FI58120B - SAOSOM HERBICID ANVAENDBAR 1,2-DIMETHYLPYRAZOLIUMFOERENING - Google Patents

Description

...... ΓβΊ ADVERTISING PUBLICATION r o i Ο Π IBJ <11) utläggningsskrift 581 20, C Patent filed 10 12 1720

Patent ooddclat v ^ (51) Kv.ik.Vci.3 C 07 D 231/12, A 01 N 43/56 FINLAND —FINLAND (21) PK ^ «lhtk * mu * -P» t * nt * iwelwJn1 266k / lk (22) HAkamitpUvt — AnaOknlnfadig 11.09.7 ^ (H) (23) Alkupiivt — Giltigti «t * da | 11.09> 7 ^ (41) Tullut | ulklMk * l - Blfvfc offuntlli 22.03.75

Patent and Register Shark Iitin (44) Nlht * rtk * lp * non j * kuL | ulkai * un pvm. - n n

Patent and registration form λ 7 Anuekan uthgtf och utUkrtften pubiicorad 29.08.80 (32) (33) (31) Pyy * · »/« ueik · »* - iqiH priority 21.09.73 2i.O9.73, 2i.O9 .73 USA (US) 399655, 399781+, 399785 Proven-Styrkt (71) American Cyanamid Company, Wayne, New Jersey, USA (72) Barrington Cross, Rocky Hill, NJ, Bryant Leonidas Walworth,

Pennington, N.J., USA (7) Oy Kolster Ah (5 * 0 1,2-Dimethylpyrazolium compound for use as a herbicide - Säsom herbicid användbar 1,2-dimethylpyrazoliumförening

The invention is directed to the 1,2-dimethyl yy r at s to be used as a herbicide, which is characterized by the formula ...

^ 'iCV "3 χ- ID

N-H

I I

C 3 -C 3 CH 3 wherein E 1 is cycloalkyl C 1 -C 6, phenyl or alkyl C 0 -C 4, R 1 is cycloalkyl C 1 -C 4, alkyl C 1 -C 4 or benzyl, X is an anion having a charge of 1 to 3, and n is

3 (2 J-X

1, 2 or 3.

DE-A-2 260 1 + 85 describes many 1,2-dialkyl-3,5-di-phenylpyrazole salts which can be used as herbicides after germination, in particular for controlling wild oats (Avena fatua). The effect of the pyrazolium sols disclosed in this DE application has not proved to be as good as that of the 1,2-dimethylpyrazolium soles of the present invention. In addition, the compounds of the DE application are proposed to be used only after germination, while the compounds of the present invention are also well suited for use before germination.

Diketone precursors of formula IV for use in the preparation of compounds of formula I.

0 0

it M

Ry-C-Cl 2 -C-R 2 IV

wherein S., and 3, have the same meaning as above, prepare my next reaction 4 /. aavi is as follows: O 0 0: i NaH ^ "" R.COCH. + C-ii.OC-R, -—-> Ά -C-CH -C-R, (II) (III) (IV)

My methyl ketone (II) is reacted with an alkyl carboxylic acid ester (lii), preferably a methyl or ethyl ester, in the presence of an alkali metal hydride, preferably sodium hydroxide, and an aprotic organic solvent such as dimethylphenyl (DilSO), dimethylformyl , in the presence of toluene, or benzene. The reaction is preferably carried out at a temperature of 0 to 3 ° C, and very preferably 0 to 25 ° C. The reaction gives the β-diketone corresponding to the reactants used. The methyl ketone and the carboxylic acid ester are reacted in β-fimolar amounts, however, it is generally desirable to use a small excess, e.g., an excess of about 10%, in the reaction mixture.

To prepare compounds of formula I, the diketone of formula IV is condensed with either hydrazine or methylhydrazine to give the corresponding pyrazolium salt of formula (I). The reaction can be schematically represented as follows: '2 2 CH 2 OH- λ. . ,.

f.fC-Cil2-C-Sk -2- „(IV) S =? = i ai3 (v) 1!, ~ ί © νΒ3 X-” li-li

I I

Cl 13 CH 3 (I) 3,58120 wherein R 1, R 2, m and X are as defined above. The symbol <- indicates alternative points of attachment of the methyl substituent.

