DE1058982B - Process for the preparation of derivatives of polymeric bisthiuram disulfides - Google Patents

Description

The invention relates to the production of new polymeric bisthiuram disulfides, which z. B. to combat from microorganisms.

It has been found that by desulfurization of obtained from salts of bisdithiocarbamic acids Oxidation products, which are essentially bisthiuram disulfides, new compounds are obtained that contain considerably less sulfur than the starting materials and have unusual properties that are not present in the starting materials.

According to the invention are bisthiuram disulfides of the general formula

[- S - CS - NH - R - NH - CS - S -] _ni

in which R is a divalent alkylene, arylene or cycloalkylene radical or the grouping

CH ₂ -CH ₂

N-CH ₂ -CH ₂
CS

Process for the preparation of derivatives polymeric bisthiuram disulfides

Applicant:.

United States Rubber Company, New York, N.Y. (V. St. A.)

Representative: Dr. E. Wiegand, Munich 15,

and Dipl.-Ing. W. Niemann, Hamburg 1, Ballindamm 26, patent attorneys

Claimed Priority: Canada May 6, 1955

Lothar Martin, Harold Randolph Chipman and Charles William Gates, Elmira, Ontario

(Canada),
have been named as inventors

and η is an integer, subjected to the action of an alkali metal cyanide under weakly basic conditions, 0.5 to 1.5 mol of alkali metal cyanide being used per mole of polymeric disulfide.

Bisthiuram disulfides suitable as starting materials are described by Klopping in a paper entitled “Chemical Constitution and Antifugal Action of Sulfur Compounds cc (published von Schotanus and Jens, Utrecht, 1951) and in German patent specification 919 350.

The starting materials, namely the polymeric bisthiuram disulfides, can then easily be prepared by oxidation of corresponding bisdithiocarbamic acids, in particular metal salts of bisdithiocarbamic acids. For this purpose, the thiocyanate, in a solvent such as water, dissolved at a _pH value which is close to neutral, are oxidized, using known oxidizing agents such as ammonium persulfate, hydrogen peroxide, nitrous acid od. The like., Can be used. Mixtures of hydrogen peroxide and sulfuric acid and mixtures of sodium nitrite and sulfuric acid are particularly suitable. In the case of oxidation, buffer substances such as inorganic phosphates can be present; it is carried out advantageously in a p _H range 6 to 8

According to one embodiment of the invention, the preparation of the polymeric disulfides (starting materials) can be carried out with their desulfurization can be linked by adding dithiocarbamate, oxidizing agent and alkali cyanide can act on each other at the same time.

In carrying out the method according to the invention, the desulphurization is preferably carried out so that one the alkali metal cyanide, z. B. sodium cyanide, in a minimal amount of a solvent such as water or Alcohol dissolves and becomes a solution of the bisthiuram disulfide in a minimal amount of an aqueous or organic Adding solvent. The degree of desulfurization depends to a large extent on the amount of alkali metal cyanide used away; according to the invention are generally about 0.5 to 1.5 moles of alkali metal cyanide, for. B. sodium cyanide, 1 mole of bisthiuram disulfide is used.

The setting of the desired, weakly basic reaction conditions can generally be achieved by not adding the sodium cyanide at a significantly higher rate than it is consumed. The _pH value in the reaction mixture is suitably below 11, preferably below 10 and particularly below. 9

Desulfurization is easy at room temperature; However, the reaction mixture can also be used for Accelerating the reaction are heated, but then care must be taken that none so intense heating occurs that decomposes appreciable amounts of the starting material or of the product obtained will.

The products obtained in the process according to the invention, which mostly do not have a sharp melting point, generally have a very yellow color

909 530/384

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Color ranging from a rich light yellow to pale light yellow over a period of 2 hours 15 minutes. A precise structural formula cannot be given for the 31 in an aqueous solution containing products obtained according to the invention. 0.825 kg of sodium cyanide added. The reaction from various elemental analyzes are empirical temperature was regulated to a value between 31 and 35 ° C formulas in the range of C ₈ H ₁₂ N ₄ S ₇ to C ₁₄ H ₂₆ N ₈ S ₉ 5; the _pH value was in the range between 7.1 has been calculated. ■ ... ^and 7.4. After all the sodium cyanide solution has been added

The products obtained according to the invention have, however, been set when the mixture has been used for ^x / ₂ hours

marked by specific X-ray diffraction patterns cooled to 22 ⁰ C. The yellow reaction mixture was

draws. In the drawing represents filtered, the filter cake was washed until it was exposed

