IL31432A

IL31432A - N-aryl pyrid-2-ones,their preparation and use for the regulation of plant growth

Info

Publication number: IL31432A
Application number: IL31432A
Authority: IL
Original assignee: Rohm & Haas
Priority date: 1968-01-16
Filing date: 1969-01-15
Publication date: 1972-09-28
Also published as: DE1900947C3; BG16424A3; GB1253293A; DE1900947A1; DK136860C; CH506943A; MY7300247A; LU57789A1; ES362532A1; IL31432A0; IE32615L; OA02978A; FR1599535A; NL6900775A; AT306428B; NO127446B; DE1900947B2; SE351428B; NL148599B; CU20608A

Description

their preparation and for the regulation of plant ROHM AND HAAS COMPANY 29689 may be hydrogen when n is 1 or 2 and there is halogen in the position of the benzene The most closely related known compound to those concerned in this invention is This known compound was prepared by Eeid et as described in Annalen Annalen 110 The method used was the condensation of cyanoacetanilide with acetylacetone to produce which was then hydrolyzed to the corresponding A of compounds provided by the invention are those of the wherein Y is or where is alkyl or a forming X is or nitre with the proviso that X may also be hydrogen when n is 1 or 2 and there is halogen located in the is methyl or and n is 1 or Typical compounds within the scope of this invention it 1 and salts of the above Based on plant growth regulatory preferred compounds of this invention includo and their Water soluble salts of the compounds of this invention where Y of Formula I is OH include the alkali metal preferably the sodium and the di and trialkylammonium wherein each alkyl group may contain up to carbon erably and and propanolamine salts such as the ammoniumi and and quaternary ammonium salts such as ammonium and Other useful salts include the alkaline earth particularly the calcium and nickel and The compounds provided by this invention may be prepared by involvoo oynthooieing N oryl derivative by any known to bo ouitablo For there may first be prepared precursor corresponding to the wherein and Aryl have the above Partial hydrolysis of the group in such precursor to results in the In many instances hydrolysis results in a mixture of the derivatives and these may be separated by conventional means such as by verting the derivative to a salt and removing the insoluble The reaction consisting essentially of the two types of hydrolysis products with generally a minor amount of the unreacted cyano precursor can be used for biological purposes directly without Tests on the cyano precursor have shown that it neither has biological activity nor does it interfere with the biological activity of the hydrolysis The may be pared by condensation of with 10 acetamides of the The reaction maybe depicted as using the form of the Compound of Formula II The may be made by the general methods described by Adams et 1220 and Johnson et Organic Syntheses 75 is a product of cyanoacetamides are known compounds which may be made by heating ethyl cyanoacetate with the appropriate aniline or and removing the ethanol as formed according to the Compound of NCCH2C00C2H5 III This is usually a facile reaction in the temperature range of The end of the reaction is when the removal of ethanol is essentially The reaction product may be purified by standard such as or may be without further Refer to Piccinini et Chemishes Zentralblatt 335 In the condensation of with the equiniolar amounts of the two reactants are nortiially although excesses of either reagent are In some it may be expedient to use an excess of the The condensation of the with an acetamide is preferably carried out in the presence of a Suitable solvents include aliphatic aromatic dimethyl sulfoxide and carbon The preferred solvents are the alcohols such as isopropanol and monoethers of ethylene Heat is required for the condensation and this is usually obtained at the reflux temperature of the solvent Temperatures in the range of to are The condensation of the with acetamide is catalyzed by basic Typical catalysts include inorganic amines and quaternary Amine catalysts are preferred and good results have been obtained with diethylamine and triethylamine for General conditions this type of condensation are reviewed in edited by Interscience in Part III on and pages The can also be prepared by the general method described in the above cited on page This consists of quaternizing a pyridine with a particularly an or thalene of the formula where Z is a halogen for effecting the and is preferably This reaction is preferably a high dielectric constant carried out in such oxidizing 5 the resulting pyridinium with alkaline potassium to the corresponding The reaction may 10 The may also be prepared by a procedure generally described in the above cited book at pages By this procedure acetone is condensed with a of the Ary1 to give compounds of Formula This reaction is 15 carried out in the presence of a polyphosphoric be prepared from a substituted according to the general procedure described in the above cited book on page The which is conveniently carried out in may be depicted as The compounds of Formula V may be converted to the corresponding carboxy compounds or their salts by standard hydrolytic In the above represents The hydrolysis of may be plified