POLLEN FORMATION INHIBITING PYRAZOLES

Abstract: Pollen formation in cereal grain plants can be inhibited by application of novel 4-carboxy(or derivative)-1-aryl-5-­ pyrazolecarboxamide. Production of hybrid seed is facili­ tated by use of the compounds.

Description: POLLEN FORMATION INHIBITING PYRAZOLES This invention relates to novel pyrazole derivatives which have been found to be useful in the inhibition of pollen formation. Very important improvements in the hardiness and yield of cultivated plants, particularly grains, have been made by the technique of hybridization. In the past, hybridizing those species, in which each plant produces both pollen and pollen-receiving organs, has been very difficult. Compounds have been found which are capable of inhibiting formation of pollen. The use of such a compound greatly simplifies hybridization. Plants of the two strains to be crossed are simply planted adjacent to one another, as in long, relatively narrow plots, and the plots of one of the strains are treated with a pollen formation inhibitor. All of the seed produced by the treated plants will be hybrid seed, originating from pollen contributed by the untreated plants, if the pollen formation inhibitor is perfectly effective. Compounds having pollen formation inhibiting activity have been taught in U.S. Patent Specification No. 4,345,934, U.S. Patent Specification No. 4,147,528 and U.S. Patent Specification No. 4,238,220. The present invention provides'the pollen formation inhibiting pyrazoles of the formula ( EMI2.1 wherein R, R1 and R2 independently represent halo, C1-C4 alkoxy, C1-C4 alkyl or hydrogen, provided that at least one of R, R and R2 represents hydrogen, and further provided that R2 may represent a group other than hydrogen only when one of R and R1, but not both, represents a group other than hydrogen; R3 represents hydroxy, C1-C4 alkoxy, C2-C4 alkenyloxy-or a phytologically-acceptable moiety forming a salt of the carboxylic acid. One class of compounds of this type which may be mentioned are those wherein R, R1 and R2 represent chloro, bromo, fluoro, C1-C3 alkyl or hydrogen, and R3 represents hydroxy, methoxy, ethoxy, allyloxy or a phytologically-acceptable moiety forming a salt of the carboxylic acid. The invention also provides pollen formation inhibiting compositions which comprise a compound of the above formula and one or more phytologically-acceptable diluents. The invention also provides a method of inhibiting pollen formation in a cereal grain plant which is sensitive to such treatment comprising supplying to the plant at a time prior to anther formation a pollen formation inhibiting amount of a compound of the above formula. Further, the invention provides a method of producing hybrid cereal grain seed having a male and a female parent variety, comprising planting seed of said male and female parent varieties in separate plots adjacent to each other, treating the female parent plants growing from said female parent seed with a pollen formation inhibiting method as just described, said female parent variety being sensitive to such treatment, allowing said treated female parent plants to be pollinated by the male parent plants growing from said male parent seed and to produce hybrid seed, and harvesting said hybrid seed from the treated female parent plants. In this document, all temperatures are described in degrees Celsius. All expressions of percentage, proportion and the like are in weight units unless otherwise stated. In the above formula, the term C1-C4 alkyl includes such groups as methyl, ethyl, propyl, isopropyl, butyl, t-butyl and isobutyl, and the terms C1-C4 alkoxy typically includes those groups linked through an oxygen atom. The salts of the above formula are formed with any phytologically-acceptable moiety capable of forming a salt of the carboxylic acid. The preferred saltforming moieties include alkali metals, amine groups, and quaternary ammonium groups. More particularly, sodium, potassium, lithium, C1-C4 alkylamino, dialkylamino and trialkylamino groups and quaternary ammonium groups wherein the nitrogen atom is substituted with four hydrogen, C1-C4 alkyl, phenyl or benzyl moieties are more highly preferred. For example, quaternary ammonium groups such as ammonium, tetramethyl ammonium, diethyl-dimethyl ammonium, diethyl-dibutyl ammonium, benzyl-trimethyl ammonium, t-butyl-trimethyl ammonium, phenyl-triethyl ammonium, diethyl-dipropyl ammonium, s-butyl-trimethyl ammonium, isobutyl-triethyl ammonium and the like are useful and may be chosen for convenience in the circumstances. Further, such amines as methylamine, butylamine, triethylamine, dipropylamine and the like are convenient for salt formation. -Certain classes of the compounds of the present invention are particularly preferred. One such class includes the carboxylic acids wherein R3 is hydroxy, and salts thereof. Another preferred class includes compounds wherein R1 is a group other than hydrogen, and R and R2 are hydrogen. Another preferred class includes compounds wherein R and R1 independently represent chloro, bromo, methoxy, ethyl or methyl. Still another preferred class includes the compounds wherein R and R2 are hydrogen and R1 is chloro, bromo, fluoro, C1-C2 alkyl or C1-C2 alkoxy; a more preferred class includes such compounds wherein R1 is chloro, ethyl, methyl or methoxy; and another more preferred class includes such compounds wherein R1 is chloro, bromo or methyl. The following group of exemplary compounds of the present invention are mentioned to assure that the reader fully understands the invention. 4-carboxy-l- (3-propylphenyl )-5-pyrazole- carboxamide; l-(4-ethylphenyl)-4-methoxycarbonyl-5pyrazolecarboxamide; 1-(2,4-dibromophenyl)-4-ethoxycarbonyl5-pyrazolecarboxamide; 4-allyloxycarbonyl-l-(2 ,3-difluorophenyl )-5- pyrazolecarboxamide; 4-carboxy-1-(3,4-diethylphenyl)-5-pyrazolecarboxamide, benzyl-trimethylammonium salt: : 4-carboxy-l-(4-isopropyl-2-methylphenyl)-5 pyrazolecarboxamide, phenyl-triethylammonium salt; 4-carboxy-1-(3-isobutylphenyl)-5-pyrazolecarboxamide; 1-(4-butylphenyl)-4-ethoxycarbonyl-5-pyra zolecarboxamide; 1- (3-t-butylphenyl )-4-methoxycarbonyl-5- pyrazolecarboxamide; 4-carboxy-1-[3-(1-methylpropyl)phenyl]-5 pyrazolecarboxamide; 4-carboxy-1-(4-methyl-3-propylphenyl)-5pyrazolecarboxamide, tetrapropylammonium salt; 4-carboxy-1-(3-isopropyl-4-propylphenyl)-5pyrazolecarboxamide, trimethylamine salt; 1- ( 3-bromo-2-chlorophenyl )-4-carboxy-5- pyrazolecarboxamide, diethyl-dipropylammonium salt; 1-(4-bromo-3-propylphenyl)-4-carboxy-5-pyra- zolecarboxamide, diphenyl-dimethylammonium salt; ; 1- (2-bromo-4-methylphenyl )-4-carboxy-5-pyra- zolecarboxamide, benzyl-triethylammonium salt; 1- (3-bromo-4-methylphenyl )-4-carboxy-5- pyrazolecarboxamide; 4-carboxy-1-(4-fluoro-3-methylphenyl)5-pyrazolecarboxamide; 4-carboxy-l-(4-ethyl-2-fluorophenyl)-5- pyrazolecarboxamide, lithium salt; 4-carboxy-l- (3 ,4-difluorophenyl )-5-pyrazole- carboxamide, tetra(isobutyl)ammonium salt; 4-carboxy-l-(2-propyl-4-fluorophenyl )-5-pyra- zolecarboxamide, butyl-trimethylammonium salt; 4-carboxy-1-(3-ethoxyphenyl)-5-pyrazolecarboxamide, sodium salt; 4-methoxycarbonyl-1-(4-propoxyphenyl)-5pyrazolecarboxamide; 1-(3-isopropoxyphenyl)-4-methoxycarbonyl-5pyrazolecarboxamide; and 4-carboxy-l-(3-methoxyphenyl)-5-pyrazole carboxamide, potassium salt. The compounds of the present invention can be prepared by a process whose first step is the reaction of an aryl hydrazine with an alkyl (alkoxymethylene)cyanoacetate to prepare the corresponding l-phenyl-5 amino-lH-4-pyrazolecarboxylate. Next, the aminopyrazole is converted to the corresponding 5-halopyrazolecarboxylate, which is then converted to the 5-cyanopyrazolecarboxylate. That compound is the key intermediate for the preparation of the present pollen formation inhibitors. In the final step of the basic process, the 5-cyano-4-pyrazolecarboxylate is hydrolyzed preferably with a strong base such as potassium hydroxide, to prepare the desired 4-carboxy-5-pyrazolecarboxamide. The reaction scheme is illustrated below. EMI7.1 In the above scheme, the term Alk refers to Cl C4 alkyl groups, and the term Halo refers to chloro or bromo. All of the steps of the processes described in this document proceed in acceptable yields without the use of unusual excess quantities of any reactant. In general, equimolar quantities can be used with satisfactory results. However, as is usual in organic reactions, it is preferable and advisable to use an excess amount of reactants which are inexpensive or easy to obtain, in order to assure full utilization of reactants which are expensive or difficult to obtain. Similarly, the steps of the process may be allowed to proceed for a long period of time, to maximize yield of the desired product, or may be halted before the reaction is complete, to maximize throughput of product from the system. Either manner of operating a process may be preferable, depending on the circumstances. In the first step of the above scheme, it is most preferred to use aqueous acetic acid as the reaction solvent. An inorganic acetate salt in the reaction mixture is also beneficial, in some cases. However, the reaction of the hydrazine with the cyanoacetate may also be carried out in any suitable organic solvent, particularly a lower alkanol such as methanol or ethanol. The preferred reaction temperature is elevated, in the range of about 50-1500. It will be understood that temperatures above the boiling point of the reaction mixture may be used at elevated pressures. However, the reactions will go at any reasonable temperature, such as about 0-2000, if appropriate operating care is used. The halogenation step of the above scheme is preferably carried out with nitrosyl chloride as both the diazotizing and halogenating agent, resulting in a 5-chloropyrazole. It is conventional to use nitrosyl chloride as a gas, by bubbling it through the vigorously mixed reaction mixture. The present chlorination is carried out in any non-reactive organic solvent, most preferably in a halogenated alkane such as chloroform, carbon tetrachloride and the like. Moderate temperatures in the range of 0-50 are preferred, in order to maximize the solubility of nitrosyl chloride in the reaction mixture. 