CS195697B2 - Method of preparing substituted n-/2,2-difluoralkanoyl /-o-phenylendiamides - Google Patents

Description

Proprietor of the patent ELI LILLY AND COMPANY, INDIANAPOLIS (Sp. St. A,) +;

(54) A process for the preparation of substituted N- (2,2-difluoroalkanoyl) -o-phenylenediamines

The invention relates to novel ring-substituted N- (2,2-difluoroalkanoyl) ^-1- phenylenediamines. These compounds are useful as herbicides.

Rumanowski, U.S. Patent No. 3,557,211 discloses Ν, Ν-bis (acetyl and ^L) phenylenediamines which are useful for controlling plants, insects and fungi.

one feature of the invention are compounds that are effective as systemic herbicides.

The invention relates to novel ring-substituted N- (2,2-difluoroalkanoyl) -o-phenylenedlamines of formula III,

NH-R ° '

NH ~ R ^Z (////) where

R c is 2,2-difluoroalkanoyl of formula '^;'-C + -CF2-Y',

\ \ \ / /

·. . . . ° where Y is a fluorine atom, ··

198897

. R ² is R ^ft , furoyl or acetyl.

R ⁶ is C 1 -C 4 alkylsulfonyl and is located at the 4 or 5 position.

The compounds of formula III are prepared by introducing a characteristic 2,2-difluoroalkanoyl group into the corresponding corresponding diamine of the starting material. The introduction of this group can be carried out by any of the available acylation reactions using different types of acylating agents of formula IV.

HO — C — CF2 — Y

II, ·.

(IV) wherein Y is as defined above, or 2,2-difluoroalkanoyl halides of formula

V, .... %., _.

hal — C — CF2 — Y •.

or 2,2-difluoronic acid anhydrides of the formula VI,

56 9 7

O-C-CF 2 -Y 12 (VI) wherein Y is as defined above.

The diamine starting materials with which the aeylation reactions are carried out are different.

A process for the preparation of compounds of formula III is provided. characterized, by reacting a compound of formula IX ( "and VA acylhaloganid JATE aeylační ;, agent is performed _in response · necessarily: in the presence of a hydrogen halide acceptor and preferably in an inert solvent, and the reaction mixture is preferably cooled to 0 In the case of any acylating agent, the product is recovered by conventional means and can optionally be purified by known methods.

For consistency, starting materials and products are named where. it is possible as ^{1 of} phenylenediamines. In accordance with normal nomenclature practice, the identification of the various positions of the substituents is as follows:.

(N 1) ⁼ wherein R ² and R ⁶ are as defined above with an acylating agent of formula IV,

......

HO-C. ^-GF2. — Y '' (IV) wherein Y is as defined above, or with its haloogenide ηβυβί · 9ήΜχφώ «α .; ., · '· ..

For compounds of formula III where R ² is .sktwiná, -Stejná is., The starting diamino., Nem compound of formula XII,

and introducing two identical acyl groups (R ° and R ' ² ' are

-C — CF2 — YJ.

^; “r ·.” . .

O

If ,, na. . second strap ,. R ² 'are the same

The 2,2-diphenyl group represented by R 0, the corresponding diamine starting material is a compound bearing the desired R ² residue of formula XV,

wherein the symbols are as defined above, and the characteristic R c group is similarly introduced by acylation.

The preparation of amides by acylation of the corresponding amines with various acylating agents is a known synthetic method. These preparations are carried out according to conventional methods known in the art. Thus, if the acylating agent is anhydride, the reaction is preferably carried out at room temperature. If used; either of the nitrogen atom containing an alkanoyl or other (R °, R ² ) substituent, the ring position numbers are identified as prime numbers to distinguish from the positions at R 0 or the R ² substituents preceding the definition of the compounds of formula H 1 _{: a} . In the present invention, the term "hal" and "halbgen", unless specified, but used alone or in conjunction as the term "halogenated alkanoyl", refers only to bromine, chlorine, fluorine or · Iodine.

The starting materials used in the process of the invention are prepared by known methods and. some of them are commercially available. Starting materials, formulas XII ''

fX / tf are prepared by multistage suntheses, which are necessary for introducing the desired groups, more preferably:. One or both of the SH 2 groups introduce by halogen transfer. Also, the amino group (s) can be introduced by nitration and subsequent reduction. The various synthetic steps are generally and most preferably carried out with starting materials which already contain the group R ⁶ . However, it is sometimes preferred that such substituents, for example, nitro or halogen; are introduced simultaneously with the synthetic steps leading to the introduction of amino groups.

