KR800000313B1 - Process for the preparation of n,n-bis(2-methoxy-3,6-dichloro benzoyloxyalkyl)anilines - Google Patents

Abstract

N, N-Bis(2-methoxy-3,6-dichlorobenzoyloxyalkyl)anilines(I; X =alkyl; t =0-3 ; Y = C2-3 straight or branched chain alkylene), useful as herbicides, were prepd. Thus, N-phenyl-N, N-diethanol-amine was reacted with 2-methoxy-3,6-dichlorobenzoyl chloride in the presence of inactive solvents and amines to give I. The property of I showed a resistance against leaching soil.

Description

Preparation of N, N-bis (2-methoxy-3.6-dichlorobenzoyloxyalkyl) aniline derivative

The present invention relates to the composition of novel herbicides and, more particularly, to a novel compound represented by formula (I).

In the formula, X is an alkyl group; t is an integer from 0-3; Y is a straight or branched chain alkylene group of 2-3 carbon atoms. The compound is useful as a herbicide having leaching resistance in soil.

More specifically, the present invention, X is a lower alkyl group having a straight or branched carbon bond of 6 or less carbon atoms.

The compounds of the present invention have unexpected properties that are useful as herbicides and resistant to leaching in soil. Many beneficial plants have deep roots in the ground, while weeds sometimes grow near the soil surface.

Therefore, in order to avoid harming beneficial plants that are partially sensitive to herbicides, it is desirable to minimize the leaching of herbicides in the soil downward. Moreover, the basis for the germination action of herbicides is often due to the difference in depth between crop seeds and weed seeds sown on the soil surface.

인치에서만 발아하므로 이것은 고농도의 화학악품에 노출된다. 약품의 농도상에 이차이를 유지하기 위하여 토양에서 걸러는데 저항하는 제초제를 갖는것이 바람직하다.Crop seeds are generally sown 1-3 inches deep to protect them from pesticides on the surface of the soil, while weed seeds are generally top soil

It germinates only in inches, so it is exposed to high concentrations of chemicals. It is desirable to have a herbicide that resists filtration in soil to maintain secondary differences in drug concentration.

The compounds of the present invention are high in resistance to gait.

The compound of the present invention can be easily prepared by reacting 1 gram molecular weight of the compound represented by the general formula (II) with 2 molecular weights of 2-methoxy-3.6-dichlorobenzoyl chloride.

Wherein X, t and Y are as described above.

This reaction is effective to combine the reactants in the presence of an acid acceptor such as a tertiary amine wave in a sulfurous organic solvent such as benzene wave. The reaction mixture is heated at reflux for 2-12 hours. After this time the mixture is washed with water and washed with dibasic acid solution and basic solution to remove unreacted starting material. The mixture is washed again and dried over anhydrous magnesium sulfate. The solvent is removed from the dried mixture under reduced pressure to give the desired product as a residue. When a compound represented by formula (II), which can be conventionally prepared from the corresponding aniline, is not readily used, it is reacted with ethylene oxide or propylene oxide.

The preparation method of the compound of the present invention will be described in detail in the following examples.

Example 1

Preparation of N, N-bis (2-methoxy-3.6-thechlorobenzoyloxyethyl) aniline

N-phenyl-N, N-dietasolamine (18.1 gr; 0.1 mol), 2-methoxy-3.6-dichlorobenzoyl chloride (47.3 gr; 0.2 mol), pyridine (16 gr; 0.2 mol) wave benzene (150 ml) Into a glass reactor equipped with a stirrer, thermometer and reflux cooler. The mixture is heated with stirring at reflux for 5 hours.

After 2 hours, the reaction mixture was washed with water, extracted with dilute hydrochloric acid solution and washed with 5% aqueous sodium carbonate solution. The solvent was removed under reduced pressure from the washed mixture to give a product containing N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxyethyl) aniline.

Example 2

Preparation of N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxypropyl) aniline

N-phenyl-N, N-dipropanolamine (21 gr; 0.1 mol), 2-methoxy-3.6-dichlorobenzoyl chloride (47.3 gr; 0.2 mol), pyridine (16 gr; 0.2 mol) and benzene (150 ml) Into a glass reactor equipped with a stirrer, thermometer and reflux condenser. The mixture is heated with stirring at reflux for 6 h. After this time the mixture is washed with water and dried over anhydrous magnesium sulfate. Removal of the solvent under reduced pressure of the dried mixture affords a product containing N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxypropyl) aniline as a residue.

