Pyrimidine derivatives

Abstract

This invention relates to pyrimidine derivatives, to compositions comprising the pyrimidine derivatives, to methods of making and using these compositions, and to the use of the pyrimidine derivatives as adjuvants, particularly for agrochemical use. In particular, the present invention relates to compositions comprising the pyrimidine derivatives selected from emulsifiable concentrates (EC), emulsions in water (EW), suspensions of particles in water (SC), soluble liquids (SL), capsule suspensions (CS), suspensions of particles with an emulsion (SE), dispersion concentrates (DC), suspensions of particles in oil (OD), water dispersible granules (WG), soluble granules (SG) and wettable powders (WP).

Claims

1. A compound of formula (I), or a salt thereof, ##STR00016## wherein R.sup.1 is selected from C.sub.4-C.sub.20-alkyl and C.sub.4-C.sub.20-alkenyl; R.sup.2 is selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl; X is either ##STR00017## n is from 2 to 30.

2. A compound or salt according to claim 1, wherein X is ##STR00018##

3. A compound or salt according to claim 1, wherein X is ##STR00019##

4. A compound or salt of claim 1 of formula (I) ##STR00020## wherein R.sup.1 is selected from C.sub.6-C.sub.18-alkyl and C.sub.6-C.sub.18-alkenyl; X is ##STR00021## n is from 2 to 20; R.sup.2 is methyl or H.

5. A compound or salt according to claim 4 wherein R.sup.2 is methyl and R.sup.1 and n are as defined in the table TABLE-US-00013 Compound R.sup.1 n 1 Hexyl 2 2 Hexyl 10 3 Hexyl 20 4 Nonyl 7 5 Nonyl 10 6 Dodecyl 7 7 Dodecyl 10 8 Hexadecyl 10 9 Oleyl 2 10 Oleyl 10 11 Oleyl 20.

6. A compound of claim 1 of formula (I) ##STR00022## wherein R.sup.1 is selected from C.sub.6-C.sub.18-alkyl and C.sub.6-C.sub.18-alkenyl; X is ##STR00023## n is from 2 to 8; R.sup.2 is methyl or H.

7. A compound of claim 6 wherein R.sup.2 is methyl, R.sup.1 is dodecyl and n is 3.

8. A composition comprising a biologically active ingredient, particularly an agrochemical active ingredient, and a compound according to claim 1.

9. A tank-mix formulation comprising a compound according to claim 1.

10. A method of controlling pests comprising applying the agrochemical composition of claim 8 to said pests or to a locus of said pests.

11. A method of making an agrochemical composition according to claim 8, comprising combining a biologically active ingredient and a compound of formula (I), or a salt thereof, ##STR00024## Wherein R.sup.1 is selected from C.sub.4-C.sub.20-alkyl and C.sub.4-C.sub.20-alkenyl; R.sup.2 is selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl; X is either ##STR00025## n is from 2 to 30.

12. A composition comprising a biologically active ingredient and a compound according to claim 1, wherein the compound acts as an adjuvant in the composition.

13. The composition of claim 12 wherein the biologically active ingredient is an agrochemical active ingredient.

Description

EXPERIMENTAL

(1) The following pyrimidine adjuvants have been prepared:

(2) TABLE-US-00002 Adjuvant R1 n Adjuvant 1  Hexyl  2 Adjuvant 2  Hexyl 10 Adjuvant 3  Hexyl 20 Adjuvant 4  Nonyl  7 Adjuvant 5  Nonyl 10 Adjuvant 6  Dodecyl  7 Adjuvant 7  Dodecyl 10 Adjuvant 8  Hexadecyl 10 Adjuvant 9  Oleyl  2 Adjuvant 10 Oleyl 10 Adjuvant 11 Oleyl 20

(3) TABLE-US-00003 Adjuvant R1 m Adjuvant 12 Dodecyl 3

(4) As an example, adjuvant 10 was prepared as follows:

(5) Step (a):

(6) To a three necked round bottomed flask equipped with a nitrogen gas inlet, bubbler and thermoprobe, was added oleyl alcohol (48 g, 0.179 mol) followed by lithium tert-butoxide (1M in THF) (179 ml, 0.179 mol) and the reaction mixture stirred at room temperature for 30 minutes. A solution of 4,6-difluoropyrimidine (21 g, 0.179 mol) in anhydrous THF (80 mL) in a three necked round bottomed flask equipped with nitrogen gas inlet/bubbler and thermoprobe was cooled to 0° C. and the pre-mixed solution of oleyl alcohol and lithium tert-butoxide was added dropwise, keeping T.sub.int<5° C. Once addition was complete, the solution was allowed to warm to room temperature over 2 hrs. Once the reaction was complete, water (500 ml) and EtOAc (500 ml) were added and the layers separated (brine required). The aqueous layer was extracted with EtOAc (2×500 ml). The combined organic layers were dried (MgSO.sub.4), filtered and concentrated in vacuo to afford the product (63 g, 95%) as an orange liquid.

