Substituted thiosemicarbazides, their manufacture and use as plant growth regulants

BRIEF SUMMARY OF THE INVENTION
The present invention is directed to a class of novel 1-benzoyl-3-thiosemicarbazides which are useful as plant growth regulants. The present invention is also directed to methods and formulations for plant growth regulation.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a class of novel 1-benzoyl-3-thiosemicarbazides of the formula I: ##STR1## wherein R is ##STR2## R.sup.1 is --OH, --NR'R", C.sub.1 -C.sub.4 alkyl or hydrogen; Q is hydrogen or C.sub.1 -C.sub.4 straight chain alkyl;
each of R' and R" independently is hydrogen or C.sub.1 -C.sub.10 alkyl, C.sub.3 -C.sub.7 alkoxyalkyl or alkoxyalkoxyalkyl, C.sub.3 -C.sub.6 cycloalkyl, phenyl C.sub.1 -C.sub.2 alkyl where the phenyl group is optionally mono-substituted by fluoro or methoxy, or R' and R" taken together with the nitrogen atom to which they are attached form a pyrrolidino, piperidino or morpholino ring;
each R.sup.2 independently is chloro, fluoro, bromo, methyl, nitro or trifluoromethyl;
m is 0, 1 or 2;
R.sup.3 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.4 alkenyl containing no .alpha.,.beta. unsaturation, 2-hydroxyethyl, phenyl or benzyl;
R.sup.4 is hydrogen or C.sub.1 -C.sub.3 alkyl;
Ar is naphthyl, anthranyl, phenanthryl or a group having one of the following formulae: ##STR3## each R.sup.5 independently is C.sub.1 -C.sub.4 alkyl, chloro, bromo, fluoro, nitro, C.sub.1 -C.sub.3 alkoxy or C.sub.1 -C.sub.3 alkylthio, provided that both ortho positions are not substituted by alkyl;
R.sup.6 is carbethoxy, phenoxy, benzyloxy, phenyl or dimethylamino;
n is 0, 1, 2 or 3;
q is 0 or 1;
the sum of n plus q does not exceed 3; and
p is 0 or 1;
or an agriculturally-acceptable salt or ester thereof.
The present invention is also directed to methods employing and formulations comprising the foregoing compounds for plant growth regulation.
SYNTHESIS OF THE COMPOUNDS
The compounds of the invention may be prepared by reacting a compound of formula II: ##STR4## with a phthalic acid derivative of formula: ##STR5## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 and m are as defined above and where X is a good leaving group, preferably a halogen atom such as chlorine.
It is highly preferred that the above reaction be effected in a homogeneous system, i.e. be a uniphase reaction. Thus, an organic solvent is advantageously utilized which is capable of dissolving both reactants. Suitable organic solvents which may be mentioned are polar organic solvents such as chloroform, ethylene dichloride, isopropanol, dioxane, 1,2-dimethoxyethane and dimethylformamide and methylenedichloride.
The reaction is preferably effected without drastic heating, temperatures in the range from -40.degree. to 100.degree. C. generally being suitable--although the utilization of temperatures in the range from room temperature to 50.degree. C. is preferred.
Many of the intermediates of formula II are believed to be novel.
Free acids of formula I (i.e. compounds in which R.sup.1 is hydroxyl) may be converted to salts or esters. To effect salt formation the acid can be neutralized with any suitable base using conventional techniques. For instance, the potassium salt can be generated from the free acid by reaction with KOH in isopropanol. Generally, any suitable inert solvent capable of dissolving at least one of the reactants to an appreciable extent may be utilized. Preferred temperatures for the neutralization lie in the range of from -40.degree. to 100.degree. C., most preferably from room temperature to 50.degree. C. As well as metal salts, ammonium and quaternary ammonium salts can be formed by the neutralization process, as can amine salts such as those formed with pyridine or diethylamine. The salts of the invention can also be formed by conventional double decomposition techniques.
The compounds of formula II in which R.sup.4 is hydrogen can be prepared by reaction of the corresponding isothiocyanate of formula V:
S.dbd.C.dbd.N--Ar V
and the corresponding hydrazine of formula:
H.sub.2 N--NHR.sup.3
at a temperature from 0.degree. to 50.degree. C. in an inert organic solvent such as toluene capable of dissolving both reactants to an appreciable extent. This procedure is described in Acta. Chemica. Scandinavica., 22 (1), 1, 1968. Compounds of formula II in which R.sup.4 is not hydrogen can be prepared by reacting the corresponding N-alkyl-N-arylthiocarbamyl chloride of formula VI: ##STR6## with a hydrazine of formula:
H.sub.2 N--NHR.sup.3
The reaction may be effected in inert organic solvents such as diethyl ether and at a temperature in the range from 0.degree. to 50.degree. C., preferably at room temperature.
Compounds of formula VI may be prepared by the general method described in Chemical Abstracts, 58, 4543, i.e. reaction of the corresponding amine of formula ArNHR.sup.4 and thiophosgene in an ethereal solvent under anhydrous conditions at a temperature between 0.degree. C. and room temperature.
Esters of formula I can be converted to other esters by methods well-known to those skilled in the art. For instance, ester exchange reactions may be accomplished by dissolving the ester in an excess of the alcohol with which exchange is desired. A small amount of base such as tertiary butylamine may be utilized to promote the reaction which is advantageously effected at temperatures in the range from -40.degree. to 60.degree. C. preferably from 0.degree. to 50.degree. C., most preferably at about room temperature.
Compounds of formula I in which R.sup.1 is NR'R" can be prepared by reacting the corresponding methyl ester (R is COOMe) with the appropriate amine of formula HNR'R".
The methyl esters of formula I (i.e. R is COOMe) can also be used to prepare the corresponding hydroxymethyl (i.e. R is CH.sub.2 OH) compounds. Thus, the methyl esters can be reduced to the corresponding hydroxymethyl derivatives by treatment with chemical reducing agents such as sodium borohydride (NaBH.sub.4). This reduction is preferably effected at a temperature in the range from 0.degree. to 50.degree. C., most preferably at 5.degree. C. to room temperature. Suitable organic solvents which may be mentioned are the alkanolic solvents such as ethanol. Similarly, compounds of formula I in which R is --CHQOH where Q is C.sub.1 -C.sub.4 alkyl can be prepared by reduction of the corresponding acyl derivatives (R is --COR.sup.1 where R.sup.1 is C.sub.1 -C.sub.4 alkyl) using chemical reducing agents such as lithium aluminum hydride or sodium borohydride as above.

The following Preparations will serve to illustrate the preparation of intermediates of use in the invention. All temperatures are in degrees Celsius.
PREPARATION 1
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--m.p. 82.5.degree.-84.degree.).
PREPARATION 2
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 to 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).
PREPARATION 3
2,4-Dimethyl-4-phenyl-3-thiosemicarbazide
To a solution of N-methyl-N-phenylthiocarbamyl chloride (79.6 g, 0.43 mole) in 250 ml dry ether, a solution of 39.5 g (0.86 mole) methylhydrazine in 100 ml of dry ether was added dropwise with stirring below 10.degree. C. The reaction temperature was allowed to increase to room temperature and the mixture was filtered. The filtrate was evaporated to low volume and diluted with about 300 ml hexane. After stirring for a few hours the hexane layer was decanted. The hexane immiscible layer was re-evaporated to remove organic solvents, giving the desired product, (70.0 g) as a thick orange liquid.
PREPARATION 4
4-Methyl-4-phenyl-3-thiosemicarbazide
To a solution of 7.7 g (0.24 mole) anhydrous hydrazine in 200 ml of dry ether, N-methyl-N-phenylthiocarbamyl chloride (20.4 g, 0.11 mole) was added below 5.degree. C. with stirring. The mixture was stirred and allowed to warm to room temperature. The mixture was filtered and the residue resuspended in about 100 ml water and stirred. Filtration gave 8.8 g of the desired product as a whitish powder, m.p. 121.degree.-22.degree..
PREPARATION 5
1-Amino-3-(2-naphthyl)thiourea
Anhydrous hydrazine (1.1 g, 0.035 mole) was dissolved in 150 ml of diethyl ether in a round-bottomed flask. 2-Naphthyl isothiocyanate (4.6 g, 0.25 mole) was added dropwise to the mixture keeping the pot temperature below 30.degree. during the addition. The reaction mixture was stirred overnight at room temperature. The reactants were then cooled and the title product filtered off. The product was air-dried, yield 4.5 g, m.p. 174.degree.-6.degree..
PREPARATION 6
2-Benzyl-4-phenyl-3-thiosemicarbazide
Benzylhydrazine (30 g, 0.0245 mole) and phenyl isothiocyanate (33.1 g, 0.0245 mole) were dissolved in 200 ml of isopropanol and cooled to 0.degree.-5.degree. C. The phenyl isothiocyanate was then added dropwise in 50 ml of petroleum ether. The title compound precipitated from solution during this phase of the operation. After addition, the reaction mixture was stirred at 40.degree.-45.degree. C. for one hour. The title product was filtered off as a white solid, m.p. 121.degree.-3.degree. C., yield 43 g.
The following Examples illustrate the preparation of compounds of formula I. All temperatures are in degrees Celsius.
EXAMPLE 1
1-(2-Carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide
A solution of 45.3 g (0.25 mole) of 2-methyl-4-phenyl-3-thiosemicarbazide and 19.8 g (0.25 mole) of pyridine in 800 ml of 1,2-dimethoxyethane was stirred at room temperature while 49.8 g (0.25 mole) of methyl phthaloyl chloride in 100 ml of 1,2-dimethoxyethane was added dropwise over a period of two hours. The resulting reaction mixture was stirred for 16 hours at room temperature. At the end of this time the contents of the flask were poured into ice water. The solid which formed was collected and amounted to 73.3 g (85%); the melting point was 153.5.degree.-154.degree..
EXAMPLE 2
1-(2-Carbomethoxybenzoyl)-2-isopropyl-4-phenyl-3-thiosemicarbazide
2-Isopropyl-4-phenyl-3-thiosemicarbazide (0.25 mole) prepared by reacting isopropylhydrazine with phenyl isothiocyanate according to the procedure of Acta. Chem. Scand. 22 (1), 1 (1968) and pyridine (0.25 mole) were dissolved in 125 ml of dimethoxyethane and placed in a 300 ml 3-necked flask equipped with funnel and thermometer. The contents were cooled to 10.degree.-15.degree. and methyl phthaloyl chloride (0.25 mole) in 25 ml of dimethoxyethane, added dropwise. The contents were then stirred overnight at room temperature. The following morning the contents were poured into ice water yielding the title product as a solid which was rinsed with hexane and ethyl acetate. No further purification was required. (m.p. 145.degree.-147.degree.), yield, 15.4 g
EXAMPLE 3
1-(2-Carbomethoxybenzoyl)-4-phenyl-3-thiosemicarbazide
The title compound was prepared by the procedure of Example 2. The resultant solid was rinsed with hexane and ethyl acetate and required no further purification. (m.p. 140.degree.-142.degree. C.) yield, 87%
EXAMPLE 4
1-(2-Carboxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide
2-Methyl-4-phenyl-3-thiosemicarbazide (0.2 mole) 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. Phthalic anhydride (0.2 mole) was added in portions at 20.degree.. The contents were stirred overnight at room temperature, then poured into ice water the following morning. The resulting solid title product was recrystallized from a mixture of hexane and ethanol. (m.p. 155.degree.-156.degree.) yield, 70%
EXAMPLE 5
1-(2-Carboxybenzoyl)-4-phenyl-3-thiosemicarbazide
The same apparatus and procedure were used as in Example 4. After all the phthalic anhydride was added the contents were heated at 80.degree. for about 3 hours. The contents were then cooled and poured into ice water resulting in production of the title compound as a solid. This solid was rinsed with a mixture of hexane and ethanol. (m.p. 149.degree.-151.degree.) yield, 66%
EXAMPLE 6
1-(2-Carboxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide, sodium salt
The free acid of Example 4 was suspended in methanol and placed in a 300 ml round-bottomed flask equipped with magnetic stirrer and condenser. Sodium methoxide was suspended in methanol and added to the reaction flask. The reaction mixture was stirred at room temperature for 30 minutes during which time all solids went into solution. The contents were then evaporated, yielding the title product. Yield, 7.6 g, m.p. 195.degree.-197.degree. (dec.)
