NZ204997A

NZ204997A - Plant growth stimulating compositions containing ions chain alkyl carboxylic acid derivatives

Info

Publication number: NZ204997A
Application number: NZ204997A
Authority: NZ
Inventors: A J Welebir
Original assignee: Biochemical Marketing Corp
Priority date: 1982-07-30
Filing date: 1983-07-22
Publication date: 1986-04-11
Also published as: KR840005315A; KR850000866B1; IT1163848B; TR21737A; IT8322222A0; AR240124A1

Description

<div class="application article clearfix" id="description"> 204997 *y -4 Priority Date(s): . 7.. U. SP Complete Specification Filed: <2?. .7 Class: tn/$7j.93j. C&J... G'f&9/ QP. p" tt'i'MiW" Publication Date: V> P.O. Journa\, No: .'$%> t ^2juLlVHi V- &l VfO NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION PLANT GROWTH STIMULATORS COMPRISING METAL IONS AND LONG-CHAIN ALKYL CARBOXYLIC ACIDS AND SALTS AND DERIVATIVES THEREOF A, J, P, & s, J. Lj fcj/ We, BIOCHEMICAL MARKETING CORPORATION, of 3506 N. Nottingham J) it" JO/7/c?M Street / Arlington, Virginia U.S.A., ^ lk^ Kfag u-u ■ W ^ hereby declare the invention for which k/ we pray that a patent may be granted to ccre/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- - 1 - (followed by page la) 204997 la DESCRIPTION PLANT GROWTH STIMULATORS COMPRISING METAL IONS AND LONG-CHAIN ALKYL CARBOXYLIC ACIDS AND SALTS AND DERIVATIVES THEREOF TECHNICAL FIELD The present inventions relates to chemical compositions which, when applied to growing plant life or seeds thereof, are effective in the growth of said plant life. More particularly, the invention relates to chemical compositions containing long-chain carboxylic acids and salts and derivatives thereof in combination with metal ions which are useful in stimulating plant growth. DISCLOSURE OF THE INVENTION In recent years, long-chain carboxylic acids and their derivatives and salts have become recognized as plant growth regulating agents, however, the practical utility of these compounds has been restricted as herbicidal agents, or chemical agents that otherwise inhibit plant growth. The present inventor has discovered, most surprisingly, that combining long-chain carboxylic acids having about 12 or more carbon atoms with metal ions having a valence of +2 or more, or salts, esters, or other derivatives of said carboxylic 2 204997 acids with said metal Ions, produces formulations that are highly effective In stimulating the growth of plant life and In Improving crop yields In the field. Furthermore, the compositions of the Invention may be combined with other agricultural products and plant growth regulators or fertilizers In order to alter their effect on plant life and lower the cost of application of applying each Individually. Accordingly, It Is an object of the present Invention to provide an Inexpensive and effective moans of Increasing the growth of plants and Increasing the yields of crops In the field, or at least to provide the public with a useful choice. Pursuant to the present Invention, there are provided Inexpensive, simple, and safe methods and compositions of long-chain carboxylic acids, and salts and derivatives thereof, with metal Ions, which are useful for stimulating the growth of plant life and Increasing the yields of crops In the field. Accordingly, In one aspect the Invention consists In a plant growth stimulator composition, comprising: at least one compound of the formula: wherein R Is a long-chain alkyl group having at least 12 carbon atoms, preferably between 15 and 47 carbon atoms and more preferably between 17 and 35 carbon atoms, containing between 0 and 6 carbon-carbon double bonds and between 0 and 4 carboxyl groups or salts or derivatives thereof; and R' Is a long-chain alkyl group having between 1 and 36 carbon atoms, preferably 1 to 30 carbon atoms, and more preferably 1 to 24 carbon atoms, containing 0 to 6 carbon-carbon double bonds, and 0 to 4 carboxyl groups or salts or derivatives thereof; or R' Is hydrogen, Including salts thereof; and R - COOR1 (1) " v * 3 204997 at least one metal Ion salt which releases In water a metal Ion having a valence of +2 or +3, wherein the ratio of said compound of the formula R-C00R' to said metal salt Is In the range of from 1:5 to 1:500,000,000 by weight. In a further aspect, the Invention consists In an aqueous plant growth stimulator formulation suitable for application to growing plants, comprising: water; less than 10 mg per liter of at least one long-chain compound of the formula: wherein R Is a long-chain alkyl group having between 15 and 47 carbon atoms, containing between 0 and 6 carbon-carbon double bonds, 0 to 4 carboxyl groups or salts or derivatives thereof; and R' Is a long-chain alkyl group having between 1 and 36 carbon atoms, containing 0 to 6 carbon-carbon double bonds, 0 to 4 carboxyl groups or salts or derivatives thereof; or R' Is hydrogen, Including salts thereof; and at least one metal Ion salt which releases In water a metal Ion having a valence of +2 or +3, wherein the weight ratio of the said compound of the formula R-COOR' to said metal salt Is In the range of from 1:5 to 1:500,000,000. Preferably said long-chain compound of the formula R-C00R' Is present In the amount of at least 0.001 mg per litre. In still a further aspect, the Invention consists In a method for stimulating plant growth which comprises: applying an effective plant growth stimulating amount of an aqueous composition comprising: at least one compound of the formula: R-COOR' R-C00R' H' \ 4 204997 wherein R Is a long-chain alkyl group having between 15 and 47 carbon atoms, containing between 0 and 6 carbon-carbon double bonds and between 0 and 4 carboxyl groups or salts or derivatives thereof; and R' Is a long-chain alkyl group having between 1 and 36 carbon atoms, containing 0 to 6 carbon-carbon double bonds and 0 to 4 carboxyl groups or salts or derivatives thereof; or R' Is hydrogen, Including salts thereof; and at least one metal salt which releases a metal Ion having a valence of +2 or +3 In water to the area where plants are growing, wherein the weight ratio between said compounds of the formula R-COOR1 is In the range of from 1:5 to 1:500,000,000 by weight and wherein said compound of the formlua R-COOR' is applied in an amount of at least 0.01 mg per acre. While straight chain saturated carboxylic acids and esters thereof are preferred, unsaturated acids and esters are also very useful, with practical utility diminishing with the number of carbon-carbon double bonds in the straight chain. If R or R' are unsaturated, it is desirable that there be 1 to 6 double bonds, preferably 1 to 3 double bonds and most preferably only 1 double bond. It is preferred that R and R' both be straight chain alkyl groups, however, compounds wherein R and/or R' are branched are also useful in accordance with the present invention. If the Compound (I) is a carboxylic acid, monobasic carboxylic acids are preferred. However, dibasic and polybasic acids show comparable activity to monobasic acids and the number of carboxyl groups attached to hydrocarbon chain influences activity to a lesser degree than the number of carbon-carbon double bonds in the straight chain of the carboxylic acid. The compounds of the present invention are preferably of the formula: R-COOR' (I) or a salt thereof wherein R is a saturated long-chafi/d .alkyl group having 15 to 47 carbon atoms and R' is O 3 OCT 1985 hydrogen or a saturated alkyl group having between 1\a <■.