Selective herbicide compositions
The present invention relates to selective herbicide compositions. More particularly, this invention concerns herbicide compositions which contain at least one herbicidal compound preferably selected from the following group: thiolcarbamate, triazine, chloracetanilide, carbamide or phenoxyacetic acid herbicides in admixture with 0.1 to 50%, (by weight of the herbicidal compound) of a dichloroacetamide derivative of the formula I ##STR2## wherein X is oxygen, sulphur, SO or SO 2 , 
     n is 0 or 1, and 
     R 1  and R 2  are identical or different and represent hydrogen, alkyl or phenyl, substituted with halogen, hydroxyl or nitro; or 
     R 1  and R 2  together form a butylene, pentylene or hexylene group which can be substituted with one or two methyl groups, 
     provided that when n=0, R 1  and R 2  are not hydrogen, alkyl or substituted phenyl. 
     The above compositions have reduced phytotoxicity against cultivated plants, and are therefore suitable for the protection thereof against undesired weeds. A process for the use of said compositions for the above-mentioned purpose is also within the scope of this invention. 
     It is well known to those skilled in the art that, in substantial part, known herbicides are harmful to cultivated plants to be protected. The extent of this undesired phytotoxic effect is strongly dependent on the dose employed and on the conditions of application, for instance on the weather and soil conditions. Other herbicides are selective when used in small doses, but in a dose required for effective weed killing show a reduced selectivity, and become detrimental to the desired plant growth. 
     In the U.S. Pat. No. 3,131,509 the use of 1,8-naphthalic acid and derivatives, such as the anhydride, esters, amides thereof, is suggested to decrease the phytotoxicity of various herbicides. 
     According to the teaching of the Hungarian Pat. No. 165,736 the phytotoxicity of herbicide compounds can be reduced by adding an N,N-disubstituted dichloroacetamide derivative in an amount of 0.0001 to 30% by weight of the herbicide. 
     Most of the compounds widely used as antidotes belong to one of the above two classes of compounds; they are not, however, a final solution for this rather complicated problem. The herbicidal compounds whose phytotoxicity is to be decreased are chemically very different, and consequently possess different kind of phytotoxic activities. It is also obvious that different cultivated plants have different reactions when treated with various herbicides, and therefore the field of application of the known herbicides is strictly limited. 
     The object of the invention is to provide compounds of a new, class capable of decreasing the phytotoxicity of certain herbicides, and which are favorable with respect to environmental protection. The new compounds facilitate economical application of known herbicides. 
     It has been found that the dichloroacetamide derivatives of the formula I are capable of decreasing the phytotoxicity of herbicides of the triazine, carbamide, dichloro-acetanilide and phenoxyacetic acid type. More particularly, it has been found that when a compound of the formula I is admixed with at least one of the above-listed herbicides, in an amount of 0.1 to 50% by weight of the herbicide, the herbicidal formulations containing the mixture obtained are practically harmless to the cultivated plants and at the same time, preserve their herbicidal activity. According to another aspect of this invention the same effect can be achieved when, before sowing, the seeds of cultivated plants are admixed with a compound of the formula I (dressing), and after sowing weed-killing is performed with a known herbicide belonging to one of the above classes of compounds. 
     New compounds of the formula I according to the invention are illustrated in the following Table I. 
     
