CA1066708A - Azol compounds useful as plant growth regulation agents - Google Patents
Azol compounds useful as plant growth regulation agentsInfo
- Publication number
- CA1066708A CA1066708A CA243,584A CA243584A CA1066708A CA 1066708 A CA1066708 A CA 1066708A CA 243584 A CA243584 A CA 243584A CA 1066708 A CA1066708 A CA 1066708A
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- CA
- Canada
- Prior art keywords
- compound
- general formula
- diyl
- plant
- carboxyphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/32—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups
- C07C65/34—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
- C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
- C07D271/107—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with two aryl or substituted aryl radicals attached in positions 2 and 5
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D277/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
ABSTRACT
A method of regulating the growth of plants using a compound of general formula:
wherein R1 to R10 are hydrogen, lower alkyl, halogen, amino, nitro, cyano, or -COR11 wherein R11 is hydroxy, lower alkoxy, arylalkoxy, aryloxy, substituted or unsubstituted amino, or a group of formula:
- O ?]n Mn? or - S ?]n Mn?
wherein Mn? is an ammonium,alkali metal or alkaline earth metal ion and n is 1 or 2 accordingly; at least one of R1, R5 R6, and R10 being -COR11 and A is a five membered cyclic moiety including two double bonds and comprising up to three heretoatoms, the said heteroatoms being either the same or different wish the proviso that A may not be a pyrazolyl group.
A method of regulating the growth of plants using a compound of general formula:
wherein R1 to R10 are hydrogen, lower alkyl, halogen, amino, nitro, cyano, or -COR11 wherein R11 is hydroxy, lower alkoxy, arylalkoxy, aryloxy, substituted or unsubstituted amino, or a group of formula:
- O ?]n Mn? or - S ?]n Mn?
wherein Mn? is an ammonium,alkali metal or alkaline earth metal ion and n is 1 or 2 accordingly; at least one of R1, R5 R6, and R10 being -COR11 and A is a five membered cyclic moiety including two double bonds and comprising up to three heretoatoms, the said heteroatoms being either the same or different wish the proviso that A may not be a pyrazolyl group.
Description
This invention relates to certain diphenylheterocyclic compounds useful in regulating the growth of, or killing, plants, to a process for preparing them and to method of regulating the growth of, or killing, plants using them.
S The compounds have the general formula (I) :
R3 ~ R5 R6 ~ R8 (I) ~2 ~ ~ Q ~ R9 wherein each of R1 to R10, which may be the same or different, is hydrogen, lower alkyl, halogen, amino, nitro, cyano or -CORll wherein Rll is hydroxy, lower alkoxy, aralkoxy, aryloxy, unsubstituted amino or ~~ 7n Mn0 or -S~ 7n Mn0 wherein Mn0 is an ammonium, alkali metal or alkaline earth metal ion and n is 1 or 2 accordingly, Rl being -CORll, at least three of R2 to RS being hydrogen and at least four of R6 to R10 being hydrogen and wherein Q is a heterocyclic ring which is isoxazole-3,5-diyl, thiazole-2,4-diyl, 1,2,4-triazole-3,5-diyl, 1,3,4-thiadiazole-2,5-diyl, 1,2,4-oxadiazole- - -3,5-diyl or 1,3,4-oxadiazole-2,5-diyl.
The halogen atom is suitably a chlorine atom preferably in the o- or ~- positions but it can be a bromine or iodine atom.
, ' ' :, ,.: ., ~:
The t~rms "lowe~ alkyl" and "lower alkoxy" as used herein refer to groups containing 1 to 6 carbon atoms.
Examples of these preferred compounds of the invention are shown in Table (I), - 3 - ::--. -'' ' - , ' s~ ~
,, " ", " ". " ,.. , ":, . . ," : .. ,:, ,, " " ,, ", ,~ ' : x; ' ~
`- 1066~708 TABLE I
O - N
__ ~43 . HN N
,` ~
. .
~ .
,, :, .. . ,. .. - . ..
- . ` . .: :
.~
.
.` ' ., ` ' '` ~ . ~.
The compositions of the invention comprise the compounds of general formula (I) and a carrier, e.g.
one comprising a diluent and/or surface active agent.
The compositions of the invention are of use either as plant growth regulants or as herbicides. The activity obtained using any particular composition depends inter alia on the concentration of the active ingredient, the time or rate of application of the composition, and upon the plant species being treated.
The compositions can be used in treating both monocotyledonous and dicotyledonous plants and may be applled in either a pre- or post-emergent manner. When applied in a post-emergent manner either the roots or foliage of the plants may be treated, the former for example by aqueous foliar spray.
The solid compositions may be in the form of seed dressings, dusting powders or granules, wherein the active ingredient is mixed with a finely divided solid diluent, e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's ; earth and gypsum. They may also be in the form of dispersible powders or grains, comprising a wetting agent to facilitate the dispersion of the powder or grains in liquid.
Liquid compositions are generally preferr`ed especially for foliar application, since they are more convenient to use.
.. ..
. . : . . . : .
~, . ... . .... ... . .. :
- . .: . ... . . . . , .
, . : . .... . , ~ . , - ' : .'' ' ' ~ :.... ' ~. .
: .: . .... .. .
,' ~, ' : " : '.,~ ' .:
Liquid compositions include aqueous solutions, dispersions or emulsions containing the active ingreaient together with surface-active agent(s) such as wetting agent(s), dispersing agent(s), emulsifying agent(s), or suspending agent(s).
Surface-active agents may be of the cationic, anionic, or non-ionic type. The cationic agents are, for example, quaternary ammonium compounds (e.g. cetyltrimethyl-ammonium bromide). Suitable anionic agents are soaps;
salts of aliphatic mono esters or sulphuric acid, for example sodium lauryl sulphate; and salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium, and ammonium lignosulphonate, butylnaphthal-enesulphonate, and a mixture of the sodium salts of di-isopropyl- and triisopropyl-naphthalene-sulphonic acid.
$uitable nonionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, or with alkylphenols such as octyl- or nonyl-phenol or octylcresol. Other non-ionic agents are .
the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate; -the condensation products of the partial esters with ethylene oxide; and the lecithins. Suitable suspending agen~s ., ~ , are hydrophilic colloids, for example polyvinylpyrrolid~ne and sodium carboxymethylcellulose, and the vegetable gums, for example gum acacia and gum tragacanth. ~-~
.
. ~ , . , , :.
6 ~ -.
.
.: .
1066~708 The aqueous solutions, dispersions or emulsions may be prepared by dissolving the active ingredient in water or an organic solvent optionally containing wetting, dispersing, or emulsifying agent(s) and then, when organic solvents are used, adding the mixture so obtained to water optionally containing wetting, dispersing or emulsifying agent(s). Suitable organic solvents are ethylene dichlorlde, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene.
The composltions for use in the form of aqueous solutions, dispersions or emulslons are generally supplied ln the form of a concentrate contalning a high proportion of the actlve ingredient, and the concentrate is then diluted with water before use. These concentrates are -` usually required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Concentrates conveniently contain 10 - 8S%, preferably 25 - 60~, by weight of the active ingredient(s). Dilute preparations ready for use may contain varying amounts of the active ingredient(s), depending upon the intended purpose; amounts of 0.01~ and 10.0%, preferably 0.1~ and 1%, by weight of active ingredient(s) are normally used.
.;
.' `' ,. . .. . .. . . . .. . . ..
-, : . :
, : , , ; . :. . :
The composit~ons for use as plant growth regulators may also contain other plant growth regulating agents, for example maleic hydrazide, chlorflurecol and carbetamide. Such plant growth regulating agents may also be herbicides effective against broad leaved weeds, particularly such herblcides which are selectlvely active agalnst broad leaved weeds, for example hormone herbicides such as 2,4-D, MCPA, mecoprop and dichlorprop.
The plant growth regulating effects are manifested chiefly as a stunting or dwarfing effect in the plants to which they are applled. Such stunting or dwarfing may be us~ful, for example, in cereals, where reduction in stem growth may reduce the risk of lodging. It may also ~ be useful in stunting the growth of sugar cane thereby - 15 increasing the concentration of sugar in the cane at harvest. Grass may be treated to siow down growth, so J that it need not be mown so often.
The compounds can also have a plant stimulating effect e.g. they can increase the shoot growth of vine seedlings.
The amount of active ingredient compound applied to regulate the growth of plants will depend upon a number of factors, for example the particular formulation i-~
selected for use, whether the compound is to be applied for foliage or root uptake, the effect desired, and the identity of the plant species in question. However, an appllcation rate of 0.5 to 20, preferably 2 to 5, kg per hectare is generally suitable. Where herbicidal effects ,. . .
' -8-_. -. . , . . - - , . - . ~ ............ , ,., , ~.. , - .
- . , . ' .: . ~:, :, '.. . - -.,- . -are desired, the rates used are naturally in general higher than for growth stunting. In all cases, routine tests are necessary to determine the best rate of application of a specific formulation for any speclfic purpose for which it is suitable.
Certain of the compounds of general formula (I) are novel compounds. The lnvention thus provides the compounds of general formula (I) wherein Rl to R and A as defined above, with the additional proviso that when A is a ring of general formula (B) and X is oxygen, then Y and Z may not both be imino nitrogen.
The compounds of general formula (I) may be prepared by known methods, the particular method being primarily chosen according to the nature of A. These methods are illustrated in Table II.
. , TABLE II
Examples of SYnthetic Routes to Compounds of Formula X A - Y
whereln X = R3 ~ RS
R
` ~1 . R6`~_ R8 and Y =
. R10 ~ ' :
_g_ : -. , , , -- , . .
.. , . , . : .
. ., ;. ~ . ~ , . ~
, , ,~ , ,, . ' ' ' ~' -1066~08 and wherein Rl to R10 and Z are as deflned above.
Moiety A Preparation - General Method - XCN + Y - C
1,2,4-Triazole ~NH-NH2 oxidiz e H
, % 1l CH2 ~ ICl ~ Y heat ~ X~Y
Isoxazole HO O - N
~ . .
`~.0 X C~O+Y ~
. H H-NH2 1,3,4-Oxadiazole hOeadi 3 ~ Y
~` I I
R5 ~ _ I
1,2,4-Oxadiazole ~ \ O ~ Y - C~
. R3- ~ C /o ~NH-N~2 :~ ~ X~y: I
`''I :, ~
~10-~
: : . , . , : , , -. ~ , . : :
, :, , , : .
. ,, . :,~ ', . ,, : , The invention therefore provid~s:
(1) a process for preparing a compound of general formula (I) wherein Q is 1,2,4-triazole-3,5-diyl and Rl is COOH, the process comprising oxidising a compound of general formula (I) wherein Q is 1,2,4-triazol.e-3,5-diyl and Rl to Rl are as defined above, subject to the proviso that R is lower alkyl;
S The compounds have the general formula (I) :
R3 ~ R5 R6 ~ R8 (I) ~2 ~ ~ Q ~ R9 wherein each of R1 to R10, which may be the same or different, is hydrogen, lower alkyl, halogen, amino, nitro, cyano or -CORll wherein Rll is hydroxy, lower alkoxy, aralkoxy, aryloxy, unsubstituted amino or ~~ 7n Mn0 or -S~ 7n Mn0 wherein Mn0 is an ammonium, alkali metal or alkaline earth metal ion and n is 1 or 2 accordingly, Rl being -CORll, at least three of R2 to RS being hydrogen and at least four of R6 to R10 being hydrogen and wherein Q is a heterocyclic ring which is isoxazole-3,5-diyl, thiazole-2,4-diyl, 1,2,4-triazole-3,5-diyl, 1,3,4-thiadiazole-2,5-diyl, 1,2,4-oxadiazole- - -3,5-diyl or 1,3,4-oxadiazole-2,5-diyl.
