IL32351A - 3-substituted-pyrido(3,2-d)pyrimidine-2,4(1h,3h)-dione compounds and 1,3-disubstituted analogues,and their use for the control of plant growth - Google Patents

Description

and CHEMICAL COMPANY 2 The invention relates to new and compounds to methods for their and to plant growth regulating compositions containing these compounds as active The new compounds according to the invention can be as plant growth selective weed killers defoliating In recent years increased crop yields have been made possible by the development and use of chemicals which are specifically toxic to yet do not damage crops around which they In the currently available chemicals which are most desired their selectivity and as total herbicides are sufficiently expensive that expense is a significant factor in their new compounds and inexpensive methods for producing such compounds are constantly being In while many compounds presently on the market are effective to control the growth of certain species of they are ineffective against Thus new herbicides which have broad spectrum effectiveness against a wide variety of weeds are continually being A family of compounds which has been found particularly effective are the substituted of the formula 3 wherein R and are different and either R is of 2 to 8 carbon cycloalkyl of to 12 carbon alkenyl of up to 8 carbon atoms or alkynyl of up to 8 carbon and is hydrogen or alkyl of 1 to 4 carbon or R is than in which the alkyl portion has 1 or 2 carbon and the aromatic portion or phenyl substituted with 1 or 2 or or a stituted alkyl group having 1 or 2 carbon a or radical or an aryl phenyl or naphthyl optionally substituted by nitro or and hydrogen or an alkyl radical having 1 to 4 carbon alkali metal alkaline earth metal or ammonium salts of the compounds of formula addition compounds of compounds of formula I with nitrogenous bases or with phenolic complexes of the compounds of formula The invention also consists in compositions taining as active ingredients compounds of formula I above or addition compounds with nitrogenous or with acids or their complexes with 4 Most of the of the invention can be produced by reacting a compound having the formula wherein is alkyl having from 2 to 8 carbon cycloalkyl having from to 8 carbon alkenyl having up to 8 carbon atoms or alkynyl having up to 8 carbon or aralkyl than where the alkyl portion has 1 or 2 carbon a toms and the aromatic portion is phenyl or phenyl substituted with or 2 methoxy or chlorine substituted alkyl groups having from 1 to 2 carbon or with sodium the reaction being carried out in the presence of sodium hydroxide and a suitable preferably at elevated The reaction illustrated Generally R having the meaning assigned in explaining the immediately preceding The reaction is and will in the absence is accelerated by heating the reaction For reason it is preferable to heat the reaction mixture to a temperature from about to the boiling temperature most desirably about and hold it at such temperature for about Thereafter the mixture is cooled temperature and neutralized at which time the reaction product reported herein and in the attached arc in degrees centigrade unless otherwise 6 The corresponding compounds can be produced by alkylating the produced as this can be done by reacting the dione with an alkyl halide in the presence of sodium hydride and a solvent such as dimethylformamide or The preparation of compounds of formula I in which R has other meanings than those defined in connection with formula II above will be described later on in the This invention can be more clearly understood by reference to the following The are not intended to be EXAMPLE I PREPARATION OP A 22 flask equipped with a stirrer and a and surrounded by a heating mantle was charged with 6 sodium hydroxide and aqueous solution containing 7 5 Stirring was and was continued throughout the When this charging was the temperature of the charge was then 2 N2 was added to the solution in the After the pyridinedicarboxamide the temperature of the reaction mixture was the reaction mixture was then heated for a total of about 50 The temperature after 20 minutes of heating was after 50 minutes of heating The heating mantle was then and the flask was immersed in an ice bath for about 1 hour 5 final temperature of th reaction product was Approximately a 75 liter receiving vessel was then charged with 600 glacial acetic and immersed in an ice The reaction product was added gradually to the acetic acid in the with The rate of addition of the reaction product was controlled so that