Typical anions suitable for use in this invention include halides such as chloride, bromide and iodide, sulfate, hydrogen sulfate, methyl sulfate, benzenesulfonate, perchlorate, C 1 -C 4 alkylbenzenesulfonate, preferably p-toluenesulfonate, phosphate, -alkanesulfonate; 2? And 2? -O-OCCR and -OC-CH-O- (ί J-Cl, 9 where R is halogen, methyl, halomethyl or dihalomethyl, R .. · and 5 ti R ^, are halogen, Rg is hydrogen or methyl, and R is chlorine or methyl.

Helogen as used herein means fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

Diketone and hydrazine react in equimolar amounts. However, a small excess of both reactants up to 10 J> can be used orally.

This reaction is usually carried out in the presence of a protic or aprotic solvent at a temperature of about 70 to 150 ° C, preferably 30 to 120 ° C. Preferred solvents for these reactions are erotic solvents such as the lower alcohols which are. methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol. Apricotic solvents suitable for use in these reactions include xylene, toluene, benzene, dimethyl sulfoxide, dimethylidene and pyridine. a ilupocatalyst such as ε-toluenesulfonic acid accelerates the condensation cyclization reaction, and is preferably used if the reaction proceeds slowly.

The initial condensation of the uiketone uses a hydrazine solution, preferably methylation of the resulting pyrazole using a known methylating agent, preferably in the presence of an acid acceptor such as an alkali metal hydroxide, alkali metal alkoxide or tertiary organic amine. Preferred acid acceptors are sodium or potassium hydroxide, sodium or potassium methoxide, ethoxide, propoxide or tybutoxide, trimethylamine, triethylamine and pyridine.

the methylations of the pyrazole are preferably carried out in the presence of a solvent at a temperature between> 0-200 ° C, and preferably between 90-120 ° C. Preferred solvents include aromatic hydrocarbons such as toluene, xylene and chlorobenzene, ketones having 1 to 7 carbon atoms such as methyl isobutyl ketone (M1biC) and methylbutyl ketone (i-ibK.); . 0, - 0 ,. alcohols, dipolar aprotic solvents such as dimethylsulfoxide, dimethylformane di (Dlf), acetonitrile, nitrobenzene and N, N-dimethylacetamide, and cyclic ethers such as dioxane and tetrahydrofuran.

U 58120

Examples of methylating agents are: methyl halides, dimethyl sulfate, methyl phosphate, methyl hydrogen sulfate and methyl toluenesulfonate.

While 3,5-disubstituted pyrazoles combine with equivalent amounts of methylating agent, in practice it is preferred to use an excess of methylating agent. Preferred molar ratios between the methylating agent and the pyrazole are 1: 1 to 1.5: 1. It will be appreciated that a moderate molar amount of methylating agent is required when hydrazine is used.

In these methylation reactions, it has often been found that upon cooling the reaction mixture, the solid or oily pyrazolium salt separates and is purified by separation from the organic layer. However, in some cases, especially where and are highly lipophilic (e.g. 3,5-dicyclohexyl, 3-cyclohexyl-5-phenyl and 3-dodecyl-5-phenyl), the separation of the pyrazolium salt from the organic phase is not easy to perform. In such cases, the product is obtained by evaporating the solvent and dissolving the residue in chloroform, washing the chloroform layer with water and evaporating the chloroform to give the pyrazolium salt as a residue.

When methyltoluenesulfonate or methylsulfate is used as the methylating agent, impure or hygroscopic substances are often obtained due to anionic contamination (such as HSO or SO 2). In these cases, the mixed anion is purified by passing an aqueous solution of this mixture through an anion exchange column. Alternatively, the aqueous solution of mixed anions can be converted to iodide using aqueous saturated potassium iodide or sodium iodide solution. The latter treatment gives a relatively water-insoluble iodide. Perchlorates are prepared by adding dilute aqueous perchloric acid to an aqueous solution of the pyrazolium salt to give a water-insoluble perchlorate. In addition, pure pyrazolium salts, e.g. CH 2 SO 4, HSO 4, SO 2 - or Cl, can be converted to the new pyrazolium salt and iodides and perchlorates by the above-mentioned anion exchange chromatographic methods as defined above. The pyrazolium halides are prepared as described above, except that the reaction is carried out in a sealed vessel or a glass-lined vessel maintained at a temperature of about 100 ° C.