EXAMPLE 7
1-(2-Carboxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide, ammonium salt
The free acid compound of Example 4 was suspended in 100 ml of ethanol and placed in a 300 ml round-bottomed flask equipped with magnetic stirrer and condenser. Twenty ml of dimethoxyethane were added to make the compound go into solution. After most of the solid had gone into solution, NH.sub.4 OH was added. There was no discernible heat evolution. Solvents were evaporated. The resulting solid (title product) was refluxed in a mixture of hexane and ethanol and was then recovered by filtration. Yield 4.3 g (m.p. 165.degree.-166.degree.)
EXAMPLE 8
1-(2-Carboisopropoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide
To a solution of 5.0 g (0.014 mole) of 1-(2-carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide in 75 ml of isopropyl alcohol was added 1.0 g (0.014 mole) of tert-butylamine and the solution was stirred at room temperature for 16-18 hours. Most of the isopropyl alcohol was removed at reduced pressure, and water was added and the resulting precipitate was collected. The title compound thus produced had a melting point of 115.degree.-117.degree..
EXAMPLE 9
2-Benzyl-1-(2-carboxybenzoyl)-4-phenyl-3-thiosemicarbazide
Phthalic anhydride (3.7 g, 0.25 mole) and 2-benzyl-4-phenyl-3-thiosemicarbazide (6.43 g, 0.25 mole) were dissolved in 100 ml of dimethylformamide and heated at 90.degree. C. for three hours. The solution was cooled then poured into ice water with stirring. The title product was filtered off as a solid material. Recrystallization gave a substance having a melting point of 140.degree.-142.degree..
EXAMPLE 10
1-(2-Carboxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide, potassium salt
1-(2-Carboxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide (60 g, 0.182 mole) was dissolved (slurried) in 400 ml ethanol. Potassium hydroxide (10.2 g) was dissolved in 200 ml ethanol and added to the acid-ethanol mixture. Ethanol was evaporated until a crystalline product precipitated, yield 51 g and m.p. 182.degree.-183.degree..
EXAMPLE 11
1-(2-Dimethylaminocarbonylbenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide
1-(2-Carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide (5 g, 0.148 mole) was suspended in aqueous dimethylamine. The pH of the suspension was adjusted to about 3. A tacky precipitate was formed which become solid after addition of diethyl ether. This solid--title product--had a melting point of 140.degree.-143.degree., yield 3.7 g.
EXAMPLE 12
1-(2-Hydroxymethylbenzoyl)-2-methyl-4-(3-fluorophenyl)-3-thiosemicarbazide
1-(2-Carbomethoxybenzoyl)-2-methyl-4-(3-fluorophenyl)-3-thiosemicarbazide (7.2 g) was dissolved in ethanol (100 ml). The solution was cooled to below 10.degree. and sodium borohydride (1.1 g) added. The mixture was then stirred at room temperature for 60 hours. Water was then added with production of an amorphous precipitate. Dilute hydrochloric acid was then added to the filtrate to bring it to pH 7 and further precipitate removed by filtration. The filtrate was thereupon acidified to yield the title product as a solid, m.p.136.degree.-137.degree., yield 3.4 g.
Using the foregoing procedures a large number of other compounds of formula I were prepared. These compounds, as well as the compounds prepared by the processes of Examples 1 to 12, are listed in the following Table I.
TABLE I__________________________________________________________________________ ##STR7##CompoundNo. R m R.sup.2 R.sup.3 R.sup.4 Ar M.P. .degree.C.__________________________________________________________________________ 597 COOCH.sub.3 O -- CH.sub.3 H phenyl 153.5-154.degree.1685 COOCH.sub.3 " -- CH(CH.sub.3).sub.2 H phenyl 145-147.degree.1686 COOCH.sub.3 " -- H H phenyl 140-142.degree.2005 COOH " -- CH.sub.3 H phenyl 155-156.degree.2008 COOH " -- H H phenyl 149-151.degree.2044 COONa " -- CH.sub.3 H phenyl High melt solid2047 COONH.sub.4 " -- CH.sub.3 H phenyl 165-166.degree.2322 COOCH.sub.3 " -- CH.sub.3 H benzyl 144-146.degree.2324 COOCH.sub.3 " -- H H benzyl 133-135.degree.2325 COOCH.sub.3 " -- CH.sub.3 H 4-methyl- 138-140.degree. phenyl2341 COONa " -- H H benzyl High melt solid2342 COONH.sub.4 " -- H H benzyl 173-175.degree.2370 COOCH.sub.2 CH.sub.2 CH.sub.3 " -- CH.sub.3 H phenyl 117-119.degree.2371 COOCH.sub.2 CH.sub.3 " -- CH.sub.3 H phenyl 142-145.degree.2372 COO(CH.sub.2).sub.3 CH.sub.3 " -- CH.sub.3 H phenyl 98-100.degree.2388 COOCH.sub.3 " -- CH.sub.3 H 3-chloro- 142-146.degree. 4-methyl- phenyl2389 COOCH.sub.3 " -- CH.sub.3 H 3-methyl- 138-140.degree. phenyl2390 COOCH.sub.3 " -- CH.sub.3 H 3-methoxy- 142-144.degree. phenyl2391 COOCH.sub.3 " -- CH.sub.3 H 2-fluoro- 152-154.degree. phenyl2392 COOCH.sub.3 " -- CH.sub.3 H 4-fluoro- 127-129.degree. 2-methyl- phenyl2414 COOCH.sub.2 CH.sub.2 Cl " -- CH.sub.3 H phenyl 126-131.degree.2415 COO(CH.sub.2).sub.6 Cl " -- CH.sub.3 H phenyl oil2418 COOH " -- benzyl H phenyl 140-142.degree.2422 COOCH.sub.3 " -- benzyl H phenyl 103-106.degree.2432 COOH 1 3-CH.sub.3 CH.sub.3 H phenyl 123-126.degree.2433 COOH " 3-CH.sub.3 H H phenyl 122- 123.degree.2434 COONH.sub.4 " 3-CH.sub.3 CH.sub.3 H phenyl 154-157.degree.2444 COO(CH.sub.2).sub.4 CH.sub.3 0 -- CH.sub.3 H phenyl 131-133.degree.2445 ##STR8## " -- CH.sub.3 H phenyl 126-129.degree.2446 COO(CH.sub.2).sub.5 CH.sub.3 " -- CH.sub.3 H phenyl 113-117.degree.2450 COOH 1 6-NO.sub.2 CH.sub.3 H phenyl 160-163.degree.2470 CONH.sub.2 0 -- CH.sub.3 H phenyl 161-163.degree.2472 CON(CH.sub.3).sub.2 " -- CH.sub.3 H phenyl 140-143.degree.2474 COOH " -- CH.sub.3 H 4-chloro- 165-166.degree. phenyl2479 COOH " -- CH.sub.3 H benzyl 161-163.degree.2480 COOH " -- H H benzyl 183-184.degree.2481 COOH " -- CH.sub.3 H 4-methyl- 156-158.degree. phenyl2482 COOH " -- CH.sub.3 H 3-methyl- 133-135.degree. phenyl2483 COOH " -- CH.sub.3 H 2-fluoro- 137-139.degree. phenyl2484 COOH " -- CH.sub.3 H 4-fluoro- 158-161.degree. 2-methyl- phenyl2487 COOH " -- CH.sub.3 H 4-fluoro- 167-168.degree. phenyl2488 COOH " -- CH.sub.3 H 3-fluoro- 165-166.degree. phenyl2563 COOCH.sub.3 " -- CH.sub.3 H 2-chloro- 151-153.degree. phenyl2564 COOCH.sub.3 " -- CH.sub.3 H 2-nitro- 171-173.degree. phenyl2567 COOCH.sub.3 " -- CH.sub.3 H 4-fluoro- 149-151.degree. phenyl2568 COOCH.sub.3 " -- CH.sub.3 H 3-fluoro- 146-148.degree. phenyl2569 COOCH.sub.3 " -- CH.sub.3 H 4-chloro- 159-161.degree. phenyl2570 COOCH.sub.3 " -- CH.sub.3 H 3-chloro- 143-145.degree. phenyl2571 COOCH.sub.3 " -- CH.sub.3 H 4-nitro- 195-197.degree. phenyl2572 COOCH.sub.3 " -- CH.sub.3 H 3-(tri- 141-143.degree. fluoro- methyl)- phenyl2573 COOCH.sub.3 " -- H H 3-methoxy- 132-134.degree. phenyl2574 COOCH.sub.3 " -- H H 3-chloro- 155-158.degree. methyl- phenyl2576 COOCH.sub. 3 " -- H H 2-nitro- 144-146.degree. phenyl2577 COOCH.sub.3 " -- H H 3-methyl- 138-140.degree. phenyl2578 COOCH.sub.3 " -- H H 2-chloro- 149-151.degree. phenyl2579 COOCH.sub.3 " -- CH.sub.3 H 2-naphthyl 135-137.degree.2580 COOCH.sub.3 " -- H H 2-fluoro- 151-153.degree. phenyl2581 COOCH.sub.3 " -- H H 4-fluoro- 163-165.degree. phenyl2583 COOCH.sub.3 " -- H H 4-methyl- 151-153.degree. phenyl2584 COOCH.sub.3 " -- H H 3-fluoro- 158-160.degree. phenyl2585 COOCH.sub.3 " -- H H 4-chloro- 162-164.degree. phenyl2586 COOCH.sub.3 " -- H H 3-chloro- 153-155.degree. phenyl2588 COOCH.sub.3 " -- H H 3-(tri- 161-163.degree. fluoro- methyl)- phenyl2589 COOCH.sub.3 " -- H H 1-naphthyl 146-148.degree.2590 COOCH.sub.3 " -- H H 2-naphthyl 148-150.degree.2591 COOH " -- CH.sub.3 H 3-chloro- 157-158.degree. phenyl2592 COOH " -- CH.sub.3 H 4-nitro- 200.degree. phenyl2594 COOH " -- CH.sub.3 H 1-naphthyl 159-160.degree.2595 COOH " -- CH.sub.3 H 2-naphthyl 112-114.degree.2597 COOH " -- CH.sub.3 H 3-(tri- 155-156.degree. fluoro- methyl)- phenyl2598 COOH " -- H H 3-methoxy- 150-152.degree. phenyl2599 COOH " -- H H 3-chloro- 178-183.degree. 4-methyl- phenyl2603 COOH " -- H H 2-nitro- 170-171.degree. phenyl2604 COOH " -- H H 3-methyl- 169-170.degree. phenyl2605 COOH " -- H H 2-chloro- 165-167.degree. phenyl2622 COO(CH.sub.2).sub.11 CH.sub.3 " -- CH.sub.3 H phenyl oil2627 COO(CH.sub.2).sub.10 CH.sub.3 " -- CH.sub.3 H phenyl oil2628 COO(CH.sub.2).sub.15 CH.sub.3 " -- CH.sub.3 H phenyl oil2633 ##STR9## " -- CH.sub. 3 H phenyl oil2634 ##STR10## " -- CH.sub.3 H phenyl oil2635 ##STR11## " -- CH.sub.3 H phenyl oil2636 ##STR12## " -- CH.sub.3 H phenyl oil2637 ##STR13## " -- CH.sub.3 H phenyl oil2641 COOH " -- CH.sub.2 CH H phenyl 105-125.degree. CH.sub.22668 ##STR14## " -- CH.sub.3 H phenyl oil2669 ##STR15## " -- CH.sub.3 H phenyl 131-133.degree.2697 COOH " -- H H 2-naphthyl 171-174.degree.2698 COOH " -- H H 1-naphthyl 158-159.degree.2699 COOH " -- H H 3-(tri- 167-170.degree. fluoro- methyl)- phenyl2700 COOH " -- H H 4-nitro- 298-302.degree. phenyl2701 COOH " -- H H 3-chloro- 169-170.degree. phenyl2702 COOH " -- H H 4-chloro- 187-189.degree. phenyl2704 COOH " -- H H 3-fluoro- 167-168.degree. phenyl2705 COOH " -- H H 4-methyl- 164-166.degree. phenyl2707 COOH " -- H H 4-fluoro- 179-181.degree. phenyl2708 COOH " -- H H 2-fluoro- 170-171.degree. phenyl2721 COOH " -- CH.sub.3 H 3,4-di- 165-166.degree. chloro- phenyl2722 COOH " -- CH.sub.3 H 4-methoxy- 168-170.degree. phenyl2723 COOH " -- CH.sub.3 H 2-methyl- 173-180.degree. phenyl2724 COOH " -- CH.sub.3 H 4-bromo- 175-176.degree. phenyl2725 COOH " -- H H 3,4-di- 