the temperature of the liquid in the receiver remained within the range of 10 to 15 The pH of the liquid in the receiver was and additions of glacial acetic acid were as to prevent the pH thereof from rising above about The which had separated as an to cream separated from the mother liquor by using a Buchner The final product was washed with tap wat and dried in a circulating air oven in which the air was maintained at a temperature within the range of 80 to The total recovery of dried product amounted to or 95 percent of It was determined by nuclear magnetic resonance analysis that the product was percen plus or minus The remainder of the product was presence of the is attributable to in the starting EXAMPLE II PREPARATION OP ONE A 22 flask equipped with a stirrer and a and surrounded by a heating mantle was charged with 81 sodium hydroxide and aqueous solution containing Stirring was and was continued throughout the When this charging was the temperature of the charge was then N2 dicarboxamide was added to the solution in the After the the temperature of the reaction mixture was the reaction mixture was then heated for a total of about The temperature after 10 minutes of heatin was after 15 minutes after 21 after 25 minutes and after 55 minutes The heating mantle was then and the flask was immersed in an ice bath for about 2 the final temperature of the reaction product was 10 The reaction mixture was then acidified by making a gradual addition of glacial acetic acid to a pH of The rate of addition of acetic acid was controlled so that the temperature of the mixture in the flask remained within the range of 10 to The dione which had separated as an to cream was separated from the mother liquor by using a Buchner The final product was washed with tap water and dried a circulating air oven The total recovery of dry point amounted to or percent of It was determined by nuclear maenetlc resonance analysis that the product was 98 plus or minus 2 The remainder of the if was The presence of the is attributable to an impurity in the amide starting It will be noted in the procedure described in Example the reaction product added to glacial acetic acid in the procedure described Example glacial acetic acid was added to the reaction It has been in some the Example II cedure causes the dione product to appear as a sticky this causes difficulty in Such difficulty is or eliminated altogether when the Example I nique is this procedure therefore XXV EXAMPLES III THROUGH other compounds of the invention have been produced by the above described Information concerning starting batch final product and yield for representative ones of such preparations is presented in Table ormula Solution NaOCl 580 dicarboxamide NaOCl pyridine carboxamide NaOCl 19 pyridine dicarboxamide 146 pyridine dicarboxamide NaOCl 97 pyridine dicarboxamide NaOCl 68 pyridine dicarboxamide NaOCl pyridine dicarboxamide NaOCl 145 2 dicarboxamide Name or Name formula Solution XI NaOCl dicarboxamide XII Naoci 194 dicarboxamide XIII NaOCl 16 260 dicarboxamide XIV N NaOCl 250 dicarboxamide XV N i NaOCl 240 dicarboxamide AVi N NaOCl 2 250 dicarboxamide I Starting Amide grams XXIII N 42 dicarboxamide dicarboxamide XXV NaOCl 250 dicarboxamide V 2 1 VII VIII IX 1 X 3 XI XII 2 XIII 8 Pinal Product Example Name XV Λ XVI hoxyethyl XVII XVIII 29 XIX XX pyriir 24 XXI XXII XXIII Product XXV pyriroidine readings for each of the represented by the Examples set forth in Table I are presente in Table II Zero time is when the amide added to reaction TABLE II Time Temperature 23 00 48 55 0 00 64 63 60 IV 15 18 39 60 78 79 00 76 00 62 16 1 TABLE II 2 Time Temperature 3 4 V 5 24 6 42 7 55 8 9 68 65 11 52 13 VI 1 22 15 O 16 17 80 18 86 19 86 20 VII 22 34 23 21 24 60 25 60 26 60 27 28 29 TABLE II E Temperature VIII 30 31 50 70 80 75 71 60 I 26 80 85 TABLE II Time Temper t X 20 41 80 84 86 84 XI 79 84 8 TABLE II Time Minutes XII 38 55 70 80 80 61 58 XIII 16 21 40 60 62 XIV 16 21 45 00 51 60 64 TABLE II Temperature XV 20 21 5 55 8 67 9 10 11 12 XVI 20 13 25 14 50 15 50 16 60 67 18 67 TABLE II TABLE Time Temperature 15 19 52 61 67 70 14 19 22 75 70 40 17 65 66 62 26 Example temperature XXIII 10 15 50 70 65 TABLE II Time 15 20 25 50 70 72 60 20 40 50 70 62 The structures of the final compounds of XXV III through XXIX were confirmed by elemental and by infrared and nuclear magnetic resonance The production of of this invention where the or is discussed subsequently The other pyrido of this invention can be made by the procedures described in Examples I and substituting the appropriate dicarboxamide