Phthalimidoguanidine plant growth regulators

Abstract

Novel compounds are disclosed which have utility as plant growth regulators. Use to produce growth regulators is specifically illustrated. The novel compounds of this invention are phthalimidoguanidines of the following general structural formulas: ##STR1## in which R, R.sup.1 and R.sup.5 are hydrogen, C.sub.1 to C.sub.5 alkyl, R.sup.2 and R.sup.3 are alike or unlike, one of which may be hydrogen but otherwise are substituents selected from C.sub.1 to C.sub.5 alkyl, alkenyl or alkynyl, branched or unbranched, C.sub.2 to C.sub.5 hydroxyalkyl or alkoxyalkyl, C.sub.3 to C.sub.5 cycloalkyl, furfuryl, pyridyl, benzyl, phenyl, C.sub.1 to C.sub.5 alkylphenyl, or --NR.sup.2 R.sup.3 together may be 2,5-dimethyl-1-pyrryl, 4-morpholinyl or 1-pyrrolidinyl, R.sup.4 is halogen, nitro, cyano, trifluoromethyl, C.sub.1 to C.sub.5 alkyl or acyl and n is zero, one or two.

Description

DESCRIPTION OF THE INVENTION

This invention is directed to a novel group of chemical substances which have, to a high degree the ability to change or modify the growth habits of plants. The invention is also directed to methods of regulating growth of plants to obtain desirable modifications, in particular the increase of fruit set, by application to living plants, their seeds, or to the soil of effective amounts of the novel compounds. Also are included methods of manufacturing the compounds, as well as agricultural formulations containing the novel compounds as growth regulators.

Briefly, the novel compounds of this invention are phthalimidoguanidines of the following general structural formulas: ##STR2## in which R, R.sup.1 and R.sup.5 are hydrogen or C.sub.1 to C.sub.5 alkyl, R.sup.2 and R.sup.3 are alike or unlike, one of which may be hydrogen but otherwise are substituents selected from C.sub.1 to C.sub.5 alkyl, alkenyl or alkynyl, branched or unbranched, C.sub.2 to C.sub.5 hydroxyalkyl or alkoxyalkyl, C.sub.3 to C.sub.5 cycloalkyl, furfuryl, pyridyl, benzyl, phenyl, C.sub.1 to C.sub.5 alkylphenyl, or --NR.sup.2 R.sup.3 together may be 2,5-dimethyl-1-pyrryl, 4-morpholinyl or 1-pyrrolidinyl, R.sup.4 is halogen, nitro, cyano, trifluoromethyl, C.sub.1 to C.sub.5 alkyl or acyl and n is zero, one or two.

Synthesis of the Growth Regulators

The compounds of this invention are readily prepared from the corresponding isothioureido isoindolediones by reaction with amines, as illustrated by the following procedure.

Preparation of 1,1,3-Trimethyl-3-phthalimido-2-phenylguanidine ##STR3##

To a saturated solution of anhydrous dimethylamine in 80 ml. of ethanol was added 4.53 g. (0.01 mol) of 2-(1,2-dimethyl-3-phenylisothioureido)-1H-isoindole-1,3-(2H)-dione, and the resulting solution was heated to 50.degree. C. for 30 minutes. Evaporation and treatment with heptane gave 3.5 g. of crystalline product, m.p. 146.degree.-8.degree. C.

The isothioureido isoindolediones employed as starting materials for the foregoing illustrative procedure may be manufactured by means of the general method comprising reacting a compound of the formula: ##STR4## in a non-reactive polar organic solvent with a compound of the formula R--X in which X is a leaving group exemplified by a chlorine, bromine, iodine or sulfate substituent. Specific procedures which are suitable for synthesis of representative compounds are outlined in the following chart and exemplified below. ##STR5##

It will be understood that when it is desired that R and R.sup.1 shall be different, the alkylation at the sulfur and amino locations is conveniently done in separate reaction steps. The following specific procedures illustrate the general methods of synthesis. All temperatures in the procedures are in .degree.C.

Synthesis of methyl hydrogen phthalate

Methanol (300 ml) was added in a single portion to 148 g (1.00 mole) of phthalic anhydride and the resulting suspension was stirred and heated at reflux for 36 hours; solution occurred during heating. The solvent was removed and the product was recrystallized from a mixture of ethyl acetate and hexane to afford 114.6 g of the title compound (Lit. Beilstein, 9,797-mp 82.5.degree., 84.degree.).

Synthesis of methyl phthaloyl chloride

Methyl hydrogen phthalate (110.0 g., 0.611 mole) and thionyl chloride (77.4 g., 0.650 mole) were mixed in 200 ml of chloroform, keeping the temperature below 30.degree.. After stirring for two hours at room temperature, the system was heated at reflux for five hours. The solvent was evaporated at reduced pressure and the crude product (120.9 g) was used without further purification (Lit.: Beilstein, 9, 797-no constants).

Synthesis of 2-(2-carboxybenzoyl)-1-methyl-N-phenylhydrazinethiocarboxamide (I)

This compound was made by reacting phthalic anhydride with 1-methyl-N-phenylhydrazinethiocarboxamide according to conventional procedures, as follows:

The hydrazinethiocarboxamide was dissolved in about 75 ml of dimethylformamide and placed in a 3-necked round-bottomed flask equipped with magnetic stirrer, condenser, additional powder funnel and thermometer. The anhydride was added in portions of 20.degree.. The contents were stirred overnight at room temperature, then poured into ice water the following morning. The resulting solid was recrystallized in hexane and ethanol (m.p. 155.degree.-156.degree. C.).

Optionally ring substituted phthalic anhydrides and substituted 2-carbomethoxybenzoyl chlorides may be condensed with substituted 1-methylhydrazinethiocarboxamides to give desired intermediate compounds as in the following scheme: ##STR6##

These methods are illustrated in the following specific procedures. The identity of the product was confirmed in each instant by means of infrared and nuclear magnetic resonance spectra. All melting points are as determined, uncorrected (Degrees C.).

N-Methyl-N-(phenylthiocarbamoyl)-2-amino-1H-isoindole-1,3-(2H)dione (II)

To an ice-cold solution of 8.25 g (0.025 mole) of 2-(2-carboxybenzoyl)-1-methyl-N-phenylhydrazinethiocarboxamide in 225 ml of 1,2-dimethoxyethane at .about.2.degree. C., a solution of 5.5 g (0.027 mole) of N,N'-dicyclohexylcarbodiimide was added dropwise below 5.degree. C. with stirring. The mixture was stirred in the ice bath and then left at room temperature overnight. The mixture was filtered to remove N,N'-dicyclohexylurea and the filtrate was evaporated below 40.degree. C., under vacuum, to give a yellow amorphous solid which was stirred in 100 ml of dry ether and warmed gently. The ether solution was allowed to stand for a few hours and filtered to give 4.6 g (59%) of whitish yellow crystals, m.p. 142.degree.-144.degree..

