CA1047534A - Haloacetanilides for influencing plant growth - Google Patents
Haloacetanilides for influencing plant growthInfo
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- CA1047534A CA1047534A CA191,039A CA191039A CA1047534A CA 1047534 A CA1047534 A CA 1047534A CA 191039 A CA191039 A CA 191039A CA 1047534 A CA1047534 A CA 1047534A
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- compound according
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- methyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
Abstract
Abstract of the Disclosure Agents for influencing plant growth, which contain as active substance a compound of the formula I
Description
~o47S34 The present invention provides N-substituted halo-ac~etanilides, a process for their manufacture, also plant regulating agents which contain these new _ompounds as active substances, as well as a method of selectively S controlling weeds in crops of cultivated plants, which comprises the use of the new active substances or of agents which contain them.
Reference is made to the following patent speci-fication as representing the prior art in respect of plant regulating haloacetanilides: French patents 1.337.529, 1.419.116 and 2.028.991, Belgian patent 746.288, and US patents 2.863.752, 3.442.945, and 3.547.620.
It is the task of this invention to provide halo-acetanilides with improved plant regulating properties, lS i.e. which in low rates of application control a larger number of weed species, and, above all, highly resistant weeds, distinctly better than the known haloacetanilides, but without having any adverse effect on the cultures of crop plants in which they are to be used.
Compared with the compounds known up till now, the new N-substituted haloacetanilides according to the invention differ fundamentally in their chemical structure to-improve their activity. They have the formula I
'' ~
10~7534 1, `
3 ~ N \ A-0~
wherein R represents an alkyl radical with at most 3 carbon atoms, an alkenyl radical with 3 or 4 carbon atoms, a cyclo-propyl radical or a cyclopropylmethyl radical, A represents an unsubstituted ethylene chain (-CH2-CH2) or an ethylene chain which is monosubstituted by ethyl or mono- or disub-stituted by methyl, Rl represents hydrogen or an alkyl radical with at most 4 carbon atoms, R2 represents an alkyl radical with at most 4 carbon atoms, R3 and R4 each inde-pendently represents a substituent which is in meta-position to the amino group, namely halogen, cyano, alkyl, alkylthio or alkoxy, each with at most 3 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 3 halogen atoms,alkoxyalkyl or alkylthioalkyl with 2 to 4 carbon atoms, and one of the 1~ substituents R3 or R4 also represents hydrogen, and X repres-ents chlorine or bromine.
By substituents which represent or contain an alkyl function are to be understood - depending on the limitation according to the definition - the lower members methyl, ethyl, propyl, isopropyl, butyl, sec. butyl, isobutyl or tert. butyl.
10~7534 By alkenyl radicals are meant the allyl group, the various methylallyl groups, and the but-3-enyl group.
The term "halogen" comprises fluorine, chlorine, bromine or iodine. Haloalkyl according to definition is to be understood as meaning the mono- to trihalogenated methyl or ethyl group~ e.g. trichloromethyl, dichloromethyl, 1,2-dichloroethyl or trifluoromethyl.
Preferred active substances are compounds in which X represents chlorine. Of these compounds, those whose substituents Rl and R2 represent alkyl radicals have in the majority of cases a particularly favourable activity spect-rum in crop plants and weeds. Advantageously, the total number of carbon atoms of both alkyl radicals Rl and R2 doés not exceed S.
A biologically interesting group of compounds is that in which A, R, Rl, R2, and X have the meanings given for the formula I, and in which one of the substituents R3 or R4 which is in meta-position to the amino group represents chlorine, the cyano, trifluoromethyl, methoxy, or methylthio group, and the other represents hydrogen.
Preeminent among these compounds are those in which A represents an ethylene chain which is monosubstituted by methyl or ethyl.
Another biologically interesting and, for specific fie~ds of use, preferred group of compounds of the formula I
is that in which A and R have the indicated meanings, X
represents chlorine, Rl represents a methyl group, R2 represents hydrogen, methyl, or ethyl, and wherein further the substituent R3 in meta-position to the amino group S represents an alkyl radical with at most 3 carbon atoms, and R4 represents hydrogen.
Particularly preferred compounds of this last named group are those of the formula Ia R
C ~ H3 f H ~ CH2 ~ - R' ~ ~ 0 - CH2Cl (Ia) wherein R2 represents hydrogen, a methyl or ethyl group, ~nd R' and R5 each independently represents a methyl or an ethyl group.
Examples of such herbicides of the formula Ia with particularly favourable selectivity between cultures of crop plants and weeds are
Reference is made to the following patent speci-fication as representing the prior art in respect of plant regulating haloacetanilides: French patents 1.337.529, 1.419.116 and 2.028.991, Belgian patent 746.288, and US patents 2.863.752, 3.442.945, and 3.547.620.
It is the task of this invention to provide halo-acetanilides with improved plant regulating properties, lS i.e. which in low rates of application control a larger number of weed species, and, above all, highly resistant weeds, distinctly better than the known haloacetanilides, but without having any adverse effect on the cultures of crop plants in which they are to be used.
Compared with the compounds known up till now, the new N-substituted haloacetanilides according to the invention differ fundamentally in their chemical structure to-improve their activity. They have the formula I
'' ~
10~7534 1, `
3 ~ N \ A-0~
wherein R represents an alkyl radical with at most 3 carbon atoms, an alkenyl radical with 3 or 4 carbon atoms, a cyclo-propyl radical or a cyclopropylmethyl radical, A represents an unsubstituted ethylene chain (-CH2-CH2) or an ethylene chain which is monosubstituted by ethyl or mono- or disub-stituted by methyl, Rl represents hydrogen or an alkyl radical with at most 4 carbon atoms, R2 represents an alkyl radical with at most 4 carbon atoms, R3 and R4 each inde-pendently represents a substituent which is in meta-position to the amino group, namely halogen, cyano, alkyl, alkylthio or alkoxy, each with at most 3 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 3 halogen atoms,alkoxyalkyl or alkylthioalkyl with 2 to 4 carbon atoms, and one of the 1~ substituents R3 or R4 also represents hydrogen, and X repres-ents chlorine or bromine.
By substituents which represent or contain an alkyl function are to be understood - depending on the limitation according to the definition - the lower members methyl, ethyl, propyl, isopropyl, butyl, sec. butyl, isobutyl or tert. butyl.
10~7534 By alkenyl radicals are meant the allyl group, the various methylallyl groups, and the but-3-enyl group.
The term "halogen" comprises fluorine, chlorine, bromine or iodine. Haloalkyl according to definition is to be understood as meaning the mono- to trihalogenated methyl or ethyl group~ e.g. trichloromethyl, dichloromethyl, 1,2-dichloroethyl or trifluoromethyl.
Preferred active substances are compounds in which X represents chlorine. Of these compounds, those whose substituents Rl and R2 represent alkyl radicals have in the majority of cases a particularly favourable activity spect-rum in crop plants and weeds. Advantageously, the total number of carbon atoms of both alkyl radicals Rl and R2 doés not exceed S.
A biologically interesting group of compounds is that in which A, R, Rl, R2, and X have the meanings given for the formula I, and in which one of the substituents R3 or R4 which is in meta-position to the amino group represents chlorine, the cyano, trifluoromethyl, methoxy, or methylthio group, and the other represents hydrogen.
Preeminent among these compounds are those in which A represents an ethylene chain which is monosubstituted by methyl or ethyl.
Another biologically interesting and, for specific fie~ds of use, preferred group of compounds of the formula I
is that in which A and R have the indicated meanings, X
represents chlorine, Rl represents a methyl group, R2 represents hydrogen, methyl, or ethyl, and wherein further the substituent R3 in meta-position to the amino group S represents an alkyl radical with at most 3 carbon atoms, and R4 represents hydrogen.
Particularly preferred compounds of this last named group are those of the formula Ia R
C ~ H3 f H ~ CH2 ~ - R' ~ ~ 0 - CH2Cl (Ia) wherein R2 represents hydrogen, a methyl or ethyl group, ~nd R' and R5 each independently represents a methyl or an ethyl group.
Examples of such herbicides of the formula Ia with particularly favourable selectivity between cultures of crop plants and weeds are
2,3-dimethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetanilide 2,3-dimethyl-N-(l'-methoxybut-2-yl)-N-chloroacetanilide 2,3-dimethyl-6-ethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetani-lide 2,3-dimethyl-6-ethyl-N-(l'-methoxybut-2'-yl)-N-chloroacetanilide also the compourlds of the formula I
2,6-dimethyl-3-chloro-N-(2'-methoxyethyl)-N-chloroacetanilide, 2,6-dimethyl-3-chloro-N-(l'-methoxyprop-2'-yl)-N-chloroacet-anilide, 2,6-dimethyl-3-methoxy-N-(2'-methoxyethyl)-N-chloroacetanilide, 2,6-dimethyl-3-methoxy-N-(l'-methoxyprop-2'-yl)-N-chloroacet-anilide, 2,6-dimethyl-3-trifluoromethyl-N-(2'-methoxyethyl)-N-chloro-acetanilide, 2,6-dimethyl-3-trifluoromethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetanilide.
There are a number of different ways of manufacturing compounds of the formula I, conditioned by the possibility of altering the sequence of different reaction steps. This applies above all to substitution reactions in the phenyl nucleus of the basic aniline. However, the substituents Rl to R4 will have been introduced with advantage first before the reactions at the amino group are effected.
The new haloacetanilides of the formula I are manufactured according to the invention by reacting a N-substîtuted aniline of the formula II
R
R3 ~ NH-A-OR (Il) R4 ~
104'7534 with a haloacetylating agent, preferably an anhydride or halide of chloroacetic or bromoacetic acid. In formula II, the symbols R, Rl to R4 and A have the same meanings as given under formula I.
It is also possible to manufacture the compounds of the formula I in such a way that an aniline which is substituted by Rl to R4 is reacted optionally with (i) 2-haloethanol or ethyl~ne oxide to introduce the hydroxy-alkyl chain -CH2-CH2-OH, or (ii) 2-halopropanol to introduce the hydroxyalkyl chain -CH-CH2-OH, or (iii) l-halopropan-2-ol or propylene oxide to introduce the ~F13 hydroxyalkyl chain -CH2- H-OH, or (iv) 3-halobutan-2-ol to introduce the hydroxyalkyl chain CH3lH3 -lH-CH-OH, or (v) l-halobutan-2-ol to introduce the hydroxyalkyl chain ~ 2H5 -CH2- H- OH, or (vi) a corresponding haloalkanol to introduce one of the 1~47534 further possible structural chains -A-OH, in which "halogen"
represents chlorine or bromine;then the resulting compound of the formula II~
1 1 .
R3 ~ NH-A-OH (II a) 4 ~
is chloroacetylated or bromoacetylated, preferably with an anhydride or halide of chloroacetic or bromoacetic acid, and, finally,the still free OH group is etherified in acid medium (e.g. HCl, H2S04) under mild conditions and in conventional manner with an alcohol R3-OH, in which the radical R3 cor-responds to the definition given under formula I.
The reactions can be carried out in the presence or absence of solvents or diluents which are inert towards the reactants. Examples of suitable solvents or diluents are:
aliphatic, aromatic or halogenated hydrocarbons, such as benzene, toluene, xylene, petroleum ether, chlo~oben~ene, me-~hylene chloride, ethylene chloride, chloroform; ethers and ethereal compounds, such as dialkyl ethers, dioxan, tetrahydro-furan; nitriles, such as acetonitrile; N,N-dialkylated amides, such as dimethyl formamide; also dimethyl sulphoxide, and also mixtures of these solvents.
~0~7534 As s~ able haloacetylating agents there are pre-ferably used haloacetic anhydrides, such as chloroacetic anhydride, and haloacetic halides, such as chloroacetyl chloride. However, it is also possible to carry out the reaction with haloacetic acids, their esters or amides.
