USRE31550E - N-(2-Chloro-4-pyridyl) ureas - Google Patents
N-(2-Chloro-4-pyridyl) ureas Download PDFInfo
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- USRE31550E USRE31550E US06/305,768 US30576881A USRE31550E US RE31550 E USRE31550 E US RE31550E US 30576881 A US30576881 A US 30576881A US RE31550 E USRE31550 E US RE31550E
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- pyridyl
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- urea
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
Definitions
- the invention relates to novel N-(2-chloro-4-pyridyl)ureas and thioureas represented by the formula(I) indicated hereinafter, agricultural compositions thereof, and a method of treating plants with them.
- British Pat. No. 1,122,662 discloses that some derivatives of urea can be used for preservation of plant materials. Further, Proc. Roy. Soc., vol. B165, page 245, London (1966) reports that some ureas produce a desirable effect for developing the plantbud, while others show a mold effect as initiators of cell division.
- This invention relates to novel N-(2-chloro-4-pyridyl)ureas and thioureas of formula(I) and acid addition salts thereof; a process for their preparation; a method of using the compounds and compositions for agricultural purposes, especially as plant growth regulators, and a process for the preparation of such compositions.
- novel compounds of formula(I) have valuable agricultural properties, especially growth-regulating effects as further elucidated hereinafter, which makes them useful as plant growth regulators.
- This invention relates to novel N-(2-chloro-4-pyridyl)ureas and thioureas, a process for their preparation, agricultural compositions which are useful as plant growth regulators containing one of the said compounds as an effective component thereof, and a method of treating plants therewith.
- Regulation of plant growth means acceleration or suppression of plant growth with a very small quantity of a chemical to regulate and control the state of plant growth as desired. Consequently, it does not indicate merely an increase or decrease in the height of a plant, but also the ability to have flowers or fruits when desired, or to obtain fruits without seeds, or to make the seeds dormant or conversely take them out of dormancy.
- One object of this invention is to provide plant growth regulators which have advantages over such known useful substances. Other advantages will become apparent hereinafter.
- the active compounds provided by this invention comprise N-(2-chloro-4-pyridyl)ureas and thioureas having the following formula(I): ##STR2## wherein R 1 represents hydrogen or alkyl of 1 to 3 carbon atoms, inclusive, such as methyl, ethyl, propyl and isopropyl; R 2 represents an aromatic group, preferably phenyl, pyridyl, naphthyl or biphenyl, which may be substituted by alkyl of 1 to 3 carbon atoms, inclusive, alkoxy of 1 to 3 carbon atoms, inclusive, hydroxyl, or halogen, especially one or two bromine, chlorine, or fluorine atoms; and X is oxygen or sulfur; and acid addition salts thereof.
- halogen-substituted phenyl is preferably chlorine and fluorine, more preferably chlorine.
- the compounds represented by formula(I), wherein X represents oxygen can be prepared by conventional methods.
- R 1 is a hydrogen atom and R 2 is unsubstituted phenyl.
- R 1 is a hydrogen atom
- R 2 is unsubstituted phenyl.
- 2-chloro-4-aminopyridine is reacted with phenyl isocyanate
- 2-chloro-4-pyridyl isocyanate is reacted with aniline
- 2-chloro-isonicotinoylacide is reacted with aniline.
- reaction it is preferred to use a slight excess of one of the reactants, although approximately equivalent amounts of reactants may also be used in the usual suitable solvents.
- Some solvents for the reaction are benzene, toluene, xylene, actone, methyl ethyl ketone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, chloroform, dichloromethane, tetrachloromethane, pyridine, and triethyl amine.
- An excess of aniline, when a reactant is particularly useful as solvent.
- the reaction is favorably conducted in the range of -5° to 150° C., including room temperature, although it is most preferred to effect the reaction at the reflux temperature of the reaction mixture. A reaction time between five-tenths and five hours is sufficient to produce a good yield of desired product.
- the compounds represented by the formula(I), wherein X represents sulfur can be also prepared by conventional methods illustrated in (a) and (b) by using the corresponding starting materials and under similar reaction conditions.
- the reaction temperature should generally be in the range of 20° to 150° C.
- N-(2-Chloro-4-pyridyl)-N'-phenylurea N-(2-chloro-4-pyridyl)-N'-(2-chlorophenyl)urea, N-(2-chloro-4-pyridyl)-N'-(3-chlorophenyl)urea, N-(2-chloro-4-pyridyl)-N'-(4-chlorophenyl)urea, N-(2-chloro-4-pyridyl)-N'-(2-methylphenyl)urea, N-(2-chloro-4-pyridyl)-N'-(3-methylphenyl)urea, N-(2-chloro-4-pyridyl)-N'-(4-methylphenyl)urea, N-(2-chloro-4-pyridyl)-N'-(2,5-dichlorophenyl)urea, N-(2-chloro-4-pyrid
- N-(2-chloro-4-pyridyl)ureas and thioureas of this invention possess accelerating action on cell mitosis, cell enlargement, and cell differentiation, and are effective in the acceleration of fruiting, prevention of fruit and flower from falling, growth acceleration, and growth suppression.
- concentration of the chemical employed By adjusting the concentration of the chemical employed, a marked suppression of growth(herbicidal) can be caused to occur at a high concentration of the chemical.
- Table A The action, field of application, use, and plants to which these chemicals are applicable, are listed in the following table (Table A).
- Table A The most prominent effective use of these chemicals is found in the increased number of fruits in pepos such as melon and watermelon, inhibition of flower shedding, accelerated growth of green vegetables, extension of tobacco leaf area, and herbicidal effect (when desired).
- the urea derivatives of this invention show the same activity in concentrations only a fraction of that required with 6-(N-benzyl)adenine and kinetin, which have hitherto been considered the most potent plant growth regulating substances available. Even in comparison with N-(4-pyridyl)-N'-phenylurea of similar structure, they show a 100-fold or greater increase in activity. This increased activity is unexpectedly observed only when a chlorine atom is present at the 2-position of the pyridine ring.
- the optimal concentration to give maximum yield of callus is 0.01 ppm for 6-(N-benzyl)adenine and 0.1 ppm for N-(4-pyridyl)-N'-phenylurea, whereas that of the potent N-(2-chloro-4-pyridyl)ureas of this invention is only 0.0005 to 0.001 ppm.
