acid nitriles for the control of harmful organisms

BACKGROUND OF THE INVENTION
The invention concerns .alpha.-alkylthiocinnamic acid nitriles, processes for the production of these compounds as well as compositions containing the same and useful for the control of harmful organisms.
3-Alkylthio-2-aryl-acrylonitrile with herbicidal effectiveness are known, for example from U.S. Pat. No. 3,828,091. However, these compounds are not suitable for the control of harmful organisms.
It is therefore an object of the present invention to make available a composition which is effective in the control of such harmful organisms.
SUMMARY OF THE INVENTION
This object is attained according to the present invention by means of a composition that is characterized by a content of at least one .alpha.-alkylthiocinnamic acid nitrile of the general formula ##STR2## in which R is an aromatic hydrocarbon which may be substituted with at least one substituent selected from the group consisting of halogen, (C.sub.1 -C.sub.4) - alkyl, (C.sub.1 -C.sub.4) - alkoxy, (C.sub.1 -C.sub.4) - alkylthio and trifluoromethyl and R.sub.1 is a straight-chain C.sub.1 -C.sub.4 - alkyl or cyanoethyl.
The composition according to the present invention is suitable in an advantageous manner for the control of plant pest populations from the insect categories of Lepidoptera and Coleoptera. The composition in accordance with the invention provides its activity particularly with respect to the freshly laid eggs or egg spawns of the insects.
The surprising good nematocidal activity of the composition described above embraces also larvicide and ovicide activities with root gall nematodes as well as an emergence restraining effect with respect to the cyst-forming root nematodes (Meloidogyne - and Heterodera types), whereby they indeed surpass the conventionally known preparations of the same general activity according to vitro results.
It is of particular advantage that the composition according to the present invention can be employed for influencing the onset of any resistance by the harmful organism populations and for modern methods of control.
The application amount is determined according to the type of harmful pests to be controlled and amounts in general to between 0.5 and 20 kg/ha.
Of the compounds characterized by general formula I, those which are distinguished by a particularly good activity have the following substituents.
R is Phenyl, 2-Fluorophenyl, 3-Fluorophenyl, 4-Fluorophenyl, 2-Chlorophenyl, 3-Chlorophenyl, 4-Chlorophenyl, 2-Bromophenyl, PG,4 3-Bromophenyl, 4-Bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2,4-Difluorophenyl, 2,6-Difluorophenyl, Pentafluorophenyl, 2,4-Dichlorophenyl, 3,4-Dichlorophenyl, 2-Chloro-6-fluorophenyl, 2-Methylphenyl, 3-Methylphenyl, 4-Methylphenyl, 2-Methoxyphenyl, 3-Methoxyphenyl, 4-Methoxyphenyl, 2-Methylthiophenyl, 3-Methylthiophenyl, 4-Methylthiophenyl, 3-Trifluoromethylphenyl, 4-Trifluoromethylphenyl, 2-Pyridyl, 3-Pyridyl, 4-Pyridyl, 2-Thienyl, 3-Thienyl or 1-Naphthyl and
R.sub.1 is Methyl, Ethyl, Propyl, Butyl or Cyanoethyl.
A particularly outstanding insecticidal and ovicidal activity is evidenced for example by the following compounds:
.alpha.-Methylthio-cinnamic acid nitrile and
.alpha.-Methylthio-2-fluorocinnamic acid nitrile.
Mention may be made by way of example of the following particularly nematocidal by effective compounds:
.alpha.-Methylthio-4-chlorocinnamic acid nitrile
.alpha.-Methylthio-4-bromocinnamic acid nitrile
.alpha.-Methylthio-4-fluorocinnamic nitrile.
The compounds to be employed according to the present invention can be used either alone, in mixture with one another or with other active substances. If necessary, other plant protection or pest control agents can be added, indeed according to the desired purpose.
To the extent that a broadening of the activity spectrum is considered, other biocides can also be added. Moreover, even non-phytotoxic agents can be employed which, together with biocides, are able to provide a synergistic increase in activity, such as wetting agents, emulsifiers, solvents and oily additives.
