IL24261A

IL24261A - Pesticidal compositions containing phenazine compounds,and new phenazine compounds

Info

Publication number: IL24261A
Application number: IL24261A
Authority: IL
Original assignee: Shell Int Research
Priority date: 1964-09-03
Filing date: 1965-09-01
Publication date: 1969-09-25
Also published as: DK116405B; DE1567114A1; NL6511395A; BE669039A; BR6572780D0; DK115157B; SE326599B; CH470135A; GB1086522A; OA01807A

Description

PeBticidal compositions containing new p enazine compounde SHELL RESEARCH This invention relates to pesticidal compositions containing certain phenazine The invention also relates to novel phenazine derivatives and to methods for their The compositions of the invention have fungicidal or activity or a combination of these The invention also relates to methods of combating fungi and The pesticidal compositions according to the invention comprise as active ingredient a phenazine derivative of the following general or its or wherein each R individually represents a hydrogen or halogen or an alkaryl group each of which may be or an amino or substituted amino or wherein two of the R substituents on adjacent carbon atoms may represent with those carbon atoms a benzene ring which may bear halogen alkyl The alkaryl and aralkyl groups referred to above may each contain up to 25 carbon atoms but up to 8 is and each group may bear one or more halogen or hydroxy The alkyl group and the alkyl portion of the alkaryl and aralkyl groups may have a straight or branched carbon The alkoxy group referred to above suitably contains up to Ik carbon atoms Certain compositions of the invention have been found to be useful for combating particularly Tetranychus telarius show greatest acaricidal fungicidal activity are those containing a halophenazine or alkylphenazine as active ient Other compositions of the invention have a useful herbicidal and those containing an or as active ingredient are Table 1 indicates the type of activity possessed by a number of novel phenazine derivatives having the above the symbols 0 and represent Table Phenazine derivative Example Aearlcide Herbicide XXXII X X X XXXI X XXVIII X 0 X III X X X V X X IV X X XVI X X XV x X X XI X X X XII X X X XIII X X 0 VI X 0 X XXV 0 0 X XXXVII X X XXXVII XIX 0 X VII X X XXII X X X XXVII X 0 XXIII X X X opoxyphenazine XXXV X X X XXXVIII X 0 X 0 na XXXVI 0 X 0 X XX X 0 X X 0 X 0 X IX X X X X X 0 0 XXIX X 0 Table 2 indicates the type of activity possessed by a number of known derivatives aving the above the symbols 0 and represent and Table 2 Active ingredient acaricide fungicide phenazine X X X X X X X X X X X 0 X X X X X X X X X X X 1 X X X 1 0 X X X X X X 0 0 X X 0 0 0 0 X 0 0 X X X X 0 0 X X 0 ne X X X X X X X X 0 X X X X X X 0 X X X X 1 lphenazine X X X X X X X X X X 0 1 X X X X X X X X X 0 X Some of the novel compounds listed in Table 1 may be prepared by known other novel compounds may be prepared by modifications of known methods or by novel methods of there is provided According to an aspect of the method for the novel the preparation derivatives having the above general and listed in Table 1 which formula reacting the appropriate with the appropriate catechol in a liquid medium in the presence of a metallic The liquid medium is preferably a solvent for the and the Examples of suitable solvents are and light petroleum Manganese dioxide is a preferred metallic The phenazine derivative formed may be isolated from the reaction mixture in any conventional For was obtained by slowly adding a solution of and in benzene to a vigorously stirred mixture of manganese dioxide in The reaction was complete after The product was recovered and purified by means of After pale yellow crystals were Other methods for the preparation of the novel phenazine listed in Table 1 derivatives the reaction of the appropriate diamine with the appropriate catechol at high temperature for a number of and subsequent oxidation with a metallic for example mercuric The known phenazine compounds may be prepared according to known synthetic for example those given in of Carbon IV by Rodd and Chemistry of Heterocyclic Compounds by Swan and or by the methods previously The pesticidal compositions of the invention may contain a carrier which may be a solid or liquid and may be of synthetic or natural Solid carriers may comprise synthetic hydrated silicon synthetic polymeric materials Surface active fertilizers other pesticides may be incorporated in the compositions of the The compositions of the invention may be formulated as wettable emulsifiable