US3885951A - Plant growth regulant compositions containing 2-haloethanesulphinic acid compounds - Google Patents
Plant growth regulant compositions containing 2-haloethanesulphinic acid compounds Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/04—Sulfinic acids; Esters thereof
Definitions
- Hal is preferably chlorine or bromine while R is preferably chlorine, bromine, hydroxyl, straight-chain or branched alkoxy of from 1 to 16 carbon atoms, straight or branched haloalkoxy of from 1 to carbon atoms, alkenyloxy of from 3 to 18 carbon atoms, alkynyloxy of from 3 to 5 carbon atoms or cyclohexyloxy.
- R is preferably chlorine, bromine, hydroxyl, straight-chain or branched alkoxy of from 1 to 16 carbon atoms, straight or branched haloalkoxy of from 1 to carbon atoms, alkenyloxy of from 3 to 18 carbon atoms, alkynyloxy of from 3 to 5 carbon atoms or cyclohexyloxy.
- R is preferably chlorine, bromine, hydroxyl, straight-chain or branched alkoxy of from 1 to 16 carbon atoms, straight or branched haloalkoxy of from 1 to carbon atoms, alken
- the 2-haloethanesulphinic acid compounds of the formula (I) show a considerably greater plant-growth-regulating activity than 2-chloroethanephosphonic acid, which is chemically the nearest active substance with the same type of activity.
- Some of the substances to be used according to this invention additionally have microbicidal and fungicidal activity.
- the compounds according to the invention hence represent a valuable enrichment of the art.
- the present invention provides a plant-growthregulating composition containing as active ingredient a compound of the formula (1) in admixture with a carrier, e.g., a solid or liquefied gaseous diluent or carrier or a liquid diluent or carrier containing a surface-active agent.
- a carrier e.g., a solid or liquefied gaseous diluent or carrier or a liquid diluent or carrier containing a surface-active agent.
- 2-chloroethanesulphinic acid chloride 2-chloroethanesulphinic acid bromide, 2-chloroethanesulphinic acid, -2chloroethanesulphinic acid methyl ester, 2-chloroethanesulphinic acid ethyl ester, 2-chloroethanesulphinic acid npropyl ester, 2-chloroethanesulphinic acid isopropyl ester, 2-chloroethanesulphinic acid n-butyl ester, 2-chloroethanesulphinic acid sec.-butyl ester, 2-chloroethanesulphinic acid tert.- butyl ester, 2-chloroethanesulphinic acid isobutyl ester, 2-chloroethanesulphinic"acid n-pen'tyl ester, 2-chloroethanesulphinic acid chloride, 2-chloroethanes
- 2-chloroethanesulphinic acid 2'-methylpropenyl ester 2-chloroethanesulphinic acid penten-l '-yl ester, 2-chloroethanesulphinic acid l',l '-dimethylallyl ester, 2-chloroethanesulphinic acid octadecen-9-yl ester, 2-chloroethanesulphinic acid propargyl ester, Z-chloroethanesulphinic acid l-methyl-propargyl ester, 2-chloroethanesulphinic acid 1',l '-dimethylpropargyl ester, 2-chloroethanesulphinic acid cyclohexyl ester and the corresponding 2-bromoethanesulphinic acid derivatives.
- a number of the substances that can be used according to this invention are known, for example 2-chloroethanesulphinic acid chloride, 2-chloroethanesulphinic acid (see Doklady Akad. SSR 157 (1964), No. 1, pages 139-142); 2-chloroethanesulphinic acid methyl ester and 2-bromoethanesulphinic acid methyl ester (see Chem. Ber.
- the compounds of the formula (I) are new but can be prepared, as can the known analogues, in a simple manner using processes that are known in principle.
- the sulphinic acid halides are obtained if the corresponding bis-(2-haloethane)- disulphides are halogenated, for example with chlorine in a molar ratio of 1:3, in the presence of inert solvents, such as methylene chloride, at temperatures between -60 C and 10 C, and the products are then reacted with alcohols.
- the reaction products are isolated by stripping off the solvent in vacuo and distilling the residue.
- the corresponding sulphinic acid halides are reacted with hydrolyzing agents or with the corresponding alcohols at temperatures between l C and +40 C in the presence of inert solvents, such as methylene chloride.
- E-chloroethanesulphinic acid chloride was prepared analogously.
- the active compounds that can be used according to this invention interefere with the physiological phenomena of plant growth and can therefore be used as plant-growth regulators.
- the different effects of the active compounds depend essentially on the point in time of the application, with reference to the development stage of the seed or the plant, as well as on the concentrations applied.
- Plant-growth regulators are used for various purposes that are connected with the development stage of the plant.
- the seed dormancy can be broken in order to cause the seeds to germinate at a certain time at which germination is desired, but at which the seed itself shows no readiness to germinate.
- the seed germination itself can, depending dogenic annual cycle, can be influenced by the active compounds, so that the plants for instance shoot or The shoot or root growth can be promoted or inhibited by the active compounds in manner dependent on the applied concentration.
- the branching to the side can be multiplied by a chemical breaking of the apical dominance. This is of interest, for example in the propagation of plants by cuttings. In a concentrationdependent manner, however, it is also possible to inhibit the growth of side-shoots, for example in order to prevent the formation of side-shoots in tobacco plants after decapitation and thus to promote the leaf growth.
- the influence of the active compounds on the foliage of the plants can be so regulated that a defoliation is achieved, for example in order to facilitate the harvest or to reduce transpiration at a time at which the plants are to be transplanted.
- Fruit initiation can be promoted so that more, or seedless, fruits are formed (parthenocarpy). Under certain conditions, the premature fall of fruit can also be prevented, or the fruit fall can be promoted to a certain extent in the sense of a chemical thinning out. The promotion of the fruit fall can, however, also be so exploited that the treatment is effected at the time of the harvest, whereby a facilitation of harvesting occurs. With growth regulators it is also possible to accelerate or retard fruit ripening, to improve the fruit coloration and to cause fruits to come to ripeness within a short period of one another.