Examples of other additives for inclusion in the composition of the invention are phospholipids, for example those from the groups Phosphatidylcholine, the hydrated Phosphatidylcholines, Phosphatidylethanolamine, the N-Acyl-phosphatidylethanolamines, Phosphatidylinosite, Phosphatidylserine, Lysolecithin and Phosphatidylglycerol.
Advantageously the active substances or their mixtures are employed in the form of preparations such as powders, spray agents, granulates, solutions, emulsions or suspensions, with the addition of liquid and/or solid carrier substances or diluting agents and, if necessary, wetting, adhering, emulsifying and/or dispersing adjuvants.
Suitable liquid carriers include, for example, water, aliphatic and aromatic hydrocarbons, such as Benzene, Toluene, Xylene, Cyclohexanone, Isophorone, Dimethylsulfoxide, moreover Mineral oil fractions and plant oils.
Suitable as solid carrier materials are mineral earths, for example Tonsil, Silicagel, Talcum, Kaolin, Attapulgite, Limestone, Silicic acid and plant derived products, for example, meal.
Surface-active substances that can be employed according to the present invention include, for example, Calcium lignin sulfonate, Polyoxyethylenealkylphenyl-ether, Naphthalene sulfonic acids and their salts, Phenol sulfonic acids and their salts, Formaldehyde condensates, fatty alcohol sulfate as well as substituted benzene sulfonic acids and their salts.
To the extent that the active substances according to the present invention are supposed to be employed for the disinfecting of seeds, even dyes can be admixed in order to provide the disinfected seeds with a clearly visible coloration.
The amount of the active substance(s) in the different preparations can vary within broad limits. For example, a composition may contain about 10 to 90 percent by weight active substance, about 90 to 10 percent by weight liquid or solid carrier material, as well as if necessary up to 20 percent by weight surface-active substance, with corresponding reduction in the amount of carrier material.
The application of the composition can take place in customary manner, for example with water as carrier in sprayable amounts of about 100 up to 1000 liter/ha. Employment of the composition in so-called "low volume" or "ultra-low volume" techniques is likewise possible, as is their application in the form of so-called microgranulates.
The following examples are set forth to illustrate production of the preparations according to the present invention:
A. SPRAY POWDER
(a)
40% by weight active substance
25% by weight clay minerals
20% by weight silicic acid
10% by weight cell pitch
5% by weight surface-active substance based upon a mixture of the calcium salt of lignin sulfonic acid with alkylphenolpolyglycolethers
(b)
25% by weight active substance
60% by weight kaolin
10% by weight silicic acid
5% by weight surface-active substance based upon the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of ligninsulfonic acid
(c)
10% by weight active substance
60% by weight clay minerals
15% by weight silicic acid
10% by weight cell pitch
5% by weight surface-active substance based upon the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of ligninsulfonic acid
B. PASTE
45% by weight active substance
5% by weight sodium aluminum silicate
15% by weight Cetylpolyglycolether with 8 Mole ethylene-oxide
2% by weight spindle oil
10% by weight Polyethyleneglycol
23 parts water
C. EMULSION CONCENTRATE
25% by weight active substance
15% by weight Cyclohexanone
55% by weight Xylene
5% by weight mixture of Nonylphenylpolyoxyethylene or Calcium dodecylbenzene sulfonate.
The compounds to be employed according to the present invention can be prepared in particularly advantageous manner by condensing an aromatic aldehyde of the general formula
R--CHO II
with an Alkylthioacetonitrile ##STR3## in the presence of 18-crown-6 as catalyst and with the addition of a base, if necessary dissolved in a solvent. Thereafter the desired reaction product is isolated in the known manner.
As a general rule Z E-isomers are produced on account of the double bond. The isomers can be separated, if desired, with the aid of traditional methods, such as fractional distillation or column chromatography. However, according to the present invention it is not only the particular Z-respectively E-components but also the Z, E-isomer mixture than can be employed.
The condensation reaction between aldehyde and alkylthioacetonitrile can be carried out with or without solvents. Suitable as solvents are mainly those substances inert with respect to the reactants, such as alcohols, ether, acetonitrile, toluene among others.
The reaction can be carried out generally within the basic pH-range, whereby alkali hydroxide can be added in small amounts (about 0.1 equivalent) as base, and with catalytic amounts of 18-crown-6.
