LT3730B - Propene acid derivatives, processes for preparing thereof, compositions and funguses, insects or ticks control method - Google Patents

Description

The present invention relates to propenoic acid derivatives useful as fungicides, insecticides and miticides, to processes for the preparation thereof, to compositions containing them, to their use in combating fungi, in particular in controlling fungal infections of the plants, or in controlling insects or mites.

The present invention provides a compound of formula (I):

R

and stereoisomers thereof, wherein A is hydrogen, halo, hydroxy G ^ _ ^ alkyl, C ^^ alkoxy, haloalkyl, C ^ _ ₄ haloalkoxy / C ^ _ ^ alkylcarbonyl, C ^^ alkoxycarbonyl, phenoxy, nitro,

2. _. . . . .

or cyano; R and R 'which may be the same or different are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted aralkyl, optionally substituted heteroarylalkyl, optionally substituted aryloxyalkyl, optionally substituted heteroaryloxy, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted heteroaryl, _r optionally substituted aryloxy, optionally substituted 'heteroaryloxy, nitro, halo, cyano, -NR ³ R ⁴ , -CO 2 R ³ , -CONR ³ R ⁴ , -COR ³ , -S (O) n R ³ , where n is 0, 1 or 2, (CH_) PO (OR) ', where m is 0 or 1, arz mz

2 ba R and R are joined to form a carbocyclic or heterocyclic ring system; R and R ', which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted aralkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl.

The compounds of the invention have at least one carbon-nitrogen double bond and at least one carbon-carbon double bond and are sometimes obtained in the form of a mixture of geometric isomers. However, these mixtures may be split into individual isomers and the present invention encompasses these isomers and mixtures thereof in any ratio.

The individual isomers, which are the result of an unsymmetrically substituted double bond of the propenoate group and the oxime, are designated by the commonly used symbols E and Z. These symbols are defined by the Cahn-Ingold-Prelog system described in detail in the literature (see e.g. J.March Advanced Organic Chemistry Modern Organic Chemistry), 3rd ed., Wiley-Interscience, p. 109 et seq.).

Due to the double bond of the propenoate group, one carbon isomer is usually more active as a fungicide than the other, and the one where the -CO _? CH and -OCH are on opposite sides of the olefinic bond of the propenoate group ((E) -isomer). These (E) -isomers represent a preferred embodiment.

Halogen includes fluorine, chlorine, bromine and iodine.

Alkyl, and alkyl moieties of alkoxy, aralkyl and aryloxyalkyl groups, may be in the form of linear or branched chains, and unless otherwise stated, will have from 1 to 6 carbon atoms, respectively. Examples include methyl, ethyl, isopropyl and tert-butyl. Possible substituents include halogen (especially chloro and fluoro), hydroxy, and C ₁ _ ₄ alkoxy. Examples of substituted alkyl and substituted alkoxy are trifluoromethyl and trifluoromethoxy.

Cycloalkyl each C ^ -gCikloalkilas, for example, cyclopropyl and cyclohexyl, and cycloalkylalkyl each C ^ _gCikloalki1 (C i _ ₄₎ alkyl, such as cyclopropyl ethyl.

Alkenyl and alkynyl have from 2 to 6 carbon atoms, respectively, typically from 2 to 4 carbon atoms, and are in the form of linear or branched chains. Examples include ethenyl, allyl, propargyl. Substituted alkenyl and alkynyl groups include optionally substituted arylalkenyl (especially optionally substituted phenylethenyl) and arylalkynyl.

Aryl and aryl moieties of aralkyl, arylalkenyl, arylalkynyl, aryloxy, and aryloxyalkyl include phenyl and naphthyl.

A carbocyclic or heterocyclic ring system which

... can form together R and R, is the C ₅ _ ^ alifatme, aromatic, or mixed aliphatic / aromatic carbocyclic ring system, for example, cyclopentyl, cyclohexyl, and cikloheksadienonilas such groups that contain a fused benzene žie4 sively and / or substituents such like methyl? or it may be a 510 membered heterocyclic ring system such as tetrahydro pyranyl.

The term heteroaryl is used to describe aromatic heterocyclic groups. Heteroaryl and heterocyclyl and heteroaryl and heterocyclyl moieties of other groups, such as heteroaryloxyalkyl and heterocycloalkyl, are typically five or six membered rings having one or more O, N or S heteroatoms which may be fused to one or more other aromatic, heteroaromatic or heterocyclic rings such as benzene ring. Examples include thienyl, furyl, pyrrolyl, triazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl and quinoxalinyl groups and their N-oxides.

The substituents which may be on the optionally substituted or heteroaryl moiety include one or more of the following substituents: ha-logene, hydroxy, mercapto, C _1-4 alkyl (especially methyl or ethyl), C _2-4 alkenyl (especially allyl), C _2-4 alkynyl (especially Propare Gil), C ^ _ ₄ alkoxy (especially methoxy), C2_ ₄ alkenyloxy (especially allyl oxy), C ₂ _ ₄ alkynyloxy (especially propargyloxy), halo (C ^ _ ₄₎ alki las (especially trifluoromethyl), halo (C ^ _ ₄₎ alkoxy (especially + Rifle rmetoksi), C ^ _ ₄ alkylthio (especially methylthio), hydroxy (C ^ _ ₄₎ alkyl, C ^ _ ₄ alkoxy (C ^ _ ₄₎ alkyl, C ^ gcikloalkilas, C 1-6 Cycloalkyl (C 1-4 alkyl - optionally substituted aryl (especially optionally substituted phenyl), optionally substituted heteroaryl (especially optionally substituted pyridyl or pyrimidinyl), optionally substituted aryloxy (especially optionally substituted phenoxy), optionally substituted heteroaryloxy (especially optionally substituted pyridyloxy or pyriraidinyloxy), optionally substituted aryl (C ₄ ) alkyl (especially optionally substituted benzyl, optionally substituted STAS and phenethyl optionally substituted with acetyl fe n-propyl) in which the alkyl moieties possibly replace the hydroxy group optionally substituted hereroaril (0 ^ _ ₄₎ alkyl (especially optionally substituted pyridyl- or pyrimidinyl () alkyl) optionally substituted aryl (C_. ) alkenyl (especially optionally substituted heteroaryl (C ₂ _ ₄₎ alkenyl (especially optionally substituted piridiletenilas or pirimidiniletenila's) optionally substituted aryl () alkoxy (especially optionally substituted benzyloxy), optionally substituted heteroaryl (C ^ _ ₄₎ alkoxy (especially optionally substituted piridilarba pyrimidinyl (C i _ ₄₎ -alkoxy), optionally substituted piridilarba pyrimidinyl (C _1-4) alkoxy, optionally substituted aryloxy (C ₁ _ _i,) alkyl (especially phenoxymethyl), optionally substituted heteroaryloxy (C i _ ₄₎ alkyl (especially optionally substituted piridiloksi- PIRIMED diniloksi or (C ^ _ ₄₎ alkyl), acyloxy, C ^^ comprising alkanoyloxy (especially acetyloxy) and bezoiloksi, cyano, thiocyanato, nitro,, -COOR ', -OSO ₂ R', _-SO? R ', and R are independently C ^ _ ₄ alkylthio, C ₂ _gCiklofenilas or benzyl possibly substituted by halo without -NHCOR', - NR'R "-NHCONR'R, -CONR'R -SO ^ ' ·, -CR '= NR or -N = CR'R " wherein R' hydrogen, C ^ _ ₄ alkyl, C ^ _ ^ alkoxy, alkyl, Cg_gCikloaIki1 (C i _ ₄₎ alkyl, the fenilinė or benzylic groups are gen, ^ _ C ₄ alkyl or C ^ _ ₄ alkoxy.

The substituents which may be present on any of the above substituents on the aryl or heteroaryl rings are one or more of the following substituents: halogen, hydroxy, mercapto, _.

C, _ ₄ al kilas C ₂ _ ₄ alkenyl, C ₂ _ ₄ alkinyl, C ^ _ ₄ alkoxy, C ₄ _ ₉ lok alke ni si, C ₂ _ _{/ 1} alkynyloxy, halo (C ^ _ ₄₎ alkyl , halo (C ^ _ ₄₎ alkoxy, C ₁ _ ₄ alki1tio, hydroxy (_ ₄₎ alkyl, C ₁ _ ₄ alkoxy (C ^ _ _A) alkyl, C _o.-cikloslki las C- _r cycloalkyl (C ,.) alkyl, alkanoyloxy, benzoyloxy, cyano, thiocyanate, nitro, -NR'R, -NHCOR ', -NHCONR'R, -CONR'R, -COOR', -SO 4 R ', OSO 4', -COR ', -CR' = NR or -N = CR'R, where R 'and R have the meanings given above.

According to one aspect the present invention provides formula (I) jun6 Ginis, wherein A is hydrogen, halo, hydroxy, methyl, methoxy, trifluoromethyl, trifluoromethoxy, C ^ _ ₉ alk.ilkarbonilas C ₂ _ ^ alkoxycarbonyl, phenoxy, nitro or cyano; R ¹ is a ^C -į_ ₄ alkyl, halo (C ₃ _ ₄₎ alkyl, C ^ _ ₄ alkoxy, halo (C) alkoxy, C ^ _ ₄ alkylcarbonyl, C - ^^ alkoxycarbonyl, cyano, phenyl (C λ) alkyl , phenyl, single or six membered J. aromatic heterocycle containing one or more 0, N or S atoms and possibly fused to a benzene ring, and the aromatic heteroaromatic moieties of any of the above groups are usually substituted with one or more of the following: halo, hydroxy, C ^^ alkyl, halo (C i _ ₄₎ alkyl, C ^^ alkoxy, halo (C _i-4) alkoxy, C ^ _ ₄ alkylcarbonyl, C ^ _ ₄ alkoxycarbonyl, nitro, cyano, phenyl, phenoxy, benzyl or benzyloxy; R is hydrogen, halogen, C ^ _ ₄ alkyl, halo (C i _ ₄₎ alkyl,

C 1-4 alkylcarbonyl, C 1-4 alkoxycarbonyl, cyano or phenyl;

1-4 1-4

1.2.

or R and R combine together to form C ₃ _ ^ gkarbociklmę ring system. ·

In another aspect, the invention provides a compound of formula (I) wherein A is hydrogen or halogen; R ^ is C ^^ alkyl, benzyl, C ^ _ ₄ alkylcarbonyl, C ^ _ ₄ alkoxycarbonyl, cyano, phenyl, thienyl, triazolyl, thiazolyl, pyridyl, pyrimidine las, pyrazinyl, pyridazinyl, triazinyl, quinolinyl or quinoxalinyl, any of the above groups aro matic or heteroaromatic moieties are optionally substituted with one or more of the following substituents: halogen, C - ^^ alkyl, trifluoromethyl, C ₃ _ ₄ alkoxy, trifluoromethoxy, nitro, cyano, feni2 las or benzyloxy; R is hydrogen, C ^^ alkyl, C ^ _ ₄ alkylcarbonyl, C ^ _ ₄ alkoxycarbonyl, cyano or phenyl; or R ^

R is joined together to form a cyclopentyl or cyclohexyl ring with which a benzene ring is possibly fused.

