US3401182A - Process for oxidizing soluble alkylene bisdithiocarbamates to produce an oxygen containing product, and the product of said process - Google Patents

Process for oxidizing soluble alkylene bisdithiocarbamates to produce an oxygen containing product, and the product of said process Download PDF

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Publication number
US3401182A
US3401182A US367620A US36762064A US3401182A US 3401182 A US3401182 A US 3401182A US 367620 A US367620 A US 367620A US 36762064 A US36762064 A US 36762064A US 3401182 A US3401182 A US 3401182A
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product
ethylene
oxidized
acid
salt
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Allan M Harvey
Lester A Brooks
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Vanderbilt Chemicals LLC
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RT Vanderbilt Co Inc
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Priority to US367620A priority Critical patent/US3401182A/en
Priority to FR8666A priority patent/FR1428360A/fr
Priority to BE660963A priority patent/BE660963A/xx
Priority to ES0310926A priority patent/ES310926A1/es
Priority to NL6504315A priority patent/NL6504315A/xx
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    • 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

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  • Such soluble oxygen containing product is thereafter treated with .a solution of soluble salt of a divalent metal of zinc, manganese, copper or cadmium, thereby to precipitate a product containing oxygen and such divalent metal.
  • a solution of soluble salt of a divalent metal of zinc, manganese, copper or cadmium thereby to precipitate a product containing oxygen and such divalent metal.
  • X is the metal zinc or divalent manganese.
  • Similar compounds of other metals are also known. These compounds can be prepared by treating the sodium salt of ethylene bisdithiocarbamic acid (nabam) in aqueous solution with a soluble zinc or manganous salt such as zinc or manganous sulfate and recovering the precipitated product that forms.
  • nabam ethylene bisdithiocarbamic acid
  • the prior art also discloses the manufacture of metal free oxidized products of soluble ethylene bisdithiocarbamates, the ethylene bisthiurarn monosulfide and ethylene bisthiuram disulfide having the following formulas:
  • the latter compounds are prepared from ammonium or soluble metal ethylene bisdithiocarbamates by treating them with any of a variety of oxidizing agents and under a variety of conditions to produce the indicated compounds or mixtures of thiuram monoand disulfides along with free sulfur and sometimes ethylenethiourea. Under acid conditions nabam oxidized with air in the presence of the manganous ion as catalyst, or the am- 3,4lll,l82 Patented Sept.
  • Hydrogen peroxide is the only oxidizing agent that has been found which will produce the compounds of the invention.
  • the optimum quantity of hydrogen peroxide is two moles per mole of dithiocarbamate. The reaction is believed to take place in accordance with the following equation:
  • the important feature of the process of the invention in addition to the use of hydrogen peroxide as the oxidizing agent is avoiding the addition of acid during the oxidation step.
  • the product will of course be substantially all the thiuram monoand disulfides described above.
  • the oxygen becomes associated with the sulfur atoms of the dithiocarbamic acid, so that when the oxidized material is subsequently treated with a divalent metal, the desired compound containing both the divalent metal and the combined oxygen is obtained.
  • no acid is added during the oxidation step.
  • the product will be a mixture of the thiuram monoand disulfides and the desired product substantially in the proportions determined by the amount of acid added.
  • the temperature of the reaction should be maintained as low as practical, that is below about 40 C., preferably in the range of 0 to 10 C. This may be accomplished, for example, by ice-cooling to remove the heat generated by the exothermic reaction.
  • the reaction is carried out with stirring over a time interval of about 30 minutes, followed by stirring an additional 0.5 to 2 hours at about 10 to 15 C. to complete the reaction.
  • a light precipitate of free sulfur may form which can be removed by filtration.
  • a water-soluble salt of the desired divalent metal is then added to precipitate the insoluble salt of oxidized alkylene bisdithiocarbamic acid as a slurry. This precipitate is filtered, washed with water and dried in a low temperature oven.
  • any soluble metal salt of an alkylene bisdithiocarbamic acid may be used such as sodium, potassium or calcium. They correspond to the structural formula:
  • the technique is also useful in determining whether chemical manipulation of a compound with a known spectrum changes that C0111- pound in such a way as to eliminate some of its characteristic groupings of atoms and linkages and to introduce others with consequent changes in the infrared spectrum. Even if a new compound cannot be completely isolated or purified because of insolubility or because of inherent lability, its infrared spectrum will provide clues to its chemical identity.
  • FIGURE 1 is an infrared absorption spectrum of the zinc salt of oxidized ethylene bisdithiocarbamic acid as determined both by the potassium bromide disc technique, and by the Nujol mull technique (which resolves the 8.2 1 absorption band);
  • FIGURE 2 shows the infrared spectrum of the zinc salt of partially oxidized nabam, that is the product formed when less than the stoichiometric two moles of hydrogen peroxide are used per mole of nabam;
  • FIGURE 3 shows the spectrum for zineb which is the zinc ethylene bisdithiocarbamate
  • FIGURE 4 shows the infrared absorption spectrum for the manganous salt of oxidized nabam
  • FIGURE 5 gives the infrared absorption spectrum for the trnanganous salt of partially oxidized nabam
  • FIGURE 6 shows the infrared absorption spectrum for maneb which is the manganous ethylene bisdithiocarba mate