- Yield increases with the aid of growth regulators can be attained by promotion of fruit initiation, by formation of larger fruits and by promotion of the vegetative growth. Further, a stimulation of the synthesis or of the outflow of secondary vegetable substances (for example latex flow of rubber trees) is possible.
- the active compounds to be used according to the present invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents.
- extenders that is, liquid or solid or liquefied gaseous diluents or carriers
- surface-active agents that is, emulsifying agents and/or dispersing agents.
- organic solvents can, for example, also be used as auxiliary solvents.
- liquid diluents or carriers there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile, as well as water.
- aromatic hydrocarbons such as xylenes, toluene, benzene or alkyl naphthalenes
- liquefied gaseous diluents or carriers liquids which would be gaseous at normal temperatures and pressures, e.g. aerosol propellants, such as halogenated hydrocarbons, e.g. freon.
- ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.
- emulsifying agents include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates, and preferred examples of dispersing agents include lignin, sulphite waste liquors and methyl cellulose.
- non-ionic and anionic emulsifiers such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates
- dispersing agents include lignin, sulphite waste liquors and methyl cellulose.
- the formulations contain, in general, from 0.1 to 95, preferably from 0.5 to 90% by weight of active compound.
- the active compounds may be applied as such or in the form of their formulations or of the application forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, spray powders, pastes, soluble powders, dusting Solvent:
- agents and granulates may take place in any usual manner, for example by watering, squirting, spraying, scattering and dusting.
- concentrations of active compound can be varied within a fairly wide range. In general, concentrations of from 0.0005 to 2%, preferably from 0.01 to 0.5%, by weight are used.
- the present invention also provides a method of regulating the growth of plants which comprises applying to the plants or a plant habitat a compound of the formula (I), alone or in the form of a composition containing as active ingredient a compound of the formula (I) in admixture with a diluent or carrier.
- Emulsifier Emulsifier:
- Young bean plants about 10 cm in height were sprayed with the preparations of active compound until dripping wet. After 14 days the growth increase was measured and the growth inhibition was calculated as a percentage of the growth increase of the control plants. means complete inhibition of growth, and 0% means no inhibition of growth.
- part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and water was added until the desired concentration was reached.
- Hal in the formula is chlorine or bromine and R is chloring, bromine, hydroxyl, alkoxy or haloalkoxy of from 1 to 8 carbon atoms, or cyclohexyloxy.
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Abstract
Compositions containing, as an active ingredient, at least one 2-haloethanesulphinic acid compound of the following formula, show exceptionally strong plant growth regulant properties:
IN WHICH Hal is halogen, and R is halogen, hydroxyl, alkoxy of from 1 to 20 carbon atoms, haloalkoxy of from 1 to 8 carbon atoms, alkenyloxy of from 2 to 20 carbon atoms, alkynyloxy of from 2 to 8 carbon atoms or cycloalkoxy of up to 12 carbon atoms.
IN WHICH Hal is halogen, and R is halogen, hydroxyl, alkoxy of from 1 to 20 carbon atoms, haloalkoxy of from 1 to 8 carbon atoms, alkenyloxy of from 2 to 20 carbon atoms, alkynyloxy of from 2 to 8 carbon atoms or cycloalkoxy of up to 12 carbon atoms.
Description
United States Patent [191 Hofer et a1.
[451 May 27, 1975 PLANT GROWTH REGULANT COMPOSITIONS CONTAINING Z-HALOETHANESULPHINIC ACID COMPOUNDS [75] Inventors: Wolfgang l-lofer,
Wuppertal-Vohwinkel; Klaus Lurssen, Konigsdorf; Robert Rudolf Schmidt, Leverkusen, all of Germany [73] Assignee: Bayer Aktiengesellschaft,
Leverkusen, Germany [22] Filed: Feb. 29, 1972 [21] Appl. No.: 230,505
[30] Foreign Application Priority Data UNITED STATES PATENTS 2,654,667 10/1953 Goodbye et a1. 71/72 2,999,105 9/1961 Louthan 260/453 3,463,803 8/ l969 Aichenegg 260/453 OTHER PUBLICATIONS Sato et al., Chem. Abst. Vol. 73 (1970), 120488u. Etlis et al., Chem. Abst. Vol. 63 (1965), 479e.
Cooke et al., Nature, Vol. 218, June 8, 1968, pg. 974-975.
Primary Examiner--Lewis Gotts Assistant Examiner-Catherine L. Mills Attorney, Agent, or FirmBurgess, Dinklage & Sprung [5 7 ABSTRACT Compositions containing, as an active ingredient, at least one 2-haloethanesulphinic acid compound of the following formula, show exceptionally strong plant growth regulant properties:
HaI-CH -CH -S-R in which Hal is halogen, and R is halogen, hydroxyl, alkoxy of from 1 to 20 carbon atoms, haloalkoxy of from 1 to 8 carbon atoms, alkenyloxy of from 2 to 20 carbon atoms, alkynyloxy of from 2 to 8 carbon atoms or cycloalkoxy of up to 12 carbon atoms.
9 Claims, No Drawings 1 PLANT GROWTH REGULANT COMPOSITIONS CONTAINING Z-HALOETHANESULPHINIC ACID COMPOUNDS in which l-lal is halogen, and R is halogen, hydroxyl, alkoxy of from 1 to 20 carbon atoms, haloalkoxy of from 1 to 8 carbon atoms, alkenyloxy of from 2 to 20 carbon atoms, alkynyloxy of from 2 to 8 carbon atoms or cycloalkoxy of up to 12 carbon atoms. I
In the above formula (1), Hal is preferably chlorine or bromine while R is preferably chlorine, bromine, hydroxyl, straight-chain or branched alkoxy of from 1 to 16 carbon atoms, straight or branched haloalkoxy of from 1 to carbon atoms, alkenyloxy of from 3 to 18 carbon atoms, alkynyloxy of from 3 to 5 carbon atoms or cyclohexyloxy. Such compounds are preferred because of their particularly high activity.
