CS208693B2

CS208693B2 - Herbicide means and method of making the active agent

Info

Publication number: CS208693B2
Application number: CS691373A
Authority: CS
Inventors: Harry Tilles
Original assignee: Stauffer Chemical Co
Priority date: 1973-06-18
Filing date: 1973-10-08
Publication date: 1981-09-15

Description

(54) Herbicidal composition and method of manufacture of an active ingredient

The present invention relates to a novel herbicidal composition which contains as active ingredient compounds which can generally be described as sulfoxide and sulfone derivatives of thiocarbamate and which are highly effective herbicides. The compounds of the invention have the following general formula (I):

O ll

RS (O) _n -CN

(1) in which n represents 1 or 2,

R is selected from the group consisting of alkyl of 1 to 6 carbon atoms and chloroalkyl of 1 to 6 carbon atoms in the alkyl group.

R 1 and R ₂ together form an alkylene group having 5 or 6 carbon atoms, an alkylene group having 5 or 6 carbon atoms, substituted with a C 1 -C 4 alkyl, or a group / CH ₂ -CH ₂ CH ₂ CH> CH-CH 2 ch ₂ ch ₂ ^x ch ₂ -ch ₂

Said compounds may be prepared by reacting an oxidizing agent, preferably peracetic acid or m-chloroperoxybenzoic acid, with a thiocarbamate compound corresponding to the following general formula:

O

II

RSC-N 'wherein R, R 1 and R ₂ are as defined above. The reaction is carried out in the presence of a solvent such as chloroform, methylene chloride, benzene or toluene and at a reduced temperature in the range of about -25 ° C to 60 ° C. The amount of oxidizing agent used must be at least one molar equivalent to form the sulfoxide derivative and at least two molar equivalents to form the sulfone derivatives.

Thiocarbamate compounds are known herbicides, the method of manufacture of which is known, for example, from U.S. Pat. Nos. 2,913,327, 2,983,747; 3,133,947; 3,175,897 and 3,185,720.

However, the use of these thiokerbamates as reactive intermediates to form other compounds that also have pesticidal activity is unexpected.

In order to further elucidate the invention, several examples are set forth below.

Example 1

OO

JJ II CjHg-SCN

XH, -CH ₂ -CH ₂ -I ^x ch ₂ -ch ₂ -ch ₂

A solution was prepared containing 11.2 g (0.055 mol) of m-chloroperoxybenzoic acid and 200 ml of methylene chloride. The solution was cooled to -14 ° C in dry ice, and then 9.4 g (0.05 mol) of S-ethylhexahydro-1H-azepine-1-carbothioate was added to the cooled solution over four minutes at a temperature of of the reaction mixture rose to -13 ° C. The reaction mixture was then cooled to -14.5 ° C and allowed to stand for 1 hour. The reaction mixture was then cooled to -5 ° C and allowed to warm to 20 ° C. The reaction mixture was then cooled to 2.5 ° C, then filtered and the filter cake was washed twice with 25 ml of methylene chloride. The combined filtrate is washed four times with 100 ml of 5% sodium carbonate solution and twice with 100 ml of water, dried over magnesium sulphate and concentrated on a rotary evaporator, initially under vacuum from a water pump and finally under high vacuum to give 9.1. g residual liquid. This liquid was redistilled to give 8 g of product; η ³⁰ = 1.5274.

Example 2

O o

II 11 ^C 2 ^H 5 - ^S - ^C - <

.CH, -CH, -CH _?

I ch ₂ -ch ₂ -ch ₂

Prepare a solution containing 22.3B (0.11 mol) of m-chloroperoxybenzoic acid in 300 ml of methylene chloride. This solution is heated to 29.5 ° C in the reaction mixture, and 9.4 g of S-ethylhexahydro-1H-azepine-1-carbothioate are added to the heated solution over a period of three minutes. During this addition, the temperature rose to 41 ° C. After 1.5 hours aa the solution was cooled to 9 ° C and filtered ea. The filter cake is washed twice with 25 ml of methylene chloride. The filtrate is washed four times with 100 ml of 556 sodium carbonate solution and twice with 100 ml of water, then dried over magnesium sulphate and concentrated on a rotary evaporator under the pressure of a water pump to give 10.3 β product; η ^ θ = 1.5000.

