BE801701A - HETEROCYCLIC COMPOUNDS - Google Patents

Description

       

  Heterocyclic compounds.

  
The present application relates to triazole compounds having herbicidal activity, to herbicidal compositions containing said compounds as active ingredients, and to the use of these compounds for controlling weeds.

  
In the U.S. patent n [deg.] 3,308,131, a general group of 1,2,4-triazoles corresponding to the general isomeric formulas has been described.

  

 <EMI ID = 1.1>


  
 <EMI ID = 2.1>

  
are aliphatic groups which together contain up to 14 carbon atoms and which can be joined together forming a heterocycle with the nitrogen atom of the carbamoyl, and R7 and R8, which together contain up to 14 carbon atoms, are free from aliphatic unsaturation and represent hydrogen, halogen, or sulfonyl, mercapto, cyano, hydrocarbyl, halohydrocarbyl, nitrohydrocarbyl, hydrocarbyloxycarbonylhydrocarbyle, hydrocarbylsulfonyl, hydrocarbylmercapto, nitrohydrocarbylmercapto, halohydrocarbocarbylmercapto, halohydrocarbocarbylmercapto, halohydrocarbocarbylmercapto. or hydrocarbyloxyhydrocarbyl. Compounds in this group are said to be effective insecticides, especially against mites and aphids. In addition, some of these compounds are said to have analgesic properties.

  
The Applicant has now discovered that a relatively narrow group of new 1,2,4-triazoles possess advantageous and valuable herbicidal properties, some of these compounds being included in the general group of 1,2,4-triazoles defined herein. -above. The new 1,2,4-triazoles are N, N-disubstituted 1-carbamoyl-1,2,4-triazoles with a sulfur function in position 3.

  
The present invention relates to compounds corresponding to the general formula

  

 <EMI ID = 3.1>


  
wherein R <3> is an alkylsulfonyl group containing from 1 to 5 carbon atoms, alkeny2 oxyalkylthio containing from 4 to 6 carbon atoms, alkoxyalkylsulfinyl containing from 2 to 6 carbon atoms, alkoxyalkylsulfonyl containing from 2 to 6 carbon atoms, haloalkylsulfinyl containing from 2 to 5 carbon atoms or haloalkylsulfonyl containing from 1 to 5 carbon atoms, R is an alkyl group containing from 2 to 6 carbon atoms, allyl, 2-methylallyl, alkoxy alkyl containing from 2 to 6 carbon atoms , alkenyloxyalkyl containing 4 to 6 carbon atoms, haloalkyl

  
 <EMI ID = 4.1> <EMI ID = 5.1>

  
alkyl containing 2 or 3 carbon atoms, 2,3-dihaloallyl or cyclopropyl, with the proviso that when R <2> is cyclopropyl R and R <3> can have any of the aforementioned meanings or that when R2 is not cyclopropyl at least one of the groups R, R <2> and R <3> contains an alkoxy substituent or one or two halogenated substituents.

  
It is preferable that any alkoxy or halo substituent in an alkoxyalkyl or haloalkyl radical is attached at a position other than the alpha position, i.e., is attached to a carbon atom other than that

  
which is attached to the nitrogen atom of the carbamoyl group

  
 <EMI ID = 6.1>

  
CONR R or the sulfur atom of the group R. In this case, when R <3> is an alkoxyalkylsulfinyl or alkoxyalkylsulphonyl group, it contains 3 to 6 carbon atoms, when R <3> is a haloalkylsulfonyl group it contains 2 to 5 carbon atoms, when R <3> is a group al-

  
 <EMI ID = 7.1>

  
when R is an alkoxyalkyl group it contains 3

  
with 6 carbon atoms, when R is an alkenyloxyalkyl group it contains 5 or 6 carbon atoms, and when

  
 <EMI ID = 8.1>

  
methylallyl) oxyalkyl.

  
The term "halo" embraces chloro, bromo, fluoro radicals and is preferably chloro or bromo, particularly chloro. The term "alkoxy" embraces alkoxy radicals of 1, 2, 3 or 4 carbon atoms, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy and isobutoxy.

  
The alkyl, alkenyl, alkoxyalkyl or halogalkyl radical in the group R <3> may have a straight or branched chain and is preferably a primary or secondary radical. The alkoxyalkyl radical in R- 'may contain 2, 3, 4, 5 or 6 carbon atoms and may be, for example, a 2-methoxyethyl, 2-ethoxyethyl, 2propoxyethyl, 2-n-butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 2-methoxypropyl or 2-ethoxypropyl. The haloalkyl radical in R <3> may contain 2, 3, 4 or 5 carbon atoms and may be, for example, a 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3bromopropyl, 4-chlorobutyl radical , 4-bromobutyl or 5-chloropentyl.

  
R <3> can be, for example, a 2-methoxy- radical

  
 <EMI ID = 9.1>

  
3-ethoxypropylsulfinyl, 2-methoxypropylsulfinyl, 2ethoxypropylsulfinyl, 2-chloroethylsulfinyl, 2-chloroethylsulfonyl, 2-bromoethylsulfinyl, 2-bromoethylsul-

  
 <EMI ID = 10.1>

  
allylsulfinyl, 2,3-dichloroallylsulfonyl, 2-allyloxyethylthio and 3-allyloxypropylthio.

  
 <EMI ID = 11.1>

  
butylaulfonyl, isobutylsulfonyl, sec.-butylsulfonyl, 2-methoxyethylsulfonyl, 2-ethoxyethylsulfonyl, 2-propoxyethylsulfonyl, 2-n-butoxy-ethylsulfonyl, 3-methoxypropylsulfonyl, 3-ethoxypropylsulfonyl, 2-ethoxypropylsulfonyl,

  
 <EMI ID = 12.1>

  
Particularly suitable groups are alkylsulfonyl groups containing 2 to 4 carbon atoms and alkoxyalkylsulfonyl containing 3 to 5 carbon atoms.

  
The radicals R <1> and R2 can be radicals with a linear or branched chain, and are preferably primary or secondary radicals. R may for example be an ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, n-pentyl, isopentyl, allyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-n- radical. drank-

  
 <EMI ID = 13.1>

  
ethyl, 3-allyloxypropyl, 2-methoxypropyl, 2-ethoxypropyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, 5chloropentyl, 6-chlorohexyl, 2- chloroallyl, 2-bromo-

  
 <EMI ID = 14.1>

  
be, for example, an ethyl, propyl, isopropyl, allyl, 2-methylallyl, prop-2-ynyl, 2-methoxyethyl, 2-

  
 <EMI ID = 15.1>

  
The carbamoyl radical -CONR <1> R <2> can be for example a dialkoylcarbamoyl radical in which the alkyl radicals are identical or different (for example diethylcarbamoyl, dipropylcarbamoyl, N-ethyl-N-propylcarbamoyl, N-butyl-N-ethylcarbamoyl , N-ethyl-N-hexylcar-

  
 <EMI ID = 16.1> butylcarbamoyl), diallylcarbamoyl, N-propyl-N-prop-2ynylcarbamoyl, N-allyl-N-alcoylcarbamoyl in which the alkyl radical contains from 2 to 6 carbon atoms

  
 <EMI ID = 17.1>

  
allyl-N- (2-methoxyethyl) carbamoyl, N-allyl-N- (2-ethoxyethyl) carbamoyl and N-allyl-N- (2-chloroethyl) carbamoyl, N-alkyl-N-methoxymethylcarbamoyl in which the alkyl radical contains from 2 to 6 carbon atoms / for example

  
 <EMI ID = 18.1>

  
methoxyethyl) carbamoyl in which the alkyl radical contains from 2 to 6 carbon atoms / for example N-ethyl-

  
 <EMI ID = 19.1>

  
carbamoyl in which the alkyl radical contains 2

  
with 6 carbon atoms, N-alkyl-N- (2-propoxyethyl) carbamoyl in which the alkyl radical contains 2 or 3 carbon atoms, N-alkyl-N- (2-isopropoxyethyl) carbamoyl in which the alkyl radical contains 2 or 3 carbon atoms

  
 <EMI ID = 20.1> alkyl contains 2-6 carbon atoms and N-alkyl-N-
(2-chloroethyl) carbamoyl in which the alkyl radical contains from 2 to 6 carbon atoms.

  
When the compound of formula (I) contains an alkoxy substituent R <3> is suitably an alkylsulfonyl radical containing from 2 to 4 carbon atoms or alkoxyalkylsulfonyl containing from 3 to 5 carbon atoms. The CONR 1 R <2> carbamoyl group is suitably a dialkoylcarbamoyl, N-alkyl-N-allylcarbamoyl, diallylcarbamoyl, N-alkyl-N-propylcarbamoyl, N-alkyl-Nalcoxyalkylcarbamoyl-N-alkylcarbamoyl-N-alkylcarbamoyl group.

  
Preferred compounds of formula (I) having one or more alkoxy substituents are those in which:
(a) R <3> is alkylsulfonyl, the alkyl group contains 2, 3 or 4 carbon atoms, and the carbamoyl group

  
 <EMI ID = 21.1>

  
or N-allyl-N-alkoxyalkylcarbamoyl, the alkyl group containing 2, 3 or 4 carbon atoms and the alkoxyalkl groups containing 3 or 4 carbon atoms, particularly

  
 <EMI ID = 22.1>
(b) R <3> is alkylalkylsulfonyl. the alkoxyalkyl group containing 3 to 5 carbon atoms, particularly 2methoxyethyl, 3-methoxypropyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, and the carbamoyl group CONR R is a diallylcarbamoyl, N-alkyl-N-allyl group. carbamoyl, N-alkyl-N-propynylcarbamoyl or dialkoylcarbamoyl, the alkyl groups containing 2, 3 or 4 carbon atoms.

  
When the compound of formula (I) contains

  
a halogen atom, a preferred group of compounds is a group in which R <3> is alkylsulfonyl containing 2 or 3 carbon atoms or alkoxyalkylsulfonyl containing 3 to 5 carbon atoms. It is preferable that the group

  
 <EMI ID = 23.1>

  
 <EMI ID = 24.1>

  
carbon atoms and the halogen atom is a chlorine atom.

  
 <EMI ID = 25.1>

  
of preferred compounds is a group in which R <3> is an alkylsulfonyl radical containing from 2 to 4 carbon atoms,

  
 <EMI ID = 26.1>

  
It is preferable that the carbamoyl group CONR <1> R <2> is an N-cyclopropyl-N-alkylcarbamoyl group in which the alkyl group contains 2, 3 or 4 carbon atoms.