by the following reaction The hydrolysis of the nitrile proceeds to either the amide or the acid under acidic conditionse Aqueous organic and mineral acids are suitable for this Typical of such acids are sulfuric and The temperature requirements for the rolysis are such that the temperature must be high enough to allow the hydrolysis to proceed but not sufficiently high to cause This is normally in the range of to a preferred range of to The cyano compounds of Formula II can be converted to the derivatives of Formula VI by hydrolysis hydrogen peroxide in dilute base or by other methods known in the can be hydrolyzed to the free acids of Formula VII by means of nitrous acid or by other hydrolytic procedures in the chemical The acids of Formula VII are readily converted to direct esterification with alcohol6 gives esters and reaction with halogenating agents such as oxalyl thionyl chloride or bromide and phosphorus pentachloride gives the acid The acid halides can in turn be converted to and other common derivatives by standard The following examples are illustrative of preparations of the compounds of the but are not to be construed as ations The example numbers correspond to those given in subsequent Tables VI and Example 2 Preparation of A reaction mixture consisting of of 10 of 5 of piperidine and 200 of ethanol was refluxed for 3 The reaction mixture was cooled to give a solid which was filtered washed with methanol and recrystallized from glacial acetic acid to give 22 of This white solid melted at It was found by analysis to contain H and N calculated for is H and It is an yield of Forty grams of was dissolved in a solution of 100 of concentrated sulfuric acid in 60 of The reaction ture was heated oh a steam bath over After cooling the the product was poured into water to give a solid which was filtered off and recrystallized from The isolated solid was of white solid which melted at This was found to contain by analysis H and calculated for is H and The product is a yield of Example 19 Preparation of A reaction mixture consisting of 777 of of centrated sulfuric acid and of water was heated on a steam bath at for 15 The cooled mixture was poured into 7 of water and the resulting solid was filtered The solid was treated with l600 of 25 aqueous sodium filtered and the solid residue treated with 2200 of aqueous sodium hydroxide with stirring for hours at room The product was filtered and from the filtrate there was isolated 326 of The insoluble which was 257 of solid melting at was washed with 1000 of aqueous sodium then with filtered and the residue dried to give 25Ο of almost white solid melting at By nmr this was shown to be essentially and as such is a A sample of the solid was recrystallized from a 50 mixture of to give the product as a white crystalline solid melting at This solid was found to contain by analysis N and calculated for N and Example 32 Preparation of the Sodium Salt of To a solution of of aqueous sodium hydroxide in of deionized water was added 722 of This was stirred until solution The solution was poured onto trays and the water allowed to evaporate to give a solid which was then dried in a oven at about for There was obtained 872 of a dry powder which melted with decomposition at Analysis showed it to contain Mass spectrographic analysis indicated The product was recrystallized from Titration with N chloric acid showed it to be It melted at The product is a quantitative yield of the sodium salt of The sodium salt of was prepared in the same The recrystallized solid was found to be pure by titration and melted at Example 35 Preparation of A reaction mixture consisting of 10 of 100 of methanol and 1 of concentrated hydrochloric acid was stirred at reflux temperature for about l6 It was cooled to to give a white solid which was filtered washed with cold methanol and The product was 8 of a light tan crystalline solid melting at Infrared spectroscopy confirmed that the product was exclusively an The solid was found to contain by analysis N and calculated for is N and The product is a yield of TABLE I Preparations of NCCH Aryl Preparation Mel 4 I Preparation 4 5 2 2 amide TABLE II of TABLE II Melting Empirical Preparation Point Formula Element C H if luoromethylp 2 TABLE II Melting Empirical Preparation Point Formula El TABLE II Melting Empirical Preparation Point Formula Ele 4 2 4 TABLE II Melting Preparation Point Formula Ele 2 2 275 TABLE II Melting Empirical Preparation Point Formula E Examples of Melting Empirical Anal Example X Point Formula Element Fou 1 Br H CI H 7 0 TABLE III Melting Empirical Analy Example X Point Formula Element Foun 7 iso H C H N 0 TABLE III Melting Empirical Ana Example Point Formula Element Fo 11 H 0 17 CI C H C1 0 15 C 65 H 5 F 6 N 5 C 61 H 4 CI 1 N 0 1 TABLE III Melting Empirical Ana Example X Point Formula Element Fo C C 61 18 CI TABLE IV Examples of Melting Empirical Ana Point Formula Element Fo E H C 65 H F 7 N 10 0 13 H C 56 H N 0 22 TABLE IV Melting Empirical Analysi Example X Point Formula Element Found 24 H 25 H 26 CI CI C H N 0 28 c H F N 29 TABLE V Examples of Derivatives of Example Sodium salt of Cupric salt of 20 32 Sodium salt of 33 Dimethylamine salt of Dimethylamine salt of 35 36 37 poi TABLE VI Examples