Spiroheterocyclically substituted tetramic acid derivatives
09809542 · 2017-11-07
Assignee
Inventors
- Reiner Fischer (Monheim, DE)
- Arnd VOERSTE (Köln, DE)
- Isolde Häuser-Hahn (Leverkusen, DE)
- Stefan Lehr (Liederbach, DE)
- Elmar Gatzweiler (Büdingen, DE)
- Ulrich Görgens (Ratingen, DE)
- Ines Heinemann (Hofheim, DE)
Cpc classification
International classification
Abstract
The invention relates to novel compounds of the formula (I) ##STR00001## in which W, X, Y, Z, A and G have the meanings given above, to a plurality of processes and intermediates for their preparation and to their use as pesticides and/or herbicides and/or fungicides. Moreover, the invention relates to selectively herbicidal compositions comprising, firstly, the spiroheterocyclically substituted tetramic acid derivatives and, secondly, a crop plant compatibility-improving compound. The present invention furthermore relates to the boosting of the action of crop protection compositions comprising in particular spiroheterocyclically substituted tetramic acid derivatives through the addition of ammonium or phosphonium salts and optionally penetrants, to the corresponding compositions, to processes for their preparation and to their use in crop protection as insecticides and/or acaricides and/or fungicides and/or for preventing unwanted vegetation.
Claims
1. A compound of formula (I-a-1): ##STR00081##
2. A pesticide composition, herbicide composition, fungicide composition, or combinations thereof, comprising the compound of formula (I-a-1) according to claim 1.
3. A method for controlling animal pests, unwanted vegetation, fungi, or combinations thereof, comprising allowing a compound of formula (I-a-1) according to claim 1 to act on pests, their habitat, or combinations thereof.
4. A compound of formula (I-a-2): ##STR00082##
5. A pesticide composition, herbicide composition, fungicide composition, or combinations thereof, comprising the compound of formula (I-a-2) according to claim 4.
6. A method for controlling animal pests, unwanted vegetation, fungi, or combinations thereof, comprising allowing a compound of formula (I-a-2) according to claim 4 to act on pests, unwanted vegetation, fungi, their habitat, or combinations thereof.
7. A compound of formula (I-a-5): ##STR00083##
8. A pesticide composition, herbicide composition, fungicide composition, or combinations thereof, comprising the compound of formula (I-a-5) according to claim 7.
9. A method for controlling animal pests, unwanted vegetation, fungi, or combinations thereof, comprising allowing a compound of formula (I-a-5) according to claim 7 to act on animals pests, unwanted vegetation, fungi, or their habitat, or combinations thereof.
Description
PREPARATION EXAMPLES
Example I-a-1
(1) Process A
(2) ##STR00069##
(3) 2.1 g (4.9 mmol) of the compound according to Ex. II-1 are initially charged in 5 ml of N,N-dimethylacetamide, and 1.45 (12.3 mmol) of potassium tert-butoxide in 5 ml of N,N-dimethylacetamide are added dropwise at 30-40° C. The mixture is stirred at 40° C. for 6 hours.
(4) A sample is removed for thin-layer chromatography, and the reaction mixture is then, at 0-10° C., adjusted to pH 4 using 1N hydrochloric acid, and the mixture is concentrated under reduced pressure. The residue is chromatographed on silica gel using n-hexane/isopropanol (gradient).
(5) Yield: 1.05 g (50.6% of theory) m.p. decomposition
(6) .sup.1H-NMR (400 MHz, d.sub.6-DMSO): δ=1.46 (br, 2H, CH.sub.2), 1.97, 2.12 (2s, 3H each, Ar—CH.sub.3), 2.67-270 (mbr, 2H, CH.sub.2—N), 3.44 (s, 3H, N—OCH.sub.3), 7.03-7.05 (d, 1H, Ar—H) 7.10-7.12 (d, 1H, Ar—H), 7.22-7.32 (m, 4H, Ar—H), 8.22 (br, 1H, NH), 10.78 (br, 1H OH).
