CH634554A5 - Sulphur- and nitrogen-containing formals and polyformals - Google Patents

Description

The present invention relates to the compounds of the formula

0- (CH2) n- (OCH2) m-O- (CH2) n-X (I)

whose symbols are defined in claim 1.

Compounds according to the invention can advantageously be used as an antioxidant, corrosion inhibitor, sulfur-containing oil additive, biocide for combating plant infections and as a rubber curing accelerator.

Preferred variants of the compounds of the formula I according to the invention are those in which m denotes 1.

To treat plant diseases, a plant or the soil in its immediate vicinity is treated with a compound of the formula I.

The following description relates, for example, to embodiments of the compound according to the invention, their preparation and their use, the details of which are explained in more detail using the preparation and use of bis (dimethyldithiocarbamylethyl) formal (II).

To prepare the compound of formula II, dimethylamine is treated with approximately stoichiometric amounts of carbon disulfide and aqueous sodium hydroxide, heat being removed from the exothermic reaction. When the reaction mixture containing the dimethyldithiocarbamic acid sodium salt becomes homogeneous, an approximately semi-equivalent amount of bis-2-chloroethyl) is formally introduced gradually with heating at a temperature between 60 ° C and the reflux temperature of the solution, preferably up to 80 ° C. The reaction mixture is then kept in this temperature range. Small doses of deionized water are added from time to time and the aqueous phase of the two-phase system is then removed until the pH of the reaction mixture stabilizes at about 7. If desired, the compound of formula II can then be recovered according to a conventional method, the cooled reaction mixture preferably being diluted by input of deionized water and the resulting precipitated product being obtained after filtration and drying.

Using other conventional amines in place of the aforementioned dimethylamine and other conventional bis (co-haloalkyl) ethers and formals in place of the above bis (2-chloro-ethyl-formal) in the similar process discussed above, other embodiments of the compound can be used the

Formula I can be obtained, where m is 1. For the preparation of compounds of the formula

Cl- (CH2) n- (0CH2) m-0- (CH2) n-Cl in which n has the meaning given above and m 2 is 30 or 3, preferably, as for the preparation of analog components when m = 1 but below Double the tripling of the formaldehyde content for m = 2 or m = 3, a-co-haloalkyl compounds condensed with formaldehyde in the presence of an acidic catalyst, the temperature being kept at the minimum value required for water removal. If desired, these compounds can be used formally instead of the bis (2-chloroethyl) mentioned above to prepare the compound of the formula I, where m is 2 or 3. 40 Monoamines are used to obtain monomer products, the control of the relative molar ratios of the dithiocarbonate salt and the dihaloformal or ether reagents permitting substitution for one halogen or for both halogens. When the amines are used, 45 the proportions of carbon disulfide and sodium hydroxide can be varied to allow reaction with one or both amino functions. If only the dithiocarbonate is formed, then the reaction will take place with the dihaloformals or ether as in the case of the monoamines. If two dithiocarbamate functions are created, the reaction with equal molar proportions of the dihalo compounds will result in polymers having up to about 1000 molecular weights. In this case, it is believed that one end of the polymer has a halo end and its other end a dithiocarbamate end, although endings are formed by only one property-determining or functional group.

60 However, if a substantial excess of dithiocarbonate or dihalo compound is used, polymer formation is inhibited, resulting in low molecular weights. With a 2: 1 molar ratio of the reagents, for example, a compound of the type D-E-D is formed, where D is the residue from the reagent with the higher molar ratio and E is the residue from the reagent with the lower molar ratio.

634 554

The mercaptothiazole derivatives, which are variants of the compound of formula I, can be obtained from sodium salts of conventional mercaptothiazoles and the above-mentioned dihalo compounds according to a method similar to that for obtaining other variants of the compound of formula I. The preparation of mer-captothiazoles from aromatic amines and carbon disulfide or from 2 hydroxy monoaliphatic monoamines and carbon disulfide are conventional methods well known to the person skilled in the art.