- substitution on the phenyl ring decreases the activity in the tobacco test for the acceleration of cell differentiation, the optimal concentration of 6-benzyladenine being 10 ppm, but less than 1 ppm of N-(2-chloro-4-pyridyl)ureas gives formation of numerous shoots.
- N-(2-Chloro-4-pyridyl)ureas of this invention show the effect of increasing weight, not only in callus cells but also on pith tissue, leaf tissue, and on plants during growth.
- the plant growth regulators of this invention can be applied to plants and crops in general, but are especially effective when applied to a member of the leguminosae, solanaceae, unbelliferae, popes vitaceal, cucurbitaceae and vitaceae families.
- the amount of a compound of this invention to be used by spraying the plant directly is generally 100 to 1000 liters per Ha as a solution of a concentration of 0.0001 to 10,000 ppm, preferably 0.01 to 10,000 ppm. When used in soil, an amount 5- to 100-fold of that given above is required. It goes without saying that the amount to be applied will differ according to the object of the control and the plant to which applied. For example, 100 to 1000 liters of a solution of the following concentration should be used per Ha.
- the compounds of this invention can be used alone or in admixture with other substances or compositions having effective components, such as other plant regulators, herbicides, insecticides, fungicides, and acericides, usually in the form of solutions, emulsions, wettable powders, granules, fine granules, or powders.
- compositions may be carried out in known manner, as by mixing, for example, 0.1 to 50%, preferably 0.1 to 10%, of a compound of this invention with a bulking agent, such as a liquid or solid diluent or carrier and, if necessary, using an emulsifying agent or dispersing agent.
- a bulking agent such as a liquid or solid diluent or carrier
- an emulsifying agent or dispersing agent emulsifying agent or dispersing agent.
- a liquid diluent or a carrier may be cited water, aromatic hydrocarbons such as xylene, benzene, and methylnaphthalene, chlorinated aromatic hydrocarbons such as chlorobenzene, mineral oil fractions such as paraffin, alcohols such as methanol and propanol, and polar solvents such as dimethylformamide and acetone.
- the substances preferably as a solid diluent or carrier are, for example, talc, clay, kaolin, white carbon, wood powder and sand.
- a emulsifying agent may be used polyoxyethylene-fatty acid esters or polyoxyethylene-fatty acid alcohol ethers.
- Dispersing agents include alkyl sulfonates, alkyl aryl sulfonates, alkali metal salts, alkaline earth metal salts, ammonium salt of lignin-sulfonic acid, and methylcellulose.
- These compounds or preparations thereof per se may be added to a medium or applied directly to the plant or onto the surface of leaves or stalks thereof, or sprayed on the soil, but are usually applied in the form of the usual preparations thereof. Further, the plant growth controlling agents of this invention may be added together with fertilizers and/or extenders.
- These compounds can also be used in the form of an inorganic or organic salt such as the hydrochloride, phosphate, or sulfate thereof.
- Tobacco callus was cultured in Murashige-Skoog medium containing 0.0001 to 0.1 ppm of N-(2-chloro-4-pyridyl)-N'-phenylurea and 2 ppm of indoleacetic acid as auxin, for 30 days at a temperature of about 26° C. Final weight of fresh callus is shown in Table I.
- the control was a tabacco callus cultured in the Murashige-Skoog medium containing only auxin, under the same condition. For the sake of comparison, values obtained in a medium containing optimal amount 6-(N-benzyl)adenine are also given in Table I. Values are all an average of six individuals.
- Tobacco callus was cultured in the same way as in Example 1 and the results shown in the following Table II were obtained.
- Section(s) of tobacco pith tissue were inoculated in Murashige-Skoog medium containing 0.01 to 10 ppm of N-(2-chloro-4-pyridyl)-N'-phenylurea. This was cultured at a temperature of about 26° C. for 30 days, and the number of pith sections forming shoots was counted. For comparison, benzyladenine was tested in a similar way. Results are shown in Table III.
- Tobacco callus was inoculated in Murashige-Skoog medium containing 0.01 to 10 ppm of N-(2-chloro-4-pyridyl)-N'-phenylurea. This was cultured at room temperature for 30 days, and the number of callus with shoot formation was counted. For comparison, benzyladenine was tested in a similar way. Results are shown in Table IV.
- Solutions containing 10, 1, and 0.1 ppm of N-(2-chloro-4-pyridyl)-N'-phenylurea in water were prepared.
- 10 pieces of the leaf of Brassica repa var. pervidis which were round leaves of a 10 mm. diameter and cut out with a corkborer, were floated on the surface of the solution, one group being in contact with the solution with the back of the leaf and the other group being in contact with the surface of the solution with the surface of the leaf.
- the dishes were allowed to stand at room temperature for 8 days, and diameter and weight of each leaf pieces determined. The control leaves were left in water.
- Watermelon (variety ⁇ Yamato ⁇ ) raised outdoors was used as test plant. Artificial pollination was made at the peak of flowering, and a solution of the selected chemical in desired concentration was pinted or sprayed on the gynophore. Fruit-bearing rate was examined two weeks after the treatment.
- Seedlings of tobacco were transplanted in unglazed pots of about 13 cm. in diameter and the pots were left in a greenhouse. Solutions of the selected chemical of desired concentration were sprayed with a sprayer, 15 ml. for each pot, homogeneously on leaves and stalk at the time when 6 to 8 leaves were out. One section of the pots was sprayed once and the other section three times at 13-day intervals. Examination of the result was made when middle leaves started to become yellow (35 days after the initial spraying of the chemical), and height of the plant, fresh weight of stalk and leaves, and average area of five lower leaves were measured, and ratio of these values to those of the non-treated plants was calculated. Experimental section was three pots per area and their average was taken. Results are listed in the following Table VIII.
- Grapevine (variety Delaware) raised in plastic house covering was used for the examination. N-(2-Chloro-4-pyridyl)-N'-phenylurea or benzyladenine (200 or 100 ppm) was dded to 100 ppm of gibberelline solution, and recemose flowers were dipped in each solution (April 14). Ten days after full bloom (May 4), all the fruit clusters were again soaked and treated with 100 ppm solution of gebberelline. The grapevines were then left to usual cultivation conditions until harvest. Grapes were harvested on June 29, and weight of each cluster, length of cluster, density of berries, number of berries on each cluster, and berry diameter were measured. These values were compared with those found with grapes with gebberelline treatment alone. Experimental area contained two new brances, three repetition, and average value of fifteen fruit clusters was calculated.
