DE2633790A1 - ISOXAZOLYLMETHYLTHIOLCARBAMATE - Google Patents

Description

Our reference: O. Z. J52 ΙΟβ Sws / Kl 67OO Ludwigshafen, July 26th, 1976

The present invention relates to new, valuable Isoxazolylmethylthiolearbamate, Herbicides containing these compounds and methods of controlling undesired vegetation with these connections.

From French patents 2 188 6O6 and 2 205 it is known that thiolcarbamic acid esters of heterocyclic Methylene thiols are herbicidally effective. As heterocyclic Components of these thiolcarbamic acid esters, which are not physically characterized in more detail, are only those of imidazole, thiazole, oxadiazole, pyridine and pyrimidine are called.

on the type of herbicidal activity, e.g. selectivity and The compatibility with crop plants and the application rates were not disclosed. The active ingredients have only a low level herbicidal effect.

Numerous thiol carbamates are known as herbicides. Some of which reached in the agricultural and horticultural Practice is of great importance in eliminating unwanted vegetation. These substances are characterized together by their good effect against undesirable grasses. They make a difference however, their effect against individual species from this family. For example, wild oats are made from Ν, Ν-dipropyl thiolethyl carbamate combats, while this species at Ν, Ν-Dipropyl-thiolpropylcarbamat is not listed in the manufacturer's recommendations. From Ν, Ν-Dipropyl-thioläthylcarbamat will have a good effect against Setaria spp. reported while the effect of N, N-diisopropy1-thiol-2,3-dichloroallylcarbamate this fell away. In addition to combating unwanted grasses, some compounds can be used this class also includes cyperaceae and some broad-leaved ones

249/76 709885/0200 - ₂ -

- / - ο. ζ. 32 io6

Weeds are destroyed. For example, N, N-dipropyl-thiolpropylcarbamate against Cyperus spp. has a very reliable effect, while N, N-diisopropyl-thiol-2,3-dichloroallylcarbamate has almost no effect on these species. An essential criterion for the use of these agents are their differences in selectivity for the individual crops. For example, N-ethyl-N-cyclohexyl-thioläthylcarbamt is mainly used in beta beets. The most important crop for N, N-diisobutyl thiolethyl carbamate is maize. Particularly surprising this difference is even with N, N-diisopropyl-thiol-2,3-dichlorallylcarbamat and N, N-diisopropyl-thiol-2,3 _J 3 trichlorallylcarbamat. Both products can easily be used in broad-leaved crops such as beets and rapeseed. Manufacturers and distributors only recommend N, N-diisopropyl-thiol-2,3,3-trichloroallylcarbamate for grain, as this is less aggressive for these crops.

Known thiol carbamates generally have a high vapor pressure, what the following list shows:

Active ingredient vapor pressure mm Hg at ⁰ C

N, N-dipropyl thiolethyl carbamate 34 x 10 ~ ³ 25

Ν, Ν-diisobutyl thiolethyl carbamate 13 x 10 " ³

Ν, Ν-Dipropyl thiolpropyl carbamate 10.4 χ 10 ~ ³ _, _

N-ethyl-N-cyclohexyl-thiolethyl-6.2 χ ΙΟ " ³ 25

carbamate

NN-Diisopropyl-thiol-a ^ -dichlor- 1,5 χ 10 "* ¹ 25

allyl carbamate

NN-Diisopropyl-thiol-a ^^ - tri- 1,2 χ ΙΟ " ⁴ 25

chlorallyl carbamate

Hexahydro-1H-azepine-1-carbamide-5,6 χ ΙΟ "" - ⁵ 25

acid urethiol ethyl ester

S- (4-chlorobenzyl) -N, N-diethyl- 1.476 χ 10 " ⁶ 20

thiol carbamate

709885/0200 _ ₃ -

- Y- OZ 32 106

With the exception of the last one, all of these active ingredients must be incorporated into the soil to avoid evaporation losses. The same purpose is likely, besides the training in the penultimate one, by damming the water in rice fields can be achieved.

Although the incorporation of herbicides is generally positive for a number of reasons, it harbors Application method has considerable disadvantages in itself. Such disadvantages are, for example, the additional workload and the need to purchase special equipment for training. This is especially true in less mechanized ones Countries uncomfortably noticeable. The soil of the seed bed is loosened excessively, so that for certain seeds when it is dry Difficulties arise. In areas with heavy driving rain this is particularly important on sloping terrain additional tillage increases the risk of erosion. as well Soil loosening in very stormy and dry zones contributes to soil erosion by wind. Tried for these reasons move the soil as little as possible to cultivate the fields under the above conditions (system minimal tillage, reduced tillage).

Active ingredients are therefore being sought that are alternatives to incorporation Offer. In the field of thiol carbmates with their specific properties, with the exception of hexahydro- IH-azepine-l-carbamic acid thiol-ethyl ester and S-CJj-chlorobenzyl) -N, N-diethylthiol carbamate, which are used in rice do not yet exist. Attempts in this direction have been made more recently by the manufacture of thiol carbamate sulfoxides made.

It has now been found that isoxazolylmethylthiol carbamates of the general formula

709885/0200

- A - OZ 52 106

in the

R is hydrogen, alkyl, optionally substituted by alkyl Cycloalkyl, aralkyl or optionally substituted aryl,

R ^{2 is} hydrogen, optionally substituted alkyl, aryl or halogen,

■ 7. U

R ^J and R hydrogen or alkyl,
R ^ and R independently of one another

Alkyl, alkenyl, cycloalkyl, alkoxyalkyl or haloalkyl optionally substituted by alkyl, and additionally R ^ and R together with the nitrogen atom, optionally 4-, 5-, 6- or 7-membered heterocyclic ring substituted by lower alkyl mean a strongly herbicidal and also have a selective effect.

In addition to a wider range of action, they offer flexibility in the application method that was previously available in this one Substance class was unknown.

The radicals R contained in the isoxazolyl methylthiol carbamates of the general formula I mean, for example:

R is hydrogen, lower alkyl with up to 6 carbon atoms, e.g. methyl, ethyl, n-propyl, i-propyl, η-butyl, sec-butyl, i-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, n-hexyl; cycloalkyl optionally substituted by lower alkyl groups and having a total of up to 8 carbon atoms e.g. Cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl; Aralkyl, e.g. benzyl, 1-phenylethyl, 2-phenylethyl; or where appropriate substituted aryls e.g. phenyl, chlorophenyl, fluorophenyl, Dichlorophenyl, trifluoromethylphenyl;

709885/0200

O.Z. 32 106

R is hydrogen, optionally substituted lower alkyl up to 6 carbon atoms, e.g. methyl, ethyl, i-propyl, chloromethyl; Aryl e.g. phenyl; or halogen, e.g. chlorine, bromine, iodine;

-r / ι

R ^ and R are hydrogen or lower alkyl, especially methyl;

R ^ and R independently of one another lower alkyl with up to 6 carbon atoms, e.g. methyl, ethyl, n-propyl, i-propyl, η-butyl, sec-butyl, i-butyl, n-pentyl, 2-pentyl, 3- Pentyl, n-hexyl; lower alkenyl with up to 4 carbon atoms, for example allyl, methallyl, but-2-en-1-yl, but-4-en-1-yl; optionally substituted by lower alkyl groups, cycloalkyl with a total of up to 8 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclopentyl; Alkoxyalkyl with a total of up to 6 carbon atoms, for example 2-methoxyethyl, 2-ethoxyethyl, 1-methoxy-2-propyl, 3-methoxypropyl; Haloalkyl with up to H carbon atoms, for example 2-chloroethyl, 1-chloro-2-propyl, 3-chloropropyl; as well as R? and R together with the nitrogen atom is a heterocyclic ring optionally substituted by one or more lower alkyl groups and having a total of up to 10 carbon atoms, for example azetidine, 2-methylazetidine, 2, ⁱ -dimethylazetidine, 2,4,4-trimethylazetidine, pyrrolidine, 2-methylpyrrolidine , 2-ethylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 2-methylpiperidine, 2-ethylpiperidine, 2-methyl-5-ethylpiperidine, azepine, 2-methylazepine, 2,3-dimethylazepine, heptamethyleneimine, bicyclo 3-azanonane, morpholine, 2,6-dimethylmorpholine, 3,5-dimethylmorpholine.