or conventional or invert The invention also relates to a method of combating fungi or weeds by bringing said fungi or weeds into contact with a pesticidal composition or a phenazine derivative as described the invention relates to a method for improving crop which comprises applying a phenazine derivative or a composition as specified above to a crop area before or after crop planting or before or after crop The pesticidal activity of the compositions of the invention is demonstrated in the following Acaricidal activity Compositions containing the phenazine derivative to be tested in an aqueous solution containing by weight of acetone and by weight of a surface active agent were sprayed onto leaf discs cut from french bean One hour after each disc was infested with 10 adult red spider mites telarius and mortality counts were made hours after The surface active agent was commercially available under the trade mark Triton By using compositions having different concentrations of the phenazine the that is the concentration necessary for killing of the spider was The results set out in the Table are toxicity index values wherein standard x 100 phenazine derivative Table 3 Name Toxicity Index 200 phenazine 500 650 300 Methyl 100 It will be seen from Table 3 that and showed an acaricidal activity considerably greater than that of methyl parathion established and are of particular Fungicidal activity Aqueous suspensions containing from to parts per million of the phenazine derivative to be and up to parts per million of a wetting agent were prepared by means of a micro wet The wetting agent used was commercially available under the trade mark Triton The compositions were sprayed on cucumber each plant having two fully expanded true 15 to 20 ml of the composition were sprayed onto each hours after the plants were inoculated with dry powdery mildew spores brushed from cucumber The plants were kept for 10 days at to and disease assessments of the two treated leaves of each plant were then carried The results of the test are shown in Table 4 wherein A represents more than control of cucumber powdery mildew at a concentration of the phenazine derivative of B represents more than control of cucumber powdery mildew at 50 100 C represents more than control of cucumber powdery mildew at 100 Table Name fungicidal activity A A A A A B B B B B B lphenazine B It will be seen that inter alia and show a high order of fungicidal activity and are of particular Herblcidal activity Compositions of the invention were tested for herbicidal activity using the representative range of oat ryegrass sweet corn pea sugar beet linseed and mustard The tests fall into two and The tests involve the spraying divided into soil drench and foliar spray operations which are carried out after seedlings have Details of the tests are given below Each composition contained the following ingredients Acetone by volume Water by volume Surface active agent by weight Phenazine derivative varying amounts The surface active agent used was an alkylaryl polyether alcohol commercially available under the trade mark Triton The seeds of the plant species mentioned above were sown and allowed to germinate in steam treated John Innes compost In the soil spray and soil drench the sown soil and the soil bearing the seedling were sprayed at a volume equivalent to 50 gallons per acre and drenched at a volume equivalent to 1000 gallons per acre In the foliar spray similar seedling plants were sprayed with a volume equivalent to 50 gallons per acre Control tests were also carried out in which sown bearing and plants were treated with the same compositions but containing no active ingredient The phytotoxic effect of the compound applied was assessed by determining the reduction in fresh weight of stem and leaf of the treated plants over the control plants and plotting a regression curve relating the growth inhibition and the dosage of compound The dosage required for and growth inhibition that weight of compound required to give a reduction in the fresh weight of plant leaf and stem of 50 or is shown in table 5 which dosage is expressed in pounds per Y and Z represent dosages greater than and 20 pounds per acre GROWTH INHI SEEDS LEVEL ACTIVE INGREDIENT SOIL SPRAY FO SC 0 RG P L SB SC 0 RG 50 90 X X X X 50 X X X 1 90 X X X X 5 50 X X X X X X X X X X 50 X X X X X X X X 0 X X 50 X X X X X X X X 90 X X 50 X X X X X X X X 90 X X 50 X X X X X X X X X 90 X lphenazlne 50 X 90 X X 50 X X X 90 X X 50 X X X X 5 90 X X X X X i Table It will be seen from Table 5 that certain