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US2973297A - Fungicidal quaternary ammonium salts of dithiocarbamic acids - Google Patents

Fungicidal quaternary ammonium salts of dithiocarbamic acids Download PDF

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US2973297A
US2973297A US814407A US81440759A US2973297A US 2973297 A US2973297 A US 2973297A US 814407 A US814407 A US 814407A US 81440759 A US81440759 A US 81440759A US 2973297 A US2973297 A US 2973297A
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ammonium
cetyl
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pyridinium
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Mattheus H C M Bakkeren
Jurrien J Schuur
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AAGRUNOL CHEMICAL WORKS NV
Nv Aagrunol Chemical Works
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    • 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
    • A01N47/08—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 one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14—Di-thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C07C333/16—Salts of dithiocarbamic acids

Definitions

  • This invention relates to fungicidal compositions and processes which employ quaternary ammonium salts of substituted dithiocarbamic'acids and of ethylenebisdithiocarbamic acid.
  • Fungi infections of plants have in the past been minimized or prevented by application to the plants of sodium, zinc, iron and other such salts of dithiocarbamic acids and similar salts of the ethylenebisdithiocarbamic acid. These materials, however, will not control a fungus infection which has become well established.
  • the fungicidal compounds employed are, speaking generally, quaternary ammonium salts of dithiocarbamic acid.
  • quaternary ammonium radical of the novel compound has a higher alkyl group attached to the nitrogen atom, the remaining radicals attached to the nitrogen atom being alkyl and/or aralkyl.
  • the quaternary ammonium radical is pyridinum
  • R is an aliphatic hydrocarbon group of 10 to 18 carbons.
  • R is hydrogen or an aliphatic hydrocarbon group of less than 5 carbons.
  • R is an aliphatic or aralkyl hydrocarbon group-of less than 13 carbons.
  • R is methyl or ethyl.
  • the compounds as above described are extremely effective as fungicides against plant pathogenic fungi and afford the valuable and unique effect of controlling such fungi even many hours after the incidence of infection. Often it is impossible to spray plants before the fungus infection occurs and, particularly in rainy periods, it is impossible to spray soon enough after infection to control the disease.
  • the compositions and methods of the present invention provide a way of controlling such plant pathogenic fungi long after they would be past control by nonmercurial fungicides heretofore available.
  • compositions and processes of the invention are especially valuable for the control of fungi which infect trees such as fruit-bearing trees. Control of such fungi can be obtained up to three days after infection.
  • composition which is used to treat the plants may include, in addition to a compound or compounds of the present invention, other fungicides, insecti- "cides, and/or other agents for controlling noxious organisms.
  • the compounds employed according to the present invention are preferably prepared by a double conversion of a soluble quaternary ammonium salt, such as chloride, with a soluble salt of a dithiocarbamic acid, such as a sodium salt.
  • R is an aliphatic hydrocarbon group ofless than 5
  • R is methyl or ethyl, or R R and R taken together with the nitrogen atom form the pyrindium group.
  • a quaternary ammonium chloride is reacted with an equimolecular amount of an appropriate alkali metal dithiocarbamate in water to produce a precipitate.
  • This precipitate will contain impurities such as the halide salt of the alkali metal and ordinarily the crude mixture thus obtained will be used as such in the composition and processes of the present invention.
  • the quaternary ammonium dithiocarbamate can be further purified to separate it from the salt and any other impurities.
  • the fungicidal activity of this product was tested according to the slide germination method of evaluating fungicides (Phytopathology, 33, 627-632) with regard to the fungi Clasterosporium carpophilum and Fusarium morass? a solani.
  • the LD-SO was found to 0.1 and 1.4 pzpnn'
  • Example 2 Reaction of sodium dimethyldithiocarbamate with cetyl pyridinium bromide to produce cetyl pyridinium dimethyldithiocarbamate.
  • Cetyl pyridinium bromide (38.4 grams, 0.1 mole) is dissolved in warm water to give a 20% solution at 55 C. This solution is added over a Zil-minute period, with stirring, to a solution of sodium dimethydithiocarbamate (14.3 grams, 0.1 mole) in 130 ml. water. A viscous brown solution forms which upon cooling to 5 C. forms a very thick slurry. The product is isolated by filtering, reslurrying in ice water, filtering and drying at room temperature. It is a brownish orange waxy solid, melting at 55-61 C., and is sufficiently pure for fungicidal application. The small amounts of water and bromide ion contained in this material may be removed by conventional means.
  • the water may be removed by vacuum drying at elevated temperatures, and the bromide ion can be removed by recrystallization or chromatography over alumina, using chloroform as bath solvent and eluent.
  • the purified product melts at LD-50 LID-50' Claszer- Fumrium ospnrium sola'ni carpophilnm Reaction product oi sodium dimethyldithio- I carbamate with:
  • cetylpyridinium chloride 1.6 4
  • stearyl dimethyl benzyl ammonium ch1oride 10
  • cetyl dimcthyl benzyl ammonium chloride 6 '1 Reaction product of sodium meihyldithiocarbamate with:
  • cetylpyridinium chloride 0:5 4 13. tetradeeyl trimethyl ammonium chloride 2 6 14. stearyl dimethyl benzy ammonium chloride 2' 10 15. cetyl dimethyl benzyl ammonium chloride 2 4 16. dodccyl dimethyl benzyl ammonium chloride 2 10 Reaction product oi sodium diethyldithiocarbamate with:
  • Cetyl trimethyl ammonium bromide to make cetyl trimethyl ammonium di-n-butyldithiocarbamate 43.
  • Cetyl pyridinium'bromide to make cetylpyridinium e'thylenebisdithiocarbamate 51.
  • Stearyl n-butyl diethyl ammonium chloride to make stearyl n-butyl diethyl ammonium ethylenebisdithiocarbamate 56.
  • Stearyl trimethyl ammonium chloride to make stearyl trimethyl ammonium ethylenebisdithiocarbamate 5 8. Decyl triethyl ammonium chloride to make decyl triethyl ammonium ethylenebisdithiocarbamate 59. Undecyl trimethyl ammonium chloride to make undecyl trimethyl ammonium ethylenebisdithiooarbamate 60. Stearyl triethyl ammonium chloride to make stearyl triethyl ammonium ethylenebisdithiocarbamate 61.
