CS209529B2 - Method of making the (pyrimidyloxy) phenoxyalcancarboxyl acids derivatives - Google Patents

Description

(54) A method for producing (pyrimidyloxy) phenoxyalkanecarboxylic acid derivatives

The invention relates to a process for the preparation of (pyrimidyloxy) phenoxyalkanecarboxylic acid derivatives having herbicidal properties. It has been found that certain novel (pyrimidyloxy) phenoxyalkanecarboxylic acids and derivatives thereof exhibit biological activity, particularly herbicidal activity.

Accordingly, the present invention provides a compound of formula I, v

B D tf (I) in which

A and D are each independently hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxycarbonyl or halogen,

B is hydrogen, halogen, cyano, (2-6C) alkoxycarbonyl, (1-6C) alkyl, (1-6C) haloalkyl or (1-6C) alkoxy,

E and V each independently represent a hydrogen atom, a halogen atom, a nitro group or an alkyl group having 1 to 6 carbon atoms,

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

W represents a hydroxymethyl group or a radical of formula

O — C — G where

G is hydroxyl, C1-C10 alkoxy optionally substituted by halogen, cyano, phenyl or C1-C6 alkoxy, C1-C10 alkylthio optionally substituted by phenyl, C2-C10 alkenyloxy C 2 -C 10 alkenylthio, C 2 -C 10 alkynyloxy, phenoxy optionally substituted by nitro, cyclohexyloxy, amino optionally substituted by one or two substituents selected from C 1 -C 6 alkyl, phenyl, optionally substituted with halogen or haloalkyl of 1 to 6 carbon atoms and thienylmethyl, further denotes a morpholino group or an OM residue, wherein M represents an alkali metal or alkaline earth metal ion, and

X and Y are each independently oxygen or sulfur, and their optical isomers and salts thereof.

Compounds of formula I wherein R ¹ and R ² do not represent the same radicals are optically active ,, and the invention also includes the individual stereoisomers of such compounds, and mixtures of such stereoisomers as well as racemic mixtures of stereoisomers.

Preferred radicals A, B and D are hydrogen, alkyl of 1 to 6 carbon atoms, alkoxycarbonyl of 2 to 6 carbon atoms, halogen atoms, alkoxy of 1 to 6 carbon atoms and haloalkyl of 1 to 6 atoms carbon.

A preferred radical R @ ¹ is a hydrogen atom or a C1 -C6 alkyl group, a preferred radical R @ ² is a hydrogen atom or a methyl group.

Preferably W represents the remainder of the formula

O — C — G, in which

G is hydroxyl, C 1 -C 10 alkoxy optionally substituted by halogen or C 1 -C 6 alkoxy, C 2 -C 10 alkenyloxy, C 2 -C 10 alkynyloxy or cyclohexyloxy.

Preferred radicals X and Y are oxygen atoms.

The following compounds are exemplified by the compounds of the invention:

unAn Z — Λ

7-OCH-CO ^C ^a

^c ° '^ ^h ' ^ch 1 ° ^{h F} i ^C

O-CH-CO _L Na.

CH-,

eviiiy / IB 77 i i <) V !: i V:) ii Ji / Ubii! VuM.h;

Specific examples of compounds of the invention are: compounds of formula XX,

ÍXXJ in which

W represents a radical of the formula —C — G,

0 listed in Table 1, compounds of formula XXb,

--N W

Y-C-W

0 shown in Table 3, compounds of formula XXIII, wherein

W represents the CH 2 OH group shown in Table 1b of the compound of formula XXI,

in which

W represents a radical of the formula —C — G,

0 listed in Table 2, compounds of formula XXII,

(XXII)

(XXIII) in which

W represents a radical of the formula —C — G,

0 listed in Table 4, and compounds of formula XXIV,

(XXIV) in which

W represents a radical of the formula —C — G,

O in which

W represents the remainder of the formula in Table 5.

Table 1

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The compounds of formula (I), as well as their optical isomers or salts, can be prepared by a number of methods.

In accordance with the invention, the compounds of formula (I) above are prepared by sequentially condensing a pyrimidine derivative of formula (V),

B D (V) in which

L represents an easily cleavable group and the remaining general symbols have the meanings given above, with the corresponding phenol or thiophenol of formula VII,

wherein the individual symbols are as defined above, the product obtained in which Q is C1 -C6 alkoxy or C1 -C6 alkylthio is dealkylated to give a compound of formula IX,

wherein the individual symbols are as defined above, and the product of formula (IX) obtained in one of the preceding reaction steps is condensed with a compound of formula (X),

R1 hal — C — W (X)

R ² wherein hal represents chlorine, bromine or iodine in the presence of an alkaline reagent.

