Derivatives of hinoklidilkarbinola exhibiting herbicide activity

 

(57) Abstract:

The invention relates to new derivatives of hinoklidilkarbinola General formula where n is an integer 1, 2, 3, R1-halogen or trihalomethyl, R2is hydrogen, R3-furanyl, tetrahydrofuranyl, DIOXOLANYL, pyranyl, tetrahydropyranyl, optionally substituted by 1, 2 or 3 substituents selected from the group comprising oxoprop and C1-C3-alkyl. The compounds exhibit a high selective herbicide activity. The formula of the compounds: 3 C.p. f-crystals, 6 PL.

The invention relates to new heterocyclic alkylene-chynoxalinilmethylen compounds which exhibit unexpectedly high selective herbicide activity.

Although many of the known compounds shown in the above publications are desirable herbicide activity, however, there is a need for selective herbicides.

According to the invention a new class of compounds having the structural formula:

< / BR>
where

n represents 1, 2 or 3;

R1and R2each independently selected from the group consisting of halogen, hydrogen, C 1 - 3 alkoxy, C 1 - 3 goloboy 5 - or 6-membered saturated, unsaturated or partially unsaturated heterocyclic ring containing 1 or 2 oxygen atom, and the specified ring optionally substituted by 1 to 3 substituents, each independently selected from the group consisting of oxo, C 1 - 3 alkyl and C 1 - 3 alkoxy.

Especially preferred compounds include:

2-tetrahydrofuranyl 2-[4-/6-chloro-2-hinoksolinov/phenoxy]-7-propanoate.

2-furylmethyl 2-[4-/6-chloro-2-hinoksolinov/phenoxy]propanoate;

2-tetrahydropyranyl 2-[4-/6-chloro-2-hinoksolinov/phenoxy]-propanoate;

2-[2-/2-methyl-1,3-dioxolane/] ethyl 2-[4-/6-chloro-2-hinoksolinov/-phenoxy]-propanoate,

4-/3,3-demethyl-2-butyrolactones/methyl 2-[4-/6-chloro-2-hinoksolinov/-phenoxy]-propanoate,

4-/2,2-dimethyl-1,3-DIOXOLANYL/methyl 2-[4-/6-chloro-2-hinoksolinov/-phenoxy]-propanoate.

The compounds of this invention can be obtained by the reaction chynoxalinilmethylen the compounds of formula:

< / BR>
where

R1, R2have the meaning as defined for structure (1) above, with the heterocyclic alkyltrimethylenedi formula:

< / BR>
where

X represents halogen, mesilate (methylsulfonyl) or tosylate (trilobites case is carried out in an organic solvent (such as dimethylformamide, dimethyl sulfoxide, Acrylonitrile or the like) in the presence of inorganic or organic bases (such as sodium carbonate, potassium hydroxide or potassium carbonate) at a suitable temperature.

Chynoxalinilmethylen starting compound can be obtained by the interaction of 2-galoidkyetonov compounds having the formula:

< / BR>
where

X represents halogen, and R1and R2have the meaning as defined for structure (1) above, with phenylbenzyl ether of the formula:

< / BR>
in the presence of an inorganic or organic base to obtain the intermediate compounds of formula:

< / BR>
and hydrogenation of this intermediate connection (using a hydrogenation catalyst such as palladium) to obtain the product dibenzylamine and education thereby chynoxalinilmethylen source material.

The heterocyclic alkylphenol-halide source connection can be obtained by the interaction of galodamadruga halogenated propionic acid with the appropriate heterocyclic alkilany alcohol.

Alternative ethyl 2-holodprombyt can undergo reaction with whom to Tetra-isopropoxide) with a heterocyclic alkyltrimethylenedi interesterification reactions.

The compositions of this invention comprise (A) at least one of chynoxalinilmethylen compounds of this invention and (B) a suitable carrier.

To obtain herbicide compositions chynoxalinilmethylen connection can be mixed with inert ingredients, giving the composition in the form of a solid, finely ground substances in the form of particles, granules, pellets, wettable powders, flowable liquids, soluble powders, solutions and dispersions or emulsions in water or an organic solvent. These are ready preparative forms can be several different physical and chemical types, any of which may be obtained by a person familiar with this technical field.

The concentration of the active chemical compounds in the composition may vary within wide limits, usually in the range of from about 1 to 95 wt.%. The concentration of the active chemical agent in the dispersion applied to the soil, seeds or leaves, in the typical case is approximately between 0,002 and 80 wt.%.

For use as preschoolage herbicide compound of the present invention typically is used in an amount from about 0.01 to 10 the deposits. Such application is made or in relation to the soil surface or in the top layer of soil to a depth of from one to three inches (2.5 to 7.5 cm). When applied as a post-harvest herbicide compound is usually applied in amounts of from about 0.01 to 10 pounds per acre (about 0,01 to 11.2 kg/ha) on the air side of the weeds (ground part).

Compounds of the present invention include isomeric forms and their mixtures, i.e. as optically active isomers and racemic mixtures. Unless otherwise indicated, the compounds described in the examples represent a racemate.

Example 1.

Getting 2-tetrahydrofuranyl 2-[4-/6-chloro-2-hinoksolinov/phenoxy]propanoate (compound 4).

A. Obtaining 2-tetrahydrofuranyl 2-bromopropionate.

In a 250-ml three-neck flask add 0.15 mol 2-/hydroxymethyl/tetrahydrofuran, 0.15 mol of triethylamine and 100 ml of diethyl ether. The flask was immersed in ice and added dropwise being 0.15 mol of 2-bromopropionitrile. The ice bath removed and the reaction mixture stirred at ambient temperature for two hours. The mixture is extracted with an equal volume of water and the organic phase is dried over sodium sulfate. Decanted and wallacea 2-tetrahydrofuranyl 2-[4-/6-chloro-2-hinoksolinov/phenoxy]propanoate.