and

Example 3

OO

II II /

O

AND

CH ₂ -CH _x CH ₂

CH-CH3

A solution was prepared containing 22.3 g (0.11 mol) of m-chloroperoxybenzoic acid in 300 mL of methylene chloride. The solution was cooled to 30.5 ° C, and 11.5 g (0.05 mol) of S-isopropyl-5-ethyl-2-methylpiperidine-1-carbothioethane was added over three minutes to the cooled solution. During this addition, the temperature rises to 41.5 ° C. The reaction mixture is maintained at this temperature and then cooled in an ice bath and filtered. The filter cake was washed with two portions of methylene chloride (2 x 25 mL) and dried in an oven. The combined filtrate is washed four times with 100 ml of 5% sodium carbonate solution and twice with 100 ml of water, dried over magnesium sulphate and concentrated on a rotary evaporator, initially under pressure from a water pump and finally under high vacuum, to give 12.2 g of product; .nu.max = 1.4871.

Example 4

A solution is prepared containing 12.8 g of S-butyldecahydroquinoline-1-carbothioate (0.05 mol) in 200 ml of methylene chloride. The solution was cooled to -14 ° C and 10.7 g (0.0525 mol) of m-chloroperoxybenzoic acid was added to the cooled solution over five minutes. The reaction mixture is then held at this temperature for one hour and ten minutes, then warmed to -5 ° C and maintained at this temperature for an additional 30 minutes. The reaction mixture was then allowed to warm to 16 ° C and filtered. The filter cake is washed twice with 25 ml of methylene chloride. The combined filtrate is washed four times with 100 ml of 5% sodium carbonate solution and twice with 100 ml of water, dried over magnesium sulphate and concentrated on a rotary evaporator, initially under pressure from a water pump and finally under high vacuum, to give 12 g of product; n ^ ° = 1.5228,

Other compounds were prepared in an analogous manner using the appropriate starting materials. These compounds are listed in Table 1 below, where they are assigned a sequence number under which they are listed in the tests described above to determine their herbicidal properties.

206693

Table 1

RS (0) _n -CN:

Compound No. R R, ® Rg n 1 -C ₂ H 5 CH, -CH, -CH, < 1 1 Physical constant: η ^ θ “.1,5274 ^X CH ₂ -CH ₂ -CH ₂ 2 -g ₂ h ₅ _/ ch ₂ -ch ₂ -ch ₂ 2 Physical constant: η ^ θ ^x ch ₂ -ch ₂ -ch ₂ »1,5000

nC-jH?

Physical constant: n ^ ® = 1.5236

CH, -CH,

Z ^{i z} \ \ / ^CH 2 CH ₂ CH ₂ n-CjHy

CH, -CH,

From ^{2 2} \ \ ^ch 2

Physical constant: η ^ θ “1.4937

1- ° 3 “7? 2 ^Η 5

Physical constant: n ^ ® »1, 5074

AND

CH, -CH2.2H-CH2

AND

CH ₂ , CH ₂

1-0 _Λ

Physical constant: η ^ θ = t, 4871 r ⁰ / CH 3 -CH 2 / ^CH

CH - CH, ^{C * i} ch ₃

-c ₃ h ₆ -ci

Physical constant: η ^ θ = 1.5272

CH,

I ^J

CH, -CH ² ^CH 2

CH —CH,

I ^I _CH3 continuation of Table 1

Compound No. R

R ₃ and R 8 c ₃ h ₆ -ci

CH,

AND

CH, -CH / ² \

Physical constant: n ^ ° = 1.5046 \ h -ch /

AND

CH,

CH, —CH, / ^L \ n C, H _q CH ₂ CH ₂ in \ Z

CH-CH _X / CH, \ /

CH3-CH3

Physical constant: n = ⁰ = 1.5228

10 ^I ^"C 3 ^H 7 _{/ C} h ₂ -ch ₂ -ch ₂ , ^x ch ₂ -ch ₂ -ch ₂ Physical constant: η ^ θ = 1.5278 11 - ^C 2 ^H 5 CH, CH, / ^{2 2} \ CH ¹ \ Z -CH ² -CH ₂ Physical constant: η ^ θ = 1.5265 ch ₃