compounds show outstanding activity as show a high order of and therefore are of particular The compositions of the some novel active phenazine and methods for their preparation are further illustrated in the following Examples in which parts by weight and parts by volume bear the same relation as the kilogram to the EXAMPLE I Wettable powder composition The following ingredients were blended together in a ribbon blender in the following proportions by weight Active ingredient Surface active agents Sodium polymethacylate Sodium lauryl sulphate Carrier Kaolinite The mixture was then and finally to the desired powder This wettable powder composition was particularly active in preventing cucumber powdery mildew and combating glasshouse red spider the slight of was apparent when the composition was used at a dose rate of about The composition was also tested for activity against existing cucumber powdery mildew Sufficient containing 75 parts per million of The suspension was sprayed on and old cucumber powdery mildew A eradication old infection and a eradication the old infection Again no phytotoxic effects were EXAMPLE II Emulsifiable concentrate composition The following ingredients were blended together at a temperature of about in the proportions shown below Active ingredient Surface active agent alkyl aryl phenol oxide blend Carrier monochlorobenzene A satisfactory emulsifiable concentrate was EXAMPLE III Preparation of and were heated together in a sealed tube at for The contents of the tube were dissolved in and warmed to with mercuric oxide for 4 The resulting solution was cooled and filtered through a cellulose The filtrate was evaporated to dissolved in a mixture of toluene and light petroleum and chromatographed through a column of acidic Brockmann Activity 1 A yellow solid was obtained and crystallised from light petroleum The desired product was obtained in point Analysis Found C 8 H EXAMPLE IV Preparation of and were reacted together in the manner described in Example Yellow needles of melting point were obtained in Analysis Found C H N C15H14N2 C H N EXAMPLE V Preparation of melting point was obtained from and in yield by the method described in Example Analysis Found C H N C H N EXAMPLE VI Preparation of melting point was obtained from catechol and by the method described in Example Analysis Found C H N C21H20N2 C N EXAMPLE VII Preparation of 1 or 8 l henazine meltin was by the method described in Example Analysis Pound C H N Cl4H12N2 C H N EXAMPLE VIII Preparation of melting point was obtained from catechol and in yield by the method described in Example Analysis Pound C H N requires C H N EXAMPLE IX Preparation of melting point was obtained from and in yield by the method described in Example Analysis Found C H N C H N EXAMPLE X Preparation of melting point was obtained from and in yield by the method described in Example Analysis Found C H N C H N EXAMPLE XI Preparation of melting point was obtained from and in yield by the method described in Example Analysis Found C H N N EXAMPLE XII Preparation of melting point was obtained from and in yield by the method described in Example Analysis Found C H N Cl8H20N2 C H N EXAMPLE XIII Preparation of melting point was obtained from and in yield by the method described in Example Analysis Found C H N N requires C H N EXAMPLE XIV Preparation of melting point was obtained from and yield by the method described in Example Analysis Pound C H N c H N EXAMPLE XV Preparation of melting point was obtained from and in yield by the method described in Example Analysis Pound C H N C H N EXAMPLE XVI Preparation of dioxide hydrogen peroxide and glacial acetic acid were mixed and kept at for 46 The resulting solution was cooled and diluted with water an orange solid Crystallisation from a mixture afforded orange needles of the desired melting point in Analysis Found C H N C H N EXAMPLE XVII Preparation of dioxide was mixed hydrogen peroxide and glacial acetic acid and allowed to stand at a temperature of to for 50 The resulting reaction mixture was poured into water and allowed to stand for 24 Long red needles separated and after crystallisation from a ater mixture melting point was obtained in Analysis Pound C H N C H N EXAMPLE XVIII Preparation of phenazine A solution of and catechol in benzene was added to a mixture of manganese dioxide and cooled to The addition was completed in minutes and the reaction mixture was stirred for a further 3 hours at After the was chromatographed through a neutral alumina column using benzene as eluent to after