for and the starting XXVI EXAMPLE PREPARATION OP A flask partially immersed in an ice bath and equipped a addition gas inlet and outlet and nitrogen atmosphere system was The nitrogen was turned and NaH in petroleum and was charged into the Agitation was begun and continued throughout the The temperature at this point was Twenty minutes later the temperature had fallen to At this time the nitrogen was turned and the addition of dissolved in 110 of was A light slurry began to turning to brown during the 20 minutes it took to complete the charging of the After completion of the charging of the CH3C1 was introduced into the reaction mixture at the rate of per A hazy light brown solution formed turning tp reddish brown as the addition The temperature at this point was Another of CH3CI was then charged at the rate of Solids forming a red orange colored The temperature at this point was and the pH was between 8 and The slurry was stirred for an additional three The total elapsed time at this point 9 The slurry was set aside Then it was quenched into 1120 of tap water 7 to 1 ratio of water to dimethylformamide forming a clear light tan The solution was stirred for 1 then the pH was adjusted to with dilute hydrochloric No solids were Then the solution was partially evaporated and the precipitate filtered and The filtrate was evaporated still more and a second crop filtered and The total yield was or percent of Infrared analysis was in agreement with the structure for other of this invention can be made by the XXVI procedure described in substituting the appropriate alkylating agent or for the starting materials used DISCUSSION OF THE REAC The best yields are obtained when one equivalent of base and one equivalent of hypohalite are used for each of the Satisfactory have been when as much as two equivalents of the hypohalite were used per mole of the While the method above described contemplates the use of alkali and alkaline earth metal hydroxides and alkali an alkaline earth metal sodium hydroxide and sodium hypohalite preferred for economic reasons The other metal hydroxides and metal hypohalites are perfectly factory but the cost thereof is much The metal hypohalite may be prepared by reacting chlorine or bromine with a water solution of an alkali metal or alkaline earth metal preferably sodium For a 1 sodium hypochlorite solution can be prepared by reacting with chlorine in sufficient water to make one It can be appreciated that one equivalent of bromine can be substituted for chlorine to produce a sodium hypobromite solution metal hydroxide can be substituted for the sodium hydroxide to produce a different metal Water is the preferred solvent medium for the reaction due to low Other solvents could be used alone or mixed with water such as alcohols or equivalents if they do not interfere with the course of the reactic There is no advantage to The exact amount of water to be used is not The best results have been achieved with approximately 2 of water per mole of the starting Satisfactory results have been achieved with as as 20 and as little as 1 of DISCUSSION OF THE REACTION METHOD In carrying out the process described in I or Example II for producing the compositions of the invention the metal hypohalite should first be admixed with i the and then the amide should be If the components are not admixed in this there is a tendency for the amide to hydrolyze to the corresponding acid resulting in a lower The temperature at which the reaction is conducted can range from to with being the most reaction mixture should be held at the desired temperature for about hour or until a negative test for hypohalite indicates the completion of the At the end of the the reaction is cooled to room temperature and neutralized with acid to a pH in the range of 10 to to precipitate the product which can then be collected by washed and The preferred pH range is from to Any acid can be used for the pH adjustment but mineral acids and simple organic acids such as acetic acid are most preferred for economic The which constitute a family of starting materials in producing the compounds of this invention can be made from corresponding acids according to the method in Example A The preparation of is used as an EXAMPLE A A flask equipped with a stirrer a and partially immersed in an oil bath was charged with OO 00 and 400 acetic Agitation was begun and continued throughout the The reaction mixture was then heated rapidly to a temperature of and held at that temperature for 2 During this period the acetic acid which was produced was distilled At the