\

-nC _;} H ₇

Physical constant: - 1.5198

CH, —CH, / * ^of \

CH, \ z ²

CH —CH,

I ²

CH,

-n-Gy4

Physical constants: θ η ^ - 1.5240 / CH ₂ -CH 2 ^- CH 2 ^x CH 2 -CH ₂ -CH ₂

-nC ₄ H ₉

Physical constant: n ^ ⁰ = 1,5181 _/ ch ₂ -ch ₂ -ch ₂ ^x ch ₂ -ch ₂ -ch ₂

-iC ₄ H ₉

Physical constant: mp = 57.0-61.5 ° C

H2 ~ CH 2 C H2 ^x ch ₂ -ch ₂ -ch ₂ continued Table 1

Compound No. R R | β Rg n 16-C, Hg-Cl ^ 2 ^H 5 1 ch ₂ -ch. / ch ₂ ^ ch-ch / 1 Physical constant: η ^ θ = 1.5184 ^C 2 ^H 5

-c ₂ h ₅ '2 ⁿ 5 c, H, ch ₂ -ch

CH,

Physical constant: n = 0 - 1.5074

CH-CH,

I, C ₂ H _5, 8

-CH,

Physical constant: η ^ θ = 1,5215 <= 2 ^H 5 _of ch ₂ -ch _x k ^CH 2 \ h - ^CH 2

I ² ch ₃ ^C 2 ^H 5

Physical constant: n = 0 = 1.5161 ^< 2 ^H 5 / ^CH 2 -CH _x ; ch ₂ ^x ch -ch /

I ² ch ₃ η-Ο ^ Ηγ 2 2 ^H 5 ch ₂ -ch _x

Physical constant: η ^ θ = 1.5123 ^X CH-CH

I ch ₃

CH

-nC ₄ H _g

Physical constant: η ^ θ - 1,5071 ch ₂ -ch.

; / ^CH 2

CH — CH,

I ² ch ₃

-iC

4 9 9, CH, —CH / ^L \

Physical constant: η ^ θ = 1.5075

CH — CH,

AND

CH,

CH, continuation of Table I

Compound No. R, R, and Rg n - <= 2 ^Η 5 23 -sec-C ^Hg ch ₂ -ch 1 ^H 2 CH-CH 1 ^z Physical constant: = 1.5089 ch ₃

Test for determination of herbicidal activity

As mentioned, the novel compounds are phytotoxic compounds which are useful for controlling various plant species. The herbicidal activity tests are carried out as follows for the compounds of the invention.

A. Assay to determine pre-emergence herbicidal activity

Using an analytical balance, weigh 20 mg of the test compound on a piece of weighing parchment paper. The compound paper was then placed in a 30 mL wide neck flask, and 3 mL of acetone was added to the flask to dissolve the compound. If the compound is not soluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is used. If dimethylformamide is used, only 0.5 ml or less is used, and another solvent is used to bring the resulting solution to a volume of 3 ml. The 3 ml solution was sprayed evenly on the soil contained in a small polystyrene (Styrofoam) culture pot, one day after the weed seeds were planted in the soil. DeVilbiss sprayers are used for spraying at a compressed air application pressure of 0.035 MPa. The application rate is 8,960 g per ha and the volume is 1,600 l per ha.

One day before application, the cultivation vessel, whose dimensions are 18 cm long, 13 cm wide and 7 cm deep, is filled with sand clay up to 5 cm. Seeds of seven different weed species are planted in individual rows, one in each row across the width of the cultivation vessel. The seeds are then covered with clay so that they are sown at a depth of 13 mm. The weeds used are the bloodweed (Digitaria sanguinalis), the yellow foxtail (Setaria glauca), the hedgehog (Echinochloa crusgalli), the oat (Avena sativa), the Amaranthus retroflexus, the mustard (Brassica juncex) and the plover. ). The seeds are introduced into the soil so that after emergence there are 20 to 50 seedlings per row.

After application, the culture vessels are placed in a greenhouse at a temperature of 21.1 to 29.4 ° C, where they are irrigated in places by sprinkling with water. Two weeks after application, the degree of damage or control is determined in comparison to plants of the same age that were not treated as described. The control efficiency is evaluated as the percentage damage to the plants, with a control efficiency of 0 corresponding to zero damage and a control efficiency of 100% corresponding to complete crop destruction.

B. Assay to determine post-emergence herbicidal activity

The seeds of six plant species, i.e. bloody dew, hedgehogs corn, oat, mustard, sorrel, and bean (Phaseoulus vulgaris), are planted in the expanded polystyrene (Styrofoam) culture vessels described above in the preemergence test. The bowls were then placed in a greenhouse where they were stored at 21.1-29.4 ° C and watered with a water spray. Aei is sprayed 10-14 days after incorporation of the seeds into the soil, when the primary leaves of the beans are almost completely developed and when the first trifoliary leaves begin to form. A spray is prepared by weighing about 20 mg of the test compound, dissolving in acetone followed by the addition of 5 µl of water. The solution is then applied as a foliar spray using a DeVilbiss sprayer at a compressed air application pressure of 0.035 MPa. The spray concentration is 0.2% and the application rate is 8,960 g / ha. The spray volume is 5,530 l per ha.