The compounds of the general formula I according to the invention can according to the reaction equation given below by reacting an isoxazolyl methyl halide or methyl alkanesulfonate be made with the salt of a thiol carbamate.

709885/0200 - ^β -

Method A:

R ¹

^UX C - X + MSCN

A »

II III

O. Z. 32 106 "2633/90

+ M-X

R to R have the meanings given above; X denoted halogen or alkanesulfonate and M an alkali metal atom or an ammonium radical optionally substituted by two or three alkyls. The starting materials of the formula II used in process A are known or can be prepared by reacting nitrile oxides with acetylene halides. Such substances are, for example, 5-chloromethyl-3-methylisoxazole _s 5-bromomethyl-3-äthylisoxazol, 5-chloromethyl-3-isopropylisoxazole, 5-bromomethyl-3-tert -butylisoxazole, 5-chloromethyl-3,4-dimethylisoxazole, 5 - (1'-Chloroethyl) -3-methylisoxazole, 5-bromomethyl-3-phenylisoxazole, 5-chloromethyl-3- (3 ', 4 ^f -dichlorophenyl) -isoxazole, 5-bromomethyl-3-cyclohexylisoxazole. The compounds 5-chloromethylisoxazole and 5-bromomethyl-3-niethyl- ⁱ -chloro (or 4-bromo) isoxazole are known from the literature (Kochetkow and coworkers, Chemical Abstracts 47, 2167 (1953); Khim, Geterotsikl Soedin 1974 , 602). The corresponding isoxazolyl-methyl-alkanesulfonates can be prepared from known isoxazolylmethanols (Gazz. Chim. Ital. 69 , 536 (1939)) in the usual way by reaction with alkanesulfonic acid chlorides in the presence of agents that bind hydrogen chloride, such as pyridine. The isoxazolylmethyl halides can be prepared, for example, as follows. 709885/0200

mm 7 »

0. line 32 106

Regulation Al

CH ₂ -Br

JTT / ν ⁶

CH,

238 g (parts by weight) of propargyl bromide, 476 g (parts by weight) of phenyl isocyanate and 158 g (parts by weight) nitroethane are dissolved in 1500 ml of toluene, and at 15 to 20 ⁰ C and 1 ml of triethylamine, which serves to activate the phenyl isocyanate, was added. The temperature is kept at 15 to 30 ° C. for 3 hours and 1 ml of triethylamine (4 ml in total) is added every hour. Thereafter, the mixture is stirred ^{at 70 ° C. for 1 hour and cooled.} The precipitate is filtered off with suction and the residue is washed with 1 l of toluene. The combined filtrates are concentrated and the residue is distilled in an oil pump vacuum. At 59 to 61 ° C./0.2 mm Hg, 310 g (= 88 % theoretical yield) of 3-bromomethyl-5-methylisoxazole _{distill over (n D} = 1.5168).

C ₅ H ₆ BrNO = (176)

Calc .: C 34.2 H 3.4 N 7.9 Br 45.5 Found: C 34.0 H 3.4 N 8.0 Br 45.4

60 MHz NMR spectrum (in CDCl ₃ ; cf values): 2.3 (3H, s) 4.44 (2H, s)

6.15 (lH, s)

¹³ C-NMR spectrum (in CDCl, ppm values relative to TMS): 167.2 (C), 160.1 (C), 104.5 (CH), 18.8 (CH ₃ ), 11, 3 (CH ₃ ).

Regulation A2

CH

3 il II CH

93.5 g (parts by weight) of acetohydroximoyl chloride (Ber. Dtsch. Former Ges. JlO, I677 (1907)) and 90 g (parts by weight) of isobutinyl chloride are stirred in 1500 ml of benzene and at 15 to 20 ° C with 105 g

709885/0200

O.Z. 32 106

(Parts by weight) triethylamine added dropwise. Then 1 hour at 20 to 25 ° C and 1 hour at 70 ⁰ C is stirred. After cooling, it is filtered and the piltrate is concentrated. The remaining distillate is distilled in an oil pump vacuum. 133 g (92 % of theory) of XI with a boiling point of 48 to 50 ° C./0.05 mm Hg are obtained; n ^ ⁵ = 1.4740.

C ₆ HgNOCl (145.5)

Calc .: C 49.6 H 5.5 N 9.7 Cl 24.5 Found: C 49.5 H 5.7 N 10.0 Cl 24.0.

60 MHz NMR spectrum (in CDCl ₃ , / values) 1.78 (d, 3H); 2.3 (s, 3H); 5.05 (9, 1H); 6.09 (s, IH).

¹ ^ C-NMR spectrum (in CDCl ₃ , ppm values relative to TMS): 171.5 (C); 159.8 (C); 102.5 (CH); 47.4 (CH); 23.3 _(CH3); 11.5

(CH ₃ ).

Regulation A3

^C 2 ^H 5 "~~ iri

119 g (parts by weight) of propargyl bromide, 95 g (parts by weight) of nitropropane and 440 g (parts by weight) of triethylamine are dissolved in 1200 ml of chloroform and 155 g (parts by weight) of phosphorus oxychloride are added dropwise ^{at 0 ° C.} It is then refluxed for 30 minutes at 20 ° C. and for 2 hours. After cooling, it is filtered and concentrated, and the residue is taken up in water. The water phase is extracted again with toluene and the combined toluene phases are washed with water and then dried over sodium sulfate. The sodium sulfate is then separated off and the piltrate is concentrated; the residue is distilled in an oil pump vacuum. 150 g (79% of theory) distill off at 78 to 79 ° C./0.1 mm Hg; n ^ ⁵ = 1.5108.

709885/0200

- y- oz 32 106

CgHgBrNO C190)

Calc .: C 37.9 H 4.7 N 7.4 Br 42.0 Found: C 38.0 H 4.6 N 7.6 Br 41.7.

In a corresponding way one obtains:

^CH 3 "T" 1

⁰ "'CH ₂ -Cl njp = 1.4806

^0H 3 ΠΙ

= 1.5500

CH,

CH-Br

CH-Cl
XC ₇ H ₁₇ -S-CH, -, II

CH-Br

CH-Cl

CH-O-CH ₂ -

CH ₂ -Cl

The compounds designated by the general formula III are salts of thiocarbamic acids. As a typical representative can nen the sodium salts or the ammonium salts of N, N-dimethylthiolcarbamic acid, optionally substituted by two or three alkyl radicals, Ν, Ν-diethylthiolcarbamic acid, N, N-diisopropylthiolcarbamic acid, NjN-Di-n-propylthiolcarbamic acid,

709885/0200

- 10 -

-W-

O ₀ line 32 106

N, N-di-n-butylthiolcarbamic acid, N, N-diisobutylthiolcarbamic acid, N-ethyl-N-n-butylthiolcarbamic acid, N-ethyl-N-isopropylthiolcarbamic acid, N-Ethyl-N-cyclohexylthiolcarbamic acid, N, N-diallylthiolcarbamic acid, also M-azetidine, N-pyrrolidine, N-piperidine, N-azepinthiolcarbamic acid and their in the ring one to three methyl and / or ethyl groups substituted derivatives are mentioned, which are prepared in the usual way can.

Process A can be carried out in the presence of any inert, organic solvent. For example with hydrocarbons, for example cyclohexane, benzene, toluene; or halogenated hydrocarbons Z ₀ B, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene; or ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether; or lower alcohols or ketones, for example methanol, ethanol, isopropanol, acetone, _s methyl ethyl ketone, cyclohexanone; or nitriles, for example acetonitrile or water, mixtures of these solvents can also be used.

Process A is used for the production of the new active ingredients preferred.

Alternatively, the isoxazolylmethylthiol carbamates according to the invention can also be used of the general formula I according to process B by reacting isoxazolylmethyl mercaptans or their Make salts with carbamic acid chlorides.

Method B:

C-S-Y + Cl-C-N

R-

CS-CO-N
R.