The halogen atom is suitably a chlorine atom preferably in the o- or ~- positions but it can be a bromine or iodine atom.
, ' ' :, ,.: ., ~:
The t~rms "lowe~ alkyl" and "lower alkoxy" as used herein refer to groups containing 1 to 6 carbon atoms.
Examples of these preferred compounds of the invention are shown in Table (I), - 3 - ::--. -'' ' - , ' s~ ~
,, " ", " ". " ,.. , ":, . . ," : .. ,:, ,, " " ,, ", ,~ ' : x; ' ~
`- 1066~708 TABLE I
O - N
__ ~43 . HN N
,` ~
. .
~ .
,, :, .. . ,. .. - . ..
- . ` . .: :
.~
.
.` ' ., ` ' '` ~ . ~.
The compositions of the invention comprise the compounds of general formula (I) and a carrier, e.g.
one comprising a diluent and/or surface active agent.
The compositions of the invention are of use either as plant growth regulants or as herbicides. The activity obtained using any particular composition depends inter alia on the concentration of the active ingredient, the time or rate of application of the composition, and upon the plant species being treated.
The compositions can be used in treating both monocotyledonous and dicotyledonous plants and may be applled in either a pre- or post-emergent manner. When applied in a post-emergent manner either the roots or foliage of the plants may be treated, the former for example by aqueous foliar spray.
The solid compositions may be in the form of seed dressings, dusting powders or granules, wherein the active ingredient is mixed with a finely divided solid diluent, e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's ; earth and gypsum. They may also be in the form of dispersible powders or grains, comprising a wetting agent to facilitate the dispersion of the powder or grains in liquid.
Liquid compositions are generally preferr`ed especially for foliar application, since they are more convenient to use.
.. ..
. . : . . . : .
~, . ... . .... ... . .. :
- . .: . ... . . . . , .
, . : . .... . , ~ . , - ' : .'' ' ' ~ :.... ' ~. .
: .: . .... .. .
,' ~, ' : " : '.,~ ' .:
Liquid compositions include aqueous solutions, dispersions or emulsions containing the active ingreaient together with surface-active agent(s) such as wetting agent(s), dispersing agent(s), emulsifying agent(s), or suspending agent(s).
Surface-active agents may be of the cationic, anionic, or non-ionic type. The cationic agents are, for example, quaternary ammonium compounds (e.g. cetyltrimethyl-ammonium bromide). Suitable anionic agents are soaps;
salts of aliphatic mono esters or sulphuric acid, for example sodium lauryl sulphate; and salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium, and ammonium lignosulphonate, butylnaphthal-enesulphonate, and a mixture of the sodium salts of di-isopropyl- and triisopropyl-naphthalene-sulphonic acid.
$uitable nonionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, or with alkylphenols such as octyl- or nonyl-phenol or octylcresol. Other non-ionic agents are .
the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate; -the condensation products of the partial esters with ethylene oxide; and the lecithins. Suitable suspending agen~s ., ~ , are hydrophilic colloids, for example polyvinylpyrrolid~ne and sodium carboxymethylcellulose, and the vegetable gums, for example gum acacia and gum tragacanth. ~-~
.
. ~ , . , , :.
6 ~ -.
.
.: .
1066~708 The aqueous solutions, dispersions or emulsions may be prepared by dissolving the active ingredient in water or an organic solvent optionally containing wetting, dispersing, or emulsifying agent(s) and then, when organic solvents are used, adding the mixture so obtained to water optionally containing wetting, dispersing or emulsifying agent(s). Suitable organic solvents are ethylene dichlorlde, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene.
The composltions for use in the form of aqueous solutions, dispersions or emulslons are generally supplied ln the form of a concentrate contalning a high proportion of the actlve ingredient, and the concentrate is then diluted with water before use. These concentrates are -` usually required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Concentrates conveniently contain 10 - 8S%, preferably 25 - 60~, by weight of the active ingredient(s). Dilute preparations ready for use may contain varying amounts of the active ingredient(s), depending upon the intended purpose; amounts of 0.01~ and 10.0%, preferably 0.1~ and 1%, by weight of active ingredient(s) are normally used.
.;
.' `' ,. . .. . .. . . . .. . . ..
-, : . :
, : , , ; . :. . :
The composit~ons for use as plant growth regulators may also contain other plant growth regulating agents, for example maleic hydrazide, chlorflurecol and carbetamide. Such plant growth regulating agents may also be herbicides effective against broad leaved weeds, particularly such herblcides which are selectlvely active agalnst broad leaved weeds, for example hormone herbicides such as 2,4-D, MCPA, mecoprop and dichlorprop.
The plant growth regulating effects are manifested chiefly as a stunting or dwarfing effect in the plants to which they are applled. Such stunting or dwarfing may be us~ful, for example, in cereals, where reduction in stem growth may reduce the risk of lodging. It may also ~ be useful in stunting the growth of sugar cane thereby - 15 increasing the concentration of sugar in the cane at harvest. Grass may be treated to siow down growth, so J that it need not be mown so often.
The compounds can also have a plant stimulating effect e.g. they can increase the shoot growth of vine seedlings.
The amount of active ingredient compound applied to regulate the growth of plants will depend upon a number of factors, for example the particular formulation i-~
selected for use, whether the compound is to be applied for foliage or root uptake, the effect desired, and the identity of the plant species in question. However, an appllcation rate of 0.5 to 20, preferably 2 to 5, kg per hectare is generally suitable. Where herbicidal effects ,. . .
' -8-_. -. . , . . - - , . - . ~ ............ , ,., , ~.. , - .
- . , . ' .: . ~:, :, '.. . - -.,- . -are desired, the rates used are naturally in general higher than for growth stunting. In all cases, routine tests are necessary to determine the best rate of application of a specific formulation for any speclfic purpose for which it is suitable.
Certain of the compounds of general formula (I) are novel compounds. The lnvention thus provides the compounds of general formula (I) wherein Rl to R and A as defined above, with the additional proviso that when A is a ring of general formula (B) and X is oxygen, then Y and Z may not both be imino nitrogen.
The compounds of general formula (I) may be prepared by known methods, the particular method being primarily chosen according to the nature of A. These methods are illustrated in Table II.
. , TABLE II
Examples of SYnthetic Routes to Compounds of Formula X A - Y
whereln X = R3 ~ RS
R
` ~1 . R6`~_ R8 and Y =
. R10 ~ ' :
_g_ : -. , , , -- , . .
.. , . , . : .
. ., ;. ~ . ~ , . ~
, , ,~ , ,, . ' ' ' ~' -1066~08 and wherein Rl to R10 and Z are as deflned above.
Moiety A Preparation - General Method - XCN + Y - C
1,2,4-Triazole ~NH-NH2 oxidiz e H
, % 1l CH2 ~ ICl ~ Y heat ~ X~Y
Isoxazole HO O - N
~ . .
`~.0 X C~O+Y ~
. H H-NH2 1,3,4-Oxadiazole hOeadi 3 ~ Y
~` I I
R5 ~ _ I
1,2,4-Oxadiazole ~ \ O ~ Y - C~
. R3- ~ C /o ~NH-N~2 :~ ~ X~y: I
`''I :, ~
~10-~
: : . , . , : , , -. ~ , . : :
, :, , , : .
. ,, . :,~ ', . ,, : , The invention therefore provid~s:
(1) a process for preparing a compound of general formula (I) wherein Q is 1,2,4-triazole-3,5-diyl and Rl is COOH, the process comprising oxidising a compound of general formula (I) wherein Q is 1,2,4-triazol.e-3,5-diyl and Rl to Rl are as defined above, subject to the proviso that R is lower alkyl;
(2) a process for preparing a compound of general formula (I) wherein Q is isoxazole-3,5-diyl, the process comprising cyclising a compound of general formula (II):
C-CH2-C ~ R9 O NOH
wherein Rl to R10 are as defined above;
,. .
; (3) a process for preparing a compound of general formula ~ (I) wherein Q is isoxazole-3,5-diyl, the process comprising `- reacting with hydroxylamine, a compound of general formula ~ ::
: 15 (III):
R3 ~ ~
_O CH-C R10 - o X o .. .. .. ..
.-, i A~ , i . .; . . . .; ... . .. . . .
.. ... , ... .. . ~ ,. .. ... .
. , " . .,~ .. ..... . ~ , .
. " , , . . ~,, ,, .
... .. ..... . . .. . . . . .
wherein Rl to R4 an~ R6 to R10 a~e as ~efined abo~e! and is halogen (e.g. chlorine, bromine or iodine);
(4) a process for preparing a compound of general formula ~I) wherein Q is 1,3,4-oxadiazole-2,5-diyl and Rl is COOH, the process comprising oxidising a compound of general formula (I) wherein Q is 1,3,4-oxadiazole-2,5-diyl and R to R10 are as defined above subject to the proviso that Rl is lower alkyl;
~5) a process for preparing a compound of general formula (I) wherein Q is 1,3,4-oxadiazole-2,5-diyl, the process comprising oxidising with cyclisation a compound`of general formula (IV): R4 R7 2 ~ CU=NNHC ~ R (IV) ; R R10 ,'' .
' wherein Rl to R10 are as defined above;
- . .
~6) a process for preparing a compound of general formula ~ 15 (I) wherein Q is thiazole-2,4-diyl, the process comprising .~ xeacting a compound of general`formula (V):
.
R ~ RCSCH2X ~V) .
. - 12 -,' ' ' ;~i' ' I
wherein Rl to R5 and X are as defined above; with a corlpound of the general formula (VI): R7 R6 ~ R8 S ~ ~ R9 (VI) wherein R6 to R10 are as defined above, and if neccssary or desired hydrolysing any ester formed; and (7) A pxocess for preparing a compound of general formula ~I) wherein A is 1,3,4-thiadiazole-2,5-diyl and Rl is COOH, the process comprising oxidising a compound of general formula (I) wherein A is 1,3,4-thiadiazole-2,5-diyl and to R10 are as defined above subject to the replacement proviso that Rl is lower alkyl.
` The invention is illustrated by the following Examples.
.~- - :.
1`~ .
This Example illustrates the method of the present `~ inventiQn wherein the growth regulant composition is applied , , .
to the roots of plants.
In the following test, the compound was applied to the roots of test plants grown in sand in flower pots. When the roots of the plants were established in this medium, 25 ml -of a dilute aqueous emulsion comprising 500 ppm of 3-(o~
carboxyphenyl)-5-phenylisoxazole was applied to saturate the sand within the pot. The percentage reduction in size of treated plant compared with untreated control plants was assessed after 10 days.
,' ` ~ ~' ' .' ~ , , ''~
" .
;, : .,: ' , ' , ', . ` ' ' : ' . ~ ' .
~ 1066708 The results are given in Table III below.
TABLE III
Test Plant% Reduction in Other Size Obser~ations Wheat 15 Increased number of sideshoots. Root growth severely inhibited.
Barley 20 Leaves paler green Brussel 20 Inhibition of apical Sprouts growth.
This Example illustrates the method o~ the invention wherein the growth regulant composition is applied to the foliage of plants.