of Melting Empirical Ana Example Aryl Y Point Formula Element Fo OH 39 ophenyl 40 OH OH C C 51 phenyl H 2 CI 21 F 5 N 4 TABLE VI Melting Empirical Ana Example Aryl Point Element Fo 42 2 4 44 4 OH 0 15 TABLE VII Examples of 1 Melting Empirical An Example Point Formula Element F CH OH 0 1 TABLE VII R R R Empirical Ana Example Y Point Formula Element Fo 48 C 9 CI CH OH C 0 The compounds of this invention have been found to produce a variety of plant These responses are a growth regulating amount of served compounds alone or in a carrier or as ions are applied to the plant as by foliar or to plant parts such as by seed treatment or to the ment or habitat of the such as by soil drenching or soil The most outstanding influencing property is suppression of This is most found to be a growth inhibitory action on the stern elongation is In other instances flowering or seed formation is In other cases malformation of leaves is particularly at high a plant species may be icidally Preemergence herbicidal activity has also been Individual plantspecies give different types of responses any one or of these plant responses may be observed for any given The major contribution of the of this invention to the field of plant growth regulation is that they provide plant growth regulants which inhibit stem elongation of many crop and woody species and alter ing and fruit A soil drench test was used as one method for evaluating plant growth regulating properties of the compounds of this In this seeds or plants were planted in pots and a given stage of growth the soil was watered with a preparation taining the compound at given dosages in terms of pounds per Growth responses were subsequently In one such test about 20 wheat seeds were planted a inch pot and allowed to grow for 11 at which time the second leaf of wheat was A solution or suspension of the chemical was prepared by dissolving the compound in about 1 of acetone or water and adding sufficient water to make 50 The amount of chemical was such as to provide 2 and 20 pounds per For example 2 give or kilos per test was in triplicate and untreated plants were cluded as Four weeks after treatment the overall height of the plants from the soil level to the leaf tip was The per cent inhibition was calculated as height of treated plant Inhibition 100 100 x height of control plant The following Table VIII gives the TABLE VIII Inhibition of Wheat by Soil Drench Inhibition at Example 2 20 11 1 52 82 2 53 71 3 15 41 4 4 74 5 18 52 6 43 63 7 0 8 20 57 9 6 25 10 0 17 11 0 24 12 31 62 46 80 34 58 15 31 60 16 20 57 17 61 84 18 48 73 19 20 52 20 0 0 21 10 15 22 0 30 23 0 13 0 0 25 0 0 26 6 37 27 0 7 28 0 24 TABLE VIII Inhibition of Wheat Plants by Soil Drench Inhibition at Example 29 0 30 59 67 31 34a 50a 32 60 74 33 60 67 63 71 35 17 52 36 0 34 37 49 64 38 41 57 39 7 29 0 21 41 56 42 16 52 3 6 40 44 0 9 47a 58a 46 5 67 47 21 47 48 18a 39a 49 34a 47a a approximately two weeks after treatment In this type of test the following compounds gave no hibition of wheat the plants were similar to untreated For foliage spray the compounds were dissolved in an appropriate usually acetone for the acids and esters and water for the salts and sprayed onto the foliage at a given dosage per acre in a carrier volume of about gallons per Growth responses were subsequently In one such test the compounds of Example and 33 were using old potted wheat The compounds were pared for testing as Example gram of was dissolved in 100 of Example of was dissolved in l8 of N sodium hydroxide and the solution diluted with water to a volume of 100 Example gram of was dissolved in dimethylamine solution and the solution diluted to a volume of 100 The above solutions were sprayed onto the potted using a calibrated sprayer at such a rate as to deliver per The solutions were appropriately diluted for lower Two months after treatment the per cent inhibition as compared to control plants was Table IX gives the TABLE IX Inhibition of Wheat Plants by Foliar Application Inhibition at Example 1 2 2 21 40 56 30 23 33 30 4 56 In seed treatment tests an aqueous solution or suspension of the test compound was prepared and diluted to various per cent Seeds were then immersed in these preparations for about 20 after which they were washed with planted in untreated and the germination and growth subsequently In one such greenhouse test the sodium salt of was dissolved in water to give a series of concentrations varying to weight from Seeds of oats and wheat were treated with these solutions as indicated above and Four weeks after planting the per cent inhibition was A inhibition indicates the seeds did not germinate or that no plants Table X gives the TABLE X Inhibition of by Seed Treatment Inhibition at Plant Specie Concentration 1 3 barley 16 21 2 100 100 oats 7 7 30 37 wheat 6 18 24 2 100 Table XI gives plant responses obtained with on a variety of plants by either the soil drench or foliar application These results are typical of the other compounds of this TABLE XI Responses Obtained with Example Plant Species Response Observed Apple Stem Leaf Epinasty Barley Initiation of flowering d Barnyardgrass Stem Seed Beans Seed Number of bean pods incr Malformation of leaves Stem malformation of burs Corn Stem