- Soil containing the subterranean stems of narrowleaf waterplantain (Alisma canaliculatum) and bulrush (Scirpus juncoides) homogeneously was filled in ceramic pots of 30 cm in diameter. Seeds of barnyard grass (Echinochloa crus-balli), umbrella plant (Cyperus diformis) were each sown in pots, fifty seeds to each pot. Then paddy rice seedlings (Variety Kinmaze) at the two-leaf stage was planted, five seedlings per pot, and the pots were filled with water so as to have a water layer of three cm. above the soil.
- Datura Sunguinea sp. (average height of 8 cm.) were transplanted outdoors. Solutions of the chemically desired concentration were sprayed with a sprayer, 15 ml. each plant, on the leaves and stalk of the plant at the time when the average height of the plant was 20 cm. Three weeks later, the plants were harvested and the height of the plant and the total weight of fresh leaves and stalks on the new brances were measured. Average values of five plants are listed in Table XI.
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Abstract
N-(2-Chloro-4-pyridyl)ureas represented by the formula (I): ##STR1## wherein R1 represents hydrogen or alkyl, R2 represents an aromatic group, especially phenyl, which may be substituted by alkyl, alkoxyl, hydroxyl or halogen, and X is oxygen or sulfur, and acid addition salts thereof, useful as plant growth regulators, are disclosed. Method of making and using same and agricultural compositions thereof are also disclosed.
Description
1. Field of the Invention
The invention relates to novel N-(2-chloro-4-pyridyl)ureas and thioureas represented by the formula(I) indicated hereinafter, agricultural compositions thereof, and a method of treating plants with them.
2. Brief Description of the Prior Art
British Pat. No. 1,122,662 discloses that some derivatives of urea can be used for preservation of plant materials. Further, Proc. Roy. Soc., vol. B165, page 245, London (1966) reports that some ureas produce a desirable effect for developing the plantbud, while others show a mold effect as initiators of cell division.
This invention relates to novel N-(2-chloro-4-pyridyl)ureas and thioureas of formula(I) and acid addition salts thereof; a process for their preparation; a method of using the compounds and compositions for agricultural purposes, especially as plant growth regulators, and a process for the preparation of such compositions.
The novel compounds of formula(I) have valuable agricultural properties, especially growth-regulating effects as further elucidated hereinafter, which makes them useful as plant growth regulators.
This invention relates to novel N-(2-chloro-4-pyridyl)ureas and thioureas, a process for their preparation, agricultural compositions which are useful as plant growth regulators containing one of the said compounds as an effective component thereof, and a method of treating plants therewith. Regulation of plant growth means acceleration or suppression of plant growth with a very small quantity of a chemical to regulate and control the state of plant growth as desired. Consequently, it does not indicate merely an increase or decrease in the height of a plant, but also the ability to have flowers or fruits when desired, or to obtain fruits without seeds, or to make the seeds dormant or conversely take them out of dormancy.
Control of plant growth with plant hormones is becoming an important technique in the agricultural and horticultural fields. Among the best and best-known plant growth regulators are cytokinine 6-(N-benzyl)adenine and kinetine.
One object of this invention is to provide plant growth regulators which have advantages over such known useful substances. Other advantages will become apparent hereinafter.
It has now been found that 4-pyridylureas and thioureas, which contain a chlorine atom in the 2-position of the pyridine ring, possess an extremely potent activity of the said type and have the ability to regulate plant growth over a wide range.
The active compounds provided by this invention comprise N-(2-chloro-4-pyridyl)ureas and thioureas having the following formula(I): ##STR2## wherein R1 represents hydrogen or alkyl of 1 to 3 carbon atoms, inclusive, such as methyl, ethyl, propyl and isopropyl; R2 represents an aromatic group, preferably phenyl, pyridyl, naphthyl or biphenyl, which may be substituted by alkyl of 1 to 3 carbon atoms, inclusive, alkoxy of 1 to 3 carbon atoms, inclusive, hydroxyl, or halogen, especially one or two bromine, chlorine, or fluorine atoms; and X is oxygen or sulfur; and acid addition salts thereof.
Of these substituents, hydrogen and methyl for R1, unsubstituted or methyl-substituted phenyl for R2 and oxygen for X are preferred. The most preferred are hydrogen for R1, unsubstituted phenyl for R2 and oxygen for X. In the case of the halogen-substituted phenyl for R2, the halogen is preferably chlorine and fluorine, more preferably chlorine.
The compounds represented by formula(I), wherein X represents oxygen, can be prepared by conventional methods. For brevity, reference is specifically made to the compound represented by formula(I), wherein R1 is a hydrogen atom and R2 is unsubstituted phenyl. Following conventional preparations, either (a) 2-chloro-4-aminopyridine is reacted with phenyl isocyanate, or (b) 2-chloro-4-pyridyl isocyanate is reacted with aniline, or (c) 2-chloro-isonicotinoylacide is reacted with aniline.
In carrying out this reaction, it is preferred to use a slight excess of one of the reactants, although approximately equivalent amounts of reactants may also be used in the usual suitable solvents. Some solvents for the reaction are benzene, toluene, xylene, actone, methyl ethyl ketone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, chloroform, dichloromethane, tetrachloromethane, pyridine, and triethyl amine. An excess of aniline, when a reactant, is particularly useful as solvent. The reaction is favorably conducted in the range of -5° to 150° C., including room temperature, although it is most preferred to effect the reaction at the reflux temperature of the reaction mixture. A reaction time between five-tenths and five hours is sufficient to produce a good yield of desired product.
The compounds represented by the formula(I), wherein X represents sulfur can be also prepared by conventional methods illustrated in (a) and (b) by using the corresponding starting materials and under similar reaction conditions. However, as the reactivity and speed of the reaction for preparing thioureas is not as great when compared with the urea compounds, the reaction temperature should generally be in the range of 20° to 150° C.
The above-mentioned preparations (a), (b) and (c) can be represented by the following chemical reaction schemes: ##STR3## wherein R1 and X have the same meanings as in formula(I) and R3 represents lower alkyl, lower alkoxyl, hydroxyl, or halogen, especially bromine, chlorine or fluorine.