(7) Step (b):

(8) To a 2 L three necked round bottomed flask equipped with stirrer bar, dropping funnel, thermoprobe, N.sub.2 inlet/bubbler and ice/water bath was added methoxypoly(ethylene glycol) (Carbowax 550™ MPEGs, average molecular weight of approximately 550, average number of oxyethylene units approximately 10, 50 g, 0.090 mol). Step (a) product (Step (a), 35 g, 0.095 mol) in DMSO (Stock, 400 ml) was added to the methoxypolyethylene glycol in one portion. A solution of potassium tert-butoxide (Stock, 10.7 g, 0.095 mol, 1.05 eq) in THF (Stock, 95 ml) (1M solution) was added in one go via a dropping funnel. The ice bath was removed and the reaction mixture stirred at room temperature over the weekend. The reaction mixture was cooled in an ice bath and water (400 ml) was added slowly dropwise over 15 minutes then extracted with EtOAc (3×400 ml). The combined organics were washed with water (600 ml) and dried (MgSO.sub.4). The crude (60 g) was purified by column chromatography (load in petrol, 9.5×17 cm silica, 120 ml fractions, TLC in 5% MeOH/dichloromethane, KMnO.sub.4 to visualize, gradient elution with EtOAc/petrol: 500 ml 30%, 1 L 50% 1 L dichloromethane then MeOH/dichloromethane: 1 L 2%, 1 L 4%, 1 L 6%, 2.5 L 8%) to afford the product (44 g mixed with DMSO). This was dissolved in dichloromethane (300 ml), washed with water (4×300 ml) and dried (MgSO.sub.4) to afford the product (36 g) as a yellow/orange oil.

(9) The other adjuvants have been prepared in a similar manner as adjuvant 10 using the appropriate reactants. For example, for adjuvants with 7 EO, Carbowax MPEG 350™ has been used, for adjuvants with 2 EO and 20 EO Methyl Carbitol™ and MPEG 1000™—Ineos/mPEG-OH, MW 1 k (Creative PEGworks) has been used, respectively. For adjuvants with 3 PO Dowanol TPM™ has been used.

(10) The structure of the compounds were confirmed by NMR and liquid chromatography using the following conditions:

(11) NMR:

(12) Spectrometer: Bruker AvIII 400 MHz

(13) Solvent: d4-methanol

(14) Techniques: 1D 1H NMR, 2D 1H, 1H DQF-COSY 2D 1H, .sup.13C HSQC, HMBC NMR

(15) Adjuvant 10:

(16) .sup.1H NMR (400 MHz, d4-methanol) δ ppm 0.82-0.95 (m, 3H), 1.28 (br s, 17H), 1.39-1.49 (m, 2H), 1.68-1.83 (m, 2H), 3.35 (s, 3H), 3.49-3.55 (m, 2H), 3.57-3.70 (m, 23H), 3.82 (dd, J=5.40, 4.00 Hz, 2H), 4.29 (t, J=6.60 Hz, 2H), 4.40-4.50 (m, 2H), 6.15 (s, 1H), 8.35 (s, 1H).

(17) Liquid Chromatography:

(18) The samples were analyzed using liquid chromatography in conjunction with diode array detection (DAD), charged aerosol detection (CAD) and mass spectrometry (MS) as follows:

(19) Sample Preparation:

(20) All samples were prepared at either 0.1 mg mL−1 concentration (CAR1224B, CAR1495B, CAR1496A) or 1 mg mL−1 concentration (all other samples), in 90:10 Acetonitrile/H2O (vol/vol), before being transferred to auto-sampler vials. For each material, the same vial was used for the C18 Reverse-Phase and the Hydrophilic Interaction Liquid Chromatography (HILIC) experiments (as outlined below).