178-179.degree. chloro- phenyl2726 COOH " -- H H 4-methoxy- 198-201.degree. phenyl2727 COOH " -- H H 2-methyl- 179-180.degree. phenyl2728 COOH " -- H H 4-bromo- 178-181.degree. phenyl2729 ##STR16## " -- H H phenyl crude solid2732 ##STR17## " -- H H 3-fluoro- phenyl crude solid2733 COO(CH.sub.2).sub.15 CH.sub.3 " -- H H phenyl crude solid2734 COO(CH.sub.2).sub.15 CH.sub.3 " -- CH.sub.3 H 3-fluoro- oil phenyl2735 COO(CH.sub.2).sub.15 CH.sub.3 " -- CH.sub.3 H 4-fluoro- crude solid phenyl2736 COO(CH.sub.2).sub.15 CH.sub.3 " -- CH.sub.3 H 4-chloro- crude solid phenyl2740 COOC.sub.2 H.sub.4 OC.sub.4 H.sub.9 " -- CH.sub.3 H 3-fluoro- crude solid phenyl2741 COOC.sub.2 H.sub.4OC.sub.4 H.sub.9 " -- CH.sub.3 H 4-fluoro- crude solid phenyl2742 COOC.sub.2 H.sub.4OC.sub.4 H.sub.9 " -- CH.sub.3 H 4-chloro- crude solid phenyl2743 COO(CH.sub.2).sub.9 CH.sub.3 " -- CH.sub.3 H phenyl oil2744 COO(CH.sub.2).sub.17 CH.sub.3 " -- CH.sub.3 H phenyl gum2745 COOCH.sub.2 CH.sub.2Br " -- CH.sub.3 H phenyl gum2746 COO(CH.sub.2).sub.7 CH.sub.3 " -- H H phenyl 117-121.degree.2749 COO(CH.sub.2).sub.9 CH.sub.3 " -- H H phenyl 103-105.degree.2750 COOCH.sub.2 CH.sub.3 " -- H H phenyl 148-150.degree.2753 COOH 1 5-CH.sub.3 CH.sub.3 H phenyl 131-132.degree.2754 COOH " 5-CH.sub.3 H H phenyl 137-139.degree.2756 COOCH.sub.3 " 6-NO.sub.2 CH.sub.3 H phenyl 130-135.degree.2760 COOCH.sub.3 " 5-CH.sub.3 H H phenyl 111-113.degree.2762 COONH.sub.4 " 5-CH.sub.3 H H phenyl 170-172.degree.2771 COONH.sub.4 " 6-CH.sub.3 CH.sub.3 H phenyl 102.degree. (0)2772 COOH " 5-NO.sub.2 CH.sub.3 H phenyl 123-124.degree.2777 ##STR18## " -- H H phenyl 119-124.degree.2778 ##STR19## " -- H H phenyl crude solid2779 ##STR20## 0 -- H H phenyl crude solid2781 COOC.sub.2 H.sub.4OCH.sub.3 " -- H H phenyl crude solid2783 COOC.sub.3 H.sub.6Br " -- H H phenyl 72-75.degree.2784 COOH 1 3-F CH.sub.3 H phenyl 134-136.degree.2787 COOH " 3-F H H phenyl 149-150.degree.2788 COOH 0 -- CH.sub.2 CH.sub.3 H phenyl 153-155.degree.2790 COOH, pyridine " -- CH.sub.3 H phenyl 126-129.degree. salt2795 COOH " -- H CH.sub.3 phenyl 168.degree.2796 COOCH.sub.3 " -- H CH.sub.3 phenyl 95-99.degree.2798 COOCH.sub.3 " -- CH.sub.3 CH.sub.3 phenyl 105-106.degree.2799 COOCH.sub.3 " -- H H 3,4-di- 155-157.degree. chloro- phenyl2800 COOCH.sub.3 " -- H H 4-methoxy- 149-151.degree. phenyl2801 COOCH.sub.3 " -- H H 2-methyl- 175-177.degree. phenyl2802 COOCH.sub.3 " -- H H 4-bromo- 163-165.degree. phenyl2803 COOCH.sub.3 " -- CH.sub.3 H 4-methoxy- 126-128.degree. phenyl2818 COOH 1 5- CH.sub.3 H phenyl 125-127.degree. chloro2819 COOH " 5- H H phenyl 280-283.degree. chloro2822 COOCH.sub.3 0 -- C.sub.2 H.sub.5 H phenyl 166-168.degree.2844 COOH, tri- " -- CH.sub.3 H phenyl 189-190.degree. ethylene- diamine salt2845 COOK " -- CH.sub.3 H phenyl 181-183.degree.2850 COOH 2 4,5- CH.sub.3 H phenyl 320-323.degree. dichloro2851 COOH " 4,5- H H phenyl 158-159.degree. dichloro2852 COONH.sub.4 " 4,5- H H phenyl 170.degree. (dec.) dichloro2853 COONH.sub.4 " 4,5- CH.sub.3 H phenyl 112-115.degree. dichloro2854 COOLi 0 -- CH.sub.3 H phenyl --2855 COOH 1 3-Br CH.sub.3 H phenyl gum2859 COONH.sub.4 " 6-F CH.sub.3 H phenyl 163-165.degree.2862 COONH.sub.4 " 6-F H H phenyl 180.degree. (dec.)2863 COOH 2 3,6- CH.sub.3 H phenyl 116-117.degree. dichloro2879 COOCH.sub.3 0 -- CH.sub.3 H 2,4-di- 155-157.degree. methyl- phenyl2882 COOH, di- " -- CH.sub.3 H phenyl 137-139.degree. methyl- morpholinium salt2883 COOH, salt " -- CH.sub.3 H phenyl 168- 170.degree. with 4H- pyrido[1,2-.alpha.]- pyrazine2885 COOH, salt " -- CH.sub.3 H phenyl 147-149.degree. with diethyl- amine2896 COOH " -- CH.sub.3 H 2,4-di- 172-178.degree. methyl- phenyl2898 COONH.sub.4 1 5- CH.sub.3 H phenyl 144-145.degree. nitro2914 COOH 0 -- CH.sub.3 CH.sub.3 phenyl oil2923 COOH 1 6-CF.sub.3 CH.sub.3 H phenyl 68-74.degree.2954 COOH 0 --phenyl H phenyl 151.degree. (dec.)2987 COOH 1 4- CH.sub.3 CH.sub.3 phenyl 83-90.degree. nitro2992 COOCH.sub.3 0 -- CH.sub.3 H 2-car- 120-122.degree. bethoxy- phenyl2994 COOCH.sub.3 " -- CH.sub.3 H 4-phenoxy- 163-165.degree. phenyl2995 COOCH.sub.3 " -- CH.sub.3 H 4-butyl- 143-145.degree. phenyl2996 COOCH.sub.3 " -- CH.sub.3 H 3-(methyl- 97-99.degree. thio)phenyl2997 COOCH.sub.3 " -- CH.sub.3 H 4-benzyl- 162-164.degree. oxyphenyl2998 COOCH.sub.3 " -- CH.sub.3 H 4-dimethyl- 138-140.degree. aminophenyl2999 COOCH.sub.3 " -- CH.sub.3 H 4-methyl- 147-149.degree. benzyl3000 COOCH.sub.3 " -- CH.sub.3 H 2,6-di- 162-164.degree. chloro- phenyl3001 COOCH.sub.3 " -- CH.sub.3 H 4-carbeth- 142-144.degree. oxyphenyl3002 COOCH.sub.3 " -- CH.sub.3 H 4-iso- 156-158.degree. propyl- phenyl3006 COOH " -- CH.sub.3 H 2-car- 158-159.degree. bethoxy- phenyl3017 COOH " -- CH.sub.3 H 4-phenoxy- 140-142.degree. phenyl3018 COOH " -- CH.sub.3 H 4-butyl- 134-135.degree. phenyl3019 COOH " -- CH.sub.3 H 3-(methyl- glassy solid thio)phenyl3022 COOH " -- CH.sub.3 H 4-iso- 116-118.degree. propyl- phenyl3023 COOH " -- CH.sub.3 H 4-benzyl- 138-139.degree. oxyphenyl3024 COOH " -- CH.sub.3 H 4-(di- 163-165.degree. methyl- amino)phenyl3025 COOH " -- CH.sub.3 H 4-methyl- 157-158.degree. benzyl3026 COOH " -- CH.sub.3 H 4-carbeth- 160-161.degree. oxyphenyl3027 COOH " -- CH.sub.3 H 2,6-di- 156-157.degree. chloro- phenyl3108 COOK " -- CH.sub.3 H 3-fluoro- 184-185.degree. phenyl3109 COONH.sub.4 " -- CH.sub.3 H 3-fluoro- 155-157.degree. phenyl3116 COCH.sub.3 " -- CH.sub.3 H phenyl oil3137 CO-1- " -- CH.sub.3 H phenyl 150-152.degree. piperidyl3146 COOH, octyl- " -- CH.sub.3 H phenyl 133-14 135.degree. amine salt3147 COOH " -- CH.sub.2 CH.sub.2 OH H phenyl 155-157.degree.3151 COOH " -- CH.sub.3 H 2,3-di- 118-120.degree. methyl- phenyl3152 COOH " -- CH.sub.3 H 2,4,5- 160.degree. (re- trimethyl- arranges) phenyl3153 COOH " -- CH.sub.3 H 2,5-di- 130.degree. (re- methyl- arranges) phenyl3158 COOH " -- CH.sub.3 H 3,5-di 107-110.degree. methyl- phenyl3159 COOH " -- CH.sub.3 H 3-ethyl- unpurified phenyl3160 COOH " -- CH.sub.3 H 3,4-di- 126-128.degree. methyl- phenyl3180 COOH, salt " -- CH.sub.3 H phenyl 68-85.degree. with benzyl- dimethylamine3181 COOH, salt " -- CH.sub.3 H phenyl 145-147.degree. with phenyl- (dec.) dimethylamine3182 COOH, salt " -- CH.sub.3 H phenyl 139-141.degree. with (2,3- (dec.) dihydroxy- propyl)di- methylamine3183 COOH, salt " -- CH.sub.3 H phenyl oil with tri- octylamine3184 COOCH.sub.3 " -- CH.sub.2 CH.sub.2 OH H phenyl 147-149.degree.3185 COOCH.sub.3 " -- CH.sub.3 H 2,3-di- 136-138.degree. methyl- phenyl3186 COOCH.sub.3 " -- CH.sub.3 H 2,4,5-tri- 150-152.degree. methyl- phenyl3187 COOCH.sub.3 " -- CH.sub.3 H 2,5-di- 146-147.degree. methyl- phenyl3194 COOCH.sub.3 " -- CH.sub.3 H 3,4-di- 142-144.degree. methyl- phenyl3195 COOCH.sub.3 " -- CH.sub.3 H 3,5-di- 153-155.degree. methyl- phenyl3196 COOCH.sub.3 " -- CH.sub.3 H 3-ethyl- 78-81.degree. phenyl3210 COOH, " -- CH.sub.3 H phenyl 155-158.degree. tetrahydro- furan adduct3284 CONHC(CH.sub.3).sub.3 " -- CH.sub.3 H phenyl 141-142.degree.3285 CONHCH.sub.2 CH.sub.2 CH.sub.3 " -- CH.sub.3 H phenyl 144-148.degree.3290 ##STR21## " -- CH.sub.3 H phenyl unpurified3349 COOCH.sub.3 " -- CH.sub.3 H 4-bromo- 156-159.degree. phenyl3350 COOCH.sub.3 " -- CH.sub.3 H 3-nitro- 178-180.degree. phenyl3352 COOCH.sub.3 " -- CH.sub. 3 H 3,4-di- 159-161.degree. chloro- phenyl3358 ##STR22## " -- CH.sub.3 H phenyl 115-117.degree.3577 (COO).sub.2 Ca " -- CH.sub.3 H phenyl >300.degree.3578 (COO).sub.2 Zn " -- CH.sub.3 H phenyl 170-175.degree. (dec.)3579 (COO).sub.2 Cu " -- CH.sub.3 H phenyl 150-153.degree. (dec.)3580 (COO).sub.3 Fe " -- CH.sub.3 H phenyl 152-157.degree. (dec.)3581 (COO).sub.2 Mn " -- CH.sub.3 H phenyl 158-160.degree. (dec.)3582 (COO).sub.2 Fe " -- CH.sub.3 H phenyl 160-180.degree. (dec.)3676 COOH 2 4,5- H H phenyl 164.degree. (dec.) dichloro3716 CH.sub.2 OH 0 -- CH.sub.3 H 3-fluoro- 136-137.degree. phenyl3873 ##STR23## " -- CH.sub.3 H phenyl 154-156.degree.3874 ##STR24## " -- CH.sub.3 H phenyl 156-158.degree.3875 CONHbenzyl " -- CH.sub.3 H phenyl 143-146.degree.3876 CONHnonyl " -- CH.sub.3 H phenyl 151-152.degree.3877 CONHCH.sub.2(4- " -- CH.sub.3 H phenyl 149-151.degree. methoxyphenyl)3879 CONH-cyclopropyl " -- CH.sub.3 H phenyl 144-146.degree.3880 CON(CH.sub.2 CH.sub.2 CH.sub.3).sub.2 " -- CH.sub.3 H phenyl 132-134.degree.3883 ##STR25## " -- CH.sub.3 H phenyl 143-145.degree.3884 CONH(CH.sub.2).sub.4 CH.sub.3 " -- CH.sub.3 H phenyl 145-147.degree.3866 ##STR26## " -- CH.sub.3 H phenyl 167-169.degree.3869 ##STR27## " -- CH.sub.3 H phenyl 132-134.degree.3872 CONHC(CH.sub.3).sub.3 2 3,6- CH.sub.3 H phenyl 173-174.degree. dichloro3974 ##STR28## 0 -- CH.sub.3 H phenyl 140-142.degree.3975 ##STR29## " -- CH.sub.3 H phenyl 146-148.degree.__________________________________________________________________________
UTILITY OF THE COMPOUNDS
The term "plant growth regulating" and cognate terms are used herein to refer to changes in the normal sequential development of a plant to agricultural maturity. Examples of such changes include shortening or lengthening of the internode distance, increasing flowering or the set of fruit, reducing plant stature, increasing branching or tillering, inhibiting sprouting, inhibiting sucker growth, fruit thinning, defoliation, desiccation, delayed flowering, increased tolerance to cold, drought, and other stress, increased root growth, and delayed senescence. Many others will be apparent to those skilled in the art.