The embodiments of the compound of the formula I, in particular when X and Q have the same meaning as defined under (A) or (B), can be used as rubber curing accelerators in combination with or instead of other conventional rubber curing accelerators in conventional rubber formulations, most of which but not necessarily, formulations that are curative with sulfur as the curing agent. Other conventional rubber curing agents can be used instead of sulfur.

Embodiments of the compound according to the invention can be used as biocides for the curative or preventive treatment of plants, depending on the most effective control method of the respective pathogen on the seed, on the entirety of the plant, only on the affected part of the plant or in the soil immediately surrounding the plant. The respective biocidal compound can be used either alone or in combination with an agriculturally acceptable carrier in powder form, in liquid form, by spraying, misting, washing or by immersing the object to be treated. The dosage must be adapted to the intensity of the infestation, the nature of the pathogen, the nature of the plant and the method of application or administration of the biocide. Since the compounds described, with the exception of certain mercaptothiazole derivatives, may not be toxic to plants, excess biocides which go beyond the minimum dose required to combat the respective pathogen are not harmful to the crops treated. The use of a graduated range of biocide concentrations allows the selection of an optimal concentration in each individual case, which is effective against the respective pathogen, but is not toxic or toxic for the particular plant. However, the biocidal compounds must be administered to food cultures in such a way that at the time of harvest there is practically no biocide residue at least in the edible or edible areas of the harvest. In general, aqueous, sprayed-on solutions with an active substance concentration of 1-10,000 millionth, preferably 100-1000 millionth, can be used successfully.

The compounds described can be used as antioxidants, corrosion inhibitors or as a sulfur-containing oil additive instead of or in combination with other conventional antioxidants, corrosion inhibitors or sulfur-containing oil additives in formulations similar to these substances.

The meaning of the term "alkyl" here includes

Without limitation, straight or branched chain alkyl radicals such as methyl, ethyl, i-butyl and other similar. The meaning of the term “alkenyl” here includes, but is not limited to, straight or branched chain alkenyl radicals, with the restriction that when combined with a nitrogen atom in the 1,2 positions no non-aromatic unsaturations may be present, such as 2-propenyl, 2-butenyl, 3-methyl-2-pentenyl and others similar. The meaning of the term «alkynyl»

includes, but is not limited to, straight or branched chain alkynyl radicals with the restriction that there must be no non-aromatic unsaturation in the 1,2 positions, such as 2-propynyl, 2-butynyl, 4 methyl-2-pentynyl and other similar.

The meaning of the expression “addition salts” here includes cation salts of thiocarbamate functions of a special molecule available for salt formation. Examples of such cation salts are those of the alkali and alkali earth metals such as sodium, potassium, calcium, magnesium and other similar, heavy metals such as iron and copper, and cations derived from ammonia or basic amine. The meaning of the expression “cation derived from ammonia or a basic amine” here includes the positively charged ammonium ion and similar ions derived from organic, nitrogen-containing bases which are sufficiently strong to form such cations. Such bases are a class, the limits of which are well known to the well-trained artisan. Examples of such bases are those of the formula

II-N-R3

V

wherein R2, R3 and R4 are separately hydrogen, alkyl of 1-10 carbon atoms, monocarbocyclic aryl of about 6 carbon atoms, monocarbocyclic arylalkyl of about 7 to about 11 carbon atoms, hydroxyalkyl of about 1 to about 3 carbon atoms or monocarbocyclic arylhydroxyalkyl of about 7 up to about 15 carbon atoms or have such a meaning that together with the nitrogen atom to which they are attached, two of R2, R3 and R4 form part of a five- or six-membered heterocyclic ring, the monocarbocyclic aryl groups being unsubstituted or mono - Or dialkyl substituted, and the alkyl groups contain 1 to about 10 carbon atoms.