recrystallisation from hexane 265 yield of of melting point Analysis Pound C H N C20H24N2 C H N EXAMPLE XIX Preparation of melting point was obtained from and manganese dioxide by the method described in Example Analysis Found C H N C H N EXAMPLE XX Preparation of melting point was obtained in yield from catechol and manganese dioxide by the method described in Example Analysis Pound C H N Br requires C H N Br EXAMPLE XXI Preparation of melting point was obtained in yield from catechol and manganese dioxide by the method described in Example Analysis Found C H CI H CI EXAMPLE XXII Preparation of was obtained from and man anese dioxide in 62 ield as a viscous ellow oil by Found ί Preparation of melting point was from catecho and manganese dioxide in yield by the method described in xam le Analysis Pound H H requires C V EXAMPLE XXIV Preparation of tetramethylbtttyljphenagine melting point was obtained from 5 and manganese dioxide in yield by the described in Example Analysis Found H F 0 F XX Preparatio of melting point was obtained om and manganese dioxide yield by the method described in Example Preparation of 1 was obtained from and manganese dioxide in 55 yield by the method described in Example Analysis Pound C H N CI H N CI EXAMPLE Preparation of in ether was added to potassium nitrosodisulphonate in water and potassium After stirring for the mixture was extracted with filtered and the filtrate allowed to react for days with chloroform in the presence of anhydrous sodium sulphate The reaction mixture was evaporated and the residue chromatographed over a neutral alumina column using toluene as The product was obtained in melting point Analysis Pound C H N EXAMPLE XXVIII Preparation of Aniline powdered potassium hydroxide and dry toluene were stirred vigorously and heated under reflux for 2 The water eliminatedduring reaction was taken by means of a Dean Stark apparatus The hot solution was filtered and the filtrate evaporated to dryness to give a melting Purification by alumina chromatography followed b recrystallisation from ethyl acetate gave phenazine as a canary yellow solid melting point Yield Analysis Pound C H N CI requires C H N CI EXAMPLE XXIX Preparation of melting point was prepared from and powdered potassium hydroxide in toluene in yield by the method described in Example Analysis Found C H N C12H5N2C15 C H N EXAMPLE XXX Preparation of melting point was prepared from and in yield by the method described in Example Analysis Found C H N C H N EXAMPLE XXXI Preparation of melting point was obtained from and aniline in yield by the method described in Example Analysis Found C H N C12H5N2CL5 C H N EXAMPLE XXXII Preparation of melting point was obtained from and aniline in yield by the method described in Example Analysis Found C H N Br C EXAMPLE XXXIII Preparation of was heated with a fold excess of anhydrous dimethylamine in a sealed tube at for 14 The reaction products were dissolved in toluene and chromatographed on basic alumina to yield melting point in Analysis Pound C H N EXAMPLE XXXIV Preparation of To a suspension of the fluoroborate of diazotised in acetic acid was added sodium azide below After shaking for 20 the solution was made alkaline and w of precipitate The precipitate was dissolved in benzene and filtered through an alumina column to give the melting point Analysis Found N requires N EXAMPLE XXXV Preparation of To potassium hydroxide in was added and the mixture was heated under reflux for 5 The reaction mixture was diluted with water to give a precipitate of melting point This product was dissolved in propanol and added to 8 hydrazine hydrate and palladium carbon and heated under reflux until the evolution of gas After filtration the mixture was diluted with water and The residue was warmed with water and a little nitric then neutralised with The resulting precipitate was purified by sublimation at at and had a melting point Analysis Pound C H C re uires H EXAMPLE XXXVI Preparation of To the of dlazdtised was added copper thiocyanate aqueoue acetic acid at Gases were evolved and the mixtur was set aside for 1 then acetic acid added and the mixture Dilution of the filtrate with water afforded a solid which was filtered off and washed with water and a little from afforded the product melting point and Starting from aniline and and its ft were prepared by the method described in Example Both products present in the The were isolated therefrom by chromatography EXAMPLE and By the method described in Example XXXV but using butanol or instead of and were insufficientOCRQuality