The reaction temperatures are between 0 and 200C, pre-ferably between 20 and 100C. Often, especially if halo-acetyl halides are used, the haloacetylation is carried oùt in the presence of an acid acceptor. Suitable acid acceptors are: tertiary amines, such as trialkylamines, e,g. triethylamine, pyridine and pyridine bases, or in-organic bases, such as the oxides and hydroxides, hydrogen carbonates and carbonates or alkali and alkaline earth metals. Furthermore, it is also possible to use the cor-responding aniline of the formula II as acid acceptor, in which case a surplus must be used.
A number of starting materials of the formula II
and corresponding hydroxyalkyl derivatives (R=H) are known, e.g. from US patent 2.381.071, 2.759.943 as well as from Am.Soc. 84, 743 and Bull. Soc. Chim. France 1962, 303 and 1965, 2037. These starting materials, as well as those not yet described in the literature, which fall under the general formula II, can be manufactured easily by one of the following known methods, for example:
'7534 a) by condensation of the aniline of the formula III which is appropriately substituted by Rl to R4 ~ ~ NH2 (III) R4 ~
with a carbonyl compound of the formula IV
0 = C - C - O - R IV
in which the substituents R5, R6, and R7 represent h~gen,methyl or ethyl, but together possess at most 2 carbon atoms, and R has the meaning given for the formula I, and simultaneous or subsequent catalytic hydrogenation of the resulting azomethine of the formula V
R3 ~ R5 R6 . (V) b) by reaction of the aniline of the formula III which is appropriately substituted by Rl to R4 with a compound of - the formula VI
~.n47534 Y - A - OR (VI) wherein A and R are defined as under formula I and Y repre-sents a halogen atom or another acid radical, in particular an alkylsulphonic acid radical or an arylsulphonic acid radical. Compounds of the formula VI with benzenesulphonic acid radica~ Y are described e.g. in Can. J. Chem. 33, 1207, and those with tosyloxy radicals (CH3-C6H4-S03-) in British patent 869,083.
There are, of course, a number of other processes ~0 for the manufacture of the starting materials of the formula II from appropriately substituted anilines.
Some alkylsubstituted anilines of the formula III
can be manufactured from natural raw materials, e.g. coal tar oil, others can be manufactured by known methods of which a number are cited hereinbelow:
a) 2-alkylanilines or 2,6-dialkylanilines with C2-C4 alkyl groups in the ortho-position of the phenyl nucleus are advantageously manufactured from the corresponding aniline with a C2-C4 alkene (e.g. ethylene, propylene, l-butene, 2-butene etc,) under pressure in the presence of aluminium at temperatures above 200C lAngew. Chemie 69, 125 (1957)~.
It is thus possible e.g. to obtain 2,3-dimethyl-6-ethyl aniline from 2,3-dimethyl aniline and ethylene, and 2,3-dimethyl-6-isopropyl aniline from 2,3-dimethyl aniline and propylene.
10~7S34 b) Starting from the appropriate toluene, ethylbenzene, isopropyl benzene, xylene etc., there are obtained by di-nitration and partial reduction metanitroanilines from which, by diazotiation via the diazonium salts, meta-nitrohalobenzenes, meta-nitrocyanobenzenes etc. are obtained, which can then be converted by reduction into corresponding anilines of the formula III (J. Chem. Soc. 1927, 1106).
c) Meta-alkoxyanilines are advantageously manufactured by alkylation of the hydroxyl group of a meta-nitrophenol IJ. Org. Chem. 26, 4749 (1962)] and subsequent reduction of the nitro group.
d) Meta-alkylthioanilines of the formula III are obtained appropriately by sulphochlorination of e.g. acylated aniline, reduction of the sulphonyl chloride group to the mercapto group and alkylation thereof (British patent 1.027.060).
e) Meta-trifluoromethyl anilines of the formula III are obtained e.g. from 2, (4)-(di)alkyl-3,5-dinitro-benzoic acid, partial reduction of the nitro group in 5-position to the amino group, diazotiation ar.d elimination thereof and subsequent conversion of the carboxyl group to the tri-fluoromethyl group, whereupon the remaining nitro group is reduced to the amino group (British patent 1.027.030).
A number of intermediate products which are of importance for this invention are cited hereinbelow:
~04'7534 2,5-dimethyl-6~ethylaniline, b.p. 70-76C (0.7 Torr) 2,3-dimethyl-6-ethylaniline, b.p. 70-76C (0.7 Torr) 2,6-dimethyl-3-bromo-(2'-ethoxyethyl)-aniline b.p. 113-118C
(0.5 Torr) 2,3,5,6-tetramethyl-(2'-methoxyethyl)-aniline, b.p. 81-92C
(0.001 Torr) 52,3-dimethyl-(2'-methoxyethyl)-aniline, b.p. 73C (0.02 Torr) 2,3-dimethyl-(1'-methoxyprop-2'-yl)-aniline, b.p. 67-76C
(0.001 Torr) 2,3-dimethyl-(2'-ethoxyethyl)-aniline, b.p. 82-86C (0.01 Torr) 2,3,5-trimethyl-(2'-methoxyethyl)-aniline, b.p. 92C (0.3 Torr) 2,3,5-trimethyl-(1'-methoxyprop-2'-yl)-aniline, b.p. 94C
(0.5 Torr) 102,5-dimethyl-6-ethyl-(2'-methoxyethyl)-aniline, b.p. 95C
(0.7 Torr) 2,5-dimethyl-6-ethyl-(2'-ethoxyethyl)-aniline, b.p. 90C
(0.4 Torr) 2,5-dimethyl-6-ethyl-(2'-n-propoxyethyl)-aniline, b.p. 98-105C
(0.4 Torr) 2,5-dimethyl-6-ethyl-(2'-isopropoxyethyl)-aniline, b.p.
103-105C (0.6 Torr) 2,5-dimethyl-6-ethyl-(2'-allyloxyethyl)-aniline, b.p. 93C
(0.1 Torr) 152,3-dimethyl-6-ethyl-(2'-methoxyethyl)-aniline, b.p. 95C
(0.7 Torr) 2 9 3-dimethyl-6-ethyl-(2'-ethoxyethyl)-aniline, b.p. 90C
(0.4 Torr) 2,3-dimethyl-6-ethyl-(2'-n-propoxyethyl)-aniline, b.p. 98-105C
(0.4 Torr) 2,3-dimethyl-6-ethyl-(2'-isopropoxyethyl)-aniline, b.p.
103-105C (0.6 Torr) 1()~l'7534 2,3-dimethyl-6-ethyl-(1'-methoxyprop-2'-yl)-aniline, b.p. 90-94C (0.8 Torr) 2,3-dimethyl-6-ethyl-(l'-metho2yprop-2'-yl)-aniline, b.p. 102-106C (0.6 Torr) The following Examples illustrate the process according to the invention, including the manufacture of starting materials. Further haloacetanilides of the formula I, which were manufactured by one of the described processes, are listed in the subsequent Table~
~047534 Example 1 a) A solution of 55.7 g (0.278 mole) of 3-bromo-2,6-dimethyl aniline and 34.0 g (0.139 mole) of p-toluenesulphonic acis-(2-ethoxyethyl)-ester in 100 ml of toluene is refluxed for 25 hours. After the reaction mixture has cooled J it is made alkaline, diluted with ether, and the organic phase is washed repeatedly with water. The dried solution is evaporated and vacuum distillation of the residue yields the desired pro-duct, N-(2'-ethoxy-ethyl)-3-bromo-2,6-dimethyl aniline, b.p. 113-118C /O.STorr.
b) A suspension of lS.0 g (O.SS mole) of N-(2'-ethoxyethyl)-
2,6-dimethyl-3-chloro-N-(2'-methoxyethyl)-N-chloroacetanilide, 2,6-dimethyl-3-chloro-N-(l'-methoxyprop-2'-yl)-N-chloroacet-anilide, 2,6-dimethyl-3-methoxy-N-(2'-methoxyethyl)-N-chloroacetanilide, 2,6-dimethyl-3-methoxy-N-(l'-methoxyprop-2'-yl)-N-chloroacet-anilide, 2,6-dimethyl-3-trifluoromethyl-N-(2'-methoxyethyl)-N-chloro-acetanilide, 2,6-dimethyl-3-trifluoromethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetanilide.
There are a number of different ways of manufacturing compounds of the formula I, conditioned by the possibility of altering the sequence of different reaction steps. This applies above all to substitution reactions in the phenyl nucleus of the basic aniline. However, the substituents Rl to R4 will have been introduced with advantage first before the reactions at the amino group are effected.
The new haloacetanilides of the formula I are manufactured according to the invention by reacting a N-substîtuted aniline of the formula II
R
R3 ~ NH-A-OR (Il) R4 ~
104'7534 with a haloacetylating agent, preferably an anhydride or halide of chloroacetic or bromoacetic acid. In formula II, the symbols R, Rl to R4 and A have the same meanings as given under formula I.
It is also possible to manufacture the compounds of the formula I in such a way that an aniline which is substituted by Rl to R4 is reacted optionally with (i) 2-haloethanol or ethyl~ne oxide to introduce the hydroxy-alkyl chain -CH2-CH2-OH, or (ii) 2-halopropanol to introduce the hydroxyalkyl chain -CH-CH2-OH, or (iii) l-halopropan-2-ol or propylene oxide to introduce the ~F13 hydroxyalkyl chain -CH2- H-OH, or (iv) 3-halobutan-2-ol to introduce the hydroxyalkyl chain CH3lH3 -lH-CH-OH, or (v) l-halobutan-2-ol to introduce the hydroxyalkyl chain ~ 2H5 -CH2- H- OH, or (vi) a corresponding haloalkanol to introduce one of the 1~47534 further possible structural chains -A-OH, in which "halogen"
represents chlorine or bromine;then the resulting compound of the formula II~
1 1 .
R3 ~ NH-A-OH (II a) 4 ~
is chloroacetylated or bromoacetylated, preferably with an anhydride or halide of chloroacetic or bromoacetic acid, and, finally,the still free OH group is etherified in acid medium (e.g. HCl, H2S04) under mild conditions and in conventional manner with an alcohol R3-OH, in which the radical R3 cor-responds to the definition given under formula I.
The reactions can be carried out in the presence or absence of solvents or diluents which are inert towards the reactants. Examples of suitable solvents or diluents are:
aliphatic, aromatic or halogenated hydrocarbons, such as benzene, toluene, xylene, petroleum ether, chlo~oben~ene, me-~hylene chloride, ethylene chloride, chloroform; ethers and ethereal compounds, such as dialkyl ethers, dioxan, tetrahydro-furan; nitriles, such as acetonitrile; N,N-dialkylated amides, such as dimethyl formamide; also dimethyl sulphoxide, and also mixtures of these solvents.
~0~7534 As s~ able haloacetylating agents there are pre-ferably used haloacetic anhydrides, such as chloroacetic anhydride, and haloacetic halides, such as chloroacetyl chloride. However, it is also possible to carry out the reaction with haloacetic acids, their esters or amides.
The reaction temperatures are between 0 and 200C, pre-ferably between 20 and 100C. Often, especially if halo-acetyl halides are used, the haloacetylation is carried oùt in the presence of an acid acceptor. Suitable acid acceptors are: tertiary amines, such as trialkylamines, e,g. triethylamine, pyridine and pyridine bases, or in-organic bases, such as the oxides and hydroxides, hydrogen carbonates and carbonates or alkali and alkaline earth metals. Furthermore, it is also possible to use the cor-responding aniline of the formula II as acid acceptor, in which case a surplus must be used.
