FR2464946A1 - NOVEL THIOCARBAMOYL-GUANIDINES WITH HIGH HERBICIDE ACTIVITY, USE THEREOF AS HERBICIDES AND PROCESS FOR THEIR PREPARATION - Google Patents

Abstract

THE SUBJECT OF THE PRESENT INVENTION IS COMPOUNDS OF GENERAL FORMULAS: (CF DRAWING IN BOPI) IN THIS FORMULA: R IS A RADICAL PHENYL POSSIBLY SUBSTITUTED BY ONE OR MORE HALOGEN ATOMS, ONE OR MORE ALKYL OR HALOALKYL RADICALS CONTAINING FROM 1 TO 3 CARBON; R AND R, SAME OR DIFFERENT, ARE A RADICAL ALKYL OR ALCOXYL WITH 1 TO 3 ATOMS OF CARBON; OR ENCORER AND R, FORM BETWEEN THEM AN ALKYLIDENE CHAIN, INCLUDING 4 TO 5ATOMS OF CARBON, POSSIBLY INTERRUPTED BY A HETEROATOM. USE OF THESE COMPOUNDS AS HERBICIDES.

Description

NEW THIOCARBAMOYL-GUANIDINES CONTAINED

  OF HIGH HERBICIDE ACTIVITY, THEIR USE AS HERBICIDES

AND PROCESS FOR PREPARING THEM

  The subject of the present invention is novel compounds having an

  herbicide cation, and relates more particularly to new thio-

  carbamoyl guanidines with high herbicidal activity; it also relates to the use of these compounds as herbicides and to the process of

their preparation.

  Held, Gross and Schubert ["Zeitschrift der Chemie" 13, 341 (1973)] have described a process which, by oxidation of N, N-dimethyl-N'-phenylthiourea by thionyl chloride, has led to the production of N, N-dimethyl-N2, N3-diphenyl-N3- [N, N-dimethyl-thiocarbamoyl] -guanidine having the formula c6HS

C, 6H5

H3c-N N

I I

CH3 S = C-N (CH3) 2

  Srivastrava et al. [J. Ind. Chem Soc., 40, 803 (1963)] prepared unsubstituted thiocarbamoyl guanidine derivatives at the 1-position hydrogen atom and the thiocarbamoyl nitrogen atom. compounds that we

  obtained in the form of bromohydrates.

  The Applicant has found, and this forms the object of the present invention that thiocarbamoyl-guanidines of general formula (II) R N II (II) Ri -N N R

R2 / 'R2

R! R s R

2 - 2 2464946

  wherein: R is a phenyl radical optionally substituted with one or more halogen atoms, one or more alkyl or haloalkyl groups having 1 to 3 carbon atoms; R1 and R2, identical or different, consisting of alkyl radicals comprising 1 to 3 carbon atoms, or alkoxyls comprising 1 to 3

carbon atoms, or else

  R1 and R2 may form between them an alkylidene chain having 4 or 5 carbon atoms, optionally interrupted by heteroatoms; with the proviso that when in formula (II): R1 = R2 = CH3, R may be

substituted phenyl.

  The compounds of formulas (II), even in the case where in the formula (II): R1 = R2 = CH3, and R is an unsubstituted phenyl radical, are provided with a herbicidal activity that can be used against monocotyledons and dicotyledons; these compounds can be used as they are or in the form of a suitable composition, in the fight against the infesting species. The methods of controlling weeds, using the compounds of formulas (II) according to the present invention or compositions

  containing them, constitute another object of the present invention.

  The preparation of the compounds of formula (II), which forms another object of the present invention, can be obtained using the procedures

described below.

  The preparation of the compounds of general formula (II) is obtained by reaction of a disulfide or formamidine sulfide (I) with a catalytic amount of a strong anhydrous acid (reaction 4):

R R

N N

  He I 4) c. C R R R -N (S) N-R 1 -p-) I R 1 i) n C (I), n

R2 R2

  n being 1 or 2 Reaction 4 is preferably effected by adding a catalytic amount of an acid having sufficient strength to salify basic sulfide or disulfide groups of formula (I). to a solution of the latter

  in an aprotic polar solvent, such as for example chloroform (CHCl 3).

  As a strong acid, it is possible to use trihaloacetic acid or a

anhydrous hydrohalic acid.