Recrystallization from ethyl acetate-hexane gave whitish crystals, m.p. 151.degree.-153.degree..

Mass spectrum: M.sup.+ 311.

N-Methyl-N (phenylthiocarbamoyl)-2-amino-4-methyl-1H-isoindole-1,3-(2H)dione

To a solution of 6.8 g (0.037 mole) of 1-methyl-N-phenylhydrazinethiocarboxamide and 3.0 g of pyridine in 100 ml dry dimethoxyethane, 2-carbomethoxy-6-methylbenzoyl chloride (8.0 g, 0.037 mole) was added and the resulting mixture was stirred at room temperature for 60 hours. The solvent was distilled and the residue was taken up in ethyl acetate, filtered and dried on anhydrous magnesium sulfate. Removal of the solvent gave 10 g (83%) of the desired product, m.p. 110.degree.-115.degree. (dec.).

2-Amino-1H-isoindole-1,3-(2H)dione

To an ice-cold suspension of 14.7 g (0.1 mole) of phthalimide in 100 ml of 95% ethyl alcohol at 5.degree. C., with stirring, 3.6 ml (0.11 mole) of 96.8% hydrazine was added dropwise. A slight exothermic reaction was observed and the mixture was allowed to stir at 5.degree. C. for two hours. The mixture was diluted with 200 ml of ice water, stirred, filtered, washed with water and dried to give 12.2 g (75%) of white powder, m.p. 199.degree.-202.degree..

Recrystallization from methanol-water gave white needles, m.p. 201.degree.-203.degree..

N-(Phenylthiocarbamoyl)-2-amino-1H-isoindole-1,3-(2H)dione (III)

To a suspension of 8.2 g (0.05 mole) of 2-amino-1H-isoindole-1,3-(2H)dione in 50 ml of dry 2-propanol, 6 ml (0.05 mole) of phenyl isothiocyanate was added. The mixture was stirred and refluxed for 3 hours, allowed to cool to room temperature and poured into 300 ml of 50% ethyl alcohol. After stirring for one hour, the solid which formed was filtered, washed with water and dried to give 12.1 g (81%) of the desired product as a white powder, m.p. 180.degree.-181.degree.. To make compounds in which Ar is benzoyl, benzoyl isothiocyanates may be employed in procedures of the type described above.

The free base was obtained by suspending the salt in dilute NH.sub.4 OH and extracting with CHCl.sub.3 which was washed with water, then with saturated aqueous NaCl and dried over anhydrous Na.sub.2 SO.sub.4. Removal of the CHCl.sub.3 at reduced pressure in a rotary evaporator gave a residual oil which was crystallized from ether-petroleum ether, wt. 4.6 g, m.p. 90.degree.-91.degree. (75%).

Preparation of 2-(2-Methyl-3-phenylisothioureido)-1H-isoindole-1,3-(2H)dione (IV)

To 100 ml of dry acetone, 5.0 g (0.018 m) of N-(phenylthiocarbamoyl)-2-amino-1-H-isoindole-1,3-(2H)dione and 2.5 g (0.018 m) powdered anhydrous potassium carbonate was added. To this suspension 1.1 ml (0.018 m) of methyl iodide was added and the mixture was stirred overnight at room temperature. The mixture was poured into .about.300 ml of water, stirred, filtered, washed with water and dried to give 4.4 g (78%) of a yellow powder, m.p. 161.degree.-164.degree.. Mass spectrum: M+311.

Preparation of 2-(1-Allyl-2-methyl-3-phenylisothioureido)-1-H-isoindole-1,3-(2H)dione

To 50 ml of dry acetone, 4.0 g (0.013 m) of the above product (IV), 2.2 g (0.016 m) of powdered anhydrous potassium carbonate, and 1.4 ml (0.016 m) of allyl bromide was added in succession and the mixture stirred overnight at room temperature. The mixture was poured into 300 ml of ice water with stirring. The aqueous layer was decanted and the residue suspended in fresh ice cold water, stirred and filtered to give a yellow semisolid product. This was purified by stirring in hexane to give a yellow powder 1.8 g (39%), m.p. 78.degree.-81.degree..

Compounds which have been made by means of the foregoing illustrative procedures are listed in Table 1 below.

TABLE 1__________________________________________________________________________COMPOUNDS OF THE FORMULAS: ##STR7## (1a) ##STR8## (1b)No. m.p. .degree.C. R R.sup.1 NR.sup.2 R.sup.3 (R.sup.4).sub.n R.sup.5__________________________________________________________________________4368 oil H CH.sub. 3 N(C.sub.2 H.sub.5).sub.2 n = 0 --4646 146-8.degree. " " N(CH.sub.3).sub.2 " --4647 192-5.degree. " " 4-morpholinyl " --4648 oil " " 1-piperidyl " --4649 159-61.degree. " " 1-pyrrolidinyl " --4650 oil " " Nmethyl benzyl " --4651 oil " " Nisopropyl benzyl " --4652 oil " " Nmethyl phenyl " --4653 oil " " Nethyl phenyl " --4654 oil " " N(CH.sub.2 CH.sub.2 CH.sub.3).sub.2 " --4655 oil " " ##STR9## " --4656 oil " " N(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2 " --4657 oil " " N propyl phenyl " --4658 oil " " N(sec. butyl).sub.2 " --4659 oil " " N(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2 " --4660 oil " " N(allyl).sub.2 " --4661 oil " " N(nonyl).sub.2 " --4702 oil " " N(isobutyl).sub.2 " --4703 oil " " Nmethyl cyclooctyl " --4704 oil " " N(octyl).sub.2 " --4705 oil " " Nmethyl propyl " --4707 oil " " Npropyl isopropyl " --4708 oil " " Npropyl isobutyl " --4709 oil " " Npropyl sec.butyl " --4710 oil " " Npropyl butyl " --4716 oil " " Nbenzyl 2-propynyl " --4717 oil " " Nallyl phenyl " --4718 oil " " Nethyl p-tolyl " --4719 233-5.degree. " " N(CH.sub.3).sub.2 3-F --4720 oil " " 4-morpholinyl " --4721 190-191.degree. " " NHCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 n = 0 --4722 136-8.degree. " " NHallyl " --4723 137-40.degree. " " NHbenzyl " --4724 154-165.degree. " " NH(CH.sub.2).sub.3 CH.sub.3 3-F --4725 52-3.degree. " " NHC(CH.sub.3).sub.3 n = 0 --4726 190-191.degree. " " NHCH.sub.2 CH.sub.2 CH.sub.3 " --4727 185-95.degree. " " NHcyclopropyl " --4728 oil " " NHcyclopentyl " --4739 52-4.degree. " " N(CH.sub.3)(CH.sub.2 CH.sub.2 OH) " --4740 glass " " N(CH.sub.3).sub.2 2,5-(CH.sub.3).sub.2 --4741 82-5.degree. " " N(CH.sub.3).sub.2 4-NO.sub.2 --4742 oil " " N(CH.sub.3).sub.2 4-F --4743 148-152.degree. " " N(CH.sub.3).sub.2 4-CN --4756 103-5.degree. " " N(CH.sub.3).sub.2 4-CF.sub.3 --4757 137-9.degree. " " N(CH.sub.3).sub.2 2,4-Cl.sub.2 --4758 glass " " N(CH.sub.3).sub.2 3-COCH.sub.3 --4759 glass " -- N(CH.sub.3).sub.3 n = 0 C.sub.2 H.sub.54760 glass " -- N(CH.sub.3).sub.2 " CH.sub.34762 164-72.degree. " H N(CH.sub.3).sub.2 3-F --4764 oil " CH.sub.3 1-pyrrolidinyl " --4850 oil 4-CH.sub.3 " NH(CH.sub.2).sub.3 CH.sub. 3 n = 0 --4956 oil H " NHCH.sub.2 CH.sub.2 OCH.sub.3 " --4957 oil " " Nmethyl furfuryl " --4958 oil " " 2,5-dimethyl-1-pyrryl " --4959 oil " " NH2-pyridyl " --__________________________________________________________________________

