IL43876A - Plant regulator compositions based on 2-hydroxycycloalkyl quaternary ammonium compounds and new compounds of this type - Google Patents

Description

PLANT REGULATOR COMPOSITIONS BASED ON 2 -HYDROXYC YCLOALKYL QUATERNARY AM- . MONIUM COMPOUNDS AND NEW COMPOUNDS OF THIS TYPE mma-in D»ooiaan; Q'nax mo'ii o'va n lniD-im 'aiyan QV JIOK p¾»Ri¾>p'j'ofnTn-2. n.T..iioD nivm This invention pertains to the general field of plant regulators and particularly to compositions which control and regulate plant growth by retarding or stimulating said growth. Plant regulators are defined in the U.S. Department of Agriculture publication Interpretation Number 3 of the Regulations for The Enforcement of the Federal Insecticide, Fungicide, and Rodenticide Act (Revision 1, November 1964) at Section 362 - 101(a) (11) It has been known that quaternary ammonium compounds exhibit biological activity, and plant regulator activity has been reported for quaternary ammonium derivatives of limonene, and trimethylammonium derivatives containing a terpenoid moiety. The unusual plant responses, such as the high order of plant regulator activity, caused by the 2-hydroxycyclohexylammonium compounds described herein, have not been previously suggested or reported.

This invention pertains to novel compositions for regulation of plant growth, comprising as an essential active ingredient either an alkyl (2-hydroxycycloalkyl) dimethylammonium salt in which the alkyl group is C6 to Ci6, or a corresponding 2-ester, such as a compound having a 2-alkanoate group in place of the 2-hydroxy.

These compositions are highly effective plant regulators, causing substantial growth retardation, growth stimulation, abscission of leaves and growing tips, and other growth anomalies on various species of plants, without causing death of the plants ; they provide a method of regulating the development of plants without killing the plants.

The invention also pertains to certain quaternary ammonium salts which are new compounds and which are 43876/2 effective in the regulation of plant growth. The invention also pertains to the enhancement of. the activity of the compositions,' particularly in terms of stimulatory effects, by certain specific spreader-activator ad uvants, The active compounds of this invention are members of the class having the general formula: • ': : < '. ' where a straight alkyl alk lene ■ of 3 ring with the l lly acceptable anion not of itself phytotoxic, the nature of which is not critical, as for example halide, sulfate, phosphate, sulfonate, and alkanoate of 1 - 8 carbon atoms.

Preferred compounds are those in which R is H, ^ R' is a straight alkyl radical of 10 - 14 carbon atoms, and R" is tetramethylene radical, which with the 1- and 2-carbon atoms forms a cyclohexane ring.

The preferred compounds may be prepared by the following sequence of reactions: The acetates may be prepared by acylation of the quaternary salt: or by acylation of the amine, followed by quaternization III Synthesis of representative compounds is exemplified in the following examples. In the examples, all temperatures are in degrees centigrade, and all parts are by weight unless otherwise stated.

Example 1 (2-Hydrox cyclohexyl) (dimethyl) octylammonium bromide a. 2-Dimethylamino-l-cyclohexanol A mixture of 50.0 g of cyclohexene oxide and 100 ml of 25 percent aqueous dimethylamine was heated with stirring at 145° in a small autoclave for 8 hours. While the mixture was being concentrated to dryness at 50° on a film evaporator, absolute ethanol was added periodically to aid in removal of water. The residue was distilled through a Nester-Faust spinning band column to give 53.0 g of 2-dimethylamino-l-cyclohexanol , b.p. 64.1 -64.2/2.4 mm. The infrared electromagnetic spectro analysis was consistent with the assigned structure. b. (2-Hydroxycyclohexyl) (dimethyl) octylammonium bromide A solution comprising 5 g of 2-dimethylamino-l-cyclohexanol , 10 g of 1-bromooctane and 5 ml of dimethylformamide was heated in a glass pressure bottle at about 95° for 16 hours. p_-Xylene (25 ml) was added and the solution was concentrated at 60° using a film evaporator to remove dimethylformamide as its azeotrope ' with xylene. A second 25 ml portion of p_-xylene was added and the azeotrope distilled until the residue was free of volatile material. This residue was dissolved in water, and the aqueous solution was extracted five times with diethyl ether. The aqueous solution was then concentrated under reduced pressure to give (2-hydroxy- cyclohexyl) (dimethyl) octylammonium bromide, a clear amorphous gum.

