CA1158882A - Agent and method for influencing plant growth containing phosphonous acid peptides - Google Patents
Agent and method for influencing plant growth containing phosphonous acid peptidesInfo
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- CA1158882A CA1158882A CA000336898A CA336898A CA1158882A CA 1158882 A CA1158882 A CA 1158882A CA 000336898 A CA000336898 A CA 000336898A CA 336898 A CA336898 A CA 336898A CA 1158882 A CA1158882 A CA 1158882A
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Abstract
5-12064/MAC 1742/=
Agent and method for influencing plant growth containing phosphonous acid peptides Abstract of the Disclosure An agent for inhibiting plant growth, in particular a herbicide and plant growth inhibiting agent comprises in addition to carriers and/or other additives, at least one compound of formula:- (I) or the corresponding zwitterion form in which R and R1 may be the same or different and each can be hydrogen, deuterium or an optionally substituted lower alkyl group, lower alkenyl, lower alkenyl, cycloalkyl, aryl or heterocyclic radical containing one or more oxygen, nitrogen or sulphur atoms and which may be fused to an aromatic ring, a lower alkyl group substituted by a cycloalkyl radical, a lower alkyl group substituted by an aryl radical, a lower alkyl group substituted by a heterocyclic radical as defined above, or R and R1 together form a polymethylene chain optionally interrupted by an oxygen, nitrogen or sulphur atoms,or R1 represents, together with the C(R) - N<
residue to which it is attached, the atoms required to complete a heterocyclic radical; and R2 and R3 may be the same or different and each can be hydrogen, optionally substituted lower alkyl, cycloalkyl, aryl or lower alkyl substituted by a cycloalkyl radical, lower alkyl substituted by a hetero-cyclic radical containing one or more nitrogen atoms;
a heterocyclic radical containing one or more nitrogen atoms;
or R2 and R3, independently, together with the C(H)-N
residue to which each is attached, may each represent the atoms required to complete a heterocyclic radical;
and n is 0, 1,'2, or 3; as well as the esters and salts thereof and all optical isomers thereof.
Agent and method for influencing plant growth containing phosphonous acid peptides Abstract of the Disclosure An agent for inhibiting plant growth, in particular a herbicide and plant growth inhibiting agent comprises in addition to carriers and/or other additives, at least one compound of formula:- (I) or the corresponding zwitterion form in which R and R1 may be the same or different and each can be hydrogen, deuterium or an optionally substituted lower alkyl group, lower alkenyl, lower alkenyl, cycloalkyl, aryl or heterocyclic radical containing one or more oxygen, nitrogen or sulphur atoms and which may be fused to an aromatic ring, a lower alkyl group substituted by a cycloalkyl radical, a lower alkyl group substituted by an aryl radical, a lower alkyl group substituted by a heterocyclic radical as defined above, or R and R1 together form a polymethylene chain optionally interrupted by an oxygen, nitrogen or sulphur atoms,or R1 represents, together with the C(R) - N<
residue to which it is attached, the atoms required to complete a heterocyclic radical; and R2 and R3 may be the same or different and each can be hydrogen, optionally substituted lower alkyl, cycloalkyl, aryl or lower alkyl substituted by a cycloalkyl radical, lower alkyl substituted by a hetero-cyclic radical containing one or more nitrogen atoms;
a heterocyclic radical containing one or more nitrogen atoms;
or R2 and R3, independently, together with the C(H)-N
residue to which each is attached, may each represent the atoms required to complete a heterocyclic radical;
and n is 0, 1,'2, or 3; as well as the esters and salts thereof and all optical isomers thereof.
Description
gZ
5- 12064/MAC 1742 /=
~gent and method for influencing plant growth containing phosphonous acid peptides The present invention relates to a novel agent for influencing plant growth, in particular to a herbicidal and plant growth regulating agent, and to a process ~or inhibiting and suppressing plant growth in monocotyledonous and dicotyledonous plants, especially grasses, cereal crops, soya, tobacco and ornamental plants.
According to the present invention, there is provided an agent for influencing plant growth, in particular a herbicide and plant growth inhibiting agent comprising, in addition . , . : -~
.. .
, ' ' ,~' ~ ."' ,, "', 81~f~
to carriers and/or other additives, at least one compound of formula 13 ~ 2_co ~ NH~C - P - H (I) n R OH
or the oorresponding zwitterion form in which R and Rl may be the same or different and each can be hydrogen, deuterium or a lower alkyl group, lower alkenyl, lower aLkynyl, C3-C7 cycloalkyl, phenyl or by a 5-membered, nitrogen containing ring containing one or mDre oxygen, nitrogen or sulphur atoms and which may be fused to an aromatic ring, a lower alkyl group substituted by a C3-C7 cycloalkyl radical, a lower alkyl group substituted by a phenyl radical, a lower alkyl group substituted by a 5 me~bered, nitrcgen oontaining ring as defined above, or R and Rl together form a polymethylene chain optionally interrupted by an oxygen, nitrogen or sulphur atoms, or ~ represents, together with the C(R) -N
residue to which it is attached, the atoms required to cc~plete a 5 nembered nitrogen containing ring and R2 and R3 may be the same or different and each can be hydrogen, lower alkyl, C3-C7 cycloalkyl, phenyl or lower alkyl substituted by a C3-C7 cycloalkyl radical, lower alkyl substituted by a heterocyclic radical oontaining one or mDre nitrogen atcms; a 5-membered ring containing one or more nitrogen atcms; or R2 and R3, independently, together with the C(H)-N residue to which each is attached, may each repre æ nt the atoms required to co~plete a 5 membered nitrogen containing ring and N is 0, 1, 2, or 3; as well as the esters and salts thereof with the physiologically ac oe ptable alcohols or acids or ba æ s respectively and all optical isomers thereof. The ~-amino acid residues or esters occurring in the peptides defined above may have the P,Lr L- or D- configuration.
5- 12064/MAC 1742 /=
~gent and method for influencing plant growth containing phosphonous acid peptides The present invention relates to a novel agent for influencing plant growth, in particular to a herbicidal and plant growth regulating agent, and to a process ~or inhibiting and suppressing plant growth in monocotyledonous and dicotyledonous plants, especially grasses, cereal crops, soya, tobacco and ornamental plants.
According to the present invention, there is provided an agent for influencing plant growth, in particular a herbicide and plant growth inhibiting agent comprising, in addition . , . : -~
.. .
, ' ' ,~' ~ ."' ,, "', 81~f~
to carriers and/or other additives, at least one compound of formula 13 ~ 2_co ~ NH~C - P - H (I) n R OH
or the oorresponding zwitterion form in which R and Rl may be the same or different and each can be hydrogen, deuterium or a lower alkyl group, lower alkenyl, lower aLkynyl, C3-C7 cycloalkyl, phenyl or by a 5-membered, nitrogen containing ring containing one or mDre oxygen, nitrogen or sulphur atoms and which may be fused to an aromatic ring, a lower alkyl group substituted by a C3-C7 cycloalkyl radical, a lower alkyl group substituted by a phenyl radical, a lower alkyl group substituted by a 5 me~bered, nitrcgen oontaining ring as defined above, or R and Rl together form a polymethylene chain optionally interrupted by an oxygen, nitrogen or sulphur atoms, or ~ represents, together with the C(R) -N
residue to which it is attached, the atoms required to cc~plete a 5 nembered nitrogen containing ring and R2 and R3 may be the same or different and each can be hydrogen, lower alkyl, C3-C7 cycloalkyl, phenyl or lower alkyl substituted by a C3-C7 cycloalkyl radical, lower alkyl substituted by a heterocyclic radical oontaining one or mDre nitrogen atcms; a 5-membered ring containing one or more nitrogen atcms; or R2 and R3, independently, together with the C(H)-N residue to which each is attached, may each repre æ nt the atoms required to co~plete a 5 membered nitrogen containing ring and N is 0, 1, 2, or 3; as well as the esters and salts thereof with the physiologically ac oe ptable alcohols or acids or ba æ s respectively and all optical isomers thereof. The ~-amino acid residues or esters occurring in the peptides defined above may have the P,Lr L- or D- configuration.
2 -.
.
'` .: ~, , , ,:
. . :, .
:.
., . . . . .....
The term "lower" referred to above and hereinafter in connection with organic radicals or compounds respectively, defines such with up to 6, preferably up to 3 carbon atoms.
me above listed radicals R, Rl, R2 and R3 optionally may be substibuted by one or m~re functionalgroups, as for example, free or etherified hydroxy or mercapto groups, optionally converted carboxyl groups, S-substituted dithio groups, optionally substituted amino groups iNR4R5- in which R4 and R5 may be the same or different and can be hydrogen or lower aIkyl or optionally substituted guanidino and~or : :: . , , . . ...
8~Z
option~lly substituted aryl groups or heterocyclic residues.
~ loreover R and Rl as lower alkyl group, aryl group or heterocyclic radical or an aryl group or heterocyclic radical as substituent of R or Rl as lower alkyl group may be substituted by one or more halogen atoms, -NR4R5 groups in which R4 and R5 together form a polymethylene chain containing up to 6 carbon atoms which may optionally be interrupted by oxygen or nitrogen or an aryloxy group optionally substituted by hydroxy or an halogen atom as for example iodine.
The substituénts ~, Rl, R2 and R3 as lower alkyl group may be a straight or branched chain alkyl group of 1 to 6 carbon atoms and may be for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-amyl, isoamyl or n-hex~l. Preferred are lower alkyl groups of 1 to 3 carbon atoms as for example methyl, ethyl, n-propyl or isopropyl.
When R, Rl, R2 or R3 is a cycloalkvl group this may be a cycloalkyl group with 3 to 7 carbon atoms as for example a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclo-heptyl group.
LS~
A lower alkyl group substituted by a cycloalkyl radical may be for example cyclopropyl-methyl, cyclopropyl-ethyl,l cyclopropyl-n-propyl, cyclobutyl-methyl, cyclobutyl-ethyl, ~.
cyclobutyl-n-p~opyl, cyclopentyl-methyl, cyclopentyl-ethyl, cyclopentyl-n-propyl, cyclohexyl-methyl, cyclohexyl-ethyl, cyclohexyl-n-propyl, cycloheptyl-methyl, cycloheptyl-ethyl j.
or cycloheptyl-n-propyl.
The term aryl preferably comprises mononuclear groups such as phenyl, which may be substituted in one or more positions by substituents such as lower alkyl, hydroxy, lower alkoxy or halogen.
Moreover in addition to the meaning above when R
:and Rl or the substituent of a lower alkyl group thereof is an aryl group, this aryl group comprises 6 to 10 carbon atoms and may be for example as mononuclear group a phenyl, tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, sec;-butylphenyl,.tert.-butyl-phenyl or naphthyl group.
If the substituents Rl, R2 or R3 can also repre~ent together with the C(R)-N~ resldue, or CH-N< residue respecti~ely, a heterocyclic. radical, it is preferably a 5-membered nitrogen-containing ring such as pyrrolidine in proline and 4-hydroxy-pyrrolidine in hydroxy-proline, and pyroglutamic acid.
. . :. , .
: ~ ' : .'' , ':;, : ' , ..
-6- llS~
A h~terocyclic residue as substituent of an optional substituted radical R, Rl, R2 and R3 may be a mono- or bicyciic, a monoaza or diazacyclic radical of aromatic character such as imidazolyl, as for example 4-imidazolyl, or indolyl, as for example 3-indolyl radical.
.
Moreover in addition when R or Rl or the substituent of a lower alkyl group thereof is a heterocyclic ring containing one or more oxy~en, nitrogen or sulphur atoms this may be, for example, aziridine, oxetane, thiopkene, furan, pyridine, aze-pine, isox~zole, thiazole, pyrimidine, dia~epine, thiadiazol, triazol, tria ine, or imidazole or indole as mentioned abo~e.
When R or Rl is a lower alkenyl group this may be a straight or branched chain alkenyl group with 2 to 6 carbon atoms, and may be, for exa~ple, an ethenyl, allyl, crotyl, methallyl, pentenyl or hexenyl group.
Uhen R or Rl represents a lower alkynyl group this may be straight or branched chain alkynyl group with 2 to 6 carbon atoms, and may be, for example, an ethynyl, propynyl, butynyl, pentynyl or hexynyl group.
When R and Rl together form a polymethylene chain, comprising a residue of 2 to 7 carbon atoms, this ~2y be `~ for example -(CH2)2-, -(CH2)3~. -(cH2)4 ( 2 5 2 6 2 7 ( 2)2cHcH3(cH2)2- or -(CH2)2NH(CH2)2-, ..
-.
~L1S813~
_, _ The term etherified hydroxy is prefer~bly lower alkoxy, such ~s methoxy, ethoxy, n-propyloxy, isopropyloxy or n-butyloxy and etherified mercapto is preferably lower alkylthio as for example methylthio, ethylthio, propylthio or isopropylthio.