The compound of the formula I is applied at about 0.28 to 11.2 kg / ha, preferably from 0.56 to 5.6 kg / ha. Surprisingly, these compounds can also be used as anti-mildew inhibitors when applied to the plant press at about 0.28-11.2 kg / ha.

The pyrazolium salts of formula (i) wherein R 1 is phenyl, R 1 is alkyl C 8 -C 4 (preferably C 1 -C 4) and m and X are as defined above have excellent selective retrospective broadleaf inhibition in the case of small grain cereals. such as barley, wheat and rice. This is particularly surprising because the known lower homologue in which R 1 is e.g. methyl is ineffective as a herbicide in all amounts tested. Surprisingly, these compounds 5,581,120 also have a prophylactic herbicidal effect.

as stated below, the pyrazolium salts of the formula (I) having a cycloalkyl C 1 -C 4 group and R 1 -C 6 and X have the same meaning as above are very effective herbicides. Preferred compounds are those wherein R is cycloalkyl C -CL or phenyl,

U ^ / · · · M

R is cycloalkyl C 1 -C 4, and X and m are as defined above.

These compounds are very effective herbicides. They are particularly effective when applied to the press of unwanted plants and are effective against both broadleaf weeds and unwanted grasses. In addition, they can be used selectively to control wild oats, broadleaf weeds and unwanted grasses, especially weeds among small-grained cereals such as barley, wheat and rice. Furthermore, it is surprising that these compounds also have a prophylactic herbicidal effect.

It is preferred that many of the pyrazolium salts of formula (i) are highly water soluble and may be used in the preparation of aqueous concentrates. Preferred salts are methyl sulfates, hydrogen sulfates, sulfates, chlorides and bromides. In practice, aqueous concentrates can be applied directly as a liquid spray to the leaves and weeds of unwanted broadleaf weeds. Alternatively, they can be further diluted with water and applied as dilute aqueous sprays to these undesired plants.

Water-miscible concentrates are prepared by dissolving 15-95% of the compound in 85-5 $ water-miscible solvent such as water itself or some other polar water-miscible solvent such as 2-methoxyethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol, diethylene glycol, and dimethylformamide. The application of the substance is carried out by placing a predetermined amount of water-miscible concentrate in a spray tank and applying the mixture as such or together with a suitable diluent, such as adding more water or with one of the above-mentioned polar solvents.

The performance of the product in all of the above formulations applied by spraying as a liquid is unexpectedly improved by the addition of a surfactant to the mixture of surfactants. Conventional anionic, cationic and anionic nonionic surfactants can be used.

6,58120

Typical non-ionic surface-active agents include: alkylpoly-oksietyleenieetterit, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monooleate, alkylaryl, alkyl-phenol ethoxylate, trimetyylinonyylipolyetyleeniglykolieetteit, alkyl phenol-ethylene oxide condensates, octyl phenoxy polyethoxy ethanol, nonyylifenyy-lipolyetyleeniglykoliteetterit, condensates of polyoxyethylenes, polyoxypropylenes, aliphatic polyethers, aliphatic polyesters, alkylaryl polyoxyethylene glycols and the like.

Examples of anionic surfactants are sodium dodecylbenzenesulfonate and sodium sulfosuccinic acid dioctyl ester.

Suitable cationic surfactants include dicococodimethylammonium chloride, stearamidopropyldimethyl p-hydroxyethylammonium nitrate and the like.

These surfactants are preferably added to the spray tank in a volume of 0.1-5 # to ensure that the leaves of the plants are well moistened with the sprayed solution.

