MXPA98008989A - Mixes and methods to delete the precipitation of cloroacetami - Google Patents

Abstract

The invention offers novel mixtures and methods to significantly lower the temperature at which chloroacetamides begin to form a solid precipitate, without significantly diluting the chloroacetamid.

Description

MIXES AND METHODS FOR DELETING THE PRECIPITATION OF CHLOROACETAMIDES FIELD OF THE INVENTION The present invention relates to mixtures and novel methods that have the effect of distinguishing the point of precipitation of loroaceta ida. BACKGROUND OF THE INVENTION Clarsacetamides are known herbicides. More particularly, they are herbicide inhibitors of plant growth that mainly inhibit the growth of roots and shoots. Examples of laracetamide herbicides are alacor, etolacar, acetoclsr, metazaclar, diett lo, prapaclar and iofenamines. An example of a known tiaf namipa which is a plant growth inhibiting herbicide is the d i -fine or whose chemical name is 2-chloro- - (2, 4-d ime i 1-3-ieni 1-N- (2-meto i-l-me i le i 1) -aceta i a.

Processes for its production, herbicidal compositions that contain it as well as its use as a herbicide are described in the North American patent no. 4,666,502, the content of which is incorporated herein by reference. Dimetenamids consist of 4 stereoisomers as iastereomeric mixtures (1S, aRS (known as S-dimethena gone) and IR, aRS (known as R-di ethenamide)) and as a racemic mixture (1RS, aRS). References here to chloroacatamides, including dimethenamid, refer to their various forms, including their various stereoisomers, unless indicated otherwise. A commercially available product is available under the trademark FRONTIER < m r (BASF AG, Germany), with either 6.0 pounds / gallon or 7.5 pounds / gallon dimethenamid together with other inert ingredients such as, for example, petroleum distillates, < i. wood or aromatic solvents of xylep rank. While the use of chloroacetamides, including dimethenamid, as growth inhibiting herbicides is known in the art, a disadvantage in terms of commercial use is their point of precipitation - the temperature, at which, at standard atmospheric pressure, the liquid clsroacetamides they begin to solidify to form a solid precipitate. The racemic mixture of dimethenamid has a precii ation point of approximately 20 ° C-22 ° C. As a result of this property, these commercial products tend to precipitate at common temperatures in the commercial use of the herbicides. For example, the product FRONTIER < mr > which comprises 7.5 pounds of dimethenamid per gallon, tends to form a solid precipitate at temperatures of 12βC-13 * 0 and even lower. The temperatures at which these formulations are subjected during normal distribution and application in the field often fall below 12 ° C - IS'C, which results in the formation of precipitate of dimatena gone. This poses a problem to the user-I eat because, among others. -T the p re i p? '-, 3 > . ion prevents q > - > = - the u = as • - is applied uniformly the herbicide on the crops. Thus, commercial users should typically heat the dimethenamid products before use, which can be expensive and time-consuming. Alternatively, the manufacturers of dimetena ida products should rotate their existence of di etenamids in heated storage with dimethenamide not used in the facilities of commercial users that has been exposed to temperatures below 12 ° C - 13'C. It is known that the temperature at which a dissolved liquid is frozen or precipitated can be lowered by decreasing the mole fraction of the solute in solution of the liquid solvent. The magnitude with which the precipitation temperature is affected is generally directly proportional to the magnitude with which the mole fraction of the solvent was decreased. If a solution is an "ideal" solution, the magnitude at which the low precipitation temperature by the addition of a solute is not affected by the composition of the solvent or solute, and a curve made by plotting the precipitation temperature. versus the concentration will not vary with the use of different compounds to dilute the liquid. The term "ideal solution" refers to a solution in which little or no specific molecular interaction occurs between its components. An "ideal solution" complies with Raoult's law. A) Yes, an alternative theoretical approach to avoid the need to heat clearacetamide herbicides before use is to significantly decrease the mole fraction of the herbicide in solution. A preferred diluent known camo gamma butyrolactone can be used to decrease the melting point of dimethenamid to -20 <; C, but to achieve this, the di-ethemid in solution must be diluted to 20K molar (45 * / weight). However, by significant dilution of the herbicide, its effectiveness is reduced. In addition, a dilution means the herbicide iva results in a significant increase in the amount of total product required to achieve the desired