Example 3

Preparation of N, N-bis (2-methoxy-3.6-dichlorobenzoyloxyethyl) -4-methylaniline

N- (4-methylphenyl) -N, N-diethanolamine (19.5 gr; 0.1 mol), 2-methoxy-3.6-dichlorobenzoyl chloride (47.3 gr; 0.2 mol) pyridine (16 gr, 0.2 mol) wave benzene ( 150 m1) are placed in a glass reactor equipped with a stirrer, reflux cooler and thermometer. The reaction mixture is heated at reflux for 5 hours. After this time the mixture is washed with water and dried over anhydrous magnesium sulfate. Removal of the solvent under reduced pressure of the dried mixture affords a product that combines N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxyethyl) -4-methylaniline as a residue. Additional compounds within the scope of the present invention may be prepared by the methods described in the previous examples.

In the following examples given as starting materials it is required to prepare the compounds pointed out and named by the methods described above.

Example 4

N- (3-propylphenyl) -N, N-diedanolamine + 2-methoxy-3.6-dichlorobenzoyl chlorard = N, N-bis (2-methoxy-3.6-theclotobenzoyl oxyethyl) -3-propylaniline.

Example 5

N- (4-hexylphenyl-N, N-diedanolamine + 2-methoxy-3.6-thechlorobenzoyl chromide = N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxyethyl) -4 -Hexyl aniline.

Example 6

N- (3.4-dimethylphenyl) -N, N-diedanolamine + 2-methoxy-3.6-dichlorobenzoyl chloride = N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxyethyl) -3.4 Dimethylaniline

Example 7

N- (3.4.5-trimethylphenyl) -N, N-diethanolamine + 2-methoxy-3.6-dichlorobenzoyl chloride = N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxyethyl) 3.4.5-trimethylaniline.

Additional compounds within the scope of the present invention include N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxyethyl) -3-ethylaniline, N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxy Ethyl) -4-butylaniline, N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxyethyl) -4-pentylaniline,

N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxyethyl) -3.4-diethylaniline. N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxyethyl) -3.4-dipropylaniline, N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxyethyl-3.4-dihexylaniline, N, N-bis (2-methoxy-3,6-dichlorobenzoyl oxypropyl-2-yl) -4-methylaniline, N, N-bis [2- (2-methoxy-3.6-dichlorobenzoyl oxy) Propyl] -2-ethylaniline, N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxypropyl) -3-propylaniline, N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxypropyl) 4-butylaniline N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxypropyl) -4-pentylaniline, N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxypropyl) -3.4- Dimethylaniline,

N, N-bis (2-methoxy-3.6-dichlorobenzoyloxypropyl) -3.4-diethylaniline, N, N-bis (2-methoxy-3.6-dichlorobenzoyl oxypropyl) -3.4-dihexylaniline, N, N-bis (2-methoxy-3.6-dichlorobenzoyloxyftfil-3.4.5-trimethylaniline, N, N-bis (2-methoxy-3.6-thechlorobenzoyl oxypropyl) -3.4.5- Similar to triethylaniline.

For practical use as herbicides, the compounds of the present invention are generally mixed in an herbicidal composition comprising an inert carrier and herbicidally toxic amounts of such compounds.

Such herbicide compositions may be referred to as formulations and may be active compounds which are commonly applied in places where weeds are prevalent at desired amounts.

These compositions can be solids such as powders, particles or wet powders, liquids such as solution aerosols or concentrated emulsions. For example, powders are prepared by grinding and mixing the active compounds with inert solid carriers such as talc, clay, silica, pyrophyllite, etc. Embed formation is generally made by saturating the compound dissolved in a suitable solvent or generally a granulated carrier such as attapulched or mica in a particle size of 0.3-1.5 mm.

Wet powder is prepared by dispersing in water or oil at a suitable concentration of the active compound and mixing the wetting agent in the concentrated powder composition. In some cases, the active compounds are sufficiently dissolved in common organic solvents such as kerosene or xylene and are therefore used directly as solutions in these solvents. Occasionally, solutions of herbicides are dispersed under superatmospheric pressure, such as aerosols. However, better liquid herbicide compositions can be incorporated into concentrates containing active compounds and inert carriers, solvents and emulsifiers according to the present invention.

Such concentrated emalons can be widened with water or oil to the appropriate concentration of active compound to apply as spraying on weed rampant areas. The most common emulsifiers used in these concentrates are nonionic or nonionic surfactants mixed with cationic surfactants. Emalzone (type W / 0), converted to the use of some emulsifiers, is manufactured for direct application to weed spread areas.

The composition of a typical herbicide according to the invention is illustrated by the following examples and the amounts are parts by weight.

Example 8

Recipe of powder

Product 10 of Example 1

Powder Talco 90

The components are mixed in a mechanical pulverizer-mixer and ground until homogeneous to eliminate free flowing powder of the desired particle size. This powder is suitable for direct action on weed rampant areas.