Surprisingly, the 2-haloethanesulphinic acid compounds of the formula (I) show a considerably greater plant-growth-regulating activity than 2-chloroethanephosphonic acid, which is chemically the nearest active substance with the same type of activity. Some of the substances to be used according to this invention additionally have microbicidal and fungicidal activity. The compounds according to the invention hence represent a valuable enrichment of the art.
The present invention provides a plant-growthregulating composition containing as active ingredient a compound of the formula (1) in admixture with a carrier, e.g., a solid or liquefied gaseous diluent or carrier or a liquid diluent or carrier containing a surface-active agent.
As individual examples of the active substances that can be used according to the present invention, there may be mentioned: 2-chloroethanesulphinic acid chloride, 2-chloroethanesulphinic acid bromide, 2-chloroethanesulphinic acid, -2chloroethanesulphinic acid methyl ester, 2-chloroethanesulphinic acid ethyl ester, 2-chloroethanesulphinic acid npropyl ester, 2-chloroethanesulphinic acid isopropyl ester, 2-chloroethanesulphinic acid n-butyl ester, 2-chloroethanesulphinic acid sec.-butyl ester, 2-chloroethanesulphinic acid tert.- butyl ester, 2-chloroethanesulphinic acid isobutyl ester, 2-chloroethanesulphinic"acid n-pen'tyl ester, 2-chloroethanesulphinic acid isopentyl ester, 2-chloroethanesulphinic acid neo-pentyl ester, 2-chloroethanesulphinic acid n-hexyl ester, 2chloroethanesulphinic acid 2- methylpentyl ester, 2-chloroethanesulphinic acid 3'- methylpentyl ester, 2-chloroethanesulphinic acid 2',2'- dimethylbutyl ester, 2-chloroethanesulphinic acid 3'- ethylbutyl ester, 2-chloroethanesulphinic acid 2- ethylbutyl ester, 2-chloroethanesulphinic acid n-heptyl ester, 2-chloroethanesulphinic acid 2'-methylhexyl ester, 2-chloroethanesulphinic acid 3-methylhexyl ester, 2-chloroethanesulphinic acid 2',2-dimethylpentyl ester, 2-chloroethanesulphinic acid 3',3'-dimethylpentyl ester, 2-chloroethanesulphinic acid 2 ',3 dimethylpentyl ester, 2-chloroethane sulphinic acid 2',4'-dimethylpentyl ester, 2-chloroethanesulphinic acid 3-ethylpentyl ester, 2-chloroethanesulphinic acid 2-ethylhexyl ester, 2-chloroethanesulphinic acid 2',3',3-trimethylbutyl ester, 2-chloroethanesulphinic acid n-octyl ester, 2-chloroethanesulphinic acid isooctyl ester, 2-chloroethanesulphinic acid 2',2'- dimethylhexyl ester, 2-chloroethanesulphinic acid nnonyl ester, 2-chloroethanesulphinic acid n-decyl ester, 2-chloroethanesulphinic acid n-undecyl ester, 2-chloroethanesulphinic acid n-dodecyl ester, 2-chloroethanesulphinic acid 2',2'-dimethyloctyl ester, 2-chloroethanesulphinic acid 2,2'-dimethyldecyl ester, 2 -chloroethanesulphinic acid tetradecyl ester,
2-chloroethanesulphinic acid hexadecyl ester, 2-chloroethanesulphinic acid chloromethyl ester, 2-chloroethanesulphinic acid chloroethyl ester, 2-chloroethanesulphinic acid chloropropyl ester,
2-chloroethanesulphinic acid l',3'-dichloroprop-2-yl ester, 2-chloroethanesulphinic acid vinyl ester, 2-chloroethanesulphinic acid propenyl ester, 2-chloroethanesulphinic acid buten-l '-yl ester, 2-chloroethanesulphinic acid buten-2 '-yl ester,
2-chloroethanesulphinic acid 2'-methylpropenyl ester, 2-chloroethanesulphinic acid penten-l '-yl ester, 2-chloroethanesulphinic acid l',l '-dimethylallyl ester, 2-chloroethanesulphinic acid octadecen-9-yl ester, 2-chloroethanesulphinic acid propargyl ester, Z-chloroethanesulphinic acid l-methyl-propargyl ester, 2-chloroethanesulphinic acid 1',l '-dimethylpropargyl ester, 2-chloroethanesulphinic acid cyclohexyl ester and the corresponding 2-bromoethanesulphinic acid derivatives.
A number of the substances that can be used according to this invention are known, for example 2-chloroethanesulphinic acid chloride, 2-chloroethanesulphinic acid (see Doklady Akad. SSR 157 (1964), No. 1, pages 139-142); 2-chloroethanesulphinic acid methyl ester and 2-bromoethanesulphinic acid methyl ester (see Chem. Ber. 86, 557 (1953) and German Published Specification No.2,005,514); 2-chloroethanesulphinic acid methyl ester and ethyl ester, 2-bromoethanesulphinic acid methyl ester and ethyl ester and 2-chloroethanesulphinic acid isopropyl ester (see Tetrahedron Letters 32, 2743 2746 (1969)); and 2-chloroethanesulphinic acid tert.-butyl ester (see Zh. obsch. Khim. 35, (3), 475 479 (1965)).