As will be evident from the foregoing types of plant growth regulation, the compounds of formula I are principally intended to alter the further growth of desirable plants. However, because of the variation among plant species, some herbicidal action has been noted. For example, at rates that provide desirable plant growth regulation of some species, numerous compounds of formula I exhibit a herbicidal effect on Digitaria sanguinalis (crabgrass). Also, many of the present compounds exhibit at the same time or sequentially on a given species a plurality of growth regulating effects, not all of which are desirable. However, the criterion of plant growth regulation is a non-lethal effect which is desirable in overall terms.
The present plant growth regulants can be utilized on a wide variety of plant species. The regulants are of special value to agriculturally important crops, such as the grains, the legumes, and the numerous vegetable and fruit crops. However, the present regulants can also be used on ornamentals, house plants, and other plants grown principally or solely for their decorative value.
The plant growth regulating effect of the compounds of formula I is exhibited upon application to plants in any of their parts or viable forms. Thus, application can be made to plant foliage, stems, flowers, fruit, roots, rhizomes, tubers, seeds, and the like. Application can also be made to soil, to exert a plant growth regulating effect on seeds sown therein or plants already growing therein.
The amount of compound to be employed is not critical so long as an effective plant growth regulating amount is used. Application rates of from 0.01 oz. to 10 pounds per acre are generally suitable, but will vary with the particular compound of formula I employed, the plant species and its stage of growth, the nature of the growth regulation sought, and other factors known to those skilled in the art. Lower rates can be employed with many of the compounds. For example, 1-(2-carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide is advantageously employed on soybeans at rates of 1 lb. per acre and less; favorable growth regulating effects have been observed as low as 1/2 oz. per acre, and the optimal rate at present appears to be about 1 oz. per acre. On strawberry fields, application of 1-(2-carboxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide at a rate of 0.1 oz. per acre increased berry production by 2400 lbs. per acre. Treatment of a dormant crab apple tree in spring with a 1000 ppm formulation of 1-(2-carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide (in 50:50 kerosene:crop oil) resulted in a delay in flowering, fewer blossoms, and enlargement of the leaves.
In the instance of application to seeds, preliminary tests on Soja max (soybeans), Hordeum vulgare (barley), Triticum aestivum (wheat), Oryza sativa (rice), Setaria italica (German millet), and Brassica napus (rape) suggest application rates of no more than about 1 percent by weight of the seed.
As illustrated below, a single application results in desirable plant growth regulation. However, multiple applications throughout the growing season can be used to obtain maximum plant growth regulation.
In one preferred embodiment, the compounds of formula I are employed on Soja max. When the compounds are applied to the foliage of Soja max, the change to more desirable modes of plant growth, including an increase in number of blooms and seed pods, has been observed to last for at least 18 days, usually stimulating increased pod set on about six nodes of the plant. The best practice is to use repeated foliar applications, every 15 to 20 days starting at the earliest blossoms to achieve maximum benefit by this method. If soil application (including application to the seed) is the chosen method, persistence of the growth regulating effect for over 30 days has been observed, including effective control of certain weeds. Depending upon the nature of the crop and the length of the growing season, a single application to the soil (or to the crop seed) at planting time may be sufficient, or will at least bring the greatest overall economic return for the expense involved.
In another preferred embodiment of the present invention, the compounds of formula I are employed on tomato plants to increase the set of fruit.
The results obtained on legumes and and tomatoes indicate that the compound possesses a unique combination of both cytokinin and auxin activity. More Chlorophyll A is present in the treated plants, as indicated by color change. More photosynthesis occurs, as indicated by increase in weight of treated plants, although the plants may be slightly shorter in stature. The stimulation of both leaf growth and fruit set at the same time is extraordinary.
Although productivity of Soja max is described herein in terms of increased "pod count," this effect is another example of enhanced "fruit set". In this term, "fruit" is used in its broad botanical meaning of the ripened ovary or ovaries of a seed-bearing plant, together with accessary parts.
The compounds of Formula I, especially those which exist as oils, can be employed alone; however, the compounds are generally employed in formulations comprising one or more of the compounds and an agriculturally acceptable adjuvant. The adjuvant can be any substance which aids in the utilization of the plant growth regulating activity of the compounds of Formula I. For example, the adjuvant can be a solvent, an inert diluent, a surface active agent, a substance for dispersing an active agent as an aerosol, or the like.
Suitable inert diluents include powdered chalk, the attapulgite clays, the kaolin clays, the montmorillonite clays, the diatomaceous earths and the silicates. Suitable surface active agents include the sulfonated lignins, the naphthalenesulfonates, the alkylbenzenesulfonates, the adducts of alkylphenols, fatty acids, fatty alcohols, and the like with ethylene and/or propylene oxide, and the like.
Wettable powder formulations are a preferred type of formulation, especially for those compounds of Formula I which exist as solids. Wettable powders comprise an intimate finely-divided mixture of the compound of Formula I, an inert carrier, and a surface active agent. The inert carrier and surface active agent can be any of those identified above. Wettable powders are typically added to water to constitute ultimate treating formulations.
Emulsifiable concentrates also constitute a suitable type of formulation of the compounds of Formula I. Such concentrates comprise a mixture of a compound of Formula I, a water-immiscible solvent, and an emulsifier. Suitable solvents include the aromatic and aliphatic hydrocarbons and derivatives, especially the xylenes, the various petroleum distillates, and oils from natural products, such as corn oil, soybean oil, and cottonseed oil. The emulsifier can be any one or more of the surface active agents exemplified above. An emulsifiable concentrate is especially adapted to be added to water to constitute an ultimate treating formulation.
Those compounds of Formula I which are relatively soluble in water can also be formulated as water soluble concentrates, either liquid or solid. Such formulations advantageously contain, in addition to the compound of Formula I, a surface active agent of the type listed above which facilitates solution of the active ingredient when added to water to form the ultimate treating formulation.
In general, formulations desirably contain from about 0.1 percent to about 95 percent of compound of Formula I and from about 0.1 to about 75 percent of surface active agent. As noted, the formulations typically serve as concentrates to be diluted to ultimate treating formulations. However, in certain specialized modes of application known to those skilled in the art, these same concentrated formulations can be employed directly as treating formulations. Attention is directed to the rotary atomizer type of low volume sprayer known as the Micron Herbi Sprayer.
The compositions which are intended for use in the form of aqueous dispersions or emulsions can also comprise a humectant, that is to say, an agent which will delay the dying of the composition in contact with the vegetation to which it has been applied. Suitable humectants include glycerol, diethylene glycol, solubilized lignins, such as calcium lignosulfonate, and the like. The compositions may contain other ingredients, for example, protective colloids such as gelatin, glue, casein, gums and polyvinyl alcohol; sodium polyphosphate; cellulose ethers, stabilizers and stickers, for example non-volatile oils.
As noted above, the compounds of Formula I sometimes exhibit a plurality of growth regulant effects, not all of which are desirable. For example, application of the compounds of Formula I sometimes results in an initial negative effect, typically stunting, which is outgrown by the plants; and the plants at their agricultural maturity have achieved a net positive growth regulating effect. It has further been observed that the initial negative side effect can be minimized by the coapplication of a source of potassium ion, typically a potassium salt such as potassium dihydrogen phosphate.
The utility of the compounds of Formula I as plant growth regulants is illustrated by the following Examples.
EXAMPLE 13
A water soluble formulation of the active ingredient in salt form was prepared by combining 120 g of 1-(2-carboxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide, 400 ml of water and 173 g of polyoxyethylene (5) soyaamine (Ethomeen S-15). The mixture was stirred at ambient temperature for 10 hours at which time a clear solution was obtained. With stirring 200 g of trimethylnonyl polyethylene glycol ether (Tergitol TMN-10) was added. An additional 107 ml of water was added, resulting in a formulation having the following percentage weight composition:
______________________________________Active Ingredient 12.0%Polyoxyethylene (5) 17.3%soyaamineTrimethylnonyl poly- 20.0%ethylene glycol etherWater 50.7%______________________________________
A sample of the above formulation was subjected to shelf-life studies. The solution was stable when stored at 15.degree.-20.degree. C.
EXAMPLE 14
A water soluble powder was prepared as follows: 60 g of potassium dihydrogen phosphate was ground in a shear-type blender and dried overnight in an oven at 50.degree. C. The potassium dihydrogen phosphate was combined with 7 g of the potassium salt of 1-(2-carboxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide, 5 g of sodium naphthalene formaldehyde condensate (Morwet D-425) and 28 g of Atwet W-13 (a commercially prepared product containing 50% polyethoxylated fatty acid esters encapsulated within an equal weight of a water soluble organic material). All components were well blended. This water soluble formulation contained the following weight percentage:
______________________________________Active Ingredient 7%Potassium dihydrogen phosphate 60%Sodium naphthalene formaldehyde 5%condensate (dispersant)Atwet W-13 (50% nonionic 28%encapsulated surfactant)______________________________________
EXAMPLE 15
By shearing and blending procedures, a water soluble formulation of the following weight percentage was prepared:
______________________________________Ammonium salt of 1-(2-carboxybenzoyl)- 25%2-methyl-4-phenyl-3-thiosemicarbazideSodium naphthalene formaldehyde 5%condensate (dispersant)Atwet W-13 (50% nonionic 70%encapsulated surfactant)______________________________________
The formulation was a white powder mixture. The pH of a one percent aqueous solution of the mixture was 5.93. The bulk density of the formulation was 22 lbs/ft.sup.3.
EXAMPLE 16
A wettable powder formulation of increased active ingredient content was prepared by thoroughly blending 150 g of 1-(2-carboxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide, 30 g of Georgia attapulgite clay, 10 g of sodium diisopropyl naphthalene sulfonate (Morwet IP) and 10 g of sodium naphthalene formaldehyde condensate (Morwet D-425). The mixture was ground in an air mill. The average particle size was determined to be about 5 microns. The resulting formulation had the following percentage weight composition:
______________________________________Active Ingredient 75%Georgia attapulgite clay 15%Sodium diisopropyl naphthalene 5%sulfonate (wetting agent)Sodium naphthalene formaldehyde 5%condensate (dispersant)______________________________________
EXAMPLE 17
A suitable wettable powder formulation was obtained by blending and milling 0.72 lb of precipitated silica (Hi-Sil 233), 0.80 lb of trimethylnonyl polyethylene glycol ether (Tergitol TMN-10), 0.40 lb 1-(2-carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide and 0.08 lb of sodium naphthalene formaldehyde condensate (Morwet D-425) as a dispersing agent. The resulting formulation had the following percentage weight composition:
______________________________________Active ingredient 20%Precipitated silica 36%Trimethylnonyl polyethylene 40%glycol etherSodium naphthalene formaldehyde 4%condensate______________________________________
The above composition had a bulk density of 15.3 lbs/ft.sup.3, an average particle size of 10.4 microns and a wetting time of 49 seconds.