  
The addition is also aimed at compounds corresponding to the general formula:

  

 <EMI ID = 27.1>


  
in which R <1> is an alkyl radical containing 1 or 2 carbon atoms, allyl, 2-methylallyl, prop-2-ynyl, alkoxyalkyl containing from 2 to 4 carbon atoms, haloalkyl containing from 1 to 4 carbon atoms, 2-haloallyl,

  
 <EMI ID = 28.1>

  
containing 2 to 8 carbon atoms, alkenyl containing

  
 <EMI ID = 29.1>

  
with 8 carbon atoms (for example allyloxyalkyl or (2methylallyl) oxyalkyl), haloalkyl containing from 2 to 8 carbon atoms, 2-haloallyl, 2,3-dihaloallyl, cyclopropyl or cyclohexyl, R <3> is an alkyl radical containing from 1 to 4 carbon atoms, allyl, 2-methylallyl, prop2-ynyl, alkoxyalkyl containing 2 to 4 carbon atoms, haloalkyl containing 1 to 4 carbon atoms, 2-haloallyl, 2,3-dihaloallyl, cyclopropyl or phenyl containing from 1 to 3 halogenated substituents, R4 is an alkyl radical containing from 1 to 8 carbon atoms, alkenyl containing from 2 to 8 carbon atoms, alkoxyalkyl containing from 2 to 8 carbon atoms, alkenyloxyalkyl containing from 4 to 8 carbon atoms carbon (for example allyloxyalkyl or (2-methylallyl) oxyalkyl, haloalkyl containing from 1 to 8 carbon atoms, 2-haloallyl, 2,3-dihaloallyl, cyclopropyl,

   or cyclohexyl, or R and R, together and with the nitrogen atom to which they are attached, form a heterocyclic ring, optionally containing from 1 to 4 lower alkyl substituents (preferably methyl), chosen from morpholino and pyrrolidino groups , 1-piperidyl, hexamethyleneimino and heptamethyleneimino, provided that the total number of carbon atoms in R and R <2> taken together is between 3 and 9, and when R <3> is a radical not containing a ring phenyl, the total number of atoms of

  
 <EMI ID = 30.1>

  
be 2 and 9.

  
Preferably, an alkoxy, alkenyloxy or halo substituent in an alkoxyalkyl, alkenyloxyalkyl or haloalkyl radical is attached at a position other than the alpha position, i.e. is attached to a carbon atom other than that which is attached on the nitrogen atom of the carbamoyl group -CONR <1> R <2> or the nitrogen atom of the sulfamoyl group
-S02NR3R4, In these cases, when R4 is an alkoxy alkyl radical, it contains from 3 to 8 carbon atoms, when <EMI ID = 31.1>

  
 <EMI ID = 32.1>

  
haloalkyl it contains from 2 to 8 carbon atoms.

  
By "halo" is meant to include chloro, bromo and

  
 <EMI ID = 33.1>

  
chloro. By "alkoxy" is meant to include alkoxy radicals containing 1, 2, 3 or 4 carbon atoms, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy and isobutoxy. The term “lower” is intended to denote an alkyl radical containing

  
from 1 to 3 carbon atoms, preferably methyl. "Alkenyloxyalkyl" preferably represents an allyloxyalkyl group, for example allyloxyethyl or 3-allyloxypropyl. Preferred alkenyl groups for R <2> and R4 are allyl and 2-methylallyl.

  
The R and R2 radicals can be radicals

  
linear or branched chain.

  
R can be, for example, a methyl, ethyl, allyl, 2-methylallyl, prop-2-ynyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, chloromethyl, 2-chloroethyl, 2-bromoethyl, 2 radical. -fluoroethyl, 3chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, 2-chloroallyl, 2-bromoallyl, 2,3-dichloroallyl, 2,3-dibromoallyl and cyclopropyl.

  
R2 can be, for example, an ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, n- radical.

  
 <EMI ID = 34.1>

  
2-methylallyl, 2-allyloxyethyl, 3-allyloxypropyl, 2chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, 5-chloropentyl, 6-chlorohexyl, 2-chloroallyl, 2-bromoallyl, 2,3-dichloroallyl, 2,3-dibromoallyl, cyclopropyl and cyclohexyl.

  
The carbamoyl group -CONR <1> R <2> can be, in particular-. ment, a dialkylcarbamoyl group / for example N-methylN-ethylcarbamoyl, diethylcarbamoyl, N-ethyl-N-propylcarbamoyl, N-ethyl-N-isopropylcarbamoyl, N-butyl-N-

  
 <EMI ID = 35.1>

  
carbamoyl in which the alkyl radical contains from 1 to

  
 <EMI ID = 36.1>

  
N-allyl-N-ethylcarbamoyl, N-allyl-N-propylcarbamoyl,

  
 <EMI ID = 37.1>

  
carbamoyl, N-allyl-N- (2-chloroethyl) carbamoyl, N-alkylN- (2-methcxyethyl) carbamoyl or N-alkyl-N- (2-ethoxyethyl) carbamoyl in which the alkyl radical contains from 2 to 6 atoms of carbon / for example N-ethyl-N- (2-methoxyethyl) -

  
 <EMI ID = 38.1>

  
N- (2-ethoxyethyl) carbamoyl and N-propyl-N- (2-ethoxyethyl) carbamoyl &#65533; 7, N-methyl-N-cyclohexylcarbamoyl, N-propyl-Nprop-2-ynyl, N-alkyl-N- (2-chloroallyl) carbamoyl in which the alkyl radical contains from 2 to 6 carbon atoms and N-alkyl-N- (2,3-dichloroallyl) carbamoyl in which the alkyl radical contains from 2 to 6 carbon atoms, Ncyclopropyl- N-propylcarbamoyl and N-cyclopropyl-N-ethylcarbamoyl.

  
 <EMI ID = 39.1>

  
linear or branched chain.

  
R <3> can be, for example, a methyl radical,

  
 <EMI ID = 40.1>

  
butyl, allyl, 2-methylallyl, prop-2-ynyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, .3-methoxypropyl, chloromethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, 2-chloroallyl, 2-bromoallyl, 2.3-dichloroallyl, 2,3dibromoallyl, cyclopropyl, 4-chlorophenyl, 4-bromophenyl and 4-fluorophenyl.

  
R can be, for example, a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.

  
 <EMI ID = 41.1>

  
tyl, allyl, 2-methylallyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-n-butoxyethyl,

  
 <EMI ID = 42.1>

  
ethoxypropyl, 2-n-butoxyethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3-bromopropyl,

  
 <EMI ID = 43.1>

  
ethyl and 3-allyloxypropyl.

  
As previously indicated, when the group

  
 <EMI ID = 44.1>

  
1 to 4 lower alkyl substituents (preferably methyl). These alkyl substituted heterocyclic groups can be, for example, 2,6-dimethylmorpholino, 4-methyl-1-piperidyl, 2-methyl-1-piperidyl and 2,6dimethyl-1-piperidyl groups.

  
As representative examples of the sulfamoyl group -SO2NR <3> R4, there may be mentioned the dimethylsul-famoyl, dipropylsulfamoyl, di-n-butylsulfamoyl, diallylsulfamoyl, d: L- (2-methylallyl) sulfamoyl, N-lower alkyl-N- groups. cyclohexylsulfamoyl (for example N-methylN-cyclohexylsulfamoyl), N-allyl-N-alkylsulfamoyl in which the alkyl radical contains from 1 to 5 carbon atoms (for example N-allyl-N-methylsulfamoyl, N-allylN-ethylsulfamoyl and N-allylN-ethylsulfamoyl allyl-N-propylsulfamoyl), N-methyl-N-alkylsulfamoyl in which the alkyl radical contains from 1 to 8 carbon atoms (for example N-methyl-

  
 <EMI ID = 45.1>

  
N-methyl-N- (4-fluorophenyl) -sulfamoyl, morpholinosulfonyl, 1-pyrrolidinylsulfonyl, 1-piperidylsulfonyl, hexamethylene-

  
 <EMI ID = 46.1>

  
 <EMI ID = 47.1>

  
carbon atoms or an allyl, 2-methylallyl, prop2-ynyl, or alkoxyalkyl group containing 2 to 4 carbon atoms.

  
 <EMI ID = 48.1>

  
carbon, allyl or 2-methylallyl. It is preferable that the carbamoyl group CONR 1 R <2> is a dialkoylcarbamoyl group, in which the alkyl groups are the same or different and together contain 3 to 6 carbon atoms, diallylcarbamoyl, N-allyl-N-alkylcarbamoyl in which the alkyl group contains 1 to 4 carbon atoms, or Nalkoxyalkoxyalkylcarbamoyl in which the alkyl group contains 2 to 4 carbon atoms and the alkoxyalkl group contains 3 or 4 carbon atoms.

  
R <3> is preferably an alkyl group containing 1 to 4 carbon atoms, allyl, 2-methylallyl, alkoxyalkyl containing 3 or 4 carbon atoms, phenyl containing

  
 <EMI ID = 49.1>

  
containing 1 to 8 carbon atoms, allyl, methylallyl or alkoxyalkyl containing 3 to 8 carbon atoms. It is preferable that the sulfamoyl group is a dialkylsulfamoyl group in which the alkyl groups are the same or different and each contain 1 to 4 carbon atoms, diallylsulfamoyl, di- (2-methylallyl) sulfamoyl or

  
 <EMI ID = 50.1>

  
contains 1 to 4 carbon atoms.

  
As particularly suitable compounds of formula (II), mention will be made of those in which:
(a) the carbamoyl group is a diallylcarbamoyl group and the sulfamoyl group is a dialkoylsulfamoyl group, <EMI ID = 51.1>
(b) the carbamoyl group is a dialkylcarbamoyl group and the sulfamoyl group is a dialkoylsulfamoyl, diallylsulfamoyl or N-allyl-N-alkylsulfamoyl group,
(c) the carbamoyl group is an N-allyl-N-alkylcar- <EMI ID = 52.1> group

  
famoyl, diallylsulfamoyl or N-allyl-N-alcoylsulfamoyl,
(c) the carbamoyl group is an N-alkyl-N-alkoxyalkylcarbamoyl group and the sulfamoyl group is a dialkylsulfamoyl, diallylsulfamoyl or N-allyl-N-alkylsulfamoyl group.