Herbicidal concentrates containing surfactants are preferably prepared as aqueous sprays, containing about 30% by weight of a suitable pyrazolium salt, about 25-50% by weight of water with the rest of the preparation being (25-45% by weight) a selected surface -active substance. Surfactants which are particularly useful in the preparation of suitable surfactant-containing concentrates include octylphenol ethylene oxide condensate, an ethanolic solution of alkylphenol ethoxylate, polyglycol ether tertiary condensate, which is prepared from ethylene oxide and an alkylene oxide.

Other combinations which may be advantageously used with the compounds of this invention include dusts, dust concentrates and wettable powders.

Dusts are usually prepared by co-grinding about 1-25% by weight of the active ingredient with about 99-75% by weight of a solid diluent such as kaolin, attapulgite, talc, pumice, diatomaceous earth, effervescent clay, wood flour and the like.

Dust seals are prepared in the same way except that about 25-95% by weight of the active ingredient is ground together with about 75-5% by weight of the diluent.

Wettable powders are prepared in the same manner as dust concentrates, except that about 1 to 5 weight-dispersing agents, such as the calcium salt of polymerized alkylarylsulfonic acid, sodium negosulfonate, or the sodium salt of condensed naphthalenesulfonic acid, are mixed into the mixture and further mixed with about 1 to 5%. a substance such as polyoxyethylated vegetable oil, alkylphenoxypolyoxyethylene ethanol and sodium alkylnaphthalenesulfonate.

7 58120 In practice, the wettable powder is dispersed in water and applied as a liquid by spraying on the press of unwanted plants. The application rates should be sufficient to give about 0.28-11.2 kg / ha of pyrazolium salt, and although 0.56-5.6 kg / ha of this salt are generally sufficient to give a satisfactory result in the treatment of unwanted broadleaf weeds and unwanted for the control of herbs, it should be noted that amounts exceeding 11.2 and even 22, U kg / ha can be used.

These larger amounts are, of course, used on railway embankments, under power lines, and along hedgerows demarcating farms and fields.

In order that the invention may be more fully understood, the following examples are set forth to illustrate the details of the invention and also to illustrate the preparation of the starting materials used therein. Unless otherwise indicated, all parts and percentages are by weight.

Example 1 Preparation of 1,3-dicyclohexyl-1,3-propanedione

Sodium hydride (39.5 g of 5-6, 0.889 moles) is cooled in an ice bath to 18 ° C in a suitable flask equipped with a stirrer, condenser, drying tube, dropping funnel and thermometer. Dimethyl sulfoxide (700 mL) dried with kA molecular sieves is slowly added. When the addition is complete, the reaction mixture is stirred for 0.5 hours at room temperature. Return to the ice bath and add dropwise a mixture of cyclohexane carboxylic acid ethyl ester (138.8 g, 0.889 mol) and cyclohexyl methyl ketone (101.9 g, 080 mol). No exotherm is observed. The reaction mixture becomes lighter in color and a few bubbles are observed. When the addition is complete, the ice bath is removed and the reaction mixture is stirred overnight at room temperature. The thick, deep brown-yellow reaction mixture is poured onto 8 L of ice containing phosphoric acid (50 mL) and extracted with ether. The ether is washed with water, dried and the golden yellow oil (20 U g) which separates strongly to the ester is filtered off in vacuo. The product can, if desired, be purified with copper complexes by conventional methods. It is pure in the form of white crystals with a melting point of 50 ~ 52 ° C.

Analysis: Calculated for C 18 H 24 N 2 O 2: C, 76.22; H, 10.21+ Found: C, 76.20; H, 10.03

Other beta-diketones can be prepared from esters and ketones containing R 1 and R 2 as described above. Thus, 1-cyclopropyl-3-phenyl-1,3-propanedione has been reported to be prepared as a solid, m.p. 36-37 ° C from ethyl benzoate and cyclopropyl methyl ketone in the presence of sodium amide. Alternatively, it has been found that the same compound m.p. 38-1 + 0 ° C can be prepared from ethyl cyclopropanecarboxylate, acetophenone and sodium 858120 hydride. In addition, a number of 1-alkyl-3-phenyl-1,5-propanediones have been prepared from carboxylic acid ethyl esters and acetophenone in the presence of sodium amide. Illustrative examples are tabulated using the following equation 0 0 0 n NaH n n

R 1 COOH 2 + C 2 H 5 OCR 4 -> R 5 CCH 2 CR 4 (II) (III) (IV) wherein R 1 and R 4 are shown in Table I below.

