CA1079746A - Nitroaryloxyalkanecarboxylic acid derivatives and their use as herbicides - Google Patents
Nitroaryloxyalkanecarboxylic acid derivatives and their use as herbicidesInfo
- Publication number
- CA1079746A CA1079746A CA259,538A CA259538A CA1079746A CA 1079746 A CA1079746 A CA 1079746A CA 259538 A CA259538 A CA 259538A CA 1079746 A CA1079746 A CA 1079746A
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- carbon atoms
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- chloro
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
- C07C205/42—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/43—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Furan Compounds (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Pyrrole Compounds (AREA)
Abstract
Abstract The present invention provides, as new compounds, the nitroaryloxyalkanecarboxylic acid derivatives of the general formula (I) in which X represents hydrogen, chlorine or nitro, Y represents chlorine or nitro, provided that either X or Y represents nitro, R represents hydrogen or methyl, R1 reoresents hydrogen, an organic radical, a metal cation or a cation of the general formula
Description
~0797~;
The present invention relstes to certain new nitroaryloxyQlksnec~rboxylic acid derivatives, to a process for their prep~ration and to their use as herbicides.
It ha~ been known for a long time that aryloxy~
aIkanecarboxylic acids and their derivatives possess herbi-cidal properties. Thus, 2,4-dichlorophenoxyacetic acid,
The present invention relstes to certain new nitroaryloxyQlksnec~rboxylic acid derivatives, to a process for their prep~ration and to their use as herbicides.
It ha~ been known for a long time that aryloxy~
aIkanecarboxylic acids and their derivatives possess herbi-cidal properties. Thus, 2,4-dichlorophenoxyacetic acid,
2,4,5-trichlorophenoxyacetic acid, 2-~ethyl-4-chlorophenoxy-acetic acid and corresponding a-aryloxypropionic acids9 snd their salts, esters and smides, sre employed in practice as agents for combating weeds. Their action is mainly manifested in the case of diocotyledon plsnts, whereas monocotyledon plants remain subst~ntially unaffected when using the customsry concentration& of active compound. The active compounds in question are therefore u~ed practically exclusively for co~batine weeds in cereal cultures a~d on Erass plots. The exten~ive experimental work carried out on a-~ryloxyalkane-carboxylic acids, which work was essentially concerned with the "growth fsctor" properties of these compounds, sho~ed that only those compounds are usable herbicides ~hich contain a halogen sub~tituent or met ffll substituent in the 2-position and 4-position, and optionslly also in the 5-position, of the aryl radical. If these substituents are present in other positionG of the aryl radical, or if the substituents are other than halogen or methyl, such variations have hitherto generally been regarded as reducing, or even annulling, the effectiveness.
The present invention provides, as new co~pounas, the nitroaryloxyalkanecarboxylic acid derivatives of the general formula ,.
~ - 2 - ~ ~
c~C!o7~7~
~ X~ 0 - C - C - O - ~ Rl (I) in which X represents hydrogen, chlorine or nitro, Y represents chlorine or ;-nitro, provided that either X or Y represents nitro, R represents hydrogen or methyl, Rl represents hydrogen, alkyl with 1-12 carbon atoms, which alkyl radical can be substituted by halogen, alkoxy with up to 12 carbon atoms, alkylmercapto with 1-12 carbon atoms, nitro, trifluoromethyl, cyano, cycloalkyl with 3-7 carbon atoms and/or phenyl; or represents alkenyl with 3-12 carbon atoms, alkinyl with 3-12 carbon atoms, cycloalkyl with 4-6 carbon atoms, or phenyl, which phenyl radical is optionally substituted by halogen, nitro, trifluoromethyl, alkyl w:ith l-4 carbon atoms, alkoxy witl~ carbon atoms or alkyl- :
morcal)to with 1-4 carbon atollls, n i.s 1 o:r 2, clepend:i.ng on tho valcncy Oe the radical Rl.
The compounds of the present invention have been ~ound to ~ .;
possess ver.y good herbicidal properties, without exhibiting the growt factor characteristics which are typical of the category of the previously known aryloxyalkanecarboxylic acids. ;~
Preferably, Rl represents hydrogen, straight chain or branched alkyl with 1 to 12 carbon atoms, which alkyl radical is optionally substituted by fluorine, chlorine, brom:ine, iodine or alkoxy with up to 6 carbon atoms; straight chain or branched alkenyl or alkynyl with, in either case, 3 to 12 carbon atoms; cyclohexyl~phenyl~ which phenyl radical may optionally be substituted by fluorine, chlorine, bromine, ~-iodine, nitro, alkyl with 1 to 4 carbon atoms and/or alkoxy with 1 to 4 carbon atoms; or Rl represents a cation of one of the m~tals lithium, sodium, potassium, magnesium, calcium> barium, aluminium, tin, lead, copper, zinc, iron, nickel and manganese.
The present invention also provides a process for the preparation of a nitroaryloxyalkanecar~oxylic acid derivative in which ~ - 3 ~ ~.
~79746 (a) a nitrophenol of the general formula X ~ -OH ~II) y in which X and Y have the meanings stated above, is reacted with an ~-halo-genoalkanecarboxylic acid derivative of the general formula C~13 ,0, Hal - C - C - -¦ Rl (III) ~ R J n in which R, Rl and n have the meanings stated above, and 11al represents chlo-rine or bromine, if appropriate in the presence of a diluent and in the pre-sence of an acid-binding agent, or (b) a compound of the general ormula Cll3O
X ~ 0~ 0~1 (lV) Y R
in which R, X and Y have the meanings stated above, is reacted with an oxide, hydroxide, carbonate, bicarbonate or alcoholate of a metal selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, aluminium, tin, lead, copper, zinc, iron, nickel and manganese, or tc) a com-pound of the genoral formula ~ ~ R ~ (V1) in which R, X and Y have the meanings stated above and R7 represents alkyl with l to ~ carbon atoms or phenyl, is saponified in an acid or alkaline medium~ if appropriate in the presence of a diluent, and the salt which may thereby be produced is converted, if appropriate, to the free nitroaryloxy-alkanecarboxylic acid by addition of acid, or (d) a compound of the general ~ .
~0797~6 formula ~ :
X ~ c C-Ac (VII) R
in which R, X and Y have the meanings stated above and Ac represents chlorine, bromine, or a group -o-Co-R9, in which R9 represents alkyl or alkoxy, each with 1 to 4 carbon atoms, or a radical of the general formula X ~O-I-C-O ' , R ; :.
in which X, Y and R have the meanings stated above is reacted with an organic ~
hydroxy compound of the general formula :
R8~0tl)n ~VII:[) in which R8 has the meanings stated for Rl ubove, with the only exception that R8 does not represent hydrogen, and _ is 1 or 2, depending on the valency of the radical R , t~ - 5 -.~, .
~079746 if appropriate in the presence of a diluent and in the presence of ~n acid-binding agent.
Surprisingly, the nitroaryloxyalkanecarboxylic acid deri~atives according to the invention exhibit a broad-er herbicidal activity than the sodium salt of 2,4-dichloro-phenoxyacetic acid, known ~rom the state of the art. The compounds according to the invention are, in particular, more suitable for combating grass-like weeds than is the previously known substance which has been mentioned.
Furthermore, the compounds according to the invention can be employed particularly ad~antageously before emergence of the plants. The active compounds according to the invention thus represent a valuable enrichment o~ the art.
I~ 3-nitro-4-chlorophenol and a-chloropropionic acid are used ~s starting materials, the course of the reac-tion according to process variant (a) can be represented by the following equation:
,' ~ ' r==~ , 3 r==~ i Cl ~ -OH ~ Cl-CH-COOH -~ Cl ~ O-CH-COOH
02N -HCl 2 If -(3-nitro-4-chlorophenoxy)-propionic acid and sodium methylate are used as starting materiQls, the course of the reaction according to process variant (b) can be represented by the following equation:
Cl- ~ -O-CH-COOH ~ ~aOCH3 . - ; :
~79746 Cl-~ - O-CH C-ONa + CH30H
If ¢-(3-nitro-4-chlorophenoxy)-propionic acid methyl ester i8 used QS the starting material and dilute sodium hydrox-ide solution and dilute hydrochloric acid as the reactants, ~ -the course of the reaction according to process variant (c) can be represented by the following equation:
Cl ~ -CH - C-OCH3 ~ Cl ~ -O-CH - C -ONa 02N 02N ~ H C1 Cl Cl ~ ~0 - CH - C - OH
02N :.
I~ a-(3-nitro-4-chlorophenoxy)-propionic acid chlo-ride and neopentyl alcohol are used as startin~ materials, the 10course of the reaction according to proces6 variant (d) can be repres~nted by the rollowing equation:
CH O CH
The present invention provides, as new co~pounas, the nitroaryloxyalkanecarboxylic acid derivatives of the general formula ,.
~ - 2 - ~ ~
c~C!o7~7~
~ X~ 0 - C - C - O - ~ Rl (I) in which X represents hydrogen, chlorine or nitro, Y represents chlorine or ;-nitro, provided that either X or Y represents nitro, R represents hydrogen or methyl, Rl represents hydrogen, alkyl with 1-12 carbon atoms, which alkyl radical can be substituted by halogen, alkoxy with up to 12 carbon atoms, alkylmercapto with 1-12 carbon atoms, nitro, trifluoromethyl, cyano, cycloalkyl with 3-7 carbon atoms and/or phenyl; or represents alkenyl with 3-12 carbon atoms, alkinyl with 3-12 carbon atoms, cycloalkyl with 4-6 carbon atoms, or phenyl, which phenyl radical is optionally substituted by halogen, nitro, trifluoromethyl, alkyl w:ith l-4 carbon atoms, alkoxy witl~ carbon atoms or alkyl- :
morcal)to with 1-4 carbon atollls, n i.s 1 o:r 2, clepend:i.ng on tho valcncy Oe the radical Rl.
The compounds of the present invention have been ~ound to ~ .;
possess ver.y good herbicidal properties, without exhibiting the growt factor characteristics which are typical of the category of the previously known aryloxyalkanecarboxylic acids. ;~
Preferably, Rl represents hydrogen, straight chain or branched alkyl with 1 to 12 carbon atoms, which alkyl radical is optionally substituted by fluorine, chlorine, brom:ine, iodine or alkoxy with up to 6 carbon atoms; straight chain or branched alkenyl or alkynyl with, in either case, 3 to 12 carbon atoms; cyclohexyl~phenyl~ which phenyl radical may optionally be substituted by fluorine, chlorine, bromine, ~-iodine, nitro, alkyl with 1 to 4 carbon atoms and/or alkoxy with 1 to 4 carbon atoms; or Rl represents a cation of one of the m~tals lithium, sodium, potassium, magnesium, calcium> barium, aluminium, tin, lead, copper, zinc, iron, nickel and manganese.
The present invention also provides a process for the preparation of a nitroaryloxyalkanecar~oxylic acid derivative in which ~ - 3 ~ ~.
~79746 (a) a nitrophenol of the general formula X ~ -OH ~II) y in which X and Y have the meanings stated above, is reacted with an ~-halo-genoalkanecarboxylic acid derivative of the general formula C~13 ,0, Hal - C - C - -¦ Rl (III) ~ R J n in which R, Rl and n have the meanings stated above, and 11al represents chlo-rine or bromine, if appropriate in the presence of a diluent and in the pre-sence of an acid-binding agent, or (b) a compound of the general ormula Cll3O
X ~ 0~ 0~1 (lV) Y R
in which R, X and Y have the meanings stated above, is reacted with an oxide, hydroxide, carbonate, bicarbonate or alcoholate of a metal selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, aluminium, tin, lead, copper, zinc, iron, nickel and manganese, or tc) a com-pound of the genoral formula ~ ~ R ~ (V1) in which R, X and Y have the meanings stated above and R7 represents alkyl with l to ~ carbon atoms or phenyl, is saponified in an acid or alkaline medium~ if appropriate in the presence of a diluent, and the salt which may thereby be produced is converted, if appropriate, to the free nitroaryloxy-alkanecarboxylic acid by addition of acid, or (d) a compound of the general ~ .
~0797~6 formula ~ :
X ~ c C-Ac (VII) R
in which R, X and Y have the meanings stated above and Ac represents chlorine, bromine, or a group -o-Co-R9, in which R9 represents alkyl or alkoxy, each with 1 to 4 carbon atoms, or a radical of the general formula X ~O-I-C-O ' , R ; :.
in which X, Y and R have the meanings stated above is reacted with an organic ~
hydroxy compound of the general formula :
R8~0tl)n ~VII:[) in which R8 has the meanings stated for Rl ubove, with the only exception that R8 does not represent hydrogen, and _ is 1 or 2, depending on the valency of the radical R , t~ - 5 -.~, .
~079746 if appropriate in the presence of a diluent and in the presence of ~n acid-binding agent.
Surprisingly, the nitroaryloxyalkanecarboxylic acid deri~atives according to the invention exhibit a broad-er herbicidal activity than the sodium salt of 2,4-dichloro-phenoxyacetic acid, known ~rom the state of the art. The compounds according to the invention are, in particular, more suitable for combating grass-like weeds than is the previously known substance which has been mentioned.
Furthermore, the compounds according to the invention can be employed particularly ad~antageously before emergence of the plants. The active compounds according to the invention thus represent a valuable enrichment o~ the art.
I~ 3-nitro-4-chlorophenol and a-chloropropionic acid are used ~s starting materials, the course of the reac-tion according to process variant (a) can be represented by the following equation:
,' ~ ' r==~ , 3 r==~ i Cl ~ -OH ~ Cl-CH-COOH -~ Cl ~ O-CH-COOH
02N -HCl 2 If -(3-nitro-4-chlorophenoxy)-propionic acid and sodium methylate are used as starting materiQls, the course of the reaction according to process variant (b) can be represented by the following equation:
Cl- ~ -O-CH-COOH ~ ~aOCH3 . - ; :
~79746 Cl-~ - O-CH C-ONa + CH30H
If ¢-(3-nitro-4-chlorophenoxy)-propionic acid methyl ester i8 used QS the starting material and dilute sodium hydrox-ide solution and dilute hydrochloric acid as the reactants, ~ -the course of the reaction according to process variant (c) can be represented by the following equation:
Cl ~ -CH - C-OCH3 ~ Cl ~ -O-CH - C -ONa 02N 02N ~ H C1 Cl Cl ~ ~0 - CH - C - OH
02N :.