(21) Chromatographic Conditions:

(22) Analyses were performed using a Waters Acquity UPLC instrument. Detection was performed using a Waters photodiode array detector (PDA or DAD) (detection λ=240 or 254 nm), a Thermo Fisher Scientific Corona Veo RS charged aerosol detector (CAD), and a Waters SQ Detector 2 mass spectrometer (MS). Each sample was analysed by two different chromatographic methods:

(23) (i) C.sub.18 Reverse-Phase Liquid Chromatography

(24) Column: Phenomenex C.sub.18 Kinetex (100×3 mm, 2.6 μm particle size, serial no. H17-143356)

(25) Temperature: 40° C.

(26) Flow rate: 0.5 mL min.sup.−1

(27) Mobile Phase A: ASTM Type I water+100 mM ammonium acetate+2.5 mL L.sup.−1 acetic acid (pH 5 approx.)

(28) Mobile Phase B: acetonitrile+2.5 mL L.sup.−1 acetic acid (pH 5)

(29) Run time: 60 minutes

(30) Mobile Phase Gradient:

(31) TABLE-US-00004 Time (mins) 0 2 20 30 45 45.1 55 55.1 60 % A 85 85 20 10 10 0 0 85 85 % B 15 15 80 90 90 100 100 15 15

(32) (ii) Hydrophilic Interaction Liquid Chromatography (HILIC)

(33) Column: Waters BEH HILIC (150×2.1 mm, 1.7 μm particle size, serial no. 03003705818509)

(34) Temperature: 30° C.

(35) Flow rate: 0.45 mL min.sup.−1

(36) Mobile Phase A: 97:3 acetonitrile/H2O+300 mM ammonium acetate (vol/vol)

(37) Mobile Phase B: 50:47:3 acetonitrile/H2O/H2O+300 mM ammonium acetate (vol/vol/vol)

(38) Run time: 40 minutes

(39) Mobile Phase Gradient:

(40) TABLE-US-00005 Time (mins) 0 5 15 21 23 25 40 % A 100 100 70 0 0 100 100 % B 0 0 30 100 100 0 0

(41) Interpretation of Data:

(42) The most abundant ethoxylate (EO) or propoxylate (PO) number of each sample was determined according to the peak of highest integrated area in the CAD chromatogram of each HILIC experiment. The identity of this peak was confirmed by examining the corresponding mass spectrum (from the MS chromatogram).

(43) Biological Data:

(44) The compounds were tested for their ability to act as adjuvants for agrochemical compositions comprising the following pesticidal active ingredients: Nicosulfuron Fomesafen Mesotrione Pinoxaden Cyantraniliprole Isopyrazam Epoxiconazole

Nicosulfuron Examples

(45) The efficacy of adjuvants 1-12 as adjuvants for the herbicide nicosulfuron were tested in a glasshouse against four weed species sown into standard soil in pots and cultivated under controlled conditions in a glasshouse (at 24/18° C. day/night; 16 hours light; 65% humidity). Nicosulfuron was added to the spray tank as a standard WG (water dispersible granule) formulation.

(46) The plants were sprayed with nicosulfuron (in the absence of an adjuvant) at rates of 15 and 60 grams of pesticide per hectare using a laboratory track sprayer which delivered the aqueous spray composition at a rate of 200 litres per hectare, using a flat fan nozzle (Teejet 11002VS) at 2 bar. The spray tests were also carried out using nicosulfuron in conjunction with adjuvants 1-12. The adjuvant was added to the spray solution at a rate of 0.2% v/v. All spray solutions also contained 12.5% v/v of iso-Propanol. The weed species and their BBCH growth stage at spraying were Abutilon theophrasti (ABUTH; growth stage 13), Chenopodium album (CHEAL; growth stage 13-14), Digitaria sanguinalis (DIGSA; growth stage 11), and Setaria viridis (SETVI; growth stage 13). Each spray test was replicated three times. The test plants were then grown in a glasshouse under controlled conditions (at 24/18° C. day/night; 16 hours light; 65% humidity) and watered twice a day. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at a time period of 21 days following application. The results shown in Table 1 below are mean averages over the two rates of nicosulfuron, and the three replicates.