The present invention is illustrated by the following compounds. In Table 1, the meti group 1 is the (E) -configuration.

listed in Table 1, -Methoxypropenoate

~ 3 cn ui. {I u w ffl c

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Table

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H □

H · o

CA. I O <n n ΟΊ Ω 3 ' CA. 1 '73 +3 H · to LO LO LO 4 * 1 LO 1 ro 1 4 ^ » 1 LO ί o hH H- o n M O cn 4 ^ Ln 42 » Ω Ω Ω Ω n -r} Ln (JI □ H · To H · H · 1 1 · » H · H · H · ^ri J aJ 0 Pi LO Gb Cb Cb UI Pb Ln Pi pi pi LO LO 1 □ 1 > b OJ H · · «· H · | □ P5 □ t i Ό cn 0 Ό N N I <37 1 u 0 0 Ω O H- OJ 1 H ' H · H n 1 '-J O | 1 1 cn cn Q - J Ω ΙΊ Pi 3 F- ¹ 'Π 1 Ω f) Ω o CP cp H · ΡΓ H · i 1 1 42 » 73 ; 3 cn cn 07 43. 42. 3 □ p- »· Oops 4 ^ O) Ό 1 H · LO Pm PlJ PP H · 1 P3 Pi 1 i H · d Ω - ► £ » 42. 42. Cb t \ J O N H · H- ΙΊ H · H · LO H · 1 · H · F- · t— ¹ , - »· Π Cb 1 3 H ' H · 3 Pi UH Cb H · 1 Ω 1 i— ^u □ J cn 0) I Cb to cn 4 ^ Pi 1 LO LO To. J. 1 | OJ CO 1 I 3 H · to H · 1 'H « H · 1 i— · H * K · F- * i— » ΓΟ ω P) ! - » Pi pi 1 ω ω P) w ω H · cn t— · Pi

cn

Table (continued) ii n

OO 00 CO CO 00 oo

CO 00 00 OO CO OO CO OO co you

O7 07

O? R ω

H ·

B

OJ cn *

Ό Ό Ό Ό Ό · » «·. * cn cn cn cn cn cn o • o CO o o O

o

J-ti

H □

H · □

H · tn

you f- * cn fu Ό fu r ¹ F ~ * Ό o F- * LH 0 H · L0 cn H · - H · o Cb ra 1 1 ra Ln ra • C_J- f- · .— · LJ. 1 LJ. c co cn Pi Ό c rr cn f— * O cn Ό cn •

tn n OJ N 3 0 (T 3 Φ ? r ft H · & cn

+

417

Isomers rel 5: 1 • ra e ω o ra ra kO U O c f-i d 2 r—! • ro TO • ro r—! • ro ΤΊ r—! « e G) G) 1 o co in e 1 E5 t) • r-l • r-l • r-l C \ • P ~ l * r- LO • r4 >! 0 r— · r ^- · r — f o »-: r — to r — Ί J Cj Γ3 r— { fC m r-l ® ω • r4 C ·. ·> • H ₄ ' c U-l CO co CO Oops kO Γ ' CM e LO LO LO LD LO LO LO LO kO r-1 * » * · · » · » • k k X o r- r- r- r- r- r-

* ra ra e

• H ra

X o

CN

Γ0

E E E C! U O n n m m

M »-γ-« r—

- <»- · - M- μίo e ro m ro ro n m

S C EEEEEE U t) U U U U

Table (continued)

ω cn cn rC rc rc r-1 r-4 r—: r-! • H • f— | • r-l  r—! 1 1 1 1 ω d ω cn o: * 5 " LO ro i rc rc 1 1 1 r-1 c cn r — i r-H c C c sort of ♦ H • H r £ ω • <-J • H • H • r-l • r — i r-H 1 73 r — i ω sort of 1 I You E • rJ • H • H G cn r-1 LO CN • r-J -r-l • H 1 i ε J r — To Gj • r-J 1 1 ε ε E C • H CM • γΊ t—! 1 C c • H • r — i • r-l 1 • H M 1 I • H rn • r-? • r3 P L. L c 73 • r-l 73 CN 1 1 t: NO ·. — I • r — 1 • H • H • H Oj • H 1 o: C H • H a £> _, a 73 E 1 L NO | • H ξ = ε 1 1 1 • r-l • r-l ro • H r3 r-l r · —1 • t — 1 • Γ ~ ί ro ro ro E P E Ω, Sj 0 0 L Li d E Cc • Γ ^- ? ♦ r-Ί Ch> 1 -4 L C • r-l H C) U U L V- o 0 & • H • H £ r Ω. 1 1 1 • H 1 1 73 1 Ο- 1 1 · <—I • fl • rd Ou m • H • H LO O ι u fO eon no 73 1 E E3 ra M O O ΓΟ 1 X E 1 i 1 r-l C.) 1 -V CM U LO f r— * C U kO LO <· c; O KC 0 (J co r »- · O o 1 1 * * * · 1 1 1 1 E kO 1 1 K? · «· OJ CM kO lo - =) · 1S. 1S. h? LO O o 33 <

O • H

C • r-l

Cn c

G)

Ll

Z to kO

Γ vt cc ^ r o

LH .H

LO o; to 'ro tr.

• tr

LO

LO io kO

LO

ΓLO

CO C) LO LO

H

-O -J 4 ^ CO

H ¹ r- ¹ -J Ό (Ό H *

στ co

H- ⁴ I— *

OT cn -O OT r- ¹ H- 'H- * —— ·

CT CT OT CT ji ω m i— · στ o

z

1

C |

C □

iQ

H ·

H ·

O

UI 1 <-n 1 CO 1 Co. 1 CO 1 to 1 t— · ►La. OT 1 Ό 3- CO rh £ CO c-o X) n O o 07 Q. n CO O f) 3 4 ^ 1 45 » 45 » 45 » H- o O f} στ »· ' H- OT M. 1 Pi 1 1 1 ii 3 cp Γ-Ρ HM co ^ 4s » ? · CL CL □ Cl Cl 2L 3 uJ ^ CO cn l J • S '<n 1 H ' 1 H * H · H · 0 tO ~ * 1 1 1 H rr 0 l ; o 1 CO 1 1 1 1 1 M H - 1 H- ¹ M 1 1 '0 i Q. i Q. n O T3 ^r o <w «· * » CO H · Ό H · Γ-- H * Cm h— ¹ , - ¹ H · H- CO CO co «· Pi H * 1 »- » cT i- ¹ CO I I d · *. 'N n H ' pi 1 pi 1 ό Ω O V> £ » l H- H · 3 (n rtj cn rr στ ^ στ N N 1 f 1 rr 3 r> ₄ H- j5 1 PC ~~ ζ 3- H * ft rr rr 1 f Ί oh, 1 M · CO σο 3 O r $ ii d ^ _t. cn CO H · Oops Pi 1 1 i-j. H · Pi 1 1 □ 3 N t \ J CO b iu Uh N _H. H ' t 1 0 1 1 N N N H · r- ¹ H- * CO f — J H- H · r- H * H · □ pi Pi 1 I 1 pu 3 2 □ 1 cn ω H * H · cn Pi pi 1 1 1 cn i- ¹ J— · | ω Cfi cn cn CH f Pi Pi H * 1 1 1 H * cn ω 'r- ⁴ H · H · H · r ^-1 P M ) - ¹ r- ¹ pi * Lfi & Pi Pi ω Cfi ω ω

d n

£ 1

Ί. \ J

-X.

'O γΗ · I 3 HH- H- * lL I I Q i co

NJ

I f + n

n -n n o q n n q n <-> o n n j .3 Z c: H-H. ± 3 Z -H '3 3h 3h —H - Ό

Ld Cd Cd Cd Cd Cd Cd Cd Cd M Cd Cd Cd Z

K) ii

E

K)

O? R w

H · ω

ω *

-Ό -0 -σ -ο -0 -0 • s >> • 'Χ στ στ iJT σπ σπ στ (Ο ο στ CO CO ί— ¹

O

H * fD

Hl

3 ·

H · cn

C0 r-j S) Si Pi —I kO F— * i— h- · -H- 1 στ H « r- ¹ · H · O co I O O Q. L_J. CO 03 CJ. l_J. '_j. UJ C C C 07 ω ω Oops

c <<

Oj r + ω

0) rr

X ω

+ · +

N

O

Φ <c:

Table (continued) +, · + &

M

Φ e

o

N w

• r ·!

> 1> 1

4J

C <0 ω

m rar— {

CT;

-P

t) o

U. tn ω LO o: ω c. 3 0 «. 3 kC O • n • ΓΊ • m Cs) co • m • Γι 1 kC · Ci .o o co kO Ci C.I. % * ' 1 • t— * r r-l • r- » 1 1 • r-i • r-l r-> kO r— ' rH t— ( o kO r - l LO ΓΪ (TJ <3 c- kO ra CC

© • r ^ c

• H c

U-l flj rH

O σ ·· C < cc o Γ- Γ- LO to to LO LO LO kO ΙΟ ΙΟ LO v ·. v s. * », * 1. K ·. r- r- r- r- S ra- ra- r- r-

* ω

fO ra {N

X X X X X X K X CL ·

C> O t! (..) O O t) u o t!

m

L ·.

