BE568662A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 



   The present invention relates to novel compounds corresponding to the general formula
 EMI1.1
 in which X denotes a halogen, is a number from 1 to 4, inclusive, Y is hydrogen or a halogen and n1 and n are identical or different numbers of value 0 or 1 and, if n1 and n are all two equal to 0.1 m is greater than 1 and the unsatisfied valences of carbon atoms 2 and 3 determine a double bond between the atoms, as well as the preparation of these compounds and their applications.



   Thus, the compounds according to the invention include those of the general formula
 EMI1.2
 wherein the substituents X1, X2, X3 and X4 are hydrogen or halogen atoms, for example fluorine, chlorine, bromine or iodine, with chlorine being the preferred halogen and one of the substituents At least X being a halogeno
More specifically, preferred compounds of formula (I) may be represented by formula
 EMI1.3
 in which X is a halogen atom, preferably a chlorine atom, at least one of the substituents X being a halogen atom.



   Typical compounds of formula I are: 3.4-dichloro-thiophene 1.1-dioxide 3-chloro-thiophene 1.1-dioxide 304-dibromo-thiophene 1.1-dioxide 3-bromo 1.1-dioxide -thiophene 1.1-dioxide 203-dichloro-thiophene 1.1-dioxide 205-dichloro-thiophene 1.1-dioxide 2.4-dichloro-thiophene 1.1-dioxide 3.4-difluoro-thiophene 1.1-dioxide 2.3.4.5 -3etrachloro-thiophene

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 EMI2.1
 1.1 - 2.3.4-tri-thiaphene 1 .1-dioxide 2.3.4-trichloro-thiophene 1.1-dioxide 2o5-dibromo-thiophene 1.1-dioxide.



   Also part of the invention are novel 1-1-dioxides of polyhalo-203-dihydro-thiophenes corresponding to the formula
 EMI2.2
 in which X is a halogen such as fluorine, chlorine, bromine or iodine, chlorine being the preferred halogen, m a number from 3 to 6, inclusive, and n a number equal to (6-m) o
Typical compounds according to the invention are:
 EMI2.3
 3.3.4.5-tetrachloro-2.3-dihydro-thiophene 1.1-dioxide 3o3.4-trichloro-2.3-dihydro-thiophene 1.1-dioxide 3.3.5-trichloro-2.3-dihydro-thiophene 1.1-dioxide.



   In general, the compounds of the present invention can be prepared by "dehydrohalogenation" (removal of halogenated hydracid) of a suitable derivative of 1.1-thiophene dioxide, for example, in an alkaline medium. The compounds of formula I can be prepared by dehydrohalogenating a compound of formula
 EMI2.4
 
 EMI2.5
 with the aid of an alkaline reagent, formula in which the substituents X11 X, X39 X4 'X5 and 6 represent hydrogen or halogen atoms9 at least X 5 and X6 and another substituent X being halogens. In this reaction, 2 molecules of HX acid are removed.



   Compounds of formula I can also be prepared by dehydrohalogenizing a compound of formula
 EMI2.6
 

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 using an alkaline reagent, with removal of an HX acid molecule. In
 EMI3.1
 this formula, the substituents X19 x2e X3 X4 and X5 are hydrogen or halogen atomsq at least X5 and another substituent X being halogenso
More especially, compounds of formula I can be prepared by reacting a compound of formula
 EMI3.2
 with an alkaline reacting substance, such as - for example an alkali metal hydroxide such as sodium or potassium hydroxide, ammonia, ammonium hydroxide, or an alkali metal carbonate such as carbonate sodium, potassium, potassium bicarbonate,

   or else an amine such as diethylamine, ethanolamine or pyridine In the formula, the substituent X denotes a halogen atom, for example fluorine, chlorine, bromine or iodine, chlorine being l 'preferred halogen
The above reactions can be carried out in a solvent, for example an organic solvent such as methanol, ethanol, acetone, cyclo-hexanone, xylene, or in water.

   These reactions are carried out at a temperature sufficient for them to take place normally, for example between 0 and the decomposition temperature of the starting substances; is desirable to operate below 1150 and preferably between 20 and 35 0
As examples of these preparations, a halogeno can be obtained.
 EMI3.3
 thiophene-lol-dioxide by reacting with an alkaline reagent, as has been said, a poly-halo-tetra-hydro-thiophene-1.1-dioxide such as 3030404-tetrachloro-tetrahydro- 1.1-dioxide thiophene, 2030404-tetrachloro-tetrahydro-thiophene 1.1-dioxide, 2.3-3.4-tetrachloro-tetrahydro-thiophene 1.1-dioxide, 3m4-dichloro-3o4-difluoro-tetrahydro-thiophene 1 .1-dioxide , 20304-tribromo-tetrahydro-thiophene 1.1-dioxide,

   4-pentachloro-tetrahydro-thiophene 1.1-dioxide 2030304a, 101-dioxide 304-dibromo-304-diahloro-tetrahydro-thiophene, 1.1-dioxide 3.3.4-trichloro-4-fluoro-tetrahydro-thio- phene, or a poly-halo-dihydrothiophene-i01-dioxide, such as 2030404-tetra-halo-dihydrothiophene-1o1-dioxide, 3.3-4.5-tetra-halo-dihydro-thiophene-1.o1-dioxide, 30304-tri-halo-dihydro-thiophene-lol-dioxide, 20304-tri-halo-dihydro-thiophene-1,1-dioxide, for example 3a3.405-tetrachloroLdihyàro-thiophene 1.1-dioxide, 1.1- 2.3.4.4-tetrachloro-dihydro-thiophene dioxide, 2.3. 1.1-dioxide,

  f-trtbromo-dihydro-thiophene 1 01-dioxide 3.4-dichloro-4-fluoro-dihydro-thiophene or 1.1-dioxide 30304-tribsono-dihydro-thiophene
The product formed can be recovered by adding to the reaction mixture a miscible solvent in which this product is relatively insoluble, until it precipitates, or by removing the initial solvent by distillation, preferably under reduced pressure.
The novel compounds of formula II can generally be prepared by removing a molecule of halogenated hydracid ("mono-dehydrohalogenation") from a compound of formula

 <Desc / Clms Page number 4>

 
 EMI4.1
 in which m is a number from 3 to 6, inclusive, and n is a number equal to (6-m) o Generally, mono-dehydrohalogenation,

     preferably the mono-dehydrochlorination of a tetra- to hepta-chloro-tetrahydro-thiophene-1.1-dioxide, to obtain a new compound according to the invention, is carried out in an organic solvent, preferably in an alkaline medium, for example in the presence of a small amount of pyridine. The operation is advantageously carried out by dissolving the compound, from which it is desired to remove a molecule of halogenated hydracid, in a solvent, such as a low molecular weight aliphatic alcohol, containing a small proportion of a soluble base, at temperature. high, for example at the boiling point of the organic solvent, then by separating the product formed, for example by adding water to the hot alcoholic solution and cooling the mixture or else by removing the solvent.