% < 2 0 4 9 9 7 i&gst* "V.1 to 56 carbon atoms. While R' may be over 36 carbons in length, these compounds are considerably more expensive to produce than the shorter chain analogs. Thus, 1 -1etracosanyl tetra-5 cosanoate shows superior effects than tetracosanoic acid, and is also superior to 1-methyl tetracosanoate. While not intending to be bound to the mechanism whereby the invention achieves its remarkable results, the longer the chain contributed by the R1 group, the better the hydro-10 phobic bonding to a plant "receptor" may be. Other derivatives of carboxylic acids are useful in carrying out the present invention, such as anhydrides, carbohydrate esters and the like, thiocarboxylic acids and esters and salts thereof, cholesteryl esters or other steroidal 15 esters, amides, triglycerides, and other related compounds. Any compounds which may release the free carboxylic acid, or salts or derivatives thereof, in aqueous solution by the action of acids or bases or other means are also within the scope of the present inventoin. Salts of the 20 carboxylic acids of the invention are also highly useful, and show a higher solubility in aqueous solution than the free acids or esters. Specific examples of saturated acids of the formula (I) include CH - (CH?) ^COOH (Stearic acid), CH, (CH-,) ^gCOOK 25 (Eicosanoic acid), CH,(CH2)2qC00H (Docosanoic acid), CH_(CH?)22COOH (Tetracosanoic acid), CH,(CH^)24COOH (Hexacosanoic acid), CH_(CH^)9^C00H (Octacosanoic acid), and CH, (CH-,) .,gCOOH (Triacontanoic acid). Of the above compounds, eicosanoic acid, tetracosanoic acid and 30 triacontanoic acid are preferred. Specific examples of saturated esters of the formula (I) include CH-(CH,) -,QCOOCH, (Methyl tria- J L L o O contanoate) , CH, (CH.,)-^COOCH. (Methyl hexatriacontanoate) , CH-(CH,)40COOCH- (Methyl dotetracontanoate), CH,(CH7)4&-35 COOCH- (Methyl octatetracontanoate) , CH, (CH2) 2 2^0 ^H -,) 7 - -CH^ (Tetracosanyl tetracosanoate), and CH-(CH7)77-COO(CH0)?gCH- (Triacontanyl tetracosanoate). Of the above compounds, Methyl triacontanoate, Tetracosanyl (* 2 0 4 9 9 7 tetracosanoate and Triacontanyl tetracosanoate arc preferred. Examples of unsaturated esters of the formula (I) include CH3CCH2)10CH=CH(CH2]4COOCH3 and CH3CCH2)22-5 COO(CH0)4CH=CH2. Examples of unsaturated carboxylic acids of the formula CI) include CH3(CH2)^CH=CH(CH2)7COOH (oleic acid) and CH3(CH2)^2CH=(CH2)gCOOH (nervonic acid). Examples of polybasic carboxylic acids include 10 H00C(CH2)16C00H (1,18-octadecanedioic acid), H00C(CH7)2q-C00H (1,22-docosanedioic acid), H00C(CH2)22C00H (1,24-tetracosanedioic acid) and H00C(CH?)^qCH(CH2)^qCOOH (1,12,24-tetracosanetrioic acid). C00H Examples of salts of the compounds of the 15 formula (I) include, but are not limited to, salts having the formula 0 R- C- 0?)nX+n (II) wherein X is Ca*2, Na+2, K+, Mg+~, La+"\ Mn+2, Zn+~, NH4 , aniliniurn, octadecyl ammonium, and the like 20 wherein n is the valence of the cation. According to the present invention, the compounds of the invention are solubilized in an aqueous solution containing at least one metal ion having a valence of +2 or more. The compounds may be dispersed in aqueous 25 solution by any method practiced in the art, including simple solubilization of the compound in the aqueous solution by stirring, heating, and the like, or may be first dissolved in an organic solvent which is subsequently dissolved in a relatively large amount of 30 water, with or without the aid of a surfactant, and preferably in a surfactant - free medium. The mo sr. preferred method of solubilizing the compounds of the present invention in aqueous solution comprises coating the carboxylic acids, or salts or derivatives thereof, 35 or combinations thereof, on the dry salts of the metal ions by means of a solvent in which any of the compounds being used to coat the metal ion salts are soluble. _ -v*l 4 2 0 4 9 9 7 Subsequent dilution in water affords a highly useful solution of the compounds of the invention with metal ions . When the composition of the present, invention is in 5 a dry form, the weight ratio of said compound to said metal salt is in the range of 1:1 to 1:5,000,000,000, preferably 1:5 to 1:500,000,000, more preferably 1:100 to 1:50,000,000 and most preferably 1:1,000 to 1:20,000,000. Optimum weight ratios will vary some-10 what depending upon the particular compounds of the formula (I) and metal salts which are utilised. The optimum weight ratio will also vary somewhat depending upon the type of plants which are being treated therewith. The composition of the present invention contains 15 the compound of the formula (I) and the metal salt in an amount effective to stimulate plant growth. When the composition is in dry form, the composition will usually contain the metal salt in an amount of 50 grams to 1000 grams per kilogram, preferably 250 grams to 20 1000 grams per kilogram, most preferably 500 grams to 1000 grams per kilogram of the composition. The compound of the formula (I) will be preferably contained in an amount of O.lyg to 10g per kilogram, preferably 50pg to 5g per kilogram, most preferably l>g to lg per kilogram of 25 the composition. As discussed hereinbelow, the composition may contain additional active ingredients which improve or do not substantially inhibit the plant growth stimulating effects of the composition of the present invention. The composition may also contain 50 various inert ingredients (liquid or solid) which are incorporated into the composition in varying amounts depending upon the mode of application to plant life. Typically, one part by weight of-a compound of the-invention, or mixtures of more than one compound, is diluted 35 to a final solution with up to about 5,000,000,000 parts of water (by weight), preferably diluted with between anour 2 0 4 9 9 / 4,000 to 2,000,000,000 parts of water, and more preferably with between about 40,000 and 200,000,000 parts of water. Thus, the effective range of concentrations of the compounds of the invention in solution with metal ions may vary widely while achieving similar results in stimulating plant growth and the yield of crops in the field. If an organic solvent is used to form a concentrate of the carboxylic acids or derivatives thereof, the compound is first dissolved in the organic solvent, with or without the application of heat. The resulting solution is then added to water, which may contain the metal ions of the invention, or the metal ions may be added after the addition of the concentrate. Typically, one part (by weight) of one or more of the carboxylic acids or derivatives thereof of the invention is dissolved in between about one to 5,000,000 parts of polar organic solvent (if no surfactant is to be added, or relatively nonpolar solvent if a surfactant is to be added),, preferably one or more of the said compounds of the invention is dissolved in between about 10,000 and 500,000 parts of polar solvent (by weight), and more preferably, 10,000 parts to about 160,000 parts of solvent may be used, and most preferably between about 10,000 and 80,000 parts of solvent may be used. If a nonpolar solvent is employed, then one part of one or more compounds of the invention (carboxylic acids, salts, esters, or other derivatives thereof), by weight, may be dissolved in between about one and 10,000 parts of nonpolar solvent, preferably between about 10 parts and 1,000 parts of nonpolar solvent, and more preferably between about 100 and 1,000 parts of nonpolar solvent (by weight). The resulting solution is then dissolved in water as previously described, with or without the use of a surfactant additive, depending on the solubility of the solvent which would be required in water to attain the cesired concentration of the compounds of the invention. 