3 4 9 58120 I Λ * "• e>

•B

O

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rH Φ T3 Π f} M rH 3 U

to * H H Λ * H: o ^ cd H: o >> Φ d rt -h> cd p »ö Φ M d ö

> · Fi -p h td ö (3 -H -H

Ö: o -P ώ Φ -H: o cd ra ra d-ΡΦβ-Ρθ -ρ ή d to S -h | 3 ö .Μ Φ t \ »H d i >>

Φ (ϋ * H d * Η Cd · * · »<!) H H

M> ►?>, «T> d> PM d O: o>. -. .——— - '- -' * 1 'O' I ri mmoo I in - - ^ £ o 'o ° · s'' O ^ t »* rj CL · O * o • CO rH CT \ CO j ? Co 0 ^, -f

Ph K \ CO -ί 4 · vh - = J "CO

C/O

B

0

1 A * 3 “5 Λ P

* A o · 1 o- LJ = “Q

c c: i «O 00 ö o_ .joo.

10,581 20

Example 2 Preparation of 3-cyclopropyl-1-methyl-5-phenylpyrazole and 5-cyclopropyl-1-methyl-3-phenylpyrazole.

1-Cyclopropyl-3-phenyl-1,3-propanedione (37.6 g, 0.2 mol) and 2-propanol (250 ml) are heated to reflux. Methylhydrazine (10.2 g, 0.22 mol) is then added dropwise and the solution is refluxed until the reaction is complete (2.5 hours). The solution is then filtered and the yellow oil (39.2 g, 99%) is separated in vacuo. Examination of the product by silica gel thin layer chromatography with chloroform and iodine shows the presence of an impurity. The product is chromatographed on silica gel using chloroform to give a white, cloudy oil. The isomers may be used as a mixture or may be isolated by conventional chemical separation methods, such as fractional crystallization.

Analysis: Calculated: for C 13 H 11 + N 2: C, 77.68; H 7.26; N, 13.52 Found: C, 77.92; H 7.33; N, 13.56

The following pyrazoles have the structural formula: 1 (r) (vi) is prepared by the method of this example using the appropriate 1,3-propanedione instead of 1-cyclopropyl-3-phenyl-1,3-propanedione. The results of the method are shown in Table II below. ί¾ ^ nboli / ^ fc - '^ indicates alternative attachment positions for the methyl substituent.

58120

β I

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o P Φ p P P

P, p, V h> j p: rt

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rt: rt: rt h Ai rt rH C · Η, β AS n B AS: rt h P «

• H p CÖ B rH: <M CP

• H cj: rt H 1> β: rf Λ h d: •> o ρ <φ λ: rt * · rt +3 ‘J. rt

3 .. R ιο, h P M K P

7; β ΝΛ -H pi rH O ί> »^ rt 2 ph s p o β o p a.

m HO H W a P rt.

® OK ·. O O H HP R W β 2 Ho cO Hi Ό K a vh

2 C h H rt rt H H pOH

«R ► H R T-3 R R P P U! o

2 ii): rt rt to o oj rt ρ P P

p oh BOrt H a> rt as h rt 7 * PH Ö P H A! H Hi p R p <°° rt h rt rt ti o h rt <'h o

Zi SH H Θ H R 0 '0) ti Π II

'rt o o now ti ti h opp' * 2 R rt H R AS R? » PI Ρ 1

£ tV ta ΕιΛ ΟΦ K t> R o rt CM

>> >> β

1-s H> H

H> ϊ H H * r! : θ t-s: c AS rt

pH

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rH ^ «—l rHTflS. "B

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r-f n i-i OS

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_____________________I

111 58120

Example 3 Preparation of 3-cyclohexyl-1,2-dimethyl-5-phenylpyrazolium methyl sulfate.