Um

tn tn ω ra ra ra ra> - o

· (- e

Table (continued)

• H 1 • H ! -H 1 C) Cs) O Ci tn tn t I 1 1 re re tn 0 ·} c c c c r—! r—; re re • r-i • H • H • p4 • r — ί rH r - l N N N N 1 1 • r-i r-1 m O rS C ' CJ 1 1 P ΡΊ k-l U) p | t Csl Cl • T — i co to • H • rJ • t — 4 C c 1 1 c. «Tr f * - ¹ kO to Ο- O., Ο- • H • H O C 1 fr ' kO C) kO Ι 1 ι N N • t — To • r-l o ~ kO O 1 U ro C 'i co O re N N c U l ^ 3 · 1 co 1 kO μΞ * T! p o re ra to P—! ►γ- d o r j U O • r-J • r4 O P • H co kO C.) O 1 X 1 Ϊ 1 1 Ο- '0 • r-i • r-4 υ X O 1 F4 » O • r-l • H • H Ι 1 a Ο- • 1-1 u 1 -H • H O LO Ό, · O ΓΟ ra) 1 ι ^r c C! Cl T * u fp 1 1 1 O £ 0 r— 1—! 1 C ►O 1 1 g LO lo c: kO O kO o C) o C.) ¹ 't ω in- * ^ r cr X X C 1 K, ». K 1 1 1 · ». 1 Γ · » · » 1 kO kO I LO ro CO LO LO tfl kO LO 'M' Cl C-J * 7T o O

o • H c

• r4 tr c

3 '

t)

Lf) ra- ro r- co oor— h r- ra ra- ra cc cc r — ό r— Ί i — 1 r—) p— 4 r— 1 cj ro m co co cc cc r— 4 i— * f — 4 i — i kO cc r—) r- co σ \ c CO CO CO C ', -j

OJ l \ J fsj ΓΡ f \ j M SJ ru i \ J (\ J r— ¹ H * r- ' H- ¹ t- ² H- * »- » P ^ r- » o O o O o O o o O O '-O <D UO <0 kO kO '.O <O kO OJ -u c and vTs UJ M r-J O UO CO -J Cl (JI UJ (SJ H

G

H □

H ·

O

UJ 1 C 1 And 1 o I C 1 cn 1 X Ρ- i cr o n c O c X Ρ- r j UI (5 H- o o n '-'C UI ί c 0 Ω O a O O Ω P P X 5 _Ί Ω X see o X X P- P- P · P- Q. n P N N and cn 1 P and I- · ¹ p ·; finger ui and P P P P x -r * N O Π * 1 <5 14th i O O UJ P P P UJ UJ P- z P- Q. σι P- 53 - 0 O 1 0 0 1 1 1 P cn P O X P X (D UJ t 1 X X 1 P N r * H and l M see X Ό X X Ρ- Ρ- cU N 0 ΙΌ 1 rc cn Ρ- P- Ρ- P- Ω Ω 1 0 PJ Ω l H · Ω P, Ω h P P P- i—> 1 X p. r- ¹ p- P- P- P N N P- * i M ii _) 1 C1j X Cb N > - »· P- P ; \ j J Ω 1 n 1 1 1 H * P P OJ 1 P- X O L UJ UJ P l 1 P- r- * X 1 1 | 1 • \ J M »- » P i \ J p4 P · P- 1 t P ω t— » r— » K-J 1 P- P- cn OJ P P P * P- * r— ^J I cn OJ OJ P ^ P P P cn cn OJ

q P

-U X UJ UJ

n n o □ 3 X) G G cj 3 ω ω σ

535 Π ίο 35 5

O ω cj i— * - no nu

35 35 35

UJ UJ UJ 'jJ X un

-J fsj

35 · * *> C U-l

O? R cn

H · £ 3

OJ '-J -J -J «·> S and UI <JJ

CO -J Ό and

-J

P P »- » i— » p. Ρ- O Ω UJ. UJ · P 00 cn

Oj r- ¹ iD _j.

cn

O r—

S cn *

O

H * (D

P □

H · □

cn ©

r · <

CL rt ω n cv N 3 O rt 3 ► <Φ X η f · rf3 cn + ·

Table (continued)

- 21 LT 3730 B

P (U e

o

N

M + + U) • I — I

X

4J

C (U tn

J tn • r-i c

iw <13 r-i o

+ <0 ra e

• H

ū) o

CM _i _yn ro _ΓΊ ^ p- _: ro ddddddddddddd oi tn ra

Table (continued)

1 σι C ω • H r — ί ω m M ♦ P p r— '' p 1 C n r— < 'J'.  P ri tr £ · r 1—: • ri ώ 1 P 1 d it • 1—) i p — i u: to you P 4.J c 1 r— ' f P ♦ H P (Z P 1 J • i—? r— « Τ- p 1 1 r— ( r— '' r-4 r-i N ♦ r * Ι ω I r — f p • l-i Τ- ♦ H 0 *. Ή 1 • 'tr ·  d c 0 1 1 Ι 1 N p; T r—> I r-P ♦ r- * N r- ' P CM P P • H t 1 τ: · • r! T3 Γ5 0 t to 1 • P »—Ί P r- T E ** r- * ♦ H 1 • t-i (f b: r — i r— r- + -P 1 • P ~ kc v n <o C P LT! F Γ5 0 0 0 1 p After C? O C.) N -r-i 1 0 ω M N N m | P 1 1 1 05 a c P N Λί m Γΐ P H- < O H-. fe- · χ-X • r — t ' 1 • ri • P .-1 0 • H P 0 o t) c o c? P o Π ^- } P, T t-l P U -P 1 1 I P P LP 4-Ϊ r • P r * ·) • H 1 1 1 * Oh ' • H • P W * ► · - T f- ' 1 rt t m ►ą ' 1 r; P p T π-η <C kO kO t? ♦ 1-1 t d P O • r * CP r - t 1 i O U u • X C p C.? C: P • "T * d U O P kO * - ' * - · CM 1 • H 1 1 1 r 1 1 1 K 1 1 1 c · Cu Pi m CO P p Ό ' CM ΓΡ p CM p % » r- '

o • H c

• H

CP

C

t)

O r — i CM P T-- P P p · CO P O r — i P) P V ' r * -i »—I r— ' t — J r ~ i r-i r— ' r-i rH rP PI P4 CM PJ CM CM CM Pi CM CM CM pi CM PI CM PI CM ΡΪ CM CM

M M M N) hO N) ix> CO CO iuO M {•• C M ί O . \ J M O L0 CO -J O cn

C- |

C

Z o D cQ • H · □

HO * n n n

ΟΛ ΟΊ ΟΊ r? ^k T? .T?

cn ui cn o

o n n o n Q οί cn cn cn co cn

Table (continued)

O X3

Z Q Q i'j cJ cj E ω ω onj .—.

tr —cr

X3

ΟΊ cn co

-J '-J -J Ί » % ΟΊ CT \ cn <n O co co

cb cb a O O 9th no 0 d n 3 < < < < 3 WITH 3 3

o

X ω

H ·

0) cn *

Φ »-h

H ·

H3

H · cn r

x o, cn o>

rr * <

X

H · cn +

+

N

O

Φ et

4 =

Compound 53 is:

compound is:

compound is:

Compound 152 is present

ch ₃ o ₂ c

153 The compound is:

continuation of the table

Compound 1 No. 2 R A Olefinini ^ ' Melting point ° C ratio of isomers 233 H 6 ^H 5 (CH ₃ ) CHS H 234 pyrimidine-2- CH ₃ O H. ilas 235 pyrazin-2-yl Cl H

Explanations:

it · Chemical shift of the singlet from the olefinic proton main oxime-isomeric isomer in the p -methoxypropenate group (parts per million from tetramethylsilane).

® Chemical shift of singlet from proton in aldoxime, where appropriate.

++ Isomers resulting from asymmetrically substituted oxime double bonds.

The R and R groups are joined to form a ring.

Table: NMR data of selected proton

The following table shows the NMR data for the selected proton for some of the compounds listed in Table 1. Chemical shifts were measured in parts per million (m.d.) of tetramethylsilane, and deutschloroform was used everywhere as a solvent. The column labeled frequency indicates the operating frequency of the NMR spectrometer. The following abbreviations are used:

pi = wide s = singlet d = doublet t = triolet kv - quartet m = multiplet

• Compound Frequency No. (MHz) 1. 2. n -f · 1 270 33.69 (3H, s), 3.82 (3H, s), 3.83 (3H, s),

5.12 (2H, s), 6.84-6.99 (2H, m), 7.11 -7.2 (1H, m), 7.25-7.4 (3 H, m), 7.5-7 , 62 ( 1H, m), 7.60 (1H, s), 7.74-7.8 (1H, m), 8.50 (1H, s) m. d. 2 400 3.70 (3H, s), 3.80 (3H, s), 3.81 (3H, s), 5.13 (2H, s), 5.9-7.54 (8H, m), 7.60 ( 1H, s) m.d. 6th 270 (pag. line nis isomer) 2.36 (3H, s), 3.63 (3H, s), 3.80 (3H, S), 5.10 (2H, s), 7, Ι- 7.5 (SH, m), 7.60 (1H, s), 8.07 (1H, έ) m.d. 11th 27 0 3.70 (3H, s), 3.81 (3H, s), 5.14 (2H, s), 7.15 -7.20 (1H, m), 7.24-7.43 (5H , m), 7.48- 7.54 (1H, m), 7.58-7.62 (1H, m), 7.59 (1H, S) 8.04 (1H, s) m.d. 17th 270 3.70 (3H, s), 3.84 (3H, s), 5.17 (2H, s), 7.16 -7.22 (1H, m), 7.32-7.39 (2H , m), 7.49-

7.58 (2H, m), 7.60 (1H, s), 7.83 8.14 (1H, s), 8.17-8.23 (1H, m), (1H, m) m .d. 20th 270 3.70 (3H, s), 3.83 (3H, s), 5.16 7.14 · -7.20 (1H, n), 7.31-7.38 (2H 7.4S · -7.55 (2H, m), 7.55-7.64 (1H 7.60 (1H, s), 7.7-7.77 (1H, d), 8.12 (1H, s) m. d. 23rd 270 2.25 (3H, s), 3.69 (3H, s), 3.81 5.16 (2H, s), 7.13-7.20 (1H, m), (5H, m), 7.5-7.55 (1H, m), 7.59 7.5- 7.66 (2H, m) m. d. 29th 270 3.58 (3H, s), 3.30 (3H, s), 5.08 5.13 (2H, s), 6.94-7.07 (1H, m), (12H / m), 7.60 (1H, s), 8.06 (1H 32 270 3.70 (3H, s), 3.83 (3H, s), 5.14 7.1- 7.9 (5H, m), 7.60 (1H, s), 8 m. d. 37 270 3.69 (3H, s), 3.81 (3H, s), 5.18 7.15 -7.82 (7H, m), 7.60 (1H, s), (1H, s), 3.5 (1H, m) m. d. 38 270 3.59 (3H, s), 3.82 (3H, s), 5.14 7.14 -7.53 (5H, m), 7.60 (1H, s), 7.9o (1H, m), 8.10 (1H, s), 8.55 (1H, tn), 8.72 (1H, m) n.d. 40 270 2.34 (3H, s), 3.69 (3H, s), 3.81 5.19 (2H, s), 7.1-7.7 (6H, m), 7 7.89 (1H, d), 8.59 (1H, d), m.d.

