The method of obtaining derivatives of pyrazole phenylseleno

 

(57) Abstract:

Describes how to obtain new derivatives phenylseleno of pyrazole of the formula (II) and their salts and esters, where X1and X2are halogen or hydrogen; R1is C1-6-alkyl; R2is C1-6-halogenation or alkylsulfonyl and R3is H or halogen, wherein the oxidized compound of the formula (III) in which X is as defined previously, oxygen or oxygen-containing gas in the presence of an oxidation catalyst in an inert solvent. The technical result - the provision of new carbocyclic (heterocyclic) substituted benzoic acids, are suitable as intermediates or precursors to obtain the corresponding ester compounds, which are useful herbicide compounds. 7 C.p. f-crystals, 1 PL.

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The present invention relates to the class of heterocyclic and carbocyclic substituted benzoic acids and to methods for their preparation from the corresponding methyltrichlorosilane and carbocyclic compounds. Benzoic acids of this type, obtained by direct oxidation with Panini, used in agriculture and medicine, in particular as intermediates for active class aprilgalenaedaline and arylalkylamines herbicides.

Prior art

From the prior art in this field known to produce a variety of oxidized derivatives alifaticheskimi aromatic compounds by oxidation of aliphatic(their) successor(s). For example, mono - and polynuclear aromatic compounds such as benzene, diphenyl, naphthalene, anthracene, phenanthrene, etc. having one or more mono - or difunctional aliphatic groups, can be partially oxidized to derivatives, such as alcohols, aldehydes, ketones, peroxides, etc., Mono - and polycarboxylic aromatic acids are also obtained by oxidation of the corresponding aliphatic substituted aromatic compounds.

Methods of oxidation of the above type are disclosed in U.S. patent N 2833816 and laid patent application Japan N 59-27850 (Kokai) N 1, aromatic hydrocarbons, containing only1-4-alkyl groups and/or halogen, are oxidized to the corresponding oxidized derivatives through ieromonah catalyst, bromine and catalyst for the oxidation of the heavy metal.

In addition, the known conversion of methylpyrazolo containing many deputies, in pyrazolylborate acid through liquid-phase reaction with molecular oxygen (U.S. patent N 5053517) and the corresponding catalysts based on metal salts.

Other methods of oxidation, known from the prior and acid products are relatively new substituted the phenylpyrazoles, which are useful as intermediates in the production of other derivatives that are servicenotification in respect of important agricultural crops, in particular it should be noted certain substituted 3-aryl-5-substituted pyrazol connection. Examples of such herbicide compounds disclosed in U.S. patent N 5032165, the main characteristic of which is that 3-aryl-5-pyrazol connection is substitution-AR5group in 5-position of the pyrazole nucleus radical, where A is O or S, and R5represents hydrogen or lower (halogen) alkyl. Previously published is parallel U.S. patent '165 application EP N EP 0361114, published 4 April 1990 Other ways in which the unity in the aforementioned U.S. patent '165 and the application EP '114 is produced by a multistage process, including:

(1) halogenoalkane methyl group in 5-position 3-phenyl-5-AR5pyrazol substrate for the formation of the corresponding 5-halogenmethyl connection; (2) the interaction of the latter with arylamines and formaldehyde in the hexamine (reaction of Complete), followed by acid hydrolysis to replace formaldehyde group on halogenmethyl radical in the 5-position of the phenyl radical, and (3) oxidation of the formaldehyde group in the carboxylic acid radical. The compound obtained is suitable as intermediate compounds for the formation of the final product, having in the phenyl ring 5-ester group by esterification of 5-COOH group of the alcohol.

Other 3-aryl-5-substituted pyrazol compounds having improved herbicide efficacy presented in the related application N 07/763762 (now U.S. patent N 5281571), in a partial continuation of application N 07/600031, now repealed, and in the patent of South Africa N 6197 (parallel application U.S. N 07/735091, now cancelled). In the above U.S. patent '571 compounds characterized by the presence halogenating substituent in the 5-position of the pyrazole nucleus of the group, while in the patent South Africa N 6197 5-projeleri, the compounds presented in the above mentioned patents, get a multistage manner.

In the preceding field is not disclosed methods direct oxidation of aryl compounds having as substituents as alkyl(s) group (s) and, in addition, the carbocyclic or heterocyclic group, as shown above, for the formation of the final complex ester required multistage processes.

Therefore, the purpose of this invention is the provision of new carbocyclic-substituted benzoic acids and geterotsiklicheskikh-substituted 3-benzoic acid, for example 5-[substituted pyrazole]-halogen-(UN) substituted benzoic acids, are suitable as intermediates or precursors to obtain the corresponding ester compounds, which are useful herbicide compounds.