end of this the mixture was the solids removed by and the filtrate set The solids were washed with cold and The yield was light tan material having a point of The filtrate which had been set acide was concentrated in and a precipitate of medium brown material having a melting point of was recovere by The total yield was dicarboxi The was used to prepare in the following A 500 flask equipped with a and addition and partially immersed in an ice was charged with dinedicarboximide and 150 Agitation of the flask contents was begun and continued throughout the duration of the An addition of amine was then commenced and charged over a 2 minute After the the reaction mixture was stirred for an additional 2 hours and 10 during which time the temperature of the reaction mixture reached a high of At the end of this the thick slurry which had formed was cooled to about the solids were removed by and the filtrate was set The solids were then washed with cold and The yield was product which had a melting of and was identified by Infrared Spectroscopy as The starting materials to produce the compositions of this invention can be made in substantially same substituting the required i amine for the isopropylamine employed in the foregoing In some instances a mixture of isomers is If separation can be accomplished either by preferential precipitation or by column Not all of compounds of this invention ca be prepared XXV in the manner described in Example For where the is an aryl group or an alkyleneimino group cannot be produced in the so far as is They can be produced by other and morpholino substituted compounds can be produced by the reactions illustrated Ethyl Ethyl Ethyl picolinate in the The following illustrates the preparation of XXVII EXAMPLE for Examples PREPARATION OF XVII to XXIX Preparation of Ethyl Ethyl was produced acid and 80 sulfuric dissolved 200 anhydrous ethanol The reagents combined and heated under reflux for and the reaction mixture then poured onto crushed and neutralized with sol potassium A solid precipitate which formed was separated from the acid phase by and was extracted with 200 hot The acid fraction was extracted times with 100 portions of methylene methylene chloride and acetone extracts were dried with anhydrous magnesium and concentrated under reduced Evaporation of the methylene chloride and acetone to leave a volume of about reaction mixture caused precipitation of solids which were recovered by recrystallized from benzene identified by infrared spectroscopy as ethyl melting point and calculated elemental analyses for another batch of ethyl which batch was found by infrared spectroscopy and melting point to be identical with that C H N Preparation of Ethyl Ethyl was produced ethyl and The ethyl produced as described above was first dissolved in dry and the resulting solution was with with dry hydrogen chloride About a temperature rise indicated the occurrence of a exothermic After about 2 hours a whitish precipitate which was the hydrochloride of ethyl picolinate began to Reaction was with for a total of approximately 8 The toluene slurry was under and saturated rapidly with an excess of Phosgenation was continued for a total of during which time the reaction mixture was kept saturated with After the toluene solvent was distilled from the reaction leaving a tan oil which was identified by infrared by nuclear magnetic and by elemental as ethyl of y urea The ethyl produced as above was dissolved in benzene and approximately a portion of was added dropwice to the resulting Λ rise indicated The reaction 1 mixture was refluxed for hours and was then acidified with acetic acid until a white precipitate The white melting point was identified by infrared spectroscopy as Preparation of The urea produced as described above was dissolved in 40 solution of equal parts by volume of hydrochloric acid and ethyl alcohol and heated under reflux for 5 The solvent was then leaving a brown which was allowed to stand during which standing solid i melting point The solid was Identified by infrared spectroscopy as the hydrochloride salt of The hydrochloride salt was dissolved in water acidified with hydrochloric acid to a pH of 2 and the resulting solution was neutralized to a pH of 8 with potassium bicarbonate to cause reprecipitation of the final melting point identified by infrared spectroscopy as After ethyl the final product had a point of and was and The elemental analysis and for purposes of were as Theory Found C H N The pyrido of this invention can be produced by the method described in Example It is necessary