42 270 1.32- -l> 40 (3H, t), 3.63 (3H, s), 3.77 (3H, s), 4.33-4.44 (2H, kv), 5.25 (2H, s), 7.13- -7.20 (1H, m), 7.26 -7.42 (4H, m), 7.56 (1H, s), 7.7-7.77 (2H, m), 7 , 66-7.71 (1H, m) m . d. 47 270 2.24 (3H, s), 3.69 <3H, s), 3.82 (3H, s),

5.11 (2H, s), 6.9-7.55 (7H, m),

7.58 (3H, s) m.d. 49 270 1.3 (6K, sq), 3.70 (3H, s), 3.83 (3H, s), 4.36 (4H, kv) , 5.2 3 (2H, s), 7.1-7.5 (4H, m), 7.53 (1H, s) m.d. 55 270 2.85 -3.12 (4H , m), 3.69 (3H, s), 3.82 (3H, s), 5.14 (2H, s), 7.1-7 , 7 (8H, m) Z 7.58 (1H, s) m. d. 65 270 (pag ordinary i z ome ras) 2.24 (3H, s), 3.58 (3H, s), 3.81 (3H, s), 5.16 (2H, s) _r

7.1-7.5 (5H, m), 7.60 (1H, s), 7.9 (1H, m),

8.57 (1H, m) , 3.83 (1H, m) m. d. 6 5 270 1.22 (5H, d) , 3.57 (1H, m), 3.69 (3H, s), 3.32 (3H, s) , 5.13 (2H, s), 7.1-7 , Δ (4H, m), 7.60 (1H, s) , 3.31 (2H, s), 9.18 (1H, s), m. d. 67 270 1.14 (6H, d) , 2.83 (1H, m), 3.66 (3H, s), 3.78 (3H, s) , 5.00 (2H, 3), 7.1-7 , 4 (4H, m) 7.53 (1H, s) , 8.56 (2H, S), 9.17 (1H, s) m. d. 92 270 2.26 (3H, s) , 3.68 (3H, 3), 3.80 (3H, s), 4.00 (3H, s) , 5.21 (3H, s), 7.1-7 , 6 (4H, m), 7, .58 C LH, s),

Table (continued)

1. 2. 3. 8.03 (1H, d), 3.16 (1H, d) m .d. 93 270 (main Indian isome ras) 2.30 (3H, s), 3.69 (3H, s), 3.83 (3H, s), 4.03 (311, s), 5.24 (2H, s), 7.1- 7.55 (4H, m), 7.50 (1H, s), 9.20 (1H, m), 9.23 (1H, m), (Tues. alpha isomer as) 2 , 30 (3H, s), 3.64 (3H, s), 3.80 (3H, s), 4.03 (3H, s), 5.12 (2H, s), 7.1- 7.55 (4H, m), 7.57 (1 H, s), 9.32 (1H, m), 9.37 (1H, m) m. d. 102 270 2.22 (3H, s), 3.63 (3H, s), 3.88 (3H, s), 3.12 (2H, s), 7.15 -7.55 (7H , m), 7.60 (1H, s) ppm. 108 270 2.20 (3H, s), 3.67 (3H, s), 3.30 (3H, s), 3.83 (3H, s), 5.14 (2H, s), 5.87- 7.60 (8H, m), 7.57 (1H , S)! m. d. 111 270 2.20 (3H, s), 2.30 (3H, s), 3.68 (3H, s), 3.80 (3H, s), 5.13 (2H, s), 7.15- 7.4 (7H, m), 7.54 (1H, m), 7.53 (1H, s) ppm. 112 270 2.23 (3H, s), 2.37 (3H, s), 3.63 (3H, s), 3.81 (3H, s), 5.16 (2H, s), 7.1-7 , 55 (3H, m), 7.58 (1H, s) m .d. 113 270 2.22 (3H, s), 2.35 (3H, S), 3.53 (3H, s), 3.31 (3H, s), 5.13 (3H, s),

7.1-7.5 (8H, m), 7.58 (1H, s) m.d.

Table (continued)

1. 2. 3. 114 270 2.26 (3H, s), 3.68 (3H, s), 3.81 (3H, s) 5.16 (2H, s), 7.0-7.55 (8H, m), 7.59 (1H, s) m.d. 115 270 2.02 (3rl, s), 3.58 (3H, s), 3.32 (3H, s) 5.15 (2H, s), 7.0-7.55 (8H, m), 7.60 (1H, s) m.d, 115 270 2.22 (3H, s), 3.68 (3H, s), 3.32 (3H, s) 5.13 (2H, s), 6.99-7.65 (8H / m), 7.59 (1H, s) m. d. 118 270 2.21 (3H, s), 3.69 (3H, s), 3.81 (3H, s) 5.15 (2H, s), 7.14-7.56 (8H r m), 7.59 (1H, s) m.d. 121 270 2.21 (3H, s), 3.69 (3H, s), 3.82 (3H, s) 5.16 (2H, s), 7.1-7.55 (7H, m), 7.59 (IK, s), 7.81 (1H, m) m. d. 127 270 2.26 (3H, s), 3.69 (3H, s), 3.83 (3H, s) 5.18 (2H, s), 7.15-7.92 (OH / m), 7.60 (1H, s) m.d. 131 270 2.22 (3H, s), 3.68 (3H, s), 3.82 (3H, s) 5.18 (2H, s), 7.1-7.8 (3H, m), 5.59 (1H, s), m. d. 143 270 (major isomer) 2.28 (3H, s), 2.53 (3H, s), 3.69 (3H, s), 3.33 (3H, s) 5.22 (2H, s), 7.1-7.5 (4H, m), 7.60 (1H, s), 7.72 (1H, s), 9.06 (1H, s)

m. d.

(major isomer) 2.27 (3H, s)

Table - (continued)

1. 2. 3.

2.48 (3H, s), 3.69 (3H, s), 3.83 (3H, s), 5.21 (2H, s), 7.1-7.5 (4H, m), 7.61 (1H, s), 7.77 (1H, s), 9.10 (1H, s) m. d. 144 270 (major isomer) 2.22 (3H, s), 2.50 (3H, s), 3.67 (3H, s), 3.81 (3H, s), 5.14 (2H, s), 7.1-7.5 (4H, m), 7.58 (1H, s), 8.53 (LH, s), 9.02 (1H, s), m. d. (major isomer) 2.17 (3H, s), 2.40 (3H, s), 3.65 (3H, s), 3.77 (3H, s), 5.00 (2H, s), 7.1-7.5 (4H, m), 7.52 (1H, s), 8.37 (1H, s), 9.05 (1H, s), m. d .. 145 270 · 2.39 (3H, s), 2.57 (3H, s), 3.69 (3H, s), 3.81 (3H, s), 5.33 (2H, s), 7.11 (1H, d),

7.1-7.55 (4H, m), 7.57 (1H, s),

3.64 (1H, d) m. d. 152 270 2.92 (2H, t) , 3.68 (311, s), 3.82 (3H, s), 4.18 (2H, t) , 5.14 (2H, s), 6.8-; 7.0 C 2H, m), 7, 1-7, Δ (5H, m), 7.53 (1H, s) , 7.87 (1H, m) m.d. 154 270 2.22 (3H, s) , 3.61 (3H, s), 3.75 (3H, s), 5.03 (2H, s) , 7.0-7 , 5 ( 7H, m), 7.52 (1H, s) , 8.12 (1H, m) m. d. 158 270 2.08 (3H, s) , 3.67 (6H, s), 3.80 (3H, s),

5.06 (2H, s), 5.08 (1H, m), 6.38 (1H, m)

Table (continued)

2.

6.06 (1H, m), 7.1-7 , Δ (4H, m), 7.57 (1H, s) m. d. 160 270 3.69 (3H, s), 3.82 (3H, s), 5, 19th (2H, s) 5.42 (2H, s), 7.1-7 , 5 (7H, m), 7.61 m. d. (1H, s), 7.77 (1H, s), 8, 05 (1H, s) 162 270 2.21 (3H, s), 2.46 (3H, s), 2, 62 (3H, s) 3.68 (3H, s), 3.82 (3H, s), 5, 10th (2H, s) 7.1-7 , 5 (4H, m), 7, 53 (1H, s) m. d. 163 270 2.16 (3H, s), 3.68 (3H, s), 3, 31st (3H, 3) 5.17 (2H, s), 5.42 (1H, m), 6, 61 (1H, rn) 7.1-7 , 55 (6H, m), 7 , 58 (1H, s) , m .d. 165 270 8.63 (3H, s), 3.76 (3H, s), 5, 22nd (2H, s) 7.1-7 , 8 (10H, m), 7 , 56 (1H, s) t 8.55 (1H, d), 8.70 (1H, d), m. d. 177 270 2.29 (3H, s), 2.71 (3H, s), 2, 53 (3H, s) 3.68 (3H, s), 3.81 (3H, s), 5, 15th (2H, s) 7.1-7 , 5 (4H, m), 7, 59 (1H, s), 8.2 4 (1H, s) m. d. 183 270 2.24 (3H, s), 3.03 (3H, s), 3, 88 (3H, s) 3.82 (3H, s), 5.20 (2H, s), 7.1-7 , 5 (4H, m), 7, 59 (1H, s), 7.8-8 , 0 (4H, m) m. d. 134 270 2.18 (3H, s), 3.67 (3H, s), 3, 78 (3H, s) 3.80 (2H, pl.s), 5, 11 (2H, s), 6.59 (2H, d), 7.1-7 , 55 (6H, m) 9th

7.58 (1H, s) n.d.

Table (continued)

1.

188

270 (major isomer) 0.65 (2H, m),

0.90 (2H, m), 2.32 (1H, m), 3.67 (3H, s), 3.80 (3H, s), 5.13 (2H, s),

7.1-7.6 (9H, m), 7.57 (1H, s) m.d.

(secondary isomer) 0.65 (2H, m),

2.32 (1H, ra), 3.63 (3H, s) , 3.76 (3H, s), 4.97 (211, s), 7.1-7 , 5 (9H, m), 7.77 (1H, s) m. d. 190 270 1.41 (3H, t), 3.64 (3H, s) , 3.76 (3H, s), 4.05 (2H, square ), 5.1 8 (2H, s), 6.8-7 , 55 (8H, m), 7 , 55 (1H , s) m .d. 191 270 2.04 (3H, s), 3.65 (3H, s) , 3.78 (3H, s), 5.19 (2H, s), 7.1-7 , 4 (8K, m), 7.5-7 , 6 (1H, m), 7, 57 (1H, s) m. d. 194 270 1.10 (9H, s), 1.81 (3H, s) , 3.68 (3H, s), 3.81 (3H, s), 4.99 (2H, s) , 7.1-7 , 5 ( 4H, m), 7.57 (1H, s) m.d. 195 270 1.76 (3H, s), 3.46 (2H, 5) , 3.67 (3H, s), 3.80 (3H, s), 5.05 (2H, S) , 7.1-7 , Δ (9H, m), 7.57 (18, s) m. d. 193 270 2.10 (3H, s), 3.69 ' (3h, s) , 3.82 (3.8, s), 5.11 (2H, s), 5.85 (2H, s) , 7.1-7 , Δ (9H, m), 7.58 (1H, s) m.d. 225 270 3.60 (3H, s), 3.70 (3H, s) , 3.78 (3H, s), 4.94 (2H, s), 7.1-7 , 5 (7H, m), 7.53 (1H, s), 7.77- 7.81 (2H, m) m. d.

Table (continued)

1. 2. 3. 226 270 3.66 (3H, s), 3.77 (3H, s), 3.98 (3H, ε), 5.04 (2H, s), 7.10-7.53 (7H, m), 7.53 (1H, s), 7.50-7.70 (2H, m) m. d. 227 2 7.0 2.88 (3H, s), 3.57 (3H, s), 3.79 (3H, s) t 5.13 (2H, dd) , 7.1-7.5 (7H, m), 7.60 (1H, s), 7.6-7.7 ( 2K, m) m.f 223 270 3.20 (3H, s), 3.67 (3H, s), 3.80 (3H, S), 5.30 (2H, s), 7.1-7.6 ( 9H, m), 7.60 (1H, s) m. d.