  
A subject of the present invention is also herbicidal compositions which contain, as active ingredient, a compound corresponding to general formula (I) or (II) in association with a diluent or a vehicle. The diluent or vehicle may be a solid or a liquid, optionally in combination with a surfactant, for example a dispersing agent, an emulsifying agent or a wetting agent.

  
The present invention also relates to a method of controlling, before their emergence, against weeds of the grass family which consists in applying to the place occupied by weeds, for example the soil, a compound corresponding to the general formula (I ) or (II). This process is aimed in particular at the selective control, before their emergence, against weeds of the grass family such as Echinochloa crusgalli ("barnyard

  
 <EMI ID = 53.1>

  
("crabgrass" hereinafter referred to as CG for short), Setaria lutescens ("yellow foxtail" foxtail hereinafter referred to as YF for short), Sorghum halepense (Aleppo sorghum, "Johnson Grass", hereinafter referred to as abbreviated JG) or Alopecurus myosuroides (blackgrass, "blackgrass"), in a cultivation zone, consisting in applying to the cultivation zone a compound corresponding to general formula (I) or (II), at a rate sufficient for fight against weeds but

  
practically non-phytotoxic to the crop.

  
The Applicant has discovered that the triazole compounds of formula (I) and (II) have valuable herbicidal properties against weeds of the grass family. For example, the compounds have a very high herbicidal activity exerted before the emergence of the weeds (hereinafter referred to as pre-emergence herbicidal activity) against the following grasses: CG, BG, YF and JG.

  
In addition, very careful greenhouse trials have shown that the compounds provide pre-emergence control against each of these weeds, at application rates that do not cause significant phytotoxic effects on crops. cotton, soybeans, peanuts and corn when the compounds are applied before the emergence of these crops. Accordingly, the compounds according to the invention can be used for the selective pre-emergence control of all these weeds in these crops. This constitutes an important advantage,

  
because CG, BG, YF and JG are all important weeds of cotton, soybean, peanut and

  
corn and are often present at the same time in these cultures. Of these four crops, the particularly preferable crops are cotton, soybeans and peanuts. Many compounds according to the invention can also be used for the pre-emergence control against weeds of the grass family, for example Alopecurus myosuroides in wheat and barley crops.

  
The compositions according to the invention comprise a triazole compound of formula (I) or (II) and not only comprise compositions in a form suitable for

  
Concentrates not only application but also primary compositions can be provided to the user and should be diluted with an appropriate amount of water or other diluent before application.

  
As representative examples of compositions according to the invention, there will be mentioned: (a) Dispersions and dispersible preparations

  
In the form of dispersions, the compositions essentially contain a triazole compound according to the invention dispersed in an aqueous medium. The consumer should be provided with a primary composition which can be diluted with water to obtain a dispersion having the desired concentration; the primary composition can be in any of the following forms. It can be supplied as a dispersible solution comprising

  
a compound according to the invention dissolved in a solvent miscible with water, with the addition of a dispersing agent. It can also be supplied in the form of a dispersible powder which comprises a compound according to the invention and

  
a dispersing agent. It can also be supplied in the form of a finely ground powder in association with a dispersing agent and be intimately mixed with water to obtain a paste or a cream. This paste or cream can optionally be added to an oil-in-oil emulsion. water to obtain a dispersion of the active ingredient in an aqueous oily emulsion.

  
(b) Emulsions and emulsifiable preparations

  
The emulsions essentially comprise a triazole compound according to the invention dissolved in a solvent immiscible with water, which is put in the form of an aqueous emulsion in the presence of an emulsifying agent. An emulsion having the desired concentration can be obtained from a primary composition of the following types. A stock concentrate emulsion can be provided, comprising a compound according to the invention in combination with an emulsifying agent, water and a solvent immiscible with water.

  
It is also possible to provide an emulsifiable concentrate comprising a solution of a compound according to the invention in a water-immiscible solvent containing an emulsifying agent.

  
(c) Sprinkle powders

  
A dusting powder comprises a triazole compound according to the invention, intimately mixed and ground with a solid pulverulent diluent, for example kaolin.

  
 <EMI ID = 54.1>

  
They can comprise a compound according to the invention combined with diluents similar to those which can be used in sprinkling powders, but. the mixture is converted into granules by known methods. They can also include the active ingredient absorbed or adsorbed onto a pre-formed granular diluent, for example fuller's earth, attapulgite and calcareous sand.

  
In addition to the aforementioned ingredients, the compositions according to the invention may also contain other substances conventionally used in the art, which may have the function of improving the ease of handling of the compositions or of improving their utility. For example, an inert diluent such as kaolin can be included in

  
dispersible powders in order to facilitate grinding and to provide sufficient mass to mix with water.

  
Compositions intended to be diluted with water before application may also contain a wetting agent in order to rapidly wet the products and ensure satisfactory soil coverage. Likewise, when preparing sprinkle powders, a lubricant such as magnesium stearate can be added to the mixture, in order to facilitate mixing of the components and to ensure that a free-flowing final product is obtained.

  
The compositions described above, in which the active ingredients are present in solid form, for example sprinkling powders and dispersible powders, should preferably contain the compound according to the invention in the form of very fine particles; the majority of the particles, on the order of 95% at least, should preferably be less than 50 microns, about 75% of the particles having? dimensions between 5 and 20 microns. The adjuvants conventionally used in these compositions generally have these particle sizes, or smaller sizes. The compositions can be prepared using conventional grinding devices, for example using a hammer mill.

  
The concentration of the compound according to the invention, in the primary compositions which can be supplied for the preparation of any of the forms in which the compositions according to the invention can be used, is very variable and can represent, for example,

  
from 2 to 95% w / w of the composition. It goes without saying that this concentration is influenced by the nature of the primary composition and the physical properties of its ingredients.

  
The concentration of the compound according to the invention in the compositions to be applied for controlling weeds should preferably be at least 0.001% w / w and particularly between 0.05 and 10% w / w.

  
In addition to a compound according to the invention, the compositions according to the invention may contain one or more additional active ingredients, for example one or more additional insecticides, nematocides or herbicides. The additional herbicide can be, for example, a substituted urea (eg, Diuron or Monouron); a triazine

  
(eg Simazine or Atrazine), a substituted acetanilide
(eg Propachlor); a nitrophenyl ether (eg Nitrofen), a carbamate (eg Chlor &#65533;propham); or a thiolcarbamate (eg ethyl N, N-di-n-propyl thiolcarbamate) or a triallate.

  
The present invention also relates to a method of pre-emergence control against weeds.

  
of the grass family, consisting of applying to the place occupied by weeds, for example the soil,

  
a compound corresponding to general formula (I) or (II). This method is particularly aimed at the selective pre-emergence control of weeds of the grass family, for example Echinochloa crusgalli, Di &#65533; itaria

  
 <EMI ID = 55.1>

  
Alopecurus myosuroides, in a growing area, consisting

  
in applying to the cultivation area a compound according to the invention at a rate sufficient to fight against weeds but substantially non-phytotoxic to the cultivation. This process can be used after the crop has emerged, for example for the pre-emergence control of weeds of the grass family such as Echino-. chloa crusgalli in seeded or transplanted rice, but generally used before crop emergence, as is usually the case for family weed control grasses in cotton, soybeans, peanuts, wheat, corn and barley.

   When the method is used before the emergence of the crop, the compounds according to the invention should be applied to the soil in which the crop is sown, at the time of sowing or just before. Thus, for example, the compounds according to the invention can be incorporated

  
to the top layer of the soil, as part of the operating protocol for sowing.

  
For controlling weeds of the grass family, the compounds according to the invention are generally used at an application rate of 0.056 to 56 kg / ha, preferably 0.112 to 22.4 kg / ha.

  
Selective pre-emergence weed control can be accomplished, in many cases, at an application rate of 0.112 to 11.2 kg / ha.

  
The selective activity on weeds, before their emergence, of the compounds according to the invention is demonstrated by the results obtained in meticulous tests carried out in a greenhouse. In these trials, soil trays are sown with seeds of various weeds

  
and various crops, and then immediately sprayed with aqueous suspensions of the test compounds, at application rates of the test compound decreasing logarithmically from 8.96 to 0.035 kg / ha. Trays of

  
bare seeded soil receiving no chemical treatment are used as controls. The weeds used are CG, BG, YF and JG. The crops used are cotton (CO), soybean (SB), maize (M) and peanuts (r).

  
With regard to weeds, the minimum application rate is recorded at which positive results in weed control are obtained, as shown by the plants that have emerged and

  
whose growth is seriously and irreparably arrested. Regarding crops, we record the

  
minimum application rate at which phytotoxic effect is observed on emerging plants. In some cases,

  
no phytotoxic effect is observed on a crop at the maximum application rate of the compound under test

  
 <EMI ID = 56.1>

  
The results obtained with various compounds according to the invention are reported in Tables I and II below. Only a selection of compounds have been shown in these tables, but testing of the properties of many other compounds meeting the

  
 <EMI ID = 57.1>

  
are representative of the compounds corresponding to these formulas. In Tables I and II, the following abbreviations are used: Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl,

  
 <EMI ID = 58.1>

  
Alkyl radicals without the designation i- or s- are normal radicals.

TABLE I

  

 <EMI ID = 59.1>
 

  
 <EMI ID = 60.1>
 <EMI ID = 61.1>
  <EMI ID = 62.1>

  
TABLE 1 (continued)
 <EMI ID = 63.1>
 -

  
 <EMI ID = 64.1>
 <EMI ID = 65.1>
  <EMI ID = 66.1>
 <EMI ID = 67.1>
 TABLE II (continued) <EMI ID = 68.1>

  

 <EMI ID = 69.1>
 

  
The Applicant has discovered that the compounds according to the invention exhibit herbicidal properties superior to those of various related 1,2,4-triazoles coming within the general scope of the compounds described in the U.S. patent. n [deg.] 3,308,131 supra, including a representative selection of the compounds particularly exemplified in this patent.

  
By way of comparison, various 1,2,4-triazoles used in the greenhouse tests described above are combined.