Use of the Growth Regulators

In highly active compounds, phytotoxic and growth-altering effects of pre-emergent and post-emergent application are often readily apparent. These effects may be demonstrated by means of the following illustrative procedures.

Pre-emergent Application

Disposable paper trays about 2 1.2 inches deep were filled with soil and sprayed with aqueous spray mixtures at a rate of 5 lb. of active chemical per acre of sprayed area, were seeded with 6 species of plant seeds and were then covered with about 1/4 inch of soil. The spray mixtures were prepared by dissolving the proper amount of growth regulant compound in 15 ml. of acetone, adding 4 ml. of a solvent-emulsifier consisting of 60 wt. percent of a commercial polyoxyethylated vegetable oil emulsifier (96 wt. percent active ingredient, Emulphor EL-719), 20 wt. percent xylene and 20 wt. percent deodorized kerosene, then bringing total volume up to 60 ml. by addition of warm water. Twenty-one days after seeding and treatment the plantings were examined and plant injury was rated according to the following schedule.

DEGREE OF EFFECT

0=no effect 1=slight effect, plants recovered 2=moderate effect, injury to 26 to 75 percent 3=severe effect, injury to 76 to 99 percent of foliage 4=maximum effect (all plants died)

Post-emergent Application

Several species of plants were grown in potting soil in disposable styrofoam trays and tomatoes were grown in four-inch pots in the greenhouse. Aqueous spray formulations were prepared and the growing plants were sprayed at a spray volume of 60 gallons per acre and an application rate of 5 lb. per acre. Spray mixtures were prepared in the manner described above. For comparative purposes, plants were also sprayed at 60 gal./acre with a spray mixture containing no growth regulant. Plant injury was again rated according to the schedule disclosed above.

Observations of growth regulant effects in both pre- and post-emergent tests were observed and recorded as follows:

______________________________________Effect Abbreviation in Tables______________________________________Formative effect on new growth FEpinasty EGrowth reduction GNecrosis NNon-emergence KChlorosis C______________________________________

In the table below there are tabulated the observations of pre- and post-emergent herbicidal and growth regulator effects resulting from use of one of the growth regulators of this invention according to the procedures set forth above.

TABLE 2__________________________________________________________________________EFFECTS OF THE COMPOUNDS ON PLANT SPECIESPre-emergent Effects Post-emergent EffectsCompound Digitaria Celosia Bromus Setaria Raphanus Beta Setaria Medicago Avena Raphanus Beta LycopersicumNo. sanguinalis plumosa inermis italica sativus vulgaris italica sativa sativa sativus vulgaris esculentum__________________________________________________________________________4368 F3G3 K4 F3G3 F3G3 F3G3 F3G3 F1G1 F3G2 F2G1 G1 F3G2 F3G1 N2F1__________________________________________________________________________

Post-emergent Application at Lower Rates on 24 Species

Twenty-four species of plants were grown in potting soil in disposable styrofoam trays and tomatoes were grown in four-inch pots in the greenhouse. Aqueous spray formulations were prepared and the growing plants were sprayed at a spray volume of 40 gallons per acre and application rates of 3 lb. and 1 lb. per acre. The spray mixtures were prepared by dissolving the proper amount of growth regulator compound in 15 ml of acetone, adding 4 ml of a solvent-emulsifier mixture consisting of 60 wt. percent of a commercial polyoxyethylated vegetable oil emulsifier (96 wt. percent active ingredient, Emulphor EL-719), 20 wt. percent xylene and 20 wt. percent deodorized kerosene, then bringing total volume up to 80 ml by addition of warm water. Of this spray mixture, a 50 ml portion was used to spray the plants at a rate of 3 lb. per acre of sprayed area. The remaining 30 ml. was diluted to 90 ml. with warm water and was used to spray the plants at a rate of 1 lb. per acre. One large, more mature tomato plant was included in the test along with the other, smaller growing plants. For comparative purposes, plants were also sprayed at a spray volume of 40 gallons per acre with a spray mixture containing no growth regulator.

Approximately fifteen days after spraying, the plants were observed and the results were evaluated according to the schedule disclosed above. Results obtained with representative compounds are presented in Table 3. The test species are as follows:

______________________________________ Common ScientificNumber Name Name______________________________________I Pigweed Amaranthus retroflexusII Lambsquarters Chenopodium albumIII Crabgrass Digitaria sanguinalisIV Downey brome Bromus tectorumV Giant foxtail Setaria faberiiVI Nutsedge Cyperus esculentusVII Peanuts Arachis hypogaeaVIII Cotton Gossypium herbaceumIX Tomato Lycopersicum esculentumX Sugar beets Beta vulgarisXI Wild buckwheat Polygonum convolvulusXII Wild mustard Brassica kaberXIII Mature tomato plant Lycopersicum esculentumXIV Cocklebur Xanthium pensylvanicumXV Morning glory Ipomea purpureaXVI Soybeans Soja maxXVII Barnyard grass Echinochloa crusgalliXVIII Green foxtail Setaria viridisXIX Alfalfa Medicago sativaXX Corn Zea maysXXI Grain sorghum Sorghum vulgareXXII Shattercane Sorghum bicolorXXIII Wheat Triticum aestivumXXIV Wild oats Avena fatuaXXV Rice Oryza sativa______________________________________ TABLE 3__________________________________________________________________________POST-EMERGENT EFFECTS ON 24 SPECIES__________________________________________________________________________Appl'n.Rate Compound Nos.Species (lb/A) 4646 4677 4648 4649 4650 4651 4652 4653 4654 4655 4656__________________________________________________________________________I 3 F2G2 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 1 F1 F3G3 F3G3 F3G2 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3II 3 F2G2 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 1 F1 F2G2 F3G3 F1G1 F3G3 F3G3 F3G3 F3G3 F3G3 F3G2 F3G3III 3 0 F1 F2G2 G1 F3G3 F2G1 F3G2 F3G2 F1 G1F1 F2G1 1 0 0 F1G1 0 F1 F2G1 F1G1 F1 F1 F1 F1G1IV 3 0 0 F1 0 F1G1 0 F1 F1 0 0 F1 1 0 0 0 0 0 0 0 0 0 0 0V 3 0 F1 F3G3 F1 F3G3 F1G1 F2 F3G2 F2G1 F2G1 F2G2 1 0 0 F2G2 0 F1 F1G1 F2 F2G1 F2 F2G1 F1VI 3 0 0 0 0 F1 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0VII 3 0 0 0 0 F1 F1 F1 F1 F1 0 F1 1 0 0 0 0 0 0 0 0 0 0 0VIII 3 0 F2 F1 F2G2 F3G3 F3G1 F2G1 F2G1 F2 F1 F3G3 1 0 F1 F1 F1 F2G1 F2G1 F2 F2 F2 F1 F2IX 3 F2 G2F3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 1 F1 F3 F3G3 F3 F3G2 F3G2 F3G3 F3G3 F3G3 F3G2 F3G3X 3 F2 F1G1 F3G3 F2G2 F3G3 F3G3 F3G3 F3G2 F3G2 F3G3 F3G3 1 F1 F1 F3G3 F1 F2G1 F2G1 F3G2 F3G2 F3G2 F3G2 F2G2XI 3 0 0 F2G2 F1G1 F2G2 F3G2 F2G2 F2G2 F2G2 F2G2 F2G2 1 0 0 F2G1 0 F1 F1 F1G1 F1 F2 F1 F1G1XII 3 F1 F1 F3G2 F1 F2G2 F3G3 F2G2 F3G2 F2G2 F3G2 F2G2 1 0 0 F3G2 0 F1 C2F1 C2F1 C2F1 F2G1 C1F1 F1C2XIII 3 F1 F2 F3 F3 F3G1 F3 F3G2 F3G3 F3G3 F3G3 F3G3 1 F1 F2 F3 F2 F3 F3 F3 F3G2 F3G1 F3G2 F3G2XIV 3 F1 0 F2G1 F1 F2G2 F2 F2G1 F2G1 F2G1 F2G1 F2G1 1 0 0 F1 0 F2G1 F1 F1 F1 -- F1 F1G1XV 3 F1 F2 F2G2 -- F3G3 F3G2 F3G2 F3G3 F3G3 F3G3 F3G3 1 0 F1 F1G1 0 F2G2 F2G1 F3G2 G2F2 F2G1 F2G2 F3G2XVI 3 F2 G2F2 F3G3 F2 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 1 F1 F2G1 F3G3 F1 F3G3 F3G2 F3G2 F3G2 F3G2 F3G2 F3G3XVII 3 0 0 F1 0 F1G1 F1 F2G1 F2G1 F1G1 F1 F1 1 0 0 F1 0 F1 0 F1 F1 0 0 0XVIII 3 0 F1 F2G1 F1 F2G2 F2G2 F2G2 F3G2 F2G2 F2G2 F2G2 1 0 0 F1 0 F1G1 F1G1 F2G2 F3G2 F2G2 F2G1 F1G1XIX 3 F1 F2 F3G3 F2 F3G3 F3G3 F3G3 F3G3 F3G2 F3G3 F3G3 1 0 F1 F3G2 F1 F3G2 F3G1 F3G2 F3G2 F3G1 F3G1 F3G2XX 3 0 0 C1 0 F1 0 F1 F2G1 F1 F1 F1G1 1 0 0 0 0 0 0 0 F1 0 0 0XXI 3 0 F1 F1 0 F2 F2 F3G1 F3G2 F2G1 F1 F2G1 1 0 0 0 0 F1 F1 F1 F1 F1 F1 0XXII 3 0 F1 F1 0 F2 F2 F3G1 F3G2 F2G1 F1 F2G1 1 0 0 0 0 0 F1 F1 F1 F1 F1 F1XXIII 3 0 F1 0 0 F1 F1 F2G1 F1G1 F1 0 F1 1 0 0 0 0 0 F1 0 0 0 0 0XXIV 3 0 0 0 0 F1 F1 F1G1 F1 F1 0 F1 1 0 0 0 0 0 0 0 0 0 0 0XXV 3 0 0 0 0 F1 F1 F1G1 F1 F1 0 F1 1 0 0 0 0 0 0 0 0 0 0 0Comments increased increased more more more more more more more more fruit set fruit set fruit fruit fruit fruit fruit tillers tillers tillers set set set, set, set tillers tillers__________________________________________________________________________Appl'n.Rate Compound Nos.Species (lb/A) 4657 4658 4659 4660 4661 4702 4703 4704 4705 4707 4708__________________________________________________________________________I 3 F3G3 F3G3 F3G3 F3G3 F3G3 C3G3 F1 F3G3 F3G3 F3G3 F3G3 1 F3G3 F3G3 F3G3 F3G2 F3G3 F3G2 F1 F3G2 F3G3 F3G3 F3G3II 3 F3G3 F3G3 F3G3 F3G3 F3G3 C3G3 F1 F3G3 F3G3 F3G3 F3G3 1 F3G3 F3G3 F3G3 F3G2 F3G3 F3G3 F1 F3G2 F3G3 F3G3 F3G3III 3 F1G1 F2G2 F1G1 G2F1 F3G2 G2F2 0 F1 F2G1 F3G2 F3G2 1 F1 F1G1 F1 G1 F2G1 F1 0 0 0 F1G1 F1G1IV 3 0 F1 0 G1 G1 G1 0 G1 G1 G1 G1 1 0 0 0 0 0 0 0 0 0 0 0V 3 F2G2 F2G2 F1 F2G2 F3G2 F3G2 0 F1G1 F2G2 F2G2 F2G2 1 F1 F1 0 F1 F2G1 F1 0 0 F1 F1 F2G1VI 3 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0VII 3 F1 F1 0 F1 F1 0 0 0 0 F1 0 1 0 0 0 0 0 0 0 0 0 0 0VIII 3 F2G1 F2G1 F2G1 F3G3 F2G1 F1 0 N3G2 F1 F2G1 F2 1 F1 F1 F1 F1 F1 0 0 NqF1 F1 F2 F1IX 3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 F2 N4 F3G3 F3G3 F3G3 1 F3G3 F3G3 F3G3 F3G3 F3G3 F3G1 F2 F3G2 F3G2 F3G3 F3G2X 3 F3G3 F3G2 F3G3 F3G2 F3G3 F3G2 F1 F3G3 F3G3 F3G3 F3G3 1 F2G2 F3G2 F3G2 F3G2 F3G2 F2 F1 F2G2 F3G2 F3C2 F3G2C2XI 3 F2G2 F2G2 F2G1 F1G1 F1G1 F1 0 F1 F1 F1 F1 1 F1 F1G1 F1 F1 F1 0 0 0 0 0 0XII 3 F2G1 F2G2 F2G1 F3G2 F3G3 C2F1 0 N4 C3F2 C3G3 C3G2 1 F1C1 F1C1 F1 G1F1 F1G1 0 0 N2F2 F1C1 C2F1 C2F1XIII 3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G1 F3 N3F3 F3G2 F3G2 F3 1 F3G3 F3G3 F3G2 F3 F3 F3 F2 N2F2 F3 F3 F3XIV 3 F3G2 F2G2 F2G1 F2G1 F2 F1 F1 F1N1 -- -- F1 1 F1 F1 F1 F2 F1 F1 F1 F1 F2 F1 F1XV 3 F3G3 F3G3 F3G3 F3G2 F3G3 F3G2 F2G2 F3G3 F2G2 F3G3 F3G2 1 F2G1 F3G3 F3G3 F3G1 F3G2 F1 F1 F2 F2G2 F2 F2G1XVI 3 F3G3 F3G3 F3G3 F3G3 F3G3 F3G2 F3G2 F3G3 F3G3 F3G3 F3G3 1 F3G2 F3G3 F3G2 F3G3 F3G3 F3G2 F2G2 F3G2 F3G3 F3G3 F3G3XVII 3 F1 F1 F1 F1 F1 0 0 0 F1G1 F2G1 F1 1 0 0 0 0 0 0 0 0 0 0 0XVIII 3 F2G2 F2G2 F2G2 F2G1 F2G2 F2G1 0 F2G1 F2G2 F2G2 F3G2 1 F2G1 F2G1 F1 F1G1 F1 F1 0 F1 F1 F1 F1XIX 3 F3G3 F3G3 F3G3 F3G2 F3G3 F3G2 F2C1 F3G3 F3G2 F3G3 F3G3 1 F3G1 F3G2 F3G1 F3G2 F3G1 C1F2 F1 F1N1 F3G1 F3G1 F2G1XX 3 F1 F1 F1 F1 F1 F1 0 F1 F1 F1 F1 1 0 F1 0 0 0 0 0 0 0 F1 F1XXI 3 F2G1 F2G1 F2 F2G1 F2G1 F2 F1 F3G2 F2G1 F2G1 F2G1 1 F1 F2 0 F1 F1 F1 0 F1 F1 F1 F1XXII 3 F2G1 F2G1 F2 F2G1 F2G1 F2 F1 F3G2 F2G1 F2G1 F2G2 1 F1 F2 0 F1 F1 F1 0 F1 F1 F2 F2XXIII 3 F1 F1 F1 F1 F1 F1 0 N1G1 F1 F1 F1 1 0 F1 0 0 0 0 0 0 0 F1 F1XXIV 3 F1 F1 F1 F1 0 F1 0 N1G1 F1 F1 F1 1 0 0 0 0 0 0 0 0 F1 F1 F1XXV 3 F1 F1 0 F1 F1 F1 0 N1G1 F2 F1 F1 1 0 0 0 0 0 0 0 0 0 F1 0Comments more more more more more more more more more more tillers fruit fruit fruit fruit fruit fruit fruit fruit fruit set set, set, set, set set set, set, set, tillers tillers tillers tillers tillers tillers__________________________________________________________________________Appl'n.Rate Compound Nos.Species (lb/A) 4709 4710 4716 4717 4718 4719 4720 4721 4722 4723 