(47) TABLE-US-00006 TABLE 1 Testing of adjuvant activities in Nicosulfuron compositions. Mean % Herbicidal Activity Average over Test Adjuvant ABUTH CHEAL DIGSA SETVI all Species 1 Adjuvant 7 59 86 84 96 81 1 No Adjuvant 39 38 18 64 40 2 Adjuvant 6 38 83 74 91 71 2 Adjuvant 8 53 85 87 96 80 2 No Adjuvant 15 13 3 80 28 3 Adjuvant 8 66 85 93 95 85 3 No Adjuvant 34 14 22 84 38 4 Adjuvant 12 66 83 93 96 85 4 Adjuvant 8 74 83 89 96 86 4 Adjuvant 2 61 80 89 97 82 4 Adjuvant 3 49 76 88 93 76 4 Adjuvant 1 64 84 88 93 83 4 Adjuvant 5 49 63 49 91 63 4 Adjuvant 4 48 78 70 94 73 4 Adjuvant 10 58 80 88 97 81 4 Adjuvant 11 64 82 88 94 82 4 Adjuvant 9 57 82 88 95 80 4 No Adjuvant 63 45 4 89 50

Fomesafen Examples

(48) The efficacy of adjuvants 1-12 as adjuvants for the herbicide fomesafen (as the sodium salt) were tested in a glasshouse against four weed species, sown into standard soil in pots and cultivated under controlled conditions in a glasshouse (at 24/18° C. day/night; 16 hours light, 65% humidity). Fomesafen sodium salt was added to the spray tank as a standard SL (soluble concentrate) formulation.

(49) The plants were sprayed with fomesafen (in the absence of an adjuvant) at rates of 100 and 200 grams of pesticide per hectare using a laboratory track sprayer which delivered the aqueous spray composition at a rate of 200 litres per hectare, using a flat fan nozzle (Teejet 11002VS) at 2 bar. The spray tests were also carried out using fomesafen in conjunction with adjuvants 1-12. Unless otherwise stated, the adjuvants were added to the spray solution at a rate of 0.2% v/v. All spray solutions also contained 12.5% v/v of iso-Propanol to normalise the retention of the sprays on the hydrophobic plant surfaces. The weed species and their BBCH growth stage at spraying were Abutilon theophrasti (ABUTH; growth stage 12-13), Chenopodium album (CHEAL; growth stage 15), Ipomea hederacea (IPOHE; growth stage 12), and Setaria viridis (SETVI; growth stage 14). Each spray test was replicated three times. The test plants were then grown in a glasshouse under controlled conditions (at 24/18° C. day/night; 16 hours light; 65% humidity) and watered twice a day.

(50) The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at a time period of 21 days following application. The results shown in Table 2 below are mean averages over the two rates of fomesafen, the three replicates and the three replicates.

(51) TABLE-US-00007 TABLE 2 Testing of adjuvant activities in Fomesafen compositions. Mean % Herbicidal Activity Average over Test Adjuvant ABUTH CHEAL IPOHE SETVI all Species 1 Adjuvant 6 31 80 64 25 50 1 Adjuvant 8 36 73 51 13 43 1 Adjuvant 10 28 88 50 17 46 1 No Adjuvant 16 19 16 34 21 2 Adjuvant 8 53 78 92 17 60 2 No Adjuvant 16 46 55 18 34 3 Adjuvant 7 46 94 98 45 71 3 No Adjuvant 43 53 56 20 43 4 Adjuvant 12 74 80 98 77 82 4 Adjuvant 8 75 65 97 65 75 4 Adjuvant 2 57 68 95 53 68 4 Adjuvant 3 47 54 88 37 56 4 Adjuvant 1 74 79 91 65 77 4 Adjuvant 5 60 55 64 49 57 4 Adjuvant 4 51 45 93 53 61 4 Adjuvant 10 56 60 92 65 68 4 No Adjuvant 66 48 50 53 54 4 Adjuvant 11 48 80 98 39 66 4 Adjuvant 9 52 64 88 64 67

Mesotrione Examples

(52) The efficacy of adjuvants 1-12 as an adjuvant for the herbicide mesotrione was tested in a glasshouse against four weed species sown into standard soil in pots and cultivated under controlled conditions in a glasshouse (at 24/18° C. day/night; 16 hours light; 65% humidity). Mesotrione was added to the spray tank as a standard SC (suspension concentrate) formulation.

(53) The plants were sprayed with mesotrione (in the absence of an adjuvant) at rates of 30 and 60 grams of pesticide per hectare using a laboratory track sprayer which delivered the aqueous spray composition at a rate of 200 litres per hectare, using a flat fan nozzle (Teejet 11002VS) and an application volume of 200 litre/ha (at 2 bar). The spray tests were also carried out using mesotrione in conjunction with adjuvants 1-12. The adjuvants were added to the spray solution at a rate of 0.2% v/v unless otherwise stated. All spray solutions also contained 10% w/w of iso-Propanol. The weed species and their BBCH growth stage at spraying were Brachiaria platyphylla (BRAPP; growth stage 13-14) or Brachiaria plantaginea (BRAPL; growth stage 13-14), Commelina benghalensis (COMBE; growth stage 13), Digitaria sanguinalis (DIGSA; growth stage 14), and Polygonum convolvulus (POLCO; growth stage 13-14). Each spray test was replicated three times.