The .alpha.-alkylthiocinnamic acid nitriles according to the present invention are generally colorless to yellow colored liquids of ester-like odor. They dissolve well in organic solvents, such as for example Benzene, Xylene, Cyclohexanone, Acetone, Methylenechloride, Chloroform, Ethanol, Acetonitrile and Dimethylformamide. They are less than one percent soluble in water.

The novel features which are considered as chacteristic for the invention are set forth in particular in the appended claims. The invention itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments.
EXAMPLE ONE
.alpha.-Methylthio-2-fluorocinnamic acid nitriles, Isomer mixture
65.36 g (0.75 Mol) Methylthioacetonitrile are dissolved in 750 ml Tetrahydrofuran. Then 5.6 g (0.1 Mol) Potassium hydroxide and 0.3 g 18-Crown-6 are added thereto. At 10.degree. C. and within a period of 20 minutes 93.08 g 2-Fluorobenzaldehyde in 250 ml Tetrahydrofuran are added dropwise. The reaction mixture is then stirred for two hours at 10.degree. C. and allowed to stand overnight. The solution is then filtered and the residue is washed with Tetrahydrofuran. It is then rotated in a vacuum, the remaining oil is withdrawn in one liter ethyl acetate and washed two times, each with 500 ml dilute sodium chloride solution. The ethyl acetate phase is dried over magnesium sulphate and after filtering off it is rotated in a vacuum. Subsequently the residue is distilled in an oil pump vacuum.
K.sub.P0.1-0.2 :98.degree.-103.degree. C. n.sub.D.sup.20 :1.6155.
Yield: 105.1 g=72.5% of Theoretical
A 60:40 E, Z-mixture is provided.
EXAMPLE TWO
Separation of Z, E-.alpha.-Methylthio-2-fluorocinnamic acid nitrile into E-.alpha.-Methylthio-2-fluorocinnamic acid nitrile and Z-.alpha.-Methylthio-2-fluorocinnamic acid nitrile
Preparative HPOC-chromotography of 210 mg Z, E-.alpha.-Methylthio-2-fluorocinnamic acid nitrile with isooctane: diisopropylether=1,000 ml: 4 ml provides:
115 mg E-.alpha.-Methylthio-2-fluorocinnamic acid nitrile ##STR4##
1H-NMR: SCH.sub.3 : 2.5 ppm(s); H-3, H-4, H-5, H C.dbd.: 6.9-7.5 ppm(m); H-6 : 8.03 ppm(m) and
84 mg Z-.alpha.-Methylthio-2-Fluorocinnamic acid nitrile ##STR5##
1H-NMR: SCH.sub.3 : 2.57 ppm(s); H-3, H-4, H-5, H C.dbd.: 6.9-7.5 ppm(m); H-6 : 7.78 ppm(m)
In a manner analogous to that set out in Example One, the following compounds have been prepared according to the present invention:
______________________________________Ex-am-pleNo. Name of Compound Physical Constant______________________________________3 .alpha.-Ethylthio-cinnamic acid Kp 136-42.degree. C./0.4 mm nitrile, Isomer mixture4 .alpha.-Ethylthio-2-chlorocinnamic Kp 155-57.degree. C./1 mm acid nitrile, Isomer mixture5 .alpha.-Ethylthio-4-chlorocinnamic Kp 130-35.degree. C./0.05 mm acid nitrile, Isomer mixture6 .alpha.-Ethylthio-2,4-dichlorocinnamic Kp 125-30.degree. C./0.05 mm acid nitrile, Isomer mixture7 .alpha.