Some of the compounds of the formula (I) are new but can be prepared, as can the known analogues, in a simple manner using processes that are known in principle. For example, the sulphinic acid halides are obtained if the corresponding bis-(2-haloethane)- disulphides are halogenated, for example with chlorine in a molar ratio of 1:3, in the presence of inert solvents, such as methylene chloride, at temperatures between -60 C and 10 C, and the products are then reacted with alcohols. The reaction products are isolated by stripping off the solvent in vacuo and distilling the residue. In order to prepare the sulphinic acids or their esters, the corresponding sulphinic acid halides are reacted with hydrolyzing agents or with the corresponding alcohols at temperatures between l C and +40 C in the presence of inert solvents, such as methylene chloride.
EXAMPLE 1 Preparation of Z-bromoethanesulphinic acid chloride 1 Br-CH -CH S-C1 (Compound 1) 213 g (3 moles) of chlorine were introduced, at -60 C, into a solution of 280 g (1 mole) of bis-(2-bromoethane)-disulphide in 800 ml of methylene chloride, and thereafter 64 g (2 moles) of methanol in 100 ml of methylene chloride were added at this temperature, with stirring. The reaction solution was allowed to come to room temperature whilst stirring was effected, in the course of which hydrogen chloride and methyl chloride were evolved. Thereafter, the solvent was stripped off in vacuo and the residue was distilled at 98 C and l 1 mm Hg 210 g (60% of theory) of 2-bromoethanesulphinic acid chloride were obtained as a brownlsh liquid of refractive index m, 1.5578.
E-chloroethanesulphinic acid chloride was prepared analogously.
1| C1-CH -CH -S-C1 (Compound 2) 240 g (82% of theory) were obtained as a colorless liquid: boiling point 72 C at 6 mm Hg; refractive index n 1.5200.
EXAMPLE 2 Preparation of 2-chloroethanesulphinic acid ethyl ester 29.4 g (0.2 mole) of 2-chloroethanesulphinic acid chloride were added dropwise at 0 C to 9.5 g (0.205 mole) of ethanol in 50 ml of methylene chloride. After the mixture had been stirred for a further 2 hours at 20 to C, the solvent was stripped off in vacuo and the residue was distilled at 30 C and 0.1 mm Hg. 20 g (64% of theory) of 2-chloroethanesulphinic acid ethyl ester were obtained as a colorless liquid of refractive index n 1.4759.
The following compounds were prepared in an analogous manner (in the boiling-point data below, the pressure, in mm Hg, is set forth first):
Com- Physical Properties Yield pound (boiling point and of No. Compound Name Structure refractive index) theory) 0 bp. 0.2/C 4 Q-chloroethanesulphinic acid isopropyl ester ClCH CH %-OCH)CH n 1.4720
I 15 Z-chloroethanesulphinic acid n-butyl ester ClCH -CH S-OC H n bp. 0.1 /63-65C I! 15 B-chloroethanesulphinic acid methyl ester Cl-CH CH SOCH bp. 6I64C I! .Z-chloroethanesulphinic acid cyclohexyl ester C1CH -CH -SO- bp.0.25/94C l1 l3 Z-chloroethanesulphinic acid n-pentyl ester ClCH CH -S-OC =,H n bp.0.05/90C II Z-chloroethanesulphinic acid n-octyl ester ClCH CH SOC H n bp. 0.1/102C I! 10 Il-bromoethanesulphinic acid n-pentyl ester Br-CH CH SOC l-l n bp. 0.01/C
II 1 1 Z-bromoethanesulphinic acid cyclohexyl ester BrCH CH -SO bp. 0.1/104-106C I 12 Z-bromoethanesulphinic acid isopropyl ester Br-CH CH S-OCH(CH bp.0.01/52C I! 13 2-bromoethanesu1phinic acid n-butyl ester BrCH -CH -SOC H -n bp.O.4/74 C 5 6 i Continued Com-d Physical Properties Yield poun (boiling point and of No. Compound Name Structure refractive index) theory) l4 2-bromoethanesulphinic acid ethyl ester BrCH CH,SOC,H bp. 0.3/55C 2-chloroethanesulphinic acid 2-chloro-ethyl ester CICH CH SOCH CH- n 1.4989 92 16 2-chloroethanesulphinic acid l',3'-dichl0ro-pr0p- C1CH CH S-O n,, 1.4958 89 CH(CH C1) 2-yl ester II 17 2-chloroethanesulphinic acid hexadecyl ester ClC1-1 CH SO(CH C1-1 n 1.4698 59 O ll 18 2-chloroethanesulphinic acid l-propynyl ester ClCH CH S-OCH- n,, 1.4990 85 19 2-chloroethanesulphinic acid octylethylideneoctyl ClCl-l C1-1 SO(CH CH=CH(CH CH;,
ester n,, 1.4724 92 I! 20 2-chloroethanesulphinic acid allyl ester ClCH CH SOC1-1- n 1.4920 80 Cl-1 H EXAMPLE 3 blossom at a point in time at which they normally show Preparation of 2-chloroethanesulphinic acid starting no readiness to or blossom It can also be achieved that the shooting of the buds material is retarded, for example in order to avoid, in frostthreatened areas, damage by frosts.
C1-CH -CH -S-OH (Compound 21) 74 g (0.5 mole) of 2-chloroethanesulphinic acid chloride were added dropwise to 200 ml of water, whilst stirring and cooling with ice were effected. After stirring for a further half-hour, the water was stripped off in vacuo, the residue was taken up in methylene chloride, the solution was dried over sodium sulphite and the solvent was stripped off in vacuo. A colorless oil of refractive index m, 1.5040 was left; yield: 60 g (94% of theory).
The active compounds that can be used according to this invention interefere with the physiological phenomena of plant growth and can therefore be used as plant-growth regulators.
The different effects of the active compounds depend essentially on the point in time of the application, with reference to the development stage of the seed or the plant, as well as on the concentrations applied.
Plant-growth regulators are used for various purposes that are connected with the development stage of the plant.
