CH666890A5 - 2- (1- (3-CHLORALLYLOXYAMINO) ALKYLIDES) -5-ALKYLTHIOALKYL-CYCLOHEXAN-1,3-DION. - Google Patents

Description

DESCRIPTION

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Technical field

This invention relates to trans-2- [l- (3-chloroallyl-amino) propylidene] -5- (2-ethylthiopropyl) cyclohexane-1,3-dione and salts thereof, their preparation and their use of such compounds as herbicides.

State of the art

In U.S. Patent No. 4,440,566, issued April 3, 1984, compounds are described which have the formula

R NO-R1

\ /

C.

have what

R is most preferably alkyl or 1 to 3 carbon atoms, most preferably ethyl or propyl;

35 R1 is most preferably 3-trans-chloroallyl or 4-chloro-benzyl;

R2 and R3 are preferably each alkyl or 1 to 3 carbon atoms, or one of the radicals R2 or R3 is hydrogen and the other is alkylthioalkyl having 2-6 carbon atoms, 40 most preferably R2 and R3 are each methyl, or one of the radicals R2 or R3 is hydrogen and the other is 2-ethyl-thiopropyl.

My patent also teaches that these compounds show herbicidal activity against grasses and are safe with respect to broad-leaved crops.

Presentation of the invention

It has now been found that one of the compounds (ie see Formula I below, wherein R is ethyl) 50 which falls under U.S. Patent No. 4,440,566 surprisingly exhibits superior herbicidal activity compared to other compounds, including their homologues, where R is propyl. This is particularly surprising because such a homolog, in which R is propyl, is a very good Herbi-55 cid.

The present compound shows both a pre-emergence activity and an excellent post-emergence herbicidal activity against «Bermuda grass», foxtail «foxtail», «crabgrass», wild maize «volunteer 60 com», wild sorghum «volunteer sorghum», "Barnyard-grass", broad-leaved signal grass "broad-leaf signalgrass", goose grass "goosegrass", red rice "red rice", "sprangletop", spilling Johnson grass "seedling Johnsongrass" and "Rhizone Johnsongrass".

65 The compound of formula I shows excellent phytotoxicity to grasses in even very small amounts, and it can be safely used with such amounts with respect to broad-leaved crops

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the. Accordingly, the present compound is especially useful for controlling grassy weeds in broad-leaved crops, and is especially useful for controlling grassy weeds in soybean plants.

The compound of the present invention can be represented by the following formula:

itfor1 //

ch3ch2c

0. ^ OH

h ch2chsch2ch3

(I)

wherein R1 is 3-trans chloroallyl.

The invention also encompasses compatible salts of the compound of formula I.

As can be clearly seen, compounds of the nature of formula I exist as tautomers. The compounds also have two asymmetric carbon atoms and they can also exist as optical isomers. The above formula is also intended to encompass the respective tautomeric forms as well as the individual optical isomers as well as mixtures thereof, and the respective tautomers and optical isomers as well as mixtures thereof are encompassed by the invention.

According to a further aspect, the invention provides a herbicidal composition which contains a compatible carrier material and a herbicidally effective amount of the compound (s) of the invention or mixtures thereof.

The present invention also provides a method of preventing or controlling the growth of unwanted grassy vegetation which comprises treating the growth medium and / or foliage of such vegetation with a herbicidally effective amount of the compound (s) of the invention or mixtures thereof.

The present invention also provides a method of regulating plant growth which comprises treating the growth medium and / or foliage of such vegetation with a plant growth regulating effective amount of the compound (s) of the invention or mixtures thereof, effective to control normal Change the growth behavior of the plants mentioned.

The present invention also provides chemical intermediates and methods for making the compounds of the invention.

The invention is described in more detail below.

Way of carrying out the invention

The compound of formula I can be conveniently prepared using the following schematic procedure:

oh ch, chsch, ch

(a)

wherein R1 is 3-trans chloroallyl.

This process can be carried out conveniently by contacting compound (A) with 3-trans-chlorolyloxyamine (B), preferably in an inert organic solvent.

