SU1598872A3 - Method of producing derivatives of acrylic acid or their stereoisomers - Google Patents

Abstract

The invention relates to heterocyclic compounds, in particular to the preparation of acrylic acid derivatives of the formula @ where W is pyridinyl or pyrimidinyl, possibly substituted by halogens, C ₁ -C ₄ alkyl, which in turn may be replaced by halogen, phenyl, C ₁ -C _4- alkoxy group

a phenoxy group which, in turn, may be substituted with 1-methoxycarbonyl, 2-methoxyethenyl, halogen, cyano or nitro, cyano, nitro, amino, formamido, or N - oxide group, or W - quinolinyl or quinazolyl possibly substituted by halogen, with W being bound to A by any carbon atom of the cycle, A is oxygen or a group of S (O) _N , where N = 0, and 1 or 2, provided that if W is 5-trifluoromethylpyridinyl-2, A is not oxygen, or their stereoisomers, which have fungicidal properties. The goal is to detect more active compounds. The preparation is carried out from the corresponding hydroxyacrylic acid or its alkali metal alcoholate of the formula @ and dimethyl sulfate, when R is an alkali metal atom, or with a base and dimethyl sulfate, when RH, in a solvent, followed by separation of the target product as a racemate or stereoisomer. 8 tab.

Description

This invention relates to a process for the preparation of new acrylic acid derivatives having valuable fungicidal properties that can be used in agriculture.

The purpose of the invention is the preparation of new acrylic acid derivatives with higher fungicidal activity.

Example 1 Preparation of (E) -me-TIL-2-C2 - (5-chloropyridin-2 -yloxy) O4

phenyl7-3-methoxyacrylate (compound 14 of table 1).

A solution of 2,5-dichloropyridine (7.70 g, 52.03 mmol), potassium carbonate (14.01 g, 101.37 mmol), and disodium o-hydroxyphenylacetic acid (10.20 g, 52.58 mmol) in dimethyl sulfate The oxide (50 ml) is stirred overnight under a nitrogen atmosphere. The dark reaction mixture is poured into water (100 ml) and extracted with ether (3 X 75 ml). The aqueous phase is acidified to pH 6 with concentrated hydrochloric acid. and then extracted with ethyl acetate (3 X 100 ml). The combined organic layers are washed with a saturated solution of sodium chloride (2 x 100 ml), dried and then evaporated under reduced pressure to give 2- (5-chloropyridin-2-yloxy) phenyl acetic acid (5.30 g). In the form of dark brown liquids (IR spectrum, V: 3500-2700, 1600, 1370, 1440, 750 cm), which is used without further purification

stki. 2- (5-Chloropyridin-2-yloxy) phenyl acetic acid (5.20 g; 19.73 mmol) calcium carbonate (5.53 g; 40 mmol) and dimethyl sulfate (2.91 g; 23.07 mmol) are stirred overnight at room temperature in DMF (dimethylformamide) (50 ml). The reaction mixture was poured into water (100 ml) and extracted with ethyl acetate (2 x 75 ml) and ether (1 X 100 ml). The combined organic layers are washed with water (3 x X 75 ml) and saturated sodium chloride solution (2 x 100 ml), then dried and evaporated under reduced pressure. Methyl-2 (5-chloropyridin-2-yloxy) phenylacetate (4.18 g) is obtained as a dark brown liquid, b.p. 150 ° C / 0.1 mm Hg

To a stirred suspension of sodium hydride (0.78 g; 50% oil dispersion) in DMF (40 ml) at -25 ° C is added dropwise a solution of methyl 2- (5-chloropyridin 2 -yloxy) phenylacetate (2 , 90 g; 10.45 mmol) and methyl formate (14.88 g, excess) in DMF. The reaction mixture is partitioned between saturated sodium carbonate solution and ether. The aqueous layer is acidified with concentrated hydrochloric acid to pH 4-5 (desired precipitate), and then extracted with ethyl acetate (3 X 100 ml). The organic extracts are combined, dried and evaporated under reduced pressure to give Methyl -2-2- (5-chloropyridin-2 -yloxy)

phenyl} -3-hydroxyacrylate as an orange-red solid (2.36 g). The solid (2.30 g; 7.54 mmol) is stirred overnight in DMF (50 ml) at room temperature with dimethyl sulfate (1, 21 g; 9.59 mmol) and potassium carbonate (2.44 g; 17, 6 mmol). The reaction mixture is poured into water (100 ml) and then extracted with ethyl acetate (3x100 ml). The combined organic layers are washed with water (3 X 75 ml) and brine (2 X 100 ml), then dried and evaporated under reduced pressure, get brown in viscous fluid. HPLC (50:50 ether / petroleum ether eluent) gave a pale yellow liquid that crystallized on standing (2.14 g). Recrystallization from methanol gives (E) -methyl-2-C2 - (5-chloropyridin-2-yloxy) phenyl 3-3-methoxy acrylate. m.p. 77-78 C.

IR spectrum, o), 1600, 1625, 1260, 1200.

 H-NMR "/ (CDC1,), MD: 3.57 (p.),

3.74 (ZN, s.), 6.75 (1H, d.), 7.41 (111, s.), 8.10 (1H. Brs), 7.1-7.6 (m ). .

Example 2. Using the procedure of Example 1, I get- (E) -methyl-2- 2 - (5 -cyanopyridin-2 -yloxy) phenyl-3-methoxyacrylate (compound 127 tab. About mp. 108.5-109, 54;

 H-NMR, /, MD: 3.58 (ZN, p.),

3.75 (ZN, pp.), 6.9 (1H, d.), 7.1 (1H, d.), 7.28-7.4 (4H, m.), 7.45 (1H, s .) 7.85 (1H. Square.), 8.45 (1H, d.).

Example 3. Preparation of (E) -methyl-2-2- (5-nitropyridine-2 -yloxy) phenyl-3-methoxyacrylate (compound 133 in Table 1).

2- (Hydroxyphenyl) acetic acid (50 g) was added to a solution of hydrogen chloride in methanol prepared from acetyl chloride (25 ml) and methanol (250 ml). This mixture is stirred at room temperature for 3 hours and then left overnight (15 hours). The mixture was concentrated under reduced pressure and the residue was taken up in ether (250 ml) and washed with an aqueous solution of sodium bicarbonate until vigorous evolution of gas ceased. The ether solution is dried and then concentrated under reduced pressure, the resulting solid is recrystallized from diethyl ether / gasoline.

515988726

methyl- (2-hydroxyphenyl) acetate is obtained under reduced pressure tat UU g, yield 92%) as a white, the resulting yellow oil solidifies after trituration with a mixture of diethyl ether and gasoline.

Recrystallization from dry methanol gives (E) -methyl-2 (2-benzyloxy-phenyl) -3-methoxyacrylate as a white crystalline solid 10 (5.44 g, yield 17%), i.e. 76-77 C. IR spectrum V, cm-: 1710, 1640. H-NMR (90 MHz) D M.D.: 3.63 (ZN,

. .x .. s.), 3.75 (ZN, s.), 5.06 (2H, s.).

bromide (23.94 g) in DMF (50 ml) with 6.80-7.40 (9H, m.), 7.50 (1H, s), stirring at room temperature | 5 (E) -methyl -2- (2 -benzoloksifenil) -3- type. After 18 hours, the mixture was poured into methoxyacrylate (5.44 g), dissolved in water (500 ml) and extracted with diethyl ethyl acetate (50 ml) and 5% pure ether (2 x 400 ml) was added. Extracts palladium on carbon (0.25 g). The mixture is washed with water (3 x 150 ml) and the salt-water mixture is hydrogenated under pressure with a withdrawal solution (100 ml), dried and the filter is removed through stirring until stirred through silica gel (50 g, Merck 60). hydrogen, then filtered, then concentrated under reduced through celite and silica gel (50 g, pressure, to obtain a yellow oil. Pe-Merk 60). The concentration of the filtrate distillation at 160 s / 0.05 mm Hg gives, under reduced pressure, gives (E) -methyl-2-benzyloxyphenylacetate in the form of 25 tyl-2- (2-hydroxyphenyl) -3-methoxy-acycid oil (26.99 g: nMvnn rilat as a white crystalline

crystals, so pl. 70-72 С

IR, v, cm: 3420, 1715.; n-NMR (90 MHz) J: 3.70 (2H, s),

3.75 (ЗН, с.), 6.80-6.95 (2Н, m.),

7.05-7.10 (1H, m.), 7.15-7.25 (1H,

m.), 7.40 (1H, p.).