only to substitute an equivalent of the appropriate or for the used in the Example The diones of this invention can be produced by the reaction illustrated below 5 6 Ethyl 12 13 14 dione 16 17 The following example illustrates the production 19 of by 20 reaction between phenylurea and ethyl 21 XXVIII 22 EXAMPLE 23 pyrido 24 was produced from ethyl and 25 phenylurea plus an excess of about A blended 26 mixture of the ethyl and of the phenylurea 27 was placed in a and the beaker was immersed in 28 30 an oil in hours and and bath t are set forth in the following ze o time that at which the beaker was immersed in the Time Temperature 0 At the end of the 1 hour 1 minute heating contained a finely divided and heating The crude product from this was combined with crude from other batches to provide total of This material was dissolved in 0 sulfoxide at carbon treated and quenched into 1 wate tan colored solids which precipitated were recovered by and identified by infrared spectroscopy as yield was i purified Other can be produced by the procedure described XXVIII above in Example merely by substituting for the phenyl urea equivalent amount of the aryl Examples of known aryl ureas which can be so used include and between the acid and phenyl isocyanate has also been utilized to produce e yr The reaction proceeds if the phenyl isocyanate and the acid are merely heated under and is illustrated by the following XXIX EXAMPLE XXXIII PREPARATION Reaction between 12 phenyl isocyanate and 7 acid was utilized to produce The picolinic acid the phenyl isocyanate were merely charged to an appropriate and heated under reflux for 1 The reaction mixture was then cooled to a of 150 percent sodium hydroxide solution was then added to the reaction and the resulting mixture was stirred at a temperature of about for approximately 1 hour and cooled to room An addition of 100 10 percent sodium hydroxide solution was then the mixture was heated to and material was separated from the solution by The filtrate was acidified to a pH of with acetic Insoluble approximately 1 was separated from the liquid by and recrystallized from methyl The recrystallized melting point in excess of was white in color and was identified by infrared spectroscopy as pyrido XXIX The procedure described above in Example XXXIII can also be used to produce other merely by substituting an equivalent amount of the appropriate isocyanate for the XXIX phenyl isocyanate used in the Example Examples of other aryl isocyanates which can be so stituted isocyanate isocyanate isocyanate substituted compounds have been found to display unexpectedly high levels of herbicidal activity and to be useful in controlling undesirable plants of both the and the dicotyledonous species on either a or a preemergence By is meant that the compound is applied to soil prior to emergence of the weed species sought This as used also means the application of the herbicidal compounds falling within the scope of this disclosure to areas wherein useful or desirable are either growing or have been but where the undesirable plants sought to be trolled have not as yet By the term is meant that the compound is applied to the plant sought to be controlled after it has emerged from the soil This term is also used to describe the application of herbicidally active compounds to soil surface in and around growing plants sought to be controlled for purposes of effecting absorption by the undesirable plant Especiall active are the compounds where the is hydrogen and the is cyclcoctyl or and the hyl of invention will be more clearly understood by reference to the following EXAMPLE The preemergence and postemergence herbicidal activity of dione achieved at various application rates is shown in Table III In using the seeds of the type of plants set forth in Table III were sown in fresh In the preemergence test the soil was sprayed with a solution of the test compound immediately after the seeds were and before any noticeable growth developed in the test The solution was about a 2 percent by weight solution of the compound in acetone The compound was applied at the rate of 16 pounds per acre of soil surface Approximately three weeks after spray the herbicidal activity the compound was determined by visual observation of the treated area in comparison with untreated control These observations are reported below in Table III wherein the average activity rating is reported as the percent control of plant the soil and were prayed about two weeks aftcr the seeds were The applied at the rate of pounds per acre about a 2 percent by