- 5 Test plants grown in pots as in Example 1 were sprayed with a dilute aqueous emulsion comprlsing
C-CH2-C ~ R9 O NOH
wherein Rl to R10 are as defined above;
,. .
; (3) a process for preparing a compound of general formula ~ (I) wherein Q is isoxazole-3,5-diyl, the process comprising `- reacting with hydroxylamine, a compound of general formula ~ ::
: 15 (III):
R3 ~ ~
_O CH-C R10 - o X o .. .. .. ..
.-, i A~ , i . .; . . . .; ... . .. . . .
.. ... , ... .. . ~ ,. .. ... .
. , " . .,~ .. ..... . ~ , .
. " , , . . ~,, ,, .
... .. ..... . . .. . . . . .
wherein Rl to R4 an~ R6 to R10 a~e as ~efined abo~e! and is halogen (e.g. chlorine, bromine or iodine);
(4) a process for preparing a compound of general formula ~I) wherein Q is 1,3,4-oxadiazole-2,5-diyl and Rl is COOH, the process comprising oxidising a compound of general formula (I) wherein Q is 1,3,4-oxadiazole-2,5-diyl and R to R10 are as defined above subject to the proviso that Rl is lower alkyl;
~5) a process for preparing a compound of general formula (I) wherein Q is 1,3,4-oxadiazole-2,5-diyl, the process comprising oxidising with cyclisation a compound`of general formula (IV): R4 R7 2 ~ CU=NNHC ~ R (IV) ; R R10 ,'' .
' wherein Rl to R10 are as defined above;
- . .
~6) a process for preparing a compound of general formula ~ 15 (I) wherein Q is thiazole-2,4-diyl, the process comprising .~ xeacting a compound of general`formula (V):
.
R ~ RCSCH2X ~V) .
. - 12 -,' ' ' ;~i' ' I
wherein Rl to R5 and X are as defined above; with a corlpound of the general formula (VI): R7 R6 ~ R8 S ~ ~ R9 (VI) wherein R6 to R10 are as defined above, and if neccssary or desired hydrolysing any ester formed; and (7) A pxocess for preparing a compound of general formula ~I) wherein A is 1,3,4-thiadiazole-2,5-diyl and Rl is COOH, the process comprising oxidising a compound of general formula (I) wherein A is 1,3,4-thiadiazole-2,5-diyl and to R10 are as defined above subject to the replacement proviso that Rl is lower alkyl.
` The invention is illustrated by the following Examples.
.~- - :.
1`~ .
This Example illustrates the method of the present `~ inventiQn wherein the growth regulant composition is applied , , .
to the roots of plants.
In the following test, the compound was applied to the roots of test plants grown in sand in flower pots. When the roots of the plants were established in this medium, 25 ml -of a dilute aqueous emulsion comprising 500 ppm of 3-(o~
carboxyphenyl)-5-phenylisoxazole was applied to saturate the sand within the pot. The percentage reduction in size of treated plant compared with untreated control plants was assessed after 10 days.
,' ` ~ ~' ' .' ~ , , ''~
" .
;, : .,: ' , ' , ', . ` ' ' : ' . ~ ' .
~ 1066708 The results are given in Table III below.
TABLE III
Test Plant% Reduction in Other Size Obser~ations Wheat 15 Increased number of sideshoots. Root growth severely inhibited.
Barley 20 Leaves paler green Brussel 20 Inhibition of apical Sprouts growth.
This Example illustrates the method o~ the invention wherein the growth regulant composition is applied to the foliage of plants.
- 5 Test plants grown in pots as in Example 1 were sprayed with a dilute aqueous emulsion comprlsing
3{o-carboxyphenyl]-5-phenylisoxazole at a rate equivalent to 5 kg/ha (the volume of liquid used being equivalent to 1000 l/ha). The plants were observed after 14 days and compared with untreated control plants. The results are shown in Table IV below.
.
TABLE IV
: , Test Plant Effect of foliar application of 3~ ~-carboxyphenyl~-5~phenylisoxazole '~i f Barley 10% reduction in growth Tomato Reduced leaf area Brussel Sprouts Accelerated leaf senescence i .- - .: , , , ;: : : . , ,: :
. , . - , . . ..
, , : , : . . , : . : .
:: , , . . . :
.: . .. ,, . ." .
, , . : , :
Example 3 A grass sward in an old pasture was cut to a constant level and then dressed with nitrogenous fertilizer to encourage vigourus new growth. Plots (3 x 2 m) were pegged out on the grass and 10 days afterwards a group of 3 such plots was sprayed with a dilute aqueous emulsion comprising 3-to-carboxyphenyl]-5-phenylisoxazole at a rate equivalent to 1 kg per hectare, and a second group ;` of 3 plots was retained untreated as a control. The a~ueous sprays were applied at a volume equivalent to 400 litres/
hectare.
Observations of the plots were made 14 days and 22 days after treatment and it was notice~ that the grass in the treated plots had grown considerably less than that in the control area. The results are presented in Table V
` below.
~ Table V
;~J
. . . ,,,.
Rate of Application of ~ Growth reduction of rass Active Ingredinet Compound After 14 days After ~ days ~. . _ .. ..
, 20 1 kg/ha 68 61 2 kg/ha 73 77 ~ . . . ._.
: . . ._ - . .. _ Example 4 This Example illustrates the method of the invention in modifying the root geotropism of plants.
Seeds of cress (LeFidium satirum) were allowed to germinate on agar in a Petri dish until the roots were 1 cm long. Agar compositions, each comprising one of the com- -pounds listed in Table VI below and present in the concentration ,, ' :' indicated therein, were prepared in Petri dishes and three seedlings were transferred to the surface of each of these compositions.
For the purpose of comparison a group of seedlings were transferred to a Petri dish containing agar comprising no active ingredient compound.
Each of these Petri dishes was then turned verti-cally so that their root tips initially pointed horizontally, and were then placed in darkness at 24C ~or 24 hours. At the end o~ this period, the plants were examined for any alteration to their normal response to gravity.
It was observed that the roots of those seedlings ; placed in the agar compositions comprising an active ingre-dient compound had continued to grow horizontally i.e.
t ~ r normal geotropic response had been destroyed. The untreated plants had exhibited a normal response i.e. their , root tips had turned downwards.
Table VI
,.. .. .. _ _. ., .. . _ Active Ingrediènt Compound Concentration (M x 10-6) 3-[o-carboxyphenyl]-5-phenyl-1~2~4-triazole 1 3-phenyl-5-to-carboxyphenyl]-1,2,4-oxadiazole 0.1 5-lo-carboxyphenyl]-3-phenylisoxazole . ' .. '-".'.'"''' .. ~ ,.' ~ ' .
,. . .
f -, ' , ....
,, : .:.... .: . .
This Example lllustrates the method of the invention in modlfylng the growth of the plant species Arabidopsis thaliana.
An aqueous nutrlent medium comprislng a suitable small concentration of each of the lngredients potassium dihydrogen phosphate, potasslum nitrate, calcium nitrate, and magneslum sulphate was prepared and the pB of this medium was adjusted to 6Ø A small amount of an acetone solutlon of each of the compounds listed in Table VII
below was added to an aliquot of the nutrient medlum to provide the active ingredient concentration shown in this Table.
Each aliquot was then mixed with sufficient molten agar to solidify it, and 7 mls of each mixture was poured into a sterilized test tube which was then plugged with cotton wool. Each test tube was then seeded with a single seed of Arabldopsis thaliana. Several test tubes containing solidified nutrient medium and not comprising - an active ingredient compound was also seeded.
After standing at 4C for 24 hours all the test tubes were maintained at 25C, at 65% humidity, and continuously illuminated at 15 t to 20,000 lux from fluorescent tubes. Germination of the seeds occurred within 72 hours and growth was allowed to proceed for 20 days. At the end of this period it was observed that the pattern of growth of both the foliage and roots of those plants grown in the agar compositions comprising an active , - :, ; ~ '' " ~ .
. " ., .' -' ' ' '' ,: .,: ~,.
.. . . . . . . . . . .
''' "; ~ ' ' .. : .:
.
. . . . .. . .
, ", :, , ' compound was markedly different from that of the untreated plants.
Table VII
Active Ingredient Compound Concentration (ppm) . .
,~ 5-(o-carboxyphenyl)-3-phenylisoxazole 0.1 2-(o-carboxyphenyl)-5-phenyl-1,3,4-oxadiazole 0.5 3-(o-carboxyphenyl)-5-phenyl-1,2,4-triazole 4.0 ~-phenyl-5-(o-carboxyphenyl-1,2,4-oxadiazole 1.0 Example 6 A dilute aqueous emulsion of each of the compounds ; listed in Table VII was sprayed onto separate plots of soil ` at a rate equivalent to 1 to 8 kg/ha of active ingredient and a volume equivalent to 1000 litres per hectare. Seeds of peas, mustard, barley, maize, linseed, and ryegrass ,,r~ were then sown in each plot and allowed to germinate and mature. Each species of plant in each plot exhibited plant ~ growth regulatory effects in the form of either leaf ``~ 20 epinasty, anti-geotropic root growth, or loss of apical dominance.
Example 7 ---This Example illustrates the plant growth regu-' lating activity of compositions of the invention when applied to s variety of plant species in both the pre- snd post-.-: .
'.
, -. ~, . . , , , - .
: ................................. -,, , . , , , :.
`` 1066708 -emergent manner.
Seeds of wheat,wild oats, ryegrass, Japanese millet, peas, ipomoea, mustard and sunflower were sprinkled onto the surface of soil in separate boxes and covered with a thin layer of sand. The contents of each box werethen sprayed with a dilute aqueous composition comprising one of the compounds listed in Table VIII and at one of the application rates indicated thereln r The contents of the boxes were then lightly watered wlth an overhead spray and placed ln a glass-house to encourage germination of the seeds. Three weeks later the boxes were removed from the glass-house and the growth pattern of emerged plants was compared to that of a set of untreated control plants to assess the pre-emergent plant growth regulating activity of the compositions applied. The results are presented in Table VIII.
In addition,seeds of whea~ wild oats, ryegrass, Japanese millet, peas, ipomoea, mustard, and sunflower were covered with sand, lightly watered in the manner described above, and then placed in a glass-house for one week to -permit germination of the seeds and plant growth to a height of 4 to 5 inches. The boxes were then removed from the glass-house and the contents of each box weresprayed with a dilute aqueous composition comprising as active ingredient one of the compounds listed in Table VIII and at one of the application rates indicated therein.
. ,,' ~, .," ' . ', ;;''.' ' . ' ... .
,. . . , -; "
- ~ 1066708 After spraying the boxes Were returned to the glass-house for a further 3 weeks. The growth pattern of the plants was then compared with that of a set of untreated plants to assess the post-emergent plant growth regulating activity of the compositions applied. The results are presented in Table VIII.
TABLE VIII
_ Actlve Ingredient Plant - Plant Growth Pattern*
Compound Species Pre-emergence Post-ëmergence at appllcation at application .~ _rate * 10 rate o~: 10 . wheatSt ep0 Sl St : Watds 0 epSl St Sl St ryegrass epep 0 Sl St 3-(o-carboxy- Japanese ep ep St St phenyl)-5-phenyl millet : -1,2,4-triazole : peasSv St St 0 0 . ipomoea St Sv St St St mustard St Sv St St 0 Sunflower Sv St Sv St Sl St St ._ wheatSt S1 St 0 0 wild 0 Sl St 0 0 3-phenyl-5- ~- oats carboxypheny~ -.~ 1,2,4-oxadiazole ryegrass St St _ 0 _ _ _ millet St St _ St .