  • Stearyl benzyl diethyl ammonium chloride to make stearyl benzyl diethyl ammonium ethylenebisdithiocarbamate Reaction product of sodium di-n-propyldithiocarbamate with 62.
  • Cetyl pyridinium bromide to make cetyl pyridinium di-n-propyldithiocarbamate 63.
  • Stearyl trimethyl ammonium chloride to make stearyl trimethyl ammonium di-n-propyldithiocarbamate Reaction product of sodium N-methyl-N-ethyldithiocar- Reaction product of sodium N-methy-l-N-isopropyldithiocarbamate with:
  • Cetyl pyridinium chloride to make cetyl pyridinium N-methyl-N-ethyldithiocarbamate 65.
  • Dodecyl benzyl diethyl ammonium chloride to make dodecyl benzyl diethyl ammonium N-methyl- N-ethylenedithiocarbamate Reaction product of sodium N-methyl-N-(n-butyl)dithio- Reaction product of sodium N-ethyl-N-(n-propyl)dithiocarbamate with:
  • Stearyl decyl dimethyl ammonium chloride to make stearyl decyl dimethyl ammonium N-ethyl- N- (n-propyl dithiocarbamate carbamate with:
  • Cetyl benzyl dimethyl ammonium chloride to make cetyl benzyl dimethyl N-(n-propyl)-N-(nbutyl) dithiocarbamate 73.
  • Cetyl pyridinium bromide to make cetyl pyri- Reaction product of sodium ethyldithiocarbamate with: 74.
  • Cetyl pyridinium bromide to make cetyl pyridinium ethyldithiocarbamate
  • Cetyl dimethyl benzyl ammonium chloride to make cetyl dimethyl benzyl ammonium ethyldithio carbamate Reaction product of sodium n-propyldithiocarbamate with:
  • Fungicidal compositions of the present invention containing at least one of the quaternary ammonium products as above described can be prepared by admixing one or more of these products with pest control adjuvants or modifiers to provide compositions in the form of waterdispersible powders, dusts, solutions, and emulsifiable solutions.
  • pest control adjuvants or modifiers to provide compositions in the form of waterdispersible powders, dusts, solutions, and emulsifiable solutions.
  • the quaternary ammonium dithiocarbamates employed in compositions of the invention can be formulated in any conventional manner and used in processes of the invention for the control of fungi, it is much preferred that they be formulated in compositions which contain a free-flowing, inert powder. Still more preferred are such. mixtures in which one or more surfactants are present.
  • the free-flowing, inert powders can be any of the extenders commonly employed in the insecticide, herbicide and fungicide art for the application of such materials and may include natural clays such as attapulgite and kaolinite clays, diatomaceous earth, talcs, synthetic mineral fillers derived from silica and silicate such as synthetic fine silica and synthetic calcium or magnesium silicate, wood flour and walnut shell flour.
  • natural clays such as attapulgite and kaolinite clays, diatomaceous earth, talcs
  • synthetic mineral fillers derived from silica and silicate such as synthetic fine silica and synthetic calcium or magnesium silicate, wood flour and walnut shell flour.
  • the amount of the extenders can vary widely and can range from about 10 to 95% by weight of a fungicidal composition.
  • the amount of dithiocarbamate will range from about 5 to
  • the particle size can vary considerably but will ordinarily be somewhat under 50 microns in the finished formulation.
  • the compositions can be prepared with a pulverulent extender or with an extender with particles above the desired size and after admixture with the quaternary ammonium dithiocarbamate the entire composition can be suitably ground so that the particle size of the extender will be small enough to give free-flowing compositions which can readily be applied. Particle size will usually run something under 50 microns in such finished products.
  • compositions as described can, in addition to the finely divided extender, contain a surfactant.
  • the surfactant can be a dispersant, a de-foamer or an emulsifying agent which will assist dispersion of the composition in the water.
  • the surfactants or surface-active agents can include such cationic and non-ionic surface-active agents as have heretofore been generally employed in pest control compositions of similar type. Suitable surface-active agents are set out, for example, in Searle US. Patent 2,426,417, Todd US. Patent 2,655,447, Jones US. Patent 2,412,510, or Lenher US. Patent 2,139,276. A detailed list of such agents is set forth by J. W. McCutcheon in Soap and Chemical Specialties, December 1957, Januseats;
  • Suitable surfactants for use in compositions of the present invention are alkyl and alkyl aryl polyether alcohols, polyoxyethylene sorbitol or sorbitan fatty acid esters, polyethylene glycol fatty esters and fatty alkylol amide condensates.
  • the amount of surface-active agent will be less than 1% by Weight.
  • the amount will range from about 0.5 to 2% of a surface-active agent.
  • Particularly preferred surface-active agents include polyvinyl alcohol, methocels, gum arabic, long chain amine acetates, substituted oxazolines and alkyl dimethylamine oxides.
  • compositions of the invention are very slightly water soluble and are cationic in nature, thus, to greater or lesser extents, various of the compounds above described act as wetting and dispersing agents. This action, however, will often be insufiicient and a suitable non-ionic or cationic dispersant should also be added.
  • compositions containing free-flowing, finely divided extenders and with or without an added wetting agent are much preferred compositions of the invention, it Will be understood that the quaternary ammonium compounds can be used in processes of the invention by formulation and application in various conventional manners.
  • the compounds though only slightly soluble can be dissolved in water at the point of use to obtain enough of the active material to obtain control of fungi.
  • the quaternary ammonium compounds to be used in the processes of the invention can also be dissolved in appropriate non-phytotoxic organic solvents.
  • a concentrate thus formed can be mixed with water, using a dispersing agent if one is necessary.
  • This cetylpyridinium dimethyldithiocarbamate can be dissolved to form a concentrated solution in dimethylformamide and this can be mixed with an appropriate quantity of water to obtain the concentration of the dithiocarbamate desired.
  • Suitable solvents are lower molecular weight aromatic hydrocarbons, usually benzene, toluene, xylene and alkylated naphthalene, volatile, low molecular weight esters, and water immiscible ketones such as ethyl to amyl acetate and methylisobutyl ketone to dibutyl ketone.