herbicidal result. This not only results in a higher cost for the user based on the amount of product purchased, but also increases significantly the cost of freight, energy and product application. Extensive experiments were carried out to try to decrease the precipitation temperature of the chloroacetic ida herbicide, the di ethamido, combining it in solution with several substances, and decreasing the temperature of the solutions in an increased manner obsevándalas to determine the formation of solid precipitate. The precipitation temperature of the di tete L for each solution was determined as the temperature, at approximately standard atmospheric pressure, in which the solutions provided at least one trace of the solid precipitate of diraetene. The term "fingerprint" is used herein to refer to a quantity of solid precipitate that can be visibly detected without the need for amplification, but which can not be removed without the aid of amplification. If the amount of solid precipitate can be measured visibly without the aid of amplification, then it is considered to be more than a trace. It is understood that most substances form ideal, or almost ideal, solutions with the dimethenamid, and therefore, if the melting point of dimethenamid does not appear to be substantially depressed without significant dilution of the dimethenamid. If the effect on the precipitation temperature is lower, the displacement of the ideal level with these substances is not significant enough to be useful, and the substances are not acceptable in commercial herbicide formulations. Accordingly, no method is currently available to inhibit the growth of solid precipitate in chloroacetamide solutions at conventional freight, almicepamt and agi ation temperatures, e. I accept the d? lu "-? n unacceptable. Accordingly, commercial users of chloracetacetazide herbicides, for example dimethyramide, can not use such liquid products, substantially free of solid precipitate, and such products have been transported or stored at substantive temperatures below 12 ° C. - 13 ° C, without having to heat the product to melt or redissolve the solid precipitate. Since the known diluents can lower the pre-ipitation point only by a substantial dilution of the herbicide, the only alternatives for the users in these conditions have been either to fill products containing solid precipitates or to use the expensive step and which requires time to heat the products to melt or dissolve the solid precipitate. SUMMARY OF THE INVENTION It has surprisingly been found that the temperature at which the chloroacetamide herbicide, dimethenamid, forms a solid precipitate can be significantly decreased with a less significant dilution of dimethepamid than is available to date. The invention of race chloroaceta ida compositions having improved stability at low temperatures and methods for decreasing the precipitation point of chloroacetamides.

The precipitation temperature of chloroacetamides is lowered and í =? n - "e the chloro-ice combination t -io * i d a cor, caiito these Chemicals from 3 to s i ii l nte formula: where R 1 is either chloro or methoxy, and R 2 is optionally hydrogen, halogen or a lower alkyl, a lower alkyl ether, or a lower alkyl halide. According to a preferred embodiment of the present invention, a herbicidal mixture comprises a herbicidally effective amount of dimethenamid and 3,6-d-chloro-2-methoxybenzoic acid, known as bicamba acid, where the molar concentration of bicamba acid is 30% at 50V , of the total molar concentration of dimethenamid and bicamba acid. The mixture can also be diluted with known inert ingredients such as, for example, gamma bu or olactone, petroleum distillate, xylem or aromatic solvents of oleic range, to adjust the concentration of the herbicidal components. BRIEF DESCRIPTION OF THE DRAWING The drawing forming a part of the original presentation of the invention: Figure 1 is a graph showing the precision point of the dimethenamid in various molar concentrations ep combines ion with bicamba and with gamma butyrolactone. DESCRIPTION OF THE PREFERRED MODALITIES In the following detailed description, preferred embodiments of the present invention are described to enable the practice of said invention. Even when specific terms are employed to describe and illustrate the preferred embodiments, such terms are not intended to limit the practice of the invention. In addition, although the invention is described with reference to the preferred embodiments, numerous variations and modifications of the invention will be apparent to those skilled in the art upon consideration of the foregoing and the following detailed description. The compositions of the invention include a herbicidally effective amount of a chloroacetamide, for example alaclsr, metolachlor, acetochlor, metazachlor, dietyl, propachlor or thiophenamyzae such as dimateamide, combined with a precipitation point depletion agent. An appropriate proportion is prepared: the chloroacetamide and the precipitation point depletion agent are added on a mole / mole basis, to approximately 2.5: 1, with a preferred ratio of about 3: 2. In accordance with the present invention, the agents s > - 'decrease of re-read point i are compue: - •.