A number of starting materials of the formula II
and corresponding hydroxyalkyl derivatives (R=H) are known, e.g. from US patent 2.381.071, 2.759.943 as well as from Am.Soc. 84, 743 and Bull. Soc. Chim. France 1962, 303 and 1965, 2037. These starting materials, as well as those not yet described in the literature, which fall under the general formula II, can be manufactured easily by one of the following known methods, for example:
'7534 a) by condensation of the aniline of the formula III which is appropriately substituted by Rl to R4 ~ ~ NH2 (III) R4 ~
with a carbonyl compound of the formula IV
0 = C - C - O - R IV
in which the substituents R5, R6, and R7 represent h~gen,methyl or ethyl, but together possess at most 2 carbon atoms, and R has the meaning given for the formula I, and simultaneous or subsequent catalytic hydrogenation of the resulting azomethine of the formula V
R3 ~ R5 R6 . (V) b) by reaction of the aniline of the formula III which is appropriately substituted by Rl to R4 with a compound of - the formula VI
~.n47534 Y - A - OR (VI) wherein A and R are defined as under formula I and Y repre-sents a halogen atom or another acid radical, in particular an alkylsulphonic acid radical or an arylsulphonic acid radical. Compounds of the formula VI with benzenesulphonic acid radica~ Y are described e.g. in Can. J. Chem. 33, 1207, and those with tosyloxy radicals (CH3-C6H4-S03-) in British patent 869,083.
There are, of course, a number of other processes ~0 for the manufacture of the starting materials of the formula II from appropriately substituted anilines.
Some alkylsubstituted anilines of the formula III
can be manufactured from natural raw materials, e.g. coal tar oil, others can be manufactured by known methods of which a number are cited hereinbelow:
a) 2-alkylanilines or 2,6-dialkylanilines with C2-C4 alkyl groups in the ortho-position of the phenyl nucleus are advantageously manufactured from the corresponding aniline with a C2-C4 alkene (e.g. ethylene, propylene, l-butene, 2-butene etc,) under pressure in the presence of aluminium at temperatures above 200C lAngew. Chemie 69, 125 (1957)~.
It is thus possible e.g. to obtain 2,3-dimethyl-6-ethyl aniline from 2,3-dimethyl aniline and ethylene, and 2,3-dimethyl-6-isopropyl aniline from 2,3-dimethyl aniline and propylene.
10~7S34 b) Starting from the appropriate toluene, ethylbenzene, isopropyl benzene, xylene etc., there are obtained by di-nitration and partial reduction metanitroanilines from which, by diazotiation via the diazonium salts, meta-nitrohalobenzenes, meta-nitrocyanobenzenes etc. are obtained, which can then be converted by reduction into corresponding anilines of the formula III (J. Chem. Soc. 1927, 1106).
c) Meta-alkoxyanilines are advantageously manufactured by alkylation of the hydroxyl group of a meta-nitrophenol IJ. Org. Chem. 26, 4749 (1962)] and subsequent reduction of the nitro group.
d) Meta-alkylthioanilines of the formula III are obtained appropriately by sulphochlorination of e.g. acylated aniline, reduction of the sulphonyl chloride group to the mercapto group and alkylation thereof (British patent 1.027.060).
e) Meta-trifluoromethyl anilines of the formula III are obtained e.g. from 2, (4)-(di)alkyl-3,5-dinitro-benzoic acid, partial reduction of the nitro group in 5-position to the amino group, diazotiation ar.d elimination thereof and subsequent conversion of the carboxyl group to the tri-fluoromethyl group, whereupon the remaining nitro group is reduced to the amino group (British patent 1.027.030).
A number of intermediate products which are of importance for this invention are cited hereinbelow:
~04'7534 2,5-dimethyl-6~ethylaniline, b.p. 70-76C (0.7 Torr) 2,3-dimethyl-6-ethylaniline, b.p. 70-76C (0.7 Torr) 2,6-dimethyl-3-bromo-(2'-ethoxyethyl)-aniline b.p. 113-118C
(0.5 Torr) 2,3,5,6-tetramethyl-(2'-methoxyethyl)-aniline, b.p. 81-92C
(0.001 Torr) 52,3-dimethyl-(2'-methoxyethyl)-aniline, b.p. 73C (0.02 Torr) 2,3-dimethyl-(1'-methoxyprop-2'-yl)-aniline, b.p. 67-76C
(0.001 Torr) 2,3-dimethyl-(2'-ethoxyethyl)-aniline, b.p. 82-86C (0.01 Torr) 2,3,5-trimethyl-(2'-methoxyethyl)-aniline, b.p. 92C (0.3 Torr) 2,3,5-trimethyl-(1'-methoxyprop-2'-yl)-aniline, b.p. 94C
(0.5 Torr) 102,5-dimethyl-6-ethyl-(2'-methoxyethyl)-aniline, b.p. 95C
(0.7 Torr) 2,5-dimethyl-6-ethyl-(2'-ethoxyethyl)-aniline, b.p. 90C
(0.4 Torr) 2,5-dimethyl-6-ethyl-(2'-n-propoxyethyl)-aniline, b.p. 98-105C
(0.4 Torr) 2,5-dimethyl-6-ethyl-(2'-isopropoxyethyl)-aniline, b.p.
103-105C (0.6 Torr) 2,5-dimethyl-6-ethyl-(2'-allyloxyethyl)-aniline, b.p. 93C
(0.1 Torr) 152,3-dimethyl-6-ethyl-(2'-methoxyethyl)-aniline, b.p. 95C
(0.7 Torr) 2 9 3-dimethyl-6-ethyl-(2'-ethoxyethyl)-aniline, b.p. 90C
(0.4 Torr) 2,3-dimethyl-6-ethyl-(2'-n-propoxyethyl)-aniline, b.p. 98-105C
(0.4 Torr) 2,3-dimethyl-6-ethyl-(2'-isopropoxyethyl)-aniline, b.p.
103-105C (0.6 Torr) 1()~l'7534 2,3-dimethyl-6-ethyl-(1'-methoxyprop-2'-yl)-aniline, b.p. 90-94C (0.8 Torr) 2,3-dimethyl-6-ethyl-(l'-metho2yprop-2'-yl)-aniline, b.p. 102-106C (0.6 Torr) The following Examples illustrate the process according to the invention, including the manufacture of starting materials. Further haloacetanilides of the formula I, which were manufactured by one of the described processes, are listed in the subsequent Table~
~047534 Example 1 a) A solution of 55.7 g (0.278 mole) of 3-bromo-2,6-dimethyl aniline and 34.0 g (0.139 mole) of p-toluenesulphonic acis-(2-ethoxyethyl)-ester in 100 ml of toluene is refluxed for 25 hours. After the reaction mixture has cooled J it is made alkaline, diluted with ether, and the organic phase is washed repeatedly with water. The dried solution is evaporated and vacuum distillation of the residue yields the desired pro-duct, N-(2'-ethoxy-ethyl)-3-bromo-2,6-dimethyl aniline, b.p. 113-118C /O.STorr.
b) A suspension of lS.0 g (O.SS mole) of N-(2'-ethoxyethyl)-
3-bromo-2,6-dimethyl aniline and 5.84 g (0.055 mole) of sodium carbonate in 60 ml of absolute ether is treated dropwise with a solution of 6.22 g (O.SS mole) of chloro-acetyl chloride in 30 ml of absolute ether and stirring is æubsequently continued for 3 hours at 30C. The reaction mixture is processed by being washed repeatedly with water, dried and evaporated in vacuo, to give the pure product, 2,6-dimethyl-3-bromo-N-(2'-ethoxyethyl)-N-chloroacetanilide in quantitative yield; nD = 1.5554 [compound 1~.
Br CH
:104'7S34 Example 2 a) A solution of 847 g (7 moles) of 2,3-dimethyl aniline an~d 855 g (3.S moles) of p-toluenesulphonic acid -(1'-methoxyprGp-2'-yl)-ester are refluxed for 25 hours in 3.8 litres of toluene. After the reaction mixture has cooled, it is made alkaline and the organic phase is washed repea-tedly with water. The dried solution is evaporated and vacuum distillation of the residue yields 69% (of theory) of 2,3-dimethyl-(1'-methoxyprop-2'-yl)-aniline, b.p. 67-76C/
0.001 Torr.
Instead of using p-toluenesulphonic acid ester, it is possible to condense methoxy acetone with 2,3-dimethyl aniline and to hydrogenate the resulting azomethine in absolute ethanol at normal pressure in the presence of palladium charcoal.
b) 15,5 g (0.08 mole) of the intermediate product obtained in a) in 100 ml of absolute ether are treated with 8.5 g (o.08 mole) of sodium carbonate. A solution of 9.1 g (0.08 mole) of chloroacetyl chloride in 30 ml of absolute ether is added dropwise to this suspension, whereupon the mixture is subsequently stirred for a further 2 hours at room temperature. The organic phase is then washed 3 times with 50 ml of water on each occassion. The ethereal solution is dried and the ether removed to yield as residue 14.3 g (=69% of theory) of 2,3-dimethyl-N-(l'-methoxyprop-2'-yl)-~047534 N-chloroacetanilide, m,p. 45-53~ (compound 33).
2) 2,6-dimethyl-3-bromo-N-(2'-methoxyethyl)-N-chloroacetan-ilide, 3) 2,6-dimethyl-3-bromo-N-(2'-propoxyethyl)-N-chloroacetan-ilide,
Br CH
:104'7S34 Example 2 a) A solution of 847 g (7 moles) of 2,3-dimethyl aniline an~d 855 g (3.S moles) of p-toluenesulphonic acid -(1'-methoxyprGp-2'-yl)-ester are refluxed for 25 hours in 3.8 litres of toluene. After the reaction mixture has cooled, it is made alkaline and the organic phase is washed repea-tedly with water. The dried solution is evaporated and vacuum distillation of the residue yields 69% (of theory) of 2,3-dimethyl-(1'-methoxyprop-2'-yl)-aniline, b.p. 67-76C/
0.001 Torr.
Instead of using p-toluenesulphonic acid ester, it is possible to condense methoxy acetone with 2,3-dimethyl aniline and to hydrogenate the resulting azomethine in absolute ethanol at normal pressure in the presence of palladium charcoal.
b) 15,5 g (0.08 mole) of the intermediate product obtained in a) in 100 ml of absolute ether are treated with 8.5 g (o.08 mole) of sodium carbonate. A solution of 9.1 g (0.08 mole) of chloroacetyl chloride in 30 ml of absolute ether is added dropwise to this suspension, whereupon the mixture is subsequently stirred for a further 2 hours at room temperature. The organic phase is then washed 3 times with 50 ml of water on each occassion. The ethereal solution is dried and the ether removed to yield as residue 14.3 g (=69% of theory) of 2,3-dimethyl-N-(l'-methoxyprop-2'-yl)-~047534 N-chloroacetanilide, m,p. 45-53~ (compound 33).