(54) The test plants were then grown in a glasshouse under controlled conditions (at 24/18° C. day/night; 16 hours light; 65% humidity) and watered twice a day. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at a time period of 21 days following application. The results shown in Table 3 below are mean averages over the two rates of mesotrione and the three replicates.

(55) TABLE-US-00008 TABLE 3 Testing of adjuvant activities in Fomesafen compositions. Mean % Herbicidal Activity Average over Test Adjuvant BRAPP COMBE DIGSA POLCO all Species 1 Adjuvant 7 68 80 70 73 1 No Adjuvant 39 47 65 50 2 Adjuvant 6 53 83 83 84 76 2 Adjuvant 8 61 85 84 82 78 2 No Adjuvant 12 60 43 19 33 3 Adjuvant 12 69 84 98 84 3 Adjuvant 8 64 81 92 79 3 Adjuvant 2 52 79 94 75 3 Adjuvant 3 38 83 92 71 3 Adjuvant 1 53 81 81 72 3 Adjuvant 5 48 72 94 71 3 Adjuvant 4 43 83 93 73 3 Adjuvant 10 61 84 95 80 3 No Adjuvant 36 45 80 54 3 Adjuvant 11 58 83 92 78 3 Adjuvant 9 69 82 92 81 Mean % Herbicidal Activity Average over Test Adjuvant BRAPL COMBE DIGSA POLCO all Species 4 Adjuvant 8 33 79 83 93 72 4 No Adjuvant 6 46 26 78 39

Pinoxaden Examples

(56) The efficacy of adjuvants 1-12 as adjuvants for the herbicide pinoxaden were tested in a glasshouse against four weed species, sown into standard soil in pots and cultivated under controlled conditions in a glasshouse (at 20/16° C. day/night; 16 hours light; 65% humidity). Pinoxaden was added to the spray tank as a standard EC (emulsifiable concentrate) formulation.

(57) The plants were sprayed with pinoxaden (in the absence of an adjuvant) at rates of 7.5 and 15 grams of pesticide per hectare using a laboratory track sprayer which delivered the aqueous spray composition at a rate of 200 litres per hectare, using a flat fan nozzle (Teejet 11002VS) at 2 bar. The spray tests were also carried out using pinoxaden in conjunction with adjuvants 1-12. The adjuvants were added to the spray solution at a rate of 0.2% v/v unless otherwise stated. All spray solutions also contained 10% w/w of iso-Propanol. The weed species and their BBCH growth stage at spraying were Avena fatua (AVEFA; growth stage 12), Lolium perenne (LOLPE; growth stage 13), Alopecurus myosuroides (ALOMY; growth stage 13), and Setaria viridis (SETVI; growth stage 13-14). Each spray test was replicated three times. The test plants were then grown in a glasshouse under controlled conditions (at 20/16° C. day/night; 16 hours light; 65% humidity) and watered twice a day. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at a time period of 21 days following application. The results shown in Table 4 below are mean averages over the two rates of pinoxaden, and the three replicates.

(58) TABLE-US-00009 TABLE 4 Testing of adjuvant activities in Pinoxaden compositions. Mean % Herbicidal Activity Test Adjuvant ALOMY AVEFA LOLPE SETVI Average over all Species 1 Adjuvant 7 63 98 78 97 84 1 No Adjuvant 14 25 10 18 17 2 Adjuvant 6 23 82 62 87 63 2 Adjuvant 8 22 84 73 89 67 2 No Adjuvant 1 0 2 2 1 3 Adjuvant 8 2 94 87 94 69 3 No Adjuvant 4 48 7 36 24 4 Adjuvant 12 23 87 76 94 70 4 Adjuvant 8 15 78 42 88 56 4 Adjuvant 2 16 56 28 87 47 4 Adjuvant 3 15 52 22 88 44 4 Adjuvant 1 20 78 41 82 55 4 Adjuvant 5 10 69 21 63 41 4 Adjuvant 4 18 78 30 82 52 4 Adjuvant 10 9 80 25 89 50 4 Adjuvant 11 11 41 15 84 38 4 Adjuvant 9 17 83 40 91 58 4 No Adjuvant 3 9 4 9 6