Compounds of formula III wherein R ² is the same acyl radical as R ⁰ are generally prepared from starting materials already containing the R ² radical. The starting materials are prepared from the corresponding diamine starting materials described above by reaction with the appropriate acyl halide. Alternatively, however, these materials may be prepared from the Q-nflafilanes of S4MP7.

acylation and subsequent reduction by a method known in the literature.

; SymttJSS ». The compounds of the formula: III. is · Can be illustrated in the following examples. Example 1 ·

The alkylsulfonyl-C 1 -phenylethylidiffine-1-4-carbon atoms in the alkyl are dissolved in the solvent and triethylamine, and trifluoromethanethane is added under stirring. The resulting reaction mixture is then heated to cotton and evaporated to give the desired NkN ² -bls (trifluoroacetyl) -alkylsulfonyl-o-phenylenediamine having 1 to 4 carbon atoms in the alkyl.

Example 2

The compounds of the invention were prepared by the procedure of the preceding example using analogous starting materials. These compounds are as follows:

N ^l, N ² -bis (trifluoroacetyl trlf] -5' (methylsulfonyl-o-onylj fenylendiamih, mp 179-181 DEG C., prepared by reaction of trifluoroacetic anhydride with 5- (methylsulfonyl oaiyl yo-tenylendiaminem.

^Lj N- trifluoroacetyl-N? -Acetyl-4 '- (. * Inethylsul foňylj-o-phenylenediamine, mp 200-201 ^D C, prepared by reacting trifluoroacetic anhydride with N ² -acetyl-4- (methylsulfonyl) -o-phenylenediamine.

N ¹ -trifluoroacetyl-N ² -furoyl-5'- (methylsulfonyl) -o-phenylenediamine mp 185-187 ° C.

All compounds of formula III may be formulated as being useful as herbicides. These compounds can be used in such a way that a broad herbicidal effect is obtained; therefore, in the broadest sense, the invention relates to a method of application which is characterized in that a plant inhibiting amount of one of the ring-substituted ones is applied to plant parts such as stalk, leaves, flowers, fruits, roots or seeds or similar reproductive units of plants. N- (2,2-difluoroalkanoyl) -O-phenylenediamine of formula III, however, these compounds can also be used by utilizing selective herbicidal activity. As is known to those skilled in the art, a mixture of more than one compound can also be used to achieve a herbicidal effect. If a mixture is used, the amount of each individual compound can be reduced so that the mixture exhibits the desired herbicidal effect.

It is not critical to the herbicidal utility of the compounds whether undesirable vegetation is completely eliminated; it is sufficient if the paused vegetation is pulled; Especially with regard to the ineffective effect, inhibition of complete killing is sufficient, in particular; when combined with natural ;: padsmi, how limited it is. humidity,. which has the most adverse effect on. vegetation selectively inhibited than to useful plants.

The compounds of formula III are suitable for various variations of herbicidal applications.

Compounds of formula III exhibit low mammalian toxicity, relative to benzimidazoles. In addition, the compounds of formula III can be dispersed as an aerosol mixture containing one or more active ingredients according to the invention. This mixture is prepared according to conventional methods, wherein the active substance is dispersed in a solvent and the resulting dispersion is mixed with the propellant in a liquid melt. These variations as to the use of a particular reagent. and the type of vegetation to be treated, determining the solvent requirements and the concentration of the active ingredient therein. Examples of suitable solvents are water, acetone, isopropanol and 2-ethoxyethanol.

Appropriate results are obtained when the active substances of the formula III or a mixture containing these ¹ active substances are mixed with other agriculturally used materials to be applied to plants, plant parts and their surroundings. These materials include fertilizers, fungicides, insecticides, other herbicides and soil conditioners.

Various compounds of formula III which are _; intended to be used as active herbicidal agents, to be evaluated after application before emergence in various plant species. In this evaluation, a soil containing one part sand and one part crushed top soil layer is prepared, perfectly mixed in a cement mixer.