2) 2,6-dimethyl-3-bromo-N-(2'-methoxyethyl)-N-chloroacetan-ilide, 3) 2,6-dimethyl-3-bromo-N-(2'-propoxyethyl)-N-chloroacetan-ilide,
4) 2,6-dimethyl-3-bromo-N-(2'-isopropoxyethyl)-N- chloro-acetanilide,
5) 2,6-dimethyl-3-bromo-N-(2'-cyclopropoxyethyl)-N-chloro-acetanilide,
6) 2,6-dimethyl-3-bromo-N-(2'-methoxypropyl)-N-chloroacetan-ilide,
7) 2,6-dimethyl-3-bromo-N-(2'-methoxypropyl)-N-chloroacetan-ilide,
8) 2,6-dimethyl-3-bromo-N-(l'-methoxyprop-2'-yl)-N-chloro-acetanilide,
9) 2,6-dimethyl-3-bromo-N-(l'-ethoxyprop-2'yl)-N-chloro-acetanilide, 0) 2,6-dimethyl-3-bromo-N-(3'-methoxybut-2'-yl)-N-chloro-acetanilide, 1) 2,6-dimethyl-3-bromo-N-(2'-allyloxyethyl)-N-chloro-acetanilide, 2) 2,6-dimethyl-3-bromo-N-(2'-methallyloxyethyl)-N-chloro-acetanilide, 3) 2,6-dimethyl-3-bromo-N-(2'-cyclopropylmethoxyethyl)-N-chloroacetanilide, 4) 2,6-dimethyl-3-bromo-N-(2'-methoxyethyl)-N-bromoacetan-ilide, 5) 2,3,6-trimethyl-N-(2'-methoxyethyl)-N-chloroacetanilide, 6) 2,3,6-trimethyl-N-(2'-ethoxyethyl)-N-chloroacetanilide, 7) 2,3,6-trimethyl-N-(2'-isopropoxyethyl)-N-chloroacetan-ilide, 8) 2,3,6-trimethyl-N-(2'-methoxypropyl)-N-chloroacetanilide, ~Q47S34 19) 2,3,6-trimethyl-N-~l'-methoxyprop-2t-yl) N-chloroacetan-ilide, 20) 2,3,6-trimethyl-N-(2'-cyclopropoxyethyl)-N-chloroacetan-ilide, 21) 2,3,6-trimethyl-N-(2'-methoxyethyl)-N-bromoacetanilide, 22) 2,3,5,6-tetramethyl-N-(2'-methoxyethyl)-N-chloroacetan-ilide, m.p. ~3C
23) 2,3,5,6-tetramethyl-N-(2'-ethoxyethyl)-N-chloroacetanilide, 24) 2,3,5,6-tetramethyl-N-(2'-propoxyethyl)-N-chloroacetan-ilide, - 25) 2,3,5,6-tetramethyl-N-(2'-isopropoxyethyl)-N-chloro-acetanilide, 26) 2,3,5,6-tetramethyl-N-(2'-methoxypropyl)-N-chloroacetan-ilide, 27) 2,3,5,6-tetramethyl-N-(l'-methoxyprop-2'-yl)-N-chloro-acetanilide, 28) 2,3,5,6-tetramethyl-N-~l'-ethoxyprop-2'-yl)-N-chloro-acetanilide, 29) 2,3-dimethyl-N-(2'-methoxyethyl)-N-chloroacetanilide, nD = 1,5351, 30) 2,3-dimethyl-N-(2'-ethoxyethyl)-N-chloroacetanilide, n20 = 1.5223, 31) 2,3-dimethyl-N-(2'-isopropoxyethyl)-N-chloroacetanilide, 32) 2,3-dimethyl-N-(2'-methoxypropyl)-N-chloroacetanilide, 33) 2,3-dimethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetanilide, - m.p. 45-53 34) 2,3-dimethyl-N-(2'-cyclopropoxyethyl)-N-chloroacetanilide, 35) 2,3-dimethyl-N-(2'-allyloxyethyl)-N-chloroacetanilide, 36) 2,3-dimethyl-N-(2'-methoxyethyl)-N-bromoacetanilide, 37) 2,5-dimethyl-N-(2'-methoxyethyl)-N-chloroacetanilide, . - 18 -~04'7534 38) 2,5-dimethyl-N-(2'-ethoxyethyl)-~-chloroacetanilide, 39) 2,5-dimethyl-N-(2'-ethoxypropyl)-N-chloroacetanilide, 40) 2,6-dimethyl-3-chloro-N-(2'-ethoxyethyl)-N-chloroacetan-ilide, 41) 2,6-dimethyl-3-chloro-N-(2'-methoxyethyl)-N-chloroacetan-ilide, m.p. 52-55 42) 2,6-dimethyl-3-chloro-N-(2'-propoxyethyl)-N~chloroacetan-ilide, 43) 2,6-dimethyl-3-chloro-N-(2'-isopropoxyethyl)-N-chloro-acetanilide, 44) 2,6-dimethyl-3-chloro-N-(2'-cyclopropoxyethyl)-N-chloro-acetanilide, 45) 2,6-dimethyl-3-chloro-N-(2'-methoxypropyl)-N-chloro-acetanilide, 46) 2,6-dimethyl-3-chloro-N-(2'-ethoxypropyl)-N-chloro-acetanilide, 47) 2,6-dimethyl-3-chloro-N-(l'-methoxyprop-2'-yl)-N-chloro-acetanilide m,p. 54-56, 48) 2,6-dimethyl-3-chloro-N-(l'-ethoxyprop-2'-yl)-N-chloro-acetanilide, 49) 2,6-dimethyl-3-chloro-N-(3'-methoxybut-2'-yl)-N-chloro-acetanilide, 50) 2,6-dimethyl-3-chloro-N-(2'-allyloxyèthyl)-N-chloro-acetanilide, 51) 2,6-dimethyl-3-chloro-N-~2'-methallyloxyethyl)-N-chloro-acetanilide, 52) 2,6-dimethyl-3-chloro-N-(2'-cyclopropylmethoxyethyl)-N-chloroacetanilide, 53) 2,6-dimethyl-3-chloro-N-(2'-methoxyethyl)-N-bromoacetan-ilide, 54) 2-methyl-3-bromo-6-ethyl-N-(2'-ethoxyethyl)-N-chloro-acetanilide, \
~047S34 55) 2-methyl-3-~romo-6-ethyl-N-(2'-methoxyethyl)-N-chloro-acetanilide, 56)1 2-methyl-3-bromo-6-ethyl-N-(2'-propoxyethyl)-N-chloro-acetanilide, 57 2-methyl-3-bromo-6-ethyl-N-(2'-isopropoxyethyl)-N-chloro-acetanilide, 58) 2-methyl-3-bromo-6-ethyl-N-(2'-cyclopropoxyethyl)-N-chloroacetanilide, 59) 2-methyl-3-bromo-6-ethyl-N-(2'-methoxypropyl)-N-chloro-acetanilide, 60) 2-methyl-3-bromo-6-ethyl-N-(2'-ethoxypropyl)-N-chloro-scetanilide, 61) 2-methyl-3-bromo-6-ethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetanilide, 62) 2-methyl-3-bromo-6-ethyl-N-(l'-ethoxyprop-2'-yl)-N-chloroacetanilide, 63) 2-methyl-3-bromo-6-ethyl-N-(3'-methoxybut-2'-yl)-N-chloroacetanilide, 64) 2-methyl-3-bromo-6-ethyl-N-(2'-allyloxyethyl)-N-chloro-acetanilide, 65~ 2-methyl-3-bromo-ethyl-N-(2'-methallyloxyethyl)-N-chloroacetanilide, 66) 2-methyl-3-bromo-6-ethyl-N-(2'-cyclopropylmethoxyethyl)-N-chloroacetanilide, 67) 2-methyl-3-bromo-6-ethyl-N-(2'-methoxyethyl)-N-bromo-acetanilide, 68) 2,6-dimethyl-3-methoxy-N-(2'-methoxyethyl)-N-chloro-acetanilide, m.p. 54-56, 69) 2,6-dimethyl-3-methoxy-N-(2'-ethoxyethyl)-N-chloro-acetanilide, 70) 2,6-dimethyl-3-methoxy-N-(2'-methoxypropyl)-N-chloro-acetanilide, 71) 2,6-dimethyl-3-methylthio-N-(2'-methoxyethyl)-N-chloro-acetanilide, m.p. 51-53,
23) 2,3,5,6-tetramethyl-N-(2'-ethoxyethyl)-N-chloroacetanilide, 24) 2,3,5,6-tetramethyl-N-(2'-propoxyethyl)-N-chloroacetan-ilide, - 25) 2,3,5,6-tetramethyl-N-(2'-isopropoxyethyl)-N-chloro-acetanilide, 26) 2,3,5,6-tetramethyl-N-(2'-methoxypropyl)-N-chloroacetan-ilide, 27) 2,3,5,6-tetramethyl-N-(l'-methoxyprop-2'-yl)-N-chloro-acetanilide, 28) 2,3,5,6-tetramethyl-N-~l'-ethoxyprop-2'-yl)-N-chloro-acetanilide, 29) 2,3-dimethyl-N-(2'-methoxyethyl)-N-chloroacetanilide, nD = 1,5351, 30) 2,3-dimethyl-N-(2'-ethoxyethyl)-N-chloroacetanilide, n20 = 1.5223, 31) 2,3-dimethyl-N-(2'-isopropoxyethyl)-N-chloroacetanilide, 32) 2,3-dimethyl-N-(2'-methoxypropyl)-N-chloroacetanilide, 33) 2,3-dimethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetanilide, - m.p. 45-53 34) 2,3-dimethyl-N-(2'-cyclopropoxyethyl)-N-chloroacetanilide, 35) 2,3-dimethyl-N-(2'-allyloxyethyl)-N-chloroacetanilide, 36) 2,3-dimethyl-N-(2'-methoxyethyl)-N-bromoacetanilide, 37) 2,5-dimethyl-N-(2'-methoxyethyl)-N-chloroacetanilide, . - 18 -~04'7534 38) 2,5-dimethyl-N-(2'-ethoxyethyl)-~-chloroacetanilide, 39) 2,5-dimethyl-N-(2'-ethoxypropyl)-N-chloroacetanilide, 40) 2,6-dimethyl-3-chloro-N-(2'-ethoxyethyl)-N-chloroacetan-ilide, 41) 2,6-dimethyl-3-chloro-N-(2'-methoxyethyl)-N-chloroacetan-ilide, m.p. 52-55 42) 2,6-dimethyl-3-chloro-N-(2'-propoxyethyl)-N~chloroacetan-ilide, 43) 2,6-dimethyl-3-chloro-N-(2'-isopropoxyethyl)-N-chloro-acetanilide, 44) 2,6-dimethyl-3-chloro-N-(2'-cyclopropoxyethyl)-N-chloro-acetanilide, 45) 2,6-dimethyl-3-chloro-N-(2'-methoxypropyl)-N-chloro-acetanilide, 46) 2,6-dimethyl-3-chloro-N-(2'-ethoxypropyl)-N-chloro-acetanilide, 47) 2,6-dimethyl-3-chloro-N-(l'-methoxyprop-2'-yl)-N-chloro-acetanilide m,p. 54-56, 48) 2,6-dimethyl-3-chloro-N-(l'-ethoxyprop-2'-yl)-N-chloro-acetanilide, 49) 2,6-dimethyl-3-chloro-N-(3'-methoxybut-2'-yl)-N-chloro-acetanilide, 50) 2,6-dimethyl-3-chloro-N-(2'-allyloxyèthyl)-N-chloro-acetanilide, 51) 2,6-dimethyl-3-chloro-N-~2'-methallyloxyethyl)-N-chloro-acetanilide, 52) 2,6-dimethyl-3-chloro-N-(2'-cyclopropylmethoxyethyl)-N-chloroacetanilide, 53) 2,6-dimethyl-3-chloro-N-(2'-methoxyethyl)-N-bromoacetan-ilide, 54) 2-methyl-3-bromo-6-ethyl-N-(2'-ethoxyethyl)-N-chloro-acetanilide, \
~047S34 55) 2-methyl-3-~romo-6-ethyl-N-(2'-methoxyethyl)-N-chloro-acetanilide, 56)1 2-methyl-3-bromo-6-ethyl-N-(2'-propoxyethyl)-N-chloro-acetanilide, 57 2-methyl-3-bromo-6-ethyl-N-(2'-isopropoxyethyl)-N-chloro-acetanilide, 58) 2-methyl-3-bromo-6-ethyl-N-(2'-cyclopropoxyethyl)-N-chloroacetanilide, 59) 2-methyl-3-bromo-6-ethyl-N-(2'-methoxypropyl)-N-chloro-acetanilide, 60) 2-methyl-3-bromo-6-ethyl-N-(2'-ethoxypropyl)-N-chloro-scetanilide, 61) 2-methyl-3-bromo-6-ethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetanilide, 62) 2-methyl-3-bromo-6-ethyl-N-(l'-ethoxyprop-2'-yl)-N-chloroacetanilide, 63) 2-methyl-3-bromo-6-ethyl-N-(3'-methoxybut-2'-yl)-N-chloroacetanilide, 64) 2-methyl-3-bromo-6-ethyl-N-(2'-allyloxyethyl)-N-chloro-acetanilide, 65~ 2-methyl-3-bromo-ethyl-N-(2'-methallyloxyethyl)-N-chloroacetanilide, 66) 2-methyl-3-bromo-6-ethyl-N-(2'-cyclopropylmethoxyethyl)-N-chloroacetanilide, 67) 2-methyl-3-bromo-6-ethyl-N-(2'-methoxyethyl)-N-bromo-acetanilide, 68) 2,6-dimethyl-3-methoxy-N-(2'-methoxyethyl)-N-chloro-acetanilide, m.p. 54-56, 69) 2,6-dimethyl-3-methoxy-N-(2'-ethoxyethyl)-N-chloro-acetanilide, 70) 2,6-dimethyl-3-methoxy-N-(2'-methoxypropyl)-N-chloro-acetanilide, 71) 2,6-dimethyl-3-methylthio-N-(2'-methoxyethyl)-N-chloro-acetanilide, m.p. 51-53,
