CS239406B1 - Esters of 2-aryloxyacetylbenzoic acid end method of theier preparation - Google Patents

Abstract

The invention relates to 2-aryloxyacetylbenzoic esters acids of general formula I and processes for the preparation of general compounds of formula I by reaction of 3-aryloxymethylenephthalde with the appropriate alcohol in the presence of a catalyst at 60 ° C to 100 ° C. The compounds have herbicidal properties.

Description

The present invention relates to 2-aryloxyacetylbenzoic acid esters of formula (I)

ABOUT

and a process for preparing compounds of formula I by reacting 3-aryloxymethylenephthalde with the corresponding alcohol in the presence of a catalyst at a temperature of 60 ° C to 100 ° C.

The compounds have herbicidal properties.

The invention relates to 2-aryloxyacetylbenzoic acid esters and to a process for preparing the same. These compounds are effective as herbicides.

It is known that the acids and sodium salts of 2-aryloxyacetylbenzoic acid are characterized by herbicidal activity (Cs. AO No. 190 706). The amines of 2-aryloxyacetylbenzoic acid (Cs. AO No. 191 633) also have herbicidal activity.

Now the gilded esters of 2-aryloxyacetylbenzoovaj acid of the formula I, the C O R • ¹

C-CH

IIo

(i) wherein r 'is alkyl of 1 to 4 carbon atoms,

R is methyl, chlorine, a condensed aromatic ring.

At the same time, a process for the preparation of compounds of formula I by reaction of 3-aryloxymethylenephthalides of formula II

ABOUT

CH with an alcohol of formula III (II) in which 2

R is as defined above

R ¹ -OH (III) wherein r 'is as previously defined in the presence of a catalyst such as sulfuric acid, phosphoric acid, p-toluenesulfonic acid and the like. at a temperature of 60 to 100 ° C, preferably at 60 to 80 ° C.

The composition of the invention may be used for agricultural and horticultural purposes as such or in admixture with conditioning aids which improve the effect of the composition of the invention or which stabilize the composition depending on its intended use. The composition of the invention may be used e.g. in the form of powder, microgranules, granules, wettable powder, liquid suspension concentrates, ultra-small volume formulation, or in the form of an emulsifiable concentrate, prepared by commonly used pesticide manufacturing methods.

In practical use, these severe types of compositions of the invention may be used as such or after dilution with water to a suitable concentration.

As used herein, the term " processing aids " refers to carriers (diluents) as well as diffusers, emulsifiers, wetting, dispersing agents, binders, fillers and the like. substances.

Liquid carriers are always understood as petroleum fractions such as petroleum and light oil, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol, glycol, ketones such as acetone, amides such as dimethylformamide sulfoxides such as dimethylsulfoxide, methylnaphthalene, cyclohexane, animal and vegetable oils, fatty acids, fatty acid esters, and the like.

Solid carriers are always understood to be clay, kaolin, calf, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, silica, alumina, sawdust.

Surfactants are used as emulsifiers or dispersing agents. Surfactants include anionic, cationic and amorphous surfactants, such as sodium higher alcohol sulfates, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ethers and laurylbetain, and others.

The 2-aryloxyacetylbenzoic acid esters of the invention may be used alone or may be applied to the soil or to a destination in admixture with fertilizers or other agricultural or horticultural preparations.

When used in the above-mentioned forms, the concentration of the active ingredient according to the invention may vary depending on the form of the composition and the agricultural auxiliaries used, and is generally from 4 to 95% by weight.

For example, in the case of a powder, the active ingredient content is 4 to 20% by weight and the excipients are 80 to 96 95; in the case of an emulsifiable concentrate, the active compound content is 5 to 40 95 and the excipients 60 to 96 95; in the case of liquid suspension concentrates, the active ingredient content is 5 to 40 95 and the excipient content 60 to 95 95; in the case of a wettable powder, the active compound content is 20 to 80% and the excipients 20 to 80 95; in the case of granules and microgranules, the content of active substances is 4 to 10% and the excipients are 90 to 96 95.

The following examples illustrate but do not limit the scope of the invention.

EXAMPLE

2- (2,4,5-Trichlorophenoxyacetyl) benzoic acid methyl ester

To 0.01 mole of 3- (2,4,5-trichlorophenoxymethylene) phthalide and 0.1 mole of methanol was added 0.005 mole of sulfuric acid with stirring. The reaction mixture is heated to reflux temperature with stirring for 1 h. Excess methanol is removed by distillation. The distillation residue is crushed and washed thoroughly with water, aqueous sodium bicarbonate solution and water. After drying, the crude product is purified by crystallization from acetone. This gives a white crystalline solid, m.p. 88 to 90 ° C of the following composition:

Analysis for C 18 H 17 Cl 2 O 4 (MW: 373.6) Off .: 51.34 95 C; 2.96 95 H, 28.46 95 Cl Zist .: 51-, 56% C, 3.21 H; 28.34 95 Cl.

