SU1600628A3 - Method of producing derivatives of acrylic acid of their stereo isomers - Google Patents

Abstract

The method of obtaining acrylic acid derivatives of general formula I, indicated in the description, or their stereoisomers, characterized in that the compounds of general formula II, where the radicals have the meanings indicated in the description, are reacted with the compound of general formula PH ₂ P ⁺ - CHOR ₂ , where ₂ has the indicated value.

Description

acetic acid was removed under reduced-pressure chromatography using applied pressure. The residue is dissolved in ethylacetate-ether as a solvent and washed successively with water. T of gasoline () is doi, aqueous sodium bicarbonate (3 times) and water (twice), then

i-a; Jenzina. Oi-os L .; (/.:ij, H NMR (COClS), O: 3.43 (2H, 23 Hz); 3.72 (d, J 1 Hz)

(2: 1), has J

D, J.

"Million

purified by chromatography using ethyl acetate-T gasoline as a solvent ()

i-a; Jenzina. Oi-os L .; (/.:ij, H NMR (COClS), O: 3.43 (2H, 23 Hz); 3.72 (d, J 1 Hz)

(2: 1), has J

D, J.

"Million

The ZE isomer is a solid, Topl. 107 ,.

IR spectrum (nudzhol), g 1717 and 1625.

L

 H NMR (CDCl3, 3.93 (3H, s); 6.33

(

: 3 „65

Ihf yes

 3.5 Hz)

6.40

(1H, dd, 3

(ZN,

J

5 and

C

2 Hz); 6.36 (1H, s) | 6.82 and 7.10 (each W, D5 J 16 Hz)

Example 7. According to the proposed method, the following examples were obtained from the table below, Ij 2, 3, and 4.

NMR Spectra of compounds are given in Table O5.

Below are the general formulas

: Connections: Obtaining a compound by formula;

Rchxh.

С02Ш

where the R group includes all the Rg groups listed in Table 4, for each of the following replacement schemes on the above hair dryer: 1 st ring. In each case, an acrylate group can have either E-gaometry, or Z-- g eometry ,.

Z

H

H

H

H

H

H

H

H

H

H

H.

H

H

H

H

H

H

5-cl

5 HO

H

H

the mutable is ended by mixing by mixing the mixtures. Soov, wt.%:

YU

40

five

ten

 35

The composition of the first three ingredients, prepared by mixing into the ultating mixture through a sieve (Rattan standard), is prepared by the required mixing agents, in wt.%:

50

25 1.5 23.3 Ingredients with obtaining ta, easily dispersion x, wt.%:

600628

The compound of example 4 Dispersol T Liesapol X Cellophas Vooboo Ytri acetate

45

5 0.5

2 47.5

Example 1). The active ingredient is dissolved in a solvent and 10 the resulting liquid is spread on kaolin clay granules. The solvent is then allowed to evaporate to form a granular composition. Content of the ingredients is 15. Comrade, wt.%:

Compound of Example 35 Kaolin clay granules 95 20 Example 2. A composition suitable for use as a dressing for seven n is prepared by mixing three ingredients, wt%;

Compound of Example 4 50 25 liHHepajibHoe oil 2 Kaolin clay 48 Example 13. The burning powder is prepared by mixing the active ingredient with talc, wt%: .30 Compound

example 35

Talc 95

Example 14. CO - composition is prepared by grinding in a mill comprising the following, mentioned below, followed by formation of an aqueous suspension of ground mixture with water, wt.%:

Compound of Example 4 40

Dispersol T10

40 Lubrol APN51

WaterEverything

PRI me R 15. Dispersible. the powder preparation is prepared by mixing the following ingredients, followed by grinding the mixture until thoroughly mixed, wt.%:

example 3.25

50 OT / B2 aerosol

Dispersol A.C.5

Kaolin clay28

Silica 40

JJ Example16. Illustrates the preparation of a dispersible powder formulation. The ingredients are mixed and the mixture is then ground in a grinding mill, wt.%:

25

one

five

in

25 34

15

Compound

of example A

Permin VH

Diperzol T

Polyvinylpyrrolidone

Silica

Kaolin clay

Example 17. The following ingredients are compiled into a dispersible powder by mixing followed by grinding the ingredients, in May,%:

Connection example 3 25

OT / B2 aerosol

Dispersol A5 Kaolin clay68

The compounds listed in Table.

15

16006

1-5 are made in a similar manner as in examples 8-17.

Below is an explanation of the compositions or substances represented by different trademarks and trade names:

Lubrol Z - nonylphenol condensate (1 mol) with ethylene oxide (1-3 mol) Aramazole H - solvent

Alkstbenzol mixture

l

R

 a mixture of sodium sulfate and formaldehyde condensate with sodium naphthalenesulfonate

nonylphenol condensate (1 mol) with naphthalene oxide (5.5 mol)

sodium carboxymethylcellulose thickener

nonylphenol condensate (1 mol) with ethylene oxide

(Per mole)

dioctyl sodium sulfosuccinate

- sodium alkylnaphthalene sulfonate 18. Compounds are tested for their effect on

yu 15

a7.

20

-

25

600623

r yes leafy mushroom plant diseases. Use the following technique:

Plants are grown in compost for John Inne type pots (No. 1 or 2) in 4 CN mini-pots. Test compounds are formulated either by grinding in a ball mill with an aqueous Disperzole T or as a solution in acetone or acetone — ethanol, which is diluted to required concentration immediately before use. In the case of diseases of the leaf cover, the compositions of 100 million (active ingredient) are used for spraying the foliage and applied to the roots of a plant in the soil. Spraying is carried out to the maximum retention of the composition on the leaves, and the soil mordant is adjusted to a final concentration equivalent to approximately 40 million active ingredient in dry soil. When applied by spraying on cereals, Tween 20 is added to obtain a final concentration of 0.05%.

In most of the tests, the compound is introduced into the soil (root treatment) and applied to the leaves (by spraying) a day or two before inoculating the plant with pathogens. An exception is the test on Erysiphe graminis when the plants are inoculated 24 hours before treatment. Leafy pathogens are sprayed as a suspension of pores on the leaves of experimental plants. After inoculation, the plants are placed in; suitable medium to ensure the development of infection, and then incubated until the disease is at a level that is suitable for assessments. The period between inoculation and evaluation varies from 4 to 14 days depending on the disease and the environment.

The control of disease progression is recorded on the following scale: 4 No disease; 3 tracks - 5% disease relative to untreated plants; , 2 6-25% disease relative to untreated plants; 1 26–59% disease relative to untreated plants; About 60-100% disease relative to untreated plants.

thirty

35

40

45

55

The results are shown in Tables 6, 7, 8 and 1 0. (The data given in Table 6 are related to the {Compounds listed in Table 1, Table 7 - to the table 2 Table 2, Table 7A - to Table 2, Table 8, to Table 4, to Table 4),

The fungicidal activity of strobilurin A and compound 9 of Table I of plant protection is compared with the aid of tests carried out in accordance with the procedure described in Example 17. A feature of these tests is that both compounds are used in the form of active concentration ingredient, 25 million In the case of compound 9, the composition was applied by foliar pollination. In the case of strobilurin A, the composition was used for foliar pollination carried out in the same way using compound 9 and the same for root irrigation. The results are shown in table.9.

These results indicate. that compound 9 is a more active anti-fungicidal plant protection agent than strobilurin A even under the condition that strobilurin A is applied by means of combined treatment with pollination and root watering, and compound 9 only as a pollination.

Test compounds were prepared in a ball mill with an aqueous dispersion T or in the form of solutions in acetone or acetone-ethanol. They were diluted to 100 ppm with water and 2.5 ml aliquots were added to Petri dishes. Aliquots were further diluted to 25 ppm (active ingredient) with potato dextrose agar.

Bowls seeded with pathogenic fungus

MI listed in Table 10, using either a spore suspension or mycelial mass, and then kept at appropriate temperatures (19-25 C). Growth control was carried out after 2 days using indexes of 0.2 or 4.

The results are shown in Table 10, where there is no effect on growth; 2 partial suppression of the growth of fungi; 4 after inhibiting the growth of fungi.

Table 10 summarizes the abbreviations of the test organisms.

ten

15

20

628

five

0

18

Acronyms Latin names Cs Cladosporium Sphaero: spermun,

Trichoderma Viride Pp Pullularia Pullulans At Alternaria Tenuis All Aspergillus Niger TV Tachoderma Viride Pd

Atrum PC Phytophthora Cinnamomi Cc Colletotrichum Coffeanum Ch Psludocercosporella

Herpotrichoides Cb Cercospora Beticola Sn Septoria l-Todorum

As can be seen from the table data, all proposed compounds exhibit a greater activity, at least j, with respect to one fungal disease, than is synthlurin A.