Typically, this process is carried out at temperatures in the range of about 0-80 ° C, preferably about 20-40 ° C, for about 1-48 hours, preferably about 4-12 hours, using about 1-2 , preferably 1.05 to 1.2 moles, of 3-trans-chloroallyloxyamine (B) per mole of compound (A). Suitable inert organic solvents that can be used include e.g. lower alkanols, e.g. Methanol, ethanol,

Ethers, e.g. Ethyl ether; Methylene chloride. Two phase water and immiscible organic solvent (e.g. hexane) and the like, and compatible mixtures thereof, can also be used.

Trans-chloroallyloxyamine is a known compound and can be prepared by known methods such as e.g. those described in my U.S. Patent No. 4,440,566. Conveniently, a hydrochloride salt of trans-chloroallyloxyamine can be used by neutralizing the salt with an alkali metal oxy in situ.

The starting materials of formula (A) can be prepared using the general procedure described in my U.S. Patent No. 4,440,566.

The compatible salts of formula (I) can be prepared by conventional methods, e.g. via the reaction of the compound of formula I with a base, such as sodium hydroxide, potassium hydroxide and the like, which has the desired cation. Further variations in the salt cation can also be brought about via ion exchange with an ion exchange resin which has the desired cation.

The reaction product can be recovered from its reaction product mixture by any suitable separation and purification method, such as, for example, chromatography. Suitable separation and purification processes are e.g. illustrated in the examples below hereinafter.

In general, the reactions described above are carried out as a liquid phase reaction and therefore the pressure is generally not significant except that it affects the temperature (boiling point) when the reactions are carried out under reflux. Therefore, these reactions are generally carried out at pressures of about 300-3000 mm of mercury, and conveniently they are carried out at around atmospheric or ambient pressure.

It should also be noted that when typical or preferred process conditions (e.g. reaction temperatures, times, molar ratios of reactants, solvents, etc.) have been given, other processes are also described

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conditions can be used. Optimal reaction conditions (e.g. temperature, reaction time, molar ratios, solvents, etc.) may vary with the specific reagents or organic solvents used, but de can be determined using routine optimization procedures.

If optically isomeric mixtures are obtained, then the respective optical instruments can be obtained using conventional resolution methods. Geometric isomers can be separated using conventional separation methods, which depend on the difference in physical properties between the geometric isomers. However, it is generally preferred to use the desired isomeric starting material in the reaction.

Definitions

As used herein, the following terms have the following meanings, unless the contrary is expressly stated:

The term "tolerable salts" refers to salts that do not significantly adversely affect the herbicidal properties of the related compound. Suitable salts include cationic salts, such as the cationic salts of lithium, sodium, potassium, alkaline earth metals, copper, zinc, ammonia, quaternary ammonium salts and the like. The term “room temperature” or “ambient temperature” refers to approximately 20-25 ° C.

Commercial usability

The compound of formula I and its salts show both pre- and post-emergent herbicidal activity, and they particularly show good herbicidal activity against grasses. The compounds show particularly good phytotoxicity towards foxtail, bermuda grass, crabgrass, rhizone Johnsongrass and wild maize, volunteer com, which are weed species which are generally very difficult to control.

For post-emergent applications, the herbicidal compounds are generally applied directly to the foliage or other parts of the plant. For pre-emergence applications, the herbicidal compounds are applied to the growth medium or to the expected growth medium for the plant. The optimal amount of herbicidal compound or composition will vary with the particular plant species, and the extent, if any, of plant growth and the particular part of the plant that is contacted and the extent of contact. The optimal dosage may also vary with the general location or the environment (e.g. protected areas such as greenhouses compared to exposed areas such as fields) and the type and degree of control desired. In general, the compounds according to the invention are used in amounts of approximately 0.02 to 60 kg / ha, preferably approximately 0.02 to 10 kg / ha, both for pre- and post-emergent control.

Although in theory the compounds can be used undiluted, in current practice they are generally used as a composition or formulation containing an effective amount of the compound (s) and an acceptable carrier. An acceptable or acceptable carrier (agriculturally acceptable carrier) is one that does not significantly adversely affect the desired biological effect achieved by the active compounds, except that it serves for dilution purposes. Typically, the composition contains from about 0.05 to 95% by weight of the compound of formula I.

or mixtures thereof. Concentrates can also be made which have high concentrations which are intended for dilution prior to use. The carrier material can be solid or liquid or an aerosol. The respective compositions can take the form of granules, powders, dusts, solutions, emulsions, slurries, aerosols and the like.

