IL31149A - Amides derived from trichlorothiophene - Google Patents

Description

31149/2 Amides derived from trichlorothio- phene PEPRO, Soci^te" pour le De eloppement et la Vente de Speciality's Chimiques - lb or R and R* may form, together with the nitrogen atom to dln~oh¾4-oxo«-which they are attached, a piperidine, oxazoll&e , aea¾)g- oxazolidj»e*;2-thione, morpholine, iinft-,/piperazine or hexamethylenelmine ring, optionally substituted With alkyl radicals with 1 to 4 carbon atoms, or wit a 3f4i»5-trichlorothienyl-2-carbonyl radical.

The compounds of the invention are prepared in three stages, from tetraohlorothiophene.

Trichloro-3,4,5-thiophene-2- arboxylic acid is prepared first by dissolving tetraohlorothiophene in tetra' hydrofuran, and treating it then with magnesium, in the presence of traces of an alkyl halide; then, carbon dioxide gas is allowed to act on the organo-magnesium compound thus obtained, and, lastly, the reaction mixture is hydrolysed with a slightly acidified aqueous solution.

The chloride of the above acid is then prepared, according to the conventional method, by using thionyl chloride.

Lastly, the acid chloride thus obtained is condensed on an amine having the formula NHRR1 (wherein R and R' have the meaning mentioned hereinabove), so as to obtain the amides or anilides forming the subject-matter of the present invention.

Using tetrachlorothiophene as the raw material is very advantageous from an economic standpoint. As a matter of fact, as is well known, this compound is readily obtained by allowing sulfur. to react with hexachlorobutadiene , the latter being in turn a by-product of the manufacture of carbon tetrachloride. Tetrachlorothiophene is therefore a raw material readily available at very low cost.

I2- The trichloro-3 , , 5- hiophene-carboxylic /-1 acid is obtained according to the method described by Steinkopf , Jacob and Penz in "Annalen der Chemie", 1934, pages 50 and upwards. The only difference lies in the fact that we used anhydrous and deperoxidised tetrahydrof uran as a solvent, whereas Steinkopf & al. used ether. As a matter of fact, we fomd that the acid yield was much better. * 2— Trichloro- ,4-,5-i'thiophene-earboxylic/i-? acid chloride is obtained through the action of thionyl chloride, according to the conventional method. The yield is exceedingly good, as shown by the following example: Example 1 : Preparation of trichloro- , ,5'-'thiophene-/carboxylic ^ acid, chloride A mixture of 23.15 g' (0.1 mole) of trichloro- ,4-,5-thiophene heated, to 50-60°C. As soon as the release of acid fumes is completed, the mixture is brought to a boil for one hour.

The excess thionyl chloride is then removed, and the acid chloride is rectified at reduced pressure. Boiling point: 124-125°C under 10 mm Hg. Yield: 92$.

The aliphatic, aromatic, and heterocyclic amides forming the subject-matter of the present invention, are obtained by allowing ammonia, or an amine which may be dissolved in an organic solvent, to act on the above acid chloride, in the presence of an acid acceptor such as triethylamine, pyridine, and the like, or in the presence of the amine itself.

Example 2 : Preparation of the trichloro-2 ,4- ,5-anilide of the .91 g (Ο.Ο25 mole) of trichloro-2, ,5-aniline , dissolved in 80 cc of anhydrous toluene, were mixed with 2.52 g (0.025 mole) of triethylamine. 6.25 g (0.025 mole) of trichloro-3 , ,5-thiophene carboxylic-2 acid chloride, dissolved in 60 cc of anhydrous toluene, were then added slowly to the mixture, at ordinary temperature .

The whole mixture was then brought to a boil (109°C) for two hours, and then allowed to cool, so that the triethylamine poured hydrochloride precipitated. The reaction mixture was then 6k3?ew« into 200 cc of water, and the supernatant organic phase was decanted off, washed free from chloride ions, and then dried over anhydrous magnesium sulfate.

After evaporating the toluene, the anilide was obtained as a crystallized solid residue. Melting point: 22 °C. Yield: 81.9%'.

