NOVEL 3-(2-BROMO-4-ALKYNYL-6-ALKOXYPHENYL)-3-PYRROLIN-2-ONES AND THEIR USE AS HERBICIDES
20220056040 · 2022-02-24
Inventors
- Guido Bojack (Wiesbaden-Naurod, DE)
- Alfred Angermann (Kriftel, DE)
- Estella Buscato Arsequell (Frankfurt am Main, DE)
- Andreas REMBIAK (Bad Soden, DE)
- Stefan Lehr (Liederbach, DE)
- Elmar Gatzweiler (Bad Nauheim, DE)
- Anu Bheemaiah Machettira (Frankfurt am Main, DE)
- Elisabeth ASMUS (Hoesbach, DE)
- Dirk Schmutzler (Hattersheim, DE)
Cpc classification
C07D491/107
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention relates to new herbicidally active 3-phenylpyrrolin-2-ones according to general formula (I) or agrochemically acceptable salts thereof, and the use thereof for controlling weeds and weed grasses in plant crops.
Claims
1. A spirocyclopentylpyrrolin-2-one of formula (I) or an agrochemically acceptable salt thereof ##STR00049## W represents oxygen, the S(O).sub.n group or a CR.sup.4R.sup.5 group; R.sup.1 represents hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.6)-haloalkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.1-C.sub.6)-alkoxy or (C.sub.1-C.sub.6)-haloalkoxy; R.sup.2 represents (C.sub.1-C.sub.6)-alkyl or (C.sub.1-C.sub.6)-haloalkyl; R.sup.3 represents hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.3-C.sub.6)-cycloalkyl or halogen; R.sup.4 represents (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-alkoxy, (C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy-(C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.6)-alkenyloxy or (C.sub.2-C.sub.6)-haloalkenyloxy; R.sup.5 represents hydrogen or methyl; or R.sup.4 and R.sup.5 together with the carbon atom to which they are bonded form a keto group or a spirocyclic (C.sub.3-C.sub.7)-cycloalkyl or (C.sub.5-C.sub.7)-cycloalkenyl ring in which one or two ring carbons may optionally be replaced by oxygen atoms and which may optionally be mono- to disubstituted independently by (C.sub.1-C.sub.2)-alkyl or (C.sub.1-C.sub.2)-alkoxy; n represents 0, 1 or 2; G represents hydrogen, a leaving group L or a cation E; where L is one of the radicals below ##STR00050## in which R.sup.6 represents (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.3)-alkoxy-(C.sub.2-C.sub.4)-alkyl; R.sup.7 represents (C.sub.1-C.sub.4)-alkyl; R.sup.8 represents an unsubstituted phenyl or a phenyl which is mono- or polysubstituted by halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy, nitro or cyano; R.sup.9, R.sup.9′ independently of one another represent methoxy or ethoxy; R.sup.10, R.sup.11 each independently of one another represent methyl, ethyl, phenyl or together form a saturated 5-, 6- or 7-membered ring, or together form a saturated 5-, 6- or 7-membered heterocycle having an oxygen or sulfur atom, E represents an alkali metal ion, one ion equivalent of an alkaline earth metal, one ion equivalent of aluminum or one ion equivalent of a transition metal, a magnesium-halogen cation or an ammonium ion, in which optionally one, two, three or all four hydrogen atoms may be replaced by identical or different radicals from the (C.sub.1-C.sub.10)-alkyl or (C.sub.3-C.sub.7)-cycloalkyl groups, where these independently of one another may each be mono- or polysubstituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms; represents a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, optionally in each case morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated 1,4-diazabicyclo[1.1.2]octane (DABCO) or 1,5-diazabicyclo[4.3.0]undec-7-ene (DBU); represents a heteroaromatic ammonium cation, optionally in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, collidine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate; or else may further represent a trimethylsulfonium ion.
2. The compound as claimed in claim 1, in which the radicals have the following meanings: W represents oxygen, the S(O).sub.n group or a CR.sup.4R.sup.5 group; R.sup.1 represents hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.4)-alkenyl, (C.sub.2-C.sub.4)-alkynyl, (C.sub.1-C.sub.4)-alkoxy or (C.sub.1-C.sub.4)-haloalkoxy; R.sup.2 represents (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-haloalkyl; R.sup.3 represents hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.3-C.sub.6)-cycloalkyl or halogen; R.sup.4 represents (C.sub.1-C.sub.4)-alkyl, (C.sub.3-C.sub.4)-cycloalkyl, (C.sub.3-C.sub.6)-alkoxy, (C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy-(C.sub.1-C.sub.4)-alkoxy, (C.sub.2-C.sub.4)-alkenyloxy or (C.sub.2-C.sub.4)-haloalkenyloxy; R.sup.5 represents hydrogen or methyl; or R.sup.4 and R.sup.5 together with the carbon atom to which they are bonded form a keto group or a spirocyclic (C.sub.3-C.sub.7)-cycloalkyl or (C.sub.5-C.sub.7)-cycloalkenyl ring in which one or two ring carbons may optionally be replaced by oxygen atoms and which may optionally be mono- to disubstituted independently by (C.sub.1-C.sub.2)-alkyl or (C.sub.1-C.sub.2)-alkoxy; n represents 0, 1 or 2; G represents hydrogen, a leaving group L or a cation E, where L is one of the radicals below ##STR00051## in which R.sup.6 represents (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.3)-alkoxy-(C.sub.2-C.sub.4)-alkyl; R.sup.7 represents (C.sub.1-C.sub.4)-alkyl; R.sup.8 represents an unsubstituted phenyl or a phenyl which is mono- or polysubstituted by halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkoxy, nitro or cyano; E represents an alkali metal ion, one ion equivalent of an alkaline earth metal, one ion equivalent of aluminum, one ion equivalent of a transition metal, a magnesium halogen cation or an ammonium ion, in which optionally one, two, three or all four hydrogen atoms may be replaced by identical or different radicals from the (C.sub.1-C.sub.10)-alkyl or (C.sub.3-C.sub.7)-cycloalkyl groups, where these independently of one another may each be mono- or polysubstituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms.