4.5 liters of this soil is placed in a 25 x 35 cm galvanized tin bowl and the cellar is below the rim. 2.5 cm deep grooves are made in three rows in about two fifths of the dish. Four corn kernels, five cotton seeds and five soybean seeds are planted in these grooves. In the remaining four grooves, the approximate number of each of the following seeds, each species in a single row, is sown in the remaining soil: 80 to 100 seeds, 40 to 50 seeds, 150 to 250 seeds and 100 to 150 blooms seeds.

A further sufficient amount of soil is then added to sufficiently cover the area.

Thus the weed seeds are covered with a layer of about 6 mm and the seeds of the useful plants with a layer of about 3 cm.

In order to determine the effect of the composition as a herbicidal composition after use before emergence, the area is prepared as described above and placed on the day of sowing or the next day in a chamber equipped with a turntable and an air outlet. The herbicidal mixture, either of the spray emulsion or of the wettable powder type, is applied to the surface with a modified De Vilbis atomizer attached to an air source.

195897 '7

Twelve and a half milliliters of the composition to be tested is then applied to each area on either the day of sowing or the following day. The intensity of the lesion and the observation of the type of lesion are performed on days 11 to 12 after treatment. Damage is assessed according to the following:

0— no damage, <

- moderate damage; - moderate damage; ......

- death.

Where more than one determination was made at the indicated amount, the average was calculated to assess damage. Each compound evaluated is sprayed by one of the following procedures. In one test, the compound is wetted by mixing in a mortar with one part polyoxyethylene sorbitan monolaurate. Five hundred parts of water are slowly added to the resulting cream-colored paste to give an aqueous dispersion with a base concentration of 0.2%. Dispersion is suitable for spray application. In a second procedure, the compound is dissolved in one part of acetone and the acetone solution is diluted with nineteen parts of water containing 0.1 percent polyoxyethylene sorbitan monolaurate. '

In the following Table I, the evaluation results are shown, column 1 shows the name of the test compound, column 2 the amount in cllograms of hectares in which the compound is applied to the test area, and the remaining columns indicate the degree of damage .

Table Γ

Damage to pre-emergence treatment kg / ha compound bayjna maize soybean goosefoot grass

1 »80IT '';

. car. .;

.V> 6>

so oo ”oo oo

if

185898> ^{rί: Α} 1S * '

Some of the compounds of formula III were suitable for the test except that the test compound was grown after application after emergence in plants, the flow was applied for 9 to 12 days in preparation and for maize and some weed species. Sowing into soil. The results are shown in the evaluation according to the following Table II.

, · T a b u 1 k and 11

Degree of damage during emergence treatment.

compound kg / ha maize maize scabbard; bloody cloudlet

N ¹ , N ² -bi (trifluoroacetyl) -5'- 8.8 2 4 4 3 4 i (methylsulfonyl) -o-phenylene- 4.4 1 4 4 4 3 dlamin 2,2 1 4 4 4 2 Nf-trlf luoracetyl-N ² - (2-f uroyl- 8.8 1 2 3 ” '3': 3 -5´-methylsulfonyl} -o-phenylene- - diamln OBJECT OF THE INVENTION

Claims (1)

bloody> N ¹ , N ² -bi (trifluoroacetyl) -5'- 8.8 2 4 4 3 4 i (methylsulfonyl) -o-phenylene- 4.4 1 4 4 4 3 dlamin 2,2 1 4 4 4 2 Nf-trlf luoracetyl-N ² - (2-f uroyl- 8.8 1 2 3 ” '3': 3 -5´-methylsulfonyl} -o-phenylene- - diamln OBJECT OF THE INVENTION A process for the preparation of substituted N- (2,2-difluoroalkanoyl) -o-phenylenedlamines of formula III, (w) R 2 is a 2,2-difluoroalkanoyl radical of the formula —C — CF2 — Y, I10 where Y is a fluorine atom, R ² is R ®, furoyl or acetyl, R ⁶ is C 1 -C 4 alkylsulfonyl located in the 4 or 5 position, characterized in that a compound of formula IX, wherein R ² and R ⁶ are as defined above, is reacted with an acylating agent of formula IV, O! L · HO-C-CF2-Y (IV) in which Y has the abovementioned ^meaning,! or with a halide or anhydride of a compound of formula IV. Sevno (ra {ii, a. P., Rfvod 7, Most