Example 2

2- (2,4,5-Trichlorophenoxyacetyl) benzoic acid butyl ester

Working procedure as in Example 1. M.p .: 148 ° C. A crystalline substance with m.p. 148 ° C of the following composition:

Analysis for C ^ HH ^O ^Cl Cl: (MW: 415.7)

Calcd: C, 54.89; H, 4.12; H, 25.58;

found: 54.52% C, 4.28% H, 25.29 Cl.

Example 3

2- (2,4,5-Trichlorophenoxyacetyl) benzoic acid ethyl ester

Working procedure as in Example 1. Mp 55-57 ° C.

Analysis for C ^ HH ^O ^Cl Cl (MW: 387.6)

Calcd: 52.67 C, 3.38 H, 27.43 Cl;

found: 52.80 C, 3.44 H, 27.53 Cl.

Example 4

2-C2,4,5-Trifluorophenoxyacetyl) benzoic acid propyl ester

Working procedure as in Example 1. Melting point 49-50 ° C.

Analysis for Ο, θΗ ^ Ο ^ ΟΙ ^ (a.h .: 401.6)

Calcd .: 53.82 C, 3.76 H, 26.47 Cl Found: 54.02 C, 3.63 H, 26.11 Cl.

Example 5

2- (2-Methyl-4-chlorophenoxyacetyl) benzoic acid propyl ester

Working procedure as in Example 1. Melting point 65-68 ° C.

Analysis for C ^ HH ^O ^Cl (MW: 346.8)

C, 5.52; H, 10.22; Cl;

found: 65.67 C, 5.69 H, 10.07 Cl.

Example 6,

2- (4-Chloro-phenoxy-acetyl) -benzoic acid ethyl ester

Working procedure as in Example 1. Melting point 30-34 ° C.

Ahalysis for C ^ HH ^O ^Cl (MW: 318.7)

C, 4.90, H, 11.16, Cl;

found: 64.16 C, 4.90 H, 11.16 Cl.

example

2- (4-Iodophenoxyacetyl) benzoic acid ethyl ester

Working procedure as in Example 1. Mp 56-58 ° C.

Analysis over C ^ HH ^O ^ I (MW: 410.2)

H, 3.68; H, 30.93%;

found: 49.56% C, 3.49% H, 31.40% I.

Example 9

2- (2,4-Dichlorophenoxyacetyl) benzoic acid ethyl ester

Working procedure as in Example 1. Melting point 85-88 ° C.

Analysis for C ^ HH ^O ^Ig (MW: 353.2)

H, 3.99; H, 20.07;

Found: C, 57.94; H, 3.71; Cl, 20.22.

EXAMPLE

2- (2-Naphtyloxyacetyl) benzoic acid methyl ester

Working procedure as in Example 1. Melting point 113-114.5 ° C.

Analysis for (m: 321.5)

H, 5.33; H, 5.33;

found: 74.88% C, 5.23.

Example 11

Labeling and composition of test compounds:

I. 2- (2,4,5-Trichlorophenoxyacetyl) benzoic acid methyl ester3

II. 2- (2,4,5-trichlorophenoxyacetyl) benzoic acid butyl ester

III. 2- (2,4,5-trichlorophenoxyacetyl) benzoic acid ethyl ester

IV. 2- (2,4,5-Trichlorophenoxyacetyl) benzoic acid, iodopropyl ester;

V. 2- (2-Methyl-4-chloro-phenoxy-acetyl) -benzoic acid methyl ester

VI. 2- (2-methyl-4-chlorophenoxyacetyl) benzoic acid propyl ester

VII. 2- (4-chlorophenoxyacetyl) benzoic acid ethyl ester

VIII. 2- (4-iodophenoxyacetyl) benzoic acid ethyl ester

IX. 2- (2,4-dichlorophenoxy) benzoic acid ethyl ester

X. 2- (2-naphthyloxy-ethyl) -benzoic acid methyl ester

XI. 2-methyl-4-chlorophenoxyacetic acid (MCIA) - assigned Standard

XII. 2,4-Dichlorophenoxyacetic acid - assigned Standard.

Test plants:

deaf oat, sown oat, hedgehog chicken leg, spring barley, millet, winter wheat, maize, buckwheat, sugar beet, savoy cabbage, buckwheat, sage, l'an, peas, white mustard, seed lids.

Workflow:

Seeds of test plants were seeded in rows filled with untreated arable soil. The soil surface was leveled and irrigated. In the pre-emergence treatment, aqueous emulsions of the substances at the rates indicated in the attached tables were applied directly to the soil and in the post-emergence treatment directly to the plants (Stage of the first leaves of monocotyledons and the first two true leaves of dicotyledonous species). The experiments were carried out under greenhouse conditions. The volume applied in all cases was 1000: 1.ha ^- '

The effect was assessed visually after the damage was avoided and expressed on a 0-5 score scale, with 0 representing healthy, undamaged and 5 dead plants;

to 4 are intermediate damage stages. The evaluation considered all significant changes affecting the viability of the test plants. Results 8U shown in Tables 1 to 4.