F

about rm y

and 3 o b p. in te

35

Method for producing acrylic acid derivatives

five

where r n

both methyl;

five

Re

X - in the ortho-position with respect to the acrylate group - hydrogen, fluorine, chlorine, bromine, C-Cg-alkyl, phenyl-C, -Sf-alkyl, in kpto; .- phenomonyl group is possibly replaced by fluorine, chlorine or methoxy - ,. dimethoxymethyl, ethylene dimethoxymethyl, trnfluoromethyl, pheno-; simethyl, possibly substituted for chlorine, pyridyl ethyl, furanylethyl, thienium. possibly substituted phenyl, trifluoromethyl, imano, C — C-alkoxycarbonyl, beisyloxy19

carbonyl, acetyl, furyl or benzthiazolyl, ethynyl substituted with phenyl or t-butyl, phenyl, C -Cg-alkoxy, benzoxazolylmethoxy, benzyloxy-, phenoxy-, possibly substituted with fluorine, chlorine, bromine, hydroxy, methyl, trifluoromethyl, formyl. Cs-C-alko-x. Possibly substituted by fluorine, propenyloxy, propargyloxy, acetoxy, methylsulfonyloxy, phenyl, phenoxy, nitro, amino, formylamino or acetylamino, naphthyloxy, isobutyryloxy, benosoxy, possibly substituted by t-butyl, benzoyl, optionally substituted by methoxy, coxycarbonyl, cyclotexyloxycarbonyl, allyloxycarbonyl, phenoxycarbonyl in which the phenyl group is optionally substituted by methoxy, nitro, benzoylamino, furoylamino or O - thienylcarbonyl-L-methylamino; Y - in the position of ortho, meta or para with respect to the acrylate group - hydrogen, fluorine, chlorine, bromine, methyl, phenylethenyl, nitro or phenoxy-;

Z is hydrogen;

or X and Y, occupying adjacent positions in the phenyl ring, together form a condensed benzene ring, possibly substituted by phenyl, a condensed naphthalene ring, a condensed benzo, -

60062820

 furanyl ring, condensed benzothienyl ring or group

X

ten

OS

(Y

Or. Cruypes Y and Z, when they occupy adjacent positions in the phenyl ring 15Ce, together form a condensed benzene ring, or their sterioisomers, which differ from the general formula

20

where RJ, X, Y and Z - have the indicated meanings, interact with a compound of the general formula, +

Ph, P

five

where r 2

- CHO%, has the specified value.

Continued tabl, 1

61

SI,

CH,

SNSO. SNSO.

62

CH,

CHj

A ocHj

cHpf snnr

63

sn.

 ishzs. osnz; :

 sn; snr tHCHjOjC

64

sn.

CHjOjC

DOS,

nn nn, nn

Sn, 2- (4-CH, 0-CgH CO)

mon, a-CiHjOCHj

CHj (CH,) jCH4

70

CH,

cn

H63-347,63E

H P2-PZ 7.62

sn

/,

CHjOjC CH

OSSNz 122-123 7,73

H

H N

Oil oil

7.32 7.59

E E E

 Singleton chemical shift from the ophinic proton on the beta-methoxyacrylate group (relative to tetramethylsipan), Solvent: CDClj Geometry of the bgata-methoxyacrylate group

29

- Chemical shift of the singlet from the olefinic group on the beta-methoxyacrylate group. (w: n-reply about tetra

- methylsilane), solvent CDClg

 The geometry of the beta-metskyacrylate group Compound 10 is:

“-If-) f

WITH

, СНзОгС SN

/

RSN

Compound P is:

СНзОзС- Н ОСН.

1600628

30 T a b e c i a 3

/

RSNg

t a b l and c a 4

CuQCH

cn

BASED

4C

; The chemical shift of the singlet from the olefinic proton on the beta-methoxyacrylate group (relative to tetramethylsilane),

solvent -If-

Geometry of beta methoxyacrylate group.

3.68 (ZN, s)

7.52 (1H, s) 5

3.60 (ЗН., С) 5

7.48 (1H, s)

3.60 (ЗН, с) §

3.80 (2H5s) 5

3.6 (ЗН, s)

3.66 () |

3.56 (ZN, s) |

7.9-8.1 (W,

3.73 (ЗН, с) |

3.53 (3N, s) |

7.32 (1H, s)

3.70 (ZN, s) |

7.59 (1H, s)

T ablitsa

3.83 (bN, s) | 7.25-7.6 (ZN, m) {7.9-8.1 (1H, m) 3.66 (ZN, s); 3.87 (2H, s);

3.70 (AH, s); 3,75 (AH, s); 7.50 (1H, s)

3.75 (ЗН, с) | 7.0-8.15 (5H, m)

3.76 (3N, s); 7.51 (1H, s)

7.73 (ZN, s); 7, -7.7 (9H, m);

i) 3s85 (3H, c); 7.54 (1H, s),

3.67 (ZN, s); 3.85 (ZN, s);

3s80 (3H, c); 4.97 (2H, s);

33160062834

Continuation of table.5

one

IIIZ

2 1 1.28 (9K, s); 3.68 (3N, s); 3.82 (2H, s); 7.54 (1H, s)

261 1.32 (3N, t); 3.70 (AH, s); 3,82 (AH, s);

4.24 (2H, d); 6.38 (1H, d); 7.15-7.40 (2H, m) ppm

271 3.68 (ЗН, s); 3.80 (3N, s) ;; 3.95 (2H, m);

4.08 (2H, m); 5.77 (1H, m); 7.15 (1H, m);

7.34 (2H, m); 7.56 (1H, s); 7.62 (1H, m) ppm

28G 3.70 (ЗН, s); 3.78 (ZN, s); 3.81 (ZN, s);

6.38 (1H, d); 7.15-7.4 (ЗН.m) .; 7.64 (1H, s); 7, b6 (2H, m) ppt

129 I 1.25 (ЗН, t); 2.50 (2H, t); 2.8.1 (2H, t);

3.70 (ЗН, s); 3.82 (ЗН, s); 4.12 (2H, d);

7.0-7.3 (4H, m); 7.59 (1H, s), ppm 131 1 3.72 (3N, s); 3.83 (ЗН, s); 7.2-7.5 (7H, m);

7.71 (1H, s); 7.75-7.80 (2H, m); 7.98 (1H, d) ppm 134 1 3.71 (3N, s); 3.74 (ЗН, s); 4.13 (2H, t, J7 Hz);

7.47 (1H, s); 7.97 (1H, shir.d) rrsh

52 3.63 (ЗН, s); 3.78 (ЗН, s); 6.80-7.40 (8H, m);

7.46 (1H, s)

62 3.60 (ЗН, s); 3.75 (ЗН, s); 6.8-7.0 (4H, m);

7.14-7.32 (4H, m); 7.45 {1H, s)

72 3.62 (ZN.s); 3., 77 (ЗН, с); 7.48 (1H, s), 28 2 3.66 (3N, s); 3.80 (ЗН, s); 3.82 (ZN, s)

6.7-7.3 (8H, m); 7.51 (1H, s) 42 2 3.55 (ZN, s); 3.71 (3H, c) j 6.81-7.61 (14H, m)

(olefinic proton is darkened by aromatic

protons) ppt 60 2 3.61 (3N, s); 3.78 (ЗН, s); 6, 3 (3H, M) j

7.55 (1H, s) ppm

632 3.59 (30N, s); 3.73 (ЗН, s); 6.3-7.3 (7H, m);

7.43 (1H, s) pp

64-2 3.49 (ЗН, s); 3.60 (ЗН, s); 6.2-7.15 (7H, m);

7.32 (1H, m) rrs

66 2 3.65 (ЗН, s); 3.79 (3N, s); 7.48 (1H, s)

82 2 3.55 (ЗН, m); 3.65 (9H, m); 6.1 and 6.8-7.3

(1H and 6H, m); 7.50 (1H, s) ppm

87 2 3.46 (ЗН, s); 3.63 (3N, s); 6.3-7.2 (7H, m);

7.38 (1K, s) rrga

153 2 3.70 (ЗН, s); 3.79 (ZN, s); 3.82 (ZN, s);

7.53 (1H, s)

1602 .3.63 (ЗН, s); 3.80 (3N, s); 4.51 (2H, d);

5.05-6.39 (ЗН, m); 6.70-7.35 (4H, m) j 7.46 (1H, s)

1612 3.60 (SH, c); 3.74 (ЗН, s); 4.66 (2H, d);

6.00-7.40 (11H, m); 7.46 (1H, s)

1812 3.54 (3N, s); 3.88 (ЗН, s); 6.60 (1H, s) 165 2 3.55 (ZN, s); 3.74 (ЗН, s); 6.80 (1H, d);

6.95 (1H, m); 7.15-7.40 (4H, m); 7.43 (1H, s); 7.65 (1H, m); 8.19 (1H, m)

1822 3.85 (6H, s); 3.90 (ЗН, s); 5.00 (1H, d, J 7 Hz);

6.70 (1H, d, J 14 Hz); 7.50 (1H, s) 125 2 3.66 (AH, s); 3.67 (ЗН, s); 3.8 (ЗН, s);

6,, 28 (7H, M) j 7.46 (1H, s) ppm 132 2 3.63 (ZN, s); 3.7 (ЗН, s); 3.73 (ЗН, s);

351600628

 Continuation of table.5

one

GENE

6.48-7.24 (7H, m); 7.49 (1H, s) ppt 2 3.75 (6H, s); 3.85 (ЗН, s); 5.50 (1H, d,;