Some of the compounds of this invention are listed in the following:
N-(2-Chloro-4-pyridyl)-N'-phenylurea, N-(2-chloro-4-pyridyl)-N'-(2-chlorophenyl)urea, N-(2-chloro-4-pyridyl)-N'-(3-chlorophenyl)urea, N-(2-chloro-4-pyridyl)-N'-(4-chlorophenyl)urea, N-(2-chloro-4-pyridyl)-N'-(2-methylphenyl)urea, N-(2-chloro-4-pyridyl)-N'-(3-methylphenyl)urea, N-(2-chloro-4-pyridyl)-N'-(4-methylphenyl)urea, N-(2-chloro-4-pyridyl)-N'-(2,5-dichlorophenyl)urea, N-(2-chloro-4-pyridyl)-N'-(2-fluorophenyl)urea, N-(2-chloro-4-pyridyl)-N'-(4-n-propylphenyl)urea, N-(2-chloro-4-pyridyl)-N'-(2-ethoxyphenyl)urea, N-(2-chloro-4-pyridyl)-N'-phenylthiourea, N-(3-bromo-4-pyridyl)-N'-phenylurea, etc.
The N-(2-chloro-4-pyridyl)ureas and thioureas of this invention possess accelerating action on cell mitosis, cell enlargement, and cell differentiation, and are effective in the acceleration of fruiting, prevention of fruit and flower from falling, growth acceleration, and growth suppression. By adjusting the concentration of the chemical employed, a marked suppression of growth(herbicidal) can be caused to occur at a high concentration of the chemical.
The action, field of application, use, and plants to which these chemicals are applicable, are listed in the following table (Table A). The most prominent effective use of these chemicals is found in the increased number of fruits in pepos such as melon and watermelon, inhibition of flower shedding, accelerated growth of green vegetables, extension of tobacco leaf area, and herbicidal effect (when desired).
TABLE A
______________________________________
Action Application, Use
Plants to be applied
______________________________________
1. Acceleration
Increased fruits
pepos, tomato, eggplant,
of fruit bearing
(flowers)(fruit)
apple, Japanese pear,
citrus, apricot, soybean
Prevention of
Inhibition of grape
fruit falling
flower shedding
2. Acceleration
Picking fruits citrus, plum, peach,
of fruit falling
(picking excess
apple, tomato, pineapple
and defoliation
fruits to
increase fruit
yield and to
make fruit size
uniform)
Picking flowers
apricot, Japanese pear,
(excess flowers
plum, peach
picked to
increase fruit
yield and to
make fruit size
uniform)
Defoliation cotton, soybean
(to remove leaves
for easier
harvesting of
cotton and soybeans)
3. Growth Acceleration of
cuttage
acceleration
root growth and
taking root
Growth accelera-
vegetables
tion(stalk, leaves,
roots)
Increased size of
citrus, apple, apricot
fruit(increase in
commercial value
by larger size of
fruit)
Increased tiller-
soybean, pineapple
ing, accelerated
bud formation
Accelerated flowering plants
flowering
4. Growth Suppression of trees, grass, flowering
suppression
height plants
Suppression of paddy rice, wheat
lodging
Suppression of potato, onion
budding
Suppression of soybean
tillering
(prevention of
excess growth)
5. Organ Renewal of new rose, fruit tree
Formation branches(buds) seedlings
6. Others Herbicidal effect
Desiccation cotton
Increased sugar
sugar cane, sugar beet
content
______________________________________
The urea derivatives of this invention show the same activity in concentrations only a fraction of that required with 6-(N-benzyl)adenine and kinetin, which have hitherto been considered the most potent plant growth regulating substances available. Even in comparison with N-(4-pyridyl)-N'-phenylurea of similar structure, they show a 100-fold or greater increase in activity. This increased activity is unexpectedly observed only when a chlorine atom is present at the 2-position of the pyridine ring.
To explain in more concrete terms, in the test for tobacco callus growth, the optimal concentration to give maximum yield of callus is 0.01 ppm for 6-(N-benzyl)adenine and 0.1 ppm for N-(4-pyridyl)-N'-phenylurea, whereas that of the potent N-(2-chloro-4-pyridyl)ureas of this invention is only 0.0005 to 0.001 ppm. Generally, substitution on the phenyl ring decreases the activity in the tobacco test for the acceleration of cell differentiation, the optimal concentration of 6-benzyladenine being 10 ppm, but less than 1 ppm of N-(2-chloro-4-pyridyl)ureas gives formation of numerous shoots.
N-(2-Chloro-4-pyridyl)ureas of this invention show the effect of increasing weight, not only in callus cells but also on pith tissue, leaf tissue, and on plants during growth.
The plant growth regulators of this invention can be applied to plants and crops in general, but are especially effective when applied to a member of the leguminosae, solanaceae, unbelliferae, popes vitaceal, cucurbitaceae and vitaceae families.
The amount of a compound of this invention to be used by spraying the plant directly is generally 100 to 1000 liters per Ha as a solution of a concentration of 0.0001 to 10,000 ppm, preferably 0.01 to 10,000 ppm. When used in soil, an amount 5- to 100-fold of that given above is required. It goes without saying that the amount to be applied will differ according to the object of the control and the plant to which applied. For example, 100 to 1000 liters of a solution of the following concentration should be used per Ha.
______________________________________
For growth acceleration and
0.01-1,000 ppm
increased fruiting
For growth acceleration of callus
0.0001-100 ppm
For acceleration of fruit
0.1-10,000 ppm
falling and defoliation
For growth suppression and herbicidal
10-more than
10,000 ppm
______________________________________
The compounds of this invention can be used alone or in admixture with other substances or compositions having effective components, such as other plant regulators, herbicides, insecticides, fungicides, and acericides, usually in the form of solutions, emulsions, wettable powders, granules, fine granules, or powders.