4 204997 1 Polar organic solvents which are useful in carrying out the present invention included solvents which are soluble in water and in which the organic compounds of the invention are also soluble (alcohols, ketones, lower aliphatic acids, 5 and the like). Nonpolar solvents include those solvents in which the compounds are soluble, but are relatively insoluble in water, requiring the aid of surfactant additives, formation of colloidal dispersions, and the like (higher ketones and alcohols, hydrocarbon solvents, ethers, and the like), If 10 surfactants are to used, these should be used at concentrations preferably up to 57„ (volume/volume), and more preferably at concentrations between 0.1% and 3%, with concentrations between 0.17o and 170 being most preferred. I'etal ions of the invention, which, in combination with ; the long-chain carboxylic acids, ar.d salts and derivatives ; I thereof, produce the remarkable growth-stimulating effects, - include any cation having a valence of +2 or more. IThile j metal ions of lower valence produce a small effect, a higher f valence is required for the full growth-stimulating effect. | 20 Typical metal ions useful in carrying out the present | +2 +2 i invention include, but are not limited to, Ca , Ba , La , s ,+2 „ +2 +2 +2 +£ +2 +2 „ +2 +3 +2 f Cd , Pb , Co , Iln , Ce , I!g , Zn , Cv , Fe , Fe , I +2 . ! Ni , and the like, however, only a limited number of metal | ions are preferred due to their superior effect and relatively f +2 ^ 25 low toxicity. Metal ions of higher toxicity, such as Pb | and Cd+^ are very useful, and may be used on plant life not I +2 utilized for food purposes. Other metal ions, such as Sr , | are especially useful, however, the most preferred metal ions | are those which show the highest degree of plant growth f 30 stimulation, such as Ca+ , Mg , Mn , and La , with Ca being the most preferred metal ion in the group. 204997 The metal ions, as in the case of the long-chain compounds of the invention, were found inactive in promoting plant life when applied thereto separately under identical conditions. In the preferred embodiment of the present invention, the compounds of the invention are either (1) added to a solution of metal ions in water in a polar organic solvent, or (2) coated on the dry salts of the metal ions of the invention by use of a suitable solvent which is subsequently allowed to evaporate, with or without the use of heat. The latter method is most preferred, since it allows for a product requiring only a single container without the need for a separate package containing a solution of the long-chain compounds. Since the long-chain compounds may be used at a very low concentration, solubility usually poses no problem when the dry product is added to water. Preferred metal ion concentrations in the final composition which is applied to plant life are between 0.1 and 50 n£:, with concentrations of between about 1 and 30 ml-' being more preferred. If a surfactant is part of the final formulation, higher metal ion concentrations may be required, and may extend up to about 1 molar. When applied to the area where plants are growing, the long-chain carboxylic acids, or esters, salts, or derivatives thereof, alone or in combination, it is desirable to apply at least 0.01 mg of the compounds per acre of land, with at least 0.03 mgof the compounds applied per acre being preferred. Up to several grams of the compounds may be applied per acre of land, however, this is not usually necessary, and a limited advantage through increasing the application rate is observed, as will become apparent in following examples of the invention. The preferred mode of applications of the compounds of the invention in solution with polyvalent metal ions is foliar spraying of the formulations as a fine mist onto the leaves of plant life. However, 204997 activity has been observed using other means of application, such as seed soaks, and soil drenches. Seed soaks have the advantage of requiring a small volume of the compositions of the invention, while soil drenches require considerably larger quantities. For seed soaks, the preferred ratio of seed to solution of the compounds of the invention including metal ions in solution is at least 2 parts solution to 1 part of seed (volume/volume), and similar results are achieved at higher solution to seed ratios, extending to about 25 to 1 or more. Soil drenches require a considerable quantity of solution, amounting to between about 1 ml per plant to 10 liters per plant, with 1 ml to 1 liter per plant being preferred, and 5 ml to 1 liter per plant being more preferred. Of course, larger plants require larger volumes of solution than smaller plants, and plants with deeper root systems likewise require more solution to be applied to the soil in which they are growing. Combinations of soil drenches, seed soaks, and foliar application are also useful, and other modes of formulation or application, such as formations of coloidal suspensions of the compounds of the invention, and the like, applied as innoculants, use of the formulations as fertilizer additives or complements, and the like, are not considered to be beyond the scope of the present invention. The formulations of the present invention are useful on plant life at all stages of development, with some plants responding better at relatively early stages as compared to other plants. The preferred stage of development is at the stage where the plant bears between about two and seven true leaves (or sets of two leaves each in the case of dicots, or up to the fifth trifoliate stage on beans and soybeans), with the preferred stage between three and six true leaves. For grasses, such as wheat, corn, sorghum, and the like, later stages of growth have shown some advantage. Corn may be treated at a stage before or after tassel initiation in the plant. Wheat is best treated in the spring rather than soon ^ 2 04V 9' after germination in the fail. Perennial plant iiie may be treated seasonally, with treatments yearly in the spring being preferred. Multiple sprayingson growing plants has also indicated that improved results may be obtained in this manner, especially on soybeans, tomatoes, and the like. While the pH of the final formulation is of no concern, best results are obtained where the degree of acidity or alkalinity is not severe, preferably between pH A and 12, and more preferably between pH 5 and 10. Due to the tolerance of the metal ion concentrations for most plants, hard water (or well water) may usually be used without concern for metal ion concentration in the water. Highly poluted water, or that known to contain large concentrations of hydrocarbons or other long chain compounds (water in which oil has formed on the surface, e.g.) should be avoided. Plants are best fertilised using normal agricultural practices, with no unusual or additional requirements, and results are observed even at suboptimum levels of fertilizers. In greenhouse trials, however, the use of concentrated water-soluble fertilizers affects results somewhat, and some guidelines for greenhouse trials are given in the following examples of the invention. Improved results have also been observed with the inclusion of foliar fertilizers into the compositions of the present invention. These include water-soluble salts which supply plants with essential nutrients, micronutrients (including the metal ions of the invention), nitrogen containing compounds, such as urea, ammonium nitrate, and the like, potassium, and other compounds or combinations thereof known in the art. Compounds which complex or precipitate the metal ions of the invention produce lesser increases when combined in solution with the compounds and metal ions of the invention, and therefore show somewhat more limitedpractical utility. The metal ions of the invention are any metal ions having a valence of +2 or more, and those released from inorganic , 2 049 97 1 metal salts are preferred, however, any organic or inorganic salt or compound capable of releasing the desired metal ions in aqueous solution nay be used. Counter ions, such as Cl", NO^ , acetate, and the like, are of minimal importance, since 5 these do not appear to influence the activity of the cations of the invention. Also, some complexed metal ions may be useful, as well as aquated metal ions. Salts of the carboxylic acids of the present invention are very useful in carrying out the methods of plant growth 10 stimulation of the invention, and show improved solubility over the