DE2109755A1 - Substituted thiadiazolidinediones - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG

Our reference: O.Z. 27 372 Sws / Wil

67OO Ludwigshafen, March 1st, 1971 Substituted thiadiazolidinediones

The present invention relates to new valuable thiadiazolidinediones, which herbicidal properties, herbicides containing these compounds and the use of these compounds as Herbicides.

It is known to use oxadiazolidinediones (Belgian patent 693 791) as herbicides. However, their effect is unsatisfactory.

It has been found that the new thiadiazolidinediones of the general formula

•NO

in which R is hydrogen or an aliphatic radical optionally substituted by halogen and having 1 to 4 carbon atoms, X alkyl, haloalkyl, alkoxy, alkylmercapto, halogen, alkylsulfonyl, the cyano radical or a substituted carbamoyl radical of the general formula

0 ^R 2

means in the R, and. Rp are the same or different and Hydrogen or an aliphatic radical which is optionally substituted by halogen, and η denotes the numbers 0, 1, 2, 3, have a strong herbicidal, especially selective herbicidal effect.

The thiadiazolidinediones according to the invention show a stronger one herbicidal effect than the well-known oxadlazolidinediones. This effect is particularly evident in relation to the undesired ones

36/71 209837/119 « ~ ² ~

ο. ζ. 27 372

Plants Echinochloa spp., Poa spp., Stellaria media, SInapis arvensis, Alopecurus myosuroides, at application rates of 0.5 to 2 kg of active ingredient per hectare. The new compounds are suitable for Use in the useful plants Triticum spp., Hordeum vulgare, Oryza sativa, Zea mays, Gossypium hirsutum, Soja hisplda.

The thiadiazolidinediones according to the invention are obtained if phenyl isothiocyanates are allowed to react with chlorine in the presence of alkyl isocyanates, and then the reaction products hydrolyzed.

Pur the starting products phenyl isothiocyanate and methyl isocyanate The reaction sequence can be determined by the following formula reproduce:

N = C = S + Cl,

+ H ^ C-N = C = O

= c:

σι

Cl

t!

he

+ H ₂ O

-2HC1 N ==

The preparation of the compounds is illustrated by the following examples explained:

example 1

2-Methyl-4-phenyl- 1,2,4-thiadiazolidine-3,5-dione In a solution of 1 ^ 5 parts by weight of phenyl! Sothiooyanate and 57 parts by weight of methyl isocyanate in 950 parts by weight of carbon tetrachloride are stirred at -5 to 0 ° C 71 Control point chlorine initiated. Then the reaction mixture

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ΐβ hours at room temperature, stirred. After adding diethyl ether, the crystalline mass is filtered off with suction and dried in a vacuum desiccator. For hydrolysis, the product obtained with stirring at 15 to 20 ⁰ C in 15ΟΟ parts by weight of water is added in portions. After the hydrolysis, the crude product is filtered off with suction, washed with water until the reaction is neutral and dried at 50 ^° C. in a vacuum drying cabinet.

This gives the a-methyl- ^ phenyl-lja ^ P.p. 182-184 ° C.

The compound has the following structural formula

Example 2

2-methyl-4- (3-methylcarbamoyloxyphenyl) -1, 2,4-thiadiazolidine-3,5-dione

14.2 parts by weight of chlorine are introduced into a suspension consisting of 41.6 parts by weight of m-methylcarbamoyloxyphenyl isothiooyanate, 11.4 parts by weight of methyl isocyanate and 400 parts by weight of carbon tetrachloride, with stirring at -5 to 0 ° C. The reaction mixture is then stirred for 16 hours at room temperature. After work-up and hydrolysis, as described in Example 1, 168 receives the 2-methyl-4- (j5-methylcarbamoyloxyphenyl) -1,2,4-thiadiazolidine-3,5-dione with the Pp. To 170 ⁰ C.

The compound has the following structural formula:

! t

0 "
Y 0

Qtm \ HAL INSPECTED? Π 98 3 7/1199

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In a corresponding way one obtains:

2-MetTiyl-4- (3-äthylcarbamoyloxyphenyl) -l, 2 _J 4-thiadiazolidine-3,5-dione, mp. 146 to 14-7 ⁰ C

2-methy 1-4- (jj-isopropylcarbamoyloxyphenyl) -1,2,4-thiadiazolidine-3,5-dione, -Fp. 151 to 153 ° C

2-Methy1-4- (3-butylcarbamoyloxypheny1) -1,2,4-thiadiazolidin-3 ,, 5-dione, Pp. 118 to 12O ⁰ C

2-Methyl-4- [3- (1-chlorobutyl-2-carbamoyloxy) -phenyl] -1,2,4-thiadiazolidine- ^ S-dione, pp. 14-143 ° C 2-methyl-4- (3 -methylsulfonylphenyl) -l _i 2,4-thiadiazolidine-3 _i 5-dione, m.p. 190 to 191 ^° C.