I~ a-(3-nitro-4-chlorophenoxy)-propionic acid chlo-ride and neopentyl alcohol are used as startin~ materials, the 10course of the reaction according to proces6 variant (d) can be repres~nted by the rollowing equation:
CH O CH
3 " , 3 Cl ~ ~ O - CH - C - Cl + HO - CE2 - C - CX3 ,, - HCl . CH3 0 CH3 Cl ~ O-CH - C - O - CH2 - C - CH3 CH
2~ 3 ., - 7 -.
1()79'7~6 The nitrophencls of the formula (II), to be used in process variant (a), are known. The follo~in~ may be men-tioned specifically: 3-nitrophenol, 3-nitro-~-chlorophenol and ~-nitro-3-chlorophenol.
The maJority of the ~-halogenoaIX~necarboxyllc acid derivatives o~ the formula (III) which can be used according to process variant (a) of the invention are already known.
The compounds of the formula (III) which have not already been described in the literature can be prepared in accordance with customary methods in a simple mar~er by reacting ~-halogeno-propionic acid chloride or a-halogenoisobutyric acid chloride with an appropriate hydroxy compound in the pre~ence of an acid-bindine agent such a~, ~or example, a tertiary aml~e.
The rollowing mu~ be mentloned a~ example~ o~ th~l con,pounds Or the ~ormula (IlI) whlch can be us0d accordin~ to the invention: q-chloro-propionic acid, ~-bromo-propionic acid, a-chloro-isobutyric acid, -bromo-isobutyric acid, ~-chloro-propionic acid methyl ester, ~-chloro-propionic acid isopropyl ester, ~-chloro-propionic acid n-butyl ester, ~-chloro-propionic acid phenyl ester, ~-chloro-propionic acid cyclohexyl ester, ~-chloro-propionic acid allyl ester, ~-chloro-propionic acid propargyl ester and ~-chloro-propionic acid naphthyl ester.
The nitroaryloxyalkanecarboxylic acids of the ~ormula (IV), which can be used as starting materials iD carrying out ~ ^
process variant (b) according to the invention were not pre-viously known, However, they can be prepared by process (a) according to the invention.
The oxides, hydroxides, carbonates, bicarbonate6 and alcoholates, which can be used as further starting materials `:
:1~797~i;
in carrving out process variant (b) according to the invention, are already generally known. The following may be mentioned as individual examples: lithium oxide, lithium methylate, sodium methylate, sodium ethylate, potassium hydroxide, potassium carbonate, magnesium bicarbonate, calcium bicarbonate, barium hydroxide, aluminium methylate, tin hydroxide, lead carbonate, copper carbonate, zinc hydroxide, iron carbonate, nickel carbonate and manganese carbonate.
The amines of the formula (V) which can be used according to process variant (b) o~ the invention are already known.
The following may be mentioned as indi~idual examples:
amMonia, methylamine, dimethylamine, trimethylamine, tri.-n-butyl-amine, N,N-dimethy~-aniline, N,N-dimethyl-benzylamine, pyridine and morpholine.
The compounds of the formula (VI), which can be used in process variant (c), were not previously known; however, they can be prepared by process variant (a) aecording to the invention.
Both strong aoids and strong bases ean be used for saponifying the eompounds of the formula (VI) in aeeordanee with proeess variant (e). The strong aeids include, for example, hydroehlorie aeid and sulphuric acid. Preferred strong bases which can be used according to the invention are alkali metal hydroxides or alkaline earth metal hydroxides, such as, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide.
The eompounds of the formula (VII), to be used in proeess variant (d), were not previously known. Eowever, they can be prepared from the eompounds of the formula (IV) in aecordance with customary methods. Thus 9 for example, ~ Le A 16 61~
1~79746 those co~pounds of the formula (VII) in which Ac represents chlorine are accessible by reacting the free acids of the formula (IV) with inorganic acid chlo:rides, such as phosphorus(III) chloride, phosphorus(V) chloride, phosphorus oxychloride, phosgene or thionyl chlo:ride. Other acid halides of the formula (VII) can be prepared analogously. The remaining compounds of the formula (VII) can be prepared in accordance with the customary methods of forming anhydrides.
The following may be rnentioned as examples o-f compounds of the formula (VII): ~-(3-ni-tro-phenoxy)-propionic acid chloride, ~-(3-nitro-phenoxy)-propionic anhydride, a-(3_ nltro-phenoxy)-propionic acid bromide, a-(~-nitro-phenoxy)-isobutyric acid chloride, a-(3-nitro-4-chloro-pheno~y)-propionic acid chloride, a-(3-nitro-~-chloro-phenoxy)-propionic acid bromide, ~-(3-nitro-4-chloro-phenoxy)-propionic anhydride, o~(3-nitro-4-chloro-phenoxy)-isobutyric acid chloride, a-(4-nitro-3-chloro-phenoxy)-proplonic acid chloride, a-(4-nitro-3-chloro-phenoxy)-propionic acid bromide, ~-(4-nitro-3-chloro-phenoxy)-propionic anhydride and ~-(4-nitro-3-chloro-phenoxy)-i~obutyric acid chloride.
The hydroxy compounds of the formula (VIII) which can be used according to process variant (d) of the invention are already known. The following may be mentioned as examples:
methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec.-butanol, 2-methyl-4-butanol, 2,2-dimethyl-propanol, hexanol, octanol, decanol, dodecanol, 2-chloro-ethanol, 2,2,2-trichloroethanol, 2,3-dibromo-propanol, 2-methoxy--ethanol, 2~phenoxy-ethanol, 2-acetoxy-ethanol, 2-methylmercapto-ethanol, 2-~henylmercapto-ethanol, 2-methylsulphonyl-ethanol, 2-phenyl-sulphonyl-ethanol, 2-nitro-ethanol, 2-dimethyla~ino--ethanol, .. ,.~ /D
i, , ) I ~ Le A 16 613 - ~
.
~79746 2-acetamino-ethanol, 2-methylsulphonylamino-ethanol, glycollie acid ethyl ester, a-hydroxy-isobutyric acid dimethylamide, a-hydroxy-i~obutyronitrile, 2,2,2-trifluoro-ethanol, benzyl alcohol, 4-chlorobenzyl alcohol, 4-nit:robenzyl alcohol, 2-(4-methyl~henyl)-ethanol, 4-cyanobenzyl alcohol, 4-thiocyanato-benzyl alcohol, 4-methoxy-benzyl aleohol, 4-carbomethoxy-benzyl alcohol, 4-dimethylamino-benzyl alcohol, cyclohexyl-methanol, hydrox~methyl-tetralin, -furfuryl alcohol,tetrahydro-furfuryl alcohol, 2-hydroxymethyl-pyrane, 2-hydroxymethyl-~0 thiophene, pyridyl-2-methanol, pyridyl-4-methanol, allyl alcohol, 2-meth~l-but-3-en-2-ol~ ethylene glycol, 2,2'-dihydroxy-diethyl ether, propane-1,2-diol, 3-chloropro~ne-1,2-diol, propane-1,3-diol, butane-1,3-diol, butane-2,3-diol, butane-1,4-diol, 2,2-dimethyl-propane-1,3-diol, but-2-ene-1,4-diol, 2-hydroxymethyl-prop-2-en-1-ol, but-2-inè-1,4-diol, glycerol, 2-methyl-2-hydroxymethyl-propane-1,3-diol, 1,4-bis-hydroxymethyl-cyelohexane, 2j2-bis-hydroxymethyl-l-butanol, eyelopentanol, eyelohexanol, 2-methyl-eyelohexanol, 3,3,5-trimethyl-cyelohexanol, menthol, borneol, 1-hydroxy-tetralin, ~0 2-hydroxy-deealin, eyelohexane-1,2-diol, eyelohe~ane-1,4-diol, .2,4-dihydroxy-1,1,3,3-tetramethyl-cyelobutane, phenol, 4-ehlorophenol, 2,4-diehlorophenol, pentachlorophenol, 4-bromo-phenol, 4-nitrophenol, 2-nitro-4-ehlorophenol, 4 methylphenol, 2-i~opropylphenol, 3-trifluoromethylphenol, 2-cyclohexylphenol, hydroquinone monomethyl ether, 4-phenoxyphenol, 4-methylmer-eaptophenol, 4-phenylmereaptophenol, 4-methylsulphonylphenol,
2~ 3 ., - 7 -.
1()79'7~6 The nitrophencls of the formula (II), to be used in process variant (a), are known. The follo~in~ may be men-tioned specifically: 3-nitrophenol, 3-nitro-~-chlorophenol and ~-nitro-3-chlorophenol.
The maJority of the ~-halogenoaIX~necarboxyllc acid derivatives o~ the formula (III) which can be used according to process variant (a) of the invention are already known.
The compounds of the formula (III) which have not already been described in the literature can be prepared in accordance with customary methods in a simple mar~er by reacting ~-halogeno-propionic acid chloride or a-halogenoisobutyric acid chloride with an appropriate hydroxy compound in the pre~ence of an acid-bindine agent such a~, ~or example, a tertiary aml~e.
The rollowing mu~ be mentloned a~ example~ o~ th~l con,pounds Or the ~ormula (IlI) whlch can be us0d accordin~ to the invention: q-chloro-propionic acid, ~-bromo-propionic acid, a-chloro-isobutyric acid, -bromo-isobutyric acid, ~-chloro-propionic acid methyl ester, ~-chloro-propionic acid isopropyl ester, ~-chloro-propionic acid n-butyl ester, ~-chloro-propionic acid phenyl ester, ~-chloro-propionic acid cyclohexyl ester, ~-chloro-propionic acid allyl ester, ~-chloro-propionic acid propargyl ester and ~-chloro-propionic acid naphthyl ester.
The nitroaryloxyalkanecarboxylic acids of the ~ormula (IV), which can be used as starting materials iD carrying out ~ ^
process variant (b) according to the invention were not pre-viously known, However, they can be prepared by process (a) according to the invention.
The oxides, hydroxides, carbonates, bicarbonate6 and alcoholates, which can be used as further starting materials `:
:1~797~i;
in carrving out process variant (b) according to the invention, are already generally known. The following may be mentioned as individual examples: lithium oxide, lithium methylate, sodium methylate, sodium ethylate, potassium hydroxide, potassium carbonate, magnesium bicarbonate, calcium bicarbonate, barium hydroxide, aluminium methylate, tin hydroxide, lead carbonate, copper carbonate, zinc hydroxide, iron carbonate, nickel carbonate and manganese carbonate.
The amines of the formula (V) which can be used according to process variant (b) o~ the invention are already known.
The following may be mentioned as indi~idual examples:
amMonia, methylamine, dimethylamine, trimethylamine, tri.-n-butyl-amine, N,N-dimethy~-aniline, N,N-dimethyl-benzylamine, pyridine and morpholine.
The compounds of the formula (VI), which can be used in process variant (c), were not previously known; however, they can be prepared by process variant (a) aecording to the invention.
Both strong aoids and strong bases ean be used for saponifying the eompounds of the formula (VI) in aeeordanee with proeess variant (e). The strong aeids include, for example, hydroehlorie aeid and sulphuric acid. Preferred strong bases which can be used according to the invention are alkali metal hydroxides or alkaline earth metal hydroxides, such as, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide.
The eompounds of the formula (VII), to be used in proeess variant (d), were not previously known. Eowever, they can be prepared from the eompounds of the formula (IV) in aecordance with customary methods. Thus 9 for example, ~ Le A 16 61~
1~79746 those co~pounds of the formula (VII) in which Ac represents chlorine are accessible by reacting the free acids of the formula (IV) with inorganic acid chlo:rides, such as phosphorus(III) chloride, phosphorus(V) chloride, phosphorus oxychloride, phosgene or thionyl chlo:ride. Other acid halides of the formula (VII) can be prepared analogously. The remaining compounds of the formula (VII) can be prepared in accordance with the customary methods of forming anhydrides.
The following may be rnentioned as examples o-f compounds of the formula (VII): ~-(3-ni-tro-phenoxy)-propionic acid chloride, ~-(3-nitro-phenoxy)-propionic anhydride, a-(3_ nltro-phenoxy)-propionic acid bromide, a-(~-nitro-phenoxy)-isobutyric acid chloride, a-(3-nitro-4-chloro-pheno~y)-propionic acid chloride, a-(3-nitro-~-chloro-phenoxy)-propionic acid bromide, ~-(3-nitro-4-chloro-phenoxy)-propionic anhydride, o~(3-nitro-4-chloro-phenoxy)-isobutyric acid chloride, a-(4-nitro-3-chloro-phenoxy)-proplonic acid chloride, a-(4-nitro-3-chloro-phenoxy)-propionic acid bromide, ~-(4-nitro-3-chloro-phenoxy)-propionic anhydride and ~-(4-nitro-3-chloro-phenoxy)-i~obutyric acid chloride.
The hydroxy compounds of the formula (VIII) which can be used according to process variant (d) of the invention are already known. The following may be mentioned as examples:
methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec.-butanol, 2-methyl-4-butanol, 2,2-dimethyl-propanol, hexanol, octanol, decanol, dodecanol, 2-chloro-ethanol, 2,2,2-trichloroethanol, 2,3-dibromo-propanol, 2-methoxy--ethanol, 2~phenoxy-ethanol, 2-acetoxy-ethanol, 2-methylmercapto-ethanol, 2-~henylmercapto-ethanol, 2-methylsulphonyl-ethanol, 2-phenyl-sulphonyl-ethanol, 2-nitro-ethanol, 2-dimethyla~ino--ethanol, .. ,.~ /D
i, , ) I ~ Le A 16 613 - ~
.