4724__________________________________________________________________________I 3 F3G3 F3G3 F3G3 F3G3 F3G3 F1 F3G3 F1 F1 F1G1 F3G3 1 F3G3 F3G3 F3G3 F3G3 F3G3 0 F3G2 0 0 0 F1II 3 F3G3 F3G3 F3G3 F3G3 F3G3 F1 F3G3 F1 F1 0 F3G3 1 F3G3 F3G3 F3G3 F3G2 F3G3 0 F3G3 0 F1 0 F2G1III 3 F3G2 F3G3 F2G1 F2G1 F1G1 0 F2G1 0 0 0 0 1 F1G1 F1G1 F1 F1 F1 0 F1G1 0 0 0 0IV 3 G1 G1 F1 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0V 3 F3G2 F3G2 F3G2 F3G2 F2G1 0 F2G2 0 0 0 0 1 F1 F2 F1 F1 F1 0 F1 0 0 0 0VI 3 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0VII 3 F1 F1 F1 F1 0 0 F1 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0VIII 3 F2 F2G1 F1 F2 F1 0 F2 0 0 0 0 1 F1 F1 F1 0 F1 0 F1 0 0 0 0IX 3 F3G3 F3G3 F3G3 F3G3 F3G3 F1 F3G3 F1 G1F2 F2G2 F3G3 1 F3G2 F3G2 F3G2 F3G1 F3G3 F1 F3G2 F1 F1 F1 F3G2X 3 C3F3G3 F3G3C3 F3G3 F3G3 F3G3C2 F1 F3G3C3 F1 F2 F1 F3G3C1 1 F2G2C2 F3G2C2 F2G2C1 F2G1 F3C2 0 F2G2C1 F1 F1 F1 F2G1XI 3 F2G1 F2G1 F1G1 F2G2 F2G1 0 F1G1 0 0 0 F1 1 0 F1 F1 F1 F1 0 F1 0 0 0 0XII 3 C3G3 C3G3 F1G1 C1F2G2 F2C2 0 F3C3G2 0 0 0 F1 1 C2F1 C2F1 F1C1 F1C1 F1C1 0 F2C2G1 0 0 0 0XIII 3 F3C1 F3G1 F3G1 F3G1 F3G1 F1 F3 F1 F3 F2 F3 1 F3 F3 F3 F3 F3 0 F2 0 F2 F2 F3XIV 3 F1 -- F1 F2 -- 0 -- 0 0 0 F1 1 F1 F1 F1 F1 F1 0 F1 0 0 0 0XV 3 F3G3 F3G3 F2G2 F3G3 F3G2 0 F3G2 0 F1 0 F2G1 1 F2G1 F2G2 F2G1 F2G1 F2G2 0 F2G1 0 0 0 F1XVI 3 F3G3 F3G3 F3G3 F3G3 F3G3 0 F3G3 F1 F1 0 F2G2 1 F3G3 F3G3 F3G3 F3G3 F3G3 0 F3G3 0 0 0 F2XVII 3 F2G1 F2G1 F1 F1 F1 0 F2G1 0 0 0 0 1 F1 F1 0 0 0 0 0 0 0 0 0XVIII 3 F2G2 F2G2 F1 F2G1 F1G1 0 F3G2 0 0 0 F1 1 F1G1 F1 F1 F1 F1 0 F2G1 0 0 0 0XIX 3 F3G3 F3G3 F3G2 F3G1 F3G2 F1 F3G3C1 F1 F1 F1 F3G2 1 F2G1 F3G2 F3 F2C1 F2C1 0 F3C1 0 0 F1 F2XX 3 F1 F2G1 F1 F1 F1 0 F1 0 0 0 0 1 0 F1 0 0 0 0 F1 0 0 0 0XXI 3 F2G1 F3G2 F2 F2 F2 0 F2G1 0 0 0 0 1 F1 F2 F1 F1 F1 0 F1 0 0 0 0XXII 3 F2G1 F3G2 F2 F2 F2 0 F2G1 0 0 0 0 1 F1 F2 F1 F1 F1 0 F1 0 0 0 0XXIII 3 F1 F1 0 0 0 0 F2G1 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0XXIV 3 F1 F2 F1 F1 F1 0 F1 0 0 0 0 1 F1 F1 F1 F1 F1 0 F1 0 0 0 0XXV 3 F1 C1F1 F1 F1 F2 0 F1G1C1 0 0 0 0 1 0 0 0 0 F1 0 0 0 0 0 0Comments more more more more more more more more more more fruit fruit fruit fruit fruit fruit fruit fruit fruit fruit set, set, set, set, set, set set, set set set tillers tillers tillers tillers tillers tillers__________________________________________________________________________Appl'n.Rate Compound Nos.Species (lb/A) 4725 4726 4727 4728 4739 4740 4741 4742 4743 4756__________________________________________________________________________I 3 F3G3 0 F3G2 F3G3 F3G3 F3G2 F1G1 F3G3 F3G3 F3G3 1 F3G3 0 G1 G3F3 F3G3 F2G2 F1G1 F3G2 F1G1 F2G1II 3 F3G3 0 F1G1 F3G3 F3G3 F3G2 F1G1 F3G3 F3G3 F3G3 1 F3G3 0 0 F3G2 F3G3 F2B2 F1 F1G1 F1G1 F2III 3 F2G2 0 0 F2G2 F2G1 0 0 F2G2 0 0 1 F1G1 0 0 F1 F1 0 0 0 0 0IV 3 G1 0 0 F3G2 0 0 0 0 0 0 1 0 0 0 F2G2 0 0 0 0 0 0V 3 F2G2 0 0 F2G2 F2G2 0 0 0 0 F1 1 F1 0 0 0 F1 0 0 0 0 0VI 3 0 0 0 0 C1 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0VII 3 0 0 0 0 F1 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0VIII 3 F1 F1 N1 0 F1 0 0 0 0 F2 1 0 0 0 0 0 0 0 0 0 F1IX 3 F3G3 F2G1 F3G3 F3G3 F3G3 F2G1 G1F2 F3G3 F3G2 F3G3 1 F3G3 F1 F3G1 F3G3 F3G3 F1 F2G1 F3G3 F2G1 F2X 3 F3G3C2 F1C1 F2G2 F3G3C2 F3G2C2 F2 F2 F3G2 F1 F2 1 F2G2C1 0 F2 F3G1 F2G2 F1 F1 F2G1 F1 F2XI 3 F2G2 0 0 F1 F1 F1 0 0 0 F1G1 1 F1 0 0 0 F1 0 0 0 0 0XII 3 F3G2C2 0 F1 F2G2C1 F1G1 C1 0 F1 F1 F2 1 F1C1 0 0 F1C1 F1C1 0 0 0 0 0XIII 3 F3G3 F1 F3 F3G3 F3G1 F3 F2 F3 F3 F3 1 F3G2 F1 F2 F3G3 F3 F1 F1 F3 F2 F2XIV 3 F2 0 0 F2 F1 0 0 0 0 F2 1 F1 0 0 F1 0 0 0 0 0 0XV 3 F2G2 0 F1 F3G3 F2G2 N2F1 N3F2 N3G3 N1 F2 1 F2G1 0 0 F3G2 F2G1 0 N1 N1G1 0 F1XVI 3 F3G3 F1 N1F2 F3G3 F3G3 F1 F1 F3G3 F1 F2 1 F3G2 0 N1 F3G3 F3G3 0 0 F2 0 F1XVII 3 F1 0 0 F1 F1 0 0 0 0 F2G1 1 0 0 0 0 F1 0 0 0 0 0XVIII 3 F3G2 0 0 F2G2 F2G2 0 0 0 0 F2 1 F2G1 0 0 F1G1 F1 0 0 0 0 0XIX 3 F3G3 F1 F2 F3G3 F3G3 F1 F1 F3G1 C1F1 F2 1 F3G2 0 F1 F3G3C2 F3G2 F1 0 F2 C1F1 F1XX 3 F1 0 0 C1 F1 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0XXI 3 F2G1 0 0 F2G1 F2 0 0 0 0 F1 1 F2 0 0 F1 F1 0 0 0 0 0XXII 3 F2G1 0 0 F2G1 F2 0 0 0 0 F1 1 F2 0 0 F1 F1 0 0 0 0 0XXIII 3 0 0 0 0 G1 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0XXIV 3 F1 0 0 F1 F1 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0XXV 3 0 0 0 0 F1C1 0 0 0 0 0 1 0 0 0 0 F0 0 0 0 0 0Comments more more more more more more more more fruit fruit fruit fruit fruit fruit fruit fruit set set set set set set set set__________________________________________________________________________Appl'n.Rate Compound No.Species (lb/A) 4758 4759 4760 4762 4764 4850 4956 4957 4958 4959__________________________________________________________________________I 3 F1G1 0 0 F3G2 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 1 0 0 0 F2G1 F3G2 F3G3 F2G2 F3G3 F3G2 F3G3II 3 F1G1 F1 0 F2G2 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 1 0 0 0 F1 F3G3 F3G2 F2G2 F3G3 F3G3 F3G3III 3 0 0 0 0 F1G1 0 F1G1 F2G1 F2G2 F2G1 1 0 0 0 0 0 0 0 0 G1F1 F1IV 3 0 0 0 0 0 0 G1 F1G1 F1G1 G1 1 0 0 0 0 0 0 0 0 0 0V 3 0 0 0 0 F2G1 0 F2G1 F2G2 F3G2 F2G2 1 0 0 0 0 C1 0 0 F1 F2G1 F1VI 3 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0VII 3 0 0 0 0 F1 0 F1 F1 F1 F1 1 0 0 0 0 F1 0 0 0 F1 0VIII 3 N1 0 0 F1 F2G1 N1 F2 F3G1 F3G2 F3G2 1 0 0 0 0 F2 0 F1 F1 F2 F1IX 3 F2G2 0 0 F1 F3G3 F3G3 F3G2 F3G3 F3G3 F3G3 1 F2 0 0 F1 F3G2 F3 F3 F3G2 F3G3 F3G3X 3 F1 F1 F1 F1 F3G3C3 F2G1 F3G2 F3G2 F3G3 F3G3 1 0 0 F1 F1 F2G2 F2 F2G1 F2G2 F3G2 F2G2XI 3 0 0 0 0 F1C1 F1 F3G3 F3G3 F3G3 F3G2 1 0 0 0 0 F1 0 F2G1 F1G1 F2G2 F2G2XII 3 0 G1 0 0 F3G2C2 -- F2G1 F3G2 F3G3 F3G3 1 0 0 0 0 F1C1 F1G1 F1 F2G1 F3G2 F2G2XIII 3 F3 N1 N1F1 F1 F3C2 F3G1 F3E3 F3G3 F3G3 F3G3 1 F2 0 0 0 F3 F3 F3#2 F3E1 F3E3 F3E2XIV 3 0 0 0 0 F2G1 F1 F1 F2 F2 F2 1 0 0 0 0 F1 F1 F1 F1 F2 F2XV 3 N1 0 0 F1 F3G2 F2G1 F2G2 F2G2 F3G2 F2G2 1 0 0 0 0 F2G1 F2 F2G1 F2G1 F3G2 F2G2XVI 3 N1F1 N1 F1 F1 F3G3 F3G3 F3G3 F3G3 F3G3 F3G3 1 0 0 0 F1 F3G3 F3G3 F3G2 F3G3 F3G3 F3G3XVII 3 0 0 0 0 F1 0 F1G1 F1 F2 F1 1 0 0 0 0 0 0 F1 F1 F1 F1XVIII 3 0 0 0 0 F2G1 F1G1 F2G1 F2G2 F3G2 F2G1 1 0 0 0 0 F1 0 F1 F1 F2 F1XIX 3 0 0 F1 F2 F3G2 F3G3 F3G2 F3G3 F3G3 F3G3 1 0 0 0 F1 F2 F3 F3G1 F3G1 F2G1 F2G2XX 3 0 0 0 0 C1 0 F1 F1 F1 F1 1 0 0 0 0 0 0 0 F1 F1 0XXI 3 0 0 0 0 0 0 F2 F2 F3G1 F2 1 0 0 0 0 0 0 F1 F1 F2 F1XXII 3 0 0 0 0 0 0 F2 F2 F3G1 F2 1 0 0 0 0 0 0 F1 F1 F2 F1XXIII 3 0 0 0 0 F1 F1 F1 F1 F2G2 F1G1 1 0 0 0 0 0 0 0 F1 F1G1 0XXIV 3 0 0 0 0 F2 F1 F1 F1 F1 F1 1 0 0 0 0 0 0 0 F1 F1 F1XXV 3 0 0 0 0 F1 0 F1 F1 F1 F1 1 0 0 0 0 0 0 0 F1 F1 0Comments more tillers__________________________________________________________________________

