FR2531953A2 - NOVEL 2- (1- (OXYAMINO) -ALKYLIDENE) -5- (2-METHYLTHIOPROPYL) -CYCLOHEXANE-1,3-DIONES HERBICIDES AND THEIR APPLICATIONS - Google Patents

Abstract

THE ADDITION CONCERNS NEW PESTICIDE COMPOUNDS FOLLOWING THE MAIN PATENT. IT HAS MORE PARTICULARLY DEALING WITH NEW 21- (OXYAMINO) -ALKYLIDENE-5- (2-ETHYLTHIOPROPYL) -CYCLOHEXANE-1,3-DIONES SUBSTITUTES OF FORMULA: (CF DRAWING IN BOPI) IN WHICH IS A GROUP, IS PROPYLE A TRANS-3-CHLORALLYL OR 4-CHLOROBENZYL GROUP, ONE OF R AND R IS HYDROGEN AND

Description

The invention which is the subject of this certificate

  This addition is an improvement to the subject of French patent application No. 81 21 680 filed on November 19, 1981 by the same Applicant, and it relates to new herbicidal compounds, compositions containing them and their processes. It has been found that new halogenalkenyl-substituted 2- (1- (substituted) -7- (ethylthiopropyl) cyclohexane-1,3-diones

  halaryl were particularly useful as herbicides

  against grasses in applications both in

  in addition to post-emergence In addition, these compounds are gifted

  excellent stability in the soil.

  The compounds of the invention respond to the

  mule (I): ## STR3 ## where R is a propyl group;

  R 1 is a trans-3-chlorallyl or 4-chloro group

robenzyle;

2 3

  one of R or R 3 is hydrogen and the other is 2-ethylthiopropyl; R 4 is hydrogen, R 5 is hydrogen, a cation or an O -CR 6 group in which R 6 is an alkyl radical having 1 to 6 carbon atoms or an aryl radical having 6 to 10

carbon atoms.

  R 1 is very advantageously a trans-3-

  chlorallyl in terms of the phytotoxic properties

  The salts (that is to say when R 5 is a

  tion) are of interest for improving solubility and

  to facilitate formulation Esters (R is a group

  pe-C (O) R 6) are interesting because they hydrolyze

  in the soil to the base compound in which R 5 is the hy-

  drogen. Representative R groups are hydrogen,

  NH 4 +, Na +, K, Ca ++, acetyl, propionyl, butyryl, isobutyl

  tyryl, isovaleryl, 3,3-dimethylbutyryl, benzoyl, 1-

  naphthoyl, 2-naphthoyl R represents advantageously

hydrogen.

  The compounds of the present invention can be prepared according to the following scheme:

O

  I R 4 + RC X = halo (I Ia) Ai C 13 _ y 7 o O o O Il -OCR + f X (1) (III)

R O

C Xc o -04 (2) (II Ia) (II) III

R -NOR 1

OH H 20

  + II Ia + H 2 NOR 1 HC 1 (IV) (3) H Cl R 4 (Ia)

  The appropriate intermediate compounds of

  mule (IV) can be prepared in accordance with the following reaction sequence:

{OH + R 1 C 1

(Va) 1 Hydrazine (5)

- 'H 2 NOR 1HC 1

  (IV) Compounds of formula (I) wherein R 5 is other than hydrogen may be prepared according to conventional methods by treating the hydroxyl compound (Ia) with a suitable basic salt to form compounds wherein R is Na +, NH 4 +, Ca ++, etc. Similarly, the hydroxyl compound (Ia) can be acylated by treatment with an acid halide

  suitable for forming compounds in which R 5 is

  This reaction can be carried out at (V) t 1 + HCl VI (4) (VI), 2HClCl

  ambient temperature, using practically

  The acid chloride (X = Cl) is preferably used equimolarly of the dione (II) and the acid halide (Ia). The reaction can be carried out in an organic solvent such as halogenated -ethers or glycols The presence of a base such as an organic amine or an alkali metal carbonate is recommended, so as to deactivate the hydrogen halide which is released. Preferred organic amines are pyridine

  and trialkylamines such as triethylamine

  pressure conditions are determining, and the pressure

  atmospheric can be used advantageously.