Suitable solid support materials which can be used include e.g. natural clays (such as kaolin, attapulgite, montmorillonite, etc.), talc, pyrophyllite, diatomaceous silica, synthetically fine silica, calcium alumosilicate, tricalcium phosphate and the like. Organic materials, such as, for example, walnut shell flour, cotton seed shells, wheat flour, wood flour, wood bark flour and the like, can also be used as carrier materials. Suitable liquid diluents that can be used include e.g. Water, organic solvents (e.g. hydrocarbons such as benzene, toluene, dimethyl sulfoxide, kerosene, diesel fuel, 20 fuel oil, petroleum naphtha, etc.) and the like. Suitable aerosol carriers that can be used include conventional aerosol carriers such as halogenated alkanes, etc.

The composition may also contain various chemical accelerators and surfactants which promote the rate of transport of the active compound into plant tissue, such as, for example, organic solvents, wetting agents and oils, and in the case of compositions intended for pre-3q emergence If intended for use, agents can be included which reduce the leachability of the compound or otherwise promote soil stability. Agricultural oils (crop oils), such as soybean oils, paraffin oils and olefinic oils, 35 are particularly advantageous as carrier materials or additives in that they promote phytotoxicity.

The composition can also contain various compatible auxiliaries, stabilizers, conditioning agents, insecticides, fungicides and, if desired, further herbicidally active compounds.

A convenient concentrate formulation which can be used comprises 23-27% by weight of the active herbicide of the invention, 2-4% by weight of an emulsifier, e.g. Calcium alkylbenzenesulfonates, octylphenol ethoxylate, etc., or 45 mixtures thereof, and about 70-75% organic solvent, e.g. Xylene, etc. The concentrate is mixed with water, and preferably with an agricultural oil, prior to use, and is used as a water emulsion containing about 0.5 to 2% 50% of an oil used in agriculture, e.g. Soybean oils, and paraffinic oils and olefinic oils. Conveniently, the herbicide is used as a water emulsion containing about 0.02 to 0.6%, preferably 0.07 to 0.15% by weight of the herbicide of the invention; about 0.001 to 0.01 55% by weight of an emulsifier; about 0.08 to 2.5% by weight of an organic solvent, and about 95-99% by weight of water. Preferably the composition also contains about 0.25 to 2% by weight of an oil used in agriculture. The application composition can be conveniently prepared by mixing the concentrate formulation with about Vi to Vi of the desired amount of water. Then the oil used in agriculture and the remaining amount of water are added. If no agricultural oil is used, the water and concentrate formulation are simply mixed together.

A further understanding of the invention can be found in the following non-limiting preparation (s) and example (s)

to have. Here, unless expressly stated to the contrary, all temperatures and temperature ranges refer to the Celsius system, and the term “ambient temperature” or “room temperature” refers to approximately 20-25 ° C. The term “percent” or “%” refers to percent by weight, and the term “mole” or “mole” refers to grams of mole. The term "equivalent" refers to an amount of reagent equivalent to moles, to the moles of the previous or subsequent reactant mentioned in this example, in limited moles or weight or volume. If indicated, the proton magnetic resonance spectrum (pmr or NMR) was determined at 60 mHz, and the signals were recorded as singlets (s), broad singlets (bs), doublets (d), double doublets (dd), triplets (t), Denoted double tri-plets (dt), quartets (q) and multiplets (m); and cps refers to revolutions per second. If necessary, examples were also repeated to provide additional starting material for subsequent examples.

example 1

Trans-2- [1- (3-chloroallyloxyamino) propylidene] -5- (2-ethylthio-propyl) cyclohexane-1,3-dione