Fig. 1 was a photographic reproduction of the X-ray of thiocyanate and dried at 54 to 57 ° C. It

Radiation diffraction pattern of a known material, namely 1.390 kg of yellow product similar to that of the

borrowed from disodium ethylenedithiocarbamate; Example 1 obtained. The melting range was 158 to

Fig. 2 is a representation of the X-ray 172 ⁰ C (decomposition),

diffraction base of a preferred product according to B is Diel 3

Invention; ■ 15

Figure 3 is a scale for use in conjunction. This example illustrates a modification of the

with the. Fig. 1 and 2. '' ... '... method according to the invention, in which the poly

Fig. 1 shows various well-defined lines of what ethyl thiuram disulfide is in place concurrently with typically for well-crystallized organic compounds, the desulfurization is produced, d. H. is of low molecular weight. Fig. 2 shows less 20 the oxidation of Dmatriumäthylenditniocarbamats and well-defined but slightly broader lines, which is typical of desulphurisation being simultaneously in the same reaction reasonably well crystallized polymeric material vessel can be carried out. is. .

According to reagents, this should be the case for the X-ray test.

of the invention, product obtained in crystalline form 25 A water 400 g

are present. The product usually falls in crystalline form (in the B ammonium persulphate 62 g

general microcrystalline); it can, if desired, water 300 g

but from a solvent such as acetone or chloro q disodium ethylenedithiocarbamate

form, recrystallized, - (19 ° / ₀ aqueous solution) 302 g

The invention is explained in more detail below with the aid of some 30 sodium cyanide .. 15 e examples:

. . The water was first in a 2-1 bottle with four

^els P ^le Hälsen, which are equipped with a condenser, two additional funnels,

A moist filter cake of freshly made was provided with a stirrer and thermometer,

Polyethylene thiuram disulfide was placed in a 1-1 bottle containing 35%. Solution B was in one funnel

three necks with a stirrer, a thermometer and the solution C placed in the second funnel. the

and a dropping funnel was placed. Solutions B and C were used simultaneously for a time

125 ml of water and 75 ml of acetone were added, added to the reaction vessel for 2 hours, being good

and the agitator was started. Was stirred in the course; the temperature was in the range

of I ¹ I ₂ hours, 75 ml of an aqueous solution of about 40 21 to 35 ⁰ C. The _pH value was during the

containing 30 g of sodium cyanide, slowly added additive mostly within the range of 6.8 to 7.3

and the temperature ^{dropped to 25 0} G by external cooling and never fell outside the range 6.0 to 7.8. the

regulated. The addition rate of the sodium cyanide reaction mixture was stirred for an additional 2 hours

solution was such that during the reaction the and then filtered. A bright yellow low

_pH value of the reaction mixture below 8 remained. That 45 hit. The dry weight of the filter cake

Stirring was continued for 1 hour · after completion of the addition was 55 g. The filter cake was made with 200 ml of acetone

continue to set the sodium cyanide solution; while undressed; 24 g of an acetone insoluble

this time was the _pH value to about 7. It has a loan product as a residue. The product had a

Insoluble yellow reaction product obtained, the off-yellow color and a melting range of 182 to 184 ° C.

filtered, washed free of inorganic salts and at 50

a temperature between 50 and 55 ⁰ C Example 4 was dried. The dried product weighed approximately 65 g.

It had a melting point range from 157 to 170 ^° C. This example illustrates the desulfurization

(Decomposition) and had the following analysis: S51,3 ° / _o, under substantially anhydrous conditions. 21g

N 17.5%, C 27.3% and H 3.12%. The product is 55 dry polyethylene thiuram disulfide and 100 ml of

practically insoluble in cold water and cold organo- ethanol were put in a 500 ml bottle with three necks,

niche solvents. It is partially in the boiling point with a stirrer, thermometer and one

Acetone and chloroform soluble. It was provided with additional funnel under decomposition. It was with the

soluble in strong alkali. Stirring has begun in a stable manner at room temperature and the mixture is warmed to 35 ° C

under normal storage conditions. 60 and kept at this temperature for a

. 19 Solution of sodium cyanide in methanol (with a

Example I content of 5 g of sodium cyanide per 100 ml) dropwise

11 kg of a moist filter cake of a thiuram was added. The rate of cyanide addition

disulfides formed by oxidation of Dinatriumäthylen- was adjusted so that the _pH value of the reaction

dithiocarbamate was obtained with hydrogen peroxide, 65 the mixture was not higher than weakly basic. To this