' ~, , , : ::
: ,. , : , ,, :
' ' '' ' , ' ' ~'' ' ;: ~ . , TA~LE VIII continued Actlve Ingredient Plant Plant Growth Pattern*
Compound Specles I _ Pre-emergence Post-emergence at application at application rate ** of: rate of:
~ -5 10 10 PeasSv St Sv St O O
ipomoead Sv St St St mustardd Sv St St St sunflower~ Sv St ¦ Sv St ¦ S
* Plant growth pattern compared to control set of untreated plants:
S1 St = slightly stunted St = stunted Sv St = severely stunted ep = leaf epinasty O = substantially unaffected d = plant died ` - = no test was performed at this concentration.
, 10 ** Kilograms per hectare of active ingredient compound.
This Example illustrates the use of compositions of the ~vention in regulating the growth of two species of grass.
Seeds of Wimmera ryegrass and cocksfoot were sprinkled onto the surface of soil in separate boxes and covered with ., ., ., : . ,., .. ~ ; . . :
.. .. . . .. . .
. .
. ., ~ , . ,, -" , ., ~ . ~; :
, : . ; ~ , . ::
. .
a thln layer of sand, lightl~ watered and then placed in a glass-house to germinate and grow When the plants were approximately 10 cm high, a box of each specles was sprayed with a volume of a dilute aqueous emulsion of one of the active ingredient compounds listed in Table IX
e~uivalent to 1000 litres per hectare and at the application rate indicated therein. The plants were then returned to the glass-house and after a period of twenty days their growth was compared to that of an untreated set of control plants. The results are presented in Table IX.
TABLE IX
:. _ _ . _ Active Ingredlent Application Reduction in height of Compound Ratecompared to control (kg/ha) plants _ , WimmeraCocksfoot ryegrass 3-lo-carboxypheny~ 1 19 12 -5-phenyl-1,2,4- 5 24 8 triazole ~
3-phenyl-5-~o- 1 19 8 carboxypheny~ - 5 19 8 - 1,2,4-oxadiazole 2-.(o-carboxyphenyl 1 10 16 -5-phenyl-1,3,4- 5 24 28 oxadiazole .
Certaln of the compounds of formula (I) were tested on various plants, e.g. chrysanthemums, Brussels sprout and soybean for growth regulating properties. The results , ,. ~ . , . . . - - . .-. .
.
- . : . , . . , , .. ,. : .
- : :, . . , : , . ~ . .
. , , - , , ' :' ' ' ,, ., ~ , , .
~066708 are shown in Tables X - XI; the compounds tested were 3-phenyl-5-(o-carboxyphenyl) isoxazole (Compound A), 2-(o-carboxyphenyl)-5-phenyl-1,3~4-oxadiazole (Compound 3~(o-car~oxyphenyl~-5-phenyl-1,2,4-tria~ole (Compound C) and 3 phenyl-5-(o-carboxyphenyl,1,2~4-oxadiazole (Compound D).
TABLE X
. . ~ ,~ .... _ ......... _ Compound Rate %Growth Reduction (52 days) kg/ha Chrysanthemums Brussels Soy-. sprout bean -........................... .
D 5 -1 22 s 73 s D 2 _16 1 s 68 s A 5 -4 26 s 80 s A 2 -10 7 58 s B 5 -27 -9 s 80 s 3 1 2 -13 -3 s 1 88 s S = side shoots :
.:In nearly all cases,compounds A and D caused side shoots on Brussels sprouts and soybean. However whilst ;Brussels sprouts were only stunted by these two compounds at the higher rate, soybean proved very sensitive to all `~10 of compounds A, B and D at both high and low rates giving ~short green plants with some leaf curl.
. . .
. : ; ;~
. . . ~ .
, ~ , . ~, : . .
' : : ,`` . . .
.
Both compounds A and B caused marked stunting of Italian rye grass (Lolium multiflorum)with a certain amount of leaf scorch; the results are shown in Table XI.
- TABLE XI
, , r _ Compound Rate % reduction in growth compared kg/ha with untreated grass .~ . . ~
First Assessment Second Assessment : _ (9) (29) ` C 2 17 54 .. _ _ . . . _ . .__ ., .
Assessments were made by ta~ing fresh weights of cut grass . 5 (g). Figures in brackets de~ote time of assessment as days : after spraying.
, s Compound C as sprayed onto plants grown in 10 cm pots at about the 4th leaf stage, at a rate of 5 kg/ha (1000 l/ha).
The results are shown in Table XII.
.
:~ , .
.
,, . . . ., . - - . -. , ..":, : , . : - -.
, ~ . : ., ... ; :., , ~ . :
1066~08 TABLE XII
.
.: . - .......... - . ........... _ , CompoundPercent growth reduction compared with untreated plants Tomato Brussels Soyabean Sprout Int. Final Int. Final Int. Final -36* -35- 10 -12 56- 67*
*epinasty. Negatlve figures are growth increases compared with check plants, Plots measurlng 2 x 2 metres were marked out on a short sward of St. Augustine grass in the field in the U.S.A. Sprays of 5,60 ! 2,24 or 1.12 kg/hectar~
; of Compound D were applied to the grass on respective ; plots. There were two replicate plots for each treatment '~ and two untreated control areas.
- Phytotoxicity of the chemical sprays was assessed 6 and 13 days after treatment and 14 days after treatment, the plots were cut and the grass weighed. Results in Table XIII below show that Compound D retarded the growth of the grass while inducing only neglible damage.
.
i ~ -25-.
, ... . .
.. .. .
.. . . . ...
,,, ~,, . ; . .
~066708 TABLE XIII
~ . . _ , __ _ . .
Compound D Percent Phytotoxlcity Fresh Wt(g) Rate _ kg/hectare 6 DAT 13 DAT 14 DAT
I .
5.60 1,5 1.5 825 2~24 2 0.5 605 1.12 O O 1190 (DAT = days after treatment) Plots 2 rows (approx. 1.2 m wide) and 15 m. in length were marked out in a crop of an indeterminate variety of soyabean growing the the field in the U.S.A. and were sprayed when 10 per cent of the plants were in flower with Compound D at rates equivalent to 4.~8, 2.24 or ;- 1.12 kg/hectare. Other plots were retained untreated as controls. There were two replicates of each treatment.
Aqueous suspensions of Compound D were prepared by diluting an appropriate volume of the miscible liquid composition of Example 20 below with a solution of 0.05 per cent Agral 90 and were sprayed in a volume equivalent ` to 300 litres/hectare.
The average height of plants in each treatment was -; 15 determined at intervals after spraying by measuring 10 plants at random in each plot. As will be seen from Table XIV below, the treated soyabean plan~s were markedly - , , .. . . . : . .. ..
. .,: . - , - .. . ... . . . .. .
,. . .. ~ .. .. .
.. . , .. . . . . . . . ~ . . ., .: . ~ , .. :
,, ::, . : . .; . -.:
. . , . ,, :
... ,, ... .. ~ , .
shortened b~ the Compound D spr~s and this growth retardation resulted in a complete absence of lodglng which was present ln the controls and in other plants in the surrounding field. The beans in each plot were picked and weighed 90 days after treatment. The average weight of bean found in each treatment is shown in the Table and indicates that at only 4.48 kg/hectare of Compound D was there a yleld decreàse. At 2.24 and 1.12 kg/hectare, Compound D increased bean yields.
TABLE XIV
. ._ ,. _ Compound DMean Plant height Final mean bean yield Rate lb/acre (cm) (kg)/plot (adjusted to zero percent . 11 DAT 18DAT 27DAT moisture).
.
TABLE IV
: , Test Plant Effect of foliar application of 3~ ~-carboxyphenyl~-5~phenylisoxazole '~i f Barley 10% reduction in growth Tomato Reduced leaf area Brussel Sprouts Accelerated leaf senescence i .- - .: , , , ;: : : . , ,: :
. , . - , . . ..
, , : , : . . , : . : .
:: , , . . . :
.: . .. ,, . ." .
, , . : , :
Example 3 A grass sward in an old pasture was cut to a constant level and then dressed with nitrogenous fertilizer to encourage vigourus new growth. Plots (3 x 2 m) were pegged out on the grass and 10 days afterwards a group of 3 such plots was sprayed with a dilute aqueous emulsion comprising 3-to-carboxyphenyl]-5-phenylisoxazole at a rate equivalent to 1 kg per hectare, and a second group ;` of 3 plots was retained untreated as a control. The a~ueous sprays were applied at a volume equivalent to 400 litres/
hectare.
Observations of the plots were made 14 days and 22 days after treatment and it was notice~ that the grass in the treated plots had grown considerably less than that in the control area. The results are presented in Table V
` below.
~ Table V
;~J
. . . ,,,.
Rate of Application of ~ Growth reduction of rass Active Ingredinet Compound After 14 days After ~ days ~. . _ .. ..
, 20 1 kg/ha 68 61 2 kg/ha 73 77 ~ . . . ._.
: . . ._ - . .. _ Example 4 This Example illustrates the method of the invention in modifying the root geotropism of plants.
Seeds of cress (LeFidium satirum) were allowed to germinate on agar in a Petri dish until the roots were 1 cm long. Agar compositions, each comprising one of the com- -pounds listed in Table VI below and present in the concentration ,, ' :' indicated therein, were prepared in Petri dishes and three seedlings were transferred to the surface of each of these compositions.
For the purpose of comparison a group of seedlings were transferred to a Petri dish containing agar comprising no active ingredient compound.
Each of these Petri dishes was then turned verti-cally so that their root tips initially pointed horizontally, and were then placed in darkness at 24C ~or 24 hours. At the end o~ this period, the plants were examined for any alteration to their normal response to gravity.
It was observed that the roots of those seedlings ; placed in the agar compositions comprising an active ingre-dient compound had continued to grow horizontally i.e.
t ~ r normal geotropic response had been destroyed. The untreated plants had exhibited a normal response i.e. their , root tips had turned downwards.
Table VI
,.. .. .. _ _. ., .. . _ Active Ingrediènt Compound Concentration (M x 10-6) 3-[o-carboxyphenyl]-5-phenyl-1~2~4-triazole 1 3-phenyl-5-to-carboxyphenyl]-1,2,4-oxadiazole 0.1 5-lo-carboxyphenyl]-3-phenylisoxazole . ' .. '-".'.'"''' .. ~ ,.' ~ ' .
,. . .
f -, ' , ....
,, : .:.... .: . .
This Example lllustrates the method of the invention in modlfylng the growth of the plant species Arabidopsis thaliana.
An aqueous nutrlent medium comprislng a suitable small concentration of each of the lngredients potassium dihydrogen phosphate, potasslum nitrate, calcium nitrate, and magneslum sulphate was prepared and the pB of this medium was adjusted to 6Ø A small amount of an acetone solutlon of each of the compounds listed in Table VII
below was added to an aliquot of the nutrient medlum to provide the active ingredient concentration shown in this Table.
Each aliquot was then mixed with sufficient molten agar to solidify it, and 7 mls of each mixture was poured into a sterilized test tube which was then plugged with cotton wool. Each test tube was then seeded with a single seed of Arabldopsis thaliana. Several test tubes containing solidified nutrient medium and not comprising - an active ingredient compound was also seeded.
After standing at 4C for 24 hours all the test tubes were maintained at 25C, at 65% humidity, and continuously illuminated at 15 t to 20,000 lux from fluorescent tubes. Germination of the seeds occurred within 72 hours and growth was allowed to proceed for 20 days. At the end of this period it was observed that the pattern of growth of both the foliage and roots of those plants grown in the agar compositions comprising an active , - :, ; ~ '' " ~ .