                                           TABLE 1                                 
__________________________________________________________________________
(Formula I)                                                               
                                                     physical const.      
Com-                                                 (melting point       
pound                                                °C.,          
                                                     refractive           
No. X  n R.sub.1     R.sub.2 compound                index)               
__________________________________________________________________________
1   O  0 pentylene   N-dichloroacetyl-1-oxa-4-azaspiro[4,5]               
                                                     105.5-107            
2   O  0 1&#39;-methylpentylene                                               
                     N-dichloroacetyl-10-methyl-1-oxa-4-azaspiro[4,5]     
                     decane                          100-102              
3   O  0 3&#39;-methylpentylene                                               
                     N-dichloroacetyl-8-methyl-1-oxa-4-azaspiro[4,5]      
                     decane                          119-120              
4   O  0 1,5&#39;-dimethyl-                                                   
                     N-dichloroacetyl-6,10-dimethyl-1-oxa-azaspiro[4,5]-  
                                                     n.sub.D.sup.26       
                                                     :1.5217              
         pentylene   decane                                               
5   O  0 butylene    N-dichloroacetyl-1-oxa-4-azaspiro[4,4]               
                                                     79-80e               
6   O  0 hexylene    N-dichloroacetyl-1-oxa-4-azaspiro[4,6]               
                                                     81-82ane             
7   S  0 pentylene   N-dichloroacetyl-1-thia-4-azaspiro[4,5]              
                                                     149-151              
8   S  0 1&#39;-methylpentylene                                               
                     N-dichloroacetyl-10-methyl-1-thia-4-azaspiro[4,5]    
                     decane                          106-109              
9   S  0 3&#39;-methylpentylene                                               
                     N-dichloroacetyl-8-methyl-1-thia-4-azaspiro[4,5]     
                     decane                          127-129              
10  S  0 butylene    N-dichloroacetyl-1-thia-4-azaspiro[4,4]              
                                                     83-85e               
11  S  0 hexylene    N-dichloroacetyl-1-thia-4-azaspiro[4,6]              
                                                     96-99ane             
12  SO 0 pentylene   N-dichloroacetyl-1-thia-4-azaspiro[4,5]              
                     decan-1-oxide                   188                  
13  SO.sub.2                                                              
       0 pentylene   N-dichloroacetyl-1-thia-4-azaspiro[4,5]              
                     decan-1,1-dioxide               180-181              
14  O  1 H H         N-dichloroacetyl-tetrahydro-1,3(2H)-oxazine          
                                                     n.sub.D.sup.26       
                                                     :1.5168              
15  O  1 CH.sub.3  CH.sub.3                                               
                     N-dichloroacetyl-2,2-dimethyl-tetrahydro-1,3(2H)-oxaz
                     ine                             n.sub.D.sup.26       
                                                     :1.507               
16  O  1 CH.sub.3  C.sub.2 H.sub.5                                        
                     N-dichloroacetyl-2-methyl-2-ethyl-tetrahydro-1,3(2H)-
                     oxazine                         n.sub.D.sup.26       
                                                     :1.4919              
17  O  1 pentylene   N-dichloroacetyl-1-oxa-5-azaspiro[5,5]               
                                                     111-112e             
18  O  1 1&#39;-methylpentylene                                               
                     N-dichloroacetyl-11-methyl-1-oxa-5-azaspiro[5,5]     
                     undecane                        135-138              
19  O  1 3&#39;methylpentylene                                                
                     N-dichloroacetyl-9-methyl-1-oxa-5-azaspiro[5,5]      
                     undecane                        115-118              
20  O  1 butylene    N-dichloroacetyl-1-oxa-5-azaspiro[5,4]               
                                                     62-64e               
21  O  1 hexylene    N-dichloroacetyl-1-oxa-5-azaspiro[5,6]               
                                                     n.sub.D.sup.26       
                                                     :1.5012              
__________________________________________________________________________
 
    
     From Table I it can be clearly seen that most of the new compounds are in a solid, crystalline state under normal conditions and only some of them are liquid at room temperature. 
     Chemically compounds of the formula I belong to the broad type of acid amides and can be prepared by various methods known in the art. 
     According to the principles of a well-known process, compounds of the formula I can be prepared by acrylating a cyclic amine or a salt thereof with dichloroacetyl chloride, in an inert solvent, in the presence of an acid binding agent [see German Patent Specifications Nos. 2,350,547 and 2,350,800; W. R. Vanghan et al., J. Org. Chem. 26, 145 to 148 (1961)]. The inert solvent can be a ketone, such as acetone, methylethyl ketone; an aliphatic hydrocarbon, such as hexane; an aromatic hydrocarbon, such as benzene, toluene, xylene; chlorobenzene; nitrobenzene; diethylether, dimethyl sulphoxide; or chlorinated aliphatic hydrocarbons, such as methylene chloride or carbon tetrachloride. Acylation, however, takes place also in the absence of an inert solvent. Suitable acid binding agents are: organic bases, such as triethyl amine, trimethyl amine, pyridine, N,N-dimethylaniline, but in organic bases such as alkali metal carbonates, alkali metal hydrocarbonates, alkali hydroxides and aqueous solutions thereof can also be used. The acylation is generally performed at a temperature between -50° C. and 160° C., preferably between -20° C. and 40° C. 
     Amines used as starting compounds are five-or six-membered heterocyclic compounds, which contain one nitrogen and one oxygen or sulphuric atom and the preparation thereof is described in a large number of publications, such as J. Am. Chem. Soc. 75, 358 to 361 (1953); J. D. Doughty et al.: J. Am. Chem. Soc. 72, 2366-2367 (1950); W. H. Watanabe: J. Am. Chem. Soc. 79, 2833-2836 (1957). Both five- and six-membered amines can be prepared by reacting a corresponding hydroxyalkylamine or mercaptoalkylamine or a hydrochloride thereof with an appropriate carbonyl compound, in a solvent or without any solvent, optionally in the presence of a catalyst, at room temperature or at an elevated temperature, optionally continuously eliminating the water formed. 
     The catalyst can be a basic catalyst, such as an alkali metal carbonate or an acid catalysts such as hydrogen chloride, hydrogen bromide or p-toluene-sulphonic acid. Suitable solvents are various aliphatic hydrocarbons, e.g. hexane, petroleum ether; halogenated derivatives thereof. e.g. methylene chloride, carbon tetrachloride; aromatic hydrocarbons, e.g. benzene, toluene, xylene; or derivatives thereof, e.g. chlorobenzene, nitrobenzene, as well as ethers or an excess amount of the carbonyl compound taking part in the reaction. 
     The reaction is accomplished at a temperature of 20° C. to 200° C. By using this reaction five-membered cyclic amines are obtained by reacting aziridine with a corresponding carbonyl compound, optionally in the presence of hydrogen sulphide. 
     In another method, compounds of the formula I are prepared starting from an N-dichloro-acetylated hydroxyalkylamine or mercaptoalkylamine, or the hydrochlorides thereof and a corresponding carbonyl compound under the above-described reaction conditions. 
     In a third method an N-nitrozo derivative of the corresponding heterocyclic amines is reacted with dichloroacetyl chloride [see German Patent Specification No. 2,035,796; K. L. Hebenbrock et al., Justus Liebig, Ann. Chem. 765, 78 to 95 (1972)]. 
     N-acylated heterocyclic amides can also be obtained by reacting a Schiff base, prepared from a corresponding aminoalcohol and a carbonyl compound, with dichloroacetyl chloride, under the reaction conditions described above [M. Businolli: Il Farmaco (Pavia) Ed. Sci. 10, 127 to 134 (1955)]. 
    