  • Emulsifiable oils can be prepared in the same fashion using an oil in which the dithiocarbamate is soluble, such as xylene.
  • Such emulsifiable oils can contain other suitable solvents for the quaternary ammonium dithiocarbamates as above.
  • suitable surfactants should be used such as cationic or non-ionic agents known to the art as emulsifying agents as above described.
  • fungicidal control is obtained by applying the active compound at a dosage, or at a rate, from about 0.05 to 5 pounds per acre.
  • the optimum amount in each instance is largely dependent upon the exact method of application, the state and condition of growth of plants to be treated, the climatic conditions and other such well-understood variables.
  • pear scab peach scab, cedar-apple rust, cherry leaf spot, .Broolrs spot, sooty blotch, bitter rot, black rot, black spot (of roses) and apple blotch.
  • Example 80 A fungicidal composition was prepared by mixing 20 parts by weight of cetylpyridinium dimethyldithiocarbamate with parts by weight of a filler (fullers earth) and 10 parts byweight of dispersing agent (refined sulfite lye powder). This composition is identified as composition A in Tests I and II below and is sprayed in the form of a. suspension containing 0.2% of composition A.
  • composition Z containing of zinc dimethyldithiocarbamate in two tests for controlling Venturia inaequalis (apple scab) on the James Grieve variety. The results were as follows:
  • Test 1 The trees were sprayed 24 hours after infection of the leaf. After spraying 20 days elapsed before the percentage of leaf surface affected by scab was determined.
  • Test II The trees were sprayed as in Test I but this time 48 hours after infection of the leaf. After spraying 19 days elapsed before the percentage of leaf surface affected by scab was determined.
  • Composition Z Average percent of leaf surface affected by scab Treatment of tree 1 Composition Z, 0.1%. Composition A, 0.2%. 0.2
  • Example 81 Percent Cetyl pyridinium dimethyldithiocarbamate 20 Attapulgite clay 80 The above composition is prepared by blending the components together and passing through a micropulven'zer until substantially all agglomerates are broken down to 50 microns or smaller.
  • This formulation is applied at the rate of 2 pounds per gallons of water to an apple orchard 48 hours after a scab infection period. Excellent curative action on the scab infection is obtained and the trees are protected from re-infection by the disease.
  • Example 82 Percent Cetyl trimethylammonium dirnethyldithiocarbamate 50 Low viscosity polyvinyl alcohol 1 Synthetic fine silica 49
  • the above wettable powder is prepared as in Example 81.
  • This formulation is applied at the rate of 1 /2 pounds per 100 gallons in the first cover spray for control of apple scab and cedar-apple rust in an apple orchard. Good control of both diseases is obtained.
  • Example 83 Percent Cetyl pyridinium dimethyldithiocarbamate 20 A blend of long chain fatty amides 2 Xylene 78 The above emulsifiable composition is prepared by simple mixing of the mutually soluble components. When dispersed in water this compositions forms a cationic emulsion. i
  • This formulation is applied at the rate of 1 pint per 100 gallons toa grove of Bartlett pears as a preventive treatment for control of pear scab. Sprayed trees are protected from the disease while unsprayed trees are severely infected with scab.
  • Example 84 Percent Dodecyl tn'methylammonium dimethyldithiocarbamate 25 Attapulgite clay 75
  • Example 85 Percent Tetradecyl trimethylammonium dimethyldithiocarbamate Diatomaceous silica The above wettable powder is prepared in the same manner as Example 81.
  • This formulation is applied at the rate of 2 pounds per 100 gallons to a pear orchard 48 hours after a scab infection period. Developing scab lesions on the leaves are eradicated and the trees protected from early reinfection by scab and also from sooty blotch disease.
  • Example 86 Percent Cetyl dimethyl benzylammonium dimethyldithiocarbamate 10 Attapulgite clay 40 Pyrophyllite 50
  • Example 87 Percent Tetradecyl trimethylammonium diethyldithiocarbamate 50 Synthetic fine silica 50
  • the above wettable powder is prepared in the same manner as Example 81.
  • This composition is included at a rate of /1 pounds per 100 gallons in the shnck-fall spray in a cherry orchard for control of cherry leaf spot. Excellent control of the disease is obtained on the treated trees.
  • Example 88 Percent Stearyl dimethyl benzylammonium diethyldithiocarbamate 50 Synthetic fine calcium silicate (neutral) 50 The above wettable powder is prepared in the same manner as Example 81.
  • This composition is applied at the rate of 1 pound per 100 gallons to an interplanted apple and peach orchard for the control of apple scab, peach scab, sooty blotch, and frog-eye leaf spot. Good control of both apple and peach diseases results.
  • Example 89 Percent Cetyl pyridinium ethylenebisdithiocarbamate 20 Mixed long chain fatty amides 2 Xylene 78 The 'above emulsifiable oil is prepared in the same manner as Example 83.
  • This composition is applied to a planting of crab apple tree for protection from attack by apple scab. A rate of 1 pint per acre is used, and good protection is afforded from the fungus disease.
  • Example 90 Percent Cetyl dimethyl benzylammonium ethylenebisdithiocarbamate l0 Attapulgite clay 30 Micaceous talc 60
  • the above dust is prepared by first blending and grinding the active component with the minor diluent until substantially all agglomerates are reduced to below 50 microns, then blending this mix with the major diluent.
  • a row of grapes is dusted just prior to bloom with this composition at the rate of 10 pounds per acre for protection against black rot. Repetition of the treatment immediately after bloom and at two weeks after bloom gives good control of the disease.
  • Example 91 Percent Cetyl trimethylammonium ethylenebisdithiocarbamate 25 Attapulgite clay The above wettable powder is prepared in the same manner as Example 81.
  • the compounds above numbered 1 to 79 can be formulated in each of the ways shown.
  • the quaternary ammonium dithiocarbamate there named can be replaced with an equal weight of the quaternary ammonium dithiocarbamate of Examples 1 to 79 and applied as shown.