   The new compounds according to the invention are useful as chemical intermediates and show a very high chemical reactivity.



  They also have a pronounced biological activity. More particularly, they are active pesticides, for example insecticides which can be used for the destruction of aphids, fungicides, for example for the destruction of fungi in soils, herbicides, for the control of harmful plants, and bactericides which serve to inhibit the growth of microorganisms, for example.



   These compounds can be used alone or in combination with other known substances endowed with biological activity, for example with other 1.1-dioxides of poly-hydrothiophenes, organic phosphates pesticides, insecticidal chlorinated hydrocarbons, fungicides for foliage and soils, herbicides to be applied before or after the plants have emerged, etc.



   The compounds of the invention can have various applications, biological or otherwise and, if they are used as substances endowed with biological activity, it is obvious that they can be applied in various formulas, liquid or solid, comprising finely divided powders and granulated materials as well as liquids, such as solutions, concentrates, emulsifiable concentrates, slurries, etc., depending on the intended application and the desired medium for the composition.



   Thus, it will be noted that the present compounds can be used to form products endowed with biologic activity and containing these compounds as essential active substance, the compositions obtained being able also to contain vehicles comprising diluents, fillers, conditioning agents, solids. or liquids, finely divided, namely various kinds of clays, diatomaceous earth, talc, spent catalysts, alumina-silica materials, solvents and diluents, etc., namely water and various organic liquids such as benzene, toluene, chlorinated benzene, acetone, cyclohexanone, xylene, carbon disulphide, and mixtures of these substances.



   If liquid compositions are used or when preparing dry products which are to be applied in liquid form, it is in some cases expedient to additionally add an emulsifying or dispersing wetting agent. facilitate the use of the composition, for example anionic or cationic surfactants, quaternary-cationic ammonium salts, alkyl-arylsulfonate surfactants (such as dodecylbenzene-

 <Desc / Clms Page number 5>

 sodium sulfonate), nonionic surfactants based on poly-oxyalkylene fatty esters, "Triton" X-155 (alkyl-aryl-poly-ether-alcohol, U.S. Patent No. 2,504,064 of April 5, 1946 ). A list of such agents is given in an article by John W.

     MoCutcheon in "Soap and Chemical Specialties", Vol.



  31, No. 7-10, 1955. In general, the compositions according to the invention contain less than 10% by weight of the surfactant, and more often less than 1%.



   The term "carrier" herein refers broadly to materials constituting a substantial part of a composition endowed with biological or other activity, and therefore includes finely divided materials, liquid or solid, above. mentioned and advantageously used in such applications
The following examples illustrate the present invention without limiting it in any way.



    EXAMPLE 1.



  Preparation of 1.1-dioxide, 3.4.-dichloro-thiophene.



   258 g (1 molecule) of 3.3.4.5.-tetra-chloro-tetrahydro-thiophene 1.1-dioxide are dissolved in 2 liters of methanol, at room temperature o 28% aqueous ammonia (approximately 150 g) with methanolic solution, while stirring, until this solution remains basic o Cooling during the addition so as to maintain a temperature of 30 to 35 o The solution is left to stand to ensure complete reaction, adding enough aqueous ammonia to keep the solution basic.



   1 liter of distilled water is then added to the methanolic solution, then the methanol is distilled off under a pressure of 20 to 25 mm of mercury, on a water bath at approximately 40 ° C. The precipitated product is separated by filtration and washed with distilled water. After recrystallization, this product is dried in a vacuum desiccator. The desired compound of the formula C4H2Cl2O2S2 is obtained, which melts at 112-113 on decomposition. The following elemental analysis shows that the desired product has indeed been obtained.
 EMI5.1
 
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  Element <SEP> <SEP> values found <SEP> Calculated <SEP> values
<tb>
<tb>% <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
<tb>
<tb>
<tb> C <SEP> 25.91 <SEP> 25.96
<tb>
<tb> C1 <SEP> 38.0 <SEP> 38.32
<tb>
 
The solubility of this 3,4-dichlorothiophene 1.1-dioxide is greater than 5% in acetone, cyclohexanone and xylene, but less than 5% in water.



  EXAMPLE 2.



   To show the insecticidal activity of the compound, male cockroaches, Blattella germanica, from 8 to 9 weeks old are anesthetized with carbon dioxide to facilitate their handling, they are immersed in a composition to be tested (2000 parts per million of the product of example 1, 5% acetone, 0.01% of "Triton" X-155, the remainder being constituted by 1 water) for 10 seconds, then they are removed, the excess liquid is removed and we put them in a cage. Two batches of 10 insects each are exposed to this composition and observations of mortality are noted after 3 days. With the product of Example 1 at the above concentration, 100% mortality was found.



  EXAMPLE 3
25 house flies 4 to 5 days old are caged over small paper cups containing a piece of cotton wool impregnated with 15 µm3 of the composition to be tested, at 10% sugar. The compositions comprise 2000 ppm and 1000 ppm respectively of the product of example i, 5% acetone, 0.01% of "Triton" X-155, the remainder being constituted by water. Mortality, noted 24

 <Desc / Clms Page number 6>

 hours after application, is greater than 80% and 60% respectively, at the above concentrations.



  EXAMPLE 4.



   Another insecticidal application is illustrated by tests on the aphidian Aphis fabae, grown on watercress plants. We do not try, in this attempt to choose insects having a specific age. The cress plants are infested with about 100 aphids and are treated by pouring in a composition (2000 ppm of the product of Example 1, 5% acetone, 0.01% "Triton" X-155, the remainder. in water) on the ground, at a rate corresponding to 73 kg per hectare. 100% aphid mortality is obtained 24 hours after the treatment with 3,4-dichloro-thiophene 1.1-dioxide EXAMPLE 5.