    
     The preparation of the compounds of the formula I and their antidote activity is further illustrated in the following non-limiting Examples. 
     EXAMPLE 1 
     Preparation of N-dichloroacetyl-1-oxa-4-azaspiro[4,5]decane (compound 1) 
     From a boiling mixture of 64 g. (0.645 moles) of cyclohexanone and 30 g. (0.491 moles) of ethanolamine in 100 ml. of benzene the water formed is continuously distilled off. Boiling is continued until 8.8 ml. of water are separated. The reaction mixture is then cooled, 55 g. (0.55 moles) of a 40% aqueous sodium hydroxide solution are added followed by dropwise addition of 74 g. (0.5 moles) of dichloroacetyl chloride with external salt/ice cooling. The mixture is stirred for two additional hours at room temperature and thereafter washed with an aqueous hydrochloric acid solution and subsequently with water. From the neutral mixture obtained benzene is distilled off in vacuo. 10 g. (0.4 moles) of a greenish-white crystalline substance are obtained. Recrystallization from absolute ethanol affords a white crystalline product melting at 105.5° to 107° C. The structure of the named compound can be verified by IR spectrum analysis. 
     Analysis: Calculated: C 47.63%; N 5.50%; Cl 28.12%; Found: C 47.12%; N 5.70%; Cl 28.56%. 
     EXAMPLE 2 
     Preparation of N-dichloroacetyl-1-thia-4-azaspiro[4,5]decane (compound 7) 
     From a boiling mixture of 9.8 g. (0.1 moles) of cyclohexanone and 7.7 g. (0.1 moles) of 2-mercaptoethylamine in 100 ml. of benzene the water formed is continuously distilled off. Boiling is continued until 1.8 ml. of water are separated. The reaction mixture is then cooled and 11 g. of a 40% aqueous sodium hydroxide solution are added followed by dropwise addition of 14.7 g. (0.1 moles) of dichloroacetyl chloride, with external salt/ice cooling. Mixture is stirred for a further two hours at room temperature and washed with aqueous hydrochloric acid solution and subsequently with water. From the neutral mixture obtained benzene is distilled off in vacuo to give 17.2 g. (0.064 moles) of a white powder. Recrystallization from absolute ethanol yields a white crystalline product melting at 149° to 151° C. The structure of the named compound can be verified by IR spectrum analysis. 
     Analysis: Calculated: C 44.77%; N 5.22%; S 11.95%; Cl 26.43%; Found: C 44.51%; N 5.31%; S 12.15%; Cl 26.29%. 
     EXAMPLE 3 
     Preparation of N-dichloroacetyl-8-methyl-1-oxa-4-azaspiro[4,5]decane (compound 3) 
     From a boiling mixture of 11.2 g. (0.1 moles) of 4-methyl-cyclohexanone and 6.1 g. (0.1 moles) of ethanolamine in 100 ml. of benzene the formed water is continuously distilled off. Boiling is continued until 1.8 ml. of water are separated. The reaction mixture is then cooled and 8 g. (0.1 moles) of pyridine are added followed by dropwise addition of 14.7 g. (0.1 moles) of dichloroacetyl chloride with external salt/ice cooling. Further following the procedure described in Example 2, 20.7 g. (0.078 moles) of a rose, oily product are obtained. Recrystallization from absolute ethanol affords a white, crystalline product melting at 119° to 120° C. The structure of the compound obtained can be verified by IR spectrum analysis. 
     Analysis: Calculated: C 49.63%; N 5.26%; Cl 26.64%; Found: C 49.45%; N 5.35%; Cl 26.92%. 
     EXAMPLE 4 
     Preparation of N-dichloroacetyl-1-oxa-5-azaspiro[5,5]undecane (compound 19) 
     From a boiling mixture of 17.6 g. (0.18 moles) of cyclohexanone and 11.2 g. (0.15 moles) of 3-aminopropanol in 50 ml. of benzene the water formed is continuously distilled off. Boiling is continued until 2.7 ml. of water are separated. The reaction mixture is then cooled and 16 ml. (0.165 moles) of a 40% aqueous sodium hydroxide solution are added followed by a subsequent dropwise addition of 22.1 g. (0.15 moles) of dichloroacetyl chloride, with external salt/ice cooling. 
     Further following the procedure described in Example 2 15.7 g. (0.059 moles) of a greenish white crystalline product are obtained. Recrystallization from absolute ethanol affords a white crystalline substance melting at 111° to 112° C. The structure of the compound obtained can be verified by IR spectrum analysis. 
     Analysis: Calculated: C 49.63%; N 5.26%; Cl 26.64%; Found: C 49.52%; N 5.32%; Cl 26.45%. 
     EXAMPLE 5 
     Preparation of N-dichloroacetyl-1-thia-4-azaspiro[4,4]nonane (compound 10) 
     From a boiling mixture of 8.4 g. (0.1 moles) of cyclopentanone and 7.7 g. (0.1 mole) of 2-mercaptoethylamine in 100 ml. of benzene the water formed is continuously distilled off. Boiling is continued until 1.8 ml. of water are separated. The reaction mixture is then cooled and 8 g. (0.1 moles) of pyridine are added followed by a dropwise addition of 14.7 g. (0.1 moles) of dichloroacetyl chloride, with external salt/ice cooling. 
