CS229700B2 - Manufacturing process of new substituted phenoxypropionate - Google Patents

Description

The present invention relates to novel substituted fenokypřopionátů which are used as active components ^{of &} herbicides.

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

Ar-O-C 6 O -t-tw-C

C-O-cH (U in which

R ¹ and R ² are each independently hydrogen or C 1 -C 6 alkyl,

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 are each independently 1 or 2 and

Ar is a group of formulas Ia or II?

Ha / (/ bf 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 of the herbicidal compositions.

According to the present invention, the novel compounds of formula (I) are prepared by the formation of a compound of formula (VI)

Ar — Z ¹ (VI) wherein

Ar and Z ¹ have the meanings given above, they act by a compound of formula VII. Q

ΜΟ-ζΥθ'θΗ ~ 'έ ~ 0

R ⁴ R ^z (VII) in which

R ¹ , R ² , X, M, and n are as defined above.

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 selective herbicidal activity against grass weeds without having any remarkable phytotoxicity against agricultural crop plants. It is particularly surprising that the tulle compounds of the present invention possess excellent properties which the structurally similar compounds of the prior art do not possess, in particular because they exhibit sufficient herbicidal activity even in small amounts, yet are well tolerated by the useful plants and 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 each independently hydrogen or methyl, ethyl, n-propyl, isopropyl, η-, iso-, sec- or tert-butyl;

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

When 4-trifluoromethylphenyl chloride and 2- (2-fluorobenzyloxyethyl) -2- (4-hydroxyphenoxy) propionate are used as starting materials, the following scheme illustrates the process:

CHS O

OCH-C-O-CH 2 CH 2 OCH 2 -

row HO

CfaO

I ³ // x \

OCH-C-O-CH 2 CH 2 OCH 2 -x + HCl

Examples of compounds of formula VI which are used as starting materials in the process of the invention include:

4- (or 2-trifluoromethylphenyl chloride, 4-fluorophenyl chloride),

2.4- dichlorophenyl chloride,

2-chloro-4-nitrophenyl chloride,

4-chloro-2-trifluoromethylphenyl chloride, 2-chloro-4H-trifluoromethylphenyl chloride,

3,5-dichloro-2-pyridinyl chloride,

5-nitropyridinyl chloride,

4-nitrophenyl chloride,

4-bromo-2-chlorophenyl chloride,

2-nitro-4-trifluoromethylphenyl chloride,

2,6-dichloro-4-trifluoromethylphenyl chloride, 2-cyano-4-trifluoromethylphenyl chloride,

2-Chloro-4-cyanophenyl chloride,

3-chloro-5-nitro-2-pyridinyl chloride,

5-Trifluoromethyl-2-pyridinyl chloride

3-chloro-5-trifluoromethyl-2-pyridinyl chloride, 5-bromo-3-chloro-2-pyridimyl chloride, and

4-chloro-2-methylphenyl chloride as well as the corresponding bromides.

Examples of other starting materials of formula VII, which are also used in the process of the invention, are:

2-Benzyloxyethyl 2- (4-hydroxyphenoxy) propionate

3-Benzyloxypropyl 1-2- (4-hydroxyphenoxy) propionate

1-Methyl-2-benzyloxy-ethyl-2- (4-hydroxy-phenoxy) -propionate

2- a-Methylbenzyloxyethyl 1-2- (4-hydroxyphenoxy) propionate

2- (2-fluorobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (4-fluorobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (2-chloro-enzyloxy) allyl-2- (4-hydroxyphenoxy) propionate,

2- (4-chlorobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (2,4-Dichlorobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (3,4-dichlorobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (2,6-dichlorobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (2-methylbenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (3-nitrobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (4-methoxybenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (4-bromobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

1-methyl-2-α-methylbenzyloxyethyl 2- (4-hydroxyphenoxy) propionate,

2- (3-chlorobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (2-thienoxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (34-Luorbenzyloxy-ethyl-2- [2- (4-hydroxy-phenoxy)] -propionate

1- Meithyl-2- (2-fluorobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate

3- (2-fluorobenzyloxy) propyl 2- (4-hydroxyphenoxy) propionate,

2- (2-nitrobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (4-mitobenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

2- (2-methoxybeinzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate,

3- (4-Fluorobenzyloxy) propyl 2- (4-hydroxyphenoxy) propionate a

2- (4-methylbenzyloxy) ethyl 2- (4-hydroxyphenoxy) propionate.

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, methyl ethyl ether, diisopropyleither, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran); ketones (such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone); nitriles (such as acetonitrile, propionitrile and acrylonitrile); alcohols (such as methanol, ethanol, isopropanol, butanol, and ethylene glycol); esters (such as ethyl acetate and amylaceitate); acid amides (such as dimethylformamide and dimethylacetamide); sulfones and salts of oxides (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. In general, the reaction is carried out at temperatures between -20 ° C and the boiling point of the reaction mixture, preferably at temperatures between 0 ° C and 100 ° C.