5-Bromopyrazole intermediates are prepared with an alkyl nitrite as the diazotizing agent, and an eppropriate halogen source. Isoamyl nitrite, t-butyl nitrite and the like are appropriate diazotizing agents, and bromoform and elemental bromine are convenient sources of bromine. The reaction conditions are substantially the same as those for chlorinations. Cyanation of the 5-halopyrazole is carried out in a conventional manner with an alkali metal cyanide, such as sodium cyanide, lithium cyanide or potassium cyanide. The cyanation can be done in inert organic solvents of which aprotic solvents are preferred. For example, dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide are particularly preferred solvents in this step. It is preferred to cyanate at elevated temperatures in the range of about 50-2000, most preferably about 80-1400. The hydrolysis step, which prepares the 4-carboxy-5-pyrazolecarboxamide, is most conveniently carried out with potassium hydroxide in aqueous ethanol. Conventionally, the base is dissolved in a minimum amount of water, and added to ethanol to prepare the reaction medium. Other alkali metal hydroxides, such as sodium hydroxide and lithium hydroxide, are also useful for the process. Similarly, other reaction solvents besides aqueous ethanol are useful, particularly other aqueous alkanols such as methanol, propanol and isopropanol. The hydrolysis is preferably carried out at a moderately elevated temperature in the range of about 50-1000, most preferably at the reflux temperature of the reaction mixture. An improved method of preparing certain alkylaryl hydrazines, particularly 3-methyl- and 3-ethylphenylhydrazines, is carried out by reacting the corresponding aniline with sodium nitrite to prepare the diazonium salt, and reacting the salt with potassium sulfite as described in Houben-Weyl, Methoden der Organische Chemie, Via1. 10/2, p. 180 (1967). The preparations below illustrate the preparation of an aryl hydrazine by the process just described. Should one not want to use an alkyl (alkoxymethylene)cyanoacetate in the cyclization, the pyrazole can also be formed by reacting the aryl hydrazine with a dialkyl alkoxymethylenemalonate under basic conditions in an aqueous reaction mixture such as aqueous ethanol. Such a cyclization prepares a pyrazole having a hydroxy group at the 5-position and an alkoxycarbonyl at the 4-position. The next step in such a sequence is to hydrolyze the hydroxypyrazole in an acid environment such as acidic alcohol, which step removes the alkoxycarbonyl group. The resulting intermediate is then reacted with a Vilsmeier reagent to replace the hydroxy group with a chlorine atom, and, simultaneously, to insert a formyl group at the 4-position. The formyl is converted to an alkoxycarbonyl by reaction in an alkanol with hydrogen peroxide in the presence of sulfuric acid. The resulting product is a 5-chloro-4alkoxycarbonylpyrazole, which is converted to the nitrile as described in the basic process discussed above. Salts of the 4-carboxy-5-pyrazolecarboxamides are readily prepared in the usual ways, as by contacting the compound with the appropriate base in an aqueous alkanol or aqueous ketone. When an alkali metal salt is desired, the base can be any appropriate alkali metal hydroxide, alkoxide, carbonate or bicarbonate. When a quaternary ammonium salt is to be made, the appropriate quaternary ammonium halide, sulfonate, hydroxide, methanesulfonate or the like is combined with the acid in a suitable organic solvent. Salts are formed at moderate temperatures in the range of 0-100 . Compounds wherein the 4-carboxy group has been esterified are easily prepared in the usual manner, by reacting the 4-carboxy compound with methanol, allyl alcohol or ethanol in an organic solvent, preferably in the presence of a small amount of a mineral acid as esterification catalyst. Esters are also prepared by reacting an alkali metal salt of the acid with an allyl, methyl or ethyl halide. Moderate temperatures in the range of 50-100 are quite satisfactory, and the reaction times are usually brief. Coupling agents may be used to assist esterifications but are not usually necessary. The following Preparations and Examples are shown further to assist the reader in preparing the compounds of the present invention. Example 1 4-Carboxy-l- (3 -chlorophenyl ) -5-pyrazole- carboxamide. To a 22-liter flask equipped with a heating mantle and condenser were added 2 L. of deionized water, 7.55 L. of acetic acid, 1.37 kg. of sodium acetate, 1.923 kg. of 3-chlorophenylhydrazine hydrochloride, and 1.854 kg. of ethyl (ethoxymethylene)cyanoacetate. The mixture was slowly warmed to the reflux temperature, about 95 , and was stirred at that temperature for 4 hours. The mixture was then cooled to about 10 , adding a little more water to keep it from becoming too thick to stir. The mixture was stirred at about 10 for 1 hour and filtered. The solids were washed with water, and dried by pulling air through the filter cake on a vacuum funnel. The solids were then dissolved in 13 L. of denatured ethanol, and the solution was heated to reflux. It was filtered at elevated temperature, and was then cooled with stirring and filtered to obtain 2.195 kg. of product. The filtrate was concentrated and 170 g. of additional intermediate product was obtained in successive crystallizations, providing in total 2.365 kg. of ethyl 5-amino-l-(3-chlorophenyl)-4-pyrazolecarboxylate. The above intermediate was dissolved in 13 L. of chloroform, and was treated by bubbling nitrosyl chloride through it at ambient temperature. The nitrosyl chloride was generated by slowly adding 1.23 kg. of sodium nitrite in aqueous solution to 7.2 L. of concentrated hydrochloric acid. The addition of the nitrite was controlled so that its addition took 2 hours, and the maximum temperature of the reaction mixture was 35 . The mixture was stirred at ambient temperature for 1 hour after the nitrosyl chloride generation was complete, and then the mixture was heated to reflux and stirred at that temperature for one hour. It was then cooled, stirred overnight, dried with sodium sulfate, and filtered. The solvent was removed under vacuum, and the solids were crystallized from denatured ethanol to obtain 2.002 kg. of ethyl 5-chloro-l-(3-chlorophenyl)4-pyrazolecarboxylate. The above intermediate was dissolved in 13 L. of anhydrous dimethylformamide, and to it was added 686 g. of anhydrous sodium cyanide. The mixture was stirred at 1000 for 4 hours, and then was cooled overnight at ambient temperature with stirring. It was then added in portions with stirring to 40 L. of ice-water. The aqueous mixture was stirred for about 45 minutes and filtered, and the solids were washed several times with water. The solids were then recrystallized from anhydrous ethanol to obtain 1.591 kg. of ethyl 1-(3 chlorophenyl )-5-cyano-4-pyrazolecarboxylate. A 1.445 kg. portion of the above intermediate was added to 14 L. of denatured ethanol and heated to about 50 . To it was added an additional 5 L. of ethanol, 1 L. of water, and 1.035 kg. of 85% potassium hydroxide. The mixture was stirred under reflux (76-77 ) for about 2 hours. It was then let stand overnight, cooling to ambient temperature. The mixture was then reheated to about 700 to dissolve all of the solids, and then 25-30 L. of ice and water were added, and the pH was dropped to 1-2 by the addition of concentrated hydrochloric acid. The mixture was stirred one hour at 100, and was filtered. The solids were washed with water and dried at 500 to obtain 1.024 kg. of the desired product, m.p. 223-225 . Its elemental analysis was as follows. Calculated for: C11H8N3O3C1 Theoretical: C, 49.73; H, 3.04; N, 15.82; Found : C, 49.81; H, .82; N, 15.61. Example 2 4-Carboxy-l-(3-fluorophenyl)-5-pyrazole- carboxamide. A 5.5 g. portion of ethyl 5-cyano-l-(3-fluorophenyl)-4-pyrazolecarboxylate and 4.7 g. of potassium hydroxide were dissolved in 100 ml. of ethanol at the reflux temperature and the mixture was stirred at that temperature for 2 hours. The mixture was then diluted to 350 ml. with cold water, and was heated slightly to obtain a solution which was made acid with concentrated hydrochloric acid. The product was precipitated by adding small amounts of ice, and the precipitated product was then collected by filtration and crystallized from ethanol-water to obtain 3.6 g. of the desired product, m.p. 215-2160, having the following elemental analysis. Calculated for: C11H8N3O3F Theoretical: C, 53.01; H, 3.21; N, 16.87; Found : C, 53.16; H, 3.27; N, 16.91. Example 3 4-Carboxy-l-phenyl-5-pyrazolecarboxamide. A 4 g. portion of ethyl 5-cyano-l-phenyl-4pyrazolecarboxylate was reacted with 2 g. of potassium hydroxide in 60 ml. of denatured ethanol substantially as described in Example 2, to obtain 2.7 g. of the desired product, m.p. 234-235 , having the following elemental analysis. Calculated for: C11H9N303. Theoretical: C, 57.14; H, 3.92; N, 18.17; Found : C, 57.38; H, 3.93; N, 18.37. Example 4 4-Carboxy-l-(4-chlorophenyl)-5-pyrazole- carboxamide. The process of Example 2 was followed, starting with 3.7 g. of ethyl l-(4-chlorophenyl)-5-cyano-4pyrazolecarboxylate and 2 g. of sodium hydroxide in 60 ml. of denatured ethanol and 60 ml. of water to obtain 2.3 g. of the desired product, m.p. 249-250 . The elemental analysis was as follows. Calculated for: C11H8N303C1 Theoretical: C, 49.73; H, 3.04; N, 15.82; Found : C, 49.94; H, 3.32; N, 15.78. Example 5 4-Carboxy-1-(2,4-dichlorophenyl)-5-pyriazolecarboxamide. A 2.5 g. portion of ethyl l-(2,4-dichlorophenyl)-5-cyano-4-pyrazolecarboxylate was reacted with 1 g. of potassium hydroxide in 60 ml. of 50% aqueous ethanol to obtain 1.2 g. of purified product, m.p. 239-2400, with the following elemental analysis. Calculated for: C11H7N3 O3C12 Theoretical: C, 44.03; H, 2.35; N, 14.01; Found : C, 44.05; H, 2.64; N, 13.83. Example 6 1- (4-Bromophenyl )-4-carboxy-5-pyrazolecarbox- amide. A 3.5 g. portion of ethyl l-(4-bromophenyl)5-cyano-4-pyrazolecarboxylate was reacted with 2.15 g. of potassium hydroxide in 50 ml. of ethanol under reflux for 2 hours to obtain 2.45 g. of the desired product, m.p. 251-252.5". The elemental analysis was as follows. Calculated for: C11H8N3 0 3Br Theoretical: C, 42.61; H, 2.60; N, 13.55; Found : C, 42.84; H, 2.72; N, 13.29. Example 7 4-Carboxy-l- (3 , 4-dichlorophenyl ) -5-pyrazole- carboxamide. Fifteen g. of ethyl l-(3,4-dichlorophenyl)-5cyano-4-pyrazolecarboxylate was dissolved in 200 ml. of ethanol, and 5.6 g. of potassium hydroxide was added. The reaction mixture was stirred under reflux for 1 hour, and was then poured over a large amount of ice and made acid with concentrated hydrochloric acid. The mixture was filtered, and the solids were found by nuclear magnetic resonance analysis to consist of the partially hydrolyzed 4-carboxy-5-cyanopyrazole. A 2 g. portion of that intermediate was held out for further examination, and the rest of the solids were redissolved in 200 ml. of ethanol and stirred under reflux for 18 hours with 5.6 g. of potassium hydroxide. The mixture was then poured over ice, made acid, and filtered. The solids were recrystallized from ethanol, and the mother liquor was chromatographed over a silica gel column with methanol as the eluent. The product-containing fractions were evaporated to dryness and the residues were recrystallized from methanol to obtain the desired product, m.p. 249-250 . The elemental analysis was as follows. Calculated for: C11 H7N3 03012 Theoretical: C, 44.03; H, 2.35; N, 14.00; Found : C, 43.93; H, 2.37; N, 13.91. Example 8 4-Carboxy-l- (4-methylphenyl )-5-pyrazolecarbox- amide. To 10 g. of ethyl 5-cyano-1-(4-methylphenyl)4-pyrazolecarboxylate was added 5.6 g. of potassium hydroxide and 200 ml. of water followed by enough water to cause solution. The mixture was stirred under reflux for 8 hours and allowed to stand for 3 days. It was then poured over ice, made acid and filtered. The solids from the filtration were heated in 100 ml. of ethyl acetate, and the undissolved solid was separated, dried and identified as 4.25 g. of the desired product, m.p. 260 dec. The product was identified by nuclear magnetic resonance analysis in DMSOd6. 62.36 (s,3), methyl; 7.32 (d,2), aromatic; 7.45 (d,2), aromatic; 8.01 (s,l), pyrazole; 7.91 (s,l), carboxamide; 8.33 (s,l), carboxamide. Example 9 1- (3-Bromophenyl )-4-carboxy-5-pyrazolecarbox- amide. A 14 g. portion of ethyl l-(3-bromophenyl)5-cyano-4-pyrazolecarboxylate was hydrolyzed by stirring under reflux in 200 ml. of ethanol with 6 g. of potassium hydroxide for 2 hours. The mixture was then poured over ice, acidified and filtered, and the solids were crystallized from ethanol/water and dried at 1680 to obtain 10 g. of the desired product, m.p. 215-217 dec. The product was identified by NMR analysis in CDCl3/DMSOd6. 67.06 (s,l), carboxamide; 7.30-7.64 (m,4), aromatic; 8.08 (s,l), pyrazole; 9.10 (s,l), carboxamide. Example 10 4-Carboxy-l-(3-methylphenyl )-5-pyrazolecarbox- amide. A 9 g. portion of ethyl 5-cyano-l-(3-methylphenyl)-4-pyrazolecarboxylate was dissolved in 200 ml. of ethanol, and 5.8 g. of potassium hydroxide was added. The mixture was stirred under reflux for 4 hours, and then was cooled, diluted with water and made acid. The mixture was filtered, and the solids were washed with ethyl acetate as shown above in Example 8 to obtain 3.8 g. of the desired product, m.p. 209-211 dec. It was identified by elemental analysis. Calculated for: C12HllN303 Theoretical: C, 58.77; H, 4.52; N, 17.13; Found : C, 58.58; H, 4.63; N, 16.85. Example 11 4-Carboxy-l- (4-fluorophenyl )-5-pyrazolecarbox- amide. A 2.5 g. portion of ethyl 5-cyano-l-(4-fluoro- phenyl)-4-pyrazolecarboxylate was combined with 2.6 g. of potassium hydroxide and stirred under reflux in 100 ml. of denatured ethanol for 4 hours It was then cooled, made acid, diluted with water, and concentrated under vacuum to obtain 2.8 g. of the desired compound, m.p. 2320 dec. after recrystallization from acetone. It was identified by elemental analysis. Calculated for: CllH8N303F Theoretical: C, 53.02; H, 3.24; N, 16.86; Found : C, 53.27; H, 3.02; m, 16.69. Example 12 4-Carboxy-1-(2,3-dichlorophenyl)-5-pyrazole- carboxamide. A 15 g. portion of ethyl l-(2,3-dichlorophenyl)-5-cyano-4-pyrazolecarboxylate was stirred under reflux overnight in 200 ml. of ethanol with 6 g. of potassium hydroxide. The reaction mixture was chromatographed over silica gel, and the product-containing fractions were combined and evaporated to dryness. The residues were recrystallized from ethanol-water to obtain 1.31 g. of the desired product, m.p. 228-230 , which was identified by elemental analysis. Calculated for: CllH7N303Cl2 Theoretical: C, 44.03; H, 2.35; N, 14.00; Found : C, 44.04; H, 2.39; N, 13.88. Example 13 4-Carboxy-1-(3-chloro-4-methylphenyl)-5-pyra- zolecarboxamide. A 9.5 g. portion of ethyl 1-(3-chloro-4 methylphenyl )-5-cyano-4-pyrazolecarboxylate was dissolved in 250 ml. of ethanol, and 2 g. of potassium hydroxide was added. The mixture was then stirred under reflux for 30 minutes. One hundred ml. of water was added, and the mixture was stirred under reflux for an additional 4 hours. Isolation of the product was attempted, but it was found to be a difficultly separable mixture, and the entire reaction mixture was returned to the flask, redissolved in aqueous ethanol and refluxed for 1 hour on the steam bath with 6 g. of additional potassium hydroxide. The mixture was then diluted with aqueous acetic acid and filtered, and the solids were dried and identified as 5.2 g. of the desired product, m.p. 228-232 dec. It was identified by elemental analysis. Calculated for: C12HloN303Cl Theoretical: C, 51.53; H, 3.60; N, 15.02; Found : C, 51.80; H, 3.36; N, 14.92. Example 14 Methyl 5-aminocarbonyl-l-(3-chlorophenyl)-4pyrazolecarboxylate. A 2.2 g. portion of 4-carboxy-l-(3-chlorophenyl)-5-pyrazolecarboxamide was suspended in 40 ml. of methanol, and hydrogen chloride was bubbled through the mixture for about 1 minute. The mixture was then stirred under reflux for 2 hours, poured into ice-water, and made basic with dilute aqueous sodium hydroxide. The mixture was filtered, and the solids were dried and crystallized from toluene to obtain 1.7 g. of the desired product, m.p. 191-1920. The elemental analysis was as follows. Calculated for: C12HloN303Cl Theoretical: C, 51.53; H, 3.60; N, 15.02; Found : C, 51.23; H, 3.71; N, 14.83. Example 15 Allyl 5-aminocarbonyl-l-(3-chlorophenyl)-4pyrazolecarboxylate. A 3.33 g. portion of 4-carboxy-l-(3-chlorophenyl)-5-pyrazolecarboxamide was slurried in 35 ml. of methanol, and 0.68 g. of sodium methoxide was added. The methanol was removed under vacuum to leave the sodium salt of the starting compound. That salt was combined with 1.26 g. of triethylamine and 1.51 g. of allyl bromide in 35 ml. of toluene, and the mixture was stirred under reflux overnight. The mixture was then poured into 150 ml. of ice-water, made basic with saturated sodium bicarbonate solution and extracted with 150 ml. of ethyl acetate. The organic layer was washed with brine, dried and evaporated under vacuum to obtain a solid, which was recrystallized from toluene to obtain 1.48 g. of purified product, m.p. 132-133 . Its elemental analysis was as follows. Calculated for: C14Hl2N303Cl Theoretical: C, 55.00; H, 3.96; N, 13.74; Found : C, 55.15; H, 3.96; N, 13.70. Example 16 Ethyl 5-aminocarbonyl-l-(3-chlorophenyl)-4pyrazolecarboxylate. A 2.5 g. portion of 4-carboxy-l-(3-chlorophenyl)-5-pyrazolecarboxamide was suspended in 50 ml. of absolute ethanol, made acid, and esterified and isolated as described in Example 14 above. The product was 1.64 g. of the desired product, m.p. 1320, and its elemental analysis was as follows. Calculated for: C13Hl2N303 Theoretical: C, 53.16; H, 4.12; N, 14.31; Found : C, 53.37; H, 4.04; N, 14.61. Example 17 Methyl 5-aminocarbonyl-l- (3-methylphenyl )-4- pyrazolecarboxylate. Hydrogen chloride gas was bubbled for 1 minute into a suspension of 3 g. of 4-carboxy-l-(3-methy1- phenyl)-5-pyrazolecarboxamide in 30 ml. of methanol. The mixture was then stirred under reflux for 2 hours and was cooled overnight. It was then poured into 150 ml. of ice and water and made basic with dilute sodium hydroxide. The precipitate was recovered by filtration, dried and recrystallized from toluene, treating with charcoal, to obtain 1.16 g of the desired product, m.p. 167-168 . It analysis was as follows. Calculated for: C13Hl3N303 Theoretical: C, 60.23; H, 5.05; N, 16.21; Found : C, 60.18; H, 4.99; n, 16.08. Example 18 4-Carboxy-1-(3-methylphenyl)-5-pyrazole- carboxamide, sodium salt. Three g. of 4-carboxy-l-(3-methylphenyl )-5- pyrazolecarboxamide was slurried in 30 ml. of methanol, and 0.66 g. of sodium methoxide was added. The mixture was stirred briefly, and was filtered and evaporated to dryness. The residue was dissolved in methanol, treated with charcoal, and recrystallized. The product was very hygroscopic and was dried for 8 hours at 100D before analysis. Calculated for: C12H10N3 O3Na Theoretical: C, 53.94; H, 3.77; N, 15.72; Found : C, 54.11; H, 3.73; N, 15.52. Example 19 4-Carboxy-l-(3-chlorophenyl)-5-pyrazole- carboxamide, sodium salt. A 6.14 g. portion of 4-carboxy-l-(3-chlorophenyl)-5-pyrazolecarboxamide was slurried in 60 ml. of methanol, and 1.25 g. of sodium methoxide was added. The mixture was stirred for a few minutes, and was then filtered. The filtrate was evaporated to dryness under vacuum, and the residue was dissolved in 50 ml. of methanol and crystallized by the addition of diethyl ether. The solids were collected by filtration and identified after drying as 4.55 g. of the desired salt, m.p. 274-276 . Its elemental analysis was as follows. Calculated for: C11H7N3 O3ClNa Theoretical: C, 45.93; H, 2.45; N, 14.61; Found : C, 46.10; H, 2.26; N, 14.58. Example 20 4-Carboxy-l-(3-chlorophenyl)-5-pyrazole- carboxamide, potassium salt. A 4.25 g. portion of 4-carboxy-l-(3-chlorophenyl)-5-pyrazolecarboxamide was slurried in 40 ml. of absolute ethanol with 1.03 g. of 85% potassium hydrox ide, and the mixture was heated to the reflux temperature. A little water was added to the refluxing mixture to obtain complete solution, and it was then allowed to cool to ambient temperature. Finally, it was chilled in the refrigerator and filtered to obtain 3.32 g. of the desired product, m.p. above 300O dec. The elemental analysis, calculated for C11H7N3O3ClK, was as follows. Theoretical: C, 43.50; B, 2,32; N, 13.83; Found : C, 43.26; H, 2.09; N, 13.5 Example 21 4-Carboxy-l- (3-chlorophenyl )-5-pyrazole- carboxamide, isopropylamine salt. A 4.25 g. portion of 