. " ., .' -' ' ' '' ,: .,: ~,.
.. . . . . . . . . . .
''' "; ~ ' ' .. : .:
.
. . . . .. . .
, ", :, , ' compound was markedly different from that of the untreated plants.
Table VII
Active Ingredient Compound Concentration (ppm) . .
,~ 5-(o-carboxyphenyl)-3-phenylisoxazole 0.1 2-(o-carboxyphenyl)-5-phenyl-1,3,4-oxadiazole 0.5 3-(o-carboxyphenyl)-5-phenyl-1,2,4-triazole 4.0 ~-phenyl-5-(o-carboxyphenyl-1,2,4-oxadiazole 1.0 Example 6 A dilute aqueous emulsion of each of the compounds ; listed in Table VII was sprayed onto separate plots of soil ` at a rate equivalent to 1 to 8 kg/ha of active ingredient and a volume equivalent to 1000 litres per hectare. Seeds of peas, mustard, barley, maize, linseed, and ryegrass ,,r~ were then sown in each plot and allowed to germinate and mature. Each species of plant in each plot exhibited plant ~ growth regulatory effects in the form of either leaf ``~ 20 epinasty, anti-geotropic root growth, or loss of apical dominance.
Example 7 ---This Example illustrates the plant growth regu-' lating activity of compositions of the invention when applied to s variety of plant species in both the pre- snd post-.-: .
'.
, -. ~, . . , , , - .
: ................................. -,, , . , , , :.
`` 1066708 -emergent manner.
Seeds of wheat,wild oats, ryegrass, Japanese millet, peas, ipomoea, mustard and sunflower were sprinkled onto the surface of soil in separate boxes and covered with a thin layer of sand. The contents of each box werethen sprayed with a dilute aqueous composition comprising one of the compounds listed in Table VIII and at one of the application rates indicated thereln r The contents of the boxes were then lightly watered wlth an overhead spray and placed ln a glass-house to encourage germination of the seeds. Three weeks later the boxes were removed from the glass-house and the growth pattern of emerged plants was compared to that of a set of untreated control plants to assess the pre-emergent plant growth regulating activity of the compositions applied. The results are presented in Table VIII.
In addition,seeds of whea~ wild oats, ryegrass, Japanese millet, peas, ipomoea, mustard, and sunflower were covered with sand, lightly watered in the manner described above, and then placed in a glass-house for one week to -permit germination of the seeds and plant growth to a height of 4 to 5 inches. The boxes were then removed from the glass-house and the contents of each box weresprayed with a dilute aqueous composition comprising as active ingredient one of the compounds listed in Table VIII and at one of the application rates indicated therein.
. ,,' ~, .," ' . ', ;;''.' ' . ' ... .
,. . . , -; "
- ~ 1066708 After spraying the boxes Were returned to the glass-house for a further 3 weeks. The growth pattern of the plants was then compared with that of a set of untreated plants to assess the post-emergent plant growth regulating activity of the compositions applied. The results are presented in Table VIII.
TABLE VIII
_ Actlve Ingredient Plant - Plant Growth Pattern*
Compound Species Pre-emergence Post-ëmergence at appllcation at application .~ _rate * 10 rate o~: 10 . wheatSt ep0 Sl St : Watds 0 epSl St Sl St ryegrass epep 0 Sl St 3-(o-carboxy- Japanese ep ep St St phenyl)-5-phenyl millet : -1,2,4-triazole : peasSv St St 0 0 . ipomoea St Sv St St St mustard St Sv St St 0 Sunflower Sv St Sv St Sl St St ._ wheatSt S1 St 0 0 wild 0 Sl St 0 0 3-phenyl-5- ~- oats carboxypheny~ -.~ 1,2,4-oxadiazole ryegrass St St _ 0 _ _ _ millet St St _ St .
' ~, , , : ::
: ,. , : , ,, :
' ' '' ' , ' ' ~'' ' ;: ~ . , TA~LE VIII continued Actlve Ingredient Plant Plant Growth Pattern*
Compound Specles I _ Pre-emergence Post-emergence at application at application rate ** of: rate of:
~ -5 10 10 PeasSv St Sv St O O
ipomoead Sv St St St mustardd Sv St St St sunflower~ Sv St ¦ Sv St ¦ S
* Plant growth pattern compared to control set of untreated plants:
S1 St = slightly stunted St = stunted Sv St = severely stunted ep = leaf epinasty O = substantially unaffected d = plant died ` - = no test was performed at this concentration.
, 10 ** Kilograms per hectare of active ingredient compound.
This Example illustrates the use of compositions of the ~vention in regulating the growth of two species of grass.
Seeds of Wimmera ryegrass and cocksfoot were sprinkled onto the surface of soil in separate boxes and covered with ., ., ., : . ,., .. ~ ; . . :
.. .. . . .. . .
. .
. ., ~ , . ,, -" , ., ~ . ~; :
, : . ; ~ , . ::
. .
a thln layer of sand, lightl~ watered and then placed in a glass-house to germinate and grow When the plants were approximately 10 cm high, a box of each specles was sprayed with a volume of a dilute aqueous emulsion of one of the active ingredient compounds listed in Table IX
e~uivalent to 1000 litres per hectare and at the application rate indicated therein. The plants were then returned to the glass-house and after a period of twenty days their growth was compared to that of an untreated set of control plants. The results are presented in Table IX.
TABLE IX
:. _ _ . _ Active Ingredlent Application Reduction in height of Compound Ratecompared to control (kg/ha) plants _ , WimmeraCocksfoot ryegrass 3-lo-carboxypheny~ 1 19 12 -5-phenyl-1,2,4- 5 24 8 triazole ~
3-phenyl-5-~o- 1 19 8 carboxypheny~ - 5 19 8 - 1,2,4-oxadiazole 2-.(o-carboxyphenyl 1 10 16 -5-phenyl-1,3,4- 5 24 28 oxadiazole .
Certaln of the compounds of formula (I) were tested on various plants, e.g. chrysanthemums, Brussels sprout and soybean for growth regulating properties. The results , ,. ~ . , . . . - - . .-. .
.
- . : . , . . , , .. ,. : .
- : :, . . , : , . ~ . .
. , , - , , ' :' ' ' ,, ., ~ , , .
~066708 are shown in Tables X - XI; the compounds tested were 3-phenyl-5-(o-carboxyphenyl) isoxazole (Compound A), 2-(o-carboxyphenyl)-5-phenyl-1,3~4-oxadiazole (Compound 3~(o-car~oxyphenyl~-5-phenyl-1,2,4-tria~ole (Compound C) and 3 phenyl-5-(o-carboxyphenyl,1,2~4-oxadiazole (Compound D).
TABLE X
. . ~ ,~ .... _ ......... _ Compound Rate %Growth Reduction (52 days) kg/ha Chrysanthemums Brussels Soy-. sprout bean -........................... .
D 5 -1 22 s 73 s D 2 _16 1 s 68 s A 5 -4 26 s 80 s A 2 -10 7 58 s B 5 -27 -9 s 80 s 3 1 2 -13 -3 s 1 88 s S = side shoots :
.:In nearly all cases,compounds A and D caused side shoots on Brussels sprouts and soybean. However whilst ;Brussels sprouts were only stunted by these two compounds at the higher rate, soybean proved very sensitive to all `~10 of compounds A, B and D at both high and low rates giving ~short green plants with some leaf curl.
. . .
. : ; ;~
. . . ~ .
, ~ , . ~, : . .
' : : ,`` . . .
.
Both compounds A and B caused marked stunting of Italian rye grass (Lolium multiflorum)with a certain amount of leaf scorch; the results are shown in Table XI.
- TABLE XI
, , r _ Compound Rate % reduction in growth compared kg/ha with untreated grass .~ . . ~
First Assessment Second Assessment : _ (9) (29) ` C 2 17 54 .. _ _ . . . _ . .__ ., .
Assessments were made by ta~ing fresh weights of cut grass . 5 (g). Figures in brackets de~ote time of assessment as days : after spraying.
, s Compound C as sprayed onto plants grown in 10 cm pots at about the 4th leaf stage, at a rate of 5 kg/ha (1000 l/ha).
The results are shown in Table XII.
.
:~ , .
.
,, . . . ., . - - . -. , ..":, : , . : - -.
, ~ . : ., ... ; :., , ~ . :
1066~08 TABLE XII
.
.: . - .......... - . ........... _ , CompoundPercent growth reduction compared with untreated plants Tomato Brussels Soyabean Sprout Int. Final Int. Final Int. Final -36* -35- 10 -12 56- 67*
*epinasty. Negatlve figures are growth increases compared with check plants, Plots measurlng 2 x 2 metres were marked out on a short sward of St. Augustine grass in the field in the U.S.A. Sprays of 5,60 ! 2,24 or 1.12 kg/hectar~
; of Compound D were applied to the grass on respective ; plots. There were two replicate plots for each treatment '~ and two untreated control areas.
- Phytotoxicity of the chemical sprays was assessed 6 and 13 days after treatment and 14 days after treatment, the plots were cut and the grass weighed. Results in Table XIII below show that Compound D retarded the growth of the grass while inducing only neglible damage.
.
i ~ -25-.
, ... . .
.. .. .
.. . . . ...
,,, ~,, . ; . .
~066708 TABLE XIII
~ . . _ , __ _ . .
Compound D Percent Phytotoxlcity Fresh Wt(g) Rate _ kg/hectare 6 DAT 13 DAT 14 DAT
I .
5.60 1,5 1.5 825 2~24 2 0.5 605 1.12 O O 1190 (DAT = days after treatment) Plots 2 rows (approx. 1.2 m wide) and 15 m. in length were marked out in a crop of an indeterminate variety of soyabean growing the the field in the U.S.A. and were sprayed when 10 per cent of the plants were in flower with Compound D at rates equivalent to 4.~8, 2.24 or ;- 1.12 kg/hectare. Other plots were retained untreated as controls. There were two replicates of each treatment.
Aqueous suspensions of Compound D were prepared by diluting an appropriate volume of the miscible liquid composition of Example 20 below with a solution of 0.05 per cent Agral 90 and were sprayed in a volume equivalent ` to 300 litres/hectare.
The average height of plants in each treatment was -; 15 determined at intervals after spraying by measuring 10 plants at random in each plot. As will be seen from Table XIV below, the treated soyabean plan~s were markedly - , , .. . . . : . .. ..
. .,: . - , - .. . ... . . . .. .
,. . .. ~ .. .. .
.. . , .. . . . . . . . ~ . . ., .: . ~ , .. :
,, ::, . : . .; . -.:
. . , . ,, :
... ,, ... .. ~ , .
shortened b~ the Compound D spr~s and this growth retardation resulted in a complete absence of lodglng which was present ln the controls and in other plants in the surrounding field. The beans in each plot were picked and weighed 90 days after treatment. The average weight of bean found in each treatment is shown in the Table and indicates that at only 4.48 kg/hectare of Compound D was there a yleld decreàse. At 2.24 and 1.12 kg/hectare, Compound D increased bean yields.
TABLE XIV
. ._ ,. _ Compound DMean Plant height Final mean bean yield Rate lb/acre (cm) (kg)/plot (adjusted to zero percent . 11 DAT 18DAT 27DAT moisture).