Cotton Stem cucumber Seed Cucumber fruit increased Eggplant Plants transplanted 2 we before treatment were de Flax Stem Seed TABLE XI Plant Species Response Observed Grape Stem Leaf epinasty Mimosa Stem Nutgrass Stem Oats Stem Seed Number and weight of heads increased Peach Stem Pigweed Stem Seed Length of flower heads decreased Rice Stem Broader leaves Rye Stem Seed Safflower Stem Seed Soybeans Stem Seed Squash Seed Number of squash fruit increased TABLE XI Plant Species Response Observed Sugar beets Decreased foliage weight and increased beet weight Tomato Flowering prolonged Fruit setting and development Turf grasses Stem Wheat Stem Seed Plants had thicker and broader and thicker leaves Stem Stem elongation inhibited Seed Sded formation inhibited In similar by foliar no appreciable growth inhibition was observed oh carrot chrysanthemum radish sunflower turnip When the compounds of this invention are applied to plants or to the habitat of they give a growth regulating response in the dosage range of about to pounds per acre to 33 kilos At the higher herbicidal responses may be Depending on the type of response the amount will vary with the plant species to be Generally the preferred range is from to pounds per Seeds may be treated with the compounds themselves or with any concentration of a solution or formulation of The compounds of this invention may be employed as plant growth response agents either individually or as a mixture of two or more of They also may be used in combination with other plant growth regulatory compounds such as maleic succinic acid choline and its triiodobenzoic polymeric phosphate and its and acid and its The compounds of this invention may also be combined with a herbicide for use on plants which are not sensitive to the herbicide at weed controlling For they may be combined with for use on plants such as eerials and turf with anilide for use on rice or Vv ether for use on rice and other The compounds of this invention may be applied in tion with one or more additives such as a fluid a solid diluent or carrier or a liquid which may for dissolve the active ingredient and which may or may not be a commonly used One preferred group of the compounds is the water soluble in which case water is the preferred Nonphytotoxic organic solvents such as dimethylformamide and dimethyl sulfoxide may be If desired a surfactant such as a wetting agent may also be used and this usually constitutes a minor part general less than 10 of the solution or The surface active agents may be cationic or For the salts cationic and surfactants are Commonly used surfactants are in the art and may be found in John publication and John McCutcheon New The compounds may also be applied in liquids containing thickening or sticking The compounds of this invention may be formulated in various ways as for example emulsifiable wettable granules and Usually for application to the plant or plant parts or the plant the formulations are extended with a suitable Emulsifiable concentrates are most usually extended with a liquid carrier such as water and granules and pellets are most usually extended with a solid carrier such as mineral Emulsifiable concentrates may be made by dissolving the compounds in an organic solvent and adding one or more soluble emulsifying solvents are usually immiscible and may be found in the chlorinated alcohol and amide classes of organic Wettable powders may be made by incorporating the compounds in an finely divided solid carrier along with a surfactant which may be one or more dispersing or spreading agents or blends of Suitable carriers may be found in the classes of carbonates and organic Solid compositions in the form of dusts may be made by pounding the compounds of this invention with inert carriers ventionally employed for the manufacture of pesticidal dusts for agricultural such as finely particled diatomaceous magnesium carbonate or wood or shell Granular or pelletized formulations may be made by corporating the compounds into granular or pelletized forms of agronomically acceptable carriers such as granular ground corn cobs or Representative compounds of this invention have shown fungicidal For the compound of Example 2 has given control of bean powdery mildew and the compounds of Example 10 and 25 have given good control of tomato late blight The growth regulatory action of the compounds of the present invention may be advantageously employed in various The production of shorter and thicker stems in cereal grains reduces the tendency toward Turf grasses may be maintained at a low height and the necessity for frequent mowing The plant growth on such as may be controlled to prevent erosion and at the same time maintain its aesthetic There may be an advantage in producing a dormant period in certain The control of flowering and fruiting may be advantageous in the production of seedless fruit and for Delaying the vegetative process or altering the time of flowering and ing may result in more advantageous harvest dates or increased fruit seed The chemical pruning of ornamentals and nursery stock may be Other applications of the compounds of the present invention will suggest themselves to those skilled in the art of agriculture and insufficientOCRQuality