  • a method for controlling plant pathogenic fungi comprising applying to a plant a fungicidally elfective amount of:
  • Q is selected from the group consisting of R is an alkyl hydrocarbon group of 10 to 18 carbons
  • R is selected from the group consisting of hydrogen and an alkyl hydrocarbon group of less than 5 carbons
  • R is an alkyl hydrocarbon group of less than 5 carbons
  • R is selected from the group consisting of an alkyl and aralkyl hydrocarbon group of less than 13 carbons, and, when R N and R taken together comprise a pyridinium group, a merged constituent of such pyri' dinium group,
  • R is selected from the group consisting of methyl and ethyl
  • V R is' selected from the group consisting of methyl, ethyl, and, when R N, and R taken together comprise a pyridinium group, a merged constituent ofsuchpyridinum group.
  • a method for controlling plant pathogenic fungi comprising applying to a plant a fungicidally' effective amount of cetyl pyridinium dimethyldithiocarbamate.
  • a method for controlling plant pathogenic fungi comprising applying to a plant a fungicidally effective amountof cetyl pyridinium ethylenebisdithiocarbamate.
  • a methodfor-controlling plant pathogenic fungi comprising applying to a planta fungicidally efl'ective amount of cetyl pyridjninm methyldithiocarbamate.
  • a method for controlling plant pathogenic fungi comprising applying to a plant a fungicidally effective amountof cetyl pyridinium diethylidthiocarbamate;

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Description

United States Tatent O FUNGICIDAL QUATERNARY ANIMONIUM SALTS OF DITHIOCARBAMIC ACIDS Mattheus H. C. 'M. Bakkeren and Jurrien J. Schuur, Groningen, Netherlands, assignors to N.V. Aagrunol Chemical Works, Groningen, Netherlands, a limitedliability company of the Netherlands No Drawing. Filed May 20, 1959, Ser. No. 814,407
6 Claims. (Cl. 16722) This invention relates to fungicidal compositions and processes which employ quaternary ammonium salts of substituted dithiocarbamic'acids and of ethylenebisdithiocarbamic acid.
Fungi infections of plants have in the past been minimized or prevented by application to the plants of sodium, zinc, iron and other such salts of dithiocarbamic acids and similar salts of the ethylenebisdithiocarbamic acid. These materials, however, will not control a fungus infection which has become well established.
Mercurial fungicides have been used for the control of established fungi infection but such mercurials are too toxic to be entirely satisfactory.
According to the present invention, the fungicidal compounds employed are, speaking generally, quaternary ammonium salts of dithiocarbamic acid. These com- A preferred scope of the invention may instead be stated by saying that according to the preferred form of the invention, the quaternary ammonium radical of the novel compound has a higher alkyl group attached to the nitrogen atom, the remaining radicals attached to the nitrogen atom being alkyl and/or aralkyl. Of course, when the quaternary ammonium radical is pyridinum,
three of the positions of the nitrogen atom constitute part methyldithiocarbamic acid, diethyldithiocarbamic acid and pounds may be applied to the objects or articles to be R is an aliphatic hydrocarbon group of 10 to 18 carbons. R is hydrogen or an aliphatic hydrocarbon group of less than 5 carbons.
carbons R is an aliphatic or aralkyl hydrocarbon group-of less than 13 carbons.
R is methyl or ethyl.
agents,
ethylenebisdithiocarbamic acid.
The compounds as above described are extremely effective as fungicides against plant pathogenic fungi and afford the valuable and unique effect of controlling such fungi even many hours after the incidence of infection. Often it is impossible to spray plants before the fungus infection occurs and, particularly in rainy periods, it is impossible to spray soon enough after infection to control the disease. The compositions and methods of the present invention provide a way of controlling such plant pathogenic fungi long after they would be past control by nonmercurial fungicides heretofore available.
The compositions and processes of the invention are especially valuable for the control of fungi which infect trees such as fruit-bearing trees. Control of such fungi can be obtained up to three days after infection.
If desired. the composition which is used to treat the plants may include, in addition to a compound or compounds of the present invention, other fungicides, insecti- "cides, and/or other agents for controlling noxious organisms.
The compounds employed according to the present invention are preferably prepared by a double conversion of a soluble quaternary ammonium salt, such as chloride, with a soluble salt of a dithiocarbamic acid, such as a sodium salt.
R is an aliphatic hydrocarbon group ofless than 5 R is methyl or ethyl, or R R and R taken together with the nitrogen atom form the pyrindium group.
While any of the dithiocarbamates above shown can be 55 employed, by far the best results for the purposes of the present invention are obtained using those of Formula 1 in which Q is 3)z 'purifietl if desired.
Thus, a quaternary ammonium chloride is reacted with an equimolecular amount of an appropriate alkali metal dithiocarbamate in water to produce a precipitate. This precipitate will contain impurities such as the halide salt of the alkali metal and ordinarily the crude mixture thus obtained will be used as such in the composition and processes of the present invention. vAlternatively, the quaternary ammonium dithiocarbamate can be further purified to separate it from the salt and any other impurities.
In like manner, two molecular equivalents of an appropriate quaternary ammonium halide can be reacted with one molecular equivalent of disodium ethylenebisdithiocarbamate, or another alkali metal ethylenebisdithio- .carbamate, in water to produce a precipitate. This can be used as such or the dithiooarbamate portion can be Example 1 g.. of cetylpyridinium chloride (0.25 mol) were dissolved in 600 ml. of water to which were added, while stirring, 3 6 g. sodium dimethyldithiocarbamate (0.252 mol), dissolved in 180 ml. of water. g. of a palebrown colored product (cetylpyridinium dimethyldithioca'rbamate) were separated from the reaction mixture.
The fungicidal activity of this product was tested according to the slide germination method of evaluating fungicides (Phytopathology, 33, 627-632) with regard to the fungi Clasterosporium carpophilum and Fusarium morass? a solani. The LD-SO was found to 0.1 and 1.4 pzpnn' Example 2 Reaction of sodium dimethyldithiocarbamate with cetyl pyridinium bromide to produce cetyl pyridinium dimethyldithiocarbamate.