In a 500-ml round bottom flask add to 0.055 mol 2-/4-hydroxyphenoxy/-6-chlorphenoxamine, by 0.055 mol 2-tetrahydrofuranyl 2-bromopropionate, 0,110 mol of anhydrous potassium carbonate and 250 ml of acetonitrile. The mixture is heated under reflux for 5.5 h and the solvent is removed. The residue is filtered through a column of alumina with dichloromethane. Removal of the solvent and recrystallization from boiling hexane yields (yield 85%) 2-tetrahydrofuranyl 2-[4-/6-chloro-2 - hinoksolinov/phenoxy] propanoate. The substance melts in the range of 52 - 55oC.

Example 2.

Using the techniques described above, receive other compounds. The structure and the melting point and/or the NMR spectra of these compounds are presented in table. 1. (Note: in the data of NMR spectra: s - singlet, d - doublet, so-triplet, q - Quartet, and m - multiplet).

Example 3.

Pre-emergence treatment.

To illustrate the effectiveness of the compounds of this invention as prescheduled herbicides 300 mg each of the following compounds dissolved in 10 ml of acetone, add 30 mg emulsifying agent is ethoxylated of sorbitanoleat. The solution Razavi 250 hours/million distilled water. Compounds are used in quantities of 10 lb/acre (11.2 kg/ha), moistening the surface of the soil in plastic pots size 4-1/2 inches (11,25 cm), which planted the seeds of the following weeds: cantica Theophrastus (Abutilon theophrasti Medic) VL, jimson weed (Datura stramonium L) JW, ipomea purple (Ipomea purpurea L. Roth) TM, switchgrass (Panicum virgatum L) SG, barnyard grass (Echinochloa crusgalli) (L) Beauv. BG and spickle green (Setaria viridis L. Beauv GF 46 ml 250 hours/million solution.

Two weeks after treatment to determine the percentage of suppression of weed growth in comparison with untreated control plants. The results are given in table. 2.

The above data show excellent selective preschedule destruction of weeds exhibited by compounds of the present invention.

Example 4.

Post-harvest handling.

To illustrate the effectiveness of the compounds of this invention as a post-harvest herbicides 3000 hours /million solutions described in example 3 is sprayed using a conventional Devilbis spray (brand), wetting the foliage to the point of dripping. In other respects, the procedure was repeated as described in example 3. Weeds are treated after 6 days after germination.

The data show selective post-harvest herbicide weed control are detected by the compounds of this invention.

Example 5.

To illustrate the effectiveness of the compounds of this invention on predsjedavao destruction of grasses compared with the compounds of the prior art several solutions of compounds were prepared according to the method similar to that described in example 1. Solutions of concentrations of 250 hours/million diluted to 3.1 hours /million distilled water to test and apply at the rate of 0.14 kg/ha, in the amount of 46 ml for impregnation of the soil in pots with a diameter of 11.25 see Similarly prepared and are solutions of compound A - benzyl 2-[4-/6-chloro-2-hinoksolinov/phenoxy]propanoate, compounds described in U.S. patent 4629493 (compound 55).

Structure of the test compounds are as follows:

Connection 2:

< / BR>
Compound 4:

< / BR>
Compound 6:

< / BR>
Connection A:

< / BR>
The test results are given in table. 4.

The above data clearly show the unexpected activity of the compounds of the present invention in comparison with known gomoti example 3 and table. 2, in which the compounds 1-4 and 6 are tested for activity against wild oat (WO), spickle green (GF) and barnyard grass (BG) at different application rates. Experience also known compound A (example 5). The results are presented in table. 5.

These results show excellent preschedule herbicide action of these compounds at such low application rates, as of 0.14 kg/ha and at least to 1.12 kg/ha Since all tested compounds give 100% destruction at the dose of 1.12 kg/ha, legitimate to expect that the same result will be obtained at any higher rate used for the connection.

Perform additional tests as described in example 4 and table. 3. The results obtained are presented in table. 6.

The results demonstrate excellent post-harvest selective herbicide effect of the present invention in a wide range of doses.

1. Derivatives of hinoklidilkarbinola General formula

< / BR>
where n = 1, 2, 3;

R1- halogen or trihalomethyl;

R2is hydrogen;

R3- furanyl, tetrahydrofuranyl, DIOXOLANYL, pyranyl or tetrahydropyranyl, optionally substituted by 1, 2 or 3 Deputy under item 1, in which R1- chlorine, trichloromethyl or trifluoromethyl.

3. Connection on p. 1, selected from the group consisting of 2-tetrahydrofuranyl-2-[4-(6-chloro-2-hinoksolinov)-phenoxy]-propanoate, 2-furylmethyl-2-[4-(6-chloro-2-hinoksolinov)phenoxy] -propanoate, 2-tetrahydropyranyloxy-2-[4- (6-chloro-2-hinoksolinov)- phenoxy]-propanoate, 2-[2-(2-methyl-1,3 - DIOXOLANYL)]ethyl-2-[4-(6-chloro-2 - hinoksolinov)phenoxy]-propanoate, 4-(3,3-dimethyl-2-butyrolactone)methyl-2- [4-(6-chloro-2-hinoksolinov)phenoxy] -propanoate, 4-(2,2-dimethyl-1,3 - DIOXOLANYL)methyl-2- [4-(6-chloro-2-hinoksolinov) phenoxy]-propanoate.

4. Connection on p. 1 where the compound is 2-tetrahydropyranyloxy-2-(4-(6-chloro-hinoksolinov) phenoxy)-propanoate.

 

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