10~7534 72) 2,6-dimethyl-3-methylthio-N-(2'-ethoxyethyl)-N-chloro-acetanilide, 73) 2,6-dimethyl-3-methylthio-N-(l'-methoxyprop-2'-yl)-N-chloroace~anilide, m.p. 49-52, 7~ 2,6-dimethyl-3-cyano-N-(2'-methoxyethyl)-N-chloro--acetanilide, m.p. 53-56, 75) 2,6-dimethyl-3-cyano-N-(2'-ethoxyethyl)-N-chloro-acetanilide, 76) 2,6-dimethyl-3-cyano-N-(2'-methoxypropyl)-N-chloro-acetanilide, 77) 2,6-dimethyl-3-cyano-N-(l'-methoxyprop-2'-yl)-N-chloro-acetanilide, m.p. 55-58C, 78) 2,6-dimethyl-3-trilfuoromethyl-N-(2'-methoxyethyl)-N-chloroacetanilide, m.p. 55-57C, 79) 2,6-dimethyl-3-trifluoromethyl-N-(2'-ethoxyethyl)-N-chloroacetanilide, 80) 2,6-dimethyl-3-methoxymethyl-N-(2'-methoxyethyl)-N-chloroacetanilide, 81) 2,6-dimethyl-3-methoxymethyl-N-(2'-ethoxyethyl)-N-chloroacetanilide, 82) 2,6-diethyl-3-bromo-N-(2'-ethoxyethyl)-N-chloroacetan-ilide, 83) 2,6-diethyl-3-bromo-N-(2'-methoxyethyl)-N-chloroacetan-ilide, 84) 2,6-diethyl-3-bromo-N-(l'-methoxyprop-2'-yl)-N-chloro-acetanilide, 85) 2,3-dimethyl-6-isopropyl-N-(2'-methoxyethyl~-N-chloro-acetanilide, 86) 2,3-dimethyl-6-isopropyl-N-(2'-ethoxyethyl)-N-chloro-- acetanilide, - 87) 2,3-dimethyl-6-isopropyl-N-(2'-methoxypropyl)-N-chloro-acetanilide, ~04'~534 88) 2,3-dimethyl-6-isopropyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetanilide, 89) 2,3-dimethyl-6-isopropyl-N-(2'-methoxyethyl)-N-bromo-acetanilide, 90) 2,5-dimethyl-6-ethyl-N-(2'-methoxyethyl)-N-chloroacetan-ilide,nD = 1.5335, 91) 2,5-dimethyl-6-ethyl-N-(2'-ethoxyethyl)-N-chloroacetan-ilide, nD = 1.5282, 92) 2,5-dimethyl-6-ethyl-N-(2'-isopropoxyethyl)-N-chloro-acetanilide, n20 = 1.5231, 93) 2,5-dimethyl-6-ethyl-N-(l'-methoxybut-2'-yl)-N-chloro-acetanilide, 94) 2,5-dimethyl-6-ethyl-N-(2'-methoxypropyl)-N-chloro-acetanilide, 95) 2,5-dimethyl-6-ethyl-N-(l'-methoxyprop-2'-yl)-N-chloro-acetanilide, 96) 2,5-dimethyl-6-ethyl-N-(l'-ethoxyprop-2'-yl)-N-chloro-acetanilide, 97) 2,5-dimethyl-6-ethyl-N-(2'-cyclopropoxyethyl)-N-chloro-acetanilide, 98) 2,5-dimethyl-6-ethyl-N-(2'-propoxyethyl)-N-chloroacetan-ilide, nD = 1.5252, 99) 2,5-dimethyl-6-ethyl-N-(2'-allyloxyethyl)-N-chloroacetan-ilide, nD = 1.5357, 00) 2,6-dimethyl-3-methoxy-N-(l'-methoxyprop-2'-yl)-N-chloro-acetanilide, m.p. 55-57C, 101) 2,6-dimethyl-3-trilfuoromethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetanilide, m.p. 55-59C, 102) 2,5-dimethyl-N-(2'-methoxyethyl)-N-chloroacetanilide, m.p. 42-45C, 103) 2,5-dimethyl-N-(2'-ethoxyethyl)-N-chloroacetanilide, ~DO= 1.5287, ~047534 10~) 2,5-dimethyl-N-(2'-propoxyethyl)-N-chloroacetanilide, n2 = 1.5219, O'j) 2,5-dimethyl-N-(2'-isopropoxyethyl)-N-chloroacetanilide, b.p. 115-120C/0.001 Torr, 06) 2,5-dimethyl-N-(2'-methoxypropyl)-N-chloroacetanilide, nD = 1.5325, 07) 2,5-dimethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetan-ilide, m.p. 44-46C, 08) 2,5-dimethyl-N-(l'-ethoxyprop-2'-yl)-N-chloroacetan-ilide, n20 = 1.5234, 09) 2,5-dimethyl-N-(2'-cyclopropoxyethyl)-N-chloroacetanilide, b.p. 118-123C/0.001 Torr, 10) 2,3-dimethyl-6-ethyl-N-(2'-methoxyethyl)-N-chloroacetan-ilide, nD = 1.5335,
11) 2,3-dimethyl-6-ethyl-N-(2'-ethoxyethyl)-N-chloroacetan-ilide, nD = 1.5282,
12) 2,3-dimethyl-6-ethyl-N-(2'-propoxyethyl)-N-chloroacetan~
ilide, nD = 1.5252,
ilide, nD = 1.5252,
13) 2,3-dimethyl-6-ethyl-N-(2'-isopropoxyethyl)-N-chloroacet-anilide, nD = 1.5231,
14) 2,3-dimethyl-6-ethyl-N-(2'-methoxypropyl)-N-chloroacetan-ilide, nD = 1.5296,
15) 2,3-dimethyl-6-ethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacet-anilide, nD = 1.5294,
16) 2,3-dimethyl-6-ethyl-N-(l'-ethoxyprop-2'-yl)-N-chloroacet-anilide, n20 = 1.5217,
17) 2,3-dimethyl-6-ethyl-N-(2'-cyclopropoxyethyl)-N-chloro-acetanilide,
18) 2,3-dimethyl-6-ethyl-N-(l'-propoxyprop-2'-yl)-N-chloro-acetanilide, ~0~'753~
119) 2,3-dimethyl-6-ethyl-N-(l'-methoxybut-2'-yl)-N-chloro-ace~anilide, b.p. 122-128C/0.001 Torr, 20) 2,3-dimethyl-6-ethyl-N-(2'-methoxybut-3'-yl)-N-chloro-acetanilide, b.p. 138-143~C/0.002 Torr, 21) 2,3-dimethyl-6-ethyl-N-(l'-methoxy-2'-methylprop-2'-yl)-N-chloroacetanilide b.p. 132-136C/0.001 Torr.
The active substances according to the invention are stable compounds and possess very good herbicidal pro-perties against annual grasses and related plants of the genera Setaria, Digitaria, etc., against grasses such as Lolium species and against dicotyledonous weeds such as Amaranthus, Sesbania, Chrysanthemum, Ipomoea, Sinapis, Galium, Pastinaca, without causing damage to the cultivated plants in respect of which the use of the active substances is in~ended, for example soya, alfalfa, peas, lentils, ground nuts, cotton, maize, coffee, tea, bananas, pineapples, sugar beet, sugar cane, potatoes, paprika, tomatoes, spinach, onions, aubergines, sun flowers, tobacco, Brassica species such as rape and cabbage, but also cereals, such as barley, oats, rye, wheat, or dry rice and water rice.
The active substances are applied either before or after the germination of the cultivated plants and of the weeds and grasses (pre-and postemergence); preemergence application is preferred. The rates of application are bet-ween 0.1 and 10 kg of active substance per hectare. But in preemergent application the weeds are virtually destroyed iO47S34 using a rate of application as low as 0,25 '~g of active substance per hectare. Normally up to 10 k~ of active substance per hectare are used to prevent railway ambankments, factory grounds, roads etc, from becoming overgrown with weeds.
Furthermore, the active substances of the formula I also exhibit growth regulating properties in that they delay the growth in height and increase the trillering of grasses (e.g. in existing grass plantations). Profusely and rapidly seeding weeds are inhibited in their germina-tion and emergence and so removed from cultivations of crop plants. The acylated amines of the formula I also possess defoliating properties and can be used for delaying blos-soming. The storage capability of substances contained in plants is improved generally by the active substances according to the invention. For example, the sugar content in sugar beet or the starch content or potatoes or the fat content of soya beans or ground nuts is increased.
As already mentioned, herbicidal haloacetanilides of comparable constitution are known from the literature.
However, these either have only alkoxymethyl groups at the nitrogen atom (US patent 3.547.620) or in one ortho-position of the phenyl radical carry other tertiary alkyl substituents, such as in particular tert. butyl (French patent 1.337.529).
It is disclosed in the literature that the N-alkoxy-10~'7534 me~hyl derivatives represent the best products and are superior at all events to the corresponding N-alkoxyethyl and N-alkoxypropyl derivatives (US patent 3.547.620, Example 85~. On the basis of this pu~lication, one skilled in the art had to assume that N-substituted haloacetanilides with alkoxy, alkenyloxy and cycloalkoxy groups which are bonded to the nitrogen atom of the anilide through alkylene radi-cals with 2 chain members, regardless of how they are sub-stituted in the phenyl nucleus, are not suitable as herbicides for practical purpose.
The surprising discovery has now been made that the new active substances of the formula I according to the invention, which do not have the supposedly most favour-able constitution for the herbicidal activity as claimed in US patent 3.547.620, and which furthermore are substituted in the phenyl ring in at least one meta-position to the amino group, are superior to these N-alkoxymethyl-2,(6)-(di) alkyl-chloroacetanilides and other closely related compounds described in the literature in the selective control of weeds.