T~e compounds containing S-substituted dithio groups are symmetrical or unsymmetrical residues of a compound of formula I bound to the other residue of a compound of formula I
by a S-S-bridge, i.e. ~
A ^ S - S - B
wherein A and B are the same or different and each is a residue of a compound of formula I formed by the loss of a hydrogen atom from a carbon atom in one of the substituents :
R~ Rl, R2 or R3-Examples of such compounds are those ha~ing the formulae Ia and Ib H2N CHCO t NH - CHC ~ NH - C - P - H
ICH2 I oL
s R3 / IR2 ~ . I H2 0 H2N CHCO t NHCHCO t NH C- P H
\ / n Rl OH
.. . . . .. . . . . ..
~....................... . .. ~. .. . . . .
, , - , , . ,: ~. .. .~.
. .
t 1 2 ~ Rl o I ~
I H t R2 ) Rl o n R OH
.
Functionatly modified carboxy is, e.g. esterified carbosy, especially lower alkoxycarbonyl, also phenyl-lower-alkoxycarbonyl or carbamoyl.
i When R, Rl, R2 or R3 is a group substituted by ~ R5, in which one or both the R4 and R5 groups are lower~
alkyl, these ~roups may be lower alkyl groups as defined above. The -NR4R5 group including the different meanings enumerated above may be for example, methylamino, dimethyl-amino, methyl-ethylamino, ethyla~ino, diethylamino, propyl amino, isopropylamino, dipropylamino or diisopropyl~mir.o.
The -NR4R5 groups in which R4 and R5 together form a polymethylene chain containing up to 6 carbon atoms which may optionally be interrupted by oxygen or nitrogen as for instance as substituent of R and Ri and are preferably the morpholino or piperidino group.
. . - , ,, ,. : :
~ . . : . ~ . . :
_g_ Furthermore when R or Rl is a group substituted by aryloxy, the aryloxy group may be phenoxy, tolyloxy, xylyloxy, diiodo-hydroxy phenoxy.
The term halogen may be bromine or iodine but is preferably fluorine or chlorine.
Esters of the compounds of formula I are preferably the esters of the compounds of formula I with low aIkyl alcohols e.g. methanol, ethanol, n-propanol and n-butanol, aralkyl alcohols e.g. benzyl alcohol and phenols e.g. phenol.
Other alcohols which may be used to form the corresponding ester of the compound of formula I are alkanoyloxymethanols e.g. acétoxymethanol or pivaloyloxymethanol; amino-lower-alkanoyloxymethanols e.g. ~-amino-lower-alkanoyloxymethanols such as glycyloxy-methanol, L-valyloxymethanol or L-leucyl-oxymethanol; and also 3-hydroxy-phthalide and 5-indanol.
Salts of the compounds of formula I are salts with either strong monobasic or polybasic or with inorganic or organlc bases. Strong aclds include all those strong acids e.g. hydrogen halide acids or allphatlc or aromatic carboxyl~c and sulphonic acids which are capable of forming salts with the amino group of the molecule and which are physiologically acceptable to plants. Inorganic and organic bases are those bases e.g. alkali metal and alkaline earth metal hydroxides or alkylamines which are capable of forming salts with the acidic hydroxyl group of the molecule and which are physiologically acceptable to plants.
., ', ' : ' , . .
~1~i&~
Particularly useful are compounds of formula I
wherei~ R and R1 may be the same or different and each is hydrogen, deuterium, optionally substituted lower alkyl,or lower alkyl substituted by cycloalkyl, aryl or by a mono- or bicyclic monoaza-or diazacyclic radicals, optionally substituted by one to three hydro~y or lower alkoxy groups; or Rl represents, together with the -CR-N< residue to which it is attached, the atoms required to complete a 2-pyrrolidinyl group;
R2 and R3 may be the same-or different and each is hydrogen, optionally substituted lower alkyl, or lower alkyl substituted by cycloalkyl, aryl, or by a mono- or bicylic monoaza or diazacylic radical optionally substituted by one to three hydro~y or lower alko~y groups or R2 or R3 each represents to~ether with the -CH-N< residue to which it is attached, the atoms required to complete the 2-pyrrolidinyl group;
and n is 0, 1, 2 or 3; as well as the esters and salts with physiolog~callY acceptable alcohols, or acids or bases, respecti~ely; and all optical isomers ther~of.
Preferred are compounds Or formula I wherein R and Rl may be the same or different and each is hydrogen deuterium.
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert~ary butyl, optionally substituted by imidazolyl, indolyl, benzyl groups optionally substituted by one to three hydroxy groups, lower aLkoxy, lower alkylthio, amino or carboxy groups or Rl represents ' .:
together with the -C~R)-N< residue to which it is attached, the atoms required to complete a 2-pyrrolidinyl group;
R2 and R3 may be the same or different and e~ch can be hydrogen, methyl, isopropyl, isobutyl, benzyl, aminobutyl, hydroxymethyl, l-hydroxyethyl, 2-methylthioethyl, imidazoly-methyl, or indolylmethyl, or R2 or R3, respecti~ely, together with the -CH~< ~ residue to which it is attached, represents the atoms required to complete a 2-pysroli~inyl group; and n is 0,1,2 or 3; as well as the esters and salts with pharmaceutically acceptable alcohols, or acids or bases, re~poctively; and all optical isomers thereof.
Especially valuable and suitable for said utility are compounds of formula ~, wherein R is hydrogen;
Rl is methyl; R2 and R3 may be the same or different and each is hydrogen, methyl, lsopropyl, isobutyl, aminobutyl, hydroxymethyl, l-hydroxyethyl, 2-methylthioethyl, imidazolylmethyl or indolylmethyl, benzyl or R2 or R3 respectively together wlth the -CR-N or -CH-N resldue to whlch lt ls attached represents the atoms requlred to complete a 2-pyrrolidinyl group; and n is 0, 1, 2 or
.
'` .: ~, , , ,:
. . :, .
:.
., . . . . .....
The term "lower" referred to above and hereinafter in connection with organic radicals or compounds respectively, defines such with up to 6, preferably up to 3 carbon atoms.
me above listed radicals R, Rl, R2 and R3 optionally may be substibuted by one or m~re functionalgroups, as for example, free or etherified hydroxy or mercapto groups, optionally converted carboxyl groups, S-substituted dithio groups, optionally substituted amino groups iNR4R5- in which R4 and R5 may be the same or different and can be hydrogen or lower aIkyl or optionally substituted guanidino and~or : :: . , , . . ...
8~Z
option~lly substituted aryl groups or heterocyclic residues.
~ loreover R and Rl as lower alkyl group, aryl group or heterocyclic radical or an aryl group or heterocyclic radical as substituent of R or Rl as lower alkyl group may be substituted by one or more halogen atoms, -NR4R5 groups in which R4 and R5 together form a polymethylene chain containing up to 6 carbon atoms which may optionally be interrupted by oxygen or nitrogen or an aryloxy group optionally substituted by hydroxy or an halogen atom as for example iodine.
The substituénts ~, Rl, R2 and R3 as lower alkyl group may be a straight or branched chain alkyl group of 1 to 6 carbon atoms and may be for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-amyl, isoamyl or n-hex~l. Preferred are lower alkyl groups of 1 to 3 carbon atoms as for example methyl, ethyl, n-propyl or isopropyl.
When R, Rl, R2 or R3 is a cycloalkvl group this may be a cycloalkyl group with 3 to 7 carbon atoms as for example a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclo-heptyl group.
LS~
A lower alkyl group substituted by a cycloalkyl radical may be for example cyclopropyl-methyl, cyclopropyl-ethyl,l cyclopropyl-n-propyl, cyclobutyl-methyl, cyclobutyl-ethyl, ~.
cyclobutyl-n-p~opyl, cyclopentyl-methyl, cyclopentyl-ethyl, cyclopentyl-n-propyl, cyclohexyl-methyl, cyclohexyl-ethyl, cyclohexyl-n-propyl, cycloheptyl-methyl, cycloheptyl-ethyl j.
or cycloheptyl-n-propyl.
The term aryl preferably comprises mononuclear groups such as phenyl, which may be substituted in one or more positions by substituents such as lower alkyl, hydroxy, lower alkoxy or halogen.
Moreover in addition to the meaning above when R
:and Rl or the substituent of a lower alkyl group thereof is an aryl group, this aryl group comprises 6 to 10 carbon atoms and may be for example as mononuclear group a phenyl, tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, sec;-butylphenyl,.tert.-butyl-phenyl or naphthyl group.
If the substituents Rl, R2 or R3 can also repre~ent together with the C(R)-N~ resldue, or CH-N< residue respecti~ely, a heterocyclic. radical, it is preferably a 5-membered nitrogen-containing ring such as pyrrolidine in proline and 4-hydroxy-pyrrolidine in hydroxy-proline, and pyroglutamic acid.
. . :. , .
: ~ ' : .'' , ':;, : ' , ..
-6- llS~
A h~terocyclic residue as substituent of an optional substituted radical R, Rl, R2 and R3 may be a mono- or bicyciic, a monoaza or diazacyclic radical of aromatic character such as imidazolyl, as for example 4-imidazolyl, or indolyl, as for example 3-indolyl radical.
.
Moreover in addition when R or Rl or the substituent of a lower alkyl group thereof is a heterocyclic ring containing one or more oxy~en, nitrogen or sulphur atoms this may be, for example, aziridine, oxetane, thiopkene, furan, pyridine, aze-pine, isox~zole, thiazole, pyrimidine, dia~epine, thiadiazol, triazol, tria ine, or imidazole or indole as mentioned abo~e.
When R or Rl is a lower alkenyl group this may be a straight or branched chain alkenyl group with 2 to 6 carbon atoms, and may be, for exa~ple, an ethenyl, allyl, crotyl, methallyl, pentenyl or hexenyl group.
Uhen R or Rl represents a lower alkynyl group this may be straight or branched chain alkynyl group with 2 to 6 carbon atoms, and may be, for example, an ethynyl, propynyl, butynyl, pentynyl or hexynyl group.
When R and Rl together form a polymethylene chain, comprising a residue of 2 to 7 carbon atoms, this ~2y be `~ for example -(CH2)2-, -(CH2)3~. -(cH2)4 ( 2 5 2 6 2 7 ( 2)2cHcH3(cH2)2- or -(CH2)2NH(CH2)2-, ..
-.
~L1S813~
_, _ The term etherified hydroxy is prefer~bly lower alkoxy, such ~s methoxy, ethoxy, n-propyloxy, isopropyloxy or n-butyloxy and etherified mercapto is preferably lower alkylthio as for example methylthio, ethylthio, propylthio or isopropylthio.
T~e compounds containing S-substituted dithio groups are symmetrical or unsymmetrical residues of a compound of formula I bound to the other residue of a compound of formula I
by a S-S-bridge, i.e. ~
A ^ S - S - B
wherein A and B are the same or different and each is a residue of a compound of formula I formed by the loss of a hydrogen atom from a carbon atom in one of the substituents :
R~ Rl, R2 or R3-Examples of such compounds are those ha~ing the formulae Ia and Ib H2N CHCO t NH - CHC ~ NH - C - P - H
ICH2 I oL
s R3 / IR2 ~ . I H2 0 H2N CHCO t NHCHCO t NH C- P H
\ / n Rl OH
.. . . . .. . . . . ..
~....................... . .. ~. .. . . . .
, , - , , . ,: ~. .. .~.
. .
t 1 2 ~ Rl o I ~
I H t R2 ) Rl o n R OH
.
Functionatly modified carboxy is, e.g. esterified carbosy, especially lower alkoxycarbonyl, also phenyl-lower-alkoxycarbonyl or carbamoyl.
i When R, Rl, R2 or R3 is a group substituted by ~ R5, in which one or both the R4 and R5 groups are lower~
alkyl, these ~roups may be lower alkyl groups as defined above. The -NR4R5 group including the different meanings enumerated above may be for example, methylamino, dimethyl-amino, methyl-ethylamino, ethyla~ino, diethylamino, propyl amino, isopropylamino, dipropylamino or diisopropyl~mir.o.
The -NR4R5 groups in which R4 and R5 together form a polymethylene chain containing up to 6 carbon atoms which may optionally be interrupted by oxygen or nitrogen as for instance as substituent of R and Ri and are preferably the morpholino or piperidino group.
. . - , ,, ,. : :
~ . . : . ~ . . :
_g_ Furthermore when R or Rl is a group substituted by aryloxy, the aryloxy group may be phenoxy, tolyloxy, xylyloxy, diiodo-hydroxy phenoxy.
The term halogen may be bromine or iodine but is preferably fluorine or chlorine.
Esters of the compounds of formula I are preferably the esters of the compounds of formula I with low aIkyl alcohols e.g. methanol, ethanol, n-propanol and n-butanol, aralkyl alcohols e.g. benzyl alcohol and phenols e.g. phenol.