     Furtheron following the procedure described in Example 2 21.6 g. (0.085 moles) of a yellowish oily product are obtained. Recrystallization from n-hexane affords a white, crystalline product melting at 83° to 85° C. The structure of the compound obtained can be verified by IR spectrum analysis. 
     Analysis: Calculated: C 42.53%; N 5.51%; S 12.61%; Cl 27.89%; Found: C 42.35%; N 5.45%; S 12.80%; Cl 27.56%. 
     EXAMPLE 6 
     Preparation of N-dichloroacetyl-1-thia-4-azaspiro[4,5]decane-1-oxide (compound 12) 
     13.41 g. (0.05 moles) of N-dichloroacetyl-1-thia-4-azaspiro[4,5]decane are dissolved in 100 ml. of methylene chloride and to the solution obtained a solution of 9.15 g. (0.053 moles) of n-chloroperbenzoic acid in 100 ml. of methylene chloride is added dropwise, at a temperature between -25° C. and -15° C. The reaction mixture is then stirred at room temperature for 2 hours and subsequently cooled to 10° C. The insoluble substances are filtered off and the filtrate is washed with two 30 ml. portions of a saturated sodium carbonate solution and subsequently with water, dried over sodium sulphate and finally, evaporated to dryness. 
     13.23 g. of a white crystalline product are obtained, corresponding to a yield of 93%. Recrystallization from absolute ethanol affords a white, crystalline product melting at 188° C. (decomp.). 
     Analysis: Calculated: C 42.26%; H 5.32%; O 11.26%; N 4.93%; Cl24.95%; S 11.28%; Found: C 42.18%; H 5.30%; O 11.35%; N 4.98%; Cl 24.90%; S 11.30%. 
     The structure of the compound obtained is verified by IR spectrum analysis. 
     EXAMPLE 7 
     Preparation of N-dichloroacetyl-1-thia-4-azaspiro[4,5]decane-1,1-dioxide (compound 13) 
     13.41 g. (0.05 moles) of N-dichloroacetyl-1-thia-4-azaspiro[4,5]decane are dissolved in 150 ml. of methylene chloride and a solution of 18.12 g. (0.105 moles) of m-chloroperbenzoic acid in 200 ml. of methylene chloride is added dropwise at a temperature of between 0° C. and 3° C. The reaction mixture is then allowed to stir at room temperature for one hour and boiled for another one hour. It is then cooled to 5° C., the precipitated solid is filtered off and washed with 50 ml. of methylene chloride. The filtrate is washed with two 50-ml. portions of a saturated sodium carbonate solution and subsequently with water, dried over anhydrous sodium sulphate and finally evaporated to dryness. 13.7 g. (91%) of a yellowish brown crystalline product are obtained, which is then recrystallized from acetone, using activated charcoal for decoloring. Melting point of the white, crystalline product obtained: 180° to 181° C. (decomp.). 
     Analysis: Calculated: C 40.00%; H 5.12%; O 15.99%; N 4.67%; Cl 23.66%; S 10.68%; Found: C 40.10%; H 5.08%; O 16.03%; N 4.70%; Cl 23.60%; S 10.72%. 
     The structure of the compound obtained can be verified by IR spectrum analysis. 
     All the other compounds listed in the Table I together with their physical characteristics may be prepared in an analogous way. 
     Some representatives of the herbicides the phytotoxicity of which is decreased by the compounds having the formula I are listed hereinbelow: 
     S-ethyl-N,N-dipropylthiocarbamate, 
     S-propyl-dipropylthiocarbamate, 
     S-ethyl-diisobutylthiocarbamate, 
     S-2,3,3-trichlorallyl-diisopropylthiocarbamate, 
     S-ethyl-cyclohexylethylthiocarbamate, 
     2-chloro-2&#39;,6&#39;-N-(methoxymethyl)acetanilide, 
     9-ethylhexahydro-1H-azepine-1-carbothioate, 
     2-chloro-N-isopropylacetanilide, 
     N,N-diallyl-2-chloroacetamide, 
     S-4-chlorobenzyldiethylthiocarbamate, 
     2-chloro-4-ethylamino-6-isoproylamino-s-triazine, 
     2-chloro-4,6-bis-(ethylamino)-sas-triazine, 
     2-(4-chloro-6-ethylamino-s-triazine-2-yl-amino)-2-methylpropionitrile, 
     2-chloro-4-cyclopropylamino-6-isopropylamino-s-triazine, 
     2,4-dichlorophenoxyacetic acid, 
     3-(3&#39;,4&#39;-dichlorophenyl)-1-methyl-1-(n-butyl)-urea, 
     2-chloro-2&#39;-ethyl-6&#39;-methyl-N-(1-methyl-2-methoxyethyl)-acetanilide, 
     2-chloro-2&#39;,6&#39;-diethyl-N-(1,3-dioxolan-2-yl-methyl)-acetanilide, 
     2-chloro-2&#39;,6&#39;-diethyl-N-(ethoxycarbonyl-methyl)-acetanilide, 
     2-chloro-N-ethoxymethyl-2&#39;-methyl-6&#39;-ethyl-acetanilide, 
     2-chloro-N-(2&#39;-methoxyethyl)-2&#34;,6&#34;-dimethyl-acetanilide, 
     2-chloro-N-butoxymethyl-2&#39;,6&#39;-diethyl-acetanilide, 
     2-chloro-N-(2&#34;-methoxy-1&#34;-methyl-ethyl)-2&#39;-methyl-6&#39;-ethylacetanilide, 
     2-chloro-N-isopropoxymethyl-2&#39;,6&#39;-dimethylacetanilide, 
     N,N-hexamethylene-S-ethyl-thiolcarbamate, 
     N-(3-chlorophenyl)-N&#39;-methyl-N&#39;-methoxyurea, 
     N-(3,4-dichlorphenyl)-N&#39;-methyl-N&#39;-methoxyurea, 