  The reaction (2) can be carried out in an inert organic solvent selected for example from halogenated hydrocarbons or ethers. At least two moles of aluminum chloride are used per mole of ester (III). must be deactivated with a proton donor, preferably a mineral acid such

  as hydrochloric acid, to produce trione (II Ia).

  Reaction (3) is a conventional oxime formation condensation Since hydrochloride (IV) is used, it is first neutralized with a base, preferably an alkali metal alkoxide, prior to its combination with trione (II Ia) or the free base from reaction 5 can be used directly. The reaction can be carried out in an inert organic solvent,

  preferably a lower alcohol.

  Reaction (4) is a conventional alkylation which can be carried out in inert organic solvents such as dimethylsulfoxide, acetonitrile, ethers, glycol ethers or hydrocarbons. The reaction is carried out in the presence of a base such as carbonate of

  potassium, at room temperature.

  The reaction (5) can be carried out at temperatures

  high temperatures, preferably at 30-100 ° C. Phthalimide

  (VI) is advantageously heated to atmospheric pressure.

  with a slight molar excess of hydrazine in a

  inert organic substance such as a lower alcohol, at the

  reflux temperature The raw mixture is then cooled

  di and optionally deactivated with a mineral acid, preferably hydrochloric acid, to give the salt (IV)

  as a product, or the free base can be used

  directly in reaction 3. As a variant relating to reactions (I) and (2) above,

  trione (II Ia) can be formed in one step by treatment

  of the dione (II) with the acid halide (I Ia) in a

  halogenated hydrocarbon solvent, preferably tetrachloro-

  carbon dioxide in the presence of trifluoromethyl sulphate

  Normally, the reaction is carried out at elevated temperature (30-150 ° C), and is completed in 90 minutes

  but it gives a mixture of products Because the

  total reaction time (1) and (2) is approximately 24 hours.

  res, and that a purer product is obtained, the sequence of reactions (1) and (2) in two steps is preferable to

variant in one step.

  The starting materials of 'for-

  mule II by known methods or after modification

  of these processes (for example by using the

  The compounds of formula II can be conveniently prepared by the following process.

  schematically represented by the reaction equations

  the following aggregates: m O O O O C = CIC-C Hi 3 + H 2 C (COR 4) '

(A) (B) 3

(I Ia) I O Coli database (3)

HAVE.

R 21 uj R,> R 3

R R 'R' R

  Wherein R is an alkyl group having 1 to 3 carbon atoms, and R and R have the meanings

data above.

  These reactions are class reactions

  The first reaction step is normally conducted by contacting the compound A with the compound B and a base (for example alkali metal alkoxides).

  under reactive conditions, preferably in soil

  inert (e.g. an alkanol such as ethanol).

  Normally, the reaction is carried out at a temperature of about 60 to 1100 C using about 0.5 to 1.5 moles, preferably 0.9 to 1.1 moles of Compound A and the base per mole of Compound B In the second step, the ester group of the

  It is hydrolysed by a base of

  for example, by contacting metallic sodium in an alkanol (such as ethanol) or an alkali metal hydride at temperatures within

  the range of about 60 to 110 C Steps 1 and 2 may

  can be conducted together by combining the reactants. In the third step, the compound C can be decarboxylated by treatment with an inorganic acid

  strong (eg hydrochloric acid, sulfuric acid).

  This step is normally conducted at temperatures in the range 25 to 1100 C and can be conveniently conducted in situ when finished

  step 2 of hydrolysis with a base.

  The compounds of formula II Ia can also be prepared by reacting the compounds of formula II with the corresponding anhydride in the presence of an organic base,

  preferably in an excess of anhydride or solvent

  This reaction is normally carried out at temperatures in the range of about 1100 C using about 5 to 0.5 moles of anhydride.

per mole of compound II.

  The respective products of the reactions above

  can be isolated and purified by conventional techniques.

  such as chromatography, distillation, crystal

  etc., depending on the appropriate operation.