Other alcohols which may be used to form the corresponding ester of the compound of formula I are alkanoyloxymethanols e.g. acétoxymethanol or pivaloyloxymethanol; amino-lower-alkanoyloxymethanols e.g. ~-amino-lower-alkanoyloxymethanols such as glycyloxy-methanol, L-valyloxymethanol or L-leucyl-oxymethanol; and also 3-hydroxy-phthalide and 5-indanol.
Salts of the compounds of formula I are salts with either strong monobasic or polybasic or with inorganic or organlc bases. Strong aclds include all those strong acids e.g. hydrogen halide acids or allphatlc or aromatic carboxyl~c and sulphonic acids which are capable of forming salts with the amino group of the molecule and which are physiologically acceptable to plants. Inorganic and organic bases are those bases e.g. alkali metal and alkaline earth metal hydroxides or alkylamines which are capable of forming salts with the acidic hydroxyl group of the molecule and which are physiologically acceptable to plants.
., ', ' : ' , . .
~1~i&~
Particularly useful are compounds of formula I
wherei~ R and R1 may be the same or different and each is hydrogen, deuterium, optionally substituted lower alkyl,or lower alkyl substituted by cycloalkyl, aryl or by a mono- or bicyclic monoaza-or diazacyclic radicals, optionally substituted by one to three hydro~y or lower alkoxy groups; or Rl represents, together with the -CR-N< residue to which it is attached, the atoms required to complete a 2-pyrrolidinyl group;
R2 and R3 may be the same-or different and each is hydrogen, optionally substituted lower alkyl, or lower alkyl substituted by cycloalkyl, aryl, or by a mono- or bicylic monoaza or diazacylic radical optionally substituted by one to three hydro~y or lower alko~y groups or R2 or R3 each represents to~ether with the -CH-N< residue to which it is attached, the atoms required to complete the 2-pyrrolidinyl group;
and n is 0, 1, 2 or 3; as well as the esters and salts with physiolog~callY acceptable alcohols, or acids or bases, respecti~ely; and all optical isomers ther~of.
Preferred are compounds Or formula I wherein R and Rl may be the same or different and each is hydrogen deuterium.
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert~ary butyl, optionally substituted by imidazolyl, indolyl, benzyl groups optionally substituted by one to three hydroxy groups, lower aLkoxy, lower alkylthio, amino or carboxy groups or Rl represents ' .:
together with the -C~R)-N< residue to which it is attached, the atoms required to complete a 2-pyrrolidinyl group;
R2 and R3 may be the same or different and e~ch can be hydrogen, methyl, isopropyl, isobutyl, benzyl, aminobutyl, hydroxymethyl, l-hydroxyethyl, 2-methylthioethyl, imidazoly-methyl, or indolylmethyl, or R2 or R3, respecti~ely, together with the -CH~< ~ residue to which it is attached, represents the atoms required to complete a 2-pysroli~inyl group; and n is 0,1,2 or 3; as well as the esters and salts with pharmaceutically acceptable alcohols, or acids or bases, re~poctively; and all optical isomers thereof.
Especially valuable and suitable for said utility are compounds of formula ~, wherein R is hydrogen;
Rl is methyl; R2 and R3 may be the same or different and each is hydrogen, methyl, lsopropyl, isobutyl, aminobutyl, hydroxymethyl, l-hydroxyethyl, 2-methylthioethyl, imidazolylmethyl or indolylmethyl, benzyl or R2 or R3 respectively together wlth the -CR-N or -CH-N resldue to whlch lt ls attached represents the atoms requlred to complete a 2-pyrrolidinyl group; and n is 0, 1, 2 or
3; and the esters and salts thereof with physiolcgically acceptable alcohols or acids or bases, respectively;
and all optical isomers thereof.
: - . I -.,: : ~ .
., , ~ .
.. . - . ,. . , . , - ..
. . .
-The production of the compounds of formula I is fully described in Canadian application Serial No. 316,450 (United States Patent No.
and all optical isomers thereof.
: - . I -.,: : ~ .
., , ~ .
.. . - . ,. . , . , - ..
. . .
-The production of the compounds of formula I is fully described in Canadian application Serial No. 316,450 (United States Patent No.
4,213,969).
The agents according to the invention are prepared in a manner which is in itself know by intimate muxing and grinding of active comEounds of the formula I with suitable carriers, if desired with addition of disEersing agents or solvents which are inert bowards the active compounds.
The active compounds may exist, and be used, in the follcwing processing forms:
Solid processing forms: dusting agents, sprinkling agents, granules, coated granules, impregnated granules and homogeneous granules;
Active compound concentrates which are dispersible in water:
wettable powders, pastes and emulsions:
Liquid processing forms: solutions.
In order to prepare solid processing fonms (dusting agents, sprinkling agents and granules), the active compounds are mixed with solid carriers. Ex~mples of carriers which can be used are kaolin, talc, bolus, loess, chalk, limestone, lime grits, attapulgite, dolomite, diatomaceous earth, preci-pitated silica, alkaline earth metal silicates, sodium and potassium aluminosilicates (feldspars and micas), calcium and magnesium sulphates, magnesium oxide, ground plastics, ferti-lisers, such as ammonium sulphate, ammonium phosphate, ammonium nitrate and urea, ground vegetable products, such as cereal flour, bark flour, wood flour, nutshell flour, cellulose powder, plant extract residues, active charcoal and the like, in each case on their own or as mixtures with one another.
Granules ca~ be prepared by, for example, dissolving the active compounds in an org~nic solvent, applying the solution thus obtained to a granulated material, for example attapulgite, SiO2, granicalcium or bentonite, and then again evaporating the organic solvent.
- It is also possible to prepare polymer granules by, for example, impregnating finished, porous polymer granules such as urea/formaldehyde polymers, polyacrylonitrile and polyesters, having a spx~iic surface area and an advantageous predetermined absorption/desorption ratio,with the active compounds, for example in the form of their solutions (in a low-boiling solvent) and removing the solvent. Such polymer granules can be applied in the form of micro-granules with bulk densities of, preferably, 300 g/litre to 600 g/litre, also with the aid of atomisers. Atomising can be effected .: ... - . . : .
' ' ~14~
over extensive treatment areas by means of aircraft.
~ ranules can also be obtained by compacting the carrier with the active compounds and additives and then comminuting the mixture.
Furthermore, it is possible to add to these agents additives which stabilise the active compound and/or non-ionic, anionic and cationic materials which, for example, improve the adhesion of the active compounds to plants and parts of plants (adhesives and glues) and/or ensure better wetta-bility (wetting agents) and dispersibility (dispersing agents).
It ~s possible to use, for example, the following materi~ls as adhesi~es: olein/lime mixture, cellulose derivati~es (methylcellulose and carboxymethylcellulose), hydroxyethylene glycol ethers of monoalkylphenols and dialkylphenols having
The agents according to the invention are prepared in a manner which is in itself know by intimate muxing and grinding of active comEounds of the formula I with suitable carriers, if desired with addition of disEersing agents or solvents which are inert bowards the active compounds.
The active compounds may exist, and be used, in the follcwing processing forms:
Solid processing forms: dusting agents, sprinkling agents, granules, coated granules, impregnated granules and homogeneous granules;
Active compound concentrates which are dispersible in water:
wettable powders, pastes and emulsions:
Liquid processing forms: solutions.
In order to prepare solid processing fonms (dusting agents, sprinkling agents and granules), the active compounds are mixed with solid carriers. Ex~mples of carriers which can be used are kaolin, talc, bolus, loess, chalk, limestone, lime grits, attapulgite, dolomite, diatomaceous earth, preci-pitated silica, alkaline earth metal silicates, sodium and potassium aluminosilicates (feldspars and micas), calcium and magnesium sulphates, magnesium oxide, ground plastics, ferti-lisers, such as ammonium sulphate, ammonium phosphate, ammonium nitrate and urea, ground vegetable products, such as cereal flour, bark flour, wood flour, nutshell flour, cellulose powder, plant extract residues, active charcoal and the like, in each case on their own or as mixtures with one another.
Granules ca~ be prepared by, for example, dissolving the active compounds in an org~nic solvent, applying the solution thus obtained to a granulated material, for example attapulgite, SiO2, granicalcium or bentonite, and then again evaporating the organic solvent.
- It is also possible to prepare polymer granules by, for example, impregnating finished, porous polymer granules such as urea/formaldehyde polymers, polyacrylonitrile and polyesters, having a spx~iic surface area and an advantageous predetermined absorption/desorption ratio,with the active compounds, for example in the form of their solutions (in a low-boiling solvent) and removing the solvent. Such polymer granules can be applied in the form of micro-granules with bulk densities of, preferably, 300 g/litre to 600 g/litre, also with the aid of atomisers. Atomising can be effected .: ... - . . : .
' ' ~14~
over extensive treatment areas by means of aircraft.
~ ranules can also be obtained by compacting the carrier with the active compounds and additives and then comminuting the mixture.
Furthermore, it is possible to add to these agents additives which stabilise the active compound and/or non-ionic, anionic and cationic materials which, for example, improve the adhesion of the active compounds to plants and parts of plants (adhesives and glues) and/or ensure better wetta-bility (wetting agents) and dispersibility (dispersing agents).
It ~s possible to use, for example, the following materi~ls as adhesi~es: olein/lime mixture, cellulose derivati~es (methylcellulose and carboxymethylcellulose), hydroxyethylene glycol ethers of monoalkylphenols and dialkylphenols having
5 to 15 ethylene oxide residues per molecule and 8 to 9 carbon atoms in the alkyl radical, ligninsulphonic acid, its aIkali metal salts and alkaline earth metal salts, polyethylene gly-col ethers (Carbowaxes), fatty alcohol polyglycol ethers ha~ing 5 to 20 ethylene oxide residues per molecule and 8 to 18 carbon atoms in the fatty alcohol part, condensation products of ethylene oxide and propylene oxide, polyvinyl-pyrrolidonesj poly~inyl alcohols, condensation products of urea/formaldehyde and latex products.
Water-dispersible active compound concentrates, i.e.
wettable powders, pastes and emulsion concentrates, are agents which can be diluted with water to any desired concentration.
~heyconsist of active compound, carrier if desired additives .
~ .
.
' . . ~ ~. .
. .
which stabilise the active compound, surface-active substances and anti-foaming agents and, if desired, solvents.
The wettable powders and pastes are obtained by mixing and grinding the active compounds with dispersing agents and pulverulent carriers in suitable devices until homogeneity is achieved. Examples of carriers are those mentioned above for the solid processing forms. In some cases it is advantageous to use mixtures of different carriers.
Examples of dispersing agents which can be used are: conden-sation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde, condensation pro-ducts of naphthalene or of naphthalenesulphonic acids with phenol and formaldehyde, and alkali met~l salts, ammonium salts and alkaline earth metal salts of ligninsulphonic acid, as well as alkylarylsulphonates, aIkali metal salts and alka-line earth metal salts of dibutyln~phthalenesulphonic acid, fatty alcohol sulphates, such as salts of sulphated hexa-decanols and heptadecanols, and salts of sulphated fatty a7cohol polyethylene glycol ethers, the sodium salt of oleyl methyl tauride, di-tertiary acetylere glycols, diaIkyldilauryl-ammonium chloride and alkali metal salts and alkaline earth metal salts of fatty acids.
Examples of anti-foaming agents which can be used are silicones.
The active compounds are mixed, ground, sieved and strained with the abovementioned additives, in such a way that the particle size of the solid component does not exceed 0.02 , , , .; . , , ~ , :
.. . . ..
', ' '' : ' . :
to 0.04 mm in the case of wettable powders and 0.03 mm in the case of pastes. To prepare emulsion concentrates and pastes, dispersing agents, such as have been listed in the preceding sections, organic solvents and water are used.
Examples of suitable solvents are the following: alcohols, benzene, xylenes, toluene, dimethylsulphoxide, N,N-dialky-lated amides and trialkylamines. me solvents must be virtually odourless and inert towards the active compounds and s~l1dnotbe readily combustible.
Furthermore, the agents according to the invention can be used in the form of solutions. For this purpose, the active compound or several active compounds of the formula I is/are dissolved in suitable organic solvents, solvent m~r water -or mixtures of organic solvents with water.
The content of active compound in the agents described above is between 0.1 and 95%, preferably between 1 and 80%.
Use forms can be diluted down to 0.001%. me amounts used are as a rule 0.1 to 10 kg of active substance/
hectare, preferably 0.25 to 5 kg of active substance/hectare.
m e active compounds of the formula I can be formulated, for example, as follows (parts are parts by weight):
Dustin~ a~ents:
m e following substances are used for the preparation of a) a 5% strength dusting agent and b) a 2% strength , .
dusting agent a) 5 parts o~ (l-RS)-l-(L-alanylamino)ethanephosphonous acid and 95 p~rts o~ talc, b) 2 parts of (1-RS)-l-(L-alanylamino)-2-methylpropane-phosphonous acid 1 part o~ highly disp~rse silica and 97 parts of talc.
The actlve compounds are mixed and ground wYth the carriers.