  The reaction rate depends not only on the nature of the compound of formula (I) which is reacted but also on the amount of acid employed. For amounts of acid equal to 0.1 equivalent per mole of compound of formula (I), reaction 4 is completed at room temperature in a few minutes. When the reaction has occurred, the chloroform solution is washed with a saturated aqueous solution of sodium bicarbonate (NaHCO 3) and is made anhydrous. The solvent is then evaporated under vacuum so as to lead to a residue consisting of the corresponding compound.

  of formula (II). which can then be purified by crystallization.

  The process for preparing the compounds of general formula (II)

  is summarized in Figure 1, below.

  The compounds of formula (II) recorded in Table I,

  also below, were prepared using the method described above.

  The compounds of formula (I) are prepared using the process described in the first divisional application No. 13 13 155 of 13.6.1980. - _

SCHEME I

S / R

R-NH-C-

  R2b I (n = 2) oxidants (III) Cl oR '(III) + R-N = C-N tR R-2 I base

(C6H5) 3P

(n = 1) (n = 1) (IV) o (1) 0% ro 0% Q

TABLE I

R N

C-N-C-N-R '

/ Iut

/ I 1 I

R1-N R S R2

  R2 (1.) Elemental analysis% Formula crude Formula Compound R R1 R2 -b Formula nCompose R values NMR values (6, ppm) P.F (C) IR (cm 1) nO values

  calculated found (1) (2) (3) P.M.

  II 26 3,4-Cl2-C6H3 CH3 CH3 C 46.57 46.08 125-127 CeHeNSC14

E 3.88 3.76

N 12.08 11.81 463.8

  ## STR2 ##

695,326.47

N 17.15 17.20 2.53 (6H, s)

  II 28 4-CH3-C6H4-CH2-CH2-O-CH2-CH2-C 65.72 65.20 C24H30N4S 2

H 6.89 6.95 142-145

N 12.74 13.01 438.59

C26H34N4S

434.65

4-CH3-C6H4

-CH2- (CH2) 3-CH2-

C 71.85

H 7.88

N 12.89

68.98 7.68 12.82 Ln, 0%) 0% /. II

193-197

  TABLE I (cont'd) elemental analysis% Crude formula Compound 1R Formula Compound R RR2 RtN (6, ppm) P.F (0 C) IR (cm-1) _ no values

  calculated found (1) (2) (3) P.M.

  II 4-CH3-C6H4 'CH3 CH3 C 67.75 66.99 170.5-C20H26N4S

H 7.39 7.33 172.5

N 15.80 16.10 354.52

  II 31 4-Cl-C6H4 CH3 CH3 C 54.68 54.46 C1sH2oN4scl2

H 5.10 4.97 161-163

N 14.17 14.22 396.36

  II 32 4-Cl-C6H-CH2- (CH2) 3-CH2-C 60.62 60.62 C24H2NN4SCI2

H, 5.93, 5.99, 186-189

N 11.78 11.83 475.49

  4-Cl-C6H4-CH2-CH2-O-CH2-CH2-C 55.12 53.29 C22H24N4SO2Cl2

H 5.04 4.86 189-194

N 11.69 11.22 479.41

  II 34 3-CF3-C6H4-CH2-CH2-O-CH2-CH2-N 10.25 9.86 174-175 546.2

174-175,546.62

F 20.86 to 20.66

  3-CF3-C6H4 OH3 CH3 S 6.93 6.72 oil 462.45 /. r1o b. 0% J.- 9- 0% TABLE I (contd) elemental analysis Compound 2% - "1 Formula Formula Formula R Rt R2 NMR (6 ppm) PF (C) IR (cm) n0 values calculated values found (1 ) (2) (3) PM, II 36 3-CF3-C6H4-CH2 (-CH2) 3-CH2-S 5.91 5.59 142-146 542.58

  II 3,4-C12-C6H3-CH2-CH2-O-CH2-CH2-C 48.19 47.29 C22H22N4O2Cl4

H 4.04 3.96 153-155

N 10.21 9.99 548.32

  II 38 3,4-C12-C6H3-CH2- (CH2) 3-CH2-C 52.95 52.08 156-160 C24H26N4SCI

M 4.81 4.75

N 10.29 10.08 544.38

  0% J-P 01% 8 s 2464946 The compounds of general formula (II) are provided with a high herbicidal activity that is exerted against both monocotyledons

and dicotyledons.

  The data relating to the activity of representative compounds of the abovementioned compounds, obtained according to the method described in Example 2 =

  are shown in the Table, below.

  The herbicidal activity is determined for the following weeds: Monocotyledons

A = Echinochloa crusgalli.

B = Avena fatua.

C = Lolizun itaticeun.

D = Sorghumwn spp.

E = Setaria glauca.

F = Digitaria sanguinalis.

G = Alopecurus myosuroides.