Examples of cations derived from ammonia or a basic amine are ammonium, mono-, di- and tri-methylammonium, mono-, di- and triethylammonium, mono-, di- and tripropylammonium (iso and normal), ethyldimethylammonium, benzyldimethylammonium, cyclohexylammonium, Benzylammonium, Dibenzylam-monium, Piperidinium, Morpholinium, Pyrrolidinium, Piperazinium, 1-Methylpiperidinium, 4-Ethylmorpholinium, 1-Isopropylpyrrolidinium, 1,4-Dimethylpiperazinium, 1-n-Butylpiperidinium, 2-Methylpiperylium, l-Me-piperidinium thylpiperidinium, mono-, di- and triethanolammonium, ethyldiethanoiammonium, n-butyl-monoethanolam-monium, tris (hydroxymethyl) methylammonium, phenyl-mono-ethanolamine and other similar. The aforementioned addition salts also include those salts of those compounds of the formula I which have a nitrogen function capable of forming such addition salts. Examples of such salts are those of organic and inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, sulfonic acid, benzenesulfonic acid and others similar.

Since free dithiocarbamic acids are unstable, one cation salt form can advantageously be converted to another by passing a solution of a salt form through a cation exchanger which is mixed with the

4th

s io

15

20th

25th

30th

35

40

45

50

55

60

65

Cation of the desired salt is loaded. The acidic addition salts can preferably be obtained by mixing and drying aqueous solutions of the acids and the suitable nitrogen base compounds, the compound to be converted into the addition salt being allowed to have no thiocarbamate salt functions.

The meaning of the term “agriculturally acceptable carrier” here includes, but is not limited to, common substances such as water, kerosene, alcohol and dimethyl sulfoxide, which are used for the formulation of suspensions, solutions or powders for application to seeds, plants or in the soil for treatment pathogen infestation or for the formulation of dry concentrates which are later reconstituted in doses ready for administration.

The following examples explain details of the production and use of specific preferred embodiments of the compound according to the invention.

example 1

Bis (2-dimethyldithiocarbamyl-ethyl) formal

A. In a 25% aqueous solution of 1.0 mol of dimethylamine, 1.0 mol of solid sodium hydroxide is added with stirring and cooling. After the mixture has cooled to 30 ° C., 1.0 mol of carbon disulfide is gradually introduced in such a way that the temperature of the stirred mixture remains at approximately 30 ° C. After stirring at 30 ° C for about 4.5 hours, the mixture becomes homogeneous.

B. In the aqueous solution of dimethyldithiocarbamic acid obtained according to A, 0.5 mol of bis (2-chloroethyl) was formally introduced with heating at 60 ° C. After entering the formal, the reaction was heated at reflux for about 0.5 hours and then stored at room temperature for 16 hours. Of the two phases obtained, the aqueous phase gives an alkaline reaction in the range of pH 12. The reaction mixture is then heated at 70-80 ° C. with stirring for about 4 hours. After about 1 hour, a small amount of deionized water is added and after thorough mixing, the aqueous layer is decanted. More deionized water is then added and decanted again after thorough mixing. This procedure is repeated twice within two hours, the pH of the aqueous layer remaining constant at 7. After the last decanting, cold deionized water is slowly added to the warm reaction mixture while stirring, a granular precipitate being obtained. After filtering and drying the precipitate to constant weight, the title product softening at 68-75 ° C and melting at 78-82 ° C is obtained (84.9%).

Example 2

Bis (-2- (2-mercaptobenzothiazolyl) ethyl) formal

1 mol of sodium hydroxide is added as a 25% solution in 1 mol of mercaptobenzothyazole and the mixture is stirred for one hour. The mixture is then heated at about 60-70 ° C and stirred for an additional hour. 0.5 mol of bis- (2-chloroethyl) formal are then gradually introduced while stirring in such a way that the temperature remains between 60 and 70. After entering the form, the raction mixture is refluxed for two hours. The heating is then switched off and about 500 ml of H20 are entered. A separating oil layer is divided and washed with water until the pH of the washing liquid is about 6. The oily product is then diluted with toluene and dried by distilling the solvent in vacuo to give an 89.4% yield of the title product.