Table 1

Efficacy of substances in pre-emergence application to 5 species of test plants A = 15 kg eff. 1.ha- ¹ ; B = 5 kg acc. I.HA '

oats Linseed buckwheat common mustard White millet siate Režucha siata A B A B A B A B A B I. 5 5 5 5 5 5 • 3 1 5 5 II. 5 3.5 4 2 5 5 3 2 5 5 III. 5 4 3.5 3 5 5 5 5 5 5 IV 5 4 4.5 3 5 5 5 3 2 5 5 in. 1 0 0 0 5 5 0 0 5 5 VI. 1 0 3 2 5 5 1 0 5 5 VII. 4 3.5 3.5 2.5 5 5 5 4 5 5 VIII. 5 3 4 2 5 5 2.5 1 5 5 IX. 3 1. 3 1 5 5 3 1 5 5 y. 1 0 0 0 5 5 2 0 5 5 XII. 2 1 3 2.5 5 5 4 3.5

Continuation of Table 2

Effectiveness of substances in post-emergence application to 5 species of test plants A = 5 kg eff. 1.ha ^-1 , B = 1 kg acc. 1.ha ^-1 .

Oats Common buckwheat White mustard Millet Sieve A B A B A B A B A B I. 2 0 5 5 5 5 2 0 5 5 IV. 2 0 5 4 5 5 2 0 5 5 XII. 0 0 5 4 5 4 0 0 -

Table 3 Efficacy in pre-emergence application on the 14 kinds test plants III. VIII. XI. (Standard.) 1 58 kg 1,58 kg 1,58 kg eq. 1 acc. 1.ha ' ¹ acc. 1.ha ^-1 h "^ Avena fatua 0 ’ 2 0 Avena sativa 0 ¹ 0 0 Echinochloa crus - galli foot) 1.5 0 2 Hordeum vulgare (Spring Barley) 3 0 1 Triticum aestivum 2 0 0 Zea mays (corn) 2 0 0 Amaranthus retroflexus 5 3 5 Beta vulgaris (sugar beet) 5 4 5 Brassica oleracea (Savoy Cabbage) 4 0 5 Fagopyrum vulgare (Common Buckwheat) 2 2.5 3 Linum usitatissimum (Tan seed) 5 4 5 Pisum sativum (Peas) 0 0 5 Sinapis alba (White Mustard) 5 5 5 Vicia sativa (Gray Wolf) 3 0 3

Table 4

Efficacy of substances in pre-emergence application on 14 species of test plants A - 1 kg eff. 1.ha ' ^{* 1} , B = 0.316 kg account. 1.ha ' ¹ , G = 0.1 kg ύδ. 1.ha ¹ .

I. IV. XI. (Standard) A B G A B C ABC

Avena fatua 0 0 0 0 0 0 0 0 0 Avena sativa (Oat) Exhinochloa crus-galli about' 0 0 0 0 0 0 0 0 (hedgehog kuria foot) 0 0 0 1 0 0 2 1 0 Hordeum vulgare Triticum aestivum (wheat 0 0 0 0 0 0 0 0 0 Winter wheat) 1 0 0 1 0 0 0 0 0 Zea mays / maize) Amaranthus retroflexus 2 0 0 1 0 0 0 0 0 (Knotweed) 5 4 3 5 4 3 5 5 2 Beta vulgaris (sugar beet) 5 4 1.5 5 5 5 5 5 5 -) Brasica oleracea IN cabbage) 5 4 2 5 5 5 5 5 5 -) Pagopyrum vulgare (buckwheat) 3 3 2 4 3 2 5 4 2 Linum usitassimum (Tan seed) 5 5 5 5 5 5 5 5 2 Pisum sativum (Peas) 5 4 2 5 4 2 4 2 1 Sinapis alba (White Mustard) 5 4 2 5 4 2 5 5 2 Vicia sativa 5 4 3 5 5 3 5 5 2

OBJECT OF THE INVENTION

Claims (2)

1. Esters of 2-aryloxyacetylbenzoic acid of general formula I ABOUT About which R ¹ is alkyl of 1 to 4 carbon atoms, R is methyl, halogen, fused benzene ring. 2. A process for the preparation of esters of the formula I according to claim 1, characterized in that the 3-aryloxymethylenephthalide of the formula II is reacted. ABOUT Ii), in which o R is as defined above, with an alcohol of formula III R ¹ - OH (III) wherein R * is as defined above, at 60 to 100 ° C, in the presence of sulfuric acid or phosphoric acid or p-toluenesulfonic acid as a catalyst.