free acids of the invention. These salts may be any known in the art which show a solubility in the concentration range useful for the carboxylic acids of the invention. The salts of alkali metals show preferred water solubility, 15 however, since the compounds of the invention show solubility at the low concentrations which are useful, described further henceforth, other metal salts are also of valuable use, such as salts of the metal ions of the invention. These polyvalent ions show a limited solubility at certain concentrations, 20 when combined with long-chain carboxylic acids, however, it is important to note that the concentrations of the carboxylic acids of the invention which show effective results may be low enough to present no solubility in aqueous solutions prepared therefrom. Also, salts of carboxylic acids, or derivatives 25 thereof, may include a plurality of metal ions, and metal ions useful in carrying out the invention may be in the forms of salts of a plurality of long-chain compounds of the invention. •It has further been four.d that different species of 30 plant life respond optimally at somewhat different concentration of metal ions while the concentration of the long-chain compounds of the invention remains at a much broader range. For example, soybeans, sweet corn, and a large variety of vegetables respond to metal ion concentrations ^ 2049 9 7 1 e.g., over a broad range of about 5 mM to 15 mM and more. In some cases, positive results are seen at lower metal ion concentrations. Field corn responds well at relatively lower metal ion concentrations, i.e., between 1 mM and 4 mM, with 5 between about 2 mM and 3 mM being preferred. Other crops, such as peas and the like, respond to formulations of the compounds of the invention containing higher metal ion concentrations. These crops are seen to respond well at metal ion concentrations ranging up to 20 ml! and more, 10 while wheat responds well at concentrations over about 15 ml! to 20 mM. From the detailed description given hereinafter, optimum concentrations of metal ions, together with concentrations of the compounds of the invention, which enhance the growth of many crops and other plants will become apparent. 15 The formulations of the present invention are found useful in stimulating the growth of all forms of plant life, including all crops and plant life used for ornamental, building, paper, food, and other purposes. Included in the group of plant life that responds favorably, but not limited thereto, are 20 corn, barley, wheat, oats, rice, rye, citrus fruits, mangoes, grapes, soybeans, beans, peas, melons, cabbage, lettuce, sugar beets, radishes, cucumbers, potatoes, sunflowers, tomatoes, peppers, alfalfa, grasses, hay, pineapples, bananas, trees, and other agricultural commodities. 25 In accordance with an additional aspect of the present invention, naturally-occurring products which contain active amounts of the compounds of the invention are highly useful when combined in the formulations with metal ions. In particular, these include naturally-occurring waxes and oils and the 30 Z 049 9 7 like, including compounds of the invention, or mixtures thereof, which are obtainable from natural sources. These usually include useful compounds such as the long-chain carboxylic acids of the invention, esters thereof, hydroxy acids, and the like, and include both saturated and unsaturated compounds. The compounds may further be present as esters of other naturally-occurring compounds containing carboxyl groups or hyriroxyl groups, such as auxins, gibberellins, sugars, etc. Useful naturally occurring compounds include, but are not limited to, candelilla wax, carnauba wax, Chinese insect wax, esparto wax, ghedda wax, Japan wax, peanut oil, olive oil, rice bran oil, shellac, sisal wax, soybean oil, beeswax, etc. The preferred members of the foregoing comprise any naturally-occurring wax, oil, and the like, which contain compounds of the invention, or mixtures thereof, such as beeswax, esparto wax, and the like. In a preferred embodiment of the present invention, such naturally-occurring waxes are used in the formulations of the invention, and may be used in any manner in which the pure compounds of the invention are utilized. Especially useful are concentrated forms of the formulations, made by coating a relatively small quantity of the naturally-occurring wax, oil, or the like, or mixtures thereof, directly on a metal salt of the metal ions of the invention, by means of an appropriate solvent or other means, as described in the foregoing description. While these naturally-occurring compounds may contain an additional active ingredient, such as 1-triacontanol, examples in the following best mode of the invention are given illustrating that this compound is inactive in the formulations as they are described herein. Many compounds and other substances are used in agricultural practice which also contain 1-triacontanol, however, the 1-triacontanol is recognized as essentially inactive. These include mulches, cow manure, paper, peat and peat moss, compost, and the like. 2 0 4 9 9 7 In accordance with another aspect of the invention, seed obtained from crops sprayed with the formulations of the invention show improved quality and may be expected to show increases in crop yields obtained through the planting of said seed with or without further application of the formulations, and, indeed, additive increases may be observed from growing season to growing season. Improved germination has been observed on seeds of crops which require longer germination time or grow slowly on germination, such as tomatoes, peppers, celery, lettuce, tobacco, and the like. The invention being thus described, other objects and further scope of the present invention will become apparent from the detailed description given hereinafter. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing a typical dose-response curve for the compounds of the invention, illustrated for the response of field corn (cv. Pioneer 3780) to formulations of the invention containing 3 mM CaCl^ and varying concentrations of 1-triacontanoic acid. Fig. 2 is a graph showing the optimum hydrocarbon chain lengths of compounds of the invention for use on tomatoes (CaCl? = 10 mM) and field corn (CaCl9 = 2 mM). Fig. 3 is a graph showing the response of field corn seedlings (cv. Pioneer 3535) to formulations of the invention +2 containing beeswax (10 pg/liter) and Ca (2 mM) at different stages of development. 2 049 97 BEST MODE EXAMPLES The following examples are presented herein as being exemplary of the present invention and, accordingly, should not be considered, in any way, as being limitative of the applicant's inventive contribution. In the preferred mode of the invention, compounds of the structure: R - COOR' wherein R is a long-chain alkyl group containing from 15 to A 7 carbon atoms, and may contain between about 0 to 6 carbon-carbon double bonds, and be substituted by about 0 to A carboxyl groups or derivatives thereof; and R' is a long-chain alkyl group having between about 1 and 36 carbon atoms, and may contain between about 0 to 6 carbon-carbon double bonds, and be substituted with about 0 to A carboxyl groups, or derivatives thereof, or is hydrogen; are considered the most preferred members of the classes of compounds disclosed in the foregoing Specification. These are used to stimulate plant growth in the formulations given by examples hereinbelow in combination with metal ions having a valence of +2 to +3. The compounds of the invention may also be contained in naturally-occurring oils, waxes, and the like, as described in the following description of the preferred embodiments of the invention. Also, compounds hydrolyzed in situ to compounds of the invention in the compositions are not considered beyond the scope of the present invention. Typical formulations useful in carrying out the present invention are outlined in Table 1. The long-chain organic compounds were dissolved in the solvents with or without the application of heat, depending on the solubility of the compounds. ■ >Ag 104 9 9 7 1 detailed examples example i A 0.1 mL quantity of Formulation 1 was added to a solution of KgC^, or other metal salt, at a metal ion 5 concentration of 3 mM in water, stirred, and sprayed on the leaves of field corn seedlings. example ii A 1.0 mL quantity of Formulation 1 was added to a solution +2 of CaCl7, or other Ca salt, in water at a concentration of 10 10 nM (200 mL total volume). The solution was shaken and sprayed on the leaves of soybean seedlings (1-triacontanoic acid concentration 0.1 mg/L). example iii A 1.0 mL aliquot of 1-tetracosanyl tetracosanoate in 15 acetone solution was dissolved in 2 L of water containing 15 r;_M of metal salts. The resulting solution was sprayed onto the leaves of pea seedlings. example iv A 40 nL aliquot of hexacosanoic acid, or salt or suitable 20 derivative thereof, in solution according to Formulation 2 or 2, was added to 10 u.s. gallons of water containing metal ions at a concentration of 3 mM. The final solution was applied as a mist to 1 acre of field corn. example v 25 A 0.5 mg quantity of 1-tetracosanoic acid was added to 109 g of anhydrous CaC^ and the mixture was allowed to dry. The granular product was dissolved in 100 u.s. gallons of water and applied to 10 acres of field corn as a fine foliar spray, said water having a metal ion concentration of between | 30 about 2 and 3 mm. X'1 2. 04997 1 EXAMPLE VI Beeswax or esparto wax was dissolved in a nonpolar solvent, such as trichloroethylene or the like, according to Formulation 7. The solution was subsequently coated 5 evenly on about SO kg of anhydrous CaCl„ and allowed to dry. +2 Dilution of the final product in water to 2 mM Ca concentration gave sufficient solution to cover 950 acres of field corn. example vii 10 A 0.67 m.L aliquot of the solution according to Formula tion 8 was added to 50 mL of acetone (or other solvent), and the solvent was added to 1,090 g of technical grade CaCl?. After the product had dried, it was dissolved in 200 gallons of water and applied to 10 acres of a vegetable crop at the 15 rate of 20 gallons/acre. While the above Examples briefly illustrate the preferred embodiments of the invention only partially, they are not intended to limit, in any way, the scope of possible combinations of formulations and methods of the present invention. 20 The formulations of the invention are applied, preferably to the leaves of growing plant life, and are also useful as seec soaks, soil drenches, and the like. The methods used to evaluate the efficacy of the foregoing Examples of the invention are outlined in the following description of 25 the methods of the invention. 1 METHODS 2 0 4 V 9 7 In greenhouse trials, plants were sown in pots 10 to 15 cm in diameter containing Peat-Lite^. Twice the number of 5 seeds per plot were sown than the actual number of plants used with the various treatments, with plants being thinned to those of similar size prior to application of the formulations of the invention. Ir, general, seedlings were fertilized on germination with a water-soluble 15-30-15 fertilizer, and 10 again the day following application (15-30-15 fertilizer in the case of dicots, and 30-10-10 fertilizer for monocots). Each plot received ca. 50 mL of fertilizer at a concentration of 2.5 g/L. In field trials, seeds were sown using standard agricul-15 tural practices or as otherwise indicated. Small plots were generally employed, and were carefully selected to minimize variation in plant size within each block. In all trials conducted (greenhouse and field trials), treatments were randomly assigned within each block using standard methods 20 practiced in the art. Plants were blocked by size in the greenhouse trials to minimized the variation due to plant size. Results obtained were found similar whether plants were grown under natural or artificial lighting (ca. 750 to 1000 25 ft-can) for many plants tested. When plants were grown under artificial lighting, 26°C day temperatures were maintained with night temperatures of about 17° C. Plants grown by natural lighting were grown at the same time of year as normal for that particular plant in the field. When applications were made at 30 varying temperatures, indoor temperatures were adjusted accordingly, and plants grown outdoors were sprayed at varying times of the day when the desired temperatures were reached. ^ 2 0 4 9 9 7 1 Plants were sprayed at various stages of development with formulations of the present invention as described in the examples given hereinafter. In all cases, randomized complete block designs were used, with each treatment 5 being replicated between about 4 to 6 times. In greenhouse trials, plants were generally harvested at least four days after treatment, including roots, and soil was removed therefrom by washing with water. Fresh weights were obtained for each plot, and plants were dried to constant weight in an 10 oven at a temperature below 100° C. Water content values were obtained by subtraction of dry weights from fresh weights, however, dry weights were used as the true indication of growth increases of treated plots over control plots. In field trials, increases in marketable yield were 15 determined, and observations were recorded regarding increases in number of fruit, size of grain, and the like. All data were analyzed statistically by standard analysis of variance methods widely practiced in the art, and using Duncan's Multiple Range Test (Biometrics, 11: 1 (1955)). Increases 20 in the dry weights of seedlings found in greenhouse trials were found particularly useful in predicting the yields of crops in field trials, and, in general, dry weights thus obtained may be expected to be lower than the actual yields found in the field. 25 Trials included determination of optimum stages of plant development for spraying or other mode of application of the compounds of the invention, optimum application rates, optimum temperatures, and other conditions which are useful in the application of the compositions of the invention to 30 plant life in the field, greenhouse, or other environment. 2 04 9 9 7 Compounds of the invention were tested in solution with the metal ions of the invention, either singularly or in combination with other compounds or metal salts of the invention. The preferred mixture of compounds used was purified beeswax, which is known to contain esters of straight- chain monohydric alcohols with even-numbered carbon chains from C^^ to C^g esterified with straight-chain acids also having even numbers of carbon atoms up to C_, (some C,0 jo 1 o hydroxy acids). Also contained therein are hydrocarbons with straight carbon chains from to C33 (inert), as described in Merck Index, 9: 1027 (1976). The long-chain esters are also found superior to the carboxylic acids, and the small amount of 1-triacontanol constituent in the wax is also shown in the following detailed description to be inert in the formulations of the present invention containing beeswax. Other naturally-occurring oils, waxes, and the like, are also useful, including those obtained from both plant and animal sources, as described in the foregoing description of the invention. The data in the following tables and examples of the invention are intended to be exemplary of the results that can be expected by applications of the compositions of the present invention on plant life using the methods outlined herein, however, the specific compounds, formulations, and methods used in the examples are not intended to be limitative, in any way, of the spirit and scope of the invention as fully described herein. 