4-carboxy-l-(3-chlorophenyl)-5-pyrazolecarboxamide and 1.42 g. of isopropylamine were added to 50 ml. of absolute ethanol and stirred for a few minutes. The mixture was then evaporated to dryness and recrystallized from methanoldiethyl ether to obtain 4.4 g. of the desired product, m.p. 157-164". The elemental analysis, calculated for C14H 14N4 O3Cl, was as follows. Theoretical: C, 52.10; H, 4.68; N, 17.36; Found : C, 52.16; H, 4.77; N, 17.19. Example 22 4-Carboxy-1-(3-chlorophenyl)-5-pyrazole- carboxamide, tetrabutylammonium salt. A 3.26 g. portion of 4-carboxy-l-(3-chlorophenyl)-5-pyrazolecarboxamide was slurried in 50 ml. of methanol and 12 ml. of 1M tetrabutyl ammonium hydroxide solution was added. The mixture was stirred for 30 minutes, and evaporated to dryness under vacuum to obtain 5.2 g. of product, m.p. 1;0-1210. The product was identified by elemental analysis. Calculated for: C27H43N403C1 Theoretical: N, 11.05; Found : N, 11.07. Example 23 4-Carboxy-l- (3 , 4-dimethylphenyl )- 5-pyrazole- carboxamide. A 2.5 g. portion of ethyl 5-cyano-1-(3,4dimethylphenyl)-4-pyrazolecarboxylate was hydrolysed in 50 ml. of ethanol and 12 ml. of water with 1.3 g. of potassium hydroxide under reflux for 2 hours. The mixture was then cooled and poured into 300 ml. of water. The aqueous mixture was filtered, made acid with concentrated hydrochloric acid, and filtered. The solids were dried and recrystallized from ethanol/water to obtain 1.62 g. of the desired product, m.p. 231232.50. Its elemental analysis was as follows: Calculated for: C13H13N3 O3 Theoretical: C, 60.23; H, 5.05; N, 16.21; Found : C, 60.47; H, 4.94; N, 16.05. Preparation 1 Ethyl 5-chloro-l- (3-methylphenyl )-4-pyrazole- carboxylate. A 38.5 g. portion of 3-methylphenylhydrazine hydrochloride and 52.4 g. of diethyl ethoxymethylenemalonate were slurried in 250 ml. of ethanol, and to the mixture was added 46 g. of 50% aqueous sodium hydroxide and 250 ml. of water. The temperature was controlled at 370 with an ice bath. The mixture was then stirred overnight at ambient temperature, and the ethanol was removed under vacuum. The resulting suspen sion was cooled and the salt was removed by filtration. The solids were washed with two 200 ml. portions of dichloromethane, and were then heated to 500 in 1 liter of water. The mixture was made acid to pH 1 with hydrochloric acid, and was stirred overnight at ambient temperature. The solids were filtered out and dried to obtain 57.4 g. of ethyl 5-hydroxy-l-(3-methylphenyl)- 4-pyrazolecarboxylate, m.p. 85-86 .5. A 54.4 g. portion of the above product was added to 100 ml. of butanol and 200 ml. of concentrated hydrochloric acid, and the mixture was heated to reflux. Heating was continued until the disappearance of the carboxylate was indicated by thin layer chromatography. The butanol was then removed under vacuum to obtain 43.4 g. of 5-hydroxy-l-(3-methylphenyl )pyrazole hydrochloride, m.p. 136-140 . A 40.4 g. portion of phosphorus oxychloride was cooled to 100 under nitrogen, and to it was slowly added 8.9 g. of dimethylformamide. The mixture was stirred for 30 minutes at ambient temperature, and to it was added in small portions 21.4 g. of the above intermediate. The mixture was then heated to 50 for a time, and then was held for 18 hours at 1000. Fifty ml. of ethanol was added to the cooled mixture, and it was then poured into 500 ml. of ice-water. The aqueous mixture was extracted three times with 250 ml. portions of ethyl acetate, and the combined organic layers were washed with brine, dried and evaporated to obtain 23.5 g. of oil. The oil was dissolved in toluene and crystallized by addition of petroleum ether to obtain 16.5 g. of 5-chloro-l-(3-methylphenyl)-4-pyrazolecar- boxaldehyde, m.p. 54-570. Five and four-tenths g. of 50% hydrogen peroxide was added dropwise to 17.2 g. of concentrated sulfuric acid at 150, and the mixture was stirred at ambient temperature for 2 hours. It was added dropwise to a 5 solution of 4.4 g. of the above intermediate pyrazole in 41.4 ml. of ethanol, while the temperature was held below 150. After the addition, the mixture was cooled to 5 and stirred for 30 minutes. It was then allowed to warm slowly to ambient temperature overnight, and was then diluted with 50 ml. of water. It was extracted with ethyl acetate, and the organic layer was dried and evaporated under vacuum to obtain 4.6 g. of ethyl 5-chloro-l-(3-methylphenyl)-4-pyrazolecarboxylate. Example 24 4-Carboxy-1- ( 3-ethylphenyl ) -5-pyrazolecarbox- amide. A 60.6 g. portion of 3-ethylaniline was added to 132 g. of concentrated hydrochloric acid and 67 g. of ice at 00, and an additional 67 g. of ice was added and the mixture was cooled to 0 again. To it was added 36.3 g. of sodium nitrite dissolved in 75 ml. of water, dropwise over a period of 1 hour while the temperature was held below 60. At the same time, a solution of potassium sulfite was prepared by bubbling sulfur dioxide through a solution of 163.8 g. of potassium hydroxide in 750 ml. of water. The sulfur dioxide addition was continued to a pH of 4.7. Then 67 g. of ice was added and the solution was cooled to 00. The two preparations were mixed together as rapidly as possible, while the temperature increased to 80. The mixture was then heated on a steam bath to 700 and stirred at that temperature for 1 hour. It was then cooled to 00, and the precipitate was separated by filtration and dried. The solids were recrystallized from a large amount of ethanol to obtain 70.9 g. of potassium 3-ethylphenylhydrazine sulfonate, m.p. dec. greater than 1950. A 15.0 g. portion of the above intermediate was stirred in 150 ml. of water and 75 ml. of hydrochloric acid with a small amount of charcoal at 800, and the mixture was filtered while hot. The filtrate was cooled to ambient temperature overnight, and precipitation began immediately upon swirling the solution. The solids were separated by filtration and dried to obtain 5.5 g. of 3-ethylphenylhydrazine hydrochloride, m.p. 147-157 . A 10.7 g. portion of the above intermediate, obtained from successive reactions, was combined with 10.5 g. of ethyl (ethoxymethylene)cyanoacetate and 10.2 g. of sodium acetate in 100 ml. of ethanol, and the mixture was stirred under reflux for about 20 hours. The mixture was then poured slowly into 400 ml. of icewater with good agitation, and the solids were separated by filtration and dried. The solids were recrystallized from aqueous ethanol to obtain 12.7 g. of ethyl 5-aminol-(3-ethylphenyl)-4-pyrazolecarboxylate, m.p. 79-79.5 . A 10.2 g. portion of the above intermediate was dissolved in the minimum amount of chloroform, and hydrogen chloride gas was bubbled through the solution for 1 minute at ambient temperature. Then nitrosyl chloride gas was bubbled through it for 20 minutes while the temperature was held in the range 20-350 with an ice bath. The mixture was then heated on a steam bath to drive off excess nitrosyl chloride, and it was dried through phase separation paper and the organic portion was evaporated under vacuum. The residue was purified by high performance liquid chromatography, eluting with 1,2-dichloroethane. The product-containing fractions were combined and evaporated under vacuum to obtain 2.9 g. of ethyl 5-chloro-l-(3-ethylphenyl)-4-pyrazolecarboxylate, an oil. An 8.9 g. portion of the above intermediate, obtained by successive reactions, was combined with 35 ml. of dimethylformamide and 3.4 g. of sodium cyanide, and the mixture was heated for 6 hours at about 1000. It was then cooled, a small amount of additional sodium cyanide was added, and the mixture was heated at 1000 for 2 hours more. It was then cooled, and poured into 300 ml. of ice-water. The mixture was extracted with 300 ml. of diethyl ether, and the organic layer was dried and evaporated to obtain 7.9 g. of oily product which was purified by high performance liquid chromatography, eluting with 1,2-dichloroethane. Evaporation of the product-containing fractions gave 6.1 g. of ethyl 5-cyano-l- (3-ethylphenyl )-4-pyrazolecarboxylate, an oil. A 2.5 g. portion of the above intermediate was added to 25 ml. of ethanol containing 1.6 g. of potassium hydroxide, and the mixture was heated at the reflux temperature for 20 minutes. Five ml. of water was added, the mixture was heated under reflux for 1.5 hours, and it was then poured into 100 ml. of water. The mixture was made acid with concentrated hydrochloric acid, and was chilled overnight and filtered to obtain 2.0 g. of the desired product, m.p. 176-177.5 . Its elemental analysis was as follows. Calculated for: C13H13N3 O3 Theoretical: C, 60.23; H, 5.05; N, 16.21; Found : C, 60.03; H, 4.83; N, 15.93. Example 25 4-Carboxy-l-(3-methoxyphenyl )-5-pyrazolecar- boxamide. A 34.9 g. portion of 3-methoxyphenylhydrazine hydrochloride was added to 300 ml. of acetic acid, 100 ml. of water, 36 g. of sodium acetate and 37.2 g. of ethyl (ethoxymethylene)cyanoacetate. The mixture was heated overnight on a steam bath, and was then cooled and poured into 1 liter of ice-water with vigorous agitation. The mixture was filtered, and the solids were air-dried and recrystallized from aqueous ethanol with charcoal to obtain 27.4 g. of ethyl 5-amino-l-(3-methoxyphenyl )-4-pyrazolecarboxylate, m.p. 66-67 . A 13.3 g. portion of the above intermediate was dissolved in 80 ml. of bromoform and the mixture was cooled to 5 . To it was added 10.5 g. of t-butyl nitrite, dropwise, and the mixture was then allowed to warm to ambient temperature and was heated on a steam bath for 15 minutes. It was then evaporated under vacuum to obtain 21.1 g. of dark oil, which was dissolved in ethyl acetate. The solution was washed with 1N hydrochloric acid, with water, with saturated sodium bicarbonate, and with brine, and was then dried and evaporated under vacuum to obtain a dark oil, which was purified by high performance liquid chromatography, eluting with 1:3 ethyl acetate:hexane, to obtain 10.6 g. of ethyl 5-bromo-l-(3-methoxyphenyl )-4-pyrazolecarboxylate, m.p. 77-79 . A 3.6 g. portion of the above intermediate was combined with 1.2 g. of sodium cyanide in 20 ml. of dimethylformamide, and the mixture was heated for 10 hours at 1000. An additional 0.3 g. of sodium cyanide was added, and the mixture was heated overnight at 1000 and was poured into 100 ml. of ice-water. The precipitate