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 starting compounds of formula VII are new. These novel compounds of formula (VII) are prepared by compounding a compound of formula (VII)

220700 acts with a compound of formula ΪΙ1

Z - CH - CO - CH h

Xa in which

R ¹ , R ² , X, and, on Z ¹ are as previously known.

When hydroquinone and 2-benzyloxyethyl-.beta.-bromopropionate are used as starting materials, the reaction for the preparation of the compounds of formula VII can be expressed by the following equation:

HIM-

OH t Br-CH-CO-CH 2 CH 2 OCH 2 -

CH ₅ O

O-CH-CO -CH2CH2CH3CH3 +

In the preparation of the compounds of formula (VII), one of the abovementioned solvents or diluents (see process of the invention) is preferably used in order to obtain highly pure reaction products and in high yield. This reaction is likewise preferably carried out in the presence of the acid binding agent described for the process according to the invention.

Reaction conditions, ti. the reaction temperature and pressure are also selected within the same limits as described above for the process of the invention.

The preparation of the novel compounds of formula III is described in U.S. Pat. No. 229,683.

The following examples illustrate the invention but do not limit it:

Example 1 a d

CH ^ Q ° ^ ^H ^ “°” ^CW 2 ^CW J ^and “ ^CH r ^ y '

33.4 g of 2- (2-fluoro-benzyloxy-ethyl-2- (4-hydroxy-phenoxy) -propionate) are dissolved in 120 ml of dimethylformamide and 15.2 g of potassium carbonate are added thereto, followed by heating at 95 ° C with stirring for 1 hour. 27.1 grams of 4-trifluoromethylchlorobenzene are then added and the reaction mixture is heated at 95-100 ° C for 5 hours, after cooling to room temperature, the reaction solution is poured over ice water and extracted with toluene. The toluene was distilled off under reduced pressure and the other volatile by-products were removed by filtration (100 ° C / 13.3 Pa) to give 20.7 g 2. - (2-fluorobenzyl oxy) ethyl 2- [4- (4-trifluoromethylphenoxy) phenoxy] propionate as reaction product.

m, ³ '- = 1.5235.

Example 2

WHAT

OCH-C-O-CH 2 -CH 2 O-CH 2 O 2

31.6 g of 2-benzyloxyethyl 2- (4-hydroxyphenoxy) propionate are dissolved in 100 ml of dimethylsulfoxide, to which 15.2 g of potassium carbonate are added, and the reaction mixture is heated at 90 DEG C. for 1 hour.

The reaction mixture was then added dropwise to 20.0 grams of 2-methyl-5-methyl-5-thiophenol and the reaction mixture was maintained at 90 ° C for 2 hours. After cooling to room temperature, the reaction solution was poured into ice water and then extracted with ether. The ether layer was dried and filtered and the ether was distilled off. 2-Benzyloxyethyl-2- [4- (5-trifluoromethyl-2-pyridyloxy-phenoxy) -propionate is obtained in 41.0 g (s), m.p. 44-47 ° C.

The other compounds of formula I are prepared in an analogous manner and are listed in the following table:

Table

R *. CH ·). or><_ v / Τ ^ λ I ^J π i I

Ar-O-CH 2 O-CH-C-O-CH (CH 3 O-CH 3) (U

NO _Z

Η H

Η H

Η H

Η H

H, n = ^20, 1.5518

H n _D ²⁰ 1.5696

H n _D ²⁰ 1.5805

H n _D ²⁰ 1.5397

8 ^F 3 ^C ~ ^ ~ H H 1 H n _D ²⁰ 1.5450 9 H H 2 H n _D ²⁰ 1.5268 10 —Ch ₃ H 1 H n _D ²⁹ 1.5280 11 H -ch ₃ 1 H n ₀ ²⁰ 1.5266 12 H H 1 2-F n _D ²⁰ 1.5235 13 ^F 3 ^C -O- H H 1 4-F n _D ²⁰ 1.5214 14 faO " H H 1 2-C1 n _D ²⁰ 1.5360

example number

R ¹ R ² n

Η Η 1

Η Η 1

Η Η 1

Η Η 1

Η Η 1

Η Η 1

Η Η 1

Η H ¹ 1

Η Η 1

Η Η 1

Η H 2

Η Η 1

Η Η 1

Η Η 1

Η Η 1

Η Η 1

X _and physical data

2-C1 no ²⁰ 1.5550 4-C1 no ²⁰ 1.5360 4-C1 n _D ²⁰ 1.5380 4-C1 no ²⁰ 1,5450 4-C1 n _D ²⁰ 1.5559 2,4-Cl ₂ n _D ²⁰ 1.5422 _3,4-Cl2 no ²⁰ 1,5428 _2-CH3 n _D 20 1.5305 3-NO ₂ n _D ²⁰ 1.5436 4-OCH3 , n _D ²⁰ 1.5343 H tench ²⁰ 1.5440 4-C1 n _D ²⁰ 1.5875 4-Br n _D 2 ° 1.5450 H n _D ²⁰ 1.5650 2-C1 n _D ²⁰ 1.5718 H 1.1. Mp 59-61 ° C