Thus, with plant-growth regulators the seed dormancy can be broken in order to cause the seeds to germinate at a certain time at which germination is desired, but at which the seed itself shows no readiness to germinate. The seed germination itself can, depending dogenic annual cycle, can be influenced by the active compounds, so that the plants for instance shoot or The shoot or root growth can be promoted or inhibited by the active compounds in manner dependent on the applied concentration. Thus, it is possible, for ex-' ample, to inhibit very strongly the growth of the fully formed plant, or to bring the plant as a whole to a more robust habitus or to produce a dwarf growth.
Of economic interest is the inhibition of plant growth at roadsides and waysides. Furthermore, the frequency of grass-cutting (of lawn-mowing) on swards can be reduced. The growth of woodlands can also be inhibited.-
During the growth of the plant, the branching to the side can be multiplied by a chemical breaking of the apical dominance. This is of interest, for example in the propagation of plants by cuttings. In a concentrationdependent manner, however, it is also possible to inhibit the growth of side-shoots, for example in order to prevent the formation of side-shoots in tobacco plants after decapitation and thus to promote the leaf growth.
The influence of the active compounds on the foliage of the plants can be so regulated that a defoliation is achieved, for example in order to facilitate the harvest or to reduce transpiration at a time at which the plants are to be transplanted.
With growth regulators it is also possible to reduce the transpiration rate of the plants in order to prevent damage by drying out.
In the cases of the influencing of blossom formation,
there can be achieved, depending on the applied concentration and the point in time of the application, either a retarding of blossom formation or an acceleration of blossom formation. Under certain circumstances, a multiplication of blossom initiation can also be attained, these effects occurring when the appropriate treatments are carried out at the time of the normal blossom formation. In addition, the formation of predominantly female or predominantly male blossoms can be achieved.
Fruit initiation can be promoted so that more, or seedless, fruits are formed (parthenocarpy). Under certain conditions, the premature fall of fruit can also be prevented, or the fruit fall can be promoted to a certain extent in the sense of a chemical thinning out. The promotion of the fruit fall can, however, also be so exploited that the treatment is effected at the time of the harvest, whereby a facilitation of harvesting occurs. With growth regulators it is also possible to accelerate or retard fruit ripening, to improve the fruit coloration and to cause fruits to come to ripeness within a short period of one another.
Yield increases with the aid of growth regulators can be attained by promotion of fruit initiation, by formation of larger fruits and by promotion of the vegetative growth. Further, a stimulation of the synthesis or of the outflow of secondary vegetable substances (for example latex flow of rubber trees) is possible.
The active compounds to be used according to the present invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and pressures, e.g. aerosol propellants, such as halogenated hydrocarbons, e.g. freon.
As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.
Preferred examples of emulsifying agents include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates, and preferred examples of dispersing agents include lignin, sulphite waste liquors and methyl cellulose.
The formulations contain, in general, from 0.1 to 95, preferably from 0.5 to 90% by weight of active compound.
The active compounds may be applied as such or in the form of their formulations or of the application forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, spray powders, pastes, soluble powders, dusting Solvent:
agents and granulates. Application may take place in any usual manner, for example by watering, squirting, spraying, scattering and dusting.
The concentrations of active compound can be varied within a fairly wide range. In general, concentrations of from 0.0005 to 2%, preferably from 0.01 to 0.5%, by weight are used.
Further, there are used, in general, 0.1 to kg, preferably 1 to 10 kg, of active compound per hectare of soil area.
Generally, application of the plant-growth regulators is effected within a preferred period of time, the precise delimitation of which is governed by the climatic and vegetative circumstances.
The present invention also provides a method of regulating the growth of plants which comprises applying to the plants or a plant habitat a compound of the formula (I), alone or in the form of a composition containing as active ingredient a compound of the formula (I) in admixture with a diluent or carrier.
The activity of the compounds used according to this invention is illustrated in the following examples.
EXAMPLE A ACCELERATION OF RIPENING IN BANANAS.
Solvent: Emulsifier:
To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and water was added until the desired concentration was reached.
In each case 3 unripe bananas were sprayed with 20 ml of the preparation of active compound. The acceleration of ripening in days was determined by comparison with the control fruits.
There is stated in days the time by which the treated fruits ripened before the untreated control fruits.
The active compounds, the concentration of the active compounds and the results can be seen from the following Table 1:
TABLE 1 Acceleration of ripening in bananas Active compound Accelerationn of ripening in days compared with the control 1000 ppm 2000 ppm (known) Compound 4 l l l 1 Compound 5 l l l 1 EXAMPLE B GERMINATION OF GROUND-NUT SEEDS l0 pans by weight methanol 2 parts by weight polyethylene sorbitan monolaurate To produce a suitable preparation of active compound, l part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and water was added until the'desired concentration was reached.
In each 'case' 20 ground-nut seeds were laid out on fil- The active compounds, the concentrations of the active compounds, and the results can be seen from the following Table 2:
TABLE 2 Germination of ground-nut seeds Active compound Concentration Number of germinated seeds Water (control) 5 ClCH CH POH 100 ppm 12 OH (known) Compound 3 100 ppm 17 Compound 4 100 ppm 16 Compound 5 100 ppm 14 Compound 21 100 ppm 15 Compound 8 100 ppm 13 EXAMPLE C RETARDMENT OF SENESCENCE IN BARLEY Solvent: Emulsifier:
10 parts by weight methanol 2 parts by weight polyethylene sorbitan monolaurate pound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and 4 water was added until the desired concentration was reached.