- ~6 -~0~753 Example 3 Control of Panicum species and other mor.ocotyledonous weeds _ various cultures of crop plants (preemergence method) One day after the test plants have been sown in seed dishes, dilute aqueous suspensions of the active substances are sprayed in such concentrations on the surface of the soil as to correspond to rates of application of 2 kg, 1 kg and 0.5 kg per hectare. The seed dishes are kept at 22 and 25C and about 70% relative humidity. The test is evaluated after 28 days according to the following rating:
9 = plants undamaged (as control test) 1 = plants destroyed 8-2 = intermediate stages of damage - = not tested Known haloacetanilides were used as comparison compounds:
Compound A: 2-methyl-N-(l'-methoxyprop-2'-yl)-N-chloro-acetanilide (French patent 2.028.991) Compound B: 2,6-diethyl-N-(methoxymethyl)-chloroacetanilide (commercial product) (US patent 3.547.620).
~04'7534 Tablel .
n ~-~ m~r ~ 3 O ~ P~ p7 ~ - O `~ 0 1_ ~ O O
3 ~ ~o~ ~.
~ ~ 1'- a~ ~'- p~ ~. p~ p) N
. oq ~o o O ~ g ~ ~ 0 Z 1~ ~ ~ ~ c~
o c~ p, ~ ~ P~ ~n _ 1~............................ .
0.5 1112224 999999_ 0.5 121-323 9999999 0,5 1112212 9999999 90 1 1112111 89999_9 0,5 1113122 99999-9 _ 0.5 1111131 . 9999999 T bl 1 ( tio4t7~3~ 4 ~ _ . .
3 ~ o I ~'s' ' 1~ 5 ~D ~" 3 ~ o p~ w' ~ o~
2 111111 - 199999 ~ 7 9~ l 111112 - 19999998 .
0.5 11 l 23 - - 19999999 2 11111 - 1 8999999 .
O.S 11121 - 3 9999999 99 1 1 i 121 - 2 9999999 . 0.5 11132 - 3 9999999 . 33 1 1111111 8989989 0.5 1113141 9999999 . 2 1 ~ 17123 7788438 . . 0.5 1319564 9999799 . ~ 1114 - 22 8598439 . L ~ 1217 - 44 L9799999 1~4753~
It is evident from the comparison results that the selecti-vity of the compounds of the present invention in the control of weeds and protection of crop plants is distinctly better than that of the closest comparable known compounds. In the rate of application of 1 kg of active substance per hectare which is of importance for practical purpose, the comparison compounds A and B have no satisfactory tolerance in crops of cultivated plants, and on the other hand, important weeds such as Alopecurus, Lolium and Rottboellia are in-sufficiently controlled.
Example 4 Control of weeds in rice Earthenware dishes filled with garden soil are sown on the one hand with rice (Oryza oryzoides) and on the other hand with weeds. The active substance solution was prepared from a 25% wettable powder and applied to the surface of the soil immediately after the sowing (amount of the solution: 100 ml/m ). The dishes were kept in a greenhouse at 24-27C and 70% relative humidity. Evaluation took place 28 days later according to the rating given in Example 3.
Table 2 Comp. Rate of applic. Cyperus Setaria Echino- Rice No. in kg AS/ha esculentusitalica chloa c.g.
0.5 1 1 1 9 9~ 1 1 1 1 8 0.5 1 1 1 9 Example 5 Growth inhibition in grasses ~postemergence method) Seeds of the grasses Lolium perenne, Poa pratensis, Pestuca ovina, and Dactylis glomerata were sown in plastic dishes filled with an earth/turf/sand mixture. After 3 weeks the germinated grasses were cut bac~ to a height of 4 cm above the soil and 2 days later sprayed with aqueous spray broths of active substances of the formula I. The amount of active substance corres-ponded to a rate of application of 5 kg of active substance per hectare.
Fourteen days after application the growth of the grasses was evaluated according to the following linear rating:
1 = strong inhibition (no growth from the time of application) 9 = no inhibition (growth as untreated control) lV~'7534 Of the tested substances, very strong growth inhibition was achieved with the following compounds (rating l to 3): 29, 30, 33, 37, 41, 68, 71, 73, 78, 90, 95, 100, 102, 107 and 110 .
The agents according to the invention are manufac-tured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may take and be used in the following forms:
Solid forms:
dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules.
Liquid forms:
a) active substances which are dispersible in water:
wettable powders, pastes, emulsions;
b) solutions.
To manufacture solid forms ~dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomacous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, 10~7S34 ground synthetic materials, fertilisers, for example a~monium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extrac-tions, activated charcoal etc. These substances can either be used singly or in admixture with one another.
The particle size of the carriers for dusts is ad-vantageously up to 0.1 mm, for tracking agents from about 0.075 to 0.2 mm, and for granules 0.2 mm or larger.
The solid forms contain the active substances in concentrations from 0.1% to 80%.
To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, which for example improve the adhesion of the acSive ingredients on plants or parts of plants Cadhesive and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following:
olein/chalk mixture, cellulose derivatives tmethyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers 1()4';'534 ~carbowaxes)*, fatty alcohol polyethylene glycol ether having 5 to 30 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation pro-duct of urea and formaldehyde, and also latex products.
The water-dispersible concentrates of the active substance i~e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substances and anti-foam agents and, optionally, solvents. The active substance concentrations in these agents are from 5-80%.
Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homo-geneity is attained. Carriers are, for example, those mentioned for the solid forms of application. In some cases it is advan-tageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulphonated naphthalene and sulphonated naphthalene deri-vatives with formaldehyde, condensation products of naphthalene or naphthalene sulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulphonic acid, in addition, alkylaryl sulphonates, *Trade Mark ~0~7534 alkali and alkaline ea~h metal ~alts of dibutyl naphthalene sulphonic acid, fa~ty alcohol sulphates such as salts of sulphated hexadecanols, heptadecanols, octadecanols, and sa'Lts of sulphated fatty alcohol glycol ethers, the sodium saLt of oleoyl ethionate, the sodium salt of oleoly methyl tauride, ditertiary acetalene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth salts.
Suitable anti-foam agents are silicones. The active substances are so mixed, ground sieved and strained with the additives mentioned above that, in wettable powders, the solid particle size of from 0.02 to 0.04 and in pastes, of 0.03 is not exeeded.. To produce emulsifiable concentrates and pastes, dispering agents such as those given in the previous paragraphs, organic solvents and water are used.
Examples of suitable solvents are: alcohols, benzene, xylenes, toluene, dimethyl sulphoxide, N.N-dialkylated amides, N-oxides of amines, especially trialkylamines, and mineral oil fractions boiling between 120 and 350C. The solvents mux~ be practically odourless, not phytotoxic, inert to the active substances and may not have too low a flash point.
Furthermore, the agents according to the invention ; can be applied in the form of solution. For this purpose the active substance, or several active substances of general formula I, is dissolved in suitable organic solvents, mixtures ~047S34 of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes and mi-neral oils singly or in admixture, can be used as organic solvents. The solutions contain the active substance in a con-centration range from 1% to 20%. These solutions can either be applied with the acid of a propellant gas (spray) or wi~h special spray (as aerosol).
The agents described according to the invention can be mixed with other biocidally active substances or agents. Thus in order to broaden the activity spectrum the new agents may contain, for example, insecticides, fungi-cides, bactericides, fungistatics, bacteriostatics, nema-tocides or further herbicides, in addition to the cited active substances of the formula I. The agents according to the invention may also contain plant fertilisers, trace elements etc.
The active substances of the formula I can, for example, be formulated as follows. The parts denote parts by weight.
Granules - The following substances are used to manufacture 5% granules:
S parts of active substance of the formula I
0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol ether, 91 parts of kaolin (particle size: 0.3-0.8 mm).
The active substance is mixed with epichlorohydrin anc3 the mixture dissolved in 6 parts of ace~one, then poly-ethylene glycol ether and cetyl polyglycol ether are added.
The resulting solution is sprayed on kaolin and then evapo-rated in vacuo.
Wettable powder The following consituents are used to manufacture a) a 50%, b) a 25% and c) a 10% wettable powder:
a)50 parts of active substance of the formula I, e.g. 2,3-dimethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetanilide, 5 parts of sodium dibutylnaphthalene sulphonate, 3 parts of naphthalenesulphonic acid/phenolsul-phonic acid/formaldehyde condensate (3:2:1), 20 parts of kaolin, 22 parts of champagne chalk;
b)25 parts of active substance of the formula I, 5 parts of oleylmethyltaurid-sodium salt, 2,5 parts of naphthalenesulphonic acid/formaldehyde condensate, 0.5 part of carboxymethyl cellulose, 5 parts of neutral potassium-aluminium-silicate, 62 parts of kaolin;
c) 10 parts of N-(2'-methoxyethyl)-~,6-diethyl-chloro-acetanilide, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate, ' 82 parts of kaolin.
The indicated active substance is applied to the corresponding carriers (kaolin and chalk) and then these are mixed and ground, to yield wettable powders of excellent wet-tability and h,aving an excellent capacity for forming sus-pension. By diluting these wettable powders with water it 15, is possible to obtain suspensions of any desired concen-tration, Paste The following substances are used to manufacture a 45% paste: .
45 parts of active substance of the formula I, 5 parts of sodium aluminium silicate, 14 parts of cetyl polyglycol ether with 8 mols of ethylene oxide, 1 part of oleyl polyglycol ether with 5 mols of ethylene oxide, ` ~047534 2 parts of spindle oil, 10 parts of polyethylene glycol, 38-18 parts of water.
The active substance is intimately mixed with the adclitives in appropriate devices and ground. A paste is obtained from which, by dilution with water, is possible to manufacture suspensions of every desired concentration of active substance.
Emulsion Concentrate To manufacture a 25% emulsion concentrate 25 parts of active substance of the formula I, 5 parts of a mixture of nonylphenolpolyoxy-ethoxy-ethylene and calcium dodecylenesulphonate, 35 parts of 3,5,5-trimethyl-2-cyclohexan-1-one, 40-30 parts of dimethyl formamide, are mixed together. this concentrate can be diluted with water to give emulsions in desired concentrations. Such emulsions are suitable for controlling weeds in cultures of crop plants.
119) 2,3-dimethyl-6-ethyl-N-(l'-methoxybut-2'-yl)-N-chloro-ace~anilide, b.p. 122-128C/0.001 Torr, 20) 2,3-dimethyl-6-ethyl-N-(2'-methoxybut-3'-yl)-N-chloro-acetanilide, b.p. 138-143~C/0.002 Torr, 21) 2,3-dimethyl-6-ethyl-N-(l'-methoxy-2'-methylprop-2'-yl)-N-chloroacetanilide b.p. 132-136C/0.001 Torr.
The active substances according to the invention are stable compounds and possess very good herbicidal pro-perties against annual grasses and related plants of the genera Setaria, Digitaria, etc., against grasses such as Lolium species and against dicotyledonous weeds such as Amaranthus, Sesbania, Chrysanthemum, Ipomoea, Sinapis, Galium, Pastinaca, without causing damage to the cultivated plants in respect of which the use of the active substances is in~ended, for example soya, alfalfa, peas, lentils, ground nuts, cotton, maize, coffee, tea, bananas, pineapples, sugar beet, sugar cane, potatoes, paprika, tomatoes, spinach, onions, aubergines, sun flowers, tobacco, Brassica species such as rape and cabbage, but also cereals, such as barley, oats, rye, wheat, or dry rice and water rice.
The active substances are applied either before or after the germination of the cultivated plants and of the weeds and grasses (pre-and postemergence); preemergence application is preferred. The rates of application are bet-ween 0.1 and 10 kg of active substance per hectare. But in preemergent application the weeds are virtually destroyed iO47S34 using a rate of application as low as 0,25 '~g of active substance per hectare. Normally up to 10 k~ of active substance per hectare are used to prevent railway ambankments, factory grounds, roads etc, from becoming overgrown with weeds.
