United States Patent 1; ‘Schott et al. [54] PLANT GROWTH REGULATORS [75] Inventors: Eberhard P. Schott, Neustadt; Hans Lang, Limburgerhof, both of Fed. Rep. of Germany [73] Assignee: BASF Aktiengesellschaft, Fed. Rep. of Germany [21] Appl. No.: 965,263 [22] Filed: Dee. 4, 1978 [30] Foreign Application Priority Data Dec. 15, 1977 [DE] Fed. Rep. of Germany... 27559406 [51] Int. cls AOIN 57/12 2] US.a. 1/86; 71/94; 71/95 [58] Field of Search - 1/86, 94 [56] References Cited PUBLICATIONS British Farmer and Stockbreeder, “Breakthrough with Barley”, Mar. 18, 1978. ny 4,447,255 [45] May 8, 1984 Arable Farming, “Barley Growth Regulator Eliminates Ear Losses”, Jan. 1979. Arable Farming, “Sorting Out Seed Rates and Top- dressings,” Jan. 1979. Irish Farmers’ Journal, “Terpal Works,” Jul. 14, 1979. ‘The Scottish Farmer, “Boost in Spring Barley Margins Expected,” Dec. 8, 1979. ‘Terpal Leaflet-Chemical, Physical and Biological Properties, (23 pp.), (BASF) Mar. 1979, Ratschiiige fr den Getreidebav, BASF (1980) pp. 2and 3. Primary Examiner—Catherine L. Mills Attorney, Agent, or Firm—Keil & Witherspoon 57) ABSTRACT ‘New agents for regulating plant growth, especially for reducing the height of plants, containing a mixture of a quaternary substituted thianium or ammonium salt and 1 phosphonic acid derivative. 2 Claims, No Drawings4,447,255 1 PLANT GROWTH REGULATORS ‘The present invention relates to agents for regulating plant growth which contain a mixture of active ingredi ents, and to processes for regulating plant growth with these agents. It has been disclosed to use quaternary ammonium compounds, e-g., N,N-dimethylpiperidinium salts (Ger- man Laid-Open Application DE-OS No. 2,207,575), and phosphonic acid derivatives, e.g., 2-chloroethane- phosphonic acid (German Printed Application DE-AS ‘No. 1,667,968) for regulating plant growth. It has also been disclosed to use mixtures of N,N,N-trimethyl-N-2- chloroethylammonium chloride and 2-chloroethane- phosphonic acid for'regulating plant growth (German Laid-Open Application DE-OS No. 2,361,410). It has further been disclosed to use salts, e.g, the N,N-dime- thylpiperidinium salt of 2-chloroethanephosphonic acid, for regulating plant growth (German Laid-Open Application DE-OS No. 2,422,807). ‘We have now found that mixtures of (@ a quaternary substituted thianium or ammonium ‘salt selected from the group consisting of N,N-dimethylazacycloheptanium salts, N,N-dimethylpiperidinium salts, N,N-dimethylhexahydropyridazinium salts, Nemetinylpyridazinium salts, N,N-dimethylpyrrolidinium salts, and ‘S-methylthiacyclohexanium salts and (©) a phosphonic acid derivative selected from the group consisting of 2echloroethylphosphonic acid, 2-chloroethylaminoethylphosphonic acid, 2-chloroethylaminobutylphosphonic acid, 2chloroethylphosphonic acid-N,N-dimethyla- ‘mide, 2-chloroethylphosphonic acid-N,N-methylamide, vvinylphosphonic acid, propylphosphonic acid, phosphonomethylalycine, bis-phosphonomethylelycine, and benzylphosphonic acid are eminently suitable for regulating plant growth. Examples of particularly suitable salts are the halides (Chlorides, bromides), and especially the chlorides. Regulation of plant growth may include for instance the following plant response Inhibition of cell elongation, e.g. reduction in stem height and internodal distance, strengthening of the stem wall, thus increasing the resistance to lodging, which is a precondition for ensuring yields in cereals and other Gramineae for com or seed production, and in fiber plants from which textile fibers are obtained: ‘compact growth in ornamentals for the economic production of improved quality plants; promotion of better fruiting, c.g. increased fruit st in pomes, drupes and aggregate fruit, erapes, citrus fruits, almonds, olives, cacao, and coffee plants; increase in number of ovaries with a view to stepping up yield, eg., in Cucurbitaceae and papays promotion of senescence or the formation of tissue ‘enabling fruit to absciss, eg., improvement in fruit drop for facilitating the mechanical harvesting of citrus fruits, drupes, pomes and aggregate fruit, olives, monds, coffee and indehiscent fru 10 1s 2s 38 ey 45 35 2 defoliation of nursery and ornamental bushes and trees for mail-order business in the fall; defoliation of trees to interrupt parasitic chains of infection, e-g., Gloeasporium heveae in Heva brasiliensis; hastening of ripening, eg., in tomatoes, citrus fruits, pineapples and coffee, with a view to programming the harvest and promoting fruit color, of, in cotton, reduc- ing the harvest to 1 to 2 pickings and interrupting the food-chain for injurious insects. ‘The new mixtures have a synergistic action particu- larly in cereals, ie., the action of the mixture is better than the sum of the actions of the individual active ingredients. The new compositions are also better toler- ated than prior art compounds and result in improved rigor in cereals—a decrease in lodging is observed. Particularly the mixtures of | N,N-dimethyl- piperidinium chloride or _N,N-dimethylhexahy- Aropyridazinium bromide with 3-chloroethanephos- phonic acid, 2-chloroethyl-O-2’-aminoethyi)-phos- phonic acid, 2-chloroethylphosphonic acid-N,N-dime- thylamide or 2-chloroethyl-O.(2'-amino-n-butyl)-phos- phonic acid have a good growth-regulating action. The ratio of the active ingredients to each other may vary within wide limits, e.g,, 10:1 to 1:10 parts by ‘weight, especially 4:1 to 1:4, and preferably 3:1 to 1.3:1. ‘The agents according to the invention may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aque us, oily’ or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting (or watering. The forms of application depend entirely ‘on the purpose for which the agents are being uses any case they should ensure a fine distribution of the active ingredient. For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kero- sene or diesel oil, further coal-tar oils, etc. and oils of vegetable or animal ‘origin, aliphatic, cyclic and aro- matic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphtha lenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isopho- rone, etc., and strongly polar solvents such as dimethyl- formamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable. ‘Acqueous formulations may be prepared from emul- sion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oi Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkyl- aryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali ‘metal and alkaline earth metal salts of dibutylnaphtha- lenesulfonic acid, lauryl ether sulfate, fatty alcohol sul- fates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and ‘octadecanols, salts of sulfated fatty alcohol glycol ether, ‘condensation products of sulfonated naphthalene and4,447,255 3 naphthalene derivatives with formaldehyde, condensa- tion products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene ‘octylphenol ethers, ethoxylated isooctylphenol, ethox- ylated octylphenol and ethoxylated nonylphenol, alkyl- 5 Phenol polyglycol ethers, tibutylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl aleo- hols, fatty alcohol ethylene oxide condensates, ethoxyl- ated castor oil, polyoxyethylene alkyl ethers, ethoxyl- ated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose. Powders, dusts and broadcasting agents may be pre- pared by mixing or grinding the active ingredients with a solid carrier. Granules, e.g., coated, impregnated or homogeneous ‘granules, may be parepared by bonding the active ingre- dients to solid carriers. Examples of solid carriers are mineral earths such as silicie acid, silica gels, silicates, tale, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, ‘magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phos. phate, ammonium nitrate, and ureas, and vegetable Products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc. ‘The formulations contain from 0.1 t0 95, and prefera- bly 0.5 to 90, % by weight of active ingredient. “There may be added to the compositions oils of vari ous types, wetting agents or adherents, herbicides, fun- gicides, nematocides, insecticides, bactericides, trace elements, fertilizers, synergists, antifoams (e.g, sili- cones), growth regulators, and antidotes. The following examples of field experiments confirm ‘the superior biological action of the compositions over their individual components. ‘The mixtures are preferably used in the form of aque- ‘ous solutions. The mixtures are applied in conventional ‘manner, e.g., by spraying, atomizing, watering or disin- fecting seed. 0 20 30 a EXAMPLE 1 Spring barley, “Villa” variety Treatment was effected with aqueous solutions of the active ingredients 74 days after sowing. 101 days after sowing, the height of the plants was measured (average from 100 measurements). The resistance of the plants to lodging was astessed 124 days after sowing, 1 denoting best resistance, gradu- ated down to 9 denoting no resistance to lodging. 4“ 50 55 i Re growth sistance em lodging 3s Improvement to lode- ‘eight ‘Appin whe © Bs S (contro bre CEPA as 08 a a as as 1 1 mm 81 10 23 6s 94 4 -continued ction Improvement eRe nai Growth growth stance ance to leds ‘eight height to ing over mem lodging cantrol DPC = NN—inetipcnon ieee CEPA = Schiroebyiporons nat ‘These results demonstrate, with regard to the reduc- tion in height, the synergistic action of the composition ‘compared with its components. EXAMPLE 2 ‘Winter barley, “Birgit” variety ‘Treatment was effected with aqueous solution of the active ingredients 219 days after sowing. Harvesting took place 281 days after sowing. “Appin rate ‘ate _Grainyikd_ ‘Active ingredient wha “echonnes/nn 005% Untreated S m4 co bre = Rs 100, CEPA a m3 18 bre 2 + ‘ sn0 no cera “a This example also demonstrates that the mixture re- sults in a synergistic increase in yield compared with the individual components. EXAMPLE 3 Oats, “Flamingskrone” variety Treatment was effected with aqueous solutions of the active ingredients 72 days after sowing. The resistance to lodging was assessed 131 days after sowing, improvencat im ‘App, rte Resistance rentance to Active ingredient “Pg/n"™ to lodging odin Untreated = 70 — bre @ a 03 CEPA m 50 ° bre io : * 63 o7 cepa a Even when the untreated plants lodge fairly severely, the mixture results in a synergistic improvement in the resistance to lodging. EXAMPLE 4 Oats, “Borrus” variety ‘Treatment was effected with aqueous solutions of the active ingredients 80 days after sowing. The height of the plants was measured 105 days after sowing. Har- vesting was carried out 4 months after sowing. ‘Appia’ Growih Radsclionin Grin yield Active rte bsight growth height. eonnes/ ingrediont g/t “em es 9 Uniretea = zr 1004,447,255 5 continued ‘Appin. Growth Reduction ia Grain ysl Active rate height’ growth height dextonnes/ ingredient _g/ta__ cm om a Dre. 4 BS © 33 cA oe os sel 50 Bre’ eo + . aM os 4200 cepa oh Dre eo * * 80 0s ono These results clearly show the synergistic action of the mixtures compared with their components. rs EXAMPLE 5 Winter rye, “Carokurz” variety Treatment was effected with aqueous solutions of the active ingredients 196 days after sowing. The height of 20 the plants was measured 235 days after sowing. ‘Retucton Appin. rate Growth elght growth Beit Active ingreient “a ca aie Untreated = a7 Sj Dre io 02, is CEPA m 1410 ib bre’ “ Fy * 145, a Gea, 21 3% As in the other cereal species, the mixture resulted in 4 synergistic reduction in growth height here too. 6 ‘These results show that a mixture in an approximate Treatment was effected with aqueous solutions of the active ingredients 60 days after sowing. The height of the plant was measured 90 days after sowing. Harvest- ing was carried out 167 days after sowing, “Appia. Growth — Redaction im Active “Inte’ “Speight” growth height Ingredient__g/ta__ om on Untrewed — — 1680 S bre. sx 64 3482 aL CEA a Set 3188p bre 20 * acy 6k Gera ‘The mixture has a synergistic action compared with its components both with regard to the reduction in growth height and to the member of cobs formed. The usually undersirable growth of the plants is restricted in favor of an increase in yield. EXAMPLE 8 ‘Winter barley, “Mirra” variety Treatment was effected with aqueous solutions of the active ingredients 200 days after sowing. The height of the plants was measured 227 days after sowing. The resistance to lodging was assessed 270 days after sow- ing. Active ingredient (Untreated @) NN—dimethytbexahydeo- priidazinium bromide ©) Aehloroetiy-O— amino-n-bat- phosphonic acid 3 ‘Growth Reduction in ‘Appln.rate tight growth height Resistance wae cm __tolodging Improvement — 40 6s ° m2 a8 40 2s mo 3 a 4s 20 0 + 73060 15 so 400 EXAMPLE 6 ‘Winter rye, “Kustro” variety s ‘Treatment was effected with aqueous solutions of the active ingredients 209 days after sowing. Harvesting ‘was carried out 282 days after sowing, ‘Appl ate ‘Grain ved a Active ingreient g/t ___deconnes/ba Unreates = “0s 109 DFC 1380 23 106 CEPA. Kaa 6 Es Dre’ ‘oo 6 cera uo The mixture has a synergistic action compared with its components both with regard to the reduction growth height and improvement in the resistance to lodging, EXAMPLE 9 Winter barley, “Ogra” variety Treatment was effected with aqueous solutions of the active ingredients 213 days after sowing. The growth hheight was measured 232 days, and the resistance (0 lodging assessed 244 days after sowing. Harvesting was carried out 288 days after sowing.4,447,255 1 8 Recon Tapovene rom Repent Dee Aine “height” "Wight Resistance ance edp> Grainy Actveingrdion “"yfin om em _toladhing ing dediomev/ta WD vavees <0 a = sar B pre wo eke a 33S B Eeeosigto oy TS 3 33a amino, fhosntens 20 o? v0 * ne a7 os us 3 i This mixture, too, exhibits synergism compared with 35 its components. The growth height, resistance to lods- oe ing and the grain yield are significantly improved. a eeaere ‘Active ngeict = a eae © Unies) a = Winter barley, “Dura” variety 20 @) «DPC sis, 65 1 Treatment was effected with aqueous solutions ofthe SEPA = active ingredients 124 days alter sowing, Harvesting twas carried out 185 days after sowing. “This example demonstrates that a mixture ofa ratio of ——__ts 41 has @ synergistic action compared with its compo- avin ae Gai a Active ington wha Eciomentnn (1) Untreated 415 100, EXAMPLE 12 ® pee kite Winter rye, “Kustro” variety 8 fo BT ag ‘Treatment was effected with aqueous solutions ofthe > imme om active ingredients 204 days after sowing. The height of #2. a a7 n_the plants was measured 232 days after sowing, and 3 5 harvesting was carried out 285 days after sowing. Reduction ex “Appin. Growth vate” height” growth height _Graln yield on cm dechomer/ta_—% = 1542 5 3370 100 mo ao sa | imo-rao E18 seme 102 ‘X= NN aiospps nm ato Prothane wo aon o Gerson Ea Bebo pen Apmicnton ‘This example illustrates to what a considerable extent the yield can be increased with the mixture. EXAMPLE 11 ‘Spring rye, “Beacon” variety Treatment was effected with aqueous solutions of the active ingredients 59-days after sowing. The height of the plants was measured 100 days after sowing. 50 The reduction in growth height and the increased grain yield demonstrate the clearly superior action of mixture 3 over that of prior art salt A. EXAMPLE 13 ‘Winter rye, “Kustro” variety Treatment was effected with aqueous solutions of the active ingredients 206 days after sowing. The resistance to lodging was assessed 261 days after sowing and har- vesting was carried out 288 days after sowing. improvenent fe” Resitunce ance to lodg- __Graln yield Active ingredient __g/ha_tolodging___ing__“devtonnex/ha Untreated = ry st 100 QA 1300 33 30 He im @) Dre + cera 15's 46523, 45 564106 [A= NN—inathyppelsom mt of chooetiaepbrpbons cd Here, too, the mixture is clearly superior to the salt A both with regard to the improvement in resistance to Jodging and increase in yield,4,447, 9 EXAMPLE 14 Spring rye, “Somro” variety Treatment was effected with aqucous solutions ofthe active ingredients 85 days after sowing. The height of * the plants was measured 100 days after sowing, and harvesting was carried out 153 days after sowing. 255 10 EXAMPLE 17 Grass of the Festuca pratensis, var. “Cosmos 11” variety Treatment was effected with aqueous solutions of the active ingredients 270 days after sowing. Harvesting ‘was carried out 45 days after treatment. “Appin. Growh — Reduction in active vate” eight) growth eight Gran wil ingredient fn om cm decitonnevna © Umeaes— —S ua 100 @a cn) sao ° © Dre+ sorb 4.9 3a1 as CEPA [A= NN dincippatan i of. Borneo it In spring rye, 100, the action of the mixture is supe- tor to that of salt A’ both with regard to the reduction in growth height and the increase in grain yield = ‘poi Sein EXAMPLE 15 os nee Perens ter barley, “Ago” variety Active ingredient inane hn ‘Treatment was effected with aqueous solutions of the ( Untested = 05 100 — active ingredients 208 days after sowing. The resistance @ NN—-dimethyhew 50351845 to lodging was assessed 271 days afier sowing, and _purcgysieciniom harvesting was carried out 279 days after sowing. ©) Fehioreetyio~ awe sms® ‘Apo Tiprovement Active sate -Resitance in reistance _ Grain yield ingretien ____p/oa___totadging to ding _dectomnevn © Unewed 75 sso @a 7) 10 as os @ pecs m04@0 50 as as 0 CEPA, [A= NN-cietyippenion kof 2lonetypbapbode ‘Treatment with minture 3 results, compared with ania? ‘treatment with salt A, in a considerably improved resi- = tance to lodging, and, due to superior erop plant toler- 4s 22 +2 Seon us os 1 ance, a clear increase in yield. EXAMPLE 16 EXAMPLE 18 Grass of the Phleum pratense, var. “Holes” variety Grass of the Trisetum flavescens, var. “Trisett $1” ‘Treatment was effected with aqueous solutions of the *° are active ingredients about 2 years after sowing. The resis- tance to lodging was assessed 90 days after treatment. ‘Treatment was effected with aqueous solutions of the active ingredients about 4 years after sowing. Harvest- ‘ng was carried out 30 days after treatment. ‘Appia Improvement ite Restance in resitance Active ingrdiont wha ___tolodging®_ to lodging (@) Unreated| = 42 — @ NN—dimethytherabydro- 5,520 40 02 pyriaziium bromide (@) Petloroetiy-O— 17200 as 04 @-aminoethy- phosphonic aid 243 cu0 + 12960 32 19 ‘= woiaigng 9 = comply Bt4,447,255 W prove Appin sent i ae Seed vid "Yield Active ingredient whra_“Te/ea kaa GD Untestes = 2s 100 — @ NNdimedyines 520 ‘kopyridcnn () Zehloreethyo— a0 mys @ramincediy- phosphono ad ois 5680+ 12.960 3204396: EXAMPLE 19 Grass of the Trisetum flavescens, “Trisett $1” variety Treatment was effected with aqueous solutions of the active ingredients about 4 years after sowing. Harvest- ing was carried out 30 days after treatment. Taprove te Seed vies “Yite Active ingredient efos___Ke/n tea ® Unweates S 10 @ Dre smo OS 2chloroethy o— ©) @-aminoety). m0 ms Phosphonic ald wre 36804 12960215 EXAMPLE 20 70 parts by weight of the mixture employed in Exam- ple 2 is mixed with 30 parts by weight of water. A solution is obtained which is suitable for application in the form of very fine drops. EXAMPLE 21 20 parts by weight of the mixture employed in Exam- ple 3 is dissolved in a mixture consisting of 80 parts by 10 1s 25 38 8s 6 12 ‘weight of water, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to I mole of oleic acid-N- ‘monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by ‘weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient. EXAMPLE 22 20 parts by weight of the mixture employed in Exam- ple 2 is dissolved in a mixture consisting of 70 parts by ‘weight of water, 20 parts by weight of the adduct of 7 moles of ethylene oxide t0 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uni- formly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active in- gredient. EXAMPLE 23 20 parts by weight of the mixture employed in Exam- ple 3 is dissolved in a mixture consisting of 90 parts by weight of water and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of ‘water and finely distributing it therein, an aqueous solu- tion is obtained containing 0.02% by weight of the active ingredient. We claim: 1. A composition for regulating plant growth, con- sisting essentially of a synergistic mixture of ‘an effective amount to regulate plant growth of (2) N.N-dimethylpiperidinium chloride and (b) 2-chloroethylphosphonic acid, the ratio of (@)(b) being from 1:4 to 4:1 parts by weight. 2. A composition as set forth in claim 1, containing an aqueous solution of the active ingredients.