Granules:
-The following substances are used ~or the preparationof 5% strength granules:
5 parts of (l-R)-l-(L-alanyl-L-alanyl-L-alanylamino)-ethanephosphonous acid, 0.25 part of epichlorohydrin, 0.25 part of cetylpolyethylene glycol ether containing 8 mols of ethylene oxide, - 3,50 parts of polyethylene glycol and 91 parts of kaolin (particle size 0.3 to 0.8mm).
The active substance is mixed with the epichlorohydrin and dissolved in -cetone, , after which polyethylene glycol and cetyl polyethylene glycol ether are added. ' The solution ,thus obtained is sprayed onto kaolin and the acetone is subsequently evaporated off in vacuo.
Wettable ~owders:
The following constituents are used for the prepara-tion of a) a 50% strength wettable powder, b) a 25% strength wettable powder and c) a 10% strength wettable powder:
,~
`, ~
-18~
a) 50 parts of (l-RS)-l-(L-valylamino)-ethanephosphonous acid, 5 parts of sodium dibutylnaphthylsulphonate, 3 parts of a naphthalenesulphonic acids/phenol-sulphonic acids/formaldehyde condensate, 3:2:1, 20 parts of kaolin and 22 parts of Champagne chalk;
b) 25 parts of the diethanolamine salt of the above active compound, 5 parts of the sodium sal~ of oleyl methyltauride, 2 5 parts of a naphthalenesulphonic acids/form~lde-hyde condensate, O.5 part of carboxymethylcellulose, 5 parts of neutral potassium aluminium silicate and 62 parts of kaolin;
c) 10 par~s Gf (l-R)-l-(L-alanylamino)-ethanephosphonous acid~
3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of a naphthalenesulphonic acids/formal-dehyde condensate and 82 parts of kaolin.
The active compound indicated is absorbed onto the appropriate carriers (kaolin and chalk) and is then mixed and ground. Wettable powders of excellent wettability and suspensibility are obtained. Suspensions of any desired active compound concentration can be obtained from such wetta~le ~, powders by dilution with water Suspensions of this type , .. .. .
, - . . ~. , ~ & ~
are used for combatting weeds and wild grasses in crops of plants by the pre-emergence process, and for the treatment of 1AWnS .
Paste:
The follo.wing substances are used for the prep~ation of a 45% strength paste:
45 parts of (l-R)-l-(L-alanyl-L-alanyl-L-alanyl-L-alanylamino)-ethanephosphonous acid 5 parts of sodium aluminium'silicate, 14 parts of cetyl polyethylene glycol ether containing 8 mols o~ ethylene oxide, 1 part of oleyl polyethylene glycol ether containing 5 mols of ethylene oxide, 2 parts of spindle oil, 23 parts of water and 10 parts of polyethylene glycol.
The active compound is intimately mixed and ground with the additivesin apparatus ~ which i8'~ suitable for this purpose. A paste is obtained, from which suspensions of any desired concentration can be prepared by dilution with water.
me suspensions are suitable for the treatment of lawns.
Emulsion concentrate:
~ ,or the preparation of a 25% strength emulsion concen-trate.
' ' . ~
25 parts of (l-R)-l-(L-alanyl-L-alanylamino)-ethane-phosphonous acid, 5 parts of a mixture of nonylphenol polyoxyethylene and calcium dodecylbenzenesulphonate, 35 parts of 3,~,5-trimethyl-2-cyclohexen-1-one and 35 parts o~ almethylformamide are mixed with one another. This concentrate can be diluted wi~hwat#rto @ve emulsions of suitable concentrations.
Instead of the particular active compound indicated in the above formulation examples, it is also possible to use other compounds from amongst those included in the formula I.
m e active compounds contained in the agents accord-ing to the invention influence the plant growth in various ways. m us they inhibit, delay or suppress, in parti-cular, the growt_ and germination. They there~he have a post-emergent herbicidal action as well as a growth ~nh~biting action.
Agents according to the lnvention, which contain at least one compound of the formula I as the active component, are suitable, in particular, for i~hibiting and suppressing p~ant growth in monocotyledonous and dicotyledonous plants by post-emergent treatment of the sown areas or of the plants, such as shrubs, trees, leguminous crops, sugar cane, onion and potato tubers, fruit trees and vines and, in particular,grasses, cereal crops, tobacco, soya and ornamental plants.
.. . .
; ; , . -.. . .~ . .. .
The action achieved, in particular, by the active com-pounds of the formula I is the desired reduction in plant size, especially the height of growth. In general, a certain change in the form of the plant is associated with this.
In direct association with the reduction of the height of growth, the plant is strengthened. The leaves and stem develop more strongly. me resistance to kinking of mono-cotyledonous plants is increased by shortening the internodaldistances. Crop losses due to a thunderstorm, continuous rain and the like, which usually lead to lodging of cereal crops and leguminous crops, can be largely prevented in this manner and harvesting can thus be made easier. As a side effect, reduced height of growth of useful plants leads to a sa~ing of fertilisers. This also applies, in the same way, to ornamental plants, ornamental lawns, sports fields or other grassed areas.
However, one of the most important problems of pure grass plantings is the actual cutting of the grass, whether in public parks in urban areas, on industrial sites, on playing fields or alongside motor-roads, aircraft landing strips, railway emb~nkments or the sloping banks of waterways. In all these cases lt is necessary to mow the lawn ox cut the growth of grass periodically. This is not only very expen-sive in terms of labour and machinery, but, in the transport sector, also in~ol~es considerable dangers for the personnel concerned and for the occupants of ~ehicles.
.
.
.
': .
.
-22- ~ 8~ ~
There is therefore, particularly in areas with large traffic networks, an urgent need on the one hand to maintain and care for the greensward which is necessary to strengthen road verges and embankments on traffic routes and, on the other hand, to keep it at a medium height of growth during the whole vegetation period, using simple measures. This need is met in a very favourable mAnner by applying active compounds of the formula I.
By treating trees, shrubs and hedges, in particular in urban and industrial areas, with compounds of the fonmula L
thelabaur-inb~E~e wingwD~kcznbe reduoedin an analogous manner. -T~e growth of shoots and/or the fertilityof fruit trees and vines can also be advantageously influenced by using the active compounds of the formula I.
Ornamental plants with pronounced longitudinal growth can be grown as compact pot plants by treatment with the active compounds mentioned.
The active compounds of the formula I are also used for inhibiting the growth of undesired side shoots, for example in tobacco and ornamental plants, whereby the labour-intensive m~nual breaking off of these shoots is avoided, and furthermore for the inhibition of sprouting in the case of stored tubers, for e*ample in the case of tubers of ornamental plants and in the case of onions and potatoes, and finally for increasing the yield in the case of crop plants having an intense vegetative growth, such as soya and sugar cane, by accelerating the trans-ition from the vegetative growth phase to the generative growth phase through application of active compounds of the formula I.
.. ..
.. ~ . . , . ~.. ;. , . .
.. . . , . -8`~Z
The active compounds of the formula I are preferably employed for inhibiting the growth of weeds, including perennial weeds, grasses, especially perennial grasses, such as Cyperus species and the like, and of cereal crops, tobacco, soya and ornamental plants.
~ he amounts used vary and depend on the time of appllcation. In general, they are between 0.1 and 5 kg of active compound per hectare for the treatment of existlng crops, preferably up to 4 kg per hectare.
The action of the active compounds according to the definition is directed towards the germinating seed(pre-emergent action) but is preferably directed towards the parts of the plant which are above ground ( contact action) in particular the leaves.
The action as a powerful growth inhibitor is shown by the fact that most of the species of plants treated in a post-emergent manner stop growing after an experimental period of three weeks, the partsof the plant treated assuming a dark-green coloration. However, the lea~es do not fall.
In the case of some spec~es of plants, this growth inhibition already occurs at a dosage of 0.5 kg/hectare and less and wlthin several days after treatment.
Since not all species of plants are equally powerfully inhibited, it is possible to use the active com-pounds selectively when a particular low dosage is chosen.
. .
, . . .
Z
The active compounds of the formula I are also interestLng combination partners for a number of herbicides of the diphenyl ether, phenylurea and triazine series for use on cereal crops, maize and sugar cane 2nd in fruit growLng and viticulture.
In areas with an increased danger of erosion, the active compounds of the formula I can be used as growth inhi-bitors on the most diverse crops.
In thls case, the weed co~er is not removed but only nh~bited to such an extent that it can no longer compete with the crop plants.
._ ., . . . . .. __ ... . . .. . .
The following Examples further illustrate the present inventlon.
Use Examples 1 and 2 The following test methods were used to demonstrate the usefulness of the actlve compounds as herblcides (post-emergent) and as growth inhibitors:
Post-emergent herbicidal action (contact herbicide) The plants of 7 weeds and crop plants, both monocotyledonous and dicotyledonous, ~ere sprayed after emergence ( in the 4-leaf to 6-leaf stage) with an aqueous actlve co~pound emulsion in a dosage of 4 kg of actlve substance per hectare, and the plants were kept at 24- 26C and a relative atmospheric humidity of 45-60%. The test was evaluated 5 days and 15 days after treatment and the result is given ln the .~ following Table I.
...
. . . . .
. : ,. . .
~1~)88~32 compound H2N-CH-CONHCHP(OH)2 H2NCHCO[NHCHCO]2NHCHP(OH)2 L R L L R
plant -Avena sa~iva . 4 5 Setania Italica 2 3 Lolium perenne 3 4 Solanum lycopersicum 3 2 Sinapis alba 2 2 Stellaria media 2 4 Phaseolus vulgaris _ 9 = plant(s) undamaged (as untreated control) --8-2 = intermediate stages of damage The results demonstrate that the compounds according to the present invention which were tested exhibited a pronounced contact herbicidal action on some plants and, as a symptom of the growth inhibiting properties, halted the growth of many plants.
.
:-'~ ' . ` ~ .. . -. . :' . ". ~ . . ' ., , Growth inhibition in ~rasses Seeds of the grasses Lolium pere~ne, Poa pratensis, Festuca ovina and Dactylis glomerata were sown in plastic bowls containing an earth/peat/sand mixture (6:3:1) and were watered normally. Every week the emergent grasses were cut back to a he-ight of 4 cm and, 40 days after being sown and 1 day after the last cutting, were sprayed with aqueous spray liquors o* an acti~e compound of the formula I. The amount of active compound corresponded to 5 kg of active substance per hectare. The growth of the grasses was evalu-ated 10 and 21 days after application.
Growth inhibition in cereals , Spring wheat tTriticum aestivum), spring barley (Hordeum vulgare) and rye (Secale) were sown in sterilised earth in plastic beakers and the plants were grown in a green-house. 5 days after being sown, the cereal shoots were treated with a spray liquor of the actlve compound. The application to the leaves corresponded to 6 kg of active compound per hectare. Evaluation is carried out after 21 days.
The compounds of Examples 3-6, 8, 17 and 18 caused a pronounced inhibition of growth of grasses, the compounds of Examples 8, 13 and 4 were most active inhibi-ting the growth of cereals.
' ',.~ '. ' . ' . ".' . '. '` . -Inhibition of the growth of side shoots of tobacco plants.
Eight weeks after sowing, tobacco Nicotiana tabacum (variety Xanthi) are transplanted to pots in a greenhouse, normally watered and treated weekly with nutrient solution.
Two weeks after potting, there are chosen per treatment three plants; of these plants one remains untopped and from the two others the growth tip is removed five days before treatment.
Per plant there is then sprayed, laterally from above onto the leading shoot and the upper leaf axils, 10 ml of liquor containing active substance (concentrations: 2.6;
1.3 and 0.6 % corresponding to 6.3 and 1.5 kg per hectare in the open). A part of the liquor consequently runs down the petioles and into the remaining lower leaf axils (con-tact with side-shoot buds).
After setting up of the tests in the greenhouse and watering, the tests are evaluated 4 and 14 days after application of the test liquor.
-Contact effect and systemic effect are evaluatedseparately.
Contact effect: Assessment of the 6 uppermost side shoots;
Syternic effect: Assessment of the uppermost side shoots.
Excellent results are obtained in these tests with the active substances of the invention, such as in particular with those of the Example 7.
.. , ....
-28- ~ 2 Example 3 aj RS -l-Aminoethanephosphonous acid (8.25g., O.075M) was dissolved in water (375 ml.) and ethanol (190 ml.) and the solution was cooled tP 10. Sodium bicarbonate (A.R. grade, 12.75g., O.L5M) was added portionwise with stirring and the resulting solution was cooled to 0.
A solution of the N-hydroxysuccinimide ester of N-benzyloxycarbonyl-L-alanine (24g., 0.075M) in hot ethanol ~260 ml.) was added over a period of lO minutes maintaining the internal temperature at 0.
The heterogeneous mixture was stirred for 2 hours at 0 and then 24 hours at room temperature. The clear solution was evaporated at room temperature to give a ~hite gummy solid. Treatment of this ~esidue with cold dilute hydrochloric acid (2N., 150 ml.) gave a white powdery solid which was allowed to stand 2 hours at room tempera~ure.