3. The compound as claimed in claim 1, in which the radicals have the following meanings: W represents oxygen or a CR.sup.4R.sup.5 group; R.sup.1 represents hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, cyclopropyl, (C.sub.2-C.sub.4)-alkenyl, (C.sub.2-C.sub.4)-alkynyl; R.sup.2 represents (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-haloalkyl; R.sup.3 represents hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.2)-haloalkyl, cyclopropyl or halogen; R.sup.4 represents (C.sub.1-C.sub.2)-alkyl, cyclopropyl, (C.sub.3-C.sub.6)-alkoxy, (C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.2)-alkoxy (C.sub.1-C.sub.4)-haloalkoxy-(C.sub.1-C.sub.2)-alkoxy, (C.sub.2-C.sub.4)-alkenyloxy or (C.sub.2-C.sub.4)-haloalkenyloxy; R.sup.5 represents hydrogen or methyl; or R.sup.4 and R.sup.5 together with the carbon atom to which they are bonded form a keto group or a spirocyclic (C.sub.5-C.sub.7)-cycloalkyl or (C.sub.5-C.sub.7)-cycloalkenyl ring in which one or two ring carbons may optionally be replaced by oxygen atoms and which may optionally be mono- to disubstituted independently by methyl or methoxy; G represents hydrogen, a leaving group L or a cation E, where L is one of the radicals below ##STR00052## in which R.sup.6 represents (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.3)-alkoxy-(C.sub.2-C.sub.4)-alkyl; R.sup.7 represents (C.sub.1-C.sub.4)-alkyl; E represents an alkali metal ion, one ion equivalent of an alkaline earth metal, one ion equivalent of aluminum, one ion equivalent of a transition metal or a magnesium-halogen cation.
4. The compound as claimed in claim 1, in which the radicals have the following meanings: W represents oxygen or a CR.sup.4R.sup.5 group; R.sup.1 represents hydrogen or methyl; R.sup.2 represents methyl or ethyl; R.sup.3 represents hydrogen, methyl, ethyl, difluoromethyl, trifluoromethyl, chlorine or bromine; R.sup.4 represents methyl, ethyl, n-propoxy, i-propoxy, methoxyethoxy, ethoxyethoxy or allyloxy; R.sup.5 represents hydrogen or methyl; or R.sup.4 and R.sup.5, together with the carbon atom to which they are attached, form a dioxolane ring; G represents hydrogen, a leaving group L or a cation E, where L is one of the radicals below ##STR00053## in which R.sup.6 represents methyl, ethyl, i-propyl or t-butyl; R.sup.7 represents methyl or ethyl; E represents a sodium ion or a potassium ion.
5. A compound of formula (XIV) in which the radicals have the following meanings: ##STR00054## R.sup.2 is methyl, ethyl; R.sup.3 is chlorine, bromine, difluoromethyl, trifluoromethyl; R.sup.14 is H, methyl.
6. A process for preparing the compound of formula (I) or an agrochemically acceptable salt thereof as claimed in claim 1 comprising cyclizing a compound of formula (II) ##STR00055## in which R.sup.12 represents alkyl, optionally methyl or ethyl, optionally in the presence of a suitable solvent or diluent, with a suitable base, by formally eliminating the R.sup.12OH group.
7. An agrochemical composition comprising a) at least one compound of formula (I) or an agrochemically acceptable salt thereof as defined in claim 1, and b) one or more auxiliaries and/or additives customary in crop protection.
8. An agrochemical composition comprising a) at least one compound of formula (I) or an agrochemically acceptable salt thereof as defined in claim 1, b) one or more active agrochemical compounds other than component a), and optionally c) one or more auxiliaries and/or additives customary in crop protection.
9. A method of controlling one or more unwanted plants or for regulating the growth of one or more plants, comprising applying an effective amount of at least one compound of formula (I) or an agrochemically acceptable salt thereof, as defined in claim 1, to the plants, seed or an area on which plants grow.
10. A product comprising one or more compounds of formula (I) or an agrochemically acceptable salt thereof, as defined in claim 1, as an herbicide or plant growth regulator.