J 14 Hz); 7.50 (1H, s); 7.50 (1H, d. J 14 Hz)

2 1.3 (ЗН, t); 3.6 (RFP, s); 3.76 (ЗН, s); 3.95

(2H, d); 6,, 34 (8H, M) j 7.44 (1H, s) ppm

2 2.31 (ЗН, s); 3.56 (3N, s); 3.7 (ЗН, s);

6.64-7.39 (ЗН, m); 7.45 (1H, s), ppm

2 3.6 (ЗН, s); 3.77 (3H, c) j. 4.46 (1H, t) {4.52

(1H, t); 5.21-5.5 (2H, m); 5.86-6.21 (1H, m) j 6.5-7.39 (8H, m); 7.47 (1H, m) ppm

2 3.14 (ЗН, s); 3.62 (ЗН, s); 3.77 (3H, c) j

6.83-7.38 (ЗН, m); 7.45 (1H, s) ppm

2 1.83 (ЗН, t); , 8 (2H, m); 3.64 (ЗН, s); 3.78

(ZN, s); 3.87 (2H, t); 6.53-7.31 (9H, m); 7.50 (1H, s) pnm

2 1.23 (6H, d); 3.54 (3N, s); 3.7 (ЗН, s);

 4.39 (1H, N); 6.34-7.27 (8H, m) {7.38 (1H, s) ppm

2 0.87 (6H, t); 1.38 (5H, m); 3.5 (3N, s); 3.64

(ZN, s); 3.72 (2H, d); 6.3-7.25 (8H, m) 7.37 (1H "s) ppm

2 3.0 (1H); 3.50 (30N, s); 3.60 (ЗН, s); 6.67, (8H, m) 5 7.28 (1H, s) ppm

2 2.61 (1Н "t); 3.62 (ЗН, s); 3.79 (ЗН, s);

4.65 (2H., D); 6.57-7.3 (8H, m); 7.45 (1H, s) ppm 3 3.6 (3N, s); 3.78 (ЗН, s); 6.8-7.3 (8H, m);

7.47 (1H, s)

3 3.69 (ЗН, s); 3.88 (ЗН, s); 6.84 (2H, d);

 7.60 (1H, s); 8.10 (1H, dd); 8.20 (1H, d)

4 0.92 {9H, s); 3.72 (ЗН, s); 3.80 (ЗН, s);

7.58 (1H, s) 4 2.81 (4H, s); 3.68 (ЗН, s); 3.80 (ЗН, s);

7.59 (1H, s) 4 2.8-3.1 (4H, m); 3.72 (ЗН, s); 3.81 (ЗН, s);

7.60 (1H, s) 4), 80-1.92 (2H, m); 2.46-2.68 (4H, m)

3.69 (ЗН, s); 3.77 (ЗН, s); 7.50 (1H, s) I 1.1-2.1 (m); 3.58 (3N, s); 3.67 (ЗН, s);

4.85 (1P, m) | 7.44 (Ui, c); 7.94 (1H, each $ d, J = 7 Hz) 1 3.32 (3N, s); 3.51 (3N, s); 3.56 (3N, s);

6.54-7.5 (8H, m) 2 3.6 (31, s) J 3.76 (ZN, s); 6,, 42 (8H, m) {

7.5 (1H, s) 2 3.62 (3N, s); 3.75 (ЗН, s); 3.8 (ЗН, s);

b, 7-7.3 (8H, m); 7.5 (1H, s) 2 3.55 (ZN, s); 3.65 (ЗН, s); 6.6-7.2 (14K, m)

2 3.66 (ЗН, s); 3.82 (ЗН, s); 6.86-8.36 (MO, m);

7.5 (1Н „с)

2 3.5 (3N, s); 3.6 (ЗН, s); 6.7-7.95 (12H, m) 1 3.67 (ЗН, s); 3.92 (311, s); 5.23 (1H, dd)}

5.63 (1H, dd); 6.52 (1H, s); 6.80 (W, dd) 2 3.58 (AH, s); 3.72 (ЗН, s); 6.88 (1H, dd);

7.1-7.5 (4H, m); 7.40 (1H, s); 7.84 (1H, dd); 8.44 (1H, br.)

 160062838

Continuation of table.5

T-tt

2 3.49 (ЗН, с) | 3.88 (ЗН, s); 6.61 (1H, s) |

6.92-7.08 (ЗН, m); 7.2-7.4 (ЗН, m); 8.148, 2 (2H, m) 1 3.49 (W.c); 3.61 (ЗН, s); 5.17 (2H, s); 7.17, 5 (m); 7.36 (1H, s); 7.95 (1H, broad doublet) l, 27 (3H, T) j 3.59 (3N, s); 3.70 (2H, q); 3.72

(ZN, s); 7.1-8.0 (4H, m); 7.40 (1H, s) I.. 3.75 (ЗН, с) | 3.85 (ЗН, s); 6.7-7.30 (ЗН, m);

7.6 (1H, s)

5 3.17 (2H, s) | 3.72 (ЗН, с) | 3.87 (ЗН, с) 7.22-7.42 (9H, m); 7.64 (N, s)

1 2.85-3.07 (2K, m) 5 3.64 (3N, s); 3.73 (3H, c) j

7.17-7.40 {9H, m) 5 7.47 (1H, s)

1 3.70 (ЗН, s); 3.85 (3H, c) j 7.00-7.10 (1H, d

J 9 Hz); 7.39-7.50 (1H, m); 7.55 (lH, c) j

7.79 (1H, s) 1 2.45 (3H, s) s 3.65 (3N, s); 3.85 (ЗН, s);

7.15-7.18 (N, m) | 7.35-7.48 (ЗН, m); 7.52

(H, s); 7.60-7.64 (1H, m); 8.24 (1H, m);

8.39 (1H, m). 1 3.71 (ZN, s) 5 3.86 (ZN, s); 7.16 (1H, d J 10 Hz);

7.27 (1H, d J 50 Hz); 7.58 (1H, s) | 7.63 (1H, s) 1 3.73 (ZN, s) e 3.86 (ZN, s); 6.75-6.80 (W, m);

6.90-7.00 (IL-0; 7, 0-7.20 (6H, m); 7.62 (1H, s) 1 7.61Sh, s); 7.72 (ЗН, s); 4.68 (2H, d);

5.05-5.5 (2H, m), 5.65-6.3 (1H, m); 7.1-7.6 (m) |

7.45 (H, s); 7 „.98 (1Н shird)

1 3.57 (ЗН, s) | 3.64 (bN, s); 6.6-6.8 (ЗН, m);

7.05-7.45 (4H, m); 7.44 (1H, s); 8.05 (1H, bd)

 3.30 (4K, m); 3.58 (4H, m); 3.69 (ЗН, s); 3.81

(ZN, s); 7.2-7.45 (m); 7.54 (1H, s) 2 Solvent;

3.39 (ЗН, s); 3, B1 (ZN.s); 6.50-7.20 (8H, s);

7.42 (1H, s) 2 3.41 (ZN, s) | 3.55 (ЗН, s); 6.75-7.20 (8H, s);

7.32 (1H, s)

2 2.22 (ЗН, s); 3.55 (ЗН, s); 3.68 (ЗН, s); b, 4-7.4 (3N, m); 7.4 (1H, s)

2 3.41 (ЗН, s); 3.78 (1H, s); 6.68-7.35 (13H, m); 7.48 OH, s)

2 3.45 (ЗН, s); 3.55 (ЗН, s); 6.55-7.25 (7I, m);

7.35 (1H, s)

2 3.45 (ЗН, s); 3.70 (ЗН, s); in, 80-7.25 (7H, m):

7.50 (1H, s) 2, 3.50 (ZN, s); 3.65 (ЗН, s); 6.70-7.30 (7H, m);

7.40 (1H, s) 2 3.60 (AH, s); 3.70 (ЗН, s); 3.71 (ЗН, s);

6.40-7.30 (7H, m); 7.45 (1H, s)

2 0.89 (ЗН, t); 1.20-1.50 (6H, m); 1.50-1.80 (2H, m) |

3.68 (ЗН, s); 3.82 (ЗН, s); 3.92 (2H, t); 6.84-7.00 (2H, m); 7.10-7.30 (2H, m); 7.47 (1H, s)

2 3.41 (ЗН, s); 3.51 (3N, s); 6.80-7.20 (8H, m);

7.31 (1H, s)

193 2 1.23 (bN, d); 2.3-3.0 (1H, m); 3.60 (ZN, s): 3.69 (ZN, s); 6.9-7.4 (M); 7.47 (1H, s)

2082 3.50 (30N, s); 3.65 (ZP, s); 6.7-7.3 (8H, m);

7.45 (1K, s); 8.1 (1H) ppm

2092 3.60 (ЗН, s); 7.76 (ЗН, s); 7.00 (1H, d);

7.32 (6H, m); 7.46 (1H, s); 7.56 (1H, s); 9.94 (1H, s) ppm

93 3.53 (ЗН, s); 3.68 (ЗН, s); 6.62-7.4 (18H, m);

7.43 (1H, s)

103 3.06-3.26 (4H, m); 3.56 (3N, s); 3.72 (ЗН, s);

6.88-7.20 (7H, m); 7.59 (1H, s)

The peak durped in many resonances belongs to the amide rotamers. As a whole, it agrees with the structure.