   Spore germination tests are carried out on microscope slides by the tube dilution method, namely according to the method recommended by the "American Phytopathological Society's Committee on standardization of fungicidal teste". In this process, the product of Example 1, in aqueous compositions at concentrations of 1000, 100, 10 and 1 parts per million, is tested to determine its power of inhibition on the germination of spores of cultures of 7 to 10 days. of Alternaria oleracea and of Monilinia fructicolao These concentrations are the initial concentrations, before dilution of 4 volumes with 1 volume of stimulant and spore suspension. Germination should be noted after 20 hours of incubation at 22, in with 100 spores.



   The results show that concentrations of less than 1 mmp control both A. oleracea and Mo fructicolao disease EXAMPLE 6
Another fungicidal activity is illustrated by the ability of 3.4-dichloro-thiophene 1.1-dio- xide to protect seeds and heavy seedlings from mold and destruction by fungi of the species Pythium and Fusarium. , we treat the infested soil, in boxes of 10 x 10 x 8 cm, by the method of watering the earth, with applications corresponding to 18, 9 and 4.5 kg per hectare. The treatment is carried out by pouring 70 cm3 of the composition tested (product of the example 5% acetone, 0.01% "Triton" X-155, the remainder being constituted by water)

   on the surface of the soil o Leave the soil to rest until the next day, then remove it from each box and mix it thoroughly before returning it to the boxes. Three days after this treatment, 25 pea seeds of the variety "Perfection" are sown at the same depth in each box. The condition of the seedlings, noted 14 days after sowing, shows respective rates of 94%, 96% and 100% at the above concentrations while an untreated control soil gives a rate of only 3%, which illustrates the high activity of the product as a fungicide in soils.



     EXAMPLE 7
The herbicidal activity before soil emergence is determined on seeds of perennial ryegrass and radish which are treated, in Petri dishes, with aqueous suspensions of the product of Example 1 at concentrations of 1000 and 100 parts per million (ie 1000 and 100 ppm of the chemical compound to be tested, 5% acetone, 0.01% "Triton" X-155, the remainder being the water). Batches of 25 seeds of each type were dispersed in individual boxes containing filter paper discs moistened with 5 cc of the composition at each of the concentrations. The concentration of the compound which inhibits the germination of half of the grains (D value 50) is determined after 7 to 10 days.

   The D 50 of 3.4-dichloro-thiophene 1.1-dioxide is between 10 and 100 parts per million, both for radish and ray seeds.

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 oily EXAMPLE 8
To also determine the effects of the product of Example 1 on seed germination in the soil, a mixture of grains from six different harvest plants is dispersed in metal cake molds 20 x 5 cm filled to the point. 1 cm from the edge of composted soil then the seeds are evenly covered with 1/2 cm of soil and watered. 24 hours later, 80 cm3 of an aqueous solution containing 320 mg of the product of Example 1 are sprayed uniformly on the surface of the molds under an air pressure of 0.7 kg. This treatment is equivalent to a application of 73 kg per hectare.

   Further determinations are made at the respective applications of 9 and 4.5 kg per hectare. The grain mixture consists of seeds of three broadleaf plants: turnip, flax and alfalfa and three grasses: wheat, millet and false rye. Two weeks after the treatment, the condition of the seedlings is noted and it is compared with that of an untreated control seedling. The results, in terms of rate (%), are given in Table 1.



   TABLE 1
 EMI7.1
 
<tb> Application, <SEP> in <SEP> Kg <SEP> Seeds <SEP> of <SEP> plants <SEP> Seeds <SEP> of
<tb> to <SEP> per hectare <SEP> broadleaf <SEP> * <SEP> grasses <SEP> @
<tb>
<tb> 73 <SEP> 1 <SEP> @@ <SEP> 20
<tb> 9 <SEP> 50 <SEP> 90
<tb> 4.5 <SEP> 60 <SEP> 100
<tb>
   @ The results express the state as a rate (%) @@ Only the alfalfa grains emerge and grow.



    EXAMPLE 9
To evaluate the herbicidal activity after soil emergence, an aqueous composition is sprayed (3200 ppm of the product of Example 1, 5% acetone, 0.01% "Triton" X-155, the remainder. consisting of water), on tomato plants of the variety "Bonny Best" from 13 to 18 cm high, on corn plants of the variety "Cornell" M-1, from 10 to 15 cm, on bean plants of the variety "Tender-green", at the stage where the tarnished leaves are just starting to open, and on oat plants of the variety "Clinton", 8 to 13 cm;

   spray 100 cm3 of the composition, under an air pressure of 2.8 kg, on the plants which turn on a rotating plate, in a spray hood o 14 days after this treatment, the effects produced are noted and the herbicidal activity using a scale from 0 (no damage) to 11 (corresponding to the death of the plant). According to this method, 304-dichlorothiophene 1.1-dioxide receives the ratings shown in Table 2 below.
TABLE 2 @
 EMI7.2
 
<tb> PLANTS
<tb>
<tb>
<tb> @ <SEP> Concentration <SEP> Tomatoes <SEP> beans <SEP> but <SEP> oats
<tb>
<tb>
<tb>
<tb> in <SEP> ppm.
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>



  3200 <SEP> 11 <SEP> 11 <SEP> 10 <SEP> 7
<tb>
<tb>
<tb>
<tb> 1600 <SEP> 11 <SEP> 9 <SEP> 8 <SEP> 6
<tb>
   @ see example 9 for the explanation of the method.



  EXAMPLE 100
To detect absorption of the product by the roots and its migration into the developing plant, tomato plants of the variety

 <Desc / Clms Page number 8>

 "Bonny Best", 13-18 µm in height, as well as corn plants of the variety "Cornell" M-1, 10-15 cm 3, by pouring 51 cm 3 of a composition comprising 1000 ppm of the compound. chemical to be tested, 5% acetone0.01% "Triton" X-155, the rest in water, on the soil of 10 cm pots, in which the plants grow. The chemical compound is applied at a rate equivalent to 36 kg per hectare.

   The plants are kept under control, in a greenhouse, for 10 days, before examining them, then the herbicidal effect is observed and it is evaluated against a scale ranging from 0 (no damage) to 11 (for the death of the plant). According to this method, the product of Example 1 received a rating of 11 for tomato plants and a rating of 8 for bean plants.



  EXAMPLE 11.