(7) The following compounds of the formula (I-a) are obtained analogously to Example (I-a-1) and in accordance with the general statements on the preparation:
(8) TABLE-US-00002 (I-a)
(9) Analysis:
(10) (I-a-2) .sup.1H NMR (600 MHz, CD.sub.3OD): δ=1.78 (t, 3H, CH.sub.2CH.sub.3), 1.60-1.65 (tm, 2H), 2.04, 2.20 (2s, 3H each, Ar—CH.sub.3), 2.25-2.34 (qm, 2H), 2.75 (m, br, 2H), 3.35-3.38 (cm, 2H), 3.76-3.79 (m, 2H, OCH.sub.2CH.sub.3), 7.06-7.08 (d, 1H, ArH), 7.10-7.14 (m, 3H, ArH), 7.26-7.30 (m, 2H) ppm.
(11) (I-a-3) .sup.1H NMR (600 MHz, CD.sub.3OD): δ=1.18 (t, 3H, CH.sub.2CH.sub.3), 1.63-1.67 (dm, 2H), 2.28 (ct. 2H), 2.75 (ct, 2H), 3.36-3.38 (dm, 2H), 3.77-3.79 (m, 2H, O—CH.sub.2CH.sub.3), 7.15-7.22 (m, 2H, ArH), 7.49-7.58 (m, 3H, ArH), 7.63-7.67 (m, 2H, ArH) ppm.
(12) (I-a-4) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.46-1.49 (dm, br, 2H), 2.12 (tm, br, 2H), 2.65-2.73 (m, br, 2H), 3.26-3.28 (dm, br, 2H), 3.44 (s, 3H, NOCH.sub.3), 7.27-7.32 (“t”, 2H, ArH), 7.47-7.61 (m, 3H, ArH), 7.68-7.71 (m, 2H, ArH), 8.31 (s, br, 1H, NH), 11.15 (s, 1H, OH) ppm.
(13) (I-a-5) .sup.1H NMR (600 MHz, CD.sub.3OD): δ=1.84-1.87, 2.06-2.08 (2d, br, 2H), 2.25 (s, 3H, ArCH.sub.3), 2.48-2.54, 2.62-2.66 (2tm, 2H), 3.53-3.57, 3.74-3.78 (2tm, 2H), 3.98-4.01, 4.08-4.10 (2dm, 2H), 4.02, 4.03 (2s, 3H, NOCH.sub.3), 7.13-7.16 (tm, 2H, ArH), 7.34-7.37 (m, 2H, ArH), 7.48-7.50 (m, 1H, ArH), 7.60-7.63 (m, 2H, ArH) ppm.
(14) (I-a-6) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.11 (t, 3H, CH.sub.2CH.sub.3), 1.44-1.46 (dm, br, 2H), 2.18 (s and m, br, 5H, ArCH.sub.3), 2.76 (cm, 2H), 3.20-3.22 (d, 2H), 3.64-3.69 (q, br, 2H, NOCH.sub.2CH.sub.3), 7.23-7.31 (m, 4H, ArH), 7.45-7.47 (m, 1H, ArH), 7.62-7.67 (m, 2H, ArH), 8.26 (s, br, 1H, NH), 10.86 (s, br, 1H, OH) ppm.
(15) (I-a-7) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.10 (t, 3H, CH.sub.2CH.sub.3), 1.42 (m, br, 2H), 2.05-2.09 (m, br, 2H), 2.66-2.71 (m, br, 2H), 3.19 (m, br, 2H), 3.63-3.68 (q, br, 2H, NOCH.sub.2CH.sub.3), 3.74 (s, 3H, ArOCH.sub.3), 7.04-7.06 (d, 1H, ArH), 7.24-7.32 (m, 3H, ArH), 7.39-7.43 (m, 2H, ArH), 8.09 (s, br, 1H, NH), 10.83 (s, br, 1H, OH) ppm.
(16) (I-a-8) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.06 (t, 3H, CH.sub.2CH.sub.3), 1.42-1.45 (d, br, 2H), 1.96 (s, 3H, ArCH.sub.3), 2.07-2.12 (br, 2H), 2.42-2.48 (q, 21H, ArCH.sub.2CH.sub.3), 2.64-2.70 (m, 2H), 3.44 (s, 3H, NOCH.sub.3), 7.07-7.13 (m, 2H), 7.22-7.33 (m, 4H), 8.20 (s, br, 1H, NH), 10.8 (s, br, 1H, OH) ppm.