2-methyl-4- (3-trifluoromethylphenyl) -1 _J 2 _i 4-thiadiazolidine-3,5-dione, bp 75 ms 76 ^° C

2-methyl-4- (4-trifluoromethylphenyl) -1,2,4-thiadiazolidine-3 _J 5-

2-methyl-4- (3-chloro-4-methoxyphenyl) -l / 2,4-thiadiazolidine-3,5-

2-methyl-4- (3,4-dichlorophenyl) -1, 2,4-thiadiazolidine-3,5-dione Mp 207-209 ° C

2-methyl-4- (4-chlorophenyl) -1,2,4-thiadiazolidine-3,5-dione, 2-methyl-4- (4-fluorophenyl) -l, 2 _J 4-thiadiazolidine-3,5- dione, pp. 180-182 ° C

2-methyl-4- (3-chloro-4-bromophenyl) -l, 2 _J 4-thiadiazolidine-3,5-

The m-alkylcarbamoyloxyphenyl isothiocyanates required as starting materials can be prepared from m-hydroxyphenyl isothiocyanate and suitable alkyl isocyanates.

In this way, for example, can be produced:

m-Methylcarbamoyloxyphenylisothiocyanat, MP. 98 to 99 C m-Ethylcarbamoyloxyphenylisothiocyanat, MP. 83 to 85 ⁰ C m-Allylcarbamoyloxyphenylisothiocyanat, MP. 59, to oil ⁰ C tn-isopropylcarbamoyloxyphenylisothiocyanat, MP 73 to 75 ° C m- (1-chloro-butyl-2-carbamoylox3 ") -phenyl isothiocyanate, m.p. 88 bis

OWKWNAL

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The compounds according to the invention can be used as solutions, emulsions, Suspensions or dusts are used. The forms of application depend entirely on the intended use; You should in any case ensure a fine distribution of the active substance.

For the production of directly sprayable solutions, hydrocarbons with boiling points higher than 150 ⁰ C, z. B. tetrahydronaphthalene or alkylated naphthalenes, or organic liquids with boiling points higher than 150 ⁰ C and one or more functional groups, z. B. the keto group, the ether group, the ester group or the amide group, this group being a substituent on a hydrocarbon chain or being part of a heterocyclic ring, can be used as spray liquids.

Aqueous application forms can be made from emulsion concentrates, Pastes or wettable powders (wettable powders) can be prepared by adding water. For the production of emulsions you can the substances as such or dissolved in a solvent, using wetting agents or dispersants, e.g. B. Polyethylene oxide addition products be homogenized in water or organic solvents. But it can also consist of active substances, Emulsifiers or dispersants and possibly solvents Concentrates are prepared that are suitable for dilution with water. Oil dispersions can be produced with oils will.

Dusts can be produced by mixing or grinding together the active substances with a solid carrier, e.g. B. kieselguhr, talc, clay or fertilizers can be produced.

The following examples explain the application of the new active ingredients:

Example 3

The plants are grown on an agricultural area Triticum aestivum, Hordeum vulgare, Oryza sativa, Sinapis arven-

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sis, Stellaria media, Poa annua, Poa trivialis, Alopecurus myosuroides and Echinochloa crus-galli at a height of 3 to 17 cm with the active ingredients

I 2-methyl-4-phenyl-1,2,4-thiadiazolidine-3,5-dione

II 2-methyl-4- (3-methylcarbamoyloxyphenyl) -1, 2,4-thiadiazolidine-3,5-dione

III 2 ~ methyl-4- (3-isopropylcarbamoyloxyphenyl) -1, 2,4-thiadiazolidine-3,5-dione

IV 2-methyl-4- (3-butylcarbamoyloxyphenyl) -1, 2,4-thiadiazolidine-3,5-dione ■

and the comparative active ingredient

V 2-methyl-4-phenyl-1,2,4-oxadiazolidine-3,5-dione

in each case at an application rate of 1.5 kg of active ingredient per hectare, dispersed treated in 500 liters of water per hectare.

After three to four weeks it was found that the active ingredients I to IV were equally well tolerated by crop plants showed a stronger herbicidal effect than the comparative active ingredient V.

The result can be seen from the following table:

Active ingredient

I II -IH IV

Triticum aestivum 5 5 10 0 5 Hordeum vulgar 5 5 5 0 5 Oryza sativa 5 5 5 0 5. Sinapis arvensis 90 90 8o 80 70 Stellaria media 90 80 90 80 65 Poa annua 85 75 75 70 50 poa trlvialis 80 75 70 70 45 Alopecurus tnyosuroides 80 75 75 75 6o Echinochloa crus-galli 95 80 90 80 40

0 = without damage
100 = total damage

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Biologically effective as I to IV are: 2-methyl-4- (5-ethylcarbamoyloxyphenyl) -l, 2,4-thiadiazolidine-; 5.5 dion and

2-methyl-4- [3- (1-chlorobutyl-2-carbamoyloxy) phenyl} -1,2,4-thiadiazolidine-3j5-dione as

2-methyl-4- (3-tert-butyl-carbamoyloxyphenyl) -1,2,4-thiadiazolidine-3,5-dione.