weight solution of the test compound in alcohol acetone The activi w s measured in the same way as the preemergence i visual observation days after and expressed as the percent of TABLE III Compound Preemergence Treatment Treatment Control Control Alfalfa 100 90 Corn 100 50 Wild Oats 100 70 Cheatgrass 100 Foxtail 100 100 100 100 100 20 50 Johnsongrass 100 90 Curled Dock 100 100 Snapbeans 100 90 Yellow Rocket 100 100 100 70 Cucumber 100 100 100 100 100 100 The same solutions the came compound can also be for example along railroad righ at an application rate about 10 to poundD per acre as a total to prevent all other disclosed herein can be used as or herbicides in a In the case of dione and substantially the same application as similar or salt solutions in are this is also generally true of the othe members of the pyrido although slightly higher application rates may be has been to be peculiarly effective because of its for applied as described at an application rate of 16 pounds per the benzyl compound showed no herbicidal against but total activity against curled pigweed and the family of compounds applied as and discussed above as having an unexpectedly high order of herbicidal is presented in the following In entries und refer to a preemergence test and those under re e to a postemergence All test results at rates 8 pounds per acre except those of certain o one Post Pre Post Pre Post Control Control Control 100 0 100 100 0 0 ICO 100 100 0 0 0 100 ICO 100 100 0 100 100 100 100 10 0 0 0 100 50 0 0 100 90 100 100 95 0 20 100 100 100 90 0 0 100 100 100 70 0 0 100 90 100 100 70 20 0 100 100 100 95 0 0 100 100 100 100 0 0 0 100 100 100 100 20 50 0 100 100 100 100 100 20 0 100 100 100 100 95 0 0 100 100 100 100 100 50 0 ICO 100 100 100 100 0 0 ICO 100 100 100 100 50 ICO 100 100 100 50 100 CO 100 100 50 80 100 100 100 100 Defermined at 2 pounds acre O d Post 20 0 0 10 0 0 Wild 90 10 0 30 0 100 30 10 20 0 30 20 50 10 0 0 80 0 20 20 0 0 100 0 SO 0 0 0 0 0 0 0 0 0 30 10 30 10 0 Curled 100 0 0 10 10 0 90 100 100 100 80 0 100 e 20 30 20 40 ICO D 50 0 100 95 0 100 0 0 70 90 ICO 0 0 70 100 0 0 0 SO 0 0 0 0 0 0 Defermined at 2 pounds per actr application rate 95 10 100 30 90 10 0 0 o 100 10 10 10 0 20 no 20 20 100 100 100 ho 90 100 100 90 100 60 100 20 30 95 100 90 100 100 90 100 100 ί 50 90 100 90 100 95 100 100 100 100 100 100 100 90 100 90 100 100 100 100 100 100 100 85 80 80 70 80 70 54 It be appreciated the foregoing data and discussion that the substituted family of compounds described herein has unexpected utility as and that this unexpected utility prevails throughout the For the showing of a high order of herbicidal activity for through alkyl substituents in the demonstrates the high order of activity where the is an alkyl group having from 2 to 8 carbon the demonstration that as a has substantially the same order of y activity as does an isopropul substituent in the 3 position shows that substituents in the same position impart activity of the same order as is imparted by alkyl substituents and in view of the showing relative to such alkyl demonstrates utility for 3 alkenyl substituents having not more than Θ carbon the demonstration of ectivity for a 3 benzyl as well as the showing of a high order of activity demonstrates utility for aralkyl substituents in the indicated When the substituent in the is a pyridyl substituted alkyl the compounds of the invention have somewhat lower but are useful because of their he high order of activity of the compound where the substituent in the is piperidino coupled with the showing relative to alkyl of of herbicidal activity for 1 and essentially no activity demonstrates the high of activity for the disubstituted where the 1 and are and where trie 1 substitiient is an ranging 1 to 4 carbon atoms in It has been found where is a cycloalkyl the pyrido has a high order of herbicidal activity when the cycloalkyl group has 3 to 8 carbon the cycloalkyl has 12 carbon the is stantially inert as a The herbicidal activity of pyrido where the cycloalkyl group has 10 or 11 carbon atoms has not presently been because the starting amines required to produce such compounds by the methods of Examples I and II are For practical use as the in the of this invention may be formulated with ventional agricultural carriers to obtain desired centration and to facilitate For these compounds may be formulated into dusts by combining them with such materials as or Wettable powder formulation may be obtained by adding a dispersing or suspending agent to the dust formulations referred to If the compounds may be