Table

4 2 О О О О 4 4 О О 4 4 4 О О О 4 4

9

3 2

4 o 3

about

4 o 4 3

 4 o o o

about

oh oh

4 4 O

about

2 4 4 2 4 О О 2 О О 2 4 3 4 4 О 2 1

About 4 4

4 o 4 o 1

O l

4 3

2

four

four

four

four

four

four

four.

four

3

one

four

four

3

four

3

ABOUT

about

4 4

41160062842

Continuation of table 6

iz: ii: rni: iz :: i

 Tested in the form of foliar spray at a concentration of 25 million

 It was tested at a concentration of 25 ppm only when spraying the leaves

 Table 7

47

I60062G

Test at 6 ppm ppm (active ingredient)

Table9

Claims (2)

Claims for plant protection than strobilurin A, even under the condition that strobilurin A is applied by means of a combined treatment of pollination and root watering, and compound 9 only in the form of pollination. Test compounds were prepared in a ball mill with an aqueous Disperser T or in the form of solutions in acetone or acetone-ethanol. They were diluted to 100 ppm with water and 2.5 ml aliquots were added to Petri dishes. Aliquots were further diluted to 25 ppm (active ingredient) with potato dextrose agar. The cups were seeded with the pathogenic fungi listed in Table 10, using either spore suspension or mycelial mass, and then kept at appropriate temperatures (19-25 ° C). Growth control was carried out after 2 days, using indices of 0.2 or 4. The results are shown in Table 10, where 0 = no effect on growth; 2 = partial suppression of fungal growth; 4 = after suppressing the growth of fungi. Table 10 shows the abbreviations of the test organisms. 35 A method of obtaining rilic acid derivatives of the general formula ax2a1 with 45 50 55. where K. | and R. £ is both methyl; X - in the ortho-position with respect to the acrylate group - hydrogen, fluorine, chlorine, bromine, C ^ -C ^ -alkyl, phenyl-C4-Cf-alkyl, in which the FeIl group is possibly replaced by fluorine, chlorine or methoxy ,, dimethoxymethyl , ethylenedimethoxymethyl, trifluoromethyl, phenok-; simet'yl, possibly substituted with chlorine, pyridylethyl, furanylethyl, thienylethyl, ethoxycarbonylethyl, 2,2-difluoro, or 2,2 dichloro-3-phenylcyclopropyl, 2-phenyl-1,2epoxyethyl, ethenyl, possibly substituted for phenyl, trifluoromethyl , piano-, C <-C2-alkoxccarbonyl, oenzyloxy19 1600628 20 carbonyl, acetyl, furyl or benzthiazolyl, ethinyl, substituted by phenyl or или-butyl, phenyl, С, -С ^ alkoxy, benzoxazolylmethoxy, benzyloxy-, phenoxy -, possibly substituted by fluorine, chlorine, bromine, hydroxy-, methyl, trifluoromethyl, formyl, —C ^ alkoxyCi, possibly substituted by fluorine, propenyloxy, prop argiloxy, acetoxy-, methylsulphonyloxy, phenyl, phenoxy, nitro, amino-, formylamino- or acetylamino-, naphthyloxy-, isobutyryloxy, benzoyloxy-, possibly replaced by 6-butyl, benzoyl, possibly substituted by methoxy, C ^ -C ^ -alkoxycarbonyl, cyclohexyloxycarbonyl, allyloxycarbonyl, phenoxycarbo. a nityl in which the phenyl group is optionally substituted by methoxy, nitro, benzoylamino, furoylamino or Nthienylcarbonyl-L-methylamino; Υ in the position of ortho, meta or para with respect to the acrylate group - hydrogen, fluorine, chlorine, bromine, methyl, phenylstenyl, nitro or phenoxy; Ζ is hydrogen; or X and Υ, occupying adjacent positions in the phenyl ring, together form a condensed benzene ring, possibly substituted by phenyl, a condensed naphthalene ring, a condensed benzofuranyl ring, a condensed benzothienyl ring or a group or г and ру groups, when they occupy adjacent positions in the phenyl ring , 5 "e" together form a condensed benzene ring, or their sterioisomers, differing in terms of the fact that the compound of the general formula 20 where Cr X, Υ I - have the indicated values, undergo interaction 30 st With a compound of the general formula PH3P +, it is a pool, where K £ has the indicated value. Table) Compound K, 2 × 3 • x '4 Υ 5 Ζ' 6 Mpl., 7 'Olefin * 8 "** Isomer about 1 CH, cn, n' to n 37-38 7.55 '£ 2 SN, Sn, Nn Oil 6.65 2. 3 Sn, Sn2 Sn, Nn Mag 7.53 K 4 Sn, Sn, Sn. and and. n Oil 7.62 £ 5 sn, sn2 sn, sn2 n 'n n Masuo 7.62 G · 6 C6I, SP2 sn, n n Oil 756 2 7 sn, SeNuSNgn n n 37-38 7.67 δ 8 (СН,), С н, н и н Oil 7,44 Е 9 СН, сн, 2- (Е-С4НрСН: СН) 'к н 107-108 7,63 I 10 нн, СИ, 2- < E-SvN, CH! CH) nn Oil 6.57 Ζ 11 Sn, Sn, Sn, 3- (B-C6H5CH; CH) N, 104-105 7.58 E13 Sn, Sn, Sn, 2- (g-C4HgCH: CH) nn Oil 7.50 ί 14 dn, dn, 2- (g-s4NuSN: sn) gn I '93-94 6.34 Ζ 15 <ch, с, sn, 2- (Yo-S, Н5СК: СН) н. Н Oil 7.37 Е 19 Sn, Sn, Sn, 2-С6Н9С1С н н 86-87, 7.58 Е 21 1600628 '4 ι: 22 Continuation of table 1 one G ““ _g --- e: gp ------ _r ~~ - 1 ⁸ 45 0 four four 2 3 four 52 four one four four 3 four 53 0 0 four 0 2 four 55 0 0 * four 3 one* four* 56 four 0 * four four 0 * four"- 57 3 0 - four 0 0 58 0 0 0 0 0 3 60 four 3 four four four four 62 0 * 0 * four* 0 * 0 * 0 * 63 2 0 0 0 0 0 66 0 3 0 0 0 67 four four four four four four 88 four four four 3 0 four ί 90 four four four 3 3 four - 91 four four four four . - four - 92 0 3 0 0 0 four - 94 four four four four 0 - four 95 0 3 0 0 0 0 0 96 0 one 0 '0 3 - - 98 0 2 - 0 four four -  100 0 0 3 0 3 0 - 101 3 3 2 . four four four - 102 3 four four four four four - 103 four four four 3 four four - 104 four 3 four 2 four four - 105 0 * about* . h K 0 * 3 * 0 ^ - 106 0 3 0 0 0 four 0 107 2 2 four 0 0 0 0 108 3 3 0 0 0 0 0 109 0 0 2 0 0 0 0 110 0 four four 2 0 0 0 111 one one 3 0 0 four 0 114 . 