was separated by filtration and dried, and was recrystal-lized from ethanol with charcoal to obtain 1.0 g. of ethyl 5-cyano-1-(3-methoxyphenyl)-4-pyrazolecarboxylate, m.p. 84-85 . An 0.95 g. portion of the above intermediate was added to 25 ml. of ethanol and 0.6 g. of potassium hydroxide, and the mixture was heated to reflux. Ten ml. of water was added, and the mixture was heated under reflux for 1.5 hours. It was then cooled and filtered, and the filtrate was poured into 100 ml. of water. The aqueous mixture was made acid with concentrated hydrochloric acid, and was vigorously stirred and then chilled overnight. The precipitate was separated by filtration and dried, and was then recrystallized from aqueous ethanol to obtain 0.4 g. of the desired product, m.p. 213-216 . Its elemental analysis was as follows. Calculated for: C12H11N3O4. Theoretical: C, 55.17; H, 4.24; N, 16.08; Found : C, 55.12; H, 3.99; N, 15.83. The compounds of the present invention have been carefully tested to demonstrate their activity in inhibiting the formation of pollen. The results of those tests are shown below. Test 1 The experiment recorded here was a field experiment carried out in central Indiana, U.S.A. The experiment was started by planting strips of Auburn and Beau wheat in the autumn. Some strips were planted on October 4, and others on October 14. The field was fertilized at the time of planting with a combination of fertilizers appropriate for the growth of wheat. Adjacent the strips of Auburn and Beau wheat were planted pollen-shedding plots of mixed Caldwell, Auburn and Titan wheat in the ratio 1:1:2. The pollen-shedding plots were planted on October 1 at the rate of 100 lb. of seed per acre. The test compound in this experiment was that of Example 1 above. The compound was formulated for application in 1:1 by volume acetone:denatured alcohol. The organic solution was diluted in water, containing 0.25% of polysorbate 20 for application. All applications were at the volume rate of 500 gallons per acre, and were applied as a foliar spray to the test plots. The first application of compound was made on April 26 following the planting of the wheat. Where multiple applications of compound were made, the later applications were at intervals of one week. The test plots were laid out in the bands of Auburn and Beau wheat, which became the female plots for the production of hybrid wheat, pollinated by the pollen-shedding plots of wheat. Each test plot was 4 rows x 13 ft. in size. At the time of wheat head emergence, some heads in each treated plot were bagged with small-grain pollinator glassine bags. Five heads in each row of each test plot were bagged. When the seed was formed, the number of seeds per head in the bagged plants provided a measure of the extent to which pollen formation was inhibited, because those seed could have been formed only by self-pollination. The number of seeds per head in unbagged plants in each test plot was also counted, as was the number of seeds per head in untreated control plots. Two plots were treated according to each treatment regime and the results are averaged in the table below. The data are reported separately below for each variety of wheat and each planting date. The earlier-planted plots are described as "age 1", and the later as "age 2". The columns headed "fertility" report the number of seeds per head of the treated bagged plants, as percentage of untreated controls, and therefore give a direct measurement of pollen formation. The columns headed "hybrid" report the difference between the number of seeds per head of treated unbagged plants and seeds per head of treated bagged plants, as percentage of untreated controls. Thus, that column reports the amount of hybrid seed produced, compared to the seed produced by untreated control plants. The purity of the hybrid seed produced may be estimated by comparing the "fertility" percentage with the "hybrid" percentage. Table 1 Age 1 Age 2 Rate Appl'ns Auburn Beau Auburn Beau Fertility Hybrid Fertility Hybrid Fertility Hybrid Fertility Hybrid 1 (1b/A) 1 90% 12% 73% 26% 100% 0% 98% 5 1 2 39 41 65 13 52 45 83 10 1 3 4 73 23 51 4 71 44 40 3 1 12 79 20 58 51 34 35 50 3 2 0 92 7 63 0 78 24 63 3 3 0 57 0 49 1 75 0 74 5 1 20 58 27 46 2 79 37 45 5 2 0 40 0 22 0 56 4 56 5 3 0 33 1 47 0 55 0 59 10 1 0 70 0 55 0 73 1 78 10 2 0 33 0 32 0 59 0 49 10 3 0 3 0 6 0 8 0 41 15 1 0 27 0 29 0 44 0 54 15 2 0 19 0 35 0 54 0 44 15 3 0 4 1 1 0 16 0 16 Additional plots in the same block of Auburn and Beau wheat plots were treated once, on either May 4 or May 10, following planting of the wheat in October. The results of these experiments are shown in the table below. Table 2 Age 1 Age 2 Rate Appl'ns Auburn Beau Auburn Beau Fertility Hybrid Fertility Hybrid Fertility Hybrid Fertility Hybrid 1 (1b/A) May 4 95 2 86 6 104 8 99 2 3 May 4 30 57 48 33 20 73 74 18 5 May 4 9 62 28 45 37 49 34 38 10 May 4 5 72 32 39 14 68 15 50 15 May 4 0 53 6 53 0 55 14 53 1 May 10 67 22 85 0 29 65 77 9 3 May 10 17 60 63 6 14 76 59 35 5 May 10 12 58 54 18 13 82 35 40 10 May 10 0 67 23 37 0 86 3 79 15 May 10 0 26 2 30 3 56 0 49 Test 2 The compound of Example 1 was applied to 61 varieties of wheat. Each test plot consisted of three 2-ft. hand-planted rows, with 2-ft. spaces between the groups of three. The plots were planted in central Indiana on October 5. On the following May 5, two of the three replicates were sprayed with the compound of Example 1 at 5 ib. per acre and 10 ib. per acre, and the third replicate provided an untreated control. Plants were bagged, and the seed set of bagged, unbagged and untreated plants were counted as described in Test 1. Pollen for these experiments was provided by bands of the same pollen-shedding mixture of wheat described in Test 1. The data from this group of experiments are reported below in summary form, as the number of the wheat varieties which exhibited fertility of the bagged treated plants in various ranges, compared to the fertility of untreated control plants. Table 3 Fertility 5 lbs./Acre 10 lbs./Acre < 10% 6 16 10-29% 4 9 30-49% 10 14 50-69% 10 9 70-89% 14 6 more than 89% 16 7 Test 3 A standardized greenhouse test was used to evaluate the compounds of the present invention. The test was begun by planting Waldron wheat in 4 inch pots, 4 seeds per pot, in a sterilized sand/loam soil. The wheat was allowed to grow in a favorable greenhouse environment, and the plants were treated 3 times with a test compound. The first application was about 22 days after the seed was planted, and the second and third applications were about 3 and about 10 days after the first. Each compound was formulated for testing by dissolving the proper amount for two replicates and three applications, depending on the concentration to be tested, in 5 ml. of 1:1 by volume acetone:denatured alcohol, containing 10% by volume of polysorbate 20. Compounds which did not dissolve were finely dispersed in the solvent. The organic mixture was then diluted to 30 ml. with deionized water at about ambient temperature, and the aqueous dispersion was evenly sprayed over the foliage of two pots of wheat. Untreated control plants were provided in each experiment. The results of experiments are reported below as the number of spike lets produced by the treated plants, and the number of seed per spikelet. The average number of spike lets per normal plant is about 15, and the number of seed per spikelet varies in the range of about 1.5 to 2.5. In the tables below, the results of replicate experiments have been averaged. When the results of an experiment were not different from the results of the contemporaneous untreated controls, the inactivity is indicated merely by "N". Table 4 1500 ppm concentration Compound of Example No. Spikelets Seed/Spikelet 1 15.2 0.17 1 15.7 0.28 1 13.0 0 2 N 3 14.6 0.35 4 15.7 0.11 5 13.3 0 6 14.6 0.13 7 14.2 0.40 8 15.7 0.64 9 16.0 0.44 10 14.7 0.24 11 16.0 0.73 14 15.0 0.67 15 16.1 0.53 16 14.8 0.47 19 14.8 0.19 20 15.2 0.33 21 15.1 0.12 Table 5 1200 ppm concentration Compound of Example No. Spikelets Seed/Spikelet 1 10.6 0 1 11.7 0.22 2 N 5 13.5 0.01 Table 6 1000 ppm concentration Compound of Example No. Spikelets Seed/Spikelet 1 9.0 0 1 9.4 0 1 12.0 0.16 1 11.2 0.27 1 N 1 N 1 N 1 12.9 0 1 13.8 0 1 13.5 0.50 1 12.3 0.41 1 13.6 0.68 1 13.7 0.84 1 15.3 1.28 1 12.7 0.89 1 15.5 0.81 1 15.6 0.69 1 14.0 0.15 1 15.3 0.08 Table 6 (continued) Compound of Example No. Spikelets Seed/Spikelet 1 15.0 0.98 1 14.3 1.10 1 16.0 0.48 1 16.7 0.32 1 15.8 0.38 1 15.8 0.34 1 16.7 0.54 1 16.7 0.32 1 15.7 1.92 1 15.5 0.68 1 14.7 0.26 1 15.8 1.22 2 9.2 0.12 2 N 3 10.9 0.14 3 N 4 N 5 13.2 0.13 5 12.9 0.23 6 N 7 N 7 15.4 0.57 8 12.0 0 8 12.5 0.63 9 N 9 14.3 1.68 10 15.0 0.95 14 11.7 0.06 14 10.5 0.65 Table 6 (continued) Compound of Example No. Spikelets Seed/Spikelet 14 14.0 0.70 15 N 16 12.3 0.45 16 14.8 1.60 16 15.5 0.93 19 13.5 0.25 19 15.7 0.09 20 17.0 0.32 20 14.3 0.07 21 14.0 0.25 21 16.0 1.30 Table 7 800 ppm concentration Compound of Example No. Spikelets Seed/Spikelet 1 9.8 0.05 1 12.8 0.04 1 12.0 0.26 1 N 1 N 1 11.5 0.75 1 14.0 1.02 1 14.3 1.27 1 15.3 1.01 1 14.0 0.42 1 14.7 0.19 1 15.5 0.92 1 14.3 0.68 Table 7 (continued) Compound of Example No. Spikelets Seed/Spikelet 1 15.7 1.67 1 16.0 1.02 1 14.0 0.07 1 15.9 0.79 5 13.0 0.09 7 14.2 0.80 8 14.0 0.42 9 16.0 1.92 10 15.7 1.06 14 12.0 0.31 14 15.5 1.47 16 14.8 1.26 19 13.3 0.23 20 15.0 0.07 21 15.0 0.95 Table 8 600 ppm concentration Compound of Example No. Spikelets Seed/Spikelet 1 9.0 0.39 1 11.2 0.64 1 N 1 N 1 N 1 12.3 1.01 1 14.5 1.93 1 13.7 1.88 1 14.8 0.99 1 13.8 0.42 1 14.0 0.27 1 14.8 0.62 1 14.8 1.48 1 14.5 1.65 1 15.8 1.25 1 14.7 0.50 1 16.0 0.67 2 N 3 N 5 13.3 0.33 5 N 7 N 7 15.6 0.77 8 13.3 0.36 8 14.0 0.49 9 15.0 1.87 10 15.3 1.90 14 N Table 8 (continued) Compound of Example No. Spikelets Seed/Spikelet 14 15.8 0.94 16 14.8 1.09 16 15.5 0.93 19 14.5 0.32 20 16.0 0.53 21 15.3 0.94 Table 9 400 ppm concentration Compound of Example No. Spikelets Seed/Spikelet 1 N 1 N 1 11.7 .1.61 1 12.7 1.18 1 14.0 1.55 1 14.0 1.54 1 16.5 0.69 1 14.3 0.65 1 14.8 0.15 1 15.0 1.03 1 15.0 1.31 1 N 1 N 1 14.3 0.44 1 N 7 15.2 1.72 8 13.3 1.55 Table 9 (continued) Compound of Example No. Spikelets Seed/Spikelet 9 N 10 N 14 N 14 N 16 N 19 14.5 0.37 20 15.3 0.63 21 16.0 1.81 Table 10 300 