In a suitable reaction vessel, 1-methyl-3 (5) -cyclohexyl-5 (3) -phenylpyrazole (8.0 g, 0.033 mol) is dissolved in dry toluene and heated to ca.

65 ° C. Dimethyl sulfate (1 +, 5 g, 0.035 mol) is then added and the mixture is heated to reflux. Thin layer chromatography ("benzene") shows a small amount of pyrazole remaining after 1.5 hours. After 2 hours, the reaction mixture begins to darken and heating is stopped. Upon cooling, a white solid forms which is filtered and washed with dry toluene. This sticky white solid is dried in vacuo at room temperature to give The hexane is then added and the solid is decomposed and collected by filtration to give a solid (6.3 g, 50 - catch) mp 1 + 8-51 ° C · On contact with air it becomes sticky (hygroscopic, The analysis gave the following values: ^

Analysis: Calculated for H 2 O: C, 56.2h; H, 7.3 * +; N, 7.29.

Found: C, 56.91; H, 7.33; N, 7.12.

Example 1+ Preparation of 5-cyclopropyl-1,2-dimethyl-3-phenylpyrazolium methyl sulfate.

A mixture of 3-cyclopropyl-1-methyl-5-phenylpyrazole and 5-cyclopropyl-1-methyl-3-phenylpyrazole (33.1 g, 0.167 mol) and dry toluene (250 ml) is heated at reflux and about 25 ml of solvent is removed with a Dean Stark separator. The solution is then cooled and dimethyl sulfate (18 mL, 0.193 mol) is added. The reaction mixture is kept at 100 ° C for 2.5 hours. A yellow-brown oil forms which solidifies on cooling. The solid is removed by filtration and dried in vacuo to give a cream solid (1 + 9.5 g, 91.5 ~ # yield) with a melting point of 163-170 ° C and analytical results as follows:

Analysis: Calculated for C 18 H 18 N 2 O 2 SO 2: C, 55.5 * +; H, 6.22; N, 8.61+; s, 9.89 Found: C, 55.27; H, 6.23; N, 9.1 + 8; S, 9.99-

Following the procedure of the example described above, the compounds of general formula III are prepared by substituting the appropriate 1-methylpyrazole for 3-cyclopropyl-1-methyl-5'-phenylpyrazole.

15 5 81 2 0

Table III

R ^ Melting point (° C) Appearance \ '\ 157 Light white _ / crystals n-Cj-H ^ oil Viscous brown 5 oil

The following pyrazoles, when reacted with dimethyl sulfate using the method described above, give products which are mixtures of methyl sulfate and hydrogen sulfate salts. In such a case, the products are completely converted to iodides and / or perchlorate salts by dissolving them in water and treating them with saturated potassium (or sodium) iodide or dilute perchloric acid, respectively. For example, using either a compound:

r CL

R 1, X 3 (viii) f R 1 is wherein R 1 is nC 2 H 2, (CH 2) 2 O-, cycloheptyl, or ch 3 Q -R 1 q methyl sulfate / hydrogen sulfate salts, using undecyl and cycloheptyl groups, do not separate on cooling the reaction mixture. In these cases, the separation from the reaction mixture is carried out in vacuo, the residue is dissolved in water and used to prepare iodide and / or perchlorate without solvent extraction.

Example 5 Preparation of 5-cyclopropyl-1,2-dimethyl-3-phenylpyrazolium perchlorate An aqueous solution (500 ml) containing 10 g of 5-cyclopropyl-1,2-dimethyl-3-phenylpyrazolium methyl sulfate is extracted with ether. The aqueous layer is separated and treated with dilute perchloric acid 16,581 g (10 mL) to give a solid. After stirring for one hour, the solid is removed by filtration and dried to give a cream solid (6.1 g, $ 60) with a melting point of 160-116 ° C. The following values are obtained for analysis:

Analysis: Calculated for C 18 H 18 ClN 2 O 2: C, 53 * 755 H, 5.48; N, 8.96; Cl 11.34 Found: C, 54.0; H, 5.40; N, 8.90; Cl, 11.48