-._ > : -_ that have the following chemical formula; where R 1 is either chloro or ratatoxy, and R 2 is optionally hydrogen, halogen, a lower alkyl, a lower alkyl ether, or a lower alkyl halide. Examples of such precipitation point reduction compounds include dicamba acid (2,6-dichloro-2-methoxybenzoic acid) and 2,6-dichlorobenzoic acid.Dicamba is a known herbicide plant growth regulator which is frequently used in herbicide control after the emergence of broad-leaved herbs in monocots and lemons, a product of commercially available dicamba is known as BANVEL (r) (BASF AG, Germany), which harbors 4.0 pounds / gallon of dicamba acid in inert diluents. Even though dicamba acid and other benzoic acids are known regulators of plant growth, they have not been combined to date with chloroacetamides, as, for example, di ethenamide, according to the proportions of the present invention and have not achieved the distribution effects of point and pre ipita tion of the pre in e m-tion. Mixtures of these compounds with the chlorineacetamide herbicide enamide within the parameters of the above proportions present surprisingly low precipitation temperatures, which allows the temperatures of said salucians to fall to below -20aC before observing a trace of solid precipitate. Also, when the temperatures of these solutions were lowered to a point at which precipitation was observed, the amount of solid precipitate formed was lower, and formed much more slowly, than when the dimethenamid is combined with other known diluents. Infrared spectra for mixtures of dimethenamid and dicamba reveal a shift in the carbonyl bands of both dimethenamid and dicamba, as compared to the infrared spectra of dimethenamid and dicamba unmixed. In addition, both substances, when in excess of stoichiometric in relation to the other, showed displaced and non-displaced carbonyl bands, which suggests a certain chemical bond in relation to the carbanylate components of the two substances. Likewise, the test of mixtures of di etendant and dicamba pair thin layer chromosome showed that the two substances are easily separated in this way. This shows that no covalent linkages are formed between the imetepami and dicamba, that the association between the DOU-SUITU; It is relatively weak and dynamic. It is interesting to note that, when determining the precipitation temperatures for solutions containing various amounts of dicamba and 2,6-dichlorobenzoic acid mixed with dimethenamid, it was found that the dicamba and the 2,6-dichlorobenzoic acid are soluble in dimetene up to molar concentrations approximately 10 equal to the molar concentration of dimethenamide. When the molar concentration of dicamba or of 6-dichlorobenzoic acid exceeds that of the dimethenamid, the dicamba or the 2,6-dichlorobenzoic acid precipitates and significant heating is required to return to the Í5 solution. In order to determine whether the anomalous depression of the precipitation temperature in dimethenamid is due to the benzoic acid structure of these compounds, the solubilities of other similar benzoic acid structures in dimethenamide were measured. Surprisingly, similar structure-like benzoic acids, such as 3,5-dicamba acid, are much less soluble in dimethenamid qua dicamba and 2,6-diclarobenzaic acid, suggesting a strong structural specificity in the interaction between dimethenamid and both dicamba and acid 2, -diclorsbenzoi or.

It is known that this structural specificity is found in the location of the lorpas and the oxy acid adjacent to the acid group both in the diam- icated zone and in the 2,6-dichlorobenzoic acid, and that the electronic affinity «Of these groups increases the interaction of the acid group of these molecules with the dimethyltene carbonyl components. The grades and formulations described herein can be prepared in a manner known per se, particularly by the agitation of compounds and other customary adjuvants of the invention. formula in the dimethenamid while stirring and optionally under heating. In a preferred embodiment, the dimethenamid is heated to about 115 ° F before the addition of the dicamba. Likewise, the concentration of the components can be varied by combining the mixtures, using methods known per se, particularly the agitation of the known diluent compounds. As used herein, the term "diluent" refers to any liquid or solid material acceptable in agriculture that can be added to the components to offer an easier or improved form of application, or to achieve an employable or desired strength of activity.