-Ethylthio-3,4-dichlorocinnamic Kp 142-48.degree. C./0.05 mm acid nitrile, Isomer mixture8 2-Ethylthio-3-(pyridine-2-yl)- Kp 145-50.degree. C./0.05 mm acylnitrile, Isomer mixture9 2-Ethylthio-3-(2-thienyl)- Kp 118-25.degree. C./0.05 mm acrylonitrile, Isomer mixture10 .alpha.-Ethylthio-2-methylcinnamic Kp 115-22.degree. C./0.05 mm acid nitrile, Isomer mixture11 .alpha.-Ethylthio-3-chlorocinnamic Kp 125-30.degree. C./0.05 mm acid nitrile, Isomer mixture12 .alpha.-Methylthio-cinnamic acid Kp 130-32.degree. C./0.4 mm nitrile, Isomer mixture13 .alpha.-Methylthio-3-chlorocinnamic Kp 128-30.degree. C./0.05 mm acid nitrile, Isomer mixture14 .alpha.-Methylthio-2-methylcinnamic Kp 115-19.degree. C./0.05 mm acid nitrile, Isomer mixture15 .alpha.-Methylthio-4-cinnamic acid n.sub.D.sup.20 : 1.6575 nitrile, Isomer mixture16 .alpha.-Methylthio-2-chlorocinnamic n.sub.D.sup.20 : 1.6401 acid nitrile, Isomer mixture17 .alpha.-Methylthio-4-bromocinnamic n.sub.D.sup.20 : 1.6780 acid nitrile, Isomer mixture18 .alpha.-Methylthio-2-methoxycinnamic n.sub.D.sup.20 : 1.6365 acid nitrile, Isomer mixture19 .alpha.-Methylthio-4-fluorocinnamic n.sub.D.sup.20 : 1.6165 acid nitrile, Isomer mixture20 2-Methylthio-3-(1-naphthyl)- n.sub.D.sup.20 : 1.6950 acrylonitrile, Isomer mixture21 2-Methylthio-3-(3-pyridyl)- n.sub.D.sup.20 : 1.6405 acrylonitrile, Isomer mixture22 2-Methylthio-3-(2-pyridyl)- n.sub.D.sup.20 : 1.6240 acrylonitrile, Isomer mixture23 .alpha.-Methylthio-2,4-dichloro- MP: 65-66.degree. C. cinnamic acid nitrile, Isomer mixture24 .alpha.-Methylthio-3-trifluorocinnamic n.sub.D.sup.20 : 1.5575 acid nitrile, Isomer mixture25 2-chloro-6-fluoro- n.sub.D.sup.20 : 1.6020 .alpha.-methylthio cinnamic acid nitrile26 .alpha.-Methylthio-4-trifluoro- n.sub.D.sup.20 : 1.5655 methylcinnamic acid nitrile, Isomer mixture27 .alpha.-Ethylthio-2-fluorocinnamic n.sub.D.sup.20 : 1.6020 acid nitrile, Isomer mixture28 .alpha.-Methylthio-4-methyl- n.sub.D.sup.20 : 1.6345 cinnamic acid nitrile, Isomer mixture______________________________________
The following operational examples serve to illustrate various use possibilities of the composition according to the present invention and which follow in the form of the above set forth preparations.
EXAMPLE TWENTY-NINE
Ovicidal activity with egg spawn of the Egyptian cotton moth (Spodoptera littoralis)
The compounds to be used according to the present invention are employed as aqueous suspensions with an active substance concentration of 0.1 percent. Into this active substance preparation there are immersed one day old egg spawns, which have been deposited onto filter paper from fertilized female moths, until complete wetting thereof. These are then placed for four days in closed Petri dishes for purposes of evaluation. Criteria for the activity valuation is the percentage of avoidance of the appearance of moths in comparison to the untreated egg spawns.