The results obtained are summarized in Table II below.

Table II

Compound No. Control effectiveness Pre-allergenic applications (56) at an application rate of 8,960 g / ha Poetemergent application 1 91 65 2 0 26 3 91 68 4 0 69 5 99.9 77 6 0 65 7 99.7 74 8 0 67 9 99.7 83 10 92 83 11 99 71 12 99.7 79 13 95 74 14 100 ALIGN! 78 15 Dec 99 79 16 98 89 17 98 78 18 93 71 19 Dec 99 82 20 May 100 ALIGN! 83 21 100 ALIGN! 82 22nd 30 0 23 100 ALIGN! 70

The values given are the average of the values obtained in the case of the pre-emergence test for seven plant species and in the case of the post-emergence test for six plant species.

Compound No. Effectiveness of controls; dose of 2t r (56) in application! 400 g / ha 2 12

This value is the average of the values obtained for seven plant species

209693

Table 111

Pre-emergence application of the herbicide at a rate of 90 kg / ha

Herbicide Bloody Deer Peka Yellow Hedgehog Corn Leg Oat Laska - thing bent

Claims

SUBJECT OF THE INVENTION

Herbicidal composition, characterized in that it contains a compound of the formula I as active ingredient:

RS (O) _n -Cl (I) wherein n is 1 or 2,

R is selected from the group consisting of alkyl of 1 to 6 carbon atoms and chloralkyl of 1 to 6 carbon atoms in the alkyl moiety,

R 1 and R 8 together form an alkylene group of 5 or 6 carbon atoms, an alkylene group of 5 or 6 carbon atoms, substituted with an alkyl of 1 to 4 carbon atoms, or a group ^CH ₂ --CH ₂

CH ₂ / ^CH 2 ^X CH-CH 2

CH ₂ , CH ₂ - / CH ₂ —ch ₂

2. A composition according to claim 1, characterized in that it comprises as active ingredient a compound of formula 1 in which R represents -CgH ^, R, and Rg are groups _/ CH ₂ -CH ₂ -CH ₂ ^X CH ₂ -CH ₂ -ch ₂ and _n means 1.

3. A herbicidal composition as claimed in claim 1, characterized in that it contains a compound of the formula I as active ingredient in which R is -CgH4, Rj and Rg are groups.

B CH ₂ - CH ₂ --CH ₂ '| and n is 2.

^x ch ₂ -ch ₂ -ch ₂

The fourth compound according to claim 1, wherein the compound of formula I wherein R is n = H ?, said compound comprises R ^ and Rg are _ru _ _u n is the first

ch ₂ ch _2x \> ^h 2 ch ₂ -ch ₂

Fifth compound according to claim 1, characterized in that it comprises as active ingredient a compound of formula I wherein R represents H ^ n ?, R and R G are -CH ₂ CH ₂ CH _{2 and} n _a is the second

ch ₂ -ch ₂

6. A herbicide composition according to claim 1, characterized in that it comprises as active ingredient a compound of formula I wherein R represents H ?, IC R ₁ and Rg are ^θ2 Η 5 _/ CH ₂ -CH AN is the first

CH — CH, I ^from CH,

CH,

7. A herbicide composition according to claim 1, characterized in that it comprises as active ingredient a compound of formula I wherein R represents H ?, IC R ₁ and Rg are C ₂ H ₅ CH ₂ -CH _x ^X _x -CH = CH

AND

CH, and n is 2.

CH,

8. A herbicidal composition according to claim 1, wherein the active ingredient is a compound of formula 1 wherein R represents C ^ Hg-Cl, R ₁ and Rg are _CH3

CH, -CH _X

CHg ch-ch ₂ ^z

CH, and n is 1.

9. A herbicidal composition according to claim 1, characterized in that it comprises as active ingredient a compound of formula I wherein R represents C ^ Hg-Cl, R, and Rg is CH ₃ CH ₂ CH _^x CH-CH /

I ch ₃ and n is 2.

10. The herbicidal composition of claim 1, wherein the active ingredient is a compound of formula (I) wherein R is n-C1-4Hg, R5 and R8 are:

CH, _CH2 _--CH2 'CHCH

CH,

CH, and n is 1.