~79746 2-acetamino-ethanol, 2-methylsulphonylamino-ethanol, glycollie acid ethyl ester, a-hydroxy-isobutyric acid dimethylamide, a-hydroxy-i~obutyronitrile, 2,2,2-trifluoro-ethanol, benzyl alcohol, 4-chlorobenzyl alcohol, 4-nit:robenzyl alcohol, 2-(4-methyl~henyl)-ethanol, 4-cyanobenzyl alcohol, 4-thiocyanato-benzyl alcohol, 4-methoxy-benzyl aleohol, 4-carbomethoxy-benzyl alcohol, 4-dimethylamino-benzyl alcohol, cyclohexyl-methanol, hydrox~methyl-tetralin, -furfuryl alcohol,tetrahydro-furfuryl alcohol, 2-hydroxymethyl-pyrane, 2-hydroxymethyl-~0 thiophene, pyridyl-2-methanol, pyridyl-4-methanol, allyl alcohol, 2-meth~l-but-3-en-2-ol~ ethylene glycol, 2,2'-dihydroxy-diethyl ether, propane-1,2-diol, 3-chloropro~ne-1,2-diol, propane-1,3-diol, butane-1,3-diol, butane-2,3-diol, butane-1,4-diol, 2,2-dimethyl-propane-1,3-diol, but-2-ene-1,4-diol, 2-hydroxymethyl-prop-2-en-1-ol, but-2-inè-1,4-diol, glycerol, 2-methyl-2-hydroxymethyl-propane-1,3-diol, 1,4-bis-hydroxymethyl-cyelohexane, 2j2-bis-hydroxymethyl-l-butanol, eyelopentanol, eyelohexanol, 2-methyl-eyelohexanol, 3,3,5-trimethyl-cyelohexanol, menthol, borneol, 1-hydroxy-tetralin, ~0 2-hydroxy-deealin, eyelohexane-1,2-diol, eyelohe~ane-1,4-diol, .2,4-dihydroxy-1,1,3,3-tetramethyl-cyelobutane, phenol, 4-ehlorophenol, 2,4-diehlorophenol, pentachlorophenol, 4-bromo-phenol, 4-nitrophenol, 2-nitro-4-ehlorophenol, 4 methylphenol, 2-i~opropylphenol, 3-trifluoromethylphenol, 2-cyclohexylphenol, hydroquinone monomethyl ether, 4-phenoxyphenol, 4-methylmer-eaptophenol, 4-phenylmereaptophenol, 4-methylsulphonylphenol,
4-phenylsulphonylphenol, 4-hydro~y-acetophenone, acetic acid 4-hydroxyphenyl ester, 3-dimethylamino-phenol, 4-acetamino-phenol~ 4-cyanophenol, 4-hydroxy-benzoic acid ethyl ester, 4-hydroxy-benzoic acid dimethylamide, 4-thiocyanato-phenol, 1-... , /
~ e A 16 613 - ~
na~hthol, 2-naphthol, 4-hydroxy-benzenesulphonic acid dimethyl-amide, 6-hydroxy-tetralin, 2-hydroxy-biphenyl, pyrocatechol, resorcinol, hydroquinone, 4,4'~-dihydroxy-diphenyl-sulphone, 1,5-dihydroxy-naphthalene, 2,6-dihydroxy-naphthalene, 4,4'-dihydroxy-diphenyl, 2,2-bis-t4-hydroxyphenyl)-propane, phloro-glucinol, 2,4-dihydroxy-acetophenone, 2-hydroxy-dibenzofurane, 3-hydroxy-6-methoxy-benzothiophene, 7-hydroxy-4-metllyl~
coumarine, 5-hydroxy-2-hydroxymethyl-4-pyrone (kojic acid), 6-hydroxy-2,4-dimethyl-1,3-dioxane, 8-hydroxy-quinoline, 2-hydroxy-carbazole, hydroxymethyl-phthalimide, 1,3,5-tris-hydroxyethyl-hexahydro-s-triazine and 6~hydroxy-2-methyl-benæothiaæole.
In carrying out process variant (a) according to the invention, all inert solvents can be used as dlluents, especially alcohols such as methanol, ethanol, isopropanol and butanol; ethers such as dibutyl ether, glycol mono-methyl ether, dioxan and tetrahydrofuran; aliphatic and arom~tic hydrocarbons, such as cyclohexane, ben~ine, toluene, benzene and xylene; ketones, such as acetone, methyl i~ropyl ketone and cyolohexanone; carboxylic acid amides such as dimethylformamide and dimethylacetamide; and strongly polar solvents such as acetonitrile and dimethylsulphoxide.
At times, water can also be employed as the solvent.
In the reaction according to process variant (a), all customary acid acceptors can be used as acid-binding agents, especially alkali metal hydroxides, alkali metal carbonates, alkali metal alcoholates, alkaline earth metal hyaroxides, ; alkaline earth metal carbonates, heavy metal oxides, ammonia and ter~ary amines. ~he following may be mentioned as being particularly suitable: sodium carbonate, potassium carbonate, .,~ /~
~e A 16 613 ; ~"
..." , r ~,~
797~6 triethyla~ine, N,N-dimeth~l-aniline, ~,N-dimethyl-benzyl-amine, pyridine and quinoline.
In process ~ariant (a), the reaction temperatures c~ be varied within a fairly wide ran~e. In general, the reaction is carried out at temperatures between 0C and 150 C, preferably between 20 C and 120 C.
In carrying out process variant (a) according to the invention, l to 1.5 moles of an ~-halogenoalkanecarboxylic acid derivative of the formula (III) and 2 to 2.5 moles, rel- , ative to base equivalents, of acid-binding agent, are pref-erably employed per mole of the nitrophenol of the for~ula (II).
In proce~ variant (a) accordiDg to the invention, the compound~ of the forml~la (L) ~re i~olated b~ conventional method6. If, for example, a nitrophenol of the formula (II) is reacted with an ester of the for~ula (III), a suitable procedure is to filter off, after completion of the reaction, the salts which have been formed, concentrate the filtrate and, if appropriate, purify the residue by recrystallisation.
If the reaction haa been carried out in a water-miscible solvent, it is al~o possible to precipitate the reaction product~ by addition of water, after prior removal of the salts, and then to filter them off. If a nitrophenol of the formula (II) is reacted with a free acid of the formula (III), the reaction products of the formula (I) are obtained in the form of salts, frequently associated with the hydrochloride or hydrobromide of the particular base employed. The salts are filtered off, converted into the free, sparingly water-soluble nitrophenyloxycarboxylic acids of the formula (I) by treatment with mineral acids in arl aqueous medium, and ~797~6 filtered off.
In carrying out process variant (b) according to the invention, all inert solvents can be used as the diluents.
They include, in particular, water and those solvents which have already been mentioned as being pre~erred in connection with nrocess variant (a).
In ~rocess variant (b), the reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at temperatures between -20C and 150C, ~referably between 0C and 1 ooa.
In carrying out process variant (b) according to the invention, 1 equivalent, or a slight excess, o~ a metal oxlde, metal hydroxide,metal carbonate,metal bicarbonate or metal alcoholate, or of an amine of the formula (V) is employed per mole of the compound of the formula (IV).
In process variant (b) according to the invention, the reaction products are isolated by customary methods. If the reaction is carried out in a solvent of low polarity, the salts are obtained ln a orystalline form and can be isolated by riltration. I~ the reaction is carried out in a strongly polar solvent, the reaction products are obtained by dis-tilling o~f the solvent.
In carrying out process variant (c) according to the invention, all inert solvents can be used as diluents, especially water-miscible alcohols such as methanol, ethanol and isopropanol.
In process variant (c) according to the invention, the reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at temperatures between 10C and 100C, preferably between 20C and 70a.
"~ 1 ' ~1 11 ~e A 16 613 107974~
In carrying out proces~ variant (c) according to the invention, an equivalent amount, or an excess, of a strong acid or of a strong, optionally aqueous, base is employed ~er mole of the compound of the formula (VI).
In process variant (c) according to the invention, the reaction products are isolated by the customary methods. If the reaction is carried out in an acid medium, a suitable procedure is to dilute the reaction mixture, after completion of the reaction, with water and to filter off the free acids of the formula (I), which are thus obtained in a crystalline form, and dry them. I-~, on the other hand, the reaction is carried out in an alknline medtum, the ~alt~ of the formula (I) are obtainecl ~n a pure ~orm by ~imply distillin~ o~ the solvent. I~ it is not the salt~ but the free acids of the formula (I) which are to be prepared by the sàponification in an alkaline medium, a suitable procedure is to acidify the reaction mixture after completion of the reaction, dilute it with water if appropriate and filter off the acids which thereupon are obtained in a crystalline form, and dry them.
In oarrying out proces~ varlant (d) aocording to the invention, all inert sol~ents can be used as diluents, especially ketones such as acetone, methyl isopropyl ketone and cyclohexanone; ethers such as diethyl ether, dibutyl ether, glycol dimethyl ether, dioxan and tetrahydro~uran;
aliphatic or aromatic hydrocarbons, such as hexane, benzine, benzene, toluene and xylene; chlorinated aliphatic or aromatic hydrocarbons, such as methylene chloride, chloro-; form, carbon tetrachloride and chlorobenzene; esters such as ethyl acetate; and strongly polar solvents such as dimethylformamide, acetonitrile and dimethylsulphoxide. At e A 16 613 ~ 5 -~079746 tir~es, the solvents can also be diluted with water. If lower alkanols are used as reactant~, these can in some cases also function a~ solvents.
In the reaction according to process variant (d), all customary ~cid acce~tor~ can be u~ed as acid-binding agents, especially those acid-binding agents which have already been mentioned preferentially in connection with process variant (a). Further preferred acid-binding agents are alkali metal a~ide~ and alkali metal hydrides, as well as the alkali metal alcoholates and alkali metal phenolates of the compounds o~
the rormula (VIII) which are employed.
The reaction temperatures in proce~ variant (d) according to the invention can be varied within a fairly wide range. In general, the reaction is carried out at temper-atures between 0C and 120C, preferably betweèn 0C and 50C.
In carrying out process variant (d) according to the invention, preferably an equivalent amount, based on the hydroxyl group to be esteri~ied, of a compound o~ the ~ormula (VIII), and an equivalent amount of acid-binding agent, are employed per mole o~ the compound o~ the ~ormula (VII).
However, it i3 also pos~ible to use a large excess of a compound of the formula (VIII) or of acid-binding agent. This is particularly advisable when a compound of the formula (VIII), or the acid-binding agent, at the same time serves as the solvent.
In process variant (d), the reaction products are suit-ably isolated by separating off, a~ter completion of the reaction, the salts which have formed, concentrating the filtrate by evaporation, and recrystallising the residue or stirring it with water and filtering off the product which /~
~ e A 16 613 -~
~(~79746 thereupon separates out. However, it is also vossible to dilute the filtrate, obtained after removal of the salts, directly with water and to filter o~f the product which here-u~on is obtained in a crystalline fo~n.
The ~ollowing may be mentioned as examples of the nitroaryloxyalkanecarboxylic acid derivative~ according to the invention, of the formula (I): à-(3-nitro-phenoxy)-propionic ~cid, a-(3-nitro-4-ch]oro-phenoxy~-propionic acid, a-(4-nitro-3-chloro-phenoxy)-propionic acid, a-(3-nitro-phenoxy)-i~obutyric acid, a-(3-nitro-~-chloro-phenoxy)-iso-but~ric acid, a-(4-nitro-3-chloro-phenoxy) isobutyri¢ aoid, the ~od~.um ~alt o~ a-(3-nitro-4-ohloro-phenoxy)-propionic acid, the ammonium ~alt o~ a-(3-nitro-4-chloro-phenoxy)-propionic acid, the methylammonium salt o~ a-(3-nitro-4-chloro-phenoxy)-propionic acid, the di-(2-hydroxyethyl)-ammonium salt of a-(3-nitro-4-chloro-phenoxy)-propionic acid, a-(3-nitro-phenoxy) propionic acid methyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid methyl ester, a-(4-nitro-3-chloro-phenoxy)-proplonic acid methyl ester, a-(3-nitro-phenoxy)-i~obutyric acid methyl e~ter, a-(3-nitro-4-chloro-phenoxy)-isobutyric acid methyl ester, a-(4-nitro-3-chloro-phenoxy)-isobutyric acid methyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid ethyl ester, a_(3-nitro-4-chloro-pheno~y)-propionic acid propyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid isopropyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid butyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid isobutyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid sec.-butyl ester, a-(3-nitro-4-chloro-phenoxy)~propionic ac:id hexyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic ac:id neopentyl ester, a-(3-nitro-~-chloro-phenoxy)-propionic acid cyclohexyl ~ ~e A 16 613 - ~ -'`'' iai79746 ester, d-(3-nitro-4-chloro-phenoxy)-propionic acid benzyl ester, ~-(3-nitro-4-chloro-phenoxy)-propionic acid allyl ester, ~-(3-nitro-4-chloro phenoxy)-propionic acid propargyl ester, ~-(3-nitro-4-chloro-phenoxy)-propionic acid 2-methoxy ethyl ester, ~-(3-nitro-4-chloro-phenoxy)-propionic acid 2-butoxy-ethyl ester, ~-(3-nitro-~-chloro-phenoxy)-propionic acid phenyl ester, ~-(3-nitro-~-chloro-phenoxy)-propionic acid 4-chlorophenyl ester, -(3-nitro-4-chloro-phenoxy)-propionic acid 4-methoxy-phenyl ester, a~(3-nitro-4-chloro-~
phenoxy)-propionic acid 4-nitrophenyl ester, ~-(4-nitro-3-chloro-phenoxy)-propionic acid ethyl ester, a~ -nitro-3-chloro-phenoxy)-propionic acid neopentyl ester, ~-(4-nitro 3-chloro-phenoxy)-propionic acid cyclohexyl ester, ~-(4-nitro-3-chloro-phenoxy)-proplon:lc acld ~en~yl e~ter and ~ -nitro-3-chloro-phenoxy) -proplonlc uci.d l~-chlorophenyl ester.
