US3312589A - Fungicidal liquid concentrate with propylene glycol - Google Patents

Fungicidal liquid concentrate with propylene glycol Download PDF

Info

Publication number
US3312589A
US3312589A US510101A US51010165A US3312589A US 3312589 A US3312589 A US 3312589A US 510101 A US510101 A US 510101A US 51010165 A US51010165 A US 51010165A US 3312589 A US3312589 A US 3312589A
Authority
US
United States
Prior art keywords
weight
propylene glycol
fungicidal
percent
dodine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US510101A
Inventor
William J Entley
Jr Harry A Stansbury
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Union Carbide Corp
Original Assignee
Union Carbide Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Union Carbide Corp filed Critical Union Carbide Corp
Priority to US510101A priority Critical patent/US3312589A/en
Priority claimed from GB646167A external-priority patent/GB1103989A/en
Application granted granted Critical
Publication of US3312589A publication Critical patent/US3312589A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof

Definitions

  • This invention relates to a liquid concentrate formulation for fungicidal mixtures.
  • U.S. Patent 3,166,469 to Pass et al. discloses the advantages of applying fungicidal compositions containing two previously known fungicides in combination, viz. 2-heptadecylglyoxalidine which is sold by Union Carbide Corporation under the common name Glyodin, and n-dodecylguanidine acetate, sold by American Cyanamid Company under the trademark Cyprex and commonly known as Dodine.
  • Glyodin and Dodine as used hereinafter are intended to refer to the commercially pure chemicals which are the fungicidally active components in formulations containing them.
  • This fungicidal mixture has, however, been limited by the solubility characteristics of the two components which are such as to have heretofore precluded development of a stable liquid formulation concentrate.
  • a concentrate is convenient to use and thus preferred by orchardists.
  • Glyodin is a waxy solid with a melting point of 62 C. to 68 C. and is thus not readily formulated as a wettable powder.
  • Commercially, it is sold in an isopropanol solution containing 30 percent by weight of Z-heptadecylglyoxalidine in the form of its acetate salt.
  • table powder formulation containing 65 percent by weight of n-dodecylguanidine acetate, the remainder being an inert particulate solid carrier, e.g., bentonite, and about 5 percent of a surfactant.
  • aqueous formulations for the fungicidal mixture are described in the Pass et al. patent in Examples 1 and 2.
  • One is a liquid mix in which a 30 percent solution of Glyodin in isopropanol and Dodine as a 65 percent wettable powder are charged into a tank full of water and the resulting mixture is continuously agitated tokeep the components in suspension.
  • a dry product is applied as a spray by suspending the dry powder in a large volume of 'water and maintaining vigorous agitation.
  • the present invention provides .a liquid concentrate in which the technical Glyodin and Dodine have been mixed in proportions optimum for fungicidal eifectiveness.
  • the invention utilizes the technically pure active fungicidal ingredients and thus obviates prior formulation of the Glyodin in isopropanol and of the Dodine as a wettable powder as required by the prior art techniques.
  • Being a liquid concentrate the present formulation is easy to handle and obviates all the problems of working with a dust described above.
  • the liquid concentrate of this invention forms a solution when added to water so that the actual spray need not be kept under constant agitation.
  • the present invention comprises liquid concentrate formulations containing Glyodin and Dodine characterized by the presence of propylene glycol. It has been found that when certain percentages of propylene Dodine is normally available as a wet' glycol are added to the two-component fungicidal mixture, a stable liquid concentrate formulation is obtained which exhibits excellent sprayability when mixed with water. In this respect the use of propylene glycol has been found critical inasmuch as the use of other common solvents did not result in usable formulations but rather led to formation of turbid suspensions not suited for mixing or spraying. V