Cetyl pyridinium bromide (38.4 grams, 0.1 mole) is dissolved in warm water to give a 20% solution at 55 C. This solution is added over a Zil-minute period, with stirring, to a solution of sodium dimethydithiocarbamate (14.3 grams, 0.1 mole) in 130 ml. water. A viscous brown solution forms which upon cooling to 5 C. forms a very thick slurry. The product is isolated by filtering, reslurrying in ice water, filtering and drying at room temperature. It is a brownish orange waxy solid, melting at 55-61 C., and is sufficiently pure for fungicidal application. The small amounts of water and bromide ion contained in this material may be removed by conventional means. For example, the water may be removed by vacuum drying at elevated temperatures, and the bromide ion can be removed by recrystallization or chromatography over alumina, using chloroform as bath solvent and eluent. The purified product melts at LD-50 LID-50' Claszer- Fumrium ospnrium sola'ni carpophilnm Reaction product oi sodium dimethyldithio- I carbamate with:
3. stearyl trimethyl ammonium chloride.. 0. 1 2 4. dodecyltrimethyl ammonium bromide. u. 1 g. 5. tetradccyl trimethyl ammonium chloride 1 2 G. stearyl dimethyl benzyl ammonium chloride 12. 5 7. rtizgtyl dimethyl benzyl ammonium chlo- 6 5 8 8. dodecyl dimethyl benzyl ammonium chloride 0.6 8 Reaction product of disodium ethylenebisdithiocarbarr'ate with:
9. cetylpyridinium chloride 1.6 4 10. stearyl dimethyl benzyl ammonium ch1oride 10 14 11. cetyl dimcthyl benzyl ammonium chloride 6 '1 Reaction product of sodium meihyldithiocarbamate with:
12. cetylpyridinium chloride 0:5 4 13. tetradeeyl trimethyl ammonium chloride 2 6 14. stearyl dimethyl benzy ammonium chloride 2' 10 15. cetyl dimethyl benzyl ammonium chloride 2 4 16. dodccyl dimethyl benzyl ammonium chloride 2 10 Reaction product oi sodium diethyldithiocarbamate with:
17. cctyl pyridinium chloride 0.3 5 1S. tetradecyl trimcthyl ammonium chloride 1.2 6 19. stearyl dimethyi benzyl ammonium chloride 0.2 2 20. cetyl dimethyl benzyl ammonium chloride 0.5 3 21. dodecyl dimethyl benzyl ammonium chloride 1 10 Further examples of quaternary ammonium dithiocarbamates which can be used in compositions and process of the invention are as follows:
Reaction product of sodium dimethyldithiocarbamate with:
22. Cetyl pyridinium chloride to make-cetyl pyridinium dimethyldithiocarbamate 23. Cetyl pyridinium bromide to make cetyl pyridinium dimethyldithiocarbamate 24. Tetradecyl pyridiniurn chloride to make tetrae decyl pyrilinium dimethyldithiocarbamate 25. Cetyl trimethyi' ammonium bromide to make cetyl trimethyl ammonium dimethyldithiocarbamate 26. Decyl isobutyl dimethyl ammonium bromide to make decyl isobutyl dimethyl ammonium dimethyl dithiocarbamate 27. Tetradecyl triethyl ammonium chloride to make tetradecyl triethyl ammonium dimcthyldithiocarbamate 28. Stearyl pyridinium chloride to make stearyl pyridinium dimeihyldithiocarbamate 29. Dodecyl pyridinium bromide to make dodecyl pyridinium dimethyldithiocarbamate 3'0. Stearyl triethyl' ammonium chloride to make stearyl triethyl ammonium dimethyldithiocarbamate 31. Undecyl pyridinium chloride to make undecyl pyridinium dimethyldithiocarbamate Reaction product of sodium diethyldithiocarbamate with:
32. Cetyl pyridinium bromide to make cetyl pyridinium diethyldithiocarbamate 33. Dodecyl pyridinium bromide to make dodecyl pyridinium diethyldithiocarbamate 34. Stearyl benzyl dimethyl ammonium chloride to make stearyl benzyl dimethyl ammonium diethyldithiocarbamate 35. Stearyl pyridinium chloride to make stearyl pyridinium diethyldithiocarbamate 36. Cetyl triethyl ammonium chloride to make cetyl triethyl ammonium diethyldithiocarbamate 37.v Tetradecyl trimethyl ammonium chloride to make tetradecyl trimethyl. ammonium diethyldithiocarbamate 38. Decyl dimethyl benzyl ammonium bromide to make decyl dimethyl-benzy'l ammonium. diethyldithiocarbamate 39. Dodecyl triethyl ammonium chloride tomake dodecyl triethyl ammonium diethyldithiocarbamate Reaction product of sodium di-n-butyldithiocarbamate with:
40. Cetyl pyridinium chloride to make cetyl pyridinium di-n-butyldithiocarbamate 4i. Tetradecyl trimethyl ammonium chloride to make tetradecyl trimethyl ammonium di-n-butyldithiocarbamate 42. Cetyl trimethyl ammonium bromide to make cetyl trimethyl ammonium di-n-butyldithiocarbamate 43. Stearyl dimethyl benzyl ammonium chloride to make stearyl dimethyl benzyl ammonium dimbutyldithiocarbarnate 44. Cetyl dimethyl benzyl ammonium chloride to make cetyl dimethyl benzyl ammonium di-n-butyldithiocarbamate 45. Dodecyl trimethyl ammonium bromide to make dodecyl trimethyl ammonium di-n-butyldithiocar.