Methyl- (2-hydroxyphenyl) acetate (21.0 g) was dissolved in DMF (200 ml), potassium carbonate (19.35 g) was added. Benzyl bromide (23.94 g) in DMF (50 ml) is added dropwise to the mixture with stirring at room temperature. After 18 hours, the mixture is poured.

colorless oil (26.99 g; yield 83%).

IR spectrum, cm -: 1730, H-NMR (90 MHz) J, M. D: 3.60

solids (3.76 g, yield 99), so pl. 125-126 C.

- .. -, ......, IR spectrum O, 3400, 1670.

(ZN, s.), 3.75 (2H, s.), 4.10 (2H, s.) 30 (270 MHz) /, ppm: 3.80 6.80-7.40 (9H , m.), (ЗН, с.), 3.90 (ЗН, с.), 6.20 (1Н, с.),

A mixture of methyl-2-brnchmppt ,, 6.80-7.PP m 7 tp / ty .. l

A mixture of methyl 2-benzyloxyphenyl acetate (26.99 g) and methyl formate (126.62 g) in dry DMF (300 ml) was added dropwise to a stirred suspension of sodium hydride (50% oil dispersion, 10, 13 g) in DMF (300 pieces) at About with. After stirring at 0 ° C for 2 hours, the mixture is decanted.

   Y - - f y - ". F- V,. | /

6.80-7.00 (2H, m), 7.10-7.30 (2H, m.), 7.60 (1H, s.).

(E) -Methyl-2- (2-hydroxyphenyl) -3- 35 methoxyacrylate (0.30 g, 1.44 mmol), 2-chloro-5-nitropyridine (0.46 g; 2.88 mmol). and potassium carbonate (0.40 g; 2.88 mmol) are stirred together with. DMF (20 ml) at room temperature in

into water (1000 ml) and washed with diethyl-10 at room temperature in viv1 ether (2 X 150 MP), Aqueous ™ solution. Through. For 18 h, the reaction is acidified to a pH of 46M hydrochloric acid and is then extracted with diethyl ether-two-diethyl ether, rum (2 x 350 kp). Extracts and the combined ethereal layers are washed

concentrated under reduced pressure s G saline, get the crude methyl 2- (2-ben-f then dried. Poluchenie solution

Zyloxyphenyl) -3-hydroxyacrylate as a yellow oil, IR spectrum, V: 1720

1660.

Crude methyl 2- (2-benchip, g, ate with silica gel (diethyl phenyl eluent) -3-hydroxyacrylate in hydride 2 G2- (2- (5-nitrous dry DMF (100 ml), added carbonate ™ P ": 2 „-ily (si) phenyl-3-methoxyaccalium (29.0 g). Then, D / n T ° 0 DMF (10 ml) is added dropwise with stirring. After s5 Allow water is added and the solution is extracted with diethyl ether (2 x 300 ml) After washing with water (3 x 150 nl) and brine, the extracts are dried and

 - “- .jr icnnoiri i cUJllstJp

filtered through silica gel and then concentrated to give a pink solid. Chromatography on a column of silica gel (eluent - diethyl

X. - 1 - lh And H - JVl.l lcHV

rilat (240 mg) as a yellow gum, which crystallizes on standing, m.p. 107-109 C.

Example 4 Using the procedure of Example 1, (E) -methyl-2-2- (4-chloropyrimidin-2 -yloxy) J-3-methoxyarylate (compound 61 of Table 1) is obtained in the form of an oil which crystallizes - MP (270 MHz) /, ppm: 3.80 (ZN, s.), 3.90 (ZN, s.), 6.20 (1H, s.),

6.80-7.PP m 7 tp / ty ..l

   Y - - f y - ". F- V,. | /

6.80-7.00 (2H, m), 7.10-7.30 (2H, m.), 7.60 (1H, s.).

(E) -Methyl-2- (2-hydroxyphenyl) -3-methoxyacrylate (0.30 g, 1.44 mmol), 2-chloro-5-nitropyridine (0.46 g; 2.88 mmol). and potassium carbonate (0.40 g; 2.88 mmol) are stirred together with. DMF (20 ml) at room temperature in

    room temperature in the pot. Through. 18 hours of reaction — ° C “Y” “- two times with diethyl ether, the combined ether layers are washed

G saline, f then dried. Half solution

 with silica gel (eluent - diethyl p1ridiG2 G2- (2- (5-nitro ™ P: 2: -ily s) phenyl-3-methoxy-ac

 - “- .jr icnnoiri i cUJllstJp

filtered through silica gel and then concentrated to give a pink solid. Chromatography on a column of silica gel (eluent - diethyl

 with silica gel (eluent - diethyl p1ridiG2 G2- (2- (5-nitro ™ P: 2: -ily s) phenyl-3-methoxy-ac

X. - 1 - lh And H - JVl.l lcHV

rilat (240 mg) as a yellow gum, which crystallizes on standing, m.p. 107-109 C.

Example 4 Using the procedure of Example 1, (E) -methyl-2-2- (4-chloropyrimidin-2 -yloxy) J-3-methoxyarylate (compound 61 of Table 1) is obtained in the form of an oil, which is crystallized by trituration with ether; m.p. 120- 121.5 S.

 H-NMR, MD: 3.60 (ZN, s.), 3.80 (ZN, s.), 6.60 (1H, d, 1 "4 Hz), 7.40 (1H, s.), 8.40 (1H, d., Hz);

EXAMPLE 5. (E) -Methyl-2-2- (5-chloro-chridin-2-ylthio) phenyl-3-methoxy-acrylate (compound 14, table 2) in the form of a resin is obtained using the procedure example 1, the IR spectrum: 1700, 1630 cmL

EXAMPLE 6 Using the procedure of Example 1, (E) -methyl-2-2 -p- (5-bromopyridin-2 -ylsulfonyl) phenyl} 3-methoxyacrylate (compound 1 of table 3) (E) -methyl is obtained -2-C2 - (5-bromopyridin-2 - shtsulfonyl) phenyl T-3-methoxy-acrylate (compound 2, table 3), (E) -metsh-1-2-G2 - (5-bromopyridin-2-ylsulfonyl) -phenyl 5 -3-methoxyacrylate (compound 2, table 3), (E) -methyl-2-2- (5-bromopyrid-2 -ylsulfonyl) phenyl} -3-methoxy-acrylate in the form of a resin and (E) -methyl -2- 12 - (5-bromopyrid-2 -ylsulfrinyl) FeN-NIL) -3-methoxyacrylate as its solid substance.

Appro. 7. Using the procedure of Example 1, (E) -methyl-2-G2 (5-methoxycarbonylpyridin-2 -yloxy) phenyl-3-methoxyacrylate (compound 141, Table 1) is obtained in the form of an oil.

H-NMR J, MD: 3.47 (ZN, s.), 3.62 (ZN; s.), 3.82 (ZN, s.), 6.75-7.3 (5H, m.), 7.32 (1H, s.), 8.15 (1H, q.), 8.72 (1H, d.).

Example 8. According to the procedure of Example 1, (E) -methyl-2-2 - (benzyloxycarbonylpyridin-2 -yloxy) -phenyl J-3m-methoxyacrylate (compound 184, Table 1) is obtained in the form of a resin.

H-NMR J, M.D .: 3.55 (3N, s.), 3.60 (3N, s.), 5.35 (2H, s.), 6.82 (1H, d), 7.18-7.48 (m.), Incl. singlet at 7.39, 8.25 (1H, apt.), 8.25 (W, d.).

Example 9. Preparation of (E) -methyl-2-2- (P-methylpyridin-3-yloxy) phenyl-3-methoxyacrylate (compound 45 tabLo 1).

b-Methyl-3-hydroxypyridine (9.5 g) is suspended in toluene (30 ml) and treated with aqueous potassium hydroxide (4.9 g in 3 ml of water). The mixture is stirred vigorously for 15, then evaporated under reduced pressure. The last traces of water are removed by repeated evaporation in the presence of toluene. The resulting brown p-black solid is treated with a mixture of 2- (2-bromophenyl) -1,3-dioxolane (10.0 g), copper chloride (60 mg) and tris-G2- (2-methoxyethoxy) ethyl} amine (0.194 g ) to solubilize copper salt in dry DMF (25 ml) and the mixture is heated at 155 ° C with stirring under nitrogen atmosphere for 30 hours. Additional copper chloride is added (60 mg) and heating is continued for another 14 hours.