The mixture was di~uted with an equal volume of water and allowed to stand 24 hQurs at ~. Filtration gave a mixture of the l~S) and l~R)~-diastereomers of l-[(N-benzyI-oxycarbonyl-L-alanyl)amino~-ethanephosphonous acid ~l2.2g., m.p. 175-6~, L~DO -45.P (2% in glacial acetic 2Ci~ .
. ~ :, , . . , :
.: , ,~: ,: ~
,, :, :;., . ``' ' :`. , ::" :,, :
8i~Z
b) This mixture of diastereomers of l-[(N-benzyloxy-carbonyl-L-Alanyl)amin~-~hanephosphonous acid (12g.) was added to a solution of hydrogen bromide in glacial acetic acid (50 ml., 45% w/w) at 0 and the mixture was stirred for thirty minutes. The solution was allowed to warm up to room temperature and then evaporated to an oily residue. This residue was dissolved in dry methanol (60 ml.) and propylene oxide was carefully added ~ith cooling. The mi;;ture was stirred for two hours at room temperature and allowed to crystallise at 0. It gave a mixture of diaste~eomers of l-(L-alanylam~no)-ethane-phosphonous acid [m.p. 276 decomp., ~a~D -75.6 (2% in water~ .
.
Example 4 The procedure described in Example 3a was repeated using ~IR) -l-aminoethanephosph~nous acid i~stead of RS -l-aminoethanephosphonous acid to give tIR) -1-[N-benzyloxycarbonyl-L-alanyl)amino] -e~hanephosphonous acid. m.p. 180-2 decomp., [~3D0 -60 (2% in glacial acetic acid). [The (+)-~-methylbenzylamine salt of this compound had m.p; 206-7 decomp. and [~ 20 _44.~ (2% in methanol)~.
.
, . :
.
. .
". ., ~' ' , . :
- . . . .
. 1. ~ . -By the same procedure described in Example 3b, this compound was converted to (lR~ -l-(L-alanylamino)-ethanephosphonous acid. m.p. 276 decomp., ~a~20 -80.1 (27~ in water).
Example S
a) ~ l-Aminoethanephosphonous acid (3.4g., 0.03LM) was dissolved in water (15S ml.) and ethanol (186 ml.) and the solution was cooled to 10. Sodium bicarbonate (A.R.grade, 5.25g., 0.062M) was added portionwise with stirring and the resulting solution was cooled to 0.
A solution of the N-hydroxysuccinimide ester of N-benzyloxy-carbonyl-L-alanine (9.9g., 0.031M) in hot et~anol (44 ml.) was added over a period of 10 minutes maintaining the internal temperature of 0. This mixture was stirred ,or 2 hours at 0 and 24 hours at room temperature. Th~ cIear solution was evaporated at r~om temperature to give a gummy sol.id. This material ~Yas stirred with ethanol (50 ml.) and the insoluble material was removed by filtration.
The iltrate was evaporated to dryness, red~.ssolved in absolute ethanol and made just acid with a solut~on of hydrogen chloride in ethanol. The cloudy solution was diluted with ether ~75 ml.) and a white solid was obtained which was dissolved in 75 ml. ethanol and clarified with .. . . ....
. : ...... ..
,. .. . ..
- . ., . ~ ";.
- , ~ . , . ,, - ..
- . . : . ...
-3~ 8~Z
filter-aid. Evaporation of the filtrate gave ~lS) [(N-benzylox~carbonyl-L-a~anyl)amino] -e,hanephGsphonous acid m.p. 143-5 decomp., t~20 + 33.8 (2% in glacial acetic acid. CThe (+)-~-methylbenzylamine sal~ of this compound had m.p. 205-6 decomp., and [~3D0 + 19.8 (2% in methanol)] .
b) By the same procedu~e described in Exampl~
this compound was converted to [l~S)~ -l-(L-alanylamino)-ethanephosphonous acid m.p. 274 decomp., [~ 20 ~ 115 (2% in water).
Example 6.
a) The procedure described in Example 3a was repeated to give a mixture of the lS_ and lR- - diastereome~s of l~[(N-benzyloxycarbonyl-L-alanyl)amino]-ethanephosphonous acid m.p. 175-6, [a]20 _45.7 (2% in glacial acetic acid);
(the filtration liqjuors from which it w~s obtained being set aside for use in Example-6b). This solid was converted to its (~ methylbenzylamine salt in ethanol so~vent and recrysta~ised from ethanol to constant melting point and constant specific rotation, identi~ to that described in ~' Example ~a, namely, m.p. 206-7 decomp., and [a]20 -44 7 (2% in methanol).
- . , ~ ~.
.
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., , . . . : . .
- . . , . - .
- ,:
.. . ., .
- . .
- : ;
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By the procedure described in Example 3b this salt was converted to (~ l-(L-alanylamino)-ethanephosphonous acid m.p. 27~ decomp., [~]D -80.1 (~% in water).
b) The filtration liquors obtained in Example 6a: were evaporated to an oil which was dissolved in ethanol and the splid which formed was collected by filtration. The filtrate was evaporated to dryness and the oil so obtained was stirred with acetone. The waxy solid which formed was collected by filtration and the filtrate again evaporated to dryness. The resultant oil was dissolved in water, extracted successively with ether, propylene oxide, and finally petroleum ether. Evaporation of the aqueous portion gave an oil which on ~reatment with (~ -methyl-benzylamine in isopropanol solvent gave the (+)-~-methyl-benzylamine salt of (lS) -l-[(N-benzy~oxycarbonyl-L-alanylj-amin~ -ethanephosphonous acid m.p. 205-6 decomp., [~ D~1~.5C
(2% in methanol), identical to that described in Example 3a.
By the procedure de~cribed in Example 3b this salt was converted to ;~lS) -l-(L-a;anylamino)-ethanephosphonous acid m.p. 275 decomp.,[~]D + 115 (2% in water) identical t~ that obtained in Example 3b.
Exam~le 7 a) ~lR) -l-(L-alanylamino)-ethanephosphonous acid (1 8g., O.OlM) was dissolved in 2 mixture of water (50 ml.) rt ' ' ' ,: . , , ' ' . .:~ ' " ' : ', ' ':
' ~ ' ` ` ,.. . ", ~ ' .. ,, , ., ., ' ' , ~', . ' '.'' ''' '''''' ".. ''.
~nd cth~nol (25 ml.) and the ~oiution uas cooled to 10 sodium bicarbonate (A.R. erade t.7g., 0.02M) addcd portlon~i~e and the ~oluticn was cooled to 0-.
A solution Or the N-hydroxyRuccinimide eotcr o~ N-~enzyl-oxycarbonyl-~-al~nine(3.2g., O.OlM3 ~n ~lOt ethanol(35 ml.) was added over a por~od of 10 m~nutcs mainta~nln~ the internal temperature at 0-. The he~erogeneous m~xture.
~as st~rred for 2 hours ~t 0- and then 24 hour~ at room tcmperature. The resulting clear solut~on ~as evaporated at roo~ temperature to give a w~te 6~mmY solid. Thi~
re~idue ~a~ stirred wit~ dilute l~ydrochlor~¢ acid(2~.25 m~
~or 2 ~ours at room temper~ture ~nd al;o~ed to crystall~se at 0. Filtration gave ~lR) -l-L(N-benzyloxycar~onyl-L-alanyl)-L-alanylamino~ -ethanephosphonous acid~
having melting point 221 , ~a] - 73.6 (1% glacial acetic acid).
b) By the same procedure as described in ExamDle 3b ~ [(N-benzyloxycarbonyl-L-alanyl)-L-alanylamin~ -ethanephosphonous acid was converted to Ll-(r~)~ l-(L-alanyl-L-alanylamino)-ethanephosphonous acid~
having melting point 263-264, La~ DO _ 112.7(1% in water).
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1~J~
Example 8 The pr~cedure described in Example7a was repeated using (IR) -l-(L-alanyl-L-alanylamino)-ethanephosphonous acid instead o~ (lR) -l-(L-alanylamino)-ethanephosphonous.
acid to give (lR) -1- (N-benzyloxycarbonyl-L-alanyl)-(L-alanyl-L-alanyl~no)-ethanephosphonous acid, of melting point 242 ~a7 20 -114.3 (1% in 2N NaOH).
By the same procedure described in Example 3b, this compound was converted to (lR) ! -1- (L-~lanyl-L-alanyl-L-alanylam~no)-ethanephosphonous acid, of melting point 67 [~ 20 _ 136.3 (1% in water).
Example g The procedure described in Example 7a was repeated usinq (lR) -l-(L-alanyl-L-alanyl-L-alanylamino)-ethane-phosphonous acid instead of; (lR) -1-(L-alanylamino)-ethane-phosphonous acid to give; 51~) -1- (N-benzyloxycarbonyl-L-alanyl)-L-alanyl-L-alanyl-L-alanylamino -ethanephosphonous acid, of melting point 274-275,~a~2 133tO 4~ in 2N NaOH).
By the same procedure described in Example 3b this compounc was converted to (1~) -I-(L- alanyl-L-alanyl-~-alanyl-L-alanylamino)ethanephosphonous acid, of melting polnt 288-289, ~a32 - 154.2 (0.6% in water).
~.:., - . , .~:
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~, . . 1 . ;~
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Example 10 a) The procedure described in Example 3a was repeated using -l-amino-2-methylpropanephosphonous acid instead of -l-amino-ethanephosphonous acid to give a mixture of the R_ and lS-diastereomers of l-[(N-benzyloxycarbonyl-L-ala-nyl)amino]-2-methyl-propanephosphonous acid as a viscous pale yellow oil, [a]D - 17 (2 % in ethanol).
b) By the same procedure described in Example 3b, this product was converted to a mixture of the diastereomers of l-(L-alanylamino)-2-methylpropanephosphonous acid, m.p. 260 decomp., [a]D -40 (1 ~ in water).
Example 11 (a) The procedure described in Example 3a was repeated using [l-(-)]-l-amino-2-methylpropanephosphonous acid instead of RS-l-aminoethanephosphonous acid to give [l-(-)-l-[(N-benzyloxycarbonyl-L-alanyl)-aminol-2-methyl-propanephosphonous acid m.p. 174-5, [a]D -70, (1 % in glacial acetic acid). [The (+)-a-methylbenzylamino salt of this compound had m.p. 183-5 and [a]D -43.9 - 49.9 (2 % in methanol) . ~, ; `:' ,'' ' :' ' - ~
~ 36-, -(b) By the same procedure as described in Example3~, this conlpound was converted to [(l-(-)l-l-(L-alanylamino)-2-methylpropanephosphonous acid m.p. 271-2 decomp., ~]D 54' (1% in w~ter~
Example 12 (a)The procedure described in Example 5a~ was repeated using tl-(+)]-l-amino-2-methylpropanephosphonous acid instead of tl-(S)~ -l-aminoetkanephosphonous acid to give [1-(+9 -1- [(N-benzyloxycarbonyl-L-alanyl)amin~ -2-methyl-propanephosphonous acid as an oil. CThe (+)-~-methylbenzyl-amine salt of this compound had m.p. 184-5 and [~]20 + 15.7 (2Z in methanol) ~
(b) By the same procedure as described in Exampl~e ~, this compou~ was converted t~ rl-(+)~-l-(L-alanrlamino)-2-methyl-propanephosphonous acid m.p. 2Ç3-4 decomp.[~ D0 ~ 79.6 (1% in water) Example 13 .... .
a) The procedure described in Example 3a was repeated using the N-hydroxysuccini~ide ester of N-benzyloxycarbonyl-L-valine instead of the N-hydroxysuccinimide ester of N-benzyloxycarbonyl-L-al2nine.
A mixture of the ~S- and ~R- diastereomers of l- (N-benzyl-oxycarbonyl-L-~alyl)amino; -ethanephosphonous acid, m.p. 202, [~ 20 -38.5 (2% in glacial acetic acid) was obtained~
~" . .~ , - . ~ .
'' ' : ':
~ _37_ ~ Z
b) By the s2m2 procedure described in Example 3P this product was con~erted to a mixture of diastereomers of l-(L-vzlyl~mino)ethane-phosp'aonous acid, m.p. > 260, i~, 25 _30 ~1% in water).
xample 14 a) The procedure described in Example ~a was repeated using th~
hydroxysuccinimide ester of N-benzyloxycarbonyl-~-alanine instead of the ~-hydroxysuccinimlde ester of N-benzyloxycarbonyl-L-alanine.