Compounds of formula (I) of the invention may be prepared by

1. Fig. 2 is shown in Scheme I. The symbols A, R and R are as defined above, X is a leaving group such as halogen (chlorine, bromine or iodine).

Scheme I

Compounds of formula (III) may be prepared by treating the aces of general formula (III) with an appropriate base (such as sodium hydride or sodium methylate) in a suitable solvent (such as N, N-dimethylpharmamide or tetrahydrofuran) to form the anion, Of a compound of formula (II).

The oximes of general formula (III) are well known in the chemical literature. A compound of the general formula (II) for which X is bromo and the propenoate moiety is of (E) -configuration is described in EP-A0203605.

Alternatively, the compounds of formula (I) of the invention may be prepared by the route shown in Scheme 2. The symbols A, R, .R and X have the meanings given above, being hydrogen or metal (such as sodium or potassium), I being a separable group such as halogen (chloride, bromide or iodide), CH 2 SO 4 anion or a sulfonyl anion. Each transformation is carried out at the right temperature and usually, though not always, in the right solvent.

The compounds of formula (I) of the invention may be obtained from the phenylacetates of formula (VI) or the compound ketoethers of formula (X) depicted in Scheme 2

In this way, the compounds of formula (I) may be obtained by treating phenylacetates of formula (VI) with a base (such as sodium hydride or sodium methylate) and methyl formate. Compounds of formula (I) may then be added to the reaction mixture, where L is as defined above, If protonic acid is added to the reaction mixture, compounds of formula (IX) are obtained wherein R is hydrogen. Alternatively, compounds of formula (IX) wherein R ⁵ is a metal (such as sodium) may be spontaneously released from the reaction mixture.

Compounds of formula (IX) wherein R is a metal may be converted to compounds of formula (I) by treatment with a compound CH 2 L where L is as defined above. Compounds of formula (IX) wherein R ³ is hydrogen may be converted into compounds of formula (I) by sequential treatment with a base (such as potassium carbonate) and a benzoate (CH 3).

Alternatively, the compounds of formula (I) may be prepared from the acetals of formula (IV) by separation of methanol, either under acidic or basic conditions. Examples of reagents or reagent mixtures that may be used for a given transphotomation are lithium diisopropylamide; acid potassium sulphate (see, e.g., T.Uamaoa, H.Hagivara, H.Uda, J.Chem. Soc. Chemical Communication, 1980, 838 and references in this work); and triethyl mines, often in the presence of a Lewes acid such as titanium tetrachloride (see, for example, K.Usunda and L.Heresi, J. Chem. Soc. Chemical Communication, 1985 (1000).

The acstals of formula (IV) may be obtained by treating the methyl-silyl-ketene-acetals of formula (V) wherein R is an alkyl group with trimethylorthoformate in the presence of Lswes acid such as titanium tetrachloride (see, for example, K.Saigo and T.Mukaigama, Chemistry Letters, 755 (1975).

Methylsilylketeneacetals of formula (V) may be obtained from phenylacetals of formula (Vii) by treatment with a base and a trialkylsilyl halide genide of formula R RSiCl or R ^SiBr such as trimethylsilyl chloride or a base (such as triethylamine) and a trialkylsilyl triflate of formula is R ^ Si-OSO ^ CF ^ (see, e.g., C.Ainswarth, F.Cheia and U.Kio, J. Organganometallic Chemistry, 1972, 46, 59).

It is not always necessary to distinguish between intermediates (IV) and (V);

under appropriate conditions, compounds of formula (I) may be prepared from phenylacetates of formula (VI) in a single vessel by sequential addition of the appropriate reagents listed above.

Phenylacetates of formula (VII) are prepared from isochromanones of formula (VIII) by treatment with HX, where X is halogen (such as bromine), in methanol. This transformation can be accomplished in two steps if isochromanone (VIII) is treated with a compound HX in a non-volatile solvent and the resulting phenylacetic acid is then etherified by standard techniques (see, e.g.

I.Matsumoto and I.Joshizava, Jpn. Kokai (Tokki Koxo) 73 133 536, 27.10.1979, Chem. Abs., 92, 180829h, 1980; and G.M.F.Lim, U.G. Reggon, R.D. Droghini, Res., Disel. 1979, 183, 672, Chem. Abs., 92, 128526 (1980)). Isochromanones of formula (VIII) are well known in the chemical literature.

Alternatively, compounds of formula (I) may be prepared by treating ketoesters of formula (XI) with methoxymethylation reagents such as methoxymethylenetrophenylphosphorane (see, e.g., W. Steglich, Gr. Schramm, T.Anke, T.Oberwinkler, EP 004448, April 04, 1930). .

The ketoesters of formula (IX) may be derived from keto ketoesters of formula (X), oximes as described in EP 0331061.

exposed to the anion joint axes above. Compound (X)

The compounds of the invention are active fungicides and can be used to control one or more of the following pathogenic organisms: rice Pyricularia oryzae, wheat Puccinia recondita, Puc cinia striiformis and other rust, barley Puccinia hordei, Puc cinia striiformis and other rust forms, e.g. , rust of coffee trees, pears, apple trees, peanuts ..- and ornamental plants, Erysiphe graminis (milte37 nis) of barley and wheat and other forms of powdery mildew in various crops such as Sphaerotheca fuliginea hops (eg Sphaerotheca macularis), Podosphaera Zeucetricha and Uncicula necator, Helmintho sporium spp., Phynosporium spp., Septoria spp., Pyrenophora spp., Pseudocercosporella herpotrichoides and Gacumannomyces graminis; peanuts Cercospora arachidicola and Cecospori dium personata, other forms of Cercospora in other crops such as sugar beet, banana, soybean and rice; tomatoes, strawberries, vegetables, grapes and other crops Botrytis cinerca (gray mold). Vegetables (for example, cucumbers), oilseed rape, apple trees, tomatoes and other crops Uterna 'ria spp .; apple Venturia inaegualis, aeol of Plasmopara viti; other mildew forms such as lettuce Bremia lactu cae, soybean, tobacco, onion and other crops, Perenospora spp .; hops Pseudoperenospora humuli and cucumber Pseudoperonos pair cubensis, Phytophthora infestans and tomato Phytophthora spp. vegetables, strawberries, avocados, peppers, ornamental plants, tobacco, cocoa and other crops; Thanaphorus cucumeris and other forms of Phizostonia in various crops such as wheat and barley, vegetables, cotton and turf.

Some of the compounds exhibit a broad spectrum of activity against fungi in vitro. They may also show activity against various post-harvest diseases of the fruit (such as Penicillum digitatum and italicum and Trichoderma viride, Gloesporium musarium and Botrytis cinerea).

- 33 LT 3730 B

ch ₃ o ₂ ^c (X)

In addition, some of the compounds may be active as a seed stain against Fusarium spp., Septoria spp., Tilletia spp. (hard stump, wheat disease occurring in seeds), Us tiliago spp. and Helminthosporium spp. cereal crops, Phi zostonia selani cotton, and Pyricularia oryzae rice.

The compounds can move systematically in plants. In addition, these compounds may be volatile enough to be active in the antifungal phase in plants.

Thus, the present invention provides a method of controlling fungi which provides for the use of a fungicidally active amount of a compound as defined above, or a composition comprising the compound, in plants, seeds or plants and seeds.

mo places.

Some of the compounds have insecticidal activity and can be used to control many harmful insects and mites by properly selecting the application rate or application rate.

Therefore, according to another aspect of the invention there is provided a method of killing or combating insects or mites in which. encompasses the use of an insecticidal or miticidally effective amount of a compound as defined herein above, or of a composition containing salt thereof, in or for insects or mites.

The compounds can be used in agriculture for any purpose, but they are conveniently transformed into compositions using carriers or diluents. Thus, the present invention provides fungicidal and miticidal compositions containing the compounds described herein above and a suitable carrier or diluent.

The compounds can be used in a variety of ways. For example, they may be used (transformed or untransformed in the form of preparations) directly on the leaves, seeds and other growing media of the plants, or intended for planting, or may be used for spraying or pollination, or may be used in the form of preparations. cream or paste, or they can be used in the form of vapors or granules to slowly release the active ingredient.

Can be used on any part of the plant, including foliage, stems, branches or roots, root soil, seed before sowing, soil in general, watered water or hydroponic culture system. The compounds of the invention may also be injectable! into plants or sprayed on vegetation using electrodynamic sprayers or other low volume methods.

As used herein, the term plants includes seedlings, shrubs and trees. In addition, the fungicidal method of the invention provides protective, preventive and curative treatments.

The best compounds are used for agricultural and horticultural purposes in the form of compositions. In any case, the type of composition used depends on the particular purpose for which the composition is used.

The compositions may take the form of dustable powders or granules containing the active ingredient (compound of the invention) and a solid diluent or carrier, for example, as a preform, such as kaolin, bentonite, infuser earth, dolomite, calcium carbonate, talc, powdered magnesia. magnesium oxide), fuller earth, gypsum, diatomite, and Chinese clay. Such pellets can be preformed as suitable for use on the soil without further processing. These granules can be prepared either by impregnating the tablet with the active ingredient or by making the tablet from a mixture of the active ingredient and a powder filler. Compositions for seed dressing may include a substance (e.g., mineral oil) that facilitates seed adhesion of the composition; alternatively, the active ingredient may be formulated as a seed dressing using an organic diluent (e.g., N-methylpyrrolidine, propylene glycol, or dimethylformamide). The compositions may also be in the form of wettable powders or water-dispersible granules, with the addition of a wetting or dispersing agent to facilitate dispersion. Powders and granules may also contain suspending agents.

Emulsifiable concentrates or emulsions may be prepared by dissolving the active ingredient in an organic solvent, usually containing a wetting agent, and then adding the mixture to water, also containing a wetting or emulsifying agent. Suitable organic solvents include aromatic solvents such as alkylbenzenes and alkylnaphthalenes; ketones such as isophorone, cyclohexanone, and methyl cyclohexanone; chlorinated hydrocarbons such as chlorobenzene and trichloroethane; and alcohols such as benzene alcohol, furfuryl alcohol, butanol and simple glyceryl ethers.

Slurry concentrates of bulk insoluble solids may be prepared by grinding in a ball mill or granulation mill with a dispersing or suspending agent which is activated to prevent the solid from settling (settling).

Formulations for nebulization may be in the form of aerosols, in which the formulation is contained in a container under the pressure of a propellant (reagent) such as fluorotrichloromethane or dichlor.

compounds that could possibly be formed for difluoromethane generation,

The present invention relates to a mixture of the compounds of the present invention in a composition suitable for use in space.

