CS229699B2 - Manufacturing process of new substituted phenoxypropionate - Google Patents

Description

(54) A method for producing new substituted phenoxypropionates

The present invention relates to a process for the preparation of novel substituted phenoxypropionates which are used as active ingredients of herbicides.

It has been found that the novel substituted phenoxypropionates of formula (I)

CH ₃ 0 RRY

IΗ I Kb

O-CH-CH 2 O-CH 2 CH 2 O-CH-ζ K * tU in which

R ¹ and R ² are independently hydrogen or alkyl having 1 to 6 carbon atoms,

X represents a hydrogen atom or a halogen atom or a nitro group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and n each independently represent 1 or 2; and

Ar is a group of formulas Ia or 1b

.............'.........

(Ia) UM where

Y is trifluoromethyl, halogen or nitro, cyano or (C1-C6) alkyl, and b is 1, 2 or 3, have herbicidal properties and can therefore be used as active ingredients in herbicidal compositions.

According to the present invention, the novel compounds of formula (I) are produced by converting to compounds of formula (IV) from -λ | ³ l! 2

ΛΓ-Ο — O-CH-C-Z + (IV) wherein

Ar is as defined above and Z ² is a hydroxyl group or a halogen atom

in which:

R ¹ , R ² , X, a and ⁿ have the above meanings, at a temperature between 0 ° C and 100 ° C.

Surprisingly, the substituted phenoxypropionates of the present invention, which have not been previously described in the literature, can be readily synthesized in high yields and are novel active compounds having excellent herbicidal activity against grass weeds without having any remarkable phytotoxicity against agricultural crop plants. It is particularly surprising that these compounds of the present invention possess excellent properties which the structurally similar compounds of the prior art do not possess, particularly in that they exhibit sufficient herbicidal activity even in small quantities, yet are well tolerated by the useful plants, against weed regeneration, in particular perennial monocotyledonous weeds, since they have an excellent long-lasting effect.

Preferred compounds produced in accordance with the present invention and accordingly the corresponding starting materials are those in which:

Ar represents a group of formula Ia or Ib, wherein

Y represents trifluoromethyl, fluorine, chlorine, bromine or iodine, or nitro, cyano, methyl, ethyl, propyl, isopropyl, η-, iso-, sec or tert-butyl;

b is 1, 2 or 3;

R ¹ and R ² are independently hydrogen or a methyl group, ethyl group, n-propyl, isopropyl, η-, iso-, sec., Or tert-butyl group;

X is hydrogen, fluorine, chlorine, bromine or iodine, nitro, methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxy, isopropyl, isopropoxy or η-, iso-, sec. or t-butyl or -butoxy, and a and n are each independently 1 or 2.

When 2- [4- (3,5-dichloro-2-pyridyloxy) phenoxy] propionyl chloride and 1-benzyloxy-2-propanol are used as starting materials, the following reaction scheme can be illustrated:

+ HC.I

Examples of compounds of the formula IV which are used as starting materials for the process according to the invention are:

2- [4- (4-Trifluoromethylphenoxy) phenoxy] propionyl chloride,

2- [4- (2-Trifluoromethylphenoxy) phenoxy] propionyl chloride,

2- [4- (4-ifluorophenoxy) phenoxy] propionyl chloride,

2- (4- (2,4-dlchlorophenoxy) phenoxy] propionyl chloride ,,

- [4- (2-chloro-4-nitrophenoxy) alkoxy] propionyl chloride,

2- [4- (2-Trifluoromethyl-4-chlorophenoxy) phenoxy] propionyl chloride,

2- (4- (3,5-dichloro-3H-pyridyl-oxy-phenoxy) -propionyl-chloride),

2- (4- (4-Trifluoromethyl-2-chlorophenoxy) phenoxy] propionyl chloride,

2- (4- (5-methyl-2-pyridyloxy) phenoxy] propionyl chloride,

2- [4- (4-nitrophenoxy) phenoxy] propionyl chloride,

2- (4- (4-bromo-2-chlorophenoxy) phenoxy] propionyl chloride,

2- [4- (4-Trifluoromethyl-2-nitro of enoxy) phenoxy] propionyl chloride,

2- [4- (2,6-dichloro-4-trifluoromethylphenoxy) phenoxy] propionyl chloride,

2- [4- (2-cyano-4-trifluoromethylphenoxy) phenoxy] propionyl chloride,

2- [4- (2-chloro-4-cyanophenoxy) phenoxy] propionyl chloride,

2- (4- (3-chloro-5-nitro-2-pyridyloxy) phenoxy] propionyl chloride,

2- [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] propionyl chloride,

2- [4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy] propionyl chloride,

2- [4- (5-bromo-3-chloro-2-ipyridyloxyphenoxy) propionyl chloride; and

2- [4- (4-chloro-2-methylphenoxy) phenoxy] propionyl chloride as well as the corresponding bromides or derivatives with a free propionic acid residue.