  
 <EMI ID = 70.1>

  
compounds according to the invention, using application rates decreasing logarithmically from
35.84 kg / ha (32 x 1.12 kg / ha). The results obtained are reported in Tables III and IV below in which "x" denotes a compound particularly exemplified in the U.S. patent. n [deg.] 3,308,131. Compounds ineffective in controlling CG, BG, YF and JG at the maximum application rate of 35.84 kg / ha are shown in Table IV. Due to their lack of activity against weeds, these compounds are not included in the crop tests. Among the compounds appearing in Table IV, those of which

  
believes that they were obtained as a mixture of isomers (corresponding to formulas A) containing significantly more than 10% of each isomer, or those in which the isomeric structure is uncertain, are designated 1 (2) - in the nomenclature of the carbamoyl group. It is believed that the other compounds are obtained substantially as the indicated isomer, or mainly as this isomer, with less than 10% of the other isomer.

TABLE III

  

 <EMI ID = 71.1>

TABLE IV.

  
Compounds having the following substituents on: the 1,2,4-triazole ring are ineffective in combating. weeds at a rate of 35.84 kg / ha (32 x 1.12 kg / ha)

  
 <EMI ID = 72.1>

  
 <EMI ID = 73.1>

  
 <EMI ID = 74.1>

  
1 (2) -diethylthiocarbamoyl-3-ethylthio

  
 <EMI ID = 75.1>

  
 <EMI ID = 76.1>

  
 <EMI ID = 77.1>

  
 <EMI ID = 78.1>

  
1-dimethylcarbamoyl-3-n-hexylthio

  
1-dimethylcarbamoyl-3-cyclohexylthio

  
1-dimethylcarbamoyl-3-dodecylthio

  
 <EMI ID = 79.1>

  
1-dimethylcarbamoyl-3-benzyl

  
 <EMI ID = 80.1>

  
 <EMI ID = 81.1>

  
ï <EMI ID = 82.1>

  
 <EMI ID = 83.1>

  
 <EMI ID = 84.1>

  
 <EMI ID = 85.1>

  
 <EMI ID = 86.1>

  
 <EMI ID = 87.1>

  
 <EMI ID = 88.1>

  
1-piperidinocarbonyl-3-ethylthio

  
 <EMI ID = 89.1>

  
1-diallylcarbamoyl

  
1 (2) -diallylcarbamoyl-3-ethylthio-5-methyl 1-toiallylcarbamoyl-3- (2-diethylaminoethylthio)

  
 <EMI ID = 90.1>

  
1-di (cyanomethyl) carbamoyl-3-ethylthio

  
The results reported above show that the compounds shown in Tables I and II are significantly superior to the compounds shown in Tables III and IV in terms of their high degree of selective pre-emergence activity against CG, BG, YF and JG in cotton, soybean, peanut and corn crops, especially cotton, soybean and peanut crops.

  
It can be seen from the above that the compounds according to the invention are valuable for the control, before their emergence, against weeds of the grass family in various crops, for example in cotton crops, legumes such as soybeans and peanuts, and grains such as corn. However, we can see

  
that, considered in isolation, the compounds according to the present invention are not all equivalent from the point of view of their characteristics of activity and herbicidal selectivity. Accordingly, the optimum compound for one particular use is not necessarily the optimum compound for another particular use.

  
Insecticidal and miticidal tests were carried out with various compounds according to the present invention. Compounds tested were found to have little or no activity against insects, e.g. Plutella maculipennis, Phaedon cochleariae, and aphids such as Aphis

  
fabae and Megoura viciae. Compounds tested were also found to have little or no activity against mites, for example Tetranychus urticae.

  
As regards the toxicity to mammals of the compounds according to the present invention, the studies

  
of acute oral toxicity in mice have given satisfactory results. During these studies, the compounds according to the invention have proved to be less toxic than certain very similar 1,2,4-triazoles, for example 1-dimethylcarbamoyl3-methylthio-1,2,4-triazole.

  
Preparation of compounds of formula (I)

  
The compounds of formula (I) can be prepared by the methods described below which are analogous to known methods for the preparation of similar compounds.

  
One of these methods consists in reacting a triazole of general formula:

  

 <EMI ID = 91.1>


  
in which R <3> is as defined for formula I, on a carbamoyl halide corresponding to the general formula Z-CONR <1> R <2> (IV) in which R <1> and R <2> have the meaning defined for formula (I) and Z is chlorine, fluorine

  
or bromine, preferably chlorine. The reaction should be carried out in the presence of an inert organic liquid as the reaction medium, which is preferably a solvent for the reactants. It is preferable to operate at a temperature

  
 <EMI ID = 92.1>

  
advantageously the reaction in the presence of a suitable acid binding agent, for example a tertiary amine such as triethylamine or pyridine, in order to absorb the hydrogen halide produced by the reaction. According to another procedure, it is possible to convert the triazole corresponding to the general formula (III) into one of its alkali metal salts (for example sodium), before the reaction with the carbamoyl halide. The alkali metal salt can be obtained by reacting the triazole of the general formula (III) with an alkali metal hydride, amide or alcoholate, according to known methods.

  
The carbamoyl halides of the general formula (X) can be prepared by reacting a

  
 <EMI ID = 93.1>

  
secondary amine corresponding to the general formula HNR R, in which R <1> and R2 are as defined with regard to formula (I), with a carbonyl halide COZ2, according to known methods.

  
1

  
 <EMI ID = 94.1>

  
r

  
 <EMI ID = 95.1>

  
carbamoyl genide corresponding to the general formula:

  

 <EMI ID = 96.1>


  
in which R <3> and Z have the meanings defined with regard to formula (I), with a secondary amine corresponding to

  
 <EMI ID = 97.1>

  
are as defined with reference to formula (I). The reaction should be carried out in the presence of an inert organic liquid as the reaction medium, which is preferably a solvent for the reactants. It is preferable to operate at a temperature of -20 to 100 [deg.] C, for example 0 to 40 [deg.] C. The reaction is advantageously carried out in the presence of a suitable acid binding agent, for example a tertiary amine such as triethylamine or pyridine.

  
The carbamoyl halides of formula (V) can be prepared from the triazoles of formula (III), by reaction with a carbonyl halide COZ2, preferably phosgene, according to known methods.

  
The triazoles corresponding to the general formula (III) can be prepared by alkylation or alkenylation of 3-mercapto-1,2,4-triazole (for example by reaction of 3-

  
 <EMI ID = 98.1>

  
is chloro or bromo) followed by oxidation of the 3-thio group, where appropriate, by known methods.

  
It is also possible to prepare the compounds of formula
(I) by a process consisting in reacting a carbonylbistriazole corresponding to the general formula:

  

 <EMI ID = 99.1>


  
where R <3> is as defined in connection with the formula
(I), on a secondary amine corresponding to the general formula HNR R in which R and R <2> are as defined in

  
 <EMI ID = 100.1>

  
tion in the presence of an inert organic liquid as reaction medium which is preferably a solvent for the reactants. It is best to operate at a temperature of -20

  
at 100 [deg.] C, for example 0 to 40 [deg.] C.

  
The carbonylbistriazoles corresponding to the general formula (VI) can be prepared by reacting a triazole corresponding to the general formula (III) defined above with approximately 0.5 molecular proportion of a halide of

  
 <EMI ID = 101.1>

  
known ceded. It is preferable to carry out the reaction in the presence of a suitable acid binding agent, for example pyridine. After obtaining carbonylbistriazole, it is often advisable to react it, without isolating it, with the amine corresponding to the general formula HNR R.

  
It is understood by those skilled in the art that the triazoles represented by the general formula (III) are tautomeric and that, for reasons of convenience, the general formula (III) represents the structure of a tautomer.

  
 <EMI ID = 102.1>

  
 <EMI ID = 103.1>

  
alkylsulfonyl, alkoxyalkylsulfonyl or haloalkylsulfonyl can also be prepared by a process consisting of oxidizing a compound of the general formula:

  

 <EMI ID = 104.1>


  
in which R is an alkyl, alkoxyalkyl or

  
 <EMI ID = 105.1>

  
About formula (I), according to known methods. The oxidation can be carried out, for example, by reaction with hydrogen peroxide or peracetic acid.

  
With the exception of the compounds in which R <3> is a methylsulfonyl group, the intermediate triazoles corresponding to the general formula (III) are new compounds.

  
It will be understood by those skilled in the art that the acylation reactions described above in connection with the preparations of the compounds of formula (I) can theoretically provide two isomeric products, one (hereinafter referred to as "isomer-1 ") corresponding to the general formula
(I) and the other (hereinafter referred to as "2-isomer") corresponding to the general formula:

  

 <EMI ID = 106.1>


  
It is believed that the solid compounds of formula (I), after purification by standard methods (for example

  
 <EMI ID = 107.1>

  
of formula (I), as isolated by p: common processes
(for example by vacuum distillation), are obtained in the form of constituents of an isomeric mixture containing mainly the isomer-1 as well as a minor proportion, generally less than about 10%, of isomer 2. Preparation of compounds of formula (II)

  
The compounds of formula (II) can be prepared by the methods described below, which are analogous to known methods for the preparation of similar compounds.

  
One of these processes consists of reacting a sulfamoyltriazole corresponding to the general formula:

  

 <EMI ID = 108.1>


  
 <EMI ID = 109.1>

  
formula (II), on a carbamoyl halide of formula

  
 <EMI ID = 110.1>

  
with regard to formula (II) and Z represents chlorine, fluorine or bromine, preferably chlorine. The reaction should be carried out in the presence of an inert organic liquid as the reaction medium, which is preferably a solvent for the reactants. It is preferable to operate at

  
 <EMI ID = 111.1>

  
Advantageously, the reaction is carried out in the presence of a suitable acid binding agent, for example a tertiary amine such as triethylamine or pyridine, in order to absorb the hydrogen halide produced by the reaction. According to another procedure, the triazole corresponding to the general formula (VIII) can be converted into one of its alkali metal salts (for example sodium) before reacting with the carbamoyl halide. The fry metal salt can be obtained by reacting the triazole of formula (VIII) with an alkali metal hydride, amide or alcoholate, according to known methods.

  
The carbamoyl halides corresponding to the general formula (IX) can be prepared by reacting a secondary amine corresponding to the general formula HNR R,

  
 <EMI ID = 112.1>

  
known.