The compounds of the present invention are used as herbicides by known techniques. One method for weed control includes contacting the area of the weeds with the composition of herbicides containing an inert carrier and the underlying active ingredient and the compounds of the present invention, such as amounts of toxic herbicides to the weeds. The concentrations of the novel compounds of the present invention in herbicide compositions vary widely with the form of formation and for the purpose designed, and herbicidal formulations generally contain about 0.05-95% by weight of the active compounds of the present invention.

More specifically, the herbicide composition contains 5-75% by weight of the active compound.

The composition contains other substances such as insecticides, nematodes, fungicides, and the like, additional substances such as insecticides, stabilizers, dusting agents, inerts, adhesives, binders, fertilizer active agents, and the like.

The compounds of the present invention are useful when combined with other herbicides or anti-killing agents, growth inhibitors and the like in the above herbicide composition. These other substances contain 5-95% of the active ingredient in the herbicide composition. The use of these other herbicides or acaricides in combination with the compound of the present invention having herbicide composition is more effective in suppressing weeds and sometimes unachievable by separate composition of herbicides.

Compounds of the present invention and other herbicides, acaricides and plant growth inhibitors are used as herbicidal compositions for inhibiting weeds. 2.4-D, 2.4. 5-T, MCPA, MCPP, Alacro, 4 (2.4-DB) 2.4-DEB, 4-CPP, 4-CPA, 4-CPP, 2.4.5-TB, 2.4.5-TES, 3.4-DA Silbex Chlorophenoxy herbicides such as these, carbamate herbicides such as IPC, CIPC, swimbarban, BCPC, CEPC, CPPC, and the like; Thiocarbamates and dithiocarbamate herbicides such as CDEC, methamsoda, EPTC, diyarade, PEBC, perbutrate, vernorate and the like; noriers, cidurons, dichloralureas, chromoxalone, cycrulones, ferrocene Substituted urea herbicides such as Nuron, Monuron, Monuron TCA, Diuron, Linuron, Monolinuron, Neburon, Buturon, Trimethuron and the like; Symmetric triazine herbicides such as simazine, crorizine, atrion, desmethrin, norazine, ifazin, poromethrin, atazine, triethazine, cimetone, promethone, propazine, amethrin and the like; α-chloro-N, N-dimethylacetamide, CDEA, CDAA, α-chloro-N-isopropylacetamide, 2-chloro-N-isopropylacetanilide, 4- (chloroacetyl Croazate amide herbicides such as) -morpholine) 1- (chloroacetyl) piperidine and the like; Chlorinated fatty acid herbicides such as TCA, Dalapon, 2.3-dichloropropionic acid, 2.2.3-TPA, and the like; 2.3.6-TBA, 2.3.5.6-TBA, tricamba, ambene, spent lacquer, PBA, 2-methoxy-3.6-dichloropentylacetic acid, 3-methoxy-2.6-dichlorophenylacetic acid; Benzoic acid chloride and phenylacetic acid herbicides such as 2-methoxy-3.5.6-trichlorophenylacetic acid 2.4-dichloro-3-nitrobenzoic acid and the like; Amiro triazole, maleic hydrazide, phenylmercuric acetate, endortal, biurel, technical crodan, dimethyl, 2.3.5.6-tetrachloro terephthalate, niquid elbonDNC, DNBP, dichrobenyl, DPA, diphenamide, diproparin, tripurarin, turbulence, dicyrylmed force, DMPA, DSMA, MSMA, potassium azide, acrolein, benepine, benzuride, AMS, bromasil, 2- (3.4 -Dichlorophenyl) -4-methyl-1.2.4-oxadiazolidine-3.5-dione, bromoxynil, cacodyric acid, CMA, CPMF, cipromide, DCB, DCPA, dichrodiphenatryl , DMTT, DNAP, EBEP, EXD, HCA, Ioxynyl, IPX, Isosil, Potassium Cyanate, MAA, MAMA, MCPES, MCPP, MH, Morinate, NPA, OCH, Paraguat, PCP, Picroram, DPA, DCA, Pycurone, Ceson, Turvaseal, Terbutol, TCBA, Brominyl, CP-50144. H-176-1, H-732. Compounds such as M-2901 pranamin, sodium tetraborate, calcium cyaneneamide, DEF, ethylchitogendisulfazide, sindon, sindon B, propanyl and the like.

Such herbicides may also be used as their salts, ester apides and giga derivatives, which can be applied to particular parent compounds in the methods and compositions of the present invention.