Furthermore, the active substances of the formula I also exhibit growth regulating properties in that they delay the growth in height and increase the trillering of grasses (e.g. in existing grass plantations). Profusely and rapidly seeding weeds are inhibited in their germina-tion and emergence and so removed from cultivations of crop plants. The acylated amines of the formula I also possess defoliating properties and can be used for delaying blos-soming. The storage capability of substances contained in plants is improved generally by the active substances according to the invention. For example, the sugar content in sugar beet or the starch content or potatoes or the fat content of soya beans or ground nuts is increased.
As already mentioned, herbicidal haloacetanilides of comparable constitution are known from the literature.
However, these either have only alkoxymethyl groups at the nitrogen atom (US patent 3.547.620) or in one ortho-position of the phenyl radical carry other tertiary alkyl substituents, such as in particular tert. butyl (French patent 1.337.529).
It is disclosed in the literature that the N-alkoxy-10~'7534 me~hyl derivatives represent the best products and are superior at all events to the corresponding N-alkoxyethyl and N-alkoxypropyl derivatives (US patent 3.547.620, Example 85~. On the basis of this pu~lication, one skilled in the art had to assume that N-substituted haloacetanilides with alkoxy, alkenyloxy and cycloalkoxy groups which are bonded to the nitrogen atom of the anilide through alkylene radi-cals with 2 chain members, regardless of how they are sub-stituted in the phenyl nucleus, are not suitable as herbicides for practical purpose.
The surprising discovery has now been made that the new active substances of the formula I according to the invention, which do not have the supposedly most favour-able constitution for the herbicidal activity as claimed in US patent 3.547.620, and which furthermore are substituted in the phenyl ring in at least one meta-position to the amino group, are superior to these N-alkoxymethyl-2,(6)-(di) alkyl-chloroacetanilides and other closely related compounds described in the literature in the selective control of weeds.
- ~6 -~0~753 Example 3 Control of Panicum species and other mor.ocotyledonous weeds _ various cultures of crop plants (preemergence method) One day after the test plants have been sown in seed dishes, dilute aqueous suspensions of the active substances are sprayed in such concentrations on the surface of the soil as to correspond to rates of application of 2 kg, 1 kg and 0.5 kg per hectare. The seed dishes are kept at 22 and 25C and about 70% relative humidity. The test is evaluated after 28 days according to the following rating:
9 = plants undamaged (as control test) 1 = plants destroyed 8-2 = intermediate stages of damage - = not tested Known haloacetanilides were used as comparison compounds:
Compound A: 2-methyl-N-(l'-methoxyprop-2'-yl)-N-chloro-acetanilide (French patent 2.028.991) Compound B: 2,6-diethyl-N-(methoxymethyl)-chloroacetanilide (commercial product) (US patent 3.547.620).
~04'7534 Tablel .
n ~-~ m~r ~ 3 O ~ P~ p7 ~ - O `~ 0 1_ ~ O O
3 ~ ~o~ ~.
~ ~ 1'- a~ ~'- p~ ~. p~ p) N
. oq ~o o O ~ g ~ ~ 0 Z 1~ ~ ~ ~ c~
o c~ p, ~ ~ P~ ~n _ 1~............................ .
0.5 1112224 999999_ 0.5 121-323 9999999 0,5 1112212 9999999 90 1 1112111 89999_9 0,5 1113122 99999-9 _ 0.5 1111131 . 9999999 T bl 1 ( tio4t7~3~ 4 ~ _ . .
3 ~ o I ~'s' ' 1~ 5 ~D ~" 3 ~ o p~ w' ~ o~
2 111111 - 199999 ~ 7 9~ l 111112 - 19999998 .
0.5 11 l 23 - - 19999999 2 11111 - 1 8999999 .
O.S 11121 - 3 9999999 99 1 1 i 121 - 2 9999999 . 0.5 11132 - 3 9999999 . 33 1 1111111 8989989 0.5 1113141 9999999 . 2 1 ~ 17123 7788438 . . 0.5 1319564 9999799 . ~ 1114 - 22 8598439 . L ~ 1217 - 44 L9799999 1~4753~
It is evident from the comparison results that the selecti-vity of the compounds of the present invention in the control of weeds and protection of crop plants is distinctly better than that of the closest comparable known compounds. In the rate of application of 1 kg of active substance per hectare which is of importance for practical purpose, the comparison compounds A and B have no satisfactory tolerance in crops of cultivated plants, and on the other hand, important weeds such as Alopecurus, Lolium and Rottboellia are in-sufficiently controlled.
Example 4 Control of weeds in rice Earthenware dishes filled with garden soil are sown on the one hand with rice (Oryza oryzoides) and on the other hand with weeds. The active substance solution was prepared from a 25% wettable powder and applied to the surface of the soil immediately after the sowing (amount of the solution: 100 ml/m ). The dishes were kept in a greenhouse at 24-27C and 70% relative humidity. Evaluation took place 28 days later according to the rating given in Example 3.
Table 2 Comp. Rate of applic. Cyperus Setaria Echino- Rice No. in kg AS/ha esculentusitalica chloa c.g.
0.5 1 1 1 9 9~ 1 1 1 1 8 0.5 1 1 1 9 Example 5 Growth inhibition in grasses ~postemergence method) Seeds of the grasses Lolium perenne, Poa pratensis, Pestuca ovina, and Dactylis glomerata were sown in plastic dishes filled with an earth/turf/sand mixture. After 3 weeks the germinated grasses were cut bac~ to a height of 4 cm above the soil and 2 days later sprayed with aqueous spray broths of active substances of the formula I. The amount of active substance corres-ponded to a rate of application of 5 kg of active substance per hectare.
Fourteen days after application the growth of the grasses was evaluated according to the following linear rating:
1 = strong inhibition (no growth from the time of application) 9 = no inhibition (growth as untreated control) lV~'7534 Of the tested substances, very strong growth inhibition was achieved with the following compounds (rating l to 3): 29, 30, 33, 37, 41, 68, 71, 73, 78, 90, 95, 100, 102, 107 and 110 .
The agents according to the invention are manufac-tured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may take and be used in the following forms:
Solid forms:
dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules.
Liquid forms:
a) active substances which are dispersible in water:
wettable powders, pastes, emulsions;
b) solutions.
To manufacture solid forms ~dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomacous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, 10~7S34 ground synthetic materials, fertilisers, for example a~monium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extrac-tions, activated charcoal etc. These substances can either be used singly or in admixture with one another.
The particle size of the carriers for dusts is ad-vantageously up to 0.1 mm, for tracking agents from about 0.075 to 0.2 mm, and for granules 0.2 mm or larger.
The solid forms contain the active substances in concentrations from 0.1% to 80%.
To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, which for example improve the adhesion of the acSive ingredients on plants or parts of plants Cadhesive and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following:
olein/chalk mixture, cellulose derivatives tmethyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers 1()4';'534 ~carbowaxes)*, fatty alcohol polyethylene glycol ether having 5 to 30 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation pro-duct of urea and formaldehyde, and also latex products.
The water-dispersible concentrates of the active substance i~e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substances and anti-foam agents and, optionally, solvents. The active substance concentrations in these agents are from 5-80%.
Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homo-geneity is attained. Carriers are, for example, those mentioned for the solid forms of application. In some cases it is advan-tageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulphonated naphthalene and sulphonated naphthalene deri-vatives with formaldehyde, condensation products of naphthalene or naphthalene sulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulphonic acid, in addition, alkylaryl sulphonates, *Trade Mark ~0~7534 alkali and alkaline ea~h metal ~alts of dibutyl naphthalene sulphonic acid, fa~ty alcohol sulphates such as salts of sulphated hexadecanols, heptadecanols, octadecanols, and sa'Lts of sulphated fatty alcohol glycol ethers, the sodium saLt of oleoyl ethionate, the sodium salt of oleoly methyl tauride, ditertiary acetalene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth salts.
Suitable anti-foam agents are silicones. The active substances are so mixed, ground sieved and strained with the additives mentioned above that, in wettable powders, the solid particle size of from 0.02 to 0.04 and in pastes, of 0.03 is not exeeded.. To produce emulsifiable concentrates and pastes, dispering agents such as those given in the previous paragraphs, organic solvents and water are used.
Examples of suitable solvents are: alcohols, benzene, xylenes, toluene, dimethyl sulphoxide, N.N-dialkylated amides, N-oxides of amines, especially trialkylamines, and mineral oil fractions boiling between 120 and 350C. The solvents mux~ be practically odourless, not phytotoxic, inert to the active substances and may not have too low a flash point.
Furthermore, the agents according to the invention ; can be applied in the form of solution. For this purpose the active substance, or several active substances of general formula I, is dissolved in suitable organic solvents, mixtures ~047S34 of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes and mi-neral oils singly or in admixture, can be used as organic solvents. The solutions contain the active substance in a con-centration range from 1% to 20%. These solutions can either be applied with the acid of a propellant gas (spray) or wi~h special spray (as aerosol).
The agents described according to the invention can be mixed with other biocidally active substances or agents. Thus in order to broaden the activity spectrum the new agents may contain, for example, insecticides, fungi-cides, bactericides, fungistatics, bacteriostatics, nema-tocides or further herbicides, in addition to the cited active substances of the formula I. The agents according to the invention may also contain plant fertilisers, trace elements etc.
The active substances of the formula I can, for example, be formulated as follows. The parts denote parts by weight.
Granules - The following substances are used to manufacture 5% granules:
S parts of active substance of the formula I
0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol ether, 91 parts of kaolin (particle size: 0.3-0.8 mm).
The active substance is mixed with epichlorohydrin anc3 the mixture dissolved in 6 parts of ace~one, then poly-ethylene glycol ether and cetyl polyglycol ether are added.
The resulting solution is sprayed on kaolin and then evapo-rated in vacuo.
Wettable powder The following consituents are used to manufacture a) a 50%, b) a 25% and c) a 10% wettable powder:
a)50 parts of active substance of the formula I, e.g. 2,3-dimethyl-N-(l'-methoxyprop-2'-yl)-N-chloroacetanilide, 5 parts of sodium dibutylnaphthalene sulphonate, 3 parts of naphthalenesulphonic acid/phenolsul-phonic acid/formaldehyde condensate (3:2:1), 20 parts of kaolin, 22 parts of champagne chalk;
b)25 parts of active substance of the formula I, 5 parts of oleylmethyltaurid-sodium salt, 2,5 parts of naphthalenesulphonic acid/formaldehyde condensate, 0.5 part of carboxymethyl cellulose, 5 parts of neutral potassium-aluminium-silicate, 62 parts of kaolin;
c) 10 parts of N-(2'-methoxyethyl)-~,6-diethyl-chloro-acetanilide, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate, ' 82 parts of kaolin.
The indicated active substance is applied to the corresponding carriers (kaolin and chalk) and then these are mixed and ground, to yield wettable powders of excellent wet-tability and h,aving an excellent capacity for forming sus-pension. By diluting these wettable powders with water it 15, is possible to obtain suspensions of any desired concen-tration, Paste The following substances are used to manufacture a 45% paste: .
45 parts of active substance of the formula I, 5 parts of sodium aluminium silicate, 14 parts of cetyl polyglycol ether with 8 mols of ethylene oxide, 1 part of oleyl polyglycol ether with 5 mols of ethylene oxide, ` ~047534 2 parts of spindle oil, 10 parts of polyethylene glycol, 38-18 parts of water.
The active substance is intimately mixed with the adclitives in appropriate devices and ground. A paste is obtained from which, by dilution with water, is possible to manufacture suspensions of every desired concentration of active substance.