The active compounds according to the invention influ-ence plant erowth and can therefore be used as defoliants, desiccants, aeents for destroying broad-leaved plants, ger-mination inhibitors and, especially, weed-killers. Weeds, in the broadest sen~e, are to be understood as all plants which grow in locations where they are undes-lred. Whether the compounds according to the invention act as total herbicides or as selective herbicides depends essentially on the amount used.
~he active compounds according to the invention can be used, for example, in connection with the ~ollowin~ plants:
Dicotyledon weeds such as mustard (Sinapis), cress (Lepidium), bed straw (Galium), chickweed (Stellaria), camomile (Matricaria), mayweed (An-themis), gallant soldier (Galinsoga), goose~oot (Chenopodium), annual nettle (Urtica)~
, . ' ,.:
107~31746 grounsel ~Senecio), plgweed (Amaranthus), puralane (Portu-laca), cocklebur (Xanthium), bindweed (Convolvulus), morning glory (Ipomoea), knotweed (Poly~onum), sesb~Dia (Sesbania), ragweed (Ambrosia), spear thistle (Cirsium)l common thistle (Carduus), sow thistle (Sonchus), nightshade (Solanum), field cress (Rorippa), toothcup (Rotala), (Lindernia), deadnettle (Lamium), speedwell (Veronica), mallow (Abutilon), emex (Emex), thornapple (Datura), violet (Viola), hemp-nettle (Galeopsis~, poppy (Papaver) and knapweed (Centaurea);
Dicotyledon cultures such as cotton (Goss~pium), soya bean (~1Y~ ), beet (Beta), carrot (Daucus), bean (Phaseolus), pea (Pisum), potato (Solanum), flax (Linum), mornin~ glory (I_omoea), broad bean (Vicia), tobacco (Nicotian~), tom~lto (Lyco~ersicon), ~roundnut (Arachia), ca~ba6e (Brasaica), lettuce (lactuca), cuc~ber ( ucumis) and marrow (Cuburblta);
Monocotyledon weeds such as barnyard grass (Echinochloa), foxtail (Setaria), wild millet (Panicum), crabgrass (DieitPria), timothy (Phleum), bluegrass (Poa), f2scue (Festuca), goosegrass (Eleusine), signalgrass (Brachiaria), ryegrass (I.olium), cheat (Bromus), oats (Avena), flatsedge (Cyperus), sorghum ( _r~ ), quackgrass (Agropyron), Bermud& erass (Cynodon), Monocharia, ~imbristylis (Fimb~isty-lis), arrowhead (Sagittaria), spikerush ( leocharis), bulrush (Scirpus), paspalum (Paspalum), Ischaemum, gooseweed (Spheno-clea), crowfoot grass (Dactyloctenium), redtop (Agrostis), meadow foxtail (Alopecurus) and silky bent-grass (~pera), and Monocotyledon cultures such as rice (Oryza), maize ~ ), wheat (Tr~ticum), barley (Hordeum)~ oats (Avena), rye (Secale), sorghum (~ ), millet (Panicum), sugar cane ~0 (Saccharum), pineapple (Ananas), asparagus (Asparaeus) and onion (Allium).
- lq _ :L~79746 The use of the active compounds according to the invention is, howe~er, in no way restricted to t~e genera indicated above, but extends, in the snme way, also to other plants.
Depending on the concentration, the compounds are suitable for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares which may or may not be planted with trees. Equally, the compounds can be employed for combating weeds in permanent cultures, for example ~fforestation, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plentations, cacao plantMtions, ~oft fruit orchards and hopfields, and for the selective co~ating of weeds in annuQl crop~.
In particular, the active compounds according to the invention are suitable for the selective combating of weeds in fields of crop plants such as maize and wheat.
~he active compounds according to the present inven- -tion can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. I'he6e may be produced in known m~mer, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optlonally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic so~vents can, for example, al80 be used as auxiliary solvents.
As liquid diluents or carriers, there are preferably used - 20 - ~
- .: ' . ': ' :, aromatic hydrocarbons, such as xylenes, toluenei benzene or alkyl na~hthalenes, chlorinated aromatic or a~iphatic hydro-carbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for exam~le mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl iso-butyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or aceto-nitrile, as well as water.
~y lique~ied gaseou~ diluents or carrier~ are meant li~uid~ which would bo ga~eous at normal temperatures and pressures, ~or examplè aerosol propellants, such as halo-genated hydrocarbons, for example freon.
As solid diluents or carriers, there are pre~erably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed 8ilicic acid, alumina or silicates.
Pre~erred examples o~ emulsi~ying and ~oam-forming agents include non-ionic and anionic emulsi~iers, such as polyoxy-ethylene-fatty acid esters, polyoxyethylene-~atty alcohol ethers, ~or example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as albumin hydrolyzation products; and pre~erred examples o~ dispersing agents include lignin sulphite waste liquors and methyl cellulose.
The active compounds according to the in~ention, as such or as their ~ormulations, can be combined with other .,~, .
~ ~o herbicidally active compoun~ order to boost and supple-.
~e A 16 613 - ~
.~ ~
ment their s~ectrum of action, depending on the intended use;
ready-mixed formulations, or tank mixing, may be employed.
In particular, the active compounds mentioned below and other members of the grou~s of active compowlds represented by these ~articular active compounds are also suitable for this purpose.
2,3,6-Trichlorobenzoic acid and its salts, 2,3,5,6-tetrachlorobenzoic acid and its ~alts, 3-nitro-2,5-dichloro-ben~oic acid and its salts, 3-amino-2,5-dichlorobenzoic acia an~1 it.s sa].ts, 2-methoxy-3,6-dichlorobenzoic acid and its salts, 2-mcthoxy-3,5,6-trichlorobcnY.~ic aoid and its salts, 2,6-di.chloro-thiobon~amide, 2,6-dlchlorobenzonitrile, 2,4-dichlorophenoxyacctlc aoid as well a~ it~ ~alt~ and ~stera, 2,4,5-trichlorophenoxyacetic acid and its salts and esters, (2-methyl-4-chlorophenoxy)-acetic acid and its salts and esters, 2-(2,4-dichlorophenoxy)-propionic acid, (2-(2-methyl-4-chloro-phenoxy)-propionic acid and 2-(2,4,5-trichlorophenoxy~-propionic acid and their salt~ and esters, 4-(2,4-dichloro-phenoxy)-butyric acid and its salts and esters, 4-(2-methyl-4-chlorophenoxy)-butyric acid and its salt~ and esters, 2,3,6-trichlorophenyl-acetic acid and it~ salt~ and 4-amino-3,5,6-trichloropicolinic acid.
Trichloroacetic acid and its salts, 2,2-dichloro-propionic acid and its salts, 2-chloro-N,N-diallylacetic acid amide, dinitrocresol, dinitro-sec.-butylphenol and its salts.
3-Phenyl-1,1-dimethyl-urea, 3-(4'-c~Loropheny:L)-1,1-dimethyl-urea, 3-(3',4'-dichloro~henyl)-1,1-dimethyl-urea, 3-(~',4'-dichloro~henyl)-1-n-butyl-1-rnethyl-urea, 3-(3',4'-dichlorophenyl)-1,1,3-trimethyl-urea, 3-(4'-chlorophenyl)-1-: 30 methoxy-1-methyl-urea, 3-(3'-trifluoromethyl-phenyl)--1,1-~2 e A 16 613 -~
~C1797~6 dimethyl-ure~, 3-(3',4'-dichlorophenyl)-1-methoxy-1-methyl-urea, 3-(4' bromophenyl)-l-methoxy-l-methyl-urea, 3-(3',4'-dichlorophenyl)-3-methoxy-1,1-dimethyl-urea, 3-(4'-chloro-phenoxyphenyl)-l,l-dimethyl-urea, N'-cyclooctyl-N,~-dimethyl-urea, 3-(benzthiazol-2-yl)-1,3-dimethyl-urea and 3-(3-chloro-4-methylphenyl)-1,1-dimethyl-urea.
N,M-Di-(n-propyl)-S-n-propyl-thiocarbamic acid ester, N-ethyl-N-(n-butyl)-S-n-propyl-thiocarbamic acid ester, ~,N-di-(n-propyl)-S-ethyl-thiocarbamic acid ester, ~-phenyl-0-isopropyl-carbamic acid ester, N-(m-chlorophenyl)-0-isopropyl-carbamic acid ester, N-(3',4'-dichlorophenyl)-0-methyl-carbamic acid ester, N-(m-chlorophenyl)-0-(4-chloro-butin-(2)-yl)-carbamic acid ester, n- ( 3'-methylphenyl)-0-(3-methoxy-carbonylaMinopheny~)-c~rbami.c acld cnter and ~,N-dilrlopropyl-~hiocarbQmlc aci.tl 2,3,3-trichloroallyl ester.
3-Cyclohexyl-5,6-trlmetbylene-uracil, 5-bromo-3-sec.-butyl-6-methyl-uracil, 3,6-dioxo-1,2,3,6-tetrahydropyridazine and 4-amino-5-chloro-1-phenyl-6-pyridazone.
2-Chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-chloro-4,6-bis-(methoxypropylamino)-s-triazine, 2-methoxy-4,6-bis-(isopropylamino)-s-triazine, 2-diethylamino-4-iso-propyl-acetamido-6-methoxy-s-triazine, 2-isopropylamino-4-methoxy-propylamino-6-methylthio-~-triazine, 2-methylthio-4,6-bis-(iso-propylamino)-s--triazine, 2-chloro-4,6-bis-(ethylamino)-s-triazine, 2-methylthio-4,6-bis-(ethylamino)-~ s-triazine, 2-methoxy-4-ethylamino-6-isopropylamino-s-: triazine, 2-methylthio-4-ethylamino-6-isopropylamino-s-triazine, 2-methoxy-4,6-bis-(ethylamino)-s-triazine and 2-chloro-4,6-bis-(isopropylamino)-s-triazine.
N,N-Diethyl-2,4-dinitro-6-tri~luoromethyl-1,3-phenylenediamine, N,N-di-n-propyl-2,6-dinitro-4-tri~luoro-- 23 - .:
iO797~6 methyl-aniline, 4'-nitro-2,4-dichloro~-diphenyl ether, ~,4-dichlorophenyl-propionamide and 2',6'--diethyl-N (methoxy-methyl)-2-chloroacetanilide.
The active compounds according to the invention can be Present in the formulations as a mixture with other active compound~, such as fungicide~, insect:Lciae~ and acaricides.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably ~rom 0.5 to 90 ~er cent by weight.
The active compound~ can be used as such, in the ~orm of their formulatlons or as the use forms~ ~repared therefrom, ~uch a~ ready-to-u~e solutions, emulsion~, ~uspen~ions, ~owdor~, pa~teB and granul0~. They may be u~ed ~n the customary manner, for example by sprayin~, atomising, du~ting, scattering and watering.
Preferably, they are used in accordance with the pre-emergence process, ~he amount of active compound employed can vary within fairly wide ranges; it depend~ es~entially on the nature of the desired effeot. In ~eneral, the amounts used are ~rom 0.1 to 20 kg o~ active compound per he¢tare, pre~erably from 0.2 to 15 kg/ha.
The present invention al~o provides a herbicidal com-po~ition containing a~ active ingredient a`compound of the present in~ention in admixture with a solid`or lique~ied gaseous diluent or carrier or in admixture with a 11quid diluent or carrier containing a ~urface-acti~e a~ent.
The pre~ent invention also provide~ a methocl o~ com-bating weeds which comprise~ applying to the weecLs or a weed habita`t a compound of the present in~ention alone or in the e A 16 613 _ ~r-. ` .
~"
~C~797~6 ~orm of a compo~ition containine a~ active ingredient a compound of the present i~ention in admixture with a diluent or carrier9 The present invention further provides crops protected from damage by weeds by being grown in areas in which i~ediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier. It will be seen that the usual methods of providing a harvested crop may be improved by the pre~ent invention.
The biote~t Example which ~ollows is intended to illu~trate the good herbicidal aotivlty of the active com-~ound~ according to the inventlon.
~ A
Pre-emergence te~t Solvent: 5 partæ by weight of acetone ~mulsi~ier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emul~ifier was added and the ooncentrate was diluted with water to the desir0d concentration.
Seed~ of the test plants were sown in normal 80il and, after 24 hours, watered with the preparation of the active compound. It was expedient to keep constant the amount o~
water per unit area. The concentration o~ the active com-pound in the preparation wa~ of no importance, only the amount of active compound applied per unit area bei~g decisive.
After three weeks, the degree o~ damage to the plants was determined in % damage in comparison to the development of ~ e A 16 613 ~"
~C9797~6 the untreated control. The figures denote:
~0 = no action (like untreated control) 100jo - total destruction The active compounds, the amounts appli.ed and the results can be seen from the table which follows:
.
~, ., .
. .
., ~
~ ~e A 16 613 1~79~74~
N
.~ 00 00 00 00 ~ ~ ~ . N ~
00 oo oo oo a) ~ C~
~1~1 oo oo rl ~
~ h 00 00 00 00 ~ l OO~ 00 ~0~
1, ~ ~1 oo oo ,~ ~ I o~ oo o a~ oa~
C~
~a ~a~ n~ Oo 00 00 00 c)~ hl ~0 d- O a~ o a~ o a~
~,~ ~1 o o o o o o o o bD~1 l ~co o ~ o o o ~ ~ ~ oa oo cra , ~ ~1 g 8 o ~ $ ~ o o~
~H ~`~
p O r O ~ ~ Q~ L~ t 0~ ..
Z
E~' ~ o -~ o o o 1~
e A 16 613 . . ~;,, .. , ., ~ .
:
~07974G
Q~
d- N ~ N, -O O O O O O
~I"JI ~ OO~) D
¢~
~1 a0 O
~1~ o o o o o o a ~1 o o o o co ¦ a al~ ~o o~o ~oo .,, 'd¦ I al ~ o o o o o oI a~ o~
o ~ OO OOD O O
i Ir~ N 15~ N Ir~N
3 ~ o D ~ ~ 0~
c,) ~o ~, e A 16 613 ~ ~ _ .