- bamate 46. Dodecyl dimethyl benzyl ammonium chloride to make dodecyl dimethyl benzyl ammonium di-nbutyldithiocarbamate 47. Tetradecyl' triethyl ammonium chloride to make tetradecyl triethyl ammonium di-n-butyldithiocarbamate 1 48. Stearyl trimethyl ammonium bromide to make stearyl trimethyl ammonium di-n-butyldithiocarbamate 49. Decyl isopropyl dimethyl ammonium chloride to make decyl isopropyl dimethyl ammonium di-nbutyldithiocarbamate Reaction product of disodium ethylenebisdithiocarbamate S0. Cetyl pyridinium'bromide to make cetylpyridinium e'thylenebisdithiocarbamate 51. Tetradecyl triethyl ammonium chloride to make tetradecyl triethyl ammonium ethylenebisdithiocarbamate 52. Tetradecyl pyridinium chloride to make tetradecyl pyridinium ethylenebisdithiocarbamate 53. Stearyl pyridinium chloride to make stearyl pyridinium ethylenebisdithiocarbamate 54. Cetyl trimethyl ammonium chloride to make cetyl trimethyl ammonium ethylenebisdithiocarbamate 55. Stearyl n-butyl diethyl ammonium chloride to make stearyl n-butyl diethyl ammonium ethylenebisdithiocarbamate 56. Dodecyl trimethyl ammonium bromide to make dodecyl trimethyl ammonium ethylenebisdithiocarbamate q 57. Stearyl trimethyl ammonium chloride to make stearyl trimethyl ammonium ethylenebisdithiocarbamate 5 8. Decyl triethyl ammonium chloride to make decyl triethyl ammonium ethylenebisdithiocarbamate 59. Undecyl trimethyl ammonium chloride to make undecyl trimethyl ammonium ethylenebisdithiooarbamate 60. Stearyl triethyl ammonium chloride to make stearyl triethyl ammonium ethylenebisdithiocarbamate 61. Stearyl benzyl diethyl ammonium chloride to make stearyl benzyl diethyl ammonium ethylenebisdithiocarbamate Reaction product of sodium di-n-propyldithiocarbamate with 62. Cetyl pyridinium bromide to make cetyl pyridinium di-n-propyldithiocarbamate 63. Stearyl trimethyl ammonium chloride to make stearyl trimethyl ammonium di-n-propyldithiocarbamate Reaction product of sodium N-methyl-N-ethyldithiocar- Reaction product of sodium N-methy-l-N-isopropyldithiocarbamate with:
bamate with:
64. Cetyl pyridinium chloride to make cetyl pyridinium N-methyl-N-ethyldithiocarbamate 65. Dodecyl benzyl diethyl ammonium chloride to make dodecyl benzyl diethyl ammonium N-methyl- N-ethylenedithiocarbamate Reaction product of sodium N-methyl-N-(n-butyl)dithio- Reaction product of sodium N-ethyl-N-(n-propyl)dithiocarbamate with:
Reaction product of sodium N-ethyl-N-isobutyldithiocarbamate with:
68. Dodecyl methyl diethyl ammonium chloride to make dodecyl methyl diethyl ammonium N- methyl-N- (n-butyl dithiocarb amate 69. Stearyl pyridinium chloride to make stearyl pyridinium N-methyl-N-(n-butyl) dithiocarbamate 70. Stearyl decyl dimethyl ammonium chloride to make stearyl decyl dimethyl ammonium N-ethyl- N- (n-propyl dithiocarbamate carbamate with:
71. Tetradecylpyridinium chloride to make tetradecyl pyridinium N-ethyl-N-isobutyldithiocarbamate Reaction product of sodium N-(n-propyl)-N-(n-butyl)- dithiocarbamate with:
72. Cetyl benzyl dimethyl ammonium chloride to make cetyl benzyl dimethyl N-(n-propyl)-N-(nbutyl) dithiocarbamate 73. Cetyl pyridinium bromide to make cetyl pyri- Reaction product of sodium ethyldithiocarbamate with: 74. Cetyl pyridinium bromide to make cetyl pyridinium ethyldithiocarbamate 75. Cetyl dimethyl benzyl ammonium chloride to make cetyl dimethyl benzyl ammonium ethyldithio carbamate Reaction product of sodium n-propyldithiocarbamate with:
76. Tetradecyl trimethyl ammonium chloride to make tetradecyl trimcthyl ammonium n-propyldithiocarbamate 77. Decyl triethyl ammonium bromide to make decyl triethyl ammonium n-propyldithiocarbamate Reaction product of sodium n-butyldithiocarbamate with:
78. Cetyl pyridinium chloride to make cetyl pyridinium n-butyldithiocarbamate 79. Dodecyl dimethyl benzyl ammonium chloride to make dodecyl dimethyl benzyl ammonium n-butyldithiocarbamate The appropriate quaternary ammonium halide was in each instance reacted with the dithiocarbamate as set out in Examples 1 and 2 above. Thus, in each instance, equimolecular amounts of the reactants are dissolved in water and reacted to form a precipitate.
Fungicidal compositions of the present invention containing at least one of the quaternary ammonium products as above described can be prepared by admixing one or more of these products with pest control adjuvants or modifiers to provide compositions in the form of waterdispersible powders, dusts, solutions, and emulsifiable solutions. While the quaternary ammonium dithiocarbamates employed in compositions of the invention can be formulated in any conventional manner and used in processes of the invention for the control of fungi, it is much preferred that they be formulated in compositions which contain a free-flowing, inert powder. Still more preferred are such. mixtures in which one or more surfactants are present.
The free-flowing, inert powders can be any of the extenders commonly employed in the insecticide, herbicide and fungicide art for the application of such materials and may include natural clays such as attapulgite and kaolinite clays, diatomaceous earth, talcs, synthetic mineral fillers derived from silica and silicate such as synthetic fine silica and synthetic calcium or magnesium silicate, wood flour and walnut shell flour.
' The amount of the extenders can vary widely and can range from about 10 to 95% by weight of a fungicidal composition. Thus the amount of dithiocarbamate will range from about 5 to ,The particle size can vary considerably but will ordinarily be somewhat under 50 microns in the finished formulation. As a'matter of convenience, the compositions can be prepared with a pulverulent extender or with an extender with particles above the desired size and after admixture with the quaternary ammonium dithiocarbamate the entire composition can be suitably ground so that the particle size of the extender will be small enough to give free-flowing compositions which can readily be applied. Particle size will usually run something under 50 microns in such finished products.