Example 4

Loamy sandy soil was filled into test vessels and the seeds of Zea mays, Gossypium hirsutum, Soja hispida, Poa annua, poa trivialis, Alopeeurus myosuroides, Echinochloa crus-galli, Sinapis arvensis and Stellaria media are sown and then with the active ingredients I, II, III and IV, each in one application rate of 2 kg of active ingredient yes ha, dispersed in 500 liters of water per ha, treated.

After four to five weeks it was found that the plants Poa annua, Poa trivialis, Alopeeurus myosuroides, Echinochloa crus-galli, Sinapis arvensis and Stellaria media were almost completely dead, while Zea mays, Gossypium hirsutum, and soy hispida continued to grow without damage. The active ingredients can be used as total herbicides at higher application rates.

Example 5

80 parts by weight of compound I are mixed with 20 parts by weight N-methyl-oC-pyrrolidone and receives a solution that for Application in the form of the smallest drops is suitable.

Example 6 ■ '

20 parts by weight of compound II are dissolved in a mixture from 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-M-rflonoethanolamide, 5 parts by weight of the calcium salt of dodecylbönzenesulfonic acid and 5 parts by weight of the adduct of 4 "O moles of ethylene oxide to 1 mole of hicinus oil.

ORIGINAL INSPECTTED 209837/1199

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Pour and finely distribute the solution in 100,000 parts by weight of water to obtain an aqueous dispersion that is 0.02 percent by weight of the active ingredient.

Example 7

20 parts by weight of compound III are dissolved in a mixture that of ^ 0 parts by weight of cyclohexanone, 30 parts by weight Isobutanol, 20 parts by weight of the adduct of 7 moles ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil consists. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02 percent by weight of the active ingredient.

Example 8

20 parts by weight of compound IV are dissolved in a mixture that from 25 parts by weight of cyclohexanol, 65 parts by weight a mineral oil fraction with a boiling point of 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide 1 mole of castor oil consists. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives a aqueous dispersion containing 0.02 percent by weight of the active ingredient.

Example 9

20 parts by weight of the active ingredient I with 3 parts by weight of the sodium salt of diisobutyl-naphthalene-oC-sulfonic acid, 17 Parts by weight of the sodium salt of a lignosulfonic acid a sulphite waste liquor and 60 parts by weight of powdered silica gel mixed well and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water a spray mixture containing 0.1 percent by weight of the active ingredient is obtained contains.

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Example 10

3 parts by weight of compound II are intimately mixed with 97 parts by weight of finely divided kaolin. One gets in this way a dust containing 3 percent by weight of the active ingredient,

Example 11

30 parts by weight of compound III become more powdery with a mixture of 92 parts by weight! Silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel are intimately mixed. In this way, a preparation of the active ingredient with good adhesion is obtained,

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Claims (10)

- 10 - O. Z. 27 372 Claims Substituted thiadiazolidinediones the discontinued in which R is hydrogen or an aliphatic radical optionally substituted by halogen and having 1 to 4 carbon-Jq (I. atoms, X alkyl, haloalkyl, alkoxy, alkylniercapto, alkylsulfonyl, Halogen, the cyano radical or a substituted carbamoyloxy radical of the general formula - ^ ^r l
-0-CN. 0 ^R 2 means in the R-, and? _t p are the same or ¹ different and are hydrogen or an aliphatic radical which is optionally substituted by halogen and η denotes the numbers 0, 1, "2, 3. 2. Herbicide containing a solid or liquid carrier Jr and a substituted thiadiazolidinedione according to claim 1. j5. 2-methyl-4-phenyl-1 _J 2,4-thiadiazolidine-3,5-dione. 4. 2-Methy 1-4- (3-methylcarbaiaoyloxyphenyl) -1, 2,4-thiadlazolidine-3,5-dione. 5. 2-F4ethyl-4- (3-ethylcarbyl ir toyloxyphenyl) -! , 2, 't-thiudiu ^ olidin-3,5-dione. 6. 2-methyl- ' ^l l - (3-ir: opiOpylcai ^a b £ mioyloxypheiiyl) -i, 2, 4-ί-1ι1; κΗα., Ο11ϋ 7. 2-MeUiy.L ~ 4- (3-butylc; arbaijiiiy Inxypheiiyl) -! , 2, Ί-t.hi.-UH.u olidia- BATH 209837/1199 " ^M. - 11 - O.Z. 27 572 8. 2-Methyl-4-jj5- (1-chlorobutyl-2-carbamoyloxy) -phenyl] -1, 2, K- thiadiazolidine-3,5-dione. 9. 2-Methyl-4- (5-methylsulfonylphenyl) -1, 2,4-thiadiazolidine-3 _i 5-dione. 10. Use of a substituted thiadiazolidinedione according to Claim 1 as a herbicide. Badische Anilin- & Soda-Fabrik AG S us 209837/1199 ORDINAL INSPECTED