The mixture is cooled, poured into water and extracted with ethyl acetate. The extract is washed with 2 n. aqueous solution of sodium hydroxide and water, followed by extraction with 2N hydrochloric acid. The acidified aqueous extract is treated with solid potassium carbonate to pH 8 and then extracted with ethyl acetate. The organic extract is dried, and then evaporated under reduced pressure, to obtain 2- (b-methylpyridin-3 -yloxy) benzaldehyde (2.2 g) as an oil.

IR spectrum V, cm-: 1697, 1606, 1480 H-NMR D M.D.: 2.58 (ЗН, с.), 6.86 (1Н, с.), 7.28 (ЗН, m. ), 7.55 (1H, t.), 7.95 (2H, m.), 8.36 (1H, m.), 10.53 (1H, s.).

2- (6-Methylpyridin-3-yloxy) benz- (2.08 g) and methylsulfinylmethyl sulfide (1.21 g) are dissolved in dry THF (15 ml) and Triton B (1.5 ml) is added slowly dropwise with stirring at room temperature. The mixture was allowed to stand overnight, diluted with water and extracted with ethyl acetate. The extract is then, and then evaporated under reduced pressure, an orange-brown oil (3.2 g) is obtained. The oil is treated with a methanolic solution of hydrogen chloride (25 ml, 2.5 N) and left at room temperature. The solution is then diluted with water and adjusted to pH 8 by the addition of sodium carbonate. The mixture is extracted with ethyl acetate, the extract is dried and evaporated, a brown oil (2.23 g) is obtained, which is purified by high-performance liquid chromatography (eluant 1: 1, ethyl acetate / hexane mixture) to give methyl 2- (b- methylpyridine-3-hydroxy-phenylacetate as a yellow oil (1.53 g).

IR spectrum 1237.

d cm-: 1747, 1488,

 , MD: 2.54 (3N, p.), 3.63 (3N, p.), 3.64 (2H, p.), 6.84 (1H, d), 7.24 ( 5H, m.), 8.3 (1H, d.).

A mixture of methyl 2- (6-methylpyridin-3-yloxy) phenyl 7-acetate (1.3 g) and methyl formate (1.52 g) in DMF (5 ml) is added dropwise to a suspension of sodium hydride (316 mg, 50% dispersion in

oil) R PMF MF V, ..1. The liquid spray spray T1 ° g and stirring 10 on attapulgite clay granules

Pii .J I.- Of GT TTOGL j nrfr-r-t «« .. ...

Calcium Fonat 5

Nonylphenol ethoxylate (13 moles of ethylene oxide) - 10 Alkylbenzene45

Example 11. The active ingredient is dissolved in methylene dichloride and the resulting liquid is sprayed.

at 5 ° C. After stirring for 4 hours, the mixture is diluted with water by adding glacial acetic acid to pH 4-5 and extracted with ethyl acetate. The extract, after drying and evaporation15 under reduced pressure, type 2-C2 - (6-methylpyridin-3-yloxy) phenyl-3-hydroxyacrylate as a yellow oil (1.15 g).

G. (ZN, -C.), 3.6320 (ZN.), 6.89 (1H, s.), 7.2 (5H, m.),

, (1H, d.).

The oil (1.14 g) was dissolved in DMF (15 ml), potassium carbonate (1.1 g) was added and the mixture was stirred for 25 minutes. Diethyl alfate (0.53 g) was dissolved in DMF (5 ml) and the solution was added to the mixture. The resulting mixture is stirred for 30 minutes.

 RST

the evaporator is then allowed to evaporate, to give a composition in the form of granules,% g

Compound 14 of Table 1. 5 5 Attapulgite granules 95 Example 12. The composition is prepared by grinding and mixing three ingredients,%:

Connection 61 table. 1 50 Mineral oil 2 Chinese clay 48 Example 13. Dust powder is prepared by grinding and mixing the active ingredient with talc Compound 61 tab. 1 5 Talc52

Example 14. A suspension concentrate is prepared by grinding the ingredients in a ball mill with 1 ison ball mill and nR- is then diluted with water and the resulting ECG / g emulsion neutralizer is formed by forming an aqueous suspension. g ,, t „,„ „.....-. M3Mti) Ib4eH

. s.), s.), 6.88

m

.), 7.51

the emulsion is extracted with ethyl acetate. The extract is dried and evaporated under reduced pressure to give a yellow oil (2.06 g), which is purified with HPL C (eluant / ethyl acetate), „(E) -methyl - (6-Methylpyridin-3-yloxy) phenylJ- 3-methoxyacrylate as a pale yellow oil (0.73 g).

IR spectrum), cm-: 1705, 1642 1488.

, 2.52 (ЗН 3.63 (ЗН, с.), 3.81 (ЗН,

(1H, d.), 7.04-7.32 (5H,

(1H, s.), 8.26 (1H, d.).

Similarly, compounds of Tables 1-3 are prepared. The structure of all compounds is confirmed by the data of the spectra of proton magnetic resonance (H NMR)

Examples of compositions for agricultural and horticultural use can be obtained from the proposed compounds.

Example 10. An emulsifiable concentrate is prepared by mixing and mixing the ingredients until they all dissolve,%:

Connection 61 table. 1 th

Benzyl alcohol AOR

Dodecylbenzenesul40

ten

one

49

iS

50

55

Noah mixture with water, “. Compound 61 Lignosulfonate sodium Bentonite clay Water

This formulation can be used as a spray after dilution with water or directly.

Example 15. A wettable powder form is prepared by mixing and grinding ingredients to form a homogeneous product,%:

Connection 61 table. 1 Sodium lauryl sulfate Lignosulfonate-sodium Silica Chinese clay

Example 16 Compounds were tested against a variety of fungal diseases of plant foliage. The technology applied in the tests was as follows.

The plants were grown in compost for John Innes pots (Jft 1 or 2) in mini-pots with a diameter of 4 cm. Test compounds were converted into a prepared form of the preparation either by grinding with a dispersion T or in solution in acetone or

25 2 5

25 43

1598872

ten

 ..1.spot liquid sprayed on attapulgite clay granules

 ...

Calcium Fonat 5

Nonylphenol ethoxylate (13 moles of ethylene oxide) - 10 Alkylbenzene45

Example 11. The active ingredient is dissolved in methylene dichloride and the resulting liquid is sprayed.

 RST

the evaporator is then allowed to evaporate, to give a composition in the form of granules,% g

Compound 14 of Table 1. 5 5 Attapulgite granules 95 Example 12. The composition is prepared by grinding and mixing three ingredients,%:

Connection 61 table. 1 50 Mineral oil 2 Chinese clay 48 Example 13. Dustov powder is removed by grinding and mixing the active ingredient with talc Compound 61 tab. 1 5 Talc52

Example 14. Suspension concentrate is prepared by grinding the ingredients in a ball mill with about 1 use of a ball mill and nR by forming an aqueous suspension of measurements. 1 is used for ball milling of nR-30 by forming an aqueous suspension. ...-. M3Mti) Ib4eH

Yu "

40

ten

one

49

iS

50

55

Noah mixture with water, “. Compound 61 Lignosulfonate sodium Bentonite clay Water

This formulation can be used as a spray after dilution with water or directly.

Example 15. A wettable powder form is prepared by mixing and grinding ingredients to form a homogeneous product,%:

Connection 61 table. 1 Sodium lauryl sulfate Lignosulfonate-sodium Silica Chinese clay

Example 16 Compounds were tested against a variety of fungal diseases of plant foliage. The technology applied in the tests was as follows.

The plants were grown in compost for John Innes pots (Jft 1 or 2) in mini-pots with a diameter of 4 cm. Test compounds were converted into a prepared form of the preparation either by grinding with a dispersion T or in solution in acetone or

25 2 5

25 43

P

mixtures of acetone and ethanol, which were diluted to the required concentration immediately before use. In the case of diseases of the foliage, preparations (100 hours, per million of the active ingredient) were sprayed onto the leaves and applied to the roots of plants in the soil. Sprays were applied to the maximum retained on the surface and the roots were moistened to a "final concentration equivalent to about 40 ppm of active ingredient in dry soil. When applied to cereal sprays, Tween 20 was added to get a final concentration. 0.05%.