In this example, 17.2 g (0.0636 mol) of 2-propionyl-5- (2-ethylthiopropyl) cyclohexane-1,3-dione; 0.9 g (0.0153 mol) of acetic acid, and 10.9 g (0.0757 mol) of 3-trans-chloroallyloxyamine in 35 ml of water were added to 20 ml of hexane and stirred. Aqueous 5% by weight sodium hydroxide was slowly added over about 15 minutes until 3.0 g (0.0757 m plus slight excess) of sodium hydroxide had been added - pH of the reaction mixture about 6. The mixture was warmed and to 40 ° C held for 2Vi hours and then cooled to room temperature. The organic (i.e. hexane) phase was separated and washed with 10 ml of aqueous 5% by weight hydrochloric acid, and then 6.25% by weight sodium hydroxide was added up to pH 12. The aqueous phase was separated and mixed with 25 ml of hexane and the pH was adjusted to 5.4 by dropwise addition of 36% by weight aqueous hydrochloric acid over an ice bath. The organic phase was separated, dried over magnesium sulfate and then concentrated by evaporation to give 18.0 g of a crude product. The crude product was purified by silica gel column chromatography eluting with hexane: methylene chloride to give the purified title compound as an oil.

Elemental analysis carbon: calculated 56.73%, found 56.63%

Hydrogen: calculated 7.28%, found 7.55%

Nitrogen: calculated 3.89%, found 3.55%

Example 2

Sodium 2- [l- (3-trans-chloroallyloxyamino) propylidene-3-oxo-5- (2-ethylthiopropyl) cyclohex-1-en-1-olate. This example illustrates a method that can be used to prepare the title compound. A solution containing 0.01 mol of sodium hydroxide dissolved in 2 ml of water became a solution containing 0.01 mol of 2- [l- (3-trans-chloroallyloxyamino) propylidene-5- (2-ethyl -thiopropyl) -cyclohexane-l, 3-dione added at room temperature. After the reaction was complete, the solvents were evaporated under vacuum;

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1 -hydroxy sodium salt of 2- [l- (3-trans-chloroallyloxyamino) propylidene-3-oxo-5- (2-ethylthiopropyl) cyclohex-1-en-1-ol was obtained.

Example 3

In this example, the title compound of Example 1, i.e. 2- [l- (3-trans-chloroallyloxyamino) propylidene] -5- (2-ethylthiopropyl) cyclohexane-1,3-dione, tested, using the methods described below for pre-emergent and post -emergic phytotoxic activity against a variety of grasses and broad-leaved plants, including a grain crop and a broad-leaf crop.

Pre-emergent herbicidal test

Pre-emergence herbicidal activity was determined in the following manner.

Test solutions of the respective compounds were prepared as follows:

355.5 mg of the test compound was dissolved in 15 ml of acetone. 2 ml of acetone containing 110 mg of a nonionic surfactant was added to the solution. 12 ml of this stock solution were then added to 47.7 ml of water, which contained the same nonionic surface agent at a concentration of 625 mg / 1.

The seed of the test vegetation was planted in a pot of soil and the test solution was sprayed uniformly onto the surface of the earth at a test compound dose of 27.5 micrograms / cm 2 unless otherwise stated in the following tables. The pot was watered and placed in a greenhouse. The pot was watered every now and then and observed for the emergence of the seedlings, the health of the emerging seedlings, etc. over a three-week period. At the end of this period, the herbicidal activity of the compound was evaluated based on the physiological observations. A 0-100 scale was used, with 0 representing no phytotoxicity and 100 representing total killing. The results of these tests are summarized in Table 1.

Post-emergent herbicidal test

The test compound was formulated in the same manner as described above for the pre-emergent test. This formulation was uniformly sprayed onto two equal pots containing 2-3 inch plants (except wild oats, wild soybean and soybean and watergrass 3-4 inches) (approximately 15-25 Plants per pot) at a test compound dose of 27.5 micrograms / cm2 unless otherwise specified in the following tables. After the plants were dry, they were placed in a greenhouse and then watered at their base every now and then if necessary. The plants were observed periodically for the phytotoxic effects and the physiological and morphological reactions to the treatment. After 3 weeks, the herbicidal activity of the compound was evaluated based on these observations. A 0-100 scale was used, with 0 representing no phytotoxicity and 100 representing complete killing. The results of these tests are summarized in Table 2.