634 554

Example 3

Bis- (2-N-morpholinothiocarbonylmercaptoethyl) formal In 1 mole of sodium hydroxide dissolved in 120 g of H20, 1 mole of morpholine is added while stirring and maintaining the temperature at about 30 ° C. After the morpholine has been entered, 1 mole of carbon disulfide is gradually introduced in such a way that the temperature of the mixture remains at 35 ° C. After the carbon disulfide has been entered, 120 ml of water are introduced to dissolve the entire solid material and the mixture is kept at 30 ° for one hour. The mixture is then heated to 60 ° C and 0.5 mol of bis (2-chloroethyl) formal is gradually added over about an hour. After the formal input has been made, the reaction mixture is heated between 90 and 100 ° C. for one hour, the reaction mixture separating into two phases.

After cooling, the aqueous phase is decanted and the remaining oil is washed with successive doses of warm water until the washing liquid on silver nitrate is negative for chloride ion and the pH is 7. Entering ice causes the remaining product to solidify, with water removal and vacuum drying using Drierit giving the title product (86.9%).

Example 4

Bis- (di-isopropanolyldithiocarbamylethyl) formal In 1 mole of sodium hydroxide dissolved in 120 ml of water, 1 mole of diisopropanolamine and 1 mole of carbon disulfide are added with stirring. After entering the carbon disulfide, the mixture is heated at about 60 ° C and 0.5 mol of bis (2-chloroethyl) are formally entered. After entering the formal, the reaction mixture is heated under reflux with stirring. After about 3.5 hours, the reaction is cooled and the separated oily product is divided, washed with successive doses of fresh water to pH 7 and negative silver nitrate chloride test, and diluted with toluene. Removal of the toluene in vacuum and drying to constant weight gives the title product (75.5%).

Example 5

Bis- (2-di-2-hydroxyethyldithiocarbamylethyl) formal From 1 mol of diethanolamine, 1 mol of sodium hydroxide, 1 mol of carbon disulfide and 0.5 mol of bis (2-chloroethyl) formal are 62.3 according to a procedure similar to that of Example 4 % of the title product received.

Example 6

Poly-bis- (2- (4-dithiocarboxylpiperazinothicarbamyl-

mercapto) ethyl) formal In 6.0 moles of sodium hydroxide dissolved in 720 ml of H20, 3.0 moles of piperazine are gradually introduced over 0.5 hours. 6.0 moles of carbon disulfide are then gradually introduced into this mixture with stirring and cooling at 35 ° C. over an hour. After entering the carbon disulfide, the mixture is cooled for an additional hour. The reaction mixture is then heated to 90 ° C. and 3.0 mol of bis (2-chloroethyl) formal are gradually introduced in such a way that the temperature remains at approximately 90 ° C. After the formal input has been made, the reaction mixture is stirred at 90 ° C. for a further 3 hours. The insoluble white product obtained is removed from the reaction, cooled, crushed and washed free of chlorine ion with water. The title product thus obtained as the sodium salt is dried to constant weight at 60 ° C. and 1.0 mm vacuum (yield 96%).

5

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

634 554

Example 7

Poly-bis- (2-dithiocarbamylethylenedithiocarbamylethyl) formal

In 6.0 mol of sodium hydroxide dissolved in 480 ml HzO, ethylenediamine is slowly added with stirring with cooling such that the temperature remains at 30 ° C. 6.0 moles of carbon disulfide are then slowly added with stirring and cooling to below the reflux temperature. After entering the carbon disulfide, the reflux is continued until the reaction is moderate. The reaction mixture is then heated to 85 ° C and 3.0 moles of bis (2-chloroethyl) formal are gradually added over an hour. After formal entry, the solution is held at 85 ° C for a further two hours. The product which separates is separated from the aqueous layer, washed with warm water to pH and negative silver nitrate / chloride test and dried at 75 ° C. and 1-2 mm vacuum, the title product being obtained as the sodium salt (yield 94.9 %).

Example 8

Bis (2- (2-mercaptothiazolyl) ethyl) formal 1 mol of monoethanolamine is introduced into 1 mol of sodium hydroxide in 120 g of water with stirring, the temperature being kept below 30 ° C. After the entry has been made, 1 mol of carbon disulfide is entered while maintaining the temperature at 35 ° C. The reaction mixture is then heated to 90 ° C., held at this temperature for about half an hour, and then 0.5 mol of bis (2-chloroethyl) is formally entered. The solution is then heated at reflux for three hours. The oil that separates on cooling is washed to pH 7 and negative silver nitrate / chloride test and vacuum dried.