3 3 four 0 four four four 115 four 0 four one four four four 117 four four four four four four four 119 3 0 - four 3 four four 120 3 0 - four 3 four four 120 2 0 0 b 0 0 0 121 four four four four four four four 122 four four four four four four four 123 0 0 3 0 0 3 0 124 0 0 3 0 0 0 one 125 2 0 four 3 0 four four 126 0 one four 0 four four four 127 0 0 0 0 0 2 0 128 four one four one 3 four four 129 3 0 four one 0 2 0 130 four 3 0 - four four 3 131 3 0 3 2 four four 0 132 four 3 four four 0 four 3 133 four four 0 2 0 four' one 134 four four four four four four 3 135 0 . 0 0 0 0 3 0 * Tested as a foliar spray at a concentration of 25 million ^-1. 43 1600628 44 Table7 Compound Wheat Barley Apple tree Pic Peanut Grapes I four four four 3 four four 2 four four four 3 four four four 3 four* 2 * 2 * 4 * 0 * - 7 four four four four- four four - 199 four four four four 0 four four 200 four four four 3 four four 0 201 four four four four 3 four four 202 four four four four four four four 203 four four four 3 3 four four 204 four four 'four four four four four 205 four four four 3 four four 3 206 3 0 four 0 - 3 0 207 0 four one four 2 four 3 208 2 0 one 2 four 2 0 209 3 2 four 0 0 3 3 * It was' tested at a concentration of 25 ppm only when splashing short leaves Table 7 Connections Wheat Barley Apple tree Pic Peanut Grapes one 2 3 th five 6 7 eight one four four four 3 3 2 - 3 four four four 3 3 four - five 0 0 0 0 0 2 - 6 four four four four four four - 7 four four four four four four - eight* 2 0 one 0 0 3 - ten ' four four - four 3 four four eleven one 2 0 . 0 four 0 9 four four four 3 four four four 15 2 * 2 * four* four* 0 four - 27 four* 3-8- L four* four* - - 33 four . four to 3 four four four 34 2 0 0 0 0 0 0 37 four four four 3 3 four - 40 0 0 0 one four. four - 43 3 one four 0 one 3 - 55 0 0 four 0 0 four 0 58 0 0 four 0 2 four - 66 3 four four 0 0 3 - 69 four four four 3 0 four four 70 four four four' 3 2 four four 92 four four four four four four 3 128 four four four four four four 0 150 0 0 3 0 0 four - 152 - - - - - 2 * - : 53 four four . four 0 3 four - 45 1600628 46 Table 7A continued 'Ί ----- ----- · P" 6 ' P 1 ° 160 0 four four 3 four " four 161 0 0 four 0 3 3 - 165 four four four four four four - 168 four four four four four four - 173 2 * - one*- four* Λ four* - - 174 3 2 four one 3 2 - 177 four four four 2 four four - 180 0 0 0 0 0 3 • - 181 four* about*- four* 0 * .0 * 0 *  - 182 0 2 one 0 one 0 - 183 3 four four four 2 four - 188 3 four four 3 four four - 189 four four four 0 four four 2 190 ^X ' ¹ one  3 0 0 0 0 3 191 four four four four 0 four four 192 four one 0 four 0 four 2 193 0 0 four 0 , 0 0 0 36 four 3 four four - four 3 42 four four four four four four four 54 one 0 0 2 four 3 0 60 2 four four one 2 0 2 63 four four four four four four four 64 four four four 2 four four four 82 0 four four 0 0 2 2 87 four four four four four four four 125 four four four 3 four four 3 132 four four four 3 four four four . 194 four four four four four four four 195 3 one four 2 2 four 3 196 3 four four - four four four 197 four 3 four four four four four 198 four ' four four four 3 four four * ** Spraying the leaves at 25 ppm Spraying the foliage at 100 ppm Table8 Compound Wheat Barley Apple tree Pic Ar ahi with Grapes one four four four 2 3 3 four four four four - 2 four 7 3 four - 3 four 0 158 0 3 0 0 0 3 165 four four 3 2 0 four 177 0 four 3 0 0 0 178 0 3 four 0 0 four . 180 four four four 3 3 four 184 3 four four 3 0 four 187 0 one four 0 0 0 Compound-mania i | Tables | | St 64 112 four five 6 and 28 "85" 87 9 " one one 1 C ^ H ^ Oil 7.59 E 2 2Г-С ₆ Н _Г - - £. 3 3-Р - С ₆ Н ₄ - - Е 31 1600628 ^{30 * 32} '"Continuation of table 4 four ² * four- five four 4-G - C ₆ H ₄ ' 44.5-45.5? 7.59 E five 2-C1-C _e H ₄ - '- E 6 3-C1-C ^ H ₄ - - E 7 4-C1-C ₆ H ₄ 49-50 7.57 E eight 2-Vg-S ₆ N ₄ - - £ 96 Z-Vg-S ₆ N ₄ - E ten 4-Br-C _th N ₄ - - Yo eleven 2-1-С ₆ Н ₄ - E 158 (CH _e ) _d C Butter 7.58 Yo 160 SN _g : SNCH _g '- - E 161 E ~ C _b H ^ CH: CHCH g - E_ 165 2-Pyridyl . 60-61 7.58 E 168 2- (5'-SG ₃ - -. - Yo Pyridyl) - - E 173 1-naphthyl - - E 174 2-Naphthyl - - E 177 ^C 6 ^H 5 Butter 6.24 Ζ 178 2-furyl Butter 7.59 E • 180 2-thiophenyl Butter 7.60 E 181 3-thiophenyl - - E 182 2-pyrrolyl - E 183 3-pyrrole.n - - E 184 SbH ^ -CH Butter 7.50 E 187 О ^ НрО ₂ С Liquid 7.59 one The chemical shift of the singlet from the olefinic proton on the beta-methoxyacrylate group (million " ^{ relative to tetramethylsilane), * solvent ΟϋΟΙ ^. Geometry of beta-methoxyacrylate group. T ab l and c and 5 Compound Table NMR spectrum one 2 3 ‘ _________________________________________3_____ 30 1 3.68 (ЗН, s); 3.83 (bN, s); 7.25-7.6 (ЗН, m); 7.52 (1Н _э с) 5 7.9-8.1 (1H, m) 40 G 3.60 (ЗН, s); 3.66 (ЗН, s); 3.87 (2H, s); 7.48 (1H, s) 42 1 3.60 (ЗН, s); 3.70 (ЗН, s); 3.75 (ЗН, s); 3.80 (2H, s); 7.50 (1H, s) 45 1 3.6 (ЗН, s); 3.75 (ЗН, s); 7.0-8.15 (5H, m) 52 1 3.66 (3rd, s); 3.76 (ЗН, s); 7.51 (1H, s) 53 1 3.56 (30N, s); 7.73 (ЗН, s); 7.1-7.7 (9H, m); 7.9-.8.1 (1H, M) 57 1 3.73 (ЗН, s); 3.85 (ЗН, s); 7.54 <1H, s) 66 1 3.53 (ЗН, s); 3.67 (ЗН, s); 3.85 (ЗН, s); 7.32 (1H, s) 3.7O (3N, s); 3.80 (ЗН, s); 4.97 (2H, s); 7.59 (1H, s) 67 33 1600628 34 Continuation of table.5 ΞΓΖΖ 92 one 1.28 (9H, s); 3.68 (ЗН, s); 3.82 (2H, s); 7.54 (1H, s) 126 one 1.32 (ЗН, t); 3.70 (ЗН, s); 3.82 (ЗН, s); 4.24 (2H, d); 6.38 (1H, d); 7.15-7.40 (2H, m) rrs 127 one 3.68 (ЗН, s); 3,80 (ЗН, s) .; 3.95 (2H, m); 4.08 (2H, m); 5.77 (1H, m); 7.15 (1H, m); 7.34 (2H, m); 7.56 (1H, s); 7.62 (1H, m) rrs 128 R 3.70 (ЗН, s); 3.78 (ЗН, s); 3.81 (ЗН, s); 6.33 (1H, d); 7.15-7.4 (ЗН, m); 7.64 (1H, s); 7.66 (2H, m) rrs 129 one 1.25 (ЗН, t); ² , 50 (2H, t); 2.81 (2H, t); 3.70 (ЗН, s); 3.82 (ЗН, s); 4.12 (2H, d); 7.0-7.3 (4H, m); 7.59 (1H, s), rrs 131 one 3.72 (ЗН, s); 3.83 (ЗН, s); 7.2-7.5 (7H, m); 7.71 (1H, s); 7.75-7.8 O (2H, m); 7.98 (1H, d) rrs 134 one 3.71 (ЗН, s); 3.74 (ЗН, s); 4.13 (2H, t, L7 Hz); '7.47 (1H, s); 7.97 (1H, shir.d) rrsh five 2 3.63 (ЗН, s); 3.78 (ЗН, s); 6.80-7.40 (8H, m); 7.46 (1H, s) 6 2 3.60 (ЗН, s); 3.75 (ЗН, s); 6.8-7.0 (4H, m); 7.14-7.32 (4H, m); 7.45 (1H, s) 7 2 3.62 (ЗН, s); 3.77 (ЗН, s); 7.48 (1H, s) 28 2 3.66 (ЗН, s); 3.80 (GI, s); 3.82 (ZN, s) 6.7-7.3 (8H, m); 7.51 (1H, s) 42 2 3.55 (ЗН, s); 3.71 (ЗН, s); 6.81-7.61 (14H, .m) (olefinic proton is darkened by aromatic protons) pp 60 2 3.61 (ЗН, s); 3.78 (ЗН, s); 6.7-7.3 (ЗН, m); 7.55 (1H, s) pp 63 2 3.59 (3N, e); 3.73 (ЗН, s); 6.3-7.3 (7H, m); 7.43 (1H, s) pp 64 '2 3.49 (ЗН, s); 3.60 (ЗН, s); 6.2-7.15 (7H, m); 7.32 (1H, m) rrs 66 2 3.65 (ЗН, s); 3.79 (ЗН, s); 7.48 (1H, s) 82 2 3.55 (ЗН, m); 3.65 (9H, m); 6.1 and 6.8-7.3 (1H and 6H, m); 7.50 (1H, s) ppm 87 2 3.46 (ЗН, s); 3.63 (ЗН, s); 6.3-7.2 (7H, m); 7.38 (1H, s) ppm 153 2 3.70 (ЗН, s); 3.79 (ЗН, s); 3.82 (ЗН, s); 7.53 (1H, s) 160 2 3.63 (ЗН, s); 3.80 (ЗН, s); 4.51 (2H, d); 5.05-6.39 (ЗН, m); 6.70-7.35 (4H, m); 7.46 (1H, s) 161 2 3.60 (ЗН, s); 3.74 (ЗН, s); 4.66 (2H, d); 6.00-7.40 (11H, m); 7.46 (1H, s) 3.54 (3N, s); 3.88 (ЗН, s); 6.6O (1H, s) 181 2 165 2 3.55 (ЗН, s); 3.74 (ЗН, s); 6.80 (1H, d); 6.95 (1H, m); 7 »15-7.40 (4H, m); 7.43 (1H, s); 7.65 (1H, m); 8.19 (1H, m) 182 2 3.85 (bN, s); 3.90 (ЗН, s); 5.00 (1H, d, L 7 Hz); 6.70 (1H, d, d 14 Hz); 7.50 (1H, s) 125 2 3.66 (ZN, s); "3.67 (ZN, s); 3.8 (ZN, s); 6.37-7.23 (7H, m); 7.46 (1H, s) ppm 132 2 3.63 (ЗН, s); 3.7 (ЗН, s); 3.73 (ЗН, s); 1600628 ³⁰ Continuation of table.5 ζ: G ---- T "---------------------------- 183 2 6.48-7.24 (7H, m); 7.49 (1H, s) ppm 3.75 (bN, s); 3.85 (ЗН, s); 5.50 (1H, d; 194 2 L 14 Hz); 7.50 (1H, s); 7.50 (1H, d. L 14 Hz) 1.3 (3N, t); 3.6 (3 ", s); 3.76 (ЗН, s); 3.95 195 2 (2H, d); 6.44-7.34 (8H, m); 7.44 (1H, s) ppc. 2.31 (3 ", s); 3.56 (3N, s); 3.7 (ЗН, s); 196 2 6.64-7.39 (ЗН, m); 7.45 (1H, s), rrs 3.6 (3 ", s); 3.77 (3N, s) 4.46 (1H, t); 4.52 197 2 (1H, t); 5.21-5.5 (2H, m); 5.86-6.21 (1 ”, m); 6.5-7.39 (8H, m); 7.47 (1H, m) rrs 3.14 (ЗН, s); 3.62 (ЗН, s); 3.77 (3 ", s); 198 2 6.83-7.38 (ЗН, m); 7.45 (1H, s) ppm 1.83 (ЗН, t); 1.8 (2H, m); 3.64 (ЗН, s); 3.78 199 2 (ZN, s); 3.87 (2H, t); 6.53-7.31 (9H, m); 7.50 (1H, s) RPT 1.23 (6H, d); 3.54 (3N, e); 3.7 (ЗН, s); 200 2 4.39 (1H, m); b; 34-7.27 (8H, m); 7.38 (1H, s) ppm 0.87 (6H, t); 1.38 (5H, m); 3.5 (3N, s); 3.64 201 2 (ZN, s); 3.72 (2H, d); 6.3-7.25 (8H, m) 7.37 (1H, s) ppm 3.0 (1H); 3.50 (30N, s); 3.60 (ЗН, s); 6,6- 202 2 7.1 (8H, m); 7.23 (1H, s) ppm 2.61 (1H, t); 3.62 (ЗН, s); 3.79 (ЗН, s); 3 3 4.65 (2H, d); 6.57-7.3 (8H, m); 7.45 (1H, s) ppm 3.61 (3N, s); 3.78 (ЗН, s); 6.8-7.3 (8H, m); five 3 7.4 / (111, s) 3.69 (ЗН, s); 3.88 (ЗН, s); 6.84 (2H, d); 165 four '7.6 O (1H, s); 8.10 (1H, dd); 8.20 (1H, d) 0.92 (9 ", s); 3.72 (3 ", s); 3.80 (ЗН, s); 178 four 7.58 (1 ”, s) 2.81 (4H, s); 3.68 (ЗН, s); 3.80 (ЗН, s); 180 four 7.59 (1H, s) 2.8-3.1 (4H, m); 3.72 (3 ", s); 3.81 (ЗН, s); 184 four 7.6O (1H, s) 1.80-1.92 (2H, m); 2.46-2.68 (4H, m) 3.69 (ЗН, s); 3.77 (ЗН, s); 7.5O (1H, s) 1.1-2.1 (m); 3.58 (3 ", s); 3.67 (ЗН, s); 39 one 95 one 4.85 (1 ", m); 7.44 (1 ", s); 7.94 (1H, apparent d, L = 7 Hz) 3.32 (ЗН, s); 3.51 (3N, s); 3.56 (3 ", s); 3 2 6.54-7.5 (8H, m) 3.6 (3 ", s); 3.76 (3 ", s); 6.56-7.42 (8H, m); 27 2 7.5 (1H, s) 3.62 (ЗН, s); 3.75 (3 ", s); 3.8 (3 ", s); 43 2 6.7-7.3 (8H, m); 7.5 (1H, s) 3.55 (3 ", s); 3.65 (ЗН, s); 6.6-7.2 (14 ", m) 173 2 3.66 (3 ", s); 3.82 (ЗН, s); 6.86-8.36 (11H, m); 174 2 7.5 (1 ”, s) 3.5 (3N, s); ‘3.6 (3N, s); 6.7-7.95 (12H, m) 98 one 3.67 (ЗН, s); 3.92 (3 ", s); 5.23 (1H, dd); 1 68 ABOUT 5.65 (1H, dd); 6.52 (1 ", s); 6.80 (1H, dd) 3.58 (3 ", s); 3.72 (ЗН, s); 6.88 (1H, dd); 7.1-7.5 (4 ", m); 7.40 (1H, s); 7.84 (1H, ds); 8.44 (1H, br.) 1600628 38 Continuation of table.5 Fri> c · -.......: 188 2 3.49 (ЗН, s); 3.88 (ЗН, s); 6.61 (1H, s); 6.92-7.08 (ЗН, m); 7.2-7.4 (ЗН, m); 8.148.2 (2H, m) 93 one 3.49 (ЗН, s); 3.61 (ЗН, s); 5.17 (2H, s); 7.17.5 (m); 7.36 (1H, s); 7.95 (1H, wide doublet 94 one 1.27 (3N, t); 3.59 (3N, s); 3.70 (2H, q); 3.72 (ЗН, s); 7.1-8.0 (4H, m); 7.40 (1H, s) 106 one . 