11. The product as claimed in claim 11, wherein the compound of formula (I) or an agrochemically acceptable salt thereof are capable of being used for controlling one or more harmful plants or for regulating growth in one or more plant crops.
12. The product as claimed in claim 12, wherein the plant crops are transgenic or nontransgenic crop plants.
Description
A. CHEMICAL EXAMPLES
[0217] The following abbreviations are used in the evaluation of NMR signals:
s (singlet), d (doublet), t (triplet), q (quartet), quint (quintet), sext (sextet), sept (septet), m (multiplet), mc (centered multiplet). The solvent used is also specified in the table in each case.
Example 1.1.01
3-[2-Bromo-6-methoxy-4-(prop-1-yn-1-yl)phenyl]-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2-one
[0218] ##STR00031##
[0219] To 1.95 g (4.59 mmol) of methyl 4-{2-[2-bromo-6-methoxy-4-(prop-1-yn-1-yl)phenyl]acetamido}tetrahydro-2H-pyran-4-carboxylate in 40 ml of DMF was slowly added dropwise, within 30 min at room temperature, a solution of 1.16 g (10 mmol) of potassium t-butoxide in 70 ml of DMF, and stirring of the mixture was continued at room temperature overnight. The reaction mixture was subsequently added cautiously to an ice/water mixture and acidified to pH 4 with 2 N hydrochloric acid. The precipitated solids were filtered off with suction, washed thoroughly with water, dried and purified by chromatography on silica gel (hexane/ethyl acetate). 0.96 g (51%) of the desired title compound was obtained.
Example 1.1.02
3-[2-Bromo-6-methoxy-4-(prop-1-yn-1-yl)phenyl]-2-oxo-8-oxa-1-azaspiro[4.5]dec-3-en-4-yl methyl carbonate
[0220] ##STR00032##
[0221] An initial charge of 123.0 mg (0.31 mmol) of 3-[2-bromo-6-methoxy-4-(prop-1-yn-1-yl) phenyl]-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2-one (example compound 1.1.01) together with 2 ml of triethylamine in 10 ml of dichloromethane was stirred at room temperature for 15 min Subsequently, 33 mg (0.32 mmol) of methyl chloroformate in 3 ml of dichloromethane was slowly added dropwise, and the mixture was then left to stir at room temperature overnight. Thereafter, it was taken up in 20 ml of dichloromethane, washed with 10 ml of sodium hydrogencarbonate solution and 2×10 ml of water and dried (magnesium sulfate), and the solvent was distilled off. After chromatography on silica gel (methyl acetate/hexane), 102 mg (69%) of the title compound was obtained.
In analogy to the above examples and according to the general details of preparation, the following compounds of the (Ib)-(Id) type are obtained:
##STR00033##
TABLE-US-00001 Example No. R.sup.2 R.sup.3 G .sup.1H NMR (400 MHz, δ in ppm) 1.1.01 Me Me H d6-DMSO: δ = 1.29 (mc, 2H), 2.04 (mc, 2H), 2.06 (s, 3H), 3.65-3.72 (s, 3H and mc, 2H), 3.82 (mc, 2H), 6.98 and 7.20 (each s, each 1H), 1.1.02 Me Me —C(O)OMe CDC1.sub.3: δ = 1.60 (mc, 2H), 2.05 (s, 3H), 2.23 (mc, 2H), 3.60 (mc, 2H), 3.66 and 3.78 (each s, each 3H), 6.88 and 7.28 each s, each 1H) 1.1.03 Me Me —C(O)OEt CDC1.sub.3: δ = 1.18 (t, 3H), 2.04 (s, 3H), 2.22 (mc, 2H), 3.59 (mc, 2H), 3.76 (s, 3H), 4.03- 4.19 (m, 4H), 6.88 and 7.25 (each s, each 1H) 1.1.04 Me Me —C(O)CHMe.sub.2 CDC1.sub.3: δ = 1.11 (d, 6H), 1.55-1.62 (m, 2H), 2.03 (s, 3H), 2.63 (hept., 1H), 3.60 (mc, 2H), 3.88 (s, 3H), 4.05 (mc, 2H), 6.88 and 7.22 (each s, each 1H)
##STR00034##