Another object of this invention is the provision of a new method for direct oxidation of aryl compounds, substituted alkyl (preferably C1-4) groups, and carbocyclic or heterocyclic groups, to obtain the corresponding carbocyclic or heterocyclic aralkylated connections.

Special purpose momentthe direct oxidation of the corresponding alkyl substituted compounds predecessor.

A special object of this invention is the provision of a new connection 5-[4-bromo-1-methyl-5-(trifluoromethyl)- 1H-pyrazole-3-yl)-2-chloro-4-fermenting acid and its synthesis by direct oxidation of the corresponding alkylphenolate. Through the esterification of the above acids are also esters mentioned benzoic acid, mainly complex isopropyl ether.

A brief summary of the invention

In one aspect the present invention relates to new derivatives of benzoic acid formula 1

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and their salts and esters, where X is halogen, C1-6- POLYHALOGENATED, C6-10-aryloxy, C6-10-alkoxy or alkylsulfonyl,4-10-tert-alkyl, NO2or CN;

n is 0-4;

Z represents (UN)substituted carbocyclic or heterocyclic ring having up to 8 ring members, and heterocyclic ring contains one or more atoms O, N or S, and the substituents of the carbon ring may be one or more X groups, and the substituents of ring heteroatoms N can be C1-6-(halo)alkyl, hydrogen, or X is a group.

Preferred compounds of formula 1 are those in which X is a group primi compounds of formula 1 are compounds such which are a subclass of pyrazoles benzoic acid of formula II

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and their salts and esters, where:

X1and X2are halogen or hydrogen;

R1is C1-8-alkyl;

R2is C1-6-halogenation or alkylsulfonyl;

R3is hydrogen or halogen.

Even more preferred compounds in accordance with formula II are those in which:

X1is fluorine;

X2is chlorine or bromine;

R1is stands;

R2is-CF3, -CF2Cl, C2F5or-CF2H;

R3is hydrogen, bromine or chlorine.

The preferred species of the compounds of formula II are:

5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazole-3-yl] -2-chloro-4 - Formentera acid;

5-[4-bromo-1-methyl-5-(trifluoromethyl)-1H-pyrazole-3-yl] -2-chloro-4 - Formentera acid;

n-propyl ester 5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazole-3-yl] -2-chloro-4-fermenting acid;

isopropyl ester 5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazole-3-yl] -2-chloro-4-fermenting acid;

n-propyl ester 5-[4-bromo-1-methyl-5-(trifluoromethyl)-1H-pyrazole-3-yl]-2-chloro-4-fermentelos.

According to another aspect of this invention relates to a new method of obtaining compounds of formulas I and II, which involves direct oxidation of compounds in accordance with formula III

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in which X, n and Z are as previously defined.

In preferred embodiments, the compound in accordance with formula III, in which both X in ortho - and paraprotex are halogen and Z represents 3 - or 5-pyrazolidine connection, are oxidized in the liquid phase with molecular oxygen or oxygen-containing gas in the presence of the oxidation catalyst. The temperature range of the reaction is about 0oC-300oC and the pressure range from below ambient to values >70,3 kg/cm2.

Detailed description of the invention

Pyrazolidinone acid obtained from metilfenidato by oxidation with molecular oxygen in a suitable solvent in the presence of a catalyst or mixture of catalysts and other auxiliary substances in the temperature range from 0oC to 300oC, preferably from 50oC to 150oC. Can be applied to any suitable solvent which does not impede the reaction, while the preferred races the art of oxygen or air in other media. On the reaction rate can favorably influence the application of pressure and, depending on the equipment and the desired speed of reaction can be used any pressure from about 1 kg/cm2to > 70,3 kg/cm2(from one atmosphere up to more than 1000 pounds/inch2). The use of pressures higher than 1 kg/cm2has a beneficial effect on the reaction rate; however, this does not prevent the use of higher or lower pressures.

For a favorable impact on the rate of oxidation using a catalyst or mixture of catalysts. Can be used a mixture of catalysts based on metal salts containing any salt or combination of salts, including salts of cobalt, manganese salt, Nickel salt, cesium salt and a zirconium salt, but not limited to. Examples of such salts are salts of aliphatic acids, acetate, cobalt (II) formate, cobalt, exiled cobalt, manganese acetate (II), cesium acetate (III), etc. compounds, chelate compounds, such as cobalt acetylacetonate, zirconium acetylacetonate (IV) etc., and metal salts such as cobalt chloride, cobalt carbonate, Nickel chloride, manganese chloride, zirconium chloride, etc. Other catalysts include the methyl hydrogen, bromide of sodium, bromoxynil acid, ammonium bromide, sodium acetate, and so on, but not limited to. The amount of catalyst or a catalyst mixture can independently vary from less than 1 mol.% up to about one molar equivalent relative to the compound of formula III.