Example 9

By dissolving known amounts of the compounds of Examples 1, 2, 3, 4, and 8 in 10 ml of acetone, entering a drop of “Tween 20” (sorbitan monolaurate polyoxyalkylene-s dérivât sold by Atlas Powder Co.) and by dilution with water to give one Series of concentrations, suspensions were made which were subsequently used to treat infected or contaminated plants. The suspension was sprayed onto the leaf surface or, in the case of root ball nematode, placed in the soil before infestation with nematode larvae.

The suspensions were then tested in a series of experiments against bacterial, cryptogamic, viral pathogens and nematodes. Comparative experiments were carried out between (a) leaf and root pathogens, (b) external (surface) and internal pathogens and (c) facultative and compulsive parasites. The most common pathogens are fungi, which are divided into three classes 20, those of the phycomycetes, the ascomycetes and the basidomycetes, each of which was represented in the experiments. All diseases examined have their economic importance.

25 The tomato plants were in leaf grades 5-6, the bean seedlings had up to two-thirds of their primary leaves, and the second leaf of wheat was just coming out at the time of the trials. One or two days after the biocide treatment 30, the plants were inoculated with the test pathogen or pathogen. Tables 1-10 below show the results of these tests.

Table 1

Early (Alternaria) patchy disease of tomato

connection

Conc.

Lesions

Disease

Remarks

Example No.

Millionth

number / sheet "

reduction,%

Untreated

_

209

_

no damage

1

1000

67

68

no damage

100

107

49

2nd

1000

22

90

Chlorosis (jaundice)

100

95

55

between the veins of new leaves

3rd

1000

72

66

no damage

100

156

25th

4th

1000

128

39

no damage

100

173

17th

6

1000

231

0

no damage

100

206

2nd

8th

1000

141

32

no damage

100

225

0

Manebb

100

105

50

no damage

10th

142

32

1

218

0

a Lesions counted on the third leaf of the cotyledon b Maneb is (ethylene bis (dithiocarbamato)) manganese

7

634 554

Table 2 Brown rust of the wheat

connection

Conc.

Pustules

Disease

Remarks

Example No.

Millionth

Number / base sheet reduction,%

Untreated

_

36

_

no damage

1

1000

4th

89

no damage

100

14

61

2nd

1000

3rd

92

no damage

100

12

67

3rd

1000

9

75

no damage

100

32

11

4th

1000

9

75

no damage

100

29

20th

6

1000

18th

50

no damage

100

27th

25th

8th

1000

4th

89

no damage

100

25th

31

Maneb

100

2nd

95

no damage

10th

9

75

1

19th

47

Table 3

Late (Phytophthora) arthropathy of the tomato

connection

Conc.

Deceased

Disease

Remarks

Example No.

Millionth

Leaves,% a reduction,%

Untreated

-

80

_

no damage

1

1000

80

0

no damage

100

77

4th

2nd

1000

83

0

Chlorosis between the

100

83

0

Veins of new leaves

3rd

1000

30th

62

no damage

100

63

21st

4th

1000

50

37

no damage

100

70

12

6

1000

67

16

no damage

100

67

16

8th

1000

57

29

no damage

100

83

0

Maneb

100

7

91

no damage

10th

16

80

1

53

44

a disease estimated on the third leaf from the cotyledon.

Table 4

Powdery mildew

connection

Conc.

Lesions

Disease

Remarks

Example No.

Millionth

Number/

reduction,%

Primary sheet

Untreated

147

no damage

1

1000

156

0

no damage

100

156

0

2nd

1000

8th

95

Many beginning

100

122

17th

Lesions. Chlorosis

between new veins

leaves

3rd

1000

162

0

no damage

100

151

0

634554

8th

Table 4 (continued)

Connection example no.