(17) (I-a-9) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.06, 1.11 (2t, 3H each, CH.sub.2CH.sub.3), 1.41-1.44 (d, br, 2H), 1.96 (s, 3H, ArCH.sub.3), 2.14 (br, 2H), 2.44-2.47 (q, 2H, ArCH.sub.2CH.sub.3), 2.72 (m, br, 2H), 3.21 (m, br, 2H), 3.64-3.69 (q, br, 2H, NOCH.sub.2CH.sub.3), 7.07-7.13 (m, 2H, ArH), 7.22-7.33 (m, 4H, ArH), 8.21 (s, br, 1H, NH), 10.8 (s, br, 1H, OH) ppm.
(18) (I-a-10) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.43 (cm, br, 2H), 2.08 (cm, br, 2H), 2.67 (cm, br, 2H), 3.25 (cm, br, 2H), 3.43 (s, 3H, NOCH.sub.3), 3.74 (s, 3H, ArOCH.sub.3), 7.04-7.06 (d, 1H, ArH), 7.24-7.32 (m, 3H, ArH), 7.38-7.43 (m, 2H, ArH), 8.10 (s, br, 1H, NH), 10.83 (s, br, 1H, OH) ppm.
(19) (I-a-11) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.11 (t, 3H, CH.sub.2CH.sub.3), 1.44 (m, br, 2H), 1.98 (s, 3H, ArCH.sub.3), 2.12 (s+mbr, 3+2H), 2.73 (m, br, 2H), 3.20-3.22 (m, br, 2H), 3.64-3.69 (q, br, 2H, OCH.sub.2CH.sub.3), 7.05-7.07 (d, 1H, ArH), 7.10-7.13 (m, 2H), 7.28-7.34 (m, 1H, ArH), 7.44-7.51 (m, 1H, ArH), 8.22 (s, br, 1H, NH), 10.79 (s, br, 1H, OH) ppm.
(20) (I-a-12) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.11 (t, 3H, CH.sub.2CH.sub.3), 1.45 (m, br, 2H), 1.97 (s, 3H, ArCH.sub.3), 2.12 (s+mbr, 3+2H), 2.73 (m, br, 2H), 3.17-3.20 (m, br, 2H), 3.64-3.69 (q, br, 2H, OCH.sub.2CH.sub.3), 7.06-7.08 (d, 1H, ArH), 7.11-7.13 (d, 1H, ArH), 7.26-7.30 (m, 1H, ArH), 7.43-7.49 (m, 2H, ArH), 8.23 (s, br, 1H, NH), 10.78 (s, br, 1H, OH) ppm.
(21) (I-a-13) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.46 (m, br, 2H), 1.98 (s, 3H, ArCH.sub.3), 2.12 (s+mbr, 3+2H), 2.66-2.70 (m, br, 2H), 3.25 (m, br, 2H), 3.44 (s, 3H, NOCH.sub.3), 7.05-7.07 (d, 1H, ArH), 7.10-7.13 (m, 2H, ArH), 7.30-7.34 (m, 1H, ArH), 7.44-7.51 (m, 1H, ArH), 8.23 (s, br, 1H, NH), 10.79 (s, br, 1H, OH) ppm.
(22) (I-a-14) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.11 (t, 3H, CH.sub.2CH.sub.3), 1.43 (m, br, 2H), 1.99 (s, 3H, ArCH.sub.3), 2.12 (s+mbr, 3H+2H), 2.65-2.68 (m, br, 2H), 3.20-3.22 (m, br, 2H), 3.64-3.69 (q, br, 2H, N—OCH.sub.2CH.sub.3), 7.07-7.09 (d, 1H, NH), 7.12-7.16 (m, 2H, ArH), 7.28-7.32 (dd, 1H, ArH), 7.63 (t, 1H, ArH), 8.22 (s, br, 1H, NH), 10.80 (s, br, 1H, OH) ppm.
(23) (I-a-15) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.46 (m, br, 2H), 1.99 (s, 3H, ArCH.sub.3), 2.12 (s+mbr, 3H+2H), 2.64-2.70 (m, br, 2H), 3.44 (s, 3H, NOCH.sub.3), 7.07-7.09 (d, 1H, ArH), 7.12-7.16 (m, 2H, ArH), 7.29-7.32 (din, 1H. ArH), 7.61-7.65 (t, 1H, ArH), 8.23 (s, br, 1H, NH), 10.80 (s, br, OH) ppm.