EXAMPLE 18
A water dispersion of the present active agent was prepared by mixing 0.06 lb of 1-(2-carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide, 0.12 lb of sorbitan monooleate ethoxylate (Tween 80) and 0.82 lb of tetrahydrofurfuryl alcohol. When diluted with water for spraying, the formulation produced microcrystals of the active ingredient, suspended uniformly by the surface active agent.
EXAMPLE 19
An emulsifiable concentrate suitable for implementing the plant growth regulant activity of the compounds of Formula I is prepared by dissolving the active ingredient and a wetting agent in an oil from a natural product or in an aromatic hydrocarbon solvent. A typical emulsifiable concentrate given in percentage weights is:
______________________________________1-(2-((2-ethylhexyloxy)carbonyl)- 12%benzoyl)-2-methyl-4-phenyl-3-thio-semicarbazideDialkylphenoxypolyethoxylated 12%ethanol (Igepal DM-530)Corn oil 76%______________________________________
EXAMPLE 20
A water soluble powder suitable for implementing the plant growth regulant activity of the compounds of Formula I is prepared by blending the active ingredient in salt form with a solid anionic surfactant such as Naxonate KX (potassium xylene sulfonate) or Naxonate KT (potassium toluene sulfonate). If further dilution is required, a compatible inorganic salt may be included. An illustrative water soluble powder has the following percentage weight composition:
______________________________________Potassium salt of 1-(2-carboxy- 6.2%benzoyl)-2-methyl-4-phenyl-3-thio-semicarbazidePotassium carbonate 50.0%Naxonate KX (potassium xylene 43.8%sulfonate)______________________________________
Solid nonionic surfactants such as Myrj 53 (polyoxyethylene (50) stearate) can also be used.
EXAMPLE 21
Another water soluble powder is prepared by conventional procedures to have the following percentage weight composition:
______________________________________Potassium salt of 1-(2-carboxy- 6.2%benzoyl)-2-methyl-4-phenyl-3-thiosemicarbazideMorwet D-425 (sodium naphthalene 5.0%formaldehyde condensate)Macol SA-40 (polyoxyethylene 44.4%(4) Lauryl alcohol)Sorbitol 44.4%______________________________________
EXAMPLE 22
A further emulsifiable concentrate formulation is prepared with the active ingredient in salt form, by mixing the following reagents given as weight percentage:
______________________________________1-(2-carboxybenzoyl)-2-methyl-4- 4.5%phenyl-3-thiosemicarbazide2,6-lutidine 1.5%Atlox 3459F (anionic-nonionic 10.0%blend of calcium dodecylbenzenesulfonate and polyethoxylatedfatty acid esters)Cyclohexanone 84%______________________________________
EXAMPLE 23
The use of the growth regulant compounds to modify and control plant growth as well as to combat unwanted vegetation may be demonstrated readily in small scale greenhouse tests according to procedures described below.
PRE-EMERGENT APPLICATION
Disposable plastic trays about 21/2 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 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 mixture consisting of 60 wt. percent of a commercial polyethoxylated vegetable oil emulsifier (96 wt. percent active ingrdient, 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 effects were rated according to the following schedule.
______________________________________ AbbreviationEffect in Tables______________________________________Formative effect Fon new growthEpinasty EGrowth reduction GNecrosis NNon-emergence K______________________________________
______________________________________Degree of Effect______________________________________ 0 = no effect 1 = slight effect, temporary 2 = moderate effect 3 = severe effect 4 = maximum effect______________________________________
In some instances more than one effect was observed and recorded with respect to a group of plants of one species.
POST-EMERGENT APPLICATION
Several species of plants were grown in potting soil in disposable polystyrene foam trays and individual plants of a miniature variety of Lycopersicum esculentum 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. per acre with a spray mixture containing no growth regulant. Effects were again rated according to the schedule disclosed above.
Observations of effects in both pre- and post-emergent tests were recorded, and are tabulated in Table I, below:
__________________________________________________________________________EFFECTS ON VEGETATIONPre-Emergent Effects Post-Emergent EffectsCompd. Digitaria Celosia Bromus Setaria Raphanus Beta Setaria Medicago Avena Raphanus Beta LycopersicumNo. sanguinalis plumosa inermis italica sativus vulgaris italica sativa sativa sativus vulgaris esculentum__________________________________________________________________________ 597 K4 F2G1 K3G3 F3G3 F3G2 F3G2 N1G1 F3 F2 G1F1 F2G1 F31685 K4 F3G3 F3G3 F3G2 F1G1 F3G3 0 0 0 0 F2 N1F11686 0 F1 F2 0 0 F2 C1 F1 0 N1 F2G1 N1F12005 K4 F3G2 K4 F3G3 G3 K4 0 F2G1 G1 G2F1 F3G1 F22008 0 K2 F1 0 K2 K1 0 F2G2 N1G1 F2G1 F2G1 02044 K4 F1G1 F3G3 F2G2 F1G2 K4 F2G1 F3G1 F2 N1G1 F2G1 F2G32047 F3G2 F1 F2G1 F2G1 F1 F2 F2G1 F2G2 F1G1 F2G1 F2G2 F2G22322 N1 N3G2 G1 0 0 N3G3 0 0 0 0 F1 02324 K1G2 0 0 0 0 K1 0 0 0 0 F1 02325 N3G3 N3G2 N3G3 N2G3 G3 K3G2 N1F1 F2 F1 F1G1 F1G1 F332341 F2G1 F1 F2 F3G2 G1 F2G1 F1 F1 0 F1G1 F1G1 02342 F1 0 F2 F2 0 F2 0 F1 0 F2G1 F1G2 F12370 K4 K4 K4 F3G3 F3G2 F3G3 F2G1 N1G3 N1G1 N1F1 F1G3 F32371 K4 K4 F3G3 F3G3 F3G2 F3G3 N1G1 F3G3 F1G1 F2G2 F1G2 F3G32372 K4 F3G3 F3G3 F3G3 F3G2 F3G3 N1G2 N1G3 N1 N1G2 F3G2 F32388 F2G2 F1G1 F3G1 F3G2 F3G2 F3G1 0 F3G1 F1 F2 F3G1 F32389 K4 K4 K3F1 F3G3 F3G3 K4 F2 F3G3 F2 F2 F3G3 F32390 K3G3 F3G2 F3G1 F3G3 F3G2 F3G2 F1 F3G2 F1 F1 F2G1 F32391 K4 K4 K3F1 F3G3 F3G3 F3G3 F2 F3G2 F2G2 F1 F3G1 F32392 F3G3 F3G3 F3G1 F3G2 F2G1 F3G1 0 F1 0 0 F2 F22414 K4 F3G3 F3G3 F3G3 F3G3 F3G3 F2 F3G3 F2 F1 F3G1 F32415 K4 F3G3 K4 F3G3 F3G2 F3G3 F2 F3G3 F1 0 F3G1 F32418 F1G1 K2 F2G1 0 0 F2G1 0 F1 0 0 F2 F22422 0 0 F2 0 0 0 -- -- -- -- -- --2432 K4 F3G3 F3G3 F3G3 F3G3 F3G3 F2 F3G2 F1 F2 F3G1 F22433 F3G2 F3G3 F2G1 F2G1 F3G2 F1G1 F1 F3G2 F1 F1 F3G2 F32434 F3G3 F3G3 F3G1 F2G1 F3G1 F3G1 F1 F3G2 F2 F1 F2G1 F32444 K4 K2G1 F3G1 F3G2 F1G2 F2G2 N2G2 -- -- F2 N2G1 F32445 F3G3 K2G1 F3G1 F3G2 F1G1 F2G2 0 F2 0 0 F2G1 F22446 K4 K4 F3G3 F3G3 F2G2 F3G2 -- F2G1 0 F1 F1G2 F12450 F2G2 K4 F2 F3G2 F2G2 F3G2 N1G1 F2G1 0 F1 F2 F12470 K4 K4 F3G3 F3G3 F3G2 0 N1 F2 0 F1 F2G2 F2G22472 F3G3 K4 F3G2 F3G3 F1G1 F2G2 0 F2G1 0 N1F1 F2G1 F3G22474 K4 K4 F3G3 F3G3 F3G2 F3G2 N1 N1G2 0 N1G1 F2G2 F32479 0 0 F1 F1 0 0 N1G2 F1 N1 F1 F1G1 02480 0 0 0 0 0 0 -- -- -- -- -- --2481 K4 K4 F3G3 F3G3 F3G2 F3G2 N1G2 N3G3 G1 F2G1 N4 F2G12482 K4 K4 F3G3 F3G3 F3G2 K4 N1G2 F2G1 F1G1 F2G1 F2G2 F2G12483 F3G3 K4 F3G3 F3G2 F3G1 F3G2 N3G3 F2G3 G1 F2G1 F2G1 F32484 F3G2 F3G3 F3G2 F3G2 F2G1 F3G2 N2G1 F1 G1 F1G1 F2G2 F12487 K4 F3G2 F3G3 F3G3 F3G3 F3G3 N1G1 -- N1 F2G2 F2G1 F22488 F3G3 F3G2 F3G3 F3G3 F3G2 F3G2 N1G2 F2G2 F1G1 N1F1 F2G1 F3G22563 F2G2 G2G1 F3G1 F3G2 F2G1 F2G1 N3G3 F1 0 0 F2G1 F3E22564 F1G1 F1G1 F3G1 F3G2 F1G1 F1G1 N1G1 0 0 0 F1 F3E22567 K4 F3G2 F3G3 F3G3 F3G2 F3G3 N4 F3G2 F1 F2 F3G2 F3G32568 F3G3 F3G3 F3G3 F3G3 F3G2 F3G3 N1G2 F3G2 F2 F2 F3G1 F3E32569 K4 F3G3 F3G3 F3G3 F3G3 F3G3 F2G2 F3G2 F1 F2G1 F3G2 F3G22570 F3G3 F3G3 F3G2 F3G2 F3G2 F3G3 F2G2 F3G2 F1 F2 F3G2 