US2974156A - Method for stabilization of manganese salts of alkylene bisdithiocarbamic acids and the products thereof - Google Patents

Method for stabilization of manganese salts of alkylene bisdithiocarbamic acids and the products thereof Download PDF

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Publication number
US2974156A
US2974156A US757939A US75793958A US2974156A US 2974156 A US2974156 A US 2974156A US 757939 A US757939 A US 757939A US 75793958 A US75793958 A US 75793958A US 2974156 A US2974156 A US 2974156A
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US
United States
Prior art keywords
manganese
hexa
ethylene bisdithiocarbamate
bisdithiocarbamate
alkylene
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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
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US757939A
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English (en)
Inventor
Raymond J Sobatzki
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.)
Rohm and Haas Co
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Rohm and Haas Co
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Filing date
Publication date
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Priority to US757939A priority Critical patent/US2974156A/en
Priority to DER26117A priority patent/DE1113607B/de
Priority to GB28195/59A priority patent/GB929210A/en
Priority to ES0251662A priority patent/ES251662A1/es
Priority to CH7750359A priority patent/CH387014A/fr
Priority to FR803830A priority patent/FR1234005A/fr
Application granted granted Critical
Publication of US2974156A publication Critical patent/US2974156A/en
Priority to OA50121A priority patent/OA00105A/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • A01N47/08—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
    • 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

Definitions

  • a further object of this invention is the preparation of manganese alkylene bisdithiocarbamate compositions which exhibit lower phytotoxicity than control samples not treated by the process of this invention.
  • Another object of this invention is the preparation of manganese alkylene bisdithiocarbamates which have much less odor than control samples not treated by the process of the present invention.
  • a further object of this invention is the preparation of stable fungicidal compositions containing as essential active ingredient stabilized manganese ethylene bisdithiocarbamate.
  • manganese salts of alkylene bisdithiocarbamic acid exhibit varying degrees of instability at elevated temperatures as evidenced by evolution of carbon disulfide and decreased fungicidal activity
  • the manganese salts appear to be even less stable than, for instance, thesodiurn or zinc salts.
  • manganese ethylene bisdithiocarbamate has been known to undergo spontaneous combustion during manufacture and,
  • Salts of dialkyl dithiocarbamic acids also undergo de- "composition on storage which, at least on the basisof the 5 net efiects noted, appears to be the same type of reaction at fi 'fO ICC 2 to which the salts of alkylene bisdithiocarbamic acids are susceptible. In both cases, it appears to be the group N-c-s- II which is unstable as suggested by the fact that the amount of-decomposition is almost directly proportional to the amount of carbon disulfide which is evolved. Thus, a measurement of the amount of carbon disulfide evolved makes possible comparisons of the relative stabilities of various samples.
  • hexamethylene tetramine (here- Patented Mar. 7,1961? 3 inafter referred to as hexa) which is required will vary somewhat depending on the specific conditions which ob tain, but from about 0.2% to about 5%, based on the weight of the bisdithiocarbamate, is effective.
  • a preferred embodiment employs from 0.5% to 1.5% of hexa, based on the weight of the bisdithiocarbamate.
  • a particularly preferred embodiment employs 1% hexa based on the weight of the bisdithiocarbamate.
  • the hexa can be incorporated into the aqueous slurry of manganese ethylene bisdithiocarbamate during manufacture and prior to the drying of the slurry to form the final solid product.
  • the slurry is to be employer per se as a fungicide, the hexa can be added to the slurry at the time of manufacture. It has been found that the hexa is more effective as a stabilizer if it is added to the dried product rather than being added to the slurry. Thus, it is preferred to add the hexa to the dried product, mixing by tumbling, etc.
  • preformed disodium ethylene bisdithiocarbamate may be employed by dissolving it in water and adding an aqueous solution of a manganese salt to the dissolved disodium ethylene bisdithiocarbamate.
  • the prep aration of the manganese ethylene bisdithiocarbamate forms no part of the present invention.
  • the manganese ethylene bisdithiocarbamate containing even as much as 5% hexa is quite as effective as the unstabilized manganese salt.
  • the addition improves its value as a fungicide by virtue of preventing loss of active fungicidal ingredient and it does not alter the type of fungicidal activity exerted by the compound.
  • the hexa-stabilized manganese ethylene bisdithiocarbamate exhibits the same order of low phytotoxicity and the same degree of safety that is characteristic of the unstabilized material.
  • the methods of use of the non-stabilized manganese ethylene bisdithiocarbamate are well-known and typical fungicidal preparations are set forth in US. Patent 2,504,404.
  • the stabilized manganese ethylene bisdithiocarbamate of the present invention can be employed in exactly the same manner as the unstabilized salt is. There need be no change in method of application or in the application rate.
  • the stabilities of the samples were tested by subjecting them to heat at a given temperature in a closed system while being swept constantly by a stream of humidified air. Any exotherm which develops during the test is re corded on a differential recorder which records the difference between the temperature of the sample and the temperature of the bath.
  • the air which is swept over the sample is bubbled through a trap containing a solution of lead acetate to collect any hydrogen sulfide that may be evolved and through a methanolic potassium hydroxide trap to collect the carbon disulfide which is evolved.
  • the stability tests were conducted at two temperatures, at C. and at 70 C.
  • the 90 C. tests were considered to be accelerated screening tests, while the 70 C. tests were conducted to simulate the most adverse conditions to which the products might be naturally subjected, i.e., without the application of artificial heat sources.
  • This temperature, 70 C. (158 F.) is commonly used by the Armed Forces as the maximum temperature to which their supplies will be subjected unless an artificial heat source is applied thereto.
  • a composition resistant to decomposition on ageing comprising manganese ethylene bisdithiocarbamate having intimately admixed therewith a stabilizing amount of hexamethylene tetramine.