H = Panicum dichotomiflorum.

I = Festuca pratense.

J = Bromus sterilis.

L = Poa annua.

dicotyledons

L = Stellaria media.

M = Ipomea purpurea.

N = Vigna sinensis.

O = Rumex acetosella.

P = Galinsoga parviflora.

Q = Convolvolus sepium.

R = Convolvolus ariensis.

S = Geraninum dissect.

T = Sida spinosa.

U = Brassica.

V = Gypsophila muralis.

W = Galium aparine.

  Herbicide activity data reported in Table II are expressed with respect to a range of values between 0 (no herbicidal activity, plant growth similar to that of the control)

  up to 4 (death of the plant or complete interruption of its growth).

TABLE III

  0% 4: N or Compound Dose Monocotyledons DicotyLedons (Table I) Treatment (Kg / ha) A [C D IE _ GIH I J K L _ N L R | IURI SI T | UV | W 26 Pre-emergence 6 2 4 4 4 4 4 4 4 4 Post-emergence 6 4 4 4 4 4 4 4 4 4 4 4 44 4 4 4 444 Pre-emergence 6 4 3 3 26 Post-emergence 2 4 4 3 4 4 4 4 4 4 4 4

1O 2464946

  Depending on the particular compound tested, the most effective herbicidal activity is obtained by pre-emergence or postemergence application, that is, when the weeds have not yet emerged from the soil,

or when they emerged.

  The herbicidal compounds according to the present invention have been found to have a selective action with respect to useful cultures such as wheat,

corn, soy and cotton.

  For agricultural applications, the active compounds are distributed on the soil as such, or preferably in the form of suitable compositions of one or more of the compounds of formula (II) acting as

  active ingredient, and one or more suitable supports.

  The compositions which may be used may be in the form of moisturizing powders, liquid pastes, granular formulations, etc. Suitable supports may consist, depending on the type of composition, silica, kaolin, diatomaceous earth, bentonite, pumice, organic solvents, water, etc. The composition may further contain additives such as surfactants, emulsifiers, thickeners, etc. A list of media and additives that can be used is

  indicated in the book "Mc Cutcheons - Detergent and Emulsifiers -

  North American and International Editions, 1977, Annual. Mc. Cutcheons Publ.

  Co., Glen Rock, New Jersey (U.S.A.) ".

  The preparation of said compositions is carried out according to the methods commonly used in the art. If desired, the compositions may further contain other active ingredients, such as fertilizers, insecticides or fungicides. The amount of active principle [Compounds of formula (II)] intended to be distributed on the soil, depends on various factors, such as the environmental conditions, the type of crop to be protected from infesting herbs, the type of composition and, in particular, the

active ingredient used.

  In general, the amounts of compounds of formulas (II) of between 1 and 6 kg / ha are perfectly suitable for obtaining good results in weed control, proportions in the order of

  2 to 3 kg / ha particularly suitable.

  Other advantages and features of the present invention are

  read the following description and examples given in

  illustrative but non-limiting title.

EXAMPLE 1

  Preparation of NIN1-dimethyl-N2, N3-diphenyl-N3 - [(N, N-dimethyl) thiocarbamoyl

  guanidine] (Compound No. 27, Table I). (Reaction 4).

  43 μl of trifluoroacetic acid are added to a solution of 2 g (5.58 moles) of Ni, N-dimethyl-N 2 -phenylformamidine disulfide, obtained according to the method described in Example 1, in a chloroform solution.

(200 ml).

  The reaction mixture is then kept at rest for 15 minutes,

  at room temperature, after which it is washed with a saturated solution

  of NaHCO3, then made anhydrous by treatment with anhydrous Na2SO4.

  After removal of the solvent by evaporation in vacuo, a residue is obtained which is recrystallized from n-hexane / benzene (70/30), which

  led to obtaining 1.3 g of the product in section (yield: 71%).

EXAMPLE 2

  * Determination of herbicidal activity.

  We prepare pots (upper diameter = 10 cm, height = 10 cm), containing a sandy soil, then plant in each pot one of the

  weeds mentioned above (Page 8).

  In each of the pots the amount of water necessary for a good humidification of the plants is added. The pots are divided into three groups: The first group is not treated with a herbicide and constitutes a

a group of witnesses.

  The second group is treated, one day after planting, with a

  hydroacetone persion (20% volume / volume) of the compounds according to this

  in order to determine the pre-emergence herbicidal activity.