In the case of most of the tests, the compound was applied by applying to the soil (to the roots) and to the foliage (spraying) one or two days before the infection of the plant with the disease "The exception was the test against Erysiphe graminis, in which the plants were inoculated 24 hours before processing. Deciduous pathogens were introduced by spraying spore suspensions onto the leaves of test plants. After inoculation, the plants were placed in an appropriate environment to allow the development of an ol disease, and then incubated until the inoculation was ready for evaluation. The period between inoculation and evaluation varied from 4 to 14 days, depending on the disease and environmental conditions. , 35

The disease control was recorded according to the following scale: 4 no disease; 3 tracks - 5% disease on untreated plants; 2 6-25% of the disease on untreated plants; 1 - 26-59% of the disease on untreated plants; About 60-100% of the disease on untreated plants. The results are shown in Table. four.

Example 17o This example illustrates the ability of compounds 14-16, 22, 61, 122 and 138-140 of the table, 1 to regulate plant growth.

These compounds were tested for the activity of regulating plant growth in six plant species. The plant species used in this screen are shown in Table 5, indicating the leaf stage at which the plants were sprayed. 55

The preparation of each compound was applied in the amount of 4000 ppm / 4 kg / ha with a field volume of 1000 l / ha with 15,98872 .12

using a crawler sprayer and nozzle SS 8004E (Teljet). Additional tests were conducted on | tomatoes using 2000 and 500 ppm After spraying, the plants were sprayed in a greenhouse with a temperature of day and night. The exception to this test was cereals of a temperate climate, wheat and barley, which were patched at daytime temperatures of 13–1 s and temperatures at night of 11–13 ° C. When necessary, an average photoperiod duration of 16 hours (minimum 14 hours) was applied. additional lighting

After 2-6 weeks of being in the greenhouse, depending on the type and time of the Year, the plants were assessed visually for morphological characteristics compared to control plants sprayed with blank formulations (without active substance). The results are presented in Table 2. five

Example 18. This example illustrates the insecticidal properties of some compounds.

The activity of each compound was determined using different insect mites and Nematode pests. The compound was used in the form of liquid preparations containing from 100 to 500 ppm by weight of the compound. The preparations were prepared by dissolving the compound in acetone and diluting the solutions with water containing 0.1% by weight of a wetting agent with the trade name SIN-PERRONIK U1H

The test procedure applied to each of the pests was basically the same and involved placing a number of pests on the environment, which was usually the host plant or the feed that the pests ate, and the treatment of the environment or pests or both of these and other drugs. Pest mortality was assessed by periods, usually varying from one to seven days after treatment.

The test results are given in Table 6 of each of the products, taken in an amount in parts per million, given in the second column, with a scale for estimating mortality as 9, 5 or O, where 9 is 80-100% mortality (70 - TOO% reduction times - 1598872

root versus untreated plants in the case of Melcidogy incognita, 5 means 50-79% mortality (50-69% reduction in root development in the case of Melcidogyne incognita) and O means less than 50% mortality (decrease in growth of roots) about

Table 7 and 8 list the pest organism used, identified by the letter code, the types of pests, the environment or feed, the type and duration of the test.

14

W - pyridinyl or pyrimidinyl, possibly substituted by halogen With-C alkyl, which, in turn, may be replaced by halogen, phenyl

The fungicidal action proposed by -, -alkoxygroup, phenoxygroup, .4. I ,, h 5 which, in turn, can be

substituted by 1-methoxycarbonyl-2-methoxy-ethenide, halogen, cyano or nitro, cyano, nitro, amino, formamido, or N-oxide group, or W-quinolinyl or quinazolyl, possibly substituted by halogen, and W is bound with A love cycle carbon atom, A - oxygen or group 8 (0),

 J l-l. , V .. .1b- "L X L .., C -I -V OC.l J

compounds (compound 11 of table. 1) were compared with strobilurin A of the formula pp.

OSI

20

thirty

- TG

2, then A is not oxygen, or their stereoisomers, characterized in that the compound of the general formula

SNS02S

The test was carried out in accordance with 25 p O or 1, or 2, provided that the VII was carried out with the procedure described in Example 5-trifluoromethylpyridinyl-16, but the compounds were tested at a concentration of 254 / ml.

Compound 11 was applied by spraying the foliage, and strobilurin A was applied to the foliage and soil under the roots. The results were obtained (using the estimates that are defined in Example 16), given in Table „9„

These results indicate that compound 11 of Table 1 is more active than strobilurin A as a plant fungicide even when strobilurin A was used by combining foliar spray and root impregnation, while compound 11 was used only by foliar spray . Compounds

35

40

1 belongs to the group of low-toxic compounds. Invention Formula

The method of obtaining derivatives of acrylic acid of the General formula

where W and A have the indicated meanings;

R is a hydrogen or an alkali metal atom,

is reacted with dimethyl sulfate when R is an alkali metal atom, or with a base and dimethyl sulfate when R is hydrogen, in a solvent followed by the introduction of a target in the form of a racemate or stereoisomer,

14

W - pyridinyl or pyrimidinyl, possibly substituted by halogen With-C alkyl, which, in turn, may be replaced by halogen, phenyl

thirty

- TG

2, then A is not oxygen, or their stereoisomers, characterized in that the compound of the general formula

 25 n O or 1 or 2, provided that 5-trifluoromethylpyridinyl

where W and A have the indicated meanings;

R is a hydrogen or an alkali metal atom,

is reacted with dimethyl sulfate when R is an alkali metal atom, or with a base and dimethyl sulfate when R is hydrogen, in a solvent followed by the introduction of a target in the form of a racemate or stereoisomer,

15

1598872. W-0 V02CH3

sixteen

Continuation of table 1

---- J -: ---------- C 1 3IZLXllZ

405 - (TDHdlTnnMPTHn lrTtTT-nj-

3 - (Trifluoromethyl) pyridine-3-yl

415 -Methoxypyridin-z -yl

426 - Fluoropyridin-Z-yl

436-Horpyridin-3-yl

446-Bromopyridin-Z-il

456-Methylpyridin-3-yl

466 - (Trifluoromethyl) pyridine-3-yl

476 -Methoxypyrim din-3-yl

482 - Fluoropyridin-4-yl

492-Chloropyridin-4-yl

502-Bromopyridin-4-yl

512, -methylpyridin-4-yl

522 - (Trifluoromethyl) pyridine-4-yl

53 2 -Methoxypyridin-4-yl

54Z - Fluoropyridin-4-yl

553-Chloropyridin-4-yl

563-Bromopyridin-4-yl

573-Methylpyridin-4-yl

583 - (Trifluoromethyl) pyridine -4-yl

593 -Methoxypyridin-4-yl

604-Fluoropyrimidine-2-yl

61 62 63 64

65 66 67 68 69 70

71 72 73 74 75 76

77 78 79 80 81 82

83 84 85

4-Chloropyrimidine 2 -yl 4 -Bromopyrimidine-2 -yl

4-Methylpyrimidin-2 -yl 4 - (Trifluoromethyl) -pyrimidin-2 -yl

4 -Mutoxypyrimidin-2 -yl 5 -Fuorpyrimidine-2 -yl

5-Chloropyrimidine-2 -yl 5 -Bromopyrimidin-2 -yl 5 -Methylpyrimidine-2 -yl 5 - (Trifluoromethyl) pyrimidin-2 -yl

5 -Methoxypyrimidin-2-yl 2 -Fluoropyrimidine-4-yl 2-Chloropyrimidine-4-yl 2 -Bromopyrimidine-4 -yl 2-Methyl pyrimidine-4 -yl

2- (Trifluoromethyl) pyrimidin-4-yl

2 -Met6xypirimidin-4-yl 5-Fluoropyrimidine-4-yl

3-Chloropyrimidine-4 -yl 5 -Bromopyrimidine-4 -yl

5 | -Methoxypyrimidine-4-yl

5- (Trifluoromethyl) pyri-midin-4-yl

5 -Methoxypyrimidin-4-yl

6-fluoropyrimidine-4 -1sh

6-Chloropyrimidine-4-yl

nnn

nnn

nnn

nnn

nnn

nnn oil

NNN

 NNN

NNN

 nn

nn

nn

nnn

nnn

nnn

nnn.