Examples are gamma bu i rsiactone, petroleum distillates,? Ylene, or aromatic solvents of xylene range. In a preferred embodiment, the present invention comprises approximately 5 pounds per gallon of dimethenamid and about 1 pound per gallon of dicamba with commercially available diluents. For example, petroleum distillates, xylene, or good xylene range aromatic preservatives. At this concentration, the dicamba has the desired effect of decreasing the temperature of the precipitate of the effluents and the mixture has the desirable viscosity to facilitate its application by commercial users. The formulations of the present invention can also include other ingredients or adjuvants commonly employed in the art, including penetrants, surfactants, crop oils, displacement control agents, foam removal agents, preservatives, antifouling agents, adhesives. , antimicrobial agents, and the like, including mixtures thereof, as are well known in the art and presented camo for example, in the aforementioned US patent no. 4,666,502. Herbicidally acceptable additives may be added to the mixtures, using methods known per se, particularly by agitation, including other compounds having a similar or suitable herbicidal activity to either compounds having an antidote, fungicidal or insecticidal activity. Particular formulations to be applied in the form of spraying may contain surfactants, such as, for example, humidification and dispersion agents, for example, a side-viewketed alkyl or a fatty alcohol bound thereto. Likewise, entas da i ni. Compatibility, such as emulsifiers. can be used for the purpose of improving the compatibility of the formulations when such formulations are combined by a final user, for example, with products containing water, for example, in one embodiment, the formulations of the present invention are combined with a mixture of nonionic / anionic surfactants, and a phosphate ester to emulsify the formulations of the present invention in water. further, the mixtures and formulations described herein can be employed in various herbicidal applications as known, per se, in the art, and are described in the aforementioned North American patent na. 4,666,502. The following examples present the effects of decreasing the crystallization point of the dime and licking of various formulations of the present invention. EXAMPLES Solutions were prepared at room temperature under standard atmospheric pressure. The solutions were cooled to a temperature of -20 ° C. Precipitation temperatures for dimethenamide solutions with dicamba were recorded as the lower temperature at which at least one trace of dimerna was produced in the solution. The results appear in Table 1 below: TABLE 1 Malar fraction tt by weight of molecular weight F of disinfectant di methane of 0.938 95 tt 0.062 .878 90 tt .122 0.820 85 V, O.180 0.762 80 tt O.238 0.706 75 tt .294 0.652 70 tt 0.348 .598 65 tt .402 0.546 60 tt 0.454 0.495 55 tt 0.505 0.445 5 tt 0.555 0.396 45 tt .604 0.348 40 tt .652 0.301 35 tt .699 0.256 30 tt 0.744 0.211 25 tt 0.789 .167 20 tt O .833 0.124 15 tt 0.876 0.082 i O tt 0. 18 0.040 5 tt .960 Molar fraction tt by weight Temperature of dimethenamid of dicamba precipitation in OC 0. 38 5. A 19 0.878 1 0.820 1 1 0.762 20 12 0.706 25 tt 9 (footprint) 0.652 30 tt - 20 0.598 35 tt - 20 0.546 40 tt - 20 0.495 45 tt - 20 0.445 50 tt 81 * 0.396 55 tt 89 * 0.348 60 K 94 * 0.301 65 tt 96 * 0.256 70 tt l O * 0. 11 75 tt 102 * 0.167 80 tt 104 * 0.124 85 tt 108 -s? - 0.082 90 tt 110 * 0.040 95 tt 112 * * Solid formulations in dicamba conceptions of 0.505 mole fraction, and below, were precipitates of dimetena ids. Above this concentration, a precipitate of dicamba was formed, which required significant heating to be redissolved in the solution.