By using a similar method, we obtained the following compounds : The compounds of the invention have advantageous pesticidal properties, which enable them to be used for solving a large number of problems, in particular in phyto-pha'rmac .

As a matter of fact, depending on the nature of the radicals R,'R.' , and on the doses and conditions of use, products are obtained, which are: -either herbicides, the activity' of which is either selective, which enables them to be used for destroying the whole of the adventitious weeds likely to interfere with the growth of a crop, or total, which enables them to be used when it is desired to remove any plant life from a given location, some of said compounds having their maximum activity in treatments effected before sowing or planting the plants, others in pre-ccming up treatments (effected after sowing the plants, but before the latter, or the ill-weeds, come up), and others in treatments effected when the plants and/or ill-weeds have come up; - or powerful nematicides, adapted to be used for treating grounds infested with nematodes; - or else fungicides, adapted to be used for fighting against the enemies of plants and crops, and for protecting materials ■ stored or worked up; - or, again, insecticides, adapted to be used for fighting agains the conveyors of human or animal diseases, against the enemies of plants and crops, and for protecting materials or products stored or worked up.

The following examples bring out some of the aspects of the pesticidal activity of the compounds of the invention. Said examples are given only by way of illustration, and the applications they describe do not limit the scope of the inventio in any way. Obviously, the present invention embraces all utilizations of the compounds having the formula (1), whatever the conditions and doses used may be.

TESTS FOR HERBICIDAL ACTIVITY Example - Product N° 3, when used at a dose of 10 kg/ha before the plants come up, destroys the turnips completely, while keeping a very good selectivity as regards ¾ΧΗ3Ϊ¾ΪΚΚ¾: millet-grass.

V/hen used at the same dose after the plants have come up, it destroys the turnips completely, while showing 3 very good selectivity as regards certain graminaceae. 42 Example - Product N° 16, when used at a dose of 8 kg/ha before the plants come up, destroys completely the followin adventitious plants: panic-grass, false oat, foxtail millet-grass, while being absolutely selective as TEST FOR NEMATICIDAL ACTION Example ^> - 10. cc of a solution of the product to be tested were poured into 250 ce screw-cap powder flasks, and then 3-4- drops of a concentrated solution of 4-day old nematodes (Coenorhabd itis elevens) were added thereto. After 48 hours, the result was observed, by means of a binocular magnifying lens, to obtain the death rate.

Under such conditions, products Nos. 4, 8, » 10, 11, 16, 18, 26, 36 and 38, at a dose of 0.1 g/1 , cause the death of 100?· of the nematodes.

TESTS FOR FUNGICIDAL ACTIVITY ON LIVING PLANTS Example These tests correspond to preventive treatments, and consist in spraying a wash containing 2 g/1 of active material over the plant. The latter is then infected with spores of the fungus selected . After from 5 to 15 days, depending on the fungus selected, the growth of said fungus is observed .

Corn-milde : in this test, products Nos. 4, 8, 9 , 10, 11 , 16, 18, 36 and 38 give a good and complete protection against Erisyphe fzraminis, which is the cause of corn-mildew.

Under the same conditions, but with a dose twice as small, products Nos. 9 , 10, 11, 18 and 36 still ensure a complete protection.

Bean brown rot: in this test, products Nos. 3, 5 ,30, 48, 75, 77 and 83 &&—½Q ensure a complete protection against Uromyces appendiculatus , which is the cause of the brown rot 45 Example Vine mildew The treatment is effected with a wettable powder containing 0.01 g/1 of active material, on a vine viticola Under such conditions, products Hos. 11, 19, 22 and 28 prevent totally the growth of the parasitic fungus.

Septoriose on celery: in this test, product No. 70 ensures a complete protection against SeTtoria apii which is the cause of the septoriose.

Alternariose on tomato: in this test , product DTo . 82 ensures a complete protection against Alternaria solani which is the cause of the alternariose.

TESTS FOR INSKCTICIDAL ACTIVITY Example 46: Activity against "Aedes aegypti" Larvae of Aedes ae,qypti are put in an aqueous solution containing 20 mg/l;of active material, and after 2 days the larvae dead and alive are counted.