2 0 4 V v 7 1 TABLE 1 Formulation Examples Useful in Carrying Out the Present Invention, Prepared by Dissolving a Solution of Compounds of the Invention in Water Solution (Method A) or Applying a Solution of Said Compounds to Dry Metal Ion Salts, Allowing the Solvent to Evaporate, and Dissolving the Product in Water (Method B). FORMULATION COMPOUND3 R R' WEIGHT (mg) SOLVENT SOLVENT VOLUME METHOD 1 30 H 5 acetone 5 0 mL A 2 24 H 5 acetone 50 A 3 24-30 1-36 5 ketone or 50 A alcohol 4 20-24 H 5 ketone 10-100 A 5 24-36 1-36 150 trichloro- 100 A ethylene 6 24 H 50 acetone, etc. 50 B . 7 c - wax - 150 trichloro- 100 B ethylene 8 wax or oiIc 150 benzene, 100 B chloroform, etc. 10 15 20 aNumbers refer to the number of carbon atoms in the R and R1 groups, respectively, of compounds having the structure R-COOR' 25 ^At least one carbon-carbon double bond in the R group. 'See text and detailed examples. 2 0 4 9 9 1 TABLE 2. Increases in the Dry Weight of Field Corn Seedlings (cv. Pioneer 3780) Treated 7 Days after Germination with and without 1-Triacontanoic Acid (0.1 tig/L, Formulation 1) and Naphthalene Acetic Acid, and with 5 Varying Concentrations of CaC^ (pH = 9, Spray Temperature =■ 25° C) . Seedlings were Harvested 4 Days after Spraying. TRIACONTANOIC ACID CaCl (n) J) NAA Cf-0 DRY WT. ■A % INCREASE LEVEL OF SIGNIFICANT 10 TRIAL 1 0. ,0 0.0 1.19 g + 1. 0 0.0 1.26 + 6 % N. S. + 3. 0 1.0 1.35 + 14 0.10 + 7. 5 1.0 1.33 + 12 0.10 15 + 10. 0 1.0 1.15 - 3 N.S. + 0. 0 0.0 1.25 + 5 N.S. TRIAL 2 0. 0 0.0 0.93 g „ .... + 1. 0 1.0 1.06 + 14 "L 0.01 20 + 5. 0 1.0 1.09 + 17 0.01 + 3. 0 0.0 1.21 + 30 0.01 + 5. 0 0.0 1.02 + 10 0.05 ^Weights are the sum of four plants per plot (avg.) replicated 5 25 times. Less variation due to plant size in Trial 2 accounts for the greater level of significance of results over Trial 1. 2 04997 10 15 20 TABLE 3. Increases in the Dry Weight of Field Corn Seedlings Sprayed 6 Days after Germination with Formulations of 1-Triacontanoic Acid (0.1 mg/L) and Various Metal Ions (3 mM), at a Temperature of 26° C and pH 9.3. Plants were Harvested 4 Days after Spraying (cv. Pioneer 3780). METAL ION DRY WT. PERCENT LEVEL OF * INCREASES SIGNIFICANCE CONTROL 0.87 g -- +2 Ca 1.14 + 31 % 0.01 T +3 La 1.02 + 17 0.01 Mg 1.04 + 20 0.01 Mn+2 1.08 + 24 0.01 Sr+2 1.10 + 26 0.01 Pb+2 1.06 + 22 0.01 +2 Ba 1.11 + 23 0.01 ,+2 Cd 1.20 + 38 0. 01 Zn+2 1. 07 + 23 0.01 Cu+2 1.07 + 23 0.01 Co+2 1. 04 + 20 0.01 *Weights are the sum of four plants per plot (averaged), replicated four times. 10 15 20 ^ Z U 4 y V 7 TABLE A. Increases in the Dry Weight of Field Corn Seedlings (cv. Pioneer 3780) Treated 7 Days after Germination with and without a Variety of Long-Chain Alkyl Carboxylic Acids and Esters of the Formula R-COOR' (Formulations 1, 2, £>. 3) and CaC^, Harvested A Days after Spraying. R R\ pH CaCl (mM) DRY WT. (g) 70 INCREASE p* TRIAL 1 - Concentrations of R-COOR' - 0.1 mg/L C24 H 9.3 3.0 1.01 g + 20 0. 01 C26 H 9.3 3.0 1.09 + 30 0. 01 C28 H 9.3 3.0 1.10 4- 31 0. 01 C30 H 9.3 3.0 1.1A + 36 0. 01 C30 ch3 9.3 3.0 1. OA + 2A 0. 01 C36 ch3 9.3 3.0 1.09 + 30 0. 01 C30 H 5.2 3.0 1.11 + 32 0. 01 CONTROL - 0.8A TRIAL 2 - Concentration of R-COOR' = 0.01 mg /L r ** U2A H 9.0 3.0 1.31 g + 25 % 0. 01 ch3 9.0 3.0 1.36 + 30 0. 01 r -V-.VVr A8 CH3 9.0 3.0 1.23 + 17 0. 01 CONTROL - ' - 1.05 — — - - — ■'•Level of Significance. 25 ,2A-Tetracosanedicarboxylic Acid. ***Concentration 1 pg/L. 2 o 4 y v 7 1 TABLE 5 30 Increases in the Dry Weights of Field Corn Seedlings Treated with Formulations 3, 6, & 7 of the Invention When Seedlings Had Three True Leaves, Harvested Soon after the Fourth True Leaf Appeared. 5 COMPOUND CONCN. (pg/L) CaCl 7 (tnM) " TEMP.3 b DRY WT. (g) % INCR. P cv. Trojan T-950 CONTROL 1.13 -- Tetracosanoic Acid 2 2 19° C 1.29 + 147„ 0.05 10 Hexacosano ic Acid 2 2 19° 1.23 + 9 N.S. Beeswax 10 2 19° 1.41 + 25 0.01 ■D c Beeswax 10 2 19° 1.25 + 11 0.10 cv. Trojan T-1100 CONTROL -- 2.14 -- 15 Beeswax 10 2 22° 2.19 + 2 N.S. Beeswax 10 2 25° 2.33 + 9 0.05 Beeswax 10 2 28° 2.50 + 17 0.01 _ d Beeswax 10 2 22° 2.37 + 11 0.05 Beeswax ® 10 2 22° 2.27 + 6 N.S. 20 cv. Troj an T-1000 CONTROL -- 1.98 -- 1-Te tracosanyl A Tetracosanoate 1 2 19.5 2.38 + 20 e 1-Triacontanyl 25 Tetracosanoate 1 2 19.5 2.07 + 5 e Nervonic Acid^ 1 2 19.5° 2.10 + 6 e Beeswax 10 2 19.5° 2.11 + 7 e Beeswax 10 2 20.5° 2.34 + 18 e Air temperature at the time of application; Weights per four plants per plot; Sprayed with 15-30-15 fertilizer, 2.5 g/L; d £ Applied with 1 g/L urea and 50 mg/L ZnC^; Not calculated; ^cis-15-Tetracosenoic acid ; ^applied with 0.15 g/L Banvel D. 2 U49 97 TABLE 6. Increases in the Dry Weight of Soybean Seedlings (cv. Williams) Sprayed with Formulations of the Invention Containing Compounds of the Structure R-COOR' (Formulations 3, A, 6 & 8, 10 pg/L) and +2 Ca (10 mM) at Varying Stages of Development and Temperatures (pH 7.4 to 7.6). R R' STACE3 TEIT. DAYb DRY 17T.C % INCREASE CONTROL -- -- 7.07 g « d Beeswax 2 sets 24° C 16 9.49 + 34 _ d Bee swax 4 sets 24° 28 8. 95 + 27 TJ d Beeswax 3 sets 33° 22 8.58 + 21 C24e H 3 sets 28° 22 7.61 + 8 » 3 sets 28° 22 8.53 + 21 C24 C24 3 sets 28° 22 9.30 + 32 C24 C30 3 sets 28° 22 7. 63 + 8 2 The number of sets of leaves refers to the number of sets of 3 leaves each(trifoliate stage). ^Numbers of days after germination upon which each treatment was sprayed. cWeights are the sum of 4 plants per plot, replicated 5 times, ^Mixture containing compounds wherein R = 24 to 36 and R' = 24 to 36, see text. Nervonic acid (cis-15-tetracosenoic acid). ^ 2 U 4 9 9 7 1 TABLE 7. Increases in the Dry Weights of Certain Crop Seedlings Treated with Formulations 3, 6, & 8 of the Invention at pH 7.3-7.7, and Harvested A to 9 Days after Treatment. 5 CROP3 COMPOUND CONCN. (ug/L) CaCl (mM) % INCR. P TOMATOES Tetradecanoic Acid 10 10 - 1A70 N .s. Hexadecanoic Acid 10 10 + 20 0 .05 Oleic Acid 10 10 + 12 N .s. 10 Eicosanoic Acid 1 10 + A5 0 .05 Docosanoic Acid 1 10 + 35 0 .05 Beeswax 100 10 + 38 0 .05 WHEAT Beeswax 15 15 -f 22 0 .05 Beeswax 20 20 . + 38 0 .01 15 PEAS Docosanoic Acid 1 15 -f 36 0 .01 Tetracosanoic Acid 1 15 ■ + A8 0, .01 TOBACCO Tetracosanoic Acid 10 10 + 2A 0, .05 Beeswax 10 10 + 26 0, .05 COTTON Tetracosanoic Acid 10 10 + 37 0, .01 20 1-Triacontanyl Tetracosanoate 10 10 + 31 0, .01 Beeswax 10 10 + A1 0. .01 ALFALFA Triacontanoic Acid 100 10 + 99 0, .01 BARLEY Triacontanoic Acid 100 10 + 3A 0. .05 25 BEANS Triacontanoic Acid 100 10 + A6 0. ,10 SWEET CORN Beeswax 10 10 + 28 0. .01 PEPPERS Triacontanoic Acid 10 10 + 21 0. ,10 Beeswax 10 10 + 2A 0. 05 POTATOES Tetracosanoic Acid 2 10 + 23 b 30 Beeswax 10 10 + 28 b KY. BLUEGRASS Beeswax 10 10 + 26 0. 01 a b Similar responses observed with all cvs. tested; Not calculated. 204997 1 TABLE 8. Increases in the Dry Weight of Field Corn Seedlings (cv. Pioneer 3535) Sprayed with Various Formulations of Compounds of the Invention (0.01 mg/L) and with 1-Triacontanol (0.1 mg/L, Prior Art) on Day 11 5 after Germination at an Equivalent Application Rate of 10 gal/a. Plants were Harvested A Days after Spraying (A Plants/Plot, 5 Replications). COMPO'JND CaCl„ NAA (rrJir (pM) PH TEMP. DRY WT. 7c INCR. P CONTROL 0.0 - - - 2.13 g -- None 2.0 7.3 21 .5° 2.19 + 3 % N. S. Tr iacontanol 2.0 - 7.3 21 .5 2.12 0 N. S. None ON O O 8.8 21 .5 2.16 + 1 N. s. Triacontanol 6.0 1.0 8.8 21 .5 2.A2 +1A 0. 01 Tr iacont anol 6.0 1.0 7.3 21 .5 2.1A 0 N. s. 1-Triacontanyl Tetracosanoate 2.0 7.3 21 .5 2.AO +13 0. 01 Beeswax 2.0 7.3 19 .0 2.AA +15 0. 01 Bee swax 2.0 7.3 21 .5 2.35 +10 0. 05 Beeswax 2.0 7.3 23 .5 2.3A +10 0. 