1 cm in length. 4 such leaf pieces were eachplaced on filter paper in a Petri dish with 4 ml of the solution of active compound. Growth regulators retarded the yellowing of the leaf pieces compared with the water control. After 4 days, this retardment of senescence was evaluated on the following scale:
To produce a suitable preparation of active com- Primary leaves of barley plants were cut into pieces Symbols:
no retardment of senescence slight retardment of senescence strong retardment of senescence very strong retardment of senescence The active compounds, the concentrations of the ac- 10 TABLE 3-Continued Retardment of senescence in barley Active compound Concentration Retardment of in ppm senescence (known) Compound 4 1000 H- 200 Compound 5 1000 -H 200 Compound 6 1000 -H- Compound 7 1000 4+ Compound l* 1000 +ll- Compound 10 1000 +H- 200 4-H- Compound 11 1000 +H- Compound 14 I000 l-H Compound 9 1000 4-H- dissolved in acetone instead of in methanol Example D Growth inhibition in beans Solvent: 10 parts by weight methanol Emulsifier: 2 parts by weight polyethylene sorbitan monolaurate To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and water was added until the desired concentration was reached.
Young bean plants about 10 cm in height were sprayed with the preparations of active compound until dripping wet. After 14 days the growth increase was measured and the growth inhibition was calculated as a percentage of the growth increase of the control plants. means complete inhibition of growth, and 0% means no inhibition of growth.
The active compounds, the concentrations of the active compounds and the results can be seen from the following Table 4:
TABLE 4 Growth inhibition in beans Inhibition com- Concentration pared with the Active Compound in ppm control in Cl-CH Cl-l P-OH 500 40 OH (known) Compound 3 500 41 Compound 4 500 45 Compound 5 S00 45 Example E Growth inhibition in cress seedlings Solvent: 10 parts by weight methanol Emulsifier: 2 parts by weight polyethylene sorbitan monolaurate To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and water was added until the desired concentration was reached. 5
5O cress seeds were laid out on a filter paper on to which the preparation of active compound had been dripped. Since the Cress seeds remained adhering to the moist filter paper, the latter was placed vertically in a glass beaker of 250 ml capacity. The glass beaker was charged with 20 ml of the preparation of active compound and covered with a glass plate.
After four days, the seedlings were measured and the percentage inhibition of growth in length compared with the control (distilled water with the corresponding 15 amounts of solvent and emulsifier) was calculated. l% means complete inhibition of growth, and 0% means no inhibition of growth.
The active compounds, the concentrations of active compound and the results can be seen from the following Table "dissolved in acetone instead of in methanol Example F Growth inhibition in tomatoes Solvent: Emulsifier:
parts by weight acetone 2 parts by weight polyethylene sorbitan monolaurate To produce a suitable preparation of active compound, part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and water was added until the desired concentration was reached.
Young tomato plants cm in height were sprayed with the preparation of active compound until dripping wet. After 14 days, the growth increase was measured and the growth inhibition was calculated as a percentage of the growth increase of the control plants. 100% means complete inhibition of growth, and 0% means no inhibition of growth.
The active compounds, the concentrations of the active compounds and the results can be seen from the following Table 6:
TABLE 6 Growth inhibition in tomatoes TABLE 6-Continued Growth inhibition in tomatoes Concentration Inhibition Active Compound in ppm in (known) Compound 2 2000 1000 90 in which Hal is halogen, and R is halogen, hydroxyl, alkoxy or haloalkoxy of from 1 to 8 carbon atoms, or cycloalkoxy of up to 12 carbon atoms.
2. Method as claimed in claim 1 wherein Hal in the formula is chlorine or bromine and R is chloring, bromine, hydroxyl, alkoxy or haloalkoxy of from 1 to 8 carbon atoms, or cyclohexyloxy.
3. Method as claimed in claim 1 wherein said compound is selected from the group consisting of 2-bromoethanesulphinic acid chloride,
2-chloroethanesulphinic acid chloride,
Z-chloroethanesulphinic acid ethyl ester,
2-chloroethanesulphinic acid isopropyl ester,
2-chloroethanesulphinic acid n-butyl ester,
Z-chloroethanesulphinic acid methyl ester,
2-chloroethanesulphinic acid cyclohexyl ester,
2-chloroethanesulphinic acid n-pentyl ester, 2-chloroethanesulphinic acid n-octyl ester, 2-bromoethanesulphinic acid n-pentyl ester, 2-bromoethanesulphinic acid cyclohexyl ester, 2-bromoethanesulphinic acid isopropyl ester, 2-bromoethanesulphinic acid n-butyl ester,
Z-bromoethanesulphinic acid ethyl ester,
2-chloroethanesulphinic acid 2'-chloro-ethyl ester,
2-chloroethanesulphinic acid l',3-dichloro-prop- Z-yl ester,
2-chloroethanesulphinic acid hexadecyl ester,
2-chl'oroethanesulphinic acid l-propynyl ester,
2-chloroethanesulphinic acid octylethylideneoctyl ester,
2-chloroethanesulphinic acid allyl ester,
and 2-chloroethanesulfinic acid.
4. Method as claimed in claim 1 wherein said compound is applied at a dosage of from 0.1 to kilograms per hectare of said area.
5. Method as claimed in claim 4 wherein said dosage is 1 to 10 kilograms of compound per hectare of said area.
13 14 6. Method as claimed in claim 1 wherein two or more 8. Method as claimed in claim 1 wherein said comof said compounds are PP slmultaneouslypound is applied to totally eradicate the plants.
7. Method as claimed in claim 1 wherein said compound is applied to a crop field infested with weeds at a dosage sufficient to injure the weeds without substan- Pound 15 PP to Stlmulate the growth of the P tial damage to the crops.
9. Method as claimed in claim 1 wherein said com- Notice of Adverse Decision in Interference In Interference No. 99,221, involving Patent No. 3,885,951, WV. I-Iofer, K. Lurssen and R. B. Schmidt, PLANT GROWTH REGULANT COMPO- SITIONS CONTAINING Q-HALOETHANESULPHINIG ACID COM- POUNDS, final judgment adverse to the patentees was rendered Oct. 4, 1977, as to claims 1 and 9.