  
It is also possible to prepare the compounds of formula
(II) by a process of reacting a halide

  
 <EMI ID = 113.1>

  

 <EMI ID = 114.1>


  
 <EMI ID = 115.1>

  
 <EMI ID = 116.1>

  
as defined with regard to formula (II). The reaction should be carried out in the presence of an inert organic liquid as the reaction medium, which is preferably a solvent for the reactants. It is preferable to operate at a temperature of -20 to 100 [deg.] C, for example 0 to 40 [deg.] C. The reaction is advantageously carried out in the presence of a suitable acid binding agent, for example a tertiary amine such as triethyl amine or pyridine.

  
The carbamoyl halides of formula (X) can be prepared from the triazoles corresponding to the general formula (VIII), by reaction with a carbonyl halide COZ2, preferably phosgene, according to known methods.

  
The sulfamoyltriazoles corresponding to the general formula (VIII) (with the exception of NR <3> R4 = dimethylamino or 1-piperidyl) are new compounds. The compounds can be prepared by a process of reacting a

  
 <EMI ID = 117.1>

  
chloride, on an amine corresponding to the general formula NHR <3> R4 (XI). The reaction can be carried out in an aqueous medium, or in a suitable inert organic liquid, which is preferably a solvent for the reactants. Diethyl ether

  
of liquids

  
that and tetrahydrofuran are suitable inert organic examples which in many cases are solvents for the reactants. It is preferable to carry out the reaction in the presence of an acid binding agent, for example triethylamine or an excess of the amine HNR <3> R4, in order to absorb the hydrogen halide produced by the reaction. . The reaction should be carried out at a temperature of 10 to 30 [deg.] C.

  
The compounds according to the present invention can also be prepared by a process comprising:

  
 <EMI ID = 118.1>

  
rale:

  

 <EMI ID = 119.1>


  
 <EMI ID = 120.1>

  
formula (II), on a secondary amine corresponding to the form

  
 <EMI ID = 121.1>

  
defined with reference to formula (II), The reaction should be carried out in the presence of an inert organic liquid as

  
 <EMI ID = 122.1>

  
The carbonylbistriazoles corresponding to the general formula (XII) can be prepared by reacting a triazole corresponding to the aforementioned general formula (VIII), with approximately 0.5 molecular proportion of a halide of

  
 <EMI ID = 123.1>

  
known ceded. It is preferable to carry out the reaction in the presence of a suitable acid binding agent, for example pyridine. After obtaining carbonylbistriazole, it is often necessary to react it, without isolating, with the amine corresponding to the general formula HNR <1> R <2>.

  
It will be understood by those skilled in the art that the triazoles represented by the general formula (VIII) are tautomeric and that, for the sake of convenience, the general formula (VIII) represents the structure of a tautomer.

  
mother. It goes without saying for those skilled in the art that the acylation reactions described above in connection with the preparation of the compounds of formula (II) can theoretically give two isomeric products, one (hereinafter referred to as "isomer 1"). corresponding to the general formula (II) and the other (hereinafter referred to as "isomer 2") corresponding to the general formula:

  

 <EMI ID = 124.1>


  
It is believed that the solid compounds of formula (II), after purification by conventional methods (eg by crystallization), are obtained as substantially pure isomer 1. It is believed that the liquid compounds of formula (II), as isolated by common methods

  
(for example by vacuum distillation) are obtained in the form of constituents of an isomeric mixture mainly consisting of isomer 1 accompanied by a minor proportion, generally less than approximately 10%, of isomer 2.

  
In the examples below, the following abbreviations are used: Me = methyl, Et = ethyl, Pr - propyl, Bu = butyl, Pen = pentyl, Hex = hexyl, i = iso and s = secondary. Alkyl radicals without the designation i- or s- are normal radicals.

  
In the compounds shown in the tables, the physical constant is: for a solid compound, its melting point; for an oil, the refractive index of the compound since a boiling point cannot be measured in this case and, when possible, an analysis value by CGL
(gas-liquid chromatography) (%) is shown in parentheses after the refractive index, to give an indication of the purity of the oil. For a liquid compound, the physical constant is the boiling point at the indicated pressure (mm of Hg).

  
The following nonlimiting examples are given

  
by way of illustration of the invention.

  
EXAMPLE 1.

  
This example illustrates the preparation of compounds

  
of formula (I).

  
A solution of 4.1 g of 3- (2-ethoxyethylsulfonyl) -1,2,4-triazole, 3.5 g of diallylcarbamoyl chloride and 4 ml of triethylamine in 40 ml of dry tetrahydrofuran is heated at reflux for 15 hours, in the middle <EMI ID = 125.1>

  
separate the triethylamine hydrochloride and evaporate

  
the filtrate to remove the solvent. The residue is triturated with petroleum ether (bp 40-60 [deg.] C), thus obtaining a solid product. This product is collected and recrystallized from an ether / petroleum ether mixture (eb.
40-60 [deg.] C), thus obtaining 1-diallylcarbamoyl-3- (2ethoxyethylsulfonyl) -1,2,4-triazole, m.p. 62-63 [deg.] C. Elemental analysis is satisfactory.

  
The novel intermediate triazole compounds used in the preparation below are prepared as follows.

  
 <EMI ID = 126.1>

  
of absolute ethanol, 52.2 g of 1,2,4-triazole-3-thiol are added. 84 g of 1-bromo-2ethoxyethane are added to the solution thus obtained and the solution thus obtained is heated under reflux for 3 hours. The cooled reaction mixture is filtered, the filtrate is evaporated under reduced pressure in order to remove the solvent and the residue is dissolved in ether. The solution thus obtained is filtered, the filtrate is evaporated in order to remove the solvent and the residue is distilled off under reduced pressure, thus obtaining 3- (2-ethoxyethylthio) 1,2,4-triazole, eb. 137-145 [deg.] C / 0.3-0.5 mm. Elemental analysis is satisfactory.

  
Hydrogen peroxide (33.6 ml of 100 volume solution) is added in small portions at a time to

  
 <EMI ID = 127.1>

  
azole in 150 ml of crystallizable acetic acid, maintaining the temperature of the reaction mixture at a value of
80 to 85 [deg.] C. Once the addition of the hydrogen peroxide is complete, the temperature of the reaction mixture is maintained at a value of 80 to 85 [deg.] C for a further 2 hours. The reaction mixture is distilled under reduced pressure in order to remove the acetic acid and the solid residue obtained is crystallized from an ethyl acetate / petroleum ether mixture (bp 40-60 [deg.] C), thus obtaining the 3- (2 - ethoxyethyl-

  
 <EMI ID = 128.1>

  
The following compounds are prepared in a similar manner.

  

 <EMI ID = 129.1>
 

  

 <EMI ID = 130.1>
 

  

 <EMI ID = 131.1>


  
Satisfactory elemental analyzes are obtained for all of the above compounds.

EXAMPLE 2.

  
This example illustrates the preparation of compounds of formula (I).

  
Maintained a solution of 5.67 g of 3-isobutylsulfonyl-1,2,4-triazole, 5.46 g of N-ethyl-N- chloride.
(2-methoxyethyl) carbamoyl, 6 ml of triethylamine and 40 ml of dry tetrahydrofuran at room temperature (20 [deg.] C) for 72 hours. The mixture is filtered in order to remove the triethylamine hydrochloride and the filtrate is evaporated, thus obtaining a residual oil. This oil was washed with petroleum ether (bp 40-60 [deg.] C) (3 x 100 ml), then dissolved in ether. The ethereal solution is filtered in order to remove a trace of insoluble substance and the filtrate is evaporated, thus obtaining a residual oil which is maintained at 100 [deg.] C under vacuum, for 2 hours, in order to remove all traces.

  
 <EMI ID = 132.1>

  
The new intermediate compound used in the preparation described above is prepared as follows. N-ethyl-N-2-methoxyethylamine, eb. 115-116 [deg.] C by reacting 3 molecular proportions of ethylamine

  
 <EMI ID = 133.1>

  
in 500 ml of dry ether at -20 [deg.] C is added a solution of
30.9 g of N-ethyl-N-2-methoxyethylamine in 50 ml of dry ether, while maintaining the temperature of the reaction mixture

  
 <EMI ID = 134.1>

  
room erases, in one hour. The reaction mixture is filtered, evaporated in vacuo below 25 [deg.] C in order to remove the solvent and to obtain the product, N- (2methoxyethyl) -N-ethylcarbamoyl chloride, in the form of d. 'a pale yellow liquid.

  
The following compounds are prepared in a similar manner:

  

 <EMI ID = 135.1>
 

  

 <EMI ID = 136.1>
 

  

 <EMI ID = 137.1>
 

  

 <EMI ID = 138.1>


  
Satisfactory elemental analyzes are obtained for all of the above compounds.

EXAMPLE 3.

  
This example illustrates the preparation of compounds of formula (I).

  
A solution of 0.03 mole of 3-prcpylsulfonyl-1,2,4-triazole, 10 ml of triethylamine, 0.03 mole is heated.

  
of N-propyl-N- (2-chloroallyl) carbamoyl chloride in 40 ml of dry tetrahydrofuran, to relux, for 15 hours. The mixture is then cooled and the triethylamine hydrochloride is filtered off. After removing the solvent, the product is dissolved in methylene chloride and the solution washed with water. The product is recrystallized from an ether /

  
 <EMI ID = 139.1>

  
m.p. 51.5-52 [deg.] C. Elemental analysis is satisfactory.

  
The new carbamoyl chloride used in the above reaction is prepared as follows:

  
80 g of sodium hydroxide pellets are dissolved in 350 ml of water, with stirring, in a two-liter flask. The solution is cooled and 295 g of propylamine are added. The temperature is adjusted to 40 [deg.] C and maintained at this value while adding 222 g of 2,3-dichloropropene, over about two hours. There is a release of heat. After stirring for a further two hours at 40 [deg.] C, the mixture is gradually brought to reflux on a steam bath. It is gently heated under reflux for two hours, then left to stand for 15 hours at room temperature. We

  
 <EMI ID = 140.1>

  
folds balls. After cooling, the upper amine layer is separated and passed, with stirring, through a cooled solution of concentrated hydrochloric acid in water.