  The terms "oxyaminoalkylidene" and "oxyiminoal-

  kyle "refer to the radical of formula:

ON = R-

  wherein R is an alkyl group For example, the

  "1-allyloxyaminobutylidene" and "1-allyloxyiminobu-

  "refers to the radical of the formula:

CH 2 = CH-CH 2 ON = C (CH 2)> 2 CH 3

  As is also well known in the case of compounds of formula I wherein R 5 is hydrogen, the compounds are generally referred to as cyclohexane-1,3-diones.

  rather than being called 3-hydroxycyclohex-2-ene-1-ones.

Example 1

  Trans-2- / T- (3-chlorallyloxyimino) butylel-5- (2-

  ethylthiopropyl) cyclohexane-3-dione (a) 86.6 grams of crotonaldehyde were added

  dropwise to a mixture containing 64.0 grams of ethanol

  nethiol and 2 ml of triethylamine in 500 ml of acetonitrile

  at room temperature (about 20-25) The resulting mixture was stirred overnight (about 15 hours)

  at room temperature and then evaporated on the rotary evaporator

  The residue was dissolved in 300 ml of ethyl ether, washed twice with water, dried over magnesium sulfate and concentrated by evaporation to give a yellow liquid concentrate of beta-ethylthiobutyraldehyde. .

  (b) A mixture containing 15.9 grams of beta

  ethylthiobutyraldehyde and 38.2 grams of triphenylphosphine

  phoranylidene-2-propanone in 300 ml of

  The ethylene was heated at reflux overnight and then evaporated to give a thick residue. The residue was mixed with hexane and the mixture was filtered. The filtrate was evaporated in vacuo and the residue was distilled.

  empty, giving 6-ethylthio-3-hept-2-one.

  (c) 2.53 grams of sodium metal was added to 100 ml of ethanol at room temperature.

  then added to the mixture 17.6 grams of malonate of

  stirring, and then 17.2 grams of 6-ethyl-

  thio-3-heptene-2-one The resulting mixture was then refluxed for 4 hours and then a solution was added.

  aqueous sodium hydroxide solution containing 9.5 grams of hy-

  sodium hydroxide in 75 ml of water and the mixture was refluxed for a further 2 hours The mixture was cooled

  at 50 ° C., then acidified by adding hydrochloric acid

  centered It was then heated until decarbonisation

  The xylation is complete and then evaporated to give a liquid residue. The residue is mixed with ethyl ether,

  washed with water and evaporated to give a brown liquid.

  quide extracted with a base and an acid gave the 5- (2-

  éthylthiopropyl) cyclohexane-l, 3-dione. (d) 0.2 gram of sodium metal was dissolved in 1 ml of methanol and then 3.2 grams of 5- (2-ethylthiopropyl) cyclohexane-1,3-dione was added to the solution. 20 ml was added of butyric anhydride and then

  the mixture for 3 hours The mixture was then evaporated

  and the residue was mixed with methylene chloride

  then extracted with an aqueous solution at 5% by weight of hy-

  sodium hydroxide The basic extract was washed with chloride

  of methylene and then acidified with hydrochloric acid

  centered and then extracted into methylene chloride This

  The extract was then evaporated to give 2-butyryl-5- (2-

  éthylthiopropyl) cyclohexane-1,3-dione.

  (e) 0.38 grams of methylamine were mixed together

  of sodium, 10 ml of methanol and 1.0 gram of 3-chlorallyloxyamine hydrochloride (H 2 NOCH 2 CH = CH Cl) and then the mixture was stirred for 10 minutes at room temperature.

  added two grams of 2-butyryl-5- (2-ethylthiopropyl) cyclohe-

  hexane-1,3 dione and the resulting mixture is stirred for

  The mixture was then concentrated by evaporation, and the concentrate was mixed with 60 ml of diethyl ether and 40 ml of water. The ether phase was extracted with 40 ml of aqueous solution. 2% by weight of sodium hydroxide, washed with 20 ml of water, dried over anhydrous magnesium sulfate and evaporated to give a small amount of the compound indicated in FIG.

  title, in the form of the trans isomer.

  The extracted phase with 2% sodium hydroxide solution was acidified to about pH 1 with 6N aqueous hydrochloric acid and extracted with 100 ml methylene chloride. The organic phase was washed with 40 ml of water, dried over magnesium sulfate and evaporated to give the trans-isomer of the title compound as residue (Compound No. 54 of Table A given below). Most of the compound indicated in the title was isolated from the extraction phase

with sodium hydroxide.