nnn

nnn

n n, l:

nn nn nn

nnn120nnn121, 5

n n

nn

nn n. n. n n

nnn resin

N nn

nn

nnn

nnn

nnn

nn n

nn -n

nnn

nnn

nnn

nnn

nnn

nnn

nnn

nnn.

nnn

nnn

nnn

HER

Yo

I

E

I

HER

Yo

E

E

E

E E E

1 I

. E

i

E

E E E

E I

Yo yo yo i

E E E

i

HER

E

E

m

E

Yo yo yo

E

E

i

Yo

Continuation of table 1

HER

Yo

E

HER

Yo

E

E

E

E E E

I

. E

i

E

E E E

E I

Yo yo yo i

E E E

i

HER

E

E

m

E

Yo yo yo

E

E

i

Yo

Continued table. one

25

1598872

26

. Continued ta bl. one

271598872.28

Continued table. 2

5-bromopyrimidine-2-yl

5-Methylpyrimidin-2-yl

5- (Trifluoromethyl) pyrimidine 5-methoxy pyrimidin-2-yl

2-Fluoropyrimidine-4-yl

2-Chloropyrimidine-4-yl

2-Bromopyrimidine-4-yl

2-Methyl pyrimidium-4-yl

2 - (Trifluoromethyl) pyrimidine

-il

H

n

H

nn nn nn

nn nn nn nn

4 nn nn nn nn

ng I

E

 E

E §

I e yo

Geometry of beta-methoxyacrylate group.

Geometry of beta-methoxyacrylate group

Table 4

33

25 ppm, spraying foliage only. 40 ppm, spraying foliage only. 10 ppm, spraying foliage only.

D Table

vegetative ma, the material used for screening

11P John Innes Pot Compost

1598872

34 Continuation of table 4

Note. Key III 2000 ppm + 500 ppm; immaturity effect G; apical lesions of the AR; tillering or formation of escape shoots T; skipping means an effect of less than 10%; NT indicates that the compound was not tested against this species.

Tetranychus uritcae

(spider mites

and ichky) Chilo partellus

(corn grinders

stem) Diabrotica balteata

(leaf beetle larvae)

. Musca domestica

(indoor flies - adults)

Meloidoqyue incognita (tomato nematode of root growths of the larvae)

Table 6

.Table 7

Contact

Residual Residual Contact

Poluinvitro Residual

T a b l and c a 8

Compound A Compound 11

tabLo 1

Table 9

About 2

Oh oh

ABOUT

four

Claims (6)