.
, ~7g'79~
~rl ~:
o o t-.
cd o o In ~
¢ 4~
s~ .,, o o ~ h oo ~
~ ~d ~ ~¢
_~ ~4 o o ~ o o a-~n ,~
t~
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$~ ~ ~ o ~ ~ . , o , U~ o 'C ~ d o ., ~ ~
~ , t~ ~ ,U) o o E~ ~
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~0~974E;
The process of the present invention is illustrated by the following preparative Examples.
l~xa~Ple 1: (Process variant (a)) ~ -O~ H-C-OCH (1) o 500 g (3.6 moles) of potassium carbonate were intro-duced, in portions, into a mixture of 278 g (2 moles) of 3-nitro~henol, 245 g (2 moles) of 2-chloro-propionic acid methyl ester and 1 litre of acetonitrile whilst stirring at room temperatl~e. The reaction mixture was gradually warmed to the boil and wa~ then boiled for lO hour~ under re~lux.
'~he salts whioh had ~ormed were then ~iltered eff and the filtrate was eva~orated under reduced pressure. 370 g (82.5~ of theory) of a_(3-nitro-phenoxy)-propionic acid methyl ester were obtained in the ~orm of an oily residue.
~urther purification was effected by dissolving the crude product in wash benzine and again evaporating the solution, a~ter filtration. ~he substance which hereupon remained, and which was liquid at room temperature, was, according to the 1H-~R spectrum and the elementary analysis, a-(3-nitro-phenoxy)-propionic acid methyl ester.
~lementary analysis C1oH11N05(22502) calculated: 53.4% C; 4.93~ H; 6-22% ~
found : 53~7% C; 5.02% H; 6.17~o N
The compounds listed in Examples 2 and 3 were obtained analogously:
CH
Example 2: 3o 02N- ~ ~~ H-C-oCH3 ~2) Cl ~ o i~ ~eiA 16 61 : , ' ' .
-~7~746 ~ -(4-Nitro-3-chloro-phenoxy)-propionic ao:id methyl e~ter of meltin~ point 73-75C ~from wash benzine).
~xam~le ~:
iH3 : Cl-~3-O-CH-C-OCH
a-(3-Nitro-4-chloro-phenoxy)-propionic acid methyl ester of melting point 43C (from wash benzine).
~xample 4:
~\ 3 Cl- @ -0-C-C-0CH3 02N C~13 (4) 173.5 g (l mole) o~ 3-nitro-4-chloro-phenol and 179 g o~ a-bromo-isobutyric acid methyl ester in 600 ml o~ aceto-nitrile were boiled with 250 g of potassium aarbonate for 10 hours under reflux. The salts were filtered o~f; and the ~iltrate wa~ evaporated in vacuo. The residue was stirred with 500 ml of chloro~orm. The ~olution was decanted from the insoluble residue and wa~ evaporated in vacuo. ~he re~idue was recry~talli~ed ~rom wash benzine. 186 g (68~ o~ ;
theory) of a-(3-nitro-4-chloro-phenoxy)-i~obutyric acid methyl ester o~ melting point 31-33C were obtained.
xample 5: (Process variant (b)) ÇH3 o Cl-@ O-CH-C-ONa (5) 24.5 (0.1 mole) of a-(3-nitro-4-chloro-pheno~y)-propionic acid were dissolved in 100 ml of methanol. A
e A 16 613 --~r-1C~7~74~
solution of 2.3 ~ (0.1 mole) oP sodium in a little methanol was added thereto, whilst stirring. The reaction mixture was cooled with ice and the salt which had separated out was filt~rcd off and rinsed with a little :Lce-cold methanol. Thi~
gave the sodium salt of a-(3-nitro-4-chloro-phenoxy)-~ropionic acid in ~ractically quantitative yield. Melting point ~300C.
J~xample 6: (~rocess variant (c)) Cl- ~ -o-CH-COOH (6) ()2N
259.5 g ~1 mole) of a-(3-nltro-4-ohloro-ph0noxy)-propionlc aoid methyl ester were dissolved in 1 litre o~
ethanol. 1 litre of 5~ strength aqueous sodium hydroxide solution was added thereto. The mixture was briefly heated to the boil, then acidified with dilute hydrochloric acid at 55-60C, and finally cooled with ice. ~he crystals which separated out were filtered off and washed with water. ~his gave 238 g (97.5% of theorg) of ~-(3-nitro-4-chloro-phenoxy)-propionic acid which, after reorystallisation ~rom toluene, had a melting point of 119-120C.
The compounds listed in Examples 7 to 9 were obtained analogously:
~xam~le 7:
-o-CH-COOH
~7) a-(3-Nitro-phenoxy)-propionic acid of melting point 102-104C (from toluene).
, 3 ~
~e~A 16 613 -~
, ~ , .
.~ , .
~07~746 Exam~le 8:
0~N _ ~ O-CH-C00H (8) ~-(4-Nitro-3-chloro-phenoxy)-prolpionic acid of melting point 116-118C (from toluene).
Example 9:
CH
Cl- ~ -O-C-COOH
o ~ CH3 (9) a-(3-Nitro-4-chloro-phenoxy)-i~obutyric aold of melting point 78-80a (~rom carbon tetrachloride).
~xam~le 10: (Proce~s variant (d)) ~H3 O
Cl- ~ -o-cH-c-oc2H5 (10) 26.4 g (0.1 mole) of a-(3-nitro-4-chloro-phenoxy)-propionic acid chloride were added dropwi3e to a ~olution of 10.1 g (0.1 mole) o~ triethylarnine in 150 ml o~ ethanol at 10-15C, whil~t cooling. ~he mixture wa~ ~tirred further for 1 hour at room temperature and 1 hour at 40-50C. The tri-; 15 ethylamine hydrochloride which had separated out was filtered off and the filtrate was evaporated in vacuo. The residue was stirred with water, filtered off and dried.
26 g (95% of theory) of a-(3-nitro-4~chloro-phenoxy)-propionic acid ethyl e~ter were obtained, melting at 38-40C a~ter recry~talli3ation from wash benzine.
The compounds listed in Table t which follow~ were - obtained analogou~ly to the de3cription in ~xample 10 with ; 6~ ~e A 16 613 - 3U~-~'7i9'74~
the alcohol employed in excess in each ca.se also ~unctioning as the d iluent .
Le A 16 613 -~-, ~ai7.~374 ., g 0 o~ o a~
~ ~ ~ ~ ~ o o h O N ~ 1 C~l q~ N,~ u~
~' ~ "
. ~ O O
. o~ 8 ., ~ ~: ~D ~D
a) ~ L~
.. V~ I r~ ~ O ~ ~ ~
l~lZ~ ~ u~ o ~ ~ .
~ ~\ / p:l, N ~ ~
C~ I I I I
a~
:' ~-~q O ~ ~ ~ ~
~i ~e A 16 613 -,~
~079'746 ~xam,rle 16:
02N ~ I " (16) Cl n20 = 1.52~2.
~xam~le 17:
CH o 3 "
Cl-~7-o-cH-c-t)-c5H1 1 2 (17) 26.~ g (0.1 mole) of a-(3-nitro-~-chloro-phenoxy)-propionic acid chloride were adcled dropwiF3e to a mixture of 8.8 g (0.1 mole) o~ n-pentanol (n-amyl alcohol)~ 10.1 g (0.1 ~, mole) of triethylamine and 150 ml of acetone at 10 to 15C, whilst cooling. The reaction mixture was stirred further for 1 hour at room temperature and 1 hour at 40-50C. The tri-j ethylamine hy~rochloride which had separated out was filtered off and the filtrate was evaporated in vacuo. The re~idue was taken up in 100 ml OI chloroform. The ~olution thu~ formed wa~ wa~hed twice with water, dried over ~odium culphate and evaporated in vacuo. The oily residue wa~
distilled. This gave 26 g (82.5% of theory) of a_(3-nitro~4-chlorophenoxy)-propionic acid n-pentyl e~ter of boiling point 135-138C at 0.1 mm Hg.
Refractive index: nD = 1.5152.
The compounds listed in Tables 2 and 3 which follow were obtained analogously to the de~cription in Example 17:
, .
.' '` ,~
~e A 16 613 -~-, ~ , 11D79~746 ~:
_, .,1 O rl ~ ~ , ~ .
~o o~ ~ ..
Q~
X
Q~
rt a~ ,_ .~
r~
C~
h O
~ 0~
O .
~J I O ^ O O O O
O-y Ql~O O O O
O ~ ~t ~ O O ~ -rlU~ I rl El I I ~ ~ ~ I
O ~1 ~ ) ao O L~~ O
~o~ ~ , ~ U~
m~-p: ~ d ~
N N p~,lo ~ N N
O OD C~ O ~ J t~
Z; ~ . N N N N
, I.e A 16 61~
~07~ 6 S: ~r-l R
O N N
p~ S~
a~
~rl ~ ~ a~
~ _~
r~l V I Cd I ~1 (1)0 U~
~_ X
~>
R
a L~
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~ U~
r~ ^
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a ~_ ., rd .~
~ ~ . ~
C) O ~~
~_ P~ ~D O O
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r-l ~ ~ O O
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E~ .
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a~
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.
. 3 ~eA 16 61~
, 1~79746 ,. ~
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o ~ o ~i I,e A 16 613 , , ,:
.
~079~
Example 32:
Cl ~ 0-~H-C-0 ~ (32) 26.4 g (0.1 mole) of ~-(3-nitro-4-chloro-phenoxy)-propionic acid chloride were added dropwise to a mixture of 9.4 g (0.1 mole) of phenol, 10.1 g (0.1 mole) of triethyl-a~ine and 150 ml of acetone at 10-15 C, whilst cooling. The mixture was stirred further for 1 hour at room temperature and 1 hour at 40 - 50 C. The triethylamine hydrochloride which had separated out was fi].tered off and the filtrate 0 wa8 evaporated in vacuo. The re~idue wa~ t~ken up in chlorororm. The solution thereby i`ormed wat-~ watlhed t~lice with water, dried over tJo(lll~m 5ulphfl:te ~nd evaporated in vacuo. The residue was recrystallised ~rom wash benzine.
This gave 24 g (74.5% of theory) of ~-(3-nitro-4-chloro-phenoxy)-propionic acid phenyl ester of melting point 66-68C.
The compounds listed in Table 4 which f'ollows were obtained analogously to the description in Example 32. '~`
-- l~o --. ~.
~L~79746
~ e A 16 613 - ~
na~hthol, 2-naphthol, 4-hydroxy-benzenesulphonic acid dimethyl-amide, 6-hydroxy-tetralin, 2-hydroxy-biphenyl, pyrocatechol, resorcinol, hydroquinone, 4,4'~-dihydroxy-diphenyl-sulphone, 1,5-dihydroxy-naphthalene, 2,6-dihydroxy-naphthalene, 4,4'-dihydroxy-diphenyl, 2,2-bis-t4-hydroxyphenyl)-propane, phloro-glucinol, 2,4-dihydroxy-acetophenone, 2-hydroxy-dibenzofurane, 3-hydroxy-6-methoxy-benzothiophene, 7-hydroxy-4-metllyl~
coumarine, 5-hydroxy-2-hydroxymethyl-4-pyrone (kojic acid), 6-hydroxy-2,4-dimethyl-1,3-dioxane, 8-hydroxy-quinoline, 2-hydroxy-carbazole, hydroxymethyl-phthalimide, 1,3,5-tris-hydroxyethyl-hexahydro-s-triazine and 6~hydroxy-2-methyl-benæothiaæole.
In carrying out process variant (a) according to the invention, all inert solvents can be used as dlluents, especially alcohols such as methanol, ethanol, isopropanol and butanol; ethers such as dibutyl ether, glycol mono-methyl ether, dioxan and tetrahydrofuran; aliphatic and arom~tic hydrocarbons, such as cyclohexane, ben~ine, toluene, benzene and xylene; ketones, such as acetone, methyl i~ropyl ketone and cyolohexanone; carboxylic acid amides such as dimethylformamide and dimethylacetamide; and strongly polar solvents such as acetonitrile and dimethylsulphoxide.
At times, water can also be employed as the solvent.
In the reaction according to process variant (a), all customary acid acceptors can be used as acid-binding agents, especially alkali metal hydroxides, alkali metal carbonates, alkali metal alcoholates, alkaline earth metal hyaroxides, ; alkaline earth metal carbonates, heavy metal oxides, ammonia and ter~ary amines. ~he following may be mentioned as being particularly suitable: sodium carbonate, potassium carbonate, .,~ /~
~e A 16 613 ; ~"
..." , r ~,~
797~6 triethyla~ine, N,N-dimeth~l-aniline, ~,N-dimethyl-benzyl-amine, pyridine and quinoline.
In process ~ariant (a), the reaction temperatures c~ be varied within a fairly wide ran~e. In general, the reaction is carried out at temperatures between 0C and 150 C, preferably between 20 C and 120 C.
In carrying out process variant (a) according to the invention, l to 1.5 moles of an ~-halogenoalkanecarboxylic acid derivative of the formula (III) and 2 to 2.5 moles, rel- , ative to base equivalents, of acid-binding agent, are pref-erably employed per mole of the nitrophenol of the for~ula (II).
In proce~ variant (a) accordiDg to the invention, the compound~ of the forml~la (L) ~re i~olated b~ conventional method6. If, for example, a nitrophenol of the formula (II) is reacted with an ester of the for~ula (III), a suitable procedure is to filter off, after completion of the reaction, the salts which have been formed, concentrate the filtrate and, if appropriate, purify the residue by recrystallisation.
If the reaction haa been carried out in a water-miscible solvent, it is al~o possible to precipitate the reaction product~ by addition of water, after prior removal of the salts, and then to filter them off. If a nitrophenol of the formula (II) is reacted with a free acid of the formula (III), the reaction products of the formula (I) are obtained in the form of salts, frequently associated with the hydrochloride or hydrobromide of the particular base employed. The salts are filtered off, converted into the free, sparingly water-soluble nitrophenyloxycarboxylic acids of the formula (I) by treatment with mineral acids in arl aqueous medium, and ~797~6 filtered off.