Conc. Millionth

Lesions

Number/

Primary sheet

Disease reduction,%

Remarks

4th

1000

156

0

no damage

100

161

0

6

1000

154

0

no damage

100

135

8th

8th

1000

148

0

no damage

100

148

0

Benomyl "

5

149

0

no harm a benomyl is methyl-l- (butylcarbamoyl) -2-benzimidazole carbamate.

Table 5 Fusarium wilt of tomato

connection

Conc.

Disease

Disease

Remarks

Example No.

Millionth

evidence3

reduction,%

Untreated

.87

no damage

1

1000

.87

0

no damage

100

.68

22

2nd

1000

1.0

0

Chlorosis between the

100

.78

10th

Veins of new leaves

3rd

1000

.65

25th

no damage

100

.91

0

4-DIPA

1000

.63

27th

no damage

100

.74

15

6

1000

.74

15

no damage

100

.87

0

8th

1000

.82

6

no damage

100

.87

0

a Ratio of the number of intermediate nodes with decolorized vessels to the total number of intermediate nodes.

Table 6 Bacterial wilted tomatoes

connection

Conc.

Disease

Disease

Remarks

Example No.

Millionth

evidence "

reduction

Untreated

-

.95

1

1000

.95

0

100

1.0

0

2nd

1000

1.0

0

Chlorosis between the

100

.95

0

Veins of new leaves

3rd

1000

.85

10th

100

.91

4th

4th

1000

.95

0

100

.81

15

6

1000

.90

5

100

.95

0

8th

1000

.91

4th

100

.95

0

a Ratio of the number of withered leaves to the total number of all leaves.

9 634 554

Table 7

Tomato bacterial blotch

connection

Conc.

Lesions

Disease

Remarks

Example No.

Millionth

Number / sheet3

reduction,%

Untreated

-

165

_

no damage

1

1000

46

72

no damage

100

39

76

2nd

1000

0

100

Many beginning

100

120

27th

Lesions. Sheet-

chlorosis and necrosis

3rd

1000

27th

84

100

44

73

4th

1000

54

67

no damage

100

129

22

6

1000

73

56

no damage

100

146

12

8th

1000

51

69

no damage

100

94

43

Streptomycin

100

33

80

no damage a lesions counted on the third leaf of the cotyledon.

Table 8

South bean mosaic virus on bean seedlings

connection

Conc.

Lesions

Disease

Comments3

Example No.

Millionth

Number / primary sheet reduction,%

Untreated

-

236

slight burn marks

1

1000

233

1

slight burn marks

100

239

0

2nd

1000

241

0

Chlorosis between the

100

215

8th

Veins of new leaves.

3rd

1000

236

0

Moderate to severe

100

224

5

Leaf burns.

4th

1000

205

13

heavy leaf burns

100

222

6

6

1000

237

0

moderate leaf burns

100

198

16

8th

1000

228

3rd

slight burn marks

100

207

12

Thiouracil

1000

1

99

moderate leaf burns a leaf damage in untreated bean plants is carborundum damage suffered during inoculation. Leaf damage worsened by treatment.

Table 9 Tomato root ball nematode

connection

Conc.

Root lesions

Disease

Remarks

Example No.

mg / 50 ml number / plant reduction,%

Untreated

_

344

_

no damage

1

50

299

13

no damage

5

305

11

2nd

50

335

3rd

no damage

5

366

0

3rd

50

390

0

no damage

5

335

3rd

4th

50

335

3rd

no damage

5

325

6

6

50

328

5

no damage

5

333

3rd

8th

50

331

4th

no damage

5

360

0

634554 10

Table 10

Summary of the results of Tables 1-9

Compound millionth disease reduction,%

Example no

Untreated

1

1000

68

89

0

0

72

100

49

61

4th

0

76

2nd

1000

90

92

0

95

100

100

55

67

0

17th

27th

3rd

1000

66

75

62

0

84

100

25th

11

21st

0

73

4th

1000

39

75

37

0

67

100

17th

20th

12

0

22

6

1000

0

50

16

0

56

100

2nd

25th

16

8th

12

8th

1000

32

89

29

0

69

100

0

31

0

0

43

Maneb

100

50

95

91

-

-

10th

32

75

80

-

-

1

0

47

41

-

-

Benomyl

5

-

-

-

0

-

Streptomycin

100

-

-

80

Example 10

Rubber formulations were prepared and cured in parallel formulations using conventional curing accelerators and embodiments of the invention. The formulations and physical properties of the hardened materials are as follows:

Formulation B

Formulation A

material

amounts

(Parts by weight)

Nordel 1070 (ethylene propylene

terpolymer, DuPont) SAF Black (carbon black) Circolite (Sun Oil Co. - hydrocarbon rubber extender) zinc oxide stearic acid

Tetramethylthiuram disulfide Mercaptobenzothiazole Compound of Example 2 Sulfur

100 130

100 130

100 100

5 5

1 1

1.5 1.5 0.5

0.5

1.5 1.5

Physical properties after curing at 160 ° C for 30 min.

Tensile strength (psi) 1650 2010

Elongation (%) 940 690

100% module 100 130

200% module 150 275

35

material

amounts

(Parts by weight)

SBR (styrene butadiene rubber) 100 100

40 HAF Black (carbon black) 40 40

Zinc oxide 5 5

Stearic acid 1 1

Circolit 1 1 Electol II (Monsanto Co.

45 condensation product

Aniline and acetone) 3 3

Mercaptobenzothiazole 2 2 Bismat (R.T. Vanderbilt Co. Inc. -

Rubber curing accelerator) 2 2

so connection of example 1-2

Sulfur 1 1 Physical properties after curing at 160 ° C for 20 min.

Tensile strength (psi) 1750 3010

55 Elongation (%) 210 430

100% module 630 360

200% module 1610 875

Duro A 63 72

so wording C

material

amounts

(Parts by weight)

65 SBR

(Styrene butadiene rubber) 100 100 100 HAF Black

(Carbon black) 40 40 40

Formulation C (continued)

11 634 554

Formulation C (continued)

Material quantities material quantities

(Parts by weight) (parts by weight)

s

zinc oxide

5

5

5

Elongation (%) 180

520 600

Stearic acid

1

1

1

100% module 925

300 270

Circolit (?)

1

1

1

200% module 2160

760 600

Flectol II

3rd

3rd

3rd

Duro A 75

62 63

Mercaptobenzothiazole

2nd

2nd

2nd

10th

Bismat

2nd

-

-

Connection of example 1

-

0.3

1

Experiments with the solid compound of Example 6

Connection of example 3

-

0.5

1

a formulation similar to formulations B, C

sulfur

1.75

1.75

1.75

Prepare because of the difficulty of the hard

Tensile strength (psi)

1880

3370

3670

Disperse compound in the formulation mixture.

Claims (15)