TABLE-US-00002 Example No. R.sup.2 R.sup.3 G .sup.1H NMR (400 MHz δ in ppm 1.2.01 Me Me —C(O)OEt CDC1.sub.3: δ = 1.16 (t, 3H), 1.72 (mc, 4H), 1.90 (mc, 2H), 2.05 (s, 3H), 2.23 (mc, 2H), 3.67 (s, 3H), 4.00 (mc, 4H), 4.05 (q, 2H), 6.87 and 7.25 (each s, each 1H) 1.2.02 Me Me —C(O)CHMe.sub.2 CDC1.sub.3: δ = 1.08 and 1.10 (each d, Σ 6H), 1.65-1.80 (m, 4H), 1.85-1.97 (m, 2H), 2.05 (s, 3H), 2.03-2.23 (m, 2H), 2.65 (hept, 1H), 3.68 (s, 3H), 3.99 (mc, 4H), 6.87 and 7.23 (each s, each 3H) 1.2.03 Me Me H d6-DMSO: δ = 1.40 (mc, 2H), 1.70 (mc, 2H), 1.85 (mc, 2H), 2.00-2.10 (m, 5H), 3.65-3.70 (m, 3H), 3.90 (s, 4H), 6.95 (s, 1H), 7.20 (s, 1H), 8.10 (s, br, 1H), 10.85 (s, 1H)
##STR00035##
TABLE-US-00003 Exunple No. R.sup.2 R.sup.3 R.sup.4 G .sup.1H NMR (400 MHz, δ in ppm) 1.3.01 Me Me —OCH.sub.2CH═CH.sub.2 H d6-DMSO: δ = 1.47-1.61 (m, 4H), 1.83 and 1.96 (each mc, each 2H), 2.07 (s, 3H), 3.29 (mc, 1H), 3.69 (s, 3H), 4.01 (mc, 2H), 5.12 and 5.25 (each d, each 1H), 5.83-5.95 (m, 1H), 6.97 and 7.19 (each s, each 1H) 1.3.02 Me Me —OCH.sub.2CH═CH.sub.2 —C(O)OMe CDCl.sub.3: δ = 1.93 (mc, 2H), 2.02 (s, 3H), 2.19 (mc, 2H), 3.28 (mc, 1H), 3.62 and 3.70 (each s, each 3H), 4.04 (mc, 2H), 5.19 and 5.29 (each d, each 1H), 5.87-5.98 (m, 1H), 6.89 and 7.25 (each s, each 1H) 1.3.03 Me Me —OCH.sub.2CH═CH.sub.2 —C(O)OEt CDCl.sub.3: δ = 1.17 (t, 3H), 1.39 (mc, 2H), 1.74-1.83 (m, 2H), 1.92 (mc, 2H), 2.02 (s, 3H), 3.39 (mc, 1H), 3.78 (s, 3H), 4.05 (q, 2H), 5.19 and 5.28 (each d, each 1H), 5.88-5.98 (m, 1H), 6.87 and 7.25 (each s, each 1H) 1.3.04 Me Me —OCH.sub.2CH═CH.sub.2 —C(O)CHMe.sub.2 CDCl.sub.3: δ = 1.07 and 1.09 (each d, Σ 6H), 1.42 (mc, 2H), 2.02 (s, 3H), 2.19 (mc, 2H), 2.61 (hept, 1H), 3.37 (mc, 1H), 3.78 (s, 3H), 4.05 (mc, 2H), 5.19 and 5.29 (each d, each 1H), 5.88-5.98 (m, 1H), 6.87 and 7.21 (each s, each 1H) 1.3.05 Me Me —OCH.sub.2CH.sub.2OMe H d6-DMSO: δ = 1.38-1.60 (m, 4H), 2.04 (s, 3H), 3.23 (mc, 1H), 3.25 (s, 3H), 3.42 and 3.54 (each mc, each 2H), 3.68 (s, 3H), 6.98 and 7.20 (each s, each 1H) 1.3.06 Me Me —OCH.sub.2CH.sub.2OMe —C(O)OMe CDCl.sub.3: δ = 1.78 and 1.92 (each mc, each 2H), 2.02 (s, 3H), 2.19 (mc, 2H), 3.38 (mc, 1H), 3.40 (s, 3H), 3.55 (mc, 3H), 3.65 (s, 3H), 3.78 (s, 3H), 6.87 and 7.29 (each s, each 3H) 1.3.07 Me Me —OCH.sub.2CH.sub.2OMe —C(O)OEt CDCl.sub.3: δ = 1.15 (t, 3H), 1.41 (mc, 2H), 1.79 and 1.92 (each mc, each 2H), 2.03 (s, 3H), 2.20 (mc, 2H), 3.38 (mc, 1H), 3.40 (s, 3H), 3.55 and 3.65 (each mc, each 3H), 3.68 (s, 3H), 4.05 (t, 2H), 6.88 and 7.29 (each s, each 1H) 1.3.08 Me Me —OCH.sub.2CH.sub.2OMe —C(O)Me CDCl.sub.3: δ = 2.05 and 2.10 (each s, each 3H), 2.18 (mc, 2H), 3.37 (mc, 1H), 3.40 (s, 3H), 3.55 and 3.65 (each mc, each 2H), 3.79 (s, 3H), 6.88 and 7.29 (each s, each 1H) 1.3.09 Me Me —O.sup.iPr H d6-DMSO: δ = 1.08 (d, 6H), 1.35-1.60 (m, 4H), 1.85 (mc, 4H), 2.06 (s, 3H), 3.30 (mc, 1H), 3.68 (s, 3H), 3.71 (hept, 1H), 6.98 and 7.20 (each s, each 1H) 1.3.11 Me Me —O.sup.iPr —C(O)OMe CDCl.sub.3: δ = 1.18 (d, 6H), 1.40, 1.78 and 1.91 (each mc, each 2H), 2.03 (s, 3H), 2.10 (mc, 2H), 3.38 (mc, 1H), 3.63 (s, 3H), 3.72 (hept, 1H), 3.78 (s, 3H), 6.88 and 7.28 (each s, each 1H) 1.3.12 Me Me —O.sup.iPr —C(O)OEt CDCl.sub.3: δ = 1.15 (t, 3H), 1.78 and 1.94 (each mc, each 2H), 2.05 (s, 3H), 3.38 (mc, 1H), 3.74 (hept, 1H), 3.78 (s, 3H), 4.04 (q, 2H), 6.87 and 7.28 (each s, each 1H)
Preparation of Starting Materials
Methyl 4-{2-[2-bromo-6-methoxy-4-(prop-1-yn-1-yl)phenyl]acetamido}tetrahydro-2H-pyran-4-carboxylate
[0222] ##STR00036##