Claims

wherein Y is -ΝΗ,, or -OR where R is hydrogen, C-^-C^ alkyl or a salt-forming cation; X is amino, fluoro, chloro, bromo, iodo, methyl, methoxy or nitro with the proviso that X may also be hydrogen when n is 1 or 2 and there is halogen located in the 3- position; X1 is fluoro, ihloro, bromo, iodo, methyl or methoxy; and n is 0, 1 or 2.

3. The compound l-(4-chlorophenyl)-3~carboxy-i,6-dimethyl- pyrid-2-one and salts thereof. . Water-soluble salts of the compound claimed in Claim 3· 5· The compound l-(3,^dichlorophenyl)-3-carboxy-½,6- dimethylpyrid-2-one and salts thereof.

6. Water-soluble salts of the compound claimed in Claim 5·

7. A compound of the formula wherein ^ and Rg are methyl and ethyl, ^ is hydrogen, methyl, ethyl or chlorine, X is amino, fluoro, chloro, bromo, iodo, alkyl of 1 to 5 carbon atoms, trifluoromethyl, methoxy or nitro; X1 is fluoro, chloro, bromo, iodo, methyl, trifluoromethyl and methoxy and n is an integer of 0, 1 or 2 with the proviso that X may be hydrogen when n is 1 or 2 and there is halogen in the 3-position. 8· Λ compound according to Claim 1 being any one of those individual compounds disclosed in the foregoing specification with the exception of the compounds claimed in Claims 3 and 5 °r salts of such individual compounds.