F3G22571 F2G2 F2G1 F3G1 F3G2 F2G1 F1G1 F1G1 F2 0 F1 F2 F3E22572 F2G1 F2G1 F1 F2G1 F1G1 F1 F1 F2 0 F2G1 F3G2 F3G22573 F1 F1 F2 F1 0 0 0 F1 0 0 F1 F12574 F1 F1 F2 0 0 0 0 F1 0 0 F2 F12476 0 0 0 0 0 0 -- -- -- -- -- --2577 F1G1 F1G1 F2 F2G1 F1 F1 N1 F1 0 0 F2 02578 F1 F1 F2 F1 0 0 0 F1 0 0 F2 F12579 K4 F3G3 F3G3 F3G3 F3G2 F3G1 F2G1 F3G3 F1 F2G1 F3G2 F3E22580 0 0 F1 0 0 0 0 F1 0 F1 F2 02581 F2G1 0 F1 0 0 0 0 F1 0 0 F1 02583 F1G1 F1 F2 F1 0 F1 0 F3G1 F1 F1 F3G1 F12584 F1 F1 F2 F1 0 0 0 F3G3 F1 F1G1 F2G1 F1E12585 F3G3 F3G2 F3G3 F3G3 F1 F3G1 F1 F3E2 F1 F1G1 F3G1 F3E22586 F1 F1 F2 F1 0 0 0 F3G2 0 F2G1 F3G1 F1E12588 F1 0 F1 0 0 0 0 0 0 F1 F1 02589 0 0 0 0 0 0 0 0 0 F1 F1 02590 0 0 F1 F1 0 0 F1 F3G2 F1 F2 F3G1 F1E12591 K4 K3G3 K3G2 F3G3 F3G2 F3G1 F3G3 F3G3 F1G1 F3G1 F3G3 F3G32592 F3G3 F3G3 F3G3 F3G3 F3G2 F2G1 F3G2 F3G1 F1 F2G1 F2G1 F3G32594 F3G3 F3G2 K4 F3G3 F3G1 F2G1 N4 F3G3 G1 F2G1 F3G1 F3G12595 F2G2 F1G1 F3G1 F2G1 G1 F2G1 N1G3 F3G3 F1G1 F1G1 F3G1 F3E32597 F1G1 F2G1 F3 F2G1 F1G1 F2G1 G3F2 F3G2 F1 F2G1 F3G2 F3G32598 0 0 F1 0 0 0 F1G1 F3G1 F1 F2G1 F3G1 F2E22599 F1 F2 F2 0 0 0 0 F3G1 0 F1 F2 F2E12603 0 0 0 0 0 0 0 F1 0 F1G1 0 F1E12604 F2 F1G1 F3G1 F3G2 0 F1 0 F2 F1 F2G1 F2G1 F2E22605 F3G1 F2G1 F2 F1G1 0 F1 0 F2G1 0 F2G1 F2G1 F2E12622 F3G3 F3G2 K4 F3G3 F3G2 F3G2 N3G3 F3G2 F1 F2G1 F3G2 F3E32627 K4 F3G3 F3G3 F3G3 F3G2 F3G3 F2G2 F3G2 F1G1 F3G3 F3G3 F3E32628 F3G3 F2G1 F3G3 F3G3 F3G2 F3G3 F2G2 F3G2 F1 F1G1 F3G2 F3E32633 K4 F3G3 K4 F3G3 F3G2 F3G3 F3G3 F3G2 F2G1 F2G1 F3G2 F3E32634 F3G3 F3G2 F3G3 F3G3 F3G2 F3G3 F1G1 F3G2 F1 F1 F2 F3E22635 F3G2 F3G2 F3G3 F2G2 F3G2 F1G1 F3G2 F1 F1G1 F2G1 F3E32636 F3G3 F3G2 F3G3 F3G2 F2G2 F2G2 F2G3 F3G2 F1 F1G1 F3G2 F3E32637 K4 F3G2 K4 F3G3 F3G2 F3G3 F3G3 F3G3 F1G1 F2G1 F3G2 F3E32641 F2G1 F2G2 F2G1 F3G2 F1G1 F2G1 F3G3 F3G3 F1 F1G1 F3G2 F3G12668 K4 F3G3 K4 F3G3 F3G1 F3G3 G2F2 F3G2 F1G1 F2G1 F3G3 F3G32669 F3G3 F3G2 K4 F3G3 F3G2 F3G3 F2G2 F3G2 F2G1 F2G1 F3G2 F3E32697 F2G3 F1G1 F3G1 F2G1 F1 F1G1 F2G1 F3G3 F2G1 F3G1 F3G1 F3E22698 F1 0 0 0 0 0 F1 F1 F1 F1G1 F2G1 F12699 F1 F1G1 F1 0 0 0 F1 F1G1 0 F2G1 F2G1 F3E12700 0 0 0 0 0 0 F1 F1 0 F1 F2 F3E12701 F1G1 F1G1 F3G1 F1 G1 0 F2G1 F3G2 F1 F2G1 F3G1 F3E22702 F3G1 F1 F3 F3G1 F1 F2G1 F2G1 F3G2 0 F2G1 F3G1 F22704 F2G1 F1G1 F3G1 F1G1 0 F1 F1 F3G1 F1 F3G1 F2G1 F3E12705 F1 F1G1 F2 F1 0 F1 F2G1 F3G2 F2 F2G1 F3G1 F22707 F1 0 0 0 0 0 F1 F2 F1 F2G2 F3G1 F12708 0 0 0 0 0 0 F1 F1 0 F1 F2 F2E12721 F3G3 F2G2 F3G2 F3G2 F3G2 F3G3 F2G2 F3G3 F2G1 F3G1 F3G2 F3G32722 K4 F2G2 F3G3 F3G2 F3G3 F3G3 F2G1 F3G2 F1 F3G1 F3G1 F3E32723 F3G3 F2G2 F3G2 F3G2 F3G2 F3G2 F2G1 F2 F1 0 F3 F3E22724 K4 F3G3 K4 F3G3 F3G3 K4 F2G2 F3G2 F1G1 F2G1 F3G2 F3E32725 F3G2 F2G1 F3G1 F3G1 F1G1 F2G2 F1 F3G1 0 F2 F3G1 F3E22726 F3G2 F1 F2 F2G1 F1G1 F2G1 F1 F3G1 F1 F1 F2 F2E12727 F1G1 F1 F2 F2G1 0 0 F1 F2G1 0 F1 F2 F22728 F3G2 F2G2 F3G1 F3G1 F1G1 F1G1 F1G1 F3G3 F2G1 F2G1 F2G1 F3E12729 F1G1 F2G2 F1 0 0 0 F1 F2 0 0 F1 F12732 F1 0 F1 F1G1 0 0 0 F1 0 0 F1 F12733 F3G2 N4 F2 F3G2 F1 F1 0 F1 0 0 F1 02734 F3G3 F2G2 F3G3 F3G3 F3G2 F3G2 F2G2 F3G2 F2 F2G1 F3G1 F3E32735 F3G3 N4 F3G3 F3G3 F3G2 F3G2 F2G2 F2G1 F2G1 F2G1 F3G1 F3E32736 F3G3 F3G2 F3G2 F3G3 F3G2 F3G2 F2G2 F3G1 F1 F2G1 F3G2 F3G32740 K4 F3G2 K4 F3G3 F3G3 N4 F2G2 F3G2 F2G1 F2G1 F3G1 F3G32741 F3G3 F3G2 F3G3 F3G3 F3G2 K4 F2G2 F3G1 F1 F2G1 F3G1 F3E22742 K4 N4 F3G3 F3G3 F3G2 F3G3 F2G2 F3G2 F2G1 F2G1 F3G2 F3G32743 K4 F3G2 F3G3 F3G2 F2G1 F2G1 F2G2 F3G2 F2G1 F2G1 F3G1 F3E22744 F3G3 F3G2 F3G3 F3G3 F3G2 F3G2 F1G1 F3G2 F1G1 F1 F3G1 F3E22745 F3G3 K4 F3G3 F3G2 F2G1 F2G2 F2G2 F3G1 F1G1 F1 F3G2 E2F22746 F2G1 F2G2 F3G1 F3G3 F2G1 F2G1 0 F1 0 F1 F2 F12749 0 0 0 0 0 0 0 0 0 0 F1 02750 0 0 F1 0 0 0 0 F1 0 0 F1G1 F12753 K2 G1 F1 0 0 G1 0 0 0 0 F1 02754 0 0 0 0 0 0 0 F1 0 0 F1 02756 F1G1 F1 F1 F3G2 F1 F2G2 F1 F3 0 F1 F2G1 F2E12760 0 G1 0 0 0 F1G1 0 F1 0 0 F1 F12762 0 0 0 0 0 0 0 F1 0 0 F1 02771 K4 F3G2 F3G3 F3G3 F3G2 F2G2 F3G3 F3G2 F1G1 F1 F3G2 F3G32772 F1 F1 F2 F1G1 F1 F1G1 0 F1 0 0 F1 F1E12777 F1 G1 F2 F1G1 F1 F1 F1 F1 0 0 F2G1 F12778 0 0 F1 0 G1 0 0 F1 0 F1 F2 F12779 0 0 F1 0 0 0 0 F1 0 0 F1 02781 0 0 F1 0 0 0 F1 F2 0 0 F2 02783 F1 0 F1 F1G1 F1 0 G1 F2 0 F2G1 F2G1 F12784 F3G2 F3G2 F3G1 F3G3 F3G3 F3G2 F3G3 F3G3 F1G1 F2G1 F3G2 F3E32787 F1 F1 F2 F2G1 F1 F1 F1 F1 0 F1 F2 F1E12788 F3G3 F2G2 F3G3 F3G3 F3G3 F3G2 F3G2 F3G2 F1G1 F1 F3G2 F3E32790 K4 F3G3 F3G3 F3G3 F3G2 F3G3 F3G2 F3G2 F2G2 F2 F3G1 F3E32795 F2G2 F1G1 F2 F3G2 F2G1 F1G1 F1 F2 F1 0 F2G2 F12796 F1 0 F2 F3G2 F1G1 F1G1 0 F1 0 0 F2 F12798 0 0 0 0 0 F1 0 F3 0 F1G1 F2G2 F3E22799 F1G1 F1 F2G1 F1G1 0 F1G1 F1G1 F3G1 F1 G1 F2G1 F2E12800 0 0 0 0 0 0 F1 F2 0 F1G1 F2G1 F12801 0 G1 F1 0 F1 F1 0 0 0 0 F1 02802 F2G2 F1 F2G1 F3G2 F2 F2G1 F1 F3G2 0 F1 F2G1 F3E22803 F3G3 F2G1 F3G3 F3G3 F3G2 F3G1 F1 F2G1 0 F1 F3G1 F3E32818 F2G2 F2G1 F2 F3G3 F2G2 F2G2 F1G1 F2G1 F1 0 F3G1 F2E22819 0 0 0 G1 0 F1 0 F2 0 F1 F2 F22822 K4 F3G2 F3G3 F3G3 F3G3 F3G3 F2G2 F3G2 F1G1 F1 F3G2 F3E32844 F2G3 F3G2 F3G3 F3G3 F2G2 F2G2 F3G2 N1G3 F1G2 F2G2 F3G2 F3G32845 K4 F3G3 F3G3 F3G3 F3G2 F3G2 N2G2 F3G3 0 N1G2 F2G3 F3G12850 0 0 0 0 0 0 -- -- -- -- -- --2851 0 0 0 0 0 0 0 N2 0 N1G1 F2 02852 0 0 0 0 0 0 0 0 0 0 F1G1 02853 F2G1 F1G1 F3 F3G3 F1G1 F2G1 0 0 0 0 F1 02854 K4 K3G3 F3G3 F3G3 F2G2 F3G3 N2G1 F2G1 N1G1 N1F1 F2G2 F32855 F3G3 F3G2 F3G2 F3G2 F1G1 F2G2 N1 F2 N1 N1G1 F2G1 F22859 K4 K4 F3G2 F3G3 F3G2 K4 N2G2 F3G1 0 0 F2G2 N1F22862 F1 0 F1 F1 0 0 N1G1 0 0 0 F2G1 F22863 F1 0 0 0 0 0 0 F1 0 0 F2 02879 F3G3 F1G1 F3G2 F3G2 F2G2 F3G3 N2G1 0 0 F2G1 F2G32882 K4 F3G2 F3G3 F3G3 F3G2 F3G3 N1G2 F2G2 F2 F1 F2G2 F32883 K4 F3G3 F3G3 F3G3 F3G3 K4 N2G2 F2G1 N1 N1G1 F1G1 F22885 F3G3 F2G2 F3G3 F3G3 F3G2 F3G3 N3G2 F2G1 N1G1 G1F1 F1G2 F22896 F3G3 F1G1 F3G2 F3G2 F2G2 F2G2 N2G3 0 N1 0 F2G2 F3G32898 0 0 F1 0 0 0 0 0 0 F1 F2G1 F12914 0 0 0 0 0 0 0 F1G1 0 F1G2 F1G3 N12923 0 0 F1 F1 0 0 0 F1 0 0 N1G2 02954 0 K1G1 F1 0 0 0 0 N1G1 0 G1 F2G3 F12987 0 0 0 0 0 0 0 0 0 0 F1G1 02992 F1G1 K2F2 F3G1 F2G2 0 K2G1 0 F1 0 0 F2G3 N12994 0 0 F1 0 0 0 0 0 0 0 F3G1 02995 0 0 F2 0 F1 0 0 0 G1 0 F2G1 G12996 K3G3 F2G2 F3G2 F3G2 K2F1 F2G2 0 0 0 F1G1 F3G2 N1F22997 F1 G1 F2 F2G2 F1 F1 0 F2G2 G1 F1G1 F2G2 F32998 0 0 0 0 0 0 0 0 0 0 F1 F12999 0 0 0 0 0 0 0 0 0 0 F2 03000 0 0 0 0 0 0 0 0 0 0 F2G1 N13001 0 0 0 0 0 0 0 0 0 0 F2G2 G13002 K4 K4 F3G3 F1 F2G1 F1G2 0 N1G1 0 F1G1 F3G3 F13006 F1F1 F1G1 F3G1 F2G1 G1 F1G1 0 F1 0 0 F2G2 030017 0 0 0 0 0 0 0 0 0 0 F1G1 F13018 K3G3 G2 F2G1 F1 F2G1 F1G1 0 0 0 0 F2G3 03019 F1G2 F2 F2 F2G1 G1 F1 0 0 0 F1 F3G2 F2G23022 F2G2 F3G1 F3G2 F1G1 F3G3 F2G2 0 N1 N1 N1G1 F2G1 03023 F2G2 F3G3 F2G2 F2G2 F2G1 F1G1 N1G1 N1G2 F1 F1G1 F2G2 F2G13024 0 0 0 0 0 0 0 0 0 0 F2G2 03025 F1 F1 F1 0 0 0 0 0 0 0 F1G1 03026 F1 G1 F2 0 0 0 0 0 0 0 F2G2 03027 0 0 0 0 0 0 N1G1 0 0 0 F2G1 N23108 F3G3 F3G2 F3G2 F3G3 F3G3 F3G3 N1G2 F3G2 N1F1 F2G2 F2G2 F2G13109 F3G3 F3G2 F3G3 F3G3 F2G2 F2G2 N2G1 F3G2 N1F1 F2G1 F2G2 F2G13116 F1 F1 F2 F2G1 F1G1 F1 N1 N1G2 0 N1 F2G1 N1F13137 F3G3 F2G2 F3G3 F3G3 F2G1 0 0 F3 N1 F2G1 F2G2 F33146 F3G3 F2G2 F3G3 F3G3 F2G2 F2G2 N2G2 N3G2 F1 N1G2 N2G3 F33147 F1 0 F1 0 0 0 0 0 0 N1 F2G2 F23151 F1 F1G1 F2G1 F2G1 F1 F1 N2G1 F1 F1 F1 F2G2 F23152 0 0 0 0 0 0 N1 0 0 0 F1 03153 F1 0 F2 F2G1 F1G1 F2G2 G1 F1 0 0 F1 F23158 F1G1 F2G1 F3G1 F3G1 F2G2 F3G3 G1 F3G1 0 F2 F2G3 F2G13159 F3G2 F2G2 F3G2 F3G2 F3G2 F3G2 N1G2 F3G2 F1 F2 N4 F3G13160 F2G2 F1G1 F3G1 F3G2 F2G2 F2G2 N1G2 F2G1 0 F2 F2G2 F33180 F3G3 F3G3 F3G3 K4 F3G2 F3G3 N1G1 F3G2 F2 F2 