Example (I-b-1)
(24) ##STR00071##
(25) At 0° C., 100 mg of sodium hydride (60%) are added to 0.4 g (1 mmol) of the compound according to Example (I-a-1) in 10 ml of tetrahydrofuran. At 20° C., 0.32 g (3 mmol) of isobutyryl chloride in 2 ml of tetrahydrofuran are added dropwise, and the mixture is boiled under reflux for 1 h. After the reaction has ended (thin-layer chromatography), the reaction mixture is concentrated under reduced pressure and the residue is purified by chromatography on silica gel using the mobile phase system methylene chloride/isopropanol (gradient). This gives 0.25 g ({circumflex over (=)}47% of theory), m.p. 74° C.
(26) .sup.1H-NMR (400 MHz, CD.sub.3CN): δ=0.96-0.98 (4s, 6H, CH(CH.sub.3).sub.2), 1.66 (br, 2H, CH.sub.2), 2.02, 2.20 (2s, 3H each, Ar—CH.sub.3), 2.09-2.17 (m, 4H, CH.sub.2), 2.58-2.66 (m, 1H, CH(CH.sub.3).sub.2), 3.35 (br, 2H, N—CH.sub.2), 3.48 (s, 3H, OCH.sub.3), 7.06-7.18 (m, 4H, Ar—H), 7.24-7.28 (m, 2H, Ar—H), 7.38 (br, 1H, NH).
(27) The following compounds of the formula (I-b) are obtained analogously to Example (I-b-1) and in accordance with the general statements on the preparation:
(28) TABLE-US-00003 (I-b)
Example (I-c-1)
(29) ##STR00073##
(30) At 0° C., 100 mg of sodium hydride (60%) are added to 0.4 g (1 mmol) of the compound according to Example (I-a-1) in 10 ml of tetrahydrofuran. At about 20° C., 0.28 ml (3 mmol) of ethyl chloroformate in 2 ml of tetrahydrofuran are added dropwise, and the mixture is stirred at room temperature. After the reaction has ended (thin-layer chromatography), the reaction mixture is concentrated under reduced pressure and the residue is purified by chromatography on silica gel using the mobile phase system methylene chloride/isopropanol (gradient). This gives 0.35 g ({circumflex over (=)}59% of theory), m.p. 90° C.
(31) .sup.1H-NMR (400 MHz, CD.sub.3CN): δ=1.05 (t, 3H, CH.sub.2CH.sub.3), 1.65-1.7 (“tbr”, 2H, CH.sub.2), 2.03, 2.19 (2s, 3H each, Ar—CH.sub.3), 3.38 (br, 2H, N—CH.sub.2), 3.50 (s, 3H, OCH.sub.3) 3.97-4.03 (q, 2H, OCH.sub.2CH.sub.3), 7.10-7.18 (m, 4H, Ar—H), 7.27-7.31 (m, 2H, Ar—H), 7.41 (br, 1H, NH).
(32) The following compounds of the formula (I-c) are obtained analogously to Example (I-c-1) and in
(33) TABLE-US-00004 (I-1-c)
Example II-1
(34) ##STR00075##
(35) Under argon, 2.5 g (11 mmol) of methyl 4-amino-1-methoxypiperidine-4-carboxylate hydrochloride and 100 ml of anhydrous tetrahydrofuran are initially charged.
(36) At 20° C., 6.4 ml (46 mmol) of triethylamine are added dropwise.
(37) The mixture is stirred at 50° C. for 1 hour, and 3.2 g (12.1 mmol) of 2,6-dimethyl-3-(4-fluorophenyl)phenylacetic acid are added at 20° C. After 15 minutes, 4.6 ml of triethylamine (33 mmol) are added dropwise, followed immediately by 0.52 ml of phosphorus oxychloride (6.6 mmol); the solution should boil gently. The reaction mixture is stirred at 40° C. for 4 hours and then concentrated under reduced pressure to a quarter of its original volume, 100 ml of saturated sodium bicarbonate solution are stirred in, the mixture is extracted with methylene chloride and dried, and the extract is concentrated under reduced pressure.
(38) The residue is purified by column chromatography on silica gel (n-hexane:isopropanol (gradient))
(39) Yield: 2.15 g (36% of theory), m.p. 131° C.