Example 2

  This example illustrates the preparation of the compounds

acyloxy of the invention.

  0.89 grams (0.011 moles) of acetyl chloride are added to a reaction mixture containing 3.0 grams

  (0.01 mole) of 2- / T (3'-chlorallyloxyamino) -butylidene 7-5-

  (2-ethylthiopropyl) -cyclohexane-1,3-dione and 0.87 grams (0.011 moles) of pyridine in 20 ml of methylene chloride

  stirring at 0 ° C. The mixture is then stirred at room temperature.

  room temperature for two hours.

  washed with water, dried over anhydrous magnesium sulphate, and filtered. The filtrate is evaporated under

  empty giving 3-acetyloxy-2- [1- (3'-chlorallyloxyamino)]

  butylidene / -5 (2-ethylthiopropyl) cyclohex-2-en-1-one.

  Following the same procedure, the corresponding 3-acetyloxy derivative of each of the products listed in Table A, which is given below, is prepared in the same manner, respectively.

Example 3

  This example illustrates the preparation of

the present invention.

  0.4 gram (0.01 mole) of sodium hydroxide dissolved in 2 ml of water at 3.0 grams (0.01 mole) is added

  2 / T- (3'-chlorallyloxyamino) -butylidene 7-5- (2-ethylthio)

  propyl) -cyclohexane-1,3-dione in 10 ml of acetone

  The solvents are evaporated under vacuum to give the sodium salt

  dium, at the level of the 3-hydroxy group, the 2 / T- (3'-chloro)

  lyloxyamino) -butylidene 7-3-hydroxy-5- (2-ethylthiopropyl) -

  cyclohex-2-en-1-one. Following the same procedure, we prepare

  respectively in the same way the sodium salts of each

  any of the products listed in Table A given below.

  The compounds of the present invention are in general

  of herbicide compounds in both pre-emergence and post-emergence applications For pre-emergence control against unwanted vegetation, herbicide compounds

  are applied in amounts effective from the her-

  bicide in place or in the middle of growth of vegetation, for example a soil infested with weeds and / or seedlings of this vegetation Such an application inhibits

  the growth of seeds, sprouts and seeds

  For post-emergent applications, the herbicidal compounds are applied directly to foliage and other plant parts. Generally, the herbicidal compounds of the invention are particularly suitable for use in post-emergence applications.

  effective weed control in the grading family.

  with a correct dose adjustment, they can be

  plowing safely to control grass or

  their development in plant crops.

  The compounds of the invention are endowed with an excellent

  slow stability in the soil This is of interest

  especially for pre-emergence application.

  When the compounds are applied over the

  soil to growing plants in select quantity-

  so that they do not destroy beneficial plants, they also exert effective regulatory actions or

  growth retardants and can be used-advantageously

  for example to prevent or delay the development of

  plant side buds and to promote the fall of superfluous fruit in the case of various fruit trees. The compounds can be applied in any one of a variety of compositions. In general, they can be diluted with a carrier of the type used and usually considered in the art, for example

  inert solid substances, water and organic liquids

S ques.

  The compounds are included in such composi-

  in an amount sufficient to exert a herbicidal or growth regulating effect.

  proportion of about 0.5 to 95% by weight of the compounds.

  Solid compositions can be prepared with inert powders.

  therefore be homogeneous powders that can be used

  As such, they are diluted with inert solids to form dusts, or suspended in a suitable liquid medium for spray application. Powders usually comprise the active ingredient mixed with low solids.

  quantities of a conditioning agent Natural clays

  absorbers such as attapulgite, or relatively nonabsorbent such as kaolinites, diatomaceous earth, synthetic fine silica, silicate-de

  calcium and other solid inert carriers of standard

  in herbicidal powder compositions can be used. The active ingredient usually represents

  a proportion of 0.5 to 90% of these powder compositions.

  Solids should ordinarily be very fine

  divided For the transformation of powders into powders

  for dusting, talc, pyrophyllic

lite etc '

  Liquid compositions containing the compositions

  The active ingredients described above can be prepared by

  mixture of the compound with a suitable liquid diluent medium.