9. A composition for treating plants containing as active ingredient at least one compound as claimed in Claltoi 1· 10*. A composition according to Claim 9 containing as active ingredient a compound as claimed in Claim 2. 11· A composition according to Claim 9 containing as active ingredient a compound as claimed in any one of Claims 3-6.

12. A composition according to Claim 9 containing also a solid diluent or carrier, a surface active agent, a liquid containing a sticking or thickening agent or a pesticide 13· A method of regulating plant growth which consists of applying to a plant, to plant seeds or other plant parts or to the habitat of a plant a growth regulating amount of a compound according to Claim 1» Ik. A method according to Claim 13 wherein the growth regulating amount of the said compound is in the range of 0·01 to 30 pounds per acre. 15· A method according to Claim I wherein the growth regulating amount of the said compound is in the range of 0,05 to 15 pounds per acre. 16« A method according to Claim lh in which the application of said compound is made to the plant foliage or to the soil in which the plant is growing,

17. A method according to Claim 13 in which the application of said compound is made to plant seeds.

18. A method according to Claim Ij5 in which said applied compound is a compound according to Claim 2. 1 . A method according to Claim lj in which the said compound is l-( -chlorophenyl)~3-carboxy-^,6-dimethylpyrid-2-one or its salts.

20. A method according to Claim 13 in which the said compound is 1-(3,^-dichlorophenyl)-35-icarboxy-i+,6-dimethylpyrid-2-one or its salts.

21. A method for the preparation of a compound according to Claim 1 which includes the step of synthesizing an N-aryl sub-stituted pyridine derivative by a technique known to be suitable for the preparation of such a compound.

22. A process according to Claim 21, wherein there is first synthesized an appropriate l-aryl-3-cyano- ,6-dimethyl-pyrid-2-one precursor, the cyano group of which is then hydrolyzed to an amide or carboxylic acid group. 23· A process according to Claim 22, wherein said precursor is synthesized by the condensation of an appropriate beta-diketone with an N-aryl cyanoacetamide of the formula: NCCH2C0NH- Aryl in which Aryl is as defined in Claim 1.
2 A process according to Claim 22, wherein the condensation is carried out in the presence of a basic catalyst.

25. A process according to Claim 22, wherein said precursor is synthesized by condensing acetone with α-β-ketoamide of the formula: CH C(0)CH(CN)C(0)NH Aryl 3 where Aryl is as defined in Claim 1. 26· A process according to Claim 25, wherein the condensation is carried out in the presence of a polyphosphoric acid. 2?· A process according to Claim 21f wherein an appropriate 3-cyan'o-pyridine is quaternized with a halobenzene of the formulai ; · X where X is as defined in Claim 1 and Z is a halogen capable of effecting the quaternization reaction, the resulting pyridinium salt of the iSryl then being oxidised to an a-pyridone.

28. A process according to Claim 27, wherein the quaternization reaction is carried out in a solvent having a high dielectric constant.

29. A process according to Claim 27 or 28, wherein the oxidation is carried out using alkaline potassium ferricyanide. as

30. A process according to Claim 21/applied to the preparation of N-31 , '-dichlorophenyl-3-carboxy-^,6-dimethyl-pyrid-2-one or a salt thereof.

31. A process according to Claim 21 as applied to the preparation of N-^ 1-chlorophenyl-3-carboxy- , 6-dimethyl-pyrid-2-one or a salt thereof.

32. A compound according to Claim 21 whenever prepared process according to any one of Claims 21-31» Poi* the k p mti DR. REiNHjfljb /OHM AND/PARTNERS By: