Substituted 2,3-dihydro-,4-oxathiin plant growth stunting agents

EXAMPLE I

Preparation of 2,3-Dihydro-5,6-diphenyl-1,4-oxathiin from 2-Phenylacetophenone and 2-Mercaptoethanol. (Method A)

Powdered 2-phenylacetophenone (1021 g., mp. 55.degree.-57.degree.) was charged into a three-necked flask equipped with a strong mechanical stirrer, a reflux condenser and a dropping funnel. Sulfuryl chloride (430 ml.) was added in a continuous stream, over 10 minutes, with vigorous stirring. The reaction mixture was kept molten by heating on a steam bath for 1/2 hour. Benzene (2.5 l.) was added to the reaction mixture and a portion (300 ml.) of the solvent was removed under reduced pressure to remove excess sulfuryl chloride. The reactor was cooled to 20.degree. in an ice bath and a stream of ammonia was bubbled into the solution. After 15 minutes, 2-mercaptoethanol (385 ml.) was added during 1/2 hour (the reaction mixture temperature remained below 50.degree.). The ammonia sparge was continued for four additional hours and the reaction mixture was left at room temperature overnight. A cold solution of hydrochloric acid (1500 ml.). prepared by pouring 37% acid (600 ml.) over crushed ice (900 ml.), was poured into the reactor with stirring. After 15 minutes, stirring was stopped and the reaction mixture separated into two layers. The benzene layer was separated, p-toluenesulfonic acid (20 g.) was added and the reaction mixture was heated under reflux for 4 hours with azeotropic water removal. After cooling, the benzene solution was successively washed with 1.0 N sodium hydroxide solution (1000 ml.), water (500 ml.), filtered, and evaporated under reduced pressure. The warm syrup was then poured slowly into isopropyl alcohol (2.5 l.) with vigorous stirring, left overnight, the solid filtered off, and dried. The light tan coloured product (1062 g., 80% yield) melted at 61.degree.-63.degree..

Anal. Calc. for C.sub.16 H.sub.14 OS: C, 75.57; H, 5.55. Found: C, 75.58; H, 5.74.

EXAMPLE 2

Preparation of 2,3-Dihydro-2-methyl-5,6-diphenyl-1,4-oxathiin from 2-Chloro-2-phenylacetophenone and 1-Mercapto-2-propanol. (Method B)

A mixture of 1-mercapto-2-propanol (19.2 g.) and triethylamine (10.1 g.) in benzene (25 ml.) was added dropwise to a stirred, cooled (20.degree.), solution of 2-chloro-2-phenylacetophenone (23.0 g.) in benzene (200 ml.). The reaction mixture was left at room temperature overnight, washed with water (200 ml.), then with aqueous 5% hydrochloric acid (100 ml.). p-Toluenesulfonic acid (1.0 g.) was added to the benzene solution and the reaction was refluxed for 3 hours with azeotropic water removal. After cooling, the benzene solution was successively washed with 1.0 N sodium hydroxide solution (100 ml.), water (100 ml.) and the benzene removed under reduced pressure. The residue was crystallized from absolute ethanol to give light tan-colored crystals (16 g., 60% yield) melting at 68.degree.-69.degree..

Anal. Calc. for C.sub.17 H.sub.16 OS: C, 76.10; H, 6.01. Found: C, 76.14, H, 6.05.

EXAMPLE 3

Preparation of 2,3-Dihydro-5,6-diphenyl-1,4-oxathiin 4-oxide from 2,3-Dihydro-5,6-diphenyl-1,4-oxathiin and 30% Hydrogen Peroxide. (Method C)

To a stirred suspension of 2,3-dihydro-5,6-diphenyl-1,4-oxathiin (63.5 g., 0.25 mole) in glacial acetic acid (200 ml.) was added dropwise 30% hydrogen peroxide (30 ml., 0.26 mole). During the addition the temperature of the reaction mixture was maintained below 25.degree. by cooling in an ice bath. After standing for 12 hours at room temperature, the reaction mixture was filtered and the filtrate was poured, with stirring, into water (1,400 ml.). The crystalline precipitate was filtered, washed with water, and recrystallized from methanol to give colorless crystals (59.6 g., 88% yield) melting at 157.degree.-159.degree. with decomposition.

Anal. Calc. for C.sub.16 H.sub.14 O.sub.2 S: C, 71.10; H, 5.22. Found: C, 71.22; H, 5.11.

EXAMPLE 4

Preparation of 2,3-Dihydro-5,6-diphenyl-1,4-oxathiin 4,4-dioxide from 2,3-Dihydro-5,6-diphenyl-1,4-oxathiin and 30% Hydrogen Peroxide. (Method D)

To a stirred mixture of 2,3-dihydro-5,6-diphenyl-1,4-oxathiin (12.7 g., 0.05 mole), toluene (25 ml.) and formic acid (4 ml.) was added dropwise 30% hydrogen peroxide (12.5 ml., 0.1 mole). The mixture was refluxed on a steam bath for two hours, cooled, and the solid product was filtered off. The product was recrystallized from absolute ethanol to give colorless crystals (12.5 g., 87%) melting at 178.degree.-179.degree..

Anal. Calc. for C.sub.16 H.sub.14 O.sub.3 S: C, 67.12; H, 4.93. Found: C, 66.91; H, 4.93.

EXAMPLES 5-51

Using the procedures of the previous examples and appropriate starting materials, the substituted 1,4-oxathiins shown in TABLE I are prepared. TABLE I gives the systematic name for each product and identifies the method used, and also gives melting point data. In subsequent examples the compounds are identified by the example numbers given in TABLE I.

TABLE I __________________________________________________________________________ SUBSTITUTED 1,4-OXATHIINS Ex. M.P. No. Chemical Name Method (.degree.C) __________________________________________________________________________ 1 2,3-dihydro-5,6-diphenyl- A 61- 1,4-oxathiin 63 2 2,3-dihydro-2-methyl-5,6- B 68- diphenyl-1,4-oxathiin 69 3 2,3-dihydro-5,6-diphenyl- C 157- 1,4-oxathiin 4-oxide 159 4 2,3-dihydro-5,6-diphenyl- D 178- 1,4-oxathiin 4,4-dioxide 179 5 2,3-dihydro-6-(4-methylphenyl)- B 86- 5-phenyl-1,4-oxathiin 87 6 2,3-dihydro-6-(4-methylphenyl)- C 155 5-phenyl-1,4-oxathiin 4-oxide 7 2-(4-chlorophenyl)-5,6-dihydro- A 92- 3-phenyl-1,4-oxathiin 94 8 2-(4-chlorophenyl)-5,6-dihydro- C 174- 3-phenyl-1,4-oxathiin 4-oxide 175 9 3-(4-chlorophenyl)-5,6-dihydro- A 68- 2-phenyl-1,4-oxathiin 70 10 3-(4-chlorophenyl)-5,6-dihydro- C 108.5- 2-phenyl-1,4-oxathiin 4-oxide 110 .about.140 dec. 11 3-(4-chlorophenyl)-5,6-dihydro- D 152- 2-phenyl-1,4-oxathiin 4,4-dioxide 157 12 2-(4-fluorophenyl)-5,6-dihydro- A 80- 3-phenyl-1,4-oxathiin 82 13 2-(4-fluorophenyl)-5,6-dihydro- C 153- 3-phenyl-1,4-oxathiin 4-oxide 154 14 2-(4-fluorophenyl)-5,6-dihydro- D 150- 3-phenyl-1,4-oxathiin 4,4-dioxide 152 15 3-(3-chlorophenyl)-5,6-dihydro- A 65.5- 2-phenyl-1,4-oxathiin 67.5 16 3-(3-chlorophenyl)-5,6-dihydro- C 130- 2-phenyl-1,4-oxathiin 4-oxide 131 17 3-(4-bromophenyl)-5,6-dihydro- A oil 2-phenyl-1,4-oxathiin 18 3-(4-bromophenyl)5,6-dihydro- C 135- 2-phenyl-1,4-oxathiin 4-oxide 136 19 2,3-dihydro-2-methyl-5,6-diphenyl- C 145- 1,4-oxathiin 4-oxide 147 20 2,3-dihydro-5-(4-methylphenyl)- A 75- 6-phenyl-1,4-oxathiin 77 21 2,3-dihydro-5-(4-methylphenyl)- C 145- 6-phenyl-1,4-oxathiin 4-oxide 147 22 2,3-dihydro-5-(4-methylphenyl)- D 172- 6-phenyl-1,4-oxathiin 4,4-dioxide 173 23 3-(4-fluorophenyl)-5,6-dihydro- A 83- 2-phenyl-1,4-oxathiin 85 24 3-(4-fluorophenyl)-5,6-dihydro- C 168 2-phenyl-1,4-oxathiin 4-oxide 25 3-(4-fluorophenyl)-5,6-dihydro- D 152- 2-phenyl-1,4-oxathiin 4,4-dioxide 153 26 5-(4-aminophenyl)-2-ethyl-2,3- hydrogenation of 122- dihydro-6-phenyl-1,4-oxathiin corresponding 124 nitro compound 27 2,3-dihydro-5-(2-methylphenyl)- A oil 6-phenyl-1,4-oxathiin 28 2,3-dihydro-5-(2-methylphenyl)- C 128- 6-phenyl-1,4-oxathiin 4-oxide 130 29 2,3-dihydro-5-(3-methylphenyl)- A 58- 6-phenyl-1,4-oxathiin 60 30 2,3-dihydro-5-(3-methylphenyl)- C 113.5- 6-phenyl-1,4-oxathiin 4-oxide 115 31 2,3-dihydro-6-[4-(methylthio)phenyl]- A 130- 5-phenyl-1,4-oxathiin 131 135 dec 32 3-(2-chlorophenyl)-5,6-dihydro- A 59- 2-phenyl-1,4-oxathiin 61 33 3-(2-chlorophenyl)-5,6-dihydro- C 141- 2-phenyl-1,4-oxathiin 4-oxide 142 34 3-(4-aminophenyl)-5,6-dihydro- hydrogenation of 96- 2-phenyl-1,4-oxathiin corresponding 97 nitro compound 35 3-(4-ethylphenyl)-5,6-dihydro- A oil 2-phenyl-1,4-oxathiin 36 3-(4-ethylphenyl)-5,6-dihydro- C oil 2-phenyl-1,4-oxathiin 4-oxide 37 2,3-dihydro-5-(4-methoxyphenyl)- A oil 2-phenyl-1,4-oxathiin 38 2,3-dihydro-5-(4-methoxyphenyl)- C 134- 6-phenyl-1,4-oxathiin 4-oxide 136 39 2-[4-(acetyloxy)phenyl]-5,6-dihydro- A 108- 3-phenyl-1,4-oxathiin 109 40 2-(4-fluorophenyl)-5,6-dihydro- A 70- 3-(4-methylphenyl)-1,4-oxathiin 72 41 3-(3,4-dimethylphenyl)-5,6-dihydro- A 72- 2-phenyl-1,4-oxathiin 73 42 3-(3,5-dimethylphenyl)-5,6-dihydro- A 76- 2-phenyl-1,4-oxathiin 77 43 3-(3,5-dimethylphenyl)-5,6-dihydro- C 143- 2-phenyl-1,4-oxathiin 4-oxide 145 44 2,3-dihydro-5-(3-methoxyphenyl)- A 73- 6-phenyl-1,4-oxathiin 76 45 2-(2-chlorophenyl)-5,6-dihydro- A 71- 3-phenyl-1,4-oxathiin 73 46 2-(3-chlorophenyl)-5,6-dihydro- A 49- 3-phenyl-1,4-oxathiin 50 47 5,6-dihydro-2-(3-methylphenyl)- A oil 3-phenyl-1,4-oxathiin 48 5,6-dihydro-2-(2-methylphenyl)- A 57- 3-phenyl-1,4-oxathiin 58 49 2,3-dihydro-2-methyl-5-(4-methylphenyl)- A oil 6-phenyl-1,4-oxathiin 50 2,3-dihydro-2-methyl-5-(4-methylphenyl)- C 150- 6-phenyl-1,4-oxathiin 4-oxide 151 51 3-(4-chloro-3-methylphenyl)-5,6-dihydro- A oil 2-phenyl-1,4-oxathiin __________________________________________________________________________

EXAMPLE 52

To illustrate effectiveness of the described oxathiins as preemergent herbicides, 600 mg chemical is dissolved in 10 ml organic solvent (e.g., acetone) to which 30 mg conventional emulsifying agent (e.g., isooctylpolyethoxyethanol, "Triton X 100" trademark) is added. The solution is diluted to 100 ml with distilled water. Twenty ml of this 6000 ppm solution is diluted to 250 ppm with distilled water. The chemical is applied at the rate of 10 lbs/A (pounds per acre) by drenching 46 ml of the 250 ppm solution on the surface of soil in 41/2 inch plastic pots which had been planted with the following weeds: rough pigweed (Amaranthus retroflexus L.), purslane (Portulaca oleracea L.), tall morningglory (Ipomea purpurea L. Roth), crabgrass (Digitaria ischaemum (Schreb.) Muhl.), Barnyardgrass (Echinochloa crusgalli (L) Beauv.) and giant foxtail (Setaria faberi Herrm.). The percent control of the weeds compared to untreated checks is determined 2 weeks after treatment. TABLE II shows the results with the preemergence herbicides of the invention prepared in accordance with the above examples.

TABLE II ______________________________________ Preemergence Herbicides Percent Control of Weeds Including - Pig- Purs- Tall M. Bnyd- Crab- Giant Ex. weed lane glory grass grass Foxtail ______________________________________ 1 100 100 0 100 0 0 3 0 0 0 100 100 100 20 0 0 75 90 100 95 21 88 100 100 100 100 100 22 0 0 0 15 90 75 28 0 -- 0 50 95 0 29 0 0 0 50 95 95 30 -- -- 0 95 100 100 38 0 0 0 95 98 100 9 0 0 0 0 50 50 10 75 50 40 95 100 100 15 0 0 0 50 90 10 16 10 0 0 95 100 95 17 0 0 0 50 90 10 18 90 90 0 90 100 98 12 0 0 0 50 95 25 13 98 100 0 100 100 100 23 0 0 0 0 98 100 24 0 90 0 100 100 100 25 0 0 0 25 95 100 40 0 0 0 75 90 100 43 0 80 0 98 100 100 2 0 100 0 75 95 90 19 100 100 0 95 98 95 ______________________________________

EXAMPLE 53

Selectivity of a herbicide is desirable since it allows control of weeds growing among desirable crop plants. To illustrate the usefulness of the oxathiins of the invention as selective preemergence herbicides, 15 mg chemical is dissolved in 5 ml organic solvent containing 25 mg conventional emulsifying agent (e.g., isooctylpolyethoxyethanol) and this solution diluted to 300 ml with distilled water. The chemical is applied at the rate of 2 lbs/A by drenching the surface of soil containing weed and crop seeds in 6-inch plastic pots with 80 ml of the 50 ppm solution. The percent weed control and crop injury are evaluated two weeks after emergence of the crops. TABLE III illustrates the usefulness of these chemicals as selective preemergence herbicides.

TABLE III ______________________________________ Selective Preemergence Herbicide Test Percent Weed Control Wild Texas % Crop Injury Wild Mus- Pani- Quack Bynd Sugar- Soy- Ex. Oats tard cum grass grass beets Corn beans ______________________________________ 3 80 70 100 100 100 0 10 0 21 80 85 100 100 100 0 0 20 ______________________________________

EXAMPLE 54

Listed below are non-limiting examples of formulations which can be prepared with chemicals of this invention.

__________________________________________________________________________ 10.2% active one lb/gallon emulsifiable concentrate a. 2,3-Dihydro-5,6-diphenyl-1,4-oxathiin 4-oxide 61.2 g. b. Chloroform 305.4 g. c. *Triton X-114 (trademark; octyl phenoxy poly ethoxy ethanol) 112.2 g. d. Toluene 121.2 g. *other surfactants such as Rohm & Haas's AH861 (trademark), anionic/nonionic blended surfactant, can be substituted 50% active wettable powder a. 2,3-Dihydro-6-phenyl-5-(4-methylphenyl)- 1,4-oxathiin 4-oxide 40.0 g. b. Emcol L-72-34 (trademark) sodium dodecyl benzene sulfonate 0.8 g. c. Polyfon F (trademark) sodium lignin sulfonate 0.96 g. d. Dixie Clay (trademark) Kaolinite clay 9.6 g. e. Hi Sil (trademark) hydrated amorphous silicates 28.64 g. 47.3% active 4 lb/gallon emulsifiable concentrate a. 5,6-Dihydro-2,3-diphenyl-1,4-oxathiin 24.00 g. b. **Triton X-114 5.00 g. c. Naphtha 21.79 g. **other surfactants such as Rohm & Haas's AH861 (trademark) anionic/nonionic blended surfactant can be substituted. __________________________________________________________________________

EXAMPLE 55

Four crop species are planted in regular potting medium contained in 12 oz styrofoam cups. The four crops are Pinto Beans -- Phaseolus vulgaris; Cotton -- Gossypium hirsutum; Soybeans -- Glycine max and Wheat -- Triticum aestivum L. Six hundred mg chemical is dissolved in 10 ml acetone, 1-3 ml toluene and 30 mg of isooctylphenylpolyethoxyethanol (Triton X100; trademark). This mixture is diluted to a volume of 100 ml with distilled water. This mixture contains 6000 ppm active ingredient by weight. The mixture is sprayed to runoff on the four species aforementioned. The plants are sprayed with a DeVilbiss atomizing sprayer at the following stages of growth.

______________________________________ Pinto Beans very early first trifoliate Cotton fully expanded primary leaf stage Soybeans first trifoliate nearly expanded Wheat 2-4 leaf stage ______________________________________

Plant growth regulant observations were made from 5 days after spraying throughout the next 3 weeks. These observations included retardation, formative effects and phytotoxicity. These data are presented in TABLE IV, wherein "retd" stands for retardation, "phyto" stands for phytotoxicity, "N.G." stands for new growth, "trif" stands for trifoliate, and "n.e." stands for no effect.

TABLE IV __________________________________________________________________________ Plant Growth Regulation Ex. Bean Cotton Soybean Wheat __________________________________________________________________________ 1 90% retd 30% retd 20% retd 20% phyto 3 n.e. 10% phyto 35% phyto 5 n.e. 10% phyto 10% phyto 50% phyto 6 n.e. N.G. sl. slight 10% phyto deformed and puckering chlorotic 20 20% retd 80% 80% N.G. 20% retd terminal retd growth retarded 21 n.e. Trifoliates N.G. 30% retd severely retd severely darker epinastic green 22 n.e. n.e. 30% retd 5% phyto 27 Trifoliate 25% phyto 75% phyto 50% phtyo retd 28 n.e. 20% phyto 30% retd n.e. 29 Trifoliate N.G. 60% 60% retd 10% phyto 50% retd retd 30 20% retd N.G. 60% 60% retd n.e. retd 35 N.G. 50% retd N.G. 60% retd 50% retd n.e. dark green 36 Trif 75% retd N.G. 60% retd 85% phyto -- 37 N.G. 50% retd N.G. 80% retd 20% retd -- 38 60% retd N.G. 20% retd 30% retd 60% retd dark green dark green 7 75% N.G. 30% retd sl 20% phyto retd forced terminal epinasty growth 8 n.e. sl epinasty N.G. 10% phyto epinasty 9 Trif 100% 100% retd 80% retd n.e. retd 10 n.e. Trif retd 80% retd 80% retd 32 Trif 80% sl epinasty 30% retd 5% phyto retd dark green 33 n.e. 5% phyto N.G. 60% n.e. retd dark green 15 10% phyto terminal 30% retd 10% phyto 80% retd 100% phyto 16 20% retd Terminal 80% N.G. 100% retd 20% retd retd 17 n.e. 80% retd term 100% retd 20% retd stopped 18 30% retd Terminal 80% 80% retd 30% retd retd 12 10% phyto N.G. 60% retd N.G. 100% retd 15% phyto 13 n.e. N.G. 30% retd 60% retd 30% retd dark green dark green 23 n.e. 20% phyto Terminals 20% retd 60% retd 24 n.e. Terminal 30% 60% retd 20% retd retd 25 n.e. n.e. 30% retd & n.e. dark green 40 n.e. N.G. 50% retd N.G. 80% retd 30% retd dark green 41 n.e. 50% retd 20% phyto 15% phyto 43 n.e. N.G. 30% retd n.e. n.e. 2 n.e. n.e. 80% retd 10% retd 19 60% retd N.G. 30% retd 60% retd 60% retd 45 75% retd N.G. mod 60% retd n.e. puckered 46 N.G. 35% N.G. 95% 80% retd n.e. retd killed 47 N.G. dark N.G. 95% 40% retd n.e. green killed 48 N.G. dark N.G. 90% 40% retd n.e. green killed 51 N.G. 80% 30% retd 50% retd n.e. retd __________________________________________________________________________

EXAMPLE 56

To further illustrate the utility of these chemicals, data are presented in this Example on the growth retarding properties of soybeans (Corsoy variety). Seventy-five mg chemical is dissolved in 10 ml acetone, 2 ml toluene and 30 mg of Triton X100 (isooctyl phenyl poly ethoxyethanol). This mixture is diluted to a 50 ml volume with distilled water. This mixture is equivalent to 1500 ppm. In some cases a lower rate of 750-800 ppm is used, thus only 38-40 mg are used respectively for the mixture. This mixture is sprayed to runoff on three pots each containing two soybean plants in the early first trifoliate leaf stage. The spray is applied with a DeVilbiss atomizing sprayer. The first height measurement is taken at spraying time and the second when the control plants began to pod or approximately 4 weeks after spraying. A percent growth figure is obtained by using the following formula ##EQU2## where G.C. stands for growth of control plants in cm, and G.T. stands for growth of treated plants. TABLE V shows the unique growth retarding properties of the chemicals on soybeans.

TABLE V ______________________________________ Soybean Retardation Ex. Rate PPM % Retardation ______________________________________ 1 750 76 20 750 90 21 750 67 6 750 57 9 1500 36 10 1500 37 17 1500 30 18 1500 39 28 800 52 29 800 58 30 800 82 37 1500 13 38 1500 76 ______________________________________

EXAMPLE 57

The unique property of these chemicals to inhibit axillary growth is exhibited in this Example. Four hundred mg chemical is dissolved in 10 ml solvent (e.g. toluene, acetone, or mixture thereof) containing 3% surfactant (e.g., isooctylphenylpolyethoxyethanol [Triton X100; trademark], polyoxyethylene sorbitan monolaurate [Tween 20; trademark] or AH831 [trademark] blend of anionic and nonionic surfactants). This mixture, diluted to 100 ml with distilled water, is equivalent to 4000 ppm chemical. Lower dosages may be made by diluting the 4000 ppm formulation or by dissolving less chemical in the solvent mixture. Twenty ml of one of the mixtures described above is sprayed on tobacco plants (Nicotiana tabacum Xanthii variety) at the early flowering stage, but with flowers removed to force axillary growth. The spray is directed to the terminal growing areas in order to facilitate wetting each node as the mixture runs down the central stalk. Percent sucker control data are calculated on the green weight of the suckers which are plucked approximately 4 weeks after spray application. The following formula is used to calculate percent sucker control: ##EQU3## where S.W.C. stands for sucker weight in grams for the control and S.W.T. stands for sucker weight in grams for the treated plant. TABLE VI shows the unique ability of the chemicals to inhibit sucker or axillary bud growth.