The obtained results are set forth and summerized in the following table:
______________________________________ Avoidance of Active Subtance Appearance Concentration of MothsCompounds in % in %______________________________________.alpha.-Ethylthio-cinnamic acid 0.1 100nitrile, Isomer mixture.alpha.-Ethylthio-2-chlorocinnamic 0.1 100acid nitrile, Isomer mixture.alpha.-Ethylthio-4-chlorocinnamic 0.1 100acid nitrile, Isomer mixture.alpha.-Ethylthio-2,4-dichloro- 0.1 100cinnamic acid nitrile, Isomermixture.alpha.-Ethylthio-3,4-dichloro- 0.1 100cinnamic acid nitrile, Isomermixture2-Ethylthio-3-(pyridine-2-yl)- 0.1 100acylnitrile, Isomer mixture2-Ethylthio-3-(2-thienyl)- 0.1 100acrylnitrile, Isomer mixture.alpha.-Ethylthio-2-methylcinnamic 0.1 100acid nitrile, Isomer mixture.alpha.-Ethylthio-3-chlorocinnamic 0.1 100acid nitrile, Isomer mixture.alpha.-Methylthiocinnamic acid 0.1 100nitrile, Isomer mixture.alpha.-Methylthio-3-chlorocinnamic 0.1 100acid nitrile, Isomer mixture.alpha.-Methylthio-2-methylcinnamic 0.1 100acid nitrile, Isomer mixture.alpha.-Methylthio-4-cinnamic acid 0.1 100nitrile, Isomer mixture.alpha.-Methylthio-2-chlorocinnamic 0.1 100acid nitrile, Isomer mixture.alpha.-Methylthio-4-bromocinnamic 0.1 100acid nitrile, Isomer mixture.alpha.-Methylthio-2-fluorocinnamic 0.1 100acid nitrile, Isomer mixture.alpha.-Methylthio-2-methoxycinnamic 0.1 100acid nitrile, Isomer mixture.alpha.-Methylthio-4-fluorocinnamic 0.1 100acid nitrile, Isomer mixture2-Methylthio-3-(1-naphthyl)- 0.1 100acrylonitrile, Isomer mixture2-Methylthio-3-(3-pyridyl)- 0.1 100acrylonitrile, Isomer mixture.alpha.-Methylthio-2,4-dichloro- 0.1 100cinnamic acid nitrile, Isomermixture.alpha.-Methylthio-3-trifluoromethyl 0.1 100cinnamic acid nitrile, Isomermixture2-Chlor-6-fluoro-.alpha.-methyl- 0.1 100thio-cinnamic acid nitrile.alpha.-Methylthio-4-trifluoro- 0.1 100methylcinnamic acid nitrile,Isomer mixture.alpha.-Ethylthio-2-fluorocinnamic 0.1 100acid nitrile, Isomer mixtureE--.alpha.-Methylthio-2-fluoro- 0.1 100cinnamic acid nitrileZ--.alpha.-Methylthio-2-fluoro- 0.1 100cinnamic acid nitrile.alpha.-Methylthio-4-methylcinnamic 0.1 100acid nitrile, Isomer mixture______________________________________
EXAMPLE THIRTY
Ovicidal activity with egg spawn of the Egyptian cotton moth (Spodoptera littoralis)
The compounds to be employed according to the present invention, as well as the comparison substances, are used as aqueous suspensions respectively emulsions having the desired concentrations. Into this active substance preparation are immersed one day old egg spawns, which have been deposited onto filter paper from fertilized female moths, until complete wetting thereof. The same are then placed for four days in closed Petri dishes for purposes of evaluation. Criteria for the activity evaluation is the percentage of avoidance of the appearance of moths in comparison to the untreated egg spawns.
The obtained results are set forth and summerized in the following table:
______________________________________ Avoidance Active Substance of Appear- Concentration ance ofCompounds in % Moth in %______________________________________.alpha.-Methylthio-cinnamic acid 0.0064 100nitrile.alpha.-Methylthio-2-fluoro- 0.0064 95cinnamic acid nitrileComparison Agent according toU.S. Pat. No. 38280912-(4-Chlorophenyl)-3-iso- 0.0064 0propylthio-acrylonitrile2-3-Butylthio-2-(4-Chloro- 0.0064 0phenyl)-acrylonitrile2-(4-Chlorophenyl)-3-ethyl- 0.0064 0thio-acrylonitrile______________________________________
EXAMPLE THIRTY-ONE
Ovicidal activity with egg spawns of the Mexican bean beetle (Epilachna varivestis)
The compounds to be used according to the present invention, as well as the comparison substances, are employed as aqueous suspensions respectively emulsions with having the desired concentrations. Into this active substance preparation are immersed one day old egg spawns, which have been deposited from fertilized female beetles onto primary leaves of the bush bean (Phaseolus vulgaris), until complete wetting. They are then deposited and kept for six days in closed Petri dishes. Criteria for the evaluation of activity is the percentage of avoidance of the appearance of moths in comparison to the untreated egg spawns.