Claims

HiOTWCr EO¾r particularly described and ascertained the nature of our dais invention and in what manner the same is t& be performed, we declare that what we claim is \

1. Pesticidal compositions comprising as active ingredient a phenazine of the following general formula :- or its mono- or di-N-oxides, wherein each R represents a hydrogen or halogen atom, or an alkyl, aryl, aralkyl, alkaryl group each of which may be substituted, or an alkoxy, hydroxy, cyano, thiocyanato, azido, nitro, amino or substituted amino group; or wherein two of the R substituents on adjacent carbon atoms may represent with those carbon atoms a benzene ring which may bear halogen and/or alkyl substituents.

2. : A composition as claimed in claim l wherein the phenazine derivative is l,4-dichlorophenazine.

3. · A composition as claimed in claim 1, wherein the phenazine derivative is 2-(l,l,3i3-tetramethylbutyl)phenazine.

4. A composition as claimed in claim 1, wherein the phenazine derivative is 2-methylphenazine .

5. A composition according to claim 1, wherein the phenazine derivative is 2-chlorophenazine.

6. A composition as claimed in claim 1, wherein the phenazine derivative is 2-isopropylphenasine.

7. A composition as claimed in any one of claims 1-6, which comprises a carrier or a surface active agent.

8. A composition as claimed in any one of claims 1-6, which 24261/3 - 28 -

9. A composition as claimed in Claim 1 substantially as hereinbefore described. ' 10* A composition as claimed In Claim 1 substantially as hereinbefore described vilth reference to the Examples I and II. 11. A novel phenazine compound of the formula given in Claim 1 selected from the group ofs 1,4-dibromophenazine

10. 1. .3-trichlorophenazlne

11. 1.2. -trichlorophenazine 2-ethylphenazine 1-isopropylphenazine 2«-lsopropylphenazine 2-lsopropylphenazine-5»lQ-dloxide 2-n-butylphenazine 2-n-pentylphenazine 2 n-hexylphenazine 2-n«^heptylphenazine 1-methyl-3-(l' ,V , 3' , 3'-tetramethylbutyl)phenazine 2^methyl-7 (or 8) ,V tV ,3'-tetramethylbutyl)phenazine 1,4-dimeth lphenazine 1,4-dimeth lphenazine-5-oxide 2, 3-dimehyl-7^(11 ,1' , 3 ' » 3 -tetramethylbutyl)phenazine 1,7 (or 8) -dimethylphenazine l*methyl-3-t-but lphenazine. , ;> 2, 3·7-trimethylphenazine 1, 3-diisoprop lphenazine 2-n-propoxyphenazine 2fn«-butoxyphenazine 2-n-pentyloxyphenazine 2-azldophenazine ,1* *V >V-tetramethylbutyl)phenazine 2-thiocyanatophenazine 2·(1*,1·, 3* , 3*-tetramethylbutyl)-7 (or 8) -chloro-phenazine l-bromo-3-(l' »1' »3 ' , 3*-tetramethylbutyl)phenazine 1-chloro-3-(l* *1' » 3' ,3'-tetramehylbutyl) henazine 2-n-stear lphenazine 24261/3 , ? * -, 29 - *

12. * A process for the preparation of phenazine derivatives according to Claim 11, which comprises reacting the appropriate ortho-phenylenediamine with the appropriate catechol in a liquid medium in the presence of a metallic oxide.

13. A process as claimed in Claim 12, wherein the liquid medium is a solvent for the ortho-phenylenediamine and the catechol*

14. * A process as claimed in Claim 13, wherein the solvent is benzene, toluene, an ether or a light petroleum fraction.

15. A process as claimed in any one of Claims 12-14, wherein the metallic oxide is manganese dioxide.

16. A process as claimed in any one of Claims 12-13, substantially as hereinbefore described.

17. Pesticidal compositions containing as active ingredient a novel phenazine derivative as claimed in Claim 11.

18. A method of combating acari, fungi or weeds, which comprises bringing said acari, fungi or weeds into contact with a composition as claimed in any one of Claims 1-10 and 17» or a phenazine derivative as claimed in Claim 11.

19. A method of combating acari, fungi or weeds substantially as hereinbefore described.

20. A process for improving crop yields, which comprises applying a phenazine derivative as claimed in Claim H or a composition as claimed in any one of Claims 1-10 and 17 to a crop area before or after crop planting or before or after crop emergence. For the/ Applicants DR. KEimOiJ), CO AFX) PARTI