(40) .sup.1H-NMR (400 MHz, CD.sub.3CN): δ=2.14, 2.33 (2s, 3H each, Ar—CH.sub.3), 3.44 (s, 3H, NOCH.sub.3), 3.58 (s, 3H, CO.sub.2CH.sub.3), 3.68 (s, 2H, CO—CH.sub.2), 6.63 (br, 1H, NH), 7.00-7.01 (d, 1H, ArH), 7.07-7.09 (d, 1H, Ar—H), 7.13-7.18 (m, 2H, Ar—H), 7.28-7.31 (m, 2H, Ar—H).
(41) The following compounds of the formula (II) are obtained analogously to Example (II-1) and in accordance with the general statements on the preparation:
(42) TABLE-US-00005 (II)
Example I-a′-1
(43) ##STR00077##
(44) 2.9 g (6.78 mmol) of the compound II′-1 are initially charged in 10 ml of N,N-dimethylacetamide (DMA). At 40° C., a solution of 2.00 g (16.9 mmol) of potassium tert-butoxide in 10 ml of DMA is added dropwise, and the mixture is stirred at 40° C. for a further 4 h. Using 1N HCl the reaction mixture is adjusted to pH 4, and the solvent is evaporated. The residue is purified on a Combi Flash chromatography system on silica gel using a methylene chloride/isopropanol gradient. This gives 2.1 g (≈71% of theory) of the compound I-a′-1 of m.p. 201° C.
(45) .sup.1H NMR (400 MHz, d.sub.6-DMSO): δ=1.10 (t, 3H, CH.sub.2CH.sub.3), 1.43 (br, 2H), 2.04 (s, 3H, ArCH.sub.3), 2.08 (br, 2H), 2.16 (s, 3H, Ar—CH.sub.3), 2.67-2.74 (cm, br, 2H), 3.19-3.21 (d, br, 2H), 3.65-3.69 (m, br, 2H, OCH.sub.2CH.sub.3), 6.99-7.00 (d, 1H, ArH), 7.42-7.44 (d, 1H, ArH), 8.25 (br, 1H, NH), 10.92 (br, 1H, OH) ppm.
(46) Example (I-a′-2) is obtained analogously to Example (I-a′-1):
(47) ##STR00078##
(48) .sup.1H NMR (600 MHz, d.sub.6-DMSO): δ=1.44-1.48 (cm, 2H), 2.04, 2.15 (2s, 3H each, ArCH.sub.3), 2.08-2.13 (cm, 2H), 2.67-2.70 (cm, 2H), 3.26-3.27 (m, br, 2H), 3.44 (s, 3H, OCH.sub.3), 6.99-7.01 (d, 1H, ArH), 7.43-7.44 (d, 1H, ArH), 8.31 (br, 1H, NH), 10.97 (br, 1H, OH) ppm.
Example II′-1
(49) ##STR00079##
(50) 2.63 (11 mmol) of ethyl 4-amino-1-ethoxypiperidine-4-carboxylate hydrochloride are initially charged in 100 ml of tetrahydrofuran, and 6.5 ml (46 mmol) of triethylamine are added dropwise. The mixture is stirred at 50° C. for one hour, cooled to 20° C., 2.94 g (12 mmol) of 3-bromo-2,6-dimethylphenylacetic acid are added, the mixture is stirred for 15 min, 4.6 ml (33 mmol) of triethylamine are added and immediately 0.52 ml (6.6 mmol) of phosphorus oxychloride is added dropwise, and the mixture is then stirred at 40° C. for 4 h. The salts are filtered off, and the mixture is dried by evaporation. The residue is purified on a Combi Flash chromatography system on silica gel using n-hexane/isopropanol (gradient). This gives 3.0 g (≈59% of theory) of the compound (II′-1) of melting point m.p. 168° C.
(51) .sup.1H NMR (400 MHz, CD.sub.3CN): δ=1.09 (t, 3H, CH.sub.2CH.sub.3), 2.08-2.17 (m, br, 4H), 2.25, 2.38 (2s, 3H each, ArCH.sub.3), 2.52 (cm, br, 2H), 3.11 (m, br, 2H), 3.58 (s, 3H, OCH.sub.3), 3.64-3.70 (m+s, 4H, OCH.sub.2, CH.sub.2CO), 6.68 (br, 1H, NH), 6.93-6.95 (d, 1H, ArH), 7.36-7.38 (d, 1, ArH) ppm.