  • compositions of this invention may contain the two active fungicidal components in a proportion of from about 0.8 part by weight to about 15 parts by weight of Glyodin per part by weight of Dodine. However, in preferred combinations, from 1 to about 8 parts of Glyodin are provided for every part of Dodine and the optimum ratio is about 4 parts of Glyodin for every part of Dodine. Use of this ratio appears to result in most eflfective disease control.
  • the compositions are further characterized in that they contain from about 10 to about 30 parts by weight of propylene glycol per part by Weight of Dodine. It has been found that at least 10 parts by weight of propylene glycol per part of Dodine are required to give readily water-dilutable concentrates.
  • compositions may contain a certain amount of isopropanol or other solvent in which the technical Glyodin material may be commercially available.
  • the liquid concentrate formulations of this invention thus contain from about 10 to about 40 percent by weight of Z-heptadecylglyoxalidine, from about 3 to about 10 percent by weight of n-dodecylguanidine acetate, and from about 50 to about 87 percent by weight of propylene glycol, provided that at least 10 parts by weight of propylene glycol are provided for every part by weight of n-dodecylguanidine acetate.
  • the liquid concentrates are prepared by'physically admixing the components in the above indicated ratios to result in a clear solution. If the concentrates are used at very low temperatures (ca 0 C.) slight warming may be necessary to maintain a clear, readily dilutable concentrate. If one of the fungicidal components is available in solution, e.g., Glyodin in isopropanol, such a solutionmay be admixed with the other components of the concentrate and the isopropanol optionally evaporated by distillation under reduced pressure.
  • the formulation of this invention was applied to combat bean mildew, bean rust, tomato early blight and cucumber anthracnose in side-by-side tests with the conventional formulations described above, according to the following procedure.
  • Bean, tomato, and cucumber plants were sprayed on a revolving turntable with the indicated formulation for 30 seconds to apply about milliliters of formulation.
  • the treated plants were then stored at room temperature for a period of 24 hours. After the storage period, one half of the plants were sprayed on the turntable with 200 milliliters of water (indicated as rain treatment) and then dried. The remaining half received no additional treatment. Then all of the test plants were infested with the indicated fungus by brushing their leaves lightly with infested plants from a stock culture, or by spraying them with a stock spore suspension.
  • n-d0decylguanidine acetate are provided for every part by weight of n-d0decylguanidine acetate.
  • a fungicidal concentrate as claimed in claim 1 comprising from about 10 to about 40 percent by weight of 2- heptadecylglyoxalidine, about 1 part by weight of n-dodecylguanidine acetate for every 4 parts of 2-heptadecylglyoxalidine, and about 10 parts by weight of propylene gylcol for every part of n-dodecylguanidine acetate.
  • a fungicidal concentrate as claimed in claim 2 comprising from about to about 28 percent by weight of 2- heptadecylglyoxalidine, from about 6 to about 8 percent by weight of n-dodecylguanidine acetate, and about 65 percent by weight of propylene glycol.
  • the concentrate contained 65 percent by weight of propylene glycol in each instance;
  • liquid formulation of this invention possesses the advantages of a liquid formulation with undiminished fungicidal efiectiveness.
  • a fungicidal liquid concentrate formulation comprising from about 10 to about 40 percent by weight of 2- heptadecylglyoxalidine, from about 3 to about 10 percent References Cited by the Examiner UNIT ED STATES PATENTS 1/1965 Pass 167-22 References Cited by the Applicant UNITED STATES PATENTS 3,166,469 1/1965 Pass et al. SAM ROSEN, Primary Examiner. S. I. FRIEDMAN, Assistant Examiner.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