  Representative examples of the usual liquid media

  The active ingredient ordinarily comprises about 0.5 to 50% of these liquid compositions. Some of these compositions are intended to be used as such and others are to be diluted. with large amounts of water.

  Compositions in the form of wettable powders

  lables or liquids may also contain one or

  several surfactants such as wetting agents

  dispersants or emulsifiers. Surfactants cause the dispersion or

  easy emulsification in water of the compositions of

  wettable liquids or liquids, by giving composi-

sprayable aqueous compositions.

  The surfactants used may be of the anionic, cationic or nonionic type. They include, for example, long chain sodium carboxylates, alkylaryl sulfonates, sodium lauryl sulphate, polyethylene oxides, lignosulfonates and others.

surfactants.

  In the case of use as a treatment in

  = pre-emergence, it is desirable to include a fertilizer,

  secticide, fungicide or other herbicide.

  The amount of active compound or composition that is administered varies with the plant part or growth medium of the plant to be affected in particular, the general location of application-that is, the areas protected areas such as greenhouses compared to open areas such as fields as well as

  the desired type of struggle In general, for the herbicidal

  in both pre-emergence and post-emergence, we apply

  of the invention at rates of 0.2 to 60 kg / ha, and the

  The recommended rate is in the range of 0.5 to 40 kg / ha.

  To obtain a regulating or retarding effect of growth

  of plants, it is essential to apply the

  at a lower concentration than for the destruction

  Therefore, application rates for regulatory or plant growth retarding effects are generally lower than rates used to kill plants.

  0.1 to 5 kg / ha and preferably 0.1 to 3 kg / ha.

  Herbicide tests on compounds

  representative of the invention have been made using

  the following methods Pre-emergence herbicidal test An acetone solution of the compound was prepared

  by mixing 500 mg of the compound, 158 mg of a

  non-ionic charge and 20 ml of acetone 20 ml of this solution was added to 80 ml of water to obtain the test solution.

  Seeds of the test vegetation were se-

* in a pot of earth and the test solution

  was applied uniformly by spraying

  27.5 pg / cm 2 The pot was watered and put in a greenhouse.

  intermittently, and the lifting of

  tules, the health status of the seedlings raised, etc.,

  At the end of this period, the herbicidal efficacy of the compound was assessed on the basis of physiological observations. A scale of 0 to 100 was used in which 0 represents the absence of phytotoxicity and 100 represents the total destruction The results of these tests are shown in Table I.

  In the continuation of the tests, the model was repeated

  above procedure using a diluted test solution which has been applied by surface spraying

  at various doses The results of these tests

appear in Table II.

Herbicide test post-emergence

  The test compound was formulated in the same way

  than for the pre-emergence test above.

  mulation was uniformly applied by spraying

  on two similar pots of 24-day old plants

  15 to 25 plants per pot) at a dose of 27.5 μg / cm

  Plants, once dry, have been placed in a

  intermittently, when this is done intermittently

  has been shown to be necessary Periodic plants have been observed

  only to detect phytotoxic effects and responses to

  physiological and morphological at treatment After three weeks, the herbicidal efficacy of the compound was evaluated on the basis of these observations. A scale of 0 to 100 was used in which O represents the absence of phytotoxicity and 100 represents a destruction. The results of these tests are shown in Table I. In the continuation of the tests, the above procedure was repeated using the diluted test solution which was applied by spraying on the soil surface to various doses The results of these tests stand out

of Table II.

TABLE A

Formula compounds

R NO R 1

\ C C) I Ol

QI OH

R R 3

2 3

  R and R each represent a methyl group, unless otherwise specified C y H N

  N O R R 1 - 'Cala Found CalTr Calc Tr.