+ Y-Cl

IV

709885/0200

- li -

Oo Z.32 ΙΟβ

In the formulas, R to R have the meanings given above and Y denotes hydrogen, an alkali metal atom or an optionally ammonium radical substituted by two or three alkyls.

The general formula IV represents starting compounds which can be prepared from the isoxazolylmethyl halides of the general formula II by conventional methods by reaction with hydrogen sulfide or its salts (e.g. Houben-Weyl, Methods of Organic Chemistry Vol _{0 IX, pp. 1-18) »} The following mercaptans of the formula IV may be mentioned in detail: 3-methylisoxazolyl-5-methyl mercaptan, 3-ethylisoxazolyl-5-methyl mercaptan, 3-phenylisoxazolyl-5-methyl mercaptan, 3-methylisoxazolyl-5- (1'-ethyl) mercaptan.

Carbamoyl chlorides are considered to be the carbamoyl chlorides of the formula V of dimethylamine, diethylamine, di-n-propylamine, des Diisopropylamine, di-n-butylamine, N-ethyl-n-butylamine, of N-ethyl-n-isopropylamine, of azetidine, of pyrrolidine, of piperidine, azepine and their derivatives substituted in the ring with one to three methyl and / or ethyl groups .

Process B is expediently carried out in the presence of a hydrogen chloride acceptor be performed. Any inorganic bases, e.g. alkali metal bicarbonates or carbonates, are suitable for this or hydroxides; or organic bases such as alkali metal alcoholates e.g. sodium methylate or tertiary amines, e.g. triethylamine, Ν, Ν-dimethylcyclohexylamine; or saturated or unsaturated Nitrogen heterocycles e.g. N-methyl-piperidine, pyridine or quinoline. The method is conveniently using one of the solvents listed in process A or mixtures thereof carried out.

Furthermore, the ixoazolylmethylthiol carbamates according to the invention of the general formula I also by the following procedure by reaction of an isoxazolylmethylthiochlorocarbonic acid ester be made with a secondary amine »

709885/0200

Method C:

R- "O ι ι» CSC-Cl +

+ HCl

VI

VII

1 f!

In the formulas, R to R have the meanings defined above.

The thiochlorocarbonic acid esters of the general formula VI can prepared by customary methods from the isoxazolylmethyl mercaptans of the general formula IV (Y = hydrogen) and phosgene will. Examples of compounds of the formula VI include: 3-methyl-isoxazolyl-5-methylthiocarbonyl chloride, 3-ethyl-isoxazolyl-5-methylthiocarbonyl chloride, 3-phenyl-isoxazolyl-5-methylthiocarbonyl chloride. As secondary amines of the general formula VII are particularly suitable those above in the Method B are listed as components of the carbamic acid chlorides. Method C can be carried out using the methods described in Method A mentioned inert solvents - less advantageously in alcohols or water - and optionally with the addition of one of the in process B mentioned hydrogen chloride binding agent carried out will.

Procedure A is carried out in detail, for example as follows:

Into a solution or suspension of at least one mole of thiolcarbamate of the general formula III, if appropriate in one of the said solvent at -20 ° to +50 ⁰ C one mole of a halide or isoxazolylmethyl -alkansulfonats of the general formula II is added dropwise. To complete the reaction is stirred until 8O ⁰ C for 3 to 12 hours at 0 "After completion of the reaction is poured into water, the product optionally extracted with a water-immiscible organic solvent and then isolated by distillation or crystallization.

709885/0200 - 13 -

"Procedure B is carried out, for example, in the following way:

A solution of one mole of isoxazolylmethyl mercaptan of the general formula IV in a solvent is reacted with at least one mole of a carbamic acid chloride of the general formula V in the presence of at least one mole of one of the abovementioned inorganic or organic bases, with temperatures of -10 ° C to 80 ⁰ C and reaction times of 1 to 12 hours are required. The thiol carbamates of the general formula I according to the invention are isolated in the manner described above.

Procedure C is carried out, for example, as follows:

A solution of one mole of a thiochlorocarbonic acid ester of the general formula VI in an inert organic solvent is reacted with at least one mole of an amine of the general formula VII, at least one mole of the inorganic or organic bases mentioned in process B can serve as acid-binding agent. The reaction temperature or time is -10 ° C to +80 ⁰ C and 1 to 12 hours as in Method B depending on the nature of the reactants, the base and the solvent. The thiol carbamates are isolated as described above.

To illustrate the process for producing the inventive Isoxazolylmethylthiolcarbamate of the general formula I are given the following examples, in which parts always Parts by weight are.

example 1

^{60.0 parts of carbon oxysulphide were gassed in at 0} ° C. to a mixture of 102 parts of N-ethyl-cyclohexylamine, 80.8 parts of triethylamine and 700 parts of methylene chloride and the mixture was stirred at room temperature for 2 hours. Then were at 0 ⁰ C 105.3

709885/0200 - ii »-

OFiIGfKAL INSPECTED

- i / r'- o.z. "52 ιοβ

Parts of 3-methyl-5-chloromethylisoxazole were added dropwise in 1 hour and stirred for 10 hours at room temperature. Do suction of the resulting salt, the filtrate was washed successively with water, 1 normal hydrochloric acid and water and dried. After removal of the solvent, the distillation of the residue gave 194.2 parts of 3-methyl = 5-isoxazolylmethyl-N-ethyl-N-cyclohexylthiol carbamate with a boiling point of 176-179 ° C at 0.2 Torr (pp. 60-62 ° C).

Example 2

To a mixture of 21.2 parts of diisopropylamine in 100 parts of toluene, 8.0 parts of carbonyl sulfide were introduced at 0 ° C and stirred for 0.5 hours at 0 ⁰ C and 1 hour at room temperature. 19.0 parts of 3-ethyl-5-bromomethylisoxazole were then added dropwise in 15 minutes and the mixture was stirred for 3 hours at room temperature. After working up as in Example 1, 21.8 parts of 3-ethyl-5-isoxazolylmethyl-N, N-diisopropylthiol carbamate were obtained Boiling point 154 - 156 ⁰ C at 0.3 Torr (n ^ ⁵ = 1.5089) obtained.

Example 3

To a mixture of 25.8 parts of 3-methylisoxazolyl-5-methyl mercaptan in 100 parts of ether and 50 parts of pyridine, 29.8 parts of Ν, Ν-diethylcarbamic acid chloride were added dropwise with cooling and then refluxed for 3 hours. After working up as described in Example 1 35.8 parts of 3-methyl-S-isoxazolylmethyl-NJN-diäthylthiolcarbamat of boiling point 136-138 ⁰ C obtained at 0.05 Torr.

The following isoxazolylmethylthio] carbamates according to the invention can be prepared by one of the processes mentioned:

709885/0200

- 15 -

No.

- 15 -

R-

OZ 32 106
R ⁶

Phys. Data (bp / tprr; pp .; g ⁵

Tp g ⁵

3
4th
5
6th
7th

ο ⁸
S 9

cn 2

ο ₁₀
to

12th
1

13th
14th

15th
16

17th

CH-

CH,
CH,
CH.
CH.

CH.

CH.

CH

CH.

CH.

CH.

CH.

CH.

CH.

CH.

CH.