1 kg of acetone and 1.8 kg of sodium chloride were in a manner 75 ml of the cyanide solution during a

Reaction vessel with a capacity of about 75 l was placed, then added for a period of 3 hours. The mix was 1 kg of water was added to make the sludge thinly orange-yellow. She was stirred for an additional hour and enough to make an effective stir. The tem- filtered. The filter cake was washed with methanol temperature of the mixture was increased to 32 ° C, and 70 and dried at room temperature. The yield

was 10.5 g of a yellow material with a melting range of 168 to 171 ° C, a sulfur content of 49.7 ° / ₀ and a nitrogen content of 18.1 ° / ₀ .

Example 5

197 g of a wet filter cake of poly-1,2-propylenethiuram disulfide was placed in a 1-1 bottle as used in Example 1. 103 ml of water, 45 g of sodium chloride and 22 ml of acetone were added; then stirring was started. The resulting slurry was heated to 30 ⁰ C and maintained between 30 and 35 ° C, while 50 ml of an aqueous solution of sodium cyanide (20 g of sodium cyanide per 100 ml solution contained) during a period of 1 hour and 50 minutes were added. The _pH value of the reaction mixture was in the range from 6.8 to 8.4. The mud was then nitrided. The filter cake was washed with water until it was free of thiocyanate, sucked dry and dried at room temperature. There were 22 g of a yellow product were obtained having a melting range of from 84.5 to 88 ⁰ C, a sulfur content of 46.8 ° / ₀ and a nitrogen content of 16.5 ° / o had.

IO

Example 6

310 g of a wet filter cake of a thiuram disulfide, which is obtained by oxidation of trisodium diethylenetrisdithiocarbamate the formula

Na - S - C - NH - CH ₉ - CH ₂ - N - CH ₂ CH ₉

NH-C-S-Na

C = S

N / A

were obtained in a 1-1 bottle, which, as described in Example 1, was equipped. 190 ml of water, 97 g of sodium chloride and 50 ml of acetone were added and stirring was started. The resulting slurry was heated to 35 ° C and maintained at this temperature, while 35 ml of an aqueous sodium cyanide solution (20 g of sodium cyanide per 100 ml contained) was added over a period of l _^3/4 hour were. The _pH value of the reaction mixture was relatively high (8.5 to 8.7), which indicated a slow reaction. After standing overnight, the _pH value had dropped to 7.6. A further 15 ml of cyanide solution were then added over a period of ¹ Z _{2 hours.} Stirring was continued for ¹ Z ₂ hours, then the reaction mixture was filtered off. The filter cake was washed with water until it was free of thiocyanate, sucked dry and dried at room temperature. 38 g of a cream-colored product with a melting range of 96 to 100 ° C. and a sulfur content of 49.6 ° / ₀ were obtained.

Example 7

In a 1-1 bottle equipped as described in Example 1, 114 g of a moist filter cake of polymeric p-phenylenebisthiuram disulnd was placed and 70 ml of water was added to make a sludge in the bottle. 18 ml of acetone and 20 g of sodium chloride were added, then the mixture was heated to 30 ⁰ C. Over a period of 2 hours, 50 ml of a solution containing 10 g of sodium cyanide were added with thorough stirring. The temperature of the reaction mixture was controlled between 28 and 3O ⁰ C; the _pH value was below 8.0. After all of the cyanide was added, the mixture was stirred for 30 minutes, cooled to room temperature and filtered. The cream colored reaction product was washed with water until it was free of thiocyanate and dried at room temperature. The dry product weighed 31 g. The material did not melt until 23O ⁰ C.

Claims (2)

Patent claims: 1. A process for the preparation of derivatives of polymeric bisthiuram disuhides, characterized in that that bisthiuram disulfide of the general formula [- S - CS- NH- R - NH- CS- S—] ", in which R is a divalent alkylene, arylene or cycloalkylene radical or the grouping CH ₂ -CH ₂ -N CS CH ₉ - CH ₉ and η is an integer, can be subjected to the action of an alkali metal cyanide under weakly basic conditions, preferably 0.5 to 1.5 mol of alkali metal cyanide being used for 1 mol of polymeric disulfide. 2. The method according to claim 1, characterized in that the preparation of the polymer Disulphides (starting materials) with their desulphurisation by adding dithiocarbamate, oxidising agent and alkali metal cyanide can act on each other at the same time. 1 sheet of drawings © 909 530/384 6.