As auxiliary substances can also be used in the intermediate or oxidized halogenated compounds obtained by derivatization of compounds of formula III. So, to the reaction mixture for beneficial effect on the reaction rate can be added derivatives benzylbromide obtained by the synthesized methylphenylene group, or benzaldehyde obtained by partial oxidation methylphenylene group. To initiate or enhance the oxidation can also be used peroxides, for example hydrogen peroxide, which are particularly suitable for initiating or strengthening okislenii occurring at atmospheric pressure, mainly before completion, when the oxidation is slowed down. The number of auxiliary substances, in particular, is not limited and can be used in any amount necessary to obtain desirable the different substances are independently less than 0.1 mol.% up to 10 mol.%.

Can be used with any suitable solvent which is stable to the reaction conditions, or the reaction can be carried out in the absence of solvent. Preferred solvents include aliphatic carboxylic acids and anhydrides, for example acetic acid and acetic anhydride, but is not limited to only them. The amount used of the solvent is not limited, but the reaction rate can be increased by applying a limited number of solvent.

General outputs and a simple implementation of the method can favorably improve through a combination of stages of halogenation and oxidation, as shown below in the case of the were-4-gidropirita formula IV, which turned into 4-halogenerators acid (compound of formula II in which R3is a halogen) in a single stage without isolation of intermediate compounds. The two-stage reaction in this method can be implemented in any of the two possible orders; oxidation with subsequent halogenoalkanes or halogenoalkane with subsequent oxidation. The preferred sequence is halogenoalkane with subsequent oxidation.

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The compounds of formula II, propisany earlier. For some derivatives herbicide of ester, amide, tiefer, thioamide, etc. by methods known in this field, you can derivateservlet carboxylic group.

For the esterification of COOH-groups, as shown below in example 6, can be used, for example, suitable alcohols, such as propyl or isopropyl alcohol.

The following examples 1-6 describe specific work options for obtaining characteristic compounds in accordance with this invention. Examples 1-3 describe the specific working versions single-stage oxidation of compounds of formula IV.

Example I.

Getting 2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H - pyrazole-3-yl]-4-fermenting acid (compound No. 1).

A 5 l round bottom flask was prepared a solution of 700 g (2,14 mole) 4-chloro-3-(4-chloro-2-fluoro-5-were)-1-methyl-5- (trifluoromethyl)-1H-pyrazole in 1000 ml of glacial acetic acid and treated with a catalytic mixture consisting of the 5.25 g of Tetra - hydrate acetate cobalt (II), 0.55 g of tetrahydrate of manganese acetate (II) and 4.2 g of sodium bromide. The contents of the flask was heated to 95oC and mixed in the reaction mixture introduced a flow of air (20.9% oxygen). After heating for two days the mixture obree solid, which was dried in the air, got a 745 g (97,4%) of white solids. An analytical sample was recrystallize from a mixture of simple ether and hexane:

melting point 179oC - 181oC;1H NMR (CDCl3+ DMSO) 11,84 (S, broad. 1H), of 8.09 (d, j = 8H, 1H), 7,21 (d, j = 10 H, 1H), 3.96 points (S, 3H);19F NMR (CDCl3+ DMSO) -63,9 (S, 3F), -110,4 (m, 1F).

Analytically calculated for C13H6N2O2F4Cl2: C 40,36; H 1,69; N 7,84.

Found: C 40,49; H 1,74; N To 7.77.

Example 2.

Getting 2-chloro-5-[1-methyl-5-(trifluoromethyl)-1H-pyrazole-3-yl]-4-fermenting acid (compound No. 2).