example number Ar R ¹ R ² n Xa physical data 31 H ch ₃ 1 H n _D ²⁰ 1.5715 32 Cl ^ct ~ Oh ' H H 2 H n _D ²⁰ 1.5721 33 H H 1 H oil 34 ° from ^N ~ O ~ Ct H H 1 3-NO ₂ oil 35 / Cí-A- H H 1 2-F mp 54-57 ° C 36 '-/IN H H 1 2-C1 mp 64-66 ° C 37 H H 1 4-C1 no ²⁰ 1.5803 38 «-Ď- H H 1 4-C1 oil 39 H H 1 3-NO ₂ n _D ²⁰ 1.5845 40 f ¹ ci-Q. H H 1 _2-CH3 1.1. Mp 83-85 ° C 41 H H 1 2,4-Cl ₂ oil 42 C1- ^or A-; H H 1 _3,4-Cl2 n _D 2 ° 1.5900 43 CI ^CI - <5. H H 1 2,6-Cl ₂ n _D ²⁰ 1.5915

229780 example number

Ar

R ¹ R ² n X _and physical data

44 Cl H 45 ^Affairs - <5- H 46 ^F 3 ^C -Q ' H 47 H 48 ^F 3 ^C O- H 49 ^r 3 ^c -Q- H 50 H 51 H

The following examples illustrate the preparation of the novel compounds of formula (52) in more detail

ch ₃ o

OCH-C-O-C (CH 2) O-CHg

H 1 4-OCH ₃ n _D 2 ° 1.5735 H 1 4-Br n _D ²⁰ 1.5870 ch ₃ 1 H n _D 2 ° 1.5254 H 1 2-CH3 n _D ²⁰ 1.5273 H . 1 2-C1 no ²⁰ 1.5349 H 1 4-Br n _D ²⁰ 1.5440 H 1 3-NO2 no ²⁰ 1.5428 H 1 2,4-Cl ₂ n _D ²⁰ 1.5424 ce VII, which is they use me as starting material

for the process according to the invention.

(compound of formula VII j

12.1 g of hydroquinone are dissolved in 60 ml of absolute dimethylformamide and in this way in a yield of 24.6 g. No ^21.5 1.5390.

31.7 g of potassium carbonate are added under a slow stream of nitrogen, and then the reaction mixture is heated to 90-95 ° C with stirring for 1 hour. After cooling the reaction mixture to 60 ° C, 28.7 g of 2-benzyloxyethyl 2-bromopropionate are added dropwise. The reaction mixture was then heated at 90 ° C for 2 hours. After cooling the reaction mixture to room temperature, the mixture was poured into ice water, adjusted to pH 7 and extracted with 100 ml of toluene. The toluene layer was dried and filtered. From the filtrate, toluene was removed by distillation under reduced pressure. Colorless oily product, i.e. 2-benzyloxy-2- (4-hydroxyphenoxy) propionate was obtained in a yield of 24.6 g. Of n _D ^21-5 = 1.5390.

The compounds of formula (VII) which are used as starting materials and which are listed in the following table are obtained in a similar manner as described above.

Table 1

Μ R ¹ R ² η Xa physical constants

H H H H H H H H H 1 1 1 H 2-F 4-CI n _D 2i-5 2i _ _D n, _D n 5 ₌ ^21.5 1,5390 1.5260 1,5473 H I.T X A H 1 3,4-Cl _{2 nD} 21,5 _ 1.5570 H CH, H 1 H n _D20 , s ₌ 1,5321 H H ch, 1 H n _D 2 <> -5 = 1,5336 H H H 2 H n _D 21i-5 = 1.5344 H H H 1 4-OCH, n _D 20.5 ₌ 1,5422

OBJECT OF THE INVENTION

Claims (1)

A process for the preparation of the novel substituted phenoxypropionates of the general formula (I). f f Ar-O- (γ-O-CH-C-O-CH in the same); R ¹ and R ² are each independently hydrogen or C 1 -C 6 alkyl, 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 are each independently 1 or 2 and Ar represents a group of formulas Ia or Ib (i.e. where Y is trifluoromethyl, halogen or nitro, cyano or (C1-C6) alkyl, and b is 1, 2 or 3, wherein the compound of formula (VI) Ar — Z * (IV) wherein Ar and Z ¹ are as defined above, with a compound of formula VII no O I Í! OCH-CR ^ R ² ' CH 2 CH 6 CH 2 O-CH · (VH) wherein R ¹ , R ² , X and a 'are as defined above, a M represents a hydrogen atom or an alkali metal atom, optionally in the presence of an acid-binding agent and optionally in the presence of a diluent at a temperature between 0 ° C and 10D degrees Celsius.