Analysis: Calc'd for C16H3uBrN0: N 4.16 Found: N 4.23 The quaternary salts in Examples 2 - 11 were prepared in the same manner, using the appropriate alkyl bromide.

Example 2 Decyl (2-hydroxycyclohexyl) dimethylammonium bromide Hygroscopic crystals.

Analysis: Calc'd for CieH3eBrNO: N 3.84 Found: N 3.78 Example 3 Dodecyl (2-hydroxycyclohexyl) dimethylammonium bromide Heavy, colorless gum.

Analysis: Calc'd for C2oHu2BrNO: N 3.56 Found: N 3.64 Example 4 (2-Hydroxycyclohexyl) (dimethyl) tetradecylammonium bromide Crystals from acetone; m.p. 89-92°.

Analysis: Calc'd for CssHueBrNO: N 3.33 Found: N 3.38 Example 5 Hexadecyl (2-hydroxycyclohexyl) dimethylammonium bromide Crystals from acetone; m.p. 97-100°.

Analysis: Calc'd for C2 H5oBrNO: N 3.12 Found: N 3.20 Example 6 (2-Hydroxycyclohexyl) (dimethyl) nonylammonium bromide Amorphous gum.

Example 7 (2-Hydroxycyclohexyl) (dimethyl) undecylammonium bromide Clear amber gum. o Example 8 (2-Hydroxycyclohexyl) (dimethyl) tridecylammonium bromide Deliquescent solid.

Example 9 (2-Hydroxycyclohexyl) (dimethyl) pentadecylammonium bromide M.p. 65-72°.

Example 10 3-Hexyl (2-hydroxycyclohexyl) dimethylammonium bromide Amorphous gum.

Example 11 Heptyl (2-hydroxycyclohexyl) dimethylammonium bromide Amorphous gum.

Example 12 (2-Acetoxycyclohexyl) (dimethyl) dodecylammonium bromide A mixture of 1.0 g of dodecyl (2-hydroxycyclohexyl) -dimethylammonium bromide prepared in Example 3 , 5 ml of acetic anhydride and 5 ml of dry pyridine was allowed to stand at room temperature for about 16 hours. Twenty-five milliliters of water was added and the mixture allowed to stand for one hour. The solution was concentrated under reduced pressure at 50° using a rotary film evaporator. Two 20 ml portions of water were added successively to aid removal of pyridine, followed by absolute ethanol for final drying. The residue was 1.11 g of (2-acetoxycyclo-hexyl) (dimethyl) dodecylammonium bromide. The infrared electromagnetic spectrum was consistent with the assigned structure and clearly showed esterification of the hydroxy group to have occurred.

Example 13 Cucumber Radicle Growth Retardation Ten seeds of cucumber (Cucumis sativus L. var.

Marketer) were placed on a piece of filter paper contained in a 9 cm Petri dish on which had been placed previously 4 ml of an aqueous solution of the compound at concentrations ranging from 2 x 10 3 to 5 x 10 " molar. The filter paper was kept just sufficiently moist to avoid drying out of the seedlings. The Petri dishes were stored in the dark at 22-24°. After three days, the length of the radicles was recorded and compared with a set of seeds which were untreated. The results summarized in Table I show that growth was retarded 80% or more by 10 of the 11 compounds when applied at a 5 x 10 4 molar level, and by 6 of the 11 compounds when applied at a 2 x 10 4 molar level.

Table I Cucumber Radicle Growth Retardation Compound Concentration , Total Growth, mm % Difference molar (sum of 3 replicates) in Total Growth Ex. 1 5 x 10~4 68 -87.3 2 x 10~4 315 -41.2 1 x 10~4 417 -22.2 5 x 10~3 533 - 0.5 2 x 10"3 505 - 0.7 Untreated 555 - Ex. 2 5 x 10~4 60 -88.8 2 x 10~4 89 -83.4 1 x 10"u 138 -74.3 5 x 10"3 282 -47.4 2 x lO-3 401 -25.2 Untreated 516 - Ex, 5 x lO-4 58 -90.8 2 x lO-4 69 -89.0 1 x 10~4 173 -72.5 5 x lO-5 313 -50.2 2 x 10~3 596 - 5.2 Untreated 629 - Ex. 4* 5 x 10~4 60 -89.4 2 x 10~4 115 -79.6 1 x 10~4 257 -54.4 5 x 10~3 511 - 9.4 2 x 10~3 633 +12.2 Untreated 564 - Ex. 5* 5 x 10"4 172 -80.0 2 x 10~4 420 -51.1 1 x 10"4 591 -31.2 5 x 10~3 755 -12.1 2 x 10"3 818 - 4.8 Untreated 859 - Ex. 6* 5 x 10"u 54 -96.4 2 x 10~4 164 -89.7 1 x 10~4 356 -76.2 5 x 10"3 533 -64.2 2 x lO-3 984 -34.1 Untreated 1498 - Ex. 7* 5 x 10~4 58 -96.5 2 x 10~4 60 -96.4 1 x 10~4 170 -89.9 5 x 10"3 453 -73.0 2 x 10~3 726 -56.8 Untreated 1680 - Table I ■ ' (continued) Compound Concentration, Total Growth, mm % Difference molar (sum of 3 Ex. 8* 5 5 xx 1100~4 5 588 -94.6 2 x 10~4 77 -92.8 1 x 10~4 166 -84.4 5 x 10~3 296 -72.2 2 x 10"3 779 -26.9 Untreated 1066 Ex. 10* 5 5 xx 1100~4 1 10044 -89.1 2 x 10~4 393 -58.6 1 x 10~4 556 -41.5 5 x 10"3 711 -25.2 2 x 10~5 939 - 1.2 Untreated 950 Ex. 11* 55 xx 1100"*4 334499 -66.2 2 x 10~4 662 -35.9 1 x 10_u 773 -25.2 5 x 10"5 977 - 5.4 2 x 10~5 1102 + 6.7 Untreated 1033 Ex. 12* 55 xx 1100~44 5566 -92.8 2 x 10~4 60 -92.3 1 x 10~4 169 -78.3 5 x 10~5 419 -46.3 2 x 10"5 668 -14.4 Untreated 780 * Read after four days Example 14 Alfalfa Seed Growth Retardation One hundred seeds of alfalfa (Medicago sativa L. var. Hairy Peruvian) were placed in a Petri dish on filter paper wet with 2 ml of an aqueous solution of the test compound at concentrations ranging from 2 x 10 4 to 5 x 10 3 molar. After 48 hours in light, the seedlings were pressed gently between dry filter papers and then were weighed. Retardation was calculated at percent reduction in weight compared to weight of untreated seedlings and results are summarized in Table II. At a treatment level of 5 x 10 3 molar, the compounds retarded seed growth by 32.6% to 45.9%.

Table II Alfalfa Seed Growth Retardation Compound Concentration, Fresh Weight, g % Difference ■ molar (avg. of 3 replicates) in Weight Ex. 1 5 x 10~3 0.6694 -37.1 2 x 10 3 0.7220 -32.2 1 x 10 3 0.7988 -25.0 5 x 10 4 0.8980 -15.7 2 x 10 4 0.9930 - 6.7 Untreated 1.0648 Ex. 2 5 x 10~3 0.6491 -37.6 2 x 10 3 0.7025 -32.5 1 x 10 3 0.7855 -24.5 5 x 10 4 0.8808 -15.4 2 x 10 4 1.0177 - 2.2 Untreated 1.0410 Ex. 3 5 x 10~3 0.6494 -45.9 2 x 10~3 0.7481 -37.7 1 x 10~3 0.8579 -28.6 5 x 10 4 1.0048 -16.3 2 x 10 4 1.1050 - 8.0 Untreated 1.2010 Ex. 4 5 x 10 3 0, 6848 -34.1 2 x 10~3 0, 8798 -15.3 1 x 10~3 0, 9501 - 8.5 5 x 10~4 1, 0479 + 0.9 2 x 10~4 1, 0748 + 3.5 Untreated 1, 0385 Ex. 5 5 x 10_3 0.7613 -35 2 x 10 3 0.9621 -18, 1 x lO-3 1.0774 - 8, 5 x 10~4 1.1821 + 0, 1.1813 + 0, 1.1790 Ex. 6 5 x 10~3 0.6447 -39.9 2 x 10 3 0.6892 -35.8 1 x 10~3 0.7726 -28.0 5 x 10 4 0.9019 -15.9 2 x 10 4 0.9896 - 7.8 Untreated 1.0730 Table II (continued) Compound Concentration, Fresh Weight, g % Difference molar (avg. of 3 replicates) in Weight Ex. 7 5 x 10~3 0.6028 -43.7 2 x 10~3 0.6865 -35.9 1 x 10~3 0.8369 -21.9 5 x 10_u 0.9333 -12.9 2 x lO-1* 1.0793 + 0.8 Untreated 1.0712 - Ex. 8 5 x 10~3 0.6611 -35.4 2 x 10~3 0.7749 -24.3 1 x 10~3 0.8221 -19.7 5 x 10 u 0.9538 - 6.8 2 x 10 4 0.9732 - 4.9 Untreated 1.0238 - Ex. 10 5 x 10~3 0.6626 -38.0 2 x 10~3 0.7316 -32.7 1 x 10~3 0.8148 -25.0 5 x 10 0.9933 - 8.6 2 x 10"4 1.0469 - 3.7 Untreated 1.0868 - Ex. 11 5 x 10~3 0.7232 -32.6 2 x 10~3 0.7546 -29.7 1 x lO-3 0.8426 -21.5 5 x 10~u 0.9813 - 8.6 2 x 10 4 1.0190 - 5.1 Untreated 1.0737 - Example 15 Grapefruit Seed Growth Retardation by Seed Soak Method For each treatment, both the outer and inner seed coats were removed from 10 mature grapefruit seeds. The peeled seeds were soaked for 16 hours in an aqueous solution containing the test compound at a specified concentration. The seeds were then planted in No. 10 metal cans lined with plastic bags and containing a 1:1 mixture of sand and expanded mica. The cans were covered with glass plates so as to retain a high humidity while the plants emerged. Thirty days after planting the seeds, the plants were harvested and the fresh weights of lateral roots, taproot and plant top were determined. ·' These values are summarized in Table III. Root weights and plant top weights were substantially reduced by treatment with a 1 x 10 3 molar solution of decyl(2-hydroxycyclohexyl) dimethylammonium bromide.

Table III Grapefruit Seed Growth Retardation by Seed Soak Method Using Compound of Example 2 Concentration, Reduc- Reduc- Reduc- molar Weight tion Weight tion Weight tion 1 x 0.108 80.8 0.898 43.6 1.773 44.7 5 x 0.399 29.0 1.293 18.7 1.498 53.3 2 x 0.456 18.9 1.421 10.7 3.031 5.5 1 x 0.429 23.7 1.478 7.1 2.907 9.4 Untreated 0.562 - 1.591 - 3.209 Example 16 Grapefruit Seed Growth Retardation by Radicle Growth Method Ten peeled grapefruit seeds were placed on filter paper which was moistened by addition thereto of 4 ml of an aqueous solution of the test compound at a specific concentration. The germinating seeds were maintained in the dark at room temperature for 14 days during which period 2 ml of water was added to each dish on each of two occasions to prevent the seedlings from drying out. At the end of 14 days, the radicles were measured. The results summarized in Table IV show substantial growth retardation, 70% or greater for each compound at a 1 x 10 3 molar level.

Table IV r Grapefruit Radicle Growth Retardation Compound Concentration, Total Growth, % Different molar mm from Untre^ Ex. 1 2 x 10~3 52 -94.5 1 x 10"3 231 -75.6 5 x 10_u 693 -26.6 2 x lO-1* 1235 +31.5 Untreated 939 - Ex. 2 2 x 10~3 17 -98.0 1 x 10~3 109 -87.7 5 x 10~4 241 -72.8 2 x 10"4 665 -24.9 Untreated 885 — Ex. 3 4 x 10_u 148 -79.7 2 x 10"u 289 -60.4 1 x 10~4 433 -40.6 Untreated 729 - Ex. 4 2 x 10~3 68 -88.6 1 x 10~3 92 -84.6 5 x 10~4 152 -74.5 2 x 10"" 277 -53.5 Untreated 596 - Ex. 5 2 x 10~3 109 -83.8 1 x 10~3 200 -70.3 5 x 10~u 258 -61.7 2 x 10_u 453 -32.8 Untreated 674 - Example 17 Grapefruit Seedling Growth Retardation Forty grapefruit seedlings selected for uniformity of growth were cut back to a uniform 25 cm from the top of the container in which they were growing. Each seedling was treated by spraying thereon exactly 15 ml of an aqueous solution of the compound of Example 2 at a specified concentration. Ten seedlings were treated with each concentration. A cover had been placed over the soil to prevent dripping of the solution onto the soil and subsequent uptake by the plant root system. New growth was measured after two weeks and again after three weeks to determine growth retardation. At the end of the fourth week, all new growth was cut from the seedlings and weighed. All plants were then cut back to a uniform six inches. After four more weeks, new growth was again trimmed off and weighed. Results are summarized in Table V.

Table V Grapefruit Seedling Growth Retardation Te Plants per Treatment Treatment, ppm Compound of Example 2 1000 2000 3000 Untreated Total no. shoots 15 days 19 31 16 29 21 days * ** 19 29 Avg. growth/shoot, mm 15 days 31.1 43.5 18.4 49.1 21 days * ** 99.0 140.4 Difference from control, % 15 days -36.7 -11.4 -62.3 21 days * ** -29.5 New growth, g 0-28 days 96.5 110.6 87.2 129.1 28-56 days 65.1 53.2 77.4 - 69.0 0-56 days 161.6 163.8 164.6 198.1 Difference from con- trol, % 0-28 days -25.3 -14.3 -32.5 28-56 days - 5.7 -22.9 +12.2 0-56 days -18.4 -17.3 -16.9 * Resembled untreated seedlings; not measured.

** Growth appeared stimulated; not measured.

Within each ten plant group, considerable variation in growth retardation was observed. The group treated at 2000 ppm appears anomalous at the 15 day reading owing to the contribution of two plants . These two plants produced 11 shoots averaging 83 mm/shoot. (From this it is seen that the other 20 shoots thus averaged approximately 20 mm/shoot.) Example 18 Grapefruit Seedling Growth Retardation Sixty grapefruit seedlings were pruned to a height of 25 cm, and after new growth had developed (22 days) , foliar sprays were applied to the point of runoff. Each of 10 seedlings was treated by spraying with 20 ml of an aqueous solution containing 3000 ppm of a test compound and 1% of Regulaid (a polyoxyethylene polypropoxypropanol , a nonionic spreader-activator) . A soil cover was used to prevent spray droplets from contacting the soil. The increase in height of the plants was measured at weekly intervals and the results are summarized in Table VI, showing retardation or acceleration in growth relative to controls sprayed with a 1% Regulaid solution.

Table VI Growth Response of Grapefruit Seedlings to 3000 ppm of Compound (+ 1% Regulaid)* % Retardation (-) or % Acceleration (+) ' Compared to Untreated Period Example 1 Example~2~ ExampleT Example"""? ExampleT 1 week -6 -69 -82 -36 -38 2 week -15 -76 -94 -42 -40 3 week -16 -76 -95 -40 -40 4 week -8 -59 -59 -22 -9 5 week 0 -53 0 0 0 6 week -6 -32 +98 +52 +39 7 week -19 +8 +102 +54 +43 8 week -16 +61 +98 +48 +52 9 week +5 +66 +72 +39 +49 0 week +16 +20 +19 +12 +19 * Average response of 10 plants per treatment.

Observations of these seedlings one week after application of the spray indicated that phytotoxicity increased with the length of the alkyl group on the quaternary compound.

Seedlings treated with the compounds of Example 1 having an 8-carbon alkyl group showed essentially no effects of phytotoxicity, with only slight leaf curl at point of spray application, but new growth normal. The compound of Example 2 with a 10-carbon chain also caused leaf curl at the point of spray application, and necrosis and some new leaf abscission. The compound of Example 3, having a 12-carbon chain, produced a general abscission of tiny new leaves, but of no older leaves, and all 10 seedlings abscissed their growing tips; this was a true avscission and not dieback, since the tips abscissed were green at the base and the pedestals from which they abscissed were also green. The compounds of Example 4 (Cn) and Example 5 (C_6) caused abscission and abnormal growth and severe leaf damage, the C16 compound the more damaging.

It is seen in Table VI that retardation declined after the third week and an acceleration of growth relative to the growth of untreated seedlings began to manifest itself in the sixth week. The original inhibition was overcome and growth was stimulated. Two of the compounds (Examples 2 and 3) were also treated at 2000 ppm and 4000 ppm levels, with results summarized in Table VII.

Table VII Growth Response of Grapefruit Seedlings Period Example 2 Example 3 2000 ppm 4000 ppm 2000 ppm 4000 ppm 1 week -33 -45 -33 -88 2 week -34 -45 -33 -89* 3 week -36 -40 -21 -95 4 week -22 - 9 +16 -66 5 week + 9 +30 +65 -43 6 week +19 +26 +56 -39 7 week - 4 - 8 +21 -51 8 week 0 -11 +20 -50 9 week -18 -26 + 5 -56 0 week -23 -31 - 2 -56 * All 10 plants experienced apical abscission.

Example 19 Black Valentine : Bean Growth Retardation Individually potted, rapidly growing young (8 days old Black Valentine bean plants were sprayed to runoff with aqueous solutions containing the compound of Example 2 at specified concentrations. Ten plants were treated at each concentration. Measurements were made of the length of the second internode and of total plant height seven days after treatment. Results summarized in Table VIII show internodal height to be severely shortened, and total plant height substantially reduced.

Table VIII Black Valentine Bean Growth Retardation with Compound of Example 2 Concentration Internodal Height Total Plant Height mm % Difference mm % Difference 3000 7.8 -92.2 149.0 -60.5 2000 8.8 -91.1 173.5 -54.0 1000 11.3 -88.7 176.8 -53.2 Untreated 99.7 377.4 A similar study using the compound of Example 4 on 5 plants per replicate is summarized in Table IX. Retar- dation comparable to that obtained with the compound of j» . Example 2 was obtained at lower levels of treatment with the compound of Example 4.

Table IX Black Valentine Bean Growth Retardation with Compound of Example 4 Length of Total Primary Leaf Second Internode Plant Height Concentration % % PPm mm Difference mm Difference mm Difference 1000 7.0 -93.9 110.6 62.9 71.8 -10.4 500 12.8 -88.8 144.2 51.7 84.3 + 5.9 250 14.6 -87.2 131.4 56.0 81.4 + 2.3 125 23.0 -79.9 143.4 60.0 77.5 - 2.7 62 72.0 -37.0 242.2 18.9 87.4 +10.2 31 91.8 -19.7 263.6 11.7 89.2 +12.1 Untreated 114.3 298.5 79.6 For application to plants , these quaternary ammonium salts are normally not used undiluted, but are combined with any of a variety of adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of that toxicant in a given application. Thus, the quaternaries may be formulated as emulsifiable concentrates, as solutions, as wettable powders, as flowable pastes, as resinous pastes, or as any of several other known types of formulations, depending on the desired mode of application. For regulation of established plant growth, sprays are most commonly used. Formulations suitable for use in these applications may contain as little as a few parts per million or as much as 95% or more by weight of active ingredient.

Emulsifiable concentrates are homogeneous liquids which may be quite free-flowing or highly viscous, which are dispersible in water or other dispersant and which ( normally also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone, and other nonvolatile organic solvents. Solvents are homogeneous compositions in which the active ingredient is soluble in the inert liquid carrier and the combination is soluble in the final dispersant.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersant. The wettable powder is ultimately applied to the plant growth either as a dry powder or as an emulsion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other highly absorbent, readily wet inorganic diluents. Wettable powders are normally prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier. They usually also contain a small amount of wetting, dispersing, or emulsifying agent for facilitating dispersion.

Typical wetting, dispersing, or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylarylsulfonates and sulfates and their sodium salts; polyoxyethylene condensates; copolymers of polyoxyethylene and polyoxypropylene ; sulfonated oils; fatty acid esters; polyhydric alcohols; and other types of surface-active agents which, in formulations where they are used, normally comprise from 1% to 15% by weight of the formulation.

Resinous paste formulations are mixtures containing the active ingredient dispersed or suspended in an inert solid or semisolid organic substance obtained as an φ exudate of various plant or animal matter or prepared synthetically. Typical examples of resinous organic substances employed as carriers for the active ingredient include lanolin, asphalt, agar, and paraffin. These resinous paste formulations may contain between 0.01% and 50% of active ingredient. For application, these resinous paste formulations are applied to plants directly to the locus of desired application as the concentrated formulation or may first be diluted to a desired concentration of active ingredient by admixture with additional inert carrier substance.

Flowable paste formulations are mixtures of very finely divided active ingredients suspended in an emulsifying agent or other surface-active agent in the case of the highly concentrated flowable paste, or are suspensions in mixtures of water or other dispersing liquid with the emulsifying agent. These flowable paste concentrations may contain between 10% and 90% of active ingredient.

Other useful formulations include dusts which are admixtures of the active ingredient with finely divided solids such as talc, attapulgite clays, kieselguhr, and other organic and inorganic solids which act as dispersants and carriers for the toxicants; these finely divided solids have an average particle size of less than 50 microns in diameter.

For application, these concentrated formulations are usually dispersed in water or other liquid carrier and applied as a spray to the plant growth to be treated.

Or, in the case of solid formulations, application is ø carried out by dusting the toxicant formulation onto the plant growth to be controlled at a time when the normal leaf surface is in a condition such that the dust particles will adhere to the leaf surface.

Due to the outstanding effectiveness of the quaternary ammonium salts described herein to regulate the growth of plants without causing death of the plants, these products are of particular value and utility where retardation of vegetative growth and development, without total elimination of vegetation, is desired: for example, inhibition of growth of nursery stock or plantings of ornamental trees or shrubs so as to provide more desirable shapes or flowering patterns, or for the treatment of brush, shrubs, and trees under power lines, along highways and railroads and in small parks so as to reduce costs of trimming and pruning.

The compounds of this invention may be combined with other active ingredients. For example, combinations with slow-acting systemic herbicides may be used for weed and brush control, wherein the quaternary ammonium salt retards the growth of the plant while the herbicide is translocated throughout the plant to eventually kill it. The compounds of this invention may also be formulated and/or applied with insecticides, fungicides, nematicides, other plant growth regulators, fertilizers, and other agricultural chemicals. In applying these active compounds, formulated alone or with other agricultural chemicals, an effective amount and concentration of the quaternary ammonium compound are of course employed.

It is apparent that various modifications may be made in the formulation and application of the novel compounds of this invention without departing from the inventive concept as defined in the following claims.

Claims (1)

1. . 43876/2 1. Plant' regulator composition characterized by , '4. The composition of claim 2 characterized in that R* is undecyl radical and X is bromine. 43876/2 5. i', The composition' of claim''2, characterized in that R' is dodecyl radical and X. is bromine. 6. " ' ' The compositlfOnvof claim 2 characterized in that R' is tetradecyl radical and, X is. bromine. 7. Method for regulation of plant growth characterized b applying to the locus where regulation is desired an effective amount of a compound of the, formula: 8 · ... The method of claim 7 characterized in that 'R'" is H, R1 is a. straight alkyl radical of 10 - 14' carbon atoms, arid R" is' a t'etrameth lene radical which, forms a cyclohexane ring with the 1- and 2-carbons, and X is chlorine, bromine, or iodine.. 9. The. method of claim ,8 characterized in that R' •v. is decyl radical and X is bromine. 10. The method of claim 8 characterized in that R 1 is undecyl radical and X is bromine. 11. The method of claim 8 characterized in that R1 is dodecyl radical and X is bromine. 12. The method of claim 8 characterized in that R1 is tetradecyl radical and X is bromine. 13. Compound of the formula: wherein R is a saturated hydrocarbon chain of 10 - 14 Θ carbon atoms, and X is chloride, bromine, or iodide. 14. Decyl (2-hydroxycyclohexyl) dimethyl-ammonium bromide. 15. (2-Hydroxycyclohexyl) (dimethyl) undecyl-ammonium bromide. 16. Dodecyl (2-hydroxycyclohexyl) dimethyl-ammonium bromide. 17. (2-Hydroxycyclohexyl) (dimethyl) tetradecyl^ ammonium bromide. S. HOROWITZ & CO. AGENTS FOR APPLICANTS