Examples of other starting materials of the formula V which are used in the process according to the invention are:

2-Benzyloxyethanol

3-Benzyloxypropanol

1-Benzyloxy-2-propanol

2-α-methylhenzyloxyethanol,

2- (2-fluorobenzyloxy) ethanol,

2- (4-fluorobenzyloxy) ethanol,

2- (2-chloro-enzyloxy) ethanol,

2- (4-chlorobenzyloxy) ethanol,

2- (2,4-dichlorobenzyloxy) ethanol,

2- (3,4-dichlorobenzyloxy) ethanol,

2- (2,6-dichlorobenzyloxy) ethanol,

2- (2-methylbemzyloxy) ethanol,

2- (3-initrobenzyloxy) ethanol

2- (4-methoxybenzyloxy) ethanol,

2- (4-bromobenzyloxy) ethanol;

1- (α-methylbenzyloxy) -2-propanol,

2- (3-Chlorobenzyloxy) eithanol

2- (2-bromobenzyloxy) ethanol,

2- (3-fluorobenzyloxy) ethanol,

1- (2-fluorobenzyloxy) -2-propanol,

3- (2-fluorobenzyloxy) propainol,

2- (2-nitrobenzyloxy) ethanol,

2- (4-nitrobenzyloxy) ethanol,

2- [4-methylbenzyloxy] ethanol,

2- (2-methoxybenzyloxy) ethanol a

3- (4-Fluorobenzyloxy) propanol.

The process of the present invention is preferably carried out in the presence of a diluent. All inert solvents can be used for this purpose.

Examples of such solvents or diluents are water, aliphatic, alicyclic and aromatic hydrocarbons, which may in each case optionally be chlorinated (such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichlorethylene and chlorobenzene). ethers (such as diethyl ether, methylethyl ether, diisopropyl ether, dibujyl ether, propylene oxide, dioxane and tetrahydrofuran); ketones (such as acetone, methyl ethyl ketone, methylisopropyl ketone and methylisobutyl ketone); esters (such as ethyl acetate and amyl acetate); acid amides (such as dimethyliformamide and dimethylacetamide); sulfones and sulfides (such as dimethylsulfoxide and sulfolane); and bases (such as pyridine).

The process according to the invention is preferably carried out in the presence of an acid binding agent. Examples of such acid binding agents include alkali metal hydroxides, carbonates, bicarbonates and alkoxides and tertiary amines such as triethylamine, diethylaniline and pyridine.

The process according to the invention can be carried out over a wide temperature range. Generally the reaction is carried out at temperatures between -20 DEG C. and the boiling point reakčiní mixture, preferably at temperatures between 0 DEG and 100 DEG C. ^q

The process according to the invention can be carried out at atmospheric pressure, although it is also possible to work at elevated or reduced pressure.

The invention is illustrated by the following examples.

Example 1

22.1 g of 2- (2,6-dichlorobenzyloxy) ethanol and 10.1 g of triethylamine are dissolved in 200 ml of toluene and the solution obtained is cooled to 0 ° C. To this solution was added dropwise at 0-10 ° C a solution of 34.5 g of 2- [4- (4-trifluoromethylphenoxy) phenoxy] propionyl chloride in 50 ml of itoluene. After completion of the dropwise addition, the reaction mixture was slowly warmed and stirred at 40 ° C for 1 hour to complete the reaction. After cooling the reaction solution to room temperature, the reaction solution was washed successively with 1% aqueous sodium hydroxide solution and water, and then dried to remove water. After the toluene was distilled off under reduced pressure, the resulting colorless viscous oil was left to rest for about 1 month, after which 49.2 grams of crystalline 2- (2,6-dichlorobenzyloxy) ethyl-2- [4- (4-trifluoromethylphenoxy) -phenol crystallized. mp 51-53 ° C.