It is shown in Table I above, when the dicamb 3 is present in higher concentrations than in the past. imadamante 0.30tt molar, < n = say, it is that the 5tt in - so, the preti t ion temperature of the low d da mi mi da da da da da da da da da da da da da da da da da da da da............. By way of comparison, the metenamide precipitation temperature was measured in a similar manner in solutions with varying concentrations of gamma but irolactopa ("Gamma Bio"), a canocid diluent. The precipitation temperatures of the dimethenamid in these solutions are presented in Table 2 below: TABLE 2 Molar fraction tt by weight of Molar fraction ds of dimethenamid d i etenami do gamma bu rol a ona 0. 856 95 tt .144 0.737 90 tt 0.263 0.639 85 tt O.361 0.555 SO tt .445 0.484 75 tt O .516 0.421 70 tt .579 0.367 65 tt O.633 0.319 60 tt O.681 0.276 55 tt 0.724 0.238 50 tt 0.762 0.203 45 tt .797 0.172 40 0.828 0.144 tt O, Fraction malar tt malar Tempera u dimetenami og mma precip i tai buti role actana 0.856 5% 18 0.737 10 tt 18 0.639 15 tt 18 0.555 20 tt 17 0.484 25 tt 15 0.421 30 tt 13 0.367 35% 9 0. 19 40 tt 7 0. 76 45 tt 4 0.238 50 tt - 7 0.203 55 tt - 20 0.172 60 tt - 20 0.144 65 tt - 20 As shown in Table 2 above, a significantly greater amount of gamma butylactapa is required to distinguish the precipitation temperature of the di etenaroids, in conjunction with the amount of dicamba required to reach a similar dimethenamide temperature. The amount of dicamba required to attain a temperature of 10% C at a temperature of -20 ° C is approximately 30%, which is equivalent to a mole fraction of approximately 0.35. However, the amount of gamma but i rolactone required to achieve a precipitation temperature of -20 ° C is approximately 55tt in weight - equivalent to a mole fraction of about 0.8 The difference in how much the precipitation temperature falls The result obtained with dicamba co or the temperature decrease agent of the ion price, compared to the normal decrease caused by the dilution of dimethenamide, was more easily observed in the graph presented in figure 1. In the figure, curve 1 indicates the temperature of the precipitate ion observed in dimethenamid and dicamba solutions As shown in figure 1, the temperature of the dimethenamidium is significantly reduced by dicamba starting at the point at which the mole fraction of dimethenamid is about 0.70 and the mole fraction of dicamba is about 0.30. The line A-A indicates the approximate point at which the dicamba begins to precipitate and requires a significant heating for the dicamba to return to a state of solution. Curve 2 in Fig. 1 illustrates the decrease in di ethenamide precipitation temperature by dilution with gamma bu irolactone. Eat the illustrated figure 1, in order to reduce the precipitation temperature of the significant dimethenamid with gamma bu i olactone, the mole fraction of dimethenamid should be significantly diluted more than with dicamba. For example, with dicamba, the mole fraction of dimethenamid in which the dimethenamid has a precipitation temperature of 10 ° C is about 0.70, while, with gamma but i rolactop, the mole fraction of the dimethenamid in which the dimethenamid has a Precipitation temperature of lO'C is approximately 0.37. Similarly, with dicamba bed precipitation temperature decrease agent, the dimethenamid has an ion precipitation temperature of -20 * C with a mole fraction of dimethenamid of about 0.65. With gamma but i alactana as diluent, in order to decrease the precipitation temperature of the dimethenamid at -0 ° C, the mole fraction of dimethenamid should be decreased to about 0.2O. Tests of a similar protocol were performed using combinations of dimethenamids with 2,6-dichlorobenzaic acid. The results of these tests showed a similar suppression of the precipitation point as what was observed with combinations of dimethenamid with dicamba acid. The results appear in Table 3 below. TABLE 3 Fr3.cc i?, Molar tt by weight of Frac in molar of dimethenamid dimethenamid 2, 6-d l lor or 0.929 95 tt 0.071 0.862 90 tt O.138 0.797 85 tt 0.203 0.735 80 V. 0.265 0.675 75 tt 0.325 0.618 70 tt 0.382 .563 65 tt 0.437 0.510 60 tt 0.490 O.458 55 tt .542 0.409 5 tt .591 0.362 45 tt O.638 0.316 40 tt O .684 Molar fraction tt molar of Temperature of dimethenamid 2, -d icloro rec ip i tac ion in ° C .929 5 tt 18 0.862 1 tt 16 0.797 15 tt 15 0.735 20 tt - 20 0.675 25 tt - 20 0.618 30 tt - 20 .563 35 tt ÍO 0.510 40 tt? O O.458 45 tt 49 ** 0. 