   To evaluate the bactericidal activity of the product of Example 1, this product is mixed, at a concentration of 256 ppm, with distilled water containing 5% acetone and 0.01% "Triton". "X-1550 5 cc of the composition is placed in four test tubes and one of the organisms is added to each of these tubes: Erwenia amylovora, Xanthamonas phaseoli, Staphylococcus aureus, and Escherichia coli, under in the form of a saline solution of a bacterial suspension from plates of potato dextrose agar. The tubes are then incubated for 4 hours at 30 minutes and then transfers to sterile broths using an ordinary 4 mm eyelet.

   The broths thus inoculated are incubated for 48 hours at 37 and the bacterial development is evaluated using a% scale, in which the value 0 corresponds to zero development. According to this method, the product of Example 1 receives ratings of 0,0,0 and 0 for each of the above organisms.



  EXAMPLE 12.



   To evaluate in vitro the product of Example 1 as a contact poison against nematodes, the parasitic nematode of non-plants, Pa- nagrellus redivivus, is exposed by contact to the action of the chemical compound, in small glasses. of watches (27 mm in diameter by 8 mm in depth) placed in a 9 cm Petri dish. Aqueous compositions at 1000 ppm and 500 ppm of the product of Example 1, 5% acetone and 0.01% "Triton" X-155, are added to the nematode, the remainder being constituted by water.

   The results are noted 24 hours after the treatment o Mortalities of 100% and 100% respectively are found at the above concentrations o EXAMPLE 13
The remarkable potency of 3.4-dichlorothiophene 1.1-dioxide as a smoke poison against nematodes is shown by exposing the non-plant parasitic nematode, Panagrellus redivivus, to the vapor of the chemical compound, in small watch glasses (27 mm in diameter 8 mm deep) placed in a 9 cmo Petri dish The compositions to be tested contain respectively 2 and 1 mg of the product of Example 1, with 5% acetone, 0.01% Triton X- 1559 the remainder being constituted by water.

   These compositions are placed in watch glasses, but are not in contact with the nematodes. Observations after 24 hours indicate mortalities of 100% and 100% respectively, with 1.1-dioxide of 3.4-dichloro -thiophene used at the above concentrations.



    EXAMPLE 14 Preparation of 2.4-dichloro-thiophene 1,1-dioxide.



   5.16 g (0.02 molecules) of 2030404-tetra-chloro-tetrahydro-thiophene 1,1-dioxide are dissolved in 20 cm3 of methanol and the solution is cooled in an ice bath. 2.85 g of concentrated NH4OH (0.06 molecules of NH3 in water) are added in several portions. A precipitate of am- chloride is formed.

 <Desc / Clms Page number 9>

   monium but, on addition of 250 om3 of water, this precipitate is redissolved and the desired product precipitates in the form of an oil. The mixture is extracted, and crystallized from chloroform, benzene and petroleum ether. The desired product is thus obtained, of formula C4H2Cl2O2S.



  EXAMPLE 15.



  Preparation of 2.3.4-trichloro-thiophene 1.1-dioxide.



   5.1 g (0.02 molecules) of 2.3.4.4-tetrachlo-ro-2.3-dihydro-thiophene 1.1-dioxide are dissolved in 50 cc of methanol, then 2 cm3 of 28% aqueous ammonia are added. and the solution is left to stand for about 15 to 24 hours. By dilution with 500 cm3 of water, the desired product precipitates in the form of an oil. After extraction and recrystallization from chloroform, carbon tetrachloride, petroleum ether, benzene and cyclohexane, the desired product C4HCl62S is obtained, the ultraviolet spectrum of which has peaks at 238 m and 312 m.



   These compounds also show markedly different biological activity from other substituted and unsubstituted tetrahydrothiophene 1,1-dioxides and substituted and unsubstituted dihydro-thiophene 1,1-dioxides, as well as other halogenated pesticides.

   Examples thereof are given in Table III below, in which certain biological activities of 1.1-dioxide 304-dichloro-thiophene, 1.1-dioxide 3.4-dichloro-2.3-dihydro-thiophene, 1.1 are compared. -3.4-dichloro-tetrahydro-thiophene dioxide ,, 4-chloro-2.3-dihydro-thiophene 1 1-dioxide and 3.4-dihydro-thiophene 1.1-dioxide

 <Desc / Clms Page number 10>

 
TABLE III BIOLOGICAL ACTIVITY.
 EMI10.1
 Compound Concentration inhibiting germina- Formula Nom tion of at least 50% of aporee Formula Name on at. Oleracea and M. Prueticola M A. Oleracea M. Pructicola 41-C C-C1 M 1.1-dioxide of 1 ppm. 1 ppm.



  3.4-dichloro- H-C S bzz thiophene 0 '! 0 H Cl-c ### 0-01 1,1-dioxide from 10 - 100 ppm. 10 - 100 ppm.



  3.4-dichloro- H-0 EC 2.3-dihydro-2 thiophene 0 ^ 10 H H C1-Q --- C¯Cl 1.1-dioxide of 1000 ppm. 1,000 ppm.



  3.4-dichloro- tetrahydro- -u2u %% S, 2 thiophene 0 \ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯ H HO - 0-01 1.1-dioxide of 100 - 1000 ppm. 100 - 1000 ppm, 4-ohloro-2.3-dihydro- H-C CH2 thiophene 0- Ô H2C CE2 1.1-dioxide of 1000 ppm. 1000 ppm. tetrahydro- thiophene H2C CH2 00¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ HC CH 1.1-dioxide 100 - 1000 ppm . 1000 ppm.



  3 ° -dihydro-, thiophene 0 OH2 0 "'0'

 <Desc / Clms Page number 11>

 EXAMPLE 16
Part A Preparation of 3.3.4.5-tetrachloro-2.3-dihydro-thiophene 1.1-DIOXIDE.



   103 g (0.352 molecules) of 2.3.3.4.4-penta-chloro-tetrahydro-thiophene 1.1-dioxide are dissolved in 700 cm3 of hot 85% ethanol and 200 cm3 of water are added. The solution is allowed to cool to room temperature; Crystallization then occurs. The solution is then cooled for 3 hours in the refrigerator and filtered. 500 cm 3 of water are added to the filtrate (900), the mixture is allowed to cool slowly overnight, then it is cooled to -25 and filtered. After two recrystallizations from petroleum ether, a total of 51 g of a solid, melting point 70.5-72, is obtained.