Weeds are undesired plants that are not economical in the growth of ornamental crops or the prosperity of pastoral crops. Many types of weeds include tusks, tomb squats, nectar, wild grass, wild mustard, field pennyless, poisonous grass, rake, chickweed, wild curie, velvet leaf, iron dandruff, half yardgrass, smartweed, Knotweed, docomari, wild buckwheat, kochia, canopy, seoncho, cucurbita, kofiweed, pau, coupia, creeper plant, corydalis, cauliflower, hemp, nettle, nawell , Lighthouse, trefoil, emmex, jingle, herbaceous plant, asteraceae, capelweed morning glory, rake grass duck ducard, naiad, barley weed, grass fan Year-rounds such as kum, white datura, witgrass, sweetgrass, witgrastyweed, wildtonsop, and spangled top; 2, such as wild carrots, matrycaria, wild barley, beetle, yellow burdock burdock, wild bovine, round leaf mallow, vulture, marsupial, moss murinein and purple and thistle Annual coloring; Or White Cockle, Perennial, Rygra, Shankgrass, Johnson Grass, Canadian Chart, Hedge, Bind Weed, Bermugrass Ship Sorel, Curry Dog, Nutgrass, Field Chic Weed, Dandelion, CapFenura, Field, Vine Weed, Tussian, Nepweed, Legume Shrub, Rhododendron, Hypnotaceae, Cromwell, Prunus Ironward Sesbania, Greater Marsh, Bud, Wintergrass, Hosnettle; It is known to include perennial plants such as nutsset, vermicelli, and Sickford.

Similarly, weeds like this are classified as broad-leaved or grassy weeds. Such growth inhibition of weeds is economically desirable without damaging beneficial plants or grasses.

The novel compounds of the present invention are particularly valuable for weed control.

Because they are relatively nontoxic to many beneficial plants, they are toxic to many groups and seeds of weeds.

The exact amount of compound required will depend on several factors, including the type of plant, application method, soil type, the strength of the patent weed seed, and the climate, beneficial in the same area and such. Therefore, application of 1 or 2 ounces of air carcass, or active compound, is sufficient for good inhibition of weed growth under adverse conditions, and application of 10 pounds or more of air carcass active compound for strong perennial weed growth under good conditions. It is required for good suppression to a rich rampant. The herbicidal toxicity of the novel compounds of the present invention is illustrated by many well-known technical tests, such as post-war expression tests.

This is illustrated by experiments conducted for the herbicide activity of the compounds of the present invention or for weed suppression of various weeds.

In these experiments, small plastic greenhouse pots filled with dry soil were planted with various weed seeds.

Pots sown in 24 hours or less are sprayed with water until the soil is wet and acetone solution containing emulsifier is formed into compound N, N-bis (2-methoxy-3,6-dichloro). Benzoyloxyethyl) -aniline was sprayed onto the surface of the soil at the desired concentration. After spraying, the soil container is transferred to the greenhouse, sprayed with water every day or more, and supplied with sufficient heat. The plant continued under these conditions for 28 days. At that time, the degree of harm to the conditional plants of the plants was rated on a scale of 0-10.

As follows. 0 = harmless, 1.2 = slight, 3.4 = reasonable, 5.6 = severe, 7.8.9 = severe, and 10 = test

Resistance to the strain of the compound of the invention is explained experimentally in the movement of the compound of the invention through the measurement of soil. In this experiment, the plastic column was already dried and filled with soil that penetrated the 30 mesh screen. The column was filled with soil about 9 inches deep. The tested compounds were applied to the soil surface with an equivalent weight of 15-20 pounds per air carcass and water equivalent to 6 inches of rainfall was poured into a single addition on top of the pillar.

The column was left for 24 hours and for 2 hours the water flowed from underneath the collected columns. After 2 hours the column was sawed into 3 inch cross sections. Water outflow and soil classification were analyzed by the test amount of the present compound. This analysis was carried out by each soil classification and ethyl ether removal, and extracted by Na OH extract. Na OH was extracted to saponify the compound, and then hydrolyzed Na salt with hydrochloric acid. Convert to oxy-3.6-dichlorobenzoic acid. The acid is esterified with its methyl ester and the resulting sample is used for gas chromatographic quantitation. The results of the analysis of the compounds tested in the Stoy Chihometric conversion and the various soil classifications and removal of water indicate resistance to the compounds of the present invention.

Claims (1)

The 1 gram molecular weight of the compound represented by the general formula (II) is reacted with the 2-methoxy-3.6-dichlorobenzoyl chloride 2 gram molecular weight in the presence of an inert solvent such as benzene and an acid acceptor such as a tertiary amine. Method for producing a compound represented by).

Wherein X is an alkyl group, t is an integer of 0-3 and Y is a straight or branched chain alkylene group of 2-3 carbon atoms.