Claim A method of obtaining derivatives of acrylic acid of the General formula SOOSNz WA £ and Υ main ₃ - * where W is pyridinium or pyrimidinyl, possibly substituted by halogens With _t -C ₄ alkyl, which, in turn, can be replaced by halogen, phenyl, C _f -C ^ -alkoxy, phenoxy, which, in turn, can be substituted by 1-methoxycarbonyl-2-methoxyethenyl, halogen, cyano or nitro, cyano, nitro, amino, formamido or N-oxide group, or W-quinolinyl or quinazolyl, possibly substituted by halogen, and W is bonded to A by any atom carbon cycle, A is oxygen or group 8 (0) ^, where η = 0 or 1, or 2, provided that if W is 5-three tormetilpiridinil2, then A is not oxygen, or their stereoisomers, characterized in that a compound of general formula СООСНз W ~ A g άу OR where W and А have the indicated values; R is hydrogen or an alkali metal atom, is reacted with dimethyl sulfate when R is an alkali metal atom, or with a base and dimethyl sulfate when R is hydrogen, in a solvent, followed by the introduction of the target product in the form of a racemate or with a temer. W-0? ° 2 ^CH 3 x-Jk C W ^h sn Ί γ6 f ¹ f Table! z main ₃ Compound W X Y Z Mp. ° C Olefin * Isomer * 1 '. ’2 3. 4 '5 6 Ί 8 1 3-fluoropyridin-2'-yl N n n 2 Z ¹ -Hlorpiridin-2'-yl N • n n 3 3'-bromopyridin-2'-yl n n n 4 3'-Methylpyridin-2 ¹ -yl N n n 5 3 '- (trifluoromethyl) pyridin-2'-yl I n n 6 3'-methoxypyridin-2'-yl N n n 7 4'-FluoropyrIdin-2'-yl N n n 8 4'-chloropyridine ~ 2'-yl n n n 9 4'-bromopyridin-2'-yl n n n 10 4'-Methylpyridin-2 '' - sludge n n n Smoda eleven 4 '- (trifluoromethyl) pyridin-2'-yl n n n Resin 12 4'-Methoxypyridin-2'-yl n n n thirteen 5'-fluoropyridine- / -yl n n n 14 5'-chloropyridin-2'-yl n and I 77-8 fifteen 5'-bromopyridin-2'-yl and n n 104.6- 105,4 16 5'-Methylpyridin-2'-yl n H I Resin 17 5 '- Methoxypyridin-2'-yl n N n 18 6 '-Fluoropyridin-2' -yl n n n 19 6'-chloropyridin-2'-yl n n n 20 b '-Bromopyridin-2'-yl n n n 21 B ¹ -methylpyridin-2'-yl n n n Resin 22 6 '- (Trifluoromethyl) pyridin-2' -yl n n n Resin 23 6'-methoxypyridin-2'-yl n n n 24 2'-Fluoropyridin-3'-yl n n n 25 2'-Chloropyridin-Z'-yl n n n 26 2'-Bromopyridin-Z'-yl n n n 27 2'-Methylpyridin-3'-yl N n n 28 2 ’- (trifluoromethyl) pyridin-3'-yl n n n 29th 2'-Methoxypyridin-3'-yl n n n thirty 4'-Fluoropyridin-3'-yl n n n 31 4'-Chloropyridin-3'-yl n n n 32 4'-Brompyridin-Z'-nl n n n 33 4'-Methylpyridin-3'-yl n n n 34 4 ^x - (Trifluoromethyl) pyridin-3'-yl n n n 35 4'-Methoxypyridin-3'-yl Ή N n 36 5 '-Fluoropyridin-3' -yl n •IN n 37 5 ^1- Chloropyridin-3 ¹ -yl n n n 38 5'-Brompyridin-Z'-yl n n n 39 5'-Methylpyridin-3'-yl n n •and 1M1Ya iniw> w> w minininimiw κιη> n> n in »n in in in m m> n. fuh-imipiiM inin in; n, nth η n.n-n 17 1598872 18 Continuation of the table 1 1 1 ³ J..L J_ ± 1 ⁶ 1 ¹ ] ⁸ 40 5 '- (Trnfluoromethyl) pyridin-3' -yl n n n E 41 5'-Methoxypyridin-3'-yl n n n Yo 42 6'-Fluoropyridin-3 ^/ -yl n n n E 43 6'-Chloropyridin-3'-yl and n n Yo 44 6'-bromopyridin-3'-yl n n n Yo 45 6'-Methylpyridin-3'-yl n n n Oil Yo 46 6 '- (trifluoromethyl) pyri- din-3'-yl n n n E 47 6 '-Metoxypyridin-Z ⁷ -yl 'N n n Yo 48 2'-Fluoropyridin-4'-yl n n n B 49 2 * -chloropyridin-4'-yl 'n n n E fifty 2'-Bromopyridin-4 ^G -yl n n n E 51 2'-Methylpyridin-4'-yl n n n E 52 2 '- (Trnfluoromethyl) pyri- din-4'-yl n n n I ^s 53 2 ^Z- Methoxypyridin-4 ^/ -yl n n n • E 54 3 '-Fluoropyridin-4 ^/ -yl n n n E ' 55 3'-Chloropyridin-4'-yl n n n Yo 56 3'-bromopyridin-4'-yl n n n E 57 3 ^x- Methylpyridin-4'-yl n n n Yo 58 3 '- (Trnfluoromethyl) pyri- din-4'-yl n n n and . E 59 3'-Methoxypyridin-4-yl n n Έ 60 4-Fluoropyrimidin-2'-yl n n . n E 61 4'-Chloropyrimidin-2'-yl n n n 120- E 62 4 '-Bromopyrimidin-2 ^/ -yl n n n 121.5 E 63 4'-Methylpyrimidin-2'-yl. n n n E 64 4 '- (Trnfluoromethyl) -piri- ’ midin-2'-yl n n n E 65 4'-methoxypyrimidin-2'-yl n n 'n E 66 5'-Fluoropyrimidin-2 '-yl n n Yo 67 5'-Chloropyrimidin-2'-yl n n n Resin Yo 68 5 ^1- Bromopyrimidin-2'-yl n n n Yo 69 5'-Methylpyrimidin-2'-yl n n n Yo 70 5 / - (Trnfluoromethyl) pyri- midin-2'-yl n n n Yo 71 5 ^x- methoxypyrimidin-2 ^x- yl n n n Yo 72 2'-Fluoropyrimidin-4'-yl n n n Yo ' 73 2'-chloropyrimidin-4'-yl n n n Yo 74 2 '-Bromopyrimidin-4' ~ yl n n  n E 75 2-Methylpyrimidin-4'-yl n n n  ‘ Yo 76 2 '- (Trnfluoromethyl) pyrimidin-4 ^/ -yl n n n E 77 2 ¹ -Met0xypyrimidin-4 ^/ -yl n n n E 78 5'-Fluoropyrimidin-4'-yl n n n Yo 79 5'-chloropyrimidin-4'-yl n n n Yo 80 5 '-Bromopyrimidin-4' -yl n n n Yo 81 . 5'-Methoxypyrimidin-4'-yl n n n • Yo 82 5 ¹ - (Trnfluoromethyl) pyrimidin-4'-yl n n n E 83 5 '-ΜετοκςΗΠΗρΗΜΗΑΗΗ-4 ^ζ -ΗΠ n n n E 84 6 '-Fluoropyrimidin-4' -yl n n Ή Yo 85 6'-Chloropyrimidin-4'-yl n n n Yo 1598872. '20 2. 100 101 102 103 104 Ί05 106 107 108 109 1 10 112 113 114 116 117 118 119 Continuation of the table. 1 I1I1 s <S1M <s1yy1y1 s> hi s <s' s · ωι ωι and * mchan ωι s> ω <ω <«1 ωι 6'-Bromopyrimidin-4 ¹ 6'-Methylpyrimidin-4'-yl 6 '- (Trifluoromethyl) pyrimidine- · ^ -yl 6 '-Metoksipir.imidin-4'-yl ^2-F -Ftorpirimidin 5'-yl 2'-chloropyrimidine-5' -yl 2 '-Brompirimidin-5' -yl 2'uMetilpirimidin-Z'-w 2 '- ( Trifluoromethyl) pyrimidin-5'-yl 2'-Methoxypyrimidin-5'4 '-Fluoropyrimidin-5'-yl 4'-Chloropyrimidin-, 5'-U U -Bromopyrimidin-5'-yl 4'-Methylpyrimidin-5'-yl 4'-Methoxypyrimidin-5' -yl 4 '- (trifluoromethyl) pyrimidin-5 ^g -yl 5 '- (trifluoromethyl) pyridin-2'-yl 3'-Fluoro-5 - (trifluoromethyl) pyridin-2'-yl 5 - (trifluoromethyl) pyridin-3 '-pl 3 ', 6'-Dichloro-5' - (trifluoromethyl) pyridin-2'-yl 5 ’, 6-Dichloro-3'- (trifluoromethyl) -pyridin-2'-yl 5-Chloro-Z '- (trifluoromethyl) pyridin-2'-yl 3'-Chloro-5 '- (trifluoromethyl) pyridin-2'-yl 6'-Chloro-4'-cyanopyridin2-yl 3’-cyano-5'-nitropyridine-2'-yl 2'-Chloro-6 '—Fluoropyridin-4'-yl 6'-Chloro-4'-fluoropyridin-2'-yl 4 ', 6'-Difluoropyridin-2-yl 3', 5'-Dichloro-6'-fluoropyridin-2-yl 6'-methoxy-3'-nitropyridin-2'-yl 4'-cyano-6'-fluoropyridin-2'-yl 6'-Chloro-5 ’-cyanopyridin-2'-yl b'-Chloro-3 '-cyanopyridin-2'-yl 4 ’-cyano-3 ', 5’, 6 ’-tri ~ fluoropyridin-2' -yl 4 '-cyano-2', 5 ', b'-trifluoropyridin-3' -yl 120 21 1598872 22 Continuation ' 1 ² I 2 „1_ 4 ¹ 1 ⁵ 1 ⁶ 1 ⁷ . 