Cyantraniliprole Example

(59) The efficacy of adjuvants 6, 7, 8 and 10 as adjuvants in compositions containing cyantraniliprole was tested in an aphid/French bean assay. The underside of two week old French bean (Phaseolus vulgaris) plants were infested with an aphid population Aphis craccivora of mixed ages contained in clip cages. One day after infestation, the tops of the plants were treated with a diluted suspension concentrate of the insecticide cyantraniliprole at rates of 3.125, 6.25, 12.5, 25, 50 mg of the insecticide per litre of spray solution, using a top-down laboratory track sprayer, which delivered the spray rate of 200 litres per hectare, using a flat fan nozzle (LU 90-01) at 2 bar. Spray tests were also carried out with a diluted suspension concentrate additionally comprising adjuvants 6, 7, 8 and 10 added to the spray solution at rates of 0.1 and/or 0.2% v/v, based on the quantity of spray liquor. The plants were incubated in the greenhouse for 5 days and the mortality evaluated for the mixed population of aphids. Each experiment was replicated twice and the results were averaged. Table 5 summarizes the results.

(60) TABLE-US-00010 TABLE 5 Testing of adjuvant activities in Cyantraniliprole compositions. Adjuvant Rate % Mean(% Adjuvant v/v MORTALITY) Adjuvant 7 0.2 66.1 Adjuvant 6 0.2 68.5 Adjuvant 8 0.1 62.1 Adjuvant 8 0.2 60.8 No Adjuvant 0 0 Adjuvant 10 0.1 49.8 Adjuvant 10 0.2 70.2

Isopyrazam Example

(61) Adjuvants 6, 7, 8 and 10 were tested as adjuvants for agrochemical compositions comprising isopyrazam.

(62) Two week old wheat plants were inoculated with the fungus Septoria tritici. Four days after inoculation, the plants were sprayed with a diluted suspension concentrate formulation of the fungicide isopyrazam at rates of 6.5, 16, 40 and 100 mg of the fungicide per litre of spray solution, using a laboratory track sprayer which delivered the spray at a rate of 200 litres per hectare, using a flat fan nozzle (LU 90-01) at 2 bar. All spray solutions also contained 10% v/v of iso-Propanol. The leaves of the plants were assessed visually 17-18 days after infection and the damage was expressed as the percentage of the leaf area infected. Each spray test was replicated four times across the four application rates.

(63) The results shown in Table 6 below are mean averages over the four rates of isopyrazam and the four replicates.

(64) TABLE-US-00011 TABLE 6 Testing of adjuvant activities in Isopyrazam compositions. Test Adjuvant Disease Damage Mean 1 Adjuvant 7 12 1 Adjuvant 6 9 1 No adjuvant 65 2 Adjuvant 6 12 2 Adjuvant 8 20 2 No adjuvant 74 2  Adjuvant 10 17 3 Adjuvant 6 7 3 No adjuvant 93 3  Adjuvant 10 14

Epoxiconazole Examples

(65) Adjuvants 6, 7, 8 and 10 were tested as adjuvants for agrochemical compositions comprising epoxiconazole.

(66) Two week old wheat plants were inoculated with the fungus Septoria tritici. Four days after inoculation, the plants were sprayed with a diluted suspension concentrate formulation of the fungicide epoxiconazole at rates of 1.5, 4, 8.5 and 20 mg of the fungicide per litre of spray solution, using a laboratory track sprayer which delivered the spray at a rate of 200 litres per hectare, using a flat fan nozzle (LU 90-01) at 2 bar. Spray tests were also carried out with a diluted suspension concentrate additionally comprising the adjuvants 6, 7, 8 and 10 added to the spray solution at a rate of 0.1% v/v, based on the quantity of spray liquor. All spray solutions also contained 10% v/v of iso-Propanol. The leaves of the plants were assessed visually 17-18 days after infection and the damage was expressed as the percentage of the leaf area infected. Each spray test was replicated four times across the four application rates and the results are shown in Table 7.

(67) TABLE-US-00012 TABLE 7 Testing of adjuvant activities in epoxyconazole compositions. Test Adjuvant Disease Damage Mean 1 Adjuvant 7 12 1 Adjuvant 6 10 1 No Adjuvant 81 2 Adjuvant 6 21 2 Adjuvant 8 36 2 No Adjuvant 86 2  Adjuvant 10 26 3 Adjuvant 6 42 3 No Adjuvant 93