     N-(3-chloro-4-bromophenyl)-N&#39;-methyl-N&#39;-methoxyurea, 
     2-butylamino-4-chloro-6-ethylamino-s-triazine, 
     2-chloro-4,6-bis-isopropylamino-s-triazine, 
     2-methylmercapto-4,6-bis-isopropylamino-s-triazine, 
     2-methylmercapto-4-ethylamino-6-tert-butylamino-s-triazine, 
     2-tert-butylamino-4-ethylamino-6-methoxy-1,3,5-triazine, 
     4-amino-6-tert-butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one, 
     2,4-dichlorophenoxyacetic acid, 
     2,4-dichlorophenoxypropionic acid, 
     B 2,4-dichlorophenoxybutyric acid, 
     2-methyl-4-chlorophenoxyacetic acid, 
     2,4,5-trichlorophenoxyacetic acid, 
     and the mixtures of the above compounds. 
     Dichloroacetamide derivatives of the formula I may be formulated alone or together with one or more of the herbicides some representatives of which have been listed hereinabove into solid or liquid compositions by means of conventional techniques widely used for the preparation of plant protecting compositions. The crystalline compounds of the formula I may for example be converted to wettable powders by the following procedure: 
     Wettable powder: 
     70.0% a compound of the formula I 
     17.0% kaoline 
     8.0% activated silica 
     2.5% fatty alcohol sulphonate 
     2.5% ligninsulphonic acid-Na 
     By admixing the above components in the given proportions in an &#34;Alpine&#34; mill, a ready-for-use wettable powder composition is obtained. When also a herbicide active ingredient is employed, 50% of a herbicide and 20% of a compound of the formula I are admixed with the other ingredients. 
     When the compounds of the formula I are intended to be used to decrease the phytotoxicity of known herbicides prior to sowing by admixing the active ingredients with the seeds, advantageously talc is used as a carrier in an amount of 20 to B 30%. 
     Some of the compounds having the formula I are liquid at room temperature, and can therefore advantageously be formulated in form of emulsifiable concentrates. A typical emulsifiable concentrate consists of the following ingredients: 
     Emulsifiable concentrate I 
     20 to 50% of a compound having the formula I, 
     74 to 45% of a solvent (e.g. xylene), 
     9% polyoxyethylenealkyl ether emulgeator. 
     The composition of another emulsifiable concentrate is as given below: 
     Emulsifiable concentrate II 
     7% of a compound of formula I 
     75% of EPTC, 
     13% of xylene, 
     5% of polyoxyethylene-alkylether emulgeator. 
     Naturally also crystalline compounds can be formulated as emulsifiable concentrates. Emulsifiable concentrates are especially advantageous when the phytotoxicity of a liquid herbicide (e.g. EPTC) is to be decreased by means of a compound of the formula I. 
     Emulsifiable concentrate III 
     2-chloro-N-(methoxymethyl)-2&#39;,6&#39;-diethylacetanilide--50%, 
     N-dichloroacetyl-1-thia-4-azaspiro[4,5]-decane--8%, 
     polyoxyalkylacyl emulgeator--5% 
     xylene--37%. 
     Granulate 
     S-propyl-N,N-diisobutylthiolcarbamate--5%, 
     N-dichloroacetyl-1-oxa-5-azaspiro[5,5]-undecane--0.5%, 
     Pumice--94.5%. 
     Compounds of the formula I exert their antidote activity when they are sprayed together with an inert herbicide--either formulated together or in form of a tank mixture prepared before spraying--but treatment can also be carried out before spraying the herbicide. According to an advantageous embodiment of the treatment seeds are treated with a formulation containing a compound of the formula I before sowing, and the herbicidal composition is sprayed to the soil immediately before or after sowing. 
     The following examples illustrate the effect of the compounds having the formula I in combination with Afalone [N-(3,4-dichlorophenyl)-N&#39;-methyl-N&#39;-methoxyurea], Eptam [N,N-dipropyl-S-ethylthiolcarbamate], Sencor [4-amino-5-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazine-5-one] and Lasso [2-chloro-N-(methoxymethyl)-2&#39;,6&#39;-diethyl-acetanilide]. For comparison 1,8-naphthalic acid anhydride and N,N-diallyl-2,2-dichloroacetamide--both known antidotes--have been used. The measure of phytotoxicity was the green weight of the plants treated. 100% was the weight of plants where were cultivated by using only mechanical weed killing. 
     EXAMPLE 8 
     The deteriorating effect of Afalone was observed in sunflower cultures. The extent of the decrease of this disadvantageous effect when compounds of the formula I were also used was also tested. 
     Four subsequent trials were carried out on plots of 20 m 2  each. Afalone 50 WP was used in a dose of 5 kg. of active ingredient/ha. Antidotes were sprayed onto the fields parallel with Afalone, in form of aqueous suspensions. The results obtained are set forth in the following Table 2. 
     