05 Note: Formulations 1, 2, and 3 were u sed for all treatments except Beeswax, where Formulation 7 v?as used • 1 TABLE 9. Increases in Che Marketable Yields of a Variety of Crops Treated with Various Formulations of the Invention under Different Conditions. CROP CULTIVAR R - coou' R R1 concn. (pg/L) CaCl-(mM) No. of leaves3 appln. rateb */. INCREASE P 5 Field Com Trojan TXS 94 -Beeswax- 10 2 4 10 gal/ a + 33 X 0.01 Field Corn Pioneer 3535d -Beeswax- 10 2 3 10 + 7 N.s. Field Com Pioneer 3535 -Beeswax- 10 2 5 10 + 7 N.s. Field Corn Pioneer 3535 -Beeswax- 10 2 7 10 + 15 0.09 Soybeans Williams C30 H 5 10 2-3e 20 + 56 0.01 10 Soybeans Williams -Beeswax 10 10 2-3e 20 + 53 0.01 Peas Alaska es H 15 is 4-5 10 + 45 0.05 Peas Alaska -Beeswax- 15 15 4-5 10 + 56 0.05 Peas Sugar Snap C22 H 2 15 4-5 10 + 44 0.05 Tomatoes Better Boy C24 H 2 10 4 20 + 64 0.05 15 Tomatoes Better Boy -Beeswax- 10 10 4 20 + 35 0.10 Sweet Corn Golden X Bantam C£^ H 2 10 4 10 + 36 0.05 Sweet Corn Golden X Bantam-Beeswax- 10 10 4 10 + 57 0.01 Peppers Red Chili C30 H 5 10 4-5 20 + 82 0.01 Cucumbers Straight 8 -Beeswax- 10 10 4 20 + 119 0.05 20 Lettuce Buttercrunch -Beeswax- 10 10 4-5 20 + 33 0.05 Radishes Champion C24 H 4 10 3 20 + 47 0.05 Alfalfa Kansas -Beeswax- 10 10 6 20 + 44 0.05 Beans Blue Lakes -Beeswax- 10 10 2-3e 20 + 48 0.10 25 aSee text for definitions; ^In U.S. gallons per acre; cMixture of C2^ to C^ carboxylic acids and esters, see text; ^Sprayed at higher air temperature than optimum; eSecond to Third trifoliate stage. / YJ o J) -o -J z. u 4 9 V 7 results The formulations of the present invention were found highly effective when used to stimulate the growth and crop yields of all plant life tested. Using the formulations provided as examples in Table 1, foliar application was the the preferred mode of application, however, soil drenches and seed soaks were also found to be effective in promoting plant growth. Preliminary research using the formulations showed that the effects could be altered by other plant growth substances (Table 2), such as auxins, gibberellins, cytokinins, and other plant growth substances. The range of metal ions useful in the formulations of the invention was found to be broad (Table 3), including metal ions having a valence of +2 or more in aqueous solution. Increases in growth were also found using a broad range of compounds of the invention, ranging up to about 48 carbon atoms in length, together with esters thereof (Table A and 5). Field corn showed varietal responses to the formulations depending on certain environmental factors and in some cases application rates (Table 5). Most cultivars tested showed a superior response when treated at a temperature less than about 21° C, while the Trojan cultivars showed better responses at somewhat higher temperatures. Application together with other commonly used agricultural products was generally effective, thereby lowering the cost of separate applications. In general, the monocots tested responded favorably at application rates as low as 10 U.S. gallons per acre, while dicots responded to a higher degree at higher application rates. Under certain conditions of low relative humidity, higher rates of application are preferred, but not required for activity. Varietal differences in com were found to influence the growth stimulating response to a lesser degree when naturally-occurring oils, waxes, and the like were employed in the formulations as a source of the long-chain compounds of the ■<S2^V /. J 4 9 9 7 1 invention. Figures 1 and 2 illustrate the effectiveness of the compounds of the invention in the formulations at very low concentrations relative to the concentrations of the metal ions in solution. Also, different crops show 5 somewhat different responses to the formulations depending on the chain length of the compounds in said formulations. The varietal differences observed with field corn were also lowered through the use of the combinations of compounds of the invention found in oils, waxes, and the like. For example, 10 cv. Pioneer 3535, the variety found to be least responsive to any formulation, showed statistically significant responses only when treated with the mixtures of compounds of the invention contained in the naturally-occurring waxes or oils. VThile the response was found to diminish at more advanced 15 stages of plant development (Figure 3), this cultivar was found to show increases in crop yield even when treated at the seven-leaf stage (when the seventh leaf was first visible). Also, the longer-chain esters present in beeswax and the like, such as tetracosanyl tetracosanoate, are apparently more 20 active in the formulations in many cases than the free carboxylic acids or salts thereof. This is also observed in the case for soybeans and other crops (Tables 6 and 7). All crop tested with the formulations of the present invention showed enhanced growth shortly after treatment in 25 greenhouse trials (Table 7). In general, monocots were treated when the third or fourth true leaf became visible, dicots were treated when the third or fourth pair of leaves became visible, and beans were treated when the second or third trifoliate was expanding. Crops such as cucumbers, 30 squash, pumpkins, and the like, were treated when the fourth true leaf started to form. All formulations found optimum in greenhouse trials were selected for use in field trials. Seed soaks and soil drenches also showed increases in growth from about 7 to 33% (dry weight). Z 0 4 V 9 7 1 The naturally-occurring oils and waxes of the invention, as hereinbefore described, contain varying amounts of compounds of the present invention, depending on the natural product selected for use. Those crops responding favorably to 5 compounds of the invention having relatively longer carbon chain lengths, such as corn, soybeans, and wheat, showed improved increases in growth and crop yield when treated with waxes and oils having constituents of these chain lengths, such as beeswax, esparto wax, and the like. Crops and other 10 plant life showing a response to a lower chain length which may be preferable to that observed when treatment is made using formulations of longer chain lengths may effectively be treated with naturally-occurring oils and waxes such as peanut oil (C^ to , jojoba oil or wax to , olive oil 15 t0 Ci8^ ' rice t>ran oi-l (C16 t0 C18^' anc3 t^6 A large variety of sources of such naturally-occurring oils and waxes will become apparent to those skilled in the art as a result of this description, and all are not to be construed as beyond the scope of the present invention. 20 Also present in many naturally-occurring oils, waxes, and the like, is a long-chain alcohol (1-triacontanol) , recently discovered to be useful for increasing the growth of plant life and crops in the field. Using the formulations found by the present inventor (U.S. Patent No. 4,333,758) under the 25 conditions used in applying the present invention, however, the alcohol constituents are found to be totally inactive (Table 8). Table 9 shows the remarkable effectiveness of the formulations of the invention in stimulating the yields of 30 a large number of crops in the field. In most cases, the use of a naturally-occurring wax or oil is preferred over the use of the pure compounds of the invention, together with preferred concentrations of metal ions of the invention. 35 204997 1 In addition to increasing the growth and yields of a number of crops in the field, the compositions of the invention are also useful in promoting the growth of other plant life, and effective results are observed on ornamental 5 plant life, such as flowers and the like, and ornamental leaf plants. For example, tulip flowers are increased in size up to about 387o, as are a number of other flowers on other plant life. The growth of trees is also increased by the promotion of lateral budding and other effects. Increases 10 in the growth of oil palms and other plant life used for similar purposes has also been observed. Many root crops, such as sugar beets, carrots, onions, and the like show markedly improved root size. Also, the yields of wheat and other grasses may be increased over about 20%. 15 The invention being thus descibed, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be 20 included in the scope of the following claims. , v C - C ^23 OCT 1985 ^ </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 36 204997 WHAT WE CLAIM IS:

1. A plant growth stimulator composition, comprising:

at least one compound of the formula:

R - COOR'

wherein R Is a long-chain alkyl group having between 15 and 47 carbon atoms, containing between 0 and 6 carbon-carbon double bonds and between 0 and 4 carboxyl groups or salts or derivatives thereof; and RT

containing 0 to 6 carbon-carbon double bonds, and 0 to 4 carboxyl groups or salts or derivatives thereof; or R' Is hydrogen, or a salt thereof; and at least one metal Ion salt which releases In water a metal Ion having a valence of +2 or +3, wherein the ratio of said compound of the formula R-COOR' to said metal salt is in the range of from 1:5 to 1:500,000,000 by weight.

2. A plant growth stimulator composition according to claim 1 wherein the ratio of said compound of the formula R-COOR' to said metal salt Is In the range of from 1:100 to 1:50,000,000 by weight.

3. A plant growth stimulator composition according to claim 1 wherein the ratio of said compound of the formula R-COOR' to said metal salt Is In the range of from 1:1000 to 1:20,000,000 by weight.

4. A plant growth stimulator composition according to any one of claims 1 to 3, wherein said metal Ion Is selected from the group consisting of Ca+2, La+3, Mg+2, Mn+2, Sr+2, Pb+2, Ba+2, Cd+2, Zn+2, Cu+2 and Co+2.

I s an alkyl group having between 1 and 36 carbon atoms

J

37

204997

5. A plant growth stimulator composition according to any one of claims I to 3 consisting essentially of at least one long-chain compound of the formula R-COOR' and a water-soluble calcium salt.

6. A plant growth stimulator composition according to any one of claims 1 to 3 wherein said metal salt Is a calcium salt.

7. A plant growth stimulator composition according to any one of claims 1 to 3 wherein said metal salt Is an Inorganic metal salt.

8. A plant growth stimulator composition according to any one of claims 1 to 3 wherein said metal salt Is calcium chloride.

9. A plant growth stimulator composition according to any one of claims 1 to 3 wherein said compound of the formula R-COOR' is contained In a naturally-occurring wax or oil.

10. A plant growth stimulator composition according to claim 9, wherein said compound of the formula R-COOR' Is contained In a naturally-occurring wax or oil selected from the group consisting of beeswax, esparto wax, peanut oil, jojoba oil, olive oil, soybean oil, and rice bran oil.

11. A plant growth stimulator composition according to claim 9, wherein said compound of the formula R-COOR' Is contained In beeswax.

12. A plant growth stimulator composition according to any^one of claims 1 to 3 In powder or granular form.

2 3 OCT 193

CO

38

204997

13. A plant growth stimulator composition according to claim 9, In powder or granular form.

14. An aqueous plant growth stimulator formulation suitable for application to growing plants, comprising:

water; less than 10 mg per liter of at least one long-chain compound of the formula:

R-COOR'

wherein R Is a long-chain alkyl group having between 15 and 47 carbon atoms, containing between 0 and 6 carbon-carbon double bonds and 0 to 4 carboxyl groups or salts or derivatives thereof; and R1 is an alkyl group having between 1 and 36 carbon atoms, containing

0 to 6 carbon-carbon double bonds and 0 to 4 carboxyl groups or salts or derivatives thereof; or R1 Is hydrogen, or a salt thereof; and at least one metal ion salt which releases In water a metal ion having a valence of +2 or +3, wherein the weight ratio of the said compound of the formula R-COOR' to said metal salt Is In the range of from 1:5 to

1 .-500,000,000.

15. An aqueous plant growth stimulator formulation according to claim 14 wherein the ratio of said compound of the formula R-COOR' to said metal salt is In the range of from 1:100 to 1:50,000,000 by weight.

16. An aqueous plant growth stimulator formulation according to claim 14 wherein the ratio of said compound of the formula R-C00R' to said metal salt Is In the range of from 1 :1000 to 1:20,000,000 by wei ght.

1 1 FEB 1986 d!

39

204997

17. The plant growth stimulator formulation according to any one of claims 14 to 16 wherein said metal Ion Is selected from the group consisting of Ca+2, La+3, Mg+2, Mn+2, Sr+2, Pb+2, Ba+2, Cd+2, Zn+2, Cu+2 and Co+2.

18. The plant growth stimulator formulation according to any one of claims 14 to 16 wherein the concentration of said metal Ions Is between 1 mM and 30 mM.

19. The plant growth stimulator formulation according to any one of claims 14 to 16 wherein the concentration of said metal Ions Is between 1 mM and 50 mM.

20. The plant growth stimulator formulation according to any one of claims 14 to 16 consisting essentially of:

water; at least one long-chain compound of the formula R-COOR'; and a water-soluble calcium salt.

21. The plant growth stimulator formulation according to any one of claims 14 to 16 wherein said long-chain compound of the formula R-COOR' Is present In the amount of at least 0.001 mg per liter.

22. A plant growth stimulator formulation according to any one of claims 14 to 16 wherein said compound of the formula R-COOR' Fs contaIned In a naturaI Iy-occurrIng wax or oil.

23. A plant growth stimulator formulation according to cla-ft5v22 wherein said compound of the formula R-COOR' Is contained In a

^23 OCT 1985

40

204997

naturally-occurring wax or oil selected from the group consisting of beeswax, esparto wax, peanut oil, jojoba oil, soybean oil, and rice bran oil.

24. A plant growth stimulator formulation according to claim 22 wherein said compound of the formula R-COOR' Is contained In beeswax.

25. A plant growth stimulator composition according to any one of claims 1 to 3 in liquid form.

26. A method for stimulating plant growth which comprises applying an effective plant growth stimulating amount of the composition according to any one of claims 1 to 3 to the area where pi ants are growIng.

27. A method for stimulating plant growth which comprises applying an effective plant growth stimulating amount of the formulation according to any one of claims 14 to 16 to the leaves of growing plants.

method for stimulating plant growth which comprises effective plant growth stimulating amount of the according to claim 17 to the leaves of growing plants.

29. A method for stimulating plant growth which comprises:

applying an effective plant growth stimulating amount of the " o\';

P

formulation according to claim 20 to the leaves of growing plants, j,\j

1^23 OCT W85

\v ..

30. A method for stimulating plant growth which comprises:

28. A applying an formulation

41

204997

applying an effective plant growth stimulating amount of the formulation according to claim 21 to the leaves of growing plants.

31. A method for stimulating plant growth which comprises: applying an effective plant growth stimulating amount of an aqueous composition comprising:

at least one compound of the formula:

wherein R Is a long-chain alkyl group having between 15 and 47 carbon atoms, containing between 0 and 6 carbon-carbon double bonds and between 0 and 4 carboxyl groups or salts or derivatives thereof; and R'

containing 0 to 6 carbon-carbon double bonds and 0 to 4 carboxyl groups thereof; and at least one metal salt which releases a metal Ion having a valence of +2 or +3 in water to the area where plants are growing,

wherein the weight ratio between said compounds of the formula R-COOR'

Is In the range of from 1:5 to 1:500,000,000 by weight and wherein said compound of the formula R-COOR' Is applied in an amount of at least 0.01 mg per acre.

32. The method according to claim 31 wherein the ratio of said compound of the formula R-COOR' to said metal salt Is in the range of from 1:100 to 1:50,000,000 by weight.

33. The method according to claim 31 wherein the ratio of said compound of the formula R-C00R' to said metal salt is in the range of from 1:1000 to 1:20,000,000 by weight. ^^ c

R-COOR'

I s an alkyl group having between 1 and 36 carbon atoms,

or salts or derivatives thereof; or R' Is hydrogen, or a salt

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34. The method according to any one of claims 31 to 33 wherein said compound of the formula R-COOR' Is contained In a naturally-occurring wax or oil.

35. The method according to any one of claims 31 to 33 wherein said compound of the formula R-COOR' Is contained in beeswax.

36. The method according to any one of claims 31 to 33 wherein said plants are selected from the group consisting of field corn, sweet corn, wheat, soybeans, alfalfa, rice, peas, tomatoes, peppers, cucumbers, lettuce, radishes, beans, tobacco, cotton, barley, potatoes, and kentucky bluegrass.

37. A method according to any one of claims 31 to 33 wherein said composition Is added to the water used for Irrigation of said area where said plants are growing.

38. A method according to any one of claims 31 to 33 wherein said composition Is applied to the seed soak or soli drench.

39. A method according to any one of claims 31 to 33 wherein said composition Is applied to said plants at a stage when said plants have between 2 and 7 true leaves.

40. A method according to any one of claims 31 to 33 wherein said composition Is In powder or granular form.

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41. A plant growth stimulator composition according to claim 1 substantially as herein described with reference to the Examples.

42. An aqueous plant growth stimulator formulation suitable for application to growing plants according to claim 14 substantially as herein described with reference to the Examples.

43. A method for stimulating plant growth according to any one of claims 26 to 31 substantially as herein described with reference to the Examples.

By His/Their authorised Agent

A. J. PARK & SON Per: (yrtS

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