applied as spray solutions which may be prepared by dissolving the compounds in suitable such as methylated common agricultural in accordance with well established agricultural The choice of solvent to be used will be dictated by the solubility of compound sought to be sprayed in that particular solvent it been found that the majority of these compounds have a relatively low order of water so that the use of common cultural organic solvents is the preferred compounds of this invention may also be emulsi or suspended in water by adding wetting agents or emulsifying agents to aqueous containing one or more of the chemical compounds falling under this These emulsified formulations are suitable for in spraying directly upon the locus to be protected from So far as been determined significan in is realized from of aqueous emulsified formulations or from solutions of these of that a imilar of is in each instance of If the compounds can be converted to their salt dissolved in water and applied as water he can also be applied as and the The alkali or alkaline earth metal and ammonium salts of the can be prepared by reactio the dione with the desired or ammonium basa addition compounds can be prepared by the addition of the desired nitrogenous base to a solution of the desired pyrido in a inert organic The addition compound can then be lated by standard Suitable bases are cyclic and acyclic amines and The amines can secondary or tertiary aryla or heterocyclic e formed by t pyrido and phenol in a to can also be by the in the same in a nonpolar solvent such as or a mixture of nitromcthane and Acid addition compounds can be prepared by a pyrido viith an appropriate at room in a liquid aromatic hydrocarbon The reaction is Generally any aromatic hydrocarbon can be it ferred that it be liquid between and Benze toluene and xylene are examples of satisfactory The acid addition compounds can be precipitated an excess of liquid paraffin such as heptane or petroleum The product precipitates as a solid or a viscous oil which can be separated by tion or vacuum the product can be separated by vacuum evaporation of the reaction medium at low preferably below Precipitation a is the usual Most acids an ionization constant x pyrido addition Preferred acids are aliphatic acids containing 2 to carbon a phcnylacctic acetic sulfonic organic phosphorJLc acids and inorganic phosphoric acids are because the pyridopyrinidinedionc compounds them are highly phytotoxic and good il preparation of various acid addition compounds the like is described Examples EXAMPLE Preparation of the of with A equipped with a stirrer and heating mantle was charged with 5 and 2 being the reaction mixture as heated to a temperature of It was maintained at for The reaction mixture was then The solid materiel was ground into a of the 2 complex of m with having a g point of Preparation of salt of A flask was and 20 The was allowed to stand for 24 fit which a clear solution of the salt of t EXAMPLE Preparation of the ethylenediamine salt A equipped with dropping and heating mantle was charged with 150 and Agitation was begun the mixture was heated dissolve the components and prepare a saturated The solution cooled to room temperature and then with The reaction mixture was then stirred for 2 hours at room The product which precipitated this time was filtered from the mixture f and The yield was of product of Ε of a of trichloroacetic with A flask equipped with a stirrer was with trichloroacetic and The reaction mixture was stirred for approximately 7 at which time an additional 20 of xylene were The reaction was stirred next 150 of was charged to the reaction with Stirring was continued and an hour later the was filtered and a white solid recovered and The yield was of product having a point of Infrared analysis showed the of ε believed to be the of trichloroacetic acid and EXAMPLE Preparation of the salt of A 100 flask equipped with a and nitrogen atmosphere system was The nitrogen was turned on and silver and water was charged to the A brown thin slurry formed reaction mixture was filtered and the filtrate the The temperature at this point was then to a ton minute reaction turned a l hour later another portion was over a ten Soma failed to After it was by and the filtrate evaporated to residue was dissolved in 10 the it is of invention unexpected properties it shown that compounds display high rate of herbicidai activity while simultaneously demonstrating selectivity with to economic far concerns the amount of herbicide to be of is to considerations as the type of treatment to be