09 50 tt 71 ** 0.362 55 tt 73 ** 0.316 60 tt 91 ** ** As in the case of the determination of precipitation temperature in relation to dicamba, starting at the point at which the molar phase of 2,6-dichlorobenzaic acid exceeds the mole fraction of dimethenamid, 2,6-dichlorobenzoic acid is it precipitates and requires an important heating to dissolve in the dimethenamid. Likewise, as in the case of dicamba, infrared spectra for mixtures of dimethenamid and 2,6-dichlorobenzaic acid show a shift in the carbonyl bands of both substances, suggesting a certain chemical bond in terms of carbon components. of the two substances. To demonstrate the commercial utility of the decrease in the precipitation temperature provided by this invention, formulations of dimethenamid and dicamba acid were prepared in weight ratios between dimethenamid and dicamba acid of 2: 1 and 3: 1, corresponding to molar proportions of 1.6: 1 and 2.4: 1, respectively. With gamma butyrolactone a known diluent, samples of the formulations were diluted so that the concentration of total active ingredients (say, di ethenamide and dic ba) were 8 pounds per gilon, "" pounds per gallon and 6 pounds per gallon. Diluted samples, and samples of dimethenamid and dicamba mixture in 2: 1 and 3: 1 by weight proportion, undiluted, were then cooled in increments of 10 ° C, seeded with solid ditetenes and solid dicamba after each increment of cooling, and observed to determine the growth of a solid precipitate. At a temperature of - 200C, none of the samples presented precipitation, even after sowing. At a temperature of -30 ° C, 4 days after sowing, the samples were diluted and the 3 to 1 mixture that had been diluted at 8 pounds per gallon began to show slight traces of solid precipitate.

The mixtures were then cooled to -40 ° C and seeded again with solid dimethenamide and solid dicamba. Three days after sowing, the mixtures having a weight ratio of 2 to 1 between dimethenamid and dicamba had only solid dimetenamide traces. The mixtures having a weight ratio of 3 to 1 between dimethenamid and dicamba showed a more significant growth of solid precipitate. The solutions were then heated in increments of 1 ° C to an O'C temperature to observe the temperatures at which only one trace of the solid precipitate remained and 1? temperature at which all the solid pieced returned to the final solution. The results appear in the following Table 4: TABLE 4 Relationship Concentration Remain Not remain weighted between after solids ° C dimetena ida diution of the solids icamba and QC 2: 1 no dilution N / A * N / A * 2: 1 8 pounds / gallon N / A * -9 2: 1 7 pounds / gallon N / A ** -11 2: 1 6 pounds / gallon N / A ** -11 3: 1 no dilution -39 N / A *** 3: 1 5 pounds / gallon -lO -3 3: 1 7 pounds / gallon -15 -8 3: 1 6 pounds / gallon -16 -12 * only solid and precipitate traces are present at the beginning of the heating (-39QC) and also at the end of the heating (0 ° 0. ** only traces of solid precipitate are present at the beginning of the heating (~ 39 ° C). ** * Traces of solid precipitate remain at the end of the heating (0 ° C).

The invention has been described in detail in relation to its preferred embodiments. However, numerous variations and modifications can be carried out within the spirit and scope of the present invention without departing from the invention as described in the above specification and defined in the appended claims.

Claims (34)

1. CLAIMS 1. A composition suitable as a herbi that includes one. effective amount of n her b .c? > With a clear acetamidog and a decreasing agent for the precipitation temperature of 3aacetaacetamide, said composition comprises at least about 40tt molar concentration of the clearcoat herbicide id, and said rate of decrease of the precipitation temperature is preset in a Sufficient amount such that said composition is substantially free of solid chlorsacetamide at a temperature below about 10 ° C.
2. 2. A composition according to claim 1, wherein said c-haloacetic ida herbicide is selected from alachlor, metaalachlor, acetochlor, etazaclar, diatathyl, propachlor and thiophenamine.
3. 3. A composition according to claim 1, wherein said cioraacetamide herbicide campdens a thien ofenamine.
4. 4. A composition according to claim 1, wherein said chloroacetic ida herbicide comprises di ethenamide.