United States Patent Ofiice 3,3 12,589 Patented Apr. 4, 1967 3,312,589 FUNGICIDAL LIQUID CONCENTRATE WITH PROPYLENE GLYCOL William J. Entley, Charleston, and Harry A. Stansbury,
In, South Charleston, W. Va., assignors to Union Carbide Corporation, a corporation of New York No Drawing. Filed Nov. 26, 1965, Ser. No. 510,101 3 Claims. (Cl. 167-42) This invention relates to a liquid concentrate formulation for fungicidal mixtures.
U.S. Patent 3,166,469 to Pass et al. discloses the advantages of applying fungicidal compositions containing two previously known fungicides in combination, viz. 2-heptadecylglyoxalidine which is sold by Union Carbide Corporation under the common name Glyodin, and n-dodecylguanidine acetate, sold by American Cyanamid Company under the trademark Cyprex and commonly known as Dodine. The terms "Glyodin and Dodine as used hereinafter are intended to refer to the commercially pure chemicals which are the fungicidally active components in formulations containing them.
The utility of this fungicidal mixture has, however, been limited by the solubility characteristics of the two components which are such as to have heretofore precluded development of a stable liquid formulation concentrate. Such a concentrate is convenient to use and thus preferred by orchardists. Glyodin is a waxy solid with a melting point of 62 C. to 68 C. and is thus not readily formulated as a wettable powder. Commercially, it is sold in an isopropanol solution containing 30 percent by weight of Z-heptadecylglyoxalidine in the form of its acetate salt. table powder formulation containing 65 percent by weight of n-dodecylguanidine acetate, the remainder being an inert particulate solid carrier, e.g., bentonite, and about 5 percent of a surfactant.
The two known aqueous formulations for the fungicidal mixture are described in the Pass et al. patent in Examples 1 and 2. One is a liquid mix in which a 30 percent solution of Glyodin in isopropanol and Dodine as a 65 percent wettable powder are charged into a tank full of water and the resulting mixture is continuously agitated tokeep the components in suspension. In the other formulation a dry product is applied as a spray by suspending the dry powder in a large volume of 'water and maintaining vigorous agitation.
The difliculty with these known formulations is that they require handling of a dust material by the applicator which involves mixing problems, contamination of persons and facilities, and waste of some material. In addition, the tank water needs to be continuously agitated to maintain suspension of the dust. I
The present invention provides .a liquid concentrate in which the technical Glyodin and Dodine have been mixed in proportions optimum for fungicidal eifectiveness. The invention utilizes the technically pure active fungicidal ingredients and thus obviates prior formulation of the Glyodin in isopropanol and of the Dodine as a wettable powder as required by the prior art techniques. Being a liquid concentrate, the present formulation is easy to handle and obviates all the problems of working with a dust described above. In addition, the liquid concentrate of this invention forms a solution when added to water so that the actual spray need not be kept under constant agitation.
Essentially, the present invention comprises liquid concentrate formulations containing Glyodin and Dodine characterized by the presence of propylene glycol. It has been found that when certain percentages of propylene Dodine is normally available as a wet' glycol are added to the two-component fungicidal mixture, a stable liquid concentrate formulation is obtained which exhibits excellent sprayability when mixed with water. In this respect the use of propylene glycol has been found critical inasmuch as the use of other common solvents did not result in usable formulations but rather led to formation of turbid suspensions not suited for mixing or spraying. V
The compositions of this invention may contain the two active fungicidal components in a proportion of from about 0.8 part by weight to about 15 parts by weight of Glyodin per part by weight of Dodine. However, in preferred combinations, from 1 to about 8 parts of Glyodin are provided for every part of Dodine and the optimum ratio is about 4 parts of Glyodin for every part of Dodine. Use of this ratio appears to result in most eflfective disease control. The compositions are further characterized in that they contain from about 10 to about 30 parts by weight of propylene glycol per part by Weight of Dodine. It has been found that at least 10 parts by weight of propylene glycol per part of Dodine are required to give readily water-dilutable concentrates. Use of more than 30 parts of propylene glycol results in low toxicant concentration in the concentrate and gives no advantages in stability or sprayability of the diluted concentrate. In addition, the compositions may contain a certain amount of isopropanol or other solvent in which the technical Glyodin material may be commercially available. The liquid concentrate formulations of this invention thus contain from about 10 to about 40 percent by weight of Z-heptadecylglyoxalidine, from about 3 to about 10 percent by weight of n-dodecylguanidine acetate, and from about 50 to about 87 percent by weight of propylene glycol, provided that at least 10 parts by weight of propylene glycol are provided for every part by weight of n-dodecylguanidine acetate.
The liquid concentrates are prepared by'physically admixing the components in the above indicated ratios to result in a clear solution. If the concentrates are used at very low temperatures (ca 0 C.) slight warming may be necessary to maintain a clear, readily dilutable concentrate. If one of the fungicidal components is available in solution, e.g., Glyodin in isopropanol, such a solutionmay be admixed with the other components of the concentrate and the isopropanol optionally evaporated by distillation under reduced pressure.
To demonstrate the criticality of using propylene glycol comparative tests were carried out using the following materials in place of propylene glycol: ethylene glycol, isopropanol, butyl Cellosolve, dimethylformamide, dimethylsulfoxide, Carbitol acetate, Cellosolve acetate, ethylene glycol diacetate, 1,3-butanediol, glycerol.
Use of each of the above materials in the amounts indicated for propylene glycol results in a cloudy, turbid suspension unsuitable for agricultural application.
To determine the effectiveness of the formulation of this invention in agricultural applications, the formulation of this invention was applied to combat bean mildew, bean rust, tomato early blight and cucumber anthracnose in side-by-side tests with the conventional formulations described above, according to the following procedure.
Bean, tomato, and cucumber plants were sprayed on a revolving turntable with the indicated formulation for 30 seconds to apply about milliliters of formulation. The treated plants were then stored at room temperature for a period of 24 hours. After the storage period, one half of the plants were sprayed on the turntable with 200 milliliters of water (indicated as rain treatment) and then dried. The remaining half received no additional treatment. Then all of the test plants were infested with the indicated fungus by brushing their leaves lightly with infested plants from a stock culture, or by spraying them with a stock spore suspension.
The plants were held for visually rated according to 1) =no activity (2)=little control (3) =about 50% effective (4) =excellent control (5 =complete control the following designations:
The results are set forth in Table 1, below. Concentrations of the active toxicants in the applied formulation are given in parts per million for each toxicant.
are provided for every part by weight of n-d0decylguanidine acetate.
2. A fungicidal concentrate as claimed in claim 1 comprising from about 10 to about 40 percent by weight of 2- heptadecylglyoxalidine, about 1 part by weight of n-dodecylguanidine acetate for every 4 parts of 2-heptadecylglyoxalidine, and about 10 parts by weight of propylene gylcol for every part of n-dodecylguanidine acetate.
3. A fungicidal concentrate as claimed in claim 2 comprising from about to about 28 percent by weight of 2- heptadecylglyoxalidine, from about 6 to about 8 percent by weight of n-dodecylguanidine acetate, and about 65 percent by weight of propylene glycol.
TABLE I.-FUNGICIDAL TEST RESULTS FOR COMBINATIONS OF GLYODIN AND DODINE IN DIFFERENT FORMULATIONS Ratings Counts 1 Concentration of active Formulation toxicant in Early Blight Bean Rust water (p.p.m.) Cucumber, Anthrac- No Rain nose, Rain 3 No Rain Rain 2 N 0 Rain Rain 2 Dodine (tehnical) 3 250 3 3 4 3 4 5 5 5 9 23 60 4 4 3 3 4 4 4 4 39 89 15 2 2 2 2 3 3 1 3 56 84 Dodine (65% wettable powder) 250 2 2 3 3 4 4 5 4 91 28 60 2 3 4 4 4 4 4 4 63 49 15 3 3 2 2 3 3 3 3 78 Dead G1 odin" 30 solution in iso ro anol 1,035 2 2 2 2 5 5 5 5 70 23 y p p 259 2 2 2 2 4 4 5 5 44 57 65 1 1 1 1 1 1 4 4 64 42 Glyodin (307 solution in isopropanol) plus Dodine (technicalyfli 1, 035-1 250 5 5 5 5 31 259+60 3 3 3 3 5 5 5 5 22 56 65-1-15 3 3 3 3 5 4 3 32 36 Glyodin (307 solution in isopropanol) plus Dodine (65% wettable powder) 1, 035+250 5 5 5 26 259+60 4 4 4 4 5 5 4 5 53 65+15 4 4 3 3 5 4 5 3 66 65 Glyodin (technical) plus Dodine (technical) in propylene glycol 1, 035+250 5 5 5 5 34 36 259+60 4 4 4 4 5 5 4 5 39 59 65-1-15 3 3 4 4 3 4 5 4 48 43 Control 1 l 1 l 1 1 1 1 136 169 1 Number of lesions per 4 leaves. 2 Water (200 m1.) sprayed on plants 24 hours after treatment. 3 Dissolved in ethyl alcohol before addition of water. The final fo 4 The sprayed plants showed a phytotoxic response.
rmulations at 250 ppm. contained 10 percent alcohol by volume.
5 The concentrate contained 65 percent by weight of propylene glycol in each instance;
It can be seen that the liquid formulation of this invention possesses the advantages of a liquid formulation with undiminished fungicidal efiectiveness.
What is claimed is:
1. A fungicidal liquid concentrate formulation comprising from about 10 to about 40 percent by weight of 2- heptadecylglyoxalidine, from about 3 to about 10 percent References Cited by the Examiner UNIT ED STATES PATENTS 1/1965 Pass 167-22 References Cited by the Applicant UNITED STATES PATENTS 3,166,469 1/1965 Pass et al. SAM ROSEN, Primary Examiner. S. I. FRIEDMAN, Assistant Examiner.

Claims (1)

1. A FUNGICIDAL LIQUID CONCENTRATE FORMULATION COMPRISING FROM ABOUT 10 TO ABOUT 40 PERCENT BY WEIGHT OF 2HEPTADECYLGLYOXALIDINE, FROM ABOUT 3 ABOUT 10 PERCENT BY WEIGHT OF N-DODECYLGUANIDINE ACETTE, AND FROM ABOUT 50 TO ABOUT 87 PERCENT BY WEIGHT OF PROPYLENE GLYCOL, PROVIDED THAT LEAST 10 PARTS BY WEIGHT OF PROPYLENE GLYCOL, ARE PROVIDED FOR EVERY PART BY WEIGHT OF N-DODECYLGUANIDINE ACETATE.
US510101A 1965-11-26 1965-11-26 Fungicidal liquid concentrate with propylene glycol Expired - Lifetime US3312589A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US510101A US3312589A (en) 1965-11-26 1965-11-26 Fungicidal liquid concentrate with propylene glycol

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US510101A US3312589A (en) 1965-11-26 1965-11-26 Fungicidal liquid concentrate with propylene glycol
GB646167A GB1103989A (en) 1967-02-10 1967-02-10 Fungicidal concentrates

Publications (1)

Publication Number Publication Date
US3312589A true US3312589A (en) 1967-04-04

Family

ID=26240712

Family Applications (1)

Application Number Title Priority Date Filing Date
US510101A Expired - Lifetime US3312589A (en) 1965-11-26 1965-11-26 Fungicidal liquid concentrate with propylene glycol

Country Status (1)

Country Link
US (1) US3312589A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163800A (en) * 1977-08-17 1979-08-07 The Procter & Gamble Company Topical composition and treatment of skin lesions therewith
EP0722658A1 (en) * 1995-01-06 1996-07-24 Calgon Corporation Storage stable biocide composition and process for making the same
WO2012152318A1 (en) * 2011-05-10 2012-11-15 Agriphar S.A. Agrochemical formulations comprising dodecylguanidine and a compatibility agent
US9226507B2 (en) 2011-07-19 2016-01-05 Alan Pirotte Method for producing emulsifiable pesticide solutions
CN107304175A (en) * 2016-04-21 2017-10-31 上海生农生化制品有限公司 A kind of synthetic method of dodine
US10582706B2 (en) 2011-08-22 2020-03-10 Alan Pirotte Aqueous suspension concentrate comprising an acid salt of dodecylguanidine

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3166469A (en) * 1961-06-13 1965-01-19 Sherwin Williams Company Of Ca Pesticidal composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3166469A (en) * 1961-06-13 1965-01-19 Sherwin Williams Company Of Ca Pesticidal composition

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163800A (en) * 1977-08-17 1979-08-07 The Procter & Gamble Company Topical composition and treatment of skin lesions therewith
EP0722658A1 (en) * 1995-01-06 1996-07-24 Calgon Corporation Storage stable biocide composition and process for making the same
WO2012152318A1 (en) * 2011-05-10 2012-11-15 Agriphar S.A. Agrochemical formulations comprising dodecylguanidine and a compatibility agent
US20140088198A1 (en) * 2011-05-10 2014-03-27 Agriphar S.A. Agrochemical formulations containing a compatibility agent
US9247732B2 (en) * 2011-05-10 2016-02-02 Alan Pirotte Agrochemical formulations containing a compatibility agent
US9226507B2 (en) 2011-07-19 2016-01-05 Alan Pirotte Method for producing emulsifiable pesticide solutions
US9770031B2 (en) 2011-07-19 2017-09-26 Arysta Lifescience Benelux Sprl Method for producing emulsifiable pesticide solutions
US10582706B2 (en) 2011-08-22 2020-03-10 Alan Pirotte Aqueous suspension concentrate comprising an acid salt of dodecylguanidine
CN107304175A (en) * 2016-04-21 2017-10-31 上海生农生化制品有限公司 A kind of synthetic method of dodine

Similar Documents

Publication Publication Date Title
US3666668A (en) Cleanser, disinfectant, combinations thereof and aerosol systems containing same
US2577969A (en) Compositions for killing weeds
US2909420A (en) Compositions and methods for influencing the growth of plants
EP0087049B1 (en) Concentrate of disinfecting agent
US5175353A (en) 2-(2'-aminoethoxy)-ethanol salt of dicamba
US4452630A (en) Stable, heat-resistant solutions of pesticidal carbamates
US3312589A (en) Fungicidal liquid concentrate with propylene glycol
US3492110A (en) Triazine herbicide formulations
US3628941A (en) Antimicrobial solutions of dodecylguanidine hydrochloride having low-temperature stability
US3986862A (en) Emulsifiable liquid concentrates containing 4-amino-6-t-butyl-3-(methylthio)-1,2,4-triazin-5-one and 2-chloro-n-(2,6-diethylphenyl)-n-methoxymethylacetamide
US3152882A (en) Method for destroying weeds
US2262454A (en) Pest control
KR920003209B1 (en) Fungicidal composition
US3173832A (en) Paraformaldehyde stabilized fungicidal compositions
US4438137A (en) Pesticidal compositions employing amitraz with stabilizer
US3697589A (en) N-(4-carboxy-benzylidene)amines
US4218444A (en) Insecticidal formulation
US2923658A (en) Fungicidal compositions and methods employing p-chloro-omega-thiocyano acetyl benzene
CS253735B2 (en) Herbicide mixture
US2884356A (en) Fish toxicant compositions and method of using them
US3639616A (en) Pesticidal formulations
US3048483A (en) Synergistic herbicidal composition
PT88005B (en) PROCESS FOR THE PREPARATION OF PHOSPHONY SALTS
US2777762A (en) Method and composition for the control of undesirable vegetation
US3961052A (en) Fungicidal compositions