Alternatively, the compounds may be used in the form of microcapsules. They can also be made in biodegradable polymeric coatings to provide a slow, controlled release of the active ingredient.

By incorporating suitable additives, such as additives to improve distribution, increase adhesive strength and rain resistance on the surfaces to be treated, various formulations are better adapted to various applications.

The compounds of the invention may be used in the form of mixtures with fertilizers (e.g. nitrogen, potassium or phosphorus-containing fertilizers). Compositions comprising only fertilizer granules containing compounds, for example in the form of a coating, are more suitable. Such granules properly contain up to 25% by weight of the compound. Thus, the present invention also provides fertilizer compositions comprising a fertilizer and a compound of the general formula (I) or a salt or metal complex thereof.

Moisturizing powders, emulsifiable concentrates and suspension concentrates generally contain a surfactant such as wetting agents, dispersants, emulsifiers or suspending agents. These materials may be cationic, anionic or nonionic.

Suitable cationic materials are quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable organic materials are soaps, salts of aliphatic sulfuric acid mono-ethers (for example, sodium lauryl sulfate); salts of sulfurated aromatic compounds (for example, sodium do decyl benzosulfonate, lignosulfonate of sodium, calcium or ammonium, a mixture of sodium diisopropyl and triisopropyl naphthalenesulfonates).

Suitable nonionic materials are condensations of ethyl oxide with fatty alcohols such as oleyl or cetyl alcohol or with alkyl phenols such as octyl or ionylphenol or octylcresol. Other non-ionic agents are partial complex ethers, which are derivatives of long chain fatty acids and hexitol anhydrides, products of ethylene oxide condensation of the specified partial ethers, and lecithins.

Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose) and swelling moles such as bentonite or ba atapulgite.

Compositions for use as aqueous dispersions or emulsions are formulated in a concentrate containing a high concentration of the active ingredient and diluted prior to use. Preferably, these concentrates can be stored for a long period of time and then diluted with water to obtain aqueous formulations which remain homogeneous for a sufficient period of time and can be applied by spraying or dusting by conventional means.

The concentrates may contain up to 95%, preferably 10-85%, for example 25-60% by weight of the active ingredient. When diluted to form an aqueous preparation, the aqueous preparation may contain a variable amount of the active ingredient depending on the intended use, but aqueous preparations containing 0.0005 or 0.01-10% by weight of the active ingredient may be used.

The compositions of the present invention may contain other compounds having biological activity, such as compounds having analogous or complementary fungicidal activity, or having plant growth regulatory, herbicidal and insecticidal activity.

The fungicidal compound which may be present in the composition of the invention may be a compound which is capable of inhibiting bell diseases (e.g. wheat) of bean diseases such as Septoria, Siberella and Helminthosporium Spp. seed diseases, as well as diseases occurring in the soil and both downy mildew and purely powdery mildew in grapes, mildew and smallpox in apple trees, etc.

After incorporation of another fungicide, the spectrum of activity of the composition may be wider than that of one compound of general formula (I). In addition, another fungicide may exhibit a synergistic effect on the fungicidal activity of a compound of general formula (I). Examples of fungicidal compounds that may be included in the compositions of the invention include (±) -2- (2,4-dichlorophenyl) -3- (1M-1,2,4-triazol-1-yl) propyl 1,1. , 2,2-Tetrafluoroethyl ether, (RS) -1-amino-propylphosphinic acid, (RS) -4- (4-chlorophenyl) -2-phenyl-2- (1H-1H, l),

2,4-Triazol-1-ylmethyl) butyronitrile, (RS) -4-Chloro-N- (cyano / ethoxy / methyl) -benzamide, (Z) -N-But-2-Enyloxymethyl-2-chloro-2 ' , 6 'Diethylacetane Aqueous, 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea, 1- (2R3, 4RS, 2RS, 4RS) -4-bromo-2- (2,4-dichlorophenyl) tetrahydrofurfuryl) -1N-1,2,4-triazole, 3- (2,4-dichlorophenyl) -2 (1N-1,2,4-triazol-1-yl (quinazolin-4 (3H) -one, 3- chloro-4- (4-methyl-2- (1H-1,2,4-triazol-1-methyl) -1,3-dioxolan-2-yl) phenyl-4-chlorophenyl ether, 4-bromo-2 -cyano-N, N-dimethyl 1-5-trifluoromethylbenzoyl-5-midazole-1-sulfonamide, 4-chlorobenzyl-N- (2,4-dichlorophenyl) -2 (1H-1,2,4-triazol-1-yl) thioacetamide, 5-ethyl-5,8-dihydro-8-oxo (1,

3) -Dioxole (4,5-g) quinoline-7-carbonic acid, © <- (N- (3-chloro-2, δ-xylyl) -2-methoxyacetamide) -Γ-butyrolactone, ana known to BA BAS 454, Benalaxyl, Benomyl, Biloxazole, Binapacryl, Biterganol, Blasticidine, Bupirimate, Buttioate, Captafol, Captan, Carbondazime, Carboxin, Chlorobenzthiazone, Chlorone, Chlorothalonil, Chlorozolinate, Copper-containing Junioes such as Copper a mixture, cycloheximide, cymoxanyl, ciproconal, ciprofurar, di-2-pyridyl disulfide 1,1'-dioxide, dichlofluanid, dichlone, diclobutrazole, dichloroezine, dichlorane, dimetamorph, dimethirimol, dinicanazole, dinocap, edifenphos, ethanol.nazole, ethanol, ethyl (Z) -N-benzyl-N- (methyl- (methylthioethylideneaminoxycarbonyl) amino] thio) -β-alaninate, etridazole, fenapanyl, fenarimol, fenfuram, fenpiconyl, fenpropidine, fenpro-pimorph, f en.tin-acetate, fentin-hi droxide, f lutolanin, flutriafol, fluzilazole, folpet, fosetylaluminium, fuberidazole, furalaxil, furconazole-cis, guazatin, hexaconazole, hydroxyisoxazole, imazalil, iprobenphos, iprodiozone, fibrinolone, isoprothiolane, as, metsulf ovax, myclobutyl nyl, neoazocin, nickel dimethyldithiocarbamate, nitrotalisopropyl, puarimol ofurac, organic mercury compounds, oxadixyl, oxycarboxin, penconazole, pencicuron, pent-4-enyl N-furfuryl-N-imidazole horaoalanine, phenazine oxide, phthalide, polixin-D, poliram, probenazole, prochloraz, procinidone, propanocarb, propiconaio!

zclas, propinob, prothiocarb, pyrazophos, pirifenox, pyroxylone, pyroxifur, pyrrolidine, quinomethionate, chinto 4 6 zeno, streptomycin, sulfur, techlophthalam, techazene, tebuconazole, thiabendazole, thiophanate-methyl, thiramethyl, thiramethyl. iminodi (octamethylene) diguanidine, triadirephone, triadimenol, triazbutyl, tricyclazole, tridemorph, triforin, validamycin A, vinclozolin, and ebb. The compounds of the general formula (I) may be combined with soil, peat or other media for the root system, without the need to protect plants against seeds, soil or foliage.

Suitable insecticides which may be included in the composition of the invention include buprofezin, carbaryl, carbofuran, carbo-sulfane, chlorpyrifos, cycloprotrine, demeton-S-methyl, diazinon, dimethoate, ethofenprox, fenitrothion, phenobucocarb, phenthion, isoxathion, monocrotophos, phentate, pirimicarb, propafos and XMC.

Compounds that regulate plant growth are compounds that inhibit the production of weeds and Eeopeao or selectively inhibit the growth of less desirable plants (such as grasses).

Examples of compounds that regulate plant growth and are useful with the compounds of the present invention include 3,6-dichloro-cholinic acid, 1- (4-chlorophenyl) -4, o-dimethyl-2-oxo-1,2-dihydro-pyridine-3 -Carbonic acid, methyl-3,6-dichloroanisate, abscisic acid, azulam, benzoylprop-ethyl, carbetamide, daminozide, difenzoquate, dicegulac, ethephon, fenpentezole, fluoride amide, glyphosate, glyphosine, hydroxybenzonitrile, isopyrimole, fatty alcohols and long chain acids, maleic hydroside, mefluidide, morphactins (such as chlorofluorecol), paclobutrazole, phenoxyacetic acids (such as 2,4-D or MC? A), substituted benzoic acid (e.g., tri-benzoic acid), substituted quaternary ammonium and phosphine yang (for example, chlormequatchlorfonium or mepiquatfluoride), techazene, auxins (for example, indolacetic acid, indolebutyric acid or naphthoxyacetic acid), cytokine inhalants (e.g., benzimidazole, benzyladenine, benzylaminopurine, diphenylurea or kinetin), hyperrelins (e.g., GA ^, GA ^ or GA?) and tripentenol.

The following examples illustrate the invention. In each of the examples, the term simple ether or ether refers to diethyl ether, magnesium sulfate was used to dry solutions and the solutions were concentrated under reduced pressure. The air and water-sensitive intermediates were run under nitrogen and the solvents were dried when needed before use. Unless otherwise stated, column chromatography was performed using silica gel as the stationary phase. When given, IR spectra and NMR data are selective: no attempt is made to list each absorbance in all cases. NMR spectra were recorded using CDCI-j solutions unless otherwise noted. The following abbreviations are used throughout the text:

THF - tetrahydrofuran

DMF = N, M-dimethylformamide

BMR = nuclear magnetic resonance

IR = infrared melt. = melting point

DESC = high performance liquid chromatography s = singlet d = doublet t - triolet multiolet

8th

EXAMPLE

This example illustrates the preparation of (E), (E) -methyl-3-methoxy-2- [2- (3-methylbenzaldoximinomethyl) phenyl] propenoate (Compound 5).

A solution of (E) -3-methylbenzaldoxime (0.23 g) in DMF (5 mL) was added dropwise to a stirred suspension of sodium hydride (0.051 g) in DMF (5 mL) at room temperature. After 0.5 h, (E) -methyl 2- (2-bromomethyl) phenyl) -3-methoxypropenoate (0.5 g), prepared as described for,-ΕΡ-0203506, in DMF (5) was added to the reaction mixture. ml) and the resulting mixture was stirred at room temperature for 4 hours. The mixture was poured into water and extracted twice with ether. The combined extracts were washed with water, then dried, concentrated and chromatographed using ether as eluant to afford the desired compound (0.132 g, 23% yield) as a pale yellow oil.

IR maximum (film) 1: 1709, 1631 cm ^-1 Lr NMR (270 MHz) δ ”: 2.35 (3H, s), 3.69 (3H, s), 3.80 (3H, s), 5.12 (2H, s), 7.1-7.55 <3H, m), 7.59 (1H, s), 8.05 (1H, s) m. d.

EXAMPLE

This example illustrates the preparation of a mixture of methyl 2- [2- (3,5-dimethylpyrazin-2-yl-acetoxymethylmethyl) phenyl] -3-methoxypropenoate (E), (E) and (Z), (E) (Compound 17S of Table 1). ).