The obtained results are set forth and summerized in the following table:
______________________________________ Avoidance Active Substance of Appear- Concentration ance ofCompounds in % Moths in %______________________________________.alpha.-Methylthio-cinnamic acid 0.04 95nitrile.alpha.-Methylthio-2-fluorocinnamic 0.04 95acid nitrile.alpha.Ethylthio-2-fluorocinnamic 0.04 50acid nitrileComparison Agent According toU.S. Pat. No. 3 828 0912-(4-Chlorophenyl)-3-Isopropyl- 0.04 0thioacrylonitrile2-3-Butylthio-2-(4-chlorophenyl)- 0.04 0acrylonitrile2-(4-Chlorophenyl)-3-ethyl- 0.04 0thioacrylonitrile______________________________________
EXAMPLE THIRTY-TWO
Nematocidal effectiveness with L.sub.2 -larvae of the root gall nemotode (Meloidogyne incognita).
The compounds to be employed according to the present invention are prepared as suspensions of powder form formulations: the comparison agents are provided as aqueous solution. Freshly evolved L.sub.2 -larvae from egg spawns of root gall nemotodes are placed in the solutions and after 24 hours the activity respectively inactivity of the larvae are determined by microscopy. The results are set forth in the following table.
______________________________________ Active Substance ConcentrationCompounds 0.01 0.005 0.0025 0.0012 0.0006%______________________________________.alpha.-Methylthio-4-chloro- 100 100 100 100 100%cinnamic acid nitrile.alpha.-Methylthio-4-bromo- 100 100 100 100 100%cinnamic acid nitrile.alpha.-Methylthio-4-fluoro- 100 100 100 100 95%cinnamic acid nitrileComparison Agent1-(Dimethylaminocarb- 100 95 70 30 0%onyl)-N--(methylamino-carbonyloxy)-thioform-hydroxamic acid-methyl-esterUntreated Control 0 0 0 0 0%______________________________________
EXAMPLE THIRTY-THREE
Ovicidal effectiveness with egg spawns of root gall nemotode (Meloidogyne incognita)
The compounds to be employed according to the present invention are prepared as a suspension of a powder form formulation, whereas the comparison agents are provided as aqueous solution. Freshly obtained egg spawns from Capsicum anuum are washed and then placed into the solution. After a period of 48 hours there is carried out a substantial washing of the treated egg spawns under flowing water. For each of the concentrations five egg spawns are put into clear water and allowed to develop at a temperature of 24.degree. C. until the emergence of larvae. The following table shows the number of appearing L.sub.2 -larvae from each five egg spawns after eight days.
______________________________________ Active Substance ConcentrationCompounds 0.01 0.005 0.0025 0.0012%______________________________________.alpha.-Methylthio-4-chloro- 0 0 0 0cinnamic acid nitrile.alpha.-Methylthio-4-bromo- 0 0 0 0cinnamic acid nitrile.alpha.-Methylthio-4-fluoro- 0 0 0 50cinnamic acid nitrileComparison Agent1-(Dimethylaminocarb- 400 400 400 400 (app.)onyl)-N--(methylamino-carbonyloxy)-thioform-hydroxamic acid-methyl-esterUntreated Control 400 400 400 400 (app.)______________________________________
EXAMPLE THIRTY-FOUR
The Emergence-restraint activity regarding the cyst content of Heterodera schachtii
The compounds to be employed according to the present invention are prepared as suspension of powder form formulations: the comparison agents are presented as aqueous solution. Cysts of the rape nematode Heterodera schachtii are thoroughly washed under flowing water after a working period of 48 hours, and are placed into root diffusate at 24.degree. C. for purposes of L.sub.2 -larvae emergence, five cysts for each concentration.
The following table shows the number of emergent L.sub.2 -larvae from each five cysts after eight days.
______________________________________ Active Substance Concentration:Compounds 0.02 0.01 0.005 0.0025%______________________________________.alpha.-Methylthio-4-chloro- 0 0 0 0cinnamic acid nitrileComparison Agent1-(Dimethylaminocarb- 400 400 400 400onyl)-N--(methylamino-carbonyloxy)-thioform-hydroxamic acid-methyl-esterUntreated Control 400 400 400 400______________________________________
Although the invention has been described as embodied in .alpha.-alkylthiocinnamic acid nitriles for the control of harmful organisms, it is not intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential chacteristics of the generic or specific aspects of this invention.

Number	Name	Date	Kind
3828091	Strong	Aug 1974
3852276	Cresswell et al.	Dec 1974

Alkylthiocinnamic acid nitriles for the control of harmful organisms

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