A mixture of the 1~ S)- and l-~R)-diastereomers or l-[(N-benzyl-oxyc~rbonyl-D-alanyl)amino~ -ethanephosphonous acid, m.p. ~75-176, , ~ 22 ~51.5 (2% in glacial ace~ic acid) was~obtained b) By ~he same procedure described in Example3b this prod~ct ~as converted to a mixture of diastereomers of l-(D-alanylamino?-e~h2nephosphonous acid, m.p. >260, L~J24 +65.5 (2% in water) Example 15 a) The procedure described in Exam~le 3a was repeated using he N-hydroxysuccir.imide ester of N-benzyloxycarbonylglycine instead of the N-hydroxysuccinimide ester of N-benzyloxycarbonyl-L-alanine. A racemic mixture of the S- and R-enantiomers of l-(N-benzyloxycarbonylglycyl)-aminoethane-phosphonous acid, m.p. 86-87 was obtained.
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:
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S~2 b) sy the same procedure described in Example 3b this pro-duct was converted to the racemate of l-glycylaminoethane-phosphonous acid, m.p. 254-255.
Example l6 lRS-l-(L-alanylamino1-ethanephosphonous acid (1.8014g, O.OlM) was dissolved in a solution of cold water (lO ml) and sodium hydroxide (0.40g., O.OlM) and the mixture was stirred for five minutes. The mixture was evaporated to dryness, stirred with absolute ethanol, and filtered to give the sodium salt of lRS-l-(L-alanylamino)-ethanephosphonous acid.
Example 17 lRs-l-(L-alanylamino)-ethanephos~honous acid (lg.) was d~ssolved in a solution of absolute ethanol saturated with dry hydrogen chloride (50 ml). The mixture was evaporated to dryness to glve the hydrochloride of lRS-l-tL-alanylamino)-ethanephosphonous acid.
Example 18 -In a way analogous to the foregoing examples, the following compounds have been obtalned as well.
l-(glycylamino)-anisyl-phosphonous acid m.p.255 (decomposition) l-(glycylamino)-2-methylpropanephosphonous acid, m.p. 253 l-(L-phenylalanylamino)-ethanephosphonous acid, m.p. 172 glycylaminomethylphosphonous acid.
. ..
:, , ` - ` ~ . :
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Water-dispersible active compound concentrates, i.e.
wettable powders, pastes and emulsion concentrates, are agents which can be diluted with water to any desired concentration.
~heyconsist of active compound, carrier if desired additives .
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which stabilise the active compound, surface-active substances and anti-foaming agents and, if desired, solvents.
The wettable powders and pastes are obtained by mixing and grinding the active compounds with dispersing agents and pulverulent carriers in suitable devices until homogeneity is achieved. Examples of carriers are those mentioned above for the solid processing forms. In some cases it is advantageous to use mixtures of different carriers.
Examples of dispersing agents which can be used are: conden-sation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde, condensation pro-ducts of naphthalene or of naphthalenesulphonic acids with phenol and formaldehyde, and alkali met~l salts, ammonium salts and alkaline earth metal salts of ligninsulphonic acid, as well as alkylarylsulphonates, aIkali metal salts and alka-line earth metal salts of dibutyln~phthalenesulphonic acid, fatty alcohol sulphates, such as salts of sulphated hexa-decanols and heptadecanols, and salts of sulphated fatty a7cohol polyethylene glycol ethers, the sodium salt of oleyl methyl tauride, di-tertiary acetylere glycols, diaIkyldilauryl-ammonium chloride and alkali metal salts and alkaline earth metal salts of fatty acids.
Examples of anti-foaming agents which can be used are silicones.
The active compounds are mixed, ground, sieved and strained with the abovementioned additives, in such a way that the particle size of the solid component does not exceed 0.02 , , , .; . , , ~ , :
.. . . ..
', ' '' : ' . :
to 0.04 mm in the case of wettable powders and 0.03 mm in the case of pastes. To prepare emulsion concentrates and pastes, dispersing agents, such as have been listed in the preceding sections, organic solvents and water are used.
Examples of suitable solvents are the following: alcohols, benzene, xylenes, toluene, dimethylsulphoxide, N,N-dialky-lated amides and trialkylamines. me solvents must be virtually odourless and inert towards the active compounds and s~l1dnotbe readily combustible.
Furthermore, the agents according to the invention can be used in the form of solutions. For this purpose, the active compound or several active compounds of the formula I is/are dissolved in suitable organic solvents, solvent m~r water -or mixtures of organic solvents with water.
The content of active compound in the agents described above is between 0.1 and 95%, preferably between 1 and 80%.
Use forms can be diluted down to 0.001%. me amounts used are as a rule 0.1 to 10 kg of active substance/
hectare, preferably 0.25 to 5 kg of active substance/hectare.
m e active compounds of the formula I can be formulated, for example, as follows (parts are parts by weight):
Dustin~ a~ents:
m e following substances are used for the preparation of a) a 5% strength dusting agent and b) a 2% strength , .
dusting agent a) 5 parts o~ (l-RS)-l-(L-alanylamino)ethanephosphonous acid and 95 p~rts o~ talc, b) 2 parts of (1-RS)-l-(L-alanylamino)-2-methylpropane-phosphonous acid 1 part o~ highly disp~rse silica and 97 parts of talc.
The actlve compounds are mixed and ground wYth the carriers.
Granules:
-The following substances are used ~or the preparationof 5% strength granules:
5 parts of (l-R)-l-(L-alanyl-L-alanyl-L-alanylamino)-ethanephosphonous acid, 0.25 part of epichlorohydrin, 0.25 part of cetylpolyethylene glycol ether containing 8 mols of ethylene oxide, - 3,50 parts of polyethylene glycol and 91 parts of kaolin (particle size 0.3 to 0.8mm).
The active substance is mixed with the epichlorohydrin and dissolved in -cetone, , after which polyethylene glycol and cetyl polyethylene glycol ether are added. ' The solution ,thus obtained is sprayed onto kaolin and the acetone is subsequently evaporated off in vacuo.
Wettable ~owders:
The following constituents are used for the prepara-tion of a) a 50% strength wettable powder, b) a 25% strength wettable powder and c) a 10% strength wettable powder:
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a) 50 parts of (l-RS)-l-(L-valylamino)-ethanephosphonous acid, 5 parts of sodium dibutylnaphthylsulphonate, 3 parts of a naphthalenesulphonic acids/phenol-sulphonic acids/formaldehyde condensate, 3:2:1, 20 parts of kaolin and 22 parts of Champagne chalk;
b) 25 parts of the diethanolamine salt of the above active compound, 5 parts of the sodium sal~ of oleyl methyltauride, 2 5 parts of a naphthalenesulphonic acids/form~lde-hyde condensate, O.5 part of carboxymethylcellulose, 5 parts of neutral potassium aluminium silicate and 62 parts of kaolin;
c) 10 par~s Gf (l-R)-l-(L-alanylamino)-ethanephosphonous acid~
3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of a naphthalenesulphonic acids/formal-dehyde condensate and 82 parts of kaolin.
The active compound indicated is absorbed onto the appropriate carriers (kaolin and chalk) and is then mixed and ground. Wettable powders of excellent wettability and suspensibility are obtained. Suspensions of any desired active compound concentration can be obtained from such wetta~le ~, powders by dilution with water Suspensions of this type , .. .. .
, - . . ~. , ~ & ~
are used for combatting weeds and wild grasses in crops of plants by the pre-emergence process, and for the treatment of 1AWnS .
Paste:
The follo.wing substances are used for the prep~ation of a 45% strength paste:
45 parts of (l-R)-l-(L-alanyl-L-alanyl-L-alanyl-L-alanylamino)-ethanephosphonous acid 5 parts of sodium aluminium'silicate, 14 parts of cetyl polyethylene glycol ether containing 8 mols o~ ethylene oxide, 1 part of oleyl polyethylene glycol ether containing 5 mols of ethylene oxide, 2 parts of spindle oil, 23 parts of water and 10 parts of polyethylene glycol.
The active compound is intimately mixed and ground with the additivesin apparatus ~ which i8'~ suitable for this purpose. A paste is obtained, from which suspensions of any desired concentration can be prepared by dilution with water.
me suspensions are suitable for the treatment of lawns.
Emulsion concentrate:
~ ,or the preparation of a 25% strength emulsion concen-trate.
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25 parts of (l-R)-l-(L-alanyl-L-alanylamino)-ethane-phosphonous acid, 5 parts of a mixture of nonylphenol polyoxyethylene and calcium dodecylbenzenesulphonate, 35 parts of 3,~,5-trimethyl-2-cyclohexen-1-one and 35 parts o~ almethylformamide are mixed with one another. This concentrate can be diluted wi~hwat#rto @ve emulsions of suitable concentrations.
Instead of the particular active compound indicated in the above formulation examples, it is also possible to use other compounds from amongst those included in the formula I.
m e active compounds contained in the agents accord-ing to the invention influence the plant growth in various ways. m us they inhibit, delay or suppress, in parti-cular, the growt_ and germination. They there~he have a post-emergent herbicidal action as well as a growth ~nh~biting action.
Agents according to the lnvention, which contain at least one compound of the formula I as the active component, are suitable, in particular, for i~hibiting and suppressing p~ant growth in monocotyledonous and dicotyledonous plants by post-emergent treatment of the sown areas or of the plants, such as shrubs, trees, leguminous crops, sugar cane, onion and potato tubers, fruit trees and vines and, in particular,grasses, cereal crops, tobacco, soya and ornamental plants.
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The action achieved, in particular, by the active com-pounds of the formula I is the desired reduction in plant size, especially the height of growth. In general, a certain change in the form of the plant is associated with this.
In direct association with the reduction of the height of growth, the plant is strengthened. The leaves and stem develop more strongly. me resistance to kinking of mono-cotyledonous plants is increased by shortening the internodaldistances. Crop losses due to a thunderstorm, continuous rain and the like, which usually lead to lodging of cereal crops and leguminous crops, can be largely prevented in this manner and harvesting can thus be made easier. As a side effect, reduced height of growth of useful plants leads to a sa~ing of fertilisers. This also applies, in the same way, to ornamental plants, ornamental lawns, sports fields or other grassed areas.
However, one of the most important problems of pure grass plantings is the actual cutting of the grass, whether in public parks in urban areas, on industrial sites, on playing fields or alongside motor-roads, aircraft landing strips, railway emb~nkments or the sloping banks of waterways. In all these cases lt is necessary to mow the lawn ox cut the growth of grass periodically. This is not only very expen-sive in terms of labour and machinery, but, in the transport sector, also in~ol~es considerable dangers for the personnel concerned and for the occupants of ~ehicles.
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There is therefore, particularly in areas with large traffic networks, an urgent need on the one hand to maintain and care for the greensward which is necessary to strengthen road verges and embankments on traffic routes and, on the other hand, to keep it at a medium height of growth during the whole vegetation period, using simple measures. This need is met in a very favourable mAnner by applying active compounds of the formula I.
By treating trees, shrubs and hedges, in particular in urban and industrial areas, with compounds of the fonmula L
thelabaur-inb~E~e wingwD~kcznbe reduoedin an analogous manner. -T~e growth of shoots and/or the fertilityof fruit trees and vines can also be advantageously influenced by using the active compounds of the formula I.
Ornamental plants with pronounced longitudinal growth can be grown as compact pot plants by treatment with the active compounds mentioned.
The active compounds of the formula I are also used for inhibiting the growth of undesired side shoots, for example in tobacco and ornamental plants, whereby the labour-intensive m~nual breaking off of these shoots is avoided, and furthermore for the inhibition of sprouting in the case of stored tubers, for e*ample in the case of tubers of ornamental plants and in the case of onions and potatoes, and finally for increasing the yield in the case of crop plants having an intense vegetative growth, such as soya and sugar cane, by accelerating the trans-ition from the vegetative growth phase to the generative growth phase through application of active compounds of the formula I.
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.. . . , . -8`~Z
The active compounds of the formula I are preferably employed for inhibiting the growth of weeds, including perennial weeds, grasses, especially perennial grasses, such as Cyperus species and the like, and of cereal crops, tobacco, soya and ornamental plants.
~ he amounts used vary and depend on the time of appllcation. In general, they are between 0.1 and 5 kg of active compound per hectare for the treatment of existlng crops, preferably up to 4 kg per hectare.
The action of the active compounds according to the definition is directed towards the germinating seed(pre-emergent action) but is preferably directed towards the parts of the plant which are above ground ( contact action) in particular the leaves.
The action as a powerful growth inhibitor is shown by the fact that most of the species of plants treated in a post-emergent manner stop growing after an experimental period of three weeks, the partsof the plant treated assuming a dark-green coloration. However, the lea~es do not fall.
In the case of some spec~es of plants, this growth inhibition already occurs at a dosage of 0.5 kg/hectare and less and wlthin several days after treatment.
Since not all species of plants are equally powerfully inhibited, it is possible to use the active com-pounds selectively when a particular low dosage is chosen.
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The active compounds of the formula I are also interestLng combination partners for a number of herbicides of the diphenyl ether, phenylurea and triazine series for use on cereal crops, maize and sugar cane 2nd in fruit growLng and viticulture.
In areas with an increased danger of erosion, the active compounds of the formula I can be used as growth inhi-bitors on the most diverse crops.