5. 5. A compliance composition as claimed in claim 1, wherein said precipitation temperature decreasing agent comprises at least one compound having the formula where R 1 is either chloro or methoxy, and R 2 is optionally hydrogen, halogen, lower alkyl, lower alkyl halide, or a lower alkyl ether.
6. 6. A composition according to claim 5, wherein said precipitation temperature decreasing agent consists essentially of dicamba acid, 2,6-dichlorobenzoic acid, or combinations thereof.
7. 7. A composition according to claim 5, wherein said precipitation temperature decreasing agent comprises dicamba acid.
8. 8. A composition according to claim 5, wherein said precipitation temperature decreasing agent comprises 2,6-dichlorobenzoic acid.
9. 9. A composition according to claim 4, wherein said precipitation temperature decreasing agent comprises at least one compound having the formula where R 1 is a chloro to ethoxy, and P 2 is, optionally, hydrogen, halogen, lower alkyl, lower alkyl halide, or b? "= - n a lower alkyl ether.
10. 10. A composition according to claim 9, wherein said precipitation temperature decreasing agent consists essentially of dicamba acid, 2,6-dichlorobenzoic acid, or compositions thereof.
11. 11. A composition according to rei indication 9, wherein said precipitation temperature decreasing agent comprises dicamba acid.
12. 12. A composition according to claim 9, wherein said precipitation temperature decreasing agent comprises 2,6-dichlorobenzaic acid.
13. 13. A composition according to claim 10, wherein said precipitating temperature decreasing agent is present in a sufficient amount such that said composition is substantially free of solid dimethenamid at a lower temperature * at approximately 5 ° C. .
14. 14. A composition according to claim 10, wherein said precipitation temperature decreasing agent is present in a sufficient amount such that said composition is substantially free of solid dimatenamide at a temperature below about 0 ° C.
15. 15. A composition according to claim 10, wherein said agent gives a decrease in the temperature of the sensation in a sufficient amount such that said composition is substantially free of said solid dimethenamid at a temperature higher than about -10 ° C,
16. 16. A composition according to claim 10, wherein said precipitation temperature decreasing agent is present in a sufficient amount such that said composition is substantially free of solid dimethenamide at a temperature lower than Approximately -20"C.
17. 17. A compliant composition with claim 10, wherein said precipitation temperature decreasing agent is present in a sufficient amount such that said composition is substantially free of solid dimethenamid at a temperature below about -30 ° C-
18. 18. A composition according to claim 10 , wherein said precipitation temperature decreasing agent is present in a sufficient amount such that said composition is substantially free of solid dimethenamid at a temperature below about -40 ° C.
19. 19. A composition suitable as a herbicide comprising 50 a herbi tively effective amount of ethenamide and an agent for lowering the temperature of the pre-ionization of the liquid, the ratio of the average to the age of the * »Gives pr .---. ?? 1 a.- i on ^ = found within a range of approximately 1: 1 to approximately 2.5: 1, and said composition is substantially free of crystalline dimethenamid at a temperature below about 5 * C.
20. 20. A composition in accordance with rei indication 19, wherein said precipitation temperature decrease agent comprises at least one compound having the formula: Rl is chloro to methoxy, and R 2 is optionally hydrogen, halogen, lower alkyl, lower alkyl halide, or a lower alkyl ether.
21. 21. A composition according to claim 20, wherein said precipitation temperature decreasing agent consists essentially of dicamba acid, 2,3-diclarobenzidoic acid, or compositions thereof.
22. 22. A composition according to claim 20, wherein said pre-ip ation temperature decreasing agent comprises dicamba acid.
23. 23. A composition in accordance with the rei indicates ion 20, wherein said precipitation temperature digestion agent comprises 2,6-dicylarobenzoic acid.
24. 24. A composition in accordance with rei indication 20, wherein said precipitation temperature decreasing agent is present in a sufficient amount such that said composition is substantially free of solid dimethenamid at a temperature not less than about 0. ° C,
25. 25. A composition according to claim 20, wherein said precipitation temperature decreasing agent is present in an amount sufficient for said composition to be substantially free of solid dimethenamid at a temperature of less than about -10 °. C.
26. 26. A composition according to claim 20 wherein said precipitation temperature decreasing agent is present in a sufficient amount of such a mill that said composition is substantially free of solid dimethenamid at a temperature of less than about 20 ° C.