The above condensations are preferably carried out in the presence of an alkaline agent and preferably in the presence of a solvent. Suitable alkaline agents include, for example, alkali metal and alkaline earth metal hydroxides and carbonates such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. Suitable solvents include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and dipolar aprotic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoramide and sulfonate.

The reaction conditions required to carry out the condensation reaction vary depending on the nature of the reactants, the alkaline reagent used and the solvent. Generally, the reaction is accelerated by heating, usually with a reaction temperature in the range of 40 ° C to 150 ° C and a reaction time of 0.5 to 20 hours. However, higher or lower reaction temperatures and / or shorter or longer reaction times may be used if desired.

A suitable leaving group L is, for example, an alkylsulfonyl group, chlorine, bromine or iodine.

The dealkylation reaction can be carried out using a variety of reagents known in the art. For example, arylalkyl ethers can be resolved using reagents such as pyridine hydrochloride, hydroiodic acid, hydrobromic acid, sodium thioethoxide in dimethylformamide, acetyl p-toluenesulfonate, sodium or potassium iodide in formic or acetic acid, lithium iodide in 2,4 , 8-collidine and boron tribromide.

Reaction times and reaction conditions vary over a wide range, depending on the dealkylating agent used and the ether cleaved. The reaction conditions generally used with the above-mentioned ether cleavage reagents are known to those skilled in the art and can be adapted without any extensive experimental verification to effect the cleavage of the ethers of formula IX.

In particular, the compounds of formula (I) above wherein the grouping of formula (I) are prepared as described above

is attached at the 2- or 4-position of the pyrimidyl ring.

Compounds of formula (Ia) below (i; w = -c-G), o

wherein G is not a hydroxyl group, can be prepared from an acid of formula Ib (I; W = -CO 2 H) by any of the conventional methods known in the art for converting carboxylic acids to salts, esters or acid amides. Such a procedure can be illustrated by the following Reaction Scheme A.

Scheme A ομ

B D in K (Ib)

(/ éú

Compounds of general formula Ic [I; W = -CH 2 OH) can be prepared from * an acid or an acid ester of formula Id (I; w = -C-G,

II o

where

G (OH or alkyl) by any of the conventional methods known in the art for converting an acid to an acid ester or an alcohol (for example, by reduction with lithium aluminum hydride). Such a process can be illustrated by the following Reaction Scheme B.

Scheme B

(Iq)

The compounds of the invention exhibit herbicidal activity against a wide variety of plants, both monocotyledonous and dicotyledonous, but are nevertheless selectively effective so that when applied to certain useful plants, including cereals, and in particular, dicotyledonous crops, they do not relatively affect these useful plants. plants when administering those doses of the compounds of the invention that are lethal or severely damaging to other plant species.

The disclosed compounds are effective both in direct application to plants (post-emergence application) and in soil application prior to emergence of plants (pre-emergence application). However, the compounds of the invention are generally more effective in postemergence application to plants.

The application rates of the compounds according to the invention depend on various factors, such as the nature of the weeds and / or crop plants to which the active compounds are applied and the nature of the compound used. In general, doses ranging from 0.01 to 20 kg per hectare are preferred, preferably from 0.1 to 2 kg per hectare. Those skilled in the art will not have difficulty finding suitable application rates using standard conventional methods without carrying out any extensive experimental verification.

Compounds No. 1, 14, 15, 16, 28, 67, 73, 74 and 75 of Table 1 exhibit particularly good selectivity in weed control in dicotyledonous crops such as sunflower, cotton, soybean, sugar beet and groundnut.

The compounds of the invention may be used as such to inhibit the growth, severe damage or control of plants, but are preferably used in the form of compositions comprising a compound of the invention in admixture with a solid or liquid diluent carrier.

Methods for preparing formulations containing the compounds of the invention as active ingredients, as well as a description of the application of these formulations and the results of efficacy tests are disclosed in our co-pending Czechoslovak Patent Specification No. 20,197,527.

The invention is illustrated by the following non-limiting examples.

Example 1

Preparation of ethyl 2- [4- (5-bromo-2-pyrimididyloxy) phenoxy] propionate (1)

(a) Mixture of 3,0 g of 5-bromo-2-chloropyrimidine,

2.5 g of p-methoxyphenol, 50 ml of methyl ethyl ketone dried over anhydrous potassium carbonate and 2.5 g of anhydrous potassium carbonate were stirred and refluxed for 6 hours. The solvent was evaporated under reduced pressure, water was added to the residue and the precipitated compound was filtered off. A 5% aqueous sodium hydroxide solution was added to the product, and the mixture was stirred for about 30 minutes. The solid material was filtered and washed with water and recrystallized from methanol / water to give 3.4 g of 5-bromo-2- (4-methoxyphenoxy) pyrimidine, m.p. 92 ° C.

bj 2.4 g of 5-bromo-2- (4-methoxyphenoxy) pyrimidine are dissolved in 50 ml of methylene chloride, the solution is cooled to -70 ° C and 12.7 g of boron tribromide is added dropwise while stirring. The reaction mixture was stirred at -65 to -75 ° C for an additional hour, then allowed to slowly warm to room temperature and water was carefully added in small portions to remove methylene chloride. heating the mixture on a water bath.