H H H H H H H H H H H H H H H H H H

H H H H H H H H H H H H H H H H H H

η-C 3 ^Η 7 3> 2 i-C 3 ^Η 7 2 CH ₂ -CH (CH CH ₂ -CH = CH C ₂ H 5 C ₂ H 5

C ₂ H ₅
1-C ₃ H ₇

C ₂ H ₅
1-C ₃ H ₇

ITC ₃ H ₇

CH ₂ -CH (CH) ₂

CH ₂ -CH = CH ₂

- (CH ₂ ) ₅ -CH (CH ₃ ) -

- CH (CH ₃ ) -CH ₂ -C (CH ₃ ) ₂ -

- CH (CH ₃ ) -CH (CH ₃ ) - (CH ₂ ) _{1 |} -

Example 3

143 / 0.05 (68 ⁰ C)

η £ ⁵ 1.5435

124 / 0.05

132 / 0.05

160 / 0.2

139 / 0.05

example

143 / 0.05 ⁰ ^

164 / 0.2

144 / 0.2

example

147 / 0.3

170 / 0.4

P.p. 72-73 ° C Ot

148 / 0.2 co

184 / 0.4

• Ρ ·

cd ft
ο fr

ra

in

kv

CM

O O

O σ ·.

co

co

α.

co

O O

τΗ

OY

ft

TH OJ KY KY OJ τΗ Ln
O τΗ O Q O O O O O O • = r
• = r
τΗ 152 / 180 / ■■ sr-
cc
τΗ O
OY
Ή CC
VD
τΗ 139 / . - = r
in
τΗ

OJ

ο "

ιη VD O VD VC CC Ή τΗ TH

W W. W W WW WWWW

^ - W. W. J I. in I. W. I. OJ OJ W. B - i G ΚΛ W. ■ S- W. OJ x-v x — v W. . = r X-V VC W. m KY O O VO OJ O KY O O OJ O KY W. O j X-V W. x-v I. W. I. ί X-V X ^ W. j - O OJ 1 C. OJ O OJ β O x — s β OJ OJ O O t ο • Η W. V-X W. KY W. W. H •H O I. O O W. O O O G O v> V.X- . >> ■ V-X -1 jr KY O I. W. W. X-V W. ρ O in - O W. W. W. V-X. w " I. OJ O W. O N.X O W. V ^ ' W. O W. O I. 1 O 1 J W. O in t- ON in t- W. W. W. W. W- OJ KY O in OJ tn KY ο O O W. m O W. O J I. a OJ W. OJ I. β C. O OJ O • Η O

W W

W WW WW W W WWWW W W

WWWWWWWWW W W

ιηιηιη in in tn in in Ln in mm

W W WW W WW W WWW W KY

OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ W

O UOO O O O O O O O O O

O TH OJ KY OJ Ln VD Ι co cn O τΗ OJ OJ OJ OJ OJ OJ OJ ΟΙ OJ OJ ΚΛ K> KY

7098B5 / 0 200

cor

■ Ρ · approx! X

. = r

• ν »

O O OJ

ο ο

VD

^^ VD

ro

• I

VD

O O

in

α fc

OJ

• v

~ ^ OJ

OJ

oo

ro ι OJ OJ ro ¹ in ro > ro ro I. OJ OJ ro OJ OJ OJ OJ E. / -Ν E. E. E. . = r E. E. ϋ E. O
O
OJ ro ϋ ϋ OJ O ϋ O OJ OJ I. O ϋ ro ro E. E.
ο I. ^^ E. OJ * _ • E. E. ι ro E. E. O E. O E. E. E. E. O O S-S ϋ O OJ ο ϋ ^^ O O O ϋ ^^ E. I. I. I. I. E.
O E.
ϋ O I. I. I. I. O I. I. OJ * ~ ^ ro E. ϋ ^^ ro E. OJ OJ E. ϋ ϋ I. ro ro O E. E. OJ O O E. O E. E. OJ O O E. ϋ

X DC K

ro ro ro O O O E E

E E

ro ro ro ro ro ro EEEEEE O O O O O

ro - = r ro ro

in vo ro ro

t- oo ro ro

rH E. O OJ ro E. O ro E. E. O O O ro

709885/0200

Examples of the herbicidal action of the new Isoxazolylmethylthiolcarbamate

To prove what was made at the beginning with regard to these active ingredients Statements a series of tests was carried out. These included essentially three groups:

I. Greenhouse trials

Paraffinic paper cups with a capacity of 200 cm served as culture vessels and loamy sandy soil with about 1.5 % (weight) humus as substrate. In this, the seeds of the test plants were sown shallow, separated by species. The active ingredients were applied immediately afterwards (pre-emergence treatment). These were suspended or emulsified in water as a distributing agent and sprayed onto the surface of the earth using finely distributing nozzles. Before the chemical treatment, the vessels were lightly sprinkled so that the agents came into contact with moist earth. After applying the agent, the vessels were covered with transparent plastic hoods until the plants had grown on. This cover prevented the evaporation of water and volatile substances. At the same time, it caused the test plants to emerge more evenly, provided they were not impaired by chemicals. In the post-emergence treatment, the plants were first grown in the test pots to a height of 3 to 10 cm, depending on their habit, and then treated. There was no cover. (10 - 20 ⁰ C) the experiments were in the cooler according to the temperature requirements of the test plants or warmer (18 - 30 ⁰ C) part of the greenhouse plants established. The test period extended over 2 1/2 to 6 weeks. During this time, the plants were tended and their reaction to the individual treatments was evaluated. The test substances, the respective dosages in kg / ha of active substance and the test plant species are listed in the attached tables. The evaluation was done on a scale of 0-100.

- 19 709885/0200

O. Z. 32 106

O = no damage or normal emergence and 100 = complete destruction or »no emergence of the plants,

II. Field trials

These were small plot trials of various sizes. The location was a loamy sandy soil with a pH of 5 - 6 and 1 - 1.5 % humus. The application dates were in the early to late autumn as well as in early and late spring according to the sowing times of the cultivated plants. The substances were applied emulsified or suspended in water as a carrier and distribution medium with the aid of a motor-driven plot sprayer mounted on an equipment carrier. The most common application methods used were pre-sowing incorporation and pre-emergence surface application. In individual tests, the effect of the agents when sprayed during emergence of cultivated weeds and weeds as well as in the post-emergence process (postemergence) after a few real leaves had formed was tested. All tests ran for several months, in which period the evaluation according to the 0 to 100 scale was carried out at certain intervals.

III. Herbicidal effect via the vapor phase

The remarkable herbicidal effects of isoxazolylmethylthiol carbamates, even if these substances are not, as is necessary with known Thiolcarbamateη, in the soil were incorporated suggested that the drug losses by evaporation with this compound were only minor. In order to investigate this, the following experiment was carried out in the greenhouse: More sensitive Cultivated oats were sown as described in Section I greenhouse experiments and treated with the herbicidal Treated active ingredients in different dosages. After that, however, the vessels were not covered with a plastic cover but put them in pairs in glass cylinders from

709885/0200 -20-

5 liter content. The pairs each consisted of one treated and one untreated vessel. Control cylinder, which only contained untreated pots were of course available for comparison. To exchange gas with To prevent the outside air, one smeared the edges of the Cylinder with Vaseline and covered the opening with a - glass plate .: easily evaporating substances could thus

; from the surface of the treated vessels escape into the cylinder space and possibly the germination and development of the test plants in the originally drug-free

, ■., P-arall-influence-all-oil-vessels. The temperature in the glass cylinder varied from 11 ° C in the morning to 30 ⁰ C in the midday

. time in sunshine. When the plants in the control cylinders had a height of 13 to 15 cm after one week and the differences between the individual treatments were clearly noticeable, an evaluation was carried out. In addition to a; Visual inspection was used to determine the fresh weight of the oat shoots grown in each vessel. The latter was: "" - ■ ν shown in Table 11 »

Result _; ^

Those gathered like a mosaic in the various experiments and tables Individual values gave the following picture:

1 * The introduction of the Isoxazolylmethylrestes in the Thiolcar-: hamate led to a shift in action, in particular to a broadening of the action compared to known thiolearbamates. For example, some compounds developed an activity similar to that of N, N-diisopropyl-thiol-2,3-dichloroallyl carbamate or N, N-diisopropyl-thiol-2,3 _i 3-trichloroallyl carbamate, as well as that of N, N-dipropyl carbamate. thiolethyl carbamate included (see: Tab, 2, 3 and 5). In other cases, herbicidal performance was found to be similar, at times somewhat weaker than that of; N-ethyl-N-cyclohexylthiolethyl carbamate. The range of selectivity towards cultivated plants, however, was incomparably much larger (see: Tab. 6) "

7098 8 5/0 2Q0

- 3 * - OZ 32 106

At this point it should be emphasized that the known thiol carbamates were only used for the tests because of their effect as herbicides. In the structure of the invention Compounds similar to substances are not yet known. A thiol carbamate known as a herbicide with a heterocyclic ring was insignificant in its activity (Tab. 3). This was completely ineffective Dithiol carbamate. Another example of the herbicidal Contains effectiveness of new Isoxazolylmethylthiolcarbamate Tab. 4.