  
The aqueous layer was extracted with ether and the extract was stirred for 10 minutes with the hydrochloric acid solution. The ether is separated, which is discarded, and the aqueous solution is evaporated in vacuo on the steam bath. Add water, cool the solution on ice and

  
 <EMI ID = 141.1>

  
amine layer, dried over successive amounts of sodium hydroxide pellets and distilled, on an oil bath, using a column filled with beads. The pro-

  
 <EMI ID = 142.1>

  
250 ml of ethyl acetate are stirred and heated to reflux, while passing a brisk stream of phosgene. A solution of 0.25 moles of N- (2-chloroallyl) propylamine in 75 ml of ethyl acetate is then added, dropwise, over approximately 4.5 hours. After passing phosgene for a further fifteen minutes, ethyl acetate was removed in vacuo and the product was distilled off in vacuo, thereby obtaining N-propyl-N- (2-chloroallyl) carbamoyl chloride, b. 97-99 [deg.] C / 17 mm.

  
The triazole intermediate used for the preparation is prepared as follows:

  
20.2 g of 3-mercapto-1,2,4-triazole are added

  
to a solution of 4.8 g of sodium in 150 ml of absolute ethanol. When the dissolution is complete, 24.6 g of propyl bromide are added. While stirring, the mixture is gradually heated to boiling under reflux, heated under reflux for one hour, cooled to room temperature and filtered. The filtrate is distilled to dryness under reduced pressure and the residue is dissolved in ether. The solution thus obtained is filtered, dried over anhydrous sodium sulfate and distilled under reduced pressure, thus obtaining 3-propylthio-1,2,4-triazole, bp. 143-144 [deg.] C / 1 mm. This product solidifies, m.p. 53-56 [deg.] C.

  
To a solution of 14.3 g of 3-propylthio-1,2,4triazole in 100 ml of crystallizable acetic acid, is added 28.5 ml of hydrogen peroxide solution at 100 volumes (2.5 molecular proportions) . The solution is gradually heated to a temperature of 95 to 100 [deg.] C, it is maintained at this temperature for 2 hours, then distilled to dryness under reduced pressure. The residue is recrystallized from toluene, thereby obtaining 3-propylsulfonyl-1,2,4triazole, m.p. 116-117 [deg.] C. Elemental analysis is satisfactory.

  
The following compounds are prepared in a similar manner:

  

 <EMI ID = 143.1>
 

  

 <EMI ID = 144.1>


  
Satisfactory elemental analyzes are obtained for all of the above compounds.

  
EXAMPLE 4.

  
This example illustrates the preparation of a compound of formula (I).

  
A solution of 7.5 g of 1-dipropylcarbamoyl-3-butyl-sulfinyl-1,2,4-triazole and 4 ml of dry pyridine in 15 ml of methylene chloride on ice is cooled, and stirred while slowly adding a solution of

  
2 ml of sulfuryl chloride in 10 ml of methylene chloride. Stirring is continued on an ice bath for one hour, then the mixture is stirred at room temperature for a further hour. The solution is washed quickly with ice water, dried over magnesium sulfate and the solvent is removed in vacuo. The product, 1-dlpropylcarbamoyl-3- (1-chlorobutylsulfinyl) -1,2,4triazole is a viscous gum which does not crystallize, even when cooled in a solid carbon dioxide / acetone mixture. Elemental analysis is satisfactory.

  
EXAMPLE 5.

  
This example illustrates the preparation of compounds of formula I.

  
A solution of 0.03 mole of 3-propylsulfonyl-1,2,4-triazole, 6 ml of triethylamine and 0.033 mole of N-ethyl-N-cyclopropylcarbamoyl chloride in 40 ml of dry tetrahydrofuran is heated at reflux for 5 hours. The cooled reaction mixture is filtered in order to remove the triethylamine hydrochloride and the filtrate is evaporated in order to remove the solvent. An ethereal solution of the liquid product is treated on charcoal, the ether is evaporated off and the residue is heated to 120 [deg.] C, under high vacuum, in order to distill the purified product, the 1- (N-ethyl -N-cyclopropylcar-

  
 <EMI ID = 145.1>

  
of isomer 1 by CGL). Elemental analysis is satisfactory.

  
The new carbamoyl chloride used in the above reaction is prepared as follows:

  
We. first prepare the new N-ethyl-

  
 <EMI ID = 146.1>

  
75 ml of absolute ethanol and cooled to below 20 [deg.] C while adding 19.8 g of acetaldehyde over 15 minutes. The solution is added to 75 ml of absolute ethanol in which 0.3 g of platinum oxide has been reduced at room temperature and pressien. The solution is added and hydrogen likewise, and the theoretical quantity of hydrogen is absorbed in about 5 hours. After separation of the catalyst by decantation, the solution is strongly acidified by adding 50 ml of concentrated hydrochloric acid and evaporated under vacuum on a steam bath. The residue is dissolved in 70 ml of water and the amine is released by adding 50 ml of 18.5N sodium hydroxide.

  
The amine layer is separated and dried over

  
successive quantities of sodium hydroxide pellets. Distilled in barium oxide, thus obtaining a liquid product, eb. 82-85 [deg.] C.

  
250 ml of ethyl acetate are stirred and heated to reflux, while passing a brisk stream of phosgene. After about 10 minutes, a solution of

  
21.95 g of cyclopropylamine in 75 ml of ethyl acetate, dropwise, below the surface of the liquid, over 2.5 hours. Fifteen minutes later, the ethyl acetate is distilled off and the residual oil is distilled off in vacuo, bp. 96 [deg.] C /

  
17 mm.

  
The following compounds are prepared in a similar manner.

  

 <EMI ID = 147.1>
 

  
EXAMPLE 6.

  
This example illustrates the preparation of a compound of formula (I) by another process, via a triazole carbamoyl chloride.

  
A mixture of 19.1 g of 3- (2-methoxyethylsulfonyl) -1,2,4-triazole and 8.25 ml of dry pyridine in 100 ml of dry tetrahydrofuran is added dropwise with stirring to a solution. of 10 g of phosgene in 100 ml of dry tetrahydrofuran, keeping the temperature below

  
 <EMI ID = 148.1>

  
mixture of ice and water. After the addition is complete, the mixture is stirred for a further 30 minutes.

  
The pyridine hydrochloride precipitate is quickly filtered off and the filtrate is stirred and cooled, in anhydrous medium, while adding a solution of 10.1 g of dipropylamine and 8.25 ml of dry pyridine in 50 ml of dry tetrahydrofuran, drop by drop, at a temperature below 20 [deg.] C. Once the addition is complete, we shake

  
mix again for 30 minutes.

  
The pyridine hydrochloride precipitate is filtered off and the solvent is removed from the filtrate by vacuum distillation, thereby obtaining a residue which is then dissolved.

  
in methylene chloride and washed with sodium hydroxide N / 2 in water, and finally with hydrochloric acid N / 2 (75 ml

  
of each). Methylene chloride is removed under reduced pressure, thus obtaining a solid which, by crystallization from a benzene / petroleum mixture (40-60 [deg.] C) gives the pure product, 1-dipropylcarbamoyl-3- (2-methoxyethylsulfonyl ) -1,2,4 triazole, mp 76-78 [deg.] C.

  
EXAMPLE 7.

  
This example will illustrate the preparation of a compound of formula (I) by another process, using a carbamoylbistriazole as an intermediate.

  
A solution of 19.1 g of 3- (2methoxyethylsulfonyl) -1,2,4-triazole and 8.25 ml of dry pyridine in 100 ml of dry tetrahydrofuran is added, dropwise, with stirring, in anhydrous medium, to a solution of 5 g of phosgene in 100 ml of tetrahydrofuran. We keep the tem-

  
 <EMI ID = 149.1>

  
chilling on a mixture of ice and water. Precipitation takes place immediately and the mixture is stirred for a further 30 minutes after the addition is complete. Then the precipitate of pyridine hydrochloride is quickly filtered.

  
A solution of 7 ml of dipropylamine in 50 ml of dry tetrahydrofuran is then added, dropwise, with stirring, to the filtrate prepared above, in anhydrous medium, while maintaining the temperature below 20 [deg.] C. during the addition. An exothermic reaction is observed and the mixture is stirred for a further 30 minutes after the addition is complete.

  
The solvent is then removed from the mixture by

  
 <EMI ID = 150.1>

  
methylene chloride. This solution is then washed with three portions of 75 ml of N / 2 sodium hydroxide solution, with 75 ml of water and finally with 75 ml of N / 2 hydrochloric acid. The solvent is removed, thus obtaining a sol product: .de which, by crystallization from a benzene / petroleum mixture; 40-60 [deg.] C) gives the pure product, 1-dipropylcarbamoyl-3- (2-me- thoxysulfonyl) -1,2,4-triazole, mp 75-78 [deg.] C.

  
EXAMPLE 8.

  
This example illustrates the preparation of a composition comprising a compound of formula (I).

  
A dispersible powder is prepared by grinding together a mixture of the following ingredients in a hammer mill.

  

 <EMI ID = 151.1>


  
Similar dispersible powders are prepared in which the triazole compound of the above composition is replaced by the following compounds:

  
1-diallylcarbamoyl-3- (2-methoxyethylsulfonyl) -1,2,4triazole,

  
 <EMI ID = 152.1>

  
triazole.

EXAMPLE 9.

  
This example illustrates the preparation of a composition comprising a compound of formula (I),

  
An emulsifiable concentrate was prepared to be diluted with water to obtain an aqueous emulsion, from the following ingredients:

  

 <EMI ID = 153.1>
 

  
 <EMI ID = 154.1>

  
 <EMI ID = 155.1>

  
nonylphenol.

  
Similar emulsifiable concentrates were prepared in which the triazole compound of the above composition was replaced by the following compounds: 1- (N-ethylN-2-ethoxyethylcarbamoyl) -3-n-butylsulfonyl-1,2,4- triazole,

  
1- (N-ethyl-N-2-ethoxyethylcarbamoyl) -3-isobutylsulfonyl1,2,4-triazole, 1- (N-propyl-N-2-methoxyethylcarbamoyl) -3n-butylsulfonyl-1,2,4- triazole.

  
EXAMPLE 10. This example illustrates the use, as herbicide, of a composition comprising a compound corresponding to formula (I).

  
In tests carried out in a greenhouse, we

  
 <EMI ID = 156.1>

  
The herbs are then sprayed immediately with aqueous suspensions of test compounds, applying the compounds at various application rates. We use as t-

  
less seeded soil trays not undergoing chemical treatment. At an application rate of 0.56 kg / ha,

  
 <EMI ID = 157.1>

  
to fight effectively against CG, BG, YF and JG (no germination, or emergence of seedlings whose growth is seriously and irreparably stopped).