4 46 56 60 5.25 2 48 60 69 6.65 1 49 62 74 7.25 0 (CoAtrol)-70 87 94 6.50 _ . . .
DAT = days after treatment The following Example illustrates the stimulation of plant growth by a compound of the invention.
Seedlings of grapevine were grown singly in 10 cm diameter pots containing compost. When they had a stem : . . ,: , . ..
.
.
' ' " `, '' ', . ' ' ' , , ': " ' ~ - ' ' :
,, ~ , . . .
', ,; ' ~ ' ' , ' :
length of approximately 5 cm, they were sprayed with Compound A at rates equivalent to 5 and lO kg/ha in a volume equivalent to 1000 l/ha of an aqueous solution of O.l per cent Agral 90. Other seedling plants were left untreated as controls. There were 8 replicate plants per treatment.
The length of the stem of each plant was measured from compost level to apex, immediately prior to spraying and at 13 and 19 days after treatment and the number of leaves per plant was counted after 29 days. The results are shown ln Table XV.
', ;
.
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, .. , . .... , :
, . ,1:~, o h ~O~
.
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r4 ~
~4 _~
~ U~ ~ ~
~ C~ 1~ ~ ~1 : ~~ a~
~ . ' ~' ~ ~ ~ ~ O
.. ; ~ _ _~ _l _l ..___ ~ S ~ u~
~:~. ~ ~ ~ _ O ~ o~
,~ ~ ,~ ~ ~1 ' ~ ~
,. C~
~' O U~
. __ ,.' ~ ~ O
~ 0~1 50 ." ,a ~0 ~ u~ O
. ~ O - . , :~ ~ ~ .`
L
~,29--, ... . ....
, -` 1066708 Although there is a slight tendency for an increased rate of leaf production after plant were sprayed with Compound A, the marked stimulations of growth were accounted for by a more rapid rate of internode extension.
2-(o-carboxyphenyl)-5-phenyl-1,3,4-thiadiazole (Compound E), 2-(o-carboxyphenyl)-5-(0-chlorophenyl)-1,3,4-thiadlazole (Compound F) and 2-(o-carbox~phenyl)-
DAT = days after treatment The following Example illustrates the stimulation of plant growth by a compound of the invention.
Seedlings of grapevine were grown singly in 10 cm diameter pots containing compost. When they had a stem : . . ,: , . ..
.
.
' ' " `, '' ', . ' ' ' , , ': " ' ~ - ' ' :
,, ~ , . . .
', ,; ' ~ ' ' , ' :
length of approximately 5 cm, they were sprayed with Compound A at rates equivalent to 5 and lO kg/ha in a volume equivalent to 1000 l/ha of an aqueous solution of O.l per cent Agral 90. Other seedling plants were left untreated as controls. There were 8 replicate plants per treatment.
The length of the stem of each plant was measured from compost level to apex, immediately prior to spraying and at 13 and 19 days after treatment and the number of leaves per plant was counted after 29 days. The results are shown ln Table XV.
', ;
.
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-28- .
, .. , . .... , :
, . ,1:~, o h ~O~
.
~ ~ ~D I
r4 ~
~4 _~
~ U~ ~ ~
~ C~ 1~ ~ ~1 : ~~ a~
~ . ' ~' ~ ~ ~ ~ O
.. ; ~ _ _~ _l _l ..___ ~ S ~ u~
~:~. ~ ~ ~ _ O ~ o~
,~ ~ ,~ ~ ~1 ' ~ ~
,. C~
~' O U~
. __ ,.' ~ ~ O
~ 0~1 50 ." ,a ~0 ~ u~ O
. ~ O - . , :~ ~ ~ .`
L
~,29--, ... . ....
, -` 1066708 Although there is a slight tendency for an increased rate of leaf production after plant were sprayed with Compound A, the marked stimulations of growth were accounted for by a more rapid rate of internode extension.
2-(o-carboxyphenyl)-5-phenyl-1,3,4-thiadiazole (Compound E), 2-(o-carboxyphenyl)-5-(0-chlorophenyl)-1,3,4-thiadlazole (Compound F) and 2-(o-carbox~phenyl)-
5-(~-chloropehnyl)-1,3,4-thiadlazole (Compound G) were tested in varlous plants.
The plants were grown in 7.5 cm pots and sprayed at approxlmately the 2~ leaf stage for the tomato, Brussels ; sprout and soyabean plants, and 11 days after sowing for the cereal. Sprays were at 5 kg/ha (1000 l/ha) of the compounds and the plants were assessed visually 9 days after treatment.
`':
-. , l COMPOUNDP ~RCENTAGE REDUCTII ~N IN GROW rH
Wheat Barley Timothy Tomato Brussels Soya-` grass sprout bean --E 15 15 15 0* 20 70*
F O 15 O 0* 30 50*
G 60 15 O 80 50* 50 i *leaf curling and stem twisting The results show that the compound have plant growth retardant activity.
.
:. , '. ',, ' . ::
This Example describes the preparation of 3-phenyl-5-to-carboxyphenyl)isoxazole (Compound A) according to the equations:
~C CH2-11 ~ 2 C-C~2-C~
heat .C\,~ , rC
, - , ,. " , ,: . ', " - - ': , ,:
'- ' ' , , . , '', ., " --` 1066708 l-o-carboxyphenyl-3-phenylpropane-1,3-dione (1.4 g) was dissolved in glacial acid (20 ml) and hydroxylamine hydrochloride (0.5 gm) and sodium acetate (1.0 gm) added.
The mixture was boiled under reflux ~or 2 hours. The yellow solution was poured into water (100 ml) and the precipitated solid was collected by filtration and then crystallised from aqueous ethanol to yield 1.1 g of the product as yellow plates, m.p. 193-195C.
:.
This Example illustrates another wa~, which i5 in fact preferred, for preparing Compound A.
2-Carboxybenzaldehyde (15 g) and acetophenone (12 g) were dissolved in ethanol (60 ml). A solution of sodium hudroxide (8 g) in water (40 ml) was added and the mixture ~stirred at room temperature for 4-6 hours. The mixture was then poured into water (500-600 ml) and the solution .` acidified. The oily product slowly solidified and was -`` collected and crystallized from ethanol td give o~-phenacyl phthalide as colourless needles, m.p. 143-145.
Yield 21-23 g (88-92%).
0~-Phenacyl phthalide (5 g) was suspended in dry benzene (75 ml) and the mlxture stirred and bo'led under reflux~
Bron~ne~ ml) was added dropwise over 15 min to:~he solution, and stirring and refluxing were continued for 1 hr. The 25 solution was then filtered and the benzene removed in vacuo. -The crude bromo compound was suspended in ethanol (50 ml) and hydroxylamine hydrochloride (4.2 g) and anhydrous sodium acetate (8.2 g) added and the mixture boiled under reflux `` 1066708 for 2 hours. About half the ethanol was xemoved in vacuo, and 5~ sodi~m bicarbonate solution (200 ml) added.
The mixture was then filtered through Celite, and the filtrate acidified with conc. hydrochloric acid. The crude product was filtered off and recrystallized from aqueous ethanol to glve the isoxazole (2.7 g, 51~) as fine buff-coloured plates, m.p. 190-193.
Benzoyl hydrazide (6,8 g) (from ethyl benzoate and hydrazine hydrate - see below) was dissolved in glacial acetlc acid (30 ml) and added to 2-carboxybenzaldehyde (7,5 g) in glacial acetic acid (50 ml). The mixture was warmed briefly and allowed to stand at room temperature for 30 mins, during which time the product crystallized.
It was filtered and washed with glacial acetic acid-lS -petroleum ether (1:2) and dried. The hydrazone ~12.6 g, 94%) was obtained as a colourless powder, m.p. 201-203.
The hydrazone (5.4 g) was suspended in glacial acetic acid (75 mlj and finely-powdered anhydrous sodium acetate I -; (8.0 g) was-added. Then bromine ( 1 ml) in glacial ¦ -acetic acid (10 ml) was added to the rapidly-stirred mixture. After stirring for about 5 mins, the brick-red precipitate was removed by filtration. The precipitate was then suspended in glacial acetic acid (40-50 ml) and the mixture boiled. The solid mhterial gradually dissoived and the solution became pale orange. After 10-li mins, the ~ ¦
volume had been reduced to about 25 ml, and then wa~er was added slowly until crystallization o~ the product commenced.
I ' .
~ ;
Cooling gave 2-(o~carboxyphenyl)-5~phenyl-1,3,4~
-oxadiazole (3.6 g, 70%) as colourless plates, m.p.
178-180. The product may be purified further by re-crystallization from aqueous ethanol.
The hydraz~de starting material can be made as follows. Ethyl benzoate` (40 g) and hydrazine hydrate (50 ml) were refluxed gently for 5-6 hrs. On cooling, the react~on mixture solidified and the solid material was crystallized from water to give the hydrazide (33 g, 90~) as fine, buff-coloured needles, m.p. 122-124.
This Example illustrates the preparation of 3-[o-carboxyphenyl]-S-phenyl-1,2,4-triazole according to the equations ~ ~N~-NN2 ~ CN ~ ) .. ..
-`. ~ / .
.~ ~C02H ~
-- ` .
.
`
. ' ' ' `
, i ' ' - .... .. .. . .
.
o-Toluhydrazide (20 g) and benzonitrile (150 ml) were treated ln an autoclave at 250 for 3 hrs. The contents were allowed to cool, diluted with ether t200 ml) and extracted with 5~ NaOH (3 x SO ml). The combined alkaline extracts were washed with ether (2 x 50 ml)and brought to pH 5 with 10% HCl. 3-o-Tolyl-5-phenyl-1,2,4_ triazole precipitated as a gummy solid (18 g, 57~) which was used without purification in the next step.
The o-tolyl-triazole (crude product, 18 g) was dissolved in 10% NaOH (300 ml) and KMnO4 (45 g) added.
The mixture was s~i~rred under reflux or 1 hr, filtered through Celite and acidified with conc.HCl. The crude product which precipitated was boiled with ethanol (100 ml) for 10 min, chilled and collected to give 3-o-carboxyphenyl- ¦
5-phenyl-1,2,4-triazole was obtained as a white microcrystalline powder (10 g, 50%)~ mp 237-239. !-o-Carboxyacetophenone (14.7 g) was dissolved in dry ' benzene (100 ml) and treated with bromine (4 5 ml). After the addition o~ the first few drops of bromine, the flask was warmed to initiate the reaction. When the solution had ~ ' ~eco~e decolourized, the remaining bromine was added rapidly dropwise, with stirring. Stirring was continued for 5 mins after the addition was complete, then the solvent was ~
removed in vacuo. The syrupy residue crystallised on trituration -''with light'petrole~m (boiling range 60-80) and the crude -o-carboxyphenacyl bromide (quantitati~e yield, m.p. 127-128) was used dlrectly in the next step. ' '-.: " . .' 1~
", ", . . ..
A solution of thiobenzamide (1.45 g) and _-carboxyphenacyl bromide (2.45 g) in ethanol (50 ml) was refluxed for 24 hrs. The solvent was removed in vacuo and the product recrystallised from aqueous ethanol to give 2-phenyl-4- (o-ethoxycarbonylphenyl)-thiazole (2.2S g, 73%) as colourless needles, m.p. 77-79. The ethyl ester (4.5 g) was heated under relux for 1 hr in ethanol (50 ml) containing 10% sodium hydroxide solution (10 ml). The mixture was then poured into water (200 ml) and acidified with 10% hydrochloric acid. On chilling, ` the product, i.e. 2-phenyl-4-(o-carboxyphenyl)-thiazole, crystallised as fine needles (4.1 g), m.p. 159-161.