                       TABLE 2                                                     
______________________________________                                    
                    Dose (kg./ha.)                                        
                    of antidote                                           
                    0.5   1.0     2.0                                     
                    green weight                                          
                    expressed in %                                        
                    related to the control                                
Afalone               41      41      41                                  
______________________________________                                    
Afalone + 1,8-naphthalic acid anhydride                                   
                      58      69      75                                  
Afalone + N,N-diallyl-2,2-dichloro-                                       
acetamide             48      51      67                                  
Afalone + compound 2  78      92      95                                  
Afalone + compound 7  67      89      90                                  
Afalone + compound 15 75      93      102                                 
Afalone + compound 17 81      95      99                                  
Control (mechanical weed killing)                                         
                      100     100     100                                 
______________________________________                                    
 
    
     From the measurement of the greed weight of sunflowers it can be unambiguously seen that heterocyclic dichloroacetamides according to the invention decrease the phytotoxicity of Afalone substantially better than either 1,8-naphthalic acid anhydride or N,N-diallyl-2,2-dichloroacetamide. It can also be seen that compound 17 exerts a practically 100% antidote effect. 
     EXAMPLE 9 
     In field trials substantially carried out as described in Example 8 the phytotoxicity of 5 kg./ha. of Afalone was tested on sunflower plants the seeds of which were treated with antidotes according to the invention, and known antidotes, respectively prior to sowing. Results of these trials were compared to the results obtained by mechanical weed killing (100%). It was found that smaller doses of the test compounds were sufficient to obtain the same effects as in the trials according to Example 8. The numerical results are shown in the following Table 3. 
     