The use of many of the growth regulator compounds may be demonstrated by treatment of soybeans (soja max) to increase the number of seed pods and by treating tomato plants (lycopersicum esculentum) to increase fruit set. In an illustrative experiment, Soja max (Evans variety) and Lycopersicum esculentum (Tinyl Tim variety) were grown in 4-inch pots (one plant per pot) filled with greenhouse potting soil (2 parts good top soil, 11/2 parts builders sand, 11/2 parts peat, fertilized with 5 lb. of 12-12-6 fertilizer and 5 lb. of finely ground limestone per cu. yd.). Aqueous spray formulations were prepared and the potted plants were sprayed at a spray volume of 40 gal. per acre and at application rates of 16, 4, 1 and 1/4 oz. per acre. The spray mixtures were prepared by dissolving the proper amount of growth regulator compound in 15 ml. of acetone, adding 2 ml. of a solvent-emulsifier mixture consisting of 60 wt. percent of a commercial polyoxyethylated vegetable oil emulsifier (96 wt. percent active ingredient, Emulphor El-719), 20 wt. percent xylene and 20 wt. percent deodorized kerosene, then bringing total volume up to 80 ml. by addition of a 0.156 wt. percent aqueous solution of liquid non-ionic dispersant (90 wt. percent active trimethylnonyl polyethylene glycol ether, Tergitol TMN-10). Two replicates were sprayed at all application rates. For comparative purposes, plants were also sprayed at 40 gal./acre with water. The number of seed pods and of fruit as percentage of arithmetic mean of the numbers on untreated plants was observed within approximately three weeks after spray treatment and the results are tabulated below. The extent of growth regulatory effect on the plants was estimated on a scale of 0 to 10 and is also recorded in the following table:

TABLE 4______________________________________GROWTH REGULATING EFFECTS ON TWO SPECIES TOMATO SOYBEAN G.R. G.R.Com- Effect Effectpound Rate 2 Rep. Fruit Increase 2 Rep. Pod IncreaseNo. oz/A. Avg. % of Check Avg. % of Check______________________________________4368 16 6.5 150 7.5 203 4 4.5 236 4 155 1 2.5 192 3 121______________________________________

The information presented in tabular form herein will enable a worker in the art to make a selection from among the growth regulator compounds of the invention and to make some judgment with regard to application rates, depending upon the effect which is desired. It may be seen, for example, that total kills of some species of vegetation may occur at application rates as high as 5 to 10 lb. per acre, whereas beneficial effects may be observed on living plants at application rates of 1 lb. per acre or less.

The growth regulator compounds are usually applied in combination with inert carriers or diluents, as in aqueous sprays, granules and dust formulations in accordance with established practice in the art. An aqueous spray is usually prepared by mixing a wettable powder or emulsifiable concentrate formulation of a growth regulator with a relatively large amount of water to form a dispersion.

Wettable powders comprise intimate, finely divided mixtures of growth regulator compounds, inert solid carriers and surface active agents. The inert solid carrier is usually chosen from among the attapulgite clays, the kaolin clays, the montmorillonite, clays, the diatomaceous earths, finely divided silica and purified silicates. Effective surfactants, which have wetting, penetrating and dispersing ability are usually present in a wettable powder formulation in proportions of from 0.5 to about 10 percent by weight. Among the surface active agents commonly used for this purpose are the sulfonated lignins, naphthalenesulfonates and condensed naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates and non-ionic surfactants such as products of condensation of ethylene oxide with alkylphenols.