   The elemental analysis below shows that the desired product has indeed been formed, of formula C4H2Cl4O2S.
 EMI11.1
 
<tb>



  Element <SEP> <SEP> values found <SEP> Calculated <SEP> values
<tb>% <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
<tb>
<tb> C <SEP> 18.72 <SEP> 18.77
<tb> H <SEP> 0.85 <SEP> 0.78
<tb> Cl <SEP> 55.6 <SEP> 5541
<tb>
 
The test compositions given below are aqueous compositions applied at the concentrations specified, unless otherwise indicated. These compositions are prepared by mixing the toxicant in water, generally with a solvent, for example with 5% acetone and an emulsifier such as "Triton" X-155 (alkyl-aryl-polyether- alcohol).



   Part b
The product of Part A is evaluated as toxic against the cockroach Blatella Germanica and against the Mexican weevil as follows: a) Cockroaches (Blattella Germanica) of 8 to 9 weeks old are anesthetized with carbon dioxide in order to facilitate their handling and then immersed in compositions of the product of Part A (2000 ppm and 1000 ppm respectively) for 10 seconds, removed, excess liquid removed and caged.

   Two batches of 10 insects each are treated in this way. Mortality observations after 3 days indicate a mortality of 100% at the concentration of 2000 ppm and of 100% also at the concentration of 1000 ppmo b) The operation is carried out on lexicon weevil larvae (Epilachna varives- tis) in their fourth moult, less than 1 day old in the moult. Dico- tyledons excised from "Tendergreen" bean plants are immersed in the compositions of the product in part A (2000 ppm and 1000 ppm respectively) until fully wetted then allowed to dry.

   Each sheet is then placed in a 9 cm Petri dish, lined internally with filter paper, and 10 larvae chosen at random are introduced into the dishes. After 3 days of exposure, a mortality of 100% at the concentration of 2000 ppm and also a mortality of 100% at the concentration of 1000 ppm.



   Part c
To show the fungicidal activity of the compounds according to the invention, germination tests are carried out with the product of part A of this example, by the method recommended by the "American Phytopathological Society". This method consists in using compositions containing the product of part A at concentrations (before dilution of 4 volumes with 1 volume of stimulant and of spore suspension) of 1000 '100, 10 and 1 ppm respectively and µ1 put them in. contact with organisms to inhibit the germination of poreso More particu-

 <Desc / Clms Page number 12>

   First, spores of 7-10 day old cultures of Alternaria oleracea and Monolinia Fructicola are contacted with the fungicide.

   The product of part A shows a D 50 value (concentration inhibiting the germination of half of the spores in the test drops), for both Ao Oleracea and M. fructiola, of 0.01 to 0.1 ppm or less, which is better than the corresponding D 50 of 1 to 10 ppm of copper sulfate as a reference material.



   Part D
To show the power of inhibition on the germination of the seeds of the product of part A, tests are carried out on English ryegrass seeds and on radish seeds. These seeds are treated in boxes of Pepper. tri, with an aqueous suspension of the product of part A, at the respective concentrations of 1000 and 100 ppm. Batches of 25 seeds of each species were scattered into individual boxes containing filter paper discs moistened with 5 cm 3 of the compositions to be tested. After 7 to 10 days, the inhibitory power of the compound was evaluated. on seed germination, in the same way as in part C of this example. D 50 values of less than 10-100 ppm are found, that is to say a strong inhibition of seed germination.



   Part E
To assess the effect of the product of part A on seed germination in soil, a mixture of seeds from 6 harvest plants is placed in a 20 x 20 x 5 cm metal cake pan filled to 1 cm. from the edge with greenhouse soil. Cover the seeds evenly with about 1/2 cm of potting soil and water them. After 24 hours, 80 cm3 of an aqueous composition containing the amounts indicated below of the product of the part are sprayed uniformly on the surface of the mold, under an air pressure of 0.7 kg. A. The treatment corresponds to the applications below, given in kg per hectare. The seed mixture includes seeds of 3 broadleaf leaves (turnip, flax and alfalfa) and seeds of 3 grasses (wheat, millet, rye).



   Condition rating (%) compared to control
 EMI12.1
 
<tb> Application, <SEP> in <SEP> Broadleaf <SEP> grasses
<tb>
<tb>
<tb>
<tb> kg / hectare
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 18 <SEP> 0 <SEP> 10
<tb>
<tb>
<tb>
<tb>
<tb> 9 <SEP> 10 <SEP> 40
<tb>
<tb>
<tb>
<tb> 4.5 <SEP> 15 <SEP> 50
<tb>
 
Part F
Tests for herbicidal activity of the product of Part A are carried out, both by direct action, for example by spraying on the leaves, and by endotherapeutic action as indicated by the watering tests of the soil.

   In the leaf spray test, 100 cm3 portions of a composition of the product of part A, at a concentration of 6400 ppm, were sprayed on tomato plants (No. 1) of the variety "Bonny Best", 13 to 18 cm in height, on maize plants (n 2) of the variety "Cornell" M-1, from 10 to 15 cm, on bean plants (n 3) of the variety "Tendergreen" and on oat plants (no. 4) of the "Clinton" variety. When the plants are dry, they are placed in a greenhouse and observed 14 days after this treatment.



   Phytotoxicity is assessed using a scale from 0 to 11, the number 11 indicating that the plant is killed o On tomatoes, beans, corn and oats, the respective values of 11, 11 are found , 2 and 3, which shows a selective action.,

 <Desc / Clms Page number 13>

 
In the soil watering trials, tomato and bean plants of the same variety and having substantially the same dimensions as in the spray trial are treated by pouring 51 om3 of a 2000 ppm composition. of the product of part A on 10 cm pots of soil containing the plants, treatment which corresponds to 146 kg per hectare. At this concentration,

   the tomato plants are completely destroyed and the number 5 is found in the bean plants
Part G
In order to determine the nematocidal activity of the product of part A, further tests are carried out with this product applied as a contact poison against nematodes of the species Panagrellus redivivus. The nematodes are exposed to the product of part A in small watch glasses (27 mm in diameter x 8 mm deep) placed in a 9 cmo Petri dish
The fumigation activity is determined by placing, in 3 individual Petri dishes, respectively 64, 32 and 16 mg of product per dish. At these concentrations, the mortalities after 24 hours are 86%,