2. While known thiol carbamates because of their inherent Phytotoxicity and the training required for the herbicidal effect, as well as issues relating to the spectrum of weeds only for use with specific crops or groups thereof (e.g. broad-leaved species) some of the new compounds showed an improved and broadened selectivity (Tab. 3, 5, 6 and 7). the The selectivity of the substances according to the invention may be can be explained both in terms of plant physiology and partly based on the method of application. The latter means that immobile substances distributed on the surface of the earth with the somewhat deeper-lying seeds and roots of the cultivated plants do not come into contact in phytotoxic quantities. This selectivity is noticeable at Compounds that can be left on the soil surface after application. It becomes obsolete when the active ingredients have to be incorporated into the soil because of their high vapor pressure or other reasons to avoid evaporation losses to avoid.

3. The new compounds of the invention were incorporated As effective before sowing as known active ingredients. When used without training, they exceeded that known thiol carbamates suitable for the respective culture (Tab. 8). What was remarkable here was the The fact that e.g. the compound 3-methyl-5-isoxazolylmethyl-Ν, Ν-diisopropylthiol carbamate as thiol carbamate at pre-

709885/0200

- 2 / - O ₁ line 3 £ 106

running application without training (surface application) undesirable Plants in maize controlled as well as major known pre-emergence herbicides of other structure (Tab. 9) · Also combats during emergence and after emergence of the unwanted plants were successful, while the crop plants remained undisturbed (Tab. 8, 10).

4. The phytotoxicity of the vapors of Ν, Ν-diisopropyl-thiol-2,3,3-trichloroallylcarbamate against plughead oats is known. These findings were confirmed in our own model tests. With regard to the new compounds it was shown that, for example, the substance 3-methyl-5-isoxazolyl-methyl-Ν, Ν-diisopropylthiol carbamate was just as aggressive towards cultivated oats as a test plant in the directly treated vessels as NjN-diisopropyl-thiol ^^ - dichloroallyl carbamate or N, N-diisopropyl-thiol.2,3,3-trichloroallyl carbamate. The plants in the untreated pots located in the same glass cylinder remained undamaged with this new compound, while their growth had suffered more or less severely in the case of the comparative preparations (Table 11). Accordingly, less active substance escaped from the directly treated vessels of the new test substance than would have been necessary to damage the neighboring test plants via the gas phase. The actual measured vapor pressure of 3-methyl-5-isoxazolylmethyl-N, N-diisopropylthiol carbamate was 1.3 10 ^ mbar at 20 ⁰ C, while comparatively for Ν, Ν-diisopropyl thiol-2,3-dichloroallyl carbamate at the same temperature 3.7 x

—Ii
10 mbar were determined.

Of course, the test results presented here are only examples of the reaction of numerous undesirable and desirable plants from various botanical families. The application rates can also be varied beyond the examples. They are based on the application goal and the local conditions caused by the location or the plant size and can, for example, between 0.1 and 10 kg active ingredient / ha vary.

- 23 709885/0200

This new group of isoxazolylmethylthiol carbamates stands out in particular by the flexibility in the possible applications compared to known thiol carbamates.

- 24 709885/0200

■■ - 24 ~ O.

1q6

Table 1 - List of the plants used in the experiments

Latin name

Abbreviation in tables German
description

English
description

Alopecurus myosuroides
Amaranthus retroflexus

Avena fatua
Beta vulgaris
Brassica napus
Chenopodium album
Cynodon dactylon
Cyperus esculent us
Echinochloa grus galli
Eleusine indica
Euphorbia geniculata

Glycine max
Gossypium hirsutum
Hordeum vulgar
Lolium multiflorum
Matricaria spp.
Poa anriuä
Setaria faberii
Setaria spp.
Solanum nigrum
Sorghum halepense
Stellaria media
Triticum aestivum
Zea mays

Alopec. myosur. Amar. retro.

Avena fat. Beta vulg.

Cynod. dactyl. Cyper. escul. Echin. e.g. Eleus, Ind. Euph. Genic.

Gossyp. hirs.

Lolium multifl, Matric. spp.

Set. fab.

Sorgh. halep. Tritic. aest. Black foxtail

curved back

Foxtail

Wild oats

sugar beet

White goosefoot

Dog tooth grass

Tigernuts

Chicken millet

south america. Milkweed chart

cotton

barley

Italian ryegrass

Chamomile species

annual panicle

Bristle millet

Millet type

black nightshade

Sudan grass

Chickweed

Wheat .

Corn :

slender foxtail pigweed

wild oat

sugarbeet

rape

lambsquart he

Bermuda grass s

yellow nutsedge

barnyardgrass ι

goosegrass

southamerican member of

the spurge family

soybeans

cotton

harley

Italian ryegrass

chamomile

annual bluegrass

giant foxtail

foxtail spp.

black nightshade

johnsongrass

chickweed 1S3

wheat CO

Indian corn <^

- 2X-

- 25 -

O.Z. 32106

Table 2 - Action against important weed grasses in the greenhouse with pre-emergence treatment

R ¹

Basic body of the molecule

FT

I «

'Jf CO

Substitutions of the active ingredient, test plants and % damage

Test substances No. Quantity Alopecurus Avena Kchinochloa

_{Λ 0} -. kg / ha myosuroides fatua crus galli R ^X R ^, R ^

S 6 0.75 60 - RO

oo 1.5 90 - 90 \

oo 3.0 100-90

^ 3 0.75 95 0 60

r: i, 5 loo 8o 70

ο 3.0 100 Ro 75

4 0.75 90 65 ^R 5

1.5 95 95 90

3.0 95 100 95

Q 0.75 90 0 95

-Cl known 1.5 95 BO 95

3.0 95 BO 95

0.75 ^J t0 80 0

C, H ₇ n C, H "n C ₀ H ₁ - known 1.5 90 90 20 ^?

³⁷³⁷²⁵ 3! O 95 95 70 g

0 = no damage 100 = total loss ^

-X-

- 26 -

0, Z.

106

Table 3 - Elimination of unwanted plants and tolerance of crops to thiol carbamates in the greenhouse with pre-emergence application

N-C-S-IT

Basic body of the molecule

Substitutions of the
Test substances

Active ingredient no.

Application rate kg / ha

Test plants and % damage

Brassica Glycine Gossy. Zea alopee. Amar. Cyperus Eohin. Eleus. Euph.Poe Setarla Solanum Sorgh. Stellaria napus max hirs. mays myosur. retro, escul. e.g. Ind. Genic. annua spp. nlgrus halep. media

CH (CH,) "CH (CiLl ₀
(FR-PS 2 205 514)

-NO _p

loading

knows

1.0 4.0

20th

90

90

0 10

0 80

0 10

1.0 0 0 10 0 100 100 42 90 100 100 100 90 90 82 20

4 2.0 0 5 20 10 100 100 85 95 100 100 100 100 90 95 30

__. _: 4.0 0 _15 27 10___100 10O _-1 §5 _____ §5 100_ 100 _100 100 100__ 97 §0

1.0 0 0 0 0 100 100 60 95 100 60 100 100 100 72 0

, 2 2.0 0 5 0 0 100 100 60 95 100 95 100 100 100 95 30

■ *** 4.0 0 15 5 - 100 100 82 95 100 95 100 100 100 95 70

CD 1.0 ο ο 20 ο 80 loo 30 57 85 60 70 0 70 45 10

ςθ 9 2.0 0 0 25 0 100 100 55 92 100 60 100 15 70 75 80

0 ₀ 4.0 0 5 45, 0 100 100 55 95 100 90 100 40 100 90 80

⁰¹ 1.0 0 0 0 0 60 100 10 55 22 50 0 30 90 15 70 - 10 2.0 0 0 0 0 70 100 32 80 85 50 0 45 90 20 80