(52) Example II′-2 is obtained analogously to Example II′-1:
(53) ##STR00080##
(54) .sup.1H NMR (400 MHz, CD.sub.3CN): δ=2.09-2.13 (m, 4H), 2.25, 2.38 (2s, 3H each, ArCH.sub.3), 2.45-2.50 (cm, br, 2H), 3.16 (m, br, 2H), 3.45 (s, 3H, NOCH.sub.3), 3.58 (s, 3H, CO.sub.2CH.sub.3), 3.67 (s, 2H, CH.sub.2—CO), 6.67 (br, 1H, NH), 6.93-6.95 (d, 1H, ArH), 7.36-7.38 (d, 1H, ArH) ppm.
USE EXAMPLES
Example 1
(55) Phaedon Test (PHAECO Spray Treatment)
(56) Solvents: 78.0 parts by weight of acetone
(57) 1.5 parts by weight of dimethylformamide
Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
(58) To produce a suitable preparation of active compound, one part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. Discs of Chinese cabbage (Brassica pekinensis) are sprayed with an active compound preparation of the desired concentration and, after drying, populated with larva of the mustard beetle (Phaedon cochleariae).
(59) After 7 days, the effect in % is determined. 100% means that all beetle larva have been killed; 0% means that none of the beetle larva have been killed.
(60) In this test, for example, the following compounds of the Preparation Examples show
(61) at an application rate of 500 g/ha, an efficacy of 83%: Ex. No. I-a-1
(62) at an application rate of 500 g/ha, an efficacy of 100%: Ex. Nos. I-a-2, I-a-3, I-a-8, I-a-9
(63) at an application rate of 100 g/ha, an efficacy of 100%: Ex. No. I-a-6
Example 2
(64) Spodoptera frugiperda Test (SPODFR Spray Treatment)
(65) Solvents: 78.0 parts by weight of acetone
(66) 1.5 parts by weight of dimethylformamide
Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
(67) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. Discs of maize leaves (Zea mays) are sprayed with an active compound preparation of the desired concentration and, after drying, populated with caterpillars of the armyworm (Spodoptera frugiperda).
(68) After 7 days, the effect in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
(69) In this test, for example, the following compounds of the Preparation Examples show
(70) at an application rate of 500 g/ha, an efficacy of 83%: Ex. Nos. I-a-1, I-a-3, I-a-4, I-a-12
(71) at an application rate of 500 g/ha, an efficacy of 100%: Ex. Nos. I-a-2, I-a-5, I-a-6, I-a-14, I-a-15, I-b-1, I-b-2, I-c-1, I-c-2
Example 3
(72) Myzus Test (MYZUPE Spray Treatment)
(73) Solvents: 78 parts by weight of acetone
(74) 1.5 parts by weight of dimethylformamide
Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
(75) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. Discs of Chinese cabbage (Brassica pekinensis) which are infested by all stages of the green peach aphid (Myzus persicae) are sprayed with an active compound preparation of the desired concentration. After 6 days, the effect in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
(76) In this test, for example, the following compounds of the Preparation Examples show
(77) at an application rate of 500 g/ha, an efficacy of 90%: Ex. Nos. I-a-1, I-a-8, I-a-9
(78) at an application rate of 500 g/ha, an efficacy of 100%: Ex. Nos. I-a-2, I-a-3, I-a-4, I-a-5, I-a-6, I-a-7, I-a-10, I-a-11, I-a-12, I-a-13, I-a-14, I-a-15, I-b-1, I-b-2, I-c-1, I-c-2
Example 4
(79) Tetranychus Test OP-Resistant (TETRUR Spray Treatment)
(80) Solvents: 78.0 parts by weight of acetone
(81) 1.5 parts by weight of dimethylformamide
Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
(82) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. Discs of bean leaves (Phaseolus vulgaris) which are infested by all stages of the greenhouse red spidermite (Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration.
(83) After 6 days, the effect in % is determined. 100% means that all spidermites have been killed; 0% means that none of the spidermites have been killed.