                       TABLE 3                                                     
______________________________________                                    
                Dose (kg./ha.) of antidote                                
                0.25   0.50     1.00                                      
                green weight expressed in                                 
                % related to the control                                  
Afalone           41       41       41                                    
______________________________________                                    
1,8-naphthalic acid anhydride +                                           
Afalone           57       69       75                                    
N,N-diallyl-2,2-dichyloracet-                                             
amide + Afalone   62       71       75                                    
Afalone + compound 2                                                      
                  89       95       98                                    
Afalone + compound 7                                                      
                  78       86       90                                    
Afalone + compound 15                                                     
                  90       94       96                                    
Afalone + compound 17                                                     
                  92       98       100                                   
Control (mechanical weed killing)                                         
                  100      100      100                                   
______________________________________                                    
 
    
     The results do not differ significantly--within the measurement&#39;s accuracy--from the results obtained in Example 1, although smaller doses of antidote were used. 
     EXAMPLE 10 
     The deteriorating effect of Eptam was observed in maize cultures. The extent of the decrease of this undesired effect when compounds according to the invention were also used was also tested. 
     Four subsequent field trials were carried out on fields of 20 m 2  each. The maized tested belonged to the hibride species &#34;Beke 270&#34;. 13 l./ha. of Eptam 6 E liquid herbicide and various doses of antidotes were sprayed to the fields in form of a tank mixture, prior to sowing. The results obtained are set forth in the following Table 4. 
     
                       TABLE 4                                                     
______________________________________                                    
                 Dose (kg./ha.) of antidote                               
                 0.5   1.0      2.0                                       
                 green weight expressed in                                
                 % related to the control                                 
Eptam              48      48       48                                    
______________________________________                                    
Eptam + 1,8-naphthalic acid an-                                           
hydride            60      64       70                                    
Eptam + N,N-diallyl-2,2-dichloro-                                         
acetamide          69      84       92                                    
Eptam + compound 1 98      102      105                                   
Eptam + compound 2 90      98       99                                    
Eptam + compound 3 94      97       100                                   
Eptam + compound 7 97      100      100                                   
Eptam + compound 9 92      97       98                                    
Eptam + compound 17                                                       
                   98      100      100                                   
Eptam + compound 19                                                       
                   96      98       102                                   
Control (mechanical weed killing)                                         
                   100     100      100                                   
______________________________________                                    
 
    
     From the above results it is apparent that five of the seven heterocyclic dichloroacetamide tested entirely eliminated the phytotoxic effect caused by Eptam, but also the remaining two compounds exerted at least the same effect as N,N-dichloroacetamide (Ardicane) widely used for this purpose. 
     EXAMPLE 11 
     Field trials were substantially carried out as described in Example 10 with the only difference that seeds were treated with various doses of antidotes before sowing into a soil treated with 13 lit./ha. of liquid Eptam 6 E. The results obtained by measuring the green weight of plants are shown in the following Table 5. 
     
                       TABLE 5                                                     
______________________________________                                    
                   Dose (kg./q. seed)                                     
                   0.25  0.50     1.00                                    
                   green                                                  
                   weight expressed in                                    
                   % related to the control                               
Eptam                48      48      48                                   
______________________________________                                    
1,8-naphthalic acid anhydride + Eptam                                     
                     68      70      72                                   
N,N-diallyl-2,2-dichloroacetamide +                                       
+ Eptam              69      75      80                                   
Eptam + compound 1   98      100     100                                  
Eptam + compound 2   95      97      97                                   
Eptam + compound 3   97      98      102                                  
Eptam + compound 7   98      102     105                                  
Eptam + compound 9   90      95      95                                   
Eptam + compound 17  95      98      98                                   
Eptam + compound 19  97      100     103                                  
Control (mechanical weed killing)                                         
                     100     100     100                                  
______________________________________                                    
 
    
     From the results set forth in Table 5 it is apparent that although smaller doses of antidotes were employed, compounds 1, 3, 7 and 19 practically entirely eliminated the deteriorating effect of Eptam. 
     EXAMPLE 12 
     The effect of the compounds having the formula I on the phytotoxic effect of Sencor in soya bean cultures was tested. Soya plants were treated with a suspension containing 1.5 kg./hectare of Sencor and various doses of antidotes immediately after sowing. The results obtained are set forth in the following Table 6. 
     
                       TABLE 6                                                     
______________________________________                                    
                 Dose (kg./ha.) of anti-                                  
                 dote                                                     
                 0.5   1.0      2.0                                       
                 green weight expressed in                                
                 % related to the control                                 
Sencor             17      17       17                                    
______________________________________                                    
Sencor + 1,8-naphthalic acid an-                                          
hydride            30      41       52                                    
Sencor + N,N-diallyl-2,2-dichloro-                                        
acetamide          20      21       26                                    
Sencor + compound 1                                                       
                   42      65       72                                    
Sencor + compound 7                                                       
                   48      70       76                                    
Sencor + compound 8                                                       
                   45      68       76                                    
Sencor + compound 17                                                      
                   48      71       82                                    
Control (mechanical weed killing)                                         
                   100     100      100                                   
______________________________________                                    
 
    
     From the above results it can clearly be seen that compounds of the formula I show a significantly better antidote effect than either 1,8-naphthalic acid anhydride or N,N-diallyl-dichloroacetamide. 
     EXAMPLE 13 
     Other trials were carried out substantially as described in Example 12 except that soya seeds were treated with antidotes and Sencor was sprayed to the soil immediately after sowing in a dose of 1.5 kg./ha. 
     The results obtained are set forth in the following Table 7. 
     