To a mixture of 2,6-dimethylpyrazole (3.24 g), sulfuric acid (15 mL of a 3.4M solution) and acetaldehyde (10 mL) was stirred at 0 ° C, iron (II) sulfate solution ( 50.1 g in 150 ml of water) and tert-butyl hydropenoxide (16.2 ml of 70% aqueous solution). The temperature during the addition was kept below 3 C. Upon completion, the reaction mixture was stirred at 0 ° C for 1 hour. Sodium metabisulphate was added until the mixture failed a negative starch-iodine test. The reaction mixture was extracted with dichloromethane, the combined extracts washed with water, then dried, concentrated and chromatographed using a mixture of ether and 50-80 C gasoline. (4: 1) as eluent to give 2-acetyl-3,5-dimethylpyrazine (2.55 g,

59% yield) as a pale yellow oil.

IR maximum (film): 1594, 1551, 1252/1175 cm \

¼ NMR (270 MHz) δ: 2.52 (3H, s), 2.70 (3H, s), 2.80 (3H, s), 8.35 (1H, s) m.d.

2-Acetyl-3,5-dimethylpyrazine (2.65 g), hydroxylamine chlorohydrate (2.5 g) and sodium acetate trihydrate (3.5 g) were heated under reflux in methanol (50 mL) for 1 h. The reaction mixture was concentrated, diluted with water (75 mL) and extracted with ethyl acetate. The combined extracts were dried and concentrated to give an oil which was quenched with ether and 60-30 ° C gasoline to give 3,5-dimethyl-2- (1-hydroxyiminoethyl) pyrazine (2.54 g, 37% yield) as a white solid (m.p. 85-89 C) in the form of 1: 1 (E / Z) isomers.

IR max (film): 2925, 1455, 1375, 1036, 930 cm (270 MHz) δ: 2.23 (3H, s), 2.33 (3H, s), 2.53 (3H, s), 2 , 55

2.55 (3H, s), 2.53 (3H, s), 2.58 (3H, s),

3.32 (1H, s), 8.35 (1H, s), 9.45 (1H, s),

m. d.

A 1: 1 mixture of (E / Z) -3,5-dimethyl-2- (1-hydroxyiminoethyl) pyrazine (0.87 g) was added portionwise to. stirring a suspension of sodium hydride (0.25 g) in DMF (20 mL) at about 5 ° C. One hour later, a solution of (F) -methyl-2- {2- (bromomethyl) -phenyl] -3-methoxypropenoate (1.5 g) in DMF (5 mL) was added to the reaction mixture at 0 ° C. After 1.5 hours, the mixture was poured into water and extracted twice with ether. The combined extracts were washed with brine, then dried, concentrated, and chromatographed using ether: hexane 1: 1 as eluent to afford the desired compound, oxime isomer mixture (major: secondary 7: 3) as a pale pink solid (0.57). g, 30% yield), m.p. 55-60 ° C.

IR max (film): 1707, 1624, 1132 cm -1 ^H NMR (270 MHz) major isomer-5: 2.39 (3H, s), 2.54

(3H, s), 2 , 57 (3H, s), 3.57 (3H, s), 3.82 (3H, , s) 5.15 (2H, s), 7.1-7.9 (4H, m), 7, r 59 (1H, s), 8.27 (III, s) m. d. Anrtaeil isomeras- chf : 2.22 (3H, s), 2.51 (3H, s) 2.57 (3H, s), 3.67 (3H , s), 3.82 (3H , s), 5.27 (2H, s), 7.1-7.9 (4H, m), 7, , 75 (1H, s), 3.33 (1H, s) m. d.

EXAMPLE

This example illustrates the preparation of (E), (E) -methyl-3-methoxy-2-C2 (phenylacetoximinomethyl) phenyl] propenoate (Compound 23 of Table 1).

Acetophenone-oxime solution (1.23 g) in DMF (5 mL) was added dropwise to a stirred suspension of sodium hydride (0.357 g) in DMF (25 mL) After 1 hour, (E) -methyl 2-C 2 (bromomethyl) was added to the reaction mixture. a solution of phenyl] -3-methoxypropenoate (2.0 g) in DMF (15 mL) and the resulting mixture was stirred at room temperature for 16 h. The mixture was poured into water and extracted twice with ether. The combined extracts were washed with water, then dried, concentrated and chromatographed using ether: 40-50 petroleum 3: 2 mixtures to give the crude oil. After DESC, 1: 1 ether: 40-60 oil, the title compound (0.55 g, 23% yield) was obtained as a pale yellow oil.

IR maximum (bead): 1703, 1631 cm

BMR is given in Table 2.

EXAMPLE

This example illustrates the preparation and decomposition of (E), (E) -, and (Z), (E) -isomers of methyl 3-methoxy-2- {2- [4- (pyrimidin-5-ylisopropyloxyimino) -O-methyl] phenylpropenoate (Table 1). Compounds 55 and 67).

A solution of oxime isopropylpyrimidin-5-yl-ketone (0.29 g of a mixture of 3: 2 (E) -: (Z) -isomers) in DME (5 mL) was added to a stirred suspension of sodium hydrate (0.09 g) in DME ( 10 ml). After 2 h, the mixture was cooled to 0 ° C and a solution of (E) -methyl 2- (2- (bromomethyl (phenyl) -3-methoxypropenoate (0.5 g)) in DME (5 mL) was added and the mixture was After stirring for 3 hours, the mixture was poured into water and extracted with ether, and the combined extracts were washed with water, dried and concentrated to give an oil, a crude mixture of (E), (E) - and (Z), (E) -isomers. for the separation of their two components, DESC was used using ether as eluent:

1. The faster elution fraction (elution) - (Z) -oxime ether, (E) -propenoate (0.115 g, 18% yield). Clear oil.

(Compound 57 of Table 1).

2. Slower elution (elution) fraction - (E) -oxime ether, (E) -propenoate (0.098 g, 15% yield). Clear oil (Compound 66 of Table 1).

BMR is given in Table 2.

EXAMPLE

This example illustrates the preparation of one stereoisomer methyl 2- (2-phenyl (methylthio) oximinomethyl] phenyl) -3-methoxypropenoate (Compound 191 of Table 1).

A solution of chlorine (1.5 g) in carbon tetrachloride (42 ml) was added portionwise to bonzaldehyde oxime (2.5 g;

NMR: a solution of 3.18 (1H, s), 9.40 (1H, pi.s.) ppm) in carbon tetrachloride (20 mL) at room temperature. The reaction mixture was then stirred at room temperature for 3 hours and then poured into water. The organic layer was separated, dried, and concentrated to give an almost pure yellow liquid o -chlorobenzaldehyde oxime (3.2 g). To a stirred solution of a portion of this -chlorobenzaldehyde-oxine (1.5 g) in methanol (15 mL) was added dropwise to a solution of sodium raethanediolate (0.68 g) in methanol (15 mL). After completion of the dropwise addition, the reaction mixture was stirred for two hours under constant cooling in ice water. Methanol was removed under reduced pressure and the residue was chromatographed using dichloromethane as eluent to give the only stereoisomer, cis -methylthiobenzaldehyde oxime (0.670 g, 42% yield) as a white crystalline solid, m.p. t. 76-73 ° C

NMR: δ 2.08 (3H, s), 9.12 (1H, s) m.d.

A solution of cis-methylthiobenzaldehyde oxime (0.575 g) in DMF (10 mL) was added to a stirred suspension of sodium hydride (85 g) in DMF (15 mL) at room temperature. After one hour, a solution of (E) -methyl 2- (2- (bromomethyl) phenyl] -3-methoxypropenoate (0.99 g) in DMF was added, and after a further 3 hours, the mixture was poured into water and extracted with ethyl acetate. rinse with water, dry, concentrate, and chromatograph using increasing ethyl acetate in hexane as eluent to afford the desired compound (1.05 g,

%) as a colorless oil,

IR: 1705 ca ' ¹ .

BMR is given in Table 2.

EXAMPLE δ

This example illustrates the only stereoisomers of methyl 2- [2- (phenylsulfinyl) oximinomethyl] phenyl] -3-methoxypropenoate and methyl 2- (2- (phenyl (methylsulfonyl) oximinomethyl) phenyl) -3-methoxypropenoate (1). Tables 227 and 228).

m-Chloro-benzoic acid (0.25 g, containing 45% m-chloro-benzoic acid) was added in portions over 30 minutes to a stirred portion of methyl 2- £ 2-Lf enyl (methylthio) oximinomethyl! Phenyl) -3-methoxypropenoate (0.30 g, obtained as described in Example 5), cooled in ice-water, cooled in dichloromethane (20 ml). After a further 15 minutes, the reaction mixture was washed successively with aqueous sodium bicarbonate solution and water, then dried, concentrated and chromatographed using a 1: 1 mixture of ethyl acetate and hexane as eluent to give the desired compounds: (1) sulfone; eluting (elution) first, barely derivatized (0.09 g, 28% yield); (2) sulfoxide, also in the form of a resin (0.15 g, 48% yield).

BMR is given in Table i2.

EXAMPLE

This example illustrates the preparation of two stereoisomers of methyl 2- [2- (phenyl (methoxy) oxyiminomethylphenyl-3-methoxypropenoate) (Compounds 225 and 226 of Table I).

The mixture of stereoisomers of -methoxybenzaldehyde-oxime was obtained in two steps from methyl benzoate by sequential treatment with Lawssson reagent and hydroxylation (see, for example, EP 0299332). The stereoisomers were separated by chromatography using dichloromethane as eluent:

(1) Isomer A, eluted (elution) first, pale yellow solid, m.p. t. 55-57 ° C, NMR: 3.83 (3H, s),

7.72 (1H, s) ppm.

(2) Isomer B, a colorless gum, ¹ H NMR: S 3.96 (3H, s), 8.84 (IR, s) ppm

The two stereoisomeric oximes are separately converted to the desired compounds in the manner described in Example 5, m.p. y. by sequential treatment with sodium hydride and (E) -methyl 2- [2- (bromomethyl) phenyl] -3-methoxypropenoate. The desired resin in the form of the desired compound 1 of Table 1 was obtained from Isomer A and the desired compound in the form of the resin (resin) in the form of the desired compound 226 of Table 1.

BMR is given in Table 2

The following are examples of compositions suitable for use in agriculture and horticulture and derived from the compounds of the present invention. These compositions form another aspect of the invention. Percentage refers to percentage by weight.

EXAMPLE _k

The emulsifiable concentrate is made by mixing and mixing the ingredients until they are dissolved.

Compound Table 45 10%

Benzyl alcohol 30%

Calcium dodecylbenzene sulphonate 5%

Nonylphenol ethoxylate (13 mol ethylene oxide) 10%

Alkylbenzenes 45%

EXAMPLE

The active ingredient is dissolved in methylene dichloride and the resulting liquid is sprayed with granules of atapulgite clay. The diluent is allowed to evaporate to form a granular composition.