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)
US757939A 1958-08-29 1958-08-29 Method for stabilization of manganese salts of alkylene bisdithiocarbamic acids and the products thereof Expired - Lifetime US2974156A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US757939A US2974156A (en) 1958-08-29 1958-08-29 Method for stabilization of manganese salts of alkylene bisdithiocarbamic acids and the products thereof
DER26117A DE1113607B (de) 1958-08-29 1959-08-07 Fungicides Mittel auf der Basis von Manganaethylenbisdithiocarbamat
GB28195/59A GB929210A (en) 1958-08-29 1959-08-18 Method for stabilization of manganese salts of alkylene bisdithiocarbamic acids and the products thereof
ES0251662A ES251662A1 (es) 1958-08-29 1959-08-21 Metodo para la estabilizaciën de salas de magneso
CH7750359A CH387014A (fr) 1958-08-29 1959-08-28 Procédé de stabilisation de l'éthylène-bis-dithiocarbamate de mangnèse et produit obtenu par ce procédé
FR803830A FR1234005A (fr) 1958-08-29 1959-08-28 Procédé de stabilisation de sels de manganèse d'acides alkylène bisdithiocarbamiques et produits obtenus par ce procédé
OA50121A OA00105A (fr) 1958-08-29 1964-05-27 Procédé de stabilisation de sels de manganèse d'acides alkylène bisdithiocarbamiques et produits obtenus par ce procédé.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US757939A US2974156A (en) 1958-08-29 1958-08-29 Method for stabilization of manganese salts of alkylene bisdithiocarbamic acids and the products thereof

Publications (1)

Publication Number Publication Date
US2974156A true US2974156A (en) 1961-03-07

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US757939A Expired - Lifetime US2974156A (en) 1958-08-29 1958-08-29 Method for stabilization of manganese salts of alkylene bisdithiocarbamic acids and the products thereof

Country Status (7)

Country Link
US (1) US2974156A (fr)
CH (1) CH387014A (fr)
DE (1) DE1113607B (fr)
ES (1) ES251662A1 (fr)
FR (1) FR1234005A (fr)
GB (1) GB929210A (fr)
OA (1) OA00105A (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3036104A (en) * 1959-07-29 1962-05-22 Mountain Copper Company Ltd Stabilization of copper chelate
US3085042A (en) * 1961-06-09 1963-04-09 Du Pont Phytotoxicity of manganese ethylene-bisdithiocarbamate reduced by the addition of zinc and cadmium ions
US3167471A (en) * 1960-07-19 1965-01-26 Siapa Spa Synergistic fungicidal compositions
US3275500A (en) * 1962-10-30 1966-09-27 Montedison Spa Stabilized fungicidal compositions
US3281316A (en) * 1964-05-16 1966-10-25 Hoechst Ag Fungicidal compositions containing salts of ethylene-bis-dithiocarbamic acid and tin compounds
US3346605A (en) * 1961-08-26 1967-10-10 Basf Ag Ammonia complex manganese salt of ethylenebisdithiocarbamic acid
US3436457A (en) * 1966-05-13 1969-04-01 Vondelingen Plaat Bv Stabilized manganese ethylene bisdithiocarbamate and process
US3449386A (en) * 1965-12-01 1969-06-10 Procida Stable alkylene-bis-dithiocarbamates
US3856836A (en) * 1972-07-18 1974-12-24 Pennwalt Corp Method for manufacturing a stabilized manganese ethylenebisdithiocarbamate product and method for manufacturing fungicidal preparations containing such stabilized product
US4344890A (en) * 1981-05-04 1982-08-17 Adams Jr John B Aqueous fungicidal formulations and their preparation
DE3340214D2 (en) * 1982-04-20 1984-05-17 Borsodi Vegyi Komb Plant protector agent
AT386194B (de) * 1982-04-20 1988-07-11 Borsodi Vegyi Komb Verfahren zur herstellung neuer, substituierter alkoxycarbonyl-dithiocarbamate und -thiolcarbamate
US4886825A (en) * 1982-06-08 1989-12-12 Ciba-Geigy Corporation Compositions for controlling plant diseases and the use thereof in plant protection
US20050154055A1 (en) * 2004-01-14 2005-07-14 Philippe Gouat Method of stabilizing alkylenebisdithiocarbamates
US20070104750A1 (en) * 2005-11-01 2007-05-10 Dow Agrosciences Llc Pesticidally active compositions having enhanced activity