The preparation of suitable compositions may be carried out in known manner, as by mixing, for example, 0.1 to 50%, preferably 0.1 to 10%, of a compound of this invention with a bulking agent, such as a liquid or solid diluent or carrier and, if necessary, using an emulsifying agent or dispersing agent. As substances preferably as a liquid diluent or a carrier may be cited water, aromatic hydrocarbons such as xylene, benzene, and methylnaphthalene, chlorinated aromatic hydrocarbons such as chlorobenzene, mineral oil fractions such as paraffin, alcohols such as methanol and propanol, and polar solvents such as dimethylformamide and acetone. Among the substances preferably as a solid diluent or carrier are, for example, talc, clay, kaolin, white carbon, wood powder and sand. As an emulsifying agent may be used polyoxyethylene-fatty acid esters or polyoxyethylene-fatty acid alcohol ethers. Dispersing agents include alkyl sulfonates, alkyl aryl sulfonates, alkali metal salts, alkaline earth metal salts, ammonium salt of lignin-sulfonic acid, and methylcellulose.
These compounds or preparations thereof per se may be added to a medium or applied directly to the plant or onto the surface of leaves or stalks thereof, or sprayed on the soil, but are usually applied in the form of the usual preparations thereof. Further, the plant growth controlling agents of this invention may be added together with fertilizers and/or extenders.
These compounds can also be used in the form of an inorganic or organic salt such as the hydrochloride, phosphate, or sulfate thereof.
The following examples and preparations are given by way of illustration only, and are not to be construed as limiting.
Some representative examples of preparative forms will be given below.
______________________________________
Preparation 1.
Wettable powder
N--(2-Chloro-4-pyridyl)-N'--
1%
phenylurea
Sodium β-naphthalenesulfonate-
2%
formaldehyde condensate
Polyoxyethylene alkyl aryl ether
2%
Clay 95%
______________________________________
These ingredients are ground, mixed and diluted with water.
______________________________________
Preparation 2.
Emulsion
N--(2-Chloro-4-pyridyl)-N'--
1%
(3-chlorophenyl)urea
Xylene 74%
Polyoxyethylene alkyl aryl ether
4.5%
Alkyl aryl sulfonate
0.5%
Isophorone 20%
______________________________________
The above ingredients are mixed to dissolve and the resulting solution is emulsified in water.
______________________________________
Preparation 3.
Liquid
N--(2-Chloro-4-pyridyl)-N'--
1%
(2-chlorophenyl)urea
Dimethylformamide 94%
Polyoxyethylenesorbitan
5%
monolaurate
Parts
Preparation 4.
Granule by Weight
N--(2-Chloro-4-pyridyl)-N'--
5%
(3-methylphenyl)urea
Bentonite 15
Talc 47.5
Clay 30
Sodium dodecylbenzene sulfonate
0.5
Sodium ligninsulfonate
2
Preparation 5.
Emulsion
N--(2-Chloro-4-pyridyl)-N'--
5%
(3-methylphenyl)urea
Xylene 70%
Polyoxyethylene alkyl aryl ether
4.5%
Alkyl aryl sulfonate
0.5%
Isophorone 20%
______________________________________
These ingredients are mixed, ground, mixed with 25 parts of water, and made into granules using an extrusion-granulation apparatus. The granules are then dried and sieved. These granules are sprayed per se.
______________________________________
Preparation 6.
Wettable powder
N--(2-Chloro-4-pyridyl-N'--
5%
(3-methylphenyl)urea
Sodium -naphthalenesulfonate-
3%
formaldehyde condensate
Polyoxyethylene alkyl aryl ether
3%
Clay 89%
Preparation 7.
Solution
N--(2-Chloro-4-pyridyl)-N'--
100 ppm
(3-chlorophenyl)urea
Acetone 20%
Water 80%
______________________________________
(1) To a solution of 257 mg. (2 mmol) of 2-chloro-4-aminopyridine dissolved in ten ml. of dry acetone, 238 mg. (2 mmol) of phenyl isocyanate is added and the mixture is stirred at room temperature for 8 hrs. The solvent is evaporated under a reduced pressure, the residue is chromatographed over alumina, and the column is developed with chloroform. Eluates containing the objective substance are collected, and the solvent is evaporated under a reduced pressure. The residue is recrystallized from acetone-ether mixture and 364 mg. of N-(2-chloro-4-pyridyl)-N'-phenylurea is obtained. Yield, 73.5%, mp 173°-174° C.
______________________________________
Analysis for C.sub.12 H.sub.10 CIN.sub.3 O
C H N
______________________________________
Calcd. 58.19 4.07 19.69
Found 58.27 4.15 16.93
______________________________________
(2) To a solution of 365 mg. (2 mmol) of 2-chloroisonicotinoyl azide dissolved in 10 ml. of dry benzene, 186 mg. (2 mmol) of aniline is added and the mixture is refluxed for 3 hrs. When cooled, the solvent is evaporated under a reduced pressure and the residue is chromatographed over alumina. The column is developed with chloroform and eluates containing the objective substance are collected. The solvent is evaporated under a reduced pressure and the residue is recrystallized from acetone-ether mixture to 453 mg. of N-(2-chloro-4-pyridyl)-N'-phenylurea, mp 183°-184° C. Yield, 91.4%.
The following compounds were also prepared in the same manner.
______________________________________
Compound mp (°C.)
______________________________________
N--(2-Chloro-4-pyridyl)-N'--(2-chlorophenyl)urea
183
N--(2-Chloro-4-pyridyl)-N'--(3-chlorophenyl)urea
198-199
N--(2-Chloro-4-pyridyl)-N'--(4-chlorophenyl)urea
201-201.5
N--(2-Chloro-4-pyridyl)-N'--(2-methylphenyl)urea
184-185
N--(2-Chloro-4-pyridyl)-N'--(3-methylphenyl)urea
93-95
N--(2-Chloro-4-pyridyl)-N'--(4-methylphenyl)urea
188.5-190
N--(2-Chloro-4-pyridyl)-N'--(2,5-dichlorophenyl)urea
215-216
N--(2-Chloro-4-pyridyl)-N'--(2-fluorophenyl)urea
186-187
N--(2-Chloro-4-pyridyl)-N'--(4-n-propylphenyl)urea
156-157
N--(2-Chloro-4-pyridyl)-N'--(2-ethoxyphenyl)urea
96-99
N--(2-Chloro-4-pyridyl)-N'--phenylthiourea
141-142
______________________________________
Tobacco callus was cultured in Murashige-Skoog medium containing 0.0001 to 0.1 ppm of N-(2-chloro-4-pyridyl)-N'-phenylurea and 2 ppm of indoleacetic acid as auxin, for 30 days at a temperature of about 26° C. Final weight of fresh callus is shown in Table I. The control was a tabacco callus cultured in the Murashige-Skoog medium containing only auxin, under the same condition. For the sake of comparison, values obtained in a medium containing optimal amount 6-(N-benzyl)adenine are also given in Table I. Values are all an average of six individuals.