Compositions as described can, in addition to the finely divided extender, contain a surfactant. The surfactant can be a dispersant, a de-foamer or an emulsifying agent which will assist dispersion of the composition in the water. The surfactants or surface-active agents can include such cationic and non-ionic surface-active agents as have heretofore been generally employed in pest control compositions of similar type. Suitable surface-active agents are set out, for example, in Searle US. Patent 2,426,417, Todd US. Patent 2,655,447, Jones US. Patent 2,412,510, or Lenher US. Patent 2,139,276. A detailed list of such agents is set forth by J. W. McCutcheon in Soap and Chemical Specialties, December 1957, Januseats;
ary, February, March and April 1958. See also Mc- Cutcheon in Chemical Industries, November 1947, page 8011 et seq., entitled Synthetic Detergents; and Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the US. Dept. of Agriculture. In general, anionic surface-active agents cannot be used.
Suitable surfactants for use in compositions of the present invention are alkyl and alkyl aryl polyether alcohols, polyoxyethylene sorbitol or sorbitan fatty acid esters, polyethylene glycol fatty esters and fatty alkylol amide condensates.
In general, less than about by weight of the surface-active agent will be used in compositions of the invention and ordinarily the amount of surface-active agent will be less than 1% by Weight. Usually, in accordance with customary practices, the amount will range from about 0.5 to 2% of a surface-active agent.
Particularly preferred surface-active agents include polyvinyl alcohol, methocels, gum arabic, long chain amine acetates, substituted oxazolines and alkyl dimethylamine oxides.
The quaternary ammonium dithiocarbamates used in compositions of the invention are very slightly water soluble and are cationic in nature, thus, to greater or lesser extents, various of the compounds above described act as wetting and dispersing agents. This action, however, will often be insufiicient and a suitable non-ionic or cationic dispersant should also be added.
While formulations containing free-flowing, finely divided extenders and with or without an added wetting agent are much preferred compositions of the invention, it Will be understood that the quaternary ammonium compounds can be used in processes of the invention by formulation and application in various conventional manners.
Thus, the compounds though only slightly soluble can be dissolved in water at the point of use to obtain enough of the active material to obtain control of fungi.
The quaternary ammonium compounds to be used in the processes of the invention can also be dissolved in appropriate non-phytotoxic organic solvents. A concentrate thus formed can be mixed with water, using a dispersing agent if one is necessary. This cetylpyridinium dimethyldithiocarbamate can be dissolved to form a concentrated solution in dimethylformamide and this can be mixed with an appropriate quantity of water to obtain the concentration of the dithiocarbamate desired. Other suitable solvents are lower molecular weight aromatic hydrocarbons, usually benzene, toluene, xylene and alkylated naphthalene, volatile, low molecular weight esters, and water immiscible ketones such as ethyl to amyl acetate and methylisobutyl ketone to dibutyl ketone.
Emulsifiable oils can be prepared in the same fashion using an oil in which the dithiocarbamate is soluble, such as xylene. Such emulsifiable oils can contain other suitable solvents for the quaternary ammonium dithiocarbamates as above. With such oils, suitable surfactants should be used such as cationic or non-ionic agents known to the art as emulsifying agents as above described.
In the application of quarternary ammonium dithiocarbamates according to the invention, fungicidal control is obtained by applying the active compound at a dosage, or at a rate, from about 0.05 to 5 pounds per acre. The optimum amount in each instance is largely dependent upon the exact method of application, the state and condition of growth of plants to be treated, the climatic conditions and other such well-understood variables.
pear scab, peach scab, cedar-apple rust, cherry leaf spot, .Broolrs spot, sooty blotch, bitter rot, black rot, black spot (of roses) and apple blotch.
. 8 Example 80 A fungicidal composition was prepared by mixing 20 parts by weight of cetylpyridinium dimethyldithiocarbamate with parts by weight of a filler (fullers earth) and 10 parts byweight of dispersing agent (refined sulfite lye powder). This composition is identified as composition A in Tests I and II below and is sprayed in the form of a. suspension containing 0.2% of composition A.
The above composition was compared with composition Z containing of zinc dimethyldithiocarbamate in two tests for controlling Venturia inaequalis (apple scab) on the James Grieve variety. The results were as follows:
Test 1.The trees were sprayed 24 hours after infection of the leaf. After spraying 20 days elapsed before the percentage of leaf surface affected by scab was determined.
Test II.-The trees were sprayed as in Test I but this time 48 hours after infection of the leaf. After spraying 19 days elapsed before the percentage of leaf surface affected by scab was determined.
Average percent of leaf surface affected by scab Treatment of tree 1 Composition Z, 0.1%. Composition A, 0.2%. 0.2
Example 81 Percent Cetyl pyridinium dimethyldithiocarbamate 20 Attapulgite clay 80 The above composition is prepared by blending the components together and passing through a micropulven'zer until substantially all agglomerates are broken down to 50 microns or smaller.
This formulation is applied at the rate of 2 pounds per gallons of water to an apple orchard 48 hours after a scab infection period. Excellent curative action on the scab infection is obtained and the trees are protected from re-infection by the disease.
Example 82 Percent Cetyl trimethylammonium dirnethyldithiocarbamate 50 Low viscosity polyvinyl alcohol 1 Synthetic fine silica 49 The above wettable powder is prepared as in Example 81.
This formulation is applied at the rate of 1 /2 pounds per 100 gallons in the first cover spray for control of apple scab and cedar-apple rust in an apple orchard. Good control of both diseases is obtained.
Example 83 Percent Cetyl pyridinium dimethyldithiocarbamate 20 A blend of long chain fatty amides 2 Xylene 78 The above emulsifiable composition is prepared by simple mixing of the mutually soluble components. When dispersed in water this compositions forms a cationic emulsion. i
This formulation is applied at the rate of 1 pint per 100 gallons toa grove of Bartlett pears as a preventive treatment for control of pear scab. Sprayed trees are protected from the disease while unsprayed trees are severely infected with scab.
Example 84 Percent Dodecyl tn'methylammonium dimethyldithiocarbamate 25 Attapulgite clay 75 Example 85 Percent Tetradecyl trimethylammonium dimethyldithiocarbamate Diatomaceous silica The above wettable powder is prepared in the same manner as Example 81.
This formulation is applied at the rate of 2 pounds per 100 gallons to a pear orchard 48 hours after a scab infection period. Developing scab lesions on the leaves are eradicated and the trees protected from early reinfection by scab and also from sooty blotch disease.