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201041509A (en) 2009-04-30 2010-12-01 Dow Agrosciences Llc Pesticide compositions exhibiting enhanced activity
TW201041507A (en) 2009-04-30 2010-12-01 Dow Agrosciences Llc Pesticide compositions exhibiting enhanced activity and methods for preparing same
TW201041510A (en) 2009-04-30 2010-12-01 Dow Agrosciences Llc Pesticide compositions exhibiting enhanced activity

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2665285A (en) * 1951-07-06 1954-01-05 Du Pont Stabilization of derivatives of dithiocarbamic acids
US2791605A (en) * 1954-07-28 1957-05-07 Stauffer Chemical Co Stabilization of salts of monoalkyldithiocarbamic acids
US2860870A (en) * 1954-01-28 1958-11-18 Monroe Auto Equipment Co Stabilizer and spring device

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2806870A (en) * 1956-01-09 1957-09-17 Tennessee Corp Methods for stabilization of the manganous salt of dimethyl dithiocarbamic acid and the products thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2665285A (en) * 1951-07-06 1954-01-05 Du Pont Stabilization of derivatives of dithiocarbamic acids
US2860870A (en) * 1954-01-28 1958-11-18 Monroe Auto Equipment Co Stabilizer and spring device
US2791605A (en) * 1954-07-28 1957-05-07 Stauffer Chemical Co Stabilization of salts of monoalkyldithiocarbamic acids

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3036104A (en) * 1959-07-29 1962-05-22 Mountain Copper Company Ltd Stabilization of copper chelate
US3167471A (en) * 1960-07-19 1965-01-26 Siapa Spa Synergistic fungicidal compositions
US3085042A (en) * 1961-06-09 1963-04-09 Du Pont Phytotoxicity of manganese ethylene-bisdithiocarbamate reduced by the addition of zinc and cadmium ions
US3346605A (en) * 1961-08-26 1967-10-10 Basf Ag Ammonia complex manganese salt of ethylenebisdithiocarbamic acid
US3275500A (en) * 1962-10-30 1966-09-27 Montedison Spa Stabilized fungicidal compositions
US3281316A (en) * 1964-05-16 1966-10-25 Hoechst Ag Fungicidal compositions containing salts of ethylene-bis-dithiocarbamic acid and tin compounds
US3449386A (en) * 1965-12-01 1969-06-10 Procida Stable alkylene-bis-dithiocarbamates
US3436456A (en) * 1966-05-13 1969-04-01 Vondelingen Plaat Bv Stabilized manganese ethylene bisdithiocarbamate and process
US3436457A (en) * 1966-05-13 1969-04-01 Vondelingen Plaat Bv Stabilized manganese ethylene bisdithiocarbamate and process
US3856836A (en) * 1972-07-18 1974-12-24 Pennwalt Corp Method for manufacturing a stabilized manganese ethylenebisdithiocarbamate product and method for manufacturing fungicidal preparations containing such stabilized product
US4344890A (en) * 1981-05-04 1982-08-17 Adams Jr John B Aqueous fungicidal formulations and their preparation
DE3340214D2 (en) * 1982-04-20 1984-05-17 Borsodi Vegyi Komb Plant protector agent
AT386194B (de) * 1982-04-20 1988-07-11 Borsodi Vegyi Komb Verfahren zur herstellung neuer, substituierter alkoxycarbonyl-dithiocarbamate und -thiolcarbamate
US4886825A (en) * 1982-06-08 1989-12-12 Ciba-Geigy Corporation Compositions for controlling plant diseases and the use thereof in plant protection
US20050154055A1 (en) * 2004-01-14 2005-07-14 Philippe Gouat Method of stabilizing alkylenebisdithiocarbamates
WO2005067717A3 (fr) * 2004-01-14 2005-11-24 Dow Agrosciences Llc Procede de stabilisation des alkylenebis dithiocarbamates
JP2007517914A (ja) * 2004-01-14 2007-07-05 ダウ アグロサイエンシィズ エルエルシー アルキレンビスジチオカルバメートを安定化する方法
US20070104750A1 (en) * 2005-11-01 2007-05-10 Dow Agrosciences Llc Pesticidally active compositions having enhanced activity

Also Published As

Publication number Publication date
CH387014A (fr) 1965-01-31
DE1113607B (de) 1961-09-07
OA00105A (fr) 1966-01-15
ES251662A1 (es) 1960-04-16
GB929210A (en) 1963-06-19
FR1234005A (fr) 1960-10-14

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