3.75 (ЗН, s); 3.85 (ЗН, s); 6.7-7, ZO (ZN, m); 7.6 (1H, s) 107 one 3.17 (2H, s); 3.72 (ЗН, s); 3.87 (ЗН, с) 7.22-7.42 (9H, m); 7.64 (14, s) 108 one 2.85-3.07 (2H, m); 3.64 (ЗН, s); 3.73 (ЗН, s); 7.17-7.40 (9H, m); 7.47 (1H, s) 109 one 3.70 (ЗН, s); 3.85 (ЗН, s); 7.00-7.10 (1H, d 3 9 Hz); 7.39-7.5 O (1H, m); 7.55 (1H, s); 7.79 (1H, s) 110 ' one 2.45 (ЗН, s); 3.65 (ЗН, s); 3.85 (ЗН, s); 7.15-7.18 (1H, m); 7.35-7.48 (ЗН, m); 7.52 (1H, s); 7.60-7.64 (1H, m); 8.24 (1H, m); 8.39 (1H, m) 1 12 one 3.71 (ЗН, s); 3.86 (ЗН, s); 7.16 (1H, d L 10 Hz) 7.27 (1H, d C 10 Hz); 7.58 (1H, s); 7.63 (1H, s) 113 one 3.73 (ЗН, s); 3.86 (ЗН, s); 6.75-6.30 (1H, m); 6.90-7.00 (1H, m); 7.10-7.20 (6H, m); 7.62 (1H, 1 17 * one 7.61 (ЗН, s); 7.72 (ЗН, s); 4.68 (2H, d); 5.05-5.5 (2H, m); 5.65-6.3 (1H, m); 7,! - 7.6 (m) 7.45 (1H, s); 7.98 (1H broad.d) 1 19 one 3.57 (ЗН, s); 3.64 (bN, s); 6.6-6.8 (ЗН, m); 7.05-7.45 (4H, m); 7.44 (1H, s); 8.05 (1H, bd) 120 one 3.30 (4H, m); 3.58 (4H, m); 3.69 (ЗН, s); 3.81 (ЗН, s); 7.2 ~ 7.45 (m); 7.54 (1H, s) 2 2 Solvent: 8 ^ -DMSO 3.39 (ЗН, s); 3.61 (ЗН, s); 6.50-7.20 (8H, s); 7.42 (1H, s) 9 2 3.41 (ЗН, s); 3.55 (ЗН, s); 6.75-7.20 (8H, s); 7.32 (1H, s) 15 2 2.22 (ЗН, s); 3.55 (ЗН, s); 3.68 (ЗН, s); 6.4-7.4 (ЗН, m); 7.4 (1H, s) 33 2 3.41 (ЗН, s); 3.78 (1H, s); 6.68-7.35 (13H, m); 7.48 (1H, s) 69 2 3.45 (ЗН, s); 3.55 (ЗН, s); 6.55-7.25 (7H, m); 7.35 (1H, s) 70 2 3.45 (ЗН, s); 3.70 (ЗН, s); 6.80-7.25 (7H, m); 7.50 (1H, s) 92 2 3.5O (3N, s); 3.65 (ЗН, s); 6.70-7.30 (7H, m); 7.40 (1H, s) 128 2 3.60 (ЗН, s); 3.70 (ЗН, s); 3.71 (ЗН, s); 6.40-7.30 (7H, m); 7.45 (1H, s) 190 2 0.89 (ЗН, t); 1.20-1.50 (6H, m); 1.50-1.80 (2H, 3.68 (ZN, s); 3.82 (ZN, s); 3.92 (2H, t); 6.847.00 (2H, m); 7.10- 7.30 (2H, m); 7.47 (1H, s) 191 2 3.41 (ЗН, s); 3.51 (3N, s); 6.80-7.20 (8H, m); 39 1600628 ⁴⁰ Continuation of table.5 H ί a 3 7.31 (1H, s) 193 2 1.23 (6H, d); 2.3-3.0 (1H, m); 3.60 (ZN, s): 3.69 (ZN, s); 6.9-7.4 (M); 7.47 (1H, s) 208 2 3.50 (30N, s); 3.65 (311, s); 6.7-7.3 (8H, m); 7.45 (1H, s); 8.1 (1H) ppb 209 2 3.60 (ЗН, s); 7.76 (ЗН, s); 7.00 (1H, d); 7.32 (6H, m); 7.46 (1H, s); 7.56 (1H, s); 9.94 (1H, s) pp 9 3 3.58 (3N, s); 3.68 (ЗН, s); 6.62-7.4 (18H, m); 7.43 (1H, s) ten 3 3.06-3.26 (4H, m); 3.56 (3N, s); 3.72 (ЗН, s); 6.88-7.20 (7H, m); 7.59 (1H, s) Peak, durping in many resonances, belongs to amide rotamers. As a whole, consistent with the structure. T a b l and c a 6 Compound Wheat Barley Apple tree . ί Pic Peanut Grapes one 2 3 four five 6 7 eight one four four four 0 2 four 2 2 0 0 0 0 0 3 0 0 0 0 0 four four 0 0 one 0 0 0 five 0 0 0 0 0 one 7 0 0 one 0 0 0 9 four four four 3 * .four four Yu - four four four 3 * four four eleven 0 0 0 0 0 3 12 0 0 0 0 0 2 13 four 2 four 2 four four 14 four four four - four four four nineteen four four four 3 0 four 20 0 2 four 3 3 four 21 0 four 0 0 four four 22 0 0 0 0 0 four 23 four 0 ' 0 0 four four 24 four 2 four 0 0 four 25 ? 0 0 0 - 3 26 one 0 - 0 - one 27 η 2 four 2 2 four 28 3 four four 3 four . four 29 2 3 four 0 0 3 thirty four four four 3 .3 four 31 0 four 2 0 0 3 32 3 0 3 ' one 3 0 35 0 • 2 0 2 four 0 37 four  one four four four - 39 0 0 four 0 2  - 40 four four four · four four four 42 3 four four four one four 41 1600628 42 Continuation of table 6 ¹ <- \ WELL CH ₃ 0 ₂ C ' 'CH Es ₃ Table ^. Compound TO M.p. ,/WITH Olefino, out * Isomer ** one 2 3 four ' ⁵ 1 with ₆ n _? 3-C1 H 85-6 7.33 E 2 C _b H _y 4-ΝΟ ^ H - - E 3 с ₆ н _у 5-C1 H Butter 7.47 E 4 С ₆ Н _? five 6-Ν0ι 5-ΝΟ, · H H Butter 7.60 E E 6 2-Pyridyl 5-E H Butter 7.40 E 7 2-pyridyl 5-C1 H 91-93 - Yo 8 2-pyridyl 5-CH ₃ : H 'Butter - E yu '' ⁹ b ~ s ₆ n ₅ o n n Butter Butter 7.43 <7.59 £ £ eleven** . n 106-107 6.53 ζ "E? * *** Chemical shift of the singlet from the olefinic group on the beta-methoxyacrylate group, (million ~ ^{1 2 3} relative to tetramethylsilane), solvent SBSGz Geometry of the beta methoxyacrylate group Compound 10 is: about· With a co СН ₃ 0 ₂ Сн # Ύ Y Compound II is: one n t 3 PT 60 2,4-di-Pc ^ H ₃ Liquid 7.55 63 3,4-di-R-C ₆ N, Liquid 7.43 64 3,5-di-RC-H, Butter 7.42 69 3,4-di-C1-C _th H C Butter 7.35 70 3,5-di-C1-C ^ Well Butter . 7.5 82 3,5-DI-CH3O-CH3 Liquid 7.43 87 3,5-Р, 4-С1-С ₆ Н _? Liquid 7.38 92 3-S1,4-G-C _b H5 Butter 7.40 125 2-C1,5-CH _? OC ₆ N _? (Resin 7.46 128 3-C1,5-CH _? OC ₆ N _? Butter 7.45 132 3-CH ₃ O, 4-C1-C ₆ Nz Resin 7.49 150 Pentafluoromethyl 79-81 7.58 151 Pentachlorophenyl - - 152 H - 153 CH ·? Butter 7.52 158 (CH) ₃ С - - 160 sn ^ gsnsng Butter 7.46 161 L-C ^ H ₄ C1!: CHCH ₂ > Butter 7.46 165 2-pyridine Butter 7.43 168 2- (5-CP _? -Pyridyl ^ 1 Oil 7.40 173 1-naphthyl Butter 7.50 174 2-Naphthyl 90-91 In aromatics 177 С ^ Н ^ СНг. 76-77 7.49 178 C ₆ H5C (CH _e ) _g - - 180 CH? 74-75 7.55 181 with _bn ^ · Butter 6.60 182 Mr. -Sn ₃ about ₂ s-sn = sn Butter 7.50 183 E-CH, O _y C 'CH = CH Butter 7.60 184 n '. 125-6 7.60 185 with _b n ^ co 73-75 7.50 187 4-0 ^^ 0-0 ^ 4 Butter 7.5 188 Ε-Ν0 ₂ -0 ₆ Ηα Butter 6.61 189 ' 2- (Benzksazolil_ \ SNL84-86 7.51. 190 ch ₅ (ch _g ) $ - Butter 7.47 191 Wed- ₅ -c ₆ n ₄ Butter 7.31 192 4th-C ₄ H ₉ -C ₆ 1C.-C0 95-96 7.52 193 (CH?) _G SNSO Butter 7.47 194 З-С ^ Nuo-С ^ Н ^ -. Resin 7.44 195 3-СН _Э СОО-С ₆ Н5- Resin 7.45 196 3-CH _? : CESN _g OC ₆ N Resin 7.47 197 s-CH _{r zo?} o with _a n _g Resin 7.45 198 s-CH ,, N _{7 O-C} n _t Resin 7.50 199 3- (SNZ) 2. CH0-SbN-Resin 7.38 200 's- (with _Mr. n ₅ ) ₂ Åsn _g of- _in H ^ Resin 7.37 201 3-СНК ₂ 'СР ^ O-С ^ Well · Liquid 7.28 202 3-CH: CCH ₄ 0-C _e K5 · Resin 7.45 203 4-CH ₇ : SNCH _th 0 -C _A H g-30-81 7.41 204 4-CH: CCH ₂ 0-C ₆ Hs 107-107.5 7.42 205 4- (CH?) = CH0-C ₆ H 86 _g 7.41 206 4-CH ₃ CO.O-OC ₆ H ^ 112 7.40 207 4tCH _? 8О _г О-С _й Н _г 93-94 7.40 208 3-NSONN-C ₆ N "g Liquid 7.45 209 s-on-s ₆ n $ - Resin 7.46 * Geometry of beta methoxyacrylate group. ! | m | m (m1m (m | n | mgm | u | and | m1n. | m | | | Ц m | n | m! μ | μιμ1ν | ρι | μ | μ | μ1μ | et1m | m1m | m | m | mrR0i | m | m | m | m (m | m | _m (mgetGm pn | and Mi be 1600628 thirty 29 T a b l and c a 3 Connecting TO Υ Ζ - M.p. Olef- ¹ isomer niya ° С new*" one . ... 