  ## STR1 ## Oil 62.32 61.54 7.13 7.14 3.30 2.93

(R 2 = HR 3 = CHCH

3 O H

253 1953

TABLE I HERBICIDE ACTIVITY

  Percentage of pre / post inhibition <27.5 gig / cm 2?) M A D P F i 0/40

2 0/30

0/20 0/10 0/0 0/18

/ 100 100/100

/ 100 100/100

  / 100/100 C = Lamb's-quarters (Chenopodiumu album) M = Mustard of the fields <Brassica arvensis) A = Amaranth (Amnaranthus retroflexus) D = Digitaria (Digitaria sanguinalis) P = Panic-footed cock (Echinochloa crusgalli) F = Wild oats < Avenua f atua) No C

TABLE II HERBICIDE ACTIVITY

  Percent pre / post inhibition <rate in g g / cm 2) NO Soybean rate il 4, 4 1, 8 op 7 O, 28 1c 48Il il 0, .27

19 27, 5

27.1 5

22 27, 5

23 27, 5

24 27, 5

  2/0 0/0 0/0 0 / - 0/0 0/0 0/0 0/0 0/10 0/0 0/0 0/20 0/0 Rice 97/72 / 30 0/0 78 / 57/10 3/3 0/0 13/0 / 60 43/55 / 10 78/50 c 0/0 0/0 0/0 0/0 0/0 0/0 0/0/0/0/0/0/0 0/55 0/30 / 23 0/38/35 m 0/0 0/0 O / O 0/0 0/0 0/0 0/0/0/068 0/0 0/60 0/98 0/75 A 0/0 0/0 0/0 0/0 63/0 / 0 0/0 0 / O 0/30 0/0 0/23 0/28 0/23 D 57/0 0/0/0/0 0 / - / 25 0/3 0/0 0/0 / 23/65/25/10

P F

/ 100 48/100

63/95 15/68

/ 73 0/7

0/0 / -

/ 100 27/92

92/98 0/15

/ 95 0/0

0/32 0/0

93/58 35/10

/ 98 20/35

/ 98 35/0

/ 70 30/10

/ 28 100/95

ru tn w D

78/38 'W *

i'n Lw

TABLE II (CONTINUED)

No Soybean Rice Rate C M A D P F

  1 414 2/0 100/100 0 / O 0/0 0 / O 94/97 100/100 99/100

  1.8 0/0 100/100 0/0 0/0 0/0 95/90 100/100 96/100

  0.7 0/0 99/100 0 / O O / O 0/0 73/58 98/98 85/100

  0.28 0/0 73/82 0 / O 0/0 O / O 13/15 58/90 73/87

  2 4.4 5/0 98/100 O / O O / O 0 / O 93/75 100/100 99/100

  1.8 2/0 87/100 O / O O / O 0/0 33/58 100/100 92/100

  0.7 0/0 57/97 O / O O / O 0 / O 0/15 98/98 77/98

  0.28 0/0 0/62 0/0 0/0 0/0 0/0 10/92 62/82

  It goes without saying that the present invention has been described only as explanatory and non-limiting, and that many modifications can be made without

get out of his frame.

Claims (7)

  Compound according to the main patent, characterized in that it corresponds to the formula: R NO-R 1 C OR X \ 4 R 2 R 3   wherein R is the propyl group;   R 1 is a trans-3-chlorallyl or 4-chloro benzyl;   one of the groups R 1 and R 2 is hydrogen and the   is the 2-ethylthiopropyl group; R is hydrogen, 0 5   i, R is hydrogen, a cation or a group   -CR 6 in which R 6 is an alkyl radical having 1 to 6 atoms;   carbons, the phenyl radical or the naphthyl radical.   Compound according to Claim 1, characterized in that   in that R is the trans-3-chlorallyl group.   Compound according to one of Claims 1 and 2,   characterized in that R is hydrogen.   Compound according to Claim 3, characterized in that R 5 is a cation.   Compound according to claim 1, characterized   what R is the trans-3-chlorallyl group and R is the hydro-   gene 6 A herbicidal composition comprising a biologically inert carrier and an effective amount of the herbicidal product of a compound of the formula of claim 1.   7 Method for destroying vegetation, characteristics   in that it consists in applying to the said vegetation or to its growth medium a herbicidally effective amount of a compound of formula following the claim 1.   8 A method for destroying panic, panicoot or wild oats, characterized in that it consists in applying to these plants or their growth medium a herbicidally effective amount   of a compound of formula according to claim 1.   A method of destroying blood panic, characterized in that it comprises applying to the plant or its growth medium an effective amount of   herbicide of a compound of formula according to the 1.