203529

The aqueous suspension is cooled to 20 ° C, the solid material is filtered off, washed with water and recrystallized from a mixture of methanol and water. 2.1 g of 4- (5-bromo-2-pyrimidyloxy) phenol, m.p. 178 DEG C., are obtained.

c) A mixture of 1.45 g of 4- (5-bromo-2-pyrimidyloxy) phenol, 1.1 g of ethyl 2-bromopropionate, 20 ml of methyl ethyl ketone dried over anhydrous potassium carbonate and 1.0 g of anhydrous potassium carbonate was stirred with 8 boiling under reflux. The solvent was evaporated under reduced pressure, water was added to the residue, the mixture was extracted with methylene chloride, the methylene chloride extract was dried over anhydrous sodium sulfate, and the methylene chloride was evaporated under reduced pressure. Purification of the residue by silica gel column chromatography using chloroform as eluent gave 0.9 g of a liquid product, identified by proton magnetic resonance spectroscopy and mass spectrometry as expected ethyl-2- [4- (5-bromo-2-pyrimidyloxy) phenoxy] propionate.

Example 2

In accordance with the procedure described in Example 1 for the preparation of Compound No. 1 of Table 1, Compounds No. 3, 11, 12, 13, 14, 24, 25 are prepared from the corresponding 2-chloropyrimidine, p-methoxyphenol and the corresponding alkyl esters of 2-bromoalkanoic acids. 26, 27, 28 and 32 of Table 1 and compounds No. 76, 78 and 79 of Table 2. The products were identified by proton magnetic resonance spectroscopy or mass spectrometry, and their characteristic data are given in Table 6 below.

Example 3

Preparation of ethyl 2- [4- (5-chloro-2-pyrimidylthio) phenoxy] propionate (42)

a] 30 g of 5-chloro-2-methylthlo-4-pyrimidinecarboxylic acid was heated to 180-200 ° C until all solid material melted and carbon dioxide evolution ceased (5 minutes). The residue was allowed to cool and then washed several times with chloroform. The chloroform washings were freed of dark insoluble material by filtration and the filtrate was concentrated to give 21 grams (89%) of 5-chloro-2-methylthiopyrimidine as a light brown crystalline solid, m.p. 55 ° C.

b) To a solution of 19 g of 5-chloro-2-methylthiopyrimidine in 45 ml of acetic acid at 20 ° C was added 45 ml of 30% hydrogen peroxide. First, a suspension is formed which is clarified after 24 hours to give a colorless solution, from which 15 g (67%) of 5-chloro-2-methylsulfonylpyrimidine precipitate in the form of large colorless crystals, m.p. 124 DEG C., over 5 days.

c) To a solution of 6.7 g of 5-chloro-2-methylsulfonylpyrimidine and 5.0 g of 4-methoxythiophenol in 50 ml of methyl ethyl ketone was added 5.8 g of potassium carbonate, and the mixture was refluxed under stirring for 3 hours. The solvent was evaporated under reduced pressure and the residue was partitioned between chloroform and 5% aqueous sodium hydroxide solution. The chloroform extracts were dried over magnesium sulfate and evaporated under reduced pressure to give 8.5 g of 5-chloro-2- (4-methoxyphenylthio) pyrimidine as a colorless solid, m.p. 75 ° C.

d) 7.5 g of 5-chloro-2- (4-methoxyphenylthio) pyrimidine are dissolved in 60 ml of methylene chloride, the solution is cooled to -78 ° C and stirred while maintaining the temperature at -65 to -75 degrees Celsius. 18 g of boron tribromide is added dropwise. After the addition was complete, the reaction mixture was stirred at -78 ° C for an additional hour, then allowed to slowly rise to 20 ° C. The reaction was quenched by the addition of 50 ml of water, the resulting suspension was cooled and filtered to give 5 g of 4- (5-chloro-2-pyrimidylthio) phenol as an almost colorless solid.

e) A mixture of 2.36 g of 4- (5-chloro-2-pyrimidylthiophenol), 1.81 g of ethyl 2-bromopropionate, 20 ml of methyl ethyl ketone and 1.55 g of anhydrous potassium carbonate was heated under reflux for 16 hours. The residue was partitioned between chloroform and water, dried over magnesium sulphate and evaporated to give 4.0 g of a liquid residue which was chromatographed on 30 g of silica gel with chloroform to give an almost colorless solid. liquid product formed by identification of PMR with ethyl 2- [4- (5-chloro-2-pyrimidylthio) phenoxy] propionate spectroscopy.