TABLE I
______________________________________
Concentration
Weight
(ppm) (mg)
______________________________________
N--(2-Chloro-4-pyridyl)-N'--urea
0.0001 782
" 0.001 4,991
" 0.01 1,235
" 0.1 519
Benzyladenine 0.01 5,150
Control 153
______________________________________
Tobacco callus was cultured in the same way as in Example 1 and the results shown in the following Table II were obtained.
TABLE II
______________________________________
Weight
Concentration(ppm)
(g.)
______________________________________
N--(2-Chloro-4-pyridyl)-N'--
0.001 1,784
(3-methylphenyl)urea
N--(2-Chloro-4-pyridyl)-N'--
0.01 6,760
(3-methylphenyl)urea
N--(2-Chloro-4-pyridyl)-N'--
0.1 4,945
(3-methylphenyl)urea
N--(2-Chloro-4-pyridyl-N'--
1 1,508
(3-methylphenyl)urea
Control 153
______________________________________
The use of N-(2-chloro-4-pyridyl)-N'-(3-chlorophenyl)urea gave a similar result.
Section(s) of tobacco pith tissue were inoculated in Murashige-Skoog medium containing 0.01 to 10 ppm of N-(2-chloro-4-pyridyl)-N'-phenylurea. This was cultured at a temperature of about 26° C. for 30 days, and the number of pith sections forming shoots was counted. For comparison, benzyladenine was tested in a similar way. Results are shown in Table III.
TABLE III
______________________________________
Shoot Formation from Pith Sections
Shoot Formation*
Conc. 6-(N--Benzyl)-
N--(2-Chloro-4-pyridyl)-
(ppm) adenine N'--phenylurea
______________________________________
10 1/24 10/24
1 12/24 13/24
0.1 2/24 10/24
0.01 0/24 0/24
______________________________________
*Number of pith sections with shoots/number of pith sections planted. One
to six shoots are formed from one pith section.
Tobacco callus was inoculated in Murashige-Skoog medium containing 0.01 to 10 ppm of N-(2-chloro-4-pyridyl)-N'-phenylurea. This was cultured at room temperature for 30 days, and the number of callus with shoot formation was counted. For comparison, benzyladenine was tested in a similar way. Results are shown in Table IV.
TABLE IV
______________________________________
Shoot Formation from Tobacco Callus
Shoot Formation Rate*
Concn. N--(2-Chloro-4-pyridyl)-
(ppm) Benzyladenine
N'--(2-methylphenyl)urea
______________________________________
10 12/12.sup.a 10/12.sup.a
1 12/12.sup.a 9/12.sup.a
0.1 2/12.sup.b 1/12.sup.b
0.01 0/12 0/12
______________________________________
*Number of callus forming shoots/number of callus inoculated
.sup.a Number of shoots. 50-70(size of individual shoots. 1-3 cm.)
.sup.b Number of shoots. 1-10(size of individual shoots. 0.5-1 cm.)
Medium solutions containing 0.0001 to 1 ppm of N-(2-chloro-4-pyridyl)-N'-phenylurea were prepared and tobacco callus culture was carried out as in Example 4. The results obtained are shown in Table V.
TABLE V
______________________________________
Shoot Formation from Tobacco Callus
Shoot Formation Rate*
Concn. N--(2-Chloro-4-pyridyl)-
(ppm) Benzyladenine
N'--phenylurea
______________________________________
10 12/12.sup.a --
1 12/12.sup.a 12/12.sup.a
0.1 2/12.sup.b 12/12.sup.a
0.01 0/12 12/12.sup.a
0.001 -- 2/12.sup.b
0.0001 -- 0/12
______________________________________
*Number of callus section forming shoots/number of callus sections
inoculated
.sup.a Number of shoots. 50-70(size of individual shoots. 1-3 cm.)
.sup.b Number of shoots. 1-10(size of individual shoots. 0.5-1 cm.)
Solutions containing 10, 1, and 0.1 ppm of N-(2-chloro-4-pyridyl)-N'-phenylurea in water were prepared. To 50 ml. of each solution placed in a petrie dish, 10 pieces of the leaf of Brassica repa var. pervidis which were round leaves of a 10 mm. diameter and cut out with a corkborer, were floated on the surface of the solution, one group being in contact with the solution with the back of the leaf and the other group being in contact with the surface of the solution with the surface of the leaf. The dishes were allowed to stand at room temperature for 8 days, and diameter and weight of each leaf pieces determined. The control leaves were left in water. These results are shown in Table VI.
TABLE VI
______________________________________
With Back of the Leaf
With Surface of the Leaf
in Contact with Water
in Contact with Water
Concn. Diameter Weight Concn. Diameter
Weight
(ppm) (mm) (mg) (ppm) (mm) (mg)
______________________________________
10 13.7 30.5 10 13.2 26.8
1 13.5 32.1 1 14.2 31.1
0.1 14.2 33.3 0.1 13.9 28.1
Control
12.1 21.7 Control 11.9 21.0
______________________________________
Watermelon (variety `Yamato`) raised outdoors was used as test plant. Artificial pollination was made at the peak of flowering, and a solution of the selected chemical in desired concentration was pinted or sprayed on the gynophore. Fruit-bearing rate was examined two weeks after the treatment.
TABLE VII
______________________________________
Concen-
tration Fruit-bearing
Treatment
Chemical (ppm) rate (%)
______________________________________
Painting
N--(2-Chloro-4-pyridyl)-
1,000 100
N'--phenylurea
BA (liquid)* 1,000 65
" 10,000 100
None 43
Spraying
N--(2-Chloro-4-pyridyl)-
1,000 90
N'--phenylurea
" 500 87
" 100 82
BA(liquid)* 10,000 83
None 35
______________________________________
*BA(liquid) is a liquid containing 3% benzyladenine[i.e.,
6(N--benzyl)aminopurine]: same as hereafter
Seedlings of tobacco (variety, Bright Yellow) were transplanted in unglazed pots of about 13 cm. in diameter and the pots were left in a greenhouse. Solutions of the selected chemical of desired concentration were sprayed with a sprayer, 15 ml. for each pot, homogeneously on leaves and stalk at the time when 6 to 8 leaves were out. One section of the pots was sprayed once and the other section three times at 13-day intervals. Examination of the result was made when middle leaves started to become yellow (35 days after the initial spraying of the chemical), and height of the plant, fresh weight of stalk and leaves, and average area of five lower leaves were measured, and ratio of these values to those of the non-treated plants was calculated. Experimental section was three pots per area and their average was taken. Results are listed in the following Table VIII.