ppm concentration Compound of Example No. Spikelets Seed/Spikelet 1 8.5 0.26 3 N 5 N 7 N Table 11 200 ppm concentration Compound of Example No. Spikelets Seed/Spikelet 1 N 1 N 1 13.0 1.10 1 13.5 1.65 1 13.8 1.66 1 14.3 1.86 1 14.3 1.29 Table 11 (continued) Compound of Example No. Spikelets Seed/Spikelet 1 14.0 0.56 1 14.3 1.42 1 14.0 1.88 1 N 1 N 1 15.0 1.08 1 N 7 N 8 13.8 1.71 9 N 10 N 14 N 14 N 16 N 19 15.3 0.12 20 16.0 1.21 21 14.3 2.01 Table 12 100 ppm concentration Compound of Example No. Spikelets Seed/Spikelet 1 9.5 1.21 1 N 1 11.7 1.79 1 10.9 1.79 1 13.5 1.78 1 14.5 1.97 1 14.0 1.77 1 14.5 0.66 1 14.3 1.60 1 14.3 1.92 1 N 1 N 3 N 5 N 7 N 7 N 8 N 8 13.0 1.81 9 N 10 N 14 N 14 N 16 N 19 15.0 1.47 20 15.5 1.36 21 14.7 1.97 Test 4 This test was carried out substantially according to the method described in Test 3 above, except that the compounds were applied only twice, at an interval of 4 days. In other respects, the test method and the method of reporting data were the same. Table 13 Compound of Concentration Seed/ Example No. ppm. Spikelets Spikelet 1 1000 13.4 0 1 1000 13.7 0.58 1 800 11.2 0 1 800 14.2 1.05 1 800 10.0 0 1 600 13.6 0 1 600 11.0 0.91 1 600 N 1 600 9.0 0.02 1 300 13.3 0.07 1 300 N 1 100 N 1 100 N Test 5 The test method of Test 4 was applied again, but in this case the interval between the two applications of compound was 6 days. Table 14 Compound of Concentration Seed/ Example No. ppm. Spikelets Spikelet 1 1500 12.2 0.57 1 1000 N 1 1000 14.5 0.03 1 1000 N 1 1000 14.2 1.04 1 1000 N 1 1000 10.7 0.06 1 1000 12.3 0.89 1 1000 13.0 0.23 1 800 15.2 0.80 1 800 11.7 0.07 1 800 N 1 800 N 1 800 N 1 800 N 1 800 N 1 800 12.7 0.18 1 600 13.3 0.03 1 600 15.3 1.41 1 600 13.0 0.81 1 600 N 1 600 N 1 600 N 1 600 N 1 600 10.8 0.26 1 600 12.5 0.06 1 400 N 1 400 13.3 0.80 1 400 11.8 0.17 Table 14 (continued) Compound of Concentration Seed/ Example No. ppm. Spikelets Spikelet 1 400 N 1 400 N 1 400 N 1 400 N 1 400 11.7 0.31 1 300 N 1 200 N 1 200 12.0 0.50 1 200 N 1 200 N 1 200 N 1 200 N 1 200 N 1 100 N 1 100 N 1 100 N 1 100 N 1 100 N 1 100 N 1 100 N 1 100 N 10 1500 12.7 0.01 10 1000 12.3 0.03 10 1000 12.6 0.03 10 1000 12.8 0.08 10 1000 14.2 0 10 1000 N 10 1000 12.0 0.46 10 1000 13.0 0.85 Table 14 (continued) Compound of Concentration Seed/ Example No. ppm. Spikelets Spikelet 10 1000 12.0 0.25 10 800 N 10 800 N 10 800 12.0 0.89 10 800 13.0 0.69 10 800 13.7 0.42 10 800 13.8 0.12 10 800 12.9 0.05 10 800 13.8 0 10 600 11.7 0 10 600 14.5 0.09 10 600 13.7 0.18 10 600 14.2 0.18 10 600 11.0 0.73 10 600 13.0 0.81 10 600 N 10 600 12.0 0.63 10 400 10.7 0.94 10 400 12.0 0.67 10 400 N 10 400 N 10 400 12.0 0.18 10 400 15.5 0.03 10 400 13.3 0.30 10 300 13.2 0.14 10 200 13.6 0.28 10 200 14.0 0.20 10 200 14.2 0.01 10 200 N Table 14 (continued) Compound of Concentration Seed/ Example No. ppm. Spikelets Spikelet 10 200 N 10 200 N 10 200 N 10 100 N 10 100 N 10 100 N 10 100 N 10 100 16.7 0.54 10 100 12.2 0.30 10 100 12.3 1.10 10 100 12.4 1.58 11 1000 N 11 800 -N 11 600 N 11 400 N 11 200 N 11 100 N 12 1500 16.0 0.50 12 1000 N 12 800 N 12 600 N 12 400 N 12 200 N 13 1500 14.7 0.20 13 1500 14.8 0.41 13 1000 12.0 0.42 13 1000 11.6 0.56 13 800 14.7 0.45 Table 14 (continued) Compound of Concentration Seed/ Example No. ppm. Spikelets Spikelet 13 800 12.7 0.27 13 600 N 13 600 N 13 400 N 13 300 N 13 200 N 13 100 N 23 1500 14.7 0.05 23 1500 12.8 0.07 23 1000 13.2 0.10 23 1000 N 23 800 12.8 0.16 23 600 N 23 600 13.8 0.26 23 300 N 23 300 13.2 0.24 23 100 N 23 100 N 24 1000 12.0 0 24 600 13.0 0 24 400 11.7 0 24 200 12.8 0.12 24 100 12.0 0.81 25 400 13.1 0.04 25 300 14.1 0.12 25 200 14.0 0.19 25 100 15.6 1.18 25 50 N 25 25 N The preferred compounds of the present invention, which are also the preferred compounds for the practice of the present pollen formation-inhibiting methods, are 4-carboxy-l- ( 3-chlorophenyl ) -5-pyrazole- carboxamide, 4-carboxy-l-(3-methylphenyl )-5-pyrazole- carboxamide, 4-carboxy-l- (3-ethylphenyl )-5-pyrazole- carboxamide, 4-carboxy-l- (3 ,4-dichlorophenyl ) -5- pyrazolecarboxamide, and 4-carboxy-l- (3-methoxyphenyl )- 5-pyrazolecarboxamide. The alkali metal salts, ammonium salts and mono, di and tri(C1-C4 alkyl)amine salts of the compounds just named are also preferred compounds of the invention. The compounds of this invention are useful for inhibiting pollen formation in cereal grain plants which are sensitive to such treatment, and the compositions in which the compounds are formulated for application, and the methods by which the compounds are applied to obtain the inhibition of pollen formation, constitute embodiments of the invention. A compound must be supplied to the plant before the formation of anthers. It must be noted that the head of a plant matures over a period of time, and different plants in a field mature at different times. Accordingly, a compound must be supplied before anther formation in the most mature plants in the field to be treated, if best results are to be obtained. In wheat and barley, anther formation occurs while the plant's head is still near ground level, and is about 2 mm. long, and the plant has about 4 to 5 true leaves. Thus, it is advisable to dissect representative plants from time to time to determine when development of the head, and therefore of the anthers, is approaching. Best results are obtained by supplying the compound when the head is only a few mm. long. Comparable indications of development in other species are used to determine the proper time for treatment. The compound must be supplied, not merely applied, to the plant before anther formation. In this document, the term "supplying is used to mean administering the compound in such a manner that it is absorbed by the plant and is available to the target organs. In all cases, the compound must be applied sufficiently early that it is absorbed and supplied to the plant before anther formation. In the practice of the present invention, it is necessary to apply an effective amount of a compound of the invention to the plant or the soil in which it grows. Effective amounts can be measured in terms of the concentration of the compound in a dispersion, when the compound is applied to the foliage, or, preferably, can be measured in terms of the amount of compound applied per unit area of land. The concentration of the compound is a useful measurement, because the amount of compound applied to foliage is limited by the amount of the dispersion which is retained by the foliage. That amount is substantially constant, for a given size of plant, and therefore the amount of compound applied by that means can be increased only by increasing the concentration of the dispersion. Depending on the circumstances, effective concentrations of compounds range from about 100 to about 2000 parts per million by weight. Factors which affect the effective amount include the succulence of the foliage, the rate at which it is growing, and the weather at the time of application. In general, preferred concentrations for foliar applications are in the range from about 500 to about 1500 parts per million by weight. Measurement of the amount of compound applied as a dose per unit area of land may be used for either application to the soil or application to the foliage. Of course, it will be understood that application to the foliage results in some soil application in all cases, since not all of the composition applied to the foliage adheres there. In general, rates of from about 1 to about 40 pounds of compound per acre of crop land are useful. It is more preferred to use rates from about 1 to about 20 pounds per acre, most preferably, from about 1 to about 10 pounds per acre of the most preferred compounds. It has been observed that application of the compound in multiple doses provides better effectiveness, and there is some indication that a smaller total amount of compound can effectively be used when applied in multiple doses. It may be that the result is explained by the fact that not all plants form anthers at the same time, and multiple applications avoid the necessity for compounds to be stored for a long period in the plant or soil. Application of a compound from 2 to 4 times, at intervals of 3 to 10 days, is preferred. More particularly, application of a compound of the invention from 2 to 3 times, where each application is of from about 1/2 to about 3 pounds of compound per acre, applied to the foliage, is particularly preferred. Further, application of the compound from 2 to 3 times, where each application is of a dispersion containing from about 200 to about 1000 parts per million by weight of compound, and the dispersion is applied so as to cover the foliage of the plants, is also preferred. Another particularly preferred method of application of a compound of the invention is application to the soil in which the plants grow at a rate of from about 1 to about 10 pounds of compound per acre, applied once. The plants to which a compound of the present invention may be applied to inhibit pollen formation are the cereal grain plants, including wheat, barley, corn, oats, rye, rice, sorghum and triticale. A preferred group of species include wheat, barley, rye and triticale. The more preferred species of plants are wheat and barley, and the most preferred species is wheat. More particularly, the plants to which the invention is applied are defined as those which are sensitive to such treatment; that is, those in which the compounds will inhibit pollen formation when properly applied. The plants are defined in that manner because considerable variation in activity between varieties, and between individuals within a variety, has been observed. In barley, for example, some varieties require several times as much compound for activity as do other varieties. On the other hand, the varietal difference in activity in wheat is relatively small. In other species, of which corn is a particularly good example, the differences in sensitivity to the compounds are more subtle than varietal differences. In corn, individual sensitive plants have been observed, although no variety wherein all plants are sensitive has been found. It is therefore necessary, in such a species, to screen for sensitive plants, and to use the seed produced by those plants to create a variety of sensitive plants for further use in