  • FIGURE 7 shows the infrared absorption spectrum for ethylene bisthiuram disulfide which is an oxidation product of the ethylene bisdithiocarbamates and is known in the prior art
  • FIGURE 8 also gives the infrared absorption spectrum for ethylene bisthiuram monosulfide, an ethylene bisdithiocarbamate oxidation product known in the prior art.
  • FIGURE 9 gives the infrared absorption spectrum for the zinc salt of oxidized isopropyleue bisdithiocarbamic acid.
  • abscissa represents the wavelength in linear fashion, expressed in microns, and the ordinate shows (to a logarithmic scale) the percent absorbance.
  • novel compositions of the invention are shown by their infrared spectra to differ from both the corresponding metal salts of unoxidized alkylene bisdithiocarbamic acid and from the prior art oxidation products thereof.
  • the same band appears in the infrared spectra of the copper and cadmium salts of oxidized ethylene bisdithiocarbamic acid.
  • the products of the invention are also seen to lack many of the bands which appear to be characteristic of the thiuram monosulfide, as well as the 10.5-1046a band present in the thiuram disulfide and in unoxidized ethylene bisdithiocarbamates.
  • composition of the invention may differ considerably in elementary analysis, apparent empirical formula, but they nevertheless still give basically the same infrared absorption spectra indicating that the different preparations indeed contain basically the same new chemical substance or substances.
  • structure of the product formed by our process may have an open chain or polymeric form of structure which may contain recurring units as shown below:
  • X is the divalent metal.
  • R, n and X have the values assigned above.
  • Example 1 --Zinc salt of oxidized ethylene bisdithiocarba-mic acid
  • sodium ethylene bisdithiocarbamate 116.4 g. of 22% active material, or 0.1 mole
  • hydrogen peroxide 13.6 g. of 50% active or 0.2 mole
  • 100 ml. water dropwise over a period of minutes while maintaining the temperature of the reaction mixture below 0., preferably at 10-20 C.
  • the mixture was filtered to remove a small quantity of pale yellow solid which precipitated during the peroxide addition.
  • To the filtrate was added, with stirring, ml. of 1 M zinc sulfate solution (0.1 mole).
  • Example 2 -Zinc salt of oxidized 1,2-propylene bisdithiocarbamic acid
  • sodium 1,2-propylene bisdithiocarbamate (the propylene group is the methyl ethylene group) (220 ml. of 24.5% active solution, 0.2 mole) in 200 ml. water was added dropwise with stirring and cooling hydrogen peroxide (27.2 g. of 50% active material, 0.4 mole) in 100 ml. water.
  • the temperature of the reaction mixture was maintained at 5 C. over the 30-minute period of peroxide addition.
  • the clear, orange-colored reaction solution was stirred for an additional 30 minutes at C. At the end of this time, the solution was still clear.
  • To this oxidized dithiocarbamate solution was then added 200 ml.
  • Example 4 Manganese salt of oxidized ethylene bisdithiocarbamic acid The procedure of Example 1 was followed, using 56 g. (0.05 mole) of sodium ethylene bisdithiocarbamate in 400 ml. water, oxidizing it with 6.8 g. of 50% active hydrogen peroxide (0.1 mole) in 80 ml. water at 10 C. over a period of one hour. To this solution was added manganese sulfate (50 ml. of 1 M solution, 0.05 mole), to obtain 8.6 g. of a light brown product which melted (with decomposition) at 250 C. Yield, 58% of theoretical. The infrared spectrum of this material determined on a potassium bromide disc had absorption bands at 5.9, 6.3, 6.9, 7.25, 7.6, 8.6, 10.1 and 11.8,u, as shown in FIGURE 4.
  • Example 5 Copper salt of oxidized ethylene bisdithiocarbamic acid 6 and melting at 160190 C. was obtained.
  • the infrared spectrum as determined on a Nujol mull of the product had absorption bands at 5.8, 6.3, 6.65, 6.8 (Nujol), 7.35 (Nujol), 8.1, 8.4, 9.6, 10.05, 10.6 and 1 1.7
  • the zinc salt of a mixture containing 25% of oxidized ethylene bisdithiocarbamic acid and 75 of unoxidized ethylene bisdithiocarbamic acid was prepared by the procedure of Example 1, using 2 moles of sodium ethylene bisdithiocarbamate (2329 g. of 22% active) and 68 g. (1 mole) of hydrogen peroxide 50% active in 200 ml. water, just sufiicient to oxidize 25% of the dithiocarbamate present.
  • Example 7 Manganese salt of oxidized ethylene bisdithiocarbamic acid 25%, with manganese salt of unoxidized ethylene bisdithiocarbamic acid (maneb) 75 characteristics of the manganese salts of both the oxidized and the unoxidized ethylene bisdithiocarbamic acids.
  • Example 8 aureus, and Salmonella typhosa were conducted by plac-' ing discs dipped in various concentrations of the test compounds on agar plates seeded with one of the test organisms, then incubating the plates for 24 hours at F. The lowest concentration of the test chemical producing a clear zone denoting absence of bacterial growth around the discs was recorded in p.p.m.
  • Example 9 Field trails of the compounds of the invention were carried out on growing potatoes in Florida.
  • the fungicides were prepared in the form of wettable powders in 8 fides, and sulfuric acid (4.9 g. concentrated acid, 0.05 mole). The addition was made over a 30-minute period, and a white precipitate formed. After stirring for 15 minutes longer, the reaction mixture was cooled to C. and
  • the experimental fungicides were mixed with water 0 8.2, 9.0, 9.45, 10.05, 10.45 and ll.75,u, indicating the presat the rate of 2 pounds Per 100 gallons and were applied ence of the zinc salt of oxidized ethylene b1sdithiocarat the rate of 125 gallons or 225 gauons per acre of bamic acid, thiuram sulfides, and a trace of the zinc salt growing Potatoes A11 Plots were Sprayed at the Same of unoxidizcd ethylene bisdithiocarbamic acid (zineb).
  • Example 12 Manganous salt of oxidized ethylene bisdithiocarbamic acid, with thiuram sulfides
  • Example 10 7 Potato field trials were carried out on the efiicacy of The procedure described in Example 11 s repeated the completely and the partially oxidized zinc and man- *P that Soluble mangaH01l$a1t Used lnstoad 0f ganese compounds in controlling early blight of potatoes.