Emulsion Concentrate To manufacture a 25% emulsion concentrate 25 parts of active substance of the formula I, 5 parts of a mixture of nonylphenolpolyoxy-ethoxy-ethylene and calcium dodecylenesulphonate, 35 parts of 3,5,5-trimethyl-2-cyclohexan-1-one, 40-30 parts of dimethyl formamide, are mixed together. this concentrate can be diluted with water to give emulsions in desired concentrations. Such emulsions are suitable for controlling weeds in cultures of crop plants.
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula I
(I) wherein R represents an alkyl radical with at most 3 carbon atoms, an alkenyl radical with 3 or 4 carbon atoms, a cyclopropyl radical, or a cyclopropyl-methyl radical, A represents an unsubstituted ethylene chain or an ethylene chain which is monosubstituted by ethyl or mono- or disubstituted by methyl, R1 represents hydrogen or an alkyl radical with at most 4 carbon atoms, R2 represents an alkyl radical with at most 4 carbon atoms, R3 and R4 each inde-pendently represents a substituent which is in meta-position to the amino group, namely halogen, cyano, alkyl, alkylthio or alkoxy, each with at most 3 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 3 halogen atoms, alkoxyalkyl or alkylthioalkyl with 2 to 4 carbon atoms, and one of the sub-stituents R3 or R4 also represents hydrogen, and X represents chlorine or bromine.
(I) wherein R represents an alkyl radical with at most 3 carbon atoms, an alkenyl radical with 3 or 4 carbon atoms, a cyclopropyl radical, or a cyclopropyl-methyl radical, A represents an unsubstituted ethylene chain or an ethylene chain which is monosubstituted by ethyl or mono- or disubstituted by methyl, R1 represents hydrogen or an alkyl radical with at most 4 carbon atoms, R2 represents an alkyl radical with at most 4 carbon atoms, R3 and R4 each inde-pendently represents a substituent which is in meta-position to the amino group, namely halogen, cyano, alkyl, alkylthio or alkoxy, each with at most 3 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 3 halogen atoms, alkoxyalkyl or alkylthioalkyl with 2 to 4 carbon atoms, and one of the sub-stituents R3 or R4 also represents hydrogen, and X represents chlorine or bromine.
2. A compound according to claim 1, wherein X represents chlorine.
3. A compound according to claim 2, wherein R1 and R2 each repre-sents an alkyl radical, the total number of carbon atoms of both alkyl radicals not exceeding 5.
4. A compound according to claim 1, wherein A, R, R1, R2 and X
have the indicated meanings, and wherein one of the substituents R3 and R4 in meta-position to the amino group represents chlorine, the cyano, trifluoromethyl, methoxy, or methylthio group, and the other substituent represents hydrogen.
have the indicated meanings, and wherein one of the substituents R3 and R4 in meta-position to the amino group represents chlorine, the cyano, trifluoromethyl, methoxy, or methylthio group, and the other substituent represents hydrogen.
5. A compound according to claim 4, wherein A represents an ethy-lene chain which is monosubstituted by methyl or ethyl.
6. A compound according to claim 1, wherein A and R have the indicated meanings, X represents chlorine, R1 represents a methyl group, R2 represents hydrogen, methyl or ethyl, and wherein the substituent R3 in meta-position to the amino group represents an alkyl radical with at most 3 carbon atoms and R4 represents hydrogen.
7. A compound according to claim 1, which contains a compound of the formula Ia (Ia) wherein R2 represents hydrogen, a methyl or ethyl group, and R' and R5 each independently represents a methyl or an ethyl group.
8. A compound according to claim 1, which is 2,3-dimethyl-N-(1'-methoxyprop-2'-yl)-N-chloroacetanilide of the formula
9. A compound according to claim 1, which is 2,3-dimethyl-6-ethyl-N-(1'-methoxyprop-2'-yl)-N-chloroacetanilide.
10. A compound according to claim 1, which is 2,6-dimethyl-3-chloro-N-(2'-methoxyethyl)-N-chloroacetanilide.
11. A compound according to claim 1, which is 2,6-dimethyl-3-methoxy-N-(2'-methoxyethyl)-N-chloroacetanilide.
12. A process for the manufacture of compounds of the formula I
(I) wherein R represents an alkyl radical with at most 3 carbon atoms, an alkenyl radical with 3 or 4 carbon atoms, a cyclopropyl radical, or a cyclopropyl methyl radical, A represents an unsubstituted ethylene chain or an ethylene chain which is monosubstituted by ethyl or mono- or disubstituted by methyl, R1 represents hydrogen or an alkyl radical with at most 4 carbon atoms, R2 represents an alkyl radical with at most 4 carbon atoms, R3 and R4 each inde-pendently represents a substituent which is in meta-position to the amino group, namely halogen, cyano, alkyl, alkylthio or alkoxy, each with at most 3 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 3 halogen atoms, alkoxyalkyl or alkylthioalkyl with 2 to 4 carbon atoms, and one of the substi-tuents R3 or R4 also represents hydrogen, and X represents chlorine or bromine, wherein a N-substituted aniline of the formula (II) in which R, R1, R2, R3, R4, and A have the meanings given hereinbefore, is reacted with a haloacetylating agent.
(I) wherein R represents an alkyl radical with at most 3 carbon atoms, an alkenyl radical with 3 or 4 carbon atoms, a cyclopropyl radical, or a cyclopropyl methyl radical, A represents an unsubstituted ethylene chain or an ethylene chain which is monosubstituted by ethyl or mono- or disubstituted by methyl, R1 represents hydrogen or an alkyl radical with at most 4 carbon atoms, R2 represents an alkyl radical with at most 4 carbon atoms, R3 and R4 each inde-pendently represents a substituent which is in meta-position to the amino group, namely halogen, cyano, alkyl, alkylthio or alkoxy, each with at most 3 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 3 halogen atoms, alkoxyalkyl or alkylthioalkyl with 2 to 4 carbon atoms, and one of the substi-tuents R3 or R4 also represents hydrogen, and X represents chlorine or bromine, wherein a N-substituted aniline of the formula (II) in which R, R1, R2, R3, R4, and A have the meanings given hereinbefore, is reacted with a haloacetylating agent.
13. A process according to claim 12, wherein the anhydride or halide of chloroacetic acid or bromoacetic acid is used as haloacetylating agent.
14. A method of selectively controlling weeds in cultures of crop plants, which comprises applying to the culture a compound according to formula I as defined in claim 1.
15. A method according to claim 14, which comprises applying to the culture a compound according to claim 2 or 3.
16. A method according to claim 14, which comprises using a compound according to claim 4 or 5.
17. A method according to claim 14, which comprises using a compound according to claim 6 or 7.
18. A method according to claim 14, which comprises using a compound according to claim 8 or 9.
19. A method according to claim 14, which comprises using a compound according to claim 10 or 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH175773A CH582470A5 (en) | 1973-02-07 | 1973-02-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1047534A true CA1047534A (en) | 1979-01-30 |
Family
ID=4217851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA191,039A Expired CA1047534A (en) | 1973-02-07 | 1974-01-28 | Haloacetanilides for influencing plant growth |
Country Status (21)
| Country | Link |
|---|---|
| JP (1) | JPS49109530A (en) |
| AT (1) | AT338554B (en) |
| BE (1) | BE810670A (en) |
| BG (1) | BG20755A3 (en) |
| BR (1) | BR7400845D0 (en) |
| CA (1) | CA1047534A (en) |
| CH (1) | CH582470A5 (en) |
| CS (1) | CS177160B2 (en) |
| DD (2) | DD118617A5 (en) |
| DE (1) | DE2405183A1 (en) |
| ES (1) | ES422953A1 (en) |
| FR (1) | FR2215899B1 (en) |
| GB (1) | GB1455471A (en) |
| HU (1) | HU167576B (en) |
| IL (1) | IL44098A (en) |
| IT (1) | IT1048110B (en) |
| NL (1) | NL7401571A (en) |
| PH (1) | PH11121A (en) |
| PL (1) | PL94680B1 (en) |
| SU (1) | SU581837A3 (en) |
| ZA (1) | ZA74767B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2825543A1 (en) * | 1978-06-10 | 1979-12-13 | Bayer Ag | N-SUBSTITUTED HALOGEN ACETANILIDES, METHOD FOR THEIR PRODUCTION AND USE AS HERBICIDES |
| FR2479198A1 (en) * | 1980-03-25 | 1981-10-02 | Monsanto Co | 2-Alkoxyalkyl-N-haloacetyl aniline derivs. - useful as herbicides for pre- or post-emergent application |
| US4721797A (en) * | 1986-09-02 | 1988-01-26 | Ciba-Geigy Corporation | Process for the preparation of N-acyl-N-alkyl-2,6-dialkyl-3-chloroanilines |
-
1973
- 1973-02-07 CH CH175773A patent/CH582470A5/xx not_active IP Right Cessation
-
1974
- 1974-01-28 CA CA191,039A patent/CA1047534A/en not_active Expired
- 1974-01-28 IL IL44098A patent/IL44098A/en unknown
- 1974-02-04 SU SU7401990653A patent/SU581837A3/en active
- 1974-02-04 CS CS738A patent/CS177160B2/cs unknown
- 1974-02-04 DE DE19742405183 patent/DE2405183A1/en not_active Withdrawn
- 1974-02-04 FR FR7403618A patent/FR2215899B1/fr not_active Expired
- 1974-02-05 DD DD184319A patent/DD118617A5/xx unknown
- 1974-02-05 DD DD176386A patent/DD110746A5/xx unknown
- 1974-02-05 NL NL7401571A patent/NL7401571A/xx not_active Application Discontinuation
- 1974-02-06 GB GB544974A patent/GB1455471A/en not_active Expired
- 1974-02-06 IT IT20254/74A patent/IT1048110B/en active
- 1974-02-06 BG BG25712A patent/BG20755A3/xx unknown
- 1974-02-06 ZA ZA740767A patent/ZA74767B/en unknown
- 1974-02-06 PL PL1974168611A patent/PL94680B1/en unknown
- 1974-02-06 HU HUCI1442A patent/HU167576B/hu unknown
- 1974-02-06 AT AT92474A patent/AT338554B/en not_active IP Right Cessation
- 1974-02-06 BR BR74845A patent/BR7400845D0/en unknown
- 1974-02-06 PH PH15481A patent/PH11121A/en unknown
- 1974-02-06 BE BE140601A patent/BE810670A/en not_active IP Right Cessation
- 1974-02-06 ES ES422953A patent/ES422953A1/en not_active Expired
- 1974-02-07 JP JP49015821A patent/JPS49109530A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE2405183A1 (en) | 1974-08-08 |
| ES422953A1 (en) | 1977-01-01 |
| SU581837A3 (en) | 1977-11-25 |
| PH11121A (en) | 1977-10-27 |
| BE810670A (en) | 1974-08-06 |
| GB1455471A (en) | 1976-11-10 |
| DD118617A5 (en) | 1976-03-12 |
| IT1048110B (en) | 1980-11-20 |
| ATA92474A (en) | 1976-12-15 |
| IL44098A0 (en) | 1974-05-16 |
| DD110746A5 (en) | 1975-01-12 |
| AT338554B (en) | 1977-09-12 |
| CS177160B2 (en) | 1977-07-29 |
| ZA74767B (en) | 1974-12-24 |
| NL7401571A (en) | 1974-08-09 |
| BG20755A3 (en) | 1975-12-20 |
| JPS49109530A (en) | 1974-10-18 |
| FR2215899A1 (en) | 1974-08-30 |
| PL94680B1 (en) | 1977-08-31 |
| HU167576B (en) | 1975-11-28 |
| CH582470A5 (en) | 1976-12-15 |
| AU6505174A (en) | 1975-07-31 |
| BR7400845D0 (en) | 1974-11-26 |
| FR2215899B1 (en) | 1976-06-25 |
| IL44098A (en) | 1977-10-31 |
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