Example 4

In accordance with the procedure described in Example 3 for the preparation of compound 42, compounds 33 and 48 of Table 1 and compounds 82 and 83 of Table 3 were also prepared from the corresponding 2- (methylsulfonyl) pyrimidine, the corresponding methoxyphenol and the corresponding bromoalkanoic acid ester. The products were identified by Proton Magnetic Resonance Spectroscopy (PMR) or Mass Spectrometry, and their characteristics are given in Table 6 below.

Example 5

Most of the compounds of the present invention are oily products that are characterized and that can be identified by PMR spectroscopy. For simplicity, PMR spectra data, mass spectrometry data, and any melting and boiling points of the compounds prepared by the process of the invention are summarized in Table 6 below.

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Legend:

(a) mass spectrum: m / e 288 (M ^& lt ^{; +} & gt ^; ), 215, 178

b) comprises a proton radical R ²

c) protons of the ethoxy group on the pyrimidyl ring

d) includes protons of the thienyl residue and its mass spectrum: m / e 407 (M ⁺ )

(f) Mass spectrum: m / e 415 (M ⁺ )

g) comprises allyl protons hj comprises one proton of a pyrimidyl residue

j) includes protons of group 3-C1-C6H4-O

s = singlet šs = broad singlet d = doublet d — d = doublet of doublets t = triplet q = quartet m = multiplet

Claims (6)

I will invent the object A process for the preparation of (pyrimidyloxy) phenoxyalkanecarboxylic acid derivatives of the general formula I, in which A and D are each independently hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxycarbonyl or halogen, B is hydrogen, halogen, cyano, (2-6C) alkoxycarbonyl, (1-6C) alkyl, (1-6C) haloalkyl or (1-6C) alkoxy, E and V each independently represent a hydrogen atom, a halogen atom, a nitro group or an alkyl group having 1 to 6 carbon atoms, R ¹ and R ² are each independently hydrogen or C 1 -C 6 alkyl, W represents a hydroxymethyl group or a radical of formula O — C — G where G is hydroxy, C1-C10 alkoxy optionally substituted by halogen, cyano, phenyl or C1-C6 alkoxy, C1-C10 alkylthio, optionally substituted phenyl, C2-C10 alkenyloxy carbon, alkenylthio of 2 to 10 carbon atoms, alkynyloxy of 2 to 10 carbon atoms, phenoxy optionally substituted by nitro, cyclohexyloxy, amino optionally substituted by one or two substituents selected from the group consisting of alkyl groups of 1 to 6 carbon atoms, phenyl, optionally substituted by halogen or (C1-C6) haloalkyl, and thienylmethyl, further being a morpholino group or an OM residue, wherein M is an alkali metal or alkaline earth metal ion, and X and Y are each independently oxygen or sulfur, their optical isomers or salts, characterized in that the formula V, a pyrimidine derivative of general formula (V) in which: L is an easily cleavable group and the remaining symbols are as defined above, with the corresponding phenol or thiophenol of formula (VII), (VII) wherein the individual symbols are as defined above, the product obtained wherein Q is a (C 1 -C 6) alkoxy group or (C 1 -C 6) alkylthio is dealkylated to form a compound of formula (IX), YH in which the individual symbols are as defined above, and the product of formula IX obtained in one of the preceding reaction steps is condensed with a compound of formula X, R ¹ hal — C — W (X) R ² in which Hal represents chlorine, bromine or iodine and the other symbols are as hereinbefore defined, in the presence of an alkali. 2. A process according to claim 1, wherein L is alkylsulfonyl, chloro, bromo or iodo. 3. The process of claim 1 wherein the dealkylation is carried out using a reagent selected from the group consisting of pyridine hydrochloride, hydroiodic acid, hydrobromic acid, sodium thioethoxide in dimethylformamide, acetyl p-toluenesulfonate, sodium or potassium iodide in formic acid. or acetic, lithium iodide in 2,4,6-collidine and boron tribromide. 4. The process of claim 3 wherein the dealkylating agent is boron tribromide. 5. A process according to any one of claims 1 to 4, wherein the alkali metal or alkaline earth metal hydroxide or carbonate is used as the alkaline agent. . 6. A process according to claim 5, wherein the alkali is potassium carbonate.