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US367620A 1964-05-15 1964-05-15 Process for oxidizing soluble alkylene bisdithiocarbamates to produce an oxygen containing product, and the product of said process Expired - Lifetime US3401182A (en)

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US367620A US3401182A (en) 1964-05-15 1964-05-15 Process for oxidizing soluble alkylene bisdithiocarbamates to produce an oxygen containing product, and the product of said process
FR8666A FR1428360A (fr) 1964-05-15 1965-03-10 Nouveaux dithiocarbamates, procédé pour leur obtention et leurs applications
BE660963A BE660963A (en]) 1964-05-15 1965-03-11
ES0310926A ES310926A1 (es) 1964-05-15 1965-03-24 El procedimiento para la preparacion de alcohileno bisditiocarbamatos oxidados.
NL6504315A NL6504315A (en]) 1964-05-15 1965-04-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4079146A (en) * 1974-11-27 1978-03-14 Rohm And Haas Company Metal salts of mixed dithiocarbamic acids

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1453515A (en) * 1921-08-08 1923-05-01 Vanderbilt Co R T Process of making vulcanization accelerators
US2766274A (en) * 1953-03-12 1956-10-09 Du Pont Organic sulfides and their preparation
US2859246A (en) * 1955-05-09 1958-11-04 Us Rubber Co Method of desulfurizing a polymeric bis thiuram disulfide
US2929846A (en) * 1957-01-28 1960-03-22 Us Rubber Co Method of making a fungicidal substance
US3318763A (en) * 1961-08-24 1967-05-09 Vanderbilt Co R T Bacterial and fungal methods
US3322802A (en) * 1963-05-27 1967-05-30 Vanderbilt Co R T Metal salts of organodithiocarbamateorganothiocarbamoyl sulfinates and the preparation thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1453515A (en) * 1921-08-08 1923-05-01 Vanderbilt Co R T Process of making vulcanization accelerators
US2766274A (en) * 1953-03-12 1956-10-09 Du Pont Organic sulfides and their preparation
US2859246A (en) * 1955-05-09 1958-11-04 Us Rubber Co Method of desulfurizing a polymeric bis thiuram disulfide
US2929846A (en) * 1957-01-28 1960-03-22 Us Rubber Co Method of making a fungicidal substance
US3318763A (en) * 1961-08-24 1967-05-09 Vanderbilt Co R T Bacterial and fungal methods
US3322802A (en) * 1963-05-27 1967-05-30 Vanderbilt Co R T Metal salts of organodithiocarbamateorganothiocarbamoyl sulfinates and the preparation thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4079146A (en) * 1974-11-27 1978-03-14 Rohm And Haas Company Metal salts of mixed dithiocarbamic acids

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BE660963A (en]) 1965-07-01
ES310926A1 (es) 1966-01-01
FR1428360A (fr) 1966-02-11

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