C> 4.0 0.5 15 0 100 100 32 80 95 95 0 65 100 50 8o

1.00 000 60 100 10 20 52 20 80 0 90 15 0

°, 13 2.0 0 0 10 20 80 100 40 85 95 20 90 0 90 45 0

O 4.0 0 0 12 20 80 100 70 95 100 70 90 55 100 67 0

1.00 10 0 is 0 90 - 60 50 - 90 10 25 10 0

27 2.0 0 10 00 10 95 - 95 90 - 100 80 60 60 0

4.0, 0,, 10, 10 10 90 100 95 90 - 100 85 90 70 0

1.0.0 0 00.900 - - -90.400 90 - 0

72.0 0 0.00900 - -90 90- 90 - 0

4.0 0 0 0 20 - 90 - - 90 100 - 100 - 0

1.0 0 0 0 0 60 95 - 60 80 30 90 20 30 10 0

20 2.0 0 0 0 0 100 - - 90 95 30 100 75 30 65 0

4.0 00 20 10 100 95 - 95 95 70 100 95 70 95 0 . ,. . - ... . ... ..., -, 'lsi)

f- 1.0 0 0 0 0 90 90 - 85, 90 100 100 55 70 60 0 CO

_ 21 2.0 0, 0 10 0 100 95 - 95 95 100 100 85 80 60 0 f- \

Z ■ 4.0 ο ίο 20 ο loo ioo - 95 loo loo loo 95 loo 70 ο T *:

-χ-

- 27 -

ο.ζ. 32

Table 3 - continued I.

Substitutions of the test substances

Effective effort test plants and % damage

substance amount Brassioa Glycine Gossyp. Zea Alopeo. Amar. Cyperus Echin. Eleus. Euph.Poa Setaria Solanum Sorgh. Stellaria

No, ka ^ ia napus max hirs. mays myosur. retro, escul. o.g. ind. genic. annua spp. nigrum halep. media

ro ο ο

C ₂ H ₅ 14th known S-Cl 1.0 0 0 Ul 0 100 90 20th 80 85 30th 90 40 90 45 0 < 0 2.0 0 0 12th 10 100 90 50 95 97 70 100 95 90 85 0 0 CHn 4.0 0 0 12th 10 100 100 77 97 100 100 100 100 80 90 0 0 2 7 known 1.0 0 0 10 0 60 100 15th 85 85 90 100 35 100 47 100 40 17th 2.0 0 0 17th 0 100 100 30th 95 100 100 100 65 100 92 100 40 Cl 4.0 0 5 32 0 100 100 42 97 100 100 100 100 100 92 100 50 1 1.0 0 0 0 0 90 90 35 55 60 45 80 5 30th 15th 0 0 CH ₂ -C - 5 2.0 0 0 2 0 90 90 40 92 97 45 90 20th 30th 40 0 0 C ₂ H ₅ 4.0 0 5 5 40 100 100 50 95 100 80 100 60 90 55 60 0 C. known 1.0 0 _ 60 _ 100 _ 10 67 82 _ 0 65 _ 10 0 2.0 0 - 92 - 100 - 40 80 92 - 30th 100 - 50 20th CHn CH 4.0 0 - 92 - 100 - 65 92 92 - 90 100 - 70 20th 4 9 2 5 known 1.0 5 0 0 _ 30th _ 20th 60 20th _ 20th 0 50 2.0 - 5 10 0 - 70 - 60 90 20th - 60 0 70 4.0 - 25th 20th 10 - 95 - 70 90 90 - 80 30th 90 PI Jl 01 known 1.0 0 0 5 0 100 4o 0 15th 92 8o 100 90 50 67 t 2.0 0 15th 17th 0 100 40 10 75 95 80 100 95 80 85 4.0 0 55 22nd 15th 100 90 40 87 100 8o 100 100 80 90 ? ι y I 1.0 0 5 5 0 70 20th 55 50 72 30th 90 65 0 4o 2.0 0 5 10 0 90 20th 75 50 95 30th 90 95 0 57 C ₂ H ₅ C ₂ H ₅ 4.0 0 25th 15th 20th 100 100 75 60 95 loo 100 100 30th 70 1.0 0 0 0 10 100 95 30th 80 100 90 100 60 50 ' 90 2.0 0 0 7th 20th 100. 95 40 95 100 90 100 100 70 90 4.0 0 10 7th 20th 100 100 40 95 100 100 100 100 90 95

0 = no damage 100 = total damage

ο. ζ. yd iö6

Table 4 - Example of herbicidal activity of new isoxazolylalkylthiol carbamates for pre- and post-emergence application in the greenhouse

Active ingredient Effort- Application- Test plants and % Damage No. Quantity d- Cyperus Echinochloa Lolium kg / ha methode escul. crus galli multifl.

3.0 VA - 90 90 3.0 NA 90 90 90 -

28 ν 3.0 VA - - 90 70 3.0 N / A 90 90 90 29 3.0 VA - ■ " 90 90 3.0. N / A 70 90 50 _ -
33 3.0 VA - 0 0 3.0 N / A 0 "90 50

3.0 VA - 90 30 3.0 NA 90 90 90

VA = pre-emergence treatment NA = post-emergence treatment 0 = no damage 100 = total damage

-29 "-709885/0200

Table 5 - Selective weed control in beets with different Thiol carbamates in the Preiland with pre-sowing incorporation

Basic body of the molecule

^ NCSR ³
0

Substitutions of the
Prüfsübstanzen

R-

Active on test plants and %

fabric wall damage

No. amount Beta Alopecurus

kg / ha vulgaris myosuroides

2 2.0 5 95 16 2.0 0 75 3 2.0 5 80 10 4.0 0 65 13th 4.0 0 50 9 4.0 50 70 14th 4.0 50 90

Cf, H_i C, H "i Cl Cl
Jl Jl ft

CH ₂ -C = C-Cl

2.0 4.0 0
0

30 80

known

C, H "n C, H ₇ n

known

2.0 4.0 10
30th

80 95

0 = no damage
100 = plants destroyed

709885/0200 - 30 -

- 30 -.

Table 6 - Herbicidal activity and crop plant tolerance of some thioloarbamates in the greenhouse with pre-emergence application

... ■ ■ ■ ■ ι ■.

Basic body of the molecule \ _ _s __3 ■. . .

Substitutions of the
Test substances

"1, 'o ²

O = no damage
100 = total damage

Active ingredient effort- ■,. Test plants and 56 damage

No. Quantity Beta Brassica Gossyp. Tritic. Amar. Cynod. Echin. Setaria Solanum Sorghum

kg / ira vulg. napus hirs. aestivum retr. dactyl, o.g. spp. nigrum halepense

1 2.0 O 0 5 0 90 75 87 50 95 70 4.0 O ₁ 0 10 0 100 95 92 65 95 75 C ₂ H ₅ ^ H known 2.0 O 30th 20th 100 85 97 92 95 30th 90 4.0 10 40 40 100 92 97 92 95 90 95 31 2.0 0 0 0 0 95 _ 95 85 80 60 4.0 0 0 10 10 100 95 90; 90 60 ) C ₂ H ₅

Table 7 - Compatibility of some thiol carbamates for rapeseed and spring wheat in the Preiland with pre-sowing incorporation _Λ

Basic body of the molecule

Substitutions of the test substances

V ₁ . _ _ "3

..IN —L / "* O — Π

Active ingredient amount no. Kg / ha

Test plants and % damage Brassica Triticum ■ Alopecurus napus aestivum myosuroides

known 2.0 0
0 0
5 82
95 I. C, H ₇ i 0, HLi Cl Cl
j I j I ft
CH ₂ -C = CH known 2.0 0
0 - 86
100 σ, Η-i C, H _v i Cl Cl
3 7 3 7 ι t
CH ₂ -C = C-Cl known 2.0
4.0 0
0 2
8th 58
92 CjjHqI C ₄ H ₉ IC ₃ H ₅ known 1.5
3.0 0
0 15th
82 30th
75 C ₃ H _7n C ₃ H _7n C ₂ H ₅ O = no damage
100 = total loss
= Spring wheat
= Weed as an indicator of herbicidal 1.5
3.0 0
10 12th
88 25th
82 O effect •
CO O

Table 8 - Effect of some thiol carbamates depending on the method of application in cereals

■■■ .. ■■ '■ outdoors ■ .. ·. ■■, '; ^: _Λ '■■,'',',. ■■ "■■■■■■■ ■ , ■. '^; · ^Λ /'. '. ■■■:' ■■ '■■■■'','■' ■ ^: ■

R "

Basic body of the molecule

Substitutions of the test substances

Active ingredient

No.