Emulsifiable concentrates of the growth regulator compounds comprise in each instance, a solution of growth regulator compound in a liquid carrier which is a mixture of water-immiscible solvent and surfactants, including emulsifiers. Useful solvents include aromatic hydrocarbon solvents such as the xylenes, alkylnaphthalenes, petroleum distillates, terpene solvents, ether-alcohols and organic ester solvents. Suitable emulsifiers, dispersing and wetting agents may be selected from the same classes of products which are employed in formulating wettable powders.

In general, the growth regulators are applied in formulations which desirably contain from 0.1 percent to 95 percent of a compound of formula (1) and from 0.1 to 75 percent of a carrier or surfactant. However, direct application to plant seeds prior to planting may be accomplished in some instances by mixing powdered solid growth regulator with seed to obtain a substantially uniform coating which is very thin and comprises only one or two percent by weight or less, based on the weight of the seed. In most instances, however, a nonphytotoxic solvent, such as methanol is employed as a carrier to facilitate the uniform distribution of growth regulator on the surface of the seed.

When a compound is to be applied to the soil, as for a pre-emergence application, granular formulations are sometimes more convenient than sprays. A typical granular formation comprises the growth regulator compound dispersed on an inert carrier such as coarsely ground clay, or clay which has been converted to granules by treatment of a rolling bed of the powdered material with a small amount of liquid in a granulating drum. In the usual process for preparing granular formulations, a solution of the active compound is sprayed on the granules while they are being agitated in a suitable mixing apparatus, after which the granules are dried with a current of air during continued agitation.

Claims

1. Compounds of the following general structural formulas: ##STR10## in which R, R.sup.1 and R.sup.5 are hydrogen or C.sub.1 to C.sub.5 alkyl, R.sup.2 and R.sup.3 are alike or unlike, one of which may be hydrogen but otherwise are substituents selected from C.sub.1 to C.sub.5 alkyl, alkenyl or alkynyl, branched or unbranched, C.sub.2 to C.sub.5 hydroxyalkyl or alkoxyalkyl, C.sub.3 to C.sub.5 cycloalkyl, furfuryl, pyridyl, benzyl, phenyl, C.sub.1 to C.sub.5 alkylphenyl, or --NR.sup.2 R.sup.3 together may be 2,5-dimethyl-1-pyrryl, 4-morpholinyl or 1-pyrrolidinyl, R.sup.4 is halogen, nitro, cyano, trifluoromethyl or C.sub.1 to C.sub.5 alkyl and n is zero, one or two.

2. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(C.sub.2 H.sub.5).sub.2 and n is zero.

3. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(CH.sub.3).sub.2 and n is zero.

4. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --4-morpholinyl and n is zero.

5. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --1-pyrrolidinyl and n is zero.

6. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-methyl benzyl and n is zero.

7. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-isopropyl benzyl and n is zero.

8. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-methyl phenyl and n is zero.

9. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-ethyl phenyl and n is zero.

10. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(CH.sub.2 CH.sub.2 CH.sub.3).sub.2 and n is zero.

11. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is ##STR11## and n is zero.

12. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2 and n is zero.

13. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-propyl phenyl and n is zero.

14. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(sec.butyl).sub.2 and n is zero.

15. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2 and n is zero.

16. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(allyl).sub.2 and n is zero.

17. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(isobutyl).sub.2 and n is zero.

18. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-methyl propyl and n is zero.

19. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-propyl isopropyl and n is zero.

20. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-propyl isobutyl and n is zero.

21. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-propyl sec.butyl and n is zero.

22. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-propyl butyl and n is zero.

23. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-benzyl 2-propynyl and n is zero.

24. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-allyl phenyl and n is zero.

25. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-ethyl p-tolyl and n is zero.

26. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is 4-morpholinyl and (R.sup.4).sub.n is 3-fluoro.

27. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --NH--(CH.sub.2).sub.3 CH.sub.3 and (R.sup.4).sub.n is 3-fluoro.

28. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --NH--C(CH.sub.3).sub.3 and n is zero.

29. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --NH-cyclopropyl and n is zero.

30. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --NH-cyclopentyl and n is zero.

31. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(CH.sub.3)(CH.sub.2 CH.sub.2 OH) and n is zero.

32. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(CH.sub.3).sub.2 and (R.sup.4).sub.n is 2,5-dimethyl.

33. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(CH.sub.3).sub.2 and (R.sup.4).sub.n is 4-nitro.

34. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(CH.sub.3).sub.2 and (R.sup.4).sub.n is 4-fluoro.

35. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(CH.sub.3).sub.2 and (R.sup.4).sub.n is 4-cyano.

36. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(CH.sub.3).sub.2 and (R.sup.4).sub.n is 4-trifluoromethyl.

37. The compound according to claim 1 in which R and R.sup.1 are hydrogen, --NR.sup.2 R.sup.3 is --N(CH.sub.3).sub.2 and (R.sup.4).sub.n is 3-fluoro.

38. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is 1-pyrrolidinyl and (R.sup.4).sub.n is 3-fluoro.

39. The compound according to claim 1 in which R is 4-methyl, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --NH(CH.sub.2).sub.3 CH.sub.3 and n is zero.

40. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --NH--CH.sub.2 CH.sub.2 OCH.sub.3 and n is zero.

41. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N-methyl furfuryl and n is zero.

42. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --2,5-dimethyl-1-pyrryl and n is zero.

43. The compound according to claim 1 in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --NH-2-pyridyl and n is zero.

44. A compound having one of the following structural formulas: ##STR12## in which R is H, R.sup.1 is CH.sub.3, --NR.sup.2 R.sup.3 is --1-piperidyl, R.sup.5 is hydrogen or C.sub.1 to C.sub.5 alkyl and n is zero.

45. A compound having one of the following structural formulas: ##STR13## in which R is H, R.sup.1 is CH.sub.3, --NR.sup.2 R.sup.3 is --N(nonyl).sub.2, R.sup.5 is hydrogen or C.sub.1 to C.sub.5 alkyl and n is zero.

46. A compound having one of the following structural formulas: ##STR14## in which R is H, R.sup.1 is CH.sub.3, --NR.sup.2 R.sup.3 is --N-methylcyclooctyl, R.sup.5 is hydrogen or C.sub.1 to C.sub.5 alkyl and n is zero.

47. A compound having one of the following structural formulas: ##STR15## in which R is H, R.sup.1 is CH.sub.3, --NR.sup.2 R.sup.3 is --N(octyl).sub.2, R.sup.5 is hydrogen or C.sub.1 to C.sub.5 alkyl and n is zero.

48. A compound having one of the following structural formulas: ##STR16## in which R is hydrogen, R.sup.1 is methyl, --NR.sup.2 R.sup.3 is --N(CH.sub.3).sub.2 and (R.sup.4).sub.n is 3-acetyl, and R.sup.5 is hydrogen or C.sub.1 to C.sub.5 alkyl.