       66% and 8% respectively o
Part H
To determine the bactericidal activity of the product of part A, this product is applied against the bacteria Erwenia amylovora and Xanthomonas phaseoli. The evaluation of the development of the two organisms, 48 hours after an exposure of 4 hours to a composition at 100 ppm, gives the value 0% while the development is 75% and 94% respectively, in a control test.
Part i
The efficacy of the product of part A for the protection of cucumber seeds against mold and rot fungi is determined. The average (%) states at various doses of active ingredient expressed as% of the weight of the seeds are The following:

   
State (%) average number of days after
Dose in% of sowing weight of seeds
 EMI13.1
 
<tb> 11 <SEP> 15 <SEP> 20
<tb>
<tb> 0.036 <SEP> 57 <SEP> 63 <SEP> 60
<tb>
<tb> 0.012 <SEP> 44 <SEP> 51 <SEP> 50
<tb>
<tb> 0.004 <SEP> 6 <SEP> 17 <SEP> 17
<tb>
 
Part J
To illustrate the fungicidal activity of the product of part A in the protection of seeds, the compound is applied in the form of a powder containing 5% of active ingredient, with pyrophyllite as vehicles. Pea seeds are treated with this composition. at 3 different doses, namely - 0.018, 0.006 and 0.002% of active ingredient relative to the weight of seeds o Each dose is applied in eight times in a soil infested with Pythium using 25 seeds each time o The following results are obtained:

   

 <Desc / Clms Page number 14>

 
 EMI14.1
 
<tb> <SEP> rate of emergence <SEP> (%)
<tb>
<tb>
<tb>
<tb>
<tb> After <SEP> 7 <SEP> days <SEP> 1 <SEP> After <SEP> 14 <SEP> days <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> Dose <SEP> of <SEP> active <SEP> material, <SEP> in <SEP>% <SEP> of <SEP> weight <SEP> of <SEP> seeds <SEP> * <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> Processing <SEP> 0.018 <SEP> 0.006 <SEP> 0.002 <SEP> 0 <SEP> 0.018 <SEP> 0.006 <SEP> 0.002 <SEP> 0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 1.1-dioxide <SEP> of
<tb>
<tb>
<tb>
<tb> 3.3.4.5-tetra- <SEP> 86 <SEP> 68 <SEP> 26- <SEP> 87 <SEP> 69 <SEP> 30 <SEP> - <SEP>
<tb>
<tb>
<tb>
<tb> chloro-203-dihy-
<tb>
<tb>
<tb>
<tb> dro-thiophene
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> <SEP> indicator of <SEP> earth
<tb>
<tb>
<tb>
<tb> not <SEP> processed- <SEP> - <SEP> - <SEP> 0,

  5 <SEP> - <SEP> - <SEP> - <SEP> 1.0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> <SEP> indicator of <SEP> earth
<tb>
<tb>
<tb>
<tb> sterile- <SEP> - <SEP> - <SEP> 65- <SEP> - <SEP> - <SEP> 97
<tb>
   @ 0.12% of the weight of seeds = 0.87 g per liter of peas 0.0625% of the weight of seeds = 0.625 g per kg of seeds.



   Part K
To show the fungicidal activity in fumigations, the same technique is applied as in part F of this example, with a 9 cm Petri dish as the test chamber. A suspension of spores (0.5 cm3 in small duplicate watch glasses, 27 mm in diameter by 8 mm deep) is placed in the Petri dish, with the product of part A contained in a watch glass. individual identical, then the box is closed with its cover. Note the inhibition of spore germination 18 hours later. For Alternaria ole- racea,

   a concentration of 4 micrograms per box completely inhibits the germination of spores
Another example of the potency of the product of part A of this example for the fumigation protection of tomato leaves against early rust is as follows: Tomato plants exposed to a suspension of ¯ spores of the species Alternaria Solani are placed under a series of inverted jars, in a tub of water. Small watch glasses containing the product of part A, which evaporates from an acetone solution, are placed on the earth under the plants which grow in 10 cmo clay pots The jars serve as humid chambers individual; an infestation thus occurs.

   Under these conditions and at the concentration of 64 micrograms of active compound per jar, early rust is completely suppressed.



    EXAMPLE 17
Part A Preparation of 3.3.4-trichloro-2.3-dihydrothiophene 1.1-dioxide.



   100 g (0.388 molecules) of 3030404-tetra-chloro-tetrahydro-thiophene 1.1-dioxide, compound described in US Patent Application No. 760,445, are dissolved in 500 cm3 of methanol containing 0.581 molecules of pyridine, for 10 minutes, then the solution thus obtained is poured into 3 liters of water.



  After several recrystallizations from a benzene-cyclohexane mixture, one obtains

 <Desc / Clms Page number 15>

 40.8 g of white crystals which melt at 108.5-109.5 cc The elemental analysis below shows that the desired compound was indeed obtained, of formula C4H3Cl62S
 EMI15.1
 
<tb> Element <SEP> Found <SEP> values <SEP> Calculated <SEP> values
<tb>
<tb>
<tb>% <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
<tb>
<tb>
<tb>
<tb> C <SEP> 22.22 <SEP> 21.69
<tb>
<tb>
<tb> H <SEP> 1.58 <SEP> 1.36
<tb>
<tb>
<tb> Cl <SEP> 48.2 <SEP> 48.02
<tb>
 
Part b
The following tests illustrate the insecticidal activity of the product of part A of this example.

   a) On the same Mexican weevil and according to the process given in part B of example 16, the product of part A of this example, at the concentration of 2000 ppm, causes 100% mortality. b) Is placed on a piece of cotton wool 10 cm3 of the above material, at a concentration of 2000 ppm, in the form of an aqueous composition containing 10% sugar.Over the cotton wool thus impregnated, it is cages 25 house flies 45 days old and after 24 hours the flies killed are counted.



  There is a 28% mortality.



   Part c
The tests described in part C of Example 16 are reproduced in order to show the fungicidal activity of the product of part A of this example. According to this method, for the product of part A of this example, D 50 values of 0.01 to 0.1 ppm or less were found against both A.

   oleracea and M.fructico- la
Part D
To illustrate the effectiveness of the product of part A as a fungicide in soils, by its power to protect seeds and seedlings against fungi of mold and rot (fungi of the species Pythium and Fusarium), we deal with infested compost, in boxes of 10 x 10 x 8 cm, watering it with an aqueous composition of the product from part Ao The treatment corresponds to 36 kg of product per hectare. The soil thus treated is left for a day, then it is removed from each box and mixed thoroughly before returning it to the boxes.