[0223] To a solution of 2.00 g (7.05 mmol) of [2-bromo-6-methoxy-4-(prop-1-yn-1-yl)phenyl]acetic acid in 30 ml of dichloromethane was added one drop of DMF. 1.79 g (14.1 mmol) of oxalyl chloride was added and the mixture was heated under reflux until the evolution of gas ended. Subsequently, the reaction solution was concentrated, followed by another two cycles of addition of 30 ml of dichloromethane each time and concentration to dryness again. The residue was dissolved in 20 ml of dichloromethane and slowly added dropwise within 20 min to a solution of 1.38 g (7.05 mmol) of methyl 4-aminotetrahydro-2H-pyran-4-carboxylate hydrochloride (CAS Registry Nummer 199330-66-0) and 4 ml of triethylamine in 20 ml of dichloromethane. After stirring at room temperature for 18 h, 30 ml of water was added, the organic phase was removed and dried (sodium sulfate), and the solvent was distilled off. After purification by column chromatography (silica gel, ethyl acetate/n-heptane), 205 g (63%) of the desired precursor was obtained.
[0224] .sup.1H NMR (400 MHz, CDCl.sub.3): δ=1.82-1.90 (m, 2H), 2.07 (s, 3H), 2.09-2.17 (m, 2H), 3.43 (mc, 2H), 3.70 (s, 3H), 3.72-3.79 (m, 2H), 3.80 (s, 2H), 3.86 (s, 3H), 6.90 and 7.29 (each s, each 1H)
In analogy to this example and the general details of preparation, the following compounds are obtained:
TABLE-US-00004 Compound .sup.1H NMR (400 MHz, CDCl.sub.3, δ in ppm)
Preparation of (2-bromo-4-ethynyl-6-methoxyphenyl)acetic Acid
Step 1: methyl (2-bromo-6-methoxy-4-nitrophenyl)acetate
[0225] ##STR00041##
[0226] 1.547 g (15.0 mmol) of tert-butyl nitrite and 1.842 g (13.7 mmol) of copper(II) chloride were suspended in 7.8 ml of acetonitrile and cooled to 0° C. Then 16.48 g (170 mmol) of vinylidene chloride was slowly added dropwise and the mixture was allowed to warm to room temperature. Subsequently, 2.470 g (10 mmol) of 2-bromo-6-methoxy-4-nitroaniline (CAS Registry Number 16618-66-9), dissolved in 10 ml of acetonitrile and 25 ml of acetone, was slowly added dropwise. Stirring at room temperature was continued until the evolution of gas had ceased. While cooling with ice, the mixture was slowly added to 2 ml of 10% aqueous hydrochloric acid and extracted with ethyl acetate, and the extract was dried with magnesium sulfate and concentrated. This gave 3.636 g of a crude product (1-bromo-3-methoxy-5-nitro-2-(2,2,2-trichloroethyl)benzene) which still contained copper salts and was used directly for the next reaction.
[0227] 3.636 g (10.0 mmol) of this intermediate was dissolved in 10 ml of methanol, and 10 ml (54.4 mol) of 30% methanolic sodium methoxide solution was added slowly, resulting in evolution of heat. This was followed by heating under reflux for 12 h. 1.1 ml of concentrated sulfuric acid was added cautiously, the mixture was heated under reflux for 1 h, and the solvent was distilled off. The residue was taken up in water, extracted with dichloromethane, dried (magnesium sulfate), the solvent was distilled off and the residue was chromatographed on silica gel with hexane/ethyl acetate.
[0228] Yield: 1.45 g (48%) of yellow oil.
[0229] .sup.1H NMR (400 MHz, δ in ppm, CDCl.sub.3): δ=3.70 (s, 3H), 3.94 (s, 3H), 3.96 (s, 2H), 7.70 (s, 1H), 8.10 (s, 1H)
Step 2: methyl (4-amino-2-bromo-6-methoxyphenyl)acetate
[0230] ##STR00042##
[0231] 1.45 g (4.76 mmol) of methyl (2-bromo-6-methoxy-4-nitrophenyl)acetate was dissolved in 11 ml of tetrahydrofuran and a solution of 2.040 g (38.1 mmol) of ammonium chloride in 5.3 ml of water and 2.494 g (38.1 mmol) of zinc was added and the mixture was stirred at room temperature for 30 min. The mixture was filtered, and the filtrate was diluted with water and extracted with ethyl acetate, with the pH set at greater than 7. Drying the organic phase with sodium sulfate and distillative removal of the solvent afforded 1.30 g (99%) of the desired compound in the form of an orange oil.