(84) In this test, for example, the following compounds of the Preparation Examples show
(85) at an application rate of 100 g/ha, an efficacy of 90%: Ex. Nos. I-a-3, I-a-5, I-a-6, I-a-7, I-a-8, I-a-9, I-a-10, I-a-14, I-c-3
(86) at an application rate of 100 g/ha, an efficacy of 100%: Ex. Nos. I-a-2, I-a-4, I-a-11, I-a-12, I-a-13, I-a-15
Example 5
(87) Boophilus microplus Test (BOOPMI Injection)
(88) Solvent: Dimethyl sulphoxide
(89) To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of solvent and the concentrate is diluted with solvent to the desired concentration. The solution of active compound is injected into the abdomen (Boophilus microplus) and the animals are transferred into dishes and stored in a climatized room. The activity is monitored for deposition of fertile eggs.
(90) After 7 days, the effect in % is determined. 100% means that none of the ticks has laid any fertile eggs.
(91) In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 20 μg/animal, an efficacy of 90%: I-a-2
(92) In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 20 μg/animal, an efficacy of 95%: I-a-1
Example 6
(93) Lucilia cuprina Test (LUCICU)
(94) Solvent: Dimethyl sulphoxide
(95) To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulphoxide and the concentrate is diluted with water to the desired concentration. Containers containing horse meat treated with the active compound preparation of the desired concentration are populated with about 20 Lucilia cuprina larva.
(96) After 2 days, the kill in % is determined. 100% means that all larva have been killed; 0% means that none of the larva have been killed.
(97) In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 100 ppm, an efficacy of 80%: I-c-2
(98) In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 100 ppm, an efficacy of 90%: I-a-1, I-a-2
Example 7
(99) 1. Herbicidal Pre-Emergence Action
(100) Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in wood fibre pots and covered with soil. The test compounds, formulated in the form of wettable powders (WP), are then, as aqueous suspension with a water application rate of 600 l/ha (converted), with 0.2% of wetting agent added, applied to the surface of the covering soil in various dosages. After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the test plants. The visual assessment of the emergence damage on the test plants is carried out after a trial period of about 3 weeks by comparison with untreated controls (herbicidal effect in %: 100% effect=the plants have died, 0% effect=like control plants). In addition to the compounds mentioned above, the following compounds, applied by the pre-emergence method at 320 g of a.i./ha, show an efficacy of 90% against Lolium multiflorum and Setaria viridis: I-1-a-1 In addition to the compounds mentioned above, the following compounds, applied by the pre-emergence method at 320 g of a.i./ha, show an efficacy of 100% against Echinocloa crus-galli: I-a-2, I-b-1, I-b-2, I-c-2
2. Herbicidal Post-Emergence Action Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in wood fibre pots, covered with soil and cultivated in a greenhouse under good growth conditions. 2-3 weeks after sowing, the test plants are treated at the one-leaf stage. The test compounds, formulated as wettable powders (WP), are, in various dosages at a water application rate of 600 l/ha (converted), with 0.2% of wetting agent added, sprayed onto the green parts of the plants. After the test plants have been kept in the greenhouse under optimum growth conditions for about 3 weeks, the effect of the preparations is rated visually in comparison to untreated controls (herbicidal effect in %: 100% effect=the plants have died, 0% effect=like control plants). In addition to the compounds mentioned above, the following compounds, applied by the post-emergence method at 80 g/ha, show an efficacy of 90% against Echinocloa crus-galli and Lolium multiflorum: I-a-3, I-a-4, I-a-5.
Example 8: Increase of Penetration into the Plant by Ammonium or Phosphonium Salts and Synergistic Increase of Penetration into the Plant by Ammonium Salts in Combination with Penetrants
(101) In this test, the penetration of active compounds through enzymatically isolated cuticles of apple tree leaves is measured.
(102) Use is made of leaves which, fully developed, are cut from apple trees of the cultivar Golden Delicious. The cuticles are isolated by initially filling leaf discs punched out and stained with dye on the underside by vacuum infiltration with a pectinase solution (0.2 to 2% strength) buffered to pH between 3 and 4, then adding sodium azide and allowing the leaf discs treated in this manner to stand until the original leaf structure has dissolved and the non-cellular cuticles have detached.