In carrying out process variant (b) according to the invention, all inert solvents can be used as the diluents.
They include, in particular, water and those solvents which have already been mentioned as being pre~erred in connection with nrocess variant (a).
In ~rocess variant (b), the reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at temperatures between -20C and 150C, ~referably between 0C and 1 ooa.
In carrying out process variant (b) according to the invention, 1 equivalent, or a slight excess, o~ a metal oxlde, metal hydroxide,metal carbonate,metal bicarbonate or metal alcoholate, or of an amine of the formula (V) is employed per mole of the compound of the formula (IV).
In process variant (b) according to the invention, the reaction products are isolated by customary methods. If the reaction is carried out in a solvent of low polarity, the salts are obtained ln a orystalline form and can be isolated by riltration. I~ the reaction is carried out in a strongly polar solvent, the reaction products are obtained by dis-tilling o~f the solvent.
In carrying out process variant (c) according to the invention, all inert solvents can be used as diluents, especially water-miscible alcohols such as methanol, ethanol and isopropanol.
In process variant (c) according to the invention, the reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at temperatures between 10C and 100C, preferably between 20C and 70a.
"~ 1 ' ~1 11 ~e A 16 613 107974~
In carrying out proces~ variant (c) according to the invention, an equivalent amount, or an excess, of a strong acid or of a strong, optionally aqueous, base is employed ~er mole of the compound of the formula (VI).
In process variant (c) according to the invention, the reaction products are isolated by the customary methods. If the reaction is carried out in an acid medium, a suitable procedure is to dilute the reaction mixture, after completion of the reaction, with water and to filter off the free acids of the formula (I), which are thus obtained in a crystalline form, and dry them. I-~, on the other hand, the reaction is carried out in an alknline medtum, the ~alt~ of the formula (I) are obtainecl ~n a pure ~orm by ~imply distillin~ o~ the solvent. I~ it is not the salt~ but the free acids of the formula (I) which are to be prepared by the sàponification in an alkaline medium, a suitable procedure is to acidify the reaction mixture after completion of the reaction, dilute it with water if appropriate and filter off the acids which thereupon are obtained in a crystalline form, and dry them.
In oarrying out proces~ varlant (d) aocording to the invention, all inert sol~ents can be used as diluents, especially ketones such as acetone, methyl isopropyl ketone and cyclohexanone; ethers such as diethyl ether, dibutyl ether, glycol dimethyl ether, dioxan and tetrahydro~uran;
aliphatic or aromatic hydrocarbons, such as hexane, benzine, benzene, toluene and xylene; chlorinated aliphatic or aromatic hydrocarbons, such as methylene chloride, chloro-; form, carbon tetrachloride and chlorobenzene; esters such as ethyl acetate; and strongly polar solvents such as dimethylformamide, acetonitrile and dimethylsulphoxide. At e A 16 613 ~ 5 -~079746 tir~es, the solvents can also be diluted with water. If lower alkanols are used as reactant~, these can in some cases also function a~ solvents.
In the reaction according to process variant (d), all customary ~cid acce~tor~ can be u~ed as acid-binding agents, especially those acid-binding agents which have already been mentioned preferentially in connection with process variant (a). Further preferred acid-binding agents are alkali metal a~ide~ and alkali metal hydrides, as well as the alkali metal alcoholates and alkali metal phenolates of the compounds o~
the rormula (VIII) which are employed.
The reaction temperatures in proce~ variant (d) according to the invention can be varied within a fairly wide range. In general, the reaction is carried out at temper-atures between 0C and 120C, preferably betweèn 0C and 50C.
In carrying out process variant (d) according to the invention, preferably an equivalent amount, based on the hydroxyl group to be esteri~ied, of a compound o~ the ~ormula (VIII), and an equivalent amount of acid-binding agent, are employed per mole o~ the compound o~ the ~ormula (VII).
However, it i3 also pos~ible to use a large excess of a compound of the formula (VIII) or of acid-binding agent. This is particularly advisable when a compound of the formula (VIII), or the acid-binding agent, at the same time serves as the solvent.
In process variant (d), the reaction products are suit-ably isolated by separating off, a~ter completion of the reaction, the salts which have formed, concentrating the filtrate by evaporation, and recrystallising the residue or stirring it with water and filtering off the product which /~
~ e A 16 613 -~
~(~79746 thereupon separates out. However, it is also vossible to dilute the filtrate, obtained after removal of the salts, directly with water and to filter o~f the product which here-u~on is obtained in a crystalline fo~n.
The ~ollowing may be mentioned as examples of the nitroaryloxyalkanecarboxylic acid derivative~ according to the invention, of the formula (I): à-(3-nitro-phenoxy)-propionic ~cid, a-(3-nitro-4-ch]oro-phenoxy~-propionic acid, a-(4-nitro-3-chloro-phenoxy)-propionic acid, a-(3-nitro-phenoxy)-i~obutyric acid, a-(3-nitro-~-chloro-phenoxy)-iso-but~ric acid, a-(4-nitro-3-chloro-phenoxy) isobutyri¢ aoid, the ~od~.um ~alt o~ a-(3-nitro-4-ohloro-phenoxy)-propionic acid, the ammonium ~alt o~ a-(3-nitro-4-chloro-phenoxy)-propionic acid, the methylammonium salt o~ a-(3-nitro-4-chloro-phenoxy)-propionic acid, the di-(2-hydroxyethyl)-ammonium salt of a-(3-nitro-4-chloro-phenoxy)-propionic acid, a-(3-nitro-phenoxy) propionic acid methyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid methyl ester, a-(4-nitro-3-chloro-phenoxy)-proplonic acid methyl ester, a-(3-nitro-phenoxy)-i~obutyric acid methyl e~ter, a-(3-nitro-4-chloro-phenoxy)-isobutyric acid methyl ester, a-(4-nitro-3-chloro-phenoxy)-isobutyric acid methyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid ethyl ester, a_(3-nitro-4-chloro-pheno~y)-propionic acid propyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid isopropyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid butyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid isobutyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic acid sec.-butyl ester, a-(3-nitro-4-chloro-phenoxy)~propionic ac:id hexyl ester, a-(3-nitro-4-chloro-phenoxy)-propionic ac:id neopentyl ester, a-(3-nitro-~-chloro-phenoxy)-propionic acid cyclohexyl ~ ~e A 16 613 - ~ -'`'' iai79746 ester, d-(3-nitro-4-chloro-phenoxy)-propionic acid benzyl ester, ~-(3-nitro-4-chloro-phenoxy)-propionic acid allyl ester, ~-(3-nitro-4-chloro phenoxy)-propionic acid propargyl ester, ~-(3-nitro-4-chloro-phenoxy)-propionic acid 2-methoxy ethyl ester, ~-(3-nitro-4-chloro-phenoxy)-propionic acid 2-butoxy-ethyl ester, ~-(3-nitro-~-chloro-phenoxy)-propionic acid phenyl ester, ~-(3-nitro-~-chloro-phenoxy)-propionic acid 4-chlorophenyl ester, -(3-nitro-4-chloro-phenoxy)-propionic acid 4-methoxy-phenyl ester, a~(3-nitro-4-chloro-~
phenoxy)-propionic acid 4-nitrophenyl ester, ~-(4-nitro-3-chloro-phenoxy)-propionic acid ethyl ester, a~ -nitro-3-chloro-phenoxy)-propionic acid neopentyl ester, ~-(4-nitro 3-chloro-phenoxy)-propionic acid cyclohexyl ester, ~-(4-nitro-3-chloro-phenoxy)-proplon:lc acld ~en~yl e~ter and ~ -nitro-3-chloro-phenoxy) -proplonlc uci.d l~-chlorophenyl ester.
The active compounds according to the invention influ-ence plant erowth and can therefore be used as defoliants, desiccants, aeents for destroying broad-leaved plants, ger-mination inhibitors and, especially, weed-killers. Weeds, in the broadest sen~e, are to be understood as all plants which grow in locations where they are undes-lred. Whether the compounds according to the invention act as total herbicides or as selective herbicides depends essentially on the amount used.
~he active compounds according to the invention can be used, for example, in connection with the ~ollowin~ plants:
Dicotyledon weeds such as mustard (Sinapis), cress (Lepidium), bed straw (Galium), chickweed (Stellaria), camomile (Matricaria), mayweed (An-themis), gallant soldier (Galinsoga), goose~oot (Chenopodium), annual nettle (Urtica)~
, . ' ,.:
107~31746 grounsel ~Senecio), plgweed (Amaranthus), puralane (Portu-laca), cocklebur (Xanthium), bindweed (Convolvulus), morning glory (Ipomoea), knotweed (Poly~onum), sesb~Dia (Sesbania), ragweed (Ambrosia), spear thistle (Cirsium)l common thistle (Carduus), sow thistle (Sonchus), nightshade (Solanum), field cress (Rorippa), toothcup (Rotala), (Lindernia), deadnettle (Lamium), speedwell (Veronica), mallow (Abutilon), emex (Emex), thornapple (Datura), violet (Viola), hemp-nettle (Galeopsis~, poppy (Papaver) and knapweed (Centaurea);
Dicotyledon cultures such as cotton (Goss~pium), soya bean (~1Y~ ), beet (Beta), carrot (Daucus), bean (Phaseolus), pea (Pisum), potato (Solanum), flax (Linum), mornin~ glory (I_omoea), broad bean (Vicia), tobacco (Nicotian~), tom~lto (Lyco~ersicon), ~roundnut (Arachia), ca~ba6e (Brasaica), lettuce (lactuca), cuc~ber ( ucumis) and marrow (Cuburblta);
Monocotyledon weeds such as barnyard grass (Echinochloa), foxtail (Setaria), wild millet (Panicum), crabgrass (DieitPria), timothy (Phleum), bluegrass (Poa), f2scue (Festuca), goosegrass (Eleusine), signalgrass (Brachiaria), ryegrass (I.olium), cheat (Bromus), oats (Avena), flatsedge (Cyperus), sorghum ( _r~ ), quackgrass (Agropyron), Bermud& erass (Cynodon), Monocharia, ~imbristylis (Fimb~isty-lis), arrowhead (Sagittaria), spikerush ( leocharis), bulrush (Scirpus), paspalum (Paspalum), Ischaemum, gooseweed (Spheno-clea), crowfoot grass (Dactyloctenium), redtop (Agrostis), meadow foxtail (Alopecurus) and silky bent-grass (~pera), and Monocotyledon cultures such as rice (Oryza), maize ~ ), wheat (Tr~ticum), barley (Hordeum)~ oats (Avena), rye (Secale), sorghum (~ ), millet (Panicum), sugar cane ~0 (Saccharum), pineapple (Ananas), asparagus (Asparaeus) and onion (Allium).
- lq _ :L~79746 The use of the active compounds according to the invention is, howe~er, in no way restricted to t~e genera indicated above, but extends, in the snme way, also to other plants.
Depending on the concentration, the compounds are suitable for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares which may or may not be planted with trees. Equally, the compounds can be employed for combating weeds in permanent cultures, for example ~fforestation, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plentations, cacao plantMtions, ~oft fruit orchards and hopfields, and for the selective co~ating of weeds in annuQl crop~.
In particular, the active compounds according to the invention are suitable for the selective combating of weeds in fields of crop plants such as maize and wheat.
~he active compounds according to the present inven- -tion can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. I'he6e may be produced in known m~mer, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optlonally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic so~vents can, for example, al80 be used as auxiliary solvents.
As liquid diluents or carriers, there are preferably used - 20 - ~
- .: ' . ': ' :, aromatic hydrocarbons, such as xylenes, toluenei benzene or alkyl na~hthalenes, chlorinated aromatic or a~iphatic hydro-carbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for exam~le mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl iso-butyl ketone or cyclohexanone, or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or aceto-nitrile, as well as water.
~y lique~ied gaseou~ diluents or carrier~ are meant li~uid~ which would bo ga~eous at normal temperatures and pressures, ~or examplè aerosol propellants, such as halo-genated hydrocarbons, for example freon.
As solid diluents or carriers, there are pre~erably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed 8ilicic acid, alumina or silicates.
Pre~erred examples o~ emulsi~ying and ~oam-forming agents include non-ionic and anionic emulsi~iers, such as polyoxy-ethylene-fatty acid esters, polyoxyethylene-~atty alcohol ethers, ~or example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as albumin hydrolyzation products; and pre~erred examples o~ dispersing agents include lignin sulphite waste liquors and methyl cellulose.
The active compounds according to the in~ention, as such or as their ~ormulations, can be combined with other .,~, .
~ ~o herbicidally active compoun~ order to boost and supple-.
~e A 16 613 - ~
.~ ~
ment their s~ectrum of action, depending on the intended use;
ready-mixed formulations, or tank mixing, may be employed.
In particular, the active compounds mentioned below and other members of the grou~s of active compowlds represented by these ~articular active compounds are also suitable for this purpose.
2,3,6-Trichlorobenzoic acid and its salts, 2,3,5,6-tetrachlorobenzoic acid and its ~alts, 3-nitro-2,5-dichloro-ben~oic acid and its salts, 3-amino-2,5-dichlorobenzoic acia an~1 it.s sa].ts, 2-methoxy-3,6-dichlorobenzoic acid and its salts, 2-mcthoxy-3,5,6-trichlorobcnY.~ic aoid and its salts, 2,6-di.chloro-thiobon~amide, 2,6-dlchlorobenzonitrile, 2,4-dichlorophenoxyacctlc aoid as well a~ it~ ~alt~ and ~stera, 2,4,5-trichlorophenoxyacetic acid and its salts and esters, (2-methyl-4-chlorophenoxy)-acetic acid and its salts and esters, 2-(2,4-dichlorophenoxy)-propionic acid, (2-(2-methyl-4-chloro-phenoxy)-propionic acid and 2-(2,4,5-trichlorophenoxy~-propionic acid and their salt~ and esters, 4-(2,4-dichloro-phenoxy)-butyric acid and its salts and esters, 4-(2-methyl-4-chlorophenoxy)-butyric acid and its salt~ and esters, 2,3,6-trichlorophenyl-acetic acid and it~ salt~ and 4-amino-3,5,6-trichloropicolinic acid.