Compound Table 45 5%

Atapulgite pellets 95%

EXAMPLE

The composition suitable for seed treatment is obtained by crushing and mixing three ingredients.

Compound of Table 45 '50%

Mineral oil 2%

Chinese Clay 43%

EXAMPLE

The dustable powder is obtained by crushing and mixing the active ingredient with talc.

Compound Table 45 5%

Talk

95%

EXAMPLE

The slurry concentrate is obtained by pulverizing the ingredients in a ball mill to form an aqueous pulverulent emulsion with water.

Table 45 compound 40%

Sodium lignosulfonate 10%

Sentonite Clay 1%

Water 49%

This formulation may be used for spraying with dilution with water or may be used directly for seeds.

EXAMPLE

The formulation as a wettable powder is obtained by mixing the crushed ingredients together until they are evenly mixed.

Table 45 compound 25%

Sodium Lauryl Sulfate 2%

Lignosulfonate Sodium 5%

Silica 25%

Chinese Clay 43%

EXAMPLE

The activity of the compounds against various plant leaf gry'elella diseases was investigated. The following method was used.

The plants were grown in compost cups by John Innes (# 1 or 2) in mini cups 4 cm in diameter. Test compounds were formulated for use in a pre-form or crushed using a granulator with aqueous Disperzole T, or as a solution in acetone or acetone / ethanol diluted to the required concentration immediately prior to use. In the case of foliage, preparative forms (100 parts per million of active ingredient) were sprayed onto the leaves or used to treat plant roots in the soil.

Spray preparations were used for maximum surface retention and root wetting to a final concentration equivalent to about 40 parts / ml. active ingredient in dry soil. When bell plants were sprayed, Tween 20 was added to give a final concentration of 0.05%.

For most of the tests, the compound was used to treat the soil (roots) and foliage (spray) one or two days before inoculation. An exception was the Erysiphe gra mins test, in which the plants were inoculated 24 hours before treatment. Leaf pathogenic organisms were used by spraying the leaves of the test plants with spore suspensions. After inoculation, the plants were placed in an appropriate environment for the infection to develop and then incubated until the condition was suitable for evaluation. The time interval between inoculation and evaluation varied from 4 to 14 days, depending on the disease and the environment.

Inhibition was recorded according to the following scale:

= no disease = traces - 5% on untreated plants

2 = 6- 25% of untreated plants = 25 - 59% of untreated plants = 60 - 100% of untreated plants. on untreated plants

The results are shown in Table 3.

EXAMPLE The insectricidal properties of the compounds of formula (I) were dsmon as follows.

The activity of the compounds was determined using various insects, mites and nematodes. Except in the case of activity against dumbbells against Musca Domestica, the assay procedure of which is described below, the compounds were used as liquid preparations containing 12.5 to 1000 parts per ml. weight of compound. The formulations were prepared by dissolving the compounds in acetone and diluting the solutions with water containing 0.1% by weight of a wetting agent sold under the trademark SINPERONIC PX to the required concentration of the product.

The test procedure for each parasitic organism was essentially the same and included introduction into the environment, which was usually the host plant, or to food which was eaten by pests, and by the preparation of harmful organisms or by the pest or the environment. Pest mortality was assessed one to seven days after treatment.

The test results are given in Table 4 for each of the units specified in the first column and the particle / rail consumption in the second column. The results are shown as the mortality rate, denoted as 9.5 or 0, where 9 represents 80-100% mortality (70-100% reduction in tubers compared to untreated plants in the in vitro assay with Meloidogyne incognita), 5 indicates 50-79%. mortality (50-69% tuber reduction in Meloidogyne incognita in vitro) and O represents less than 50% mortality.

Pests used in the table are identified by an alphabetical code. The meaning of the code, the medium or food, the type and duration of the test are given in Table 5.

The ability to create a knockout for Musca domestica was demonstrated as follows.

A sample of the compound was diluted with 0.1% ethanol / acetone (50:50) and the concentration was made at 1000 parts / ml using 0.1% SINPERONIK PX in water. The solution (1 mL) was sprayed onto the mixed sex flies stored in a drink cup with a piece of sugar that was also sprayed.

After spraying, the cups were inverted immediately and left to dry. Knockdown assessment was performed after 15 minutes, when the cups were returned to normal. The flies were then covered with a damp cotton swab to assess mortality and kept for 43 hours in a room at 25 ° C and 65% relative humidity.

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Table ^ continued)

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144 140 125 112 101 Compound No. 500 500 500 12.5 500 12.5 500 12.5 Consumption (parts per million) > H n a rt h O G Z o a o 'o kO o 5ί S O ^r 0 o kO o UI o Z 3 o n o o cn o z z cn n o o tn o o > z z: o o o 43 o cn > S n a o o O o o Z 03 rt O o o O o o Z C3 n o o o o o o c z rt < kO o o O cn C Lu cn < o CD irt rt λ rt o O crt rt O rt kO o o kO o crt a rt W _ o o o Ml , JC

Table (continued)

Table (continued)

M U 2 ' o O CO K D 03 o o σ o σ Cl. Oh to Oh o o o Lf) Cl. p-, to O> o O o LD > O K OI o o 0> to > CK E OI o σ p o o C U CO 23 o o o o o O ether Z o o o o o Q C? r < o o o o o o tz 23 rt3 o o σ o o O U 23 23 o O ia U u Z in σ o o σ o. o 2 S o o LT) o σ> TU NG o O O F U? o D U F rtT o Consumption (parts per million) m o · O CM m r-i in o · O CM LO r —i o o LT) o o m o o ID Compound No. CM m r-1 ro LT) r-l r- LO r * H co m fH cn LA F "<

177 1 1 176 175 M -U 160 Compound No. 500 12.5 1 i 500 12.5 1 i 500 12.5 tn M O • O tn 500 12.5 - cn Ii c Q) <. (- ¹ Ini • n \ rt 3 0 H · LJ. To-r · H- • 3 - ftl ω H f: C TU EO 2 H O G o o o o ui 'V —9 O '0 o o o o o 2 2 O fl o o o o o 2 2 tn o ui LO o LO 10 P 2 π σ o kO tn LO O > \ s. n a o o o o O 2 CO Λ O o o o tn o 2 tO n o o o o o o X X X < o o o LO o n to ιΩ < χ ω Λ X r · m O Ό ui o tn LO o χ σ ta to o o 1 o O o <2 2 n y

Table (continued)

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Claims (7)

DEFINITION OF INVENTION A compound of formula (I): io and stereoisomers thereof, wherein A is hydrogen, halo, hydroxy, C, _ ₄ alkyl, C ^ alkoxy, C- ^ halogenalki las C ^ _ jhalogenalkoksi C _n _ _Λ alkylcarbonyl, C _ _{n d} alkoxycarbonyl, phenoxy , nitro or cyano; 1.2 R and R, which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted cyclo + r * alkyl, optionally substituted heterocyclylalkyl, optionally substituted cycloalkylalkyl, optionally substituted aralkyl, optionally substituted heteroarylalkyl, optionally substituted aryloxyalkyl, optionally substituted heteroaryl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted aryloxy, optionally substituted heteroaryloxy, nitro, nalogen, cyano, -NR R, -CO ₉ R ~, -CONR R, 3 3 3 -COR ', -S (0) R where n is 0, 1 or 2, (CH_) P0 (0R)' where n · * z m 2, 1. 2 m is 0 or 1, or R and R are joined to form a carbocyclic or heterocyclic ring system; 3. 4. . _. . R and R, which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted aralkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, or optionally substituted heteroaryl-. 2. A compound according to claim 1 wherein A is hydrogen, halogen, hydroxy, ethoxy, trifluoromethyl, trifluoromethoxy, C _1-2 alkylcarbonyl, C _1-2 alkoxycarbonyl, phenoxy, nitro or cyano; R ^ is C ^ _ ^ alkyl, halo (C) alkyl, C ^^ alkoxy, halo (_ ₄₎ alkoxy, alkylcarbonyl, C ^ _ ₄ alkoxycarbonyl, cyano, phenyl () s kilas, phenyl, five or six membered aromatic hetero rociklas It is containing one or more oxygen, nitrogen or sulfur atoms and which is optionally fused with a benzene ring, in addition to any of the above oakaitų aromatic or heteroaromatic moieties are optionally substituted with one or more substituents selected from halo, hydroxy, C ₁ _ _{/ J} alkyl, halo (C) alkyl, C ^ _ ₄ alkoxy, halo (C) alkoxy, alkylcarbonyl, C ^ _ ^ alkoxycarbonyl, nitro, cyano, phenyl, phenoxy, benzyl or benzrloksi; and R is hydrogen, halogen, C ₁ _ ₄ alkyl, halo (C-I__ ,,) alkyl, C ₃ _ ^ 1 2 alkilkarboni las C ₄ alkoxycarbonyl, cyano or phenyl; or R and R are joined together to form a CL_ ^ _n carbocyclic ring system. 3. The compound of claim 1, characterized in that A is hydrogen or halogen, R ^ is C ₁ ^ alkyl, benzyl, C ^ _ ₄ alkylcarbonyl, C ^ _ ₄ alkoxycarbonyl, cyano, phenyl, thienyl, triazolyl, thiazolyl, piricilas , Piriri dinilas, pyrazinyl, triazinyl, quinolinyl, or chinok salinilas, in addition to any of the preceding radicals flavoring and the heteroaromatic moieties are optionally substituted with one or more substituents selected from halo, C ^ _ ^ alkyl, trifluoromethyl, Cy_ _z alkoxy , trifluoromethoxy, nitro, cyano, phenyl or benzyloxy; R is hydrogen, C ^ _ ^ Alk · las alkylcarbonyl, C _ _d alkoxycarbonyl, cyano or phenyl; 1 1 7 proves R r are joined together through ciklooentilinį _z ~ or ba cikloheksilinį ring, usually with a fused benzene ring. Process for the preparation of a compound according to claim 1, characterized in that the compound of formula (II) CH _? X where A has the meanings given in claim 1 and X is a leaving group, is affected by the oxime salt of formula (111) _r 2 ho.n =: Where R and R have the meanings given in point 1, in the base! terms. Process for the preparation of compounds according to claim 1, characterized in that (a) Compound of Formula (IX): affects the formulaCK ^ Link; or (b) separating the methanolic elements from the compound of formula (IV): CH (OCH ₃ >, in acidic or basic conditions; or c) a ketoester of formula (XI): i. 1.2 affects: with methoxymethyleninin reagent; where A, R and R have _v . In the 5 values defined in claim 1, L is a leaving group and R is a metal atom. 6. Fungicidal, insecticidal or miticidal composition, h? s is an active ingredient as defined in claim 1 and a fungicidally acceptable carrier, wherein the ingredient is a compound, disks, insecticides or diluent. A method of controlling fungi, eradicating or controlling insects or mites, comprising treating the plants, plant seeds, insects or mites or their distribution sites with a compound according to claim 1 in a fungicidal, insecticidal or micro-effective amount.