   Three days after this treatment, 25 pea seeds of the variety "Perfection" are sown in each box at a uniform depth. As controls, seeds were also planted in untreated soil and in sterilized soil. 14 days after inoculation, the state (in%) is noted.

   According to this process, at the application rate of 36 kg per hectare, we find a state of 1% for the untreated control soil, 85% for the sterilized control soil and 100% for the treated soil. with the compound tested, which shows a very high activity of the product as a fungicide in solso \
Part E
Bean plants of the variety "Tendergreen" and tomato plants of the variety "Bonny Best", growing in 10 cm pots, are treated by pouring into the pots the composition of the product of part A at the concentration. tion of 2000 ppm. The treatment is equivalent to an application of 146 kg per hectare (102 mg per pot). It is observed, 9 and 14 days after this treatment, that the two kinds of plants, tomatoes and beans, are killed.

   Further tests are carried out to show the phytotoxicity of the product both by direct action eg by spraying on the leaves and by endotherapeutic action, as indicated by the soil watering tests. In the spray test on

 <Desc / Clms Page number 16>

 leaves, is sprayed on tomato plants of the variety "Bonny Best", 13 to 18 cm in height, 100 cm3 portions of a composition of the product of part A of this example, at a concentration of 6400 ppmo When the plants are dry, they are placed in a greenhouse and examined 14 days after treatment. Phytotoxicity is rated on a scale of 0 to 11, with 11 indicating complete destruction.

   In this test the value 11 is found for the tomato plants o In the soil watering tests, tomato and bean plants of the same variety and substantially the same dimensions are treated as in the spray tests, by pouring 51 cm3 of a composition at 2000 ppm of the product of part A into 10 cm pots of soil containing the plants, the treatment corresponding to an application of 146 kg per hectareo A la concentration used, both kinds of plants, tomatoes and beans, are killed.



   Part F
The baotericidal activity of the product of part A is determined according to the test method of part H of Example 16, but by operating on the bacteria Staphylococcus aureus and Escherichia colio. The development of the two organisms, 48 hours after a 4 hour exposure to the action of the compound at the concentration of 1000 ppm is 25% and 40% respectively, while the growth of control organisms is 68% and 60% respectively.



   Part G
According to the method of part D of Example 16, values of D 50 of 10 to 100 ppm are found, both for perennial ryegrass seeds and for radish seeds.



   Part H
According to the test method of part G of example 16, the following results are obtained:
 EMI16.1
 
<tb> Dose <SEP> Status <SEP> (%) <SEP> evaluated, <SEP> compared <SEP> to <SEP> control
<tb>
<tb> in <SEP> kg <SEP> to <SEP> per hectare <SEP> broadleaf <SEP> grasses
<tb>
<tb> 73 <SEP> 0 <SEP> 0
<tb>
<tb> 36.5 <SEP> 0 <SEP> 1
<tb>
<tb> 18.25 <SEP> 0 <SEP> 115
<tb>
 
Part 1
Parasitic nematodes of non-plants (Panagrellus redivi- vus) are exposed to the action of the product of part A in small watch glasses (27 mm in diameter x 8 mm in depth) in a 9 cm Petri dish and the results are noted 24 hours after the treatment. According to the above method, there is a mortality of 100% both by contact action and by smoke action,

   at concentrations of 1000 and 500 ppm.



   Part J
The method of Part K of Example 16 is reproduced with the compound of part A of this example. The same high activity is found by smoke action.



   In addition to the particular applications which have just been illustrated, it will be noted that the application as a fungicide covers both plant and non-plant fungi. In addition, the biological activity comprises the activity both against the parasites of plants. plants and non-plants, including micro-organisms, this term being taken in a broad sense which includes both animal and plant organisms
It goes without saying that modifications can be made to the methods of

 <Desc / Clms Page number 17>

 realization which has just been described, in particular by substitution of equivalent technical means, without going beyond the scope of the present invention,
CLAIMS.



   1. - As new industrial products: Compounds corresponding to the formula:
 EMI17.1
 wherein X denotes halogen, m a number from 1 to 4 inclusive Y is selected from the group consisting of hydrogen and halogen and n1 and n2 are the same or different numbers with a value of 0 to 1 inclusive and, if n1 and n2 are all two equal to 0, m is greater than 1 and the unsatisfied valences of carbon atoms 2 and 3 determine a double bond between these atoms.



   20 - Compounds corresponding to the formula:
 EMI17.2
 in which X1, X2, X3 and X4 denote hydrogen or halogen atoms, at least one of the substituents X being a halogen.