EXAMPLE 2 · ^ 'w-- / ^Cl CH ₃ a CH

Cl -OH-O - ^ - O-CH-C-O-CH _Z <h ^ 2>

16.6 g of 1-benzyloxy-2-propanol and 10.6 g of triethylamine are dissolved in 200 ml of toluene and the solution obtained is cooled to 0 ° C. A solution of 34.7 g of 2- [4- (3,5-dichloro-2-pyridyloxy) phenoxy] propionyl chloride in 80 ml of toluene was added dropwise with stirring at 0 ^(C to 5 ° C). The mixture is slowly warmed to 40-50 [deg.] C. to complete the reaction for 1 hour. After cooling to room temperature, the reaction mixture is washed successively with 1% aqueous sodium hydroxide solution and water and then dried. viscous olejovatého l-methyl-2-benzyloxy-2- [4- (3,5-dichloro-2-yloxy py chlorides her phenoxy opionátu j pr. n _i ²⁰ = 1.5710.

Examples 3 to 11

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The compounds of the following table are prepared in an analogous manner: Table

CH 3 R ¹ S * _χ

CH-C-O-CH (CH 2 O <

X _and physical daita

H n _D ²⁰ 1.5322

H n _D ²⁰ 1.5518

H n _D ²⁰ 1.5696

H n _D ²⁰ 1.5805

H n _D ²⁰ 1.5397

H n _D ²⁰ 1.5450

H, _r = 1.5268

H n _D ²⁰ 1.5260

H n _D ²⁰ 1.5266

2-F n _D ²⁰ 1.5235

4-F n _D 2 ° 1.5214

2-C1 n _D ²⁰ 1.5360

2-Cl n _D ²⁰ 1.5550

4-C1n _D ²⁰ 1.5360

4-C1n _D ²⁰ 1.5380

example number Ar R ¹ R ² n Xa physical dalta 27 Mar: π H H 1 4-C1 n _D ²⁰ 1.5450 28 r- (y H H 1 4-C1 LV ²⁰ 1.5559 29 f ₃ ^c -0- H H 1 2,4-Cla n _D ²⁰ 1.5422 30 H H 1 _3,4-Cl2 LV ²⁰ 1.5428 31 H H 1 2-CH3 n _D ²⁰ 1.5305 32 H H 1 3-NO ₂ n _D ²⁰ 1.5436 33 H H 1 4-OCH ₃ n _D ²⁰ 1.5343 NO, y _t * 34 F _and ^c "^ 2 / H H 2 H n _D ²⁰ 1.5440 Cl 35 H H 1 4-C1 n _D ²⁰ 1.5875 36 f ₃ ^c ~ O- H H 1 4-Br n _D ²⁰ 1.5450 Ctfj 37 / ^Ci ~ - \ Z / H H 1 H n _D ²⁰ 1.5650 38 ./ / ¾ící-O- Cř H H 1 2-C1 in _D ²⁰ 1.5718 39 «-Q- H H 1 H mp 59-61 ° C 40 H ch ₃ 1 H n _D ²⁰ 1.5715 Cl 41 ^Ci ~ ^ ~ H H 2 H n _D ²¹³ 1.5721 42 v-Q- H H 1 H oil

Claims (1)

OBJECT OF INVENTION A process for the preparation of the novel substituted phenoxypropionates of the formula I Ar ~ O / 1 CH, o R R at | 3 II J J X.S O-CH-C-O-CH 2 Cl 2 O-CH-? -y * • (!) in which R ¹ and R ² are independently hydrogen or alkyl having 1 to 6 carbon atoms, X represents a hydrogen atom or a halogen atom or a nitro group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n each independently represent 1 or 2, and Ar is a group of formulas Ia or Ib CH ³ O ^{3 3} H 2 O-CH-C-Z (IV) wherein Ar is as defined above and Z ² is a hydroxyl group or a halogen atom, acts by a compound of formula V (IA) (Ib> ho-cm-their ^ o-ch- ^ * Y is trifluoromethyl, halogen or nitro, cyano or (C1-C6) alkyl; and b is 1, 2 or 3, wherein the compound of formula (IV): R ¹ , R ² , X a and ⁿ are as defined above, optionally in the presence of an acid binding agent and optionally in the presence of a diluent, at temperatures between 0 ° C and 100 ° C.