[Ofiicial Gazette F ebruowy 14, 1.978.]
Claims (9)
1. METHOD OF INFLUENCING THE GROWTH OF PLANTS WHICH COMPRISES APPLYING PLANT GROWTH REGULATINGLY EFFECTIVE AMOUNTS OF A 2-HALOETHANESULPHINIC ACID COMPOUND OF THE FORMULA
2. Method as claimed in claim 1 wherein Hal in the formula is chlorine or bromine and R is chloring, bromine, hydroxyl, alkoxy or haloalkoxy of from 1 to 8 carbon atoms, or cyclohexyloxy.
3. Method as claimed in claim 1 wherein said compound is selected from the group consisting of 2-bromoethanesulphinic acid chloride, 2-chloroethanesulphinic acid chloride, 2-chloroethanesulphinic acid ethyl ester, 2-chloroethanesulphinic acid isopropyl ester, 2-chloroethanesulphinic acid n-butyl ester, 2-chloroethanesulphinic acid methyl ester, 2-chloroethanesulphinic acid cyclohexyl ester, 2-chloroethanesulphinic acid n-pentyl ester, 2-chloroethanesulphinic acid n-octyl ester, 2-bromoethanesulphinic acid n-pentyl ester, 2-bromoethanesulphinic acid cyclohexyl ester, 2-bromoethanesulphinic acid isopropyl ester, 2-bromoethanesulphinic acid n-butyl ester, 2-bromoethanesulphinic acid ethyl ester, 2-chloroethanesulphinic acid 2''-chloro-ethyl ester, 2-chloroethanesulphinic acid 1'',3''-dichloro-prop-2-yl ester, 2-chloroethanesulphinic acid hexadecyl ester, 2-chloroethanesulphinic acid 1-propynyl ester, 2-chloroethanesulphinic acid octylethylideneoctyl ester, 2-chloroethanesulphinic acid allyl ester, and 2-chloroethanesulfinic acid.
4. Method as claimed in claim 1 wherein said compound is applied at a dosage of from 0.1 to 100 kilograms per hectare of said area.
5. Method as claimed in claim 4 wherein said dosage is 1 to 10 kilograms of compound per hectare of said area.
6. Method as claimed in claim 1 wherein two or more of said compounds are applied simultaneously.
7. Method as claimed in claim 1 wherein said compound is applied to a crop field infested with weeds at a dosage sufficient to injure the weeds without substantial damage to the crops.
8. Method as claimed in claim 1 wherein said compound is applied to totally eradicate the plants.
9. Method as claimed in claim 1 wherein said compound is applied to stimulate the growth of the plant.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712110773 DE2110773C3 (en) | 1971-03-06 | Use of 2-haloethanesulfinic acids and their derivatives to regulate plant growth |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3885951A true US3885951A (en) | 1975-05-27 |
Family
ID=5800736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US230505A Expired - Lifetime US3885951A (en) | 1971-03-06 | 1972-02-29 | Plant growth regulant compositions containing 2-haloethanesulphinic acid compounds |
Country Status (24)
| Country | Link |
|---|---|
| US (1) | US3885951A (en) |
| JP (1) | JPS5618562B1 (en) |
| AT (1) | AT314271B (en) |
| BE (1) | BE780256A (en) |
| BR (1) | BR7201239D0 (en) |
| CA (1) | CA987127A (en) |
| CH (1) | CH568003A5 (en) |
| CS (1) | CS176188B2 (en) |
| DD (1) | DD96626A5 (en) |
| EG (1) | EG10407A (en) |
| ES (1) | ES400452A1 (en) |
| FR (1) | FR2128660B1 (en) |
| GB (1) | GB1320667A (en) |
| HU (1) | HU164190B (en) |
| IL (1) | IL38891A (en) |
| IT (1) | IT953442B (en) |
| KE (1) | KE2617A (en) |
| MY (1) | MY7500057A (en) |
| NL (1) | NL169401C (en) |
| PL (1) | PL83269B1 (en) |
| RO (1) | RO70848A (en) |
| SU (1) | SU512691A3 (en) |
| TR (1) | TR16683A (en) |
| ZA (1) | ZA721461B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3927062A (en) * | 1972-05-15 | 1975-12-16 | Shell Oil Co | Plant growth regulators |
| US4149873A (en) * | 1977-01-12 | 1979-04-17 | Ciba-Geigy Corporation | Composition for the regulation of plant metabolism |
| US4227918A (en) * | 1976-12-17 | 1980-10-14 | Bayer Aktiengesellschaft | Novel halogenoethyl sulphones and their use as plant growth regulators |
| US4357159A (en) * | 1977-01-12 | 1982-11-02 | Ciba-Geigy Corporation | Haloethylthienylsulphonates for the regulation of plant metabolism |
| US4359334A (en) * | 1980-04-28 | 1982-11-16 | Gaf Corporation | Composition for plant growth regulation |
| US4427439A (en) | 1980-04-28 | 1984-01-24 | Gaf Corporation | Composition for plant growth regulation |
| WO1987005781A2 (en) | 1986-03-31 | 1987-10-08 | Rhone-Poulenc Nederlands B.V. | Synergistic plant growth regulator compositions |
| US5123951A (en) * | 1986-03-31 | 1992-06-23 | Rhone-Poulenc Nederland B.V. | Synergistic plant growth regulator compositions |