[0232] .sup.1H NMR (400 MHz, δ in ppm, CDCl.sub.3): δ=3.70 (s, 3H), 3.75 (s, 5H), 6.15 (s, 1H), 6.55 (s, 1H)
Step 3: methyl (2-bromo-4-iodo-6-methoxyphenyl)acetate
[0233] ##STR00043##
[0234] A suspension of 1.300 g (4.74 mmol) of methyl (4-amino-2-bromo-6-methoxyphenyl)acetate and 2.706 g (14.2 mmol) of p-toluenesulfonic acid in 19 ml of acetonitrile was cooled to 10-15° C., and a solution of 0.654 g (9.48 mmol) of sodium nitrite and 1.968 g (11.08 mmol) of potassium iodide in 1.8 ml of water was added gradually. After 10 min, the mixture was warmed to room temperature and stirred at 20° C. for a further 30 min. 15 ml of water was added, the pH was adjusted to pH 8 with saturated sodium hydrogencarbonate solution, and then saturated sodium thiosulfate solution was added. After extraction with ethyl acetate, drying (sodium sulfate) and distillative removal of the solvent, the residue was purified by chromatography on silica gel (ethyl acetate/hexane). This gave 1.005 g (55%) of the iodine compound as a yellow oil.
[0235] .sup.1H NMR (400 MHz, δ in ppm, CDCl.sub.3): δ=3.70 (s, 3H), 3.80 (s, 3H), 3.85 (s, 2H), 7.10 (s, 1H), 7.55 (s, 1H)
Step 4: methyl (2-bromo-4-ethynyl-6-methoxyphenyl)acetate
[0236] ##STR00044##
[0237] To a suspension of 2.18 g (5.66 mmol) of methyl (2-bromo-4-iodo-6-methoxyphenyl)acetate, 10.77 mg (0.06 mmol) of copper(I) iodide and 39.80 mg (0.057 mmol) of bis(triphenylphosphine)-palladium(II) dichloride in 12 ml of triarylamine was added 8 ml of dimethylformamide. The solution was degassed with argon, and 610 mg (6.22 mmol) of trimethylsilylacetylene was added. On completion of conversion of the iodide (monitoring by LCMS), water and dichloromethane were added and the phases were separated. After drying and concentration, a brownish residue was obtained, which was purified by chromatography. The purified trimethylsilyl derivative thus obtained was dissolved in 10 ml of methanol, 1.56 g (11.31 mmol) of potassium carbonate was added, and the mixture was stirred for a further 2 h. The solution was admixed with water and ethyl acetate, separated, and the aqueous phase was extracted twice more with ethyl acetate. Drying of the combined organic phases (sodium sulfate), distillative removal of the solvent and chromatography of the residue on silica gel (ethyl acetate/hexane) afforded 883 mg (55%) of the desired product.
[0238] .sup.1H NMR (400 MHz, δ in ppm, CDCl.sub.3): δ=3.10 (s, 1H), 3.70 (s, 3H), 3.80 (s, 3H), 3.85 (s, 2H), 6.90 (s, 1H), 7.35 (s, 1H)
Step 5: (2-bromo-4-ethynyl-6-methoxyphenyl)acetic Acid
[0239] ##STR00045##
[0240] To a solution of 0.88 g (3.12 mmol) of methyl (2-bromo-4-ethynyl-6-methoxyphenyl)acetate in 5 ml of methanol and 2 ml of water at room temperature was added 0.19 g (7.80 mmol) of lithium hydroxide, and the reaction mixture was stirred at room temperature for 48 h, then a further 0.19 g (7.80 mmol) of lithium hydroxide was added and the mixture was stirred for a further 48 h. The reaction mixture was concentrated to dryness under reduced pressure, 10 ml of water was added, and the mixture was acidified to pH=1 with 2N hydrochloric acid and extracted with ethyl acetate. Washing with water, drying (magnesium sulfate) and distillative removal of the solvent afforded 0.82 g (97%) of the desired product.