-CSR ³

ti

Application rate application kg / ha method
D.

Test plants and % damage Hordeum Tritic. Alopec. Matric. vulgar aest. myosur. spp.

2)

3)

C, H ₇ i CH ₇ X Cl Cl H 2.0 I. . 2.5 0 68 ': ■: 9, ■ ■> ι 3 7 I t
CH ₂ -C = C 2.0 II 0 1.2 85 . 54 O Cl 2.0 III 0 ο ■ 93 65 CO 2.0 IV 0 - 72 20th OO C ₀ Hf- OI CH- / A) -Cl known 2.0 - I. 0 2.5 70 6th /O; 2.0
2.0 II
III 0
0 0
0 51 23
20th PO
O 2.0 IV - '. - 65 5 O known 2.0 I. 2.5 0 57 0 2.0 II 0 0 64 30th 2.0 III 0 5 65 2.0 IV 8th 59 " ⁶ '■'

1) Application method: I.

■ '' '' ■■ ■■ ■ '■ ■ II

III IV

2) winter barley

3) winter wheat

= Incorporation before sowing (preplant incorporation)

= Preemergence after sowing

= Spraying during emergence (Application to emerging plants) γό

= Postemergence treatment σ>

■ '■■. ■■■■; ' ■■■■ '. ■' 'co

¹ , ''. ■ ^: ',' ^{,: 'Z 1} . ¹ CO

0 = no damage 100 = total damage

CO CD

Table 9 - Effect of 3-methyl-5-isoxazolylmethyl-N, N-diisopropylthiol carbamate on pre-emergence use without training in the field compared to known active ingredients

Test substances

Effort test plants and % damage

lot of Zea mays Echinochloa Chenopodium

crus galli album

O N> O O

CH.

.

N-C-S-CH,

^

CHi ⁷ (active ingredient No. 4)

2.0 4.0

C, H _n I

Cl Cl

J-C-S-CH "-C ⁼ CH

C ₃ H ₇ I.

2.0 4.0

known

CH

2.0

4.0

η τι ti 2 ^Π 5

known

25 60

15 35

20 70

CH ^ -CH-CH,

■ J j J

known

2.0 4.0

= no damage 100 = total damage

62 75

O lsi O

- 34 - O.Z. 32

Table 10 - Herbicidal activity and crop plant tolerance of some thiol carbamates im Post-emergence greenhouse

Basic body of the molecule ν,

Active ingredient

No.

JN-CSR- < . ti ■ R ⁴ V

Effort test plants and % damage

amount of Beta Gossyp. Alop. Avena Cyper. Echin. Eleus. Set, kg / ha vulg. hirs. myo. fat. escul. e.g. indie, fab

CH i Cl Cl 4th 1.0 0 0 80 75 / 65 78 20th 55 1 I.
CH ₂ -C = CH 2.0 ■ o 0 90 88 65 78 60 ■ 70 C ₃ H ₇ I. CpH be 1.0 0 _ 50 70 _ C _p H > -Cl knows 2.0 0 90 70 be 1.0 - 0 20th 10 45 10 55 knows 2.0 5 60 30th 48 50 55

0 = no damage 100 = total damage

.co co

Table 11 - Phytotoxicity of the vapor phase of some thiol carbamates against cultivated oats im Model test

Basic body of the molecule

NCSR ⁵
0

ο ro ο

CH ₀ -C

Cl CH

Active effort fresh weight of Avena sativa substance quantity directly in parallel vessel

No. kg / ha treated

CH ₇ X C, H ₇ i Cl Cl 1 , 0 1 , 3 CDE 2 , 7 PG 3 7 3 7 CH ₂ -C = CH 2 , 0
, 0 0
0 , 6
, 2 ABC
AWAY 1
1 , 9
,1 EP
BCDE

1.0 1.8 DEP 2 , 7 PG 2.0 1.0 BCDE 1 , 5 CDE 4.0 0.82 ABCD 1 , 7 DEP

Cl 1,
2, O
O 0.8
0.2 CDE
ABCD
AWAY 3.7
3.6
3.5 H
- GH
GH - 3.7 H Untreated control

Values that share a single letter are not significantly different (Duncan's new multiple range test, level 0.05) isj

22. Steel, R.G.D. and Torrie, J.H. - Principles and Procedures of Statistics, New York, co Toronto, London 1960, pp. 481 "co

O ₁ line 32 106

33

The new isoxazolylalkylthiol carbamates according to the invention can be mixed with numerous representatives of other herbicidal groups of active ingredients. These combinations yield a Broadening the spectrum of action and in some cases synergistic Effects. Some compounds are listed below as examples of such mixing partners:

1 row

CH-

i-propyl

CH ₃ -CH-C = CH.

CH, -CH-CH ₂ OCH ₃

C ₂ H ₅ C ₂ H ₅

-CH ₂ -OCH ₃

C ₂ H ₅ C ₂ H ₅

-CH ₀ -C-OC ₀ H, - ^ it ^ 0 0

CH, CH-

-CH,

CH-CH.

CH ₂ -CH ₂ -OCH ₃

70988570200

■ ³ / -

CH ₂ = CH-CH ₂ -

R-

CH ₂ = CH-CH ₂ -

CH,

O. Z. 32 106

N-C-N R O

R-

CH.

Cl

p-

CH.

CH.

^H 3 ^C \ J /

Cl

CH.

CH ₃ CH-CHCH

CH.

CH.

CH.

OCH.

OCH.

709885/0200

- 38 -

Cl
Cl

tert.
tert.

-CH-

-N

/ ^CH 3

"CH ₃

/ ^CH 3
'C-CH,

H J

- 3 * -, R ¹

NO

NH,

-N = CH-CH \

NH.

CH.

OZ J> 2

OCH.

OCH.

NS,

NS.

CH-

09885/0200 - 39 -

- 4a,

R ^λ ΝΟ

CH,

R-

CP

CP.

CP.

CH.

η. C ₃ H ₇ η. C ₃ H ₇ η. C ₃ H ₇ CH ₂ CH ₂ C η. C ₃ H ₇ η. CH ₇

CH

CH '

• 's.

CF-

NH.

η.C ₃ H ₇

η.C ₃ H ₇

NHR-

R-HN

tert.

1.C ₃ H ₇

C ₂ H ₅

C ₂ H ₅

R-

C ₂ H ₅

C "H _r

-C-CN CH

709885/0200

NS,

Cl

Cl

Cl

Cl

-Μ

CH

-C-CN CH O.Z. > 2 iC6

Cl

C ₂ H ₅

-CH-CH ₀ -O-CH. t * - "-

CH ₃ Cl

CH ₃ CH anion

H
CH.

CH -.- CCl ₀ -C-ONa 0

CCl ^ -C-ONa

J ti

Cl-

CH ₃

-N-CH-COC ₀ H ₁ . C = Q 0

Cl

s.

^CH

70988 5/0200

NC-

and salts

O.Z. 32 106

NC-

and salts

Br

, N - / ^ - ON = CH- ^ 3 ~ ^{OH and} salts NO. Br.

HNf,, NC-NH-CH ₂ -CH /

CH.

CH.

H ₃ C _H 0

N- <H

H °

° 2 ^N ~ \ / ~ ° ~ ^C ~ ^CH 3

^ NO, O ₂ N- /% -OH

and salts

709885/0200

G Cl

Vn 'V-NHCH ₃

CF ₃ O Cl

0 CH and salts

H.

and salts

O-CH ₃

H N-CH.