TABLE VI ______________________________________ SUCKER CONTROL Ex. Rate PPM % Axillary Bud Control ______________________________________ 1 4000 99 3 1000 88 9 4000 91 10 4000 68 12 4000 100 13 4000 80 20 3000 99 21 3000 99 6 3000 63 30 4000 77 15 3000 76 16 3000 99 17 3000 95 18 3000 91 ______________________________________

EXAMPLE 58

To explain more clearly the activity of this invention on flowering, the following test on chrysanthemum is described. A sprayable formulation is made by emulsifying 1.06 g of a 4 lb active gallon (see Example 54 formulation 3 for composition) containing 2,3-dihydro-5,6-diphenyl-1,4-oxathiin and diluting this mixture to 100 ml volume with water. This mixture is equivalent to 5000 ppm. A respective dosage of 2500 is made by diluting the 5000 ml emulsion. This sprayable formulation is applied to Fred Shoesmith mums that had been exposed to 16 and 23 Short Days (10 hours) to induce flowering. The spray is applied to runoff with a DeVilbiss atomizing sprayer. The plants are placed back in the growth chamber until the total short day period of 6 weeks is completed. They are then removed and placed in a greenhouse until flowering. Data are taken by counting the number of axillary flower buds 1/2 inch or longer below the terminal flower. These data are presented in TABLE VII. The date in TABLE VII illustrate the unique properties of this invention in reducing the number of flower buds that would ordinarily require hand removal.

TABLE VII ______________________________________ Chrysanthemum Flowering Average Axillary Rate Spray Flower Buds Treatment PPM Timing Per Plant ______________________________________ Ex. I Chem. 5000 16 days 4.5 after 2500 first 10- 5.3 hour day 5000 23 days 4.0 after 2500 first 10- 5.9 hour day Checks 12.0 ______________________________________

EXAMPLE 59

To illustrate further the growth regulating properties of the chemicals on the metabolic activity of plants, 45.6 cc of chemical (formulated as a four pound active gallon -- see Example 54 formulation 3 for composition) were brought up to an 1,892 ml volume with water. This solution was applied at a 3 lb per acre rate in 30 gallons of water to sugarbeets, Beta vulgaris, three weeks before harvest.

The yield data were determined by hand harvesting each of three treatment replicates which consisted of one row 15 feet long. The sugar content was determined by measuring the sucrose content of beets that were randomly selected from each plot.

The data are given in TABLE VIII illustrating the increase in sugar content due to the chemical application. Based on an average yield of 40,000 pounds of beets per acre, the one percent increase would add 400 pounds of extra sugar per acre.

TABLE VIII ______________________________________ SUGAR INCREASE Rate Sugar Treatment (lbs/A) (%) ______________________________________ Ex 1 Chem. 3 16.08 " 11/2 15.62 Check 15.05 ______________________________________

EXAMPLE 60

To illustrate further the unique growth regulating properties of the chemicals on flowering, 8.5 g. of the chemical of EXAMPLE 1 (formulated as a four pound active gallon -- see EXAMPLE 54 for composition) was brought up to a 400 ml volume with water. This emulsion was applied to four replicate branches of Red Haven peaches that were in the second year of bearing. The flower buds at this time were in the tight bud stage. The chemical emulsion was applied to the branches to the point of run off, with a 1/2 inch brush. The buds were counted and recorded for each branch. Each branch had an average of 35 flower buds. The number of flower buds open were counted 28 and 33 days after application and compared to the original bud count. The percent flowers open figure was established from these two counts, with the results shown in TABLE IX.

A peach farmer is often faced with yield losses due to late frost. The chemicals herein described inhibit flower opening and hence flower kill.

TABLE IX ______________________________________ INHIBITION OF FLOWER OPENING ______________________________________ Percent Flowers Open 28 days 33 days after after Chemical Rate PPM Application Application ______________________________________ Ex. 1 10,000 10.2 17.6 5,000 64.3 91.6 2,500 62.5 100.0 Check 80.0 100.0 ______________________________________