| US6274632B1 (en) * | 1997-03-12 | 2001-08-14 | Zeneca Limited | Derivatives of 4,4-difluorobut-3-enylsulfinic acid and their use as pesticides |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2442833A1 (en) * | 1978-11-29 | 1980-06-27 | Conservatoire Nal Arts Metiers | Prepn. of plant growth regulating metal sulphonate(s) - by treating a sulphonyl chloride with the metal and iodine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2654667A (en) * | 1950-11-29 | 1953-10-06 | Phillips Petroleum Co | Sulfoxides as plant defoliants |
| US2999105A (en) * | 1957-05-20 | 1961-09-05 | Phillips Petroleum Co | Process for preparation of esters of thiosulfinic acids |
| US3463803A (en) * | 1966-10-28 | 1969-08-26 | Chemagro Corp | Polyhaloethyl and polyhalovinyl sulfinate and thiosulfinate esters |
-
1972
- 1972-02-25 SU SU1752211A patent/SU512691A3/en active
- 1972-02-26 EG EG70/72A patent/EG10407A/en active
- 1972-02-29 US US230505A patent/US3885951A/en not_active Expired - Lifetime
- 1972-03-01 RO RO7269945A patent/RO70848A/en unknown
- 1972-03-01 TR TR16683A patent/TR16683A/en unknown
- 1972-03-03 DD DD161302A patent/DD96626A5/xx unknown
- 1972-03-03 IL IL38891A patent/IL38891A/en unknown
- 1972-03-03 AT AT178972A patent/AT314271B/en not_active IP Right Cessation
- 1972-03-03 CH CH317172A patent/CH568003A5/xx not_active IP Right Cessation
- 1972-03-03 NL NLAANVRAGE7202864,A patent/NL169401C/en not_active IP Right Cessation
- 1972-03-03 ZA ZA721461A patent/ZA721461B/en unknown
- 1972-03-03 CA CA136,160A patent/CA987127A/en not_active Expired
- 1972-03-03 BR BR1239/72*[A patent/BR7201239D0/en unknown
- 1972-03-04 PL PL1972153870A patent/PL83269B1/pl unknown
- 1972-03-04 ES ES400452A patent/ES400452A1/en not_active Expired
- 1972-03-04 HU HUBA2709A patent/HU164190B/hu unknown
- 1972-03-04 IT IT21449/72A patent/IT953442B/en active
- 1972-03-06 JP JP2239872A patent/JPS5618562B1/ja active Pending
- 1972-03-06 FR FR7207690A patent/FR2128660B1/fr not_active Expired
- 1972-03-06 GB GB1030772A patent/GB1320667A/en not_active Expired
- 1972-03-06 BE BE780256A patent/BE780256A/en unknown
- 1972-03-06 CS CS1485A patent/CS176188B2/cs unknown
-
1975
- 1975-12-30 MY MY57/75A patent/MY7500057A/en unknown
-
1976
- 1976-04-13 KE KE2617*UA patent/KE2617A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2654667A (en) * | 1950-11-29 | 1953-10-06 | Phillips Petroleum Co | Sulfoxides as plant defoliants |
| US2999105A (en) * | 1957-05-20 | 1961-09-05 | Phillips Petroleum Co | Process for preparation of esters of thiosulfinic acids |
| US3463803A (en) * | 1966-10-28 | 1969-08-26 | Chemagro Corp | Polyhaloethyl and polyhalovinyl sulfinate and thiosulfinate esters |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3927062A (en) * | 1972-05-15 | 1975-12-16 | Shell Oil Co | Plant growth regulators |
| US4227918A (en) * | 1976-12-17 | 1980-10-14 | Bayer Aktiengesellschaft | Novel halogenoethyl sulphones and their use as plant growth regulators |
| US4149873A (en) * | 1977-01-12 | 1979-04-17 | Ciba-Geigy Corporation | Composition for the regulation of plant metabolism |
| US4357159A (en) * | 1977-01-12 | 1982-11-02 | Ciba-Geigy Corporation | Haloethylthienylsulphonates for the regulation of plant metabolism |
| US4359334A (en) * | 1980-04-28 | 1982-11-16 | Gaf Corporation | Composition for plant growth regulation |
| US4427439A (en) | 1980-04-28 | 1984-01-24 | Gaf Corporation | Composition for plant growth regulation |
| WO1987005781A2 (en) | 1986-03-31 | 1987-10-08 | Rhone-Poulenc Nederlands B.V. | Synergistic plant growth regulator compositions |
| US5123951A (en) * | 1986-03-31 | 1992-06-23 | Rhone-Poulenc Nederland B.V. | Synergistic plant growth regulator compositions |
| US6274632B1 (en) * | 1997-03-12 | 2001-08-14 | Zeneca Limited | Derivatives of 4,4-difluorobut-3-enylsulfinic acid and their use as pesticides |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2110773B2 (en) | 1976-12-02 |
| BR7201239D0 (en) | 1973-05-03 |
| IL38891A0 (en) | 1972-05-30 |
| NL7202864A (en) | 1972-09-07 |
| AT314271B (en) | 1974-03-25 |
| ZA721461B (en) | 1972-11-29 |
| DD96626A5 (en) | 1973-04-05 |
| CA987127A (en) | 1976-04-13 |
| FR2128660B1 (en) | 1975-10-24 |
| NL169401B (en) | 1982-02-16 |
| KE2617A (en) | 1976-04-30 |
| CS176188B2 (en) | 1977-06-30 |
| FR2128660A1 (en) | 1972-10-20 |
| DE2110773A1 (en) | 1972-09-28 |
| JPS5618562B1 (en) | 1981-04-30 |
| PL83269B1 (en) | 1975-12-31 |
| ES400452A1 (en) | 1975-07-01 |
| MY7500057A (en) | 1975-12-31 |
| EG10407A (en) | 1976-05-31 |
| GB1320667A (en) | 1973-06-20 |
| IT953442B (en) | 1973-08-10 |
| RO70848A (en) | 1980-08-15 |
| CH568003A5 (en) | 1975-10-31 |
| IL38891A (en) | 1974-12-31 |
| HU164190B (en) | 1974-01-28 |
| TR16683A (en) | 1973-03-01 |
| SU512691A3 (en) | 1976-04-30 |
| NL169401C (en) | 1982-07-16 |
| BE780256A (en) | 1972-09-06 |
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