(103) Only the cuticles, free from hairs and stoma, of the upper sides of the leaves are then used further. They are washed repeatedly alternately with water and a buffer solution of pH 7. The clean cuticles obtained are then mounted on Teflon plates and smoothed and dried with a gentle stream of air.
(104) In the next step, the cuticle membranes obtained in this manner are placed into stainless steel diffusion cells (=transport chambers) for membrane transport studies. To this end, the cuticles are placed with a pincette into the centre of the edges, coated with silicone fat, of the diffusion cells and closed with a ring, which is also treated with fat. The arrangement is chosen such that the morphological outside of the cuticles is facing outwards, i.e. is exposed to air, whereas the original inside is facing the interior of the diffusion cell.
(105) The diffusion cells are filled with a 30% strength ethylene glycol/water solution. To determine the penetration, in each case 10 μl of the spray liquor of the composition below are applied to the outside of the cuticles. The spray liquor is prepared using local tap water of medium hardness.
(106) After the application of the spray liquors, the water is allowed to evaporate and the chambers are inverted and placed into thermostated tubs in which the temperature and atmospheric humidity over the cuticles can be adjusted using a gentle stream of air onto the cuticles with the spray coating (20° C., 60% rh). At regular intervals, an autosampler takes aliquots and the active compound content is determined by HPLC.
(107) The test results are shown in the table below. The stated numbers are average values of 8 to 10 measurements. It is clearly evident that even ammonium sulphate on its own improves the penetration markedly, and that, together with RME, a superadditive (synergistic) effect is present.
(108) TABLE-US-00006 TABLE Penetration after 24 h/% EC + Active compound EC RME (1 g/l) EC + AS EC + RME (1 g/l) + (1 g/l) AS (1 g/l) Example I-a-1 <0.2 3.8 0.8 19 300 ppm in EC + DAHP EC + RME (1 g/l) + DMF/emulsifier (1 g/l) DAHP (1 g/l) W 7:1 (w/w) <0.2 2.3 0.8 15 RME = Rapeseed oil methyl ester (formulated as 500 EW, concentration stated in g of active compound/l) AS = Ammonium sulphate DAHP = Diammonium hydrogenphosphate EC = Emulsifiable concentrate
(109) TABLE-US-00007 TABLE Penetration after 24 h/% EC + Active compound EC RME (1 g/l) EC + AS EC + RME (1 g/l) + (1 g/l) AS (1 g/l) Example I-1-a-2 1.4 3.8 1.7 17 300 ppm in EC + DAHP EC + RME (1 g/l) + DMF/emulsifier (1 g/l) DAHP (1 g/l) W 7:1 (w/w) 1.4 3.9 1.7 21
Example 9: Activity Boost by Ammonium Salts in Combination with Penetrants
(110) Myzus persicae Test
(111) Solvent: 7 parts by weight of dimethylformamide
(112) Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
(113) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. For application with ammonium salts and penetrants (rapeseed oil methyl ester 500 EW) these are in each case added in a concentration of 1000 ppm of a.i. to the spray liquor.
(114) Bell pepper plants (Capsicum annuum) heavily infested by the green peach aphid (Myzus persicae) are sprayed to runoff point with the preparation of active compound at the desired concentration. After the desired period of time, the kill in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.
(115) TABLE-US-00008 TABLE Kill rate/% after 6 days +RME +RME + AS Active Concentration/ +AS (1000 (1000 ppm compound ppm (1000 ppm) ppm) each) I-a-1 20 60 90 95 100 4 0 30 55 100 I-a-2 4 0 20 95 95 0.8 0 0 0 40
Example 10
(116) Aphis gossypii Test
(117) Solvent: 7 parts by weight of dimethylformamide
(118) Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
(119) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. For application with ammonium salts and penetrants (rapeseed oil methyl esters 500 EW) these are in each case added in a concentration of 1000 ppm of a.i. to the spray liquor.
(120) Cotton plants (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are sprayed to runoff point with the preparation of active compound at the desired concentration.
(121) After the desired period of time, the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
(122) TABLE-US-00009 TABLE Kill rate/% after 6 days +RME +RME + AS Active Concentration/ +AS (1000 (1000 (1000 ppm compound ppm ppm) ppm) each) I-a-1 20 0 40 55 100 I-a-2 20 0 25 20 90 4 0 0 0 45