A mixture of 40.6 g of 3-(4-chloro-2-fluoro-5-were)- 1-methyl-5-(trifluoromethyl)-1H-pyrazole in 70 ml of glacial acetic acid, 0.34 g of acetate tetrahydrate cobalt (II) 0,033 g acetate tetrahydrate manganese (II), 0.28 g of sodium bromide and 0.1 g of 2-chloro-5-(4-chloro-1-methyl-5-trifluoromethyl)-1H-pyrazole-3-yl)-4 - forventelige was placed in a 300 ml Parr autoclave (Hastaloy), equipped with a mixing device, in the autoclave has created increased pressure with gas of oxygen, equal to 7.0 kg/cm2. The vessel was heated to 145oC and by adding a certain amount of oxygen maintained pressure of oxygen equal to 10.5 kg/with the/of 10.5 kg/cm3(150 pounds/inch2) for the next 90 minutes. Then the autoclave was cooled, reduced pressure, and the contents added to 400 ml of cold water. The suspension was filtered, the solid washed with cold water and dried in the air, got to 42.2 g (94,3%) of white solids. By recrystallization from ethyl acetate obtained analytical sample:

melting point 195oC-197oC;

1H NMR (CDCl3) to 4.01 (S, 3H), 6,93 (S, 1H), 7,18 (d, 1H), 8,67 (d, 1H).

Analytically calculated for C12H7ClF4N2O2: OF 44.67; H 2,19; N 8,68.

Found: Of 44.67; H 2,18; N 8,63.

Example 3.

Getting 2-chloro-5-[1-methyl-5-(trifluoromethyl)-1H-pyrazole-3-yl] -4-fermenting acid (compound No. 2).

In a 1 l flask type Morton flask was prepared a solution of 100 g (0,34 mole) of 3-(4-chloro-2-fluoro-5-were)-1-methyl-5- (trifluoromethyl)-1H-pyrazole in 400 ml of glacial acetic acid and treated with a catalytic mixture of 0.85 g of the acetate tetrahydrate cobalt (II), 0.10 g of tetrahydrate of manganese acetate (II) and 1.05 g of sodium bromide. The contents of the flask was heated to 109oC and at a flow rate of 150 ml/min mixed in the reaction mixture introduced a flow of air (20.9% oxygen). To initiate the reaction dopatka, emerging from the reaction mixture, fell from 20.9% to 8.9%. After 22 hours the mixture was treated with 750 ml of cold water and provided cooling to room temperature. The obtained solid was collected by filtration, washed 1 l of cold water and dried in the air, got a 104 g (97,4%), pale-reddish solid. Of ethyl acetate was recrystallize the analytical sample: melting point 195oC-197oC.

Examples 4 and 5 describe specific work options combined sequence of oxidation-halogenoalkane to obtain the compounds of formula II in which R3is halogen.

Example 4.

Getting 2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H - pyrazole-3-yl]-4-fermenting acid (compound No. 1).

In a 1 l flask type Morton flask was prepared a solution of 100 g (0,34 mole) of 3-(4-chloro-2-fluoro-5-were)-1-methyl-5- (trifluoromethyl)-1H-pyrazole in 400 ml of glacial acetic acid and treated with a catalytic mixture of 0.85 g of the acetate tetrahydrate cobalt (II), 0.10 g of tetrahydrate of manganese acetate (II) and of 1.65 g of sodium bromide. The contents of the flask was heated to 105oC and stirred the mixture with a flow rate of 150 ml/min introduced a flow of air (20.9% oxygen). To initiate re the atmospheric temperature, the result obtained suspension containing benzoic acid (compound No. 2). To the stirred suspension over 10 minutes added to 25.5 g (0,34 mole) of chlorine. The mixture was maintained at 30oC overnight and then treated with 700 ml of cold water. When filtering the suspension obtained, which is washed three times with 500 ml of water and after air drying has received 114 g (93,7%) of a white solid: melting point 179-181oC.

Example 5.

Getting 5-[4-bromo-1-methyl-5-(trifluoromethyl)-1H-(pyrazole - 3-yl] -2-chloro-4-fermenting acid (compound No. 3).

In a 1 l flask type Morton flask was prepared a solution of 100 g (0,34 mole) of 3-(4-chloro-2-fluoro-5-were)-1-methyl-5- (trifluoromethyl)-IH-pyrazole in 400 ml of glacial acetic acid and treated with a catalytic mixture of 0.85 g of the acetate tetrahydrate cobalt (II), 0.10 g of tetrahydrate of manganese acetate (II) and of 1.65 g of sodium bromide. The contents of the flask was heated to 105oC and stirred the mixture with a flow rate of 150 ml/min introduced a flow of air (20.9% oxygen). To initiate the reaction was added five drops of 50% hydrogen peroxide. After 24 hours, provided the cooling of the mixture to the 50oC, resulting in a suspension containing benzoic acid the mixture was treated with 25 ml of water and 12 hours later another 25 ml of water and then added 3.5 g of bromine. After a reaction time of generally within 24 hours the mixture was treated with 185 ml of a 23% solution of sodium sulfite to destroy excess bromine. To establish the temperature of the 26oC the resulting mixture was treated with 150 ml of ice. When filtering the suspension obtained, which was washed with cold water and then dried in the air, receiving to 127.9 g (93,3%) of white powder:

melting point 171-173oC;1H NMR (CDCl3) 4,22 (S, 3H), 7,49 (d, 1H); 8,39 (d, 1H).