                       TABLE 7                                                     
______________________________________                                    
                   Dose (kg./q) of seed                                   
                   0.25  0.50    1.0                                      
                   green                                                  
                   weight expressed in                                    
                   % related to the control                               
Sencor               17      17      17                                   
______________________________________                                    
Sencor + 1,8-naphthalic acid anhydride                                    
                     51      64      70                                   
Sencor + N,N-diallyl-2,2-dichloro-                                        
acetamide            26      28      51                                   
Sencor + compound 1  52      75      80                                   
Sencor + compound 7  58      79      87                                   
Sencor + compound 8  55      75      82                                   
Sencor + compound 17 61      82      92                                   
Control (mechanical weed killing)                                         
                     100     100     100                                  
______________________________________                                    
 
    
     The above results illustrate that on soya pre-treated with compounds of the formula I--especially with compound 17--Sencor has practically no injurious effect while 1,8-naphthalic acid anhydride and N,N-diallyl-2,2-dichloroacetamide show a much weaker antidote activity. 
     EXAMPLE 14 
     Tests were carried out to determine the phytotoxic effect of &#34;Lasso&#34;, a composition containing 2-chloro-N-(methoxymethyl)-2&#39;,6&#39;-diethyl-acetanilide as active ingredient in sorghum cultures and to observe how this undesired effect was influenced by adding compounds of formula I. 
     Four subsequent field trials were carried out on plots of 20 m 2  each, with 4.5 lit./ha. doses and Lasso 48 EC. 
     Wettable powder compositions containing a compound of the formula I as an active ingredient, were suspended in water, and subsequently admixed with an aqueous emulsion of Lasso 48 EC in a quantity corresponding to the doses indicated in Table 8 below. The mixture obtained in this way was applied to the soil after sowing the sorghum, but prior to emergence (preemergent treatment). The results were evaluated by comparing the green weight of four weeks old plants to that of the control, which was treated by mechanical weed killing. 
     
                       TABLE 8                                                     
______________________________________                                    
                 Dose (kg./ha.) of active                                 
                 ingredient                                               
                 0.5   1.0      2.0                                       
                   green weight expressed in %                            
Treatment          related to the control                                 
Lasso 48 EC        37      37       37                                    
______________________________________                                    
Lasso 48 EC + 1,8-naphthalic                                              
acid anhydride     61      65       70                                    
Lasso 48 EC + N,N-diallyl-2,2                                             
dichloroacetanilide                                                       
                   72      78       82                                    
Lasso 48 EC + compound 1                                                  
                   95      97       102                                   
Lasso 48 EC + compound 2                                                  
                   80      87       92                                    
Lasso EC + compound 7                                                     
                   90      95       98                                    
Lasso 48 EC + compound 12                                                 
                   75      78       83                                    
Lasso 48 EC + compound 13                                                 
                   92      98       100                                   
Lasso 48 EC + compound 14                                                 
                   90      96       98                                    
Control (mechanical weed killing)                                         
                   100     100      100                                   
______________________________________                                    
 
    
     EXAMPLE 15 
     Field trials were substantially carried out as described in Example 10 with the only difference that seeds were treated with various doses of antidotes of the formula I before sowing, and after sowing a 4.5 lit./ha. dose of Lasso 48 EC was applied to the fields. The results obtained by measuring the green weight of four weeks old plants and expressed in % related to the control are shown in the following Table 9. 
     
                       TABLE 9                                                     
______________________________________                                    
                Dose (kg. of active ingre-                                
                dient/q of seed)                                          
                0.25    0.50     1.0                                      
                  green weight expressed in %                             
Treatment         related to the control                                  
Lasso 48 EC       37        37       37                                   
______________________________________                                    
Lasso 48 EC + 1,8-naphthalic                                              
acid anhydride    68        71       73                                   
Lasso 48 EC + N,N-diallyl-2,2                                             
dichloroacetamide 75        80       85                                   
Lasso 48 EC + compound 1                                                  
                  98        105      110                                  
Lasso 48 EC + compound 2                                                  
                  95        98       96                                   
Lasso 48 EC + compound 7                                                  
                  97        102      105                                  
Lasso 48 EC + compound 12                                                 
                  93        96       96                                   
Lasso 48 EC + compound 13                                                 
                  94        98       107                                  
Lasso 48 EC + compound 14                                                 
                  87        91       85                                   
Control (mechanical weed killing)                                         
                  100       100      100                                  
______________________________________                                    
 
    
     The conclusion can be drawn that the compounds of the formula I tested without exception considerably decreased or even totally eliminated phytotoxic activity of Lasso 48 EC on sorghum plants. In some instances--see for example compounds 1, 7 and 13--even a certain stimulating effect could be observed.