hybridization. Of course, some experimentation is needed to use the present invention properly, particularly in species such as corn. The experimentation, however, is well understood and routinely carried out by plant breeders. The nature of the tests is clearly shown above in the test portion of this document, and so the skilled reader can readily plan routine experiments which will identify sensitive plants or varieties and determine the proper application rate of a compound, by the ordinary skills of the art, and the teaching in this document. A further aspect of the present invention is the production of hybrid seed by use of the present pollen formation inhibiting method. Seed of the varieties which will be the male and female parents is planted in separate but adjacent plots. The female parent variety, of course, must be sensitive to the treatment of the present invention. The size and location of the plots may be important. Some species, such as wheat and barley, do not produce great quantities of pollen, as corn does, and so the pollen cannot be expected to travel very far and still fertilize a high percentage of the female plants. Therefore, the female plots should be relatively narrow. For example, the female and male parent seed may usefully be planted in long alternate plots, only a few rows wide, with their long axes oriented across the prevailing wind. It has been observed to be advantageous to plant the female parent variety seed densely enough to inhibit the plants from developing tillers. The reason is that tillers develop later than the main plants, and therefore their presence confuses the determination of the proper time to apply the compound. At the proper time, as discussed above in detail, the compound is applied to the female parent plots to inhibit those plants from producing pollen. Those plants are then pollinated by the male parent plants and produce hybrid seed, which is harvested in the usual ways. The compositions in which a compound of the present invention may be formulated are of many types. Since the compounds are effective when applied both to the foliage of the plants, and to the soil in which the plants grow, substantially all of the physical types of agricultural chemical compositions may be used. Most economical and preferred compositions are concentrated water-emulsifiable or water-dispersable compositions. Such compositions include, in general, emulsifiable concentrates, suspension concentrates and wettable powders and granules, all of which are common in the agricultural chemical art. Some discussion of them will be provided, however, to assure complete understanding. The concentration of a compound in a concentrated composition is entirely irrelevant to the use of the compound. Such compositions are diluted in water for application, and the application rate of the compound is determined by the ratio at which the composition is diluted in water, or by the amount of the composition which is applied per area of crop land. Thus, any desired application rate can be obtained from any concentrated composition. Such compositions will typically contain from about 1 to about 95 percent of the active ingredient. Emulsifiable concentrates of the compounds comprise a convenient concentration of the compound dissolved in a phytologically-acceptable diluent which is a mixture of water-miscible organic solvent and emulsifiers. Useful- organic solvents, in general, include aromatics, especially xylenes, and the petroleum fractions, especially the napthalenic and olefinic portions of petroleum, such as those called heavy aromatic naphthas. Terpenic solvents including rosin derivatives, and complex alcohols such as 2-ethoxyethanol are also often used, and amides such as dimethylacetamide may be particularly useful with the present compounds. Suitable emulsifiers for emulsifiable concentrates, generally used in amounts in the range of from about 1% to about 10% by weight of the concentrate, are frequently found among the alkylbenzenesulfonates, the alkyl sulfates, the non-ionics such as ethylene oxide adducts of alkyl phenol, and especially among the metal and amine salts of alkyl sulfates. Wettable powders comprise an intimate mixture of the compound and a phytologically-acceptable diluent made up of an inert carrier and surfactants. The inept carrier is usually chosen from among easily water di spers able powdery substances such as attapulgite clay, the montmorillonite clays, the diatomaceous earths and the purified silicates. Surfactants for wettable powders are found among the same types just mentioned for emulsifiable concentrates, as well as the sulfonated lignins and the naphthalenesulfonates. It is possible to compact a wettable powder into granular form, and thereby to produce a wettable granule, which has the advantage of being non-dusty and easy to measure and pour. When added to water, a properly formulated wettable granular product will disperse and become a fine suspension. The compounds may also be formulated as suspensions, which consist of a relatively high concentration, in the interest of economy, of the compound in finely powdered form, dispersed and suspended in a phytologically-acceptable aqueous diluent. A surfactant system for a suspension product is much like that used in a wettable powder, but it must be capable of maintaining the compound in dispersed form over a long period of time. It is sometimes advisable to adjust the density of the liquid, as by dissolving an inert salt in it, in order to assist in the suspension of the relatively dense particles of compound. When an aqueous dispersion of a compound, prepared by the dilution of a concentrated composition, is to be applied to foliage, an adjuvant is often used to improve the ability of the dispersion to wet and adhere to the foliage. Such adjuvants as vegetable gums, emulsified polybutenes, cationic and other surfactants and lignin derivatives are often used. The use of an adjuvant in aqueous dispersions of the present compounds is highly preferred, and regularly improves results. Not only the commercial adjuvants, which are commonly known to growers, but also ordinary surfactants, are beneficially used, at concentrations in the range of a few tenths of a percent in the dispersion. Agueous dispersions of concentrated compositions may be applied either to foliage or to the soil in which plants grow. When the application is to be to the soil, a granular composition can also be effectively used. A granular agricultural composition consists of the compound, applied1 usually in a relatively low concentration such as from about 1 to about 10% by weight, to a granular carrier having a convenient particle size for application. Typically, the particle size range is from 20 to 60 mesh, on the standard U.S. sieve size scale. Such carriers as clay, sand, pulverized stone, corncob grits and the like are frequently used and may be chosen for convenience and economy. It is usually unnecessary to use any adjuvant or other ingredient other than the compound and the carrier, with perhaps a small amount of solvent in which the compound is applied to the carrier. The carrier may also be supplied in powdered form, and formulated by mixing the powdered carrier with the powdered compound and then compacting the mixture and granulating it to the desired particle size range. The following specific examples of formulations of compounds of the present invention are provided to assist the reader. It will be understood that the following formulations, all of which were used in the tests described above in the specification, are merely exemplary of the manners of formulating the compounds. An agricultural chemist, using the following formulations as guides, can readily prepare any desired type of formulation, using any of the compounds of the invention as the active ingredient. Formulation 1 0.4% Granules compound of Example 1 0.4% 30/60 mesh attapulgite 99.6% Formulation 2 1% Granules compound of Example 1 1.03% 30/60 mesh attapulgite 98.97% Formulation 3 1.2% Granules compound of Example 1 1.24% 30/60 mesh attapulgite 98.76% Formulation 4 2% Granules compound of Example 1 2.06% 30/60 mesh attapulgite 97.94% Formulation 5 3% Granules compound of Example 1 3.09% 30/60 mesh attapulgite 96.91% Formulation 6 4% Granules compound of Example 1 4.12% 30/60 mesh attapulgite 95.88% Formulation 7 5% Granules compound of Example 1 5.15% 30/60 mesh attapulgite 94.85% Formulation 8 6% Granules compound of Example 1 6.19% 30/60 mesh attapulgite 93.81% Formulation 9 10% Granules compound of Example 1 10.31% 30/60 mesh attapulgite 89.69% Formulation 10 15% Granules compound of Example 1 15.46% 30/60 mesh attapulgite 84.54% Formulation 11 0.5% Granules compound of Example 10 0.52% 30/60 mesh attapulgite 99.48% Formulation 12 1.5% Granules compound of Example 10 1.55% 30/60 mesh attapulgite 98.45% Formulation 13 2.5% Granules compound of Example 10 2.58% 30/60 mesh attapulgite 97.42% Formulation 14 3.75% Granules compound of Example 10 3.75% 30/60 mesh attapulgite 96.132 All of formulations 1-14 were prepared by dissolving the compound in an appropriate amount of dimethylformamide and impregnating the carrier with the solution. The solvent was then evaporated, at high temperature if necessary. Formulation 15 1 lb./gal. Suspension compound of Example 10 12.1% Pluronic P-104 (non-ionic 1.0% surfactant) silicone antifoam 0.2% propylene glycol 6.0% magnesium aluminum silicate 1.0% xanthan gum 0.1% water 79.6% The compound was ground with the P-104, the anti foam and part of the water in an attrition mill for 45 minutes, and was then mixed with the rest of the ingre2ients. Formulation 16 25% Wettable Powder compound of Example 10 26.9% sodium salt of lignin with anionic wetting agents 10.0% purified silica 10.0% kaolin clay 53.1% The above ingredients were thoroughly mixed, and the mixture was then milled through a hammermill and then through an air impact mill. Formulation 17 0.5 lb./gal. Suspension compound of Example 10 6.2% Tergitol TMN-6 (non-ionic surfactant) 5.0% purified silica 0.5% silicone antifoam 0.1% 2% xanthan gum 5.0% water 83.2% The compound was ground with part of the water, the silica and the anti foam in an attrition mill until 50% of the particles were smaller than 1 micron by