F2G3 F33181 F3G3 F3G2 F3G3 F3G3 F2G2 F3G2 N1G2 F3G2 F2G1 F2G1 F2G2 F33182 F3G3 F3G2 F3g3 F3G3 F3G2 F3G2 N1G2 F3G2 F3G2 F2G1 F2G1 F33183 F3G3 F2G2 F3G3 F3G3 F2G2 F2G2 N2G2 F3G3 N1G1 N2G2 F2G3 N2G13184 F1 0 F1 0 0 0 0 0 0 F1 F1 03185 F2G2 F1 F2 F3G2 F1 F1G1 0 F1 0 F1 F2 F23186 0 0 0 0 0 0 0 F2 0 0 F2 F13187 F1 F1 F2 F2G1 G1 F1G1 0 0 0 0 N2G2 F23194 F1G1 F2 F3G1 F3G3 F2 F2G1 F2G1 F2G2 F1 F2 F3G1 F33195 F2G2 F2G1 F3G1 F3G3 F2G1 F2G1 0 F2G1 0 F1 F3G1 F33196 F3G3 F3G2 F3G3 F3G3 F2G2 F2G2 N1G2 F2G1 0 F1 F2G2 F33210 F2G2 F2G2 F3G3 F3G3 F2G2 F3G2 N2G3 F3G2 N1G2 F1 N3G3 F33284 F3G3 F3G2 F3G3 F3G3 F3G2 F3G2 F3G2 F2G2 F3G2 F3 F2G3 F23285 F1 F1 F2 F2G1 0 F2G1 0 F3G2 0 F1 F3G2 N13290 F3G3 F3G3 F3G3 F3G3 F3G2 F3G2 N1G2 F3G2 F2G1 F2G1 F3G3 F23349 K4 F3G3 K4 K3G3 F3G2 F3G3 N1G2 F3G3 F1G1 F3G2 F3G2 N1F13350 F2G1 F2G2 F3G3 F3G2 F2G2 F2G2 F1G1 F2G2 F1G1 F3G2 F2G2 F3G13352 F3G2 F2G2 F3G3 F3G2 F2G2 F3G2 0 F3G2 0 F1G3 N3G2 F2G13358 K4 F2G2 F3G3 F3G2 F3G2 F3G2 F2G1 F2G3 F1 C1G2 F3G2 F43577 K4 F3G3 F3G3 F3G2 F3G3 K4 G2 F3G2 F1G2 F2G1 F3G3 F33578 K4 F3G3 K4 F3G3 F3G3 F3G3 F1G2 F3G2 F1G3 F1G1 F3G3 F33579 K4 K4 F3G3 F3G3 F3G3 K4 G2 F3G2 F1G2 F2G1 F3G3 F33580 K4 F3G2 F3G3 F3G2 F3G3 F3G3 G2 F3G2 F1G3 F2G2 F3G3 F33581 K4 K4 F3G3 F3G3 F3G2 F3G3 G2 F3G2 F1G2 F2G1 F3G3 F33582 F3G3 F3G3 K4 F3G2 F3G2 F3G3 G2 F3G2 F1G2 F2G1 F3G2 F33676 0 0 0 0 0 0 0 0 0 0 F1 03716 F1G1 F2 F3G1 F2G1 F2G1 F2G1 F1G1 F2 -- G2N1F1 F3G2 F2N1G1__________________________________________________________________________
EXAMPLE 24
Seeds of Soja max were planted in 12 in..times.10 in. polystyrene foam trays, 3 inches deep, filled with greenhouse potting soil. Spray mixtures containing 1-(2-carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide were prepared as in Example 23 and were applied to seeded trays at rates of 2, 1 and 1/2 lb per acre. The plants which subsequently emerged from treated soil had some leaves with 4 to 6 leaflets instead of the usual trifoliate leaves. Similar results are obtained by seed treatment at low rates of application, for instance, 0.0625 percent by weight of seed.
EXAMPLE 25
The use of many of the growth regulant 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 (Tiny 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 (374 liters per hectare) and at application rates of 16, 4, and 1 oz. per acre. (1.12 kg, 280 g, and 70 g per hectare) The spray mixtures were prepared by dissolving the proper amount of growth regulant compound in 15 ml of acetone, adding 2 ml of a solvent-emulsifier mixture consisting of 60 wt. percent of a commercial polyethoxylated 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 other growth regulatory effects observed on the plants was estimated on a scale of 0 to 10 (with 0=no other effect and 10=maximum effect) and is also recorded in the following table:
TABLE III______________________________________GROWTH REGULATING EFFECTS ON TWO SPECIES Soja max Lycopersicum esculentum Pod Count Growth Fruit Count Growth (Percent in Regula- (Percent in Regula-Com- Rate Comparison ting Ef- Comparison ting Ef-pound (oz/ to Untreated fect (Av- to Untreated fect (Av-No. A) Plants) erage) Plants) erage)______________________________________ 597 16 171.sup.a,c 9 400.sup.b 9 4 177.sup.a,c 4.5 291 7 1 151 2 436 1.51686 16 137 3 36 0 4 120 0.5 36 0 1 94 0 145 02005 16 169.sup.a,c 9 255.sup.b 9 4 163.sup.a,c 7.5 327 7.5 1 160 3 364 3.52322 16 107 0.5 145 0 4 103 0 218 0 1 94 0 182 02324 16 97 0 73 1 4 114 0 109 0 1 97 0 36 02474 16 146.sup.a,c 9 300.sup.a 9 4 154 7.5 382.sup.e 8.5 1 115 3.5 191 4.52481 16 157.sup.a,c 8.5 136.sup.d 7.5 4 135 3.5 191 2.5 1 104 1 164 0.52568 16 163.sup.a,c 9 109.sup.a,b 9 4 166.sup.a,c 5.5 327 7.5 1 140 1.5 327 3.52584 16 120 2 145 0.5 4 111 0 182 0 1 103 0 145 02592 16 118 1.5 237.sup.c 5 4 115 1 245 1.5 1 107 0 82 02622 16 115 3 327 1 4 98 0 109 0 1 95 0 136 02627 16 121 6.5 273 5.5 4 104 1.5 245 1 1 95 0 164 02628 16 159.sup.c 8 273.sup.d,e 8.5 4 136 3.5 191 2.5 1 95 0.5 136 02633 16 173.sup.a 9 436.sup.d,e 9 4 138 3.5 245 3.5 1 127 1 355 0.52634 16 173.sup.c 8.5 300.sup.e 8 4 130 4.5 327 5 1 113 0.5 164 0.52636 16 130.sup.a,c 9 191.sup.a,b,d 9 4 133 4.5 436 4.5 1 130 1.5 355 0.52637 16 147 6 327.sup.a,d 9 4 141 2.5 273.sup.e 2.5 1 104 1 245 02641 16 101 2 382.sup.d 7.5 4 101 0 245.sup.e 1.5 1 92 0 109 02668 16 144 8.5 300.sup.d 8.5 4 144 2.5 273.sup.e 1.5 1 124 0.5 327 0.52721 16 129.sup.a,c 9 300.sup.a 9 4 129 5.5 245 5.5 1 112 2.5 300 12722 16 143.sup.c 7.5 218.sup.d,e 7 4 149 2.5 245 1.5 1 126 0.5 300 02743 16 144 8 273.sup.d 8.5 4 170 2.5 245.sup.c 3.5 1 113 0 191 0.52744 16 124 7.5 245.sup.d 9 4 127 3 245.sup.e 3 1 104 0 382 12788 16 147.sup.c 7.5 327.sup.a,d 9 4 130 2.5 355.sup.e 4.5 1 138 0 300 1.52790 16 191.sup.a,c 9 364 8.5 4 180.sup.a,c 5 218 6.5 1 169 2 255 32798 16 124 1.5 355 1 4 101 0 82 0 1 96 0 136 03116 16 132 3 191 1.5 4 126 1 109 0 1 110 0 164 03358 16 159.sup.c 9 273.sup.a,d 9 4 156 5.5 300.sup.e 2.5 1 136 1.5 355 12598 16 111 8.5 150 3 4 120 2 133 0 1 111 0.5 150 02604 16 153 8.5 100 1.5 4 147 4 167 0 1 141 1 150 02605 16 123 5.5 133 1 4 120 1.5 167 0.5 1 120 0 117 02699 16 168 7 183 1.5 4 159 2.5 67 0 1 141 1 83 02701 16 138 8 83 2 4 129 7 33 0.5 1 123 1.5 67 02702 16 174 7.5 183 1.5 4 174 5 100 0.5 1 153 2 117 02707 16 159 7.5 100 0 4 156 3 117 0 1 108 0.5 83 02725 16 171 8.5 50 1 4 177 4.5 150 0 1 132 1 100 02726 16 147 8 33 0.5 4 132 3.5 133 0 1 99 0 83 02728 16 180 9 67 2 4 159 6.5 67 0.5 1 165 2.5 183 02389 16 159.sup.c 6 286.sup.b 8.5 4 115 3.5 200 2.5 1 105 1 229 12391 16 169.sup.c 4.5 243.sup.b 8.5 4 150 1.5 271 5 1 131 1 171 1.52487 16 169.sup.c 6.5 229.sup.b 8 4 150 2.5 271 5 1 131 1 171 1.52563 16 137 3.5 200 5 4 108 1 157 0.5 1 92 0 114 02570 16 150.sup.a,c 9 171.sup.b,d 8.5 4 169 5.5 243 5.5 1 143 2 271 22572 16 150 4.5 186 2.5 4 108 1 100 0.5 1 96 0 57 02574 16 134 6 143 2 4 127 2.5 214 0.5 1 96 0 186 02879 16 137 3.5 186 2.5 4 140 1 143 0.5 1 108 0 129 02996 16 137 2.5 171 3 4 150 1 171 0.5 1 124 0 114 03017 16 105 2.5 143 1 4 99 0 186 0 1 96 0 86 03018 16 108 3.5 129 2 4 105 0.5 157 0 1 115 0 129 03350 16 131.sup.a,c 9 129.sup.d 7.5 4 150 4.5 243 2 1 118 1.5 214 23022 16 124 3.5 143 2.5 4 108 0.5 129 0 1 92 0 114 03023 16 127 4.5 157 3.5 4 124 1.5 143 1 1 99 0 157 02418 16 150 3.5 103 3.5 4 125 1 169 1 1 125 0 94 0______________________________________ Footnotes .sup.a Injurious .sup.b Malformed fruit .sup.c Smaller pods .sup.d Stimulated growth .sup.e Pear-shaped fruit
EXAMPLE 26
Several species of plants were grown in potting soil in four-inch pots in the greenhouse. Aqueous spray formulations containing 1-(2-carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide were prepared and the potted plants were sprayed at a spray volume of 40 gallons per acre (374 liters per hectare) and application rates of 16, 4, 1 and 1/4 oz. per acre (1.12 kg, 280 g, 70 g and 17.5 g per hectare). The spray mixtures were prepared by dissolving the proper amount of 1-(2-carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide in 15 ml of acetone, adding 2 ml of a solvent-emulsifier mixture consisting of 60 wt. percent of a commercial polyethoxylated 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 a corresponding solvent-surfactant mixture dispersed in water.