Analytically calculated for C12H6BrClF4N2O2: 35,87; H 1,50; N 6,97.

Found: 35,79; H 1,64; N 6,90.

Example 6 describes a particular workflow option of making the compounds of formula II derived arylpyrazole.

Example 6.

Getting 1-methylethyl-5-[4-bromo-1-methyl-5-(trifluoromethyl) - 1H-pyrazole-3-yl]-2-chloro-4-perbenzoate.

Prepared in a solution of 100 g (0.25 mole) of 5-[4-bromo-l-methyl-5- (trifluoromethyl)-IH-pyrazole-3-yl] -2-chloro-4-fermenting acid in 580 ml of toluene and treated with 1 g of dimethylformamide (DMF). The stirred mixture was heated to 45oC was treated with 30 g (0,252 mole) of thionyl chloride and then heated for one hour to 60oC-65oC. After cooling to 40oC immediately added a solution of 30 g (0,50 masgutova chloranhydride connection to the target product was heated to 55oC. By treatment with 650 ml of water and 45 g of acetone received two transparent layer. Removed the water layer and the organic portion was washed with water, saturated brine, dried MgSO4and concentrated to obtain a viscous oil. By dissolving the oil in 250 g of hot isopropanol, cooling the mixture to room temperature and slow processing 600 ml of cold water has been solid. The precipitate was collected by filtration, washed with water and dried in the air, got a 105 g (94,7%) of white solids:

the melting point of 79.5oC - 80,5oC.1H NMR (CDCl3) 1,49 (d, 6N), IS 4.21 (S, 3H), 5,38 (m, 1H), 7,43 (d, IH), 8,14 (d, 1H).

Analytically calculated for C15H12BrClF4N2O2: 40,59; H 2,71; N OF 6.31.

Found: 40,60; H 2,73; N 6,29.

The following table shows examples of compounds of formula II, obtained by the above methods.

Heterocyclic or carbocyclic substituted acid of the present invention are suitable as intermediates for the receipt or production of chemicals for agriculture and medicine, mainly for more herbicides of type substituted phenylpyrazole. This pic is analnogo ring arylpyrazole for subsequent transformation into various derivatives of ester and amide. In addition, as halogenoalkane heterocyclic ring and oxidation of the methyl group in the phenyl ring can be made in the form of a one-stage process, this eliminates the stage of selection of the intermediate product.

For professionals in this field are obvious various equivalent modifications of the invention described here.

1. The method of obtaining derivatives phenylseleno of pyrazole of the formula

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and their salts and esters, where

X1and X2is halogen or hydrogen;

R1is1-6- alkyl;

R2is1-6- halogenation or alkylsulfonyl, and

R3is H or halogen,

characterized in that the oxidized compound of the formula III

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in which X is as defined previously,

oxygen or oxygen-containing gas in the presence of an oxidation catalyst in an inert solvent.

2. The method according to p. 1, characterized in that the oxidation reaction is carried out at a temperature in the range of about 0 to 300oC and the pressure from low to 70,3 kg/cm2.

3. The method according to p. 1, characterized in that the catalyst is a salt or scale> is fluorine, X2is chlorine, R1is stands, R2is-CF3-CF2Cl-C2F5or CF2H and R3is H, bromine or chlorine.

5. The method according to PP. 1 and 4, characterized in that the said compound of formula II is chosen from the group consisting of 5-[4-chloro-1-methyl-5-trifluoromethyl)-1H-pyrazole-3] -2-chloro-4-fermenting acid and its complex n - and isopropyl esters.

6. The method according to PP.1 and 4, characterized in that the said compound of formula II is chosen from the group consisting of 5[4-bromo-1-methyl-5-(trifluoromethyl)-1H-pyrazole-3-yl] -2-chloro-4-fermenting acid and its complex n - and isopropyl esters.

7. The method according to p. 1, characterized in that at least one X in formula III represents a halogen.

8. The method according to p. 7, characterized in that both groups of X is independently selected from halogen.

 

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in which R1is phenyl, substituted cyclo(lower)alkyl, hydroxy(lower)alkyl, cyano, lower alkylenedioxy, carboxy, (lower alkoxy)carbonyl group, a lower alkanoyl, lower alkanoyloxy, lower alkoxy, phenoxy or carbamoyl, optionally substituted lower alkyl;

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