Example 86 Percent Cetyl dimethyl benzylammonium dimethyldithiocarbamate 10 Attapulgite clay 40 Pyrophyllite 50 Example 87 Percent Tetradecyl trimethylammonium diethyldithiocarbamate 50 Synthetic fine silica 50 The above wettable powder is prepared in the same manner as Example 81.
This composition is included at a rate of /1 pounds per 100 gallons in the shnck-fall spray in a cherry orchard for control of cherry leaf spot. Excellent control of the disease is obtained on the treated trees.
Example 88 Percent Stearyl dimethyl benzylammonium diethyldithiocarbamate 50 Synthetic fine calcium silicate (neutral) 50 The above wettable powder is prepared in the same manner as Example 81.
This composition is applied at the rate of 1 pound per 100 gallons to an interplanted apple and peach orchard for the control of apple scab, peach scab, sooty blotch, and frog-eye leaf spot. Good control of both apple and peach diseases results.
Example 89 Percent Cetyl pyridinium ethylenebisdithiocarbamate 20 Mixed long chain fatty amides 2 Xylene 78 The 'above emulsifiable oil is prepared in the same manner as Example 83.
This composition is applied to a planting of crab apple tree for protection from attack by apple scab. A rate of 1 pint per acre is used, and good protection is afforded from the fungus disease.
Example 90 Percent Cetyl dimethyl benzylammonium ethylenebisdithiocarbamate l0 Attapulgite clay 30 Micaceous talc 60 The above dust is prepared by first blending and grinding the active component with the minor diluent until substantially all agglomerates are reduced to below 50 microns, then blending this mix with the major diluent.
A row of grapes is dusted just prior to bloom with this composition at the rate of 10 pounds per acre for protection against black rot. Repetition of the treatment immediately after bloom and at two weeks after bloom gives good control of the disease.
Example 91 Percent Cetyl trimethylammonium ethylenebisdithiocarbamate 25 Attapulgite clay The above wettable powder is prepared in the same manner as Example 81.
An apple orchard is sprayed 24 hours after a scab infection period with this composition at a rate of 1 pound per 100 gallons. Scab lesions which have begun are eradicated from the leaves and the trees are thus protected from this disease.
The compounds above numbered 1 to 79 can be formulated in each of the ways shown. Thus in each of the Examples to 91 above, the quaternary ammonium dithiocarbamate there named can be replaced with an equal weight of the quaternary ammonium dithiocarbamate of Examples 1 to 79 and applied as shown.
This application is a continuation-in-part of copending application Serial No. 779,559, filed December 11, 1958, now abandoned.
The claims are:
1. A method for controlling plant pathogenic fungi comprising applying to a plant a fungicidally elfective amount of:
R1 s R4I 1"i i 3Q R|/ Rs in which:
Q is selected from the group consisting of R is an alkyl hydrocarbon group of 10 to 18 carbons R is selected from the group consisting of hydrogen and an alkyl hydrocarbon group of less than 5 carbons,
R is an alkyl hydrocarbon group of less than 5 carbons,
R is selected from the group consisting of an alkyl and aralkyl hydrocarbon group of less than 13 carbons, and, when R N and R taken together comprise a pyridinium group, a merged constituent of such pyri' dinium group,
R is selected from the group consisting of methyl and ethyl,
. 1-1 V R, is' selected from the group consisting of methyl, ethyl, and, when R N, and R taken together comprise a pyridinium group, a merged constituent ofsuchpyridinum group.
2. A method for controlling plant pathogenic fungi comprising applying to a plant a fungicidally' effective amount of cetyl pyridinium dimethyldithiocarbamate.
3. A method for controlling plant pathogenic fungi comprising applying to a plant a fungicidally effective amountof cetyl pyridinium ethylenebisdithiocarbamate.
4. A methodfor-controlling plant pathogenic fungi comprising applying to a planta fungicidally efl'ective amount of cetyl pyridjninm methyldithiocarbamate.
5-. A method for controlling plant pathogenic fungi" comprising applying to a plant a fungicidally effective amountof cetyl pyridinium diethylidthiocarbamate;
6. A fungicidal formulation containing 5 to 90% ofthe compound described in claim 1, the balance consisting essentially of a finely divided, free-flowing, inert extender and: containing additionally a surface-active.
UNITED STATES PATENTS 2,457,674 Heuberger t. -j.. Dec. 28, 1948.
Baird Sept. 27, 1938

Claims (1)

1. A METHOD FOR CONTROLLING PLANT PATHOGENIC FUNGI COMPRISING APPLYING TO A PLANT A FUNGICIDALLY EFFECTIVE AMOUNT OF:
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3227614A (en) * 1960-09-29 1966-01-04 Dustikin Products Inc Germicidal paper
US3354085A (en) * 1965-05-28 1967-11-21 Chevron Res Lubricants containing quaternary ammonium dithiocarbamates
US3364108A (en) * 1963-03-05 1968-01-16 Tokyo Yuki Kagaku Kogyo Kabush Pesticidal nicotine alkaloid salts of dithiocarbazic or dithiocarbamic acids
RU2787372C1 (en) * 2021-07-13 2023-01-09 Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) Method for production of anti-wear additive for silicone lubricating materials

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2131210A (en) * 1933-07-07 1938-09-27 Ici Ltd Accelerator for the vulcanization of rubber
US2457674A (en) * 1944-12-02 1948-12-28 Rohm & Haas Fungicidal compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2131210A (en) * 1933-07-07 1938-09-27 Ici Ltd Accelerator for the vulcanization of rubber
US2457674A (en) * 1944-12-02 1948-12-28 Rohm & Haas Fungicidal compositions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3227614A (en) * 1960-09-29 1966-01-04 Dustikin Products Inc Germicidal paper
US3364108A (en) * 1963-03-05 1968-01-16 Tokyo Yuki Kagaku Kogyo Kabush Pesticidal nicotine alkaloid salts of dithiocarbazic or dithiocarbamic acids
US3354085A (en) * 1965-05-28 1967-11-21 Chevron Res Lubricants containing quaternary ammonium dithiocarbamates
RU2787372C1 (en) * 2021-07-13 2023-01-09 Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) Method for production of anti-wear additive for silicone lubricating materials

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