the area to the type of weed sought to be controlled and the stage of of the species being treated as well as the particular herbicide centrated herbicidai compositions of the present invention are so as to contain from to about βθ percent the active herbicidai Compositions which are suitable for application generally contain from percent percent ctive herbicidai to have a found to be useful a a aquatic where the is a p ferred for this by way of 1 o d and 5 do 5 py been found to provide one hundred percent kill of duckweed and in concentrations of ten parts per million parts of while cycloheptyl py p has been found to provide one hundred percent kill of these three species in a concentration of five parts per million part of by weight in both insufficientOCRQuality

Claims (1)

1. CLAIMS and oompounde of the formula wherein R and are different and either R is of 2 to 8 carbon cycloalkyl of 5 to carbon alkenyl of up to 8 carbon atoms or alkynyl of up to 8 carbon and is hydrogen or alkyl of 1 to 4 carbon or R is aralkyl than in which the alkyl portion has 1 or 2 carbon atoms and the portion is or phenyl substituted with 1 or 2 or chlorine or a alkyl group having 1 or carbon a homopiperldino or heptamethyleneimino radical or an phenyl or naphthyl optionally ted by nitro or and is hydrogen or an alkyl radical having to 4 oarbo alkali lkaline earth metal or ammonium salts of the oompounde of formula addition of the oompounde of formula Z with genous bases or with phenolic oomplexes of the compounds of formula i Compounds of formula I in which R and are defined in of Claim 1 substantially as described herein with reference to Examples I to Compounds of formula I in which R and are defined in of Claim 1 substantially as described herein with reference to Examples XIII to Alkali alkaline earth metal and ammonium salts the compounds of Claim addition compounds with or with and phenolic complexes of the compounds according to Claim substantially described herein with to Examples to A process for the preparation of compounds of I in Claim 1 in which R is alkyl having from 2 to 8 carbon cycloalkyl having from 3 to 8 carbon alkenyl having up to 8 carbon atoms or alkynyl having up to 8 carbon atoms and is hydrogen or alkyl which comprises reacting a compound of the formula in which has the same meanings as with sodium hypochlorite in the presence sodium hydroxide and a solvent 67 preferably at elevated temperatures thereby a compound of formula I in which is hydrogen and if desired alkylating the latter the A process for the preparation of compounds of formula I in Claim 1 in which is aralkyl than where the alkyl portion has 1 or 2 carbon atoms and the aromatic portion is phenyl or phenyl substituted with 1 or 2 methoxy or chlorine pyridyl substituted alkyl groups having from 1 to 2 carbo or and is hydrogen or which comprises reacting a of formula in Claim 11 in which has the same meanings as above with sodium hypochlorite in the presence of sodium hydroxide and a solvent preferably at elevated tures thereby producing a compound of formula which is hydrogen and if desired alkylating the latter in the A process the preparation of compounds of formula I in Claim in which is a group and is hydrogen or alkyl which comprises reacting of the formula with phosgene to firm the corresponding ethyl nate of the formula reacting this compound with an alkyleneimlne to form the corresponding 68 as an active ingredient a compound of formula I in Claim 1 in which R and are as in of Claim Compositions according to Claim 15 wherein the active ingredient is a compound of any of Claims 2 Compositions fo controlling plant growth containing an active ingredient a compound of formula I in Claim 1 in which R and are as defined in of Claim 969 Compositions to Claim 17 wherei the active is a compound according to Claim 69 Compositions for controlling plant growth containing as active ingredients alkali alkaline earth metal ammonium salts of the compounds of Claim addition compounds or with introgenous bases or with phenolic complexes of the compounds according to Claim Compositions according to Claim 19 wherein the active ingredient is a compound according to Claim A method of controlling plant growth comprising applying to the locus to be protected a composition according to Claim 15 or A method controlling plant growth comprising applying to the locus to be protected a composition according to Claim 17 or method of controlling plant growth comprising applying to the locus to be a eomposition according to Claim 19 or For e Applicants insufficientOCRQuality