[0241] .sup.1H NMR (400 MHz, δ in ppm, d6-DMSO): δ=3.70 (s, 2H), 3.80 (s, 3H), 4.30 (s, 1H), 7.10 (s, 1H), 7.30 (s, 1H)
Preparation of (2-bromo-4-(prop-1-yn-1-yl)-6-methoxyphenyl)acetic Acid
Step 1: methyl [2-bromo-6-methoxy-4-(prop-1-yn-1-yl)phenyl]acetate
[0242] ##STR00046##
[0243] To a solution of 3.50 g (25.7 mmol) of dry zinc chloride and 1.09 g (25.7 mmol) of drylithium chloride in 300 ml of degassed tetrahydrofuran was added dropwise, under a nitrogen atmosphere at 0° C. while stirring, 1.5 ml (0.75 mmol) of a 0.5 M solution of 1-propynylmagnesium bromide in tetrahydrofuran. The solution was warmed to room temperature while stirring within 1.5 h (solution 1). 2.8 mg (0.01 mmol) of palladium(II) acetate and 10.6 mg (0.02 mmol) of 1,4-bis(diphenylphosphino)butane in 3 ml of dry tetrahydrofuran were stirred under a nitrogen atmosphere at room temperature for 30 min (solution 2). 0.2 g (0.5 mmol) of methyl (2-bromo-6-methoxy-4-iodophenyl)acetate was dissolved in 2 ml of dry tetrahydrofuran under a nitrogen atmosphere, and the mixture was stirred at room temperature for 30 min (solution 3). Solution 2 and then solution 3 were each added dropwise at room temperature to solution 1 while stirring and this mixture was stirred at 60° C. for 3.5 h. After cooling to room temperature, water and saturated ammonium chloride solution were added cautiously, the mixture was extracted with ethyl acetate, the organic phase was dried (sodium sulfate), and the solvent was distilled off Chromatography on silica gel (ethyl acetate/hexane) gave 98 mg of the desired compound (63% yield).
[0244] .sup.1H NMR (400 MHz, δ in ppm, CDCl.sub.3): δ=1.37 (t, 3H), 2.03 (s, 3H), 3.69 (s, 3H), 3.85 (s, 2H), 4.00 (q, 2H), 6.82 and 7.23 (each s, each 1H)
Step 2: (2-Bromo-4-(Prop-1-Yn-1-Yl)-6-Methoxyphenyl)Acetic Acid
[0245] ##STR00047##
[0246] 2.10 g (7.06 mmol) of methyl (2-bromo-4-(prop-1-yn-1-yl)-6-methoxyphenyl)acetate and 0.86 g (35.2 mmol) of lithium hydroxide in 20 ml of methanol and 5 ml of water were heated at reflux for 4 days. This was followed by concentration, addition of 30 ml of water, acidification to pH=2 with 2N hydrochloric acid and repeated extraction with ethyl acetate. Drying of the combined organic phases and distillative removal of the solvent afforded 1.88 g of the desired phenylacetic acid.
[0247] .sup.1H NMR (400 MHz, CDCl.sub.3): δ=2.05 (s, 3H), 3.80 (s, 3H), 3.90 (s, 2H), 6.80 (s, 1H), 7.25 (s, 1H)
The following compounds were prepared analogously:
##STR00048##
TABLE-US-00005 R.sup.2 R.sup.3 R.sup.14 .sup.1H NMR (400 MHz, δ in ppm) Ethyl Methyl Methyl CDCl.sub.3: δ = 1.37 (t, 3H), 2.03 (s, 3H), 3.69 (s, 3H), 3.85 (s, 2H), 4.00 (q, 2H), 6.81 and 7.25 (each s, each 1H) Ethyl Methyl H DMSO-d6: δ = 1.30 (t, 3H), 2.05 (s, 3H), 3.65 (s, 2H), 4.05 (q, 2H), 7.00 (s, 1H), 7.20 (s, 1H)
B. FORMULATION EXAMPLES
[0248] a) A dusting product is obtained by mixing 10 parts by weight of a compound of the formula (I) and/or salts thereof and 90 parts by weight of talc as inert substance and comminuting the mixture in an impact mill.
b) A readily water-dispersible, wettable powder is obtained by mixing 25 parts by weight of a compound of the formula (I) and/or salts thereof, 64 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as wetting agent and dispersant and grinding in a pinned-disc mill.
c) A readily water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of a compound of the formula (I) and/or salts thereof with 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range e.g. about 255 to more than 277° C.) and grinding to a fineness of below 5 microns in an attrition ball mill.
d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I) and/or salts thereof, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonylphenol as emulsifier.
e) Water-dispersible granules are obtained by mixing
75 parts by weight of a compound of the formula (I) and/or salts thereof,
10 parts by weight of calcium lignosulfonate,
5 parts by weight of sodium laurylsulfate,
3 parts by weight of polyvinyl alcohol and
7 parts by weight of kaolin,
grinding the mixture in a pinned-disk mill, and granulating the powder in a fluidized bed by spray application of water as a granulating liquid.
f) Water-dispersible granules are also obtained by homogenizing and precomminuting, in a colloid mill,
25 parts by weight of a compound of the formula (I) and/or salts thereof,
5 parts by weight of sodium 2,2′-dinaphthylmethane-6,6′-disulfonate,
2 parts by weight of sodium oleoylmethyltaurate,
1 part by weight of polyvinyl alcohol,
17 parts by weight of calcium carbonate and
50 parts by weight of water,
then grinding the mixture in a bead mill and atomizing and drying the resulting suspension in a spray tower by means of a one-phase nozzle.
C. BIOLOGICAL EXAMPLES
1. Pre-Emergence Herbicidal Effect and Crop Plant Compatibility
[0249] Seeds of monocotyledonous and dicotyledonous weed plants and crop plants are laid out in sandy loam soil in wood-fiber pots and covered with soil. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then applied to the surface of the covering soil as aqueous suspension or emulsion at a water application rate equating to 600 to 800 L/ha with addition of 0.2% wetting agent.