TABLE VIII
______________________________________
No. of
Percent to Non-treated Area
Compound Concn. spray- Fresh Leaf
tested (ppm) ings Height
Weight Area
______________________________________
N--(2-Chloro-4-
500 1 74 171 158
pyridyl)-N'--
phenylurea
3 42 169 145
5% WP* 100 1 78 188 175
3 72 206 185
20 1 102 178 172
3 98 160 152
BA(liquid) 500 1 99 151 118
3 85 138 111
100 1 98 118 141
3 90 115 124
20 1 106 109 120
3 98 113 121
None(%) 100 100 100
" (74.6 (126.6 (278
cm) g/stock)
cm.sup.2 /leaf
______________________________________
*5% WP: Wettable powder containing 5%
N--(2chloro-4-pyridyl)-N'--phenylurea
Grapevine (variety Delaware) raised in plastic house covering was used for the examination. N-(2-Chloro-4-pyridyl)-N'-phenylurea or benzyladenine (200 or 100 ppm) was dded to 100 ppm of gibberelline solution, and recemose flowers were dipped in each solution (April 14). Ten days after full bloom (May 4), all the fruit clusters were again soaked and treated with 100 ppm solution of gebberelline. The grapevines were then left to usual cultivation conditions until harvest. Grapes were harvested on June 29, and weight of each cluster, length of cluster, density of berries, number of berries on each cluster, and berry diameter were measured. These values were compared with those found with grapes with gebberelline treatment alone. Experimental area contained two new brances, three repetition, and average value of fifteen fruit clusters was calculated.
Results are shown in Table IX.
TABLE IX
__________________________________________________________________________
Effect on Inhibition of Flower Shedding of Delaware-Grape (Average of 15
Clusters)
Items
Examined No. of
Compound Weight
Length
Density
Berries
Seed-
Diameter
Weight
Hardness
added to of Berry
of One
of per less
of of of
GA (100
concn.
Cluster
Cluster
Berries
Cluster
Berries
Gynophore
Gynophore
Gynophore
ppm)Soln.
(ppm)
(g) (cm)
(No./cm)
(No.)
(%) (mm) (g) (feel)
__________________________________________________________________________
N--(2-
200 195.6
13.7
14.3 136.6
100 5.08 5.96 Hard
Chloro- (190)
(91)
(210)
(194) (213) (248)
4-pyridyl)-
N'--phenyl-
urea
100 196.3
14.5
13.5 136.3
100 5.60 5.47 slightly
(109)
(97)
(199)
(194) (192) (228) hard to hard
50 189.8
14.4
13.5 129.6
100 4.62 4.71 slightly
(184)
(94)
(199)
(184) (193) (196) hard to hard
25 180.8
15.0
13.5 129.6
100 3.82 4.71 slightly
(175)
(100)
(178)
(202) (160) (196) hard to hard
BA 200 136.8
14.8
9.2 93.3
100 3.82 2.75 Ordinary
3% Soln. (132)
(99)
(135)
(133) (139) (115)
100 125.3
15.5
8.1 73.9
100 3.02 2.46 slightly soft
(122)
(103)
(119)
(105) (126) (103) to ordinary
GA alone
(100)
103.1
15.0
6.8 70.3
100 2.39 2.40 slightly
(100)
(100)
(100)
(100) (100) (100) soft
__________________________________________________________________________
BA = 6(N--benzyl)aminopurine.
GA = Gibberellin
Values in parentheses denote percentage to the values obtained with the
use of GA alone.
Soil containing the subterranean stems of narrowleaf waterplantain (Alisma canaliculatum) and bulrush (Scirpus juncoides) homogeneously was filled in ceramic pots of 30 cm in diameter. Seeds of barnyard grass (Echinochloa crus-balli), umbrella plant (Cyperus diformis) were each sown in pots, fifty seeds to each pot. Then paddy rice seedlings (Variety Kinmaze) at the two-leaf stage was planted, five seedlings per pot, and the pots were filled with water so as to have a water layer of three cm. above the soil. When the barnyard grass reached the one-leaf stage, the desired quantity of the solution of the selected test chemical(s), prepared according to Preparation 1, was sprayed uniformly over the surface of the water. Herbicidal effect was examined fourteen days after the chemical treatment. Result of this test was expressed by the following index (Table X):
TABLE X
__________________________________________________________________________
Narrow
Effect
Control of Weeds leaf on
Amount
Barnyard
Unbrella
Mono-
Bul-
water
paddy
Compound
(kg/Ha)
grass
plant
choria
rush
plantain
rice
__________________________________________________________________________
N--(2-Chloro-
1 5 5 5 4 5 0
4-pyridyl)-
N'--phenylurea
0.5 4 4 4.5 3 4.5 0
__________________________________________________________________________
5: Complete control of weeds
4: Over 80% control of weeds
3: Over 60% control of weeds
2: Over 40% control of weeds
1: Over 20% control of weeds
0: No effect
Datura Sunguinea sp. (average height of 8 cm.) were transplanted outdoors. Solutions of the chemically desired concentration were sprayed with a sprayer, 15 ml. each plant, on the leaves and stalk of the plant at the time when the average height of the plant was 20 cm. Three weeks later, the plants were harvested and the height of the plant and the total weight of fresh leaves and stalks on the new brances were measured. Average values of five plants are listed in Table XI.
TABLE XI
______________________________________
Concn. Height Total Weight
New Branches
Compound (ppm) (cm) (g) (g)
______________________________________
N--(2-Chloro-
20 80 450 80
4-pyridyl)-
N'--phenyl-
urea
N--(2-Chloro-
100 75 500 100
4-pyridyl)-
N'--phenyl
urea
BA(liquid)
500 90 402 70
Control 103 348 40
______________________________________
Datura Sunguina sp. (average height of 8 cm.) were transplanted outdoors and test using N-(2-chloro-4-pyridyl)-N'-(3-bromophenyl)urea were conducted as in Example 11. The results shown in Table XII were obtained.