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Table 1 Pre-emergence herbicidal activity Application amount: 27.5 micrograms / cm2 unless otherwise stated broad-leaved plants grasses

Compound% phytotoxicity% phytotoxicity

Lambsquarter Mustard Pigweed Soybean Barnyard Grass Crabgrass Wild Oats Rice

1 25 30 25 30 100 100 100 100

Table 2 Post-emergence herbicidal activity application amount: 27.5 micrograms / cm2 unless otherwise stated broad-leaved plants grasses

Compound% phytotoxicity% phytotoxicity

Lambsquarter Mustard Pigweed Soybean Barnyard Grass Crabgrass Wild Oats Rice

1 30 45 40 40

Example 3

In this example, the title compound of Example 1 of the present invention, ("1") was post-emergence herbicidal activity at moderately low dosage levels side by side with its butylidene homolog, i.e. trans-2- [1- (3-chloroallyloxyamino) butylidene] -5- (2-ethylthiopropyl) cyclohexane-1,3-dione.

The tests were carried out in the same manner as described in Example 2 hereinabove, except that the applications listed in Table 3 were 100 100 100 100

quantities were used and 4 repeat pots were used instead of 2 per test. The average result of the four replicates is given in Table 3 below, where 0 indicates no phytotoxicity and 100 represents complete killing. In general, phytotoxicity below about 20-30% is not considered significant because the plant can typically continue to grow from this amount of damage.

Table 3 Post-emergence herbicidal activity Moderately low dose tests

broad-leaved plants

Grasses

% Phytotoxicity

% Phytotoxicity

connection

dosage

Lambs

Mustard

Pigweed

Soybean

Crabgrass

Barnyard

Wild oats

Rice

No.*

y / cm2 **

quarter

Grass

1

1.8

0

3rd

0

7

100

100

98

98

1

0.7

0

0

0

2nd

100

100

80

85

C-l

1.8

0

0

0

N.T.

87

100

95

97

C-l

0.7

0

0

0

N.T.

60

98

80

87

N.T. = Not tested, but based on other tests, the comparative compound is also safe with respect to soybeans at this dosage level.

1 = trans-2- [l- (3-chloroallyloxyamino) propylidene] -5- (2-ethylthiopropyl) cyclohexane-1,3-dione C-1 = trans-2- [1 - (3-chloroallyloxyamino) butylidene] -5- (2-ethylthiopropyl) cyclohexane-1,3-dione ** y / cm2 = micrograms per square centimeter

As can be seen from Table 3, Compound 1 was significantly superior to comparative Compound C-1 over crabgrass, even at moderately low doses. The superiority of Compound 1 becomes even more apparent at the low dosages used in Example 4 below.

Example 4

In this example, the title compound («1») was compared with trans-2- [l- (3-chloroallyloxyamino) butylidene] -5- (2-ethylthiopropyl) cyclohexane for post-emergence herbicidal activity at a very small dose -l, 3-dione ("Cl") and the commercially available herbi-

55

ziden Sethoxdm («C-2») (i.e. 2- [l- (ethoxyamino) butylidene] -5- (2-ethylthiopropyl) cyclohexane-1,3-dione tested against an expanded list of weed grasses.

These tests were carried out in the same manner as described in Example 3 hereinabove, except that the dosages shown in Table 4 were used. The results of this testing are summarized in Table 4, with 0 indicating no phytotoxicity and 100 indicating complete killing. In general, phytotoxicity below about 20-30% is not considered significant because the plant can typically continue to grow from this amount of damage.