In thls case, the weed co~er is not removed but only nh~bited to such an extent that it can no longer compete with the crop plants.
._ ., . . . . .. __ ... . . .. . .
The following Examples further illustrate the present inventlon.
Use Examples 1 and 2 The following test methods were used to demonstrate the usefulness of the actlve compounds as herblcides (post-emergent) and as growth inhibitors:
Post-emergent herbicidal action (contact herbicide) The plants of 7 weeds and crop plants, both monocotyledonous and dicotyledonous, ~ere sprayed after emergence ( in the 4-leaf to 6-leaf stage) with an aqueous actlve co~pound emulsion in a dosage of 4 kg of actlve substance per hectare, and the plants were kept at 24- 26C and a relative atmospheric humidity of 45-60%. The test was evaluated 5 days and 15 days after treatment and the result is given ln the .~ following Table I.
...
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~1~)88~32 compound H2N-CH-CONHCHP(OH)2 H2NCHCO[NHCHCO]2NHCHP(OH)2 L R L L R
plant -Avena sa~iva . 4 5 Setania Italica 2 3 Lolium perenne 3 4 Solanum lycopersicum 3 2 Sinapis alba 2 2 Stellaria media 2 4 Phaseolus vulgaris _ 9 = plant(s) undamaged (as untreated control) --8-2 = intermediate stages of damage The results demonstrate that the compounds according to the present invention which were tested exhibited a pronounced contact herbicidal action on some plants and, as a symptom of the growth inhibiting properties, halted the growth of many plants.
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:-'~ ' . ` ~ .. . -. . :' . ". ~ . . ' ., , Growth inhibition in ~rasses Seeds of the grasses Lolium pere~ne, Poa pratensis, Festuca ovina and Dactylis glomerata were sown in plastic bowls containing an earth/peat/sand mixture (6:3:1) and were watered normally. Every week the emergent grasses were cut back to a he-ight of 4 cm and, 40 days after being sown and 1 day after the last cutting, were sprayed with aqueous spray liquors o* an acti~e compound of the formula I. The amount of active compound corresponded to 5 kg of active substance per hectare. The growth of the grasses was evalu-ated 10 and 21 days after application.
Growth inhibition in cereals , Spring wheat tTriticum aestivum), spring barley (Hordeum vulgare) and rye (Secale) were sown in sterilised earth in plastic beakers and the plants were grown in a green-house. 5 days after being sown, the cereal shoots were treated with a spray liquor of the actlve compound. The application to the leaves corresponded to 6 kg of active compound per hectare. Evaluation is carried out after 21 days.
The compounds of Examples 3-6, 8, 17 and 18 caused a pronounced inhibition of growth of grasses, the compounds of Examples 8, 13 and 4 were most active inhibi-ting the growth of cereals.
' ',.~ '. ' . ' . ".' . '. '` . -Inhibition of the growth of side shoots of tobacco plants.
Eight weeks after sowing, tobacco Nicotiana tabacum (variety Xanthi) are transplanted to pots in a greenhouse, normally watered and treated weekly with nutrient solution.
Two weeks after potting, there are chosen per treatment three plants; of these plants one remains untopped and from the two others the growth tip is removed five days before treatment.
Per plant there is then sprayed, laterally from above onto the leading shoot and the upper leaf axils, 10 ml of liquor containing active substance (concentrations: 2.6;
1.3 and 0.6 % corresponding to 6.3 and 1.5 kg per hectare in the open). A part of the liquor consequently runs down the petioles and into the remaining lower leaf axils (con-tact with side-shoot buds).
After setting up of the tests in the greenhouse and watering, the tests are evaluated 4 and 14 days after application of the test liquor.
-Contact effect and systemic effect are evaluatedseparately.
Contact effect: Assessment of the 6 uppermost side shoots;
Syternic effect: Assessment of the uppermost side shoots.
Excellent results are obtained in these tests with the active substances of the invention, such as in particular with those of the Example 7.
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-28- ~ 2 Example 3 aj RS -l-Aminoethanephosphonous acid (8.25g., O.075M) was dissolved in water (375 ml.) and ethanol (190 ml.) and the solution was cooled tP 10. Sodium bicarbonate (A.R. grade, 12.75g., O.L5M) was added portionwise with stirring and the resulting solution was cooled to 0.
A solution of the N-hydroxysuccinimide ester of N-benzyloxycarbonyl-L-alanine (24g., 0.075M) in hot ethanol ~260 ml.) was added over a period of lO minutes maintaining the internal temperature at 0.
The heterogeneous mixture was stirred for 2 hours at 0 and then 24 hours at room temperature. The clear solution was evaporated at room temperature to give a ~hite gummy solid. Treatment of this ~esidue with cold dilute hydrochloric acid (2N., 150 ml.) gave a white powdery solid which was allowed to stand 2 hours at room tempera~ure.
The mixture was di~uted with an equal volume of water and allowed to stand 24 hQurs at ~. Filtration gave a mixture of the l~S) and l~R)~-diastereomers of l-[(N-benzyI-oxycarbonyl-L-alanyl)amino~-ethanephosphonous acid ~l2.2g., m.p. 175-6~, L~DO -45.P (2% in glacial acetic 2Ci~ .
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b) This mixture of diastereomers of l-[(N-benzyloxy-carbonyl-L-Alanyl)amin~-~hanephosphonous acid (12g.) was added to a solution of hydrogen bromide in glacial acetic acid (50 ml., 45% w/w) at 0 and the mixture was stirred for thirty minutes. The solution was allowed to warm up to room temperature and then evaporated to an oily residue. This residue was dissolved in dry methanol (60 ml.) and propylene oxide was carefully added ~ith cooling. The mi;;ture was stirred for two hours at room temperature and allowed to crystallise at 0. It gave a mixture of diaste~eomers of l-(L-alanylam~no)-ethane-phosphonous acid [m.p. 276 decomp., ~a~D -75.6 (2% in water~ .
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Example 4 The procedure described in Example 3a was repeated using ~IR) -l-aminoethanephosph~nous acid i~stead of RS -l-aminoethanephosphonous acid to give tIR) -1-[N-benzyloxycarbonyl-L-alanyl)amino] -e~hanephosphonous acid. m.p. 180-2 decomp., [~3D0 -60 (2% in glacial acetic acid). [The (+)-~-methylbenzylamine salt of this compound had m.p; 206-7 decomp. and [~ 20 _44.~ (2% in methanol)~.
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, . :
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". ., ~' ' , . :
- . . . .
. 1. ~ . -By the same procedure described in Example 3b, this compound was converted to (lR~ -l-(L-alanylamino)-ethanephosphonous acid. m.p. 276 decomp., ~a~20 -80.1 (27~ in water).
Example S
a) ~ l-Aminoethanephosphonous acid (3.4g., 0.03LM) was dissolved in water (15S ml.) and ethanol (186 ml.) and the solution was cooled to 10. Sodium bicarbonate (A.R.grade, 5.25g., 0.062M) was added portionwise with stirring and the resulting solution was cooled to 0.
A solution of the N-hydroxysuccinimide ester of N-benzyloxy-carbonyl-L-alanine (9.9g., 0.031M) in hot et~anol (44 ml.) was added over a period of 10 minutes maintaining the internal temperature of 0. This mixture was stirred ,or 2 hours at 0 and 24 hours at room temperature. Th~ cIear solution was evaporated at r~om temperature to give a gummy sol.id. This material ~Yas stirred with ethanol (50 ml.) and the insoluble material was removed by filtration.
The iltrate was evaporated to dryness, red~.ssolved in absolute ethanol and made just acid with a solut~on of hydrogen chloride in ethanol. The cloudy solution was diluted with ether ~75 ml.) and a white solid was obtained which was dissolved in 75 ml. ethanol and clarified with .. . . ....
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filter-aid. Evaporation of the filtrate gave ~lS) [(N-benzylox~carbonyl-L-a~anyl)amino] -e,hanephGsphonous acid m.p. 143-5 decomp., t~20 + 33.8 (2% in glacial acetic acid. CThe (+)-~-methylbenzylamine sal~ of this compound had m.p. 205-6 decomp., and [~3D0 + 19.8 (2% in methanol)] .
b) By the same procedu~e described in Exampl~
this compound was converted to [l~S)~ -l-(L-alanylamino)-ethanephosphonous acid m.p. 274 decomp., [~ 20 ~ 115 (2% in water).
Example 6.
a) The procedure described in Example 3a was repeated to give a mixture of the lS_ and lR- - diastereome~s of l~[(N-benzyloxycarbonyl-L-alanyl)amino]-ethanephosphonous acid m.p. 175-6, [a]20 _45.7 (2% in glacial acetic acid);
(the filtration liqjuors from which it w~s obtained being set aside for use in Example-6b). This solid was converted to its (~ methylbenzylamine salt in ethanol so~vent and recrysta~ised from ethanol to constant melting point and constant specific rotation, identi~ to that described in ~' Example ~a, namely, m.p. 206-7 decomp., and [a]20 -44 7 (2% in methanol).
- . , ~ ~.
.
-l . -: ; . - ': .
., , . . . : . .
- . . , . - .
- ,:
.. . ., .
- . .
- : ;
- , .. .. ..
,, , , :
-32~ 8 8~
By the procedure described in Example 3b this salt was converted to (~ l-(L-alanylamino)-ethanephosphonous acid m.p. 27~ decomp., [~]D -80.1 (~% in water).
b) The filtration liquors obtained in Example 6a: were evaporated to an oil which was dissolved in ethanol and the splid which formed was collected by filtration. The filtrate was evaporated to dryness and the oil so obtained was stirred with acetone. The waxy solid which formed was collected by filtration and the filtrate again evaporated to dryness. The resultant oil was dissolved in water, extracted successively with ether, propylene oxide, and finally petroleum ether. Evaporation of the aqueous portion gave an oil which on ~reatment with (~ -methyl-benzylamine in isopropanol solvent gave the (+)-~-methyl-benzylamine salt of (lS) -l-[(N-benzy~oxycarbonyl-L-alanylj-amin~ -ethanephosphonous acid m.p. 205-6 decomp., [~ D~1~.5C
(2% in methanol), identical to that described in Example 3a.
By the procedure de~cribed in Example 3b this salt was converted to ;~lS) -l-(L-a;anylamino)-ethanephosphonous acid m.p. 275 decomp.,[~]D + 115 (2% in water) identical t~ that obtained in Example 3b.
Exam~le 7 a) ~lR) -l-(L-alanylamino)-ethanephosphonous acid (1 8g., O.OlM) was dissolved in 2 mixture of water (50 ml.) rt ' ' ' ,: . , , ' ' . .:~ ' " ' : ', ' ':
' ~ ' ` ` ,.. . ", ~ ' .. ,, , ., ., ' ' , ~', . ' '.'' ''' '''''' ".. ''.
~nd cth~nol (25 ml.) and the ~oiution uas cooled to 10 sodium bicarbonate (A.R. erade t.7g., 0.02M) addcd portlon~i~e and the ~oluticn was cooled to 0-.
A solution Or the N-hydroxyRuccinimide eotcr o~ N-~enzyl-oxycarbonyl-~-al~nine(3.2g., O.OlM3 ~n ~lOt ethanol(35 ml.) was added over a por~od of 10 m~nutcs mainta~nln~ the internal temperature at 0-. The he~erogeneous m~xture.
~as st~rred for 2 hours ~t 0- and then 24 hour~ at room tcmperature. The resulting clear solut~on ~as evaporated at roo~ temperature to give a w~te 6~mmY solid. Thi~
re~idue ~a~ stirred wit~ dilute l~ydrochlor~¢ acid(2~.25 m~
~or 2 ~ours at room temper~ture ~nd al;o~ed to crystall~se at 0. Filtration gave ~lR) -l-L(N-benzyloxycar~onyl-L-alanyl)-L-alanylamino~ -ethanephosphonous acid~
having melting point 221 , ~a] - 73.6 (1% glacial acetic acid).
b) By the same procedure as described in ExamDle 3b ~ [(N-benzyloxycarbonyl-L-alanyl)-L-alanylamin~ -ethanephosphonous acid was converted to Ll-(r~)~ l-(L-alanyl-L-alanylamino)-ethanephosphonous acid~
having melting point 263-264, La~ DO _ 112.7(1% in water).
.
.
, . .
, .
1~J~
Example 8 The pr~cedure described in Example7a was repeated using (IR) -l-(L-alanyl-L-alanylamino)-ethanephosphonous acid instead o~ (lR) -l-(L-alanylamino)-ethanephosphonous.
acid to give (lR) -1- (N-benzyloxycarbonyl-L-alanyl)-(L-alanyl-L-alanyl~no)-ethanephosphonous acid, of melting point 242 ~a7 20 -114.3 (1% in 2N NaOH).
By the same procedure described in Example 3b, this compound was converted to (lR) ! -1- (L-~lanyl-L-alanyl-L-alanylam~no)-ethanephosphonous acid, of melting point 67 [~ 20 _ 136.3 (1% in water).