11th herbicidal compound CH ₂ -CH ₂ composition according to claim 1, characterized in TIA the formula 1 wherein R is -ic = H ?, R, CH, CH, CH ₂ 2 | ch ₂ - ch ₂ - ch ₂ contains as active substance and R g are _n and are 1.

12. A herbicidal compound of the composition of claim 1 wherein the formula I in which R ₂ represents -C Hg, R, and

CH, —CH, .CH,

CH-CH

AND

CH, as the active ingredient contains R ₂ , and _n is 1.

13. A herbicidal compound of the composition according to claim 1, wherein the formula 1 wherein R is -NO ?, R = H, / ^CH 2 ^CH 2 \ \ - / ^CH 2 ^X-CH CH /

Also, ^from CH, as the active ingredient, and R 8 are and n is 1.

14th herbicidal compound as in claim 1, wherein the Formula I wherein R is -NHC = H ?, R, comprises as active ingredient _2, and R = CH ₂ - CH ₂ - CH ₂ and n is the first

ch ₂ -ch ₂ -ch ₂

15. A herbicidal composition as claimed in claim 1, wherein the active ingredient is a compound of formula (I) wherein R is -I-C1-Hg, R1 and Rg are:

CHg- CH ₂ - CH ₂ and n is the first

16th herbicidal composition according to claim 1, characterized in that it comprises as active ingredient a compound of formula I in which R represents -ic ^ Hg, Rg and R are CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ - CH ₂ and _n means 1.

17. A herbicidal composition as claimed in claim 1, wherein the active ingredient is a compound of formula (I) wherein R is -n-C1-C4-Cl, Rj and Rg are 2

AND

CH, —CH.

\ ^CH 2 CH-CH,

^LC 2 ^H 5 and n = 1.

18th herbicidal compound as in claim 1, wherein said compound comprises the formula I, wherein R is "CGH ^, ^ 1 ^and ^ 2 ^ ^sou? 2 ^H 5, CH ₂ -CH

CH-CH> _{2 and} n 4 is the first

19th herbicidal compound as in claim 1, wherein said compound comprises the formula I in which R represents -CH =, R and Rg are? 2 ^H 5

CH, -CH,

CH — CH I

CH ₂ _{/ C} h ₂ and _n = 1.

20th herbicidal compound as in claim 1, wherein said compound comprises the formula 1 in which R represents -CgHg, R and Rg are? CH 2 ^H 5, -CH ² CH ₂ ^x CH-CH ^ n means 1.

AND

CH,

21st herbicidal compound as in claim 1, characterized in that contains as active 1'átku formula I in which R represents -NC ^ Hy, R, and R ₂ is? CH 2 ^H 5 -CH ₂ _X

CH-CH ₂

CH, and n is 1,

CH,

22. A herbicidal compound according to claim 1, wherein the active ingredient is of the formula (I) in which R is -n-C1-Hg, R, and Rg are:

C, H, '2 _of 5 -CH ₂ CH CH _^S CH.

AND

CH,

CH, Z ² and ⁿ are 1.

23. A herbicidal compound as claimed in claim 1, wherein the active ingredient is of the formula (I) wherein R is i-C1-Hg, R1 and Rg are:

CH, —CH 2 ^H 5

CH-CH.

Z is ^CH 2 and ⁿ is 1.

ch ₃

24th herbicidal composition according to claim 1, characterized in that it comprises as active ingredient a compound of formula 1 wherein R is -sec-C ^ H ^, R and Rg jeou / CH ₂ -CH

CH-CH

AND

CH ₂ _{/ C} h ₂ and _n = 1.

25. A process for the preparation of an active compound according to formula I,

II

R-S (O) -C-N (I) wherein n is 1 or 2,

Rj 'and Rg together form an alkylene group of 5 or 6 carbon atoms, an alkylene group of 5 or 6 carbon atoms, substituted with a C1-C4 alkyl group, or a group _of ch ₂ -ch ₂ ch ₂ \ h ₂

J? CH-CH = CH ₂ CH ₂ ^* CH ₂ CH ₂ ^/, wherein the compound of formula II (II) where R, R and Rg are as defined above, operating in a solvent system with an oxidizing agent at a temperature of -25 ° C to 60 ° C, wherein the oxidizing agent is used in an amount of at least one stoichiometric equivalent and at most two stoichiometric equivalents.

26. The process of claim 25, wherein the oxidizing agent is m-chloroperbenzoic acid.