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Table 4 Post-emergent herbicidal activity Low dose testing broad-leaved plant grasses

% Phytotoxicity% phytotoxicity

Compound Dosage Crabgrass Barnyard Wild Oats Rhizone Yellow Yellow Soybean Rice

No. * y / cm2 * grass Johnsongrass Foxtail Nutsedge

1

0.28

71

99

66

99

99

0

0

93

1

0.11

63

90

46

92

92

0

0

83

1

0.05

40

60

6

63

63

0

0

71

1

0.02

5

8th

0

21st

21st

0

0

1

C-l

0.28

55

96

60

68

80

0

0

78

C-l

0.11

25th

70

43

43

53

0

0

70

C-l

0.05

15

40

26

21st

40

0

0

40

C-l

0.02

0

8th

0

0

0

0

0

10th

C-2

0.28

53

80

36

73

68

0

0

63

C-2

0.11

16

68

16

31

48

0

0

41

C-2

0.05

10th

20th

0

0

10th

0

0

10th

C-2

0.02

0

0

0

0

0

0

0

0

As can be seen from Table 4, with the exception of wild oats and yellow nutsedge, Compound 1 was superior to comparative Compound C-1 with respect to each of the other weed species tested. Compounds 1 and C-1 were roughly equivalent to wild oats, and both compounds were inactive at these dosages of yellow nutsedge. Compounds 1 and C-1 were both superior to Compound C-2.

Regarding the dosage required to produce equivalent reactions, an amount of 0.11 q / cm2 of compound 1 is about equivalent to an amount of compound C-1 of 0.28 q / cm2 to control crabgrass and barnyardgrass. An application amount of compound 1 of 0.05 q / cm2 was approximately equivalent to an application amount of compound Cl of 0.28 q / cm2 to control yellow foxtail 30 and an application amount of compound 1 of 0.11 q / cm2 was superior to an application amount of the compound Cl of 0.28 q / cm2 in order to control "Johnsongrass".

It is apparent that many modifications and variations of the invention described hereinabove and below can be made without departing from the spirit and scope thereof.

G

Claims (5)

666 890 PATENT CLAIMS 1. Compound representing the formula CH, CH9 NOR1 wherein R1 is 3-trans chloroallyl; and compatible salts thereof. 2. A compound according to claim 1, characterized in that said compound is 2- [1- (3-trans-chloroallyloxy-amino) propylidene] -5- (2-ethylthiopropyl) cyclohexane-1,3-dione. 3. Herbicidal composition, characterized in that it contains a herbicidally effective amount of a compound according to claim 1 and a compatible carrier material. 4. Herbicidal composition according to claim 3, characterized in that it contains a herbicidally effective amount of the compound according to claim 2 and a compatible carrier material. 5. Herbicidal composition according to claim 3, characterized in that it contains a herbicidally effective amount of the compound of claim 1 and an agricultural oil (crop oil). 6. Herbicidal composition according to claim 3, characterized in that it contains 0.02 to 0.6% by weight of a compound according to claim 1.0.001 to 0.15% by weight of an emulsifier, 0.08 to 2.5% by weight of an organic solvent and about Contains 95 to 99 wt .-% water. 7. Herbicidal composition according to claim 6, characterized in that said composition contains about 0.25 to 2% by weight of an oil used in agriculture. 8. Herbicidal composition according to claim 3 in the form of a concentrate, characterized in that it contains 23-27 wt .-% of a compound according to claim 1.2 to 4 wt .-% of an emulsifier and about 70-75 wt .-% of an organic Contains solvent. 9. A method of controlling grassy plants, characterized in that it comprises applying a herbicidally effective amount of a compound according to claim 1 to the foliage or the growing environment of said plants. 10. A method of controlling grassy plants, characterized in that it comprises applying a herbicidally effective amount of the compound of claim 2 to the foliage or the growing environment of said plants. 11. The method according to claim 9 for checking grass species of foxtail "foxtail", Bermuda grass "Bermuda grass", wild sorghum "volunteer sorghum", broad-leaved signal grass "broad-leaf signalgrass", goose grass "goose-grass", red rice "red rice" , "Sprangletop", "Johnsongrass" or wild corn "volunteer com", characterized in that it comprises the application of a herbicidally effective amount of the compound according to claim 1 to said grass species or their growth environment. 12. A process for the preparation of the compound according to claim 1, characterized in that 2-propionyl 5- (2-ethyl-thiopropyl) -cyclohexane-1,3-dione is reacted with 3-trans-chloro-allyloxyamine under reactive conditions, the corresponding compound of the formula I being prepared. 13. The method according to claim 12, characterized in that the said method is carried out in an inert organic solvent at temperatures in the range of about 0-80 ° C.