This Example illustrates a composition according to the invention in the form of an emulslfiable concentrate formulation, suitable for dilution with water.
Weight %
`~ 3-Phenyl-S-(o-carboxyphenyl)-1,2,4~oxadiazole 20 Condensate of 2 moles ethylene oxide with a ; mixture of oleyl a~d cetyl alcohols 5 Mixture of calcium dodecyl benzene sulphonate with ethoxylated castor oil S
Technical grade methylcyclohexanone 70 100~ , -.: ' ', . ' ' ` ' . . ': , . ~ ' . ' ''. ' ' . .' ' .
, ' ' ' ` ' ', ' ' ` ','' '; ," ~
.. . . . . . .
`--` 1066708 This Example illustrates a solid composition according to the invention suitable for application in the form of granules.
Weight 2-(o carboxyphenyl)-5~phenyl-1,3,4-oxadiazole 3 Pumice granules 97 This Example illustrates a miscible liquid composition.
Weight 3-Phenyl-5-(o-carboxyphenyl)-1,2,4-oxadiazole 20 Triethanolamine 12.2 Isopropanol 20 Water to 100 R~P/SG 37 ', . :
''''. ~ . : ~ ' : ' ' ' " ' ''' ~",' ' "' ~ :
The plants were grown in 7.5 cm pots and sprayed at approxlmately the 2~ leaf stage for the tomato, Brussels ; sprout and soyabean plants, and 11 days after sowing for the cereal. Sprays were at 5 kg/ha (1000 l/ha) of the compounds and the plants were assessed visually 9 days after treatment.
`':
-. , l COMPOUNDP ~RCENTAGE REDUCTII ~N IN GROW rH
Wheat Barley Timothy Tomato Brussels Soya-` grass sprout bean --E 15 15 15 0* 20 70*
F O 15 O 0* 30 50*
G 60 15 O 80 50* 50 i *leaf curling and stem twisting The results show that the compound have plant growth retardant activity.
.
:. , '. ',, ' . ::
This Example describes the preparation of 3-phenyl-5-to-carboxyphenyl)isoxazole (Compound A) according to the equations:
~C CH2-11 ~ 2 C-C~2-C~
heat .C\,~ , rC
, - , ,. " , ,: . ', " - - ': , ,:
'- ' ' , , . , '', ., " --` 1066708 l-o-carboxyphenyl-3-phenylpropane-1,3-dione (1.4 g) was dissolved in glacial acid (20 ml) and hydroxylamine hydrochloride (0.5 gm) and sodium acetate (1.0 gm) added.
The mixture was boiled under reflux ~or 2 hours. The yellow solution was poured into water (100 ml) and the precipitated solid was collected by filtration and then crystallised from aqueous ethanol to yield 1.1 g of the product as yellow plates, m.p. 193-195C.
:.
This Example illustrates another wa~, which i5 in fact preferred, for preparing Compound A.
2-Carboxybenzaldehyde (15 g) and acetophenone (12 g) were dissolved in ethanol (60 ml). A solution of sodium hudroxide (8 g) in water (40 ml) was added and the mixture ~stirred at room temperature for 4-6 hours. The mixture was then poured into water (500-600 ml) and the solution .` acidified. The oily product slowly solidified and was -`` collected and crystallized from ethanol td give o~-phenacyl phthalide as colourless needles, m.p. 143-145.
Yield 21-23 g (88-92%).
0~-Phenacyl phthalide (5 g) was suspended in dry benzene (75 ml) and the mlxture stirred and bo'led under reflux~
Bron~ne~ ml) was added dropwise over 15 min to:~he solution, and stirring and refluxing were continued for 1 hr. The 25 solution was then filtered and the benzene removed in vacuo. -The crude bromo compound was suspended in ethanol (50 ml) and hydroxylamine hydrochloride (4.2 g) and anhydrous sodium acetate (8.2 g) added and the mixture boiled under reflux `` 1066708 for 2 hours. About half the ethanol was xemoved in vacuo, and 5~ sodi~m bicarbonate solution (200 ml) added.
The mixture was then filtered through Celite, and the filtrate acidified with conc. hydrochloric acid. The crude product was filtered off and recrystallized from aqueous ethanol to glve the isoxazole (2.7 g, 51~) as fine buff-coloured plates, m.p. 190-193.
Benzoyl hydrazide (6,8 g) (from ethyl benzoate and hydrazine hydrate - see below) was dissolved in glacial acetlc acid (30 ml) and added to 2-carboxybenzaldehyde (7,5 g) in glacial acetic acid (50 ml). The mixture was warmed briefly and allowed to stand at room temperature for 30 mins, during which time the product crystallized.
It was filtered and washed with glacial acetic acid-lS -petroleum ether (1:2) and dried. The hydrazone ~12.6 g, 94%) was obtained as a colourless powder, m.p. 201-203.
The hydrazone (5.4 g) was suspended in glacial acetic acid (75 mlj and finely-powdered anhydrous sodium acetate I -; (8.0 g) was-added. Then bromine ( 1 ml) in glacial ¦ -acetic acid (10 ml) was added to the rapidly-stirred mixture. After stirring for about 5 mins, the brick-red precipitate was removed by filtration. The precipitate was then suspended in glacial acetic acid (40-50 ml) and the mixture boiled. The solid mhterial gradually dissoived and the solution became pale orange. After 10-li mins, the ~ ¦
volume had been reduced to about 25 ml, and then wa~er was added slowly until crystallization o~ the product commenced.
I ' .
~ ;
Cooling gave 2-(o~carboxyphenyl)-5~phenyl-1,3,4~
-oxadiazole (3.6 g, 70%) as colourless plates, m.p.
178-180. The product may be purified further by re-crystallization from aqueous ethanol.
The hydraz~de starting material can be made as follows. Ethyl benzoate` (40 g) and hydrazine hydrate (50 ml) were refluxed gently for 5-6 hrs. On cooling, the react~on mixture solidified and the solid material was crystallized from water to give the hydrazide (33 g, 90~) as fine, buff-coloured needles, m.p. 122-124.
This Example illustrates the preparation of 3-[o-carboxyphenyl]-S-phenyl-1,2,4-triazole according to the equations ~ ~N~-NN2 ~ CN ~ ) .. ..
-`. ~ / .
.~ ~C02H ~
-- ` .
.
`
. ' ' ' `
, i ' ' - .... .. .. . .
.
o-Toluhydrazide (20 g) and benzonitrile (150 ml) were treated ln an autoclave at 250 for 3 hrs. The contents were allowed to cool, diluted with ether t200 ml) and extracted with 5~ NaOH (3 x SO ml). The combined alkaline extracts were washed with ether (2 x 50 ml)and brought to pH 5 with 10% HCl. 3-o-Tolyl-5-phenyl-1,2,4_ triazole precipitated as a gummy solid (18 g, 57~) which was used without purification in the next step.
The o-tolyl-triazole (crude product, 18 g) was dissolved in 10% NaOH (300 ml) and KMnO4 (45 g) added.
The mixture was s~i~rred under reflux or 1 hr, filtered through Celite and acidified with conc.HCl. The crude product which precipitated was boiled with ethanol (100 ml) for 10 min, chilled and collected to give 3-o-carboxyphenyl- ¦
5-phenyl-1,2,4-triazole was obtained as a white microcrystalline powder (10 g, 50%)~ mp 237-239. !-o-Carboxyacetophenone (14.7 g) was dissolved in dry ' benzene (100 ml) and treated with bromine (4 5 ml). After the addition o~ the first few drops of bromine, the flask was warmed to initiate the reaction. When the solution had ~ ' ~eco~e decolourized, the remaining bromine was added rapidly dropwise, with stirring. Stirring was continued for 5 mins after the addition was complete, then the solvent was ~
removed in vacuo. The syrupy residue crystallised on trituration -''with light'petrole~m (boiling range 60-80) and the crude -o-carboxyphenacyl bromide (quantitati~e yield, m.p. 127-128) was used dlrectly in the next step. ' '-.: " . .' 1~
", ", . . ..
A solution of thiobenzamide (1.45 g) and _-carboxyphenacyl bromide (2.45 g) in ethanol (50 ml) was refluxed for 24 hrs. The solvent was removed in vacuo and the product recrystallised from aqueous ethanol to give 2-phenyl-4- (o-ethoxycarbonylphenyl)-thiazole (2.2S g, 73%) as colourless needles, m.p. 77-79. The ethyl ester (4.5 g) was heated under relux for 1 hr in ethanol (50 ml) containing 10% sodium hydroxide solution (10 ml). The mixture was then poured into water (200 ml) and acidified with 10% hydrochloric acid. On chilling, ` the product, i.e. 2-phenyl-4-(o-carboxyphenyl)-thiazole, crystallised as fine needles (4.1 g), m.p. 159-161.
This Example illustrates a composition according to the invention in the form of an emulslfiable concentrate formulation, suitable for dilution with water.
Weight %
`~ 3-Phenyl-S-(o-carboxyphenyl)-1,2,4~oxadiazole 20 Condensate of 2 moles ethylene oxide with a ; mixture of oleyl a~d cetyl alcohols 5 Mixture of calcium dodecyl benzene sulphonate with ethoxylated castor oil S
Technical grade methylcyclohexanone 70 100~ , -.: ' ', . ' ' ` ' . . ': , . ~ ' . ' ''. ' ' . .' ' .
, ' ' ' ` ' ', ' ' ` ','' '; ," ~
.. . . . . . .
`--` 1066708 This Example illustrates a solid composition according to the invention suitable for application in the form of granules.
Weight 2-(o carboxyphenyl)-5~phenyl-1,3,4-oxadiazole 3 Pumice granules 97 This Example illustrates a miscible liquid composition.
Weight 3-Phenyl-5-(o-carboxyphenyl)-1,2,4-oxadiazole 20 Triethanolamine 12.2 Isopropanol 20 Water to 100 R~P/SG 37 ', . :
''''. ~ . : ~ ' : ' ' ' " ' ''' ~",' ' "' ~ :
Claims (13)
1. A compound of general formula (I):
(I) wherein each of R1 to R10, which may be the same or different, is hydrogen, lower alkyl, halogen, amino, nitro, cyano or -COR11 wherein R11 is hydroxy, lower alkoxy, aralkoxy, aryloxy, unsubstituted amino or -O?]nMn? or -S]Mn? wherein Mn? is an ammonium, alkali metal or alkaline earth metal ion and n is 1 or 2 accordinqly, R1 being -COR11 at least three of R2 to R5 being hydrogen and at least four of R6 to R10 being hydrogen, and wherein Q is a heterocyclic ring which is isoxazole-3,5-diyl, thiazole-2,4-diyl, 1,2,4-triazole-3,5-diyl, 1,3,4-thiadiazole-2,5-diyl, 1,2,4-oxadiazole-3,5-diyl, or 1,3,4-oxadiazole-2,5-diyl.
(I) wherein each of R1 to R10, which may be the same or different, is hydrogen, lower alkyl, halogen, amino, nitro, cyano or -COR11 wherein R11 is hydroxy, lower alkoxy, aralkoxy, aryloxy, unsubstituted amino or -O?]nMn? or -S]Mn? wherein Mn? is an ammonium, alkali metal or alkaline earth metal ion and n is 1 or 2 accordinqly, R1 being -COR11 at least three of R2 to R5 being hydrogen and at least four of R6 to R10 being hydrogen, and wherein Q is a heterocyclic ring which is isoxazole-3,5-diyl, thiazole-2,4-diyl, 1,2,4-triazole-3,5-diyl, 1,3,4-thiadiazole-2,5-diyl, 1,2,4-oxadiazole-3,5-diyl, or 1,3,4-oxadiazole-2,5-diyl.