121 6'-Chloro-5'-nitropyridin-2'-yl _f n n n 122 6'-Chloro-3-nitropyridine- -2'-silt n n n 123 5'-cyano-b'-fluoropyridin-2'-yl n n n 124 3'-cyano-6'-fluoropyridin-2'-yl n n n 125 4 ', 6' -Dicyanopyridin-2 '-yl n n n 126 5 '- (Trichloromethyl) pyridin-2' -yl n n n 127 5'-cyanopyridin-2'-yl 5'-Bromo-4 '- (trifluoro- n n n 108.5- 109.5 128 n n n methyl) pyridin-2'-yl 129 3'-Nitro-5 '- (trifluoro- 'methyl) pyridin-2' -yl n n , n 113-114 13Q 5 '- Formamidopyridine - -2'-silt n n n Resin 131 5'-aminopyridin-2 '-yl 2', 3 ', 5', 6 '-Tetrafluoro- n n n Resin 132 pyridin-4'-yl n n n Resin 133 5'-nitropyridin-2'-yl n n n 107-109 134 4'-methyl-5-nitropyridin-2'-yl n n n 135 5 '- (Difluoromethyl) pyridin-2' -yl n n n 136 5 '- (Fluoromethyl) pyridine- 2'-yl n n n 137 4 ', 6' -Difluoropyrimidin-2 '-yl n n n Resin 138 2 ', 6'-difluoropyrimidine- -4 '-il n n n 79-80 139 2'-Chloro-6 '- (trichloromethyl) pyrimidin-4'-yl n n n 113-114 140 2 ', 6'-Dichloropyrimidine- -4'-silt n n n 93-94 141 5 '- (methoxycarbonyl) pyridin-2'-yl n n n Oil 142 5'-Chloro-6'-fluoropyridin-2'-yl n n n 143 5'-Chloro-6'-hydroxypyridin-2'-yl n n n 144 5'-Chloro-6'-methoxypyridin-2'-yl n n n 145 5'-Chloro-6'-cyanopyridin-2'-yl n n n 146 5 ', 6'-Dichloropyridin-2'-yl n n n 147 6'-bromo-5'-chloropyridin-2'-yl n n n 148 5'-Chloro-6'-acetoxypyridin-2'-yl. n n n 149 5'-bromo-6'-fluoropyridin-2'-yl n n n S1 Ml Ml Ml mi. j S.1M1 Ml Ml MIMI MIMI Ml Ml HI Ml Ml Ml. Mi Μ »HI HI MIMI Ml Ml 1 1 1 1 1 1 1 t ΐ 'l ^ω 1 1 I 1 1 1 1 1 1 1 1 1 1 1 I 1 598872 24 Continuation tab. ' 1 ___________________1 2.J. 4 1 = I ⁶ 1I 8 150 5'-Bromo-6'-chloropyridin-2 ¹ -yl n Η Η E 151 5'-bromo-6'-cyanopyridin-2'-yl n Η Η E 152 5'-bromo-b'-hydroxypyridin-2'-yl n Η Η E 153. 5'-bromo-6'-methoxypyridin-2'-yl n Η Η E 154 5 'j6'T dibromopyridin-2'-yl n Η Η E 155 4 ’-cyanopyridin-2'-yl n Η Η Yo 156 6'-cyanopyridin-2'-yl n Η Η Yo 157 5'-chloropyridin-2'-yl 5-f Η Η _Ё 158 ' 5'-Chloropyridin-2'-yl 3-f 5-f Η Yo 159 5'-chloropyridin-2'-yl 4-f 6-f Η E 160 5 ^G- Chloropyridin-2'-yl 4-f 5-f 6-f 161 .5'-Chloropyridin-2'-yl 5-C1 Η Η E 162 5'-Chloropyridin-2'-yl 5-CH ₃ Η Η _Ё 162. 5'-Chloropyridine - ^ 2 '-yl 5-chjo Η Η Yo 163 5 '-Fluoropyridin-2' -yl 5-C1 Η Η Yo 164 5'-Fluoropyridin-2'-yl 5-C1 3-f Η E 165 ooh. , N 4-Chloro-6-methylpyri- Η Η Η Oil E 166 midin-2'-yl- Η Η Η 115-130 E 167 2'-Chloro-6'-fluoropyridin-4'-yl Η Η Η Oil E 168 5’-Bromo-4 '- (trifluoromethyl) pyridin-2'-yl Η Η Η E 169 4 ', 5' -Dichloropyridin-Z'-yl Η Η Η Yo 170 4 ', 5'-Dibromopyridin-2'-yl Η Η Η Yo 171 5 ', 6' -Dichloropyridin-2-yl Η Η Η Yo 172 4 ', 6'-Dichloropyridin-2'-yl Η Η Η E 173 4, 6 '-Dibromopyridin-2'-yl Η Η Η Yo 174 5 ', 6'-dibromopyridin-2'-yl Η Η Η E 175 4 '-Bromo-5' -chloropyridine- -2'-yl Η Η Η E 176 6 '-Bromo-5-chloropyridin-2' -yl Η Η Η E 177 5'-bromo-4'-chloropyridine- -2 -il . Η Η Η . E 178 5'-bromo-b'-chloropyridine Q ( -2 -il Η Η Η E 179 6 '-Bromo-4 ’-chloropyridin-2'-yl • Η Η Η E 180 4'-Bromo-6'-chloropyridin-2'-yl Η Η Η E 181 6'-Chloro-4'-methoxypyri- din-2'-yl  Η Η Η £ 182 6'-Bromo-4'-methoxypyridin-2 '-yl p. · FROM Η Η Η E 183 Η Η Η Έ . , N 184 5 - (BenzyloxycarOonyl) pyridin-2-yl Η Η Η Resin E 185 4'-Formylpyridin-2'-yl Η Η Η Oil E Continuation of table 1 - I Ί 3 4 eleven from 7 ί 186 5'-Formylpyridin-2'-yl N n n E 187 6'-Formylpyridin-2'-yl N n n Yo 188 4'-cyanopyridin-2'-yl n n n Yo 189 6'-cyanopyridin-2'-yl n n and E 190 5'-Hydroxymethylpyridin-2'-yl n n n E 191 b'-chloro-4'-trifluoromethylpyrid-2 ^g -yl n n n E 192 6'-Chloro-4'-trifluoromethylpyrid-2'-yl n n n E 193 6'-Chloro-4'-methylpyridin-2'-yl 'n N n E 194. 2 ', 5'-Dichloro-6'-cyanopyridin-2' -yl n n n E__ 195 2 ', 5' -Dichloro-6'-carboxypyridin-2'-yl n n n E 196 2 ', 5'-Dichloro-6'-methoxycarbonylpyridin-2'-yl n n n E 197 6'-Trifluoromethylpyridin-2'-yl n n n g 198 6'-Methoxycarbonylpyridin-2'-yl n n n E 199 6'-Carboxypyridin-2'-yl n n n E 200 4 '-Phenoxypyridin-2' -yl n n n Yo 201 5 '-Phenoxypyridin-2'-yl n n n E 202 6 '-Phenoxypyridin-2'-yl  n n n Yo 203 6'-chloropyridan-3'-yl n n n Z * Geometry of the beta-methoxyacrylate group. WS? ° ^2CH Z main ₃ Compound W X Y Z Mp, ° C Isomer * 1 2 3 4 5 6 7 1 3'-Fluoropyridin-2'-yl N . n n ' E 2 3'-chloropyridin-2'-yl N n n E 3 3 '-Bromopyridin-2' -yl n n n Yo 4 3'-Methylpyridin-2'-yl n n n Yo 5 3 '- (Trifluoromethyl) pyridin-2' -yl n n n Έ 6 3'-Methoxypyridin-2'-yl n n n Έ 7 4 '-Fluoropyridin-2' -yl n n n Yo 8 4 ^1- Chloropyridin-2'-yl n n n Yo 9 4'-bromopyridin-2'-yl n n n Yo 10 4 ^1- Methyridin-2'-yl . n n n E eleven 4 '- (Trifluoromethyl) pyridin-2' -yl n and n Yo 2 4'-Methoxypyridin-2'yl i n n • N E 3 5'-Fluoropyridin-2 · -yl n n n E Continuation of the table. 2 4 .5 14 5-chloropyridin-2'-yl N n n fifteen 5'-bromopyridin-2'-yl in n n 16 5'-Methylpyridin-2'-yl n n in 17 5'-methoxypyridin-2'-yl n n n 18 6 '-Fluoropyridin-2 ^/ -yl n n in 19 6 * -chloropyridin-2'-yl n n n 20 6 * -Bromopyridin-2'-yl n N - n 21 6'-pMetylpyridin-2'-yl n n n 22 6 '- (Trifluoromethyl) -pyridin-2'-yl in in in. 23 6'-Methoxy. Pyridin-2'-yl in and n ' 24 2'-Fluoropyridin-3'-yl n n in 25 2'-Chloropyrid-3'-yl in n n 26 2'-Brompyrid-3'-yl n in n 27 2'-Methylpyridin-3'-yl n n in 28 2 ^/ - (trifluoromethyl) pyridin-3 ^/ -yl n n n 29th 2'-Methoxypyridin-3'-yl n n n thirty 4'-Fluoropyridin-3'-yl n n n 31 4'-chloropyridin-3'-yl n n n 32 4'-bromopyridin-3'-yl in in n 33 4'-Methylpyridin-3'-yl n n n 34 4 '- (Trifluoromethyl) pyridin-Z'-yl n n in 35 4'-Methoxypyridin-3'-yl n in n 36 5'-.Fluoropyridin-3'-yl n n n 37 5 ’-Chloropyridin-3 '-yl n n n 38 5 '-Bromopyridin-3' -yl n n n 39 5'-Methylpyridin-3'-yl n in n 40 5 * - (Trifluoromethyl) pyridin-Z'-yl n n n 41 5'-methoxypyridin-3'-yl n n n 42 6-Fluoropyridin-3'-yl n in in 43 6-chloropyridin-3'-yl n n n 44 6 '-Bromopyridin-3' -yl n n n 45 6'-Methylpyridin-3'-yl in n n 46 6 ’- (Trifluoromethyl) pyridin-Z'-yl n n n 47 6-Methoxypyridin-3'-yl n n in 48 2'-Fluoropyridin-4'-yl n n n 49 2'-Chloropyridin-A '-yl n n n fifty 2'-bromopyridin-4-yl n n n 51 2'-Methylpyridin-4'-yl n n in 52 2 '- (Trifluoromethyl) pyridin-4'-yl n n in 53 2'-Methoxypyridin-4'-yl n in n 54 3'-Fluoropyridin-4'-yl n n in 55 