TABLE XII
______________________________________
Concn. Height Total Weight
New Branches
Compound (ppm) (cm) (g) (g)
______________________________________
N--(2-chloro-
60 81 450 78
4-pyridyl)-
N'--(3-bromo-
phenyl)urea
N--(2-chloro-
300 74 490 98
4-pyridyl)-
N'--(3-bromo-
phenyl)urea
BA(liquid)
500 91 391 68
Control 102 352 41
______________________________________
Various modifications and equivalents will be apparent to one skilled in the art and may be made in the compounds, compositions and methods of the present invention without departing from the spirit or scope thereof, and it is therefore to be understood that the invention is not to be limited to the specific examples and embodiments disclosed herein.
Claims (17)
1. A compound selected from the group consisting of N-(2-chloro-4-pyridyl)ureas of the following formula ##STR4## wherein R1 represents hydrogen or alkyl of from 1 to 3 carbon atoms, inclusive; R2 represents aryl selected from the group consisting of phenyl, which may be substituted by alkyl of from 1 to 3carbon atoms, inclusive; alkoxy; of from 1 to 3 carbon atoms, inclusive; or halogen; and X stands for oxygen or sulfur; and acid addition salts thereof.
2. An N-(2-chloro-4-pyridyl)urea as claimed in claim 1 wherein X is an oxygen atom.
3. An N-(2-chloro-4-pyridyl)urea as claimed in claim 1 wherein R1 is hydrogen.
4. A compound of claim 1 which is selected from the group consisting of N-(2-chloro-4-pyridyl)-N'-phenylurea and an acid addition salt thereof.
5. An agricultural composition useful as a plant growth regulator comprising as active ingredient a compound selected from the group consisting of an N-(2-chloro-4-pyridyl)urea of claim 1, of the formula: ##STR5## wherein R1 represents hydrogen or alkyl of from 1 to 3 carbon atoms, inclusive; R2 represents aryl selected from the group consisting of phenyl, .[.pyridyl, naphthyl, and biphenyl,.]. which may be substituted by alkyl of from 1 to 3 carbon atoms, inclusive; alkoxy of from 1 to 3 carbon atoms, inclusive; hydroxyl or halogen; and X is oxygen or sulfur; and an acid addition salt thereof, in an effective plant-growth regulating amount, together with an inert carrier or diluent.
6. The agricultural composition of claim 5 which further contains an emulsifying or dispersing agent.
7. The agricultural composition of claim 5 wherein said N-(2-chloro-4-pyridyl)urea is present in a herbicidally-effective amount.
8. A method of controlling plant growth which comprises contacting a plant or part thereof with a compound selected from the group consisting of an N-(2-chloro-4-pyridyl)urea of claim 1, of the formula: ##STR6## wherein R1 represents hydrogen or alkyl of from 1 to 3 carbon atoms, inclusive; R2 represents aryl selected from the group consisting of phenyl, .[.pyridyl, naphthyl, and biphenyl,.]. which may be substituted by alkyl of from 1 to 3 carbon atoms, inclusive; alkoxy of from 1 to 3 carbon atoms, inclusive; hydroxyl or halogen; and X is oxygen or sulfur; and acid addition salt thereof, in an amount effective for regulation of the growth of the plant involved.
9. The method of claim 8, wherein the compound is in admixture with an inert carrier or diluent.
10. The method of claim 8, wherein the compound is contacted with the plant in a herbicidally-effective amount thereof.
11. The composition according to claim 5, wherein X is oxygen and R2 is phenyl.
12. The composition according to claim 11, wherein R1 is hydrogen.
13. The method of controlling plant growth according to claim 8, wherein X is oxygen and R2 is phenyl.
14. The method of controlling plant growth according to claim 13, wherein R1 is hydrogen.
15. A compound of claim 1, wherein X is sulfur. .[.16. A compound of claim
1, wherein R2 is pyridyl..]. 17. A composition of claim 5, wherein X is sulfur. .[.18. A composition of claim 5, wherein R2 is pyridyl..].
9. A method of claim 8, wherein X is sulfur. .[.20. A method of claim 8, wherein R2 is pyridyl..].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/305,768 USRE31550E (en) | 1977-10-08 | 1981-09-25 | N-(2-Chloro-4-pyridyl) ureas |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12128577A JPS5481275A (en) | 1977-10-08 | 1977-10-08 | Nn*22chlorr44pyridyl*ureas*manufacture and vegetable growth regulating agent |
| KR1019780003042A KR830000128B1 (en) | 1977-10-08 | 1978-10-05 | Preparation of N- (2-chloro-4-pyridyl) urea |
| US06/305,768 USRE31550E (en) | 1977-10-08 | 1981-09-25 | N-(2-Chloro-4-pyridyl) ureas |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/947,468 Reissue US4193788A (en) | 1977-10-08 | 1978-10-02 | N-(2-Chloro-4-pyridyl)ureas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE31550E true USRE31550E (en) | 1984-04-10 |
Family
ID=27314219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/305,768 Expired - Lifetime USRE31550E (en) | 1977-10-08 | 1981-09-25 | N-(2-Chloro-4-pyridyl) ureas |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE31550E (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012087980A1 (en) | 2010-12-21 | 2012-06-28 | Agraquest, Inc. | Sandpaper mutants of bacillus and methods of their use to enhance plant growth, promote plant health and control diseases and pests |
| WO2013039937A1 (en) | 2011-09-12 | 2013-03-21 | Agraquest, Inc. | Methods of enhancing health and/or promoting growth of a plant and/or of improving fruit ripening |
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| Deutsche Gold et al., "Substituted Pyridylureas." (1965), CA 65, pp. 15340-15341 (1966). |
| Deutsche Gold et al., Substituted Pyridylureas. (1965), CA 65, pp. 15340 15341 (1966). * |
| Lesiak et al., "New Derivatives of Urea", (1971), CA 76, No. 113031v, (1972), Also Orig. Publication. |
| Lesiak et al., New Derivatives of Urea , (1971), CA 76, No. 113031v, (1972), Also Orig. Publication. * |
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