Trichloroacetic acid and its salts, 2,2-dichloro-propionic acid and its salts, 2-chloro-N,N-diallylacetic acid amide, dinitrocresol, dinitro-sec.-butylphenol and its salts.
3-Phenyl-1,1-dimethyl-urea, 3-(4'-c~Loropheny:L)-1,1-dimethyl-urea, 3-(3',4'-dichloro~henyl)-1,1-dimethyl-urea, 3-(~',4'-dichloro~henyl)-1-n-butyl-1-rnethyl-urea, 3-(3',4'-dichlorophenyl)-1,1,3-trimethyl-urea, 3-(4'-chlorophenyl)-1-: 30 methoxy-1-methyl-urea, 3-(3'-trifluoromethyl-phenyl)--1,1-~2 e A 16 613 -~
~C1797~6 dimethyl-ure~, 3-(3',4'-dichlorophenyl)-1-methoxy-1-methyl-urea, 3-(4' bromophenyl)-l-methoxy-l-methyl-urea, 3-(3',4'-dichlorophenyl)-3-methoxy-1,1-dimethyl-urea, 3-(4'-chloro-phenoxyphenyl)-l,l-dimethyl-urea, N'-cyclooctyl-N,~-dimethyl-urea, 3-(benzthiazol-2-yl)-1,3-dimethyl-urea and 3-(3-chloro-4-methylphenyl)-1,1-dimethyl-urea.
N,M-Di-(n-propyl)-S-n-propyl-thiocarbamic acid ester, N-ethyl-N-(n-butyl)-S-n-propyl-thiocarbamic acid ester, ~,N-di-(n-propyl)-S-ethyl-thiocarbamic acid ester, ~-phenyl-0-isopropyl-carbamic acid ester, N-(m-chlorophenyl)-0-isopropyl-carbamic acid ester, N-(3',4'-dichlorophenyl)-0-methyl-carbamic acid ester, N-(m-chlorophenyl)-0-(4-chloro-butin-(2)-yl)-carbamic acid ester, n- ( 3'-methylphenyl)-0-(3-methoxy-carbonylaMinopheny~)-c~rbami.c acld cnter and ~,N-dilrlopropyl-~hiocarbQmlc aci.tl 2,3,3-trichloroallyl ester.
3-Cyclohexyl-5,6-trlmetbylene-uracil, 5-bromo-3-sec.-butyl-6-methyl-uracil, 3,6-dioxo-1,2,3,6-tetrahydropyridazine and 4-amino-5-chloro-1-phenyl-6-pyridazone.
2-Chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-chloro-4,6-bis-(methoxypropylamino)-s-triazine, 2-methoxy-4,6-bis-(isopropylamino)-s-triazine, 2-diethylamino-4-iso-propyl-acetamido-6-methoxy-s-triazine, 2-isopropylamino-4-methoxy-propylamino-6-methylthio-~-triazine, 2-methylthio-4,6-bis-(iso-propylamino)-s--triazine, 2-chloro-4,6-bis-(ethylamino)-s-triazine, 2-methylthio-4,6-bis-(ethylamino)-~ s-triazine, 2-methoxy-4-ethylamino-6-isopropylamino-s-: triazine, 2-methylthio-4-ethylamino-6-isopropylamino-s-triazine, 2-methoxy-4,6-bis-(ethylamino)-s-triazine and 2-chloro-4,6-bis-(isopropylamino)-s-triazine.
N,N-Diethyl-2,4-dinitro-6-tri~luoromethyl-1,3-phenylenediamine, N,N-di-n-propyl-2,6-dinitro-4-tri~luoro-- 23 - .:
iO797~6 methyl-aniline, 4'-nitro-2,4-dichloro~-diphenyl ether, ~,4-dichlorophenyl-propionamide and 2',6'--diethyl-N (methoxy-methyl)-2-chloroacetanilide.
The active compounds according to the invention can be Present in the formulations as a mixture with other active compound~, such as fungicide~, insect:Lciae~ and acaricides.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably ~rom 0.5 to 90 ~er cent by weight.
The active compound~ can be used as such, in the ~orm of their formulatlons or as the use forms~ ~repared therefrom, ~uch a~ ready-to-u~e solutions, emulsion~, ~uspen~ions, ~owdor~, pa~teB and granul0~. They may be u~ed ~n the customary manner, for example by sprayin~, atomising, du~ting, scattering and watering.
Preferably, they are used in accordance with the pre-emergence process, ~he amount of active compound employed can vary within fairly wide ranges; it depend~ es~entially on the nature of the desired effeot. In ~eneral, the amounts used are ~rom 0.1 to 20 kg o~ active compound per he¢tare, pre~erably from 0.2 to 15 kg/ha.
The present invention al~o provides a herbicidal com-po~ition containing a~ active ingredient a`compound of the present in~ention in admixture with a solid`or lique~ied gaseous diluent or carrier or in admixture with a 11quid diluent or carrier containing a ~urface-acti~e a~ent.
The pre~ent invention also provide~ a methocl o~ com-bating weeds which comprise~ applying to the weecLs or a weed habita`t a compound of the present in~ention alone or in the e A 16 613 _ ~r-. ` .
~"
~C~797~6 ~orm of a compo~ition containine a~ active ingredient a compound of the present i~ention in admixture with a diluent or carrier9 The present invention further provides crops protected from damage by weeds by being grown in areas in which i~ediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier. It will be seen that the usual methods of providing a harvested crop may be improved by the pre~ent invention.
The biote~t Example which ~ollows is intended to illu~trate the good herbicidal aotivlty of the active com-~ound~ according to the inventlon.
~ A
Pre-emergence te~t Solvent: 5 partæ by weight of acetone ~mulsi~ier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emul~ifier was added and the ooncentrate was diluted with water to the desir0d concentration.
Seed~ of the test plants were sown in normal 80il and, after 24 hours, watered with the preparation of the active compound. It was expedient to keep constant the amount o~
water per unit area. The concentration o~ the active com-pound in the preparation wa~ of no importance, only the amount of active compound applied per unit area bei~g decisive.
After three weeks, the degree o~ damage to the plants was determined in % damage in comparison to the development of ~ e A 16 613 ~"
~C9797~6 the untreated control. The figures denote:
~0 = no action (like untreated control) 100jo - total destruction The active compounds, the amounts appli.ed and the results can be seen from the table which follows:
.
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N
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C~
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The process of the present invention is illustrated by the following preparative Examples.
l~xa~Ple 1: (Process variant (a)) ~ -O~ H-C-OCH (1) o 500 g (3.6 moles) of potassium carbonate were intro-duced, in portions, into a mixture of 278 g (2 moles) of 3-nitro~henol, 245 g (2 moles) of 2-chloro-propionic acid methyl ester and 1 litre of acetonitrile whilst stirring at room temperatl~e. The reaction mixture was gradually warmed to the boil and wa~ then boiled for lO hour~ under re~lux.
'~he salts whioh had ~ormed were then ~iltered eff and the filtrate was eva~orated under reduced pressure. 370 g (82.5~ of theory) of a_(3-nitro-phenoxy)-propionic acid methyl ester were obtained in the ~orm of an oily residue.
~urther purification was effected by dissolving the crude product in wash benzine and again evaporating the solution, a~ter filtration. ~he substance which hereupon remained, and which was liquid at room temperature, was, according to the 1H-~R spectrum and the elementary analysis, a-(3-nitro-phenoxy)-propionic acid methyl ester.
~lementary analysis C1oH11N05(22502) calculated: 53.4% C; 4.93~ H; 6-22% ~
found : 53~7% C; 5.02% H; 6.17~o N
The compounds listed in Examples 2 and 3 were obtained analogously:
CH
Example 2: 3o 02N- ~ ~~ H-C-oCH3 ~2) Cl ~ o i~ ~eiA 16 61 : , ' ' .
-~7~746 ~ -(4-Nitro-3-chloro-phenoxy)-propionic ao:id methyl e~ter of meltin~ point 73-75C ~from wash benzine).
~xam~le ~:
iH3 : Cl-~3-O-CH-C-OCH
a-(3-Nitro-4-chloro-phenoxy)-propionic acid methyl ester of melting point 43C (from wash benzine).
~xample 4:
~\ 3 Cl- @ -0-C-C-0CH3 02N C~13 (4) 173.5 g (l mole) o~ 3-nitro-4-chloro-phenol and 179 g o~ a-bromo-isobutyric acid methyl ester in 600 ml o~ aceto-nitrile were boiled with 250 g of potassium aarbonate for 10 hours under reflux. The salts were filtered o~f; and the ~iltrate wa~ evaporated in vacuo. The residue was stirred with 500 ml of chloro~orm. The ~olution was decanted from the insoluble residue and wa~ evaporated in vacuo. ~he re~idue was recry~talli~ed ~rom wash benzine. 186 g (68~ o~ ;
theory) of a-(3-nitro-4-chloro-phenoxy)-i~obutyric acid methyl ester o~ melting point 31-33C were obtained.
xample 5: (Process variant (b)) ÇH3 o Cl-@ O-CH-C-ONa (5) 24.5 (0.1 mole) of a-(3-nitro-4-chloro-pheno~y)-propionic acid were dissolved in 100 ml of methanol. A
e A 16 613 --~r-1C~7~74~
solution of 2.3 ~ (0.1 mole) oP sodium in a little methanol was added thereto, whilst stirring. The reaction mixture was cooled with ice and the salt which had separated out was filt~rcd off and rinsed with a little :Lce-cold methanol. Thi~
gave the sodium salt of a-(3-nitro-4-chloro-phenoxy)-~ropionic acid in ~ractically quantitative yield. Melting point ~300C.
J~xample 6: (~rocess variant (c)) Cl- ~ -o-CH-COOH (6) ()2N
259.5 g ~1 mole) of a-(3-nltro-4-ohloro-ph0noxy)-propionlc aoid methyl ester were dissolved in 1 litre o~
ethanol. 1 litre of 5~ strength aqueous sodium hydroxide solution was added thereto. The mixture was briefly heated to the boil, then acidified with dilute hydrochloric acid at 55-60C, and finally cooled with ice. ~he crystals which separated out were filtered off and washed with water. ~his gave 238 g (97.5% of theorg) of ~-(3-nitro-4-chloro-phenoxy)-propionic acid which, after reorystallisation ~rom toluene, had a melting point of 119-120C.
The compounds listed in Examples 7 to 9 were obtained analogously:
~xam~le 7:
-o-CH-COOH
~7) a-(3-Nitro-phenoxy)-propionic acid of melting point 102-104C (from toluene).
, 3 ~
~e~A 16 613 -~
, ~ , .
.~ , .
~07~746 Exam~le 8:
0~N _ ~ O-CH-C00H (8) ~-(4-Nitro-3-chloro-phenoxy)-prolpionic acid of melting point 116-118C (from toluene).
Example 9:
CH
Cl- ~ -O-C-COOH
o ~ CH3 (9) a-(3-Nitro-4-chloro-phenoxy)-i~obutyric aold of melting point 78-80a (~rom carbon tetrachloride).
~xam~le 10: (Proce~s variant (d)) ~H3 O
Cl- ~ -o-cH-c-oc2H5 (10) 26.4 g (0.1 mole) of a-(3-nitro-4-chloro-phenoxy)-propionic acid chloride were added dropwi3e to a ~olution of 10.1 g (0.1 mole) o~ triethylarnine in 150 ml o~ ethanol at 10-15C, whil~t cooling. ~he mixture wa~ ~tirred further for 1 hour at room temperature and 1 hour at 40-50C. The tri-; 15 ethylamine hydrochloride which had separated out was filtered off and the filtrate was evaporated in vacuo. The residue was stirred with water, filtered off and dried.
26 g (95% of theory) of a-(3-nitro-4~chloro-phenoxy)-propionic acid ethyl e~ter were obtained, melting at 38-40C a~ter recry~talli3ation from wash benzine.
The compounds listed in Table t which follow~ were - obtained analogou~ly to the de3cription in ~xample 10 with ; 6~ ~e A 16 613 - 3U~-~'7i9'74~
the alcohol employed in excess in each ca.se also ~unctioning as the d iluent .
Le A 16 613 -~-, ~ai7.~374 ., g 0 o~ o a~
~ ~ ~ ~ ~ o o h O N ~ 1 C~l q~ N,~ u~
~' ~ "
. ~ O O
. o~ 8 ., ~ ~: ~D ~D
a) ~ L~
.. V~ I r~ ~ O ~ ~ ~
l~lZ~ ~ u~ o ~ ~ .
~ ~\ / p:l, N ~ ~
C~ I I I I
a~
:' ~-~q O ~ ~ ~ ~
~i ~e A 16 613 -,~
~079'746 ~xam,rle 16:
02N ~ I " (16) Cl n20 = 1.52~2.
~xam~le 17:
CH o 3 "
Cl-~7-o-cH-c-t)-c5H1 1 2 (17) 26.~ g (0.1 mole) of a-(3-nitro-~-chloro-phenoxy)-propionic acid chloride were adcled dropwiF3e to a mixture of 8.8 g (0.1 mole) o~ n-pentanol (n-amyl alcohol)~ 10.1 g (0.1 ~, mole) of triethylamine and 150 ml of acetone at 10 to 15C, whilst cooling. The reaction mixture was stirred further for 1 hour at room temperature and 1 hour at 40-50C. The tri-j ethylamine hy~rochloride which had separated out was filtered off and the filtrate was evaporated in vacuo. The re~idue was taken up in 100 ml OI chloroform. The ~olution thu~ formed wa~ wa~hed twice with water, dried over ~odium culphate and evaporated in vacuo. The oily residue wa~
distilled. This gave 26 g (82.5% of theory) of a_(3-nitro~4-chlorophenoxy)-propionic acid n-pentyl e~ter of boiling point 135-138C at 0.1 mm Hg.