Example g The procedure described in Example 7a was repeated usinq (lR) -l-(L-alanyl-L-alanyl-L-alanylamino)-ethane-phosphonous acid instead of; (lR) -1-(L-alanylamino)-ethane-phosphonous acid to give; 51~) -1- (N-benzyloxycarbonyl-L-alanyl)-L-alanyl-L-alanyl-L-alanylamino -ethanephosphonous acid, of melting point 274-275,~a~2 133tO 4~ in 2N NaOH).
By the same procedure described in Example 3b this compounc was converted to (1~) -I-(L- alanyl-L-alanyl-~-alanyl-L-alanylamino)ethanephosphonous acid, of melting polnt 288-289, ~a32 - 154.2 (0.6% in water).
~.:., - . , .~:
.,~,. ., . ~.. .~.. ..
~, . . 1 . ;~
li';:~8~13Z
Example 10 a) The procedure described in Example 3a was repeated using -l-amino-2-methylpropanephosphonous acid instead of -l-amino-ethanephosphonous acid to give a mixture of the R_ and lS-diastereomers of l-[(N-benzyloxycarbonyl-L-ala-nyl)amino]-2-methyl-propanephosphonous acid as a viscous pale yellow oil, [a]D - 17 (2 % in ethanol).
b) By the same procedure described in Example 3b, this product was converted to a mixture of the diastereomers of l-(L-alanylamino)-2-methylpropanephosphonous acid, m.p. 260 decomp., [a]D -40 (1 ~ in water).
Example 11 (a) The procedure described in Example 3a was repeated using [l-(-)]-l-amino-2-methylpropanephosphonous acid instead of RS-l-aminoethanephosphonous acid to give [l-(-)-l-[(N-benzyloxycarbonyl-L-alanyl)-aminol-2-methyl-propanephosphonous acid m.p. 174-5, [a]D -70, (1 % in glacial acetic acid). [The (+)-a-methylbenzylamino salt of this compound had m.p. 183-5 and [a]D -43.9 - 49.9 (2 % in methanol) . ~, ; `:' ,'' ' :' ' - ~
~ 36-, -(b) By the same procedure as described in Example3~, this conlpound was converted to [(l-(-)l-l-(L-alanylamino)-2-methylpropanephosphonous acid m.p. 271-2 decomp., ~]D 54' (1% in w~ter~
Example 12 (a)The procedure described in Example 5a~ was repeated using tl-(+)]-l-amino-2-methylpropanephosphonous acid instead of tl-(S)~ -l-aminoetkanephosphonous acid to give [1-(+9 -1- [(N-benzyloxycarbonyl-L-alanyl)amin~ -2-methyl-propanephosphonous acid as an oil. CThe (+)-~-methylbenzyl-amine salt of this compound had m.p. 184-5 and [~]20 + 15.7 (2Z in methanol) ~
(b) By the same procedure as described in Exampl~e ~, this compou~ was converted t~ rl-(+)~-l-(L-alanrlamino)-2-methyl-propanephosphonous acid m.p. 2Ç3-4 decomp.[~ D0 ~ 79.6 (1% in water) Example 13 .... .
a) The procedure described in Example 3a was repeated using the N-hydroxysuccini~ide ester of N-benzyloxycarbonyl-L-valine instead of the N-hydroxysuccinimide ester of N-benzyloxycarbonyl-L-al2nine.
A mixture of the ~S- and ~R- diastereomers of l- (N-benzyl-oxycarbonyl-L-~alyl)amino; -ethanephosphonous acid, m.p. 202, [~ 20 -38.5 (2% in glacial acetic acid) was obtained~
~" . .~ , - . ~ .
'' ' : ':
~ _37_ ~ Z
b) By the s2m2 procedure described in Example 3P this product was con~erted to a mixture of diastereomers of l-(L-vzlyl~mino)ethane-phosp'aonous acid, m.p. > 260, i~, 25 _30 ~1% in water).
xample 14 a) The procedure described in Example ~a was repeated using th~
hydroxysuccinimide ester of N-benzyloxycarbonyl-~-alanine instead of the ~-hydroxysuccinimlde ester of N-benzyloxycarbonyl-L-alanine.
A mixture of the 1~ S)- and l-~R)-diastereomers or l-[(N-benzyl-oxyc~rbonyl-D-alanyl)amino~ -ethanephosphonous acid, m.p. ~75-176, , ~ 22 ~51.5 (2% in glacial ace~ic acid) was~obtained b) By ~he same procedure described in Example3b this prod~ct ~as converted to a mixture of diastereomers of l-(D-alanylamino?-e~h2nephosphonous acid, m.p. >260, L~J24 +65.5 (2% in water) Example 15 a) The procedure described in Exam~le 3a was repeated using he N-hydroxysuccir.imide ester of N-benzyloxycarbonylglycine instead of the N-hydroxysuccinimide ester of N-benzyloxycarbonyl-L-alanine. A racemic mixture of the S- and R-enantiomers of l-(N-benzyloxycarbonylglycyl)-aminoethane-phosphonous acid, m.p. 86-87 was obtained.
. .
:
' . ' :
S~2 b) sy the same procedure described in Example 3b this pro-duct was converted to the racemate of l-glycylaminoethane-phosphonous acid, m.p. 254-255.
Example l6 lRS-l-(L-alanylamino1-ethanephosphonous acid (1.8014g, O.OlM) was dissolved in a solution of cold water (lO ml) and sodium hydroxide (0.40g., O.OlM) and the mixture was stirred for five minutes. The mixture was evaporated to dryness, stirred with absolute ethanol, and filtered to give the sodium salt of lRS-l-(L-alanylamino)-ethanephosphonous acid.
Example 17 lRs-l-(L-alanylamino)-ethanephos~honous acid (lg.) was d~ssolved in a solution of absolute ethanol saturated with dry hydrogen chloride (50 ml). The mixture was evaporated to dryness to glve the hydrochloride of lRS-l-tL-alanylamino)-ethanephosphonous acid.
Example 18 -In a way analogous to the foregoing examples, the following compounds have been obtalned as well.
l-(glycylamino)-anisyl-phosphonous acid m.p.255 (decomposition) l-(glycylamino)-2-methylpropanephosphonous acid, m.p. 253 l-(L-phenylalanylamino)-ethanephosphonous acid, m.p. 172 glycylaminomethylphosphonous acid.
. ..
:, , ` - ` ~ . :
.
Claims (17)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An agent for influencing plant growth comprising, in addition to carriers and/or other additives, at least one compound of formula:- (I) or the corresponding zwitterion form in which R and R1 may be the same or different and each can be hydrogen, deutrium or a lower alkyl group, lower alkenyl, lower alkynyl, C3-C7 cycloalkyl, phenyl or a 5-membered nitrogen containing ring containing one or more oxygen, nitrogen or sulphur atoms and which may be fused to an aromatic ring, a lower alkyl group substituted by a C3-C7 cycloalkyl radical, a lower alkyl group substituted by a phenylradical,a lower alkyl group substituted by a 5-membered, nitrogen containing ring as defined above, or R and R1 together form a polymethylene chain optionally interrupted by an oxygen, nitrogen or sulphur atoms, or R1 represents, together with the C(R) - N< residue to which it is attached, the atoms required to complete a 5-membered nitrogen containing ring and R2 and R3 may be the same or different and each can be hydrogen, lower alkyl, C3-C7 cycloalkyl, phenyl or lower alkyl substituted by a C3-C7 cycloalkyl radical, lower alkyl substituted by a 5-membered ring containing one or more nitrogen atoms; a 5-membered ring containing one or more nitrogen atoms; or R2 and R3, independently, together with the C(H)-N residue to which each is attached, may each represent the atoms required to complete a heterocyclic radical; and n is 0, 1, 2 or 3; as well as the esters and salts thereof with physiologically acceptable alcohols or acids or bases respectively and all optical isomers thereof.
2. An agent as claimed in claim 1 wherein R and R1 may be the same or different and each is hydrogen, deuterium, lower alkyl, or lower alkyl substituted by C3-C7 cycloalkyl, phenyl or a 5-membered nitrogen containing ring, optionally substituted by one to three hydroxy or lower alkoxy groups; or R1 represents, together with the -CR-N< residue to which it is attached, the atoms required to complete a 2-pyrrolidinyl group; R2 and R3 may be the same or different and each is hydrogen, lower alkyl, or lower alkyl substituted by C3-C7 cycloalkyl, phenyl or by a 5-membered nitrogen containing ring optionally substituted by one to three hydroxy or lower alkoxy groups or R2 or R3 each represents together with the -CH-N< residue to which it is attached, the atoms required to complete the 2-pyrrolidinyl group; and n is 0, 1, 2 or 3; as well as the esters and salts with physiologically acceptable alcohols, or acids or bases, respectively; and all optical isomers thereof.
3. An agent as claimed in claim 1 wherein R and R1 may be the same or different and each is hydrogen deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, optionally substituted by imidazolyl, indolyl,benzyl groups optionally substituted by one to three hydroxy groups, lower alkoxy, lower alkylthio, amino or carboxy groups or R1 represents together with the -C(R)-N< residue to which it is attached, the atoms required to complete a 2-pyrrolidinyl group; R2 and R3 may be the same or different and each can be hydrogen, methyl, isopropyl, isobutyl, benzyl, aminobutyl, hydroxymethyl, 1-hydroxyethyl, 2-methylthioethyl, imidazolymethyl, or indolylmethyl, or R2 or R3, respectively, together with the -CH-N< residue to which it is attached, represents the atoms required to complete a 2-pyrrolidinyl group; and n is 0, 1, 2 or 3; as well as the esters and salts with physiologically acceptable alcohols, or acids or bases, respectively;
and all optical isomers thereof.
and all optical isomers thereof.
4. An agent as claimed in claim 1 wherein R is hydrogen; R1 is methyl;
R2 and R3 may be the same or different and each is hydrogen, methyl, isopropyl, isobutyl, aminobutyl, hydroxymethyl, l-hydroxyethyl, 2-methylthioethyl, imidazolylmethyl or indolylmethyl, benzyl or R2 or R3 respectively, together with the -CR-N or -CH-N residue to which it is attached represents the atoms required to complete a 2-pyrrolidinyl group; and n is 0, 1, 2 or 3; and the esters and salts thereof with physiologically acceptable alcohols or acids or bases, respectively; and all optical isomers thereof.
R2 and R3 may be the same or different and each is hydrogen, methyl, isopropyl, isobutyl, aminobutyl, hydroxymethyl, l-hydroxyethyl, 2-methylthioethyl, imidazolylmethyl or indolylmethyl, benzyl or R2 or R3 respectively, together with the -CR-N or -CH-N residue to which it is attached represents the atoms required to complete a 2-pyrrolidinyl group; and n is 0, 1, 2 or 3; and the esters and salts thereof with physiologically acceptable alcohols or acids or bases, respectively; and all optical isomers thereof.
5. An agent as claimed in claim 1 wherein the agent is in the form of a solid processing form, an active compound concentrate which is dispersible in water or a liquid processing form.
6. An agent as claimed in claim 1 or 5, wherein the content of the compound of formula I is between 0.1 to 95 %.
7. An agent as claimed in claim 1 or 5 wherein the content of the compound of formula I is between 1 and 80 %.
8. An agent according to claim 1 for influencing plant growth containing as active ingredient 1-(D-alanylamino)-ethanephosphonous acid.
9. An agent according to claim 1 containing as active ingredient 1-(L-alanylamino)-ethanephosphonous acid.
10. An agent according to claim 1 containing as active ingredient 1-glycylamino-ethanephosphonous acid.
11. An agent according to claim 1 containing as active ingredient 1-(L-valylamino-ethanephosphonous acid.
12. An agent according to claim 1 containing as active ingredient 1-(L-alanyl-L-alanylamino)-ethanephosphonous acid.
13. A method for inhibiting or supressing plant growth in mono- and dicotyledonous plants by post emergence treatment, comprising applying to the plants an effective amount of at least one compound of formula I
as defined in claim 1.
as defined in claim 1.
14. A method as claimed in claim 13 wherein the compound is applied to sown areas or to the plants.
15. A method as claimed in claim 13, wherein the plant is a grass, cereal crop, tobacco, soya or an ornamental plant.
16. A method as claimed in claim 13 wherein the amount applied of the compound of formula I is between 0.1 and 5 kg of active compound per hectare, for the treatment of existing crops.
17. A method as claimed in claim 13 wherein the amount applied of the compound of formula I is up to 4 kg of active compound, per hectare.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7939400 | 1979-10-05 | ||
| GB39400/78 | 1979-10-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1158882A true CA1158882A (en) | 1983-12-20 |
Family
ID=10509189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000336898A Expired CA1158882A (en) | 1979-10-05 | 1979-10-03 | Agent and method for influencing plant growth containing phosphonous acid peptides |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1158882A (en) |
-
1979
- 1979-10-03 CA CA000336898A patent/CA1158882A/en not_active Expired
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