Il ^ CH,

CH ₂ -O-CH ₃

and salts

i-c-o-cH:

/ ^CH 3

NH-CO-CH ₀ -C = C-CH ₀ Cl

ti «- ί-

709885/0200

- hb

Oci -CH ₂ -CH-CO-CH

0.Z, 32

Cl

-CH -C-OCH,

I! I

CH ₃

Cl

OCH -CO-CH ₀ -CH CH .CH-CH.

^F 3 ^C "\ / °"

CH -C-O-Na

I Il

CH ₃

? 3

HC = CC-NH-C II CH ₃ O

Cl

Cl

OR

C-NH-O-CH ₀ -CH = CH.

HC '
HC ' C-OCH,
Il 3
O H or Na R = COOCH Ύ ^ ν ^σι Cl ^ Cl " COOCH_

and salts

709385/0200

32 1Ό6

COOH Cl Cl and and salts or 2633790 Λ / ^ Vo-CH. Cl NH ₂ Salts > - \ 3-C-OH
^ Il
0 and or ClH f Λ-0-CH
Cl ·. Ester Salts ₀ -C-0H
<- Il
0 ClH Ester

Cl-

, -C-OH and salts or esters

NC-CH ₀ -OS-NHCH, 0 0

H _x C

HO

As-ONa

Il

The application takes place e.g. in the form of directly sprayable Solutions, powders, suspensions, including highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, grit, granules by spraying, misting, dusting, scattering or watering. The application forms depend entirely on the intended use; in any case they should have the finest possible ensure division of the active ingredients according to the invention.

70 9 8 85/0 200

^; O. Z. 32 106

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, mineral oil fractions of medium-sized to a high boiling point, such as kerosene or diesel oil, also coal tar oils etc., as well as oils of vegetable or animal origin Origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives e.g. methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, Cyclohexanol, cyclohexanone, chlorobenzene, isophorone etc., strongly polar solvents such as dimethylformamide, Dimethyl sulfoxide, N-methyl! Pyrrolidone, water, etc. into consideration.

Aqueous application forms can be made from emulsion concentrates, Pastes or wettable powders (wettable powders), oil dispersions can be prepared by adding water. For production of Emulsions, pastes or oil dispersions can use the substances as such or dissolved in an oil or solvent Wetting agents, adhesives, dispersants or emulsifiers are homogenized in water. But it can also consist of active substances, Wetting agents, adhesives, dispersants or emulsifiers and possibly concentrates consisting of solvents or oils are produced, which are suitable for dilution with water.

The following surface-active substances should be mentioned:

Alkali, alkaline earth, ammonium salts of lignin sulfonic acid, Naphthalenesulfonic acids, phenolsulfonic acids, alkylarylsulfonates, Alkyl sulfates, alkyl sulfonates, alkali and alkaline earth salts of dibutylnaphthalene sulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, Fatty acid alkali and alkaline earth salts, salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulfated Fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, Condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, Alkylphenol polyglycol ether, trxbutylphenol polyglycol ether,

709885/0200. ,. _

ο.ζ. 3? 106

Alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, Sorbitol esters, lignin, sulphite waste liquors and methyl cellulose.

Powder, grit and dust can be mixed or mixed together Milling of the active substances with a solid carrier.

Granules, e.g. coating, impregnation and homogeneous granules, can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. mineral earth such as silica gel, silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, talc, bolus, loess, Clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, Magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as grain flours, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 percent by weight.

In addition to the mixtures or individual active ingredients, oils can be different Type, wetting or adhesive agents, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoam agents (e.g. silicones), growth regulators, antidote agents or other herbicidally active compounds are added will.

If necessary, they can also be added immediately before use (tank mix). The last mentioned herbicides Compounds can also be used before or after the individual active ingredients or mixtures according to the invention will.

709885/0200 - 47 -

W ο. ζ, y ?. ιο6

The admixture of these agents to the herbicides according to the invention can be in a weight ratio of 1:10 to 10; 1 »The same applies to oils, wetting agents or adhesives, fungicides, Nematocides, insecticides, bactericides, antidotes and growth regulators »

Example 4

90 parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl -; - pyrrolidone and a solution is obtained, which for Application in the form of the smallest drops is suitable.

Example 5

20 parts by weight of compound 2 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-N-monoethanolamide, 5 parts by weight calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the addition product of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring out and finer distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02 percent by weight of the Contains active ingredient,

Example 6

20 parts by weight of compound 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol and 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 10 parts by weight of the addition product 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.

709885/0200 - 48 -

O. Z.> 2 106

Example 7

20 parts by weight of compound 4 are dissolved in a mixture composed of 25 parts by weight of cyclohexanol and 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280.degree and 10 parts by weight of the addition product of 40 moles Ethylene oxide consists of 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein an aqueous dispersion is obtained which contains 0.02 percent by weight of the active ingredient.

Example 8

20 parts by weight of the active ingredient 4 are 3 parts by weight of the sodium salt of diisobutylnaphthalene- · '-sulphonic acid, 17 Parts by weight of the sodium salt of a ligninsulphonic acid from a SuIfit 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 gives a spray mixture containing 0.1 percent by weight of the active ingredient contains. '

Example 9

3 parts by weight of compound 4 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way, one obtains a dust containing 3 percent by weight of the active ingredient.

Example 10

30 parts by weight of compound 4 with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, which is on the surface of this silica gel was sprayed, intimately mixed. In this way, a preparation of the active ingredient with good adhesion is obtained,

709885/0200

- ψ- ο. ζ. 3? ΐοβ

Example 11

40 parts by weight of the active ingredient 5 with 10 parts of sodium salts a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water are intimately mixed. A stable aqueous dispersion is obtained. By diluting with 100,000 parts by weight of water give an aqueous dispersion which contains 0.04 percent by weight of active ingredient.

Example 12

20 parts of the active ingredient 6 are mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of petroleum alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil mixed. A stable oily dispersion is obtained.

- 50 709885/0200

Claims (5)

O.Z. JG. 106 claims 7633790 1. Isoxazoy Iy lmethy! Thiocarbamate of the general formula in the R is hydrogen, alkyl, optionally substituted by alkyl cycloalkyl, aralkyl or optionally substituted aryl,
2 R is hydrogen, optionally substituted alkyl, aryl or halogen, R- and R hydrogen or alkyl, R and R independently of one another denote alkyl, alkenyl, cycloalkyl, alkoxyalkyl or haloalkyl optionally substituted by alkyl and in addition R and R together with the nitrogen atom form an H , 5-, 6-, 7-membered heterocyclic ring which is substituted by lower alkyl groups can be. 2. Isoxazolylmethylthiolcarbamate according to claim 1 of the general formula in which R, R, R ^ and R have the meanings given in claim 1 and R · ^{5 are} hydrogen or alkyl with up to 3 carbon atoms. 709885/0200 - 51 - OWQINAL WSPECTED - 51 - O. Z. ^ P 1) 6 3. A process for preparing Isoxazolylmethylthiolcarbamaten according to claim 1, characterized in that _t a) Isoxyzolyl methyl halides or methyl alkanesulfonates of the general formula R ¹ R ² W R ' 0 C-X 1 H. in which R to R have the meanings given in claim 1 and X is halogen or alkanesulfonate, with thiol carbamates of the formula 0 R ⁵ MSC-N ' converts, in which R and R are those specified in claim 1 Have meanings and M is an alkali metal atom or one which is optionally substituted by two or three alkyls Ammonium radical means, or b) isoxazolylmethyl mercaptans of the general formula R ¹ R ² 0 'C-S-Y, r " 1 4 in which R to R have the meanings given in claim 1 and Y is hydrogen, an alkali metal atom or denotes an ammonium radical, optionally substituted by two or three alkyls, with carbamic acid chlorides the general formula 709885/0200 - 52 - .τ .. y ± io6 O, R ⁵ ι » / Cl-C-N \ _R 6 converts, in which R and R are specified in claim 1 Have meaning. 4. Herbicide containing an isoxazolylmethylthiol carbamate according to claim 1. 5. Use of an isoxazolylmethylthiol carbamate according to claim 1 as a herbicide. BASF Aktiengesellschaft 709885/0200