27. 27. A composition according to claim 20, wherein said precipitation temperature decreasing agent is present in a sufficient amount such that said composition is substantially in the solid state at a temper- ature lower than approximately -30 ° C.
28. 28. A composition according to claim 20, wherein said precipitating temperature decreasing agent is present in a sufficient amount such that said composition is substantially free of solid di-ethenamide at a temperature less than about -40"C.
29. 29. A composition according to claim 25, wherein the malar ratio between the dimethenamid and the precipitator temperature decreasing agent is within a range of about 1.5: 1 to about 2: 5. A composition according to claim 25, wherein the molar ratio between the di ethenamide and the precipitation temperature decreasing agent is about 1.5: 1. 31. A composition according to claim 25, further comprising a diluent. acceptable in agriculture 32. A method to form a composition of stable diTetanamids during the storage or at low temperatures, which comprises the combination of dimethenamid with an agent for decreasing the temperature of precipitation of the dimethenamid and of molar Ott at about 50tt molar gives an acceptable diluent in agriculture, to form a composition qua a molar concentration gives greater dimethenamide that approximately 40tt molar based on the total amount of said dimethenamid, precipitation temperature decrease agent, and diluent in said composition, said precipitating temperature decreasing agent is present in a sufficient amount such that said composition is substantially free of solid dimethenamid at a temperature below about 0 ° C. 33. A method according to claim 32, wherein said precipation temperature decreasing agent is present in a sufficient amount such that said composition is free of solid dimetenamide at a temperature less than about -10. ° C. 34. A method of conformance with rei indication 32, wherein said precipitation temperature decreasing agent is present in a sufficient amount such that said composition is substantially free of solid diεtene at a temperature less than about -20 °. C. A method of conformance with the rei indicates ion 32, wherein said precipitator temperature decreasing agent finds a sufficient amount in such a way that such a composition is sufficient. S'a.- s. d >; - d imetenami do s lide .. - a al ... r infa. IOG at approx. -3"C. 36. A method according to claim 32, wherein said precipitation temperature decreasing agent is present in a sufficient amount such that said composition is substantially free of solid dimethenamid at 37. A method according to claim 32, wherein said ion precipitation temperature decreasing agent comprises at least one compound having the formula: where R 1 is either chloro or methoxy, and R 2 is optionally hydrogen, halogen or a lower alkyl ether. 38. A method according to claim 37, wherein said precipitation temperature decreasing agent consists essentially of dicamba acid, 2,6-d iclorobanzoics, or combinations thereof. 39. According to the method in accordance with the invention, Honda said a decrease in the temperature of the crystal, including the dicamba. 40. A method according to claim 37, wherein said agent for lowering the crystallization temperature comprises 2,6-dichlorobenzoic acid. 41. A method according to claim 37, wherein the concentration of the precipitation temperature decreasing agent in said composition is less than about 40tt molar based on the total amount of said dimetenamide, precipitation temperature decreasing agent, and diluent in said composition. 42. A method for forming a stable dimetenamide composition in storage at low temperatures, comprising the combination of dimethenamid with aprimax imatically 30tt molar to about SOtt molar of dicamba and molar Ott to about SOtt molar of an acceptable diluent in agriculture , to form a composition having a mole concentration of dimethenamid greater than imtimately 40tt molar mole based on the total amount of said di ethenamide, dicamba and di luent in said composition, said dicamba is present in a sufficient amount such that said composition is substantially free of solid dimethenamid at a temperature below about -0 ° C. 43. A method to form a composition of stable dimetenamids in 3 ma anami-low -reperes turis, which compteda 1 - "comination of dimatena gone with ap apros * 30ad molar to approximately 50tt molar gives acid 2, 6-d? Clarabenzo? Co and from Ott molar to about SOtt molar of a diluent acceptable in agriculture, to form a composition having a molar concentration of dimethenamid greater than about 40tt molar based on the total amount of said dimetenamids, acid 2,6-diclarobenzaic and diluent in said composition, said 2,6-d-chlorobenzoic acid is present in a sufficient amount such that said composition is substantially free of solid di ethenamide at a temperature less than -20aC approximately.