Under such coj¾ditions, products Hos* 3» 4, 5» 6, 8, 9 10, 11, 16, 17, 20, 26, 28, 36, 49, 50, 51, 54, 55, 58, 61, 62, 64, 70, 71, 73, 74, 76 and 77 cause a 100?S death rate among the larvae.

Example 47: Activity against "Ephestia kuhniella" Small cups made of azyme are soaked with 3 drops of an acetone solution containing 2 g/l of active material.

After evaporation of the solvent, 10 eggs of Ephestia kuhniella are disposed at , the bottom of each cup, which is then closed by means of a glass plate. After 7 days the larvae dead .and alive are counted.

Under such conditions, prodicts J5ios* 3, 5» 8, 9, 10, 11, 16, 17, 36 and 74 cause the death (or prevent the hatching) - of 100$ of the larvae (or the eggs). Under the same conditions, "but at a dose .of 0.5 g/l, product No. 36 still causes the death (or prevents the hatching) of 100 of the larvae (or of the eggs).

Activity against "Tetranychus urticae" Small round pieces of leaves of bean stro¾ly contaidnated with Tetranychus urticae are treated with an acetonic solution containing 1 g/l of active material.

After ti?o days the larvae dead and alive are counted. Under such conditions, products Dioa. 64, 70 and 71 cause the death (or prevent the hatching) of 100$ of the larvae (or of the eggs) · Further examples of compounds according to the invention given in the following Table: 31149/;! ! . 31149/1 # - 14 31149/2 The compounds of the invention should for the practical use thereof, be formulated according to the technics conventionally used in the pesticide industry. ' ' Thus, they may be used as powders to be sprinkled, wettable powders, solutions, direct or reversed emulsions of water in oil, or oil xn water, and the like.

Such various types of formulations require then the addition of inert carriers, such as clays, talc, or the like, and/or solvents, such as water or organic solvents, as. well as the addition of various adjuvants adapted to further the use and improve the physical properties of the compositions produced. Such adjuvants, depending on the particular composition, may be emulsifying agents, and/or antleaking agents, and/or wettin agents, · and/or ' sticking agents , and the like, the addition of which to parasiticidal compositions is well known of those skilled in the art. 31149/3 - 15 - <

Claims (5)

1. Amides derived from trichlorothiophene and having the formula wherein R and ' are the same or different and are each hydrogen, straight or branched alkyl radicals containing from 1 to 6 carbon atoms or alkenyl radicals containing from 2 to 6 carbon atoms all of which may optionally be substituted with halogen atoms or cyano radicals} alkoxyalkyl radicals, cycloalkyl radicals; and where R and R' are different one of them may also be a) an aryl radical (in particular phenyl, naphthyl or diphenyl), optionally substituted by one or more Identical or different alkyl, halogenated alkyl (in particular, CP^, CCl^) or alkoxy radicals with 1 to 4 carbon atoms in the alkyl moiety, N02» CN, halogens or by a 3»4,5-trichlorothlenyl-2-amino radical? b) furyl, tetrahydrofuryl, thiazolyl, pyridyl or 1,2,4-triazolyl optionally substituted with alkyl with 1 to 4 carbon atoms or nltro radicals and attached to the nitrogen atom either by a direct bond, or through an alkylene chain? or R and R' may form, together with the nitrogen atom dinone .. to which they are attached, a plperidine, oxazoline, / 4-oxo-oxazolidine-2-thione , morpholine, piperazine or hexamethyleneimine ring, 31149/2 - 16 -

2. '. Amide compounds of ±>rmula (l) in Claim 1 substantially as described herein with reference to the Examples and tables herein.

3. A process for the preparation of compounds of formula (1) in Claim 1 which comprises preparing trichloro-3 »4t 5-thiophone- 2-carboxyllc S acid, converting the acid by reaction with thionyl chloride into the corresponding acid chloride and condensing the the latter with an amine of the formula wherein R and R' have the same meanings as in Claim 1.

4. A process according to Claim 3i substantially as described herein with reference to the Examples.

5. Parasiticidal, in particular Insec'ticidal, fungicidal nematioidal and herbicidal compositions containing as an active ingredient a compound of formul (1) in Claim 1. For the Applicants DR.REINHOLD COH AND PARTNERS PC:BH