634 554 2. A compound according to claim 1, in which m is 1. 2nd PATENT CLAIMS 1. Compound of formula 0- (CH2) n- (OCH2) m-O- (CH2) n-X (I) where Q S II (A) J> N-C-S- means where R and R 'are separated hydrogen, alkyl with 1-10 carbon atoms, cyclohexyl, alkenyl with 3-10 carbon atoms, 2-cyclohexenyl, alkynyl with 3-10 carbon atoms, carbocyclic aryl with 6-10 carbon atoms in the aryl nucleus, heterocyclic aryl with 1 or 2 heteroatoms and 3-9 carbon atoms in the aryl nucleus or aralkyl, where the aryl part is heterocyclic or carbocyclic aryl as defined above, the alkyl is alkyl as defined above and the hydrocarbon parts of each of the groups R and R 'mentioned above are unsubstituted or with alkyl as defined above , alkenyl, alkynyl, hydroxy or alkoxy as defined above, are substituted with 1-10 carbon atoms or R and R 'are linked such that they together with the nitrogen atom to which they are attached, piperidino, pyrrolidino, morpholino, piperazino , Pyridino, pyridazino, tetrahydrothiazolyl, di-hydroindolyl, tetrahydrooxazolyl or he form thiamorpholino, where the radicals formed by chaining are unsubstituted or alkyl-substituted, and its addition salts; or Q (B) means 2-mercapto-thiazolyl which is unsubstituted, substituted with alkyl, carbocyclic aryl 5 as defined above or with heterocyclic aryl as defined above, or fused to a mono- or bicyclic carbocyclic aryl nucleus or a heterocyclic aryl nucleus as defined above is; or Q 3,634,554 22. A method for combating plant diseases, characterized in that the plant or the immediately surrounding soil is treated with a compound according to claim 1. 23. The method according to claim 22, characterized in that the compound according to claim 5 is used. 24. The method according to claim 22, characterized in that one uses the compound according to claim 6. 25. The method according to claim 22, characterized in that the connection according to claim 9 is used. 26. The method according to claim 22, characterized in that one uses the connection according to claim 11. 27. The method according to claim 22, characterized in that one uses the compound according to claim 13. 3. A compound according to claim 2, in which X is Q. 4. A compound according to claim 3, in which Q S means, where R and R 'are alkyl or hydroxyalkyl having 1-10 carbon atoms. 5. A compound according to claim 4 which is formal bis (2-dimethyldi-thiocarbamylethyl). The compound of claim 4 which is bis (2-diisohydroxy-propyldithiocarbamylethyl) formal. 7. A compound according to claim 4 which is formal bis (2-di-2-hydro-xyethyldithiocarbamylethyl). 8. A compound according to claim 3, in which Q S 50 means, where R and R 'are linked and have such a meaning that together with the nitrogen atom they form a heterocyclic ring as defined in claim 1. 55 The compound of claim 8 which is bis (2-N-morpho-linothiocarbonylmercaptoethyl) formal. 10. A compound according to claim 3 in which Q is 2-mer captothiazolyl. 10th (C) »(+> | fl (-) S-C-Y-C-S- 15 means where M (+) is a cation and Y is alkylenediamino with 2-10 carbon atoms, cycloalkylenediamino with 5-6 carbon atoms in the cyclic ring, alkenylenediamino with 4-10 carbon atoms, cycloalkenylenediamino with 5 20 or 6 carbon atoms in the cyclic ring, alkynylene diamino with 4-10 carbon atoms or / ~ \ 25 -N N- \ / means, wherein the hydrocarbon parts of the Y radicals 30 are unsubstituted or substituted by alkyl, alkynyl, carbocyclic aryl defined above or heterocyclic aryl defined above; X Q, Cl or S S II II -S-C-Y-C-Sr (CII2) n- (OCII2) nrO- (CII2) n- Z. x means in which Y has the meaning given above, ZQ or Cl, x has such a meaning that it is sufficient to achieve a molecular weight of up to 1000 of the compound, n is an integer from 2-10 and m is an integer from 1 -3 mean. 11. A compound according to claim 3 which is bis (2- (2-mercapto-60 benzothiazolyl) ethyl) formal. . 12. A compound according to claim 1 which is poly-bis (2- (4-di-thiocarboxylpiperazinothiocarbonylmercapto) ethyl) formal. 13. The compound of claim 1 which is poly-bis- [2- (N- (2-65 dithiocarboxylaminoethyl) thiocarbamoylthio) ethyl] formal. 14. A compound according to claim 1 which is bis (2- (2-mercap-tothiazolyl) ethyl) formal. 15. A biocidal composition for combating plant pathogens, which contains a compound according to claim 1 and an agriculturally acceptable carrier. 16. A biocidal composition according to claim 15, which contains the compound according to claim 5. 17. A biocidal composition according to claim 15, which contains the compound according to claim 6. 18. A biocidal composition according to claim 15, which contains the compound according to claim 9. 19. A biocidal composition according to claim 15, which contains the compound according to claim 11. 20. A biocidal composition according to claim 15, which contains the compound according to claim 13. 21. A biocidal composition according to claim 15, which contains the compound according to claim 14. 15. The method according to claim 22, characterized in that one uses the connection according to claim 14.