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

30 - Compounds corresponding to the formula: EMI17.3 in which X denotes a halogeno EMI17.4 - 204-dichloro-thiopheneo 1.1-dioxide 5a - 34-dichlorothiopheneo 1.1-dioxide 60 - 2.3o4-trichloro-thiopheneo lol-dioxide 7. - Process for preparing a compound of formulas <Desc / Clms Page number 18> EMI18.1 which comprises dehydrohalogenization of a compound of formula-. EMI18.2 wherein X1, X2, X3, X4, X5 and X6 are selected from the group consisting of hydrogen and halogen atoms, at least three of these Xs being halogen, with an alkylene reagent. 8. - A method according to claim 7 characterized in that the alkylene reagent is ammonia. 9. - Process for preparing a compound represented by the formula: EMI18.3 wherein X is selected from the group consisting of hydrogen and halogen atoms, at least one X being halogen, characterized in that a compound of the formula is chemically reacted: EMI18.4 wherein X2, X2, X5 and X6 are selected from the group consisting of hydrogen and halogen atoms, at least three of such X being halogen, with an alkyleneo reagent 10. - Process according to claim 9, characterized in that the alkylene reagent is ammonia <Desc / Clms Page number 19> 11.- Process for preparing a compound of formula: EMI19.1 in which Z1, Z2, Z3 and Z4 are chosen from the group consisting of hydrogen and halogen atoms, at least one Z being a halogen, characterized in that a compound of formula is dehydrohalogenized: EMI19.2 wherein X1, X2, X3, X4, and X5 are selected from the group consisting of hydrogen and halogen atoms, at least X2 and another X being halogen, two moles of HX being removed, with a reagent alkylene. 120 - Process according to claim 11, characterized in that the alkylene reagent is ammonia. 13. - Process for the preparation of a polychlorothiophene 1,1-dioxide characterized in that dehydrohalogenizes a polychlorotetrahydrothiophene 1,1-dioxide with ammonia. 140 - Process according to claim 13, characterized in that the reaction is carried out in the presence of an inert solvent at a temperature below 115 C. 15.- A process for preparing a polychlorothiophene 1,1-dioxide characterized in that dehydrohalogenizes a polychlorodihydrothiophene 1,1-dioxide with ammonia. 16. - Process according to claim 15, characterized in that the reaction is carried out in the presence of an inert solvent at a temperature below 115 C. 170 - Process for the preparation of a 1,1-dioxide 3,4-dihalothiophene characterized by chemically reacting a 1,1-dioxide 3,3,4,4-tetrahalotetrahydrothiophene with an alkaline reagent 18. A process according to claim 17, characterized in that the alkaline reagent is ammonia and in that the reaction is carried out at a temperature below 115 ° C. in the presence of an inert solvent. 19.- Process for the preparation of a 191-dioxide 3,4-dichlorothiophene characterized in that a 1,1-dioxide 3,3,4,4-tetrachlo-rotetrahydrothiophene is chemically reacted with an alkaline reagent 200 - Process according to claim 19, characterized in that the alkaline reagent is ammonia and in that the reaction is carried out at a temperature below 1150C in the presence of an inert solvent. 21. - A process for preparing a 1 ', 1-dioxide 23,4-trichlorothiophè- ne, characterized in that dehydrohalogenizes a 1,1-dioxide 2,3,4,4-tetrachloro- <Desc / Clms Page number 20> dihydrothiophene with ammonia at a temperature below 115 ° C, in the presence of an inert solvent. 220 - Process for the preparation of 1'.1-dioxide 2,4-dichlorothiophene EMI20.1 characterized in that dehydrohalogenizes a 1,1-dioxide 2y344-érachloroté = rahdrohio with ammonia at a temperature below 115 ± 1C in the presence of an inert solvent 23. - Composition of biologically active material characterized in that it comprises as active ingredients a compound represented by the formulas EMI20.2 X2 C ¯X3 X2-1 * - X1-0 S / O-X3 0 / - '---. È 0 wherein X 19 X29 X3 and X4 are selected from the group consisting of atoms of hydrogen and halogen, at least one X being halogen, and a supporto 24. - Compositions of biologically active material, characterized in EMI20.3 which it comprises as active ingredients a 3g4-d.ihaZothiophene lel-dioxide and a carrier. 250 - Method of controlling the growth of insects, characterized in that these insects are brought into contact with an active amount of 1,1-dioxide EMI20.4 3,4-dichlorothiophene 26. - Method for controlling the growth of fungi, characterized in that these fungi are brought into contact with an active amount of 1,1- EMI20.5 34-diohlorothiophenec dioxide 270 - A method of controlling the growth of plant parasites, characterized in that these plants are brought into contact with an active amount of 1,1-dioxide 3,4-dichlorothiophene. 28. - Process for controlling the growth of microorganisms, characterized in that these microorganisms are brought into contact with an active quantity EMI20.6 1,1-dioxide 3,4-dichloro-thiopheneo 29. - A method of controlling the growth of nematodes, characterized in that these nematodes are brought into contact with an active amount of 1,1-dioxide EMI20.7 3,4-dichlorothiophènao 30. - Polyhalotetrahydrothiophenes 1,1-dioxide having the formula: - EMI20.8 wherein X is halogen, m is a number from 3 to 6 inclusive and n is a number equal to (6-m). EMI20.9 310 - 1,1-Dio-xyde 393,495-tetrahydrothiophene. 32 0 - 1,1-diode 3,3,4-trichloro-2,3-dihydrothiopheneo 330 - 1,1-dioxide 3s35- riohloro23-dihydrothiophene 34. - Process for preparing a compound having the formula: <Desc / Clms Page number 21> EMI21.1 in which X is a halogen, m is a number from 3 to 6 inclusive, and n is a number equal to (6-m), characterized in that a reagent having the formula is monodehydrohalogenized EMI21.2 where X is halogen, m is a number from 3 to 6 inclusive, and n is a number equal to (6-m) o 350 - Process according to claim 34, characterized in that the monodehydrohalogenization is carried out in the presence of an organic liquid. 360 - A method according to claim 34, characterized in that the monodehydrohalogenization is carried out in an alkaline medium 37. - Process according to claim 34, characterized in that the monodehydrohalogenization is carried out by dissolving the reagent in an aqueous alkanol 380 - Process according to claim 34, characterized in that the monodehydrohalogenization is carried out by dissolving the reagent in a boiling alkanol 'containing a small amount of a soluble base, and in that the product is then separated. 39. - Composition of biologically active material, characterized in that it comprises a major proportion of a carrier and a biologically active amount of a compound of formulas EMI21.3 where X is halogen and m is a number from 2 to 6 inclusive 40. - Composition of biologically active material, characterized in that it comprises a major proportion of a carrier and a biologically active amount of a compound of claim 31 41. - Composition of biologically active material, characterized in that it comprises a major proportion of a carrier and a biologically active amount of a compound of claim 32. 420 - A composition of biologically active material, characterized in that it comprises a major proportion of a carrier and a biologically active amount of a compound of claim 33. 43. - Composition of biologically active material, characterized in that <Desc / Clms Page number 22> that it comprises a major proportion of a carrier and a biological quantity EMI22.1 active ment of 1,1-dioxide 39Q.dichloro-z $ 3-dihydrothiophene. 44. - A method of regulating the growth of plants, characterized in that the composition of the claim 39 is applied to the growing plants. 45. - A method of regulating the growth of plants characterized in that the composition of claim 400 is applied to the growing plants. 460 - A method of regulating the growth of plants characterized in that the composition of claim 410 is applied to the growing plants 47. - A method of regulating the growth of plants, characterized in that the composition of the claim is applied to growing plants 42. 480 - A method of regulating the growth of plants, characterized in that the composition of claim 43 is applied to growing plants. 49. - Process for the extermination of microorganisms characterized in that these microorganisms are brought into contact with a compound of formula.- EMI22.2 where X is halogen, 1 is a number from 3 to 6 inolusively and n is a number equal to (6-m) 500 - Process according to claim 49, characterized in that the ex- determination is carried out by a smoke action 51. - All elements, combinations of elements, process phases or combinations of new phases or processes described and claimed above.