[0250] After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the trial plants. The damage to the test plants is scored visually after a test period of 3 weeks by comparison with untreated controls (herbicidal activity in percent (%): 100% activity=the plants have died, 0% activity=like control plants).
Undesired Plants/Weeds:
[0251]
TABLE-US-00006 ALOMY: Alopecurus myosuroides SETVI: Setaria viridis AMARE: Amaranthus retroflexus AVEFA: Avena fatua CYPES: Cyperus esculentus ECHCG: Echinochloa crus-galli LOLRI: Lolium rigidum STEME: Stellaria media VERPE: Veronica persica VIOTR: Viola tricolor POLCO: Polygonum convolvulus ABUTH: Abutylon threophrasti HORMU: Hordeum murinum DIGSA: Digitaria sanguinalis
1. Pre-Emergence Effectiveness
[0252] As the results from Table 1 show, compounds of the invention have a good herbicidal pre-emergence effectiveness against a broad spectrum of weed grasses and weeds.
[0253] For example, at an application rate of 80 g/ha, the compounds each show 90-100% efficacy against Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium rigidum and Setaria viridis. The compounds of the invention are therefore suitable for control of unwanted plant growth by the pre-emergence method.
TABLE-US-00007 TABLE 1 Pre-emergence action at 80 g/ha Example number Dosage [g/ha] ALOMY AVEFA DIGSA ECHCG LOLRI SETVI 1.2.03 80 100 100 100 100 100 100 1.3.09 80 100 100 100 90 100 100 1.3.07 80 100 100 100 100 100 100 1.3.03 80 100 90 100 100 100 100 1.3.06 80 100 100 100 100 100 100 1.3.01 80 100 100 100 90 100 100 1.3.02 80 100 90 100 100 100 100 1.3.04 80 90 90 100 100 100 100 1.3.05 80 100 90 100 100 100 100 1.3.12 80 100 80 100 100 100 100 1.3.11 80 100 90 100 100 100 100 1.2.01 80 90 100 100 100 100 100 1.1.02 80 90 80 100 80 100 100 1.1.01 80 90 100 100 100 100 100 1.3.08 80 100 90 100 100 100 100
2. Post-Emergence Herbicidal Effect
[0254] Seeds of monocotyledonous and dicotyledonous weed and crop plants are laid out in sandyloam soil in wood-fiber pots, covered with soil and cultivated in a greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated at the one-leaf stage. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then sprayed onto the green parts of the plants as aqueous suspension or emulsion at a water application rate equating to 600 to 800 l/ha with addition of 0.2% wetting agent. After the test plants have been left to stand in the greenhouse under optimal growth conditions for about 3 weeks, the action of the preparations is assessed visually in comparison to untreated controls (herbicidal action in percent (%): 100% activity=the plants have died, 0% activity=like control plants).
Undesired Plants/Weeds:
[0255]
TABLE-US-00008 ALOMY: Alopecurus myosuroides SETVI: Setaria viridis AMARE: Amaranthus retroflexus AVEFA: Avena fatua CYPES: Cyperus esculentus ECHCG: Echinochloa crus-galli LOLRI: Lolium rigidum STEME: Stellaria media VERPE: Veronica persica VIOTR: Viola tricolor POLCO: Polygonum convolvulus ABUTH: Abutylon threophrasti HORMU: Hordeum murinum DIGSA: Digitaria sanguinalis
[0256] As the results from Tables 2 to 4 show, the compounds of the invention have good herbicidal post-emergence efficacy against a broad spectrum of weed grasses and weeds.
TABLE-US-00009 TABLE 2 Post-emergence action against ALOMY, ECHCG, LOLRI and SETVI Example Dosage No. [g/ha] ALOMY ECHCG LOLRI SETVI 1.3.04 80 90 100 100 100 1.3.01 80 100 100 100 100 1.2.03 80 90 100 100 100 1.1.01 80 100 100 100 100 1.2.01 80 100 100 100 100 1.1.02 80 100 100 100 100 1.3.03 80 100 100 100 100 1.3.02 80 100 90 80 100 1.1.03 80 80 100 100 100
TABLE-US-00010 TABLE 3 Post-emergence action against DIGSA Example Dosage No. [g/ha] DIGSA 1.3.04 80 100 1.3.01 80 100 1.2.03 80 100 1.1.01 80 100 1.1.02 80 100 1.3.03 80 100 1.3.02 80 100 1.1.03 80 100 1.1.04 80 100
TABLE-US-00011 TABLE 4 Post-emergence action against HORMU Example Dosage number [g/ha] HORMU 1.3.04 80 100 1.3.01 80 100 1.2.03 80 100 1.1.01 80 100 1.2.01 80 100
[0257] For example, the compounds in Tables 2-4 at an application rate of 80 g/ha each show 80-100% efficacy against Alopecurus myosuroides, Echinochloa crus-galli, Setaria viridis, Lolium multiflorum, Digitaria sanguinahs and Hordeum murinum. The compounds of the invention are therefore suitable for control of unwanted plant growth by the post-emergence method.