microscopic inspection, and the suspension was then mixed with the rest of the ingredients. Formulation 18 1 lb./gal. Suspension compound of Example 10 12.1% Tergitol TMN-6 1.0% Polyfon H (lignin sulfonate salt) 2.0% 5% magnesium aluminum silicate suspension 20.0% 2% xanthan gum suspension 5.0% silicone antifoam 0.2% water 59.7% The compound was ground in an attrition mill with the Tergitol, the Polyfon and part of the water, and was then mixed with the rest of the ingredients. Formulation 19 1 lb./gal. Suspension compound of Example 10 12.1% Tergitol TMN-6 1.0% Polyfon H 2.0% 5% magnesium aluminum silicate suspension 20.0% 2% xanthan gum suspension 5.0% propylene glycol 6.0% silicone antifoam 0.2% water 53.7% The compound was ground in an attrition mill with the Tergitol, the Polyfon and part of the water, and was then mixed with the rest of the ingredients. Formulation 20 1 lb./gal. Suspension compound of Example 10 12.1% Makon 12 (non-ionic surfactant) 1.0% 5% magnesium aluminum silicate suspension 20.0% 2% xanthan gum suspension 5.0% silicone anti foam 0.2% water 61.7% The compound was ground in an attrition mill with the Makon, the anti foam and part of the water and was then mixed with the rest of the ingredients. Formulation 21 1 lb./gal. Suspension compound of Example 10 12.1% Makon 12 1.0% propylene glycol 6.0% 5% magnesium aluminum silicate suspension 20.0% 2% xanthan gum suspension 5.0% silicone antifoam 0.2% water 55.7% The compound was ground in an attrition mill with the Makon, the anti foam and part of the water, and was then mixed with the rest of the ingredients. Formulation 22 1 lb./gal. Suspension compound of Example 10 12.1% Pluronic P-104 1.0% 5% magnesium aluminum silicate suspension 20.0% 2% xanthan gum suspension 5.0% silicone antifoam 0.2% water 61.7% The compound was ground in an attrition mill with the Pluronic, the anti foam and part of the water, and was then mixed with the rest of the ingredients. Formulation 23 1 lb./gal. Suspension compound of Example 10 12.1% Pluronic P-104 1.0% 5% magnesium aluminum silicate suspension 20.0% 2% xanthan gum suspension 5.0% silicone antifoam 0.2% propylene glycol 6.0% water 55.7% The compound was ground in an attrition mill with the Pluronic, the antifoam and part of the water, and was then mixed with the rest of the ingredients. Formulation 24 1 lb./gal. Suspension compound of Example 1 12.1% Makon 12 5.0% propylene glycol 6.0% magnesium aluminum silicate 1.0% xanthan gum suspension 0.1% silicone antifoam 0.2% water 75.6% The compound was ground with the Makon, the anti foam and part of the water, and was then mixed with the rest of the ingredients. Formulation 25 1 lb./gal. Suspension compound of Example 10 12.1% Makon 12 10.0% propylene glycol 6.0% magnesium aluminum silicate 1.0% xanthan gum suspension 0.1% silicone antifoam 0.2% water 70.6% The compound was ground in an attrition mill with half of the Makon, the anti foam and part of the water, and was then mixed with the rest of the ingredients. Formulation 26 1 lb./gal. Suspension compound of Example 1 12.2% Tergitol TMN-6 10.0% purified silica 1.0% 2% xanthan gum suspension 10.0% silicone antifoam 0.2% Polyfon H 0.3% water 66.3% The compound was ground in an attrition mill with the silica, the Tergitol and part of the water until the size of 50% of the particles was smaller than 1.9 microns by Coulter Counter. The ground suspension was then mixed with the rest of the ingredients. Formulation 27 25% wettable powder compound of Example 1 25.8% sodium salt of lignin plus anionic wetting agents 10.0% purified silica 10.0% kaolin clay 54.2 The mixture was ground through a laboratorysize air impact mill until the size of 50% of the particles was smaller than 4.1 microns by Coulter Counter. Formulation 28 5% Suspension compound of Example 1 5.0% sodium napthaleneformaldehyde condensate 3.0% 30% formaldehyde 0.4% xanthan gum 0.4% propylene glycol 5.0% water 86.2% The mixture was ground until the average particle size was 3 microns. Formulation 29 5% Suspension This formulation was identical to that of Formulation 28, except that the mixture was ground only until the average particle size was 6 microns. Formulation 30 5% Granules compound of Example 1 5.0% 25/50 mesh attapulgite 95.0% Formulation 31 5% Granules compound of Example 1 5.0% dye 1.0% 25/50 mesh attapulgite 94.0% Formulation 32 5% Granules compound of Example 1 5.0% sand 95.0% All of Formulations 30-32 were prepared by dissolving the compound in N-methylpyrrolidone, mixing the appropriate amount of the solution with the carrier, and evaporating the solvent.

Claims: CLAIMS 1. A compound of formula (I) EMI79.1 wherein R, R1 and R2 independently represent halo, C1-C4 alkoxy, C1-C4 alkyl or hydrogen, provided that at least one of R, R1 and R2 represents hydrogen, and further provided that R2 may represent a group other than hydrogen only when one of R and R1, but not both, represents a group other than hydrogen; R3 represents hydroxy, C1-C4 alkoxy, C2 -C4 alkenyloxy or a phytologically-acceptable moiety forming a salt of the carboxylic acid. 2. A compound of formula (1) as claimed in Claim 1, wherein R, R1 and R2 independently represent chloro, bromo, fluoro, C1-C3 alkyl or hydrogen, and R3 represents methoxy, ethoxy, allyloxy or a phytologically-acceptable moiety forming a salt of the carboxylic acid. 3. A compound of formula (I) as claimed in claim 1 or 2 wherein R3 represents hydroxy or a phytologically-acceptable moiety forming a salt of the carboxylic acid. 4. A compound of formula (I) as claimed in any one of claims 1 to 3, wherein R and R2 represent hydrogen, and R1is other than hydrogen. 5. 4-Carboxy-l-(3-chlorophenyl)-5-pyrazole- carboxamide or a salt thereof. 6. 4-Carboxy-1-(3-methylphenyl)-5-pyrazole- carboxamide or a salt thereof. 7. A pollen formation inhibiting composition comprising one or more phytologically-acceptable diluents and a compound of formula (I) as claimed in any one of claims 1 to 6. 8. A method of inhibiting pollen formation in a cereal grain plant which is sensitive to such treatment comprising supplying to the plant at a time prior to anther formation a pollen formation inhibiting amount of a compound of formula (I) as claimed in any one of claims 1 to 6. 9. A method of producing hybrid cereal grain seed having a male and a female parent variety, comprising planting seed of said male and female parent varieties in separate plots adjacent to each other, treating the female parent plants growing from said female parent seed with a pollen formation inhibiting method of Claim 8, said female parent variety being sensitive to said treatment, allowing said treated female parent plants to be pollinated by the male parent plants growing from said male parent seed and to produce hybrid seed, and harvesting said hybrid seed from the treated female parent plants. 10. A process for preparing a compound of formula (I) as claimed in any one of claims 1 to 6 which comprises hydrolyzing a nitrile of formula: EMI81.1 where R, R1 and R2 are as defined in claim 1, so as to prepare a compound of formula (I) in which R3 is hydroxy, optionally followed, if necessary, by appropriate salification or esterification so as to provide a compound of formula (I) in which R3 is not hydroxy. CLAIMS 1. A pollen formation inhibiting composition which comprises as an active ingredient a compound of formula (I) EMI82.1 wherein R, R1 and R2 independently represent halo, C1-C4 alkoxy, C1-C4 alkyl or hydrogen, provided that at least one of R, R1 and R2 represents hydrogen, and further provided that R2 may represent a group other than hydrogen only when one of R and R1, but not both, represents a group other than hydrogen; R3 represents hydroxy, C1-C4 alkoxy, C2-C4 alkenyloxy or a phytologically-acceptable moiety forming a salt of the carboxylic acid; associated with one or more phytologically-acceptable diluents therefor. 2. A pollen formation inhibiting composition as claimed in Claim 1, wherein r, R1 and R2 independently represent chloro, bromo, fluoro, C1 -C3 alkyl or hydrogen, and R3 represents methoxy, ethoxy, allyloxy or a phytologically-acceptable moiety forming a salt of the carboxylic acid. 3. A pollen formation inhibiting composition as claimed in claim 1 or 2 wherein R3 represents hydroxy or a phytologically-acceptable moiety forming a salt of the carboxylic acid. 4. A pollen formation inhibiting composition as claimed in any one of claims 1 to 3, wherein R and R2 represent hydrogen, and R1 is other than hydrogen. 5. A pollen formation inhibiting composition which comprises as an active ingredient 4-carboxy-l (3-chlorophenyl)-5-pyrazolecarboxamide or a salt thereof. 6. A pollen formation inhibiting composition which comprises as an active ingredient 4-carboxy-l- (3-methylphenyl)-5-pyrazolecarboxamide or a salt thereof. 7. A method of inhibiting pollen formation in a cereal grain plant which is sensitive to such treatment comprising supplying to the plant at a time prior to anther formation a pollen formation inhibiting amount of a compound of formula (I) as defined in any one of claims 1 to 6. 8. A method of producing hybrid cereal grain seed having a male and a female parent variety, comprising planting seed of said male and female parent varieties in separate plots adjacent to each other, treating the female parent plants growing from said female parent seed with a pollen formation inhibiting method of Claim 7, said female parent variety being sensitive to said treatment, allowing said treated female parent plants to be pollinated by the male parent plants growing from said male parent seed and to produce hybrid seed, and harvesting said hybrid seed from the treated female parent plants. 9. A process for preparing a compound of formula (I) as defined in any one of claims 1 to 6 which comprises hydrolyzing a nitrile of formula: EMI84.1 where R, R1 and R2 are as defined in claim 1, so as to prepare a compound of formula (I) in which R3 is hydroxy, optionally followed, if necessary, by appropriate salification or esterification so as to provide a compound of formula (I) in which R3 is not hydroxy.

Inventors: BECK, JAMES RICHARD, PRICE, CAROLE WENDELLYNN
Applicants: ELI LILLY AND COMPANY
Application year: 1985
Main classification: C07D231
IPC codes: A01H1, A01P21, A01H3, A01N43, C07D231