The following growth regulating effects were observed and evaluated:
Epinasty
Drooping leaves
Stunting
Formative effects on new growth
The total of all effects was scored on a scale of 0=no effect to 10=maximum effect. The results are summarized in the following table.
TABLE IV__________________________________________________________________________ Appl'nPlant species, variety rateand stage of growth (oz/A.) Score Description of effects__________________________________________________________________________Setaria italica 16 0 No visible effect10-12 inches, 6-7 leaves 4 0 1 0 1/4 0Sorghum vulgare 16 0 No visible effectDeKalb E-57 4 012-15 in., 6 leaves 1 0 1/4 0Zea mays, DeKalb XL-373 16 0 No visible effect16-18 in., 6-7 leaves 4 0 1 0 1/4 0Hordeum vulgare, Larker 16 0 No visible effect10-12 in., 4-5 leaves 4 0 1 0 1/4 0Oryza sativa, Labelle 16 0 No visible effect6-8 in., 3-4 leaves 4 0 1 0 1/4 0Soja max, Williams 16 9 At 16 oz. new leaves much smaller.9-11 in., 2 trifoliates 4 9 Epinasty on stems, formative effectplus 1/2 of next leaf 1 4 on leaves, plants darker green in 1/4 1 color.Gossypium herbaceum, 16 3 Leaves were in vertical position,Stoneville 213 4 0 rather than horizonal.8-10 in., 3 true leaves 1 0 1/4 0Arachis hypogaea, 16 3 Leaves drooping, slight epinasty.Florunner 4 06-8 in., 6 leaves 1 0 1/4 0Medicago sativa, Kansas 16 8 Epinasty, formative effect on newCommon 4 3 growth; many new stems at base with 1 0 formative effects. 1/4 0Linum usitatissimum, Linott 16 2 Slight increase in axillary growth.6-7 in., 26-32 leaves 4 0 1 0 1/4 0Beta vulgaris, Great 16 8 Formative effect (rolling) ofWestern 4 5 leaves, stunting, new growth5-6 in., 4 true leaves 1 4 inhibited. 1/4 0Brassica napus, Torch 16 7 Formative effect on new growth.5-6 in., 4-5 true leaves 4 4 Stunting. 1 2 1/4 0Phaseolus vulgaris, UI-114 16 9 Epinasty, drooping of leaves,14-16 in., 3-4 trifoliate 4 8 formative effect on newleaves 1 5 growth. Stunting at higher 1/4 3 application rates.Phaseolus vulgaris, Topcrop 16 9 Epinasty, drooping of leaves,11-13 in., 3 trifoliate 4 9 formative effect on new growth,leaves 1 8 earlier set of beans, stunting at 1/4 3 higher application rates.Cucumis sativus, Marketer 16 3 At 16 and 4 oz. per A. new growth11-13 in., 4 true leaves 4 0 stopped. 1 0 1/4 0Cucumis melo, Hearts of 16 2 Stunting, axillary growthGold 4 0 inhibited.9-11 in., 3-4 true leaves 1 0 1/4 0Citrullus vulgaris, Congo 16 1 Slight increase in fruit set.8-10 in., 3 true leaves 4 0 Vines 18 in. in length had melons. 1 0 1/4 0Raphanus sativus, Scarlet 16 2 Formative effect on new leaves atGlobe 5-7 in. 4-5 true 4 1 highest rates.leaves 1 0 1/4 0Caucus carota, Gold Pak 16 2 Formative effect on leaves.3-4 in., 3-4 true leaves 4 1 1 0 1/4 0Allium cepa, Yellow 16 0 No visible effect.Bermuda 5-6 in., 2 leaves 4 0 1 0 1/4 0Beta vulgaris, Detroit 16 9 Severe drooping of leaves andDark Red 4 9 stunting. Leaves rolled together.4-5 in., 4-5 true leaves 1 9 1/4 8Lactuca sativa, Black 16 0 No visible effect.Seeded Simpson 4 0 1 0 1/4 0Lycopersicum esculentum, 16 9 Formative effect on new leaves atTiny Tim 4 8 all application rates, epinasty,7-8 in., 6-8 true leaves, 1 8 drooping of leaves within 24 hours,blooming (6 weeks old) 1/4 7 much earlier and increased fruit set (8-10 tomatoes versus 1-2 for untreated plants)__________________________________________________________________________
EXAMPLE 27
Seeds of Williams variety Soja max were planted in a field in Missouri on May 15th. The compound 1-(2-carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide was applied at five different rates, (16, 4, 1, 1/4 and 1/16 oz. per acre) at four different times, July 7th, July 18th, July 27th and August 8th. Each application rate was replicated four times in four different soil fertilization programs. On July 15th there was severe hail damage to the plots in a spotty, non-uniform pattern which made it impossible to score the final results quantitatively. It was observed on July 18th that in damaged areas, some of the best plants containing the most seed pods had received the most severe injuries. An inspection of plants in less damaged areas on August 8th indicated that the application of 4 oz. per acre of growth regulant on July 18th had increased the size and number of seed pots, particularly in the upper one-third of the plants. Counts showed an average of 109 seed pods on the treated plants versus 86 pods on untreated plants. At the time of spraying the plants had been 30 to 33 inches tall, in bloom and with 8 to 10 small pods on each plant. On September 7th it was observed that both treated and untreated plots had shown substantial recovery from hail damage. Although many stems had been bent or broken off, new growth had occurred and more seed pods had set. Treated plants, particularly those treated at 4, 1 and 1/4 oz. per acre were still green and had many well-filled pods all the way to the top of each plant. Untreated plants had begun to change color, indicating that growth of beans had ceased and the ripening stage was beginning.
In a similar test plot of Williams variety of Soja max in Kansas, which was planted on May 30th and was treated with the same compound on July 28th at 1 oz. and 4 oz. per acre, a substantial increase in pod set was observed in August. On September 5th the plants were mature and had stopped blooming and setting pods. A count was made of pods and seeds on the best of three untreated plants selected at random and on randomly selected individual treated plants. Results were as follows:
______________________________________Application rate,oz. per acre 0 1 4______________________________________Number of pods, 54 81 64one plantNumber of beans, 132 212 181one plantPlant increase 0 61% 37%______________________________________
In another test plot in Kansas about 135 miles south of the one discussed above, seeds of Soja max of the York variety were planted in drilled rows 36 cm. apart on July 10th, after the harvesting of wheat in the area. The plants were sprayed with 1-(2-carbomethoxybenzoyl)-2-methyl-4-phenyl-3-thiosemicarbazide at rates of 1, 2 and 4 oz. per acre on August 24th. The plants at the time of spraying were about 21 inches (53 cm.) high and were in budding and blooming stage. On September 7th the plants were examined and were found to be still green and almost through with budding and blooming. Counts were made on groups of five randomly selected plants from each treatment of the number of pods set on plants. Results were as follows:
______________________________________Application rate,oz. per acre 0 1 2 4______________________________________Total No. of pods, 109 184 183 1775 plantsPercent Increase 0 69% 67% 62%______________________________________
EXAMPLE 28
Among the compounds referred to in the foregoing tables, interesting and useful growth regulating effects are also observed on other species. For example, tillering of Avena sativa (oats) and in some instances also of Triticum aestivum (wheat) was observed with resulting increase in number of seed heads by compounds numbered as follows:
______________________________________2790 2882 31462822 2883 31802844 2885 31812845 3108 32102854 3109 3284______________________________________
Among the preferred compounds of this invention are those wherein R is ##STR30## m is 0, R.sup.3 is hydrogen or C.sub.1 -C.sub.4 alkyl, R.sup.4 is hydrogen and Ar is phenyl or benzyl, either of which can be substituted as shown in formula I. A more preferred class of compounds are those wherein Ar is phenyl or phenyl monosubstituted with fluoro, chloro, bromo, methyl, benzyloxy, methoxy or triifluoromethyl. The most preferred R.sup.3 substituent is methyl.
Another preferred class of compounds are those compounds of formula I wherein R is ##STR31## m is 0, R.sup.3 is hydrogen or methyl, R.sup.4 is hydrogen. Ar is ##STR32## n is 0 or 1 and q is 0, or an agriculturally acceptable salt or ester thereof.
Still another preferred class of compounds are those of the formula ##STR33## wherein R.sup.12 is hydrogen, lower alkyl or an agriculturally-acceptable cation and
R.sup.13 is hydrogen or lower alkyl.
A still further preferred class of compounds are those of the formula ##STR34## wherein R.sup.7 is --OH, --OR.sup.11, --OA or --NR'"R"";
R.sup.11 is C.sub.1 -C.sub.18 alkyl, C.sub.1 -C.sub.8 haloalkyl or C.sub.3 -C.sub.8 alkoxyalkyl;
A is Na.sup.+, K.sup.+, Li.sup.+, NH.sub.4.sup.+ or other agriculturally acceptable cation;
R''' and R'''' are hydrogen or methyl;
R.sup.8 is hydrogen, methyl, nitro, chloro or fluoro;
R.sup.9 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.4 alkenyl containing no .alpha.,.beta. unsaturation or benzyl;
Ar' is naphthyl, anthranyl or phenanthryl, or benzyl which may have one of methyl, methoxy, bromo, chloro, fluoro and tri fluoromethyl substituents thereon, or phenyl which may have one to three of methyl, methoxy, bromo, chloro, fluoro and trifluoromethyl substituents thereon provided that both ortho positions of phenyl are not substituted by methyl; and
R.sup.10 is hydrogen or C.sub.1 -C.sub.3 alkyl.
A still further class of preferred compounds are those wherein R is --CH.sub.2 OH, R.sup.3 is hydrogen or C.sub.1 -C.sub.4 alkyl, m is 0, R.sup.4 is hydrogen and Ar is naphthyl or a group having one of the following formulae: ##STR35##
By the term "agriculturally-acceptable salts and esters" is meant salts and esters of the compounds of this invention which may be used in plant growth regulation in the same manner as the parent compounds to achieve the same effects. Such salts and esters do not adversely affect the activity of the compounds nor do they have a substantial adverse effect upon the plants to which they are applied for the purpose of achieving a beneficial effect.
Among such agriculturally-acceptable esters are those prepared from primary and secondary alkanols, such as those containing from one to about eighteen carbon atoms, haloalkanols containing from one to about eight carbon atoms, alkoxyalkanols containing about three to about eight carbon atoms and arylalkanols containing from seven to about ten carbon atoms. Exemplary of acceptable alkanols are methanol, ethanol, isopropanol, neopentyl alcohol, undecanol, hexadecanol, and octadecanol. Among exemplary haloalkanols are chloroethanol, 3-bromopropanol and chlorohexanol. Useful alkoxyalkanols include methoxyethanol, ethoxyethanol, butoxyethanol and such alkoxyalkoxyalkanols as butoxyethoxyethanol and ethoxyethoxyethanol. Suitable arylalkanols include benzyl alcohol and phenethanol.
Salts of the compounds of this invention include metal salts, ammonium salts, quaternary ammonium salts and amine salts. Numerous examples of such salts are found in the Examples of this specification.

Number	Date	Country
53-74549	Jul 1978	JPX
1272920	May 1972	GBX

Substituted thiosemicarbazides, their manufacture and use as plant growth regulants

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Meran, Rev. Stiintifica, vol. 32 (1946), pp. 136-138.
Buu-Hoi et al., Bul. Soc. Chim. France (1965), 363-369.