2 3 four one Butter 7.47 2 2-E-C ^ H ^. Butter 7.42 * (and _y- dmso) 3 3-РС С ₆ Н ₄ Butter 7.5 four 4-hc _th nts. 77-78 7.5 five 2-C1-C ₆ H ₄ Butter 7.46 6 s-c1-c _e n ₄ Butter 7.45 7 4-C1-C _b NF Butter 7.48 eight 2-Br-C _th H ₄ - - 9 3-Br-C ₆ n ₄ Butter 7.32 ten 4-Br-C ₆ H ₄ - - eleven 2-1-С ₆ Н ₄ - - 13 4-1-С ₆ Н ₄ - - 14 2-CH ^ -C ₆ H ₄ - - 15 3-CH _{? J} H ₄ -C Butter 7.4 sixteen 4-CH _? -C _b N ₄ 80-81 7.5 nineteen 4-CH, CH _g -C ₆ H ₄ - 20 2- (CH ₈ ) ₂ CH-C ₆ H4 - - 21 3- (СН _Я ) ₂ СН-С _Й Н ₄ - - 22 4- (CH _? ) ₂ CH-C _b H ₄ - - 23 2- (snr ₃ C- _{C and} N ₄ - - 24 3- (СН _? ) ₃ -С-С _Й Н ₄ - - 25 4- (СН,), С-С _Й Н ₄ - - 26 2-CH ₃ O-C ₆ H ₄ - - 27 s-CH ₃ O-N ₄ with _d Butter 7.5 28 4-CH _? OS ₆ H ₄ Butter 7.51 29 2-CE _? OS _B N ₄ - - thirty w-fr _{5 is 6} n ₄ - - 31 4-СК, О-С ₆ Н ₄ - - 32 2 _{nd th ?} OS ₆ K ₄ - - 33 Z-S ^ N ^ O-SbNf Butter 7.48 34 4-0 ^ 0-0 ^ 131-131,5 7.55 35 UQ 2 -C _r H _{4 minutes} - - 36 3-Ы0 _£ -С _with Н ₄ 109-110 7.71 37 4-I0 _x -C ₆ N ₄ 107-108 7.49 39 з-ин ₂ -с _б н ₄ - - 40 4-Ing. - C _b N ₄ 113.5-114.5 7.52 42 З-с ₆ н _г -с _й and ₄ Resin Not out 43 L- ₆ K; -c ₆ and ₄ 108-109 In the aroma tick 45 З-но _г с-с _й н ₄ - - 54 з-но-с _й н ₄ 115-116 7.40 55 4-H0-SYN ₄ 137-138 7.54 57 s-CH _z C (O) pl-C ₆ H ₄ - 58 4-CH _} C (O) IN-C ₆ n ₄ 43-45 7.48 ιμ | "| m ι m> m | m) m 1 m) m ιμ I m 1 m 1 m> m 1 m | m 1 m) m | m | m 1 m 1 m 1 m | m mind ιμ them” m | m | m | m | m Um | m 1 m cm "m (m | m) m | m 1 m mIm | 28 27 1600628 Continuation of table 2 ¹ 1 2 1 h 20 sn, sn, 21 sn, sn, 22 sn, sn, 23 sn, sn, 24 sn. cn 25 sn, sn, 26 sn, sn, 27 sn, sn, 28 sn, sn, 29 CH, sn. thirty sn, sn, 31 sn, sn, 32 sn, sn, 33 sn, CH, 34 sn, sn, 35 sn, sn, 37 sn, sn, 39 sn, sn, 40 sn, sn, 42 sn, sn, 43 CH, sn, 45 sn, sn, 52 sn, sn, 53 sn, sn, 55 sn, sn, ⁵⁶ sn. sn. 57 SI, sn, 58 sn. sn, 60 sn, sn, CH, sn, with 62 sn, sn, 63 sn, SI, ( 64 sn, sn, 66 sn, sn, 67 sn, sn, 69 sn, sn, 70 sn, sn, 2-CH _g : CH 2-C1 4-C1 2-C1 2- C1 3- C1 3-C1 2-C1 2-CH, 2-CH, 2- (CO ₂ CH,) 2-CP, 2-С _to Н, 2g-С _in Н, Н (СН,) СО 2-С ₆ Н ₅ СОН (СН ₅ ) 2-С ₆ 1ЦСО 2-С _in Н _at СО _g 2- {Tsnkoheksil) C0 _g 2-C ₆ N, CH _g 2- (4-СН} О-С ₆ Н ₄ ) СН ₂ 2-С ₄ Н, (СН,) _г С 2-ЫО ₂ 2-С ₆ Н _у 2-С ₆ Н, (О) 2- (E GZ-SShSN) ^{2_ (} - O-CH-.CH) with est _{e x} and n n 4-C1 6-C1 5- C1 5- C1 6- Р н n n n n n n n n n Ying n to n n n n n n n n and n and to n n n n n n n n n n n n n n n n n n Oil 65-66 61-62 68-69 141-142 '126-127 Oil 79-80 Oil 62-63 Oil 65-66 106-107 82-85 Butter Butter Butter Butter 84-85 Butter Butter Butter Butter 97-98 63-84 Sn ₃ about _and with ^x \ η ^ζ Λ / ^main » SNFS SNSOTS SN ; SNFS 7.57 7.60 7.56 7.56 7.61 7.58 6.70 7.62 7.55 6.52 7.52 7.56 7.34 E Yo B E Eb B E B B 2 E E 7.30 7.43. 7.44 7.48 7.50 In aromatics 7.51 In aromatics 7.63 B E Yo B E 107.5-110 6.56 124-125 7.54 7.54 7.47 7.63 112-113 7.82 / and hons sire ABOUT?? one ^and C _x osn ₃ θ £ CH ₃ 0 # CH CHZO1C '\ n II H H CH, 2- <O = CH. 152-153 In the aroma , DOS ₃ Η 122-123 7,73 H Oil 7.32 H Oil. 7.59 E Yo E 23 1600628 24 Continuation of table.1 “· < 9 ΤΊ: οΞθΞΞζ ::: ιτΞΐΞΐ: Ξ: ζΕΞΈ: 88 CH, CH, 90 CH, CH, 91 ’CH CH, 2-С ₆ Н, СОНН M ^ SDON) H 99-100 V a-E mate H 124-125,5 7.67 E хЧ х ⁰ ^ 'хЧ х ° С «3 СН ₃ О, С ОН СН ₃ О ₂ С ОН And 106-107, 7.81 92 93 95 CH, CH, CH, CH, CH, CH, CH, CH, ' 2 - ((СН,), С.С »С) 2-С ₆ Н, СН _g О _г С 2-С ₆ Н, О ₂ С ² СХсЫсн ^, H H H H n n n n Butter Butter Butter 131-132 7.54 7.36 7.40 7.43 96 CH, CH, 2 -, (СНаСН ^ О ^ С) n n 118-119 6.42 106 CH, CH, 2-G C1 C1 4-E n Butter ?, " 107 CH, CH, 2— (trans) H n Butter 7.64 108 CH, CH, 'Ρ PM 2- (trans-C ₆ H5- ~ ^< ~'"-) H n Butter 7.47. 109 ‘CH, ' CH, 2-VE 4-BE n Butter 7.55 110 CH, CH, 2- (2-CHa-pyrid-3-yl) H n Butter 7.52 Ό 111 CH, CH, 2- (trance “SsNe N. n 136-137 7.50 112 CH, CH, 2-BP ¹ 4-C1 n Butter 7.58 113 CH, CH, 2- (ЕС С ₆ Н, С (СР,): СН) H n Butter . 7.62 114 CH, CH, 2-С ₆ Н, СН _g З H n 65-68 7.54 115 CH, CH, 2-C _b N, ZS0 · H n 101-105 7.46 116 CH, CH, С-С ₆ Н ₅ СН ₂ О _Х С H n Butter 6.49 117 CH, HH, 2-CH ₂ : SNCH _g O _g C n n Butter 7.45 118 CH, CH, 2-С ₆ Н „М (СН,) СО n n Butter 7.50 119 CH, CH, 2- (3-CH, 0-C ₆ H ₄ ) n n Butter 7.53 · 120 CH, CH, 2- (about (2heo) 7.44 • n n Butter . 7.54 121 CH, CH, 2- (3-C1-C ₆ H ₄ 0) CH ₂ n n ' 82 7.59 · 122 CH, CH, 2- (4-C1-C ₆ H ₄ O) CH, n n • 104 7.59 123 CH, sn, 2-CHO · n n 67-69 7,69 124 CH, sn, 2- (СН, b) _g СН · n n 56 7.54 125 CH, CH, 2-С ₂ Н, 0 _g С «С (СН): СН n n 93-96 7.67 126 CH, sn, 2-C _g N, O _g S. CH: CH n n Butter 7.63 127 CH, CH, n n Butter 7.56 128 CH, sn ·,. 2-СН, 0 ₂ С · СН: СН n n Butter 7.64 ’ 129 CH, sn, 2-CH, C0-CH: CH n n 90-91 7.65 130 CH, sn, n 123-127 7.75 СНзОгС ^ СН ' , 6sn. 131 sn, CH, ² TO ^ -СН'СН H 132 CH, CH, 2-С ₆ Н, СН _g О-СО СН: СН n 133 CH, CH, 134 CH, CH, 2-С, Н _g 0С0 n 135 CH, CH, 2-VgSN _g · n * Chemical Singlet shift from olefinic proton Solid 106-108 161-162 7.71 7.61 7.72 | ГЧ | Я »М | М ΙΜΙΜί 1Я | Я1Я1М | Я | М | Я | Я. , Я1М | Я1ШЯ "Ч1" 1RLYA | I! I I »1Я group (mn ’relative to tetramethyl £ & Geometry of Oet-methoxy Acrylate Group Liquid 84 7.47 7.61 on beta-methoxyacryl solvent: C0C1, 25 1600628 26 Table 2 Yu? ° * ^CH s '% ng Es ₃ Compound M.p. ----------- _g ----- Olefin Isomer 2 2 2 2 2 2 2 BEHIND 47 1600623 48 / T a b and c a 9 Compound Wheat Barley Apple tree Pic Peanut Grapes Strobe Lurin ". 9 0 0 0 0 0 0 (table 1) four 3 four 3 four four ' Table 1L AH Al 2 2 2 2 four 2 2 2 Τν ra 13 The sun RS Se Ss СЬ C1 8o Test at 6 ", 35- ν / million (active ingredient)