  
EXAMPLE 11. This example illustrates the preparation of a compound

  
posed of formula (II).

  
A mixture of 6.9 g of 3-diallyl-sulfamoyl-1,2,4-triazole, 4.5 g of diethylcarbamoyl chloride, is heated,

  
i 6 ml of triethylamine and 25 ml of dry tetrahydrofuran, at reflux, in anhydrous medium, for 1.5 hours. The cooled reaction mixture is filtered in order to remove the triethylamine hydrochloride and the filtrate is evaporated in order to remove the solvent. The solid residue is recrystallized from petroleum ether (bp 60-80 [deg.] C), thereby obtaining 1-diethylcarbamoyl3-diallylsulfamoyl-1,2,4-triazole, m.p. 49-51 [deg.] C. Elemental analysis is satisfactory.

  
The novel 3-diallylsulfamoyl-1,2,4triazole intermediate is prepared as follows. A stream of chlorine is passed through a solution of 20.2 g of 1.2,4 triazole-3-thiol in 330 ml of 2N hydrochloric acid, while maintaining the temperature of the mixture at a temperature of

  
0 to -2 [deg.] C, cooling externally. When there is presence of an excess of chlorine (after 1.5 hours) the solid product is collected by filtration, washed with water and filtered off so as to obtain a product which is as dry as possible. In this way 1,2,4-triazole-3-sulfonyl chloride is obtained in the form of a wet solid which is used immediately for the next stage of the preparation. This wet solid is gradually added, with stirring, to a solution of 48.5 g of diallylamine in 100 ml of water, while maintaining the temperature of the reaction mixture at 20 [deg.] C. The reaction mixture was allowed to stand at 20 ° C. for 20 minutes, then acidified to pH 4.0 with concentrated hydrochloric acid.

   The resulting solid product was collected by filtration, washed with water and recrystallized from water, thereby obtaining 3-diallylsulfamoyl-1,2,4-triazole, m.p. 131-133 [deg.] C. Elemental analysis is satisfactory.

  
EXAMPLE 12.

  
This example illustrates the preparation of compounds of formula (II).

  
By reacting the appropriate carbamoyl chloride with the appropriate 3-sulfamoyl-1,2,4-triazole, in a manner analogous to that described in Example 11, the following compounds are prepared:

  

 <EMI ID = 158.1>
 

  

 <EMI ID = 159.1>


  
Satisfactory elemental analyzes are obtained for all of the above compounds.

EXAMPLE 13.

  
This example illustrates the preparation of compounds of formula (II).

  
By reacting the appropriate carbamoyl chloride with the appropriate 3-sulfamoyl-1,2,4-triazole, in a manner analogous to that described in Example 11, the following compounds are prepared:

  

 <EMI ID = 160.1>
 

  

 <EMI ID = 161.1>
 

  

 <EMI ID = 162.1>
 

  

 <EMI ID = 163.1>
 

  

 <EMI ID = 164.1>
 

  

 <EMI ID = 165.1>
 

  

 <EMI ID = 166.1>


  
Satisfactory elemental analyzes are obtained for all the abovementioned compounds.

  
EXAMPLE 14.

  
This example illustrates the preparation of compounds of formula (II).

  
Maintaining a solution of 0.03 mol of 3-diallylsulfamoyl-1,2,4-triazole, 8 ml of triethylamine and

  
0.03 mole of N-ethyl-N-2-methoxyethylcarbamoyl chloride

  
in 40 ml of dry tetrahydrofuran at room temperature for 3 days. The amine hydrochloride is filtered off and the solvent is removed by evaporation. 100 ml of petroleum ether are added to the mixture and the petroleum ether is decanted from the liquid layer formed. It is then dissolved in ether, filtered and the solvent is removed by evaporation on a bath of

  
 <EMI ID = 167.1>

  
100 [deg.] C under vacuum for 3 hours, at a pressure of less than 0.2 mm, in order to remove all traces of carbamoyl chloride. The compound, which is an oily liquid, has an index

  
 <EMI ID = 168.1>

  
presence of 96.1% of isomer 1. Elemental analysis is satisfactory.

  
The 3 - allylsulfamoyl-1,2,4-triazole intermediate used in the above preparation is prepared as in Example 11.

  
The carbamoyl chloride used as reagent is prepared as follows:

  
N-ethyl-N-2methoxyethylamine, eb. 115-116 [deg.] C, by reacting 3 molecular proportions of ethylamine on 1 molecular proportion.

  
 <EMI ID = 169.1>

  
1 equivalent of sodium hydroxide, at a temperature of 30 to
50 [deg.] C.

  
Add, while stirring, to a solution of
89.1 g of phosgene in 500 ml of dry ether at -20 [deg.] C, a solution of 30.9 g of N-ethyl-N-2-methoxyethylamine in 50 ml of dry ether, while maintaining the temperature of the reaction mixture to -20 [deg.] C. While stirring, the mixture is allowed to reach room temperature over one hour. The reaction mixture is filtered and the filtrate is evaporated in vacuo at a temperature below 25 [deg.] C, in order to remove the solvent and to obtain the product, N- (2-methoxyethyl) -Nethylcarbamoyl chloride, as a pale yellow liquid.

  
The following compounds are prepared in a similar manner:

  

 <EMI ID = 170.1>


  
Satisfactory elemental analyzes are obtained for all of the above compounds.

  
EXAMPLE 15.

  
This example illustrates the preparation of a compound of formula (II) by another process, using a triazole carbamoyl chloride as an intermediate.

  
A solution of 10.8 g of 3-piperidinosulfonyl-1,2,4-triazole and 7 ml of triethylamine in 100 ml of dry tetrahydrofuran is added dropwise with stirring to a solution of 5 g of phosgene in 100 ml of tetrahydrofuran dry, while maintaining the temperature at

  
 <EMI ID = 171.1>

  
using a mixture of ice and water. A precipitate formed immediately and the mixture was stirred for a further 30 minutes after the addition was complete. The precipitate of triethylamine hydrochloride is filtered off.

  
Is added to the filtrate prepared above, a solution of 6 g of N-propyl-N-2-methoxyethylamine in

  
50 ml of dry tetrahydrofuran as well as 7 ml of triethylamine, dropwise, with cooling and stirring, while maintaining the temperature below 20 [deg.] C. A precipitate forms immediately, and the mixture is stirred for a further
30 minutes after the end of the addition.

  
The triethylamine hydrochloride precipitate is separated by filtration and the solvent is separated from the filtrate by vacuum distillation. The residue is dissolved in

  
methylene chloride and washed successively with 50

  
ml of N / 2 sodium hydroxide solution, 50 ml of water and, finally, 50 ml of N / 2 hydrochloric acid. The residue is dissolved in methylene chloride, then washed with three 75 ml portions of N / 2 sodium hydroxide solution in order to remove the triazole by-product, with 75 ml of water and, finally, with 75 ml of N / 2 hydrochloric acid, the sclvant is removed, thus obtaining a solid product which, after two recrystallization? in a benzene / petroleum mixture 40-60 [deg.] C,

  
 <EMI ID = 172.1>

  
EXAMPLE 16.

  
This example illustrates the preparation of a compound of formula (II) by another process using, as an intermediate, a carbonylbistriazole.

  
Add a solution of 21.6 g of 3-piperidinosulfonyl-1,2,4-triazole and 14 ml of triethylamine in 100 ml of dry tetrahydrofuran, dropwise, with stirring, to a solution of 5 g of phosgene in 100 ml of dry tetrahydrofuran, while maintaining the temperature below 15 [deg.] C during the addition, cooling with a mixture of ice and water. A precipitate forms immediately and the mixture is stirred for a further
30 minutes after the end of the addition. The precipitate of triethylamine hydrochloride is then separated by filtration.

  
Is added to the filtrate prepared above,

  
 <EMI ID = 173.1>

  
50 ml of dry tetrahydrofuran, dropwise and with stirring. An exothermic reaction occurs and the reaction mixture is cooled to maintain the temperature below 20 [deg.] C. The mixture is stirred for a further 30 minutes after the addition is complete.

  
The solvent is removed from the mixture by vacuum distillation, thus obtaining a solid product m.p.
68-71 [deg.] C. After crystallization from a benzene / petroleum mixture

  
 <EMI ID = 174.1>

  
m.p. 72-74 [deg.] C.

EXAMPLE 17.

  
This example illustrates compositions containing a compound of formula (II).

  
A dispersible powder is prepared by grinding together a mixture of the following ingredients in a hammer mill:

  

 <EMI ID = 175.1>


  
Similar dispersible powders are prepared using the following active ingredients to

  
the place of the triazole compound of the above composition:
1-diallylcarbamoyl-3-dipropylsulfamoyl-1,2,4-triazole,

  
1-diallylcarbamoyl-3-pyrrolidinosulfonyl-1,2,4-triazole, 1-diethylcarbamoyl-3-diallylsulfamoyl-1,2,4-triazole, 1-diallylcarbamoyl-3-diethylsulfamoyl-1,2,4-triazole , 1-

  
 <EMI ID = 176.1>

EXAMPLE 18.

  
This example illustrates compositions containing a compound of formula (II).

  
An emulsifiable concentrate is prepared to be diluted with water to obtain an aqueous emulsion, from the following ingredients:

  

 <EMI ID = 177.1>
 

  
 <EMI ID = 178.1>

  
on average 14 moles of ethylene oxide per mole of nonylphenol.

  
A similar emulsifiable concentrate is prepared in which the triazole compound of the above composition is replaced by the following compound: 1- (N-allylN-propylcarbamoyl) -3-diethylsulfamoyl-1,2,4-triazole.

  
EXAMPLE 19.

  
This example illustrates the use of compositions comprising a compound of formula (II).

  
In tests carried out in a greenhouse,

  
Soil trays are seeded with seeds of various weeds, then immediately sprayed with aqueous suspensions of the test compounds, at varying application rates of the test compound. We use

  
as witnesses, unseeded soil trays are not

  
 <EMI ID = 179.1>

  
0.56 kg / ha, all the triazoles mentioned in Examples 17 and
18 allow effective control of CG, BG, YF and JG (no germination, or the seedlings which have emerged show a seriously and irreparably stopped growth).

EXAMPLE 20.