Refractive index: nD = 1.5152.
The compounds listed in Tables 2 and 3 which follow were obtained analogously to the de~cription in Example 17:
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m~-p: ~ d ~
N N p~,lo ~ N N
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Example 32:
Cl ~ 0-~H-C-0 ~ (32) 26.4 g (0.1 mole) of ~-(3-nitro-4-chloro-phenoxy)-propionic acid chloride were added dropwise to a mixture of 9.4 g (0.1 mole) of phenol, 10.1 g (0.1 mole) of triethyl-a~ine and 150 ml of acetone at 10-15 C, whilst cooling. The mixture was stirred further for 1 hour at room temperature and 1 hour at 40 - 50 C. The triethylamine hydrochloride which had separated out was fi].tered off and the filtrate 0 wa8 evaporated in vacuo. The re~idue wa~ t~ken up in chlorororm. The solution thereby i`ormed wat-~ watlhed t~lice with water, dried over tJo(lll~m 5ulphfl:te ~nd evaporated in vacuo. The residue was recrystallised ~rom wash benzine.
This gave 24 g (74.5% of theory) of ~-(3-nitro-4-chloro-phenoxy)-propionic acid phenyl ester of melting point 66-68C.
The compounds listed in Table 4 which f'ollows were obtained analogously to the description in Example 32. '~`
-- l~o --. ~.
~L~79746
5~
rl O
~ Q~ h ~ Q
tn ~rt ~rl ~rl rl ~rl r. N
a~ a) a~
,Q ~ ~ ,Q
h ~q r-l U2 U2 +~
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: "'' i `~ . . . . . .
~7~746 Prep~ratiorl o~ start n~_aterials:
Exa~e I:
.
~ 0-CH-C-Cl 211 g (1 mole) of ~-(3-nitro-phenoxy)-propionic acid were introduced in yortions into 1 litre of thionyl chloride.
The mixture was gradually heated to the boi:L and was boiled until neither hydrogen chloride nor ~ulphur dioxide was evolved any longer. The excess thionyl chloride was dis-tilled off and the residue obtained wae warmed to 100 C in a waterpump vacuum. This gave ~-(3-nitro phenoxy)-propionic acid chloride, in almo1t quantltative yield, aL~ an oily liquid wbich could be used, without additiorlal purification, ~or further reactions.
Example II:
Cl ~O_IH-C-Cl ; 02N
:~, Analogou~1y to the description in Example I, reaction of ~-(3-nitro-4-chloro-phenoxy)-propionic acid with thionyl chloride ga~e ~-(3-nitro~4-chloro-phenoxy)-propionlc acid chloride as an oily liquid which could be used, without additional purification, for further reactions.
~' ;
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tn ~rt ~rl ~rl rl ~rl r. N
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~ e A 16 613 `:
,' ~"
: "'' i `~ . . . . . .
~7~746 Prep~ratiorl o~ start n~_aterials:
Exa~e I:
.
~ 0-CH-C-Cl 211 g (1 mole) of ~-(3-nitro-phenoxy)-propionic acid were introduced in yortions into 1 litre of thionyl chloride.
The mixture was gradually heated to the boi:L and was boiled until neither hydrogen chloride nor ~ulphur dioxide was evolved any longer. The excess thionyl chloride was dis-tilled off and the residue obtained wae warmed to 100 C in a waterpump vacuum. This gave ~-(3-nitro phenoxy)-propionic acid chloride, in almo1t quantltative yield, aL~ an oily liquid wbich could be used, without additiorlal purification, ~or further reactions.
Example II:
Cl ~O_IH-C-Cl ; 02N
:~, Analogou~1y to the description in Example I, reaction of ~-(3-nitro-4-chloro-phenoxy)-propionic acid with thionyl chloride ga~e ~-(3-nitro~4-chloro-phenoxy)-propionlc acid chloride as an oily liquid which could be used, without additional purification, for further reactions.
~' ;
;
: ' .
Claims (18)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Nitroaryloxyalkanecarboxylic acid derivatives of the general formula (I) in which one of X and Y represents chlorine and the other represents nitro, R represents hydrogen or methyl, R1 represents hydrogen, alkyl with 1 to 12 carbon atoms, which alkyl radical can be substituted by halogen, alkoxy with up to 12 carbon atoms, alkylmercapto with 1 to 12 carbon atoms, nitro, trifluoromethyl, cyano, cycloalkyl with 3 to 7 carbon atoms and/or phenyl; or represents alkenyl with 3 to 12 carbon atoms, alkinyl with 3 to 12 carbon atoms, cycloalkyl with 4 to 6 carbon atoms, or phenyl, which phenyl radical is optionally substituted by halogen, nitro, trifluoromethyl, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or alkyl-mercapto with 1 to 4 carbon atoms; or represents a metal cation, and n is 1 or 2, depending on the valency of the radical R1.
2. Compounds according to claim 1, in which R1 represents hydrogen;
straight chain or branched alkyl with 1 to 12 carbon atoms, which alkyl radical is optionally substituted by fluorine, chlorine, bromine, iodine, or alkoxy with up to 6 carbon atoms; straight chain or branched alkenyl or alkynyl with, in either case, 3 to 12 carbon atoms; cyclohexyl,phenyl, which phenyl radical may optionally be substituted by fluorine, chlorine, bromine, iodine, nitro, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms; or R1 represents a cation of one of the metals lithium, sodium, potassium, magnesium, calcium, barium, aluminium, tin, lead, copper, zinc, iron, nickel and manganese.
straight chain or branched alkyl with 1 to 12 carbon atoms, which alkyl radical is optionally substituted by fluorine, chlorine, bromine, iodine, or alkoxy with up to 6 carbon atoms; straight chain or branched alkenyl or alkynyl with, in either case, 3 to 12 carbon atoms; cyclohexyl,phenyl, which phenyl radical may optionally be substituted by fluorine, chlorine, bromine, iodine, nitro, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms; or R1 represents a cation of one of the metals lithium, sodium, potassium, magnesium, calcium, barium, aluminium, tin, lead, copper, zinc, iron, nickel and manganese.
3. Compounds according to claim 1, in which R represents hydrogen, straight or branched alkyl with 1 to 12 carbon atoms, benzyl, phenyl or nitrophenyl.
4. The compound of the formula (3)
5. The compound of the formula (6)
6. The compound of the formula (10)
7. The compound of the formula (27)
8. The compound of the formula (32)
9. The compound of the formula (34)
10. A process for the preparation of a nitroaryloxyalkanecarboxylic acid derivative according to claim 1, in which (a) a nitrophenol of the general formula (II) in which X and Y have the meanings stated in claim 1, is reacted with an .alpha.-halogenoalkanecarboxylic acid derivative of the general formula (III), in which R, R1 and n have the meanings stated in claim 1, and Hal represents chlorine or bromine, if appropriate in the presence of a diluent and in the presence of an acid-binding agent, or (b) a compound of the general formula (IV), in which R, X and Y have the meanings stated in claim 1, is reacted with an oxide, hydroxide, carbonate, bicarbonate or alcoholate of a metal selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, aluminium, tin, lead, copper, zinc, iron, nickel and manganese, or (c) a compound of the general formula (VI), in which R, X and Y have the meanings stated in claim 1 and R7 represents alkyl with 1 to 4 carbon atoms or phenyl, is saponified in an acid or alkaline medium, if appropriate in the presence of a diluent, and the salt which may thereby be produced is converted, if appropriate, to the free nitroaryloxy-alkanecarboxylic acid by addition of acid, or (d) a compound of the general formula (VII) in which R, X and Y have the meanings stated in claim 1 and Ac represents chlorine, bromine, or a group -O-CO-R9, in which R9 represents alkyl or alkoxy, each with 1 to 4 carbon atoms, or a radical of the general formula in which X, Y and R have the meanings stated in claim 1, is reacted with an organic hydroxy compound of the general formula R8(OH)n (VIII) in which R8 has the meanings stated for R1 in claim 1, with the only ex-ception that R8 does not represent hydrogen, and n is 1 or 2, depending on the valency of the radical R8, if appropriate in the presence of a diluent and in the presence of an acid-binding agent.
11. A method of combatting weeds which comprises applying to the weeds or to a weed habitat a compound according to claim 1.
12. A method according to claim 11 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a diluent or carrier.
13. A method according to claim 11 in which the compound is applied to an area of agriculture in an amount of 0.1 to 20 kg per hectare.
14. A method according to claim 13 in which the compound is applied in an amount of 0.2 to 15 kg per hectare.
15. A method according to claim 11 wherein the compound is a compound according to claim 2 or 3.
16. A method according to claim 11 wherein the compound is a compound according to claim 4 or 5.
17. A method according to claim 11 wherein the compound is a compound according to claim 6 or 7.
18. A method according to claim 11 wherein the compound is a compound according to claim 8 or 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752537201 DE2537201A1 (en) | 1975-08-21 | 1975-08-21 | NITROARYLOXY-ALKANE-CARBONIC ACID DERIVATIVES, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE AS HERBICIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1079746A true CA1079746A (en) | 1980-06-17 |
Family
ID=5954482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA259,538A Expired CA1079746A (en) | 1975-08-21 | 1976-08-20 | Nitroaryloxyalkanecarboxylic acid derivatives and their use as herbicides |
Country Status (23)
| Country | Link |
|---|---|
| JP (1) | JPS5321128A (en) |
| AR (1) | AR216905A1 (en) |
| AT (1) | AT348823B (en) |
| AU (1) | AU504239B2 (en) |
| BE (1) | BE845382A (en) |
| BR (1) | BR7605397A (en) |
| CA (1) | CA1079746A (en) |
| CS (1) | CS189023B2 (en) |
| DD (1) | DD127556A5 (en) |
| DE (1) | DE2537201A1 (en) |
| DK (1) | DK376676A (en) |
| ES (1) | ES450853A1 (en) |
| FR (1) | FR2321478A1 (en) |
| GB (1) | GB1501528A (en) |
| IE (1) | IE43527B1 (en) |
| IL (1) | IL50297A0 (en) |
| LU (1) | LU75633A1 (en) |
| NL (1) | NL7609308A (en) |
| PL (1) | PL105489B1 (en) |
| SE (1) | SE7609228L (en) |
| SU (1) | SU604458A3 (en) |
| TR (1) | TR19460A (en) |
| ZA (1) | ZA765006B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310682A (en) * | 1992-06-17 | 1994-05-10 | Indiana University Foundation | Fluorogenic reagents for detection of glycoconjugates, α-ketoacids and diketones |
| MX2009008934A (en) * | 2007-02-26 | 2009-08-28 | Dow Agrosciences Llc | Process for the preparation of certain substituted sulfilimines. |
-
1975
- 1975-08-21 DE DE19752537201 patent/DE2537201A1/en active Pending
-
1976
- 1976-08-18 IL IL50297A patent/IL50297A0/en unknown
- 1976-08-18 BR BR7605397A patent/BR7605397A/en unknown
- 1976-08-19 PL PL1976191899A patent/PL105489B1/en unknown
- 1976-08-19 DD DD194399A patent/DD127556A5/xx unknown
- 1976-08-19 TR TR19460A patent/TR19460A/en unknown
- 1976-08-19 SE SE7609228A patent/SE7609228L/en unknown
- 1976-08-19 SU SU762387321A patent/SU604458A3/en active
- 1976-08-19 GB GB34608/76A patent/GB1501528A/en not_active Expired
- 1976-08-19 CS CS765400A patent/CS189023B2/en unknown
- 1976-08-20 BE BE169963A patent/BE845382A/en unknown
- 1976-08-20 CA CA259,538A patent/CA1079746A/en not_active Expired
- 1976-08-20 NL NL7609308A patent/NL7609308A/en not_active Application Discontinuation
- 1976-08-20 IE IE1857/76A patent/IE43527B1/en unknown
- 1976-08-20 FR FR7625277A patent/FR2321478A1/en not_active Withdrawn
- 1976-08-20 AR AR264400A patent/AR216905A1/en active
- 1976-08-20 AT AT619476A patent/AT348823B/en not_active IP Right Cessation
- 1976-08-20 DK DK376676A patent/DK376676A/en unknown
- 1976-08-20 ZA ZA765006A patent/ZA765006B/en unknown
- 1976-08-20 ES ES450853A patent/ES450853A1/en not_active Expired
- 1976-08-20 LU LU75633A patent/LU75633A1/xx unknown
- 1976-08-21 JP JP9923576A patent/JPS5321128A/en active Pending
- 1976-08-23 AU AU17046/76A patent/AU504239B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ZA765006B (en) | 1977-07-27 |
| BE845382A (en) | 1977-02-21 |
| TR19460A (en) | 1979-05-01 |
| IE43527B1 (en) | 1981-03-25 |
| DD127556A5 (en) | 1977-09-28 |
| FR2321478A1 (en) | 1977-03-18 |
| DE2537201A1 (en) | 1977-03-03 |
| AU504239B2 (en) | 1979-10-04 |
| SE7609228L (en) | 1977-02-22 |
| IE43527L (en) | 1977-02-21 |
| BR7605397A (en) | 1977-08-16 |
| CS189023B2 (en) | 1979-03-30 |
| AT348823B (en) | 1979-03-12 |
| ATA619476A (en) | 1978-07-15 |
| IL50297A0 (en) | 1976-10-31 |
| NL7609308A (en) | 1977-02-23 |
| LU75633A1 (en) | 1977-04-22 |
| GB1501528A (en) | 1978-02-15 |
| SU604458A3 (en) | 1978-04-25 |
| AR216905A1 (en) | 1980-02-15 |
| JPS5321128A (en) | 1978-02-27 |
| PL105489B1 (en) | 1979-10-31 |
| ES450853A1 (en) | 1977-12-01 |
| DK376676A (en) | 1977-02-22 |
| AU1704676A (en) | 1978-03-02 |
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