As can be seen from the following Table IV, by way of example, several perchlorates are prepared according to the procedure described in Example 5 above using the appropriate pure, technical or crude 1,2-dimethyl-3 * 5-substituted pyrazolium methylmethyl sulfate salt having the structure ch5 Ί CH3 R4 -r + N ^ CIO "

1 II

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Example 6 Preparation of 5-cyclopropyl-1,2-dimethyl-3-phenylpyrazolium iodide A solution of 5-cyclopropyl-1,2-dimethyl-3-phenylpyrazolium methyl sulfate (12.3 g) dissolved in water (100 ml) is extracted with ether. . The aqueous layer is separated and treated with saturated aqueous potassium iodide solution. After stirring for 0.5 h, the solid is filtered off and dried to give a straw-colored solid (k, 7 g, 36%) with a melting point of 150-152 ° C. The analysis gave the following results:

Analysis: Calculated for ClUH17N21: C »k9 * k2i H '5.04; N> 8'2h Found: C, 1 + 9.07; H, 5.06; N, 8.16.

Typical iodides shown in Table V below are prepared by the method of Example 6 described above, substituting 5-cyclopropyl-1,2-dimethyl-3-phenylpyrazolium methyl sulfate of formula

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Example 7 The selective post-herbicidal activity of the compounds of this invention is demonstrated by the following tests in which various monocotyledonous and dicotyledonous plants have been treated with test compounds dispersed in aqueous acetone mixtures. In the tests, seedling seedlings are grown in special machines for about two weeks. The test compounds are dispersed in 50/50 acetone / water mixtures containing 0.5% polyoxyethylene sorbitan monolaurate surfactant in an amount sufficient to give an amount of active compound of about 0.56-U, U8 kg / ha when applied. applied to the plants through a spray nozzle operating at a pressure of 276 kPa at a predetermined time. After spraying, the seedlings are placed on greenhouse pallets and treated in the usual manner, in accordance with standard greenhouse practice. 5 weeks after treatment, the seed plants are examined and evaluated according to the following evaluation. The values obtained are shown in the following Tables VI and VII, from which it can be seen that the compounds are very effective in killing many broadleaf weeds and unwanted herbs.

Grading system Growth percentage difference • X) vertical plants 0 - no effect 0 1 - possibly effect 1-10 2 - mild effect 11-25 3 - moderate effect 26 —U0 5 - clear damage 1 + 1-60 6 - herbicidal effect 6l ~ 75 7 - good herbicidal effect 76-90 8 - almost complete destruction 91 ~ 99 9 - complete destruction 100 1+ - deficient growth, ie clear physiological malformation but with a lower overall effect than point 5 on the rating scale. x).

- Determination of vertical stability, size, strength, green canopy deformity and overall plant appearance.

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Example 8 The preliminary activity of the compounds of this invention is demonstrated by the following tests in which a mixture of a 50/50 acetone / water mixture containing 0.5% by volume of polyoxyethylene sorbitan monolaurate surfactant and sufficient test compound to give 11.2 kg / ha of the compound. compound when the mixture is applied to pots planted with seeds of the test plant species.

The pots are prepared on the same day as the herbicide treatment by placing 100 ml of mold in each plastic pot as a medium, then the sunflower, tomato, wild oat, and walnut seeds are placed on this medium and covered with 50 ml (10-13 mm) of soil. The seeds of each of the other eight plant species listed below are mixed separately with the soil and 50 ml of the soil / seed mixture is added to the pot. The soil is then sealed evenly in pots and pre-moistened with water before applying the carbide. Pre-wetting ensures that the herbicide treatment solution spreads evenly on the surface of the pot and protects the grass seeds from acetone damage. Each of the 12 Ruohola jigs is placed in a separate pot. The pots are arranged in 26 x 30 cm baskets before chemical treatment.

The planted pots are treated with 5 ml of test solution and then placed on greenhouse trays. The pots are watered after treatment and kept in the greenhouse for 3 weeks, after which the results are recorded as shown in Table VIII.

Plant species used in the evaluation of prior herbicide treatment Common name Abbreviation Scientific name

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