  
This example illustrates the use of compositions comprising a compound of formula (I).

  
Greenhouse trials are carried out in which soil trays are sown with seeds

  
 <EMI ID = 180.1>

  
mediate the trays using aqueous suspensions of various test compounds, at application rates of the test compound decreasing logarithmically from 4.48 to 0.140 kg /

  
 <EMI ID = 181.1>

  
Alopecurus myosuroides (as shown by emergent seedlings that are severely and irreparably stunted), at an application rate of 0.280 kg / ha. None of the compounds exhibit phytotoxicity to wheat and barley crops at an application rate below 2.24 kg / ha. Thus, the following compounds exhibit selective pre-emergence activity against Alopecurus myosuroides in wheat and barley crops:
1-Diethylcarbamoyl-3- (2-propoxyethylsulfonyl) -1,2,4-triazole, 1- (N-butyl-N-ethylcarbamoyl) -3- (2-ethoxyethylsulfonyl) -1,2,4-triazole, 1- (N-allyl-N-propylcarbamoyl) -3-

  
 <EMI ID = 182.1>

  
EXAMPLE 21.

  
This example illustrates the use of compositions comprising a compound of formula (II).

  
Greenhouse trials are carried out in which soil trays are seeded with seeds of Alopecurus myosuroides, wheat and barley. The trays are immediately sprayed with aqueous suspensions.

  
of various test compounds, at a logarithmically decreasing test compound application rate between 4.48 and 0.140 kg / ha. The following compounds have been shown to effectively control Alopecurus myosuroides (as shown by plants which have emerged and whose growth is severely and irreparably stopped) at an application rate of 0.280 kg / ha. None of the compounds show phytotoxicity to wheat and barley crops at an application rate less than 2.24 kg / ha. This is how these compounds have a


    

Claims (1)

selective pre-emergence activity against Alopecurus myosuroides in wheat and barley crops: 1- (N-butyl-Nethylcarbamoyl) -3- (N-allyl-N-methylsulfamoyl) -1,2,4-triazole, 1- (N-Butyl-N-methylcarbamoyl) -3-diallylsulfamoyl-1,2,4triazole, 1-diethylcarbamoyl-3- (N-ethyl-N-methylsulfamoyl) - <EMI ID = 183.1> 3-piperidinosulfonyl-1,2,4-triazole. CLAIMS. 1.- Composed of the general formula: <EMI ID = 184.1> in which : <EMI ID = 185.1> to C6, C2 to C6 haloalkyl, halo-2-allyl or dihalo-2,3allyl; <EMI ID = 186.1> allyl, propynyl-2, alkoxyalkyl C2 to C4, haloalkyl C2 or C3, dihalo-2,3-allyl or cyclopropyl: <EMI ID = 187.1> at least one of the groups R, R and R being substituted by an alkoxy radical or by one or two halogen atoms in the case where R <2> is not a cyclopropyl radical. 2.- Composed of the formula: <EMI ID = 188.1> in which R <1> and R2 have the meanings defined in claim 1 and R <3> denotes a C to C4 alkyl or C2 to C6 alkoxyalkylsulfonyl radical, at least one of the groups R, R and R being substituted with an alkoxy radical or one or two halogen atoms, in the case where R2 is not a cyclopropyl radical ' <EMI ID = 189.1> <EMI ID = 190.1> a C2 or C3 alkyl, allyl, methyl-2-allyl, <EMI ID = 191.1> <EMI ID = 192.1> C 1 to C 4 coylsulfonyl or C 3 to C alkoxyalkyl sulfonyl C6, at least one of the groups R, R <2> and R <3> being substituted by an alkoxy radical. 4.- A compound according to claim 3, characterized <EMI ID = 193.1> <EMI ID = 194.1> <EMI ID = 195.1> cyclopropyl. 5.- A compound according to claim 4, characterized in that R <3> denotes a C2 to C4 alkylsulfonyl radical <EMI ID = 196.1> 6.- A compound according to claim 1, characterized in that R3 denotes an alkylsulfonyl radical C2 to C4 and the carbamoyl group CONR <1> R <2> is an N-alkyl-Nalcoxyalcoylcarbamoyl or N-allyl-N-alkoxyalcoylcarbamoyl group . 7.- A compound according to claim 1, characterized <EMI ID = 197.1> <EMI ID = 198.1> bamoyl, N-alkyl-N-allylcarbamoyl, N-alkyl-N-propinylcarbamoyl or N-dialcoylcarbamoyl. 8.- Compound according to claim 1, characterized in that R <3> denotes a C2 or C3 alkylsulfonyl radical <EMI ID = 199.1> 9.-. Compound according to Claim 1, characterized in that R <3> denotes a C2 to C4 alkyl or C3 to C 6 alkoxyalkylsulfonyl radical and the carbamoyl group CONR 1 R <2> is an N-cyclopropyl-N-alkylcarbamoyl group, of which <EMI ID = 200.1> 10.- herbicidal composition, characterized in that it contains as active ingredient or as one of the active ingredients a triazole according to claim 1, combined with a diluent or vehicle. 11. A herbicidal composition according to claim 10, characterized in that the triazole is a compound according to claim 2 and the diluent or vehicle is a solid or a liquid containing a surfactant. 12.- Method for combating pre-emergent weeds, characterized in that a triazole according to the claim 1 is applied to the soil. 13.- A method for combating pre-emergent weeds, characterized in that a triazole according to claim 2 is applied to the soil. 14.- A method for selectively combating weeds among cultivated plants, characterized in that a triazole according to either of claims 1 and 2 is applied in an amount sufficient to combat weeds, but showing virtually no phytotoxicity to cultivated plants. 15.- Process for preparing a compound according to claim 1, characterized in that one reacts a compound of the general formula R <1> R <2> NY with a compound of the general formula: <EMI ID = 201.1> in which R <1>, R <2> and R <3> have the meanings defined in claim 1 and Y or Q denote a hydrogen atom, the other group being a COC1, COBr or COF radical, or Y denotes a hydrogen atom and Q denotes the group of the formula: <EMI ID = 202.1> 16. A process according to claim 15, characterized in that Y or Q is a hydrogen atom, the other group being COC1. 17.- Process for the preparation of a compound of the general formula defined in claim 1, in which R <3> denotes an alkoxyalkylsulfinyl, haloalkyl- <EMI ID = 203.1> alkylsulfonyl, characterized in that one oxidizes a compound of the general formula <EMI ID = 204.1> in which R denotes an alkyl or alkoxyalkyl radical or <EMI ID = 205.1> defined in claim 1. 18.- Composed of the general formula: <EMI ID = 206.1> in which : <EMI ID = 207.1> dihalo-2,3-allyl, cyclopropyl or cyclohexyl; <EMI ID = 208.1> <EMI ID = 209.1> halo-2-allyl, dihalo-2,3-allyl, cyclopropyl or phenyl substituted with 1 to 3 halogen atoms; <EMI ID = 210.1> cyclohexyl, or R <3> and R4 together with the adjacent nitrogen atom form a heterogeneous ring <EMI ID = 211.1> 1-piperidyl, hexamethylene-imine and heptamethylene-imine, optionally substituted with one to four lower alkyl radicals, the total number of carbon atoms of R <1> and R2 being 3 to 9 inclusive, and when R <3> is a radical not containing a phenyl ring, the total number of carbon atoms of R <3> and R4 is from 2 to 9 inclusive. 19.- A compound according to claim 18, characterized in that R1 denotes a C1 or C2 alkyl radical, <EMI ID = 212.1> 2-allyl, dihalo-2,3-allyl, cyclopropyl or phenyl substituted by a single halogen atom, R4 being an alkyl radical <EMI ID = 213.1> allyl, dihalo-2,3-allyl, cyclopropyl or cyclohexyl, R <3> and R4 possibly also forming with the adjacent nitrogen atom a heterocyclic ring, chosen from morpholine, pyrrolidine, 1-piperidine, hexamethylene- rings imine and heptamethyleneimine, optionally substituted with 1 to 4 methyl radicals. 20. A compound according to claim 19, character- <EMI ID = 214.1> allyl, methyl-2-allyl, propinyl-2 or C2 to alkoxyalkyl <EMI ID = 215.1> C8. 220- A compound according to claim 18, characterized in that the carbamoyl group CONR <1> R <2> is a group <EMI ID = 216.1> dialkylsulfamoyl, di- (methyl-2-allyl) -sulfamoyl or N-allyl-N-alkylsulfamoyl group. 23.- A compound according to claim 18, characterized in that the carbamoyl group CONR <1> R <2> is a dialkoylcarbamoyl group and the sulfamoyl group S02NR <3> R4 is a dialkoylsulfamoyl, diallylsulfamoyl or N-allyl-Nalcoylsulfamoyl group. 24.- A compound according to claim 18, characterized in that the carbamoyl group CONR <1> R <2> is an N- group <EMI ID = 217.1> 250- A compound according to: claim 18, characterized in that the carbamoyl group CONR <1> R <2> is an N-alkyl-N-alkoxyalkylcarbamoyl group and the sulfamoyl group <EMI ID = 218.1> or N-allyl-N-alkylsulfamoyl. 26.- Herbicidal composition, characterized in that it comprises as active ingredient or as one of the active ingredients a triazole according to claim 18, combined with a diluent or vehicle. 27.- herbicjde composition, characterized in that it comprises as ingredient e, ctif or as one of the active ingredients a traizole according to one or the other of claims 19 to 25, the diluent or vehicle being a solid or a liquid containing a tonsioactive agent. 28.- Process for combating pre-emergent weeds, characterized in that a triazole according to one or the other of claims 18 to is applied to the soil. 25. 29.- A method for selectively controlling weeds among cultivated plants, characterized in that a triazole according to any one of claims 18 to 25 is applied in an amount sufficient to effectively combat weeds, but showing no phytotoxicity to cultivated plants. 30.- Process for the preparation of a compound according to claim 18, characterized in that a compound of the formula R <1> R <2> NY is reacted with a compound of the general formula <EMI ID = 219.1> <EMI ID = 220.1> defined in claim 18, Y or Q being a hydrogen atom, the other a COC1, COBr or COF group, or Y is a hydrogen atom and Q a group of the formula <EMI ID = 221.1> 31.- A method according to claim 30, characterized in that Y or Q denotes a hydrogen atom, the other <EMI ID = 222.1>