2. 3-Phenyl-5-(o-carboxyphenyl) isoxazole.
3. 2-(o-Carboxyphenyl)-5-phenyl-1,3,4-oxadiazole.
4. 3-(o-Carboxyphenyl)-5-phenyl-1,2,4-triazole.
5. 3-Phenyl-5-(o-carboxyphenyl)-1,2,4-oxadiazole.
6. 2-Phenyl-4-(o-carboxyphenyl)-thiazole.
7. 2-(o-Carboxyphenyl)-5-phenyl-1,3,4-thiadiazole.
8. 2-(o-Carboxyphenyl)-5-(o-chlorophenyl)-1,3,4-thiadiazole.
9. 2-(o-Carboxyphenyl-5-(o-chlorophenyl)-1,3,4-thiadiazole.
10. A process for preparing a compound according to claim 1, the process comprising :
(1) when a compound of general formula (I) wherein Q
is 1,2,4-triazole-3,5-diyl and R1 is COOH, is required, oxidising a compound of general formula (I) wherein Q is 1,2,4-triazole-3,5-diyl and R1 to R10 are as defined in Claim 1, subject to the replacement proviso that R1 is lower alkyl; or (2) when a compound of general formula (I) wherein Q
is isoxazole-3,5-diyl is required, cyclising a compound of general formula (II):
(II) wherein R1 to R10 are as defined in Claim 1; or (3) when a compound of general formula (I) wherein Q
is isoxazole-3,5-diyl is required, reacting a compound of general formula (III):
(III) wherein R2 to R10 are as defined in claim 1, and X is halogen, with hydroxylamine; or (4) when a compound of general formula (I) wherein Q
is 1,3,4-oxadiazole-2,5-diyl and R1 is COOH is required, oxidising a compound of general formula (I) wherein Q is 1,3,4-oxadiazole-2,5-diyl and R1 to R10 are as defined in claim 1 subject to the replacement proviso that R1 is lower alkyl; or (5) when a compound of general formula (I) wherein Q
is 1,3,4-oxadiazole-2,5-diyl is required oxidising with cyclisation a compound of general formula (IV):
(IV) wherein R1 to R10 are as defined in claim 1; or (6) when a compound of general formula (I) wherein Q
is thiazole-2,4-diyl is required, reacting a compound of general formula (V):
(V) wherein R1 to R5 are as defined in claim 1 and X
is halogen; with a compound of general formula (VI):
(VI) wherein R6 to R10 are as defined in claim 1, and if necessary or desired hydrolysing any ester formed; or (7) when a compound of general formula (I) wherein Q
is 1,3,4-thiadiazole-2,5-diyl and R1 is COOH is required, oxidising a compound of general formula (I) wherein Q is 1,3,4-thiadiazole-2,5-diyl and R1 to R10 are as defined in claim 1 subject to the replacement proviso that R1 is lower alkyl.
(1) when a compound of general formula (I) wherein Q
is 1,2,4-triazole-3,5-diyl and R1 is COOH, is required, oxidising a compound of general formula (I) wherein Q is 1,2,4-triazole-3,5-diyl and R1 to R10 are as defined in Claim 1, subject to the replacement proviso that R1 is lower alkyl; or (2) when a compound of general formula (I) wherein Q
is isoxazole-3,5-diyl is required, cyclising a compound of general formula (II):
(II) wherein R1 to R10 are as defined in Claim 1; or (3) when a compound of general formula (I) wherein Q
is isoxazole-3,5-diyl is required, reacting a compound of general formula (III):
(III) wherein R2 to R10 are as defined in claim 1, and X is halogen, with hydroxylamine; or (4) when a compound of general formula (I) wherein Q
is 1,3,4-oxadiazole-2,5-diyl and R1 is COOH is required, oxidising a compound of general formula (I) wherein Q is 1,3,4-oxadiazole-2,5-diyl and R1 to R10 are as defined in claim 1 subject to the replacement proviso that R1 is lower alkyl; or (5) when a compound of general formula (I) wherein Q
is 1,3,4-oxadiazole-2,5-diyl is required oxidising with cyclisation a compound of general formula (IV):
(IV) wherein R1 to R10 are as defined in claim 1; or (6) when a compound of general formula (I) wherein Q
is thiazole-2,4-diyl is required, reacting a compound of general formula (V):
(V) wherein R1 to R5 are as defined in claim 1 and X
is halogen; with a compound of general formula (VI):
(VI) wherein R6 to R10 are as defined in claim 1, and if necessary or desired hydrolysing any ester formed; or (7) when a compound of general formula (I) wherein Q
is 1,3,4-thiadiazole-2,5-diyl and R1 is COOH is required, oxidising a compound of general formula (I) wherein Q is 1,3,4-thiadiazole-2,5-diyl and R1 to R10 are as defined in claim 1 subject to the replacement proviso that R1 is lower alkyl.
11. A method of regulating the growth of, or killing, a plant, the method comprising applying to the plant or to the locus of the plant, a compound according to any one of claims 1 to 3.
12. A method of regulating the growth of, or killing, a plant, the method comprising applying to the plant or to the locus of the plant, a compound according to any one of claims 4 to 6.
13. A method of regulating the growth of, or killing, a plant the method comprising applying to the plant or to the locus of the plant, a compound according to any one of claim 7 to 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPC023575 | 1975-01-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1066708A true CA1066708A (en) | 1979-11-20 |
Family
ID=3766094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA243,584A Expired CA1066708A (en) | 1975-01-10 | 1976-01-12 | Azol compounds useful as plant growth regulation agents |
Country Status (13)
| Country | Link |
|---|---|
| AU (1) | AU497898B2 (en) |
| BE (1) | BE837454A (en) |
| BR (1) | BR7600132A (en) |
| CA (1) | CA1066708A (en) |
| CH (1) | CH603044A5 (en) |
| DE (1) | DE2600655A1 (en) |
| FR (1) | FR2332705A1 (en) |
| GB (1) | GB1494877A (en) |
| IL (1) | IL48803A0 (en) |
| IT (1) | IT1054759B (en) |
| NL (1) | NL7600152A (en) |
| NZ (1) | NZ179684A (en) |
| ZA (1) | ZA7638B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1579352A (en) * | 1977-05-06 | 1980-11-19 | Lepetit Spa | 3,5-disubstituted-1h-1,2,4-triazoles |
| US4140515A (en) * | 1977-05-12 | 1979-02-20 | Monsanto Company | Aryl-3-isoxazole benzoates as plant growth regulants and herbicides |
| US4135910A (en) | 1977-05-12 | 1979-01-23 | Monsanto Company | Oxadiazol-3-yl-benzoates as plant growth regulants |
| US4210762A (en) * | 1978-08-17 | 1980-07-01 | Monsanto Company | 2[5-(3-Trifluoromethylphenyl)-1,3,4-oxadiazol-2-yl] benzoates |
| US4268299A (en) * | 1978-08-17 | 1981-05-19 | Monsanto Company | Method and composition for plant growth regulation containing trifluoromethyl 1,3,4 oxadiazol benzoates |
| US4229204A (en) * | 1978-12-04 | 1980-10-21 | Monsanto Company | Trifluoromethylphenyl isoxazolyl benzoates |
| US4209629A (en) | 1978-12-20 | 1980-06-24 | Monsanto Company | 3'-(Substituted phenyl)-spiro[isobenzofuran-1(3H),5'(4'H)-isoxazol]-3-ones |
| US4208510A (en) * | 1978-12-20 | 1980-06-17 | Monsanto Company | Preparation of 3-aryl-isoxazol-5-yl benzoates |
| US4223154A (en) * | 1979-03-09 | 1980-09-16 | Monsanto Company | Preparation of 2-(3-aryl-5-isoxazol) benzoyl halide |
| US4197405A (en) * | 1979-02-22 | 1980-04-08 | Monsanto Company | Thermolysis of 3'-(Aryl)-spiro[isobenzofuran-1(3H),5'(4'H)-isoxazol]-3-one |
| US4230866A (en) * | 1979-05-17 | 1980-10-28 | Monsanto Company | Preparation of 3-aryl-isoxazol-5-yl-benzoic acid and salts thereof |
| US4401457A (en) | 1980-06-18 | 1983-08-30 | Monsanto Company | 3'-(Substituted phenyl)-spiro[isobenzofuran-1(3H),5'(4'H)-isoxazol]-3-ones and their use as herbicides |
| DE3623302A1 (en) * | 1985-11-09 | 1987-05-14 | Bayer Ag | NICOTINE ACID DERIVATIVES |
| EP1815206B1 (en) * | 2004-10-13 | 2016-04-06 | PTC Therapeutics, Inc. | Compounds for nonsense suppression, and methods for their use |
| AU2009271328B2 (en) * | 2008-06-24 | 2012-09-06 | Irm Llc | Compounds and methods for modulating G protein-coupled receptors |
| CN114773330B (en) * | 2022-05-24 | 2024-03-15 | 贵州医科大学 | Butylphthalide-oxa/thiadiazole compound and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1024971B (en) * | 1956-11-05 | 1958-02-27 | Bayer Ag | Process for the preparation of 2,5-diaryl-1,3,4-oxdiazoles |
| FR1368390A (en) * | 1963-07-25 | 1964-07-31 | Basf Ag | Process for the production of chlorides of heterocyclic carboxylic acids and of heterocyclic carboxylic acids |
-
1975
- 1975-01-10 AU AU10078/76A patent/AU497898B2/en not_active Expired
-
1976
- 1976-01-05 ZA ZA00760038A patent/ZA7638B/en unknown
- 1976-01-06 NZ NZ179684A patent/NZ179684A/en unknown
- 1976-01-07 IL IL48803A patent/IL48803A0/en unknown
- 1976-01-07 GB GB515/76A patent/GB1494877A/en not_active Expired
- 1976-01-08 NL NL7600152A patent/NL7600152A/en not_active Application Discontinuation
- 1976-01-09 DE DE19762600655 patent/DE2600655A1/en not_active Withdrawn
- 1976-01-09 BE BE163425A patent/BE837454A/en unknown
- 1976-01-09 FR FR7600526A patent/FR2332705A1/en not_active Withdrawn
- 1976-01-09 IT IT19140/76A patent/IT1054759B/en active
- 1976-01-12 CA CA243,584A patent/CA1066708A/en not_active Expired
- 1976-01-12 CH CH29376A patent/CH603044A5/xx not_active IP Right Cessation
- 1976-01-12 BR BR7600132A patent/BR7600132A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2600655A1 (en) | 1976-07-15 |
| GB1494877A (en) | 1977-12-14 |
| IT1054759B (en) | 1981-11-30 |
| FR2332705A1 (en) | 1977-06-24 |
| NZ179684A (en) | 1978-04-03 |
| BE837454A (en) | 1976-07-09 |
| BR7600132A (en) | 1976-08-03 |
| NL7600152A (en) | 1976-07-13 |
| ZA7638B (en) | 1976-12-29 |
| AU497898B2 (en) | 1979-01-18 |
| IL48803A0 (en) | 1976-03-31 |
| AU1007876A (en) | 1977-07-14 |
| CH603044A5 (en) | 1978-08-15 |
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