3'-chloropyridin-4'-yl n n n 56 Z-bromopyridin-4'-yl n n n 57 3'-Methylpyridin-4'-yl n n in 58 3 '- (trifluoromethyl) pyridin-4-yl n in in 59 3-Methoxypyridin-4-yl in in n 60 4-fluoropyrimidin-2-yl n , n n 61 4-chloropyrimidin-2-yl n in in 62 4-bromopyrimidin-2-yl n n in 63 4-methylpyrimidin-2-yl n n in 64 4- (trifluoromethyl) pyrimidin-2-yl n n in 65 4-methoxypyrimidin-2-yl in in n 66 5-fluoropyrimidin-2-yl n n 'n · 67 5-chloropyrimidin-2-yl n I n ΞΣ’Ζ: Oil Oil Мι m <n <mini mi mi m · m> hi m> mi mi mihimimiwi mimimimimimimi m> mi mini mi mi mi mi mi mi mi mi kiwi mi mi mi mi mi mi mi mi mi mi mi m < Continuation of Table 2 68 5-bromopyrimidine ~ 2-yl IN N N 69 5-methylpyrimidin-2-yl n n IN 70 5- (trifluoromethyl) pyrimidin-2 ~ yl n n IN 71 5-methoxy'pyrimidin-2-yl n n n 72 2-fluoropyrimidin-4-yl in n in 73 2-chloropyrimidin-4-yl n n in 74 2-bromopyrimidin-4-yl n n in 75 2'-Methylpyrimidin-4'-yl n n in' 76 2 '- (Trifluoromethyl) pyrimidin-4'- -il n n in 77 2 '-Metoxypyrimidin-4 ^, -yl_ n n in 78 5'-Fluoropyrimidin-4 ^/ -yl n n in 79 5'-Chloropyrimidin-4'-yl n in in 80 5'-bromopyrimidin-4'-yl n n in 81 5'-methoxypyrimidin-4'-yl in n in 82. 5 '- (trifluoromethyl) pyrimidin-4'-yl n n in 83 '5' -Metoxypyrimidin-4 ^/ -yl n n n 84 6 '-Fluoropyrimidin-4' -yl n n in 85 6'-Chloropyrimidine ^ '-yl n n in 86 6 '-Bromopyrimidine-4'-jut n in in 87 6'-methylpyrimidin-4'-yl n n in 88 6 '- (trifluoromethyl) pyrimidin-4-yl H n in 89 6'-Methoxypyrimidin-4'-yl n n n 90 2'-Fluoropyrimidin-5'-yl n n in 91 2'-chloropyrimidin-5-yl Ή. n in 92 2'-Bromopyrimidin-5-yl in n in 93 2'-Methylpyrimidin-5'-yl n n in 94 2 '- (Trifluoromethyl) pyrimidin-5'-yl H • n in 95 2'-Methoxypyrimidin-5'-yl n n in 96 4 '-Fluoropyrimidin-5' -yl n in in 97 4'-chloropyrimidin-5'-yl n in in 98 4'-bromopyrimidin-5'-yl n in in 99 4'-Methylpyrimidin-5'-yl n in in 100 4 '- (trifluoromethyl) pyrimidin-5'-yl n in  in 101 4'-Methoxypyrimidin-5'-yl n in in 102 5 '- (trifluoromethyl) pyridin-2'-yl 4-f n in 103 5 '- (trifluoromethyl) pyridin-2'-yl n n in Oil 104 5'-Chloropyridin-E '-yl 5-F ^; n in 105 5'-chloropyridin-2'-yl 3-f 5-f n 106 5'-Chloropyridin-2'-yl 4-F. 5-f 6th 107 5'-chloropyridin-2'-yl 5-C1 n in 108 5'-chloropyridin-2'-yl 5-CH.O in in 109 5'-Chloropyridin-2'-yl 5-CH,  n n 110 5’-Fluoropyridin-2 '-yl 5-C1 in in 111 5 '-Fluoropyridin-2' -yl 5-C1 3-f in * The geometry of the beta-methoxyacrylate group. " _1M > _{M. I} > _AND 1 _{M) I1} PX _M1M >"> M | M < _{I (} M | _M , _I > _I , I ₁ I _(I | _P5 , _I , m _1I , _{I. I4I} ; _I 1 _m fW.WlWiWtW.M IWfMlWlWlWiMiWfM W _t 4 COoCHa (0) n = S 1 ^{2 3} '3 Table 3 Compound W η X Υ Ζ Mp, ° C Isomer * 1 5 ^ί -Brompiridin-2 '-yl 1 N n . n Resin E 2 5'-Brompiridine-2 '-yl ’ 2 n n n Resin E 3 5'-chloropyridin-2'-yl 1 n n n E 4 5'-Chloropyridin-2'-yl 2 n n n Yo 5 5 '- (Trifluoromethyl) -pyridin-2' -yl 1 5-f n n Yo * The geometry of the beta-methoxyacrylate group. Table 4 Compound Table Wheat Barley Apple tree Rice Peanut Grape Tomatoes 1 2 3 4 5 6 7 8. 9 10 1 4 4 4 4 3 4 4 eleven 1 3 * 4* 4* 2 * 0 * 4* 4* 14 ' 1 4 . 4 2 4 4 4 - fifteen 1 4 4 - 3 3 4 - 16 1 2 4 4' 4 4 4 4 21 1 3 4 4 4 4 4  3 22 1 4 4 4' 4 4 4 3 61 1 3 4 4 0 •4 1 0 67 1 h ** 2 ** 0 ** 0 ** 4** 4** 0 ** 129 1 0 4 4 0 0 0 0 130 1 3 0 0 0 4 0 0 131 1 3 0 0 0 0 0 0 133 1 4 4 4 4 - 4 0 137 1 2 0 4 0 0 0 0 138 1 . 4 0 3 0 0 4 0 139 1 4 0 .3 0 0, .. 4 0 140 1 2 0 0 0 0 4 0 ¹⁶⁵ 1 2 4 4 2 4 4 3 166 1 4 4 4 1 4 3 3 167 1 4 4 • 4 3 0 4 0 14 2 4 4 4 3 4 4 ' 0 fifteen 2 2 3 0 0 1 4 0 1 3 0 * 0 * 3 * 0 * 0 * 0 * 0 * " 2 3 3 0 . 3 0 0 0 0 thirteen 1 4 4 4 4 4 4 - 18 1 4 4 4 4 4 0 - 19 1 4 4 4 4 4 4 - 20 1 4 4 4 4 4 4 - 23 1 4 4 4 4 4 4 - 127 1 0 * 4* 4* 4* 3 * 0 * - 128 1 4 4 4 4 4 4 - Continuation of table 4 1 2 3 4 ABOUT 6 1 g 3 192 1 4 4 4 1 0 4 4 - 200 1 4 4 4 4 4 4 - 202 1 4 4 4 4 4 4 - 204 1 4 4 4 4 4 4 205 1 4 4 4 4 4 4 - 207 1 2 4 4 2 0 0 - 208 1 2 4 ' 4 0 0 4 - 209 1 4 4 4 3 0 4 - 210 1 4 ' 4 4 0 0 4 4 211 1 4 3. 4 - 4 4 4 212 1 4 4 4 4 4 4 4 213 1 4 4 4 4 4 4 0 85 1 3 4 4 3 4 4 3 89 1 4 4 4 - 3 4 4 214 1 4 4 4 4 4 4 3 215. 1 4 4 4 3 4* 4* 4* 216 1 3 * 4* 4* 3 * 4 4 4 217 1 4 4 4 - . 4 4 3 218 1 4 4 4 - 4' 4 4 219 1 4*** 4*** 4 - s *** 4*** 4*** 220 1 4 4 4*** s *** 4  4 221 1 4 4 ' 4 - 4 4 4 222 1 - 4 4 4 4 4 3 223 1 - 4 4 4 * 25 ppm, spraying only foliage. ** 40 ppm, spraying only foliage. *** 10 ppm, spraying only foliage. Table 5 Plant material used for screening View The code Variety Stage. processing growth The number of plants per pot Type of com fasting Barley BR Atem 1-1.5 sheets 4 IIP * Wheat WW Titnmo 1-1.5 sheets 4 I1P Corn Mz Eareiking 2.25-2.5 sheets 1 Peat Apple tree AR Red Sweet 4-5 leaves 1 I1P Rice RC Ishikari 2-2.5 sheets 4 IIP Tomatoes TO Ailse craig 2-2.5 sheets 1 Peat * 11P Pot Compost John Innes. Table 6 Compound Table BR W RC AP MX TO TO * TO * 14 1 NT NT NT NT NT NT 2AT 2AT fifteen 1 1 2A NT 1AT 1AT 16 1 NT NT NT NT NT BEHIND NT NT 22 1 NT NT NT . 1A NT NT NT 61 1 NT NT NT N1 NT NT 1 132 ¹ 1 'NT NT NT NT 1 1 138 1 • 3 NT NT 139 . 1 NT NT 140 1 G NT NT Note. Key III * 2000 ppm + 500 ppm; immaturity effect = G; apical lesions = AR; tillering or formation of lateral shoots = T; a pass means an effect of less than 10%; NT indicates that the compound has not been tested against this species. ________ _ _ < Table 7 Alphabetic the code Test species Carrier / Feed Test type Duration 1 , Tue Tetranychus uritcae (spider mites and testes) French bean leaves Contact 3 CP Chilo partellus leaves (corn stalk sharpeners) rapeseed Residual 3 DB Diabrotica balteata (leaf beetle larvae) Filter paper // seeds Residual 3 MD .. Musca domestica (house flies adults) Cotton / Sugar Contact 1 MI Meloidoqyue incognita (tomato nematode of root growths of the larva) Semi-winro Residual 7 Table 8 Compound Consumption rate Types (tab. 7) T and e j CP I DB I MD MI 14 500 0 9. 5 9 - fifteen 500 0 .9 0 - fifteen 250 - - 9 Table 9 Compound Puccinia Recondita Wheat Erysiphe Gramipis Hordei Barley Venturia Inaequalis Apple tree Pyricularia ryzae Rice Cercospora arachidicola Peanut Plaemopara viticola Grape Compound A 0 0 0 0 0 0 Compound 1 ' scoreboard 1 3 4 4 2 0 4