  The third group is treated 15 days after planting (that is to say when the small plants have already reached a height of the order of 5 to cm, depending on the species), by a hydroacetonic dispersion (20% by volume / volume) of the compounds according to the present invention to determine

  herbicidal activity in the post-emergence state.

  All pots are kept under observation in a chamber whose temperature is kept between 15 and 24 C, the relative humidity is 70%,

  the photoperiod is 12 hours, and the luminous intensity is 2500 lux.

  Every two days, the pots are sprayed uniformly to ensure a sufficient humidification rate to

plant growth.

12 2464946

  28 days after treatment, tests are carried out to determine the condition of the plants, and are given a value according to the scale of values

  O (growth similar to that of control plants) and 4 (total

  ruption of growth, or complete destruction of plants).

  Of course, the present invention is not limited to the examples

  and modes of implementation mentioned above; it is likely to

  Many variants accessible to those skilled in the art, depending on the applications

  contemplated and without departing from the spirit of the invention.

13 2464946

Claims (10)

CLAIMS CATIONS   1.- As new industrial products, compounds of general formulas: R N Il C R1 - N N - C - N - R1 I I It 1I R2 R S R2 (II)   in which: R is a phenyl radical optionally substituted by one or more halogen atoms, one or more alkyl or haloalkyl radicals comprising 1 to 3 carbon atoms; R1 and R2, which may be identical or different, are an alkyl or alkoxyl radical containing 1 to 3 carbon atoms; or else R1 and R2 form between them an alkylidene chain comprising 4 to 5 atoms   of carbon, optionally interrupted by a heteroatom,   provided that when in formula (II): R1 = R2 = CH3, R is a substituted phenyl radical.   2.- Herbicidal Compounds Having the General Formula (II): RN C (II) R1 - N N - C - N - R I I I I R2 R S R2   wherein: R is a phenyl radical optionally substituted by one or more halogen atoms, one or more alkyl or haloalkyl radicals comprising 1 to 3 carbon atoms; R1 and R2, which may be identical or different, are an alkyl or alkoxyl radical comprising 1 to 3 carbon atoms; or alternatively, R1 and R2 form between them an alkylidene chain comprising 4 to 5 carbon atoms, optionally interrupted by a heteroatom, it being understood that, when in this formula: R1 = R2 = CH3, R is a substituted phenyl radical. 14 2464946   3. Compounds according to one of claims 1 or 2, characterized   in that: R1 and R2, which are identical or different, are alkyl radicals comprising 1 to 3 carbon atoms.   4. Compounds according to any one of claims 1 to 3, characterized in that:   R 1 and R 2 together form the group -CH 2 - (CH 2) 3 -CH 2 - or the group -CH 2 CH 2 -O-CH 2 -CH 2   5.- Method for controlling infestations of monocotyledons and di-   cotyledons, whether pre-emergence or post-emergence, characterized in   what is sprayed on the ground the compound according to any one of the   dications 1 to 4, used as is or in suitable compositions, in one   quantity of the order of 1 to 6 kg / ha.   6. A herbicidal composition according to any one of claims 1 to   4, characterized in that it contains as active ingredient one or more   siers of the compounds of general formula (II).   7. Process for the preparation of compounds according to any one of   Claims 1 to 4, characterized in that a trisubstituted thiourea of general formula (III): S R1 II R - NH - C - N R2 (III)   Wherein R, R 1 and R 2 are as defined above, is treated with an oxidant in the presence of a base and an inert solvent   (Reaction 1) to give compounds of general formula (I) in -   which n = 2, compounds which are treated with a triphenyl phosphine in diethyl ether at about 0 C (reaction 2) so as to lead to the compounds of general formula (I) in which n = 1, then, by treatment of compound of formula I in which n = 1 or 2 by a strong anhydrous acid in an aprotic polar solvent at room temperature (reaction 4), the compounds of formula (II) are obtained, these reactions being carried out according to the following reaction scheme: 1) R-N- -N oxidants R- = c () - = N- NKR - NH - S 'C - NR2   R1 (n = 2) R-N-R2 R2-N-R '(C6H5s) 3P2) I (n = 2) - I (n = 1) 4) I (n = 1 or 2) acid II 2464946.   8. A process according to claim 7, characterized in that the reaction i is carried out in the presence of bromine or iodine, acting as an oxidant. 9. A process according to claim 7 or 8, characterized in that reaction 4 is carried out in the presence of a strong anhydrous acid consisting of   trihaloacetic acid or halohydric acid.   10. A process according to any one of claims 7 to 9,   characterized in that in reactions 1 and 4 it is used as a solvent   methylene chloride (CH2Cl2) or chloroform (CHCl3).